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Application of numerical methods in analysis of fixed bed adsorption fractionation.

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Application of numerical methods in analysis of fixed bed adsorption fractionation.
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Johnson, Adrain Earl Jr.
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Gainesville, Fla.
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University of Florida
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Adsorbents ( jstor )
Adsorption ( jstor )
Fractionation ( jstor )
Gels ( jstor )
Liquid phases ( jstor )
Liquids ( jstor )
Mass transfer ( jstor )
Phase diagrams ( jstor )
Silica gel ( jstor )
Velocity ( jstor )

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University of Florida
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Copyright Adrain Earl Johnson Jr. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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APPLICATION OF NUMERICAL METHODS

IN ANALYSIS OF FIXED

BED ADSORPTION FRACTIONATION












By

ADRAIN EARL JOHN SON, JR.


A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY













UNIVERSITY OF FLORIDA
February, 1958














ACKNOWLEDGEM1EETS


The author wishes to express his deep appreciation and sincere thanks to Professor R. D. Walker, Jr., for his encouragement, interest, and many suggestions during the course of this investigation; to Mr. Carlis Taylor of the University of Florida Statistical Laboratory for his very valuable help in the preparation of the computer program and in the obtaining of the computer solutions; to Dr. H. A. Meyer for authorizing the use of the facilities of the Statistical Laboratory and Computing Center for this work; to Dr. Mack Tyner, Dr. T. M. Reed, Dr. E. E. Muschlitz, and Dr. R...W. Cowan, of the graduate committee, for their helpful suggestions and criticisms; to the faculty and graduate students of the Department of Chemical Engineering for their cooperation and interest; and to his wife for the assistance and unwavering support which she has given.


ii














TABLE OF CONTENTS

Page

ACKNOWLEDGEMENTS......................................... i

LIST OF TABLES............................................. V

LIST OF ILLUSTRATIONS..................................... vii

I. INTRODUCTION .......................................1

II. BACKGROUND....................................... .3

III. PREVIOUS WORK..................................... 6

IV. THEORY........................................... 16

A. The Fixed Bed Binary Liquid Adsorption
Process ...........................16
B. Derivation of Eqain............21
C. The Dimensionless Parameters H and T .........24
D. Boundary Conditions for the Liquid Phase
Fixed Bed Process............................ 26

V. NUMERICAL ANALYSIS............................... 29

A. Numerical Methods............................ 29
B. Description of Integration Procedure .........32 C. Computer Program............................. 37

VI. RESULTS OF CALCULATIONS.......................... 40

A. Problem Solutions ...................40
B. The Asymptotic or Ultimate Adsoption Wave. 43
C. The Shape of the Asymptotic Wave ..............48
D. Computation of HETS From Fixed Bed Data 52

VII. EXPERIMENTAL..................................... 56

A. Adsorbent.................................... 56
B. Adsorbates .....................................56
C. Experimental Procedures...................... 57


iii











TABLE OF CONTENTS (Continued)


Page

VIII. COMPARISONS BETWEEN EXPERIMENTAL AND CALCULATED RESULTS............................... 62

A. Adsorption Fractionation Experiments of
Lombardo..................................... 63
B. Toluene-Methylcyclohexane Fractionation
on Silica Gel................................ 64
C. Toluene-Methylcyclohexane Adsorption on
Activated Alumina .......................67
D. Use of Constant-Alpha Type Equiibriu~m
Diagram...................................... 68
E. HETS of Column Packing....................... 69
F. Discussion of Calculations................... 71
G. Discussion of Intraparticle Diffusional
Resistance................................... 72

IX. CONCLUSIONS...................................... 75

X. LIST OF SYMBOLS.................................. 131

X1. LITERATURE CITED................................. 133

APPENDIX. - IBM 650 COMPUTER PROGRAM FOR SOLVING
ADSORPTION FRACTIONATION EQUATIONS ...................139

BIOGRAPHICAL SKETCH....................................... 173


iv














LIST OF TABLES


Table Page

1. Numerical Integration Formulae...................... 77

2. Summary of Adsorption Fra ctionation Calculations 78 3. Determination of Specific Pore Volumes ..............80

4. Adsorption Equilibrium Data for Toluene-Methylcyclohexane on Davison 6-12 Mesh Silica Gel .........81

5. Adsorption Equilibrium Data for Toluene-Methylcyclohexane on Alcoa 8-14 Mesh Activated Alumina.. 82

6. Adsorption Equilibrium Data for Benzene-NHexane on Davison "Thru 200"1 Mesh Silica Gel ........83

7. Summary of Fractionation Experiments ................84

8. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel....................... 86

9. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel........................ 87

10. Toluene-Methylcyclohexane Fractionation on Davison 6-12 Mesh Silica Gel.............................. 88

11. Toluene-Methylcyclohexane Fractionation on Davison 6-12 Mesh Silica Gel........................ 89

12. Toluene-Methylcyclohexane Fractionation on Davison 6-12 Mesh Silica Gel........................90o

13. Toluene-Methylcyclohexane Fractionation on Davison 6-12 Mesh Silica Gel........................ 91

14. Toluene-Methylcyclohexane Fractionation on Davison 6-12 Mesh Silica Gel........................ 92

15. Toluene-Methylcyclohexane Fractionation on Davison 6-12 Mesh Silica Gel........................ 93


V












LIST OF TABLES (Continued


Table Page

16. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel...................... 94

17. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina ..................95

18. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina ..................96

19. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina ..................97

20. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina ..................98

21. Toluene-Mechylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina ..................99

2.Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina .................100

23. Benzene-N-Hexane Fractionation on Davison
"Thru 200"1 Mesh Silica Gel........................ 101

24. Benzene-N-Hexane Fractionation on Davison
"Thru 20011 Mesh Silica Gel........................ 102

25. Benzene-N-Hexane Fractionation on Davison
"Thru 2001' Mesh Silica Gel.......... ............ 103

26. Calibration of Refractometer for MCH-Toluene
Solutions at 300C.......................... ...... 104


vi













LIST OF ILLUSTRATIONS


Figure Page

1. Flow Diagram of Computer Program ..................105

2. Liquid Phase Composition History, Computer
Solution to Problem 1............................. 106

3. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 1............................ 107
4. Liquid Phase Composition History, Computer
Solution to Problem 9............................. 108

5. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 9............................. 109
6. Liquid Phase Composition History, Computer
Solution to Problem 51............................ 110

7. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 51............................ 111
8. Liquid Phase Composition History, Computer
Solution to Problem 52............................ 112

9. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 52............................ 113
10. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 52............................ 114

11. Liquid Phase Composition History, Computer
Solution to Problem 99............................ 115

12. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 99............................ 116

13. Adsorption Equilibrium Diagram for MCH-Toluene
on Davison 6-12 Mesh Silica Gel ...................117

14. Adsorption Equilibrium Diagram for MCH-Toluene
on Alcoa 8-14 Mesh Activated Alumina ..............118


vii











LIST OF ILLUSTRATIONS (Continued)


Figure Page

15. Adsorption Equilibrium Diagram for BenzeneHexane on Davison Y!Thru 200" Mesh Silica Gel 119

16. Benzene-Hexane Fractionation With Silica Gel 120 17. Benzene-Hexane Fractionation With Silica Gel 121 18. Benzene-Hexane Fractionation With Silica Gel 122 19. MCH-Toluene Fractionation With Silica Gel .........123

20. MCH-Toluene Fractionation With Silica Gel .........124

21. MCH-Toluene Fractionation With Silica Gel .........125

22. MCH-Toluene Fractionation With Alumina ............126

23. MCH-Toluene Fractionation With Alumina ............127

24. Effect of Liquid Velocity on Overall Mass
Transfer Coefficient............. ................ 128
25. Effect of Liquid Velocity on HETS.. ...............129

26. Calibration of Refractometer for MCH-Toluene
Solutions........................................ 130


viii














1. INTRODUCTION


This dissertation describes the results of a study made on the process of adsorption fractionation of binary liquid solutions. Based on a theoretical analysis of the factors controlling the process, mathematical partial differential equations expressing column operation were derived and solved by numerical integration with the aid of an IBM 650 digital computer. Particular emphasis was placed upon the statement of the boundary conditions for the liquid adsorption process, as it is believed that the proper boundary conditions have not been used in previous work.

Computed solutions to column operation were compared with experimental data taken in this study and with other published data. It was found that good agreement between calculated and experimental data may be obtained in systems in which the external particle film resistance to diffusion apparently controls. Agreement in cases where intraparticle diffusion contributes to the total diffusional resistance is not as good, but is considered useful. The success with the external film controlling case indicates that when a suitable theory on intraparticle resistance is derived, numerical integration by means of a computer will prove the best means of obtaining satisfactory solutions,


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because of the apparent impossibility of obtaining analytical solutions to the equations.

It was found that, through a fortuitous circumstance, computer solutions based on constant-alpha type equilibrium diagrams fit the data for the case of intraparticle diffusion contributing more closely than solutions using the actual equilibrium diagram of the system.

In the course of this work equations were developed for determining the rate of advance and the shape of the ultimate adsorption wave, which is formed in columns of sufficient length. In addition, a method was developed for evaluating the height of an equilibrium stage (lIFTS) in an adsorbent bed from data of fixed bed adsorption fractionation experiments. The determination of HETS is of importance in the design of continuous countercurrent adsorption columns.

This work also included the development of a comnputer program for solving the partial differential equations. The resulting program and a brief description of the numerical methods used are presented.















Il. BACKGROUND


Historically, the most frequently encountered problem in the chemical and related industries has been the necessity of separating relatively pure materials from mixtures of. two or more components, thereby producing either finished products for sale or intermediate products to be further processed. One portion of chemical engineering science, the unit operations, is devoted entirely to the study of the various methods for separating materials.

Research in the unit operations is usually aimed

either at the development of new, more economical, or more exacting separation methods, or at the development of more precise theories and formulae for expressing the phenomena of the known methods so that they may be put to better use. In the past decade, a new tool has been made available which can help the scientist and engineer to investigate mathematical theories and methods in a manner undreamed of twenty years ago. This tool is the high speed electronic computer, digital or analog. Such machines have many capabilities, but one of the most important to technical research is their ability to solve complicated mathematical equations, both algebraic and differential, which are otherwise insoluble.

In the past, many a theorist has been forced to

abandon a set of equations which he believed might express a

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phenomenon because the solution to the equations could not be provided by the most expert mathematician; instead, the, theorist resolved the difficulty by making restricting assumptions about the process 'which simplified the equations and permitted a solution. Such solutions are quite useful in the design of a process, but they are always only approximations. Sometimes their use leads to serious and costly mistakes, not only in the design of industrial processes, but in the interpretationi of the phenomenon being investigated.

In June, 1957, an electronic digital computer, IBM type 650, was installed at the University of Florida Statistical Laboratory. This machine, with its auxiliary equipment, represents the beginnings of a computing center, which will be available to the University and the State on a basis similar to that of the other facilities of the Laboratory.

In anticipation of the installation of this computer, the subject research was initiated in the field of chemical engineering unit operations with the view of utilizing the computer for providing a solution to equations which promise to express a theory more precisely than previous treatments. The unit operation chosen for a study was adsorption, which is a relatively new entrant to the commercial field of largescale separation process. The 'Arosorb" (1) and "Hypersorption" (2, 60) processes for the separation of petroleum hydrocarbons are examples of commercial applications of









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adsorption.

The analysis of fixed bed liquid phase adsorption fractionation is complicated by the fact that it is inherently unsteady-state, or transient; partial differential equations are required to express the process behavior mathematically. The fixed bed adsorption fractionation process, being mathematically complex and hence in an early stage of treatment, wvas chosen for study with the dual purpose in mind of advancing the frontier of knowledge in this field and of demonstrating what the computer can mean to research.














III. PREVIOUS WORK


In this section, the progress in adsorption research is traced from the turn of the century to the present. In general only those publications which deal with multicomponent adsorption equilibria or rate of adsorption are discussed. However, any paper of unusual interest is also mentioned.


1900-1920

The early investigators concerned themselves with

the nature of adsorption and with the equilibrium relationships of various systems of adsorbate and adsorbent. Freundlich (3) proposed his now famous isotherm for correlating the adsorption data of many systems. He was an early exponent of the theory that adsorption is a surface phenomenon (4), (5), which was not altogether accepted by the scientists of his day. Travers (6) suggested that since adsorption depends upon temperature it should be considered a "solid solution" phenomenon; this was refuted, by Wohlers

(7), who concluded that chemical bonds must account for the process because the adsorbed material usually does not react normally. Michaelis and Rona (8) suggested that adsorption is caused by a lowering of the surface tension of the solvent by the adsorbent. Reychler (9) demonstrated that the

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Freundlich isotherm was compatible with his own chemical reaction theory; Duclaux (10) theorized that adsorption is a result of differences in temperature which exist in minute cavities of the solid, causing liquifaction. Many investigators, Geddes (11), Schmidt (12), Katz (13), Langmuir (14), Polanyi (15), Williams (16), proposed equations different from that of Freundlich. Some of these proposals were merely the result of curve fitting, but others, such as those made by Langmuir and Polanyi, were based on theories which adequately explain certain features of adsorption. By 1920,

when Polanyi introduced his equation, which utilized one "characteristic" curve to account for the adsorption of a vapor or gas under all conditions of temperature and pressure of a given system, it was generally recognized that adsorption may be explained by more than one theory, depending upon the system, and may involve physical forces, chemical forces, or a combination of both.

Theoretical analyses based on thermodynamic considerations became prevalent towards the last of this period; speculations concerning the heat of adsorption were made. Polanyi (17) discussed adsorption from the standpoint of the 3rd law, Langmuir (14) suggested that unbalanced crystal forces account for physical adsorption, Williams (18) derived an adsorption isostere equation from thermodynamic reasoning, Lamb and Coolidge (19) concluded that the total heat of ad-











sorption equals the heat of condensation plus the work of compression. Very little was done with liquid adsorbates; interest in vapor phase adsorption predominated. Gurvich

(20), however, noted that, on the same adsorbent and at their own vapor pressure, approximately equal volumes of various liquids were adsorbed.

One of the earliest investigations of the rate of adsorption was performed by Berzter in 1912 (21). As with most of the early studies, Berzter used a gas-air mixture, from which he adsorbed the gas onto activated charcoal. He fitted an empirical equation to his rate data without determining the significance of the factors. Other investigations of similar systems were made by Rakovskii (22), Gurvich (23), who discovered that subdivision of the adsorbent particles affected the rate of adsorption but not the adsorption equilibrium, Freundlich (24), Dietl (25), and Hernad

(26). Little was concluded from these studies except that the velocity of batch-type adsorption decreased as the adsorption progressed, and that diffusion might play a role in determining the rate.


1920-1930

The role of adsorption in catalysis was foreseen by Polanyi, who in 1921 showed in a theoretical paper (27) that adsorbents should by their nature accelerate chemical reactions, because of the reduction in the required activation









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energy upon adsorption. However, Kruyt (28) disagreed; he believed that adsorption should decrease the rate of reactions because of the immobility of the adsorbed molecules.

An important concept was developed by Mathews (29) who, in 1921, pointed out that the term adsorption should properly be used to describe a phenomenon in which the concentration of a substance tends to be different at the interface between two phases from the concentration in the main body of either phase, thus broadening the scope of adsorption..

A typical early paper on kinetics was published by Ilin (30), who proposed that the rate of adsorption of a

constituent from a gas in a batch process is proportional to e-kt. Such a relation, although it may fit a set of data, sheds little light on the factors which determine the instantaneous rate of adsorption.

During the late 1920's interest was aroused in the

equilibrium relationships for a system in which the adsorbate contains more than one component attracted by the adsorbent. Levy (31), and Klosky (32) submitted equations for correlating such data. These studies probably suggested the concept that adsorption could be used to fractionate binary mixtures. 1930-1940

Additional equations for correlating the kinetics of batch adsorption were proposed by Tolloizko (33), Constable









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(34), Kondrashon (35), Ilin (36), Rogenskei (37), and Crespi (38, 39), most of which were still rather empirical. The idea that the rate depends upon the approach to the equilibrium condition was appearing in various mathematical forms in most of this work. A few workers began to consider the kinetics as similar to those of chemical reactions, requiring activation energies, etc. Taylor (40) approached the subject in this manner; but Nizovkin (41) decided that diffusion of the gases controls the entire process. Crespi

(42) derived a rate equation from Langmuir and Freundlich isotherms which was also of the chemical kinetics type.

Laer Damkohler (43) showed that the Langmuir derived equation applies only where establishment of the equilibrium takes 10-5 seconds, otherwise diffusion of the material to the adsorption site is controlling.

Brunauer, Emmett, and Teller published their important paper which dealt with the derivation of adsorption isotherms on the assumption that condensation forces are responsible for multimolecular layer adsorption (44). Statistical mechanical approaches to the explanation of adsorption equilibrium were presented by Wilkins (45) and Kimball

(46). Experimental studies of adsorption from binary liquid solutions were performed by Ruff (47), Jones, et. al. (48), and Kane and Jatkar (49).









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1940-1950

In 1940 Drunauer, Deming, and Teller (50) combined the recognized five types of vapor isotherms into one equation.

One of the first papers dealing with the kinetics of adsorption in a column was that of Wilson (51) who developed equations assuming instantaneous equilibrium, no void space between particles, and a single adsorbed component. This paper showed mathematically the existence of an adsorption band which moves through the adsorbent column, and thus qualititatively agreed with known facts. Martin and Synge

(52) pointed out the analogy between a moving bed adsorption column and distillation. Mathematical equations were developed, for the steady state case to compute the number of equilibrium stages required for a given separation.

DeVault (53) extended the work of Wilson by developing differential equations and their solutions for single solute adsorption which considered the void space between particles. Differential equations for multiple solutes were derived but not solved. There wvas reasonable agreement with selected previously published data.

Thomas (54) proposed a kinetic theory which leads to a Langmuir type isotherm at equilibrium. The adsorption step was assumed to control with no diffusional resistance. Solutions for the case of multiple solutes were impossible.









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Amundsen in his first paper on the mathematics of bed adsorption (55) developed differential equations based on the assumptions of irreversible adsorption and a rate proportional to the concentration of the adsorbate in the gas stream and to the approach to equilibrium on the adsorbent. In a later paper he took into account the desorption pressure exerted. by the adsorbate.

In 1947 Hougen and Marshall (56) developed methods for calculating relations between time, position, temperature, and concentration, in both gas and solid phase in a fixed, bed, with the restriction that the adsorption isotherms be linear. Analytical solutions of the partial differential

equations were obtained and plots of the solutions were made.

The interest in multicomponent adsorption equilibria grew rapidly in the late 1940's. Many papers were published for both gases and liquids showing isotherms for various experimentally investigated systems, and various modifications of the Brunauer, Emmett, and Teller isotherms were proposed. Such papers were authored by Wieke (57), Mair (58), Arnold (59), Spengler and Kaenker (61), Lewis and Gilliland

(62), and Eagle and Scott (63). Industrial applications were described by Berg (60), who explained the Hypersorption process for separation of light hydrocarbons, and by Weiss

(64).









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1950 to Present

Since 1950 the mathematics of adsorption kinetics

have been even more intensively investigated. Amundsen and Kasten (65, 66) have continued to approach the problem analytically, mainly in the field of ion exchange, which is closely related, but also in the field of adsorption. They developed very complicated analytical solutions to the adsorption of gases in fluidized beds, assuming intraparticle diffusion controlling and/or the adsorption process itself controlling, but still restricting the equilibrium relations to straight lines.

Eagle and Scott (63) presented extensive data for

equilibria of binary liquid systems and some batch kinetic data, which permitted the evaluation of apparent diffusivities within the particles of adsorbent.

Mair (67) treated fixed bed adsorption fractionation as a distillation process, and developed design equations utilizing a theoretical stage concept. Experimental results were given for separation factors and for HETS.

Kasten and Amundsen (68) showed that in liquid

systems the rate is most often controlled by the diffusional process instead of the adsorption process. They also developed equations based on mass transfer and intraparticle diffusion for a gas-solid moving bed adsorber, for the case of one adsorbate, or multiple adsorbates assuming individual isotherms for each. The effects of fluid phase resistance,










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intraparticle diffusion, and adsorption resistance, on the solution of the bed height required were shown.

Iliester (69) considered the performance of ion

exchange and adsorption columns mathematically. Approximate solutions of mass transfer differential equations were given which can be used to predict column behavior.

J. B. Rosen (70) published a solution of the general problem of transient behavior of a linear fixed-bed system when the rate is determined by liquid film and particle diffusion.

Gilliland and Baddour (71) considered the kinetics

of ion exchange, wherein an overall coefficient representing all resistances to transfer was used successfully, and presented a solution to the partial differential equations previously derived by Thomas. This is an isolated instance where the equilibrium equation used was not restricted to a straight line. Experimental data correlated very well, so that use of experimentally determined rate constants predicted the elution curves of other experiments satisfactorily.

Lombardo (72) considered the problem of binary

liquid adsorption fractionation from the pseudo-theoretical stage standpoint, and obtained solutions to the stepwise equations which he proposed by means of a card programmed calculator.










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Hirschler and Mertes (1) performed experiments batchwise, similar to those of Eagle and Scott for liquid phase binary adsorption. Internal diffusivities were computed from the data.

Lapidus and Rosen (73), considering ion exchange, developed equations similar to adsorption fractionation equations, using a lumped resistance, and were able to show that an asymptotic solution usually exists. Solutions to the asymptotic equation were obtained with a Langmuir type isotherm.














IV. THEORY


It can be seen from the foregoing literature survey that there has been some very creditable work done towards the mathematical treatment of adsorption and ion exchange kinetics, especially in recent years. Nevertheless, it appears that there are enough variations in the different phenomena of vapor phase adsorption, ion exchange, and liquid phase adsorption to warrant a treatment based specifically on the system being considered. The electronic computer is best suited for individual treatment of a difficult problem, since the results obtained by computer analysis are in the form of numerical answers to the specific problem with particular boundary conditions. To obtain general answers comparable to an analytical solution, it is necessary to run the problem repeatedly on the computer, varying the parameters and boundary conditions each time, until enough answers are computed to permit the drawing of graphs and curves which present the desired coverage of the variables. A. The Fixed Bed Binary Liquid Adsorption Process


The basic assumptions made to define the fixed bed

fractionation of a binary liquid are described below. These are the conditions on which the calculations made in this study were based. The following discussion points out the

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-.17

conditions which are peculiar to the liquid phase process.

1. A constant composition feed liquid consisting only of the two completely miscible components A and B, is fed at a constant rate into a column of solid adsorbent. The selectivity of the adsorbent results in a gradual removal of A from the liquid as it travels through the bed.

2. The velocity profile of the liquid flowing through the column is assumed to be rod-like. [To promote this condition experimentally, especially at the liquid front during the filling of the bed, the liquid was fed through the adsorbent column from bottom to top.]

3. The adsorbent is initially free of adsorbate liquid.

4. Equal volumes of pure A, pure B, or any mixture of the two are adsorbed per unit of adsorbent; i.e. the pore volume of the adsorbent is the same for both A and B.

5. Mixtures of A and B are volumetrically additive.

6. The activation energy of the adsorption process at the surface of the adsorbent is considered small enough to permit the diffusion process to control the rate of adsorption. 7. The combined resistance to diffusion, consisting of both the external surface film and an intraparticle resistance,. is considered together as one diffusional resistance, expressible in the usual manner of the mass transfer "film" theory.

Items 1 and 2 above are standard with the fixed bed adsorption process. The development of the theory has not









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progressed to the point that a better account of the velocity profile of a fluid in a fixed bed can be made. This is an item which could conceivably be included in a computer analysis when a suitable fluid flow theory is available.

Item 3 is a deceivingly simple statement which needs further discussion. In the gas phase process, which is used as a model by almost every published paper on adsorption fractionation, the bed is initially free of adsorbate, but contains inert gas or carrier vapor. Since the bed is initially already full of fluid, there is little effect of the adsorption process upon the quantity of fluid flowing while the bed is filling. The mathematical boundary conditions used to express this case state that when the feed fluid reaches a given position in the bed the quantity of adsorbate on the adsorbent is zero. In addition, the time required for the fluid to reach a bed point is that required to push the original gas out of the void space between the adsorbent particles. Neither of these conditions is typical of binary liquid adsorption. First, the time required to fill the bed to a given point is that required to fill the void space and the pore volume of the adsorbent bed to that point. Secondly, the composition of the liquid on the adsorbent at the foremost point of liquid penetration into the bed continually changes as the filling "front" progresses. In a sufficiently long bed, the composition eventually










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becomes zero with respect to component A, the more strongly adsorbed component , but the length of bed required to arrive at this condition is of importance. To the author's knowledge, no treatment of the liquid phase process to date has considered either of these two points. As will be seen later, the development of the boundary conditions accurately describing the binary liquid adsorption case is involved.

Item 4 has been shown to be true of liquid phase

adsorption in a great many instances , and is usually assumed. It is particularly true of members of homologous series and otherwise chemically related compounds. As a consequence of item 4, it is generally convenient to assume item 5 also, thus permitting compositions to be expressed in volume fractions rather than mole fractions.

Although some investigators continue to use a chemical kinetics type of rate equation, it is generally accepted that, as stated in item 6, diffusion controls liquid phase adsorption processes.

The manner in which the diffusion is taken into

account is a topic of considerable interest. As stated in item 7 the subject treatment assumes that the external and intraparticle resistance can be lumped together as one overall resistance. This admittedly is not as precise a theory as desired; however, other investigators have not devised. a theory .of intraparticle diffusion for liquid adsorption which is acceptable to the author, nor has the author. One con-









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trolling factor in this study was the limitation of the storage capacity of the IBM 650 computer. It was found that over 60 per cent of the machine capacity was required to store the "program," the sequence of instructions which the machine follows to solve the problem. The remaining storage was not sufficient to permit the addition of a third independent variable, particle radius, to the other two, time and bed depth. It would have been necessary to include particle radius if intraparticle diffusion were treated as a separate item. The required storage is available on larger computers, however. Based on the results of the computations of this study, it now appears that particle radius might have been handled with the IBM 650, if the ranges covered by the other two variables, time and bed depth, were suitably restricted.

All analytical solutions which have been published to date have of necessity each been based on a particular form of the adsorption equilibrium relationship, which expresses the relation between x, the composition of the unadsorbed liquid phase, and y, the composition of the adsorbent-free adsorbed phase. This diagram is similar in appearance to the usual vapor-liquid equilibrium diagram. Because of the extreme difficulty in solving the equations, most have assumed a straight line relationship, which is strictly applicable only to dilute gas phase adsorption.









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The Langmuir equation, (y =x/a+bx) has been used for an approximate solution, assuming chemical kinetics to be the controlling rate. Neither of these forms expresses satisfactorily the equilibrium of liquid phase adsorption over a very wide range. In fact, usually no one algebraic expression fits adsorption equilibria over the complete diagram. It is quite often necessary to fit two or more algebraic expressions to liquid phase adsorption equilibrium data. Because of this an analytical solution cannot be generally applicable to different systems. Moreover, an analytical solution is very complex, even when based on the simplest straight line equilibrium relation. The computation of the infinite series which usually result in analytical solutions could easily require a computer. It ks of importance that a computer solution can be obtained no matter how complex the equilibrium relationship, thus "tailoring" the solution to the particular system under study, and thereby removing a basis for conjecture when comparing the calculated solution with the experimental results.


B. Derivation of Equations


A material balance (using volume fraction compositions) for component A, the more strongly adsorbed component, can be made over a differential section of the adsorption bed. Equating the loss from the fluid stream to the gain by the









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adsorbed and unadsorbed phases,

!(QX1
- [Lde dLdO + AdLde [fv(6X/6o)L + PbVp(6y/6e)L-, rearranging gives:

O6x/A3)e + (Afv/9)(6x/6e)L -(PbVpA/Q)O6y/be)L (1)


which is the equation of continuity written in volume fractions.

The classical mass transfer rate equation for diffusion of component A between phase 1 and 2 across a film whose area per unit volume of bed is unknown is, rA =K La (CA1 .- CA2)

for equimolar countercurrent diffusion of components A and B.

It is assumed that the conditions of equimolar

countercurrent diffusion are approximated closely enough by the adsorption process, in which component B is displaced by component A, to permit this form of mass transfer equation to be used. The coefficient, KLa, is assumed to remain constant as CA varies. Thermodynamically, it is possible that the coefficient, K a would be more constant if based upon activities instead of molar concentrations; use of the above equation may assume ideal solutions. If such is true, a further refinement would be to include the activity coefficient in the above relation.

Writing the mass transfer rate equation for a differential section of an adsorption bed,









-23-


KLa (CA - CA *) (AdLde) -(PbvpA/vm)(6Y/60)L(dLde)


Here, CA represents the composition of the unadsorbed bulk liquid phase, and CA* i's the composition of the liquid phase which is in equilibrium with the adsorbed phase. Note the assumption that the resistance of the adsorption process itself is negligible, so that CA * may be used in the above equation.

Rearrangement gives:

CA - C A* (PbVp/KLaVm) (6y/00)L


but by definition CA -x/Vm substitution for CA gives:

x- x* =(PbVp/KLa)(6y/6e)L (2)


Equations (1) and (2), with the equilibrium x-y

relation for the system under consideration, represent the mathematical problem to be solved, given suitable boundary conditions.

Before attempting a solution, it is desirable to

transform equations (1) and (2) into a dimensionless form so that a solution using a particular equilibrium relation will be as general as possible, thereby permitting evaluation of the solution without prior knowledge of such parameters as fv PbP Vi,, Q, A, and KLa. To effect such a transformation, two new independent variables are chosen:









-24

Let T - (KLa/pbVP ) [i0 - (Af,/Q)(L)l (3)

and H - (KLaA/Q)(L) (4)

The resulting transformation equations are,

(Y6y/d)1, (6y/6T)H(KLa/PbVV)

O ~ (x/60) (x'T)H(KLa/PbV,)

(Ox/cL)e =-(AfVKLa/QPbV )ix/6T)H + (KLaA/Q)Qbx/6H)T Substitution of these relations into equations (1) and (2) gives,



x - x* (3y/6,T)H (6)

Equations (5) and (6) together with the x-y equilibrium relationship, express, in the desired dimensionless form, the mathematical relations which the adsorption process obeys, according to the assumptions listed originally. A solution of these equations, based on the proper boundary conditions, should be correlatable with experimental data. It should. be noted that all of the physical properties involved in def ining H and T are readily measured experimentally except KLa. The evaluation of K a must hinge upon the matching of the calculated solution with experimental data. C. The Dimensionless Parameters H and T


It is important to the statement of the boundary conditions and to the understanding of the results of the calculation that the physical significance of the dimensionless parameters, H and T, be understood. Multiplication of










-25

both sides of equations (3) and (4) by (pbVp/KLa) gives,

(PbVIJ/KLa)(T) - 0 - (Afv/Q)(L) (7)

(PbVp/KLa)(H) =(4bVp/Q)(L) (8)
The net dimension of both sides of equations (7) and

(8) is time. A study of the right hand side of these equations will reveal the following interpretation of T and H.

The parameter T is proportional to the actual time elapsed since introducing feed liquid into the adsorption bed in excess of that which is required to fill the void volume of the bed to point L by the feed flow rate Q.

The parameter H is proportional to the time that

would be required to fill the adsorbed phase volume of the bed to point L by the feed flow rate Q. The proportionality constant is the same as the one for T.

An alternate way of expressing the above would be to state that T is proportional to the volume of liquid which has entered the bed in excess of that required to fill the void volume to point L, and H is proportional to the volume of liquid which is required to fill the adsorbed phase (pore) volume of the bed to point L.

Some reflection will show that for a given bed depth, L, if H - T, then the liquid front has just reached point L and both the void and pore volumes of the bed are filled to the point L.









1 -26D. Boundary Conditions for the Liquid
Phase Fixed Bed Process

Inspection of equations (5) and (6) shows that there are two dependent variables, x and y, and two independent variables H and T. Only first order partial derivatives are present, suggesting that only two boundary conditions, one fixing x and one fixing y along two different axes, will suffice. Physically, it can be seen-that for a given bed and given flow rate, the inlet feed composition and the initial condition of the bed determine the resulting column operation. Since the properties of the bed, the flow rate, etc., are contained 'within H and T, they need not be considered mathematically.

The condition of constant inlet feed composition corresponds to the condition that at L =0

x -xp, for all 0 > 0

This is easily converted to the dimensionless system by the condition

at H =O

x -xF, for all T > 0

In other papers, the second boundary condition has been met by considering that at T -0 y -0, for all H > 0

which is equivalent to the physical case of a bed saturated at 0 -0 with a liquid of composition pure B. This would insure that y -0 initially, and that when the feed liquid










-27

front arrives at point L by pushing out the liquid in the void volume of the bed, the composition, y, of the liquid on the adsorbent is zero. This, however, is not the case for an initially dry bed.

For the initially dry bed, it was seen above that the instant of filling corresponds to T =H. It then will suffice to state a boundary condition for y along the boundary T =H, if possible. Considering the physical problem, as a given adsorbent particle fills, there are two extreme cases which may occur. The liquid phase and the adsorbed phase at the moment of filling may be in complete equilibrium, indicating that diffusion of components A and B happened more rapidly than the filling; or, the other extreme, the liquid phase and the adsorbed phase may be of the same composition at the moment of filling, indicating that the diffusion process is very slow compared to the rate of filling. In actual fact, it is of course probable that the physical process which occurs is somewhere between the two extremes, depending upon the filling rate. However, for lack of a better criterion, it is certainly more probable that in the majority of cases the diffusion rate. is quite slow compared to the filling rate. It has been shown (73) that each individual particle takes something on the order of one minute or more to come to equilibrium in batch experiments, and. the filling process, even in the smallest columns, is completed at the rate of


many, many particles per minute.









-28

The boundary condition chosen in this study, based on the above observations, is

for T H, all Tand allH_>O0 X y

which expresses mathematically that as each particle in the bed fills, the rate of diffusion of components A and B is negligible compared to the filling rate. Note that such a boundary condition is not easily applied when attempting an analytical solution to a set of equations, but, as will be seen in the description of the numerical method, it presented no insurmountable problem in computer analysis.














V. NUJMERICAL ANALYSIS


A. Numerical Methods


The general procedure for solving differential equations by means of numerical techniques is covered by many texts.

To solve a partial differential equation or equations, it is necessary to substitute, in effect, a set of simultaneous differential equations, which are integrated numerically and simultaneously by standard numerical techniques. The voluminous number of computations required and the quantity of numbers to keep track of during the integration make it imperative that the modern high speed computer be used when dealing with partial differential equations.

The adsorption problem can be demonstrated graphically in the following manner.


x


XFy

x - x(T,H)
__H





T/ \H-T


y


y XF

y - y (T, H)
H


F



y
H-T


-29-









-30

The two sketches portray the three dimensional picture of the desired relationships. The surface, x -x(TH) and the surface y =y(T,H) represent the functions which satisfy the partial differential equation and its boundary conditions. Along the boundary H = 0, x is shown to be constant, xFj the feed composition. Also along this boundary, y increases from xF, its initial value as the first drop fills the first section of the column, to YF *,the value in equilibrium with the feed. Along the boundary H =T, both the x and y surfaces follow the same curve, as prescribed by the second boundary condition. The general shape of the curve is known before hand, but the actual boundary condition is merely that x =y. The values of the two function between these two boundaries make up the surfaces representing the solution to the problem.

A rectangular grid has been superposed at the base of the figures. This grid represents the finite values of H and T at which the numerical solution provides values of x and y. As the grid is made smaller the resulting numerical solution will approach the true solution very closely, but also many more points must be computed. In this problem, capacity was available in the computer to compute values for a grid composed of 200 T and 200 H points. From the sketch one can see that this would involve the computation of x and y for a total of 20,000 grid points each time the problem is worked. As the computer required about four seconds to










-31

compute each point, the computer time required would have been prohibitive, except that it was found unnecessary to compute all of the points. Since the physical problem is such that an adsorption "wave" is formed in both the liquid and adsorbed phases, and that this "wave" moves through the column, there are a great many points before and behind the wave whose composition is fixed. In front of the wave is a section of the column containing pure B, where both x and y are zero; behind the wave is a section of a column in which the liquid composition is XF and the adsorbed phase composition is YF ,the value in equilibrium with the feed liquid composition. In both of these sections no mass transfer takes place, and it is not necessary to compute changes in the values of x and y. This fact was incorporated into the computer "Program," and the computer did not bother to compute values for x and y outside of the wave itself. The criteria chosen for the wave boundaries were that a point was considered inside the wave whenever the compositions of the point immediately adjacent to it were such that either y > 0.00005 or xF-x > 0.00005. A check computation made without these restrictions revealed that the results of the solution were not affected within four significant figures, which was considered sufficient precision. This maneuver cut the computation time down to 5-10 hours per solution.









-32

B. Description of Integration Procedure

li + + +

- - -j1-2



1+2I



T


The numerical integration procedure can be described as follows:

Given the value of (x-,y)ij for a particular grid

point, (i,j), (see sketch above) within the desired H and T boundary, x - x* at this point may be computed from the equilibrium x - y relationship. From equations (5) and (6), p. 24, the partial derivatives (6x/5H)T and (6y/6T)H at (i,j) should equal -(x - x*) and ( x - x*), respectively. The value of x at the neighboring grid point (i+l,j) may be estimated by a suitable formula for numerical integration. The simplest formula is that used by Schmidt in heat transfer calculations, which consists of assuming that (b5x/c6H)T is constant between the point (i,j) and the point (i+lij). To put it more elegantly, a straight line may be fit over the AH increment from (i,j) to (i+l,j) utilizing the value of x and the slope, (86x/Z)H)T, both evaluated at (i,j). Similarly, the value of y at the grid point (i,j+l) may be









-33

computed by fitting a straight line over the AT increment from (ij) to (i,j+l) utilizing the slope Oy/6T)H and value of y at the point (i,j). However, this is the crudest of the numerical integration formulae. For the resulting solution to be even approximately close to the true solution, it is necessary to use very small AH and AT increments. If integration formulae be used which fit higher degree polynomials to the curve in the neighborhood of the point (i,j), the precision of the integration process is vastly improved, and much larger LH and AT increment sizes can be used.

It was decided, by trying alternate integration

formulae on the computer, that, to obtain the degree of precision required and yet cover a large range of the H and T variables with the 200 increments allotted, it would be necessary to use integration formulae which fit at least second degree polynomials to each integration step. The formulae used are listed in Table 1.

Formula number 1, which fits a second degree polynomial over two increments, was used to compute values of y at points corresponding to (i,j+l) in the sketch. This equation requires no trial and error. Formula number 2, which fits a third degree polynomial over two increments (thus requiring a trial and error solution) was used to compute values of x at points corresponding to (i+l,j) in the sketch. Two different formulae were u sed simply because it was









-34

impractical to fit a third degree equation in both directions, as a double trial and error procedure would have been required. Use of such a double trial and error procedure would have increased the computing time by a factor of about 20. It was, therefore, necessary to compute in one direction without a trial and error procedure, and the T direction was arbitrarily chosen.

The above discussion holds for the computation of all "normal"' interior points; however, for points near the boundaries T - 0 and T - H different formulae were required to maintain at least second degree precision for all calculations.

It is of interest to describe in detail the first few steps in the computation of a solution, so that an accurate picture of the manner in which the boundary conditions were applied may be seen. The procedure followed in starting a numerical integration is outlined below:
0 MH

1 2

31
6i7 9









H~ T
T









-35

1. Refer to the above sketch of the H and T axis with the superposed grid. At T - 0 and H - 0, both x and y were set equal to xF, the feed liquid composition. This corresponds to the condition that the first differential layer of particles in the column is filled with feed liquid in both void and pore volume.

2. The value of x for points 1, 3, 6, 10, etc., was'fixed equal to xF. This meets the boundary condition that x is always xF at the column inlet.

3. The value of y at grid number 1 was computed first, using integration formula number 3, Table 1. This formula fits by trial and error a second degree curve over one increment to the desired relationship that dy/dT - x - x* at constant H. The equilibrium relationship must of course be used to compute x* from values of y.

4. The value of both x and y at grid point 2 was computed next using integration formula number 4, since x -y along the H - T axis. This computation is also trial and error, fitting a second degree equation over one increment to the desired relationship that dx/dlI - -(x - x*) at constant T.

5. The value of y at point 3 was next computed using integration formula 5 which fits a third degree equation over two increments. All subsequent values of y along the H - 0 axis were computed by this formula.

6. The values of x and y at point 4 were next computed by trial and error simultaneously using formulae 4 and 6, which









-36

fit second degree equations over one time increment. Since it was desired to fit at least second degree equations in every integration step, the simultaneous calculation of x and y for this point was required.

7. The value of x and y (equal) for grid point 5 was computed using formula 2, which fits a third degree equation by trial and error over two time increments. All subsequent points along the H -T diagonal were calculated using this formula.

8. The value of y at point 7 was computed by formula 1, which fits a second degree equation over two time increments without trial and error. This is the first instance in which formula number 1, for a "normal" point, was used.

9. The value of y at point number 6 was computed by formula

5.

10. The value of x at point 7 was computed by formula 4, which fits a second degree equation by trial and error over one increment. All subsequent values of x along the H - tLH axis were computed by formula 4. 11. Values of x and y at point 8 were computed simultaneously in order to use at least second degree equation accuracy. Formulae 2 and, 3 were used, involving a double trial and error. All subsequent values of x and y along the diagonal neighboring the H - T diagonal were computed with these formulae. This is the only instance of double trial and error involved in this procedure.









-37

12. The value of x and y (equal) for grid point 9 was computed by formula 2.

13. Subsequent calculations proceeded, using formula 1 to compute values of y, and using formula 2 to compute values of x for all normal interior points. Points on and neighboring to the boundaries H - 0 and H - T were calculated as noted in steps 5, 7, 10, and 11. C. Computer Program


The development of a computer program to perform the computations described above was a tedious, drawn-out process rife with rewirites and changes in procedure. The IBM programming procedures first had to be learned, largely from the manuals available for this purpose, but with a good deal of help from the University of Florida Statistical Laboratory personnel. The specific programming method chosen was the IBM SOAP II method, developed for the Type 650 machine. The program itself is much too long and complicated to be discussed here, although a complete copy of the SOAP II program is included in the Appendix. The SOAP II procedure has the advantage that the program is listed in a symbolic code as well as the numerical machine code. The printed program also includes comments inserted specifically to help orient the operator as to the calculations being performed in each particular section of the program. In Figure 1 a "Flow Diagram" of the program is presented. It must suffice











to point out here that if the program as listed in the Appendix be punched into standard IBM cards according to the SOAP II format, and if the instructions accompanying the program be followed, any competent 650 operator could utilize this program to solve a binary liquid phase adsorption fractionation problem, limited, of course, to the basic assumption as to the mechanism involved on which the work was based. The program listed in the Appendix uses the alphatype equilibrium diagram familiar to distillation processes. To work a problem, it is necessary only to read the program into the Type 650, then to read in one "problem" card, which provides the information as to the feed composition, magnitude of alpha, size of the AT and 6Hl increment, and frequency desired in the punching of the answer cards. The computed answers are punched by the machine at pre-determined increments of AT, chosen arbitrarily for each problem on the problem card.

If it is desired to perform a calculation using the

equilibrium diagram of a specific system, as was done in this work, a sub-routine for computing x*~ from y must be added to the program listed here in such a way that it replaces the equilibrium diagram calculation of the listed program. Again, this is a fairly simple task for an experienced IBM programmer. The author will be glad to furnish additional information other than that given herein to enable any interested party to make use of the program. Although the development of the









-39

program represents some four to six months of intensive effort, it, like any other computer program, is now available for future use at any time.













VI. RESULTS OF CALCULATIONS


A. Problem Solutions


The numerical solution to the binary liquid adsorption fractionation problem was run twenty-three times on the IBM 650 computer. Each time the problem was solved, there were two parameters which were subject to change. These were the composition of the feed liquid, xF, and the shape of the x-y equilibrium diagram relating the composition of the adsorbed and unadsorbed phases at equilibrium. The latter parameter actually consists of one or more equations which express the x-y relationship over the range x =0 to x =1. These equations were included as a subroutine of the computer program, and to make a change it was merely necessary to place in the deck of program cards the proper subroutine deck for the x-y relationship desired.

The problems which were computed are summarized as to the parameters used in each solution in Table 2. Four of the solutions were run for comparison with experimental data of Lombardo (73) (Benzene-Hexane fractionation on Silica gel) and with experimental data of this study (TolueneMethylcyclohexane on Silica gel). The remaining solutions were run to provide a set of curves for use in evaluating the effect of the parameters on column operation. This latter

-40-










-41

group of nineteen solutions was based on a constant-alpha. type of equilibrium diagram as is used in correlating vaporliquid equilibria of distillation systems. In adsorption, alpha is defined exactly as in distillation: (y/]l-y) (1-x/x) -a~ Although adsorption equilibria seldom correlate perfectly with a constant alpha, this is one of the few algebraic formulae which approximate the general shape of' the adsorption x-y diagram over the complete range. It was believed that a set of solutions based on the constantalpha equation should prove useful in interpreting the effect on column performance of varying the two parameters, and it was hoped that solutions obtained with constant-alpha diagrams which approximate the experimental equilibrium data might be used successfully to predict column performance.

The answers to the solutions were punched by the computer onto standard IBM cards as they were calculated. Each card contained six answers plus identifying information., The six answers were actually three sets of x and y values corresponding to three bed grid points (H) at a given time increment (T. To provide enough answers to draw smooth curves through the points, it was not necessary to punch out x and y values for every one of the grid point intersections. In fact, this was not desirable at all, because the relative change in the values of x and y between adjacent grid points was quite small (in numerical integration this is a necessary prerequisite for accuracy). Usually the choice was to punch










-42

out answers for every tenth dimensionless time (T) increment. The entire adsorption wave was punched out at this time increment, but, as explained before, the constant composition sections in front of and following the wave were not punched.

The information from the cards was then printed in list form by means of an IBM 403 tabulating machine. From these lists of calculated data points, graphs of the solution were prepared. It was found that there were three graphs required to portray the information from each solution. On one, values of x, the liquid phase composition, were plotted against H, the dimensionless bed depth parameter, along lines of constant T, the dimensionless time parameter. A second plot was required to give the same information about Y, the adsorbed phase composition. A third plot was made of the ultimate, or asymptotic, wave shapes which are reached by the adsorption wave as it travels down the bed. Typical graphs of problem solutions are shown in Figures 2-11. Only those solutions referred to in this dissertation are shown. The tabulated data from which the graphs were computed were much too voluminous to include here. It is planned to compile the data and graphs for all of the twenty-three solutions under a separate cover for ready reference.

It was found that in every problem solution an ultimate wave shape was formed provided sufficient distance along









-.43

the bed depth parameter H was covered. Several authors have discussed the existence of the adsorption wave, and some have speculated upon the conditions or requirements that an ultimate or invariant shape be formed. The discovery that an invariant wave shape was formed in these problem solutions prompted a further analysis of the conditions necessary for its formation.


B. The Asymptotic or Ultimate Adsorption Wave


It is an experimental fact that if an adsorption

column is long enough (and if there is no adsorption azeotrope) eventually there will be set up three distinct zones which travel through the column. Refer to the following di agram.





zone one zone 3



0


*14
44 1

0
Bed Depth, L









-44

In zone 1, the adsorbent has preferentially adsorbed component A from the liquid phase passing over it until the composition of the adsorbed phase has reached yF *, the compo-. sition in equilibrium with the feed. When this occurs, there is no tendency for further eXchange of material between the two phases, and XF is also constant in zone 1. In zone 2, mass transfer is taking place, and the composition of both y and x vary 'with bed depth, L, and with time, e Zone 2 is the adsorption wave. However, the continual removal of component A from the liquid phase as it travels through the bed eventually becomes complete, and the composition of the liquid at the head of the wave becomes zero with respect to component A. Zone 3 represents the portion of the bed over which pure component B is passing. As in zone 1, there is no tendency for mass exchange between the phases and compositions are constant with e in this section. Remember, however, that all three zones are traveling through the column.

Although these three zones will be formed in any

adsorption fractionation experiment (with the exception of azeotropes), the questions of importance are (1) How soon will the three zones be formed? (2) What is the width of zone 2? (3) Does zone 2 reach an ultimate non-changing shape?

(4) If so, at what rate does zone 2 travel through the co lun?










-45

The numerical solutions obtained with the IBM 650

in this work provided the answers to these questions in each case investigated, but did not shed light upon other cases, e.g., equilibrium diagrams of different shape from those studied here. This, admittedly, is one of the main drawbacks to numerical solutions.

If one starts with the assumption that a zone 2 of

non-changing shape is formed, its velocity may be calculated. Since zone 3 is continually building up in length as the adsorption progresses, zone 2 must move through the column at a rate slower than the rate that the liquid passes through. Therefore, if we imagine a column in which the adsorbent is made to move in the opposite direction from the liquid, there is a certain rate of adsorbent movement which will cause zone 2 to remain stationary. There is, then, a countercurrent moving bed which is exactly analogous to the fixed bed operation. See the following diagram.
Countercurrent Case Fixed Bed Case
Zone 2 Stationary Zone 2 Moves

MO{ JXWO ~X-0





Zone Konel
22





Yx-xF Q
x~xF









-46

If Q is the volumetric flow rate of the liquid through the stationary bed, Q/Af is the velocity of the liquid through the bed void volu me. This velocity would have to be reduced by an amount equal to the velocity of travel of the adsorbent in the countercurrent case, in order to maintain the same relative velocity of fluid through the bed in the two cases. If W is the mass rate of flow of adsorbent required to maintain zone 2 stationary, W/pbA is the velocity of the adsorbent through the bed. Therefore, the countercurrent liquid feed velocity may be related to the fixed bed velocity.

Q1Av =Q/Afv -W/%bA(9 where Q' represents the volumetric liquid, feed rate in the countercurrent case. and Q represents the volumetric liquid feed rate in the fixed bed case. A volumetric material balance on component A about zone 2 for the countercurrent case gives, (WV P)YF* -(Q?) (xF) (10)

Substituting for Q1 from equation (9), (WVV)YF* -(Q - fvW/Pb)(xF) (11)

A little study will show that the velocity of the wave, Vw, when the liquid feed rate is Q, is equal to the velocity of the adsorbent bed required to maintain zone 2 stationary when the liquid feed rate is Q'. Solving equation (11) for W/pbA, the adsorbent bed velocity, gives,









-47-


VW W .0 xFf v (Q )(12)
PbA (XFf v + VpPbYF)(Qf)

Therefore, equation (12) above gives the velocity of the wave traveling through a bed, based on the assumption that a wave of invariant shape is formed.

It is desirable to transform this velocity into a velocity in terms of the dimensionless parameters H and T. VW may be considered as the ratio of AL/AO which is required to maintain a given x or y composition in the wave constant. Similarly, the adsorption wave velocity in dimensionless parameters would be the value of the ratio of AH/6T corresponding to Vw. This transformation may be obtained by substituting for ALH/AT using equations (3) and (4), which define T and H in terms of 0 and L.
AT - (KLa/PbV, )(AG0) - (Kaf/~~)A)(13) LH - (KLaA/Q)(AL) (14)

From (13) and (14),

AT/All - (Q/APbVP)(LO/AL) - (fv/PbVp) (15)

Therefore, designating the wave velocity in terms of the dimensionless parameters as Vwd,

1/Vwd =(Q/APbVli)(l/Vw) - (f/Pb~p) (16)

Substitution for Vw from equation (12) above, yields the simple relation,

V'wd =XF/YF * (17)

Equation (17) points out that the velocity at

which the adsorption wave moves through the column in terms









-48

of the dimensionless parameters is merely the ratio of the feed liquid composition to the adsorbed phase composition in equilibrium with the feed. Note that the physical properties of the bed do not enter into the relation. This relation can be verified readily by inspection of the calculated solutions (Figures 2-10) to the adsorption fractionation problem. In every case, after sufficient bed depth H was reached, the wave reached an ultimate shape and a velocity, All/AT, which equalled xF/yF*


C. The Shape of the Asymptotic Wave


The concept of a stationary wave maintained by a

movement of the adsorbent bed countercurrent to the liquid flow can also be utilized in computing the ultimate wave shape. Consider again a diagram of the liquid and adsorbed phase composition plotted vs. bed depth, L, for the countercurrent bed, and assume that the wave is being maintained stationary by appropriate flow of the liquid and adsorbent.





F
0

k XF

0





Bed Depth, L










-49

A volumetric balance for component A over section dL yields,

(dy/dL)WV P)(dL) -(dx/dL)(Q'dL) (18)

Note that total differentials may be used since the wave is assumed to be stationary. Rearrangement and integration between limits gives,


YF *dy - Q'/WVpfxdx


0 0

This integration is easily performed, so that, YF/F-Q'/WVp (19)

Equation (19) relates the flow rates required for maintenance of the stationary bed to the feed liquid composition and equilibrium adsorbed phase composition. Equation (19) is equivalent to equation (12); note that Q' is used in the former and Q in the latter. If the upper limit of the above integration be made indefinite, there results,

y -(Q'/WVP)x - (yF*/YF)x (20)

Equation (20) points out the relation that must hold between y and x at a given point in the adsorption wave, if the wave is to become invariant, as was assumed. This, then, places a restriction upon the shape of the equilibrium~ x-y diagram which will permit an adsorption wave of ultimate or invariant shape to become established. Consider the following diagram.









-50-


YF



y





0 XF

x

The straight line OA, which connects the origin with the equilibrium curve at the point representing the feed condition, can be thought of as the operating line for this process. Everywhere along the invariant adsorption wave, whether the wave is stationary or moving down the column, x and y for a given bed point at a given instant must fall on the line OA, that is obey equation (20). This relation may also be verified by referring to any of the calculated curves for the ultimate wave shapes (Figures 2-10).

It is apparent that if the equilibrium curve were to cross the line OA, then the liquid and adsorbed phase compositions could not possibly follow line OA. Hence, a requirement for the formation of an invariant adsorption wave is that the equilibrium diagram may not cross the "operating" line connecting (xF,yF*) with the origin.









-51

Further information about the invariant wave may

be derived by equating the rate of mass transfer between the two phases using the proposed mass transfer rate equation. Again considering section dL in the countercurrent bed,

(dy/dL)(WV P)(dL) =K La(x - x*~)(A dL) - (dx/dL)(Q')(dL) Thus, rearranging and integrating,

2L

d/xx (KLaA/Q') d= aA(L2 - L1) (21)



The integration is indicated between two arbitrary compositions because, theoretically, an infinite length of bed, based on the assumed rate mechanism, is required for the entire wave; this is because at the two ends of the wave the driving force for mass transfer is zero. However, by integrating between two compositions other than the extreme ends of the wave, the wave shape as a function of depth, L, can be obtained. The left hand integral can be evaluated because x *is related to y from the equilibrium diagram, and y is related to x by equation (20).- A convenient lower limit for the integration is xF/2, so that by integrating in both directions to various values of x, the ultimate wave shape may be obtained and plotted. Since the right hand side of equation (21) before integration equals dHi, the wave shape equation may be written in terms of the dimensionless parameter:










-52-


x

f dx/ (x -x* = x - H XF2(22)
xXF/2


In most cases the left-hand integral must be obtained by numerical means because of the difficulty in integrating the expression analytically. In effect, the computer solutions which were run in this work performed this integration, as evidenced by the ultimate wave shapes which were obtained. It is important to remember that the computer solutions also provided the relations for column operation before the ultimate wave shape was formed. An inspection of the graphs of the solutions shows that in general, 90 per cent of the wave (excluding the ends) becomes invariant by the time the composition of the liquid at the filling front drops to less than 5 per cent of the feed composition. Therefore, with a knowledge of the rate of advance of the adsorption wave (Vwd =xF/YIF*), the computer solution for the ultimate wave shape, and the computer solution during filling of the first portion of the bed, the composition of both phases may be quickly calculated for any H and T thereafter.


D. Computation of IIETS From Fixed Bed Data


Because continuous countercurrent moving bed adsorbers are readily analyzed by an equilibrium stage concept, in which the number of theoretical stages in the column









-53

necessary to give a given separation may be readily determined, the experimental determination of the height equivalent to a theoretical stage (HETS) has always been of interest. It is apparent that an experimental apparatus utilizing the countercurrent principle could be built and the determination of IIETS made by suitable experiments. However, it is not easy to construct true countercurrent apparatus in the laboratory. It would be more desirable to devise a means of predicting the HETS of a moving bed from a simple fixed bed experiment.

The analysis of the adsorption process made in the previous sections affords a way of doing this. It has been pointed out how the establishment of an invariant wave shape is possibly subject to one restriction concerning the shape of the equilibrium diagram, a restriction which is almost always met. It was also shown that the movement of the ultimate wave through the column is equivalent to a countercurrent experiment in which the adsorbent and liquid feed rates are adjusted to maintain the same velocity of feed liquid through the bed and to maintain the adsorption wave stationary. It was further shown that the flow rates between the two cases can easily be related.

This leads to the conclusion that every fixed bed experiment in which the column is long enough for the adsorption wave to be established is exactly equivalent to a continuous countercurrent experiment. The one difficulty










-54

is that the operating line for the continuous countercurrent experiment is such that the adsorbent at both ends of the column is in equilibrium with the liquid.

If the number of plates required for this separation were to be stepped off, there would, of course, result an infinity of plates because of the two pinched sections. However, it is suggested that the IIETS may nevertheless be obtained from the fixed bed experiment.

Since the experimental effluent volume vs. composition curve for the adsorption wave can be readily obtained, it may be transformed into a liquid composition vs. bed length quite readily, assuming the void fraction of the bed has been measured. Then, instead of determining the number of stages required for the complete separation, it is suggested that the number of stages be stepped off between the equilibrium and operating line for some arbitrary separation, say from O.9xF to O-lx'. See the following diagram.




O.9Xr YF A

HETS N/L2-Ll







O-lxF - -L7__-___0 LF x


L


x









-55

The bed depth required for the liquid composition to change from O.9xF to O.lxF can be determined from the wave shape which was computed from the experimental effluent curve, and a simple division by the number of theoretical stages stepped off will give the HETS. Whether or not this HETS will be constant for any pair of compositions is subject to conjecture. Nevertheless, the procedure described above affords a method of determining HETS from fixed bed experiments which should, if correlatable, be exactly analogous to the HETS required in the design of a continuous countercurrent bed.














VII. EXPERIMENTAL


A. Adsorbent


Commercial Davison silica gel (6-12 mesh) and Alcoa alumina (8-14 mesh) were used as adsorbents. A large particle size was chosen as there were already available in the literature both equilibrium data and kinetic data on systems using small particle size adsorbents. It was planned to secure data in this work with large particle sizes, which together with the previously published data of Lombardo (73) for 200 mesh silica gel would provide a good basis for comparison with calculated results. Both the silica gel and the alumina were heated to 2000C. and stored in airtight desiccators prior to use. This insured that their pore volumes were free of volatile contaminants, thereby promoting the reproducibility of experimental data. B. Adsorbates


Methylcyclohexane and toluene were used as adsorbates. These compounds have similar molecular weights, but ftre of different chemical configuration. There is a definite selective adsorption exhibited by both the silica gel and the alumina for toluene when binary solutions of these two liquids are adsorbed onto the adsorbents. Toluene is, therefore, component "All for these systems.

-56-









-57-


C. Experimental Procedures


1. Specific Pore Volume, V

A weighing bottle containing a weighed quantity of adsorbent was exposed in a closed desiccator, maintained at normal room temperature, to the vapors of the pure adsorbate (contained in a beaker also placed in the desiccator) for a period of two weeks. At the end of this time, which had previously been shown to be adequate for equilibrium to be established, the adsorbent was re-weighed to determine the weight of adsorbate taken up by the adsorbent. From these data the weight of adsorbate adsorbed per gram of adsorbent and V., the specific pore volume of the adsorbent, milliliters per gram, were calculated. The results of these experiments are presented in Table 3.

2. Determination of x-y Equilibria

Approximately 20 grams of adsorbent was measured

into a 50 ml. flask, to which 20 ml. of a particular mixture of toluene and. methylcyclohexane was added. The flasks were closed and left at room temperature for a minimum of four hours. A sample of the liquid phase was removed and its refractive index determined. From a refractive index calibration curve (Figure 26, Table 26, Appendix) previously obtained for toluene-MCH solutions, the composition of the liquid phase, x, was determined. Values of y *, the composition of the adsorbed phase in equilibrium with the liquid









-58

phase, were calculated from a material balance of the system. This method of equilibrium determination has been used previously by Lombardo (73), Eagle and Scott (63), and Perez

(75). It has proven to be quite accurate over the largest portion of the x-y diagram, assuming that the specific pore volumes of the two adsorbents are very nearly the same. The equilibrium data and diagrams for the two systems investigated here are presented in Tables 4 and 5 and in Figures 13 and 14. The equilibrium data and diagram of Lombardo (73) for the Benzene-Hexane silica gel system are shown in Table 6 and Figure 15. In order to make the computations for adsorption fractionation, suitable empirical equations had to be fitted to the x-y diagrams. The equations which were used for each system are given in each table.

3. Adsorption Fractionation Experiments

The experimental apparatus used was quite simple, consisting of three pyrex glass adsorption columns, each

2.43 cm. in diameter, of varying lengths. The lengths were approximately six inches, twelve inches, and twenty-four inches. Each column was equipped with a side arm near the top for removal of the effluent, since the liquid was fed through the columns from bottom to top. A metal charging bomb of approximately 400 ml. capacity was connected to a nitrogen cylinder. The bomb was equipped with a filling connection and valve which could be closed after charging the bomb with feed liquid. During a run the feed liquid was









-59

forced by nitrogen pressure from the bomb through polyethylene tubing through a capillary tube flowmeter into the inlet at the bottom of a column. A pressure regulating valve on the nitrogen cylinder permitted very precise control of the flow rate, as indicated by a manometer attached to the capillary. It was thus possible to make a set of three runs (one each through the three columns) in which the flow rate and feed composition were maintained constant.

The columns were packed with adsorbent prior to a

run by carefully pouring the adsorbent into the column while tapping continuously wvith a rubber mallet. The tapping was continued and adsorbent was added until the top of the adsorbent was level with the exit side arm, and the surface of the adsorbent ceased to settle. By weighing the columns before and after packing, the quantity of adsorbent added was ascertained.

A run was started by opening the stopcock at the bottom of the column and adjusting the nitrogen pressure to give the desired manometer reading. The small capillary orifices used in the flowmeter produced pressure drops of about ten inches of mercury, so that only minor adjustments of the nitrogen regulating valve were required during a run to compensate for the rise in liquid level as the column filled.

The effluent liquid was collected. in graduated

cylinders, and samples of five drops (1/4 ml.) were collected









-60

at regular intervals. The large diameter column was chosen so that samples of five drops could be taken at about 5-10 ml. intervals, thereby giving instantaneous compositions rather than average compositions, which would, have resulted if a very smallcolumn diameter were used.

An electric stopclocl: was started at the moment the liquid reached the first particle of adsorbent, and recordings of the time vs. volume of effluent liquid collected were made. The average flow rate during the run was ascertained from this time and volume record. The refractive indices of the samples collected were measured after completion of a run, and tables and charts of effluent liquid composition vs. quantity of liquid collected were prepared.

The column experiments and the data obtained during

the course of these experiments are shown in Tables 8-22. The experiments shown are only those which are referred to in this dissertation. In addition, the data of Lombardo for the beiuzene-hexane-silica gel system are presented in Tables 239-25. Table 7 summarizes these data as to the nature of the run and certain other factors.

4. Determination of Fraction Voids and, Bed Density

In order to compare experimental data for the adsorption fractionation runs with the calculated results obtained with the computer, it was necessary to evaluate the bed density and the fraction voids in each adsorbent bed. This was done by taking various sizes of graduated. cylinders,









-61

50, 100, and 200 ml., and filling them carefully with adsorbent. Bed densities were calculated from the weights before and after filling and the cylinder volumes. By tapping the cylinders with rubber mallets during the filling, as was done when packing the adsorption columns, it was possible to obtain reproducible bed densities. The bed density, Pb' used in the equations of this dissertation, is the grams of dry adsorbent per total volume of dry bed. It was assumed that since the bed densities were reproducible, the void volumes would also be reproducible. Consequently, after weighing the cylinders filled with dry adsorbent, the cylinders were then filled with pure toluene or methylcyclohexane. Time was allowed for the pore volumes to fill, and additional liquid was added until the liquid remained level with the top of the adsorbent. A third weighing ascertained how much liquid was added, and the void space in the bed was then computed as the difference between the volume of liquid added and the volume of liquid known to have been adsorbed. into the adsorbent pore volumes. The void fractions and bed densities obtained in this manner for the adsorbent beds are listed at the top of Tables 8-25, which present the results of the adsorption fractionation runs.














VIII. COMPARISONS BETWEEN EXPERIMENTAL AND CALCULATED RESULTS


The only method of comparing the results of the

computer calculations with the experimental data obtained in this study and in thie work of Lombardo is to test whether the effluent composition curves of the adsorption fractionation experiments can be satisfactorily correlated by the computed solutions.

It has been explained that there is one unmeasured property of the system, KLa, which is contained in both of the dimensionless parameters, H and T, used in the calculations. The success of the calculations depends on whether for a given experiment a value of KLa can be found which results in a good agreement between the experimental and the calculated effluent curves, and whether the values of KLa so obtained correlate with the flow rate of liquid through the bed.

In fitting the calculated results to the experimental data, there are two criteria which are considered. First, the general shape of the adsorption wave should be approximated, and second, the wave should be at the proper location in the bed at the proper time. It has been pointed. out that in a long enough column, the wave will eventually come to an ultimate shape and an ultimate velocity. In the experiments

-62-









-63

performed by Lombardo, the columns were sufficiently long for this to occur. Since Lombardo did not make duplicate runs at different column lengths, there was only one check point for each run.

In those cases where the length of the column is

large compared to the length of the adsorption wave, there is very little interest (other than academic) in an exact solution to the problem of wave shape. A rough estimate of the wave length in such a case, combined with the assumption that the wave reaches the ultimate velocity within a few wave lengths into the column (which it usually does) will suffice to predict with good accuracy the quantity of pure B which can be produced with a given column.

It is those cases in which the wave length is a substantial fraction of the column length that a more accurate knowledge of the adsorption wave shape and position is required. It is precisely this case that cannot be handled by the ultimate wave velocity and shape, but which requires the complete solution, which was provided by the computer. ,The experiments performed in this work were aimed at creating conditionsiof column operation which would require the computer solution.


A. Adsorption Fractionation Experiments of Lombardo


The effluent volume vs. composition curves for three fractionation experiments on the benzene-hexane-silica gel









-64

system are presented in Figures 16, 17, and 18. The experimental data for each curve are listed in Tables 23, 24, and 25. These data which were published by Lombardo (72) were the results of a Ph.D. thesis on adsorption fractionation. Since the columns were long enough for the establishment of the ultimate wave shape, the data were fitted to the calculations by means of the ultimate wave shape. The calculated curve at H - constant of Figure 12 was compared with the experimental curves, and the value of KLa which best fit each was chosen. The computed points using the chosen values of KLa are also plotted in Figures 16, 17, and 18, and curves are drawn through both the computed and the experimental data. It can be seen that there is good agreement between the shapes of the computed and the experimental curves. The values of KLa used are plotted vs. the superficial fluid velocity, Q/A, in Figure 24, curve A. It can be seen that there was a good correlation between KLa and the liquid velocity for the three runs. 1B. Toluene-Methylcyclohexane Fractionation on Silica Gel


The effluent volume vs. composition curves for three sets of fractionation experiments with the toluene-MCHsilica gel system are shown in Figures 19, 20, and 21. The experimental data for each of the nine runs are listed in Tables 8, 16. A summary of all adsorption fractionation runs is given in Table 7.









-65

Each set consists of three separate fractionation

runs made under identical conditions except for the quantity of gel used. It was desired to perform duplicate experiments with different column heights so that the value of KLa would be subject to three separate checks. These experiments

were run at rates which insured that the invariant or asumptotic wave front was not established. Two computer solutions, one at xF of 0.5 and one at XF at 0.1, both based on the equilibrium diagram for this system, are shown in Figures 6-10.

In order to fit the calculated solutions to the experimental data it was necessary, as with the Lombardo data, to find the value of KLa which best fit the curve shapes and positions in the bed. Here, however, there were three curves to be checked by the same KLa. The computed solutions are plotted on the graphs of the experimental data for comparison.

It can be seen that the agreement between wave shapes was not as good as resulted with Lombardo's data, although the rate of movement of the waves through the column correlated well. In each set only one value of KLa was needed to correlate all three runs. The values of KLa used are plotted vs. superficial liquid velocity, Q/A, in Figure 24, curve B.

The calculated curves are steeper and show .the characteristic I's" shape more definitely than the experimental curves. Previous investigators (76), have pointed out that in ion exchange two factors may affect the steepness of the










-66

curves. These factors are the relative adsorbability of the adsorbent, and the relative contribution of intraparticle diffusion to the total diffusional resistance. Two calculated curves using the same xF and KLa but using equilibrium diagrams exhibiting considerable differences in relative adsorbability will have different shapes. If the adsorbent selectivity is low, the wave will be less steep, for a given mass transfer coefficient, than if the selectivity is quite high. This is because the magnitude of x-x* P the driving force for mass transfer, is much lower for the column of low selectivity. A similar effect will occur if the intraparticle diffusion resistance contributes appreciably to the total diffusional resistance. The concentration gradients set up inside the particle tend to increase the quantity of co mponent A near the external film above the value of x*, which is computed from the average adsorbed phase composition. This causes the adsorption wave to have a shape which cannot be duplicated exactly by adjusting KLa in the assumed rate relation.

It may be concluded that intraparticle diffusion is a definite contributor to the diffusional resistance in the large particle size gel used in these experiments. This is in qualitative agreement with theory, since the average length of the internal diffusion paths per unit of surface area increases with particle size. On the other hand, the Davison









-67

"thru 20011 mesh silica gel used by Lombardo was apparently of a particle size small enough to permit the external film resistance to control.

The values of KLa which best fit the computed curves to the experimental data for the large particle size gel did correlate with superficial liquid velocity, however, as seen in Figure 24. It was gratifying to find that such a correlation was possible even though feed compositions of 0.1 volume fraction toluene and 0.5 volume fraction toluene were used. Apparently the intraparticle diffusional resistance was not altogether controlling at these flow rates, since there was an increase in effective KLa when the fluid velocity through the bed was raised.


C. Toluene-Methylcyclohexane Adsorption on
Activated Alumina


Data for the adsorption fractionation of toluene and MCH- mixtures on activated. alumina are plotted in Figures 21 and 22. There were no computer calculations made using the equilibrium diagram of this system, so that there is no comparison presented here between experiment and calculations. It can be seen, however, that for the same feed compositions and range of liquid flow rates as was used in the silica gel, the sharpness of the fractionation, as measured by the shape of the effluent curves, was better than that of the silica gel.









-68

D. Use of Constant-Alpha Type Equilibrium Diagrams


In the previous discussion of the numerical integration process, it was mentioned that a number of computer solutions were obtained to the adsorption fractionation problem using equilibrium curves of the constant-alpha type in anticipation of the possibility of using them for approximate solutions to specific cases, whenever the true equilibrium curve of the system could be approximated by a constant alpha curve. The results of such an approximation would certainly be more valuable than the application of solutions based on straight line equilibrium diagrams, which can approximate only a very small portion of an equilibrium curve.

It was hoped that a constant-alpha curve based on an average alpha over the range of the fractionation experiment would approximate the solution closely enough to be used in many systems. It was discovered, however, that it is quite important to use an equilibrium diagram which exhibits the exact relative adsorbability, alpha, for the system at the feed composition. That this is necessary was shown in the previous discussion on ultimate velocity of the adsorption wave. For the wave to come to the proper ultimate velocity (and, presumably, approach it in the proper manner) the value Of xF/YF * used in a calculation must be exact. This means that, not an average alpha, but the alpha of the feed composition must be used. In adsorption systems, alpha is very









-69

high at low values of x, and decreases with an increase in x. This is demonstrated in Figures 13, 14, and 15.

An example of the results when a constant-alpha type equilibrium diagram is substituted for the true diagram can be seen in Figure 19. The computer solution for an alpha of 3.0 (Figures 4 and 5) was fitted to the experimental data of a run by choosing an appropriate value of KLa, as before, which best fit the data. The resulting curves are shown in Figure 19 on the same plot with the experimental data and the curves obtained from the computer solution. It can be seen that the approximate x-y diagram fit the experimental wave shape better than the true x-y diagram. This anomaly is explained by reference to the previous discussion concerning the effect of intraparticle diffusion on the adsorption wave shape. Internal diffusion broadens the wave in a manner similar to a low adsorbent selectivity. Since the alpha of 3.0 was lower average selectivity than the true equilibrium curve, yet was the proper value at the feed composition, the effect of intraparticle diffusion caused this solution to fit the experimental data more closely. E. HETS of Column Packing


A method was derived in the Results of Calculations

section for determining the IiETS of column packing from fixed bed experiments. It was suggested that the effluent curves from fixed bed runs, when known to-be of the ultimate or









-70

asymptotic shape, can be transformed into column length units; and the number of stages required for a given change in x for a countercurrent column equivalent to the fixed bed experiment may be determined by a graphical procedure. Dividing the column length by the number of stages required for the composition change results in a value for HETS which may then be used in the design of countercurrent adsorption columns operating with the same relative velocity of liquid through the adsorbent as was maintained in the fixed bed experiment.

This procedure was applied to the experimental runs of Lombardo, since the effluent composition curves were thought to be invariant. The calculated values of HETS for the three runs are plotted vs. Q/A, the superficial liquid velocity in Figure 25, curve A. A definite correlation is noted, with a strong dependence of ITETS on the liquid velocity. The number of stages required for a change in x from 0.05 to

0.45 was graphically determined in Figure 15. Three equilibrium stages were stepped off.

The suggested procedure could not be applied to the runs made with the toluene-MCH-silica gel system, as the asymptotic adsorption waves were obviously not established. However, an estimate was made based on the calculated ultimate wave shapes and the relation between H and L which had been established by choosing KLa values. In this case about 3.2 stages were required for the separation from an x of 0.05 to 0.45, and 3.0 stages were required in run F-4 for a









-71

separation from an x of 0.02 to 0.09. The values of HETS f or the toluene-MCH--silica gel system are also plotted in Figure 25 against Q/A.

It is significant that in both cases a trend is

established. There is a marked increase in HETS with the velocity of the liquid through the bed. It is apparent that more data of this type are required to establish whether HIETS is actually as strongly dependent upon liquid velocity as is indicated here. If, however, the trends indicated here are true, it would be very important in the design of a countercurrent adsorber to size the column diameter for a given service properly.


F. Discussion of Calculations


The comparison of the computed curves for adsorption fractionation with two systems has shown that a very good agreement with experimental adsorption fractionation results when the adsorbent particle size and liquid flow rates are such that the external film is the major resistance to mass transfer between the adsorbed and liquid phases. In these cases the apparent or effective overall coefficient correlates well with liquid velocity through the adsorbent bed. It was found that a fair approximation of the column operation is obtained when the intraparticle diffusion contributes to the diffusional resistance. However, the wave shape is definitely not duplicated by the calculated curves. Through









-72

a fortuitous circumstance, namely, that increased intraparticle resistance affects the adsorption wave shape similarly to a decreased adsorbent selectivity, it was seen that when intraparticle resistance contributes to the diffusional resistance, computer solutions based on constantalpha equilibrium diagrams may correlate better than solution using the true equilibrium diagram, if care is taken to use a constant-alpha solution which is exactly equal to the value of alpha at the feed composition. The latter restriction was found to be required in order for the velocity of the calculated ultimate adsorption wave to be correct. It is recognized that the use of constant-alpha diagrams in cases where the external film resistance controls would. probably result in an incorrect wave shape.

The method. proposed in this dissertation for evaluation of HETS was used on the data presented here with some success. A correlation of HETS with liquid velocity through
th e a otiebut the indicated dependence of HETS upon liquid velocity seemed high. G. Discussion of Intraparticle Diffusional Resistance


Since the computed solutions of this work do not yield. an exact fit with data of large particle size adsorbent, the next logical improvement in the method of analysis which was used here would be to include in the basic equations a mathematical expression for the intraparticle resistance.









-73

The most important new consideration in such an

analysis would be that the adsorbed liquid phase would no longer have just one composition, y, at a given L and e, but its composition would also be a function of r, the radius of the particle.

It is very difficult to propose a mathematical model to explain the adsorption forces when intraparticle diffusion is considered. One possible procedure would be to assume an external film resistance, characterized by KLa, with the bulk unadsorbed liquid phase composition, x, on one side and a pseudo-liquid phase composition, xR *, on the other, where xR *is the liquid phase composition in equilibrium with YR, the composition of the adsorbed phase liquid at the external particle radius r =R. Diffusion within the particle in the adsorbed phase could be assumed to follow Fick's lawi for diffusion within a sphere, using an effective diffusivity, D, for the diffusion inside the particle.

By equating the rates of mass transfer across the external film to the Fick's law expression for the diffusion rate at r -R, the intraparticle and external diffusion may be related. Numerical integration of the resulting equations, applying the proper boundary conditions, should provide a solution.

One important limitation which would be encountered is that both KLa and D, the effective internal diffusivity, would be unknown parameters. Experiments would have to be










-74

designed to evaluate D when KLa was negligible, and then to add the effect of KLa in cases where D had previously been evaluated.

The addition of an extra unknown parameter, D, and an additional independent variable, r, makes the problem a much more difficult one than was solved in this work. It is believed, however, that the techniques demonstrated here will be applied in the future, using faster and larger capacity computers if necessary, to approach more closely

the exact solution to adsorption fractionation problems.













IX. CONCLUSIONS


1. The application of the proposed equations for adsorption

fractionation was demonstrated for systems with small

adsorbent particle size and low flow rates, in which the

external film resistance presumably controls.

2. The boundary conditions of the liquid phase adsorption

fractionation process were properly defined and applied

in a numerical solution.

3. A complete IBM 650 program for solving the proposed

equations has been developed and presented.

4. The basic thesis, that a numerical approach can provide

useful solutions to problems otherwise insoluble, has

been proved.

5. The use of a solution based on a constant-alpha type

equilibrium curve which approximates the true equilibrium

curve was found to give qualitative accuracy. The shape

of the adsorption wave is distorted, but its rate of travel down the column is closely approximated. The

results of this distortion can be used to advantage in systems in which intraparticle diffusion contributes to

the total diffusional resistance.

6. Differential equations for evaluating the ultimate wave

shape were derived, and the velocity of the ultimate wave wvas found to be dependent upon xF, the feed liquid compo-75-









-76

sition, and yF ,the adsorbed phase composition in
equilibrium with the feed liquid.

7. A method for determining from fixed bed experiments the

height equivalent to a theoretical stage (IIETS) and of

an adsorbent bed was proposed and demonstrated.









-77-


TABLE 1

NUMERICAL INTEGRATION FORMULAE


Yi~~j y~j+ [ T (3/2) (y/6T)i, d/6

This formula fits a second degree polynomial over
two AT increments.


L.+AH] [(5/l2)(x/&H)i,j+i + (2)

(2/3)( x/oH) i~ - (1/12) (Ox/aH)i I j-l]


This formula fits a third degree polynomial over two AH increments. Trial and error is required.

r A](/)~/T l2(Y5.ilj 3
Yil~ y~j+ A ][(/2 (y/6T +(l2)bybT1)ilj1(3

This formula fits a second degree polynomial over
one AT increment. Trial and error is required.


xi~+1 iij+ [AH] [l/2(x/6H~,j + (l/2)(6x/63H)i,j+1] (4)

This formula fits a second degree polynomial over
one AH increment. Trial and error is required.

Yi+l,j Y~ + [AT] [(5/12) (y/6T)i+,133 + ()

(2/3(6ybT)i~i- (l/l2)(6y/T)i..i


This formula fits a third degree polynomial over one AT increment. Trial and error is required.









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TABLE 2

SUMMARY OF
ADSORPTION FRACTIONATION CALCULATIONS


XFI
Calculation Vol. Frac. Comp.
Number A in Feed

51 0.5

52 0.1

98 0.1

99 0.5

2 0.5

3 0.3

4 0.1

5 0.7

6 0.9

7 0.9

8 0.7

9 0.5

10 0.3

11 0.1

12 0.1

13 0.3

14 0.5

15 0.1

16 0.3


x-y Equilibria

Toluene-MCH-Silica Gel** Toluene-MOR-Silica Gel ** Benzene-Hexane-Silica Gel* Denzene-Hexane-Silica Gel*

a = 2.0 a =2.0 a =2.0 a = 2.0 a- 2.0 a= 3.0 a= 3.0 a = 3.0 a = 3.0 a - 3.0 a- 5.0 a - 5.0 m - 5.0 a - 7.0 a= 7.0









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Table 2 (Continued)


XFP
Calculation Vol. Frac. Comp.
Number A in Feed

17 0.5

18 0.1

19 0.3

20 0.5


x-y Equilibria

*-7.0

*= 9.0

*- 9.0

*a- 9.0


*Data of Lombardo (73)

*Data of this work










TABLE 3

DETERMINATION OF SPECIFIC PORE


Run No. Adsorbent Adsorbate

1 6-12 Mesh Toluene
Silica Gel
2tII


II I,


Methyl cyc lohexane


8-14 Mesh MethylAct. Alumina cyclohexanE


'II


Toluene
11


WVt. Adsorbent, g.

29.56 21.'28

33.44 21.17 43.73 23.8 21.30 36.48


Wt. adso rba te,

10.77 7.85 9.98 6.. 26 6.36

3.473 3.563 5.636


g.


g. Adsorbate
g. Adsorbent .366 .369 . 299 . 296

1455 1467 . 1673 . 1616


Adsorbate Density, g./cc.

. 872 .872 .774 .774 .774 .774 . 872 . 872


For 6-12 Mesh Silica Gel., Aver age VP - .402

For 8-14 Mesh Activated Alumina Average V~ pa .188


VOLUMIES


3

4

5

6

7

8


V P
cc. /g.

.420 .424 . 387 .382 . 188 . 189 192 . 185


0









-81-


TABLE 4

ADSORPTION EQUILIBRIUM-DATA FOR
TOLUENE-METHYLCYCLOHEXANE ON DAVISON 6-12 MESH SILICA GEL
(cf. Figure 13)


x
Volume Fraction Toluene in Liquid
Phase


.0350 .0372
.0647 .0847
. 124 128
. 149 182
.210
132
-243
.304 .344 .411 .489 .526 .578
.641 .704 .741 .796 .871 .933


y
Volume Fraction Toluene in
Adsorbed Phase


. 289 . 269
.344 .420 .462 .476 .499 .540 .570
.467 .605 .656 .687 .726 .768 .787 817 . 839 .866 . 877 .906
. 943 949


Relative
Adsorbability (Y/l-y) (l-x/x)


11.211 9.526 7.581 7 .825
6.064 6.188 5.688 5.276 4.987 5.761 4.770 4.366
4.186 3.798
3.459 3.330 3.259 2.919 2.717
2.492 2.470 2.450 1.336


Empirical


EQuations


x =.203y


9


(x/1-x) - .1725(y/l-y)1.412; x/l-x -.459(y/1-y) - .589;


0 y 0. 15 0.15 y 1.776


.776 _< y _< 1









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TABLE 5

ADSORPTION EQUILIBRIUM DATA FOR
TOLUENE-METHYLCYCLOHEXANE ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
(cf. Figure 14)


x
Volume Fraction
Toluene in Liquid
Phase


y
Volume Fraction
Toluene in
Adsorbed Phase


Relative
Adsorbability. (y/l-y) (l-x/x)


.0178 .127 8.03
.0475 .214 5.46
.233 .480 3.04
.417 .685 3.04
.648 .832 2.69
.874 .960 3.46









-83-


TABLE 6

ADSORPTION EQUILIBRIUM DATA
BENZENE-N-HEXANE ON
DAVISON "THRU 200" MESH SILICA GEL
(Data of Lombardo)
(cf. Figure 15)


x
Volume Fraction Benzene in Liquid


y
Volume Fraction
Benzene in
Adsorbed Phase


.
Relative
Adsorbability (y/l-y) (l-x/x)


0.045 0.298 9.009
0.115 0.485 7.247
0.209 0.615 6.046
0.319 0.723 5.572
0.428 0.771 4.500,
0.546 0.841 4.398
0.653 0.875 3.72
0.771 0.922 3.51
0.882 0.966


Empirical Equations


y = x/(.9398x-+ .1475)


.226 < x< .500


y -x/(l.1354x + .1032) 0; <.2


0 < x < .226









TABLE 7

SUMMARY OF FRACTIONATION EXPERIMENTS


Run No. System Adsorbent


Toluene-MCH 6-12 Mesh
Silica Gel
it it


I I


Column Diam.,
Cm.

2.47
it it


I I


I T


I I


'II


F-la F-lb

F-ic

F-2a.

F-2b

F-2c F -4 a

F-4b F -4 c

F-5a F -Sb

F-Sc

F-6a


8-14 Mesh Alumina
I T


I'f


Pt 'P


I I


Wt. Adsorbent,
g.

195

95.2

45.35

191.2 95.2

47.55 195.35

96.6

45.3

255.2 121.5

59.7 62.8


Inverse Rate., sec ./cc.

12.73

12.7 12.7

20

20

20

5.75 5.75 5.75 8.13 3.13 8.13 16


XF
Feed Comup.

0.5 0.5 0.5 0.5 0.5 0.5 0.1 0.1 0.1 0.1 0.1 0.1 0.5


? I


PP Pt


Pt I? I,


I









TABLE 7 (Continued)


Run No. System Adsorbent


F -GbI

F-6c It

B-2(Lom- Benzenebardo) N-Hexane

B-3 I

B-4 t


It It


"Thru 200" Mesh Silica Gel
It


I t


Column Diam.,
cm.


'I It


0.8


I t


1.9


Wt. Adsorbent,
g.

129.9 267.9

20


10

20


Inverse Rate sec./icc.

16 16 880


650

246


Fee dComp.

0.5 0.5 0.5


0.5 0.5


I'









-86-


TABLE 8

TOLUENX-METHYLCYCLOHEXANE FRACT IONAT ION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F - la (cf. Figure 19)


Col. Diam. Wt. Gel.


Pb

XF


Sam~1e No.


1
2
3
4
5
6
7
8
9
10 11
12 13
14 15 16
17 18 19


-2. 47 cm.

-195. 0 g. S.679 g./cc.

0.500 Vol. f3
Toluenl


Time. sec.


2155

2305 2380
2450 2512 2590


2790



3135 3195 3270 3335 3395


Ave. Inverse Rate - 12.7 sec./cc.


V


'= .402 cc./g.


-.293


7. Sample Size Total Vol. Effluent, cc.


. 15 5.50 10.85 16.20 21.55 26.90 32.25 37. 60
42.85 48.30 59.00 64.35 69.70 75.05
80.40 85.75 91.10
96.45 111.80


7 drops

x
Vol. Fraction Toluene


.02 .055
. 102 . 150 199
. 240 . 279, .308 .328 .356 .380 .395
.408 .412 .428 .439 .441 .453 .466


Samule No.









-87-


TABLE 9

TOLUENE-IETHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F - lb (cf. Figure 19)


Col. Diam. Wt. Gel.


- 2. 47 cm.

- 95. 20 g.


Ave. Inverse Rate - 12.7 sec./cc.


V P


=.402 cc./g.


-.679 g./cc.

-0.500 Vol. fr.
Toluene


Sample Size


Sample No.


1
2
3
4
5
6
7
8
9
10 11
12 13
14 15 16 17 18 19
20


Time. sec.


1487 1539
1604 1666

1797 1869 1933


Total Vol. Effluent, cc.


*15
2.'50 4.85 7. 20
9.55 11.90
14.15 16.50 18.85
21.10 23.45 28.80
34.15 39.50
44.85 50.20 55.55 60.90 66.25 71.60


x
Vol. Fraction
To luene


125 . 208
. 240 268 290 321 327
.343 .359 .370 .370 .395
.408 420 .428 .435 .437 .453 .463 .465


Pb

XF


M .293


-7 drops









-88-


TABLE 10

TOLUENE-METHYLCYCLOHEXANE FRACTI ONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F - lc (cf. Figure 19)


Col. Diam. -2.47 cm.


Ave. Inverse Rate = 12.73 sec./cc.


Pb

XF


- 45.35g.


=.679 g./cc.


V
p
f
v


0.500 Vol. fr. Sample Size
Toluene


Total Vol.


Sample No.


3


6
7

9
10 11
12 13


Time, sec.


(1ml.


It


Effluent, cc.


.15
0.70 1.70 2.70 3.70
4.70 5.70 6.70 7.70 8.70 30.70 36.05
41.40


=.402 cc./g.

-.293

=7 drops
(except as
noted)


x
Vol. Fraction
Toluene


196 230 . 255 . 282 . 300 .310 .330
.342 356 367
. 438 .448 .450


Wt. Gel.









-89-


TABLE 11

TOLUENE-METHYLCYCLOHEXANE FRACTI ONATI ON ON
DAVISON 6-12 MESH SILICA GEL
Run No. F - 2a (cf. Figure 20)


Col. Diam. = 2.47 cm.


Ave. Inverse Rate -20 sec./cc.


Wt. Gel.


P b

XF


= 191. 20 g. M .679 g./cc.

-0.500 Vol. fr.
Toluene


V P


= .402 cc./g.


= . 293


Sample Size


=5 drops


Sample No.


1
2
3
4
5
6
7
8
9 10 11
12 13
14 15 16 17 18


Time, sec.


3644 3747 3853 3957
4065 4180 4275

4515 4606 4710 4825 4924 5020 5121 5216


Total Vol. Effluent, cc.


.10 5.35 10.60 15.85
21.10 26.35 31.60 36.85
42.10 47.35 52.60 57.85 63.10 68.35 73.60 78.85
84.10 89.35


Vol. Fraction
Toluene


.004 .004 .050

112 172 230 278 305 .339 .368 385 .396
.408 . 418 .425 .430 .438









-90-


TABLE 12

TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F - 2b (cf. Figure 20)


Col. Diam. -2.47 cm.


Ave. Inverse Rate =20 sec./cc.


Wt. Gel.


- 95.15 g.


VP


M.402 cc./g.


M .679 g./cc.


Vol. f r. Tol1ue ne


Sample Size


- 5 drops


~mn1e No.


1
2
3
4
5
6
7
8
9
10 11
12 13
14 15 16 17 18 19


Time. sec.


1650 1725 1762 1809 1847 1890 1930 1975
2022 2066 2183 2298 2398
2499 2611 2713 2828

3037


Total Vol. Effluent.


Vol. Fraction
Toluene _


CC.


.10
4.35 6.60 8.85 11.10 13.35 15.60 17.85
20.10 22.35 27.60 32.85 38.10
43.35 48.60 53.85 59.10 64 35
69.60


.035 .090 136 100 .060
*205 180 . 278 .328
.341 .366 .390
.405 .406 .436 .440 .444 .452 460


XF


M .293


Sample No Time sec









-91-


TABLE 13

TOLUENE-METHYLCYCLOHEXANE FRACT IONATI ON ON
DAVISON 6-12 MESH SILICA GEL
Run No. F - 2c (cf. Figure 20)


Col. Diam. Wt. Gel.


= 2.47 cm. = 47. 55 g.


Ave. Inverse Rate =20 sec./cc.


V p


=.402 cc./g.


=.679 g./cc.


=0.500 Vol. fr. Sample Size
Toluene


Sample No.


1
2
3
4
5
6
7
8
9 10 11
12 13
14


Time, sec.


835 868 935 975
1020 1050 1118 1156 1198

1283
1394 1491


Total Vol. Effluent, cc.


* 10 2.35 4.60 6.85
9.10 11.35 13.60 15.85 18.10 20.35 22.60 2'?.85
33.10 48.85


x
Vol. Fraction Toluene


122 . 210 . 252 312 .326
. 340 .370 395
.405 .416 .425; .440 .450 .468


Pb

XF


= . 293


-5 drops









-92-


TABLE 14

TOLUENE-METHYLCYCLOHEXANE FRACTI ONATI ON ON
DAVISON 6-12 MESH SILICA GEL
Run No. F - 4a (cf. Figure 21)


Col. Diam. - 2.47 cm.


Ave. Inverse Rate -5.75 sec./cc.


Wt. Gel.


P b

XF


-195.35 g. M.679 g./cc.

-0.100 Vol. fr.
Toluene


VP


-..402 cc./g.


= . 293


Sample Size


= 5 drops


Sample No.


1
2
3
4
5
6
7
8
9 10
11
12 13
14 15 16
17


Time, sec.


983
1041

1163
1222 1272 1337 1393
1445
1560 1619

1730

1906 1969


Total Vol. Effluent, cc.


10
20 30
40 50 60
70
80 90
100 110
120 130
140 150 170 180


x
Vol. Fraction
To luene


.0
.0
.0
.0
.0
.0
.0
,0 .0
.0
.006 .010 .016 :.019 .023 032 035




Full Text
H, Dimensionless Bed Depth
FIGURE 8.- LIQUID PHASE COMPOSITION HISTORY,
COMPUTER SOLUTION TO PROBLEM 52.
-112-


-58-
phase, were calculated from a material balance of the system.
This method of equilibrium determination has been used pre
viously by Lombardo (73), Eagle and Scott (63), and Perez
(75). It has proven to be quite accurate over the largest
portion of the x-y diagram, assuming that the specific pore
volumes of the two adsorbents are very nearly the same. The
equilibrium data and diagrams for the two systems inves
tigated here are presented in Tables 4 and 5 and in Figures
13 and 14. The equilibrium data and diagram of Lombardo (73)
for the Benzene-Hexane silica gel system are shown in Table 6
and Figure 15. In order to make the computations for ad
sorption fractionation, suitable empirical equations had
to be fitted to the x-y diagrams. The equations which were
used for each system are given in each table.
3. Adsorption Fractionation Experiments
The experimental apparatus used was quite simple,
consisting of three pyrex glass adsorption columns, each
2.43 cm. in diameter, of varying lengths. The lengths were
approximately six inches, twelve inches, and twenty-four
inches. Each column was equipped with a side arm near the
top for removal of the effluent, since the liquid was fed
through the columns from bottom to top. A metal charging
bomb of approximately 400 ml. capacity was connected to a
nitrogen cylinder. The bomb was equipped with a filling
connection and valve which could be closed after charging
the bomb with feed liquid. During a run the feed liquid was


H, Dimensionless Bed Depth, Or T, Dimensionless Time
FIGURE 5.- ULTIMATE ADSORPTION WAVE SHAPES,
COMPUTER SOLUTION TO PROBLEM 9.
-10 9-


-82
TABLE 5
ADSORPTION EQUILIBRIUM DATA FOR
TOLUENE-METHYLCYCLOHEXANE ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
(cf. Figure 14)
X
Volume Fraction
Toluene in Liquid
Phase
y
Volume Fraction
Toluene in
Adsorbed Phase
a
Relative
Adsorbability
(y/l~y)(1-x/x)
.0178
. 127
8.03
.0475
.214
5.46
.233
.480
3.04
.417
.685
3.04
.648
.832
2.69
.874
.960
3.46


VII. EXPERIMENTAL


A. Adsorbent
Commercial Davison silica gel (6-12 mesh) and Alcoa
alumina (8-14 mesh) were used as adsorbents. A large parti
cle size was chosen as there were already available in the
literature both equilibrium data and kinetic data on systems
using small particle size adsorbents. It was planned to
secure data in this work with large particle sizes, which
together with the previously published data of Lombardo (73)
for 200 mesh silica gel would provide a good basis for com
parison with calculated results. Both the silica gel and
the alumina were heated to 200C. and stored in airtight
desiccators prior to use. This insured that their pore
volumes were free of volatile contaminants, thereby promot
ing the reproducibility of experimental data.
B. Adsorbates
Methylcyclohexane and toluene were used as adsorb
ates. These compounds have similar molecular weights, but
hre of different chemical configuration. There is a definite
selective adsorption exhibited by both the silica gel and
the alumina for toluene when binary solutions of these two
liquids are adsorbed onto the adsorbents. Toluene is, there
fore, component "A" for these systems.
-56-


-70-
asymptotic shape, can be transformed into column length units;
and the number of stages required for a given change in x for
a countercurrent column equivalent to the fixed bed experi
ment may be determined by a graphical procedure. Dividing
i
the column length by the number of stages required for the
composition change results in a value for HETS which may then
be used in the design of countercurrent adsorption columns
operating with the same relative velocity of liquid through
the adsorbent as was maintained in the fixed bed experiment.
This procedure was applied to the experimental runs
of Lombardo, since the effluent composition curves were
thought to be invariant. The calculated values of HETS for
) the three runs are plotted vs. Q/A, the superficial liquid
velocity in Figure 25, curve A. A definite correlation is
noted, with a strong dependence of HETS on the liquid velocity.
The number of stages required for a change in x from 0.05 to
0.45 was graphically determined in Figure 15. Three equi
librium stages were stepped off.
The suggested procedure could not be applied to the
runs made with the toluene-MCH-silica gel system, as the
^ asymptotic adsorption waves were obviously not established.
However, an estimate was made based on the calculated ulti
mate wave shapes and the relation between H and L which had
been established by choosing Kj^a values. In this case about
3.2 stages were required for the separation from an x of 0.05
to 0.45, and 3.0 stages were required in run F-4 for a


-9-
energy upon adsorption. However, Kruyt (28) disagreed; he
believed that adsorption should decrease the rate of reac-
tions because of the immobility of the adsorbed molecules.
An important concept was developed by Mathews (29)
who, in 1921, pointed out that the term adsorption should
properly be used to describe a phenomenon in which the con
centration of a substance tends to be different at the
interface between two phases from the concentration in the
main body of either phase, thus broadening the scope of
adsorption.
A typical early paper on kinetics was published by
Ilin (30), who proposed that the rate of adsorption of a
constituent from a gas in a batch process is proportional
to ek*:. Such a relation, although it may fit a set of data,
sheds little light on the factors which determine the
instantaneous rate of adsorption.
During the late 1920's interest was aroused in the
equilibrium relationships for a system in which the adsorbate
contains more than one component attracted by the adsorbent.
Levy (31), and Klosky (32) submitted equations for correlat
ing such data. These studies probably suggested the concept
that adsorption could be used to fractionate binary mixtures.
1930-1940
Additional equations for correlating the kinetics of
batch adsorption were proposed by Tolloizko (33), Constable


-65-
Each set consists of three separate fractionation
runs made under identical conditions except for the quantity
of gel used. It was desired to perform duplicate experi
ments with different column heights so that the value of KLa
would be subject to three separate checks. These experiments
were run at rates which insured that the invariant or asump-
totic wave front was not established. Two computer solu
tions, one at Xj. of 0.5 and one at Xp at 0.1, both based on
the equilibrium diagram for this system, are shown in Figures
6-10.
In order to fit the calculated solutions to the experi
mental data it was necessary, as with the Lombardo data, to
find the value of KLa which best fit the curve shapes and
positions in the bed. Here, however, there were three curves
to be checked by the same KLa. The computed solutions are
plotted on the graphs of the experimental data for comparison.
It can be seen that the agreement between wave shapes
was not as good as resulted with Lombardos data, although
the rate of movement of the waves through the column corre
lated well. In each set only one value of KLa was needed to
correlate all three runs. The values of K^a used are plotted
vs. superficial liquid velocity, Q/A, in Figure 24, curve B.
The calculated curves are steeper and show .the charac
teristic "s" shape more definitely than the experimental
curves. Previous investigators (76), have pointed out that
in ion exchange two factors may affect the steepness of the


-39-
program represents some four to six months of intensive
effort, it, like any other computer program, is now
available for future use at any time.


FIGURE 12- ULTIMATE ADSORPTION WAVE SHAPES,
COMPUTER SOLUTION TO PROBLEM 99.


152
SLT
0001
1090
35
0001
0797
AUP
SUMDF
0797
10
0025
1229
SRT
0002
1229
30
0002
0935
- DVR
TWLVE
0935
64
0038
0998
RAU
8002
0998
60
8002
1457
MPY
B I NCR
1457
19
0078
1048
5RD
0009
1048
31
0009
1221
ALO
XNOW
1221
15
0074
1279
A'JP
XF.ST
1279
10
0033
1437
SLO
8002
1437
16
8002
1195
STD
XEST
1195
24
0033
1236
SUP
8001
1236
11
8001
0643
RAL
8003
0643
65
8 003
0751
SRD
0001
0751
31
0001
1507
NZE
CNXSF
1507
45
1410
1061
LDD
XEST
CL 1 PD
1061
69
0033
062 5
CL1PD
STD
0 30 3
CL1PE
0625
24
0303
0656
CL1PE
STD
XFSDP
RSETA
0656
24
0883
0633
CNXSF
RAU
8001
1410
60
8001
1317
MPY
HLFBF
1317
19
0870
1140
SRD
0009
1140
31
0009
1413
ALO
XEST
1413
15
0033
1487
STL
XEST
CL1PB
1487
20
0033
0778
CONSTANTS
HLFBE
05
0724
05
HLFBF
05
0870
05
RESET ADDRESSES
RSETA RAL
RSTKA
0633
65
1236
0941
LDD
TNLPA
0941
69
0050
0903
SDA
TNLPA
0903
22
0050
0953
LDD
CL1PC
0953
69
0008
1111
SDA
CL1PC
1111
22
0008
1161
RAL
RSTKB
1161
65
0614
0969
LDD
CNPWB
0969
69
0019
0722
SDA
CNPWB
0722
22
0019
0772
LDD
CNPWH
0772
69
0009
0712
SDA
CNPWH
0712
22
0009
0762
LDD
CNPWJ
0762
69
0736
1089


Volume Fraction Toluene in Adsorbed Phase
118-
x, Volume Fraction Toluene in Liquid Phase
FIGURE 14.- ADSORPTION EQUILIBRIUM DIAGRAM FOR MCH-
TOLUENE ON ALCOA 8-14 MESH ACTIVATED ALUMINA
Relative Adsorbability


-158-
S IA
AVPIR
TNLPA
0706
23
0603
0050
STPCB
RAL
SPCKD
0826
65
1479
1083
LDD
TSENC
1083
69
0679
1182
S IA
TSENC
1182
23
0679
1232
LDD
TSNWA
1232
69
0088
1391
SDA
TSNWA
1391
22
0088
1441
S IA
TSNWA
1441
23
0038
1491
RAL
SPCKE
1491
65
0994
0699
LDD
CL 1PE
0699
69
0656
0959
S IA
CL1PE
0959
23
0656
1009
RAL
SPCKC
1009
65
0862
1717
LDD
AVPIB
1717
69
0603
0756
S IA
AVPIB
TNLPA
0756
23
0603
0050
5TPCC
STU
TMCTR
0950
21
0034
1887
RAL
SPCKG
1887
65
1440
1745
LDD
CL1PE
1745
69
0656
1059
S IA
CL1PE
TNLPA
1059
23
0656
0050
CONSTANTS
SPCKA
01
TSWDA
PCHAA
1390
01
0650
0700
SPCKB
01
SPCKB
PCHBA
0944
01
0944
0800
SPCKC
01
SPCKC
TNLPA
0862
01
0862
0050
SPCKD
01
AVPIA
RSETA
1479
01
0092
0633
SPCKE
01
SPCKE
RSETA
0994
01
0994
0633
SPCKF
01
SPCKF
AVPIC
0812
01
0812
0720
SPCKG
01
spEkg
PCHCA
1440
01
1440
0850
TMONE
0001
1190
0001
ADVANCE WAVE ONE POINT
ADVWA RAL
AVV/KA
1003
65
0806
1261
AUP
8001
1261
10
8001
1169
ALO
RSTKA
1169
15
1286
1541
SLO
8002
1541
16
8002
0749
STD
RSTKA
0749
24
1286
1489
ALO
RSTKB
148 9
15
0614
1219
ALO
8003
1219
15
8003
1027
SLO
' 8002
1027
16
8 002
1235


-131-
X. LIST OF SYMBOLS
A Cross sectional area of adsorbent bed, sq. cm.
C Molar concentration, grams moles/1.
fv Fraction interstitial void space in adsorbent bed
H Dimensionless bed depth parameter defined by equation (4)
KLa Overall coefficient for mass transfer, 1/sec.
L Adsorbent bed depth, measured from entrance, cm.
Q Volumetric flow rate of liquid through adsorbent bed,
cc./sec.
Q- Volumetric flow rate of liquid through moving bed,
cc./sec.
r^ Rate of exchange of component A between two phases,
gram moles/(sec.)(cc.)
T Dimensionless time parameter, defined by equation (3)
Vp Pore volume of adsorbent, cc./g.
vm Molar volume of component A, l./gram mole
Vw Ultimate velocity of adsorption wave through fixed
adsorbent bed, cm./sec.
Vwd Ultimate velocity of adsorbent wave through fixed
adsorbent bed in units of parameters H and T
W Weight rate of flow of adsorbent through a continuous
countercurrent adsorption column, g./sec.
x Volume fraction of more adsorbable component A in liquid
phase
xjr Composition of liquid feed to adsorbent bed, volume
fraction component A
y
Volume fraction of more adsorbable component A in
adsorbent-free adsorbed phase


-7-
Freundlich isotherm was compatible with his own chemical
reaction theory; Duclaux (10) theorized that adsorption is
a result of differences in temperature which exist in minute
cavities of the solid, causing liquifaction. Many investi
gators, Geddes (11), Schmidt (12), Katz (13), Langmuir (14),
Polanyi (15), Williams (16), proposed equations different
from that of Freundlich. Some of these proposals were merly
the result of curve fitting, but others, such as those made
by Langmuir and Polanyi, were based on theories which ade
quately explain certain features of adsorption. By 1920,
when Polanyi introduced his equation, which utilized one
"characteristic" curve to account for the adsorption of a
vapor or gas under all conditions of temperature and pressure
of a given system, it was generally recognized that adsorp
tion may be explained by more than one theory, depending
upon the system, and may involve physical forces, chemical
forces, or a combination of both.
Theoretical analyses based on thermodynamic considera
tions became prevalent towards the last of this period;
speculations concerning the heat of adsorption were made.
Polanyi (17) discussed adsorption from the standpoint of the
3rd law, Langmuir (14) suggested that unbalanced crystal
forces account for physical adsorption, Williams (18) derived
an adsorption isostere equation from thermodynamic reasoning,
Lamb and Coolidge (19) concluded that the total heat of ad-


-143-
CNPWJ
STL
0302 TSENB
0736
20 0302 0055
CONSTANTS
HLFAR
05
0024
05
HLFAS
05
0070
05
HLFAT
05
0660
05
EIGHT
80
0020
80
FIVE
50
0069
50
TWLVE
12
0038
12
TEST FOR END OF BED
TSENB
RAL
CNPWF
0055
65
0717
0721
SLO
TSEBK TSENC
0721
16
0624
0679
TSENC
NZE
TSNWV RSETA
0679
45
0032
0633
CONSTANTS
TSEBK
SUP
0299 CNPW4
0624
11
0299
0707
TEST FOP
! END OF WAVE
TSNWV
RAL
xnov;
TSNWB
TEST FOR
0032
65
0074
0729
TSNWB
SRD
0001
TSNWC
END OF
0729
31
0001
0085
TSNWC
NZE
TSNWA
WAVE
0085
45
0088
0039
RAL
SKPKA
AFTER
0039
65
0042
0097
LDD
TSNWB
FIRST DROP
0097
69
0729
0 08 2
S IA
TSNWB
BECOMES
0082
23
0729
0632
RAL
SKPKB
PURE COMPA
0632
65
0635
0089
LDD
TNLP1
SKIP CALC
0089
69
0007
0710
S IA
TNLP1
OF LAST 2
0710
23
0007
0760
SLO
8002
TSNWA
POINTS
0760
16
8002
0088
TSNWA
NZE
AVPIA
RSETA
0088
45
0092
0633
CONSTANTS
SKPKA
01
SKPKA
TSNWA
0042
01
0042
0088
SKPKB
01
SKPKB
CNPWA
0635
01
0635
0010
ADVANCE ONE POINT
INSIDE WAVE


-54-
is that the operating line for the continuous countercurrent
experiment is such that the adsorbent at both ends of the
column is in equilibrium with the liquid.
If the number of plates required for this separation
were to be stepped off, there would, of course, result an
infinity of plates because of the two pinched sections.
However, it is suggested that the HETS may nevertheless be
obtained from the fixed bed experiment.
Since the experimental effluent volume vs. composition
curve for the adsorption wave can be readily obtained, it may
be transformed into a liquid composition vs. bed length quite
readily, assuming the void fraction of the bed has been
measured. Then, instead of determining the number of stages
required for the complete separation, it is suggested that
the number of stages be stepped off between the equilibrium
and operating line for some arbitrary separation, say from
0.9xp to O.Ixf. See the following diagram.


160 -
AVWKA
PARTA
SOA
SRYFE
1817
22
0764
1867
SLO
8002
1867
16
8002
1525
STD
SRYFP
1525
24
0088
1691
ALO
SRYFA
1691
15
0916
1571
ALO
8003
1571
15
8003
1629
LDD
SRYFC
1629
69
1713
1066
SDA
SRYFC
1066
22
1713
1116
LDD
SRYFF
1116
69
0966
1269
SDA
SRYFF
1269
22
0966
1319
SLO
0002
1319
16
8002
1227
STD
SRYFA TSENP
1227
24
0916
0900
CONSTANTS
0001
0806
0001
CALCULATION OF FIRST
TWO TIME
: INCREMENTS
LDD
XFEED
PUNCH
1000
69
1087
1490
STD
1926
CARD
1490
24
1928
0981
STD
1931
FOR ZERO
0981
24
1931
0784
SLO
8002
TIME
0784
16
8 002
1043
STL
1929
INCREMENT
1043
20
1929
1282
STD
1930
1282
24
1930
1183
STD
1932
1183
24
1932
143 5
STD
1933
1435
24
1933
163 6
RAU
1927
1636
60
1927
1031
AUP
CDCSA
1031
10
0834
1589
STU
1927
1589
21
1927
1330
PCH
1927
PUNCH CARD
1330
71
1927
1277
RAL
XFEED
COMPUTE
1277
65
1087
1741
LDD
0503
DRVF FOR
1741
69
1044
0503
RAU
XFEED
FIRST BED
1044
60
1087
1791
STD
1928
POINT
1791
24
1928
1081
SUP
XSTAR
1081
11
0090
1795
STU
0100
1795
21
0100
1203
STD
DFEED
1203
24
0672
1575
MPY
TI NCR
COMPUTE
1575
19
0 666
1686
SRD
0009
YEST BY
1686
31
0009
1109
ALO
XFEED
LINEAR
1109
15
1087
1841


START
[NILZ
JLiQO.
Initialize
PARTA
J.Q-QQ.
Compute
First Two AT
Increments
RSETA
Reset
Addresses
TSWFA
0723
Test For
Wave Front
No
L
ADVWA j 1003
SRYF
Yes
ZD
Advance
Compute
Wave One AH
First Point
Increment
In Wave
TSENP
-Q9Q0-
TSTIM
Test For
End of Problem
JSi

0754
CONSOLE *
r 8000
Read A
Card
'
Test Time
For Punch
No 1 Yes
STPCB
''0826 STPCi*0977
Set To
Skip Punch
Set To
Punch
TNLPA
0050
Test For Next
To Last Point
Yes | No
CL2PA E~ 0011
Compute Next
To Last Point
CNPWA
0010
Compute
Normal Point
CL1PA 1205
TSENB
0055
Compute Last
Test For
Point in Wave
End of Bed
(T -
H)
(H 200AH)
No I Yes
TSNWY t QQ32-
Test For
End of Wave
(y o)
3¡q I Yes
AVPIA
0092
Advance One
AH Increment
Inside Wave
FIGURE 1.- FLOW DIAGRAM OF COMPUTER PROGRAM


-60-
at regular intervals. The large diameter column was chosen
so that samples of five drops could be taken at about 5-10
ml. intervals, thereby giving instantaneous compositions
rather than average compositions, which would have resulted
if a very small column diameter were used.
An electric stopclock was started at the moment the
liquid reached the first particle of adsorbent, and record
ings of the time vs. volume of effluent liquid collected
were made. The average flow rate during the run was ascer
tained from this time and volume record. The refractive
indices of the samples collected were measured after com
pletion of a run, and tables and charts of effluent liquid
composition vs. quantity of liquid collected were prepared.
The column experiments and the data obtained during
the course of these experiments are shown in Tables 8-22.
The experiments shown are only those which are referred to
in this dissertation. In addition, the data of Lombardo
for the benzene-hexane-silica gel system are presented in
Tables 23-25. Table 7 summarizes these data as to the
nature of the run and certain other factors.
4. Determination of Fraction Voids and Bed Density
In order to compare experimental data for the ad
sorption fractionation runs with the calculated results
obtained with the computer, it was necessary to evaluate
the bed density and the fraction voids in each adsorbent bed
This was done by taking various sizes of graduated cylinders


APPENDIX
IBM 650 COMPUTER PROGRAM FOR SOLVING
ADSORPTION FRACTIONATION EQUATIONS
In the following pages the SOAP II program which was
developed to solve the partial differential equations derived
in section IV, Theory, is listed. This listing was printed
by an IBM 407 tabulating machine from the program deck of
punched cards, which was also used to read the program into
the computer. Both the machine language program and the
symbolic program, with descriptive comments, are listed. The
program listing is not arranged in the order of the flow
diagram of the problem (Figure 1), but it is arranged in the
order which was required for the SOAP II assembly program to
assign the machine language instruction and data addresses
optimally. By referring to the flow diagram (Figure 1) for
guidance, the program can be traced step-by-step through the
multiplicity of computations and logical decisions which the
computer makes in performing the computations.
In the original draft of the program, only the sym
bolic portion was written. This symbolic program was punched
into cards (following the SOAP II format); the SOAP II
assembly program was stored in the computer; and the symbolic
program cards were read into the computer. The computer,
-139-


-20-
troll i ng factor in this study was the limitation of the
storage capacity of the IBM 650 computer. It was found
that over 60 per cent of the machine capacity was required
to store the 'program, the sequence of instructions which
the machine follows to solve the problem. The remaining
storage was not sufficient to permit the addition of a third
independent variable, particle radius, to the other two,
time and bed depth. It would have been necessary to include
particle radius if intraparticle diffusion were treated as
a separate item. The required storage is available on larger
computers, however. Based on the results of the computations
of this study, it now appears that particle radius might
have been handled with the IBM 650, if the ranges covered by
the other two variables, time and bed depth, were suitably
restricted.
All analytical solutions which have been published
to date have of necessity each been based on a particular
form of the adsorption equilibrium relationship, which
expresses the relation between x, the composition of the
unadsorbed liquid phase, and y, the composition of the ad
sorbent-free adsorbed phase. This diagram is similar in
appearance to the usual vapor-liquid equilibrium diagram.
Because of the extreme difficulty in solving the equations,
most have assumed a straight line relationship, which is
strictly applicable only to dilute gas phase adsorption.


-142
STL
XEST
0029
20
0033
0036
LDD
DRFNW
0036
69
0013
0066
STD
DRFPV
CNPWB
0066
24
0016
0019
CNPWB
RAL
0302
CNPW2
COMPUTE
0019
65
0302
0057
CNPW2
LDD
CNPWC
0503
X BY CUBIC
0057
69
0060
0503
CNPWC
RAU
XEST
AVGING
0060
60
0033
0037
SUP
XSTAR
METHOD AND
0037
11
0090
0045
STU
DRFNW
COMPARE
0045
21
0013
0616
MPY
FIVE
WITH XEST
0616
19
0069
0640
SLT
0001
0640
35
0001
0047
A UP
SUMDF
0047
10
0025
0079
SRT
0002
0079
30
0002
0035
DVR
TV/LVE
0035
64
0033
0098
RAU
8002
0098
60
8002
0607
MPY
BI NCR
0607
19
0078
0648
SRD
0009
0648
31
0009
0671
ALO
XNOW
0671
15
0074
0629
AUP
XEST
0629
10
0033
0087
SLO
8002
0087
16
8002
0095
STD
XEST
0095
24
0033
0086
SUP
8001
0086
11
8001
0043
RAL
8003
0043
65
8003
0001
SRD
0001
0001
31
0001
0657
NZE
CNXSD
0657
45
0610
0061
LDD
XEST
CNPWD
0061
69
0033
0636
CNPWD
STD
1930
CNPW3
0636
24
1930
0083
CNPW3
STD
XNOW
CNPWE
0083
24
0074
0027
CNXSD
RAU
8001
COMPUTE
0610
60
8001
0667
MPY
HLFAS
NEWXEST
0667
19
0070
0690
SRD
0009
AND LOOP
0690
31
0009
0613
ALO
XEST
0613
15
0033
063 7
STL
XEST
CNPWC
0637
20
0033
0060
CNPWE
RAU
DRFNW
CNPWF
COMPUTE
0027
60
0013
0717
CNPV/F
SUP
0102
CNPW4
Y PRIME
0717
11
0102
0707
CNPW4
MPY
HLFAT
BY ADAMS
0707
19
0660
0030
SRD
0009
QUADRATIC
0030
31
0009
0003
ALO
DRFNW
CNPWG
METHOD
0003
15
0013
0767
CNPWG
STD
0102
CNPW5
0767
24
0102
0005
CNPW5
RAU
8 00 2
0005
60
8002
0663
MPY
TI NCR
0663
19
0666
0686
SRD
0009
CNPWH
0686
31
0009
0009
CNPWH
ALO
0302
CNPV/I
0009
15
0302
0757
cnpwi
STD
1933
CNPWJ
0757
24
1933
0736


-34-
impractical to fit a third degree equation in both direc
tions, as a double trial and error procedure would have
been required. Use of such a double trial and error proce
dure would have increased the computing time by a factor of
about 20. It was, therefore, necessary to compute in one
direction without a trial and error procedure, and the T
direction was arbitrarily chosen.
The above discussion holds for the computation of
all "normal" interior points; however, for points near the
boundaries T 0 and T H different formulae were required
to maintain at least second degree precision for all cal
culations .
It is of interest to describe in detail the first
few steps in the computation of a solution, so that an
accurate picture of the manner in which the boundary condi
tions were applied may be seen. The procedure followed in
starting a numerical integration is outlined below:


-132-
>
yp* Composition of adsorbed phase in equilibrium with feed
liquid, volume fraction component A
a Relative adsorbability of adsorbent for components A
and B, defined as (y/l-y)(1-x/x) at equilibrium
Pb Bulk density of dry adsorbent bed, g./cc.
6 Time elapsed since liquid first entered bed, sec.
i,j Subscripts used to denote a point on a grid
A,B Subscripts used to denote components A and B
Subscript used to denote that the designated phase is
in equilibrium with the opposite phase


-91
TABLE 13
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 2c (cf. Figure 20)
Col. Diam.
= 2.47 cm.
Ave. Inverse
Rate = 20 sec./cc.
Wt. Gel.
= 47.55 g.
vp
= .402 cc./g.
Pb
= .679 g./cc.
fv
- .293
XF
- 0.500 Vol. fr.
Toluene
Sample Size
= 5 drops
Sample No.
Time, sec.
Total Vol.
Effluent, cc.
X
Vol. Fraction
Toluene
1
835
.10
.122
2
86S
2.35
.210
3
935
4.60
.252
4
975
6.85
.312
5
1020
9.10
.326
6
1050
11.35
.340
7
1118
13.60
.370
8
1156
15.85
.395
9
1198
18.10
.405
10

20.35
.416
11
1283
22.60
.425
12
1394
27.85
.440
13
1491
33.10
.450
14

48.85
.468


-169-
STD
TSTMB
1793
24
0622
0976
RAL
RSTK7
INITIALIZE
0976
65
1880
1885
LDD
CFPWB
1885
69
1436
1843
SDA
CFPWB
ADDRESSES
1843
22
1436
1893
LDD
CFPWG
1893
69
0809
1262
SDA
CFPV/G
AT 0301
1262
22
0809
1312
LDD
CFPWH
1312
69
1185
1144
SDA
CFPWH
1144
22
1185
1194
RAL
RSTK8
INITIALIZE
1194
65
1147
1401
LDD
CFPWE
ADDRESSES
1401
69
1567
1370
SDA
CFPWE
AT 0101
1370
22
1567
1420
LDD
CFPWF
1420
69
1617
1470
SDA
CFPWF
1470
22
1617
1520
RAL
TSWFK
INITIALIZE
1520
65
1173
1627
LDD
SATBD
ADDRESSES
1627
69
0773
1026
SDA
SATBD
AT 0300
1026
22
0773
1076
LDD
SRYFP
1076
69
0888
1244
SDA
SRYFP
1244
22
0888
1294
LDD
SRYFB
1294
69
0709
1362
SDA
SRYFB
1362
22
0709
1412
LDD
SRYFD
1412
69
0759
1462
SDA
SRYFD
1462
22
0759
1512
LDD
SRYFE
1512
69
0764
1668
SDA
SRYFE
1668
22
0764
1718
LDD
TSWFA
1718
69
0723
1126
SDA
T SWF A
1126
22
0723
1176
RAL
SRYFK
INITIALIZE
1176
65
1431
1344
LDD
SRYFA
ADDRESSES
1344
69
0916
1719
SDA
SRYFA
AT 0100
1719
22
0916
1769
LDD
SRYFC
1769
69
1713
1366
SDA
SRYFC
1366
22
1713
1416
LDD
SRYFF
1416
69
0966
1819
SDA
SRYFF
1819
22
0966
1869
LDD
ITNWB
INITIALIZE
1869
69
1772
1226
STD
TSMWB
TEST FOR
1226
24
0729
1482
LDD
ITNLP
NEXT TO
1482
69
1394
1197
STD
TNLP1
LAST POINT
1197
24
0007
1760
LDD
INLZA
PLACEZERO
1760
69
1564
1768
STD
INLZD INLZC
INTO BED
1768
24
1822
1276


-31-
compute each point, the computer time required would have
been prohibitive, except that it was found unnecessary to
compute all of the points. Since the physical problem is
such that an adsorption "wave" is formed in both the liquid
and adsorbed phases, and that this "wave" moves through the
column, there are a great many points before and behind the
wave whose composition is fixed. In front of the wave is a
section of the column containing pure B, where both x and y
are zero; behind the wave is a section of a column in which
the liquid composition is Xj, and the adsorbed phase compo
sition is yp*, the value in equilibrium with the feed liquid
composition. In both of these sections no mass transfer
takes place, and it is not necessary to compute changes in
the values of x and y. This fact was incorporated into the
computer "program," and the computer did not bother to com
pute values for x and y outside of the wave itself. The
criteria chosen for the wave boundaries were that a point
was considered inside the wave whenever the compositions of
the point immediately adjacent to it were such that either
y 0.00005 or xp-x > 0.00005. A check computation made with
out these restrictions revealed that the results of the
solution were not affected within four significant figures,
which was considered sufficient precision. This maneuver
cut the computation time down to 5-10 hours per solution.


-171-
AUP
YCALC
0539
10
0513
0567
SLO
8002
0567
16
8002
0525
SRT
0001
0525
30
0001
0531
DVR
8001
0531
64
8001
0544
STL
XSTAR
SRXSZ
0 544
20
0090
0506
YLOWR RAU
YCALC
0550
60
0513
0518
MPY
1M13
0518
19
0521
0542
SRD
0009
0542
31
0009
0515
ALO
B
0515
15
1343
0597
AUP
YCALC
0597
10
0513
0568
SLO
3002
0568
16
8002
0527
SRT
0001
0527
30
0001
0533
DVR
8001
0533
64
8001
0546
STL
XSTAR
SRXSZ
0546
20
0090
0506
SUBROUTINE FOR YSTAR
0502
STD
SRYSZ
0502
24
0505
0508
RAU
XFEED .
0508
60
1087
0541
SUP
C
0 541
11
1393
0548
BMI
XLOWR XUPPR
0548
46
0552
0553
XUPPR
AUP
8001
0553
10
8001
0511
MPY
AM 11
0511
19
0514
0534
SRD
0009
0534
31
0009
0507
ALO
ALONE
0507
15
0510
0565
STL
DVSRA
0565
20
0519
0522
RAU
XFEED
0522
60
1087
0591
MPY
A
0591
19
1785
0556
DVR
DVSRA
0556
64
0519
0530
STL
YEQFD SRYSZ
0530
20
0758
0505
XLOWR
AUP
8001
0552
10
8001
0559
MPY
BMI1
0559
19
0512
0532
SRD
0009
0532
31
0009
0555
ALO
ALONE
0555
15
0510
0566
STL
DVSRA
0566
20
0519
0572
RAU
XFEED
0572
60
1087
0592
MPY
B
0592
19
1343
0 564
DVR
DVSRA
0564
64
0519
0580
STL
YEQFD SRYSZ
0580
20
0758
0505
SUBROUTINE FOR CONSTANTS


II. BACKGROUND
Historically, the most frequently encountered prob
lem in the chemical and related industries has been the
necessity of separating relatively pure materials from
mixtures of. two or more components, thereby producing either
finished products for sale or intermediate products to be
further processed. One portion of chemical engineering
science, the unit operations, is devoted entirely to the study
of the various methods for separating materials.
Research in the unit operations is usually aimed
either at the development of new, more economical, or more
exacting separation methods, or at the development of more
precise theories and formulae for expressing the phenomena
of the known methods so that they may be put to better use.
In the past decade, a new tool has been made available which
can help the scientist and engineer to investigate mathe
matical theories and methods in a manner undreamed of twenty
years ago. This tool is the high speed electronic computer,
digital or analog. Such machines have many capabilities,
but one of the most important to technical research is their
ability to solve complicated mathematical equations, both
algebraic and differential, which are otherwise insoluble.
In the past, many a theorist has been forced to
abandon a set of equations which he believed might express a
-3-


0501 STD
SRKEZ
0501
24
0504
0 5 57
RAU
A
0557
60
1785
0539
ALO
B
0589
15
1343
0598
SUP
ALONE
0598
11
0510
0 569
SLO
3001
0569
16
8001
0577
STU
AM 11
0577
21
0514
0570
STL
BM 11
0570
20
0512
0571
RAU
ALONE
0571
60
0510
0523
SUP
A
0523
11
1785
0590
STU
1MIA
0590
21
0520
0573
RAU
ALONE
0573
60
0510
0 524
SUP
B
0524
11
1343
0 549
STU
1MIB SRKEZ
0549
21
0521
0504
CONSTANTS
ALONE
10
0510
10


III. PREVIOUS WORK
In this section, the progress in adsorption research
is traced from the turn of the century to the present. In
general only those publications which deal with multicom
ponent adsorption equilibria or rate of adsorption are
discussed. However, any paper of unusual interest is also
mentioned.
1900-1920
The early investigators concerned themselves with
the nature of adsorption and with the equilibrium relation
ships of various systems of adsorbate and adsorbent.
Freundlich (3) proposed his now famous isotherm for correlat
ing the adsorption data of many systems. He was an early
exponent of the theory that adsorption is a surface pheno
menon (4), (5), which was not altogether accepted by the
scientists of his day. Travers (6) suggested that since
adsorption depends upon temperature it should be considered
a "solid solution" phenomenon; this was refuted by Wohlers
(7), who concluded that chemical bonds must account for the
process because the adsorbed material usually does not react
normally. Michaelis and Rona (8) suggested that adsorption
is caused by a lowering of the surface tension of the sol
vent by the adsorbent. Reychler (9) demonstrated that the
-6-


high at low values of x, and decreases with an increase in x.
This is demonstrated in Figures 13, 14, and 15.
An example of the results when a constant-alpha type
equilibrium diagram is substituted for the true diagram can
be seen in Figure 19. The computer solution for an alpha
of 3.0 (Figures 4 and 5) was fitted to the experimental data
of a run by choosing an appropriate value of KLa, as before,
which best fit the data. The resulting curves are shown in
Figure 19 on the same plot with the experimental data and the
curves obtained from the computer solution. It can be seen
that the approximate x-y diagram fit the experimental wave
shape better than the true x-y diagram. This anomaly is ex
plained by reference to the previous discussion concerning
the effect of intraparticle diffusion on the adsorption wave
shape. Internal diffusion broadens the wave in a manner
similar to a low adsorbent selectivity. Since the alpha of
3.0 was lower average selectivity than the true equilibrium
curve, yet was the proper value at the feed composition, the
effect of intraparticle diffusion caused this solution to fit
the experimental data more closely.
E. HETS of Column Packing
A method was derived in the Results of Calculations
section for determining the HETS of column packing from fixed
bed experiments. It was suggested that the effluent curves
from fixed bed runs, when known to be of the ultimate or


-14-
intraparticle diffusion, and adsorption resistance, on the
solution of the bed height required were shown.
Hiester (69) considered the performance of ion
exchange and adsorption columns mathematically. Approxi
mate solutions of mass transfer differential equations were
given which can be used to predict column behavior.
J. B. Rosen (70) published a solution of the general
problem of transient behavior of a linear fixed-bed system
when the rate is determined by liquid film and particle
diffusion.
Gilliland and Baddour (71) considered the kinetics
of ion exchange, wherein an overall coefficient representing
all resistances to transfer was used successfully, and pre
sented a solution to the partial differential equations
previously derived by Thomas. This is an isolated instance
where the equilibrium equation used was not restricted to
a straight line. Experimental data correlated very well,
so that use of experimentally determined rate constants pre
dicted the elution curves of other experiments satisfac
torily .
Lombardo (72) considered the problem of binary
liquid adsorption fractionation from the pseudo-theoretical
stage standpoint, and obtained solutions to the stepwise
equations which he proposed by means of a card programmed
calculator.


-47-
vw JL. ...... *gfy.. (Q/Afv)
pbA (Xpiy + VppbYp*)
(12)
Therefore, equation (12) above gives the velocity of the
wave traveling through a bed, based on the assumption that
a wave of invariant shape is formed.
It is desirable to transform this velocity into a
velocity in terms of the dimensionless parameters H and T.
Vw may be considered as the ratio of AL/A0 which is required
to maintain a given x or y composition in the wave constant.
Similarly, the adsorption wave velocity in dimensionless
parameters would be the value of the ratio of aH/aT corre
sponding to V\V. This transformation may be obtained by
substituting for AH/aT using equations (3) and (4), which
define T and H in terms of 0 and L.
AT (KLa/pbVp)(AS) (KLaAfv/QpbVp)(AL) (13)
AH (KLaA/Q)(AL) (14)
From (13) and (14),
AT/AH (Q/ApbVp)(A0/AL) (fv/PbVp) (15)
Therefore, designating the wave velocity in terms of the
dimensionless parameters as Vwcj,
1/Vwd (Q/ApbVp)(l/Vw) (f/pbVp) (16)
Substitution for Vw from equation (12) above, yields the
simple relation,
vwd xF/yF* (17)
Equation (17) points out that the velocity at
which the adsorption wave moves through the column in terms


-8
sorption equals the heat of condensation plus the work of
compression. Very little was done with liquid adsorbates;
interest in vapor phase adsorption predominated. Gurvich
(20), however, noted that, on the same adsorbent and at
their own vapor pressure, approximately equal volumes of
various liquids were adsorbed.
One of the earliest investigations of the rate of
adsorption was performed by Berzter in 1912 (21). As with
most of the early studies, Berzter used a gas-air mixture,
from which he adsorbed the gas onto activated charcoal. He
fitted an empirical equation to his rate data without
determining the significance of the factors. Other inves
tigations of similar systems were made by Rakovskii (22),
Gurvich (23), who discovered that subdivision of the adsorbent
particles affected the rate of adsorption but not the ad
sorption equilibrium, Freundlich (24), Dietl (25), and Hernad
(26). Little was concluded from these studies except that
the velocity of batch-type adsorption decreased as the ad
sorption progressed, and that diffusion might play a role in
determining the rate.
1920-1930
The role of adsorption in catalysis was foreseen by
Polanyi, who in 1921 showed in a theoretical paper (27) that
adsorbents should by their nature accelerate chemical reac
tions, because of the reduction in the required activation


-49-
A volumetric balance for component A over section dL yields,
(dy/dL)WVp)(dL) (dx/dL)(Q*dL) (18)
Note that total differentials may be used since the wave is
assumed to be stationary. Rearrangement and integration
between limits gives,
0 0
This integration is easily performed, so that,
yF*/xF Q/WVp (19)
Equation (19) relates the flow rates required for main
tenance of the stationary bed to the feed liquid composition
and equilibrium adsorbed phase composition. Equation (19)
is equivalent to equation (12); note that Q is used in the
former and Q in the latter. If the upper limit of the above
integration be made indefinite, there results,
y (Q'/WVp)x (yFVyF)x (20)
Equation (20) points out the relation that must hold between
y and x at a given point in the adsorption wave, if the
wave is to become invariant, as was assumed. This, then,
places a restriction upon the shape of the equilibrium x-y
diagram which will permit an adsorption wave of ultimate
or invariant shape to become established. Consider the
following diagram.


-87-
TABLE 9
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F lb (cf. Figure 19)
Col. Diara.
Wt. Gel.
Pb
XF
2.47 cm.
95.20 g.
.679 g./cc.
0.500 Vol. fr.
Toluene
Ave. Inverse Rate
vp
*v
Sample Size
12.7 sec./cc.
.402 cc./g.
.293
7 drops
Total Vol.
Sample No.Time, sec.Effluent, cc.
x
Vol. Fraction
Toluene
1
-
.15
.125
2

2.50
.208
3

4.85
.240
4
7.20
.268
5

9.55
.290
6
11.90
.321
7
14.15
.327
8
16.50
.343
9

18.85
.359
10

21.10
.370
11
-
23.45
.370
12
1487
28.80
.395
13
1539
34.15
.408
14
1604
39.50
.420
15
1666
44.85
.428
16

50.20
.435
17
1797
55.55
.437
18
1869
60.90
.453
19
1933
66.25
.463
20

71.60
.465


-55-
The bed depth required for the liquid composition to change
from 0.9xf to 0.1xF can be determined from the wave shape
which was computed from the experimental effluent curve,
and a simple division by the number of theoretical stages
stepped off will give the HETS, Whether or not this HETS
will be constant for any pair of compositions is subject to
conjecture. Nevertheless, the procedure described above
affords a method of determining HETS from fixed bed experi
ments which should, if correlatable, be exactly analogous to
the HETS required in the design of a continuous counter
current bed.


APPLICATION OF NUMERICAL METHODS
IN ANALYSIS OF FIXED
BED ADSORPTION FRACTIONATION
By
ADRAIN EARL JOHNSON, JR.
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
February, 1958


147-
CONSTANTS
THREE
3000
0678
3000
TWO
0002
0054
0002
CDCST
0001
0740
0001
WDKTA
01
1927
WDKTA
0626
01
1927
0626
WDKTB
01
1930
WDKTB
0058
01
1930
0058
WDONE
1000
0750
1000
PCHBA
RAL
CNPWJ
SET WORD
0800
65
0736
0791
SRT
0001
COUNT AND
0791
30
0001
0697
ALO
WDONE
LOCATION
0697
15
0750
0905
SLO
WDCTR
OF FIRST
0 90 5
16
0 77 0
1025
SRT
0003
WORD IN
1025
30
0003
0833
ALO
0001
PUNCH ZONE
0833
15
8 001
0841
LDD
1927
0841
69
1927
0880
S IA
1927
0880
23
1927
0930
RAL
8001
ADD ONE TO
0930
65
8001
0937
ALO
CDCST
CARD COUNT
0937
15
0740
0945
STL
1927
0945
20
1927
0980
STU
TMCTR
ZERO TMCTR
0980
21
0034
0987
PCH
1927
PUNCH
0987
71
1927
0677
RAL
CL1PD
SET WORD
0677
65
062 5
0929
SRT
0004
COUNT AND
0929
30
0 0 04
0889
ALO
WDONE
LOCATION
0889
15
0750
0955
LDD
1927
OF FIRST
0955
69
1927
1030
S I A
1927
DROP IN
1030
23
1927
1080
RAL
8001
PUNCH ZONE
1080
65
8001
1037
ALO
CDCST
1037
15
0740
0995
STL
1927
0995
20
1927
1130
LDD
XFSDP
STORE CONC
1130
69
0883
0786
STD
1928
OF FIRST
0786
24
1928
0631
STD
1931
DROP INTO
0631
24
1931
0084
STU
1929
PUNCH ZONE
0084
21
1929
0782
STD
1930
0782
24
1930
0933
STD
1932
0933
24
1932
0735
STD
1933
0735
24
1933
0836
PCH
1927
RSETA
PUNCH
0836
71
1927
0633
PCHCA
LDD
0310
0850
69
0310
0913


-21-
The Langmuir equation, (y x/a+bx) has been used for an
approximate solution, assuming chemical kinetics to be the
controlling rate. Neither of these forms expresses satis
factorily the equilibrium of liquid phase adsorption over a
very wide range. In fact, usually no one algebraic expression
fits adsorption equilibria over the complete diagram. It is
quite often necessary to fit two or more algebraic expressions
to liquid phase adsorption equilibrium data. Because of this
an analytical solution cannot be generally applicable to
different systems. Moreover, an analytical solution is very
complex, even when based on the simplest straight line
equilibrium relation. The computation of the infinite series
which usually result in analytical solutions could easily
require a computer. It is of importance that a computer
solution can be obtained no matter how complex the equilibrium
relationship, thus "tailoring" the solution to the particular
system under study, and thereby removing a basis for conjec
ture when comparing the calculated solution v/ith the experi
mental results.
B. Derivation of Equations
A material balance (using volume fraction composi
tions) for component A, the more strongly adsorbed component,
can be made over a differential section of the adsorption bed.
Equating the loss from the fluid stream to the gain by the


-30-
The two sketches portray the three dimensional pic
ture of the desired relationships. The surface, x x(T,H)
and the surface y * y(T,H) represent the functions which
satisfy the partial differential equation and its boundary
conditions. Along the boundary H = O, x is shown to be con
stant, xF, the feed composition. Also along this boundary,
y increases from xjr, its initial value as the first drop fills
the first section of the column, to yF*, the value in equi
librium with the feed. Along the boundary H = T, both the
x and y surfaces follow the same curve, as prescribed by
the second boundary condition. The general shape of the
curve is known before hand, but the actual boundary condi
tion is merely that x = y. The values of the two function
between these two boundaries make up the surfaces represent
ing the solution to the problem.
A rectangular grid has been superposed at the base
of the figures. This grid represents the finite values of
H and T at which the numerical solution provides values of
x and y. As the grid is made smaller the resulting numeri
cal solution will approach the true solution very closely,
but also many more points must be computed. In this problem,
capacity was available in the computer to compute values for
a grid composed of 200 T and 200 H points. From the sketch
one can see that this would involve the computation of x and
y for a total of 20,000 grid points each time the problem is
worked. As the computer required about four seconds to


-42-
out answers for every tenth dimensionless time (T) incre
ment. The entire adsorption wave was punched out at this
time increment, but, as explained before, the constant
composition sections in front of and following the wave were
not punched.
The information from the cards was then printed in
list form by means of an IBM 403 tabulating machine. From
these lists of calculated data points, graphs of the solu
tion were prepared. It was found that there were three
graphs required to portray the information from each solu
tion. On one, values of x, the liquid phase composition,
were plotted against H, the dimensionless bed depth para
meter, along lines of constant T, the dimensionless time
parameter. A second plot was required to give the same
information about y, the adsorbed phase composition. A
third plot was made of the ultimate, or asymptotic, wave
shapes which are reached by the adsorption wave as it travels
down the bed. Typical graphs of problem solutions are shown
in Figures 2-11. Only those solutions referred to in this
dissertation are shown. The tabulated data from which the
graphs were computed were much too voluminous to include here.
It is planned to compile the data and graphs for all of the
twenty-three solutions under a separate cover for ready
reference.
It was found that in every problem solution an ulti
mate wave shape was formed provided sufficient distance along


Volume Fraction Toluene
i
i
FIGURE 26.- CALIBRATION OF REFRACTOMETER FOR MCH-TOLUENE SOLUTIONS
130


5-
adsorption.
The analysis of fixed bed liquid phase adsorption
fractionation is complicated by the fact that it is
inherently unsteady-state, or transient; partial differen
tial equations are required to express the process behavior
mathematically. The fixed bed adsorption fractionation
process, being mathematically complex and hence in an early
stage of treatment, was chosen for study with the dual
purpose in mind of advancing the frontier of knowledge in
this field and of demonstrating what the computer can mean
to research.


-14 5-
AVPIB
AVPIC
LDD
CNPWG
0829
69
0767
0620
SDA
CNPWG
0620
22
0767
0670
LDD
CL2PB
0670
69
0073
0026
SDA
CL2PB
0026
22
0073
0076
LDD
CL2PE
0076
69
0879
0682
SDA
CL2PE
0682
22
0879
0732
LDD
CL2PK
0732
69
0685
0638
SDA
CL2PK
0638
22
0685
0688
LDD
CL2PL
0688
69
0041
0094
SDA
CL2PL
0094
22
0041
0644
SLO
3002
AVP I B
0644
16
8002
0603
STD
CNPWF
AVPIC
0603
24
0717
0720
ALO
CNPWD
0720
15
0636
0091
ALO
8003
0091
15
8003
0099
LDD
CL2PG
0099
69
0002
0655
SDA
CL2PG
0655
22
0002
0705
SLO
8002
0705
16
8 002
0813
STD
CNPWD
0813
24
0636
0739
ALO
CNPWI
0739
15
0757
0711
ALO
8003
0711
15
8003
0769
LDD
CL2PH
0769
69
0072.
0675
SDA
CL2PH
0675
22
0072
0725
SLO
8002
0725
16
8002
0683
STD
CNPWI
0683
24
0757
0860
SRT
0001
ADD ONE TO
0860
30
0001
0817
AUP
WDCTR
WORD
0817
10
0770
0775
STU
WDCTR
TNLPA
COUNTER
0775
21
0770
0050
CONSTANTS
AVPKA
0001
0645
0001


LIST OF ILLUSTRATIONS
Figure Page
1. Flow Diagram of Computer Program 105
2. Liquid Phase Composition History, Computer
Solution to Problem 1 106
3. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 1 107
4. Liquid Phase Composition History, Computer
Solution to Problem 9 108
5. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 9 109
6. Liquid Phase Composition History, Computer
Solution to Problem 51 110
7. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 51 Ill
8. Liquid Phase Composition History, Computer
Solution to Problem 52 112
9. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 52 113
10. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 52 114
11. Liquid Phase Composition History, Computer
Solution to Problem 99 115
12. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 99 116
13. Adsorption Equilibrium Diagram for MCH-Toluene
on Davison 6-12 Mesh Silica Gel 117
14. Adsorption Equilibrium Diagram for MCH-Toluene
on Alcoa 8-14 Mesh Activated Alumina 118
vii


H, Dimensionless Bed Depth, Or T, Dimensionless Time
FIGURE 3.- ULTIMATE ADSORPTION WAVE SHAPES
COMPUTER SOLUTION TO PROBLEM 1.
-107


-74-
designed to evaluate D when KL,a was negligible, and then to
add the effect of KLa in cases where D had previously been
evaluated.
The addition of an extra unknown parameter, D, and
an additional independent variable, r, makes the problem a
much more difficult one than was solved in this work. It
is believed, however, that the techniques demonstrated here
will be applied in the future, using faster and larger
capacity computers if necessary, to approach more closely
the exact solution to adsorption fractionation problems.


TABLE OF CONTENTS (Continued)
Page
VIII. COMPARISONS BETWEEN EXPERIMENTAL AND
CALCULATED RESULTS 62
A. Adsorption Fractionation Experiments of
Lombardo 63
B. Toluene-Methylcyclohexane Fractionation
on Silica Gel 64
C. Toluene-Methylcyclohexane Adsorption on
Activated Alumina 67
D. Use of Constant-Alpha Type Equilibrium
Diagram 68
E. HETS of Column Packing 69
F. Discussion of Calculations 71
G. Discussion of Intraparticle Diffusional
Resistance 72
IX. CONCLUSIONS 75
X. LIST OF SYMBOLS 131
XI. LITERATURE CITED 133
APPENDIX.- IBM 650 COMPUTER PROGRAM FOR SOLVING
ADSORPTION FRACTIONATION EQUATIONS 139
BIOGRAPHICAL SKETCH 173
iv


LIST OF TABLES (Continued
Table Page
16. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 94
17. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 95
i
18. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 96
19. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 97
20. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 98
21. Toluene-Mechylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 99
22. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 100
23. Benzene-N-Hexane Fractionation on Davison
"Thru 200 Mesh Silica Gel 101
24. Benzene-N-Hexane Fractionation on Davison
"Thru 200" Mesh Silica Gel. 102
25. Benzene-N-Hexane Fractionation on Davison
"Thru 200" Mesh Silica Gel 103
26. Calibration of Refractometer for MCH-Toluene
Solutions at 30C 104
vi


-38-
to point out here that if the program as listed in the
Appendix be punched into standard IBM cards according to
the SOAP II format, and if the instructions accompanying
the program be followed, any competent 650 operator could
utilize this program to solve a binary liquid phase adsorp
tion fractionation problem, limited, of course, to the basic
assumption as to the mechanism involved on which the v/ork
was based. The program listed in the Appendix uses the alpha-
type equilibrium diagram familiar to distillation processes.
To work a problem, it is necessary only to read the program
into the Type 650, then to read in one problem" card, v/hich
provides the information as to the feed composition, magni
tude of alpha, size of the AT and AH increment, and frequency
desired in the punching of the answer cards. The computed
answers are punched by the machine at pre-determined incre
ments of AT, chosen arbitrarily for each problem on the
problem card.
If it is desired to perform a calculation using the
equilibrium diagram of a specific system, as was done in this
work, a sub-routine for computing x* from y must be added to
the program listed here in such a way that it replaces the
equilibrium diagram calculation of the listed program. Again,
this is a fairly simple task for an experienced IBM programmer.
The author will be glad to furnish additional information
other than that given herein to enable any interested party
to make use of the program. Although the development of the


-66-
curves. These factors are the relative adsorbability of the
adsorbent, and the relative contribution of intraparticle
diffusion to the total diffusional resistance. Two calcu
lated curves using the same xjr and K^a but using equilibrium
diagrams exhibiting considerable differences in relative
adsorbability will have different shapes. If the adsorbent
selectivity is low, the wave will be less steep, for a given
mass transfer coefficient, than if the selectivity is quite
high. This is because the magnitude of x-x*, the driving
force for mass transfer, is much lower for the column of low
selectivity. A similar effect will occur if the intraparticle
diffusion resistance contributes appreciably to the total
diffusional resistance. The concentration gradients set up
inside the particle tend to increase the quantity of compo
nent A near the external film above the value of x*, which is
computed from the average adsorbed phase composition. This
causes the adsorption wave to have a shape which cannot be
duplicated exactly by adjusting K^a in the assumed rate
relation.
It may be concluded that intraparticle diffusion is
a definite contributor to the diffusional resistance in the
large particle size gel used in these experiments. This is
in qualitative agreement with theory, since the average length
of the internal diffusion paths per unit of surface area in
creases with particle size. On the other hand, the Davison


148-
STD
0301
0913
24
0301
0604
STD
1929
0604
24
1929
0832
STD
1932
0832
24
1932
0785
LDD
0110
0785
69
0110
0963
STD
0101
0963
24
0101
0654
LDD
YFSPT
0654
69
0957
1010
STD
1931
1010
24
1931
0634
LDD
XFEED
0634
69
1087
0790
STD
1928
0790
24
1928
0681
SLO
8002
0681
16
8002
0939
STL
1930
0939
20
1930
0983
STD
1933
0983
24
1933
08 8 6
LDD
1957
0886
69
1957
1060
STD
TMCST
1060
24
1013
0766
RAL
1958
0766
65
1958
1063
STL
TI NCR
1063
20
0666
0819
RSL
8002
0819
66
8002
0727
STL
BI NCR
0727
20
0078
0731
SLO
3002
0731
16
8002
0989
STU
0302
0989
21
0302
1005
STD
0303
1005
24
0303
0006
STD
0304
0006
24
0304
1007
STD
0305
1007
24
0305
0608
STD
0306
0608
24
0306
0609
STD
0307
0609
24
0307
1110
STD
0308
1110
24
0308
0761
STD
0309
0761
24
0309
0612
STD
0310
0612
24
0310
1113
STD
0102
1113
24
0102
1055
STD
0103
1055
24
0103
0056
STD
0104
0056
24
0104
1057
STD
0105
1057
24
0105
0658
STD
0106
0658
24
0106
0659
STD
0107
0659
24
0107
1160
STD
0108
1160
24
0108
0311
STD
0109
0311
24
0109
0662
STD
0110
0662
24
0110
1163
LDD
RSTKO
1163
69
0816
0869
STD
TSTMB
0869
24
0622
1075
LDD
0100
1075
69
0100
0653
STD
DRFPV
0653
24
0016
0919
LDD
DFEED
0919
69
0672
1125
STD
0100
1125
24
0100
0703
LDD
YFSPT
0703
69
0957
1210
STD
0300
1210
24
0300
0753


Volume Fraction Toluene in Effluent
-126-
Total Volume of Effluent, cc.
FIGURE 22.- MCH-TOLUENE FRACTIONATION WITH ALUMINA
JOHNSON RUN F-5.


-78-
TABLE 2
SUMMARY OF
ADSORPTION FRACTIONATION CALCULATIONS
Calculation
Number
XF >
Vol. Frac. Comp.
A in Feed
x-y Equilibria
51
0.5
Toluene-MCH-Silica Gel**
52
0.1
Toluene-MCH-Silica Gel**
98
0.1
Benzene-Hexane-Silica Gel
99
0.5
Benzene-Hexane-Silica Gel
2
0.5
a = 2.0
3
0.3
a *> 2.0
4
0.1
a = 2.0
5
0.7
a = 2.0
6
0.9
a 2.0
7
0.9
a = 3.0
8
0.7
a *= 3.0
9
0.5
a = 3.0
10
0.3
a = 3.0
11
0.1
a 3.0
12
0.1
a * 5.0
13
o

to
a. 5.0
14
0.5
a e 5.0
15
0.1
P
1
<
o
16
0.3
a = 7.0


-163-
MPY
TI NCR
1131
19
0666
1288
SRD
0009
1288
31
0009
1361
ALO
0300
1361
15
0300
0906
STL
YEST
LOOP
0906
20
0911 .
.0964
LOOP
LDD
0503
COMPUTE
0964
69
0968
0503
RA
XFEED
Y PRIME
0968
60
1087
0992
SUP
XSTAR
BY CUBIC
0992
11
0090
0096
MPY
FIVE
AVGRAGING
0096
19
0069
1590
SLT
0001
1590
35
0001
1047
AUP
SUMDF
1047
10
0025
1729
SRT
0002
1729
30
0002
1585
DVR
TWLVE
1585
64
0038
1448
RAU
3002
1448
60
8002
1807
MPY
TI NCR
1807
1.9
0666
1338
SRD
0009
1338
31
0009
1411
ALO
0300
1411
15
0300
0956
AUP
YEST
0956
10
0911
0965
SLO
8002
0965
16
8002
0923
STD
YEST
0923
24
0911
1014
SUP
8001
1014
11
8001
1072
RAL
8003
1072
65
8003
1779
SRD
0001
1779
31
0001
1635
NZE
RCYES
1635
45
1388
1739
LDD
DRFPV
1739
69
0016
1419
STD
0100
1419
24
0100
1303
LDD
YEST
1303
69
C/911
1064
STD
0300
PRTCA
1064
24
0300
1353
ROYES
RAU
3001
1388
60
8001
0646
MPY
HLFAB
0646
19
1298
1018
SRD
0009
1018
31
0009
1042
ALO
YEST
1042
15
0911
1015
STL
YEST
LOOP
1015
20
0911
0964
PRTCA
RAL
TMCTR
ADD ONE TO
135 3
65
0034
1789
AUP
1934
TIME CNTR
1789
10
1934
1339
ALO
TMONE
AND TEST
1839
15
1190
0696
AUP
8001
TO PUNCH
0696
10
8001
1403
SUP
8003
1403
11
8 003
1461
STD
1934
1461
24
1934
1438
STL
TMCTR
1438
20
003 4
148 8
SLO
TMCST
1488
16
1013
1068
NZE
PARTD
1068
45
1122
0973
STL
TMCTR
0973
20
0034
1538
RAU
1927
1538
60
1927
1181


-93
TABLE 15
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 4b (cf. Figure 21)
Col
. Diam.
- 2.47 cm.
Ave. Inverse
Rate <= 5.75 sec./cc.
wt.
Gel.
* 96.6 g.
vp
= .402 cc./g.
P b
= .679 g./cc.
fv
- .293
- 0.100 Vol. fr.
Sample Size
5 drops
F
Toluene
Total Vol.
X
Vol. Fraction
Sample No.
Time, sec.
Effluent, cc.
Toluene
1
470
0
.014
2
590
20
.019
3
708
40
.027
4
818
60
.039
5
933
80
.048
6
1042
100
.056
7
1104
110
.060
8
1214
130
.068
9
1326
150
.074
10
1434
170
.081
11
1546
190
.081
12
1652
210
.085
13
1766
230
.087
14
1877
250
.087
15
1990
270
.087
16
~
290
.090


HETS, cm

Q/A, cm./sec.
FIGURE 25.- EFFECT OF LIQUID VELOCITY ON HETS
129


I. INTRODUCTION
This dissertation describes the results of a study
made on the process of adsorption fractionation of binary
liquid solutions. Based on a theoretical analysis of the
factors controlling the process, mathematical partial dif
ferential equations expressing column operation were derived
and solved by numerical integration with the aid of an IBM
650 digital computer. Particular emphasis was placed upon
the statement of the boundary conditions for the liquid
adsorption process, as it is believed that the proper bound
ary conditions have not been used in previous work.
Computed solutions to column operation were com
pared with experimental data taken in this study and with
other published data. It was found that good agreement be
tween calculated and experimental data may be obtained in
systems in which the external particle film resistance to
diffusion apparently controls. Agreement in cases where
intraparticle diffusion contributes to the total diffusional
resistance is not as good, but is considered useful. The
success with the external film controlling case indicates
that when a suitable theory on intraparticle resistance is
derived, numerical integration by means of a computer will
prove the best means of obtaining satisfactory solutions,
-1-


164-
AUP
CDCSB
1181
10
1050
1006
STU
1927
1006
21
1927
1380
PCH
1927
PARTD
PUNCH CARD
1380
71
1927
1122
PARTD
LDD
SRYF
COMPUTE Y
1122
69
1625
0982
RAU
0101
162 5
60
0101
1056
MPY
T I NCR
COMPUTE
1056
19
0666
1588
SRD
0009
ESTIMATES
1588
31
0009
1511
ALO
0301
OF X AND Y
1511
15
0301
1106
STL
YEST
FOR NEXT
1106
20
0911
1114
RAU
DRFPV
BED POINT
1114
60
0016
1172
MPY
BI NCR
1172
19
0078
1493
SRD
0009
1498
31
0009
1222
ALO
XFEED
1222
15
1087
1092
STL
XEST
AVGYB
1092
20
0033
1638
AVGYB
RAL
YEST
1638
65
0911
1065
LDD
0503
1065
69
1113
0503
RAU
XEST
COMPUTE
1118
60
0033
1688
SUP
XSTAR
Y BY
1688
11
0090
0746
STU
DRFNW
AVGRAGING
0746
21
0013
1266
AUP
0101
METHOD AND
1266
10
0101
1156
MPY
HLFAE
COMPARE
1156
19
1259
1430
SRD
0009
WITH YEST
1430
31
0009
1453
RAU
8002
1453
60
8002
1561
MPY
TI NCR
1561
19
0666
1738
SRD
0009
1738
31
0009
1611
ALO
0301
1611
15
0301
12 06
AUP
YEST
1206
10
0911
1115
SLO
8002
1115
16
8 002
1023
STD
YEST
1023
24
0911
1164
SUP
8001
1164
11
8001
1272
RAL
8003
1272
65
8003
.1829
SRD
0001
1829
31
0001
1685
NZE
CNYSA
AVGXB
1685
45
1788
1889
C NY'S A
RAU
8001
COMPUTE
1788
60
0001
0796
MPY
HLFAF
NEW YEST
0796
19
0899
1320
SRD
0009
AND LOOP
1320
31
0009
1143
ALO
YEST
1143
15
0911
1165
STL
YEST
AVGYB
1165
20
0911
1638
AVGXB
RAU
DRFNW
COMPUTE
1889
60
0013
1168
AUP
DRFPV
X BY
1168
10
0016
1322


Volume Fraction Benzene in Effluent
-120-
Total Volume of Effluent, cc.
FIGURE 16.- BENZENE-HEXANE FRACTIONATION WITH SILICA
GEL LOMBARDO RUN B-2.


FIGURE 10.- ULTIMATE ADSORPTION WAVE SHAPES
COMPUTER SOLUTION TO PROBLEM 52.
i


11-
1940-1950
In 1940 Brunauer, Deming, and Teller (50) combined
the recognized live types of vapor isotherms into one equa
tion.
One of the first papers dealing with the kinetics of
adsorption in a column was that of Wilson (51) who developed
equations assuming instantaneous equilibrium, no void space
between particles, and a single adsorbed component. This
paper showed mathematically the existence of an adsorption
band which moves through the adsorbent column, and thus
quantitatively agreed with known facts. Martin and Synge
(52) pointed out the analogy between a moving bed adsorption
column and distillation. Mathematical equations were developed
for the steady state case to compute the number of equilibrium
stages required for a given separation.
DeVault (53) extended the work of Wilson by develop
ing differential equations and their solutions for single
solute adsorption which considered the void space between
particles. Differential equations for multiple solutes were
derived but not solved. There was reasonable agreement with
selected previously published data.
Thomas (54) proposed a kinetic theory which leads to
a Langmuir type isotherm at equilibrium. The adsorption
step was assumed to control with no diffusional resistance.
Solutions for the case of multiple solutes were impossible.


-53-
necessary to give a given separation may be readily deter
mined, the experimental determination of the height equiva
lent to a theoretical stage (HETS) has always been of
interest. It is apparent that an experimental apparatus
utilizing the countercurrent principle could be built and
the determination of HETS made by suitable experiments.
However, it is not easy to construct true countercurrent
apparatus in the laboratory. It would be more desirable to
r
devise a means of predicting the HETS of a moving bed from
a simple fixed bed experiment.
The analysis of the adsorption process made in the
previous sections affords a way of doing this. It has been
pointed out how the establishment of an invariant wave shape
is possibly subject to one restriction concerning the shape
of the equilibrium diagram, a restriction which is almost
always met. It was also shown that the movement of the
ultimate wave through the column is equivalent to a counter-
current experiment in which the adsorbent and liquid feed
rates are adjusted to maintain the same velocity of feed
liquid through the bed and to maintain the adsorption wave
stationary. It was further shown that the flow rates between
the two cases can easily be related.
This leads to the conclusion that every fixed bed
experiment in which the column is long enough for the ad
sorption wave to be established is exactly equivalent to a
continuous countercurrent experiment. The one difficulty


-46-
If Q is the volumetric flow rate of the liquid
through the stationary bed, Q/Af is the velocity of the
liquid through the bed void volume. This velocity would
have to be reduced by an amount equal to the velocity of
travel of the adsorbent in the countercurrent case, in order
to maintain the same relative velocity of fluid through the
bed in the two cases. If W is the mass rate of flow of ad
sorbent required to maintain zone 2 stationary, W/p^A is the
velocity of the adsorbent through the bed. Therefore, the
countercurrent liquid feed velocity may be related to the
fixed bed velocity.
Q' /Af v = Q/Afy W/^A (9)
where Q' represents the volumetric liquid
feed rate in the countercurrent case.
and Q represents the volumetric liquid
feed rate in the fixed bed case.
A volumetric material balance on component A about zone 2 for
the countercurrent case gives,
(WVp)yF* (Q)(xf) (10)
Substituting for Q' from equation (9),
(WVp)yF* (Q fvW/pb)(xF) (11)
A little study will show that the velocity of the wave, VWj
when the liquid feed rate is Q, is equal to the velocity of
the adsorbent bed required to maintain zone 2 stationary when
the liquid feed rate is Q'. Solving equation (11) for W/pbA,
the adsorbent bed velocity, gives,


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'2012-02-11T09:21:36-05:00'
describe
'976248' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKG' 'sip-files00005.tif'
f62b7bdb029fb356c57eeeb9c655d87f
035c67565bd8f02f06970f69c87e9c9647c0c967
'2012-02-11T09:21:40-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1307' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKH' 'sip-files00005.txt'
5c8880c9408a1351e36c6e4fd8717b48
7fa9453d974ede5848441d2110dfe7dc25904a3b
'2012-02-11T09:22:32-05:00'
describe
'4998' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKI' 'sip-files00005thm.jpg'
ee920b5c1bde1c9a741a4ed55a7b870b
e6f2e7c5d31e65a394387902d15e473aa13bbbef
'2012-02-11T09:20:16-05:00'
describe
'1002665' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKJ' 'sip-files00006.jp2'
98ff8c9811c7de1f45ae1232ef4734c7
d44fc710fc506582a351e539a8d952475f9bf78b
'2012-02-11T09:20:10-05:00'
describe
'77200' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKK' 'sip-files00006.jpg'
daf098a113805c642379cdc8c63e289c
64a423806e0134cce4e54b1df87f70dc59d2bb0e
'2012-02-11T09:24:00-05:00'
describe
'37557' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKL' 'sip-files00006.pro'
8dfd86043f7f3d8036abeeb5ccf31462
bd9d4ac955e6f36cbf35f47472433a85cedd71d3
'2012-02-11T09:21:56-05:00'
describe
'23854' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKM' 'sip-files00006.QC.jpg'
74b1d79d7b1f2bfc146035974dad5616
ee626aba98feaa6c8afe05cc1edde55a7d31bd60
'2012-02-11T09:20:57-05:00'
describe
'8223764' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKN' 'sip-files00006.tif'
fcd708100ffbf676e49fcfeb37f450c0
5d0bf45d21ae26e29546ed70ceb1eb53d9ca01da
'2012-02-11T09:21:48-05:00'
describe
'1626' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKO' 'sip-files00006.txt'
cfa9fa1fb496bf7ec8cb2e83fce03485
2f4a25bfa129b1063ee0eeab142db895d120f0fe
'2012-02-11T09:23:54-05:00'
describe
'6431' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKP' 'sip-files00006thm.jpg'
4e2718adb039dfffeb0b37a40d412060
79e3d0ccc06e8a1a1344f892659eddc3e0e13d2c
'2012-02-11T09:23:22-05:00'
describe
'80253' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKQ' 'sip-files00007.jp2'
5aa3e2a936a73f114a5b35de57687aea
b6a09b4e147b98b1d5247dc6e860e598d22b7bec
'2012-02-11T09:30:46-05:00'
describe
'65272' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKR' 'sip-files00007.jpg'
de859c255e2f1185d76d72f8a35bf6c7
a41e77b3743680366d37f62cbe2cf14869afe1ec
'2012-02-11T09:21:20-05:00'
describe
'31084' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKS' 'sip-files00007.pro'
eac7fdab0167d04cdb7582385b7b5c0b
b82c816cc798b9acfb5a90a571be0008266e6211
'2012-02-11T09:22:05-05:00'
describe
'21338' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKT' 'sip-files00007.QC.jpg'
7c2ea25400b8b0f77b3cc81112e27ca3
8687332157606ef72c890445e26fad0284e6ebe8
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANKU' 'sip-files00007.tif'
0f54486cde319965b1e855d949fe49d1
d3be13650726cde5ebbb1a613f66de1084432119
'2012-02-11T09:22:16-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1387' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKV' 'sip-files00007.txt'
a5c069696a7f7fcb4bd1f33bcf364e22
57e049d856ab2b6128bf9a16ffcbcd1e08ca38a6
'2012-02-11T09:20:54-05:00'
describe
'5981' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKW' 'sip-files00007thm.jpg'
058c5c9d5b735f0f0593298f299d55d8
e1f2543544f5c5216a3278c93552a22f274e8519
'2012-02-11T09:24:13-05:00'
describe
'92574' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKX' 'sip-files00008.jp2'
e58e08c0e23724a5ba6b0c111bec2b21
8fbf3869f896bb92b4f77fadfcf1fb3c0cc01112
'2012-02-11T09:29:18-05:00'
describe
'76306' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKY' 'sip-files00008.jpg'
1f679759868770d4833e6d8994f9c3c1
534b52ee1cf51571d34f03576183bd22b5659a76
'2012-02-11T09:21:01-05:00'
describe
'38729' 'info:fdaE20090607_AAAAAMfileF20090607_AAANKZ' 'sip-files00008.pro'
9441791c275cbf3c203de28a34a4cf45
6ea464c1019369b85075aadd2afd6ef504a41b0a
'2012-02-11T09:31:30-05:00'
describe
'25124' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLA' 'sip-files00008.QC.jpg'
5a5cc7a68d2b9550994f9557a51e92e2
ce7c2a11a1cba3f9fa6d9cc78cad847387036da2
'2012-02-11T09:25:12-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANLB' 'sip-files00008.tif'
cc400a0aaac5683f0e55463c56379da7
4486296ee8c4f7a19e02547077266a895b966271
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1680' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLC' 'sip-files00008.txt'
8327feae5c91b4602487af93bd7150c5
9d061aaca2e5cf9a643725360be9b13a0233578e
'2012-02-11T09:21:15-05:00'
describe
'6854' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLD' 'sip-files00008thm.jpg'
314530acd4ab5bb3cc5244c98ebb452b
f9d68eac7332ecc73183f5f057cab858d23606b4
'2012-02-11T09:25:55-05:00'
describe
'65191' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLE' 'sip-files00009.jp2'
cbde415a31c5d78777c0e0d320ca5c96
d10dacfcaa8051c2ed0e83405e5ffe19b1159e90
'2012-02-11T09:22:35-05:00'
describe
'52990' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLF' 'sip-files00009.jpg'
2e2b446040e7051e3def29f140a6ea25
214c6c6f85b1b1a93b73bf4dcf7aec5e1c561472
describe
'24003' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLG' 'sip-files00009.pro'
4d7104d9e874756435320b50ebba95b3
129a2c56d107f9ac862ed1fb2ac6bc82058f0653
'2012-02-11T09:23:13-05:00'
describe
'17983' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLH' 'sip-files00009.QC.jpg'
fc11e78910909eb09df70794281a4ac3
45b259c3b09d42b3b44348fc51722669fe83d02f
'2012-02-11T09:20:40-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANLI' 'sip-files00009.tif'
c9eeb0ae671e3b5dbfdb7a7e67ec1ef9
39a90aa4a72813b322546751f19f848d8a092529
'2012-02-11T09:21:34-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1052' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLJ' 'sip-files00009.txt'
ac699132bd5c084e8f19987df7023e5b
ba27818faa647b880b385cf93f21acab33080f8e
'2012-02-11T09:21:47-05:00'
describe
'5259' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLK' 'sip-files00009thm.jpg'
4827ad2290cf9342ecca7482850a2aac
9a02c22d8698f142d8e8f722e08347b40b81016e
'2012-02-11T09:24:48-05:00'
describe
'101198' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLL' 'sip-files00010.jp2'
687e55b98ab453413aac3c3fcf9aa90c
bf99c9fbd027cc02af8699a5f00338b6e1c1075f
'2012-02-11T09:30:57-05:00'
describe
'78423' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLM' 'sip-files00010.jpg'
04dea8495164f4237ed7eb9843c731e4
d322895952ffb5e2be2d4c0a54a2a71412e396f4
'2012-02-11T09:26:59-05:00'
describe
'34525' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLN' 'sip-files00010.pro'
8fb78730428bd7fc616c164a19e3180f
5c9d56c623e9cada9d0aa761baf8b1d7a341533d
'2012-02-11T09:27:06-05:00'
describe
'27900' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLO' 'sip-files00010.QC.jpg'
62a773e01476ff027844568eb5ab9a08
94ea1bfbb99984f3ac004825ab6deee4beb1d6c3
'2012-02-11T09:22:34-05:00'
describe
'975040' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLP' 'sip-files00010.tif'
de7d60ce2a282e444117bad6caa501e7
5d897590524aa47f6d57364d2e0c91078d85e0e2
'2012-02-11T09:23:32-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1397' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLQ' 'sip-files00010.txt'
3784cb135872639d4f8f6a5da911ae10
f75b17e0391190325581f16513ee73e3ea6ea0e7
describe
'7446' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLR' 'sip-files00010thm.jpg'
21ee23178627db6107057d1689f8449f
1932152e820f0b07b61bf9b98216e43f4ef22b9a
'2012-02-11T09:22:27-05:00'
describe
'84550' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLS' 'sip-files00011.jp2'
8c4a0464212682011f3365bb5691205c
6be368eaf34cb4b0182980724b2a2236e30254a7
describe
'64821' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLT' 'sip-files00011.jpg'
970a1128e600932ff0a0190a2dbd028a
02db444f7f38c59aa40e9bcccd7fec0d03f765ef
'2012-02-11T09:28:45-05:00'
describe
'27427' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLU' 'sip-files00011.pro'
47d9dc78f3880b3c5ab08b2bb1d33468
f1188b7ef9afc803bd1a09a3d355899131a3031e
describe
'22485' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLV' 'sip-files00011.QC.jpg'
5b2e4bcfeba384c9f48115a693aee7a5
02bc8587db5d3b290084dc6f1c17f2dffe8dd4b4
'2012-02-11T09:22:18-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANLW' 'sip-files00011.tif'
17c65fdf5ff86199969d246b247abde4
45c4905c3dfaa4eae9fd3bd519778c4fe81f0a5b
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1169' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLX' 'sip-files00011.txt'
4be470421dea17270822996396b9e960
f97c5fcb19e151ebcf265dfddc62c65dad9b8051
'2012-02-11T09:20:08-05:00'
describe
'6721' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLY' 'sip-files00011thm.jpg'
c9f60ae1d9f5acfbf58f943e85351b8d
21744b022e83fb207e393e89eb51f5da816d358f
'2012-02-11T09:20:33-05:00'
describe
'105963' 'info:fdaE20090607_AAAAAMfileF20090607_AAANLZ' 'sip-files00012.jp2'
af1dab9722b8168790f4611d0c84eec2
dab446e99df0f7b7ef5dd81f9d0788ff02a2c4c0
'2012-02-11T09:24:06-05:00'
describe
'79530' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMA' 'sip-files00012.jpg'
f870c498372a0e009f4aa9307e76c06d
7e5b348bb38727c2fe9328dba9c6a9c71b6d7e78
'2012-02-11T09:19:56-05:00'
describe
'36063' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMB' 'sip-files00012.pro'
902e618b9150a08522fd799f8ca993de
db6c29d1ac87a10784e9f9550c9fac705efb9651
'2012-02-11T09:30:52-05:00'
describe
'28850' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMC' 'sip-files00012.QC.jpg'
4c2dcb14770617ee3c4ea6c934c58795
efa8111aecc142377be97d11ae418d6c7ad033e8
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANMD' 'sip-files00012.tif'
a903d0adaa3ec9e9a8dd7527335d94ea
db749da6bc81d6c310e29844d5cf407578b31f19
'2012-02-11T09:25:27-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1496' 'info:fdaE20090607_AAAAAMfileF20090607_AAANME' 'sip-files00012.txt'
9df9fb25d914a9b8470f5175ec274246
6d92423c7287c50a303da411f6e0164324584b68
'2012-02-11T09:31:02-05:00'
describe
'7881' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMF' 'sip-files00012thm.jpg'
51881503b99b17701a5c484cec532257
a572efff63eacf96bd3ace0e73ce2f777e7cdb0c
'2012-02-11T09:30:58-05:00'
describe
'115755' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMG' 'sip-files00013.jp2'
05eb6179c25155a2901d7316e339540c
1f3d44026ce7c4ba0bc356dbd5f71713c35414ec
'2012-02-11T09:20:37-05:00'
describe
'88694' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMH' 'sip-files00013.jpg'
2d65f22d65929af7e83b1727e7ebb9ef
93c1ae822e1bf0b4a863791907538d5fe705b488
describe
'39624' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMI' 'sip-files00013.pro'
28768a511d6f1edbb98273478c3cdf75
b856f0562a521f015939032906d0029202409a99
describe
'31093' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMJ' 'sip-files00013.QC.jpg'
7583ad7b943eb4fe46cedacdeb1db895
bf44b5f0a04ff9c7b2ae83be8a0b3e6413a3a29e
'2012-02-11T09:30:27-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANMK' 'sip-files00013.tif'
06e76e4c267603b19185d14e571ca989
144f97e07d7883348d41d8bb066cd429f80238be
'2012-02-11T09:29:45-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1618' 'info:fdaE20090607_AAAAAMfileF20090607_AAANML' 'sip-files00013.txt'
264675ac570086ffb157ac1462bef008
450e21d09140bc0d9d73bb4949200171e61fdef4
'2012-02-11T09:29:00-05:00'
describe
'8645' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMM' 'sip-files00013thm.jpg'
67a9c78a16df278b69ed490f81811c6f
60d4ebfa829c78ebc87af237625b682618d08115
'2012-02-11T09:21:28-05:00'
describe
'46500' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMN' 'sip-files00014.jp2'
ac6ecd197e8daf6362982741756ec010
2483aee17f38625ec29abf81bc1b64f0613fd2d7
'2012-02-11T09:23:16-05:00'
describe
'38171' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMO' 'sip-files00014.jpg'
49a5ca673a8af1e9ee753047a6a57ca2
9a9eaec00fa1b0f327c70e4f1c57446ca7af976c
'2012-02-11T09:21:00-05:00'
describe
'14433' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMP' 'sip-files00014.pro'
4cbb4eab1fb3c12807e7a6cece313ae2
029f811f4f2a65f9e2f555cf1075ff966fba3d4d
describe
'13393' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMQ' 'sip-files00014.QC.jpg'
a0ff583425a22f3f5c19608b7311ae27
3706b29e85a4ad6988e93354cba2bcd5262c74d5
'2012-02-11T09:23:08-05:00'
describe
'974436' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMR' 'sip-files00014.tif'
89ba2d97f46d32114bfb561e98323a23
c1a13c9a96bec3b7a3ec82a936e055e9e0e151aa
'2012-02-11T09:20:00-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'596' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMS' 'sip-files00014.txt'
2b6084560c8d00a7a178bb293eb71751
0733fefc74ed5bfcdc11b71acb788a82064a9fc5
'2012-02-11T09:24:31-05:00'
describe
'4082' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMT' 'sip-files00014thm.jpg'
73440d94f540c649795914bec5149515
13e4dc7930f17435217c44b7de62ea44a3e18c61
describe
'96124' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMU' 'sip-files00015.jp2'
a6fd073dbf051ce164398e30d72ec5d1
1bfafe472a4b79abb952167f905247dfd72e7727
'2012-02-11T09:23:01-05:00'
describe
'73894' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMV' 'sip-files00015.jpg'
127da562f618f0fe419ca43e6064be2b
4d3d0d7cc489597da70b3b57d520b46e32ece74c
'2012-02-11T09:20:15-05:00'
describe
'32280' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMW' 'sip-files00015.pro'
268a53f84511c0bce20e6d29d22e2518
51b538cb57916cd3c900cc88b567112202828631
'2012-02-11T09:19:51-05:00'
describe
'26536' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMX' 'sip-files00015.QC.jpg'
bd8bba7790949bc02f139126c9c25aba
05453b837e1bb4e158b7cf1ce423d3a95d1ef3e0
'2012-02-11T09:20:41-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANMY' 'sip-files00015.tif'
bcfb3d6079c57d658cee4830c75bd5ed
19761dcc97101723ae33b585cd6885d7e066dad6
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1347' 'info:fdaE20090607_AAAAAMfileF20090607_AAANMZ' 'sip-files00015.txt'
e95ddefd0dd69984f320e2ba28e9e55e
b6ad771516588970515762b32155afe628b47ff7
'2012-02-11T09:24:39-05:00'
describe
'7360' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNA' 'sip-files00015thm.jpg'
4df11f5bb120f7b0a669dadae67b28a4
89a688c50662a1b9daa84d878be3cbb224eaa9ab
'2012-02-11T09:23:39-05:00'
describe
'116788' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNB' 'sip-files00016.jp2'
ef8520592bbe2bc62e64e82720bca707
377ee8d46a35a6fc93abad60ed74551ae756f859
'2012-02-11T09:24:37-05:00'
describe
'89488' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNC' 'sip-files00016.jpg'
c843168fe61c553e017dd4ec35849c40
f976817bfd43e23ba42d7d970c1a05ed839ba8f0
'2012-02-11T09:21:09-05:00'
describe
'38905' 'info:fdaE20090607_AAAAAMfileF20090607_AAANND' 'sip-files00016.pro'
fccd86438efd44e2380d8439ffd5a623
f0e0ca076bde84a2e8a8af81e70885fbd19761e6
'2012-02-11T09:27:05-05:00'
describe
'32025' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNE' 'sip-files00016.QC.jpg'
ecfcb99e3c5e3862e6086662a4f53e48
20043ef2206d6316b4ff5096db6add8a5a5c94f2
'2012-02-11T09:21:06-05:00'
describe
'971813' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNF' 'sip-files00016.tif'
0b6d98fbc08d573f303a2378d4e7f93e
eb4285ddc417f159abaa1db64e6996f5e52eb2e6
'2012-02-11T09:25:01-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1590' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNG' 'sip-files00016.txt'
1ffbd3943d95d7aa9a3492d95c0631c6
8b94d5e0059c0fe633809fcb96c0602b191f65bf
'2012-02-11T09:23:34-05:00'
describe
'8629' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNH' 'sip-files00016thm.jpg'
9b1265fa38a93cc807f7e051e88e7bc6
dab412fe801cded99e5b9c018bf34f1bff2361ce
'2012-02-11T09:23:57-05:00'
describe
'106589' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNI' 'sip-files00017.jp2'
65a5c595f28712b2ae00e56f9d9d2b1a
343c9791db5b5b7f79b6200ae4db68797ed29df2
'2012-02-11T09:22:56-05:00'
describe
'80777' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNJ' 'sip-files00017.jpg'
db6eb3df26ad8bc66c5cefbb709961cd
38e2c3d3a801f1c2a221a86941d0781e33e82795
'2012-02-11T09:22:52-05:00'
describe
'35975' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNK' 'sip-files00017.pro'
4505320c1a705eb3251d6d60c198cc85
84bf10ff8b645e8f97cb72e49695f4b655615686
describe
'28957' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNL' 'sip-files00017.QC.jpg'
91c4fd88f1e0451e3bd15562e27fcb8d
2745809afcf0a5c5dc9ac1935b86d5b068186962
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANNM' 'sip-files00017.tif'
223d5733a79e205a9dcfed9d1fa76527
506892b13d47a30633c3ee5d26f7b588f0fa24e8
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1484' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNN' 'sip-files00017.txt'
9f881a4518325f9811cac63ac9a25f8a
d96f725608cb51cd384ddda6a1dcb0fb2f922a76
describe
'8082' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNO' 'sip-files00017thm.jpg'
65cb15f56526a5377121c62b37e5126a
6eab19bb7e95c417661c50d69074fe2cad0785fc
'2012-02-11T09:25:18-05:00'
describe
'106608' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNP' 'sip-files00018.jp2'
7f690749d44e418260212bbd912ed156
c8b93aa3dfd7e09aa8289153db1bd080c6f6e5ea
describe
'82313' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNQ' 'sip-files00018.jpg'
edf78bf44abfbff011e564d252869136
819ad7bb3f4bc7c6eec876c595809278bfeff7be
'2012-02-11T09:30:35-05:00'
describe
'35467' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNR' 'sip-files00018.pro'
946c6fa232f38acbe3a8fedc67b74ed8
2ec9823747e31ece935acff3150e4299e391be15
describe
'29991' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNS' 'sip-files00018.QC.jpg'
47e36efde7b7bee01bd64c3c36ac88aa
550d878c7bacdcdc912757af97be37d112ca4f60
'2012-02-11T09:23:24-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANNT' 'sip-files00018.tif'
2d150efb2b35b4e2f1c84e63e6fee04f
c3aea97ec0a7dc6db3f80de7216ac743c97dfe63
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1495' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNU' 'sip-files00018.txt'
f22aa24f990644d272322c29f5fc1a10
78de741b76964e0387ebb1b00b42ac5d05774196
'2012-02-11T09:22:23-05:00'
describe
'8145' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNV' 'sip-files00018thm.jpg'
65e3af7acba3b4d8d0ff0e7937d9a244
556da90ffa2528c47cb3d98a25242d5af7b15e64
'2012-02-11T09:24:21-05:00'
describe
'107942' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNW' 'sip-files00019.jp2'
ad3e44c9d4b87d7ff7c2227761c1f571
bda9f7e01ee4908842ff369a2b0a4a133a1ce8f2
describe
'83566' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNX' 'sip-files00019.jpg'
e8908138a204f9f89a04ed57ede07c46
6558b42bc4d36633f4c04894740d69061de41acc
'2012-02-11T09:22:15-05:00'
describe
'35882' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNY' 'sip-files00019.pro'
a586b018844bc972719392c21e2c7891
2c1953a04c01d96668baebac3fa80851d51171b5
'2012-02-11T09:21:58-05:00'
describe
'29750' 'info:fdaE20090607_AAAAAMfileF20090607_AAANNZ' 'sip-files00019.QC.jpg'
9cc790fc50609ca237bd1ada5e9b890a
e2a805edfe70fc9ed6ea576ae58524495baa5a9a
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANOA' 'sip-files00019.tif'
60745945baa7ea6db822bbc9f02f819e
0ca704e096ebbbdc7f491e832584683e404d38b7
'2012-02-11T09:21:14-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1487' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOB' 'sip-files00019.txt'
58c342aa4552c5b17d2a2750cb891c9e
c19ce42df53e518fe6441e2bbd4cb0a2692dcd9e
'2012-02-11T09:23:28-05:00'
describe
'8124' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOC' 'sip-files00019thm.jpg'
09eb388ecc01f3b2df16b44b805fe51c
2f8f6de0486491b6234ff5006ea242bfcf8805f2
'2012-02-11T09:31:13-05:00'
describe
'106553' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOD' 'sip-files00020.jp2'
a87890e46cbcecdc0cb7286efc7fae31
d67461f288f1dd7e2730d9de6ea0102305067cf7
'2012-02-11T09:20:17-05:00'
describe
'81548' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOE' 'sip-files00020.jpg'
dabc0f710b610fea90c2e98a8c014192
82447db5262eefe4d68d97cb56835f0d1521a574
'2012-02-11T09:24:45-05:00'
describe
'35383' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOF' 'sip-files00020.pro'
667babb5705e6865d713b241b82172b6
eaba63814c37c100a084d2744a51f90cfea3550d
'2012-02-11T09:21:45-05:00'
describe
'28484' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOG' 'sip-files00020.QC.jpg'
8ec8e87bd7a4e3c47b77d23b78362f8e
19cb27d24c4d439ff6aec1469587936606917e90
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANOH' 'sip-files00020.tif'
54bbb240ccf5776fe7a356ee21b3cdd8
b397a90222b7f0e6ecefc5302ee4f7c2af70c4e6
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1452' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOI' 'sip-files00020.txt'
4300b253ed53e77fb1cb0e84eee06f60
9c4eaaa959ac8569bbd3f8352846cd9aa5ae938d
describe
'7893' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOJ' 'sip-files00020thm.jpg'
4f09e07d95e843c509224ac5b5b1ce70
2a28bc74d404aba983ee1065eaa73ca3f9c5770d
describe
'107589' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOK' 'sip-files00021.jp2'
8402d9d93c92ba9777482c781089dcdf
f6387d57d5ddaaba4d5682e50746f5bd558d572a
'2012-02-11T09:25:23-05:00'
describe
'82497' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOL' 'sip-files00021.jpg'
92d65ceb9955e03e7881d767ca791900
d86ddac57d21f5327ce3b74c1430e37e7cc53d08
'2012-02-11T09:22:11-05:00'
describe
'35437' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOM' 'sip-files00021.pro'
11bfeb7409e269dc2bd4f057120afdc8
2a4f89a07ea360e7f3c6ecfaa536db4fe4b438d4
'2012-02-11T09:25:22-05:00'
describe
'29218' 'info:fdaE20090607_AAAAAMfileF20090607_AAANON' 'sip-files00021.QC.jpg'
72667fe97f48eac183a1202b7a9467be
b00b9851ae380c5ebed8276a17e3b49894196c4a
'2012-02-11T09:23:06-05:00'
describe
'970609' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOO' 'sip-files00021.tif'
fd7f09b262f139dab17096ac9b2984a7
e8291492c4e9163061356f2be008365b755789bb
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1468' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOP' 'sip-files00021.txt'
6961f7d5680cd6016b8a55d90ef86c48
4b195a793fb856529508d3f3b9930e7bac1386fc
'2012-02-11T09:25:08-05:00'
describe
'7970' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOQ' 'sip-files00021thm.jpg'
e319751c6108bca3b32a896044eb23ce
b7711dcf2386204fa742c61de064ec105e896c76
'2012-02-11T09:31:00-05:00'
describe
'113249' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOR' 'sip-files00022.jp2'
25c4f28ca4da4dab9add3006188c1063
2d6011fca6ab75354b8dedf186765f77fcb07ee2
describe
'86970' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOS' 'sip-files00022.jpg'
6d565c084d846be4eadf32898a279867
ed5fbe1c1a11e78cc6caaced0fdcaafab9bc5359
describe
'37634' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOT' 'sip-files00022.pro'
15dc5a71941522ad6f1e2caebffe01ff
7daef711840733c84c55f9ea3b56157e38e99fdc
describe
'30995' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOU' 'sip-files00022.QC.jpg'
81c88c6564928a3eec141c18740b5ea8
12865267b7f2d08ba5572987c6caf5416a581db7
'2012-02-11T09:25:20-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANOV' 'sip-files00022.tif'
2945b268246319353adef9586ca0cd52
0816b14f1d8d69b6e41b39949267fdb584d85e46
'2012-02-11T09:23:46-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1526' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOW' 'sip-files00022.txt'
b91ecc95deccb7bff8d7837bba72d84a
c8dbecde0c99648e7a8c5408b05240bf20076c27
'2012-02-11T09:30:55-05:00'
describe
'8594' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOX' 'sip-files00022thm.jpg'
06a1254cdb42177d733df3ba01bc049b
485b9b5477495ab493c516dbd0871b3755fe4630
'2012-02-11T09:24:46-05:00'
describe
'100495' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOY' 'sip-files00023.jp2'
9ad465c52c0fa8b002f61f0a3e8325fb
b82b5f33f8320b5770d72e23ffd8d9491f58a912
'2012-02-11T09:23:49-05:00'
describe
'78006' 'info:fdaE20090607_AAAAAMfileF20090607_AAANOZ' 'sip-files00023.jpg'
231c8eac00d7bb9b163aaec7eb7637db
0c995e32ed6245d45bf84e6f1002cb1f007b23bf
describe
'33988' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPA' 'sip-files00023.pro'
7d9ae9fb97fc1b1d039e0a42f2097dbb
99d13a2608262c2c4a5ae422b9c8a93ac21896fb
describe
'27581' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPB' 'sip-files00023.QC.jpg'
7c43b147beeb7ae7333bb50bb644aab0
5a21438cbe08e432bca6c08f57612351659bc5ed
'2012-02-11T09:30:31-05:00'
describe
'954957' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPC' 'sip-files00023.tif'
0d81c8aedc5beeed396d1020e36d25c6
9056c08f2914d6394c6a008e5777fc9edc9fa04e
'2012-02-11T09:21:16-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1437' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPD' 'sip-files00023.txt'
d7dde8692215ef8c4f2a72e4be9c9fce
d80719b492f7253d05a3529485be6767173bddd2
'2012-02-11T09:24:05-05:00'
describe
'7327' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPE' 'sip-files00023thm.jpg'
37dd21e4d20322385f322b04d9f2974b
12f95ac56889b44ad79b14667e9e484680476236
'2012-02-11T09:22:17-05:00'
describe
'410942' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPF' 'sip-files00024.jp2'
5357aee9d000bb51a9c5c9c53a51ca7a
7879513b66a62a9065e8e96032042a47e35f4ce7
'2012-02-11T09:24:49-05:00'
describe
'34769' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPG' 'sip-files00024.jpg'
489c7c9902655c5674b2fbd07db0066b
b157a36786b9ccefe80c5f1651fc1c6ed521bb5c
'2012-02-11T09:24:36-05:00'
describe
'12900' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPH' 'sip-files00024.pro'
e2ef0a9421066fd2ceae85bc27afbb22
a3be0401b6aafc88564acf7c6d3843a60e9a9dde
'2012-02-11T09:19:59-05:00'
describe
'11468' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPI' 'sip-files00024.QC.jpg'
0c84f773ddbf201e1257724eb9b28110
59b8b42c20cd9ce527e7d7507d1416337c08b922
'2012-02-11T09:31:11-05:00'
describe
'8077144' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPJ' 'sip-files00024.tif'
7e816c19790883eb5104774f6c0c7a65
12d77a15bd84854b6825bafd3e3bcc221a2caa93
describe
'575' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPK' 'sip-files00024.txt'
2681a4e378a58430392d4040b83fee31
0bf441abab61eb2ee4946c933abc5dd731347b81
'2012-02-11T09:23:35-05:00'
describe
'3271' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPL' 'sip-files00024thm.jpg'
1f5786cf733bafa35ff1c5e5f245e28d
8dff44117dbc06a7ec765af7c271f0f09260772e
describe
'102109' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPM' 'sip-files00025.jp2'
b8015b7eeef352ff371ea21abb2ae8eb
7e1f6e4849e275982d1e8675103ce27c3468a7e4
'2012-02-11T09:28:57-05:00'
describe
'78983' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPN' 'sip-files00025.jpg'
6e2e5e5138c8119a98034d62f4a865e3
98b7ba584d71b2025319496d8e3adae2cbadf290
describe
'34445' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPO' 'sip-files00025.pro'
f25cff56befe69e10654d59f678cc9af
a859f6b6815521b0dfa61de5bae42b76d6c5e5cb
'2012-02-11T09:31:08-05:00'
describe
'28026' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPP' 'sip-files00025.QC.jpg'
ee12305756d104458a64791c8da6c655
8d276b4cc4ba4ab818164debd547e4844c865594
'2012-02-11T09:21:21-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANPQ' 'sip-files00025.tif'
fa1b3afa52f15daef370404037723380
49ee6dba18175800199a1f505882407e3b1405e6
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1430' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPR' 'sip-files00025.txt'
cf93d5def6fea112436bab79e07f93c0
aa9d36d2bd7b7cfe43966cc8be616d62664c3c21
describe
'7666' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPS' 'sip-files00025thm.jpg'
27c5d5e5a8b3d050ab755d7f0ae52974
f74e05c63ba0a81444adda53ff39d37f4195b21b
'2012-02-11T09:21:19-05:00'
describe
'999700' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPT' 'sip-files00026.jp2'
7b88357677cecb1551dc812624487e02
514ce501102f353530f44e2e2c5865f6dab5b520
'2012-02-11T09:28:22-05:00'
describe
'85864' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPU' 'sip-files00026.jpg'
a101dfea528b867b60b7319d791771ed
8f471014b8ed14517e5b12cd2a2659e06c62f2e0
describe
'37918' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPV' 'sip-files00026.pro'
c284fdb09bd1ffbb7a6c96d798ff4f2d
de3214959ba9bcb265b60d691959d72432f90642
describe
'30559' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPW' 'sip-files00026.QC.jpg'
f76ebc6c582e8a2d4640d1e1d425c330
94922c4c109bf3b2e6b168b04b25d4011b975fc5
describe
'8018776' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPX' 'sip-files00026.tif'
7dc2e05c80d8c92825ab75e352654420
a8a32d0dda4db10f8d0540f57422bc529fd1eca1
'2012-02-11T09:31:10-05:00'
describe
'1549' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPY' 'sip-files00026.txt'
28028914b20db26292bccdfa5b5a00f4
e677c996ec1c6deb339adcc23503623a1f0785f7
describe
'7825' 'info:fdaE20090607_AAAAAMfileF20090607_AAANPZ' 'sip-files00026thm.jpg'
c1c53eeef4fcffa590a8f2672b016a3b
fcb0ac657bceab6142811ba7442d5f24e67752f0
'2012-02-11T09:20:19-05:00'
describe
'112278' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQA' 'sip-files00027.jp2'
fe64dd688ff435545824260bce48c987
034f75e484150fc16ce0b1a75e19cb2afb07f244
'2012-02-11T09:21:13-05:00'
describe
'87436' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQB' 'sip-files00027.jpg'
999c4e0180275188faad352ab9c6fc99
e01425bf658cc26ff93e2b52515038f66f91ff6e
'2012-02-11T09:31:27-05:00'
describe
'39046' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQC' 'sip-files00027.pro'
592c1e48001c6fa273d9795e41d117ab
4712d927510ef4e8ae6dcce9b57f2f2672205dcd
describe
'31128' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQD' 'sip-files00027.QC.jpg'
d06c138f578cc633301f59935a36c26d
c4c23ff68d8f632113139450ca990dca08aa7d3f
'2012-02-11T09:23:59-05:00'
describe
'972415' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQE' 'sip-files00027.tif'
a8d1827ea9ec5f73281bb1e54b1e0473
27a4ff771225a03f74df0fecfadc871c55b53a04
'2012-02-11T09:22:41-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1588' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQF' 'sip-files00027.txt'
c629d4f598ffbc8fa5f8b4196881f11e
73c1543141c105a54abb1f1ba4dd9077604c9c11
'2012-02-11T09:20:55-05:00'
describe
'8019' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQG' 'sip-files00027thm.jpg'
a2d510accc7634a89e2596cff22e1f9b
0d777b988d29eb819c9cfcacee23dfd8682dc4ef
'2012-02-11T09:23:48-05:00'
describe
'113852' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQH' 'sip-files00028.jp2'
53923383e0482700086c0ce2b6cd911b
72cd852c494d9df8a54acc8abee3d98765a315ea
describe
'87064' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQI' 'sip-files00028.jpg'
4c78ebb8ca6c8d949590e22bd8a58de6
566839b97a1c602534f1493650d1ca5d986776f3
'2012-02-11T09:20:01-05:00'
describe
'39247' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQJ' 'sip-files00028.pro'
f9e983d037e03f3279baf733ea5f5ec6
62bb6e5d6f1a52c4057abf01379ea717677a7cfd
'2012-02-11T09:31:20-05:00'
describe
'31065' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQK' 'sip-files00028.QC.jpg'
e961879677170a2ab6b449fab9bfa3af
17e0ce8430ab134db096932ae97fe63fe55403a3
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANQL' 'sip-files00028.tif'
928b4a3eb9f08f17d992efea7f42b65e
0e2984cefd0df5e59787c49398d02441583d9529
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1611' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQM' 'sip-files00028.txt'
7c8379218c8745f6c8aa24dc8f073e16
20e424e42948519ad087ff4c4b99b17aebb2dde7
'2012-02-11T09:21:22-05:00'
describe
'8546' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQN' 'sip-files00028thm.jpg'
adbe0c31b154bc23d1cc0d5caa6d0757
dd4b7b183e9fecc783b0cf5b44af1696389a24c3
describe
'110043' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQO' 'sip-files00029.jp2'
5e7ff7b7a383f21cb2e18aaedba86ffd
02a738fe63de6cd601e0ea01778d65cce3e0b891
'2012-02-11T09:19:54-05:00'
describe
'84337' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQP' 'sip-files00029.jpg'
610d858e54b185e8e27d6d6bb3870ad9
dd856d5814fd40e92f9f2998848891793d3c3c9d
'2012-02-11T09:22:59-05:00'
describe
'37640' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQQ' 'sip-files00029.pro'
79c52384bfe0eb6e17a345cb2d9c321c
14ba9ecf70a85390f239d692f66ff11646e04218
describe
'30076' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQR' 'sip-files00029.QC.jpg'
6e9cb2223fd8ec30cfb1f8a44767055d
7e45be5e014c807cd4ec62a9440a81ff78aea7c5
'2012-02-11T09:22:08-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANQS' 'sip-files00029.tif'
4cebb19a28db73791bade9cc65a703c6
13aadf9c51ddccdf8bf576330657ac33eed35eaa
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1534' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQT' 'sip-files00029.txt'
e7746c2aa054edd35af655fecf9c1b31
c3b570e6176c0bcb2b05e321a311b25eb93567c5
'2012-02-11T09:23:43-05:00'
describe
'8278' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQU' 'sip-files00029thm.jpg'
3b870239b793f5f31063342213ea0186
69f4c19edda2e48f6bf7bde5b7577ac9b6794715
describe
'107215' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQV' 'sip-files00030.jp2'
ae9fb987384fbd9363ee926ebe5462df
68c26d3d627d2a4c6ac881945cb6f2b126f2cb11
describe
'83255' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQW' 'sip-files00030.jpg'
25fb9953410570de50a5db1477428925
9073dcdea6f701ced2bf76798807ddd9d8c448fc
'2012-02-11T09:31:04-05:00'
describe
'36356' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQX' 'sip-files00030.pro'
b324e54404638f4416dd04a259699e48
95a43d23f6b694b985a03373c79fde3d01beccb1
'2012-02-11T09:20:48-05:00'
describe
'29315' 'info:fdaE20090607_AAAAAMfileF20090607_AAANQY' 'sip-files00030.QC.jpg'
77d48ccc1c5f41f26314bb71531dbcf9
e246e0dd5ea09fe3750ee4b730abb98ba9f5c112
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANQZ' 'sip-files00030.tif'
947a94de0cc0c7e59861ca8a31397fb1
f57b4e6d72494e5087de8d4ae6e9ed63a207b67b
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1490' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRA' 'sip-files00030.txt'
9883082f06693ecb7a48d15058f4528a
29c3cf8cdf15c30edb3bf664da9cfa614109779e
'2012-02-11T09:31:12-05:00'
describe
'8074' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRB' 'sip-files00030thm.jpg'
b3311e5a6be788c590cee254848bfbb5
511746f03bcbbea1eeb141d2fce6573ff78cee34
'2012-02-11T09:21:44-05:00'
describe
'93587' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRC' 'sip-files00031.jp2'
f5376f5675cba8c080e7e9133ed81449
543e5284338fc4f6cbf0a641dbb202f83afd0e8b
'2012-02-11T09:25:13-05:00'
describe
'71755' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRD' 'sip-files00031.jpg'
9c1d98cca502b829626ef52b384113d9
cdb6bd4c767d237794e904382fcc58fb9e55bf0b
'2012-02-11T09:23:02-05:00'
describe
'31571' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRE' 'sip-files00031.pro'
cbee45a8f5ec41b23c58aaaa3a292717
4757ee28c765ecaa59faa6a6e442c53015f3de93
describe
'25391' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRF' 'sip-files00031.QC.jpg'
54c786e10f0f53dc1afd5bd3e76e1162
91a6bf27135f73d987fe4baf9eddd06072cb5ab7
'2012-02-11T09:22:30-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANRG' 'sip-files00031.tif'
fbf041122b0d21e84b2c5efaa4d4e957
1fbf0ed616c0097ca84ad310df37926ed77f4d89
'2012-02-11T09:21:12-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1323' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRH' 'sip-files00031.txt'
9866550ad9e0f9e5c31f1ea34a0d7c80
f1b015a29a4bc072134cfaa119d6233236fc0fa1
describe
'7415' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRI' 'sip-files00031thm.jpg'
cdea7d77768e5a9190e465fe570867dd
6c550fe7d1de560f63f0db3034bd33553203fdf4
describe
'89970' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRJ' 'sip-files00032.jp2'
c6953ac3f6a2ea13ec6e6ee246950308
27263eaebe949e47691c4b70f4355e995af5c0ce
'2012-02-11T09:23:29-05:00'
describe
'69771' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRK' 'sip-files00032.jpg'
ff54a7e87d280a33bc42a63f13335bec
9aaeef2837e6b097d271792a9d9966ba86fedbd9
'2012-02-11T09:23:04-05:00'
describe
'29113' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRL' 'sip-files00032.pro'
347f4c410a6a065a2571c0fb30b7b3eb
6f22a4d4f03673406d2a5b90c152eb79e52712b7
describe
'24920' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRM' 'sip-files00032.QC.jpg'
ef2cd26ec4ac758444adbb62e464a106
8a8547126fe730fcac3fba3bb9a108cc6b7061fe
'2012-02-11T09:25:16-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANRN' 'sip-files00032.tif'
a3c4ddccbdf0986636ae4ebb13862d79
f0d11bfb1cd4dd80919e45a854eb702180bcc5b6
'2012-02-11T09:20:13-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1244' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRO' 'sip-files00032.txt'
054fb69c26cf3924224d751a8b60eaa7
e595c3a25bc93294992894ee1fb3011f4eb14787
'2012-02-11T09:21:54-05:00'
describe
'7158' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRP' 'sip-files00032thm.jpg'
d2a968589a44006e5062cb4d0ecc8eaf
86dd678cbe01986cb602cfcc3a17d2735e101e86
'2012-02-11T09:23:31-05:00'
describe
'99432' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRQ' 'sip-files00033.jp2'
15585fe2e0b749caff7b5fb8e855b27c
b1c88e1378924e590a28c6ad85373e2b48776c66
'2012-02-11T09:26:50-05:00'
describe
'76638' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRR' 'sip-files00033.jpg'
094332489e743a121ad9d1055abb728c
05c79aedb7b058b58f7f4b4ffde4e9615de079bf
'2012-02-11T09:20:28-05:00'
describe
'33384' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRS' 'sip-files00033.pro'
d09cf1329d1aa27f357e582e37a67bce
59039dd275edbaa5b3068ee46d573b1beb030573
'2012-02-11T09:22:47-05:00'
describe
'27367' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRT' 'sip-files00033.QC.jpg'
9c42e0bb4fba4c06347c46b32bd53983
dd711a45e8de04c1d74abf9995a36a252e38c700
'2012-02-11T09:28:31-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANRU' 'sip-files00033.tif'
d1f207428a3b6dd2ac163c7196d13316
29ff74010681739a05c79c5b634791654e23461b
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAANRV' 'sip-files00033.txt'
8bf783ea23252ce3c6205f29e3946f80
a6e1a3165d3bde0702742c6603af62e451efd792
'2012-02-11T09:22:58-05:00'
describe
'7873' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRW' 'sip-files00033thm.jpg'
1192b9ee06042873e662173431883e50
7e462b887de4e4f1ce8ee494e59a7768ab4eda45
describe
'95852' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRX' 'sip-files00034.jp2'
cebad3bca7da04914e93c05abd8c0348
0b5b98f5a176bc252b54b3ede92f2f5b392c2667
'2012-02-11T09:26:13-05:00'
describe
'76246' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRY' 'sip-files00034.jpg'
bc39e13126e230e09943edcaa125dea2
bf764af445614c16f09c4eccf06ddde8790337a0
describe
'33479' 'info:fdaE20090607_AAAAAMfileF20090607_AAANRZ' 'sip-files00034.pro'
88d5def88accb3535a6a9901801703d5
4025602bc19f8eee5d4b8b1a41e18ca6bc9c90a3
'2012-02-11T09:20:56-05:00'
describe
'27622' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSA' 'sip-files00034.QC.jpg'
66a86cddbdeb13b03e34ce70a2e25061
e00a6f8e79e212abe8c6d77d65c7b9a81cb29039
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANSB' 'sip-files00034.tif'
fc49f9918163ca54bf7a3eb7c9b4374e
fe349e527a8bdf4c46eb288a666faa79d2758e1b
'2012-02-11T09:20:18-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1459' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSC' 'sip-files00034.txt'
e568671e3d996b92354481825559d5e0
c5d536d0d39c0697e1b9c0003ddc360b1615ab45
'2012-02-11T09:24:57-05:00'
describe
'7427' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSD' 'sip-files00034thm.jpg'
81ee7894c02fa381c1a60b3257a1f400
6e2cc67db50bf2b787a52dc93ae009fb9384a4b2
describe
'92926' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSE' 'sip-files00035.jp2'
b56535db1c5f6c62e59fdbb2e22de4cb
b31187f7c1ff8707d56ba5b08859541d45c037a7
'2012-02-11T09:24:28-05:00'
describe
'72668' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSF' 'sip-files00035.jpg'
0b30f2cb92da18bb2d1ee41bf645b2ec
c6666802ed6d2cb67afc34256d51c1cb9b2f560f
'2012-02-11T09:23:05-05:00'
describe
'31499' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSG' 'sip-files00035.pro'
18b3166e8a2f7b2e39d419254078305b
4241d906764895663edfee0e25026ec54fb490b0
'2012-02-11T09:22:04-05:00'
describe
'26179' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSH' 'sip-files00035.QC.jpg'
87b7c304128796d5cfa135a14306a469
d3aad410b0231910f5c4534fd73ad8380eefbc41
'2012-02-11T09:25:38-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANSI' 'sip-files00035.tif'
b81f8231a016bad2e64167774f099335
da0f64d8b2664aa8b1b4500c2832224db3e8bc48
'2012-02-11T09:22:13-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAANSJ' 'sip-files00035.txt'
2e0d88432809da3f0cb374e25ed7f5df
5526c2c215ed1df11624eec77a32ba3877f7de28
'2012-02-11T09:22:21-05:00'
describe
'7109' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSK' 'sip-files00035thm.jpg'
fb517f250a0f10d54bfb78084f55df59
dc91e904a44e8d1dc7c62463fda535c4fa658182
describe
'114196' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSL' 'sip-files00036.jp2'
afc5b6434f88f35e5e2b6d54909cbfe9
76efd857287803b4eb06843bce20fb23ff6c689f
'2012-02-11T09:21:59-05:00'
describe
'89073' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSM' 'sip-files00036.jpg'
e0e8eb750ac5e7892a085d230bac8de2
eb56f079c624f0cb05b3c9a802ace9c9c98ae66e
'2012-02-11T09:23:47-05:00'
describe
'39736' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSN' 'sip-files00036.pro'
eabd19ce065051ff64cdda32da8e3c08
899a34b58458896bb55fc6a3879755a14f06c09b
'2012-02-11T09:21:11-05:00'
describe
'31855' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSO' 'sip-files00036.QC.jpg'
360b9847463f96efe4c112bbd46e3b71
5974d38a3e34a714a3e71a314de85ef5c0088667
'2012-02-11T09:30:26-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANSP' 'sip-files00036.tif'
b29af250e71cdce9d2748f1fab71047c
db83cf53b1ca6fa3c34e523a99c46ee639444c6d
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1616' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSQ' 'sip-files00036.txt'
12ce90fd0d36f134cbfa520a74139fdc
76c6d5a169d08fde274ffea3763afb2620cc357e
describe
'8726' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSR' 'sip-files00036thm.jpg'
80213a3fda4880e32b83d41203614471
aa78aba64c56ab2b274144bbe7020f78a284ff79
'2012-02-11T09:29:25-05:00'
describe
'45054' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSS' 'sip-files00037.jp2'
5a8e9ea1525d201d52e3cbf8771cf8ca
3d839680bfb2efc80c96fab89fecd36a28531056
'2012-02-11T09:21:26-05:00'
describe
'37902' 'info:fdaE20090607_AAAAAMfileF20090607_AAANST' 'sip-files00037.jpg'
4a09cd5dc142280d9c3bc91fe1aeb941
31671f49e57bede7d5e48557da0ad75bbac8da95
'2012-02-11T09:30:25-05:00'
describe
'14139' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSU' 'sip-files00037.pro'
61b59db6dba07a38ce5e2630bc68ab1f
aef7c297d9dbd3e36e5eff2c413b339eb2ad611a
describe
'13090' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSV' 'sip-files00037.QC.jpg'
4953443d688df2d56eceb311f6997366
18f290a3b95a0c801f1c9a8dfecdd22aa270190b
'2012-02-11T09:25:30-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANSW' 'sip-files00037.tif'
c90bdbd698dbf7d64a8b8da784651ef7
93473366d328afeaad62fe99b3cd52a4dd841991
'2012-02-11T09:26:25-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'649' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSX' 'sip-files00037.txt'
0d8d558f972987299bf74a02b4c8af8a
9ed8a94cf720114eb33541a9d4f4949f48f1e6ed
'2012-02-11T09:21:02-05:00'
describe
'4036' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSY' 'sip-files00037thm.jpg'
f4f45e55eb7f754485aa7001b07bb78b
ec31d07792a164da5b5c6c430fa823cbc85463c5
'2012-02-11T09:21:39-05:00'
describe
'81077' 'info:fdaE20090607_AAAAAMfileF20090607_AAANSZ' 'sip-files00038.jp2'
9acb956dfe25c2aeadbdbd40ed64cf8c
843fb9ab8bac53546edd7832eea8c2bd2934479e
'2012-02-11T09:22:22-05:00'
describe
'62673' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTA' 'sip-files00038.jpg'
3ee704af97f108a6d30a825657f67280
e0966559ab853588e0b0b0c82b6a7f6824bf0a60
'2012-02-11T09:20:59-05:00'
describe
'22610' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTB' 'sip-files00038.pro'
c8dfef04ac8f0d073cd03b8abb44141d
d83807c9b1e2a5a54e4dc3e24e66dee09713c483
'2012-02-11T09:31:34-05:00'
describe
'21758' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTC' 'sip-files00038.QC.jpg'
860b77c3424e1c4b929cb64cc1e3b5eb
3129379837839418edc36f381a1b2587caf76538
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANTD' 'sip-files00038.tif'
9529bf04014df0ea0717581cbfee1fdc
34919d939d5c2357f45c14918d14be39d440d5d7
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1099' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTE' 'sip-files00038.txt'
7d5cfea58fdea45beea5fdc4dd86141f
7b6351ba1715d9ca90612658f625fdb4c1de7e27
describe
'6145' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTF' 'sip-files00038thm.jpg'
c362a9da5809f0094183431b97a2a4e1
7a0125dfb2a027701d323476c69fdadbab6041f9
describe
'113738' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTG' 'sip-files00039.jp2'
4adac8a89d70650a7a3ae9ff3aaf1368
63b3f561ebcc2b33b792251d713414ca08b9b75b
'2012-02-11T09:21:49-05:00'
describe
'89026' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTH' 'sip-files00039.jpg'
5c7e39b70354866bd2198f35056ba834
7d481e1aa1ac618c441e537f39decf6fd839be33
'2012-02-11T09:25:00-05:00'
describe
'40215' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTI' 'sip-files00039.pro'
a29d773f09350592fccd66ae5c43a71f
4e02b57096ab003f492dbd255510c27946de25a3
'2012-02-11T09:30:28-05:00'
describe
'32251' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTJ' 'sip-files00039.QC.jpg'
77216bb4cc0e17a588211495468394d3
e33421b5f3800c37f72a45e23b5d7e8aef75fab7
describe
'968586' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTK' 'sip-files00039.tif'
fbde7e2cbad92b94737883ab98685f4b
19472f593a8b5060e909220387ed7beb3c6af5e4
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1639' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTL' 'sip-files00039.txt'
e0c90a129be4350cb92ac38ec54c0790
2f4f876ee29a39292dd064441befc8e95991daab
'2012-02-11T09:24:40-05:00'
describe
'8570' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTM' 'sip-files00039thm.jpg'
d1576575a1506bf4851f9616531cf5f4
695b21789f8b2441056d9c721c77b30345c4ea8e
describe
'109566' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTN' 'sip-files00040.jp2'
d53af6b7a56421221966e0b698cf06fa
8176f820c1cac6be09025b8ad1ca379b0228dab3
'2012-02-11T09:24:47-05:00'
describe
'85791' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTO' 'sip-files00040.jpg'
c89b7b8718743dabef26be14506db80e
cc1dd02f813db718b4cd63c02b050ee637923a24
'2012-02-11T09:24:55-05:00'
describe
'37797' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTP' 'sip-files00040.pro'
83cf32820db84912b494915bf95450ac
4006bdf22c6349142510de29aba65fa65bddc0b4
describe
'30401' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTQ' 'sip-files00040.QC.jpg'
b5d0ca3cf2a44ce8d5d2667e8a672b76
f1663810a8a1626f98928357fc9e8dada58175de
'2012-02-11T09:21:10-05:00'
describe
'969186' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTR' 'sip-files00040.tif'
c1d7a03020790b378ddd72a279b82b42
75710f212efe43fc94e94083785192a1d0fa3cfe
'2012-02-11T09:31:18-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1559' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTS' 'sip-files00040.txt'
f57eb05312e014fa7584388f5acd7f52
3c5048f1d41e4e4d77c582f54a3a02e7978fa600
'2012-02-11T09:30:29-05:00'
describe
'8345' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTT' 'sip-files00040thm.jpg'
d4267ccc24ae7f2b7ddcc8710f8511b9
f5738c962dcfa11e6e749c1d641a5875b63fc8b7
describe
'85588' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTU' 'sip-files00041.jp2'
2e3ca495c28181dd1cd73d31fd470afd
0a156fd690116b5c1891f585fa1c49dce38d3401
describe
'69092' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTV' 'sip-files00041.jpg'
cbcf429a0650fb3c734914e56d6cb9b2
978b0a4686844df5ba947c52263d9a730717336a
'2012-02-11T09:20:21-05:00'
describe
'28166' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTW' 'sip-files00041.pro'
c2b40b4c64ab500bb932f97a914a6232
3e5777f8970b09f7fba89c54d17a8f49e75cc14b
'2012-02-11T09:31:38-05:00'
describe
'24401' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTX' 'sip-files00041.QC.jpg'
c0cc8da5d42ff82602dd9dc8075781a8
753be270fde2afda929e9ef301065bbdc8ec27ac
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANTY' 'sip-files00041.tif'
eee60b1feaefa040e4976fcd03ea186f
04fb7a9bb7c8243bcd8d3cee99fdcb2b791b4bcd
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1410' 'info:fdaE20090607_AAAAAMfileF20090607_AAANTZ' 'sip-files00041.txt'
02c26fe80e8bb46a5048929cfcfa32dd
2a2aacca50138e5cadbf3b7f190494af8d500573
describe
'6835' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUA' 'sip-files00041thm.jpg'
92db447026de5dadecee0866b68cc71b
fbcee2dcae54e40c5e99f4013c874b9010699a6e
describe
'110810' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUB' 'sip-files00042.jp2'
2e869477bac40387cfe8d6284fb1e2f8
c09fa73037b514ee22c00a67cd9d74b3cffebb58
describe
'86612' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUC' 'sip-files00042.jpg'
7832689438e7398e2974e00041fed5e6
059153782986a7cfd4614da5c647090b09bf69ae
'2012-02-11T09:31:21-05:00'
describe
'38186' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUD' 'sip-files00042.pro'
78a44232c55602f5320b83c004a1457a
661aac6131fa716f6f5c00a6b80ea82702edc591
'2012-02-11T09:28:42-05:00'
describe
'31086' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUE' 'sip-files00042.QC.jpg'
6dd840524248e5de1f527ebee2c6090c
bd78226977b41b640c50e76bdc75c1237f7dbdbe
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANUF' 'sip-files00042.tif'
ca7dfb90776134bb1e7890d7b2feb401
477b49e8d391484db296bdbc8de624619fcca6b8
'2012-02-11T09:23:20-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1563' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUG' 'sip-files00042.txt'
e6a8c55db20c67fa06ee26cee4847b49
fa4b43672911aea3b88055394f5f8f2c2c8f7151
'2012-02-11T09:24:25-05:00'
describe
'8431' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUH' 'sip-files00042thm.jpg'
fc0414de1c258254c06a90c9089d91bd
2b4e3a719be1bdb676eaaf04c44e439d1b13c2cd
'2012-02-11T09:23:33-05:00'
describe
'80236' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUI' 'sip-files00043.jp2'
4f5f8898b40682ac531b68ed569c2a68
7a26e4a500a4332cac7705e11b8fc37de2bbe2af
'2012-02-11T09:25:41-05:00'
describe
'64453' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUJ' 'sip-files00043.jpg'
4e9ac97225cba250164a65eca4a5623b
4ce38e3c46ca0c8d10c808aeea1b08c0af5cfcfd
'2012-02-11T09:20:45-05:00'
describe
'25370' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUK' 'sip-files00043.pro'
dfcb9c88839ef13b00f0fad209fe37a4
1f2272d4f95288d8b8f96c38c1c3a28d433706d1
describe
'23214' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUL' 'sip-files00043.QC.jpg'
14c6747906b9e586497c7c821cc6d7a1
3bfd0b6af68e53210d511d2f544477b793532aa4
'2012-02-11T09:25:19-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANUM' 'sip-files00043.tif'
e3332f4d2b3b70f6c122ffefea3ffe75
62413a4003d95d07d8b937c8c18b86e29fc78d07
'2012-02-11T09:23:53-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1248' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUN' 'sip-files00043.txt'
f9320f104f93b20f9e88318017e9e79c
2f61534f7b0fba93a0dfbe2731a15eda46111a78
'2012-02-11T09:30:49-05:00'
describe
'6692' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUO' 'sip-files00043thm.jpg'
23e3e4907fb155e6ee1f603bec6f9189
da7cde977c0b551e0a9a7056dba8c304c3f801a2
'2012-02-11T09:21:50-05:00'
describe
'106719' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUP' 'sip-files00044.jp2'
ef346ee661114093a71e5a13a013670e
05ead8e59a18ab4507c9abf82c23ae8f417d9a23
'2012-02-11T09:27:23-05:00'
describe
'83213' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUQ' 'sip-files00044.jpg'
6115e454474111d13268ca096c809a48
5781210b31031d6007b655b5b6128d39c970818a
'2012-02-11T09:20:52-05:00'
describe
'37878' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUR' 'sip-files00044.pro'
083ef0f09c9a12a7d92e5c6515694376
6d8eecbe5856de31d9d35dd7180fe2524ab53def
'2012-02-11T09:23:27-05:00'
describe
'30716' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUS' 'sip-files00044.QC.jpg'
95342a8538caa8d6304949ac6ba06b5b
2118529d2c473c2e7febd4582696c99d091aad51
'2012-02-11T09:20:44-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANUT' 'sip-files00044.tif'
20297b83be60aba53b77c22a94f0af50
81b95fbe42546f1e8dbb917ceecd42fe0238ae32
'2012-02-11T09:21:25-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAANUU' 'sip-files00044.txt'
f27434665896760ad509d5dbfed4afcd
14925d1fc139c219fbf607fd411d21fe5c13a3ad
'2012-02-11T09:20:32-05:00'
describe
'8484' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUV' 'sip-files00044thm.jpg'
6e90042971c070654e2e5d0d3d5e3830
7ac0fbedf856e58cde25d44f823d11f0d54f7247
describe
'103489' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUW' 'sip-files00045.jp2'
bb49c1fba7d0194cd893631b203de2a0
e074cea4b0b687dcc1724d018056f55b806a5977
'2012-02-11T09:23:12-05:00'
describe
'80371' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUX' 'sip-files00045.jpg'
5c9a27f752a2b92884b2e258b1cd544c
31a16483c43b777decddf6433d2e8bb71ae06ac6
describe
'35971' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUY' 'sip-files00045.pro'
1aaa641672438e6f05891a55575403a9
b4e6263181bd69bc2b9dfca86ba4963534fa6368
'2012-02-11T09:30:05-05:00'
describe
'29322' 'info:fdaE20090607_AAAAAMfileF20090607_AAANUZ' 'sip-files00045.QC.jpg'
44176b30d3ba343aaf3ecdef5889aa4a
41dbed27d14871e6f6d6a83828c5285892f9a20a
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANVA' 'sip-files00045.tif'
d7b572006f4120e2b08bd879c11c07eb
1a193901e48f2324bea26533cfcd94d72b0ed88d
'2012-02-11T09:23:15-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1464' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVB' 'sip-files00045.txt'
0d64d0f6f9408366444b8511bfce7061
26cbae6c097c117135f184bd469c122d70ec3200
'2012-02-11T09:21:53-05:00'
describe
'8031' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVC' 'sip-files00045thm.jpg'
108c39a443c4dfbb333e051fb14388bc
2aaca63e12f07ee5d2e65af2adae57598f7567bb
'2012-02-11T09:24:53-05:00'
describe
'106447' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVD' 'sip-files00046.jp2'
a46700801857faf589a33a0ee22b43d4
55259ef010ae7375c4a45f7887b5a76f57da948e
'2012-02-11T09:19:55-05:00'
describe
'81575' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVE' 'sip-files00046.jpg'
10e3ec48e3ceca42bacd560556c41ea7
e75fdcb75f45c079003d93c8aaeb6dc1907063c2
'2012-02-11T09:21:27-05:00'
describe
'36577' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVF' 'sip-files00046.pro'
2ecf934d0fc17d9bd0908e5d641ff4d8
e0dfc588a82b4849c4072c998439610fbcd379fd
'2012-02-11T09:20:07-05:00'
describe
'29740' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVG' 'sip-files00046.QC.jpg'
69f8924047de70343e1a0c9052a284d3
0b2ddb6d0d24f4876133639dafcb59e407890ec2
'2012-02-11T09:30:43-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANVH' 'sip-files00046.tif'
34729859d602564501554568fea2b748
e75d642c1b7586894f250ac2faf0383ee7dfea35
'2012-02-11T09:21:51-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1493' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVI' 'sip-files00046.txt'
4e6784ad9da941f20099cf398ce019d4
ca46c27ec406aa4180d7b2c6a921a4563e900c9b
'2012-02-11T09:27:33-05:00'
describe
'7956' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVJ' 'sip-files00046thm.jpg'
ce0cf9e8313c013d086d4c7139051738
d9b837fe16138e23c00854cb336d44663f9fbb8c
'2012-02-11T09:25:10-05:00'
describe
'116384' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVK' 'sip-files00047.jp2'
06c58309b5ef12b79b659d021fdce902
98dd52da3198a3951ed005c45ad97e7f50982a66
describe
'91047' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVL' 'sip-files00047.jpg'
2de02b4aae613c9a65f9cbeec34a75f2
dcfb65d6e9bb1161152489eb98b0b249ad6b9a63
describe
'40320' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVM' 'sip-files00047.pro'
a20ce371e832bc86a231f62e6fb431d8
13a76a48a3eff7a2e649b8bdb8afd1a158127d59
'2012-02-11T09:23:07-05:00'
describe
'32213' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVN' 'sip-files00047.QC.jpg'
4aacd4c096910c47769a947ed22ce11d
30d229b6fdfc23ea177186686904dfc725123b1d
'2012-02-11T09:30:38-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANVO' 'sip-files00047.tif'
a87b76052d631ed5ab705813145398fc
62bdfdddf98b3aacca58403f9f362e748f8a4d9d
'2012-02-11T09:23:03-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1634' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVP' 'sip-files00047.txt'
1733251363144ce857157953a738a71a
5ded3a9b89be5ffff7e6bac7c784f89cf5d14923
'2012-02-11T09:23:41-05:00'
describe
'8539' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVQ' 'sip-files00047thm.jpg'
0ef0c91436e405fbe70e100c8be9cbfe
fb9e18a8b6573e16172216e35b3cf5c979f3328f
describe
'17867' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVR' 'sip-files00048.jp2'
5c8d1c242fbacda4228f244e20ba80a4
bb44c8ef27f582859f2290851b0edb09d3721aa5
'2012-02-11T09:25:26-05:00'
describe
'17620' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVS' 'sip-files00048.jpg'
f0bc381942dfe6f97cce8ae649fd6f99
68cdcec5c7296de623a1d999023e3a7ddd506686
'2012-02-11T09:21:24-05:00'
describe
'4214' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVT' 'sip-files00048.pro'
fc474bbe6b4f38321b52d760e4e1f856
02a50ea32e34e2808e429735d5a390915c58e2e0
'2012-02-11T09:24:01-05:00'
describe
'6032' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVU' 'sip-files00048.QC.jpg'
2f8ca81b863affbd753f44c4349df6bc
7e80c76f073b5e9b6cd0177d4f8a8389aa6ec1f2
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANVV' 'sip-files00048.tif'
b92cc7d5601c6212837e7552653ca3a3
3bb8b0a145fd48315180cdd03e96da106258e8fa
'2012-02-11T09:30:36-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'205' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVW' 'sip-files00048.txt'
55e3e7bf381fc6289e350394d0b9b5e3
7c179d13bbba806d8323a0fc8c58b22580a72d32
describe
'2055' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVX' 'sip-files00048thm.jpg'
8d821c4a6368e18b91a3b841692dc984
9b5d7a6f5307901a6ffd93341e4f32c9530fb8bf
'2012-02-11T09:22:28-05:00'
describe
'101310' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVY' 'sip-files00049.jp2'
0622073ac0808a3b40a2f74b68b986ba
a7fac15c33e843ceec844f04847f877c068fc743
'2012-02-11T09:21:32-05:00'
describe
'77768' 'info:fdaE20090607_AAAAAMfileF20090607_AAANVZ' 'sip-files00049.jpg'
b1356439cc133bd6ba8f0beeceed6edc
7fdac456cc25415e8c108f2b114cde1ace4d3c68
describe
'33999' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWA' 'sip-files00049.pro'
fea4b4221a6130d849c32e6fce715f42
a249e4a52c23694520589576d46d1d19865c8340
'2012-02-11T09:23:40-05:00'
describe
'27817' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWB' 'sip-files00049.QC.jpg'
49ff40166600c0ae8da918a2142e464a
ab1cf6869f197225ff6cedc5dd1f02c90c49a08b
describe
'978873' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWC' 'sip-files00049.tif'
09586dff44b03eb6c5a41d62fda32cf7
89378b19202c378418ce635b5a8a5c1e341608f6
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1405' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWD' 'sip-files00049.txt'
bbf9692a40569e311e0fb9a42c3ec5b4
8c670e5d53e280e04cc50e08cd07d9a11d885451
describe
'7460' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWE' 'sip-files00049thm.jpg'
2c23a948c7454ea0d652657d99db02fd
8e0a9325b254a1d8e3d83ef41031752ff3262415
'2012-02-11T09:20:09-05:00'
describe
'122450' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWF' 'sip-files00050.jp2'
67a534229128695d0059dece28b5f9f1
6b8ef950f5edadd9dac8e4d483d5fc41124620d1
describe
'93612' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWG' 'sip-files00050.jpg'
9c22f1236dc080abb1e416071c1848b4
3c330fdc5ff2ad8fae27cc293779689b9b401b54
describe
'41261' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWH' 'sip-files00050.pro'
1dc015a3012e590224b6a2a3aa04aa52
46a7d75776ed0b38547700895b0873c0a98376ea
describe
'33325' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWI' 'sip-files00050.QC.jpg'
a84e5f0717b242217743637315efd615
5c8c7392c0075f934e405ce1e9f336df6ff57774
'2012-02-11T09:24:50-05:00'
describe
'978267' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWJ' 'sip-files00050.tif'
e12d55d4d1f0e21419b48c102d33e74f
e77b313a7eec4836086b0f4a9148b98645ea8e4d
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1698' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWK' 'sip-files00050.txt'
106dd8ce709f5e2b7c94d76184c09616
df5d05b3256f17ff492e7711599aca6a1e291713
'2012-02-11T09:23:30-05:00'
describe
'9186' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWL' 'sip-files00050thm.jpg'
357991608e7f7f22dfb5b96180bab556
5f71e0076488f4a0cd7af02cf549e00e1825e40c
describe
'966890' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWM' 'sip-files00051.jp2'
8e262597668254664eb92320cceea3e0
6af7fec12490ff55e4323467839a1dc5ec2c3685
describe
'85287' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWN' 'sip-files00051.jpg'
080d9723a330fd1d292fd4173e34ecc6
523e722b6b927a2163c031a8c18b19771570197a
'2012-02-11T09:20:14-05:00'
describe
'37826' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWO' 'sip-files00051.pro'
51d8a57bdeed235078f7642d2ddec642
dbac86d2904eecb1a94494f776afcb301a3aae21
'2012-02-11T09:25:07-05:00'
describe
'30364' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWP' 'sip-files00051.QC.jpg'
8fc614c51fa3dceda6a018bebfa1da27
ea09e1c92ff9fdb529065598e6c9f6cc988af268
'2012-02-11T09:20:39-05:00'
describe
'7756132' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWQ' 'sip-files00051.tif'
550749c17b2cf75680369203c173eb26
246ba2be4ec2dfb49f0ee9d626cb4046329498b4
describe
'1555' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWR' 'sip-files00051.txt'
44549a95ffb85a721ac39ee8cf11e8ba
2a21f51d90f8a319ba709dc501f6c3807b853769
'2012-02-11T09:25:44-05:00'
describe
'8437' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWS' 'sip-files00051thm.jpg'
006697b7d8e3b1196513501818e9115d
ac2c84f39c6b9bfa6d27aad9c7d715b2e87db130
'2012-02-11T09:25:11-05:00'
describe
'67747' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWT' 'sip-files00052.jp2'
7b93f630a64ed8b14d9f101ef4af22a3
df0d2280a93d1f5263e909d15818ab124f1f3914
'2012-02-11T09:22:53-05:00'
describe
'53875' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWU' 'sip-files00052.jpg'
47d404fe47876cceec359a5face88e29
ebb470a4b5743f90ca497626846583be0ce3003d
describe
'19782' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWV' 'sip-files00052.pro'
093310346db807595371f530971c2217
b80cbb980a7825ed497286b2e2843cb2eff5c902
describe
'19132' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWW' 'sip-files00052.QC.jpg'
f8fb6bc8cf9ab6690c82153401bf0308
2272f1a5953d89067f06d6794ee1002a6b394d9d
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANWX' 'sip-files00052.tif'
21589b25bbd76b07087626d292853d92
e048fc01f8ef179463e79da30e82b24e5043ca66
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'929' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWY' 'sip-files00052.txt'
810959f5796b560ce9a613f60ae35cb8
ace785f9149a51a5f3833332534a76d2b27d6ca8
'2012-02-11T09:30:21-05:00'
describe
'5700' 'info:fdaE20090607_AAAAAMfileF20090607_AAANWZ' 'sip-files00052thm.jpg'
12456e2b7ee4d8c5926858a724d5a17b
dbedba29c344ea351c237ea972fc5c73441a5b56
'2012-02-11T09:27:56-05:00'
describe
'963408' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXA' 'sip-files00053.jp2'
220ab3f4a838fe51d6f0f167602c4d35
b537bf73848a4d5a098cce7f5d4779e4f636b0b4
describe
'90011' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXB' 'sip-files00053.jpg'
263dbad63d960db3fd92a5b8d1f05f2d
90db2ea84f823f9a9e8a2808f05184dbaa923479
'2012-02-11T09:31:03-05:00'
describe
'36236' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXC' 'sip-files00053.pro'
b19e8729145c46122bd3c4cfeec9521d
5e5b1f1dd9d8c79ac9357f10d9cc2dc5614ee1f5
describe
'30276' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXD' 'sip-files00053.QC.jpg'
9864bf306574e924b3c63b4c7ae60fcc
8561a2528a248665632c5880becf82296b29baec
describe
'7726848' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXE' 'sip-files00053.tif'
5be799a34bc0c12d472c614490cb048c
39534e2dcf487335089ea0c9a4e021f707632363
'2012-02-11T09:23:14-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANXF' 'sip-files00053.txt'
1de0ea4017dc4fbf353728fa509bf2c9
9433b0b03e29de48f213daf6be488a80bb3da020
describe
'7714' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXG' 'sip-files00053thm.jpg'
c669dda40993d01f8d46e4690ca4cf6c
f6111c2ffc1e94ba313fc5347736e0a007faa0fb
'2012-02-11T09:24:38-05:00'
describe
'936018' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXH' 'sip-files00054.jp2'
ec20a4ee2c36fe8c2a6a3b08984eb5cb
f8e35d2afc902cb63d7c19e58a7fc5f96f4ffda4
describe
'70949' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXI' 'sip-files00054.jpg'
3322be4cf3eacf19f50ce0b430db222c
be23936d17892c5df9efbd8e3443340afa8cc237
describe
'29895' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXJ' 'sip-files00054.pro'
6436362964d4ae0b356123fa13f9cc7c
cb864bacbd35011c7e4c42350d0dcf38b2e338df
'2012-02-11T09:30:56-05:00'
describe
'24420' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXK' 'sip-files00054.QC.jpg'
99ed78d7b58a85dc3b8263eebd394649
4af8face24eb7761be218c3e1a74c9aa12421ac7
'2012-02-11T09:24:23-05:00'
describe
'8010252' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXL' 'sip-files00054.tif'
b430c3640a45d110a8adf9bb6f577f28
6585017ce40587f7bc6f767b6751b248476d0f7a
'2012-02-11T09:22:25-05:00'
describe
'1476' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXM' 'sip-files00054.txt'
f5c4a990af0ada4eddc0b77dd6f418f0
7f8781a3991ed71a37c42eeb69110ffdbc995b4b
describe
'6476' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXN' 'sip-files00054thm.jpg'
c7c69161927e04504c99c8a863389f16
a32fb8eed90cc5d81f99efd26e4d56a22df67601
'2012-02-11T09:19:57-05:00'
describe
'96101' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXO' 'sip-files00055.jp2'
33b4967b71b74bacb49f32a6bbe3df20
654654200bb14f139a86c3541556c4561a01336d
describe
'76254' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXP' 'sip-files00055.jpg'
442b62fb1d2e5d5b6cd24ecfc50d0d84
5744934fca390ce5d1314d9f4811d72580162851
describe
'34004' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXQ' 'sip-files00055.pro'
4961c814dac955350fe8f26c33943128
2a3c90dc1fdaf085c1c9346f6c66134c0520c081
'2012-02-11T09:30:32-05:00'
describe
'26388' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXR' 'sip-files00055.QC.jpg'
3d500f91c6dc16f253eb7d2a1ab1194f
12edfe7e7a5d75773eaa1f2cc2ec0e89a12cc362
'2012-02-11T09:22:29-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANXS' 'sip-files00055.tif'
599dfd1b264eab7768b87e75b362b77c
b6170fc2419f42afa9f2c273ee49e89241523041
'2012-02-11T09:23:09-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1550' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXT' 'sip-files00055.txt'
af21313adc4c32a74764f186804bc646
c0a0f1ffeae263e8bc0627f6a0ac4b8a9632bd33
describe
'7664' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXU' 'sip-files00055thm.jpg'
3f08738c1581b95c0cecbde0758ce5ee
41024970385ccd32fd5664d42c52711d5534f8e1
describe
'92993' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXV' 'sip-files00056.jp2'
33f2fe9cb7d61cdaed59cf42c92d9323
a7909a1a1c4b8662dd1dd7408cf87e070ea446d3
'2012-02-11T09:27:44-05:00'
describe
'73133' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXW' 'sip-files00056.jpg'
c0951131a37213f7c2173c3da8606c37
7dafc1a395f0199bbab738e70cf2f6071267dd25
'2012-02-11T09:31:19-05:00'
describe
'32781' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXX' 'sip-files00056.pro'
12e6b9529023e4183a4272d626648587
44cf3bbeea91aa7137e1aa384359540386fec369
'2012-02-11T09:21:29-05:00'
describe
'25610' 'info:fdaE20090607_AAAAAMfileF20090607_AAANXY' 'sip-files00056.QC.jpg'
0c4a43e1b5aaffaf8dc0063715a8634d
759efebf8b5aa97de1797dd9e52c8525c1ce83a1
'2012-02-11T09:20:27-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANXZ' 'sip-files00056.tif'
db3f94dbc833093ccb973f37be16ff50
2ea1a42b238f1bbbcee87d3ca1fa38e72afc1d99
'2012-02-11T09:25:29-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAANYA' 'sip-files00056.txt'
795cf2e23b693b7eddb7e0599c1122ca
7b9f2dd2327d044e2c02237daec7c421cfe87973
describe
'7375' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYB' 'sip-files00056thm.jpg'
edc397fe5c0f1c47f7c576a7facbd690
b418631323045765798a13b06e7112c6f932b697
'2012-02-11T09:31:06-05:00'
describe
'86031' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYC' 'sip-files00057.jp2'
88585bd108e1a1abff34cb3603ec6cc2
e934bbee5b09bd2c1ea7420acd09110ffb39a348
'2012-02-11T09:26:53-05:00'
describe
'67668' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYD' 'sip-files00057.jpg'
948f13ef80583b90383edffbd3b73fee
c9c5444358847764091e624ecbff768140d0f7d6
'2012-02-11T09:28:51-05:00'
describe
'26687' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYE' 'sip-files00057.pro'
640bcb01bf0c098c4fe4476772184a68
5e38b971b0422dc3bd56a0fa3f8042c6960834de
'2012-02-11T09:24:43-05:00'
describe
'23495' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYF' 'sip-files00057.QC.jpg'
bf5cda563dee4500a42c85319c4df6ef
04fe4c53d16038b4fa66c22e45de8366f32747e0
'2012-02-11T09:31:23-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANYG' 'sip-files00057.tif'
32aee88ec1be8bb8414a0424ede70f52
6a59ce44ea2ddda590b09e5c96504dfca75dad7d
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1224' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYH' 'sip-files00057.txt'
32cf9c88745a9895bfffed60b60972e5
93d059d91e0387bd2d2359f53991bcb0e6e78d97
describe
'6632' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYI' 'sip-files00057thm.jpg'
770b54e73f062691cfcc03b6b1a49c55
8b7caa7d9fa6adb8b05c13a86150e7c933691f12
describe
'88286' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYJ' 'sip-files00058.jp2'
a72f2ec26e8ba0ad30a1ce2a849205fc
dd3fa0b40a7fd611aea5d8a95fd7728e8435d824
describe
'68543' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYK' 'sip-files00058.jpg'
716abf9cffe12192e66b37fc46013572
40d9513cbd34504217ccbc191c95e44230cda194
'2012-02-11T09:22:03-05:00'
describe
'29816' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYL' 'sip-files00058.pro'
84f3874d2d07ca29914966122e3e51da
faecef63edd9f5bb00be7501eda5c0b487bb891d
'2012-02-11T09:30:02-05:00'
describe
'24081' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYM' 'sip-files00058.QC.jpg'
526d3c9a4a6c5a14d8bb688727c578cb
7d2596fb8b791b8e474fe8c541a4c99f032df8b3
'2012-02-11T09:31:35-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANYN' 'sip-files00058.tif'
88e6e8deed1f061644e00b42f86fc891
cc9bb451a0f45155b9473f83da68e1655f09c923
'2012-02-11T09:20:24-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1378' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYO' 'sip-files00058.txt'
475ecbeb32885860d03d3ea394e3fee6
59c5852f154b326cf5835cca376ae85094d80b09
'2012-02-11T09:26:04-05:00'
describe
'6971' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYP' 'sip-files00058thm.jpg'
789e2d44e2d35273a1a47d7ad510fbf1
8df84e946e124fb38b16301368de14411d7e91e2
'2012-02-11T09:23:56-05:00'
describe
'74267' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYQ' 'sip-files00059.jp2'
f782a7544ca4345f585323141dee4629
d48381fd2c6caeebafc11e51c5857fcbbe9ad7aa
'2012-02-11T09:20:34-05:00'
describe
'59557' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYR' 'sip-files00059.jpg'
a27640b10682f1fda97ad0a39adc17ad
f49e880cf6b8adb93df815d0b662f30c2d49ec1c
'2012-02-11T09:23:52-05:00'
describe
'23561' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYS' 'sip-files00059.pro'
e93db0d8305fb3099a49b271a7ed1491
f7dbe7da9db80be647e640cb4c4fb54d07a8370e
'2012-02-11T09:23:36-05:00'
describe
'21049' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYT' 'sip-files00059.QC.jpg'
b2f0430120e678d60818f63159a065c5
fd95c2bf03ec4b248d80224bd95c8b93273df25a
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANYU' 'sip-files00059.tif'
337b7d5f330f2305d7b58b3db0d73ce0
3d33e87e4575ef6f6b6cdd77992d4809b823d0fa
'2012-02-11T09:27:59-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1065' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYV' 'sip-files00059.txt'
9f2bf459801d783ba34fecff5a57c7e1
23d710c93809a407b4eb775e7570560606032da8
'2012-02-11T09:25:09-05:00'
describe
'6112' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYW' 'sip-files00059thm.jpg'
18ed84f652dc07c342f69d435b2096d4
2b92e768e3345b7bd526777cd8cb76dd25b1e44f
'2012-02-11T09:20:42-05:00'
describe
'102133' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYX' 'sip-files00060.jp2'
23d5ab9aeb945796f4d8199d2179d7e7
e7c075632e6eeb178d5f36faac8c3db24ed77bb4
'2012-02-11T09:20:03-05:00'
describe
'78335' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYY' 'sip-files00060.jpg'
8f15cabdb63715835f8218d79b48aa47
06cfa5a2e5a63aacda7b78876f46d545b6e721ae
describe
'35386' 'info:fdaE20090607_AAAAAMfileF20090607_AAANYZ' 'sip-files00060.pro'
df7b5d3745a61490b8f5958c8551a9c7
7208fb8c5a56ad7e2617bc71655bdf1033d8fa3e
'2012-02-11T09:19:49-05:00'
describe
'27778' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZA' 'sip-files00060.QC.jpg'
98b9357e65ef48774414e1ce297f277d
cdce4aaf5bbbacdf88f180fa2505ce29fe1ca048
'2012-02-11T09:31:36-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANZB' 'sip-files00060.tif'
9c73fcc4409a4710128961fa45dd8e0b
099b8a1a234d9f5da7a0ac64eac6e3d4a602fab5
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAANZC' 'sip-files00060.txt'
d5fe041c4eb439bdd4f456eb147f999e
8088d47001a20a16c28d9634615675a4808c3898
describe
'7867' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZD' 'sip-files00060thm.jpg'
deb9d1add200b6f5f1b75b5d5e61d612
f34e394495b263e23e18987da512f27dbad3379a
'2012-02-11T09:31:05-05:00'
describe
'100572' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZE' 'sip-files00061.jp2'
179eb15308f0df947e08a8d5dc8d66be
4ed3e36fc731a9004d73434110b4da329d58f7dc
'2012-02-11T09:21:42-05:00'
describe
'76781' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZF' 'sip-files00061.jpg'
4512a6d358755e9d5de4baf2484d4819
4a5b430417aafa1735051d72d76fa9427c28a57d
describe
'33795' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZG' 'sip-files00061.pro'
5b9a86ce6d26172bcd56de4254bd7d68
0dce93eaadf19f4e45f5036458aaf07f80b5609b
describe
'27668' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZH' 'sip-files00061.QC.jpg'
a8cc26e5dbb24b66fc5e25f02911a4e8
129919458821239c40ed1eee66609002b33b8250
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANZI' 'sip-files00061.tif'
6dce801f340e842c20e43b1518224e0a
4721eb7cd7f64d3932068d393eb3918bef6968c4
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1434' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZJ' 'sip-files00061.txt'
70c08c69dd4e44705814b22be3758795
e6300a1381b2411d3e66da6c6c49efd185ad7818
describe
'7673' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZK' 'sip-files00061thm.jpg'
56267c4a7f43c5c9629acae28f1d5052
a88fa1c65c5caae1dd950b400335f9687605ead1
'2012-02-11T09:23:21-05:00'
describe
'113493' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZL' 'sip-files00062.jp2'
2cd61de3cc2a4b5b9645e3ebcd5bcf96
225d6c9d048faba2020554dadb3139dc92677670
'2012-02-11T09:25:15-05:00'
describe
'87733' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZM' 'sip-files00062.jpg'
13f6b8b46b56e4642f140f59c99941c8
99ac12ef51cd579b60c5d51e554aac3c8440027d
'2012-02-11T09:22:49-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANZN' 'sip-files00062.pro'
523da61bc9d83db1e2f487fa07aea7b9
5f0848c43dc6fec91bb7f03577cbdb1373d5c921
describe
'31067' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZO' 'sip-files00062.QC.jpg'
494d77868b6dabebd4b151b97d4c7d43
39ecf0f610e2e638b3402de557101e4ed25bc759
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANZP' 'sip-files00062.tif'
385df986762e6c4a102e9a961ced59d3
f06e4be45ba5c180eb6251f794f9546c9a64e753
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1647' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZQ' 'sip-files00062.txt'
3f2c6916d66dd0bb0009542716570b50
f8e8e732ce0123324c0ed9d093644bf595d00b47
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAANZR' 'sip-files00062thm.jpg'
b1a0b1dd553646d5d27c4ee164eaaf0a
81c9fb64dfc9e14ba9b4a378107e6978a58373ce
describe
'92263' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZS' 'sip-files00063.jp2'
e0d34eeabb823d79c2c7133f93395ee9
4a19cf8808332c2486f413b3b060e063b3b84ad5
'2012-02-11T09:24:10-05:00'
describe
'71223' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZT' 'sip-files00063.jpg'
c424829c3e2f59a3497017580db752fe
dc50896798539a33feaad18f6d912de030423cac
'2012-02-11T09:23:23-05:00'
describe
'29237' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZU' 'sip-files00063.pro'
d6c34ac31e77eaddfaf4c72bb4e5b8ef
3526f23c9d613ccafeee189a94f9991ae4d103fb
'2012-02-11T09:23:25-05:00'
describe
'25126' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZV' 'sip-files00063.QC.jpg'
3a20769ff3c21971b9cdda94105b1cf1
d379d1b440977e2404a316ddd051a5a9858ed1ea
describe
'973832' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZW' 'sip-files00063.tif'
2dcc2fc752ad1dea00c187bf1a6a2391
9212d79583a9d7d7a776f7d5efddde111206dbb2
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1409' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZX' 'sip-files00063.txt'
c6b84b2f24d4514b7ea3b2241c4170b2
76859b95e5cd3d364ff61bc21fe4ca072a7c0891
describe
'7544' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZY' 'sip-files00063thm.jpg'
6d98ef90297fac3c2c7d122ee17fa214
863480e47405f9af443aad6016915a60c3a3fb0c
'2012-02-11T09:24:32-05:00'
describe
'51158' 'info:fdaE20090607_AAAAAMfileF20090607_AAANZZ' 'sip-files00064.jp2'
1c4a0cccad6cb801e991cdeda60696b8
8ff1b9b1517aedabb201c173428774dc72808b62
'2012-02-11T09:27:18-05:00'
describe
'42033' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAA' 'sip-files00064.jpg'
06a1aa4c9d130aead78835a195b450ff
4284cc6a20cbc8259e5abbcd0d2289e58f453ebd
describe
'16063' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAB' 'sip-files00064.pro'
2c8d507264c3cb973021f2ac73ffa4b4
d57ad0c4ee9293ba0061669316305838227debce
describe
'14802' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAC' 'sip-files00064.QC.jpg'
103c53fe6c8b786485098eb5ecf701d6
22ad28125bcb99083abbf570abb8fe200e56e5ff
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOAD' 'sip-files00064.tif'
8f3a84a415a7c1f7c5a6c26d230b19d9
a908ed40d0b5e474beceda2b13ed7ab74cc1858e
'2012-02-11T09:24:52-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'681' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAE' 'sip-files00064.txt'
e0993ab4b790efcfabb2a67c61c32824
8228b5582f91301c51ed3fbf186c24ad55ada5b9
'2012-02-11T09:20:35-05:00'
describe
'4307' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAF' 'sip-files00064thm.jpg'
cf3f78af433da24f3a974179788a6f94
b500b3d4406d1acfa8d585650b771cc5ee8b7aee
describe
'94951' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAG' 'sip-files00065.jp2'
948827feea2d67ace3e317e0fa1aa769
e3f039fcdd7b693b6aa55a439834327b01d7d150
describe
'73299' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAH' 'sip-files00065.jpg'
1d424e0de5574f6c398921114322839f
a53e88fca3c6fb9de7e51c7e2e0545454b6efe82
describe
'31877' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAI' 'sip-files00065.pro'
059b615f775fb7206050b81508ba032b
28d2b1f1bb172bebf35d18269a521ec98fcaf34b
describe
'25593' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAJ' 'sip-files00065.QC.jpg'
b380b8fa71bed1ad29d2c820ec98e8d5
7ef4afce2996135e8213b178571dcc1f38080c94
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOAK' 'sip-files00065.tif'
7634f77f9d65f493456c59f1ec275b58
871d7c8c1495c0266f7422a6eac120d224cf7d39
'2012-02-11T09:25:06-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1326' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAL' 'sip-files00065.txt'
01678a595f5db140516d12b098e30f09
d7c2954dff496767f0777290241cf8985b45ba43
'2012-02-11T09:27:50-05:00'
describe
'7240' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAM' 'sip-files00065thm.jpg'
5bd55c38be822e570b605915f00a6eaf
ce4bee7142b3d417e2de402e75f0bcd2d412526d
describe
'108682' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAN' 'sip-files00066.jp2'
c5ec6a81f537aca6331268f58636046c
89d24e0ec9d1eb329501be5db2f4146438521a38
describe
'82406' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAO' 'sip-files00066.jpg'
e2ff9da7590fab6c735d7c2920efb7a6
139f1de9f5fddc7d86b28ccb06869c1035eff57a
'2012-02-11T09:20:47-05:00'
describe
'36173' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAP' 'sip-files00066.pro'
63746bd72bf5a64eea4285cb8eb00029
ce9e0c91bb18ac28987efb09c529ac8ecc9bace7
'2012-02-11T09:20:58-05:00'
describe
'29885' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAQ' 'sip-files00066.QC.jpg'
a8a8815c87c1464c8abc81b493d88a17
7ca12ff003d1e790d09888194db95c6f5ce42ca2
'2012-02-11T09:20:11-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOAR' 'sip-files00066.tif'
adcc611d7634efa88907f14b05817e45
c381089172c242074fe3ebcfe68f84b2801c8108
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1458' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAS' 'sip-files00066.txt'
ef4e5e3409be08afb51cb3019e5c5f71
3df5ad2a17d9f8bf770bee74b3087983c3d02f72
describe
'8101' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAT' 'sip-files00066thm.jpg'
5e6eae05f3e3e08398b0a57c340ce86c
28c8d10e9479f47681eab2296529a7db03484593
'2012-02-11T09:19:53-05:00'
describe
'115834' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAU' 'sip-files00067.jp2'
91198758fceb505bd93e0fb3f6715806
e16f24601aae4cebfe4603be16394b7bb9c9b16d
'2012-02-11T09:26:01-05:00'
describe
'86567' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAV' 'sip-files00067.jpg'
ff13121359580b2cc98d94828f4c48d9
85b07d1df88410fa4b7fc1500110b8e857e8defc
describe
'39953' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAW' 'sip-files00067.pro'
1125d4c60c584269e72c86a93f06b4be
fb374960490154bc9d1e29cbfd2e63f449aa71c6
'2012-02-11T09:20:20-05:00'
describe
'31311' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAX' 'sip-files00067.QC.jpg'
b93fae1a0ef3d57e8dcfa519e4f23f61
acaf7b55696dae8e86d1d677cd071b3d60239d21
'2012-02-11T09:30:53-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOAY' 'sip-files00067.tif'
c75412c926cdea527fd8567faadce3da
46cced76a68baba4b32fd923b015b8189a9527d2
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1621' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOAZ' 'sip-files00067.txt'
429d337ba5bc46967e0176cb642101fc
db264ef4f398a17dd97ab03489ac9d0017fc91d7
describe
'8340' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBA' 'sip-files00067thm.jpg'
b89f4d0bf6e9f089dca97358f5d43317
10110faede31ead1efa60634a724c688312688fc
describe
'109376' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBB' 'sip-files00068.jp2'
5858db5aed44fd48d2a22029f13bc6e4
c1eb3c0ae92a75d115cedda98d7b8918357eb640
describe
'81541' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBC' 'sip-files00068.jpg'
4053ae0e80830c9afda2e2d5486874fa
e0a09a9ff1f2ce61d0d02ec6f5109155789eb640
'2012-02-11T09:24:51-05:00'
describe
'37633' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBD' 'sip-files00068.pro'
832ffbe8b67b9a1a81f8d2e7534dd8bc
863fc7aded22d79c27348d3911c1822faaa4b6dd
describe
'29082' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBE' 'sip-files00068.QC.jpg'
1d40812ea2ad2091a1213ccfd3d2e8ab
41d73bec5ab8a59cfc232074323df081323cfae2
'2012-02-11T09:24:20-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOBF' 'sip-files00068.tif'
f0d250201cdc87e6af2bf07b5a12f61f
1ba5edd6b707dd11b34a1518189dbb82116f92f6
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1562' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBG' 'sip-files00068.txt'
caf32ca4b174808f17a596a5d7ae4df1
bac3de490da1871e21d0894b88ac8258ba1036dc
describe
'7926' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBH' 'sip-files00068thm.jpg'
6411ce11b6d159de02a82a24f0a7cf26
0a591d90c34af1b9a230e9debf80b1b1e219abe5
'2012-02-11T09:22:12-05:00'
describe
'112710' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBI' 'sip-files00069.jp2'
4dd526268b3f141b059203b95b97ee30
98e6dd9cc27c1e77b60e1d97564cf5e35077f469
'2012-02-11T09:22:54-05:00'
describe
'84237' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBJ' 'sip-files00069.jpg'
18bad47c3e879f4db424882142e642f7
aa4b776edb18a884295d78eabf1bbecc902b72f0
'2012-02-11T09:30:22-05:00'
describe
'39273' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBK' 'sip-files00069.pro'
b65695cfa51d37aac9a295e632a214f7
e04aeb71d5f1452838c639ffdf562bbf46b449d1
describe
'30417' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBL' 'sip-files00069.QC.jpg'
58c244825771f34a6025fab91d066225
79ec24b6bbaf0477b88788f32ef5175b0e4f72ab
'2012-02-11T09:22:10-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOBM' 'sip-files00069.tif'
adcd2043472da5bdbb279d7120db8e34
9020b3fb2948b343bd5229f50317da0e6fd8988c
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAAOBN' 'sip-files00069.txt'
9db1e0d3695f760b071cc293b48e060f
c347050f6e7e936be3ff1c7c7869c1317c7e1ac3
'2012-02-11T09:25:53-05:00'
describe
'7859' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBO' 'sip-files00069thm.jpg'
ad03e78e1dc182ffc61b417a3f389b33
f784ca2eda602f711c928fecd1a8f3d5c67044e5
'2012-02-11T09:21:08-05:00'
describe
'968658' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBP' 'sip-files00070.jp2'
c468453fe5aee0b4c600c90ce438c32b
4983a22bd3fcc71452800b4f80ed7767eb95382d
describe
'83715' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBQ' 'sip-files00070.jpg'
14f61c19552782728b63d9b8549b20d7
ba0c335b80e6eca164cee40a250396abb61c059f
describe
'34058' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBR' 'sip-files00070.pro'
a2ea7f387d72b587aba4f1c9ef7e2412
98446ab8f8cfc1dca2e75004cab325a4d0023525
describe
'28312' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBS' 'sip-files00070.QC.jpg'
3e3cd2d96f988794932fc52944285a59
1a7a1e1620f9c03bb636a231fbc77823b6ff4f84
'2012-02-11T09:28:48-05:00'
describe
'7768120' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBT' 'sip-files00070.tif'
eb38fe2e2b9caa91808c77cc40a31f3e
c0ac6f62de2f486e1ad99df88b5521c4b7c7d908
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOBU' 'sip-files00070.txt'
1f5149621b12d1ba54f1480048d77880
f8ab40ebc60a269609bb42fba4f902e663c34205
describe
'7225' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBV' 'sip-files00070thm.jpg'
0c634d2f8a7c1314e552bb0b3841942d
32d4e1adcdc90e1aaf24779737559cec74925728
'2012-02-11T09:31:14-05:00'
describe
'99572' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBW' 'sip-files00071.jp2'
ce839041cd5bf66671642e9697007c57
c0ff75fb7246ff16a3e9eff7453ff2f980a49a12
describe
'77079' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBX' 'sip-files00071.jpg'
27cfd9f26f86848cd4b9d5091b07ea78
ab7cf6369726a84474ea67b2a853ba0c580fdf8c
describe
'33868' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBY' 'sip-files00071.pro'
ecadf3e27e3eebdd4091d42fed065747
cbe4369b36b93b8c58aa456f3b0da397593fe21a
'2012-02-11T09:23:50-05:00'
describe
'27081' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOBZ' 'sip-files00071.QC.jpg'
9d7c0b4483d5a7bbed032002f097a2d5
e06d9338d0ef70e8876a630bdb8954e834753742
'2012-02-11T09:21:18-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOCA' 'sip-files00071.tif'
a58041a90cd63fceb85cb891e3654690
85b7e1c257b1d8a0ebc16d8fade9341498d93e30
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1442' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCB' 'sip-files00071.txt'
d673b6ca76188ca7e0aadc389aa21e19
d142a712982e710e5f9917f5292e9cb8094039e4
describe
'7788' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCC' 'sip-files00071thm.jpg'
0b66de1f7de5066574377641757d3237
4bfc0d5d1cfbd02d56b287ee7c25347e8e8d824f
'2012-02-11T09:20:46-05:00'
describe
'106600' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCD' 'sip-files00072.jp2'
6965e85aa637e5e176a1598b9bf1cd34
b06ca3f94beff53974d3ece0a0e800aa1d720324
'2012-02-11T09:28:19-05:00'
describe
'82132' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCE' 'sip-files00072.jpg'
b142f53025ad46ab7c9b1658dc92c2f2
56f37d54a4ab4b78c402abedbc9a756e004393b2
'2012-02-11T09:30:59-05:00'
describe
'36216' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCF' 'sip-files00072.pro'
5e8382e6b39f46b8eff0573e8b941638
3402cac655d5bd1a5e00f89df04bc98885c71ce7
'2012-02-11T09:31:32-05:00'
describe
'29808' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCG' 'sip-files00072.QC.jpg'
b56972bf07dca06ceb5bcc905595c718
29fccdb3fd142c668d09015ad957a9b2acfeb01e
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOCH' 'sip-files00072.tif'
967ccd96019b5e903f9d981d87e0ad23
3ea8d2ff1f72739d031c9fcdb8f2ee0d67e17739
'2012-02-11T09:30:33-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1515' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCI' 'sip-files00072.txt'
90f98080c69631201e73af2edd740754
888ad6ade168d4a26b62262183beb5425021b507
describe
'7875' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCJ' 'sip-files00072thm.jpg'
cb75bc1cc9d1d5b32d68b1e8cbcc640e
4e222b83fd97b27d9f1892207a813ffe761673a5
'2012-02-11T09:30:24-05:00'
describe
'110164' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCK' 'sip-files00073.jp2'
d39c10ace35c866d4ea2f8f908db2f9a
6d8eaae22696028142a6e940fe9f51e6fd5a4ad6
describe
'84012' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCL' 'sip-files00073.jpg'
c7044321788689e69cf1cb3983b7810e
7245fedd0f9a125ea8167aac201a86b37cbae856
describe
'37608' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCM' 'sip-files00073.pro'
6f00ca4ac625ce9446ee52eb35987b2b
d4870f2516549d1e7953fd9fed8f361ddcb64427
describe
'30296' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCN' 'sip-files00073.QC.jpg'
caf46d75a49f83750d27bb646b6d46f7
4050ab0f7bf95593ac8488a43011afc9cf24503c
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOCO' 'sip-files00073.tif'
ca9572524ec0d5fbef83bbeb1864efb9
994878de0efecd3ea3f784eb55b699a2f498b06c
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1541' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCP' 'sip-files00073.txt'
e1b73cbd2b4047df52a99c17fa9adcff
12f2feb0d8ab32a9d48881bdf32b4d62a7b0b382
'2012-02-11T09:30:20-05:00'
describe
'7999' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCQ' 'sip-files00073thm.jpg'
d33d2c20bc341ae11c7e980f8f9f0717
1845b0a902129223c2cebe15ad875dd049331875
'2012-02-11T09:24:09-05:00'
describe
'113175' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCR' 'sip-files00074.jp2'
54ad3d31674b5e92115ea46a18596535
130832919676c46186007da981be22eacad5afa9
describe
'87766' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCS' 'sip-files00074.jpg'
a8fa91f1a922ee1de2cef19bd39f0d15
0cc9deb30abeb6b1e0efde39711390afaa73b39b
'2012-02-11T09:22:01-05:00'
describe
'39875' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCT' 'sip-files00074.pro'
f590df7e18f5f016af8c0559a4113c1a
8c786808d151aba86aa55619a8534dc675cbb573
'2012-02-11T09:25:02-05:00'
describe
'31297' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCU' 'sip-files00074.QC.jpg'
4878ed1f5e0256498e85aed4459743fd
0c346b9ffc51547012084428e62cc0f13d95306d
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOCV' 'sip-files00074.tif'
72b25d9fb2e6db20bb0261a60dd65823
99a2a9b870f1186f5a72481eaa71d255e0aa9303
'2012-02-11T09:30:39-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1658' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCW' 'sip-files00074.txt'
b8ab8cbe95b1aa5fe8de4afa018a777b
24e2c88ab71d8d89017ed1cf67c7548e9cee15f0
describe
'8373' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCX' 'sip-files00074thm.jpg'
69ad16d203f40b2beacee16e629df115
34d55a20b548ad7cbb985aa7c93e45a4fda846c4
'2012-02-11T09:27:38-05:00'
describe
'1011362' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCY' 'sip-files00075.jp2'
c34d520821f855481ce9e91d06f35bcc
e33a446fde8b3798b1797676f3d5445a0639b6fc
'2012-02-11T09:22:14-05:00'
describe
'84300' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOCZ' 'sip-files00075.jpg'
ce3dea9154ff7b614c649e95fb90d361
efde9354cb7d1ac1eec6b583d2ccdfc20d492b2d
describe
'38440' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODA' 'sip-files00075.pro'
587f3518df1c7bb73f5e9c796b57e460
7d2916a62fd33f3a137a988fd3eec77b041ca295
describe
'28796' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODB' 'sip-files00075.QC.jpg'
b00d7dad027210a8a917109ef77ad0d9
ae983bf008bed3043d8876703eb6f5b630884076
'2012-02-11T09:24:27-05:00'
describe
'8111524' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODC' 'sip-files00075.tif'
e4660d277f449db7749143408a340dda
59e63af4199cb69393ecc63d7e9fbf00fec9523f
'2012-02-11T09:23:55-05:00'
describe
'1567' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODD' 'sip-files00075.txt'
9caac402426bda9f539991430db26a5a
de51699eedae5d2193d6f7825e3405e26a723cfb
describe
'7786' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODE' 'sip-files00075thm.jpg'
d492e38e7c878ac0c8d1d70e83a1cedb
ba5b36abccf6f2e9d8cc55bc1af55b9e91bd8ccb
describe
'104149' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODF' 'sip-files00076.jp2'
399774bed0b9404466addd861664a4a8
6432a3e37baf74f57ec67387e5dc3d60ad626785
describe
'80171' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODG' 'sip-files00076.jpg'
d55e6b014e1c5755b868301a3de4c013
683002fc3ef507665f03a9ab28fb0ed74ab4bd98
describe
'35053' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODH' 'sip-files00076.pro'
1b7724613e780b7c03bbd6efd8081375
665e1fef42f78cb19acf5cf71183b3d2a2c87aab
'2012-02-11T09:22:00-05:00'
describe
'28470' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODI' 'sip-files00076.QC.jpg'
140771efe9d72c3313b47e936f8af582
bd97369755a8e8f7c252bda27165e04a637f2e75
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAODJ' 'sip-files00076.tif'
a975220eff485148b251458df88320b6
60e05c491c7db87aee4537ccec3abe4f8a9e7378
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1450' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODK' 'sip-files00076.txt'
2dcb8402921ace5aa93da3f6c4bd19bd
6a41ffc64824f6b0b7f1cf91f348d932897d5403
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAODL' 'sip-files00076thm.jpg'
ebb54cd56d4467f267d5766c9ab4cce9
ba8582248a1799a494f54b94ff1b09a0755393a0
describe
'114594' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODM' 'sip-files00077.jp2'
567e05d89789477de2f624d60c7aba52
ff6a4d6cf52ff8b10e7a58e793f7fc64215d8079
describe
'87427' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODN' 'sip-files00077.jpg'
e90feae48714d844dbe9e298f14e1a9b
e475b90b319e94a1e7d30cd96cbc5e2cb55e9af2
describe
'39292' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODO' 'sip-files00077.pro'
f3b117bce3dc44885cf5ea757b77e75a
3475965f5257f455319ba3db94cae0610a2f8f37
describe
'31879' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODP' 'sip-files00077.QC.jpg'
873a9a5e1ce2a548f92bbc78291627b4
e52ded326412a1991811169ed8ae92179216e31c
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAODQ' 'sip-files00077.tif'
0386cbf2890938dd3449ed9a7d818d2f
57108ba07407f710f45e51d4cdd8835ff6f22f16
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1607' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODR' 'sip-files00077.txt'
e46c818929239cc68b8af9a7595c83a2
f6ec8181e1d4fcc600e19a6e66bc65b7579fbdbe
describe
'8537' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODS' 'sip-files00077thm.jpg'
bda9219783b78221c434c4fea5f308b0
4b77df5fe6a36cd49688466554a0d164cbef5318
describe
'109768' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODT' 'sip-files00078.jp2'
61df1f83ba07694496bf4af01b570955
52ef2327ec40cdf502487211fa8c19651d04903e
'2012-02-11T09:23:51-05:00'
describe
'85776' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODU' 'sip-files00078.jpg'
80c8a585cdda00538645f6a1fbfa4f14
fe2cdc1242dc8b5266a502f689cf2d2b77b05d01
describe
'37923' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODV' 'sip-files00078.pro'
c878e6bbb3a5134972377c43fcf6f9a4
a29f075090053e84cebe9f2a8d3fcc362b7eedaa
describe
'30581' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODW' 'sip-files00078.QC.jpg'
dabc9379dd0a486e6d52d56bba4e1df7
ded4b313460f2727acf87a4727f70e231dbcb291
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAODX' 'sip-files00078.tif'
b959e2dad7efa1ddc99e29fd19da7085
92c905a850d803878a2c0d82b408828f5c0fe32f
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1556' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODY' 'sip-files00078.txt'
988d997e37c6042374e7fb14c6cc1f7f
5f403a503a424a7872c8e0ced4003243349e33f2
describe
'8274' 'info:fdaE20090607_AAAAAMfileF20090607_AAAODZ' 'sip-files00078thm.jpg'
31ebf738739c2067783665badf69478a
c77f10156b5c9dc0fb1d61a27fadf9f811ea5c4b
'2012-02-11T09:27:14-05:00'
describe
'117139' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEA' 'sip-files00079.jp2'
8970e6095d6930da19978b5766ac03c0
e3f0674d254714bc42db60babbd9bd926e1a9ad7
describe
'90210' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEB' 'sip-files00079.jpg'
f23e53197a9780458dbe2d2870683e0f
dd87be7b101ba05c76cf837582d425c157eeed93
describe
'40582' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEC' 'sip-files00079.pro'
9c1fbc391779f7bf3cbc6e8c0454faf8
829c66e59cfd803cda86c3b4ee7d8084cb95cb40
'2012-02-11T09:22:02-05:00'
describe
'31878' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOED' 'sip-files00079.QC.jpg'
5dbc5e71430fc719ed8cf6a027c4042e
adc7ba986742c9f94812ea0d6b8b5e9ae51dc1a8
'2012-02-11T09:31:09-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOEE' 'sip-files00079.tif'
4327546b152ac75e10a8cdca477a8125
5986b9209bcb6e08fc4e657f4cc9f7ab9ec9232a
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1687' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEF' 'sip-files00079.txt'
92a1ea3347b54296e85c0c5929149e8b
66c3921a2e81a2c0b23d77953ac2b1c7d5a6d8b5
'2012-02-11T09:29:39-05:00'
describe
'8390' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEG' 'sip-files00079thm.jpg'
8bc842747fdd2de6ea6b3613a0d4cb8c
ddfb8a07a0769b3d8cfc57f60117e2a424c4e3d2
describe
'106317' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEH' 'sip-files00080.jp2'
9b4a6f6d8223d419e0d65f51411867e9
d4b987296d68979819b77b83cf24a5420c6d718b
describe
'81748' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEI' 'sip-files00080.jpg'
92cd3d8bbb9702e4a9042c8a2de7b844
21b3726704daa67521d388f8dafdc2fe007b313b
describe
'36656' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEJ' 'sip-files00080.pro'
9f1eeade7b9e9983f64a1883d2ba4d53
7f7961a4e1b6368f6583a57a20e4897785ad1153
describe
'29165' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEK' 'sip-files00080.QC.jpg'
3735403b5aa40f3cc2176107a4420183
78825919702535c0df0aa0be70e79a9f23593dbc
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOEL' 'sip-files00080.tif'
88bfab8c84d748665750784658c4888d
c41fb1302274bb6fc776493f11debe6e0484733e
'2012-02-11T09:20:50-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1503' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEM' 'sip-files00080.txt'
26bde484bb57ce3333407b9e268538d0
6df26458f3916719c83a1cc9b9f93707882595e7
'2012-02-11T09:26:07-05:00'
describe
'8084' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEN' 'sip-files00080thm.jpg'
e2994d2996ab547e38b0ba445712682e
7505153cafa7472d02ec2666dc4eadcee23e4cb8
describe
'113118' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEO' 'sip-files00081.jp2'
756f7a565f105e36043b053fc7218aa3
ff12267b82cc2d6f1bdc5e5265bdd6d310480834
'2012-02-11T09:20:22-05:00'
describe
'84800' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEP' 'sip-files00081.jpg'
fa27602cad4e8bbdb5fd07f9284bea76
08f5fec6da82cfc6ad92c046793ad89dba9f89a6
'2012-02-11T09:19:50-05:00'
describe
'38098' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEQ' 'sip-files00081.pro'
fffe15f65abf27cd98853407fad8710a
21902356ea3ddaab461fba6626446229563abbce
describe
'29909' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOER' 'sip-files00081.QC.jpg'
6082e30d1a372ef54e60ee4806aecdc7
ca12e02c27a15dd96b90875e50eaf7b941fb4ad6
'2012-02-11T09:24:42-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOES' 'sip-files00081.tif'
ffd8bb24cec690fd81b8fa8f25a2cab0
d6623cb3152a7655bab89ca331534e3168540572
'2012-02-11T09:23:37-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAAOET' 'sip-files00081.txt'
b7b67bc267f11f5afd702544ba93e58d
7966b2e01e88d9524df0280e1f63a3ffb20203b3
describe
'7949' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEU' 'sip-files00081thm.jpg'
ce3640bfa9ce428334fbb0123e6e367d
449913900cda47e5584b62e8e5a522e82e628445
describe
'108831' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEV' 'sip-files00082.jp2'
4c61bd21d0c491cd389c6a552520f926
347b52aaaa3d7435075ab4b4c34a4c3c18f22c9c
'2012-02-11T09:29:06-05:00'
describe
'85720' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEW' 'sip-files00082.jpg'
1395989b4c0f1b13587dbec10129f76a
f7fc69aa7f765428ed031159441898ceb29626d1
'2012-02-11T09:27:11-05:00'
describe
'37897' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEX' 'sip-files00082.pro'
bab9154df9c938794ad86ba9ee60379e
fd29e4b3e90ca98cc8f796b2097100f348c92e85
'2012-02-11T09:26:44-05:00'
describe
'30224' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOEY' 'sip-files00082.QC.jpg'
d101cabd8707c0d4fbb78f1bc1478bd9
8989ee6ba80adeafd16b0251c5fbb61d5e3bac8f
'2012-02-11T09:20:43-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOEZ' 'sip-files00082.tif'
2a35ea08888df62d08b9f1f3d8d73fcf
2da38b36d73e422aa64f3c532091296b886e699d
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1571' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFA' 'sip-files00082.txt'
f12250d1b09c716f89aff0f31e30f1a2
82dd0cf4debfd0a3269fd41a029306d633d34095
'2012-02-11T09:21:46-05:00'
describe
'8279' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFB' 'sip-files00082thm.jpg'
3b8f3a1bf835cc5c75e6d50c1ff27568
4d4d05bb1e2782aa412219b3a751e5063bde30ca
describe
'46313' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFC' 'sip-files00083.jp2'
41e9997d2917af3f843ad0ca8a85e4f7
771334f74f2e6c7fa6563825613268f0dad43467
describe
'37824' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFD' 'sip-files00083.jpg'
c06cbb16a470ab2c217687b248034106
42d6df71b4006d6e032a482e923e8599873f22c1
describe
'14226' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFE' 'sip-files00083.pro'
5063f8eaf10afc72d4eb40aafddbb70a
41e36230c32142db0851d8a6b4139426d686e8e4
describe
'13282' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFF' 'sip-files00083.QC.jpg'
e66d693c5dbca326e23475ee73642c0d
c3731b1e9079169f2730b2c9f3b850756f22d9e7
'2012-02-11T09:24:59-05:00'
describe
'962728' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFG' 'sip-files00083.tif'
0a6e4a1bd0c9c0d8e4b98e1cac68b0bd
5ef791694644cc307b7877f0115482b102af7ce7
'2012-02-11T09:26:41-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'617' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFH' 'sip-files00083.txt'
9b6077cab3af5db243d766045808b5bd
2356d13c8c27b7447fadae3e0236541fed4c57d6
'2012-02-11T09:30:54-05:00'
describe
'4132' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFI' 'sip-files00083thm.jpg'
63bd5f954b3cc02aaabcd9b252fd59b1
4968ec5690d763529a164ed3db77bb3f5f6df433
describe
'95337' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFJ' 'sip-files00084.jp2'
976d4ad64d94140e259b5d5cf0342a61
4ef412119f0ce8505471f8114692b54e7827ca57
'2012-02-11T09:21:05-05:00'
describe
'75236' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFK' 'sip-files00084.jpg'
6404bb57ec7d6a410b151ece23f8e63a
132ad8dfd6c01901ff03f9a226dff35c4b25049b
describe
'32260' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFL' 'sip-files00084.pro'
14c1b9baf9452bcd9fd3a0f15d86e6f1
3b2897ba6f42a631dde7cc8f008d8678960d9cc2
'2012-02-11T09:22:50-05:00'
describe
'26526' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFM' 'sip-files00084.QC.jpg'
3ce418feb7b11a8446d9c13d2b0a9f74
b82a675a36e23ca46598d3de8b0c41ed40d7eff0
describe
'963324' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFN' 'sip-files00084.tif'
056c96d663969f0c488e24cf04ece7a0
a54e7b8d6859dcb46ee36af05b77dc53e06784f8
'2012-02-11T09:21:41-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1393' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFO' 'sip-files00084.txt'
04ece9f27096578c9eced240083b1bdf
7e202dbb143d05f4c610ae7383e3132541442493
describe
'7417' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFP' 'sip-files00084thm.jpg'
faca8cd73316c754f031003ef4565c03
1bdf3e04cbf2ee4a5c1770c34576aa865168e594
'2012-02-11T09:24:44-05:00'
describe
'25084' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFQ' 'sip-files00085.jp2'
c7b1c629e931c00bfbf5b61abcfef27e
74da40fcec96dfdc134af204697141b804ff2e2d
describe
'23326' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFR' 'sip-files00085.jpg'
3fc8466ecd43e8f9bc5da4c74bc8c605
f29260eeca92c28237f37b29c1ecd0132e3b286c
'2012-02-11T09:31:33-05:00'
describe
'6869' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFS' 'sip-files00085.pro'
fa997a936663611896ff6198cc87c134
d62fbc21a2d17130328b3c6a852fd04741b36442
'2012-02-11T09:27:53-05:00'
describe
'7703' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFT' 'sip-files00085.QC.jpg'
6c1cb2a6dd2f33fb7cf15741c5e61d08
435fa538253bd4d280df6fcc4c901b96a4bea954
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOFU' 'sip-files00085.tif'
505b3f7b7e043235b91ed6a616e314b1
db624cdeb59b85f05137ef888af7acb347996f48
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'330' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFV' 'sip-files00085.txt'
dc8f11242fc772e437855ad36440d7ea
81f61be7c450755fac6060e1f70d3fa09f2e4380
describe
'2484' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFW' 'sip-files00085thm.jpg'
9785095cd89d9dfaaec02835f736c646
37d5f9069e96c7ef6a799e8343cfd38daef485ae
'2012-02-11T09:29:35-05:00'
describe
'69728' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFX' 'sip-files00086.jp2'
4194f6f9ef898668fcebce43bd1ab150
73f36000dd5fd9bdbf0037e4d010a425d7e302d0
describe
'60363' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFY' 'sip-files00086.jpg'
3af060692a306b8595c7b2fb1fcaaed9
6a42aa9e237c8e3cf77a34b969bc72d285c9012d
describe
'23824' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOFZ' 'sip-files00086.pro'
bb511217a1ca271918e22fdc9c8ca173
017f8c0e59fd3a8c7a6f286fa608a13bc156a819
describe
'19827' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGA' 'sip-files00086.QC.jpg'
4b3715024db81f1f4012391f8eef716c
70c91a180256e1ef28fb718815fcf29624d91d76
describe
'967153' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGB' 'sip-files00086.tif'
921b8c4998e747c78665039cb131564e
63586e9e6bbf2eeaf1773c0a71a02661faf194b1
'2012-02-11T09:26:34-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1198' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGC' 'sip-files00086.txt'
731919bff479791eca0b5bfdb535e94f
665e0c4cba550983d2885dcb93ac14411c32d967
describe
Invalid character
'6082' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGD' 'sip-files00086thm.jpg'
a5f611ed865738bd32020fe7c8417e0b
78088cc278b251c4b44615fb3d41d380962b9517
'2012-02-11T09:30:44-05:00'
describe
'41411' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGE' 'sip-files00087.jp2'
457a3eab3e319ac80468c9b80b73ffb6
a44679a53f7a7c0aeb11d59ed3390355ae9c6b11
'2012-02-11T09:24:24-05:00'
describe
'34592' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGF' 'sip-files00087.jpg'
b9ce8807e0d218109ff23f459192cf36
e70032b0dde6c1afb4ace8b9569ac8f3553a9bd6
describe
'16103' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGG' 'sip-files00087.pro'
6d8426ec2ac36113613b9de85fba1021
ef5da7832ad595ba1b3c4b67fd1fb3b21a7d331d
'2012-02-11T09:22:24-05:00'
describe
'12663' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGH' 'sip-files00087.QC.jpg'
a14786fe619f4936fe7585bc7a225a7f
bc5a52fcebf0c6abac51847b61f98d17ece1ae0c
describe
'964516' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGI' 'sip-files00087.tif'
6e319a588c6f24a7dd41fc513e4b713e
993d09176aed32b0a9b4ecb5a0986f076335c674
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1026' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGJ' 'sip-files00087.txt'
f4534b405f1836a2a4cf543418d3009b
064f58d6ddd4a82a984e9b87d13c5a3cceb4174e
describe
'3922' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGK' 'sip-files00087thm.jpg'
8ee8a9a7a41d3208eee25963db9d9764
72f756118b054654625566f1b7b4f757692bf443
describe
'23269' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGL' 'sip-files00088.jp2'
12c8f5516eafd3c088ac4ea2c6d1b6f3
d9971c45bff27e2d7c89f535161daed54e037e86
'2012-02-11T09:20:38-05:00'
describe
'21946' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGM' 'sip-files00088.jpg'
9b39277f3396d9726a1c4068a4fa75fa
6b02284c36bb0200c89a50a57f58d3bda946b6ac
describe
'6502' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGN' 'sip-files00088.pro'
87c7bd00a7a02f7b314a07f1317b0741
042ba0338b4f20ecc3d92ed2b11e6e4df6951455
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOGO' 'sip-files00088.QC.jpg'
067c82a0c171e76f4bb67b08765af898
c9712c385d37a555e2088b1bf6b87f81cd82327a
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOGP' 'sip-files00088.tif'
9aff5db08915cc1888e181e252191cba
5b75fa8d694e5800438c2c1464dd046ad81f15e1
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'349' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGQ' 'sip-files00088.txt'
2f77fec6663e8785d464dfdb491d31c4
9e7cf43b2273c713e1ff44ae8fd2e35020d42af6
'2012-02-11T09:30:34-05:00'
describe
'2621' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGR' 'sip-files00088thm.jpg'
8945b0bce92b2d4b60a40dbca7af54c9
c889bf1a534c82049c1c10558e10a35be9cbc489
'2012-02-11T09:25:25-05:00'
describe
'57464' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGS' 'sip-files00089.jp2'
06c682773a6f7d4283c5ccd2d4412ca2
ef18ca8c50ae95af6b5d8575b994856cecd8e672
'2012-02-11T09:24:08-05:00'
describe
'29485' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGT' 'sip-files00089.jpg'
ef593bd895a8825ace0237f1232bb41c
15d71678482588c7ccb7d45dd842bde3f9135c08
'2012-02-11T09:20:06-05:00'
describe
'18686' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGU' 'sip-files00089.pro'
66f9ff6565f2d34cce6947af9e370cd4
ef020a21a6805c0e6eb44db0563d84c7b7b4139c
'2012-02-11T09:29:03-05:00'
describe
'9930' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGV' 'sip-files00089.QC.jpg'
f6e9f7813c206c0ad7c7367d31018a2c
fa779b8bab9fb660cec036b155d2e217c6a83089
'2012-02-11T09:29:44-05:00'
describe
'965430' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGW' 'sip-files00089.tif'
cf7da3df2a7447d35348977a10f5d630
fa1e9e79872f56828b18badd1b1e7761009de530
'2012-02-11T09:24:30-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'894' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGX' 'sip-files00089.txt'
de37c679a34d98ecbd6d572272386dee
ad4bdd57bfca7ebcca810be4d6d485413cbccab4
'2012-02-11T09:22:07-05:00'
describe
'3265' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGY' 'sip-files00089thm.jpg'
e89f849ba4ad2ab96594f423ca9c68be
8de6cfc406956dd96b91f369c784f54810536515
describe
'65553' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOGZ' 'sip-files00090.jp2'
8938023e37dcd32005a20eaf4a11b14e
ffd01dd80933717def813fdebdc5b036ab598baf
describe
'51471' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHA' 'sip-files00090.jpg'
cdd377c99048a7eb723903386d52e85f
c0148a9687856d8e695ab15d1bb28b80fbabe3fa
describe
'23446' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHB' 'sip-files00090.pro'
60b638a45ddfbee20b0115099ec07f7b
a60915e3a882408e73fb03adf1d4348a700dea31
describe
'15774' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHC' 'sip-files00090.QC.jpg'
a52c438305884af0e5019fa772931417
1e59bf596f0652ca0945835c9785ff0bd36b29e6
'2012-02-11T09:26:56-05:00'
describe
'966555' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHD' 'sip-files00090.tif'
dad9450d37761dced582c7e24bac6f32
84879edef82b656458d29aafb30450e584dec9ac
'2012-02-11T09:30:08-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1022' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHE' 'sip-files00090.txt'
b75dd57bcd4bda9bc8e41e0caf483f50
72e91b4d09e1257da9e102feca23a753e8b316bf
'2012-02-11T09:28:16-05:00'
describe
Invalid character
'4884' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHF' 'sip-files00090thm.jpg'
1e5205c61112e3b66cd90fbf32655367
78420bdb19bd749f22c7952892fa1515bd3500f2
describe
'35381' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHG' 'sip-files00091.jp2'
fa39839422a5ebe609f37c00d4c67007
be2b8858cfe71bb34eb15da5615aebf030fa62f6
'2012-02-11T09:30:41-05:00'
describe
'30427' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHH' 'sip-files00091.jpg'
679e791a5ef388951da890e6cd6aa3e8
c6b171b7dae78626aa0c0e0cda0162e5093ac71f
describe
'12434' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHI' 'sip-files00091.pro'
065d1c2dca65b0b5a7e0d3866dacd972
e16f3279b23f7e69bbd8761e18fc4d57c959fcb9
describe
'9433' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHJ' 'sip-files00091.QC.jpg'
66b73a4eb336ab30db4fc1162070b6fe
c388900cf0b0fc44e93cf969a43f88374fada2fd
'2012-02-11T09:25:05-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOHK' 'sip-files00091.tif'
bdbb3b6a3b901f0cd2a1937d07d5d140
824ea3e46ef33c4a487a1bbfefde28de2f66e362
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'655' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHL' 'sip-files00091.txt'
e2c3afa8b54b9e6672594811904c2ab7
c4a3e40a23fdd74d983bdc072c3663e2e318d234
describe
'3012' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHM' 'sip-files00091thm.jpg'
7f03bab2897bc64131fdf188a64712da
90f8601688d4ac5b3d82933c43e1c2f3ccd59d05
'2012-02-11T09:21:57-05:00'
describe
'49279' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHN' 'sip-files00092.jp2'
d30e3507cb20da88a1ec8999fc902bd2
5c5f7ba7665dc1b1d4efb60eff7e84b624b8fb69
'2012-02-11T09:26:28-05:00'
describe
'39133' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHO' 'sip-files00092.jpg'
c8859bee1a9c946b93f8f5dc9c8acc83
a87c63a54c1ab3bd5ad6f1514d864bd881c30c05
'2012-02-11T09:24:58-05:00'
describe
'18108' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHP' 'sip-files00092.pro'
8b332dd5827d9cae25f258af2f0316e2
d57a228a439a54cb9831a49bd7d1a1a7e6c535f2
describe
'12687' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHQ' 'sip-files00092.QC.jpg'
677cd1940d046814d78f6e7bb79705c9
7a1043740932c9abe0b48d941c06c20ddbcedb9b
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOHR' 'sip-files00092.tif'
571d00e1a9d2437db4ebf8a9c3915abe
9c7872028d0e7cb36a4e37fc3c549aa17453d28b
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAAOHS' 'sip-files00092.txt'
2d4318b2e585e6b1491843d8ea68b102
b147f40b8435b7c8767b966677d09d4fe4242ba6
describe
'3887' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHT' 'sip-files00092thm.jpg'
a8918325d98102b403c09dcb180ed823
628ce064e9eaa17407fbefd9f786997d370f391a
describe
'46031' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHU' 'sip-files00093.jp2'
b58a5aa38fb14c0b5ddde51eddc887f4
e893db209dadaf037a1b5345858c4d4b542ec199
'2012-02-11T09:20:31-05:00'
describe
'23915' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHV' 'sip-files00093.jpg'
d8e0fa69346b06c10eb628fd6725486a
46da7919b9416f02f5ba14bafca895d9a4ec0570
describe
'14266' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHW' 'sip-files00093.pro'
bf86a8d2f396d0c2e5f93afcf29546a1
113bd22296b3be8bc2217dcb783d330dd7cdb7c9
describe
'9107' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHX' 'sip-files00093.QC.jpg'
5359791f90dc21a168fd05222fdc28b7
bfbef0a2b0a86863ee29120fb597e11bccc8c90d
describe
'967008' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHY' 'sip-files00093.tif'
ea394fe7412423ce1c6b0c436305d802
42f035a08438978020f700b6b4d0076bea9d7057
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'842' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOHZ' 'sip-files00093.txt'
8955a97d385fba2ad676dbc25befeec8
c714b254bce9cc2e93bbb9c80c85185c0466773b
describe
'2901' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIA' 'sip-files00093thm.jpg'
58a1c0fdd77a64c9f5dedc4e1b4c8381
1b39c191e4dd9b79eb75f6a40b07c4859f07a3e2
describe
'33240' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIB' 'sip-files00094.jp2'
e0d9fd734f6f03beecb0a3729d22922b
8fc5028fd4230a7757932f11078e292085d5d716
'2012-02-11T09:23:45-05:00'
describe
'17969' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIC' 'sip-files00094.jpg'
e93774192dc041e55d42b3ae6948e7c4
7dfb167bcca6078517e2642ab198c3c9cb88b6ac
describe
'9133' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOID' 'sip-files00094.pro'
dae48d21b8a026f2da7250a7f76fb341
9a3dc0ccc00ca773ddb9960404a1117e99a21c00
'2012-02-11T09:30:48-05:00'
describe
'6592' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIE' 'sip-files00094.QC.jpg'
c8b229454c098c544d1f75c314437696
1dfa27ccb2be4f8f85656532df42a0f2beae4211
describe
'967818' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIF' 'sip-files00094.tif'
caf233aaef04f7d45f662565a77c3838
85013f4ae3f901a5b0bb95a7e642867f8e5e05b7
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'462' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIG' 'sip-files00094.txt'
8d0f5848acede28d6411f3f939389c26
f79edc3d5fc9e776abc432f63eb8f4bbc6daed8d
describe
'2443' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIH' 'sip-files00094thm.jpg'
9f3a20285ef82d75b28d23cb1dde8637
47fc7df21e82087d91f7903856130dd076f4c402
describe
'58801' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOII' 'sip-files00095.jp2'
2a2833481e9329ad98e6ca624efd146f
a3dc1fcf89dca08daf976287448bec890a0508e8
'2012-02-11T09:22:06-05:00'
describe
'46794' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIJ' 'sip-files00095.jpg'
78d7a12bd64e87448baf1189be0f6a02
91028f62d53a9d7825a19625c48526cb45b548b9
describe
'18890' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIK' 'sip-files00095.pro'
df20e46b86d505465b112da279a7efd1
09d0cd10f5fc065ed00dae78488dcd875ce4bddb
describe
'15690' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIL' 'sip-files00095.QC.jpg'
8b64cc4f385d14fbf4d56d251f8fb928
bc59569db8d82a010e54b01063d8974609697ac1
'2012-02-11T09:24:33-05:00'
describe
'967751' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIM' 'sip-files00095.tif'
160806a2172c3b14a44953c06bc685b0
8e992f4b9b2fc18fa5d246509fc24bd6eb31f6ef
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'893' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIN' 'sip-files00095.txt'
c1f7587424331d81c6c6d1e38346f9a9
25db285604c1bc7cee3be67827e26b1282661d74
describe
'4615' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIO' 'sip-files00095thm.jpg'
2ae0c79da58286d5e71335e984c59a5b
7df9027575836accd3e0e04f09e5f196dc020d8d
'2012-02-11T09:26:22-05:00'
describe
'58814' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIP' 'sip-files00096.jp2'
ddc1525d56183616fe205e69b2b85b0c
ce8d7296e8ed970b4528d8122fdd6dcae6cae2e1
describe
'46496' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIQ' 'sip-files00096.jpg'
d3aeb06ffa8fdd1700d53bf3e945a8a0
a9b3e33c9a6e2f9d9882e0147bdd7ab7db02f460
describe
'17889' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIR' 'sip-files00096.pro'
480255c38e8c8bf34a5dd5011992ea02
2337a42f3a52568bbcc469bddb96d46869bd5fd2
describe
'15698' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIS' 'sip-files00096.QC.jpg'
bda9ea0ef15d9d8c92edb209ffa3124a
fe03a7624306adfde2c632f6ba1934799060dbb3
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOIT' 'sip-files00096.tif'
190570bff8d1ec9d6edc9411817c1f23
c507c9757f2602741e5ef207884c8f0bc0f611af
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'810' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIU' 'sip-files00096.txt'
fffad922ce7c39cb8fc6888dfb49bd26
a9aae4e8359d06b6ea0c2c83b3e83b050c6923d0
describe
'4691' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIV' 'sip-files00096thm.jpg'
6608043bf726a9d1b4ba2ffd62542c1f
55366786359a7682c5e8570e7d8d7b578b3836fe
'2012-02-11T09:23:00-05:00'
describe
'51354' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIW' 'sip-files00097.jp2'
d414d1788bbbfd3e0d02dfa3d96d58a6
55c91934c3137f8001c4dbb120a88725777a9879
describe
'41915' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIX' 'sip-files00097.jpg'
0a449252273cd699e5fa65f3e5079ead
fcfd0b52062c1a62dcd7b264b6408496e7171afa
describe
'15878' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIY' 'sip-files00097.pro'
8e9ebedbdd42356c21a055e340f8fd42
b8d982326542757ff1fb1f9cad57d1c0c5e9f166
describe
'13868' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOIZ' 'sip-files00097.QC.jpg'
495ca96268e001bb93c9a97fa5a367be
d1654e91b5885b108f899f39b163b152fe9b38ac
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOJA' 'sip-files00097.tif'
657be75d866fc4095fbf8d8a06140e8a
5a043bac7eb8404bcf1573e4aeecdc719c49c9ff
'2012-02-11T09:30:42-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'775' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJB' 'sip-files00097.txt'
15f1739c021628d52339e533445b545f
6848ac5f4279aaa9727f628fff1b00c2718440d7
describe
'4473' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJC' 'sip-files00097thm.jpg'
31bf4b79e099ea5c5809b7b430652251
d7775cdf87ee724ce16787c7e962ac48a1ecff06
describe
'58782' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJD' 'sip-files00098.jp2'
42c43de4703bac4e57e1182c64b2cddd
9f7306ac523607d3544880a7a03824c6a2232198
describe
'46273' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJE' 'sip-files00098.jpg'
fc5182e67f0f9fb503f4f6fa8c55656e
5fb5d728f109161b5480a090674f9a98485dc25c
describe
'18685' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJF' 'sip-files00098.pro'
bc17cf15cb193d3d67ffbb213ec0829b
b2479ef6dd2c58adca5970243e27ad906195e977
describe
'15034' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJG' 'sip-files00098.QC.jpg'
5c353dbb91b0a5903b4dbce5dd7a24d5
916b1ef62f57faa274e6bddab02779a34c247d84
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOJH' 'sip-files00098.tif'
0eb46b8cd48d1fc5ea9a6c8fa449efcc
20c7d8c59485f0307fb3fa2509c3124f3e3a761d
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'835' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJI' 'sip-files00098.txt'
a0983a03534f32b8d05a5b0ef30eda2d
849797f442f6b67fbe4e2dcac785ec2431464352
describe
'4506' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJJ' 'sip-files00098thm.jpg'
d98d14c955e8bdc1b8ee44660a3f57d7
6b41c1ee955ca93bb651e0744cdf6160f9367632
'2012-02-11T09:28:39-05:00'
describe
'59623' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJK' 'sip-files00099.jp2'
44c8aefe16e93cae4021121f6d8e0f3b
f5644a2de25d2076900fd0624552c36485dcc6b5
'2012-02-11T09:28:28-05:00'
describe
'45592' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJL' 'sip-files00099.jpg'
6e4f7f7d8a5de36a34b501006edb0f8c
9b4e2966d1c950daae98ec61daf46692fc2c56a4
describe
'20171' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJM' 'sip-files00099.pro'
4158af18d1bbb328a5bf13eb2d04dd1a
17e6cd51d6dbef3f62418b9f4adaa4c609957e72
describe
'14293' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJN' 'sip-files00099.QC.jpg'
e1e148eec4e3c1cef3ed814d88793bd7
7910211833086b45d7964286e82d629a638082f1
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOJO' 'sip-files00099.tif'
892305ef835775ebb75ea8de8b4dda7b
2bd8a06319a06f6ec04315bbdaaacede5a31c2d2
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'899' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJP' 'sip-files00099.txt'
0c13a40eee404324435faaa2b8fd09c9
1b6c90e2f1f7ecedf01c29499cd17b92b2998ef8
describe
'4502' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJQ' 'sip-files00099thm.jpg'
defb4a40550c45fa5115203713137e9c
97570d9d9df1bb6d01ca8980ee2a7eb25c1a2aaa
describe
'52299' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJR' 'sip-files00100.jp2'
832dd9bc0b64cde5311ba34d5240116d
7ea114b7d632962b40ad5bc6854cb6263be9d131
'2012-02-11T09:29:09-05:00'
describe
'41673' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJS' 'sip-files00100.jpg'
7dc2cee033e70850ac42b75b23c966a9
1ac3b2ea4da035b8f3ad1a15e347bb60a14f36b2
describe
'16654' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJT' 'sip-files00100.pro'
9077cd60d587a12657ef276bf4e80bff
805f07cb4484444ebedb734d586dc35ae6810055
describe
'13977' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJU' 'sip-files00100.QC.jpg'
2abbc28dc8a53ead317871356e660db9
9c3b693021c041756b1022b3042d4fe95f3f9a6b
describe
'965957' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJV' 'sip-files00100.tif'
169413ce6c9e663d5af4f659ca760034
1689ddf09ccbc689f346984d6e39ce15eb432cd7
'2012-02-11T09:31:16-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'760' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJW' 'sip-files00100.txt'
70c384be1aec8607573087bba8d1fea5
e70a244006189fef604a42880db3bbef1b947a88
describe
'4186' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJX' 'sip-files00100thm.jpg'
88d7b359a4260c3584354843f4893f7d
9b71183d31ca284b1dd0f354d77093a4fe2806be
describe
'52010' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJY' 'sip-files00101.jp2'
b51e9ae7a11d4374683421960b8366d1
eee8e823db178d2807a84bebbc6d528730918a3d
describe
'44264' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOJZ' 'sip-files00101.jpg'
820ae5f11f97cd8a757eee9c04b873a1
c9ef0b9c0b0f51a87bf32e3684f710aab0cf5378
describe
'16507' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKA' 'sip-files00101.pro'
f86d021172b9d236c1409d60db0b356f
c52b3d7cd218687ea836c46aa8b46e084bd2af6b
describe
'14860' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKB' 'sip-files00101.QC.jpg'
4f18a82837cfbbfd089e4892eefa0208
03b88b566c1a181efd1b3b0d30957643b134af5f
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOKC' 'sip-files00101.tif'
60d92d920e1964dd96d4ba5d2c238a21
d752a91ea37076c1ba3754129adcd849962978c5
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'757' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKD' 'sip-files00101.txt'
e178ddee81c2cc5cf06d285d1095f484
8939f16da43a309ee00ddbf646fb35b681c9c2a6
describe
'4430' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKE' 'sip-files00101thm.jpg'
fbef8138deff8a6292df48d520076fa3
9035b676bf4fa3bb7b936540fe95e17630c2de74
'2012-02-11T09:25:58-05:00'
describe
'52302' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKF' 'sip-files00102.jp2'
327bfdd9bdb795bb297e0a9a2626ad8c
9e58ff4a3f349ff3fbe94e8c61710ab0dd3c5e08
describe
'43421' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKG' 'sip-files00102.jpg'
4fb727deb4c232f326a780221671f3c9
e59231b0c0c3e581db1aa6705a26d6c60dfced7e
describe
'17112' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKH' 'sip-files00102.pro'
ce0a7147298824ac05c7b4fd82548a9b
c274b3bf94fe304cd2e51388630ad8e5aba23602
'2012-02-11T09:21:03-05:00'
describe
'14858' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKI' 'sip-files00102.QC.jpg'
014a39bd706ea6661f559a7f23ef247e
995bcaaa3282efd8a8bbad62e7b16e0281825902
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOKJ' 'sip-files00102.tif'
e8b80b1b467224953676bc0338e97b26
ebce2856df8bdf9b8d373d086bd693d491dac214
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'781' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKK' 'sip-files00102.txt'
10746a55407d7e6dffbdad811eb3a194
4e935f70cba8927547631447220c4948e8ee1c32
'2012-02-11T09:30:47-05:00'
describe
Invalid character
'4459' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKL' 'sip-files00102thm.jpg'
7163c3e2c894aec9aa32b88db6e17d79
93c0717665cbdd7a3912c17e620d7e4aa23b0a99
describe
'45049' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKM' 'sip-files00103.jp2'
d4b87d8d259bd74b737c7651dd1bfa79
4fdcbe47ac5701b5fdf07a19eaa6ca6dfdc98f30
describe
'36751' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKN' 'sip-files00103.jpg'
4da98498d8364ba0806a76d22d9348f8
4d6dc290d1795e7b9206fc4b8df968f708373aad
describe
'18044' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKO' 'sip-files00103.pro'
4f1d017e48a17fa4fad5f4fe1292a50b
53882a908b16091b0957d90ffbf6f34f74b08ab6
describe
'11893' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKP' 'sip-files00103.QC.jpg'
4f9e199c676e5c6be8b99a7376ce2204
f66345e4e9e28e64bfde8df7f9fed71c4a323086
'2012-02-11T09:23:44-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOKQ' 'sip-files00103.tif'
9afdae4ed617558b707f147c8fde06d8
251cfe92f85009be6149431c67f030a09c03c3e9
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'981' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKR' 'sip-files00103.txt'
f16efc9bf6a7f5f44c0ca328e32e2b02
2a2d1adcf9f0e26d040e9ca5314d9513ec2402d1
'2012-02-11T09:30:11-05:00'
describe
'4019' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKS' 'sip-files00103thm.jpg'
d9ecb21ca75fb06164ef0dac9d96e4ed
3fa26facafcc38da79b3f6cff0ea36ce2ccd72b2
'2012-02-11T09:30:45-05:00'
describe
'58998' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKT' 'sip-files00104.jp2'
a730a384fd57c93c78f1d4b91d3090a8
01533c632f7f558144e59e17500c70883067e57c
'2012-02-11T09:20:02-05:00'
describe
'47485' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKU' 'sip-files00104.jpg'
86cd5a34737e1c63e03b7a5951ec3118
fdd677830b029c6c16d74425f7a7eaa33d0d7d00
describe
'19315' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKV' 'sip-files00104.pro'
6ee7c5fe2f23a752ccb58b176f4cfdc2
ae494fcc0288efdfae6be9d38d8f2bcaffa4621b
describe
'15763' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKW' 'sip-files00104.QC.jpg'
b677e2009abe500a627e4e94ce2c375a
fadf7344155d81d8c372ca2e04094149a6e398c3
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOKX' 'sip-files00104.tif'
686af76df1af6ff023590c3d4cab5d6e
4af5eabc0cea5491e9fa0a6dc627fe88c344408d
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'888' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKY' 'sip-files00104.txt'
11637eb3ba0fad093971641edecd41cc
3015aaf08168fea8b76d98a0a13f8463b13e1c63
describe
'4591' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOKZ' 'sip-files00104thm.jpg'
32f9951de1525a4aff078892b1a43849
03622b68465a01675b749f686b9cb795690baf31
'2012-02-11T09:30:23-05:00'
describe
'52963' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLA' 'sip-files00105.jp2'
2d78ebe5333022d07a539268f01fd414
ddb30d41d1211b80b3668e50c614c3788a64cfa3
'2012-02-11T09:21:23-05:00'
describe
'43271' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLB' 'sip-files00105.jpg'
29f44894f3e531ba5aec13d37183e06b
dcd9dbf8442571060428119d69e169df1e0d30d8
describe
'17336' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLC' 'sip-files00105.pro'
bf6a1a60206853657fe218ffeacc5efb
078039769347cc58c2626ec225b6f3afbf1b1fd2
describe
'14825' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLD' 'sip-files00105.QC.jpg'
4495c58780529004ed1aa64afbaa45ca
1144923beeabf0ca44498ddc4d09778c23b0b672
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOLE' 'sip-files00105.tif'
8f6d5fb283601ba6a22abc000a527ece
56eaa341313029d1630490e861792dcfe36a80c9
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'772' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLF' 'sip-files00105.txt'
3d4de16bc79d503f264e85194feff9bc
758c74f59ff1652498224f03b49c37c1eeb4ec5d
'2012-02-11T09:19:58-05:00'
describe
'4400' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLG' 'sip-files00105thm.jpg'
9f8ae612dbe384f0736881d6ec26ceea
6369f2237dae59600d69b4d58e7db70c4a0b0378
describe
'46642' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLH' 'sip-files00106.jp2'
c2dcf3cebd20c4ba6ffa47187652e3a7
d924ada94e19a375eae9cd07e4299a9bb7a792e2
describe
'39037' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLI' 'sip-files00106.jpg'
3ed8c5782933e8ee7d9c29135562b5e9
3e9a5c5ed847ccbd4a9a78779f2b08551609c396
describe
'18433' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLJ' 'sip-files00106.pro'
f9f63f8a6b6557404d87ab6a3eef0ee6
ce4d428f15cfd842194cafa37b05506621b86c63
describe
'13418' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLK' 'sip-files00106.QC.jpg'
d3a24b98cba62e828eb697c78931cf50
8a0fcfd22f472788e894a40e64cd194c01703f25
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOLL' 'sip-files00106.tif'
9bdaf086d51ba6bb381d66a1d0ffeb45
95e48eea6339fcc87e7ef0728eb56390cdc69ee7
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'966' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLM' 'sip-files00106.txt'
9f468a827ea4262de2f89d5e277fd123
05880a4f63cfcc779066eb936417394502e471d6
'2012-02-11T09:24:11-05:00'
describe
'3949' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLN' 'sip-files00106thm.jpg'
15858586133fd3785c3dd4238b586463
95874f81163d727764cc65601925c30589d9f8e1
'2012-02-11T09:29:12-05:00'
describe
'60324' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLO' 'sip-files00107.jp2'
91b639b9a7fac5f1acf149da3de6216b
1490db17a9385258fabc5127fb57e34109292908
describe
'48014' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLP' 'sip-files00107.jpg'
474fcde398ab03dc0bd0ea367337c46e
1f55caee2af3e94fc2e7cf5368808ed42e53d40b
describe
'19867' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLQ' 'sip-files00107.pro'
b59515bcd0bc4d4cf8cb25d67f4d6a32
66296b079afb87a2f0c144b94877fd35aa868a07
describe
'16641' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLR' 'sip-files00107.QC.jpg'
d7fee35a17a8156ffee006329b9886ce
992b91614ff79f24904c8e6c267419a796909ae1
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOLS' 'sip-files00107.tif'
1e233060f6ab842e657c137277ba5a4b
610dc31780b0bf1c19a556c0d511f10ec141ce4b
'2012-02-11T09:30:37-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAAOLT' 'sip-files00107.txt'
08b8b0741d23de23c3dae6cebf4665cc
1185cfc938efc9535726df4ec07679492f9ac92c
'2012-02-11T09:24:29-05:00'
describe
'4600' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLU' 'sip-files00107thm.jpg'
c25c2e6e30332e9cef382428f0d7d757
f1dc2ad6930d46273c788275776c8447636f23fd
describe
'61683' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLV' 'sip-files00108.jp2'
6af72b6e15b1a24e5a2ef8b879256c96
c2fb449bcc02ad7e032d19d0c69b7251be798167
'2012-02-11T09:30:40-05:00'
describe
'49102' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLW' 'sip-files00108.jpg'
1e9508101e0d36600e91564cf42854ea
26eeacfff8b683d88dc43cc5584f88695b353f4b
'2012-02-11T09:26:16-05:00'
describe
'19811' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLX' 'sip-files00108.pro'
31a52f7cb5de31bffbd0fc724f9e4522
904fc95e87b9797778e1baf260ad6a3d853d80a3
describe
'16196' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOLY' 'sip-files00108.QC.jpg'
ee9a144ca5d3cdc6a158385941db2ac9
852ba0083569fcf585238a66f1374806db8a0878
'2012-02-11T09:29:15-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOLZ' 'sip-files00108.tif'
5486eb66cb2f0c4b3731a9804e709bc3
18a575a4c2e8fe11a972933f2c812fd6710956f9
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'875' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMA' 'sip-files00108.txt'
9a68444c03a07f3adb31576b21077329
451678ab40baee77122e9ee74b6b6b85ab79a927
describe
'4651' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMB' 'sip-files00108thm.jpg'
385feaa62a52c11560b3ba134f7ef7ef
95cef681f61453b89b7b9a746327bf1a4fd0a47a
describe
'63144' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMC' 'sip-files00109.jp2'
e07e4ab86f5e8bbe83371e7b9e9c1830
dbfa943fe9c6503d0981428e0ca29d51f63752b2
describe
'50162' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMD' 'sip-files00109.jpg'
cc2d48ba5624c7853f018c09ff307c05
05676f558a025b33bf9d82c7586c3334ad5c8282
describe
'20027' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOME' 'sip-files00109.pro'
20bb629c433a111dfa6b80650989ccab
1bd99584f9c8ced1b49ca2ce2de4cfa982bbea1a
describe
'15926' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMF' 'sip-files00109.QC.jpg'
5c1ac1cba5a2a45328e2bbdfa62e507b
780ec38f8a1ff22147474bb7b8b262da0921193f
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOMG' 'sip-files00109.tif'
24749269058090f8d4d65ca9a9d26840
b50ec283c3f7d954473fba445161a51302408175
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAAOMH' 'sip-files00109.txt'
f1984fad39c45e53fa2ae8d64197620d
509390fbcacb0a5147613f9d3210d6c2f5309386
describe
'4770' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMI' 'sip-files00109thm.jpg'
0209cda4a97c0a0642df0186cc6f4746
b99bc5ba45ad6cc64a784dc662fcdfd05a4cb88e
describe
'43850' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMJ' 'sip-files00110.jp2'
04181f1df05ae387b050db0214e6df50
84b7dc8e9a7a30f8175588bc1ce46980e9c04be4
describe
'36080' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMK' 'sip-files00110.jpg'
12bed8b3f480cf697f7b958eb6d99041
dde0fd26fada088068d8774ffa1189cf886874cc
describe
'14291' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOML' 'sip-files00110.pro'
2618dee4bbb60d13a6be9e80fc592574
5744f519383ebcf63fe544b37bd2f107ac26baa9
describe
'11778' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMM' 'sip-files00110.QC.jpg'
c0083db574401c40a28157198bc40e8b
8dfd418f542e16192bb0fd52b6910b80057ee4d6
'2012-02-11T09:20:51-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOMN' 'sip-files00110.tif'
6c6ef12cb7e83523990f3ad4467463ab
39c82905aa82b36c56010a367c29a1a6c50a3fd5
'2012-02-11T09:29:54-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'647' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMO' 'sip-files00110.txt'
de3bd76b1ecad65650d4db74b3ac7aeb
603a03a647231ad77b136e72bc897d6dff802131
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOMP' 'sip-files00110thm.jpg'
0124ddb83f8825ec60e29b0eb5518128
6b8f3af4e52a5c3267d269594af6e67521035fd5
describe
'40851' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMQ' 'sip-files00111.jp2'
53bd52ee463ded2e71e0d2e16638dcbc
7debeae94f3cacb4b01ed03a54304f613bb9e9d0
'2012-02-11T09:23:26-05:00'
describe
'34715' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMR' 'sip-files00111.jpg'
7858ab347725ea3a5703c5aff628463a
66a49dc5f9d82dccdc5e96386e35fd4d32050a92
describe
'16428' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMS' 'sip-files00111.pro'
365873bb9b781d206b0bada6f98f44fd
f8f99c5902212bebf444b45ccbea6ae5ce6a02cc
'2012-02-11T09:31:28-05:00'
describe
'11899' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMT' 'sip-files00111.QC.jpg'
d04c13951b98891d0b4eddb0b9f511e3
816fabdda5f25e3ab9a6e58c4e25c12dcd490698
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOMU' 'sip-files00111.tif'
c2131ce8b365ee3f3e6c05e4088c4d4c
818fed38f5a441970f3a5c711ba96c79f04a25c1
'2012-02-11T09:25:03-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'857' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMV' 'sip-files00111.txt'
962ebccf8732fca5ea34c6096af3c435
9558be90058b73b3dbb35b5ce624e78cdc84991d
describe
'3771' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMW' 'sip-files00111thm.jpg'
e88b4eafe5f5e615bd636709ca4a1f24
f8f1ab35790f0b200eb6af5ecdfe416db982df9f
'2012-02-11T09:27:35-05:00'
describe
'48753' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMX' 'sip-files00112.jp2'
b45b6175d403ad895eb07148a00ffc29
a33d3cb608ee7d26bbd01d3601f108258ee79d6a
describe
'38632' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMY' 'sip-files00112.jpg'
66e8cb9953c8d2101c2ebfe85cd748de
10ce92c2959d6c852bad6bc4ed1f10ab6478535e
describe
'16836' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOMZ' 'sip-files00112.pro'
a1cc3796b5ce03464805cccb20f6127c
4c83a1eeaecb6a473d0a7b40f71082d7e643c6e1
'2012-02-11T09:26:31-05:00'
describe
'12954' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONA' 'sip-files00112.QC.jpg'
7d66fdda8c3bbe6020f2a69b387f73b5
0b74401e66ede8784e50d61c4063c8a6b1b6a858
describe
'969786' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONB' 'sip-files00112.tif'
b492c3b8fb4d8bc3b4fff92ca0479367
65661878afa0c0c81564e072981f2ff6d0e03474
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'808' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONC' 'sip-files00112.txt'
cead6c7265081d38a4e6131d182ae51b
4f3b10c4510f3a839d3e804ddb9941e4e79b67d4
describe
'4348' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOND' 'sip-files00112thm.jpg'
0327b270b72778f7890b09120d12f7b9
a4157ce2bbd2175c1d0d9995ed0fbcb946d1c5c1
'2012-02-11T09:22:31-05:00'
describe
'37791' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONE' 'sip-files00113.jp2'
15dd6d203b161b982c1d604eefd39490
65b8a731e06ad791f3638720ead39beb9bc771b0
describe
'31824' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONF' 'sip-files00113.jpg'
9381656611f472129a2d794549581103
b009c732c00cd0c5a5e843186635eef786b2da2d
describe
'11474' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONG' 'sip-files00113.pro'
f2237f7ffd0a9f9640bbe52c148df20c
2dc23524f042da22c3ac9d217236785b24fc8f75
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAONH' 'sip-files00113.QC.jpg'
a20ee22d52a1adbffa5132a37514a05a
85fd3c2664d0e09f4cce365f889d334542c34cd4
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAONI' 'sip-files00113.tif'
88b1cd3c55d09242367a873f6a6b54de
21d669c4301d49f9fb2e07b1e4684224a3f60e06
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'607' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONJ' 'sip-files00113.txt'
17d0b1a02d751ff5422282c774503676
da7a996084a8dc3e219ad427c48b861aa27a1fe2
describe
'1635636' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONK' 'sip-files00113a.jp2'
fd61b3f173e42a2b46543635a3913653
dc3bafebfea7adbc331cba6e1b4b84a00122e4a0
describe
'55438' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONL' 'sip-files00113a.jpg'
6472c0c6e8024de62a1910e3225661d4
5d560521f6e78cf4786d01fc4ad23cca93c1c437
describe
'3471' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONM' 'sip-files00113a.pro'
dbd486f14863c597d554c836cc749ca0
f8bb3fe1c19a1ac6ff4ee017f5da69c02e6fe596
describe
'15200' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONN' 'sip-files00113a.QC.jpg'
cba40cf2ee3c255d43eafa35fd65ee13
4a2b35c2931be60e742b0154ecd64c5db0586efd
describe
'39267736' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONO' 'sip-files00113a.tif'
81cb316673784284369e8c8be98333d8
a3d49362f14a4c2a59a28366b6a459036f8a79e2
'2012-02-11T09:31:26-05:00'
describe
'145' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONP' 'sip-files00113a.txt'
3f3a8160d68de68d34df14f4afa256b3
dde4ffb66fd31a051e2fbf79cd796ac302863b3e
describe
'4387' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONQ' 'sip-files00113athm.jpg'
7f7caf6e38c2055eaf9c16aa8674bafc
57f74c0a86e819bb470a05c2c2dd9aecb8bceab7
describe
'1804881' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONR' 'sip-files00113b.jp2'
b79423782d75c4aad345099f72126495
d2e2e71d45b005c3fa1d80ad35382ba09dcef369
describe
'39062' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONS' 'sip-files00113b.jpg'
58f00e8cc5b3e90e0dc53143837942fb
401cb119e3d25b23df619f92701cd92ae8c3a1c4
'2012-02-11T09:20:12-05:00'
describe
'5739' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONT' 'sip-files00113b.pro'
0fa24ca2c165f397508b069e0c07e64f
8454c286f9839f18980c49d42e0966780837eac1
'2012-02-11T09:21:35-05:00'
describe
'10745' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONU' 'sip-files00113b.QC.jpg'
243f52981db723fa434ecc0c6f857e4a
a476e177006cd1431c08a80dc039a36b4be7499c
describe
'43330404' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONV' 'sip-files00113b.tif'
7bf8749f6dda134a529b95a12df3ebc3
e2a5a6f622f490f090a5dac6031427aa03a99ed9
'2012-02-11T09:24:03-05:00'
describe
'303' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONW' 'sip-files00113b.txt'
42a1694839ad50cf69caf7b5e6e549a7
d122613ae99feef49dd71e9281e1e1e6e7fa85ca
'2012-02-11T09:20:25-05:00'
describe
'3253' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONX' 'sip-files00113bthm.jpg'
d4b6f50f2b9639804b5b57d5f199a2b8
ade828481594dcb0b028c83928c65bd24923219a
describe
'1807238' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONY' 'sip-files00113c.jp2'
b2e28f7fdaf2cc8487d10edb95441ae8
8ac2e7cb6bf9b7df32ca9fb1c88fd23241329107
describe
'40874' 'info:fdaE20090607_AAAAAMfileF20090607_AAAONZ' 'sip-files00113c.jpg'
f35c9fd5d7cd2b443af510c501868769
5e006c5299fd35881da7bb2ce35dbbd0697e6ee3
describe
'7770' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOA' 'sip-files00113c.pro'
aa727bf880d9f0d19b35d4cfea3d5f60
4ccf1ec968b04a673e78608a8335e35948d999f6
describe
'10921' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOB' 'sip-files00113c.QC.jpg'
d7d849aa907dab0b6aeac386b6a5dbc9
e82003bc938e0e28d43a612207de5e9556dad412
describe
'43385356' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOC' 'sip-files00113c.tif'
0582d3ba691a6beffeb0e0186886fed1
774d72811240dc78385b61c472ceeb3e0ec80b77
describe
'492' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOD' 'sip-files00113c.txt'
ea6075357df94d42e0c09bf085595a9c
93278e889ff5f489daa62cacc4e12458ca87a2c5
'2012-02-11T09:31:29-05:00'
describe
'3386' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOE' 'sip-files00113cthm.jpg'
72a94d11f53aa717e832847a1c039fa3
fce42f4ab3b1cdfd9631d022f9eb245b949118ba
describe
'1727665' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOF' 'sip-files00113d.jp2'
b4497035dedf69fe187c35fbad012b38
09705624e6746d238ec1213c83bf7862fd9353d5
'2012-02-11T09:24:04-05:00'
describe
'36875' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOG' 'sip-files00113d.jpg'
b6a3a21105bdb29f70963e17be777ebb
d31583a0b93b1a1b17cb11da53ffcad1a9eb8a19
describe
'5447' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOH' 'sip-files00113d.pro'
272170e00458c2ae110b7497c4f8bd3a
6e5847a24827c3be96491cc6c0375e8453e98348
describe
'10301' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOI' 'sip-files00113d.QC.jpg'
b9213a0219a0692073c53e29ec576588
9e85a8512ff357660a258c3ab42d76c02108d947
describe
'13831752' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOJ' 'sip-files00113d.tif'
d90c8869b020106e04e49cc0d45c6477
2db146491d34cca260072d92f301ddc3ba9b1abc
'2012-02-11T09:26:38-05:00'
describe
'300' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOK' 'sip-files00113d.txt'
d1ae53ef6153563668f6f7dd32d8397e
733475b4f66289674e109c755b0b555432d5e7b8
'2012-02-11T09:21:31-05:00'
describe
'2920' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOL' 'sip-files00113dthm.jpg'
137ed80350be888cc8a0b1da3f15171f
85fd5964e2e7e1551f3ac8322091e9de89f762a7
describe
'1747806' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOM' 'sip-files00113e.jp2'
1a8743621d0aeb1cb92715a4024d9489
638e0a2a6b6be89b1849e4440d40073a278ace8a
'2012-02-11T09:22:51-05:00'
describe
'36607' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOON' 'sip-files00113e.jpg'
e8c27317c697df481c9741be39c35fb8
fe3a91111fe49b5e4f6b6a4dd1e5b4d4d694c72a
describe
'5869' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOO' 'sip-files00113e.pro'
71fc79c2613f4fd2cbeefea1c80d8e58
7f9e620385bd28bdcf32d8bff26de8fb6bcf4bf9
describe
'10297' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOP' 'sip-files00113e.QC.jpg'
affe489e99a5fb0e3d45713781391b33
23c80d8d5b253d77bc36ce072f5cdf609589b103
describe
'13992392' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOQ' 'sip-files00113e.tif'
b8d81b91638edfedb2f5fde6daff7566
2033ddf90e61c74524c08af571055f0e096265a6
describe
'396' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOR' 'sip-files00113e.txt'
776f77d555c35813be476e82db24992f
70e05ef3848745efb122ea32b78e1719a5928497
describe
'3053' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOS' 'sip-files00113ethm.jpg'
92236fedfb5b3c080992e6c123319063
53d335799f648d65ea7a1281085a141bfc109174
'2012-02-11T09:28:10-05:00'
describe
'1745365' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOT' 'sip-files00113f.jp2'
b71022981478eb3caa96df803de9ccf0
dbb04981709a2c35d8087c161e548db3b15a6f54
describe
'40614' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOU' 'sip-files00113f.jpg'
7011237039c5e9140ff24ec2bc8f7b66
d656acdccda54f8a01cc4a5a435f21047aed9912
describe
'5327' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOV' 'sip-files00113f.pro'
6213ffc2bfb3a9cb7116bfb8c3e58e66
4d266efb2e26693500aeedbbe519705467889d7c
describe
'11682' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOW' 'sip-files00113f.QC.jpg'
5872b67190add7a69165ad03452c85bd
6589104b9ef146624b5717b225989af76480dd22
'2012-02-11T09:25:28-05:00'
describe
'13973388' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOX' 'sip-files00113f.tif'
4f987e089eff567322fcf3f853fc6ccb
1381aa9a63e6257d765c995c39a3aa0703ef12a8
describe
'350' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOY' 'sip-files00113f.txt'
95a39c299c1bac60e125e84d9758fcd1
623cbb49692cd8039904ddf7d17bb30997a3f950
describe
'3302' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOOZ' 'sip-files00113fthm.jpg'
c287b5c70b92bfd01cfacf24ee613b87
2bc222aa3efa4455874ab069caa2464cbb62036e
describe
'1717703' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPA' 'sip-files00113g.jp2'
6255313f881dca5a43ed4fa6c43aff8d
3e013e0e16b355ce4f52e06445275229669d5120
describe
'36717' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPB' 'sip-files00113g.jpg'
50af6c5ec935164379370ad0fed03994
a2c9c2367d70b522c84376efe1becd814733cd76
describe
'8565' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPC' 'sip-files00113g.pro'
77c4934161ba2c29037d68c7f09447fd
2f2021eb958aa9b2b479d0be04a4d5945cae5e1b
describe
'10546' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPD' 'sip-files00113g.QC.jpg'
98fbec47f347ed66578a55baa207ba6d
77c395011806f0c4612d68c92fc9b8c026705e17
describe
'13751792' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPE' 'sip-files00113g.tif'
33554b77f74c3b1defca5dc8d90ec268
d3d9a729b4b918ccc7fa6c8436ad6128ffc12c76
describe
'513' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPF' 'sip-files00113g.txt'
30932eb35aad6d2531c16472c61df602
3db84a5b67988b477e960935c74a642acfc359bf
describe
'3034' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPG' 'sip-files00113gthm.jpg'
ef609077532bb92f2554b372d20624af
cb252ea6c8d05a9433b5797da58b05d1f00b96ea
describe
'1696217' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPH' 'sip-files00113h.jp2'
4f2cd2639e8674ad09a41672d50eec1f
07fce7671c2d65ad9ac2bdb0ee82f525b9a6a475
describe
'43736' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPI' 'sip-files00113h.jpg'
c869089d9b7abb55f5fa5d71479ca78e
6c3ecb54c77288eb39e2a4e5e69cea2db9c601f2
describe
'5459' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPJ' 'sip-files00113h.pro'
3fe4c1987a19f4f435859e400a2d04f2
228c120290f82e5a801db0b7b49b17f223e551ae
describe
'12718' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPK' 'sip-files00113h.QC.jpg'
7065ad4608b0e9b02243dac4b1fad150
71d6391364d96a4c77991074ff8c35bab1222b3a
describe
'13581036' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPL' 'sip-files00113h.tif'
e10062fa35c28bb7358131370e386441
7faaa2d2b1584d672cca9efbefdf07a246da54a2
describe
'382' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPM' 'sip-files00113h.txt'
661c9095150f113ebb3b21fdaaf0e1fe
35019d04caa5b4771c929e34761cc018b48dce5d
describe
'3469' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPN' 'sip-files00113hthm.jpg'
e9b883677ee47741c93e567b395187bc
7b0f00c71687cc9ff32f77cabc69b674a77e68e8
'2012-02-11T09:28:34-05:00'
describe
'1748468' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPO' 'sip-files00113i.jp2'
73a8eac86694d931f3735e59f27749d7
adff70329b684aca695ca9916c5001d617e2fcf3
describe
'32387' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPP' 'sip-files00113i.jpg'
b72ad3f678d579905172627420eb8bc8
dfa110c50f8ef13cd92c46d89a4a76fbf2686f28
'2012-02-11T09:22:55-05:00'
describe
'8958' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPQ' 'sip-files00113i.pro'
3bc3e5605153faf060b97914b216f8f1
f522b80ea3309ca33650f384574fa590ac694c2b
'2012-02-11T09:28:13-05:00'
describe
'9368' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPR' 'sip-files00113i.QC.jpg'
c2cc5a541dd37a4e185125c0712ae9dd
3010e3817a101601347c6e4d010bc298fb8248c3
describe
'13997404' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPS' 'sip-files00113i.tif'
ba9f893fb6087bafcad1a2f474a4c227
ce74cad0187dfb7aa44570aa47eae516eec9fccf
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOPT' 'sip-files00113i.txt'
e21b022f3293ac9d54c40e89a1e71d55
7b756da1e5adec992914a0492106c41fdffd9464
describe
'2865' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPU' 'sip-files00113ithm.jpg'
db823b320d458bbf8413be3f297e856c
400d234f31f0287a6e90e94a7ee2089314b52b97
describe
'1575836' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPV' 'sip-files00113j.jp2'
1af84a7ba80edc48e69436d07c54b914
d9e2ad9732bf3f0c99a487a8502a1c2a2f123d91
'2012-02-11T09:23:10-05:00'
describe
'32780' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPW' 'sip-files00113j.jpg'
fcb47d9ffb9a59c82ec5528a83a3187c
92ae053e579de1dc34f440ed874b480b81fdd570
describe
'6659' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPX' 'sip-files00113j.pro'
ece7b5853431847b644b2c217ad84d93
3cd51168a3a6578bd8eda95cc4dc2c490894dc35
describe
'9238' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPY' 'sip-files00113j.QC.jpg'
475872e35fa1145026f044a34bbdbc1a
3aa506c8ba3369f7c77fb299bc1e6acf876355ff
describe
'12617096' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOPZ' 'sip-files00113j.tif'
91dba041bcd378b425375ab94b0c3c1c
3939066ff82602fa8f65c98ec4268d97904da143
'2012-02-11T09:27:29-05:00'
describe
'417' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQA' 'sip-files00113j.txt'
3313a145ffc83253bdee452ee4039628
28b1264c43b1c38be8c81e5be06a30daff3fb915
describe
'2841' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQB' 'sip-files00113jthm.jpg'
ab564622ff896714af3bbcb91aaed7fe
5ebc194516c326c863a20f55181f3c0ca8762dde
describe
'1610382' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQC' 'sip-files00113k.jp2'
29b3ca0691740f61aa85b334837889b2
924de4d7693f506bb2eeb6f5c4202663940f01ee
'2012-02-11T09:29:29-05:00'
describe
'41783' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQD' 'sip-files00113k.jpg'
9c94f87534abf247a27c9348aaf6624c
2dfed73bfeb14af0832c489a863f6e13d863c287
describe
'5302' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQE' 'sip-files00113k.pro'
c768c02d072c14db2e72047c53a95bfe
e7367d0128a7376d29ddc6a5728e8d1ab73240db
describe
'12650' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQF' 'sip-files00113k.QC.jpg'
59a6e009c9d8b1ab1aca98eded0faa2d
df82aa441edfbfff4ef7c25ff74c6642a7d68cac
describe
'12894964' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQG' 'sip-files00113k.tif'
fa3c311f36746550c07ae0e98c64a326
d169ad51995346b4c22052ec4273889686e8f083
describe
'278' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQH' 'sip-files00113k.txt'
ad620dc08f8114dcd9c86f4c2e02f7a8
711e3a2fea713237d828f39cae1714b036680783
'2012-02-11T09:22:20-05:00'
describe
'3708' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQI' 'sip-files00113kthm.jpg'
eefafba011072e3f5682dde1a90e58f0
b99a87aa3c231169be0d27e7ba20e623de1accfc
describe
'1638501' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQJ' 'sip-files00113l.jp2'
5814b7dac1a54b1555d7d825a8530f0f
f19157a05ed5c1ca3faa30e66dc09830ad727120
'2012-02-11T09:22:09-05:00'
describe
'38387' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQK' 'sip-files00113l.jpg'
fb3a5933ff30e8cd613d9b6d96f1a493
72abd6ca05021b7fe33896a7173dbbb734267218
describe
'12720' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQL' 'sip-files00113l.pro'
e98ed08d39ca75ba599cc8852c92b616
cd6bbd720d411eff87f6f313e372dd060912fad5
describe
'11025' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQM' 'sip-files00113l.QC.jpg'
0dabdc752e24a36976ab6f3d507dc249
4c404c3d587819e55bd753c3e5cd1c4c244dc1c9
'2012-02-11T09:25:04-05:00'
describe
'13119060' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQN' 'sip-files00113l.tif'
0c67e9d126bab66bc8ce859b3b749a82
2c485a5221c602c4dad66d11e07538dfe3060f06
describe
'1019' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQO' 'sip-files00113l.txt'
1d344bde6590a85a9e8222ffa75c7f5d
6829aa50a4488cbdc6603fae380a29aeb23adc6a
describe
'3235' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQP' 'sip-files00113lthm.jpg'
80ff17f4503c020e684db51da30c1866
97c4c9d4358678a7ed467695d48eb714922f1038
'2012-02-11T09:24:54-05:00'
describe
'3589' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQQ' 'sip-files00113thm.jpg'
8644cae6490c4e6e438b9f2c7fdf2001
8d5a40fc8e76dd10d09b2dcac503ebc2e73d01c4
describe
'48613' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQR' 'sip-files00114.jp2'
26ab683c0e5a0af36a1d95ecb7702a1a
2d8d4b5160e2bd17dc1a930b9ce934a3c4c3c1a9
describe
'41725' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQS' 'sip-files00114.jpg'
81aa8ab96938bba7c91ee2cfd9ae45c3
fb28adeb61082c2318808b701c8931b6fc3f6232
describe
'6142' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQT' 'sip-files00114.pro'
f56a86d4babec5083661f7f5edc5a5f1
235de0679a7d606851597a1464410ef8cb919bb5
describe
'14708' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQU' 'sip-files00114.QC.jpg'
cdd1b84166ff34e9b63e0b0e82e4f454
028b454599f3ca0f45dded6f5c85e18568ac8a2a
describe
'973619' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQV' 'sip-files00114.tif'
155633f21e6c9afa0724b8dff5138719
3f57eaf1b182867aec1df5d60ec86b18295473fc
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'385' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQW' 'sip-files00114.txt'
1cdc536531bbefd7e256af1fdd507776
dd29fd8286c0d8a345919ae512dcd1ff748f827b
describe
'4780' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQX' 'sip-files00114thm.jpg'
54f8a2649e07bebcc6ed643d3cc19f7d
061a7531ac4b24932a4ea5003a5e05cdc4a07881
describe
'44039' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQY' 'sip-files00115.jp2'
c55524f19eec5b9a5d8c526f572526b2
0cf189a2fdff375f48da7469429cc4f02f97f029
describe
'37540' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOQZ' 'sip-files00115.jpg'
f5c995cacdab21ef98492ac33ed786d9
0c33a509251e4def7e06cfa0cd80689fa716fd08
describe
'11248' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORA' 'sip-files00115.pro'
1a3a0aa15927f77938e90c52f7462721
0ff7d07fd499f3bd2f97d9b6a9f8cf5ea6e58a67
describe
'13575' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORB' 'sip-files00115.QC.jpg'
fd05a2218ebb8fd46c8dd8e5b22a5342
be69abce07e2d86aa9d72e696130910dd1426c31
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAORC' 'sip-files00115.tif'
474fb2d7ba03afe2c09cb83c14cdabf0
2253d23b56a47d753cb76baa1c22187f851688e5
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'732' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORD' 'sip-files00115.txt'
3066dbb30cda34b71a6a3e50f395160c
4e79ff216bee60ada0f928f7a0a012de27b8b65b
'2012-02-11T09:27:41-05:00'
describe
'4597' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORE' 'sip-files00115thm.jpg'
101928f67b7ede816e3e4ea944cba4be
7668e58367b36c6102b17b933df5e8e33fb83c82
describe
'48339' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORF' 'sip-files00116.jp2'
da37846b90584c6afe35848d64087feb
bed21faaafbca80dce62a6326d7b2c8650abf68e
describe
'41090' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORG' 'sip-files00116.jpg'
cccbd89ce89de2fe2b14a6cf84dcd699
6a59001bf081a468e99309f6cc225d522925d8c9
describe
'11563' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORH' 'sip-files00116.pro'
eaa9ba06012e7a047ec0ec24855b9da3
e3a0c81bf5f887e19f6350ac77cc7cb4600cb1bd
describe
'14113' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORI' 'sip-files00116.QC.jpg'
6361c1193f8c460c160be85e58d25aa4
43bb9c39f606ee7dcfc65b44bcbb255ec537fe87
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAORJ' 'sip-files00116.tif'
ce69ac486f33fb398c2ca02219823f89
d2802a73c7802d65d4406919c3c029496e7699af
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'830' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORK' 'sip-files00116.txt'
15e147fba5f90e5c310bb5c157a4642a
7c3fec65b80ce34578c19b8528730a4a43f09123
describe
Invalid character
'4758' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORL' 'sip-files00116thm.jpg'
29ce62f89edca02fe1d6c79d03e61e2b
5f4623a89b8a467b4662f3b68637395c482c2604
describe
'32375' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORM' 'sip-files00117.jp2'
58ea0cde5c347a7e83dd499eb13f7259
f8687c9b139f08cd90d305e37b635552f8fd5473
describe
'28919' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORN' 'sip-files00117.jpg'
3d79b8df1fd1009105f4506fd432e160
4edaea10d81dbe3bb7171b097940ef44c6d20604
describe
'8240' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORO' 'sip-files00117.pro'
51f4d44be6caf0a6bb401bb834654657
37de9d668b570a2c4f4a202315d2dbd8a98b2ffb
'2012-02-11T09:24:41-05:00'
describe
'9976' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORP' 'sip-files00117.QC.jpg'
de60f6a863f8fd5da0ccf6ed27d60084
31699a975eefb3248d5633c06bee4e2a4a687943
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAORQ' 'sip-files00117.tif'
ce40db3413d93371ad6ed216e6798729
6f52af301fcce1cd01fb20f20e99f0e9a9cbe960
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'516' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORR' 'sip-files00117.txt'
015c379608ecb87cdaf6d884c31c6f30
3159cd9309ff2332e10ab4db0e3096eb0eebe1c1
describe
'3568' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORS' 'sip-files00117thm.jpg'
e8845a7b8908f6f364a99e5b2913b2f2
1f539cfd974fee9dd4678a744089e9690b9d407e
describe
'32686' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORT' 'sip-files00118.jp2'
34456eba4a9ce348e01a44ce4ac5a72b
3fd59a96d05ea2bc162034111f4ff9b62b72442a
describe
'28840' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORU' 'sip-files00118.jpg'
02173de9267b0c4b2ca4a4119ace45ab
af1491c67ee1c11a0d8134ae8289be270074d20a
describe
'7679' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORV' 'sip-files00118.pro'
6d4a7a8430edfe3d94b4631fd511d715
9f960024716770dcbe9ef101f39db9946e9c6f7f
describe
'10340' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORW' 'sip-files00118.QC.jpg'
3602e121d3c743d25d94715b0a043d7c
d3cec153fd2e5d865bec3ad4d1dba13252346659
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAORX' 'sip-files00118.tif'
bd9f34afa94e37dc870d83d79c495486
00e2691b6d185288773d6a3708a57b34e5d7af7a
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'444' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORY' 'sip-files00118.txt'
3413eadf7f307a6d15463c64b08379b6
78ec0477f516780fb40dc5c30a5312ccc366453c
'2012-02-11T09:19:52-05:00'
describe
'3630' 'info:fdaE20090607_AAAAAMfileF20090607_AAAORZ' 'sip-files00118thm.jpg'
e0a20ba61505a02ad289119dcdab93e6
7c453eec6b2905b71e831491322fbfe947efefaf
describe
'35445' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSA' 'sip-files00119.jp2'
ddc0c9ac98aee222e6b893e28c9c1792
b46df9bc63888e4fd6b719d8d601971bfd38307b
describe
'31137' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSB' 'sip-files00119.jpg'
cb7148927f61689c3ccd276740b11f21
26bf1479fd905e4513fc3dde626e3b4082df9a37
describe
'8108' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSC' 'sip-files00119.pro'
648bcadfd09db71d6bf60f8ac3413a02
7140b977fd5b09b029614cac9c411c513ff5ff6d
describe
'10654' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSD' 'sip-files00119.QC.jpg'
fc887a1ef012a302814eff7269cc72fc
a111f54c3117ad03b92640d0c431cbda6b74b643
describe
'976852' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSE' 'sip-files00119.tif'
bdf4dbb8be4fd0d32f433336964cceb8
eaade98a6fb64db7afdb2c487f2a9b648cc43805
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'477' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSF' 'sip-files00119.txt'
4e7ca8c6146d069d0c9553b565504ca3
b989760574a64594348c1bf6b92548bf5b077af0
describe
Invalid character
'3884' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSG' 'sip-files00119thm.jpg'
810428cd553ea6aafa8cd986487717a7
9506f1ad8cfd66722e371b5ec2aeb0e9010dd418
'2012-02-11T09:28:02-05:00'
describe
'49168' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSH' 'sip-files00120.jp2'
ddb8fccdf5fdd9eb37f56fbf5d9a2b29
f64fd890b0659b31e707c753b0e4337a5a3fa03b
'2012-02-11T09:28:25-05:00'
describe
'40710' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSI' 'sip-files00120.jpg'
0adccce879dceac7a98ddf67e00f8587
2c2b6a0076934f79fb4ce6f4a1bfced84b3830a5
describe
'12051' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSJ' 'sip-files00120.pro'
715848e9e04d488cd7d6275f2058e9b4
79778e3cb2fd76d02441983da71478b734ad8cee
describe
'14124' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSK' 'sip-files00120.QC.jpg'
2632a1d11b253e7977ec155905df7180
e9da00aea146584c718e3da6a2ff3238c1664980
describe
'977456' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSL' 'sip-files00120.tif'
932c939c85e91fa53f8f8f069a4b19e5
05fe73c6faafe3bd4470805559f738c0b8c4b370
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'709' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSM' 'sip-files00120.txt'
6bb90b8e78e6d07af2b71285258a45d7
6a080f8aef2a76e8feb40d1535598c43be28c909
describe
'4900' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSN' 'sip-files00120thm.jpg'
9a4edb5e4b1b350a1d497f0622002f66
77e183dcf430cfaeff63e95fda337a21ee21cbf4
describe
'46418' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSO' 'sip-files00121.jp2'
4cf37918877b13d94365e683699c727f
b40112404d51fa6673e7e87d989a48c47adedaa7
describe
'38545' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSP' 'sip-files00121.jpg'
d64abfe134fe5e10914f63abd4c95e04
33f011fafc0a89824c0747ab7af7ebd7689d863f
describe
'9836' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSQ' 'sip-files00121.pro'
eac7d7fd2c37a616c796ab8c4ca0633b
46b50b07fb637a3192fb2e3d9141831cef38336f
describe
'14353' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSR' 'sip-files00121.QC.jpg'
33b9d6b40ef3e6285f18c457bcb0df68
dbf6e0de7889564bee481ed4ff12299122fbf25c
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOSS' 'sip-files00121.tif'
e0cbc9d81a46a447cb23b50b92df181a
acd7fe89497aa4d6736c5eb4c5f39779ac1e1dab
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'488' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOST' 'sip-files00121.txt'
f07255f71bc8642d742c3a69913a627c
bd2cb9ec889e2452ef83c396aa1276ab42249a57
describe
'4693' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSU' 'sip-files00121thm.jpg'
ecef4e79f5aabe682d2ea6e2a5d099ee
839ab7468d940cc6350c24edeb9ae8c04031b41f
'2012-02-11T09:30:14-05:00'
describe
'47070' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSV' 'sip-files00122.jp2'
5baed7310d2868ad3ea80a57df082548
7d3914229d4b7b249134fb931e15ac14f51180e5
describe
'39631' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSW' 'sip-files00122.jpg'
dad570633b930673abd1a44cadb884f5
351e4d39c60fe98ce0ebffebc1638368866d3648
describe
'9717' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSX' 'sip-files00122.pro'
fde3911a68f872f6aec93fe77157d9b4
02bfe918bbc1106065fe3ac772f60222d1df9903
describe
'14395' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOSY' 'sip-files00122.QC.jpg'
64d1a97b9fee7344af76937d309dde77
9d1cfb2b26aed835ee46770404393449713919cc
'2012-02-11T09:24:12-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOSZ' 'sip-files00122.tif'
25d91eb2118619fdf081f905016c01a6
9d109dd2f3407800fe7a9d44d1960a6e8ef61150
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'581' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTA' 'sip-files00122.txt'
2548d19906ed40d1de1379fc349b8d93
5baa2faec9d7b89bbaf5a018e84c78788edf2486
describe
'4787' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTB' 'sip-files00122thm.jpg'
b9c6f072e5a0c75b37c35cfbe0ef5125
6210f5b39f70606652b6d4bd637a8e6ca9d82f04
describe
'37740' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTC' 'sip-files00123.jp2'
3de4bd80c426b75d75408ace3806ed97
3fa8e151fedf1eceff3017c570f5b36c1b260f46
describe
'32647' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTD' 'sip-files00123.jpg'
9d6e959aef17b78109744a36c54f261f
e9ebebaf320dc60e9a0ae3324462a0e179e69364
describe
'9324' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTE' 'sip-files00123.pro'
92c9c4065a20d2b6a8d30a834101b044
b7709410f253c5864ef11e4e1aa1c0eeaeb5dff0
describe
'11812' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTF' 'sip-files00123.QC.jpg'
0802dca04573121e60a7dc46a0a1d4c4
94e03926d6933744cfbeb364fd4f110f2257e1a6
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOTG' 'sip-files00123.tif'
cda9de268b0d27e6553dcc8efe5a733f
72e18d070a07f8a0829fc92443021516e445fcbd
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'560' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTH' 'sip-files00123.txt'
42189932e0f71ee63ae1aea969a22f7b
633fac6cea669a8f2905ede160cc1e0f6dd47b06
describe
'4155' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTI' 'sip-files00123thm.jpg'
398a2fcc23f1853840b73ef3729f4d0b
71e9e1dcf2ee86ec3838bb955a7c5b4901b2c0d3
describe
'37984' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTJ' 'sip-files00124.jp2'
2662346f2aba38d3d9ad0f1a038c2bf7
a93ac72112d9470523ad8e08bfe5a3500a019611
describe
'33180' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTK' 'sip-files00124.jpg'
87f1e4cc388cb24e3f9ceac0cefa635b
fb393ddc082b4fcc6ff57ef8dd1046d91e8cfdd4
'2012-02-11T09:24:56-05:00'
describe
'8334' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTL' 'sip-files00124.pro'
ec137caadd996b873b09f42aab704a86
7da6ac094aa628f83dc14cb04cf656b97393c12c
describe
'12073' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTM' 'sip-files00124.QC.jpg'
0d8d9d1870fe14985621c722d5e36398
c555914e8b1ca5594ff2ea1ad1d9eb29f1812490
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOTN' 'sip-files00124.tif'
d174f1f7f68822309dfb869a153c6780
e4e17e4ab1335765cfe4f5762736ebf36986b2be
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'461' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTO' 'sip-files00124.txt'
97b9bc29d023e1b0e0c7cfd3dd264643
d32650c2d166648ce28eac661f03ca2d92cbedf9
describe
'3875' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTP' 'sip-files00124thm.jpg'
6453de9853c2061a2a4d437ecf8754e2
2e747d53a5c6984fe45abe99662ed65a902d4fa0
describe
'35295' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTQ' 'sip-files00125.jp2'
2093da3f09ed2f85a5afb321833140bb
7e154d62fd0d5e9b347b4e01ad8be165fbc0c818
describe
'19951' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTR' 'sip-files00125.jpg'
9ce06e6fee4f1f38fd4a22b4090014ee
249357499775ec8ee32fa54c7f400c8a34d53309
describe
'10306' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTS' 'sip-files00125.pro'
0b3702cb97b32f3e5fb7b9beccd7c7b0
fb65be02f9458ce9a19bcaacecf4d091157d1cc3
describe
'7025' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTT' 'sip-files00125.QC.jpg'
e3f94ede1f70ab25e959c8c452677c99
82465bf8ee7f435c5be1ac8899ff50e2c85c8e7c
describe
'979166' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTU' 'sip-files00125.tif'
b1d5a2d778cb7c736a908c0c9835f884
6d9b97024ac8c903d6585aa6ea81e69c68a5ed48
'2012-02-11T09:31:31-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'495' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTV' 'sip-files00125.txt'
9f90ba3c61a650ff1c9d17556640ed2e
5ae196888b0027cd38d83b4fbd293978596f2b64
describe
'2686' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTW' 'sip-files00125thm.jpg'
93892c2879a1507f17a832f77e21a4a2
cc4cc0b2bf0514a22b563a1ed8fff7374a796878
describe
'38157' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTX' 'sip-files00126.jp2'
64259648fc5146c8bea6a7afa0e88141
46afa26cedcc4d38c8444ed1e1532e3c868fdd78
describe
'21733' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTY' 'sip-files00126.jpg'
404ec338da2c25cde1310100ff70d775
ddb4255ed53c95291b01f6ed430ae22690f97c6e
describe
'10466' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOTZ' 'sip-files00126.pro'
0883bbbb3c24f9c5e7e840eadf98fbf1
1b4e27155175965f0a7279333e0a1cf4fe975d25
describe
'7885' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUA' 'sip-files00126.QC.jpg'
62e2c4916e87a9db6d74e0e715f9dab0
ac68fdd4d2dde39985990bd2dc55b7bc45e31ef9
describe
'978356' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUB' 'sip-files00126.tif'
7107c7a3207ffc7ce2bc6d637e2a9363
bfda40774c994f78ffd009287b606fc66c64ab3f
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'468' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUC' 'sip-files00126.txt'
fd55d9e7c4cafb4f00ebffd5db362307
e065b848a54b417520da1f0a9b8c0adcf4e40b2d
describe
'2752' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUD' 'sip-files00126thm.jpg'
8860823c101c151310ce511b2f05b83c
7680f7ec74983c5918355bd85d4f3949d3da5870
describe
'34353' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUE' 'sip-files00127.jp2'
aa01a6c1bb0e87a1268bcac4b4ceafab
bfe2941dff8b20739bb5a3e30c3740aa1ee0eb9a
describe
'18523' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUF' 'sip-files00127.jpg'
f87c17c31a03e785d1fd557a40d4fbf2
90da1f25724a5b6d6186caed94c76b4cedc393a8
describe
'5755' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUG' 'sip-files00127.pro'
9daf6b15251a68bb81d2748184b67a94
c54010ca44304ede6c110bd149c26c77562d4036
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOUH' 'sip-files00127.QC.jpg'
0814413acca00c8d1fc874cbf6434557
2ac74866ddff3a1603bbf7c549c46cba410436df
describe
'976750' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUI' 'sip-files00127.tif'
2f4f378b90900c072eda55631917c0b0
0471f5dc0745b59841acd423bc9f5c0f4ae308e4
'2012-02-11T09:28:36-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'info:fdaE20090607_AAAAAMfileF20090607_AAAOUJ' 'sip-files00127.txt'
861fb2cc82af0e17629708197c4fa36c
b751c07428696cec304c56520a95add341e0f1a4
'2012-02-11T09:30:30-05:00'
describe
'2551' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUK' 'sip-files00127thm.jpg'
dd3b259a742d78fe7be9df311215acde
18ad2b72b1478931ded9895e7bf669379d2e58e5
describe
'93925' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUL' 'sip-files00128.jp2'
027b7cbe84d52ab8ccd166ffc201b17a
d7d04eb436505614545c10e3e59209c4784fd830
describe
'74684' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUM' 'sip-files00128.jpg'
85929a4760bd0e96d784da6d1193e100
31207305c39e1990b8163e6c8bd2615e2bb787e7
describe
'31891' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUN' 'sip-files00128.pro'
dc3593a7d1b4fbad9a9d427782d81177
90f47e33ac0420ef01e57dee8d6be3297be14675
describe
'26150' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUO' 'sip-files00128.QC.jpg'
89a602ea3eb87cde6789d51f4f23c57b
244cce9a3b37ba593be53a3a933094a43459e202
'2012-02-11T09:20:30-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOUP' 'sip-files00128.tif'
0e96fb9b21c3580864e85fc5a307a45b
95d593b009d7b0c6a75881891787ff445ccbb2d8
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1385' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUQ' 'sip-files00128.txt'
1c593ea768122fbdda489b88c4fb9ca0
feec645f97d86c35e626115f862ef18077801a87
describe
'7265' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUR' 'sip-files00128thm.jpg'
f1d5b34313052d3388eae36640166222
9edb805e130d9deb9a05df04e75c26c6f3b7cda8
describe
'44198' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUS' 'sip-files00129.jp2'
d6a1be80ff45dbffc540256a5d6ed0f8
df5aca86d0b114ec16a9823ec406119e6f1282f6
describe
'36123' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUT' 'sip-files00129.jpg'
f720427b4e26f16962e056e932805d77
622fba43878650eacd4fd1fc1f20e63aec625133
describe
'13408' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUU' 'sip-files00129.pro'
015a1c6a11f49c3654515e4fa962da43
c069812f5667261c44fe10b1ac61fc699876d44b
describe
'12259' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUV' 'sip-files00129.QC.jpg'
a86b2ff0db4393c4474b2c55bae8517a
85a45b9550ff3f772801a3e701d975b9bcab355f
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOUW' 'sip-files00129.tif'
56404d8fc2b2ba50653064997d7924b8
384748fbeca918ef7e908196f534e4c84c6c801c
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'599' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUX' 'sip-files00129.txt'
41b67ce5bcf1edcfd26ce7ca6e43068e
4379ebaa693d8bc2c8d7827d25eff835a235747d
describe
'3696' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUY' 'sip-files00129thm.jpg'
df12b834b6aafa366cca2d53cd00877e
6b52370193a3dc9a6d1740b81c34dd81c9e17f59
describe
'96330' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOUZ' 'sip-files00130.jp2'
aacc3359508167be2c3d4f95103481de
30eb7c749d74fee43b4ceb1e3218858d3bce63a4
describe
'76937' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVA' 'sip-files00130.jpg'
b4d841f4a44b7d0a4bb6186c1a92fb9c
ea64025125a0d681de29ba0ac7489763380a395b
describe
'33887' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVB' 'sip-files00130.pro'
f820216f3074ab05f7a2ef19314ffe1b
33d7fdc6b24a0b48fdc38f602a6e6f4a6e2bb082
describe
'26354' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVC' 'sip-files00130.QC.jpg'
8f83a05e2bd4d2d3f55840f52747d8cc
1122044a86e8456a5b235b125c1b50e81567d072
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOVD' 'sip-files00130.tif'
7f21d318b81055d6f4ffa47357f39aaa
a195816deae516f00b8ed9c7ccec4634e4a71eaf
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1540' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVE' 'sip-files00130.txt'
8f5204205bf9301a54cc08336c11968b
2381d9750408b28cf9772c9a7985a63ffc4a1068
describe
'7644' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVF' 'sip-files00130thm.jpg'
d5753ca03155ee53f81a884f54dc4071
62e2f3903218b3afdbbdb99220587948d8ba94c6
'2012-02-11T09:27:15-05:00'
describe
'109955' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVG' 'sip-files00131.jp2'
36318f6eab66079cb3ce84bf82a5edc6
48de8910f5501971367d225274421b99100d7ce1
describe
'86719' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVH' 'sip-files00131.jpg'
90c4bf4b46412d17ab92ab586a017431
9e2873558492c94a32fd41009b1b435bbff2784c
describe
'39013' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVI' 'sip-files00131.pro'
9fae04c920ca548b972f573a727f0412
e73a2cc2fa2fe733a2fcce53557dcb5f3753733a
describe
'28811' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVJ' 'sip-files00131.QC.jpg'
3c786d0ce59a30f4f314143f82baeabd
2a6dfb64947eaf24c9e17e20405c1b6dde2633f6
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOVK' 'sip-files00131.tif'
15ad775feb1f7df062733d558df0d427
3b675b9c61c3e3791188a369c843503b5aecb407
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1754' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVL' 'sip-files00131.txt'
d73ca66a499f19ce3b24646a1a094b4c
384650390667bfe42bae03bb1250f13ddd1f57ea
describe
'8500' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVM' 'sip-files00131thm.jpg'
e4a54c59159d6380e02147c7cc2f4717
a32bdf92aad1392f4dd6667be5c75844726fe4d3
describe
'110988' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVN' 'sip-files00132.jp2'
3d7577f71a9cc69ec7751aa90c298d37
40484bd6aba50efd832885b6ad517ce2a9f60b92
describe
'86561' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVO' 'sip-files00132.jpg'
359555ea38f2a52458ee0d67a06453d0
68debd9e6a2217cbb9b99aacd109fd6dd5ed16db
describe
'39330' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVP' 'sip-files00132.pro'
406400bd0e3b29f9224d8530857b35bc
0dee4070d7ed1baaab182ed53f3c964b45f4e96f
describe
'28444' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVQ' 'sip-files00132.QC.jpg'
1f96e2986b384dd2481b3b46f3e53a6b
7907549bbe9fc3102c68f6cfa87e7b43cf0f0a9e
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOVR' 'sip-files00132.tif'
741374a782c22e27cf4f0cc42997d071
a7dc3b268e37676611e6de3dfd901268132fa03b
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1721' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVS' 'sip-files00132.txt'
6d7473c29b42c313d5b83718468c9923
e336a64e754576cf61f06a1efa4a47c1fb027776
describe
'8077' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVT' 'sip-files00132thm.jpg'
969ea521737f433e885f22b6eb9ea4f0
f51463ee1a1d3c3aba2b503a821be85364d789a9
describe
'128748' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVU' 'sip-files00133.jp2'
32a5361db3d230c34ba36182e00b8bfe
7797926e74dd91e08ca194a0c4cbb773e28214f6
describe
'97344' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVV' 'sip-files00133.jpg'
556f72c5ea7a07209cc50cc059578376
68b8c3a81a900cdf75892937ff87744ddff1eadb
describe
'46392' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVW' 'sip-files00133.pro'
719c4678259cf8e42810e1545430852b
9ea000d46b6e9a48c14d28fc5a99943267b752a8
describe
'32220' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVX' 'sip-files00133.QC.jpg'
a2d0b88720d0c710ea289157f71cbcd8
5198678c6093fd1246258c748a7e97d1c19a4e97
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOVY' 'sip-files00133.tif'
6599c928da7c49b53ef1bf0ad97190de
731cf2e5c1820c28546d6055b0b7fee2c7c41d77
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1980' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOVZ' 'sip-files00133.txt'
47f08f22a032a137e9ea0325a0198f27
429c080d69541eabe543cb5002d99ff482fe008b
describe
'9233' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWA' 'sip-files00133thm.jpg'
5aacb1c9485c6652f329353f9351bb1a
46d48b757d38752cbc94476d3c59be1b653bdcf3
describe
'123705' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWB' 'sip-files00134.jp2'
e2904e3c90814ce42ffff6ccc4428b2b
f9e6f24028e95cb7fe104d59724775109e4f6803
describe
'94474' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWC' 'sip-files00134.jpg'
d1177d3a306311631c2039141aa1c7dc
5d6a59809cc5b2ae94da1f27da68450be0eb7460
describe
'44074' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWD' 'sip-files00134.pro'
1fb4622081419874881c4d6a27efd95f
2c296b170b9f1e83227ea11880f73b907d61035c
describe
'30809' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWE' 'sip-files00134.QC.jpg'
8c15c31fb9996bb3d95aa2f1a4f34759
4c9476bcb333218ec3aa3131cc2bc3e6a3df0d6e
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOWF' 'sip-files00134.tif'
a1b45d7f396f07d324c073ee0a08cc11
ca8dfcecaacefb2523b173d0df4b568c37f1edfa
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1893' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWG' 'sip-files00134.txt'
710225ed9144d70220fa643b57fa2622
a0f3df78630bc825ae89b93bda9d9639201ece63
describe
'8626' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWH' 'sip-files00134thm.jpg'
59a66709e32663ad7600444a0653f51b
f0a638c070c5aec3ffc913a518823f3f7bb202ff
describe
'41121' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWI' 'sip-files00135.jp2'
824450916a56c17e68100279c289ea34
82595eb8ced22067386541ddc44e7461dea08eb0
'2012-02-11T09:22:33-05:00'
describe
'34251' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWJ' 'sip-files00135.jpg'
dbd74837e19015603fbec66e447c32a3
70224b6b7c12762b67ff4ed1e2c85b481266cf9d
describe
'13134' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWK' 'sip-files00135.pro'
e88f0cd0439b0ce84d95a9dfc2e57420
95aa479c9659f3e314a232c8c10702021d69915b
'2012-02-11T09:30:00-05:00'
describe
'10955' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWL' 'sip-files00135.QC.jpg'
cd814672cb185abf97f4660d17ce2c6a
1a3817048ef6d187cd172cf6e264920b81c75849
describe
'970986' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWM' 'sip-files00135.tif'
c67a102115aaaa7e26cc3476d7465a9c
274565e04cd0036b8cbbe5974f0bcf095400bd8f
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'608' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWN' 'sip-files00135.txt'
c9c9cdd1b377a8116bdccf2fc0a269eb
a745b8faf21da9d216dd71207f47a06b4af4c65c
describe
'3405' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWO' 'sip-files00135thm.jpg'
db4192fa3816f7c841da79ebdfa8d2f2
245aa6bbec3eed9ecb2040e5c0e28bc7da1d01c9
describe
'101709' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWP' 'sip-files00136.jp2'
bb149eb56fd3965f56164312801a3dff
ef5fefabd3969534adbadeb14f12dedce813e438
'2012-02-11T09:23:58-05:00'
describe
'78109' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWQ' 'sip-files00136.jpg'
7655bdf4af90b7d27a8817cb40c3c414
e78965b63d984a8aeef7c71d43528da9b93e0cb9
describe
'33516' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWR' 'sip-files00136.pro'
bb9b1edee1e1fca2ef4463ede71f35b0
cc01ea5a1569777ed022d9bdba263bfa737cb5bc
describe
'27997' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWS' 'sip-files00136.QC.jpg'
b7122f8febeb7a3a80935d86c67beb99
f300046d262bdda321738df5f87d3be6049690fe
'2012-02-11T09:25:32-05:00'
describe
'970386' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWT' 'sip-files00136.tif'
eeb4e586373e4e54b3f298b09dffe543
0ce1fa3078350fa0a0ff42e87d2f38d0a2b0cc3b
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1440' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWU' 'sip-files00136.txt'
444c936335e542d281b0585e1800d82b
884ccbeb5764cf47282b5bfb7f6a034af9e0631e
describe
'7690' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWV' 'sip-files00136thm.jpg'
30df7abe5b45c40b761545a55844245c
3ac1db2fd35eff3972abd666344c031853fa0805
describe
'89932' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWW' 'sip-files00137.jp2'
22e8655826654d5decbbd3ed2364eadd
d8567cd5c28ff463c08ba765027688271fc3e533
describe
'69800' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWX' 'sip-files00137.jpg'
80b1a351eb0768ea4207c400171764b7
28904b337c929179a603ff612a2d6ee9563d5697
'2012-02-11T09:24:26-05:00'
describe
'30006' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWY' 'sip-files00137.pro'
e48f09f57b72ad1fda087dcdd48bfe5e
b5e55d2ccdcc2a045cd2c3bed0e2ec092aad9cc0
describe
'23560' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOWZ' 'sip-files00137.QC.jpg'
9d90caf6109fc8e4049acbb80035f55c
fb6c968cf5c55d8918f774d8af04aa20cbb97726
'2012-02-11T09:26:10-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOXA' 'sip-files00137.tif'
ee80d6ebfb47586398439c3e44cd16f8
d1a69f912eb6ea056b71d5e8a0339a5b5ccba4ef
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1271' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXB' 'sip-files00137.txt'
66b7c96ecbefbabb847a4ac099fbac85
bce04b82fedf9a759de1891ca0e24bff821e6712
describe
'6484' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXC' 'sip-files00137thm.jpg'
f80eaf0d3f7bf0b3a6dfa6479ab718c0
58a22b4fc92607411c7aacc127ef09c8431148bd
describe
'72033' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXD' 'sip-files00138.jp2'
2e70295b42b4cee4718172068b4782eb
48da0e21df13051833a8502da4f44d1e742e42b4
describe
'53792' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXE' 'sip-files00138.jpg'
bd199ee380a2440fabb5cbda7ca02ce9
28712678337e358ccb96081c7def4f35238e2b70
describe
'26576' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXF' 'sip-files00138.pro'
04d236cb28b859c70c134337acfbe6df
6e50de28d5c3de3d4883ee9267f4b98ba3dc9926
describe
'16043' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXG' 'sip-files00138.QC.jpg'
17524918f20271791561d1e7ce8c82ff
b1e05c4469f906235cebd7e4b2e5b698d4a65257
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOXH' 'sip-files00138.tif'
9e0b408712671acc2dc27a8bc3937fe9
ba035caedcea6525310f8d76935ce97d56cebf95
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1284' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXI' 'sip-files00138.txt'
8b77197dd60b0f39b31ced8c28e960dd
64c6be5d9c028e76fdaf14d1f6a93332732f07ec
describe
'4624' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXJ' 'sip-files00138thm.jpg'
74afe75a43efbfc553023af7a5f03f31
a90478b7c7f5f615142e1848ba8202ae685d0212
describe
'106291' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXK' 'sip-files00139.jp2'
bf9cb51577729edcad416ed38abf86dc
a07af7ffccc3bde72796c8dd8ce54e97e7c74688
describe
'76323' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXL' 'sip-files00139.jpg'
4993d977ff2a1526dba8f3fc9d1e5431
68befcd40f8a614506ea29d0c7d4ae27703139e6
'2012-02-11T09:29:32-05:00'
describe
'39741' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXM' 'sip-files00139.pro'
40a13af190ba69be7280f9839488805b
984501b0fa29ca1aca5e381389f6e0291ccb137e
describe
'20944' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXN' 'sip-files00139.QC.jpg'
43cdc443e55a896bc208c9731bac578c
4a26eafcc873a00184acfa94c2ce23653c5b2476
describe
'971586' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXO' 'sip-files00139.tif'
58ce44af78f18f1a1a038fa22b8b92dc
802c9532181c98906b00b302e4e20a1f25b49bbe
'2012-02-11T09:29:36-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1865' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXP' 'sip-files00139.txt'
11bf4a67624635aae6ad37d5648e6e8e
60e84e230523f84f9161926e9d572417bd76ef28
describe
'5840' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXQ' 'sip-files00139thm.jpg'
63ea28b3f7714b03ff15f88e36fef6c1
a178936a9bcd326687688ae6ef22ee756d79fea6
describe
'71321' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXR' 'sip-files00140.jp2'
87a2b763d1a81d7733dccc45a74e8439
51983199759cc24c070261b806325997087b7311
'2012-02-11T09:31:07-05:00'
describe
'53472' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXS' 'sip-files00140.jpg'
b9ac92a0403f30a468a2b94e4061ae07
5ed48845f25bb70b8a8971fb6915066bad94abc6
describe
'25201' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXT' 'sip-files00140.pro'
bfa2687e49aceba66b935a3503bd044c
2878544c72c363c82aee06c21a408dcc277acd64
describe
'15860' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXU' 'sip-files00140.QC.jpg'
869f68f9d80a991659a9fef680793ab6
bac16a7eb72afd84d3a21b9be52c3d00c5279115
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOXV' 'sip-files00140.tif'
0ee53667e9a2a2a50ce92e77b9ab032f
4f9b21a0715e899ab481041353eb4f17925ab65f
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1159' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXW' 'sip-files00140.txt'
06c8cde67ae7ca303b39ae12854d2cf7
358d72c3db4aef87b04fab849f0d574fe843880a
describe
'4920' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXX' 'sip-files00140thm.jpg'
ef6b5f02eb97edb216697607acef8e40
5ca9a1825ed442c7a1161c916e45db435a41c33c
describe
'65799' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXY' 'sip-files00141.jp2'
43cde137b16acead735483ef947d28ed
7ec2dbcf13d15305d14961ab07b1a6746e683cd3
'2012-02-11T09:20:04-05:00'
describe
'51109' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOXZ' 'sip-files00141.jpg'
ae4342d832ccb89b108117027859b824
bc278c757f62ccc1cd33140c21ce1273ee3f7858
describe
'23398' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYA' 'sip-files00141.pro'
e1c2ebbbfb2115d583ad7adeda8b385e
4188c132cc5688bd717b3ea111bb860b51660524
describe
'13822' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYB' 'sip-files00141.QC.jpg'
0c7bc472640e98764cbd7699a88d67e5
379836816c462e0f5f845beb2c3b4ce6c444dd80
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOYC' 'sip-files00141.tif'
a850caf6f5a9b8ac9366a93fbb8bb301
4829873e28371d4c71253f7b4866f5f35e964b83
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1215' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYD' 'sip-files00141.txt'
bc10dd363d63f5972ed1809fd35087a2
423999015397300467c17a96c7455fb4e02ac724
'2012-02-11T09:25:47-05:00'
describe
'3939' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYE' 'sip-files00141thm.jpg'
1cd902a57fb24c35afedc17640aa6611
020a24c7113431996b00255393e387604183d053
describe
'63914' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYF' 'sip-files00142.jp2'
9e10c66766a53b5e8557bc5ebe2e71fe
fec16cd5570cdf261875690fec6c6490f50f4556
'2012-02-11T09:26:19-05:00'
describe
'50524' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYG' 'sip-files00142.jpg'
61d9e527d268b920b35ee288843546c7
4166a25e7c118f680bfe5f222e931f29f86b40eb
'2012-02-11T09:25:21-05:00'
describe
'31763' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYH' 'sip-files00142.pro'
1f45273f2393b524db88ca68c77f9260
17d360f82b5ce716684b64dc7f94a7f3101efa49
describe
'14555' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYI' 'sip-files00142.QC.jpg'
8baa5e1ab5d0eb0a5cfcc4fe858d36f6
8a38144e6f14fdec5c6b62ea5c08f8f4e3ab3a95
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOYJ' 'sip-files00142.tif'
731d41f7d846a2eb8bca25feea6bf4fd
dcfe744d7cd361a565311748592a3df74949c0bd
'2012-02-11T09:29:22-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1735' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYK' 'sip-files00142.txt'
978b9c74f6684daca17eb572ad3f2c23
46dc24228ec45b20fa85609278eb00e321074f48
describe
'4039' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYL' 'sip-files00142thm.jpg'
3e3bb4dd78cea7f473611fa7ec0371ac
b3ec542f7378cff10940f032c8cfc485d39f8dda
describe
'98098' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYM' 'sip-files00143.jp2'
5c1e8dc49d7d9fa7282b5760fe623fd7
29e18521cc514840f05db2639bc5e5f1fc8633ed
'2012-02-11T09:24:34-05:00'
describe
'71215' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYN' 'sip-files00143.jpg'
7074914b833906cada10fd19522fdfc0
57fbee16ae9dbc03ffb63ee2ed1a6fa3a9610ae2
describe
'37346' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYO' 'sip-files00143.pro'
aa556e843cd8771f5d05ddd5a8335830
244ad6ff47387151ab7240d3d79e59ec5fcf3eb7
describe
'20198' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYP' 'sip-files00143.QC.jpg'
d6619f52fd1b6b23e33c988b2c74027e
a8ca618a42e7d384929a3172337221168faa3705
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOYQ' 'sip-files00143.tif'
a076582173f30864de0380f3ea05eac4
9c8990287055622b7e1d07726b97cc5fd97b02ed
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1775' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYR' 'sip-files00143.txt'
d7aab404ab1e79206ac4e517fe86a85f
935260458f7c4a1bde35e19b6e37c60884394e21
describe
'5740' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYS' 'sip-files00143thm.jpg'
50c96fb7387dcabbbc6ab8c374da728d
ba5556ad1d8c41d30421a048083879cfd59c0478
describe
'88181' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYT' 'sip-files00144.jp2'
7b5b29ec471fd3e7c899cfe8c85b9522
24e671f07253445af0ecb24d0bbc3efd46b9ad70
'2012-02-11T09:25:24-05:00'
describe
'67792' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYU' 'sip-files00144.jpg'
74f216c66a9b47ceb73d2e55fb0d5688
35ab4855e39d6a6d9d5fa4a9b159fd742d2c991d
describe
'34161' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYV' 'sip-files00144.pro'
53e37dca360099d0e6d9bb0a742fa092
570e8046db1ce0df1dc78bd0739387cc2e90daf9
describe
'20035' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYW' 'sip-files00144.QC.jpg'
1e2a017d09453985e949d24205201aad
01be7d3a7efb6cc10d3ab00235c50de0d9829abd
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOYX' 'sip-files00144.tif'
8eb3d73103cf60fe09a690a2450c2729
d2d204246c0743ec1c84b8a144a138cf1e6a1aad
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1538' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYY' 'sip-files00144.txt'
1f0d9f046c08d35ab8ebc9bbfc37c4e8
b673a298e9b085ccbe8c6bd4ec29f57bc8bb8dcc
describe
'5307' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOYZ' 'sip-files00144thm.jpg'
87e234735bd2b619ddb68e8e00b7d903
e8b154016dab8c777da72af406f4b761b5d1d152
describe
'86443' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZA' 'sip-files00145.jp2'
15c8922a068c9613d8065677106fe744
d769e5f2e1c9b484d99e24e18dc566e87e928278
describe
'65907' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZB' 'sip-files00145.jpg'
3d89640dabba0161a4a281c37b936f2f
564147ec21ec31b35b122e527a9d6ed82d4e7b54
'2012-02-11T09:22:46-05:00'
describe
'32857' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZC' 'sip-files00145.pro'
1cc5a052d1f0cc876f71d151ff0c6da4
ce76876dfb4d304963a7b3b0ed2da352333964e7
describe
'18212' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZD' 'sip-files00145.QC.jpg'
413abd21d909b6cccf150ed96294e881
6571924766f1d32ca614bf4e2ce1654930f27a4a
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOZE' 'sip-files00145.tif'
f0bcc6a04dabe8f8260f8ddd6cc33719
f155c659117ab209d856d8bb8dc73ff34f3747a8
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1488' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZF' 'sip-files00145.txt'
7ad85f0c2e2fae707f1d26f470a4262e
2348f336f4635dab39eb688e042d5ddfca5eeb68
describe
'4663' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZG' 'sip-files00145thm.jpg'
7199675ff3ff33075ac972df863a6131
7dd5eda87f5a51404bb76be5966103abd8514528
describe
'96591' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZH' 'sip-files00146.jp2'
16f563c2a67683c7985dd137b850185e
e1703daddaa614ce679f2c3bd78496531fd7a939
describe
'71063' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZI' 'sip-files00146.jpg'
e96b2036506a1c3d640cedf11260a074
abc955a9951b2a85d3daaeea4b8b8f84d421161d
'2012-02-11T09:28:54-05:00'
describe
'37054' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZJ' 'sip-files00146.pro'
fc17ca6f32d779db97e5c2741837122a
b5dea0291195da0854f25ae320c34cced6aaa810
describe
'20409' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZK' 'sip-files00146.QC.jpg'
f820e7601fead8d3e765144130390231
30955a1d48dfe2aa9b18068abbf858241664207c
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOZL' 'sip-files00146.tif'
8952ed29d5a29d545a4ce26faeb8356a
3cff9b3e6fad4e67aafa443134878361e719baad
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1928' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZM' 'sip-files00146.txt'
e15b579b0e9bc2c62bcafe258fdae964
5e294fdbe15dc06968826d9d7a73f33083116880
describe
'5571' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZN' 'sip-files00146thm.jpg'
8940876f39266cae2061f3aaeb3a1015
a6f7226a4a7131dc9dcab8a75978affa508cd2ea
describe
'94630' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZO' 'sip-files00147.jp2'
d9e76e37d2e461a327b6b324fbdb7c82
125faccf00ac518bc149d1e6feee7d3fef50e752
describe
'70344' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZP' 'sip-files00147.jpg'
e66d53871f64f677a7ee95442808d898
6049a2319455e197cd7ff597f9187f20a572d771
describe
'36307' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZQ' 'sip-files00147.pro'
4da1393fbd376104c80f44f28fcc99b8
f16f7ecaed766047bdfcca061b6d6d246b9ee110
describe
'20373' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZR' 'sip-files00147.QC.jpg'
db484b011a77f4819de1eacf5c5149b7
d0b4a26d9880ca9254a738e2a735bc16553a2671
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOZS' 'sip-files00147.tif'
b346a7ba44b3103028ecbbafa626fad1
2d1872f6f384522c77c321c5833febf4a9a0677c
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1921' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZT' 'sip-files00147.txt'
39a580fa2daf54f201e146854528cf29
f4108d792f908703c7c3c76c7c142d1ff08ac774
describe
'5464' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZU' 'sip-files00147thm.jpg'
add2bc4e4273537e716cc42375b21383
008e47e6471a522d4b350bf75cc133af4dedab85
describe
'84591' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZV' 'sip-files00148.jp2'
c5691c3acfc1f5660edc401bac883aa9
0a4a627a6a2309bd4d43f285890594bd750527ae
describe
'63265' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZW' 'sip-files00148.jpg'
c0266edf0cc125367dc938c7c5c44521
85b982be8365480194ac1243cbb8b613359bc81f
describe
'32864' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZX' 'sip-files00148.pro'
21ba9041372e49b6e17a6537c54b7310
079fe3f42afacedf33d9b1aa51b41e4baef5103a
'2012-02-11T09:28:04-05:00'
describe
'19267' 'info:fdaE20090607_AAAAAMfileF20090607_AAAOZY' 'sip-files00148.QC.jpg'
69f8c1e46b4dc12413aefb0289c9ce66
abd55dc5e007feacddfeab9f23ac611c14825642
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAOZZ' 'sip-files00148.tif'
757a5b4a408536762d89dc822f50baa3
0fcdaf7a2212a186dc6e31e3becf2695d7e980b5
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1660' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAA' 'sip-files00148.txt'
330ad0ea144245ddc8a3749c66342312
5033d6421ff6bd191e6e93cfccf433c1618007fb
describe
'5174' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAB' 'sip-files00148thm.jpg'
e77bd50e1ea90ad38c67a195e9b1120d
4aad3f340af13acde2cdc9a97f2c3602f9129fb6
describe
'76503' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAC' 'sip-files00149.jp2'
93521acebc632e3b1521d7a84113b52b
2e87f82aa84976b2f735f50295db1d8c88d52590
describe
'58884' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAD' 'sip-files00149.jpg'
d12f4bb886ae44eaac7a9ea9fce59d5f
c35942ca10e0ea852ba125e91ee16efbbc311745
describe
'41100' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAE' 'sip-files00149.pro'
8e6a3306f60fa6eeb96b79ee257f3f78
669a0d0091bc7f15ddd6a30d79499b21438065a0
describe
'16908' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAF' 'sip-files00149.QC.jpg'
4c6158ad6cb8a23df9ee9e8b659d72ed
290bcb47516f36b6b0ce483c49b1917065edf8b2
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPAG' 'sip-files00149.tif'
011306ae430be43b930bd54ae7553a57
92a67066ece695f0c1d18a73b0f7571fc37ba508
'2012-02-11T09:20:53-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'2268' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAH' 'sip-files00149.txt'
09f0df9406e76dcc1245d2b97767de96
26479cf34f449a0315592aec1c263c054e7b251d
describe
'4604' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAI' 'sip-files00149thm.jpg'
9886d9030207e5fb14a39ecc1cff35bf
a6f91048292b82ea844dc1c24effc0da1e925ac5
describe
'78282' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAJ' 'sip-files00150.jp2'
eaab34668fbc81872fdb65f31e15202a
e9e0308e5142fce7beae4e9d16c32a8628a4a921
describe
'59900' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAK' 'sip-files00150.jpg'
f4b698c728db63b6d9c32167dd1ef492
8e2b08047daf8979c950a572f70fa4151945ac62
'2012-02-11T09:23:11-05:00'
describe
'29449' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAL' 'sip-files00150.pro'
9242ef6cf89a69d8470dd9d8de7061f3
ff81738223ffe9f13b63f45947703a780da52385
describe
'17362' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAM' 'sip-files00150.QC.jpg'
de3e4f83ee70341a2edf276c5b215959
4e9cf554e471a5770be2f3449c14d5086031cc82
describe
'973017' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAN' 'sip-files00150.tif'
e31005562ff95b1ffd7b5b4f3f677fb3
9caaf61693d1f3af67114366f76e58323c24943f
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1255' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAO' 'sip-files00150.txt'
c10bf237bf6a11b68116e89fa8bad11c
bd68eb259aa6e155aa7e2ebd7501b41bcc4eb70f
describe
'4547' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAP' 'sip-files00150thm.jpg'
dff7ee78a8b0df030fccad3a1ff2db10
3aa06c2b88e7f5c7ff747a1281a1fd2d1f5a7b06
describe
'77915' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAQ' 'sip-files00151.jp2'
63467c89a7b8cede5b6790bd6c019ae7
576286764f9ebd0ab80b76f5cbc061726c52f542
describe
'57708' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAR' 'sip-files00151.jpg'
d9f4516336f2f43557af2069d86a056a
212062c8f6ec90a795b27b491392ee734a119393
describe
'30586' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAS' 'sip-files00151.pro'
e5d7083bf8e4fa28c84bec86107c023d
4ff37e14e09015a4cfd9dc03e9da2dfbfbd8ac4e
describe
'17902' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAT' 'sip-files00151.QC.jpg'
efcbde6282db0bdf9b49ce5a1f13f028
3f62bfa16a964d89709247fb9024f5a51340f5b8
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPAU' 'sip-files00151.tif'
f7d3780ede9ba3b4bd625dd61aaa4286
07b14aee0ec59e8397fc555bd6ecb25320fa3dd5
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1389' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAV' 'sip-files00151.txt'
cf9803c31b8a320dc615500fb0b5d948
7a26fd62c0481917c1567ef79feeec1849d6526c
describe
'4905' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAW' 'sip-files00151thm.jpg'
e50fa1d588332ebcfc3b891fdd4e869c
411ae8f73271358c0d531a07a1657c22bcccfb05
describe
'105607' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAX' 'sip-files00152.jp2'
11c04808eeb8769a78fdba4266425ded
c5282d349bbf126ce87957db8633f83a93dc8306
describe
'78308' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAY' 'sip-files00152.jpg'
71f6b890d646f465ff1c624379e01afc
e303ecba8f4b547458275f65868e037609ccecbe
describe
'39998' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPAZ' 'sip-files00152.pro'
84a1a0cca283af9ae765c2359fde07e9
da39acd5c9d1278a2b2aa4c5cbd4ab1dd162d9e8
describe
'22388' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBA' 'sip-files00152.QC.jpg'
47e904f22bc98b80bc17c2d76a28cead
dd5187b680c3711350c36a52047319496b5d6862
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPBB' 'sip-files00152.tif'
62e2e1997b337eb3b5ca033e64a94726
969de45bf0781516d68e65921258c5c7c8465d24
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1947' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBC' 'sip-files00152.txt'
41390973b19ec11b918f22581b6643c6
e314d67a338d6a5086b089b3dffc3f639cff46fe
describe
'5663' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBD' 'sip-files00152thm.jpg'
8bcf61b1c857057cc51a67d6e4c3713c
859002e6d929e4878eed6a4543f2d1d459b7059a
describe
'99684' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBE' 'sip-files00153.jp2'
ee4530a76a00b648d7c0ecbfefff125b
5dcc34ca2ea9eee004e810ff9e6e72394b404dc3
describe
'74385' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBF' 'sip-files00153.jpg'
8991a4e838546f397b439e30b1fa8a00
c3cf8628fbfe01f3ba073a3474ac45f0a4d6d299
'2012-02-11T09:27:47-05:00'
describe
'38826' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBG' 'sip-files00153.pro'
9a03aabde7613ae086112d7dddaab57d
ea84e2488b7d8e446bcae18b7d24ec1c322d8798
describe
'22138' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBH' 'sip-files00153.QC.jpg'
938877c16898f5b26b5e624cfdaf0c6e
2adcd301acb394aaee5d48b1f174cad4d027aa3d
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPBI' 'sip-files00153.tif'
3481036431c0ea952a27679dda1dc1fb
823a27203554b6d2610a845726adae73dc50fcfa
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1837' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBJ' 'sip-files00153.txt'
6d13d63558a44fa71ed837a172eb2fec
920b18592c2bcd9ad9eed352707536cdee558f8f
describe
'5770' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBK' 'sip-files00153thm.jpg'
5186c3f443d453ee6e8d77ab8d979074
e21ec48a94b65789d2cfa2438fb277b9fc87b9be
describe
'80560' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBL' 'sip-files00154.jp2'
76d73484897de211511693aaa93a76d6
14a4a60d574f16840947bc3f4014545c500efbe9
describe
'59297' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBM' 'sip-files00154.jpg'
ab50100800d48c93e1e6f917c9b5d8cd
0a4c0991a94435293ff24f05fc572b1ac4d2347a
describe
'30205' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBN' 'sip-files00154.pro'
fc34697cebec995f2c9df2e3248d00a2
ebf1b01fc7def4cca52e0b5d8d40b16c6436bab3
describe
'18131' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBO' 'sip-files00154.QC.jpg'
2c751804ec27153aa45065bee34cc884
30724a11813e97cc00f57ebc0e22bf6add1718b9
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPBP' 'sip-files00154.tif'
5dd29529b3b7233d9cf1f16c3a42a000
167fbce3cd297a4bbe051d349a9e78e2bdf13186
'2012-02-11T09:30:50-05:00'
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1415' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBQ' 'sip-files00154.txt'
5110af4ee066ee0f746677c1a592072a
03ef1314b53b861941e6b17a76435e53eca5ba88
describe
'4939' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBR' 'sip-files00154thm.jpg'
23bac2b970024ffb3864d01a927f5c25
07e5013b6c55bfb64c35779894c36f4f76574bc6
describe
'79111' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBS' 'sip-files00155.jp2'
b9f3830d5b6da518bfe9621b67d81df0
d504239dbdf4897ea7e99aaa93fe297febeb4940
describe
'59085' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBT' 'sip-files00155.jpg'
17118e8d99b82607cf50c53cf8cca867
84891da59df9563dc0fd84fca94a824ca89fa51d
describe
'29993' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBU' 'sip-files00155.pro'
593c0411a501db684d410767f3448f28
dfbf9020ae75a5f97ba69715045486601e6f7d4e
describe
'17930' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBV' 'sip-files00155.QC.jpg'
9a827f8dd82481e490f175e6b3e9990a
1ff3962c7310efaafa62a507ec8e31a8e8d1a623
describe
'974221' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBW' 'sip-files00155.tif'
5918d69258b2d79102f864d66733b7f3
b6e27617becab853efa2740e33c9996ebd23fc4c
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1447' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBX' 'sip-files00155.txt'
0e8df9eb06d8adf3e7e4a32519b2df2a
7843e31c380ee04d942b4d0554cb6f754533acae
describe
'4863' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBY' 'sip-files00155thm.jpg'
cf7c32aa697a07a2420c6f0591e286dd
5d56f9774389c68352ebf1df470706b04163cdf1
'2012-02-11T09:30:17-05:00'
describe
'76944' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPBZ' 'sip-files00156.jp2'
a506cbb37b7f1aa4b5490bfa741364dd
73484f1032da44f6b1daa00fa0733a6638a7b884
describe
'58443' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCA' 'sip-files00156.jpg'
8827f116f255d138a504011a1e366527
c51db1d338be449e3c23d7625ca654756134b01a
'2012-02-11T09:27:26-05:00'
describe
'28477' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCB' 'sip-files00156.pro'
5fd6bb93cf21433b2c86a418a1b7a925
f0ffe7fc520455bea7056494b8d4dba666b86d84
describe
'17501' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCC' 'sip-files00156.QC.jpg'
9d27259536000c2caa83b019d6bcab39
57047efe5495f08c5bc3e7618419ad0578c23b25
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPCD' 'sip-files00156.tif'
bf517e05e06011c2214caf8dde67b2f3
7aff2ba37082a22aab0597fd67988788db7fc9b7
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1293' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCE' 'sip-files00156.txt'
217ce727868816b21d28b05611d5e6f6
f426c1b96877b5c9e025246e72000e55c53a7854
describe
'4519' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCF' 'sip-files00156thm.jpg'
80898dbf3a47b8b9976607f14af0289d
6850705a94c9181ce00822a81152b1addfccfbeb
describe
'80436' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCG' 'sip-files00157.jp2'
077a7daad761db5e617e05b65238a933
9f1f99efe5768cac38aaeea2b3c3d65bd79cafe3
describe
'59938' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCH' 'sip-files00157.jpg'
035ece79184f1fd9f735cee3231ace91
b8c68f5e77df0abf89e2eb844a7d16c8fc026e11
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPCI' 'sip-files00157.pro'
313bab05af04df66c63dea13122b1e0a
5b28ca7a987ab771aafb547291cc0dfca18f429c
describe
'17334' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCJ' 'sip-files00157.QC.jpg'
81129382451b20a59129f6d9867e64a3
f8e257e179b8eb34312545afc2c14c33930d521e
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPCK' 'sip-files00157.tif'
dee029a8c1222bf19b5631f7638adc44
bd741dca0ab615a3f2e1c2dafa1cd3f57ce48575
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1424' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCL' 'sip-files00157.txt'
b56760a289675f5b041792f8639bd86f
c4c878314f3216472ca93db7c2c0c3d11ab1ff3c
describe
'4938' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCM' 'sip-files00157thm.jpg'
1bd210c32c4ded6afb25f05f80faf097
3d47d1203a2236324b51e777dc52915a96767760
describe
'88796' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCN' 'sip-files00158.jp2'
01493dd7626ed582005b55bf31773335
432082ec05377497912360ceace731af3636d5a6
describe
'64900' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCO' 'sip-files00158.jpg'
8bd06de91b8fe413c849e1491bcc6f81
659dcabf23228ee3dfd017f0652ab47f1610c128
'2012-02-11T09:25:50-05:00'
describe
'33989' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCP' 'sip-files00158.pro'
64fe9f19674521bde8ebc03d6444fa9d
41595edb6b8163a4740595adb53eb82a26ec7cf2
describe
'19363' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCQ' 'sip-files00158.QC.jpg'
0807a7ab10ecb885a5e8aab55059bf72
eee85ecc6c557709ef3367b92f487dc08d744f6a
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPCR' 'sip-files00158.tif'
633fdfe7ac7175054891318d983ad085
3781a5fdb5e2f3d65b0c546da614c0de8b5be518
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1738' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCS' 'sip-files00158.txt'
a215fb022ce74d81b0977fa63e1c7f95
a532d74337ab3af6b06ef078ec5bf6ba67658824
describe
'5342' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCT' 'sip-files00158thm.jpg'
0e08a89d7bd196b20a77cb0b50a4dc2d
9a4651af2c495d07fce80368ff098687bb59d35c
describe
'94786' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCU' 'sip-files00159.jp2'
a5dd1ce16b230fbca2c38d7a5602a9a6
e252d5eafe55d83764263857609bd717ed6647e4
describe
'69674' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCV' 'sip-files00159.jpg'
ccc9a2176bfe692cd7b7e39f795d1afa
1ce9d273c020a1a71246c9cdb0d780bcdaa651c9
describe
'36101' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCW' 'sip-files00159.pro'
433c40d441d09ee56abaf43a0a93ec54
92b7417f5a8b3e5b12ffa25459ee971660a3f811
describe
'19564' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCX' 'sip-files00159.QC.jpg'
f67dfb476f4403e1909fba6729d75498
9cf327c350dd6863f9944f2c78d2a5fb9c778627
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPCY' 'sip-files00159.tif'
c7b9ba57090e065daca365c1a2323774
e0ce70f41dfd3f1e32bad7db56cbf36ae0978e6e
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1731' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPCZ' 'sip-files00159.txt'
f2c1d3a1798869272398db2bda4f59b3
55ec641cd16928ddafb84e53fd1992c41899f6bd
describe
'5197' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDA' 'sip-files00159thm.jpg'
8de89db5b7370c8bafa6511656817f7a
c58a3440d2c3cea7203a51cd402b8766e6b150cb
describe
'91555' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDB' 'sip-files00160.jp2'
88085ee3751b68f1eeab4885e1a21163
eb15cf823a44ca01a85a1724db91ce62f9f104b4
describe
'66608' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDC' 'sip-files00160.jpg'
5de9b703d6d1a398fec8071cefff475c
76171849215da94b9c7cec1a1849db6e0c8233c1
describe
'34794' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDD' 'sip-files00160.pro'
2cf74a5a1dad1d7240ffaca3238b5f6c
0fa1db5e6c021edc131d2f210c2f80e1bb6b10ab
describe
'19497' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDE' 'sip-files00160.QC.jpg'
e71555290bbc7a0639c5fa3e00184955
0877d85392bbc0dbd14a686ef6dd9b5a7366f437
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPDF' 'sip-files00160.tif'
b8895e97e04b04fac4ab4b585afcef39
cdc95f0fa79b95789b28c72dd31ccf9cded3c0b7
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1873' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDG' 'sip-files00160.txt'
a5376878415a0de5ed67794e0e73600f
40a72df3b7239e7fe504501bd072f00f0d18af11
'2012-02-11T09:26:47-05:00'
describe
'5072' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDH' 'sip-files00160thm.jpg'
eaf800982b9cc281f674a2e1c01920c7
e63107b5db0c0a46298987724e6443213c1c538b
describe
'93152' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDI' 'sip-files00161.jp2'
83b7319adaeecce974de491af1f7e99d
774f23aa88666d2cd37d9493afb3bb1a2d7417bf
describe
'70795' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDJ' 'sip-files00161.jpg'
bc5ec2959b430b816f060c7ba4b1db70
69487c647040a1a8b089b1b7371c19caaa757582
describe
'36521' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDK' 'sip-files00161.pro'
43490b693fc4165eac636aba55423bbb
694e3b8065962357a86433f0f557f9034aff158d
describe
'20814' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDL' 'sip-files00161.QC.jpg'
2b830f656a56df3534494a519642abd6
32d813e69e77405c7565b1d04a46f8822f069df7
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPDM' 'sip-files00161.tif'
18462eadedbdd7844f5c06c6be115422
7b7db6fdf8c76a072e042c98718d7d8219a03dde
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1800' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDN' 'sip-files00161.txt'
e75ec48000b725d9265dceff21b6d398
cd17ad15e40430a14ae1f99e297ca7567ce92c10
describe
'5266' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDO' 'sip-files00161thm.jpg'
44366098c89e4437e490be48df67bc7f
3cedd5d361d6f792e7e1ff05bf28345254b82669
describe
'85930' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDP' 'sip-files00162.jp2'
a6836c142ad8cd47f8445f8f51a833ef
b0fd1ef4a53f7efd29f8a269d976b2c612201c58
describe
'62833' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDQ' 'sip-files00162.jpg'
cdf5cd4e463e7a48d90e2d5facbf07ce
a773753a52cbaefc09bbcc06a019eda594a56f71
describe
'31779' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDR' 'sip-files00162.pro'
f2b0d03e98ba58c9e652d92baa7b23cc
9b919513451e797b6663f65545bfaa4b45c61a98
'2012-02-11T09:22:48-05:00'
describe
'18548' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDS' 'sip-files00162.QC.jpg'
abacf8a4c6daaf8d5cb79f2c7793ed18
33fa49feba90c051d085de0dd29e150a22c339c2
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPDT' 'sip-files00162.tif'
46b577ca876d7445910eb0f45b2329c5
fba1b247b5dd5380474484b46dcdf2d9e4f4d94c
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1587' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDU' 'sip-files00162.txt'
7b474df6b169b8e117683647ea3ac8da
2b05da02e7cd3020654d659543ac22cc4fd2c736
describe
'4926' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDV' 'sip-files00162thm.jpg'
18b54250637b55a501083aa54d1e88a0
b58766d202149cd8e94e55305f3951a997b031e8
describe
'98335' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDW' 'sip-files00163.jp2'
45c50e5e5293795ff063c7a929a010c4
408fd204971b2b1c35dcbabfd5669be8113a3601
describe
'71053' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDX' 'sip-files00163.jpg'
c3ce3fef8b73fa5c533022bf0c1c9577
bc262b1d59ac628e386f49860b1b63dc43ea8f85
describe
'37579' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDY' 'sip-files00163.pro'
6eec522400ff5740dfa8554c315774dd
aa641f45ba588fd41c33192a5748179033c913fd
describe
'21149' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPDZ' 'sip-files00163.QC.jpg'
cd62e8addfd36cc034035aa0490b2b47
6abc140cd88d3966963c129445403ebd11e546fd
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPEA' 'sip-files00163.tif'
69be9c43924715a7b225e9a77637151d
b5876bc1552db1d27fabd8fd8b989b8213337e7b
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1954' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEB' 'sip-files00163.txt'
f1e8202bbe68866846c1814d2a5473ba
05b7f26ccae1665c5862966688855bdb5d0bae52
describe
'5332' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEC' 'sip-files00163thm.jpg'
f09c54430766d126bc725038f4ebc69a
7578fdaf77294431e95c54bdc8ae9b9eb38537b1
describe
'78340' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPED' 'sip-files00164.jp2'
aad250d6bccd8d07a144ef4e3d953ee0
402fb51ed2057f7552049a661dc9709ee8c05f87
describe
'58085' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEE' 'sip-files00164.jpg'
b74f2cc8a9b614b530ee2e1d7125fecd
300cd2572d524963d10dc18653f606b570958f32
describe
'30920' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEF' 'sip-files00164.pro'
1e21bedce8b4adbde993599147491320
9fd0d40ad3f8b89610370a06acc4551b291e3646
describe
'17721' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEG' 'sip-files00164.QC.jpg'
968e3ca90e49b077124e7d0381295360
bc235fa62f4602923e28766cadcd56628eb4e718
describe
'978060' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEH' 'sip-files00164.tif'
eb331ce550ba8220a00c97dd408f2f28
71c53d6416a3cb910d4d742032bfd041138bdf1a
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1497' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEI' 'sip-files00164.txt'
18a9a83ba40c793a0bea6b96e27d3908
a604b9d37ff52dd17eaa55e4c4705d71e3999b52
describe
'4842' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEJ' 'sip-files00164thm.jpg'
323a14e2b53c5fd57686e38e04e4ca93
3b0473e58b1a8fa963aa98b8a66f357a8bfd95db
describe
'78376' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEK' 'sip-files00165.jp2'
9cdde0cb85cd9352c822f63ceb8037c6
b1a3a918a8618d8d03e499a3fc43a76191add670
describe
'58310' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEL' 'sip-files00165.jpg'
e7e773a2b1ee59f918d95e621e6883b2
883bb054fe3f715b16c92656e508eb239fabd661
describe
'31545' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEM' 'sip-files00165.pro'
7f482063de94b092609923b07e11f6e2
3d99ad707688e150506a6847d5c36d1fc50442f4
describe
'18126' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEN' 'sip-files00165.QC.jpg'
32bf07c4a799958d377c664e2e9ae95d
c33668e3fc1d4f5c91428f416f5dc32a1f7e61bf
'2012-02-11T09:27:02-05:00'
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPEO' 'sip-files00165.tif'
fbe0ce2522f8217b92ddfef6362f8d91
09772e8d273e369912de91bc02c8493f96259512
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1333' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEP' 'sip-files00165.txt'
dd754131aaba705950acdb93638de5f9
e956863f5ceea6fb811b7c3b172f54e6b2f243a6
describe
'4643' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEQ' 'sip-files00165thm.jpg'
05364d0d1d2d1a0c74a9043cfc6a11c1
534b633b8a70994f7dafd38451515cfc8267de85
describe
'90291' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPER' 'sip-files00166.jp2'
bc55019bc791d461b9122378b1bf44da
b5bbca091dc3cd64027d21afa32c8b9a6881b848
describe
'71462' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPES' 'sip-files00166.jpg'
d80422c3941910746b72304af24ac69c
651b6179ff1dc9a70525a9c7781d7846a3acb0d1
'2012-02-11T09:29:50-05:00'
describe
'34839' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPET' 'sip-files00166.pro'
fbcef82c893fb111780587dc8005999e
7ac8559d1a8de662666ab0f0caefa80efe62f967
describe
'19822' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEU' 'sip-files00166.QC.jpg'
2e9d9f2f4edf8b4b08533e9e9b9a856d
a3e797d327d58f3680767ac540ffb2671b527f3f
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPEV' 'sip-files00166.tif'
cd7a3d10d0a6e2ee501483de4afa3339
a0ae2ed7689adf0ffcf2e4506fdc7ed2d0cc6d79
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1523' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEW' 'sip-files00166.txt'
997cea10ada409fa38a47082cbe03105
6aa7e7a1c8346ded4af27abea41a5aa0223c8efb
describe
'5183' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEX' 'sip-files00166thm.jpg'
4f981a43b2d05544ea180a7adf61cff4
6bb7a99750d1b2efd170a3911c97f13be69a08db
describe
'90097' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEY' 'sip-files00167.jp2'
b0757e98633964a7184560c93ffb3f17
37fed95515bc62e08b65c06aacd1ee0bc5c99fa3
describe
'70707' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPEZ' 'sip-files00167.jpg'
ebb6b8d3abb8c5fd79e4400287000f2e
481f054743536b4e8ebe3a3a328f7f357e5a9afd
describe
'43491' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFA' 'sip-files00167.pro'
4ae78238177de5baa80bed99656fbc45
6de74f690f619bf06f72f18c072028335f442f50
describe
'20771' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFB' 'sip-files00167.QC.jpg'
ba0595c07b9f65c9f03152d29506d633
5f5a8a89f3641f7ab9185418dbd2e51fd2565ea5
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPFC' 'sip-files00167.tif'
5777d30f7a40bcea33d067603524c814
5ddaa4a8b9cd78864a3dee058ce98da417b928c3
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'2171' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFD' 'sip-files00167.txt'
420f9e0a41422c4e86bad5f1e1a877ea
fb176d642c8e77d2aa48598d609e21d1b4976181
describe
'5216' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFE' 'sip-files00167thm.jpg'
f1b8dac58eef8afe892e7f3f9e10b010
fb44cda0be388e8420d8bfad139deef3ca041905
describe
'80226' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFF' 'sip-files00168.jp2'
4ebd5671d10367333fd8bb0d033f34e0
6ff14dbe33bfeb5c8039be546e0f696be3156000
describe
'60036' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFG' 'sip-files00168.jpg'
715328f2ec18257faf7da580dbaaba4a
e66c8771a691d3345b0d4f639e8e158953b2300a
describe
'29710' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFH' 'sip-files00168.pro'
070624941f805d317f9895459e430e05
fba810dfc30ca4e91c584f564bf50634dd7af336
describe
'17865' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFI' 'sip-files00168.QC.jpg'
6787ecf2db068d23eb5d3a85e259d2fd
10ab99d6493e95871977ce5169336b4a37b86215
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPFJ' 'sip-files00168.tif'
cd639c36a01a5b09e5c8c4c17b4624b3
412247bf9a5b8a8f25a2de9b957c5507315406ea
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'1505' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFK' 'sip-files00168.txt'
55959f3e623d732a24d1649f83acedc7
49f4caa326c5fb2e182feeff76720f20054650d2
describe
'4578' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFL' 'sip-files00168thm.jpg'
23c3c68c11997ccca76a2c5dde2242fa
61360a1037c4a5645bdbf1d9a9d5491951c9690a
describe
'32911' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFM' 'sip-files00169.jp2'
107af6811192c04d6059a0b9046c747b
f94c09a46ce930d7254dd7759d08b9df7bdb08b9
describe
'28055' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFN' 'sip-files00169.jpg'
cd9a8cc94e366dff6b9c5742500e90be
a6da0a391ac39b0d16e5d2d8cd1fc9b833f1973d
describe
'11317' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFO' 'sip-files00169.pro'
07bda5b761b9c2c51f80995eec6bf5ca
00c19c82c39d2a5791d22c3d4b5c50c4f805e881
'2012-02-11T09:23:42-05:00'
describe
'8150' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFP' 'sip-files00169.QC.jpg'
81f3f736c632c3ca142e2b0803313083
150c62ecd4eaae8c875a2c6d55c670c161283f53
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPFQ' 'sip-files00169.tif'
abd4ddc5c2752d783bac01d6471df327
a24d7ff523f5f995e63d9da5c06d744462f56565
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'539' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFR' 'sip-files00169.txt'
452b076064b6f1450c9db13739f1f732
ade960dbf88bd31959ede24eabf89120054ae185
describe
'2475' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFS' 'sip-files00169thm.jpg'
fad167af827bd54b884188fc4ee26168
9a783bbbf033a0a677c817084a1d5e4571deef26
describe
'69987' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFT' 'sip-files00170.jp2'
8edcfcdbd7b725ab55efc457a16763e2
37fda850a819291f92f94d97cc55b20e5ee5cb9e
describe
'54957' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFU' 'sip-files00170.jpg'
c84b9e7fe7b8398d73c767d984e077f8
ccda552d6013421424519ab46d92b606f8ebce01
describe
'21841' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFV' 'sip-files00170.pro'
78ebe80061b68757ed7b4b0031bd33de
2df748b88e40265da9ade9cf7b7f199067cec0ca
describe
'19710' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFW' 'sip-files00170.QC.jpg'
9c92ab90a862d5553873460f18d2ce2b
15ce9e3f83a9cc5298923f280880ad31afe7acc0
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPFX' 'sip-files00170.tif'
1d03ab331a63d8bb51c4d8042efd16d8
470b42382d1a784d1e0bfc8b6d10357c22d5a5f8
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'957' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFY' 'sip-files00170.txt'
3524c5ead77d32e7e8d29822d32f691c
89f50b92a87feea575916cb76f232c48fca0d88e
describe
'5400' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPFZ' 'sip-files00170thm.jpg'
e4e17c6413c8259b3b95b0e8b9bb8d30
3025d5acc5a2d38fa3d735a1f8f42bed8b3a5164
describe
'62582' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPGA' 'sip-files00171.jp2'
ee5eaaf66380b629e00bce4ccead6fba
fead340589e778be40c030d19bc33c7d147a644a
describe
'46683' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPGB' 'sip-files00171.jpg'
ded52e7dea84e8f6a2551a45386cee09
3af98f549fe5aa7b750daabeb1861885a52583f2
describe
'13690' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPGC' 'sip-files00171.pro'
0e5e316342cc86fefda40aadde5e85c2
e43a34b250ddeca719f37ba842384be585c71a64
describe
'16343' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPGD' 'sip-files00171.QC.jpg'
84b20710fb9e748145f363e6947cffac
36b25928a85cf45814ce2445116df07f49548189
describe
'info:fdaE20090607_AAAAAMfileF20090607_AAAPGE' 'sip-files00171.tif'
134c594703702b2751d2bc6f1f3061a5
f139649c4c3ef95d2902a57e8f8a9c520ea4c3e3
describe
Invalid DateTime length:
Invalid DateTime length
Invalid DateTime length
'675' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPGF' 'sip-files00171.txt'
627c05550538f94d18ee6028f38d40b4
4d09c33c27fbda24e8f7af2bf957a8802447dc13
describe
Invalid character
'4781' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPGG' 'sip-files00171thm.jpg'
43f4063e0b03b1771eee254b3382dbba
b53ff7b6625eaf87c836a8cbd74fcbe9b4285d30
describe
'1048778' 'info:fdaE20090607_AAAAAMfileF20090607_AAAPGH' 'sip-filesCopyright.jp2'
864c1ee5d6a629621edeb7d4ff18d731
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81-
TABLE 4
ADSORPTION EQUILIBRIUM DATA FOR
TOLUENE-METHYLCYCLOHEXANE ON
DAVISON 6-12 MESH SILICA GEL
(cf. Figure 13)
X
Volume Fraction
Toluene in Liquid
Phase
y
Volume Fraction
Toluene in
Adsorbed Phase
a
Relative
Adsorbability
(y/l-y)(1-x/x)
.0350
.289
11.211
.0372
.269
9.526
.0647
.344
7.581
.0847
.420
7.825
124
.462
6.064
.128
.476
6.188
.149
.499
5.688
. 182
.540
5.276
.210
.570
4.987
.132
.467
5.761
.243
.605
4.770
.304
.656
4.366
.344
.687
4.186
.411
.726
3.798
.489
.768
3.459
.526
.787
3.330
.578
.817
3.259
.641
.839
2.919
.704
.866
2.717
.741
.877
2.492
.796
.906
2.470
.871
.943
2.450
.933
.949
1.336
Empirical Equations
(x/l-x)
x/l-x
. 203y
.1725(y/l-y)1*412
.459(y/l-y) .589
0 i y -15
0.15 y .776
.776 y 1


-13-
1950 to Present
Since 1950 the mathematics of adsorption kinetics
have been even more intensively investigated. Amundsen and
Hasten (65, 66) have continued to approach the problem
analytically, mainly in the field of ion exchange, which is
closely related, but also in the field of adsorption. They
developed very complicated analytical solutions to the ad
sorption of gases in fluidized beds, assuming intraparticle
diffusion controlling and/or the adsorption process itself
controlling, but still restricting the equilibrium rela
tions to straight lines.
Eagle and Scott (63) presented extensive data for
equilibria of binary liquid systems and some batch kinetic
data, which permitted the evaluation of apparent diffusi-
vities within the particles of adsorbent.
Mair (67) treated fixed bed adsorption fractiona
tion as a distillation process, and developed design equa
tions utilizing a theoretical stage concept. Experimental
results were given for separation factors and for HETS.
Hasten and Amundsen (68) showed that in liquid
systems the rate is most often controlled by the diffusional
process instead of the adsorption process. They also
developed equations based on mass transfer and intraparticle
diffusion for a gas-solid moving bed adsorber, for the case
of one adsorbate, or multiple adsorbates assuming individual
isotherms for each. The effects of fluid phase resistance,


-76-
jjc
sition, and yp the adsorbed phase composition in
equilibrium with the feed liquid.
7. A method for determining from fixed bed experiments the
height equivalent to a theoretical stage (HETS) and of
an adsorbent bed v/as proposed and demonstrated.


TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS i i
LIST OF TABLES v
LIST OF ILLUSTRATIONS vii
I. INTRODUCTION 1
II. BACKGROUND 3
III. PREVIOUS WORK 6
IV. THEORY 16
A. The Fixed Bed Binary Liquid Adsorption
Process 16
B. Derivation of Equations 21
C. The Dimensionless Parameters H and T 24
D. Boundary Conditions for the Liquid Phase
Fixed Bed Process 26
V. NUMERICAL ANALYSIS 29
A. Numerical Methods 29
B. Description of Integration Procedure 32
C. Computer Program 37
VI. RESULTS OF CALCULATIONS 40
A. Problem Solutions 40
B. The Asymptotic or Ultimate Adsorption Wave. 43
C. The Shape of the Asymptotic Wave 48
D. Computation of HETS From Fixed Bed Data.... 52
VII. EXPERIMENTAL 56
A. Adsorbent 56
B. Adsorbates .... 56
C. Experimental Procedures 57
iii


-35-
1. Refer to the above sketch of the H and T axis with the
superposed grid. At T 0 and H 0, both x and y were set
equal to xp, the feed liquid composition. This corresponds
to the condition that the first differential layer of parti
cles in the column is filled with feed liquid in both void
and pore volume.
2. The value of x for points 1, 3, 6, 10, etc., was fixed
equal to xp. This meets the boundary condition that x is
always Xp at the column inlet.
3. The value of y at grid number 1 was computed first, using
integration formula number 3, Table 1. This formula fits
by trial and error a second degree curve over one increment
to the desired relationship that dy/dT x x* at constant
H. The equilibrium relationship must of course be used to
compute x* from values of y.
4. The value of both x and y at grid point 2 was computed
next using integration formula number 4, since x y along
the H T axis. This computation is also trial and error,
fitting a second degree equation over one increment to the
desired relationship that dx/dH -(x x*) at constant T.
5. The value of y at point 3 was next computed using inte
gration formula 5 which fits a third degree equation over
two increments. All subsequent values of y along the H 0
axis were computed by this formula.
6. The values of x and y at point 4 were next computed by
trial and error simultaneously using formulae 4 and 6, which


95-
TABLE 17
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 5a (cf. Figure 22)
Col. Diam. 2.47 cm.
Wt. Alumina* 255.2 g.
P b
.883 g./cc.
Xj,
0.100 Vol.
Toluene
Ave. Inverse Rate
Sample Size
8.13 sec./cc
.1888 cc./g.
.425
5 drops
x
Sample No.
Time, sec.
Total Vol.
Effluent, cc.
Vol, Fraction
Toluene
1
1610
0.10
.0
2
1698
10.35
.0
3
1779
20.60
.0
4
1866
30.85
.0
5
2034
51.10
.0
6
2113
61.35
.036
7
2196
71.60
.044
8
2275
81.85
.057
9

92.10
.067
10
-
102.35
.071
11
2530
112.60
.082
12
2699
132.85
.093
13

143.10
.097
14
-
153.35
.097
15
-
163.60
.097
16
3025
173.85
.097
17
3107
184.10
.097
18
-
184.35
.099
19
3283
204.60
.099


-28-
The boundary condition chosen in this study, based
on the above observations, is
for T = H, all T and all H > 0
x = y
which expresses mathematically that as each particle in the
bed fills, the rate of diffusion of components A and B is
negligible compared to the filling rate. Note that such a
boundary condition is not easily applied when attempting
an analytical solution to a set of equations, but, as will
be seen in the description of the numerical method, it pre
sented no insurmountable problem in computer analysis.
)


-151-
MPY
HLFCA
BY ADAMS
1407
19
1360
1230
SRD
0009
QUADRATIC
1230
31
0009
0853
ALO
DRFNW
CL2PL
METHOD
0853
15
0013
0041
CL2PL
STD
0102
0041
24
0102
1155
RAU
8002
1155
60
8002
1313
MPY
T I NCR
1313
19
0666
1136
SRD
0009
CL2PM
1136
31
0009
0810
CL 2 PM
ALO
0302
CL2PN
0810
15
0302
0716
CL2PN
STL
0302
CL1PA
0716
20
0302
1205
CONSTANTS
HLFBA
05
0674
05
HLFBB
05
1260
05
HLFBC
05
0798
05
HLFBD
05
0820
05
HLFCA
05
1360
05
COMPUTE LAST POINT IN WAVE
OR FIRST DROP OF LIQUID
CL1PA
RAU
DRFNW
COMPUTE
1205
60
0013
1117
SUP
DRFPV
XEST BY
1117
11
0016
1071
MPY
HLFBE
ADAMS
1071
19
0724
0744
SRD
0009
QUADRATIC
0744
31
0009
1167
ALO
DRFNW
METHOD
1167
15
0013
1217
RAU
8002
1217
60
8002
1225
MPY
BI NCR
1225
19
0078
0948
SRD
0009
0948
31
0009
1121
ALO
KNOW
1121
15
0074
1179
STL
XEST
1179
20
0033
1186
RAU
DRFNW
COMPUTE
1186
60
0013
1267
MPY
EIGHT
CONTRIBUTN
1267
19
0020
0990
SRD
0009
OF PRESENT
0990
31
0009
1363
SLO
DRFPV
AND PREV
1363
16
0016
1171
STL
SUMDF
CL1PB DRF
1171
20
0025
0778
CL1PB
RAL
XEST
0778
65
0033
1337
LDD
0503
1337
69
1040
0503
RAU
XEST
1040
60
0033
1387
SUP
XSTAR
CL1PC
1387
11
0090
0008
CL1PC
STU
0103
CL1P1
0008
21
0103
0606
CL 1P1
MPY
FIVE
0606
19
0069
1090


-17-
conditions which are peculiar to the liquid phase process.
1. A constant composition feed liquid consisting only of the
two completely miscible components A and B, is fed at a con
stant rate into a column of solid adsorbent. The selectivity
of the adsorbent results in a gradual removal of A from the
liquid as it travels through the bed.
2. The velocity profile of the liquid flowing through the
column is assumed to be rod-like. [to promote this condition
experimentally, especially at the liquid front during the
filling of the bed, the liquid was fed through the adsorbent
column from bottom to top.]
3. The adsorbent is initially free of adsorbate liquid.
4. Equal volumes of pure A, pure B, or any mixture of the
two are adsorbed per unit of adsorbent; i.e. the pore volume
of the adsorbent is the same for both A and B.
5. Mixtures of A and B are volumetrically additive.
6. The activation energy of the adsorption process at the
surface of the adsorbent is considered small enough to per
mit the diffusion process to control the rate of adsorption.
7. The combined resistance to diffusion, consisting of both
the external surface film and an intraparticle resistance,
is considered together as one diffusional resistance, express
ible in the usual manner of the mass transfer "film' theory.
Items 1 and 2 above are standard with the fixed bed
adsorption process. The development of the theory has not


Hirschler and Mertes (1) performed experiments batch-
wise, similar to those of Eagle and Scott for liquid phase
binary adsorption. Internal diffusivities were computed
from the data.
Lapidus and Rosen (73), considering ion exchange,
developed equations similar to adsorption fractionation
equations, using a lumped resistance, and were able.to show
that an asymptotic solution usually exists. Solutions to
the asymptotic equation were obtained with a Langmuir type
isotherm.


-138-
(74) Lapidus, Leon, and Rosen, J. B. Exp. Investigations of
Ion Exchange Mechanisms in Fixed Beds by Means of An
Asymptotic Solution. Chem. Engr. Symposia on Ion
Exchange. 50: No. 14. 97-102. 1954.
(75) Heister, Nevin K., et. al. Interpretation and Correla
tion of Ion Exchange Column Performance Under Nonlinear
Equilibria. A. I. Ch. E. Journal. 2: No. 4. 404-411.
1956.
(76) Selke, W. A., et. al. Mass Transfer Rates in Ion Exchange.
A. I. Ch. E. Journal. 2; No. 4. 468-470. 1956.


-92-
TABLE 14
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 4a (cf. Figure 21)
Col
. Diam.
2.47 cm.
Ave. Inverse
Rate = 5.75 sec./(
wt.
Gel.
=* 195.35 g.
VP
= .402 cc./g
Pb
- .679 g./cc.
fv
* 293
xjr
- 0.100 Vol. fr.
Sample Size
*= 5 drops
Toluene
X
Total Vol.
Vol. Fraction
Sample No.
Time, sec.
Eifluent, cc.
Toluene
1
983
10
.0
2
1041
20
.0
3
......
30
.0
4
1163
40
.0
5
1222
50
.0
6
1272
60
.0
7
1337
70
.0
8
1393
80
.0
9
1445
90
.0
10

100
.0
11
1560
110
.006
12
1619
120
.010
13

130
.016
14
1730
140
.019
15

150
.023
16
1906
170
.032
17
1969
180
.035


-104-
TABLE 26
CALIBRATION OF REFRACTOMETER FOR
MCH-TOLUENE SOLUTIONS AT 30C.
Vol. Fraction
Ref. Index
Vol. MCH, cc.
Vol. Toluene, cc.
Toluene
1.4178


0
1.4245
17.75
1.966
.0996
1.4313
7.85
1.970
. 2005
1.4381
6.87
2.971
.302
1.4452
5.925
3.955
.400
1.4525
9.80
9.77
.500
1.4600
7.90
11.73
.598
1.4676
5.925
13.70
.698
1.4748
3.755
14.72
.7965
1.4830
1.949
17.70
.9009
1.4906
|
1.000


-156-
CNYSC
RAU
8001
COMPUTE
0938
60
8001
1445
MPY
HLFAL
NEW YEST
1445
19
1143
0668
SRD
0009
AND LOOP
0668
31
0009
1091
ALO
YEST
1091
15
0911
0765
STL
YEST
AVGYC
0765
20
0911
0978
CFPWA
RAU
DRFPV
COMPUTE
1329
60
0016
1321
MPY
81 NCR
XEST
1321
19
0078
1198
SRD
0009
AT NEXT
1198
31
0009
1371
ALO
XFEED
POINT BY
1371
15
1087
1141
STL
XEST
CFPWB
LNEAR METH
1141
20
0033
1436
CFPWB
RAL
0301
CFPW1
COMPUTE
1436
65
0301
1655
CFPW1
LDD
CFPWC
0503
XSTAR AT
1655
69
0858
0503
CFPWC
RAU
XEST
NEXT POINT
0858
60
0033
1587
SUP
XSTAR
1587
11
0090
1495
STU
DRFNW
COMPUTE
1495
21
0013
1016
AUP
DRFPV
X AT NEXT
1016
10
0016
1421
MPY
HLFAN
POINT BY
1421
19
0774
0894
SRD
0009
AVGING AND
0894
31
0009
1467
RAU
8002
COMPARE
1467
60
8002
1425
MPY
BI NCR
WITH XEST
142 5
19
0078
1248
SRD
0009
1248
31
0009
1471
ALO
XFEED
1471
15
1087
1191
AUP
XEST
1191
10
0033
1637
SLO
8002
1637
16
8002
1545
STD
XEST
1545
24
0033
1486
SUP
8001
1486
11
8001
0793
RAL
8003
079 3
65
0003
1051
SRD
0001
1051
31
0001
1707
NZE
CNXSC
1707
45
1610
1211
LDD
XEST
1211
69
0033
1536
STD
1929
1536
24
1929
1032
STD
XNOW
CFPWD
1032
24
0074
0927
CNXSC
RAU
0001
COMPUTE
1610
60
8001
1517
MPY
HLFAP
NEW XEST
1517
19
1120
1340
SRD
0009
AND LOOP
1340
31
0009
1763
. ALO
XEST
1763
15
0033
1687
STL
XEST
CFPWC
1687
20
0033
0858
CFPWD
RAU
DRFNW
CFPWE
COMPUTE
0927
60
0013
1567
CFPWE
SUP
0101
CFPW2
Y PRIME
1567
11
0101
1705
CFPW2
MPY
HLFAM
BY ADAMS
1705
19
0908
1028


-73
)
The most important new consideration in such an
analysis would be that the adsorbed liquid phase would no
longer have just one composition, y, at a given L and e ,
but its composition would also be a function of r, the radius
of the particle.
It is very difficult to propose a mathematical model
to explain the adsorption forces when intraparticle diffu
sion is considered. One possible procedure would be to
assume an external film resistance, characterized by K^a,
with the bulk unadsorbed liquid phase composition, x, on one
side and a pseudo-liquid phase composition, xr*, on the other,
where xr is the liquid phase composition in equilibrium with
yR, the composition of the adsorbed phase liquid at the ex
ternal particle radius r = R. Diffusion within the particle
in the adsorbed phase could be assumed to follow Fick's law
for diffusion within a sphere, using an effective diffusivity,
D, for the diffusion inside the particle.
By equating the rates of mass transfer across the ex
ternal film to the Fick's law expression for the diffusion
rate at r R, the intraparticle and external diffusion may
be related. Numerical integration of the resulting equations,
applying the proper boundary conditions, should provide a
solution.
One important limitation which would be encountered
is that both K^a and D, the effective internal diffusivity,
would be unknown parameters. Experiments would have to be


-162-
SUP
XSTAR
FOR LAST
1138
11
0090
0046
STU
DRFNW
POINT
0046
21
0013
1166
AUP
DRFPV
BY AVGING
1166
10
0016
1771
MPY
HLFAC
METHOD AND
1771
19
0824
1094
SRD
0009
COMPARE
1094
31
0009
0818
RAU
8002
WITH XEST
0818
60
8002
1327
MPY
BI NCR
1327
19
0078
1398
SRD
0009
1398
31
0009
1821
ALO
XFEED
1821
15
1087
0842
AUP
XEST
0842
10
0033
1188
SLO
8002
1188
16
8002
0997
STD
XEST
0997
24
003 3
1836
SUP
8001
1836
11
8001
1093
RAL
8003
1093
65
8003
1251
SRD
0001
1251
31
0001
1757
NZE
CNXES
1757
45
1660
1311
LDD
XEST
PREPARE TO
1311
69
0033
1886
STD
1929
ADVANCE TO
1886
24
1929
1332
STD
1932
PART C
1332
24
1932
1535
STD
0301
1535
24
0301
0804
LDD
DRFNW
0804
69
0013
1216
STD
0101
PARTC
1216
24
0101
1137
CNXES
RAU
8001
COMPUTE
1660
60
8001
0868
MPY
HLFAD
NEW XEST
0868
19
1071
0892
SRD
0009
AND LOOP
0892
31
0009
0915
ALO
XEST
0915
15
0033
1238
STL
XEST
AVGXA
1238
20
0033
1786
CONSTANTS
HLFAC
05
0824
05
HLFAD
05
1871
05
TMONE
0001
1190
0001
CDCSB
0001
1000
1050
0001
1000
PARTC
RAU
DRFPV
COMPUTE
1137
60
0016
0922
MPY
EIGHT
YEST PRIME
0922
19
0020
1540
SRD
0009
BY ADAMS
1540
31
0009
1863
SLO
0100
METHOD
1863
16
0100
1855
STL
SUMDF
1855
20
0025
1128
RAU
DRFPV
1128
60
0016
0972
SUP
0100
0972
11
0100
0856
MPY
HLFAB
0856
19
1298
0918
SRD
0009
0918
31
0009
0942
ALO
DRFPV
0942
15
0016
1022
RAU
8002
1022
60
8002
1131


-103-
TABLE 25
BENZENE-N-HEXANE FRACTIONATION ON
DAVISON "THRU 200" MESH SILICA GEL
(Data of Lombardo)
Run No. B 4 (cf. Figure 18)
Col. Diam. = 19 mm. Ave
Wt. Gel. = 20 g. Vp
pb = .545 g./cc. xp
fv
Inverse Rate = 246 sec./cc.
= .357 cc./g.
= 0.500 Vol. fr
Benzene
= 406
x
Sample No.
Time, sec.
Sample
Volume, cc.
Vol. Fraction
Benzene
0
.
. ,
1
133
0.5
0
2
250
M
0
3
365
0
4
480
tt
0
5
595
if
0
6
708
ft
0.009
7
830
ft
0.061
8
955
ft
0.177
9
1075
tt
0.320
10
1200
ft
0.404
11

tl
0.444
12
1455
tt
0.471
13
1587
tt
0.484
14
1720
tf
0.492
15
1852
ft
0.494
16
1985
ft
0.495


XI. LITERATURE CITED
(1) Hirschler, A. E., and Mertes, T. S. Liquid Phase Adsorp
tion Studies Related to the Arosorb Process. I.E.C.
47_: No. 2. 193-202. Feb., 1955.
(2) Hypersorption Process Flow Sheet. Petroleum Refiner. 29:
No. 9. 1950.
(3) Freundlich, H., and Losev, G. Z. Physik Chem. 59: 284-312.
1907.
(4) Freundlich, H. Adsorption and Occlusion. Z. Physik Chem.
61: 249. 1908.
(5) Freundlich, H. Theory of Adsorption. Z. Chem. Ind.
Kolloide. 3: 49-76. 1909.
(6) Travers, Morris W. Adsorption and Occlusion. Z. Physik
Chem. 61: 241. 1908.
(7) Wohlers, H. E. Adsorption Phenomena of Inorganic Salts.
A. Anorg. Chem. 59: 203-212. July 25, 1908.
(8) Michaelis, L., and Roa, P. Adsorption. Z. Chem. Ind.
kolloide. 4: 18-19. 1909.
(9) Reychler, A. Adsorption of Acids by Carbon. J. Chem.
Phys. 7: 497-505. 1909.
(10) Duclaux, Jacques. Adsorption of Gases by Porous Bodies.
Compt. Rend. 153: 1217. 1912.
(11) Geddes, A. E. M. Adsorption of CO2 by Charcoal. Ann.
Physik. 29: 797-808. 1909.
(12) Schmidt, G. C. Adsorption of Solutions. Z. Physik. Chem.
74: 689-737. 1912.
(13) Katz, J. R. Laws of Surface Adsorption and Potential of
Molecular Attraction. J. Chem. Soc. 104: 27. 1913.
(14)Langmuir, Irving. Theory of Adsorption. Phys. Rev. 6:
79-80. 1915.
-133-


PUNCH SUBROUTINES
TSWDA
RAL
V/DCTR
SET WORD
0650
65
0770
0825
SLO
THREE
COUNT AMD
0825
16
0678
0733
NZE
AVPIA
LOCATION
0733
45
0092
073 7
RAL
CNPWJ
OF FIRST
0737
65
0736
0641
SRT
0004
WORD IN
0641
30
0004
0651
SLO
TV/O
PUNCH ZONE
0651
16
0054
0059
ALO
V/DCTR
0059
15
0770
0875
LDD
1927
0875
69
1927
0080
S IA
1927
0080
23
1927
063 0
RAL
8001
0630
65
8001
0737
ALO
CDCST
ADD ONE TO
0787
15
0740
0845
5TL
1927
CARD COUNT
0845
20
1927
0680
PCH
1927
PUNCH
0680
71
1927
0627
STU
V/DCTR
ZERO WORD
0627
21
0770
0623
RAL
WDKTA
COUNTER
0623
65
0626
0081
LDD
CNPWD
0081
69
0636
0789
SDA
CNPWD
RESET
0789
22
0636
0839
LDD
CL2PG
ADDRESSES
0839
69
0002
0755
SDA
CL2PG
OF INSTRUC
0755
22
0002
0805
TIONS THAT
RAL
V/DKTB
STORE ANS
0805
65
0058
0863
LDD
CNPWI
IN PUNCH
0863
69
0757
0910
SDA
CNPWI
ZONE
0910
22
0757
0960
LDD
CL2PH
0960
69
0072
0925
SDA
CL2PH
AVPIA
092 5
22
0072
0092
PCHAA
RAL
CNPWJ
SETWORD
0700
65
0736
0691
SRT
0001
COUNT AND
0691
30
0001
0647
ALO
WDONE
COUNT AND
0647
15
0750
0855
SLO
V/DCTR
LOCATION
0855
16
0770
0975
SRT
0003
WORD IN
0975
30
0003
0783
ALO
8001
OF FIRST
0783
15
8001
0741
LDD
1927
PUNCH ZONE
0741
69
1927
0730
S IA
1927
0730
23
1927
0780
RAL
8001
ADD ONE TO
0780
65
8001
0837
ALO
CDCST
CARD COUNT
0837
15
0740
0895
STL
1927
0895
20
1927
0830
STU
TMCTR
ZERO TMCTR
0830
21
0034
0887
PCH
1927
R5ETA
PUNCH
0887
71
1927
0633


72-
a fortuitous circumstance, namely, that increased intra
particle resistance affects the adsorption wave shape
similarly to a decreased adsorbent selectivity, it was seen
that when intraparticle resistance contributes to the diffu-
sional resistance, computer solutions based on constant-
alpha equilibrium diagrams may correlate better than solution
using the true equilibrium diagram, if care is taken to use a
constant-alpha solution which is exactly equal to the value
of alpha at the feed composition. The latter restriction was
found to be required in order for the velocity of the calcu
lated ultimate adsorption wave to be correct. It is recog
nized that the use of constant-alpha diagrams in cases where
the external film resistance controls would probably result
in an incorrect wave shape.
The method proposed in this dissertation for evalua
tion of HETS was used on the data presented here with some
success. A correlation of HETS with liquid velocity through
the bed was obtained, but the indicated dependence of HETS
upon liquid velocity seemed high.
G, Discussion of Intraparticle Diffusional Resistance
Since the computed solutions of this work do not yield
an exact fit with data of large particle size adsorbent, the
next logical improvement in the method of analysis which was
used here would be to include in the basic equations a mathe
matical expression for the intraparticle resistance.


-67-
I
)
thru 200 mesh silica gel used by Lombardo was apparently
of a particle size small enough to permit the external film
resistance to control.
The values of KLa which best fit the computed curves
to the experimental data for the large particle size gel did
correlate with superficial liquid velocity, however, as seen
in Figure 24. It was gratifying to find that such a correla
tion was possible even though feed compositions of 0.1 volume
fraction toluene and 0.5 volume fraction toluene were used.
Apparently the intraparticle diffusional resistance was not
altogether controlling at these flow rates, since there was
an increase in effective KLa when the fluid velocity through
the bed was raised.
C. Toluene-Methylcyclohexane Adsorption on
Activated Alumina
Data for the adsorption fractionation of toluene and
MCH mixtures on activated alumina are plotted in Figures 21
and 22. There were no computer calculations made using the
equilibrium diagram of this system, so that there is no com
parison presented here between experiment and calculations.
It can be seen, however, that for the same feed compositions
and range of liquid flow rates as was used in the silica gel,
the sharpness of the fractionation, as measured by the shape
of the effluent curves, was better than that of the silica
gel.


174-
This dissertation was prepared under the direction
of the chairman of the candidate's supervisory committee and
has been approved by all members of that committee. It was
submitted to the Dean of the College of Engineering and to
the Graduate Council, and was approved as partial fulfillment
of the requirements for the degree of Doctor of Philosophy
in Engineering.
February 1, 1958
Dean, dDollegeof Engineering
Dean, Gradate School
SUPERVISORY COMMITTEE:
airman y'
n-rlini rmnn is
rman


-140-
using the SOAP II assembly program, translated the symbolic
program into a machine language program and punched out both
the symbolic and machine language programs into a fresh card
deck. This deck was used (after extensive "debugging") both
for printing the program and for reading the program into the
computer when it was desired to work the problem.
The steps followed in placing a problem into the
computer are described briefly below:
1. Read the entire program deck into the computer.
2. Provide the punch hopper of the computers read-punch
unit with fresh cards. (The read-punch unit should be
wired to punch and read eighty digits in normal order
on a card).
3. Place in the read hopper of the computer's read-punch
unit one or more "problem" cards. Each problem card
contains information as to the problem number, magnitude
of xjr, size of integration increment, and the frequency
desired in the punching of answer cards.
4. Place an instruction manually into the computer console
to read a card and proceed to location 1100 ( the first
instruction in the program).
5. Start the computer at the console instruction.


-137-
I
>
>
(60) Berg, Clyde. Hypersorption. Petroleum Eng. jL8: 115-118.
1947.
(61) Spengler, Gunter and Kaenker, Karl. Selective Adsorp
tion of Hydrocarbon Mixtures. Erdol U. Kohle
317-321. 1950.
(62) Lewis, W. K., and Gilliland, E. G. Adsorption Equilibri
of Hydrocarbon Mixtures. Inc. Eng. Chem. 42: 1319-
1326. 1950.
(63) Eagle, Sam, and Scott, John. Liquid Phase Adsorption
Equilibrium and Kinetics. Ind. Eng. Chem. 42: 1287-
1294. 1950.
(64) Weiss, D. E. Industrial Fractional Adsorption. Roy.
Australian Chem. Inst. Proc. 17: 141-156. 1950.
(65) Amundsen, Neal R. Mathematics of Adsorption in Bed II.
J. Phys. and Colloid Chem. 54: 812-820. 1950.
(66) Kasten, Paul R. and Amundson, Neal R. An Elementary-
Theory of Adsorption in Fluidized Beds. Ind. Eng.
Chem. 42: 1341-1346. 1950.
(67) Mair, B.J. Theoretical Analysis of Adsorption Fractiona
tion. Ind. Eng. Chem. 42: 1279-1286. 1950.
(68) Amundsen, N. R. Effect of Intraparticle Diffusion. Ind.
Eng. Chem. 44: 1698-1703, 1704-1711. 1952.
(69) Hiester, N. K. Performance of Ion-Exchange and Adsorp
tion Columns. Chem. Eng. Prog. 48: 505-516. 1952.
(70) Rosen, J. B. Kinetics of a Fixed Bed System for Solid
Diffusion Into Spherical Particles. J. Chem. Phys.
20: 387-394. 1952.
(71) Gilliland and Baddour. Rate of Ion Exchange. I.E.C. 145
No. 2. 330-337. Feb., 1953.
(72) Rose, Arthur, Lombardo, R. J., and Williams, T. J.
Selective Adsorption Computations with Digital Com
puters. I.E.C. 43: No. 11. 2454-2458. Nov., 1951.
(73) Lombardo, R. J. Prediction of Composition Changes and
Gradients in Selective Adsorption Columns. Ph.D.
Thesis, Penn. State Col., Dept, of Ch. E. 1951.


KLa (CA CA*) (AdLde) (pbVpA/Vm)(dy/d0)L(dLd0)
Here, CA represents the composition of the unad
sorbed bulk liquid phase, and CA* is the composition of the
liquid phase which is in equilibrium with the adsorbed phase.
Note the assumption that the resistance of the adsorption
process itself is negligible, so that CA* way be used in
the above equation.
Rearrangement gives:
CA CA* (Sy/ae)L
but by definition CA = x/Vra
substitution for CA gives:
x x* (Pbvp/KLa>(y/d0>L (2)
Equations (1) and (2), with the equilibrium x-y
relation for the system under consideration, represent the
mathematical problem to be solved, given suitable boundary
conditions.
Before attempting a solution, it is desirable to
transform equations (1) and (2) into a dimensionless form so
that a solution using a particular equilibrium relation will
be as general as possible, thereby permitting evaluation of
the solution without prior knowledge of such parameters as
fy, Pb, Vp, Q, A, and KLa. To effect such a transformation,
two new independent variables are chosen:


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INGEST IEID E2O1Y9EH9_QY9W7S INGEST_TIME 2016-05-25T21:57:46Z PACKAGE UF00089981_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES


-88-
TABLE 10
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F lc (cf. Figure 19)
Col. Diam. = 2.47 era.
Ave. Inverse Rate 12.73 sec./cc.
Wt. Gel. 45.35g. V
P
pb .679 g./cc. f
.402 cc./g.
.293
xF
0.500 Vol. fr. Sample Size
Toluene
7 drops
(except as
noted)
Sample No.
Time, sec.
Total Vol. x
Vol. Fraction
Effluent, cc.Toluene
1
.15
.196
2 (1 ml.)
0.70
.230
3

1.70
.255
4 "

2.70
.282
5

3.70
.300
6
4.70
.310
7
5.70
.330
8
-.
6.70
.342
' 9

7.70
.356
10

8.70
.367
11
--
30.70
.438
12
36.05
.448
13
41.40
.450


TABLE 7 (Continued)
Run No.
System
Adsorbent Column Diam.,
cm.
Wt. Adsorbent,
g.
Inverse Rate
sec./cc.
Xp
Feed Comp.
F-6b
tf
ft
tt
129.9
16
0.5
F-6c
It
tf
?
267.9
16
0.5
B-2(Lom
bardo)
Benzene-
N-Hexane
Thru 200
Mesh Silica
Gel
0.8
20
880
0.5
B-3
Tt
tt
tt
10
650
0.5
B-4
tt
tt
1.9
20
246
0.5
l
OD
cn
I


-64
system are presented in Figures 16, 17, and 18. The experi
mental data for each curve are listed in Tables 23, 24, and
25. These data which were published by Lombardo (72) were
the results of a Ph.D. thesis on adsorption fractionation.
Since the columns were long enough for the establishment of
the ultimate wave shape, the data were fitted to the calcula
tions by means of the ultimate wave shape. The calculated
curve at fi constant of Figure 12 v/as compared with the
experimental curves, and the value of I^a which best fit
each was chosen. The computed points using the chosen values
of K^a are also plotted in Figures 16, 17, and 18, and
curves are drawn through both the computed and the experi
mental data. It can be seen that there is good agreement
between the shapes of the computed and the experimental
curves. The values of K^a used are plotted vs. the super
ficial fluid velocity, Q/A, in Figure 24, curve A. It can
be seen that there was a good correlation between KLa and
the liquid velocity for the three runs.
B. Toluene-Methylcyclohexane Fractionation on Silica Gel
The effluent volume vs. composition curves for three
sets of fractionation experiments with the toluene-MCH-
silica gel system are shov/n in Figures 19, 20, and 21. The
experimental data for each of the nine runs are listed in
Tables 8, 16. A summary of all adsorption fractionation runs
is given in Table 7.


157-
SRD
0009
QUADRATIC
1028
31
0009
1101
ALO
DRFNW
CFPWF
METHOD
1101
15
0013
1617
CFPWF
STD
0101
CFPW3
1617
24
0101
0 704
CFPW3
RAU
8002
0 704
60
8002
1813
MPY
TI NCR
1813
19
0666
1586
SRD
0009
CFPWG
1586
31
0009
0809
CFPWG
ALO
0301
CFPW4
0809
15
0301
1755
CFPW4
STD
1932
CFPWH
1755
24
1932
1185
CFPVJH
STL
0301
TSTIM
1185
20
0301
0754
CONSTANTS
HLFAJ
05
0808
05
HLFAL
05
1148
05
HLFAM
05
0908
05
HLFAN
05
0774
05
HLFAP
05
1120
05
TEST'- TIME FOR PUNCHING
TSTIM
RAL
TMCTR
ADD ONE TO
0754
65
0034
1389
ALO
TMONE
TIME CTRS
1389
15
1190
1595
AUP
8001
AND TEST
1595
10
8001
1153
AUP
1934
FOR PUNCH
1153
10
193 4
1439
STU
1934
1439
21
1934
1737
STL
TMCTR
1737
20
0034
1787
SUP
8003
1787
11
8003
1645
SLO
TMCST
TSTMB
1645
16
1013
0622
TSTMB
NZE
STPCB
STPCA
0622
45
0826
0977
STPCA
STU
TMCTR
0977
21
0034
1837
RAL
SPCKA
1837
65
1390
1695
LDD
TSENC
1695
69
0679
1082
S IA
TSENC
1082
23
0679
1132
LDD
TSNWA
1132
69
0088
1241
SDA
TSNWA
1241
22
0088
1291
S IA
TSNWA
1291
23
0080
1341
RAL
SPCKB
1341
65
0944
0649
LDD
CL1PE
0649
69
0656
0859
S IA
CL1PE
0859
23
0656
0909
RAL
SPCKF
0909
65
0 812
1667
LDD
A VP IB
1667
69
0603
0706


Copyright hy
Adrain Earl Johnson, Jr.
1961

APPLICATION OF NUMERICAL METHODS
IN ANALYSIS OF FIXED
BED ADSORPTION FRACTIONATION
By
ADRAIN EARL JOHNSON, JR.
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
February, 1958

ACKNOWLEDGEMENTS
The author wishes to express his deep appreciation
and sincere thanks to Professor R. D. Walker, Jr., for his
encouragement, interest, and many suggestions during the
course of this investigation; to Mr. Carlis Taylor of the
University of Florida Statistical Laboratory for his very
valuable help in the preparation of the computer program and
in the obtaining of the computer solutions; to Dr. H. A.
Meyer for authorizing the use of the facilities of the
Statistical Laboratory and Computing Center for this work;
to Dr. Mack Tyner, Dr. T. M. Reed, Dr. E. E. Muschlitz, and
Dr. R. ,W. Cowan, of the graduate committee, for their help
ful suggestions and criticisms; to the faculty and graduate
students of the Department of Chemical Engineering for
their cooperation and interest; and to his wife for the
assistance and unwavering support which she has given.

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS i i
LIST OF TABLES v
LIST OF ILLUSTRATIONS vii
I. INTRODUCTION 1
II. BACKGROUND 3
III. PREVIOUS WORK 6
IV. THEORY 16
A. The Fixed Bed Binary Liquid Adsorption
Process 16
B. Derivation of Equations 21
C. The Dimensionless Parameters H and T 24
D. Boundary Conditions for the Liquid Phase
Fixed Bed Process 26
V. NUMERICAL ANALYSIS 29
A. Numerical Methods 29
B. Description of Integration Procedure 32
C. Computer Program 37
VI. RESULTS OF CALCULATIONS 40
A. Problem Solutions 40
B. The Asymptotic or Ultimate Adsorption Wave. 43
C. The Shape of the Asymptotic Wave 48
D. Computation of HETS From Fixed Bed Data.... 52
VII. EXPERIMENTAL 56
A. Adsorbent 56
B. Adsorbates .... 56
C. Experimental Procedures 57
iii

TABLE OF CONTENTS (Continued)
Page
VIII. COMPARISONS BETWEEN EXPERIMENTAL AND
CALCULATED RESULTS 62
A. Adsorption Fractionation Experiments of
Lombardo 63
B. Toluene-Methylcyclohexane Fractionation
on Silica Gel 64
C. Toluene-Methylcyclohexane Adsorption on
Activated Alumina 67
D. Use of Constant-Alpha Type Equilibrium
Diagram 68
E. HETS of Column Packing 69
F. Discussion of Calculations 71
G. Discussion of Intraparticle Diffusional
Resistance 72
IX. CONCLUSIONS 75
X. LIST OF SYMBOLS 131
XI. LITERATURE CITED 133
APPENDIX.- IBM 650 COMPUTER PROGRAM FOR SOLVING
ADSORPTION FRACTIONATION EQUATIONS 139
BIOGRAPHICAL SKETCH 173
iv

LIST OF TABLES
>

Table Page
1. Numerical Integration Formulae 77
2. Summary of Adsorption Fractionation Calculations.. 78
3. Determination of Specific Pore Volumes 80
4. Adsorption Equilibrium Data for Toluene-Methyl
cyclohexane on Davison 6-12 Mesh Silica Gel 81
5.Adsorption Equilibrium Data for Toluene-Methyl
cyclohexane on Alcoa 8-14 Mesh Activated Alumina.. 82
6. Adsorption Equilibrium Data for Benzene-N-
Hexane on Davison Thru 200 Mesh Silica Gel 83
7. Summary of Fractionation Experiments 84
8. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 86
9. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 87
10. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 88
11. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel !... 89
12. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 90
13. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 91
14. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 92
15. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 93
v

LIST OF TABLES (Continued
Table Page
16. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 94
17. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 95
i
18. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 96
19. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 97
20. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 98
21. Toluene-Mechylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 99
22. Toluene-Methylcyclohexane Fractionation on
Alcoa 8-14 Mesh Activated Alumina 100
23. Benzene-N-Hexane Fractionation on Davison
"Thru 200 Mesh Silica Gel 101
24. Benzene-N-Hexane Fractionation on Davison
"Thru 200" Mesh Silica Gel. 102
25. Benzene-N-Hexane Fractionation on Davison
"Thru 200" Mesh Silica Gel 103
26. Calibration of Refractometer for MCH-Toluene
Solutions at 30C 104
vi

LIST OF ILLUSTRATIONS
Figure Page
1. Flow Diagram of Computer Program 105
2. Liquid Phase Composition History, Computer
Solution to Problem 1 106
3. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 1 107
4. Liquid Phase Composition History, Computer
Solution to Problem 9 108
5. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 9 109
6. Liquid Phase Composition History, Computer
Solution to Problem 51 110
7. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 51 Ill
8. Liquid Phase Composition History, Computer
Solution to Problem 52 112
9. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 52 113
10. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 52 114
11. Liquid Phase Composition History, Computer
Solution to Problem 99 115
12. Ultimate Adsorption Wave Shapes, Computer
Solution to Problem 99 116
13. Adsorption Equilibrium Diagram for MCH-Toluene
on Davison 6-12 Mesh Silica Gel 117
14. Adsorption Equilibrium Diagram for MCH-Toluene
on Alcoa 8-14 Mesh Activated Alumina 118
vii

LIST OF ILLUSTRATIONS (Continued)
Figure Page
15. Adsorption Equilibrium Diagram for Benzene-
Hexane on Davison "Thru 200" Mesh Silica Gel.,.. 119
16. Benzene-Hexane Fractionation With Silica Gel.... 120
17. Benzene-Hexane Fractionation With Silica Gel.... 121
18. Benzene-Hexane Fractionation With Silica Gel.... 122
19. MCH-Toluene Fractionation With Silica Gel 123
20. MCH-Toluene Fractionation With Silica Gel 124
21. MCH-Toluene Fractionation With Silica Gel 125
22. MCH-Toluene Fiactionation With Alumina 126
23. MCH-Toluene Fractionation With Alumina 127
24. Effect of Liquid Velocity on Overall Mass
Transfer Coefficient 128
25. Effect of Liquid Velocity on HETS.. 129
26. Calibration of Refractometer for MCH-Toluene
Solutions 130
viii

I. INTRODUCTION
This dissertation describes the results of a study
made on the process of adsorption fractionation of binary
liquid solutions. Based on a theoretical analysis of the
factors controlling the process, mathematical partial dif
ferential equations expressing column operation were derived
and solved by numerical integration with the aid of an IBM
650 digital computer. Particular emphasis was placed upon
the statement of the boundary conditions for the liquid
adsorption process, as it is believed that the proper bound
ary conditions have not been used in previous work.
Computed solutions to column operation were com
pared with experimental data taken in this study and with
other published data. It was found that good agreement be
tween calculated and experimental data may be obtained in
systems in which the external particle film resistance to
diffusion apparently controls. Agreement in cases where
intraparticle diffusion contributes to the total diffusional
resistance is not as good, but is considered useful. The
success with the external film controlling case indicates
that when a suitable theory on intraparticle resistance is
derived, numerical integration by means of a computer will
prove the best means of obtaining satisfactory solutions,
-1-

-2-
because of the apparent impossibility of obtaining analytical
solutions to the equations.
It was found that, through a fortuitous circumstance,
computer solutions based on constant-alpha type equilibrium
diagrams fit the data for the case of intraparticle diffu
sion contributing more closely than solutions using the
actual equilibrium diagram of the system.
In the course of this work equations were developed
for determining the rate of advance and the shape of the
ultimate adsorption wave, which is formed in columns of
sufficient length. In addition, a method was developed for
evaluating the height of an equilibrium stage (HETS) in an
adsorbent bed from data of fixed bed adsorption fractiona
tion experiments. The determination of HETS is of importance
in the design of continuous countercurrent adsorption
columns.
This work also included the development of a com
puter program for solving the partial differential equations.
The resulting program and a brief description of the
numerical methods used are presented.

II. BACKGROUND
Historically, the most frequently encountered prob
lem in the chemical and related industries has been the
necessity of separating relatively pure materials from
mixtures of. two or more components, thereby producing either
finished products for sale or intermediate products to be
further processed. One portion of chemical engineering
science, the unit operations, is devoted entirely to the study
of the various methods for separating materials.
Research in the unit operations is usually aimed
either at the development of new, more economical, or more
exacting separation methods, or at the development of more
precise theories and formulae for expressing the phenomena
of the known methods so that they may be put to better use.
In the past decade, a new tool has been made available which
can help the scientist and engineer to investigate mathe
matical theories and methods in a manner undreamed of twenty
years ago. This tool is the high speed electronic computer,
digital or analog. Such machines have many capabilities,
but one of the most important to technical research is their
ability to solve complicated mathematical equations, both
algebraic and differential, which are otherwise insoluble.
In the past, many a theorist has been forced to
abandon a set of equations which he believed might express a
-3-

-4-
phenomenon because the solution to the equations could not
be provided by the most expert mathematician; instead, the
theorist resolved the difficulty by making restricting
assumptions about the process which simplified the equations
and permitted a solution. Such solutions are quite useful
in the design of a process, but they are always only approxi
mations. Sometimes their use leads to serious and costly
mistakes, not only in the design of industrial processes,
but in the interpretation of the phenomenon being investigated.
In June, 1957, an electronic digital computer, IBM
type 650, was installed at the University of Florida Sta
tistical Laboratory. This machine, with its auxiliary
equipment, represents the beginnings of a computing center,
which will be available to the University and the State on a
basis similar to that of the other facilities of the Labora
tory.
In anticipation of the installation of this computer,
the subject research was initiated in the field of chemical
engineering unit operations with the view of utilizing the
computer for providing a solution to equations which promise
to express a theory more precisely than previous treatments.
The unit operation chosen for a study was adsorption, which
is a relatively new entrant to the commercial field of large-
scale separation process. The "Arosorb" (1) and "Hyper
sorption" (2, 60) processes for the separation of petroleum
hydrocarbons are examples of commercial applications of

5-
adsorption.
The analysis of fixed bed liquid phase adsorption
fractionation is complicated by the fact that it is
inherently unsteady-state, or transient; partial differen
tial equations are required to express the process behavior
mathematically. The fixed bed adsorption fractionation
process, being mathematically complex and hence in an early
stage of treatment, was chosen for study with the dual
purpose in mind of advancing the frontier of knowledge in
this field and of demonstrating what the computer can mean
to research.

III. PREVIOUS WORK
In this section, the progress in adsorption research
is traced from the turn of the century to the present. In
general only those publications which deal with multicom
ponent adsorption equilibria or rate of adsorption are
discussed. However, any paper of unusual interest is also
mentioned.
1900-1920
The early investigators concerned themselves with
the nature of adsorption and with the equilibrium relation
ships of various systems of adsorbate and adsorbent.
Freundlich (3) proposed his now famous isotherm for correlat
ing the adsorption data of many systems. He was an early
exponent of the theory that adsorption is a surface pheno
menon (4), (5), which was not altogether accepted by the
scientists of his day. Travers (6) suggested that since
adsorption depends upon temperature it should be considered
a "solid solution" phenomenon; this was refuted by Wohlers
(7), who concluded that chemical bonds must account for the
process because the adsorbed material usually does not react
normally. Michaelis and Rona (8) suggested that adsorption
is caused by a lowering of the surface tension of the sol
vent by the adsorbent. Reychler (9) demonstrated that the
-6-

-7-
Freundlich isotherm was compatible with his own chemical
reaction theory; Duclaux (10) theorized that adsorption is
a result of differences in temperature which exist in minute
cavities of the solid, causing liquifaction. Many investi
gators, Geddes (11), Schmidt (12), Katz (13), Langmuir (14),
Polanyi (15), Williams (16), proposed equations different
from that of Freundlich. Some of these proposals were merly
the result of curve fitting, but others, such as those made
by Langmuir and Polanyi, were based on theories which ade
quately explain certain features of adsorption. By 1920,
when Polanyi introduced his equation, which utilized one
"characteristic" curve to account for the adsorption of a
vapor or gas under all conditions of temperature and pressure
of a given system, it was generally recognized that adsorp
tion may be explained by more than one theory, depending
upon the system, and may involve physical forces, chemical
forces, or a combination of both.
Theoretical analyses based on thermodynamic considera
tions became prevalent towards the last of this period;
speculations concerning the heat of adsorption were made.
Polanyi (17) discussed adsorption from the standpoint of the
3rd law, Langmuir (14) suggested that unbalanced crystal
forces account for physical adsorption, Williams (18) derived
an adsorption isostere equation from thermodynamic reasoning,
Lamb and Coolidge (19) concluded that the total heat of ad-

-8
sorption equals the heat of condensation plus the work of
compression. Very little was done with liquid adsorbates;
interest in vapor phase adsorption predominated. Gurvich
(20), however, noted that, on the same adsorbent and at
their own vapor pressure, approximately equal volumes of
various liquids were adsorbed.
One of the earliest investigations of the rate of
adsorption was performed by Berzter in 1912 (21). As with
most of the early studies, Berzter used a gas-air mixture,
from which he adsorbed the gas onto activated charcoal. He
fitted an empirical equation to his rate data without
determining the significance of the factors. Other inves
tigations of similar systems were made by Rakovskii (22),
Gurvich (23), who discovered that subdivision of the adsorbent
particles affected the rate of adsorption but not the ad
sorption equilibrium, Freundlich (24), Dietl (25), and Hernad
(26). Little was concluded from these studies except that
the velocity of batch-type adsorption decreased as the ad
sorption progressed, and that diffusion might play a role in
determining the rate.
1920-1930
The role of adsorption in catalysis was foreseen by
Polanyi, who in 1921 showed in a theoretical paper (27) that
adsorbents should by their nature accelerate chemical reac
tions, because of the reduction in the required activation

-9-
energy upon adsorption. However, Kruyt (28) disagreed; he
believed that adsorption should decrease the rate of reac-
tions because of the immobility of the adsorbed molecules.
An important concept was developed by Mathews (29)
who, in 1921, pointed out that the term adsorption should
properly be used to describe a phenomenon in which the con
centration of a substance tends to be different at the
interface between two phases from the concentration in the
main body of either phase, thus broadening the scope of
adsorption.
A typical early paper on kinetics was published by
Ilin (30), who proposed that the rate of adsorption of a
constituent from a gas in a batch process is proportional
to ek*:. Such a relation, although it may fit a set of data,
sheds little light on the factors which determine the
instantaneous rate of adsorption.
During the late 1920's interest was aroused in the
equilibrium relationships for a system in which the adsorbate
contains more than one component attracted by the adsorbent.
Levy (31), and Klosky (32) submitted equations for correlat
ing such data. These studies probably suggested the concept
that adsorption could be used to fractionate binary mixtures.
1930-1940
Additional equations for correlating the kinetics of
batch adsorption were proposed by Tolloizko (33), Constable

(34), Kondrashon (35), Ilin (36), Rogenskei (37), and
Crespi (38, 39), most of which were still rather empirical.
The idea that the rate depends upon the approach to the
equilibrium condition was appearing in various mathematical
forms in most of this work. A few workers began to consider
the kinetics as similar to those of chemical reactions,
requiring activation energies, etc. Taylor (40) approached
the subject in this manner; but Nizovkin (41) decided that
diffusion of the gases controls the entire process. Crespi
(42) derived a rate equation from Langmuir and Freundlich
isotherms which was also of the chemical kinetics type.
Later, Damkohler (43) showed that the Langmuir derived equa
tion applies only where establishment of the equilibrium
r
takes 10" seconds, otherwise diffusion of the material to
the adsorption site is controlling.
Brunauer, Emmett, and Teller published their impor
tant paper which dealt with the derivation of adsorption
isotherms on the assumption that condensation forces are
responsible for multimolecular layer adsorption (44). Sta
tistical mechanical approaches to the explanation of adsorp
tion equilibrium were presented by Wilkins (45) and Kimball
(46). Experimental studies of adsorption from binary liquid
solutions were performed by Ruff (47), Jones, et. al. (48),
and Kane and Jatkar (49).

11-
1940-1950
In 1940 Brunauer, Deming, and Teller (50) combined
the recognized live types of vapor isotherms into one equa
tion.
One of the first papers dealing with the kinetics of
adsorption in a column was that of Wilson (51) who developed
equations assuming instantaneous equilibrium, no void space
between particles, and a single adsorbed component. This
paper showed mathematically the existence of an adsorption
band which moves through the adsorbent column, and thus
quantitatively agreed with known facts. Martin and Synge
(52) pointed out the analogy between a moving bed adsorption
column and distillation. Mathematical equations were developed
for the steady state case to compute the number of equilibrium
stages required for a given separation.
DeVault (53) extended the work of Wilson by develop
ing differential equations and their solutions for single
solute adsorption which considered the void space between
particles. Differential equations for multiple solutes were
derived but not solved. There was reasonable agreement with
selected previously published data.
Thomas (54) proposed a kinetic theory which leads to
a Langmuir type isotherm at equilibrium. The adsorption
step was assumed to control with no diffusional resistance.
Solutions for the case of multiple solutes were impossible.

-12-
Amundsen in his first paper on the mathematics of
bed adsorption (55) developed differential equations based
on the assumptions of irreversible adsorption and a rate
proportional to the concentration of the adsorbate in the
gas stream and to the approach to equilibrium on the ad
sorbent. In a later paper he took into account the desorp
tion pressure exerted by the adsorbate.
In 1947 Hougen and Marshall (56) developed methods
for calculating relations between time, position, tempera
ture, and concentration, in both gas and solid phase in a
fixed bed, with the restriction that the adsorption isotherms
be linear. Analytical solutions of the partial differential
equations were obtained and plots of the solutions were made.
The interest in multicomponent adsorption equilibria
grew rapidly in the late 1940's. Many papers were published
for both gases and liquids showing isotherms for various
experimentally investigated systems, and various modifica
tions of the Brunauer, Emmett, and Teller isotherms were
proposed. Such papers were authored by Wieke (57), Mair (58),
Arnold (59), Spengler and Kaenker (61), Lewis and Gilliland
(62), and Eagle and Scott (63). Industrial applications
were described by Berg (60), who explained the Hypersorption
process for separation of light hydrocarbons, and by Weiss
(64).

-13-
1950 to Present
Since 1950 the mathematics of adsorption kinetics
have been even more intensively investigated. Amundsen and
Hasten (65, 66) have continued to approach the problem
analytically, mainly in the field of ion exchange, which is
closely related, but also in the field of adsorption. They
developed very complicated analytical solutions to the ad
sorption of gases in fluidized beds, assuming intraparticle
diffusion controlling and/or the adsorption process itself
controlling, but still restricting the equilibrium rela
tions to straight lines.
Eagle and Scott (63) presented extensive data for
equilibria of binary liquid systems and some batch kinetic
data, which permitted the evaluation of apparent diffusi-
vities within the particles of adsorbent.
Mair (67) treated fixed bed adsorption fractiona
tion as a distillation process, and developed design equa
tions utilizing a theoretical stage concept. Experimental
results were given for separation factors and for HETS.
Hasten and Amundsen (68) showed that in liquid
systems the rate is most often controlled by the diffusional
process instead of the adsorption process. They also
developed equations based on mass transfer and intraparticle
diffusion for a gas-solid moving bed adsorber, for the case
of one adsorbate, or multiple adsorbates assuming individual
isotherms for each. The effects of fluid phase resistance,

-14-
intraparticle diffusion, and adsorption resistance, on the
solution of the bed height required were shown.
Hiester (69) considered the performance of ion
exchange and adsorption columns mathematically. Approxi
mate solutions of mass transfer differential equations were
given which can be used to predict column behavior.
J. B. Rosen (70) published a solution of the general
problem of transient behavior of a linear fixed-bed system
when the rate is determined by liquid film and particle
diffusion.
Gilliland and Baddour (71) considered the kinetics
of ion exchange, wherein an overall coefficient representing
all resistances to transfer was used successfully, and pre
sented a solution to the partial differential equations
previously derived by Thomas. This is an isolated instance
where the equilibrium equation used was not restricted to
a straight line. Experimental data correlated very well,
so that use of experimentally determined rate constants pre
dicted the elution curves of other experiments satisfac
torily .
Lombardo (72) considered the problem of binary
liquid adsorption fractionation from the pseudo-theoretical
stage standpoint, and obtained solutions to the stepwise
equations which he proposed by means of a card programmed
calculator.

Hirschler and Mertes (1) performed experiments batch-
wise, similar to those of Eagle and Scott for liquid phase
binary adsorption. Internal diffusivities were computed
from the data.
Lapidus and Rosen (73), considering ion exchange,
developed equations similar to adsorption fractionation
equations, using a lumped resistance, and were able.to show
that an asymptotic solution usually exists. Solutions to
the asymptotic equation were obtained with a Langmuir type
isotherm.

IV. THEORY
It can be seen from the foregoing literature survey
that there has been some very creditable work done towards
the mathematical treatment of adsorption and ion exchange
kinetics, especially in recent years. Nevertheless, it
appears that there are enough variations in the different
phenomena of vapor phase adsorption, ion exchange, and liquid
phase adsorption to warrant a treatment based specifically
on the system being considered. The electronic computer is
best suited for individual treatment of a difficult problem,
since the results obtained by computer analysis are in the
form of numerical answers to the specific problem with par
ticular boundary conditions. To obtain general answers
comparable to an analytical solution, it is necessary to run
the problem repeatedly on the computer, varying the para
meters and boundary conditions each time, until enough
answers are computed to permit the drawing of graphs and
curves which present the desired coverage of the variables.
A. The Fixed Bed Binary Liquid Adsorption Process
The basic assumptions made to define the fixed bed
fractionation of a binary liquid are described below. These
are the conditions on which the calculations made in this
study were based. The following discussion points out the

-17-
conditions which are peculiar to the liquid phase process.
1. A constant composition feed liquid consisting only of the
two completely miscible components A and B, is fed at a con
stant rate into a column of solid adsorbent. The selectivity
of the adsorbent results in a gradual removal of A from the
liquid as it travels through the bed.
2. The velocity profile of the liquid flowing through the
column is assumed to be rod-like. [to promote this condition
experimentally, especially at the liquid front during the
filling of the bed, the liquid was fed through the adsorbent
column from bottom to top.]
3. The adsorbent is initially free of adsorbate liquid.
4. Equal volumes of pure A, pure B, or any mixture of the
two are adsorbed per unit of adsorbent; i.e. the pore volume
of the adsorbent is the same for both A and B.
5. Mixtures of A and B are volumetrically additive.
6. The activation energy of the adsorption process at the
surface of the adsorbent is considered small enough to per
mit the diffusion process to control the rate of adsorption.
7. The combined resistance to diffusion, consisting of both
the external surface film and an intraparticle resistance,
is considered together as one diffusional resistance, express
ible in the usual manner of the mass transfer "film' theory.
Items 1 and 2 above are standard with the fixed bed
adsorption process. The development of the theory has not

-IB-
progressed to the point that a better account of the velo
city profile of a fluid in a fixed bed can be made. This is
an item which could conceivably be included in a computer
^ analysis when a suitable fluid flow theory is available.
Item 3 is a deceivingly simple statement which needs
further discussion. In the gas phase process, which is used
as a model by almost every published paper on adsorption
fractionation, the bed is initially free of adsorbate, but
contains inert gas or carrier vapor. Since the bed is
initially already full of fluid, there is little effect of
the adsorption process upon the quantity of fluid flowing
while the bed is filling. The mathematical boundary con
ditions used to express this case state that when the feed
fluid reaches a given position in the bed the quantity of
adsorbate on the adsorbent is zero. In addition, the time
required for the fluid to reach a bed point is that required
to push the original gas out of the void space between the
adsorbent particles. Neither of these conditions is typical
of binary liquid adsorption. First, the time required to
fill the bed to a given point is that required to fill the
I void space and the pore volume of the adsorbent bed to that
point. Secondly, the composition of the liquid on the ad
sorbent at the foremost point of liquid penetration into the
bed continually changes as the filling "front progresses.
In a sufficiently long bed, the composition eventually

becomes zero with respect to component A, the more strongly
adsorbed component, but the length of bed required to arrive
at this condition is of importance. To the author's know
ledge, no treatment of the liquid phase process to date has
considered either of these two points. As will be seen later,
the development of the boundary conditions accurately
describing the binary liquid adsorption case is involved.
Item 4 has been shown to be true of liquid phase
adsorption in a great many instances, and is usually assumed.
It is particularly true of members of homologous series and
otherwise chemically related compounds. As a consequence
of item 4, it is generally convenient to assume item 5 also,
thus permitting compositions to be expressed in volume frac
tions rather than mole fractions.
Although some investigators continue to use a chemical
kinetics type of rate equation, it is generally accepted that,
as stated in item 6, diffusion controls liquid phase adsorp
tion processes.
The manner in which the diffusion is taken into
account is a topic of considerable interest. As stated in
item 7 the subject treatment assumes that the external and
intraparticle resistance can be lumped together as one over
all resistance. This admittedly is not as precise a theory
as desired; however, other investigators have not devised a
theory of intraparticle diffusion for liquid adsorption which
is acceptable to the author, nor has the author. One con-

-20-
troll i ng factor in this study was the limitation of the
storage capacity of the IBM 650 computer. It was found
that over 60 per cent of the machine capacity was required
to store the 'program, the sequence of instructions which
the machine follows to solve the problem. The remaining
storage was not sufficient to permit the addition of a third
independent variable, particle radius, to the other two,
time and bed depth. It would have been necessary to include
particle radius if intraparticle diffusion were treated as
a separate item. The required storage is available on larger
computers, however. Based on the results of the computations
of this study, it now appears that particle radius might
have been handled with the IBM 650, if the ranges covered by
the other two variables, time and bed depth, were suitably
restricted.
All analytical solutions which have been published
to date have of necessity each been based on a particular
form of the adsorption equilibrium relationship, which
expresses the relation between x, the composition of the
unadsorbed liquid phase, and y, the composition of the ad
sorbent-free adsorbed phase. This diagram is similar in
appearance to the usual vapor-liquid equilibrium diagram.
Because of the extreme difficulty in solving the equations,
most have assumed a straight line relationship, which is
strictly applicable only to dilute gas phase adsorption.

-21-
The Langmuir equation, (y x/a+bx) has been used for an
approximate solution, assuming chemical kinetics to be the
controlling rate. Neither of these forms expresses satis
factorily the equilibrium of liquid phase adsorption over a
very wide range. In fact, usually no one algebraic expression
fits adsorption equilibria over the complete diagram. It is
quite often necessary to fit two or more algebraic expressions
to liquid phase adsorption equilibrium data. Because of this
an analytical solution cannot be generally applicable to
different systems. Moreover, an analytical solution is very
complex, even when based on the simplest straight line
equilibrium relation. The computation of the infinite series
which usually result in analytical solutions could easily
require a computer. It is of importance that a computer
solution can be obtained no matter how complex the equilibrium
relationship, thus "tailoring" the solution to the particular
system under study, and thereby removing a basis for conjec
ture when comparing the calculated solution v/ith the experi
mental results.
B. Derivation of Equations
A material balance (using volume fraction composi
tions) for component A, the more strongly adsorbed component,
can be made over a differential section of the adsorption bed.
Equating the loss from the fluid stream to the gain by the

-22-
adsorbed and unadsorbed phases
d(Qx)
- ran
e
dLrdg
+ AdLdg
rearranging gives:
(dx/dL)g + (Afv/Q)(dx/dg)L
+ (Sy/c)0)l J
- (PbVpA/Q)(dy/de)L
(1)
which is the equation of continuity written in volume
fractions.
The classical mass transfer rate equation for dif
fusion of component A between phase 1 and 2 across a film
whose area per unit volume of bed is unknown is,
rA -= KLa (CAl CA2)
for equimolar countercurrent diffusion of components A and B.
It is assumed that the conditions of equimolar
countercurrent diffusion are approximated closely enough by
the adsorption process, in which component B is displaced by
component A, to permit this form of mass transfer equation
to be used. The coefficient, Kj^a, is assumed to remain con
stant as CA varies. Thermodynamically, it is possible that
the coefficient, K^a, would be more constant if based upon
activities instead of molar concentrations; use of the above
equation may assume ideal solutions. If such is true, a
further refinement would be to include the activity coef
ficient in the above relation.
Writing the mass transfer rate equation for a
differential section of an adsorption bed,

KLa (CA CA*) (AdLde) (pbVpA/Vm)(dy/d0)L(dLd0)
Here, CA represents the composition of the unad
sorbed bulk liquid phase, and CA* is the composition of the
liquid phase which is in equilibrium with the adsorbed phase.
Note the assumption that the resistance of the adsorption
process itself is negligible, so that CA* way be used in
the above equation.
Rearrangement gives:
CA CA* (Sy/ae)L
but by definition CA = x/Vra
substitution for CA gives:
x x* (Pbvp/KLa>(y/d0>L (2)
Equations (1) and (2), with the equilibrium x-y
relation for the system under consideration, represent the
mathematical problem to be solved, given suitable boundary
conditions.
Before attempting a solution, it is desirable to
transform equations (1) and (2) into a dimensionless form so
that a solution using a particular equilibrium relation will
be as general as possible, thereby permitting evaluation of
the solution without prior knowledge of such parameters as
fy, Pb, Vp, Q, A, and KLa. To effect such a transformation,
two new independent variables are chosen:

Let T
(3)
(4)
-24-
- and H (KLaA/Q)(L)
The resulting transformation equations are,
(dy/c)0)L 13 fy/dT)jj(Kba/pbVp)
tix/de )h (x/dT)H(KLa/pbVp)
(dx/^L)e -(AfvKLa/QpbVp)(ax/3T)H + (KLaA/Q) (^x/^H)T
Substitution of these relations into equations (1) and (2)
gives,
(px/dH)T = -(dy/dT)H (5)
x x* = (ay/dT)H (6)
Equations (5) and (6) together with the x-y equilibrium
relationship, express, in the desired dimensionless form, the
mathematical relations which the adsorption process obeys,
according to the assumptions listed originally. A solution
of these equations, based on the proper boundary conditions,
should be correlatable with experimental data. It should be
noted that all of the physical properties involved in defin
ing H and T are readily measured experimentally except KLa.
The evaluation of KLa must hinge upon the matching of the
calculated solution with experimental data.
C. The Dimensionless Parameters H and T
It is important to the statement of the boundary
conditions and to the understanding of the results of the
calculation that the physical significance of the dimension
less parameters, H and T, be understood. Multiplication of

-25-
bo th sides of equations (3) and (4) by (pbVp/KLa) gives,
(PbVp/KLa)(T) 9 (Afv/Q)(L) (7)
(pbVp/KLa)(H) (ApbVp/Q)(L) (8)
The net dimension of both sides of equations (7) and
(8) is time. A study of the right hand side of these equa
tions will revel the following interpretation of T and H.
The parameter T is proportional to the actual time
elapsed since introducing feed liquid into the adsorption
bed in excess of that which is required to fill the void
volume of the bed to point L by the feed flow rate Q.
The parameter H is proportional to the time that
would be required to fill the adsorbed phase volume of the
bed to point L by the feed flow rate Q. The proportionality
constant is the same as the one for T.
An alternate way of expressing the above would be to
state that T is proportional to the volume of liquid which
has entered the bed in excess of that required to fill the
void volume to point L, and H is proportional to the volume
of liquid which is required to fill the adsorbed phase (pore)
volume of the bed to point L.
Some reflection will show that for a given bed depth,
L, if H *=> T, then the liquid front has just reached point L
and both the void and pore volumes of the bed are filled to
the point L.

-26-
D. Boundary Conditions for the Liquid
~ ^Phase Fixed feed Process
Inspection of equations (5) and (6) shows that there
are two dependent variables, x and y, and two independent
variables H and T. Only first order partial derivatives are
present, suggesting that only two boundary conditions, one
fixing x and one fixing y along two different axes, will
suffice. Physically, it can be seen that for a given bed
and given flow rate, the inlet feed composition and the
initial condition of the bed determine the resulting column
operation. Since the properties of the bed, the flow rate,
etc., are contained within H and T, they need not be con
sidered mathematically.
The condition of constant inlet feed composition
corresponds to the condition that at L = 0
x xy, for all 6 > 0
This is easily converted to the dimensionless system by
the condition
at H O
x = Xp, for all T ;>_ O
In other papers, the second boundary condition has
been met by considering that at T = 0
y 0, for all H > 0
which is equivalent to the physical case of a bed saturated
at 0 0 with a liquid of composition pure B. This would
insure that y * 0 initially, and that when the feed liquid

front arrives at point L by pushing out the liquid in the
void volume of the bed, the composition, y, of the liquid on
the adsorbent is zero. This, however, is not the case for
an initially dry bed.
For the initially dry bed, it was seen above that the
instant of filling corresponds to T = H. It then will suffice
to state a boundary condition for y along the boundary T = H,
if possible. Considering the physical problem, as a given
adsorbent particle fills, there are two extreme cases which
may occur. The liquid phase and the adsorbed phase at the
moment of filling may be in complete equilibrium, indicating
that diffusion of components A and B happened more rapidly
than the filling; or, the other extreme, the liquid phase and
the adsorbed phase may be of the same composition at the
moment of filling, indicating that the diffusion process is
very slow compared to the rate of filling. In actual fact,
it is of course probable that the physical process which
occurs is somewhere between the two extremes, depending upon
the filling rate. However, for lack of a better criterion,
it is certainly more probable that in the majority of cases
the diffusion rate is quite slow compared to the filling rate.
It has been shown (73) that each individual particle takes
something on the order of one minute or more to come to
equilibrium in batch experiments, and the filling process,
even in the smallest columns, is completed at the rate of
many, many particles per minute.

-28-
The boundary condition chosen in this study, based
on the above observations, is
for T = H, all T and all H > 0
x = y
which expresses mathematically that as each particle in the
bed fills, the rate of diffusion of components A and B is
negligible compared to the filling rate. Note that such a
boundary condition is not easily applied when attempting
an analytical solution to a set of equations, but, as will
be seen in the description of the numerical method, it pre
sented no insurmountable problem in computer analysis.
)

V. NUMERICAL ANALYSIS
A. Numerical Methods
The general procedure for solving differential equa
tions by means of numerical techniques is covered by many
texts.
To solve a partial differential equation or equa
tions, it is necessary to substitute, in effect, a set of
simultaneous differential equations, which are integrated
numerically and simultaneously by standard numerical tech
niques. The voluminous number of computations required and
the quantity of numbers to keep track of during the integra
tion make it imperative that the modern high speed computer
be used when dealing with partial differential equations.
The adsorption problem can be demonstrated graph
ically in the following manner.
29-

-30-
The two sketches portray the three dimensional pic
ture of the desired relationships. The surface, x x(T,H)
and the surface y * y(T,H) represent the functions which
satisfy the partial differential equation and its boundary
conditions. Along the boundary H = O, x is shown to be con
stant, xF, the feed composition. Also along this boundary,
y increases from xjr, its initial value as the first drop fills
the first section of the column, to yF*, the value in equi
librium with the feed. Along the boundary H = T, both the
x and y surfaces follow the same curve, as prescribed by
the second boundary condition. The general shape of the
curve is known before hand, but the actual boundary condi
tion is merely that x = y. The values of the two function
between these two boundaries make up the surfaces represent
ing the solution to the problem.
A rectangular grid has been superposed at the base
of the figures. This grid represents the finite values of
H and T at which the numerical solution provides values of
x and y. As the grid is made smaller the resulting numeri
cal solution will approach the true solution very closely,
but also many more points must be computed. In this problem,
capacity was available in the computer to compute values for
a grid composed of 200 T and 200 H points. From the sketch
one can see that this would involve the computation of x and
y for a total of 20,000 grid points each time the problem is
worked. As the computer required about four seconds to

-31-
compute each point, the computer time required would have
been prohibitive, except that it was found unnecessary to
compute all of the points. Since the physical problem is
such that an adsorption "wave" is formed in both the liquid
and adsorbed phases, and that this "wave" moves through the
column, there are a great many points before and behind the
wave whose composition is fixed. In front of the wave is a
section of the column containing pure B, where both x and y
are zero; behind the wave is a section of a column in which
the liquid composition is Xj, and the adsorbed phase compo
sition is yp*, the value in equilibrium with the feed liquid
composition. In both of these sections no mass transfer
takes place, and it is not necessary to compute changes in
the values of x and y. This fact was incorporated into the
computer "program," and the computer did not bother to com
pute values for x and y outside of the wave itself. The
criteria chosen for the wave boundaries were that a point
was considered inside the wave whenever the compositions of
the point immediately adjacent to it were such that either
y 0.00005 or xp-x > 0.00005. A check computation made with
out these restrictions revealed that the results of the
solution were not affected within four significant figures,
which was considered sufficient precision. This maneuver
cut the computation time down to 5-10 hours per solution.

-32-
B. Description of Integration Procedure
n m h h m n
ill + + +
t-j t-j t-j -r-j -r-j -r-j -r-j
i-2
-i-1 H
i
(
)

i+1
i 4-9

T
The numerical integration procedure can be described
as follows:
Given the value of (x,y)ij for a particular grid
point, (i,j), (see sketch above) within the desired H and T
boundary, x x* at this point may be computed from the
equilibrium x y relationship. From equations (5) and (6),
p. 24, the partial derivatives (Sx/ctH)x and (y/dT)n at
(i,j) should equal -(x x*) and ( x x*^ respectively.
The value of x at the neighboring grid point (i+l,j) may be
estimated by a suitable formula for numerical integration.
The simplest formula is that used by Schmidt in heat trans
fer calculations, which consists of assuming that (dx/0H)T
is constant between the point (i,j) and the point (i+l,j).
To put it more elegantly, a straight line may be fit over
the AH increment from (i,j) to (i+l,j) utilizing the value
of x and the slope, (c5x/c>H)T, both evaluated at (i,j).
Similarly, the value of y at the grid point (i,j+1) may be

-33-
computed by fitting a straight line over the AT increment
from (i,j) to (i,j+l) utilizing the slope C5y/dT)n and value
of y at the point (i,j). However, this is the crudest of the
numerical integration formulae. For the resulting solution
to be even approximately close to the true solution, it is
necessary to use very small AH and AT increments. If inte
gration formulae be used which fit higher degree polynomials
to the curve in the neighborhood of the point (i,j), the
precision of the integration process is vastly improved, and
much larger AH and AT increment sizes can be used.
It was decided, by trying alternate integration
formulae on the computer, that, to obtain the degree of pre
cision required and yet cover a large range of the H and T
variables with the 200 increments allotted, it would be
necessary to use integration formulae which fit at least
second degree polynomials to each integration step. The
formulae used are listed in Table 1.
Formula number 1, which fits a second degree poly
nomial over two increments, was used to compute values of y
at points corresponding to (i,j+l) in the sketch. This equa
tion requires no trial and error. Formula number 2, which
fits a third degree polynomial over two increments (thus
requiring a trial and error solution) was used to compute
values of x at points corresponding to (i+l,j) in the sketch.
Two different formulae were used simply because it was

-34-
impractical to fit a third degree equation in both direc
tions, as a double trial and error procedure would have
been required. Use of such a double trial and error proce
dure would have increased the computing time by a factor of
about 20. It was, therefore, necessary to compute in one
direction without a trial and error procedure, and the T
direction was arbitrarily chosen.
The above discussion holds for the computation of
all "normal" interior points; however, for points near the
boundaries T 0 and T H different formulae were required
to maintain at least second degree precision for all cal
culations .
It is of interest to describe in detail the first
few steps in the computation of a solution, so that an
accurate picture of the manner in which the boundary condi
tions were applied may be seen. The procedure followed in
starting a numerical integration is outlined below:

-35-
1. Refer to the above sketch of the H and T axis with the
superposed grid. At T 0 and H 0, both x and y were set
equal to xp, the feed liquid composition. This corresponds
to the condition that the first differential layer of parti
cles in the column is filled with feed liquid in both void
and pore volume.
2. The value of x for points 1, 3, 6, 10, etc., was fixed
equal to xp. This meets the boundary condition that x is
always Xp at the column inlet.
3. The value of y at grid number 1 was computed first, using
integration formula number 3, Table 1. This formula fits
by trial and error a second degree curve over one increment
to the desired relationship that dy/dT x x* at constant
H. The equilibrium relationship must of course be used to
compute x* from values of y.
4. The value of both x and y at grid point 2 was computed
next using integration formula number 4, since x y along
the H T axis. This computation is also trial and error,
fitting a second degree equation over one increment to the
desired relationship that dx/dH -(x x*) at constant T.
5. The value of y at point 3 was next computed using inte
gration formula 5 which fits a third degree equation over
two increments. All subsequent values of y along the H 0
axis were computed by this formula.
6. The values of x and y at point 4 were next computed by
trial and error simultaneously using formulae 4 and 6, which

-36-
fit second degree equations over one time increment. Since
it was desired to fit at least second degree equations in
every integration step, the simultaneous calculation of
x and y for this point was required.
7. The value of x and y (equal) for grid point 5 was com
puted using formula 2, which fits a third degree equation
by trial and error over two time increments. All subsequent
points along the H * T diagonal were calculated using this
formula.
8. The value of y at point 7 was computed by formula 1,
which fits a second degree equation over two time increments
without trial and error. This is the first instance in which
formula number 1, for a "normal" point, was used.
9. The value of y at point number 6 was computed by formula
5.
10. The value of x at point 7 was computed by formula 4,
which fits a second degree equation by trial and error over
one increment. All subsequent values of x along the H AH
axis were computed by formula 4.
11. Values of x and y at point 8 were computed simultaneously
in order to use at least second degree equation accuracy.
Formulae 2 and 3 were used, involving a double trial and
error. All subsequent values of x and y along the diagonal
neighboring the H * T diagonal were computed with these
formulae. This is the only instance of double trial and
error involved.in this procedure.

12. The value of x and y (equal) for grid point 9 was
computed by formula 2.
13. Subsequent calculations proceeded, using formula 1 to
compute values of y, and using formula 2 to compute values
of x for all normal interior points. Points on and neighbor
ing to the boundaries H ~ 0 and H T were calculated as
noted in steps 5, 7, 10, and 11.
C. Computer Program
The development of a computer program to perform
the computations described above was a tedious, drawn-out
process rife with rewrites and changes in procedure. The
IBM programming procedures first had to be learned, largely
from the manuals available for this purpose, but with a good
deal of help from the University of Florida Statistical
Laboratory personnel. The specific programming method chosen
was the IBM SOAP II method, developed for the Type 650
machine. The program itself is much too long and complicated
to be discussed here, although a complete copy of the SOAP II
program is included in the Appendix. The SOAP II procedure
has the advantage that the program is listed in a symbolic
code as well as the numerical machine code. The printed
program also includes comments inserted specifically to help
orient the operator as to the calculations being performed
in each particular section of the program. In Figure 1 a
"Flow Diagram" of the program is presented. It must suffice

-38-
to point out here that if the program as listed in the
Appendix be punched into standard IBM cards according to
the SOAP II format, and if the instructions accompanying
the program be followed, any competent 650 operator could
utilize this program to solve a binary liquid phase adsorp
tion fractionation problem, limited, of course, to the basic
assumption as to the mechanism involved on which the v/ork
was based. The program listed in the Appendix uses the alpha-
type equilibrium diagram familiar to distillation processes.
To work a problem, it is necessary only to read the program
into the Type 650, then to read in one problem" card, v/hich
provides the information as to the feed composition, magni
tude of alpha, size of the AT and AH increment, and frequency
desired in the punching of the answer cards. The computed
answers are punched by the machine at pre-determined incre
ments of AT, chosen arbitrarily for each problem on the
problem card.
If it is desired to perform a calculation using the
equilibrium diagram of a specific system, as was done in this
work, a sub-routine for computing x* from y must be added to
the program listed here in such a way that it replaces the
equilibrium diagram calculation of the listed program. Again,
this is a fairly simple task for an experienced IBM programmer.
The author will be glad to furnish additional information
other than that given herein to enable any interested party
to make use of the program. Although the development of the

-39-
program represents some four to six months of intensive
effort, it, like any other computer program, is now
available for future use at any time.

VI. RESULTS OF CALCULATIONS
A. Problem Solutions
The numerical solution to the binary liquid adsorp
tion fractionation problem was run twenty-three times on
the IBM 650 computer. Each time the problem was solved,
there were two parameters which were subject to change.
These were the composition of the feed liquid, xjp, and the
shape of the x-y equilibrium diagram relating the composi
tion of the adsorbed and unadsorbed phases at equilibrium.
The latter parameter actually consists of one or more equa
tions which express the x-y relationship over the range
x O to x = 1. These equations were included as a sub
routine of the computer program, and to make a change it was
merely necessary to place in the deck of program cards the
proper subroutine deck for the x-y relationship desired.
The problems which were computed are summarized as
to the parameters used in each solution in Table 2. Four
of the solutions were run for comparison with experimental
data of Lombardo (73) (Benzene-Hexane fractionation on
Silica gel) and with experimental data of this study (Toluene-
Methylcyclohexane on Silica gel). The remaining solutions
were run to provide a set of curves for use in evaluating the
effect of the parameters on column operation. This latter
-40-

-41-
group of nineteen solutions was based on a constant-alpha
type of equilibrium diagram as is used in correlating vapor-
liquid equilibria of distillation systems. In adsorption,
alpha is defined exactly as in distillation: (y/l-y)
(1-x/x) -a Although adsorption equilibria seldom cor
relate perfectly with a constant alpha, this is one of the
few algebraic formulae which approximate the general shape
of the adsorption x-y diagram over the complete range. It
was believed that a set of solutions based on the constant-
alpha equation should prove useful in interpreting the effect
on column performance of varying the two parameters, and it
was hoped that solutions obtained with constant-alpha dia
grams which approximate the experimental equilibrium data
might be used successfully to predict column performance.
The answers to the solutions were punched by the
computer onto standard IBM cards as they were calculated.
Each card contained six answers plus identifying informa
tion. The six answers were actually three sets of x and y
values corresponding to three bed grid points (H) at a given
time increment (T). To provide enough answers to draw smooth
curves through the points, it was not necessary to punch out
x and y values for every one of the grid point intersections.
In fact, this was not desirable at all, because the relative
change in the values of x and y between adjacent grid points
was quite small (in numerical integration this is a necessary
prerequisite for accuracy). Usually the choice was to punch

-42-
out answers for every tenth dimensionless time (T) incre
ment. The entire adsorption wave was punched out at this
time increment, but, as explained before, the constant
composition sections in front of and following the wave were
not punched.
The information from the cards was then printed in
list form by means of an IBM 403 tabulating machine. From
these lists of calculated data points, graphs of the solu
tion were prepared. It was found that there were three
graphs required to portray the information from each solu
tion. On one, values of x, the liquid phase composition,
were plotted against H, the dimensionless bed depth para
meter, along lines of constant T, the dimensionless time
parameter. A second plot was required to give the same
information about y, the adsorbed phase composition. A
third plot was made of the ultimate, or asymptotic, wave
shapes which are reached by the adsorption wave as it travels
down the bed. Typical graphs of problem solutions are shown
in Figures 2-11. Only those solutions referred to in this
dissertation are shown. The tabulated data from which the
graphs were computed were much too voluminous to include here.
It is planned to compile the data and graphs for all of the
twenty-three solutions under a separate cover for ready
reference.
It was found that in every problem solution an ulti
mate wave shape was formed provided sufficient distance along

-43-
the bed depth parameter H was covered. Several authors have
discussed the existence of the adsorption wave, and some have
speculated upon the conditions or requirements that an ulti
mate or invariant shape be formed. The discovery that an
invariant wave shape was formed in these problem solutions
prompted a further analysis of the conditions necessary for
its formation.
B. The Asymptotic or Ultimate Adsorption Wave
It is an experimental fact that if an adsorption
column is long enough (and if there is no adsorption azeo
trope) eventually there will be set up three distinct zones
which travel through the column. Refer to the following
diagram.
Bed Depth, L

-44-
In zone 1, the adsorbent has preferentially adsorbed
component A from the liquid phase passing over it until the
composition of the adsorbed phase has reached the compo
sition in equilibrium with the feed. When this occurs, there
is no tendency for further exchange of material between the
two phases, and XF is also constant in zone 1. In zone 2,
mass transfer is taking place, and the composition of both
y and x vary with bed depth, L, and with time, 0 Zone 2
is the adsorption wave. However, the continual removal of
component A from the liquid phase as it travels through the
bed eventually becomes complete, and the composition of the
liquid at the head of the wave becomes zero with respect to
component A. Zone 3 represents the portion of the bed over
which pure component B is passing. As in zone 1, there is
no tendency for mass exchange between the phases and compo
sitions are constant with 0 in this section. Remember, how
ever, that all three zones are traveling through the column.
Although these three zones will be formed in any
adsorption fractionation experiment (with the exception of
azeotropes), the questions of importance are (1) How soon
will the three zones be formed? (2) V/hat is the width of
zone 2? (3) Does zone 2 reach an ultimate non-changing shape?
(4) If so, at what rate does zone 2 travel through the
column?

-45-
The numerical solutions obtained with the IBM 650
in this work provided the answers to these questions in each
case investigated, but did not shed light upon other cases,
e.g., equilibrium diagrams of different shape from those
studied here. This, admittedly, is one of the main draw
backs to numerical solutions.
If one starts with the assumption that a zone 2 of
non-changing shape is formed, its velocity may be calculated.
Since zone 3 is continually building up in length as the
adsorption progresses, zone 2 must move through the column
at a rate slower than the rate that the liquid passes through.
Therefore, if we imagine a column in which the adsorbent is
made to move in the opposite direction from the liquid, there
is a certain rate of adsorbent movement which will cause
zone 2 to remain stationary. There is, then, a counter-
current moving bed which is exactly analogous to the fixed
bed operation. See the following diagram.
Countercurrent Case
Zone 2 Stationary
w £ *
y-0 t x-0
Fixed Bed Case
Zone 2 Moves-
y-yf* x-xy

-46-
If Q is the volumetric flow rate of the liquid
through the stationary bed, Q/Af is the velocity of the
liquid through the bed void volume. This velocity would
have to be reduced by an amount equal to the velocity of
travel of the adsorbent in the countercurrent case, in order
to maintain the same relative velocity of fluid through the
bed in the two cases. If W is the mass rate of flow of ad
sorbent required to maintain zone 2 stationary, W/p^A is the
velocity of the adsorbent through the bed. Therefore, the
countercurrent liquid feed velocity may be related to the
fixed bed velocity.
Q' /Af v = Q/Afy W/^A (9)
where Q' represents the volumetric liquid
feed rate in the countercurrent case.
and Q represents the volumetric liquid
feed rate in the fixed bed case.
A volumetric material balance on component A about zone 2 for
the countercurrent case gives,
(WVp)yF* (Q)(xf) (10)
Substituting for Q' from equation (9),
(WVp)yF* (Q fvW/pb)(xF) (11)
A little study will show that the velocity of the wave, VWj
when the liquid feed rate is Q, is equal to the velocity of
the adsorbent bed required to maintain zone 2 stationary when
the liquid feed rate is Q'. Solving equation (11) for W/pbA,
the adsorbent bed velocity, gives,

-47-
vw JL. ...... *gfy.. (Q/Afv)
pbA (Xpiy + VppbYp*)
(12)
Therefore, equation (12) above gives the velocity of the
wave traveling through a bed, based on the assumption that
a wave of invariant shape is formed.
It is desirable to transform this velocity into a
velocity in terms of the dimensionless parameters H and T.
Vw may be considered as the ratio of AL/A0 which is required
to maintain a given x or y composition in the wave constant.
Similarly, the adsorption wave velocity in dimensionless
parameters would be the value of the ratio of aH/aT corre
sponding to V\V. This transformation may be obtained by
substituting for AH/aT using equations (3) and (4), which
define T and H in terms of 0 and L.
AT (KLa/pbVp)(AS) (KLaAfv/QpbVp)(AL) (13)
AH (KLaA/Q)(AL) (14)
From (13) and (14),
AT/AH (Q/ApbVp)(A0/AL) (fv/PbVp) (15)
Therefore, designating the wave velocity in terms of the
dimensionless parameters as Vwcj,
1/Vwd (Q/ApbVp)(l/Vw) (f/pbVp) (16)
Substitution for Vw from equation (12) above, yields the
simple relation,
vwd xF/yF* (17)
Equation (17) points out that the velocity at
which the adsorption wave moves through the column in terms

-48-
of the dimensionless parameters is merely the ratio of the
feed liquid composition to the adsorbed phase composition in
equilibrium with the feed. Note that the physical properties
of the bed do not enter into the relation. This relation can
be verified readily by inspection of the calculated solu
tions (Figures 2-10) to the adsorption fractionation problem.
In every case, after sufficient bed depth H was reached, the
wave reached an ultimate shape and a velocity, AH/AT, which
JL.
equalled xp/yp .
C. The Shape of the Asymptotic Wave
The concept of a stationary wave maintained by a
movement of the adsorbent bed countercurrent to the liquid
flow can also be utilized in computing the ultimate wave
shape. Consider again a diagram of the liquid and adsorbed
phase composition plotted vs. bed depth, L, for the counter-
current bed, and assume that the wave is being maintained
stationary by appropriate flow of the liquid and adsorbent.
Bed Depth, L

-49-
A volumetric balance for component A over section dL yields,
(dy/dL)WVp)(dL) (dx/dL)(Q*dL) (18)
Note that total differentials may be used since the wave is
assumed to be stationary. Rearrangement and integration
between limits gives,
0 0
This integration is easily performed, so that,
yF*/xF Q/WVp (19)
Equation (19) relates the flow rates required for main
tenance of the stationary bed to the feed liquid composition
and equilibrium adsorbed phase composition. Equation (19)
is equivalent to equation (12); note that Q is used in the
former and Q in the latter. If the upper limit of the above
integration be made indefinite, there results,
y (Q'/WVp)x (yFVyF)x (20)
Equation (20) points out the relation that must hold between
y and x at a given point in the adsorption wave, if the
wave is to become invariant, as was assumed. This, then,
places a restriction upon the shape of the equilibrium x-y
diagram which will permit an adsorption wave of ultimate
or invariant shape to become established. Consider the
following diagram.

-50-
x
The straight line OA, which connects the origin with the
equilibrium curve at the point representing the feed condi
tion, can be thought of as the operating line for this process.
Everywhere along the invariant adsorption wave, whether the
wave is stationary or moving down the column, x and y for a
given bed point at a given instant must fall on the line
OA, that is obey equation (20). This relation may also be
verified by referring to any of the calculated curves for the
ultimate wave shapes (Figures 2-10).
It is apparent that if the equilibrium curve were to
cross the line OA, then the liquid and adsorbed phase compo
sitions could not possibly follow line OA. Hence, a require
ment for the formation of an invariant adsorption wave is
that the equilibrium diagram may not cross the operating"
line connecting (xjr,yF*) with the origin.

-51-
Further information about the invariant wave may
be derived by equating the rate of mass transfer between the
two phases using the proposed mass transfer rate equation.
Again considering section dL in the countercurrent bed,
(dy/dL)(WVp)(dL) = K^a(x x*)(A dL) = (dx/dL)(Q')(dL)
Thus, rearranging and integrating,
dx/(x-x*)
(KLaA/Q)
dL
Kp,aA
Q^
(L2 L,)
(21)
The integration is indicated between two arbitrary composi
tions because, theoretically, an infinite length of bed,
based on the assumed rate mechanism, is required for the
entire wave; this is because at the two ends of the wave the
driving force for mass transfer is zero. However, by inte
grating between two compositions other than the extreme ends
of the wave, the wave shape as a function of depth, L, can
be obtained. The left hand integral can be evaluated because
x is related to y from the equilibrium diagram, and y is
related to x by equation (20). A convenient lower limit
for the integration is xF/2, so that by integrating in both
directions to various values of x, the ultimate wave shape
may be obtained and plotted. Since the right hand side of
equation (21) before integration equals dH, the wave shape
equation may be written in terms of the dimensionless para
meter:

-52-
x
Xp/2
In most cases the left-hand integral must be ob
/
(22)
tained by numerical means because of the difficulty in
integrating the expression analytically. In effect, the
computer solutions which were run in this work performed
this integration, as evidenced by the ultimate wave shapes
which were obtained. It is important to remember that the
computer solutions also provided the relations for column
operation before the ultimate wave shape was formed. An
inspection of the graphs of the solutions shows that in
general, 90 per cent of the wave (excluding the ends) becomes
invariant by the time the composition of the liquid at the
filling front drops to less than 5 per cent of the feed
composition. Therefore, with a knowledge of the rate of
advance of the adsorption wave (VW(j => xp/yj.*), the computer
solution for the ultimate wave shape, and the computer solu
tion during filling of the first portion of the bed, the
composition of both phases may be quickly calculated for
any H and T thereafter.
D. Computation f HETS From Fixed Bed Data
Because continuous countercurrent moving bed ad
sorbers are readily analyzed by an equilibrium stage concept,
in which the number of theoretical stages in the column

-53-
necessary to give a given separation may be readily deter
mined, the experimental determination of the height equiva
lent to a theoretical stage (HETS) has always been of
interest. It is apparent that an experimental apparatus
utilizing the countercurrent principle could be built and
the determination of HETS made by suitable experiments.
However, it is not easy to construct true countercurrent
apparatus in the laboratory. It would be more desirable to
r
devise a means of predicting the HETS of a moving bed from
a simple fixed bed experiment.
The analysis of the adsorption process made in the
previous sections affords a way of doing this. It has been
pointed out how the establishment of an invariant wave shape
is possibly subject to one restriction concerning the shape
of the equilibrium diagram, a restriction which is almost
always met. It was also shown that the movement of the
ultimate wave through the column is equivalent to a counter-
current experiment in which the adsorbent and liquid feed
rates are adjusted to maintain the same velocity of feed
liquid through the bed and to maintain the adsorption wave
stationary. It was further shown that the flow rates between
the two cases can easily be related.
This leads to the conclusion that every fixed bed
experiment in which the column is long enough for the ad
sorption wave to be established is exactly equivalent to a
continuous countercurrent experiment. The one difficulty

-54-
is that the operating line for the continuous countercurrent
experiment is such that the adsorbent at both ends of the
column is in equilibrium with the liquid.
If the number of plates required for this separation
were to be stepped off, there would, of course, result an
infinity of plates because of the two pinched sections.
However, it is suggested that the HETS may nevertheless be
obtained from the fixed bed experiment.
Since the experimental effluent volume vs. composition
curve for the adsorption wave can be readily obtained, it may
be transformed into a liquid composition vs. bed length quite
readily, assuming the void fraction of the bed has been
measured. Then, instead of determining the number of stages
required for the complete separation, it is suggested that
the number of stages be stepped off between the equilibrium
and operating line for some arbitrary separation, say from
0.9xp to O.Ixf. See the following diagram.

-55-
The bed depth required for the liquid composition to change
from 0.9xf to 0.1xF can be determined from the wave shape
which was computed from the experimental effluent curve,
and a simple division by the number of theoretical stages
stepped off will give the HETS, Whether or not this HETS
will be constant for any pair of compositions is subject to
conjecture. Nevertheless, the procedure described above
affords a method of determining HETS from fixed bed experi
ments which should, if correlatable, be exactly analogous to
the HETS required in the design of a continuous counter
current bed.

VII. EXPERIMENTAL


A. Adsorbent
Commercial Davison silica gel (6-12 mesh) and Alcoa
alumina (8-14 mesh) were used as adsorbents. A large parti
cle size was chosen as there were already available in the
literature both equilibrium data and kinetic data on systems
using small particle size adsorbents. It was planned to
secure data in this work with large particle sizes, which
together with the previously published data of Lombardo (73)
for 200 mesh silica gel would provide a good basis for com
parison with calculated results. Both the silica gel and
the alumina were heated to 200C. and stored in airtight
desiccators prior to use. This insured that their pore
volumes were free of volatile contaminants, thereby promot
ing the reproducibility of experimental data.
B. Adsorbates
Methylcyclohexane and toluene were used as adsorb
ates. These compounds have similar molecular weights, but
hre of different chemical configuration. There is a definite
selective adsorption exhibited by both the silica gel and
the alumina for toluene when binary solutions of these two
liquids are adsorbed onto the adsorbents. Toluene is, there
fore, component "A" for these systems.
-56-

-57-
C. Experimental Procedures
1. Specific Pore Volume, Vp
A weighing bottle containing a weighed quantity of
adsorbent was exposed in a closed desiccator, maintained at
normal room temperature, to the vapors of the pure adsorbate
(contained in a beaker also placed in the desiccator) for a
period of two weeks. At the end of this time, which had
previously been shown to be adequate for equilibrium to be
established, the adsorbent was re-weighed to determine the
weight of adsorbate taken up by the adsorbent. From these
data the weight of adsorbate adsorbed per gram of adsorbent
and Vp, the specific pore volume of the adsorbent, milli
liters per gram, were calculated. The results of these
experiments are presented in Table 3.
2. Determination of x-y Equilibria
Approximately 20 grams of adsorbent was measured
into a 50 ml. flask, to which 20 ml. of a particular mixture
of toluene and methylcyclohexane was added. The flasks were
closed and left at room temperature for a minimum of four
hours. A sample of the liquid phase was removed and its
refractive index determined. From a refractive index cali
bration curve (Figure 26, Table 26, Appendix) previously
obtained for toluene-MCH solutions, the composition of the
liquid phase, x, was determined. Values of y the composi
tion of the adsorbed phase in equilibrium with the liquid

-58-
phase, were calculated from a material balance of the system.
This method of equilibrium determination has been used pre
viously by Lombardo (73), Eagle and Scott (63), and Perez
(75). It has proven to be quite accurate over the largest
portion of the x-y diagram, assuming that the specific pore
volumes of the two adsorbents are very nearly the same. The
equilibrium data and diagrams for the two systems inves
tigated here are presented in Tables 4 and 5 and in Figures
13 and 14. The equilibrium data and diagram of Lombardo (73)
for the Benzene-Hexane silica gel system are shown in Table 6
and Figure 15. In order to make the computations for ad
sorption fractionation, suitable empirical equations had
to be fitted to the x-y diagrams. The equations which were
used for each system are given in each table.
3. Adsorption Fractionation Experiments
The experimental apparatus used was quite simple,
consisting of three pyrex glass adsorption columns, each
2.43 cm. in diameter, of varying lengths. The lengths were
approximately six inches, twelve inches, and twenty-four
inches. Each column was equipped with a side arm near the
top for removal of the effluent, since the liquid was fed
through the columns from bottom to top. A metal charging
bomb of approximately 400 ml. capacity was connected to a
nitrogen cylinder. The bomb was equipped with a filling
connection and valve which could be closed after charging
the bomb with feed liquid. During a run the feed liquid was

-59-
forced by nitrogen pressure from the bomb through poly
ethylene tubing through a capillary tube flowmeter into the
inlet at the bottom of a column. A pressure regulating valve
on the nitrogen cylinder permitted very precise control of
the flow rate, as indicated by a manometer attached to the
capillary. It was thus possible to make a set of three runs
(one each through the three columns) in which the flow rate
and feed composition were maintained constant.
The columns were packed with adsorbent prior to a
run by carefully pouring the adsorbent into the column while
tapping continuously with a rubber mallet. The tapping was
continued and adsorbent was added until the top of the ad
sorbent was level with the exit side arm, and the surface
of the adsorbent ceased to settle. By weighing the columns
before and after packing, the quantity of adsorbent added
was ascertained.
A run was started by opening the stopcock at the
bottom of the column and adjusting the nitrogen pressure
to give the desired manometer reading. The small capillary
orifices used in the flowmeter produced pressure drops of
about ten inches of mercury, so that only minor adjustments
of the nitrogen regulating valve were required during a run
to compensate for the rise in liquid level as the column
filled.
The effluent liquid was collected in graduated
cylinders, and samples of five drops (1/4 ml.) were collected

-60-
at regular intervals. The large diameter column was chosen
so that samples of five drops could be taken at about 5-10
ml. intervals, thereby giving instantaneous compositions
rather than average compositions, which would have resulted
if a very small column diameter were used.
An electric stopclock was started at the moment the
liquid reached the first particle of adsorbent, and record
ings of the time vs. volume of effluent liquid collected
were made. The average flow rate during the run was ascer
tained from this time and volume record. The refractive
indices of the samples collected were measured after com
pletion of a run, and tables and charts of effluent liquid
composition vs. quantity of liquid collected were prepared.
The column experiments and the data obtained during
the course of these experiments are shown in Tables 8-22.
The experiments shown are only those which are referred to
in this dissertation. In addition, the data of Lombardo
for the benzene-hexane-silica gel system are presented in
Tables 23-25. Table 7 summarizes these data as to the
nature of the run and certain other factors.
4. Determination of Fraction Voids and Bed Density
In order to compare experimental data for the ad
sorption fractionation runs with the calculated results
obtained with the computer, it was necessary to evaluate
the bed density and the fraction voids in each adsorbent bed
This was done by taking various sizes of graduated cylinders

-61-
50, 100, and 200 ml., and filling them carefully with ad
sorbent. Bed densities were calculated from the weights
before and after filling and the cylinder volumes. By
tapping the cylinders with rubber mallets during the filling,
as was done when packing the adsorption columns, it was
possible to obtain reproducible bed densities. The bed
density, p^, used in the equations of this dissertation, is
the grams of dry adsorbent per total volume of dry bed. It
was assumed that since the bed densities were reproducible,
the void volumes would also be reproducible. Consequently,
after weighing the cylinders filled with dry adsorbent, the
cylinders were then filled with pure toluene or methylcyclo-
hexane. Time was allowed for the pore volumes to fill, and
additional liquid was added until the liquid remained level
with the top of the adsorbent. A third weighing ascertained
how much liquid was added, and the void space in the bed
was then computed as the difference between the volume of
liquid added and the volume of liquid known to have been
adsorbed into the adsorbent pore volumes. The void fractions
and bed densities obtained in this manner for the adsorbent
beds are listed at the top of Tables 8-25, which present
the results of the adsorption fractionation runs.

VIII. COMPARISONS BETWEEN EXPERIMENTAL
AND CALCULATED RESULTS
The only method of comparing the results of the
computer calculations with the experimental data obtained
in this study and in the work of Lombardo is to test whether
the effluent composition curves of the adsorption fractiona
tion experiments can be satisfactorily correlated by the
computed solutions.
It has been explained that there is one unmeasured
property of the system, KLa, which is contained in both of
the dimensionless parameters, H and T, used in the calcula
tions. The success of the calculations depends on whether
for a given experiment a value of KLa can be found which
results in a good agreement between the experimental and the
calculated effluent curves, and whether the values of K^a so
obtained correlate with the flow rate of liquid through the
bed.
In fitting the calculated results to the experimental
data, there are two criteria which are considered. First,
the general shape of the adsorption wave should be approxi
mated, and second, the wave should be at the proper location
in the bed at the proper time. It has been pointed out that
in a long enough column, the wave will eventually come to an
ultimate shape and an ultimate velocity. In the experiments
-62-

-63-
performed by Lombardo, the columns were sufficiently long
for this to occur. Since Lombardo did not make duplicate
runs at different column lengths, there was only one check
point for each run.
In those cases where the length of the column is
large compared to the length of the adsorption wave, there
is very little interest (other than academic) in an exact
solution to the problem of wave shape. A rough estimate of
the wave length in such a case, combined with the assumption
that the wave reaches the ultimate velocity within a few
wave lengths into the column (which it usually does) will
suffice to predict with good accuracy the quantity of pure
B which can be produced with a given column.
It is those cases in which the wave length is a sub
stantial fraction of the column length that a more accurate
knowledge of the adsorption wave shape and position is re
quired. It is precisely this case that cannot be handled
by the ultimate wave velocity and shape, but which requires
the complete solution, which was provided by the computer.
The experiments performed in this work were aimed at creat-
j
ing conditions I of column operation which would require the
computer solution.
A. Adsorption Fractionation Experiments of Lombardo
The effluent volume vs. composition curves for three
fractionation experiments on the benzene-hexane-silica gel

-64
system are presented in Figures 16, 17, and 18. The experi
mental data for each curve are listed in Tables 23, 24, and
25. These data which were published by Lombardo (72) were
the results of a Ph.D. thesis on adsorption fractionation.
Since the columns were long enough for the establishment of
the ultimate wave shape, the data were fitted to the calcula
tions by means of the ultimate wave shape. The calculated
curve at fi constant of Figure 12 v/as compared with the
experimental curves, and the value of I^a which best fit
each was chosen. The computed points using the chosen values
of K^a are also plotted in Figures 16, 17, and 18, and
curves are drawn through both the computed and the experi
mental data. It can be seen that there is good agreement
between the shapes of the computed and the experimental
curves. The values of K^a used are plotted vs. the super
ficial fluid velocity, Q/A, in Figure 24, curve A. It can
be seen that there was a good correlation between KLa and
the liquid velocity for the three runs.
B. Toluene-Methylcyclohexane Fractionation on Silica Gel
The effluent volume vs. composition curves for three
sets of fractionation experiments with the toluene-MCH-
silica gel system are shov/n in Figures 19, 20, and 21. The
experimental data for each of the nine runs are listed in
Tables 8, 16. A summary of all adsorption fractionation runs
is given in Table 7.

-65-
Each set consists of three separate fractionation
runs made under identical conditions except for the quantity
of gel used. It was desired to perform duplicate experi
ments with different column heights so that the value of KLa
would be subject to three separate checks. These experiments
were run at rates which insured that the invariant or asump-
totic wave front was not established. Two computer solu
tions, one at Xj. of 0.5 and one at Xp at 0.1, both based on
the equilibrium diagram for this system, are shown in Figures
6-10.
In order to fit the calculated solutions to the experi
mental data it was necessary, as with the Lombardo data, to
find the value of KLa which best fit the curve shapes and
positions in the bed. Here, however, there were three curves
to be checked by the same KLa. The computed solutions are
plotted on the graphs of the experimental data for comparison.
It can be seen that the agreement between wave shapes
was not as good as resulted with Lombardos data, although
the rate of movement of the waves through the column corre
lated well. In each set only one value of KLa was needed to
correlate all three runs. The values of K^a used are plotted
vs. superficial liquid velocity, Q/A, in Figure 24, curve B.
The calculated curves are steeper and show .the charac
teristic "s" shape more definitely than the experimental
curves. Previous investigators (76), have pointed out that
in ion exchange two factors may affect the steepness of the

-66-
curves. These factors are the relative adsorbability of the
adsorbent, and the relative contribution of intraparticle
diffusion to the total diffusional resistance. Two calcu
lated curves using the same xjr and K^a but using equilibrium
diagrams exhibiting considerable differences in relative
adsorbability will have different shapes. If the adsorbent
selectivity is low, the wave will be less steep, for a given
mass transfer coefficient, than if the selectivity is quite
high. This is because the magnitude of x-x*, the driving
force for mass transfer, is much lower for the column of low
selectivity. A similar effect will occur if the intraparticle
diffusion resistance contributes appreciably to the total
diffusional resistance. The concentration gradients set up
inside the particle tend to increase the quantity of compo
nent A near the external film above the value of x*, which is
computed from the average adsorbed phase composition. This
causes the adsorption wave to have a shape which cannot be
duplicated exactly by adjusting K^a in the assumed rate
relation.
It may be concluded that intraparticle diffusion is
a definite contributor to the diffusional resistance in the
large particle size gel used in these experiments. This is
in qualitative agreement with theory, since the average length
of the internal diffusion paths per unit of surface area in
creases with particle size. On the other hand, the Davison

-67-
I
)
thru 200 mesh silica gel used by Lombardo was apparently
of a particle size small enough to permit the external film
resistance to control.
The values of KLa which best fit the computed curves
to the experimental data for the large particle size gel did
correlate with superficial liquid velocity, however, as seen
in Figure 24. It was gratifying to find that such a correla
tion was possible even though feed compositions of 0.1 volume
fraction toluene and 0.5 volume fraction toluene were used.
Apparently the intraparticle diffusional resistance was not
altogether controlling at these flow rates, since there was
an increase in effective KLa when the fluid velocity through
the bed was raised.
C. Toluene-Methylcyclohexane Adsorption on
Activated Alumina
Data for the adsorption fractionation of toluene and
MCH mixtures on activated alumina are plotted in Figures 21
and 22. There were no computer calculations made using the
equilibrium diagram of this system, so that there is no com
parison presented here between experiment and calculations.
It can be seen, however, that for the same feed compositions
and range of liquid flow rates as was used in the silica gel,
the sharpness of the fractionation, as measured by the shape
of the effluent curves, was better than that of the silica
gel.

D. Use of Constant-Alpha Type Equilibrium Diagrams
In the previous discussion of the numerical integra
tion process, it was mentioned that a number of computer
solutions were obtained to the adsorption fractionation
problem using equilibrium curves of the constant-alpha type
in anticipation of the possibility of using them for approxi
mate solutions to specific cases, whenever the true equilib
rium curve of the system could be approximated by a constant
alpha curve. The results of such an approximation would
certainly be more valuable than the application of solutions
based on straight line equilibrium diagrams, which can approxi
mate only a very small portion of an equilibrium curve.
It was hoped that a constant-alpha curve based on an
average alpha over the range of the fractionation experiment
would approximate the solution closely enough to be used in
many systems. It was discovered, however, that it is quite
important to use an equilibrium diagram which exhibits the
exact relative adsorbability, alpha, for the system at the
feed composition. That this is necessary was shown in the
previous discussion on ultimate velocity of the adsorption
wave. For the wave to come to the proper ultimate velocity
(and, presumably, approach it in the proper manner) the value
of xp/yF* used in a calculation must be exact. This means
that, not an average alpha, but the alpha of the feed compo
sition must be used. In adsorption systems, alpha is very

high at low values of x, and decreases with an increase in x.
This is demonstrated in Figures 13, 14, and 15.
An example of the results when a constant-alpha type
equilibrium diagram is substituted for the true diagram can
be seen in Figure 19. The computer solution for an alpha
of 3.0 (Figures 4 and 5) was fitted to the experimental data
of a run by choosing an appropriate value of KLa, as before,
which best fit the data. The resulting curves are shown in
Figure 19 on the same plot with the experimental data and the
curves obtained from the computer solution. It can be seen
that the approximate x-y diagram fit the experimental wave
shape better than the true x-y diagram. This anomaly is ex
plained by reference to the previous discussion concerning
the effect of intraparticle diffusion on the adsorption wave
shape. Internal diffusion broadens the wave in a manner
similar to a low adsorbent selectivity. Since the alpha of
3.0 was lower average selectivity than the true equilibrium
curve, yet was the proper value at the feed composition, the
effect of intraparticle diffusion caused this solution to fit
the experimental data more closely.
E. HETS of Column Packing
A method was derived in the Results of Calculations
section for determining the HETS of column packing from fixed
bed experiments. It was suggested that the effluent curves
from fixed bed runs, when known to be of the ultimate or

-70-
asymptotic shape, can be transformed into column length units;
and the number of stages required for a given change in x for
a countercurrent column equivalent to the fixed bed experi
ment may be determined by a graphical procedure. Dividing
i
the column length by the number of stages required for the
composition change results in a value for HETS which may then
be used in the design of countercurrent adsorption columns
operating with the same relative velocity of liquid through
the adsorbent as was maintained in the fixed bed experiment.
This procedure was applied to the experimental runs
of Lombardo, since the effluent composition curves were
thought to be invariant. The calculated values of HETS for
) the three runs are plotted vs. Q/A, the superficial liquid
velocity in Figure 25, curve A. A definite correlation is
noted, with a strong dependence of HETS on the liquid velocity.
The number of stages required for a change in x from 0.05 to
0.45 was graphically determined in Figure 15. Three equi
librium stages were stepped off.
The suggested procedure could not be applied to the
runs made with the toluene-MCH-silica gel system, as the
^ asymptotic adsorption waves were obviously not established.
However, an estimate was made based on the calculated ulti
mate wave shapes and the relation between H and L which had
been established by choosing Kj^a values. In this case about
3.2 stages were required for the separation from an x of 0.05
to 0.45, and 3.0 stages were required in run F-4 for a

-71-
separation from an x of 0.02 to 0.09. The values of HETS for
the toluene-MCH-silica gel system are also plotted in Figure
25 against Q/A.
It is significant that in both cases a trend is
established. There is a marked increase in HETS with the
velocity of the liquid through the bed. It is apparent that
more data of this type are required to establish whether HETS
is actually as strongly dependent upon liquid velocity as is
indicated here. If, however, the trends indicated here are
true, it would be very important in the design of a counter-
current adsorber to size the column diameter for a given
service properly.
F. Discussion of Calculations
The comparison of the computed curves for adsorption
fractionation with two systems has shown that a very good
agreement with experimental adsorption fractionation results
when the adsorbent particle size and liquid flow rates are
such that the external film is the major resistance to mass
transfer between the adsorbed and liquid phases. In these
cases the apparent or effective overall coefficient corre
lates well v/ith liquid velocity through the adsorbent bed.
It was found that a fair approximation of the column opera
tion is obtained when the intraparticle diffusion contributes
to the diffusional resistance. However, the wave shape is
definitely not duplicated by the calculated curves. Through

72-
a fortuitous circumstance, namely, that increased intra
particle resistance affects the adsorption wave shape
similarly to a decreased adsorbent selectivity, it was seen
that when intraparticle resistance contributes to the diffu-
sional resistance, computer solutions based on constant-
alpha equilibrium diagrams may correlate better than solution
using the true equilibrium diagram, if care is taken to use a
constant-alpha solution which is exactly equal to the value
of alpha at the feed composition. The latter restriction was
found to be required in order for the velocity of the calcu
lated ultimate adsorption wave to be correct. It is recog
nized that the use of constant-alpha diagrams in cases where
the external film resistance controls would probably result
in an incorrect wave shape.
The method proposed in this dissertation for evalua
tion of HETS was used on the data presented here with some
success. A correlation of HETS with liquid velocity through
the bed was obtained, but the indicated dependence of HETS
upon liquid velocity seemed high.
G, Discussion of Intraparticle Diffusional Resistance
Since the computed solutions of this work do not yield
an exact fit with data of large particle size adsorbent, the
next logical improvement in the method of analysis which was
used here would be to include in the basic equations a mathe
matical expression for the intraparticle resistance.

-73
)
The most important new consideration in such an
analysis would be that the adsorbed liquid phase would no
longer have just one composition, y, at a given L and e ,
but its composition would also be a function of r, the radius
of the particle.
It is very difficult to propose a mathematical model
to explain the adsorption forces when intraparticle diffu
sion is considered. One possible procedure would be to
assume an external film resistance, characterized by K^a,
with the bulk unadsorbed liquid phase composition, x, on one
side and a pseudo-liquid phase composition, xr*, on the other,
where xr is the liquid phase composition in equilibrium with
yR, the composition of the adsorbed phase liquid at the ex
ternal particle radius r = R. Diffusion within the particle
in the adsorbed phase could be assumed to follow Fick's law
for diffusion within a sphere, using an effective diffusivity,
D, for the diffusion inside the particle.
By equating the rates of mass transfer across the ex
ternal film to the Fick's law expression for the diffusion
rate at r R, the intraparticle and external diffusion may
be related. Numerical integration of the resulting equations,
applying the proper boundary conditions, should provide a
solution.
One important limitation which would be encountered
is that both K^a and D, the effective internal diffusivity,
would be unknown parameters. Experiments would have to be

-74-
designed to evaluate D when KL,a was negligible, and then to
add the effect of KLa in cases where D had previously been
evaluated.
The addition of an extra unknown parameter, D, and
an additional independent variable, r, makes the problem a
much more difficult one than was solved in this work. It
is believed, however, that the techniques demonstrated here
will be applied in the future, using faster and larger
capacity computers if necessary, to approach more closely
the exact solution to adsorption fractionation problems.

IX. CONCLUSIONS
1. The application of the proposed equations for adsorption
fractionation was demonstrated for systems with small
adsorbent particle size and low flow rates, in which the
external film resistance presumably controls.
2. The boundary conditions of the liquid phase adsorption
fractionation process were properly defined and applied
in a numerical solution.
3. A complete IBM 650 program for solving the proposed
equations has been developed and presented.
4. The basic thesis, that a numerical approach can provide
useful solutions to problems otherwise insoluble, has
been proved.
5. The use of a solution based on a constant-alpha type
equilibrium curve which approximates the true equilibrium
curve was found to give qualitative accuracy. The shape
of the adsorption wave is distorted, but its rate of
travel down the column is closely approximated. The
results of this distortion can be used to advantage in
systems in which intraparticle diffusion contributes to
the total diffusional resistance.
6. Differential equations for evaluating the ultimate wave
shape were derived, and the velocity of the ultimate wave
was found to. be dependent upon xy, the feed liquid compo-
-75-

-76-
jjc
sition, and yp the adsorbed phase composition in
equilibrium with the feed liquid.
7. A method for determining from fixed bed experiments the
height equivalent to a theoretical stage (HETS) and of
an adsorbent bed v/as proposed and demonstrated.

-77-
TABLE 1
NUMERICAL INTEGRATION FORMULAE
yi+l,j + [ ATj [(3/2)y/dT)if j (1/2) (oy/T)^ jj (1)
This formula fits a second degree polynomial over
two aT increments.
- xi,j +i-A] [(5/12)(Sx/SH)ljj+1 +
(2/3)(5x/oH)i>J a/12'H2>x/*E)
This formula fits a third degree polynomial over
two AH increments. Trial and error is required.
Yi+l,j ~ Yi,j + LAT][(l/2)(dy/dT)i>J + (1/2) (dy/6 T)i+1> j] (3)
This formula fits a second degree polynomial over
one aT increment. Trial and error is required.
xi,j+l xi,j + f-AHj [(l/2)(Sx/dH)i>j + (l/2)(dx/dH)i(J+1] (4)
This formula fits a second degree polynomial over
one AH increment. Trial and error is required.
*1+1, J yi(J + [at] [<5/12)(dy/T)i+1;j +
(2/3)(dy/T)i j (l/12)(dy/dT)i_1>jJ
This formula fits a third degree polynomial over
one AT increment. Trial and error is required.

-78-
TABLE 2
SUMMARY OF
ADSORPTION FRACTIONATION CALCULATIONS
Calculation
Number
XF >
Vol. Frac. Comp.
A in Feed
x-y Equilibria
51
0.5
Toluene-MCH-Silica Gel**
52
0.1
Toluene-MCH-Silica Gel**
98
0.1
Benzene-Hexane-Silica Gel
99
0.5
Benzene-Hexane-Silica Gel
2
0.5
a = 2.0
3
0.3
a *> 2.0
4
0.1
a = 2.0
5
0.7
a = 2.0
6
0.9
a 2.0
7
0.9
a = 3.0
8
0.7
a *= 3.0
9
0.5
a = 3.0
10
0.3
a = 3.0
11
0.1
a 3.0
12
0.1
a * 5.0
13
o

to
a. 5.0
14
0.5
a e 5.0
15
0.1
P
1
<
o
16
0.3
a = 7.0

-79-
Table 2 (Continued)
xF,
Calculation Vol. Frac. Comp.
Number A in Feed x-y Equilibria
17
0.5
a
= 7.0
18
0.1
a
= 9.0
19
0.3
a
9.0
20
0.5
a
- 9.0
* Data of Lombardo (73)
** Data of this work

TABLE 3
DETERMINATION OF SPECIFIC PORE VOLUMES
Run
No. Adsorbent
Adsorbate
Wt. Ad
sorbent, g.
Wt. ad
sorbate, g.
g. Adsorbate
g. Adsorbent
Adsorbate
Density,
g./cc.
VP
cc./g.
1
6-12 Mesh
Silica Gel
Toluene
29.56
10.77
. 366
.872
.420
2
tf
TT
21.28
7.85
.369
.872
.424
3
" Methyl-
cyclohexane
33.44
9.98
.299
.774
.387
4
1t
It
21.17
6.26
.296
.774
.382
5
8-14 Mesh
Act. Alumina
Methyl- 43.73
cyclohexane
6.36
. 1455
.774
.188
6
tl
u
23.68
3.473
.1467
.774
.189
7
If
Toluene
21.30
3.563
.1673
.872
.192
8
?T
! 1
36.48
5.636
. 1616
.872
. 185
For
6-12
Mesh
Silica Gel., Average Vp *
.402
For
8-14
Mesh
Activated Alumina Average Vp -
.188

81-
TABLE 4
ADSORPTION EQUILIBRIUM DATA FOR
TOLUENE-METHYLCYCLOHEXANE ON
DAVISON 6-12 MESH SILICA GEL
(cf. Figure 13)
X
Volume Fraction
Toluene in Liquid
Phase
y
Volume Fraction
Toluene in
Adsorbed Phase
a
Relative
Adsorbability
(y/l-y)(1-x/x)
.0350
.289
11.211
.0372
.269
9.526
.0647
.344
7.581
.0847
.420
7.825
124
.462
6.064
.128
.476
6.188
.149
.499
5.688
. 182
.540
5.276
.210
.570
4.987
.132
.467
5.761
.243
.605
4.770
.304
.656
4.366
.344
.687
4.186
.411
.726
3.798
.489
.768
3.459
.526
.787
3.330
.578
.817
3.259
.641
.839
2.919
.704
.866
2.717
.741
.877
2.492
.796
.906
2.470
.871
.943
2.450
.933
.949
1.336
Empirical Equations
(x/l-x)
x/l-x
. 203y
.1725(y/l-y)1*412
.459(y/l-y) .589
0 i y -15
0.15 y .776
.776 y 1

-82
TABLE 5
ADSORPTION EQUILIBRIUM DATA FOR
TOLUENE-METHYLCYCLOHEXANE ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
(cf. Figure 14)
X
Volume Fraction
Toluene in Liquid
Phase
y
Volume Fraction
Toluene in
Adsorbed Phase
a
Relative
Adsorbability
(y/l~y)(1-x/x)
.0178
. 127
8.03
.0475
.214
5.46
.233
.480
3.04
.417
.685
3.04
.648
.832
2.69
.874
.960
3.46

-83-
TABLE 6
ADSORPTION EQUILIBRIUM DATA
BENZENE-N-HEXANE ON
DAVISON THRU 200 MESH SILICA GEL
(Data of Lombardo)
(cf. Figure 15)
X
Volume Fraction
Benzene in Liquid
Phase
y
Volume Fraction
Benzene in
Adsorbed Phase
a
Relative
Adsorbability
(y/i-y)(1-x/x)
0.045
0.298
9.009
0.115
0.485
7.247
0.209
0.615
6.046
0.319
0.723
5.572
0.428
0.771
4.500
0.546
0.841
4.398
0.653
0.875
3.72
0.771
0.922
3.51
0.882
0.966
Empirical Equations
y -= x/(.9398x + .1475) ; .226 < x < .500
y x/(l.1354x + .1032) ; 0 < x < .226

TABLE 7
SUMMARY OF FRACTIONATION EXPERIMENTS
Run No. System Adsorbent Column Diam.,
cm.
F-la Toluene-MCH
F-lb
F-lc
F-2a
F-2b
F-2c
F-4a
F-4b
F-4c
F-5a
F-5b
F-5c
Wt. Adsorbent, Inverse Rate, xp
g.sec,/cc.Feed Comp.
195
12.73
0.5
95.2
12.7
0.5
45.35
12.7
0.5
191.2
20
0.5
95.2
20
0.5
47.55
20
0.5
195.35
5.75
0.1
96.6
5.75
0.1
45.3
5.75
0.1
255.2
8.13
0.1
121.5
8.13
0.1
59.7
8.13
0.1
62.8
16
0.5
6-12 Mesh 2.47
Silica Gel
ft If
tf ft
! ? Tt
tf IT
Tl Tf
tt tf
tr tt
ft tt
8-14 Mesh
Alumina
tt Tf
tt ft
Tt tt
F-6a

TABLE 7 (Continued)
Run No.
System
Adsorbent Column Diam.,
cm.
Wt. Adsorbent,
g.
Inverse Rate
sec./cc.
Xp
Feed Comp.
F-6b
tf
ft
tt
129.9
16
0.5
F-6c
It
tf
?
267.9
16
0.5
B-2(Lom
bardo)
Benzene-
N-Hexane
Thru 200
Mesh Silica
Gel
0.8
20
880
0.5
B-3
Tt
tt
tt
10
650
0.5
B-4
tt
tt
1.9
20
246
0.5
l
OD
cn
I

86-
TABLE 8
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F la (cf. Figure 19)
Col. Diam.
Wt. Gel.
Pb
XF
Sample No.
*** 2.47 cm.
*= 195.0 g.
= .679 g./cc.
- 0.500 Vol. fr.
Toluene
Ave. Inverse Rate
V m
P
fv
Sample Size *
12.7 sec./cc.
.402 cc./g.
.293
7 drops
Time, sec.
x
Total Vol. Vol. Fraction
Effluent, cc.Toluene
1
2155
.15
.02
2

5.50
.055
3
2305
10.85
.102
4
2380
16.20
.150
5
2450
21.55
.199
6
2512
26.90
.240
7
2590
32. 25
.279
8
37.60
.308
9
...
42.85
.328
10
2790
48.30
.356
11
...
59.00
.380
12
_
64.35
.395
13
...
69.70
.408
14
3135
75.05
.412
15
3195
80.40
.428
16
3270
85.75
.439
17
3335
91.10
.441
18
3395
96.45
.453
19
...
111.80
.466

-87-
TABLE 9
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F lb (cf. Figure 19)
Col. Diara.
Wt. Gel.
Pb
XF
2.47 cm.
95.20 g.
.679 g./cc.
0.500 Vol. fr.
Toluene
Ave. Inverse Rate
vp
*v
Sample Size
12.7 sec./cc.
.402 cc./g.
.293
7 drops
Total Vol.
Sample No.Time, sec.Effluent, cc.
x
Vol. Fraction
Toluene
1
-
.15
.125
2

2.50
.208
3

4.85
.240
4
7.20
.268
5

9.55
.290
6
11.90
.321
7
14.15
.327
8
16.50
.343
9

18.85
.359
10

21.10
.370
11
-
23.45
.370
12
1487
28.80
.395
13
1539
34.15
.408
14
1604
39.50
.420
15
1666
44.85
.428
16

50.20
.435
17
1797
55.55
.437
18
1869
60.90
.453
19
1933
66.25
.463
20

71.60
.465

-88-
TABLE 10
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F lc (cf. Figure 19)
Col. Diam. = 2.47 era.
Ave. Inverse Rate 12.73 sec./cc.
Wt. Gel. 45.35g. V
P
pb .679 g./cc. f
.402 cc./g.
.293
xF
0.500 Vol. fr. Sample Size
Toluene
7 drops
(except as
noted)
Sample No.
Time, sec.
Total Vol. x
Vol. Fraction
Effluent, cc.Toluene
1
.15
.196
2 (1 ml.)
0.70
.230
3

1.70
.255
4 "

2.70
.282
5

3.70
.300
6
4.70
.310
7
5.70
.330
8
-.
6.70
.342
' 9

7.70
.356
10

8.70
.367
11
--
30.70
.438
12
36.05
.448
13
41.40
.450

-89
TABLE 11
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 2a (cf. Figure 20)
Col
. Diam.
= 2.47 cm.
Ave. Inverse
Rate * 20 sec./cc.
Wt.
Gel.
- 191.20 g.
VP
= .402 cc./g.
Pb
- .679 g,/cc.
*v
- .293
xF
- 0.500 Vol. fr.
Sample Size
= 5 drops
Toluene
X
Total Vol.
Vol. Fraction
Sample No.
Time, sec.
Effluent, cc.
Toluene
1
.10
.004
2
3644
5.35
.004
3
3747
10.60
.050
4
3853
15.85
Q50
5
3957
21.10
.112
6
4065
26.35
.172
7
4180
31.60
.230
8
4275
36.85
.278
9
~ ~
42.10
.305
10
4515
47.35
.339
11
4606
52.60
.368
12
4710
57.85
.385
13
4825
63.10
.396
14
4924
68.35
.408
15
5020
73.60
.418
16
5121
78.85
.425
17
5216
84.10
.430
18

89.35
.438

-90-
TABLE 12
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 2b (cf. Figure 20)
Col. Diam.
* 2.47 cm.
Ave. Inverse
Rate *= 20 sec./cc.
Wt. Gel.
- 95.15 g.
VP
*= .402 cc./g.
Pb
- .679 g./cc.
fv
= .293
*F
- Vol. fr.
Toluene
Sample Size
5 drops
Sample No.
Time, sec.
Total Vol.
Effluent, cc
X
Vol. Fraction
. Toluene
1
1650
.10
.035
2
1725
4.35
.090
3
1762
6.60
.136
4
1809
8.85
.100
5
1847
11.10
.060
6
1890
13.35
.205
7
1930
15.60
. ISO
8
1975
17.85
.278
9
2022
20.10
.328
10
2066
22.35
.341
11
2183
27.60
.366
12
2298
32.85
.390
13
2398
38.10
.405
14
2499
43.35
.406
15
2611
48.60
.436
16
2713
53.85
.440
17
2828
59.10
.444
18

64.35
.452
19
3037
69.60
.460

-91
TABLE 13
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 2c (cf. Figure 20)
Col. Diam.
= 2.47 cm.
Ave. Inverse
Rate = 20 sec./cc.
Wt. Gel.
= 47.55 g.
vp
= .402 cc./g.
Pb
= .679 g./cc.
fv
- .293
XF
- 0.500 Vol. fr.
Toluene
Sample Size
= 5 drops
Sample No.
Time, sec.
Total Vol.
Effluent, cc.
X
Vol. Fraction
Toluene
1
835
.10
.122
2
86S
2.35
.210
3
935
4.60
.252
4
975
6.85
.312
5
1020
9.10
.326
6
1050
11.35
.340
7
1118
13.60
.370
8
1156
15.85
.395
9
1198
18.10
.405
10

20.35
.416
11
1283
22.60
.425
12
1394
27.85
.440
13
1491
33.10
.450
14

48.85
.468

-92-
TABLE 14
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 4a (cf. Figure 21)
Col
. Diam.
2.47 cm.
Ave. Inverse
Rate = 5.75 sec./(
wt.
Gel.
=* 195.35 g.
VP
= .402 cc./g
Pb
- .679 g./cc.
fv
* 293
xjr
- 0.100 Vol. fr.
Sample Size
*= 5 drops
Toluene
X
Total Vol.
Vol. Fraction
Sample No.
Time, sec.
Eifluent, cc.
Toluene
1
983
10
.0
2
1041
20
.0
3
......
30
.0
4
1163
40
.0
5
1222
50
.0
6
1272
60
.0
7
1337
70
.0
8
1393
80
.0
9
1445
90
.0
10

100
.0
11
1560
110
.006
12
1619
120
.010
13

130
.016
14
1730
140
.019
15

150
.023
16
1906
170
.032
17
1969
180
.035

-93
TABLE 15
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 4b (cf. Figure 21)
Col
. Diam.
- 2.47 cm.
Ave. Inverse
Rate <= 5.75 sec./cc.
wt.
Gel.
* 96.6 g.
vp
= .402 cc./g.
P b
= .679 g./cc.
fv
- .293
- 0.100 Vol. fr.
Sample Size
5 drops
F
Toluene
Total Vol.
X
Vol. Fraction
Sample No.
Time, sec.
Effluent, cc.
Toluene
1
470
0
.014
2
590
20
.019
3
708
40
.027
4
818
60
.039
5
933
80
.048
6
1042
100
.056
7
1104
110
.060
8
1214
130
.068
9
1326
150
.074
10
1434
170
.081
11
1546
190
.081
12
1652
210
.085
13
1766
230
.087
14
1877
250
.087
15
1990
270
.087
16
~
290
.090

94-
TABLE 16
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 4c (cf. Figure 21)
Col. Diam. 2.47 cm.
Wt. Gel. 45.3 g.
P b .679 g./cc.
Xy 0.100 Vol. fr.
Toluene
Ave. Inverse Rate
vp
*v
Sample Size
5,75 sec./cc.
.402 cc./g.
.293
5 drops
x
Sample No.
Time, sec.
Total Vol.
Effluent, cc.
Vol. Fraction
Toluene
1
345
20
.048
2
465
40
.061
3
575
60
.069
4
694
80
.074
5
805
100
.079
6
920
120
.082
7
1036
140
.082
8
1146
160
.084
9
1257
180
.085

95-
TABLE 17
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 5a (cf. Figure 22)
Col. Diam. 2.47 cm.
Wt. Alumina* 255.2 g.
P b
.883 g./cc.
Xj,
0.100 Vol.
Toluene
Ave. Inverse Rate
Sample Size
8.13 sec./cc
.1888 cc./g.
.425
5 drops
x
Sample No.
Time, sec.
Total Vol.
Effluent, cc.
Vol, Fraction
Toluene
1
1610
0.10
.0
2
1698
10.35
.0
3
1779
20.60
.0
4
1866
30.85
.0
5
2034
51.10
.0
6
2113
61.35
.036
7
2196
71.60
.044
8
2275
81.85
.057
9

92.10
.067
10
-
102.35
.071
11
2530
112.60
.082
12
2699
132.85
.093
13

143.10
.097
14
-
153.35
.097
15
-
163.60
.097
16
3025
173.85
.097
17
3107
184.10
.097
18
-
184.35
.099
19
3283
204.60
.099

-96-
TABLE 18
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 5b (cf. Figure 22)
Col. Diara.
2.47 cm.
Ave. Inverse
Rate = 8.13 sec./cc.
Wt. Alumina -
121.5 g.
V
P
- .1888 cc./g.
P b
.883 g./cc.
fv
.425
xv
0.100 Vol. fr.
Sample Size
= 5 drops
X
Toluene
Total Vol.
X
Vol. Fraction
Sample No.
Time, sec.
Effluent, cc.
Toluene
1
835
.10
.003
2

10.35
.016
3
1008
20.60
.023
4
......
30.85
.041
5

41.10
.059
6
1258
51.35
.072
7
1344
61.60
.082
8
1427
71.85
.088
9
82.10
.090
10
1598
92.35
.094
11

102.60
.095
12
1763
112.85
.097
13
1844
123.10
.099
14
2016
143.60
.099

-97-
TABLE 19
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 5c (ci. Figure 22)
Col. Diara.
- 2.47 cm.
Ave. Inverse
Rate 8.13 sec./cc
Wt. Alumina
- 59.7 g.
p
** 1888 cc. /g.
P b
*= .883 g./cc.
fv
- .425
Xj,
~ 0.100 Vol. fr.
Toluene
Sample Size
*> 5 drops
Sample No.
Time, sec.
Total Vol.
Effluent, cc.
X
Vol. Fraction
Toluene
1
410
.10
.016
2
497
10.35
.044
3
581
20.60
.066
4
30.85
.079
5
750
41.10
.087
6
833
51.35
.095
7
916
61.60
.097
8

71.85
.099
9

82.10
.100

-98
TABLE 20
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 6a (cf. Figure 23)
Col. Diara.
Wt. Alumina
Pb
XF
2.47 cm.
Ave. Inverse
Rate = 16 sec/cc.
62.8 g.
vp
= .1888 cc./g.
.883 g./cc.
*v
= .425
0.5 Vol. fr.
Toluene
Sample Size
5 drops
Sample No.Time, sec.
x
Total Vol. Vol. Fraction
Effluent, cc.Toluene
1
852
.10
.252
2
945
5.35
.370
3
1025
10.60
.435
4
1112
15.85
.458
5
1198
21.10
.478
6
1286
26.35
.484
7
1370
31.60
.488
8
1454
36.85
.492
9
1538
42.10
.493
10
1623
47.35
.493
11
1707
52.60
.493
12
1782
57.85
.494
13
1865
63.10
.494
14
1948
68.35
.494
15
2032
73.60
.495
16
2116
78.85
.495
17
2198
84.10
.495
18
2280
89.35
.495
19
2361
94.60
.496

-99
TABLE 21
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 6b (cf. Figure 23)
Rate = 16 sec./cc.
= .1888 cc./g.
- .425
5 drops
x
Total Vol. Vol. Fraction
Sample No.Time, sec.Effluent, cc.Toluene
Col.
Diam.
2.47 cm.
Ave. Inverse
wt.
Alumina *=
129.9 g.
vp
Pb
es
.883 g./cc.
*v
xF
cs
0.5 Vol. fr.
Toluene
Sample Size
1
1660
.10
.128
2
1745
5.35
.256
3
1823
10.60
.350
4
1908
15.85
.408
5
1994
21.10
.440
6
2078
26.35
.461
7
2163
31.60
.474
8
2245
36.85
.479
9
2330
42.10
.481
10
2415
47.35
.485
11
2497
52.60
.488
12
2582
57.85
.490
13
2665
63.10
.492
14
2748
68.35
.492
15
2828
73.60
.493
16
2912
78.85
.494
17
2995
84.10
.496
18
3078
89.35
.498
19
3165
94.60
.500

-100-
TABLE 22
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 6c (cf. Figure 23)
Col. Diam.
Wt. Alumina
Pb
Xp
2.47 cm.
267.9 g.
.883 g. /cc.
0.5 Vol. fr.
Toluene
Ave. Inverse Rate
VP
fv
Sample Size
16 sec./cc.
.1888 cc./g.
.425
5 drops
Sample No.Time, sec.
x
Total Vol. Vol. Fraction
Effluent, cc.Toluene
1
3283
.10
.025
2
3372
5.35
.105
3
3453
10.60
.198
4
3538
15.85
.281
5
3626
21.10
.350
6
3714
26.35
.396
7
3800
31.60
.422
8
3886
36.85
.446
9
3974
42.10
.454
10
4059
47.35
.466
11
4145
53.60
.475
12
4230
57.85
.480
13
4314
63.10
.481
14
4398
68.35
.482
15
4486
73.60
.484
16
4572
78.85
.489
17
4656
84.10
.491
18
4740
89.35
.491
19
4823
94.60
.491
20
4907
95.85
.495

-101-
TABLE 23
BENZENE-N-HEXANE FRACTIONATION ON
DAVISON "THRU 200" MESH SILICA GEL
(Data of Lombardo)
Run No. B 2 (cf. Figure 16)
Col. Diam.
Wt. Gel.
Pb
8 mm.
20 g. p
.712 g./cc. xF
Ave. Inverse Rate
Vr
880 sec./cc.
.357
0.500 Vol. fr.
Benzene
.528
Sample No.
Sample
Time, min.Volume, cc.
x
Vol. Fraction
Benzene
1
2
3
4
5
6
7
8
9
10
11
0
7:00
13:50
20:20
27:00
33:50
40:40
47:45
55:00
63:40
72:00
80:00
0.5
0
0
0
0
0
0
0
0
0.325
0.485
0.500

-102-
TABLE 24
BENZENE-N-HEXANE FRACTIONATION ON
DAVISON "THRU 200" MESH SILICA GEL
(Data of Lombardo)
Run No. B 3 (cf. Figure 17)
Col. Diam.
8 mm.
Ave.
Inverse Rate = 650 sec./cc.
Wt. Gel.
B 10 g.
vp
.357 cc./g.
Pb
.623 g./cc.
- 0.500 Vol. fr.
Benzene
fv
464
Sample No
Time, sec.
Sample
Volume, cc.
X
Vol. Fraction
Benzene
1
0
320
0.5
0
2
595
11
0
3
880
ft
0
4
1190
11
0
5
1500
It
0.281
6
1820
11
0.481
7
2140
11
0.500

-103-
TABLE 25
BENZENE-N-HEXANE FRACTIONATION ON
DAVISON "THRU 200" MESH SILICA GEL
(Data of Lombardo)
Run No. B 4 (cf. Figure 18)
Col. Diam. = 19 mm. Ave
Wt. Gel. = 20 g. Vp
pb = .545 g./cc. xp
fv
Inverse Rate = 246 sec./cc.
= .357 cc./g.
= 0.500 Vol. fr
Benzene
= 406
x
Sample No.
Time, sec.
Sample
Volume, cc.
Vol. Fraction
Benzene
0
.
. ,
1
133
0.5
0
2
250
M
0
3
365
0
4
480
tt
0
5
595
if
0
6
708
ft
0.009
7
830
ft
0.061
8
955
ft
0.177
9
1075
tt
0.320
10
1200
ft
0.404
11

tl
0.444
12
1455
tt
0.471
13
1587
tt
0.484
14
1720
tf
0.492
15
1852
ft
0.494
16
1985
ft
0.495

-104-
TABLE 26
CALIBRATION OF REFRACTOMETER FOR
MCH-TOLUENE SOLUTIONS AT 30C.
Vol. Fraction
Ref. Index
Vol. MCH, cc.
Vol. Toluene, cc.
Toluene
1.4178


0
1.4245
17.75
1.966
.0996
1.4313
7.85
1.970
. 2005
1.4381
6.87
2.971
.302
1.4452
5.925
3.955
.400
1.4525
9.80
9.77
.500
1.4600
7.90
11.73
.598
1.4676
5.925
13.70
.698
1.4748
3.755
14.72
.7965
1.4830
1.949
17.70
.9009
1.4906
|
1.000

START
[NILZ
JLiQO.
Initialize
PARTA
J.Q-QQ.
Compute
First Two AT
Increments
RSETA
Reset
Addresses
TSWFA
0723
Test For
Wave Front
No
L
ADVWA j 1003
SRYF
Yes
ZD
Advance
Compute
Wave One AH
First Point
Increment
In Wave
TSENP
-Q9Q0-
TSTIM
Test For
End of Problem
JSi

0754
CONSOLE *
r 8000
Read A
Card
'
Test Time
For Punch
No 1 Yes
STPCB
''0826 STPCi*0977
Set To
Skip Punch
Set To
Punch
TNLPA
0050
Test For Next
To Last Point
Yes | No
CL2PA E~ 0011
Compute Next
To Last Point
CNPWA
0010
Compute
Normal Point
CL1PA 1205
TSENB
0055
Compute Last
Test For
Point in Wave
End of Bed
(T -
H)
(H 200AH)
No I Yes
TSNWY t QQ32-
Test For
End of Wave
(y o)
3¡q I Yes
AVPIA
0092
Advance One
AH Increment
Inside Wave
FIGURE 1.- FLOW DIAGRAM OF COMPUTER PROGRAM

H, Dimensionless Bed Depth
FIGURE 2.- LIQUID PHASE COMPOSITION HISTORY,
COMPUTER SOLUTION TO PROBLEM 1.

H, Dimensionless Bed Depth, Or T, Dimensionless Time
FIGURE 3.- ULTIMATE ADSORPTION WAVE SHAPES
COMPUTER SOLUTION TO PROBLEM 1.
-107

H, Dimensionless Bed Depth
FIGURE 4.- LIQUID PHASE COMPOSITION HISTORY,
COMPUTER SOLUTION TO PROBLEM 9.
-108-

H, Dimensionless Bed Depth, Or T, Dimensionless Time
FIGURE 5.- ULTIMATE ADSORPTION WAVE SHAPES,
COMPUTER SOLUTION TO PROBLEM 9.
-10 9-

FIGURE 6.- LIQUID PHASE COMPOSITION HISTORY,
COMPUTER SOLUTION TO PROBLEM 51.
i

X,
Volume
Fraction
Component A
In Liquid
Phase
FIGURE 7.- ULTIMATE ADSORPTION WAVE SHAPES
COMPUTER SOLUTION TO PROBLEM 51

H, Dimensionless Bed Depth
FIGURE 8.- LIQUID PHASE COMPOSITION HISTORY,
COMPUTER SOLUTION TO PROBLEM 52.
-112-

1.00
0.50
y,
Volume
Fraction
Component A
In Adsorbed Phase
0.10
0.05
0o01
FIGURE 9.- ULTIMATE ADSORPTION WAVE SHAPES
COMPUTER SOLUTION TO PROBLEM 52

FIGURE 10.- ULTIMATE ADSORPTION WAVE SHAPES
COMPUTER SOLUTION TO PROBLEM 52.
i

/
07
/

FIGURE 12- ULTIMATE ADSORPTION WAVE SHAPES,
COMPUTER SOLUTION TO PROBLEM 99.

Volume Fraction Toluene in Adsorbed Phase
-117
x, Volume Fraction Toluene in Liquid Phase
FIGURE 13.- ADSORPTION EQUILIBRIUM DIAGRAM FOR MCH-
TOLUENE ON DAVISON 6-12 MESH SILICA GEL
Relative Adsorbability

Volume Fraction Toluene in Adsorbed Phase
118-
x, Volume Fraction Toluene in Liquid Phase
FIGURE 14.- ADSORPTION EQUILIBRIUM DIAGRAM FOR MCH-
TOLUENE ON ALCOA 8-14 MESH ACTIVATED ALUMINA
Relative Adsorbability

Volume Fraction Benzene in Adsorbed Phase
-119-
x, Volume Fraction Benzene in Liquid Phase
FIGURE 15.- ADSORPTION EQUILIBRIUM DIAGRAM FOR BENZENE-
HEXANE ON DAVISON "THRU 200" MESH SILICA
GEL
a, Relative Adsorbability

Volume Fraction Benzene in Effluent
-120-
Total Volume of Effluent, cc.
FIGURE 16.- BENZENE-HEXANE FRACTIONATION WITH SILICA
GEL LOMBARDO RUN B-2.

Volume Fraction Benzene in Effluent
-121-
Total Volume of Effluent, cc.
FIGURE 17.- BENZENE-HEXANE FRACTIONATION WITH SILICA GEL
LOMBARDO RUN B-3.

Volume Fraction Benzene in Effluent
122
Total Volume of Effluent, cc.
FIGURE 18.- BENZENE-HEXANE FRACTIONATION WITH SILICA GEL
LOMBARDO RUN B-4.

Volume Fraction Toluene in Effluent
-123-
Total Volume of Effluent, cc.
FIGURE 19.- MCH-TOLUENE FRACTIONATION WITH SILICA GEL
JOHNSON RUN F-l.

Volume Fraction Toluene in Effluent
FIGURE 20.- MCH-TOLUENE FRACTIONATION WITH SILICA GEL
JOHNSON RUN F-2.

Volume Fraction Toluene in Effluent
-125-
, Total Volume of Effluent, cc.
FIGURE 21.- MCH-TOLUENE FRACTIONATION WITH SILICA GEL
JOHNSON RUN F-4.

Volume Fraction Toluene in Effluent
-126-
Total Volume of Effluent, cc.
FIGURE 22.- MCH-TOLUENE FRACTIONATION WITH ALUMINA
JOHNSON RUN F-5.

-127-
Total Volume of Effluent, cc.
FIGURE 23.- MCH-TOLUENE FRACTIONATION WITH ALUMINA
JOHNSON RUN F-6.

Q/A, cm./sec.
FIGURE 24.- EFFECT OF LIQUID VELOCITY ON OVERALL MASS TRANSFER COEFFICIENT

HETS, cm

Q/A, cm./sec.
FIGURE 25.- EFFECT OF LIQUID VELOCITY ON HETS
129

Volume Fraction Toluene
i
i
FIGURE 26.- CALIBRATION OF REFRACTOMETER FOR MCH-TOLUENE SOLUTIONS
130

-131-
X. LIST OF SYMBOLS
A Cross sectional area of adsorbent bed, sq. cm.
C Molar concentration, grams moles/1.
fv Fraction interstitial void space in adsorbent bed
H Dimensionless bed depth parameter defined by equation (4)
KLa Overall coefficient for mass transfer, 1/sec.
L Adsorbent bed depth, measured from entrance, cm.
Q Volumetric flow rate of liquid through adsorbent bed,
cc./sec.
Q- Volumetric flow rate of liquid through moving bed,
cc./sec.
r^ Rate of exchange of component A between two phases,
gram moles/(sec.)(cc.)
T Dimensionless time parameter, defined by equation (3)
Vp Pore volume of adsorbent, cc./g.
vm Molar volume of component A, l./gram mole
Vw Ultimate velocity of adsorption wave through fixed
adsorbent bed, cm./sec.
Vwd Ultimate velocity of adsorbent wave through fixed
adsorbent bed in units of parameters H and T
W Weight rate of flow of adsorbent through a continuous
countercurrent adsorption column, g./sec.
x Volume fraction of more adsorbable component A in liquid
phase
xjr Composition of liquid feed to adsorbent bed, volume
fraction component A
y
Volume fraction of more adsorbable component A in
adsorbent-free adsorbed phase

-132-
>
yp* Composition of adsorbed phase in equilibrium with feed
liquid, volume fraction component A
a Relative adsorbability of adsorbent for components A
and B, defined as (y/l-y)(1-x/x) at equilibrium
Pb Bulk density of dry adsorbent bed, g./cc.
6 Time elapsed since liquid first entered bed, sec.
i,j Subscripts used to denote a point on a grid
A,B Subscripts used to denote components A and B
Subscript used to denote that the designated phase is
in equilibrium with the opposite phase

XI. LITERATURE CITED
(1) Hirschler, A. E., and Mertes, T. S. Liquid Phase Adsorp
tion Studies Related to the Arosorb Process. I.E.C.
47_: No. 2. 193-202. Feb., 1955.
(2) Hypersorption Process Flow Sheet. Petroleum Refiner. 29:
No. 9. 1950.
(3) Freundlich, H., and Losev, G. Z. Physik Chem. 59: 284-312.
1907.
(4) Freundlich, H. Adsorption and Occlusion. Z. Physik Chem.
61: 249. 1908.
(5) Freundlich, H. Theory of Adsorption. Z. Chem. Ind.
Kolloide. 3: 49-76. 1909.
(6) Travers, Morris W. Adsorption and Occlusion. Z. Physik
Chem. 61: 241. 1908.
(7) Wohlers, H. E. Adsorption Phenomena of Inorganic Salts.
A. Anorg. Chem. 59: 203-212. July 25, 1908.
(8) Michaelis, L., and Roa, P. Adsorption. Z. Chem. Ind.
kolloide. 4: 18-19. 1909.
(9) Reychler, A. Adsorption of Acids by Carbon. J. Chem.
Phys. 7: 497-505. 1909.
(10) Duclaux, Jacques. Adsorption of Gases by Porous Bodies.
Compt. Rend. 153: 1217. 1912.
(11) Geddes, A. E. M. Adsorption of CO2 by Charcoal. Ann.
Physik. 29: 797-808. 1909.
(12) Schmidt, G. C. Adsorption of Solutions. Z. Physik. Chem.
74: 689-737. 1912.
(13) Katz, J. R. Laws of Surface Adsorption and Potential of
Molecular Attraction. J. Chem. Soc. 104: 27. 1913.
(14)Langmuir, Irving. Theory of Adsorption. Phys. Rev. 6:
79-80. 1915.
-133-

-134-
(15) Polanyi, M. Adsorption of Gases by Solid Adsorbent.
Verh. Deut. Physik. Soc. 18: 55-80. 1916.
(16) Williams, A. M. Adsorption Isotherm at Low Temperatures.
Proc. Roy. Soc. Edinburgh. 3£: 48-55. 1918.
(17) Polanyi, M. Adsorption From Standpoint of 3rd Law of
Thermodynamics. Verh. Deut. Physik. Soc. 16:
1012-1016. 1914.
(18) Williams, A. M. Adsorption of Gases at Low and Moderate
Concentration. Proc. Roy. Soc. London. 96A: 287-297,
298-311. 1919.
(19) Lamb, A. B., and Coolidge, H. Sprague. Heat of Adsorp
tion of Vapors on Charcoal. J. Am. Chem. Soc. 42:
1146-1170. 1920.
(20) Gurvich, L. G. Physico Chemical Attractive Force. J.
Russ. Phys. Chem. 47: 805-827. 1915.
(21) Berzter, F. Rate of Adsorption of Gases by Charcoal.
Ann. Physik. 37: 472-507. 1912.
(22) Rakovskii, V. Adsorption Kinetics of Hydration and
Dehydration. J. Russ. Phys. Chem. Soc. 44:
836-849. 1912.
(23) Gurvich, L. Adsorption. Z. Chem. Ind. Kolloide. 11;
17-19. 1913.
(24) Freundlich. Desorption-Velocities. Z. Physik. Chem.
85: 660-680. 1914.
(25) Dietl, A. Kinetics of Adsorption. Koll. Chem. Beiheste.
6: 127. 1914.
(26) Hernad, H. S. Velocity of Adsorption of CCI4 by Charcoal.
J. Am. Chem. Soc. 42: 372-391. 1920.
(27) Polanyi, M. Adsorption Catalysis. Elektrochem. 27:
142-150. 1921.
(28) Kruyt, H. R. Heterogeneous Catalysis and Adsorption.
Rec. Tran. Chem. 40: 249-280. 1921.
(29) Mathews, Albert P. Principle of Adsorption. Physiol.
Review. 1: 553-597. 1921.

-135-
(30) Ilin, B. Molecular Kinetic Theory of Adsorption. J.
Russ. Phys. Chem. Soc. 1925.
(31) Levy, L. S. Adsorption From Binary System. Compt. Rend.
186: 1619-1621. 1928.
(32) Klosky, S. Adsorption of Mixtures of Vapors. J. Phys.
Chem. 32: 1387-1395. 1928.
(33) Tolloizko, Stanislaw, A General Equation for the Speed
of Pure Adsorption. Collection Czeck Chem. Communica
tions. 2: 344-346. 1930.
(34) Constable, F. H. Kinetics of Adsorption with Relation
to Reaction Velocity. Trans. Faraday Soc. 28: 227-
228. 1932.
(35) Swikin, J. K., and Kondrashon, A. I. Adsorption Kinetics
of Vapors in Air Stream. Kolloid Z. 56: 295:299.
1931.
(36) Ilin, B. V. Kinetics of Adsorption of High Mol. Wt.
Substances by Porous Powder. J. Gen. Chem. (U.S.S.R.)
2: 431-441. 1932.
(37) Rogenskei, S. Equation for Kinetics of Activated Ad
sorption. Nature. 134: 935. 1934.
(38) Crespi, M. Kinetics of Adsorption I. Anale. Soc. Espan.
Fis. Quim. 32: 30-42. 1934.
(39) Crespi, M., and Alexandre, V. Kinetics of Adsorption III.
Anale. Soc. Espan. Fis. Quim. J3: 350-359. 1935.
(40) Taylor, Hugh S. The Activation Energy of Adsorption
Processes. J. Am. Chem. Soc. £>3: 578-597. 1931.
(41) Nizovkin, V. K. Dynamics of Chemical Adsorption. Trans.
VI. Mendelien Engrs. 2: 218-232. 1935.
(42) Crespi, M. Kinetics of Adsorption II. Anale. Soc. Espan.
Fis. Quim. 32: 639-657. 1934.
(43) Damkohler, G. The Adsorption Velocity of Gases on
Powdered Adsorbents. Z. Physik. Chem. A174: 222-238.

-136-
I
)
>
(44) Brunauer, Emmett, Teller. Adsorption of Gases in Multi-
molecular Layers. J. Am. Chem. Soc. 60: 309-318. 1938.
(45) Wilkins, F. J. Statistical Mechanics of the Adsorption
of Gases at Solid Surfaces. Proc. Roy. Soc. London.
A164: 496-509. 1938.
(46) Kimball, Geo. E. The Absolute Rate of Heterogeneous
Reactions. J. Chem. Phys. 6: 447-453. 1938.
(47) Ruff, Walter, A Study of the Adsorption Dynamics of
Mixed Dissolved Substances. V. Wasser. 1JL: 251-265.
1936.
(48) Jones, W. J., et. al. Simultaneous Adsorption from Dilute
Aqueous Solutions. J. Chem. Soc. 269-271. 1938.
(49) Kane, J. C., and Jatkar, S. K. K. Studies in Binary
Systems. J. Indian I. Soc. 21A: 385-394, 407-411,
413-416. 1938.
(50) Brunauer, Doming, Teller. A Theory of Van der Waal's Ad
sorption of Gases. J. Am. Chem. Soc. 62: 1723-1732.
1940.
(51) Wilson, J. Norton. A Theory of Chromotography. J. Am.
Chem. Soc. 62: 1583-1591. 1940.
(52) Martin, J. P., and Synge, R. L. M. A Theory of Chromo
tography. Brochen. J. 3j3: 1358-1368. 1941.
(53) De Vault. The Theory of Chromotography. J. Am. Chem.
Soc. 65: 532-540. 1943.
(54) Thomas, H. C. J. Am Chem. Soc. 166: 1664. 1944.
(55) Amundsen, Neal R. Mathematics of Adsorption in Bed.
J. Phys. and Colloid Chem. 52: 1153-1157. 1948.
(56) Hougen, 0. A., and Marshall, W. R. Adsorption From A
Fluid Stream Flowing Through A Granular Bed. Chem.
Engr. Progress. 43: 197-208. 1947.
(57) Wieke, E. The Separation of Gas Mixtures by Flow Through
Adsorbents. Angewandte Chem. B19: 15-21. 1947.
(58) Mair, B. J. Assembly and Testing of 52 Foot Lab.
Columns-Separation of Hydrocarbons. Ind. Eng. Chem.
39: 1072-1081. 1947.
(59) Arnold, James R. Adsorption of Gas Mixture. J. Am.
Chem. Soc. 71: 104-110. 1949.

-137-
I
>
>
(60) Berg, Clyde. Hypersorption. Petroleum Eng. jL8: 115-118.
1947.
(61) Spengler, Gunter and Kaenker, Karl. Selective Adsorp
tion of Hydrocarbon Mixtures. Erdol U. Kohle
317-321. 1950.
(62) Lewis, W. K., and Gilliland, E. G. Adsorption Equilibri
of Hydrocarbon Mixtures. Inc. Eng. Chem. 42: 1319-
1326. 1950.
(63) Eagle, Sam, and Scott, John. Liquid Phase Adsorption
Equilibrium and Kinetics. Ind. Eng. Chem. 42: 1287-
1294. 1950.
(64) Weiss, D. E. Industrial Fractional Adsorption. Roy.
Australian Chem. Inst. Proc. 17: 141-156. 1950.
(65) Amundsen, Neal R. Mathematics of Adsorption in Bed II.
J. Phys. and Colloid Chem. 54: 812-820. 1950.
(66) Kasten, Paul R. and Amundson, Neal R. An Elementary-
Theory of Adsorption in Fluidized Beds. Ind. Eng.
Chem. 42: 1341-1346. 1950.
(67) Mair, B.J. Theoretical Analysis of Adsorption Fractiona
tion. Ind. Eng. Chem. 42: 1279-1286. 1950.
(68) Amundsen, N. R. Effect of Intraparticle Diffusion. Ind.
Eng. Chem. 44: 1698-1703, 1704-1711. 1952.
(69) Hiester, N. K. Performance of Ion-Exchange and Adsorp
tion Columns. Chem. Eng. Prog. 48: 505-516. 1952.
(70) Rosen, J. B. Kinetics of a Fixed Bed System for Solid
Diffusion Into Spherical Particles. J. Chem. Phys.
20: 387-394. 1952.
(71) Gilliland and Baddour. Rate of Ion Exchange. I.E.C. 145
No. 2. 330-337. Feb., 1953.
(72) Rose, Arthur, Lombardo, R. J., and Williams, T. J.
Selective Adsorption Computations with Digital Com
puters. I.E.C. 43: No. 11. 2454-2458. Nov., 1951.
(73) Lombardo, R. J. Prediction of Composition Changes and
Gradients in Selective Adsorption Columns. Ph.D.
Thesis, Penn. State Col., Dept, of Ch. E. 1951.

-138-
(74) Lapidus, Leon, and Rosen, J. B. Exp. Investigations of
Ion Exchange Mechanisms in Fixed Beds by Means of An
Asymptotic Solution. Chem. Engr. Symposia on Ion
Exchange. 50: No. 14. 97-102. 1954.
(75) Heister, Nevin K., et. al. Interpretation and Correla
tion of Ion Exchange Column Performance Under Nonlinear
Equilibria. A. I. Ch. E. Journal. 2: No. 4. 404-411.
1956.
(76) Selke, W. A., et. al. Mass Transfer Rates in Ion Exchange.
A. I. Ch. E. Journal. 2; No. 4. 468-470. 1956.

APPENDIX
IBM 650 COMPUTER PROGRAM FOR SOLVING
ADSORPTION FRACTIONATION EQUATIONS
In the following pages the SOAP II program which was
developed to solve the partial differential equations derived
in section IV, Theory, is listed. This listing was printed
by an IBM 407 tabulating machine from the program deck of
punched cards, which was also used to read the program into
the computer. Both the machine language program and the
symbolic program, with descriptive comments, are listed. The
program listing is not arranged in the order of the flow
diagram of the problem (Figure 1), but it is arranged in the
order which was required for the SOAP II assembly program to
assign the machine language instruction and data addresses
optimally. By referring to the flow diagram (Figure 1) for
guidance, the program can be traced step-by-step through the
multiplicity of computations and logical decisions which the
computer makes in performing the computations.
In the original draft of the program, only the sym
bolic portion was written. This symbolic program was punched
into cards (following the SOAP II format); the SOAP II
assembly program was stored in the computer; and the symbolic
program cards were read into the computer. The computer,
-139-

-140-
using the SOAP II assembly program, translated the symbolic
program into a machine language program and punched out both
the symbolic and machine language programs into a fresh card
deck. This deck was used (after extensive "debugging") both
for printing the program and for reading the program into the
computer when it was desired to work the problem.
The steps followed in placing a problem into the
computer are described briefly below:
1. Read the entire program deck into the computer.
2. Provide the punch hopper of the computers read-punch
unit with fresh cards. (The read-punch unit should be
wired to punch and read eighty digits in normal order
on a card).
3. Place in the read hopper of the computer's read-punch
unit one or more "problem" cards. Each problem card
contains information as to the problem number, magnitude
of xjr, size of integration increment, and the frequency
desired in the punching of answer cards.
4. Place an instruction manually into the computer console
to read a card and proceed to location 1100 ( the first
instruction in the program).
5. Start the computer at the console instruction.

141
IBM 650 PROGRAM FOR
THE COMPUTATION OF
FIXED BED ADSORPTION
FRACTIONATION OF
BINARY LIQUID SOLUTIONS
RESERVE DRUM SPACE FOR
FUTURE USE
BLR
RESVE ZERO
01
9999
FOR STOP
0000 01
9999
BLR
0100
0500
STRAGE FOR
Y AND DRF
BLR
0501
0600
INITLIZING
SUBRTINES
BLR
1900
1999
DRUM PUNCH
OUT AND
READ IN
ZONE
COMPUTE
BLOCK FOR
NORMAL
POINT IN WAVE
TNLPA
RAL
0103
TNLP1
TEST FOR
0050
65
0103
0007
TNLP1
NZE
CNPWA
CL2PA
NEXT TO
LAST POINT
0007
45
0010
0011
CNPWA
RAU
DRFNW
COMPUTE
0010
60
0013
0017
MPY
EIGHT
CONTRIBUTN
0017
19
0020
0040
SRD
0009
OF PRESENT
0040
31
0009
0063
SLO
DRFPV
AND PREV
0063
16
0016
0021
STL
SUMDF
DRF TO
0021
20
0025
0028
CUBIC EQTN
RAU
DRFNW
COMPUTE
0028
60
0013
0067
SUP
DRFPV
ESTIMATE
0067
11
0016
0071
MPY
HLFAR
OF X BY
0071
19
0024
0044
SRD
0009
ADAMS
0044
31
0009
0617
RAU
8002
QUADRATIC
0617
60
8002-
0075
MPY
BI NCR
METHOD
0075
19
0078
0048
SRD
0009
0048
31
0009
0621
ALO
XNOW
0621
15
0074
0029

-142
STL
XEST
0029
20
0033
0036
LDD
DRFNW
0036
69
0013
0066
STD
DRFPV
CNPWB
0066
24
0016
0019
CNPWB
RAL
0302
CNPW2
COMPUTE
0019
65
0302
0057
CNPW2
LDD
CNPWC
0503
X BY CUBIC
0057
69
0060
0503
CNPWC
RAU
XEST
AVGING
0060
60
0033
0037
SUP
XSTAR
METHOD AND
0037
11
0090
0045
STU
DRFNW
COMPARE
0045
21
0013
0616
MPY
FIVE
WITH XEST
0616
19
0069
0640
SLT
0001
0640
35
0001
0047
A UP
SUMDF
0047
10
0025
0079
SRT
0002
0079
30
0002
0035
DVR
TV/LVE
0035
64
0033
0098
RAU
8002
0098
60
8002
0607
MPY
BI NCR
0607
19
0078
0648
SRD
0009
0648
31
0009
0671
ALO
XNOW
0671
15
0074
0629
AUP
XEST
0629
10
0033
0087
SLO
8002
0087
16
8002
0095
STD
XEST
0095
24
0033
0086
SUP
8001
0086
11
8001
0043
RAL
8003
0043
65
8003
0001
SRD
0001
0001
31
0001
0657
NZE
CNXSD
0657
45
0610
0061
LDD
XEST
CNPWD
0061
69
0033
0636
CNPWD
STD
1930
CNPW3
0636
24
1930
0083
CNPW3
STD
XNOW
CNPWE
0083
24
0074
0027
CNXSD
RAU
8001
COMPUTE
0610
60
8001
0667
MPY
HLFAS
NEWXEST
0667
19
0070
0690
SRD
0009
AND LOOP
0690
31
0009
0613
ALO
XEST
0613
15
0033
063 7
STL
XEST
CNPWC
0637
20
0033
0060
CNPWE
RAU
DRFNW
CNPWF
COMPUTE
0027
60
0013
0717
CNPV/F
SUP
0102
CNPW4
Y PRIME
0717
11
0102
0707
CNPW4
MPY
HLFAT
BY ADAMS
0707
19
0660
0030
SRD
0009
QUADRATIC
0030
31
0009
0003
ALO
DRFNW
CNPWG
METHOD
0003
15
0013
0767
CNPWG
STD
0102
CNPW5
0767
24
0102
0005
CNPW5
RAU
8 00 2
0005
60
8002
0663
MPY
TI NCR
0663
19
0666
0686
SRD
0009
CNPWH
0686
31
0009
0009
CNPWH
ALO
0302
CNPV/I
0009
15
0302
0757
cnpwi
STD
1933
CNPWJ
0757
24
1933
0736

-143-
CNPWJ
STL
0302 TSENB
0736
20 0302 0055
CONSTANTS
HLFAR
05
0024
05
HLFAS
05
0070
05
HLFAT
05
0660
05
EIGHT
80
0020
80
FIVE
50
0069
50
TWLVE
12
0038
12
TEST FOR END OF BED
TSENB
RAL
CNPWF
0055
65
0717
0721
SLO
TSEBK TSENC
0721
16
0624
0679
TSENC
NZE
TSNWV RSETA
0679
45
0032
0633
CONSTANTS
TSEBK
SUP
0299 CNPW4
0624
11
0299
0707
TEST FOP
! END OF WAVE
TSNWV
RAL
xnov;
TSNWB
TEST FOR
0032
65
0074
0729
TSNWB
SRD
0001
TSNWC
END OF
0729
31
0001
0085
TSNWC
NZE
TSNWA
WAVE
0085
45
0088
0039
RAL
SKPKA
AFTER
0039
65
0042
0097
LDD
TSNWB
FIRST DROP
0097
69
0729
0 08 2
S IA
TSNWB
BECOMES
0082
23
0729
0632
RAL
SKPKB
PURE COMPA
0632
65
0635
0089
LDD
TNLP1
SKIP CALC
0089
69
0007
0710
S IA
TNLP1
OF LAST 2
0710
23
0007
0760
SLO
8002
TSNWA
POINTS
0760
16
8002
0088
TSNWA
NZE
AVPIA
RSETA
0088
45
0092
0633
CONSTANTS
SKPKA
01
SKPKA
TSNWA
0042
01
0042
0088
SKPKB
01
SKPKB
CNPWA
0635
01
0635
0010
ADVANCE ONE POINT
INSIDE WAVE

AVPIA
RAL
AVPKA
0092
65
0645
0049
AUP
8001
0049
10
8001
0807
ALO
TNLPA
0807
15
0050
0605
LDD
CL1PC
0605
69
0008
0611
SDA
CL1PC
0611
22
0008
0661
SLO
8002
0661
16
8002
0619
STD
TNLPA
0619
24
0050
0053
ALO
CNPWB
0053
15
0019
0023
ALO
8003
0023
15
8003
0031
LDD
CNPWH
0031
69
0009
0012
SDA
CNPWH
0012
22
0009
0062
LDD
CNPWJ
0062
69
0736
0639
SDA
CNPWJ
0639
22
0736
0689
LDD
CL2PC
0689
69
0642
0695
SDA
CL2PC
0695
22
0642
0745
LDD
CL2PI
0745
69
0698
0051
SDA
CL2PI
0051
22
0698
0601
LDD
CL2P4
0601
69
0004
0857
SDA
CL2P4
0857
22
0004
0907
LDD
CL2PM
0907
69
0810
0713
SDA
CL2PM
0713
22
0810
0763
LDD
CL2PN
0763
69
0716
0669
SDA
CL2PN
0669
22
0716
0719
SLO
8 002
0719
16
8 002
0077
STD
CNPWB
0077
24
0019
0022
ALO
CL1PD
0022
15
062 5
0779
ALO
8003
0779
15
8003
0687
SLO
8002
0687
16
8002
0795
STD
CL1PD
0795
24
0625
0628
ALO
CNPWF
0628
15
0717
0771
ALO
8003
0771
15
8003
0829

-14 5-
AVPIB
AVPIC
LDD
CNPWG
0829
69
0767
0620
SDA
CNPWG
0620
22
0767
0670
LDD
CL2PB
0670
69
0073
0026
SDA
CL2PB
0026
22
0073
0076
LDD
CL2PE
0076
69
0879
0682
SDA
CL2PE
0682
22
0879
0732
LDD
CL2PK
0732
69
0685
0638
SDA
CL2PK
0638
22
0685
0688
LDD
CL2PL
0688
69
0041
0094
SDA
CL2PL
0094
22
0041
0644
SLO
3002
AVP I B
0644
16
8002
0603
STD
CNPWF
AVPIC
0603
24
0717
0720
ALO
CNPWD
0720
15
0636
0091
ALO
8003
0091
15
8003
0099
LDD
CL2PG
0099
69
0002
0655
SDA
CL2PG
0655
22
0002
0705
SLO
8002
0705
16
8 002
0813
STD
CNPWD
0813
24
0636
0739
ALO
CNPWI
0739
15
0757
0711
ALO
8003
0711
15
8003
0769
LDD
CL2PH
0769
69
0072.
0675
SDA
CL2PH
0675
22
0072
0725
SLO
8002
0725
16
8002
0683
STD
CNPWI
0683
24
0757
0860
SRT
0001
ADD ONE TO
0860
30
0001
0817
AUP
WDCTR
WORD
0817
10
0770
0775
STU
WDCTR
TNLPA
COUNTER
0775
21
0770
0050
CONSTANTS
AVPKA
0001
0645
0001

PUNCH SUBROUTINES
TSWDA
RAL
V/DCTR
SET WORD
0650
65
0770
0825
SLO
THREE
COUNT AMD
0825
16
0678
0733
NZE
AVPIA
LOCATION
0733
45
0092
073 7
RAL
CNPWJ
OF FIRST
0737
65
0736
0641
SRT
0004
WORD IN
0641
30
0004
0651
SLO
TV/O
PUNCH ZONE
0651
16
0054
0059
ALO
V/DCTR
0059
15
0770
0875
LDD
1927
0875
69
1927
0080
S IA
1927
0080
23
1927
063 0
RAL
8001
0630
65
8001
0737
ALO
CDCST
ADD ONE TO
0787
15
0740
0845
5TL
1927
CARD COUNT
0845
20
1927
0680
PCH
1927
PUNCH
0680
71
1927
0627
STU
V/DCTR
ZERO WORD
0627
21
0770
0623
RAL
WDKTA
COUNTER
0623
65
0626
0081
LDD
CNPWD
0081
69
0636
0789
SDA
CNPWD
RESET
0789
22
0636
0839
LDD
CL2PG
ADDRESSES
0839
69
0002
0755
SDA
CL2PG
OF INSTRUC
0755
22
0002
0805
TIONS THAT
RAL
V/DKTB
STORE ANS
0805
65
0058
0863
LDD
CNPWI
IN PUNCH
0863
69
0757
0910
SDA
CNPWI
ZONE
0910
22
0757
0960
LDD
CL2PH
0960
69
0072
0925
SDA
CL2PH
AVPIA
092 5
22
0072
0092
PCHAA
RAL
CNPWJ
SETWORD
0700
65
0736
0691
SRT
0001
COUNT AND
0691
30
0001
0647
ALO
WDONE
COUNT AND
0647
15
0750
0855
SLO
V/DCTR
LOCATION
0855
16
0770
0975
SRT
0003
WORD IN
0975
30
0003
0783
ALO
8001
OF FIRST
0783
15
8001
0741
LDD
1927
PUNCH ZONE
0741
69
1927
0730
S IA
1927
0730
23
1927
0780
RAL
8001
ADD ONE TO
0780
65
8001
0837
ALO
CDCST
CARD COUNT
0837
15
0740
0895
STL
1927
0895
20
1927
0830
STU
TMCTR
ZERO TMCTR
0830
21
0034
0887
PCH
1927
R5ETA
PUNCH
0887
71
1927
0633

147-
CONSTANTS
THREE
3000
0678
3000
TWO
0002
0054
0002
CDCST
0001
0740
0001
WDKTA
01
1927
WDKTA
0626
01
1927
0626
WDKTB
01
1930
WDKTB
0058
01
1930
0058
WDONE
1000
0750
1000
PCHBA
RAL
CNPWJ
SET WORD
0800
65
0736
0791
SRT
0001
COUNT AND
0791
30
0001
0697
ALO
WDONE
LOCATION
0697
15
0750
0905
SLO
WDCTR
OF FIRST
0 90 5
16
0 77 0
1025
SRT
0003
WORD IN
1025
30
0003
0833
ALO
0001
PUNCH ZONE
0833
15
8 001
0841
LDD
1927
0841
69
1927
0880
S IA
1927
0880
23
1927
0930
RAL
8001
ADD ONE TO
0930
65
8001
0937
ALO
CDCST
CARD COUNT
0937
15
0740
0945
STL
1927
0945
20
1927
0980
STU
TMCTR
ZERO TMCTR
0980
21
0034
0987
PCH
1927
PUNCH
0987
71
1927
0677
RAL
CL1PD
SET WORD
0677
65
062 5
0929
SRT
0004
COUNT AND
0929
30
0 0 04
0889
ALO
WDONE
LOCATION
0889
15
0750
0955
LDD
1927
OF FIRST
0955
69
1927
1030
S I A
1927
DROP IN
1030
23
1927
1080
RAL
8001
PUNCH ZONE
1080
65
8001
1037
ALO
CDCST
1037
15
0740
0995
STL
1927
0995
20
1927
1130
LDD
XFSDP
STORE CONC
1130
69
0883
0786
STD
1928
OF FIRST
0786
24
1928
0631
STD
1931
DROP INTO
0631
24
1931
0084
STU
1929
PUNCH ZONE
0084
21
1929
0782
STD
1930
0782
24
1930
0933
STD
1932
0933
24
1932
0735
STD
1933
0735
24
1933
0836
PCH
1927
RSETA
PUNCH
0836
71
1927
0633
PCHCA
LDD
0310
0850
69
0310
0913

148-
STD
0301
0913
24
0301
0604
STD
1929
0604
24
1929
0832
STD
1932
0832
24
1932
0785
LDD
0110
0785
69
0110
0963
STD
0101
0963
24
0101
0654
LDD
YFSPT
0654
69
0957
1010
STD
1931
1010
24
1931
0634
LDD
XFEED
0634
69
1087
0790
STD
1928
0790
24
1928
0681
SLO
8002
0681
16
8002
0939
STL
1930
0939
20
1930
0983
STD
1933
0983
24
1933
08 8 6
LDD
1957
0886
69
1957
1060
STD
TMCST
1060
24
1013
0766
RAL
1958
0766
65
1958
1063
STL
TI NCR
1063
20
0666
0819
RSL
8002
0819
66
8002
0727
STL
BI NCR
0727
20
0078
0731
SLO
3002
0731
16
8002
0989
STU
0302
0989
21
0302
1005
STD
0303
1005
24
0303
0006
STD
0304
0006
24
0304
1007
STD
0305
1007
24
0305
0608
STD
0306
0608
24
0306
0609
STD
0307
0609
24
0307
1110
STD
0308
1110
24
0308
0761
STD
0309
0761
24
0309
0612
STD
0310
0612
24
0310
1113
STD
0102
1113
24
0102
1055
STD
0103
1055
24
0103
0056
STD
0104
0056
24
0104
1057
STD
0105
1057
24
0105
0658
STD
0106
0658
24
0106
0659
STD
0107
0659
24
0107
1160
STD
0108
1160
24
0108
0311
STD
0109
0311
24
0109
0662
STD
0110
0662
24
0110
1163
LDD
RSTKO
1163
69
0816
0869
STD
TSTMB
0869
24
0622
1075
LDD
0100
1075
69
0100
0653
STD
DRFPV
0653
24
0016
0919
LDD
DFEED
0919
69
0672
1125
STD
0100
1125
24
0100
0703
LDD
YFSPT
0703
69
0957
1210
STD
0300
1210
24
0300
0753

-149-
LDD
1958
0753
69
1958
0861
STD
1934 PARTC
0861
24
1934
1137
COMPUTE
NEXT TO LAST
POINT
IN
WAVE
CL2PA
RAU
DRFNW
COMPUTE
0011
60
0013
0867
MPY
EIGHT
CONTRIBUTM
0867
19
0020
08 40
SRD
0009
OF PRESENT
0040
31
0009
1213
SLO
DRFPV
AND PREV
1213
16
0016
0821
STL
SUMDF
DRF TO
0821
20
0025
0728
CUBIC EQTN
RAU
DRFNW
COMPUTE
0728
60
0013
0917
SUP
DRFPV
ESTIMATE 0
0917
11
0016
0871
MPY
HLFBA
X BY ADAMS
0871
19
0674
0694
SRD
0009
QUADRATIC
0694
31
0009
0967
RAU
8002
METHOD
0967
60
8002
1175
MPY
31 NCR
1175
19
0078
0748
SRD
0009
0748
31
0009
0921
ALO
XNOW
0921
15
0074
0979
STL
XEST
0979
20
0033
0936
LDD
DRFNW
0936
69
0013
0866
STD
DRFPV
CL2PB
0866
24
0016
0073
CL2PB
RAU
0102
CL2P1
COMPUTE
0073
60
0102
1107
CL2P1
MPY
T I NCR
ESTIMATE
1107
19
0666
0986
SRD
0009
CL2PC
OF Y BY
0986
31
0009
0642
CL2PC
ALO
0302
CL2P2
LINEAR
0642
15
0302
1157
CL2P2
STL
YEST
CL2PD
METHOD
1157
20
0911
0 014
CL2PD
RAL
YEST
COMPUTE
0014
65
0911
0015
LDD
0503
NEW Y BY
0015
69
0018
0503
RAU
XEST
AVGING
0018
60
0033
1187
SUP
XSTAR
METHOD
1187
11
0090
1045
STU
DRFNW
CL2PE
AND COMP
1045
21
0013
0879
CL2PE
AUP
0102
CL2P3
WITH YEST
0879
10
0102
1207
CL2P3
MPY
HLFBB
1207
19
1260
1180
SRD
0009
1180
31
0009
0803
RAU
8002
0803
60
8002
0961
MPY
T I NCR
0961
19
0666
1036
SRD
0009
CL2P4
1036
31
0009
0004
CL2P4
ALO
0302
0004
15
0302
1257
AUP
YEST
1257
10
0911
0065
SLO
8002
0065
16
8002
0673

150
STD
YEST
0673
24
0911
0064
SUP
8001
0064
11
8001
0971
RAL
8003
0971
65
8003
1029
SRD
0001
1029
31
0001
0835
NZE
CNYSB
CL2PF
0835
45
0738
1039
CNYSB
RAU
8001
COMPUTE
073 8
60
8001
1095
MPY
HLFBC
NEW YEST
1095
19
0793
0068
SRD
0009
AMD LOOP
0068
31
0009
0891
ALO
YEST
0891
15
0911
0615
STL
YEST
CL2PD
0615
20
0911
0014
CL2.PF
RAU
DRFNW
COMPUTE
1039
60
0013
1017
MPY
FIVE
X BY CUBIC
1017
19
0069
0890
SLT
0001
AVGING
0890
35
0001
0747
AUP
SUMDF
METHOD AMD
0747
10
0025
1079
SRT
0002
COMPARE
1079
30
0002
0885
DVR
TWLVE
WITH XEST
0385
64
0038
0848
RAU
0002
0848
60
8002
1307
MPY
BI NCR
1307
19
0078
0898
SRD
0009
0898
31
0009
1021
ALO
XNOW
1021
15
0074
1129
AUP
XEST
1129
10
0033
1237
SLO
0002
1237
16
8002
1145
STD
XEST
1145
24
0033
1086
SUP
0001
1086
11
8001
0093
RAL
8003
0093
65
8003
0701
SRD
0001
0701
31
0001
1357
NZE
CNXSE
1357
45
1310
1011
LDD
XEST
CL2PG
1011
69
0033
0002
CL2PG
STD
1930
0002
24
1930
1033
STD
XNOW
1033
24
0074
0777
LDD
YEST
CL2PH
0777
69
0911
0072
CL2PH
STD
1933
CL2PI
0072
24
1933
0698
CL2PI
STD
0302
CL2PJ
0698
24
0302
1105
CMXSE
RAU
8001
COMPUTE
1310
60
8001
1067
MPY
HLFBD
NEW XEST
1067
19
0820
0940
SRD
0009
AND LOOP
0940
31
0009
1263
ALO
XEST
1263
15
0033
1287
STL
XEST
CL2PD
1287
20
0033
0014
CL2PJ
RAU
DRFNW
CL2PK
COMPUTE
1105
60
0013
0685
CL 2PK
SUP
0102
Y PRIME
0685
11
0102
1407

-151-
MPY
HLFCA
BY ADAMS
1407
19
1360
1230
SRD
0009
QUADRATIC
1230
31
0009
0853
ALO
DRFNW
CL2PL
METHOD
0853
15
0013
0041
CL2PL
STD
0102
0041
24
0102
1155
RAU
8002
1155
60
8002
1313
MPY
T I NCR
1313
19
0666
1136
SRD
0009
CL2PM
1136
31
0009
0810
CL 2 PM
ALO
0302
CL2PN
0810
15
0302
0716
CL2PN
STL
0302
CL1PA
0716
20
0302
1205
CONSTANTS
HLFBA
05
0674
05
HLFBB
05
1260
05
HLFBC
05
0798
05
HLFBD
05
0820
05
HLFCA
05
1360
05
COMPUTE LAST POINT IN WAVE
OR FIRST DROP OF LIQUID
CL1PA
RAU
DRFNW
COMPUTE
1205
60
0013
1117
SUP
DRFPV
XEST BY
1117
11
0016
1071
MPY
HLFBE
ADAMS
1071
19
0724
0744
SRD
0009
QUADRATIC
0744
31
0009
1167
ALO
DRFNW
METHOD
1167
15
0013
1217
RAU
8002
1217
60
8002
1225
MPY
BI NCR
1225
19
0078
0948
SRD
0009
0948
31
0009
1121
ALO
KNOW
1121
15
0074
1179
STL
XEST
1179
20
0033
1186
RAU
DRFNW
COMPUTE
1186
60
0013
1267
MPY
EIGHT
CONTRIBUTN
1267
19
0020
0990
SRD
0009
OF PRESENT
0990
31
0009
1363
SLO
DRFPV
AND PREV
1363
16
0016
1171
STL
SUMDF
CL1PB DRF
1171
20
0025
0778
CL1PB
RAL
XEST
0778
65
0033
1337
LDD
0503
1337
69
1040
0503
RAU
XEST
1040
60
0033
1387
SUP
XSTAR
CL1PC
1387
11
0090
0008
CL1PC
STU
0103
CL1P1
0008
21
0103
0606
CL 1P1
MPY
FIVE
0606
19
0069
1090

152
SLT
0001
1090
35
0001
0797
AUP
SUMDF
0797
10
0025
1229
SRT
0002
1229
30
0002
0935
- DVR
TWLVE
0935
64
0038
0998
RAU
8002
0998
60
8002
1457
MPY
B I NCR
1457
19
0078
1048
5RD
0009
1048
31
0009
1221
ALO
XNOW
1221
15
0074
1279
A'JP
XF.ST
1279
10
0033
1437
SLO
8002
1437
16
8002
1195
STD
XEST
1195
24
0033
1236
SUP
8001
1236
11
8001
0643
RAL
8003
0643
65
8 003
0751
SRD
0001
0751
31
0001
1507
NZE
CNXSF
1507
45
1410
1061
LDD
XEST
CL 1 PD
1061
69
0033
062 5
CL1PD
STD
0 30 3
CL1PE
0625
24
0303
0656
CL1PE
STD
XFSDP
RSETA
0656
24
0883
0633
CNXSF
RAU
8001
1410
60
8001
1317
MPY
HLFBF
1317
19
0870
1140
SRD
0009
1140
31
0009
1413
ALO
XEST
1413
15
0033
1487
STL
XEST
CL1PB
1487
20
0033
0778
CONSTANTS
HLFBE
05
0724
05
HLFBF
05
0870
05
RESET ADDRESSES
RSETA RAL
RSTKA
0633
65
1236
0941
LDD
TNLPA
0941
69
0050
0903
SDA
TNLPA
0903
22
0050
0953
LDD
CL1PC
0953
69
0008
1111
SDA
CL1PC
1111
22
0008
1161
RAL
RSTKB
1161
65
0614
0969
LDD
CNPWB
0969
69
0019
0722
SDA
CNPWB
0722
22
0019
0772
LDD
CNPWH
0772
69
0009
0712
SDA
CNPWH
0712
22
0009
0762
LDD
CNPWJ
0762
69
0736
1089

-153-
SDA CNPWJ
LDD CL2PC
SDA CL2PC
LDD CL2PI
SDA CL2PI
LDD CL2P4
SDA CL2P4
LDD CL2PM
SDA CL2PM
LDD CL2PN
SDA CL2PN
RAL RSTKC
LDD CNPWF
SDA CNPWF
LDD CNPWG
SDA CNPWG
LDD CL2PB
SDA CL2PB
LDD CL2PE
SDA CL2PE
LDD CL2PK
SDA CL2PK
LDD CL2PL
SDA CL2PL
RAL RSTKD
LDD CNPWD
SDA CNPWD
LDD CL2PG
SDA CL2PG
RAL RSTKE
LDD CNPWI
SDA CNPWI
LDD CL2PH
SDA CL2PH
LDD RSTKF
STD CL1PD
LDD RSTKG
STD WDCTR TSWFA
1089
22
0736
1139
1139
69
0642
1245
1245
22
0642
1295
1295
69
0698
0801
0801
22
0698
0851
0851
69
0004
1557
1557
22
0004
1607
1607
69
0810
1463
1463
22
0810
1513
1513
69
0716
1019
1019
22
0716
1069
1069
65
0822
0827
0827
69
0717
0920
0920
22
0717
0970
0970
69
0767
102 0
1020
22
0767
1070
1070
69
0073
0676
0676
22
0073
0726
0726
69
0879
0882
0882
22
0879
0932
0932
69
0685
0788
0788
22
0685
0838
0838
69
0041
0794
0794
22
0041
0844
0844
65
0847
0901
0901
69
0636
1189
1189
22
0636
1239
1239
69
0002
1255
1255
22
0002
1305
1305
65
0708
1563
1563
69
0757
1460
1460
22
0757
1510
1510
69
0072
1275
127 5
22
0072
1325
1325
69
0828
0781
0781
24
0625
0878
0878
69
0831
0684
0684
24
0770
0723
CONSTANTS

154-
RSTKA
01
0103
RSTKA
1286
01
0103
1286
RSTKB
01
0302
RSTKB
0614
01
0302
0614
RSTKC
01
0102
RSTKC
0822
01
0102
0822
RSTKO
01
1930
RSTKD
0 847
01
1930
0847
RSTKE
01
1933
RSTKE
0708
01
1933
0708
RSTKF
STD
0303
CL1PE
0828
24
0303
0656
RSTKG
3000
0831
3000
TEST FOR WAVE FRONT
TSWFA
RAL
0300
TSV/F1
0723
65
0300
1355
TSV/F1
SLO
YEQFD
1355
16
0758
1613
SRD
0001
1613
31
0001
1119
BMI
SATBD
1119
46
0872
0773
NZE
SATBD
0872
45
0776
0773
LDD
CFPWA
SRYF
0776
69
1329
0982
SATBD
STD
0300
AD V Vi A
0773
24
0300
1003
TEST FOR
END OF PROBLEM
TSENP
RAL
TSWFA
0900
65
0723
0877
SLO
ENPRK
0877
16
1280
0985
BMI
RSETA
0985
46
0633
1289
NZE
8000
1289
45
8000
0693
RAU
8003
ARRANGE
0693
60
8003
0951
STL
TMCTR
TO PUNCH
0951
20
0034
1537
LDD
TMONE
LAST TIME
1537
69
1190
0743
STD
TMCST
RSETA
INCREMENT
0743
24
1013
0633
CONSTANTS
ENPRK
RAL
0497
TSWF1
1280
65
0497
1355
CALCULATION OF FIRST
POINT
IN
WAVE
SRYF
STD
SRYFZ
SRYFP
0982
24
1035
0888
SRYFP
RAL
0300
SRYFG
COMPUTE
0888
65
0300
1405
SRYFG
STD
1931
1405
24
1931
0734
STD
YFSPT
0734
24
0957
1560

-155
LDD
0503
PRESENT
1560
69
1663
0 5 03
RAU
XFEED
DRIVING
1663
60
1087
0991
STD
1928
0991
24
1928
0881
SUP
XSTAR
FORCE
0881
11
0090
1345
STU
DRFNW
SRYFA
COMPUTE
1345
21
0013
0916
SRYFA
SUP
0100
SRYF2
ESTIMATE
0916
11
0100
145 5
SRYF2
MPY
HLFAJ
OF Y BY
145 5
19
0803
0928
SRD
0009
ADAMS
0928
31
0009
1001
ALO
DRFNW
1001
15
0013
1367
RAU
8002
QUADRATIC
1367
60
8002
1375
MPY
T I NCR
METHOD
1375
19
0666
1336
SRD
0009
SRYFB
1336
31
0009
0709
SRYFB
ALO
0300
SRYF3
0709
15
0300
1505
SRYF3
STL
YEST
1505
20
0911
0664
RAU
DRFNW
0664
60
0013
1417
MPY
EIGHT
1417
19
0 02 0
1240
SRD
0009
SRYFC
1240
31
0009
1713
5RYFC
SLO
0100
SRYFA
1713
16
0100
1555
SRYF4
STL
SUMDF
AVGYC
1555
20
0025
0978
AVGYC
RAL
YEST
COMPUTE
0978
65
0911
0665
LDD
0503
Y PRIME
0665
69
0618
0503
RAU
XFEED
BY CUBIC
0618
60
1087
1041
SUP
XSTAR
METHOD AND
1041
11
0090
1395
MPY
FIVE
COMPARE
1395
19
0069
1290
SLT
0001
WITH YEST
1290
35
0001
0897
AUP
SUMDF
0897
10
0025
1379
SRT
0002
1379
30
0002
1085
DVR
TWLVE
1085
64
0038
1098
RAU
8002
1098
60
8002
1657
MPY
TI NCR
1657
19
0666
1386
SRD
0009
SRYFD
1386
31
0009
0759
SRYFD
ALO
0300
SRYF5
0759
15
0300
1605
SRYF5
AUP
YEST
1605
10
0911
0715
SLO
8002
0715
16
8002
0823
STD
YEST
0823
24
0911
0 714
SUP
8001
0714
11
8001
1271
RAL
8003
1271
65
8003
1429
SRD
0001
1429
31
0001
1135
NZE
CNYSC
1135
45
0938
1339
LDD
YEST
SRYFE
1339
69
0911
0764
SRYFE
STD
0300
0764
24
0300
1053
LDD
DRFNW
SRYFF
1053
69
0013
0966
SRYFF
STD
0100
SRYF7
0966
24
0100
1103
SRYF7
STD
DRFPV
SRYFZ
1103
24
0016
1035

-156-
CNYSC
RAU
8001
COMPUTE
0938
60
8001
1445
MPY
HLFAL
NEW YEST
1445
19
1143
0668
SRD
0009
AND LOOP
0668
31
0009
1091
ALO
YEST
1091
15
0911
0765
STL
YEST
AVGYC
0765
20
0911
0978
CFPWA
RAU
DRFPV
COMPUTE
1329
60
0016
1321
MPY
81 NCR
XEST
1321
19
0078
1198
SRD
0009
AT NEXT
1198
31
0009
1371
ALO
XFEED
POINT BY
1371
15
1087
1141
STL
XEST
CFPWB
LNEAR METH
1141
20
0033
1436
CFPWB
RAL
0301
CFPW1
COMPUTE
1436
65
0301
1655
CFPW1
LDD
CFPWC
0503
XSTAR AT
1655
69
0858
0503
CFPWC
RAU
XEST
NEXT POINT
0858
60
0033
1587
SUP
XSTAR
1587
11
0090
1495
STU
DRFNW
COMPUTE
1495
21
0013
1016
AUP
DRFPV
X AT NEXT
1016
10
0016
1421
MPY
HLFAN
POINT BY
1421
19
0774
0894
SRD
0009
AVGING AND
0894
31
0009
1467
RAU
8002
COMPARE
1467
60
8002
1425
MPY
BI NCR
WITH XEST
142 5
19
0078
1248
SRD
0009
1248
31
0009
1471
ALO
XFEED
1471
15
1087
1191
AUP
XEST
1191
10
0033
1637
SLO
8002
1637
16
8002
1545
STD
XEST
1545
24
0033
1486
SUP
8001
1486
11
8001
0793
RAL
8003
079 3
65
0003
1051
SRD
0001
1051
31
0001
1707
NZE
CNXSC
1707
45
1610
1211
LDD
XEST
1211
69
0033
1536
STD
1929
1536
24
1929
1032
STD
XNOW
CFPWD
1032
24
0074
0927
CNXSC
RAU
0001
COMPUTE
1610
60
8001
1517
MPY
HLFAP
NEW XEST
1517
19
1120
1340
SRD
0009
AND LOOP
1340
31
0009
1763
. ALO
XEST
1763
15
0033
1687
STL
XEST
CFPWC
1687
20
0033
0858
CFPWD
RAU
DRFNW
CFPWE
COMPUTE
0927
60
0013
1567
CFPWE
SUP
0101
CFPW2
Y PRIME
1567
11
0101
1705
CFPW2
MPY
HLFAM
BY ADAMS
1705
19
0908
1028

157-
SRD
0009
QUADRATIC
1028
31
0009
1101
ALO
DRFNW
CFPWF
METHOD
1101
15
0013
1617
CFPWF
STD
0101
CFPW3
1617
24
0101
0 704
CFPW3
RAU
8002
0 704
60
8002
1813
MPY
TI NCR
1813
19
0666
1586
SRD
0009
CFPWG
1586
31
0009
0809
CFPWG
ALO
0301
CFPW4
0809
15
0301
1755
CFPW4
STD
1932
CFPWH
1755
24
1932
1185
CFPVJH
STL
0301
TSTIM
1185
20
0301
0754
CONSTANTS
HLFAJ
05
0808
05
HLFAL
05
1148
05
HLFAM
05
0908
05
HLFAN
05
0774
05
HLFAP
05
1120
05
TEST'- TIME FOR PUNCHING
TSTIM
RAL
TMCTR
ADD ONE TO
0754
65
0034
1389
ALO
TMONE
TIME CTRS
1389
15
1190
1595
AUP
8001
AND TEST
1595
10
8001
1153
AUP
1934
FOR PUNCH
1153
10
193 4
1439
STU
1934
1439
21
1934
1737
STL
TMCTR
1737
20
0034
1787
SUP
8003
1787
11
8003
1645
SLO
TMCST
TSTMB
1645
16
1013
0622
TSTMB
NZE
STPCB
STPCA
0622
45
0826
0977
STPCA
STU
TMCTR
0977
21
0034
1837
RAL
SPCKA
1837
65
1390
1695
LDD
TSENC
1695
69
0679
1082
S IA
TSENC
1082
23
0679
1132
LDD
TSNWA
1132
69
0088
1241
SDA
TSNWA
1241
22
0088
1291
S IA
TSNWA
1291
23
0080
1341
RAL
SPCKB
1341
65
0944
0649
LDD
CL1PE
0649
69
0656
0859
S IA
CL1PE
0859
23
0656
0909
RAL
SPCKF
0909
65
0 812
1667
LDD
A VP IB
1667
69
0603
0706

-158-
S IA
AVPIR
TNLPA
0706
23
0603
0050
STPCB
RAL
SPCKD
0826
65
1479
1083
LDD
TSENC
1083
69
0679
1182
S IA
TSENC
1182
23
0679
1232
LDD
TSNWA
1232
69
0088
1391
SDA
TSNWA
1391
22
0088
1441
S IA
TSNWA
1441
23
0038
1491
RAL
SPCKE
1491
65
0994
0699
LDD
CL 1PE
0699
69
0656
0959
S IA
CL1PE
0959
23
0656
1009
RAL
SPCKC
1009
65
0862
1717
LDD
AVPIB
1717
69
0603
0756
S IA
AVPIB
TNLPA
0756
23
0603
0050
5TPCC
STU
TMCTR
0950
21
0034
1887
RAL
SPCKG
1887
65
1440
1745
LDD
CL1PE
1745
69
0656
1059
S IA
CL1PE
TNLPA
1059
23
0656
0050
CONSTANTS
SPCKA
01
TSWDA
PCHAA
1390
01
0650
0700
SPCKB
01
SPCKB
PCHBA
0944
01
0944
0800
SPCKC
01
SPCKC
TNLPA
0862
01
0862
0050
SPCKD
01
AVPIA
RSETA
1479
01
0092
0633
SPCKE
01
SPCKE
RSETA
0994
01
0994
0633
SPCKF
01
SPCKF
AVPIC
0812
01
0812
0720
SPCKG
01
spEkg
PCHCA
1440
01
1440
0850
TMONE
0001
1190
0001
ADVANCE WAVE ONE POINT
ADVWA RAL
AVV/KA
1003
65
0806
1261
AUP
8001
1261
10
8001
1169
ALO
RSTKA
1169
15
1286
1541
SLO
8002
1541
16
8002
0749
STD
RSTKA
0749
24
1286
1489
ALO
RSTKB
148 9
15
0614
1219
ALO
8003
1219
15
8003
1027
SLO
' 8002
1027
16
8 002
1235

-15 9-
STD
RSTKB
1235
24
0614
1767
ALO
RSTKC
1767
15
0822
1077
ALO
S003
1077
15
8 003
1285
SLO
8002
1285
16
8002
0843
STD
RSTKC
0343
24
0822
1475
ALO
RSTKF
1475
15
0823
1133
ALO
8003
1133
15
3003
1591
SLO
8002
1591
16
8002
0799
5TD
RSTKF
0799
24
0828
0931
ALO
TSWFA
0931
15
0723
1127
ALO
8003
1127
15
8 003
1335
SLO
8002
1335
16
8002
0893
STD
TSWFA
0893
24
0723
0876
ALO
SATBD
0876
15
0773
1177
ALO
8003
1177
15
8003
1385
SLO
8002
1385
16
8002
0943
STD
SATBD
0943
24
0773
0926
ALO
CFPWB
0926
15
1436
1641
ALO
8003
1641
15
8003
0849
LDD
CFPWG
0849
69
0809
0912
SDA
CFPWG
0912
22
0809
0962
LDD
CFPWH
0962
69
1185
0988
SDA
CFPWH
0988
22
1185
1038
SLO
8002
1038
16
8002
0947
STD
CFPWB
0947
24
1436
1539
ALO
CFPWE
1539
15
1567
1521
ALO
8003
1521
15
8003
1529
LDD
CFPWF
1529
69
1617
1170
SDA
CFPWF
1170
22
1617
1220
SLO
8002
1220
16
8002
1579
STD
CFPWE
1579
24
1567
1270
ALO
SRYFP
1270
15
0888
0993
ALO
8003
0993
15
8003
1151
LDD
SRYFB
1151
69
0709
1012
SDA
SRYFB
1012
22
0709
1062
LDD
SRYFD
1062
69
0759
1112
SDA
SRYFD
1112
22
0759
1162
LDD
SRYFE
1162
69
0764
1817

160 -
AVWKA
PARTA
SOA
SRYFE
1817
22
0764
1867
SLO
8002
1867
16
8002
1525
STD
SRYFP
1525
24
0088
1691
ALO
SRYFA
1691
15
0916
1571
ALO
8003
1571
15
8003
1629
LDD
SRYFC
1629
69
1713
1066
SDA
SRYFC
1066
22
1713
1116
LDD
SRYFF
1116
69
0966
1269
SDA
SRYFF
1269
22
0966
1319
SLO
0002
1319
16
8002
1227
STD
SRYFA TSENP
1227
24
0916
0900
CONSTANTS
0001
0806
0001
CALCULATION OF FIRST
TWO TIME
: INCREMENTS
LDD
XFEED
PUNCH
1000
69
1087
1490
STD
1926
CARD
1490
24
1928
0981
STD
1931
FOR ZERO
0981
24
1931
0784
SLO
8002
TIME
0784
16
8 002
1043
STL
1929
INCREMENT
1043
20
1929
1282
STD
1930
1282
24
1930
1183
STD
1932
1183
24
1932
143 5
STD
1933
1435
24
1933
163 6
RAU
1927
1636
60
1927
1031
AUP
CDCSA
1031
10
0834
1589
STU
1927
1589
21
1927
1330
PCH
1927
PUNCH CARD
1330
71
1927
1277
RAL
XFEED
COMPUTE
1277
65
1087
1741
LDD
0503
DRVF FOR
1741
69
1044
0503
RAU
XFEED
FIRST BED
1044
60
1087
1791
STD
1928
POINT
1791
24
1928
1081
SUP
XSTAR
1081
11
0090
1795
STU
0100
1795
21
0100
1203
STD
DFEED
1203
24
0672
1575
MPY
TI NCR
COMPUTE
1575
19
0 666
1686
SRD
0009
YEST BY
1686
31
0009
1109
ALO
XFEED
LINEAR
1109
15
1087
1841

-161-
STL
YEST
AVGYA
METHOD
1841
20
0911
0814
AVGYA
LDD
0503
COMPUTE Y
0814
69
0718
0503
RAU
XFEED
BY AVGING
0718
60
1087
1891
SUP
XSTAR
METHOD AND
1891
11
0090
1845
STU
DRFPV
COMPARE
1845
21
0016
1369
AUP
0100
1369
10
0100
1305
MPY
HLFAA
WITH YEST
1805
19
0958
1078
SRD
0009
1078
31
0 009
1201
RAU
8002
1201
60
8002
1159
MPY
T I NCR
1159
19
0666
1736
SRD
0009
1736
31
0009
1209
ALO
XFEED
1209
15
1087
0692
AUP
YEST
0692
10
0911
0815
SLO
8002
0815
16
8002
0373
STD
YEST
0873
24
0911
0864
SUP
8001
0864
11
8001
1621
RAL
8003
1621
65
8003
1679
SRD
0001
1679
31
0001
1485
NZE
CNYES
1485
45
1088
1639
LDD
YEST
PREPARE TO
1639
69
0911
0914
STD
0300
ADVANCE TO
0914
24
0300
1253
STD
1931
PARTB
NXT BED PT
1253
24
1931
0884
CNYES
RAU
8001
COMPUTE
1088
60
8001
1895
MPY
HLFAB
NEWYEST
1895
19
1298
0768
SRD
00 0 9
AND LOOP
0768
31
0009
0742
ALO
YEST
0742
15
0911
0865
STL
YEST
AVGYA
0865
20
0911
0814
CONSTANTS
CDCSA
0001
1300
0834
0001
1300
HLFAA
05
0958
05
HLFAB
05
1298
05
PARTB
RAU
DRFPV
COMPUTE
0884
60
0016
1671
MPY
BI NCR
XEST BY
1671
19
0078
1343
SRD
0009
LINEAR
1348
31
0009
1721
ALO
XFEED
METHOD
1721
15
108 7
0792
STL
XEST
AVGXA
0792
20
0033
1786
AVGXA
LDD
0503
COMPUTE
1786
69
1689
0503
RAU
XEST
X AND Y
1689
60
0033
1138

-162-
SUP
XSTAR
FOR LAST
1138
11
0090
0046
STU
DRFNW
POINT
0046
21
0013
1166
AUP
DRFPV
BY AVGING
1166
10
0016
1771
MPY
HLFAC
METHOD AND
1771
19
0824
1094
SRD
0009
COMPARE
1094
31
0009
0818
RAU
8002
WITH XEST
0818
60
8002
1327
MPY
BI NCR
1327
19
0078
1398
SRD
0009
1398
31
0009
1821
ALO
XFEED
1821
15
1087
0842
AUP
XEST
0842
10
0033
1188
SLO
8002
1188
16
8002
0997
STD
XEST
0997
24
003 3
1836
SUP
8001
1836
11
8001
1093
RAL
8003
1093
65
8003
1251
SRD
0001
1251
31
0001
1757
NZE
CNXES
1757
45
1660
1311
LDD
XEST
PREPARE TO
1311
69
0033
1886
STD
1929
ADVANCE TO
1886
24
1929
1332
STD
1932
PART C
1332
24
1932
1535
STD
0301
1535
24
0301
0804
LDD
DRFNW
0804
69
0013
1216
STD
0101
PARTC
1216
24
0101
1137
CNXES
RAU
8001
COMPUTE
1660
60
8001
0868
MPY
HLFAD
NEW XEST
0868
19
1071
0892
SRD
0009
AND LOOP
0892
31
0009
0915
ALO
XEST
0915
15
0033
1238
STL
XEST
AVGXA
1238
20
0033
1786
CONSTANTS
HLFAC
05
0824
05
HLFAD
05
1871
05
TMONE
0001
1190
0001
CDCSB
0001
1000
1050
0001
1000
PARTC
RAU
DRFPV
COMPUTE
1137
60
0016
0922
MPY
EIGHT
YEST PRIME
0922
19
0020
1540
SRD
0009
BY ADAMS
1540
31
0009
1863
SLO
0100
METHOD
1863
16
0100
1855
STL
SUMDF
1855
20
0025
1128
RAU
DRFPV
1128
60
0016
0972
SUP
0100
0972
11
0100
0856
MPY
HLFAB
0856
19
1298
0918
SRD
0009
0918
31
0009
0942
ALO
DRFPV
0942
15
0016
1022
RAU
8002
1022
60
8002
1131

-163-
MPY
TI NCR
1131
19
0666
1288
SRD
0009
1288
31
0009
1361
ALO
0300
1361
15
0300
0906
STL
YEST
LOOP
0906
20
0911 .
.0964
LOOP
LDD
0503
COMPUTE
0964
69
0968
0503
RA
XFEED
Y PRIME
0968
60
1087
0992
SUP
XSTAR
BY CUBIC
0992
11
0090
0096
MPY
FIVE
AVGRAGING
0096
19
0069
1590
SLT
0001
1590
35
0001
1047
AUP
SUMDF
1047
10
0025
1729
SRT
0002
1729
30
0002
1585
DVR
TWLVE
1585
64
0038
1448
RAU
3002
1448
60
8002
1807
MPY
TI NCR
1807
1.9
0666
1338
SRD
0009
1338
31
0009
1411
ALO
0300
1411
15
0300
0956
AUP
YEST
0956
10
0911
0965
SLO
8002
0965
16
8002
0923
STD
YEST
0923
24
0911
1014
SUP
8001
1014
11
8001
1072
RAL
8003
1072
65
8003
1779
SRD
0001
1779
31
0001
1635
NZE
RCYES
1635
45
1388
1739
LDD
DRFPV
1739
69
0016
1419
STD
0100
1419
24
0100
1303
LDD
YEST
1303
69
C/911
1064
STD
0300
PRTCA
1064
24
0300
1353
ROYES
RAU
3001
1388
60
8001
0646
MPY
HLFAB
0646
19
1298
1018
SRD
0009
1018
31
0009
1042
ALO
YEST
1042
15
0911
1015
STL
YEST
LOOP
1015
20
0911
0964
PRTCA
RAL
TMCTR
ADD ONE TO
135 3
65
0034
1789
AUP
1934
TIME CNTR
1789
10
1934
1339
ALO
TMONE
AND TEST
1839
15
1190
0696
AUP
8001
TO PUNCH
0696
10
8001
1403
SUP
8003
1403
11
8 003
1461
STD
1934
1461
24
1934
1438
STL
TMCTR
1438
20
003 4
148 8
SLO
TMCST
1488
16
1013
1068
NZE
PARTD
1068
45
1122
0973
STL
TMCTR
0973
20
0034
1538
RAU
1927
1538
60
1927
1181

164-
AUP
CDCSB
1181
10
1050
1006
STU
1927
1006
21
1927
1380
PCH
1927
PARTD
PUNCH CARD
1380
71
1927
1122
PARTD
LDD
SRYF
COMPUTE Y
1122
69
1625
0982
RAU
0101
162 5
60
0101
1056
MPY
T I NCR
COMPUTE
1056
19
0666
1588
SRD
0009
ESTIMATES
1588
31
0009
1511
ALO
0301
OF X AND Y
1511
15
0301
1106
STL
YEST
FOR NEXT
1106
20
0911
1114
RAU
DRFPV
BED POINT
1114
60
0016
1172
MPY
BI NCR
1172
19
0078
1493
SRD
0009
1498
31
0009
1222
ALO
XFEED
1222
15
1087
1092
STL
XEST
AVGYB
1092
20
0033
1638
AVGYB
RAL
YEST
1638
65
0911
1065
LDD
0503
1065
69
1113
0503
RAU
XEST
COMPUTE
1118
60
0033
1688
SUP
XSTAR
Y BY
1688
11
0090
0746
STU
DRFNW
AVGRAGING
0746
21
0013
1266
AUP
0101
METHOD AND
1266
10
0101
1156
MPY
HLFAE
COMPARE
1156
19
1259
1430
SRD
0009
WITH YEST
1430
31
0009
1453
RAU
8002
1453
60
8002
1561
MPY
TI NCR
1561
19
0666
1738
SRD
0009
1738
31
0009
1611
ALO
0301
1611
15
0301
12 06
AUP
YEST
1206
10
0911
1115
SLO
8002
1115
16
8 002
1023
STD
YEST
1023
24
0911
1164
SUP
8001
1164
11
8001
1272
RAL
8003
1272
65
8003
.1829
SRD
0001
1829
31
0001
1685
NZE
CNYSA
AVGXB
1685
45
1788
1889
C NY'S A
RAU
8001
COMPUTE
1788
60
0001
0796
MPY
HLFAF
NEW YEST
0796
19
0899
1320
SRD
0009
AND LOOP
1320
31
0009
1143
ALO
YEST
1143
15
0911
1165
STL
YEST
AVGYB
1165
20
0911
1638
AVGXB
RAU
DRFNW
COMPUTE
1889
60
0013
1168
AUP
DRFPV
X BY
1168
10
0016
1322

-165-
MPY
HLFAG
AVGRAGING
1322
19
1675
08 46
SRD
0009
METHOD AND
0 846
31
0009
1469
RAU
8002
COMPARE
1469
60
8002
1377
MPY
B I NCR
WITH XEST
1377
19
0078
1548
SRD
0009
1548
31
0009
13 72
ALO
XFEED
1372
15
1087
1142
AUP
XEST
1142
10
003 3
1838
SLO
8002
1838
16
8002
1097
STD
XEST
1097
24
0033
1886
SUP
8001
1888
11
8001
0896
RAL
8003
0896
65
8003
1503
SRD
0001
1503
31
0001
1309
NZE
CNXSA
1309
45
1212
1214
LDD
XEST
1214
69
0033
1640
STD
1929
1640
24
1929
1382
STD
XNOW
1382
24
0074
1427
LDD
YEST
1427
69
0911
1264
STD
1932
1264
24
1932
1735
STD
0301
PARTE
1735
24
0301
0054
CNXSA
RAU
8001
COMPUTE
1212
60
8001
1519
MPY
HLFAH
NEW XEST
1519
19
1422
1192
SRD
0009
AND LOOP
1192
31
0009
1215
ALO
XEST
1215
15
0033
1690
STL
XEST
AVGYB
1690
20
0033
1638
CONSTANTS
HLFAE
05
1259
05
HLFAF
05
0899
05
HLFAG
05
1675
05
HLFAH
05
1422
05
PARTE
RAU
DRFNW
COMPUTE
0854
60
0013
1218
SUP
0101
Y PRIME
1213
11
0101
1256
MPY
HLFAT
BY ADAMS
1256
19
0660
1480
SRD
0009
QUADRATIC
1480
31
0009
1553
ALO
DRFNW
METHOD
1553
15
0013
1268
STD
0101
1268
24
0101
0904
RAU
8002
0904
60
8002
1314
MPY
T I NCR
1314
19
0666
1740
SRD
0009
1740
31
0009
1364
ALO
0301
1364
15
0301
1306
STL
0301
1306
20
0301
0954

166-
PARTF
AVGXC
CNXSB
RAU
DRFNW
COMPUTE
0954
60
0013
1318
SUP
DRFPV
X AND Y
1318
11
0016
1472
MPY
HLFAK
EST FOR
1472
19
1725
0946
SRD
0009
NEXT POINT
0946
31
0009
1569
ALO
DRFNW
3Y ADAMS
1569
15
0013
1368
RAU
8002
QUADRATIC
1368
60
8002
1477
MPY
81 NCR
METHOD
1477
19
0078
1598
SRD
0009
1598
31
0009
1522
ALO
XNOW
1522
15
0074
1879
STL
XEST
PARTF
1879
20
0033
1790
RAU
DRFNW
COMPUTE
1790
60
0013
1418
MPY
EIGHT
CONTRIBUTN
1418
19
0020
18 40
SRD
0009
OF DRF PV
1840
31
0009
1414
SLO
DRFPV
AND DRFNW
1414
16
0016
1572
STL
SUMDF
AVGXC
TO AVGDF
1572
20
0025
1178
RAL
XEST
COMPUTE
1178
65
0033
1890
LDD
0503
X AMD Y
1890
69
1193
0503
RAU
XEST
BY CUBIC
1193
60
0033
1242
SUP
XSTAR
AVGRAGING
1242
11
0090
0996
STU
010 2
AND COMPAR
0996
21
0102
1356
MPY
FIVE
WITH XEST
1356
19
0069
1292
SLT
0001
1292
35
0001
0949
AUP
SUMDF
0949
10
0025
1530
SRT
0002
1530
30
0002
1342
DVR
TWLVE
1342
6 4
0038
1648
RAU
8002
1648
60
8002
1857
MPY
BI NCR
1857
19
0078
1698
SRD
0009
1698
31
0009
1622
ALO
XNOW
1622
15
0074
1580
AUP
XEST
1580
10
0033
1392
SLO
8002
1392
16
8002
1301
STD
XEST
1301
24
0033
1442
SUP
8001
1442
11
8001
0999
RAL
8003
0999
65
8003
1008
SRD
0001
1008
31
0001
1265
NZE
CNXSB
1265
45
1468
1619
LDD
XEST
1619
69
0033
1492
STD
1930
1492
24
1930
1233
STD
1933
1233
24
1933
1542
STD
0302
PARTG
1542
24
0302
1406
RAU
8001
COMPUTE
1468
60
8001
1775
MPY
HLFAI
NEW XEST
1775
19
1223
1748

-167
SRD
0009
AND LOOP
1748
31
0009
1672
ALO
XEST
1672
15
0033
1592
STL
XEST
AVGXC
1592
20
0033
1178
CONSTANTS
HLFAI
03
1228
05
HLFAK
05
1725
05
PARTG
RAL
TMCTR
ADD ONE TO
1406
65
0034
1642
AUP
1934
TIME CTR
1642
10
193 4
1692
ALO
TMONE
AND TEST
1692
15
1190
1046
AUP
8001
TO PUNCH
1046
10
8001
1603
SUP
8003
1603
11
8003
1661
STD
1934
1661
24
1934
1742
STL
TMCTR
1742
20
0034
1792
SLO
TMCST
1792
16
1013
1518
NZE
RSETA
1518
45
0633
1073
STL
TMCTR
1073
20
0034
1842
RAL
CDCSC
1842
65
1096
1351
LDD
1927
1351
69
1927
1630
S IA
1927
1630
23
1927
1680
RAL
0001
1680
65
8001
1892
ALO
CDCST
1892
15
0740
1146
STL
1927
1146
20
1927
1730
PCH
1927
RSETA
1730
71
1927
0633
CONSTANTS
CDCSC
01
CDCSC
3300
1096
01
1096
3300
CDCST
0001
0740
0001
INILZ LDD
1951
INITIALIZATION
MOVE DATA
1100
69
1951
1004
STD
1927
FROM INPUT
1004
2 4
1927
1780
LDD
1952
CARD TO
1780
69
1952
1456
STD
XFEED
VARIOUS
1456
24
1087
1243
STD
1928
STORAGE
124 3
24
192 8
1231
LDD
1953
SPOTS
1231
69
1953
1506
STD
1929
1506
24
1929
1432
STD
A
1432
24
1785
1293
LDD
1954
1293
69
1954
1058
STD
1930
1058
24
1930
1283

168-
STD
B
1283
24
1343
1196
LDD
1955
1196
69
1955
1108
STD
1931
1108
24
1931
0934
STD
C
0934
24
1393
1246
LDD
1956
1246
69
1956
1359
STD
1932
1359
24
1932
1835
STD
D
1835
24
1443
1296
LDD
1957
1296
69
1957
1710
STD
1933
1710
24
1933
1493
RAL
1958
1493
65
1958
1464
STL
1934
1464
20
1934
1543
SRT
0001
1543
30
0001
1049
STL
TI NCR
1049
20
0666
1669
RSL
8002
1669
66
8 002
1527
STL
B I NCR
1527
20
0078
1281
LDD
TMTEN
1281
69
0984
1593
STD
TMCST
1593
24
1013
1316
RAU
8003
1316
60
8003
1123
STL
TMCTR
1123
20
0034
1643
PCH
1927
PCH DUP
OF INPUT C
1643
71
1927
1577
LDD
0501
COMPUTE
CONSTANTS
FOR EQUILB
EQUATIONS
1577
69
1830
0501
LDD
0502
COMPUTE
Y IN EQLBR
WITH FEED
1830
69
1333
0502
LDD
RSTK1
INITIALIZE
1333
69
1693
1346
STD
RSTKA
RESET
1346
24
1286
1743
LDD
RSTK2
INSTRUCTNS
1743
69
1396
1099
STD
RSTKB
1099
24
0614
1568
LDD
RSTK3
1568
69
1722
1825
STD
RSTKC
1825
24
0822
1875
LDD
RSTK5
1875
69
1278
1331
STD
RSTKD
1331
24
0847
1150
LDD
RSTK.6
1150
69
1653
1556
STD
RSTKE
1556
24
0708
1711
LDD
RSTK4
1711
69
1514
1618
STD
RSTKF
1618
24
0828
1381
LDD
RSTK.9
1381
69
1034
1793

-169-
STD
TSTMB
1793
24
0622
0976
RAL
RSTK7
INITIALIZE
0976
65
1880
1885
LDD
CFPWB
1885
69
1436
1843
SDA
CFPWB
ADDRESSES
1843
22
1436
1893
LDD
CFPWG
1893
69
0809
1262
SDA
CFPV/G
AT 0301
1262
22
0809
1312
LDD
CFPWH
1312
69
1185
1144
SDA
CFPWH
1144
22
1185
1194
RAL
RSTK8
INITIALIZE
1194
65
1147
1401
LDD
CFPWE
ADDRESSES
1401
69
1567
1370
SDA
CFPWE
AT 0101
1370
22
1567
1420
LDD
CFPWF
1420
69
1617
1470
SDA
CFPWF
1470
22
1617
1520
RAL
TSWFK
INITIALIZE
1520
65
1173
1627
LDD
SATBD
ADDRESSES
1627
69
0773
1026
SDA
SATBD
AT 0300
1026
22
0773
1076
LDD
SRYFP
1076
69
0888
1244
SDA
SRYFP
1244
22
0888
1294
LDD
SRYFB
1294
69
0709
1362
SDA
SRYFB
1362
22
0709
1412
LDD
SRYFD
1412
69
0759
1462
SDA
SRYFD
1462
22
0759
1512
LDD
SRYFE
1512
69
0764
1668
SDA
SRYFE
1668
22
0764
1718
LDD
TSWFA
1718
69
0723
1126
SDA
T SWF A
1126
22
0723
1176
RAL
SRYFK
INITIALIZE
1176
65
1431
1344
LDD
SRYFA
ADDRESSES
1344
69
0916
1719
SDA
SRYFA
AT 0100
1719
22
0916
1769
LDD
SRYFC
1769
69
1713
1366
SDA
SRYFC
1366
22
1713
1416
LDD
SRYFF
1416
69
0966
1819
SDA
SRYFF
1819
22
0966
1869
LDD
ITNWB
INITIALIZE
1869
69
1772
1226
STD
TSMWB
TEST FOR
1226
24
0729
1482
LDD
ITNLP
NEXT TO
1482
69
1394
1197
STD
TNLP1
LAST POINT
1197
24
0007
1760
LDD
INLZA
PLACEZERO
1760
69
1564
1768
STD
INLZD INLZC
INTO BED
1768
24
1822
1276

-170-
INLZC
RAU
8002
INLZD
AND DRF
1276
60
8002
1822
INLZD
STL
0100
INLZE
LOCATIONS
1822
20
0100
1703
INLZE
RAL
INLZD
1703
65
1822
1677
ALO
INLZK
1677
15
1481
1444
STL
INLZD
1444
20
1822
1326
SLO
INLZQ
1326
16
1531
1494
NZE
INLZC
PARTA
1494
45
1276
1000
CONSTANTS
TMTEN
0010
0984
0010
INLZA
STL
0100
INLZE
1564
20
0100
1703
INLZK
0001
1481
0001
INLZQ
STL
0501
INLZE
1531
20
0501
1703
RSTK1
01
0103
RSTKA
1693
01
0103
1286
RSTK2
01
0302
RSTKB
1396
01
0302
0614
RSTK3
01
0102
RSTKC
1722
01
0102
0822
RSTK4
STD
0303
CL1PE
1514
24
0303
0656
RSTK5
01
1930
RSTKD
1278
01
1930
0847
RSTK6
01
1933
RSTKE
1653
01
1933
0708
RSTK7
01
0301
RSTK7
1880
01
0301
1880
RSTK8
01
0101
RSTK8
1147
01
0101
1147
RSTK9
NZE
STPCB
STPCC
1034
45
0826
0950
RSTKO
NZE
STPCB
STPCA
0816
45
0826
0977
TSWFK
01
0300
TSWFK
1173
01
0300
1173
SRYFK
01
0100
SRYFK
1431
01
0100
1431
ITNWB
SRD
0001
TSNWC
1772
31
0001
0085
ITNLP
NZE
CNPWA
CL2PA
1394
45
0010
0011
BLA
0504
0600
BLR
0503
BLR
0601
1999
SUBROUTINE FOR XSTAR
0503
STD
SRXSZ
0503
24
0506
0509
STL
YCALC
0509
20
0513
0516
SLO
D
0516
16
1443
0547
BMI
YLOWR
YUPPR
0547
46
0550
0551
YUPPR
RAU
YCALC
0551
60
0513
0517
MPY
IF! IA
0517
19
0520
0540
SRD
0009
0540
31
0009
0563
ALO
A
0563
15
1785
0539

-171-
AUP
YCALC
0539
10
0513
0567
SLO
8002
0567
16
8002
0525
SRT
0001
0525
30
0001
0531
DVR
8001
0531
64
8001
0544
STL
XSTAR
SRXSZ
0 544
20
0090
0506
YLOWR RAU
YCALC
0550
60
0513
0518
MPY
1M13
0518
19
0521
0542
SRD
0009
0542
31
0009
0515
ALO
B
0515
15
1343
0597
AUP
YCALC
0597
10
0513
0568
SLO
3002
0568
16
8002
0527
SRT
0001
0527
30
0001
0533
DVR
8001
0533
64
8001
0546
STL
XSTAR
SRXSZ
0546
20
0090
0506
SUBROUTINE FOR YSTAR
0502
STD
SRYSZ
0502
24
0505
0508
RAU
XFEED .
0508
60
1087
0541
SUP
C
0 541
11
1393
0548
BMI
XLOWR XUPPR
0548
46
0552
0553
XUPPR
AUP
8001
0553
10
8001
0511
MPY
AM 11
0511
19
0514
0534
SRD
0009
0534
31
0009
0507
ALO
ALONE
0507
15
0510
0565
STL
DVSRA
0565
20
0519
0522
RAU
XFEED
0522
60
1087
0591
MPY
A
0591
19
1785
0556
DVR
DVSRA
0556
64
0519
0530
STL
YEQFD SRYSZ
0530
20
0758
0505
XLOWR
AUP
8001
0552
10
8001
0559
MPY
BMI1
0559
19
0512
0532
SRD
0009
0532
31
0009
0555
ALO
ALONE
0555
15
0510
0566
STL
DVSRA
0566
20
0519
0572
RAU
XFEED
0572
60
1087
0592
MPY
B
0592
19
1343
0 564
DVR
DVSRA
0564
64
0519
0580
STL
YEQFD SRYSZ
0580
20
0758
0505
SUBROUTINE FOR CONSTANTS

0501 STD
SRKEZ
0501
24
0504
0 5 57
RAU
A
0557
60
1785
0539
ALO
B
0589
15
1343
0598
SUP
ALONE
0598
11
0510
0 569
SLO
3001
0569
16
8001
0577
STU
AM 11
0577
21
0514
0570
STL
BM 11
0570
20
0512
0571
RAU
ALONE
0571
60
0510
0523
SUP
A
0523
11
1785
0590
STU
1MIA
0590
21
0520
0573
RAU
ALONE
0573
60
0510
0 524
SUP
B
0524
11
1343
0 549
STU
1MIB SRKEZ
0549
21
0521
0504
CONSTANTS
ALONE
10
0510
10

-173-
BIOGRAPHICAL SKETCH
The author was born December 17, 1928, In Port Arthur,
Texas. He received the degree of B. S. in Chemical Engineer
ing from Louisiana State University in June, 1948, and the
degree of S. M. in Chemical Engineering Practice from
Massachusetts Institute of Technology in June, 1949.
He worked as a chemical engineer for the Magnolia
Petroleum Company, Beaumont, Texas, from 1949 to 1953. He
was an Assistant Professor of Chemical Engineering at Lamar
State College of Technology, Beaumont, Texas, from 1953 to
June, 1954, when he entered the University of Florida
graduate school. He is currently employed by the Dow Chemical
Company, Baton Rouge, Louisiana, as a senior design engineer.
He is a member of the American Institute of Chemical
I
* J
Engineers, Sigma Xi, Tau Beta Pi, and Alpha Chi Sigma.

174-
This dissertation was prepared under the direction
of the chairman of the candidate's supervisory committee and
has been approved by all members of that committee. It was
submitted to the Dean of the College of Engineering and to
the Graduate Council, and was approved as partial fulfillment
of the requirements for the degree of Doctor of Philosophy
in Engineering.
February 1, 1958
Dean, dDollegeof Engineering
Dean, Gradate School
SUPERVISORY COMMITTEE:
airman y'
n-rlini rmnn is
rman

Page 2 of3
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In reference to the following dissertation:
AUTHOR: Johnson, Adrain
TITLE: Application of numerical methods in analysis of fixed bed adsorption
fractionation., (record number: 541549)
PUBLICATION DATE: 1958
I,
ram
as copyright holder for the aforementioned
£ 'Johnson 'Jr.
dissertation, hereby grant specific and limited archive and distribution rights to the Board of Trustees of
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Personal information blurred
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Date m Signature
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-43-
the bed depth parameter H was covered. Several authors have
discussed the existence of the adsorption wave, and some have
speculated upon the conditions or requirements that an ulti
mate or invariant shape be formed. The discovery that an
invariant wave shape was formed in these problem solutions
prompted a further analysis of the conditions necessary for
its formation.
B. The Asymptotic or Ultimate Adsorption Wave
It is an experimental fact that if an adsorption
column is long enough (and if there is no adsorption azeo
trope) eventually there will be set up three distinct zones
which travel through the column. Refer to the following
diagram.
Bed Depth, L


-100-
TABLE 22
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 6c (cf. Figure 23)
Col. Diam.
Wt. Alumina
Pb
Xp
2.47 cm.
267.9 g.
.883 g. /cc.
0.5 Vol. fr.
Toluene
Ave. Inverse Rate
VP
fv
Sample Size
16 sec./cc.
.1888 cc./g.
.425
5 drops
Sample No.Time, sec.
x
Total Vol. Vol. Fraction
Effluent, cc.Toluene
1
3283
.10
.025
2
3372
5.35
.105
3
3453
10.60
.198
4
3538
15.85
.281
5
3626
21.10
.350
6
3714
26.35
.396
7
3800
31.60
.422
8
3886
36.85
.446
9
3974
42.10
.454
10
4059
47.35
.466
11
4145
53.60
.475
12
4230
57.85
.480
13
4314
63.10
.481
14
4398
68.35
.482
15
4486
73.60
.484
16
4572
78.85
.489
17
4656
84.10
.491
18
4740
89.35
.491
19
4823
94.60
.491
20
4907
95.85
.495


-135-
(30) Ilin, B. Molecular Kinetic Theory of Adsorption. J.
Russ. Phys. Chem. Soc. 1925.
(31) Levy, L. S. Adsorption From Binary System. Compt. Rend.
186: 1619-1621. 1928.
(32) Klosky, S. Adsorption of Mixtures of Vapors. J. Phys.
Chem. 32: 1387-1395. 1928.
(33) Tolloizko, Stanislaw, A General Equation for the Speed
of Pure Adsorption. Collection Czeck Chem. Communica
tions. 2: 344-346. 1930.
(34) Constable, F. H. Kinetics of Adsorption with Relation
to Reaction Velocity. Trans. Faraday Soc. 28: 227-
228. 1932.
(35) Swikin, J. K., and Kondrashon, A. I. Adsorption Kinetics
of Vapors in Air Stream. Kolloid Z. 56: 295:299.
1931.
(36) Ilin, B. V. Kinetics of Adsorption of High Mol. Wt.
Substances by Porous Powder. J. Gen. Chem. (U.S.S.R.)
2: 431-441. 1932.
(37) Rogenskei, S. Equation for Kinetics of Activated Ad
sorption. Nature. 134: 935. 1934.
(38) Crespi, M. Kinetics of Adsorption I. Anale. Soc. Espan.
Fis. Quim. 32: 30-42. 1934.
(39) Crespi, M., and Alexandre, V. Kinetics of Adsorption III.
Anale. Soc. Espan. Fis. Quim. J3: 350-359. 1935.
(40) Taylor, Hugh S. The Activation Energy of Adsorption
Processes. J. Am. Chem. Soc. £>3: 578-597. 1931.
(41) Nizovkin, V. K. Dynamics of Chemical Adsorption. Trans.
VI. Mendelien Engrs. 2: 218-232. 1935.
(42) Crespi, M. Kinetics of Adsorption II. Anale. Soc. Espan.
Fis. Quim. 32: 639-657. 1934.
(43) Damkohler, G. The Adsorption Velocity of Gases on
Powdered Adsorbents. Z. Physik. Chem. A174: 222-238.


-57-
C. Experimental Procedures
1. Specific Pore Volume, Vp
A weighing bottle containing a weighed quantity of
adsorbent was exposed in a closed desiccator, maintained at
normal room temperature, to the vapors of the pure adsorbate
(contained in a beaker also placed in the desiccator) for a
period of two weeks. At the end of this time, which had
previously been shown to be adequate for equilibrium to be
established, the adsorbent was re-weighed to determine the
weight of adsorbate taken up by the adsorbent. From these
data the weight of adsorbate adsorbed per gram of adsorbent
and Vp, the specific pore volume of the adsorbent, milli
liters per gram, were calculated. The results of these
experiments are presented in Table 3.
2. Determination of x-y Equilibria
Approximately 20 grams of adsorbent was measured
into a 50 ml. flask, to which 20 ml. of a particular mixture
of toluene and methylcyclohexane was added. The flasks were
closed and left at room temperature for a minimum of four
hours. A sample of the liquid phase was removed and its
refractive index determined. From a refractive index cali
bration curve (Figure 26, Table 26, Appendix) previously
obtained for toluene-MCH solutions, the composition of the
liquid phase, x, was determined. Values of y the composi
tion of the adsorbed phase in equilibrium with the liquid


/
07
/


-155
LDD
0503
PRESENT
1560
69
1663
0 5 03
RAU
XFEED
DRIVING
1663
60
1087
0991
STD
1928
0991
24
1928
0881
SUP
XSTAR
FORCE
0881
11
0090
1345
STU
DRFNW
SRYFA
COMPUTE
1345
21
0013
0916
SRYFA
SUP
0100
SRYF2
ESTIMATE
0916
11
0100
145 5
SRYF2
MPY
HLFAJ
OF Y BY
145 5
19
0803
0928
SRD
0009
ADAMS
0928
31
0009
1001
ALO
DRFNW
1001
15
0013
1367
RAU
8002
QUADRATIC
1367
60
8002
1375
MPY
T I NCR
METHOD
1375
19
0666
1336
SRD
0009
SRYFB
1336
31
0009
0709
SRYFB
ALO
0300
SRYF3
0709
15
0300
1505
SRYF3
STL
YEST
1505
20
0911
0664
RAU
DRFNW
0664
60
0013
1417
MPY
EIGHT
1417
19
0 02 0
1240
SRD
0009
SRYFC
1240
31
0009
1713
5RYFC
SLO
0100
SRYFA
1713
16
0100
1555
SRYF4
STL
SUMDF
AVGYC
1555
20
0025
0978
AVGYC
RAL
YEST
COMPUTE
0978
65
0911
0665
LDD
0503
Y PRIME
0665
69
0618
0503
RAU
XFEED
BY CUBIC
0618
60
1087
1041
SUP
XSTAR
METHOD AND
1041
11
0090
1395
MPY
FIVE
COMPARE
1395
19
0069
1290
SLT
0001
WITH YEST
1290
35
0001
0897
AUP
SUMDF
0897
10
0025
1379
SRT
0002
1379
30
0002
1085
DVR
TWLVE
1085
64
0038
1098
RAU
8002
1098
60
8002
1657
MPY
TI NCR
1657
19
0666
1386
SRD
0009
SRYFD
1386
31
0009
0759
SRYFD
ALO
0300
SRYF5
0759
15
0300
1605
SRYF5
AUP
YEST
1605
10
0911
0715
SLO
8002
0715
16
8002
0823
STD
YEST
0823
24
0911
0 714
SUP
8001
0714
11
8001
1271
RAL
8003
1271
65
8003
1429
SRD
0001
1429
31
0001
1135
NZE
CNYSC
1135
45
0938
1339
LDD
YEST
SRYFE
1339
69
0911
0764
SRYFE
STD
0300
0764
24
0300
1053
LDD
DRFNW
SRYFF
1053
69
0013
0966
SRYFF
STD
0100
SRYF7
0966
24
0100
1103
SRYF7
STD
DRFPV
SRYFZ
1103
24
0016
1035


-173-
BIOGRAPHICAL SKETCH
The author was born December 17, 1928, In Port Arthur,
Texas. He received the degree of B. S. in Chemical Engineer
ing from Louisiana State University in June, 1948, and the
degree of S. M. in Chemical Engineering Practice from
Massachusetts Institute of Technology in June, 1949.
He worked as a chemical engineer for the Magnolia
Petroleum Company, Beaumont, Texas, from 1949 to 1953. He
was an Assistant Professor of Chemical Engineering at Lamar
State College of Technology, Beaumont, Texas, from 1953 to
June, 1954, when he entered the University of Florida
graduate school. He is currently employed by the Dow Chemical
Company, Baton Rouge, Louisiana, as a senior design engineer.
He is a member of the American Institute of Chemical
I
* J
Engineers, Sigma Xi, Tau Beta Pi, and Alpha Chi Sigma.


xml record header identifier oai:www.uflib.ufl.edu.ufdc:UF0008998100001datestamp 2009-02-12setSpec [UFDC_OAI_SET]metadata oai_dc:dc xmlns:oai_dc http:www.openarchives.orgOAI2.0oai_dc xmlns:dc http:purl.orgdcelements1.1 xmlns:xsi http:www.w3.org2001XMLSchema-instance xsi:schemaLocation http:www.openarchives.orgOAI2.0oai_dc.xsd dc:title Application of numerical methods in analysis of fixed bed adsorption fractionation.dc:creator Johnson, Adrain Earl Jr.dc:publisher Adrain Earl Johnson, Jr.dc:type Bookdc:identifier http://www.uflib.ufl.edu/ufdc/?b=UF00089981&v=00001000541549 (alephbibnum)13053948 (oclc)dc:source University of Floridadc:language English


-63-
performed by Lombardo, the columns were sufficiently long
for this to occur. Since Lombardo did not make duplicate
runs at different column lengths, there was only one check
point for each run.
In those cases where the length of the column is
large compared to the length of the adsorption wave, there
is very little interest (other than academic) in an exact
solution to the problem of wave shape. A rough estimate of
the wave length in such a case, combined with the assumption
that the wave reaches the ultimate velocity within a few
wave lengths into the column (which it usually does) will
suffice to predict with good accuracy the quantity of pure
B which can be produced with a given column.
It is those cases in which the wave length is a sub
stantial fraction of the column length that a more accurate
knowledge of the adsorption wave shape and position is re
quired. It is precisely this case that cannot be handled
by the ultimate wave velocity and shape, but which requires
the complete solution, which was provided by the computer.
The experiments performed in this work were aimed at creat-
j
ing conditions I of column operation which would require the
computer solution.
A. Adsorption Fractionation Experiments of Lombardo
The effluent volume vs. composition curves for three
fractionation experiments on the benzene-hexane-silica gel


Volume Fraction Benzene in Effluent
122
Total Volume of Effluent, cc.
FIGURE 18.- BENZENE-HEXANE FRACTIONATION WITH SILICA GEL
LOMBARDO RUN B-4.


-44-
In zone 1, the adsorbent has preferentially adsorbed
component A from the liquid phase passing over it until the
composition of the adsorbed phase has reached the compo
sition in equilibrium with the feed. When this occurs, there
is no tendency for further exchange of material between the
two phases, and XF is also constant in zone 1. In zone 2,
mass transfer is taking place, and the composition of both
y and x vary with bed depth, L, and with time, 0 Zone 2
is the adsorption wave. However, the continual removal of
component A from the liquid phase as it travels through the
bed eventually becomes complete, and the composition of the
liquid at the head of the wave becomes zero with respect to
component A. Zone 3 represents the portion of the bed over
which pure component B is passing. As in zone 1, there is
no tendency for mass exchange between the phases and compo
sitions are constant with 0 in this section. Remember, how
ever, that all three zones are traveling through the column.
Although these three zones will be formed in any
adsorption fractionation experiment (with the exception of
azeotropes), the questions of importance are (1) How soon
will the three zones be formed? (2) V/hat is the width of
zone 2? (3) Does zone 2 reach an ultimate non-changing shape?
(4) If so, at what rate does zone 2 travel through the
column?


-99
TABLE 21
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 6b (cf. Figure 23)
Rate = 16 sec./cc.
= .1888 cc./g.
- .425
5 drops
x
Total Vol. Vol. Fraction
Sample No.Time, sec.Effluent, cc.Toluene
Col.
Diam.
2.47 cm.
Ave. Inverse
wt.
Alumina *=
129.9 g.
vp
Pb
es
.883 g./cc.
*v
xF
cs
0.5 Vol. fr.
Toluene
Sample Size
1
1660
.10
.128
2
1745
5.35
.256
3
1823
10.60
.350
4
1908
15.85
.408
5
1994
21.10
.440
6
2078
26.35
.461
7
2163
31.60
.474
8
2245
36.85
.479
9
2330
42.10
.481
10
2415
47.35
.485
11
2497
52.60
.488
12
2582
57.85
.490
13
2665
63.10
.492
14
2748
68.35
.492
15
2828
73.60
.493
16
2912
78.85
.494
17
2995
84.10
.496
18
3078
89.35
.498
19
3165
94.60
.500


V. NUMERICAL ANALYSIS
A. Numerical Methods
The general procedure for solving differential equa
tions by means of numerical techniques is covered by many
texts.
To solve a partial differential equation or equa
tions, it is necessary to substitute, in effect, a set of
simultaneous differential equations, which are integrated
numerically and simultaneously by standard numerical tech
niques. The voluminous number of computations required and
the quantity of numbers to keep track of during the integra
tion make it imperative that the modern high speed computer
be used when dealing with partial differential equations.
The adsorption problem can be demonstrated graph
ically in the following manner.
29-


-25-
bo th sides of equations (3) and (4) by (pbVp/KLa) gives,
(PbVp/KLa)(T) 9 (Afv/Q)(L) (7)
(pbVp/KLa)(H) (ApbVp/Q)(L) (8)
The net dimension of both sides of equations (7) and
(8) is time. A study of the right hand side of these equa
tions will revel the following interpretation of T and H.
The parameter T is proportional to the actual time
elapsed since introducing feed liquid into the adsorption
bed in excess of that which is required to fill the void
volume of the bed to point L by the feed flow rate Q.
The parameter H is proportional to the time that
would be required to fill the adsorbed phase volume of the
bed to point L by the feed flow rate Q. The proportionality
constant is the same as the one for T.
An alternate way of expressing the above would be to
state that T is proportional to the volume of liquid which
has entered the bed in excess of that required to fill the
void volume to point L, and H is proportional to the volume
of liquid which is required to fill the adsorbed phase (pore)
volume of the bed to point L.
Some reflection will show that for a given bed depth,
L, if H *=> T, then the liquid front has just reached point L
and both the void and pore volumes of the bed are filled to
the point L.


X,
Volume
Fraction
Component A
In Liquid
Phase
FIGURE 7.- ULTIMATE ADSORPTION WAVE SHAPES
COMPUTER SOLUTION TO PROBLEM 51


TABLE 3
DETERMINATION OF SPECIFIC PORE VOLUMES
Run
No. Adsorbent
Adsorbate
Wt. Ad
sorbent, g.
Wt. ad
sorbate, g.
g. Adsorbate
g. Adsorbent
Adsorbate
Density,
g./cc.
VP
cc./g.
1
6-12 Mesh
Silica Gel
Toluene
29.56
10.77
. 366
.872
.420
2
tf
TT
21.28
7.85
.369
.872
.424
3
" Methyl-
cyclohexane
33.44
9.98
.299
.774
.387
4
1t
It
21.17
6.26
.296
.774
.382
5
8-14 Mesh
Act. Alumina
Methyl- 43.73
cyclohexane
6.36
. 1455
.774
.188
6
tl
u
23.68
3.473
.1467
.774
.189
7
If
Toluene
21.30
3.563
.1673
.872
.192
8
?T
! 1
36.48
5.636
. 1616
.872
. 185
For
6-12
Mesh
Silica Gel., Average Vp *
.402
For
8-14
Mesh
Activated Alumina Average Vp -
.188


-165-
MPY
HLFAG
AVGRAGING
1322
19
1675
08 46
SRD
0009
METHOD AND
0 846
31
0009
1469
RAU
8002
COMPARE
1469
60
8002
1377
MPY
B I NCR
WITH XEST
1377
19
0078
1548
SRD
0009
1548
31
0009
13 72
ALO
XFEED
1372
15
1087
1142
AUP
XEST
1142
10
003 3
1838
SLO
8002
1838
16
8002
1097
STD
XEST
1097
24
0033
1886
SUP
8001
1888
11
8001
0896
RAL
8003
0896
65
8003
1503
SRD
0001
1503
31
0001
1309
NZE
CNXSA
1309
45
1212
1214
LDD
XEST
1214
69
0033
1640
STD
1929
1640
24
1929
1382
STD
XNOW
1382
24
0074
1427
LDD
YEST
1427
69
0911
1264
STD
1932
1264
24
1932
1735
STD
0301
PARTE
1735
24
0301
0054
CNXSA
RAU
8001
COMPUTE
1212
60
8001
1519
MPY
HLFAH
NEW XEST
1519
19
1422
1192
SRD
0009
AND LOOP
1192
31
0009
1215
ALO
XEST
1215
15
0033
1690
STL
XEST
AVGYB
1690
20
0033
1638
CONSTANTS
HLFAE
05
1259
05
HLFAF
05
0899
05
HLFAG
05
1675
05
HLFAH
05
1422
05
PARTE
RAU
DRFNW
COMPUTE
0854
60
0013
1218
SUP
0101
Y PRIME
1213
11
0101
1256
MPY
HLFAT
BY ADAMS
1256
19
0660
1480
SRD
0009
QUADRATIC
1480
31
0009
1553
ALO
DRFNW
METHOD
1553
15
0013
1268
STD
0101
1268
24
0101
0904
RAU
8002
0904
60
8002
1314
MPY
T I NCR
1314
19
0666
1740
SRD
0009
1740
31
0009
1364
ALO
0301
1364
15
0301
1306
STL
0301
1306
20
0301
0954


-89
TABLE 11
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 2a (cf. Figure 20)
Col
. Diam.
= 2.47 cm.
Ave. Inverse
Rate * 20 sec./cc.
Wt.
Gel.
- 191.20 g.
VP
= .402 cc./g.
Pb
- .679 g,/cc.
*v
- .293
xF
- 0.500 Vol. fr.
Sample Size
= 5 drops
Toluene
X
Total Vol.
Vol. Fraction
Sample No.
Time, sec.
Effluent, cc.
Toluene
1
.10
.004
2
3644
5.35
.004
3
3747
10.60
.050
4
3853
15.85
Q50
5
3957
21.10
.112
6
4065
26.35
.172
7
4180
31.60
.230
8
4275
36.85
.278
9
~ ~
42.10
.305
10
4515
47.35
.339
11
4606
52.60
.368
12
4710
57.85
.385
13
4825
63.10
.396
14
4924
68.35
.408
15
5020
73.60
.418
16
5121
78.85
.425
17
5216
84.10
.430
18

89.35
.438


-96-
TABLE 18
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 5b (cf. Figure 22)
Col. Diara.
2.47 cm.
Ave. Inverse
Rate = 8.13 sec./cc.
Wt. Alumina -
121.5 g.
V
P
- .1888 cc./g.
P b
.883 g./cc.
fv
.425
xv
0.100 Vol. fr.
Sample Size
= 5 drops
X
Toluene
Total Vol.
X
Vol. Fraction
Sample No.
Time, sec.
Effluent, cc.
Toluene
1
835
.10
.003
2

10.35
.016
3
1008
20.60
.023
4
......
30.85
.041
5

41.10
.059
6
1258
51.35
.072
7
1344
61.60
.082
8
1427
71.85
.088
9
82.10
.090
10
1598
92.35
.094
11

102.60
.095
12
1763
112.85
.097
13
1844
123.10
.099
14
2016
143.60
.099


150
STD
YEST
0673
24
0911
0064
SUP
8001
0064
11
8001
0971
RAL
8003
0971
65
8003
1029
SRD
0001
1029
31
0001
0835
NZE
CNYSB
CL2PF
0835
45
0738
1039
CNYSB
RAU
8001
COMPUTE
073 8
60
8001
1095
MPY
HLFBC
NEW YEST
1095
19
0793
0068
SRD
0009
AMD LOOP
0068
31
0009
0891
ALO
YEST
0891
15
0911
0615
STL
YEST
CL2PD
0615
20
0911
0014
CL2.PF
RAU
DRFNW
COMPUTE
1039
60
0013
1017
MPY
FIVE
X BY CUBIC
1017
19
0069
0890
SLT
0001
AVGING
0890
35
0001
0747
AUP
SUMDF
METHOD AMD
0747
10
0025
1079
SRT
0002
COMPARE
1079
30
0002
0885
DVR
TWLVE
WITH XEST
0385
64
0038
0848
RAU
0002
0848
60
8002
1307
MPY
BI NCR
1307
19
0078
0898
SRD
0009
0898
31
0009
1021
ALO
XNOW
1021
15
0074
1129
AUP
XEST
1129
10
0033
1237
SLO
0002
1237
16
8002
1145
STD
XEST
1145
24
0033
1086
SUP
0001
1086
11
8001
0093
RAL
8003
0093
65
8003
0701
SRD
0001
0701
31
0001
1357
NZE
CNXSE
1357
45
1310
1011
LDD
XEST
CL2PG
1011
69
0033
0002
CL2PG
STD
1930
0002
24
1930
1033
STD
XNOW
1033
24
0074
0777
LDD
YEST
CL2PH
0777
69
0911
0072
CL2PH
STD
1933
CL2PI
0072
24
1933
0698
CL2PI
STD
0302
CL2PJ
0698
24
0302
1105
CMXSE
RAU
8001
COMPUTE
1310
60
8001
1067
MPY
HLFBD
NEW XEST
1067
19
0820
0940
SRD
0009
AND LOOP
0940
31
0009
1263
ALO
XEST
1263
15
0033
1287
STL
XEST
CL2PD
1287
20
0033
0014
CL2PJ
RAU
DRFNW
CL2PK
COMPUTE
1105
60
0013
0685
CL 2PK
SUP
0102
Y PRIME
0685
11
0102
1407


-2-
because of the apparent impossibility of obtaining analytical
solutions to the equations.
It was found that, through a fortuitous circumstance,
computer solutions based on constant-alpha type equilibrium
diagrams fit the data for the case of intraparticle diffu
sion contributing more closely than solutions using the
actual equilibrium diagram of the system.
In the course of this work equations were developed
for determining the rate of advance and the shape of the
ultimate adsorption wave, which is formed in columns of
sufficient length. In addition, a method was developed for
evaluating the height of an equilibrium stage (HETS) in an
adsorbent bed from data of fixed bed adsorption fractiona
tion experiments. The determination of HETS is of importance
in the design of continuous countercurrent adsorption
columns.
This work also included the development of a com
puter program for solving the partial differential equations.
The resulting program and a brief description of the
numerical methods used are presented.


94-
TABLE 16
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 4c (cf. Figure 21)
Col. Diam. 2.47 cm.
Wt. Gel. 45.3 g.
P b .679 g./cc.
Xy 0.100 Vol. fr.
Toluene
Ave. Inverse Rate
vp
*v
Sample Size
5,75 sec./cc.
.402 cc./g.
.293
5 drops
x
Sample No.
Time, sec.
Total Vol.
Effluent, cc.
Vol. Fraction
Toluene
1
345
20
.048
2
465
40
.061
3
575
60
.069
4
694
80
.074
5
805
100
.079
6
920
120
.082
7
1036
140
.082
8
1146
160
.084
9
1257
180
.085


AVPIA
RAL
AVPKA
0092
65
0645
0049
AUP
8001
0049
10
8001
0807
ALO
TNLPA
0807
15
0050
0605
LDD
CL1PC
0605
69
0008
0611
SDA
CL1PC
0611
22
0008
0661
SLO
8002
0661
16
8002
0619
STD
TNLPA
0619
24
0050
0053
ALO
CNPWB
0053
15
0019
0023
ALO
8003
0023
15
8003
0031
LDD
CNPWH
0031
69
0009
0012
SDA
CNPWH
0012
22
0009
0062
LDD
CNPWJ
0062
69
0736
0639
SDA
CNPWJ
0639
22
0736
0689
LDD
CL2PC
0689
69
0642
0695
SDA
CL2PC
0695
22
0642
0745
LDD
CL2PI
0745
69
0698
0051
SDA
CL2PI
0051
22
0698
0601
LDD
CL2P4
0601
69
0004
0857
SDA
CL2P4
0857
22
0004
0907
LDD
CL2PM
0907
69
0810
0713
SDA
CL2PM
0713
22
0810
0763
LDD
CL2PN
0763
69
0716
0669
SDA
CL2PN
0669
22
0716
0719
SLO
8 002
0719
16
8 002
0077
STD
CNPWB
0077
24
0019
0022
ALO
CL1PD
0022
15
062 5
0779
ALO
8003
0779
15
8003
0687
SLO
8002
0687
16
8002
0795
STD
CL1PD
0795
24
0625
0628
ALO
CNPWF
0628
15
0717
0771
ALO
8003
0771
15
8003
0829


Volume Fraction Toluene in Adsorbed Phase
-117
x, Volume Fraction Toluene in Liquid Phase
FIGURE 13.- ADSORPTION EQUILIBRIUM DIAGRAM FOR MCH-
TOLUENE ON DAVISON 6-12 MESH SILICA GEL
Relative Adsorbability


-153-
SDA CNPWJ
LDD CL2PC
SDA CL2PC
LDD CL2PI
SDA CL2PI
LDD CL2P4
SDA CL2P4
LDD CL2PM
SDA CL2PM
LDD CL2PN
SDA CL2PN
RAL RSTKC
LDD CNPWF
SDA CNPWF
LDD CNPWG
SDA CNPWG
LDD CL2PB
SDA CL2PB
LDD CL2PE
SDA CL2PE
LDD CL2PK
SDA CL2PK
LDD CL2PL
SDA CL2PL
RAL RSTKD
LDD CNPWD
SDA CNPWD
LDD CL2PG
SDA CL2PG
RAL RSTKE
LDD CNPWI
SDA CNPWI
LDD CL2PH
SDA CL2PH
LDD RSTKF
STD CL1PD
LDD RSTKG
STD WDCTR TSWFA
1089
22
0736
1139
1139
69
0642
1245
1245
22
0642
1295
1295
69
0698
0801
0801
22
0698
0851
0851
69
0004
1557
1557
22
0004
1607
1607
69
0810
1463
1463
22
0810
1513
1513
69
0716
1019
1019
22
0716
1069
1069
65
0822
0827
0827
69
0717
0920
0920
22
0717
0970
0970
69
0767
102 0
1020
22
0767
1070
1070
69
0073
0676
0676
22
0073
0726
0726
69
0879
0882
0882
22
0879
0932
0932
69
0685
0788
0788
22
0685
0838
0838
69
0041
0794
0794
22
0041
0844
0844
65
0847
0901
0901
69
0636
1189
1189
22
0636
1239
1239
69
0002
1255
1255
22
0002
1305
1305
65
0708
1563
1563
69
0757
1460
1460
22
0757
1510
1510
69
0072
1275
127 5
22
0072
1325
1325
69
0828
0781
0781
24
0625
0878
0878
69
0831
0684
0684
24
0770
0723
CONSTANTS


Q/A, cm./sec.
FIGURE 24.- EFFECT OF LIQUID VELOCITY ON OVERALL MASS TRANSFER COEFFICIENT


-127-
Total Volume of Effluent, cc.
FIGURE 23.- MCH-TOLUENE FRACTIONATION WITH ALUMINA
JOHNSON RUN F-6.


front arrives at point L by pushing out the liquid in the
void volume of the bed, the composition, y, of the liquid on
the adsorbent is zero. This, however, is not the case for
an initially dry bed.
For the initially dry bed, it was seen above that the
instant of filling corresponds to T = H. It then will suffice
to state a boundary condition for y along the boundary T = H,
if possible. Considering the physical problem, as a given
adsorbent particle fills, there are two extreme cases which
may occur. The liquid phase and the adsorbed phase at the
moment of filling may be in complete equilibrium, indicating
that diffusion of components A and B happened more rapidly
than the filling; or, the other extreme, the liquid phase and
the adsorbed phase may be of the same composition at the
moment of filling, indicating that the diffusion process is
very slow compared to the rate of filling. In actual fact,
it is of course probable that the physical process which
occurs is somewhere between the two extremes, depending upon
the filling rate. However, for lack of a better criterion,
it is certainly more probable that in the majority of cases
the diffusion rate is quite slow compared to the filling rate.
It has been shown (73) that each individual particle takes
something on the order of one minute or more to come to
equilibrium in batch experiments, and the filling process,
even in the smallest columns, is completed at the rate of
many, many particles per minute.


-83-
TABLE 6
ADSORPTION EQUILIBRIUM DATA
BENZENE-N-HEXANE ON
DAVISON THRU 200 MESH SILICA GEL
(Data of Lombardo)
(cf. Figure 15)
X
Volume Fraction
Benzene in Liquid
Phase
y
Volume Fraction
Benzene in
Adsorbed Phase
a
Relative
Adsorbability
(y/i-y)(1-x/x)
0.045
0.298
9.009
0.115
0.485
7.247
0.209
0.615
6.046
0.319
0.723
5.572
0.428
0.771
4.500
0.546
0.841
4.398
0.653
0.875
3.72
0.771
0.922
3.51
0.882
0.966
Empirical Equations
y -= x/(.9398x + .1475) ; .226 < x < .500
y x/(l.1354x + .1032) ; 0 < x < .226


Volume Fraction Benzene in Adsorbed Phase
-119-
x, Volume Fraction Benzene in Liquid Phase
FIGURE 15.- ADSORPTION EQUILIBRIUM DIAGRAM FOR BENZENE-
HEXANE ON DAVISON "THRU 200" MESH SILICA
GEL
a, Relative Adsorbability


IX. CONCLUSIONS
1. The application of the proposed equations for adsorption
fractionation was demonstrated for systems with small
adsorbent particle size and low flow rates, in which the
external film resistance presumably controls.
2. The boundary conditions of the liquid phase adsorption
fractionation process were properly defined and applied
in a numerical solution.
3. A complete IBM 650 program for solving the proposed
equations has been developed and presented.
4. The basic thesis, that a numerical approach can provide
useful solutions to problems otherwise insoluble, has
been proved.
5. The use of a solution based on a constant-alpha type
equilibrium curve which approximates the true equilibrium
curve was found to give qualitative accuracy. The shape
of the adsorption wave is distorted, but its rate of
travel down the column is closely approximated. The
results of this distortion can be used to advantage in
systems in which intraparticle diffusion contributes to
the total diffusional resistance.
6. Differential equations for evaluating the ultimate wave
shape were derived, and the velocity of the ultimate wave
was found to. be dependent upon xy, the feed liquid compo-
-75-


Volume Fraction Toluene in Effluent
-125-
, Total Volume of Effluent, cc.
FIGURE 21.- MCH-TOLUENE FRACTIONATION WITH SILICA GEL
JOHNSON RUN F-4.


-26-
D. Boundary Conditions for the Liquid
~ ^Phase Fixed feed Process
Inspection of equations (5) and (6) shows that there
are two dependent variables, x and y, and two independent
variables H and T. Only first order partial derivatives are
present, suggesting that only two boundary conditions, one
fixing x and one fixing y along two different axes, will
suffice. Physically, it can be seen that for a given bed
and given flow rate, the inlet feed composition and the
initial condition of the bed determine the resulting column
operation. Since the properties of the bed, the flow rate,
etc., are contained within H and T, they need not be con
sidered mathematically.
The condition of constant inlet feed composition
corresponds to the condition that at L = 0
x xy, for all 6 > 0
This is easily converted to the dimensionless system by
the condition
at H O
x = Xp, for all T ;>_ O
In other papers, the second boundary condition has
been met by considering that at T = 0
y 0, for all H > 0
which is equivalent to the physical case of a bed saturated
at 0 0 with a liquid of composition pure B. This would
insure that y * 0 initially, and that when the feed liquid


-61-
50, 100, and 200 ml., and filling them carefully with ad
sorbent. Bed densities were calculated from the weights
before and after filling and the cylinder volumes. By
tapping the cylinders with rubber mallets during the filling,
as was done when packing the adsorption columns, it was
possible to obtain reproducible bed densities. The bed
density, p^, used in the equations of this dissertation, is
the grams of dry adsorbent per total volume of dry bed. It
was assumed that since the bed densities were reproducible,
the void volumes would also be reproducible. Consequently,
after weighing the cylinders filled with dry adsorbent, the
cylinders were then filled with pure toluene or methylcyclo-
hexane. Time was allowed for the pore volumes to fill, and
additional liquid was added until the liquid remained level
with the top of the adsorbent. A third weighing ascertained
how much liquid was added, and the void space in the bed
was then computed as the difference between the volume of
liquid added and the volume of liquid known to have been
adsorbed into the adsorbent pore volumes. The void fractions
and bed densities obtained in this manner for the adsorbent
beds are listed at the top of Tables 8-25, which present
the results of the adsorption fractionation runs.


-33-
computed by fitting a straight line over the AT increment
from (i,j) to (i,j+l) utilizing the slope C5y/dT)n and value
of y at the point (i,j). However, this is the crudest of the
numerical integration formulae. For the resulting solution
to be even approximately close to the true solution, it is
necessary to use very small AH and AT increments. If inte
gration formulae be used which fit higher degree polynomials
to the curve in the neighborhood of the point (i,j), the
precision of the integration process is vastly improved, and
much larger AH and AT increment sizes can be used.
It was decided, by trying alternate integration
formulae on the computer, that, to obtain the degree of pre
cision required and yet cover a large range of the H and T
variables with the 200 increments allotted, it would be
necessary to use integration formulae which fit at least
second degree polynomials to each integration step. The
formulae used are listed in Table 1.
Formula number 1, which fits a second degree poly
nomial over two increments, was used to compute values of y
at points corresponding to (i,j+l) in the sketch. This equa
tion requires no trial and error. Formula number 2, which
fits a third degree polynomial over two increments (thus
requiring a trial and error solution) was used to compute
values of x at points corresponding to (i+l,j) in the sketch.
Two different formulae were used simply because it was


-59-
forced by nitrogen pressure from the bomb through poly
ethylene tubing through a capillary tube flowmeter into the
inlet at the bottom of a column. A pressure regulating valve
on the nitrogen cylinder permitted very precise control of
the flow rate, as indicated by a manometer attached to the
capillary. It was thus possible to make a set of three runs
(one each through the three columns) in which the flow rate
and feed composition were maintained constant.
The columns were packed with adsorbent prior to a
run by carefully pouring the adsorbent into the column while
tapping continuously with a rubber mallet. The tapping was
continued and adsorbent was added until the top of the ad
sorbent was level with the exit side arm, and the surface
of the adsorbent ceased to settle. By weighing the columns
before and after packing, the quantity of adsorbent added
was ascertained.
A run was started by opening the stopcock at the
bottom of the column and adjusting the nitrogen pressure
to give the desired manometer reading. The small capillary
orifices used in the flowmeter produced pressure drops of
about ten inches of mercury, so that only minor adjustments
of the nitrogen regulating valve were required during a run
to compensate for the rise in liquid level as the column
filled.
The effluent liquid was collected in graduated
cylinders, and samples of five drops (1/4 ml.) were collected


-IB-
progressed to the point that a better account of the velo
city profile of a fluid in a fixed bed can be made. This is
an item which could conceivably be included in a computer
^ analysis when a suitable fluid flow theory is available.
Item 3 is a deceivingly simple statement which needs
further discussion. In the gas phase process, which is used
as a model by almost every published paper on adsorption
fractionation, the bed is initially free of adsorbate, but
contains inert gas or carrier vapor. Since the bed is
initially already full of fluid, there is little effect of
the adsorption process upon the quantity of fluid flowing
while the bed is filling. The mathematical boundary con
ditions used to express this case state that when the feed
fluid reaches a given position in the bed the quantity of
adsorbate on the adsorbent is zero. In addition, the time
required for the fluid to reach a bed point is that required
to push the original gas out of the void space between the
adsorbent particles. Neither of these conditions is typical
of binary liquid adsorption. First, the time required to
fill the bed to a given point is that required to fill the
I void space and the pore volume of the adsorbent bed to that
point. Secondly, the composition of the liquid on the ad
sorbent at the foremost point of liquid penetration into the
bed continually changes as the filling "front progresses.
In a sufficiently long bed, the composition eventually


-101-
TABLE 23
BENZENE-N-HEXANE FRACTIONATION ON
DAVISON "THRU 200" MESH SILICA GEL
(Data of Lombardo)
Run No. B 2 (cf. Figure 16)
Col. Diam.
Wt. Gel.
Pb
8 mm.
20 g. p
.712 g./cc. xF
Ave. Inverse Rate
Vr
880 sec./cc.
.357
0.500 Vol. fr.
Benzene
.528
Sample No.
Sample
Time, min.Volume, cc.
x
Vol. Fraction
Benzene
1
2
3
4
5
6
7
8
9
10
11
0
7:00
13:50
20:20
27:00
33:50
40:40
47:45
55:00
63:40
72:00
80:00
0.5
0
0
0
0
0
0
0
0
0.325
0.485
0.500


86-
TABLE 8
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F la (cf. Figure 19)
Col. Diam.
Wt. Gel.
Pb
XF
Sample No.
*** 2.47 cm.
*= 195.0 g.
= .679 g./cc.
- 0.500 Vol. fr.
Toluene
Ave. Inverse Rate
V m
P
fv
Sample Size *
12.7 sec./cc.
.402 cc./g.
.293
7 drops
Time, sec.
x
Total Vol. Vol. Fraction
Effluent, cc.Toluene
1
2155
.15
.02
2

5.50
.055
3
2305
10.85
.102
4
2380
16.20
.150
5
2450
21.55
.199
6
2512
26.90
.240
7
2590
32. 25
.279
8
37.60
.308
9
...
42.85
.328
10
2790
48.30
.356
11
...
59.00
.380
12
_
64.35
.395
13
...
69.70
.408
14
3135
75.05
.412
15
3195
80.40
.428
16
3270
85.75
.439
17
3335
91.10
.441
18
3395
96.45
.453
19
...
111.80
.466


-52-
x
Xp/2
In most cases the left-hand integral must be ob
/
(22)
tained by numerical means because of the difficulty in
integrating the expression analytically. In effect, the
computer solutions which were run in this work performed
this integration, as evidenced by the ultimate wave shapes
which were obtained. It is important to remember that the
computer solutions also provided the relations for column
operation before the ultimate wave shape was formed. An
inspection of the graphs of the solutions shows that in
general, 90 per cent of the wave (excluding the ends) becomes
invariant by the time the composition of the liquid at the
filling front drops to less than 5 per cent of the feed
composition. Therefore, with a knowledge of the rate of
advance of the adsorption wave (VW(j => xp/yj.*), the computer
solution for the ultimate wave shape, and the computer solu
tion during filling of the first portion of the bed, the
composition of both phases may be quickly calculated for
any H and T thereafter.
D. Computation f HETS From Fixed Bed Data
Because continuous countercurrent moving bed ad
sorbers are readily analyzed by an equilibrium stage concept,
in which the number of theoretical stages in the column


-51-
Further information about the invariant wave may
be derived by equating the rate of mass transfer between the
two phases using the proposed mass transfer rate equation.
Again considering section dL in the countercurrent bed,
(dy/dL)(WVp)(dL) = K^a(x x*)(A dL) = (dx/dL)(Q')(dL)
Thus, rearranging and integrating,
dx/(x-x*)
(KLaA/Q)
dL
Kp,aA
Q^
(L2 L,)
(21)
The integration is indicated between two arbitrary composi
tions because, theoretically, an infinite length of bed,
based on the assumed rate mechanism, is required for the
entire wave; this is because at the two ends of the wave the
driving force for mass transfer is zero. However, by inte
grating between two compositions other than the extreme ends
of the wave, the wave shape as a function of depth, L, can
be obtained. The left hand integral can be evaluated because
x is related to y from the equilibrium diagram, and y is
related to x by equation (20). A convenient lower limit
for the integration is xF/2, so that by integrating in both
directions to various values of x, the ultimate wave shape
may be obtained and plotted. Since the right hand side of
equation (21) before integration equals dH, the wave shape
equation may be written in terms of the dimensionless para
meter:


-90-
TABLE 12
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
DAVISON 6-12 MESH SILICA GEL
Run No. F 2b (cf. Figure 20)
Col. Diam.
* 2.47 cm.
Ave. Inverse
Rate *= 20 sec./cc.
Wt. Gel.
- 95.15 g.
VP
*= .402 cc./g.
Pb
- .679 g./cc.
fv
= .293
*F
- Vol. fr.
Toluene
Sample Size
5 drops
Sample No.
Time, sec.
Total Vol.
Effluent, cc
X
Vol. Fraction
. Toluene
1
1650
.10
.035
2
1725
4.35
.090
3
1762
6.60
.136
4
1809
8.85
.100
5
1847
11.10
.060
6
1890
13.35
.205
7
1930
15.60
. ISO
8
1975
17.85
.278
9
2022
20.10
.328
10
2066
22.35
.341
11
2183
27.60
.366
12
2298
32.85
.390
13
2398
38.10
.405
14
2499
43.35
.406
15
2611
48.60
.436
16
2713
53.85
.440
17
2828
59.10
.444
18

64.35
.452
19
3037
69.60
.460


12. The value of x and y (equal) for grid point 9 was
computed by formula 2.
13. Subsequent calculations proceeded, using formula 1 to
compute values of y, and using formula 2 to compute values
of x for all normal interior points. Points on and neighbor
ing to the boundaries H ~ 0 and H T were calculated as
noted in steps 5, 7, 10, and 11.
C. Computer Program
The development of a computer program to perform
the computations described above was a tedious, drawn-out
process rife with rewrites and changes in procedure. The
IBM programming procedures first had to be learned, largely
from the manuals available for this purpose, but with a good
deal of help from the University of Florida Statistical
Laboratory personnel. The specific programming method chosen
was the IBM SOAP II method, developed for the Type 650
machine. The program itself is much too long and complicated
to be discussed here, although a complete copy of the SOAP II
program is included in the Appendix. The SOAP II procedure
has the advantage that the program is listed in a symbolic
code as well as the numerical machine code. The printed
program also includes comments inserted specifically to help
orient the operator as to the calculations being performed
in each particular section of the program. In Figure 1 a
"Flow Diagram" of the program is presented. It must suffice


-77-
TABLE 1
NUMERICAL INTEGRATION FORMULAE
yi+l,j + [ ATj [(3/2)y/dT)if j (1/2) (oy/T)^ jj (1)
This formula fits a second degree polynomial over
two aT increments.
- xi,j +i-A] [(5/12)(Sx/SH)ljj+1 +
(2/3)(5x/oH)i>J a/12'H2>x/*E)
This formula fits a third degree polynomial over
two AH increments. Trial and error is required.
Yi+l,j ~ Yi,j + LAT][(l/2)(dy/dT)i>J + (1/2) (dy/6 T)i+1> j] (3)
This formula fits a second degree polynomial over
one aT increment. Trial and error is required.
xi,j+l xi,j + f-AHj [(l/2)(Sx/dH)i>j + (l/2)(dx/dH)i(J+1] (4)
This formula fits a second degree polynomial over
one AH increment. Trial and error is required.
*1+1, J yi(J + [at] [<5/12)(dy/T)i+1;j +
(2/3)(dy/T)i j (l/12)(dy/dT)i_1>jJ
This formula fits a third degree polynomial over
one AT increment. Trial and error is required.


(34), Kondrashon (35), Ilin (36), Rogenskei (37), and
Crespi (38, 39), most of which were still rather empirical.
The idea that the rate depends upon the approach to the
equilibrium condition was appearing in various mathematical
forms in most of this work. A few workers began to consider
the kinetics as similar to those of chemical reactions,
requiring activation energies, etc. Taylor (40) approached
the subject in this manner; but Nizovkin (41) decided that
diffusion of the gases controls the entire process. Crespi
(42) derived a rate equation from Langmuir and Freundlich
isotherms which was also of the chemical kinetics type.
Later, Damkohler (43) showed that the Langmuir derived equa
tion applies only where establishment of the equilibrium
r
takes 10" seconds, otherwise diffusion of the material to
the adsorption site is controlling.
Brunauer, Emmett, and Teller published their impor
tant paper which dealt with the derivation of adsorption
isotherms on the assumption that condensation forces are
responsible for multimolecular layer adsorption (44). Sta
tistical mechanical approaches to the explanation of adsorp
tion equilibrium were presented by Wilkins (45) and Kimball
(46). Experimental studies of adsorption from binary liquid
solutions were performed by Ruff (47), Jones, et. al. (48),
and Kane and Jatkar (49).


-12-
Amundsen in his first paper on the mathematics of
bed adsorption (55) developed differential equations based
on the assumptions of irreversible adsorption and a rate
proportional to the concentration of the adsorbate in the
gas stream and to the approach to equilibrium on the ad
sorbent. In a later paper he took into account the desorp
tion pressure exerted by the adsorbate.
In 1947 Hougen and Marshall (56) developed methods
for calculating relations between time, position, tempera
ture, and concentration, in both gas and solid phase in a
fixed bed, with the restriction that the adsorption isotherms
be linear. Analytical solutions of the partial differential
equations were obtained and plots of the solutions were made.
The interest in multicomponent adsorption equilibria
grew rapidly in the late 1940's. Many papers were published
for both gases and liquids showing isotherms for various
experimentally investigated systems, and various modifica
tions of the Brunauer, Emmett, and Teller isotherms were
proposed. Such papers were authored by Wieke (57), Mair (58),
Arnold (59), Spengler and Kaenker (61), Lewis and Gilliland
(62), and Eagle and Scott (63). Industrial applications
were described by Berg (60), who explained the Hypersorption
process for separation of light hydrocarbons, and by Weiss
(64).


Let T
(3)
(4)
-24-
- and H (KLaA/Q)(L)
The resulting transformation equations are,
(dy/c)0)L 13 fy/dT)jj(Kba/pbVp)
tix/de )h (x/dT)H(KLa/pbVp)
(dx/^L)e -(AfvKLa/QpbVp)(ax/3T)H + (KLaA/Q) (^x/^H)T
Substitution of these relations into equations (1) and (2)
gives,
(px/dH)T = -(dy/dT)H (5)
x x* = (ay/dT)H (6)
Equations (5) and (6) together with the x-y equilibrium
relationship, express, in the desired dimensionless form, the
mathematical relations which the adsorption process obeys,
according to the assumptions listed originally. A solution
of these equations, based on the proper boundary conditions,
should be correlatable with experimental data. It should be
noted that all of the physical properties involved in defin
ing H and T are readily measured experimentally except KLa.
The evaluation of KLa must hinge upon the matching of the
calculated solution with experimental data.
C. The Dimensionless Parameters H and T
It is important to the statement of the boundary
conditions and to the understanding of the results of the
calculation that the physical significance of the dimension
less parameters, H and T, be understood. Multiplication of


H, Dimensionless Bed Depth
FIGURE 2.- LIQUID PHASE COMPOSITION HISTORY,
COMPUTER SOLUTION TO PROBLEM 1.


-134-
(15) Polanyi, M. Adsorption of Gases by Solid Adsorbent.
Verh. Deut. Physik. Soc. 18: 55-80. 1916.
(16) Williams, A. M. Adsorption Isotherm at Low Temperatures.
Proc. Roy. Soc. Edinburgh. 3£: 48-55. 1918.
(17) Polanyi, M. Adsorption From Standpoint of 3rd Law of
Thermodynamics. Verh. Deut. Physik. Soc. 16:
1012-1016. 1914.
(18) Williams, A. M. Adsorption of Gases at Low and Moderate
Concentration. Proc. Roy. Soc. London. 96A: 287-297,
298-311. 1919.
(19) Lamb, A. B., and Coolidge, H. Sprague. Heat of Adsorp
tion of Vapors on Charcoal. J. Am. Chem. Soc. 42:
1146-1170. 1920.
(20) Gurvich, L. G. Physico Chemical Attractive Force. J.
Russ. Phys. Chem. 47: 805-827. 1915.
(21) Berzter, F. Rate of Adsorption of Gases by Charcoal.
Ann. Physik. 37: 472-507. 1912.
(22) Rakovskii, V. Adsorption Kinetics of Hydration and
Dehydration. J. Russ. Phys. Chem. Soc. 44:
836-849. 1912.
(23) Gurvich, L. Adsorption. Z. Chem. Ind. Kolloide. 11;
17-19. 1913.
(24) Freundlich. Desorption-Velocities. Z. Physik. Chem.
85: 660-680. 1914.
(25) Dietl, A. Kinetics of Adsorption. Koll. Chem. Beiheste.
6: 127. 1914.
(26) Hernad, H. S. Velocity of Adsorption of CCI4 by Charcoal.
J. Am. Chem. Soc. 42: 372-391. 1920.
(27) Polanyi, M. Adsorption Catalysis. Elektrochem. 27:
142-150. 1921.
(28) Kruyt, H. R. Heterogeneous Catalysis and Adsorption.
Rec. Tran. Chem. 40: 249-280. 1921.
(29) Mathews, Albert P. Principle of Adsorption. Physiol.
Review. 1: 553-597. 1921.


-170-
INLZC
RAU
8002
INLZD
AND DRF
1276
60
8002
1822
INLZD
STL
0100
INLZE
LOCATIONS
1822
20
0100
1703
INLZE
RAL
INLZD
1703
65
1822
1677
ALO
INLZK
1677
15
1481
1444
STL
INLZD
1444
20
1822
1326
SLO
INLZQ
1326
16
1531
1494
NZE
INLZC
PARTA
1494
45
1276
1000
CONSTANTS
TMTEN
0010
0984
0010
INLZA
STL
0100
INLZE
1564
20
0100
1703
INLZK
0001
1481
0001
INLZQ
STL
0501
INLZE
1531
20
0501
1703
RSTK1
01
0103
RSTKA
1693
01
0103
1286
RSTK2
01
0302
RSTKB
1396
01
0302
0614
RSTK3
01
0102
RSTKC
1722
01
0102
0822
RSTK4
STD
0303
CL1PE
1514
24
0303
0656
RSTK5
01
1930
RSTKD
1278
01
1930
0847
RSTK6
01
1933
RSTKE
1653
01
1933
0708
RSTK7
01
0301
RSTK7
1880
01
0301
1880
RSTK8
01
0101
RSTK8
1147
01
0101
1147
RSTK9
NZE
STPCB
STPCC
1034
45
0826
0950
RSTKO
NZE
STPCB
STPCA
0816
45
0826
0977
TSWFK
01
0300
TSWFK
1173
01
0300
1173
SRYFK
01
0100
SRYFK
1431
01
0100
1431
ITNWB
SRD
0001
TSNWC
1772
31
0001
0085
ITNLP
NZE
CNPWA
CL2PA
1394
45
0010
0011
BLA
0504
0600
BLR
0503
BLR
0601
1999
SUBROUTINE FOR XSTAR
0503
STD
SRXSZ
0503
24
0506
0509
STL
YCALC
0509
20
0513
0516
SLO
D
0516
16
1443
0547
BMI
YLOWR
YUPPR
0547
46
0550
0551
YUPPR
RAU
YCALC
0551
60
0513
0517
MPY
IF! IA
0517
19
0520
0540
SRD
0009
0540
31
0009
0563
ALO
A
0563
15
1785
0539


VI. RESULTS OF CALCULATIONS
A. Problem Solutions
The numerical solution to the binary liquid adsorp
tion fractionation problem was run twenty-three times on
the IBM 650 computer. Each time the problem was solved,
there were two parameters which were subject to change.
These were the composition of the feed liquid, xjp, and the
shape of the x-y equilibrium diagram relating the composi
tion of the adsorbed and unadsorbed phases at equilibrium.
The latter parameter actually consists of one or more equa
tions which express the x-y relationship over the range
x O to x = 1. These equations were included as a sub
routine of the computer program, and to make a change it was
merely necessary to place in the deck of program cards the
proper subroutine deck for the x-y relationship desired.
The problems which were computed are summarized as
to the parameters used in each solution in Table 2. Four
of the solutions were run for comparison with experimental
data of Lombardo (73) (Benzene-Hexane fractionation on
Silica gel) and with experimental data of this study (Toluene-
Methylcyclohexane on Silica gel). The remaining solutions
were run to provide a set of curves for use in evaluating the
effect of the parameters on column operation. This latter
-40-


Volume Fraction Benzene in Effluent
-121-
Total Volume of Effluent, cc.
FIGURE 17.- BENZENE-HEXANE FRACTIONATION WITH SILICA GEL
LOMBARDO RUN B-3.


LIST OF TABLES
>

Table Page
1. Numerical Integration Formulae 77
2. Summary of Adsorption Fractionation Calculations.. 78
3. Determination of Specific Pore Volumes 80
4. Adsorption Equilibrium Data for Toluene-Methyl
cyclohexane on Davison 6-12 Mesh Silica Gel 81
5.Adsorption Equilibrium Data for Toluene-Methyl
cyclohexane on Alcoa 8-14 Mesh Activated Alumina.. 82
6. Adsorption Equilibrium Data for Benzene-N-
Hexane on Davison Thru 200 Mesh Silica Gel 83
7. Summary of Fractionation Experiments 84
8. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 86
9. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 87
10. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 88
11. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel !... 89
12. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 90
13. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 91
14. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 92
15. Toluene-Methylcyclohexane Fractionation on
Davison 6-12 Mesh Silica Gel 93
v


Page 2 of3
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PUBLICATION DATE: 1958
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ram
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168-
STD
B
1283
24
1343
1196
LDD
1955
1196
69
1955
1108
STD
1931
1108
24
1931
0934
STD
C
0934
24
1393
1246
LDD
1956
1246
69
1956
1359
STD
1932
1359
24
1932
1835
STD
D
1835
24
1443
1296
LDD
1957
1296
69
1957
1710
STD
1933
1710
24
1933
1493
RAL
1958
1493
65
1958
1464
STL
1934
1464
20
1934
1543
SRT
0001
1543
30
0001
1049
STL
TI NCR
1049
20
0666
1669
RSL
8002
1669
66
8 002
1527
STL
B I NCR
1527
20
0078
1281
LDD
TMTEN
1281
69
0984
1593
STD
TMCST
1593
24
1013
1316
RAU
8003
1316
60
8003
1123
STL
TMCTR
1123
20
0034
1643
PCH
1927
PCH DUP
OF INPUT C
1643
71
1927
1577
LDD
0501
COMPUTE
CONSTANTS
FOR EQUILB
EQUATIONS
1577
69
1830
0501
LDD
0502
COMPUTE
Y IN EQLBR
WITH FEED
1830
69
1333
0502
LDD
RSTK1
INITIALIZE
1333
69
1693
1346
STD
RSTKA
RESET
1346
24
1286
1743
LDD
RSTK2
INSTRUCTNS
1743
69
1396
1099
STD
RSTKB
1099
24
0614
1568
LDD
RSTK3
1568
69
1722
1825
STD
RSTKC
1825
24
0822
1875
LDD
RSTK5
1875
69
1278
1331
STD
RSTKD
1331
24
0847
1150
LDD
RSTK.6
1150
69
1653
1556
STD
RSTKE
1556
24
0708
1711
LDD
RSTK4
1711
69
1514
1618
STD
RSTKF
1618
24
0828
1381
LDD
RSTK.9
1381
69
1034
1793


-167
SRD
0009
AND LOOP
1748
31
0009
1672
ALO
XEST
1672
15
0033
1592
STL
XEST
AVGXC
1592
20
0033
1178
CONSTANTS
HLFAI
03
1228
05
HLFAK
05
1725
05
PARTG
RAL
TMCTR
ADD ONE TO
1406
65
0034
1642
AUP
1934
TIME CTR
1642
10
193 4
1692
ALO
TMONE
AND TEST
1692
15
1190
1046
AUP
8001
TO PUNCH
1046
10
8001
1603
SUP
8003
1603
11
8003
1661
STD
1934
1661
24
1934
1742
STL
TMCTR
1742
20
0034
1792
SLO
TMCST
1792
16
1013
1518
NZE
RSETA
1518
45
0633
1073
STL
TMCTR
1073
20
0034
1842
RAL
CDCSC
1842
65
1096
1351
LDD
1927
1351
69
1927
1630
S IA
1927
1630
23
1927
1680
RAL
0001
1680
65
8001
1892
ALO
CDCST
1892
15
0740
1146
STL
1927
1146
20
1927
1730
PCH
1927
RSETA
1730
71
1927
0633
CONSTANTS
CDCSC
01
CDCSC
3300
1096
01
1096
3300
CDCST
0001
0740
0001
INILZ LDD
1951
INITIALIZATION
MOVE DATA
1100
69
1951
1004
STD
1927
FROM INPUT
1004
2 4
1927
1780
LDD
1952
CARD TO
1780
69
1952
1456
STD
XFEED
VARIOUS
1456
24
1087
1243
STD
1928
STORAGE
124 3
24
192 8
1231
LDD
1953
SPOTS
1231
69
1953
1506
STD
1929
1506
24
1929
1432
STD
A
1432
24
1785
1293
LDD
1954
1293
69
1954
1058
STD
1930
1058
24
1930
1283


IV. THEORY
It can be seen from the foregoing literature survey
that there has been some very creditable work done towards
the mathematical treatment of adsorption and ion exchange
kinetics, especially in recent years. Nevertheless, it
appears that there are enough variations in the different
phenomena of vapor phase adsorption, ion exchange, and liquid
phase adsorption to warrant a treatment based specifically
on the system being considered. The electronic computer is
best suited for individual treatment of a difficult problem,
since the results obtained by computer analysis are in the
form of numerical answers to the specific problem with par
ticular boundary conditions. To obtain general answers
comparable to an analytical solution, it is necessary to run
the problem repeatedly on the computer, varying the para
meters and boundary conditions each time, until enough
answers are computed to permit the drawing of graphs and
curves which present the desired coverage of the variables.
A. The Fixed Bed Binary Liquid Adsorption Process
The basic assumptions made to define the fixed bed
fractionation of a binary liquid are described below. These
are the conditions on which the calculations made in this
study were based. The following discussion points out the


141
IBM 650 PROGRAM FOR
THE COMPUTATION OF
FIXED BED ADSORPTION
FRACTIONATION OF
BINARY LIQUID SOLUTIONS
RESERVE DRUM SPACE FOR
FUTURE USE
BLR
RESVE ZERO
01
9999
FOR STOP
0000 01
9999
BLR
0100
0500
STRAGE FOR
Y AND DRF
BLR
0501
0600
INITLIZING
SUBRTINES
BLR
1900
1999
DRUM PUNCH
OUT AND
READ IN
ZONE
COMPUTE
BLOCK FOR
NORMAL
POINT IN WAVE
TNLPA
RAL
0103
TNLP1
TEST FOR
0050
65
0103
0007
TNLP1
NZE
CNPWA
CL2PA
NEXT TO
LAST POINT
0007
45
0010
0011
CNPWA
RAU
DRFNW
COMPUTE
0010
60
0013
0017
MPY
EIGHT
CONTRIBUTN
0017
19
0020
0040
SRD
0009
OF PRESENT
0040
31
0009
0063
SLO
DRFPV
AND PREV
0063
16
0016
0021
STL
SUMDF
DRF TO
0021
20
0025
0028
CUBIC EQTN
RAU
DRFNW
COMPUTE
0028
60
0013
0067
SUP
DRFPV
ESTIMATE
0067
11
0016
0071
MPY
HLFAR
OF X BY
0071
19
0024
0044
SRD
0009
ADAMS
0044
31
0009
0617
RAU
8002
QUADRATIC
0617
60
8002-
0075
MPY
BI NCR
METHOD
0075
19
0078
0048
SRD
0009
0048
31
0009
0621
ALO
XNOW
0621
15
0074
0029


-149-
LDD
1958
0753
69
1958
0861
STD
1934 PARTC
0861
24
1934
1137
COMPUTE
NEXT TO LAST
POINT
IN
WAVE
CL2PA
RAU
DRFNW
COMPUTE
0011
60
0013
0867
MPY
EIGHT
CONTRIBUTM
0867
19
0020
08 40
SRD
0009
OF PRESENT
0040
31
0009
1213
SLO
DRFPV
AND PREV
1213
16
0016
0821
STL
SUMDF
DRF TO
0821
20
0025
0728
CUBIC EQTN
RAU
DRFNW
COMPUTE
0728
60
0013
0917
SUP
DRFPV
ESTIMATE 0
0917
11
0016
0871
MPY
HLFBA
X BY ADAMS
0871
19
0674
0694
SRD
0009
QUADRATIC
0694
31
0009
0967
RAU
8002
METHOD
0967
60
8002
1175
MPY
31 NCR
1175
19
0078
0748
SRD
0009
0748
31
0009
0921
ALO
XNOW
0921
15
0074
0979
STL
XEST
0979
20
0033
0936
LDD
DRFNW
0936
69
0013
0866
STD
DRFPV
CL2PB
0866
24
0016
0073
CL2PB
RAU
0102
CL2P1
COMPUTE
0073
60
0102
1107
CL2P1
MPY
T I NCR
ESTIMATE
1107
19
0666
0986
SRD
0009
CL2PC
OF Y BY
0986
31
0009
0642
CL2PC
ALO
0302
CL2P2
LINEAR
0642
15
0302
1157
CL2P2
STL
YEST
CL2PD
METHOD
1157
20
0911
0 014
CL2PD
RAL
YEST
COMPUTE
0014
65
0911
0015
LDD
0503
NEW Y BY
0015
69
0018
0503
RAU
XEST
AVGING
0018
60
0033
1187
SUP
XSTAR
METHOD
1187
11
0090
1045
STU
DRFNW
CL2PE
AND COMP
1045
21
0013
0879
CL2PE
AUP
0102
CL2P3
WITH YEST
0879
10
0102
1207
CL2P3
MPY
HLFBB
1207
19
1260
1180
SRD
0009
1180
31
0009
0803
RAU
8002
0803
60
8002
0961
MPY
T I NCR
0961
19
0666
1036
SRD
0009
CL2P4
1036
31
0009
0004
CL2P4
ALO
0302
0004
15
0302
1257
AUP
YEST
1257
10
0911
0065
SLO
8002
0065
16
8002
0673


166-
PARTF
AVGXC
CNXSB
RAU
DRFNW
COMPUTE
0954
60
0013
1318
SUP
DRFPV
X AND Y
1318
11
0016
1472
MPY
HLFAK
EST FOR
1472
19
1725
0946
SRD
0009
NEXT POINT
0946
31
0009
1569
ALO
DRFNW
3Y ADAMS
1569
15
0013
1368
RAU
8002
QUADRATIC
1368
60
8002
1477
MPY
81 NCR
METHOD
1477
19
0078
1598
SRD
0009
1598
31
0009
1522
ALO
XNOW
1522
15
0074
1879
STL
XEST
PARTF
1879
20
0033
1790
RAU
DRFNW
COMPUTE
1790
60
0013
1418
MPY
EIGHT
CONTRIBUTN
1418
19
0020
18 40
SRD
0009
OF DRF PV
1840
31
0009
1414
SLO
DRFPV
AND DRFNW
1414
16
0016
1572
STL
SUMDF
AVGXC
TO AVGDF
1572
20
0025
1178
RAL
XEST
COMPUTE
1178
65
0033
1890
LDD
0503
X AMD Y
1890
69
1193
0503
RAU
XEST
BY CUBIC
1193
60
0033
1242
SUP
XSTAR
AVGRAGING
1242
11
0090
0996
STU
010 2
AND COMPAR
0996
21
0102
1356
MPY
FIVE
WITH XEST
1356
19
0069
1292
SLT
0001
1292
35
0001
0949
AUP
SUMDF
0949
10
0025
1530
SRT
0002
1530
30
0002
1342
DVR
TWLVE
1342
6 4
0038
1648
RAU
8002
1648
60
8002
1857
MPY
BI NCR
1857
19
0078
1698
SRD
0009
1698
31
0009
1622
ALO
XNOW
1622
15
0074
1580
AUP
XEST
1580
10
0033
1392
SLO
8002
1392
16
8002
1301
STD
XEST
1301
24
0033
1442
SUP
8001
1442
11
8001
0999
RAL
8003
0999
65
8003
1008
SRD
0001
1008
31
0001
1265
NZE
CNXSB
1265
45
1468
1619
LDD
XEST
1619
69
0033
1492
STD
1930
1492
24
1930
1233
STD
1933
1233
24
1933
1542
STD
0302
PARTG
1542
24
0302
1406
RAU
8001
COMPUTE
1468
60
8001
1775
MPY
HLFAI
NEW XEST
1775
19
1223
1748


-36-
fit second degree equations over one time increment. Since
it was desired to fit at least second degree equations in
every integration step, the simultaneous calculation of
x and y for this point was required.
7. The value of x and y (equal) for grid point 5 was com
puted using formula 2, which fits a third degree equation
by trial and error over two time increments. All subsequent
points along the H * T diagonal were calculated using this
formula.
8. The value of y at point 7 was computed by formula 1,
which fits a second degree equation over two time increments
without trial and error. This is the first instance in which
formula number 1, for a "normal" point, was used.
9. The value of y at point number 6 was computed by formula
5.
10. The value of x at point 7 was computed by formula 4,
which fits a second degree equation by trial and error over
one increment. All subsequent values of x along the H AH
axis were computed by formula 4.
11. Values of x and y at point 8 were computed simultaneously
in order to use at least second degree equation accuracy.
Formulae 2 and 3 were used, involving a double trial and
error. All subsequent values of x and y along the diagonal
neighboring the H * T diagonal were computed with these
formulae. This is the only instance of double trial and
error involved.in this procedure.


Volume Fraction Toluene in Effluent
-123-
Total Volume of Effluent, cc.
FIGURE 19.- MCH-TOLUENE FRACTIONATION WITH SILICA GEL
JOHNSON RUN F-l.


-98
TABLE 20
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 6a (cf. Figure 23)
Col. Diara.
Wt. Alumina
Pb
XF
2.47 cm.
Ave. Inverse
Rate = 16 sec/cc.
62.8 g.
vp
= .1888 cc./g.
.883 g./cc.
*v
= .425
0.5 Vol. fr.
Toluene
Sample Size
5 drops
Sample No.Time, sec.
x
Total Vol. Vol. Fraction
Effluent, cc.Toluene
1
852
.10
.252
2
945
5.35
.370
3
1025
10.60
.435
4
1112
15.85
.458
5
1198
21.10
.478
6
1286
26.35
.484
7
1370
31.60
.488
8
1454
36.85
.492
9
1538
42.10
.493
10
1623
47.35
.493
11
1707
52.60
.493
12
1782
57.85
.494
13
1865
63.10
.494
14
1948
68.35
.494
15
2032
73.60
.495
16
2116
78.85
.495
17
2198
84.10
.495
18
2280
89.35
.495
19
2361
94.60
.496


Copyright hy
Adrain Earl Johnson, Jr.
1961


-45-
The numerical solutions obtained with the IBM 650
in this work provided the answers to these questions in each
case investigated, but did not shed light upon other cases,
e.g., equilibrium diagrams of different shape from those
studied here. This, admittedly, is one of the main draw
backs to numerical solutions.
If one starts with the assumption that a zone 2 of
non-changing shape is formed, its velocity may be calculated.
Since zone 3 is continually building up in length as the
adsorption progresses, zone 2 must move through the column
at a rate slower than the rate that the liquid passes through.
Therefore, if we imagine a column in which the adsorbent is
made to move in the opposite direction from the liquid, there
is a certain rate of adsorbent movement which will cause
zone 2 to remain stationary. There is, then, a counter-
current moving bed which is exactly analogous to the fixed
bed operation. See the following diagram.
Countercurrent Case
Zone 2 Stationary
w £ *
y-0 t x-0
Fixed Bed Case
Zone 2 Moves-
y-yf* x-xy


-102-
TABLE 24
BENZENE-N-HEXANE FRACTIONATION ON
DAVISON "THRU 200" MESH SILICA GEL
(Data of Lombardo)
Run No. B 3 (cf. Figure 17)
Col. Diam.
8 mm.
Ave.
Inverse Rate = 650 sec./cc.
Wt. Gel.
B 10 g.
vp
.357 cc./g.
Pb
.623 g./cc.
- 0.500 Vol. fr.
Benzene
fv
464
Sample No
Time, sec.
Sample
Volume, cc.
X
Vol. Fraction
Benzene
1
0
320
0.5
0
2
595
11
0
3
880
ft
0
4
1190
11
0
5
1500
It
0.281
6
1820
11
0.481
7
2140
11
0.500


D. Use of Constant-Alpha Type Equilibrium Diagrams
In the previous discussion of the numerical integra
tion process, it was mentioned that a number of computer
solutions were obtained to the adsorption fractionation
problem using equilibrium curves of the constant-alpha type
in anticipation of the possibility of using them for approxi
mate solutions to specific cases, whenever the true equilib
rium curve of the system could be approximated by a constant
alpha curve. The results of such an approximation would
certainly be more valuable than the application of solutions
based on straight line equilibrium diagrams, which can approxi
mate only a very small portion of an equilibrium curve.
It was hoped that a constant-alpha curve based on an
average alpha over the range of the fractionation experiment
would approximate the solution closely enough to be used in
many systems. It was discovered, however, that it is quite
important to use an equilibrium diagram which exhibits the
exact relative adsorbability, alpha, for the system at the
feed composition. That this is necessary was shown in the
previous discussion on ultimate velocity of the adsorption
wave. For the wave to come to the proper ultimate velocity
(and, presumably, approach it in the proper manner) the value
of xp/yF* used in a calculation must be exact. This means
that, not an average alpha, but the alpha of the feed compo
sition must be used. In adsorption systems, alpha is very


-136-
I
)
>
(44) Brunauer, Emmett, Teller. Adsorption of Gases in Multi-
molecular Layers. J. Am. Chem. Soc. 60: 309-318. 1938.
(45) Wilkins, F. J. Statistical Mechanics of the Adsorption
of Gases at Solid Surfaces. Proc. Roy. Soc. London.
A164: 496-509. 1938.
(46) Kimball, Geo. E. The Absolute Rate of Heterogeneous
Reactions. J. Chem. Phys. 6: 447-453. 1938.
(47) Ruff, Walter, A Study of the Adsorption Dynamics of
Mixed Dissolved Substances. V. Wasser. 1JL: 251-265.
1936.
(48) Jones, W. J., et. al. Simultaneous Adsorption from Dilute
Aqueous Solutions. J. Chem. Soc. 269-271. 1938.
(49) Kane, J. C., and Jatkar, S. K. K. Studies in Binary
Systems. J. Indian I. Soc. 21A: 385-394, 407-411,
413-416. 1938.
(50) Brunauer, Doming, Teller. A Theory of Van der Waal's Ad
sorption of Gases. J. Am. Chem. Soc. 62: 1723-1732.
1940.
(51) Wilson, J. Norton. A Theory of Chromotography. J. Am.
Chem. Soc. 62: 1583-1591. 1940.
(52) Martin, J. P., and Synge, R. L. M. A Theory of Chromo
tography. Brochen. J. 3j3: 1358-1368. 1941.
(53) De Vault. The Theory of Chromotography. J. Am. Chem.
Soc. 65: 532-540. 1943.
(54) Thomas, H. C. J. Am Chem. Soc. 166: 1664. 1944.
(55) Amundsen, Neal R. Mathematics of Adsorption in Bed.
J. Phys. and Colloid Chem. 52: 1153-1157. 1948.
(56) Hougen, 0. A., and Marshall, W. R. Adsorption From A
Fluid Stream Flowing Through A Granular Bed. Chem.
Engr. Progress. 43: 197-208. 1947.
(57) Wieke, E. The Separation of Gas Mixtures by Flow Through
Adsorbents. Angewandte Chem. B19: 15-21. 1947.
(58) Mair, B. J. Assembly and Testing of 52 Foot Lab.
Columns-Separation of Hydrocarbons. Ind. Eng. Chem.
39: 1072-1081. 1947.
(59) Arnold, James R. Adsorption of Gas Mixture. J. Am.
Chem. Soc. 71: 104-110. 1949.


H, Dimensionless Bed Depth
FIGURE 4.- LIQUID PHASE COMPOSITION HISTORY,
COMPUTER SOLUTION TO PROBLEM 9.
-108-


154-
RSTKA
01
0103
RSTKA
1286
01
0103
1286
RSTKB
01
0302
RSTKB
0614
01
0302
0614
RSTKC
01
0102
RSTKC
0822
01
0102
0822
RSTKO
01
1930
RSTKD
0 847
01
1930
0847
RSTKE
01
1933
RSTKE
0708
01
1933
0708
RSTKF
STD
0303
CL1PE
0828
24
0303
0656
RSTKG
3000
0831
3000
TEST FOR WAVE FRONT
TSWFA
RAL
0300
TSV/F1
0723
65
0300
1355
TSV/F1
SLO
YEQFD
1355
16
0758
1613
SRD
0001
1613
31
0001
1119
BMI
SATBD
1119
46
0872
0773
NZE
SATBD
0872
45
0776
0773
LDD
CFPWA
SRYF
0776
69
1329
0982
SATBD
STD
0300
AD V Vi A
0773
24
0300
1003
TEST FOR
END OF PROBLEM
TSENP
RAL
TSWFA
0900
65
0723
0877
SLO
ENPRK
0877
16
1280
0985
BMI
RSETA
0985
46
0633
1289
NZE
8000
1289
45
8000
0693
RAU
8003
ARRANGE
0693
60
8003
0951
STL
TMCTR
TO PUNCH
0951
20
0034
1537
LDD
TMONE
LAST TIME
1537
69
1190
0743
STD
TMCST
RSETA
INCREMENT
0743
24
1013
0633
CONSTANTS
ENPRK
RAL
0497
TSWF1
1280
65
0497
1355
CALCULATION OF FIRST
POINT
IN
WAVE
SRYF
STD
SRYFZ
SRYFP
0982
24
1035
0888
SRYFP
RAL
0300
SRYFG
COMPUTE
0888
65
0300
1405
SRYFG
STD
1931
1405
24
1931
0734
STD
YFSPT
0734
24
0957
1560


-4-
phenomenon because the solution to the equations could not
be provided by the most expert mathematician; instead, the
theorist resolved the difficulty by making restricting
assumptions about the process which simplified the equations
and permitted a solution. Such solutions are quite useful
in the design of a process, but they are always only approxi
mations. Sometimes their use leads to serious and costly
mistakes, not only in the design of industrial processes,
but in the interpretation of the phenomenon being investigated.
In June, 1957, an electronic digital computer, IBM
type 650, was installed at the University of Florida Sta
tistical Laboratory. This machine, with its auxiliary
equipment, represents the beginnings of a computing center,
which will be available to the University and the State on a
basis similar to that of the other facilities of the Labora
tory.
In anticipation of the installation of this computer,
the subject research was initiated in the field of chemical
engineering unit operations with the view of utilizing the
computer for providing a solution to equations which promise
to express a theory more precisely than previous treatments.
The unit operation chosen for a study was adsorption, which
is a relatively new entrant to the commercial field of large-
scale separation process. The "Arosorb" (1) and "Hyper
sorption" (2, 60) processes for the separation of petroleum
hydrocarbons are examples of commercial applications of


-97-
TABLE 19
TOLUENE-METHYLCYCLOHEXANE FRACTIONATION ON
ALCOA 8-14 MESH ACTIVATED ALUMINA
Run No. F 5c (ci. Figure 22)
Col. Diara.
- 2.47 cm.
Ave. Inverse
Rate 8.13 sec./cc
Wt. Alumina
- 59.7 g.
p
** 1888 cc. /g.
P b
*= .883 g./cc.
fv
- .425
Xj,
~ 0.100 Vol. fr.
Toluene
Sample Size
*> 5 drops
Sample No.
Time, sec.
Total Vol.
Effluent, cc.
X
Vol. Fraction
Toluene
1
410
.10
.016
2
497
10.35
.044
3
581
20.60
.066
4
30.85
.079
5
750
41.10
.087
6
833
51.35
.095
7
916
61.60
.097
8

71.85
.099
9

82.10
.100


TABLE 7
SUMMARY OF FRACTIONATION EXPERIMENTS
Run No. System Adsorbent Column Diam.,
cm.
F-la Toluene-MCH
F-lb
F-lc
F-2a
F-2b
F-2c
F-4a
F-4b
F-4c
F-5a
F-5b
F-5c
Wt. Adsorbent, Inverse Rate, xp
g.sec,/cc.Feed Comp.
195
12.73
0.5
95.2
12.7
0.5
45.35
12.7
0.5
191.2
20
0.5
95.2
20
0.5
47.55
20
0.5
195.35
5.75
0.1
96.6
5.75
0.1
45.3
5.75
0.1
255.2
8.13
0.1
121.5
8.13
0.1
59.7
8.13
0.1
62.8
16
0.5
6-12 Mesh 2.47
Silica Gel
ft If
tf ft
! ? Tt
tf IT
Tl Tf
tt tf
tr tt
ft tt
8-14 Mesh
Alumina
tt Tf
tt ft
Tt tt
F-6a


-22-
adsorbed and unadsorbed phases
d(Qx)
- ran
e
dLrdg
+ AdLdg
rearranging gives:
(dx/dL)g + (Afv/Q)(dx/dg)L
+ (Sy/c)0)l J
- (PbVpA/Q)(dy/de)L
(1)
which is the equation of continuity written in volume
fractions.
The classical mass transfer rate equation for dif
fusion of component A between phase 1 and 2 across a film
whose area per unit volume of bed is unknown is,
rA -= KLa (CAl CA2)
for equimolar countercurrent diffusion of components A and B.
It is assumed that the conditions of equimolar
countercurrent diffusion are approximated closely enough by
the adsorption process, in which component B is displaced by
component A, to permit this form of mass transfer equation
to be used. The coefficient, Kj^a, is assumed to remain con
stant as CA varies. Thermodynamically, it is possible that
the coefficient, K^a, would be more constant if based upon
activities instead of molar concentrations; use of the above
equation may assume ideal solutions. If such is true, a
further refinement would be to include the activity coef
ficient in the above relation.
Writing the mass transfer rate equation for a
differential section of an adsorption bed,


-161-
STL
YEST
AVGYA
METHOD
1841
20
0911
0814
AVGYA
LDD
0503
COMPUTE Y
0814
69
0718
0503
RAU
XFEED
BY AVGING
0718
60
1087
1891
SUP
XSTAR
METHOD AND
1891
11
0090
1845
STU
DRFPV
COMPARE
1845
21
0016
1369
AUP
0100
1369
10
0100
1305
MPY
HLFAA
WITH YEST
1805
19
0958
1078
SRD
0009
1078
31
0 009
1201
RAU
8002
1201
60
8002
1159
MPY
T I NCR
1159
19
0666
1736
SRD
0009
1736
31
0009
1209
ALO
XFEED
1209
15
1087
0692
AUP
YEST
0692
10
0911
0815
SLO
8002
0815
16
8002
0373
STD
YEST
0873
24
0911
0864
SUP
8001
0864
11
8001
1621
RAL
8003
1621
65
8003
1679
SRD
0001
1679
31
0001
1485
NZE
CNYES
1485
45
1088
1639
LDD
YEST
PREPARE TO
1639
69
0911
0914
STD
0300
ADVANCE TO
0914
24
0300
1253
STD
1931
PARTB
NXT BED PT
1253
24
1931
0884
CNYES
RAU
8001
COMPUTE
1088
60
8001
1895
MPY
HLFAB
NEWYEST
1895
19
1298
0768
SRD
00 0 9
AND LOOP
0768
31
0009
0742
ALO
YEST
0742
15
0911
0865
STL
YEST
AVGYA
0865
20
0911
0814
CONSTANTS
CDCSA
0001
1300
0834
0001
1300
HLFAA
05
0958
05
HLFAB
05
1298
05
PARTB
RAU
DRFPV
COMPUTE
0884
60
0016
1671
MPY
BI NCR
XEST BY
1671
19
0078
1343
SRD
0009
LINEAR
1348
31
0009
1721
ALO
XFEED
METHOD
1721
15
108 7
0792
STL
XEST
AVGXA
0792
20
0033
1786
AVGXA
LDD
0503
COMPUTE
1786
69
1689
0503
RAU
XEST
X AND Y
1689
60
0033
1138


-50-
x
The straight line OA, which connects the origin with the
equilibrium curve at the point representing the feed condi
tion, can be thought of as the operating line for this process.
Everywhere along the invariant adsorption wave, whether the
wave is stationary or moving down the column, x and y for a
given bed point at a given instant must fall on the line
OA, that is obey equation (20). This relation may also be
verified by referring to any of the calculated curves for the
ultimate wave shapes (Figures 2-10).
It is apparent that if the equilibrium curve were to
cross the line OA, then the liquid and adsorbed phase compo
sitions could not possibly follow line OA. Hence, a require
ment for the formation of an invariant adsorption wave is
that the equilibrium diagram may not cross the operating"
line connecting (xjr,yF*) with the origin.


LIST OF ILLUSTRATIONS (Continued)
Figure Page
15. Adsorption Equilibrium Diagram for Benzene-
Hexane on Davison "Thru 200" Mesh Silica Gel.,.. 119
16. Benzene-Hexane Fractionation With Silica Gel.... 120
17. Benzene-Hexane Fractionation With Silica Gel.... 121
18. Benzene-Hexane Fractionation With Silica Gel.... 122
19. MCH-Toluene Fractionation With Silica Gel 123
20. MCH-Toluene Fractionation With Silica Gel 124
21. MCH-Toluene Fractionation With Silica Gel 125
22. MCH-Toluene Fiactionation With Alumina 126
23. MCH-Toluene Fractionation With Alumina 127
24. Effect of Liquid Velocity on Overall Mass
Transfer Coefficient 128
25. Effect of Liquid Velocity on HETS.. 129
26. Calibration of Refractometer for MCH-Toluene
Solutions 130
viii


VIII. COMPARISONS BETWEEN EXPERIMENTAL
AND CALCULATED RESULTS
The only method of comparing the results of the
computer calculations with the experimental data obtained
in this study and in the work of Lombardo is to test whether
the effluent composition curves of the adsorption fractiona
tion experiments can be satisfactorily correlated by the
computed solutions.
It has been explained that there is one unmeasured
property of the system, KLa, which is contained in both of
the dimensionless parameters, H and T, used in the calcula
tions. The success of the calculations depends on whether
for a given experiment a value of KLa can be found which
results in a good agreement between the experimental and the
calculated effluent curves, and whether the values of K^a so
obtained correlate with the flow rate of liquid through the
bed.
In fitting the calculated results to the experimental
data, there are two criteria which are considered. First,
the general shape of the adsorption wave should be approxi
mated, and second, the wave should be at the proper location
in the bed at the proper time. It has been pointed out that
in a long enough column, the wave will eventually come to an
ultimate shape and an ultimate velocity. In the experiments
-62-


-32-
B. Description of Integration Procedure
n m h h m n
ill + + +
t-j t-j t-j -r-j -r-j -r-j -r-j
i-2
-i-1 H
i
(
)

i+1
i 4-9

T
The numerical integration procedure can be described
as follows:
Given the value of (x,y)ij for a particular grid
point, (i,j), (see sketch above) within the desired H and T
boundary, x x* at this point may be computed from the
equilibrium x y relationship. From equations (5) and (6),
p. 24, the partial derivatives (Sx/ctH)x and (y/dT)n at
(i,j) should equal -(x x*) and ( x x*^ respectively.
The value of x at the neighboring grid point (i+l,j) may be
estimated by a suitable formula for numerical integration.
The simplest formula is that used by Schmidt in heat trans
fer calculations, which consists of assuming that (dx/0H)T
is constant between the point (i,j) and the point (i+l,j).
To put it more elegantly, a straight line may be fit over
the AH increment from (i,j) to (i+l,j) utilizing the value
of x and the slope, (c5x/c>H)T, both evaluated at (i,j).
Similarly, the value of y at the grid point (i,j+1) may be


Volume Fraction Toluene in Effluent
FIGURE 20.- MCH-TOLUENE FRACTIONATION WITH SILICA GEL
JOHNSON RUN F-2.


1.00
0.50
y,
Volume
Fraction
Component A
In Adsorbed Phase
0.10
0.05
0o01
FIGURE 9.- ULTIMATE ADSORPTION WAVE SHAPES
COMPUTER SOLUTION TO PROBLEM 52


FIGURE 6.- LIQUID PHASE COMPOSITION HISTORY,
COMPUTER SOLUTION TO PROBLEM 51.
i


-79-
Table 2 (Continued)
xF,
Calculation Vol. Frac. Comp.
Number A in Feed x-y Equilibria
17
0.5
a
= 7.0
18
0.1
a
= 9.0
19
0.3
a
9.0
20
0.5
a
- 9.0
* Data of Lombardo (73)
** Data of this work


-48-
of the dimensionless parameters is merely the ratio of the
feed liquid composition to the adsorbed phase composition in
equilibrium with the feed. Note that the physical properties
of the bed do not enter into the relation. This relation can
be verified readily by inspection of the calculated solu
tions (Figures 2-10) to the adsorption fractionation problem.
In every case, after sufficient bed depth H was reached, the
wave reached an ultimate shape and a velocity, AH/AT, which
JL.
equalled xp/yp .
C. The Shape of the Asymptotic Wave
The concept of a stationary wave maintained by a
movement of the adsorbent bed countercurrent to the liquid
flow can also be utilized in computing the ultimate wave
shape. Consider again a diagram of the liquid and adsorbed
phase composition plotted vs. bed depth, L, for the counter-
current bed, and assume that the wave is being maintained
stationary by appropriate flow of the liquid and adsorbent.
Bed Depth, L


-71-
separation from an x of 0.02 to 0.09. The values of HETS for
the toluene-MCH-silica gel system are also plotted in Figure
25 against Q/A.
It is significant that in both cases a trend is
established. There is a marked increase in HETS with the
velocity of the liquid through the bed. It is apparent that
more data of this type are required to establish whether HETS
is actually as strongly dependent upon liquid velocity as is
indicated here. If, however, the trends indicated here are
true, it would be very important in the design of a counter-
current adsorber to size the column diameter for a given
service properly.
F. Discussion of Calculations
The comparison of the computed curves for adsorption
fractionation with two systems has shown that a very good
agreement with experimental adsorption fractionation results
when the adsorbent particle size and liquid flow rates are
such that the external film is the major resistance to mass
transfer between the adsorbed and liquid phases. In these
cases the apparent or effective overall coefficient corre
lates well v/ith liquid velocity through the adsorbent bed.
It was found that a fair approximation of the column opera
tion is obtained when the intraparticle diffusion contributes
to the diffusional resistance. However, the wave shape is
definitely not duplicated by the calculated curves. Through


becomes zero with respect to component A, the more strongly
adsorbed component, but the length of bed required to arrive
at this condition is of importance. To the author's know
ledge, no treatment of the liquid phase process to date has
considered either of these two points. As will be seen later,
the development of the boundary conditions accurately
describing the binary liquid adsorption case is involved.
Item 4 has been shown to be true of liquid phase
adsorption in a great many instances, and is usually assumed.
It is particularly true of members of homologous series and
otherwise chemically related compounds. As a consequence
of item 4, it is generally convenient to assume item 5 also,
thus permitting compositions to be expressed in volume frac
tions rather than mole fractions.
Although some investigators continue to use a chemical
kinetics type of rate equation, it is generally accepted that,
as stated in item 6, diffusion controls liquid phase adsorp
tion processes.
The manner in which the diffusion is taken into
account is a topic of considerable interest. As stated in
item 7 the subject treatment assumes that the external and
intraparticle resistance can be lumped together as one over
all resistance. This admittedly is not as precise a theory
as desired; however, other investigators have not devised a
theory of intraparticle diffusion for liquid adsorption which
is acceptable to the author, nor has the author. One con-


-41-
group of nineteen solutions was based on a constant-alpha
type of equilibrium diagram as is used in correlating vapor-
liquid equilibria of distillation systems. In adsorption,
alpha is defined exactly as in distillation: (y/l-y)
(1-x/x) -a Although adsorption equilibria seldom cor
relate perfectly with a constant alpha, this is one of the
few algebraic formulae which approximate the general shape
of the adsorption x-y diagram over the complete range. It
was believed that a set of solutions based on the constant-
alpha equation should prove useful in interpreting the effect
on column performance of varying the two parameters, and it
was hoped that solutions obtained with constant-alpha dia
grams which approximate the experimental equilibrium data
might be used successfully to predict column performance.
The answers to the solutions were punched by the
computer onto standard IBM cards as they were calculated.
Each card contained six answers plus identifying informa
tion. The six answers were actually three sets of x and y
values corresponding to three bed grid points (H) at a given
time increment (T). To provide enough answers to draw smooth
curves through the points, it was not necessary to punch out
x and y values for every one of the grid point intersections.
In fact, this was not desirable at all, because the relative
change in the values of x and y between adjacent grid points
was quite small (in numerical integration this is a necessary
prerequisite for accuracy). Usually the choice was to punch


-15 9-
STD
RSTKB
1235
24
0614
1767
ALO
RSTKC
1767
15
0822
1077
ALO
S003
1077
15
8 003
1285
SLO
8002
1285
16
8002
0843
STD
RSTKC
0343
24
0822
1475
ALO
RSTKF
1475
15
0823
1133
ALO
8003
1133
15
3003
1591
SLO
8002
1591
16
8002
0799
5TD
RSTKF
0799
24
0828
0931
ALO
TSWFA
0931
15
0723
1127
ALO
8003
1127
15
8 003
1335
SLO
8002
1335
16
8002
0893
STD
TSWFA
0893
24
0723
0876
ALO
SATBD
0876
15
0773
1177
ALO
8003
1177
15
8003
1385
SLO
8002
1385
16
8002
0943
STD
SATBD
0943
24
0773
0926
ALO
CFPWB
0926
15
1436
1641
ALO
8003
1641
15
8003
0849
LDD
CFPWG
0849
69
0809
0912
SDA
CFPWG
0912
22
0809
0962
LDD
CFPWH
0962
69
1185
0988
SDA
CFPWH
0988
22
1185
1038
SLO
8002
1038
16
8002
0947
STD
CFPWB
0947
24
1436
1539
ALO
CFPWE
1539
15
1567
1521
ALO
8003
1521
15
8003
1529
LDD
CFPWF
1529
69
1617
1170
SDA
CFPWF
1170
22
1617
1220
SLO
8002
1220
16
8002
1579
STD
CFPWE
1579
24
1567
1270
ALO
SRYFP
1270
15
0888
0993
ALO
8003
0993
15
8003
1151
LDD
SRYFB
1151
69
0709
1012
SDA
SRYFB
1012
22
0709
1062
LDD
SRYFD
1062
69
0759
1112
SDA
SRYFD
1112
22
0759
1162
LDD
SRYFE
1162
69
0764
1817


ACKNOWLEDGEMENTS
The author wishes to express his deep appreciation
and sincere thanks to Professor R. D. Walker, Jr., for his
encouragement, interest, and many suggestions during the
course of this investigation; to Mr. Carlis Taylor of the
University of Florida Statistical Laboratory for his very
valuable help in the preparation of the computer program and
in the obtaining of the computer solutions; to Dr. H. A.
Meyer for authorizing the use of the facilities of the
Statistical Laboratory and Computing Center for this work;
to Dr. Mack Tyner, Dr. T. M. Reed, Dr. E. E. Muschlitz, and
Dr. R. ,W. Cowan, of the graduate committee, for their help
ful suggestions and criticisms; to the faculty and graduate
students of the Department of Chemical Engineering for
their cooperation and interest; and to his wife for the
assistance and unwavering support which she has given.