Calculation of The Cloud Point and The Spinodal Curve For T 2002 Fluid Phase

Fluid Phase Equilibria 194–197 (2002) 451–467
Calculation of the cloud-point and the spinodal curve for the

system methylcyclohexane/polystyrene at high pressures
D. Browarzik∗ , M. Kowalewski
Institute of Physical Chemistry, Martin Luther University Halle-Wittenberg, Fachbereich Chemie 06217 Merseburg, Germany
Received 20 May 2001; accepted 10 July 2001
Abstract
Cloud-point and spinodal curves of the system methylcyclohexane (MCH)/polystyrene (PS) are calculated with
the aid of the Sako–Wu–Prausnitz equation of state (SWP-EOS). To describe the molecular-weight polydispersity of
the polymer influencing the phase equilibrium and the stability, continuous thermodynamics is applied. The system
MCH/PS is particularly interesting. In a certain temperature region its pressure–concentration diagram shows both
a curve with a lower critical point (LCP) and a curve with an upper critical point (UCP). Lowering the temperature
both curves become closer and merge, finally, forming a hour-glass shaped two-phase region. For several years
this behaviour has been well known from experimental data concerning a nearly monodisperse PS sample. Firstly,
we prove the SWP-EOS to be able to describe these data. Secondly, by computer simulations we investigate the
transition of the UCP/LCP curves into the hour-glass shaped curves for the polydisperse case never studied before.
This transition is demonstrated to be quite different from that of solutions of monodisperse PS samples in MCH.
Thirdly, we apply the SWP-EOS to a real system consisting of MCH and a PS sample with a broad molecular
weight distribution and, compare the results with the experimental findings. © 2002 Elsevier Science B.V. All rights
reserved.
Keywords: Method of calculation; Equation of state; Continuous thermodynamics; Spinodal curve; Cloud-point curve;
Polymer systems
1. Introduction
Measuring cloud-point and spinodal curves of the system methylcyclohexane (MCH)/polystyrene (PS)
at high pressure for some temperatures the pressure–concentration diagram shows two curves. If the
PS sample is monodisperse, there is an upper curve with a lower critical point (LCP) as minimum
and a lower curve with an upper critical point (UCP) as maximum. Changing the temperature both
curves can become closer and merge, finally, forming a hour-glass shaped two-phase region. The system
MCH/PS was often experimentally investigated [1–6]. Vanhee et al. [2] studied particularly the transition
∗
Corresponding author. Tel.: +49-3461-2133; fax: +49-3461-2129.
E-mail address: browazik@chemie.uni-halle.de (D. Browarzik).
0378-3812/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 ( 0 1 ) 0 0 6 9 3 - 8
452 D. Browarzik, M. Kowalewski / Fluid Phase Equilibria 194–197 (2002) 451–467
of the UCP/LCP curves into the hour-glass shaped curves using a nearly monodisperse PS sample. They
measured both spinodal and cloud-point pressures applying a pressure-pulse-induced critical scattering
(PPICS) technique [3]. So, they could prove that the LCP curve and the UCP curve coincidence at their
critical points which, in the monodisperse case, are the extreme values too. Once the hour-glass shaped
curves have been formed critical points no longer exist. However, the knowledge about the monodisperse
case does not permit conclusions about how the transformation is going on in the polydisperse case.
We know that the polydispersity can considerably influence phase equilibrium and stability. Thus, it is
well known that in the polydisperse case the critical point is located neither in an extreme value of the
cloud-point curve nor in an extreme value of the spinodal curve. Fortunately, Enders and de Loos [5]
investigated the same system but using a polymer sample with a broad molecular-weight distribution.
They also measured numerous spinodal and cloud-point data applying the PPICS technique. However, the
experimental data do not involve the transformation temperature and, therefore, with only the experimental
data one can not explain what happens in detail if the LCP curve and the UCP curve coincidence. So, the
authors [5] try to understand the formation of the hour-glass two-phase region by performing calculations.
These show that the spinodal curves (UCP/LCP) coincidence at their extreme values forming a cross of
straight lines. However, it is not clear what happens to the critical points and to the cloud-point curves.
Furthermore, the authors [5] applied an activity coefficient model instead of an equation of state (EOS)
that should be preferred in modelling at high pressures. So, our goal is to calculate both spinodal and
cloud-point curves based on an EOS. We have chosen the simple cubic EOS introduced by Sako, Wu
and Prausnitz (SWP-EOS, [7]) which has proven to be suitable for polymer systems. We want to explain
the transition of the UCP/LCP behaviour into the hour-glass shape in the polydisperse case discussing
spinodal curves, cloud-point curves, shadow curves and critical points.
To take into account the molecular-weight polydispersity, continuous thermodynamics is a powerful
tool. In continuous thermodynamics the composition of the polymer is described by a continuous distri-
bution function with respect to the molecular weight. So, instead of the weight fractions of hundreds of
polymer species, only distribution function is needed. Introduced in 1980 [8] already some years later
continuous thermodynamics has been applied to calculate cloud-point curves [9] and stability [10] of
polymer systems. However, the stability treatment was firstly restricted to activity coefficient models.
More recently, stability theory of continuous thermodynamics was extended to equations of state too
[11–13]. In 1999, this stability treatment was applied to polymer systems the first time [13].
2. Calculation of the spinodal and the cloud-point curve with continuous thermodynamics
Recently, we published a paper [13] concerning the question how to calculate the spinodal curve based
on an EOS for a system consisting of a polydisperse polymer, a solvent and a gas. Here, we consider
solutions of a polydisperse polymer B in a solvent A. The polydispersity of the polymer is considered
with the aid of continuous thermodynamics [14,15]. Because the treatment is very similar to that of
the pseudo-ternary system [13] only the basic steps are to be outlined once more. We start with the
segment–molar Helmholtz energy, the non-linear part of which is given by:

ψ 1−ψ RT
As = RT Ws (r)ln [ψWs (r)] dr + ln(1 − ψ) − M ln Vs + Js (1)
r rA r̄
D. Browarzik, M. Kowalewski / Fluid Phase Equilibria 194–197 (2002) 451–467 453
A detailed derivation of Eq. (1) and the reason why the segment–molar notation should be preferred for
polymer systems one can find in an earlier paper [13]. In Eq. (1), R is the universal gas constant and T is the
temperature. The quantities r and rA denote the segment numbers of the molecules of the polymer species
and of the solvent. We assume the segment numbers to be proportional to the molecular weight. ψ is the
total weight fraction of the polymer. Ws (r) is the segment–molar distribution function of the polymer.
The integral of this distribution function is the weight fraction of all polymer species with values of r
between the limits of the integral if there is no solvent (ψ = 1). Corresponding to that, integration for
the total domain of definition of the segment number r yields the value 1 (normalization condition). The
integral in Eq. (1) and all following ones of this type are related to the whole domain of definition of the
segment number r. In most cases the limits are 0 and ∞. The number average of the segment number r̄ M
of the mixture is governed by the equations

1 1−ψ ψ 1 Ws (r)
M
= + ; = dr (2)
r̄ rA r̄B r̄B r
where r̄B is the number average of the segment number of the polymer being proportional to the number
average M̄n of the molecular weight. The quantity Js includes the information about the equation of state
and reads
∞
RT
Js = p− M dVs (3)
Vs r̄ Vs
Here, Vs is the segment–molar volume which is obtained from the molar volume by division through r̄ M .
Eq. (1) only involves such terms being non-linear with respect to the weight fractions and to the distribution
function. For the spinodal condition the linear terms do not matter. The terms in braces of Eq. (1) present
the ideal athermic contribution of the segment–molar Helmholtz energy. In the framework of activity
coefficient models this term is well known as Flory–Huggins contribution. It describes the entropic effect
arising from the size differences of the molecules due to a statistical background. Surprisingly, using
an EOS the calculation of the segment–molar Helmholtz energy from the corresponding molar quantity
yields this contribution to Eq. (1) with no need of any statistical treatment [13].
To find the spinodal condition, firstly, one has to form the second differential δ 2 As of the segment–molar
Helmholtz energy with respect to the variations δVs , δψ and δ[ψWs (r)]. The next step is to find that
variation function δ[ψWs (r)]∗ minimizing the second differential of the segment–molar Helmholtz energy.
In this, the condition

δ[ψWs (r)] dr = δψ (4)
has to be taken into account. Eq. (4) originates from the normalization condition of the distribution func-
tion. Therefore, as minimization procedure Lagrange’s method of undetermined multipliers is applied. If
the variation function δ[ψWs (r)]∗ is known this expression has to be introduced into the second differential
δ 2 As giving δ 2 A∗s = δ 2 As {δ[ψWs (r)]∗ }. In detail one finds
δ 2 A∗s = αVV (δVs )2 + 2αV ψ δVs δψ + αψψ (δψ)2 (5)
with

RT 1−ψ ψ
αVV = JVV + + (6a)
(Vs )2 rA r̄B (1 + U )

RT 1 1
αV ψ = JV ψ + − (6b)
Vs rA r̄B (1 + U )

1 1
αψψ = Jψψ + RT + (6c)
rA (1 − ψ) r̄B (1 + U )ψ
U is the so-called non-uniformity obtained from the quotient of the weight average M̄w and the number
average M̄n of the molecular weight subtracting 1. Eqs. (6) are restricted to equations of state resulting
in a function Js that depends on Vs and ψ only. The SWP-EOS [7] is one of this type. The quantities JV V ,
JV ψ , Jψψ are the second derivatives of Js with respect to Vs and ψ.
The following steps are the same as in the monodisperse case. The variation δψ ∗ as function of δVs
minimizing δ 2 A∗s has to be found. It is easy to get δψ ∗ = −(αV ψ /αψψ )δVs . Introducing this variation
into Eq. (5) and setting this expression of the second differential equal to zero one obtains as spinodal
condition

αVV αV ψ
K0 = αVV αψψ − (αV ψ ) =
2 =0 (7)
αV ψ αψψ
It should be mentioned that continuing the procedure described previously one can find an additional
necessary condition for the critical point. For this purpose, based on Eq. (7), δK0 has to be formed with
respect to δVs , δψ and δ[ψWs (r)]. Introducing the expressions of δ[ψWs (r)]∗ and δψ ∗ into δK0 and setting
the expression derived in this way equal to zero one can obtain the second necessary critical condition.
In calculation of phase equilibrium by means of EOS, the fugacity coefficients are the most important
quantities. Continuous thermodynamics results in the following expressions for the fugacity coefficients
of the solvent A and the species of the polymer B identified by their segment number r [13]:

M pVs
ln φA = rA BA − ln r̄ − ln (8a)
RT

M pVs
ln φB (r) = rBB − ln r̄ − ln (8b)
RT
These are general expressions valid for any EOS. Only, the quantities Bi (i = A, B) depend on the nature
of the EOS. Eqs. (8a) and (8b) are not very different from the corresponding notation in traditional
thermodynamics. The only difference is that Eq. (8b) is not related to a real discrete component but rather
to a polymer species identified by the segment number r which can take any value between 0 and ∞. The
quantities Bi (i = A, B) can be derived in the usual way of traditional thermodynamics or by continuous
thermodynamics [16]. In the next section expressions for the SWP-EOS are presented. Here, the general
treatment based on continuous thermodynamics is to be discussed. With the fugacity coefficients being
known the equilibrium conditions for the feed phase I and the incipient phase II in segment–molar notation
[13] read
(1 − ψ I )φAI r̄ MI = (1 − ψ II )φAII r̄ MII (9a)
ψ I WsI (r)φBI (r)r̄ MI = ψ II WsII (r)φBII (r)r̄ MII (9b)
With the aid of Eq. (8a) one can find

1 (1 − ψ I )VsII
ln + BAI − BAII = 0 (10)
rA (1 − ψ II )VsI
For further treatment of Eq. (9b) the distribution function of the phase I has to be known. We presume a
Schulz–Flory distribution
k
kk r r
Ws (r) =
I
exp −k I (11)
Γ (k)r̄BI r̄BI r̄B
Originally, this distribution relates to the molecular weight but, assuming the segment number to be
proportional to the molecular weight the same type of function results. Here Γ denotes the Γ -function
and k relates to U by k = 1/U . Introducing Eq. (11) into Eq. (9b) by integration of Eq. (9b) within the
limits 0 and ∞ one obtains
I II
1 ψ Vs 1 + 1/U
ln − ln{1 − r̄BI U (BBI − BBII )} = 0 (12)
r̄B
I ψ Vs
II I r̄BI
Introducing Eq. (11) into Eq. (9b) and, multiplying Eq. (9b) by r and integrating this expression in the
limits 0 and ∞ an equation for the number average of the segment number of the incipient phase II is
obtained.
II I U/U +1
ψ Vs
r̄B = r̄B
II I
(13)
ψ I VsII
Additionally, one can show the distribution function of the phase II is also one of the Schulz–Flory
type with the parameters r̄BII and k where k has in both phases the same value. The segment–molar
volumes VsI and VsII have to be computed by solving the EOS for both phases. For given temperature,
the equilibrium pressure p and the mass fraction ψ II of the polymer in the phase II have to be calculated
solving the non-linear set of the Eqs. (10) and (12). The function p(ψ I ) is the cloud-point curve. p(ψ II ) is
the so-called shadow curve that coincidences with the cloud-point curve only in the monodisperse case.
3. Equation of state
For calculation an equation of state (EOS) has to be chosen. The polydispersity of polymers compli-
cates the calculation of spinodals and cloud-point curves. Therefore, on the one hand, the EOS should
be relatively simple. But, on the other hand, the EOS has to be appropriate to polymers. These require-
ments are fulfilled by a simple cubic EOS introduced in 1989 by Sako, Wu and Prausnitz [7] describ-
ing the high-pressure equilibrium of the system ethylene/polyethylene. In a preceding paper [13] we
applied the SWP-EOS to calculate stability and phase equilibrium of the system cyclohexane/carbon
dioxide/polystyrene at high pressures. The SWP-EOS of the mixture reads in segment–molar notation:
RT RTbs cs as
p= + − (14)
r̄ M V s Vs (Vs − bs ) Vs (Vs + bs )
The segment–molar parameters as , bs , cs are obtained from molar parameters a, b, and c by division
through (r̄ M )2 (for the parameter a) or through r̄ M (for the parameters b and c). If all molecules are so
small that they can be presented by one segment, Eq. (14) reduces to the Soave–Redlich–Kwong EOS.
Here, 3c is the total number of external degrees of freedom per molecule. In this, the external rotational and
vibrational degrees of freedom are considered as equivalent translational degrees of freedom. Depending
on the chain flexibility the parameter c of a pure species can take values between 1 and the number r of
segments of the molecule. According to that, the values of cs have to be positive but not larger than 1.
To calculate the parameters as , bs , cs of the mixture mixing rules are needed. As usually for cubic
equations of state we assume arithmetic mixing rules for b and c and a geometric mixing rule with a
correction of the following type for the parameter a.
√
aij = aii ajj (1 − kij ) (15)
Then, the segment–molar parameters of the system solvent (A) + polymer (B) are given by
√ √ √
as = {(1 − ψ) as,A + ψ as,B }2 − 2ψ(1 − ψ) as,A as,B kAB (16a)
bs = (1 − ψ)bs,A + ψbs,B (16b)
cs = (1 − ψ)cs,A + ψcs,B (16c)
To calculate the segment numbers a standard segment has to be chosen. We choose the methylcyclohexane
molecules as reference segments with r A = 1. Assuming the segment number to be proportional to the
molecular weight M the segment number r of a polystyrene species is related to M by
M
r = 10.1852 (17)
1000
The determination of the pure-component parameters for MCH is relatively simple. The segment–molar
quantities do not differ from the molar ones because of r A = 1. Furthermore, for the sake of simplicity
we set cA = cs,A = 1. Then the procedure is the same as in the case of the Soave–Redlich–Kwong
EOS. To determine the parameters as , bs for a volatile component as MCH the critical temperature and
the critical pressure may be used. For MCH the critical temperature and pressure amount 572.19 K and
3.4714 MPa [17]. In this way the parameter bs,A = 0.1187373 l mol−1 and at the critical temperature the
parameter a s,A = 2.787113 MPa l2 mol−2 were found. The temperature dependence of the parameter as,A
is calculated by an equation proposed by Sako et al. [7] (Eqs. (12) and (13) ). The van der Waals volume
needed in this equation was taken from Bondi’s well known tables [18]. In this way, we obtained

1.686389 + 0.313611(T /572.19)2
as,A = 2.787113 (18)
1 + (T /572.19)2
The determination of the pure-component parameters of polystyrene is very difficult because critical
data are not available. Therefore, these parameters are adjusted to the experimental spinodal data of
the pseudo-binary system MCH/PS assuming for as,B the same temperature dependence as for as,A .In
calculation of the spinodal the quantity Js plays an important role. Introducing the SWP-EOS into Eq. (3)
one can find easily

Vs as Vs
Js = RTcs ln + ln (19)
Vs − b s bs Vs + b s
Based on Eq. (19) the derivatives JV V , JV ψ , Jψψ needed in Eq. (6) may be derived. In this, one has to take
into account that the dependence of the weight fraction ψ is hidden in the segment–molar parameters as ,
bs , cs .
To calculate the fugacities the quantities Bi (i = A, B)of Eq. (8) are needed. With ψA = 1−ψ; ψB = ψ
one can derive or find from the literature [7] the following equation:

bs cs bs,i as bs,i
Bi = −cs,i ln 1 − + −
Vs Vs − bs RTbs (Vs + bs )
  

ln(1 + bs /Vs ) as bs,i √  
√ 
+ − 2 as,i ψj as,j (1 − kij ) (20)
RTbs  bs 
j
4. Parameter fit
There are four parameters to have to be adjusted to experimental data. These are the three pure-component
parameters of PS and the mixing parameter kAB . (The parameter as,B is assumed to have the same temper-
ature dependence as the parameter as,B for MCH. So, only the quotient as,B /as,A has to be determined.)
Modelling the transition of the UCP/LCP curves into the hour-glass shaped curves for the parameter fit a
temperature range including this transition should be considered. Vanhee et al. [2] measured spinodal and
cloud-point pressures of the system MCH/PS within this temperature range. The PS sample used was a
nearly monodisperse one (U = 0.06) with a number average M̄n of the molecular weight of 16,500 g/mol.
Firstly, the parameters were fitted to the experimental spinodal pressures at 20.8 ◦ C, particularly, to the
experimental UCP points (Fig. 1). The parameter values obtained are:
as,B (T ) = 0.95316as,A (T ); bs,B = 0.1260 l mol−1 ; cs,B = 0.028; (21a)
kAB = 0.00296 (21b)
Obviously, in Fig. 1 the calculated LCP curve is too small. The reason is, that three parameters are needed
to describe the UCP curve with respect to maximum and breadth. One parameter remains to fit the pressure
Fig. 1. Calculated spinodal curves of the system MCH/PS at 20.6 and 20.8 ◦ C compared with the experimental data; (䊏) 20.6 ◦ C,
(䉬) 20.8 ◦ C).
Fig. 2. Calculated cloud-point curves of the system MCH/PS at 20.6, 20.8 and 21.2 ◦ C compared with the experimental data;
(䊏) 20.6 ◦ C, (䉬) 20.8 ◦ C, ( ) 21.2 ◦ C.
minimum of the LCP curve. So, for description of the LCP curve no parameter is left. Unfortunately, the
pure-component parameters for PS of Eq. (21a) do not take the same values as estimated for the system
cyclohexane/carbon dioxide/polystyrene in a previous paper [13]. The parameter cs,B of Eq. (21a) is
remarkably small which could originate from the low flexibility of the polystyrene chains. Higher values
of cs would result in smaller spinodal curves in the pressure–concentration diagram.
Including other temperatures than 20.8 ◦ C a temperature independent parameter kAB as suggested
by Eq. (21b) is not sufficient. Therefore, a linear temperature function kAB was chosen to fit to the
experimental spinodal points at 20.7 and 20.6 ◦ C) and the cloud-point pressures at 20.6, 21.0 and 21.2 ◦ C.
In this, Eq. (21a) remains valid. Eq. (21b) is replaced by the generalized equation
kAB = 0.00296 − 0.00017(T − 293.95) (22)
Fig. 1 shows the results for the spinodal curves at the temperatures 20.8 and 20.6 ◦ C. At 20.8 ◦ C there are
still UCP/LCP curves. Lowering the temperature only by 0.2 K the hour-glass shaped curves are formed.
Corresponding to that, a very small inaccuracy of the kAB - parameter results in a considerable pressure
change. Therefore, it is not surprising that at 20.6 ◦ C the calculated values deviate from the experimental
ones somewhat.
In Fig. 2, the cloud-point curves at three temperatures are compared with the experimental data. Con-
sidering that the parameters were practically fitted to spinodal pressures these results are satisfactory.
5. Formation of the hour-glass shaped curves in polydisperse systems
Once the parameters were determined computer simulations can demonstrate the effect of polydisper-
sity. So, we consider the same system with the same number average M̄n (16,500 g/mol) for polystyrene
but, with a non-uniformity of U = 1 (corresponding to a weight average M̄w of 33,000 g/mol). The
Fig. 3. Calculated cloud-point curves (—), spinodal curves (· · · ) and critical points (䊏) for a mixture of MCH and polydisperse
PS (M̄n = 16,500 g/mol; U = 1) at 23.5 ◦ C.
pure-component parameters of PS and the mixing parameter kAB as function of the temperature are given
by Eqs. (21a) and (22). In Figs. 3–10 the transition of the UCP/LCP curves into the hour-glass shaped
curves originating from a lowering of the temperature is demonstrated for the spinodal, the cloud-point
and the shadow curves. Even though merely the temperature range 23.5–22.35 ◦ C is considered essential
changes in the phase diagram occur. We start with the temperature 23.5 ◦ C.
In Fig. 3 the cloud-point curves, the spinodal curves and the critical points are presented. At this
temperature there are a LCP curve and an UCP curve in each case. Because of the molecular-weight
Fig. 4. Calculated cloud-point curves (—), shadow curves (- - -) and critical points (䊏) for a mixture of MCH and polydisperse
PS (M̄n = 16,500 g/mol; U = 1) at 23.5 ◦ C.
PS (M̄n = 16,500 g/mol; U = 1) at 23.35 ◦ C.
polydispersity of the polymer (U = 1) the extreme values of the spinodal curves, of the cloud-point
curves and the critical points no longer coincidence. One can see a large distance between the both
spinodal curves, but the both cloud-point curves are relatively close to each other at this temperature.
Fig. 4 shows the cloud-point curves 1, 2 and the corresponding shadow curves 1∗ , 2∗ at 23.5 ◦ C. As
usually, the critical points are the intersection points of the cloud-point and the shadow curves.
Lowering the temperature further the cloud-point curves become closer and, finally merge at their
extreme values forming a cross with straight lines. At the lower temperature 23.35 ◦ C, there are hour-glass
PS (M̄n = 16,500 g/mol; U = 1) at 23.35 ◦ C.
PS (M̄n = 16,500 g/mol; U = 1) at 23.168 ◦ C.
shaped cloud-point curves presented in Fig. 5. The little temperature difference (0.15 K) is sufficient to
change the phase diagram qualitatively. Differing to the cloud-point curves the spinodals still show an
UCP/LCP behaviour. Both critical points are located on the cloud-point curve of the polymer rich region.
It is interesting to have a look at the corresponding shadow curves presented in Fig. 6. There are a
cloud-point curve 1 and shadow curve 1∗ which do not cross and, there are a cloud-point curve 2 and a
shadow curve 2∗ with two intersection points being the critical points.
PS (M̄n = 16,500 g/mol; U = 1) at 23.15 ◦ C.
PS (M̄n = 16,500 g/mol; U = 1) at 22.35 ◦ C.
At the temperature 23.168 ◦ C the spinodals merge forming a cross with straight lines (Fig. 7). The
cloud-point curves and the shadow curves are similar to those presented in Figs. 5 and 6.
At the temperature 23.15 ◦ C both the cloud-point curves and the spinodal curves show the hour-glassed
shape (Fig. 8). The critical points still exist. The cloud-point and the spinodal curve are very close to
each other within a wide pressure range. This behaviour is forced by the critical points which have to be
located both on the spinodal curve and on the cloud-point curve.
Lowering the temperature the critical points become closer and, finally, merge to form a double critical
point that is the only contact point of cloud-point and shadow curve. Fig. 9 shows the cloud-point curves
PS (M̄n = 16,500 g/mol; U = 1) at 22.35 ◦ C.
and the spinodals at the temperature 22.35 ◦ C. Now, there are no longer critical points. According to that,
the spinodal and the cloud-point curve on the right hand side of the diagram are separated. In Fig. 10, at
the same temperature the cloud-point curves and the shadow curves are pictured. The cloud-point curve
2 and the shadow curve 2∗ no longer intersect because there are no critical points.
6. Results for a real polydisperse system
The calculations of the last section are very interesting because they illustrate the complexity of the
formation of hour-glass shaped diagrams in polydisperse systems. However, there are no experimental
data for comparison in the case considered. So, we do not know the accuracy of the EOS applied to a real
polydisperse system. Fortunately, Enders and de Loos [5] measured numerous spinodal and cloud-point
pressures for a polydisperse system MCH/PS. The PS sample has a number average M̄n of 143,000 g/mol
which is essentially higher than that of the sample considered before. Corresponding to the weight average
M̄w = 405,000 g/mol the non-uniformity accounts U = 1.832. The pure-component parameters of MCH
and PS are known from the preceding calculations. The mixing parameter kAB should be fitted newly
because kAB can depend on the molecular weight. Furthermore, kAB is needed in a wide temperature range
because there are experimental data in two temperature regions widely separated from each other. The
low temperature region is about 316–332 K and, the high temperature region is about 500–520 K. There
are cloud-point data in both temperature ranges measured in a Cailletet apparatus and, spinodal data in the
low temperature range measured in a PPICS equipment. The low temperature range corresponds to curves
with an upper critical solution temperature (UCST) and the high temperature range corresponds to a lower
critical solution temperature (LCST). We tried to find a temperature function kAB (T) which is suitable for
both temperature regions mentioned. Firstly, we fitted kAB separately to the UCST spinodal data and to
the LCST cloud-point pressures. In this way we found a linear function for the UCST region and another
linear function for the LCST region. A function kAB (T) describing simultaneously both regions needs at
least four parameters. We found the following expression for kAB (T):
kAB = A + BT + CT2 + DT3 A = −1.5772578; B = 1.2493527 × 10−2 K −1 ;
C = −3.1444661 × 10−5 K −2 ; D = 2.444442 × 10−8 K−3 (23)
For illustration in Fig. 11 the function kAB (T) is presented. Experimental data for parameter fit were
available in the both temperature regions indicated by the bold lined parts of the curve.
For comparison of the calculated spinodal curves there are experimental data for polymer weight
fractions between 0.0067 and 0.0682. In Fig. 12, the calculated and the experimental spinodal pressures
in dependence on the temperature are shown for a small (ψ = 0.018) and the highest polymer weight
fraction (ψ = 0.0682). The agreement between the calculated and the experimental values is reasonably
well. In the pressure–concentration diagram the experimental data correspond to the UCP curves. For the
LCP curves there are no experimental data. If one would plot the temperature against the pressure each of
the two curves would possess a minimum indicating the temperature at which the spinodal curves begin
to be hour-glass shaped.
Furthermore, there are experimental cloud-point pressures (LCST) at temperatures between 500 and
520 K for the polymer weight fractions ψ = 0.065 and ψ = 0.187 [5]. The data at ψ = 0.187 were
involved in the fit of the function kAB (T) given by Eq. (23). In Fig. 13 the calculated and the experimental
values are compared. The experimental cloud-point pressures for ψ = 0.065 are approximately 1 MPa
Fig. 11. Temperature dependence of the parameter kAB in the system MCH/PS.
higher than those for ψ = 0.187. Unfortunately, the calculated ones are more than 2 MPa too high.
Therefore, Fig. 12 does not contain these findings. The reason for the unsatisfactory result is the calculated
critical point that is located at a very low polymer concentration. Only matching the parameter kAB it is not
possible to shift the critical point to higher polymer concentrations. So, the pure-component parameters
of PS would have to be changed. However, the parameters bs , cs should not be dependent on temperature.
Only, the temperature dependence of the parameter as (assumed to be the same as for MCH) could be
changed. However, to restrict the number of parameters to have to be fitted we did not try this way.
Fig. 12. Calculated temperature dependence of the spinodal pressure in the UCST region for two polymer weight fractions ψ of
the system MCH/PS compared with experimental values: (䊏) ψ = 0.018; (䉬) ψ = 0.0682.
Fig. 13. Calculated temperature dependence of the cloud-point pressure in the LCST region of the system MCH/PS (ψ = 0.187)
compared with experimental data.
7. Conclusions
Spinodal and cloud-point curves of the system methylcyclohexane (MCH)/polystyrene (PS) may be
described using the Sako–Wu–Prausnitz equation of state (SWP-EOS). The pressure-concentration dia-
grams of the system MCH/PS in a certain temperature region shows both a curve with an upper critical
point (UCP) and a curve with a lower critical point (LCP). A small temperature decrease induces a qual-
itative change of the diagram producing a hour-glass shaped two-phase region. The SWP-EOS is able
to describe the transition of the UCP/LCP behaviour into the hour-glass diagram. If the PS sample of
the system is polydisperse the hour-glass shape for the spinodal curves and for the cloud-point curves
are formed at different temperatures. What happens in detail may be shown by computer simulation. In
this the polydispersity may be best considered by continuous thermodynamics Lowering the temperature
firstly the cloud-point curves merge at their extreme values. For the spinodal curves the formation of the
hour-glass shaped curves requires a further lowering of the temperature. On contrary to the monodisperse
case after formation of the hour-glass shaped curves the critical points do exist longer. Only an additional
temperature decrease results in the disappearing of the critical points. The treatment introduced may be
successfully applied to the real polydisperse system too. However, there are difficulties if the calculations
are to be extended to a wide temperature range.
List of symbols
a parameter of the SWP-EOS, Eq. (14)
A Helmholtz energy
b parameter of the SWP-EOS), Eq. (14)
Bi quantity introduced by Eqs. (8a) and (8b) describing the fugacity coefficient
of a component i in its dependence on the segment number
c parameter of the SWP-EOS), Eq. (14)
Js basic quantity to calculate the spinodal curve, defined by Eq. (3)

k parameter of the Schulz–Flory distribution, Eq. (11), k = 1/U
kAB binary parameter for the components A and B of the mixing rule Eq. (15)
M molecular weight
M̄n number average of the molecular weight
M̄w weight average of the molecular weight
p pressure
r segment number assumed to be proportional to the molecular weight, Eq. (17)
r̄B number-averaged segment number of the polymer B
r̄ M number-averaged segment number of the total mixture
R universal gas constant
T temperature (K)
U non-uniformity of the polymer, U = M̄w /M̄n − 1
V volume
W(r) continuous segment–molar (weight) distribution function depending on the segment number r
Greek letters
α ij quantities of the spinodal determinant Eq. (7) defined by Eqs. (6a)–(6c), i,j = V , ψ
φi fugacity coefficient of the component i
ψ total weight fraction of the polymer
Subscripts
A methylcyclohexane (MCH)
B polystyrene (PS)
i component i
s segment–molar quantity
s,i segment–molar quantity of the pure component i
Superscripts
I,II phases (I is considered to be the feed phase)
M mixture
Acknowledgements
The authors are grateful for the financial support by the Deutsche Forschungsgemeinschaft to accom-
plish this work.
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Calculation of The Cloud Point and The Spinodal Curve For T 2002 Fluid Phase

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Calculation of The Cloud Point and The Spinodal Curve For T 2002 Fluid Phase

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Fluid Phase Equilibria 194–197 (2002) 451–467

Calculation of the cloud-point and the spinodal curve for the

bs = (1 − ψ)bs,A + ψbs,B (16b)

cs = (1 − ψ)cs,A + ψcs,B (16c)

5. Formation of the hour-glass shaped curves in polydisperse systems

6. Results for a real polydisperse system

Js basic quantity to calculate the spinodal curve, defined by Eq. (3)

[1] S. Saeki, N. Kuwahara, S. Komno, M. Kaneko, Macromolecules 6 (1973) 246–250.

[4] H. Hosokawa, M. Nakata, T. Dobashi, J. Chem. Phys. 98 (1993) 10078–10084.

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