The photochemistry of the formation of sulfuryl chloride

87 Pages·011.216 MB·English

by  Londergan, Martin Christopher

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♦WSS S M f W Sflt W W AW
f8S FORMATION OF SULFURYL CHLORIDE
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Martin Christopher Londergan
Tbesi* Submitted to the Graduate Faculty
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for the Degree of
DOCTOR PHILOSOPHY
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State College
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1942
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UMI Number: DP12102
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table of contents
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BITBQDUCTIQlf*. ..s.**......**...******.*..******.* ****** %
HISTORICAL*. .*.**. *.♦.*# 4
•HFlRIMEiTAL IMlfls^IQ&TIGli** **«****»«***.*.*•**«*.•****. . f-
A. Apparatus**......*.**....*.******.*.******..** f
1. Light souree*******.*..****.*..**•******** f!
2* Reaction chamber and method of stirring**. S'
3. Manometer and measurements*...... 11
B* Bi*©parati<m of the Materials*#**...*..***■*.... IS
1* gfaLoria©*#***.*.**. *#*****.**********. .*** IS
2* sulfur dicadUI**. *-*#****.****.. *****......** is
3* sulfuryl chloride* #•»•**.**.•****•«.******** IS
f* Mwteii*aiMe&s»******** **
1* Th© nmetl©a**,*,****•«,**#**■*•*...*..**... 10
2* Light lot«n*l%ff *-**«••««•*#*#*.»**...*«.*** IS
IJfTBRPBmTIOU OF RESULTS*..**».****.******....*,***..* 33
4* Light Absorption and Qmatom Efficiency. ****** 3i
1* Absorption of light by the chlorine* *...** 33
2* The quantum #ffiei#a#jr **************••»•«* §§'
B* The Reaction.................................. #3
0* Dissociation of Sulfuryi Chloride*.*****...*** ft
D. Calculation of the Free Energy................ W
SOMIAHJr ****** ** *** * * * *» * *,**♦♦♦* *♦* TS
LITERATURE CITED* »***} w# * m- »,**>» »■** ■* m * * *♦** * * * ** * *; * -m m- * * * * so
T T 4 - 4 - T
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I* HIT RODtlCT101
The fundamental laws of photochemistry date hack to
Grotthus {1} in 1817• Adi formulated by him -and later by Draper (2)
1« 1839, th© law which tears their mama »%m%m that only the
light which la absorbed can produce a chemical ©tenge*
The developMisf of photochemistry mm. m «»ct aa$moitm pro*,
ceeded very slowly, and it was not until the application of the
quantum theory to chemical reactions by Einstein (3) in 1912
ttaii the wma&tm could be placed mm m fsaafitetiv© tests* later
developments have indicated that radiations are absorbed in a
aalsrtal body 1ft units or taanta' and through this absorption the.
hefty becomes activated and in some cases capable of reacting.
If m reaction takes pitto, th© primary process should be one la
which on© atom or molecule should react for each quantum of light
absorbed* fh© over-all reaction differs from the primary process
la tint s©©©aiiiry reactions, wall effect#, an#. dto&fclis&le&ft #f
ssany types show the result that the numbers of molecules reacting
for each quantum of radiation absorbed (quantum efficiency) may
vary from a very swill fraction t# 1#* It I* accepted
that the primary process in © photochemical reaction depend* upon
the activation of mm mf®» or molecule by the absorption of m
quantum of light* Th© ovsr-all reaction would result .from any
secondary reactions added to this primary process*
A survey mmm mad* is the field of photoch«l#try for a
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.wtileh might h# used $m the separation of isotopesI th®
reaotion oi sulfur dioxide and chlorine offered tht best p©#*
sIMI.it I«s*
The theory to be tested in this method of isotopic separa­
tion depends upon th© selective absorption of light by mam tip#
of an t sot ©pic atom or molecule over another la as., isotopic
mixture. Taking chlorine as an example* there are about 3*35
chlorine mbmm with an atomic weight, of -.38 t# otory ©hlorl*®
atom with an atomic weight of ST.* This gives a mixture of
three types of molecules C135C135> C135C1S7» and C137C137 is
the ratio 11*3 to 8*7 to 1. being one tube of chlorine gas mm
a filter to remove all the light which could be absorbed by
the Cl3gCl3& molecule* there should lie a larger f reel ten of the
light passing through the filter which could be absorbed by the
C137C1S7 molecule. This light, which had already through
th© first tube of chlorine, would then enter a second tub©.-that
also contains chlorine gas* This second tube would contain
another substance -b®ai#oa't..te§ oblorSafr; which would.- react with,
the activated chlorine molecules* The light entering the second
tub# could activate only the C137C137 molecule as all had been
absorbed which would activate the C135C135. The resulting
product after activation should contain a much larger percentage
of Cl37 than one formed using the usual chlorine gas* If art far
dioxide were the second molecule present, the sulfuryl chloride
which was formed should be enriched in Clgy
**
These values are given by Elliot; Pros* Hoy. See. (London)»
A123, 629-44. 3.989* *
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5-
In th®- choic® of a resetion of this type several factors
had to b® considered, There must of a©Oi»sity be isotopes
present' in the absorbing molecule in ®neb a ratio that th®
light would b© selectively absorbed by one type of.the isotopic
ssapOBent* Tear© .should b® no chain reactions and y#ry.f#w.*.
if any, sido reactleas* fb@ tmatum efficiency,,, which 1© the'
ratio of the mmhse. of molecules of the product f®r»«d to the
number of quants of light.absorbed,.should be- ene«
The reaction of .sulfur dioxide and chlorine upon, th®
activation by aoMOChresatic light seemed to folfill thee# con*
dttim** it.«&#. assess*??.though that a thorough staty of
this reaction 'be mad® wader various experimental conditions
before' a&sttsGipt could he nsde.ta aoparai®. the Isotopes of
chlorine by-this method* It is sa this phase of th® problem
that this .investIgatloa has been performed.
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IX. HISTORICAL
Regnault (4) in 18X1 has given tie first recorded observa­
tion that sulfur dioxide and chlorine combine under the influence
#f light. W» #i#®rv#d that if the two gas®# mm® stiihsA maA «-*
posed to th® strong rays of the summer sun, a liquid condensed
#s the walls of th® vessel* lifeawia** he 8gt4@#ft ttm* very
little or none of the liquid formed when the mixture was exposed
t# the rays of the winter sua, indicating that the reme^Xm wtm
probably due to the shorter radiations which would be much «*&**
during the winter months*
■tramt*. -ff! la- IWI smmmsvwX the vmpor ien«tei 'of iwlfnrfi
chloride aad determined the decomposition of the gas in the
region of 100° to 200° C. From these data K® calculated th®
constants in the Bernsi specific heat equation, mast fro® ttufet*
calculations be has given m curve to show th® deeompoa it ion of
the $»*pemat tmm ■ -80® to 3©0* &« 1% -mm- ■wmmmmy t® sat a
catalyst for if® at ii® beaj^rftburit which h# vorfetd*
Activated «.tor®oal gave the best results in this dec capos it ion♦
in « t0bm paper Trauts stowed that th® photochemical
formation of sulfuryl chloride gave a stationary concentration
which-was higher t feats th# tfesmfttel #q«|Mbri»v «t ito wmm'
temperature*
L® llanc, Andrich and Eangro (?) uiMt# a study of th© .ptoto-
chiffiical #yst«Bi of » mixture of sulfur dioxide, chlorine *a$
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auifuryi etslerM#. la order to establish the effect of light- of
different wave lengths upon the reaction mixture* fhe absorption
spectra of chlorine, sulfur dioxide ant neitvryl chloride -atsw.
strong maxima in different regions of the spectrum, That of
chlorine is about 3400 A, sulfur dioxide is about 3000 and
m ifuryl chloride shows a m a x i m of absorption below Hit# A*
Ttstr afforded a method of studying the effect of light ap§» ttet
atxtiir© which would activate only one of m b of the three types
of molecules in the mixture* They found that light below 2300 A*
which ws#. absorbed by the suLftaryl chloride, caused decomposition
Sato sulfur -digaids mmft chlorine as well £* possibly aon* other
products is mm%& amounts* When tie mixture was illuminated
with light t» th# m g £ m of lf©0 % which was absorbed by the
sulfur dioxide, they found a slight decomposition of the sulfur
dioxide but no other reaction, if a mixture of sulfur dioxide
and ehloriise was illuminated with light above 3000 A, this light-
being absorbed by the chlorine, the reaction proceeded toward
the mmrnMrn #f iJfftfuryX chloride. Air was present as &
to keep the chlorine and sulfur dioxide from coming in contact
with the mercury in tb© manometerf water vapor and more air were
aided in sea#, reactions-, but these t*w4 wmw little effect m the
formation #f a id fur yl chloride* Thus, they established the feet
that It is. tb© light which is absorbed by the chlorine in a
mixture of sulfur dioxide and chlorine which causes the photo**
chemical formation of sulfuryl chloride to take place*
Tram fsl indicate# that pm® m€ thoroughly dried .chlorine
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