Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Study of modeling of cyclohexanol and polystyrene polymer solution at

T = 453.15 K and T = 493.15 K using UNIFAC-FV
Prithwi Raj Nayak a,⇑, Binay Prakash Akhouri b
a
Department of Physics , Deoghar College, Deoghar, Jharkhand, India
b
Department of Physics, Suraj Singh Memorial, College, Ranchi 834008, Jharkhand India

a r t i c l e i n f o a b s t r a c t

Article history: This study assesses the utility of the group contribution approach for predicting vapour-liquid equilib-
Available online xxxx rium (VLE) of cyclohexanol (CH,CH2,OH) in polystyrene(CH2,ACH,AC-CH) using the universal functional
activity coefficients-free volume (UNIFAC-FV). The calculated findings and the experiment show good
Keywords: agreement. The absolute average deviations (AADs) between theory and experiment for the polymer
UNIFAC-FV solution i.e., cyclohexanol in polystyrene (Mw = 200,000 g/mol) at T ¼ 453:5 and T ¼ 493:15 are found
Cyclohexanol to be 0.012 and 0, respectively for weight fraction activity coefficients and 0.024 and 0.007, respectively,
Polystyrene
for activity or activities coefficients.
Group contribution method
Absolute average deviations
Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Second Global Confer-
ence on Recent Advances in Sustainable Materials 2022.

1. Introduction ing formula for the weight fraction activity coefficient of a solvent
in a polymer solution after adding a free volume contribution to
The original UNIFAC model [1–5] is known to underestimate the original UNIFAC model:
experimental solvent activities in polymer solutions. Oishi and
ai fv
Prausnitz [6] added a free-volume contribution derived from the ln ci ¼ ln ¼ ln ccom
i þ ln cres
i þ ln ci ð1Þ
wi
Prigogine-Flory-Patterson theory [7–9] to the extremely effective
UNIFAC (UNIQUAC Functional Group Activity Coefficient) model where, ln ci is the activity coefficient of solvent i at temperature T.
[1]. The abbreviation UNIQUAC stands for Universal Quasi- Here, ln ccom
i is the combinatorial contribution (entropy term) to
chemical Equations, and it represents both vapour-liquid equilibria the activity coefficient, ln cres
i is the residual contribution (enthalpic
(VLE) and liquid–liquid equilibria (LLE) for binary and multicompo-
term) to the activity coefficient and ln cfi v the free volume contribu-
nent mixtures as well. Oishi and Prausnitz recognized that the UNI-
tion (Flory equation of state) to the activity coefficient. T is the tem-
FAC combinatorial contribution does not account for free volume
perature of solution, in Kelvin. The expressions for the
differences between the polymer and the solvent. The arisen
combinatorial term of the UNIFAC-FV model, presented by Danner
UNIFAC-FV model [6] represents a group contribution method,
and High [11] are:
which can be fairly applied to polymer solutions since the differ-
ence in thermal expansion behavior of polymer and solvent is /i hi / Mi X wj ‘j
ln ccom ¼ ln þ 5qi ln þ ‘i  i ð2Þ
explicitly taken into account by the free volume contribution Fig. 1. i
wi /i wi j
MJ
They extended UNIFAC to polymer solutions by adding a free-
volume contribution to account for the free-volume difference where,i; j = 1; 2; ::::::::m(number of components in the solution). /i is
between polymer and solvent molecules, which was first proposed the molecular volume fraction of component i, given by Eq. (3), wi is
by Prigogine-Flory-Patterson theory [7–9]. While this difference is the weight fraction of component, i in the polymer solution, qi is the
usually insignificant for liquid mixtures of small molecules, it is surface area parameter of component,i, given by Eq. (7), hi is the
important for polymer/solvent systems. They arrived at the follow- molecular area fraction of component i, given by Eq. (5), ‘i is a
parameter for component i, given by Eq. (6), Mi is molecular weight
⇑ Corresponding author. of component i, kilogram per kilo mole. The molecular volume frac-
E-mail address: prithwiraj336@gmail.com (P.R. Nayak). tion, /i for each component i is given by

https://doi.org/10.1016/j.matpr.2022.11.133
2214-7853/Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Second Global Conference on Recent Advances in Sustainable Materials 2022.

Please cite this article as: P.R. Nayak and B.P. Akhouri, Study of modeling of cyclohexanol and polystyrene polymer solution at T = 453.15 K and
T = 493.15 K using UNIFAC-FV, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2022.11.133
P.R. Nayak and B.P. Akhouri Materials Today: Proceedings xxx (xxxx) xxx

Fig. 1. Folecular structure of the styrene repeat unit (component 1, left hand side) and of cyclohexanol (component 2, right hand side).

r i wi
Mi where,X m = mole fraction of group m in the solution, given by Eq.
/i ¼ P r j wj ð3Þ (11). The group mole fraction X m is calculated from the following
j Mj
equation.
where r i is the volume parameter for component i, given by Eq. (4) PM v ðiÞ
m wi
X i Mi
ri ¼ v ðiÞ
ð4Þ Xm ¼ ð11Þ
k Rk PM PN v ðiÞ
j
wi
k i j Mi

where,v k is the number of groups of type k in molecule i.Rk is the

ðiÞ
where, v m is the number of groups of type m in component i and j =
ðiÞ

group volume parameter for group k[1,6,11].k = 1, 2,. . .. . ...n(num- 1,2,. . .. . ...m(number of components in the mixture). The residual
ber of groups in the solution). The molecular area fraction hi for each activity coefficient of group k in a reference solution containing only
component i is given by ðiÞ
component i,Ck , is similarly determined using Eqs. (9) through (11)
qi wi
M
with the exception that the summation indices k,m, and j refer only
hi ¼ P qi j wj ð5Þ to the groups present in the pure component and the summations
j Mj
over each component j are calculated only for the single component
The parameter ‘i is given by the equation present in the reference solution. The group interaction parameter
function Wmn is determined for each possible binary group pair, m
‘i ¼ 5ðr i  qi Þ  ðr i  1Þ ð6Þ and n, by the following equation,
The area parameter qi for each component i is determined by   h a i
U mn  U nn mn
X Wmn ¼ exp  ¼ exp  ð12Þ
qi ¼ v ðiÞ
k Qk ð7Þ RT RT
k
where,amn is the group interaction parameter resulting from the
where, Q k is the group area parameter for group k [1,6,11].The interaction of main groups m and n, given in Ref. [11] and has units
residual contribution is also given by of degree Kelvin. U mn is a measure of the interaction energy
h i between groups m and n.
X
groups
ln cres
i ¼ v kðiÞ ðiÞ
ln Ck  ln Ck ð8Þ The free volume contribution to the activity coefficient cfi v for
k each component i is given by
where,Ck is the residual activity coefficient of group k in the defined 0 1 !0 11
 1=3 
ðiÞ fv v  1A vi @1  1 A
solution at the given temperature T , given by Eq. (9). C is the k ln c ¼ 3ci ln @ i  ci  1 ð13Þ
residual activity coefficient (residual activity) of group k in a refer-
i
vm
 1=3
1 vm  1=3
vi
ence solution containing pure component i(or solvent molecules) at
where:ci represents the number of external degrees of freedom
the given temperature T , given by Eq. (9).
parameter per solvent (i.e., component 1) molecule. It is usually
The residual activity coefficient of group k in the given solution 
is given by: set to 1.1.The reduced volume vi of solvent i, is given by Eq. (14).

" ! # The reduced volume of the mixture v m , is given by Eq. (15). Oishi
X X Hm Wkm
ln Ck ¼ Q k 1  ln Hm Wmk  ð9Þ and Prausnitz suggested the following equation for the calculation
m m
Hn Wnm of the reduced volume for the solvent i as:
where,m and n = 1,2,. . .. . ...N(number of groups in the solution), Hm  v i Mi
vi ¼ ð14Þ
is the groups surface area fraction of group m in the given solution, 0:01517br i
given in Eq. (9).Wmk is the group interaction parameter for the inter-
where,v i is the specific volume of component i, cubic meters per
action of group m with group k, given by Eq. (12). A similar equation
ð1Þ
kilogram, b is the proportionality factor of order unity(it is usually
of (9) can be written for ln Ck . The group surface area fraction Hm 
taken to be1.28), the reduced volume of the mixture,v m is calcu-
for group m is given by
lated from,
Q Xm P
Hm ¼ P m ð10Þ i v i Mi

n Q n Xn
vm ¼ P ð15Þ
0:01517b rMi wi i

2
P.R. Nayak and B.P. Akhouri Materials Today: Proceedings xxx (xxxx) xxx

Here,wi is the weight fraction of component i.

UNIFAC-FV [10–21] has been very successful in the prediction
of solvent activities for polymer solutions. The experimental and
theoretical weight fraction activity coefficients and activity for
Cyclohexanol (1) + Polystyrene (2) at column temperature,
T ¼ 453:15K and T ¼ 493:15K are given in Table 1 and Table 2,
respectively. This is illustrated in this work for polystyrene/cyclo-
hexanol with the determination of AADs between theory and
experiment. The AADs reported are given in Table 3.

Table 1
The experimental and theoretical weight fraction activity coefficients and activity at
column temperature, T ¼ 453:15K for Cyclohexanol (1) + Polystyrene (2).

wi EXPERIMENTAL THEORETICAL
Xi ai Xi ai
WFAC ACTIVITY WFAC ACTIVITY Fig. 2. Calculated and observed activities of cyclohexanol in polystyrene at
453.15 K.
0.0000 6.26 0.0000 5.98 0.0000
0.0006 5.88 0.0033 5.89 0.0035
0.0037 5.80 0.0215 5.84 0.0215
0.0119 5.65 0.0671 5.69 0.0677
0.0265 5.36 0.1420 5.44 0.1442
0.0883 4.97 0.4389 4.54 0.4016
0.1312 4.22 0.5536 4.05 0.5315

Table 2
The experimental and theoretical weight fraction activity coefficients and activity at
column temperature, T ¼ 493:15K for Cyclohexanol (1) + Polystyrene (2).

wi EXPERIMENTAL THEORETICAL
Xi ai Xi ai
WFAC ACTIVITY WFAC ACTIVITY
0.0000 5.35 0.0000 4.35 0.0000
0.0003 4.75 0.0013 4.34 0.0013
0.0018 4.69 0.0086 4.32 0.0079
0.0052 4.56 0.0236 4.30 0.0223
0.0152 4.18 0.0635 4.20 0.0639
0.0450 3.51 0.1578 3.96 0.1782
0.0465 3.49 0.1624 3.94 0.1836 Fig. 3. Calculated and observed activities of cyclohexanol in polystyrene at
493.15 K.

Table 3
Deviations calculated by the UNIFAC FV Model for the binary system Cyclohexanol (1) - Polystyrene (2) at 453.15 K and 493.15 K.

Experimental Calculated by
UNIFAC-FV- Model
Standard deviation for Xi Relative deviation for Xi Standard deviation for ai Relative deviation for ai

wi Xi ai DXi Dai DXi  DXi Dai  Dai


T ¼ 453:15K
0.0000 6.26 0.0000 0.28 4.473 0.0000 9.923 0.179- 0.0080
0.0006 5.88 0.0033 10.10-3 0.1270 6.061 6.255 0.110 0.0082
0.00.37 5.80 0.0215 0.04 0.690 0.0000 0.723 0.141 0.0080
0.0119 5.65 0.0671 0.04 0.708 0.8940 2.683 0.140 0.0086
0.0265 5.36 0.1420 0.08 1.493 1.5490 1.188 0.181- 0.0000
0.0883 4.97 0.4389 0.43 8.652 8.4990 1.549 0.329 0.0290
0.1312 4.22 0.5536 0.17 4.028 3.9920 2.741 0.069 0.01400
Average 0.101 2.013 0.57 2.747 0.012 0.0240
Xi AAD ai AAD
T ¼ 493:15K
0.0000 5.35 0.0000 1.000 18.692 0.0000 0.0000 0.84 0.00587
0.0003 4.75 0.0013 0.410 8.6320 0.0000 0.0000 0.25 0.00587
0.0018 4.69 0.0086 0.370 7.8890 0.0000 0.0000 0.21 0.00587
0.0052 4.56 0.0236 0.260 5.7020 0.0013 0.0236 0.10 0.00717
0.0152 4.18 0.0635 0.020 0.4780 0.0004 0.630 0.18 0.05470
0.0450 3.51 0.1578 0.450 12.821 0.0204 12.92 0.61 0.01450
0.0465 3.49 0.1624 0.450 12.894 0.0212 13.05 0.61 0.01533
Average 0.16 2.103 0.00587 3.015 0.00 0.007
Xi AAD aAAD

3
P.R. Nayak and B.P. Akhouri Materials Today: Proceedings xxx (xxxx) xxx

Table 4
Parameters of sub groups.

Functional Groups j Rk Qk mð1Þ

j
mð2Þ
j
Cyclohexagonal PS repeat unit (2)
(1)
CH2 1 0.6744 0.540 5 1
CH 2 0.4469 0.228 1 0
ACH 3 0.5313 0.400 0 5
AC-CH 4 0.8121 0.348 0 1
OH 5 0.5299 0.584 1 0

Table 5
Interaction Parameter Matrix for Cyclohexanol and Polystyrene solution.

Main Group 1 Main Group 2 Main Group 3 Main Group 4

j¼1 j¼1 j¼2 j¼3 j¼4

Main Group 1 j¼1 0.00 0.00 61.13 76.50 986.5
j¼1 0.00 0.00 61.13 76.50 986.5
Main Group 2 j¼2 11.12 11.12 0.00 167.0 636.1
Main Group 3 j¼3 69.70 69.70 146.8 0.00 803.2
Main Group 4 j¼4 156.4 156.4 89.60 25.82 0.00

2. Result and discussion Data availability

The calculated and observed activities of cyclohexanol in poly- Data will be made available on request.
styrene at 453.15 K and 493.5 K are shown in Fig. 2 and Fig. 3. The
values of specific volumes and molecular weight are considered as Declaration of Competing Interest
the specific volume of cyclohexanol at 453.15 K is
m1 ¼ 1:2510  103 m3/kg, the specific volume of cyclohexanol at The authors declare that they have no known competing finan-
493.15 K is m2 ¼ 1:075  103 m3/kg, and specific volume of poly- cial interests or personal relationships that could have appeared
styrene (P: 0.1 MPa-200 MPa; T: 389 K-496 K) is to influence the work reported in this paper.
This manuscript has not been submitted to ,another journal or
m1 ¼ 1:2510  103 m3/kg whereas molecular weight of cyclohex-
other publishing venue.
anol is Mw ¼ 100:161 g/mol, mass of styrene repeat unit is
The authors have no affiliation with organization with direct and
Mw ¼ 104:153 g/mol, Number of repeat units is N repeat ¼ 104:153.
indirect financial interest in the subject matter discuss in the
We can see that there are five functional groups: CH2 (j=1), CH
manuscript.
(j=2), ACH (j=3), AC-CH2 (j=4) and OH (j=5). Table 4 shows the sub-
groups, their identification numbers k, values of parameters Rk and
References
Q k , and mj , which represents the number of j groups in component
ðiÞ

i. CH2, CH belongs to the main group 1, ACH belongs to the main
group 2, AC-CH2 belongs to the main group 3, and OH belongs to
the main group4. Thus we can construct the amn parameter matrix
as shown in Table 5.
3. Conclusions
The calculations show that the UNIFAC-FV model is in general
suitable for describing weight fraction activity coefficients and
activity coefficients or activities. It appears that the best strategy
to explain polymer solutions of this type is to use a model that
takes into account the contribution of all structural units to the sol-
vent residual activities. The UNIFAC-FV results corroborate this. It
would be preferable to account for all structural information pro-
vided by NMR data, for example within the attracting and repulsive
parts of an equation of state.
CRediT authorship contribution statement
Prithwi Raj Nayak: Data curation, Investigation, Visualization,
Writing - review & editing. Binay Prakash Akhouri: Writing –
review & editing.
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