Ind. Eng. Chem. Res.

1989, 28, 1441-1446 1441

added directlv to obtain low-visocitv melts or it may be Literature Cited

prereacted with diallylbisphenol A and the resuiting
product and then blended with bidmaleimide) to obtain
thermoset powders. The fully cured powder compositions
display higher Tg's than the networks obtained from the
in situ reaction of the epoxy resins. All of the compositions
are thermally stable in air up to 375 "C. The results
demonstrate that relatively inexpensive and readily
available epoxies can be employed to obtain easily pro-
cessable bis(ma1eimide) and diallylbisphenol A high-tem-
perature polymeric compositions.
Acknowledgment
The authors thank D. M. Muschott and L. M. Skewes
for their technical assistance during the course of this work.
Registry No. (1)(2)(Epon 828) (copolymer), 65720-88-9;
(1)(2)(Araldite) (copolymer), 122093-48-5.
Carduner, K. R.; Chattha, M. S. Cross-linked Polymers: Chemistry,
Properties, and Applications; Dickie, R. A., Bauer, R. S., Labana,
S. S., Eds.; (America1 Chemical Society: Washington, DC, 1988);
pp 379-394.
Carduner, K. R.; Chattha, M. S. Polym. Mat. Sci. Eng. 1987,56,660.
Chattha, M. S.; Dickie, R. A. J . Appl. Polym. Sci. 1989, in press.
Chaudhari, M. A.; Galvin, T. J.; King, J. J. Proceedings of the 30th
National SAMPE Conference, 1985; pp 735-746.
Fukushima, E. N.; Roeder, S. B. W. Experimental Pulse NMR;
Addison-Wesley: Ontario, 1981.
King, J. J.; Chaudhari, M. A.; Zahir, S. A. Proceedings of the 29th
National SAMPE Conference, 1984; pp 392-408.
Shoolery, J. N. Prog. N M R Spectrosc. 1977, 11, 79.
Zahir, S. A.; Renner, A. US.Patent No. a4,100,140, to Ciba-Geigy
Corporation, July 11, 1978.
Received for review January 30, 1989
Accepted June 15, 1989

COMMUNICATIONS

A Simple Expression for the Nonrandomness Parameter crii in the NRTL

Equation for Completely Miscible Systems
+
The substitution aij = 1 / ( 2 GijGji)is proposed for modifying the original three-parameter NRTL
equation to make it a true two-parameter model for completely miscible systems. The performance
of the proposed expression is compared with the value of aij set according t o the rules of Renon and
Prausnitz, in correlating VLE data of binary systems, as well as in predicting binary systems from
infinite-dilution activity coefficients and ternary systems from binary data. Very good results are
obtained, a t least as good as when aij is set according t o the Renon rules, for both correlation and
prediction of VLE data. The expression proposed in this paper is applicable only to the vapor-liquid
equilibria of systems t h a t are completely miscible in the liquid phase.

Combination of the two-liquid theory of Scott (1956)and
the local composition idea suggested by Wilson and ex-
pressing the local composition in terms of mole fractions
rather than volume fractions lead to the NRTL (nonran-
dom two-liquid) equation derived by Renon and Prausnitz
(1968).
The expression for the excess Gibbs energy of the liquid
mixture is
c c
the i-j interaction. The parameter aij = aji is related to
the nonrandomness in the liquid mixture; when aij is zero,
the mixture is completely random and the NRTL equation
is reduced to the two-suffix Margules equation.
For a binary system, the activity coefficients are given
by

and the liquid-phase activity coefficients are given by

L

[ C

In yi =

where
c
j=1 TjiGjiXj

k=l
GkiXk
+ c
j=1
kcGji
-T.'-

xkGkj
1J
k=l

c
XkTkjGkj

k=l
c
XkGkj 1 (2)
The NRTL equation provides a good representation of
binary vapor-liquid equilibrium (VLE) experimental data,
and it is readily generalized for multicomponent mixtures
with only binary parameters. It is superior to the Wilson
equation in that it can represent liquid-liquid equilibrium
(LLE). Also, it is simpler in form than the UNIQUAC
(Abrams and Prausnitz, 1975) equation but has the main
g 11. . - g I1. . disadvantage of involving three adjustable parameters (G,,
Gij = exp(-aijsijl rij = ~ RT Gji,and aij = aji)for each pair of components. From both
practical and theoretical standpoints, it is desirable to
The significance of gij is similar to that of hij in Wilson's minimize the number of parameters needed to describe as
equation, namely, an energy parameter characteristic of wide a variety of systems as possible.
0888-5885/89/2628-1441$01.50/0 0 1989 American Chemical Society
1442 Ind. Eng. Chem. Res., Vol. 28, No. 9, 1989

In order to reduce the number of adjustable parameters Table I. Standard Deviations in Fitting Liquid-Phase
from three to two in the NRTL equation and to overcome Activity Coefficients of Binary Systems
the forecited disadvantage, Renon and Prausnitz (1968) std dev
recommend all = 0.20 for partially miscible systems, and no. of no. of 3- Renon's this
all data in the DECHMA LLE collection are correlated YW- data sets data pts parameter rules work
with this value for aIJ. <0.5 14 156 0.054 0.065 0.058
For completely miscible systems, Renon and Prausnitz 0.5-1.5 62 1095 0.028 0.028 0.028
(1968),from the reduction of experimental data for a large 1.5-5.0 82 1442 0.032 0.034 0.034
number of binary systems, found that the third parameter, 5.0-15 47 728 0.031 0.039 0.040
a,],varies from 0.20 to 0.47, depending on the chemical >15 17 303 0.040 0.062 0.053
nature of the constituents. Consequently, they consider total 222 3724
all to be an empirical constant, independent of tempera- av of all data 0.033 0.037 0.037
ture, for which an adequate value can be specified a priori sets
according to empirical rules based on the chemical nature
of the mixture's components. However, in a later paper, for the standard deviation, which has been used as the
Renon et al. (1971) represent all as a linear function of objective function
temperature for several mixtures. When aLJis assigned,
the NRTL equation has two adjustable parameters, G, and
'JI'
The rules proposed by Renon and Prausnitz (1968),
which are occasionally ambiguous, classify binary systems
into seven main groups (according to polarity and asso- 1
ciation of the components in the mixture), assigning dis-
crete values (0.2,0.30,0.40, and 0.47) for the all parameter In this fitting procedure, a correction for vapor-phase
in these groups. Although cylJ has almost no influence for nonideality was incorporated, and the activity coefficients
low values of the maximum of the excess Gibbs energy of were obtained from both isothermal and isobaric x , y, T ,
a binary mixture, it is very useful for strongly nonideal P data for completely miscible binary systems. The va-
binaries such as alcohol-hydrocarbon systems. This fact por-phase fugacity coefficients were calculated with the
susggests a close relationship between nonideality of the Peng and Robinson (1976) equation of state and the me-
mixture and the value of the a,, parameter and, conse- thod of Hayden and O'Connell(1975). Similar results were
quently, the likely existence of an expression for cylJ in obtained from both equations of state, with the exception
terms of G,, and GI,. In such a way, for a given system, of the systems n-pentane + acetone at 149.5, 124.6, and
cylJ should change with temperature in a continuous way,
99.6 "C. For these systems, the values obtained by the
decreasing at the same time as temperature increases. method of Hayden and O'Connell were used.
The results are summarized in Table I, where the cor-
Expression for aij related binary systems have been classified into five groups
according to the average infinite dilution activity coeffi-
The aim of this work is to find an adequate expression cients:
for aijin terms of Gij and Cji in order to reduce the NRTL
equation to a true two-parameter model for systems that 7av" = (71"+ 7 , " ) / 2 (6)
are completely miscible in the liquid phase.
Considering the inherent requirements of the ai, pa- The results lead to the following conclusions: (1) All
rameter and the observed variation of this one with Gij and forms of the NRTL equation perform well, and as one
Gji,we have developed several empirical expressions which might expect, the best results are obtained from the
lead to values of aij, in terms of G , and G,;, ranging from three-parameter form since this equation uses three ad-
0 to 0.5. The selected expressions were tested by corre- justable parameters to minimize the objective function. (2)
lation of experimental VLE data, and we have found that For systems with relatively high positive deviations and
the following simple equation exhibits very good behavior: both positive and negative moderate deviations from
ideality (0.5 < -yavm < 15),the Renon rules and this work
a.. = 1 forms of the NRTL equation perform well and exhibit
(4)
2 + GijGji similar behavior. (3) For systems showing both very strong
positive ( Y > ~15) ~and~very strong negative (-yavm < 0.5)
Substitution of aij from eq 4 into eq 2 gives the equation deviations from ideality, the this work form shows some-
referred to here as the this work form of the NRTL what better performance than the Renon rules form.
equation. In order to verify the performance of the this
work form, an extensive study was carried out by com- Temperature Influence on ail
paring its behavior in VLE data correlations and predic- To illustrate the influence of temperature on ai,, such
tions with the other two forms of the NRTL equation: (1) as was suggested in the introduction of this work, in Table
three adjustable parameters and (2) ai, parameter set ac- I1 the results of the fittings of six sets of experimental
cording to Renon's rules. isothermal VLE data, corresponding to the n-pentane +
In the first place, for this study, 222 reliable VLE data acetone system at temperatures ranging from -35 to 149.5
sets on completely miscible binary systems, at low or "C, are presented.
moderate pressures, were fitted with the three forecited As shown in Table 11, a12has almost no influence on the
equations. The systems' components include hydrocarbons standard deviation in the case of high temperatures, from
(paraffinic, naphthenic, and aromatic), ethers, esters, ke- 99.6 to 149.5 "C, and both the Renon rules and this work
tones, alcohols, phenol, n-cresol, water, and halogen-, forms of the NRTL equation lead to similar results.
nitrogen-, and sulfur-containing compounds. A fitting However, at low temperatures, from -35 to 25 "C, the
procedure, based on an algorithm developed by Marquardt influence of a I 2is very important, and the standard de-
(1963), was established to minimize the following equation viation for the Renon rules form (with respect to the this
 Ind. Eng. Chem. Res., Vol. 28, No. 9, 1989 1443

Table 11. Fit of Experimental VLE Data for the o-Pentane nonrandomness parameter in terms of the absolute tem-
+
( I ) Acetone (2) System from -35 to 149.5 "C perature, with an overall average deviation in a12of only
Renon's 0.10%.
rules this work
T , "C 7."- aI2 std dev aI2 std dev data source Infinite-Dilution Activity Coefficients
-35.0 16.4 0.20 0.046 0.463 0.016 Rall and Schlifer Infinite-dilution activity coefficients play an important
(1959) role in the analysis of separation processes, and the many
-15.0 10.2 0.20 0.036 0.445 0.022 Rall and Schafter
(1959)
advantages of y in characterizing miscible solution be-
25.0 6.7 0.20 0.031 0.419 0.021 Rall and Schafer havior are well documented (Tassios, 1971; Eckert et al.,
(1959) 1981). On the other hand, in recent years a number of new
99.6 3.7 0.20 0.029 0.385 0.027 CamDbell e t al. techniques, primarily chromatographic, have been devel-
(1986) oped for the relatively easy and rapid determination of
124.6 2.4 0.20 0.021 0.377 0.021 Camubell et al. activity coefficients in the limit of infinite dilution, and
(1986) a considerable amount of information on limiting activity
149.5 2.2 0.20 0.016 0.371 0.016 Campbell e t al.
(1986) coefficients is available in the literature (Gmehling et al.,
1982; Thomas et al., 1982; Macedo et al., 1983; Tiegs et al.,
av 0.030 0.021
1986; Bastos et al., 1988).
work form) greatly increases as the temperature reduces. The this work form of the NRTL equation is a true
These results suggest that the aij parameter should be set two-parameter model, and consequently, the parameters
according not only to the chemical nature of mixture can be calculated from a single experimental data or from
components but also to the temperature. Therefore, as- a pair of infinite-dilution activity coefficients. Thus, for
suming that a linear reciprocal absolute temperature de- infinite dilution conditions, eq 3 become
pendence for the logarithm of cyl2 exists, the values of a12
for this work form of the NRTL equation shown in Table
In Y~~ = -(2 + G12G21)(lnGzl + GI2 In G12)
I1 were correlated with temperature to obtain the following
expression
In a12= -1.27986 + 121.541/T Therefore, a further test of the this work form was
carried out, studying its ability to predict binary VLE from
which provides a very accurate representation of the infinite-dilution activity coefficients.

Table 111. Prediction of Experimental Data from Two Infinite-Dilution Activity Coefficients
av abs error in
vapor mole
fraction
exptl Renon's this
no. system 1-2 T , "C 77- 7,- a,, rules work data source
1 water-hydrazine 58-75 0.17 0.03 0.30 0.008 0.008 Burtle (1952)
2 quinoline-m-cresol 180.3 0.10 0.18 0.30 0.012 0.012 Krevor et al. (1986)
3 quinoline-m-cresol 160.4 0.15 0.19 0.30 0.007 0.007 Krevor e t al. (1986)
4 quinoline-m-cresol 200.3 0.12 0.30 0.30 0.010 0.010 Krevor et al. (1986)
5 diethyl ether-halothane 30.0 0.23 0.21 0.30 0.005 0.005 Gmehling et al. (1980)
6 diethyl ether-halothane 33-51 0.31 0.26 0.30 0.002 0.002 Gmehling e t al. (1980)
7 benzothiazole-m-cresol 160.3 0.36 0.43 0.30 0.010 0.010 Krevor et al. (1986)
8 chloroform-ethyl acetate 63-78 0.54 0.36 0.30 0.003 0.003 Nagata (1962)
9 acetone-chloroform 45.0 0.44 0.47 0.30 0.008 0.008 Kudryavtseva and Susarev (1963)
10 acetone-acetonitrile 45.0 1.05 1.04 0.30 0.008 0.008 Brown and Smith (1960)
11 n-octane-2-methylpentane 40.0 1.18 1.04 0.30 0.006 0.006 Liu and Davison (1981)
12 methylcyclopentane-benzene 71-80 1.47 1.34 0.30 0.002 0.002 Myers (1956)
13 acetone-benzene 45.0 1.65 1.52 0.30 0.005 0.005 Brown and Smith (1957)
14 acetone-carbon tetrachloride 45.0 3.00 2.15 0.30 0.009 0.009 Brown and Smith (1957)
15 n-pentane-acetone 149.5 2.82 2.50 0.20 0.030 0.029 Campbell et al. (1986)
16 benzene-acetonitrile 70.0 2.70 2.65 0.30 0.007 0.007 Monfort (1983)
17 benzene-acetonitrile 73-82 2.55 3.15 0.30 0.008 0.008 Mato and S h c h e z (1967a)
18 n-pentane-acetone 124.6 3.15 2.98 0.20 0.027 0.026 Campbell e t al. (1986)
.19 n-pentane-acetone 99.6 3.57 3.64 0.20 0.027 0.025 Campbell e t al. (1986)
20 diethylamine-acetonitrile 24.8 3.65 4.10 0.30 0.008 0.007 Srivastava and Smith (1985)
21 n-pentane-acetone 25.0 6.56 8.04 0.20 0.028 0.017 Rall and Schafer (1959)
22 acetone-cyclohexane 25.0 8.50 6.50 0.20 0.016 0.005 Tasic et al. (1978)
23 ethanol-benzene 45.0 10.60 4.45 0.47 0.005 0.006 Brown and Smith (1954)
24 butanol-carbon disulfide 30.0 13.00 2.60 0.47 0.003 0.004 McKeigue and Gulari (1986)
25 acetonitrile-triethylamine 70-87 9.00 9.00 0.47 0.010 0.011 Mato and S h c h e z (1967b)
26 nitromethane-carbon tetrachloride 45.0 10.60 7.45 0.47 0.007 0.005 Brown and Smith (1955)
27 carbon tetrachloride-acetonitrile 65-80 5.00 15.00 0.47 0.020 0.020 Mato and S h c h e z (1967a)
28 n-pentane-acetone -15.0 11.48 12.36 0.20 0.038 0.012 Rall and Schiifer (1959)
29 ethanol-methylcyclopentane 60-77 20.00 5.75 0.47 0.012 0.011 Sinor and Weber (1960)
30 ethanol-n-hexane 58-68 18.10 9.05 0.47 0.009 0.010 Wehe and Coates (1955)
31 n-pentane-acetone -35.0 14.13 15.21 0.20 0.035 0.003 Rall and Schlifer (1959)
32 ethanol-n-heptane 30.0 20.00 14.00 0.47 0.012 0.012 Ronc and Ratcliff (1976)
33 ethanol-n- heptane 30.1 23.00 12.50 0.47 0.005 0.005 Berro et dl. (1982)
34 ethanol-isooctane 50.0 27.50 10.80 0.47 0.014 0.015 Kretschmer et al. (1948)
35 ethanol-carbon disulfide 30.0 53.00 6.50 0.47 0.010 0.010 McKeigue and Gulari (1986)
av 0.012 0.010
1444 Ind. Eng. Chem. Res., Vol. 28, No. 9, 1989
In Table 111, the average absolute error in the vapor mole
fraction, calculated using parameters obtained from infi-
nite-dilution activity coefficients, is shown for the Renon
rules and this work forms of the NRTL equation. The cyl2
parameter set according to Renon's rules for each system
is also shown in Table 111. The experimental values of ylm
and y2- were obtained by graphic extrapolation to infinite
dilution in both dilute regions for each binary pair.
As shown in Table 111, both forms of the NRTL equation
exhibit generally a very good performance, providing sim-
ilar results, with the exception of the n-pentane + acetone
systems at low temperatures (25, -15, and -35 "C) and the
acetone + cyclohexane system at 25 " C , where the this
work form predicts substantially better than the Renon
rules form.

Prediction of Ternary Vapor-Liquid Equilibrium

from Binary Data
A study covering 13 ternary miscible systems was carried
out in order to compare the performance of the three-
parameter, Renon rules, and this work forms of the NRTL
equation in predicting multicomponent VLE from binary
data. Equation 2 was employed for each form of the
NRTL equation, with binary parameters obtained from
fitting the binary systems, and the corresponding activity
coefficients and vapor mole fractions were calculated for
each ternary system.
The results are presented in Table IV and indicate that
good prediction of ternary VLE can be achieved with all
three forms of the NRTL equation. In opposition to what
would be expected, both the this work and Renon rules
forms give slightly better results than the original three-
parameter NRTL equation. This conclusion agrees with
that previously obtained by Larson and Tassios (1972),
who studied the accuracy of the three-parameter and
Renon rules forms of the NRTL equation in predicting the
activity coefficients for ternary systems from binary data
only. It is interesting to remark that the this work form a
provides very good prediction of ternary VLE data from .
4

binary, at least as good as the NRTL equation with the E

value of aij set according to the rules of Renon and 4
Prausnitz. 5
5
a
Conclusions C
ti
In this work, we have proposed the simple expression E
cui, = 1 / ( 2 + GijG,,) in order to reduce the number of ad- t alal
justable parameters from three to two in the original rl e,
NRTL equation. The resulting equation, referred to in
this paper as the this work form of the NRTL equation, 6
is a true two-parameter model which eliminates the am- r
I
>
biguity encountered sometimes in choosing the proper c1
value of the nonrandomness parameter aij according to the
rules recommended by Renon and Prausnitz for completely i
miscible systems. L

The performance of both the this work and Renon rules E

forms of the NRTL equation is compared in correlating .C

VLE data of binary systems and in predicting binary .-z

c

systems from infinite-dilution activity coefficients and t

e
ternary systems from binary data only.
The this work form of the NRTL equation exhibits a i
very good behavior for both correlation and prediction of G
5
VLE data of completely miscible systems. It appears to
give at least as good results as the Renon rules form for $
correlation of VLE data of binary systems and prediction
of ternary systems from binary data only, and it gives
slightly better results than the Renon rules form in pre-
dicting binary systems from infinite-dilution activity
coefficients.

The substitution ai' = 1/(2 + GijGjJ qroposed in this
work is only applicabie for completely miscible systems,
and therefore, it can't be used for representation of liq-
uid-liquid equilibria. In this case, the value aii = 0.20,
recommended by Renon and Prausnitz, will be used.
Nomenclature
C = number of components
g = molar Gibbs energy
gij = energies of interaction between i-j pair of molecules
Gij = parameter in the NRTL equation
N = number of data points
R = gas constant
T = absolute temperature
x = liquid mole fraction
x i j = local mole fraction of molecule i in the neighborhood of
molecule j
y = vapor mole fraction
Greek Letters
aij = nonrandomness parameter for binary i-j interactions
T~~ = parameter in the NRTL equation
y = activity coefficient
Superscripts
E = excess property
= = infinite dilution
Subscripts
av = average
cal = calculated
exp = experimental
i , J , k = components,
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Fidel A. Mato, Rafael B. Mato, Fidel Mato*
Departamento de Ingenieria Quimica
Facultad de Ciencias
Universidad de Valladolid
47011 Valladolid, Spain
Received for review December 13, 1988
Revised manuscript received May 22, 1989
Accepted J u n e 13, 1989

Selective Fines Destruction in Batch Crystallization

Batch crystallization of pentaerythritol was carried out with and without fines removal and dissolution.
With fines destruction, the number of small crystals in the product was decreased, giving a corre-
sponding increase in the average size. Crystal size distribution (CSD) changes due to fines destruction
were modeled with a population balance approach. Good correlation between predicted and ex-
perimental CSDs was observed.

In most crystallization systems, the final CSD is an
important consideration. An increase in the average crystal
size and a decrease in the number of small crystals will
usually increase the filtration rate, lower the amount of
mother liquor entrained on the crystals, and possibly in-
crease the value of the product.
Fines destruction is commonly used to increase the
particle size in a continuous crystallizer (Randolph and
Larson, 1988). Previous studies by Jones et al. (1984) and
Jones and Chianese (1987) have shown its applicability to
batch crystallization. In the present study, pentaerythritol
was crystallized in a batch crystallizer with and without
fines destruction. The runs were otherwise identical. CSD
and solution concentration were monitored during the
crystallization process in both systems. Comparison of
CSDs in these two cases shows the effect of fines de-
struction.
Population balance equations can be used to predict the
changes in CSD caused by fines destruction, showing that
fines destruction will result in a decrease in the population
density of crystals smaller than the fines cut-off size ( L F )
and an increase of the population density of crystals larger
than LF.
Theoretical Considerations
A general population balance can be written for a con-
stant batch crystallizer with fines destruction related
analogously to the continuous case as
dn/dt + d(Gn)/dL + Q ( L ) n / V = 0
where n(L)is the population density, t is the time, L is the
crystal size, G is the linear growth rate, Vis the crystallizer
volume, and Q(L)is the size-dependent removal of crystals
(fines in this case). Thus,
0888-5885/89/2628-1446$01.50/0
The solution of eq 1 and 2 for the final crystal size
distribution requires values of growth and nucleation rates
and a knowledge of the concentration profile followed
during crystallization. Because growth and nucleation
rates depend on the concentration, a simultaneous solution
of equations describing growth, nucleation, solubility, and
solution temperature must be solved to determine the
CSD.
CSD changes due to fines destruction can be predicted
qualitatively if the following assumptions are made: (1)
The growth rate is constant, (2) no nucleation occurs, and
(3) there is no size dependence or dispersion of the growth
rate. In a time period At, crystal growth can be approx-
imated by AL = Gat. Without fines destruction, this
would result in a shift of the entire population density
curve in the amount AL. This is shown as the dotted line
in Figure 1. If fines destruction is used, crystals larger
than the fines cut-off size, LF, will not be affected, so there
will be no change in their population density. Crystals
smaller than LF - AL at the beginning of the time period,
At, will be exposed to fines destruction for the entire time
period and their population density will be reduced ac-
cordingly. Crystals between the size of LF - AL and LF
will be exposed to fines destruction for varying amounts
of time depending upon their size. The resulting CSD
changes are shown as the solid line in Figure 1.
The population density a t any time t + At for fine
crystals can be represented as
n(L,t+At) = n(L-AL,t) exp(-At/rF) (3)
(1)
where At/rF represents the number of turnovers in the
time period At. Equation 3 merely represents changes in
population density as a particle moves along a character-
istic in the L-t plane.
Experimental Procedure
A clear cast acrylic crystallizer with an internal draft
tube and four radially spaced baffles was used for the
experiments. Draft tube circulation is not typically used
0 1989 American Chemical Society