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Advanced mass spectrometric methods of jet fuel analysis

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Advanced mass spectrometric methods of jet fuel analysis
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Gehron, Michael Joe, 1956-
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viii, 160 leaves : ill. ; 28 cm.

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Alkenes ( jstor )
Arithmetic mean ( jstor )
Calibration ( jstor )
Carbon ( jstor )
Hydrocarbons ( jstor )
Ionization ( jstor )
Ions ( jstor )
Jet fuel ( jstor )
Mass spectrometers ( jstor )
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Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Jet planes -- Fuel -- Analysis ( lcsh )
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Spectrometer ( lcsh )
City of Fort Lauderdale ( local )
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Thesis:
Thesis (Ph. D.)--University of Florida, 1988.
Bibliography:
Includes bibliographical references.
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Typescript.
General Note:
Vita.
Statement of Responsibility:
by Michael Joe Gehron.

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Full Text


ADVANCED MASS SPECTROMETRIC METHODS
OF JET FUEL ANALYSIS
BY
MICHAEL JOE GEHRON
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1988


To the Glory of GOD
whose grace through Jesus Christ
has brought me here and is taking me there.
To 0. Dean Martin
Minister of Trinity United Method Church of Gainesville
whose teachings and courage has been an inspiration in my life.
To the "Original Little Leaguer"
Harold "Major" Gehron
who passed away on November 15, 1987.
To Mom and Dad


ACKNOWLEDGEMENTS
I would like to thank ray research director and friend Richard A.
Yost for the great discussions, time and effort he put into the
preparation of this research and dissertation. I would also like to
thank him for making my graduate career at the University of Florida
quite enjoyable.
I sincerely thank Gerhard M. Schmid and James D. Winefordner for
seeing me through till the end. Special thanks go to Joseph J. Delfino
and Kirk S. Schanze for also serving on my committee and reviewing this
work.
I would like to thank the entire group for making me feel at home
after the big switch. Special thanks go to Jodie Johnson, Mike Lee,
Ken Matuzsak, Todd Gillespie, Randy Pedder, and Mark Hail for all their
help; I mean all their help.
Special thanks go to a special friend, Bill Davis.
Thanks go to Dave White who taught me to do it rather than sit
around and theorize on the outcome.
I love my wife Cheryl, my little Laura, and the Bun in the oven.
They are what its all about.
iii


TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
ABSTRACT vii
CHAPTERS
I INTRODUCTION 1
Objectives 1
Background 2
Type Analysis 2
Total Fuel Analysis 5
History and Reviews of Hydrocarbon Type Analysis 5
Specifications of Jet Fuels 9
Instrumental Methods of Analysis 14
Sample Introduction 14
Short Column GC/MS and Simulated Distillation 15
Long Column GC/MS for TFA 16
Ancillary Jet Fuel Analysis Techniques 17
Alternative Ionization Methods 17
Mass Spectrometry/Mass Spectrometry 18
Outline of Thesis 19
II EXPERIMENTAL 21
Materials 21
Apparatus 22
Mass Spectrometry 22
Gas Chromatography Conditions 22
Other Gas Chromatography Studies 23
Data Handling Techniques 24
Clarification of ASTM D-2789 24
Computer Hardware and Software 28
Ion Summation Chromatography 28
Simulated Distillation for Determining
Numbers 30
Occupational Hazards 30
iv


III GAS CHROMATOGRAPHIC/MASS SPECTROMETRIC HYDROCARBON TYPE
ANALYSIS 32
GC Sample Introduction 32
Ancillary Short-Column Experiments 40
Analytical Figures of Merit 42
Characterization of the GC/MS/HTA Method 48
Comparison of ASTM and GC/MS/HTA Results 48
Simple Mixture Analysis 52
Inverse Calibration Matrix Variation 60
Evaluation of Olefin and Cycloparaffin Isomers 69
Evaluation of Methods for Average Carbon Number
Determinations 78
GC/MS Simulated Distillation 79
Comparison Between GC/MS/SD and GC/MS/HTA 83
Comparison Between GC/MS/HTA and ASTM 83
Effect of Chromatographic Resolution on Carbon
Number Calculations 86
Summary of Results 87
IV PRELIMINARY INVESTIGATIONS OF ALTERNATIVE IONIZATION
TECHNIQUES FOR JET FUEL ANALYSIS 90
Background 90
Low Energy Electron Ionization 90
Methane Chemical Ionization 91
Experimental 92
Electron Energy Variation 92
Methane Cl 92
Results and Discussions 93
Low Energy Electron Ionization 93
Methane Chemical Ionization 97
Summary of Results 101
V PRELIMINARY INVESTIGATIONS OF GC/MS/MS TECHNIQUES
FOR JET FUEL ANALYSIS 104
Background 104
Mass Spectrometry/Mass Spectrometry 104
Application of GC/MS/MS to Jet Fuel Analysis 105
Experimental 107
Results and Discussion 108
MS/MS for Hydrocarbon Type Analysis 108
Other GC/MS/MS Modes of Analysis 115
Differentiation of Isomeric Hydrocarbon
Types 117
Summary of Results 124
v


VI CONCLUSIONS AND FUTURE WORK 126
Summary of Results 126
Hydrocarbon Type Analysis 126
Calculation of Average Carbon Number 127
Ancillary Mass Spectrometric Methods 128
APPENDICES
A MATRIX INVERSION METHOD 130
B EXAMPLE GC/MS/HTA CALCULATION 131
C GC/MS/HTA TURBO BASIC PROGRAM CODE 136
D PRELIMINARY TEST METHOD FOR HYDROCARBON TYPE ANALYSIS
OF JET FUEL BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY .. 146
BIBLIOGRAPHY 155
BIOGRAPHICAL SKETCH 160
vi


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
ADVANCED MASS SPECTROMETRIC METHODS
OF JET FUEL ANALYSIS
BY
MICHAEL JOE GEHRON
April, 1988
Chairman: Richard A. Yost
Major Department: Chemistry
Hydrocarbon type analysis (HTA) is widely used to evaluate the
chemical composition of petroleum and shale-derived products, such as
jet fuels. The HTA methods provide a knowledge of the macro
composition of the jet fuels which is important in engine design and
performance. Presently the methods used for HTA of jet fuels are
limited by the boiling point range of the analysis and the
instrumentation requirements. The HTA method for gasolines (used for
jet fuels), American Society of Testing and Materials standard test
method D-2789, was developed in the mid-1950s on magnetic sector mass
spectrometers which are no longer commercially available.
A gas chromatography/mass spectrometry (GC/MS) method has been
developed for the hydrocarbon type analysis (HTA) of jet fuels. The
method employs a short-column capillary (3 meters) which is interfaced
directly into a Finnigan TSQ45 tandem mass spectrometer. Advantages
vii


of this method include employment of present day GC/MS instrumentation
and simple GC sample introduction. Additionally, a simulated
distillation profile may be obtained based on specific hydrocarbon
types which allows for the determination of more accurate average
carbon numbers of each hydrocarbon type. The results of the HTA on a
series of fuels and synthetic fuel mixtures will be reported along with
a complete characterization of the GC/MS/HTA method and results. The
results and methodology of the GC/MS simulated distillation method for
average carbon numbers will be reported.
A preliminary investigation of alternative MS techniques for jet
fuel analysis has been performed for the development of methods for
total fuel analysis (TFA) (determination of 95% of all components
present at 0.05% weight or greater). These techniques include
alternative ionization techniques such as low energy electron
ionization and methane chemical ionization; and tandem mass
spectrometry techniques such as daughter scan MS and parent scan MS.
The application and results of these techniques will be presented in
regards to the HTA and TFA of jet fuels.
viii


CHAPTER I
INTRODUCTION
The need to understand the chemical composition of aviation fuels
has never been more important than in the last decade. This need stems
from two important aspects: the recent world-wide shortages of
petroleum crude reserves which have resulted in a transition to
alternative crude sources; and the desire to design and operate high
performance jet engines with the knowledge of fuel composition as a
controlling criterion. This has led to a resurgence in the development
of new analytical techniques for petroleum analyses and more
specifically aviation fuel analyses. In this laboratory investigations
are presently underway for the application of gas chromatography/mass
spectrometry (GC/MS) and GC/MS/MS for analysis of aviation fuels (in
particular turbine jet fuels). There are two modes of analysis of
interest, hydrocarbon type analysis (HTA) and total fuel analysis
(TFA). The concept of each application will be discussed below.
Objectives
This research project is organized around two goals. The first is
to develop, implement, and characterize a gas chromatography/mass
spectrometry (GC/MS) hydrocarbon type analysis (HTA) for jet fuels.
1


2
These fuels represent a specific boiling point fraction or range of
components of crude oil. The second goal is to begin preliminary
investigations into the development of a GC/MS method for total fuel
analysis (TFA) (determination of 95% of all components present at 0.05%
weight or more) of these jet fuels. Vast differences in
chromatographic separation will be required in these two tasks. The
ability to integrate the two methods with one instrumental
configuration (GC/MS) is a goal of significant importance.
Background
This section will discuss the idea of type analysis or more
specifically hydrocarbon type analysis of fossil fuels and the need and
significance of new methods. Total fuel analysis will also be
discussed illustrating the need for specific detection systems.
Type Analysis
The concept of "Type Analysis" is not widely known among analytical
chemists. One may ask, "what type (of) analysis did you perform on the
samples?" And one may reply, "a type analysis was performed on the
samples." Thus the confusion begins. Type analysis in general does
not provide information on specific individual components in a mixture
but rather supplies information on the relative amounts of certain
classes of compounds. In many applications the quantitation of
specific compounds is not required and may provide much more
information then is actually desired. This is particularly true in
cases where the analyst is only interested in the overall macro
composition of a very complex mixture. The type analysis of


3
hydrocarbon mixtures, such as gasoline and heavier oils, represents
such an application of type analysis. Hydrocarbon type analysis is a
widely used procedure for the evaluation of petroleum feedstocks and
other complex mixtures. In 1951 Ralph Brown of the Atlantic Richfield
Corporation developed the first mass spectrometric technique for
Hydrocarbon Type Analysis (HTA) (1). The Brown method operates on the
premise that certain classes of compounds or homologous series, for
example paraffins, form a specific series of fragmentation ions in the
electron ionization source of the mass spectrometer. In this example
the paraffins form the series of mass fragments 43, 57, 71, 85, and 91.
Not all species of this series form all or only these ions. Similarly
the paraffin series is not the only class or homologous series of
compounds which contain any of these ions. Therefore an extensive
calibration scheme is required to normalize for this mixing of
fragmentation series between hydrocarbon types. Details of the present
method will be discussed in Chapter II, Clarification of ASTM D-2789.
Since the Brown method, there have been numerous improvements on his
method due to improved calibration schemes (2,3), and improved
instrumentation (4,5). In 1962 standard Hydrocarbon Type Analysis
methods for gasoline (6) and diesel fuels (7) were adopted into the
American Society of Testing and Materials (ASTM) standards. There have
been several revisions of these methods over the years, but the basis
of the methods remains the same. The methods, ASTM D-2789 and D-2425,
perform the analysis on magnetic sector instruments which are no longer
in commercial production. Because of this limitation, there is a much
greater demand for samples to be analyzed than there are laboratories


4
equipped to perform them. Additionally, the means of sample
introduction into the mass spectrometer, which is via a heated glass
inlet volume or microburette, is a time-consuming procedure and
facilitates component discrimination (8). The technique also relies on
manual measurements of peak height intensity which eliminates the
ability to computerize the calculations. Consideration of these
limitations illustrates the need for a modern HTA method performed on a
widely available modern instrument.
At the 1987 meeting of The American Society of Mass Spectrometry
in Denver, the ASTM committee on petroleum analyses (9) expressed
interest in the development of new and/or improved methods of HTA in
the fuels area. Presently several methods are used for hydrocarbon
type analysis such as the fluorescent indicator adsorption (FIA)
procedure which covers the determination of saturates, non-aromatic
olefins, and aromatics (10). Limitations of this method include long
analysis time (3-4 hours per sample) poor precision, and lack of
automation capabilities. Limitations of these methods led to the
development of several liquid chromatographic methods (11), but
limitations of these methods include the inability to separate and
quantitate enough classes. With the development of a GC/MS/HTA several
advantages would be realized. First, convenience in instrumentation,
since most modern analytical laboratories are equipped with a GC/MS,
many laboratories will be able to perform the analysis, and the sample
load will be decreased. Second, GC introduction will provide improved
sample introduction techniques which are more convenient and less prone
to component discrimination. Additionally, the use of chromatography


5
will provide information such as distribution of components as a
function of boiling point and make possible the extension of the method
to total fuel analysis by increasing the chromatographic resolution.
Total Fuel Analysis
The concept of total fuel analysis (TFA) is one to which most
analytical chemists may relate. The objectives are to quantitatively
determine specific components or classes of components of jet fuel.
One must be knowledgeable of the complexity of jet fuels to appreciate
the formidable task at hand. A typical jet fuel may contain from 400
up to 4000 individual components. Davis and Giddings (12) and Martin
and co-workers (13) have shown theoretically that, in order to
chromatographically resolve 90% of the components in a 100 component
mixture, 20,000,000 theoretical plates would be required. Considering
a standard capillary GC column of 0.25 mm i.d. and 0.25 /jm thickness, a
column length of 5 km or 3 miles would be required for such an
analysis. This theoretical calculation merely illustrates the need for
more selective detection methods which could utilize normal high
resolution chromatography.
History and Reviews of Hydrocarbon Type Analysis
Discussions on the history of HTA of petroleum-derived mixtures
such as fuels will quickly lead one to a general discussion of the
early history and development of mass spectrometry. The impetus for
early mass spectrometry research was generally fueled by the petroleum
industry and the war-time demands on the industry to supply aviation
fuels of superior quality with good quality control and assurance.


6
Recently there have been several review articles which deal
specifically with this history (14,15). The Consolidated Engineering
Corporation (CEC) enjoyed the first commercially successful mass
spectrometer (CEC Model 21-101) which became the prototype instrument
which was be utilized by Ralph Brown (1) in the first mass
spectrometric HTA of gasoline mentioned above.
There have been many methods developed in the past for the
determination of hydrocarbon types in gasolines and fuels. Some of
these methods relied on rather laborious and time-consuming
separations, chemical reactions, and physical determinations. One
procedure developed by Kurtz et al. (16) required 24 man-hours for
fractionation, chemical treatment and determination by refractive
indices. Rampton (17) employed distillation, silica gel percolation,
hydrogenation, and measurements of refractive indices for the
determination of paraffins, cycloparaffins, aromatics, olefins, and
cycloolefins. The first applications of mass spectrometry to
hydrocarbon fractions were to the analysis of gaseous mixtures (18).
Later, with the advent of improved mass spectrometers and inlet
systems, the analysis of the lower-boiling fraction of gasolines was
performed (19-21). In 1951 Ralph Brown introduced the HTA method for
gasolines which represented a new concept and application of mass
spectrometry. The application of MS HTA soon expanded to the analysis
of heavier fractions such as kerosene and heating oils (2,22). At this
time O'Neal and Wier (4) and Brown et al. (23) independently described
an improved all-glass heated inlet system which would not only expand
the boiling point range of MS analysis even greater, allowing for the


7
analysis of waxes and other low vapor pressure compounds, but also
improve the precision and accuracy of the method as a whole. Of
particular interest at that time was more in-depth analysis of the
aromatic fractions of these complex heavier mixtures (24-27). Previous
to these MS techniques, little was known of the chemical make-up of
such aromatic fractions. From the middle 1950s, which may be regarded
as the end of the rapid growth period of mass spectrometry research in
the applications of petroleum-derived mixtures, there have been very
few publications appearing in the literature. However, with the advent
of high resolution mass spectrometers in the early 1960s, there was an
additional surge of interest in MS techniques for the analysis of
petroleum-derived complex mixtures (28-31). Traditionally, the major
use of high resolution MS was for the identification and structural
determination of pure compounds or major components of a simple
mixture. Since heavier petroleum fractions contain such a large
variety of compounds compared to lower boiling fractions such as
gasoline, a single low resolution mass spectrum cannot be interpreted
in terms of hydrocarbon types. The high resolution MS techniques could
single out each hydrocarbon type based on the exact mass of the
fragment ions and/or molecular ions. The classification scheme became
known as the "Z number" classification based on the formula CnH2n+z
where z is a number which represents the degree of unsaturation and/or
ring closure and signifies the hydrocarbon type. A more extensive
discussion on "Z number" classification may be found in the paper by
Teeter (29) which introduces an improved high resolution MS hydrocarbon
type analysis for 22 hydrocarbon types. This method determines the


8
relative amounts of eight types of saturates, ten types of aromatics,
and four types of sulfur-containing aromatics. In addition to high
resolution techniques a number of low resolution techniques began to
appear in the literature. The Robinson and Cook method (32) followed
by the Amoco method (26) took advantage of the appearance of saturate
fragments at lower masses and aromatic fragments at higher masses.
This enabled the spectra to be subdivided into a saturate and aromatic
region allowing mathematical treatment and normalization. The
elemental analysis, carbon number distribution, average molecular
weight, and the general aromaticity of coal-derived distillates were
determined by the combination of low-voltage, high resolution MS (33).
Other analytical techniques apart from MS techniques have been
utilized in the pursuit of a suitable HTA of fuels and other complex
petroleum mixtures. Based on the classic silica gel separation of
saturates, olefins, and aromatics, new high performance liquid
chromatographic methods have been developed which utilize silver-coated
silica gel particles and n-pentane mobile phases (34). Separation of
saturates, single ring aromatics, double ring aromatics, and
polynuclear aromatics was obtained for olefin free kerosenes and diesel
fuels using bonded aminosilane stationary phases (35) An excellent
review is available on the application of HPLC and GC to hydrocarbon
group analysis (36-38). Most recently several workers have evaluated
supercritical fluid chromatography (SFC) for the separation of
hydrocarbon types (39). Separation of paraffins, olefins, and
aromatics was obtained in two reports; using SFg mobile phase, pressure


9
programming, and FID detection (40); and using silver nitrate
impregnated silica gel stationary phases with CO2 mobile phase and
refractive index detection (41). Combination of SFC with MS shows
great promise for future applications to fuels analysis.
Specifications of Jet Fuels
With the world-wide shortage of conventional high quality crude
oils, there has been a dramatic decrease in the availability of jet
fuels. As a result of this shortage, the industry has experienced a
transition from petroleum sources towards utilization of alternative
sources such as oil shale, tar sands, coal liquid, and heavy oils for
the production of jet fuels. Additionally fuels are being synthesized
by blending various refinery streams and mixing of pure compounds.
This shift has created increases in processing cost as well as many
uncertainties in market stability. More importantly here, new unknowns
have been generated in the physical and chemical characteristics of
these new source fuels. Recently it has become more important in the
design and operation of jet engines to be able to correlate the
physical parameters of jet fuels with their chemical composition. With
the addition of these new source fuels, there is a need for new and
improved physical and chemical methods of jet fuel analysis.
Traditionally the determination of the physical parameters of jet fuels
has been the focus of jet fuel analysis. Table 1.1 lists some of the
more common physical parameters determined for jet fuels (42). The
importance of a few of these parameters is as follows: thermal


10
Table 1.1
List of Important Physical Parameters Determined for
Aviation Fuels and the Corresponding ASTM Methods Used
Physical Parameter Test ASTM Method
Volatility
Distillation
Specific Gravity
Vapor Pressure
D- 86
D-287
D-328 D-2551
Fluidity
Freezing Point
D-2386
Combustion
Heat of Combustion
Aniline-Gravity Product
Knock Rating: Lean Fuel
Rich Fuel
D-240, D-2382
D-611, D-287
D-2700
D-909
Corrosion
Copper Strip Test
D-130
Stability
Potential Gum
Precipitate
D- 873
D- 873
Contaminants
Existent Gum
Water Reaction:
Interface Rating
Volume Change
D- 381
D-1094
D-1094
Additives
Tetraethyllead Content
Dye Content
D-3341, D-2599 D-2547
D-2392


11
stability is important since jet fuels are exposed to extremely high
temperatures and minimal decomposition is desired; viscosity of fuels
as a function of temperature is important since the fuels must remain
fluid in flights where
the
fuels are
exposed
to
extremely low
temperatures in storage;
the
density of
fuels
(or
the volumetric
energy) determines the ultimate range in miles of the aircraft. For
more information on any of the specifications listed in Table 1.1,
refer to the appropriate reference listed. Most methods used in the
determination of the above mentioned physical parameters are ASTM
standard methods and represent important contributions to fuel and jet
engine research.
As mentioned above, the specifications of jet fuels are based
mainly on the physical parameters or usage requirements. The single
composition requirement common to all aviation fuels is they must
consist almost completely of hydrocarbon compounds. There are specific
limitations on particular hydrocarbon types such as aromatics and
olefins due to performance criteria. Additionally, low level additives
may be present as well as low level contaminants of various sorts.
Jet fuels or more specifically turbine jet fuels are made up of
hundreds of hydrocarbons that may be divided into four subgroups or
hydrocarbon types: paraffins and isoparaffins (branched paraffins);
cycloparaffins or naphthens; aromatics; and olefins. The former two
types make up the saturates and the latter two types the unsaturates.
Figure 1.1 illustrates some example compounds of each hydrocarbon type.
Paraffins and cycloparaffins are generally the major type component
of jet fuels. The paraffins are the most stable components and do not


12
Paraffin
ch3
CH3(CHz)nCHCH,
Monocycloparaffin
isopropyl-cyclohexane
Dicycloparaffin
decal in
Alkylbenzene
ethylbenzene
''u CH
3
Indane/Tetralin
Naphthalene
2-methyl naphthalene
CH3
Figure 1.1.
Structures of some example compounds representative of
the six hydrocarbon types. Some specific examples are
also shown.


13
readily react with materials in which they come in contact with such as
elastomers, paints, and various metals. They are clean-burning
compared to other hydrocarbons and have a very high heat release per
unit weight. Both of these advantages are due to the high hydrogen-to-
carbon ratio. Cycloparaffins have a lower hydrogen-to-carbon ratio
which lowers their heat release per unit weight, but increases their
density or volumetric energy. Cycloparaffins are also clean-burning
and stable and have a lower freezing point compared to paraffins of
equal carbon number.
Aromatics are fully unsaturated ring structures which may also
incorporate saturated structures. Because of the very low hydrogen-to-
carbon ratio, they have a much greater volumetric energy but a lower
heat release per unit weight than the paraffins. The aromatics are
reactive and tend to cause swelling of rubber seals. They produce
large amounts of smoke while burning, and a high-luminosity flame.
This particular aspect is important when considering secret
reconnaissance missions of the Armed Forces. Because of these factors
the maximum concentration of aromatics permitted in jet fuels is 20-25%
Virgin fuels generally contain no more than 10-20% aromatics.
Olefins are the most reactive hydrocarbon types and are capable of
reacting with many materials. They react with air to form varnishes or
rubber-like materials. They can dimerize or polymerize forming high
molecular weight contaminants. Because of their high reactivity,
olefins are generally not found in natural or virgin crudes. They may,
however, be formed in the refinery cracking processes. Specifications


14
limit the content of olefins to less than 5 percent in order to reduce
varnish and gum formation.
Other non-hydrocarbon types which may be found in aviation fuels
include heteroatomic species such as sulfur-, oxygen-, and nitrogen-
containing compounds. These include mercaptans, sulfides, thiophenes,
and free sulfur as example sulfur types; alcohols and naphthenic acids
as example oxygen types; and aza and amino polynuclear aromatics as
example nitrogen types. Combinations of these contaminants tend to
form high molecular weight gums and deposits when exposed to air during
storage. This creates many problems such as filter clogging, sticking
of valves, and plugging of orifices. Additives present which help to
eliminate some of these problems include antioxidants, metal
deactivators, fuel icing inhibitors, and corrosion inhibitors.
Instrumental Methods of Analysis
Sample Introduction
The utilization of GC/MS techniques can provide more up-to-date
methods of sample introduction into the mass spectrometer. This is a
direct advantage over the traditional ASTM methods, in which a heated
glass inlet or microburette is employed, and the sample is introduced
by effusion through a small orifice. A small fraction of the total
sample is analyzed with the microburette technique, in order to
minimize component discrimination which increases as the effusion of
the sample into the mass spectrometer proceeds. The method is time-
consuming and requires the maintenance of many instrumental parameters.
The GC/MS technique will vaporize the entire sample and analyze the


15
entire volume which has been loaded onto the column. Because of the
possibility of component discrimination during sample loading onto the
GC column, component discrimination must be evaluated as a function of
injection port temperature and injection techniques.
Short Column GC/MS and Simulated Distillation
An important concept of this HTA method is that chromatographic
resolution of the jet fuel components is not a matter of pursuit.
Trehy, Yost, and Dorsey (43) have discussed some of the important
instrumental considerations of normal GC/MS using short capillary
columns. In the GC/MS/HTA application of short capillary columns, the
GC is mainly used as a convenient device for sample introduction into
the mass spectrometer. The short columns, along with providing short
analysis times, provide the ability to observe the distribution profile
of the eluting jet fuel as function of column temperature. This
concept is similar to that of simulated distillation (44,45) which has
been utilized by the petroleum industry for many years to provide a
breakdown of the boiling point distribution of the hydrocarbon mixture.
The area percent of the eluting fuel is determined at various points
along the profile or chromatogram. Each area percent corresponds to a
specific retention time or boiling point. These boiling points are
determined by a parallel eluting sample of n-paraffin homologous series
in which the boiling points are known. A non-polar column must be
employed to assure the correlation of retention to boiling point. The
temperature corresponding to the 50 percent area point corresponds to
the average boiling point of the fuel. This is a useful physical
parameter, although the extraction of an average carbon number from the


16
results is not accurate. Application of GC/MS, however, can provide
not only average boiling points but also average carbon number. This
is provided by the ability of the mass spectrometer to distinguish
between hydrocarbon types within the fuel mixture. Corresponding
homologous series may be compared to the corresponding ion summation
chromatogram of the particular hydrocarbon type and an average carbon
number may be obtained. These experiments represent an important
advancement in the development and understanding of hydrocarbon type
analysis.
Long Column GC/MS for TFA
The quest for a GC/MS technique for TFA will require high
resolution (long-column) capillary gas chromatography. Since only a
select number of chromatographic peaks will be pure components,
additional selectivity in addition to chromatographic resolution will
be required. Many researchers have reported work in the fuels area
with chromatography alone (46,47). Here the application of MS, which
includes various modes of ionization, and MS/MS will be evaluated for
means of chromatographic peak deconvolution. There have been numerous
reports in the literature which have applied GC/MS techniques to fuel
analysis. Gallegos (48) has described a high resolution GC/MS method
for the analysis of a shale derived oil. Aczel has determined compound
type distribution in refinery streams and synfuels using GC/MS (49) .
The compound distribution of a jet fuel has been determined by
recombination of separately determined components using GC/MS (50).


17
Ancillary Jet Fuel Analysis Techniques
The development of GC/MS methods for total fuel analysis (TFA) will
require the utilization of ancillary MS techniques such as low-energy
electron ionization, chemical ionization, and MS/MS techniques. These
techniques, when combined with chromatographic separation, will provide
specific detectors for the deconvolution of multicomponent
chromatographic peaks discussed earlier. The following is a review of
the application of such MS techniques.
Alternative Ionization Methods
Chemical ionization (Cl) (51) is a softer ionization technique
which is capable of producing an increased abundance of molecular ion
and minimal fragmentation compared to conventional electron ionization
(El). Harrison discusses the use of CIMS with various reagent
compounds for the characterization of hydrocarbons (52). Although
there have been significant applications of Cl to the characterization
of single classes of compounds in fuels and other complex mixtures,
there have been no known publications on the application of Cl to an
overall hydrocarbon type analysis of jet fuels. Sieck characterized
gasolines for their aromatic content using low-energy photoionization
cyclohexane Cl (53). Sieck, Burke, and Jennings (54) used N2O Cl for
screening of aviation fuels. The OH' ion was employed for negative ion
Cl, which eliminated ionization of aliphatic compounds. Other
applications of CIMS have been devoted to the determination of
polynuclear aromatic hydrocarbons (PAH) in fuels (55), as well as aza
and amino PAH in coal derived liquids (56). Negative ion ammonia Cl
GC/MS has been used for the quantitation of sulfur-containing compounds


18
in gasoline (57). Bauer, Schubert and Enke (58) used methanol Cl for
the characterization of heterospecies in the presence of hydrocarbons.
The essential aspect of Cl GC/MS techniques in regard to total fuel
analysis is the ability to deconvolute co-eluting components of the
fuel. In the current research only methane chemical ionization is
evaluated.
Electron ionization (El) is considered the work-horse of mass
spectrometry. One aspect of EI/MS which is rarely explored in
petroleum analysis is the utilization of low-energy El. Since various
compound types have different ionization potentials, these differences
may be utilized as a source of compound-type discrimination. One of
the earliest applications of low-energy ionization MS (referred to as
low-voltage MS) was the determination of the unsaturated hydrocarbon
fraction in a petroleum naphtha (59) In this method only molecular
ions of the unsaturated species are formed, thus eliminating saturate
interferences. Aczel and Johnson utilized low-energy electron
ionization in conjunction with high resolution MS for the analysis of
aromatic fractions of complex petroleum mixtures (31). As mentioned
above, low energy photochemical ionization was used for the analysis of
aromatics in gasoline (53). The use of low-energy electron ionization
GC/MS is evaluated here for the characterization of separate
hydrocarbon classes. This technique and its usefulness will be
discussed.
Mass Spectrometry/Mass Spectrometry
Mass spectrometry/mass spectrometry (MS/MS) is quite useful for the
direct analysis of complex mixtures such as coal derived liquids.


19
Recently there have appeared in the literature many applications of
MS/MS to the analysis of complex petroleum mixtures (56,58,60-71).
There exist two MS/MS instrumental techniques which are generally used,
mass-analyzed ion kinetic energy spectrometry (MIKES) (72,73) and
triple quadrupole mass spectrometry (TQMS) (74). To date, no known
application of MS/MS to HTA of fuels has appeared in the literature;
however, as with Cl applications, most MS/MS applications have been
dedicated to the determination of a single class of compounds or a
single component. In the current research, several aspects of TQMS
have been evaluated for possible HTA methods or TFA methods of jet
fuels. These results will be discussed along with the possibility of
combining MS/MS with alternative ionization techniques.
Outline of Thesis
The remainder of the thesis is divided into five chapters. Chapter
II, Experimental, will describe all experimental, instrumental, and
computational techniques. Chapter III, Gas Chromatography/Mass
Spectrometry/Hydrocarbon Type Analysis, will contain experimental
results and discussions based solely on the development,
implementation, and characterization of the GC/MS/HTA method. Chapter
IV, Alternative Ionization Techniques, will contain results and
discussions on the use of these techniques in the application of TFA
and HTA of jet fuels. Chapter V, Gas Chromatography/Mass
Spectrometry/Mass Spectrometry, will contain results and discussions on
the use of GC/MS/MS in the application of TFA and HTA of jet fuels.


20
Finally Chapter VI, Conclusions and Future Work, will summarize the
total effort and describe suggested future work. As in any research
effort each question answered brings about several new questions. This
project is no exception.


CHAPTER II
EXPERIMENTAL
The following chapter will discuss the experimental parameters
which are involved in the development, characterization, and
implementation of the hydrocarbon type analysis of jet fuels. The
experimental parameters which deal specifically with studies in total
fuel analysis, such as chemical ionization and MS/MS will be discussed
in those specific chapters. The general experimental parameters, such
as materials, jet fuel preparation, and instrumentation will also be
discussed here.
Materials
All chemicals were ACS grade unless otherwise specified and were
used as received without further purification. Standards were
purchased from various vendors and were used as received without
further purification. All jet fuel samples were obtained from Pratt &
Whitney-Fuels Division, West Palm Beach, Florida. The fuels were
shipped at ambient temperatures without refrigeration in vials with
screw-cap or crimped cap teflon-lined replaceable septa. After every
use in the laboratory, the septa were replaced with new ones and
samples were refrigerated at 5 C.
21


22
Apparatus
Mass Spectrometer
A Finnigan MAT TSQ45 gas chromatograph/triple stage quadrupole mass
spectrometer/data system was used in all GC/MS studies. An electron
energy of 70 eV and an electron current of 300 /iA were used. The mass
spectrometer was mass calibrated with FC43 (perfluorotributylamine) in
accordance with the instrument's specifications. The mass spectrometer
was tuned, also with FC43, to obtain a specific ion intensity ratio of
m/z 69 to m/z 219, and m/z 502 to m/z 220. These ratios were monitored
to insure reproducible relative abundances of the fragmentation pattern
in regards to instrumental tuning alone. The low mass ratio is of
greater importance in these studies since this is the general mass
range in question. The mass spectrometer was scanned from 35 to 650
amu at a total scan time of 1.0 s. The electron multiplier was
operated between 950 and 1000 V, with the conversion dynodes at 3000
O
V. The preamplifier gain was set at 10 V/A with the fine adjustment
(zeroing) set for minimal acquisition of baseline noise. The mass
spectrometer was interfaced to a Finnigan Model 9610 gas chromatograph.
All GC operations were under computer control. The capillary GC
columns were inserted directly into the ion source of the mass
spectrometer through a heated interface. The ion source pressure was
0.3-0.6 Torr depending on the column head pressure. The ion source
temperature was 190 C.
Gas Chromatography Conditions
A 3 m DuraBond fused silica bonded phase open tubular (capillary)
column (J&W, Rancho Nuevo, CA) with an inner diameter of 0.25 mm and a


23
DB5 bonded phase (SE-54 equivalent or 5% phenyl-methyl silicone) of 1.0
nm thickness was operated at a head pressure of 8 pounds per square
inch of helium carrier gas. Split-type injection was used with a split
flow of 50 mL/min and a septum sweep of 2 mL/min. The injection port
temperature was 250 C and the transfer line was 280 C. The injection
port teflon lined septum was replaced after 30 40 injections and the
injection port glass insert was checked frequently and cleaned whenever
needed. The column temperature was programmed from 50 C to 250 C at 15
C/min after a hold time of 1 minute. Usually the column would not
require the full temperature to elute the entire jet fuel sample.
Generally 0.5-1.0 injections of neat jet fuel samples were made.
The injection technique used was as follows in order to reduce
injection error: the GC injection syringe (Hamilton) was thoroughly
rinsed between samples with hexane, followed by the sample jet fuel of
interest; the sample volume was pulled up from the needle volume into
the syringe volume; the needle was inserted into the GC injector; a
count of three allowed the needle to come to equilibrium temperature;
the sample was injected at a rate of approximately 1 /L/s; this
position was held for a count of three and the needle was removed.
This method decreases injection discrimination due to uneven heating of
the needle and components contained therein (75,76).
Other Gas Chromatographic Studies
Besides GC/MS, studies involved the application of GC with flame
ionization detection. A Varian 3300 gas chromatograph was used with a
flame ionization detector (FID). The same chromatographic conditions
were used as stated above including the column head pressure. However,


24
although the column head pressures were equivalent for the two systems,
different flow rates would result due to the different exit pressures.
This instrument was used for the studies of component discrimination as
a function of injection port temperatures and injection modes (split,
splitless, and on-column). Acquisition of peak area, peak height, and
retention time was obtained with an IBM 9000 minicomputer and the IBM
CAPMC4 Chromatography Applications Program. Additionally, the FID
system provided two advantages: a continuous mode of detection which
resulted in more highly resolved chromatograms, and increased
sensitivity (compared to full scan MS) which when combined with high
resolution gas chromatography (longer columns, 30 meters) would
demonstrate the extreme complexity of the jet fuels.
Data Handling Techniques
This section covers aspects of the data handling and reduction
which proved to be a major effort in obtaining the stated goals.
Considering the hydrocarbon type analysis alone, the mathematical
computations were quite abstract and had to be figured out conceptually
before application could be made. Below, these computations will be
discussed, along with the hardware used and the software generated to
deal with them.
Clarification of ASTM D-2789
The purpose of this section is to clarify the computational aspects
of ASTM D-2789 standard test method (6), which is the computational
basis of the GC/MS/HTA method developed here. The ASTM method, as it
is referred to, determines the volume percent of six separate


25
hydrocarbon types in low olefinic gasolines: paraffins,
monocycloparaffins, dicycloparaffins, alkylbenzenes, indanes and
tetralins, and naphthalenes. Each hydrocarbon type is determined based
on a characteristic set of ions as shown in Table 2.1. The method also
calculates the average aromatic and average paraffinic carbon numbers
based on mass spectral data. Calculations are made based on the
inverse calibration tables shown in Table 1 of the ASTM D-2789 standard
method (6) and are dependent upon the average carbon numbers. It is
these aspects of the ASTM method, development and application of the
inverse calibration matrices, which require clarification. The
calculations are similar to six simultaneous equations with six
unknowns; however, the unknowns are made up of a complex array of
variables and the set of equations used are chosen based on two other
variables as well.
The inverse calibration matrices were prepared by determining the
values E43/T, E41/T, etc. for each hydrocarbon class mixture at each
carbon number, where T=E(E43+E41+E67+E77+E103+E128), the sum of all the
characteristic hydrocarbon sums (E) The compositions of the
hydrocarbon class mixtures at each carbon number (up to carbon number
nine) used in these determinations are given in Table 3 of the ASTM
standard (6). Consider this example calculation of the inverse
calibration matrix for carbon number six: the E43/T, E41/T, E67/T, and
E77/T are determined for each of the three hydrocarbon type mixtures as
shown in the ASTM Table 3 under C6 blends. The results are given in
Table 4 of the ASTM standard (6) under the appropriate hydrocarbon type
and C6 listing along with the results for larger carbon numbers. For a


26
Table 2.1
The Characteristic Ion Summations Used For Each Hydrocarbon Type
in the Hydrocarbon Type Analysis
HYDROCARBON TYPE
MASSES OF EACH CHARACTERISTIC ION SUM (2) (m/z)
PARAFFINS
243 = 43+57+71+85+99
MONOCYCLOPARAFFINS
241 = 41+55+69+83+97
DICYCLOPARAFFINS
267 = 67+68+81+82+95+96
ALKYLBENZENES
277 = 77+78+79+91+92+105+106+119+120+133+134
147+148+161+162
INDANES/TETRALINS
2103= 103+104+117+118+131+132+145+146+159+160
NAPHTHALENES
2128= 128+141+142+155


27
given hydrocarbon type, all values (Z/T) are divided by the largest
value of that set. The numbers are arranged in a matrix in proper
order. All elements of the array are then multiplied by an appropriate
pressure sensitivity factor. Table 5 of the ASTM standard (6) gives
the pressure sensitivity factors for each hydrocarbon class and carbon
number. These values represent the instrumental response as a function
of microburette pressure. The means of measuring the amount of sample
introduced into the mass spectrometer was via this monitoring
procedure. The C6 matrix is then inverted after multiplication by the
pressure sensitivity factors. The methods used for inverting a 3x3 and
3x4 matrix (77) are shown in Appendix A; this procedure is best handled
by computer programs. The elements of the C6 matrix are then
multiplied by the corresponding liquid volume factors, also given in
Table 5 of the ASTM standard, which are an indication of the liquid
volume per unit pressure. The matrix values are then divided by 100
and are in units of volume/counts.
Examination of the elements of the inverse calibration matrices
reveals much information on the use of the table. The carbon number 6
matrix illustrates this quite well. A relatively large positive entry,
such as +0.009016 for Z43/T/paraffins, is a good similarity
coefficient, as expected since paraffins response will contain a large
abundance of E43 ions. Similarly, the -0.000003 for Z77/T/paraffins
indicates a low similarity coefficient, which is also expected since
very little Z77 ions will be present for paraffin compounds. The
inverse relationship of these numbers represent the normalization
function of the inverse calibration matrices described above. A


28
thorough evaluation of the application of the inverse calibration
matrices will not be made since the method is quite common in
multicomponent analysis problems. The method involves the
multiplication of a 1x6 matrix (a paraffinic 1x3 and a aromatic 1x3) to
a 6x6 matrix and normalizing the results to 100%. However, as
mentioned above, the matrix used is dependent upon the average carbon
number of the sample in question. Since an integral average carbon
number is rarely obtained, two inverses should be applied with weighted
results. An example calculation of the GC/MS/HTA method is given in
Appendix B.
Computer Hardware and Software
The GC/MS/HTA method required extensive computations once the mass
spectral data had been obtained. This is evident from the discussion
above which described the methods and complexities of the calculations
used. A series of TURBO BASIC programs was written to completely
automate these computations. Additionally, a terminal emulator program
(Persoft, Smarterm 240) was utilized for the direct transfer of data
from the MS data system to an IBM PC. The program used for calculating
the volume % results and the average carbon numbers is shown in
Appendix C. Other programs included an inverse calibration development
program for carbon number 6; and a program which translates the
emulator-captured data to usable format for the HTA program.
Ion Summation Chromatograms
The characteristic ion sums listed in Table 2.1 were plotted as
separate mass chromatograms. These mass chromatograms, as shown in
Figure 2.1, are referred to as ion summation chromatograms and


Reconstructed Ion Current
Figure 2.1
Paraffin
16016
Monocycloparaffin
44006
. i
\
r.v\.
Dicycloparaffin
27040
Alkyl benzene
34368
Retention Time (min)
The ion summation chromatograms of each hydrocarbon type
with the relative areas of each for jet fuel JP-8X 2414.


30
represent the chromatogram of each ion sum listed in Table 2.1. The
area of each ion summation chromatogram was determined and normalized
to 100%. The area percents were then calibrated with the ASTM inverse
calibration matrices after determination of the average aromatic and
average paraffinic carbon numbers. All these calculations were done
automatically, as mentioned above.
Simulated Distillation for Determining Carbon Numbers
The application of ion summation chromatograms provided the
opportunity to investigate the average carbon numbers of the jet fuels.
Figure 2.2 illustrates how the average aromatic carbon number was
obtained using this method. The ion summation chromatogram represents
the aromatic ion series. After determination of the area centroid of
this chromatogram the line may be projected down to the chromatogram of
the corresponding homologous series. The value indicates the aromatic
average carbon number of the fuel. Variations were made using this
technique, such as combinations of ion summation chromatograms, as will
be discussed in the next chapter.
Occupational Hazards
As a final note, the occupational hazards of working with jet fuels
are quite evident considering the nature of these complex mixtures. It
should go without saying to avoid exposure to these materials by using
a well ventilated hood, wearing gloves, and keeping the samples in
properly sealed vials. The major concern of working with these fuels
is the effect of long term exposure. Many of the components in these
mixtures are fat-soluble and therefore bio-accumulation is likely (78).


130.0-1
31
TOTAL.
100.0-1
K1L
Figure 2
n
500 SCAN
8:20 TIME
.2. The aromatic ion summation chromatogram of a jet fuel
JP-8X 2414 on a 3 meter DB5 column. The centroid of the
total area, indicated by the arrows, is referenced to the
alkylbenzene homologous series. The carbon number is
calculated to be 10.95.


CHAPTER III
GAS CHROMATOGRAPHIC/MASS SPECTROMETRIC
HYDROCARBON TYPE ANALYSIS
Characterization of the hydrocarbon type analysis (HTA) method was
performed by evaluation of simple and complex synthetic mixtures,
perturbation of jet fuels, and comparison of results to existing ASTM
results. The experiments performed were to determine the effects of
various instrumental and method parameters on the results of the HTA of
jet fuels. The results of these experiments, as well as the simulated
distillation method for the determination of average carbon numbers,
will be discussed.
GC Sample Introduction
With the application of gas chromatography (GC), a new method of
sample introduction into the mass spectrometer was used for HTA. It
was therefore important to evaluate the specifics of sample
discrimination with respect to this sample introduction technique.
There are several injection techniques used in capillary gas
chromatography. These are split and splitless, which depend on the
flash vaporization of the sample within a heated glass-lined injection
volume, and on-column injection which allows the sample to be loaded
directly onto the capillary column at ambient temperatures. Specifics
32


33
of these capillary GC injection techniques are discussed elsewhere
(75,76). An aromatic mixture containing C12, C14, C16, and C18
straight chain alkylbenzene in equal concentrations was used for the
evaluation of component discrimination. The effect of injection port
temperature and injection technique was evaluated. Figure 3.1 and
Figure 3.2 illustrate the effect of injection port temperature on
component discrimination for splitless and split injections,
respectively, with flame ionization detection. In both cases the
ratios of peak areas were normalized to the C14/C12 ratio at the 280 C
injection port temperature to help illustrate the matter of
discrimination. Both cases indicate component discrimination taking
place at lower temperatures by the ratios being lower. This was due to
less efficient vaporization of the heavier components at lower
temperatures, as was expected. As the temperature was raised, the
ratios increased and leveled off, indicating a lack of discrimination
and the absence of component decomposition at higher injection port
temperatures. A larger degree of discrimination takes place for the
higher carbon number alkylbenzenes, as indicated by the larger ratio
spread between the low and high injection port temperatures. The
splitless technique more clearly illustrates these trends. A minimum
injection port temperature of 250 C should therefore be maintained to
avoid component discrimination. These results also demonstrate the
improvement in reproducibility obtained using splitless injections over
that obtained with split injection technique. A similar evaluation of
component discrimination was performed on the GC/MS instrument. Figure
3.3 illustrates the results which are similar to those from the GC/FID


Normalized Peak Height Ratio
Injection Port Temperature (C)
Figure 3.1. Plot of injection port temperature versus area ratios of
C12, C14, C16, and C18 alkylbenzenes for splitless
injections on a 3 meter DB5 capillary column, with FID
detection.


Normalized Peak Height Ratio
* 1.40
1.20 t
l.oo -
0.80 ~
0.60 ~
0.40 ~
0.20 ~
A
0
90 130 170
In jection
i i i i i i i | i i i i i i i i i | i i i i i i i i i | r
210 250 290
Port Temperature (C)
T
Figure 3.2.
Plot of injection port temperature versus area ratios of
C12, C14, C16, and C18 alkylbenzenes for split injections
on a 3 meter DB5 capillary column, with FID detection.
co
cn


Normalized Peak Height Ratio
Injection Port Temperature (C)
Figure 3.3. Plot of injection port temperature versus area ratios of
C12, C14, Cl 4, and C18 alkylbenzenes for split injections
on a 3 meter UHb capillary column and MS detection.
w
o\


37
technique. However, discrimination effects are less with GC/MS, as
indicated by the smaller spread of area ratios compared to GC/FID. The
vacuum outlet conditions result in a large pressure drop across the
short capillary column, giving higher flow rates and decreased
discrimination as a function of injection port temperatures.
On-column injection was also evaluated in terms of component
discrimination. It has already been demonstrated that on-column
techniques provide the best precision when compared to the other modes
of injection (79). Figure 3.4 illustrates component discrimination as
a function of initial column temperature. The initial column
temperature in on-column injection corresponds roughly to the injection
port temperature in split/splitless injections. For this reason,
evaluations were not possible at initial column temperatures above 120
C, since the early eluting C12 alkylbenzene component was lost in the
solvent front. The results indicated no discrimination, as would be
expected for on-column injections. However, there appears to be a
small enhancement effect for the less volatile components at lower
initial column temperatures. This cannot be explained at the present
time. Table 3.1 compares splitless and on-column injection
techniques for accuracy and precision. A mixture containing known
weight ratios was prepared and analyzed with GC/FID. The FID response
is proportional to the mass flux of analyte, and therefore direct
correlations may be made between weight ratios and area ratios.
Results for both splitless and on-column injections were high compared
to the actual weight ratio, which may be due to some systematic error.


Peak Area Ratio
38
1.35
1.30
1.25
1.20
1.15
1.10
1.05
1.00
C16IC12
ii n i i M i I i i n i i i i i [ i i i i i i i i i l i i i i i i i i i I i i i i i i i" !
20 40 60 80 100 120
Initial Column Temperature (C)
Plot of initial column temperature versus area ratios for
C12, C14, C16, and C18 alkylbenzenes for on-column
injections on a 3 meter DB5 column with FID detection.
Figure 3.4.


39
Table 3.1
Comparisons of Accuracy and Precision of Area Ratios
Components Between Splitless and On-Column Injection
Butvlbenzene
Decane
Hexamethvlbenzene
Decane
Actual Wt. 0.785 0.280
Ratio
Splitless
Area Ratio
%RSD
On-Column
Area Ratio 0.905(.004) 0.330(.009)
%RSD 0.44 2.82
0.894(.005)
0.54
0.30(.01)
4.32
of Various
Techniques
t-Stilbene
Decane
0.374
0.41(.03)
7.24
0.49(.01)
2.02
Note:
number of replicates n=3
number in parenthesis indicates standard deviation


40
The splitless results agreed more closely with the weight ratios, while
the precision of the on-column results was somewhat better.
These results indicate that, as long as the minimum injection port
temperature is maintained, component discrimination is greatly reduced
if not eliminated. Also, better reproducibility is obtained using
splitless injections.
Ancillary Short-Column Experiments
The use of short (3 m) capillary columns in these studies has led
to the discovery of some interesting chromatographic aspects. The
injection technique previously described in the Experimental chapter,
in which the bulk of the sample volume was removed from the syringe
needle volume in order to let the needle equilibrate to the injection
port temperature, was used to eliminate component discrimination and to
obtain more reproducible injections. This technique when used with
short columns, however, leads to the splitting of the early eluting
chromatographic peaks (Figure 3.5). This was determined to be a
function of injection port temperature. At high injection port
temperatures, the residual amount of sample which remains in the
syringe needle is vaporized prior to the injection and vaporization of
the sample contained in the syringe itself. This results in a "pre
peak" at high injection port temperatures which is absent at the lower
injection port temperature.
It was also observed that splitless injections provide better
chromatographic resolution than on-column techniques for short
capillary columns. This is presumably due to the large amount of band


Chromatograms of nonane (1), cyclooctane (2),
propylbenzene (3), and decalin (4) using split injections
on a 3 meter column, a) injection port 280 C, b)
injection port temperature 130 C.
Figure 3.5.


42
spreading incurred for on-column injections relative to the column
length. Figure 3.6 and Figure 3.7 illustrate the comparison of
injection techniques for chromatographic resolution for a narrow
boiling point range fuel and a wide boiling point range fuel,
respectively. The improved chromatographic resolution for the
splitless case is indicated by the sharper peaks, which are most
noticeable for the late eluting peaks.
Analytical Figures of Merit
The limits of detection which are determined here do not reflect
the limits that would actually be obtained if individual components
were to be determined. Figure 3.8 illustrates the reconstructed ion
current (RIC) full-scan mass spectra of a four-component mixture at 0.5
volume percent each, which corresponds to approximately 0.4 ng injected
on the column. The signal-to-noise in the RIC was approximately 3,
which represents the limit of detection for the HTA method. The
sensitivities of the four components are given by the slope of the
calibration curves illustrated in Figure 3.9. These sensitivities were
determined in order to compare the results to the actual ASTM
sensitivities in Table 5 of the ASTM D-2789 standard (6). Table 3.2
compares the sensitivities (slopes of the response curves in Figure
3.9) to the sensitivities of Table 5 of the ASTM standard (6), after
normalization to the C9 paraffin (nonane). The results indicate that
similar trends in sensitivities for the four components were observed
for the two methods, although the propylbenzene sensitivity was
significantly greater in the ASTM results.


Response
43
Retention Time (min) Retention Time (min)
Figure 3.6. Chromatograms of JP-7 jet fuel on a 3 meter column
comparing on-column and splitless injections.


44
Figure 3.7.
Chromatograms of JP-4 jet fuel on a 3 meter column
comparing on-column and splitless injections.


Figure 3.8. Chromatogram of nonane (1), cyclooctane (2),
propyIbenzcne (3), and decalin (4) at 0.5 volume X each 4>
using 0.4 /(L split injection on a 3 meter column.


PEAK AREA
46
DECAUN
- 1 1 ! l
0 2 4 6 8
VOLUME PERCENT
Response curve obtained by linear regression for nonane,
cyclooctane, propylbenzene, and decalin at various volume
percentages.
Figure 3.9.


47
Table 3.2
Comparison of Sensitivities of ASTM and GC/MS/HTA
Results for a Four-Component Mixture
Normalized to the ASTM Sensitivity of Nonane
(Response per Volume %)
COMPONENT
ASTM
SENSITIVITY
GC/MS/HTA
SENSITIVITY
DECALIN
1.99
2.15
PROPYL-
2.52
2.06
BENZENE
CYCLO-
1.72
1.74
OCTANE
NONANE
1.72
1.72


48
The precision of the HTA method was determined by replicate
analyses of several jet fuel samples. The precision was dependent upon
the jet fuel analyzed or the composition of the fuels. The precision
of the HTA method is summarized in Table 3.3, in which the average
percent relative standard deviation is listed by hydrocarbon type for
all fuels analyzed in replicate. The high average relative standard
deviations were a result of that particular volume percent being very
low. The dashed lines indicate a consistent result of zero volume
percent.
Characterization of the GC/MS/HTA Method
Comparisons of ASTM and GC/MS/HTA Results
One of the major tasks in this research effort was to analyze a
number of real jet fuel samples with the newly developed GC/MS/HTA
method and to compare the results to those from the long-established
ASTM D-2789 method. These comparisons would provide information on the
validity of the ASTM inverse calibration matrices with GC sample
introduction and quadrupole mass analysis. Table 3.4 shows these
comparisons for five jet fuels. Several methods were used to evaluate
trends in the comparison versus composition, but none could be found.
The accuracy of the ASTM method has not been evaluated; therefore, the
comparison does not necessarily reflect the accuracy of the GC/MS/HTA
method.
Table 3.5 demonstrates the comparisons of several synthetically
prepared jet fuels. The "recipe" results were calculated from the
known volumes of the components added. Again these comparisons do not
necessarily represent accuracy of the GC/MS/HTA method, since the


49
Table 3.3
The Average Relative Standard Deviation for the GC/MS/HTA of
all Replicate Analyses and Separate Jet Fuels
HYDROCARBON
TYPE
AVERAGE
OF ALL FUELS
JP-4
2455
JP-7
JP-8X
2414
JP-8X
2429
PARAFFIN
3.0
2.1
1.2
7.1
1.7
MONOCYCLO-
PARAFFIN
3.8
2.5
0.6
6.8
5.3
DICYCLO
PARAFFIN
5.6
18.1
1.2
1.4
1.8
ALKYLBENZENE
7.6
3.8
18.8
2.5
5.4
INDANE/
TETRALIN
5.0
10.7
-
2.0
2.4
NAPHTHALENE
7.7
-
-
8.7
6.7
AVERAGE CARBON
NUMBER
AROMATIC
0.5
0.5
0.9
0.5
0.2
PARAFFIN
0.3
0.7
0.3
0.1
0.0


Table 3.4
Comparison of GC/MS/HTA and ASTM D-2789 Results
on Various Fuels, in Volume %
Fuel
Paraffin
Monocyclo
paraffin
Dicyclo
paraffin
Alkyl-
benzene
Indane-
Tetralin
Naphthalene
Aromatic
c//
Paraffin
c//
JP-4 2455
GC/MS/HTA
61.5(.2)
18.5(.8)
3(1)
14.8(.9)
2.0(.4)
0
9.06(.07)
9.50(.08)
ASTM D 2789
70.8
18.0
2.1
7.6
1.4
0.1
8.69
8.01
JP-8X 2429
GC/MS/HTA
0
3.2 (. 8)
68(2)
6.6(.7)
21.4( .8)
1 3(.3)
8.0 (. 1)
9.01(.01)
ASTM D 2789
1.3
21.5
56.0
7.2
13.1
0.9
8.14
8.91
JP-8X 2414
GC/MS/HTA
7.0(.5)
10.3(.7)
35.0(.5)
15.7(.4)
29.7(.6)
2.3(.2)
9.87(.05)
9.40(.01)
ASTM D 2789 14.2
JP-8X SIMULATED
27.0
26.6
15.3
14.5
2.3
9.18
9.46
GC/MS/HTA
11.5(.2)
17.0(.9)
54.9(.9)
7.4(.4)
8.5 ( 2 )
0.6(.04)
8.53(.02)
9.00(0)
ASTM D 2789
12.1
23.1
58.7
2.9
4.1
0.2
7.65
8.69
JET-A 2532
GC/MS/HTA
18.1
38.1
33.4
5.7
4.6
0
9.32
9.30
ASTM D 2789
27.4
44.7
20.8
4.9
2.1
0.2
8.41
8.86
Ln
o
Note: Numbers in parenthesis indicate the standard deviation n-3.


Table 3.5
Comparison of GC/MS/HTA Results and Synthetic Fuel Recipes
for Various Synthetic Fuels, in Volume X
Fuel
Paraffin
Monocyclo
paraffin
Dicyclo
paraffin
Alkyl-
benzene
Indane-
Tetralin
Naphthalene
Olefins
JP-8X SIMUIATED
GC/MS/HTA
11.5
17.5
54.9
7.4
8.5
0.6
-
RECIPE
12
20
60
(combined unsaturates 8 %)
-
HIGH AROMATIC
GC/MS/HTA
13.5
4.0
3.8
51.0
13.9
13.8
-
RECIPE
30
(combi
ned 10 %)
45
10
5
-
GRAND MIX
GC/MS/HTA
23.0
14.0
14.8
30.3
0.1
17.5
-
RECIPE
40
10
20
20
0.0
5
5
ALL GROUPS
GC/MS/HTA
36.6
17.2
2.9
26.7
4.7
11.8
-
RECIPE
60
(combined 10 %)
17
3
5
5


52
synthetic mixtures were formulated from complex petroleum fractions
(Exxon Corporation) such as Isopar C, G, and M (isoparaffinic and
paraffinic mixtures), and Aromatic 100 and 150 (aromatic mixtures).
These mixtures were obtained by simple fractionation and bulk
separation techniques, and were not intended for analytical standards.
Two of these mixtures were analyzed by GC/MS for specific group
components. The Isopar M mixture contained significant amounts of
cycloparaffinic components, with trace aromatics. The Aromatic 150
contained indanes and naphthalenes; the paraffin content was not
determined. The monocycloparaffin recipe results of the olefin-
containing fuels (Grand Mix and All Groups) agree better when the
olefin content is added to the monocycloparaffin content. These two
hydrocarbon types produce similar fragmentation patterns which tend to
equate the two types under the HTA method. More details of the
olefin/cycloalkane effects on the GC/MS/HTA method will be covered
later in this chapter and in Chapter V.
Simple Mixture Analysis
Simple mixtures were used to evaluate the accuracy of the GC/MS/HTA
method. Teeter states in his paper on high resolution mass
spectrometry for 22 hydrocarbon type analysis (29) that no sample can
be prepared which is complex enough to be a valid test for any HTA
method. This "Teeter Rule," as it has become known in our laboratory,
poses a real paradox for validation of these methods: any mixture
which is complex enough to be a valid test of the HTA matrix
calculation is too complex to be prepared. Certainly such a paradox is
difficult for any analytical chemist to accept. These experiments were


53
designed to test this rule as well as to evaluate the accuracy of the
GC/MS/HTA method. Table 3.6 shows the GC/MS/HTA results of a simple C6
mixture compared to the actual calculated volume percentages. The
mixtures were prepared solely of C6 components. The results clearly
indicate the inaccuracy in the analysis of such a simple sample,
although the zero percent components are correctly identified and the
aromatic average carbon numbers agree quite well. Table 3.7 shows the
GC/MS/HTA results of a simple CIO mixture compared to the actual
calculated volume percentages. In this case, better agreement was
obtained for those types present as well as the zero percent types.
The aromatic average carbon was well off the mark, yet the paraffin
average carbon number was very close.
The next step was to evaluate a mixture which contained a spread in
carbon numbers. Table 3.8 shows the GC/MS/HTA results of a simple C8-
C9 mixture compared to the actual calculated volume percents. The
results again indicated the inaccuracy of the method for simple
mixtures, although the precision of the analysis was quite good, as
indicated by the average percent relative standard deviation of 2.3%
for replicate injections. Again, the average aromatic carbon numbers
do not agree as well as the average paraffinic carbon numbers. Table
3.9 shows the GC/MS/HTA results of a simple C8-C10 mixture compared to
the actual calculated volume percents. The monocycloparaffin volume
percent was quite low, which resulted in a larger volume percent for
the dicycloparaffin and the two other hydrocarbon types present. The
average aromatic carbon number was low while the average paraffinic
carbon number was high compared to the calculated results. This seems


54
Table 3.6
Comparison of HTA on a Simple C6 Mixture
With Actual Volume Calculated Results
Simple
HYDROCARBON
TYPE
PREPARED
BY VOLUME %
HTA
VOLUME %
PARAFFIN
70.6
52.3
MONOCYCLO-
PARAFFIN
17.6
23.7
DICYCLO-
PARAFFIN
0.0
0.0
ALKYLBENZENES
11.8
24.0
INDANE/
TETRALIN
0.0
0.0
NAPHTHALENE
0.0
0.0
AVERAGE CARBON
NUMBER
AROMATIC
6.0
6.00
PARAFFIN
6.0
6.75
Mixture Make-up: Paraffin:
300
200
100
fj.L hexane
/L 3-methylpentane
L 2,2-dimethylbutane
Monocyclo-
paraffin:
100
50
fiL cyclohexane
fiL methylcyclopentane
Alkylbenzene:
100
/L benzene


Table 3.7
Comparison of HTA on a Simple CIO Mixture
With Actual Volume Calculated Results
HYDROCARBON PREPARED HTA
TYPE BY VOLUME % VOLUME %
PARAFFIN 33.3 29.8
MONOCYCLO- 0.0 0.0
PARAFFIN
DICYCLO- 33.3 35.8
PARAFFIN
ALKYLBENZENE 33.3 34.3
INDANE/ 0.0 0.0
TETRALIN
NAPHTHALENE 0.0 0.0
AVERAGE CARBON
NUMBER
AROMATIC 10.0 8.44
PARAFFIN 10.0 9.96


56
Table 3.8
Comparison of HTA on a Simple C8-C9 Mixture
With Actual Volume Calculated Results
HYDROCARBON
PREPARED
HTA
TYPE
BY VOLUME
% VOLUME %
PARAFFIN
44.5
39.2 (.5)
M0N0CYCL0-
PARAFFIN
33.4
21.3 (.2)
DICYCLO-
PARAFFIN
0.0
6.9 (.07)
ALKYLBENZENE
13.9
17.1 (.4)
INDANE/
TETRALIN
8.3
15.4 (.9)
NAPHTHALENE
0.0
0.0
AVERAGE CARBON
NUMBER
AROMATIC
9.00
8.68
PARAFFIN
8.43
8.44
Mixture Composition
(fiL) C8:
octane 50
2,5-dimethylhexane 50
2,3,4-trimethylpentane
octane 50
ethylcyclohexane 20
C9:
nonane 50
2,2,5 -trimethylhexane 20
isopropylcyclohexane 50
indane 30
propylbenzene 50


Table 3.9
Comparison of HTA on a Four-Component Mixture
With Actual Volume Calculated Results
(in Volume Percent)
HYDROCARBON CALCULATED HTA
TYPE BY VOLUME EXPERIMENTAL
PARAFFIN
25
27.0
MONOCYCLO-
PARAFFIN
25
9.8
DICYCLO-
PARAFFIN
25
33.7
ALKYLBENZENE
25
29.2
INDANE/
TETRALIN
-
0.0
NAPHTHALENE
-
0.3
AVERAGE CARBON
NUMBER
AROMATIC
9.0
8.68
PARAFFIN
9.0
9.59


58
to be the normal trend for these simple mixtures. Table 3.10 shows
the analysis of the same mixture as in Table 3.9 with the hexane
solvent included in the HTA calculation. The changing HTA volume
percent results generally agree with those expected, with the exception
of the monocycloparaffin results, which increase rather than decrease.
This would be expected since the mass spectrum of hexane contains a
large relative abundance of m/z 41, which is an ion of the
monocycloparaffin 2-series. The average aromatic carbon number for the
GC/MS/HTA results remains constant when hexane is included in the
calculation, as it should. The average paraffinic carbon number
decreases as expected and shows excellent agreement within the
predicted value.
To summarize, the analysis of simple mixtures by GC/MS/HTA does not
result in correct volume percent, which may simply be a verification of
the Teeter Rule. The paraffin and alkylbenzene volume percents showed
the best and most consistent agreement. The average paraffinic carbon
numbers consistently showed the best agreement except for the simple C6
mixture. The average aromatic carbon number was consistently low
compared to the actual results. The CIO mixture analysis was quite
accurate, unlike the other two simple mixtures. This may be an
erroneous result or may have some significance. Perhaps the sample
make-up of the CIO mixture more closely matches that of the original
CIO mixture used in the calibration matrix, or the matrix calculation
works better for a more closely distributed (single carbon number)
mixture distribution.


59
Table 3.10
Comparison of HTA on a Four-Component Mixture
With Actual Volume Calculated Results
With the Hexane Solvent Included in the Calculation
(in Volume Percent)
HYDROCARBON
TYPE
CALCULATED HTA
BY VOLUME EXPERIMENTAL
PARAFFIN
79
70.5
M0N0CYCL0-
PARAFFIN
7
16.2
DICYCLO-
PARAFFIN
7
5.5
ALKYLBENZENE
7
7.7
INDANE/
TETRALIN
-
0.0
NAPHTHALENE
-
0.0
AVERAGE CARBON
NUMBER
AROMATIC
9.0
8.72
PARAFFIN
6.7
6.70
100 /iL nonane
100 iL cyclooctane
100 iL n-propylbenzene
100 iL decalin
Sample Mixture in 1000 iL hexane:


60
Inverse Calibration Matrix Variation
An initial goal of this project was to validate the use of the
existing (ASTM D-2789) inverse calibration matrix with quadrupole mass
analysis. Since the matrix was prepared with one specific set of
calibration mixtures, it was desired to determine the effect of
calibration sample make-up on the inverse calibration matrix. A series
of C6 components was used to prepare an inverse calibration matrix for
carbon number 6 only. The hydrocarbon types were limited to paraffins,
monocycloparaffins, and aromatics because there are no C6 members of
the other types. Table 3.11 indicates the sample make-up used for the
determination of each hydrocarbon type similarity coefficient in the
inverse calibration matrix. The similarity coefficients are
normalization factors for the mixing of mass spectral ions of the
characteristic ion series. Various combinations were used for the
inverse calibration matrix. The calculational method used is similar
to that outlined in the experimental chapter. A computer program was
written to calculate the C6 inverse calibration matrix based on the
calculational method shown in Appendix A. A simple C6 mixture was
prepared and analyzed using the various inverse calibration matrices.
The results are compared to the actual volume calculated results in
Table 3.12. The results show a significant amount of fluctuation,
indicating the dependence of the calibration sample make-up on the
matrix results. The closest agreement comes with the P4C2B1
combination, whose monocycloparaffin make-up is similar to the test
mixture make-up but whose paraffin make-up is not. The worst agreement
comes with the P4C1B1 combination, which is expected since the paraffin


61
Table 3.11
Component Codes and Make-Up for Preparation of Samples
Used in the Various Carbon Number 6 Inverse Calibration Matrices
Component Code
Sample Make-Up (in L)
Paraffins
hexane
3-methylpentane
2,2-dimethylbutane
PI
500
250
100
P2
250
100
500
P3
100
500
250
P4
1000
250
100
Monocyclo-
paraffins
cyclohexane
methylcyclopentane
Cl
500
250
C2
250
500
Alkylbenzenes
benzene
B1
1000


62
Table 3.12
Comparison of Volume Percent Results on a Simple Carbon Number 6
Mixture Using the Various Combinations of Calibration Mixtures as Listed
in Table 3.11 Previously Shown
Calibration Standard
Composition
by Component Codes
Paraffin
Monocyclo-
paraffin
Alkylbenzene
(benzene)
P1C1B1
74
10
16
P1C2B1
74
10
16
P2C1B1
67
19
14
P2C2B1
67
19
14
P3C1B1
68
18
15
P3C2B1
68
18
15
P4C1B1
53
36
11
P4C2B1
69
17
15
ACTUAL VOLUME CALCULATED
70.6
17.6
11.8
Simple C6 Mixture Make-up: Paraffin: 300 /iL hexane
200 /iL 3-methylpentane
100 /iL 2,2-dimethylbutane
Monocyclo
paraffin: 100 /iL cyclohexane
50 /iL methylcyclopentane
Alkylbenzene : 100 /iL benzene


63
and monocycloparaffin make-up is quite different from the test mixture
make-up. The aromatic results, however, are in the closest agreement
with this combination. This series of experiments illustrates the
importance of the make-up of each single type component in
determination of the similarity coefficients and the inverse
calibration matrices. This C6 example represents the simplest case in
this analysis. The complications faced with increasingly higher carbon
number mixtures and matrices are unknown. The complexities of these
mixtures may tend to eliminate these problems or enhance them.
Perturbation Jet Fuel Analysis
The GC/MS/HTA validation experiments described so far indicate that
there still remains a need for validation of the GC/MS/HTA method since
the above validation experiments contained limitations such as the
Teeter Rule in the simple mixture analysis, and the unknown composition
of the petroleum fractions in the synthetic fuel comparisons. To
maintain the required complexity of the mixtures to be analyzed (to
avoid complications due to the Teeter Rule), the jet fuels were
perturbed by addition of a pure component of known volume. Table 3.13
shows the GC/MS/HTA results for a JP8X jet fuel before and after
spiking the fuel with different amounts of various pure components.
The paraffin volume percent of the first three spiked fuels should be
increased to a calculated 28.6%. The fourth spiked fuel, which
contains no paraffin spike, should agree with the "fuel only" results.
These were in fact the results observed. The fuel containing the
nonane and undecane spike showed the closest agreement. The volume


64
Table 3.13
Comparison of GC/MS/HTA of 86-POSF-2429 JP8X FUEL
After Spiking with Various Hydrocarbon Types
in Volume %
HYDROCARBON FUEL SPIKE 1* SPIKE 2 SPIKE 3 SPIKE 4
TYPE
PARAFFIN
0.0
29.6
(28.6)
24.6
(28.6)
32.0 (28.6)
0.2
(0.0)
MONOCYCLO-
PARAFFIN
6.6
1.2
(4.7)
6.7
(4.7)
0.2 (4.7)
15.1
(19.0)
DICYCLO-
PARAFFIN
72.5
53.8
(57.8)
52.0
(57.8)
52.2 (57.8)
52.0
(57.8)
ALKYLBENZENE
6.2
4.6
(4.4)
4.9
(4.4)
4.7 (4.4)
22.9
(18.7)
INDANE/
TETRALIN
14.4
10.6
(10.3)
11.6
(10.3)
10.4 (10.3)
9.3
(10.3)
NAPHTHALENE
0.3
0.2
(0.2)
0.2
(0.2)
0.4 (0.2)
0.5
(0.2)
AVERAGE CARBON
NUMBER
AROMATIC
7.50
7.32
7
53
7.48
8
53
PARAFFIN
9.02
9.35
8
55
9.51
9
01
*
SPIKE 1: 500
AtL FUEL
+ 100
pL n-nonane + 100 /L undecane
SPIKE 2:
II
+ 200
/I n-octane
SPIKE 3:
II
+ 200
fil n-decane
SPIKE 4:
It
+ 100
/L butylbenzene + 10C
AL cyclooctane
Note: numbers in parenthesis indicate the expected results due to
dilution or addition of that specific type.


65
percent of the remaining hydrocarbon types of the first three spiked
fuels (paraffinic spikes) should decrease due to dilution and remain
relatively constant. The calculated values are monocycloparaffin,
4.7%; dicycloparaffin, 51.8%; alkylbezenes, 4.4%; indane/tetralin,
10.3%; and naphthalene, 0.2%. On examination of Table 3.13, excellent
agreement is observed for all types for the first three spikes, with
the exceptions of the monocycloparaffin results. Attempts were made to
explain this behavior by analysis of the mass spectra of each
particular component, but no distinctions could be made. Most
paraffins contain a large relative abundance of m/z 41 (30-50%) and
m/z 55 (5-15%) which are ions indicative of the monocycloparaffin type.
The fourth spiked fuel also demonstrates excellent agreement with the
calculated perturbations for the hydrocarbon types not present in the
spike. The monocycloparaffin results were low compared to the
calculated (19.0%), and the alkylbenzene was high compared to the
calculated (18.7%). Again no explanation could be drawn by examination
of the component spectra; however, the sum of the two types
(monocycloparaffin and alkylbenzene) did equal the sum of the
calculated results. The average carbon numbers demonstrated good
correlation with the perturbation of the fuel. The average aromatic
carbon number remained relatively constant for paraffin perturbation
but increased with the butylbenzene (CIO) addition. The average
paraffinic carbon number also correlated with the paraffin
perturbation; 9.35 for nonane and undecane (CIO average) addition;
8.55 for octane addition; 9.51 for decane addition; and no change with
the addition of spike number four.


66
This perturbation approach appears to- be a much more successful
approach for validation of the GC/MS/HTA method than the previous two
methods (simple mixture analysis and ASTM comparisons). The much
better agreement seems to further support the "Teeter Rule" and
indicates that additional experiments should be performed.
A second set of fuel perturbation experiments was performed using
the standard addition method. Figure 3.10 illustrates the GC/MS/HTA
results for standard addition of n-propylbenzene to JP-4 2455 jet fuel.
The HTA aromatic type response was compared to the theoretical aromatic
type response of the volume percent added. The more positive slope of
the experimental line indicates that upon increased additions of n-
propylbenzene to the jet fuel an above-average GC/MS/HTA aromatic
response will result. However, the negative x-intercept (-13.2
aromatic volume percent), which indicates the volume percent of the
original fuel, agree to within experimental error with the original HTA
result (12.8). To test the hypothesis stated above in regard to the
above average GC/MS/HTA response of the n-propylbenzene alkylbenzene,
the same fuel was spiked with the Aromatic 150 mixture. Figure 3.11
illustrates the results of this standard addition experiment. The
"real line" intersects with the theoretical line and adheres more
closely to it in the region of the data points. This confirms the
above average response hypothesis of the n-propylbenzene. This may
indicate that the Aromatic 150 better represents the composition of the
original calibration solution used in the preparation of the inverse
calibration matrix. The larger negative x-intercept of the Aromatic
150 indicates that a larger volume percent must be added to equal the


Aromatic Volume Percent
67
Volume Percent Added
Figure 3.10. Plot of volume percent standard addition of
n-propylbenzene to jet fuel JP-4 2455. The real line
indicates the experimental results.


Aromatic Volume Percent
68
Volume Percent Added
Figure 3.11. Plot of volume percent standard addition of Aromatic 150
to jet fuel JP-4 2455. The real line indicates the
experimental results.


69
theoretical volume percent. This result is consistent with the
composition of the Aromatic 150 mix which is known to contain
components other than alkylbenzenes such as indanes, tetralins, and
naphthalenes. Figure 3.12 compares the mass spectrum of n-
propylbenzene and the average mass spectra of the Aromatic 150 mixture.
The presence of non-alkylbenzene aromatics in the Aromatic 150 is
evident by the presence of m/z 117 and m/z 118, indanes and tetralins;
m/z 128 and m/z 142, naphthalenes.
The above analysis of the standard addition plots was formulated
based on the linear regression of the experimental standard additions.
This seems appropriate when considering the linear theoretical plots;
however, in both cases there was a clear curvature to the data points.
This effect is illustrated in Figure 3.13 in which the experimental n-
propylbenzene data have been connected by a spline fit. The decreasing
slope with increasing volume percent added could possibly be explained
by the partial molal volume of mixing theory, but the degree of change
is much too large. The more negative x-intercept which was obtained
in both of the previous results is not consistent with the types of
additions made and otherwise has no explainable significance. These
results confirmed the original linearization assumptions used above.
Evaluation of Olefin and Cvcloparaffin Isomers
A major concern of the ASTM and GC/MS/HTA methods is the presence
of olefins and how they effect the results of the monocycloparaffin
volume percentages. In the ASTM method it is assumed that there is no
difference between the fragmentation pattern of any two olefinic or
cycloparaffin isomers of equal carbon number. This results in an


% Relative Abundance
miz
Figure 3.12. Mass spectra of n-propylbenzene and Aromatic 150.
o


Aromatic Volume Percent
71
Figure 3.13.
Spline fit to experimental volume percent standard
addition of n-propylbenzene to jet fuel JP-4 2455
compared to theoretical addition.


72
uncertainty in the HTA analysis if the presence of olefins is uncertain
or if their concentrations are unknown. The ASTM procedure requires
the subtraction of the olefin volume percent from the monocycloparaffin
volume percent when the olefin content is known. The olefin content
may be determined using the ASTM D-875 standard method. We were
interested in evaluating the effects of the olefin content on the
GC/MS/HTA results and how they would compare to the isomeric
monocycloparaffin content. Table 3.14 shows the differences in the
GC/MS/HTA paraffin, monocycloparaffin, and dicycloparaffin results for
the JP-4 2455 jet fuel after the addition of C7, C9, and CIO olefin and
monocycloparaffin isomers. It should be noted that the CIO case was
analyzed on a separate day which resulted in a slight variation in the
"FUEL ONLY" results. The table also compares these results to the
theoretical content expected. The results of the unsaturated
hydrocarbon types are not shown since changes were incurred only
through dilution. In all cases, the monocycloparaffin demonstrated a
larger increase in the monocycloparaffin content than the olefin.
Examination of the paraffin and dicycloparaffin content after
perturbation of the fuels demonstrates some interesting results which
can be evaluated in terms of the differences in the mass spectra of
each and reference to the characteristic ion series for each
hydrocarbon type (Table 2.1). Figure 3.14 shows the mass spectra of
the C7 isomers cycloheptane and 1-heptene. A larger relative abundance
of molecular ion (m/z 98) and [M-15]+ (m/z 83) was obtained for the
cycloheptane but produced little differences between the GC/MS/HTA
results. Figure 3.15 shows the mass spectra of the C9 isomers


73
Table 3.14
Comparison of HTA of JP-4 2455 Jet Fuel
After Spiking with C7, C9, and CIO Cycloalkane and Olefin Isomers
(in Volume Percent)
HYDROCARBON
TYPE
FUEL ONLY
500 /zL
Fuel+50 n~L
cycloheptane
Fuel+50 /L
1-heptene
Expected
Result
PARAFFIN
61.5
57.9
59.9
55.9
MONOCYCLO-
PARAFFIN
18.5
24.8
22.2
25.9
DICYCLO-
PARAFFIN
3.1
1.1
1.8
2.8
HYDROCARBON
TYPE
FUEL ONLY
500 nL
Fuel+50 /j.L
propylcyclohexane
Fuel+50 nL
1-nonene
Expected
Result
PARAFFIN
61.5
55.1
61.4
55.9
MONOCYCLO-
PARAFFIN
18.5
24.5
22.3
25.9
DICYCLO-
PARAFFIN
3.1
6.4
1.4
2.8
HYDROCARBON
TYPE
FUEL ONLY
500 fiL
Fuel+50 /L iso
butyl cyclohexane
Fuel+50 /L
1-decene
Expected
Result
PARAFFIN
58.8
52.2
58.3
53.4
MONOCYCLO-
PARAFFIN
17.8
27.4
21.4
25.3
DICYCLO-
PARAFFIN
4.0
3.7
3.4
3.6


% Relative Abundance
miz
Figure 3.14.
Comparison of mass spectra of C7 isomers cycloheptane and
1-heptene.
-4


% Relative Abundance
160.0
50.0
100.0
50.0
miz
Figure 3.15. Comparison of mass spectra of C9 isomers isopropyl-
cyclohexane and 1-nonene.
U1


76
isopropylcyclohexane and 1-nonene. Again a larger relative abundance
of molecular ion (m/z 126) was obtained for the cycloparaffin, but also
the fragmentation pattern was quite different than that of the olefin.
The large relative abundances of the m/z 82 fragment (96%) and the m/z
67 fragment (42%) for the cycloparaffin isomer, which were very low for
the olefin (9%) caused the dicycloparaffin volume percent of the
cycloparaffin-spiked fuel determined by HTA to be high. Similarly the
large relative abundances of paraffinic fragment ions (m/z 43, 57, and
71) for the olefin isomer caused the paraffin volume percent of the
olefin-spiked fuel to be well above that of the cycloparaffin-spiked
fuel. Figure 3.16 shows the mass spectra of the CIO isomers
isobutylcyclohexane and 1-decene. Again a larger relative abundance of
molecular ion (m/z 140) was obtained for the cycloparaffin. The
fragmentation patterns, although different, both contributed response
to the dicycloparaffin volume percent of the spiked fuels. The
slightly higher volume percent calculated for the cycloparaffin-spiked
fuel was due to the larger relative abundance of m/z 82 fragment. The
paraffinic volume percent was again larger for the olefin spiked fuel
because of the large relative abundances of the paraffinic fragment
ions, especially m/z 43.
These studies validate the need for separate determinations of
cycloparaffin and olefin content in the HTA of jet fuels. New
complications have been introduced as to the effects on the HTA
calculated paraffin and dicycloparaffin content. Examination of the
differences in the mass spectra of the isomeric monocycloalkanes and


% Relative Abundance
100.0-1
33
50.0
100.0
50.0
55
ISO-BUTYLCYCLOHEXhHE
140
T ' I ' I ' '' | I'
5b
41
70
r||l|l|i |
40 60
OECEHE
83
37
111
' I 11 '' 11 | b I ' |
1 I'1 |1 i1 1 I ' i
30 100 120 140 160
m/z
'nr1
180
200
Figure 3.16. Comparison of mass spectra of CIO isomers isobutyl-
cyclohexane and decene.


78
olefins of the three carbon numbers studied suggest the possibility of
developing techniques which could identify and quantitate each isomer
separately in the presence of the other.
Evaluation of Methods for Average Carbon Number Determinations
The GC/MS/HTA method relies heavily on the accuracy of the average
carbon number calculations, since the inverse calibration matrices
chosen are dependent upon these results. As in the ASTM methods, these
average carbon numbers (aromatic and paraffinic) are determined based
on the intensities of the paraffin and alkylbenzene molecular and
fragment ion series such as [M-15]+. This has raised a certain degree
of speculation concerning the accuracy of this method. First, as
mentioned, the method is based on the intensities of molecular and
fragment ions, which are generally of very low relative abundance.
This is particularly true for paraffins, whose molecular ion relative
abundances are on the order of 1-5%. Alkylbenzenes, however have
relatively abundant molecular ions, on the order of 20-50%. Therefore
less error would be expected for the aromatic results. Second, the
volume percent results of the remaining hydrocarbon types are dependent
upon the average carbon number results of the paraffins and
alkylbenzenes. For example, the dicycloparaffin volume percent is
calculated based on the inverse calibration matrix determined by the
average paraffin carbon number. This would obviously cause even
greater error in the results for those samples which contain small
amounts of paraffins relative to the dicycloparaffins. To clarify some
of these uncertainties, a new method of calculating the average carbon
numbers of a jet fuel was developed.


79
As was shown in Figure 2.2, the GC/MS simulated distillation
(GC/MS/SD) method determines the centroid of the total area of a
chromatographic profile. The GC/MS facilitates the ability to profile
an ion series characteristic of a certain hydrocarbon type with an ion
summation chromatogram, which may then be compared to a similar
chromatogram of a homologous series of that hydrocarbon type. Figure
3.17 again illustrates this method, only in this case showing the
paraffin series (E43) of the JP-8X fuel with the corresponding n-
paraffin homologous series in parallel. Several variations in this
technique were used for the determination of the average carbon
numbers. These variations were obtained by variations in the
particular set of ions used in the ion summation chromatograms. Table
3.15 shows the results of these carbon number determinations for
several jet fuels. From this table, three comparisons can be made for
both aromatic and paraffinic average carbon numbers: comparison between
the two GC/MS/SD methods (which will be explained below); comparison
between the two GC/MS/SD methods and the GC/MS/HTA method; and
comparison between the GC/MS/HTA and the ASTM method.
GC/MS Simulated Distillation
Table 3.15 provides data for the comparison of the two GC/MS/SD
methods, SIM DIST #1 and SIM DIST //2 for both aromatic average carbon
numbers and paraffinic average carbon numbers. The comparisons
demonstrate the variations which were due to the characteristic set of
ions used in the calculations as discussed above. The methods used for
the two GC/MS/SD average carbon numbers determinations were as follows:
the SIM DIST //I method calculates the paraffinic carbon number based


100.0-
80
i
Figure 3.17. The paraffinic (X43) ion summation chromatogram of jet
fuel JP-8X 2414 on a 3 meter DB5 column. The centroid of
the total area, indicated by the arrows, is referenced to
the n-paraffin homologous series. The average paraffinic
carbon number is calculated to be 12.89.


Table 3.15
Comparison of Average Paraffin and Aromatic Carbon Numbers
for Various Fuels Using
Aromatic Average Carbon Number
Fuel
SIM DIST //Ia
SIM DIST //2b
CC/MS/HTA
JP-4 2455
10.4(.4)
10.9(.2)
9.06(.07)
JP-8X 2429
12.1
10.7
8.0 ( 1)
JP-8X 2414
10.9
11.9
9.87(.05)
JP-8X
SIMULATED
10.2
10.7
8.53(.02)
JET-A 2532
11.8
11.8
9.32
JP-7 NARROW
B.P. RANGE
11.6(.1)
11.85(.01)
10.5(.1)
PETROLEUM
JP-8 2400
10.1
10.3
9.51
PETROLEUM
JP-4 0988
9.9
10.2
9.16
everal Calculational Techniques
Paraffin Average
Carbon Number
A STM
SIM DIST //Ia
SIM DIST
#2^ GC/MS/HTA
A STM
8.69
12.1(.2)
12.0(.3)
9.50(.08)
8.01
8.14
14
11.1
9.01(.01)
8.91
9.18
13.1
11.8
9.40(.01)
9.46
7.65
12.4
11.1
9.00(0)
8.69
8.41
12.6
12.5
9.30
8.86
-
12.4(.2)
12.3(.2)
11.52(.03)
-
-
10.8
10.6
9.83
-
10.7
10.8
10.03
a SIM DIST y/1 Area centroid based on paraffin and alkylbenzene ion summation chromatograms,
b SIM DIST //2 Area centroid based on saturates and unsaturates ion summation chromatograms.
Note: Numbers in parenthesis are standard deviations.


82
solely on the ion summation chromatogram of the 243 ions (paraffin) ,
and the aromatic carbon number based on the ion summation chromatogram
of the 277 ions (alkylbenzene) ; the SIM DIST #2 method calculates the
paraffinic carbon numbers based on the ion summation chromatogram of
all the saturated ion sets, 243, 241, and 267, (paraffin,
monocycloparaffin, and dicycloparaffin) and the aromatic carbon
numbers based on the ion summation chromatograms of all the unsaturated
ion sets, 277, 2103, 2128, (alkylbenzene, indane/tetralin, and
naphthalene). To make a proper evaluation of these results, reference
must be made to the composition of these jet fuels, as shown in Table
3.4. For those fuels whose saturated and unsaturated compositions were
made up mainly of paraffins and alkylbenzenes, respectively, there were
only small differences between the average carbon numbers obtained by
two techniques. For example, the JP-4 2455 jet fuel has a saturated
fraction composed mainly of paraffin, which results in little
difference between the average paraffinic carbon numbers from the two
techniques, 12.1 and 12.0. The JP-8X 2429 jet fuel, on the contrary,
has a saturated fraction composed mainly of dicycloparaffin which has
resulted in a large difference between the average paraffinic carbon
numbers of the two techniques, 14 and 11.1. For this fuel the same
trend was observed for the average aromatic carbon numbers, 12.1 and
10.7, since the unsaturated fraction was composed mainly of
indane/tetralin rather than alkylbenzenes. In summary these two
techniques of average carbon numbers determinations demonstrate a large
dependency upon the composition of the jet fuel, which demonstrates the
failures of the present ASTM method and the need for more specific


83
methods for carbon number determinations of each particular hydrocarbon
type. These conclusions are further supported by the second set of
comparisons between the GC/MS/SD and GC/MS/HTA results.
Comparison Between GC/MS/SD and GC/MS/HTA
Table 3.15 provides data for the comparison of the GC/MS/SD and
GC/MS/HTA methods of average carbon number determination. The original
purpose of the development of the GC/MS/SD method was to demonstrate
the dependence of the average carbon number results on the sample
concentration, and the limitations of calculating the paraffinic
(saturated) and aromatic (unsaturated) average carbon number based on
the paraffin and alkylbenzene composition only (both discussed above).
The large differences between the GC/MS/SD and GC/MS/HTA results were
not expected. In all cases a larger average carbon number (sometimes
larger by 3 or 4 carbons) was obtained for the GC/MS/SD results than
for the GC/MS/HTA results. This raised uncertainty in the results of
the GC/MS/SD technique, although the simulated distillation methods
seemed scientifically sound and much more tangible than the mass
spectral technique of the GC/MS/HTA method discussed above.
Consultation with the engineers at the Pratt and Whitney Fuels
Division, who have analyzed many jet fuels for average boiling point by
the ASTM simulated distillation method (44,45), suggested a consistent
underestimation of the average carbon numbers by the ASTM D-2789
method.
Comparison Between GC/MS/HTA and ASTM
The final set of comparisons made in Table 3.15 were between the
GC/MS/HTA and ASTM D-2789 results. These results were determined based


84
on the same computational technique as discussed at the beginning of
this section. Large deviations between the results of the two
techniques were apparent for most fuels, with the GC/MS/HTA values
generally larger. The results of jet fuel JP-8X 2429 showed the best
paraffinic and aromatic average carbon number agreement, while jet fuel
JP-4 2455 showed the worst. The measure of paraffinic carbon number
agreement may be correlated to the saturate composition of the fuels
(see Table 3.4), since the JP-8X fuels (such as 2429 and 2414) were
composed mainly of dicycloparaffins, and the JP-4 fuel was composed
mainly of paraffins. These correlations are of course dependent upon
the accuracy of the volume percent results, which are themselves
dependent upon the average carbon number results. No correlation
between the composition of the jet fuels and the aromatic carbon
numbers could be determined. However, agreement between the two
methods was generally better for the aromatic carbon numbers than for
the paraffinic carbon numbers. This may be due to the increased
accuracy of the technique as reflected in the larger relative abundance
of the alkylbenzene molecular ions, as discussed above.
The presence of large amounts of naphthalenes in jet fuels can
cause a large amount of error in the paraffinic average carbon number
and ultimately in the final volume percent results (6), since the m/z
128, m/z 142, and m/z 156 ions used in the ASTM average paraffinic
carbon number determination correspond to abundant molecular ions of
naphthalene, methylnaphthalene, and dimethylnaphthalene, respectively.
Investigations of the effect of this perturbation were made by spiking
the JP-4 2455 jet fuel with dimethylnaphthalene. Table 3.16


Table 3.16
Comparison of GC/MS/HTA of JP4 Fuel
After Spiking with Dimethylnaphthalene
in Volume Percent
HYDROCARBON
TYPE
FUEL ONLY
500 fiL
Fuel+100 fiL
Dimethylnaphthalene
Expected
Result
PARAFFIN
61.5
43.9
51.3
MONOCYCLO-
PARAFFIN
18.5
18.0
15.4
DICYCLO
PARAFFIN
3.1
0.0
2.6
ALKYLBENZENE
14.8
11.4
12.3
INDANE/
TETRALIN
2.0
2.2
1.7
NAPHTHALENE
0.0
24.5
16.7
AVERAGE CARBON
NUMBER
AROMATIC
9.06
8.91
9.55
PARAFFIN
9.50
10.58
9.50


86
illustrates the results of this perturbation of the jet fuel. The
drastic increase in the paraffinic average carbon number from 9.50 to
10.58 reflects the effect of the addition of the C12
dimethylnaphthalene. An increase in the aromatic average carbon number
was expected since dimethylnaphthalene is a C12 aromatic; however the
results actually decreased. This is due in fact to the average
aromatic carbon number calculational method which is based solely on
ions of the alkylbenzene series. The mass spectra of
dimethylnaphthalene contains a small relative abundance of m/z 91,
which is an ion of the alkylbenzene series, which explains the decrease
in aromatic average carbon number. The saturate volume percent results
of the spiked fuel did not agree with changes expected due simply to
dilution. This may be attributed to the incorrect average paraffinic
carbon number on which the volume percent calculation is now based. It
should be noted that the naphthalene volume percent increased to 24.5%
for the spiked fuel which was close to the expected 16.7% theoretical
value. These results illustrate the significance of the naphthalene
content on the hydrocarbon type analysis results, not only on
paraffinic carbon numbers, but on volume percent results as well.
Effect of Chromatographic Resolution on Carbon Number Calculations
The evaluations and comparisons above were made under the
assumption that the carbon number calculational techniques produced
valid average carbon number results. Since chromatographic separation
played such an important role in these determinations, especially for
the GC/MS/SD techniques, it was desired to determine the effect of
increased chromatographic resolution on the average carbon number


87
results. Table 3.17 shows the effect of chromatographic separation on
the average carbon number results for the four calculational techniques
and two separate jet fuels, JP-4 2455 and JP-8X 2429. The
chromatographic resolution was increased by changing from a 3 meter
column to a 30 meter column. Both fuels demonstrated a dependence on
chromatographic separation for all carbon number calculational
techniques. In all cases the determination of carbon numbers with
increased chromatographic separation, with the exception of the
aromatic average carbon number for JP-8X using the SIM DIST #2 method,
better agreement was obtained between the GC/MS/DS and the GC/MS/HTA
results, and between the GC/MS/HTA and ASTM results. Increased
chromatographic separation reduced all average carbon numbers for the
JP-4 fuel. Increased chromatographic separation decreased all average
carbon numbers for the JP-8X fuel with the exception of the paraffinic
average carbon number using the SIM DIST //I method. These results
indicate that the average carbon number results are very much dependent
upon the degree of chromatographic separation employed, and that
increased chromatographic resolution results in more accurate average
carbon number determinations.
Summary of Results
An extensive amount of effort was dedicated to characterization of
the GC/MS/HTA method. The injection methods were evaluated in terms of
component discrimination which resulted in the development of a non
discriminating injection technique. The method was evaluated in terms
of sensitivity and precision. Similar sensitivities were determined to


Table 3.17
CHROMATOGRAPHY
CONDITIONS
3 METER DB5
30 METER DB5
3 METER DB5
30 METER DB5
Comparison of Average Paraffin and Aromatic Carbon Numbers
for JP-4 2455 and JP-8X 2429 Fuels as a Function of Chromatographic
Separation Using Several Calculational Techniques
Aromatic Average Carbon Number Paraffin Average Carbon Number
SIM DIST #la SIM DIST #2b GC/MS/HTA ASTM SIM DIST #1 SIM DIST #2 GC/MS/HTA
JP 4 2455 FUEL
10,4(.4) 10.9(.2) 9.06(.07) 12.1(.2) 12.0(.3) 9.50(.08)
8.69
9.22(.01) 9.58(.01) 9.00(0) 8.64(.02) 8.68(.04) 8.95(.06)
JP 8X 2429 FUEL
12.1 10.7 8.0(.1) 14 11.1 9.01(.01)
8.14
12.07 (. 06) 12.7K.01) 8.19( .01) 13.07(,05) 11.59(.06) 9.20(.03)
ASTM
8.01
8.91
SIM DIST //I Area centroid based on paraffin and alkylbenzene ion summation chromatograms.
SIM DIST #2 Area centroid based on saturates and unsaturates ion summation chromatograms.
Note: Numbers in parenthesis indicate standard deviations.
00
oo


89
those calculated in the ASTM technique. The precision was dependent on
hydrocarbon type and volume percent.
To characterize and validate the GC/MS/HTA method, a series of
experiments were performed. Comparisons of GC/MS/HTA results with the
ASTM results were inconsistent and followed no trends. Evaluations of
GC/MS/HTA results of synthetic mixtures showed good agreement in some
cases but were still inconsistent. The analysis of simple mixtures
seemed to validate the Teeter Rule, although excellent agreement was
often present. The perturbation fuel analysis introduced a new method
for the characterization of HTA methods. The results obtained here
were consistent with the expected results and represented a significant
contribution towards validation of the method.
A new method for carbon number determination was developed based on
GC/MS/simulated distillation. A critical evaluation of this method,
the GC/MS/HTA method, and the ASTM method was performed. The results
indicated that the GC/MS/HTA and ASTM method underestimate the average
carbon numbers which have a significant effect on the volume percent
results of HTA methods. Chromatographic resolution affected the
GC/MS/SD determination of average carbon numbers. The results
indicated better agreement with mass spectral methods upon increased
chromatographic resolution.
Finally, as an intricate part of this project, the developed
GC/MS/HTA method was documented in the standard ASTM format which was
to be utilized by the Pratt and Whitney engineers of the Fuels
Division. A duplication of the ASTM standardized GC/MS/HTA method is
shown in Appendix D.


CHAPTER IV
PRELIMINARY INVESTIGATIONS OF ALTERNATIVE IONIZATION
TECHNIQUES FOR JET FUEL ANALYSIS
The primary goal of this area of study was to investigate
alternative ionization techniques in mass spectrometry for the analysis
of jet fuels. These studies will cover aspects of both hydrocarbon
type analysis and total fuel analysis. The combination of high
resolution gas chromatography and alternative ionization techniques
such as low-energy electron ionization and methane chemical ionization,
will be a powerful tool for the determination of specific components in
jet fuels.
Background
Low Energy Electron Ionization
The main effort in the application of low energy electron
ionization GC/MS is to evaluate a technique for the specific detection
of aromatic type compounds in jet fuels. Studies have been reported
(31,53,59) on the determination of specific aromatic components in
fuels and coal-derived liquids by such methods. Aromatic compounds
have a lower ionization potential than aliphatic molecules which allows
for the selective ionization of aromatics in the presence of aliphatics
(53).
90


91
In the present study the utilization of GC separation, combined
with the specific detection of aromatics, is demonstrated as a
potential method for the determination of specific aromatic components
in jet fuels. A method such as this would contribute to the
development of a total fuel analysis method which was previously
discussed.
Methane Chemical Ionization
The main effort in the application of methane chemical ionization
(Cl) GC/MS to the analysis of jet fuels was to demonstrate the
potential of the technique as a new method for hydrocarbon type
analysis. Much work has been reported on the analysis of fuels and
other coal derived liquids using CI/MS (53-58) for the determination of
specific fuel components and specific classes of components. With
chemical ionization, a large array of specific ionization schemes are
available by choosing an appropriate Cl reagent gas. Harrison (52) in
his book on chemical ionization mass spectrometry, discusses in detail
the fundamentals, instrumentation, and applications of CI/MS. In
general terms, the ionization specificity in CI/MS is obtained by the
specific reactions and energetics encountered by the ionized reagent
compound and the analyte. For example, in positive methane CI/MS
(which is used in this study) a methane molecule is first ionized to
CH4+ (and CH3+, CH2+, etc.) by electron impact ionization. Collisions
of these ions with another methane molecule leads to proton transfer to
form CH5+. This process continues to form higher m/z ions such as
C2H5+. Only those analytes with a higher proton affinity than CH4 and
C2H4 (the conjugate bases of CH5+ and the C2H5+ ions) will be ionized.


Full Text
ADVANCED MASS SPECTROMETRIC METHODS
OF JET FUEL ANALYSIS
BY
MICHAEL JOE GEHRON
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1988

To the Glory of GOD
whose grace through Jesus Christ
has brought me here and is taking me there.
To 0. Dean Martin
Minister of Trinity United Method Church of Gainesville
whose teachings and courage has been an inspiration in my life.
To the "Original Little Leaguer"
Harold "Major" Gehron
who passed away on November 15, 1987.
To Mom and Dad

ACKNOWLEDGEMENTS
I would like to thank ray research director and friend Richard A.
Yost for the great discussions, time and effort he put into the
preparation of this research and dissertation. I would also like to
thank him for making my graduate career at the University of Florida
quite enjoyable.
I sincerely thank Gerhard M. Schmid and James D. Winefordner for
seeing me through till the end. Special thanks go to Joseph J. Delfino
and Kirk S. Schanze for also serving on my committee and reviewing this
work.
I would like to thank the entire group for making me feel at home
after the big switch. Special thanks go to Jodie Johnson, Mike Lee,
Ken Matuzsak, Todd Gillespie, Randy Pedder, and Mark Hail for all their
help; I mean all their help.
Special thanks go to a special friend, Bill Davis.
Thanks go to Dave White who taught me to do it rather than sit
around and theorize on the outcome.
I love my wife Cheryl, my little Laura, and the Bun in the oven.
They are what its all about.
iii

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
ABSTRACT vii
CHAPTERS
I INTRODUCTION 1
Objectives 1
Background 2
Type Analysis 2
Total Fuel Analysis 5
History and Reviews of Hydrocarbon Type Analysis 5
Specifications of Jet Fuels 9
Instrumental Methods of Analysis 14
Sample Introduction 14
Short Column GC/MS and Simulated Distillation 15
Long Column GC/MS for TFA 16
Ancillary Jet Fuel Analysis Techniques 17
Alternative Ionization Methods 17
Mass Spectrometry/Mass Spectrometry 18
Outline of Thesis 19
II EXPERIMENTAL 21
Materials 21
Apparatus 22
Mass Spectrometry 22
Gas Chromatography Conditions 22
Other Gas Chromatography Studies 23
Data Handling Techniques 24
Clarification of ASTM D-2789 24
Computer Hardware and Software 28
Ion Summation Chromatography 28
Simulated Distillation for Determining
Numbers 30
Occupational Hazards 30
iv

III GAS CHROMATOGRAPHIC/MASS SPECTROMETRIC HYDROCARBON TYPE
ANALYSIS 32
GC Sample Introduction 32
Ancillary Short-Column Experiments 40
Analytical Figures of Merit 42
Characterization of the GC/MS/HTA Method 48
Comparison of ASTM and GC/MS/HTA Results 48
Simple Mixture Analysis 52
Inverse Calibration Matrix Variation 60
Evaluation of Olefin and Cycloparaffin Isomers 69
Evaluation of Methods for Average Carbon Number
Determinations 78
GC/MS Simulated Distillation 79
Comparison Between GC/MS/SD and GC/MS/HTA 83
Comparison Between GC/MS/HTA and ASTM 83
Effect of Chromatographic Resolution on Carbon
Number Calculations 86
Summary of Results 87
IV PRELIMINARY INVESTIGATIONS OF ALTERNATIVE IONIZATION
TECHNIQUES FOR JET FUEL ANALYSIS 90
Background 90
Low Energy Electron Ionization 90
Methane Chemical Ionization 91
Experimental 92
Electron Energy Variation 92
Methane Cl 92
Results and Discussions 93
Low Energy Electron Ionization 93
Methane Chemical Ionization 97
Summary of Results 101
V PRELIMINARY INVESTIGATIONS OF GC/MS/MS TECHNIQUES
FOR JET FUEL ANALYSIS 104
Background 104
Mass Spectrometry/Mass Spectrometry 104
Application of GC/MS/MS to Jet Fuel Analysis 105
Experimental 107
Results and Discussion 108
MS/MS for Hydrocarbon Type Analysis 108
Other GC/MS/MS Modes of Analysis 115
Differentiation of Isomeric Hydrocarbon
Types 117
Summary of Results 124
v

VI CONCLUSIONS AND FUTURE WORK 126
Summary of Results 126
Hydrocarbon Type Analysis 126
Calculation of Average Carbon Number 127
Ancillary Mass Spectrometric Methods 128
APPENDICES
A MATRIX INVERSION METHOD 130
B EXAMPLE GC/MS/HTA CALCULATION 131
C GC/MS/HTA TURBO BASIC PROGRAM CODE 136
D PRELIMINARY TEST METHOD FOR HYDROCARBON TYPE ANALYSIS
OF JET FUEL BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY .. 146
BIBLIOGRAPHY 155
BIOGRAPHICAL SKETCH 160
vi

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
ADVANCED MASS SPECTROMETRIC METHODS
OF JET FUEL ANALYSIS
BY
MICHAEL JOE GEHRON
April, 1988
Chairman: Richard A. Yost
Major Department: Chemistry
Hydrocarbon type analysis (HTA) is widely used to evaluate the
chemical composition of petroleum and shale-derived products, such as
jet fuels. The HTA methods provide a knowledge of the macro¬
composition of the jet fuels which is important in engine design and
performance. Presently the methods used for HTA of jet fuels are
limited by the boiling point range of the analysis and the
instrumentation requirements. The HTA method for gasolines (used for
jet fuels), American Society of Testing and Materials standard test
method D-2789, was developed in the mid-1950s on magnetic sector mass
spectrometers which are no longer commercially available.
A gas chromatography/mass spectrometry (GC/MS) method has been
developed for the hydrocarbon type analysis (HTA) of jet fuels. The
method employs a short-column capillary (3 meters) which is interfaced
directly into a Finnigan TSQ45 tandem mass spectrometer. Advantages
vii

of this method include employment of present day GC/MS instrumentation
and simple GC sample introduction. Additionally, a simulated
distillation profile may be obtained based on specific hydrocarbon
types which allows for the determination of more accurate average
carbon numbers of each hydrocarbon type. The results of the HTA on a
series of fuels and synthetic fuel mixtures will be reported along with
a complete characterization of the GC/MS/HTA method and results. The
results and methodology of the GC/MS simulated distillation method for
average carbon numbers will be reported.
A preliminary investigation of alternative MS techniques for jet
fuel analysis has been performed for the development of methods for
total fuel analysis (TFA) (determination of 95% of all components
present at 0.05% weight or greater). These techniques include
alternative ionization techniques such as low energy electron
ionization and methane chemical ionization; and tandem mass
spectrometry techniques such as daughter scan MS and parent scan MS.
The application and results of these techniques will be presented in
regards to the HTA and TFA of jet fuels.
viii

CHAPTER I
INTRODUCTION
The need to understand the chemical composition of aviation fuels
has never been more important than in the last decade. This need stems
from two important aspects: the recent world-wide shortages of
petroleum crude reserves which have resulted in a transition to
alternative crude sources; and the desire to design and operate high
performance jet engines with the knowledge of fuel composition as a
controlling criterion. This has led to a resurgence in the development
of new analytical techniques for petroleum analyses and more
specifically aviation fuel analyses. In this laboratory investigations
are presently underway for the application of gas chromatography/mass
spectrometry (GC/MS) and GC/MS/MS for analysis of aviation fuels (in
particular turbine jet fuels). There are two modes of analysis of
interest, hydrocarbon type analysis (HTA) and total fuel analysis
(TFA). The concept of each application will be discussed below.
Objectives
This research project is organized around two goals. The first is
to develop, implement, and characterize a gas chromatography/mass
spectrometry (GC/MS) hydrocarbon type analysis (HTA) for jet fuels.
1

2
These fuels represent a specific boiling point fraction or range of
components of crude oil. The second goal is to begin preliminary
investigations into the development of a GC/MS method for total fuel
analysis (TFA) (determination of 95% of all components present at 0.05%
weight or more) of these jet fuels. Vast differences in
chromatographic separation will be required in these two tasks. The
ability to integrate the two methods with one instrumental
configuration (GC/MS) is a goal of significant importance.
Background
This section will discuss the idea of type analysis or more
specifically hydrocarbon type analysis of fossil fuels and the need and
significance of new methods. Total fuel analysis will also be
discussed illustrating the need for specific detection systems.
Type Analysis
The concept of "Type Analysis" is not widely known among analytical
chemists. One may ask, "what type (of) analysis did you perform on the
samples?" And one may reply, "a type analysis was performed on the
samples." Thus the confusion begins. Type analysis in general does
not provide information on specific individual components in a mixture
but rather supplies information on the relative amounts of certain
classes of compounds. In many applications the quantitation of
specific compounds is not required and may provide much more
information then is actually desired. This is particularly true in
cases where the analyst is only interested in the overall macro¬
composition of a very complex mixture. The type analysis of

3
hydrocarbon mixtures, such as gasoline and heavier oils, represents
such an application of type analysis. Hydrocarbon type analysis is a
widely used procedure for the evaluation of petroleum feedstocks and
other complex mixtures. In 1951 Ralph Brown of the Atlantic Richfield
Corporation developed the first mass spectrometric technique for
Hydrocarbon Type Analysis (HTA) (1). The Brown method operates on the
premise that certain classes of compounds or homologous series, for
example paraffins, form a specific series of fragmentation ions in the
electron ionization source of the mass spectrometer. In this example
the paraffins form the series of mass fragments 43, 57, 71, 85, and 91.
Not all species of this series form all or only these ions. Similarly
the paraffin series is not the only class or homologous series of
compounds which contain any of these ions. Therefore an extensive
calibration scheme is required to normalize for this mixing of
fragmentation series between hydrocarbon types. Details of the present
method will be discussed in Chapter II, Clarification of ASTM D-2789.
Since the Brown method, there have been numerous improvements on his
method due to improved calibration schemes (2,3), and improved
instrumentation (4,5). In 1962 standard Hydrocarbon Type Analysis
methods for gasoline (6) and diesel fuels (7) were adopted into the
American Society of Testing and Materials (ASTM) standards. There have
been several revisions of these methods over the years, but the basis
of the methods remains the same. The methods, ASTM D-2789 and D-2425,
perform the analysis on magnetic sector instruments which are no longer
in commercial production. Because of this limitation, there is a much
greater demand for samples to be analyzed than there are laboratories

4
equipped to perform them. Additionally, the means of sample
introduction into the mass spectrometer, which is via a heated glass
inlet volume or microburette, is a time-consuming procedure and
facilitates component discrimination (8). The technique also relies on
manual measurements of peak height intensity which eliminates the
ability to computerize the calculations. Consideration of these
limitations illustrates the need for a modern HTA method performed on a
widely available modern instrument.
At the 1987 meeting of The American Society of Mass Spectrometry
in Denver, the ASTM committee on petroleum analyses (9) expressed
interest in the development of new and/or improved methods of HTA in
the fuels area. Presently several methods are used for hydrocarbon
type analysis such as the fluorescent indicator adsorption (FIA)
procedure which covers the determination of saturates, non-aromatic
olefins, and aromatics (10). Limitations of this method include long
analysis time (3-4 hours per sample) , poor precision, and lack of
automation capabilities. Limitations of these methods led to the
development of several liquid chromatographic methods (11), but
limitations of these methods include the inability to separate and
quantitate enough classes. With the development of a GC/MS/HTA several
advantages would be realized. First, convenience in instrumentation,
since most modern analytical laboratories are equipped with a GC/MS,
many laboratories will be able to perform the analysis, and the sample
load will be decreased. Second, GC introduction will provide improved
sample introduction techniques which are more convenient and less prone
to component discrimination. Additionally, the use of chromatography

5
will provide information such as distribution of components as a
function of boiling point and make possible the extension of the method
to total fuel analysis by increasing the chromatographic resolution.
Total Fuel Analysis
The concept of total fuel analysis (TFA) is one to which most
analytical chemists may relate. The objectives are to quantitatively
determine specific components or classes of components of jet fuel.
One must be knowledgeable of the complexity of jet fuels to appreciate
the formidable task at hand. A typical jet fuel may contain from 400
up to 4000 individual components. Davis and Giddings (12) and Martin
and co-workers (13) have shown theoretically that, in order to
chromatographically resolve 90% of the components in a 100 component
mixture, 20,000,000 theoretical plates would be required. Considering
a standard capillary GC column of 0.25 mm i.d. and 0.25 /jm thickness, a
column length of 5 km or 3 miles would be required for such an
analysis. This theoretical calculation merely illustrates the need for
more selective detection methods which could utilize normal high
resolution chromatography.
History and Reviews of Hydrocarbon Type Analysis
Discussions on the history of HTA of petroleum-derived mixtures
such as fuels will quickly lead one to a general discussion of the
early history and development of mass spectrometry. The impetus for
early mass spectrometry research was generally fueled by the petroleum
industry and the war-time demands on the industry to supply aviation
fuels of superior quality with good quality control and assurance.

6
Recently there have been several review articles which deal
specifically with this history (14,15). The Consolidated Engineering
Corporation (CEC) enjoyed the first commercially successful mass
spectrometer (CEC Model 21-101) which became the prototype instrument
which was be utilized by Ralph Brown (1) in the first mass
spectrometric HTA of gasoline mentioned above.
There have been many methods developed in the past for the
determination of hydrocarbon types in gasolines and fuels. Some of
these methods relied on rather laborious and time-consuming
separations, chemical reactions, and physical determinations. One
procedure developed by Kurtz et al. (16) required 24 man-hours for
fractionation, chemical treatment and determination by refractive
indices. Rampton (17) employed distillation, silica gel percolation,
hydrogenation, and measurements of refractive indices for the
determination of paraffins, cycloparaffins, aromatics, olefins, and
cycloolefins. The first applications of mass spectrometry to
hydrocarbon fractions were to the analysis of gaseous mixtures (18).
Later, with the advent of improved mass spectrometers and inlet
systems, the analysis of the lower-boiling fraction of gasolines was
performed (19-21). In 1951 Ralph Brown introduced the HTA method for
gasolines which represented a new concept and application of mass
spectrometry. The application of MS HTA soon expanded to the analysis
of heavier fractions such as kerosene and heating oils (2,22). At this
time O'Neal and Wier (4) and Brown et al. (23) independently described
an improved all-glass heated inlet system which would not only expand
the boiling point range of MS analysis even greater, allowing for the

7
analysis of waxes and other low vapor pressure compounds, but also
improve the precision and accuracy of the method as a whole. Of
particular interest at that time was more in-depth analysis of the
aromatic fractions of these complex heavier mixtures (24-27). Previous
to these MS techniques, little was known of the chemical make-up of
such aromatic fractions. From the middle 1950s, which may be regarded
as the end of the rapid growth period of mass spectrometry research in
the applications of petroleum-derived mixtures, there have been very
few publications appearing in the literature. However, with the advent
of high resolution mass spectrometers in the early 1960s, there was an
additional surge of interest in MS techniques for the analysis of
petroleum-derived complex mixtures (28-31). Traditionally, the major
use of high resolution MS was for the identification and structural
determination of pure compounds or major components of a simple
mixture. Since heavier petroleum fractions contain such a large
variety of compounds compared to lower boiling fractions such as
gasoline, a single low resolution mass spectrum cannot be interpreted
in terms of hydrocarbon types. The high resolution MS techniques could
single out each hydrocarbon type based on the exact mass of the
fragment ions and/or molecular ions. The classification scheme became
known as the "Z number" classification based on the formula CnH2n+z
where z is a number which represents the degree of unsaturation and/or
ring closure and signifies the hydrocarbon type. A more extensive
discussion on "Z number" classification may be found in the paper by
Teeter (29) which introduces an improved high resolution MS hydrocarbon
type analysis for 22 hydrocarbon types. This method determines the

8
relative amounts of eight types of saturates, ten types of aromatics,
and four types of sulfur-containing aromatics. In addition to high
resolution techniques a number of low resolution techniques began to
appear in the literature. The Robinson and Cook method (32) followed
by the Amoco method (26) took advantage of the appearance of saturate
fragments at lower masses and aromatic fragments at higher masses.
This enabled the spectra to be subdivided into a saturate and aromatic
region allowing mathematical treatment and normalization. The
elemental analysis, carbon number distribution, average molecular
weight, and the general aromaticity of coal-derived distillates were
determined by the combination of low-voltage, high resolution MS (33).
Other analytical techniques apart from MS techniques have been
utilized in the pursuit of a suitable HTA of fuels and other complex
petroleum mixtures. Based on the classic silica gel separation of
saturates, olefins, and aromatics, new high performance liquid
chromatographic methods have been developed which utilize silver-coated
silica gel particles and n-pentane mobile phases (34). Separation of
saturates, single ring aromatics, double ring aromatics, and
polynuclear aromatics was obtained for olefin free kerosenes and diesel
fuels using bonded aminosilane stationary phases (35) . An excellent
review is available on the application of HPLC and GC to hydrocarbon
group analysis (36-38). Most recently several workers have evaluated
supercritical fluid chromatography (SFC) for the separation of
hydrocarbon types (39). Separation of paraffins, olefins, and
aromatics was obtained in two reports; using SFg mobile phase, pressure

9
programming, and FID detection (40); and using silver nitrate
impregnated silica gel stationary phases with CO2 mobile phase and
refractive index detection (41). Combination of SFC with MS shows
great promise for future applications to fuels analysis.
Specifications of Jet Fuels
With the world-wide shortage of conventional high quality crude
oils, there has been a dramatic decrease in the availability of jet
fuels. As a result of this shortage, the industry has experienced a
transition from petroleum sources towards utilization of alternative
sources such as oil shale, tar sands, coal liquid, and heavy oils for
the production of jet fuels. Additionally fuels are being synthesized
by blending various refinery streams and mixing of pure compounds.
This shift has created increases in processing cost as well as many
uncertainties in market stability. More importantly here, new unknowns
have been generated in the physical and chemical characteristics of
these new source fuels. Recently it has become more important in the
design and operation of jet engines to be able to correlate the
physical parameters of jet fuels with their chemical composition. With
the addition of these new source fuels, there is a need for new and
improved physical and chemical methods of jet fuel analysis.
Traditionally the determination of the physical parameters of jet fuels
has been the focus of jet fuel analysis. Table 1.1 lists some of the
more common physical parameters determined for jet fuels (42). The
importance of a few of these parameters is as follows: thermal

10
Table 1.1
List of Important Physical Parameters Determined for
Aviation Fuels and the Corresponding ASTM Methods Used
Physical Parameter Test ASTM Method
Volatility
Distillation
Specific Gravity
Vapor Pressure
D- 86
D-287
D-328 , D-2551
Fluidity
Freezing Point
D-2386
Combustion
Heat of Combustion
Aniline-Gravity Product
Knock Rating: Lean Fuel
Rich Fuel
D-240, D-2382
D-611, D-287
D-2700
D-909
Corrosion
Copper Strip Test
D-130
Stability
Potential Gum
Precipitate
D- 873
D- 873
Contaminants
Existent Gum
Water Reaction:
Interface Rating
Volume Change
D- 381
D-1094
D-1094
Additives
Tetraethyllead Content
Dye Content
D-3341, D-2599 , D-2547
D-2392

11
stability is important since jet fuels are exposed to extremely high
temperatures and minimal decomposition is desired; viscosity of fuels
as a function of temperature is important since the fuels must remain
fluid in flights where
the
fuels are
exposed
to
extremely low
temperatures in storage;
the
density of
fuels
(or
the volumetric
energy) determines the ultimate range in miles of the aircraft. For
more information on any of the specifications listed in Table 1.1,
refer to the appropriate reference listed. Most methods used in the
determination of the above mentioned physical parameters are ASTM
standard methods and represent important contributions to fuel and jet
engine research.
As mentioned above, the specifications of jet fuels are based
mainly on the physical parameters or usage requirements. The single
composition requirement common to all aviation fuels is they must
consist almost completely of hydrocarbon compounds. There are specific
limitations on particular hydrocarbon types such as aromatics and
olefins due to performance criteria. Additionally, low level additives
may be present as well as low level contaminants of various sorts.
Jet fuels or more specifically turbine jet fuels are made up of
hundreds of hydrocarbons that may be divided into four subgroups or
hydrocarbon types: paraffins and isoparaffins (branched paraffins);
cycloparaffins or naphthens; aromatics; and olefins. The former two
types make up the saturates and the latter two types the unsaturates.
Figure 1.1 illustrates some example compounds of each hydrocarbon type.
Paraffins and cycloparaffins are generally the major type component
of jet fuels. The paraffins are the most stable components and do not

12
Paraffin
ch3
CH3(CH2)nCHCH3
Monocycloparaffin
isopropyl-cyclohexane
Dicycloparaffin
decal in
Alkylbenzene
ethylbenzene
'â– 'u CH
3
Indane/Tetralin
Naphthalene
2-methyl naphthalene
CH3
Figure 1.1.
Structures of some example compounds representative of
the six hydrocarbon types. Some specific examples are
also shown.

13
readily react with materials in which they come in contact with such as
elastomers, paints, and various metals. They are clean-burning
compared to other hydrocarbons and have a very high heat release per
unit weight. Both of these advantages are due to the high hydrogen-to-
carbon ratio. Cycloparaffins have a lower hydrogen-to-carbon ratio
which lowers their heat release per unit weight, but increases their
density or volumetric energy. Cycloparaffins are also clean-burning
and stable and have a lower freezing point compared to paraffins of
equal carbon number.
Aromatics are fully unsaturated ring structures which may also
incorporate saturated structures. Because of the very low hydrogen-to-
carbon ratio, they have a much greater volumetric energy but a lower
heat release per unit weight than the paraffins. The aromatics are
reactive and tend to cause swelling of rubber seals. They produce
large amounts of smoke while burning, and a high-luminosity flame.
This particular aspect is important when considering secret
reconnaissance missions of the Armed Forces. Because of these factors
the maximum concentration of aromatics permitted in jet fuels is 20-25%
Virgin fuels generally contain no more than 10-20% aromatics.
Olefins are the most reactive hydrocarbon types and are capable of
reacting with many materials. They react with air to form varnishes or
rubber-like materials. They can dimerize or polymerize forming high
molecular weight contaminants. Because of their high reactivity,
olefins are generally not found in natural or virgin crudes. They may,
however, be formed in the refinery cracking processes. Specifications

14
limit the content of olefins to less than 5 percent in order to reduce
varnish and gum formation.
Other non-hydrocarbon types which may be found in aviation fuels
include heteroatomic species such as sulfur-, oxygen-, and nitrogen-
containing compounds. These include mercaptans, sulfides, thiophenes,
and free sulfur as example sulfur types; alcohols and naphthenic acids
as example oxygen types; and aza and amino polynuclear aromatics as
example nitrogen types. Combinations of these contaminants tend to
form high molecular weight gums and deposits when exposed to air during
storage. This creates many problems such as filter clogging, sticking
of valves, and plugging of orifices. Additives present which help to
eliminate some of these problems include antioxidants, metal
deactivators, fuel icing inhibitors, and corrosion inhibitors.
Instrumental Methods of Analysis
Sample Introduction
The utilization of GC/MS techniques can provide more up-to-date
methods of sample introduction into the mass spectrometer. This is a
direct advantage over the traditional ASTM methods, in which a heated
glass inlet or microburette is employed, and the sample is introduced
by effusion through a small orifice. A small fraction of the total
sample is analyzed with the microburette technique, in order to
minimize component discrimination which increases as the effusion of
the sample into the mass spectrometer proceeds. The method is time-
consuming and requires the maintenance of many instrumental parameters.
The GC/MS technique will vaporize the entire sample and analyze the

15
entire volume which has been loaded onto the column. Because of the
possibility of component discrimination during sample loading onto the
GC column, component discrimination must be evaluated as a function of
injection port temperature and injection techniques.
Short Column GC/MS and Simulated Distillation
An important concept of this HTA method is that chromatographic
resolution of the jet fuel components is not a matter of pursuit.
Trehy, Yost, and Dorsey (43) have discussed some of the important
instrumental considerations of normal GC/MS using short capillary
columns. In the GC/MS/HTA application of short capillary columns, the
GC is mainly used as a convenient device for sample introduction into
the mass spectrometer. The short columns, along with providing short
analysis times, provide the ability to observe the distribution profile
of the eluting jet fuel as function of column temperature. This
concept is similar to that of simulated distillation (44,45) which has
been utilized by the petroleum industry for many years to provide a
breakdown of the boiling point distribution of the hydrocarbon mixture.
The area percent of the eluting fuel is determined at various points
along the profile or chromatogram. Each area percent corresponds to a
specific retention time or boiling point. These boiling points are
determined by a parallel eluting sample of n-paraffin homologous series
in which the boiling points are known. A non-polar column must be
employed to assure the correlation of retention to boiling point. The
temperature corresponding to the 50 percent area point corresponds to
the average boiling point of the fuel. This is a useful physical
parameter, although the extraction of an average carbon number from the

16
results is not accurate. Application of GC/MS, however, can provide
not only average boiling points but also average carbon number. This
is provided by the ability of the mass spectrometer to distinguish
between hydrocarbon types within the fuel mixture. Corresponding
homologous series may be compared to the corresponding ion summation
chromatogram of the particular hydrocarbon type and an average carbon
number may be obtained. These experiments represent an important
advancement in the development and understanding of hydrocarbon type
analysis.
Long Column GC/MS for TFA
The quest for a GC/MS technique for TFA will require high
resolution (long-column) capillary gas chromatography. Since only a
select number of chromatographic peaks will be pure components,
additional selectivity in addition to chromatographic resolution will
be required. Many researchers have reported work in the fuels area
with chromatography alone (46,47). Here the application of MS, which
includes various modes of ionization, and MS/MS will be evaluated for
means of chromatographic peak deconvolution. There have been numerous
reports in the literature which have applied GC/MS techniques to fuel
analysis. Gallegos (48) has described a high resolution GC/MS method
for the analysis of a shale derived oil. Aczel has determined compound
type distribution in refinery streams and synfuels using GC/MS (49) .
The compound distribution of a jet fuel has been determined by
recombination of separately determined components using GC/MS (50).

17
Ancillary Jet Fuel Analysis Techniques
The development of GC/MS methods for total fuel analysis (TFA) will
require the utilization of ancillary MS techniques such as low-energy
electron ionization, chemical ionization, and MS/MS techniques. These
techniques, when combined with chromatographic separation, will provide
specific detectors for the deconvolution of multicomponent
chromatographic peaks discussed earlier. The following is a review of
the application of such MS techniques.
Alternative Ionization Methods
Chemical ionization (Cl) (51) is a softer ionization technique
which is capable of producing an increased abundance of molecular ion
and minimal fragmentation compared to conventional electron ionization
(El). Harrison discusses the use of CIMS with various reagent
compounds for the characterization of hydrocarbons (52). Although
there have been significant applications of Cl to the characterization
of single classes of compounds in fuels and other complex mixtures,
there have been no known publications on the application of Cl to an
overall hydrocarbon type analysis of jet fuels. Sieck characterized
gasolines for their aromatic content using low-energy photoionization
cyclohexane Cl (53). Sieck, Burke, and Jennings (54) used N2O Cl for
screening of aviation fuels. The OH' ion was employed for negative ion
Cl, which eliminated ionization of aliphatic compounds. Other
applications of CIMS have been devoted to the determination of
polynuclear aromatic hydrocarbons (PAH) in fuels (55) , as well as aza
and amino PAH in coal derived liquids (56). Negative ion ammonia Cl
GC/MS has been used for the quantitation of sulfur-containing compounds

18
in gasoline (57). Bauer, Schubert and Enke (58) used methanol Cl for
the characterization of heterospecies in the presence of hydrocarbons.
The essential aspect of Cl GC/MS techniques in regard to total fuel
analysis is the ability to deconvolute co-eluting components of the
fuel. In the current research only methane chemical ionization is
evaluated.
Electron ionization (El) is considered the work-horse of mass
spectrometry. One aspect of EI/MS which is rarely explored in
petroleum analysis is the utilization of low-energy El. Since various
compound types have different ionization potentials, these differences
may be utilized as a source of compound-type discrimination. One of
the earliest applications of low-energy ionization MS (referred to as
low-voltage MS) was the determination of the unsaturated hydrocarbon
fraction in a petroleum naphtha (59). In this method only molecular
ions of the unsaturated species are formed, thus eliminating saturate
interferences. Aczel and Johnson utilized low-energy electron
ionization in conjunction with high resolution MS for the analysis of
aromatic fractions of complex petroleum mixtures (31). As mentioned
above, low energy photochemical ionization was used for the analysis of
aromatics in gasoline (53). The use of low-energy electron ionization
GC/MS is evaluated here for the characterization of separate
hydrocarbon classes. This technique and its usefulness will be
discussed.
Mass Spectrometry/Mass Spectrometry
Mass spectrometry/mass spectrometry (MS/MS) is quite useful for the
direct analysis of complex mixtures such as coal derived liquids.

19
Recently there have appeared in the literature many applications of
MS/MS to the analysis of complex petroleum mixtures (56,58,60-71).
There exist two MS/MS instrumental techniques which are generally used,
mass-analyzed ion kinetic energy spectrometry (MIKES) (72,73) and
triple quadrupole mass spectrometry (TQMS) (74). To date, no known
application of MS/MS to HTA of fuels has appeared in the literature;
however, as with Cl applications, most MS/MS applications have been
dedicated to the determination of a single class of compounds or a
single component. In the current research, several aspects of TQMS
have been evaluated for possible HTA methods or TFA methods of jet
fuels. These results will be discussed along with the possibility of
combining MS/MS with alternative ionization techniques.
Outline of Thesis
The remainder of the thesis is divided into five chapters. Chapter
II, Experimental, will describe all experimental, instrumental, and
computational techniques. Chapter III, Gas Chromatography/Mass
Spectrometry/Hydrocarbon Type Analysis, will contain experimental
results and discussions based solely on the development,
implementation, and characterization of the GC/MS/HTA method. Chapter
IV, Alternative Ionization Techniques, will contain results and
discussions on the use of these techniques in the application of TFA
and HTA of jet fuels. Chapter V, Gas Chromatography/Mass
Spectrometry/Mass Spectrometry, will contain results and discussions on
the use of GC/MS/MS in the application of TFA and HTA of jet fuels.

20
Finally Chapter VI, Conclusions and Future Work, will summarize the
total effort and describe suggested future work. As in any research
effort each question answered brings about several new questions. This
project is no exception.

CHAPTER II
EXPERIMENTAL
The following chapter will discuss the experimental parameters
which are involved in the development, characterization, and
implementation of the hydrocarbon type analysis of jet fuels. The
experimental parameters which deal specifically with studies in total
fuel analysis, such as chemical ionization and MS/MS will be discussed
in those specific chapters. The general experimental parameters, such
as materials, jet fuel preparation, and instrumentation will also be
discussed here.
Materials
All chemicals were ACS grade unless otherwise specified and were
used as received without further purification. Standards were
purchased from various vendors and were used as received without
further purification. All jet fuel samples were obtained from Pratt &
Whitney-Fuels Division, West Palm Beach, Florida. The fuels were
shipped at ambient temperatures without refrigeration in vials with
screw-cap or crimped cap teflon-lined replaceable septa. After every
use in the laboratory, the septa were replaced with new ones and
samples were refrigerated at 5 C.
21

22
Apparatus
Mass Spectrometer
A Finnigan MAT TSQ45 gas chromatograph/triple - stage quadrupole mass
spectrometer/data system was used in all GC/MS studies. An electron
energy of 70 eV and an electron current of 300 /iA were used. The mass
spectrometer was mass calibrated with FC43 (perfluorotributylamine) in
accordance with the instrument's specifications. The mass spectrometer
was tuned, also with FC43, to obtain a specific ion intensity ratio of
m/z 69 to m/z 219, and m/z 502 to m/z 220. These ratios were monitored
to insure reproducible relative abundances of the fragmentation pattern
in regards to instrumental tuning alone. The low mass ratio is of
greater importance in these studies since this is the general mass
range in question. The mass spectrometer was scanned from 35 to 650
amu at a total scan time of 1.0 s. The electron multiplier was
operated between 950 and 1000 V, with the conversion dynodes at ±3000
O
V. The preamplifier gain was set at 10° V/A with the fine adjustment
(zeroing) set for minimal acquisition of baseline noise. The mass
spectrometer was interfaced to a Finnigan Model 9610 gas chromatograph.
All GC operations were under computer control. The capillary GC
columns were inserted directly into the ion source of the mass
spectrometer through a heated interface. The ion source pressure was
0.3-0.6 Torr depending on the column head pressure. The ion source
temperature was 190 C.
Gas Chromatography Conditions
A 3 m DuraBond fused silica bonded phase open tubular (capillary)
column (J&W, Rancho Nuevo, CA) with an inner diameter of 0.25 mm and a

23
DB5 bonded phase (SE-54 equivalent or 5% phenyl-methyl silicone) of 1.0
nm thickness was operated at a head pressure of 8 pounds per square
inch of helium carrier gas. Split-type injection was used with a split
flow of 50 mL/min and a septum sweep of 2 mL/min. The injection port
temperature was 250 C and the transfer line was 280 C. The injection
port teflon lined septum was replaced after 30 - 40 injections and the
injection port glass insert was checked frequently and cleaned whenever
needed. The column temperature was programmed from 50 C to 250 C at 15
C/min after a hold time of 1 minute. Usually the column would not
require the full temperature to elute the entire jet fuel sample.
Generally 0.5-1.0 injections of neat jet fuel samples were made.
The injection technique used was as follows in order to reduce
injection error: the GC injection syringe (Hamilton) was thoroughly
rinsed between samples with hexane, followed by the sample jet fuel of
interest; the sample volume was pulled up from the needle volume into
the syringe volume; the needle was inserted into the GC injector; a
count of three allowed the needle to come to equilibrium temperature;
the sample was injected at a rate of approximately 1 /¿L/s; this
position was held for a count of three and the needle was removed.
This method decreases injection discrimination due to uneven heating of
the needle and components contained therein (75,76).
Other Gas Chromatographic Studies
Besides GC/MS, studies involved the application of GC with flame
ionization detection. A Varian 3300 gas chromatograph was used with a
flame ionization detector (FID). The same chromatographic conditions
were used as stated above including the column head pressure. However,

24
although the column head pressures were equivalent for the two systems,
different flow rates would result due to the different exit pressures.
This instrument was used for the studies of component discrimination as
a function of injection port temperatures and injection modes (split,
splitless, and on-column). Acquisition of peak area, peak height, and
retention time was obtained with an IBM 9000 minicomputer and the IBM
CAPMC4 Chromatography Applications Program. Additionally, the FID
system provided two advantages: a continuous mode of detection which
resulted in more highly resolved chromatograms, and increased
sensitivity (compared to full scan MS) which when combined with high
resolution gas chromatography (longer columns, 30 meters) would
demonstrate the extreme complexity of the jet fuels.
Data Handling Techniques
This section covers aspects of the data handling and reduction
which proved to be a major effort in obtaining the stated goals.
Considering the hydrocarbon type analysis alone, the mathematical
computations were quite abstract and had to be figured out conceptually
before application could be made. Below, these computations will be
discussed, along with the hardware used and the software generated to
deal with them.
Clarification of ASTM D-2789
The purpose of this section is to clarify the computational aspects
of ASTM D-2789 standard test method (6), which is the computational
basis of the GC/MS/HTA method developed here. The ASTM method, as it
is referred to, determines the volume percent of six separate

25
hydrocarbon types in low olefinic gasolines: paraffins,
monocycloparaffins, dicycloparaffins, alkylbenzenes, indanes and
tetralins, and naphthalenes. Each hydrocarbon type is determined based
on a characteristic set of ions as shown in Table 2.1. The method also
calculates the average aromatic and average paraffinic carbon numbers
based on mass spectral data. Calculations are made based on the
inverse calibration tables shown in Table 1 of the ASTM D-2789 standard
method (6) and are dependent upon the average carbon numbers. It is
these aspects of the ASTM method, development and application of the
inverse calibration matrices, which require clarification. The
calculations are similar to six simultaneous equations with six
unknowns; however, the unknowns are made up of a complex array of
variables and the set of equations used are chosen based on two other
variables as well.
The inverse calibration matrices were prepared by determining the
values E43/T, E41/T, etc. for each hydrocarbon class mixture at each
carbon number, where T=E(E43+E41+E67+E77+E103+E128), the sum of all the
characteristic hydrocarbon sums (E) . The compositions of the
hydrocarbon class mixtures at each carbon number (up to carbon number
nine) used in these determinations are given in Table 3 of the ASTM
standard (6). Consider this example calculation of the inverse
calibration matrix for carbon number six: the E43/T, S41/T, E67/T, and
E77/T are determined for each of the three hydrocarbon type mixtures as
shown in the ASTM Table 3 under C6 blends. The results are given in
Table 4 of the ASTM standard (6) under the appropriate hydrocarbon type
and C6 listing along with the results for larger carbon numbers. For a

26
Table 2.1
The Characteristic Ion Summations Used For Each Hydrocarbon Type
in the Hydrocarbon Type Analysis
HYDROCARBON TYPE
MASSES OF EACH CHARACTERISTIC ION SUM (2) (m/z)
PARAFFINS
243 - 43+57+71+85+99
MONOCYCLOPARAFFINS
241 = 41+55+69+83+97
DICYCLOPARAFFINS
267 = 67+68+81+82+95+96
ALKYLBENZENES
277 = 77+78+79+91+92+105+106+119+120+133+134
147+148+161+162
INDANES/TETRALINS
2103= 103+104+117+118+131+132+145+146+159+160
NAPHTHALENES
2128= 128+141+142+155

27
given hydrocarbon type, all values (Z/T) are divided by the largest
value of that set. The numbers are arranged in a matrix in proper
order. All elements of the array are then multiplied by an appropriate
pressure sensitivity factor. Table 5 of the ASTM standard (6) gives
the pressure sensitivity factors for each hydrocarbon class and carbon
number. These values represent the instrumental response as a function
of microburette pressure. The means of measuring the amount of sample
introduced into the mass spectrometer was via this monitoring
procedure. The C6 matrix is then inverted after multiplication by the
pressure sensitivity factors. The methods used for inverting a 3x3 and
3x4 matrix (77) are shown in Appendix A; this procedure is best handled
by computer programs. The elements of the C6 matrix are then
multiplied by the corresponding liquid volume factors, also given in
Table 5 of the ASTM standard, which are an indication of the liquid
volume per unit pressure. The matrix values are then divided by 100
and are in units of volume/counts.
Examination of the elements of the inverse calibration matrices
reveals much information on the use of the table. The carbon number 6
matrix illustrates this quite well. A relatively large positive entry,
such as +0.009016 for Z43/T/paraffins, is a good similarity
coefficient, as expected since paraffins response will contain a large
abundance of 243 ions. Similarly, the -0.000003 for 277/T/paraffins
indicates a low similarity coefficient, which is also expected since
very little 277 ions will be present for paraffin compounds. The
inverse relationship of these numbers represent the normalization
function of the inverse calibration matrices described above. A

28
thorough evaluation of the application of the inverse calibration
matrices will not be made since the method is quite common in
multicomponent analysis problems. The method involves the
multiplication of a 1x6 matrix (a paraffinic 1x3 and a aromatic 1x3) to
a 6x6 matrix and normalizing the results to 100%. However, as
mentioned above, the matrix used is dependent upon the average carbon
number of the sample in question. Since an integral average carbon
number is rarely obtained, two inverses should be applied with weighted
results. An example calculation of the GC/MS/HTA method is given in
Appendix B.
Computer Hardware and Software
The GC/MS/HTA method required extensive computations once the mass
spectral data had been obtained. This is evident from the discussion
above which described the methods and complexities of the calculations
used. A series of TURBO BASIC programs was written to completely
automate these computations. Additionally, a terminal emulator program
(Persoft, Smarterm 240) was utilized for the direct transfer of data
from the MS data system to an IBM PC. The program used for calculating
the volume % results and the average carbon numbers is shown in
Appendix C. Other programs included an inverse calibration development
program for carbon number 6; and a program which translates the
emulator-captured data to usable format for the HTA program.
Ion Summation Chromatograms
The characteristic ion sums listed in Table 2.1 were plotted as
separate mass chromatograms. These mass chromatograms, as shown in
Figure 2.1, are referred to as ion summation chromatograms and

Reconstructed Ion Current
Figure 2.1
Paraffin
16016
Monocycloparaffin
44006
\
Dicycloparaffin
27040
Alkyl benzene
34368
Retention Time (min)
The ion summation chromatograms of each hydrocarbon type
with the relative areas of each for jet fuel JP-8X 2414.

30
represent the chromatogram of each ion sum listed in Table 2.1. The
area of each ion summation chromatogram was determined and normalized
to 100%. The area percents were then calibrated with the ASTM inverse
calibration matrices after determination of the average aromatic and
average paraffinic carbon numbers. All these calculations were done
automatically, as mentioned above.
Simulated Distillation for Determining Carbon Numbers
The application of ion summation chromatograms provided the
opportunity to investigate the average carbon numbers of the jet fuels.
Figure 2.2 illustrates how the average aromatic carbon number was
obtained using this method. The ion summation chromatogram represents
the aromatic ion series. After determination of the area centroid of
this chromatogram the line may be projected down to the chromatogram of
the corresponding homologous series. The value indicates the aromatic
average carbon number of the fuel. Variations were made using this
technique, such as combinations of ion summation chromatograms, as will
be discussed in the next chapter.
Occupational Hazards
As a final note, the occupational hazards of working with jet fuels
are quite evident considering the nature of these complex mixtures. It
should go without saying to avoid exposure to these materials by using
a well ventilated hood, wearing gloves, and keeping the samples in
properly sealed vials. The major concern of working with these fuels
is the effect of long term exposure. Many of the components in these
mixtures are fat-soluble and therefore bio-accumulation is likely (78).

130.0-1
31
i
i
Figure 2.2. The aromatic ion summation chromatogram of a jet fuel
JP-8X 2414 on a 3 meter DB5 column. The centroid of the
total area, indicated by the arrows, is referenced to the
alkylbenzene homologous series. The carbon number is
calculated to be 10.95.

CHAPTER III
GAS CHROMATOGRAPHIC/MASS SPECTROMETRIC
HYDROCARBON TYPE ANALYSIS
Characterization of the hydrocarbon type analysis (HTA) method was
performed by evaluation of simple and complex synthetic mixtures,
perturbation of jet fuels, and comparison of results to existing ASTM
results. The experiments performed were to determine the effects of
various instrumental and method parameters on the results of the HTA of
jet fuels. The results of these experiments, as well as the simulated
distillation method for the determination of average carbon numbers,
will be discussed.
GC Sample Introduction
With the application of gas chromatography (GC), a new method of
sample introduction into the mass spectrometer was used for HTA. It
was therefore important to evaluate the specifics of sample
discrimination with respect to this sample introduction technique.
There are several injection techniques used in capillary gas
chromatography. These are split and splitless, which depend on the
flash vaporization of the sample within a heated glass-lined injection
volume, and on-column injection which allows the sample to be loaded
directly onto the capillary column at ambient temperatures. Specifics
32

33
of these capillary GC injection techniques are discussed elsewhere
(75,76). An aromatic mixture containing C12, C14, C16, and C18
straight chain alkylbenzene in equal concentrations was used for the
evaluation of component discrimination. The effect of injection port
temperature and injection technique was evaluated. Figure 3.1 and
Figure 3.2 illustrate the effect of injection port temperature on
component discrimination for splitless and split injections,
respectively, with flame ionization detection. In both cases the
ratios of peak areas were normalized to the C14/C12 ratio at the 280 C
injection port temperature to help illustrate the matter of
discrimination. Both cases indicate component discrimination taking
place at lower temperatures by the ratios being lower. This was due to
less efficient vaporization of the heavier components at lower
temperatures, as was expected. As the temperature was raised, the
ratios increased and leveled off, indicating a lack of discrimination
and the absence of component decomposition at higher injection port
temperatures. A larger degree of discrimination takes place for the
higher carbon number alkylbenzenes, as indicated by the larger ratio
spread between the low and high injection port temperatures. The
splitless technique more clearly illustrates these trends. A minimum
injection port temperature of 250 C should therefore be maintained to
avoid component discrimination. These results also demonstrate the
improvement in reproducibility obtained using splitless injections over
that obtained with split injection technique. A similar evaluation of
component discrimination was performed on the GC/MS instrument. Figure
3.3 illustrates the results which are similar to those from the GC/FID

Normalized Peak Height Ratio
Injection Port Temperature (C)
Figure 3.1. Plot of injection port temperature versus area ratios of
C12, C14, C16, and C18 alkylbenzenes for splitless
injections on a 3 meter DB5 capillary column, with FID
detection.
4>

Normalized Peak Height Ratio
* 1.40
1.20 t
1.00 -
0.80 ~
0.60 ~
0.40 ~
0.20 ~
A
0
0.00
i ti i i i i i i | i i i i i i i i i | i i i i i i i i i | ri v i i i i i i | i i i i i i i i i | i
90 130 170 210 250 290
Injection Port Temperature (C)
Figure 3.2.
Plot of injection port temperature versus area ratios of
C12, C14, C16, and C18 alkylbenzenes for split injections
on a 3 meter DB5 capillary column, with FID detection.
co
l_n

Normalized Peak Height Ratio
Injection Port Temperature (C)
Figure 3.3. Plot of injection port temperature versus area ratios of
C12, C14, C16, and C18 alkylbenzenes for split injections
on a 3 meter UHb capillary column and MS detection.
w
o\

37
technique. However, discrimination effects are less with GC/MS, as
indicated by the smaller spread of area ratios compared to GC/FID. The
vacuum outlet conditions result in a large pressure drop across the
short capillary column, giving higher flow rates and decreased
discrimination as a function of injection port temperatures.
On-column injection was also evaluated in terms of component
discrimination. It has already been demonstrated that on-column
techniques provide the best precision when compared to the other modes
of injection (79). Figure 3.4 illustrates component discrimination as
a function of initial column temperature. The initial column
temperature in on-column injection corresponds roughly to the injection
port temperature in split/splitless injections. For this reason,
evaluations were not possible at initial column temperatures above 120
C, since the early eluting C12 alkylbenzene component was lost in the
solvent front. The results indicated no discrimination, as would be
expected for on-column injections. However, there appears to be a
small enhancement effect for the less volatile components at lower
initial column temperatures. This cannot be explained at the present
time. Table 3.1 compares splitless and on-column injection
techniques for accuracy and precision. A mixture containing known
weight ratios was prepared and analyzed with GC/FID. The FID response
is proportional to the mass flux of analyte, and therefore direct
correlations may be made between weight ratios and area ratios.
Results for both splitless and on-column injections were high compared
to the actual weight ratio, which may be due to some systematic error.

Peak Area Ratio
38
1.35
1.30
1.25
1.20
1.15
1.10
1.05
1.00
C16IC12
—ii n i i M i I i i n i i i i i [ i i i i i i i i i l i i i i i i i i i I i i i i i i i" !
20 40 60 80 100 120
Initial Column Temperature (C)
Plot of initial column temperature versus area ratios for
C12, C14, C16, and C18 alkylbenzenes for on-column
injections on a 3 meter DB5 column with FID detection.
Figure 3.4.

39
Table 3.1
Comparisons of Accuracy and Precision of Area Ratios
Components Between Splitless and On-Column Injection
Butvlbenzene
Decane
Hexamethvlbenzene
Decane
Actual Wt. 0.785 0.280
Ratio
Splitless
Area Ratio
%RSD
On-Column
Area Ratio 0.905(.004) 0.330(.009)
%RSD 0.44 2.82
0.894(.005)
0.54
0.30(.01)
4.32
of Various
Techniques
t-Stilbene
Decane
0.374
0.41(.03)
7.24
0.49(.01)
2.02
Note:
number of replicates n=3
number in parenthesis indicates standard deviation

40
The splitless results agreed more closely with the weight ratios, while
the precision of the on-column results was somewhat better.
These results indicate that, as long as the minimum injection port
temperature is maintained, component discrimination is greatly reduced
if not eliminated. Also, better reproducibility is obtained using
splitless injections.
Ancillary Short-Column Experiments
The use of short (3 m) capillary columns in these studies has led
to the discovery of some interesting chromatographic aspects. The
injection technique previously described in the Experimental chapter,
in which the bulk of the sample volume was removed from the syringe
needle volume in order to let the needle equilibrate to the injection
port temperature, was used to eliminate component discrimination and to
obtain more reproducible injections. This technique when used with
short columns, however, leads to the splitting of the early eluting
chromatographic peaks (Figure 3.5). This was determined to be a
function of injection port temperature. At high injection port
temperatures, the residual amount of sample which remains in the
syringe needle is vaporized prior to the injection and vaporization of
the sample contained in the syringe itself. This results in a "pre¬
peak" at high injection port temperatures which is absent at the lower
injection port temperature.
It was also observed that splitless injections provide better
chromatographic resolution than on-column techniques for short
capillary columns. This is presumably due to the large amount of band

Chromatograms of nonane (1), cyclooctane (2),
propylbenzene (3), and decalin (4) using split injections
on a 3 meter column, a) injection port 280 C, b)
injection port temperature 130 C.
Figure 3.5.

42
spreading incurred for on-column injections relative to the column
length. Figure 3.6 and Figure 3.7 illustrate the comparison of
injection techniques for chromatographic resolution for a narrow
boiling point range fuel and a wide boiling point range fuel,
respectively. The improved chromatographic resolution for the
splitless case is indicated by the sharper peaks, which are most
noticeable for the late eluting peaks.
Analytical Figures of Merit
The limits of detection which are determined here do not reflect
the limits that would actually be obtained if individual components
were to be determined. Figure 3.8 illustrates the reconstructed ion
current (RIC) full-scan mass spectra of a four-component mixture at 0.5
volume percent each, which corresponds to approximately 0.4 ng injected
on the column. The signal-to-noise in the RIC was approximately 3,
which represents the limit of detection for the HTA method. The
sensitivities of the four components are given by the slope of the
calibration curves illustrated in Figure 3.9. These sensitivities were
determined in order to compare the results to the actual ASTM
sensitivities in Table 5 of the ASTM D-2789 standard (6). Table 3.2
compares the sensitivities (slopes of the response curves in Figure
3.9) to the sensitivities of Table 5 of the ASTM standard (6), after
normalization to the C9 paraffin (nonane). The results indicate that
similar trends in sensitivities for the four components were observed
for the two methods, although the propylbenzene sensitivity was
significantly greater in the ASTM results.

Response
43
Retention Time (min) Retention Time (min)
Figure 3.6. Chromatograms of JP-7 jet fuel on a 3 meter column
comparing on-column and splitless injections.

44
Figure 3.7.
Chromatograms of JP-4 jet fuel on a 3 meter column
comparing on-column and splitless injections.

Figure 3.8. Chromatogram of nonane (1), cyclooctane (2),
propyIbenzcne (3), and decalin (4) at 0.5 volume °L each 4>
using 0.4 /¿L split injection on a 3 meter column.

PEAK AREA
46
DECALIN
—i i i i i i i—i i | i i i i i i i i i | i i i i i i i i i >
0 2 4 6 8
VOLUME PERCENT
Response curve obtained by linear regression for nonane,
cyclooctane, propylbenzene, and decalin at various volume
percentages.
Figure 3.9.

47
Table 3.2
Comparison of Sensitivities of ASTM and GC/MS/HTA
Results for a Four-Component Mixture
Normalized to the ASTM Sensitivity of Nonane
(Response per Volume %)
COMPONENT
ASTM
SENSITIVITY
GC/MS/HTA
SENSITIVITY
DECALIN
1.99
2.15
PROPYL-
2.52
2.06
BENZENE
CYCLO-
1.72
1.74
OCTANE
NONANE
1.72
1.72

48
The precision of the HTA method was determined by replicate
analyses of several jet fuel samples. The precision was dependent upon
the jet fuel analyzed or the composition of the fuels. The precision
of the HTA method is summarized in Table 3.3, in which the average
percent relative standard deviation is listed by hydrocarbon type for
all fuels analyzed in replicate. The high average relative standard
deviations were a result of that particular volume percent being very
low. The dashed lines indicate a consistent result of zero volume
percent.
Characterization of the GC/MS/HTA Method
Comparisons of ASTM and GC/MS/HTA Results
One of the major tasks in this research effort was to analyze a
number of real jet fuel samples with the newly developed GC/MS/HTA
method and to compare the results to those from the long-established
ASTM D-2789 method. These comparisons would provide information on the
validity of the ASTM inverse calibration matrices with GC sample
introduction and quadrupole mass analysis. Table 3.4 shows these
comparisons for five jet fuels. Several methods were used to evaluate
trends in the comparison versus composition, but none could be found.
The accuracy of the ASTM method has not been evaluated; therefore, the
comparison does not necessarily reflect the accuracy of the GC/MS/HTA
method.
Table 3.5 demonstrates the comparisons of several synthetically
prepared jet fuels. The "recipe" results were calculated from the
known volumes of the components added. Again these comparisons do not
necessarily represent accuracy of the GC/MS/HTA method, since the

49
Table 3.3
The Average Relative Standard Deviation for the GC/MS/HTA of
all Replicate Analyses and Separate Jet Fuels
HYDROCARBON
TYPE
AVERAGE
OF ALL FUELS
JP-4
2455
JP-7
JP-8X
2414
JP-8X
2429
PARAFFIN
3.0
2.1
1.2
7.1
1.7
MONOCYCLO-
PARAFFIN
3.8
2.5
0.6
6.8
5.3
DICYCLO¬
PARAFFIN
5.6
18.1
1.2
1.4
1.8
ALKYLBENZENE
7.6
3.8
18.8
2.5
5.4
INDANE/
TETRALIN
5.0
10.7
-
2.0
2.4
NAPHTHALENE
7.7
-
-
8.7
6.7
AVERAGE CARBON
NUMBER
AROMATIC
0.5
0.5
0.9
0.5
0.2
PARAFFIN
0.3
0.7
0.3
0.1
0.0

Table 3.4
Comparison of GC/MS/HTA and ASTM D-2789 Results
on Various Fuels, in Volume %
Fuel
Paraffin
Monocyclo¬
paraffin
Dicyclo¬
paraffin
Alkyl-
benzene
Indane-
Te tralin
Naphthalene
Aromatic
c//
Paraffin
c//
JP-4 2455
GC/MS/HTA
61.5(.2)
18.5(.8)
3(1)
14.8(.9)
2.0(.4)
0
9.06(.07)
9.50(.08)
ASTM D 2789
70.8
18.0
2.1
7.6
1.4
0.1
8.69
8.01
JP-8X 2429
GC/MS/HTA
0
3.2 (. 8)
68(2)
6.6 (. 7)
21.4( .8)
1 â–  3(.3)
8•0(.1)
9.01(.01)
ASTM D 2789
1.3
21.5
56.0
7.2
13.1
0.9
8.14
8.91
JP-8X 2414
GC/MS/HTA
7.0(.5)
10.3(.7)
35.0(.5)
15.7(.4)
29.7(.6)
2.3(.2)
9.87(.05)
9.40(.01)
ASTM D 2789 14.2
JP-8X SIMULATED
27.0
26.6
15.3
14.5
2.3
9.18
9.46
GC/MS/HTA
11.5(.2)
17.0(.9)
54.9(.9)
7.4(.4)
8.5 ( . 2 )
0.6( .04)
8.53(.02)
9.00(0)
ASTM D 2789
12.1
23.1
58.7
2.9
4.1
0.2
7.65
8.69
JET-A 2532
GC/MS/HTA
18.1
38.1
33.4
5.7
4.6
0
9.32
9.30
ASTM D 2789
27.4
44.7
20.8
4.9
2.1.
0.2
8.41
8.86
Ln
o
Note: Numbers in parenthesis indicate the standard deviation 11-3.

Table 3.5
Comparison of GC/MS/HTA Results and Synthetic Fuel Recipes
for Various Synthetic Fuels, in Volume X
Fuel
Paraffin
Monocyclo
paraffin
Dicyclo¬
paraffin
Alkyl-
benzene
Indane-
Tetralin
Naphthalene
Olefins
JP-8X SIMUIATED
GC/MS/HTA
11.5
17.5
54.9
7.4
8.5
0.6
-
RECIPE
12
20
60
(combined unsaturates 8 %)
-
HIGH AROMATIC
GC/MS/HTA
13.5
4.0
3.8
51.0
13.9
13.8
-
RECIPE
30
(combi
ned 10 %)
45
10
5
-
GRAND MIX
GC/MS/HTA
23.0
14.0
14.8
30.3
0.1
17.5
-
RECIPE
40
10
20
20
0.0
5
5
ALL GROUPS
GC/MS/HTA
36.6
17.2
2.9
26.7
4.7
11.8
-
RECIPE
60
(combined 10 %)
17
3
5
5

52
synthetic mixtures were formulated from complex petroleum fractions
(Exxon Corporation) such as Isopar C, G, and M (isoparaffinic and
paraffinic mixtures), and Aromatic 100 and 150 (aromatic mixtures).
These mixtures were obtained by simple fractionation and bulk
separation techniques, and were not intended for analytical standards.
Two of these mixtures were analyzed by GC/MS for specific group
components. The Isopar M mixture contained significant amounts of
cycloparaffinic components, with trace aromatics. The Aromatic 150
contained indanes and naphthalenes; the paraffin content was not
determined. The monocycloparaffin recipe results of the olefin-
containing fuels (Grand Mix and All Groups) agree better when the
olefin content is added to the monocycloparaffin content. These two
hydrocarbon types produce similar fragmentation patterns which tend to
equate the two types under the HTA method. More details of the
olefin/cycloalkane effects on the GC/MS/HTA method will be covered
later in this chapter and in Chapter V.
Simple Mixture Analysis
Simple mixtures were used to evaluate the accuracy of the GC/MS/HTA
method. Teeter states in his paper on high resolution mass
spectrometry for 22 hydrocarbon type analysis (29) that no sample can
be prepared which is complex enough to be a valid test for any HTA
method. This "Teeter Rule," as it has become known in our laboratory,
poses a real paradox for validation of these methods: any mixture
which is complex enough to be a valid test of the HTA matrix
calculation is too complex to be prepared. Certainly such a paradox is
difficult for any analytical chemist to accept. These experiments were

53
designed to test this rule as well as to evaluate the accuracy of the
GC/MS/HTA method. Table 3.6 shows the GC/MS/HTA results of a simple C6
mixture compared to the actual calculated volume percentages. The
mixtures were prepared solely of C6 components. The results clearly
indicate the inaccuracy in the analysis of such a simple sample,
although the zero percent components are correctly identified and the
aromatic average carbon numbers agree quite well. Table 3.7 shows the
GC/MS/HTA results of a simple CIO mixture compared to the actual
calculated volume percentages. In this case, better agreement was
obtained for those types present as well as the zero percent types.
The aromatic average carbon was well off the mark, yet the paraffin
average carbon number was very close.
The next step was to evaluate a mixture which contained a spread in
carbon numbers. Table 3.8 shows the GC/MS/HTA results of a simple C8-
C9 mixture compared to the actual calculated volume percents. The
results again indicated the inaccuracy of the method for simple
mixtures, although the precision of the analysis was quite good, as
indicated by the average percent relative standard deviation of 2.3%
for replicate injections. Again, the average aromatic carbon numbers
do not agree as well as the average paraffinic carbon numbers. Table
3.9 shows the GC/MS/HTA results of a simple C8-C10 mixture compared to
the actual calculated volume percents. The monocycloparaffin volume
percent was quite low, which resulted in a larger volume percent for
the dicycloparaffin and the two other hydrocarbon types present. The
average aromatic carbon number was low while the average paraffinic
carbon number was high compared to the calculated results. This seems

54
Table 3.6
Comparison of HTA on a Simple C6 Mixture
With Actual Volume Calculated Results
Simple
HYDROCARBON
TYPE
PREPARED
BY VOLUME %
HTA
VOLUME %
PARAFFIN
70.6
52.3
MONOCYCLO-
PARAFFIN
17.6
23.7
DICYCLO-
PARAFFIN
0.0
0.0
ALKYLBENZENES
11.8
24.0
INDANE/
TETRALIN
0.0
0.0
NAPHTHALENE
0.0
0.0
AVERAGE CARBON
NUMBER
AROMATIC
6.0
6.00
PARAFFIN
6.0
6.75
Mixture Make-up: Paraffin:
300
200
100
fj.L hexane
/¿L 3-methylpentane
¿¿L 2,2-dimethylbutane
Monocyclo-
paraffin:
100
50
fiL cyclohexane
fiL methylcyclopentane
Alkylbenzene:
100
/¿L benzene

Table 3.7
Comparison of HTA on a Simple CIO Mixture
With Actual Volume Calculated Results
HYDROCARBON PREPARED HTA
TYPE BY VOLUME % VOLUME %
PARAFFIN 33.3 29.8
MONOCYCLO- 0.0 0.0
PARAFFIN
DICYCLO- 33.3 35.8
PARAFFIN
ALKYLBENZENE 33.3 34.3
INDANE/ 0.0 0.0
TETRALIN
NAPHTHALENE 0.0 0.0
AVERAGE CARBON
NUMBER
AROMATIC 10.0 8.44
PARAFFIN 10.0 9.96

56
Table 3.8
Comparison of HTA on a Simple C8-C9 Mixture
With Actual Volume Calculated Results
HYDROCARBON
PREPARED
HTA
TYPE
BY VOLUME
% VOLUME %
PARAFFIN
44.5
39.2 (.5)
M0N0CYCL0-
PARAFFIN
33.4
21.3 (.2)
DICYCLO-
PARAFFIN
0.0
6.9 (.07)
ALKYLBENZENE
13.9
17.1 (.4)
INDANE/
TETRALIN
8.3
15.4 (.9)
NAPHTHALENE
0.0
0.0
AVERAGE CARBON
NUMBER
AROMATIC
9.00
8.68
PARAFFIN
8.43
8.44
Mixture Composition
(fiL) C8:
octane 50
2,5-dimethylhexane 50
2,3,4-trimethylpentane
octane 50
ethylcyclohexane 20
C9:
nonane 50
2,2,5 -trimethylhexane 20
isopropylcyclohexane 50
indane 30
propylbenzene 50

Table 3.9
Comparison of HTA on a Four-Component Mixture
With Actual Volume Calculated Results
(in Volume Percent)
HYDROCARBON CALCULATED HTA
TYPE BY VOLUME EXPERIMENTAL
PARAFFIN
25
27.0
MONOCYCLO-
PARAFFIN
25
9.8
DICYCLO-
PARAFFIN
25
33.7
ALKYLBENZENE
25
29.2
INDANE/
TETRALIN
-
0.0
NAPHTHALENE
-
0.3
AVERAGE CARBON
NUMBER
AROMATIC
9.0
8.68
PARAFFIN
9.0
9.59

58
to be the normal trend for these simple mixtures. Table 3.10 shows
the analysis of the same mixture as in Table 3.9 with the hexane
solvent included in the HTA calculation. The changing HTA volume
percent results generally agree with those expected, with the exception
of the monocycloparaffin results, which increase rather than decrease.
This would be expected since the mass spectrum of hexane contains a
large relative abundance of m/z 41, which is an ion of the
monocycloparaffin 2-series. The average aromatic carbon number for the
GC/MS/HTA results remains constant when hexane is included in the
calculation, as it should. The average paraffinic carbon number
decreases as expected and shows excellent agreement within the
predicted value.
To summarize, the analysis of simple mixtures by GC/MS/HTA does not
result in correct volume percent, which may simply be a verification of
the Teeter Rule. The paraffin and alkylbenzene volume percents showed
the best and most consistent agreement. The average paraffinic carbon
numbers consistently showed the best agreement except for the simple C6
mixture. The average aromatic carbon number was consistently low
compared to the actual results. The CIO mixture analysis was quite
accurate, unlike the other two simple mixtures. This may be an
erroneous result or may have some significance. Perhaps the sample
make-up of the CIO mixture more closely matches that of the original
CIO mixture used in the calibration matrix, or the matrix calculation
works better for a more closely distributed (single carbon number)
mixture distribution.

59
Table 3.10
Comparison of HTA on a Four-Component Mixture
With Actual Volume Calculated Results
With the Hexane Solvent Included in the Calculation
(in Volume Percent)
HYDROCARBON
TYPE
CALCULATED HTA
BY VOLUME EXPERIMENTAL
PARAFFIN
79
70.5
M0N0CYCL0-
PARAFFIN
7
16.2
DICYCLO-
PARAFFIN
7
5.5
ALKYLBENZENE
7
7.7
INDANE/
TETRALIN
-
0.0
NAPHTHALENE
-
0.0
AVERAGE CARBON
NUMBER
AROMATIC
9.0
8.72
PARAFFIN
6.7
6.70
100 /iL nonane
100 ¿iL cyclooctane
100 ¿iL n-propylbenzene
100 ¿iL decalin
Sample Mixture in 1000 ¿iL hexane:

60
Inverse Calibration Matrix Variation
An initial goal of this project was to validate the use of the
existing (ASTM D-2789) inverse calibration matrix with quadrupole mass
analysis. Since the matrix was prepared with one specific set of
calibration mixtures, it was desired to determine the effect of
calibration sample make-up on the inverse calibration matrix. A series
of C6 components was used to prepare an inverse calibration matrix for
carbon number 6 only. The hydrocarbon types were limited to paraffins,
monocycloparaffins, and aromatics because there are no C6 members of
the other types. Table 3.11 indicates the sample make-up used for the
determination of each hydrocarbon type similarity coefficient in the
inverse calibration matrix. The similarity coefficients are
normalization factors for the mixing of mass spectral ions of the
characteristic ion series. Various combinations were used for the
inverse calibration matrix. The calculational method used is similar
to that outlined in the experimental chapter. A computer program was
written to calculate the C6 inverse calibration matrix based on the
calculational method shown in Appendix A. A simple C6 mixture was
prepared and analyzed using the various inverse calibration matrices.
The results are compared to the actual volume calculated results in
Table 3.12. The results show a significant amount of fluctuation,
indicating the dependence of the calibration sample make-up on the
matrix results. The closest agreement comes with the P4C2B1
combination, whose monocycloparaffin make-up is similar to the test
mixture make-up but whose paraffin make-up is not. The worst agreement
comes with the P4C1B1 combination, which is expected since the paraffin

61
Table 3.11
Component Codes and Make-Up for Preparation of Samples
Used in the Various Carbon Number 6 Inverse Calibration Matrices
Component Code
Sample Make-Up (in ¿¿L)
Paraffins
hexane
3-methylpentane
2,2-dimethylbutane
PI
500
250
100
P2
250
100
500
P3
100
500
250
P4
1000
250
100
Monocyclo-
paraffins
cyclohexane
methylcyclopentane
Cl
500
250
C2
250
500
Alkylbenzenes
benzene
B1
1000

62
Table 3.12
Comparison of Volume Percent Results on a Simple Carbon Number 6
Mixture Using the Various Combinations of Calibration Mixtures as Listed
in Table 3.11 Previously Shown
Calibration Standard
Composition
by Component Codes
Paraffin
Monocyclo-
paraffin
Alkylbenzene
(benzene)
P1C1B1
74
10
16
P1C2B1
74
10
16
P2C1B1
67
19
14
P2C2B1
67
19
14
P3C1B1
68
18
15
P3C2B1
68
18
15
P4C1B1
53
36
11
P4C2B1
69
17
15
ACTUAL VOLUME CALCULATED
70.6
17.6
11.8
Simple C6 Mixture Make-up: Paraffin: 300 /iL hexane
200 /iL 3-methylpentane
100 /iL 2,2-dimethylbutane
Monocyclo¬
paraffin: 100 /iL cyclohexane
50 /iL methylcyclopentane
Alkylbenzene : 100 /iL benzene

63
and monocycloparaffin make-up is quite different from the test mixture
make-up. The aromatic results, however, are in the closest agreement
with this combination. This series of experiments illustrates the
importance of the make-up of each single type component in
determination of the similarity coefficients and the inverse
calibration matrices. This C6 example represents the simplest case in
this analysis. The complications faced with increasingly higher carbon
number mixtures and matrices are unknown. The complexities of these
mixtures may tend to eliminate these problems or enhance them.
Perturbation Jet Fuel Analysis
The GC/MS/HTA validation experiments described so far indicate that
there still remains a need for validation of the GC/MS/HTA method since
the above validation experiments contained limitations such as the
Teeter Rule in the simple mixture analysis, and the unknown composition
of the petroleum fractions in the synthetic fuel comparisons. To
maintain the required complexity of the mixtures to be analyzed (to
avoid complications due to the Teeter Rule), the jet fuels were
perturbed by addition of a pure component of known volume. Table 3.13
shows the GC/MS/HTA results for a JP8X jet fuel before and after
spiking the fuel with different amounts of various pure components.
The paraffin volume percent of the first three spiked fuels should be
increased to a calculated 28.6%. The fourth spiked fuel, which
contains no paraffin spike, should agree with the "fuel only" results.
These were in fact the results observed. The fuel containing the
nonane and undecane spike showed the closest agreement. The volume

64
Table 3.13
Comparison of GC/MS/HTA of 86-POSF-2429 JP8X FUEL
After Spiking with Various Hydrocarbon Types
in Volume %
HYDROCARBON FUEL SPIKE 1* SPIKE 2 SPIKE 3 SPIKE 4
TYPE
PARAFFIN
o
o
29.6
(28.6)
24.6
(28.6)
32.0 (28.6)
CM
O
(0.0)
MONOCYCLO-
PARAFFIN
6.6
1.2
(4.7)
6.7
(4.7)
0.2 (4.7)
15.1
(19.0)
DICYCLO-
PARAFFIN
72.5
53.8
(57.8)
52.0
(57.8)
52.2 (57.8)
52.0
(57.8)
ALKYLBENZENE
6.2
4.6
(4.4)
4.9
(4.4)
4.7 (4.4)
22.9
(18.7)
INDANE/
TETRALIN
14.4
10.6
(10.3)
11.6
(10.3)
10.4 (10.3)
9.3
(10.3)
NAPHTHALENE
0.3
0.2
(0.2)
0.2
(0.2)
0.4 (0.2)
0.5
(0.2)
AVERAGE CARBON
NUMBER
AROMATIC
7.50
7.32
7
53
7.48
8
53
PARAFFIN
9.02
9.35
8
55
9.51
9
01
*
SPIKE 1: 500
AtL FUEL
+ 100
pL n-nonane + 100 /¿L undecane
SPIKE 2:
II
+ 200
/¿I n-octane
SPIKE 3:
II
+ 200
Ail n-decane
SPIKE 4:
It
+ 100
AiL butylbenzene + 10C
AiL cyclooctane
Note: numbers in parenthesis indicate the expected results due to
dilution or addition of that specific type.

65
percent of the remaining hydrocarbon types of the first three spiked
fuels (paraffinic spikes) should decrease due to dilution and remain
relatively constant. The calculated values are monocycloparaffin,
4.7%; dicycloparaffin, 51.8%; alkylbezenes, 4.4%; indane/tetralin,
10.3%; and naphthalene, 0.2%. On examination of Table 3.13, excellent
agreement is observed for all types for the first three spikes, with
the exceptions of the monocycloparaffin results. Attempts were made to
explain this behavior by analysis of the mass spectra of each
particular component, but no distinctions could be made. Most
paraffins contain a large relative abundance of m/z 41 (30-50%) and
m/z 55 (5-15%) which are ions indicative of the monocycloparaffin type.
The fourth spiked fuel also demonstrates excellent agreement with the
calculated perturbations for the hydrocarbon types not present in the
spike. The monocycloparaffin results were low compared to the
calculated (19.0%), and the alkylbenzene was high compared to the
calculated (18.7%). Again no explanation could be drawn by examination
of the component spectra; however, the sum of the two types
(monocycloparaffin and alkylbenzene) did equal the sum of the
calculated results. The average carbon numbers demonstrated good
correlation with the perturbation of the fuel. The average aromatic
carbon number remained relatively constant for paraffin perturbation
but increased with the butylbenzene (CIO) addition. The average
paraffinic carbon number also correlated with the paraffin
perturbation; 9.35 for nonane and undecane (CIO average) addition;
8.55 for octane addition; 9.51 for decane addition; and no change with
the addition of spike number four.

66
This perturbation approach appears to- be a much more successful
approach for validation of the GC/MS/HTA method than the previous two
methods (simple mixture analysis and ASTM comparisons). The much
better agreement seems to further support the "Teeter Rule" and
indicates that additional experiments should be performed.
A second set of fuel perturbation experiments was performed using
the standard addition method. Figure 3.10 illustrates the GC/MS/HTA
results for standard addition of n-propylbenzene to JP-4 2455 jet fuel.
The HTA aromatic type response was compared to the theoretical aromatic
type response of the volume percent added. The more positive slope of
the experimental line indicates that upon increased additions of n-
propylbenzene to the jet fuel an above-average GC/MS/HTA aromatic
response will result. However, the negative x-intercept (-13.2
aromatic volume percent), which indicates the volume percent of the
original fuel, agree to within experimental error with the original HTA
result (12.8). To test the hypothesis stated above in regard to the
above average GC/MS/HTA response of the n-propylbenzene alkylbenzene,
the same fuel was spiked with the Aromatic 150 mixture. Figure 3.11
illustrates the results of this standard addition experiment. The
"real line" intersects with the theoretical line and adheres more
closely to it in the region of the data points. This confirms the
above average response hypothesis of the n-propylbenzene. This may
indicate that the Aromatic 150 better represents the composition of the
original calibration solution used in the preparation of the inverse
calibration matrix. The larger negative x-intercept of the Aromatic
150 indicates that a larger volume percent must be added to equal the

Aromatic Volume Percent
67
Volume Percent Added
Figure 3.10. Plot of volume percent standard addition of
n-propylbenzene to jet fuel JP-4 2455. The real line
indicates the experimental results.

Aromatic Volume Percent
68
Volume Percent Added
Figure 3.11. Plot of volume percent standard addition of Aromatic 150
to jet fuel JP-4 2455. The real line indicates the
experimental results.

69
theoretical volume percent. This result is consistent with the
composition of the Aromatic 150 mix which is known to contain
components other than alkylbenzenes such as indanes, tetralins, and
naphthalenes. Figure 3.12 compares the mass spectrum of n-
propylbenzene and the average mass spectra of the Aromatic 150 mixture.
The presence of non-alkylbenzene aromatics in the Aromatic 150 is
evident by the presence of m/z 117 and m/z 118, indanes and tetralins;
m/z 128 and m/z 142, naphthalenes.
The above analysis of the standard addition plots was formulated
based on the linear regression of the experimental standard additions.
This seems appropriate when considering the linear theoretical plots;
however, in both cases there was a clear curvature to the data points.
This effect is illustrated in Figure 3.13 in which the experimental n-
propylbenzene data have been connected by a spline fit. The decreasing
slope with increasing volume percent added could possibly be explained
by the partial molal volume of mixing theory, but the degree of change
is much too large. The more negative x-intercept which was obtained
in both of the previous results is not consistent with the types of
additions made and otherwise has no explainable significance. These
results confirmed the original linearization assumptions used above.
Evaluation of Olefin and Cvcloparaffin Isomers
A major concern of the ASTM and GC/MS/HTA methods is the presence
of olefins and how they effect the results of the monocycloparaffin
volume percentages. In the ASTM method it is assumed that there is no
difference between the fragmentation pattern of any two olefinic or
cycloparaffin isomers of equal carbon number. This results in an

% Relative Abundance
miz
Figure 3.12. Mass spectra of n-propylbenzene and Aromatic 150.
o

Aromatic Volume Percent
71
Figure 3.13.
Spline fit to experimental volume percent standard
addition of n-propylbenzene to jet fuel JP-4 2455
compared to theoretical addition.

72
uncertainty in the HTA analysis if the presence of olefins is uncertain
or if their concentrations are unknown. The ASTM procedure requires
the subtraction of the olefin volume percent from the monocycloparaffin
volume percent when the olefin content is known. The olefin content
may be determined using the ASTM D-875 standard method. We were
interested in evaluating the effects of the olefin content on the
GC/MS/HTA results and how they would compare to the isomeric
monocycloparaffin content. Table 3.14 shows the differences in the
GC/MS/HTA paraffin, monocycloparaffin, and dicycloparaffin results for
the JP-4 2455 jet fuel after the addition of C7, C9, and CIO olefin and
monocycloparaffin isomers. It should be noted that the CIO case was
analyzed on a separate day which resulted in a slight variation in the
"FUEL ONLY" results. The table also compares these results to the
theoretical content expected. The results of the unsaturated
hydrocarbon types are not shown since changes were incurred only
through dilution. In all cases, the monocycloparaffin demonstrated a
larger increase in the monocycloparaffin content than the olefin.
Examination of the paraffin and dicycloparaffin content after
perturbation of the fuels demonstrates some interesting results which
can be evaluated in terms of the differences in the mass spectra of
each and reference to the characteristic ion series for each
hydrocarbon type (Table 2.1). Figure 3.14 shows the mass spectra of
the C7 isomers cycloheptane and 1-heptene. A larger relative abundance
of molecular ion (m/z 98) and [M-15]+ (m/z 83) was obtained for the
cycloheptane but produced little differences between the GC/MS/HTA
results. Figure 3.15 shows the mass spectra of the C9 isomers

73
Table 3.14
Comparison of HTA of JP-4 2455 Jet Fuel
After Spiking with C7, C9, and CIO Cycloalkane and Olefin Isomers
(in Volume Percent)
HYDROCARBON
TYPE
FUEL ONLY
500 nL
Fuel+50 n~L
cycloheptane
Fuel+50 /¿L
1-heptene
Expected
Result
PARAFFIN
61.5
57.9
59.9
55.9
MONOCYCLO-
PARAFFIN
18.5
24.8
22.2
25.9
DICYCLO-
PARAFFIN
3.1
1.1
1.8
2.8
HYDROCARBON
TYPE
FUEL ONLY
500 nL
Fuel+50 /j.L
propylcyclohexane
Fuel+50 ¡jlL
1-nonene
Expected
Result
PARAFFIN
61.5
55.1
61.4
55.9
MONOCYCLO-
PARAFFIN
18.5
24.5
22.3
25.9
DICYCLO-
PARAFFIN
3.1
6.4
1.4
2.8
HYDROCARBON
TYPE
FUEL ONLY
500 fiL
Fuel+50 /¿L iso¬
butyl cyclohexane
Fuel+50 /¿L
1-decene
Expected
Result
PARAFFIN
58.8
52.2
58.3
53.4
MONOCYCLO-
PARAFFIN
17.8
27.4
21.4
25.3
DICYCLO-
PARAFFIN
4.0
3.7
3.4
3.6

% Relative Abundance
m/z
Figure 3.14.
Comparison of inass spectra of C7 isomers cycloheptane and
1-heptene.
•~4

% Relative Abundance
160.0
50.0
100.0
50.0
miz
Figure 3.15. Comparison of mass spectra of C9 isomers isopropyl-
cyclohexane and 1-nonene.
Ui

76
isopropylcyclohexane and 1-nonene. Again a larger relative abundance
of molecular ion (m/z 126) was obtained for the cycloparaffin, but also
the fragmentation pattern was quite different than that of the olefin.
The large relative abundances of the m/z 82 fragment (96%) and the m/z
67 fragment (42%) for the cycloparaffin isomer, which were very low for
the olefin (9%) , caused the dicycloparaffin volume percent of the
cycloparaffin-spiked fuel determined by HTA to be high. Similarly the
large relative abundances of paraffinic fragment ions (m/z 43, 57, and
71) for the olefin isomer caused the paraffin volume percent of the
olefin-spiked fuel to be well above that of the cycloparaffin-spiked
fuel. Figure 3.16 shows the mass spectra of the CIO isomers
isobutylcyclohexane and 1-decene. Again a larger relative abundance of
molecular ion (m/z 140) was obtained for the cycloparaffin. The
fragmentation patterns, although different, both contributed response
to the dicycloparaffin volume percent of the spiked fuels. The
slightly higher volume percent calculated for the cycloparaffin-spiked
fuel was due to the larger relative abundance of m/z 82 fragment. The
paraffinic volume percent was again larger for the olefin spiked fuel
because of the large relative abundances of the paraffinic fragment
ions, especially m/z 43.
These studies validate the need for separate determinations of
cycloparaffin and olefin content in the HTA of jet fuels. New
complications have been introduced as to the effects on the HTA
calculated paraffin and dicycloparaffin content. Examination of the
differences in the mass spectra of the isomeric monocycloalkanes and

% Relative Abundance
100.0-1
33
50.0-
55
41
nrm
â–  l |
67
ISO-BUTYLCYCLOHEXhME
140
I ' ’ ' I ' '
-n-rr
" 1 ' " • I
T
m/z
Figure 3.16. Comparison of mass spectra of CIO isomers isobutyl-
cyclohexane and decene.

78
olefins of the three carbon numbers studied suggest the possibility of
developing techniques which could identify and quantitate each isomer
separately in the presence of the other.
Evaluation of Methods for Average Carbon Number Determinations
The GC/MS/HTA method relies heavily on the accuracy of the average
carbon number calculations, since the inverse calibration matrices
chosen are dependent upon these results. As in the ASTM methods, these
average carbon numbers (aromatic and paraffinic) are determined based
on the intensities of the paraffin and alkylbenzene molecular and
fragment ion series such as [M-15]+. This has raised a certain degree
of speculation concerning the accuracy of this method. First, as
mentioned, the method is based on the intensities of molecular and
fragment ions, which are generally of very low relative abundance.
This is particularly true for paraffins, whose molecular ion relative
abundances are on the order of 1-5%. Alkylbenzenes, however have
relatively abundant molecular ions, on the order of 20-50%. Therefore
less error would be expected for the aromatic results. Second, the
volume percent results of the remaining hydrocarbon types are dependent
upon the average carbon number results of the paraffins and
alkylbenzenes. For example, the dicycloparaffin volume percent is
calculated based on the inverse calibration matrix determined by the
average paraffin carbon number. This would obviously cause even
greater error in the results for those samples which contain small
amounts of paraffins relative to the dicycloparaffins. To clarify some
of these uncertainties, a new method of calculating the average carbon
numbers of a jet fuel was developed.

79
As was shown in Figure 2.2, the GC/MS simulated distillation
(GC/MS/SD) method determines the centroid of the total area of a
chromatographic profile. The GC/MS facilitates the ability to profile
an ion series characteristic of a certain hydrocarbon type with an ion
summation chromatogram, which may then be compared to a similar
chromatogram of a homologous series of that hydrocarbon type. Figure
3.17 again illustrates this method, only in this case showing the
paraffin series (E43) of the JP-8X fuel with the corresponding n-
paraffin homologous series in parallel. Several variations in this
technique were used for the determination of the average carbon
numbers. These variations were obtained by variations in the
particular set of ions used in the ion summation chromatograms. Table
3.15 shows the results of these carbon number determinations for
several jet fuels. From this table, three comparisons can be made for
both aromatic and paraffinic average carbon numbers: comparison between
the two GC/MS/SD methods (which will be explained below); comparison
between the two GC/MS/SD methods and the GC/MS/HTA method; and
comparison between the GC/MS/HTA and the ASTM method.
GC/MS Simulated Distillation
Table 3.15 provides data for the comparison of the two GC/MS/SD
methods, SIM DIST #1 and SIM DIST #2 for both aromatic average carbon
numbers and paraffinic average carbon numbers. The comparisons
demonstrate the variations which were due to the characteristic set of
ions used in the calculations as discussed above. The methods used for
the two GC/MS/SD average carbon numbers determinations were as follows:
the SIM DIST #1 method calculates the paraffinic carbon number based

190.a—
80
i
Figure 3.17. The paraffinic (X43) ion summation chromatogram of jet
fuel JP-8X 2414 on a 3 meter DB5 column. The centroid of
the total area, indicated by the arrows, is referenced to
the n-paraffin homologous series. The average paraffinic
carbon number is calculated to be 12.89.

Table 3.15
Comparison of Average Paraffin and Aromatic Carbon Numbers
for Various Fuels Using
Aromatic Average Carbon Number
Fuel
sim dist y/ia
SIM DIST y/2b
CC/MS/HTA
JP-4 2455
10.4(.4)
10.9(.2)
9.06(.07)
JP-8X 2429
12.1
10.7
8 • 0 ( . 1)
JP-8X 2414
10.9
11.9
9.87(.05)
JP-8X
SIMULATED
10.2
10.7
8.53(.02)
JET-A 2532
11.8
11.8
9.32
JP-7 NARROW
B.P. RANGE
11•6(.1)
11.85(.01)
10.5(.1)
PETROLEUM
JP-8 2400
10.1
10.3
9.51
PETROLEUM
JP-4 0988
9.9
10.2
9.16
everal Calculational Techniques
Paraffin Average
Carbon Number
A STM
SIM DIST //Ia
SIM DIST
GC/MS/HTA
A STM
8.69
12.1(.2)
12.0(.3)
9.50(.08)
8.01
8.14
14
11.1
9.01(.01)
8.91
9.18
13.1
11.8
9.40(.01)
9.46
7.65
12.4
11.1
9.00(0)
8.69
8.41
12.6
12.5
9.30
8.86
-
12.4(.2)
12.3(.2)
11.52(.03)
-
-
10.8
10.6
9.83
-
10.7
10.8
10.03
a SIM DIST y/1 Area centroid based on paraffin and alkylbenzene ion summation chromatograms,
b SIM DIST #2 Area centroid based on saturates and unsaturates ion summation chromatograms.
Note: Numbers in parenthesis are standard deviations.

82
solely on the ion summation chromatogram of the 243 ions (paraffin) ,
and the aromatic carbon number based on the ion summation chromatogram
of the 277 ions (alkylbenzene) ; the SIM DIST #2 method calculates the
paraffinic carbon numbers based on the ion summation chromatogram of
all the saturated ion sets, 243, 241, and 267, (paraffin,
monocycloparaffin, and dicycloparaffin) , and the aromatic carbon
numbers based on the ion summation chromatograms of all the unsaturated
ion sets, 277, 2103, 2128, (alkylbenzene, indane/tetralin, and
naphthalene). To make a proper evaluation of these results, reference
must be made to the composition of these jet fuels, as shown in Table
3.4. For those fuels whose saturated and unsaturated compositions were
made up mainly of paraffins and alkylbenzenes, respectively, there were
only small differences between the average carbon numbers obtained by
two techniques. For example, the JP-4 2455 jet fuel has a saturated
fraction composed mainly of paraffin, which results in little
difference between the average paraffinic carbon numbers from the two
techniques, 12.1 and 12.0. The JP-8X 2429 jet fuel, on the contrary,
has a saturated fraction composed mainly of dicycloparaffin which has
resulted in a large difference between the average paraffinic carbon
numbers of the two techniques, 14 and 11.1. For this fuel the same
trend was observed for the average aromatic carbon numbers, 12.1 and
10.7, since the unsaturated fraction was composed mainly of
indane/tetralin rather than alkylbenzenes. In summary these two
techniques of average carbon numbers determinations demonstrate a large
dependency upon the composition of the jet fuel, which demonstrates the
failures of the present ASTM method and the need for more specific

83
methods for carbon number determinations of each particular hydrocarbon
type. These conclusions are further supported by the second set of
comparisons between the GC/MS/SD and GC/MS/HTA results.
Comparison Between GC/MS/SD and GC/MS/HTA
Table 3.15 provides data for the comparison of the GC/MS/SD and
GC/MS/HTA methods of average carbon number determination. The original
purpose of the development of the GC/MS/SD method was to demonstrate
the dependence of the average carbon number results on the sample
concentration, and the limitations of calculating the paraffinic
(saturated) and aromatic (unsaturated) average carbon number based on
the paraffin and alkylbenzene composition only (both discussed above).
The large differences between the GC/MS/SD and GC/MS/HTA results were
not expected. In all cases a larger average carbon number (sometimes
larger by 3 or 4 carbons) was obtained for the GC/MS/SD results than
for the GC/MS/HTA results. This raised uncertainty in the results of
the GC/MS/SD technique, although the simulated distillation methods
seemed scientifically sound and much more tangible than the mass
spectral technique of the GC/MS/HTA method discussed above.
Consultation with the engineers at the Pratt and Whitney Fuels
Division, who have analyzed many jet fuels for average boiling point by
the ASTM simulated distillation method (44,45), suggested a consistent
underestimation of the average carbon numbers by the ASTM D-2789
method.
Comparison Between GC/MS/HTA and ASTM
The final set of comparisons made in Table 3.15 were between the
GC/MS/HTA and ASTM D-2789 results. These results were determined based

84
on the same computational technique as discussed at the beginning of
this section. Large deviations between the results of the two
techniques were apparent for most fuels, with the GC/MS/HTA values
generally larger. The results of jet fuel JP-8X 2429 showed the best
paraffinic and aromatic average carbon number agreement, while jet fuel
JP-4 2455 showed the worst. The measure of paraffinic carbon number
agreement may be correlated to the saturate composition of the fuels
(see Table 3.4), since the JP-8X fuels (such as 2429 and 2414) were
composed mainly of dicycloparaffins, and the JP-4 fuel was composed
mainly of paraffins. These correlations are of course dependent upon
the accuracy of the volume percent results, which are themselves
dependent upon the average carbon number results. No correlation
between the composition of the jet fuels and the aromatic carbon
numbers could be determined. However, agreement between the two
methods was generally better for the aromatic carbon numbers than for
the paraffinic carbon numbers. This may be due to the increased
accuracy of the technique as reflected in the larger relative abundance
of the alkylbenzene molecular ions, as discussed above.
The presence of large amounts of naphthalenes in jet fuels can
cause a large amount of error in the paraffinic average carbon number
and ultimately in the final volume percent results (6), since the m/z
128, m/z 142, and m/z 156 ions used in the ASTM average paraffinic
carbon number determination correspond to abundant molecular ions of
naphthalene, methylnaphthalene, and dimethylnaphthalene, respectively.
Investigations of the effect of this perturbation were made by spiking
the JP-4 2455 jet fuel with dimethylnaphthalene. Table 3.16

Table 3.16
Comparison of GC/MS/HTA of JP4 Fuel
After Spiking with Dimethylnaphthalene
in Volume Percent
HYDROCARBON
TYPE
FUEL ONLY
500 fiL
Fuel+100 fiL
Dimethylnaphthalene
Expected
Result
PARAFFIN
61.5
43.9
51.3
MONOCYCLO-
PARAFFIN
18.5
18.0
15.4
DICYCLO¬
PARAFFIN
3.1
0.0
2.6
ALKYLBENZENE
14.8
11.4
12.3
INDANE/
TETRALIN
2.0
2.2
1.7
NAPHTHALENE
0.0
24.5
16.7
AVERAGE CARBON
NUMBER
AROMATIC
9.06
8.91
9.55
PARAFFIN
9.50
10.58
9.50

86
illustrates the results of this perturbation of the jet fuel. The
drastic increase in the paraffinic average carbon number from 9.50 to
10.58 reflects the effect of the addition of the C12
dimethylnaphthalene. An increase in the aromatic average carbon number
was expected since dimethylnaphthalene is a C12 aromatic; however the
results actually decreased. This is due in fact to the average
aromatic carbon number calculational method which is based solely on
ions of the alkylbenzene series. The mass spectra of
dimethylnaphthalene contains a small relative abundance of m/z 91,
which is an ion of the alkylbenzene series, which explains the decrease
in aromatic average carbon number. The saturate volume percent results
of the spiked fuel did not agree with changes expected due simply to
dilution. This may be attributed to the incorrect average paraffinic
carbon number on which the volume percent calculation is now based. It
should be noted that the naphthalene volume percent increased to 24.5%
for the spiked fuel which was close to the expected 16.7% theoretical
value. These results illustrate the significance of the naphthalene
content on the hydrocarbon type analysis results, not only on
paraffinic carbon numbers, but on volume percent results as well.
Effect of Chromatographic Resolution on Carbon Number Calculations
The evaluations and comparisons above were made under the
assumption that the carbon number calculational techniques produced
valid average carbon number results. Since chromatographic separation
played such an important role in these determinations, especially for
the GC/MS/SD techniques, it was desired to determine the effect of
increased chromatographic resolution on the average carbon number

87
results. Table 3.17 shows the effect of chromatographic separation on
the average carbon number results for the four calculational techniques
and two separate jet fuels, JP-4 2455 and JP-8X 2429. The
chromatographic resolution was increased by changing from a 3 meter
column to a 30 meter column. Both fuels demonstrated a dependence on
chromatographic separation for all carbon number calculational
techniques. In all cases the determination of carbon numbers with
increased chromatographic separation, with the exception of the
aromatic average carbon number for JP-8X using the SIM DIST #2 method,
better agreement was obtained between the GC/MS/DS and the GC/MS/HTA
results, and between the GC/MS/HTA and ASTM results. Increased
chromatographic separation reduced all average carbon numbers for the
JP-4 fuel. Increased chromatographic separation decreased all average
carbon numbers for the JP-8X fuel with the exception of the paraffinic
average carbon number using the SIM DIST //I method. These results
indicate that the average carbon number results are very much dependent
upon the degree of chromatographic separation employed, and that
increased chromatographic resolution results in more accurate average
carbon number determinations.
Summary of Results
An extensive amount of effort was dedicated to characterization of
the GC/MS/HTA method. The injection methods were evaluated in terms of
component discrimination which resulted in the development of a non¬
discriminating injection technique. The method was evaluated in terms
of sensitivity and precision. Similar sensitivities were determined to

Table 3.17
CHROMATOGRAPHY
CONDITIONS
3 METER DB5
30 METER DB5
3 METER DB5
30 METER DB5
Comparison of Average Paraffin and Aromatic Carbon Numbers
for JP-4 2453 and JP-8X 2429 Fuels as a Function of Chromatographic
Separation Using Several Calculational Techniques
Aromatic Average Carbon Number Paraffin Average Carbon Number
SIM DIST #la SIM DIST #2b GC/MS/HTA ASTM SIM DIST #1 SIM DIST #2 GC/MS/HTA
JP 4 2455 FUEL
10,4(.4) 10.9(.2) 9.06(.07) 12.1(.2) 12.0(.3) 9.50(,08)
8.69
9.22(.01) 9.58(.01) 9.00(0) 8.64(.02) 8.68(.04) 8.95(.06)
JP 8X 2429 FUEL
12.1 10.7 8.0(.1) 14 11.1 9.01(.01)
8.14
12.07(.06) 12.71(.01) 8.19(.01) 13.07(,05) 11.59(.06) 9.20(.03)
ASTM
8.01
8.91
SIM DIST //I Area centroid based on paraffin and alkylbenzene ion summation chromatograms.
SIM DIST #2 Area centroid based on saturates and unsaturates ion summation chromatograms.
Note: Numbers in parenthesis indicate standard deviations.
00
oo

89
those calculated in the ASTM technique. The precision was dependent on
hydrocarbon type and volume percent.
To characterize and validate the GC/MS/HTA method, a series of
experiments were performed. Comparisons of GC/MS/HTA results with the
ASTM results were inconsistent and followed no trends. Evaluations of
GC/MS/HTA results of synthetic mixtures showed good agreement in some
cases but were still inconsistent. The analysis of simple mixtures
seemed to validate the Teeter Rule, although excellent agreement was
often present. The perturbation fuel analysis introduced a new method
for the characterization of HTA methods. The results obtained here
were consistent with the expected results and represented a significant
contribution towards validation of the method.
A new method for carbon number determination was developed based on
GC/MS/simulated distillation. A critical evaluation of this method,
the GC/MS/HTA method, and the ASTM method was performed. The results
indicated that the GC/MS/HTA and ASTM method underestimate the average
carbon numbers which have a significant effect on the volume percent
results of HTA methods. Chromatographic resolution affected the
GC/MS/SD determination of average carbon numbers. The results
indicated better agreement with mass spectral methods upon increased
chromatographic resolution.
Finally, as an intricate part of this project, the developed
GC/MS/HTA method was documented in the standard ASTM format which was
to be utilized by the Pratt and Whitney engineers of the Fuels
Division. A duplication of the ASTM standardized GC/MS/HTA method is
shown in Appendix D.

CHAPTER IV
PRELIMINARY INVESTIGATIONS OF ALTERNATIVE IONIZATION
TECHNIQUES FOR JET FUEL ANALYSIS
The primary goal of this area of study was to investigate
alternative ionization techniques in mass spectrometry for the analysis
of jet fuels. These studies will cover aspects of both hydrocarbon
type analysis and total fuel analysis. The combination of high
resolution gas chromatography and alternative ionization techniques
such as low-energy electron ionization and methane chemical ionization,
will be a powerful tool for the determination of specific components in
jet fuels.
Background
Low Energy Electron Ionization
The main effort in the application of low energy electron
ionization GC/MS is to evaluate a technique for the specific detection
of aromatic type compounds in jet fuels. Studies have been reported
(31,53,59) on the determination of specific aromatic components in
fuels and coal-derived liquids by such methods. Aromatic compounds
have a lower ionization potential than aliphatic molecules which allows
for the selective ionization of aromatics in the presence of aliphatics
(53).
90

91
In the present study the utilization of GC separation, combined
with the specific detection of aromatics, is demonstrated as a
potential method for the determination of specific aromatic components
in jet fuels. A method such as this would contribute to the
development of a total fuel analysis method which was previously
discussed.
Methane Chemical Ionization
The main effort in the application of methane chemical ionization
(Cl) GC/MS to the analysis of jet fuels was to demonstrate the
potential of the technique as a new method for hydrocarbon type
analysis. Much work has been reported on the analysis of fuels and
other coal derived liquids using CI/MS (53-58) for the determination of
specific fuel components and specific classes of components. With
chemical ionization, a large array of specific ionization schemes are
available by choosing an appropriate Cl reagent gas. Harrison (52) in
his book on chemical ionization mass spectrometry, discusses in detail
the fundamentals, instrumentation, and applications of CI/MS. In
general terms, the ionization specificity in CI/MS is obtained by the
specific reactions and energetics encountered by the ionized reagent
compound and the analyte. For example, in positive methane CI/MS
(which is used in this study) , a methane molecule is first ionized to
CH4+ (and CH3+, CH2+, etc.) by electron impact ionization. Collisions
of these ions with another methane molecule leads to proton transfer to
form CH5+. This process continues to form higher m/z ions such as
C2H5+. Only those analytes with a higher proton affinity than CH4 and
C2H4 (the conjugate bases of CH5+ and the C2H5+ ions) will be ionized.

92
The application of methane CI/MS will be demonstrated as a
potential new method of hydrocarbon type analysis of jet fuel. The
results are only preliminary and demonstrate the need for continued
experimentation. An additional potential for CI/MS is combined gas
chromatography CI/MS. This would enable the determination of specific
components of specific classes which would contribute to the total fuel
analysis effort.
Experimental
All instrumental parameters were unchanged unless otherwise
specified in this section.
Electron Energy Variation
The electron energy variation was obtained by manual adjustment of
the electron energy control knob. The electron current was maintained
at 300 ¿iA which limited the lowest electron energy to 11.7 eV. The
high end of the electron energy was 100 eV.
The sample analyzed was a 50/50 mixture of the Aromatic 150 and
Isopar M mixtures. Analysis of the sample at each electron energy was
performed separately after adjustment to the proper energy.
Methane Cl
Methane Cl was performed at an electron energy of 100 eV and a
methane source pressure between 0.2 and 0.3 Torr. The mass
spectrometer was scanned from 65 to 650 amu with a total scan time of
1.0 s. The samples were analyzed by separate injections of pure
components diluted in hexane.

93
Results and Discussion
The experimental results which follow represent preliminary
investigations on the use of alternative ionization MS techniques as
specific detectors for hydrocarbon types in jet fuels. The development
of a complete method based on these techniques was not the objective
these investigations.
Low Energy Electron Ionization
By varying the electron energy in the ion source of the mass
spectrometer, the specific detection of aromatic components was
obtained in the presence of paraffin components. This is illustrated
in Figure 4.1 in which only a select group of aromatic compounds show
response. The low energy El analysis suffers from low sensitivities,
as reflected by the total area of each chromatogram, but the
selectivity is greatly enhanced. Table 4.1 shows the variation in the
combined saturate and unsaturate hydrocarbon type analysis results of
this 50/50 aromatic/paraffinic mixture as a function of electron
energy. The results illustrate the selective ionization of aromatics
(unsaturates) at lower electron energies. To further illustrate the
increased selectivity of this ionization method, the mass spectrum of a
single chromatographic peak is shown as a function of electron energy
in Figure 4.2. The lowest electron energy (11.7 eV) was very selective
for the C4-benzene (possibly butylbenzene), but the response was quite
low. In this example only the M+ ion was produced. As the energy was
increased (13.0 eV) other aromatic mass spectral peaks appeared such as
m/z 148 which is indicative of a C5-benzene M+ ion. At 50.1 eV a
series of paraffinic peaks appeared which clearly indicated the

94
SChM
â– 5 TIME
Figure 4.1
The reconstructed ion current chromatograms for a 50/50
paraffin and aromatic mixture at two different electron
ionization energies, A) 13.0 eV, B) 50.1 eV.

95
Table 4.1
Results of Combined Saturates and Combined Unsaturates GC/MS/HTA
of a 50/50 Aromatic 150/Isopar M Mixture
as a Function of Electron Energy
in Volume %
Electron Energy
(eV)
Saturates
(paraffins)
Unsaturates
(aromatics)
11.7
0
100.0
13.0
0.2
99.2
20.0
37.6
62.4
31.0
49.9
51.1
50.1
50.6
49.4
100.0
44.2
55.8

96
100.0
50.0
M/E
134
A
11.7 EU El
‘
I i I â–  "T 1 ' " ' I ' ' I- 1 " ' ' ' 1 ' " | '
40 S0 30 100 120 140 1S0 180 200
21.
Figure 4.2. The mass spectra of the peaks marked by scan number 179
and 178 in Fig. 4 above at different electron energies,
A) 11.7 eV (chromatogram not shown in Fig. 4), B) 13.0
eV, and C) 50.1 eV.

97
multicomponent nature of this chromatographic peak and the selectivity
provided by low electron energies.
These results were obtained on a 3 m column with minimal
chromatographic separation. Application of increased GC separation
would surely provide a means of specific component analysis of aromatic
types in jet fuels.
Methane Chemical Ionization
The ideal method for hydrocarbon type analysis would be to have
available a specific detection system for each hydrocarbon type, thus
eliminating the need for matrix normalization. This ideal system would
best be performed on one instrumental configuration. The methane
chemical ionization mass spectra of common hydrocarbons of jet fuels
have demonstrated potential as such a detection system. These results
are illustrated in the set of figures below in which example compounds
of each hydrocarbon class have been analyzed by methane (positive)
CI/MS. In most cases a distinct series of ions was formed for each
hydrocarbon type. These distinctions for each hydrocarbon type will be
briefly discussed. Figure 4.3 illustrates the mass spectra of three
different paraffinic compounds. The common fragment ions are m/z 71,
85, and 99. The relative abundance of each seems dependent upon the
degree and position of branching. The other major ions are the [M-l]+,
and the [M-15]+ for highly branched molecules such as the 2,2,4,6,6-
pentamethylheptane. Figure 4.4 illustrates the mass spectra of three
cycloparaffinic compounds. The distinction here is the low relative
abundance of any fragment ions, with the exception of [M-l]+ ion (base
peak), for both substituted and unsubstituted rings. Figure 4.5

% Relative Abundance
98
miz
Figure 4.3. Methane chemical ionization mass spectra of a) 2,2,5-
trimethylhexane, b) n-decane, c) 2,2,4,6,6-
pentamethylheptane.

% Relative Abundance
M-l
99
Figure
100.0-1
c)
13?
M-1+
50.0-
50
59
““T
83
A
97 I.
1 ‘ ¡ 1 1 1 1 1 ■'1 ' i ■ ' • i 1 i ' i ' | 1
100 150 200
m/z
.4.
Methane chemical ionization mass spectra
cyclooctane, b) methylcyclohexane, c) decalin.
of a)

% Relative Abundance
100
miz
Figure 4.5.
Methane chemical ionization of a)p-xylene, b)
propylbenzene, c) n-butylbenzene.
n-

101
illustrates the mass spectra of several alkylbenzenes. The distinction
here is the formation of the [M+l]+ base peak. Problems arise by the
formation of molecular adduct ions such as [M+29]+ and [M+41]+ which
are the same mass as the [M+l]+ ions of higher mass alkylbenzenes.
However, at least the ions are common within the alkylbenzene type.
Figure 4.6 illustrates the mass spectra of indane, tetralin, methyl-
and dimethylnaphthalene which also show behavior similar to the
alkylbenzenes, except the ions are distinctive for the molecular
weights of each of these types. If one were to inspect the mass
spectral peaks of all these examples, at 20% or greater relative
abundance, there would be no overlap of peaks among the six hydrocarbon
types for the examples studied. Such a result is a step towards the
development of the ideal detector for hydrocarbon type analysis. This
system is by no means complete, since only a few example compounds of
each hydrocarbon type have been tested and no real applications have
been made towards jet fuel analysis. However, the results do suggest
future directions to pursue.
Summary of Results
The above discussion illustrates the utility of alternative
ionization techniques for the analysis of mixtures such as jet fuels.
Although no results were given for actual jet fuels, several potential
methods have been introduced for future work in jet fuel analysis. For
the electron energy study, a simple and specific detection scheme for
the analysis of the aromatic fraction of fuels was introduced. For the
CI/MS study a potentially new hydrocarbon type analysis method was

% Relative Abundance
102
M+l+
m/z
Figure 4.6. Methane chemical ionization mass spectra of a) indane,
b) tetralin, c) methylnaphthalene,
d) dimethylnaphthalene.

103
suggested as a result of class specific ions of each hydrocarbon type.
This technique be potentially useful not only as an HTA method, but
also for specific component analysis when combined with GC separation.

CHAPTER V
PRELIMINARY INVESTIGATIONS OF GC/MS/MS TECHNIQUES
FOR JET FUEL ANALYSIS
The primary goal of this area of study was to investigate GC/MS/MS
techniques for the analysis of jet fuels. This chapter will mainly
cover aspects of hydrocarbon type analysis, although the major effort
was directed toward total fuel analysis. The combination of high
resolution gas chromatography and tandem mass spectrometry will be a
powerful approach for the determination of specific components in jet
fuels.
Background
Mass Spectrometry/Mass Spectrometry
In these studies tandem quadrupole mass spectrometry (TQMS) was
used for the evaluation of jet fuel detection schemes. The application
of TQMS for the analysis of complex mixtures was first introduced by
Yost and Enke (74). The ability to achieve low limits of detection is
greatly enhanced over conventional MS systems because of the increased
selectivity of MS/MS. McLafferty's book on tandem mass spectrometry
(80), has several reviews which deal with the fundamentals,
instrumentation, advantages and disadvantages, and applications of
MS/MS. The tandem mass spectrometer may operate under several modes
104

105
depending on the application. These operational or scan modes are
shown in Figure 5.1. Normal mass spectrometry may be obtained by
scanning quadrupole one (Ql) or quadrupole three (Q3). The center
quadrupole (Q2) is pressurized with an inert gas for collision induced
dissociation (CID) reactions. A daughter scan mass spectrum is
obtained by selecting a particular m/z (parent ion) with Ql. This ion
is fragmented in Q2 by the CID process. The resulting daughter ions
are mass-analyzed by Q3, which results in a daughter mass spectrum of
the chosen parent ion. This technique is mainly used for structure
elucidation and validation of unknown components. A knowledge of the
ions observed in the daughter scan mass spectra from a sample is
helpful when using the parent scan MS/MS operational mode. A parent
scan mass spectrum is obtained by scanning Ql to sequentially pass all
ions produced in the ion source. These ions are fragmented in Q2 by
the CID process as Q3 passes an ion of a certain mass (daughter ion) .
The resulting parent mass spectrum illustrates those parent ions which
produce the particular daughter ion by CID. Parent scan mass spectra
are quite useful as a screening technique for a particular class of
compounds since components within a class of compounds may undergo CID
to generate the same daughter ions.
Application of GC/MS/MS to Jet Fuel Analysis
Many applications of MS/MS to fuel analysis have appeared in the
literature, as discussed in Chapter I. These application have dealt
mainly with the determination of specific components, or a few
components of similar classes.

106
03 FULL SCAN MODE
02
0 3
nr
DAUGHTER SCAN MODE
PARENT SCAN MODE
OI 02 Q3
Figure 5.1. Some scan modes of the triple quadrupole mass
spectrometer.

107
The application of combined GC/MS/MS techniques for hydrocarbon
type analysis of jet fuels is a novel idea which has been investigated
in this study. The success of this technique will be dependent on the
ability to implement MS/MS scan modes which are specific for given
hydrocarbon types. In other words, the system will be useful only if
MS/MS can provide a specific detection method for specific hydrocarbon
types (which may vary depending on the number of class distinction
pursued). The results of these investigations are discussed below.
The major application of GC/MS/MS foreseen for the analysis of jet
fuels is the development of methods for total fuel analysis. For
example, a certain hydrocarbon type may be evaluated for specific
components by retention time if a type - specific MS/MS scan mode is
available for that hydrocarbon type. Of particular importance would be
the analysis of jet fuels for trace components such as heteroatomics
and fuel additives.
Experimental
All instrumental parameters were unchanged unless otherwise
specified in this section.
All MS/MS experiments were performed with nitrogen collision gas at
a pressure between 0.1 and 0.2 mTorr. The collision induced
dissociation energy was 25 eV. The collision energies were varied
under computer control in the energy-resolved study.

108
Results and Discussion
The following experimental results are preliminary investigations
on the use of GC/MS/MS scan modes as specific detectors for hydrocarbon
types in jet fuels. The development of a complete GC/MS/MS method was
not the objective of these investigations.
MS/MS for Hydrocarbon Type Analysis
To simplify the investigation of GC/MS/MS/HTA methods, only the
paraffins and alkylbenzenes were targeted for study. Parent scan mass
spectrometry was used since it is best suited for class (or type)
screening which was the goal of this study. For these investigations,
Isopar M and Aromatic 150 were used as the paraffin and alkylbenzene
mixtures, respectively. The daughter ions used in the parent scan mass
spectra were determined from the daughter scan mass spectra obtained
from each of these complex mixtures. The paraffin daughter ions were
those ions contained in the paraffin summation series (243) in Table
2.1. The most intense of these ions were the m/z 43, m/z 57, m/z 71,
and m/z 85. Of course the choice of parent ions of these daughter ions
may affect the results, but the average daughter ion mass spectra of
the entire range of paraffinic molecular ions (m/z 100, 114, 128,... up
to m/z 170) were evaluated. These four ions (m/z 43, 57, 71, and 85)
were chosen as the daughter ions used in the paraffin parent scan mass
spectra.
Figure 5.2 illustrates the average daughter scan mass spectrum of
m/z 134 of Aromatic 150. The remaining parent ions of the alkylbenzene
series (m/z 120, m/z 148, and m/z 162) produced similar daughter scan
mass spectra. Therefore the four most intense daughter ions (m/z 77,

% Relative Abundance
100.0 -|
50. ft -
119
Aromatic 150
â– 
Daughters of m/z 134
9
1 K
15
*7
i 1
124
53 ||
i ■■ i—>—i—i—r
i, 1
, r—
50
l 00
150
mlz
Figure 5.2.
Average daughter ion mass spectrum of m/z 134 of
Aromatic 150.
250

110
m/z 91, m/z 105, and m/z 119) were chosen as the daughter ions used in
the alkylbenzene parent scan mass spectra. Figure 5.3 and Figure 5.4
illustrates the selectivity of these two parent scan modes. The parent
scans of alkylbenzenes daughter ions respond to Aromatic 150 and not to
Isopar M, whereas the parent scans of paraffin daughter ions respond to
Isopar M and not to Aromatic 150. This would provide a HTA method if
distinction were desired between only these two classes. The Finnigan
TSQ45 mass spectrometer is limited by the number of parent scan mass
spectra it may acquire under one run. Ultimately parent scans for all
six hydrocarbon types would be desired. Therefore, one or two parent
scans would have to be chosen for each hydrocarbon type. Because of
this, investigations were made into the differences between parent
scans of different daughter ions. Figure 5.5 illustrates the Isopar M
chromatograms of the four paraffin parent scans. Little difference is
observed between the chromatograms for parent ions of m/z 43, m/z 57,
and m/z 71, except that the parents of m/z 71 were only 25% of the
response of the others. The chromatogram for the parents of m/z 85
shows very little response. Therefore a single parent scan for m/z 43
or m/z 57 might be used for detection of all paraffins since little
discrimination is observed for either daughter with respect to
retention.
The chromatograms for the parents of the alkylbenzene daughter ions
were quite different in comparison. Figure 5.6 illustrates the
Aromatic 150 chromatograms from the four alkylbenzene parent scans.
There are obviously some distinctions between the four parent scans, as
evident by the different chromatographic profiles produced. Clearly,

The GC/MS/MS (parents of alkylbenzene ions, m/z 77, m/z
91, m/z 105, and m/z 119) reconstructed ion current
chromatograms of a) Isopar M and b) aromatic 150.
Figure 5.3.

100. ¡H
112
Figure 5.4. The GC/MS/MS (parents of paraffin ions, m/z 43, m/z 57,
m/z 71, and m/z 85) reconstructed ion current
chromatograms of a) Isopar M and b) Aromatic 150
(enlarged X10).

Figuro 5 S The t'C/MS/MS (parents of paraffin ions, m/z 43, m/z 57,
in.'/. /1, and m/z 85) reconstructed ion current chromatograms for
each individual parent scan for Isopar M.
113

Figure 5.6. The GC/MS/MS (parents of alkylbenzene ions, m/z 77, m/z 91,
m/z 105, and m/z 119) reconstructed ion current chromatograms for
each individual parent scan for Aromatic 150.
114

115
alkylbenzenes of higher molecular weight (longer retention times)
fragment upon CID to form different daughter ions. Therefore it is not
possible to choose one particular parent scan to represent the
alkylbenzenes as a whole.
It would be quite useful to perform the parent scan analysis of all
hydrocarbon types for each characteristic daughter ion, but as
mentioned above, the method would be limited due to the sampling time
required by the mass spectrometer to scan over the various daughter
ions. A preliminary investigation was made into the application of
parent scan GC/MS/MS for HTA of a jet fuel (JP-7) to provide an example
of how the method could be applied. Figure 5.7 illustrates the results
of this experiment, in which one parent scan was performed for each of
the six hydrocarbon types (parents of paraffins, m/z 57; parents of
monocycloparaffins, m/z 69; parents of dicycloparaffins, m/z 81;
parents of alkylbenzenes, m/z 119; parents of indanes and tetralins,
m/z 117; and parents of naphthalenes, m/z 128. The corresponding HTA
results were: paraffins, 50%, dicycloparaffins, 17%; alkylbenzenes,
20%; and indanes and tetralins, 1%. The maximum intensities in the
parent scan chromatograms correlate with the HTA results quite well
except for the alkylbenzene parent scan for m/z 119 which would not be
expected to detect all alkylbenzenes as discussed above.
Other GC/MS/MS Modes of Analysis
As mentioned above, the greatest potential for GC/MS/MS analysis of
jet fuels involves the determination of specific components or specific
classes of components. The tandem mass spectrometer has the ability to
profile the molecular weight parent ion distribution of a daughter ion

Reconstructed Ion Current
116
I
11;
Dicycloparaffins
Parents of m/z 81
â– m
Paraffins
Parents of m/z 57
Total of All Parents
« .o io oo u jo it «o :o oo
Retention Time (min:sec)
Figure 5.7. The MS/MS reconstructed ion current chromatogram of a
select set of 4 parent scans (hydrocarbon types) for JP-7
jet fuel.

117
from a specific class of compounds. Figure 5.8 shows the results of a
parent scan of m/z 105 for Aromatic 150. A profile of each parent ion
is displayed which corresponds to the particular parent/daughter ion
pair. The distribution of molecular weights of the alkylbenzenes may
be visualized from this display. Furthermore, quantitation may be
obtained for each particular parent/daughter pair. One might assume
that the same information could be obtained using mass chromatograms
obtained by normal GC/MS. Figure 5.9 shows the same Aromatic 150
mixture analyzed by normal mass spectrometry and the results displayed
as mass chromatograms. It is quite evident that GC/MS does not provide
the distinct molecular weight distribution obtained with the GC/MS/MS.
Differentiation of Isomeric Hydrocarbon Types
As discussed previously in Chapter III, there is a need to
differentiate between cycloalkane and olefin hydrocarbon types in jet
fuels. In the HTA methods, no differentiation is made between the two
isomers in the final volume percent results. As shown in Chapter III,
erroneous behavior may result where large concentrations of olefins are
present. Therefore, the ability to assess the olefin concentration
separate from the cycloalkane concentration would be very beneficial in
the hydrocarbon type analysis of fuels.
The ability to differentiate between isomeric cycloparaffins and
olefins of the same carbon number by normal EI/MS has already been
presented in Figure 3.14-3.16. However, not all isomers of the same
carbon number produce such different El mass spectra. Figure 5.10
illustrates the El mass spectra obtained for cyclooctane, 1-octene, and
ethylcyclohexane, all C8 isomers. Subtle differences in the mass

118
m/z 140
1
f*. â– J \ ,'A'i
--4 ^-V- ,J" . Vf U ' A,
m/z 162
-jLwV>
v/w.
Figure 5.8. The MS/MS (parents of m/z 105) reconstructed ion current
chromatogram for Aromatic 150 and the corresponding mass
chromatograms of the common alkylbenzene parent masses.

GC! MS
119
35.7-
A
)â– 
yv
m/z
120
100.0-
m/z
134
22.5-
j \
m/z
148
0.6q
m/z 162 ,
A
ftlf
1
0.0-
m/z
176
709.7-
PIC.
. i
Total
50 100
0:50 1:40
i
150
2:20
2f
;
GCIMS/MS-Parents of m/z 105
Figure 5.9. Comparison of normal GC/MS mass chromatograms and
GC/MS/MS parent scan mass chromatograms for molecular
weight distribution.

% Relative Abundance
120
miz
Figure 5.10. The El mass spectra of cyclooctane, 1-octene, and
ethylcyclohexane isomers.

121
spectra can be seen between the cyclooctane and octene isomers when
compared to the significantly different ethylcyclohexane isomer. This
demonstrates the need for new GC/MS methods for the differentiation of
cycloparaffin and olefin isomers.
The application of MS/MS in the daughter scan mode may provide the
capability to distinguish between cycloalkane and olefin isomers.
Fetterolf and Yost (81) have demonstrated the ability to differentiate
between isomeric ion structures by energy-resolved CID breakdown
curves. In such a study the relative abundances of a characteristic
set of ions is plotted versus the CID collision energy. Each isomer
may produce a distinguishable energy breakdown curve different from the
other isomer. Figure 5.11 and Figure 5.12 illustrates the variation in
the fragmentation pattern of the daughter ion mass spectra obtained for
M+ ions of cyclooctane and 1-octene, respectively, at two different
collision energies. At higher collision energies (25 eV), greater
fragmentation has resulted, as indicated by the presence of low mass
fragments arising from single bond cleavage and the absence of higher
mass fragments. At lower collision energies (5 eV), less fragmentation
was observed as indicated by the higher mass fragments arising from
rearrangement reactions (even m/z). It is evident from these results
that the low energy CID process resulted in a more distinguishable
daughter ion mass spectrum. Certainly these results demonstrate the
possibility of applying energy-resolved breakdown studies for the
differentiation of cycloalkane and olefin isomers. However, the
discovery of some characteristic fragmentation ion which distinguishes
between cycloparaffin and olefin isomers for all carbon numbers would

% Relative Abundance
miz
Figure 5.11. The MS/MS daughter ion mass spectra of the M+ ion (m/z 112) of
cyclooctane at two CID collision energies. 5 eV and 25 eV.
122

% Relative Abundance
miz
Figure 5.12. The MS/MS daughter ion mass spectra of the M+ ion (m/z 112) of
octene at two CID collision energies, 5 eV and 25 eV.
123

124
be much more desirable. The possibilities of such a case are
illustrated in Figure 5.13 in which the 5 eV daughter ion mass spectra
of the molecular ions of the two isomers are compared. For the
cyclooctane isomer, much larger relative abundances were observed for
m/z 83 and m/z 84 which correspond to neutral losses of C2H3 and C2H4.
This neutral loss is greater for the strained cyclic structure than for
the linear olefin molecule (81) . The behavior of this isomeric pair
does not necessarily reflect the behavior of all cycloparaffin/olefin
isomeric pairs; however, further investigations may prove quite useful.
Summary of Results
The application of GC/MS/MS to the analysis of jet fuels has been
demonstrated to have a significant potential for solving some of the
existing problems associated with jet fuel analysis. The
differentiation between paraffinic and aromatic mixtures was made using
parent scan GC/MS/MS. Differentiation of hydrocarbon types in a jet
fuel was demonstrated using a single parent scan for each hydrocarbon
type. The relative intensity of the mass chromatograms for each parent
scan agreed with the GC/MS/HTA results. The molecular weight
distribution may be displayed using mass chromatograms and parent scan
MS/MS. Finally, the potential of daughter scan MS/MS as a technique
for differentiation between cycloalkane and olefin isomers was
demonstrated.

Relative Abundance
100.0-1
70
1-Octene
50.0-
43
8
4
4*tt i'h*» i rrfn
55
T-rfr-tT r|vm
i■ i ■1-1’•
82
â– ? t n rt m i rr r
86
1 1*1 l 1 I 1 1 1
9/ 106
I'lill [ FI r T i l | l i
127 133
i t i i ti «"I iVrrrrtn J r r rr| n rr rrrJ
100.0-1
50.0
70
8
3
Cyclooctane
c
41
i r J-l T i | . rr 1-1 \ 1 I 1
6
112
li it i 1
' " ' 1 ' ' " 1 'I
86
•1 t i
97
~t~» > i1! T*T rS i f i
122 133
TT-TT-H [ 1 t l‘ » | l*m | 1 rS-l'J-l-fl 1 I I 1 i T | I T 1 M I 1 J
40
60
80
m/z
100
120
140
Figure 5.13.
Comparison of MS/MS daughter ion mass
(m/z 112) of cyclooctane and I m l i n.
energy.
spectra of the M4 ions
at 5 eV CID collision
125

CHAPTER VI
CONCLUSIONS AND FUTURE WORK
This research project was organized around two goals. The main
effort was devoted to the development, characterization, and
implementation of a new gas chromatographic/mass spectrometric (GC/MS)
method of hydrocarbon type analysis (HTA) of jet fuels. The secondary
effort was for the evaluation of ancillary techniques of mass
spectrometry, such as alternative ionization and tandem mass
spectrometry, for the determination of specific components or specific
classes of components in jet fuels. A major advantage of these GC/MS
techniques will be the ability to have a wide range of analyses
available under one instrumental configuration. That is, a jet fuel
sample may be analyzed by the hydrocarbon type method, and with minimal
effort the instrumental configuration could be changed (for example to
methane Cl) in order to analyze the aromatic fraction in greater
detail.
Summary of Results
Hydrocarbon Type Analysis
To most analytical chemists, the idea of type analysis is not very
well known or understood. In this study much has been learned in
regard to type analysis, specifically, hydrocarbon type analysis.
126

127
A new HTA method was developed for the analysis of jet fuels using
GC/MS and the pre-existing ASTM inverse calibration matrix. The
GC/MS/HTA method was characterized by several analytical techniques.
The results of the GC/MS/HTA of fuels were compared to ASTM results.
This did not provide much information since the accuracy of the ASTM
results are not known.
The analysis of simple mixtures was conducted and compared to
actual volume calculated results. These experiments were generally
unsuccessful for the characterization of the GC/MS/HTA analysis due to
the simplicity of the sample make-up which caused errors in the matrix
calculation. However, results tend to support the "Teeter Rule" which
basically states that no sample could be synthetically prepared which
would be complex enough for the inverse calibration calculation to be
valid.
A new method was applied for the characterization of this HTA
analysis. In this method, jet fuel samples were perturbed by spiking
the fuel with a known volume of a pure component or a mixture of a
specific hydrocarbon type (such as Aromatic 150) . This method
maintained the required sample complexity for proper matrix calculation
and allowed for an accurate assessment of the added spike. This method
proved to be the most valuable technique for the characterization of
the GC/MS/HTA method.
Calculation of Average Carbon Number
The most novel part of this research was the development of a new
method for the determination of average carbon numbers. This method
was based on GC/MS simulated distillation whereby the average carbon

128
number was determined based on the chromatographic separation. The
average carbon number results were generally higher than the results
calculated by the matrix method in the present GC/MS/HTA method or the
ASTM method. We have more confidence in the simulated distillation
methods, which suggest a serious limitation in the other two
techniques. The GC/MS/HTA and ASTM methods both rely heavily on the
average carbon number results, which therefore suggest a serious
limitation in the volume percent results.
Ancillary Mass Spectrometric Methods
Summary of the studies of these ancillary MS techniques may well be
considered suggestions for future work. No final methods were
developed; rather suggestions were made for potential methods which
could be developed.
Two alternative ionization techniques in mass spectrometry were
evaluated for specific detectors of hydrocarbon types. Low energy
electron ionization was demonstrated to be a specific detector for
aromatics in the presence of aliphatic components. Methane chemical
ionization, of common fuel components demonstrated very selective ion
patterns for each specific hydrocarbon type. This method has good
potential as a new hydrocarbon type analysis method, but would require
extensive standardization.
Mass Spectrometry/mass spectrometry demonstrated great potential as
a selective means of determining aromatics in the presence of paraffins
as well as paraffins in the presence of aromatics. This was obtained
using parent scan MS of selective daughter ions specific for each type.
An actual jet fuel was analyzed using parent scan MS/MS. Good

129
agreement was obtained between the relative intensities of the mass
chromatograms of each parent scan and the GC/MS/HTA results.
Differentiation between isomers of cycloparaffins and olefins was
demonstrated using daughter scan MS/MS. These differences were
dependent upon the collision energy, which demonstrates the potential
use of energy-resolved collision-induced dissociation breakdown curve
analysis. The ability to differentiate between these isomers is very
important in regards to hydrocarbon type analysis, since large
quantities of olefins may result in erroneous behavior of the GC/MS/HTA
method.
The methods developed and the techniques evaluated represent a
significant contribution to the analysis of jet fuels. Already, the
GC/MS/HTA method has been implemented in the industrial sector. The
method is simple and may be performed on most GC/MS instruments.

APPENDIX A
MATRIX INVERSION METHOD
Consider the matrices 5, 9, and T in which S=the calibration
mixture matrix, 0=the calibration data matrix of the 2-ion series, and
T=the inverse calibration matrix. The 9-calibration data matrix may be
a square or unsymmetrical matrix, while the other matrices, 5 and r are
always square. The methods used for calculating both cases are shown
below for the simplest examples, a 3x3 and a 3x4 9-matrix. In both
cases the 9-matrix equals the diagonal matrix shown below.
9= 100 0 0
0 100 0
0 0 100
For both cases, 9=8*r (the normalization function) enables the
determination of the inverse calibration matrix, T since both 5 and 9
are known. The inverse calibration matrix is obtained by solving for T
in the following way:
for the 3x3 5-example;
T=9*6~1
for the 3x4 5-example;
r=(6+8)-18T9.
The functions 5+, and ST are the complex conjugate and transpose of the
matrix 6, respectively.
130

APPENDIX B
EXAMPLE GC/MS/HTA CALCULATION
The fuel used for the example calculation is 87-POSF-2532, a Jet-A
type fuel. The results of the hydrocarbon type analysis for this fuel
may be found in Chapter III.
The aromatic and paraffinic average carbon numbers for the example
fuel were calculated to be 9.29 and 9.04, respectively. A weighted
mixture of the carbon no. 9 and carbon no. 10 matrices must be used in
calculating the volume percent of hydrocarbon type. The procedure
involves calculating the volume percent twice; first based on carbon
no. 9, then based on carbon no. 10. The final result is then
determined by weighing the two results as determined by the actual
aromatic and paraffinic average carbon numbers.
The example which follows will first illustrate the generic
expressions for calculating the paraffin result for carbon no. 9. This
is similar for calculations of all types and carbon numbers as is shown
in the calculation of hydrocarbon type using the example fuel results
and carbon no. 9 matrix. Finally the results hydrocarbon type analysis
will be used for both Carbon No. 9 and 10 and the weighted result
determined.
131

132
I. Generic Expression For Type Analysis
C9 Paraffin = C9(l,1)(243%) + C9(1,2)(241%) + C9(1,3)(267%)
+ C9(l,4)(277%) + C9(l,5)(2103%) + C9(1,6)(2128%)
Where C9(l,l) represents row one column one entry of the Carbon No. 9
inverse calibration matrix. The 243% represents the percent
contribution of 243 to the 2T ion count.
II. Sample calculation of the Carbon No. 9 results.
C9 Paraffin = (.006043)(20.04)-(.000673)(35.79)+(.000071)(29.92)
-(.000018)(9.79)-(.000095)(4.20)-(.000075)(0.26)
= 0.9854E-1
C9 Monocycloparaffin = -(.001933)(20.04)+(.006183)(35.79)
-(.001929)(29.92)-(.000130)(9.79)-(.000017)(4.20)+(.000011)(0.26)
= 0.1235
C9 Dicycloparaffin = (.000212)(20.04)-(.000822)(35.79)
+(.006809)(29.92)+(.000003)(9.79)+(.000004)(4.20)-(.000006)(0.26)
= 0.1786
C9 Alkylbenzenes = (. 000007)(20.04)-(.000040)(35.79)
-(.000261)(29.92)+(.004015)(9.79)-(.000787)(4.20)-(.000248)(0.26)
= 0.2684E-1

133
C9 Indanes/Tetralins = (.000001)(20.04) + (.000002)(35.79)
+(.000020)(29.92)-(.000361)(9.79>+(.005496)(4.20)-(.000016)(0.26)
= 0.2023E-1
C9 Naphthalenes = -(.000090)(20.04)+(.000008)(35.79)+ 0+0
+(.000001)(4.20)+(.005759)(0.26)
= -0.1574E-4
The negative result for naphthalene is correct. This is a limitation
of the matrix method since the volume percent value will ultimately be
truncated to zero. Including the results for each type using carbon
no. 10 matrix:
CIO Paraffin = 0.7766E-1
CIO Monocycloparaffin = 0.1265
CIO Dicycloparaffin = 0.1413
CIO Alkylbenzene = 0.2756E-1
CIO Indanes/Tetralins = 0.2465E-1
CIO Naphthalenes =-0.8744E-3
and application of the weighing expression:
Weighted Type (paraffins)=
(C9 Type) + (C9 Type - CIO Type)(paraffin carbon number - 9)

134
Weighted Type (aromatic)=
(C9 Type) + (C9 Type - CIO Type)(aromatic carbon number - 9).
It should be pointed out again that the paraffin carbon number is used
for the three saturated types and the aromatic for the three
unsaturated types.
The example calculations are as follows:
Paraffins = (0.9854E-1) + (0.7766E-1 - 0.9854E-1)(9.0355 - 9)
= 0.9780E-1
Monocycloparaffins = (0.1235) + (0.1265 - 0.1235)(9.0355 - 9)
= 0.1236
Dicycloparaffins = (0.1786) + (0.1413 - 0.1786)(9.0355 - 9)
= 0.1773
Alkylbenzenes = (0.2684E-1) + (0.2756E-1 - 0.2684E-1)(9.2914 - 9)
= 0.2705E-1
Indane/Tetralin = (0.2023E-1) + (0.2465E-1 - 0.2023E-1)(9.2914 - 9)
= 0.2152E-1
Naphthalenes = -(0.1574E-4) - (0.8744E-3 + 0.1574E-4)(9.2914 - 9)
= -0.2751E-3 = 0 since a negative volume percent is undefined.
Total = 0.4472
Note that the saturated components use the paraffin carbon number and
the unsaturated components use the aromatic carbon number. A negative
result is truncated to zero. The values are now normalized to 100% and
represent the final volume percent of each hydrocarbon type.

135
The results are:
Paraffins = (0.9780E-1/0.4472)*100 = 21.87
Monocycloparaffins = (0.1236/0.4472)*100 = 27.64
Dicycloparaffins = (0.1773/0.4472)*100 = 39.64
Alkylbenzenes = (0.2705E-1/0.4472)*100 = 6.05
Indane/Tetralin = (0.2705E-1/0.4472)*100 = 4.81
Naphthalenes = (0/0.4472)*100 = 0.00

APPENDIX C
GC/MS/HTA TURBO BASIC PROGRAM
Turbo Basic Program September 15, 1987
GCMSHTA.BAS
This program was written to perform the calculations set out in the
GC/MS Hydrocarbon Type Analysis Method for Jet Fuels developed by
Michael J. Gehron and Richard A. Yost at the University of Florida,
Department of Chemistry. Funding and support was provided by
Wright-Patterson Air Force Base-Fuels Division contract
no. F33615-85-C-2508, through United Technologies-Pratt & Whitney.
GC/MS HYDROCARBON TYPE ANALYSIS PROGRAM
MAJOR VARIABLES
C78 , C91, etc ION INTENSITIES FROM GC/MS
ISUM(N) ION SUMMATION VALUES FOR EACH HYDROCARBON TYPE
CALCULATED FROM THE GC/MS MASS CHROMATOGRAMS
AACN AROMATIC AVERAGE CARBON NUMBER
PACN PARAFFIN AVERAGE CARBON NUMBER
C6(J,I) - C10(J,I) VARIABLE ARRAYS FOR INVERSE CALIBRATION MATRIX
DATA STORAGE
READING IN OF ION INTENSITY DATA
CLS
136

137
PRINT "ENTER DATA INPUT SOURCE KEYBOARD(K) OR DISK(D)
DIM ISUM(6)
INPUT A$
IF A$="D" OR A$="d" GOTO 10
INPUT "ENTER DATA FILE NAME TO CREATE
(DRIVE:\PATH\FILENAME.DAT)";B$
OPEN "0", 1, B$
PRINT "ENTER AROMATIC ION INTENSITIES 78,91,92,105,106,
119,120,133,134"
PRINT "147,148,161,162"
PRINT " "
INPUT C78,C91,C92,C105,C106,C119,C120,C133,C134,C147,C148,C161,C162
PRINT "ENTER PARAFFINIC ION INTENSITIES 84,85,86,98,99,100,
112,113,114"
PRINT "126,127,128,140,141,142,154,155,156,168,169,170"
INPUT C84,C85,C86,C98,C99,C100,C112,C113,C114,C126,C127,C128
INPUT C140,C141,C142,C154,C155,C156,C168,C169,C170
PRINT#1,C78,C91,C92,C105,C106,C119,C120,C133,C134,
C147,C148,C161,C162
PRINT #1,C84,C85,C86,C98,C99,C100,C112,C113,C114,C126,C127,C128
PRINT #1,C140,C141,C142,C154,C155,C156,C168,C169,C170
PRINT "ENTER ION SUMMATION VALUES FOR EACH HYDROCARBON TYPE"
FOR N=1 TO 6
INPUT ISUM(N)
PRINT #1,ISUM(N)
NEXT N
CLOSE //I
GOTO 40
10 PRINT "ENTER DATA FILE NAME (DRIVE:\PATH\FILENAME.DAT)"
PRINT " "
INPUT B$
OPEN "I",2,B$
INPUT#2 , C78 , C91, C92 , C105 , C106 , C119 , C120 ,
C133,C134,C147,C148,C161,C162
INPUT #2,C84,C85,C86,C98,C99,C100,C112,C113,C114,C126,C127,C128
INPUT #2,C140,C141,C142,C154,C155,C156,C168,C169,C170
DECIDE IF ION SUMMATION VALUES WILL BE ENTERED WITH KEYBOARD OR
FILE
INPUT "IS THERE A HTA ION SUMMATION FILE ???? (Y)ES OR (N)O"; C$
IF C$="Y" OR C$="y" GOTO 15
CLOSE #2
PRINT "ENTER ION SUMMATION VALUES FOR EACH HYDROCARBON TYPE”
OPEN "A",2,B$
FOR N=1 TO 6
INPUT ISUM(N)
PRINT #2,ISUM(N)
NEXT N

CLOSE #2
GOTO 40
15 FOR N=1 TO 6
INPUT #2,ISUM(N)
NEXT N
30 CLOSE #2
CALCULATION OF AROMATIC AVERAGE CARBON NUMBER
CALCULATION OF MONOISOTOPIC PEAKS
40 M92=C92-(.0769*C91)
M106=C106-(.0880*C105)
M120=C120-(.0991*C119)
M134=C134-(.1102*C133)
M148=C148-(.1212*C147)
M162=C162-(.1323*C161)
CONVERT MONOISOTOPIC PEAKS TO MOLAR BASIS
MB78=C78*1.0
IF MB78<0 THEN MB78=0
MB92=M92*1.7
IF MB92<0 THEN MB92=0
MB106=M106*2.2
IF MB106C0 THEN MB106=0
MB120=M120*2.4
IF MB120<0 THEN MB120=0
MB134=M134*2.7
IF MB134<0 THEN MB134=0
MB148=M148*2.8
IF MB148C0 THEN MB148=0
MB162=M162*2.9
IF MB162C0 THEN MB162=0
MBTOT=MB78+MB92+MB106+MB12O+MB134+MB148+MB162
NORMALIZE MOLAR BASIS AND CONVERT TO RELATIVE MOLE FRACTION
MF7 8=MB7 8/MBTOT*6
MF92=MB92/MBTOT*7
MF106=MB106/MBTOT*8
MF120=MB120/MBTOT*9
MF134=MB134/MBTOT*10
MF148=MB148/MBTOT*ll
MF162=MB162/MBTOT*12
AROMATIC AVERAGE CARBON NUMBER
AACN=MF78+MF92+MF106+MF120+MF134+MF148+MF162
PRINT "AROMATIC AVERAGE CARBON NUMBER EQUALS",AACN
CALCULATION OF PARAFFIN AVERAGE CARBON NUMBER

139
CALCULATION OF MONOISOTOPIC PEAKS
M86=C86-(.0668*C85)+(.0026*C84)-(.014*M92)-(.008*M106)-(.008*M120)
M100=C100-(,0779*C99)+(.0034*C98)
M114=C114-(.0890*C113)+(.0044*C112)
M128=C128-(.1001*C127)+(.0055*0126)
M142=C142-(.1130*C141)+(.0068*C140)
M156=C156-(.1224*C155)+(.0081*C154)
M170=C170-(.1335*C169)+(.0096*C168)
CONVERT MONOISOTOPIC PEAKS TO MOLAR BASIS
MB86=M86*1.0
IF MB86<0 THEN MB86=0
MB100=M100*.92
IF MB100<0 THEN MB100=0
MB114=M114*1.4
IF MB114C0 THEN MB114=0
MB128=M128*1.8
IF MB128C0 THEN MB128=0
MB142=M142*1.9
IF MB142<0 THEN MB142=0
MB156=M156*2.0
IF MB156C0 THEN MB156=0
MB170=M170*2.1
IF MB170<0 THEN MB170=0
MBTOL=MB86+MB100+MB114+MB128+MB142+MB156+MB170
NORMALIZE MOLAR BASIS AND CONVERT TO RELATIVE MOLE FRACTION
MF86=MB86/MBTOL*6
MF100=MB100/MBTOL*7
MF114=MB114/MBT0L*8
MF128=MB128/MBTOL*9
MF142=MB142/MBTOL*10
MF156=MB156/MBTOL*ll
MF17 0=MB17 O/MBTOL*12
PARAFFINIC AVERAGE CARBON NUMBER
PACN=MF86+MF100+MF114+MF128+MF142+MF156+MF170
PRINT "PARAFFIN AVERAGE CARBON NUMBER",PACN
CALCULATION OF VOLUME % OF HYDROCARBON TYPES
DIMENSIONING OF VARIABLE ARRAYS
DIM C6(6,6),C7(6,6),C8(6,6),C9(6,6),C10(6,6),V(6),M6(4),M7(5)
DIM M8(6),M9(6),M10(6)
READING OF CALIBRATION MATRIX DATA FOR C6
FOR J=1 TO 4
FOR 1=1 TO 4

140
READ C6(J,I)
NEXT I
NEXT J
DATA .009016,-.001368,.000257,-.000003,-.004471,.010285,-.002391
DATA -.000002,.000100,-.000258,.004325,0,.000017,-.000048,-.000149,
DATA .005117
READING OF CALIBRATION MATRIX DATA FOR C7
FOR J=1 TO 5
FOR 1=1 TO 5
READ C7(J,I)
NEXT I
NEXT J
DATA .007241,-.000655,.000105,-.000100,-.000100,-.002542,.007283,
DATA -.001695,-.000051,-.000035,.000167,-.000523,.004387,.000001
DATA,.000003,.000010,-.000044,-.000134,.004576,-.000897,0,0
DATA -.000002,0,.005424
READING OF CALIBRATION MATRIX DATA FOR C8
FOR J=1 TO 6
FOR 1=1 TO 6
READ C8(J,I)
NEXT I
NEXT J
DATA .006449 , -.000584,.000090,-.000011,-.000105,-.000082,-.001902
DATA .006132,-.001428,-.000063,-.000029,.000006,.000128,-.000469
DATA .004375,.000001,.000003,-.000004
DATA .000007,-.000049,-.000125,.004375,-.000857,-.000271,0,.000002
DATA .000004,-.000207,.005465,-.000026,0,0,0,0,0,.005757
READING OF CALIBRATION MATRIX DATA FOR C9
FOR J=1 TO 6
FOR 1=1 TO 6
READ C9(J,I)
NEXT I
NEXT J
DATA .006043,-.000673,.000071,-.000018,-.000095,-.000075,-.001933
DATA .006183,- . 001929 , - . 000130,-.000017,.000011,.000212,-.000822
DATA .006809,.000003,.000004,-.000006
DATA .000007,-.000040,-.000261,.004015,-.000787,-.000248,.000001
DATA .000002,.000020,-.000361,.005496,-.000016,-.000090,.000008
DATA 0,0,.000001,.005759
READING OF CALIBRATION MATRIX DATA FOR CIO
FOR J=1 TO 6
FOR 1=1 TO 6
READ C10(J,I)
NEXT I
NEXT J
DATA.005766,-.001562,.000606,.000001,
-.000025,-.000070,-.001897,.007443

141
DATA -.003315,-.000270,-.000004,.000015,.000666,
-.002792, .007592, .000087
DATA -.000032,-.000009
DATA -.000006,.000021,-.000201,.003903,
-.001240,-.000238,.000002,-.000001
DATA .000029,-.000709,.007315,-.000007 ,
-.000120,.000033,-.000012,-.000006
DATA -.000174,.005761
DETERMINATION OF CARBON NUMBER MATRIX TO BE USED FOR ALKYLBENZENES
AND CALCULATION OF VOLUME PERCENT OF AROMATIC TYPES
IF AACN>=6 AND AACN<=10 GOTO 100
PRINT "AROMATIC CARBON NUMBER";AACNIS OUTSIDE RANGE OF MATRIX"
IF AACN<6 THEN AACN=6
IF AACN>10 THEN AACN=10
100 FOR 1=6 TO 10
IF AACN NEXT I
200 AM1=I
AM2=I-1
SEND=AM2
300 IF SEND=6 THEN GOSUB 1000
IF SEND=7 THEN GOSUB 1100
IF SEND=8 THEN GOSUB 1200
IF SEND=9 THEN GOSUB 1300
IF SEND=10 THEN GOSUB 1400
IF SEND=AM1 THEN GOTO 400
X4=V(4)
X5=V(5)
X6=V(6)
SEND=AM1
GOTO 300
400 Y4=V(4)
Y5=V(5)
Y6=V(6)
R=1
IF AM2 Z4=R*(Y4-X4)+X4
Z5=R*(Y5-X5)+X5
Z6=R*(Y6-X6)+X6
DETERMINATION OF CARBON NUMBER MATRIX TO BE USED FOR PARAFFINS
'AND CALCULATION OF VOLUME PERCENT OF PARAFFINIC TYPES
IF PACN>=6 AND PACN<=10 GOTO 500
PRINT "PARAFFIN CARBON NUMBER";PACN;"IS OUTSIDE RANGE OF MATRIX"
IF PACN<6 THEN PACN=6
IF PACN>10 THEN PACN=10
500 FOR 1=6 TO 10
IF PACNCI THEN GOTO 600
NEXT I

142
600 PM1=I
PM2=I-1
SEND=PM2
700 IF SEND=6 THEN GOSUB 1000
IF SEND=7 THEN GOSUB 1100
IF SEND=8 THEN GOSUB 1200
IF SEND=9 THEN GOSUB 1300
IF SEND=10 THEN GOSUB 1400
IF SEND=PM1 THEN GOTO 800
X1=V(1)
X2=V(2)
X3=V(3)
SEND=PM1
GOTO 700
800 Yl-V(l)
Y2=V(2)
Y3=V(3)
R=1
IF PM2 Z1=R*(Y1-X1)+X1
Z2=R*(Y2-X2)+X2
Z3=R*(Y3-X3)+X3
VOLUME FRACTION RESULTS AT LEAST ZERO PERCENT
IF ZKO THEN Z1=0
IF Z2<0 THEN Z2=0
IF Z3<0 THEN Z3=0
IF Z4<0 THEN Z4=0
IF Z5<0 THEN Z5=0
IF Z6<0 THEN Z6=0
NORMALIZATION OF RESULTS TO 100%
Z=Z1+Z2+Z3+Z4+Z5+Z6
Z1=Z1/Z*100
Z2=Z2/Z*100
Z3=Z3/Z*100
Z4=Z4/Z*100
Z5=Z5/Z*100
Z6=Z6/Z*100
PRINTING OF RESULTS
INPUT DATA
LPRINT "HYDROCARBON TYPE ANALYSIS ON ";B$
LPRINT " "
LPRINT " "
LPRINT "AROMATIC ION INTESITIES ENTERED FOR CARBON NUMBER
CALCULATION"

143
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
LPRINT
It
" C78 C91
C92
C105
C106"
C78,C91,C92,C105,C106
tt
" C119 C120
C119,C120,C133,C134
tt
C133
C134"
" C147 C148
C147,C148,C161,C162
It
C161
C162
"PARAFFIN ION INTENSITIES ENTERED FOR CARBON NUMBER
CALCULATION"
II It
" C84 C85
C99"
C84,C85,C86,C98,C99
II It
" C100 C112
C126"
C100,C112,C113,C114,C126
It tt
" C127 C128
C142"
C127.C128,C140,C141,C142
It tt
" C154 C155
C169"
C154,C155,C156,C168,C169
tt tt
" C170"
C170
tt tt
"ION SUMMATION VALUES ENTERED FOR VOLUME PERCENT
CALCULATION"
C86 C98
C113 C114
C140 C141
C156 C168
LPRINT " "
LPRINT USING
LPRINT USING
LPRINT USING
LPRINT USING
LPRINT USING
LPRINT USING
LPRINT " "
LPRINT " "
"PARAFFINS
"MONOCYCLOPARAFFINS
"DICYCLOPARAFFINS
"ALKYLBENZENES
"INDANES/TETRALINS
"NAPHTHALENES
##.##";ISUM(1)
##.##";ISUM(2)
ISUM(3)
##.##";ISUM(4)
##.##";ISUM(5)
##.##";ISUM(6)
OUTPUT DATA (RESULTS)
LPRINT "HYDROCARBON TYPE ANALYSIS RESULTS--"
LPRINT "
LPRINT " "
LPRINT USING "AROMATIC AVERAGE CARBON NUMBER ##.####";AACN
LPRINT " "

144
LPRINT USING "PARAFFINIC AVERAGE CARBON NUMBER ##.####";PACN
LPRINT " "
LPRINT "VOLUME PERCENT OF HYDROCARBON TYPES"
LPRINT " "
LPRINT USING "PARAFFINS ##.##";Z1
LPRINT USING "MONOCYCLOPARAFFINS ##.##";Z2
LPRINT USING "DICYCLOPARAFFINS ##.##";Z3
LPRINT USING "AROMATICS ## .//#"; Z4
LPRINT USING "INDANES/TETRALINS ##.##";Z5
LPRINT USING "NAPHTHALENES ##.##";Z6
LPRINT CHR$(12)
STOP
MATRIX CALCULATION SUBROUTINES
C6 SUBROUTINE
1000 FOR J=1 TO 4
FOR 1=1 TO 4
M6(I)=ISUM(I)*C6(J,I)
NEXT I
FOR K=1 TO 4
SUM6=SUM6+M6(K)
NEXT K
V(J)=SUM6
SUM6=0
NEXT J
V(5)=0
V(6)=0
RETURN
C7 SUBROUTINE
1100 FOR J=1 TO 5
FOR 1=1 TO 5
M7(I)=ISUM(I)*C7(J,I)
NEXT I
FOR K=1 TO 5
SUM7=SUM7+M7(K)
NEXT K
V(J)=SUM7
SUM7=0
NEXT J
V(6)=0
RETURN
C8 SUBROUTINE
1200 FOR J=1 TO 6
FOR 1=1 TO 6
M8(I)=ISUM(I)*C8(J,I)
NEXT I
FOR K=1 TO 6
SUM8=SUM8+M8(K)

NEXT K
V(J)=SUM8
SUM8=0
NEXT J
RETURN
C9 SUBROUTINE
1300 FOR J=1 TO 6
FOR 1=1 TO 6
M9(I)=ISUM(I)*C9(J,I)
NEXT I
FOR K=1 TO 6
SUM9=SUM9+M9(K)
NEXT K
V(J)=SUM9
SUM9=0
NEXT J
RETURN
CIO SUBROUTINE
1400 FOR J=1 TO 6
FOR 1=1 TO 6
M10(I)=ISUM(I)*C10(J,I)
NEXT I
FOR K=1 TO 6
SUM10=SUM10+M10(K)
NEXT K
V(J)=SUM10
SUM10=0
NEXT J
RETURN

APPENDIX D
PRELIMINARY TEST METHOD FOR HYDROCARBON TYPE ANALYSIS
OF JET FUEL BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY
This is a preliminary standard test method developed By Michael J.
Gehron and Richard A. Yost at the University of Florida Chemistry
Department. The format of the ASTM Standard D-2789-81 was used in
preparation of this document. Funding and support was provided by
Wright-Patterson Air Force Base-Fuels Division contract no. F33615-85-
C-2508, through United Technologies-Pratt & Whitney. Special
acknowledgements are extended to Bill Edwards of Pratt & Whitney for
his guidance in the fuels area and also to Sue Guisinger, also of Pratt
& Whitney, for her contribution to the BASIC program for hydrocarbon
type analysis.
1. Scope
1.1 This method covers the determination by Gas
Chromatography/Mass Spectrometry of the total paraffins,
monocycloparaffins, dicycloparaffins, alkylbenzenes, indanes and
tetralins, and naphthalenes in jet fuels with an average carbon number
of the saturated and unsaturated fractions between six and ten.
146

147
2. Applicable Documents
2.1 ASTM Standards
D 2789 Test Method for Hydrocarbon Types in Low Olefinic Gasoline
by Mass Spectrometry
D 86 Method for Distillation of Petroleum Products
D 875 Method for Calculation of Olefin and Aromatics in Petroleum
Distillates from Bromine Number and Acid Absorption
D 1319 Test Method for Hydrocarbon Types in Liquid Petroleum
Products by Fluorescent Indicator
D 2001 Test Method for Depentanization of Gasoline and Naphthas
D 2002 Method for Isolation of Representative Saturates Fraction
from Low-Olefinic Petroleum Naphthas
2.2 Other Documents
Brown, R.A. Anal. Chem. 1951, 23, 430.
3. Summary of Method
Samples are analyzed by GC/MS using the classical ASTM 2789
inverse calibration matrices (section 2.1). The neat jet fuel samples
are introduced into the mass spectrometer with a short bonded phase
capillary column and split mode injection.
Data is collected using mass summation chromatography of the
characteristic mass fragments of each hydrocarbon type (see section 5).
Data is also collected for the individual mass fragments used in the
calculation of average carbon number (see section 11). These results
are subjected to a BASIC computer program which calculates the average
carbon numbers of the combined saturated and combined unsaturated

148
fractions, and the volume percent of each hydrocarbon type.
4. Significance and Use
It is desired to have a hydrocarbon type analysis which may be
applied the boiling point range of modern jet fuels and be amenable to
modern mass spectrometric instrumentation. Hydrocarbon type analysis
(HTA) of jet fuel is important for the design, operation, and
maintenance of jet engines.
5. Definitions
5.1 Summation ions of characteristic hydrocarbon types
5.1.1 243(paraffins)=total intensity of (m/z) 43+57+71+99.
5.1.2 241(monocycloparaffins)=total intensity of (m/z)
41+55+69+83+97.
5.1.3 267(dicycloparaffins)=total intensity of (m/z)
67+68+81+82+95+96.
5.1.4 277(alkylbenzenes)=total intensity of (m/z) 77+78+79+91+92+
105+106+119+120+133+134+147+148+161+162.
5.1.5 2103(indans/tetralins)=total ion intensity of (m/z) 103+104
117+118+131+132+145+146+159+160.
5.1.6 2128(naphthalenes)=total ion intensity of (m/z)
128+141+142+155.
5.1.7 2T=Total ion summation of 243+241+267+277+2103+2128.
5.2 Mass summation chromatogram is the mass chromatogram of each
ion summation value (2 values) for example, the mass summation
chromatogram of the 243 ion series is the mass chromatogram of the
combined (summed) 243 ion series as shown in section 5.1.1 above.

149
6. Apparatus
6.1 Mass Spectrometry
The mass spectrometer used is a Finnigan TSQ 45 operated in the
single stage quadrupole mode. Any single stage quadrupole mass
spectrometer capable of interfacing to a capillary gas chromatograph
may be used. The ionization source is operated in the electron
ionization (El) mode; filament current,
300 ¿¿A; electron energy, 70 eV; source temperature, 190°C. The mass
spectrometer is scanned from 35 to 650 amu in 0.95 sec with a rest time
of 0.05 sec.
6.2 Sample Introduction
The sample fuel is injected onto a 3 meter capillary column which
is inserted directly into the ion source of the mass spectrometer.
Split type injections of 0.1 to 0.5 ¿tL are made with a ratio of 50:1.
Care must be taken in developing a reproducible injection technique.
The syringe must be thoroughly rinsed with hexane or another suitable
solvent to remove the previous fuel sample left over in the syringe
barrel. The syringe must then be thoroughly rinsed with the fuel
sample to be injected in order to insure removal of any remaining
hexane. Alternatively a 1 (iL hexane plug may be maintained in the
syringe volume. This eliminates syringe sample memory and aids in
reproducible injections. The hexane peak, however, must be resolved
from the components of the sample fuel. For fuels which contain
components in the hexane eluting range, a longer column and/or sub¬
ambient column temperatures may also be considered as methods of

150
resolving the fuel components. If the fuel contains hexane or any co¬
eluting component, neat sample injection is required.
6.3 Chromatography
The capillary column used is a J&W Durabond DB5, 3 m long x 0.25 mm
i.d. x 1.0 fim film thickness nonpolar column. The column carrier gas
is helium, column temperature, 40°C for 0.5 min, then programmed to
280°C at 15°C/min. A longer column may be substituted if desired, but
increased analysis times will result.
7. Reference Samples
Synthetic JP-8X or another synthetic mixture or a jet fuel of known
composition is used for the performance test.
8. Performance Test
Calibrate (mass assignment) the instrument according to its own
specifications. Tune the instrument to obtain the proper relative ion
abundances for the calibration compound used. Maintain a constant ion
ratio for two or more sets of characteristic ions of the calibration
compound. In this laboratory, the Finnigan MAT Model TSQ 45 uses
perfluorotri-n-butylamine as the calibration compound. An ion
intensity ratio between 1.2 and 1.8 is maintained for m/z 69 : m/z 219
and between 1.5 and 2.0 for m/z 502 : m/z 220. These ion ratios cover
the total mass range of interest. Reproducible tuning of the mass
range is critical in maintaining day to day accuracy.
Perform a HTA on the reference standard mixture (section 10). The

151
results should agree to known concentrations to within the same limits
specified in ASTM D-2789 as shown in Table I.
Table I
Performance Test Limits of Error
Hvdrocarbon Tvoe
Percent
Total Paraffins
± 0.8
Total Cycloparaffins
± 1.3
Total Aromatics
± 0.7
9. Sample Preparation
9.1 Depentanize the sample in accordance to Method D2001.
9.2 Determine the olefin content of the depentanized sample in
accordance with Method D1319 or D 875.
9.3 Alternate GC/MS/MS method for the determination of olefin
content is currently being developed in this laboratory.
9.4 Store the working sample in a septum vial in which the septum
is easily puncturable by a standard gas chromatographic syringe and
which can be easily replaced by a new septum for storage.
10. Procedure
10.1 Tune the Mass Spectrometer as described in Section 6.1.
10.2 Run the performance test and compare results to Table I.

152
Replicate analyses of the performance standard may be performed to
obtain daily precision values. Any jet fuel sample within the scope of
the analysis may serve as a precision check sample. If the accuracy of
the performance test is not inadequate, one should consider the state
of the reference standard, the tuning of the mass spectrometer or the
ability of the analyst. If the precision of the analysis is
inadequate, one should consider the sample injection technique, the
instrumental noise of the mass spectrometer, or the ability of the
analyst.
10.3 Injection Technique- Using a 5 fiL syringe (a 10 pL syringe
may be substituted) obtain 1 to 1.5 n~L of fuel. Pull back on the
syringe plunger, removing the fuel from the needle, and record the
sample volume. Pierce the injection port septum with the syringe
needle and count to three, allowing the entire injection needle to
equilibrate to the injection port temperature and minimizing component
discrimination. Inject the sample at a rate of 1 ¿¿L per second and
hold for another three count. Remove the syringe and record the
volume. The difference will indicate the exact volume injected.
10.4 Instrumentation- The gas chromatographic conditions should be
set as described in section 6.3. The mass spectrometer conditions
should be set as described in section 6.1.
10.5 Data Analysis- Obtain the ion intensities which are used for
carbon number calculations (section 11) , as well as the relative
percentage of each hydrocarbon type from the mass summation
chromatograms (section 11) . Input these values into the accompanying
BASIC program (see Appendix B).

153
11. Calculations
11.1 Average Carbon Number- The method of calculation of aromatic
and paraffinic carbon number is covered in the ASTM 2789 standard
(section 11.2) and will not be reproduced here. The values are
calculated using the BASIC program.
11.2 Calculation of Hydrocarbon Type- The method of calculation of
hydrocarbon type is covered somewhat briefly in the ASTM 2789 standard
(section 11.3). A sample calculation and result is given in the
appendix. The BASIC program calculates the volume percent of each
hydrocarbon type.
11.3 Olefinic Content- At present the monocycloparaffin result
represents the contribution of monocycloparaffin and olefin content.
If the olefinic content is determined by additional means and the
content is less than 3%, subtract this amount from the
monocycloparaffin results.
12. Calibration
Calibration is obtained in accordance to the ASTM 2789 standard
inverse calibration matrices (section 12 and Table I of the standard).
The inverse calibration matrices are incorporated into the BASIC
program which calculates volume percent of hydrocarbon types.
13. Precision and Accuracy
13.1 Precision- There has been no interlaboratory precision test
of the method. Day to day precision of the method for several test

154
fuels are shown in the appendix results section.
13.2 Accuracy- The results of several test fuels are compared to
actual ASTM 2789 results. It should be noted however, that ASTM 2789
results may not necessarily represent the actual hydrocarbon type make¬
up. Examination of recipe fuels (pseudo fuels with known make-up) may
indicate accuracy, but there is some controversy as to the validity of
such relatively simple pseudo-fuels for the matrix calculation method.

BIBLIOGRAPHY
1. Brown, R.A. Anal.Chem. 1951, 23, 430.
2. Lumpkin, H.E.; Thomas, B.W.; Elliott, A. Anal. Chem. 1952, 24,
1389.
3. Hood, A. Anal. Chem. 1958, 30, 1218.
4. O'Neal, M.J., Jr.; Wier, T.P., Jr. Anal. Chem. 1951, 23, 830.
5. Teeter, R.M.; Doty, W.R, Rev. Sci. Instru. 1966, 37, 792.
6.
Book
of
ASTM
Standards. Vol. 05.02.
D-2789,
ASTM,
Philadelphia,
1986.
7.
Book
of
ASTM
Standards. Vol. 05.02.
D-2425,
ASTM,
Philadelphia,
1986.
8.
Bieman,
K.
Mass Stiectrometrv: Oreanic Chemical
Applications:
Mcgraw Hill,
New York, NY, 1962.
9.
ASTM
Committee E-14 on Mass Spectrometry, Denver,
1987.
10.
Book
of
ASTM
Standards. Vol. 05.01,
D-1319,
ASTM,
Philadelphia,
1986.
11. McKay, J.F.; Latham, D.R. Anal.Chem. 1980, 52, 1618.
12. Davis, J.M.; Giddings, J.C. Anal. Chem. 1983, 55, 418.
13. Martin, M. ; Herman, D.P.; Guiochon, G. Anal. Chem. 1986, 58,
2200.
14. Meyerson, S. Org. Mass Spectro. 1986, 21, 197.
15. Borman, S.A. Anal. Chem. 1984, 56, 1272A.
16. Kurtz, Jr., S.S.; Mills, I.W.; Martin, C.C.; Harvey, W.T.;
Lipkin, M.R. Anal. Chem. 1947, 19, 175.
17. Rampton, H.C. J. Inst. Petrolem 1949, 35, 42.
155

156
18. Washburn, H.W.; Wiley, H.F.; Rock, S.M.; Berry, C.E. Ind. Eng.
Chem., 1945, 17, 74.
19. Brown, R.A.; Taylor, R.C.; Melpolder, F.W.; Young, W.S. Anal.
Chem. 1948, 20, 5.
20. Feldman, J.; Orchin, M. Ind. Eng. Chem. 1952, 44, 2852.
21. Melpolder, F.W.; Brown, R.A.; Young, W.S.; Headington, C.E.
Ind. Eng. Chem. 1952, 44, 1142.
22. Brown, R.A.; Melpolder, F.W.; Young, W.S. Petroleum Processing
1952, 7, 204.
23. Brown, R.A.; Doherty, W. ; Spontak, J. Consolidated Engineering
Corp., Mass Spectrometry Report 84, 1950.
24. Hastings, S.H.; Johnson, B.H.; Lumpkin, H.E. Anal. Chem. 1956,
28, 1243.
25. Robinson, C.J.; Cook, G.L. Anal. Chem. 1969, 41, 1548.
26. Robinson, C.J. Anal. Chem. 1971, 43, 1425.
27. Gordon, R.J.; Moore, R.J.; Muller, C.E. Anal. Chem. 1958, 30,
1223.
28. Gallegos, E.J.; Green, J.W.; Lindeman, L.P.; LeTourneau, R.L
Anal. Chem. 1967, 39, 1833.
29. Teeter, R.M. Mass Spec. Rev. 1985, 4, 123.
30. Lumpkin, H.E. Anal. Chem. 1964, 36, 2399.
31. Johnson, B.H.; Aczel, T. Anal. Chem. 1967, 39, 682.
32. Robinson, C.J.; Cook, G.L. Anal. Chem. 1969, 41,1548.
33. Schmidt, C.E.; Sprecher, R.F.; Batts, B.D. Anal. Chem. 1987, 59,
2027.
34. Chartier, P.; Gariel, P.; Caude, M.; Rosset, R.; Neff, B.;
Bourgognon, H.; Husson, J.F. J. Chromatogr. 1986, 357, 381.
35. Cookson, D.J.; Rix, C.J.; Shaw, I.M.; Smith, B.E. J. Chromatogr.
1984, 312, 237.
36. Johansen, N.G.; Ettre, L.S.; Miller, R.C. J. Chromatogr. 1983,
256, 393.

157
37. Johansen, N.G.; Ettre, L.S.; Miller, R.C. J. Chromatogr. 1983,
259, 393.
38. Johansen, N.G.; Ettre, L.S.; Miller, R.C. J. Chromatogr. 1983,
264, 19.
39. Schwartz, H.E. LC-GC 1987, 5, 14.
40. Schwartz, H.E.; Brownlee, R.G. J. Chromatogr. 1986, 353, 77.
41. Norris, T.A.; Rawdon, M.G. Anal. Chem. 1984, 56, 1767.
42. Coordinating Research Council, Handbook of Aviation Fuel
Properties. CRC Report No. 530, 1983, 1.
43. Trehy, M.L.; Yost, R.A.; Dorsey, J.G. Anal. Chem. 1986, 58, 14.
44. Book of ASTM Standards. Vol. 05.02, D-2887, ASTM, Philadelphia,
1986.
45. Book of ASTM Standards. Vol. 05.03, D-3710, ASTM, Philadelphia,
1986.
46. Schultz, R.; Jorgensen, J.; Maskarinec, M.; Novotny, M.;
Todd, L. Fuel 1979, 58, 783.
47. Leveque, R.E. Anal. Chem. 1967, 39, 1811.
48. Gallegos, E.J. Special Technical Publication 902. ASTM,
Philadelphia, 1986, 5.
49. Colgrove, S.G.; Aczel, T. Abstracts of the American Society of
Mass Spectrometry. Minneapolis, 1981, 73.
50. Blanton, W.E.; Heppner, R.A.; Netzel, D.A. Abstracts of the
American Society of Mass Spectrometry. San Antonio, 1984, 434.
51. Mauson, M.S.B.; Field, F.H. J. Am. Chem. Soc. 1966, 88, 2621.
52. Harrison, A.G. Chemical Ionization Mass Spectrometry: CRC Press
Inc., Boca Raton, FL, 1982.
53. Sieck, W.L. Anal.Chem. 1979, 51, 128.
54. Sieck, L.W.; Jennings, K.R.; Burke, P.D. Anal. Chem. 1979, 51,
2232.
55. Brotherton, A.A.; Gulick, Jr., W.M. Anal. Chim. Acta 1985, 186,
101.
56. Ciupek, J.D.; Zakett, D.; Cooks, R.G. Anal. Chem. 1982, 54,
2215.

158
57. Guieze; Devant; Loyaux Abstracts of the American Society of
Mass Spectrometry. Honolulu, 1982, 807.
58. Bauer, M.R.; Schubert, A.J.;Enke, C.G. Abstracts of the American
Society of Mass Spectrometry. San Diego, 1985, 972.
59. Field, F.H.; Hastings, S.H. Anal.Chem. 1956, 28, 1248.
60. Zakett, D.; Cooks, R.G. New Approaches in Coal Chemistry. ACS
Symposium Series 169, B.D Blaustien; B.C. Bockrath; S. Friedman
Eds., American Chemical Society, Washington, D.C., 1981, Chapter
16.
61. Ciupek, J.D.; Cooks, R.G; Wood, K.V.; Ferguson, C.R. Fuel 1983,
62,829.
62. Zakett, D.; Ciupek, J.D.; Cooks, R.G. Anal. Chem. 1981, 53, 726.
63. Zakett, D.; Shaddock, V.M.; Cooks, R.G. Anal. Chem. 1979, 51,
1849.
64. Wong, C.M.; Crawford, R.W.; Yost, R.A. Special Technical
Publication 902. ASTM, Philadelphia, 1986, 106.
65. Wood, K.V.; Albright, L.F.; Brodbelt, J.S.; Cooks, R.G. Anal.
Chem. Acta. 1985, 173, 117.
66. Myerholtz, C.A.; Enke, C.G. Abstracts of the American Society of
Mass Spectrometry. Honolulu, 1982 812.
67. Zhong-min Li; Ciupek, J.D.; Wood, K.V.; Cooks, R.G. Abstracts of
the American Society of Mass Spectrometry. Honolulu, 1982, 798.
68. Wong, C.M.; Crawford, R.W.; Burnham, A.K. Abstracts of the
American Society of Mass Spectrometry. Boston, 1983, 91.
69. Schmidt, C.E.; Lett, R.G.; Wood, K.V.; Batts, R.F. Abstracts of
the American Society of Mass Spectrometry. Boston, 1983, 89.
70. Wood, K.V.; Laugal, J.A.; Benkeser, R.A. Abstracts of the
American Society of Mass Spectrometry. San Antonio, 1984, 428.
71. Schubert, A.J.; Myerholtz, C.A. Abstracts of the American
Society of Mass Spectrometry. San Antonio, 1984, 426.
72. Beynon, J.H.; Cooks, R.G.; Amy, J.W.; Baitinger, W.E.; Ridley,
T.Y. Anal. Chem. 1973, 45, 1023.
73. Kondrat, R.W.; Cooks, R.G. Anal. Chem. 1978, 50, 81A.
74. Yost, R.A.; Enke, C.G. Anal. Chem. 1979, 51, 1251A.

159
75.
76.
77.
78.
79.
80.
81.
Grob, K; Grob, G Chromatographia, 1972, 5, 3.
Grob, K; Grob, K, Jr. J. Chromatogr. 1974, 94, 53.
Anton, H. Elementary Linear Algebra. 3rd Edition: John
Wiley & Sons, New York, NY, 1981.
Knave, M.D; Olson, B.A.; Elofsson, S.; Gamberale, F.; Isaksson
A.; Mindus, P.; Persson, H.E.; Struwe, G.; Wennberg, A.
Westerholm, P., Scand. J. Environ. & Heath, 1978, 4, 19.
McMahon, D.H. J. Chromatogr. Sci. 1985, 23, 137.
McLafferty, F.W. Tandem Mass Spectrometry: John Wiley & Sons,
New York, NY, 1983.
Fetterolf, D.D.; Yost, R.A. Int. J. Mass Spectrom. Ion Phys
1982, 44, 37.

BIOGRAPHICAL SKETCH
Michael Joe Gehron was born in Fort Lauderdale, Florida, on June
27, 1956 as a third generation Fort Lauderdale native. He attended
Nova High School in Fort Lauderdale, Florida, and graduated in May,
1974. He then attended Broward Community College and graduated with an
A.A. degree on June, 1977. He then attended Florida State University
and received his B.S. degree in chemistry in December, 1979. Mike then
worked with David C. White, an environmental microbiologist-chemist,
for the next four years as a chemist. He came to the University of
Florida in July, 1983, and received a Master of Science in
electroanalytical chemistry in May, 1985. He continued on with Rick
Yost at the university and is receiving his Ph.D. in analytical
chemistry. Mike is the proud father of Laura Ann Gehron and his soon
to be second child. Mike will continue his work in GC/MS and
analytical methods at the materials laboratory of Pratt and Whitney in
West Palm Beach, Florida.
160

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
'irf
Richard A. Yost, Chai
Associate Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
tí^rhard M.Schmid
Associate Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
(/LtfV
â–  V-0
Jl
uL-
Winefoi/dner
Research Professor
of Chemistry
fames D.
/Graduate

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
Joseph J. Delfino^^
Professor of Environmental
Engineering Sciences
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
S- ^cd-y —
Kirk S. Schanze
Assistant Professor of Chemistry
This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences and
to the Graduate School and was accepted as partial fulfillment of the
requirements for the degree of Doctor of Philosophy.
April, 1988
Dean, Graduate School

UNIVERSITY OF FLORIDA
1262 08556 7724




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