Prediction of Vapor-Liquid Equilibria

and Enthalpies of Mixtures at Low Temperatures

Matthew G. Zellnerl and 1. Carroll Claitor
Air Products and Chemicals, Inc., Allentown, Pa. 18106

John M. Prausnitz
Department of Chemical Engineering, University of California, Berkeley, Calif. 94720

In a computerized system for prediction of vapor-liquid equilibria and enthalpies of multicomponent mix-
tures, separate correlations are used for vapor and liquid phases; the virial equation of state i s used to de-
scribe nonidealities of the vapor phase, and liquid-phase activity coefficients are correlated with a four-
suffix Margules equation. The reference state for pure-component, liquid-phase fugacities and enthalpies i s
the saturated liquid adjusted to zero pressure; however, for highly supercritical components, the reference
fugacities are given by Henry's constants. Heat-of-mixing and pressure corrections are applied to liquid mix-
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ture enthalpies. Comparisons are made with experimental data for low temperature systems as encountered
in liquefaction of natural gas and purification of hydrogen. The calculation procedure described i s modular
and can readily b e extended to systems a t higher temperatures.
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

Thermodynamic properties of vapor-liquid mixtures can be
predicted by either of two methods. The first utilizes an
empirical equation of state to describe deviations froni ideality
of both the vapor and liquid phases. For example, the eight-
parameter Benedict-Webb-Rubiii equatioii and the tno-
parameter Redlich-Kwong equation have been applied suc-
cessfully toward prediction of fluid-phase properties (Bene-
diet et al., 1940, 1942, 1951a,b; Wilson, 1964a). In the second
method, an equation of state is applied only to the vapor
phase, while liquid-phase deviations froni ideal-solution
behavior are calculated with empirical equations for thernio-
dynamic excess functions (Chao and Seader, 1961 : Chueh
and Prausnitz, 1968; Prausnitz et al., 1967; Prausiiitz and
Chueh, 1968).
The latter method forms the basis for the present correla-
tioii. The use of separate therinodyiianiic equations for the
vapor aiid liquid phases affords a high degree of flexibility,
which is required for accurate correlation and prediction of
thermodynamic properties. The virial equation of state is
used to describe noiiidealities of the vapor phase with a high
degree of accuracy (Claitor, 1948; Claitor aiid Crawford,
1949; Prausnitz, 1959). Liquid-phase activity coefficients are
correlat,ed with a four-suffix Margules equation (.idler et al.,
1966; Kohl, 1946, 1953). Particular care has been taken to
avoid discontinuities of paraiiieter-correlating functions and
of mixing rules. With the aid of generalized thermodynamic
correlations and by judicious ext,rapolation of pure-coni-
poiieiit properties into hypot'hetical regions, calculations can
be made over the entire temperature range of practical inter-
est'.
Two difficulties are encountered in the use of separate cor-
relations for the vapor and liquid phases: First', there is a lack
of continuity between t'he separate vapor and liquid equations
a t the critical point. The present correlat,ioii is not intended
for use in the crit'ical region, but is sometimes surprisingly
accurate a t conditions close to critical. Second, a hypothetical
To whom correspondence should be sent.
liquid state must be assumed for each component at a tem-
perature above its critical temperature. For a highly super-
critical gas such as hydrogen, this difficulty is avoided by
using Henry's constant to define the fugacity of the liquid-
phase reference state.
Computerization of the correlation has made it a valuable
tool for the design of low-t'emperature processing plants for
the liquefaction of natural gas and purificat'ion of hydrogen
and helium (Gaunier, 1967). The reported parameters apply
primarily to the range +looo to -300OF and pressures up
to 1500 p i a ; for our purposes this range corresponds to re-
duced vapor densities not exceeding 0.7. Polar materials are
not included in the present correlation. Extensions to other
components, temperat'ures, and pressures can be made in a
modular fashion by modification or esteiision of the thermo-
dynamic equations and/or by adjustment of numerical
values of parameters as new theoretical aiid esperimental
information becomes available.
Vapor-Phase Properties
The virial equation of state forins a sound bask for the
prediction of vapor-phase thermodynamic properties (Praus-
iiitz, 1959, 1969). It, can be derived by the methods of statis-
tical thermodynamics, which indicate that the virial co-
efficients are directly related to interniolecular forces. The
virial equation can be applied t o mixtures on n theoretical
basis, using only pure-component properties and a set of
semiempirical mixing rules for interaction virial coefficients.
For the limited density range of interest' here, the virial
equation (Equation 1) is truncated after the third virial
coefficient :
The second virial coefficient of a mixture is calculated using
the work of Pitzer et al. (Pitzer, 1955; Pitzer and Curl, 1957;
Pitzer et al., 1955).

Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970 549

 Table 1. Equation Reference List VCii= (8)
2
Equation Reference

1 Dodge, 1944; Hirschfelder et al., 1954;

Prausnitz, 1959 (9)
2 Hirschfelder et al., 1954; Prausnitz, 1959
3 Pitzer, 1955; Pitzer and Curl, 1957; Pitzer wz = -log (P,,) - 1.000 (10)
et al., 1955
4, 5, 6 Prausnitz, 1959 where P,, is evaluated a t T,, = 0.7.
7 Hudson and RIcCoubrey, 1960; Huff and Literature references, where appropriate, for equations
Reed, 1963; Prausnitz, 1959
appearing in the text are given in Table I.
8 Hudson and McCoubrey, 1960; Huff and
Reed, 1963 Equation 7 adequately represents the available data when
9 Prausnitz, 1959 the Lorenz conibining rule (Equation 8) is used for Vcs,
10 Orentlicher and Prausnitz, 1964 (Hudson and IIcCoubrey, 1960; Huff and Reed, 1963;
11 Hirschfelder et al., 1954; Prausnitz, 1959 Prausnitz, 1959). Use of an arithnietic nieaii for V,,, results
12 Gunn, 1958 in k,, values that are too large. The kHZ-cH4 binary inter-
14-20 Prausnitz, 1959 action coefficient was determined from binary hydrogen-
21, 22 Lyckman et al., 1965a methane vapor-liquid equilibria data (Air Products and
27, 28, 29 OConnell and Prausnitz, 1964 Chemicals, Inc., 1969) to be 0.0 instead of 0.07 predicted by
40 Lyckman et al., 1965b Equation 7 . This gives a better prediction of B H ~ - - c which
H~,
45 Orentlicher and Prausnitz, 1964
is important in Equatioii 18 for the calculation of $cH,.
46, 47 Hildebrand and Scott, 1950
48 Lyckman et al., 1965b Pseudocritical properties (Table 11) were developed for hy-
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54, 55, 56 Wohl, 1946 drogen, which is a quantum fluid for use in Pitzers equation
59 Adler et al., 1966 by a regression analysis of experimental second virial co-
60 Kohl, 1946 efficient data (Knapp et al., 1962; Michels et al., 1960).
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

61, 62, 63 Brown and Smiley, 1966 The third virial coefficient of a mixture is calculated accord-
64 Wohl, 1946 ing to
73 Klaus and Van Ness, 1967
74 Dodge, 1944
80,87-90 Prausnitz and Chueh, 1968

Table 11. Pure Component Properties Cor,,,= 0.08357 - 0.0004014Tri, +

Cu Ft Ionization
T,, O R Vo Lb-Mole Z, w Potentiol, Ev 0.3835 0.04694
(13)
H2 8 1 . OOa 0.64164 0 . 2860a 0 . 0624a 15.60 Tr<jhZ TT;>bG5

Nz 227.22 1.444 0.2916 0.040 14.48

CHd 343.50 1.588 0.2900 0.013 12.99
C2HG 550.09 2.368 0.2840 0.105 11.65
CsH, 666.24 3.218 0.2780 0.152 11.08
C4Hm 765.60 4.093 0.2740 0.2010 10.63
a Pseudoproperties.

T
Tr,,, = ~ (17)
TCs,k

Theoretical knowledge and empirical verification of the

combining rules for interaction third virial coefficients are
much less advanced than for second virial coefficients.
Therefore, the accuracy in calculating third virial cross
coefficients for mixtures is not high. Fortunately, a t the vapor-
phase densities of interest here, third virial coefficients are
much less important than second virial coefficients. ?;everthe-
less, for reliable results it is better to include an approximate
third virial coefficient than to truncate the swies in Equation 1
after the second term.
An empirical correlation for third virial coefficients of simple
molecules is given by Equation 13 and Figure 1. This correla-
tion yields more accurate predictions of therrnodynaniic prop-
erties a t moderate vapor deiisities than that based on the
Lennard-Jones (6-1 2) potential, which predicts third virial
coefficients that are too small near T r = 1.0.
(7)
The vapor-phase fugacity coefficient can be derived from

550 Ind. Eng. Cham. Fundam., Vol. 9, No. 4, 1970

 0 NITROGEN(CLAIT0R AND CRAWFORD,1948,1949; HILSENRATH, E T A L , 1 9 5 5 )
V OXYGEN (CLAITOR AND CRAWFORD, 1948,1949)
@ ARGON ( C L A I T O R AND CRAWFORD, 1948,1949)
A METHANE(DAVI0 AND HAMANN, 19581

- LENNARD- JONES 16421 POTENTIAL

0 0 0
n
EMPIRICAL CORREUTION

-0.1 ,
I
,
2 3
I
4
, 5
I

Tr
Figure 1. Reduced third virial coefficients
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the virial equation by standard thermodynamic procedures.

+ 0 671231 - 1.20483
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

It is given by (log $)(I) = 0.567069

T,

3 s 'V
pm2 Y ~ Y L C-
~ J In
I , 2, (18)
2 3=1 k=l
Equations 24 and 26 are extrapolations to low reduced
The isothermal effect of pressure on enthalpy is given by temperatures to yield agreement wit,h the vapor pressure of
methane. The fuiictioiis (log and (log #)(I) have lieen
(II* - H ) = -RT extrapolated through the critical region to reduced tempera-
tures greater than 1.0 to avoid the rapid rate of illcrease of

Pm2
(c, - d">]
2 d T
(19)
fugacity with temperature in the critical region. This es-
trapolation provides a good approximation to the behavior
in mixtures of components a t temperatures near and above
Vapor-liquid Equilibria their critical temperatures. This correlation has been used to
calculate hypothetical liquid fugacities, j",for methane and
At equilibrium, the fugacity of every component i in the nitrogen up to ambient temperature correspondiiig to re-
vapor phase is equal to that in the liquid phase: duced temperatures of 1.6 and 2.5, respectively. In aeg-
menting the above curve fits, and subsequent curve fits of
other parameters, continuity of the fuiictioiis and their first
derivatives was maintained a t the junction point..
Reference Liquid Fugacity for Highly Supercritical
The fugacity coefficient, + i , is obtained from Equation 18.
Components. T h e standard-stat,e liquid fugacity, f", in
P u r e Component Liquid Fugacity. The standard-state
Equation 22 is based on the valior pressure of the pure
liquid fugacity, jZo,is t h a t of the pure liquid component,
component and cannot be conveniently estrapolated t o
a t t h e system temperature, corrected t'o zero pressure.
high reduced temperatures for a highly supercritical
This fugacity is obtained from the generalized correlation
of Lyckmari et al. (1965a) : component such as hydrogen which has a pseudoreduced
temperature of 7.0 a t ambient temperature. hypothetical
log $ = (log 4)CO) + w (log $)(I) (21) reference liquid-phase fugacity can be developed for such
components through the use of a Henr
where juiict'ioii with an activity coefficient norninlized in the u ~ i -
symmetric convention (O'Connell and Prausiiitz, 1964).
$ = - so (22) Accordingly, Equation 20 becomes
pc
0.598649 0.519884
(log $)(O) = 0.870693 - ___ - ___
T, T,2
where subscript 2 denotes the solute or light component.
T , 2 0.62 (23)
For activity coefficieiits iiorriialized in the synnletrica
coiiveiitioii, Equation 20:
(log $)cO) = 2.22315 - 2'27569
-__ T, < 0.62 (24)
T, y i + 1.0 as zi+ 1.0 (for all i) (28)

Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970 551

 b AKERS 8 EUBANKS 119571 0 VOW 8HALSM (19601 Eyuabion 31 then becomes
0 GONIKBERG,ETAL.(l9391 v BENK4MBKAl7(19571
p MAlMONl (19611 A FASTOVSKI 8 GONIKBERG
- AI*
Inf2' = In ;212,1" (36)
(19401
A similar analysis for solute 2 in a binary with another sol-
vent 3 yields
In fz0 = In 1 1 . 1 2 , ~ -
~ (37)
Since fz" is independent of composition or the solvent,

In M2,10- In ;Zi2,30
= ill*- AQ3 (38)
Equation 38 is the "consistency test" derived by O'Connell
and Prausnitz (1964). This test is oversimplified because it
I 1 I assumes that the one-parameter Margules expansion (Equa.
100 200 300 4 00 tion 32) adequately describes the activity coefficient over the
TEMPEWTURE, O R
entire composition range. The failure of the consistency test
Figure 2. Henry's constants for hydrogen to fit experimental data for hydrogen in even simple solvents
(nitrogen, argon, and met'hane) is demonstrated in Figures 2
and 3. The correlating lines are drawn for the Henry's con-
'CONSISTENCY TEST' WITH stants, as indicated in Figure 2. If nitrogen is bhen chosen as
3 Nz AS REFERENCE SOLVENT the reference solvent, the consistency test then dictates the
Xargules parameters indicated in Figure 3. The test fails
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quantitatively for methane and is even qualitatively incorrect

.- 2 for argon with reference to nitrogen.
I
N
Unfortunately, the accuracy of the available experimental
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

data is insufficient to justify the use of more than one Margules

I
parameter per binary. Hence, an empirical equation is used
3 0 0
here to define a reference-state liquid fugacity for a highly
A,D CH4
0 supercritical component dissolved in one or more solvents:
VOLK 8 HALSEYl19601 WITH
AR VAPOR PHASE DATA OF MULLIN' 1 s
8 ZIEGLER (19651
I
I 200
TEMPERATURE,'R
300 ;# 2
Figure 3. Margules parameters for hydrogen-solvent This definition has the desirable characteristic of yielding
interactions the proper f2" in the constituent binaries and providiug a
couvenient rneaiis of extending the calculations to multi-
For the unsynimetric convention in a binary mixture, Equa- componeiit mistures.
tion 27: For mixtures containing hydrogen, the esperinient~aldata
have been correlated using Henry's coiistants and unsym-
yr* + 1.0 as x2 -+ 0 (for the solute only) (29) metrical activity coefficients defined by Equation 27. How-
ever, for predicting vapor-liquid equilibria, supercritical
The nornialization of yz* a t infinite dilution is convenient
hydrogen is treated in a niaiiner identical t o that used for
for a light coniponent since its solubility in the liquid phase is
subcritical components; the only difference is that for hydro-
usually only a few per cent-for example, the solubilit,y of
gen j" is calculated from Equation 39, whereas for subcritical
hydrogen in the liquid phase rarely reaches 20yc, and then
c o m p o ~ i e n t sis
j ~calculated using Equatioiis 21 to 26.
only a t high pressures.
Partial Molar Liquid Volumes. Partial molar liquid
Comparison of Equations 20 and 27 yield?
volumes are required to determine the effect of pressure
Y2f2" = y**Jf*,Io (30) on fugacity in the exponential Poynt,ing terms of Equat'ioms
or 20 and 27. I n general, they are functions of t'emperature,
111 f@ = 111 X*J@ + in y2* - In y2 (31)
pressure, and composition. -4t moderate pressures, t h e
Poynting correction is relatively small and usually 011 the
Assume that the activity coefficient of the solvent, I n yl,is order of 5 to 10%. Hence, iii the absence of sufficient esperi-
gii-eii by a one-parameter llargules expalision: mental iiiformation, the partial molar liquid volumes are
assuriied to be indepeiident of composition and pressure and
111 y1 = A 1 2 2 r 2 (32) are takeu equal to the pure-componeut saturated liquid
The Gibbs-Duheni equation can then be used to obtain an ten1 temperature. The liquid volumes are
expression for 111 y?*: obtained from the generalized correlation of L>-ckninn et al.
(196513) :
(33) J', = TJ7m + wTJT(l) + w*117(*) (40)
Sub-titution of Equation 32 into Equation 33 yields The Viii) functions h a r e been curve-fitted to obtain useful
estrapolatious t o reduced temperature3 greater than 1.0.
111 Y?* = =ll?(xl* - 1) (34) Extrapolation is started lielon. the critical temperature to
01' avoid the estremely rapid rate of increase of volume with
111 y?* = 111 y2 - AI? (35) temperature in the critical region. This yields a better approxi-

552 Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970

 iiiation t o the partial molar volume and avoids excessively
large hypothetical volumes in the supercritical region.

V,@)= 0.383252 T,5 0.558 (41)

0.8579705 0.2394401
V,(o) = 1.151829 - _____
Tr 4- TT2
T , > 0.558 (42)
V,(l) = 0.0719319 -
0.610601
0.56245 X -~

0.610601

V,(*)= -0.202816 +
0.657466
0.1620136 X ___

0 v3 213 I
XI
Equation 43 asymptotically approaches values of -0.277
and 0.0719 at low :ind high reduced temperatures, respectively. Figure 4. Graphical determination of binary Margules
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Siniilnr limitiiig values in Equation 44 are 0.147 and -0.2025. para meters
The partial molar volume of a supercritical compoiient in
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

the liquid phase is determined froni the hard-sphere model

given by Oreiitlicher and Praumitz (1964) : p:iranieter,* whenever one of the components was highly
supercritical (Gauiiier, 1967). The biliary Margules parani-
eters are not redricted iu a ternary .;y,?teni. a- are the van
Laar parniiieter5. For the vnii Laar equation iii a ternary
where

but there i y 110 4inilar re.trictioii for the llargulez constants.

The foiir->uffixXarguleh equation reduce-: to the simpler two-
and three-suffix equations when the paraincter~arc selected
i=l appropriately.
For a supercritical component in Equation 46, = 0. In For a 11iiiary~
Equation 47, VZ = b2 is used to avoid a trial-and-error pro-
cedure.
111 y1 = 2??[.41? + 2(=121 - d l 2 - Dl?)Tl + 3D122121 (55)
Solulility paranieters are obtained from the generalized 111 79 = ~ 1 2 [ . 4 ? l + 2(A12 - =I91 - D1 + 3 D 1 2 ~ 2 2(56)
]
correlation of Lycknian et al. (196%): where
A,? = 111 y i 0 (57)
A?, = 111 y20 (58)
The functions have been curl-e-fitted as The teiiiperature dependelice of the llargules parameters
hi 6,") = -0.104423 + 1.02489TT- (Xdler et a / . , 1966) is correlated hy
1.4406 T T 2 T , 2 0.5 (49a) Ta4ij = ai, bi,T + (59)
111 = 0.25572 - 0.4157 T , T, < 0.5 (491)) The l l a r g u l e ~iiawnietcr,<c n n lie cottl-enieiitly determined
111 6,") 1.34055 - 2.13473 T , from experinieiitnl data by a graphical procedure a. bhon-n in
= (50)
Figure 4.
S T ' * ) = 1.51291 4-4.38252 T,' T , < 0.5 (51) For a tertiary,
6,(') = -4.503624 + +
2r1(.421- -Al? - D12)
In yl = r22[A419 + 3x12&] +
11.96286 T , - 7.580341 T r 2 0.5 5 T , 5 0.7891 (52) 23'[~4ia + 211(-131 - --ii,j - 013) + 3Ti2ni3] +
6,m = 0.216095 T, > 0.7891 (53) T.yJ3[l ' 2 ( & + *412 + A,, + *A13 - -423 - AS?) +
Liquid-Phase Coefficients. T h e four-suffix
Activity 1.1(;1?1 -dl? + A31 - -413) + (J.2 - T3)(A23 - A??) +
Rlargules equation (.idler et a / . . 1966; Browii and Smiley,
1966; K o h l , 1946, 1953) \vas selected for tlie correlation of 32'2JaD23 - Tic] - (1 - 3.l'i)(~lci T I C ? f + 2:3c3)] (60)
activity coefficie~itsbecause in a binary] t,wo of the Mar- The activity coefficieiits for components 2 and 3 are ob-
gules parameters are directly determined by t h e infinite taiiied by rotating sulwcri1)t~in the order 1 2 .--, 3 -+ 1. .-f

dilution activity coefficients of tlie two comiionenta. Similar The ternary activity coefficient exiirei+ioiii require nine
coiiveiiience is not obtaiiied with the Redlich-Kister or TT'ilsoii binary ntid three teri1x-j. linranieters. For siiiilile
equatiow (Hougen et a / . , 1959; Kil-on, 1964b). Experience the ah.sence of sufficietit experitucntal iiiforniiition, ternary
with ternary mixtures indicated the need for ternary llargules 1iaranieters C aiitl liinary 1)arameters D ma\- be set t o zero.

Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970 553

 For a multicomponent system (Brown and Smiley, 1966),
t h e general excess Gibbs free energy expansiou for the four-
suffix Ilargules equation is
A--3 .v-2 .v-1 s system, since L 4 ~ 2 -=~ A~C 4H ~ - - N * and DK,-c,, = 0, corre-
#m,n #m
>n
The activity coefficients are obtained from Equation 61 by
The quantity ( E i j k l - Cijkl) was assumed to be ztro. The
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resulting expression for the activity coefficients can he ar-
ranged in the following form, which is very efficient for
digital coniput'ation.
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005
The digital evaluation of the eiitire set of [ln 7 h ]in Equa-
tion 65 can be accomplished in one complete cycling of the
subscripts by including the k-part of the triple sumniation
inside the double sumniation with appropriate tests. Thus,
for each unique subscript combination, each In Y h is up-
dated as indicated by the value of h. The two summations
involving h = 1, 2 , . , . , 11- can be accumulated duriiig the
summation process and t,he total added to each ln y h a t the
elid of the summation process.
Data Reduction and Prediction of Vapor-Liquid Equi-
libria. Henry's constants and Llargules parameters for
binaries coiltailling hydrogen were obt,ained graphically
according to the equation
When the left side of Equation 66 is plotted against (xI2-
l ) , 1n d 1 2 , , " is the intercept and A2] is the slope.
Henry's constants were correlated with temperature by the
empirical relation
554 Ind. Eng. Chem. Fundam., Vol. 9, No. 4 , 1970
The parameters in Equation 67 are given in Table 111.
The parameters were correlated according to Equation 59
and are presented in Table IV.
The Margules parameters for binary systems not containing
hydrogen were determined graphically, as indicated in Figure
4, aiid are given in Table IV. An example of the composition
dependence of liquid-phase activity coefficients is given in
Figure 5 for the nitrogen-methane binary. This is a simple
sponding to a two-suffix Nargules expailsion. If 311 attempt
is made to improve the fit on the methane activity coeffi-
cients in Figure 5 , the Gibbs-Duhem equation requires a
corresponding change in the nitrogen activity coefficients,
which will not be as good a fit as that in Figure 5 . In most
cases, only the data for the lighter compoiient in a binary
mixture are sufficiently accurate to determilie the IIargules
parameters in Equations 55 and 56. Therefore, the procedure
followed was to determine all three Nargules parameters in
Equation 55 based on the activity coefficients of only the
lighter component in the binary. The activity coefficient of the
heavier component is then automatically established through
the Gibbs-Duhem equation. The temperature dependence of
A N 2 - c H a is indicated in Figure 6. The slope of this plot gives
248 Btu per mole for the partial molar heat of mixing in the
nitrogen-methane binary a t iiifiiiite dilut'ion.
The activity coefficients in the methane-ethane binary a t
-100F are presented in Figure 7 . If the data of Price and
Kobayashi (1959) and those of Ruheiiianii (1939) are weighted
equally, the dashed lines would best represent the data.
However, data for the H2-CH.,-C2H6 ternary (iiir Products
and Chemicals, h e . , 1969) indicated that activity coeffi-
cients based on Price and Kobayashi's data produced better
predictions ill the ternary. Subiequently, the solid lines based
on these data were selected. The CH4-C?H6 data of Chang and
Lu (196T) were also examined hut, found to be extremely
scattered.
Predicted aiid experirnental K-values for the CH4-C'Hs
biliary are shown in Figure 8. .It O'F, methane is highly
supercritical and ethane is approaching its critical tempera-
ture. Under these conditions, the t,liermodynamic model is
less reliable than a t lower temperatures. Ilence, the - 100'
and -200F isotherms were weighted inore heavily in de-
velopment of the correlation. .Is a result, the predicted
methane K-value is consistently high by about 1070 a t O O F .
The correlation was further verified by comparing pre-
dicted methane li-values with experimental data for the
H2-CH4-C2H6 ternary systeni (Figure 9 ) . The liquid phase in
this ternary system is primarily methane and ethane, with
 Table 111. Henry's Constants for Hydrogen
In Mzl0 = czj + dzlT
M o l psia
T , OR
Temp.
Solvent, j C2j -d2j X lo3 D a t a Ref. Range, "R

Nz 10.17 9.36 Akers and Eubanks, 1957; 142-196

Gonikberg et al., 1939;
Maimoni, 1961
CH4 11.69 9.36 Benham and Katz, 1957; 162-310
Fastovski and Gonikberg,
1940
CZHG 11.91 5.04 Williams and Katz, 1954 259-510
C3Hs 12.22 5.04 Williams and Katz, 1954 309-535
c4H10 12.32 5.04 Aroyan and Katz, 1951 359-535
~~

Table IV. Margules Parameters

TAij = ail + bijT("R)
Binary Parameters

component Ai2 Azi Diz Data Temp.

1 2 0 b 0 b 0 b Ref. Range, O R
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Hz N2 270 0 27 0 0 0 0 0 142-196
Hz c1 360 0 360 0 0 0 b 162-310
Hz cz 630 -0.268 630 -0.268 0 0 c 259-510
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

c
Hz c3 500 0 500 0 0 0 309-535
Hz C4 320 0 320 0 0 0 d 359-535
Nz c1 125 0.128 125 0.128 0 0 e
163-310
NZ cz 184 1.34 184 1.34 0 0 f 311-438
Nz c3 7 67 0 1315 0 0 0 0 ...
Nz C4 918 0 1898 0 0 0 0 ...
C1 cz 6 0.4 26 0.63 179 -0.33 h 311-510
c1 c3 285 0 651,9 -0.45 2024 -4.49 313-510
c1 c4 100 0.474 51 1 0.733 2549 -4.49 j 380-500
cz c3 24.4 0 24.4 0 0 0 k 410-620
cz c4 27 0 43 0 0 0 0 ...
C8 e
4 7 0 9 0 0 0 I ...
Ternary Parameters
Component
- c1123 c1223 c1233 . Data Temp.
1 2 3 0 b 0 b 0 b Ref. Range, O R

Hz CH4 CZHG 14715 -58.540 -2358.8 6.0300 871.50 -3.3635 ' 260-360
Hz CH, C3H8 -1065.1 -15.067 2250.0 -7.7828 1620.2 -5.8080 260-460
Akers and Eubanks, 1957; Gonikberg et al., 1939; RIaimoni, 1961.
Benham and Katz, 19.57; Fastovski and Gonikberg, 1940.
c Williams and Katz, 1954.
Aroyan and Katz, 1951.
e Cheung and Wang, 1964; Cines et a!., 1953; Sprow and Prausnitz, 1966.
f Eakin et al., 1955.
0 Estimated from the Scatchard-Hildebrand equation.
Price and Kobayashi, 1959; Ruhemann, 1939.
i Price and Kobayashi, 1959; Akers et al., 1954.
j Roberts et al., 1962.
hfatschke and Thodos, 1962.
Cosway and Katz, 1959.
m Benham and Kat'z, 1957.

less than 9% hydrogen. Figure 9 indicates that the effect of Hence,

composition on the activity coefficient of methane is accu-
v1
rately predicted a t a temperature 50F lower than the range A12 = - (61 - 62)Z (69)
in which the methane-ethane binary activity coefficients were R
correlated.
V
I n the absence of experimental data for a binary system, A21 = 2 (61 - 62)' (70)
the Margules parameters were estimated from the Scatchard- R
equation l950; Hollgen The solubility parameters and liquid volumes in Equations
et al., 1959) : 69 and 70 were evaluated a t a reduced temperature based on
VI Equation 5 for which the Scatchard-Hildebrand equation
In y1 = - (a1 - 62)2@22
RT (68) was reasonably accurate for similar binaries.

Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970 555

 0.8i CH4

0
0
0 OF

Figure 5.
At -296.5F
XN2
Nz-CHd activity coefficients
(Data from S p r a w a n d Praurnitz, 1 9 6 6 )
ool \ -200
0 PRICE 8 KOBAYASHI (19591
-CALC ULATE0

0 CINES,ETAL.(1953)

I
0.01
0 CHEUNG 8 WANG (1964) IO 100 1000
X SPROW 8 PRAUSNITZ (1966) PRESSURE, PSIA
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Figure 8. CH*-C& K values

1.0
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

T=-250F

50 PSIA
0.4 1
0.4
03 0.4 0.5 0.6 0.7
IOO/T, *R-
Figure 6. As~--cH~
temperature dependence
0.2 1
30C 0 205
200

REFERENCE E % 300
APRICEa 0503 400
KOEAYASHI(1959) -100 0 0

--
2oc RUHEMANN(l939) -94 A A J73 600
800
RUHEMANN(1939) -112 v L1012 1000
DATA WEIGHTED EOUALU -EXPERIMENTAL PRESSURE
a BASED ON DATAOF 0.04
PRICE a KOBAYASHI
b.
5 0 COHEN,HIPKIN, 8 KOPPANY(1967)
-CALCULATE0
G 100 I
0.02
0 0.2 0.4 0.6 0.6 IO
XCH4

Figure 9. Methane K values in the Hz-CH4-CzH6 system

0
A
case, ternary parameters were uaed in addition to the biliary
f I ! I
parameters. The ternary Margules parameters were deter-
0.2 0.4 0.6 0.8 niined by a regression analysis 011 the experimental ternary
xCHq activity coefficients of hydrogen only, using the binary
Figure 7. CHd-CPHG activity coefficients Margules parameters obtained from binary data. Use of the
ternary Margules parameters based on hydrogen only has
essentially no effect on the activity coefficients of methane
The effect of using ternary Xargules parameters is dernon- and ethane. Without using ternary Margules parameters, the
strated in Figure 10 for the activity coefficient of h-drogeii predicted activity coefficients of hydrogen are consistently
in the H2-CH.&H6 ternary. Coinpariso~i,~ of calculated and lorn and result in a deviation of approsiiiiately 60y0 at dilute
experinieiital activity coefficients are shown for two cases. hydrogen coiicentrntions iii the liquid. TYheii ternary Mar-
111 the first case, only binary JIargules paraiiieters were gules parameters are uaed, the consistciit deviation is elim-
used to predict the ternary activity coefficients. I n the second inated.

556 Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970

 Enthalpy of Mixtures MARGULES PARAMETERS
BINARY BINARY
ONLY a TERNARY
Enthalpy of Gaseous Mixtures. T h e enthalpy of a gas- -100 3 0
-200 0
eous mixture is calculated using Equation 19 together with C
0
H, = H,* - ( H * - H ) , (71)
.v
H,* = ytHi* 0
0
i=l c1
8 C
0
Baqed on the accuracy of the virial coefficients, (H* - H )
is estimated to be accurate within =tlOyoup to moderate
0
: eo 3

vapor densities. Ideal-gas enthalpies, H a * , are calculated

from spline curve fits of value5 determined from spectroscopic
information (Herah and Zellner, 1969; Klaus and Van Sess,
* m.
1967). The spline representation of enthalpy as a function of ."
0 2 4 6 8
temperature is
MOLE PERCENT H Z IN L I Q U I D

Figure 10. Effect of ternary Margules parameters on

activity coefficient of hydrogen
15, - - H", + 2H",-1 +
H ~ - C H ~ - C ~ HdSa t a of C o r w a y a n d K a t z ( 1 9 5 9 )

[
H,-1
(T - T7l-i) Hn-1
Ln 6
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(73)
where L , = T, - T,-,, the length of a spline interval, and
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

the H",, are the spline curve fit coefficients which correspond
to d21i/dT2.Spliiie coefficients for ideal-gas enthalpies are
given in Table V. The accuracy of the ideal-gas enthalpy
values and spline curve fits is indicated in Table VI.
Enthalpy of Liquid Mixtures. T h e partial molar en-
thalpy of a component in a liquid iiiisture can be derived
b y differentiating its liquid-phase fugacity with respect to
temperahre:

or

For h,('ef) = H,*and upon substituting Equation 20, the

(75)
1 ,' TTP
I

TEMPERATURE
partial molar liquid enthalpy i q Figure 1 1 . Zero-pressure liquid enthalpy

The first term in Equation i i is the ideal enthalpy of the

The first term in Equation 76 is the pure-cornpoilent liquid
enthalpy a t zero pressure, h i 0 : as determined with reference
to the ideal-gas enthalpy through differentintioii of Equation
21. Thermodynamic consistency dictates that, the pure coni-
poiient liquid enthalpy, h i 0 , and fugacity, j l " , be related in this
manner. However, the differentiation process introduces
subitaiitial e n o r and the fugacity, .Tio, has been extrapolated
through the critical region in T-iew of the uncertaintj- in the
partial molar liquid volumes. The enthalliies, h $", therefore
are more accurately obtained by adjusting pure-conipoiient
saturated liquid enthalpies to zero pressure through the in-
tegral term in Equation 76. Hence, for a misture,
liquid mixture a t zero pre,-sure, the second term is the heat of
niixing at zero pressure, and the third term is the pressure
correction for the liquid misture from zero prebsure to the
system pressure, P. Spline coefficients for 11," are lkted in
Table T'II and the spline fit error3 in T:iblc T'III. Thebe
spliiie fit5 were made by adjustjiig ,saturated liquid enthalpy
information to zero prewwe for teriiperatures froin the triple
point to T , = 0.8. Below the triljle point and above T , = 0.8,
empirical niethod.: were used t o extend the siiline fits into
hypothetical regioni, as indicated qualitatively in Figure 11.
The hypothetical 1)ure-cornl)oiieiit liquid eiithall)ies for nitro-
gen and methane above T , = 0.8 and into the bupercritical
region have been selected to yield agreement with esperi-
mental enthalpy data on mistures (-\ir Products and Chem-
icals, Inc., 1905-69 a,b), The ideal gas enthalpy is wed for the
hypothetical enthalpy of hydrogen in the liquid p1ia.e. This
neglects the term R
(" ~

b (111l /jTl ")>p=o

iii Equation 76, which

for hydrogen dissolved in liquid iiiethane a t 200"R is 28

Htu per niole. This is negligible when multiplied by the small

Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970 557

 Table V. Ideal-Gas Enthalpy Spline Coefficients
Component r, OR H * , Btu/Lb. M o l e H*"

Hydrogen 0.180000E 02 0.254626E 04 -0,255658E-03

0.900000E 02 0,2903843 04 0,4987753-03
0.162000E 03 0,3269333 04 0,7423023-02
0.234000E 03 0.366766E 04 0.7816513-02
0.306000E 03 0.410379E 04 0.507240E-02
0,3780003 03 0,456714E 04 0,339315E-02
0.450000E 03 0,504817E 04 0,180968E-02
0.594000E 03 0.603651E 04 0.480097E-03
0.738000E 03 0.703813E 04 0.114119E-03
0.102600E 04 0.905040E 04 0.712084E-04
0.153000E 04 0,1259913 05 0.3534503-03
0.2250003 04 0.178292E 05 0.6069453-03
0,306000E 04 0.2405iOE 05 0.538510E-03
Sitrogen 0.180000E 02 0.212166E 04 0.164554E-03
0,900000E 02 0.262218E 04 - 0,942212E-04
0.162000E 03 0.312258E 04 0,871553E-04
0,2340003 03 0.362318E 04 -0.348548E-04
0,594000E 03 0.612655E 04 0.834550E-04
0.810000E 03 0.763505E 04 0,445373E-03
0.8820003 03 0,814167E 04 0.574665E-03
0.954000E 03 0.865122E 04 0.639852E-03
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0.109800E 04 0.968085E 04 0.840151E-03

0.131400E 04 0.112574E 05 0,902744E-03
0.153000E 04 0,1287553 05 0.886024E-03
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

0.225000E 04 0.1853963 05 0.557931E-03

0.306000E 04 0.252591E 05 0,280621E-03
Methane 0.0 0.200017E 04 0.193103E-03
0,309690E 03 0.44610lE 04 -0.185558E-04
0,5276903 03 0.623509E 04 0,509560E-02
0.810000E 03 0.888239E 04 0,8292993-02
0.1559693 04 0.188196E 05 0.628XOE-02
0,175969E 04 0.221077E 05 0,477865E-02
0.215969E 04 0.292839E 05 0,502427E-02
0,234000E 04 0,3276413 05 0.234973E-02
0,2520003 04 0.3634153 05 0.466672E-02
0.2700003 04 0.400079E 05 -0.452749E-02
Ethane 0.0 0.199865E 04 0.170858E-02
0,5196903 03 0.692621E 04 0.157241E-01
0.709690E 03 0.956505E 04 0.170279E-01
0.8096903 03 0.111965E 05 0,169136E-01
0.1659693 04 0.3087553 05 0,8452833-02
0,185969E 04 0.36644iE 05 0.1018883-01
0,2059693 04 0.42773lE 05 0.467877E-02
0,225969E 04 0.491499E 05 0,836726E-02
0,2459693 04 0.557999E 05 0.283127E-02
0.270000E 04 0.6406493 05 0.112110E-01
Propane 0.0 0.199999E 04 0.165336E-01
0.259690E 03 0,437007E 04 0.179455E-01
0.519690E 03 0.802637E 04 0.256586E-01
0.536690E 03 0,8320343 04 0,293478E-01
0,609690E 03 0.967573E 04 0.264869E-01
0.709690E 03 0.117657E 05 0.268922E-01
0.900000E 03 0.164595E 05 0.2271683-01
0.165969E 04 0,424380E 05 0.117325E-01
0.185969E 04 0.5068783 05 0.12'i185E-01
0,205969E 04 0,5940983 05 0.8210363-02
0,2459693 04 0.778682E 05 0.706131E-02
0.2700003 04 0,895221E 05 0,7359923-02
Butane 0.0 0,2000003 04 0.6550063 02
0.409690E 03 0,7652613 04 0.3644733-01
0.4916903 03 0,9340213 04 0,265098E-01
0.5276903 03 0.1014693 05 0,479074E-01
0.540000E03 0.103349E 05 0,276914E-01
0.630000E 03 0.126825E 05 0.3562OjE-01
0.135969E 04 0.400508E 05 0.1961523-01
0.2700003 03 0 . 115806E OG 0.513785E-02

558 Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970

 ~ ~~

Table VI. Accuracy of Ideal-Gas Data and Spline Fits0

Temperature Range
RMS Error, Max. Error, 100-500'R 500-1 500'R l500-300O0R
Component Btu/Lb-Mole Btu/Lb-Mole Uncertainty in Published H*, Btu/Lb-Mole Ref.

Hydrogen 0.076 0.465 0.02 2.0 6.0 Hilsenr a t h

et al., 1955
Xitrogen 0.033 0.215 0.06 2.0 6.0 Hilsenrath
et al., 1956
Methane 1.269 5.988 20 to 150 5 to 50 9 to 90 Taff, 1966
Ethane 2.509 11.490 20 to 150 5 to 50 9 to 90 Taff, 1966
Propane 3.949 22.625 20 to 150 5 to 50 9 to 90 Taff, 1966
Butane 4.496 15,750 20 to 150 5 to 50 9 to 90 Taff, 1966
a Enthalpy base: 2000 Btu/lb-mole for ideal gas at OOR.
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Table VII. Zero-Pressure liquid Enthalpy Spline Coefficients

Component r, h o , Btu/Lb Mole
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

OR

Hydrogen (Same as ideal-gas enthalpy, H * )

Sitrogen 0.1136703 03 0.171120E 03 -0.7276843-01

0.1817763 03 0.113864E 04 0.113919E 00
0.327916E 03 0,3472213 04 - 0.2277643 00
0.3329163 03 0,3508553 04 0.0
0.2520003 04 0.1898913 05 0.0

Methane 0.900000E 02 -0.140307E 04 0.0

0 180000E 03 - 0.2457203 03 0.4440393-02
0.2700003 03 0.1002023 04 0.491978E-01
0.274800E 03 0.1076693 04 0.902582E-01
0 372268E 03 0.263008E 04 -0.168425E 00
0.377268E 03 0.268834E 04 0.0
0.2520003 04 0.2735233 05 0.0

Ethane 0,900000E 02 - 0,5560863 04 0.0

0.161784E 03 - 0.4387543 04 -0,2840313-04
0.396000E 03 - 0.3931943 03 0.1823663-01
0 4400723 03 0,4546823 03 0.6723843-01
0.5738873 03 0.322121E 04 -0.1203973 00
0.578887E 03 0,3304223 04 0.0
0,252000E 04 0.3533703 05 0.0

Propane 0,900000E 02 - 0.8590633 04 0.0

0.153000E 03 -0,7321483 04 0.315910E-Q2
0.369000E 03 -0.2768163 04 0 178099E-01
0.396000E 03 - 0.215366E 04 0 2719033-01
0.415979E 03 - 0.1688253 04 0.8765393-02
0.516419E 03 0.769357E 03 0 4372423-01
0,532992E 03 0,1209273 04 0 811782E-01
0.657002E 03 0.4733153 04 -0,9931183-01
0.662002E 03 0.4862263 04 0.0
0,252000E 04 0.526869E 05 0.0

But'ane 0.900002E 02 -0.105291E 05 0.2114273-01

0.3852003 03 -0.3709493 04 0,4643423-01
0.4392003 03 -0.209693E 04 0,350586E-01
0.493199E 03 -0 376723E 03 0,3483903-01
0.6011993 03 0 337787E 04 0.395650E-01
0.612480E 03 0.3'795793 04 0.4368333-01
0 72172552 03 0.801006E 04 - 0,164924E-01
0.726725E 03 0.820377E 04 0.0
0.2520003 04 0 7765443 05 0.0

Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1 9 7 0 559

 These extrapolated volumes are in good agreement with
Table VIII. Accuracy of Zero-Pressure the approximate correlation of Prausnitz and Chueh (1968).
liquid Enthalpy Spline Fits Above T , = 0.8, Equation 84 was developed to yield zero for
RMS Error, Max Error, the liquid-enthalpy pressure correction a t reduced tempera-
Component Btu/Lb-Mole Btu/Lb-Mole Ref. tures approaching 1.0 for liquid mixtures. The empirical
Hydrogen (Same as ideal gas enthalpy, H * ) elimination of negative pressure corrections by Equation 84
Nitrogen 0 914 3 016 Strobr idge, is in agreement with experimental data ou mixture enthalpies
1963 (Air Products and Chemicals, Inc., 1965-69a,b).
Methane 0.215 0.552 Din, 1961
Ethane 0 802 2.796 Din, 1961 H,(P) - H,(P = 0) = PV,a exp [P(Tr - 0.8)]
Propane 0.334 1.331 a

Butane 0.485 1.141 a Tr > 0.8 (84)

a Calculated using latent heats. See text.
Continuity of the liquid-enthalpy pressure correction and its
first temperature derivative is maintained by evaluating
constants a and p with Equation 80 a t T , = 0.8 as
mole fraction of hydrogen in the liquid phase. The liquid
enthalpies of propane and butane were obtained from Riedel's
correlations (Air Products aiid Chemicalq, Inc., 1961; Reid and
Sherwood, 1966) for vapor pressure and latent heat with
the following equation:
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For liquid mixtures (Prausnitz and Chueh, 1968),

The heat of mixing terms in Equation 77 are obtained by

Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

differentiation of Equation 65, using the temperature de-

pendence of the Llargules parameters given by Equation 59:

(79)

Thus the temperature dependence in Equation 59 yields par- 2

v

tial molar heats of mixing which are independent of tempera- v,, = ziv,
ture. Strictly, this is not correct, but no more call be justified i=l

by the available experimental data or until additional theo-

retical information becomes available.
The liquid mixture volumes in Equation 77 are calculated
as suggested by Chueh aiid Prausnitz (1968).
The V,@) functions used in Equation 40 should be the
same for w e in calculating both the partial molar liquid
volumes aiid liquid enthalpy pressure correction. However,
Equations 41 to 44 were developed before publication of
Equation 80. I n view of the assumptions made in the calcu-
latioii of partial molar liquid volumes and the inherent loss of
accuracy in the differentiation process to obtain the effect
of pressure on liquid enthalpies, separate V r ( i functions
) were
used empirically in the correlation of the data.
The coefficients for Equation 80 are given in Table IX. Prediction of Mixture Enthalpies. The vapor-liquid
Below T , = 0.56, Equation 80 was extrapolated linearly, equilibria aiid enthalpy prediction iiiethods determine t h e
such that the Tir(') functions and their first derivatives match enthalpy of a vapor-liquid inisture as
Equation 80 a t T , = 0.56.
H, = noHm + nzh, (91)
V7@)= 0.306322 + 0.134081 T , T,5 0.56 (81)
Predicted and experimental enthnlpiei (-Gr Products and
T7,'1) = 0.566317 + 0.765870 T, T , 5 0.56 (82) Chemical-, h e . , 1965-69a,b; Clark and McKinley, 1969;
Sahgal et al., 1965) are cornpared for three niiytures in Tables
) 1.21184 - 1.92778 T,
V r ( 2= T,_< 0.56 (83) X, XI, and XI1 and Figures 12, 13, and 14. The contributions

Table IX. Coefficients in Equation 80 for Saturated liquid Volumes

l 0 b C d e f
1 0.11917 0.009513 0.21091 -0.06922 0.07480 - 0.084476
2 0.98465 - 1.60378 1,82484 -0.61432 -0.34546 0.087037
3 -0.55314 -0.15793 - 1,01601 0.34095 0,46795 - 0,239938

560 Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970

 Table X. Cooling Curve A, 488.5 PSlA
Mixture Composition, Mole yo
KZ 26.347
CH4 71.358
CzHs 2.295
Dew point = - 135.2"F
Bubble point = -179.8'F
Liquid-Phase Liquid-Phase
Heat of Mixing, Pressure Correction, (H*-H), Enthalpy Difference, Btu/Mole
r, OF % Liquid Btu/Mole of Liquid Btu/Male of Liquid Btu/Mole of Vapor Exptl. Calcd. Dev.

100.00 0.00 ... ... 182 0 0 0

- 110.35 0.00 ... . . I 512 2010 2008 - 2
- 130.47 0.00 ... ... 620 2270 2271 + 1
-150.23 19.26 25.4 0.02 717 2820 2940 +120
- 169.78 74.24 40.6 0.03 733 4000 4119 +119
- 189.65 100.00 49.5 0.19 ... 4710 4762 + 52
- 209,87
- 230.27
100.00
100~00
49.5
49.5
6.23
19.8
...
, . .
5020
5330
5074
5374
++ 54
44
- 250.24 100.00 49.5 29.1 ... 5610 5663 f 53
-270.23 100.00 49.5 36.8 ... 5890 5943 + 53
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Table XI. Cooling Curve B, 44.8 PSlA

Mixture Composition, Mole %a

C&
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

H2 8.25 1.157
9 2 1.391 C4H10 0,0545
CHI 69.86 co 0.07
CzHs 18.46 0 2 and Ar 0,758
Dew point = - 124,O"F
Liquid-Phase liquid-Phase
Heat of Mixing, Pressure Correction, (H*-H), Enthalpy Difference, Btu/Mole
r, OF % Liquid Btu/Mole of Liquid Btu/Mole of Liquid Btu/Mole of Vapor Exptl. Calcd. Dev.
100.00 0.00 ... ... 24 0 0 0
- 50.77 0.00 ... ... 42 1359 1364 $ 5
- 50.85 0.00 ... ... 42 1369 1364 -5
- 70.26 0.00 ... ... 46 1524 1533 +9
- 90.59 0.00 ... ... 52 1692 1708 +I6
-111.19 0.00 ... ... 58 1876 1886 +IO
- 120.59 0.00 ... ... 61 1956 1967 +11
-130.87 0.88 25.5 5.52 64 2118 2117 - 1
- 150.03 7.96 14.4 5.07 63 2722 2728 f 6
-150.51 8.19 14.2 5.07 62 2746 2746 0
-170.17 16.21 9.81 5.05 60 3354 3400 -46
- 188.09
- 200.44
21.57
25,46
7.99
6.52
4.94
4.83
62
65
3814
4104
3852 + 38
4140 +36
-210.05
-219.64
29,86
38.08
5.33
5.46
4.71
4.54
67
69
4357
4714
4400
4780
+ 43
f66
- 229,81
-238.95
57.60
75.07
9.11
11.6
4.26
4.17
66
51
5518
6231
5540
6230
+ 22
- 1
-239.93 76.26 11.8 4.18 49 6323 6282 -41
- 240.39 76.78 11.9 4.19 49 6254 6305 $51
- 259.42 87.07 13.9 4.18 24 6816 6891 +75
-259.63 87.12 13.9 4.18 24 6820 6896 +76
02, rlr, and CO considered as ?j2 in calculations.

to the enthalpy calculations are illustrated by the tabulated Conclusions

values of (N* - H ) , liquid-phase heat of mixing, liquid-
phase pressure correction, and per cent' liquid. The enthalpy
comparisons are prehented a'; "cooling curves" which are
useful for heat-exchanger design. Figure 12 is representative
of a stream encountered in a natural gas liquefaction plant.
Figures 13 and 14 correspond to fuel and feed streams,
respectively, in a hydrogen purification plant. This thermo-
dynaniic correlation has been wed in the design of loy-
temperature heat exchangers with temlierature differences as
small as 2'F.
The thermodynamic framework dewribed here affords a
high degree of flexibility for the correlation and accurate
prediction of thermodynainic Iroperties through the use of
separate correlations for the vapor and liquid phases. The
system is modular and can therefore be modified easily as
new theoretical and experimental information becomes avail-
able. If desired, new correlations can readily be substit,uted
for those used here for second or third virial coefficients, pure
component liquid fugacities, activity coefficients, etc.
At present', the system is limited to moderate densities.

Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970 561

 Table XII. Cooling Curve C, 738.5 PSIA
Mixture Composition, Mole
H2 70.72 C8Hs 0.37
N2 0.36 C4H10 0.11
CH4 23.55 co 0.04
C2H6 4.76 0 2 0.09
Dew point = -70.2'F
liquid-Phase liquid-Phase (H*-HI,
Heat of Mixing, Pressure Correction, Btu/Mole Enthalpy Difference, Btu/Mole
T, OF % liquid Btu/Mole of liquid Btu/Mole of liquid of Vapor Exptl. Calcd. Dev.
- 50 0.00 ... ... 102 0 0 0
- 70 0.00 ... ... 114 165 157 - 8
- 90 0.61 65.4 56.6 123 325 347 +22
-110 2.15 53.8 51.5 126 550 57 5 + 25
- 130 4.25 44.5 52.6 125 805 822 +17
- 150 6.29 40.7 54.7 127 1045 1058 +13
- 170 8.58 41 . O 55.0 130 1295 1292 - 3
-190 12.09 45.1 53.2 127 1565 1549 - 16
-210 17.38 48.4 53.4 111 1855 1846 - 9
- 230 22.46 46.8 58.8 91 2155 2142 - 13
- 250 25.92 42.4 66.9 78 2415 2402 -13
a CO and 0
2 considered as Nz in calculations.
Downloaded by TEXAS A&M INTL UNIV on August 31, 2015 | http://pubs.acs.org
Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

LL
-100
I\
-
488.5 psia

Np
MOLE %
26347
CH4 71.358
O t 738.5 psia

Hp
Np
CH4
MOLE %
7072
.36
36
2355
CpH6 2.295
a
hi
CpH6 4 76
$ C ~ H E ) .37
8 C4h0 I1

e -200 -
0 AIR PRODUCTS AND
CO
02
04
.09
CHEMICALS, INC (1965)
- CALCULATED +
-200 - 0 AIR PRODUCTS AND
CHEMICALS, INC (1967)
1 - CALCULATED \ I
I I I I
-300

-300
0 500 1000 IMO 2000 2500
AH, BTU/LB MOLE

Figure 14. Cooling curve C

MOLE % Extension to higher densities will require improved second

44.8 psia
n2 8.25
and third virial coefficient predictions and the inclusion of
N2 1.391 either higher virial or empirical terms. For bet,ter predict'ions
LL -100 CH4 69.86 of vapor-liquid equilibria and enthalpies, an improved correla-
CpH6 18.46
tion of partial molar liquiJ volumes is needed to determine
C3H8 I. 157
more accurately the effect of pressure on thermodynamic
C~HIO ,0545
CO .07 properties in t,he critical region. hlso, additional information
w @BAR ,758 011 the temperature dependence of activity coefficients is
I-
needed to obtain temperature-dependent liquid-phase heats
-2ooc "h of mixing.
0 AIR PRODUCTS AND
CHEMICALS, INC. (1968)
Acknowledgment

The authors are grateful to Air Product9 and Chemicals,

Inc., for permission to publish this work, which was per-
-300
loo0 Zoo0 3000 4000 5000 6CQO 7Ci10 fornied over a period of several years in support of engineering
AH,B T W L B MOLE design and concurrently with experimental research. During
Figure 13. Cooling curve B this time, valuable contributions were made by I?. W. Wang,

562 Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970

 D. J. Hersh, and L. Israel. The experimental work directed
by C. McKinley made possible the development of parameters
required in this work.
Nomenclature
A,D = biliary Margules parameters
d , e , f = constants
= second virial coefficient, cu ft/lb-mole
= van der Waals constant, cu ft/lb-mole
= third virial coefficient, (cu ft/lb-mole)Z;
ternary hlargules parameter
E = quaternary hIargules parameter
f = pure component liquid-phase fugacity, psia
G = Gibbs free energy, Btu/lb-mole
H = vapor-phase enthalpy, Btu/lb-mole; vapor
or liquid-phase enthalpy in Equation 7 3 ,
Air Products and Chemicals, Inc., experimental mixture en-
thalpy data, 1965-69b.
Air Products and Chemicals, Inc., internal communication, 1961.
Akers, W.W., Burns, J. F., Fairchild, W. R., Ind. Eng. Chem. 46,
2531 119543.
Akery W. W., Eubanks, L. S., I n t . Advan. Cryog. Eng. 3, 275
( l h
Aroi&H. J., Katz, D. L., Ind. Eng. Chem. 43, 185 (1951).
Benedict, Il.,\TTebb,G. B., Rubin, L. C., Chem. Eng. Progr. 47,
419, 440 (1951a).
Benedict. M.,Webb, G. B., Rubin, I,. C., J . Chern. Phys. 8, 334
(1940).
Benedict, )I., Webb, G. B., Rubin, L. C., J . Cheiri. Phys. 10, 747
(19421.
Benedict, lI.,Webb, G. B., Rubin, L. C., Friend, L., Chem. Eng.
Progr. 47, 571, 609 (195lb).
Benhani, A. L., Katz, I). L., -4.Z.Ch.E.J. 3,33 (1957).
Brown, G. JI., Smiley, H. lI.>A.I.Ch.E.J. 12,609 (1966).
Chang, S. D., LU, B. C. Y., Chenz. Eng. Progr. 63, No. 81, 18
( l a w ,.
)
, I Y V .

Chao, K. C., Seader, J. D., A.Z.Ch.E.J. 7,598 (1961).

B tuilb-mole
= liquid-phase enthalpy, Btu/lb-mole
= ionization potential, electron volts
k = characteristic parameter defined by Equation
7 Cines, AI. R., Roach, J. T., Hogan, R. J Roland, C. H., Chem.
L = length of spline interval
111 = Henrys constant, p i a
x = number of components in a mixture
Downloaded by TEXAS A&M INTL UNIV on August 31, 2015 | http://pubs.acs.org
Chueh, P. L., Prausnitz, J. lI.,Zncl. Eng. Chem. 60,No. 3, 34-52
(1968).
Cheung, H., wang, D. I. J., I K DESG.
. C H i x r . FCKD.W.3, 355
(1964).
Eng. Progr. Symp. Ser. 49, S o . 6, 1 ( 1 6 3 ) .
Claitor, L. C., The Second Sirial Coefficieiit of the Ilajor
Atmospheric Gases at Low Temperatiire., 31,s. thesis,
Agricultural and llechanical College of Texas, 1948.

n = number of moles Claitor, L. C., Crawford, D. B., Trans. A.S.JI.E. 71, 885 (1949).
P = pressure, psia Clark, 13. G., lIcKinley, C., Znt. d d v a n . Crvog. Eng. 14, 55
R = gas constant ilSflSi.
\ - - I - / .

T = temperature, OR Cohen, A. E., Hipkin, H. G., Koppany, C. R.,Chem. Eng. Progr.

Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

v = molar volume, cu ft/lb-mole Synzp. Srr. 63, KO.81, 10 (1967).

Cozwav, H. F., Katz, I>. L., A.Z.Ch.E.J. 5,46 (1939).
X = mole fraction in liquid phase

s = mole fraction in vapor phase

= compressibility factor
David; H. G . , Hamann, S. D.! I n f . Illech. Eng. (London), 74
11958).
Diii, F., Thermodynamic Fintctions of Gases, Tol. 3, Britter-
wnrths.
_. T,nndnn. 1061
... .~
Dodge, B. F., Chemical Engineering Thermodynamics,
G R E E KLETTERS McGraw-Hill, Kew York, 1944.
A = change in a property Eakin, B. E., Ellinnton. 11. T., Gami, 11. C., Institute of Gas
Technolog?: Res. Bii11.26 (1955).
ff, P = constants Fastovski, S. G., Gonikberg, AI. G., J . r h u s . Chem. ( C S S R ) 14,
6 = qolubility parameter, (cal cc)I * in Equation 427 (1940).
48 n h e n P,is in atni Gaiimer, L. S., Chem. Eng. Progr. 63,72 (1967).
= solubility parameter of a mixture, (cal cc) Gonikberg, 11. G., Fastoviki, \. G., Gurech, I. G., Acta Physico-
= liquid-phase activity coefficient chim. (CSSX) 1 1 , S65 (1939).
= vapor-phase fugacity coefficient Gnnri, It. D.j 31,s. thesis, Chemical Engineering I)epartmeiit,
= volume fraction University of California, Berkelej-, 1958.
= density, lb-molescu ft Her>h, I). J., Zellner, 11. G., Interval Location in the Spline
= reduced fugacity function Fit Technique, iiiternal conimrniicatioii, .4ir Products and
Chemicals. Inc.. 1969.
= acentric factor Hildebrand, Jl H., Scott, R . L., Solubility of Nonelectrolytes,
= latent heat of vaporization Ileinhold, Sew York, 1950.
Hilsenrath, J., Beckett, C. W,, Benedict, W.Y., Fano, L., Hoge,
H. J., lIasi, J. F., Xiittall, 11. L., Touloukian, Y. S., Woolley,
SUBSCRIPTS H. IT., Tables of Thermal Proeerties of Gases, XBS Circ.
564 11955).
C = critical Hirschfelder, J. O., Curtiss, C. F., Bird, 11. B., Xolecular Theory
h, i,, I , k . 1 = components of Gases and Liquids, p. 230, Wiley, Sew York, 1954.
1 = liquid Hoiigen, 0. A,, Watson, K . AI.> Ilagatz, 1:. A,, Chemical Pro-
nz = misture cess Principles, Part 11, Thermodyiiamics, 2nd ed., Wiley,
n = spline interval boundary New York, 1959.
T = reduced Hudson, G. H., JIcCoiibrey, J. C., Trans. Faraday Soc. 56, 761
V = vapor (1960).
= components Huff, J. A, Reed, T. AI., J . Chem. Eng. Data 8 , 306 (1963).
1, 2, Klaus, R . L., Tan Xes?, H. C., A.I.Ch.E.J. 13, 1132 (1967).
Knapp, H. F. P., Knoester, lI,,Kiiobler, C. 11.)Beenakker,
SUPERSCRIPTS J. J. JI.,Physzca 28, 21 (1962).
0
Lyckman, E. W., Eckert, C. A , >Praiihnitz, J. ll.,Chenz. Eng. Sci.
= stnndard or reference state; vapor pressure 20. 685 (1965,).
coiidit ions Lyckman, E . IT., Eckert, C. A., Praii-nitz, J. lI.,Chem. Eng. Sci.
- = partial molar property 20, 703 (1965b).
* = ideal gas state; unsymmetrical normalization llaimoni, -i., -4.i.Ch.E.J. 7, 371 11961).
of activity coefficients Matschke, 11. E., Thodou, G., J . Chern. Eng. Data 7, 232 (1962).
I
= second derivative or spline coefficient lIichels, d.,DeGraaff, W., Ten Seldam, C. h.,Physica 26, 393
(ref) = reference state (1960).
AIullina, J. C., Ziegler, W. T., Int. Advan. Cryog. Eng. 10, 171
(1965).
literature Cited OConiiell, J. P., Prausnitz, J. 11.)ISD.ESG. CHERT. FCSD.W. 3,
347 (1964).
iidler, S.B., Friend, L., Pigford, R . L., d.Z.Ch.E.J. 12, 629 (1966). Orentlicher, l I . >Prausnitz, J. 31,, Chem. Eng. Sei. 19, 775 (1964).
Air Prodiicts and Chemical<, I n c . , coiifidential experimental Pitzer, K. S . , J . .Inier. Cheirz. Soc. 77, 3472 (1955).
pha-e-eqiiilibriiim data, 1969. Pitzer, IC. 8..Ciirl, It. F., J . --liner. Chem. Soc. 79,2369 (1957).
Air Prodricts and Cheniicals, Iiic., confidential experimental Pitzer; K . S,, Lippmaiii;, I). Z., Curl, It. F., Hrigginr, C. ll.,
enthalpy data, 1965-69a. Petersen, D. E., J . A l r n e T . Cheni. Soc. 77, 3433 (1955).

Ind. Eng. Chem. Fundam., Vol. 9, No. 4, 1970 563

 Prausnitz, J. RI., A.I.Ch.E.J. 5 , 3 (1959).
Prausnitz, J. AI., RIolecular Thermodynamics of Fluid-Phase
Equilibria, Prentice-Hall, Englewood Cliffs, N. J., 1969.
Prausnitz, J. AI., Chueh, P. L., Computer Calculations for High-
Pressure Vapor-Liquid Equilibria, Prentice-Hall, Englewood
Cliffs, Pi. J., 1968.
Prausnitz, J. AT., Eckert, C. A,, Orye, R. V., OConnell, J. P.,
Computer Calculations for Rlulticomponent Vapor-Liquid
Equilibria, Prentice-Hall, Englewood Cliffs, N. J., 1967.
Price, A. R., Kobayashi, R., J . Chem. Eng. Data 4,40 (1959).
Reid, 11. C., Sherwood, T. K., Properties of Gasea and Liquids,
2nd ed., RIcGraw-Hill, New York, 1966.
Roberts, L. R., Wang, R . H., RIcKetta, J. J., J . Chem. Eng. Data
7, 484 (1962).
Ruhemann, hl., Proc. Roy. SOC.171A, 121 (1939).
Sahgal, P. N., Geist, J. RI., Jambhekar, il., Wilson, G. RI.,
Int. Adaan. Cryog. Eng. 10, 224 (1965).
Sprow, F. B., Prausnitz, J. RI., A.I.Ch.E.J. 12,780 (1966).
Strobridge, T. R., Thermodynamic Properties of Nitrogen from
144 to 540OR between 1.0 and 3000 psia, National Bureau
of Standards, Tech. Note 129A (1963).
Taff, W. O., Selected Values of Properties of Hydrocarbons
and Related Compounds, American Petroleum Institute
Research Project 44, TexaT A&lI University, 1966.
Volk, H., Halsey, G. D., J . Chem. Phys. 33, 1132 (1960).
Williams, R. B., Katz, 1).L., Ind. Eng. Chem. 46, 2512 (1954).
Wilson, G. RI., Int. Aduan. Cryog. Eng. 9, 168 (1964a).
Wilson, G. XI., J . Amer. Chem. SOC.8 6 , 127 (196413).
Wohl, K., Chem. Engr. Progr. 49, 218 (1953).
Wohl, K., Trans. A.I.Ch.E. 42, 215 (1946).
RECEIVED for review February 24, 1970
ACCEPTED August 19, 1970
Division of Industrial and Engineering Chemistry, Symposium
on Enthalpy of RIixtures, 159th Meeting, ACS, Houston, Tex.,
February 1970.

Quasilattice Theory and Paraffin-Alcohol Systems

Chia-Ming Kuo, R. L. Robinson, Jr., and Kwang-Chu Chao2
Downloaded by TEXAS A&M INTL UNIV on August 31, 2015 | http://pubs.acs.org

Oklahoma State University, Stillwater, Okla. 74074

Publication Date: November 1, 1970 | doi: 10.1021/i160036a005

The quasilattice theory advanced b y Guggenheim and Barker, re-expressed in canonical partition function
of group interactions, i s applied to the representation of excess thermodynamic properties of n-alcohol-
n-paraffin mixtures. Six exchange energies of the groups involved are determined b y fitting the equations
of excess enthalpy to experimental data on eight binary systems over the entire composition range. The ex-
change energies thus determined are employed to predict excess free energy and excess entropy for com-
parison with experimental data on two binary systems. Reasonable agreement i s obtained for all three
excess properties for the systems studied.

groups) placed on well-defined lattice sites. Each type of

T h e representation of excess thermodynamic properties in
liquid systems coiitaiiiing polar substances presents a chal-
lenging problem in solution thermodynamics. Recent data on
heat:: of mixing (Savini et al., 1965) and phase equilibria
(Van S e s s et al., 1967a,b) for a number of n-alcohol-n-paraffin
binary systems provide a n opportuiiity for critical com-
parison;; of various theories that, describe the behavior of
these solutioiis.
Previous investigators have applied group solution (Chao
et al., 1967) and association-type (Renon and Prausnitz, 1967;
Kiehe and Bagley, 1967) models to describe alcohol-paraffiii
systems. However, 110 similar results have used the quasi-
lattice theory (Barker, 1952; Guggeiiheini, 1944). T h e present
work examines the quasilattice model in its ability to describe
the excess enthalpy and free energy of alcohol-paraffin
systems.
The quasilattice theory advanced by Guggenheim (1944)
and Barker (1952) re-expreqsed in canonical partition function
of group interactions, is used in the present study. The
present, equations serve as a convenient basis for further
development and use in cell-theory calculations.
segment i possesses a number, zit of contact points, where it
interacts with adjacent segments-for example, a pentane
molecule could be considered t o coil of two methyl seg-
ments and three methylene segments. The configuration
energy of the solution is the sum of contributions from inter-
action3 bet,weeii pairs of adjacent segments.
Guggenheini (1944) developed the quasilattice theory of
molecules of different sizes and occupying different numbers of
lattice sites. Segment:: of the same molecule interact in the
same n a y . Barker (1952) extended Guggenheinis theory to
allow one molecule to have different kinds of segments.
Earlier.; results are iii terms of grand partitioil functions.
I n the following we re-express Guggenheinis results to allow
one molecule to have more than one kind of segmeiit. Our
prereiit results are in the caiioiiical form and appear to be well
suited for further developnieiit into the language of the cell
theories.
The configurational energy, E! of a lattice solution is com-
pletely determined by a set of numbers, S i j , that represent the
numbers of contacts bettTeen segments of types i and j.
The caiioiiical partition function is given by

Quasilattice Theory Q = g exp ( - E I k T ) (1)

Ni,
Basically, the quasilattice theory considers each molecule -4 where g denotes the degeneracy of the configuration described
in solution to be composed of a number, rA, of segments (or by the set of S i j s .
Let e i j stand for t,he energj- of interaction between an i
Present address, Esso Production Research Co., Houston, segment and a j segment. Then,
Tex. 7T001
2 Present address, Purdue Universitj-, Lafayette, Ind. 47907 E = Yiji3 (2)
To whom correspondence should be sent. z 33i

564 Ind. Eng. Chem. Fundam., Vol. 9 No. 4, 1970