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The pulse radiolysis of sodium tetraphenylborate and sodium hexachloroiridate in aqueous solution

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The pulse radiolysis of sodium tetraphenylborate and sodium hexachloroiridate in aqueous solution
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Crawford, Charles L., 1963-
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xi, 169 leaves : ill. ; 29 cm.

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Absorption spectra ( jstor )
Anions ( jstor )
Aqueous solutions ( jstor )
Chemicals ( jstor )
Dosimetry ( jstor )
Electrons ( jstor )
Free radicals ( jstor )
Radiation chemistry ( jstor )
Radiolysis ( jstor )
Signals ( jstor )
Chemical kinetics ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Pulse radiolysis ( lcsh )
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Thesis (Ph. D.)--University of Florida, 1991.
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Includes bibliographical references (leaves 155-168)
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Typescript.
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Vita.
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by Charles L. Crawford.

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THE PULSE RADIOLYSIS OF SODIUM TETRAPHENYLBORATE AND
SODIUM HEXACHLOROIRIDATE IN AQUEOUS SOLUTION














BY
CHARLES L. CRAWFORD














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


1991



































Dedicated to

my parents, Nathan and Doris















ACKNOWLEDGMENTS

The author expresses his sincere appreciation to his

research director, Prof. Robert J. Hanrahan, and to Prof. M.

Luis Muga for their advice, encouragement, and friendship

throughout this work.

Special thanks are given to Avinash Gupta and Zuoqian

Li for their friendship and assistance.

Appreciation is given to Ravi Bhave for his efforts in

initiating the experimental setup. Mohammad Gholami and

Sandra Roberts are also acknowledged for their contributions

towards much of the data collection.

Thanks to Prof. D. N. Silverman of the J. Hillis Miller

Health Science Center for the use of the stopped-flow appa-

ratus. Experimental assistance with this instrument, pro-

vided by Dr. Chingkuan Tu, is also gratefully acknowledged.

The author's deepest thanks are expressed to Kama

Siegel for her unprecedented companionship and editorial

prowess -- both of which have helped make this work possi-

ble.

Thanks to Dave Burnsed for his assistance with the

electronics.


iii
















TABLE OF CONTENTS


ACKNOWLEDGEMENTS .................................. iii

LIST OF TABLES ..................................... vi

LIST OF FIGURES .................................... vii

ABSTRACT .... ..................................... X

1. INTRODUCTION .................................. 1

1.1 Foreword .............................. 1
1.2 Review of Previous Work ................. 3


2. EXPERIMENTAL APPARATUS AND PROCEDURES ......... 19

2.1 Pulse Radiolysis Setup ................... 19
2.2 Absorption Spectrophotometry ............. 22
2.3 Light Source Systems ................... 30
2.4 Reaction Cells and Cellholder ............ 37
2.5 Monochromators .......................... 47
2.6 Febetron 706 System ..................... 50
2.7 Transient Recorder and Computer System ... 59
2.8 Computer Program ....................... 63
2.9 Reagents and Their Purification .......... 65
2.10 Sample Irradiation ....................... 67

3. PULSE RADIOLYSIS OF SODIUM TETRAPHENYLBORATE
IN AQUEOUS SOLUTION .................... 69

3.1 Experimental Results ..................... 69
3.2 Discussion .................... ........ 83
3.3 Conclusions .............................. 91

4. PULSE RADIOLYSIS OF SODIUM HEXACHLOROIRIDATE
IN AQUEOUS SOLUTION ..................... 93

4.1 Experimental Results ................... 93
4.2 Discussion ............................ 101
4.3 Conclusions ............................. 114











APPENDIX A


APPENDIX B

APPENDIX C


APPENDIX D


CHEMICAL DOSIMETRY FOR A PULSED
RADIATION SOURCE ...................

RELEVANT REACTION SYSTEMS ...........

INPUT DATA FILES FOR COMPUTER
INTEGRATION SIMULATIONS .............

PULSE RADIOLYSIS COMPUTER PROGRAM ...


REFERENCES .......................... ..............

BIOGRAPHICAL SKETCH .............................


118

128


132

138

155

169















LIST OF TABLES


Table Page

1 Radiation Chemical Yields for Water ........... 9

2 Transient Decay Rate Constants ............... 78

3 Physical Constants for Chemical Dosimetry
Systems .............. .. .................. 120

4 Absorbed Dose for Chemical Dosimetry Systems .. 127

5 Chemical Reaction Systems for Computer
Simulation Studies ....... .................. 129















LIST OF FIGURES


Figure Eae

1 Scheme for the radiolysis of water ............ 8

2 University of Florida pulse radiolysis system 21

3 Experimental arrangement using the McPherson
218 monochromator ............................. 26

4 Experimental arrangement using the Jarrell-Ash
monochromator ................................. 27

5 Photomultiplier tube-base schematic used with
the EMI 9250 QB PMT in the model 3262 housing 29

6 Lead shields for PMT photocathodes in the
Pacific Precision Instruments PMT housings .... 31

7 Photomultiplier tube-base schematic used with
the Hamamatsu R928 side window PMT and Model
3150 housing ................................. 32

8 Xenon-arc lamp spectrum ...................... 34

9 Xenon-arc lamp schematic diagram .............. 35

10 Flow-reaction cell with modified UV-VIS
cuvette ........................ ................ 39

11 Non-flow-reaction cell from UV-VIS cuvette .... 41

12 Reaction cellholder with adjustable razor
blades mounts and wire-mesh screens ........... 42

13 Depth-dose curves for microscope coverslide
experiment ................................... 45

14 Absorbance change with number of pulses
delivered for microscope coverslide experiment 46

15 Entrance and exit slit system flange adaption
to the Jarrell-Ash monochromator .............. 51


vii









Figure Page

16 Febetron 706 system schematic ................. 53

17 Refurbished electron beam tube with ion pump .. 56

18 Total beam calorimetric dosimetry arrangement 58

19 Timing sequence for pulse radiolysis experiment 62

20 Graphical display of optical signal versus time
following pulse radiolysis of a N20-saturated
solution containing 10 mM NaTPB .............. 71

21 Transient absorption spectrum ................. 72

22 Graphical display of optical signal versus time
following pulse radiolysis of a N20-saturated
NaTPB and NaN3 solution ...................... 74

23 Curve fit of data from Fig. 20 (a) ............ 76

24 Curve fit of data from Fig. 20 (b) ............ 77

25 Carbonate competition experiment for determining
the OH + TPB- rate constant ................. 80

26 Graphical display of optical signal versus time
following pulse radiolysis of a N2-saturated
solution contain NaTPB and t-butanol ......... 82

27 Comparison of experimental and computer
simulated concentration versus time plots ..... 90

28 UV-VIS spectrum ......... ............ .......... 94

29 Carbonate competition experiment for determining
the OH + Ir(III) rate constant .............. 96

30 Transient digitizer traces of Ir(IV) absorption
recorded at 488 nm with N20-saturation ........ 98

31 Transient digitizer traces of Ir(IV) absorption
recorded at 488 nm with N2 and air saturation 100

32 Change in first order decay of hydrated electron
with Ir(III) concentration .................... 102

33 Comparison of experimental and computer
simulated Ir(IV) concentration verses
time plots; N20, alkaline ..................... 109


viii









Page


34 Comparison of experimental and computer
simulated Ir(IV) concentration verses
time plots; nitrogen-saturated ............... 111

35 Comparison of experimental and computer
simulated Ir(IV) concentration verses
time plots; aerated ........................... 112


36 Computer simulations of the transient
Ir(IV) trace ................................. 113

37 Change in absorbance with accumulated
irradiation pulses for the modified
Fricke system ................................... 124

38 Thiocyanate dosimetry ........................ 125

39 Hydrated electron dosimetry .................. 126















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

THE PULSE RADIOLYSIS OF SODIUM TETRAPHENYLBORATE AND
SODIUM HEXACHLOROIRIDATE IN AQUEOUS SOLUTION

By

Charles L. Crawford

December, 1991

Chairman: Dr. R. J. Hanrahan
Major Department: Chemistry

A pulse radiolysis facility for the study of fast

chemical kinetics in aqueous solution, based on a Febetron

706 electron beam accelerator, has been established at the

University of Florida Radiation Chemistry Laboratory.

In previous work on the radiolysis of tetraphenylborate

(TPB)'solutions carried out in this laboratory, it was found

that several organic products, including benzene, phenol,

and biphenyl, are produced with substantial yield. However,

the reaction mechanism has not been determined. Since the

tetraphenylborate anion, TPB-, is a reducing species, it

should be more readily subject to attack by OH- than by eaq

or by H.. The lack of reactivity between TPB and eaq- has

been confirmed by directly monitoring the transient signal

due to eaq-. Concerning the reaction with OH., two schemes

were investigated: (1) a rapid electron transfer from









B(C6H5)4~ to OH.; (2) OH. addition to B(C6H5)4~. Comparison

of transient absorption spectra resulting from the two

different schemes above suggests that the OH. addition is

the dominant reaction under conditions of N20 saturation,

with an experimentally determined second-order rate constant

of 6.2 x 109 M-is-1. A mechanism based on an initial first-

order self-decomposition of the OH* adduct, (C6H5)3BC6H50H,

is proposed.

Reactions initiated by OH. radicals or eaq- in aqueous

IrCl63- solutions were studied. The rate constant for the

respective reactions were found to be 4.9 x 109 M-1s-1 and

6.1 x 109 M-1s-1. The oxidation product, IrC162- disappears

rapidly in N20-saturated basic solution or in either neutral

N2-saturated or aerated solution, but is nearly inert in

neutral solution with N20 present. The complex IrCl62-

reacts rapidly with hydrogen peroxide in basic media, as

confirmed on the benchtop and by stopped-flow kinetics. It

is therefore inferred that reaction with HO2- may account

for the loss of IrCl62- under basic conditions. Loss of

Ir(IV) in neutral N2-saturated solution without added N20

may involve electron transfer from Ir(II), and loss of

Ir(IV) in aerated solution is attributed to reduction by

superoxide ion, 02-.

Kinetic modeling on the respective mechanistic schemes

of the above systems gives good agreement with our experi-

mental results.















CHAPTER I
INTRODUCTION

1.1 Foreword


The pulse radiolysis technique offers a convenient way

of generating a variety of unstable or transient species

under well-defined conditions. This technique involves the

initiation of a chemical reaction process via a short pulse

of ionizing radiation. Of major interest is the kinetics

of, as well as both the qualitative and quantitative meas-

urement of these transient species involved in the fast

elementary steps of the reaction process.

The modification of a gas-phase pulse radiolysis system

to a liquid-phase pulse radiolysis system was undertaken to

expand the chemical kinetics facility of the University of

Florida Radiation Chemistry Laboratory. Efforts to obtain

kinetic information related to various aqueous solution

systems were made in order to supplement existing aqueous-

solution-based studies carried out in this laboratory in-

volving techniques such as steady-state Co-60 --radiolysis

and solar-assisted photoelectrochemistry.

To study fast chemical reaction systems, two necessary

requirements are the initiation of the process on a time-

scale that is shorter than or comparable to the process

being observed, and the detection of a physicochemical









change associated with the process. Our liquid-phase pulse

radiolysis system was developed around a Febetron 706 elec-

tron beam (e-beam) accelerator capable of delivering a

short, 3 nanosecond full width at half-max (FWHM) pulse of

600 KeV electrons with a peak current of 8 x 103 amps. The

monitoring technique employed was time-resolved absorption

spectroscopy.

A microcomputer-based data acquisition system was

integrated into the pulse radiolysis system to acquire,

analyze, and store data obtained from the study of fast

chemical processes.

The kinetic studies involving aqueous solutions of

sodium tetraphenylborate (NaTPB) were undertaken to aid in

developing a plausible mechanism concerning the radiolytic

degradation of the TPB- ion. Examination of the iridium

chloride system was carried out to expand the solution

conditions under which this system had been previously

studied by pulse radiolysis. Due to the similarities of

flash photolysis and pulse radiolysis, specifically in the

case of radiation-induced redox reactions, previous photoly-

sis work on the iridium chlorides served as a reference to

the pulse radiolysis data collected in this study.

Various chemical dosimeter methods applicable to pulsed

electron sources were studied to establish the proper dose

delivered to the liquid sample in the Febetron 706 system,

as modified for liquid-phase work.











1.2 Review of Previous Work


1.2.1 Pulse Radiolysis


At the University of Florida Radiation Chemistry Labo-

ratory, Febetron 706 studies have been completed on the gas

phase reaction kinetics and mechanisms of various chemical

systems such as the alkyl and perfluoroalkyl iodides,1

oxygen/ozone,2 and OH reaction dynamics with small mole-

cules.3-5 The identity and reactivity of important tran-

sient species generated in the pulse radiolysis of gaseous

systems, at atmospheric pressures or less, was of previous

interest in these studies.

Historically, pulse radiolysis was developed to eluci-

date postulated transient behavior in radiation-induced

chemical reaction systems, and apparatus was first brought

into operation in about 1960.6,7 Early pulse radiolysis

systems used visible absorption spectroscopy to monitor

intermediates produced from intense single electron acceler-

ator pulses lasting typically around one microsecond or

less, and much of the developmental work on pulse radiolysis

involved liquid phase systems.8-10 Development of the pulse

radiolysis technique has since brought about variations of

the method to include stroboscopic techniques capable of

picosecond resolution11 and multiple time-resolved observa-

tion techniques such as electron spin resonance (ESR),12-14









conductivity,15-17 emission spectroscopy,18 and resonance

Raman spectroscopy,19-21 to monitor reaction intermediates.

The pulse radiolysis method is the radiation chemistry

analog of flash photolysis, in that the photoflash and

photodissociation of molecules is replaced by a short, high-

energy pulse of electrons, causing excitation and ionization

of molecules by electron impact.22 The technique of pulse

radiolysis, used to study fast reactions, has been applied

in areas of aqueous inorganic, organic, and biochemistry.

Other fast reaction techniques such as flash photolysis,

stopped-flow techniques, and temperature jump or pressure

jump relaxation methods have been designed to monitor con-

centrations and to measure rate coefficients.23 However,

the pulse radiolysis technique was the first method capable

of studying processes occurring at or below 10-9 seconds.24

The characteristics of the electron pulse used in

electron beam pulse radiolysis are its time profile, peak

current and energy, cross-sectional homogeneity, and diver-

gence. For adequate time resolution of the observed tran-

sient signal, the time profile of the pulse should be very

short compared to the relaxation of the intermediates. The

pulse current determines the number of interactions between

the chemical system and the e-beam which, in turn, deter-

mines the concentration or amount of species formed. The

maximum electron energy determines the penetration depth of

the e-beam into the reaction cell and should be high enough

to adequately irradiate the volume of the chemical system









being monitored. The cross-sectional homogeneity and diver-

gence of the beam determine how uniformly irradiated the

optically-sampled reaction region is.

Transformations over the years of the standard pulse

radiolysis installation have led to increasingly sophisti-

cated experimental setups.25-28 Spectrographic methods

involving oscilloscopes and Polaroid cameras have been

largely replaced by digital signal processors, or transient

digitizers that have an interface for computer control.11

Signal processing has been aided by the use of backing-off

circuits which can measure small transients on top of the

analyzing light.29 Lasers and the capability of commercial

xenon-arc lamps to supply pulse current on top of DC current

have provided intense analyzing light sources.30-32 Lastly,

on-line computer systems have been developed which not only

greatly reduce the time required for data analysis but also

improve both quantity and quality of the data

processed.29,33-35


1.2.2 Radiolysis of Water and Aqueous Solutions


Early investigations on the radiolysis of water have

played a significant role in the development of radiation

chemistry.36-39 In addition, sophisticated pulse radiolysis

techniques achieving the time resolution of radiation in-

duced chemical events have been applied more often in the

radiolysis of water than in any other liquid.40 As a









result, most of the aspects of the radiation chemistry of

water and aqueous solutions are now reasonably well under-

stood.

A few practical purposes for water irradiation studies

arise from 1) the importance of understanding the effect of

radiation on biological systems in which water is the main

substrate, and 2) various aspects of nuclear reactor tech-

nology concerning water's use as both a coolant and modera-

tor.41,42 Water and aqueous solutions have been studied, in

particular, for three reasons: (1) their role as solvents is

central to chemistry in general and to radiochemistry in

particular; (2) they are readily available and easy to work

with; (3) water is a polar liquid that responds in charac-

teristic ways to radiation.

Important features of the radiation chemistry of water

are: (1) a description of the primary radical and molecular

products and how they evolve in both time and space; (2) the

effect of pH on the radiation chemical yields of primary

products; (3) the track structure and related phenomena

associated with the passage of a charged particle through a

liquid; and (4) a detailed account of all the radical reac-

tions involving the primary radicals and radiolysis

products.43

Upon initial ionization of a water molecule by a fast

primary charged particle such as an electron, the liberated

electron from the ionization event will typically have

sufficient energy to further ionize several adjacent water









molecules, which leads to the creation of clusters of ions

along the track of the ionizing particle. These clusters

are called spurs; detailed descriptions of their structure

and distribution along the particle tracks can be found in

the literature.44 Once the dry electrons have been slowed

to thermal energy, they undergo a hydration (or solvation)

process which involves the water molecules becoming oriented

about the charged species. This process occurs on the order

of 10-11 seconds, which is the relaxation time for dipoles

in water. Alternatively, some water molecules are excited

to upper electronic states from which they can autoionize,

dissociate, or fall back to the ground electronic state.

Figure 1 from Buxton43 shows the time scale of events initi-

ated by the absorption of energy by water from an incident

ionizing radiation, such as an energetic photon or charged

particle. Also shown are the various routes to formation of

the primary radical and molecular products.

At approximately 10-10 seconds after the ionizing

event, all the physicochemical processes are complete and

the chemical stage begins. Initially, this process involves

diffusion of the radiolysis products out of the spurs where

they either react together to form molecular and secondary

radical products, or they escape to the bulk solution,

becoming homogeneously distributed. Appendix B lists the

elementary reaction steps in the radiolysis of liquid water,

along with their appropriate rate constants.










SEvent
H20

- \


H20O

i


(H20)


OH + H3 +


H2+O


eaq


* molecular products form in the spurs
* diffusion of radicals out of the spurs


eaq ,H, OH,H21 H 202, H3O


Note: A//-

e


e
aq


, upon interaction with ionizing radiation


,the electron in a presolvated, or "dry" state


, hydrated electron


Fig. 1. Scheme for the radiolysis of water.


STime scale (sec)


H+OH


10-16
10


10-14

10-13
10


10-7


-W









At approximately 10-7 seconds, the spur expansion is

complete, resulting in the so-called "primary yield" of the

radiolysis products eaq-, H30+, OH, H, H2, H202, and HO2.

Radiation chemical yields are expressed as G-values, as

shown in Table 1,38 where G is the number of species (repre-

sented by X) created or destroyed per 100 eV of absorbed

dose, and are written as G(X).

Table 1

Radical and Molecular Product Yields in Irradiated Water



Primary yield eaq- H+ OH H H2 H202 HO2

G( molecules ) 2.63 2.63 2.72 .55 .45 .68 0.026
100 eV




The yields are essentially independent of pH except for

extreme acidic conditions (pH < 3). The G-values are also

dependent on the quality of the ionizing radiation, or the

mean linear energy transfer (LET). Under extremely intense

irradiations, at dose rates so high that the spurs overlap,

yields may also depend on the dose rate.40 In the case of

high-LET radiation45 such as a particles, heavy ions or

fission fragments, or very high dose rates ( > 109

rad/sec),46-49 lower radical and larger molecular yields

result.

In the radiolysis of dilute solutions, most of the

energy is absorbed by the solvent, and effects due to energy









deposited directly in the solute are unimportant for solute

concentrations less than about 0.01 M. Thus all the ob-

served chemical changes in irradiated dilute aqueous solu-

tions are brought about indirectly by the molecular and

radical products of the water radiolysis; this phenomenon is

referred to as the "indirect effect."40 In the presence of

a solute, transient species and final products result from

attack of H, eaq-, OH, and H202 on the added substrate.

Radicals derived from the substrate may also react to form

final products. As evinced by the G-values of the primary

radicals, the radiolysis of water produces approximately

equal numbers of powerful oxidizing and reducing radicals.

The standard reduction potentials for the hydroxyl radical,

OH, and the hydrated electron, eaq-, are 2.72 V and -2.9 V,

respectively.40

For pulse radiolysis chemical applications, well-de-

fined conditions, i.e. either totally oxidizing or totally

reducing, are desirable, and these conditions can be

achieved by interconversion of the primary radicals.50

Briefly, for a convenient way of obtaining almost totally

oxidizing conditions, N20-saturated (N20 = 2.5 x 10-2 M)

solutions are used. N20 converts eaq- to OH, or

eaq + N20 ----> N2 + 0 ----> OH + OH" 129

Acidic conditions of pH s 3 should be avoided due to the

interconversion of eaq- to the hydrogen atom, which is a

major reducing species in acidic media,

eaq- + H+ ----> H 103
aq










For the creation of almost totally reducing conditions,

addition of an organic solute to an inert gas-saturated

solution leaves eaq- as the predominant reducing primary

species. Reactions involved are


OH + ROH ----> R(CH.)OH + H20 I-1

H + ROH ----> R(CH.)OH + H2 I-2


In general, the organic radicals formed, R(CH-)OH are less

powerful reductants than eaq- and are rather unreactive. In

particular, N2-saturated solutions with added tertiary

butanol were used in our work.


1.2.3 Aqueous Solution Studies of Aromatic Systems


In aqueous systems containing organic solutes, reac-

tions occurring between solute and the primary products of

water radiolysis are predominately abstraction, addition,

and one-electron reduction. Organic radicals produced by

these processes can further react before being converted to

stable products, thus leading to complex radiolysis mecha-

nisms, which have been reviewed.51-53

Mechanisms can be somewhat generalized within families

of organic compounds containing the same functional group

due to the tendency of the primary products, eaq-, H and OH,

to react with these functional groups as opposed to the

molecule as a whole.40 Particularly, benzene can be uti-

lized as an analogous system for many aromatic compounds,









with addition to the unsaturated bonds being the character-

istic reaction path. Reaction of the primary radicals from

water radiolysis with aromatic systems exhibit rate con-

stants in the range of 105 to 107 M-s -1 for eaq-, and > 109

M-1s-1 for H and OH.40


C6H6 + eaq ----> C6H6- (+ H20) ---> C6H7. + OH- I-3

C6H6 + H ----> C6H7. I-4

C6H6 + OH ----> C6H60H. I-5


Products of these addition reactions are cyclohexadiene

systems containing an unpaired electron delocalized about

the benzene ring. The dienyl radicals, namely cyclohexadi-

ene, C6H7., and hydroxycyclohexadiene, C6H6OH., have been

investigated by electron spin resonance techniques that

indicate a positive electron density assignment to the

ortho- and para-carbon atoms.54

Extensive pulse radiolysis work has shown these dienyls

exhibit a reasonably strong absorption (e = 5 x 103 Mlom-I)

in the 310-315 nm range.55,56 Rate constants involving the

primary radicals with benzene as well as the dimerization

and disproportionation of the resulting cyclohexa- and

hydroxycyclohexadienyls have also been reported.55-61

Steady-state y-radiolysis studies involving liquid

chromatography,62 radio-liquid chromatography,63 and gas

chromatography,64,65 as analyzing methods, indicate a com-

plex mixture of products formed from the combination and

disproportionation of the cyclohexa- and hydroxycyclohexa-










dienyl radicals. Phenol and biphenyl are the major products

reported, in addition to mixed dienyls and regenerated

benzene. All of the previous studies were carried out in

N20-saturated or deoxygenated aqueous benzene solutions. In

aerated aqueous benzene solutions, eaq- and H are scavenged

by 02. The hydroxycyclohexadiene radical reacts with 02

forming phenol and phenol-like products.66'67


1.2.4 Sodium Tetraphenylborate System


Pulse radiolysis studies of the aqueous NaTPB solutions

have been carried out in this laboratory to help establish a

mechanism consistent with the end product yields obtained

from Co-60 7-radiolysis on aqueous NaTPB solutions.68 These

steady-state radiolysis studies were done in conjunction

with the United States Department of Energy operation at the

Savannah River Plant in South Carolina and concerned the

problem of cesium-137 separation and removal from nuclear

waste obtained from spent fuel reprocessing.69 Precipita-

tion of the radiocesium as its insoluble tetraphenylborate

salt is a method of separating it from the nonradioactive

components and concentrating it to reduce the volume of the

liquid radioactive waste. Other decontamination methods

include ion exchange and evaporation techniques.70'71 The

radioactive precipitate will be stored in large underground

steel tanks until it is sent to the Defense Waste Processing

Facility (DWPF) for immobilization in glass.72'73










The TPB precipitate will undergo intense B- and 7-

radiation from the cesium-137 during processing and storage

that will partially decompose the tetraphenylborate, produc-

ing several organic compounds. Understanding the reaction

scheme which leads to these various organic products as well

as their impact on subsequent processing of the precipitate

are important aspects concerning the design and operation of

the DWPF.68

Since the tetraphenylborate anion, TPB-, is rather

different structurally from benzene or simple aromatics, it

is not obvious that previous work on the mechanism of ben-

zene radiolysis is relevant. However, several lines of

evidence will be presented in this dissertation which indi-

cate that there is a substantial connection. The prepara-

tion and properties of aqueous metal tetraphenylborate salts

have been described by Flaschka and Barnard.74 LiTPB and

NaTPB are found to be the only TPB salts that are apprecia-

bly soluble in water; all TPB salts tend to be soluble in

polar organic solvents.

Only a few mechanistic studies involving primary radi-

olysis radical reactions with the TPB- anion have been found

in the literature. Horii and Taniguchi, using pulse radiol-

ysis, studied the oxidation intermediates of the TPB- anion

in aqueous solutions using the oxidizing radicals N3', Br27,

and SCN2 .75 Kinetic as well as spectral information was

reported for the resulting intermediate, B(C6H5)4', which










was produced in all cases by an electron transfer from the

TPB- anion to the oxidizing radical. Liu et al. reported an

absorbing species at A = 300 nm for the expected radical

derived by OH" addition to the phenyl group of the TPB~

anion.76 Another transient, derived from H' addition to the

phenyl group was also discussed; however, no kinetic infor-

mation was supplied regarding the fate of these resulting

transient species.

Other pulse radiolysis investigations involving the

NaTPB salt include ion association studies, in which the

spectra of the diamagnetic species, Na-, the solvated elec-

tron, eaq-, and the ion pair species (Na+,eaq-) are reported

for alkali metal solutions in various non-aqueous

solvents.77-82

The photochemistry literature of the metal tetraphenyl-

borates was surveyed to find possible mechanisms concerning

the reactions of the TPB- anion and subsequent intermediates

under UV-irradiation. Photolysis of aqueous solutions of

NaTPB using UV light with a wavelength of 2537 A generates

biphenyl as the major product in oxygenated solutions and 1-

phenyl-l,4-cyclohexadiene as the major product in the ab-

sence of 02.83,84 Other photochemical studies involve the

photolysis of tetraphenylborates in non-aqueous organic

solvents.85-87

Additional photochemical studies involving TPB- report

on photochemically-induced electron transfer from the TPB









anion to oxygen,88 and various intermolecular charge-trans-

fer transitions of donor-acceptor ion pairs involving the

TPB- anion.89-91


1.2.5 Aqueous Solution Studies of Transition-metal Complexes


In aqueous systems containing transition metal complex-

es, the predominant reaction occurring between the solute

and the primary products of water radiolysis is a one-elec-

tron transfer, either oxidation or reduction. This electron

transfer can occur by an inner- or outer-sphere

mechanism,92,93 often leaving the complex ion in an unstable

oxidation state. Aqueous solutions of both transition

metals and their complexes, most notably bio-inorganic

molecules, have been irradiated and the radiation chemical

processes which occur have been extensively reviewed.94'95

In aqueous systems, equation of the metal complex from

ligand exchange with water molecules can occur, and has been

reported in both pulse radiolysis studies96-99 and photo-

chemical studies.100,101 Changes in the stereochemistry

and coordination number of the transition metal complex upon

pulse irradiation have also been investigated.102,103


1.2.6 Hexachloroiridate System


The redox chemistry of the IrCl62- and IrCl63- complex-

es has been of recent interest due to the prospect of using

the system to produce molecular hydrogen by the solar photo-

chemical reduction of protons in acidic aqueous solu-










tions.104 The solar chemistry of metal complexes has been

reported by Gray and Maverick.105 Solar chemistry is de-

fined as that area of photochemistry in which the excitation

energies fall within the spectrum of solar irradiation at

the earth's surface. The proposed scheme involving aqueous

HC1 solutions of IrC162-/3- is


IrC163- + H ----> IrC162- + 1/2H2 I-6

IrC162- + Cl- ----> IrC163- + 1/2C12 I-7


The net result is the conversion of HC1 to hydrogen and

chlorine using UV and visible light as the only energy

sources. While Gray reports that the second reaction occurs

with low efficiency at wavelengths higher than 430 nm, the

first unfortunately occurs only with UV light, e.g. at 254

nm.

In this study we attempt to further elucidate the

radiation chemistry of the chloroiridates under various

aqueous solution conditions, namely in alkaline, N20-satu-

rated solutions and in neutral, aerated solutions.

Dynamic processes occurring in the IrCl62- / IrCl63-

system have been previously investigated by photochemical

techniques.100,101,106,107 Dainton and Rumfeldt made perti-

nent observations concerning the chemistry of the system,

although their experimental procedure involved Co-60 y-

radiolysis rather than direct studies of the transients.108









Mills and Henglein used steady-state gamma radiolysis

of aqueous IrCl63- to explore the formation of colloidal

iridium and the catalytic properties of the colloid with

respect to H2 formation.109'110 Pulse radiolysis of NaIrClg

aqueous solutions, carried out by Mills and Henglein, exam-

ined the reduction of IrCl63- by eaq- and the (CH3)2COH'

radical. A fundamental pulse radiolysis study on the aque-

ous solution redox reactions of hexachloroiridate complexes

by Broszkiewicz addressed both the reduction and oxidation

of aqueous IrC163".111 From his work, the author concluded

that octahedral IrCl63- is oxidized by a single electron

transfer to octahedral IrCl62- without changing its struc-

ture or ligand composition, i.e. equation. Edwards also

commented that the iridium chlorides are typical examples of

complex ions that are relatively inert toward substitution,

but which undergo rapid electron transfer reactions.112

Further pulse radiolysis studies on transition metal

hexachloride complexes have been reported by

Broszkiewicz.113-115 Other pulse radiolysis studies involv-

ing aqueous IrCl63- have examined its oxidation by the

azidyl radical, N3*,116 and the hydroxyl radical, OH*.93














CHAPTER II
EXPERIMENTAL APPARATUS AND PROCEDURES

2.1 Pulse Radiolysis Instrumentation


Reactive intermediates generated in radiation-induced

chemical processes are short-lived; thus the pulse radioly-

sis instrumentation must be able to monitor the transient

behavior with a high degree of resolution over extremely

short intervals. Since the concentration of such intermedi-

ates can influence both the mechanistic pathway and the

final product yields, detection techniques that are sensi-

tive to very low concentrations of radicals are necessary

for a complete characterization of the transient behavior.

The University of Florida pulse radiolysis system

configuration incorporating computer control is shown in

Figure 2. The accelerator used is a Febetron (brand name

for the impulse generator produced by Field Emission Corp.)

706, which operates on the principle of the Marx-bank cir-

cuit. Other accelerators used in time-resolved studies

include the linear accelerator linacc), and the Van de

Graaff generator. One may see that the other components

shown comprise an absorption spectrophotometer. Absorption

spectroscopy is the most widely used technique among others

mentioned previously, for monitoring transient behavior in

pulse radiolysis.






















S4-
>, < O
10 0
>1 r- >1
a 4 k
,-4 s4i (1)
S4 3 : 0 (U N 4 -N


O O 0 -- 0 *4 0
aO O 6 Oi a) E


O 4 O ,- 0 4 4
00 n E o rA 0 > 0
S0 c N O .M 0 > (0

O 2. -.r-4 r m m
4 toCd -4 0 O
(E C --ri O ) 4 ) C ) U U

-C 0 4 t3) -H r-l 0 4 -
o 0 3-4 3-i : -4 o 3- r 0 0


U* E ** **4 *-4
S> p, 4 cn E & > > > o



S4O
E3 3 C C*4*





















O 10 O 5M3 O
r-4

4-O
0















4
O)


-l
(U






>1
00


*-I O >4 4 ** f *
U0 H : p

0 0 )0f 04 0 P

04 rd o 0 (0 a)
z a) 04 ,- .44J4.J >4
C 0 0 E 0 (
0 0 P 0 m -40 U) 0 r Cd
003 4- 04 (4 1 4 0 5-
-P r-A 0) Z 04 010 P- O't
C Eo Ei r c o_ e 0 P- 4-) 1D
S 0) z 0 C d (a (o -C 0. 0)
0 'O h P4 Wd 0 r-4 r-4 0 4 1- r4
U) X a04














LL ----


I


I z
0


CD
W
m
LL


0-I
0c
- To




i

T


I. ~it


m



10


J~~Q-, 0


-i





'c'



-J


7J
i Li


H







CI


ii


i0


J


I cl i
i
i i


i









2.2 Absorption Spectrophotometry


Components involved in an absorption spectrophotometer

are the light source, an optical train including all lenses,

mirrors and absorption cell, the monochromator, the detector

and a recorder. In flash photolysis and pulse radiolysis,

the absorption cell also serves as the reaction region.


2.2.1 Light Source


The light source used should provide high monitoring

light output to optimize the signal-to-noise ratio, S/N,

which is directly related to the intensity of light striking

the photocathode of a photomultiplier by the equation:

S/N = (Is/ A f)1/2 II-1


where Is is the light intensity at the photocathode and

delta f is the bandwidth of the recorder system.117,118

This relationship is applicable when signal shot noise is

the limiting S/N determining factor as is the case in fast

( > 1 kHz) kinetic spectrophotometry. Lasers provide high

monitoring light intensities but are limited as to their

wavelength of operation. Thus in order to utilize an ab-

sorption technique that is applicable to all transients or

combination of transients throughout the ultraviolet and

visible spectrum, a high power spectral lamp with a continu-

ous distribution is preferred. Xenon-arc lamps filled with









xenon gas at above atmospheric pressures provide the follow-

ing features: high arc stability and luminous flux, high

reliability and long operating lifetimes up to 1000 hours.

In addition, high-current pulses can be delivered to the arc

lamp, which enable very high monitoring lamp outputs during

transient measurement times of microseconds to milliseconds.


2.2.2 Absorption Path and Monochromators


The flow reaction cell previously mentioned allows for

the production of transient species in the irradiated volume

which can be directly monitored by absorption spectrophotom-

etry. For example, using the Beer-Lambert relationship,

A = e bc II-2

where e = molar extinction coefficient (M-1cm-1)

b = pathlength (cm)

c = concentration (M)

and assuming 1) a transient molar absorption coefficient, e,

of approximately 1000 mol-ldm3cm-1, 2) a transient popula-

tion which produces a 10% deflection in the initial light

intensity, and 3) a 1 cm absorption pathlength, one calcu-

lates the initial transient concentration formed in the

irradiated volume immediately following the pulse to be

approximately 4.5 x 10-5 M.

Monochromators function to isolate a small wavelength

band from a polychromatic source and consist of a dispersive

element, either a prism or grating, and an image transfer










system of slits and mirrors. By using a monochromator with

an adequate light flux throughput and a varying wavelength

range, transient signals can be recorded as a function of

wavelength to build a time-resolved transient spectrum.

The throughput factors which determine the radiant

power passing out of the exit slit of a monochromator are

the source spectral radiance, Bx in units of Wmm-2 sr-1 nm1,

and the monochromator throughput factor, Y in units of mm2

sr nm. The product of these two factors gives the output

spectral radiant power, Q, in watts.118 For operating a

monochromator with a broadband or continuum source the

monochromator throughput factor, Y, is defined as

S(1r/4)
Y =w2 h TopRd II-3
(F/n)

where w = slit width (mm)

h = slit height (mm)

F/n = f-number or effective aperture

Top = optical transmission factor (unitless)

Rd = reciprocal linear dispersion (nm/mm)

Since the light image is usually focused down on the en-

trance slits by a condensing lens, the slit width is the

only experimental variable parameter in determining the

light throughput at a particular wavelength for a monochro-

mator with a fixed optical transmission factor, effective

aperture and reciprocal linear dispersion.117









2.2.3 Photomultipliers


The advantages of using photomultiplier detectors to

display transient absorption signals on transient recorders

are high sensitivity due to secondary emission multiplica-

tion, fast response times relative to the half-life of the

relaxation processes being monitored, and the ability to

handle high light flux levels while maintaining a linear

signal at high output photocurrents.119 Two types of photo-

multipliers were used in this work which have different

spectral response ranges. An EMI Model 9250 QB end-on 50 mm

window PMT fitted in a Pacific Precision Instruments Model

3262 housing was used initially with the geometry shown in

Figure 3. Because of its extended spectral response range

above 600 nm, a Hamamatsu Model R928 side-on 30 mm window

PMT fit into a Pacific Precision Instruments Model 3150

housing was eventually incorporated into the geometry shown

in Figure 4.

The photomultipliers were powered by a John Fluke, Inc.

Model 412A High Voltage DC power supply, which proved to be

a well regulated and stable dc source. The overall gain on

the PMT could be altered by changing the applied voltage,

typically from 1000 Vdc to 1250 Vdc in increments of 10 or

100 volts, while maintaining maximum gain on the operational

amplifier.

The EMI end-on tube has a bialkali photocathode, a

Spectrosil quartz window, and an optical range of 165-650 nm













Cell holder


Febetron

IP 706

-1


IL LE


V


McPherson
218
Monochromator


L Xenon arc lamp
LE Condensing lense
IP Ion pump
PB Lead cave / shield
PH PMT housing


PM
*


PB


PMT- ::

S-PH


PM Parabolic mirror
PMT Photomultiplier tube
RB Adjustable razor blades
SC Solution cell


Fig. 3. Experimental arrangement using the McPherson 218
monochromator.


SC


RB









'MT PH


PB


Febetron 706


/
/
/ ;


IP

Cell
Shoulder

L RB

SC PM

L Xenon arc lamp or laser
LE Condensing lense
IP Ion pump
PB Lead cave / shield


Fig. 4. Experimental arrangement
monochromator.


-- Jarrell-Ash
4 'Monochromator

- LE


Inset


i__ P
PMT


PH


PH PMT housing
PM Parabolic mirror
PMT Photomultiplier
RB Adjustable razor blades
SC Solution cell


using the Jarrell-Ash


F
,.----'iT_ F









with a peak wavelength, or maximum radiant sensitivity

(mA/W), at 420 nm. Figure 5 shows a diagram of the base

components which were customized to achieve optimum rise

times, gains and linearities for use in the pulse radiolysis

system. The EMI Model GB 1001A fast electronic switching

circuit connected through an optoisolator and switching

transistor gates off the first dynode voltage of the PMT to

eliminate overloading problems caused by short burst expo-

sure to high light intensities. The gating circuit offers a

precise way to regulate the PMT from a + 5 volt gate signal

and has the specifications of an on-to-off fall-time of 0.5

microseconds and an off-to-on rise-time of 1.5 microseconds.

This circuit which is normally applied in flashlamp or laser

systems to protect from overloading conditions was original-

ly employed to eliminate the overloading of the PMT by

fluorescence of OH radicals which occurred in previous gas

phase studies on the argon sensitized pulse radiolysis of

water vapor.3 In the present liquid phase work, such severe

fluorescence problems derived from radiation interactions

with either the aqueous chemical system or the quartz cell

have not been encountered.

Gating of the PMT was applied to reduce the effect of

high levels of electromagnetic interference (EMI) associat-

ed with the high beam current Febetron 706 machine. Ac-

counts of these electromagnetic fields and their effects on

detection electronics are discussed in the literature.26'120














.




0
o




0 I
O


|,, -


0o 0
o 0


0 0

0 0
LO
co




3----r-'L(
I *


6
C-


a)
-0
In o


-o


4-'


.-
Sa


1)1
VI
0


0)
O



)

0


E



S> a




0 0 Sn 0)
o r -




0- 0-- o)

c CO

<<<(D









0
-0
0)



00
-. m "3


oo


CN
0



O-
P


(0
4-'
0


-C


-H
to

0
C



0






rH
C











-H
Ln








4)
r-
UQ












a)

.r
0











-4-
o











4o
0





*4
*il


0








CO











*H

o-





3~









By gating off the initial dynode of the PMT during the

radiation pulse, overloading of the photocathode by the X-

ray (X-radiation) and the radio-frequency (RF) noise coinci-

dent with the electron pulse was significantly attenuated.

Further attempts to reduce the EMI effects included the use

of lead shields inserted into the entrance of the PMT hous-

ings, Figure 6, and extensive lead shielding around the

outside of the PMT housing.

The Hamamatsu side-on PMT was obtained to expand the

wavelength range to allow transient absorption measurements

above 600 nm, and was used in all subsequent experiments

after installation. This PMT has a multialkali photocath-

ode, a UV-glass window, and an optical range of 195-900 nm

with a peak wavelength at 400 nm. Figure 7 shows a diagram

of the customized base components used with this PMT along

with a gating circuit that is analogous to the one previous-

ly described.


2.3 Light Source Systems


For a versatile pulse radiolysis system with capabili-

ties of nanosecond sampling times in the UV-VIS region of

the spectrum, stable and high analyzing light intensities

are needed in order to permit the observation of weak or

long-lived absorption signals, to reduce shot noise, and to

increase the signal to noise ratio.119























a) 2 1/16 inch diameter x 1/2 inch thick lead shield
for end-on PMT housing, Model 3262.


b) 1 1/4 inch diameter x 1/2 inch thick lead shield
for side window PMT housing, Model 3150.


Fig. 6. Lead shields for PMT photocathodes in the Pacific
Precision Instruments PMT housings.












0
0* : ---
S00 C-

0o ___





7 oo I
S-T -i i


0










r:



-J
0 0


0


0














-0

CO

j!o al.
c-
4--a
.- r


d 0- E

II c

-^ --.^---- _() ^
6o-
0 >0 a


co
0 0






O a
I--- --------C C ) 7CO
0 0a











.E
-o o
00 ;


n -





D o


0o


-g4
= 0
a:c,)


a,
C


o
4-a
0

r-
0)
-CI


Q.

CD
ii


4-*-

L


0
o .

CO
r- I









2.3.1 Xenon-Arc Lamp


The lamp system used in this work consisted of a xenon-

arc high pressure discharge lamp contained in a water-cooled

housing and powered by a water-cooled ignition device / DC

power supply. Several different bulbs including an Advance

Radiation Corporation XSA 350 and 500 watt and a Ushio UXL

302-0 300 watt were used throughout the work. The ARC bulbs

were of the deep UV design, in which a metal vapor, such as

mercury, is present in addition to the xenon gas providing a

strong distribution in the deep UV region (190 to 250 nm).

The Ushio bulb was not seeded with such a metal and its

continuous spectrum is shown in Figure 8. This spectrum was

generated by feeding the PMT output across a load resistor

and into a Linear Instruments Corporation Model 591 chart

recorder.

The bulb was contained in a PRA-Canada ALH 220 housing

with dual water cooling loops and powered by a PRA-Canada

Model M301 ignition-power supply. The power supply uses a

continuous feedback, constant current mode of operation to

give excellent current stability. Current programming with

square, triangular, or sine wave modulation can be used in

this unit to vary the optical output of the lamp. As shown

in Figure 9, a 2-3 L/minute cooling line was in series with

the power supply and top face plate portion of the housing

which was oriented vertically. A separate 0.25 L/minute



































0
Ln
ml


LO









0
*lZ

















0
*n
CO









Febetron 706


M




LE


----------- -- ---------------
i- i !
SH SC
SH SC


to drain
i ---- ___- -

Y- (Lam& water in
Lamp& 2-3 I/mi
Housing 2-3
-- 1--


to drain


M 301 Power
Supply


DC volts DC amps


LE Condensing lense


EC Electrical connectors
I(o) Initial light intensity
I(t) Transmitted light intensity


M Mirror
SC Solution cell
SH -Shutter


Fig. 9. Xenon-arc lamp schematic diagram.


It


i

r


in


water in
0.25 1/min


L









cooling line was used for cooling of the lamp electrodes.

The approximate dimensions of the different optical arrange-

ments are also shown for the lamp housing which contains an

f/2.4 exit lens.

For conditions of 1) low absorbance monitoring on the

order of a 1% change in light intensity or less, or 2) lower

relative light output (i.e. the lower and upper regions of

the lamp output spectrum shown in Figure 8) a short dura-

tion, very high monitoring light output is desired. This

was accomplished by using a conventional signal generator

feeding a BNC connector in the rear panel of the M301 power

supply. The timing and magnitude of the positive going

square pulse was determined by the specifications given by

the manufacturer.121 The pulse width is required to be < 1

second to eliminate damage to the bulb. The pulse magnitude

can be varied between 0 and 1 volt according to the follow-

ing equation

out = idle + [Vmod/4) x 50] II-4
where Iout = M301 output current

Iidle = idle current, typically 3-5 amps
Vmod = output voltage of the signal generator

The upper limit of Vmod, 1 volt, is determined so that Iout

does not exceed the listed nominal operating current of the

lamp which for the Ushio UXL 300 W bulb is approximately 15

amps. To attenuate and fine control the 5-volt TTL type

signal from the pulse generator, a potentiometer voltage










divider circuit was placed in series with the pulse genera-

tor and M301 power supply. Preliminary monitoring of the

pulse parameters was done through a Tektronix Model 35A

oscilloscope prior to actually pulsing the lamp.


2.3.2 He-Ne Laser


A Spectra Physics Model 155 helium-neon laser was used

for alignment of the optical systems, calibration of the

monochromator gratings, and as a light source for absorption

spectrophotometry involving the kinetics of the hydrated

electron, eaq-. Characteristics of the monochromatic 632.8

laser light such as high collimation, low divergence, and

high intensity make this source ideally suited for eaq

studies.122 Figure 4 shows the optical arrangement used for

the He-Ne laser, the Jarrell-Ash monochromator and side-on

PMT. Attempts to monitor the 632.8 nm light with the end-on

EMI PMT were unsuccessful due to this tube's lack of sensi-

tivity above 600 nm.


2.4 Reaction Cells and Cellholder


Two types of reaction cells, both consisting of modi-

fied quartz UV-VIS spectrophotometric cuvettes, were con-

structed for this study. Previous accounts of similar

reaction cells for use in low energy electron beam radioly-

sis studies involving liquids indicated the importance of









using very thin electron entrance windows that would mini-

mize the attenuation of the low energy electron beam in the

liquid.123 A cuvette fitted with a reservoir and flow exit

for flushing purposes was used in all the on-line absorption

detection work and a non-flow cell was used exclusively for

the Fricke dosimetry experiments.40 Both cells were fitted

into an aluminum cell holder to provide reproducible posi-

tioning and to assure the delivery of equal doses.


2.4.1 Flow Reaction Cell


The flow cell, Figure 10, was constructed from a 60 ml

separatory funnel, a 9 2 stopcock, a $ 5/20 glass joint, a

glass/quartz connector seal and a modified quartz UV-VIS

cuvette. A thin mylar sheet = 200 microns thick was held by

epoxy glue to the quartz cell and served as the electron

entrance window. In the initial construction of the cell,

FISHER brand microscopic optical glass cover slides with a

thickness of 0.13 to 0.17 mm were used.124 However, the

mylar sheet material was chosen as the electron entrance

window due to its lesser thickness and the ease by which it

could be mounted and trimmed on the cuvette. The optical

pathlength was 1 cm, and with an electron penetration depth

of ca. 1.5 mm for 600 KeV electrons in water,122 the irradi-

ated volume was 1 x 1 x 0.15 cm. This electron penetration

depth, which is less than the extrapolated range of 1.9 mm,

is taken as the depth over which a reasonably uniform dose









N20 gas










Stopcock, E 2


Separatory funnel,
60 ml






Glass joint,
S5/20


Modified quartz
cuvette, mylar window


Fig. 10. Flow-reaction cell with modified UV-VIS cuvette.









deposition can be assumed.125 For studies using purging

gases, the gas was continuously bubbled into the upper

reservoir for the duration of the experiment.


2.4.2 Non-Flow Reaction Cell


This cell, Figure 11, was constructed from a UV-VIS

cuvette to provide detection of 304 nm light associated with

the maximum absorption of the ferric ion, Fe3+, the oxida-

tion product derived from the radiolysis of an acid solution

of ferrous ion, Fe2+, in the Fricke dosimetry system as

discussed in Appendix B.40 The electron entrance window was

identical to that of the flow cell and a total volume of 1.4

ml was delivered by syringe to the cell prior to radiolysis.

This cell could be readily removed from the aluminum cell

holder in the pulse radiolysis system and transferred to a

Beckman DU model 2400 spectrophotometer with Gilford solid-

state electronics, allowing absorption measurements to be

made as a function of the number of radiation pulses re-

ceived. A dilution factor involving the actual irradiated

volume of 0.15 ml and the total volume of 1.4 ml was used in

all dose calculations.


2.4.3 Cell Holder


An aluminum cell holder, Figure 12, was used to enable

reproducible placement of the solution cell with respect to

both the electron beam and analyzing light. The holder










FRONT VIEW





1 cm



1 cm


mylar sheet e-beam
entrance window


solution injection
by syringe


SIDE VIEW


total volume =


1.40 +/- 0.02 ml


Fig. 11.


Non-flow-reaction cell formed from UV-VIS cuvette.
Reaction volume consists of 1 x 1 x 0.15 cm region
immediately behind mylar entrance window.









6.0 "


0
4 thru holes


8.0 "


wire mesh screens,
60 80 %
beam reduction


ANALYZING


LIGHT


adjustable razor blades,
entrance and exit


apertures


Reaction cellholder with adjustable razor blade
mounts and wire-mesh screens. Electron beam
enters through rear flange and traverses 8.0
inches in air. Radiation-induced reaction region
occurs in cell (not shown) located at intersection
of e-beam and analyzing light.


Fig. 12.









consists of a 1 x 1 inch open rectangular aluminum column

eight inches in length fitted to a six-inch diameter alumi-

num flange that is attached by four threaded screws to the

outer edge of the short-pulse adapter chamber of the Febe-

tron 706. Adjustable razor blades mounted at the entrance

and exit apertures at right angles to the electron beam axis

defined the width of the analyzing light beam. The use of a

very narrow analyzing light-beam allowed for the study of

the solution kinetics by monitoring only a narrow cross-

section for which the dose could be reasonably defined.

Using this arrangement, the electron beam traversed ca.

8 inches of air between the field emission tube exit window

and the thin mylar entrance window of the reaction cell.

This distance creates a slight attenuation of the electron

beam intensity which is primarily associated with a spread-

ing of the effective beam diameter away from the tube face.

For a distance of eight inches the beam will have an effec-

tive diameter of three centimeters as compared to a diameter

of 1.5 centimeters as it exits the tube face. The loss of

beam intensity due to absorption in air should be negligible

due to the maximum penetration range of 80 inches for 600

KeV electrons in air.125,126

Experiments with FISHER brand optical glass microscopic

coverslides placed in the cell holder at the solution cell

position were performed to determine the depth distribution

of the electron beam. Typical depth-dose curves are shown










in Figure 13 which includes data for two experimental condi-

tions. Initially a stack of approximately 20 slides was

exposed to a single Febetron shot with maximum charging of

30KeV. Absorption measurements were then made on each

individual slide to detect the amount of discoloration in

the glass due to the e-beam penetration. Secondly, a simi-

lar stack of coverslides was exposed to 10 cumulative shots

at full charge, followed by individual absorption measure-

ments. Both data sets indicate an extrapolated range for

the 600 keV electrons in the glass to be approximately 7

slides. Using a slide thickness of 0.15 mm, the extrapolat-

ed depth in glass is found to be 1.0 mm. Assuming that

glass is approximately twice as dense as water, these data

indicate a maximum range for 600 Key electrons in water to

be approximately 2.0 mm, which agrees with the earlier

reported value of 1.9 mm.125

Figure 14 shows the absorption due to the discoloration

in a single slide as a function of the number of pulses

delivered at maximum charging. The accumulated discolora-

tion resulting from the e-beam passage through the glass

slide was found to be non-linear, with the absorption fall-

ing off as a function of pulse-number.

Wire mesh screens capable of 60% to 80% electron beam

reductions could be positioned in the cell holder two inches

from the field emission tube window (Figure 12) to aid in














Ten pulses delivered


One pulse delivered
IC-


i I L ------ .....
2 4 6 8
Coverslide #


Depth-dose curves for glass coverslide experiment.


-- -.


20








15



O
O
0



010
C

O
n
I_
0


5 -


Fig. 13.












35





30







C
5O
0


-25
U)

20








15






10


Absorbance change with number of pulses delivered
for glass coverslide experiment.


5 10 15 20
Pulse #


Fig. 14.









acquiring transient formation signals occurring during the

first few microseconds immediately following the radiolysis

pulse. These screens restrict the flux of the electron

beam which was maintained at a maximum charging voltage of

30 KeV. With the wire mesh screens inserted, attenuation of

the beam intensity decreases the total average population of

initial radicals formed. This beam flux attenuation helps

to prevent radical-radical interactions and provide favora-

ble radical-solute interaction conditions. However, due to

both a malfunction in the fastest data acquisition mode of

the transient digitizer, and electromagnetic interference

associated with the Febetron 706 system that were discussed

earlier, attempts to capture transient formation signals

with enough resolution for kinetic analysis were not suc-

cessful.


2.5 Monochromators


In the early stages of this work a 0.3 meter McPherson

218 monochromator was used. Later, efforts were made to

reduce electronic interference associated with the electron

beam pulse by removing the monochromator and PMT couple away

from and to the rear of the field emission tube. Due to the

rather permanent fixture of the Mcpherson 218 and its asso-

ciated vacuum pump assembly relative to the initial experi-

mental geometry, a second 0.25 meter Jarrell-Ash 82-41550

monochromator was employed.










2.5.1 0.3 Meter Monochromator


Initial studies were carried out using a McPherson 218

vacuum/atmospheric monochromator which has an f/5.3, a 2400

G/mm plane grating and a 1.33 nm/mm linear dispersion. The

vacuum capabilities were not employed for any of this work

and the 2400 G/mm grating having a 0 5,000 angstrom wave-

length range was eventually replaced with a 1200 G/mm grat-

ing capable of operating in the wavelength range from 0 -

10,000 angstroms. A synchronous motor-driven gear box

supplies 12 scanning speeds from 0.5 angstroms/minute to 200

angstroms/minute and slit widths were adjustable from 10

microns to 2 millimeters. Slit widths of 1.5 millimeters

and a fixed slit height of 8 millimeters were used. Figure

3 shows the optical configuration used with the McPherson

monochromator. Light exiting the xenon arc lamp was passed

through a condensing lens onto a first surface mirror and

reflected through the solution cell. The beam was then

focused on the entrance slit of the monochromator and after

wavelength dispersion the exiting beam was reflected onto

the photocathode of the PMT by a 2.5 cm focal length para-

bolic mirror.


2.5.2 0.25 Meter Monochromator


Initial testing of the Jarrell-Ash monochromator cou-

pled to the end-on PMT with both components located approxi-









mately 2 meters away from the field emission tube showed a

marked improvement in reducing the electromagnetic noise

interference. Using the McPherson monochromator in the

previously shown geometry in conjunction with the gating

circuit produced a net dead-time, caused by gross overload-

ing of the PMT, of > 5 microseconds in the detection system.

When the detection system was relocated, as shown in Figure

4, net dead-times of 2 to 3 microseconds could be attained

without the use of the gating circuit. All subsequent work

was completed with this arrangement and eventually the end-

on PMT was replaced by the side-on PMT. To attain further

reduction of the EMI effects, the entire detection system

and signal lines would have to be either completely removed

from the room containing the Febetron 706 or extensively

shielded.120,127

In this modified configuration the analyzing light,

after passing through the solution, was reflected by a first

surface mirror back to a plano-convex f/2.5 condensing lens

and focused onto the entrance slit of the Jarrell-Ash mono-

chromator. This monochromator has an f/3.5, a 1180 G/mm

grating and a 3.3 nm/mm linear dispersion. A wavelength

motor drive of 100 nm/minute was coupled to a wavelength

drive knob to enable scanning of the light source spectrum.

The slit arrangement provided with this monochromator

was altered to accommodate the direct coupling of the Jar-

rell-Ash monochromator to both a previous gas phase aluminum








reaction cell, and the Pacific Precision Instruments PMT

housing.128 In this work only, the direct couple of the

monochromator and PMT housing was utilized. This was accom-

plished by screwing the PMT housing containing the side-on

Hamamatsu tube directly to the exit slit flange adapter.

Figure 15 shows the entrance and exit system flange adapt-

ers. Brass slit bodies of fixed width and height, 0.71 mm

and 15 mm respectively, were screwed into the aluminum

flange by turning the two small holes in the slit body with

a sharp tool.


2.6 Febetron 706 System


The principle of pulse radiolysis involves the delivery

of ionizing radiation to a chemical system in the form of a

short pulse that creates a non-equilibrium system with an

adequate amount of transient species that are monitored in

time. An accelerator is used as the source of the high

kinetic energy ions and several related parameters are

important in pulse radiolysis measurements. Primarily, the

radiolytic pulse should be very short relative to relaxation

of the transient system, and the pulse current should be

large enough to produce an observable concentration of

transients. Energy deposition, which depends on 1) the

particle's mass, charge, and velocity, and 2) the medium

density, is critical in determining the distribution (either

homogeneous or non-homogeneous) of radical concentrations

produced.












slit area = 0.71 mm x 15 mm


/ / /


front view






I--



side view


_---_ "4 bolt holes



slit holder
flange


'0-ring


o-ring
groove


zIzz


o-ring
groove



4 thru holes


Fig. 15.


Entrance and exit slit system flange adaption to
the Jarrell-Ash monochromator.


!o









The Febetron 706 electron accelerator used in this work

is fitted with a Model 5515 high vacuum field emission

electron tube and has the following specifications: 12

joules maximum pulse energy, 8,000 amperes of peak current,

3 nanosecond pulse duration (FWHM), 5% peak to peak repeat-

ability, and a maximum electron energy of 600 KeV. The

extremely high currents make this model particularly ap-

plicable to gas phase studies.

However, it was suspected that the high vacuum electron

tube had become gaseous due to intermittent use in previous

years and the extended lifetime of the electron tube beyond

its suggested 3500 pulses. The e-beam tube had failed after

ca. 8000 pulses; the beam had burned microscopic holes in

the window which allowed the pressure in the tube to rise to

atmospheric. It was expected that partial operation could

be restored by replacing the window and reevacuating the

tube. This attenuated beam feature would be beneficial to

condensed phase studies by eliminating radical-radical

interactions caused by the absorbance of enormous radiation

doses. Encouraged by other somewhat analogous and confirm-

ing reports,122,129-132 we pursued the application of the

Febetron 706 accelerator to aqueous solution work.

Details of the Febetron 706 system can be found else-

where.125,126,133 Figure 16 shows a block diagram of the

Model 706/2677 system. The Febetron 706 system was main-

tained by keeping the various chambers with their associated











on c ; E
"-Ca 00



SO' -


c a
(10)0 -
CVi~


oD


0) -
?a)

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pressure regulators and gauges properly pressurized. A

compressed air tank is used to pressurize the module chamber

at a maximum of 80 psi and the short pulse adapter at a

maximum of 240 psi. Freon-12 was maintained at 13 psi in

the pulser case. The transformer oil in the short pulse

adapter was circulated daily by an electric pump connected

to a large oil reservoir.

The accelerator operates on the principle of the Marx-

bank circuit which consists of a number of connected high

voltage capacitors that are charged in parallel and subse-

quently rapidly switched to a series arrangement through

spark gaps. This circuit, located in the Marx-surge stage

of the pulser, produces a high voltage, extremely high peak

power pulse that is used to pulse charge through a series

spark gap in the central electrode of the short pulse adapt-

er stage of the pulser. This short pulse adapter then

discharges an extremely short 3 ns high current pulse to the

field emission electron tube. This pulse generates electron

emission from the cathode and the electrons are then accel-

erated toward an exit window that functions as the anode.

As mentioned above, due to the lack of an inward de-

flection in the thin exit window of the field emission tube,

it was decided that gaseous conditions existed inside the

tube. Under normal conditions, the thin metal window would

be noticeably drawn in by the high vacuum. Experiments

using the technique of calorimetric dosimetry carried out










directly in front of the tube exit window showed negligible

energy outputs. Therefore a modified electron beam tube

exit system was fabricated.


2.6.1 Refurbished Beam Tube


A modified electron beam tube flange and exit window

system132 was constructed to renew the output of the Febe-

tron 706 system. This modification, Figure 17, was formed

from a stainless steel chamber 4.75 inches in diameter and

1.25 inches thick, and fit with a Model 202-100 Perkin-Elmer

2 liter/second differential ion pump powered by a Model 222-

0200 Perkin-Elmer IONPAK 200 power supply. The high vacuum

current limiting power supply operated at a voltage between

+4000 volts DC and +6000 volts DC and the system was capable

of attaining pressures below 1 x 10-6 Torr.

The former anodic window of the field emission tube was

cut away and a thin, approximately 0.001 inch stainless

steel window and o-ring were set into the compartment. The

compartment was attached by three threaded screws to the

field emission tube window face plate flange of the Febetron

706 with a second o-ring seal. Initially, the thin window

was placed 0.8 inches away from the original anode window

location. Although an adequate vacuum was attained, further

dosimetry experiments showed no improvement with this geome-

try so the window was set further into the compartment 0.4


















4-..
i! C

0n --


S------- > 0L


C,)

>0 0
",' 6o
--L uj w


=- o
o N
a


iii


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inches away from the original window location. After rough

pumping the chamber down to a few microns of pressure and

attaining the minimum +4000 volts DC required for proper

operation of the ion pump, calorimetric dosimetry measure-

ments were again performed.


2.6.2 Calorimetric Dosimetry


The total-beam calorimetric technique, as illustrated

in Figure 18, involves the measurement of the heat deposi-

tion in an aluminum disk upon firing the Febetron 706 at

maximum charge. The thickness and diameter of the disk,

0.033 inches and 1.385 inches respectively, were chosen to

assure complete e-beam deposition. Aluminum is suitable due

to its high thermal conductivity, specific heat, and low

backscatter energy coefficient. The temperature of the

calorimeter was conveniently measured by attaching a thermo-

couple and measuring the voltage output with a recording

millivoltmeter. The thermocouple was attached to the alumi-

num disc in this particular calorimeter by drilling a small

hole in the center, inserting the thermocouple wires, and

swaging the aluminum around them with a punch. The calibra-

tion of the thermocouple/chart recorder was accomplished

using room temperature of = 25 C as the base line and

normal body temperature of = 37 C as the maximum scale

value. For the maximum temperature reading, the disk was

held firmly in the palm of the hand until a steady equili-

brated signal was obtained.









Febetron 706


ion pump


e-beam


styrofoam
mount


chart recording
millivoltmeter

37.0 C

thermocouple
T cooling
S25.0 C


S aluminum disc





thermocouple
wires
(4 ft.)


Fig. 18. Total beam calorimetric dosimetry arrangement.





Using the equation

Q = m Cp A T II-5

with Q = heat required to raise the specific heat of the

calorimeter by A J, Joules

m = 2.3 +/- 0.05 grams (mass of the aluminum disk)

Cp = 0.22 cal/ C gram (specific heat of aluminum)

A T = 0.53 C (difference between pre- and post- pulse

read from chart recorder)

a value of 1.12 +/- 0.06 Joules was determined as the beam

energy absorbed per pulse. These positive results indicated

that the placement of the new anode window was a critical

factor with possible arcing complications arising when the

new window was not located close enough in to the original

window position.


2.7 Transient Recorder and Computer System


While early pulse radiolysis studies used the oscillo-

scope-Polaroid photograph technique for recording transient

signals, development of sophisticated transient recorders

followed that now have replaced this manual data analysis

method.117 Digital recorders now digitize the input signal

in real time and can resolve the signal into separate chan-

nels thus providing a stored digitized record of the tran-

sient trace as a function of time. In addition, interfacing

of the recorder with a computer allows for integrated con-

trol of the operational parameters such as time base, sensi-

tivity, delays, signal processing, and data transfer.










The data acquisition and analysis system developed for

this work is a second generation system having been preceed-

ed by a Biomation Model 610B transient recorder supported by

an IMSAI 8080 S-100 bus microcomputer.128 Current instru-

ments include an Analogic Data Precision DATA 6000 waveform

analyzer fitted with a Model 620 2-channel plug-in digitizer

interfaced through a serial port at 9600 baud to a Tandy

1200 IBM-PC/compatible laboratory microcomputer.

The DATA 6000 has two signal-input ranges of +/- 1.2

and +/- 3.6 volts full scale, and a maximum sampling rate of

100 MHz. This sampling rate gives a period (time between

sampled points) of 10 nanoseconds for collection of 512

points using an 8-bit recorder. Although the maximum period

attainable is 300 seconds, a maximum period of 1 microsecond

was used in this work giving a sampling rate of 1 MHz. The

DATA 6000 is noted for its versatile capabilities of signal

capture, processing and data transfer, although the lack of

any fine control on the input voltage parameter was found to

be a rather severe experimental limitation in this work.

The DATA 6000 is controlled by a single internal 68000

microprocessor and a CRT display screen enables visual

inspection of signals before data transfer.134

Data recording parameters were selected either manually

through keypads on the front panel or remotely via computer

control. Remote control of the DATA 6000 via an RS-232









serial interface port utilized three basic functions: con-

trol of data recording parameters, use of processing and

display, and transfer of data to and from the digitizer. To

use these functions, a computer program written in BASIC

language provided either keystroke emulation by key code

number or direct control using English commands. These

operations were sent to the DATA 6000 as string commands and

data transfers to the computer were sent in ASCII number

format. Various timing loops set up in the BASIC program

assured proper hand-shaking. During operation several

parameters such as trigger source, timebase, screen display

and marking were initially set manually and subsequently

controlled remotely through the computer program. For

short-lived transient signals, the multiple trace delayed

mode with signal averaging was used which provides an en-

hancement to the S/N ratio in proportion to the square root

of the number, n, of signals averaged.118 Otherwise, the

single trace delay mode was used with no signal averaging.

As shown in Figure 2, the triggering and delays were

originated from a single initial manual trigger pendant

delivering a 90 volt pulse derived from three 30 volt bat-

teries in series with a standard RC trigger circuit. A

typical timing sequence is presented in Figure 19. Delay of

the Febetron firing was accomplished using an Evans Associ-

ates programmable time delay (PTD) module, Model 4145-2.

Three such modules are present which could be used in series

















U)
Cn





Z
O






0


Z U-









c z
I-I



+ I
oo
00


0

Oi

0
0
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0
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4-


0
LU)








F-
0





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V


----------



li






LU,
LL,


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;- I c i


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i
-- -


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I


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01
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for a maximum delay of 3 milliseconds. The voltage divider

and amplifier in the circuit are required because the incom-

ing trigger for the Febetron must be 90 volts in magnitude

while the PTD uses a TTL type input and output. The lamp

pulsing and shutter control was provided by a Vincent Asso-

ciates shutter driver and timing unit, Model SD 10, which

controlled a Model 225L Vincent Associates UNIBLITZ shutter.

The shutter was not incorporated into the timing sequence

but was manually switched on and off during a calibration

procedure to set the zero and full light levels, Vo and Vm

respectively. The lamp pulse duration was controlled by the

shutter driver and timing unit which provides a positive

going 5 volt square pulse with a variable 8 to 8,000 milli-

second duration.


2.8 Computer Program


Full interaction between the operator and the

computer/transient recorder was provided by a single BASIC

program. This program, developed by J. Brogdon and R. J.

Hanrahan with assistance from B. Yarborough and Brent Jones,

was locally written in accordance with suggested BASIC rou-

tines provided by the DATA 6000 manufacturer.135 A complete

listing is provided in Appendix C. The BASIC source code

was compiled from the RUN menu of Microsoft Quick BASIC

version 4.0, and was executed directly from memory or from a

separate executable program written to disk.









Initially, the opening menu would offer all options

available, and upon full completion of any commands the main

menu would again be presented. Prior to data collection the

CALIBRATION command was used to set all data recording

parameters and to provide a dark or no light trace, VO, and

a full light trace, VM. The DATA command was entered during

collection, storage, and averaging of actual traces by the

DATA 6000. Upon completion of this loop three files were

stored into computer memory: all digitized voltage values

(QY(I)), a time dependent concentration file [QX(I),

CON(I)], and a time dependent optical density file [QX(I),

OD(I)]. After transfer of the data from the digitizer to

the computer, the SAVE command could be executed to save a

disk copy of the digitized voltage values. Using the PLOT-

TER command provided a graphical presentation of the digi-

tized voltage optical trace on the computer CRT screen.

Often hard copy of the graphical displays would be obtained

to catalog the data.

The subroutine at line 1570 (LEFT & RIGHT BORDERS)

allowed for selection of any portion of the trace followed

by storage of either a concentration or optical density file

corresponding to the section of the trace within the bor-

ders. The subroutine at line 3980 (LINEAR REGRESSIONS)

provided linear least squares analysis of the concentration

data to aid in determining the kinetics involved in the

transient decays. Operation of the MANUAL command enables









adjustment for the true full light signal, VM. Even though

the 100% light signal was set during the calibration steps,

any fluctuation in the light during the actual data collec-

tion mode could be accounted for by taking an average of the

light signal immediately preceding the pulse as an accurate

measure of the true 100% light intensity. Selection of the

molar absorption coefficient, E, which was dependent on the

specific transient being observed was also done through the

MANUAL command. The DIRECTORY command provided directory

inspection to insure the storage of all files to disk and to

access available memory.


2.9 Reagents and Sample Preparation


2.9.1 Sodium Tetraphenylborate and Sodium Azide


Kodak reagent-grade sodium tetraphenylborate and sodium

azide were used as received.


2.9.2 IrC163-(hydrate) and IrC162-



The sodium hexachloroiridate(III) hydrate and sodium

hexachloridate(IV) complexes, which were obtained from Al-

drich Chemical Company, were stored in a dessicator and used

without purification.


2.9.3 Sodium Carbonate


Fisher Scientific Company-supplied Na2CO3 was used in

all the carbonate competition experiments.









2.9.4 Sodium Hydroxide and Ethanol


Fisher Scientific Company-supplied NaOH and USP reagent

quality 200 proof absolute CH3CH2OH from Florida Distillers

Company were used in the hydrated electron dosimetry stud-

ies.


2.9.5 Sulfuric Acid and Ferrous Ammonium Sulfate


Fisher Scientific Company H2SO4 and Fe(NH4)2(SO4)2'6H20

were used as received for the Fricke dosimetry studies.


2.9.6 Potassium Thiocyanate


Fisher Scientific Company KSCN was used as received for

the thiocyanate dosimetry studies.


2.9.7 Tert-Butyl Alcohol


Fisher Scientific Company reagent-grade (CH3)3COH was

used as received for the hydrated electron rate-constant

studies.


2.9.8 Potassium Permanganate


Fisher Scientific Company reagent-grade KMNO4 and NaOH

were used as received for the water distillation procedure.

KMNO4 solid was dissolved in laboratory-distilled water that

was made alkaline by addition of NaOH. Upon distillation,

any organic impurities were removed by an oxidation reaction

involving the MnO4- ion.










2.9.9 Oxygen and Nitrogen


Liquid Air Corporation-supplied 02 and N2, both of

which were > 98% purity, were used as received for purging

gases in the 'Super' Fricke studies and the hydrated elec-

tron studies, respectively.


2.9.10 Nitrous Oxide


Matheson CP-grade N20 with > 99.0% purity was used as

received for generating oxidizing conditions for all studies

involving the OH' radical reactions.


2.9.11 Sample Preparation


Aqueous solutions were prepared by dissolving known

amounts of solid reagents in doubly distilled water. A

Model B5 Mettler analytical balance with 200 gram capacity

and +/- 0.05 milligram accuracy was used in all mass meas-

urements. Reference spectra of the Iridium(III) chloride

complex, Iridium(IV) chloride complex, and the Sodium Tetra-

phenylborate solution were measured using a Hewlett-Packard

model 2400 UV/VIS spectrophotometer.


2.10 Sample Irradiation


Prior to radiolysis, solutions which were to be irradi-

ated under oxidizing conditions were purged for approximate-

ly thirty minutes with nitrous oxide, N20. For work in-










volving reducing conditions, nitrogen, N2, was used as the

purge gas. Purging of the solutions was done by introducing

a disposable pipette directly into the 60 milliliter separa-

tory funnel serving as the upper reservoir of the solution

flow cell. Gas flow was maintained throughout the pulse

experiments. Prior to calibrating the DATA 6000, the solu-

tion was introduced by gravity flow into the modified cu-

vette, which was then inserted into the aluminum cell hold-

er. The cell holder was designed to accommodate the solu-

tion cell to give reproducible positioning and uniform

irradiation in the region that was sampled by the analyzing

light beam. After completing the calibration procedure, the

data collection routine was executed and the Febetron was

charged and triggered. Typically, due to product buildup or

gas bubble evolution on the inner surface of the electron

beam entrance window, a fresh aliquot was flushed into the

cell and the system was recalibrated after each pulse.














CHAPTER III
THE PULSE RADIOLYSIS OF
SODIUM TETRAPHENYLBORATE IN AQUEOUS SOLUTION

3.1 Experimental Results


3.1.1 Oxidation Intermediates of Tetraphenylborate Ions


The pulse radiolysis of aqueous sodium tetraphenylbo-

rate (TBP) solutions under oxidizing conditions was studied

with two different methods of generating the oxidizing

species. As mentioned previously, using N20-saturated

solutions the predominant oxidant produced is the OH- radi-

cal generated from the direct radiolysis of water and the

interconversion of eaq to OH. by N20. Alternatively, a

secondary oxidant, N3., is prepared under conditions of N20-

saturation and the addition of excess sodium azide, NaN3.

The azidyl radical, N3*, is formed from the oxidation of the

azide anion by the OH. radical,


OH. + N3 --> OH- + N3. III-1


Both the N3" anion and N3. radical have absorption maxima at

wavelengths < 280 nm.136 Experiments with N3. radical were

carried out to utilize the selective electron transfer path-

way of oxidation as compared to other possible reactions of

the OH- radical with aromatic systems, namely abstraction of

an H atom and addition of the OH. radical to the aromatic

ring.








The pulse radiolysis of a nitrous oxide-saturated (N20

S2.4 x 10-2 M) solution of 10 mM NaTPB was carried out at

room temperature. Using the Xenon arc lamp in the pulsing

mode, the transient absorption signals were recorded at

various wavelengths from 300 to 800 nm. Figure 20 shows the

absorption signal recorded at 330 nm for a single pulse

experiment. The appearance of an incipient secondary ab-

sorption occurring approximately 20 to 30 microseconds after

the initiating e-beam pulse was characteristic in all the

time-concentration traces recorded in the 300-400 nm range.

A transient absorption spectrum, Figure 21, was gener-

ated by plotting the maximum absorption or "end of pulse"

values as a function of the wavelength at which they were

recorded. This spectrum shows an absorption maximum at 330

nm; the only other transient spectral feature is a small

absorption (ca. 10% of the main peak) centered at about 750

nm. This spectrum is to be compared with that reported by

Liu et al. for the radical derived by OH- addition to the

phenyl groups of TPB- -- a spectrum with a large absorption

at 300 nm that was reported to change only slightly over the

first few microseconds.76

Assuming the absorption at 330 nm is caused by the

radical derived by the addition of OH* to the phenyl groups

of TPB-, its extinction coefficient at the absorption maxi-

mum of 330 nm can be calculated from the transient spectra

shown in Figure 21 (a) by making use of the value for G(OH)

in N20-saturated solutions equal to 5.4 (= G(OH) + G(eaq-).











MULT, X-AXIS BY 8.18E-83 Sec. Y-AXIS BY 8,19E+81 Units. SOURCE:TPB338.1









(a)


0.0 0.2 8.4 0.6 0.8 1.8 1.2
WOULD YOU LIKE TO LEAST SQUARES FIT DATA ON GRAPH
?l


MULT. X-AXIS BY 8.18E-83 Sec. Y-AXIS BY 8.1IE+81 Units, SOURCE:TPB345.3


(b)


8.8 8.5 1.9 1,5 2.8 2,5 3.8
WOULD YOU LIKE TO LEAST SQUARES FIT DATA ON GRAPH
?l


Fig. 20.


Graphical displays of optical signal versus time
following pulse radiolysis of N20-saturated 10 mM
NaTPB solution. a) recorded at 330 nm, 200 nsec
period, 100 usec full scale; b) recorded at 345
nm, 500 nsec period, 250 usec full scale.


0.5

0.8 *


-0.5



-1.8


0.8



-8.5



-1.8
















I co
z
C2

ci
O

p-nm
F- F-
o n
E-1-- h

EE
00
o o

* r


I I


oo uj os d d
eoueqJosqv


T1



i


I ....A


o


0
o




0
Ir



E


0)

0)








o





0
0









In N20-saturated TPB- solutions, this total OH* yield of 5.4

will have been completely converted to the TPBOH-" radical

by the time optical measurements can be made. Thus the end

of pulse optical density can be used to measure the extinc-

tion coefficient of the TPBOH-" adduct. The value obtained

from Figure 21 is approximately (10,000 +/- 10%) M-icm-1 for

the maximum peak at 330 nm.

The optical densities were calculated from the initial

pre-pulse light intensity determined during calibration, Vf,

and from the transmitted optical signal, Vt, using the

equation


OD = -log (Vt / Vf) = -log[ (QY(I) Vo) / Vf) ] III-2


Vf is obtained from subtracting the dark signal, Vo, from

the initial 100% light intensity, Vm, determined under the

experimental conditions prior to irradiation and Vt is ob-

tained from subtracting Vo from the digitized optical sig-

nal, QY(I).

The pulse radiolysis of a N20-saturated solution of 10

mM NaTPB with excess NaN3 z 0.2 M, was carried out at

various wavelengths yielding typical absorption traces, as

shown in Figure 22. The accompanying transient absorption

spectrum is plotted in Figure 21. The transient absorption

traces resulting from the NaTPB with added NaN3 conditions

also illustrate a secondary transient production. The









MOLT, X-AXIS BY 8.18E-83 Sec, Y-AXIS BY 8.16E+01 Units, SOURCE:TPBN3.13



(a)


--,.


8.8 8.2 6.4 8.6 8.8 1.8 1.2
WOULD YOU LIRE TO LEAST SQUARES FIT DATA ON GRAPH
?I


MULT. X-AXIS BY 8.18E-83 Sec, Y-AXIS BY 8.10E+01 Units. SOURCE:TPBN3.12



(b)





v---^


8.0 0.5 1.8 1.5 2.0 2.5 3.0
WOULD YOU LIKE TO LEAST SQUARES FIT DATA ON GRAPH
? I


Fig. 22.


Graphical display of optical signal versus time
following pulse radiolysis of N20-saturated 10 mM
NaTPB, 0.2 M NaN3 solution. a) recorded at 330
nm, 200 nsec period, 100 usec full scale; b)
recorded at 330 nm, 500 nsec period, 250 usec full
scale.


-0.4


-8.6


-8,8


-1.2


-1.2


-0.4


-0,6


-0,8


-1.,


-1.2








transient absorption spectrum contains two absorption bands,

one at 330 nm and a broad band above 700 nm. This transient

absorption spectrum as well as the associated kinetics of

the 330 nm decay are in good agreement with published re-

sults obtained under similar solution conditions.75'76


3.1.2 Transient Kinetics


Kinetic analysis of the optical traces was carried out

using a curve fitting routine from the BASIC program, and

the best fit was judged from the correlation coefficient and

visual inspection. Figures 23 and 24 show typical curve

fits for both the initial and secondary transients produced

under N20-saturated millimolar NaTPB conditions. Analogous

curve fitting was carried out on the experimental absorption

traces obtained from N20-saturated solutions of NaTPB con-

taining excess NaN3. The resulting decay rate constants are

presented in Table 2.


3.1.3 Carbonate Competition Method


The reaction of OH. radicals with the TPB- anion occurs

too rapidly to be observed directly using the experimental

conditions previously described. However, the formation

rate of the OH. radical reaction with TPB~ can be obtained

by the carbonate competition method137 using a secondary

scavenger, CO32-, which competes with the TPB~ anion for the

OH. radical. The two competing reactions are









MULT. X-AXIS BY 8.18E-83 Sec. Y-AXIS BY 8.19E+81 Units. SOURCE:TPB338.1

\ (a)


8.0
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TO LEAST SQUARES


2.4 MULT. X-AXIS
[ K= 69382.1
2.4


BY 0.10E-84


0.6
FIT DATA OH GRAPH


Sec. Y-AXIS BY 8.18E+82 Units. SOURCE:TPB338.1
ln(C):ln(Co)-*t


2.4 1


2.9 2.5 3.0 3.5 4.0
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? I


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INTCPT: 2.16E+01 (STD DEV= 1.27E-02) SLOPE: 6.94E+04 (STD
R= .9983794 E= 18800 STD DEU PTS= 2.820695E-92


DEU= 4.26E+02)


Fig. 23. Curve fit of data; a) transient trace presented
from Figure 20 (a); b) First-order fitting routine
applied to data between x = 20 and x = 40 micro-
seconds.


9,5



8.8



-8.5



-1.8


I I I '









Y-AXIS BY 8.18E+81 Units. SOURCE:TPB345.3


(a


2.0


E= 3.6322


G IL +


2.5


3.0


(1/C)=(lfCo)+X*t


o. (b)
(b)


0.5 1.8 1.5 2.0 2.5
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INTCPT=-5.18E+03 (STD DEV= 4.49E+82) SLOPE= 3.63E+88 (STD DEV= 2,66E+06)
R= .9912943 E= 3800 STD DEV PTS: 2388.339


Fig. 24.


Curve fit of data; a) transient trace presented
from Figure 20 (b); b) Second-order fitting rou-
tine applied to data between x = 80 and x = 250
microseconds.


8.5



80.



-0,5



-1.8


8,0

7.0

6.0

5,0

4.0

3.8


1


MULT, X-AXIS BY 0.18E-03 Sec.















Table 2

Transient Decay Rate Constants


N20-saturated Initial Transient Secondary Transient

Solutions Decay Rate Constant Decay Rate Constant

( x 104 sec-1 ) ( x 108 Msec )


10 mM NaTPB 5.88 0.98 3.76 0.42


10 mM NaTPB 8.25 0.59 3.10 0.91
0.2 M NaN3
a) 2 a) 4

b) 3.9 0.2 b) -


a) reported by Horii and Taniguchi

b) reported by Liu et al.








OH- + TPB ---> products k III1-3

OH- + C032- --> OH + CO3 (detected) k2 130


Using the He-Ne laser experimental setup, the CO3- radical

anion was monitored as a function of added TPB- anion. The

CO3- radical anion has an extinction coefficient on the

order of 1000 M-1 cm-1, a known formation rate constant of

4.1 x 108 M-1 -1, and a broad absorption band centered on

600-610 nm.138 The equation representing the competition is


k2[C032-]
[C03 ]inf. = x [OH.]o III-4
k2[CO32-] + kl[TPB-]


with [C03-]inf. = end of pulse concentration of C03- ion

[OH.]o = initial concentration of OH- (includes

primary OH' from water radiolysis and

from interconversion of eaq- by N20)


Taking [OH.]o as equivalent to the [C03-]inf. generated with

no TPB- present, or [C03-]o, equation III-4 can be rear-

ranged to


[C03-]o kI[TPB-]
= 1 + III-5
[C03 ]inf. k2[CO32-]

From a plot of [CO03-o / [CO3-]inf. versus [TPB-] / [C032-],

as shown in Figure 25, kl/k2 is found to be 15. Substitu-

tion of k2, the C03- reference formation rate constant gives

a rate constant for the formation (reaction III-3 above) of

the initial transient = (6.2 0.6) x 109 M'-sec-1.




























/
/
/


/
/
/
/


0.05


0.15


0.2


0.25


(TPB ) / (CO3 )





Carbonate competition experiment for determining
the OH + TPB- rate constant.


4.5



4



3.5


**-


O



0
0
.0-,%,

0


1.5



1



0.5


Fig. 25.


i I i i I i








Radical formation rate constants for TPB' equal to 1.4 x 109

M-1s-1 and 7.1 x 108 M-1 s-1 have been reported for the

electron transfer reaction involving TPB- and N3..75,76


3.1.4 Reduction Intermediates of Tetraphenylborate Ions


Pulse radiolysis experiments were performed using

reducing conditions to examine the possibility of a rapid

reaction between the TPB~ ion and eaq. Because the TPB~

anion is a strong reducing agent and negatively charged,

this reaction was presumed unlikely. However, by monitoring

the eaq- transient signal as a function of added TPB~ any

such reaction would be evinced by either a decrease in the

magnitude of the end of pulse eaq- transient absorption or a

change in the eaq- transient decay kinetics. A typical

transient trace of the pulse experiments conducted on ap-

proximately 10 mM NaTPB solutions under reducing conditions

is shown in Figure 26. The life-time of the eaq transient

was found to be approximately 8-10 microseconds with a best

fit analysis giving a second order decay rate constant of

5.7 x 1010 M-s-1.


3.1.5 Computer Simulation


Modeling calculations were utilized to help establish

the detailed chemical mechanism of multi-step reactions

found in aqueous pulse radiolysis systems. Differential

rate equations for the suspected reaction sequence are










-9.5 MULT. X-AXIS BY 8.18E-04 Sec. Y-AXIS BY 9.18E+91 Units. SOURCE:TPBEAQ38

-1.8
(a)
-1.5 .

-2.9

-2,5

-3.8

-3.5

8.0 8.2 9.4 8.6 0.8 1.8 1.2
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? I

MULT. X-AXIS BY 8.19E-85 Sec. Y-AXIS BY 8.19E+06 Units. SOURCE:TPBEAQ38
3.5 (1/C):(1/Co)+K*t
-K 5.736563E+10
3.

2.5 ... --


2.9

1.5 .(b)

1.8


2.8 3.8 4.8 5.8 6.0 7.8
MOULD YOU LIKE TO LEAST SQUARES FIT DATA ON GRAPH
?1
WOULD YOU LIKE TO LEAST SQUARES FIT DATA ON GRAPH
INTCPT=-8.54E+04 (STD DEV= 2.85E+03) SLOPE= 5.74E+10 (STD DEV: 5,63E+08)
R= .9901459 E- 14860 STD DEU PTS: 9860.368



Fig. 26. a) Graphical display of optical signal versus time
following pulse radiolysis of an N2-saturated 10
mM NaTPB, 0.04 M t-butanol solution; 20 nsec
period, 10 usec full scale; b) Curve fit of data
between x = 3 and x = 7 microseconds.








integrated to give computer-simulated time-dependent concen-

tration profiles that are compared with those measured

experimentally. These comparisons help to establish, or

validate, proposed mechanisms. The computer modeling was

done using a Gear integrator program.139 This program,

written by R. L. Brown140 of NIST, was modified in this

laboratory to run under Microsoft FORTRAN 77 on an MS-DOS-

based microcomputer.

The input parameters to the program consist of a list-

ing of all mechanistic steps and their rate constants (see

Appendix B), the identification of all reactants with their

initial concentrations, and the time-step which controls the

50 computation intervals.


3.2 Discussion


3.2.1 Electron Transfer


The oxidation intermediates of TPB- ions in aqueous

solutions have been examined by Horii and Taniguchi,75 and

Liu et al..76 From their results with N20-saturated solu-

tions of NaTPB and NaN3, the proposed route to the formation

of several major products is a rapid electron transfer from

B(C6H5)4 to N3 yielding the B(C6H5)4 radical and N3", or


B(C6H5)4- + N3' ----> B(C6H5)4' + N3 III1-6


As shown earlier the azidyl radical, N3', is produced ini-

tially from primary OH radical reaction with N3-, reaction









III-1. The transient absorbing at 330 nm and 800 nm (Figure

21) is attributed to the B(C6H5)4' radical. Both peaks

decay with the same first-order rate constant, indicating

that they represent different absorbances of the same tran-

sient species.76 Loss of the 330 nm peak is attributed to a

rapid self-decomposition first-order decay, producing a

second transient that undergoes a relatively slower decay.

Horii and Taniguchi proposed the reaction,75


B(C6H5)4' ----> B(C6H5)2' + (C6H5)2 III-7

The secondarily-produced transient B(C6H5)2* was suggested

to disappear following second-order kinetics, although no

product species were discussed.75

The pulse results from our oxidation experiments on TPB

solutions containing no added N3- anion could be interpreted

as above, i.e. a rapid electron transfer from B(C6H5)4- to

OH', instead of N3*, or


B(C6H5)4- + OH' ----> B(C6H5)4' + OH- III-8

yielding the B(C6H5)4' radical. As shown in Table 2, the

decay kinetics of the transients produced with and without

added N3- are similar, that is a rapid, first-order decay

followed by a secondary transient decay. However, compari-

son of the transient spectra, Figure 21, suggests that two

different transients are formed. With added azide, the

transient spectral feature at 750 800 nm is about 70% of









the magnitude of the main peak centered at 330 nm. With no

added azide, the transient spectral feature at 750 800 nm

is < 10% of the magnitude of the main peak centered at 330

nm.


3.2.2 OH Addition


An alternate mechanism to the electron transfer from

TPB~ to OH', as described above, is the addition of the OH*

radical to the aromatic ring, which would lead to an OH*

adduct transient species different from the TPB- radical, or


B(C6H5)4" + OH' ----> (C6H5)3BC6H50H" 301


The following self-decomposition first-order decay

scheme has been considered for the observed loss of this OH'

addition adduct.


(C6H5)3BC6H50H- ----> B(C6H5)3 + C6H50H'- 302

C6H50H'- + H20 ----> C6H60H' + OH- 303


Triphenylborate and its hydrolysis products, (C6H5)B(OH)2

and (C6H5)2BOH, all have absorptions at wavelengths below

300 nm.74 The secondarily-produced transient C6H50H'-, is

suggested to undergo a rapid hydrolysis, yielding the hy-

droxycyclohexadienyl radical C6H60H.. The hydrolysis of

C6H5OH-" has been reported in a previous aqueous phenol

pulse radiolysis study.141 In neutral solutions a slow

reaction between the solvated electron, eaq-, and phenol








that forms C6H5OH-' was reported. The radical anion,

C6H5OH-', subsequently undergoes rapid protonation by H20 to

yield (C6H5)(OH)H'. This species is a structural isomer of

the hydroxycyclohexadienyl radical, C6H6OH*. A molar ex-

tinction coefficient of (3800 +/- 800) M-1 cm-1 at a wave-

length maximum of 330 nm was assigned to the (C6H5)(OH)H'

radical.

Another possible competing reaction pathway for the

C6H50H'- radical anion would be a bimolecular radical anion

reaction. The bimolecular disappearance of negatively

charged radical species has been previously suggested in

pulse radiolysis studies involving the reaction of the

hydrated electron, eaq-, with benzene.58 In this aqueous

benzene study, C6H6-, the addition product of eaq- and

benzene, was reported to decay via a rapid bimolecular proc-

ess before protonation in solutions of pH neutral to 13.


C6H6 + eaq ----> C6H6 III-9

C6H6g + C6H6" ----> products III-10


No specific products of the radical anion reaction, III-10,

were discussed.

In the present study, concerning the combination reac-

tion of C6H50H'-, a possible reaction forming a charged

dimer species, with subsequent formation of biphenyl and

hydroxide ion, is proposed below


C6H50H'- + C6H5OH'- ----> [HO(C6H5)-(C6H5)OH]2- 304

[HO(C6H5)-(C6H5)OH]2- ----> C6H5-C6H5 + 2 OH- 305








The scheme involving radical combination leading to an

intermediate dimer is prominent in the mechanism involving

the radiolysis of aqueous benzene, discussed below.

The hydroxycyclohexadienyl radical, C6H60H', mentioned

above (reaction 303), is an important intermediate in the

formation of major products in the radiolysis of aqueous

benzene solutions; the results of which are in good agree-

ment with the end products derived from Co-60 steady-state

r-radiolysis of NaTPB solutions carried out in this lab.86

The proposed mechanism concerning the benzene

oxidation55'64'65 is described as


C6H6 + OH' ----> C6H6OH' III-9

2 C6H60H' ----> [HO(C6H6)-(C6H6)OH] 306

[HO(C6H6)-(C6H6)OH] ----> C6H5-C6H5 + 2H20 307

2 C6H60H' ----> C6H6 + C6H5OH + H20 308


The hydroxycyclohexadienyl radical, C6H6gH*, has a reported

absorption maxima at 313 nm.58 The combined bimolecular

rate constant for its disappearance via reactions 306 and

308 has been determined to be (7.05 0.35) x 108 M-is-1.58

The disproportionation to combination ratio for the disap-

pearance of C6H6OH" was found to be < 0.4, indicating that

the combination reaction 306 is predominant.63 The major

products produced are biphenyl, benzene and phenol. In the

Co-60 r-radiolysis of aerated 0.05 M sodium tetraphenylbo-

rate solutions the products and their G-values were found to

be biphenyl, 1.9; benzene, 1.3; and phenol, 0.41.68








It is also reasonable to expect the H. atom to add to TPB-

ion, giving a transient species that decomposes via a two-

step process giving the cyclohexadienyl radical


B(C6H5)4- + H. ----> (C6H5)3BC6H6* 309

(C6H5)3BC6H6 ----> B(C6H5)3 + C6H67 310

C6H67 + H20 ----> C6H7' + OH- 311


The (C6H5)3BC6H67 transient has been proposed by Liu et al.

as the weakly absorbing species at higher wavelengths

(Figure 21) in the pulse radiolysis of TPB- solutions with-

out added azide.76 The cyclohexadienyl radical could also

react with the hydroxycyclohexadienyl radical in a bimolecu-

lar process producing benzene56


C6H7* + C6H60H' ----> 2 C6H6 + H20 312


Concerning the reduction of TPB-, a rapid reaction

between eaq- and TPB~ appears to be negligible from the

results of the NaTPB pulse radiolysis under reducing condi-

tions. Comparison of Figure 26 with eaq- traces found in

the hydrated electron dosimetry experiments, Appendix A,

shows little difference in either the magnitude or kinetic

behavior of the eaq- transient signal. The eaq- transient

signal decayed with a second order rate constant of 5.7 x

1010 M-1s-1 with added TPB~; for the eaq- dosimetry experi-

ments, the eaq- signal exhibited a second-order decay = 4.4

x 1010 M-s1-1.









3.2.3 Computer Simulations


Computer simulations were carried out with a Gear

integrator utilizing the data set consisting of the elemen-

tary reaction steps describing the transients of irradiated

pure water (Appendix B). The mechanistic scheme also in-

cludes reactions of eaq- with N20, and OH* with TPB-.

Figure 27 illustrates typical results of the simulated

calculations for conditions involving N20-saturated solu-

tions containing 10 mM TPB-. Time-concentration profiles

for all species in the system are predicted over the ca. 200

microsecond data collection time period. Experimental data

points indicate the observed decay of the transient trace

produced in a typical experimental run, recorded at 330 nm

(Figure 20 (b)). These experimental data points represent

the combined absorbance of all the components in the system

contributing to the absorption trace at 330 nm. Dotted

lines show predicted yields of the various individual tran-

sients formed. The solid line represents the combined

concentrations of the following intermediates; the initial

OH* adduct (C6H5)3BC6H5OH' with a molar extinction coefi-

cient of 10,000 M-1 cm-1, the radical anion C6H5OH" and the

hydroxycyclohexadienyl radical C6H60H' with molar extinction

coefficients of 3800 M-1cm-1, and the intermediate dimers,

[HO(C6H6)-(C6H6)OH] and [HO(C6H5)-(C6H5)OH]2- with molar

extinction coeffiecients of 7,500 M-cm-1.




Full Text

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XQLYHUVLW\ RI )ORULGD 0O LQ PX PX DL DQ U .8$ R D QR LS ‘L


THE PULSE RADIOLYSIS OF SODIUM TETRAPHENYLBORATE AND
SODIUM HEXACHLOROIRIDATE IN AQUEOUS SOLUTION
BY
CHARLES L. CRAWFORD
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
1991

Dedicated to
my parents, Nathan and Doris

ACKNOWLEDGMENTS
The author expresses his sincere appreciation to his
research director, Prof. Robert J. Hanrahan, and to Prof. M.
Luis Muga for their advice, encouragement, and friendship
throughout this work.
Special thanks are given to Avinash Gupta and Zuogian
Li for their friendship and assistance.
Appreciation is given to Ravi Bhave for his efforts in
initiating the experimental setup. Mohammad Gholami and
Sandra Roberts are also acknowledged for their contributions
towards much of the data collection.
Thanks to Prof. D. N. Silverman of the J. Hillis Miller
Health Science Center for the use of the stopped-flow appa¬
ratus. Experimental assistance with this instrument, pro¬
vided by Dr. Chingkuan Tu, is also gratefully acknowledged.
The author's deepest thanks are expressed to Kama
Siegel for her unprecedented companionship and editorial
prowess — both of which have helped make this work possi¬
ble.
Thanks to Dave Burnsed for his assistance with the
electronics.
iii

TABLE OF CONTENTS
page
ACKNOWLEDGEMENTS iii
LIST OF TABLES vi
LIST OF FIGURES VÜ
ABSTRACT X
1. INTRODUCTION 1
1.1 Foreword 1
1.2 Review of Previous Work 3
2. EXPERIMENTAL APPARATUS AND PROCEDURES 19
2.1 Pulse Radiolysis Setup 19
2.2 Absorption Spectrophotometry 22
2.3 Light Source Systems 30
2.4 Reaction Cells and Cellholder 37
2.5 Monochromators 47
2.6 Febetron 706 System 50
2.7 Transient Recorder and Computer System ... 59
2.8 Computer Program 63
2.9 Reagents and Their Purification 65
2.10 Sample Irradiation 67
3. PULSE RADIOLYSIS OF SODIUM TETRAPHENYLBORATE
IN AQUEOUS SOLUTION 69
3.1 Experimental Results 69
3.2 Discussion 83
3.3 Conclusions 91
4. PULSE RADIOLYSIS OF SODIUM HEXACHLOROIRIDATE
IN AQUEOUS SOLUTION 93
4.1 Experimental Results 93
4.2 Discussion 101
4.3 Conclusions 114
iv

page
APPENDIX A CHEMICAL DOSIMETRY FOR A PULSED
RADIATION SOURCE 118
APPENDIX B RELEVANT REACTION SYSTEMS 128
APPENDIX C INPUT DATA FILES FOR COMPUTER
INTEGRATION SIMULATIONS 132
APPENDIX D PULSE RADIOLYSIS COMPUTER PROGRAM ... 138
REFERENCES 155
BIOGRAPHICAL SKETCH 169
v

LIST OF TABLES
Table Page
1 Radiation Chemical Yields for Water 9
2 Transient Decay Rate Constants 78
3 Physical Constants for Chemical Dosimetry
Systems 120
4 Absorbed Dose for Chemical Dosimetry Systems .. 127
5 Chemical Reaction Systems for Computer
Simulation Studies 129
vi

LIST OF FIGURES
Figure Page
1 Scheme for the radiolysis of water 8
2 University of Florida pulse radiolysis system . 21
3 Experimental arrangement using the McPherson
218 monochromator 26
4 Experimental arrangement using the Jarrell-Ash
monochromator 27
5 Photomultiplier tube-base schematic used with
the EMI 9250 QB PMT in the model 3262 housing . 29
6 Lead shields for PMT photocathodes in the
Pacific Precision Instruments PMT housings .... 31
7 Photomultiplier tube-base schematic used with
the Hamamatsu R928 side window PMT and Model
3150 housing 32
8 Xenon-arc lamp spectrum 34
9 Xenon-arc lamp schematic diagram 35
10 Flow-reaction cell with modified UV-VIS
cuvette 39
11 Non-flow-reaction cell from UV-VIS cuvette .... 41
12 Reaction cellholder with adjustable razor
blades mounts and wire-mesh screens 42
13 Depth-dose curves for microscope coverslide
experiment 45
14 Absorbance change with number of pulses
delivered for microscope coverslide experiment 46
15 Entrance and exit slit system flange adaption
to the Jarrell-Ash monochromator 51
vii

Figure Page
16 Febetron 706 system schematic 53
17 Refurbished electron beam tube with ion pump .. 56
18 Total beam calorimetric dosimetry arrangement . 58
19 Timing sequence for pulse radiolysis experiment 62
20 Graphical display of optical signal versus time
following pulse radiolysis of a N20-saturated
solution containing 10 mM NaTPB 71
21 Transient absorption spectrum 72
22 Graphical display of optical signal versus time
following pulse radiolysis of a N20-saturated
NaTPB and NaN3 solution 74
23 Curve fit of data from Fig. 20 (a) 76
24 Curve fit of data from Fig. 20 (b) 77
25 Carbonate competition experiment for determining
the OH + TPB- rate constant 80
26 Graphical display of optical signal versus time
following pulse radiolysis of a N2-saturated
solution containg NaTPB and t-butanol 82
27 Comparison of experimental and computer
simulated concentration versus time plots 90
28 UV-VIS spectrum 94
29 Carbonate competition experiment for determining
the OH + Ir(III) rate constant 96
30 Transient digitizer traces of Ir(IV) absorption
recorded at 488 nm with N20-saturation 98
31 Transient digitizer traces of Ir(IV) absorption
recorded at 488 nm with N2 and air saturation . 100
32 Change in first order decay of hydrated electron
with Ir(III) concentration 102
33 Comparison of experimental and computer
simulated Ir(IV) concentration verses
time plots; N20, alkaline 109
viii

Figure Page
34 Comparison of experimental and computer
simulated Ir(IV) concentration verses
time plots; nitrogen-saturated Ill
35 Comparison of experimental and computer
simulated Ir(IV) concentration verses
time plots; aerated 112
36 Computer simulations of the transient
Ir(IV) trace 113
37 Change in absorbance with accumulated
irradiation pulses for the modified
Fricke system 124
38 Thiocyanate dosimetry 125
39 Hydrated electron dosimetry 126
ix

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
THE PULSE RADIOLYSIS OF SODIUM TETRAPHENYLBORATE AND
SODIUM HEXACHLOROIRIDATE IN AQUEOUS SOLUTION
By
Charles L. Crawford
December, 1991
Chairman: Dr. R. J. Hanrahan
Major Department: Chemistry
A pulse radiolysis facility for the study of fast
chemical kinetics in aqueous solution, based on a Febetron
706 electron beam accelerator, has been established at the
University of Florida Radiation Chemistry Laboratory.
In previous work on the radiolysis of tetraphenylborate
(TPB)'solutions carried out in this laboratory, it was found
that several organic products, including benzene, phenol,
and biphenyl, are produced with substantial yield. However,
the reaction mechanism has not been determined. Since the
tetraphenylborate anion, TPB-, is a reducing species, it
should be more readily subject to attack by OH* than by eag“
or by H*. The lack of reactivity between TPB and eaq- has
been confirmed by directly monitoring the transient signal
due to eaq“. Concerning the reaction with OH*, two schemes
were investigated: (1) a rapid electron transfer from
x

B(C6H5)4~ to OH»; (2) OH* addition to B(C6H5)4“. Comparison
of transient absorption spectra resulting from the two
different schemes above suggests that the OH* addition is
the dominant reaction under conditions of N20 saturation,
with an experimentally determined second-order rate constant
of 6.2 x 109 M-1s-1. A mechanism based on an initial first-
order self-decomposition of the OH' adduct, (C6H5)3BC6H5OHT,
is proposed.
Reactions initiated by OH* radicals or eag~ in aqueous
IrCl63- solutions were studied. The rate constant for the
respective reactions were found to be 4.9 x 10^ M xs and
6.1 x 109 M-1s-1. The oxidation product, IrCl62- disappears
rapidly in N20-saturated basic solution or in either neutral
N2-saturated or aerated solution, but is nearly inert in
neutral solution with N20 present. The complex IrCl62-
reacts rapidly with hydrogen peroxide in basic media, as
confirmed on the benchtop and by stopped-flow kinetics. It
is therefore inferred that reaction with H02“ may account
for the loss of IrCl62- under basic conditions. Loss of
Ir(IV) in neutral N2~saturated solution without added N20
may involve electron transfer from Ir(II), and loss of
Ir(IV) in aerated solution is attributed to reduction by
superoxide ion, 02“.
Kinetic modeling on the respective mechanistic schemes
of the above systems gives good agreement with our experi¬
mental results.
xi

CHAPTER I
INTRODUCTION
1.1 Foreword
The pulse radiolysis technique offers a convenient way
of generating a variety of unstable or transient species
under well-defined conditions. This technique involves the
initiation of a chemical reaction process via a short pulse
of ionizing radiation. Of major interest is the kinetics
of, as well as both the qualitative and quantitative meas¬
urement of these transient species involved in the fast
elementary steps of the reaction process.
The modification of a gas-phase pulse radiolysis system
to a liquid-phase pulse radiolysis system was undertaken to
expand the chemical kinetics facility of the University of
Florida Radiation Chemistry Laboratory. Efforts to obtain
kinetic information related to various aqueous solution
systems were made in order to supplement existing aqueous-
solution-based studies carried out in this laboratory in¬
volving techniques such as steady-state Co-60 7-radiolysis
and solar-assisted photoelectrochemistry.
To study fast chemical reaction systems, two necessary
requirements are the initiation of the process on a time-
scale that is shorter than or comparable to the process
being observed, and the detection of a physicochemical
1

2
change associated with the process. Our liquid-phase pulse
radiolysis system was developed around a Febetron 706 elec¬
tron beam (e-beam) accelerator capable of delivering a
short, 3 nanosecond full width at half-max (FWHM) pulse of
600 KeV electrons with a peak current of 8 x 103 amps. The
monitoring technique employed was time-resolved absorption
spectroscopy.
A microcomputer-based data acquisition system was
integrated into the pulse radiolysis system to acquire,
analyze, and store data obtained from the study of fast
chemical processes.
The kinetic studies involving aqueous solutions of
sodium tetraphenylborate (NaTPB) were undertaken to aid in
developing a plausible mechanism concerning the radiolytic
degradation of the TPB- ion. Examination of the iridium
chloride system was carried out to expand the solution
conditions under which this system had been previously
studied by pulse radiolysis. Due to the similarities of
flash photolysis and pulse radiolysis, specifically in the
case of radiation-induced redox reactions, previous photoly¬
sis work on the iridium chlorides served as a reference to
the pulse radiolysis data collected in this study.
Various chemical dosimeter methods applicable to pulsed
electron sources were studied to establish the proper dose
delivered to the liquid sample in the Febetron 706 system,
as modified for liquid-phase work.

3
1.2 Review of Previous Work
1.2.1 Pulse Radiolysis
At the University of Florida Radiation Chemistry Labo¬
ratory, Febetron 706 studies have been completed on the gas
phase reaction kinetics and mechanisms of various chemical
systems such as the alkyl and perfluoroalkyl iodides,1
oxygen/ozone,2 and OH reaction dynamics with small mole¬
cules.3-5 The identity and reactivity of important tran¬
sient species generated in the pulse radiolysis of gaseous
systems, at atmospheric pressures or less, was of previous
interest in these studies.
Historically, pulse radiolysis was developed to eluci¬
date postulated transient behavior in radiation-induced
chemical reaction systems, and apparatus was first brought
into operation in about I960.6'7 Early pulse radiolysis
systems used visible absorption spectroscopy to monitor
intermediates produced from intense single electron acceler¬
ator pulses lasting typically around one microsecond or
less, and much of the developmental work on pulse radiolysis
involved liquid phase systems.8-10 Development of the pulse
radiolysis technique has since brought about variations of
the method to include stroboscopic techniques capable of
picosecond resolution11 and multiple time-resolved observa¬
tion techniques such as electron spin resonance (ESR),12-14

4
conductivity,15-17 emission spectroscopy,18 and resonance
Raman spectroscopy,19-21 to monitor reaction intermediates.
The pulse radiolysis method is the radiation chemistry
analog of flash photolysis, in that the photoflash and
photodissociation of molecules is replaced by a short, high-
energy pulse of electrons, causing excitation and ionization
of molecules by electron impact.22 The technique of pulse
radiolysis, used to study fast reactions, has been applied
in areas of aqueous inorganic, organic, and biochemistry.
Other fast reaction techniques such as flash photolysis,
stopped-flow techniques, and temperature jump or pressure
jump relaxation methods have been designed to monitor con¬
centrations and to measure rate coefficients.23 However,
the pulse radiolysis technique was the first method capable
of studying processes occurring at or below 10-9 seconds.24
The characteristics of the electron pulse used in
electron beam pulse radiolysis are its time profile, peak
current and energy, cross-sectional homogeneity, and diver¬
gence. For adequate time resolution of the observed tran¬
sient signal, the time profile of the pulse should be very
short compared to the relaxation of the intermediates. The
pulse current determines the number of interactions between
the chemical system and the e-beam which, in turn, deter¬
mines the concentration or amount of species formed. The
maximum electron energy determines the penetration depth of
the e-beam into the reaction cell and should be high enough
to adequately irradiate the volume of the chemical system

5
being monitored. The cross-sectional homogeneity and diver¬
gence of the beam determine how uniformly irradiated the
optically-sampled reaction region is.
Transformations over the years of the standard pulse
radiolysis installation have led to increasingly sophisti¬
cated experimental setups.25-28 Spectrographic methods
involving oscilloscopes and Polaroid cameras have been
largely replaced by digital signal processors, or transient
digitizers that have an interface for computer control.11
Signal processing has been aided by the use of backing-off
circuits which can measure small transients on top of the
analyzing light.29 Lasers and the capability of commercial
xenon-arc lamps to supply pulse current on top of DC current
• • o n o o
have provided intense analyzing light sources. u Lastly,
on-line computer systems have been developed which not only
greatly reduce the time required for data analysis but also
improve both quantity and quality of the data
processed.29'33-35
1.2.2 Radiolvsis of Water and Aqueous Solutions
Early investigations on the radiolysis of water have
played a significant role in the development of radiation
chemistry.36-39 In addition, sophisticated pulse radiolysis
techniques achieving the time resolution of radiation in¬
duced chemical events have been applied more often in the
radiolysis of water than in any other liquid.40
As a

6
result, most of the aspects of the radiation chemistry of
water and aqueous solutions are now reasonably well under¬
stood.
A few practical purposes for water irradiation studies
arise from 1) the importance of understanding the effect of
radiation on biological systems in which water is the main
substrate, and 2) various aspects of nuclear reactor tech¬
nology concerning water's use as both a coolant and modera¬
tor.41'42 Water and aqueous solutions have been studied, in
particular, for three reasons: (1) their role as solvents is
central to chemistry in general and to radiochemistry in
particular; (2) they are readily available and easy to work
with; (3) water is a polar liquid that responds in charac¬
teristic ways to radiation.
Important features of the radiation chemistry of water
are: (1) a description of the primary radical and molecular
products and how they evolve in both time and space; (2) the
effect of pH on the radiation chemical yields of primary
products; (3) the track structure and related phenomena
associated with the passage of a charged particle through a
liquid; and (4) a detailed account of all the radical reac¬
tions involving the primary radicals and radiolysis
products.43
Upon initial ionization of a water molecule by a fast
primary charged particle such as an electron, the liberated
electron from the ionization event will typically have
sufficient energy to further ionize several adjacent water

7
molecules, which leads to the creation of clusters of ions
along the track of the ionizing particle. These clusters
are called spurs; detailed descriptions of their structure
and distribution along the particle tracks can be found in
the literature.44 Once the dry electrons have been slowed
to thermal energy, they undergo a hydration (or solvation)
process which involves the water molecules becoming oriented
about the charged species. This process occurs on the order
of 10-11 seconds, which is the relaxation time for dipoles
in water. Alternatively, some water molecules are excited
to upper electronic states from which they can autoionize,
dissociate, or fall back to the ground electronic state.
Figure 1 from Buxton43 shows the time scale of events initi¬
ated by the absorption of energy by water from an incident
ionizing radiation, such as an energetic photon or charged
particle. Also shown are the various routes to formation of
the primary radical and molecular products.
At approximately 10-10 seconds after the ionizing
event, all the physicochemical processes are complete and
the chemical stage begins. Initially, this process involves
diffusion of the radiolysis products out of the spurs where
they either react together to form molecular and secondary
radical products, or they escape to the bulk solution,
becoming homogeneously distributed. Appendix B lists the
elementary reaction steps in the radiolysis of liguid water,
along with their appropriate rate constants.

Event
HpO
%
%
Time scale (sec)
h2o
H20+ + e
r i
H + OH H2+0
OH + H30 +
>
s
10
-16
10
-14
10
-13
aq
* molecular products form in the spurs
* diffusion of radicals out of the spurs
aq
t
, H, OH , H2 , H202 , H30 +
10
-7
Note: /w
, upon interaction with ionizing radiation
e , the electron in a presolvated, or "dry" state
e , hydrated electron
aq
Fig. 1
Scheme for the radiolysis of water.

9
At approximately 10~7 seconds, the spur expansion is
complete, resulting in the so-called "primary yield" of the
radiolysis products eag~, H30+, OH, H, H2, H202, and H02.
Radiation chemical yields are expressed as G-values, as
shown in Table l,38 where G is the number of species (repre¬
sented by X) created or destroyed per 100 eV of absorbed
dose, and are written as G(X).
Table 1
Radical and Molecular Product Yields in Irradiated Water
Primary yield eag H+ OH H H2 H202 H02
G( molecules ^ 2.63 2.63 2.72 .55 .45 .68 0.026
100 eV
The yields are essentially independent of pH except for
extreme acidic conditions (pH < 3). The G-values are also
dependent on the quality of the ionizing radiation, or the
mean linear energy transfer (LET). Under extremely intense
irradiations, at dose rates so high that the spurs overlap,
yields may also depend on the dose rate.40 In the case of
high-LET radiation45 such as a particles, heavy ions or
. . . Q
fission fragments, or very high dose rates ( > 1CK
rad/sec),46-49 lower radical and larger molecular yields
result.
In the radiolysis of dilute solutions, most of the
energy is absorbed by the solvent, and effects due to energy

10
deposited directly in the solute are unimportant for solute
concentrations less than about 0.01 M. Thus all the ob¬
served chemical changes in irradiated dilute aqueous solu¬
tions are brought about indirectly by the molecular and
radical products of the water radiolysis; this phenomenon is
referred to as the "indirect effect."40 In the presence of
a solute, transient species and final products result from
attack of H, eaq~, OH, and H202 on the added substrate.
Radicals derived from the substrate may also react to form
final products. As evinced by the G-values of the primary
radicals, the radiolysis of water produces approximately
equal numbers of powerful oxidizing and reducing radicals.
The standard reduction potentials for the hydroxyl radical,
OH, and the hydrated electron, eaq“, are 2.72 V and -2.9 V,
respectively.40
For pulse radiolysis chemical applications, well-de¬
fined conditions, i.e. either totally oxidizing or totally
reducing, are desirable, and these conditions can be
achieved by interconversion of the primary radicals.50
Briefly, for a convenient way of obtaining almost totally
t • • • . — 9
oxidizing conditions, N20-saturated (N20 = 2.5 x 10 ¿ M)
solutions are used. N20 converts eaq“ to OH, or
eaq“ + N20 > N2 + O" > OH + OH" 129
Acidic conditions of pH < 3 should be avoided due to the
interconversion of eaq~ to the hydrogen atom, which is a
major reducing species in acidic media,
eaq~ + H+ > H 103

11
For the creation of almost totally reducing conditions,
addition of an organic solute to an inert gas-saturated
solution leaves eag~ as the predominant reducing primary
species. Reactions involved are
OH + ROH > R(CH-)OH + h20 1-1
H + ROH > R(CH* )OH + H2 1-2
In general, the organic radicals formed, R(CH*)OH , are less
powerful reductants than eag- and are rather unreactive. In
particular, N2-saturated solutions with added tertiary
butanol were used in our work.
1.2.3 Aqueous Solution Studies of Aromatic Systems
In aqueous systems containing organic solutes, reac¬
tions occurring between solute and the primary products of
water radiolysis are predominately abstraction, addition,
and one-electron reduction. Organic radicals produced by
these processes can further react before being converted to
stable products, thus leading to complex radiolysis mecha¬
nisms, which have been reviewed.51-53
Mechanisms can be somewhat generalized within families
of organic compounds containing the same functional group
due to the tendency of the primary products, eag-, H and OH,
to react with these functional groups as opposed to the
molecule as a whole.40 Particularly, benzene can be uti¬
lized as an analogous system for many aromatic compounds,

12
with addition to the unsaturated bonds being the character¬
istic reaction path. Reaction of the primary radicals from
water radiolysis with aromatic systems exhibit rate con¬
stants in the range of 105 to 107 M-1s-1 for eaq-, and > 109
M-1s-1 for H and OH.40
C6H6 + eaq~ > C6H6- (+ H20) > C6H7. + OH" 1-3
C6H6 + H > C6H7 * 1-4
C6H6 + OH > C6H6OH. 1-5
Products of these addition reactions are cyclohexadiene
systems containing an unpaired electron delocalized about
the benzene ring. The dienyl radicals, namely cyclohexadi¬
ene, C6H7*, and hydroxycyclohexadiene, C6H6OH«, have been
investigated by electron spin resonance technigues that
indicate a positive electron density assignment to the
ortho- and para-carbon atoms.54
Extensive pulse radiolysis work has shown these dienyls
exhibit a reasonably strong absorption (e = 5 x 10 3 M-1cm-1)
in the 310-315 nm range.55,56 Rate constants involving the
primary radicals with benzene as well as the dimerization
and disproportionation of the resulting cyclohexa- and
hydroxycyclohexadienyls have also been reported.55-61
Steady-state 7-radiolysis studies involving liguid
chromatography,62 radio-liquid chromatography,63 and gas
chromatography,64'65 as analyzing methods, indicate a com¬
plex mixture of products formed from the combination and
disproportionation of the cyclohexa- and hydroxycyclohexa-

13
dienyl radicals. Phenol and biphenyl are the major products
reported, in addition to mixed dienyls and regenerated
benzene. All of the previous studies were carried out in
N20-saturated or deoxygenated agueous benzene solutions. In
aerated aqueous benzene solutions, eag“ and H are scavenged
by 02. The hydroxycyclohexadiene radical reacts with 02
forming phenol and phenol-like products.66'67
1.2.4 Sodium Tetraphenylborate System
Pulse radiolysis studies of the aqueous NaTPB solutions
have been carried out in this laboratory to help establish a
mechanism consistent with the end product yields obtained
from Co-60 7-radiolysis on aqueous NaTPB solutions.68 These
steady-state radiolysis studies were done in conjunction
with the United States Department of Energy operation at the
Savannah River Plant in South Carolina and concerned the
problem of cesium-137 separation and removal from nuclear
waste obtained from spent fuel reprocessing.69 Precipita¬
tion of the radiocesium as its insoluble tetraphenylborate
salt is a method of separating it from the nonradioactive
components and concentrating it to reduce the volume of the
liquid radioactive waste. Other decontamination methods
include ion exchange and evaporation techniques.70'71 The
radioactive precipitate will be stored in large underground
steel tanks until it is sent to the Defense Waste Processing
Facility (DWPF) for immobilization in glass.72'73

14
The TPB precipitate will undergo intense p- and 7-
radiation from the cesium-137 during processing and storage
that will partially decompose the tetraphenylborate, produc¬
ing several organic compounds. Understanding the reaction
scheme which leads to these various organic products as well
as their impact on subsequent processing of the precipitate
are important aspects concerning the design and operation of
the DWPF.68
Since the tetraphenylborate anion, TPB-, is rather
different structurally from benzene or simple aromatics, it
is not obvious that previous work on the mechanism of ben¬
zene radiolysis is relevant. However, several lines of
evidence will be presented in this dissertation which indi¬
cate that there is a substantial connection. The prepara¬
tion and properties of aqueous metal tetraphenylborate salts
have been described by Flaschka and Barnard.74 LiTPB and
NaTPB are found to be the only TPB salts that are apprecia¬
bly soluble in water; all TPB salts tend to be soluble in
polar organic solvents.
Only a few mechanistic studies involving primary radi¬
olysis radical reactions with the TPB- anion have been found
in the literature. Horii and Taniguchi, using pulse radiol¬
ysis, studied the oxidation intermediates of the TPB- anion
in aqueous solutions using the oxidizing radicals N3-, Br2T,
and SCN2t.75 Kinetic as well as spectral information was
reported for che resulting intermediate, B(C6H5)4', which

15
was produced in all cases by an electron transfer from the
TPB- anion to the oxidizing radical. Liu et al. reported an
absorbing species at A = 300 nm for the expected radical
derived by OH* addition to the phenyl group of the TPB-
anion.76 Another transient, derived from H* addition to the
phenyl group was also discussed; however, no kinetic infor¬
mation was supplied regarding the fate of these resulting
transient species.
Other pulse radiolysis investigations involving the
NaTPB salt include ion association studies, in which the
spectra of the diamagnetic species, Na-, the solvated elec¬
tron, eaq“, and the ion pair species (Na+,eag-) are reported
for alkali metal solutions in various non-aqueous
solvents.77-82
The photochemistry literature of the metal tetraphenyl-
borates was surveyed to find possible mechanisms concerning
the reactions of the TPB- anion and subsequent intermediates
under UV-irradiation. Photolysis of aqueous solutions of
NaTPB using UV light with a wavelength of 2537 Á generates
biphenyl as the major product in oxygenated solutions and 1-
phenyl-1,4-cyclohexadiene as the major product in the ab¬
sence of 02.83'84 Other photochemical studies involve the
photolysis of tetraphenylborates in non-aqueous organic
solvents.85-87
Additional photochemical studies involving TPB- report
on photochemically-induced electron transfer from the TPB-

16
• Q Q ,
anion to oxygen,00 and various intermolecular charge-trans¬
fer transitions of donor-acceptor ion pairs involving the
TPB- anion.89-91
1.2.5 Aqueous Solution Studies of Transition-metal Complexes
In aqueous systems containing transition metal complex¬
es, the predominant reaction occurring between the solute
and the primary products of water radiolysis is a one-elec¬
tron transfer, either oxidation or reduction. This electron
transfer can occur by an inner- or outer-sphere
mechanism,92,93 often leaving the complex ion in an unstable
oxidation state. Aqueous solutions of both transition
metals and their complexes, most notably bio-inorganic
molecules, have been irradiated and the radiation chemical
processes which occur have been extensively reviewed.
In aqueous systems, aquation of the metal complex from
ligand exchange with water molecules can occur, and has been
reported in both pulse radiolysis studies96-99 and photo¬
chemical studies.100'101 Changes in the stereochemistry
and coordination number of the transition metal complex upon
pulse irradiation have also been investigated.
1.2.6 Hexachloroiridate System
The redox chemistry of the IrCl62- and IrCl63- complex¬
es has been of recent interest due to the prospect of using
the system to produce molecular hydrogen by the solar photo¬
chemical reduction of protons in acidic aqueous solu-

17
tions.104 The solar chemistry of metal complexes has been
reported by Gray and Maverick.105 Solar chemistry is de¬
fined as that area of photochemistry in which the excitation
energies fall within the spectrum of solar irradiation at
the earth's surface. The proposed scheme involving aqueous
HCl solutions of IrCl62-/3- is
IrCl63-
+ H+ > IrCl62- + 1/2H2
1-6
IrCl62-
+ Cl- > IrCl63- + 1/2C12
1-7
The net result is the conversion of HCl to hydrogen and
chlorine using UV and visible light as the only energy
sources. While Gray reports that the second reaction occurs
with low efficiency at wavelengths higher than 430 nm, the
first unfortunately occurs only with UV light, e.g. at 254
nm.
In this study we attempt to further elucidate the
radiation chemistry of the chloroiridates under various
aqueous solution conditions, namely in alkaline, N20-satu-
rated solutions and in neutral, aerated solutions.
Dynamic processes occurring in the IrCl6 / IrCl6J
system have been previously investigated by photochemical
techniques.100'101'106'107 Dainton and Rumfeldt made perti¬
nent observations concerning the chemistry of the system,
although their experimental procedure involved Co-60 y-
radiolysis rather than direct studies of the transients.108

18
Mills and Henglein used steady-state gamma radiolysis
of aqueous IrClg to explore the formation of colloidal
iridium and the catalytic properties of the colloid with
respect to H2 formation.109'110 Pulse radiolysis of NalrClg
aqueous solutions, carried out by Mills and Henglein, exam¬
ined the reduction of IrCl63- by eag“ and the (CH3)2COH*
radical. A fundamental pulse radiolysis study on the aque¬
ous solution redox reactions of hexachloroiridate complexes
by Broszkiewicz addressed both the reduction and oxidation
of aqueous IrClg3-.111 From his work, the author concluded
that octahedral IrCl63- is oxidized by a single electron
transfer to octahedral IrCl62- without changing its struc¬
ture or ligand composition, i.e. aquation. Edwards also
commented that the iridium chlorides are typical examples of
complex ions that are relatively inert toward substitution,
but which undergo rapid electron transfer reactions. -L‘6
Further pulse radiolysis studies on transition metal
hexachloride complexes have been reported by
Broszkiewicz.113-115 Other pulse radiolysis studies involv¬
ing aqueous IrCl63- have examined its oxidation by the
azidyl radical, N3*,116 and the hydroxyl radical, OH".93

CHAPTER II
EXPERIMENTAL APPARATUS AND PROCEDURES
2.1 Pulse Radiolysis Instrumentation
Reactive intermediates generated in radiation-induced
chemical processes are short-lived; thus the pulse radioly¬
sis instrumentation must be able to monitor the transient
behavior with a high degree of resolution over extremely
short intervals. Since the concentration of such intermedi¬
ates can influence both the mechanistic pathway and the
final product yields, detection techniques that are sensi¬
tive to very low concentrations of radicals are necessary
for a complete characterization of the transient behavior.
The University of Florida pulse radiolysis system
configuration incorporating computer control is shown in
Figure 2. The accelerator used is a Febetron (brand name
for the impulse generator produced by Field Emission Corp.)
706, which operates on the principle of the Marx-bank cir¬
cuit. Other accelerators used in time-resolved studies
include the linear accelerator (linac), and the Van de
Graaff generator. One may see that the other components
shown comprise an absorption spectrophotometer. Absorption
spectroscopy is the most widely used technique among others
mentioned previously, for monitoring transient behavior in
pulse radiolysis.
19

C: solution flow cell
DO: dual op amp
FP: Febetron power supply
HV: PMT power supply
IP: ion pump
L: xenon-arc lamp
LP: lamp power supply
LS: lamp, shutter drive
M: monochromator
MR: mirror
P: photomultiplier
PB: lead cave
PC: lab microcomputer
PP: ion pump power supply
PR: printer
PT: programmable time delay
S: shutter
SC: digitized recorder screen
TD: transient digitizer
TR: trigger source
V: video display
VA: voltage amplifier
VD: voltage divider
Fig. 2. University of Florida pulse radiolysis system.

FP
FEBETRON
706
TR |
H VD I
I [ Se.
j '7
/ /
/ j .
M
—
-c*
-s*
P
PB
DO
VA
HV
/
K)

22
2.2 Absorption Spectrophotometry
Components involved in an absorption spectrophotometer
are the light source, an optical train including all lenses,
mirrors and absorption cell, the monochromator, the detector
and a recorder. In flash photolysis and pulse radiolysis,
the absorption cell also serves as the reaction region.
2.2.1 Light Source
The light source used should provide high monitoring
light output to optimize the signal-to-noise ratio, S/N,
which is directly related to the intensity of light striking
the photocathode of a photomultiplier by the equation:
S/N = (Is/ A f)1/2 II-l
where Is is the light intensity at the photocathode and
delta f is the bandwidth of the recorder system. x'' A-LO
This relationship is applicable when signal shot noise is
the limiting S/N determining factor as is the case in fast
( > 1 kHz) kinetic spectrophotometry. Lasers provide high
monitoring light intensities but are limited as to their
wavelength of operation. Thus in order to utilize an ab¬
sorption technique that is applicable to all transients or
combination of transients throughout the ultraviolet and
visible spectrum, a high power spectral lamp with a continu¬
ous distribution is preferred. Xenon-arc lamps filled with

23
xenon gas at above atmospheric pressures provide the follow¬
ing features: high arc stability and luminous flux, high
reliability and long operating lifetimes up to 1000 hours.
In addition, high-current pulses can be delivered to the arc
lamp, which enable very high monitoring lamp outputs during
transient measurement times of microseconds to milliseconds.
2.2.2 Absorption Path and Monochromators
The flow reaction cell previously mentioned allows for
the production of transient species in the irradiated volume
which can be directly monitored by absorption spectrophotom¬
etry. For example, using the Beer-Lambert relationship,
A = e b c I1-2
where e = molar extinction coefficient (M-1cm-1)
b = pathlength (cm)
c = concentration (M)
and assuming 1) a transient molar absorption coefficient, e,
of approximately 1000 mol-1dm3cm-1, 2) a transient popula¬
tion which produces a 10% deflection in the initial light
intensity, and 3) a 1 cm absorption pathlength, one calcu¬
lates the initial transient concentration formed in the
irradiated volume immediately following the pulse to be
approximately 4.5 x 10-5 M.
Monochromators function to isolate a small wavelength
band from a polychromatic source and consist of a dispersive
element, either a prism or grating, and an image transfer

system of slits and mirrors. By using a monochromator with
an adequate light flux throughput and a varying wavelength
range, transient signals can be recorded as a function of
wavelength to build a time-resolved transient spectrum.
The throughput factors which determine the radiant
power passing out of the exit slit of a monochromator are
the source spectral radiance, BA in units of Wmm-2 sr-1 nm"
and the monochromator throughput factor, Y in units of mm2
sr nm. The product of these two factors gives the output
spectral radiant power, Q, in watts.118 For operating a
monochromator with a broadband or continuum source the
monochromator throughput factor, Y, is defined as
Y = w2 h
(n/4)
TopRd
II-3
(F/n)
where w = slit width (mm)
h = slit height (mm)
F/n = f-number or effective aperture
TQp = optical transmission factor (unitless)
Rd = reciprocal linear dispersion (nm/mm)
Since the light image is usually focused down on the en¬
trance slits by a condensing lens, the slit width is the
only experimental variable parameter in determining the
light throughput at a particular wavelength for a monochro¬
mator with a fixed optical transmission factor, effective
aperture and reciprocal linear dispersion.±±'

25
2.2.3 Photomultipliers
The advantages of using photomultiplier detectors to
display transient absorption signals on transient recorders
are high sensitivity due to secondary emission multiplica¬
tion, fast response times relative to the half-life of the
relaxation processes being monitored, and the ability to
handle high light flux levels while maintaining a linear
signal at high output photocurrents.119 Two types of photo¬
multipliers were used in this work which have different
spectral response ranges. An EMI Model 9250 QB end-on 50 mm
window PMT fitted in a Pacific Precision Instruments Model
3262 housing was used initially with the geometry shown in
Figure 3. Because of its extended spectral response range
above 600 nm, a Hamamatsu Model R928 side-on 30 mm window
PMT fit into a Pacific Precision Instruments Model 3150
housing was eventually incorporated into the geometry shown
in Figure 4.
The photomultipliers were powered by a John Fluke, Inc.
Model 412A High Voltage DC power supply, which proved to be
a well regulated and stable dc source. The overall gain on
the PMT could be altered by changing the applied voltage,
typically from 1000 Vdc to 1250 Vdc in increments of 10 or
100 volts, while maintaining maximum gain on the operational
amplifier.
The EMI end-on tube has a bialkali photocathode, a
Spectrosil quartz window, and an optical range of 165-650 nm

sc
L
RB
Cell holder
_ LE
PM
i
L
\
McPherson
218
Monochromator
IP
26
Febetron
706
PB
X '
' ' AV \
' PMT
PH
X /
L - Xenon arc lamp
LE - Condensing lense
IP - Ion pump
PB - Lead cave / shield
PH - PMT housing
PM - Parabolic mirror
PMT - Photomultiplier tube
RB - Adjustable razor blades
SC - Solution cell
Fig. 3. Experimental arrangement using the McPherson 218
monochromator.

27
PMT , PH
IP
PB
L - Xenon arc lamp or laser
LE - Condensing lense
IP - Ion pump
PB - Lead cave / shield
i
Jarrell-Ash
Monochromator
LE
Inset
1
Cell
holder
*
1
i
i
L
1
, RB
i
| â– 
SC
1
i
PM
\
PMT
PH
UlJ
PM - Parabolic mirror
PMT - Photomultiplier
RB - Adjustable razor blades
SC - Solution cell
Fig. 4. Experimental arrangement using the Jarrell-Ash
monochromator.

28
with a peak wavelength, or maximum radiant sensitivity
(mA/W), at 420 nm. Figure 5 shows a diagram of the base
components which were customized to achieve optimum rise
times, gains and linearities for use in the pulse radiolysis
system. The EMI Model GB 1001A fast electronic switching
circuit connected through an optoisolator and switching
transistor gates off the first dynode voltage of the PMT to
eliminate overloading problems caused by short burst expo¬
sure to high light intensities. The gating circuit offers a
precise way to regulate the PMT from a + 5 volt gate signal
and has the specifications of an on-to-off fall-time of 0.5
microseconds and an off-to-on rise-time of 1.5 microseconds.
This circuit which is normally applied in flashlamp or laser
systems to protect from overloading conditions was original¬
ly employed to eliminate the overloading of the PMT by
fluorescence of OH radicals which occurred in previous gas
phase studies on the argon sensitized pulse radiolysis of
water vapor.3 In the present liquid phase work, such severe
fluorescence problems derived from radiation interactions
with either the aqueous chemical system or the quartz cell
have not been encountered.
Gating of the PMT was applied to reduce the effect of
high levels of electromagnetic interferences (EMI) associat¬
ed with the high beam current Febetron 706 machine. Ac¬
counts of these electromagnetic fields and their effects on
detection electronics are discussed in the literature. °'

GB 1001
gating circuit
high voltage
_ri_ gate input
CL
0.1
H H
(150 V)
IN3048
51 K 51 K
51 K
i—iH-—» ■-)-■) |—»—|
7
19
10 M
10 %
51 K 51 K
>|CC
6
51 K
-Cl
Cathode
4 5 6
dynode no.
PHOTOMULTIPLIER
.002
I I i
005
L 1 1
01
I I
02
. i ( n
1 1 i
1 11 '
, l (
1 1
200 K
200 K
400 K
200 K
fr>i
rCCH
K"'~H
» L J- T
8
9
10 11
pin no.
7 8 9 10
Anode
to magnetic
shield
All capacitors 1 kV
All capacitor values in microfarads 12
All resistors 1% metal film unless noted
Socket: B19A
Fig. 5. Photomultiplier tube base schematic used with EMI 9250 QB in model 3262 housing.
to
to

30
By gating off the initial dynode of the PMT during the
radiation pulse, overloading of the photocathode by the X-
ray (X-radiation) and the radio-frequency (RF) noise coinci¬
dent with the electron pulse was significantly attenuated.
Further attempts to reduce the EMI effects included the use
of lead shields inserted into the entrance of the PMT hous¬
ings, Figure 6, and extensive lead shielding around the
outside of the PMT housing.
The Hamamatsu side-on PMT was obtained to expand the
wavelength range to allow transient absorption measurements
above 600 nm, and was used in all subsequent experiments
after installation. This PMT has a multialkali photocath¬
ode, a UV-glass window, and an optical range of 195-900 nm
with a peak wavelength at 400 nm. Figure 7 shows a diagram
of the customized base components used with this PMT along
with a gating circuit that is analogous to the one previous¬
ly described.
2.3 Light Source Systems
For a versatile pulse radiolysis system with capabili¬
ties of nanosecond sampling times in the UV-VIS region of
the spectrum, stable and high analyzing light intensities
are needed in order to permit the observation of weak or
long-lived absorption signals, to reduce shot noise, and to
increase the signal to noise ratio.

31
a) 2 1/16 inch diameter x 1/2 inch thick lead shield
for end-on PMT housing, Model 3262.
b) 1 1/4 inch diameter x 1/2 inch thick lead shield
for side window PMT housing, Model 3150.
Fig. 6. Lead shields for PMT photocathodes in the Pacific
Precision Instruments PMT housings.

GB 1001
gating circuit
high voltage input
gate input
1
-v-
—
01 01 01 01
(150 V)
IN3048
39 K 39 K 39 K 39 K 39 K
10 M
10 %
—<
—«
h—
1
—4
â–º
__
—«
11
h
1
2
3
4
V.
y -t—
47 K
<$â– 
110 K
110 K
L_
68.1 K
8
180 K
150 K
—i
Cathode
4 5 6 7
dynode no.
PHOTOMULTIPLIER
8
pin no.
9 !
Anode
to magnetic
shield
All capacitors 1 kV
All capacitor values in microfarad
All resistors 5 % unless noted
Socket: Amphenol 77MIP-IIT
10
Fig. 7. Photomultiplier tube base schematic used with Hamamatsu R928 side-window
PMT and model 3150 housing.

33
2.3.1 Xenon-Arc Lamp
The lamp system used in this work consisted of a xenon-
arc high pressure discharge lamp contained in a water-cooled
housing and powered by a water-cooled ignition device / DC
power supply. Several different bulbs including an Advance
Radiation Corporation XSA 350 and 500 watt and a Ushio UXL
302-0 300 watt were used throughout the work. The ARC bulbs
were of the deep UV design, in which a metal vapor, such as
mercury, is present in addition to the xenon gas providing a
strong distribution in the deep UV region (190 to 250 nm).
The Ushio bulb was not seeded with such a metal and its
continuous spectrum is shown in Figure 8. This spectrum was
generated by feeding the PMT output across a load resistor
and into a Linear Instruments Corporation Model 591 chart
recorder.
The bulb was contained in a PRA-Canada ALH 220 housing
with dual water cooling loops and powered by a PRA-Canada
Model M301 ignition-power supply. The power supply uses a
continuous feedback, constant current mode of operation to
give excellent current stability. Current programming with
sguare, triangular, or sine wave modulation can be used in
this unit to vary the optical output of the lamp. As shown
in Figure 9, a 2-3 L/minute cooling line was in series with
the power supply and top face plate portion of the housing
which was oriented vertically. A separate 0.25 L/minute

Fig. 8. Xenon-arc lamp spectrum, (nm)
U>
4^

Febetron 706
EC - Electrical connectors
l(o) - Initial light intensity
l(t) - Transmitted light intensity
LE - Condensing lense
M - Mirror
SC - Solution cell
3H - Shutter
Fig. 9. Xenon-arc lamp schematic diagram.

36
cooling line was used for cooling of the lamp electrodes.
The approximate dimensions of the different optical arrange¬
ments are also shown for the lamp housing which contains an
f/2.4 exit lens.
For conditions of 1) low absorbance monitoring on the
order of a 1% change in light intensity or less, or 2) lower
relative light output (i.e. the lower and upper regions of
the lamp output spectrum shown in Figure 8) a short dura¬
tion, very high monitoring light output is desired. This
was accomplished by using a conventional signal generator
feeding a BNC connector in the rear panel of the M301 power
supply. The timing and magnitude of the positive going
sguare pulse was determined by the specifications given by
the manufacturer.121 The pulse width is reguired to be < 1
second to eliminate damage to the bulb. The pulse magnitude
can be varied between 0 and 1 volt according to the follow¬
ing equation
W = lidie + tvmod/4) * 50] JI"4
where 1out = M301 output current
lidie = idle current, typically 3-5 amps
vmod = outPut voltage of the signal generator
The upper limit of Vmod, 1 volt, is determined so that Iout
does not exceed the listed nominal operating current of the
lamp which for the Ushio UXL 300 W bulb is approximately 15
amps. To attenuate and fine control the 5-volt TTL type
signal from the pulse generator, a potentiometer voltage

37
divider circuit was placed in series with the pulse genera¬
tor and M301 power supply. Preliminary monitoring of the
pulse parameters was done through a Tektronix Model 35A
oscilloscope prior to actually pulsing the lamp.
2.3.2 He-Ne Laser
A Spectra Physics Model 155 helium-neon laser was used
for alignment of the optical systems, calibration of the
monochromator gratings, and as a light source for absorption
spectrophotometry involving the kinetics of the hydrated
electron, eag“. Characteristics of the monochromatic 632.8
laser light such as high collimation, low divergence, and
high intensity make this source ideally suited for eag-
studies.122 Figure 4 shows the optical arrangement used for
the He-Ne laser, the Jarrell-Ash monochromator and side-on
PMT. Attempts to monitor the 632.8 nm light with the end-on
EMI PMT were unsuccessful due to this tube's lack of sensi¬
tivity above 600 nm.
2.4 Reaction Cells and Cellholder
Two types of reaction cells, both consisting of modi¬
fied guartz UV-VIS spectrophotometric cuvettes, were con¬
structed for this study. Previous accounts of similar
reaction cells for use in low energy electron beam radioly¬
sis studies involving liquids indicated the importance of

38
using very thin electron entrance windows that would mini¬
mize the attenuation of the low energy electron beam in the
liquid.123 A cuvette fitted with a reservoir and flow exit
for flushing purposes was used in all the on-line absorption
detection work and a non-flow cell was used exclusively for
the Fricke dosimetry experiments.40 Both cells were fitted
into an aluminum cell holder to provide reproducible posi¬
tioning and to assure the delivery of equal doses.
2.4.1 Flow Reaction Cell
The flow cell, Figure 10, was constructed from a 60 ml
separatory funnel, a 3 2 stopcock, a 3? 5/20 glass joint, a
glass/quartz connector seal and a modified quartz UV-VIS
cuvette. A thin mylar sheet = 200 microns thick was held by
epoxy glue to the quartz cell and served as the electron
entrance window. In the initial construction of the cell,
FISHER brand microscopic optical glass cover slides with a
thickness of 0.13 to 0.17 mm were used.124 However, the
mylar sheet material was chosen as the electron entrance
window due to its lesser thickness and the ease by which it
could be mounted and trimmed on the cuvette. The optical
pathlength was 1 cm, and with an electron penetration depth
of ca. 1.5 mm for 600 KeV electrons in water,122 the irradi¬
ated volume was 1 x 1 x 0.15 cm. This electron penetration
depth, which is less than the extrapolated range of 1.9 mm,
is taken as the depth over which a reasonably uniform dose

39
Fig. 10. Flow-reaction cell with modified UV-VIS cuvette.

40
deposition can be assumed.125 For studies using purging
gases, the gas was continuously bubbled into the upper
reservoir for the duration of the experiment.
2.4.2 Non-Flow Reaction Cell
This cell, Figure 11, was constructed from a UV-VIS
cuvette to provide detection of 304 nm light associated with
the maximum absorption of the ferric ion, Fe3+, the oxida¬
tion product derived from the radiolysis of an acid solution
of ferrous ion, Fe2+, in the Fricke dosimetry system as
discussed in Appendix B.40 The electron entrance window was
identical to that of the flow cell and a total volume of 1.4
ml was delivered by syringe to the cell prior to radiolysis.
This cell could be readily removed from the aluminum cell
holder in the pulse radiolysis system and transferred to a
Beckman DU model 2400 spectrophotometer with Gilford solid-
state electronics, allowing absorption measurements to be
made as a function of the number of radiation pulses re¬
ceived. A dilution factor involving the actual irradiated
volume of 0.15 ml and the total volume of 1.4 ml was used in
all dose calculations.
2.4.3 Cell Holder
An aluminum cell holder, Figure 12, was used to enable
reproducible placement of the solution cell with respect to
both the electron beam and analyzing light. The holder

41
entrance window
SIDE VIEW
solution injection
by syringe
i
total volume = 1.40 +/- 0.02 ml
Fig. 11. Non-flow-reaction cell formed from UV-VIS cuvette.
Reaction volume consists of 1 x 1 x 0.15 cm region
immediately behind mylar entrance window.

42
Fig. 12. Reaction cellholder with adjustable razor blade
mounts and wire-mesh screens. Electron beam
enters through rear flange and traverses 8.0
inches in air. Radiation-induced reaction region
occurs in cell (not shown) located at intersection
of e-beam and analyzing light.

43
consists of a 1 x 1 inch open rectangular aluminum column
eight inches in length fitted to a six-inch diameter alumi¬
num flange that is attached by four threaded screws to the
outer edge of the short-pulse adapter chamber of the Febe-
tron 706. Adjustable razor blades mounted at the entrance
and exit apertures at right angles to the electron beam axis
defined the width of the analyzing light beam. The use of a
very narrow analyzing light-beam allowed for the study of
the solution kinetics by monitoring only a narrow cross-
section for which the dose could be reasonably defined.
Using this arrangement, the electron beam traversed ca.
8 inches of air between the field emission tube exit window
and the thin mylar entrance window of the reaction cell.
This distance creates a slight attenuation of the electron
beam intensity which is primarily associated with a spread¬
ing of the effective beam diameter away from the tube face.
For a distance of eight inches the beam will have an effec¬
tive diameter of three centimeters as compared to a diameter
of 1.5 centimeters as it exits the tube face. The loss of
beam intensity due to absorption in air should be negligible
due to the maximum penetration range of 80 inches for 600
KeV electrons in air.125/126
Experiments with FISHER brand optical glass microscopic
coverslides placed in the cell holder at the solution cell
position were performed to determine the depth distribution
of the electron beam. Typical depth-dose curves are shown

44
in Figure 13 which includes data for two experimental condi¬
tions. Initially a stack of approximately 20 slides was
exposed to a single Febetron shot with maximum charging of
30KeV. Absorption measurements were then made on each
individual slide to detect the amount of discoloration in
the glass due to the e-beam penetration. Secondly, a simi¬
lar stack of coverslides was exposed to 10 cumulative shots
at full charge, followed by individual absorption measure¬
ments. Both data sets indicate an extrapolated range for
the 600 keV electrons in the glass to be approximately 7
slides. Using a slide thickness of 0.15 mm, the extrapolat¬
ed depth in glass is found to be 1.0 mm. Assuming that
glass is approximately twice as dense as water, these data
indicate a maximum range for 600 Kev electrons in water to
be approximately 2.0 mm, which agrees with the earlier
reported value of 1.9 mm.125
Figure 14 shows the absorption due to the discoloration
in a single slide as a function of the number of pulses
delivered at maximum charging. The accumulated discolora¬
tion resulting from the e-beam passage through the glass
slide was found to be non-linear, with the absorption fall¬
ing off as a function of pulse-number.
Wire mesh screens capable of 60% to 80% electron beam
reductions could be positioned in the cell holder two inches
from the field emission tube window (Figure 12) to aid in

Absorbance (x 1000)
45
20
15
10
5
0
Ten puises delivered
One pulse delivered
0 2 4 6 8 10
Coverslide #
Fig. 13. Depth-dose curves for glass coverslide experiment.

Absorbance (x 1000)
46
35
30
25
20
15
10
0 5 10 15 20
Pulse #
Fig. 14. Absorbance change with number of pulses delivered
for glass coverslide experiment.

47
acquiring transient formation signals occurring during the
first few microseconds immediately following the radiolysis
pulse. These screens restrict the flux of the electron
beam which was maintained at a maximum charging voltage of
30 KeV. With the wire mesh screens inserted, attenuation of
the beam intensity decreases the total average population of
initial radicals formed. This beam flux attenuation helps
to prevent radical-radical interactions and provide favora¬
ble radical-solute interaction conditions. However, due to
both a malfunction in the fastest data acquisition mode of
the transient digitizer, and electromagnetic interferences
associated with the Febetron 706 system that were discussed
earlier, attempts to capture transient formation signals
with enough resolution for kinetic analysis were not suc¬
cessful .
2.5 Monochromators
In the early stages of this work a 0.3 meter McPherson
218 monochromator was used. Later, efforts were made to
reduce electronic interferences associated with the electron
beam pulse by removing the monochromator and PMT couple away
from and to the rear of the field emission tube. Due to the
rather permanent fixture of the Mcpherson 218 and its asso¬
ciated vacuum pump assembly relative to the initial experi¬
mental geometry, a second 0.25 meter Jarrell-Ash 82-41550
monochromator was employed.

48
2.5.1 0.3 Meter Monochromator
Initial studies were carried out using a McPherson 218
vacuum/atmospheric monochromator which has an f/5.3, a 2400
G/mm plane grating and a 1.33 nm/mm linear dispersion. The
vacuum capabilities were not employed for any of this work
and the 2400 G/mm grating having a 0 - 5,000 angstrom wave¬
length range was eventually replaced with a 1200 G/mm grat¬
ing capable of operating in the wavelength range from 0 -
10,000 angstroms. A synchronous motor-driven gear box
supplies 12 scanning speeds from 0.5 angstroms/minute to 200
angstroms/minute and slit widths were adjustable from 10
microns to 2 millimeters. Slit widths of 1.5 millimeters
and a fixed slit height of 8 millimeters were used. Figure
3 shows the optical configuration used with the McPherson
monochromator. Light exiting the xenon arc lamp was passed
through a condensing lens onto a first surface mirror and
reflected through the solution cell. The beam was then
focused on the entrance slit of the monochromator and after
wavelength dispersion the exiting beam was reflected onto
the photocathode of the PMT by a 2.5 cm focal length para¬
bolic mirror.
2.5.2 0.25 Meter Monochromator
Initial testing of the Jarrell-Ash monochromator cou¬
pled to the end-on PMT with both components located approxi-

49
mately 2 meters away from the field emission tube showed a
marked improvement in reducing the electromagnetic noise
interferences. Using the McPherson monochromator in the
previously shown geometry in conjunction with the gating
circuit produced a net dead-time, caused by gross overload¬
ing of the PMT, of > 5 microseconds in the detection system.
When the detection system was relocated, as shown in Figure
4, net dead-times of 2 to 3 microseconds could be attained
without the use of the gating circuit. All subsequent work
was completed with this arrangement and eventually the end-
on PMT was replaced by the side-on PMT. To attain further
reduction of the EMI effects, the entire detection system
and signal lines would have to be either completely removed
from the room containing the Febetron 706 or extensively
shielded.120'127
In this modified configuration the analyzing light,
after passing through the solution, was reflected by a first
surface mirror back to a plano-convex f/2.5 condensing lens
and focused onto the entrance slit of the Jarrell-Ash mono¬
chromator. This monochromator has an f/3.5, a 1180 G/mm
grating and a 3.3 nm/mra linear dispersion. A wavelength
motor drive of 100 nm/minute was coupled to a wavelength
drive knob to enable scanning of the light source spectrum.
The slit arrangement provided with this monochromator
was altered to accommodate the direct coupling of the Jar¬
rell-Ash monochromator to both a previous gas phase aluminum

50
reaction cell, and the Pacific Precision Instruments PMT
housing.128 In this work only, the direct couple of the
monochromator and PMT housing was utilized. This was accom¬
plished by screwing the PMT housing containing the side-on
Hamamatsu tube directly to the exit slit flange adapter.
Figure 15 shows the entrance and exit system flange adapt¬
ers. Brass slit bodies of fixed width and height, 0.71 mm
and 15 mm respectively, were screwed into the aluminum
flange by turning the two small holes in the slit body with
a sharp tool.
2.6 Febetron 706 System
The principle of pulse radiolysis involves the delivery
of ionizing radiation to a chemical system in the form of a
short pulse that creates a non-eguilibrium system with an
adeguate amount of transient species that are monitored in
time. An accelerator is used as the source of the high
kinetic energy ions and several related parameters are
important in pulse radiolysis measurements. Primarily, the
radiolytic pulse should be very short relative to relaxation
of the transient system, and the pulse current should be
large enough to produce an observable concentration of
transients. Energy deposition, which depends on 1) the
particle's mass, charge, and velocity, and 2) the medium
density, is critical in determining the distribution (either
homogeneous or non-homogeneous) of radical concentrations
produced.

51
slit area = 0.71 mm x 15 mm
Fig. 15.
Entrance and exit slit system flange adaption to
the Jarrell-Ash monochromator.

52
The Febetron 706 electron accelerator used in this work
is fitted with a Model 5515 high vacuum field emission
electron tube and has the following specifications: 12
joules maximum pulse energy, 8,000 amperes of peak current,
3 nanosecond pulse duration (FWHM), 5% peak to peak repeat¬
ability, and a maximum electron energy of 600 KeV. The
extremely high currents make this model particularly ap¬
plicable to gas phase studies.
However, it was suspected that the high vacuum electron
tube had become gaseous due to intermittent use in previous
years and the extended lifetime of the electron tube beyond
its suggested 3500 pulses. The e-beam tube had failed after
ca. 8000 pulses; the beam had burned microscopic holes in
the window which allowed the pressure in the tube to rise to
atmospheric. It was expected that partial operation could
be restored by replacing the window and reevacuating the
tube. This attenuated beam feature would be beneficial to
condensed phase studies by eliminating radical-radical
interactions caused by the absorbance of enormous radiation
doses. Encouraged by other somewhat analogous and confirm¬
ing reports,122'129-132 we pursued the application of the
Febetron 706 accelerator to aqueous solution work.
Details of the Febetron 706 system can be found else¬
where.125'126,133 Figure 16 shows a block diagram of the
Model 706/2677 system. The Febetron 706 system was main¬
tained by keeping the various chambers with their associated

high voltage
power supply
delayed trigger freon regulator
amplifier , (15 psi Freon-12)
trigger
-
(90 V)
T
short pulse switch
& adaptor chamber
Marx-surge circuit
(module chamber)
air/nitrogen regulators
(0-80 psi) (0-240 psi)
?
field
emission
tube
transformer
oil
pump
assembly
Fig. 16. Febetron 706 system schematic.
u:
oj

54
pressure regulators and gauges properly pressurized. A
compressed air tank is used to pressurize the module chamber
at a maximum of 80 psi and the short pulse adapter at a
maximum of 240 psi. Freon-12 was maintained at 13 psi in
the pulser case. The transformer oil in the short pulse
adapter was circulated daily by an electric pump connected
to a large oil reservoir.
The accelerator operates on the principle of the Marx-
bank circuit which consists of a number of connected high
voltage capacitors that are charged in parallel and subse¬
quently rapidly switched to a series arrangement through
spark gaps. This circuit, located in the Marx-surge stage
of the pulser, produces a high voltage, extremely high peak
power pulse that is used to pulse charge through a series
spark gap in the central electrode of the short pulse adapt¬
er stage of the pulser. This short pulse adapter then
discharges an extremely short 3 ns high current pulse to the
field emission electron tube. This pulse generates electron
emission from the cathode and the electrons are then accel¬
erated toward an exit window that functions as the anode.
As mentioned above, due to the lack of an inward de¬
flection in the thin exit window of the field emission tube,
it was decided that gaseous conditions existed inside the
tube. Under normal conditions, the thin metal window would
be noticeably drawn in by the high vacuum. Experiments
using the technique of calorimetric dosimetry carried out

55
directly in front of the tube exit window showed negligible
energy outputs. Therefore a modified electron beam tube
exit system was fabricated.
2.6.1 Refurbished Beam Tube
A modified electron beam tube flange and exit window
system132 was constructed to renew the output of the Febe-
tron 706 system. This modification, Figure 17, was formed
from a stainless steel chamber 4.75 inches in diameter and
1.25 inches thick, and fit with a Model 202-100 Perkin-Elmer
2 liter/second differential ion pump powered by a Model 222-
0200 Perkin-Elmer IONPAK 200 power supply. The high vacuum
current limiting power supply operated at a voltage between
+4000 volts DC and +6000 volts DC and the system was capable
of attaining pressures below 1 x 10-6 Torr.
The former anodic window of the field emission tube was
cut away and a thin, approximately 0.001 inch stainless
steel window and o-ring were set into the compartment. The
compartment was attached by three threaded screws to the
field emission tube window face plate flange of the Febetron
706 with a second o-ring seal. Initially, the thin window
was placed 0.8 inches away from the original anode window
location. Although an adeguate vacuum was attained, further
dosimetry experiments showed no improvement with this geome¬
try so the window was set further into the compartment 0.4

stainless steel 2 l/sec
anode window differential
ion pump
4 thru holes
cell holder
adjustable razor
blades
o-ring
grooves
A,B indicate initial and final anode
window placement, respectively
?
needle valve
roughing pump
4 thru holes
Febetron
706
3 threaded
insets
Fig. 17. Refurbished electron-beam tube with ion pump.

57
inches away from the original window location. After rough
pumping the chamber down to a few microns of pressure and
attaining the minimum +4000 volts DC required for proper
operation of the ion pump, calorimetric dosimetry measure¬
ments were again performed.
2.6.2 Calorimetric Dosimetry
The total-beam calorimetric technique, as illustrated
in Figure 18, involves the measurement of the heat deposi¬
tion in an aluminum disk upon firing the Febetron 706 at
maximum charge. The thickness and diameter of the disk,
0.033 inches and 1.385 inches respectively, were chosen to
assure complete e-beam deposition. Aluminum is suitable due
to its high thermal conductivity, specific heat, and low
backscatter energy coefficient. The temperature of the
calorimeter was conveniently measured by attaching a thermo¬
couple and measuring the voltage output with a recording
millivoltmeter. The thermocouple was attached to the alumi¬
num disc in this particular calorimeter by drilling a small
hole in the center, inserting the thermocouple wires, and
swaging the aluminum around them with a punch. The calibra¬
tion of the thermocouple/chart recorder was accomplished
using room temperature of ~ 25 °C as the base line and
normal body temperature of ~ 37 °C as the maximum scale
value. For the maximum temperature reading, the disk was
held firmly in the palm of the hand until a steady equili¬
brated signal was obtained.

58
e-beam
styrofoam
mount
aluminum disc
chart recording
millivoltmeter
37.0 C
thermocouple
T j cooling
' ~r 25.0 C
thermocouple
wires
(4 ft.)
Fig. 18. Total beam calorimetric dosimetry arrangement.

59
Using the equation
Q = m Cp A T II-5
with Q = heat required to raise the specific heat of the
calorimeter by A J, Joules
m = 2.3 +/- 0.05 grams (mass of the aluminum disk)
Cp = 0.22 cal/ °C gram (specific heat of aluminum)
AT = 0.53 °C (difference between pre- and post- pulse
read from chart recorder)
a value of 1.12 +/- 0.06 Joules was determined as the beam
energy absorbed per pulse. These positive results indicated
that the placement of the new anode window was a critical
factor with possible arcing complications arising when the
new window was not located close enough in to the original
window position.
2.7 Transient Recorder and Computer System
While early pulse radiolysis studies used the oscillo-
scope-Polaroid photograph technique for recording transient
signals, development of sophisticated transient recorders
followed that now have replaced this manual data analysis
method.117 Digital recorders now digitize the input signal
in real time and can resolve the signal into separate chan¬
nels thus providing a stored digitized record of the tran¬
sient trace as a function of time. In addition, interfacing
of the recorder with a computer allows for integrated con¬
trol of the operational parameters such as time base, sensi¬
tivity, delays, signal processing, and data transfer.

60
The data acquisition and analysis system developed for
this work is a second generation system having been preceed-
ed by a Biomation Model 610B transient recorder supported by
an IMSAI 8080 S-100 bus microcomputer.128 Current instru¬
ments include an Analogic Data Precision DATA 6000 waveform
analyzer fitted with a Model 620 2-channel plug-in digitizer
interfaced through a serial port at 9600 baud to a Tandy
1200 IBM-PC/compatible laboratory microcomputer.
The DATA 6000 has two signal-input ranges of +/- 1.2
and +/- 3.6 volts full scale, and a maximum sampling rate of
100 MHz. This sampling rate gives a period (time between
sampled points) of 10 nanoseconds for collection of 512
points using an 8-bit recorder. Although the maximum period
attainable is 300 seconds, a maximum period of 1 microsecond
was used in this work giving a sampling rate of 1 MHz. The
DATA 6000 is noted for its versatile capabilities of signal
capture, processing and data transfer, although the lack of
any fine control on the input voltage parameter was found to
be a rather severe experimental limitation in this work.
The DATA 6000 is controlled by a single internal 68000
microprocessor and a CRT display screen enables visual
inspection of signals before data transfer.124
Data recording parameters were selected either manually
through keypads on the front panel or remotely via computer
control. Remote control of the DATA 6000 via an RS-232

61
serial interface port utilized three basic functions: con¬
trol of data recording parameters, use of processing and
display, and transfer of data to and from the digitizer. To
use these functions, a computer program written in BASIC
language provided either keystroke emulation by key code
number or direct control using English commands. These
operations were sent to the DATA 6000 as string commands and
data transfers to the computer were sent in ASCII number
format. Various timing loops set up in the BASIC program
assured proper hand-shaking. During operation several
parameters such as trigger source, timebase, screen display
and marking were initially set manually and subsequently
controlled remotely through the computer program. For
short-lived transient signals, the multiple trace delayed
mode with signal averaging was used which provides an en¬
hancement to the S/N ratio in proportion to the square root
of the number, n, of signals averaged.118 Otherwise, the
single trace delay mode was used with no signal averaging.
As shown in Figure 2, the triggering and delays were
originated from a single initial manual trigger pendant
delivering a 90 volt pulse derived from three 30 volt bat¬
teries in series with a standard RC trigger circuit. A
typical timing sequence is presented in Figure 19. Delay of
the Febetron firing was accomplished using an Evans Associ¬
ates programmable time delay (PTD) module, Model 4145-2.
Three such modules are present which could be used in series

0%T
light
intensity
100%T
TRANSIENT
ABSORPTION DYNAMICS
FEB
LAMP
VAR.
TRIG
AMPLITUDE (volts)
TIME SCALE DELAY
TRIG
90
nSec
LAMP
^•1
< 1 Sec
FEB
90
3 nSec 0 -- 100 uSec
TDR
+/- 1.2, +/- 3.6
10 uSec - 1 mSec
Fig. 19. Timing sequence for pulse radiolysis experiment.

63
for a maximum delay of 3 milliseconds. The voltage divider
and amplifier in the circuit are required because the incom¬
ing trigger for the Febetron must be 90 volts in magnitude
while the PTD uses a TTL type input and output. The lamp
pulsing and shutter control was provided by a Vincent Asso¬
ciates shutter driver and timing unit, Model SD 10, which
controlled a Model 225L Vincent Associates UNIBLITZ shutter.
The shutter was not incorporated into the timing sequence
but was manually switched on and off during a calibration
procedure to set the zero and full light levels, VQ and Vm
respectively. The lamp pulse duration was controlled by the
shutter driver and timing unit which provides a positive
going 5 volt square pulse with a variable 8 to 8,000 milli¬
second duration.
2.8 Computer Program
Full interaction between the operator and the
computer/transient recorder was provided by a single BASIC
program. This program, developed by J. Brogdon and R. J.
Hanrahan with assistance from B. Yarborough and Brent Jones,
was locally written in accordance with suggested BASIC rou¬
tines provided by the DATA 6000 manufacturer.135 A complete
listing is provided in Appendix C. The BASIC source code
was compiled from the RUN menu of Microsoft Quick BASIC
version 4.0, and was executed directly from memory or from a
separate executable program written to disk.

64
Initially, the opening menu would offer all options
available, and upon full completion of any commands the main
menu would again be presented. Prior to data collection the
CALIBRATION command was used to set all data recording
parameters and to provide a dark or no light trace, VO, and
a full light trace, VM. The DATA command was entered during
collection, storage, and averaging of actual traces by the
DATA 6000. Upon completion of this loop three files were
stored into computer memory: all digitized voltage values
(QY(I)), a time dependent concentration file [QX(I),
CON(I)], and a time dependent optical density file [QX(I),
OD(I)]. After transfer of the data from the digitizer to
the computer, the SAVE command could be executed to save a
disk copy of the digitized voltage values. Using the PLOT¬
TER command provided a graphical presentation of the digi¬
tized voltage optical trace on the computer CRT screen.
Often hard copy of the graphical displays would be obtained
to catalog the data.
The subroutine at line 1570 (LEFT & RIGHT BORDERS)
allowed for selection of any portion of the trace followed
by storage of either a concentration or optical density file
corresponding to the section of the trace within the bor¬
ders. The subroutine at line 3980 (LINEAR REGRESSIONS)
provided linear least sguares analysis of the concentration
data to aid in determining the kinetics involved in the
transient decays. Operation of the MANUAL command enables

65
adjustment for the true full light signal, VM. Even though
the 100% light signal was set during the calibration steps,
any fluctuation in the light during the actual data collec¬
tion mode could be accounted for by taking an average of the
light signal immediately preceding the pulse as an accurate
measure of the true 100% light intensity. Selection of the
molar absorption coefficient, E, which was dependent on the
specific transient being observed was also done through the
MANUAL command. The DIRECTORY command provided directory
inspection to insure the storage of all files to disk and to
access available memory.
2.9 Reagents and Sample Preparation
2.9.1 Sodium Tetraphenylborate and Sodium Azide
Kodak reagent-grade sodium tetraphenylborate and sodium
azide were used as received.
2.9.2 IrCl63"(hydrate) and IrCl62-
The sodium hexachloroiridate(III) hydrate and sodium
hexachloridate(IV) complexes, which were obtained from Al¬
drich Chemical Company, were stored in a dessicator and used
without purification.
2.9.3 Sodium Carbonate
Fisher Scientific Company-supplied Na2C03 was used in
all the carbonate competition experiments.

66
2.9.4 Sodium Hydroxide and Ethanol
Fisher Scientific Company-supplied NaOH and USP reagent
quality 200 proof absolute CH3CH2OH from Florida Distillers
Company were used in the hydrated electron dosimetry stud¬
ies .
2.9.5 Sulfuric Acid and Ferrous Ammonium Sulfate
Fisher Scientific Company H2S04 and Fe(NH4)2(S04)2*6H20
were used as received for the Fricke dosimetry studies.
2.9.6 Potassium Thiocyanate
Fisher Scientific Company KSCN was used as received for
the thiocyanate dosimetry studies.
2.9.7 Tert-Butyl Alcohol
Fisher Scientific Company reagent-grade (CH3)3COH was
used as received for the hydrated electron rate-constant
studies.
2.9.8 Potassium Permanganate
Fisher Scientific Company reagent-grade KMN04 and NaOH
were used as received for the water distillation procedure.
KMN04 solid was dissolved in laboratory-distilled water that
was made alkaline by addition of NaOH. Upon distillation,
any organic impurities were removed by an oxidation reaction
involving the Mn04“ ion.

67
2.9.9 Oxygen and Nitrogen
Liquid Air Corporation-supplied 02 and N2, both of
which were > 98% purity, were used as received for purging
gases in the 'Super' Fricke studies and the hydrated elec¬
tron studies, respectively.
2.9.10 Nitrous Oxide
Matheson CP-grade N20 with > 99.0% purity was used as
received for generating oxidizing conditions for all studies
involving the OH* radical reactions.
2.9.11 Sample Preparation
Aqueous solutions were prepared by dissolving known
amounts of solid reagents in doubly distilled water. A
Model B5 Mettler analytical balance with 200 gram capacity
and +/- 0.05 milligram accuracy was used in all mass meas¬
urements. Reference spectra of the Iridium(III) chloride
complex, Iridium(IV) chloride complex, and the Sodium Tetra-
phenylborate solution were measured using a Hewlett-Packard
model 2400 UV/VIS spectrophotometer.
2.10 Sample Irradiation
Prior to radiolysis, solutions which were to be irradi¬
ated under oxidizing conditions were purged for approximate¬
ly thirty minutes with nitrous oxide, N20. For work in-

68
volving reducing conditions, nitrogen, N2, was used as the
purge gas. Purging of the solutions was done by introducing
a disposable pipette directly into the 60 milliliter separa¬
tory funnel serving as the upper reservoir of the solution
flow cell. Gas flow was maintained throughout the pulse
experiments. Prior to calibrating the DATA 6000, the solu¬
tion was introduced by gravity flow into the modified cu¬
vette, which was then inserted into the aluminum cell hold¬
er. The cell holder was designed to accommodate the solu¬
tion cell to give reproducible positioning and uniform
irradiation in the region that was sampled by the analyzing
light beam. After completing the calibration procedure, the
data collection routine was executed and the Febetron was
charged and triggered. Typically, due to product buildup or
gas bubble evolution on the inner surface of the electron
beam entrance window, a fresh aliguot was flushed into the
cell and the system was recalibrated after each pulse.

CHAPTER III
THE PULSE RADIOLYSIS OF
SODIUM TETRAPHENYLBORATE IN AQUEOUS SOLUTION
3.1 Experimental Results
3.1.1 Oxidation Intermediates of Tetraphenylborate Ions
The pulse radiolysis of aqueous sodium tetraphenylbo¬
rate (TBP) solutions under oxidizing conditions was studied
with two different methods of generating the oxidizing
species. As mentioned previously, using N20-saturated
solutions the predominant oxidant produced is the OH* radi¬
cal generated from the direct radiolysis of water and the
interconversion of eag~ to OH* by N20. Alternatively, a
secondary oxidant, N3*, is prepared under conditions of N20-
saturation and the addition of excess sodium azide, NaN3.
The azidyl radical, N3 • , is formed from the oxidation of the
azide anion by the OH* radical,
OH* + N3" —> OH- + N3* III-l
Both the N3“ anion and N3* radical have absorption maxima at
wavelengths < 280 nm.136 Experiments with N3* radical were
carried out to utilize the selective electron transfer path¬
way of oxidation as compared to other possible reactions of
the OH* radical with aromatic systems, namely abstraction of
an H atom and addition of the OH* radical to the aromatic
ring.
69

70
The pulse radiolysis of a nitrous oxide-saturated (N20
a 2.4 x 10-2 M) solution of 10 mM NaTPB was carried out at
room temperature. Using the Xenon arc lamp in the pulsing
mode, the transient absorption signals were recorded at
various wavelengths from 300 to 800 nm. Figure 20 shows the
absorption signal recorded at 330 nm for a single pulse
experiment. The appearance of an incipient secondary ab¬
sorption occurring approximately 20 to 30 microseconds after
the initiating e-beam pulse was characteristic in all the
time-concentration traces recorded in the 300-400 nm range.
A transient absorption spectrum, Figure 21, was gener¬
ated by plotting the maximum absorption or "end of pulse"
values as a function of the wavelength at which they were
recorded. This spectrum shows an absorption maximum at 330
nm; the only other transient spectral feature is a small
absorption (ca. 10% of the main peak) centered at about 750
nm. This spectrum is to be compared with that reported by
Liu et al. for the radical derived by OH* addition to the
phenyl groups of TPB- — a spectrum with a large absorption
at 300 nm that was reported to change only slightly over the
first few microseconds.76
Assuming the absorption at 330 nm is caused by the
radical derived by the addition of OH* to the phenyl groups
of TPB-, its extinction coefficient at the absorption maxi¬
mum of 330 nm can be calculated from the transient spectra
shown in Figure 21 (a) by making use of the value for G(0H)
in N20-saturated solutions egual to 5.4 (= G(OH) + G(eaq-).

71
MULT. X-AXIS BV 0.10E-03 Sec. V-AXIS BY 0.10E+01 Units. SOURCE:TPB330.1
? I
Fig. 20. Graphical displays of optical signal versus time
following pulse radiolysis of N20-saturated 10 mM
NaTPB solution. a) recorded at 330 nm, 200 nsec
period, 100 usee full scale; b) recorded at 345
nm, 500 nsec period, 250 usee full scale.

Absorbance
300 400 500 600 700 800
Wavelength / nm
Fig. 21. Transient absorption spectra for:
a) ^O-saturated 10 mM NaTPB
b) ^O-saturated 10 mM NaTPB, 0.2 M NaN^
NJ

73
In N20-saturated TPB- solutions, this total OH* yield of 5.4
will have been completely converted to the TPBOH-* radical
by the time optical measurements can be made. Thus the end
of pulse optical density can be used to measure the extinc¬
tion coefficient of the TPBOH-* adduct. The value obtained
from Figure 21 is approximately (10,000 +/- 10%) M-1cm-1 for
the maximum peak at 330 nm.
The optical densities were calculated from the initial
pre-pulse light intensity determined during calibration, Vf,•
and from the transmitted optical signal, Vt, using the
eguation
OD = -log (Vt / Vf) = -log[ (QY(I) - VQ) / Vf) ] III-2
Vf is obtained from subtracting the dark signal, VQ, from
the initial 100% light intensity, Vm, determined under the
experimental conditions prior to irradiation and V^. is ob¬
tained from subtracting VQ from the digitized optical sig¬
nal , QY(I).
The pulse radiolysis of a N20-saturated solution of 10
mM NaTPB , with excess NaN3 « 0.2 M, was carried out at
various wavelengths yielding typical absorption traces, as
shown in Figure 22. The accompanying transient absorption
spectrum is plotted in Figure 21. The transient absorption
traces resulting from the NaTPB with added NaN3 conditions
also illustrate a secondary transient production. The

74
MULT. X-AXIS BV 0.10E-03 Sec. V-AXIS BÂ¥ 0.10E+01 Units. SOURCE:TPBN3.13
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0.8
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Fig. 22. Graphical display of optical signal versus time
following pulse radiolysis of ^O-saturated 10 mM
NaTPB, 0.2 M NaN^ solution. a) recorded at 330
nm, 200 nsec period, 100 usee full scale; b)
recorded at 330 nm, 500 nsec period, 250 usee full
scale.

75
transient absorption spectrum contains two absorption bands,
one at 330 nm and a broad band above 700 nm. This transient
absorption spectrum as well as the associated kinetics of
the 330 nm decay are in good agreement with published re¬
sults obtained under similar solution conditions.75'76
3.1.2 Transient Kinetics
Kinetic analysis of the optical traces was carried out
using a curve fitting routine from the BASIC program, and
the best fit was judged from the correlation coefficient and
visual inspection. Figures 23 and 24 show typical curve
fits for both the initial and secondary transients produced
under N20-saturated millimolar NaTPB conditions. Analogous
curve fitting was carried out on the experimental absorption
traces obtained from N20-saturated solutions of NaTPB con¬
taining excess NaN3. The resulting decay rate constants are
presented in Table 2.
3.1.3 Carbonate Competition Method
The reaction of OH* radicals with the TPB- anion occurs
too rapidly to be observed directly using the experimental
conditions previously described. However, the formation
rate of the OH* radical reaction with TPB- can be obtained
by the carbonate competition method137 using a secondary
scavenger, C032-, which competes with the TPB- anion for the
OH* radical. The two competing reactions are

76
MULT. X-AXIS BV 8.10E-03 Sec. Y-AXIS BY 0.10E+01 Units. SOURCE:TPB330.1
? I
WOULD YOU LIKE TO LEAST SQUARES FIT DATA ON GRAPH
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WOULD YOU LIKE TO LEAST SQUARES FIT DATA ON GRAPH
INTCPT: 2.16E+01 (STD DEV: 1.27E-02) SLOPE: 6.94E+04 (STD DEV: 4.26E+02)
R= .9983794 E= 10000 STD DEV PIS: 2.020695E-02
Fig. 23. Curve fit of data; a) transient trace presented
from Figure 20 (a); b) First-order fitting routine
applied to data between x = 20 and x = 40 micro¬
seconds .

77
MULT, X-AXIS BV 0.10E-03 Sec. Y-AXIS BV 0.10E+01 Units. SOURCE:TPB345.3
INTCPT=-5.18E+03 (STD DEV: 4.49E+02) SLOPE: 3.63E+08 (STD DEV: 2.66E+06)
R: .9912943 E= 3080 STD DEV PTS: 2308.339
Curve fit of data; a) transient trace presented
from Figure 20 (b); b) Second-order fitting rou¬
tine applied to data between x = 80 and x = 250
microseconds.
Fig. 24.

78
Table 2
Transient Decay Rate Constants
N20-saturated
Initial Transient
Secondary Transient
Solutions
Decay Rate Constant
Decay Rate Constant
( x 104 sec-1 )
( x 108 M-1sec-1 )
10 mM NaTPB
5.88 ± 0.98
3.76 ± 0.42
10 mM NaTPB
8.25 ± 0.59
3.10 ± 0.91
0.2 M NaN3
a) 2
a) 4
b) 3.9 ± 0.2
b) —
a) reported
by
Horii and Taniguchi
b) reported
by
Liu et al.

OH* + TPB
—>
79
products , k-^
OH* + C032- > OH- + CO3- (detected)
III-3
k2 130
Using the He-Ne laser experimental setup, the CO3- radical
anion was monitored as a function of added TPB- anion. The
CO3- radical anion has an extinction coefficient on the
order of 1000 M-1 cm-1, a known formation rate constant of
4.1 x 108 M-1 s-1, and a broad absorption band centered on
600-610 nm.128 The equation representing the competition is
Cco3 Unf. “
k2[c°32 ]
X [OH•]Q III-4
k2[C032-] + k1[TPB“]
with [co3~]inf = end of pulse concentration of 003” ion
[0H*]o = initial concentration of OH* (includes
primary OH' from water radiolysis and
from interconversion of eag- by N20)
Taking [0H*]o as equivalent to the [co3_]inf generated with
no TPB- present, or [C03~]o, equation III-4 can be rear¬
ranged to
[C03"]o kx[TPB- ]
= 1 +
[co3~Unf. k2[C032-]
III-5
From a plot of [C03-]o / [C03-]^nf# versus [TPB-] / [CO32-],
as shown in Figure 25, k1/k2 is found to be 15. Substitu¬
tion of k2, the CO3- reference formation rate constant gives
a rate constant for the formation (reaction III-3 above) of
the initial transient = (6.2 ± 0.6) x 109 M-1sec-1.

30
Fig. 25. Carbonate competition experiment for determining
the OH + TPB- rate constant.

81
Radical formation rate constants for TPB* equal to 1.4 x 109
M-1s-1 and 7.1 x 108 M-1 s-1 have been reported for the
electron transfer reaction involving TPB- and N3*.75,76
3.1.4 Reduction Intermediates of Tetraphenylborate Ions
Pulse radiolysis experiments were performed using
reducing conditions to examine the possibility of a rapid
reaction between the TPB- ion and eaq-. Because the TPB-
anion is a strong reducing agent and negatively charged,
this reaction was presumed unlikely. However, by monitoring
the eaq- transient signal as a function of added TPB- any
such reaction would be evinced by either a decrease in the
magnitude of the end of pulse eaq- transient absorption or a
change in the eaq- transient decay kinetics. A typical
transient trace of the pulse experiments conducted on ap¬
proximately 10 mM NaTPB solutions under reducing conditions
is shown in Figure 26. The life-time of the eaq- transient
was found to be approximately 8-10 microseconds with a best
fit analysis giving a second order decay rate constant of
5.7 x 1010 M-1s-1.
3.1.5 Computer Simulation
Modeling calculations were utilized to help establish
the detailed chemical mechanism of multi-step reactions
found in aqueous pulse radiolysis systems. Differential
rate equations for the suspected reaction sequence are

82
-0.5
-1.0
-1.5
-2.0
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MULT. X-AXIS BY 0.10E-04 Sec. Y-AXIS BY 0.10E+01 Units. SOURCE:TPBEAQ38
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FCns;2¿24E+0S (HILBEV= 2.85E+03) SLOPE: 5.74E+10 (SID DEU: 5.63E+08)
R: .9901459 E: 14860 SID DEU PTS: 9860.368
Fig. 26. a) Graphical display of optical signal versus time
following pulse radiolysis of an N2_saturated 10
mM NaTPB, 0.04 M t-butanol solution; 20 nsec
period, 10 usee full scale; b) Curve fit of data
between x = 3 and x = 7 microseconds.

83
integrated to give computer-simulated time-dependent concen¬
tration profiles that are compared with those measured
experimentally. These comparisons help to establish, or
validate, proposed mechanisms. The computer modeling was
done using a Gear integrator program.139 This program,
written by R. L. Brown140 of NIST, was modified in this
laboratory to run under Microsoft FORTRAN 77 on an MS-DOS-
based microcomputer.
The input parameters to the program consist of a list¬
ing of all mechanistic steps and their rate constants (see
Appendix B), the identification of all reactants with their
initial concentrations, and the time-step which controls the
50 computation intervals.
3.2 Discussion
3.2.1 Electron Transfer
The oxidation intermediates of TPB- ions in aqueous
solutions have been examined by Horii and Taniguchi,75 and
Liu et al.. From their results with N20-saturated solu¬
tions of NaTPB and NaN3, the proposed route to the formation
of several major products is a rapid electron transfer from
B(C6H5)4- to N3- yielding the B(C6H5)4‘ radical and N3~, or
B (C6H5 ) 4~ + N3* > B(C6H5)4- + N3- HI-6
As shown earlier the azidyl radical, N3•, is produced ini¬
tially from primary OH radical reaction with N3“, reaction

84
III-l. The transient absorbing at 330 nm and 800 nm (Figure
21) is attributed to the B(C6H5)4* radical. Both peaks
decay with the same first-order rate constant, indicating
that they represent different absorbances of the same tran-
sient species.'a Loss of the 330 nm peak is attributed to a
rapid self-decomposition first-order decay, producing a
second transient that undergoes a relatively slower decay.
Horii and Taniguchi proposed the reaction,75
B (C6H5 ) 4 * > B(C6H5)2‘ + (C6H5)2 111-7
The secondarily-produced transient B(C6H5)2* was suggested
to disappear following second-order kinetics, although no
product species were discussed.75
The pulse results from our oxidation experiments on TPB
solutions containing no added N3- anion could be interpreted
as above, i.e. a rapid electron transfer from B(C6H5)4“ to
OH*, instead of N3*, or
B (C6H5 ) 4~ + 0H’ > b(C6H5V + 0H" 111-8
yielding the B(C6H5)4* radical. As shown in Table 2, the
decay kinetics of the transients produced with and without
added N3“ are similar, that is a rapid, first-order decay
followed by a secondary transient decay. However, compari¬
son of the transient spectra, Figure 21, suggests that two
different transients are formed. With added azide, the
transient spectral feature at 750 - 800 nm is about 70% of

85
the magnitude of the main peak centered at 330 nm. With no
added azide, the transient spectral feature at 750 - 800 nm
is < 10% of the magnitude of the main peak centered at 330
nm.
3.2.2 OH Addition
An alternate mechanism to the electron transfer from
TPB- to OH’, as described above, is the addition of the OH-
radical to the aromatic ring, which would lead to an OH*
adduct transient species different from the TPB» radical, or
B(C6H5)4~ + 0H' > (C6H5)3BC6H5OH‘~ 301
The following self-decomposition first-order decay
scheme has been considered for the observed loss of this OH-
addition adduct.
(C6H5)3BC6H5OH-_ > B(C6H5)3 + C6H5OH-" 302
C6H50H-- + H20 > C6H6OH- + OH" 303
Triphenylborate and its hydrolysis products, (C6H5)B(OH)2
and (C5H5)2BOH, all have absorptions at wavelengths below
300 nm.74 The secondarily-produced transient C6H5OH--, is
suggested to undergo a rapid hydrolysis, yielding the hy-
droxycyclohexadienyl radical C6H6OH*. The hydrolysis of
C6H50H-- has been reported in a previous agueous phenol
pulse radiolysis study.141 In neutral solutions a slow
reaction between the solvated electron, eag~, and phenol

86
that forms C6H5OH“‘ was reported. The radical anion,
C6H5OH-’, subsequently undergoes rapid protonation by H20 to
yield (C6H5)(OH)H*. This species is a structural isomer of
the hydroxycyclohexadienyl radical, C6H6OH*. A molar ex¬
tinction coefficient of (3800 +/- 800) M-1 cm-1 at a wave¬
length maximum of 330 nm was assigned to the (C6H5)(OH)H*
radical.
Another possible competing reaction pathway for the
C6H5OH*“ radical anion would be a bimolecular radical anion
reaction. The bimolecular disappearance of negatively
charged radical species has been previously suggested in
pulse radiolysis studies involving the reaction of the
hydrated electron, eag“, with benzene.58 In this aqueous
benzene study, C6H6“, the addition product of eag- and
benzene, was reported to decay via a rapid bimolecular proc¬
ess before protonation in solutions of pH neutral to 13.
C6H6 + eaq" > C6H6~ I^"9
C6H6~ + C6H6~ > Products III-10
No specific products of the radical anion reaction, III-10,
were discussed.
In the present study, concerning the combination reac¬
tion of C6H5OH*~, a possible reaction forming a charged
dimer species, with subsequent formation of biphenyl and
hydroxide ion, is proposed below
C6H5OH‘" + C6H5OH-“ > [HO(C6H5)-(C6H5)OH]2- 304
[HO(C6H5)-(C6H5)OH]2~ > C6H5-C6H5 + 2 OH- 305

87
The scheme involving radical combination leading to an
intermediate dimer is prominent in the mechanism involving
the radiolysis of agueous benzene, discussed below.
The hydroxycyclohexadienyl radical, C6H6OH-, mentioned
above (reaction 303), is an important intermediate in the
formation of major products in the radiolysis of agueous
benzene solutions; the results of which are in good agree¬
ment with the end products derived from Co-60 steady-state
T-radiolysis of NaTPB solutions carried out in this lab.86
The proposed mechanism concerning the benzene
oxidation55'64,65 is described as
C6H6 + OH- > C6H6OH- III-9
2 C6H6OH- > [HO(C6H6)-(C6H6)OH] 306
[HO(C6H6)-(C6H6)OH] > C6H5-C6H5 + 2H20 307
2 C6H60H- > C6H6 + C6H5OH + H20 308
The hydroxycyclohexadienyl radical, C6H6OH*, has a reported
absorption maxima at 313 nm.58 The combined bimolecular
rate constant for its disappearance via reactions 306 and
308 has been determined to be (7.05 ± 0.35) x 108 M_1s-1.58
The disproportionation to combination ratio for the disap¬
pearance of C6H6OH* was found to be < 0.4, indicating that
the combination reaction 306 is predominant.63 The major
products produced are biphenyl, benzene and phenol. In the
Co-60 r-radiolysis of aerated 0.05 M sodium tetraphenylbo-
rate solutions the products and their G-values were found to
be biphenyl, 1.9; benzene, 1.3; and phenol, 0.41.68

88
It is also reasonable to expect the H* atom to add to TPB"
ion, giving a transient species that decomposes via a two-
step process giving the cyclohexadienyl radical
B(C6H5)4~ + H* > (C6H5)3BC6H6T 309
(C6H5)3BC6H67 > B(C6H5)3 + C6H6T 310
C6H6~ + H20 > C6H7. + OH" 311
The (C6H5)3BC6H6~ transient has been proposed by Liu et al.
as the weakly absorbing species at higher wavelengths
(Figure 21) in the pulse radiolysis of TPB- solutions with¬
out added azide.76 The cyclohexadienyl radical could also
react with the hydroxycyclohexadienyl radical in a bimolecu-
lar process producing benzene56
C6H?. + C6H6OH* > 2 C6H6 + H20 312
Concerning the reduction of TPB", a rapid reaction
between eag~ and TPB" appears to be negligible from the
results of the NaTPB pulse radiolysis under reducing condi¬
tions. Comparison of Figure 26 with eag~ traces found in
the hydrated electron dosimetry experiments, Appendix A,
shows little difference in either the magnitude or kinetic
behavior of the eag“ transient signal. The eag~ transient
signal decayed with a second order rate constant of 5.7 x
1010 M~1s~1 with added TPB"; for the eag" dosimetry experi¬
ments, the eag" signal exhibited a second-order decay = 4.4
x 1010 M"1s"1.

89
3.2.3 Computer Simulations
Computer simulations were carried out with a Gear
integrator utilizing the data set consisting of the elemen¬
tary reaction steps describing the transients of irradiated
pure water (Appendix B). The mechanistic scheme also in¬
cludes reactions of eag~ with N20, and OH' with TPB-.
Figure 27 illustrates typical results of the simulated
calculations for conditions involving N20-saturated solu¬
tions containing 10 mM TPB-. Time-concentration profiles
for all species in the system are predicted over the ca. 200
microsecond data collection time period. Experimental data
points indicate the observed decay of the transient trace
produced in a typical experimental run, recorded at 330 nm
(Figure 20 (b)). These experimental data points represent
the combined absorbance of all the components in the system
contributing to the absorption trace at 330 nm. Dotted
lines show predicted yields of the various individual tran¬
sients formed. The solid line represents the combined
concentrations of the following intermediates; the initial
OH* adduct (C6h5)3bc6h5ohT with a molar extinction coeffi¬
cient of 10,000 M-1 cm-1, the radical anion C6H5OHT and the
hydroxycyclohexadienyl radical C6H6OH* with molar extinction
coefficients of 3800 M-1cm-1, and the intermediate dimers,
[HO(C6H6)-(C6H6)OH] and [HO(C6H5)-(C6H5)OH]2- with molar
extinction coeffiecients of 7,500 M-1cm-1.

90
Fig. 27. Comparison of experimental and computer-simulated
transient concentrations versus time plots during
the pulse radiolysis of a 10 mM NaTPB solution;
(—) summation of individual transients;
(’) typical experimental results;
( ) computed individual transient traces.

91
3.3 Conclusions
Results obtained in this work lead to the conclusion
that the identity of the transient species, absorbing upon
pulse radiolysis of N20-saturated NaTPB solutions, is very
much dependent on the nature of the oxidizing species pro¬
duced in the system. The aqueous azide NaTPB solution
experiments presented here, taken together with the results
of others,75'76 indicate that the one electron oxidation
product of TPB-, the TPB* radical, is the species that
absorbs at 330 and 775 nm.
However, experiments in aqueous NaTPB solutions without
added azide indicate formation of a different transient
species, proposed to be the OH* adduct of TPB-, or
(C6H5)3B(C6H5)OHt. This OH* addition product exhibits a
strong absorption at 330 nm. A weak absorption at 750 nm
constitutes approximately 10% of the magnitude of the main
330 nm peak. As mentioned earlier, this weak absorbance
could be due to the H* addition product of TPB-, since the
addition of H* to aromatic systems with resonating 7r-bond
systems has been observed. Alternatively, the weak 750 nm
absorption could be indicative of the TPB* radical product
formation, which would indicate that the one electron trans¬
fer mechanism occurs to a small extent in the N20-saturated
TPB solutions without added azide.
The present study provides information regarding the
fate of the TPB0Ht adduct immediately following its forma-

92
tion, whereas the previous account mentioned only alluded to
the TPBOHt adduct transient absorption spectrum.76 Kinetic
analysis of this transient species indicates that it under¬
goes a rapid first-order disappearance within the first 20
microseconds that is suggested to be a self-decomposition.
It is presumed that this initial transient loss leads to the
observed secondary absorption, which was found to decay on a
longer timescale by second order decay kinetics.
A primary interest in this work was to establish a
plausible reaction mechanism involving the radiolysis of TPB
solutions. Evidence obtained from the pulse radiolysis
experiments has lead to the formulation of a scheme that can
explain the production of various organic products such as
biphenyl, benzene, and phenol, reported from previous
steady-state radiolysis studies on agueous aerated TPB
solutions sealed from the atmosphere.68 For further valida¬
tion of the mechanism presented in this study for the pulse
radiolysis conditions, one could perform numerical integra¬
tion of the scheme for both the pulse and steady-state
radiolysis systems under equivalent solution conditions.
Initial attempts to carry out this work have been
encouraging.

CHAPTER IV
THE PULSE RADIOLYSIS OF IRIDIUM HEXACHLOROIRIDATE
IN AQUEOUS SOLUTION
4.1Results
4.1.1 Absorption Spectra
Initial experiments performed with the IrCl63- and
IrCl62- ions involved measurement of the aqueous solution
absorption spectra of these complexes. These absorption
spectra, Figure 28, of millimolar aqueous solutions of the
IrCl63- and IrCl62- complex ions were in agreement with the
results of other authors.111'142 Between 400 and 500 nm,
9— . • •
IrClg has a characteristic spectrum with an absorption
maximum at 488 nm (extinction coefficient ca. 4000). In
contrast, the IrCl63- complex has no appreciable absorption
in this wavelength range. Thus all pulse absorption data
were recorded at 488 nm.
4.1.2 N20-Saturated Iridium(III) Solutions
The reaction of OH« radicals with IrCl63- occurs too
rapidly to be observed directly under our experimental
kconditions. A method involving competition kinetics, the
carbonate competition method described earlier, was used to
determine the rate constant for the reaction
OH• + IrCl63- = OH- + IrCl62“ 201
93

ABSORBANCE
WAVELENGTH (na)
Fig. 28. UV-VIS spectra of:
a) 1 mM IrClg^ ; b) 0.5 mM IrClg^
VO
65C

95
A series of experiments was performed using N20-
saturated solutions containing, typically, 1 x 10“3 M
IrCl63- and various amounts of C032- from 2 to 14 x 10-3M.
Under these conditions the hydrated electron, eag~, is
converted to OH*. The equations representing the competi¬
tion are
OH* + C032- > OH" + C03" 130
OH* + IrCl63- > OH" + IrCl62" 201
The end-of-pulse Ir(IV) absorption, Ir(IV)Q, was first
monitored for a millimolar solution of Ir(III) to obtain the
maximum Ir(IV) produced, i.e. without any added C032-. The
end-of-pulse Ir(IV) absorption, Ir(IV)^nf , was then ob¬
tained for a series of solutions with added C032". A plot,
Figure 29, of [Ir(IV)Q]/[Ir(IV)^nf.] versus the added C032-
concentration yields a slope, k130/(k20i[Ir(III)]), equal to
85 M"1. Substitution of the Ir(III) concentration of 1
mM and k130 = 4.1 x 108 into the slope expression above
gives a rate constant for reaction 130 above, equal to (4.9
± 0.6) x 109 Broszkiewicz measured a somewhat
higher value of 8.9 x 109 M~1s"-1- for this reaction. 3-
However, the lower value gives satisfactory results in the
computer simulation studies.
In all the experiments on the pulse radiolysis of C032-
/IrCl63- solutions, using concentrations of IrCl63" of 1 x
10“3 M and concentrations of C032" from 2 to 14 x 10"3 M,

(lr(IV))0 / (Ir(IV)) jnf
96
Fig. 29. Carbonate competition experiment for the determi¬
nation of the OH + Ir(IV) rate constant.

97
the product, IrCl62-, disappears rather rapidly as shown
in Figure 30 (a). If the decay is fitted as a simple sec¬
ond-order process in IrCl62-, an apparent rate constant of 4
x 107 M-1s-1 is obtained. However, loss of the Ir(IV) via a
bimolecular disproportionation reaction is not reasonable
mechanistically. An interpretation of the cause of the
decay of the IrCl62- optical signal in these experiments is
discussed below. Interestingly, as seen in Figure 30 (b),
the product iridium (IV) complex is almost inert, or stable
over approximately 400 microseconds, when the experiment is
performed with added N20 using a neutral medium, i.e. with
no added NaOH or Na2C03.
4.1.3 Nitrogen and Air-saturated IríIII^ Solutions
Experiments were performed on the pulse radiolysis of
both nitrogen and air-saturated Ir(III) aqueous solutions to
further investigate the reactivity of the Ir(IV) species.
Using N2-saturated solutions, roughly equal amounts of the
reducing and oxidizing species, eag“ and OH* respectively,
are produced. The N2~saturation purges all dissolved atmos¬
pheric oxygen, an efficient electron scavenger, from the
solution, thus eliminating the reaction
eaq" + °2 > °2~ 113
In the pulse radiolysis of air-saturated solutions, which
contain 02 at 0.25 mM, the superoxide anion, 02“, plays an
important role40 due to its formation from the reaction

98
Graphical display of IrCl62- optical signal versus
time following pulse radiolysis of N20-saturated
solutions of (a) 1 mM IrCl63- and 5 mM C032-; (b)
1 mM IrClg-.
Fig. 30.

99
above, and the reaction
H + 02 > H02
117
With a pK of 4.88 for H02, 02“ is the predominant species
above pH = 5. The perhydroxyl radical, H02', or 02" in
basic media, can act as an oxidizing or reducing agent
depending on the solute present.
The transient Ir(IV) oxidation product was found to be
unstable in both N2~ and air-saturated solutions, as shown
in Figure 31. The spectra of Ir(IV) disappeared rapidly in
the N2~saturated solutions with a second-order rate constant
of 5 x 108 M-1s-1 and moderately rapid with a second-order
rate constant of 1 x 107 in the case of air-saturated solu¬
tions. These rate constants establish the time-scale of the
phenomena. Additionally, since concentrations of the oxi¬
dizing and reducing reactants (originating from OH and eaq“
respectively) are expected to be nearly equivalent, the rate
constants should correctly describe the actual reactions.
4.1.4 Reduction of Ir(III)
The rate constant for the reduction of the IrCl63-
complex
IrCl63" + eaq
202
was obtained by applying pseudo-first-order kinetics.
Formation of the hydrated electron in water was observed

100
Fig. 31. Graphical display of IrCl62- optical signal versus
time following pulse radiolysis of neutral 1 mM
IrCl63- solutions saturated with (a) N2; (b)
air.

101
using a 50 MHz sampling rate with our transient digitizer
and its decay was followed at 632.8 nm. The rate expression
for reaction 202 above is
-d[eaq']/dt = k2Q2 [Ir(III)] [eaq-] IV-1
By making the concentration of Ir(III) high compared to the
expected concentration of eaq-, k202 [Ir(III)] is treated
as a constant and the rate expression reduces to
“dteaq~]/dt = r/ teaq~] IV-2
where k* = k202 [Ir(III)]. Expression IV-2 is a first-order
rate expression. The first-order decay rate constant for
e_ k', was determined using the appropriate fit routine
in the BASIC data analysis program found in Appendix C.
These first-order rate constants for the eaq~ decay were
determined and plotted versus the concentration of added
Ir(III) complex, Figure 32. The nitrogen-saturated solu¬
tions were made 0.1 M in t-Butanol to remove OH* radicals.
The value for the rate constant corresponding to reaction
202 above was found to be (6.1 ± 0.3) x 109 M-1s-1.
4.2 Discussion
The results presented above agree in general respects
with those of Broszkiewicz; OH* radicals react rapidly with
IrCl63- to produce the (IV) oxidation state of iridium via
reaction 201 (Table 5). Our measured rate constant is

k(obsd.) , 1/Sec
1.6x10
6
15x10
6
1.4x 10
6
1.3 X 10
6
12X10
6
2 3 4 5 6 7 8
[Ir(lll)] x 105 , M
Fig. 32.
Change in first-order decay of the hydrated elec¬
tron with IrCl63- concentration.

103
slower than that seen by Broszkiewicz, as mentioned earlier.
Broszkiewicz also noted that IrCl62- is "stable within the
period of ca. 0.5 ms, though its relative instability, when
compared with solutions of IrCl62- as prepared from solid
salt indicates that radiation produces either an active form
of IrCl62- of higher reactivity towards water, or a system
in which this compound is more readily reduced."111 In
addition, Broszkiewicz reported that IrCl62- is not capable
of being further oxidized by any primary radiolysis product,
but that it is capable of being reduced within a few micro¬
seconds .
In agreement with the earlier work mentioned,111 it
was found that the IrCl62- species is stable when formed in
neutral solutions saturated with N20, which converts eaq- to
OH- radical. In contrast, however, the Ir(IV) complex is
rather short-lived under our circumstances in either of
three conditions: 1) when formed in a neutral N2~saturated
solution, 2) when formed in an air-saturated solution in the
absence of N20 (i.e., with both eag“ and OH* transients
present, and 3) when formed in an alkaline, N20-saturated
solution.
4.2.1 Loss of Iridium ÍIV1 in Nitrogen-Saturated Solutions
As noted in the earlier work,111 iridium (III) is
readily reduced to iridium (II) by either hydrated electrons
via reaction 202 or by hydrogen atoms via reaction 203

104
lrci63- + eaq = IrCl64- 202
IrCl63- + H* = IrCl64- + H+ 203
Our measured rate constant for the reduction of IrCl63- by
reaction 202 is in good agreement with earlier reported
values.110'111
Broszkiewicz suggested that the oxidation state (II)
compound disappears rapidly via disproportionation to
Ir(III) and Ir(I). While no evidence was found contrary
to this possibility, an alternate suggestion is discussed
below. N2~saturated solutions pulse-irradiated in the
absence of N20 contained Ir(II) formed by reactions 202 and
203. In addition, Ir(IV) formed from reaction 201 was
produced under these conditions. Thus it is suggested that
under these circumstances, the most likely route of disap¬
pearance of Ir(II) is an electron transfer involving Ir(IV)
IrCl62- + IrCl64- = 2 IrCl63- 206
Interestingly, this reaction was proposed by Dainton108 in
connection with steady-state radiolysis of iridium (III)
systems at natural pH, as studied by endproduct analysis.
4.2.2 Loss of Iridium CIV'l in Aerated Solutions
Air-saturated solutions showed a similar decay of the
IrCl64- absorption, although to a lesser extent than the N2~
saturated solutions. However, in the aerated solutions

105
millimolar concentrations of dissolved 02 (an effective eag“
scavenger) were in competition with Ir(III) for eag- and H*
atoms. Thus only a portion of the H* atom and eag“ yields
reacted via processes 202 and 203. The superoxide anion,
02“, formed from reactions 113 and 117, can act as either an
oxidant or reductant depending on the solute present. The
IrCl62- complex has a standard reduction potential, E°, =
+1.02 V.143 Thus the 02~ anion, with a standard reduction
potential of -0.33,143 is identified as the reductant of
IrCl62- in the aerated system.
4.2.3 Loss of Iridium (IV) in Basic, N20-Saturated Solutions
As indicated previously, our experimental conditions
differ somewhat from those used by Broszkiewicz in that
there exists a much higher instantaneous concentration of
OH* radicals leading to net formation of H202. As suggested
by Broszkiewicz, there is no obvious method to oxidize the
iridium (IV) compound, but its disappearance by reduction is
a clear possibility. For this disappearance to occur, it is
necessary that some other component in the solution be
oxidizable. After elimination of all other obvious possi¬
bilities, it was concluded that the only plausible reductant
is hydrogen peroxide, or actually the H02“ anion in basic
solution.

106
As noted by several workers,144-146 iridium (IV) chlo¬
ride will ultimately decompose in alkaline aqueous solution,
with formation of hydrated species. However, this process
requires hundreds of hours and is far too slow to be rele¬
vant to our pulse radiolysis conditions. Fine147 reports a
rapid and quantitative reduction of iridium (IV) chloride in
aqueous solutions at pH > 11 as a necessary preliminary step
to any subsequent hydroxylation reactions. In concentrated
alkaline solution and in the absence of other reducinq
agents, a reaction with hydroxide ion was suggested by
Fine147
2 IrCl62- + 2 OH- = 2 IrCl63- + 0.5 02 + H20 IV-3
However, in view of the rate constants reported by Fine,
this reaction is too slow to explain our results obtained at
the pH values of our solutions (pH ca. 10). It was con¬
firmed by simple benchtop experiments that the decay of the
characteristic IrCl62- spectrum in millimolar alkaline
solution is very slow.
Dainton108 proposed that iridium (IV) is capable of
oxidizing hydrogen peroxide according to the net reaction
H202 + 2 IrCl62- = 2 IrCl63- + 02 + 2 H+ IV-4
This reaction has also been mentioned by Waltz and
Adamson.101 However, it was found in the present study that
the reaction of H202 with IrCl62- in neutral solution is

107
only moderately rapid, requiring typically ten to fifteen
minutes to produce a substantial color change in neutral,
millimolar solutions of each reagent.
In contrast with the above observations, it was found
that if millimolar solutions of H202 and IrCl62- were sud¬
denly also made ca. 1 millimolar in OH- by adding three
drops of 0.1 molar NaOH to 20 ml. of solution, the color
change indicating transformation of Ir (IV) to Ir (III) was
essentially instantaneous; that is, the color changed as
rapidly as the solution could be mixed by swirling. These
results suggest that the redox process that causes a de¬
struction of the IrCl62- optical signal in the experiments
mentioned above, involves the peroxide anion
IrCl62~ + H02" = IrCl63- + H02* 208
The peroxide anion, H02~, can act as either an oxidant or
reductant depending on the solute present. As mentioned
earlier, the IrCl62- complex has a standard reduction poten¬
tial, E°, = +1.02 V.142 Thus the H02“ anion, with a stand¬
ard reduction potential of -0.15 V,143 is attributed as the
reductant of IrCl62- for the conditions described above.
The hydroperoxy free radical is consumed by several subse¬
quent processes, in particular
ho2 • + ho2* = h2o2 + o2
111

108
Also, in solutions of pH > 5, H02• is converted into the
reducing species 02~ which could also contribute to the loss
of the IrCl62- optical signal
IrCl62- + 02" = IrCl63- + 02 207
Reaction 208 was confirmed directly by stopped-flow experi¬
ments using a Durrum Model 110 instrument with a Nicolet
digital oscilloscope. A rate constant of approximately 1 x
106 M-1s-1 was found for this process. Since the time
response of the stopped-flow apparatus is limited by a
finite mixing time, this value may represent a lower limit
on the rate constant. Computer simulations of our pulse
radiolysis data indicate a rate constant of 4.7 x 108 M-1
s-1 for this reaction.
4.2.4 Computer Simulations
The consistency of the above postulates has been exam¬
ined by carrying out computer simulations with a Gear inte¬
grator utilizing the data set consisting of the elementary
reaction steps describing transients of irradiated pure
water (Appendix B). The mechanistic scheme also includes
reactions of eag- with N20 and with IrCl63-, and of OH*
radical with IrCl63-, or with C032- (if present).
Figure 33 shows a typical result of the simulation
calculations for conditions involving 5 x 10“3 M carbonate,
2.5 x 10“2 M N20, and 1 x 10~3 M IrCl63-. Experimental data

109
: i ' ~ ! i i i i
0 100 200 300 400
Time, microseconds
Fig. 33.
Comparison of experimental and computer-simulated
IrCl62- concentration versus time plots during the
pulse radiolysis of a N^O-saturated solution con¬
taining 1 mM IrCl63- ana 5 mM Na2C03. (—) comput¬
ed; (•) typical experimental results.

110
. . 9— .
points showing formation and decay of the IrClg transient
in a typical run are indicated. The Gear integrator pre¬
dicts time-concentration behavior of all species in the
system; the figure also illustrates predicted yields of
C03'r, C042-, IrCl62-, IrCl64- and H02~.
Further simulation calculations for conditions involv¬
ing 1 x 10-3 M IrCl63- solutions saturated with air, and
nitrogen are presented in Figures 34 and 35 respectively.
It will be seen that the agreement between measured and
predicted behavior for IrCl62- is reasonable but not perfect
for the various solution conditions.
The results of simulated calculations performed for all
solution conditions mentioned previously are presented in
Figure 36. These concentration-versus-time profiles are to
be compared with the experimental digitized optical traces
of the IrCl62- species shown in Figures 30 and 31.

Ill
1 I I I I I
50 100 150 200
Time, microseconds
Fig. 34. Comparison of experimental and computer-simulated
IrCl62- concentration versus time plots during the
pulse radiolysis of a nitrogen-saturated solution
containing 1 mM IrCl63-. (—) computed; (•)
typical experimental results.

Concentration, micromoles / liter
112
i | i r— 1—— i l_
0 100 200 300 400
Time, microseconds
Fig. 35. Comparison of experimental and computer-simulated
IrCl62- concentration versus time plots during the
pulse radiolysis of an air-saturated solution
containing 1 mM IrCl63-. (—) computed; (•)
typical experimental results.

113
Fig. 36. Computer simulations of the transient IrCl62
trace under various solution conditions.

114
4.3 Conclusions
Aqueous solutions of IrCl63-' and the one-electron
oxidation or reduction products, IrCl62- and IrCl64- respec¬
tively, form a relatively complex reaction system. However,
the method of pulse radiolysis allows for the collection of
some experimental evidence on the early stages of the redox
reactions involved. It is entirely possible there are
further nuances in the chemistry of the iridium complexes
that have not been included at this time. For instance,
several authors have suggested the participation of partial¬
ly hydrolyzed iridium chloride complexes, such as
IrCl5(OH2)“.148-150
Results from this work lead to the following conclu¬
sions. The reported relative stability, i.e. no evidence of
decay for the ca. 500-microsecond period of observation, of
the IrCl62- under neutral N20-saturated conditions was
confirmed. The transient IrCl62- complex formed during the
pulse radiolysis of aqueous millimolar IrCl63- solutions was
found to be unstable under conditions of neutral air satura¬
tion, neutral nitrogen saturation, and alkaline nitrous-
oxide saturation. For each of the solution conditions, an
appropriate species has been identified and discussed as the
most likely reductant for the one-electron reduction of the
IrCl62- complex. In the case of alkaline N20-saturated
IrCl63- solutions, pertinent benchtop experiments, as well

115
as stopped-flow techniques, were utilized to identify the
peroxide anion, H02-, as the reducing species.
Further work might confirm the proposed reaction be¬
tween the Ir(IV) and Ir(II) species produced from the pulse
radiolysis of nitrogen-saturated Ir(III) solutions, reaction
206. The Ir(II) complex could be exclusively formed by
pulse irradiating, under totally reducing conditions,
Ir(III) solutions containing trace amounts of Ir(IV) added
as a minor solute. Subsequent analysis and comparison of
the resulting Ir(IV) decay to the Ir(IV) decay presented
earlier in this study could substantiate an electron trans¬
fer involving Ir(II) and Ir(IV).
Lastly, as mentioned previously the reaction rate
constant of 4.9 x 109 M-1s-1 for the oxidation of Ir(III) by
OH* was attained by the carbonate competition method. This
value is somewhat less than the reported value of 8.9 x 109
M-1s-1.1;L1 This referenced value was attained by applying
the kinetic competition method using t-butyl alcohol as the
competing species, rather than the carbonate anion. It is
suspected that the lower value reported under the experimen¬
ta conditions in this study could be due to complications
arising from the data analysis of the end-of-pulse Ir(IV)
concentrations. In the presence of added carbonate under
alkaline conditions, the Ir(IV) complex undergoes a rapid
decay immediately upon its formation from OH* reaction with

116
Ir(III). However, these end-of-pulse Ir(IV) concentrations
must be referenced to the end-of-pulse Ir(IV) concentrations
derived from stable Ir(IV) traces that are obtained when no
competing species, i.e. carbonate, is present. The discrep¬
ancy in the rate constants could be explored by attempting
the t-butyl alcohol competition method for the reaction of
OH* with Ir(IV) under the experimental conditions described
in this work.

APPENDICES

APPENDIX A
CHEMICAL DOSIMETRY FOR A PULSED RADIATION SOURCE
Chemical dosimetry involves the determination of the
average absorbed dose in a material from a radiation-
induced chemical change produced in a suitable substrate.
The fraction of the total dose or flux from the radiation
source that is absorbed will induce the chemical change in
the system, and the most common unit of absorbed dose is
the rad, which is defined as
1 rad = 100 erg/g = 6.24 x 1013 ev/g = 0.01 J/kg A-l
These systems consist of a bulk component, which absorbs
the deposited radiation, and a minor component, which
reacts with any radiation-induced species of the bulk to
produce the observed chemical change that is quantitative¬
ly measured. Calculation of the absorbed dose requires
the knowledge of an accurate G-value or radiation chemical
yield which is defined as
G(x) = n(x)/E = # molecules/ 100 eV A-2
with n(x) = the amount of x produced, destroyed, or changed
by an absorbed energy, E. The dosimetry system should have
the same atomic composition and density as the sample to
be irradiated; thus all systems presented in this work are
aqueous solutions that contain various solutes dissolved
in the bulk water solvent. Optimal response characteris-
118

119
tics of the chemical dosimeter are as follows: the dosime¬
ter should be 1) proportional to the radiation dose over
a large range that covers from 10 rads up to 100 Mrads for
radiation chemistry experiments, 2) independent of both
the dose rate and the radiation's energy and LET, 3)
independent of temperature and 4) highly precise, i.e. to
< 5%.40
Chemical dosimetry procedures for use with pulsed
radiation sources are different from standard systems used
with steady-state radiolysis. Larger dose rates occur
with pulsed sources (108 to 1012 rad sec-1) compared to
continuous dose rates ( 10 to 103 rad sec-1) from Co-60 t-
ray sources. The possibility of primary radical-radical
interactions, as opposed to primary radical-solute inter¬
actions, lead to a net loss of measured product. This
effect causes the G-value determined at lower dose rates
to be inaccurate for pulse experiments. Also, with the
pulse radiolysis experimental setup, one can measure tran¬
sient species on the microsecond-to-millisecond time
scales as opposed to chemical analysis carried out after
the completion of a series of radiation-induced
reactions.40
Multiple chemical dosimetry systems were utilized in
this work, and Table 3 shows the various properties in¬
volved in the chemical analysis for each respective sys¬
tem. The first system applied, using the 1.4 ml non-flow

120
reaction cell, was a modified version of the standard
Ferrous sulfate or Fricke system.151 This system (ImM
Fe(NH4)2(SO4)3•6H20, 0.4 M H2S04, air-saturated) involves
the radiation-induced oxidation of ferrous ions to the
ferric state (Fe2+ —> Fe3+) in the presence of oxygen at
low pH. In the modified version (lOmM
Fe(NH4)2(S04)3*6H20, 0.4 M H2S04, 02~saturated) recommend¬
ed for pulse experiments, the solution is oxygen-saturated
and a relatively higher initial [Fe2+] is used. Detection
of the product species, Fe3+, was carried out after the
completion of all relevant reactions, approximately thirty
minutes, as is the practice with the standard Fricke
system.
Table 3
Physical Constants of the Dosimetry Systems*
Super Fricke
Thiocyanate
Hydrated
Electron
Species
detected
Fe3 +
(CNS)2“
e_ _
aq
G(product)
¿molecules
100 eV
16.1
5.8
2.63
A, monitored
(nm)
304
(Beckman)
472
(xenon-arc)
632.8
(laser)
e, (M-1cm-1)
2205
7580
14860
p, (g/ml)
1.024
1.001
1.012
* See references 40 and 151

121
The other systems used — thiocyanate and hydrated
electron — involved transient species detection methods
using the pulse radiolysis detection instrumentation. The
thiocyanate system (10 mM KCNS, N20-saturated) involves a
potassium thiocyanate aqueous solution that, when irradi¬
ated under oxidizing conditions, produces a transient
species, (CNS)2~/ formed in a two-step sequence from the
OH’ radical
OH* + CNS- —> OH" + CNS A-3
CNS + CNS" —> (CNS)2- A-4
The purpose of the N20 saturation is to convert the hy¬
drated electron, eaq-, to OH that eliminates any optical
interferences from eag- and produces a larger yield of the
product species, (CNS)2~, which decays via a second-order
process with a rate constant of 3 x 109 M-1sec-1.151
In the hydrated electron system (0.1 M NaOH, 0.1 M
ethanol, N2-saturated) the hydrated electron, eag-, a
primary radical species produced by the direct interaction
of the radiolysis of water, is monitored. Alkaline condi¬
tions, alcohol addition, and nitrogen-purging help to
minimize the following reactions of the primary eag“.
0 _ „
aq
+
H+ —> H
103
6aq"
+
OH —> OH- + H20
102
0 ~~
aq
+
i
(N
O
A
1
1
CM
O
113

122
The hydrated electron decays via a bimolecular reaction
eaq~ + eaq~ H2 + 20H_ 101
with a rate constant of 2k = 1.2 x 1010 M-1 sec-1.151
Fiqure 35 shows the results of the accumulated ab¬
sorbance detected in a 1.4 ml volume of a modified Fricke
solution contained in the non-flow cell described earlier.
The absorbance is plotted as a function of the number of
pulses delivered with the resultinq slope of 0.1 equal to
the change in optical density per pulse.
Figures 36 and 37 show the transient traces of the
(CNS)2~ and hydrated electron, eag-, respectively. The
life-time of the (CNS)2~ transient is shown to be approxi¬
mately 30-40 microseconds and a best fit analysis gives a
second order decay with k = 3.3 x 109 M-1sec-1 while the life¬
time of the eaq~ transient is approximately 8-10 microsec¬
onds with a best fit curve giving a second order decay
with k = 4.3 x 1010 M-1sec-1.
Using the experimental AA values determined along
with the various constants collected in Table 3, the
absorbed dose (DD), presented in Table 4, can be calcu-
40
lated as

123
Dd = moles product formed per kg
(mol)
(kg)
X 6.022 X 10
23
x 1.602 x 10
-19
(molecules)
(mol)
(J)
100 (eV)
x
G(product) (molecule)
(kg rad)
100 A-5
(eV)
(J)
moles product formed per kg
= 9.647 x 108 x rads
G(product)
or,
moles product formed per liter
Dd = 9.647 x 108 x rads
p G(product)
with,
aA
moles product formed per liter =
A e 1
then,
A A
Dd = 9.647 x 108 x rads
A £ 1 p G(product)
with,
AA = difference in absorbance between irradiated and
non-irradiated solution
Ae = difference in molar extinction coefficient
of reactant and product at monitored wavelength
1 = optical pathlength, cm
p = density of solution, g/ml
G(product) = number of moles of product formed
per 100 eV of energy absorbed

Absorbance
124
Fig. 37. Change in absorbance with accumulated radiation
pulses for the modified Fricke dosimetry system.

125
MULT. X-AXIS BY 0.10E-04 Sec. Y-AXIS BY 0.10E+01 Units. SOURCE:SCNDS.10
? I
MULT. X-AXIS BY 0.10E-04 Sec. Y-AXIS BY 0.10E+06 Units. SOURCE:SCNDS.10
0 â– 
Fig. 38. Thiocyanate dosimetry system (a) graphical
display of the optical signal following pulse
radiolysis of N20-saturated solution containing
10 mM KCNS; data recorded at 472 nra, 100 nsec
period, 50 usee full scale; (b) curve fit of
data between x = 10 to x = 40 usee.

126
MULT. X-AXIS BÂ¥ 8.18E-34 Sec. V-AXIS BV 8.18E+81 Units. SOURCE:HCHEAQ83
MULT. X-AXIS BV B.18E-85 Sec. V-AXIS BV 0.18E+86 Units. SOURCE:MCHEAQ83
Fig. 39. Hydrated electron dosimetry system (a) graphical
display of optical signal following pulse radi¬
olysis of N2~saturated solution containing 0.1 M
NaOH and 0.1 M ethanol; data recorded at 632 nm,
20 nsec period, 10 usee full scale; (b) curve
fit of data between x = 3 and x = 8 usee.

127
Table 4
Absorbance Change and Absorbed Dose for
Chemical Dosimetry Systems
System
AA / pulse
Dd, rads
Super Fricke
0.
101 ± 0.005
(2.5027 ± .2741) X
i—>
o
>p>
Thiocyanate
a)
0.418 ± 0.076
(8.709 ± 1.739) X
10 3
b)
1.129 ± 0.332
(2.3542 ± .5056) X
10 4
Hydrated
a)
0.378 ± 0.137
(9.220 ± 2.001) X
10 3
Electron
b)
1.103 ± 0.267
(2.6894 ± .6521) X
I-*
o
4*
a) Maximum end of pulse absorption from transient trace
b) Results from extrapolation of best fit

APPENDIX B
RELEVANT REACTION SYSTEMS
The reactions used for the calculations of product
concentrations in the aqueous tetraphenylborate and hexa-
chloroiridate systems are listed in Table 5. The 100 series
involves the well-known reactions describing transients of
irradiated pure water152,153 as well as the reactions rele¬
vant to N20- and air-saturated solutions. Reactions 101 -
107 and 118 describe the recombination of the primary radi¬
cal species. Reactions 108-117 describe the reactions
between the radicals and the molecular products.
Reactions 118-123 give the dissociation equilibria of
H20, HO2, and H202. Reactions 124-128 should be important
at pH 10 and above. Reactions 130-134 describe the carbon¬
ate anion and the carbonate radical anion, C037, produced
in the pulse radiolysis of carbonate solutions containing
n2°.
The 200 series involves all the reactions in the mecha¬
nistic scheme describing the IrCl63- complex under the
various conditions presented in the text. The 300 series
involves all the reactions in the mechanistic scheme for the
pulse radiolysis of N20-saturated solutions containing the
TBP- anion.
128

129
Table 5
Chemical Reaction Systems
for Computer Simulation
Studies
No. Reaction
Rate Constant
(M-1s-1)
Ref.
101
0_ + 0_ „
aq aq
—>
H2 + 20H"
5.4
X
cn
o
rH
(a)
102
eaq~ + 0H
— >
OH" + H20
3.0
X
1010
(a)
103
eaq~ + H+
—>
H
2.4
X
1010
(a)
104
eaq + H
—>
H2 + OH"
2.5
X
1010
(a)
105
H + H
—>
H2
7.8
X
109
(a)
106
OH + OH
—>
H2°2
5.3
X
109
(a)
107
H + OH
—>
h2°
7
X
109
(a)
108
eaq + H2°2
—>
OH + OH"
1.2
X
1010
(a)
109
OH + H2
—>
H + H20
4.9
X
107
(a)
110
OH + H202
—>
ho2 + h2o
2.7
X
107
(a)
111
ho2 + ho2
—>
h2o2 + o2
2.7
X
106
(a)
112
°2~ + H02
—>
HO 2 +0 2
4.4
X
107
(a)
113
eaq~ + °2
—>
°2
1.9
X
1010
(a)
114
H + H202
—>
OH + H20
1
X
1010
(a)
115
H02 + H
—>
H2°2
1
X
1010
(a)
116
H02 + OH
—>
h2o + o2
6.6
X
109
(a)
117
H + 02
—>
ho2
1.9
X
1010
(a)
118
H+ + OH-
—>
h2°
1.4
X
1011
(b)
119
h2o
—>
H+ + OH"
2.6
X
10"5
(b)
120
02" + H+
—>
ho2
4.5
X
1010
(c)
121
ho2
—>
H+ + 02"
8
X
105
(d)

122
123
124
125
126
127
128
129
130
131
132
133
134
201
202
203
204
205
206
207
208
209
130
H+ + H02~ —>
H2°2
3
X
1010
(C)
H2°2 >
H+ + H02“
3
X
10~2
(e)
H202 + OH" —>
ho2“ + h2o
1
X
1010
(c)
ho2" + h2o —>
H202 + OH"
5
X
107
(f)
OH + OH" —>
h2o + O"
1.2
X
1010
(g)
A
1
o
CM
X
+
1
O
OH + OH"
9.3
X
107
(g)
O
to
1
+
o
sc
i
i
V
OH" + 02
1.0
X
1010
(h)
n2° + eaq” —>
OH" + OH
8.7
X
109
(a)
OH + C032" —>
OH" + C03"
4.1
X
108
(i)
O
O
w
i
+
O
o
w
1
1
V
co2 + co42"
2
X
107
(i)
co3~ + o2" —>
co32" + o2
4
X
108
(j)
co32" + h2o —>
HC03" + OH"
1.78
X
104
(k)
HC03~ + OH" —>
co32" + h2o
1
X
108
(c)
IrCl63" + OH —>
IrCl62" + OH"
4
X
109
(1)
IrCl63" + eaq" —>
IrCl64-
6.8
X
109
(1)
IrCl63" + H —>
IrCl64" + H+
6
X
109
(m)
IrCl62" + eaq" —>
IrCl63-
9.9
X
109
(n)
IrCl62" + H —>
IrCl63" + H+
9.2
X
109
(n)
IrCl64" + IrCl62"
—>
2IrCl63"
6 X
108
(1)
IrCl62" + 02~ —>
IrCl63" + 02
1
X
107
(1)
IrCl62" + H02" —>
IrCl63" + H02
4.7
X
108
(o)
IrCl64" + IrCl64"
—>
IrCl63" + IrCl6
5-
5
X 108
(n)

131
301
B(C6H5)4~ + 0H- __> (C6H5)3BC6H5OH*
6 X 10y
(1)
302
(c6h5)3bc6h5oht —> B(C6H5)3 + C6H5OHT
5.5 X 104
(1)
303
c6h5oh“ + h2o —> C6H6OH* + OH~
1 X 105
(P)
304
c6h5oh“* + c6h5oh“-
—> [HO(C6H5)-(C6H5)OH]2_
2 X 108
(c)
305
[HO(C6H5)-(C6H5)OH]2- —> C6H5-C6H5 + 20H" .5 X 104
(c)
306
c6h6oh + c6h6oh —> [HO(C6H6)-(C6H5)OH]
6 X 108
(q)
307
[HO(C6H6)-(C6H5)OH] —> c6H5-c6H5 + 2H20
.3 x 104
(o)
308
c6h6°h + C6H6OH —> c6h6 + c6h5oh + h2o
3 X 108
(q)
309
B(C6H5) 4_ + H* ”> (C6H5)3BC6H67
2 X 107
(c)
310
(c6h5)3bc6h6t —> B(C6H5)3 + c6h67
1 x 104
(c)
311
C6H67 + H20 —> C6H7* + OH“
1 x 105
(c)
312
c6h7- + c6h6oh* —> 2c6h6 + h2o
3 x 107
(q)
nref. ill.
°to give best fit.
Pref. 141
^refs. 58, 60.
gref. 43.
*Vef. 154.
xref. 138.
3ref. 155.
^to give pK = 3.74 with k134.
1this work.
manalogous to reaction 205.
aref. 153
bref. 37.
cassuined.
dto give pK
eto give pK
fto give pK
= 4.8 with k
120 '
= 11.8 with k
122'
= 2.3 with k
124*

132
APPENDIX C
INPUT DATA FILES
The data files used in the various computer integration
simulations for the aqueous TPB and Iridium Chloride systems
are presented below. Each input file consist of 1) title
line, 2) reaction steps and appropriate rate constants, 3)
initial reactant molar concentrations, 4) integration step
size and time period parameters, 5) 1-50 time increments.
Simulation Tetraphenylborate System; N20 saturated
1110
1,EAQ+EAQ=H2+H 2 02 —,5.4E9
2,EAQ+0H=0H-+H20,3.0E10
3,EAQ+HPLUS=H,2.4E10
4,EAQ+H=H2+OH-,2.5E10
5,H+H=H2,1.0E10
6,0H+0H=H202,5.3E9
7,H+0H=H20,2.4E10
8,HPLUS+0H-=H20,3E10
9,H20=HPLUS+0H-,5.5E-6
10,EAQ+H202=0H+0H-,1.2E10
11,0H+H2=H+H20,4.9E7
12,0H+H202=H02.+H20,2.7E7
13,H02.+H02.=H202+02,2.7E6
14,02—I-H02 . =H02—1-02,4.4E7
15,EAQ+02=02-,1.9E10
16,H+H202=0H+H20,1E10
17,H02.+H=H202,1E10
18,H02.+0H=H20+02,1E10
19,H+02=H02.,1E10
20,O2-+HPLUS=HO2.,3E10
21,HPLUS+H02-=H202,3E10
22,HO2.=HPLUS+02-,1E6
23,H202=HPLUS+H02-,3E-2
24,H202+0H-=H02-,1E10
25,H02-=H202+0H-,3E7
26,N 20+EAQ=0H-+0H,8.7E9
27,0H+0H-=0-+H20,1.2E10
28,0-+H20=0H+0H-,9.3E7
29,BP4-+0H=BP40H-,6E9
30,BP40H-=BP3+P0H-,5.5E4
31,P0H-=PH0H+0H-,1E5
32,PHOH+PHOH=X,6E8
33,X=C6H5-C6H5,.3E4
34,PHOH+PHOH=POH+C6H6,3E8

133
35,P0H-+P0H-=Y,2E8
36,Y=C6H5-C6H5,.5E4
37 ,BP4-+H=BP4H-,1E5
38,BP4H-=BP3+PH-,1E4
39 , PH—!-H20=PH+0H- , 1.0E7
40,PHOH+PH=C6H6+C6H6,3.5E7
END
EAQ,1.12E-4
HPLUS,1.12E-4
OH,1.12E-4
H,2.91E-5
H2,.975E-5
H202,1.5E-5
H20,55
OH-,IE-7
N20,2.5E-2
BP4-,IE-2
END
I.0E-30,1.OE-33,4E-6,0.00345
I,2,3,4,5,6,7,8,9,10,
II,12,13,14,15,16,17,18,19,20,
21,22,23,24,25,26,27,28,29,30,
31,32,33,34,35,36,37,38,39,40,
41,42,43,44,45,46,47,48,49,50
Simulation Hexachloroiridate System; N20 saturated, alkaline
1110
1,EAQ+EAQ=H2+H202—,5.4E9
2,EAQ+0H=0H-+H20,3.0E10
3,EAQ+HPLUS=H,2.4 E10
4,EAQ+H=H2+OH-,2.5E10
5,H+H=H2,7.8E9
6,0H+0H=H202,5.3E9
7,H+OH=H20,7E9
8,HPLUS+OH-=H20,1.43E11
9,H20=HPLUS+OH-,2.6E-5
10,EAQ+H202=0H+0H-,1.2E10
11,0H+H2=H+H20,4.9E7
12,0H+H202=H02.+H20,2.7E7
13,HO2.+H02.=H202+02,2.7E6
14,02—I-H02 . =H02—1-02,4.4E7
15,EAQ+02=02-,1.9E10
16,H+H202=0H+H20,1E10
17,H02.+H=H202,1E10
18,HO2.+0H=H20+02,6.6E9
19,H+02=H02.,1.9E10
20,02-+HPLUS=H02.,4.5E10
21,HPLUS+H02-=H202,3E10
22,HO2.=HPLUS+02-,8E5
23,H202=HPLUS+H02-,3E-2
24,H202+0H-=H02-,1E10
25,H02-=H202+0H-,5E7
26,0H+0H-=0-+H20,1.2E10

134
27,0-+H20=0H+0H-,9.3E7
28,N20+EAQ=0H-+0H,8.7E9
29,0H+C03—=0H-+C03-,4.1E8
30,C03-+C03-=C02+C04—,2E7
31,C03—=HC03-+0H-,1.78E4
32,HC03-+0H-=C03—,1E8
33 , C03—t-02-=C03—+02,4E8
34,02-+0H=0H-+02,1.01E10
35,IR3+OH=IR4+OH-,4E9
36,IR3+EAQ=IR2,6.8E9
37,IR2+IR4=IR3+IR3,6E8
38,IR4+EAQ=IR3,9.9E9
39,IR4+H=IR3+HPLUS,9.2E9
40,IR3+H=IR2+HPLUS,6E9
41,IR4+H02-=IR3+H02.,4.7E8
42,IR4+02-=IR3+02,1E7
43,IR2+IR2=IR3+IR1,5E8
END
EAQ,1.5E-4
HPLUS,1.5E-4
OH,1.55E-4
H,3.14E-5
H2,2.57E-5
H202,3.88E-5
H02,1.48E-6
H02-,.53E-5
H20,55
OH-,9E-4
IR3,IE-3
N20,2.5E-2
CO3—,5E-3
HC03-,9E-4
02-,2E-7
END
I.0E-30,1.0E-33,9.25E-6,0.00345
I,2,3,4,5,6,7,8,9,10,
II,12,13,14,15,16,17,18,19,20,
21,22,23,24,25,26,27,28,29,30,
31,32,33,34,35,36,37,38,39,40,
41,42,43,44,45,46,47,48,49,50
Simulation Hexachloroiridate System; N20 saturated, neutral
1110
1,EAQ+EAQ=H2+H202—,5.4E9
2,EAQ+OH=OH-+H20,3.0E10
3,EAQ+HPLUS=H,2.4E10
4,EAQ+H=H2+OH-,2.5E10
5,H+H=H2,7.8E9
6,0H+0H=H202,5.3E9
7,H+0H=H20,7E9
8,HPLUS+0H-=H20,1.43Ell
9,H20=HPLUS+0H-,2.6E-5
10,EAQ+H202=0H+0H-,1.2E10

135
11,0H+H2=H+H20,4.9E7
12,0H+H202=H02.+H20,2.7E7
13,H02.+H02.=H202+02,2.7E6
14,02—I-H02 .=H02—K)2,4.4E7
15,EAQ+02=02-,1.9E10
16,H+H202=0H+H20,1E10
17,H02.+H=H202,1E10
18,HO2.+0H=H20+02,6.6E9
19,H+02=H02.,1.9E10
20,02—l-HPLUS=H02 . ,4.5E10
21,HPLUS+H02-=H202,3E10
22,HO2.=HPLUS+02-,8E5
23,H202=HPLUS+H02-,3E-2
2 4,N20+EAQ=0H—fOH,8.7E9
25,02-+0H=0H-+02,1.01E10
26,IR3+OH=IR4+OH-,4E9
27,IR3+EAQ=IR2,6.8E9
28,IR2+IR4=IR3+IR3,6E8
29,IR4+EAQ=IR3,9.9E9
30,IR4+H=IR3+HPLUS,9.2E9
31, IR3+H=IR2+HPLUS,6E9
32,IR4+H02-=IR3+H02.,4.7E8
33,IR4+02-=IR3+02,1E7
34,IR2+IR2=IR3+IR1,5E8
END
EAQ,1.5E-4
HPLUS,1.5E-4
OH,1.55E-4
H,3.14E-5
H2,2.57E-5
H202,3•88E-5
H02,1•48E-6
H20,55
OH-,IE-7
IR3,IE-3
N20,2.5E-2
END
I.0E-30,1.OE-33,9.25E-6,0.00345
I,2,3,4,5,6,7,8,9,10,
II,12,13,14,15,16,17,18,19,20,
21,22,23,24,25,26,27,28,29,30,
31,32,33,34,35,36,37,38,39,40,
41,42,43,44,45,46,47,48,49,50
Simulation Hexachloroiridate System; Nitrogen saturated
1110
1,EAQ+EAQ=H2+H202—,5.4E9
2,EAQ+0H=0H-+H20,3.0E10
3,EAQ+HPLUS=H,2.4E10
4,EAQ+H=H2+OH-,2.5E10
5,H+H=H2,7.8E9
6,0H+0H=H202,5.3E9
7,H+0H=H20,7E9

136
8,HPLUS+0H-=H20,1.43E11
9,H20=HPLUS+0H-,2.6E-5
10,EAQ+H202=0H+0H-,1.2E10
11,0H+H2=H+H20,4.9E7
12,0H+H202=H02.+H20,2.7E7
13,HO2.+H02.=H202+02,2.7E6
14,02-+H02.=H02-+02,4.4E7
15,EAQ+02=02-,1.9E10
16,H+H202=OH+H20,1E10
17,HO2.+H=H202,1E10
18,H02.+0H=H20+02,6.6E9
19,H+02=H02.,1.9E10
20,02-+HPLUS=H02.,4.5E10
21,HPLUS+H02-=H202,3E10
22,HO2.=HPLUS+02-,8E5
23,H202=HPLUS+H02-,3E-2
24,02-+0H=0H-+02,1.01E10
25,IR3+OH=IR4+OH-,4E9
26,IR3+EAQ=IR2,6.8E9
27,IR2+IR4=IR3+IR3,6E8
28,IR4+EAQ=IR3,9.9E9
29,IR4+H=IR3+HPLUS,9.2E9
30,IR3+H=IR2+HPLUS,6E9
31,IR4+H02-=IR3+H02.,4.7E8
32,IR4+02-=IR3+02,1E7
33,IR2+IR2=IR3+IR1,5E8
END
EAQ,1.5E-4
HPLUS,1.5E-4
OH,1.55E-4
H,3.14E-5
H2,2.57E-5
H202,3.88E-5
H02,1.48E-6
H20,55
OH-,IE-7
IR3,IE-3
END
I.0E-30,1.OE-33,9.25E-6,0.00345
I,2,3,4,5,6,7,8,9,10,
II,12,13,14,15,16,17,18,19,20,
21,22,23,24,25,26,27,28,29,30,
31,32,33,34,35,36,37,38,39,40,
41,42,43,44,45,46,47,48,49,50
Simulation Hexachloroiridate System; Aerated
1110
1,EAQ+EAQ=H2+H 2O 2—,5.4E9
2,EAQ+OH=OH-+H20,3.0E10
3,EAQ+HPLUS=H,2.4 El0
4,EAQ+H=H 2 +OH-,2.5E10
5,H+H=H2,7.8E9
6,0H+0H=H202,5.3E9

137
7,H+0H=H20,7E9
8,HPLUS+0H-=H20,1.4 3 El1
9,H20=HPLUS+0H-,2.6E-5
10,EAQ+H202=0H+0H-,1.2E10
11,0H+H2=H+H20,4.9E7
12,0H+H202=H02.+H20,2.7E7
13,H02.+H02.=H202+02,2.7E6
14,02-+H02 . =H02—1-02,4.4E7
15,EAQ+02=02-,1.9E10
16,H+H202=0H+H20,1E10
17,H02.+H=H202,1E10
18,HO2.+0H=H20+02,6.6E9
19,H+02=H02.,1.9E10
20,02—HHPLUS=H02.,4.5E10
21,HPLUS+H02-=H202, 3E10
22,HO2.=HPLUS+02-,8E5
23,H202=HPLUS+H02-,3E-2
24,02—t-OH=OH—1-02,1.01E10
25,IR3+OH=IR4+OH-,4E9
26,IR3+EAQ=IR2,6.8E9
27,IR2+IR4=IR3+IR3,6E8
28,IR4+EAQ=IR3,9.9E9
29,IR4+H=IR3+HPLUS,9.2E9
30,IR3+H=IR2+HPLUS,6E9
31,IR4+H02-=IR3+H02.,4.7E8
32,IR4+02-=IR3+02,1E7
33,IR2+IR2=IR3+IR1,5E8
END
EAQ,1.5E-4
HPLUS,1.5E-4
OH,1.55E-4
H,3•14E-5
H2,2.57E-5
H202,3.88E-5
H02,1.48E-6
H20,55
OH-,IE-7
IR3,IE-3
02,2.5E-4
END
I.0E-30,1.0E-33,9.4E-6,0.00345
I,2,3,4,5,6,7,8,9,10,
II,12,13,14,15,16,17,18,19,20,
21,22,23,24,25,26,27,28,29,30,
31,32,33,34,35,36,37,38,39,40,
41,42,43,44,45,46,47,48,49,50

1
2
3
4
5
6
7
8
9
10
11
12
15
18
19
20
21
23
24
25
26
28
33
35
40
43
45
48
50
52
72
73
APPENDIX D
PULSE RADIOLYSIS COMPUTER PROGRAM
7 ********** DATA GRABBER ****************
/
/ ***** File DEBEST8.BAS, OCT. 12, 1989 *****
/
' PULSE RADIOLYSIS DATA ACQUISITION PROGRAM FOR DATA
PRECISION 6000
' TRANSIENT DIGITIZER INTERFACED THROUGH A SERIAL PORT AT
9600 BAUD
7 WITH AN IBM-PC COMPATIBLE MICROCOMPUTER.
7 FOR USE WITH MICROSOFT QUICK
WITH 8087
7 COPYRIGHT 1988, 1989 BY JOHN
HANRAHAN
7 RADIATION CHEMISTRY LAB, 406
32611
7 TEL 904-392-1442 OR 376-7754
/
7 WORK DONE UNDER DOE CONTRACT
/
BASIC COMPILER VERSION 4.0
BROGDON AND ROBERT
NSC, U OF FLA GAINESVILLE
DE-ASO5-76ERO-3106
7 COMPILE FROM THE QBASIC DIRECTORY WITH THE WORKFILE ON
B:, AS FOLLOWS
7 BC B: DEBEST8/0/X/E/C:6000; THE LAST SETS UP THE
7 COMMUNICATION BUFFER; THEN LINK. IN TURBO BASIC THE
7 METACOMMAND $C0M1 6000 IS SUPPOSED TO WORK BUT WE GET
ERRORS
7 ABOUT EVERY NINTH DATA POINT WHEN WE TAKE DATASET FROM
DP 6000.
7 IN BASICA, THE BUFFER MAY BE CHANGED WITH THE COMMAND
"BASIC/C:6000"
7 WHEN ENTERING INTO THE BASIC MODE, BUT INTERPRETER IS
VERY SLOW
7 AND SEVERAL TIMING LOOPS MUST BE CHANGED. SOME TIMING
LOOPS
7 PRESENTLY MAY BE LONGER THAN NECESSARY ON A STANDARD
SPEED 4.77 MHz
7 COMPUTER **** BUT MIGHT NEED TO BE LONGER ON A FASTER
MACHINE
7 **** NOTE, THE UNDERLINE IS A LINE CONTINUATION
IN QBASIC ****
7 WARNING — NOT ALL FEATURES HAVE BEEN FULLY TESTED. IN
PARTICULAR,
7 THE COMMAND TO COMPARE SPECTRA HAS NOT BEEN USED
EXTENSIVELY.
138

75
80
90
100
110
120
130
140
145
150
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
432
433
435
436
437
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500
139
DIM AGI$(100), BGI$(100), DSPM$(10), TRGSRC$(10), OD(512)
DIM QY(520), QX(512), VERLN(147), QLY(512), BTARY(3400),
CON(512)
OPEN "comí:9600,n,8,1,es,ds,cd" FOR RANDOM AS #1
ON ERROR GOTO 5220
SCREEN 2: KEY ON: CLS : GET (1, 80)-(639, 99), BTARY
DLY$ = "-3.0US": PER$ = "200nS": SWP$ = "3"
DSPM = 2: YSC$ = "1.0": TRGSRC = 5
PRINT "FIRST TURN ON THE DP6000, THEN PRESS CONT"
FOR KKQ = 1 TO 520: QY(KKQ) = 0: NEXT
L = 1: EE = 3000: FLORD = 0: FLCAL = 0: FLDATA = 0
KEY OFF: B$ = "PROG;KEYSRQ=1;KEY=1017;KEY=1033;REMOTE"
GOSUB 1090
INPUT "IS MODE ON RUN OR EDIT"; B$
B$ = LEFT$(B$, 1)
IF B$ <> "R" AND B$ <> "E" GOTO 190
IF B$ = "R" GOTO 250
B$ = "KEY=1017"
GOSUB 1090
INPUT "IS EXECUTE ON RUN/STOP (YES or NO)"; B$
B$ = LEFT$(B$, 1)
IF B$ <> "Y" AND B$ <> "N" GOTO 250
IF B$ = "Y" GOTO 320
B$ = "KEY=1033"
GOSUB 1090
GOTO 250
DEF FNQSC (QS, QXS, QNS, QXO, QNO) = INT(QXO - (QXO - QNO)
/ (QXS - QNS) * (QXS - QS) + .5)
PRINT : GOTO 350
'*************** MENU ************************************
PRINT
PRINT "RETURNING TO MENU": PRINT
PRINT "CALIBRATION
PRINT "DATA
PRINT "PLOTTER
PRINT "LEAST SQUARES
PRINT "LOAD
PRINT "SAVE
PRINT "ORDER
PRINT "COMPARE
PRINT "MAN
PRINT "DIR
PRINT "END
= 1 TO 25
* 1000
CALIBRATE DP6000 FOR EXPERIMENT"
AQUIRE DATA FROM DP6000"
PLOT RAW DATA ON SCREEN"
LINEAR REGRESION FOR CURRENT DATA"
LOAD DATA FROM DISK"
SAVE DATA ON DISK"
CHOOSE ORDER OF REACTION"
COMPARE DATA SETS ON GRAPH"
MANUAL CHANGE VO,VM,L,OR E"
DISK DIRECTORY"
END SESSION "
FOR I
SOUND RND * 1000 + 37, 2
NEXT I
PRINT : INPUT "COMMAND"; B$
B$ = LEFT$(B$, 3)
IF B$ = "END" THEN END
RESTORE
FOR I = 1 TO 11
IF I = 11 THEN PRINT "BAD COMMAND":
READ A$
IF B$ = A$ THEN GOTO 520
PRINT
GOTO 440

510
520
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550
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570
580
585
586
590
592
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600
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640
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690
695
700
702
705
710
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734
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750
760
770
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790
792
794
NEXT I
ON I GOSUB 570, 1140, 1480, 3950, 4940, 4780, 5140, 5330,
8000, 9800
PRINT : GOTO 350
DATA "CAL","DAT","PLO","LEA","LOA","SAV","ORD","COM",
"MAN","DIR"
GOTO 9999
'************ CALIBRATION ********************************
PRINT : PRINT TAB(25); : PRINT "CALIBRATION"
DSPM$(1) = "SINGLE": DSPM$(2) = "2 SEPR": DSPM$(3) =
"2 OVLY"
TRGSRC$(1) = "NONE": TRGSRC$(2) = "CH 1": TRGSRC$(3) =
"CH 2"
TRGSRC$(4) = "LINE": TRGSRC$(5) = "EXT TRIG"
PRINT
PRINT "1)TIME DELAY=" + DLY$, "2)PERIOD=" + PER$, "3)#
SWEEPS=" + SWP$,
PRINT "4)DSPL MODE=" + DSPM$(DSPM), "5) Y SCALE=" + YSC$
"6)NO CHANGE"
PRINT "7)TRIGGER=" + TRGSRC$(TRGSRC)
FLCAL = 1
PRINT
PRINT "WHICH NUMBER": B$ = INPUT$(1)
B = VAL(B$)
IF B < 1 OR B > 7 GOTO 620
ON B GOTO 660, 670, 680, 690, 700, 710, 702
INPUT "1)TIME DELAY= ", DLY$: GOTO 590
INPUT "2)PERIOD=", PER$: GOTO 590
INPUT "3)# SWEEPS=", SWP$: GOTO 590
PRINT : PRINT "CHOICES:", "1) SINGLE", "2) 2 SEPR",
"3) 2 OVLY"
PRINT : INPUT "4)DSPL MODE=", DSPM: GOTO 590
INPUT "5)Y SCALE=", YSC$: GOTO 590
PRINT : PRINT "CHOICES:", "l)NONE", "2)CH 1", "3)CH 2",
"4)LINE",
PRINT "5)EXT TRIG": INPUT "7)TRIGGER=", TRGSR: GOTO 590
PRINT "INIALIZING DP6000"
TRG$ = STR$(TRGSR)
B$ = "DARM;PROMPT=l;TRIG;TRGM=1;TMB;PERIOD=" + PER$ +
";TRGSRC=" + TRG$
GOSUB 1090
B$ = "TMB;KEY=1008;PERIOD=" + PER$ + ";KEY=1004;
PERIOD=" + PER$ + ""
GOSUB 1090
B$ = "DELAY=" + DLY$ + ";DISP;DSPM=" + STR$(DSPM)
GOSUB 1090
B$ = "TRACE=1;X;TRCSRC=BUF.A2;XFILL=2;Y;YSCL=" + YSC$ +"
;TRACE=2"
GOSUB 1090
B$ = "TRCSRC=BUF•A2;YSCL=" +YSC$ + ";X;XFILL=2;GRID=2;ARM
GOSUB 1090
B$ = "TMB"
GOSUB 1090

800
810
820
830
832
834
836
838
840
850
860
870
880
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884
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910
912
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141
PRINT : PRINT "V0="; VO, "VM="; VM + VO: PRINT
INPUT "DO YOU WANT TO CHANGE THE PARAMETERS OF THE
EXPERIMENT"; B$
B$ = LEFT$(B$, 1)
IF B$ <> "Y" AND B$ <> "N" GOTO 810
B$ = "KEY=4001"
GOSUB 1090
B$ = "KEY=1008"
GOSUB 1090
IF B$ = "N" AND VM <> 0 THEN B$ = "DARM": GOSUB 1090: GOTO
990
IF VM = 0 AND B$ = "N" THEN PRINT "YOU HAVE NO CHOICE (VM-
V0=0)"
PRINT : INPUT "HAVE YOU TRIGGERED FOR NO LIGHT"; B$
B$ = LEFT$(B$, 1): IF B$ <> "Y" THEN 860
"BUF.A2(2)" :
GOSUB 7000
MYINFO:
B$ =
"BUF.A2(150)":
GOSUB
7000
MYINFO:
B$ =
"BUF.A2(250)" :
GOSUB
7000
MYINFO:
B$ =
"BUF.A2(350)" :
GOSUB
7000
Y3 = MYINFO
VO = (Y1 + Y2 + Y3) / 3
B$ = "KEY=4001"
GOSUB 1090
B$ = "KEY=1008"
GOSUB 1090
PRINT : INPUT "HAVE YOU TRIGGERED FOR FULL LIGHT"; B$
B$ = LEFT$(B$, 1): IF B$ <> "Y" THEN 920
B$ = "BUF.A2(2)": GOSUB 7000
NO = MYINFO: B$ = "BUF.A2(150)": GOSUB 7000
Y1 = MYINFO: B$ = "BUF.A2(250)": GOSUB 7000
Y2 = MYINFO: B$ = "BUF.A2(350)": GOSUB 7000
Y3 = MYINFO
REM B$="BUF.A2(2);BUF.A2(400);BUF.A2(300);BUF.A2(500);DARM"
REM GOSUB 1090
REM INPUT #1,NO,Y1,Y2,Y3
VM = (Y1 + Y2 + Y3) / 3
VFULL = VM - VO
REM L = L / EE
PRINT : PRINT "VMAX = "; VM; " VO = "; VO; "L="; L,
"E="; EE: PRINT
PRINT "L-CHANGE L", "E-CHANGE E", "N-NO CHANGE ": B$ =
INPUT$(1)
IF B$ <> "L" AND B$ <> "E" AND B$ <> "N" GOTO 1010
IF B$ = "L" THEN INPUT "L=", L: GOTO 1000
IF B$ = "E" THEN INPUT "E=", EE: GOTO 1000
LEFF = L * EE * 2.303
QY(516) = VO: QY(517) = VM: QY(518) = L: QY(519) = EE
RETURN
********* OUTPUT B$ TO DP6000 ***************************
PRINT #1, B$
FOR I = 1 TO 8000
QQWER = LOG(I)
NEXT I

142
1120 RETURN
1130 '*********** DATA ***************************************
1140 PRINT TAB(40); "DATA"
1150 IF FLCAL = 0 THEN PRINT "CALIBRATION NEEDED FIRST": GOSUB
570
1160 B$ = "DARM;X;TRACE=1;TRCSRC=BUF.A2"
1170 GOSUB 1090
1172 B$ = "X;TRACE=2;TRCSRC=AVEGA2"
1173 GOSUB 1090
1174 FOR BADDOG = 1 TO 500: AHUNK1 = LOG(BADDOG): NEXT
1175 REM B$ = "PROG;SAVG;AVGCLR;AVGCNT=0;NAVG=" + SWP$ +
";KEY=1067;DISP;"
1176 B$ = "PROG;SAVG;AVGCLR;AVGCNT=0;"
1177 GOSUB 1090
1178 B$ = "NAVG=" + SWP$ + ";KEY=1067;DISP;"
1179 GOSUB 1090
1182 B$ = "AVGCLR;AVGCNT=0;CLRSUM"
1184 GOSUB 1090
1192 B$ = "X;TRACE=1;TRCSRC=BUF.A2;ARM"
1194 GOSUB 1090
1200 SWP = VAL(SWP$)
1210 FOR K = 1 TO SWP
1212 B$ = "KEY=4001"
1214 GOSUB 1090
1216 B$ = "KEY=1008"
1218 GOSUB 1090
1220 PRINT "TYPE T FOR TRIGGERED OR S FOR STOP. ";
1230 B$ = INPUT$(1): PRINT B$
1240 IF B$ <> "T" AND B$ <> "S" THEN GOTO 1220
1250 IF B$ = "S" GOTO 1300
1260 B$ = "KEY=2001"
1270 GOSUB 1090
1280 PRINT "# SWEEPS="; K
1290 NEXT K
1300 B$ = "DARM;X;TRACE=2;TRCSRC=AVEGA2"
1309 GOSUB 1090
1310 REM GOSUB 7000
1311 B$ = "PERIOD": GOSUB 7000
1312 NO = MYINFO
1313 B$ = "PERIOD": GOSUB 7000
1314 PER = MYINFO
1315 B$ = "MIN": GOSUB 7000
1316 QMINY = MYINFO
1317 B$ = "MAX": GOSUB 7000
1318 QMAXY = MYINFO
1319 B$ = "DELAY": GOSUB 7000
1320 N = MYINFO
1329 REM INPUT #1,NO,PER,QMINY,QMAXY,N
1330 IF QMAXY <> QMINY THEN GOTO 1370
1340 PRINT "BAD DATA": PRINT NO, PER, QMINY, QMAXY, N
1350 REM IF LOC(1)<3 GOTO 1300
1360 REM INPUT #l,PER:GOTO 1300
1365 GOTO 350

143
1370 PRINT "creating file from avega2"
1371 PRINT #1, "AVEGA2¡"
1372 FOR AAA = 1 TO 200: SAM = SAM + 3: NEXT
1378 PRINT "finist sam stall"
1380 FOR I = 1 TO 512
1383 REM QWQWQE = 2+3
1390 INPUT #1, QY(I)
1400 NEXT I
1405 PRINT "FINISH W INPUT INTO #1"
1410 FOR I = 1 TO 512
1420 QX(I) = I * PER
1425 IF VM = 0 THEN VM = -3: IF L = 0 THEN L = 39: IF V0 = 0
THEN VO = -1
1430 CON(I) = -LOG(ABS((QY(I) - VO) / VFULL)) / LEFF
1431 OD(I) = -LOG(ABS((QY(I) - VO) / VFULL)) / 2.303
1440 NEXT I
1450 QY(513) = PER: QY(514) = QMAXY: QY(515) = QMINY
1460 FLDATA = 1
1465 PRINT "going to main menu"
1470 RETURN
1480 '**************** PLOTTER ******************************
1490 N = 1: QMINX = QX(1): QMAXX = QX(512)
1491 RHGRFLAG = 0
1500 IF FLDATA > 0 THEN GOTO 1520
1510 PRINT "NO DATA SOURCE. RETURNING TO MENU": RETURN
1520 INPUT "WHAT RESOLUTION WOULD YOU LIKE TO GRAPH (1 TO 20)";
QRES
1525 IF QRES < 1 OR QRES > 20 THEN QRES = 1
1530 QN = 512: QFLG = 0: GOSUB 2160
1540 GOSUB 1570
1550 RETURN
1560 '**************** LEFT & RIGHT BORDERS ******************
1561 RHGRFLAG = 0
1570 PUT (0, QLNB + 11), BTARY, PSET: LOCATE INT((QLNB / 200) *
25 + 1) + 2, 1
1571 IF RHGRFLAG = 1 THEN FOR ASEC = 1 TO 12000: AMIN =
LOG(ASEC): NEXT
1575 PRINT "WOULD YOU LIKE TO LEAST SQUARES FIT DATA ON GRAPH"
1590 INPUT B$: B$ = LEFT$(B$, 1)
1600 IF B$ = "N" THEN RETURN
1610 IF B$ <> "Y" THEN GOTO 1590
1620 GET (QLNL, QLNT)-(QLNL, QLNB), VERLN
1630 PUT (0, QLNB +11), BTARY, PSET: LOCATE INT((QLNB / 200) *
25 + 1) + 2, 1
1640 INPUT "DO YOU WISH TO MOVE THE LEFT BORDER"; B$
1650 B$ = LEFT$(B$, 1)
1660 LNPOS = QLNL
1670 IF B$ = "N" THEN GOTO 1830
1680 IF B$ <> "Y" THEN GOTO 1630
1690 LNPOS = QLNL + 25
1700 C$ = "R"
1710 PUT (LNPOS, QLNT), VERLN

1720
1730
1740
1750
1760
1770
1780
1790
1800
1810
1820
1830
1840
1850
1860
1870
1880
1890
1900
1910
1920
1930
1940
1950
1960
1970
1980
1990
2000
2010
2020
2030
2040
2060
2070
2075
2076
2077
2078
2079
2080
2081
2082
2083
2084
2093
144
PUT (0, QLNB + 11), BTARY, PSET: LOCATE INT((QLNB / 200) *
25 + 1) + 2, 1
PRINT "L-LEFT,R-RIGHT,S-STOP OR NUMBER OF SPACES : B$
= INPUT$(1)
D = VAL(B$) A 2
IF D = 0 AND (B$ = "L" OR B$ = "R" OR B$ = "S")THEN C$= B$
IF C$ = "S" THEN GOTO 1830
PUT (LNPOS, QLNT), VERLN
IF C$ = "R" THEN LNPOS = LNPOS + D
IF C$ = "L" THEN LNPOS = LNPOS - D
IF LNPOS < QLNL THEN LNPOS = QLNL: C$ = "R"
IF LNPOS > QLNR THEN LNPOS = QLNR: C$ = "L"
PUT (LNPOS, QLNT), VERLN: GOTO 1720
N = ((QMAXPX - QMINPX) * QSCLX * (LNPOS - QLNL)) / (QLNR -
QLNL)
N = INT((N - QX(1)) / QY(513 ) )
PUT (0, QLNB + 11), BTARY, PSET: LOCATE INT((QLNB / 200) *
25 + 1) + 2, 1
INPUT "DO YOU WISH TO MOVE THE RIGHT BORDER"; B$
B$ = LEFT$(B$, 1)
LNPOS = QLNR
IF B$ = "N" THEN GOTO 2060
IF B$ <> "Y" THEN GOTO 1850
LNPOS = QLNR - 100
C$ = "L"
PUT (LNPOS, QLNT), VERLN
PUT (0, QLNB + 11), BTARY, PSET: LOCATE INT((QLNB / 200) *
25 + 1) + 2, 1
PRINT "L-LEFT,R-RIGHT,S-STOP OR NUMBER OF SPACES : B$
= INPUT$(1)
D = VAL(B$) A 2
IF D = 0 AND (B$ = "L" OR B$ = "R" OR B$ = "S")THEN C$= B$
IF C$ = "S" THEN GOTO 2060
PUT (LNPOS, QLNT), VERLN
IF C$ = "L" THEN LNPOS = LNPOS - D
IF C$ = "R" THEN LNPOS = LNPOS + D
IF LNPOS < QLNL THEN LNPOS = QLNL: C$ = "R"
IF LNPOS > QLNR THEN LNPOS = QLNR: C$ = "L"
PUT (LNPOS, QLNT), VERLN: GOTO 1940
J = ((QMAXPX - QMINPX)*QSCLX *(LNPOS - QLNL))/(QLNR - QLNL)
J = INT((J - QX(1)) / QY(513 ) )
IF J < N THEN CC = J: J=N: N=CC
IF J > 512 THEN J = 512
IF N < 1 THEN N = 1
CLOSE #1
INPUT "CREATE A NEW FILE FOR COMP SIMU ?"; RNBANS$
C$ = (LEFT$(RNBANS$, 1))
IF C$ = "N" OR C$ = "" THEN GOTO 2106
INPUT "CREAT 'OD' FILE (YES) ELSE CON FILE CREATED?";
CLCANS$
C$ = (LEFT$(CLCANS$, 1))
IF C$ = "Y" THEN GOTO 9892
INPUT "WHICH DRIVE"; DRV$: IF DRV$ = " " THEN DRV$ = "C"

145
2094 DRV$ = LEFT$ ( DRV$ , 1)
2095 IF DRV$ = "A" OR DRV$ = "B" GOTO 2098
2096 IF DRV$ = "C" OR DRV$ = "D" GOTO 2098
2097 GOTO 2093
2098 DRV$ = DRV$ +
2099 INPUT "FILE NAME"; FILENAME$
2100 B$ = DRV$ + LEFT$(FILENAME$, 8)
2101 OPEN "O", #1, B$
2102 FOR I = N TO J STEP 5
2103 PRINT #1, QX(I), »,», CON(I),
2104 NEXT I
2105 CLOSE #1
2106 PUT (0, QLNB +11), BTARY, PSET: LOCATE INT((QLNB / 200) *
25 + 1) + 2, 1
2110 INPUT "ORDER OF REACTION (0,1,2 or 3)"; ORDER
2120 IF ORDER < 0 OR ORDER > 3 GOTO 2100
2130 PUT (0, QLNB + 11), BTARY, PSET: LOCATE INT((QLNB / 200) *
25 + 1) + 2, 1
2140 GOSUB 3980
2150 RETURN
2160 '************* HERE COMES PLOTTER**********************
2170 QQYY = 95: QQXX = 317
2180 REM qflg=0 - grid and plot , = 1 - grid only, = 2 - plot
only
2190 IF QFLG > 1 THEN 2910
2200 Q$ = "##.#"
2210 REM approximate number of vertical and horizontal
intervals
2220 QNINX = 5: QNINY =4.8
2230 REM left and right borders
2240 QLNL = 40: QLNR = 639
2250 REM bottom and top borders
2260 QLNB = 164: QLNT = 9: QLOCX1 = 1
2270 SCREEN 2: CLS : KEY OFF
2280 QLOCY1 = INT(QLNT / 8 + .5)
2290 QLOCY2 = QLOCY1 + 1
2300 QLOCY3 = INT(QLNB / 8 + .625)
2310 QLOCY4 = QLOCY3 + 1
2320 QLOCY5 = QLOCY4 + 1
2330 QLOCX2 = INT(QLNL / 8 - 4)
2340 QLOCX3 = QLOCX2 + 1
2350 QLOCX4 = QLOCX3 + INT((QLNR - QLNL) / 8 + .625) - 1
2360 REM find "nice" x-scale intervals
2370 QMIN = QMINX: QMAX = QMAXX: QNIN = QNINX
2380 GOSUB 3500
2390 QSCLX = QSCL: QMINPX = QMINP: QMAXPX = QMAXP
2400 QNINPX = QNINP: QWDTX = QWDT
2410 REM find "nice" y-scale interals
2420 QMIN = QMINY: QMAX = QMAXY: QNIN = QNINY
2430 GOSUB 3500
2440 QSCLY = QSCL: QMINPY = QMINP: QMAXPY = QMAXP
2450 QNINPY = QNINP: QWDTY = QWDT
2460 REM draw title

146
2470
2480
2490
2492
2500
2501
2502
2503
2510
2520
2530
2540
2550
2560
2570
2580
2590
2600
2610
2620
2630
2640
2650
2660
2670
2680
2690
2700
2710
2720
2730
2740
2750
2760
2770
2780
2790
2800
2810
2820
2830
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2850
2860
2870
2880
2890
2900
2910
2920
2930
2940
LOCATE 1, 9
IF FLDATA = 1 THEN DSRC$ = "DP6000"
IF FLDATA = 2 THEN DSRC$ = FILENAME$
RH33 = QSCLX: RH33 = RH33 * (1.0001)
REM PRINT "MULTIPLY Y-AXIS BY";QSCLY;"Units
PRINT "MULT. X-AXIS BY ";
PRINT USING "#.##AAAA"; RH33; : PRINT " Sec.
PRINT USING "#.##AAAA"; QSCLY; : PRINT " Units
DSRC$
IF FLORD = 0 GOTO 2620
LOCATE 2, 35
IF ORDER = 1 THEN B$ = "ln(C)=ln(Co)-K*t"
IF ORDER = 2 THEN B$ = "(1/C)=(l/Co)+K*t"
IF ORDER = 3 THEN B$ = "(1/C)A2=(1/Co)A2+2*K*t
IF ORDER = 4 THEN B$ = "C=Co-K*t"
PRINT B$
IF B > 0 THEN LOCATE 3, 8
IF B < 0 THEN LOCATE 3, INT(QLNR * 80 / 640 -
PRINT "K="; K
FLORD = 0
QLOCWY = (QLOCY3 - QLOCY2 + 1) / QNINPY
QLNWY = (QLNB - QLNT) / QNINPY
REM draw vertical grid and labels
Y-AXIS BY "
. SOURCE:";
.5) - 15
FOR QI = 0 TO QNINPY
IF QI = 0 THEN 2690
LOCATE INT(QLOCY3 - QI * QLOCWY + 1), QLOCX2
PRINT USING Q$; QMINPY + QI * QWDTY;
QNLY1 = QNLB - QI * QLNWY
NEXT QI
GOSUB 3840
LINE (QLNL, QLNB)-(QLNR, QLNB)
QLOCWX = (QLOCX4 - QLOCX3 + 1) / QNINPX
QLNWX = (QLNR - QLNL) / QNINPX
REM draw horizontal grid and labels
FOR QI = 0 TO QNINPX
QLOC = QLOCY4
LOCATE QLOC, INT(QLOCX3 + QI * QLOCWX + .5)
PRINT USING Q$; QMINPX + QI * QWDTX;
QNLX1 = QLNL + QI * QLNWX
NEXT QI
LINE (QLNL, QLNB)-(QLNL, QLNT)
GOSUB 3730
IF QFLG = 1 THEN RETURN
REM draw gx-gy array
FOR QI = N TO QN STEP QRES
GOSUB 3440
LINE (QX2, QY2)-(QX2, QY2), , B
NEXT QI
RETURN
IF QSCL > 0 THEN 2930
PRINT "NO GRID DRAWN, CHECK QFLG PARAMETER": RETURN
FOR QI = N TO QN STEP QRES
GOSUB 3440

2950 REM chek for points outside the grid
2970 IF QX2 < QLNL OR QX2 > QLNR OR QY2 > QLNB OR QY2 < QLNT
THEN QFL2 = 1 ELSE QFL2 = 0
2980 IF QFL2 = 0 THEN LINE (QX2, QY2)-(QX2, QY2), , B
3110 NEXT QI
3430 RETURN
3440 REM routine for linear transformation from subject to
object space
3460 QX2 = FNQSC(QX(QI) / QSCLX, QMAXPX, QMINPX, QLNR, QLNL)
3480 QY2 = FNQSC(QY(QI) / QSCLY, QMAXPY, QMINPY, QLNT, QLNB)
3490 RETURN
3500 REM routine to find "nice" scale intervals
3510 IF QMIN >= QMAX THEN BEEP: PRINT "Array can not be
plotted": STOP
3520 QEPS = .025: QA = ABS(QMIN)
3530 IF ABS(QMIN) < ABS(QMAX) THEN QA = ABS(QMAX)
3540 QSCL = 10 A INT(LOG(ABS(QA)) / LOG(IO))
3550 QMINA = QMIN / QSCL: QMAXA = QMAX / QSCL
3560 IF QMIN = 0 THEN QMIN = -1
3570 QD = (QMAXA - QMINA) / QNIN: QJ = QD * QEPS
3580 QE = INT(LOG(ABS(QD)) / LOG(IO))
3590 QF = QD / 10 A QE: QV = 10
3600 IF QF < SQR(50) THEN QV = 5
3610 IF QF < SQR(10) THEN QV = 2
3620 IF QF < SQR(2) THEN QV = 1
3630 QWDT = QV * 10 A QE
3640 QG = INT(QMINA / QWDT)
3650 IF ABS(QG + 1 - QMINA / QWDT) < QJ THEN QG = QG + 1
3660 QMINP = QWDT * QG
3670 QH = INT(QMAXA / QWDT) + 1
3680 IF ABS(QMAXA / QWDT + 1 - QH) < QJ THEN QH = QH - 1
3690 QMAXP = QWDT * QH
3700 QNINP = QH - QG
3710 IF ABS(QMAXP) >= 10 OR ABS(QMINP) >= 10 THEN QSCL = QSCL
10: GOTO 3550
3720 RETURN
3730 REM routine to draw x tic marks
3740 QLNXB1 = QLNR
3750 QDTXP = INT((QLNR - QLNL) / QNINPX)
3760 QLNXB1 = QLNXB1 + QDTXP
3770 FOR QQ = 1 TO QNINPX
3780 QLNXB1 = QLNXB1 - QDTXP
3790 IF QLNXB1 < QLNL THEN RETURN
3800 QLNB3 = QLNB - 3
3810 LINE (QLNXB1, QLNB)-(QLNXB1, QLNB3)
3820 NEXT QQ
3830 RETURN
3840 REM routine to draw y tic marks
3850 QYLNB1 = QLNB
3860 QDTYP = INT((QLNB - QLNT) / QNINPY)
3870 FOR QQ = 1 TO QNINPY
3880 QYLNB1 = QYLNB1 - QDTYP
3890 QLNL4 = QLNL + 4

148
3900
3920
3925
3930
3940
3950
3960
3970
3980
3990
4000
4010
4020
4030
4040
4050
4060
4061
4070
4080
4090
4100
4110
4120
4130
4140
4150
4160
4170
4180
4190
4200
4210
4220
4230
4240
4250
4260
4270
4280
4290
4300
4305
4310
4315
4320
4330
4340
4350
4360
4370
LINE (QLNL, QYLNB1)-(QLNL4, QYLNB1)
IF QQ = QNINPY AND QDTYP = 1 THEN QQ = QQ - 34
NEXT QQ
RETURN
'********** LINEAR REGRESSION***************************
INPUT "LEFT MOST BORDER (1-512)"; N
INPUT "RIGHT MOST BORDER (1-512)"? J
QLNB = 164
DEFDBL P, S
M = J - N + 1
SX = 0; SY = 0: PX = 0: PY = 0: PC = 0
IF ORDER < 1 OR ORDER > 4 THEN ORDER = 4
TO J
= 4 THEN QLY(I) = CON(I)
THEN QLY(I) = LOG(ABS(CON(I)))
THEN QLY(I) = 1 / CON(I)
THEN QLY(I) = (1 / CON(I)) A 2
FOR I = N
IF ORDER
IF ORDER
IF ORDER
IF ORDER
RHGRFLAG
SX = SX +
PX = PX +
PC =
NEXT
D# =
A =
B =
VX#
VY#
RR#
R =
E =
RE
GB
GA
GP
= 1
= 2
= 3
= 1
QX( i)
QX( i)
QX (i)
SY = SY
* QX(I):
* QLY(I)
+ QLY(I)
PY = PY + QLY(I) * QLY(I)
PC
I
M * PX - SX * SX
(SY * PX - PC * SX) / D#
(M * PC - SX * SY) / D#
= (PX - SX * SX / M) / (M - 1)
= (PY - SY * SY / M) / (M - 1)
= B * B * VX# / VY#
SQR(RR#)
SQR((1 - RR#) / (M - 2)) / R
= (M - 1) * VY# * (1 - RR#)
= ABS(E * B)
= GB * SQR(PX / M)
= SQR(RE / (M - 1))
K = ABS(B): IF ORDER = 3 THEN K = K / 2
PRINT "INTCPT="; : PRINT USING "##.##AAAA"; A;
" (STD DEV="; : PRINT USING "##.##AAAA"? GA;
") SLOPE="; : PRINT USING "##.##AAAA"; B;
"(STD DEV="; : PRINT USING "##.##AAAA"; GB;:PRINT
"R="; R; " E="; EE; " STD DEV PTS="; GP;
.8 GOTO 4320
PRINT
PRINT
PRINT
PRINT
IF R
it ^ ti
PUT (0, QLNB - 64), BTARY, PSET
LOCATE INT(((QLNB - 64) / 200) * 25 + 1) + 1, 1
PRINT TAB(30); ; PRINT "THIS IS NOT A WELL FIT CURVE"
REM FOR LLKK = 1 TO 2000:MYBADDOG=LOG(LLKK):NEXT
IF INKEY$ = "" THEN 4320
PUT (0, QLNB +11), BTARY, PSET; LOCATE INT((QLNB / 200) *
25 + 1) + 2, 1
INPUT "WOULD YOU LIKE A PLOT OF THE RESULTS"; B$
B$ = LEFT$(B$, 1)
IF B$ = "N" THEN RETURN
PUT (0,
25 + 1)
QLNB
+ 2 ,
11), BTARY, PSET: LOCATE INT((QLNB / 200) *

149
4380 IF B$ <> "Y" THEN GOTO 4330
4390 FLORD = 1
4400 INPUT "WHAT RESOLUTION WOULD YOU LIKE TO GRAPH (1 TO 10)";
QRES
4405 IF QRES < 1 OR QRES > 20 THEN QRES = 1
4410 FOR I = N TO J
4420 CC = QY(I)
4430 QY(I) = QLY(I)
4440 QLY(I) = CC
4450 NEXT I
4460 QFLG = 0: QMINX = QX(N): QMAXX = QX(J): QMINY = QY(N)
4465 QMAXY = QY(J): QN = J
4470 QYN = B * QX(N) + A
4480 QYJ = B * QX(J) + A
4490 IF B < 0 GOTO 4520
4500 IF QYN < QY(N) THEN QMINY = QYN ELSE QMINY = QY(N)
4510 IF QYJ > QY(J) THEN QMAXY = QYJ ELSE QMAXY = QY(J)
4520 IF B > 0 GOTO 4550
4530 IF QYN > QY(N) THEN QMAXY = QYN ELSE QMAXY = QY(N)
4540 IF QYJ < QY(J) THEN QMINY = QYJ ELSE QMINY = QY(J)
4550 GOSUB 2160
4560 QYN = FNQSC(QYN / QSCLY, QMAXPY, QMINPY, QLNT, QLNB)
4570 QXN = FNQSC(QX(N) / QSCLX, QMAXPX, QMINPX, QLNR, QLNL)
4580 QY2 = FNQSC(QYJ / QSCLY, QMAXPY, QMINPY, QLNT, QLNB)
4590 QX2 = FNQSC(QX(J) / QSCLX, QMAXPX, QMINPX, QLNR, QLNL)
4600 LINE (QXN, QYN)-(QX2, QY2)
4610 FOR I = N TO J
4620 CC = QY(I)
4630 QY(I) = QLY(I)
4640 QLY(I) = CC
4650 NEXT I
4660 QMINX = QX(1): QMAXX = QX(512): QMINY = QY(515)
4665 QMAXY = QY(514): QN = 512
4670 FLLOOP = 1 + FLLOOP
4680 IF FLLOOP > 1 THEN GOTO 4765 ELSE GOSUB 1570
4690 PUT (0, QLNB +11), BTARY, PSET
4695 LOCATE INT((QLNB / 200) * 25 + 1) + 2, 1
4700 PRINT "INTCPT="; : PRINT USING "##.##AAAA"; A;
4710 PRINT " (STD DEV="; : PRINT USING "##.##AAAA"; GA;
4720 PRINT "( SLOPE="; : PRINT USING "##. ##AAAA"; B;
4730 PRINT " (STD DEV="; :PRINT USING "##.##AAAA"; GB;:PRINT ")"
4740 PRINT "R="; R; " E="; EE; " STD DEV PTS="; GP;
4745 REM FOR LLKK = 1 TO 2000:MYBADDOG=LOG(LLKK):NEXT
4750 IF INKEY$ = "" THEN GOTO 4750
4760 FLLOOP = 0
4765 REM GOSUB 1570
4770 RETURN
4780 '************* SAVE **************************************
4790 CLOSE #1
4800 IF FLDATA > 0 THEN GOTO 4820
4810 PRINT "NO DATA SOURCE. RETURNING TO MENU": GOTO 4910
4820 IF FLDATA = 2 THEN PRINT "DATA PREVIOUSLY SAVED"
4821 INPUT "SAVE AGAIN UNDER ANOTHER NAME? "; RJHANS$

150
4822 IF LEFT$(RJHANS$, 1) = "N" THEN GOTO 4900
4823 INPUT "WHICH DRIVE DRV$: IF DRV$ = "" THEN DRV$ = "C"
4824 DRV$ = LEFT$(DRV$, 1)
4825 IF DRV$ = "A" OR DRV$ = "B" GOTO 4829
4826 IF DRV$ = "C" OR DRV$ = "D" GOTO 4829
4827 GOTO 4823
4829 DRV$ = DRV$ +
4830 INPUT "FILENAME " ; FILENAME$
4840 B$ = DRV$ + LEFT$(FILENAME$, 8)
4850 OPEN "0", #1, B$
4860 SIZE = 518
4870 FOR I = 1 TO SIZE STEP 5
4880 PRINT #1, QY(I), QY(I + 1), QY(I + 2),QY(I + 3),QY(I + 4)
4890 NEXT I
4900 CLOSE #1
4910 OPEN "coral:9600,n,8,1,CS,ds,Cd" FOR RANDOM AS #1
4920 FLDATA = 2
4930 RETURN
4940 '*************** LOAD ***********************************
4950 CLOSE #1
4951 INPUT "WHICH DRIVE DRV$: IF DRV$ = "" THEN DRV$ = "C"
4952 DRV$ = LEFT$(DRV$, 1)
4953 IF DRV$ = "A" OR DRV$ = "B" GOTO 4959
4954 IF DRV$ = "C" OR DRV$ = "D" GOTO 4959
4955 GOTO 4951
4959 DRV$ = DRV$ +
4960 INPUT "FILENAME"; FILENAME$
4970 B$ = DRV$ + LEFT$(FILENAME$, 8)
4980 OPEN "I", #1, B$
4982 ON ERROR GOTO 5230
4990 SIZE = 518
5000 FOR I = 1 TO SIZE STEP 5
5010 INPUT #1, QY(I), QY(I + 1), QY(I + 2),QY(I + 3),QY(I + 4)
5020 NEXT I
5030 PER = QY(513): QMAXY = QY(514): QMINY = QY(515)
5035 VO = QY(516): VM = QY(517); L = QY(518): EE = QY(519)
5040 PRINT "FILE "; B$; " FOUND."
5050 CLOSE #1
5060 OPEN "coml:9600,n,8,l,cs,ds,cd" FOR RANDOM AS #1
5061 LEFF = 2.303 * L * EE: VFULL = VM - VO
5062 PRINT "VO,VM,VFULL,L,LEFF,E": PRINT VO, VM, VFULL, L; "
"? LEFF, EE
5063 INPUT "WANT TO CHANGE VO,VM,L,OR E ANANS$
5064 IF ANANS$ = "Y" THEN GOSUB 8000
5068 LEFF = 2.303 * L * EE: VFULL = VM - VO
5070 REM FOR ZSAM = 1 TO 5000: ZSAM = LOG(ZSAM): NEXT
5085 FOR I = 1 TO 512
5088 QX(I) = I * PER
5090 CON(I) = -LOG(ABS((QY(I) - VO) / VFULL)) / LEFF
5092 OD(I) = -LOG(ABS((QY(I) - VO) / VFULL)) / 2.303
5095 REM PRINT CON(I)
5100 NEXT I
5110 FLDATA = 2

5115
5120
5130
5140
5150
5160
5170
5180
5190
5200
5210
5220
5230
5240
5250
5255
5256
5260
5270
5280
5290
5300
5310
5320
5330
5340
5350
5360
5370
5380
5390
5400
5410
5420
5430
5440
5450
5460
5470
5480
5490
5500
5510
5520
5530
5540
5550
5560
5570
5580
5585
5590
5600
151
RHGRFLAG = 1
RETURN
/*************** N'th ORDER *****************************
PRINT
PRINT
PRINT
PRINT
PRINT
INPUT
IF ORDER
RETURN
PRINT "CHOOSE THE ORDER OF THE REACTION": PRINT
"1) FIRST ORDER
"2) SECOND ORDER
"3) THIRD ORDER
"4) ABSORBANCE ONLY
"WHICH NUMBER"; ORDER
< 1 OR ORDER > 4 GOTO
ln(C)=ln(Co)-K*t"
(1/C)=(l/Co)+K*t"
(1/C)A2=(1/Co)A2+2*K*t"
C=Co-K*t": PRINT
5140
'********************** ERROR ***************************
/IF(57=ERR)AND(180 > ERL) THEN RESUME 160
IF 57 = ERR THEN PRINT"DP600 OR DISK I/O ERROR":RESUME 140
IF 53 = ERR GOTO 5290
IF 4970 = ERL THEN GOTO 5290
IF 4980 = ERL THEN GOTO 5290
REM PRINT "STOP": PRINT ERR, ERL
REM IF ERR=6 THEN BAD=ERL:GOTO ERL
RESUME NEXT
PRINT "FILE B$; " NOT FOUND"
FILENAME$ = ""
CLOSE #1
RESUME 4950
'****************** COMPARE **************************:
INPUT "HOW MANY PLOTS DO YOU WISH TO MAKE (1 TO 3)"; NOPLO
IF NOPLO < 1 OR NOPLO > 3 GOTO 5340
PRINT : PRINT "LOAD FIRST DATA SET FROM DISK": PRINT
'LOAD
'PLOTTER
GOSUB 4940
GOSUB 1480
N1 = N: J1 = J
DIM QY1(515)
FOR I = N TO J
QY1(I) = QLY(I)
NEXT I
IF B < 0 GOTO 5460
QY1(515) = QY1(N): QY1(514) = QY1(J): GOTO 5470
QY1(515) = QY1(J): QY1(514) = QY1(N)
IF NOPLO = 1 GOTO 5750
PRINT : PRINT "LOAD SECOND DATA SET FROM DISK": PRINT
GOSUB 4940
GOSUB 1480
N2 = N: J2 = J
DIM QY2(J)
FOR I = N TO J
QY2(I) = QLY(I)
NEXT I
IF B < 0 GOTO 5590
'LOAD
'PLOTTER
IF QY2(N)
IF QY2(J)
GOTO 5610
IF QY2(N)
IF QY2(J)
QY1(515)
QY1(514)
QY1(514)
QY1(515)
THEN
THEN
THEN
THEN
QY1(515)
QY1(514)
QY1(514)
QY1(515)
QY2(N)
QY2(J)
QY2(N)
QY2(J)

5610
5620
5630
5640
5650
5660
5670
5680
5690
5700
5710
5720
5725
5730
5740
5750
5760
5770
5780
5790
5800
5805
5810
5820
5830
5840
5850
5860
5870
5880
5890
5900
5910
5920
5930
5940
5950
5960
5970
5980
5990
6000
6010
6020
6030
6040
6050
6060
6070
152
IF NOPLO = 2 GOTO 5750
PRINT : PRINT "LOAD THIRD DATA SET FROM DISK"
GOSUB 4940
PRINT
GOSUB 1480
N3 = N: J3 = J
DIM QY3(J)
FOR I = N TO J
QY3(I) = QLY(I)
NEXT I
IF B < 0 GOTO 5730
'LOAD
'PLOTTER
IF QY3(N)
IF QY3(J)
GOTO 5750
IF QY3(N)
IF QY3(J)
N = Nl:
IF N2 <
IF J2 >
IF N3 <
IF J3 >
QY1(515)
QY1(514)
THEN
THEN
QY1(515)
QY1(514)
QY3(N)
QY3(J)
QY1(514)
QY1(515)
QY3(N)
QY3(J)
(1
> QY1(514) THEN
< QY1(515) THEN
J = J1
Nl AND NOPLO > 1 THEN N = N2
J1 AND NOPLO > 1 THEN J = J2
N AND NOPLO > 2 THEN N = N3
J AND NOPLO > 2 THEN J = J3
QFLG = 0: FLORD = 0: QMINX = QX(N): QMAXX = QX(J)
QMINY = QY1(515): QMAXY = QY1(514): QN = Jl: N = Nl
PRINT : INPUT "WHAT RESOLUTION WOULD YOU LIKE TO GRAPH
TO 10)"; QRES
FOR I = Nl TO Jl
QY(I) = QY1(I)
NEXT I
ERASE QY1
FLORD = 0
GOSUB 2170
LOCATE 1, 59
PRINT " "
IF NOPLO = 1 GOTO 6040
QFLG =2: QN = J2: N = N2
FOR I = N2 TO J2
QY(I) = QY2(I)
NEXT I
ERASE QY2
GOSUB 2170
IF NOPLO = 2 GOTO 6040
QN = J3: N = N3
FOR I = N3 TO J3
QY(I) = QY3(I)
NEXT I
GOSUB 2170
ERASE QY3
PUT (0, QLNB + 11), BTARY, PSET: LOCATE INT((QLNB / 200) *
25 + 1) + 2, 1
PRINT "YOU WILL NEED A NEW DATA SOURCE AFTER RETURNING TO
MENU"
IF INKEY$ = •
PUT (0, QLNB
25 + 1) + 2,
THEN
11)/
GOTO 6060
BTARY, PSET:
LOCATE INT((QLNB / 200) *

6080 PRINT "PRESS ANY KEY ONCE TO GET A SCREEN DUMP"
6085 PRINT "TWICE TO RETURN TO MENU";
6090 IF INKEY$ = "" THEN GOTO 6090
6100 PUT (0, QLNB + 11), BTARY, PSET: LOCATE INT((QLNB / 200)
25 + 1) + 2, 1
6110 IF INKEY$ = "" THEN GOTO 6110
6120 FLDATA = 0
6130 RETURN
7000 REM SUBROUTINE GET INFO
7040 '
7070 CLS
7080 REM OPEN "coml:9600,n,8,1,cs,ds,cd" AS #1
7100 BOUT$ = B$
7110 PRINT #1, BOUT$
7120 FOR I = 1 TO 1500: QWERT1 = QWERT1 + 1
7140 NEXT I
7150 J = 1
7160 V = LOC(l): IF V < 1 THEN PRINT "NO MESSAGE": GOTO 7350
7170 FOR ZQQZ = 1 TO 500: FF = ZQQZ * ZQQZ: NEXT
7180 AGI$(J) = INPUT$(V, #1)
7190 ON ERROR GOTO 5220
7200 V = LOC(l): IF V < 1 THEN GOTO 7230
7210 J = J + 1
7220 GOTO 7160
7230 FOR HH = 1 TO J
7240 BGI$(HH) = ""
7250 REM PRINT AGI$(HH), VAL(AGI$(HH))
7260 FOR UU = 1 TO LEN(AGI$(HH))
7270 QAQ$ = MID$(AGI$(HH), 1)
7280 ZORP$ = BGI$(HH)
7285 IF ASC(QAQ$) = 45 THEN GOTO 7300
7290 IF ASC(QAQ$) < 48 OR ASC(QAQ$) > 91 THEN GOTO 7330
7300 BGI$(HH) = BGI$(BB) + QAQ$
7310 NEXT UU
7320 NEXT HH
7330 MYINFO = VAL(ZORP$)
7350 RETURN
8000 REM CHANGE V0,VMAX **********************************
8010 INPUT "DO YOU WANT TO CHECK ACTUAL VOLTAGE VALUES OF
DATASET"; ANANS$
8020 IF LEFT$(ANANS$, 1) = "N" THEN GOTO 8090
8030 INPUT "FIRST , LAST DATA TO USE POINT1, POINT2
8035 TEMPSUM = 0
8040 FOR KZ = POINT1 TO POINT2
8050 TEMPSUM = TEMPSUM + QY(KZ)
8060 NEXT KZ
8070 VNOW = TEMPSUM / (POINT2 - POINT1 + 1)
8080 PRINT "AVERAGE VOLTAGE FOR THAT RANGE IS VNOW
8090 INPUT "CHANGE VO "; ANANS$
8100 IF ANANS$ = "N" THEN GOTO 8200
8110 INPUT "NEW VO"; VO
8200 INPUT "CHECK VOLTAGES AGAIN "; ANANS$
8210 IF LEFT$(ANANS$, 1) = "Y" THEN GOTO 8030

8240
8250
8260
8270
8300
8320
8330
8400
8420
8430
8500
8510
8520
8515
8530
8540
8550
8560
8570
8580
8600
9800
9810
9820
9830
9840
9850
9860
9870
9875
9880
9890
9892
9894
9896
9898
9900
9905
9910
9915
9920
9925
9930
9940
9945
9946
9999
154
INPUT "CHANGE VM ANANS$
IF ANANS$ = "N" THEN GOTO 8300
INPUT "NEW VMAX "? VM
VFULL = VM - VO
PRINT "L IS NOW L: INPUT "CHANGE L ANANS$
IF ANANS$ = "N" THEN GOTO 8400
INPUT "NEW L"; L
PRINT "E IS NOW EE: INPUT "CHANGE E "; ANANS$
IF ANANS$ = "N" THEN GOTO 8500
INPUT "NEW E EE
LEFF = 2.303 * L * EE: VFULL = VM - VO
QY(516) = VO: QY(517) = VM: QY(518) = L: QY(519) = EE
PRINT "VO,VM,VFULL,L,LEFF,E": PRINT VO, VM, VFULL, L; "
LEFF, EE
IF VFULL = 0 OR LEFF = 0 THEN PRINT "BAD CONSTS. ": GOTO
8010
FOR I = 1 TO 512
QX(I) = I * PER
CON(I) = -LOG(ABS((QY(I) - VO) / VFULL)) / LEFF
REM PRINT CON(I)
NEXT I
FLDATA = 2
RETURN
REM *****************DISK DIR***********************
CLOSE #1
INPUT "WHICH DRIVE «; DRV$: IF DRV$ = "" THEN DRV$ = "C"
DRV$ = LEFT$(DRV$, 1)
IF DRV$ = "A" OR DRV$ = "B" GOTO 9870
IF DRV$ = "C" OR DRV$ = "D" GOTO 9870
GOTO 9820
MYCALL$ = DRV$ + ":"
FILES MYCALL$
OPEN "coml:9600,n,8,1,cs,ds,cd" FOR RANDOM AS #1
RETURN
INPUT "WHICH DRIVE"; DRV$: IF DRV$ = " " THEN DRV$ = "C"
DRV$ = LEFTS(DRV$, 1)
IF DRV$ = "A" OR DRV$ = "B" GOTO 9905
IF DRV$ = "C" OR DRV$ = "D" GOTO 9905
GOTO 9892
DRV$ = DRV$ +
INPUT "FILE NAME"; FILENAMES
B$ = DRV$ + LEFTS(FILENAMES, 8)
OPEN "0", #1, B$
FOR I = N TO J STEP 5
PRINT #1, QX(I), OD(I),
NEXT I
CLOSE #1
GOTO 2106
END

REFERENCES
1. Ramirez, J. E.; Bera, R. K. ; Hanrahan, R. J. "Measure¬
ment of Kinetic Parameters Relevant to the Operation
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2. Ramirez, J. E.; Bera, R. K. ; Hanrahan, R. J. "Forma¬
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3. Bera, R. K.; Hanrahan, R. J. "Investigation of OH
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Water Vapor," J*. Appl. Phys. 1986, 60(6), 2115.
4. Bera, R. K.; Hanrahan, R. J. "Investigation of OH-H2
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5. Bera, R. K.; Hanrahan, R. J. "Investigation of Gas
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6. McCarthy, R. L.; MacLachlan, A. "Transient Benzyl
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7. Matheson, M. S.; Dorfman, L. M. "Detection of Short-
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8. Ebert, M.; Keen, J. P.; Swallow, A. J. Pulse Radioly-
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9. Matheson, M. S.; Dorfman, L. M. Pulse Radiolysisf The
MIT Press: Cambridge, Massachusetts, 1969.
10. Matheson, M. S. "Pulse Radiolysis," in Advances in
Radiation Research. Physics and Chemistry. J. F.
Duplan and A. Chápiro, eds., Vol. 1, Gordon and Breach
Science Publishers: New York, New York, 1973.
11. Tabata, Y., ed. CRC Handbook of Radiation Chemistry,
CRC Press: Boca Raton, Florida, 1991; Chapters 2 and
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155

156
12. Verma, N. C.; Fessenden, R. W. "Time Resolved ESR
Spectroscopy. II. The Behavior of H Atom Signals," J.
Chem. Phvs. 1973, 58(6), 2501.
13. Fessenden, R. W. "Time Resolved ESR Spectroscopy. I. A
Kinetic Treatment of Signal Enhancements," J_s_ Chem.
Phys. 1973. 58(6), 2489.
14. Trifunac, A. D.; Norris, J. R.; Lawler, R. G. "Nano¬
second Time-Resolved EPR in Pulse Radiolysis via the
Spin Echo Method," J_¡_ Chem. Phys. 1979, 71(11), 4380.
15. Maughan, R. L.; Michael, B. D.; Anderson, R. F. "The
Application of Wide Band Transformers to the Study of
Transient Conductivity in Pulse Irradiated Aqueous
Solutions by the D.C. Method," Radiat. Phys. Chem.
1978, 11, 229.
16. Janata, E. "Submicrosecond Pulse Radiolysis Conductiv¬
ity Measurements in Aqueous Solutions—I," Radiat.
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17. Janata, E.; Veltwisch, D.; Asmus, K.-D. "Submicrosec¬
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43.
18. Hodgson, B. W.? Keene, J. P.; Land, E. J.; Swallow, A.
J. "Light-Induced Fluorescence of Short-Lived Species
Produced by a Pulse of Radiation: The Benzophenone
Ketyl Radical," J^. Chem. Phvs. 1975, 63(8), 3671.
19. Dallinger, R. F.; Guanci, J. J.; Woodruff, W. H.;
Rodgers, M. A. J. "Vibrational Spectroscopy of the
Electronically Excited State: Pulse Radiolysis/Time-
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2206.

BIOGRAPHICAL SKETCH
Charles L. Crawford was born in Orlando, Florida on
November 24, 1963. He moved with his family to Charlotte,
North Carolina in 1966, where he resided until moving to
Gainesville, Florida in 1986.
He received the Bachelor of Science degree in Chemistry
at the University of North Carolina, Chapel Hill in 1986.
During graduate school at the University of Florida he
held graduate teaching and research assistantships in the
Department of Chemistry and a graduate research assistant-
ship at Los Alamos National Lab in Los Alamos, New Mexico.
Charles is the youngest son of Nathan and Doris and his
older brother is John.
169

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 deqree of Doctor of Philosophy.
irahan, Chairman
Professdy 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.
ÍT! Luis Muga U
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.
vyy.
12.
SfL
:he
Eyler
essor 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.
Phillip }4. Achey
Professor of Microbiology
and Cell Science

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.
December 1991
Dean, Graduate School

university of Florida
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