Chapter 4. Activity Coefficient Models. Part 1.

Random-mixing
based models
Problem 1. Azeotropes with the one-parameter Margules equation
The molar excess Gibbs energy for some simple (symmetric) binary systems can be
represented by the one-parameter Margules equation, where B is a parameter
characteristic of the mixture:
!
x Bx g
E
"#"$
i# %how that the acti&ity coefficient of component 1 is gi&en as:

!
ln x
RT
B

"#"'
(hat is the &alue of the acti&ity coefficient at infinite dilution of the component 1)
ii# *ssume that the &apor phase is ideal and that the system is at low pressures# %how,
using the one-parameter Margules equation, that at e&ery temperature for which an
a+eotrope exists (concentration where y=x for all components), the a+eotropic
composition of compound ! x1
az
and the a+eotropic pressure P
az
are related by the
following equation:
, !

!
!
) , ln(
) , ln(
!
!
1
]
1

+
sat az
sat az
az
P P
P P
x
"#-.
Problem 2. Henrys law constants and ininite dilution acti!ity coeicients
*t /.. 0, some experimental data are a&ailable for dilute liquid mixtures of components
! and # (hen ! is dilute in an excess of , the 1enry2s law constant is H1,23 bar# (hen
is dilute in an excess of !, the 1enry2s law constant is H2,13!#4. bar# 5stimate the
&apour composition, which is in equilibrium with an equimolar liquid mixture of ! and
at /.. 0# *ssume that the &apour is an ideal gas# *t /.. 0, the pure-component &apour
pressures are !#.6 bar for pure liquid ! and !#// for pure liquid #
(hy can2t we use the one-parameter Margules of the pre&ious problem)
Hint: Assume the validity of a simle t!o"a#amete# a$tivity $oeffi$ient model e%g% van
&aa# o# 'a#gules t!o"a#amete##
Problem ". #omparison with e$perimental data
The &apour-liquid equilibrium data reported in Table "#4 ((mehling et al%, )ao#"li*uid
e*uili+#ium data $olle$tion, 7echema 8hemistry 7ata %eries, 7echema, 9ran:furt, 1%&%)
are for the system acetone (!),cyclohexane () at -
o
8# *ssume for simplicity that, at the
low pressures in&ol&ed, we ha&e ideal &apour beha&iour#
!
'able (.). ;<5 of acetone (!),cyclohexane () at -
o
8#
Pressure
*mmHg+
$1 y1 Acti!ity
#oeicient o
compound *1+
Acti!ity
#oeicient o
compound *2+
'6#"- .#. .#.
!!$#.- .#.!!- .#!$!.
!6#'. .#.-6- .#"-$.
-/#'. .#"/- .#4$..
-'#". .#-64. .#6.-.
-#.. .#'-. .#$-$.
"/#$. .#'4- .#'!4.
/.#". !#.... !#....
i# 8alculate the experimental acti&ity coefficients of the two compounds and complete
the table abo&e# 7o we ha&e positi&e or negati&e de&iations from =aoult2s law)
ii# >se a single experimental data point (at ?3-/#' mm 1g) to estimate the parameters
of an acti&ity coefficient model and then calculate the equilibrium pressure and
&apour compositions at liquid acetone concentrations: .#.!!-, .#-64. and .#'4-#
?repare a table showing for these three compositions the percentage de&iations
between calculated and experimental acti&ity coefficients (for both components),
equilibrium pressures and &apour phase mole fractions# 8ompare the results to the
experimental data and comment on the results#
Hint% ,o# the van &aa# e*uation, sho! that the a#amete#s A and B fo# a +ina#y system
$an +e o+tained using the a$tivity $oeffi$ient values fo# the t!o $omounds using the
e*uations:

ln
ln
ln
ln
! ln

,
_

1
]
1

+
x
x
B A
x
x
B

"#-!
Problem (. 'he !an ,aar equation
i# %how that the two forms of the &an <aar equation @equations "#' and "#!.A are
equi&alent# (hat is the &alue of

!
ln using the two forms of the &an <aar
equation )
ii# %how that when the &an der (aals parameters are obtained from the critical
point, then $
P
(where is defined as in equation "#')#
iii# 8hlorine (

$
P
6#6! M?a) and carbon tetrachloride (

$
P
"#-4 M?a) form an
ideal solution# Bn the other hand, carbon disulfide (

$
P
6#' M?a) and
methanol (

$
P
$#!. M?a) split into two liquid phases# 8an the &an <aar
equation explain these obser&ations )

i&# %tarting from ( )

! !
+ g
E
deri&e the expression for the acti&ity
coefficient (eq# "#') for a binary mixture (+ is the mixture co-&olume
parameter and is defined as in equation "#')# The CsegmentD fractions are
defined in equation "#' and Table "#"#
Hint: -ho! fi#st that the ex$ess (i++s ene#gy fo# the van &aa# e*uation $an +e
!#itten as:
( )

!
! !

+
+ + x x
g
E
"#-
Problem -. .-actors or distillations using the /egular 0olution 'heory *Modiied
rom Prausnit et al.
)
+
9or distillation-column design, we need 0 factors (.i=yi/xi)# * liquid mixture at -.
o
8
contains /. molE n-hexane and 6. molE ben+ene# *t -.
o
8, the pure component &apour
pressure of n-hexane is .#-// bar and of ben+ene is equal to .#/$. bar#
!# 8alculate the 0 factors of n-hexane and ben+ene in this mixture# *ssume that the
pressure is sufficiently low to neglect gas-phase corrections and ?oynting factors#
Then calculate the relati&e &olatility of hexane,ben+ene#
# (hat would be the relati&e &olatility assuming an ideal liquid solution)
The molar &olumes and solubility parameters are presented in Table "#6#
'able (.&. Molar &olumes and solubility parameters for n-hexane and ben+ene (all &alues
at -
o
8)#
#ompound 1olume *cm
"
2mol+ 0olubility parameter
*3 cm
-"
+
122
n-hexane !/ !"#'
Fen+ene $' !$#$
Problem ). Azeotropes with the /egular 0olution 'heory *Modiied rom Prausnit
et al.
)
+
* binary liquid mixture contains the non-polar components ! and # The mixture is to be
separated by ordinary distillation# To determine if this is feasible, it is necessary to :now
whether or not the mixture has an a+eotrope# The pure component &apour pressures at
/.. 0 and the solubility parameters are gi&en for the two compounds in Table "#$# The
pure-component molar &olumes are for both compounds equal to !4. cm
/
,mol# *t /.. 0,
does this mixture ha&e an a+eotrope) Gf so, what is its composition) *ssume that the
&apour phase is ideal# (hat would the result be if both liquid and &apor phases are
considered ideal )
'able (.4. ?ure component &apour pressures and solubility parameters at /.. 0 for the
two components#
/
#ompound 1apor Pressure *5Pa+ 0olubility parameter
*3 cm
-"
+
122
(!) -/#/ !"#/
() $. !6#"
Problem &. 6sing azeotropic data to predict 1,7 or a binary mi$ture 0,#om
-andle#, -%1%, 2hemi$al and Enginee#ing The#modynami$s 03
#d
edition4% 5ohn 6iley 7
-ons, 18884
Fen+ene and cyclohexane form an a+eotrope at .#-- mole fraction ben+ene, temperature
of 66#4
o
8 and a total pressure of !#.!/ bar# *t this temperature the &apour pressure of
pure ben+ene is .#''/ bar and that or pure cyclohexane is .#'$. bar#
i# >sing the &an <aar model, estimate the acti&ity coefficients of ben+ene and
cyclohexane at liquid mole fractions (ben+ene) .#., .#, .#-, .#$ and !#.# >sing this
acti&ity coefficient information, compute the equilibrium pressure &ersus liquid and
&apour composition at the same temperature#
ii# Ma:e predictions for the acti&ity coefficients of ben+ene and cyclohexane using the
regular solution theory and compare these with the results obtained in question (i)#
;olume and solubility parameters of ben+ene are gi&en in problem -, while for
cyclohexane they are !.' cm
/
,mol and !4#$ (H,cm
/
)
!,
#
Problem 4. 8nterrelations between models 9 :eri!ations
!# %tarting from the expression of the regular solution theory for multicomponent
systems using li93., deri&e the expression for binary systems (equation "#!!)#
# The excess Gibbs free energy equation of the &an <aar equation is prior to the
assumption of any mixing rules gi&en as:
+
a
x g
i
i i
E

,
_

"#-/
8onsider a binary mixture# 7eri&e the expression for the acti&ity coefficient of
compound (!) in the following cases (types of mixing rules):
i#

i
i i
x
"#-"
ii#

i 9
i9 9 i
x x
9 i i9

"#--
iii# the classical &an der (aals one fluid mixing rules for the energy and co-&olume
parameters (a,+) using also the well-:nown geometric mean combining rule for the
cross energy parameter and the arithmetic mean rule for the cross co-&olume
parameter (equations /# and /#/ in 8hapter /)# *ssume that all interaction parameters
(:i9 and li9) are equal to +ero#
8omment on the results and mention examples of mixtures your three models can
potentially be applied to#
Problem %. Permeability o pharmaceuticals through polymers using the /egular
0olution 'heory
"
%tarting from 9ic:2s law:
dx
d2
; 5
"#-4
7eri&e the equation for the permeability of pharmaceuticals through polymers using the
9lory-1uggins,=egular solution theory, according to 'i$haels et al#
-
(equation "#-):
[ ]
max
ln exp(! ) ! ln ( )
f
m
-
T
5 l ;
R T

_
+ +

,
"#-6
where the maximum attainable flux of a pharmaceutical through the polymer is gi&en by:
l
2 ;
5
I
max
#
"#-$
; is the diffusion coefficient, l is the thic:ness of the film and 2
<
is the concentration of
the pharmaceutical in the polymer at equilibrium with crystalline solid steroid#
Hint: -ho! fi#st that the ,H e*uation fo# the a$tivity of the ha#ma$euti$al at ve#y lo!
solu+ilities $an +e given +y the e*uation: ) ! ( ln ln
! ! !
+ + a #
Problem 1;. 0creening o sol!ents or pharmaceuticals using the regular solution
theory */0'+
i# %tarting from the expression for the acti&ity coefficient of =%T (liJ3.) for
multicomponent systems:
( )

!
ln
av i
i i
m
av
i i
i
)
RT

_


,

"#!!
deri&e the expression for a binary mixture (components ! and )
ii# (hat are the expressions for the infinite dilution acti&ity coefficients of compounds 1
and 2 )
iii# %how that in the case of solid-liquid equilibria, the (real) solubility of a solid () in a
liquid (!) is gi&en by the equation:

ideal
#eal
x
x
"#"
i&# 0olar et al#, (,luid Phase E*uili+#ia, 2;;2, 18="18>, 66!-6$) and *bilds:o& and
B28onnell (1nd% Eng% 2hem% Res%, 2;;", =2, -4--4/") ha&e illustrated how the =%T can
be used for screening sol&ents for pharmaceuticals# The :ey concept deri&ed from =%T is
that (at low solute concentrations) the solubility x2 is a parabola with respect to the
solubility parameter of the sol&ent
!
with a maximum located at:
!
@

is the
solubility parameter of the pharmaceuticalA# Gllustrate this by showing that for the =%T
and for low solute () concentrations, the following equation is deri&ed:
-

,
_

,
_

,
_

ln ln
RT
)
x
RT
)
RT
)
x
&
id
& &
"#-'
9igure "#!. shows the lnx -
!
plot of hydrocortisone at '$#!- 0# The enthalpy of
fusion, liquid &olume and melting point of this solid are /"#$6 :H,mol, .#'/ m
/
,:mol and
"$-#- 0, respecti&ely#
<igure (.1;. ?lot of lnx -
!
of hydrocortisone at '$#!- 0# 9rom *bilds:o& and
B28onnell (1nd% Eng% 2hem% Res%, 2;;", =2, -4--4/")# =eprinted with permission from
*merican 8hemical %ociety (../)#
i# calculate the ideal solubility at '$#!- 0 and pro&ide, based on the plot, an
estimate of the solubility parameter of the solid#
ii# what is the solubility of hydrocortisone in carbon tetrachloride, based on the
plot and on the equation shown in this problem)
iii# 5xplain, with reference to figure "#", why =%T performs well for morphine
but not for the other pharmaceutical#
Problem 11. ,,7 with the regular solution theory
%how for the =%T that a mixture of two components (1and 2) will gi&e two liquid phases
if ( $
T
3 critical solution temperature):
( )
( )

!
/
! !

! !

) x ) x
) ) x x
RT
$
"#4.
4
!
! !

!
!
) )
) ) ) ) )
x

+
"#4!
(hat are the <<5 conditions if the two components ha&e equal liquid &olumes)
Problem 12. 8ninite dilution conditions
i# 9or polymers, weight fraction acti&ity coefficients are often used:
!
!
!
!

"#4
%how that, for a binary sol&ent(!),polymer() solution, the infinite dilution acti&ity
coefficients of the sol&ent based on molar and weight fractions are related &ia the
equation:

,
_

! !
'
'

"#4/
where M! is the molecular weight of the sol&ent and M is the molecular weight of the
polymer#
ii# 9or the ben+ene,?GF(-.... g,mole) solution with sol&entKs weight fraction equal to
.#.-4" and molar acti&ity coefficient
!
3.#//'4, show that:
- the mole fraction of the sol&ent is equal to .#'6"-#
- the acti&ity of the sol&ent is equal to .#//!#
- the weight fraction acti&ity coefficient of the sol&ent is equal to -#$4$#
Problem 1". 0olubility Parameters
i# Mixed %ol&ents
8ellulose nitrate (!.#6 1) is insoluble in both ethyl ether (6#" 1) and ethanol (!#6
1)# 8an this polymer be soluble in a mixture of the two ) (hy,(hy not ) *t which
composition) (the &alues in parentheses are the solubility parameters in 1ildebrand
units, i#e# cal
!,
,cm
/,
)#
ii# 1ansen solubility parameters
* polymer has a solubility parameter equal to '#'- (with dispersion, polar and
hydrogen bonding parts equal to 6#., -#. and -#.) and a solubility =adius equal to /#.#
Gs it certain that a sol&ent with a solubility parameter equal to !. ($#., 4#., .#. are the
dispersion, polar and hydrogen bonding parts, respecti&ely) will dissol&e it)
(hy,(hy not)
The solubility parameter and radius &alues are in 1ildebrand units, i#e# cal
!,
,cm
/,
#
Problem 1(. 0olubility o mi$ed sol!ents in commercial paint resins - An industrial
case
Mixed sol&ents are often used in the paints and coatings industry# The choice of suitable
sol&ents is often based on the three-dimensional 1ansen theory# 9or a mixed sol&ent, the
solubility parameter is gi&en by the equation:
6

i
i i

"#4"
where i

is the &olume fraction of the sol&ent i and i

are its solubility parameters

(either total solubility parameter or the 1ansen solubility parameters: h p d
, ,
)#
9or two resins, a polyester resin :nown as 7esmophen (product of Fayer) and an epoxy
resin :nown as 5pi:ote !..! (product of %hell) and for two possible sol&ents, n-butanol
and xylene, the 1ansen solubility parameters are gi&en in Table "#'#
The solubility radius is for the polyester resin equal to R3$# and for the epoxy resin is
R34#.#
i# *re the two resins soluble in xylene)
ii# Gs the polyester resin soluble in a mixed sol&ent composed of n-butanol,xylene with
$.E &olume fraction of xylene)
iii# Gs the epoxy resin soluble in a mixed sol&ent composed of n-butanol,xylene with --E
&olume fraction of xylene)
i&# 5xplain briefly the results#
The solubility parameter and radii &alues are in 1ildebrand units, i#e# cal
!,
,cm
/,
#
Hint: The +asi$ e*uation !hi$h dete#mines the solu+ility #ange a$$o#ding to Hansen?s
method is: ( ) ( ) ( ) R
h h d d
+ +

!
" "#4-
'able (.%. 1ansen solubility parameters for 7esmophen and 5pi:ote !..! for two
possible sol&ents, n-butanol and xylene#
#ompound
d

n-butanol 6#$ #$ 6#6

Lylene $#6 .#- !#-
5pi:ote !..! '#'- -#$$ -#4!
7esmophen !.#-/ 6#/. 4#.
Problem 1-. 7!aporation o isopropanol rom a P1A# ilm *Modiied rom
Prausnit et al.
)
+
* film of poly(&inyl acetate), ?;*8, contains traces of isopropanol# 9or health reasons,
the alcohol content of the film must be reduced to a &ery low &alue: go&ernment
regulations require that that the &olume fraction of isopropanol should obey the
relationship:
"
!
!.

# To remo&e the alcohol, it is proposed to e&aporate it at !-

o
8#
*t this temperature, chromatographic experiments, which are carried at infinite dilution
of alcohol, gi&e a &alue of the 9lory-1uggins parameter equal to .#""# The &apor pressure
of alcohol is "#"' bar# *ssuming that the ?;*8 is of &ery high molecular weight,
calculate the low pressure, which must be maintained in the e&aporator to achie&e the
required purity of the film# (hat would the &alue of pressure be if i) the 9lory-1uggins
parameter is assumed equal to +ero (near-athermal solution), ii) if the solution is assumed
ideal#
$
8omment on the results#
Hint: @nde# the $onditions #evailed he#e, the a$tivity of the solvent is simly given as
the #atio of the a#tial #essu#e to the solvent vao# #essu#e and the olyme# is assumed
to +e $omletely non"volatile#
Problem 1). 'he <lory-Huggins model
i# %how that, for the 9lory-1uggins model, one of the most widely-used models for
polymers, the molar-based acti&ity coefficient at infinite dilution is, for a binary
solution, gi&en by the equation:

+ +
!

!
!
! ln ln
)
)
)
)
"#44
7eri&e also the infinite dilution acti&ity coefficient expression for compound (!) in a
binary solution for the 5ntropic-9; combinatorial-9ree ;olume term (equation "#!')#
ii# *t the critical solution temperature, the following conditions apply:
.
ln

"#46a
.
ln

"#46b
7eri&e the following equations for the critical 9lory-1uggins interaction parameter and
the critical &olume fraction:
#
$#it
+

!
!
"#4$a

!
!
!

,
_

+
#
$#it
"#4$b
(hat are the &alues of the critical &olume fraction and 91 parameters for ChighD
polymers (i#e# polymers of high molecular weight))
Hint: @se the ,H model !#itten fo# the solvent a$tivity as:

! ! !
!
! ln ln +
,
_

+
#
"#4'
Problem 1&. Are phthalates completely miscible in P1#=
There are, especially in the recent years, many debates regarding the use of phthalates
li:e 7B? (dioctyl phthalate) as plastici+ers in se&eral polymers and especially ?;8
(poly&inyl chloride)# ?lastici+ers are added in ?;8 because they can lower the glass
transition temperature of the polymer, but it has now been established that 7B? and other
plastici+ers sometimes migrate to the surface# This phenomenon results to the destruction
of the plastic material and may cause health problems as well, since certain phthalates are
considered to be dangerous chemicals (carcinogenic)# Tables "#!. and "#!! present &alues
of the 1ildebrand and 1ansen solubility parameters, the 1ansen solubility radius as well
'
as the 9lory-1uggins parameters for ?;8 and 7B?# 9igure "#!! shows how the 9lory-
1uggins parameter for ?;8,7B? depends on concentration, according to %u et al#, (5%
Al% Polyme# -$i%, 1%&), 2A, !.--!./")#
Bn basis of this information, can we conclude that 7B? is completely soluble (miscible)
in ?;8) (Gf yes, this would imply that the cause of 7B? migration $annot be fully
explained by thermodynamics)# Hustify your answer#
'able (.1;. %olubility parameters of ?;8 and 7B? (all &alues are gi&en in 1ildebrand
units 3 (cal,cm
/
)
!,
) from &arious sources: *#9#M# Farton# 2R2 Hand+oo: of olyme#"
li*uid inte#a$tion a#amete#s and solu+ility a#amete#s# 8=8 ?ress, !''.M 8#M# 1ansen#
Hansen -olu+ility Pa#amete#s% A @se#?s Hand+oo:% 8=8 ?ress, ...#
#ompound total
!alue
dispersion polar hydrogen
bonding
/-Hansen
7B?-! 6#'"
7B?- $#' $#!" /# !#-
?;8-! '#/!"
?;8- !!#./ '#" "#- /#- /#
?;8-/ !.#"' $#'! /#4$ "#.$ !#6
'able (.11. 9lory-1uggins (91) parameters for the ?;8,7B? system obtained from
&arious measurements#
/eerence ' *
o
#+ <H parameter
7oty and Nable -/ .#.!
64 .#./
*nagnostopoulos et al# !!4-!!$ -.#./
.#.4 - extrapolated from
swelling data
Figg .#.-
?atel and Gilbert !!/-!!" -.#!/
?#M# 7oty, 1#%# Nable, 5% Polym% -$i%, 1%(), 1, '.M 8#5# *naglostopoulos, *#O# 8oran, 1#=#
Gamrath, 5% Al% Polym% -$i%, 1%);, =, !$!M 7#8#1# Figg, 5% Al% Polym% -$i%, 1%&-, 18, /!!'M
%#;# ?atel, M# Gilbert, Plast% Ru++e# P#o$ess Al%, 1%4), B, /!#
Problem 14. 'he <lory-Huggins model
9or the polymer solution cyclohexane (!) , polystyrene () @?%A the 91 parameter is
a&ailable at sol&ent &olume fraction
!
3.#4. and it is
!
3.#6# The density of
cyclohexane is .#6-6-x!.
/
:g,m
/
and the density of the polymer is .#!."$x!.
"
:g,m
/
#
The a&erage molecular weight of ?% is -'.. g,mol# *ll data are reported at the same
temperature (3/6/#!- 0)#
!.
i# 5stimate the acti&ity of the sol&ent as well as the acti&ity coefficient of the sol&ent
(based on weight fractions) at sol&ent weight fraction !13.#--# (hat is the percentage
de&iation as compared to the experimental &alue
!
3!#$. reported by 0rigbaum
and Geymer, 5% Ame#% 2hem% -o$iety, 1%-%, C10C4, !$-'-!'-')
ii# 5stimate the 91-parameter &alue so that the experimental acti&ity coefficient &alue
(at w!3.#--) is reproduced#
<igure (.11. The 9lory-1uggins interaction parameter for the ?;8,7B? system ( /

) as
a function of concentration (&olume fraction of ?;8)# 9rom %u, ?atterson and %chreiber
H# Al% Polyme# -$i%, 1%&), 2A, !.--!./"# =eprinted with permission from (iley
(!'64)#
Problem 1%. Pressure o a polymer solution using <lory-Huggins *<rom Prausnitz et
al.
)
+.
5stimate using the 9lory-1uggins model, the total pressure of a liquid solution containing
-.E (weight-based) poly&inyl acetate (with molecular weight equal to $/".. g,mol) and
-.E &inyl acetate (molecular weight 3 $"#! g,mol) at !-
o
8# *t this temperature, the
density of the polymer is !#!! g,cm
/
and that of the sol&ent is .#6$/ g,cm
/
# The &apor
pressure of the sol&ent is //". Torr (mm1g)# 9rom experiments, we :now that the ratio
of the pressure to the sol&ent weight fraction at infinite dilution, i#e# the so-called 1enry2s
law constant is !$#/ bar:
+a#
!
P
! / # !$ ) . lim(
!
!

1
]
1

(hat is the most important assumption in&ol&ed in the calculations)

!!
Problem 2;. 8ninite dilution acti!ity coeicients !ia <lory-Huggins
*shworth and ?rice, ('a$#omole$ules, 1%4), 18024, /-$-4/) published the 9lory-
1uggins interaction parameter &alues for the system ben+ene (!) , polydimethylsiloxane
() at &arious concentrations and at temperature T 3 /.
o
8#
i# 5stimate the acti&ity and the weight-fraction acti&ity coefficient of the sol&ent at
&olume fraction
!

3.#.!4-# *t this concentration the &alue of the 91 parameter is

.#6/!6#
ii# ?ro&e that, for the 9lory-1uggins model, the molar-based and weight-based acti&ity
coefficients at infinite dilution are gi&en by the equations:
!

!
!
! ln ln + +

)
)
)
)
"#6.
and

,
_

# '
'
#
!
! exp
!
!
!

!

"#6!
iii# 5stimate the &alues of the abo&e two acti&ity coefficients at infinite dilution of the
sol&ent (at molar basis and weight-fraction basis)
7ata:
sol&ent: density 3 !!#!! g,cm
/
, molecular weight36$#!! g,mol#
polymer: density3.#'-/ g,cm
/
, a&erage molecular weight3//-. g,mol#
Problem 21. 0electi!e dissolution
%electi&e dissolution is a separation process which has been proposed for recycling of
polymers# The separation is possible because the indi&idual polymers in a mixture of
different polymers are dissol&ed in different sol&ents# * typical mixture of polymers is
composed of polyethylene (?5), polystyrene (?%) and poly&inylchloride (?;8)# 8hoose
based on the data a&ailable in tables "#! and "#!/ three suitable sol&ents for each
polymer and fulfill table "#!" indicating also the method used for the sol&ent selection#
!
'able (.12. %olubility parameters for &arious polymers and sol&ents#
Polymer 0olubility parameter
*32cm
"
+
122
0ol!ent 0olubility parameter
*32cm
"
+
122
?olyethylene (?5) !-#$-!6#! *cetone .#/
?olystyrene (?%) !6#"-!'#. *cetonitrile "#$
?oly&inylchloride (?;8) !'#-#! Fen+ene !$#$
Futanol $#6
8arbondisulfide .#-
8arbontetrachloride !6#4
8hloroben+ene !#/
8hloroform !'#.
8yclohexane !4#$
8yclohexanone !#/
7ecalin !6#4
7ioxan .#-
5thanol 4#!
5thylacetate !$#
1exane !"#'
Methanol '#6
Methylethyl:etone !'#.
Pitroben+ene #-
Ponane !-#4
Bctene-! !-#-
?henol "#4
Tetrahydrofuran !$#-
Toluene !$#/
(ater "$#.
Lylene !$#!
!/
'able (.1". Gnfinite dilution acti&ity coefficients of sol&ents in polymers#
!nfinite "ilution Activity
Coefficient #alues $

!
%
Polyethylene
*P7+
Polystyrene
*P0+
Poly!inylchloride
*P1#+
*cetone !.-!4 !4 '#.-.
*cenonitrile - !"-// !"-4
Fen+ene /#.--#. "#.-4#. 6#.-'#.
Futanol --/- !.-. -/
8arbondisulfide - "#- -
8arbon tetrachloride #. #--/#. $#.
8hloroben+ene "#. /#.-4#. 4#.
8hloroform #4 "#--- 4#.-'#.
8yclohexane "#. $#.-!. !4-!$
8yclohexanone - /#" -
7ecalin #- -#.-4#. -
7ioxane - "#- -#.
5thanol /.-!". '#--$ "-#-
5thylacetate - $#.-!/ !-!6
1exane -#" !.-. -"-64"
Methanol /.-!.. !.--. !'-!
Methylethyl:etone 4#.-!! 6#/ $,.-!.
Pitroben+ene - 4#.-$#. -
Ponane - $#.-'#. /-
Bctene-! "#6 $#.-'#. -
?henol !. - !!
Tetrahydrofuran 4#.-!4 "#.-6#. 6#/
Toluene /#. "#.-4#. 6#--!
(ater - 64--. -
Lylene - /#- -
!"
'able (.1(. 8hoose three suitable sol&ents for each polymer indicating also the method
for sol&ent selection#
%ol&ent Method for sol&ent selection
?5
?;8
?%
Problem 22. :eri!ing the <lory-Huggins acti!ity e$pressions
9or a binary sol&ent(!)-polymer() system, the total Gibbs energy change of mixing is
gi&en for the 9lory-1uggins model by the equation:
! ! ! !
ln ln + +

n n n
RT
(
mix
"#6
*ssuming that the 91 interaction parameter is independent of concentration, show that
the acti&ities of sol&ent and polymer are gi&en by the equations:

! ! !
!
! ln ln +
,
_

+
#
a
"#6/a
( )

! ! !
! ln ln + + # # a "#6/b
where #=)2/)1
Hint: ,#om +asi$ the#modynami$s 0e*%1%134:
i 9
n P T
mix
i
i
RT
( n
n
a

,
_

, ,
ln
"#6"
Problem 2". <eatures rom the <H equation combined with /0'
!-
The 91 interaction parameter can be related to the =%T-based solubility parameters (of
sol&ent, 1 and polymer, 2) as (including also its entropic part):
( )

!
!
+ +
RT
)
- h -
"#6-
9lory himself used the following notation for the entropic and enthalpic parts of the 91
parameters and the theta temperature, (3critical solution temperature, 8%T, at infinite
polymer molecular weight):
T
h
-

!
!

!



"#64
i# %how that the 91 parameter is a linear function of the in&erse temperature (
T + a , +
) and determine the two constants as a function of the
, ,
#
ii# 7eri&e the %chult+-9lory plot equation for the relationship between 8%T and theta
temperature (starting from the critical &alue of the 91 parameter, see problem !4):
1
]
1

,
_

+ +

#
#
2-T
! ! !
!
! !
!

"#66
iii# 7eri&e the following equation:
1
]
1

+
1
]
1

,
_

!
) (
) RT RT ) RT
-

"#6$
i&# 1ow do you thin: the abo&e two equations ("#66 and "#6$) can be used in data
analysis)
Problem 2(. /ules o thumb rom the <lory-Huggins model
The rules of thumb based on infinite dilution acti&ity coefficients shown in *ppendix "#F
can be (approximately) deri&ed from the rule of thumb based on the 9lory-1uggins
model i#e#
- # .
!
4
!

"#6'
%tarting from the 9lory-1uggins model, and assuming constant densities for the sol&ent
and the polymer, show that miscible mixtures are obtained if - # "
!

#
Hint: P#ove that fo# ve#y high mole$ula# !eight olyme#s, the solvent 014 infinite
dilution a$tivity $oeffi$ient o+tained f#om the ,H model is given +y the e*uation:

,
_

+ +

! !
ln ! ln

"#$.
!he#e i

a#e the densities of the solvent and the olyme# 01=solvent, 2=olyme#4%
Problem 2-. About the <lory-Huggins model
!4
i# %how that the two forms of the 9lory-1uggins (91) model, here written for the
sol&ent (!) acti&ity coefficient of a binary sol&ent(!),polymer()solution:

!
!
!
!
!
!
! ln ln +

,
_

,
_

x x
"#$!a

!
!
!
!
!
! ln ln +
,
_

,
_

# x
"#$!b
are equi&alent, if # is the ratio of the polymer (),sol&ent(!) &olume i#e# #=)2/)1
ii# Gt is often stated that the 91 parameter is a function of concentration and sometimes a
simple linear function can be used:
!
+ + a # Gs it appropriate to use this expression
for the 91 parameter in the abo&e-mentioned expressions for the 91 equation (equations
"#$!a and "#$!b) ) (hy,why not) Hustify your answer#
iii# *ssume that the 91 parameter is +ero for nearly athermal solutions such as mixtures
for al:anes# Then, using the 91 model estimate the n-pentane acti&ity coefficient at
infinite dilution in mixtures with n-decane, n-eicosane and n-8""# *ssume that T3!..
o
8# >se two &ersions of the concentration fractions, i

, both based on molar

&olumes and on the &an der (aals &olumes as estimated using the Fondi R-&alues
gi&en in Table "#!-# (hat do you obser&e) 8ompare the results obtained with the two
&ersions of the 91 model#
'able (.1-. ;alues of R and D for the groups of problem -# The &an der (aals &olumes
can be calculated from the R &alues by multiplying them with !-#!6 (thus expressing the
&an der (aals &olumes in cm
/
,mole)#
>roup R &
81/ .#'.!! .#$"$
81 .#46"" .#-".
Hint% The mola# volumes $an +e estimated e%g% using the (2")E& method 0El+#o, H%-%,
,#edenslund, Aa%, and Rasmussen, P%, 1881% 1nd% Eng% 2hem% Res%, 3A0124: 2F>B"2FC24 o#
the van .#evelen method, !hi$h is +ased on the van de# 6aals volumes%
!6