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Vapor-Liquid Equilibria of Nonideal Solutions
Harrison C. Carlson, and Allan P. Colburn
Ind. Eng. Chem., 1942, 34 (5), 581-589 DOI: 10.1021/ie50389a013
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Vapor-Liquid Equi l i bri a of
Nonideal Solutions
Uti l i zati on of Theoreti cal
A- e. e& area A& P. e-
E. l . du Pont de Nemours & Company, Inc., Wilmington, Del.
t o Extend Data
Vapor-liquid equilibrium data may be readily evaluated
and extended when they are calculated as activity coef-
ficients. The equations proposed by van Law, Margulas,
and Scatchard and Hamer, which express the activity
coefficients of both components of a binary mixture as
functions of the liquid composition and empirical con-
stants, are capable of fitting most of the available vapor-
liquid equilibrium dab.
Experimental data may be examined for accuracy by
noting the relation of the activity coefficients for the equi-
molal mixture to the terminal values, and may be smoothed
by fitting the data with one or another of these equations.
With these integrated forms of the Gibbr-Duhem equrtion,
complete vapor-liquld equilibria may be calculated from
measurements of azeotropic composition, total pressure or
boiling point curves, or liquid-liquid solubility.
The terminal values of the activity Coefficients and the
constants OF the van Laar equations for a homologous series
of alcohols in binary mixtures with water or benzene are
shown to progress regularly with increasing molecular
weight. The effect of pressure or temperature on the
curves of equilibrium liquid and vapor composition may be
calculated. Approximate procedures for estimating tern-
ary equilibrium data from those on the three binary systems
are given. Liquid-liquid distribution coefficients may be
predicted from the activity coefficients.
ESPITE the wide utilization of dis%illation and similar
D contacting apparatus and the need of reliable data on
vapor-liquid equilibria to design such apparatus, relatively
little attention has been paid to the important problem of
evaluating and extending such data for nonideal solutions.
Although considerable work has been done on the effect
of deviation from the gas lbws under conditions of pressure
distillation, this work is largely limited to those mixtures
which form ideal solutions in the liquid, such as members
of a homologous series. I n chemical industry a large share of
distillation problems involves materials of dissimilar chemical
nature, such as aqueous mixtures, and here large deviations
from Raoults law are encountered. The practice has usually
been to determine data experimentally for any system under
the exact conditions of later use, but this is time consuming
and sometimes too difficult to be practicable. Therefore,
the purpose of this investigation was to study the theoretical
background of nonideal mixtures and to derive convenient
methods of evaluating and extending data on vapor-liquid
equilibrium.
1 Present address, University of Delaware. Newark. Del.
When experimental data on vapor-liquid equilibrium are
plotted in the customary manner of y, mole fraction of the
more volatile component in the vapor, against 2, the mole
fraction of the more volatile component in the liquid, curves
of the types shown in Figure 1 are obtained. On such a plot
there appears to be little rhyme or reason. If these same
data are calculated in terms of deviation factors from Raoults
law by the equations,
and the deviation factors are plotted on semilog paper again&
the composition of one of the components in the liquid,
characteristic ourves are obtained like those in Figure 2.
These are orderly and consistent. Such plots obviously
permit a ready detection of poor experimental data. They
are more valuable than a mere graphical representation, how-
ever, as will be discuased below.
Theoretical Equations
GIBBS-DWEM EQUATION. The term introduced as devia-
tion factor from Raoults law is, under conditions to be de-
iined immediately, equivalent to the thermodynamic prop-
erty, activity coefficient. As such, there is a definite rela-
tion between the values for the several components. This
relation, according to Lewis and Randall ( I $) , follows from
the Gibbs relation between the partial molal free energies,
PI, F,, etc.:
21 (3) dX1 P , T f s (3) dxl P.T +.... =0
Since
dF1 =RT b lnfi, and Equation 2 becomes:
=RT In fi +constant, at constant temperature
In this equation f, the fugacity, can be regarded as the
ideal partial pressure, and is identical with partial pres-
sure p for conditions under which the gas laws hold.
Lewis and Randall (IS) define activity, a, as the relative
fugacity, or the ratio between the fugacity of the substance
in solution and its fugacity as a pure liquid. Thus, a1 =
fl/f; and a2 =f2/fi1 where al and a2 are the activities of com-
ponents 1 and 2, and f: and fi are the fugacities of the pure
liquids. Activity coefficients y are simply the activities
divided by their respective mole fractions, or y1 =at / z~,
71 =a*/%*, etc. Thus:
YI =I f1Kx1, etc. (4)
581
582 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 34, No. 5
Y I
0 0.2 0.4 0.6 0.8 1.0
Figure I . Equilibrium Mol e Fraction of Low-
Boiler i n the Vapor, yl, VI. Mo l e Fraction in
the Li qui d, x1
Curve System Conditions Citation
A Chloroform-ethyl alcohol 3 5 O c. (20)
B n-Butyl alcohol-water 1 atm. (23)
C Isopropyl alcohol-isopropyl ether 1 atm. (76)
D Acetone-chloroform 35.17"C. (44)
E n-Propyl alcohol-water 1 atm. ( 6)
Where the vapors are perfect gases, fl =pl and f; =PI, so
that:
( 5 )
It is thus apparent that the deviation factors defined by
Equation 1 are equivalent to values of activity coefficient
under conditions that the vapors approximate perfect gases.
Scatchard and Raymond (go) applied a slight correction for
gas law deviation even at atmospheric pressure.
The Gibbs-Duhem equation, expressed by Equation 3,
can be more conveniently used when in terms of activity
coefficients. Substituting for fi, fi, etc., in Equation 3 their
values from Equation 4, and noting that values off;, fi, etc.,
are constant at constant temperature and that d( zl +z2 +
71 =PI/PIXI =Pyl/Plx1, etc.
.
) =d(1) =0,
For binary mixtures, axl =-ax2, so that
Equations 6 and 7 are of immediate value in studying
experimental data on vapor-liquid equilibrium by relating
the slopes of such curves as those of Figure 2. Inasmuch
as the magnitudes of slopes are diflicult to determine pre-
cisely, however, studies have been made to obtain convenient
mathematical solutions of this differential equation. The
results of some of these studies are proving to be helpful and
will be discussed below.
Perhaps the most useful of the
solutions are the equations derived by van Laar (IO) from a
thermodynamic study; they are given below in a slightly re-
arranged form :
VAN LAAR EQVATIONS.
I n this symmetrical form, constants A and B have the prop-
erty of being equal to the terminal values of log y of the two
curves. Thus, at 21 =0, log y1 =A, and at $1 =1 when
2 2 =0, log yz =B. It is of interest, too, to observe that at
z1 =0, log yz =0 or y2 =1, and at z1 =1, log yl =0 or
y1 =1, which satisfy the limiting condition that Raoult's
law holds for a component whose concentration approaches
100 mole per cent. By performing the differential operations
indicated by Equation 7 , the van Laar equations are readily
proved to be a true solution of Equation 7 .
The curves represented by Equations 8 and 9 have a
peculiar property which is readily shown at the mid-points
on the curves. When x1 =0.5,
If A =B, the term AB/ ( A +B) 2 =1/4. As A and B differ,
the ratio decreases slightly; e. g., when A =2B, AB/ ( A +
B) ? =219. According to Equation 10, the halfway value
on one curve is approximately one fourth the end value on
the other curve. Thus the curve having the higher end value
will be the lower at $1 =0.5. This particular property can
be readily seen on plots of experimental data similar to those
of Figure 2 and permits at once a qualitative check on the
data.
For the special case of A =B, Equations 8 and 9 become:
log =11x2, log 7 2 AX: (11)
On semilog paper these are ordinary parabolas passing
through their respective origins, and the values at z =0.5
are one fourth the end values, as stated above. Many
systems have values of A and B close together and, for a
few, A and B are equal.
MARGULES EQUATIONS. Margules (14) integrated the
Gibbs-Duhem equation in terms of a pair of exponential
series with unlimited numbers of terms and then derived the
constants for one of the equations from those of the other by
applying Equation 7 . He was hopeful that only two terms
would be needed to apply the equations because more would
be unwieldy. We have slightly revised the constants of
these equations in the same manner as for those of van Laar
in order to utilize the end values as constants. So expressed.
the Margules two-term equations are:
( 12)
(13)
As a check one readily finds that at z1 =0, log y1 =A and
log y2 =0; at z1 =1, log yl =0 and log 7 2 =B. It is of
interest that for these equations, at zl =0.5, log 71 =B/4
and log yz =A/4, regardless of the values of A and B.
The Margules equations become identical with those of
van Laar when A =B and are then also expressed by Equa-
tion 11. When A and B are different, however, the two sets
trf equations represent different curves, with the difference
growing as the ratio A/ B departs more widely from unity.
To distinguish between the two sets of equations, therefore,
data are needed which will yield considerably different values of
A and B. For other data either set of equations is satis-
factory, but the van Laar equations are generally somewhat
more convenient.
QCATCWRD EQUATIONS. Scatchard and Hamer (19) ex-
tended the methods of van Laar to obtain equations which
log 71 =( 2B - A ) 2% +2(A - B) X;
log y2 =(2A - B) X: +2(B - A ) 1,9
May, 1942 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 583
we have again revised so that the constants represent end Scatchard (17) derived an equation in which all the con-
values of the curves as follows : stants represent physical properties for systems in which the
change of entropy on mixing is the same as that for an ideal
mixture, designated a "regular solution" by Hildebrand :
log y1 =A (y - 1) z; - 2A (A*2BV - 1) z: (14)
AV
(15)
logy2 =B ( 2 g - 1)z; - 2 B ( B 7 A VZ - 1)z:
where VI, VS =molar volumes
Noting that z1 =V1xl/(V1xl +V2xJj the following special
cases are found:
When the molar volumes are equal, i. e., VI =VL, then
z1 =zl, et?., and Equations 14 and 15 reduce to the Margules
equations given by Equations 12 and 13.
When the ratio A / B is equal to the ratio Vl/V*--i. e.,
when AV~ / BVI =1-Equations 14 and 15 reduce to those of
van Laar, Equations 8 and 9.
When the ratio AVz/BVI lies between A/ B and 1, the
curves will lie between those of Margulea and van Law.
zl, z2 =volume fractions of the components
1.
2.
I I
and AE is the change in internal energy for vaporization of
the pure liquids. Scatchard, Wood, and Mochel ( d l ) , from
a study of the three binary systems formed by benzene, cyclo-
hexane, and carbon tetrachloride, have concluded that
Equation 18 did not give values of b agreeing with those
found by measurement of vapor-liquid equilibria. If b,
V1, and VZ are regarded as empirical constants, Equations 16
and 17 may he arranged in a form equivalent to the van Laar
equations.
I
0.4 0.6
XI
Figure Q. A ' ' Coef-
ficients vs. Mole ct'v'? ractions
A. Isopropyl ether in isopropyl
alcohol. Curve calculated by
van Ldar equation with A =
0.49 and &? =0.60. Points are
measured values of Miller and
Bliss (76) at atmospheric pres-
sure.
B. n-Propyl alcohol in water.
Curve calculated by van Laar
equation with A = 1.13 and
B =0.49. Points are the ob-
served ddta of Gadwa (6) at
atmospheric pressure.
C. Acetone in chloroform.
Curve calculated by van Laar
equation with A =-0.44 and
B =-0.34. Points are the ob-
served data of Zawidski ( 24) at
35.17"C.
D. Chloroform in ethyl alcohol.
Curve calculated by Mar des
equation with A =0.21 an35 =
0.71. Points are the observed
data of Scatchard and Raymond
(no) st 35" c.
E. Water in n-butyl alcohol.
Curve calculated by van Ladr
equation with A =0.61 and B
=1.34. Points were measured
by Stockhardt and Hull (93) at
atmospheric pressure. Two liq-
uid phases are present for com-
positions between the two
(dashed lines.
5&1 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 34, No. 5
As stated previously, the van Laar and hlargules equations
differ most when the ratio A/ B departs considerably from
unity. To compare the sets of equations, Figure 3 has been
caloulated with the value of A =3B for each set. One of
the Margules curves has a maximum and the other a minimum
with this large ratio of A/ B. By their mathematical nature
the van Laar equations cannot show such shapes. Figure 3
also shows curves for the Scatchard-Hamer equations for a
value of AV2/ BVl different from those listed under special
cases 1 and 2.
8.0
6.0
5.0
4.0
2( 3.0
2.0
1.5
1.0
0.2 0.4 0.6 8.8 1.0
0.9; ' ' 1 ' I I I ' '
XI
Figure 3. Comparison of Acti vi ty Coef-
ficients Predicted by vdn bar , Margules, and
Scatchard-Harner Equations
Curves pass through the same terminal values and
with a ratio of the logarithms OF the terminal activity
coefficients =3-i. e., A =38. The Scatchard-
Hamer equation is for AVZ/BV, =9.
van Laar
Margules- - - - -
Scatchard-Hamer - __
COMPARISON OF EQUATIONS WITH DATA. Two sets of
reliable experimental data, for which A values are consider-
ably different from B values, are those of Gadwa (6) on n-
propyl alcohol-water and of Scatchard and Raymond (go) on
chloroform-ethyl alcohol (Figure 2, B and D). The n-propyl
alcohol-water data are represented closely by the van Laar
equations, with A =1.13 and B =0.49, whence A/ B =
2.31. I n this case the Margules equations would not have
been good. On the other hand, the chloroform-ethyl alcohol
data agree with the Margules equations when A =0.21 and
B =0.71 ( A/ B =0.296), while the van Laar equations do
not apply. The clue as to which equations to use apparently
follows from the values of molar volume. These values for
wpropyl alcohol and water are 75 and 18, respectively (at
room temperat.ure), which are in the ratio of 4.16/1 On the
other hand, the values of molar volume for chloroform and
ethyl alcohol are 81 and 58.5, respectively, which is a ratio
of 1.38/1. The former case approaches Scatchard and
Hamer's special case 2, and the latter approaches case 1
since the molar volumes are more nearly equal.
I n general, the van Laar equations have been found to fit
many systems well. Since many important binaries include
water, the molar volumes are bound to be different and
the van Laar equations are then indicated. The example of
ohloroform-ethyl alcohol is the only one wehave encountered
where the Margules equations were definitely called for, but
they no doubt will have other application on systems with
molar volumes which are nearly equal but where the values
of A and B differ considerably. Further work should show
whether the complete form of the Scatchard-Hamer equations
should sometimes be employed.
Although the large
proportion of nonideal systems shows positive deviations
(meaning the values of log y are positive-i. e., the values of
y are above unity), some have negative deviations (y is
fractional) such as acetone-chloroform (Figure 2C). Nega-
tive deviations occur in electrolytes and other liquids where
association or compound formation of some type reduces the
volatility. Such systems encountered include, in addition
to electrolytes: chloroform-acetone, chloroform-benzene,
chloroform-ethyl ether, acetylene-acetone, acetylene-ethanol,
formic acid-water, methylamine-n-ater, hydrogen peroxide-
water, and acetic acid-pyridine.
Although these equations represent satis-
factorily a large share of existing reliable data, some pre-
cautions are necessary in their use. These have to be con-
sidered chiefly where the vapors depart appreciably from the
ideal. Thus the experimental curves of values of log y us. x
show unusual shapes for such systems as acetaldehyde-water,
acetic acid-water, and acetic acid-benzene. Here the vapors
are associated and one cannot use Equation 5 as an approxima-
tion for Equation 4. Similarly, for cases of high pressure the
values of y must be defined by Equation 4, although at
moderate pressures Equation .5 has proved satisfactory.
One aqueous system has been found where no set of
equations appears to apply exactly-namely, butyl alcohol-
water (Figure 2E). Here there is a wide difference between
the end values of the two curves and also an immiscible
region; hence the system is not common. There is need of
considerable research on partially miscible mixtures.
One must conclude at this time that although the van Laar
equations fit many systems very closely, there are a few
where the agreement is not satisfactory. However, they can
be employed as B first approximation and thereby provide a
powerful tool for the extension of data, as described below.
POSITIVE us. KEGATWE DEVIATIONS.
LIMITATIONS.
Examination of Vapor-Li qui d Equilibrium Data
I n examining vapor-liquid equilibrium data to determine
their reliability, several procedures have been proposed.
Plots of y vs. z similar to Figure 1, or of the relative volatility,
a, us. x can be made. These methods show only the spread
of the experimental points from a smooth curve and do not
give any idea of the thermodynamic consistency.
The differential form of the Gibbs-Duhem equation per-
mits a few qualitative conclusions to be drawn from an
inspection of a plot of log y us. zl. If the slope of the activity
coefficient curve for one component on this type of plot is
zero, corresponding to a maximum, the slope of the curve for
the other component must be zero at the same composition;
Figure 20 is an example. I n some cases the activity coef-
ficients for compositions approaching 2 =1.0 are below unity
without any indication of a maximum in the activity coef-
ficient curve of the other component; this indicates some error
in the data.
The Gibbs-Duhem equation indicates that plots of log yl
and log y~ us. z1 should have slopes of opposite sign at a given
composition. (Xumerically, the slopes are in the ratio
zl/xz.) Thus, if one curve starts at log y p =0 and constantly
increases, the other curve must steadily decrease as we
pass from x1 =0 to z1 =1.0. If one component has activity
coefficients always greater than unity and is without a maxi-
mum point, the activity coefficient curve for the other coni-
ponent must always be greater than unity. If the activity
May, 1942 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 585
Cour t esy, Texas Gull Sulphur Company
High-pressure Air Makes Possible the Efficient Production of Sulfur
Every day 1,500,000 cubic Feet of air at 500-600 pounds per square inch pressure are used to liFt the molten sulfur
to the surface.
coefficient of one component is less than unity and without
an inflection point, the activity coefficient of the other com-
ponent must always be less than unity.
An integrated form of the Gibbs-Duhem equation, such
as the van Laar equation, permits quantitative conclusions
as to the reliability of vapor-liquid equilibrium data more
rapidly than the differential form of the Gibbs-Duhem
equation. Comparison of the value of log y1 and log YZ
measured at z1 =0.5 and that usually extrapolated to XI =
0 and xl g =1.0 affords a rapid test of data. An earfier section
of this paper showed that at z =0.5, log y2is approximately
one fourth of A, and log y1 is approximately one fourth of B.
Measurement of the relative values of log y at the mid-point
and end point on a semilog plot will give a rapid test of the
data. Likewise the curve having the higher end value will
be lower at the mid-point.
Since Figures 2A, B, and C show that the van Laar or
Margules equations are capable of fitting reliable determina-
tions of activity coefficients for miscible systems, vapor-
liquid equilibrium data may be smoothed with some confi-
dence by fitting the activity coefficient curves with van Laar
or Margules equations. An inspection of data on a number
of systems indicated that the majority of the determinations
could be fitted better by the van Laar equation, as the type
of curve shown in Figure 2 0 is relatively rare. Only a few
determinations of vapor-liquid equilibria are so precise that
they could not be improved by fitting the activity coefficients
with an analytical equation, followed by calculation of
equilibrium liquid and vapor compositions and boiling points
from the smoothed activity coefficients. This method of
smoothing activity coefficients rather than liquid and vapor
compositions presupposes that the boiling points have been
measured accurately and that the vapor pressures of the pure
components are known.
For convenience in calculating the constants of the van
Laar and Margules equations, they have been solved simul-
taneously for A and B to give:
B =log yn (1 +x - > *
xz log YZ
For the Margules equations written in terms of the terminal
activity Coefficients:
log Y2 I 2 log Y1
B =(21 - w) r:
xz
(22)
Extension of Incomplete Data
I n industrial work it is often necessary to estimate distilla-
tion apparatus on systems where complete equilibrium data
for the conditions chosen are not available. Some of the
types of data discussed below can sometimes be readily
located, however, and, in lieu of complete information, will
be found helpful.
Estimation of Equilibrium Curve from Azeot r opi c Data
When complete measurements of the equilibrium liquid
and vapor compositions are lacking, one may estimate the
activity coefficients from the azeotropic compositions and
boiling point. A wealth of azeotropic data has been tabu-
lated by Lecat (11). Since the azeotropic liquid and vapor
compositions are identical, the activity coefficients simplify
to
7 1 =P/P1 ( 5 4
YZ =P/Pa (5B)
One may solve for the constants in the van Laar or Margulea
equations from these two values of the activity coefficient
586 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 34, No. 5
TABLE I. EFFECT OF PRESSURE ON ETHYL .kCETATE-&HYL
ALCOHOL AZEOTROPE
Mole Fraction of Ethyl Acetate Total Pressure,
Temp., C P ~ / P I Calculated Measured (1.5: Mm. H g
18. 7 0.598 0. 787 0, 734 77. 4
40. 5 0. 725 0.677 0, 660 220
56. 3 0. 827 0. 602 0. 601 423
71. 8 0. 921 0. 539 0. 539 760
83. 1 0. 994 0. 498 0. 490 1121
91. 4 1.049 0.480 0. 461 1476
by Equations 19 to 22. The whole activity coefficient curve
and subsequently the x- y values may be calculated by sub-
stituting these constants in the van Laar or Margules equa-
tions. Allen (1) employed the original form of the Margules
equation for this purpose. This procedure is most accurate
when the azeotrope lies in the middle half of the composition
range. When the azeotrope lies betv-een x =0.75 and z =
1.0, only the value of B will be accurate. Inspection of many
systems has shown that more cases are fitted by the van Laar
equations than by the hfargules expansion.
0 20 40 60 80 100
t ' C. AND MOLE PER CENT ETHYL ACETATE
Figure 4. Effect of Temperature on the
Composition of the Ethyl Acetate-
Ethyl Alcohol Azeotrope
At a given temperature the azeotropic composi-
tion i s where Pz/Pi =Y I / Y ~.
For example, Smith and Rojciechowski's measurement
(29) of the dioxane-water azeotrope of 0.53 mole fraction
water, boiling at 87.8" C. at atmospheric pressure, may be
used to calculate that y1 =1.57 and y~ =1.55. The con-
stants in the van Laar equation, A and B, may be calculated
to be 0.68 and 0.88, respectively, which are close to the
values calculated from total pressure data in a later section.
Effect of Pressure on Azeotropic Composition
The change in composition of the azeotropic mixture with
pressure may be estimated from the activity coefficients
at one pressure and the vapor pressures of the pure compo-
nents. By dividing Equation 5A by 5B, the ratio of the ac-
tivity coefficients for the azeotropic mixture is the inverse
of the vapor pressures of the components. To illustrate the
procedure, Merriman's values (15) for the composition and
boiling point at atmospheric pressure of the ethyl acetate-
ethyl alcohol azeotrope have been used to calculate the con-
stants of .the van Laar equation, A =0.39 and B =0.374.
Values of the activity coefficients were calculated at several
compositions, and their ratio was plotted against composi-
tion on Figure 4. The ratio of the vapor pressures was plotted
against temperature. Lacking any data on the effect of
temperature on A and B, the ratio of the activity coefficients
w5s assumed independent of temperature. At a given tem-
perature the composition of the azeotropic mixture was
found for which the ratio of the vapor pressures equded the
ratio of the activity coefficients. Comparison of the pre-
dicted values with those measured by Merriman is shown in
Table I.
Calculation of x - y Data from Total Pressure or Boi l i ng
Poi nt Curves
From an isothermal measurement of total pressure us.
liquid composition or an isopiestic boiling point-composition
curve, the van Laar or Margules equations may be employed
to estimate equilibrium liquid and vapor compositions. Levy
(12) reviewed the numerous procedures proposed in the past
and developed one for use mith the Margules equation. The
following method may be employed with either type of
equation. Use of the method to calculate x-y values from
boiling point curves is based upon the assumption that the
activity coefficients do not change with temperature Whether
working with total pressure or boiling point data, the pro-
cedure is the same. By definition,
As x1 approaches 1.0, yz approaches 1.0 so that we may
calculate an approximate activity coefficient for component
1 by assuming y2 =1.0. By plotting these apparent activity
coefficients on semilog paper similar to Figure 2, we may
extrapolate to find the terminal values of the activity coef-
ficients, whose logarithms are the constants in the van Laar
or Margules equations. The procedure is illustrated in
Table I1 with the isothermal total pressure data of Hovorka,
Schaefer, and Dreisbach (9) for the system dioxane-water at
80" c.
TABLE 11. CALCULATION OF vhi LUR CONSTANTS FROM TOTAL
PRESSURE DATA
0 . 1 476 35. 5 345 3. 69 . .
0 . 2 526. 5 71. 0 307 3. 08
0 . 3 556 2. 70 .. 106. 5 268
0 . 4 571 142.1 229 2. 40
0 . 6 575. 6 213 153. 5 2. 36
0 . 7 669. 5 248 115 2. 79
0 . 8 550 284 76. 6 3. 47
0 . 9 601. 5 319 38. 3 4. 78
Extrapolation of the approximate values of 71 and y2 to
x1 =0 and x1 =: 1.0, gives y1 =4.36 and y~ =7.4. The
logarithms of these terminal values of the activity coefficients
give the constants in the van Laar equation, A =0.64 and
B =0.87. These constants have been used in the van Laar
equation to recalculate the total pressure for comparison with
the measured values (Table 111). If an acceptable fit is not
obtained on the Grst try, approximate values of 72 may be
substituted in Equation 23 for 71, leading to new values of
A and B by extrapolation.
TABLE 111. COMPARI SON OF CALCULATEDAND 31EASURED
TOTAL PRESSURES
0 . 1 0 . 2 0. 4 0.6 0. 8 0 9
3. 51 2. 85 1. 94 1. 40 1. 10 1 025
1.012 1.05 1. 24 1. 74 3. 06 4. 32
zb
Yl
7 2
PI
P2
Poalcd.
P0bS"d.
IOO(Pobsvd. - Ponlad.)/Pobsvd.
124.6 202 276 298 312 328
358 322 285 266 234 173
482. 5 524 561 564 546 501
476 526.6 571 575. 6 550 501. 3
- 1 . 4 +0.5 +1 . 8 f2.0 +O. 7 + O 1
May, 1942 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 587
Prediction of Vapor -Li qui d Equilibria for Partially
Mi sci bl e Solutions
Binary liquid systems frequently form two liquid phases
over a range of compositions. For systems said to have an
upper critical solution temperature, the immiscible zone de-
creases as the temperature rises until the liquids become com-
pletely miscible at the critical solution temperature. Since
the partial pressure or activity of a component is the same
from each liquid phase at constant temperature, it is pos-
sible to calculate the vapor-liquid equilibria from measure-
ments of liquid-liquid solubility.
For systems which are mutually insoluble, the vapor
pressures of the pure components are additive. For systems
so slightly soluble that Raoult's and Henry's laws may be
assumed, Carey (4) describes a procedure for calculating the
equilibrium liquid and vapor compositions. For a system
near the critical solution temperature, these assumptions are
no longer valid. Scatchard and Hamer (19) employed
Equations 12 to 15, calculating the parameters from the
liquid-liquid solubility of aniline-water, phenol-water, aniline-
hexane, and platinum-gold. They found that Equations
14 and 15 in terms of volume fractions gave better agreement
with the limited amount of experimental data than the
Margules equations in terms of mole fractions. Equations
for calculating the parameters of either the Margules or
Scatchard-Hamer equations may be developed by denoting
the mole fraction, volume fraction, and activity coefficients
of component 1 in one of the liquid phases by xl, z,, and yl,
respectively, and by 21, Zl, and rl in the Other liquid phase.
Since the activities of component 1 in both phases are equal,
Taking the logarithms of both sides of these equations and
substituting Equations 14 and 15,
Figure 5. Plot of van Laar Constants Ac-
cording to Equation 18
For binary mixtures of benzene with methyl, ethyl n-
and isopropyl, sec- and tert-butyl alcohols. f he
squares are the van Laar constants OF the alcohols,
and the circles are those for benzene! the number OF
radiating lines denotes the number of carbon atoms in
the alcohol.
agreement with the measured values is rather poor. These
methods may be expected to give only rough estimates of
the deviations from Raoult's law.
Interpretation of x-y Data, Lacki ng Temperature
Measurements
It is frequently necessary to estimate an z-y curve for re-
duced pressure when only z-y data are available at atmos-
pheric pressure. A procedure similar to that for calculating
activity coefficients from total pressure-composition data
may be used to calculate the constants in the van Laar or
Margules equations. Employing these constants, assuming
no variation with temDerature or bv
-
making some estimate*of the change,
log : =log 3 iE A [ (% - ') ( I' - ") -
l og2 =log- x2 x2 =B [(2$ - 1) (2," - 2:) - 2 ( g - 1) ( I : - 5,9)]
Dividing Equation 25 by Equation 26, and solving for A/ B,
(2 -
) (" - ''11(25)
(26)
the x-y curve may be calculated at
The trial-and-error procedure of cal-
culating the activity coefficient is
started by assuming Raoult's law for
the component present in excess, cal-
culating the boiling point to satisfy
the known x, y, and pressure by Raoult's
law, This boiling point permits cal-
culation of an amroximate activity
71 XI
- reduced pressure.
7 2
(" log 2) (.: - .i; - 2; +i : ) +(log 2 ) ( r : - z: - 22: +2 4
) (27).
AJB =
+5;) +(log 5) (%I - i: - 22; f 2ig
Substitution of A/ B in Equation 25 or 26 will solve for A or
B. When VI =Vz, this will give the solution to the Margules
Equations 12 and 13.
By a similar procedure, a solution for the van Laar con-
tants may be obtained as:
(E +ig) (log -) w x 1 -2
(28)
A 5 2 log x2/&
z =3 a, 2x1 5 log %/ X I
2 2 +h - 5 2 2 2 log x2/&
A = log %/ X I
From the mutual solubility of n-butyl alcohol-water at
100" C. (XI =0.9765 and Z1 =0.677), the constants in the
* van Laar equations may be calculated to be A =0.334 and
B =1.60. Since A V*/BVl =1.07 for the system, the param-
eters of the Scatchard-Hamer equations are the same.
Comparison of these values with Figure 2E shows that
coefficient for the c-omponent present
small quantities. These approximate activity coefficients may
be plotted on semilog paper and extrapolated to obtain A
and B. Activity coefficients and values of z and y are cal-
culated by the van Laar or Margules equations. Further
adjustment of A and B may be required to obtain a good
representation of the xy curve. This second trial may be
carried out using approximate activity coefficients of the
component present in excess in calculating the boiling point.
Homol ogous Series
It is occasionally desired to extrapolate or interpolate to
find the deviations from Raoult's law for a member of a
homologous series of compounds with another type of com-
pound. For instance, one might want to predict the activity
coefficients for n-propyl alcohol-water mixtures, knowing
those for methyl and ethyl alcohol with water.
The similarity of Scatchard's equation for regular solutions
with the van Laar equation suggested that Equation 18
might serve a.a a basis for correlating the constants of the van
Laar equation. Thus, one would plot A and B against
588 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 34, No. 5
ferent. Hildebrand (7) noted that isomeric nitrobenzenes
have the same activity coefficients in benzene solutions.
Further improvements in the method are needed before the
correlation of the isomers on Figures 5 and 6 will be satis-
factory.
Effect of Temperature on Vapor -Li qui d Equilibria
Figure 6. Plot of Activity Coefficients According to
Equation 18
At infinite dilution for mixtures of methyl, ethyl, n- and isopropyl,
n-, iso-, sec-, and tert-butyl alcohols in water. The squares give
values for water,, and the circles represent those For alcohol; the
number of radiating lines denotes the number of carbon atoms in
the alcohol.
AE / AE2 '/
V [(+)I ' - (K) '1 J placing VI outside the bracket
when plotting against A and Siz when against B. Figures
5 and 6 are plots of this type for the homologous series of
aliphatic alcohols with benzene and water. The binary
vapor-liquid equilibria for mixtures of benzene with the
alcohols taken from measurements between 25" C. and the
normal boiling point were fitted with van Laar equations.
Since the activity coefficients of the higher alcohols in water
cannot be fitted exactly with a van Laar equation, terminal
values of log y, obtained by extrapolation, were used in
Figure 6.
Although Figure 6 shows that log y is roughly proportional
to Vb for the aqueous solutions of the alcohols, log y is five
to seven times greater than predicted by Equation 18. The
values of A and B in Figure 5 for the benzene solutions are
not proportional to Vb, although the relation is linear. Ex-
trapolation or interpolation on this type of plot should enable
a rough prediction'of activity coefficients to be made. It
should be noted that the mathematical form of Equation 18
will not predict negative deviations for Raoult's law. In-
spection of Figures 5 and 6 shows that activity coefficients
of the aqueous solutions increase with increasing molecular
weight of the alcohol, while those in benzene solutions de-
crease with increasing molecular weight. The original
equations of van Laar ( I O) relating the constants to those of
the van der Waals equation give no better correlation, and
the van der Wads constants would usually have to be pre-
dicted from the critical data.
Butler (2) measured the partial pressures of esters, nitriles,
amines, alcohols, and acids in dilute solutions in water at
25" C. Butler and Harrower (3) presented similar data for
alcohols and alkyl halides in benzene, carbon tetrachloride,
and cyclohexane. They noticed that, while the activity
coefficients change rather rapidly with the molecular weight
of the solute, the quantity RT In ( p / s ) increases or decreases
regularly. With benzene, carbon tetrachloride, or cyclo-
hexane solvents, RT In ( p / z ) decreases 600 calories/mole
for each carbon atom added to the alkyl halide or alcohol.
I n aqueous solutions RT In ( pi %) increases between 100 and
240 calories/mole for each carbon atom added to the radical.
As Figures 5 and 6 shorn, isomeric alcohols do not have the
same van Laar constants, although they are not widely dif-
When s-y data are available at atmospheric pressure and
an estimate of the x-y curve at reduced pressure is desired,
the effect of temperature on the activity coefficients needs to
be considered. There is a similar problem in the fitting of
a van Laar or Margules equation to isopiestic data covering
a range of 2040" C., because the Gibbs-Duhem equation
and its integrated forms are valid only at constant tem-
perature. The change of the activity coefficient with tem-
perature is related to the relative partial molal enthalpy, L,
by the thermodynamic equation,
h
RT2
._
L1is the partial molal enthalpy of component 1 in solution
minus the enthalpy of the pure liquid at the same tempera-
ture, and may be visualized as the heat absorbed on adding
a mole of component 1 to an infinite quantity of solution.
When heat is evolved on mixing two liquids, Lis negative and
the activity coefficient rises with the temperature.
The labor of calculating the effect of temperature on the
2-y diagram is considerably reduced when the activity coef-
ficient curves can be fitted with van Laar or Margules
equations. These equations have been written in the form
so that the constants are terminal values of log y. Thus,
the change of A and B with temperature may be related to
L at z1 =0 and z1=1.0, respectively.
An inspection of the values of L at infinite dilution cal-
culated from heats of mixing liquids in the International
Critical Tables reveals values as high as 2000 calories/mole
for mixtures of organic liquids. For mixtures of alcohols
with water, the partial molal enthalpy may reach 5000
caloriesimole. As a general rule, systems of organic liquids
having positive deviations from Raoult's law have positive
values of L; and for systems having negative deviations, L
is negative. As a result, activity coefficients for systems of
organic liquids, having either positive or negative deviations
from Raoult's law, approach unity as the temperature rises
and thus approach Raoult's law as a limit. For aqueous
solutions the change is not so simple inasmuch as the value
of L frequently reverses its sign in the ordinary temperature
range. Activity coefficients for immiscible systems with an
upper critical solution temperature must decrease with rise
in temperature.
To give an idea of the order of magnitude of the change in
the activity coefficient with temperature, a change of 6 per
cent in the activity coefficient results from a 30" C. tem-
perature change with L =500 calories/mole. If the left-
hand side of the various equations had been written RT In y
instead of log y, and the resulting parameters had been re-
garded as independent of temperature, the activity coef-
ficients would approach unity as the temperature increased,
agreeing with the general rule for organic liquids. Un-
fortunately, most of the available data on L have been
measured only at room temperature, and there are indications
that L changes rapidly with temperature.
Ternary Vapor -Li qui d Equilibria
Methods of predicting ternary equilibrium dsts from
known data on the three binary systems and of extending
the available ternary data are of increasing importance to the
May, 1942 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY 589
organic chemical industry. Where experimental data on a
ternary system are available, they may be tested by cal-
culating the activity coefficients of the three components and
making three separate plots of log y of one component vs.
x of that component. On each plot two reference curves
can be drawn representing the given component with each of
the other two in a binary mixture. On such plots many of
the existing data on ternary systems have been found incon-
sistent and therefore unreliable.
Lacking precise data, to suggest a general method of pre-
dicting intermediate values of y from those in binary mix-
tures only, a few possibilities were studied theoretically. At
first glance i t might be expected that the logarithm of the
activity coefficient for, say, component 1 could be inter-
polated linearly between the two binary curves, depending
upon the relative amounts of components 2 and 3. While this
procedure is workable aqd has been used in the absence of
ternary data, nevertheless in one hypothetical case the re-
sulting curves were not in agreement with the Gibbs-Duhem
equation ;
(31)
Scatchard (18) developed the equations for the activity
coefficients of a regular ternary mixture, and Scatchard,
Wood, and Mochel (M) applied a slightly modified form to
predict ternary data for benzene-carbon tetrachloride-
cyclohexane mixtures. These equations for the regular
ternary solutions obey the Gibbs-Duhem equation. Their
use is limited because there are few regular binary solutions
or even solutions whose values of A and B are in the same
ratio as the molal volumes. By substituting arbitrary
values of the constants in one case, we found that the curve
of activity coefficients for component 1 plotted against
for equal amounts of components 2 and 3 crossed the lower
binary curve. I n this case a linear interpolation would have
been greatly in error.
z1 d In yI +z2 d In yz +z3 d In ys =0
Calculation of Extraction Equi l i bri a
When values of y1 are available for the solute in each of
two solvent liquids, partition coefficients may be calculated
by employing the principle that the activity of the solute is
the same in both solvents. Denoting the activity coefficient
of component 1 in solvents 2 and 3 as ylz and 713, respectively,
wemay express the equality of activities as:
YlZzl2 =?I3213 (32)
where z12 and 213 are the mole fractions of component 1 in
the liquid phases, composed mainly of components 2 and 3,
respectively. The ratio of 212/213, recognized as a partition
coefficient, is then equal to y13/yl2. A convenient method of
evaluating equilibrium values of x12 and 213, as shown by
Hildebrand (8), is to plot ylz zI2 against xIzJ and 718 5 1 3 against
xla. From the same ordinate, values of zls and 2 1 3 as abscissas
are read from the two curves. When the mutual solubilities
are small, the activity coefficients may be taken from the
binary activity coefficient curves. For systems of higher
mutual solubility, knowledge of the activity coefficients in
ternary systems would be necessary.
Conclusion
This paper has been offered to point out to the engineer
ways of evaluating and extending the available data relating
to vapor-liquid equilibria. It is hoped that some of the
methods reviewed will also be found useful by the experi-
menter in smoothing and presenting new data. The authors
are hopeful that the paper may stimulate further research in
the field of vapor-liquid equilibrium, particularly of homolo-
gous series of compounds, of ternary systems, and of heats of
solution above room temperature. Above all, i t is hoped
that the paper will show the importance of the measurement
and publication of the complete data on compositions, prFs-
sure, and boiling point required for calculation of actmty
coefficients for binary and ternary systems.
Nomencl ature
A =arbitrary constant in van Laar, Margules, and Scatchard-
H-er equations, and equal to log y1 at 21 =0
a =activity referred to pure substance as the standard state
B =arbitrary constant in van Laar, Margules, and Scatchard-
Hamer equations, and equal to log yz at zz =0
b =constant in Equations 16 and 17, defined by Equation 18
AE =change in internal energy on vaporization of pure com-
ponent, cal./mole
F =free energy, cal./mole
=fugacity
$0 =fugacity of pure component
L =partial molal enthalpy referred to pure liquid, cal./mole
P =total pressure, mm. Hg.
PI, Pa =vapor pressures of pure components, mm. Hg
=partial pressure =Py, mm. Hg
H =gas law constant, 1.9870cal./(mole)(0 K.)
T =absolute temperature, K.
V =molal volume of pure liquid, usually evaluated at room
temperature, cc./mole
x =molefraction in liquid
y =molefraction in va or in equilibrium with z
z =volume fraction in {quid
a =relative volatility, ylsr/y~zl
y =activity coefficient
Subscripts
1 =component of binary mixture with lower boiling point
=components of progressively higher boiling points
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