Molecular Polarisation: An Investigation of the Fundamental Relationship Between the Molecular Polarisation of a Solute and the Nature of the Solvent

180 Pages·021.066 MB·English

by  Witten, Leslie B

M O L E C U L A R P O L i E I S i f l O l
AN INVESTIGATION OF THE FUNDAMENTAL RELATIONSHIP
BETWEEN THE MOLECULAR POLARISATION OF A SOLUTE
AND . THE NATURE s OF ' THE SOLVENT '
Thesis presented to the University of London
in the Faculty of Science
hy
Leslie B. Witten
for the Degree of Doctor of Philosophy
ProQuest Number: 10803955
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xs***? "I** *. ??S •*';r-.u*(v.f* ;•..■»•-**. ■*r/^~« .-I <r^s «<P‘.'/V--r *• .»*«■•*:'*• * ,. ,.,., ^ ..,
- ^tfrr- r* 5 rm^ ,
ha iarestivatioa lias been iimoa of tli© laaXeotftar polarisation of jn butyl
- Chloride and cyanide is aolntloa in i&s^yolg? solvents. ®be sareXX
Mig© of dielectric cmstaats ancoaaterod renii.rcd ilia acoumsj of their -.
.dctesxdn&tiaft to M 00 high as pomaM.% sad pcxi&ci&ar attention ms given
to the daairp of o_g?cuvi&us earn the reduction of easpertasntsl eirors. fhe
polarisation at Infinite dilution is impendent of the method of essbvarJ'-
polstion used provided the aocmrnoj of the e^erdraeiital results is Mgh but
a method islxlok treats the separate pi^rsical constants of 'each eolation is .
preferable to any cadent on a derived function (e»g* laoXecul&r polaris­
ation). "-$hat proposed by .Eodvcrstadt aadKmter is satisfactory and is
also vory critical - of, the data Q3s&ilne&»... .......
~: Based [email protected]\ o ^cootli Classics relationship and' if the vqpour
plmsc data &m mrmct, . tbo-t^^-ront .isolooular polarisation of tptmtyl V
c&doridc is greater in solt'ticm than in tha: vigour p‘*acc m ile that for
saeUiyl cy_vtv~e is less. / - SMs is the only effect directly attribu&abXe-to-- •..•••
nolecdsr and according to the theories of frmfs and ^tigasS italics
that m tli t. ovtyl chloride the axis of rredL an poXarisability is at right
apglea to that of the dipole. Hot/cr/er, th® resnlfec for tfbntyl cl&ori&e
jaust be considered anorrjotis since they do not cQJifl,n t’icse. authors*,
•predictions tliat tlae total taolecrdiar polarisation at infi^iite dil'otioa slmdd ^
increase 7/ith iiweasi^i dielectric e of tlia solvent* Em r t
•■
£§>oeifio folmes of the solntos wry fr^*i Bolrent to and aXwioufi :
variations do flot' ^rrd a te mth tlie variations of the polarisnfejonj ttc / are.
-©iidlar for eacb solute, tlmse for imstliyl cyanide beii^g the groater*
«
fhe e^erir^ital ■ msrlts bave been, essrained by ^plioation of:
eqimtions proposed by vasriens mo&kmm but in- _m case are the resets
correlated for all solvents. illl. tlie c:eirossi0:2c ngro® iai giving tlie •
ilghc'st polarisations for solutions in or contsiniag oie:nn is probably
die to bonding, tlio oivatatioB being aasociated mth tlie orientation
polarin *tioa only# Hie nomsl paral^tes are anDiacdoae x>olarisaticns -
lovier than those fo\xrJi in sc?vvcnts of Mglncr dielectrio co ici. ^dle ird^<od '
solvents; give different polarisations from that in a pore solvent mtii thk ,■■
sens dielectric constant.: i"-?"
■ -. .. : - . . . . /
In genex^l, none of tlie eqimtioiis cm alone predict tlie e^eri^Etal. .
remits sad it seeos probable that eacli solution must be treated as a ..■•
separate problem' •• /
«-.—ooOoo«w*w»
1* General Theory ••
2* Ste&suresients in Solution "
3* Solvent Effect
4* Scope of Investigation ■■ • , --
Experiment at - «* •• **' *« ' * *
1. Accuracy and Significance of.'
■ -• '• Observational. • Errors t
2* Apparatus ■ - a
- 3* Preparation of''Solutions —
4* Order of - Determinations
' 5* Purification of -Solutes and Solvents.,.
6* Examination and .Interpretation
of Experimental Results ~
Discussion *.» .a**
1* General : ;/
2* The lormal ■ Paraffins and'Hixed Solvents'
3* The Relationship ?roposed;/fcy'Sugden
4* Corrections'for Molecular Shape
and-Anisotropy- ■■■.
5* Modifications to •• the" Internal -
field. Hypothesis.- -
6* IXtermtive Approaches to the-
■ Fundamental Theory
7* Combined Corrections for Anisotropy ■
and . the.Internal field .
qonclu Sxons. #. * < * - # ■ * » - * » : ■ » * * * •
References ♦. »« * * •« »« . **.
Tables and figures ' ** h * * * * .* .. .
(Tables 1-26)
(Figures 1 - 14) •
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