Determination of velocity constants in free radical systems

84 Pages·04.406 MB·English

by  Trick, Gordon S

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DETERMINATION OF VHDCITY CONSTANTS
IN FREE RADICAL SYSTEMS
by
Gordon S. Trick
Submitted in partial fulfillment of the
requirements for the degree of
Master of Science
University of Western Ontario
1950
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UMI Number: EC45424
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The author would like to express hla appreciation
to Canadian Industries United for a Graduate Research Fellowship
in Chemistry and to the National Research Council for a aaaaer
scholarship which allowed this work to be carried out*
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(U)
AGKSOWLBDGMMS
This work was carried eat under the direction of
Dr. C. Sirertz and the author would like to express his
appreciation for the advice and encouragement given.
HLs thanks are also extended to all aesbers of
the Faculty and Graduate School of the Department of Chemistry
for advice and helpful discussions, and in particular to
a. A. Back, C. C. McDonald, and £. P. Strickland.
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Errata “ calculation of rate constants, and values given on pages 37, 38,
40 and 41, should be as follows:
Styrene-Butyl Merdaptan System -
k(l) * 1.0 z 10“7 aoles of radicals formed/litre/second (instead of 5 x 10*
(fiSB) - 4.04 sole s/litre
"SiMl ■ 9,79 x 10"5 moles/litre/Becond (instead of 1,15 x 10*"6 moles/sec,)
dt
X ■ 10“* seconds
Calculating from these experimental values, we get:
<A) - k(I)x X - 1,0 x lo”7 x lo”1 - 1,0 x 10~* moles/litre
-d(M)
-5
9.79 x 10 •a -I -I
kct * - 2,4 x 10 litre moles sec.
(A)(HSH) 4.04 x 1.0 x 10-8
k(I) 1.0 x 10“7 , „ Q , -1 „ -1
Ic* * --------- - l.o x 10 litres moles seconds
[A]2 1.0 x 10“16
-dli
>-5
_dt_ I.T?'XJQ_ m 9#8 x 102
vk -
k(I) 1.0 x 10~7
Summarizing these values,
k(I) - 1.0 x 10"7 moles/litre/sec.
kct - 2.4 x 103 11tres-molea”^sec•
kt - 1.0 x 109 li tres-moles”* sec•
▼k - 9.8 x 102
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Errata (continued)
Pentene-l-Butyl Meroaptaa syatea -
k(I) » 1.0 x 10 7 aoles/lltre/seeond (inatead of 5 x 10"8)
[M] ■ 8 x 10"1 moles/litre
-dM -3
dt “ 1,05 x 10 aolea/litre/second (instead of 1.2 x 10"5 molea/sec.)
X « 3 x 10“® seoonda
Calculating from these experimental values, we get
[RSj - k(I) x X - 1.0 x 10®7! 3 x lo"3 ■ 3.0 x lo“10 moles/litre
-dM
dt 1.05x10 . -1 -1
k< » r~~7r t ------- V7T-----""" “ 4,4* 10° litrea/molea sec.
1 [HS][M] 3.0 x 10“1° x 8x 101
k(I) 1.0 x 10“7 ,_l2 / , -1 -1
k. - — r—_ » '■ ... ■ 1.1 x 10 litres/nolea see.
Z [HSj 3 x^ 3 X, 1i0n -20
-dM
. J»L . l.q» x 10-8 . 1>lI104
k k(I) 5 x 10"8
Summarizing these values:
Ed) - 1.0 x 10“7 moles/litres/seo•
- 4.4 x 106 litres-*oles“13ee."1
*i
- 1.1 x 1018 litres-moles^sec.
*t
» 1.1 x 104
▼k
It should he noted that k^ values here are "cross termination".
For further discussion of this, see p. 56, U.W.O. M«Sc. Thesis, R.A. Back,
Sept. 1951.
Corrections made by
R» A. BACK,
Oct. 8, 1951.
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(iii)
CONTENTS
peg*
AC2DSOWLKDGEHE5TS ................. ....... (ii)
CONTENTS .... (iii)
LIST 0? ILLUSTRATIONS. .... (It)
ABSTRACT........................... (▼)
INTRODUCTION .......... 1
THEORY... ........ 5
General ........................................... 5
Theory of Intermit tent Illumination .... 8
Application to Model Molecule System.............. 19
ExpmammL,....,.......... 23
Purification of Cheoieals......... 23
Apparatus. ..... 24
Irradiation Experiaenta. .... 23
HS#8LTS......... 33
DISCUSSION AND CONCLUSIONS ....... 47
ILLUSTRATIONS. ...... 52
BIBLIOGRAPHY................. 69
VITA
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