GTUDIES IN REGULAR SOLUTION THEORY

ABHIJIT PURKAYASTHA
B.Sc.(~~ons), Jadavpur University, 1965

A THESIS SUBMITTED IN PARTIAL FULFILLXENT

,OF THE REQUIREPJENTS FOR THE DEGHEE OF
DOCTOR OF PHLLOSOPHY
,in the Department
of
Chemistry
Simon Fraser University

@ ABHIJIT PURKAYASTRA 1970

S,IMONPiUSER UNIVERSITY
August, 1970
 EXAMINING COMMITTEE APPROVAL

Name : Abhijit Purkayastha

Degree : Doctor of Philosophy
Title of Thesis: Studies in Regular Solution Theory
Date : October 27, 1970

( ~ r .John Walkley)
Research Supervisor

(Dr. D. k. Tuck)
Examining Committee

(Dr. R', G. Korteling)

Examining Committee

(Dr. E. Brian Smith)

External Examiner
Department of Chemistry
University of Oxford, England.
 The d e v e l o p n e n t o f R e g u l ~ rS o l u t i o n t h e o r y f o r

b i n a r y and t e r n f l r y r ~ i x t u r e si s d i s c u s s e d and t h e r e a -
sons f o r i t s f a i l u r e a r e noted.
The t h e r n o d y n a n i c p r o n e r t l e s o f t e r n a r y n o n p o l a r
n i x t u r e s have been p r e d i c t e d u s i n g a m o d i f i e d v e r s i o n
of t h e s o l u b i l - i t y p a r m e t e r s f o r t h e mixed s o l v e n t s .
E x c e l l e n t a p r e e n e n t between t h e o r e t i c a l and e x p e r i n e n -
t e l p r o p e r t i e s i s observed f o r d i l u t e t e r n a r y r?ixtures.
The t h e o r y h a s e l s o been e x t e n d e d t o t h e c o n c e n t r c t e d
solutions b u t n o t w i t h r ~ u c hs u c c e s s , and t h e n r o b ~ b l e
r e a s o n s f o r t h i s f a i l u r e a r e a l s o noted.
The " s c a l e d p e r t i c l e v t h e o r y o f f l u i d s f s u s e d i n
c f i l c u l a t i n p t h e p a r t i a l r n o l ~ le n t r o y o f s o l u t i o n o f
s o l i d s o l u t e s and h a s been found t o be i n e r c e l l e n t
L

agreement w i t h t h e e x n e r i n e n t ~ lr e s u l t s f r o n d i f f e r e n t ,
sources.
 - iii -
!TABLE OF CONTENTS

LIST OF TABLES

LIST OF FIGURES viii

INTRODUCTION 1

CHAPTER I. A general discussion on Regular 6

Solution theory

CHAPTER 11. Solubility of solid solutes in

mixed solvents
Heat of solution and Regular Solution
theory for three component systems
Experimental
Results
Discussion
Excess properties in mixed solvent:
Introduction
Theory
Discussion
Concentrated solution
Introduction
List of notation
Results
Discussion
Conclusion
CHAPTER 111. Calculation of entropy of
solution from scaled particle
theory
Introduction
Method of calculation
Discussion
Conclusion

REFERENCES

APPENDIX AI.l. Important thermodynamic

relations

APPENDIX AI.2. Repulsive forces

APPENDIX AII.l. Derivation of excess volume

of mixing,

APPENDIX AII.2. Derivation of al(rnax) for

APPENDIX AII.3.

APPENDIX AIII.l. Entropy of compressing a

mixture of rigid spheres

APPENDIX AIII.2. Calculation of hard sphere

diameter
 LIST OF TABLES
Table 1.1: Solubility parameter for SnI
4
--
calculated from saturation solubility
data 39

Table 1.2: Comparision of observed and experimental

max
values of xp 41

Table 1.3: Comparioson between calculated and

experimental values of partial molal
volumes of different solutes. 45

Table 11.1: Saturation solubility and partial molal

volume of iodine in mixed benzene -
cyclohexane solvent 121

Table 11.2: Iodine in benzene - cyclohexane solvent 122

Table 11.3: Iodine in benzene - carbon tetrachloride

solvent L 123

Table 11.4: Iodine in benzene - cyclohexane

and benzene - CC14 mixed solvents 124

Table 11.5: SnI in benzene

4
- c-C6H12 solvent 125

Table 11.6: Solubility parameters of C6H6- C-C6H 12

mixed solvents for C6H6 - Sni4 -
c-C6HI system

Table 11.7: AV E in mixed solvents

Table 11.8 Partial molal volume of solute in
pure solvents 128

Table 11.9: Saturation solubility of naphthalene

in CC14 - c-C6H12 mixed solvent at
298'~ 129

Table 11.10: Saturation solubility of naphthalene

in CH212 - c-C6H12 mixed solvent at
25'~

Table 11.11: Solubility parameters of mixed sol-

vents in the CC14 - naphthalene -
c-C6H12 system 131

Table 11.12: 6 values for CH212 - c-C6H12 mixed

solvent for CH212 - naphthalene -
c-C6H12 system 132

Table 11.13: bm(expt) for CC14 - C-C6H12 in CH212

- naphthalene 2 c-c6H12 system along
with N ~ / I $ values 133

Table 11.14: hm(expt) for CH212 - c- C6H12 in CH212

- naphthalene - c-C6H12 system along
with N~/N* 134

Table 11.15: Values for mm/m1 for CC14 - naphthalene

- c-C6H12 and CH212 - naphthalene -
c-C6H12 systems 135

Table 111.1: Hard sphere diameters of different

solvents and solutes 211.

Table 111.2: ii sP
for different nonpolar binary
2
mixtures 212 '
 - vii -
Table 111.3: Excess entropy of mixing for different
nonpolar binary mixtures 213

Table 111.4: Saturation solubility of Sn(c 6F5) 4

Table 111.5: Partial molal volumes of S ~ ( C F )

6 5 4

Table AI. 1.1: A summary of relations between

thermodynamic functions 224

Table A I . 1 . 2 : Thermodynamic functions for fusion

 - viii -
LIST OF FIGURES

Figure 1.1: Parameters used in describing pair

potential 9

Figure 1.2: Partial and total pressure of an

ideal mixture 22

Figure 1.3: Positive deviation from Raoultls Law 22

Figure 1.4: Negative deviation from Raoultls 22

Law

Figure 11.1: Saturation solubility of iodine in

benzene - C-C6H12 mixed solvent
versus volume fraction of benzene 136

Figure 11.2: Excess saturation solubility and

partial molal volume of I2 in benzene
- c-C6HI2 mixed solvent versus volume
fraction of benzene 137

i m
Figqre 11.3: (In ap - In x2P of I2 in benzene -
c-C6H12 mixed solvent versus volume
fraction and "effective volume frac-
tion" of benzene 139

Figure 11.4: Saturation solubility of I2 in benzene-

cyclohexane mixed solvent versus lleffce-
tive volume fraction" of benzene 140
Figure 11.5: Partial molal volume of iodine in
benzene - cyclohexane mixed
solvent versus "effective volume
fraction l1 of benzene 141

i m r
Figure 11.6: (In a2 - In x2)2 of I2 in benzene -
carbon tetrachloride mixed solvent
versus "effective volume fraction"
of benzene 142

Figure 11.7: Saturation solubility of iodine in

benzene - CC1 mixed solvent versus
4
volume fraction and "effective volume
' fraction" of benzene 143

i - In):x 71 of I2 in CC14 -
(In a2
Figure 11.8:
n-C7FI6 mixed solvent versus volume
fraction and "effective volume
fraction " of benzene 144

Figure 11.9: Saturation solubility of Sn14 in

benzene - cyclohexane mixed solvent
versu,s the volume fraction of
benzene

i
Figure 11.10: (In a2 - In):x 5 of SnI4 in
benzene - cyclohexane mixed solvent
versus volume fraction and "effective
volume fraction1#of benzene 148

Figure 1111: Saturation solubility of Sn14 in

benzene - cyclohexane mixed solvent
versus "effective volume fraction"
of benzene 150
Figure 11.12: 6, for benzene - c-C6H12 in
benzene - I2 - c-C6HI2 system versus
volume fraction and "effective volume
fraction" of benzene 151

Figure 11.13: bm for benzene - CC1 in benzene -

4
I2 - CC1 system versus volume frac-
4
tion and "effective volume fra~tion'~
benzene 152

Figure 11.14: 6, for benzene - c-C6HI2 in benzene-

Sn14 - c-C6H12 system vesus volume
fraction and "effective volume
fractionw of benzene 154

Figure 11.15: Excess saturation solubility terms

in a hypothetical system versus i l 155

Figure 11.16: Excess saturation solubility terms

for I2 in C6H6 - c-C6H12 mixed
solvent versus volume fraction of
benzene 156

Figure 11.17: Excess saturation solubility terms

for I2 in C6H6- c-C6HI2 mixed solvent
versus volume fraction of benzene 158

Figure 11.18: Excess saturation solubility terms

for Sn14 in C6H6 - CCl mixed
4
solvent versus volume fraction of
benzene

Figure 11.19: Excess saturation solubility terms

for I2 in CC14 - n-C F
7 16 mixed solvent
versus volume fraction of CC14 162
.Figure 11.20: Saturation solubility of I2 in
CC14 - n-C7F16 mixed solvent
versus volume fraction of CC1
4

,Figure 11.21: Excess saturation solubility of

naphthalene in a hypothetical
mixed solvent versus G l

i - In x2)
Figure 11.22: (In a2 'I2 of naphthalene
in a hypothetical mixed solvent
versus G
1

Figure 11-23: Excess saturation solubility of

SnI, in a hypothetical mixed
Lt
0
solvent versus

i
Figure 11.24: (In ap - In x2) I/* of S ~ in
I a~
hypothetical solvent versus Gland G r 170

Figure 11-25: Partial molal volume of Br2 in CC14

- c-C4C12F6 @xed solvent versus
effective volume fraction of CC1 171
4

Figure 11.26: for I2 in benzene - c-C6H12

mixed solvent versus volume
fraction of benzene 173

Figure 11-27: AVE ~ M for Br2 in CC14 - C - C ~ C ~ ~ F ~

mixed solvent versus volume fraction

Figure 11.28: Saturation solubility of naphthalene

in CC14 - c-C6HI2 mixed solvent
versus temperature
Figure Saturation solubility of naphthalene
in CH212 - c-C6H12 mixed solvent
versus mole fraction of CH212 179

Figure Saturation solubility of naphthalene

in CH212 - c-C6H12 mixed solvent
versus volume fraction of CH212

Figure i - In x2)
(In a2 for naphthalene
in CC14 - c-C6H1 mixed solvent
versus volume fraction and "effec-
tive volume fraction" of c-C6H12

Figure i - In x2)
(In a2 for naphthalene
in CH212 - c-C6H 12 mixed solvent
versus volume fraction and "effec-
tive volume fractionu of c-C6H12

Figure i - In x2)
(In a2 m 1/2 / mm of naphtha-
lene in CC14 - c-C6H12 mixed
solvent versus volume fraction
and "effective volume fraction" of
'-gH1 2

Figure i - In xz) 'I2/,@ of naphtha-

(In a2
lene in CH212 - c-C6HI2 mixed
solvent versus volume fraction and
fleffectivevolume fractionu of
C-C6H1 2
 - xiii -
ACKNOWLEDGEMENTS

I would like to take this opportunity to thank

my research supervisor Dr. John Walkley, for his ideas,
many of which appear here, for his interest, and most
of all for his constant approachability.
Thanks for reading the first manuscript are due
to Dow Maharajh who has been my research colleague for
the last two years. This period has been marked by
discussions, arguments and debates but nore importantly
by a good friendship.
I also thank Mr. R. McMillan for computational
assistance, Miss I. Cheveldayoff for reading the final
draft of this thesis, and other fellow students of the
group for their help during this work.
I thank the National Research Council of Canada
for financial support.
Last but not least, I would like to thank Mr. Fred
Jones and Miss Philadel hfarples who typed this thesis.

C-8024 Abhi jit Purkayastha.

Simon Fraser University
Burnaby, B.C., Canada
August, 1970
 The p r o p e r t i e s of n o n e l e c t r o l y t e s o l u t i - o n s a r e of
p e n t interest to chemical e n g i n e e r s f o r when t h e y
r e p r e s e n t d e s i g n d n t a and t o c h e n i s t s f o r vhon t h e y
r e p r e s e n t a source of i n f o r u a t ion about internol-
e c u l a r f o r c e s m d t h e t h e r 3 o d y n n n i c behnviour of mol-
ecules i n solutions. Fron e i t h e r p o i n t of view t h e
a i 9 i s t o develop methods t h ~ will..
t be ~ b l et o p r e d i c t
t h e n r o n e r t i e s o f s o l u t i o n s e i t h e r from t h e r e s u l t s o f
a few rqeesurenents on s o l u t i o n s o r n o r e h o p e f u l l y from
t h e n r o p e r t i e s o f p u r e connonents.
S i n c e t h e e a r l y t w e n t i e t h c e n t u r y , many a t t e r i n t s
have been made t o d e v e l o p t h e o r i e s o f t h e s o l ~ ~ t l o no fs
n o n e l e c t r o l y t e s b u t t h e n o s t v ~ i d e l yused and t h e most
successful theory i n i t s l i n i t e d f i e l d i s t h e Reculnr
Solution theory. T h i s t h e o r y was f l r s t develoned by
H i l d e b r a n d t o c a l c u l e t e t h e thernodyn:mic n r o n e r t i e s
of s o l u t i o n s of n o n e l e c t r o l y t e s . It i s one o f t h e s i n -
p l - e s t t h e o r i e s nronosed on t h i s s u b j e c t and o v e r t h e
d e c a d e s it h ~ been
s t h e b a s i s o f mnny d i s c u s s i o n s ~ n d
nany improvernents on t h e t h e o r i e s of' s o l u t i o n s . In
C h a p t e r I ;ve s h a l l d i s c u s s t h e d i f f e r e n t a s n e c t s o f
R e p u l ~ rS o l u t i o n t h e o r y and i t s l l r l i t a t i o n s .
The :lost ~ t t r n c t i v es y s t e w f o r study in^ on t,he

b a s i s o f i i e g u l ~ rS o l u t i o n t h e o r y ? r e t h e t h r e e c o m o n -
e n t s y s t e n s whose corlnonents h:ive n l n o s t s i n i l t l r n o l e r
volumes. I n s u c h c n s e s t h e e f f e c t s o f m o l m volume d i s -

p c r i t i e s o f t h e c o n n o n e n t s on t h e f r e e e n e r g y o f n i x i n g
v ~ o u l dbe n e ~ l l i p i b l e . The e x t e n s i o n o f t h e R e g u l a r S o l -
u t i o n theory, which WRS o r i p i n a l l y develoned f o r b i n m y

s y s t e n s , t o t e r n n r y s y s t e n s assumes t h a t t h e t e r n ~ r y
s y s t e n s !my be c o n s i d e r e d a s a p s e u d o - b i n n r v s y s t e n

of one s o l u t e and one n i x e d s o l v e n t whose s o l u b i l i t v

p a r m e t e r i s p i v e n by t h e volurrle f r e c t i o n n v e r a c e o f

t h e s o l u b i l i t y n o r m e t e r s of t h e cormonents o f t,he rlixed

solvent. Although t h e r e s u l t a n t s p l u b i l i t p e q u ~ t i o n
i s a v e r y s i m p l e one, u n f o r t u n a t e l y it h a s been o b s e r v e d
frori s o l u b i l i t y s t u d i e s o f s o l i d s o l u t e s I n n i x e d s o l -
v e n t s ( a 1 1 t h r e e components Hre n o n e l e c t r o l y t e s ) t h ~ t
t h e e x p e r i n e n t a l s ~ t u r a t i o ns o l u b i l i t y i s ~ 1 : v a y s p r e a t e r
t h n n t h e p r e d i c t e d vccllue. In e n r l i e r studles of the
n~rtian
l o l a l v o l m e s of Br2
L
in CC14 - n-C 7F 16 """
in CC14 - c-C4C12F6 n i x e d s o l v e n t s , it vias shown t h a t

t h e y e r t i e l n o l n l volume o f Br2 i s l e s s t h ~ nt h e cal-

culnted v s l u e s derived f r o n t h e 2ssu3ption t h n t t h e
s o l u b i l i t y p a r w n e t e r of t h e n i x e d s o l v e n t s i s p i v e n by
t h e volunle f r a c t i o n w e r a g e o f t h e s o l u b i l i t y p a r a m e t e r s
o f t h e corrlponents o f t h e n i x e d s o l v e n t . Such Rn ~ssunp-

t i o n about t h e s o l u b i l i t y parameter of t h e nixed s o l -

v e n t s i m p l i e s t h ~ t h e d i s t r i b u t i o n o f component s of
t h e rnlxed s o l v e n t s round t h e s o l u t e n o l e c u l e depends

upon t h e v u l u n c f r r c t i o n o f t h e cosmonents ~ n dn o t on

t h e i n t e r n c t i o n s of t h e s o l u t e m o l e c u l e s w i t h t h e
 - 3 -
i n d i v i d u a l comnonents. I n t h i s t h e s i s it i s pronosed
t o study t h e e f f e c t of s o l u t e - tmre solvent i n t e r z c -
t i o n s on t h e s o l u b i l i t y s t u d i e s o f s o l i d s o l u t e s i n
t h e mixed s o l v e n t s . A d e t a i l e d account of t h e s t u d i e s
of i o d i n e , s t a n n i c i o d i d e and o t h e r s o l l d s o l ~ r t e si n
mixed s o l v e n t s w i l l be p r e s e n t e d , and a t h e o r y d e v e l -
oped which ~ 1 l o . vt h~ e r a t i o o f t h e " n e a r e s t n e i ~ t h b o ~ i r s "
mixed s o l v e n t cornnonent m o l e c u l e s around t h e s o l u t e
r i a l e c u l e s t o be c f l l c u l a t e d . T h i s nev t e r n , denoted
~s t h e f f e f f e c t i v e volume f r a c t i o n , l f i s i n t r o d u c e d t o
r e p r e s e n t t h e n e a r e s t environr?ent o f t h e s o l u t e n o l e -
c u l e i n t h e mixed s o l v e n t s .
T h i s t t e f f e c t i v e f fvolune f r ~ c t i o ne s s e n t i a l l y i n -
p l i e s a p r e f e r e n t i a l s o l v a t i o n of t h e s o l u t e n o l e c u l e s
by one s o l v e n t p a r t n e r i n t h e mixed s o l v e n t . Ry rnakinc
e l l o w ~ n c e sf o r t h i s p r e f e r e n t i a l s o l v a t i o n o f t h e s o l -
u t e n o l e c u l e , it w i l l be shown t h a t t h e R e p u l a r Solu-
t i o n t h e o r y can be s u c c e s s f u l l y q p l i e d t o e x p l e i n ~ l l
t h e ~ v a i l a b l ed a t a on t h e s o l u t i o n s o f t h e n o n n o l a r
s o l i d s o l u t e s i n nonpolar nixed solvents.
I n Chapter I1 o f t h i s t h e s i s we s h a l l d i s c u s s t h e
d i f f e r e n t ~ s p e c t so f t h e t h r e e component s y s t e n s .
The o t h e r i n t e r e s t i n g phenoxenon t o s t u d y i s t h e
e f f e c t o f s o l v e n t - s o l u t e volume c t i s p ~ t r i t yi n t h e b i n -
a r y systevns becrilise it, i s w e l l known t h z t i f t h e s o l -
v e n t - s o l u t e vol1u1e d i s n n r i t y i s t o o ! - ~ r c e , t h e e n t r o p y
of mixing of supercooled l i q u i d ( t h e assuned s t ~ n d a r d
s t a t e of t h e s o l i d s i n t h e Regular Solution t h e o r y )
s o l u t e nnd t h e l i q u i d s o l v e n t s e r e no l o n p e r z e r o end
R e g u l a r S o l u t i o n t h e o r y can n o t be a p n l i e d s u c c e s s f u l l y
i n these cases. It i s d i f f i c u l t t o cc?lcul-ate t h e n m -
n i t u d e o f t h e e x c e s s e n t r o p y becmlse it h e s been o b s e r v e d

t h a t f o r s p h e r i c a l s o l i d s o l u t e x o l e c u l e s such e s t e t r e -

p h e n y l t i n t h e u s u ~ l l yused w F l o r y - I : u ~ ~ i n sew
ntronv
o f n i x i n g t o t a k e a c c o u n t of t h e volume d i s p a r i t y between
s o l u t e and s o l v e n t a r e u s u ~ l l yu n r e l i a b l e . To examine
t h e e f f e c t o f t h e s o l v e n t - s o l u t e v o l u a e d i s p a r i t y on
t h e s o l u b i l i t i e s o f t h e s o l i d s , we have c a r r i e d o u t t h e
s o l u b i l i t y s t u d i e s along with t h e experimental d e t e r -
m i n ~ t i o nof t h e p m t i a l rnolol v o l u n e o f t e t r a perfluoro
-phenyl t i n ( s ~ ( c ~ F) whose
~ ) ~ n o l ~ rv o l u n e i s
404.4 c c i n d i f f e r e n t o r g a n i c s o l v e n t s o f molnr v o l w e s

around 100 c c . L

I n t h i s t h e s i s we s h a l l a l s o p r e s e n t R method t o

c a l c u l a t e p a r t i ~ mlo l d e n t r o n y of' rrixing s o l i d s o l u t e s

i n liquid solvents. T h i s x e t h o d w f l l be developed from

t h e s c a l e d p e r t i c l e t h e o r y o f d e n s e f l u i d s and it w i l l
a l s o be shown t h a t t h i s flethod c a n s u c c e s s f u l l y be a p p l i e d

e n~t r o ~ i e sof i o d i n e ,
i n p r e d i c t i n g t h e p ~ r t i a ln o l ~
stnnnic iodide, t e t r m h e n y l t i n , along w i t h tetra

perfluoro~hcnyltin. ,,Je developed t h i s n e t h o d t o

c e l c u l e t e p a r t i a l molal entropy because, a s nentioned

e n r l i e r , t h e R e m l a r S o l u t i o n t h e o r y u s u s l l v cnn n o t

cope w i t h systerns such AS o u r s ~ n dt h e F l o r y - I i w p i n s

entropy term is unreliable.
In Chapter 111 we shall discuss the sczlrd particle
theory and its application in derivinr the ?roperties
of pure liwid and binary liquid mixtures.
 Cha,nter - I

Regular Solution Theory

 krly cornnlete u n d e r s t a n d i n p : o f m i x t u r e s o f n o n e l e c -
t r o l y t e s must need R c l e a r s o l u t i o n o f t h e problems

involving i n t e r n o l e c u l a r f o r c e s i n t h e theory of t h e
l i q u i d s t ~ t e . To d a t e t h e r e e x i s t o n l y Rnproxirwte
t r e a t n e n t s b u t it i s s u r p r i s i n p t h ~ tt h e s e t h e o r i e s
c m be ~ p p l i e dmore s u c c e s s f u l l y i n f o r n u l n t i n g t h e
t h e o r y o f s o l u t i o n s t h a n one ~ v o u l de x p e c t from t h e d r a s -
t i c ap?roximations involved i n then, O r conversely

i t c o u l d be s ~ i dt h 8 t t h e e r n p i r i c ~ ls u c c e s s of t h e t h e o -
ries 01' t h e s o l u t i o n s mny n o t be u s e d t o j u s t i f y t h e
t h e o r i e s o f t h e l i q u i d s t a t e o r o f i n t e r n o l e c u l ~ rf o r c e s
fro11 which t h e p o s t u l ~ t e dt h e o r y h ~ been
s derived.
Under t h e s e c i r c u n s t a n c e s v e s h a l l d i s c u s s t h e t h e o r i e s
on t h e l i q u i d s t ~ t em d i n t e m o l e c u l n r f o r c e s v e r y b r i e f -
l y and t h e n s i n t o n i c o f o u r d i s c u s s i o n i n t h i s c h a p t e r
w i l l be t h e H e g u l ~ rS o l u t i o n t h e o r y which,
L
RS Scott c 11
w r o t e i n 1956, l f . . . o f f e r s n u s e f u l i n i t i a l annroach t o

a v e r y wide are,? o f s o l u t i o n l i k e R s m a l l - s c f i l e map f o r

a v e r y broad l o n g d i s t e n c e a i r view o f t h e s u b c o n t i n -
ent. ''
The s u c c e s s o f R e g u l a r S o l u t i o n t h e o r y l i e s i n i t s
~ b i l i t yt o p r e d i c t t h e e x c e s s f r e e energy o f m i x i n c
and hence t h e w t u r e t i o n s o l u b i l i t i e s w i t h i n a fevr p e r -
c e n t of t h e e x p e r i n e n t ~ lv a l u e s , However t h e t h e o r y
i s n o t ~ c c u r n t ei n p r e d i c t fng many o t h e r t h e r m o d y n m i c
p r o p e r t i e s such n s t h e h e n t of s o l u t i o n o r t h e volume

change upon n i r l n c .
I n t e r ~ o l e c u l a rF o r c e s
The n r o p e r t i e s o f s o l u t i o n s depend unon t h e n a t u r e

of t h e i n t e r a c t i o n s between t h e v e r l o u s t y p e s o f n o l e -
c u l e s , b o t h l i k e and u n l i k e , i n t h e s o l u t i o n . Two com-
nonly used p o t e n t i a l f u n c t i o n s f o r t h e i n t e r e c t i o n s of
s p h e r i c a l m o l e c u l e s e r e Lennnrd-Jones ( L - J ) p o t e n t i a l ,C21
i.e. 12-6 p o t e n t i n l find exp-6 p o t e n t i a l . The Lennard-

Jones p o t e n t i a l i s defined RS

The exp-6 p o t e n t i a l i s d e f i n e d n s

I n b o t h of t h e s e e x p r e s s i o n s represents the
depth of the potential well, r i s t h e d i s t a n c e and r
0

i s t h e s e p a r ~ t i o na t which t h e minirrum i n t h e p o t e n t i a l
occurs. The a i n t h e equntion ( l b ) i s t h e d i s t m c e

~t ~ v h i c ht h e p o t e n t i e l i s z e r o ( s e e F i p u r e 1 ) . The a
i n t h e e q u c t i o n ( 2 ) i s t h e s t e e m e s s of t h e e x a o n e n t i a l
r e p u l s i o n end i s u s u e l l y a b o u t 13.5.
 F i g u r e 1 .l The p a r a m e t e r s u s e d i n e x p r e s s i n g
the pair potentials.
The 12-6 p o t e n t i a l h a s o n l y two a d j u s t a b l e 7 7 ~ 8 -

m e t e r s w h e r e a s t h e exp-6 p o t e n t i a l h a s t h r e e . One nod-

i f i c a t i o n o f t h e L-J p o t e n t i a l i s t h e X i h a r a c o r e po-

t e n t i a l i n which t h e p o i n t c e n t e r o f t h e L-J p o t e n t i a l
i s r e p l a c e d by a h a r d c o r e . The p o t e n t i a l i s c i v e n by

where o i s t h e s h o r t e s t d i s t a n c e betrveen h a r d c o r e s
end r, i s i t s v ~ l u ea t t h e p o t e n t i a l n i n i n u n . The
n e t e f f e c t of t h e Kihara core p o t e n t i n l i s t o m k e t h e
~ t t r ~ c t i ve nee r c y a m i l d l y s t e e p e r f u n c t i o n o f r and
t h e r e p u l s i v e e n e r g y a much s t e e p e r f u n c t i o n i n conpar-

ison t o L-J p o t e n t i a l .
 F o r i n t e r a c t i o n s between unlike ~ o l e c u l e s ,
t h e f o l l o w i n f t cormonly used r u l e s m e ~ v n i l ~ b l et h
: e
g e o m e t r i c mean r u l e f o r t h e e n e r g y p a r a m e t e r s i s

~ n dt h e a r i t h m e t i c combining r u l e f o r t h e d i s t a n c e p a r -
meters is

I n us in^ t h e s e "combination r u l e s " one must rernex-

b e r t h a t i n t h e c 8 s e s where t h e p o t e n t i a l f u n c t i o n s
f o r t h e components o f a s o l u t i o n h v e d i f f e r e n t s h ~ p e s ,
t h e r e l a t i o n s of t h i s k i n d cannot g i v e f u l l i n f o r n a t i o n
on t h e i n t e r a c t i o n s between t h e unlike, nzolecules.C 41 - V
Recent p u b l i c a t i o n s C4-91 elonp: w i t h e a r l i e r r e v i e w s

o u r p r e s e n t knowledpe about t h e i n t e r r ? o l e c u l a r f o r c e s .
A s n o r e k i n d s o f i n f o r n a t i o n on i n t e r n o l e c u l z r f o r c e s
become a v a i l a b l e , it s e e n s t h n t t h e s i x p l e e n ~ l y t i c a l
p o t e n t i e l e x p r e s s i o n s n s d i s c u s s e d above a r e n o t ade-
q u ~ t ei n d e s c r i b i n g t h e i n t e r m o l e c u l m i n t e r ~ c t i o n , even

f o r t h e s p h e r i c 8 1 molecules.C 13,141
Another i m n o r t a n t a s p e c t of t h e i n t e r r n o l e c u l ~ r
p o t e n t i a l i s t h e nonndditivity of t h e Lnternoleculsr A

f o r c e s (1,vhich hns been known f o r a l o n p t i m e ) yet, t h e

most u s u a l method of d e s c r i b i n p t h e i n t e r ~ o l e c u l a ren-
e r c y of R c r o u p o f m o l e c u l e s i s t o ~ s s u r n et,hrit, t h e
i n t e r m o l e c u l ~ renergy m y be r e p r e s e n t e d by t h e sum
of t h e p a i r enerpies, i,e.

o r i n o t h e r words t h e c o n t r i b u t i o n o f t h e t r i ~ l e ti n t e r -
a c t i o n term i n t h e t o t a l i n t e r g o l e c u l a r enerpv i s v e r y
small. There h a s been a r e c e n t r e v i v a l o f i n t e r e s t
concerning t h e c o n t r i b u t i o n of t h e t r i p l e t i n t e r a c t i o n
e n e r g i e s ( i n e x c e s s over t h e sun o f t h e p a i r e n e r p i e s
i n e q u a t i o n ( 6 ) ) t o t h e t o t a l i n t e r a c t i o n of 8 Froup
of' molecules. The m ~ i nproblem w i t h t h e t r i ~ l e ti n t e r -
~ c t i o nt e r m i s t h e u n c e r t a i n t y a b o u t t h e rnapnitude o f
t h i s c o n t r i b u t i o n t o t h e t o t a l enerey: t h e e s t i m a t e f o r
argon r n ~ yv a r y from l e s s t h ~ 1% ~r14,151
t t o a s h i q h a s 1540.
F o r lic-mids t h e r e i s no d e f i n i t e w ~ yo f d e c i d i n g wheth-
L

e r t h e contribution of t h e t r i n k e t i n t e r a c t i o n t e r n w i l l
be n e g l i p i b l e o r n o t . Rut f r o n t h e n h y s i c a l n i c t u r e s
it seems, a s n e n t i o n e d by l i i l d e b r a n d e t e l . ,[ 19! t h a t
the different orientations i n the liquid s t a t e "largely
e l i m i n a t e s t h i s f a c t o r f o r l m g e number o f atoms ss
c l o s e l y packed a s i n a l i q u i d , " and t h r o u g h o u t a l l o u r
d i s c u s s i o n we s h e l l a s s u n e t n p t t h e c o n t r i b u t i o n due
t o t h e t r i p l e t i n t e r ~ c t i o nterm i s n e @ i p i b l e ,
I n f o r m ~ t i o nabout i n t e r r ~ i o l e c u l a rf o r c e s can be

o b t ~ i n e dfrom qusntum mechanical c ~ l c u l e t i o n s ,from

m o l e c u l m b e m s c ~ t t e r i n ce x p e r l n e n t s , from t,he meFis-
urement o f t r a n s p o r t p r o p e r t i e s i n t h e paseous s t e t e
and t h e n e ~ s u r e m e n t ,o f t h e e q u i l i b r i u n thernodvnamic

p r o p e r t i e s of l i q u i d s and p e s e s . 1n.fo r n ~i ot n
a b o u t i n t e r n o l e c u l ~ rf o r c e s c a n a l s o be o b t ~ i n e dfrom
t h e heat 3f v ~ p o r i s ~ t i odna t a m d from t h e m e ~ s u r e n e n t
of t h e ($$>
of n o r m 1 llquids!219221 The l ~ s two
t
s o u r c e s o f i n f o r m a t i o n w i l l be d i s c u s s e d b e c e u s e of t h e

u s e of t h e s e p r o p e r t i e s i n Regular S o l u t i o n theory.

H i l d e b r a n d ~ n c ?!Yood C231 showed t h r t t h e p o t e n t i a l

e n e r g y o f l i a u i d c a n be e x p r e s s e d i n t e r n s of i t s n o l -
e c u l a r p a i r p o t e n t i a l and i t s d i s t r i b u t i o n f u n c t i o n 8s

L
v i s A v o g a d r o q s number when t h e e q y n t i o n ( 7 )
where
No
i s m i t t e n f o r one mole o f l i q u i d , E i s t h e t o t a l
p o t e n t i a l energy p e r n o l e o f l i q u i d , v is t h e nolar
volume, end g(r) i s t h e r ~ d i a ld i s t r i b u t i o n f u n c t i o n
of t h e l i q u i d .
They e x p r e s s e d ~ ( r )i n t e r n s o f an n-6 ~ o t e n t -

i a l defined a s
 - 13 -
7
S u b s t i t u t i n g t h e e q u a t i o n ( A ) i n t h e e q u n t i o n (%)
one o b t n i n s

YIakehnn and Boyd L2l1 s v a l u n t e d k, j

snd n f o r mercury by s e t t i @ E = -AE'~*, t h e heat of

vaporisntion, m d Sy u s i n g t h e e x ~ e r i n e n t a l l yd e t e r -
mined v a l u e f o r g ( r ) , t h e y o b t a i n e d t h e vcllues f o r k,
j end n which n r e i n remnrkably good a p r e e n e n t w i t h
,
t h e s e v n l u e s d e t e r n i n e d from t h e o t h e r s o u r c e s . This
agreenent has a considernble s i p n i f i c n n c e i n f o r n u l a t -
ion o f t h e Regular Solution theory because i n t h i s t h e -
o r y t h e i n t e r a c t i o n t e r n s a r e d e s c r i b e d i n t e r ~ sof
t h e cohesive energy d e n s i t y , here t h e c o h e s i v e e n e r p y

d e n s i t y i s d e f i n e d a s t h s h e a t o f v n n o r i s ~ t i o nd i v i d e d
by t h e n o l a r volume a t t h e same ( e x t r a n o l a t e d ) t e m p e r a t u r e .

!heasurements of t h e GF-h o f n o ~ n l ~l ilq u f d s

F u r t h e r evidence about t h e i n t e r n o l e c u l 8 r p o t e n t -
i a l e n e r g i e s n r e o b t ~ i n e dfrom t h e behnviour o f a v a n
d e r Tlnals l i q u i d , f o r which

Compnrinp e c l u ~ion
t (10) w i t h t h e thernodynnnic
equction of s t ~ t e
one o b t a i n s

Smith and 1Iildehrand r221d e t e r m i n e d fgh for

d i f f e r e n t l i q u i d s and t h e y o b s e r v e d t h a t T de-
creRses f o r c-C6FI1CF3 with incrensinr: t e n p e r ~ t u r e .
.
S i m i l m phenomenon was a l s o o b s e r v e d by S c o t t e t a l .r251
for CC14 . r
T h i s d r i f t i n p v r ~ sc o r r e l e t e d by F r m k 261
a
by w r i t i n g E = - f o r d i l u t e vapors. T h l s allovrs o n e
vn
t o write
v ~ + ~ T ~ ~ ~ = n V" A E ~ =
~ constant
P

f o r d i l u t e vapors.
From t h e e q u a t i o n ( 1 3 ) 8 d e f i n i t i o n of n cen a l s o

be found a s n i s t h e r a t i o of to (As;? of

the liquid. Smith m d H i l d e b r m d found t h a t n h ~ s

value l a r g e r than u n i t y f o r t h e l i q u i d s they studied.

P o t e n t i a l e n e r p i e s between u n l i k e m o l e c u l e s
The vnn d e r i'lRa1s c o n s t a n t a f o r one ole o f
b i n a r y m i x t u r e and t h e c o n s t a n t s f o r the mire compon-

e n t s a r e r e l a t e d by
where aI2 i s t h e i n t e r n c t i o n between t h e u n l i k e 301-
e c u l e s end t h e x's are the ole f r a c t i o n s .

Plrit ing 1
a12 = (a1a2)F

~ n dt h e n s u b s t i t u t i n g e q u n t i o n ( 1 5 ) i n equr?tion ( 1 4 )
one o b t a i n s

The v a l i d i t y o f t h e ~ e o n e t r i cmem a s s u r 3 ~ t i o ni n
t h e e q u e t i o n ( 1 5 ) was t e s t e d by H i l d e b r a n d and ~ a r t e r [ 2 7 3
by m e ~ s u r i n pt h e o f t h e three pure l i q u i d s m d
of t h e i r b i n a r y l i q u i d n i x t u r e s . The C ~ l C u l ~ t evda l u e s
for a from t h e a q u n t i o n ( 1 5 ) :.?ere w i t h i n 1% o f t h e
12
experinental values f o r
12
a .(Another i n t e r e s t i n g
d i s c u s s i o n about t h e g e o m e t r i c mem a s s u n p t i o n i s g i v e n
by ~ a r k e r l )~ ] The p o t e n t i a l e n e r g i e s betmeen t h e un-

l i k e n o l e c u l e s w i l l be c o n s i d e r e d i n the, l a t t e r n s r t of
t h i s chapter. I n t h i s s e c t i o n we d i s c u s s e d t h e impor-
t m c e o f t h e thernodynnmic measurements i n r e l a t i o n t o
the int,erqolecul8r forces.

Liquid S t a t e
I n t h e b e g i n n i n p o f t h i s c h n n t e r we mentioned t h e
two n n p r o x i x a t i o n s t h a t n r e i n v o l v e d i n f o r t i u l a t i n p
any t h e o r y o f s o l u t i o n s : one i n v o l v e s u s e o f a f o r m a l
 - 16 -
expression f o r t h e intermolecular p o t e n t i a l function
( a s h a s been d i s c u s s e d a b o v e ) and t h e o t h e r i n v o l v e s

t h e a p p r o x i m ~ t i o n si n t h e l i a u i d s t a t e t h e o r v u s e d ,
D e t a i l e d d i s c u s s i o n and t h e e x t e n s i v e r e v i e w o f

t h e t h e o r i e s o f l i q u i d s and d e n s e g a s e s which w i l l be
beyond t h e scope o f t h i s c h a p t e r may b e found e l s e -

where,C28-301b u t t h e r e Rre n n i n l y two a p p r o a c h e s t o

t h e formulation of t h e l i q u i d s t a t e . One a p n r o a c h Is
t h e f o r m a l a p p r o a c h u s e d by Mayer, K i r h o o d and o t h e r s .

T h i s a p p r o a c h i s based on t h e u s e o f a r a d i ~ ld i s t r i b -
ution function. A t p r e s e n t t h e most p r o m i s i n g and i n -
t e r e s t i n g t h e o r i e s based on t h i s a p p r o a c h m e t h e S c e l e d
P a r t i c l e t h e o r y and t h e p e r t u r b a t i o n t h e o r y o f B a r k e r
and Hender SOL [ 29 3. The S c ~ l e dP a r t i c l e t h e o r y

w i l l be d i s c u s s e d i n a l a t e r c h a p t e r .
The o t h e r a p p r o ~ c hi s t o u s e t h e o r i e s based on em-
p i r i c a l m a t h e m a t i c a l models. The n o s t c o n m n l y u s e d

model t h e o r i e s a r e c e l l t h e o r y C331 nnd t h e s i p n i f i c n n t

s t r u c t u r e theory. Both t h e s e t h e o r i e s have been wfde-

l y used i n c a l c u l n t i n g t h e p r o n e r t i e s o f l i q u i d s [ 29931932]
>-I
Hut a s o u r main t o p i c o f d i s c u s s i o n i s t h e H e ~ u l a r 1
S o l u t i o n t h e o r y and i t s a p c l i c n t i o n s , and 8 s t h e R e p u l a r '
\ I
' S o l u t i o n t h e o r y i s based on t h e assumption o f llnaxinur?
r n n d o m e s s , " t h e whole i d e a o f t-i model a p p r o a c h i s un-
a c c e p t a b l e b e c e u s e a l l t h e t h e o r i e s b ~ s e don t h e n o d e l

a p p r o a c h assume sone s o r t o f l l q u a s i - l n t t i c e l l o r d e r i n

the liquid state.

 The c o n t r o v e r s y o v e r t h e p r o p e r t i e s ~ n dt h e " s t r u c -
t u r e " of l i q u i d s hns been b e s t s u n n ~ r i s e di n on a r t i c l e
R i c e C331i n 1963.
w r i t t e n by E y r i n g , I I i l d e b r m d ~ n d
H i l d e b r ~ n d 341 i n t h e book nnmed R e m l a r S o l u t i o n s ~ l s o
d i s c u s s e d t h e e x ~ e r i n e n t n le v i d e n c e i n f n v o u r o f t h e
nnaximun r n n d o m e s s " i n t h e l i q u i d s . consider in^ t h ~ t
our i n t e r e s t i s t o a7ply t h e Regular Solution t h e o r y i n
t h e s t u d i e s o f s o l u t i o n s o f n o n e l e c t r o l g t e s , we s h a l l
a c c e p t t h e f o r n n l nnpronch i n t h e f o l l o w i n g d i s c u s s i o n .

Regular S o l u t i o n s
~ ~ f i r s t proposed by
The n m e "Regular S o l ~ t i o nwas
H i l d e b r a n d C361 i n 1 9 2 9 i n d e s c r i b i n e t h e s o l u b i l i t i e s
of i o d i n e i n d i f f e r e n t nonpolnr s o l v e n t s , I n 1931,
G . S c a t c h a r d [ 371 p u t fonvnrd 8 theory t o e m l o i n t h e
b e h a v i o r o f such r e ~ u l a rs o l u t i o n s . T h i s t h e o r y of
S c ~ t c h o r di s known 8s t h e R e c u l ~ rS o l u t i o n t h e o r y . A

r e g u l a r s o l u t i o n nny be d e f i n e d a s
... one i n v o l v i n c no e n t r o n y chance when a s x a l l
m o u n t of i t s conponent i s t r z n s f e r r e d t o it
from En i d e a l s o l u t i o n o f t h e sane c o a n o s i t i o n ,
t h e t o t a l volume r e m i n i n e unchanged.
C 381

Sone Important Therr~odvnarlicI i e l ~i to n s

R e f o r e d i s c u s s i n c t h e d i f f e r e n t n s a e c t s of t h e
R e g u l a r S o l u t i o n t h e o r y it s e e l s i n p o r t ~ n tt o s n e c i f y
some of t h e n o t n t i o n nnd t h e m o d y n n n i c r e l n t i o n s a h i c h
w i l l be u s e d f r e q u e n t l y i n t h i s t h e s i s .
The f o l l o w i n g s u p e r s c r i p t s w i l l b e u s e d t o d i s t i n g -
u i s h t h e s t ~ t eand t h e k i n d o f p r o c e s s :

1 = liquid e = excess over i d e n l

solutions
o = standmd s t a t e m = nixinf-t o r i n mixed
( i n t h i s discus- solvent
sion t h e stan-
dard s t a t e i s r =r e m l ~ r
always p u r e l i q -
uid)
The f o l l o w i n g n o t a t i o n s w i l l h e used f o r t h e t h e r a -
o d y n ~ m i cf u n c t i o n s :
F = Gibbs f r e e e n e r e y P = pressure

A = Helmholtz f r e e v = volurze
energy
E = energy
H = enthalpy T = temnerature i n
degrees ahsolute
S = entropy
The thermodyntmic r e l e t i o n s vrhich w i l l be needed
frequently ere:

The o t h e r i n p o r t a n t t h e r n o d y n a n i c r e l ~ t i o n sa r e
g i v e n i n A g e n d i x 111 .l.

Ideal Solution
The concept o f i d e ~ ls o l u t i o n s e r v e s t h e same p u r -
pose i n the s t u d i e s of r e a l s o l u t i o n s n s t h e concept
o f i d e a l c a s d o e s i n t h e s t u d i e s o f r e ~ wises.
l Per-
h a p s v e r y fey7 s o l u t i o n s m e i d e a l , which i s n o t s u r n r i s -
i n c , b u t t h e advantage o f i n t r o d u c i n r t h e c o n c e p t o f
i d e a l solution i n thernodynmic s t u d i e s of solutions i s
t h a t it i s t h e r n o d y n a n i c n l l y w e l l - d e f i n e d . ' An ide~l
solution[391 i s d e f i n e d n s one i n v h i c h t h e f u p n c i t y
of ench c o q o n e n t i s p r o p o r t i o n n l t o t h e 3 o l e f r ~ c t i o n
of t h ~ coxponent
t i n t h e s o l u t i o n and t h i s - ~ r o p o r t i o n -
a l i t y i s obeyed o v e r t h e c o n p l e t e c o q y o s i t i o n r a n g e o f
t h e solution. , So a c c o r d i n g t o t h i s d e f i n i t i o n t h e f u g -
a c i t y of conponent 1, f
:
, of m i d e a l s o l u t i o n i s piven

where fy i s t h e proportionality c o n s t n n t f o r R fiiven

t e n p e r ~ t u r efind p r e s s u r e . I f we c m proceed o v e r t h e

whole r e n e e o f c o n c e n t r a t i o n t o xl = 1, fy Rpnenrs
RS t h e f u g a c i t y o f t h e p u r e conponent 1.
From t h e d e f i n i t i o n o f e c t i v i t y , a , we obtain

I f t h e f u g a c i t i e s c m be r e p l ~ c e dby vnpor p r e s -

s u r e s t h e n we !my w r i t e e q u a t i o n ( 2 1 ) a s
 - 20 -
The f r e e e n e r g y c h ~ n p ef o r an i d e a l s o l u t i o n can
be d e r i v e d from e q u ~ t i o n ( 2 1 ) RS

If t h e e q u a t i o n s (2%) find ( 2 3 b ) h o l d o v e r 8 rmge

of' t e m p e r a t u r e and p r e s s u r e , t h e f o l l o w i n g o c c u r s :

= - ~ ( ni n ~x 1 + n2 i n x2)

From t h e t h e r n o d y n ~ n i cr e l ~ t i o n
 - 21 -
we o b t a i n

S i m i l n r l y f o r t h e volume chnnpe on n i x i n g we f i n d

Thus t h e t h e r m o d y n m i c p r o p e r t i e s o f an i d e a l s o l u -
t i o n formed f r o n l i a u i d conponents c a n be s t i a u l n t e d a s
follows:
(1) T h e r e i s no volume change on mixing f o r an
ideal solution;
( 2 ) t h e r e i s no h e a t o f mixine f o r an i d e a l s o l u -
t ion;
( 3 ) t h e e n t r o p y o f mixing f o r n b i n a r y i d e a l s o l u -

t i o n i s e i v e n by

I n t h i s s e c t i o n we have d e f i n e d t h e i d e a l s o l u t i o n
frorq t h e thernodgnnmic p o i n t of view m d we w i l l u s e
t h i s d e f i n i t i o n f o r t h e i d e ~ ls o l u t i o n t h r o u n h o u t t h i s
 Fig. 1.3.
Mole f r a c t i o n of A i n a P a r t i a l and t o t a l
h y p o t h e t i c a l i d e a l mix- pressure f o r a nonideal
t u r e of A and B - partial mixture of A and B
and t o t a l p r e s s u r e of A w i t h y > 1.
and B.

Pressure

Fig. I.4.
P a r t i a l and t o t a l p r e s s u r e
of a n o n i d e a l s o l u t i o n of A
and B w i t h y < 1.
discussion*

N o n i d e ~ lo r Heal S o l u t i o n
I n t h e e m l i e r s e c t i o n we d e f i n e d an i d e a l s o l u t i o n
a s a s o l u t i o n f o r which t h e ~ c t i v i t yof n conponent i n
t h e s o l u t i o n i s e q u ~ lt o t h e n o l e f r ~ c t i o nof t h a t com-
ponent i n t h e s o l u t i o n such t h a t
a2 = X2
i

But f o r n o s t of t h e s o l u t i o n s , t h i s i s n o t t h e c a s e ,
and f o r convenience we d e f i n e n t e r n c a l l e d a c t i v i t y
c o e f f i c i e n t ( s e e Appendix A l . 1 ) RS

and

So f o r an i d e a l s o l u t i o n ,

and

Again f r o n t h e e q u a t i o n t h e p a r t i a l r n o l ~ lf r e e en-
ergy o f mixing may be w r i t t e n 8 s
 - 24 -
I n e q u a t i o n s ( 3 2 a ) , (32b) and (33) we s e e t h a t t h e
f i r s t t e r n s i n t h e r i g h t hand s i d e a r e i d e a l f r e e ener-
g i e s of n i x i n p so t h e second t e r n s m e t h e e x c e s s over
t h e i d e a l f r e e e n e r g i e s of xixinp: and t h e y a r e known
a s t h e w e x c e s s wf r e e e n e r ~ i e sof n i x i n p . So t h e e x c e s s
f r e e energy of mixing i s d e f i n e d a s

S i m i l a r l y o t h e r e x c e s s p r o p e r t i e s may be d e f i n e d
with reference t o t h e ideal solutions.
The p o s i t i v e v a l u e o f t h e e x c e s s f r e e energy of
nixing, i,e. y, i s g r e a t e r t h a n u n i t y , ~ n di s known
a s a p o s i t i v e d e v i e t i o n from Raoult s Law. Similarly
t h e n e g ~ t i v ev a l u e of t h e e x c e s s f r e e energy o f n i x i n g ,
i.e. y, i s l e s s t h a n u n i t y , and i s knovm RS a neg~tive
d e v i e t i o n f r o n Raoult s Lav?.
I n F i g u r e s 2-4 we show t h e d i f f e r e n t therxodynamic
p r o p e r t i e s o f i d e a l and non-ideal s o l u t i o n s f o r m i x t u r e s
of h y p o t h e t i c a l l i q u i d s A and R e

S o l u b i l i t y of H o n e l e c t r o l y t e s and H e ~ u l ~ S
t ro l u t i o n
-
Theoz
I n t h i s s e c t i o n we l i n i t our d i s c u s s i o n t o t h e
s o l u b i l i t i e s of n o n e l e c t r o l y t e s becnuse t h e long-range
n a t u r e o f t h e e l e c t r o s t ~ t i cf o r c e s y i e l d s p r o b l e x s which
 - 25 -
a r e beyond t h e scope o f t h i s t h e s i s .
Primary c o n s i d e r a t i o n l v i l l be criven t o n i x t u r e s o f
two o r More l i q u i d s . For m i x t u r e s w i t h a s o l i d n s t h e
s o l u t e we s h a l l nssurne t h a t t h e s t a n d a r d s t ~ t eo f t h e
solids i s t h e h y p o t h e t i c a l s u p e r c o o l e d l i q u i d of t h e
s o l i d a t t h a t tempereture.
A s mentioned e a r l i e r , H i l d e b r e n d i n 1929 drew n t -
t e n t i o n t o t h e very s i g n i f i c a n t s i m i l a r i t y i n behavior
of a c l a s s o f n o n i d e a l s o l u t i o n s which h e naned r e c u l a r
solutions. The absence o f any s p e c i f i c i n t e r r c t i o n s -,I
-
is t h e n o s t i n p o r t ~ n tf e o t u r e o f t h e s e s o l u t i o n s . The)
pure conponents o f a r e p u l a r s o l u t i o n hnve t h e proper-
t i e s of simple f l u i d s o r l i q u i d s .
The d i f f e r e n c e between n r e g u l a r s o l u t , i o n and a n
ideal solution i s t h a t f o r R r e m l a r solution t h e heat
I
o f mixing h e s F. p o s i t i v e v a l u e whereas f o r i d e s 1 s o l u t - :-
i o n t h e h e s t o f mixinp i s z e r o . A s nentioned e a r l i e r
t h e entropy of nixing f o r a r e g u l a r s o l u t i o n i s equal t o -.-A
7
t h e i d e a l e n t r o p y of n i x i n p .

Heat of Nixinp e.nd H i l d e b r m d - S c a t c h a r d Equntion

The f i r s t atternpt t o c a l c u l a t e t h e chenpe i n en-
t r o p y o r enthel-ny when tyro l.iquic',s R r e n i x e d , lves nnde
by van Lnar i n 1906 b u t it w n s n o t v e r y s u c c e s s f u l .
I n 1931, G. S c n t c h m d C373p u b l i s h e d n n ~ p e vrhere
r
M
he d e r i v e d an e q u n t i o n t o calculate bEv o r energy

c h ~ n g eon mixing two l i q u i d s n t c o n s t n n t volume. To

 - 26 -
(1)The r n u t u ~ lenergy of two n o l e c u l e s depends
only upon t h e d i s t a n c e between t h e n end t h e i r
r e l e t i v e o r i e n t a t i o n find n o t ~t a l l on t h e
n a t u r e of t h e o t h e r n o l e c u l e s between o r oround
t h e n , o r on t e n p e r a t u r e ;
( 2 ) t h e d i s t i r b u t i o n of t h e n o l e c u l e s i n p o s i t i o n

and i n o r i e n t a t i o n i s r ~ n d o n , i . e . it i s n o t
dependent on t h e t e n r e r n t u r e o r on t h e n a t u r e
of o t h e r molecules p r e s e n t ;
( 3 ) t h e change of volune on n i x i n g i s z e r o .

These a s s u n p t i o n s ~ l l o v r e dhim t o w r i t e t h e "cohes-

i v e energyff of n mole of l i q u i d m i x t u r e ,

For pure l i q u i d s -E = C1lV1,L etc. For l i q u i d s t h e

vapor i s n e z r l y i d e a l a t o r d i n a r y t e n p e r ~ t u r eso -E
can he i d e n t i f i e d v i t h t h e enerpy o f v e p o r i z a t l o n AEVaP

O r %
V ~ P
V . I n t e r n s of t h e volurne f r a c t i o n s equa-
t i o n ( 3 6 ) becones

where C = NlVl m d so on.

N1V 1 + N2V2
So t h e enercy of nixint? i s piven by
here
A12 = Cll + Cg2 - PCl2-
Then it i s assuned t h a t

and s u b s t i t u t i n g Cii = i n e q u a t i o n (38) t h e e n e r ~ g

i'
c h ~ n g eon n i x i n g b e c o x s

The s q u m e r o o t o f t h e vlcohesive m e r c y T Td e n s i t y , i . e .
( ) i s c a l l e d t h e l T s o l u b i l i t yp 8 r ; n e t e r T ? and i n .-J

denoted by 6. So e q u a t i o n ( 2 4 ) nay be w r i t t e n RS

A s e a u n t i o n ( 4 2 ) m s d e r i v e d f r o 3 t h e ~ s s u m t i o nt h e t
t h e v o l u n e chnnge on nixinp: i s z e r o , A E ~i n e o u a t i o n
(42) i s a c t u e l l y
m
AE,.

Since A V ~i s v e r y s m a l l , t h e n

By d e f i n i t i o n = f o r r e g u l a r s o l u t i o n , so

Conbining e q u e t i o n ( 4 1 ) w i t h e n u n t i o n ( 4 4 ) , one o b t n i n s
The c o r r e s p o n d i n ~p a r t i a l n o l ~ fl r e e energy f o r R solute

where y2 i s t h e a c t i v i t y c o e f f i c i e n t of s o l u t e 2 , o r

R e ~ r r a n g i n ge q u ~ t i o n( 4 7 ) , one 0 b t ~ f n s

where a2 i s t h e a c t i v i t y f o r s o l u t e 2.
Xildebrand and '.load d e r i v e d t h e s m e e q u ~ t i o nby
i n t e e r a t i n g t h e i n t e r m o l e c u l a r p o t e n t i a l between p i r s
t h r o u g h o u t t h e l i q u i d w i t h t h e a i d of a c o n t i n u o u s d i s -
t r i b u t i o n f u n c t i o n [ 231
I n e q u ~ t i o n( 4 0 ) , we s e e t h a t t h e Scatchard-Hilde--,
b r m d equetion i s v a l i d only f o r t h e s o l u t i o n s f o r nhrch /-

t h e excess f r e e energies a r e p o s i t i v e , i.e. those solu-

t i o n s ~ v h i c hshow p o s i t i v e d e v i a t i o n s f r o n Haoult ' s Lav,
T h i s i s t h e d i r e c t consecl_~enceo f t h e g e o n e t r i c n e m
~ s s u n p t i o ni n e q u a t i o n ( 3 9 ) .
Hildebrend find i'loodC271 d e r i v e d nn e q u o t i o n s i n i l -
ar t o e q u c t i o n ( 4 1 ) f o r h e ~ o
t f n i x l n p by i n t e p r e t i n ~
t h e i n t e r m o l e c u l a r p n i r n o t e n t i n l s t h r o u ~ h o u tt h e l i a u i d
using a continious d i s t r i b u t i o n function,
I n a n u r e l i q u i d o f s p h e r i c ~ l l gs y . m e t r i c n l n o l e -
c u l e s , n s p h e r i c a l s h e l l of r o d i u s r around n d e s i g -
 - 29 -
\
n ~ t e dc e n t r ~ molecule
l and t h i c k n e s s dr vrill cont~in I

2
%nr
v g(r)dr m o l e c u l e s where g(r) is the r ~ d i d is-

t r i b u t i o n function. The p o t e n t i a l e n e r p y , E, o f p u r e

l i q u i d of N m o l e c u l e s i n volume V i s fliven by

E = -2vP J u g ( r ) r2 d r

where ~ ( r )i s t h e -ir p o t e n t i a l at a d i s t ~ n c e r , No
is A v o c ~ d r o ' s number, find n i s t h e nunber of' moles.
S i m i l a r l y f o r a b i n ~ r ym i x t u r e o f l i q u i d s c o n t a i n -
ing n1 moles o f t y p e 1 ~ n d n 2 moles o f t g y e 2 , t h e
p o t e n t i d e n e r g y of t h e m i x t u r e o f t o t 8 1 v o l u ~ e

'The e n e r p y o f IX~IOunnixed coxnonents i s c i v e n by

 - 30 -
T h e r e f o r e t h e e n e r g y o f mixing i s

The hEM i n e q u n t i o n ( 5 3 ) i s t h e ennrpy o f mixin@

~t c o n s t n n t v o l u n e and t h e t e r n s i n t h e b r a c k e t s i n
e q u ~ t i o n( 5 3 ) c c a be i d e n t i f i e d w i t h S c a t c h e r d t s
(C1l +

C22 - "12) term i n equntion (38).

Next H i l d e b r ~ n de t a l . w r o t e t h e i n t e r m o l e c u l n r
p a i r p o t e n t i a l as

From t h e d i s c u s s i o n of t h e i n t e r n o l e c u l a r f o r c e s
~ i v e ne ~ r l i e r j , t h e c o e f f i c i e n t of t h e r e p u l s i v e i n -
t e r a c t i o n c m be e x p r e s s e d i n t e r m s o f k the eauil-
~ n d

ibriun distence, ( s e e Appendix Al.2) 8.s

(where ro i s t h e e q u i l i b r i u m d i s t a n c e )

S u b s t i t u t i n g e q u e t i o n ( 5 5 ) i n e a u n t i o n ( 5 4 ) , one

obtnins
 It was t h e n assumed r401 t h a t g t s e r e f u n c t i o n s 3
r r
of o r - where o i s t h e c o l l i s i o n d i a m e t e r of
r,u
n o l e c u l e s . T h i s a s s u n p t i o n can be j u s t i f i e d from t h e
o b s e r v a t i o n by Hildebrnnd e t a l . t h e t t h e d i s t r i b u t i o n
f u n c t i o n s o f d i f f e r e n t s p e c i e s cnn be sunerimposed r'rhen
o o n ~ a r e dat equp.1 d e g r e e o f expansion by y l o t t i n r ? g ( r )
r
versus - r mx , where rmx i s t h e p o s i t i o n of t h e f i r s t
maxinum. A s 0 end ro m e p r o o o r t i o n n l t o r max ~ n d
if t h e s u b s t a n c e s have s m e t p e o f n o t e n t i e l , t h e n

S u b s t i t u t i n p e a u z t i o n ( 5 7 ) i n e q u c t i o n ( 5 6 ) one
obtains

Assurninp r
0
= 0 (59) \i /
end t h e n s u b s t i t u t i n t ? o for ro i n e q u ~ t i o n(58) one
obt~ins
 S u b s t i t u t i n a equntion ( 6 0 ) i n t o equntion ( 5 3 ) nnd
t h e n assuninp t h ~ each
t r a d i ~ ld i s t r i b u t30x1
l function
i s independent of c o n p o s i t i o n o f t h e s o l u t i o n , i . e .

t h e e x p r e s s i o n f o r t h e energy of mixing, BE^ , of a.

r e g u l a r s o l u t i o n m y be r e l v r i t t e n a s

Equetion ( 6 1 ) i s t h e m ~ t h e n f i t i c ~statement
l of
S c ~ t c h r . r ds' n s s u q t i o n t h n t "... t h e d i s t r i b u t i o n of t h e
molecules i n n o s i t i o n nnd i n o r i e n t e t i o n is rendom, i . e .
it i s n o t dependent on...the n a t u r e of o t h e r n o l e c u l e s
p r e s e n t ( i n a repmulors o l u t i o n ) ."
Heturning t o e o u ~ t i o n( 6 2 ) , t h e v n l u e s f o r k12
cen be found i n London's r e l n t i o n r41

where 1's e r e the ionizction potentials.

 - 33 -
S u b s t i t u t i n g e q u e t i o n ( 6 3 ~ )i n t o e a u ~ t i o n( 6 2 ) ,

The e q u a t i o n ( 6 3 b ) w i l l r e d u c e t o S c a t c h 8 r d T s equa-
t i o n if one assumes " c o h e s i v e enerFy d e n s i t i e s " , c's,
as

Geometric I l e ~ nA s s u m t i o n
Before discuss in^ t h e o t h e r t-isnects of t h e R e p u l -
a r S o l u t i o n t h e o r y , it i s i m p o r t e n t t o c o n s i d e r t h e
 - 34 -
r e l i a b i l i t y o f t h e geometric n e m ~ s s u m p t i o npiven i n
equntion ( 3 9 ) , i . e .

m d i t s e f f e c t on t h e m a m i t u d e of t h e i n t e r a c t i o n con-

stmt, *12' i n equation ( 3 9 ) .

Fron equation ( 6 4 c ) we s e e t h a t

From e q u ~ t i o n( 6 5 ) we s e e t h ~ ti f

I1 = I2 and -
Oil - O22

t h e n only
'12 = J C11C~2
For a n u - b e r of systems t h e s e c o n d i t i o n s a r e n o t I
- J
satisfied. For e x m p l e , hydrocarbons and f l u o r o c n r b o n s
hnve i o n i z a t i o n p o t e n t i a l s bout 10 ev and 1 6 ev respec-
t i v e l y and it i s now g e n e r a l l y ~ c c e p t e C411
d t h ~ st y s t e n s

such a s h y d r o c a r b o n - f l u o r o c n r b o n n i x t u r e s do n o t obey
geometric mean ~ s s u n pions.
t Reed,[ 421 i n an a t t e n n t t o
~ l c c o u n tf o r t h e l a r g e excess f r e e m e r c i e s v h i c h hnve
been observed f o r hydrocnrbon-fluorocnrbon g i x t u r e s ,
 - 35 -
reexanined t h e r o l e o f t h e d i f f e r e n c e s i n i o n i z n t i o n
p o t e n t i a l s and t h e c o l l i s i o n d i n n e t e r s of t h e connon-
e n t s i n t h e eeometric nssunptions. He v r o t e

A,, = C 11+C22 - 2 C 12 = ( 6 1- 6 2 )
2 +26162(l-fIf0)
(67)

where
6 !I
2 Ii
-
f~ - I +
1
I*

and
f0 ={ 2o,$o,B 13
9 1 -I- O22
Reed e s t i m a t e d t h a t , f o r hydrocnrbon-fluorocnrbon
mixtures, fI i s nbout 0.97 snd fo i s about 0.995.
So f o r b l = 7.5 nnd b 2 = 6.0 ~ a l ~ / ~ c r n - ~t fhle, second

term i n equation ( 6 7 ) becones about 3 c n l c d 3 which

when coupled w i t h n o l n r volume from 100 t o 200 cn3 can
produce an energy of mixing a t c o n s t a n t volwle a s much
a s 150 c a l moleg1 i n e x c e s s of t h a t p r e d i c t e d f r o n equn-

--
The c o n s i d e r e t i o n of t h e d i f f e r e n c e i n i o n i z a t i o n
p o t e n t i a l s o f f e r s a s a t i s f a c t o r y explanation f o r t h e
anonnlously l n r g e h e a t of mixing end e x c e s s f r e e energy
of mixing observed f o r hydrocarbon-fluorocarbon n i x t -
ures. It would p r e d i c t f o r o t h e r s o l u t i o n s s i r n i l a r
anomalies which a r e not observed e x p e r i x n t a l l y , eg.
CC14 and 1, have i o n i z a t i o n p o t e n t i n l s o f * 1 1 . 0 and 3.7
av r e s p e c t i v e l y but t h e i r m i x t u r e s v i t h f ~ u o r o c n r b o n s
&o?r excess f r e e enerpy i n pood apreenent w i t h equntion -
(:3R) w i t h no need f o r n c o r r e c t i o n t e r n . On t h e o t h e r
 - 36 -
hand it h a s a l s o been r e p o r t e d 1433 t h a t f o r a benzene-
t o l u e n e m i x t u r e , where t h e d i f f e r e n c e s i n i o n i z ~ t i o n
p o t e n t i a l of t h e conponents a r e n o t v e r y l a r g e , t h e
v a l u e s of C12 c ~ l c u l n t e df r o n e x p e r i m e n t a l l y d e t e r -
mined *$ a r e c o n s i s t e n t l y lower t h a n v a l u e s c a l c u l - >
atedfron 6
1
and b2 . Recent neasurementsCW of
a c t i v i t y c o e f f i c i e n t s of hydrocarbon s o l u t e s i n nlkane
s o l v e n t s such a s n-C24H50 , n-c30H62 and n-Cj6HT4 ,
by g a s - l i q u i d p a r t i t i o n chromatography, a l s o i n d i c a t e
t h a t f o r a r o n n t i c hydrocarbons, t h e 6 v n l u e of t h e
solvent n-C30H62 h a s t o be c h a n ~ e df r o n 7.730 t o
6.850 t o f i t t h e e x p e r i n e n t ~ lv a l u e s f o r a c t i v i t y coef-

f i c i e n t s whereas f o r a l k a n e hydrocarbons no such ~ d j u s t -

n e n t i s needed.
iludson and KcCoubrey [551 e x m i n e d t h e e f f e c t of
t h e d i f f e r e n c e s i n t h e c o l l i s i o n d i a m e t e r s of n o l e c u l e s
on t h e g e o x e t r i c mean assunption. Assuming t h a t 11 =

Ip t h e y r e w r o t e t h e equntion ( 6 5 ) as

They used t h e equntion ( 6 8 ) t o c n l c u l n t e t h e c r i t -

i c a l t e n n e r ~ t u r ef o r t h e b i n a r y l i q u i d mixture of c-C6HI2
- c-C6Flg and obtained a b e t t e r apreenent w i t h t h e
e x p e r i n e n t a l vnlues.
 Vitoria ~ n ~
d a l k l e ~ [ ~looked
31 into the effects
of t h e d i f f e r e n c e s of t h e m o l a r volumes upon C l p t sof
tetraphenyl t i n - o r g a n i c s o l v e n t s mixtures. They wrote

where

and t h e n t h e y relwote t h e e x p e r i n e n t a l l y determined

where b , in t h e l e f t h ~ n ds i d e of t h e equation, was

c ~ l c u l e t e dfrorl t h e s a t u r a t i o n s o l u b i l i t , i e s . They found
t h a t f o r tetrephenyl t i n k i s much s n a l l e r t h a n u n i t y
0
but b i s n e ~ r l yequal t o u n i t y i f e x c e s s entropy of
n i x i n g i s included i n ~ v r i t i n et h e s ~ t u r ~ t i os n
olubility
equation. O r i n o t h e r words t h e experiment ell-y d e t e r -

mined b i n d i c a t e s t h n t t h e e f f e c t s of s o l v e n t - s o l u t e
molnr volume d i s p n r i t y on t h e peometric mem ~ s s l m p t i o n
i s rmch s m a l l e r f o r t h e systems c o n t r i n i n g t e t r a n h e n y l
t i n 8s s o l u t e thnn one would h w e exnected f r o q equa-
t i o n s such RS t h e equation ( 6 9 ) .
 I n c o n c l u s i o n , t h o u e h t h e g e o m e t r t c mem Rssumpt-

i o n i s based on R narrow t h e o r e t i c a l b s s i s , %?ITS a s s m p -

t i o n when u s e d i n t h e form of s o l u b i l i t y p 8 r a n e t e r s h a s
been proven t o be q u i t e u s e f u l i n c n l c u l ~ t i nt h~e t h e r -
m o i i y n ~ n i c p r o p e r t i e s of t h e s o l u t i o n s o f n o n e l e c t r o l y t e s .

D e t e r n i n e t i o n o f f f S o l u b i li t y P a r a m e t e r "
The R e g u l ~ rs o l u t i o n t h e o r y r e q u i r e s 6 t o be a
----/
self-consistent parmeter. The 6 v a l u e h a s been c a l c -
u l a t e d f o r a l a r g e number of s u b s t a n c e either
aEv $
(1) f r o n t h e r e l a t i o n 6 = IT}, which i s u s u a l -
v
ly u s e d f o r s u b s t a n c e s v h i c h a r e l i q u i d ~t
room t e n p e r a t u r e , o r
( 2 ) by d e t e r m i n i n g s a t u r a t i o n s o l u b i l i t y , i .e. x
2
~ n dt h e n s u b s t i t u t i n g xg i n t h e equntion (48),

provided i s known.
L

The bp v ~ l u ef o r Sn14 was d e t e r n i n e d by E. R. S x i t h

and J. ! l ~ l k l e j [r 453 from i t s s o l u b i l i t y i n s l m e e nun-

b e r of' o r ~ o n i cs o l v e n t s . I n T a b l e 1 bg v a l u e f o r Sn14

i s g i v e n t o shov t h a t t h e r e e x i s t a r e n s o n a b l e c o n s i s -
tency i n b2 vhen determined f r o n s a t m a t i o n s o l u b i l i t y .
The lf s o l u b i l i t y p e r m e t e r " can a l s o be c a l c u l a t e d

from t h e c a l o r i m e t r i c h e s t o f v a p o r i z a t i o n . k t low

vnpour p r e s s u r e , t h e vapour i n e q u i l i b r i u m w i t h l i q u i d
i s e s s e n t i a l l y i d e a l ~ n d-E can be r e p l a c e d by A Ev ,-
b

t h e e n e r g y of v a p o r i z ~ t i o n ,which i n t u r n oan h e r e p l a c e d
by AH' - RT where AH' is t h e heat of vnporizntion.
T a b l e I. 1; S o l u b i l i t y p a r a m e t e r f o r Sn14 - c a l c u l a t e d from
s a t u r a t i o n s o l u b i l i t y d a t a .145 1

Solvent Solubility ' 1 for 62 for

100x2 solvent Sn I4

C H CH
6 5 3
(toluene)

2
6 ' s a r e expressed i n cal.* CZ.~
 R , L. S c o t t proposed an e n p i r i c n l r u l e f o r h e n t o f
v a p o r i z a t i o n a t 298: K and a t b o i l i n p p o i n t o f t h e l i q -
u i d ~ v h i c hi s given below,

v
AH298 (call mole) = -2950 + 23.7TB + 0.02TB2 (72

T~ i s t h e b o i l i n g p o i n t of t h e l i q u i d . It should be
mentioned h e r e t h a t 6 c a l c u l a t e d from e q u a t i o n ( 7 1 )
may n o t be a p p r o p r i a t e f o r s o l i d s becRuse of t h e l o n g

e x t r ~ i n o l a t i o ninvolved i n such c a s e s ,

It h a s been assumed b e f o r e t h a t t h e volune change

on mixing i s z e r o f o r r e g u l a r s o l u t i o n , o r I n o t h e r ltrords
t h e h e e t of mixing c m be i d e n t i f i e d w i t h t h e enerpy of
max
nixing, So x2 o r mole f r ~ c t i o nof component 2 a t
which t h e h e a t o f mixing w i l l be nexinurn c m be c ~ l c u l -
a t e d from e q u a t i o n (11) .
The e x p e r i n e n t a l and t h e p r e d i c t e d v ~ l u e sf o r xmax
2
a r e given i n Table 2. These v a l u e s m e t a k e n from r e f -
erence [46]. It i s c l e a r f r o 3 Table 2 t h a t t h e c c l c -
u l - ~ t e dv n l u e of xmax n u i t e o f t e n d o e s n o t ngree w i t h
2
t h e experiment01 val.ue. One of t h e reflsons, RS suppest-
ed by G , S c n t c h a r dr47]
, is t h ~ tth e Avm o r t h e volume
 rnax
Observed and predicted values for x2
Table 1.2:
(i.e., mole fraction of component 2 at which the heat
of mixing is mbximum).

System M TOA
max
v~ v2 *max X2
cc cc cal/mole obs. calc'd

iso-CaH1
+ 166 294
hexadecane
change on n i x i n g i s never z e r o f o r a r e ~ u l ns o~l u t i o n . j
So it becones n e c e s s a r y t o c o n v e r t t h e e x ~ e r i m e n t o l
numbers which a r e u s u a l l y determined e t constRnt p r e s -
s u r e t o t h e c o n s t a n t volume nuabers.
The method of making t h e s e thernodynamic c o r r e c -
t i o n s was f i r s t o u t l i n e d by G . Scatchard.C473 ~ i i sequa-

t i o n s were d e r i v e d f r o a a two-step p r o c e s s , a mixing o f

two coxponents a t c o n s t a n t v o l m e followed .by an expan-
s i o n o r c o n t r a c t i o n of t h e n i x t u r e (RS t h e c e s e nay b e )
t o recover t h e pressure, i.e. t h e i n i t i n 1 nressure. Iie
M
o b t a i n e d t h e c o n s t e n t volume f u n c t i o n s AAV, AS: ~ n d

bq by e x p ~ n d i n at h e c o n s t m t n r e s s u r e f u n c t i o n s M
AAp ,
AS! m d AE; i n t h e form of a Taylor s e r i e s e x p ~ n s b n
around vM = VO + *vE AS

AF; and AH! Rre obtnined by adding APV t o equation

( 7 4 ) and e q u a t i o n ( 7 6 ) r e s p e c t i v e l y . A s t h e i n i t i a l end
f i n n l p r e s s u r e s Rre t h e same, APV i s nerely PAV
M , or
 The a and $ i n equation (78) m e t h e coeffic-

i e n t s o f t h e r n a l expansion and i s o t h e r m 1 c o n n r e s s i b i l -
i t y of t h e m i x t u r e , r e s p e c t i v e l y .
Hearranginp t h e e q u z t i o n ( 7 8 ) , one o b t a i n s

s o t h e knowledge of a ~ n dp ~ l l o w sone t o conpare

e x p e r i m e n t a l l y determined A ~ Mw i t h c e l c u l a t e d A
P
From e q u ~ t i o n ( 7 7 ) we a l s o s e e t h e t t h e d i f f e r e n c e
M M
between hFp and AAV i s dependent on (vE12 ~ n dn o t
E
on vE o r a s lonp a s V i s small, t h e d i f f e r e n c e .
M M J'
betveen AFp and AAV i s s m a l l . It h a s been observed
t h ~ Hegultir
t S o l u t i o n t h e o r y p r e d i c t s f r e e energy of -
n i x i n g w i t h i n a few p e r c e n t of t h e e x p e r i m e n t a l v a l u e s
hereas as f o r t h e h e a t and t h e e n t r o p y of l n i x i n ~t h e agree-

ment between t h e experiments1 and t h e p r e d i c t e d v 8 l u e s

ilagnitude of Volu3e C h ~ n g e~t C o n s t ~ n tP r e s s u r e

vE , t h e e x c e s s volume o f n i x i n g , i s piven by en

e x a c t thermodynmic r e l n t i o n ~s
and w r i t i n g

and if

~ T , V )
VE

, or
F~ = A ~ ( T , v )

is smnll (vE)*
+ --1
2 VP , ( VE ) 2

can be n e p l e c t e d t o makc F~ =

For r e g u l a r s o l u t i o n s = 0 , end it i-s independent

of p r e s s u r e . So e q u a t i o n ( 8 0 ) becones

u i n e q u a t i o n (81) c o r r e s p o n d s t o t h e p r e s s u r e , volune,
c o m p r e s s i b i l i t y , e t c . of t h e unnixed i n i t i a l s t a t e of
t h e systen. Movr i f %E = Em - EU where Em is the
energy of t h e n i x t u r e and cTT -E
i s r e p l e c e d by n(T)
where n i s t h e r s t i o of i n t e r n 2 1 p r e s s u r e t o c o h e s i v e
energy d e n s i t y , e q u ~ t i o n(81) becones

Assuninp nm and nu a r e t h e sane f o r t h e n i x + . u r e s and

t h e unmixed connonents and t h e n i n v o k l n c t h e c o n d i t i o n
E
that SV = 0 nnd A% =F , vE cnn be w r i t t e n a s
P a r t i a l n o l a l volume i n d i l u t e s o-
l u t-
ions
Of special i n t e r e s t are t h e p a r t i a l n o l a l volunes
of s o l u t e s i n t h e h i c h l y d i l u t e s o l u t i o n s . Different-
i a t i a t i o n of e q u ~ t i o n(83a) i n t h e l i m i t a s x + 0
2
y i e l d s t h e equation

I n T ~ b l e3 a comparison between experimental find pre-

d i c t e d v a l u e s f o r t h e p m t i ~ molal
l volumes m e given.
-3
TabIeI.
- -E -E
Solute Solvent V: v2( obs) vp( obs) v2( c a l c f d )

v2( c a l c ' d) i n Tnble 3 w8s c a l c u l a t e d from eqnntion

( 8 2 ~ ) . It should be nentioned h e r e t h ~ though
t f o r Br
2
t h e agreement between t h e c n l c u l ~ t e dV ~ ~n
R ~ U de x p e r i x e n t -
~1 v a l u e i s n o t b a d , t h e e q u n t i o n s ( 8 3 a , b , c ) m e very
a p p r o x i n a t e eqnat ions. But t h e s e e q u n t i o n s c m e x p l a i n
the results qualitatively.

Entropy of mixin@ molecules of unequnl s i z e I-84-911

So f a r we have assumed t h a t a s o l u t i o n i s i d e ~ l
if t h e h e a t of mixing i s z e r o ( s e e e q u a t i o n ( 4 7 ) ) .
But it h a s been knovm since 1 9 3 3 t h ~ tt h e entropy o f
n i x i n g u n e q u ~ lmolecules may n o t be i d e e l even i f t h e
h e a t of s o l u t i o n m d t h e volume change on mixing m e
zero.
3. H. H i l d e b r ~ nC511
d derived t h e expression f o r
t h e entropy of n i x i n g of unequal molecules f,70m t h e
n f r e e volune t h e o r y " p o i n t of view a s

f o r one mole of s o l u t i o n formed a t constant, p r e s s u r e .

By d i f f e r e n t i c t i n g equation ( 8 4 ) ,

v =1
Then he assumed t h a t 1 vL .So equntion ( 8 5 ) becones
f
V2 VE
 - 47 -
When V1 V2, t h e e q u a t i o n (86b) becones

Adding e q u ~ t i o n( 8 7 ) t o t h e h e ~ o
t f mixing t e r m n s d e r -
i v e d p r e v i o u s l y , t h e e q u a t i o n ( 4 7 ) becones

~f x2 e xl such t h a t x1 - 1, t h e n

So e q u ~ t i o n(88)can be w r i t t e n 8s

Entrony o f s o l u t i o n of a s o l i d
I n d e r i v i n g t h e H e m l n r S o l u t i o n t h e o r y , it h a s
been assumed t h a t t h e mixing i s " r ~ n d o 9 . l ~ It i s pos-
s i b l e t o d e t e r m i n e t h e p s r t i ~ no181
l e n t r o y chnnee o f
solid solute f o r R v e r y d i l u t e s o l u t i o n from t h e temp-
e r a t u r e dependence of t h e s n t u r n t i o n s o l u b i l i t y ~ n dcnn
 - 48 -
be conpmed w i t h t h e p r e d i c t e d v a l u e s . It i s r e l a t e d

t o t h e t e ~ p e r n t u r ec o e f f i c i e n t of t h e s o l u b i l i t y by
means of t h e thermodynamic e q u a t i o n

The second f ~ c t o ron t h e r i g h t hand s i d e of t h e equntion

( 9 2 ) i s j u s t t h e change of s o l u b i l i t y w i t h t e m p e r a t u r e
S
a t constant pressure i f
F2 - F~ = 0 , i n t h e f i r s t ~ R C -
f
tor, F ~ - =F RT~ I n ( + ) , where f2 i s t h e fugncity
f2
of t h e s o l u t e i n t h e s o l u t i o n and f:
is thnt in the

solid state. I f t h e solid s t n t e i s t h e pure solute

(i.e. i f no s o l i d s o l u t i o n i s formed), f: i s indepen-
d e n t of X2 and so it can b e w r i t t e n a sL

G :"n;Ip,r~
i s t h e l I e n r y T s Lwr c o r r e c t i o n f a c t o r ; it

i s c l o s e t o u n i t y f o r a d i l u t e s o l u t i o n of s o l i d s .
S i n c e a t s n t u r ~ t i o ns o l u b i l i t y , thehe~tof
F~ = F~
s o l u t i o n rwy be w r i t t e n 8s

- - H2S
H2 = ~ ( - 2s:) ~= RT [,
a In x
T2 (9 5 ~
Sat . p
 - 49 -
The a l t e r n a t e form of e q u a t i o n (95fi),

i s t h e lVvan1tHoff e q u a t i o n " and i s e x t e n s i v e l y used t o

c a l c u l a t e t h e h e a t o f s o l u t i o n of a d i l u t e s o l u t e .
E q u ~ t i o n ( 9 4 ) g i v e s t h o e n t r o n y of s o l u t i o n a t

c o n s t a n t p r e s s u r e but R e p u l m S o l u t i o n t h e o r y i s main-
l y concerned w i t h c o n s t a n t voluqe q u ~ n t i t i e s . So equn-
t i o n ( 9 5 ) h a s t o be converted t o t h e c o n s t a n t volume
e n t r o p y chenge. Fron e q u a t i o n ( 7 5 ) ,

at X2 + 0 where a end p of t h e m i x t u r e ~ n n r o a c h

t h e v ~ l u e sof t h e pure s o l v e n t .

-D i s c u s s i o n
From t h e Regular S o l u t i o n t h e o r y , it i s expected

thst
v ,
AS2 1.e. (z2- s:)~ i s nlotted against
-R i n x2 , a s t r ~ i g h tl i n e should be ohtnined whose
s l o p e i s exaected t o be e q m l t o u n i t y a n d t h e i n t e r -
c e p t t o be e q u ~ lt o t h e e n t r o p y o f f u s i o n of t h e s o l i d

s o l u t e a t t h a t temperature.
E. B. S ~ i t hand J. 'l'lalkleyr521 p l o t t e d (z2- s:)~
and (z2- s:)~ i in st -R in x2 for Sn14 and t h e y

o b t a i n e d a s t r ~ i p h tl i n e which hnd a u n i t s l o p e nnd a

correct intercept. J. H. Hildebrand ? l o t t e d (3
2 - s:)~
versus -R in x2 f o r iodine. He o b t ~ i n e dR s t r e i p h t
l i n e but t h e s l o p e was 1.10 m d t h e i n t e r c e p t was d i f -
f e r e n t from t h e expected v ~ l u e . It s3ould be mentioned
h e r e t h a t t h e r e e r e u n c e r t a i n t i e s involved r e g a r d i n g t h e
d e t e r m i n a t i o n of V; of a s o l i d with h i ~ h
meltinn ~ o i n t .
of a s o l i d a t nny t e m p e r a t u r e i s t h e volune of t h e
:V
h y p o t h e t i c a l l i q u i d supercooled below m e l t in^: p o i n t .
U s u a l l y it i n v o l v e s a l o n g e x t r n p o l ~ion.
t
I n t h e c a s e of n o n - v i o l e t s o l u t i o n of i o d i n e , t h e
e n t r o p y of s o l u t i o n should n o t be expected t o be i d e n 1
as it h e s been supgested t h a t t h e chenge of c o l o u r of
t h e iodine solution f r o n t h e v i o l e t t o t h e non-violet
i s due t o t h e f o r n e t i o n o f " c h e r g e - t r m s f e r " conplex.
A s e x p e c t e d , t h e agreement betveen t h e c n l c u l ~ a t e d

(z2 - s:)~ from -R in x2 ~ n dexperiments1 (S2 -

becomes worse when t h e d i f f e r e n c e b e t ~ w e nt h e molnr
volume becones l a r p e r ~s i n t h e c a s e o f t e t r a p h e n y l t i n
i n o r d i n n r y n o n p o l ~ rs o l v e n t s C 5 3 y 5 4 1 0 r h r o m i n e in

Regarding v2 , a s p r e d i c t e d by e o u ~ t l o n( 0 3 ) , i t
h e s been mentioned b e f o r e t h a t t h i s i s o n l y an anprox-
incite e q u ~ t i o nnnd i s only q u a l i t a t i v e i n n a t u r e . It
p r e d i c t s t h e i n c r e a s e of V2 of s o l u t e with t h e increese

of (bl - be)' v a l u e which hes been v e r i f i e d by E. H.

Smith iind J. WRlkley C521 and M. V i t o r i n cnd J. ' I ~ L k l e y

C53y541 by p l o t t i n g B2 *eninst 6 1 of t h e s o l v e n t .
 - 51 -
The n ~ p l i c ai to n o f t h e simn1.e H e ~ u l e rS o l u t i o n
t h e o r y t o n i x t u r e s o f u n e q u ~ lr i o l e c u l e s r n i s e s FI few
y e t - u n s o l v e d p r o b l e m , p o r t i c u l c i r l y when t h e e n t r o p v
of n i x i n g u n e q u a l i ? o l e c u l e s i s elnost, i n v ~ r i ~ h l non-
-y
I
- !

i d e a l , even i f t h e n o l e c u l e s a r e s p h e r i c a l m d heve

i s known a s t h e "Flory-IIupyins t e r m w i s o f t e n used t o

celcul~te (z2 - s:)~ but t h e r e are doubts about i t s
r e l i n b i l i t y . [ 53,541
T h i s ~ r o h l e nw i l l he d i s c u s s e d i n n o r e d e t a i l i n
l a t e r chapters.
 Chapter - I1

Solubility S t u d i e s in Mixed Solvents

 - 53 -
IIildebrand and ~ c o t t [ ~c a~l c]u l a t e d t h e h e a t of

n i x i n g f o r t h r e e component s y s t e n s f o l l o v r i n ~t h e s i n -
i l a r p r o c e d u r e used by ~ c a t c h ~ r d [ 3 7f]o r b i n a r y nonelec-

t r o l y t e systens. They w r o t e t h e c o h e s i v e e n e r c y n e r
n o l e of a t e r n a r y m i x t u r e a s

where x's, Q 1 s ,and V 1 s have t h e meaning of n o l e

f r a c t i o n , volume f r a c t i o n s and volumes, and C 1 s are

t h e c o h e s i v e energy d e n s i t i e s .
I n e q u e t i o n ( I ) , C 1 s a r e t h e c o n s t a n t s of b i n a r y
s y s t e n s m d t h e r e a r e n o t c o n s t a n t s degendinc on a l l

t h r e e components s i r m l t a n e o u s l y . This i s t h e d i r e c t
consequence of t h e essumption t h a t t h e energy o f t h r e e
s e t s o f n o l e c u l e s can be r e p r e s e n t e d by t h e surn of t h e

t h r e e p a i r s t a k e n independently.
Hecalling t h a t -Ell = C
11V 1 etc., t h e h e a t of

nixing, AH^ , may be w r i t t e n a s

where

The A ' s a r e t h e i n t e r a c t i o n c o n s t a n t s of t h r e e

s e p ~ r a t eb i n e r y systems; s o t h e t e r n a r y s y s t e m s ?my be

completely d e s c r i b e d i f a l l t h r e e two-com~onent s y s t m s

a r e known.
D i f f e r e n t i ~ t i n pe q u a t i o n ( 2 ) , one o b t a i n s p e r t i a l

n o l a l h e u t s o f mixing:

I f t h e a s s u p t i o n t h a t t h e i n t e r a c t i o n e n e r p y be-
tween t h e u n l i k e p a i r i s t h e g e o m e t r i c n e s n o f t h a t
between t h e l i k e p a i r s , t h e n

and t h e e q u ~ t i o n s( 4 ~ , b , c )r e d u c e t o
 - 55 -
The e q u a t i o n s ( 6 a , b , c ) c m b e r e a r r ~ n g e dIn d i f f e r e n t
wFlys:
( i ) Each of t h e e q u a t i o n s n a y be r e e r r ~ n g e di n
such R \my a s t o show t h n t t h e h e r t o f mixing o f l i q u i d
2 w i t h l i q u i d s 1 and 3 i s e q u i v ~ l e n tt o t h e h e a t of

mixing o f l i q u i d 2 w i t h R h y p o t h e t i c ~ ll i q u i d whose 6
i s t h e volume f r a c t i o n Rverage o f 1 ond 3.

where

and

The e q u a t i o n s ( 7 1 , ( 8 ) , end ( 9 ) c m be r e a r r a n g e d
f u r t h e r i n t e r x s of t h e volume f r a c t i o n s g o f com-
ponent 1 and 3 i n p u r e n i x e d s o l v e n t s when comnonent 2
h e s n o t y e t been ~ d d e d , such t h a t

whereas a n a l y s i s o f t h e e q , u ~ t i o n s( 7 ) , ( 8 ), ~ n d( 9 )
yields
6, + m2 = 1

The t r m s f o m z t i o n o f t h e e q u a t i o n s ( 7 ) , ( R ) , find
( 9 ) i n . t e r m s o f e q u n t i o n ( 1 0 ) can be done i n R r~uch
s i m p l e r mmner i n t h e f o l l o r i n g w ~ y :
From e q u ~ t i o n ( 7 ) ,

Now t h e r e e x i s t s n r e l a t i o n s h i p between t h e @ y ls
i n p u r e n i x e d s o l v e n t s and mils i n t h r e e

systems such t h a t

Substituting and Q 3ls from t h e

~ n d( 1 5 ) i n e q u ~ t i o n(12) one o b t a i n s

Again i f one d e f i n e s 8, i n t e r n s of @;) and @; then

 A s e q u e t i o n s ( 1 6 ) end ( 1 7 ) m e i d e n t i c 8 1 nnd )m ' s
i n both t h e e q u n t i o n s a r e t h e sane, &,(I) = 6, or 6,

for ci nixed s o l v e n t csn be d e f i n e d i n t e r n s of t h e v o l -

ume f r e c t i o n s of comgonent 1 m d 3 i n p u r e . nixed s o l v e n t
such thcit
' m = @;bl + @;b3

such t h a t
I; + PO =
3
1

( i i ) An K i t e r n a t e t r a n s f o r m e t i o n of t h e equatFons
( 6 a , b , c ) l e a d s t o t h e p a r t i ~ ln o l a l he& of mixing a s
A f u n c t i o n of t h e 6 o f t h e pure substance m d t h e
averege 6 of t h e t e r n a r y mixture:

where

--
A c t i v i t y C o e f f i c i e n t i n R e p u l ~ rTernary Svst;e:?s
For r e g u l m s o l u t i o n s , t h e entropy i s i d e n 1 and
the activity coefficients m e directly relEted t o the
 - 58 -
p ~ r t i molal
~ l h e a t s o f mixing. Hence f o r t h e e q u ~ t i o n s
( 7 ) ~ n d(19), one may w r i t e ,

o r t h e s a t u r a t i o n s o l u b i l i t y of t h e s o l u t e 2 c m be
formulated a s

where ai i s t h e i d e a l s o l u b i l i t y o f conponent, 2 .
2
I n t h i s c h a p t e r we i n v e s t i e e t e t h e r e l e t i o n s h i p

6m = @;)bl + @;6j
and o t h e r e x c e s s thernlodynmic prop-
e r t i e s o f component 2 i n mixed s o l v e n t s . O u r i n v e s t i -
g a t i o n sufrpests t h ~ st u c h a r e l n t i o n s h i n of
cm 6
m
o n l y be assumed i f we a r e sllowed t o d e f i n e an " e f f e c -
t i v e volume f r a c t i o n v term. This re-definition a r i s e s

due t o t h e f a c t t h a t t h e s o l v e n t n o l e c u l e environment
mound R s a l u t e nolecule is not adequately described
by t h e sirngle volume f r a c t i o n s , s o that one has t o t a k e ac-
count of t h e p o s s i b i l i t y t h p t t h e s o l u t e r ? ~ y
be ? r e f -
e r e n t i a l l y s o l v a t e d by a p ~ r t i c u l a rs o l v e n t n ~ r t n e r .
I n o r d e r t o emphasize t h i s p r e f e r e n t i e l s o l v e t i o n , we
f i r s t chose benzene a s a mixed solvent, p m t n e r i n ' t h e ben-

zene- iodine-cyclohexfine system. L a t e r we determined

the solubility of stannic iodide in benzene - c-C6H12
mixtures. We selected I2 and Sn14 as solutes and
C6H6 - c-C6H12 as the solvents because of the fact
that all necessary thermodynamic data for these systems
are available and the binary systems of each solute in
each solvent are well studied.[69,70,71-731
Experimental
Temperature Control
The temperature of the bath in which the saturated
solutions were prepared was controlled by means of a
contact thermoregulator and an electronic relay box
- both supplied by Fisher Scientific Co. Ltd.
A Beckmann thermometer was inserted in the bath to
determine any temperature fluctuations.
The thermoregulator was connected to an electronic
relay box as was a heating co'il. In addition to the
heating coil and thermoregulator, one pump for circu-
I
lating water and a cooling coil were immersed in the bath.
The cooling coil was connected to the cold water supply
in the laboratory, which is sufficiently cold to keep
temperature of the bath at 20•‹C (the lowest temperature
used in this experiment). The temperature of the bath
was held within 2 0 . 0 1 ~of
~ the desired value.
For the determination of the partial molal volume
of the solute a toluene regulator instead of thermo-
regulator was used. No fluctuation of the liquid level
in the stem of the dilatometer was observed using a
cathetometer.
Determination of the solubility:
The method used in determining the saturation
solubility was a simple and quick one. The procedure
can be described in the following way:
The solvent and excess solute were placed in 50
ml flask along with a small teflon-coated magnet bar.
The flask was placed at the side wall of the thermo-
stated bath. A Fisher "Thermix" magnetic stirrer was
placed outside the bath in contact with the side wall.
With such an arrangement the solution can be stirred
as long as needed. Usually the solution was stirred for
24 hours and the solution allowed to settle for further '

12 hours. Then the flask was opened and the required

amount of solution was taken out by means of a volume-
tric pipet. Two test solutions were pigetted out.
Then the flask was closed again and the whole proced-
ure was repeated. This procedure was repeated for
each solvent-solute system at one temperature, until
three consecutive self-consistent pairs of values were
found.
The amoung of solute in the solution was measured
spectroscopically at an appripriate absorption peak of
the solute ( I ~
: 520 mp; Sn14 : 320 rnV; and s ~ ( c ~ F ~ ) ~

: 267 mV). A Ueerts law calibration plot was constructed

 for each solute, using known quantities solute in diff-
erent solvent mixtures.
The saturated solution of solute pipetted out
(1-2 ml) was too concentrated for direct spectroscopic
studies. Each sample removed from the dissolution cell
was diluted (usually 1 : 250 for I2 and 1 : 500 for
Sn14 and Sn(C6F5)4) with c-C6H12 and then the optical
density of the diluted solution was measured at the
absorption peak of the solute using a Cary - 14 spec-
trometer.
The accuracy of this technique was verified by
comparing the solubility data obtained by this method
with available solubility data obtained by other means.
A comparison of the solubility of I2 determined spec-
troscopically with the solubility of I2 determined by
means of chemical analysis (titration) is given below.

Solvent Temperatu$e X2 X2
(spectro- (titra-
scopic method) tion)

. 6%
Q

. CgH6 25'~ 0.0481 0,.&,[75I

n-heptane 25'~ 0.00676 0.00679 C75I

The general consistency of the final results also con-

firmed the accuracy of this technique (the percentage
average error in the saturation solubility is 2 1$).
 -62-

The spectrcscopic analysis is simpler in tech-

nique and quicker in determining the amount of solute
in solution than any other method of chemical analysis.
The solvents were spectroscopic grade (supplied
by Fisher Scientific Co. Ltd.) and were used without
further purification.
A typical experimental result: - Saturation solubility
of I2 in a benzene - cyclohexane mixed solvent at 25'~.
-
Volume fraction of benzene in solute-free mixed
solvent = 0.7604
Number of Saturation solubility of I2
observation in gms/liter of solvent.

Average = 108.9
Average error = -
+ 0.9%
or, the saturation solubility of I 2 = 108.9 -
+ 0.9 gms/liter
of solvent.
Effect of average error on b m I-

(a) Effect of positive error on 6 ,

Saturation solubility of L 2 = 108.0 + 0.9 gms/liter of
solvent
or, x2 = 0.0392
Writing the saturation soliability as

we obtain,

(where b2 = 14.1, V2 = 59 cc and

(b) Effect of negative deviation on bm

Saturation solubility of I2 in gms/liter of solvent

= 108.9 - 0.9
or, x2 = 0.0385
or, brn = 9.73
6, determined from the average saturation solubility
= 9.74. So, we see that a 1% average error affects
6, for the benzene - I* - cyclohexane system by one in
second decimal place, so that the effect is one in
thousand. I

The effect of -
+ 1$ error on 6, for the benzene -
Sn14 -
cyclohexane system will be much smaller because
for %I4, (v~/RT)'I2 = 1.98 in comparison to (v*/RT) 1/2
= 3.168 for 12.

Determination of partial molal volume

The common method of determining partial molal
volume, by determining the density of solution of known
composition, requires that the density be measured with
an accuracy difficult to obtain with volatile compounds;
moreover the method is inaccurate if the solution is
 -64-
diluteC951 We, therefore, adopted a simple dilato-
metric method, which has been applied successfully
previously for measuring the partial molal volume of
iodine, C951 stannic iodideC5*' and tetraphenyl tin[%I.
The two dilatometers which were built by Dr. M. VitoriaL-541
consisted of cylindrical glass bulbs -- one being of
150 ml capacity, the other of 10 ml capacity to conserve
solvent. The stem of the dilatometer is calibrated
capillary of uniform internal diameter of 0.2 crn [541
The dilatometer bulb was placed in the thermostated
water bath whose temperature was kept constant at 25
+
- 0.01~~.A weighed amount of solute was sealed into
a long thin-walled capillary, narrow enough to slip
down through the stem into the bulb. This was broken
under the solvent by a glass ball sealed in the dila-
tometer and the solute was dissolved by carefully shaking
the glass ball. The rise of the liquid level in the
capillary was determined by using a cathetometer, after
equilibrium of the solution was reached, A correction
was made for the amount of glass added and the partial
molal volume of the solute was calculated from the
expression
- (nr
2
A L & I ~ /W2
)
V2 =
where r is the radius of the capillary, AC is the cor-
rected rise in the liquid level, W2 is the weight of
the solute and 1\T2 is the molecular weight of the solute. A
typical experimental result along with error analysis
is given belowIr 711
A typical experimental result:
Composition of mixed solvent:
iP 0
= iP1 = 0.6927
Benzene

Wt. of glass = 0.0324 gm

wt. of glass + I2 = 0.0456 -
+ 0.0001 m s

so, wt. of I2 = 0.0141 -

+ 0.0001 gms.
Total rise of liquid level = 0.565 + 0.001 cm.
Rise due to glass = 0.453 2 0.002 cm.
(~ensityof glass was taken as 2.26 -
+ 0.01 gm/cc C721. )
Rise due to I2 in solution = 0.112 -+ 0.003 cm.
Partial m o l d volume of I2 = V2
-

i
Results
-P
Saturation solubility, entropy of solution (\s2 ),
partial molal volumes and other relevant data for I2
in c6H6 - c-C6H12 are given in Table 11.1. In Figure
11.1 we give -R In x2 versus O
1 (volume fractions of
benzene) plots at 20•‹, 25' and 30'~. In Figure 11.2
we plot the excess quantities
in):x = R[ ~n :x - (@, in xi
3 ]
+ a 3 in x2)
R(
and
-m
V2(excess) -m
= V2 -
- (GFV2 + @ ~ 3 )
3 2
Assyrnetry of both the excess curves was noted.
In Table 11.5 we give the saturation solubility
and other relevant data for Sn14 in benzene - c-C6H12.
m
In Figure I119 we plot -R in x2 (for Snl4 )
against m l0 (volume fraction of benzene) at 25'~.
The saturation solubility of naphthalene in
CH212 - c-C6H12 mixed solvent determined spectroscopi-
cally is given in Table 11.10. The saturation solu-
bility of Sn(C6F5)4 determined spectroscopically is
given in Table 111.4 and the partial molal volumes of
sn(C P ) in different organic solvents are given in
6 5 4
Table 111.5.
Discussion
I n t e r m s of RegulRr S o l u t i o n t h e o r y , t h e s f i t u r ~ t i o n
s o l u b i l i t y of i o d i n e i n t h e nixed s o l v e n t and i o d i n e i n
pure c-C6H12 s o l v e n t a r e given by

where s u b s c r i p t m r e f e r s t o t h e p a r t i c u l ~ rp r o n e r t y
o r q u e n t i t y o f t h e n i x e d al v e n t f o r I2 i n C6H6 -
c-C6HI2 system, s u b s c r i p t 1 always r e f e r s t o benzene,
2 t o i o d i n e and 3 to c-C6H12 .

xm i s t h e s a t u r a t i o n sore f r a c t f o n solubility of 2
2 L

i n t h e mixed s o l v e h t ; s i n i l ~ r l y x32 is the s ~ t u r n t i o n

mole f r ~ c t i o ns o l u b i l i t y of 3 i n pure s o l v e n t 3 ( h e r e
~ - c ~) H For
~ a~ d i l u t e s o l u t i o n an i n t h e oase of I2
in c-C6H12 or I2 in C6H6 - c-C6Hl2 nixed s o l v e n t ,
t h e i o d i n e mole f r a c t i o n s o l u b i l i t i e s a r e of t h e o r d e r
of loB2, and
@3
~ n d
m
can be ~ssllmedt o be noun1
t o 1. So e q u n t i o n s ( 2 2 ) and ( 2 3 ) cen be r e w r i t t e n a s
 S i n i l a r l y f o r i o d i n e i n t h e pure s o l v e n t 3,

Dividing e q u ~ t i o n( 2 4 ) by e q u ~ t i o n ( 2 5 ) and t h e n r e a r -
r m g i n p , one o b t a i n s

- i
(ln a2 - In x 3~ 1) 0~ G 62~ - 66 ,3 ) (26)

E q u ~ t i o n( 2 6 ) i m p l i e s t h a t a l i n e a r r e l a t i o n s h i p
i 1
e x i s t s between t h e (In a2 - In x;)~ end I; f o r which
t h e intercept value n t GI = 0 c a n be conoarad t o an

experimental q u a n t i t y and f o r which t h e r a t i o o f t h e

s 1 o p e : i n t e r c e p t may be conpmed w i t h bits.

(ln a2i
1
The r e l ~ t i o n s h i pbetween - In "):x and $;

f o r i o d i n e i n C6H6 -
C-C6H12 i s s h o w i n F i p u r e 11.3
i
and (In a2 - In x2)
m 4 nnd :I i . a . volune f r a c t i o n of
benzene f o r Sn14 in C6H6 - c-C6Hlg i s shown i n F k -
u r e 11.10, Assurnine t h ~ an
t expected l i n e ~ rp r o p o r t i o n -
a l i t y e x i s t s , t h e b e s t i n t e r c e p t vnlue f o r i o d i n e i n

, C6H6 - c-C6H12 nixed s o l v e n t obtained by drawinp t h e

b e s t l i n e i s 1.755 which compares bedly w i t h t h e exper-
i m e n t ~ lvnlue of 1.835 f o r (In ai
2
- 3:
In x2) An

n n ~ l y s i so f t h e p l o t i n F i g u r e 11.3 s u g g e s t s t h a t t h e
r e l ~ t i o n s h i pi s n o t i n f a c t l i n e a r . On t h e c o n t r n r y ,
if R smooth curve i s drmm through t h e e x p e r i n e n t ~ l
p o i n t s , t h e n t h e i n t e r c e p t o f t h e p l o t compnres f ~ v o u r -
a b l y w i t h t h e exnected value. The nbove a n e l y s i s r e s t s
0 0
on t h e v a l i d i t y of t h e assumption t h a t = 9 6
1 1 4- (363
but n o t on any nssuqntion of t h e n c t u ~ l 6 vnlues.
I n Table 11.2 6, for C6H6 - c-C6HI2 mixed s o l v e n t i n
C6H6 - Ig - c-C6Hl2 s y s t e ~ qc a l c u l ~ t e df r 0 n t h e SO~U-

b i l i t y r e l a t i o n s h i p , e q u a t i o n (22), find t h o s e c a l c u l e t e d
0
according t o t h e r e l - a t i o n s h i p = G:b1 4- G3b3 for
b 3 = 8.2 and cS1 ( f o r benzene) of both 9.2 and 9.99,
a r e compared. The former b1 v a l u e beinp t h e thermo-
dynamic AE h v a l u e , t h e l ~ t t e rbeing d e r i v e d f r o 9
t h e experimental s a t u r a t i o n s o l u b i l i t y of i o d i n e i n
.."
pure benzene. The f i r s t s e t o f t h e c a l c u l a t e d brn
v ~ l u e sa r e q u i t e incompatible w i t h t h e brn(experinent-
81) and t h e l a t t e r a r e only i n n o d e r z t e aereement.
The disagreement between t h e L c ~ l c ~ ~ . l ~ 6 rnt 'esd and t h e
experinenta1 values sugpests e i t h e r t h a t a pair-
6m
wise a d d i t i v i t y a p ~ r o x i n a t i o ndoes n o t hold, o r t h a t
t h e n e a r e s t s o l u t e n e i g h b o w s of' s o l u t e i n t h e nixed
s o l v e n t a r e probably n o t r e f l e c t e d by t h e volume f r ~ c -
t i o n s c o n n o s i t i o n of t h e bulk s o l v e n t mixture.
I n a n a l y s i n g t h e f i r s t assuizption, r.?e s e e t h a t i n
t h e absence of d i p o l e i n t e r a c t i o n s and rnolar volume d i f -
f e r e n c e of t h e s o l u t e and s o l v e n t s , t h i s ~ s s u r ? n t i o ni s
s i n i l a r t o t h e one t h n t i s u s u a l l y :>lade i n f o r ~ u l a t i n p
t h e a d d i t i v i t y r u l e f o r d i s p e r s i o n o r v m d e r 7Janls
f o r c e s i n c a l c u l ~ t i n gi n t e r m o l e c u l a r f o r c e s . Although
it h n s been shown by Axilord and ~ e l l e r C 5 9 9 ~ 0(nnd
3
l a t e r by J ~ n s e n~ n dc o - ~ o r k e r s [ ~ ~ - ~t 3
h nl )t t h e ~ d d i t i v -
i t y r u l e f o r van d e r Waals o r d i s p e r s i o n f o r c e s a r e o n l y
approximate but t h e magnitude of t h e c o n t r i b u t i o n o f
t h e nonadditivity t o t h e t o t a l intermolecular f o r c e s

and t h e i r importance a r e not v e r y c l e ~ ra t p r e s e n t ,

Anyway it seems t h ~ at t room t e n p e r a t u r e , t h e c o n t r i b u -
t i o n due t o t h e n o n a d d i t i v i t y i s negligible provided
no d i p o l e and s t e r i c i n t e r a c t i o n s a r e p r e s e n t , A sim-
i l a r conclusion was drawn by H i l d e b r m d e t a l . r 191
The second assumption o r i g i n ~ t e sfrom t h e e m l i e r
a s s u p t i o n t h a t t h e p a r t i a l h e a t of mixing of l i q u i d 2
w i t h l i q u i d s 1 and 3 i s e q u i v a l e n t t o t h e h e ~ to f mixing
o f l i q u i d 2 w i t h a h y p o t h e t i c a l new l i q u i d whose 6 is
t h e volume f r a c t i o n average of 1 and 3 i n s o l u t e f r e e
p u r e mixed s o l v e n t s , In R p r e v i o u s work r643 concerning
t h e p a r t i a l m o l d volur?e of bronine i n CC14- C - C ~ C ~ ~ F ~

a p r e f e r e n t i a l c o n t a c t between bronine and cc14 WRS

needed t o e x p l a i n t h e experimen%al r e s u l t s . Christian

e t a l .r 6 $ ' ~ 1i n t h e i r s t u d i e s of t h e e f f e c t of t h e s o l -
v e n t s on t h e format ion of e l e c t r o n donor-acceptor com-
p l e x e s , proposed a l l d i s t r i b u t i o n c o e f f i c i e n t w o f t h e
a c c e p t o r m d donor i n t h e s o l v e n t s , T h i s i d e a was i n -
troduced i n o r d e r t o c o r r e l a t e t h e v ~ r i a t i o nof e q u i l i b -
rium c o n s t a n t of donor a c c e p t o r complexes w i t h s o l v e n t s ,
I n o t h e r words f o r a given donor and a c c e p t o r , t h e nun-
ber of donor molecules around t h e a c c e p t o r molecules

depends upon t h e a b i l i t y of s o l v e n t t o s o l v a t e t h e ac-

c e p t o r , provided t h e number of t h e n e e r e s t neiphbour
of t h e a c c e p t o r does n o t chanee. The d i s t r i -

bution coefficient, of ~ c c e p t ~ oAr i n a solvent

K ~i,
i with respect t o R reference solvent, ref , was
,' C661
written ,, ref
YD
-C
K ~i,

where yD * s e r e t h e a c t i v i t y c o e f f i c i e n t s of con?onent
of a c c e p t o r i n r e f e r e n c e s o l v e n t md t h e s o l v e n t i,
vref i s t h e n o l ~ rvolume of r e f e r e n c e ...s o l v e n t , m d
Vi
is t h e molar volume of s o l v e n t i .
C h r i s t i ~ nd e f i n e d y I s o f t h e s o l u t e ( h e r e accep-

t o r ) from R e g u l ~ rS o l u t i o n t h e o r y 8s

ref - v~ - 2
Y2 - ('ref

where VD i s t h e molar volume of D ,~ n d6 ' s are the

s o l u b i l i t y parameters.
Defining t h e d i s t r i b u t i o n c o e f f i c i e n t s of t h e donor
i n t e r m s of t h e e q u a t i o n s ( 2 7 ) and ( 2 0 ) , C h r i s t i a n vms
able t o c o r r e l a t e f o r ~ y r i d i n e - i o d i n ei n vnrious
Keq
nonpolnr s o l v e n t s w i t h t h e d i s t r i h u t i o n c o e f f i c i e n t KDZi .
Murrell e t d..t67'683introduced t h e i d e ~of 8 "well
defined s o l v a t i o n s h e l l " which i s supnosed t o form nround
t h e ~ c c e p t o rn o l e c u l e i n t h e s o l u t i o n . The f o r ? " I ~ t i o n
o f an
e l e c t r o n donor a c c e p t o r complex i n s o l u t i o n r e s u l t s i n
t h e e l i m i n a t i o n of t h e s o l v e n t n o l e c u l e s o f t h e s o - c a l l e d
llwell clef ined s o l v a t ion s h e l l . "
These experimental r e s u l t s d e f i n i t e l y i n d i c a t e
t h ~ it n t h r e e component systems t h e r e i s a p r e f e r e n t i a l
s o l v e t i o n mound t h e s o l u t e by one of t h e s o l v e n t s , o r
i n o t h e r words t h e volume f r ~ c t i o n sof components 1 ~ n d
3 i n pure mixed s o l v e n t do n o t a d e q u e t e l y 6 e f i n e t h e

environment ero~mclt h e s o l u t e molecules i n t k nixed s o l -

vent. Considering t h e p o s s i b i l i t y t h ~ t h e r e may be
some p r e f e r e n t i a l solvfit ion e f f e c t around t h e s o l u t e
molecule, we s e l e c t e d benzene es one o f t h e component$
of t h e mixed s o l v e n t , because of t h e well-known " l i k e -
n e s s " of i o d i n e f o r benzene (3ue t o t h e f o r n a t i o n of
e l e c t r o n donor ~ c c e p t o rcomplex between benzene m d
i o d i n e . C69,70l1
b

The r e l a t i v e nunber of n e a r e s t neighbour molecules

of a p a r t i c u l a r s o l v e n t around a s o l u t e n o l e c u l e i n t h e
t h r e e coxnonent system csn be c a l c u l ~ t e dfrom t h e ex-
perimental 6, fron t h e equations

and it ++
Il+m = 1
3
where 6" s e r e now defined RS t h e e f f e c t i v e volume
f r a c t i o n s , which m e t h e measure of t h e r e l a t i v e nunber
of benzene and c y c l o h e x ~ n er?olecules around t h e i o d i n e
s o l u t e molecule.
 - 73 -
W e may a l s o d e f i n e t h e " e f f e c t i v e volume f r a c t i o n s n
@* i n terms of t h e r e l n t i v e nunber of s o l v e n t
molecules around t h e s o l u t e n o l e c u l e a s

Although we h ~ v en o t been ~ b l et o j u s t i f y t h i s
of'&finition f o r $" from t h e complete rnsthema-
t i c a l d e r i v a t i o n s , it can be c l e a r l y seen t h a t e q u a t i o n s
(31) m d ( 3 2 ) a r e b ~ s e dupon t h e i n t e r n c t i o n c o n s t a n t s
L

f o r 1-3 and 2-3 systems g i v e n i n t h e s a t u r ~ t i o nsolu-

b i l i t y e q u a t i o n f o r two component systems. These equa-
t i o n s say t h a t t h e r a t i o of t h e l m d 3 t y p e s of t h e
n e a r e s t neichbour molecules i s t h e b u I k s o l v e n t mixture
r a t i o w e i ~ h t e dby t h e r e s p e c t i v e b e t s of n i x i n g o f
i o d i n e i n pure s o l v e n t s . The t o t a l e f f e c t of t h e "ef-
f e c t i v e volume f r a c t i o n w q'' d e f i n e d by e q u a t i o n s (31)
m d ( 3 2 ) i s t h e n i n i ~ i z a t i o nof p a r t i n l n o l a l e x c e s s
f r e e enercy of component 2 i n t h e t h r e e conponent sys-
tens. A s we a r e uneble t o j u s t i f y t h e s e e q u n t i o n s f r o ?

t h e mathematics1 d e r i v a t i o n s of an e s t a b l i s h e d e a u e t i o n ,
 - 74 -
t h e s e e q u ~ t i o n sc m be j u s t i f i e d from e x n e r i r n e n t ~ lr e -
s u l t s from d i f f e r e n t s o u r c e s ~ n dfrom t h e e f f e c t s of
t h e s e e q u ~ t i o n son o t h e r t h e r n o d y n ~ m i cp r o p e r t i e s of
t h r e e component systems. From t h e y h y s i c ~ 1s i p n i f i c ~ n c e
o f t h e l t p r e f e r r e d environment mound t h e s o l u t e mole-
culel1 ( i . e . 2 ) we expect t h p t t h e numbers of t h e pre-

f e r r e d molecules, i n t h i s c a s e benzene, i n t h e s o l u t i o n
must be g r e ~ t e rt h a n t h e number of molecules of compon-
ent 2 i n t h e solution. A s i n t h i s s e c t i o n vJe a r e d e a l -
i n g w i t h very d i l u t e s o l u t i o n s of comnonent 2 , where
t h e composition o f t h r e e conyonent a r e s u c h t h ~ tt h e
/'

nunber of l l p r e f e r r e d molecules11 Rre always g r e a t e r t h e n

t h e s o l u t e molecules, we need n o t mention t h e s e r e s t r i c -
tions. But f o r n o n d i l u t e s o l u t i o n s , a s w i l l be d i s c u s s e d
l ~ t e r ,t h i s r e s t r i c t i o n w i l l p l a y A. v e r y important r o l e
i n determining t h e thermodynmic p r o p e r t i e s .
Using b2, 61 ~ n d 63 v a l u e s of 14.1, 9.99 and
8.2 r e s p e c t i v e l y f o r i o d i n e i n benzene-cyclohexme mixed
4e
s o l v e n t , we c a l c u l ~ t e d 6, from t h e r e l a t i o n s h i p

C l e a r l y 6,
++ ' s e r e i n
These m e . ~ i v e n: i n Table 11.2.

'
e x c e l l e n t ~ p r e e m e n tw i t h 6,(experinente1). I n Figure
11.3 t h e (In 3) versus PI
46
i s also plotted. An

e x c e l l e n t l i n e ~ r e l a t i o n s h i p i s seen t o e x i s t , t h e
i n t e r c e p t o f 1.85 a g r e e i n g w e l l w i t h t h e e x ? e r i m e n t ~ l
v ~ l u e1.835 end from t h e r ~ t i oof' t h e s l o p e * t o inter-
 - 75 -
c e p t , 6 1 i s c a l c u l a t e d as 9.9, /
bn e x ~ c ts e l f - c o n s i s t e n t
~ g r e e m e n tw i t h t h e v a l u e p r e v i o u s l y used.

I n F i g u r e 11.4 m d 11.5 we p l o t t e d b o t h m
-R in x2
it
and p a r t i a l n o l a l volume a g a i n s t bl. These p l o t s m e
i n s h a r p c o n t r ~ s tw i t h t h e dependence of -R in x2 md
The F i g u r e s 11.4 end 11.5 s u a e e s t a l n o s t
1i n e a r dependence of -R in :x and on v a l u e s,
1
;
such t h a t

1
it- *-3
= ilV2 + m3V2

Although F i g u r e s 11.4 and 11.5 s u g g e s t a l i n e a r

r e l ~ t i o n s h i pbetween 1
; and -R in :x and T! , we
w i l l see i n R l a t e r s e c t i o n of t h i s c h ~ p t e rt h a t eque-

t i o n s ( 3 4 ) and (35) m e merely l i m i t i n g c a s e s of more

L

rigorous e q u ~ t i o n s .
It i s u s e f u l t o examine t h e *1 term f o r o t h e r

systems. Tile c o n s i d e r d ~ t af o r t h e s o l u b i l i t y of i o d i n e

i n a n i x e d benzene - cerbon t e t r a c h l o r i d e s o l v e n t r e -
1
p o r t e d by S. 3. Pood e t a l [73'
. he i
( in a2 - m E
ln x2)
versus ~ ( 1plot i s piven i n F i g u r e 11.6. The l i n e a r i t y
i 3
i s seen t o be e x c e l l e n t m d t h e i n t e r c e n t (ln a2 - In x2)
= 1.785 i s i n good e p r e e n e n t w i t h e x p e r i m e n t n l
v a l u e 1.80. I n t h i s c a l c u l ~ t i o ns u p e r s c r i p t m d sub-

script f o r benzene, f o r iodine ~ n d for

CC14 . ( xz i.e. mole f r ~ c t i o ns a t u r n t i o n s o l u b i l i t y

of i o d i n e i n CC14 was token from 7iood's dots.)
(for CC14 ) w ~ csa l c u l a t e d from '.
x2
63
Fron t h e s l o p e
?ye ~ g ~ fii nnd t h a t f o r i o d i n e s o l u t e t h e " b e s t "
6 pnrameter f o r benzene i s of v 8 l u e 9.99. I n Tnble
11.3 we c o n p ~ r et h e e x p e r i n e n t ~ l 6, v e l u e vlith t h o s e
v a l u e s c n l c u l a t e d u s i n g both volwle f r a c t i o n ~ n de f f e c -
t i v e volume f r a c t i o n terms. The l n t t e r d ~ t nshow nn
e x c e l l e n t ~ g r e e m e n tw i t h t h e experimental velue. In
F i g u r e 11.7 we p l o t in :X aminst @ and my a nd
using ,@. , the e x p e r i m e n t ~ ld a t a appears t o be addi-
t i v e i n terms of t h e s a t u r a t i o n s o l u b i l i t y o f iod:ine
i n two p u r e s o l v e n t s . C l e ~ r l yt h i s l i n e a r dependence
of both in :x and v2 upon @", , with t h e inference
of "zero e x c e s s p r o p e r t y of mixine term1? i s a s p e c l n l
cRse of a more g e n e r a l i z e d f o r m u l a t i o n of H e ~ u l ~
Solu-
r
t i o n t h e o r y , which w i l l be d i s c u s s e d l a t e r . In this
s e c t i o n we m e more i n t e r e s t e d i n e x ~ n i n i n ct h e v a l i d -
+$
i t y of t h e d e f i n i t i o n of H 's. A s mentioned above, tve
chose benzene RS one component of o u r s o l v e n t mixture
h e c a u s e of t h e e l e c t r o n donor a c c e p t o r i n t e r a c t i o n be-
tween benzene and i o d i n e . The enhsncement of t h e h1
p a r m e t e r f o r benzene from 9.2 t o 9.99 r e f l e c t s t h i s .
So f a r , we have l i m i t e d our d i s c u s s i o n t o s y s t e m
where t h e s o l u t e h a s a s p e c i a l l i k i n g f o r one s o l v e n t ,
t h u s enlereing t h e e f f e c t of preferenti81 solvatlon.

Nov we examine t h e c a s e s where no such s p e c i a l i n t e r -

~ t c t i o n ssuch a s t h e e l e c t r o n donor Rcceptor i n t e r a c t i o n
exist. This i s t h e case with iodine i n a nixed CC14 -
n-C F 16 s o l v e n t C741-- o n l y two d a t a p o i n t s e x i s t f o r
t h i s system. The agreement between e q u a t i o n ( 2 6 ) and
above d ~ t ai s exanined by recognizinf? t h a t t h e
i
a2 - I ' n):x r e l a t i o n s h i p c m be p r e d i c t e d know-
t h e s a t u r a t i o n s o l u b i l i t y of t h e s o l u t e i n t h e pure
s o l v e n t , t h e i d e a l s ~ t u r a t i o ns o l u b i l i t y and t h e t h r e e
bi values. I n F i p u r e 11.8 t h i s r e l ~ t i o n s h i pi s p l o t t e d
f o r t h e iodine - C C 1 4 -n-C7F16 s y s t e n and it i s seen
t h a t dRta p o i n t s l i e on t h e observed l i n e o n l y i f t h e y
are plotted against @: value,
From t h e ~ b o v ed i s c u s s i o n s , it i s c l e a r t h a t i f
bl and b3 a r e adjusted with respect t o a constant
v a l u e from t h e s a t u r a t i o n s o l u b i l i t y f o r 2 i n 1 m d
62
2 i n 3, no f o r t h e r adjustment of 6 p a r m e t e r s i s needed
f o r t h r e e component systems. Besides we a l s o showed t h e
importance of i n c a l c u l ~ t i n gt h e s a t u r a t i o n solu-
b i l i t y and of 2 i n a mixed s o l v e n t . To v e r i f y
t h e s e s t a t e n e n t s we changed t h e s o l u t e from i o d i n e t o
s t ~ n n i ci o d i d e -- but we kee? t h e mixed s o l v e n t s a s
benzene - c-C6H12 mixture, The r e a s o n f o r t h i s can
be found i n t h e f ~ c t h a t f o r Sn14 , bl i,e. solu-
b i l i t y p ~ r a m e t e rof benzene, c a l c u l a t e d f r o n t h e s a t -
uration s o l u b i l i t y data, a s s u ~ i n q 62 ( s o l u b i l i t y p w a -
meter of s t s n n i c i o d i d e ) equal t o 11.8, w n s found t o
1
be 9.24 i n ( calpn?: an e x c e l l e n t agreement. w i t h t h e
v a l u e 9.2, c a l c u l ~ t e df r o n t h e h e a t of v ~ p o r i z n t i o n
1
 I

1
- 7d -
In x2)
m 8
versus
*
P1 ) i s found t o be 0.38 which i s
i n good agreement w i t h t h e v a l u e 0.376, c s l c u l ~ t e df o r
t h e s l o p e from e q u ~ t i o n( 2 6 ) ~ 1 1 t h 6 1 = 9.24 , -
1
62 -
11.8 63 = 8.5 (cal/cm?.' I n t h e c a s e of Sn14 in
C6H6 - c-C6H12 nixed s o l v e n t , we s e e t h ~ we
t definite-
l y need a p r e f e r e n t i a l s o l v ~ t i o naround t h e SnIb mole-
c u l e by one of t h e s o l v e n t s , i . e . benzene, even though
t h e r e a r e no s p e c i f i c i n t e r a c t i o n s between Sn14 and
benzene molecules. Hut because of t h e c l o s e proximity
of 61 and 63 v a l u e s , t h e actual preferential sol-
u b i l i t y i s nuch l e s s t h ~ nt h a t i n t h e c a s e o f in
I2
benzene - c-C6H12 or I2 i n benzene - CC14 nixed
solvents.
I n F i g u r e 11.11 we p l o t in :x versus for
Sn14 i n benzene - c-C6H12 . TJnlike I2 i n benzene -
c-C6H12 or I2 i n benzene - CC14 , t h e experimental
In X; i s n o t l i n e ~ r l ydenendent on (* , which i n d i -
1
c a t e s t h a t t h e "excess p r o p e r t y of mixingu i s no long-
e r z e r o f o r t h i s system.

I
F i n ~ l l ywe t e s t t h e v a l i d i t y of t h e d e f i n i t i o n o f
9 ts from t h e expected l i n e a r i t y of 6m(experinentnl)
 - 79 -
data. Yhereas f o r iodine-benzene system, a s mentioned
enrlier, b1 f o r benzene had t o be s h i f t e d t o 9.99
(assuming t h a t t h e s o l u b i l i t y parnmeter of i o d i n e i s
e q u a l t o 14.1) t o t ~ k eaccount of t h e e l e c t r o n donor
a c c e p t o r i n t e r n c t i o n between benzene and iodine.

From t h e s a t u r a t i o n s o l u b i l i t y of s t a n n i c i o d i d e i n
cyclohexnne, 63 ( i . e . t h e s o l u b i l i t v ~ R r a n e t e rof
cyclohexane) was found t o be 8.50 incompnrison t o 8.2
c a l c u l a t e d from t h e h e a t of v n p o r i z a t i o n d a t a .
I n Table 11.5 we have g i v e n t h e s a t u r n t i o n solu-
i
b i l i t y along w i t h t h e v a l u e s f o r ( I n a2 I n x!)* of -
Sn14 i n f i v e nixed s o l v e n t s a t 25O C. I n Table 11.6
w e conpare 6 m ( e x p e r i m e n t a l ) c a l c u l a t e d from t h e s a t u r -
tio on s o l u b i l i t i e s of Sn14 i n t h e mixed s o l v e n t s as-

suming 6 2 = 11.8 .with 6 m ( c a l c ' d ) c ~ l c u l e t e dfrom t h e

r e l a t ionship

iF
Clearly 6, v e l u e s a r e i n nuch b e t t e r ngreement w i t h
t h e experimental 6, values than 6, c a l c u l a t e d f rorn
t h e simple volurle f r a c t i o n s . I n F i g u r e 11.10 (ln a; -
m $
I n x2) for S ~ Ii n ~ C6H6 - c-c6HI2 i s pl6tted ~ c ~ i n s t
both el nnd
16
.
Again we s e e t h a t Rn e x c e l l e n t l i n -
i m g
e a r r e l a t i o n s h i p e x i s t s between t h e ( l n a2 - I n x2)
and
++
r a t h e r than I1 . i
The s l o p e l i n e ( ( l n a;, -
t h e n one s h o u l d e x p e c t a s t r n i g h t l i n e lwhen 6 (exper-
m
imentnl) i s plotted e i t h e r n ~ a i n s t . @? o r :@ , with
an i n t e r c e p t e q u a l t o b3
and R s l o p e e q u a l t o ( 61 -
6 . I n F i g u r e 1 1 - 1 2 we p l o t 6, ( e x p e r i n e n t ~ l )n ~ e i n s t
@; ( v o l u ~ ef r a c t i o n o f benzene) nnd 0,
036
, for I2 i n
benzene - c-C6H12 system. Clenrly bm(exneriment~l)
when p l o t t e d a g a i n s t
*
PI i s i n nuoh b e t t e r ~ p r e e m e n t
w i t h t h e e x p e c t e d l i n e t h a n when p l o t t e d n ~ ~ i n Gs It
I n F i g u r e 11.13 6 m ( e x p e r i n f ? n t a 1 ) f o r C6H6 - CC14
mixed s o l v e n t i n C6H6 - I2 - CC14 system i s p l o t t e d
against my and * (volume f r ~ c t i o no f benzene) ,and i n
Figure 11-14 6m(experixental) f o r C6H6 - C - C ~ H ~ ~

mixed s o l v e n t i n C6H6 -S ~ -I c -~C ~ H , ~ is plotted

aeainst. and 9;" (volume f r a c t i o n o f b e n z e n e ) .
From b o t h o f t h e f i g u r e s , it i s c l e ~ rt h a t b,(exper-
i m e n t s l ) i s b e t t e r d e s c r i b e d i n t e r n s of @"'sr n t b e r
than g1, o r i n o t h e r v o r d s , an a s s u z p t i o n o f p r e f e r e n -
t i a l s o l v a t i o n of s o l u t e by one s o l v e n t i s def i n i t e l v
needed t o d e s c r i b e t h e d i f f e r e n t n r o p e r t i e s o f s o l u t e s
i n mixed s o l v e n t s . R y v d e s c r i b i n p " -:re mean t o c o r r e l a t e
t h e s o l u b i l i t y and thermodynanic p r o p e r t i e s o f s o l u t e
w i t h t h o s e p r o p e r t i e s o f s o l u t e end s o l v e n t s i n two
sornponent systems c o n t a i n i n g s o l u t e 2 ~ n ds o l v e n t 1,
end s o l u t e 2 nnd s o l v e n t 3.
 - 81 -
Excess P r o p e r t i e s of Xixina f o r D i l u t e Solutions

Introduction
I n p r e v i o u s s e c t i o n s , we h ~ v e~ t t e m p t e dt o s h o ~
t h a t Regular S o l u t i o n t h e o r y mag be u s e f u l l y employed
t o i n t e r p r e t t h e s o l u b i l i t y p r o p e r t i e s of R d i l u t e sol-
u t e i n mixed s o l v e n t s . Sle ~ l s ot r i e d t o show t h a t t h e r e

i s needed a t e r n c a l l e d t h e " e f f e c t i v e volurne f r n c t i o n , l l

46
Qi , t o d e f i n e t h e immediate e n v i r o n r ~ e n t of s o l u t e n o l -

e c u l e s i n a mixed s o l v e n t . i'le a l s o showed t h a t i n some

m
cRses t h e r e e x i s t l i n e a r r e l ~ t i o n s h i p sbetween in x2 ,
$ , and 4b
li such a s

and V2 =
-M P it-1V2
1 + G3V2
if-3

( t h e n o t a t i o n s a r e t h e sane a s i n p r e v i o u s s e c t i o n ) .
The r e l a t i o n s h i p between 6, and Q* satisfies
t h e c o n d i t i o n t h a t a mixed s o l v e n t may be c o n s i d e r e d
a s a hy-pothetical s o l v e n t whose s o l u b i l i t y p a r a m e t e r

(here 6, ) i s t h e volune f r a c t i o n average of t h e two

p u r e conponents. The o t h e r two r e l a t i o n s h i p s , a l t h o u p h

v e r y n t t r a o t i v e a t f i r s t p l m c e , do have R very l i m i t e d

R p p l i ~ t 3 b i l i t ybecause, a s s u e p s t e d e ~ r l i e r ,t h e s e t v o
r e l ~ t i o n s h i p shold because of t h e llzero e r c e s s p r o p e r t y

of mixinp..ll I n t h i s section ve w i l l derive t h e excess

p r o p e r t i e s w i t h respect, t o t h e h i n ~ r vs v s t e n s , end frorn

 - 82 -
t h e Regular S o l u t i o n t h e o r y we w i l l t r y t o p r e d i c t t h e s e
excess quantities. ille s h a l l a l s o t r y t o show t h a t
*
'
i
i s needed t o d e f i n e t h e e x c e s s p r o p e r t i e s and t h e volune
f r a c t i o n of t h e n i x t u r e , where t h e naximun o f t h e "ex-
c e s s p r o p e r t i e s v vwould be observed.
The main g u r p o s e of t h i s c h a p t e r i s t o g e n e r a l i z e

t h e s o l u b i l i t y r e l a t i o n s h i p s f o r t h r e e coriponent systems
~ n dso d e r i v e t h e l i m i t i n g c o n d i t i o n s where t h e s a t u r -
tio on s o l u b i l i t i e s of t h e s o l u t e i n mixed s o l v e n t s can
depend l i n e ~ r l yon, m y ,
@ . I n t h e f i r s t p a r t of
t h i s s e c t i o n we l i m i t our d i s c u s s i o n s t o v e r y d i l u t e
s o l u t i o n s such t h a t

i*e. the (5.e . t h e voltme f r a c t i o n of t h e s o 1 u t e ) i n

@2
t h e s o l u t i o n 8.pproaches z e r o ,

Theory

Excess S e t u r a t i o n S o l u b i l i t y
*
H8ving e s t 8 b l i s h e d t h e def i n f t ion of and t h e
'
i
i m p o r t m c e of t h i s term i n t h r e e component systems, we
novr t u r n t o t h e e e n e r a l i z e d properties of s o l u b i l i t y
r e l a t i o n s h i p s f o r t h r e e component systems. In fill the

d i s c u s s i o n s i n t h e p r e v i o u s s e c t i o n we l i n i t e d o u r s e l v e s

t o t h e c a s e where b1 < 62 > 6 3 . For t h o s e c a m s where

 6 1 > 6, > 6 3 , a t c e r t a i n volume f r a c t i o n of
* , the

6 v a l u e becones equal t o t h e 62 value (of t h e s o l u t e )

~ n dt h o p a r t i a l molal hent of s o l u t i o n of conponent, 2

' t h e n becomes zero m d t h e s a t u r a t i o n s o l u b i l i t y of t h e
s o l u t e ( x2 ) i s equal t o t h e i d e ~ ls o l u b i l i t y ( a; )
of t h e s o l u t e . A l l t h e d e r i v a t i o n s discussed i n t h e
p r e v i o u s s e c t i o n n r e a p p l i c ~ b l ewhere b1 > 6 2 > 6 3 8s
long n s t h e s o l u b i l i t y of coxponent 2 i s very s m ~ I 1 ,
i.e. where @: + 'P 3 - 1 .
We s h a l l a c c e p t t h a t t h e s a t u r a t i o n s o l u b i l i t y o f
some d i l u t e s o l u t e 2 i n a s o l v e n t S may be w r i t t e n
w i t h t h e u s u ~ Regular
l S o l u t i o n n o t a t i o n s 8s

where

--
v2 ( f o r a dilute solution) (39)
RT

For t h e cRses where t h e s o l v e n t i s a b i n a r y mix-

t u r e of co:iponents 1 and 3 , we t h e n assune

I f one w r i t e s t h e s a t u r f i t i o n s o l u b i l i t y of compon-
e n t 2 i n nixed s o l v e n t i n t e r n s of t h e s ~ t u r ~ t i osolu-
n
b i l i t y of t h e s o l u t e i n p u r e s o l v e n t s 1 end 3, as done
i n equet ion ( 34) , t h e n
 m
In x2(i) =
0
l n xi + i n x2
3
(41)
3

S u b s t i t u t i n g e q u o t i o n (38) i n t o e q u a t i o n ( 4 1 ) f o r
t h e c n s e f o r which 6S = b1 o r 6 then
3
m i
I n x p ( i ) = In a2 - A[ h2 - 26,(@:6, + @363)
2
+ @161 +
0
5,a320
I (42)

A ~ n i ns u b s t i t u t i n g e q u n t i o n ( 4 0 ) i n t o e q u ~ t i o n( 3 8 ) :.re
find
In x2m =
i
In a2 - ~ ( - 66,) 2
~

=
i
ln a2 - ~ (
2
-6 2 6 2~6 m + 6 2 ) (43)

A p ~ i ns u b s t i t u t i n g e a u a t i o n ( 4 0 ) i n t o e q u a t i o n ( 4 2 ) nnd
t h e n comparing e q u a t i o n ( 4 2 ) w i t h e q u a t i o n ( 4 3 ) we s e e
that

a requireaent vhich i s obviously i n contradiction with

t h e c o n d i t i o n g i v e n i n e q u ~ t i o n( 4 0 ) f o r
6m
I n e q u a t i o n ( 4 1 ) we used t h e n o t n t i o n in x:(i) to
i d e n t i f y t h i s a s t h e l l t h e r ~ o d y n n n i c "s a t u r n t i o n s o l u b i l -
i t y i n riixed s o l v e n t , r e l a t i v e t o t h e s a t u r e t i o n s o l u -
b i l i t i e s of 8 s o l u t e i n two n u r e s o l v e n t s .
The t h e r r l o d y n a r ~ i c j u s t i f i c n t i o n of t h i s n o t n t i o n
i s based on t h e f a c t t h n t t h e g r > r t i , ~nolar
l excess f r e e
ener&?yi s ~ l s ozero :vith r e s n e c t t o t , h e t of t k e s o l u t e
i n t he puye s o l v e n t s . (Note t h n t In x:(i) is not
 - 85 -
i
I n a2 which i s t h e i d e ~ lsolubility of s o l u t e i r r e s p e c -
t i v e of s o l v e n t s . ) So we can d e f i n e t h e e x c e s s s n t u r -
a t ion s o l u b i l i t y a s

Using e q u ~ t i o n( 4 1 ) , we s e e thrrt ~ ( l xg)

n can he
evalunted from t h e e x p e r i m e n t a l l y determined q u a n t i t i e s
1 , i n x2
I n x2 and i n :x .
It can a l s o be d e t e r n i n e d
from t h e Hegulm S o l u t i o n t h e o r y . E q u ~ t i o n(38) i s
d e f i n e d i n t e r m s of t h e pure s o l v e n t s 1 m d 3, m d t h e
mixed s o l v e n t s , m , as

So f a r we have n o t used t h e e f f e c t i v e volume f r n c -

t i o n n , b u t i f one w r i t e s t h e l n $(i) i n t e r m s of' t h e
e f f e c t i v e volume f r a c t i o n , t h e n

To be r i g o r o u s , even i f we allovi o u r s e l v e s t o use

t h e l t e f f e c t i v e volune f r s c t i o n W terms i n d e f i n i n p t h e

'm 9
end i f w e r e c o c n i z e t h ~ tt h e e f f e c t i v e volune
f r a c t i o n d e s c r i b e s o n l y t h e i m n e d i ~ t es o l v e n t environ-
ment o f t h e s o l u t e molecule, we must s t i l l d e f i n e t h e
m 0 *
In x 2 ( i ) i n t e r x s of @ ls and n o t @ ls because t h e

w i t l e d " term must r e f e r t o t h e composition of t h e bulk

$

solvent, RS i n equation ( 4 1 ) . So, w r i t i n e 6, as

m
i n t h e expression f o r ~ l x2
n ,

one o b t a i n s t h e excess s ~ t u r a t i o ns o l u b i l i t y a s

I n e q u a t i o n ( 5 0 ) one : c a n . c l e a r l y s e e t h a t we h ~ v e

and n o t
1 1
' m = GO6 + @;b3

The n o t a t i o n of s u b s c r i p t 2* h ~ i sbeen used t o

denote thst t h e p o s s i b i l i t y of t h e i m e d i a t e s o l u t e 2
environment i s d i f f e r e n t f r o n t h e "averapef' bulk s o l -
v e n t environnent .
Excess Volune of ]fixing
p-

For a v e r y d i l u t e s o l u t i o n of n o n - e l e c t r o l y t e s
one rrlny c a l c u l a t e t h e p ~ r t i n lmolal volune of s o l u t e
 - 37 -
from Regular S o l u t i o n t h e o r y .r783 nay w r i t e f o r n

very d i l u t e solution

-
where V2 i s t h e p a r t i a l molnl volune o f t h e s o l u t e i n
solution, V; i s t h e r e f e r e n c e volune of the s o l u t e ,

ni i s t h e r a t i o of t h e i n t e r n ~ lp r e s s u r e o f t h e s o l -
v e n t t o i t s cohesive energy d e n s i t y , and pi is the
c o e f f i c i e n t of i s o t h e r m a l c o m p r e s s i b i l i t y of t h e pure
solvent, i .
From t h e Regular S o l u t i o n t h e o r y ,

o r we nag o b t a i n a very u s e f u l e q u a t i o n such a s

where a i s t h e c o e f f i c i e n t of thermal expcnsion.

i
A s mentioned e e r l i e r , e q u a t i o n s ( 5 1 ) ~ n d( 5 2 ) were
d e r i v e d 8 s approximate e q u a t i o n s and t h e i r a p p l i c a b i l i t y
i s f a r l e s s t h a n t h e a p p l i c f i b i l i t y of Hegular S o l u t i o n
t h e o r y i n p r e d i c t i n g t h e e x c e s s f r e e e n e r v of mixinp.
iiernemberine: t h e l i r n i t ~ t i o n aof t h e s e e q u c t i o n s , :ve now
define 8 tern A+ R s
So f a r t h e e x p r e s s i o n s f o r T h ~ v ebeen w r i t t e n f o r
b i n m y systems. For t h e mixed s o l v e n t s , t h e ~ n r t i a l
-
V2 , i s given by
n o l a 1 volume of s o l u t e ,

or,

I n t h e f o l l o w i n g d e r i v ~ t i o n s ,we w i l l assume that

4t
only G ' s describe 6, c o r r e c t l y r ~ t h e rt h ~ n @ f s .
Now we d e f i n e a n o t h e r term M,193
aV i n t e r n s of
t h e p r o p e r t i e s of t h e s o l u t e i n each of t h e pure s o l -
vents 8s
M,193
*v = Q I A V1 + G3Av 3

o r we may d e f i n e t h e e x c e s s p ~ r t i a lm o l d volume of n i x -
i n g f o r s o l u t e 2 i n a mixed s o l v e n t system w i t h r e s p e c t
f o r t h e excess p ~ r t i a no181
l volune of s o l u t e ( 2 ) i n
pure s o l v e n t s , i.e.

-E,M M
v = -v~(A , (56)

S u b s t i t u t i n g t h e r e s n e c t i v e eq11ntion.s i n e q u ~ t i o n
( 5 5 ) we o b t e i n
o r u s i n g t h e ~ s s u m p t i o nt h ~ t

+ ( ,,al + m3a3)T

We may s i m i l ~ r l yr e w r i t e t h e e q u ~ t i o n( 5 6 ) a s

We map f u r t h e r essune t h a t t h e mech~.nical p r o p e r t i e s

t h e mixed s o l v e n t mRy be e x p r e s s e d i n t e r m s of t h o s e
*
t h e pure s o l v e n t s by

* Probobly a n o r e r e a s o n a b l e approximation would be t o

w r i t e nmB, i n t h e f o l l o w i n g manner:

= @lnlB1 + @ 3n3B 3 - (G3

2
n 3B 1 + ml2n1~,)
Neglecting t h e higher t e r n s i n @ ' s we o b t a i n e q u n t i o n
(61)
 - go -
and

am = Ilal + m 3a 3

Besides equation ( 6 1 ) and ( 6 2 ) , we a l s o nssume t h a t

S u b s t i t u t i n g e q u a t i o n s ( 6 l ) , ( 6 2 ) and ( 6 3 ) i n e q u a t i o n
( 5 6 ) , t h e excess t e r n s , i . e . A , becomes

I f we do n o t choose t o u s e aiVs, then t h e excess

volme, 8 q r M becones n o r e c o n ~ l e x , ( see A p ~ e n d i x

AII.l f o r d e r i v a t i o n s ) and i s c i v e n by

A s seen i n e q u a t i o n ( 6 5 ) we have n o t ~ s s u m e dt h a t

( RS i n e q u a t i o n ( 6 3 ) ) which i s probably an i n c o r r e c t
a s s u n p t ion.
The e x p r e s s i o n A;jM(expt) cRn be w i t t e n a s
 - 91 -
I n t h e following d i s c u s s i o n we w i l l r e f e r t o
( c a l c t d ) a s it i s given i n e q u a t i o n ( 6 5 ) and n o t a s i n
equation (64) .
I n o u r above d i s c u s s i o n of t h e volume of mixing
term we have developed b o t h e q u a t i o n ( 6 4 ) and ( 6 5 ) with-
out defining 6, , i.e. t h e s e e q u a t i o n s a r e independent
o f t h e d e f i n i t i o n o f 6, I n t h e s e e q u ~ t i o n s ,m y
derivation of 6, can be s u b s t i t u t e d a s l o n g RS the
solution i s d i l u t e i n solute, But, a s we h ~ v ementioned
earlier, 6, ts a r e b e t t e r d e s c r i b e d by @
* values. In
f u r t h e r d i s c u s s i o n s on e x c e s s volumes we w i l l u s e only
* 's.
6, ' s c a l c u l a t e d from iP

Discussion
Vle s h a l l f i r s t d i s c u s s t h o s e s y s t e m i n vrhich t h e
s o l u t e s o l u b i l i t y parameters a r e g r e ~ t e rt h a n t h o s e of
e i t h e r component m i x t u r e s , i.e. b1 < b 2 > b 3 We
s e e from t h e e q u ~ t i o n( 4 8 ) t h a t t h e rnapnitude sf t h e
e x c e s s t e r n , i.e. -Ah ( l n):x , i s governed by t h e square
of t h e d i f f e r e n c e of t h e s o l u b i l i t y p a r a m e t e r s of t h e
conponents o f t h e mixed s o l v e n t s . The maxinum v a l u e
f o r t h e e x c e s s term w i l l o c c u r a t
 S i m i l a r l y , t h e e x c e s s term LA*( ~x
)n
; i n equa-
A
t i o n ( 4 4 ) w i l l have i t s maximum v a l u e d i s p l a c e d from
Bl = 0.5 by t h e r e l a t i v e (a2 - b3)* and (a2 - bl)*
k
values. (See t h e d e f i n i t i o n of i values,) It c a n
be shown t h a t t h e p o s i t i o n of t h i s mtixinum, piven by

c a n be formulated a s a simple a n a l y t i c e l e x p r e s s i o n , v i z .

(See Appendix AII.2 f o r t h e d e r i v a t i o n . )

From t h e e q u a t i o n ( 6 9 ) we s e e t h a t i n t h o s e c a s e s
*
where 162 - b3( = 6 - 6 , (i.e. f o r which =

w i t h t h e i r n p l i c ~ t i o nt h a t t h e r e i s no p r e f e r e n t i a l s o l -
v a t i o n of t h e s o l u t e molecules by e i t h e r of t h e s o l v e n t
molecules) t h e e q u a t i o n r e d u c e s t o i(max) = 0.5 in
agreement w i t h t h e p o s i t i o n of miximum f o r t h e $(ln ):x
term, We a l s o s e e from e q u a t i o n ( 6 9 ) t h a t f o r a s o l u t e
i n a mixed s o l v e n t whose omponents a r e o f w i d e l y d i s p a r -
ate 6 such t h a t (b2 - 6 6 - 6 , a consider-
able s h i f t i n ~(rnax) w i l l occur f o r t h e s e e q u a t i o n s .
I n F i p u r e 11.15, we i l l u s t r a t e t h e t h r e e e x c e s s f u n c t -
ions, equation ( M ) , equation (49) m d equation (50)
f o r h y p o t h e t i c e l systems w i t h a s o l u t e o f 62 = 14 in
R mixed s o l v e n t o f components b1 = 12 and = 6 .
 - 93 -
W e i g n o r e t h e p o s s i b i l i t y of t h e l i k e l y i m i s c i b i l i t y
of t h e s o l v e n t m i x t u r e s , From t h e e q u ~i to n ( 6 9 ) , t h e
p o s i t i o n o f t h e maximum of t h e &*(In ):x curve w i l l
A
be s h i f t e d t o Bl(max) ,0.5 The p o s i t i o n of t h e
maximum of t h e e x c e s s L~(1l-l
A
):x does n o t appear cap-
a b l e of any simple f o r m u l a t i o n b u t it i s seen t o be
a t a position 0 . We f u r t h e r s e e from F i e u r e
11-15 t h e c o n s i d e r a b l y l a r g e r v a l u e o f t h e e x c e s s func-
tion for the A ) f o r r n u l ~ t i o no v e r t h e whole
r a n g e o f s o l v e n t composition,
I n F i g u r e 11.16, we p r e s e n t t h e e x c e s s s a t u r a t i o n
s o l u b i l i t y terms ~ ( lx
)n
: and ~ ( l xn:*) for the
system o f s o l u t e i o d i n e i n mixed benzene-cyclohexme
solvent. I n F i g u r e 11.17 we p r e s e n t s i m i l e r p l o t s of
e x c e s s p r o p e r t i e s o f i o d i n e i n benzene - CC14 mixed
solvents. Both t h e s e systems .were d i s c u s s e d e e r l i e r ,
partic'ularly with respect t o equation ( 2 2 ) . A s comen-
t e d e a r l i e r , t h i s e q u a t i o n depends q u i t e c r i t i c a l l y
*
on t h e u s e o f B1 or GI i n t h e expression f o r 6m ,
The agreement between t h e experimental c u r v e s and t h e
c a l c u l a t e d e x c e s s c u r v e s ~ ( l xn:*) r a t h e r than
~ ( l):x
n curve observed i n F i g u r e s 11.16 and 1 1 - 1 7
gain a r p u e s w e l l f o r t h e use of t h e e f f e c t i v e volume

f r a c t i o n s i n t h e d e s c r i p t i o n of 6, . It i s obvious
from t h e d a t a p r e s e n t e d i n F i g u r e 11.15 t h a t A * ( l n xm)
2

curve w i l l f i t t h e experiment81 d ~ not b e~t t e r t h a n

does A(ln x
): curve, because f o r b o t h t h e s e c u r v e s
t h e maximum v a l u e o f t h e e x c e s s p r o p e r t i e s i s t h e same
even i f ~ ( m a x *) s a r e d i f f e r e n t .
E a r l i e r i t was shown t h a t f o r b o t h t h e s e systems,
t h e experimental d a t a obey t h e r e l a t i o n s h i p

Recognizing t h a t t h e s a t u r a t i o n s o l u b i l i t y i n t h e
nixed s o l v e n t i s given by

if 6, i s w r i t t e n 8s
*
tjm = g l b l + g j*b 3 we s e e t h a t t h e
magnitude o f any divergence from t h e in :x versus
@ 1
l i n e a r i t y w i l l be equal t o t h e e x c e s s s a t u r a t i o n s o l -
ubility tern, A(ln $,) and n o t A ( l n):x because
t h e 6,(experimental)
0
i s n o t d e s c r i b e d by @161 + $363
m *
0
.
S i m i l a r l y , t h e n o n l i n e a r i t y of i n X2 v e r s u s P I p l o t
w i l l be o f t h e magnitude o f t h e e x c e s s A*(ln):xc term.
*
A ( I n):x s e e n s t o be v e r y s n a l l f o r
The e x c e s s term
t h e two s y s t e n s w i t h i o d i n e as s o l u t e . Hence t h e l i n -
i n :x
*
e a r i t y observed i n versus p l o t s (Figures
11.4 and 11.6) f o r i o d i n e i n benzene-cyclohexane and

i o d i n e i n benzene - carbon t e t r a c h l o r i d e mixed s o l v e n t s ,

i s due t o t h e n e g l i g i b l e macnitude o f t h e e x c e s s term,
 - 95 -
a s concluded e a r l i e r , (See e q u a t i o n ( 4 5 ) .) In these
cases, b m 2 = 2
0
+ $;a3 i s a f ~ i ar s s u n ~ t i o n .
I n F i g u r e 11.18 we p l o t A ( l n xm) , *
A (In x
): and
2
~ ( l xn
),: for S ~ I i n~ benzene - c-C6H12 mixtures.
For Sn14 , although (6
3
- 6 ) i s smaller than t h a t
f o r i o d i n e , t h e :V of Sn14 is alaost three tines
bigger than V; of iodine ( c f . 151 cc f o r Sn14 to
59 c c f o r i o d i n e ) . T h i s makes t h e magnitude of e x c e s s
terms bigger f o r Sn14 i n benzene - c-C6H12 systems
t h a n f o r i o d i n e i n benzene - c-C6H12 system. This
e x p l a i n s t h e n o n l i n e a r i t y of i n x: (for on @: .
I n t h e c a s e of Sn14 , we t r i e d t o denonstrnte t h e e f f e c t
of V2 ? O s~o l u t e on t h e e x c e s s p r o p e r t y -- because
a t t h e same temperature, t h e e x c e s s of s o l u b i l i t y o f
two s o l u t e s i n mixed s o l v e n t s depends s i m l t a n e o u s l y
on t h e V; of t h e s o l u t e ~ n dt h e s q u a r e of t h e d i f f e r -
ence of t h e s o l u b i l i t y p a r m e t e r s o f t h e s o l v e n t s.
Next we c o n s i d e r t h e system i o d i n e ( 6 2 = 14.1 )
i n t h e mixed s o l v e n t CC14 ( 6 1 = 8.6 ) plus n-C F
7 16
( b3 = 5.6 ) which o f f e r s a g r e a t e r test f o r t h e proposed

theory. T h i s system h a s a l a r g e m i s c i b i l i t y - Dm
~ R d on-
l y two d a t a p o i n t s e x i s t f o r t h e m i x t u r e s . It h a s been
s h o w e a r l i e r t h a t t h i s s y s t e n was b e s t e x ~ r e s s e dby t h e
@
St
formulation f o r 6, . InFigure II.19we show t h e
*
n2 , A ( l n x):
e x c e s s s ~ t u r a t i o ns o l u b i l i t y c u r v e s ~ ( l xm)
and A X ) and i n F i g u r e 11.20 we p l o t t h e i n x2
m
*
against nnd B1 , where i n xk and i n xz are the
 - 96 -
a c t u a l experimental v a l u e s . It i s seen i n F i g u r e 11.19
t h a t t h e available experiaental date points l i e well
on t h e ~ ( l )*:xn curve. Again t h e A * ( l n xm) curve
2
f o r t h i s system i s o f small magnitude and consequently
m
t h e two d a t a p o i n t s l i e on a l i n e a r l n X2 v e r s u s
*
p l o t a s seen i n Figure 11.5.
From t h e s a t u r a t i o n s o l u b i l i t y e q u ~ t i o n

w i t h t h e assumption t h a t 6 m = glbl
0
+ 0
@363 it i s eas-
i l y shovm t h a t ( s e e Appendix A11 -3)

T h i s l a t t e r r e l a t i o n i s seen t o p r e d i c t a maxinun
b

v a l u e of g1 which i s meaningful ( i . e . 0 < el < 1 )

only i f bi > > 6 ( i,j = 1'3 i f j ) In other
3
words, i n t h e c a s e s where 6i > 62 > 6 and 6, --
j
406.
1 1
+ @?6
J 3 , a t c e r t a i n volume f r a c t i o n s o f t h e ith
and jth component o f mixed s o l v e n t , 6, w i l l be equal
m i
to 62 and consequently x2 = a2 ; i.e. i n t h a t mix-
ture, in :X v r i 1 1 be a naximum. O r t h e volume f r a c t i o n

of component 1 of mixed s o l v e n t at, which 6 m = 62 , is

t h e . max i n e q u a t i o n ( 70) ,
S i m i l ~ r l yi f one d e f i n e d 6, i n terms of lleffec-
t i v e volunel' f r a c t i o n s , t h e p o s i t i o n o f t h e m~xirnumi s
 - 97 -

-
g i v e n by
a l n x:
= 0 where
-
- b2 -
6l-
63
63

o r converting @Imxt o vnlues, i.e. ):(max,*) ,

one o b t a i n s ( s e e Appendix AII.3 f o r d e r i v n t i o n )

The e q u a t i o n s ( 7 1 ) and ( 7 2 ) a r e w a i n o n l y v a l i d
if 6i > 6 2 > 6
j
. Comparing e q u a t i o n ( 7 0 ) w i t h ( 7 2 )
we a l s o s e e
+ax,*) + g 0l , W X = 1

For t h e systems where \62 - bll = b2 - b31 , @l(maxl

el(Wx,*) = 0.5 . Such a behavior p a t t e r n i s shown i n
F i g u r e 11.21 f o r naphthalene ( 6 2 = 10 ) i n h y p o t h e t i c a l
s o l v e n t m i x t u r e s ( i ) 61 = 12', ~ n d(ii)
3
= 8 'p', =
1
14 , b 3 = 6 , I n t h i s p l o t we only g i v e x ~ ( l nx
):
term b e c ~ u s e ( 6 2 - bll = 1b2 - 631 a d
*
*1
a r e equnl over t h e c o n p l e t e r m p n o f composition. A l l
1
t h r e e e x c e s s s o l u b i l i t y e q u ~ t i o n sreduce t o $ ( I n- x
): A

form. I n F i g u r e 11-22, we p l o t ( I n a2
i
-m 2
I n x2) ag-

a i n s t 6,
3k
. i
It i s seen t h n t a t a2 = x2 ( i , e . t h e max-

agreement w i t h t h e di s c u s s i o n g i v e n above. Furthermore,

we can s e e from t h e r e l a t i o n s h i p
t h a t t h i s r e l ~ t i o n s h i pi s v a l i d o n l y o v e r t h e r a n g e
* * *
B1=O to $1
*,mx
$1 . The range
qrnx
< @ p l

can be determined i f t h e r e f e r e n c e s t a t e i s changed from

t h e s a t u r a t i o n s o l u b i l i t y of s o l u t e 2 i n p u r e s o l v e n t
3, ( i . e .
3
x2 ) t o saturation s o l u b i l i t y of s o l u t e 2 i n

pure solvent 1 (i.e. x21 ). The r e l a t i o n s h i p t h e n can

( I n a,i - In = ( I n a,i - 1
I n x2) +

The a p p r o p r i a t e p l o t s f o r naphthalene i n two h y p o t h e t i c a l

s o l v e n t m i x t u r e s a r e given i n F i g u r e 11.23. As

16, - blI = 162 - 5

1 , the symmetry of t h e s e p l o t s i s
retained.
I n F i g u r e 11-23 we extmine t h e t h r e e e x c e s s s a t u r -
it
a t i o n s o l u b i l i t y terms ~ ( l):x
n , A ( I n):x and
~ ( )
l,:xn f o r m o t h e r h y p o t h e t i c a l s y s t e n f o r which

62
= 11.7 (eon. S a 4 ) i n mixed s o l v e n t s whose com-

ponents have b1 = 5.6 and b 3 = 14.0 . The consider-

a b l e asyrnrletry due t o t h e l a r g e d i f f e r e n c e i n t h e
16, - 611 find 16, - 631 t e r n i s rrlso shown i n F i g u r e
 - 99 -1
11.24 where 5.
( l n ag - '):x
In i s n l o t t e d agni?lst both
St
P1 aid IIO ; only t h e ? l o t of ( I n a; - l n x2) * against
is linear. The purposa of t h e s e h y ~ o t h e t i c a lsys-
tems ~ n dt h e p l o t s i s t o show t h e e f f e c t of t h e d i f f e r -
ence between bg - bll and b2 - b31 on t h e d i f f e r -
e n t p r o p e r t i e s of mixed s o l v e n t s .
So f a r we have o n l y d i s c u s s e d t h e e x c e s s s a t u r a -
tion solubilities. I n t h e remaining p a r t of t h i s d i s -
c u s s i o n we w i l l c o n s i d e r t h e e x c e s s volume o f n i x i n g ,
AV' , and t h e e f f e c t o f t h e v v e f f e c t i v e l v
volur-~ef r r r c t i o n s
on t h i s q u a n t i t y .
I n t h e d e r i v a t i o n of t h e e q u a t i o n s d e s c r i b i n g t h e
e x c e s s v o l m e of n i x i n g , we mentioned t h a t b a s i c equa-
t i o n s a s d e r i v e d from t h e Regular S o l u t i o n t h e o r y a r e
o n l y approxinate. I n g e n e r a l f o r s i n g l e connonent s o l -
v e n t systems both e q u a t i o n ( 5 1 ) and e q u o t i o n ( 5 2 ) are
found t o p r e d i c t v a l u e s i n good agreenent w i t h t h e
2
experinental data. Rut o u r c a l c u l a t i o n s on e x c e s s v o l -
ume o f mixing a r e c o n p l e t e l y dependent on t h e a b i l i t y
of t h e s e b a s i c e q u a t i o n s t o p r e d i c t t h e p a r t i a l molal
v o l m e of s o l u t e i n a one-component s o l v e n t .
E a r l i e r , we have shown ( s e e F i e u r e 11.5) t h a t t h e
p a r t i a l molsl volume d a t a f o r i o d i n e , i . e . , in
c6H6 - C-c6H 12 nixed s o l v e n t system was a good l i n e a r
f u n c t i o n of t h e " e f f e c t i v e v f volune f r e c t i o n s of t h e
nixed s o l v e n t ( c f . e q u a t i o n (35) ) . I n F i g u r e 11.25
we p l o t f o r bromine i n nixed CC14 - c-C6HI2 sys-
tern, Althoughthe experimental s c a t t e r f o r t h i s system
i s l a r g e , it would appear t h a t t h e r e o c c u r s fi l a r g e
-M
d e v i n t i o n from t h e l i n e a r i t y f o r V2 even a s a func-
k
tion (i.e. t h e e f f e c t i v e volume f r a c t i o n o f CC14 1.
I n F i g u r e 11.26 vre p l o t t h e e x c e s s f u n c t i o n A V ~ 'f o
~r
iodine i n C6H6 - C-C6H12 n i x t u r e and conpnre it w i t h
t h e experimental v a l u e s , ' hvEjM(expt) i n e q u a t i o n ( 6 6 ) .
The e x p e r i n e n t a l d a t a compare extremely w e l l w i t h t h e
c a l c u l ~ t e dl i n e which h a s been C ~ l c u l ~ t ewdr i t i n g 6 =
* * m
@161 4- @363 . W e p l o t t h e e x c e s s volume of n i x i n g t e r m s

f o r bromine - C C 1 4 - c-C4C12F6 mixed s o l v e n t i n Fig-

ure 11.27, The t h e o r e t i c a l e x p r e s s i o n a p p e a r s t o un-
d e r e s t i m a t e t h e magnitude of t h e e x c e s s term, F o r bro-
mine i n n i x e d CC14 - n-C7F16 solvent t h e t h e o r e t i c a l
hvE t e r m i s o f a m ~ g n i t u d ef a r g r e a t e r t h a n t h a t found
from t h e experimental d a t a , YJle g i v e d a t a f o r a l l t h e s e
s y s t a n s i n Table 11.7 . It i s worth n o t ine, t h a t hV2E,M
( e x p t ) v a l u e i s v e r y dependent upon t h e accuracy o f t h e
- v a l u e s of t h e s o l u t e i n each p u r e s o l v e n t and AV2E,M
V2
( c a l c T d ) v a l u e i s v e r y dependent upon t h e accuracy of
e q u a t i o n ( 5 1 ) i n p r e d i c t i n g t h e p a r t i a l rnolal volume o f
the solute, I n deriving t h e excess t e r n (calculated)
we used equntion ( 5 1 ) t o d e s c r i b e O: nnd v
-E,M
f o r experimental AV2 we used e x p e r i m e n t a l l y d e t e r -
mined and ti: . I n Table 11.8
-V 2 ' s
:ve conpare t h e c n l -
c u l a t e d and experimental i n d i f f e r e n t solvents.
 From Table 11.8 we s e e t h a t f o r Br n-CF
2
in
7 16 '
t h e c a l c u l a t e d V2
- i s e q u a l t o 77.08 cc/mole i n com-
p a r i s o n t o t h e experimental v a l u e 71.8 cc/mole, whereas
for Br2 i n CC14 , the c a l c u l a t e d and experimental
v a l u e s a r e i n good acreement. A s e q u a t i o n (51) p r e d i c t s
bigger 2 t h a n t h e e x p e r i n e n t a l -3
V2 f o r bromine i n
n-C7FI6 , this e r r o r w i l l be manifested i n a l l q u a n t i t -
i e s d e r i v e d from e q u a t i o n (51) f o r t h i s system; f o r B r p
i n c-C4C12F6 , t h e v 23 ( c a 1 c t d ) = 60.69 c c i n compnrison
t o t h e v 2 ( e x p t ) = 64.3 c c , i.e. t h e e q u ~ t i o n ( 5 1 ) pre-
d i c t s a lower v a u e f o r T L
for Br, L
in c-C4C12F6
whereas f o r B r 2 in n-C F 16 , it p r e d i c t s a h i g h e r v a l -
ue. Or i n o t h e r words e r r o r s introduced i n
( e q u ~ t i o n( 6 5 ) ) because of t h e inadequacy

(51) w i l l have t h e o p p o s i t e s i g n (which h a s been o b s e r v e d )

f o r Brg in CC14 - C-C4C12F6 and Br2 i n CC14 -
n-C F 16 . I n one c a s e e q u a t i o n ( 6 5 ) o v e r e s t i m ~ t e st h e

e x c e s s term whereas i n t h e o t h e r c a s e it u n d e r e s t i m a t e s .
A s t h e b a s i c t h e o r e t i c a l e x p r e s s i o n ( v i z . equa-
t i o n (51) ) i s i n a d e q u ~ t ei n p r e d i c t i n g t h e p a r t i a l
n 0 l ~ volume
l o f s o l u t e i n p u r e s o l v e n t , any e x t e n s i v e
compnrison of t h e c a l c u l a t e d and experiment a1 e x c e s s
term, , is n o t worth while.
Concentrated S o l u t i o n
So f a r we have l i m i t e d o u r d i s c u s s i o n t o t h e d i -
l u t e s o l u t i o n such t h a t -0 , i.e. the solubility
of t h e . s o l u t e i s so small t h ~ tt h e volune f r a c t i o n
of t h e s o l u t e i n t h e s o l u t i o n i s n e p l i g i b l e , a c o n d i t i o n
s a t i s f i e d i n t h e e ~ r l i e rd i s c u s s i o n because i n a l l t h e
cases discussed e a r l i e r , :P < 0.01 and t h e b a s i c s o l -
ubility equ~tion

reduces t o i m
In a2 = In x2 + v2 (62 - 6,)
2

as + 0 , (m - 1 .
But t h e r e a r e c a s e s where t h e s o l u b i l i t y of t h e
s o l u t e i s h i g h enough t o make' )
: # o such t h a t
i Sl + is = 1
9;
3
+ .
I n t h i s s e c t i o n we s h s l l d i s c u s s
a few of t h e s e c a s e s . blost of t h e experiniental d a t ~
R v a i h b l e e r e f o r t h e s o l u t e naphthalene i n - 3 i f f e r e n t
o r g a n i c s o l v e n t s , and hence our di:r%ssion w i l l be l i m i t e d
t o t h e case o f naphat-halene i n d i f f e r e n t rzixed s o l -
v e n t s.

Not a t i o n
Before d i s c u s s i n g t h e problems ~ s s o c i ~ t ewdi t h
c o n c e n t r a t e d s o l u t i o n s , we must f i r s t d e s c r i b e some of
t h e n o t a t i o n we s h a l l use i n t h i s s e c t i o n .
 - 103 -
We s h a l l u s e t h e s u p e r s c r i p t o , such as xy
'Pi , i n t h e Following d i s c u s s i o n t o denote t h e s e
0
md

two q u a n t i t i e s i n s o l u t e - f r e e ( o r p u r e ) mixed s o l v e n t s
such t h a t

We s h a l l a l s o u s e t h e s u p e r s c r i p t s , such as
s
Xi and
S
ii , to denote t h e s e q u a n t i t i e s i n t h e s a t u r -
a t e d s o l u t i o n s such t h a t

( f o r s o l u t e we s h ~ l ul s e s u p e r s c r i p t m t o be consis-
t e n t with e a r l i e r discussion). Comparing e q u a t i o n s
( 7 6 ) and ( 7 7 ) w i t h ( 7 8 ) and (?9), one s e e s t h a t t h e r e
e x i s t r e l ~ t i o n s h i p ssuch t h a t

0 0
which connect xi * s ~ n dPi w i t h xs and @f respec-
Results: Naphthalene in CC14 - c-C6H12 mixed solvent

The solubility of naphthalene in CC14 - c-C6H12

mixed solvent was studied by Heric et al. [791 from 10'
to 70'~. They used a "static method" to determine the
saturation solubility. Unfortunately no data was re-
ported at 25'~. For that reason, we plotted their
results of the mole fraction saturation solubility of
naphthalene, x2, in a particular solvent against the
absolute temperature (see Figure 11.28) and the satura-
tion solubility at 298'~. was read from the plot. The
mole fraction saturation solubility of naphthalene cal-
culated in this manner is given in Table 11.9 along with
the mole fractions and the volume fractions of CC14 (sub-
script 1) and c-C6H12 (subscript 3) in a solute free
pure mixed solvent denoted with subscript o.
b

Naphthalene in methylene iodide - c-C6H12 mixed solvent

In Table 11.10 we show the saturation solubility

of naphthalene in methylene iodide - cyclohexane mixed
solvents. These solubilities were determined by J. LeeC8Ql
in this laboratory.
In Figure II.29a we plot the mole fraction of naph-
thalene in saturated solution against the xy, i. e. the
mole fraction of methylene iodide in pure mixed solvents.
By pure mixed solvent we meant solute free mixed solvent
such that xy + xO
2 = 1
 --105 -
similarly

I n F i g u r e II.29b we plot -In :x of naphthalene

i n t h e nethylene iodide - c-C6H12 mixed s z l v e n t a g a i n s t

Discussion
A s mentioned e a r l i e r and can be seen i n T a b l e s
11.8 and 11.9, i n t h e c a s e s of naphthalene B can no
l o n g e r be assumed zero, For d i l u t e s o l u t i o n s , we have
assuned a2 - 0 f o r a l l t h e expressions -- t h e excess
t e r m s and even t h e l i n e a r r e l a t i o n s h i p between (ln ai -
I n):x versus B10 . 2
C l e a r l y t h o s e e x p r e s s i o n s a r e no
longer v a l i d i n these cases,
The obvious d i f f i c u l t y i n c a l c u l a t i n g t h e thermo-
dynamic p r o p e r t i e s f o r t h e c o i o e n t r a t e d s o l u t i o n s a r i s e s
due t o t h e f a c t t h a t :P f. 0. There i s a n o t h e r prob-
lem a s s o c i a t e d ~ i t h n a ~ h t h a l e n tgh:e r e i s no d e f i n i t e
v a l u e f o r t h e i d e a l s o l u b i l i t y of naphthalene t o be found
in the literature. The v a l u e s r e p o r t e d by d i f f e r e n t
~ u t h o r srange from 0.298 t o 0.322 depending upon t h e
source o f data. t81,821
Te! decided t o c a l c u l a t e a; f o r n a n t h a l e n e by
o t h e r nems. Recalling t h e o r i g i n a l eauation f o r t h e
s o l u b i l i t y i n mixed s o l v e n t , i . e ,
it i s seen t h a t f o r t h e c a s e s where 6 . > b2 > 6
1 j
, i.e.
t h e s o l u b i l i t y parameter o f t h e s o l u t e l i e s between t h e
s o l u b i l i t y p a r m e t e r o f t h e two s o l v e n t s , a t c e r t ~ i n
n i x e d s o l v e n t composition, 6, = b2 and t h e s o l u b i l i t y
o f s o l u t e i n t h a t mixture becomes e q u ~ lt o t h e i d e a l
s o l u b i l i t y of t h e s o l u t e . We choose naphthalene as s o l -
u t e i n methylene i o d i d e - c-C6H12 nixed s o l v e n t because
t h e s o l u b i l i t y p a r m e t e r o f naphthalene (6* ) l i e s i n
between t h e s o l u b i l i t y p a r a m e t e r s o f methylene i o d i d e
( bl(therm) = 11.8 ) ~ n d
t h a t of c-C6H12 ( 6,(therm) =

8.2 ) T h e r e f o r e t h i s p a r t i c u l a r system s a t i s f i e s t h e
condition b1 > 6
2 ' 63 . If t h e Regular S o l u t i o n t h e -
o r y i s a p p l i c a b l e t a t h 8 system, t h e n we should be a b l e
t o determine ai f o r naphthalene by d e t e r n i n i n g t h e s o l -
2
u b i l i t y of naphthalene for.the complete range of CH212 -
cmC6H12 mixed s o l v e n t cornyo s i t ion. b
From F i g u r e 11.28
where t h e s a t u r a t i o n mole f r a c t i o n s o l u b i l i t y of naphthal-
-
ene i n C H ~ I ~ C - C ~ H ~X2~ ' i s p l o t t e d a g s r n s t G; ,
we s e e t h ~ tt h e maximum v a l u e f o r x: i s 0.300 which
i s i n e x c e l l e n t ~ g r e e r n e n tw i t h t h e r a n g e 0.298 t o 0.322.
( t h e r e p o r t e d v a l u e s f o r a$ a r e found i n t h e l i t e r -
a t u r e 819821 ) Considering t h a t t h e u n c e r t a i n t y involved
i n c a l c u l a t i n g ai2 from t h e t h e ~ n d~alt a because of t h e
long e x t r a p o l a t i o n involved i n t h e s e c a s e s , we decided
t o u s e x:(max) = 0.300 a s t h e ai
2
f o r haphthalene in
f u r t h e r discussions. So f a r a s we know, t h i s i s t h e
m
o n l y c a s e where t h e x2(max) f o r a s i n p l e s o l i d s o l u t e
 i n a mixed s o l v e n t s y s t e a such t h a t 6
1 > e2 > 63
goes t o i d e d s o l u b i l i t y . The o n l y o t h e r s t u d i e s r e -
p o r t e d i n systems where 6 > 62 > 6 a r e those f o r
3
t h e s o l u b i l i t y o f phenanthrene i n CH212 - c-C6HI2
mixed s o l v e n t . T h i s work was done by S c o t t e t alL833
i n 1952. Although t h e y observed t h e expected enhance-
ment o f t h e s o l u b i l i t y o f phenanthrene, t h e s o l u b i l i t y
i n t h e best solvent mixture f e l l short of t h e i d e a l .
Phenanthrene and naphthalene have s o l u b i l i t y parameters
s i n i l a r t o one a n o t h e r , i.e. 9.8 f o r phenanthrene and 9.9
f o r naphthalene , but t h e nature of t h e i r i n t e r a c t i o n
w i t h c y c l o h e x ~ n ei s v e r y d i f f e r e n t . S c o t t e t a1. found
t h a t t h e s o l u b i l i t y p a r m e t e r of c-C6H12 h a s t o be
s h i f t e d from 8.2' ( t h e thermodynmic v a l u e f o r c-C6H12 )

t o 7.0 t o s a t i s f y t h e s o l u b i l i t y e q u a t i o n f o r phenanthrene
i n cyclohexane, whereas f o r naphthalene inc-C6H12 ,
although a r e - e v a l u a t i o n o f 6 s o l u b i l i t y parameter f o r
cyclohexane i s needed, t h e magnitude of s h i f t f r o n 8.2
t o 7.66 i s much s m a l l e r t h a n t h a t f o r phenanthrene i n
cyclohexane. A t p r e s e n t , t h e r e a s o n f o r t h i s l a c k of
agreement between t h e p r e d i c t e d and e x y e r i m e n t ~ l v a l u e s
f o r t h e s o l u b i l i t y of phenanthrene i n t h e b e s t s o l v e n t
mixture i s n o t c l e a r .
A c l o s e e x ~ r n i n a t i o no f t h e phase diagram f o r t h e

b i n a r y s y s t e n o f methylene i o d i d e - cyclohexnne as giv-

en by Gordon m d S c o t t r e v e ~ l l st h ~ at t 298 O K there is
a d e f i n i t e m i s c i b i l i t y gap i n t h e n e t h y l e n e i o d i d e -
 0
cyclohexane system when l i e s between 0.28 and 0.58.
X3
Thus t h e s t o i c h i o m e t r i c composition o f t h e b e s t s o l v e n t
m i x t u r e f o r phenanthrene l i e s c l o s e t o t h e CH21g -
c-C6H12 s o l v e n t - s o l v e n t c r i t i c a l t e m p e r a t u r e and com-
position, From t h i s o b s e r v a t i o n S c o t t e t al.'*'Isugges-
t e d t h a t t h e r e i s an e x t e n s i v e l f c l u s t e r i n g v mound t h e

phenanthrene molecule i n i t s b e s t s o l v e n t m i x t u r e and

t h i s c l u s t e r i n g i s t h e r e a s o n f o r t h e apparent l a c k of
agreement between t h e i d e a l s o l u b i l i t y and t h e maximum
s o l u b i l i t y o f phenanthrene i n i t s b e s t s o l v e n t mixture.
It i s t r u e t h ~ tt h e r e i s a s o l v e n t - s o l v e n t m i s c i b i l i t y
gap when t h e mole f r a c t i o n o f cyclohexane i n pure mixed
s o l v e n t l i e s between 0.28 and 0.58. But we a l s o observed
t h ~ tth e s o l v e n t - s o l v e n t m i s c i b i l i t y gap d i s ~ p p e a r si n t h e
presence -,of naphthalene i n t h e t e r n a r y systems o f
CH212- naphthalene - C-C6H12: Besides, f o r naphthal-
ene, t h e s t o i c h i o n e t r i c composition of t h e b e s t s o l v e n t
n i x t u r e i s a l s o near t o t h e solvent-solvent c r i t i c a l
composition and temperature. Rut o u r o b s e r v a t i o n t h a t
t h e maximum s o l u b i l i t y of naphthalene i n t h e b e s t s o l v e n t
m i x t u r e i s equal t o the i d e a l s o l u b i l i t y of n ~ p t h a l e n e ,
s u g g e s t s t h a t t h e w c l u s t e r i n g v as mentioned by S c o t t
c ~ n n o tbe a main f a c t o r f o r t h e d i s c r e p a n c i e s observed
i n t h e c a s e o f phenanthrene i n CH212 - c-C6H12 mixed
solvents.
Subsequently we e s t a b l i s h e d t h a t i n t h e c a s e o f
n a p h t h a l e n e , x:(max) i n t h e b e s t s o l v e n t c m be used
safely t o replace a: for naphthalene i n f u r t h e r c a l c -
ulntions. Using a: = 0.300 , we calculated 6r n ' 61s
and b3 f o r systems w i t h n a p h t h a l e n e as s o l u t e . I n
Table 11.11 we g i v e t h e experimental 6 m ' s f o r C C 1 4 - nap
hthalene - c-C6HI2 and i n Table 11.12 we show t h e ex-
perimental bm values f o r CH212- naphthalene - c-C6HI2.
In these calculations the 62 v a l u e T o r naphthalene was
t a k e n a s 9.9 -- t h e thermodynmic s o l u b i l i t y p a r m e t e r
f o r naphthalene.
Next we chose t o c a l c u l a t e 6, f o r t h e nixed sol-
vent. We showed e a r l i e r t h a t 6, can be c a l c u l a t e d

such t h a t
q + 9"3 = 1

such t h a t * *
G I + @ = 1
3
and
* and @
* a r e defined a s

I n Table 11.13 we compare t h e 6m c a l c u l a t e d from

t h e experimental s a t u r a t i o n s o l u b i l i t y of naphthalene
with t h e 6 w r i t t e n i n terms of 9 and i n t e r m s o f
*
for CC14 - c-C6H12 system. Clearly 6, (writ-
t e n i n terms of
*
Q l ls) i s i n b e t t e r agreement w i t h t h e
b,(experimental) -- a s i t u r l t i o n we ~ l s of a c e d i n d i l u t e
solutions. But we a l s o s e e i n t h e Table 11.13 thrlt t h e
agreement between t h e experimental and t h e 6*
'm m
( c a l c u l a t e d from Q
* l s ) m e n o t so good for t h e nixed
s o l v e n t i n which t h e c o n c e n t r a t i o n of carbon t e t r a c h l o -
r i d e i s v e r y smd.1. From t h e d e f i n i t i o n of ' r e f f e c t i v e n
volume f r a c t i o n , we c l e a r l y s e e t h a t i n t h e c a s e of
carbon t e t r a c h l o r i d e - naphthalene - cyclohexane system,
c ~ i r b o nt e t r a c h l o r i d e i s a pre'ferred s o l v e n t f o r naph-
t h a l e n e t h a n cyclohexane. VJe a l s o s e e thrlt i n t h e c a s e
of t h e n i x e d s o l v e n t where @: = 0.1575 , the volume
f r a c t i o n o f naghthalene, @ , i n solution i s greater
t h a n t h e volume f r a c t i o n , @*, of carbon t e t r a c h l o r i d e
i n t h e solution -- a s i t u a t i o n we d i d n o t cone a c r o s s
i n t h e c a s e of d i l u t e s o l u t i o n . T h i s phenomenon becomes
more prominent f o r naphthalene i n CH212 - c- C6H12 nixed
solvents. I n Table 11.14 we conpare bm(expt) with
6,(calc1d) and
*
6,'s. We s e e i n Table 11.14 t h a t 6,

c a l c u l a t e d from t h e e x p e r i m e n t ~ ls o l u b i l i t y of naphthal-
ene a g r e e s w i t h
*
6, ( c a l c u l a t e d from 4
* 's) when t h e
volume f r a c t i o n of n e t h y l e n e i o d i d e i n p u r e mixed s o l -
v e n t i s p ; r e ~ t e rt h a n 0.403. Ye a l s o s e e i n Table 11.14
t h a t a t v e r y low c o n c e n t r a t i o n of mnthylene i o d i d e 6, ls
( c a l c u l a t e d from 9; ) r a t h e r thrln 6,
* '9 ( calculated
*
from @ ' s ) i s i n much b e t t e r twreenent w i t h em (expt).
But i n most of t h e c a s e s where 4; 0.403 we s e e t h a t
 - 111 -
6,(expt) l i e s between b m t s ( c a l c u l a t e d from 4' ) and
* *
6,ls ( c a l c u l a t e d from 4 ) O r i n o t h e r words we could

s a y t h e r e i s a minimum v a l u e f o r t h e volume f r a c t i o n
of CH212 up t o which t h e t t e f f e c t i v e v tvolume f r a c t i o n s
concept i s a c c e p t a b l e . But i f t h e volume f r ~ c t i o no f
u e t h y l e n e i o d i d e i s l e s s t h a n t h a t lrinimuu v a l u e , t h e
n e a r e s t neighbour o f t h e s o l u t e i s n e i t h e r d e f i n e d by
*
t h e " e f f e c t i v e f f volume f r a c t i o n s @ nor by H 's.
The r e a s o n why 4's do n o t a d e q u a t e l y d e s c r i b e t h e
n e a r e s t environment of t h e s o l u t e h a s been d i s c u s s e d
earlier.
For c o n c e n t r a t e d s o l u t i o n s , it seems t h a t t h e r e
e x i s t s a ninimwn v a l u e f o r t h e number of moles o f t h e
p r e f e r r e d s o l v e n t s which must e x i s t i n t h e s o l u t i o n
s o t h a t t h e near.est neighhours of t h e s o l u t e i n a nixed
s o l v e n t may be a d e q u ~ t e l yd e s c r i b e d by t h e e f f e c t i v e
volume f r a c t i o n s . A t p r e s e n t we were n o t a b l e t o pre-
d i c t t h i s minimum v a l u e f o r t h e p r e f e r r e d s o l v e n t b u t
from t h e experimentril r e s u l t s it i s c l e a r t h a t (the
volume f r a c t i o n o f t h e p r e f e r r e d s o l v e n t i n t h e s o l u t i o n )
must be g r e a t e r t h a n t h e ( t h e v o l m e f r r i c t i o n of
the solute i n solution). I n Table 11.13 we compare
t h e 6,(experimental) w i t h both b m and 6,
* for CClb -
naphthalene - c-C6HI2 system. The s i t u a t i o n i s analysed
i n nore d e t a i l i n t h e c a s e o f methylene i o d i d e -naphtha--
lene - c y c l o h e x ~ n ebecause more experimental d a t a a r e
a v a i l a b l e f o r t h i s system. I n T ~ b l e11.14 b m (expt.)
 - 112 -
i s c o q a r e d with b m ( c n l c t d ) nnd bm
* . I n T a b l e 11.14
we a l s o g i v e t h e v a l u e s of 4; and I: f o r t h i s system.
It c m be seen t h a t when 9; is l e s s than 9; , 6,

(expt) i s l e s s than
*
6, but p r e n t e r t h s n b m ( c a l cl d )
*
.
However b m ( e x p t ) i s a d e q u a t e l y d e s c r i b e d by bm when
S
Il 2
s
g2 . For t h e methylene i o d i d e - n a p h t h a l ~ n e cyclo- -
hexane system, t h e experiment a 1 r e s u l t s suggest t h a t
t h e mininum v a l u e f o r ,
"
Qr
i n t h e s o l u t i o n n u s t be e q u a l
t o one i f t h e n e a r e s t n e i g h b o w environment of t h e s o l -
u t e may be adequately d e s c r i b e d by t h e u e f f e c t i v e l f vol-
m e f r a c t i o n term. When
S
< 12
S
, neither I: nor
*
d e s c r i b e s t h e inmediate environment of s o l u t e cor-
rectly.
Next we looked i n t o t h e problem o f t h e s q u a r e r o o t
plot, i,e. ( l n :a - I n x:)~
1
versus I: (or
*
Q1 ) as

d e s c r i b e d i n S e c t i o n s 1 and 2 of t h i s c h a p t e r , A s men-
i - I n "):x
t i o n e d i n t h o s e s e c t i o n s ( I n a2
1
and Q 1
*
have a l i n e a r r e l a t i o n s h i p i f and only i f Q2 0 , i.e.
v e r y d i l u t e solut9on. For c o n c e n t r a t e d s o l u t i o n such
1
r e l a t i o n s h i p s nay be found between ( I n
i
a2 I n -
m z
x2)
versus
*
. A v e r y similar r e l a t i o n s h i p i s d e r i v e d by
followine, t h e sane procedure RS before. Writing t h e

s o l u b i l i t y e q u ~ t i o nf o r component 2 i n a mixed s o l v e n t
i n t e r n s o f Regular S o l u t i o n t h e o r y we f ind
Eouetion ( 8 2 ) was d e r i v e d by w r i t i n g

S i m i l a r l y t h e s o l u b i l i t y e q u ~ t i o nf o r component 2 i n
a pure s o l v e n t 1 i s

or i Vp
( I n a2 - I n xi)* = (m)2Ql(61 - 62)2

Dividing e q u a t i o n (82) by e q u ~ t i o n(83) r e o b t a i n

i
( I n a2 - m $
1n x2)
i
( I n a2 - In

where @I i n e q u a t i o n s (83) and (84) i s t h e same m d

d e n o t e s t h e voluile f r a c t i o n of component 1 i n t h e s a t -
u r a t e d s o l u t i o n of s o l u t e 2 i n p u r e s o l v e n t 1; is
@1
a c o n s t a n t i n e q u a t i o n ( 8 4 ) because it i s the o r o p e r t y
of t h e b i n a r y system containinp. conponents 1 and 2 only.
E q u ~ t i o n( 8 4 ) c a n be p l o t t e d two ways:
Q
( i ) I f we assune --L i s c o n s t a n t and Q m FJ
@1 @1
then J
Q 1 o r equation (84) reduces t o
@ 1
EquRtfon ( 8 5 ) i s t h e same a s e q u a t i o n ( 2 6 ) i n s e c t i o n
1 o f t h i s c h a p t e r except t h a t i n t h e d e r i v a t i o n o f equa-
t i o n ( 2 6 ) live assumed 4 0 and i n t h e c a s e o f equa-
12
.
-
4
t i o n (85) we assumed t h a t f
1
1
I n Table 11.15 we shov~t h e r a t i o 4 f o r carbon
Q 1

t e t r a c h l o r i d e - naphthalene - cycl-ohexane mid

CH212 - naphthalene - c y c l o h e x ~ n esystems. For t h e
CC14- naphthalene - c y c l o h e x ~ n esystem, 9
"
Q1
i s very
c l o s e t o u n i t y and we should expect a s t r a i g h t l i n e f o r
t h i s system when ( I n a2 i
In x2) -
m $ i s plotted against
*
either P or 93 because e q u a t i o n s ( 8 4 ) ~ n d( 8 5 )
can be d e r i v e d i n t e r n s of P
*
by w r i t i n g 6,
*
= 1 6 +
3
6 . I n F i g u r e 11.30 w e p l o t t e d ( I n a2
i
- rn111
1" x2)
2

f o r t h e CCld- naphthalene - c-C6H12 system a g a i n s t

both I; and
*
m3 . A s i s found i n t h e c a s e o f d i l u t e
s o l u t i o n s , we s e e t h a t f o r c o n c e n t r a t e d s o l u t i o n s ,
( I n a2 i - m $
I n x2) v e r s u s I; p l o t i s f a r f r o n a s t r a i g h t
l i n e , i. e. no l i n e a r r e l a t i o n s h i p e x i s t s between
( I n a2 i - m $ and G o3
I n x2) .
But i n F i g u r e 11.30 t h e r e
e x i s t s a l i n e ~ r e l a t i o n s h i p of ( I n a$ - I 'n):x ver-
*
sus e3 -- w i t h a s l o p e e q u a l t o 0.41, conpnred t o
0.39, t h e expected v ~ l u ef o r t h e slope. The i n t e r c e p t
of
i
( I n a2 - m
l n x2)
* versus B3
u
p l o t s was made e q u a l
t o t h e expected v a l u e , I n F i g u r e 11.30 we show R sim-
i l a r plot for CH212- mphthaleqe - c-C6HI2 system,
For t h i s system, w i t h b 1 > b 2 > 63 , we observe t h a t
1
m
when 6, = b2 , i
( I n a2 - 1 n x2) -2
i s z e r o and we ob-
t a i n two s t r a i g h t l i n e s -- one w i t h t h e s a t u r ~ t i o ns o l -
u b i l i t y o f conponent 2 i n p u r e s o l v e n t 1 a s r e f e r e n c e
s*ate, and t h e o t h e r w i t h t h e s a t u r a t i o n s o l u b i l i t y of
component 2 i n p u r e s o l v e n t 3 a s t h e r e f e r e n c e s t a t e ,
These: t y p e s of systems, where b1 > b2 > b3 , have been
d i s c u s s e d e a r l i e r i n t e r m s of d i l u t e s o l u t i o n s and we
f i n d t h a t t h e sane t h i n g can be s a i d about t h e concen-
t r a t e d solutions. I n F i g u r e 11.30 w e p l o t t e d ( I n a:-
1
I n x:)~ against and found t h a t t h e s l o p e s o f t h e
b e s t l i n e drawn through t h e experimental p o i n t s a r e
-1.19 and 1.40 which compare f a i r l y w e l l w i t h t h e c a l c -
u l a t e d Values -1 .I8 and 1.45 r e s p e c t i v e l y .
The first s e t of t h e c a l c u l a t e d and experimental v a l u e s
f o r t h e slopes a r e with a s t h e r e f e r e n c e s t a t e and
xk

.
t h e second s e t of v ~ l u e sf o r s l o p e s a r e w i t h x3 RS t h e
2
reference s t a t e . I n t h a t p n r t o f t h e p l o t we assume
i s e q u a l t o one i n s t e a d o f -
Q1
e q u a l t o one. In
Table 11.15, we show t h e r a t i o o f and for this
Q 1 Q3
system. It i s seen t h a t
m i s v e r y c l o s e t o u n i t y and
Q 1
*
so we o b t a i n a s t r ~ i g h tl i n e up t o B j = 0.4 when
i
( l n a2 -
1 n x2)
1
'
i s plotted against a s i n Ficure
9,
11.31. It can a l s o bee seen from T ~ b l e11.15 t h a t -
Q3
 - 116 -
i s n o t e q u a l t o u n i t y f o r c a s e s where
*
@3 < 0.4 and i n
F i g u r e 11.31 t h e agreement between t h e experimental p o i n t s
nnd t h e c a l c u l a t e d l i n e i s n o t good i n t h e r e g i o n )3 < .4,
But i n g e n e r n l we s e e t h n t i n a f n i r ~ p p r o x i m n t i o n , -
Pm
Q1
i s e q u a l t o u n i t y , and t h e r e e x i s t s a l i n e a r r e l ~ t i o n -
i 1 *
s h i p between ( I n a2 - 1" x :
)
~ and P even f o r t h e
concentrated solution,
( i i )Equation (84) can a l s o be r e w r i t t e n a s

i
(In a2 - m 4
I n x2) i m -?-1
= -I ( ~ a2
n - I n x2)
em @I

Equation (86),which i s w r i t t e n i n t e r m s of t h e
s m e n o t s t i o n a s i n equation (A4), i m p l i e s a l i n e a r
r e l a t i o n s h i p e x i s t s f o r n conc,entrated s o l u t i o n between
1
m -
( I n a2
i
- 0
I n x ~ ) ~P m/ and P3 f o r which t h e s l o p e should

and t h e i n t e r c e p t a t O = 0 would be e q u a l t o
@3

Both s l o p e s and i n t e r c e p t can be conpnred w i t h t h e ex-

p e r iment a 1 v8.lues.
 -- 117 -
Equation ( 8 6 ) i s a d i r e c t consequence of t h e Reg-
u l a r S o l u t i o n t h e o r y f o r a t e r n a r y system and so f a r no
a d d i t i o n ~ lassumption has been made, even though it i s
more r i g o r o u s t h a n t h e e q u a t i o n ( 8 5 ) . From our e ~ r l l e r
experience, we know t h a t 6, ( e x p t ) i s b e t t e r d e s c r i b e d
by 6
*
i n s t e a d of 6 . If t h e s o l u b i l i t y equation
f o r component 2 i n a mixed s o l v e n t i s w r i t t e n i n t e r m s
*
of 6 i n s t e a d of 6, , e q u a t i o n ( 8 6 ) becomes

( I n a2
i - m
I n x2)
+ +-
= -I ( I n a2
i - I n x2)
m
@m @I

+ -1 ( I n a: - 1 3I*
I n x2) 61-63
3 62 - h1 (87)
@1

The o n l y d i f f e r e n c e between e q u ~ t i o n s( 8 6 ) And ( 8 7 )

i s t h a t e q u a t i o n ( 8 7 ) implied a l i n e a r r e l a t i o n s h i p
between ( I n a2
i
- m *
I n x2) '/@,pnd ij ( n o t I ; as i n
t h e c a s e of e q u ~ t i o n(91) ) f o r which s l o p e and i n t e r -
c e p t s a r e t h e same a s f o r e q u ~ t i o n( 8 6 ) .
I n F i g u r e 11.32 we p l o t ( I n a: - I n xm~ ) ' / @ a-
~
gainst and I
* for the CC14 -naphthalene - c-C6H12
system. I n F i g u r e 11.93 we show t h e same p l o t f o r t h e
C1212 - naphthalene - c-C6H12 system.
For t h e naphthalene i n CC1
4
- c-C6H12 s y s t e n , we
conpare t h e t h e o r e t i c a l l i n e gain st t h e experimental

p o i n t s and t h e agreement between t h e experimental p o i n t s

and t h e t h e o r e t i c a l v ~ l u e si s good when p l o t t e d a q a i n s t
and n o t ~ @ O
3
. But t h e agreement i s n o t so good f o r
naphthalene i n n e t h y l e n e i o d i d e - c-C6HI2 , This is not
s u r p r i s i n g because a s we s ~ i de a r l i e r , n e i t h e r @ nor
* J

d e s c r i b e s t h e n e a r e s t s o l u t e environment c o r r e c t l y
e3
when 97 i s l e s s than @ . I n F i g u r e 11.33 we s e e
t h a t aereement between t h e expected l i n e and t h e exner-
i m e n t a l p o i n t i s good f o r t h e mixed s o l v e n t s concent-
r a t e d i n rnethylene i o d i d e and i s bad f o r mixed s o l v e n t s
d i l u t e i n nethylene iodide -- a s i t u a t i o n vhich concurs
w i t h our e a r l i e r d i s c u s s i o n on 6,'s f o r concentrnted
solull ions.
A s i n t h e s o l u b i l i t y equations, , i j and @ m t ~

a r e r e t a i n e d and no a t t e m p t t o calculate e x c e s s proper-

t i e s f o r concentrnted s o l u t i o n i s made because t h e equa-
t i o n s cannot be d e r i v e d i n terms o f t h e p r o p e r t i e s o f
t h e p u r e s o l v e n t es was done i n t h e c a s e of d i l u t e s o l -
utions. So we d i d n o t t r y t o L p ? o t any e x c e s s proper-
t i e s f o r t h e concentrated s o l u t i o n s ,

Conclusion
I n g e n e r a l it i s seen t h a t t h e p r e s e n t l y a v a i l ~ b l e
e x p e r i u e n t a l d a t a i s w e l l i n t e r p r e t e d by t h i s e x t e n s i o n
of t h e Regular S o l u t i o n t h e o r y t o two component s o l v e n t
systens. The p o s t u l a t e d "pref e r e n t f a 1 s o l v a t i o n w o f t h e
s o l u t e by one component of t h e s o l v e n t mixture i s w e l l
borne o u t f o r d i l u t e s o l u t i o n s . For t h e c o n c e n t r a t e d
s o l u t i o n s of R s o l u t e i n a two conponent s o l v e n t n i x t u r e
we showed t h a t t h e r e e x i s t s a minimum v a l u e f o r t h e
number of n o l e c u l e s o f t h e p r e f e r r e d s o l v e n t which must
e x i s t i n t h e s o l u t i o n i n o r d e r t o observe t h e f u l l e f -
f e c t of t h e " p r e f e r e n t i a l s o l v a t i o n " i n t h e s t u d i e s o f
t h e s o l u b i l i t y of s o l u t e 2 i n t h e two component s o l v e n t
systems.
The r e l a t i o n s h i p between i
( I n a2 - m $
I n x2) and
*
or f o r d i l u t e t h r e e component systems, depends
o n l y upon t h e d e f i n i t i o n of 6, . A l l systems consid-
e r e d a s d i l u t e s o l u t i o n s show t h a t t h e expected l i n e a r -
*
i t y i s found only i f , the e f f e c t i v e volume f r a c -
t i o n term, i s used. For t h e c o n c e n t r ~ t e dt h r e e compon-
e n t systems, t h e l i n e a r r e l a t i o n s h i p e x i s t s between
( l n at - 1
m z/
I n x2) , i n s t e a d o f ( l n a2i I n xp) m 21 - ,
and 0
or *
II . For c o n c e n t r a t e d s o l u t i o n s we a l s o
show t h a t , i n c e r t a i n c a s e s , a l i n e a r r e l a t i o n s h i p can
be observed between ( I n :a - '):x
;Ln
1
and or @I
* .
However, t h i s l i n e a r r e l a t i o n s h i p between i
( l n a2 -
m Q and @
I n x2) or * depends upon t h e v a l i d i t y of
t h e assumption t h a t t h e volume f r a c t i o n o f t h e nixed
solvent i n t h e saturated solution of t h e s o l u t e 2 i n
t h e mixed s o l v e n t i s e q u ~ lo r a p p r o x i n a t e l y equal t o
t h e volume f r a c t i o n of t h e r e f e r e n c e s o l v e n t i n t h e s a t -
urated solution. IJe a l s o s e e t h a t , f o r a c o n c e n t r a t e d
s o l u t i o n , t h e above-ment ioned l i n e a r r e l a t i o n s h i p e x i s t s
between @
*
* s i n s t e a d of @O .
The n e c e s s i t y of u s i n g t h e e f f e c t i v e volune f r a c -
t i o n , which r e f l e c t s t h e i n t e r a c t i o n of t h e s o l u t e mol-
 -: 120 -
e c u l e w i t h i t s immediate s o l v e n t e n v i r o m e n t , is again
shown by t h e t h r e e e x c e s s s a t u r a t i o n s o l u b i l i t y t e r m s
f o r t h e d i l u t e s o l u t i o n of 2 i n two component n i x e d
solvents. (We have n o t d e r i v e d any e x p r e s s i o n f o r ex-
c e s s s ~ t u r a t i o ns o l u b i l i t y t e r m s f o r c o n c e n t r a t e d s o l -
u t i o n of 2 i n two component mixed s o l v e n t . ) If we con-

trast the ~(lnx:) and t h e h ( l n x:*) t e r m s (i.e.

i n each t h e therrnodynmic r e f e r e n c e s t a t e i s Q1 , the
bulk s o l v e n t volume f r a c t i o n ) , we n o t e t h ~ tth e m ~ g n i -
t u d e o f t h e e x c e s s t e r m a r i s e s mainly from t h e need t o
define 6 using
*
il .
S e t u r ~ t i o ns o l u b i l i t y m d p a r t i e l m o l ~ lvolune of
i o d i n e i n a nixed benzene-cyclohexene s o l v e n t :
fl1 d ~ t a t 25 O C.

Volune f r a c t i o n S ~ t u r ~ t i o ,Xntropy
n of P m t i a l 1.lolal
of benzene, Solubility Solution Volune,
 - 122 -
Table 11.2

I o d i n e in benzene-cyclohexane solvent:
data at 25 O C.

Volume f'r~ction 6, '

m
of benzene, us ing
@4 ( expt 1 0,

- -

( 6 values used i n this calculation are:

-
'
1 - 'benzene = 9-99
- = 14.1
6 2 - 'iodine
Iodine i n benzene - c ~ r b o nt e t r ~ c h l o r i d es o l v e n t :
All d ~ t ef i t 25O 6 .

Volurw f r a c t i o n
of benzene,
@1
6m
(exd
m
'
using a,
'
a
using Pi,
*

( 6 v a l u e s used i n t h i s c ~ ~ l c u l ~ t ia o
r en:

-
6l - 'benzene = 9-99
- 14.1
62 - 'iodine =
 Table 11.4

Iodine in benzene-cyclohex~ne ~ n dbenzene - cnrbon

tetrachloride solvents:
All data at 25 O C.

(In):x = el In x21 + P 3 In x23

Benzene-Cyclohexane
Solvent I Benzene - Carbon Tetra-
chloride Solvent
 - 125 -
Table I I , 5

Sn14 i n benzene - c-C6HI2 mixture:

(a: a2 ~f o~r ~sn14

f o r sn14 = 0 . 1 1 ~ ~ ; = 11.8C241)

Volune f r ~ c t i o n S ~ t u r a t i o n m 1
of benzene, solubility ( h a 2i- lnx,m ) z
@I -In x2
x; x 1 0 - ~

0 0,7279 4,9236 1,6653

 -126 -
Table 11.6

S 0 2 . u b i l i t ~ p ~ r ~ ~ n e otf e rC6H6
~ - c-C6Hi2 nixed
solvents f o r C6H6 - Sn14 - c-C6H12 systems:
 - 127 - .

Table 11.7

A# i n mixed s o l v e n t s :

rolwe
'ract.
Ienzene
'
Volume
frmt .
CC14

0.0525
0,108
0,1615
0.28
0.72
0 -94

B r 2 in CC14 - n-C 7F 16:

Volume A V ~ nvE
fract. cc mole-' cc mole -1
CC14 ( calcl d) ( expt)

0,031 -5 004 -0 045

0.063 -5.29 -0.69

0,122 -6.38 -3.84

0,175 -9.58 -6 020

i v
P n r t i a l molnl volume of s o l u t e i n pure solvents:

- -
Solute Solvent v2( e x ~ t ) v2( c a l c t d )
cc/mol e cc/mole

( b f o r benzene was ~ s s u n e dt o be equal t o 9.99)

 - 129 -
Table 11.9

S e t u r n t i o n s o l u b i l i t y of naphthalene i n CC14 - C - C ~ H ~ ~
mixed s o l v e n t a t 298 oK.1791.

Volume f r a c t . Volme f r a c t . Volume f r a c t .

of C C 1 4 i n of C C 1 4 i n of naphthalene 6,
solute-f r e e solution, i n solution,
solvent,
QP
s a t u r a t i o n s o l u b i l i t y of naphthalene i n CH212 - C-C6H1 2
mixed s o l v e n t a t 25 O C:

Mole f r a c t i o n volune f r a c t i o n saturation

of net hylene o f I2 i n solubility
iodide i n pure p u r e mixed of naphthalene,
nixed s o l v e n t , solvent,
0 m
X , @: - I n x,
 Table 11.11

S o l u b i l i t y p a r m e t e r s of nixed s o l v e n t s i n t h e
CC14- naphthalene - c-C6HI2 system.L791

- -
Volme f r a c t i o n effective pol, 6- 6m - *6 m -
o f CCIB , f r a c t i o n of I11
~ 9 6 1+ hal +
BY CCl4 ,
@: (expt)
0 g6 3
*
Q363

( 6 v a l u e s used i n t h i s c a l c u l ~ t i o nm e :
 - 132 -
Table 11-12

6 v d u e s for CH212 - c-C6HI2 mixed solvent for

CH212- naphthalene - c-C6HI2 system:
 - 133-r
T a b l e 11.13

( exI?t)
'rn for CC14 - c-C6H12 in CC14 - naphthalene
system, alonlz: with values:
c-C6Hi2 NE
 - 134 -
Table 11.14

6, for CH212 - c-C6HI2 in -

C H ~ I ~naphthalene
Values for 5
)1
for CC14- naphthalene - c-C6H1
md CH212 - haphthalene - C-C6H12 systems:

CC14 - naphthalene CH212 - naphthalene- c-C6H12:

e1(1,2) is t h e volume f r n c t i o n of 1 i n the saturnted

solution of 2 in solvent 1.
Figure 11.2. Excess saturation solubility term ,

(hln):x and excess partial molal volume term (AT!)

plotted as a function of benzene volume fraction in
the mixed benzene-cgclohexane solvent. Data at 25 O C .
- Figure 11.4. Saturation solubility
of iodine in mixed C6H6 - C-C6H.12 /
(

solvent ( plotted as R in x2)

as a function of the :effectiv<
v o l q e fraction" of benzene.
Data at 25'~.

-
- as a function of benzeneweffective volume fraction"
( ) Dafaat~5~~.
Figure 11.8. I o d i n e i n mixed carbon t e t r a c h l o r i d e
perfluoroheptane s o l v e n t . Data p o i n t s p l o t t e d a g a i n s t
simple volume f r a c t i o n of carbon t e t r a c h l o r i d e i n mixed
solvent (a) and a g a i n s t " e f f e c t i v e volume f r a c t i o n "
of carbon t e t r a c h l o r i d e ( 0 ) . S o l i d l i n e r e p r e s e n t s
*
t h e t h e o r e t i c a l ( I n a;- I n $)* versus el o r G 1
r e l a t i o n s h i p . Data a t 25.O'C.
Figure 11.8
Figure 11.9. S a t u r a t i o n s o l u b i l i t y of Sn14 i n
mixed benzene-cyclohexane s o l v e n t p l o t t e d ( a s i n x):
as a f u n c t i o n of volume f r a c t i o n of benzene. Data
a t 25OC.
0.4 0.8 1-0
61
Figure 11.9
Fipure 11.10. Sn14 i n benzene-cyclohexan6 nixed
1
solvent. Y (i.e. i
( l n ag - I n x:)~ ) plotted a
f u n c t i o n of volume f r a c t i o n o r benzene ( 0 ) and as R

f u n c t i o n o f e f f e c t i v e volume f r a c t i o n of benzene ( E l ).
Data a t 25' C.
F i g u r e 11.10
solubility of Sn14 in

?*effectivevo1um-=-$i+%ctionw
of benzene.
hj cuc 4-r
F i g u r e 11.13. bm( experimental) f o r benzene-cyclo-
h e x m e i n benzene - Sn14 - c y c l o h e x ~ n esystem. Plotted
as FI f u n c t i o n of volume f r a c t i o n o f benzene ( a ) and
t t e f f e c t i v e v o l m e f r n c t i o n " o f benzene (O ) . Solid
line r e p r e s e n t s t h e o r e t i c a l
6m
versus or :9 .
Data a t 25' C.
Figure 11-15
Excess saturation
solubility terms.
Curve A - z(
1
Aln x;
.
)
Curve B - 1 aln):x
Curve C - A-(
1 A + In):x
for solute b2 (=14) in
mixed solvent b1=12
bj=6
F i g u r e I1 .l6. Excess s a t u r a t i o n s o l u b i l i t y t a m
f o r i o d i n e i n a nixed benzene-cyclohexnns s o l v e n t .
25O C.

c u r v e A: A ( ln x&)

Curve B: ~ ( l):n
x

Curve C: hw(ln xz)

Emerimental data @
F i g u r e 11.16
Figure 11.17. Excess s a t u r a t i o n s o l u b i l i t y curve
f o r i o d i n e i n mixed benzene - carbon t e t r a c h l o r i d e
solvent. 25OC.

Curve A: ~ ( l xF*)
n

curve B: A ( I n x;)

Experimental d a t a p o i n t s 0
F i g u r e II.lC(
F i g u r e 11.18. Excess s ~ t u r ai ot n s o l u b i l i t y curve
for Sn14 i n benzene-cyclohexane nixed s o l v e n t .

o experimental p o i n t s .

A l l data at 25' C.
0 04
F i g u r e 11.18
Figure 11.19. Excess s a t u r a t i o n s o l u b i l i t y term
f o r iodine i n a mixed carbon t e t r a c h l o r i d e - per-
fluoroheptane solvent. 25OC.

Curve A: ~ ( l xn
),:

Curve B: A(ln x
):

Experimental data points

F i g u r e 11.19
Figure II.20.Saturation solubility of iodine in CC14 -
n-c F 6 mixed solvent plotted ( as in :x as a function
7 1
of the "effective volume fractionu and the volume
C.
fraction of CC1
4' Data at 25'
Figure 11.21. Excess saturation solubility curves,
h(ln xF*) for naphthglene ( 62 = 10) in hypothetical
mixed solvents.

Curve A: b l = 6; 6 3 = 14

Curve B: = 8; 6 3 = 12.
F i g u r e 11.22.
i
( l n a2 - m &
I n x2) p l o t t e d a g a i n s t
* f o r naph$haldne i n
e f f e c t i v e volume f r a c t i o n
h y p o t h e t i c a l mixed s o l v e n t s .

Curve A: b1 = 6; b 3 = 14.

Curve B: bl=8; b 3 = 12.

( f o r t h i s system I l
* - a1)
O.!

Figure 11.22
Figure 11.23; Excess saturation solubility for Sn14
"
( 6 = 11.7) in hypothetical mixed solvent ( b l = 5.6;
b 3 = 14.0).
rn
Curve A: ~(ln
xz,); Curve B: ~ r ( l nx3);
Curve C: ~ ( l):x
n
Figure 11.24. (ln :a - m $ plotted as a
In x2)
i+
function of el (linear plot A) and as a function
of (curve B) for stannic iodide ( 6 2 = 11.7)
in hypothetical mixed solvent b 1 = 5.6; a3 = 14.0.
I.!

Figure I I . 2 4
Figure 11.26. Excess volume of mixing function -AV E
f o r iodine i n a mixed C6H6 - C-C6H12 solvent, a s a
function of volume f r a c t i o n 4 (assuming e f f e c t i v e
volume f r a c t i o n d e f i n i t i o n f o r bm). Data a t 25OC.

F u l l curve - calculated from equation (65) .

Experimental data p o i n t s (according t o equation (66) )
Figure 11.26
F i g u r e 11.27. Excess volume of mixinp t e m i -bvE for
bromine i n a nixed CC14 - c-C4C12F6 s o l v e n t , 25 O C ,
p l o t t e d a g a i n s t volune f r ~ c t i o nof CC14 .
T h e o r e t i c a l curve - full line - assmine effective
volume f r a c t i o n d e f i n i t i o n o f 6m.

Experimental d a t a p o i n t s @
Figure 11.27
 -
Figure 11.28 Saturation solubility of naphthalene
in CC14 - c-C6HI2 mixed solvent of different composition,
plotted ( as):x as a function of temperature.
Curve A: pure CC14
Curve B: '? = ' ~ ~ 1= 40.5518
Curve C:
'? = @C!c14= 0.3637
Curve D: 4: = "cc14= 0.1575
Curve E: pure c-C6HI2
( All data taken from the reference- 79)
Figure II.29b. Saturation solubility of naphthalene
m ) as a function of volume fraction of
plotted ( as -In x2
methylene iodide in solute-free methylene iodide -
cyclohexane mixed solvent. Data at 2 5 ' ~ .
F i g u r e XI .BOO Naphthalene i n c ~ r b o nt e t r a c h l o r i d e -
n .\
cyclohexane mixea s o l v e n t . Y ( i . a . ( l n a; ";
m S
In x2) ) p l o t t e d n s a f u n c t i o n o f volume f r a c t i o n
of cyclohexane ( 0 ) and t h e ef f e c t i v e volume f r a c -
t i o n of c y c l o h e x m e ( @ ) . I n t h i s p l o t t i n g it h a s
been ~ s s w n e dt h ~ t @, FJ 1 . ( see T a b l e I1 .I5

and Table 11.9) Data a t 25 C,

F i g u r e I1 .3l. Naphthalene i n methylene i o d i d e -
cyclohexane nixed solvent. Y (i.e. (In api -
-I

Pn xm ) 2 ) p l o t t e d a s a f u n c t i o n of volume f r a c t i o n
2
of cyclohexane ( ) and e f f e c t i v e volume f r ~ c t i o n

o f cyclohexane ( ). I n t h i s p l o t it has been

assumed t h a t a r e equal t o
unity. ( s e e Table 11-15 ~ n dTable 11.10) A l l data
F i g u r e 11.32. Naphthalene I n carbon t e t r a c h l o r i d e -
i
cyclohexane mixed s o l v e n t . Y / I m ( i.e. ( l n ag -
1
I n xm ) z/Im ) p l o t t e d as a f u n c t i o n of volume f r a c t i o n
2
of cyclohexane ( o ) and as a f u n c t i o n of " e f f e c t i v e
volume f r a c t i o n " ( ) of cyclohexane. Data a t 2 5 " ~ .
( s e e Table 11.13)
Figure 11.83. Ndphthalene i n methylene i o d i d e -
cyclohexane nixed s o l v e n t . Y (i.e. ( I n a ip -
m
I n x~)~/@,) p l o t t e d as a f u n c t i o n o f volume f r ~ c t i o n
of cyclohexane ( 0 ) and a s a f u n c t l o n of e f f e c t i v e
volume f r a c t i o n of cyclohexane ( @ ) . (see T ~ h l e
11.15) A 1 1 d a t a a t 25O C.
 Chapter - 111

Calculation of Entropy of Solution from Scaled Particle Theory

 - 190 -
The s c ~ l e dp n r t i c l e t h e o r y o f f l u i d s i s e s s e n t i ~ l -
l y an e q u i l i b r i u n t h e o r y concerned w i t h t h e p r e d i c t i o n
of t h e bulk thermodynmic p r o p e r t i e s o f f l u i d s o v e r
t h e whole e x i s t e n c e r e p i o n of t h e f l u i d . The c l a s s i c -
a l hard sphere c o n s i s t s of l l f d e n t i c a l v n ~ r t i c l e so r
n o l e c u l e s which m e r i g i d s p h e r e s of dinmeter a , ohey-
i n g c l a s s i c a l mechanical laws. Two such molecules i n -
t e r a c t w i t h one a n o t h e r o n l y when t h e y c o l l i d e e l f i s t i c -
ally. The i n p o r t a n c e o f t h i s model i s due t o t h e con-
s i d e r a b l e mathematical s i m p l i f i c a t i o n i n t h e mmy-body
problem r e s u l t i n g from i t s u s e , a s w e l l 8s i t s useful-
n e s s i n d e s c r i b i n g t h e b e h a v l o u r o f r e a l f l u i d s under
extrene conditions, Thus, a t v e r y h i p h t e m p e r a t u r e s ,
when t h e avernpe k i n e t i c energy of t h e g a s molecule i s
much g r e a t e r t h a n t h e nininum v a l u e of t h e i n t e r n o l e c -
u l ~ p
r o t e n t i a l enerpy, t h e hard c o r e ( o f d i a m e t e r a )
of t h i s p o t e n t i a l enereg i s i m p o r t m t i n d e t e r n i n i n g
t h e p r o p e r t i e s of t h e f l u i d . A t very high d e n s i t y , on
t h e o t h e r hand, t h e ~ t t r a c t i v ep a r t of a more r e a l i s -
t i c i n t e r m o l e c u l a r p o t e n t i n 1 can be thought of a s a
smooth average p o t e n t i a l n o t g r e a t l y a f f e c t i n g t h e prop-
e r t i e s of t h e f l u i d ,
The s c a l e d p a r t i c l e t h e o r y was f i r s t develoned by
R e i s s , F r i s c h and LebowitzC961 i n 1959 and i s mainly
concerned w i t h hnrd spheres. Since then R number o f
p a p e r s and a couple of reviews have concerned t h e n s e l v e s
w i t h v a r i o u s i d e a l i s e d systems such a s h ~ r ds ~ h e r e s ,
 - 194 -
hard d i s c s and one dimensional systems, RS well a s r e a l
f l u i d s , p a r t i c u l a r l y w i t h a t t e m p t s t o provide n u m e r i c ~ l
r e s u l t s which can be compared w i t h t h e experiments.
The s c a l e d p a r t i c l e t h e o r y i s R formal t h e o r y i n
t h e same sense a s c l u s t e r t h e o r y , t h e r a d i a l d i s t r i b u -
C1241
t i o n f u n c t i o n , end t h e Percus-Yerick theory. The sctiled
p n r t i c l e t h e o r y h e s been used t o c a l c u l a t e h e a t o f va-
p o r i z a t i o n , s u r f ace t e n s i o n , nnd h e ~ tc ~ p a c f t i e sof r e a l
f l u i d s . r97-1031 S c ~ l e dp a r t i c l e t h e o r y can a l s o be ~ p -
p l i e d t o f u s e d s a l t s . 104-1061 Besides, s c ~ l e dp a r t i c l e
t h e o r y does n o t need any ad j u s t a b l e p ~ r m e t e r si f t h e
hard c o r e d i m e t e r of t h e molecule i s known. For s i n -
p l e nonpolar l i q u i d s , t h e h e a t of v a p o r i z ~ t i o ncRn usu-
a l l y be used t o c a l c u l a t e t h e hard sphere diameter.
Hard s_nhere d i ~ m e t e r sc a l c u l ~ t e dt h i s way can be used
t o c ~ l c u l a t eo t h e r thermodyn~micp r o p e r t i e s of r e d
l i q u i d s and u s u a l l y t h e c a l c u l a t e d thermodynmic 'prop-
e r t i e s egree w e l l w i t h t h e e x p e r i n e n t n l v e l u e s when
compared.
C 961
From t h e s c n l e d p a r t i c l e t h e o r y R e i s s e t a l . ob-
t a i n e d an e x p r e s s i o n f o r an e q u a t i o n o f s t ~ t ef o r herd
sphere f l u i d s a s f o l l o w s :

where P i s pressure, p i s t h e number d e n s i t y N

-
V'
T i s temperature i n fibsolute s c a l e , k is Roltzm~nn's
c o n s t a n t , and

An e x a c t l y s i n i l ~ re q u ~ t i o nf o r P ( a s i n equa-

t i o n (1) ) was o b t a i n e d by E. Thele [ lo8' and M. S. v e r -

theirn['07] by s i n u l t a n e o u s s o l u t i o n o f t h e Percos-Yerik
e q u a t i o n find t h e Ornstein-Zernike c o m p r e s s i b i l i t y equa-
t ion.['lgl Besides, t h i s e q u a t i o n i s i n r e n a r k a b l e Rgree-
ment w i t h t h e machine c a l c u l a t i o n s o f YJ, W. Wood and
J. D. Jacobson,[ 1201 and o f B. J. Alder and T. E. Wain-

w i g h t .[ le6' The v i r i a l development

where t h e B n t s a r e t h e v i r i a l c o e f f i c i e n t s o f e q u a t i o n
(1)y i e l d s : ( s e e H. L. F r i s c h i n r e f e r e n c e [ 100) )

Equation ( 3 ) compares f a v o u r a b l y w i t h t h e e x a c t v i r i a l
series
- = i + 4y + ioy2 + 18.36 y3
PkT

Compnring e q u ~ t i o n( 3 ) w i t h e q u ~ t i o n( 4 ) one s e e s t h ~ t
t h e f i r s t t h r e e c o e f f i c i e n t s a r e e x ~ c ti n equntion ( 3 )
 -193 -
b u t t h e f o u r t h i s i n e r r o r by 3b w h i l e t h e f i f t h lies
w i t h i n 57; of t h e u n c e r t a i n t y \ 96,971
Attempts t o extend t h e s c a l e d p a r t i c l e t h e o r y t o
r e a l f l u i d s i n an e f f o r t t o d e r i v e t h e i r e q u a t i o n o f
s t a t e h a s n o t met w i t h t h e sane s u c c e s s ~ n dt h i s a s p e c t
of t h e t h e o r y i s s t i l l under develonment. The n o s t
notable contribution i n t h i s f i e l d is t h e perturbntion
t h e o r y of Henderson ~ n d
Barker [122-124,114,1251 where
t h e y t r e a t e d t h e s o f t p a r t of t h e i n t e r m o l e c u l a r poten-
t i a l of f l u i d molecules a s R snall perturbation t o t h e
h ~ r dsphere system.
Recently Lebowitz e t a l . 9 1131 o b t a i n e d ex-

p r e s s i o n f o r t h e e q u a t i o n o f s t a t e f o r hard sphere mix-

tures:

(1
5152
- 53)
2 I-

i n e q u a t i o n ( 5 ) a r e d e f i n e d ns
% ts

where m i s t h e nunber of conponents of t h e m i x t u r e s .

Ri i s t h e r a d i u s of t h e f l u i d p ~ r t i c l e sof i t h con-
ponent .
The s c a l e d p ~ r t i c l et h e o r y 8s developed by H e i s s
and h i s coworkers h ~ been
s used by d i f f e r e n t a u t h o r s
t o c a l c u l a t e d i f f e r e n t thermodynamic p r o p e r t i e s of f l u i d s
and f l u i d mixtures. P i e r o t t i C115-61 used t h e s c n l c d pnr-
t i c l e t h e o r y f o r p r e d i c t i n g t h e s o l u b i l i t y , t h e hent
of s o l u t i o n and t h e p a r t i n l riolar volume of simple cases
i n nonpolar s o l v e n t s ond i n vmter. Elosirn used t h e s m e
t h e o r y t o c a l c u l a t e t h e e x c e s s e n t r o p y o f n i x i n c of s i n -
p l e nonpolar l i q u i d s . The method used b?r Yosin [ 1031
t o c a l c u l a t e t h e e x c e s s e n t r o p y of mixing o f two f l u i d s
w a s derived f r o n t h e entrony o f mixing of two r i p i d
sphere f l u i d s , each a t t h e volume o f t h e corresgondlng
l i q u i d comyonent and t h e r e s u l t ~ n tmixture of t h e h ~ r d
s p h e r e s a t t h e volune o f t h e m i x t u r e o f two r e a l l i q -
uids. Snider e t al. used Longuet-Higpins l and Bi-
dom ' s model t o c a l c u l a t e t h e e x c e s s t h e r n o d y n n i i c
f u n c t i o n s of 10 e q u i n o l a r m i x t u r e s of nonpolnr l i q u i d s
~ n dfound t h a t t h e w r e e n e n t betveen t h e c a l c u l n t e d v a l -
u e s and t h e e x p e r i n e n t a l v a l u e s was ~ e n e r n l l ygood.
Longuet-IIIgpinst and '."lidom1s model may be c o n s i d e r e d a s
fin inprovenent of the t h e o r y develoned by R e i s s e t alC 96 1
a s t h i s nodel h a s f l n i t e conf i ~ u r n t i o n a li n t e r n a l ener-
gy but t h e e f f e c t s of t h e c o n f i ~ u r 8 t i o n a li n t e r n 8 1 ener-
gy on t h e entropy change a r e expected t o b e e i t h e r cfin-
c e l l e d o u t o r t o be v e r y s m l l w i t h r e s p e c t t o t h i s as-
sunptron. We w i l l u s e t h e s c a l e d p a r t i c l e t h e o r y t o
c ~ l c u l a t et h e p ~ r t i a ln o l ~ re n t r o y g change o f 8 solid
s o l u t e d i s s o l v e d i n nonpolar s o l v e n t s .
Method o f C a l c u l a t i o n of P a r t i ~ li[olal Entrony of
solution
A s o u r i n t e r e s t l i e s i n c a l c u l ~ t i n gt h e p a r t i a l
molal e n t r o p y change of a s o l i d s o l u t e when d i s s o l v e d
i n s o l u t i o n , i.e. (g2 - s): , we w i l l devise R ther-
modynmic c y c l e t o d i s s o l v e t h e s o l i d s o l u t e i n t h e
solution. The thermodynamic c y c l e we w i l l u s e i n t h e
following discussion c o n s i s t s o f s i x steps. These s t e p s
can be d e s c r i b e d i n t h e f o l l o y v i n g manner:

S t e p I. Pure s o l i d s o l u t e a t room t e n p e r a t u r e i s con-

v e r t e d t o supercooled l i q u i d a t t h a t temperature. Un-
f o r t u n ~ t e l y ,we cannot use t h e scaled p a r t i c l e theory
i n c a l c u l a t i n g t h e e n t r o p y change involved i n t h i s s t e p
a s it i s w e l l known t h a t s c a l e d p a r t i c l e t h e o r y can n o t
be extended t o t h e s o l i d s t a t e s and it does n o t d e s c r i b e
c o r r e c t l y t h e m e l t i n g p r o c e s s of s o l i d s (even i n a s i n -
p l e ctise l i k e t h e m e l t i n g of s o l i d argon.C 1073 ) * $*,

decided, t h e r e f o r e , t o u s e t h e e x p e r i n e n t ~ lv a l u e t o
c a l c u l a t e t h e e n t r o p y change involved i n t h i s s t e p .
T h i s c m be c a l c u l ~ t e dby t h e usua1 thermodynamic pro-
cedure. Let t h e entropy c h m g e involved i n t h i s s t e p
be denoted AS: where t h e s u p e r s c r i ~ hr e f e r s t o t h e
s t e p nunber, i n t h i s ;I because t h l s e n t r o p y c h ~ n ~ r e
r e f e r s t o t h e e n t r o p y change involved due t o S t e p I ,
S u b s c r i p t 2 . r e f e r s t o t h e s o l u t e , our u s u e l n o t e t i o n
f o r solute.
 Therefore, we see t h a t A S is t h e e n t r o p y of
f u s i o n of t h e s o l u t e a t room temperature. From u s u a l

thernodynamic r e l a t i o n s we f i n d

where AS i s t h e e n t r o p y of f u s i o n a t t h e m e l t i n g
m-p t
point , i s t h e e n t r o p y of f u s i o n a t 298O
Tmp t ;
K; AC;-' i s t h e d i f f e r e n c e of t h e h e ~ ct a p a c i t i e s
between s o l i d m d l i q u i d s o l u t e ; and n2 i s t h e number
of moles of s o l i d s o l u t e .
Besides t h e obvious problem of t h e n o n e p p l i c c i b i l i t y
of t h e s c a l e d p a r t i c l e t h e o r y i n d e s c r i b i n c t h e >recess
of n e l t i n g , t h e r e i s a n o t h e r reRson f o r i n t r o d u c i n g
S t e p I. I n most of t h e s o l i d s o l u b i l i t i e s s t u d i e s , t h e
supercooled l i q u i d of t h e s o l i d s o l u t e e x t r a p o l ~ t e dt o
t h e temperature a t which t h e e x p e r i n e n t was performed
i s t h e s t a n d a r d s t a t e f o r t h e s e s t u d i e s ~ n da l l t h e
t h e r r ~ o d y n a n i cd a t a f o r t h e s o l i d s o l u t e s were c o l l e c t e d
with respect t o t h i s standard s t ~ t e .

S t e p IIi The l i q u i d s o l v e n t and t h e l i q u i d s o l u t e c r e -

a t e d i n S t e p I a r e s e p a r ~ t e l y"dischnrgedw f~tc o n s t n n t

volume t o hard spheres.

L e t t h e entropy c h m g e of t h i s s t e p be denoted by
TT
-where n t s a r e t h e nuaber o f moles, is the
*'charg
e n t r o p y change due t o charging o f t h e hard s p h e r e s t o
r e a l liquids.

Step 111. The h a r d s p h e r e f l u i d s produced i n S t e p I1

a r e now vaporized a t t h a t t e m p e r ~ t u r e . I f t h e vapor

of t h e hard s p h e r e g a s e s a t t h a t t e m p e r a t u r e i s asswled
t o be i d e a l such t h a t POVO = RT , then t h e entropy
change o f t h i s s t e p con be c a l c u l a t e d from t h e s c ~ l e d
p a r t i c l e theory. Yosim o b t a i n e d t h e e n t r o p y of vapor-
i z ~ t i o nof hard sphere f l u i d s a t t h e b o i l i n g p o i n t of
t h e corresponding l i q u i d a s
1: 103 1 . ..

where i s t h e volume of t h e l i q u i d a t t h e b o i l i n g
bpt
point, TrNo where N
C i s --b i s Avogadrots number, a
0

i s t h e hard s p h e r e d i a m e t e r o f t h e i f n u i d , nnd ept

i s t h e volune of t h e s u b s t m c e i n t h e g a s phase and t h e
g a s obeys t h e i d e a l pas l a v .

From t h e t h e r n o d y n m i c r e l a t i o n s h i p , t h e e n t r o n y
of v a p o r i m t i o n a t 298' X i s plven by
 - 198 -
where TB i s t h e b o i l i n g p o i n t and AC*-g
P is the differ-

ence of t h e h e a t c a p a c i t i e s o f l i q u i d and vapor nhnse.

I n w r i t i n g equntion (lo), we assumed that, t h e A C4.4-g
P
i s independent of t h e t e u p e r a t u r e .
The A t-g
C ~ f o r l i q u i d s cRn a l s o be c ~ l c u l ~ t e d
from t h e s c a l e d p ~ r t i c l et h e o r y of t h o f l u i d s . The
C1021
~ ~ 4 - igs g i v e n by
P

where ad i s t h e c o e f f i c i e n t o f t h e r m ~ le x p a n s i v i t y of
t h e l i q u i d , and 3
ca,

T h e r e f o r e , combining e q u n t i o n s ( 1 0 ) and (11),

The renson we used f o r t h e r e a l l i q u i d (i.e. the

at
c o e f f i c i e n t of t h e t h e r m ~ le x p a n v i v i t i e s of t h e l i q u i d )

find n o t a hnrd s p h e r e l i q u i d i s due t o t h e f ~ c tth n t

 - 199-
we a r e c a l c u l ~ t i n gt h e h m t o f v a p o r i z ~ t i o nn t t h e b o i l -

i n g p o i n t ~ n d8 s we m e w i n e t h e e x p e r i m e n t ~ l l yd e t e r -
mined V
B P ~
, w e have t o u s e a
4,
t o be c o n s i s t e n t i n
out calculations.

IV.
S t e ~ The i d e ~ lhnrd s p h e r e wises produced i n S t e p
111 a r e mixed ~t c o n s t a n t p r e s s u r e . If' we essunle t h a t

t h e n i x i n g i s i d e a l t h e n t h e entropy of t h i s s t e p i s
g i v e n by
AS" = -n 1R in x 1 - n2 R i n x2 (14

where x ' s a r e the mole f r a c t i o n s .

S t e n V. The m i x t u r e of t h e hard s p h e r e s i s cornpressed

t o t h e v o l u ~ eof t h e s o l u t i o n . The entropy of t h i s
s t e p cnn be d e r i v e d from L e b o n i t z f s e q u a t i o n of s t a t e
f o r a m i x t u r e of h m d s p h e r e s and i s given by ( s e e Ap-
pendix A I I I . 1 )
Step VI. The compressed m i x t u r e s of t h e r i c i d s y h e r e s
a r e f f r e c h a r q e d , wi . e . the internolecular a t t r ~ c t i v e
p o t e n t i a l i s brought back and t h e r e p u l s i v e p o t e n t i a l
i s changed t o t h a t of t h e s o l u t i o n . Then, t h e e n t r o p y
change o f t h i s s t e p i s

S i n c e we a r e i n t e r e s t e d i n nonpolar Z i a u i d s , it i s r e a s -
onable t o essume t h a t t h e e n t r o n y change due t o charg-
i n g and d i s c h a r g i n g i s v e r y small m d t h e d i f f e r e n c e
between charping pure components and s o l u t i o n w i l l be
v e r y small, o r i n o t h e r words we can assume

The e x c e s s entropy i s d e f i n e d a s

where Asrn i s t h e t o t a l entropy of mixing. Collecting

a l l t h e entropy changes involved from S t e p I t o S t e p
V I and s u b t r a c t i n ? fro!? t h e n t h e i d e n 1 entropy o f solu-
t i o n , one o b t a i n s t h e e x c e s s e n t r o ~ yof t h e n i x i n g , AsE
I f t h e s o l u t i o n i s d i l u t e w i t h r e s p e c t t o component 2,
i.e. s o l u t e , t h e n any term i n v o l v i n g x1x2 o r m y high-
e r power of x2 c?a be n e e l e c t e d ~ n de q u a t i o n ( 1 7 )
simplifies t o

AS* = n2hs1 + nlR i n V1€59 P + n2R in 9 9 P

- "lRl n ( < , B p t - ca:) - n2R i n ( $ 9 P - caz)

 Substituting % = nlvl + n2;fi2 where B s a r e t h e
p a r t i a l molal volune and t h e n d i f f e r e n t i a t i n g e q u ~ t i o n
(18) w i t h r e s p e c t t o n2 and t h e n c o n v e r t i n g t h e equa-
t i o n f o r l mole of mixture, i.e. N1 + N2 = 1 , one
obtains t h e e x c e s s p a r t i a l molal entronv of connonent

-
V, - ca,3

Equation ( 1 9 ) i s f u r t h e r s l n p l i f i e d f o r a v e r y
d i l u t e s o l u t i o n a4 we a r e i n t e r e s t e d i n a very d i l u t e
s o l u t i o n where x2 i s of t h e o r d e r of
For a very d i l u t e s o l u t i o n , - or the p a r t i d
m o l ~ lvolune of s o l v e n t i n t h e s o l u t i o n can be t ~ k e n
fis equal t o V1 o r t h e molal volune of p u r e solvent.
a t t h a t t e m p n r ~ t u r e , and 8s d i l u t e s o l u t i o n x2 i s very
s m a l l , e q u a t i o n ( 1 9 ) becomes

A s we have assumed b e f o r e , t h e vapor behaves RS

an i d e ~ g
l as so t h a t vg o r t h e volu!!e in the RRS phase

can be c a l c u l ~ t e dfrom t h e & d e a l (?as l a w , i e e e .W = RT .

E q u ~ t i o n ( 2 0 ) g i v e s t h e e n t r o p y of s o l u t i o n a t
constant pressure. This equation WRS applied t o c ~ l c u -

late A o r t h e p ~ r t i a ln o l a l e n t r o a y o f s o l u t e a t

constant pressure f o r I2 , s , s ~ ( c ~ HRnd~ ) ~

S~(C~F,-=
i n) ~t h e fo1lo:ving solvent,^: ( i ) CS2 , (ii)
toluene, ( i i i ) CC12F.CF2C1, ( i v ) CC14 , ( v ) rn-xylene,
( v i ) iso-octane, ( v i i ) C2H2Clg .
For Sn( Q F ~no) ~e x p e r i m n t a l v a l u e s f o r AS' ere
knovrn. Elowever t h e d i f f e r e n c e between t h e e x p e r i m e n t ~ l
P
and t h e o r e t i r n l AS2 v a l u e s f o r ~ n ( Q ~ ~ ) iR - rienn g e

of s o l v e n t s should be a c o n s t ~ n tv ~ l u e( i . e . the v ~ l u e

of AS' which i s given by

 - 204 -
The o t h e r s o l i d s o l u t e which h a s been s t u d i e d
is % e m pe-rfluosophenyl tin , and f o r t h i s con-
pound no l i t e r a t u r e v a l u e f o r boil-inp p o i n t i s e v a i l -
able. Also t h e value f o r entropy o f f u s i o n a t room
t e n p e r a t u r e i s n o t known. For t h i s s o l u t e vre decided
t o c n l c u l a t e only AS^ + AS: and s u b t r a c t it f r o n t h e
experimental vnlue of AS^ P
.
T h i s should ftive R v ~ l u e
I 'I1 , which would be c o n s t a n t f o r a par-
f o r AS2 + ASp
t i c u l a r solute.
I n Table 111.2 a l l t h e c a l c u l a t e d v a l u e s f o r
2
a r e coripared w i t h t h e experiment e l v a l u e s .
In Table 111.1 we g i v e t h e v a l u e s of hard s p h e r e
d i ~ m e t e r sused i n t h i s c a l c u l a t i o n .

Discussion
From t h e d a t ~p r e s e n t e d i n Table 113.2, i t can be
seen t h a t ~(rreernentbetveen t h e calculatect v a l u e s m d
e q e r i n e n t n l v a l u e s f o r I2 and sn14 i s extrenely
pood. These a r e t h e o n l y two s o l i d s o l u t e s f o r which
a l l t h e n e c e s s a r y d a t a a r e ~ v n i l a b l e-- p a r t i c u l ~ r l y
h e a t of v a p o r i z a t i o n , entropy of f u s i o n , LC:-' , i.e.
t h e d i f f e r e n c e of hent c a p a c i t i e s o f s o l i d ~ n dl i q u i d
s t ~ t eo f t h e s o l u t e . For S a 4 , t h e entropy of f u s i o n
~t 298O K was token a s 9.1 ell as c ~ l c u l ~ t ebyd l i i l d e -
brnnd e t a l . For i o d i n e t h i s v e l u e was cfilculeted from
t h e d a t a g i v e n by Hildebrand e t a l . a n d found t o be 8.4 eu.
Hildebrand' s Hegulw S o l u t i o n t h e o r y ( s e e C h ~ p t e rI )
d e a l s w i t h t h e entropy of mix in^ ~t c o n s t m t v o l u r e which
i s r e l ~ t e dt o t h e entro?y of mixinc ~t constant, p r e s s u r e
(which we a r e i n t e r e s t e d i n ) by t h e e q u a t i o n

where AS: i s t h e p a r t i a l n o l a l entropy of s o l u t r o n

a t c o n s t a n t volume, AS; i s t h n t a t constant nressure,
($$4V t h e i s o c h o r e of t h e s o l v e n t e t c o n s t a n t v o l -
is
-E i s t h e excess p a r t i 8 1 m o l d volume of t h e
m e , and V2
solute i n solution.
It i s c l e a r t h a t t h i s method cRn be used t o c a l -
culate V because a l l o t h e r q u a n t i t i e s i n e q u ~ t i o n
AS2
(15) a r e u s u a l l y o b t ~ i n e dfrom t h e e x p e r i n e n t a l r e s u l t s . ,

Or, i f t h e scaled p a r t i c l e theory p r e d i c t s cor-

2
r e c t l y , then one i s ~ s s u r e dof o b t ~ i n i n ca c o r r e c t v a l u e
for A a s long 8s e q u ~ t i o n( 2 1 ) is v a l i d . In the
cnse of i o d i n e , it has been observed t h a t when V
AS^
is plotted gain st -R in xg one o b t a i n s 8 strnight
l i n e whose i n t e r c e p t i s e q u a l t o 9.1 eu and s l o p e i s
equal t o 1.1 i n c o m p ~ r i s o nt o t h e expected V A ~ U ~8.4
S

and 1.0 r e s p e c t i v e l y . O r i n o t h e r words, ~ l t h o u ~t hhe

A ~ z l sAre n e n r l y i d e n 1 f o r i o d i n e n s shovm by J. Iiild-

e b r ~ n de t a l . , t h e excess entrony even a t c o n s t n n t vol-
ume i s n o t e x ~ c t l yzero. A s mentioned e e r l i e r , we m e

not dealing w i t h . I n t h e cnse o f i o d i n e it, i s

shown i n Table N . 2 t h ~ tt h e agreement between t h e ex-
 mixing can be applied t o t e t r a p h e n y l t i n - orcanic sol-
vent systems. I n Table 111.2 w e p i v e t h e v a l u e of I
bS2
for s ~ ( c ~ H
c a l~c u)l a~
ted i n t h i s fashion i n d i f f e r e n t
o r g a n i c s o l v e n t s . Except f o r t h e t o l u e n e -
s~(c~H,-)~
-1 v a l u e s d e t e r n i n e d i n t h i s f ~ s h l o na r e r e a s -
s y s t e n , AS,
onably s e l f - c o n s i s t e n t even though we ~ s s u m e di n S t e p
I T t h a t t h e entropy o f mixing two i d e a l h ~ r dsphere g a s e s
i s ideal.
The a b i l i t y t o p r e d i c t such a l a r e e e x c e s s e n t r o ~ y
i n t h i s c a s e i n i=m i n t e r e s t i n c f e a t u r e o f t h e e n t r o n y
c y c l e vie have used t o c e l c ~ ; . l a t ep a r t i a l molal entropy
of t h e s o l u t e because i n t h i s c a l c u l ~ t i o nt h e e f f e c t of
t h e volume d i s p a r i t y between t h e s o l v e n t and s o l u t e
does not need t o be considered.
For . s ~ ( c ~)F
5 4
, a s mentioned e a r l i e r , we c a l c u l e t e d

AS: + -I1
AS, by s u b t r a c t i n g AS'I1 + AS': + AS,V + AS,VI
from t h e experimental A . The c e l c u l a t e d v a l u e s f o r
-11 f o r s ~ ( c
AS: -I- AS2 ~ Fi n~d i) f f~e r e n tsolvents a r e
a l s o gLven i n Table 111.2. A s before, -11 f o r
AS: + AS,
R s o l u t e should he c o n s t a n t i r r e s p e c t i v e of t h e s o l v e n t s .
T h i s i s observed i n t h e case o f S n ( c F ) for differ-
6 5 4
e n t o r g a n i c s o l v e n t s a s shown i n Table 111.2.
Considerine: t h 8 t no ~ l l o w a n c ef o r v011~nled i f f e r e n c e
on t h e entropy of mixing was mnde i n t h i s c a l c u l a t i o n ,
it i s i n t e r e s t i n g t o n o t e t h a t t h e e n t r o p y c y c l e we used
here may be ~ p p l i e ds u c c e s s f u l l y i n c a s e s where t h e
r a t i o of t h e s o l u t e - s o l v e n t molar v o l m e i s a s l a r e e
a s five. C o n s i d e r h e t h e s u c c e s s of ~ p p l y i n pt h i s en-
t r o p y c y c l e i n predict in^ such a l m e e e x c e s s e n t r o p y ,
it s e e m that; f o r s p h e r i c e l molecules t h e l a r p e e x c e s s
entropy of mixing may n o t be due t o molar volume d i f f e r -
ences alone.
Going back t o Table 111.2 again, we can see that
T

f o r tetraphenyl t i n t h e AS; c a l c u l a t e d bv t h e proce-

d u r e d e s c r i b e d Above i s r e ~ s o n n b l yc o n s t a n t except f o r
t o l u e n e , where t h e c ~ l c u l a t e de x c e s s entropy i s nuch
l a r g e r t h a n t h e e x p e r i n e n t a l one, VJe have no d e f i n i t e
i d e a a s t o why t h e t o l u e n e - SnPh4 system d e v i a t e s t o
[ 1291
such a l a r g e e x t e n t . It h a s been suggestea t 6 t SriPh4
forms a complex w i t h benzene, a l t h o u g h no such s t u d i e s
have been r e p o r t e d f o r t h e t o l u e n e - SnPhq system; it
may be t h a t SnPh4 a l s o forms a complex with t o l u e n e .
I n t h a t c a s e t h e s e c a l c u l a t i o n s do n o t have any mean-
i n g f u l s i g n i f i c m c e because t h e y a r e based on t h e Assunp-
t i o n t h a t molecules i n t e r a c t ~ c c o r d l n gt o t h e hard s p h e r e
-

p o t e n t i a l and t h e "chareingW and lvdischarpingTv

proces-
ses have almost n e g l i g i b l e e f f e c t on t h e e n t r o p y of t h e
solution. T h i s i s n o t t h e c a s e where more s p e c i f i c
interactions a r e present.
For ' t e t r a ~erfluoro~henyl
tin the situation
becomes more complicated. A s nent ioned e a r l i e r t h e

- + AS2
entropy change f o r AS I'' i s n o t known, So
2 98
we looked f o r R c o n s t m t v ~ l u eof
AS I''
+AS2 for
298
SnPf by t h e nethod d e s c r i b e d e a r l i e r . The c a l c u l a t e d
perimental A ~ n dt h e A calculnted i r o n t h e scaled
p a r t l c l e theory a r e i n good a g r e e n e n t , it i s c l e n r from
e q u ~ t i o n(15) t h ~ t ~3:~shave t o be i n good nprennent,
provided equntion (15) i s v a l i d .
The d i f f e r e n c e between t h e method d e s c r i b e d h e r e
t o c a l c u l ~ t et h e e n t r o p of t h e mixinft and Refsular Sol-
u t i o n t h e o r y i s t h a t i n t h i s method we Rssumed t h a t t h e
entropy of mixing i s i d e a l when two i d e a l hard s p h e r e
g a s e s a r e mixed, whereas i n Regular S o l u t i o n t h e o r y it
was assumed t h a t t h e entropy of mixing i s i d e e l when
two l i q u i d s a r e n i x e d , A s mentioned e a r l i e r , t h e two
s o l i d s o l u t e s which have been s t u d i e d e x t e n s i v e l y i n
t e r n s of t h e Regulm S o l u t i o n t h e o r y do seen t o have
a v e r y small e x c e s s entropy,
Rut f o r t e t r ~ p h e n y lt i n : t h e e x c e s s entropy o f
mixinp, i s q u i t e l a r g e and a s shotvn by V i t o r i a m d i'!al)r-
ley, t e X e g u l a r S o l u t i o n t h e o r y b r e a k s down f o r t e t r a -
L54'h

phenyl t i n - o r ~ a n i cs o l v e n t systems due t o t h e l a r c e

e x c e s s e n t r o y of mixing. 'de were unnble t o c a l c u l a t e
the AS: f o r s ~ ( c ~ Hi n~d)i f f~e r e n t s o l v e n t s due t o
t h e u n a v a i l ~ b i l i t yof n e c e s s m y d a t a t o c s l c u l a t e t h e
entropy of f u s i o n f o r ~ nc( ~ H ~a t )298O
~ K, i , e . ~3: .
But RS A i s c o n s t ~ n tf o r t h e s o l u t e i r r e s p e c t i v e
-I
of t h e s o l v e n t s , we s h a l l be nble t o c a l c u l ~ t e AS2 by

the experiment~l A -- and t h i s v ~ l u ef o r AS: should

be a c o n s t ~ n ti f t h i s method of c a l c u E ~ t i n ce n t r o p y of
 - 2'09 -
'I1
values of AS
2 98
+ AS2 come to be constant within a
few per cent ( which can be cosidered to be good).
f
But as there is exact method by which can be
f
seperated from As298 + AS2I11 , this procedure is not
very helpful in calculating the excess partial molal
entropy of mixing of Sn(C F ) in organic solvent.
6 5 4

Conclusion
In this chapter we showed that the scaled particle
theory can be used in calculating the partial molal entropy
of mixing of a solute and we also showed that the calcu-
lated*valuesof As2P are in good agreement with the expe-
rimental values. But as the major contributions in calcu-
P f
lating h S p come from AS298 ( the entropy of fusion
IV (-R in x2), a more critical
at 289'~) and from AS2
test of the method of calculation will be the comparision
of calculated and experimental values of excess partial
molal entropies. For solids , we shall compare the calcu-
-P
lated and the experimental values of rAS2Iexcess where
-P -P
[~S21
excess is dfine as AS2 + R i n x2. We subtracted

~'&38
-P
from r hs21 because hS2g8 cannot '
be calculated from the scaled particle theory and moreover
its contribution to A is quite lqrge ( approximately
8 eu. ). In table 111.3, we give both calculated and
 experimental values for [ ~ z- ]
s'
298
~
for I2 and
It can be seen from Table 111.3 that the calculated
~
SnI4.
- values are not widely different from the experimental
values. Within the limits of the assumption of a hard
sphere interaction potential and the uncertainty involved
in calculating hard sphere diametersC 1151 , the results
can be considered to be good. These results could prob-
ably be improved by using a more realistic interaction
potential. Until a rigorous method is developed using
the scaled particle theory approach for a realistic in-
teracting potential allowing the equation state to be
formulated, no real improvement is possible. [1181
After completion of this work, a paper was published
by Benson et a1[1261, where they used the perturbation
theory as developed by Barker and Henderson[291 to cal-
culate the heat of mixing and the entropy of mixing for
nonelectrolyte solutions. They showed that the perturbation
of hard sphere potential does not affect the entropy of
mixing, i.e. the entropy of mixing of two nonelectrolyte
I

liquids in absence of any specific interactions is equal

to the entropy of two hard sphere fluids -- a conclusion
similar to our assumption that the entropy change during
the "chargingf'and "discharging" processes cancel out
each other.
 Table 1II.l
Hard sphere d i ~ n e t e r sof d i f f e r e n t s o l v e n t s and s o l u t e s :
( s e e Aypendix -4IV.1 f o r t h e methods o f calcu3.rltion)

a x 1.0-u a
v a l u e s used abHV8 a a@
inthis x 10- x lo-8
calculation
cm cm cm

toluene 5.46 5 .46 5.42

m-xylene 5.77 5.77 5.75

4,42 4,42 4.33
CS2

( &bvts a r e t h e hard s p h e r e d i m e t e r s c a l c u l a t e d f r o 3
t h e h e a t of v a p o r i z a t i o n d a t a by S n i d e r - H a r r i n g t o n ' s
equation; aa a r e t h e hard sphere d i n n e t e r s c a l c u l ~ t e d
from thermal e r p n n s i v i t i e s d a t n ; a $ ' s a r e t h e hard
sphere d i m e t e r s c a l c u l a t e d from t h e c o e f f i c i e n t of
isothermal corlpressibility d ~ t a )
 - 2,12 -
Table fII.2

P
AS2 f o r d i f f e r e n t nonpolar b i n a r y mixtures:

System

c-C6H12 - I2
CC14 - I2
CC12F .CF2C1 - I2
CS2 - I2
i-octane - I2

CC14 - Sn14
toluene - Sn14
CC12F.CF2C1 - SnI4

c-c6H12 - SnPh4

toluene - SnPh4 " + 19.45

CC12F. CF2Cl - SnPh4 \ " + 25.0

,-C6H12 - SnPf4 I1 + I1
+ 9.31
(ASI+ASI~'
= 24.10)
33.41

toluene - SnPf4' 11 + 11
+ 5.55 30.22
(AsI+AsII'
= 24.65)

isooctane - snPf4 " + " + 5.8

( A S'+A s"'
29.0
= 23.2 )
 Table - 111.3
A comparision of excess partial molal entropy of
solution for solid solue calculated by means of equation-
(20) of chapter I11 with those determined experimntally.

-P
System -R 3.n x2 ~ ~ ~ ~ 1 rAS2~excess
~ , ~ ~ ~
2 98
- @JI2 98 -4s1
( c a l c Td) ( experimental)
 Table ." 111.4

Saturation solubility of Sn(C6 F 5 ) 4 at different temperature.

Solvent

toluene

isooctane
 - 2'15 -
Table 111.5

Values of v2 and A 3; for Sn(C6F5)4 - organic solvent

systems:

Solvent V2 in cc.rnole-' A 5;

CC14

~-~6*12
toluene
isooctane
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Appendix A I , 1
Important T h e r n o d v n ~ n i cR e l a t i o n s

%z heat capacity a t constant volume

= cav
e heat capacity a t constant p r e s s u r e
C~

= cap
a E c o e f f i c i e n t of thermal expansion

= + ($%, (A1.1*3)

fl z c o e f f i c i e n t of i s o t h e r m a l c o m p r e s s i b i l i t y

(A1.1 .4)

a (AIele5)

We ~ l s o
used t h e t e r n " f u g ~ . c i t y ?d~e s i g n n t e d by f l

Tho f u p a o i t y i n two s t n t e s A and B is related t o

t h e rnolal f r e e energy i n t h e s e s t ~ t o sby t h e e q u a t i o n

A sumnary of r e l ~ t i o n sbetween thermodynnnic f u n c t i o n s

 - 225 -
A c t i v i t y and Choice o f S t m d a r d S t a t e
The o t h e r i n p o r t a n t t h e r n o d y n m i c q u a n t i t y we have

u s e d i s t h e ~ c t i v i t y ,d e s i g n a t e d a s a . The a c t i v i t y
a o f a substance i n a p a r t i c u l a r s o l u t i o n i s t h e r a t i o
of i t s f u g a c i t y i n t h a t s o l u t i o n t o i t s f u g a c i t y i n
some a r b i t r a r i l y chosen s t a n d a r d s t a t e which i n t h i s
t h e o r y i s always p u r e l i q u i d . F o r s t a n d n r d s t n t e a0 =

1 w h i l e i n any o t h e r s t a t e it i s p i v e n by .

where s u p e r s c r i p t o d e n o t e s s t a n d a r d s t ~ l t eand
i s t h e chemical p o t e n t i a l i n m y g i v e n s t a t e .
Any s t e t e c m be chosen a s t h e s t m d a r d s t a t e .
Thus f o r nqueous s o l u t i o n e l e c t r o l y t e s t h e i n f i n i t e

d i l u t e solution of t h e e l e c t r o l y t e is usually selected

a s s t a n d ~ r ds t a t e . Rut i n t h i s work, o n l y t h e p u r e
l i q u i d w i l l be c o n s i d e r e d a s t h e s t a n d ~ r ds t a t e . For
s o l i d , t h e standard stcite i s t h e pure h y n o t h e t i c a l l i q -
u i d s u p e r c o o l e d below t h e n e l t i n g p o i n t . This standard
s t a t e was ~ c c e p t n dby ~ i l d e b r a n d L
241
The e d v a n t a c e o f t h i s c o n v e n t i o n i s t h a t it y i e l d s

e q u a t i o n s o f same form f o r a 1 1 components and a v o i d s a

d i s t i n c t i o n between s o l v e n t and s o l u t e . To d i s t i n y u i s h

t h o s o l u t e , ~ i l d e b r n n d ru s~e~d ~subscript 2 . In this

 - 226 -
work, sone n o t a t i o n s w i l l be used t o d i s t i n g u i s h s o l u t e
in R solution -- i r r e s p e c t i v e o f whether it i s a b i n a r y
o r t e r n ~ r yn i x t u r e ,

A c t i v i t y of S o l i d s
A s s o l i d s o l u t e i s used i n a l l experiments a e n t i o n e d

i n t h i s work, and RS t h e pure l i q u i d h a s been t ~ k e na s

t h e standard s t a t e , one needs t o knov t h e ~ c t i v i t yof
a s o l i d substance which i s given by

I n denline; with t h e s o l u b i l i t y of s o l i d s , sometimes it

i s i n p o r t a n t t o know i t s ~ c t i v i t yr e f e r r e d t o t h e hypo-
t h e t i c a l l i q u i d supercooled below the m e l t i n g p o i n t .
The t h e r n o d y n m i c r e l a t i o n s h i p

(where AH^ i s the h e a t of f u s i o n a t t h a t t e m p e r a t u r e

T ) can be i n t e g r a t e d from temperature T t o t h e nel-
t i n e point T, under t h e a s s u n p t i o n t h a t t h e h e a t of
fusion i s constant, giving
 - 227 -
where t h e d i f f e r e n c e between the n o l a l h e ~ tc ~ p a c i t i e s
o f l i q u i d ~ n ds o l i d a r e known t h e n

C~
- CpS = ACp arnd AH^ = bHm
F
- AC~(T, - T) (~1.1~11)

where AH: i s t h e h e a t of f u s i o n of t h e m e l t i n g p o i n t ;

:C i s t h e heat capacity of l i q u i d ;
i s t h e heat capacity of t h e solid.
c;
S u b s t i t u t i o n of e q u a t i o n ( A I . l . l l ) i n e q u a t i o n (AI.1.9)
and i n t e g r a t i o n of e q u a t i o n ( 9 0 ) y i e l d s

Equation (AI.l.12) r e d u c e s t o e q u ~ t i o n( A I . 1 . 1 1 ) when

i s z e r o , o r i n o t h e r words, t h e h e a t o f f u s i o n i s
A C~
c o n s t ~ n t ,t h e assumption which h a s been invoked i n d e r -

i v i n g equation ( A I . l . l O ) .
Again r e w r i t i n g e q u a t i o n (AI.1.10), one o b t a i n s

o r it AC i s z e r o , t h e n p l o t t i n e of in as v e r s u s
P
11 T should gLve R s t r a i g h t l i n e .

However, i f AC i s n o t z e r o nnd f o r o t h e r y i r n o s e
P
which w i l l be e x p l a b e d l ~ t e r ,it i s ~ d v a n t a n e o u st o
plot log a s (or log x2 ) versus log T . The l i n -
e a r i t y of such R curve cr\n be t e s t e d i n t h e f o l l o w i n g

manner :
 - 228 -
The e q u ~ t i o n ( A I . l . l O ) is rewritten as

Then t ~ k i n gt h e second d e r i v a t i v e w i t h r e s p e c t t o
one o b t a i n s

A t t h e melting p o i n t , T, , AH,F = TAS,F , so t h e second

d e r i v ~ t i v ewould be z e r o (and t h e c u r v e s t r n i ~ h t ,a t
l e ~ s ta t t h i s p o i n t ) f f AS: i s equal t o A C ~ . T~ble

AI.1.3, compares and AS: f o r a group o f s o l i d

A C~ -
sol.utes. The r a t i o o f A CP to A S r a n g e s from 0 . 4 -GI

t o 2.1, which does n o t s u p p o r t t h e ~ s s u z l p t i o n ACp = AS; ,

but, c e r t a i n l y t h i s assumption i s b e t t e r t h a n ~ s s u m i n g

F
In a -
ASm 1
s( ~ 1 . 1 . 1 5 )
- R and In as w
R *m
 Tnble AI.1.Z
Therr~odynanic F u n c t i o n s f o r F u s i o n M I

Substance AS: ( c a l l deg) ACp ( c a l l deg) h C p / bSm

F

Consequently, log T instead of -

T
TVRS used by
Hil-debrand e t zl. f o r g r a p h s b u t t h e as is corrected
if ACp i s known. I n t h i s d e r i v a t i o n , it h a s been
assuned t h a t AC i s c o n s t a n t which i s n o t an e x a c t
P
c o n d i t i o n and t h u s even i f A C Is known, t h e v a l u e s
P
f o r a: Rre s u b j e c t e d t o R c e r t a i n d e g r e e of u n c e r t a i n t y
p a r t i c u l a r l y a t a t e r z p e r a t u r e ftir below t h e m e l t i n g

point. 3 u t it h a s been o b s e r v e d t h a t a p l o t of log x2

versus log T gives straight l i n e s in the repion x2 <
r-,Lt
0.1 h her ens l o g x2 versus -
T curved 1i n e s t h r o 1 l ~ h o ~ 5 i - a
 - 230/-
T a b l e AI.1.2
Thermodynamic F u n c t i o n s f o r Fusion l 2 4 1

F F
Suhstmce ASm ( c a l l deg) ACp ( c a l l deg) ACP/ AS,

Consequently, log T instead of T was used by

Hildebrand e t e l . f o r g r q h s b u t t h e as i s corrected
if A C ~ i s known. I n t h i s d e r i v a t i o n , it h a s been
assumed t h a t AC i s c o n s t a n t which i s n o t an e x a c t
P
c o n d i t i o n and t h u s even i f A C Is known, t h e v a l u e s
P
f o r as a r e s u b j e c t e d t o a c e r t a i n d e g r e e o f u n c e r t a i n t y
2
p ~ r t i c u l ~ r la yt a t e r ~ p e r a t u r ef a r below t h e m e l t i n g

point. g u t it h a s been observed t h n t a p l o t of log x2

versus log T g i v e s s t m i g h t l i n e s i n t h e r e ~ ~ o xn <
2
0.1 vherens l o g x2 versus -T curved l i n e s t h r o u e h o u t C241 .
Measures of Connosition
The cornnosition of a s o l u t i o n c m be exnressed
in A v n r i e t y of ways, e . ~ .
(1) c o n c e n t r ~ t i o ni n p r m s o r n o l e s p e r u n i t volune;
( 2 ) t h e r ~ t i oof t h e nunber of moles of one com-

ponent of a b i n a r y s o l u t i o n t o t h e nunber of moles of

t h e second cormonent, i.e. 111 ;
n2
(3) nole f r a c t i o n , i s t h e nost extensively
used u n i t of e x p r e s s i n g t h e s o l u b i l i t y of n o n e l e c t r o -
l y t e s i n solution. The n o l e f r ~ c t i o n xi o f any con-
ponent i i n s o l u t i o n i s d e f i n e d 8s

evidently xl + x 2 + m e +xi = 1

o r i n t h e case o f b i n a r y s o l u t i o n ,

X1 + x2 = 1

and dxl = -dx2 ( A 1 . 1 .18)

( 4 ) volune f r e c t i o n @ . The Pi , volune fr~ction

of any conyonent, i s given by

A s mentioned e a r l i e r , t h e volune o f n s o l u t i o n i s n o t
e q u a l t o t h e sun of t h e volumes of i t s components but
 - 231 -
it i s t h e f r a c t i o n sum of i t s ~ a r t i a nl o l n r volunes.
Thus

I f one assumes t h a t voluiie change due t o mixing

i s m a l l , t h e volune f r a c t i o n Qi o f t h e ith coflpon-
e n t i s given by

where v i s t h e molar volume o f p u r e l i q u i d conmon-

ents .
Throughout t h i s work volume f r a c t i o n a s d e f i n e d
by equntion (AI.1.21) w i l l be used i n s t e n d o f t h e vol-
ume f r a c t i o n d e f i n e d i n t e r n s of p a r t i a l molal volumes
AS i n e q u a t i o n (~1.1.20). The advantage of u s i n g t h e
volune f r a c t i o n a s t h e measure of c o n p o s i t i o n of a x i x -
t u r e i s t h a t t h e u n i t of volune f r a c t i o n t ~ k e scrrre of
t h e d i f f e r e n c e i n n o l ~ rvolumes o f d i f f e r e n t c o ~ ~ o n e n t s .
Since t h e d i f f e r e n t l i a u i d s nay have d i f f e r e n t
c o e f f i c i e n t s of thermal e r p a n s i o n , t h e volllne f r a o t Lon
w i l l be s l i p h t l y dependent on t h e t e n ? e r a t u r e , b u t t h i s
dependence w i l l be n e g l e c t e d i n t h i s vork because t h e
t e n p e r n t u r e rnnge used i n t h i s work i s very s n ~ 1 1 .
Appendix A1 .2
Repulsive Forces

A s mentioned e a r l i e r , t h e i n t e r r a o l e c u l ~ rp o t e n t i a l
may be w r i t t e n a s

It i s w e l l known t h a t p o t e n t i a l e n e r m of R moleculnr
p a i r p a s s e s throueh a minimum a t which dU = 0 .
T h i s c o n d i t i o n nay be used t o d e f i n e a d i s t m c e
ro
and a minimum ( n e g a t i v e ) energy c0 . Differentiation
of equation ( A I , 2 , 1 ) w i t h r e s p e c t t o r plives

I f one s e t s t h e d e r i v a t i v e e q u a l t o z e r o , t h e r e s u l t i n g

equntions f o r Yo end c0 ere

which i s t h e e q u ~ t i o nused i n t h e t e x t f o r
€0
Appendix AII.1
Derivntion of Excess Volume of fix in^, A
VE,M
7

We d e f i n e d
 - 2-34. -
O r f r o n (AII.P.S),

S i n i l n r l y from t h e e q u a t i o n ( A I I . l . 4 ) ,

Again we d e f i n e -E,M
AV2 i.e. t h e e x c e s s term i n t h e t e x t

as

1 3
= -V;[A; - (11~, + $9, (AI1.1.8)

Denoting 11~,
1
+ m3~, 3 = ,A M,1,3 we o b t a i n e q u a t i o n ( 5 6 )

i n the text. S u b s t i t u t i n g e q u a t i o n (AII.I.6) nnd ( A I I .

1.7) i n equation (AII.1.8) we o b t a i n

2
= ~ g [ ( @ ~ n+ ~@3n3$3)62
$~

2
- 262(@1"18161 + @ 3n3B 36 3) - nmPmb2

+ (@1n1~16
2 1+ @ 3n 3p 3b 32 )
and s u b s t i t u t i n g ( A I I . l . l O ) i n e q u a t i o n (A11.1.9),

The equation ( A I I . 1 . 1 1 ) i s equivalent t o equation ( 6 5 )

i n the text. Notv i f we assume t h a t

nmpm6; = n 16 16 1 + n 3p 36 32

t h e n long with t h e assumption made i n e q u a t i o n ( A I I .

1 . 1 0 ) , t h e e q u a t i o n (AII.1.9) reduces t o
Again w r i t i n g

and t h e n s u b s t i t u t i n g e q u e t i o n ( A I I . 1 . 1 3 ) i n equation
(AII.1.12) we o b t a i n

The e q u a t i o n (AII.1.14) i s equivalent t o equation (64)

i n t h e text.
 1 *
A A (ln):x = 1
* - *
@1)(62 - h3)
2

and

Adding 1 i n both t h e sides of t h e e q u a t i o n (AII.2.4)

Dividing

to e *l , 1
we s e e t h a t t h e maximum v a l u e for -a
A *(ln )x:
w i l l occur a t
S u b s t i t u t i n g equation (AII.2.6) i n t h e equation ( M I .
2.8) w e o b t a i n

Rearranging t h e equation (AII .2.9) ,

2
= { (62 - + l y l
(a, - a l l 2
 - 239 -
Appendix AII.3

The s o l u b i l i t y e q u ~ t i o ncan be w r i t t e n a s

t v r it i n g o
6m = + @3b3

such t h a t

S u b s t i t u t i n g equation ( A I I . 3 . 3 ) i n t h e equotion ( A I I .

S u b s t i t u t i n g e q u a t i o n (AII.3.4) i n e q u ~ t i o n( A I I . 3 . l ) ,

Differentiating
m
in x2 + @;(a,
with respect t o
-
b312}
@; and t h e n
w r i t i n g t h e c o n d i t i o n f o r maximum, we o b t a i n
 *
S i n i l a r l y , i f one w r i t e s 6, i n terms of , then

*
R e c a l l i n g t h e r e l a t i o n s h i p between and @; , i.e.

we o b t a i n
@y'si n equation (AII.3.0) t o (AII.3.10) a r e t h e cor-
.L

*,mx
responding P: value of
Entropy of Compressing n I f i x t u r e o f I i i c i d Syheres

For a b i n a r y raixture of hard s p h e r e s Lebowitz,

C"2J
Helfand and P r a e s t p ~ m d e r i v e d t h e f o l l o n i n p e q u ~ t i o n
of s t a t e f r o n t h e s c a l e d p a r t i c l e t h e o r y :

where nNi
'i =T

and

I n t h e above e q a t i o n s , P is t h e pressure a t
tenperature T find volume V, k i s B o l t z n a n n ' s con-
stant, pi i s t h e number d e n s i t y Ni/ V and ai is
t h e herd sphere d i a n e t e r of' i .
If e q u a t i o n s A I I I . 1 . 2 and A.III.3 are substit-
u t e d i n e q u a t i o n ~.111.'1,1 ~ n dt h e n , n u l t i p l y i n g n u m r -
a t o r md denoninator by v3 , one obt~ins

where A = rr(Nla: + N2a2) 6

Thus the entropy of t h e compression i s piven by

.
( A - 111. 1 5 )

S u b s t i t u t i o n of e q u a t i o n A I I I . 1 . 4 i n equation
~ 1 1 1 ~ 1 . 5 followed by i n t e g r a t i o n y i e l d s

+( +
2 ~ 4BA]v1 I/ 2(v1 - a12

- [(D - CA - 3 ~ ~ +
2 () 2 ~ BA)v,]/ + 2(v2 - a)2}(~1~1.1.6)

The constants D - CA + J B A ~find 2 C + ~ B A are:

- 4 2
+ 6"1a2)
3 3

- N1N2(6aZaZ - 2 4
3ala2

Gala;) - 3 6
3N2a21 (~111.1.7)

nnd 2C + 4AB = n[N;a: + ~ ~ ~ ~ (":a2) +

a ~ +$a:~.~111.1.8)
a :
 The conpression i s c a r r i e d o u t f r o n t h e volune o f
t h e gaseous s o l u t i o n Vl = vgS t o t h e volune of t h e
liquid solution V2 = :V . As V1 i s l e r g e , t h e scc-
ond t e r n i n e q u a t i o n AIII.1.6 can be n e g l e c t e d . Fur-
t h e r , i n t h e f i r s t term A ( :V . Equntion A I I I . 1.6
c m be converted t o n o l e q u m t i t i e s i f one w r i t e s down

where i s Avogadrol s number, x r s a r e t h e mole f r a c -

No
t i o n s , and n Ts e r e t h e number of n o l e s .
 - 245 -
Appendix A I I I . 2
C a l c u l ~ t i o nof Hard Sphere D i ~ f l e t e r

The most important p a r t i n any t h e o r y on h m d sphere

f l u i d s i s t h e choice of a meaningful v a l u e f o r hard
sphere diameter, I n e a r l i e r c a l c u l a t i o n s , workers h ~ v e
used t h e e q u i l i b r i u m d i s t a n c e a a l c u l ~ t e df o r Lennard-
Jones p o t e n t i a l RS t h e hard sphere d i ~ n e t e rwhich i s
a c t u a l l y a bad choice because of t h e f a c t t h a t t h e re-
p u l s i v e p a r t of Lennard-Jones 6:12 p o t e n t i ~ li s n o t 8s
steep RS t h e hard sphere p o t e n t i 8 1 and t h e e q u i l i b r i u m
d i s t a n c e i n t h a t c a s e cRn n o t be equated w i t h t h e hard
sphere p o t e n t i a l .
used hard sphere diameter c a l c u l a t e d from
s u r f a c e t e n s i o n , t h e c o e f f i c i e n t o f i s o t h e r m a l conpres-
s i b i l i t y and t h e c o e f f i c i e n t of thermal e x p a n s i v i t y o f
€1151 I3181
l i q u i d s . P i e r o t i and S n i d e r c a l c u l a t e d hard sphere
diameter from t h e hefit of v a . p o r i z ~ t i o no f t h e l i q u i d s .
From s c a l e d p a r t i c l e t h e o r y , t h e c o e f f i c i e n t of
isothermal compressibility p o f a l i q u i d i s given by
4

S i n ~ i l a r l yt h e c o e f f i c i e n t of thermal e x p a n s i v i t y of a
l i q u i d i s given by
whereas S n i d e r e t a1.C118] c a l c u l a t e d h e a t o f vrrporiz-
a t i o n of n o r n a l l i q u i d from L o n c u e t - H i e ~ i n s ~
model and
d e r i v e d an e x p r e s s i o n

AH; 1 + y + y 2
-= + 1
NkT
(1 - y)3

The s u r f a c e t e n s i o n a of a l i q u i d i s related t o Y as

The hard sphere diameter h a s a l s o been c a l c u l ~ t e dfrom

t h e v i s c o s i t y of t h e d i l u t e gas, (qi)gas as

where a i s t h e hard sphere diameter, m is the m 8 s s

and k i s Roltzmm-mTs c o n s t a n t .
I n t h i s connection it s e e n s t h a t t h e c h o i c e of t h e
c o e f f i c i e n t of thermal e x p a n s i v i t y o f r e a l l i q u i d s w i l l
be EI bad c h o i c e because t h e ~ t t r ~ c t i vf oer c e s a r e n o t
considered i n t h e s c a l e d p a r t i c l e t h e o r y of R e i s s , F r i s c h
C961
and Lebowitz but t h e y e n t e r i n t o t h e t h e o r y i n t h e den-
s i t y and t h e thermal e x p a n s i v i t y of t h e l i q u d.
p o l lT h i s
raises R p o i n t which v r ~ smentioned e ~ r l i e r ,t h a t i n t h e
s c a l e d p ~ r t i c l et h e o r y , t h e e q u ~ t i o nof st,n%e of R renl
l i q u i d i s n o t knovm. Hence t h e c o e f f i c i e n t of t h e r m ~ l
e x p m s i v i t y and t h e d e n s i t y of t h e l i q u i d can n o t be
c n l c u l ~ t e db u t h ~ v et o be measured.
 - 247 -
For t h e r e n n i n i n g t h r e e methods, t h e r e i s no reRson
t y p a r t i c u l ~ rone g i v e s t h e b e s t
f o r supposing t h ~ m a
velue. But i f t h e s e d e r i v a t i o n s e r e c o r r e c t , t h e n a's
d e t e r n i n e d by t h e s e t h r e e methods should n o t he v e r y d i f -
f e r e n t from each o t h e r , Next t h e problem l i e s w i t h t h e
n o n s p h e r i c ~ lmolecules and t h e p h y s i c 8 1 meaning o f a in
t h a t case. H e i s s e t a l . suggested t h ~ it f t h e molecules

a r e n o t t o o bedly n o n s p h e r i c ~ l , due t o t h e e f f e c t of
r o t a t i o n a l everaging it i s p o s s i b l e t o h ~ v ea meaning-

f u l v a l u e of a .
Another a s p e c t t h e t h a s t o be emphasized i s t h a t
i n t h e scaled p n r t i c l e theory, a i s t r e a t e d ns con-
s t a n t ~ n ddoes not, v a r y w i t h t h e t e m p e r a t u r e . This
assumption l e a d s t o an i n c o r r e c t t e n p e r a t u r e dependence
for .
at [ lo*] B e s i d e s , S t i l l i n e m o a l c u l n t e d t h e ef-
f e c t i v e v a l u e of a f r o n t h e compressibility ~ n dd e n s l -
t i e s of t h e molten s a l t s and observed t h a t a decre~ises

with temperature. 14ayer noted t h z t t h e surfnce

C961
t e n s i o n equntion d e r i v e d by R e i s s e t a l . a l s o h a s an
i n c o r r e c t t e n p e r a t u r e dependence. IIe suggested thfit
a ought t o d e c r e n s e w i t h t e m p e r a t u r e r a t h e r t h a n r e -
mein c o n s t a n t . This decrease of a with tempercture
o r i g i n n t e s f r o n t h e f a c t t h n t w i t h I n c r e n s i n g temper-
a t u r e , t h e a b i l i t y of t h e n o l e c u l e s t o p e n e t r a t e one

m o t h e r ' s r e p u l s i v e f i e l d i s n o r e e f f e c t i v e l y due t o

t h e i n c r e a s e i n t h e avernge t h e r m a l m e r c y . A real

molecule hns, i n f a c t , 1
8 ' s o f t t , not R (hardp repulsive

p o t e n t i ~31.
 - 248 -
But t h e problem s t i l l remains what numerical v a l -
u e s can be accepted f o r a 8s a r e a s o n a b l e v a l u e .
Ye chose t o c a l c u l a t e a v ~ l u e sfrom t h e hent of vanor-
i z a t i o n a t t h e b o i l i n e p o i n t where t h e v a l u e f o r h e a t
of v a n o r i z a t i o n i s known by g e m s of t h e equation of
ma1
S n i d e r e t a1. Also we have c ~ ~ l c u l a t e da v n l u e s f r o n

8,
But RS we a r e i n t e r e s t e d i n t h o s e s o l u t e s which
Are s o l i d a t room terilperature and i n most of t h e cfises,
f o r t h e rqolten s o l i d s a r e n o t knovm, f o r t h e sake
@
,

of c o n s i s t e n c y w e ? r e f e r r e d a v ~ l u e scfilculnted from
t h e h e e t of v a p o r i z ~ t i o nc a l c u l a t e d f r o n e q u a t i o n A I I I .
2.3 . I n t h e c a s e of s o l u t e s , where h e ~ of
t v~porize-
t i o n dctta Rre not known, we a r e f o r c e d t o u s e a C R ~ -

c u l a t e d from t h e at of t h e molten s o l i d above m e l t i n g

point.
I n t h e case where a v a l u e s a r e a v ~ i l a b l ef o r
both h e s t of v ~ p o r i z a t i o nand t h e c o e f f i c i e n t of i s o -
t h e r m l comnressibi-1-ity, it can be seen ih t h e t a b l e
below t h a t a v a l u e s d e t e r n i n e d bv b o t h t h e n e t h o d s
a r e c o r ~ p a r a b l e . So i n a l l t h e f o l l o w i n g c ~ l l c u l a t i o n s
we used a v ~ l u e sc ~ l c u l ~ t ef rdo n t h e h e a t s of vanor-
i z a t i o n f o r both s o l v e n t and s o l u t e excent i n such cnses
a s t e t r a p h e n y l t i n and t e t r ~ k i s~ e n t ~ f l u o rnhenyl
o tin
when a values R r e c ~ l c l r l n t e dfrom t h e
a&
The a .
v a l u e s i n t h e s e calcult-itions n r e ~ s s u n e dt o be indapen-
 - 249 -
dent of t h e temperature because a ' s a r e involved d i -
r e c t l y b u t t h e y m e involved a s Y and any c h ~ n ~i ne
a will have R v e r y small e f f e c t on Y .
Also, i n t h i s c a l c u l ~ t i o n ,we used t h e ex-perinent,al
values f o r $' and ad i n s t e n d of t h e c a l c u l a t e d v a l u e s
due t o r e a s o n s mentioned e a r l i e r ,
\+?eh ~ v er e j e c t e d t h e method o f d e t e r x i n i n g a by

v i s c o s i t y due t o t h e f a c t t h n t t h e v i s c o s i t y d a t a g i v e s
some v e r y u n r e ~ s o n ~ b lvea l u e s f o r a .