Research: Science and Education
Thermodynamics of Mixing Real Gases
Simeen Sattar
Department of Chemistry, Bard College, Annandale-on-Hudson, NY 12504-5000; sattar@bard.edu
Undergraduate physical chemistry textbooks commonly
treat the thermodynamics of mixing ideal gases but neglect
that of mixing real gases. This often prompts students, who
are accustomed to considering the behavior of ideal and real
gases in tandem in a thermodynamics course, to ask about
real gas mixtures. Although the thermodynamics of mixing
real gases can be subtle, it is worth considering inclusion of
this topic in the syllabus. Not only does it complete the
parallel with ideal gases and anticipate the comparison between
ideal and real solutions, but students will find study of real
gas mixtures rewarding because it draws on their existing
knowledge of gases and intermolecular forces and connects
to newly learned topics such as the relationships among
thermodynamic functions, fugacities, and virial coefficients.
Moreover, the abundance of experimental data on real gas
mixtures allows students to compare their expectations to
actual behavior. An added benefit of the data is that it provides
a rich and ready source of literature-based problems and class-
room presentations.
Although mixtures of real gases are addressed in advanced
treatises on thermodynamics (e.g., refs 1–3), the following
discussion is designed to be continuous with the coverage of
ideal gas mixtures usually found in undergraduate texts. It
draws heavily from recent experimental studies of gas mixtures,
with the goal of impressing upon students that gas-phase
thermodynamics is a vital and engaging subject that can test
their understanding of molecular behavior.
Gibbs Energy of Mixing Real Gases
The thermodynamics of mixing real gases at constant
temperature and pressure is approached in exactly the same
way as for the mixing of ideal gases. An expression for the
Gibbs energy of mixing, ∆ mixG, is the fundamental result, and
from this, expressions for the entropy, enthalpy, and volume
of mixing easily follow.
The Gibbs energy of a system of unmixed gases is given by
Ginitial = Σi ni µi* (1)
where ni is the amount of component i, µi* is its chemical
potential (an asterisk denotes a pure component), and the
summation extends over all components of the system. For
a real gas at a temperature T and pressure p, the chemical
potential is stated in terms of its ideal gas standard state
chemical potential µi° and fugacity fi *:
µi*( p,T ) = µi°(T ) + RT ln[ fi *( p,T )/p°] (2)
Once the gases are mixed, the Gibbs energy of the system
becomes
Gfinal = Σi ni µi (3)
with
µi( p,T ) = µi°(T ) + RT ln[ f i ( p,T )/p°] (4)
Here f i ( p,T ) refers to the fugacity of component i in a
mixture whose total pressure is p.
JChemEd.chem.wisc.edu • Vol. 77 No. 10 October 2000 • Journal of Chemical Education
The change in the Gibbs energy on mixing is found by
subtracting eq 1 from eq 3:
∆ mixG = RT Σi ni ln (fi/fi*) (5)
One way to evaluate this expression is to appeal to the
empirical rule of Lewis and Randall, which states that fi/fi * = yi,
where yi is the mole fraction of component i. (Note that for
an ideal gas mixture, this rule reduces to Dalton’s law.) Although
extremely convenient, this rule is not generally correct. For
instance, a pair of gases might obey it under some conditions
of temperature and pressure but not others (4 ). Substituting
the Lewis and Randall rule into eq 5 yields
∆ mixG = RT Σi ni ln yi (6)
which is identical to the expression for mixing ideal gases—
an uninformative result.
Thus a more accurate means of evaluating the fugacities
required by eq 5 must be found. Examining the definition
of fugacity is helpful here. For a pure gas fugacity is given by
the relation
p
V m*
f i* = p exp – 1 dp′ (7)
RT p′
0
and for a component of a mixture it is given by the analogous
relation
p
V i,m
f i = p i exp – 1 dp′ (8)
RT p′
0
Note that eq 8 is very similar to eq 7, except that a component’s
partial pressure p i ≡ y i p and partial molar volume Vi, m ≡
(∂V/ ∂ni )T, p, nj ≠ni replace the total pressure and molar volume. In
both cases, the total pressure p is the upper limit of integration.
Just as the fugacities in eq 7 are evaluated from p,V,T
measurements on pure gases, those in eq 8 may be evaluated
from similar measurements on gas mixtures, with composi-
tion as an added variable. These p,V,T data are then fitted to
an equation of state such as the virial equation, in which the
compression factor Z is expanded in powers of Vm
1 :
Z ≡ pVm/RT = 1 + BVm
1 + CVm
2 + … (9)
B and C are the second and third virial coefficients, and they
are functions of temperature and composition. Virial coefficients
for mixtures retain the same microscopic significance as for
pure gases: B accounts for two-body interactions, C for three-
body interactions, and so on. Therefore, for mixtures, B must
be an average of the second virial coefficients for all possible pairs
of like and unlike molecules, each weighted by the probability
that the corresponding two-body interaction will occur:
B = Σ Σ yi yj Bi j (10)
i j
A binary mixture, for instance, is described by one cross-term
1361
 Research: Science and Education
(B12) and two pure-component (B11, B 22) second virial co-
efficients.
Especially if students have encountered some statistical
mechanics, it is worth pointing out that virial coefficients
are intimately related to molecular interactions through the
equation
∞ coefficients and the methods by which they were obtained. In
B ij =
2π NA exp
ui j r′ /kT – 1 r′ 2dr′ (11)
0
where the function uij (r) is the pair potential for molecules
separated by a distance r. Negative values of Bi j indicate that
attractive forces are predominant between species i and j,
whereas positive values indicate that repulsive forces are pre-
dominant. Of course, temperature plays a decisive role in
determining the sign of Bi j . By assuming a form for the
potential energy function, it is sometimes possible to extract
its parameters from knowledge of the second virial coefficients
(5). Consequently, virial coefficients are quantities of both
fundamental and practical import.
It is not difficult to deduce the form of a mixture’s third
virial coefficient from eq 10:
C = Σ Σ Σ yi yj yk Ci jk (12)
i j k
A term in the sum such as yi2yjCiij accounts for the likelihood
and strength of simultaneous interaction between two molecules
of species i and one of species j. The relationship between
Ci jk and pair potentials can be found in books on statistical
mechanics (6 ).
Returning to the task of determining f i , the next step
would be to solve eq 9 for Vm and obtain the corresponding
Vi, m. However, even when the series in eq 9 is truncated after
the second term, it is still quadratic in Vm. To circumvent
this difficulty, Z is instead expressed as a polynomial in p:
Z ≡ pVm/RT = 1 + Bp/RT + (C – B 2)(p/RT ) 2 + … (13)
Now, solving for Vm is straightforward. The series on the right
can be simplified by assuming that the gas mixture is only
slightly imperfect, a definition that omits all terms beyond
Bp/RT. Because the parameter B accounts for pairwise inter-
actions between the gas molecules, the approximation limits
subsequent discussion to moderate pressures, a limit sensitive
not only to the identity of the gases but also to the composition
of the mixture. (From the familiar plot of Z( p), students might
anticipate that this should be true. At 273 K for example, Z
is fairly linear to 10 MPa for hydrogen but to only 1 MPa for
nitrogen. Mixtures of the two should, and do, show intermedi-
ate behavior [7 ].) Truncating eq 13 after the second term,
substituting for B using eq 10, and evaluating the partial
derivative (∂V /∂ni)T, p, nj ≠ ni yields an expression for the partial
molar volume of component i (8):
Vi, m = RT /p + Σ Σ yj yk (2Bij – Bjk ) (14)
j k
As before, the summations extend over all components of the
system, including species i. Substituting this intermediate result
into eq 8 yields
fi = pi exp[Σ Σ yj yk (2Bij – Bjk )p/RT ] (15)
j k
As a check, note that eq 15 reduces to the correct expression
for the fugacity of a slightly imperfect pure gas:
f i* = p exp(Bii p/RT ) (16)
1362 Journal of Chemical Education • Vol. 77 No. 10 October 2000 • JChemEd.chem.wisc.edu
Thus for slightly imperfect gas mixtures the problem of
determining the fugacities of its components devolves to ob-
taining a complete set of second virial coefficients. Besides
compression factor measurements, second virial coefficients
may be derived from data such as pressure or enthalpy changes
on mixing. Reference 5 is an invaluable compendium of virial
the absence of experimental results, second virial coefficients
may be calculated from correlations based on the principle
of corresponding states (1–3) and pair potential functions (2).
Substituting eqs 15 and 16 into eq 5 yields a general
expression for the Gibbs energy for mixing slightly imper-
fect gases:
∆ mixG = RT Σ ni ln yi + Σ ni[Σ Σ yj yk (2Bij – Bjk ) – Bii ]p (17)
i i j k
The first term on the right is the Gibbs energy for mixing
ideal gases ∆ mixG (0); it is necessarily negative. The second term
accounts for deviations; it may be positive or negative.
Discussion is greatly simplified by considering two-com-
ponent mixtures. In this case, equation 17 reduces to
∆mixG = nRT ( y1 ln y1 + y 2 ln y 2) +
(18)
ny1 y 2(2B12 – B11 – B22 )p
where n is the total amount of gas. All the quantities on the
right can be determined experimentally. Within the slightly
imperfect gas approximation, for (2B12 – B11 – B22)p/RT ≤ 2,
∆ mixG attains its minimum value when an equal number of
moles of the two components are mixed, just as is true for
binary mixtures of ideal gases. For values of this ratio greater
than 2, more complex behavior occurs, but such values are
unlikely within this approximation.
Before leaving this section, it is worth noting that in
developing an expression for ∆ mixG, only deriving eq 14
might present a substantive difficulty to students; even this
difficulty vanishes if discussion is confined to binary systems
at the outset.
Excess Thermodynamic Functions for Binary Mixtures
It is natural at this point to introduce excess thermody-
namic functions, which focus attention on deviations from
ideality. From eq 18, the excess molar Gibbs energy is given by
G Em(1) = y1 y 2(2B12 – B11 – B22 )p (19)
where the superscript (1) serves as a reminder that this is just
a first-order correction. The term on the right merits close
examination. Its magnitude increases with the pressure of the
mixture, since increasing pressure at a fixed temperature in-
creases interactions, whether favorable or not, by bringing
molecules closer together. (Of course, this linear relationship
is not true at high pressures, where the slightly imperfect gas
approximation fails.) As p → 0, gas mixtures, like pure gases,
behave ideally. The factor y1 y 2 weights deviations by the prob-
ability of interaction between unlike molecules. The term
2B12 – B11 – B22 (henceforth the excess second virial coefficient
B E ) can be negative, zero, or positive, depending on whether,
loosely speaking, interactions between unlike molecules (1–2)
are stronger than, identical to, or weaker than the average
interactions between like molecules (1–1 and 2–2). (Care
must be taken not to confuse this statement with averages of
pair potentials.) When B E < 0, there is an additional driving
 Research: Science and Education

force that favors mixing beyond the larger volume available Table 1. Selected Thermodynamic Data for Equimolar
to each component, and conversely for B E > 0. Whether Mixtures of Various Gases
enthalpy or entropy effects are predominant is a question to be BE / G E m (1 )(p°)/ ∆m ix Gm (0 )/
Mixture T/K Ref
examined shortly. When BE = 0, the mixture is said to be ideal 3
cm mol
1
J mol
1 a J mol
1
(9, p 312), even though the gas molecules may be interacting CO/N2 303.2
1.5 b
0.038
1746 10
with one another. The concept that ideality for a gas mixture CH3 Cl/C2 H5 Cl 290.2 71 c
.
1.8
1672 11
includes molecular interactions aids students in developing a
CH3 CN/n-C4 H1 0 373.1 1822 d .
45.56
2150 12
definition of ideal solutions that is applicable to any phase.
Of the mixtures included in Figures 1 and 2 (10–16 ), B E C2 H5 OH/C6 H1 2 363.2 970 c .
24.3
2093 13
is most nearly zero for N2/CO, a system in which the compo- CH2 FCF3 /C3 H8 299.9 248.8 .
b
6.22
1729 14
nents are well matched in size, dipole moment, and polariz- CHCl3 /C6 H1 2 353.2 118 e .
2.94
2036 15a
ability. A second such example is the system CH3Cl/C2H5Cl. CHCl3 /C6 H6 353.2
274 e .

6.85
2036 15a
Even though both component molecules are polar, their similar
CH3 OH/(CH3 )3 N 308
11,980 c
299.5
1775 16
sizes and dipole moments (1.87 and 2.02 D, respectively)
give rise to fairly small values of B E. Systems consisting of
a Forthe 1st-order correction to the excess Gibbs function, p° = 1 MPa.
b± 2.1 cm3 mol
1.
disparate species tend to have large, positive excess second c Uncertainty not reported.

virial coefficients. Negative values of BE are indicative of a
specific interaction between unlike species, such as complex
formation or hydrogen bonding. For instance, the strongly
negative values of B E for the system CH3OH/(CH3)3N arise
from formation of a hydrogen-bonded alcohol–amine complex.
It is reasonable to expect that molecular interactions will become
less significant at high temperatures, causing the magnitude
of BE to decrease with increasing temperature. Figures 1 and
2 bear out this expectation. Small discrepancies attributable
to uncertainties in B11, B22, and B12 may be noted.
An alternative way of gauging the significance of deviations
from ideality is to compare the quantity G Em(1) to ∆ mixGm(0).
Except for CH3OH/(CH3)3N, the magnitudes of G Em(1) given
in Table 1 are not more than 2% of ∆ mixGm(0) and they are
frequently much smaller. It is important to bear in mind that
G Em(1) is merely the first term in the complete expression for
G Em. Phase separation (gas–gas immiscibility) has been observed
in some binary systems above the critical point of the pure
components (17 ), implying that the excess Gibbs energy can
become significant in comparison to ∆ mixG(0).
d Minimum uncertainty is ± 57 cm3 mol
1, as error in B
22 is not available.
e Maximum uncertainty is ± 58 cm3 mol
1.
Since the excess molar entropy for a slightly imperfect
gas mixture is given by
S Em(1) =
(∂G Em(1)/∂T )p, y 1 =
y1 y 2(dBE/dT )p p (20)
then S Em(1) E
> 0 when dB /dT < 0. This suggests that mixtures
such as CH3CN/n-C4H10 have a greater entropy than they
would if they were ideal. When dBE/dT > 0, as is true for
CHCl3/C6H6, then S Em(1) < 0. To what can the excess entropy
be attributed? For ideal gases, it is the larger volume available
to the individual components that accounts for all the entropy
of mixing at constant T and p, even though the net volume
of the system does not change as a result of mixing (18). For
real gases, then, one contribution to the excess entropy must
come from any net volume change on mixing; it may be
positive or negative. A second (negative) contribution might
arise when unlike species form a complex that constrains the

-8

2000

-10

1500
B E / (dm3 mol −1)
B E / (cm3 mol −1)

-12
1000

-14
500

-16
0

-500 -18
250 300 350 400 450 500 550 295 300 305 310 315 320

T/K T/K
Figure 1. BE
vs T for the systems ( 䊊) CH3CN/n-C4H10; (ⵧ) C2H5OH/ Figure 2. BE
versus T for CH3OH/(CH3)3N. B11, B22, and B12 are
C6H12); (䉫) CH2FCF3/C3H8; (䉭) CHCl3/C6H12); (䊉) CH3Cl/C2H5Cl; read from Fig. 5-28 in ref 2, which is based, in part, on ref 16.
(䉱) N2/CO; (䉬) CHCl3/C6H6. See Table 1 for references. Note the change in units from Fig. 1.

JChemEd.chem.wisc.edu • Vol. 77 No. 10 October 2000 • Journal of Chemical Education 1363

 Research: Science and Education

freedom of motion of the individual components. Figures 1 Table 2. Selected Thermodynamic Data for Equimolar
and 2 show that because the rate of change of B E becomes Mixtures of CHCl3 /C6 H1 2 and CHCl3 /C6 H6 at pⴗ = 0.1 MPa
smaller with increasing temperature, the excess entropy becomes B E/ dBE /dT/ H E m ( p°)/ H E m ( p°) (1 )/ S E m ( p°) (1 )/
T/K
smaller as well. cm3 mol
1 a , b cm3 K
1 mol
1 a J mol
1 c J mol
1 J K
1 mol
1
The temperature dependence of B E also has implications CHCl3 /C6 H1 2
for the excess enthalpy. (In practice, excess enthalpy 353 114
1.49 17.5 16.0 0.0372
measurements may themselves be the source of second virial 363 90
1.19 14.6 13.1 0.0299
coefficients.) For a slightly imperfect binary gas mixture 373 89
1.13 13.2 12.8 0.0283
H Em(1) = G Em(1) + TS Em(1) = y1 y 2[BE – T(dBE/dT )p ]p (21) 383 92
1.07 13.2 12.6 0.0267
393 66
0.84 10.8 9.9 0.0210
Since the ideal enthalpy of mixing is zero, H Em is identical
403 39
0.62 8.6 7.2 0.0155
to ∆ mixHm. It is reasonable that H Em(1) depends on the pressure,
413 64
0.76 9.0 9.4 0.0189
since increasing pressure is expected to increase interactions,
423 31
0.50 7.1 6.1 0.0125
whether favorable or not. Plots of H Em(p) for equimolar
mixtures of H2O/C6H12 up to p = 12.5 MPa (see Fig. 3)
CHCl3 /C6 H6
confirm this behavior only to an extent; at sufficiently high
353
274 3.55
40.9
38.2
0.0888
pressures, the excess enthalpy actually decreases with increasing
363
240 2.87
32.7
32.1
0.0718
pressure (19). Two additional features of Figure 3 are in-
373
206 2.30
28.0
26.6
0.0575
structive: (i) at the highest temperature, not only is H Em
smallest, but it is also most nearly linear, implying once again 383
189 1.94
24.2
23.4
0.0486
that the slightly imperfect gas approximation holds best at 393
172 1.66
19.9
20.6
0.0414
high temperatures; and (ii) at all temperatures, H Em→0 as 403
165 1.45
18.5
18.8
0.0363
p →0. Equation 21 predicts that the magnitude of H Em(1) will 413
136 1.11
16.4
14.9
0.0278
be largest for an equimolar mixture. Though this is apparently 423
145 1.09
9.4
15.2
0.0274
correct near atmospheric pressure, a plot of H Em( yCO2) for a Calculated from data in refs 15a (mixtures), 15b (chloroform), and
CO2/C2H6 at a near-critical pressure exhibits a slight asym- 15c (hydrocarbons).
b Maximum uncertainty is ± 58 cm3 mol
1 .
metry, as shown in Figure 4 (20). Figures 3 and 4 together c ± (0.7–2.0) J mol
1.
demonstrate that the slightly imperfect gas approximation
fails at high densities. Properties of gas mixtures at high
pressures are discussed in ref 1. side of eq 21. Further correction involves the term C(p/RT )2
Even near atmospheric pressure, values of H Em(1) generated and introduces third virial coefficients into expressions for
from eq 21 are not identical to measured values of the en- fugacity and excess thermodynamic functions (21).
thalpy of mixing (see Table 2). This discrepancy arises, of Like excess entropy, whether the excess enthalpy is
course, because eqs 19–21 are based on a truncated virial negative or positive, its magnitude diminishes as temperature
equation of state. At the next level of approximation, the term is raised, reflecting the fact that the kinetic energy (~kT ) of

(Bp/RT )2 in eq 13 is included in the derivation of an ex- the molecules begins to overwhelm their interaction energy
pression for f i , adding a term proportional to p 2 to the right (ui j (r)). From the observation that B E(dB E/dT )p < 0 (see

6000 500

5000
400

4000
HmE / (J mol −1)

HmE / (J mol −1)

300

3000

200

2000

100
1000

0 0
0 2 4 6 8 10 12 14 0.0 0.2 0.4 0.6 0.8 1.0

p / MPa
Figure 3. Measured values of H Em vs p for H2O/C6H12 at different
temperatures: ( 䊊) 498.2 K; (ⵧ) 598.2 K; ( 䉭) 698.2 K. Points are
connected solely to guide the eye. Adapted from ref 19.
y CO2
Figure 4. Measured values of H Em vs yCO2 for the system CO2/C2H6
at 3.10 MPa and 291.6 K compared with H Em(1) calculated from a
fit to the data using eq 21. Note that the data are skewed toward
ethane-rich mixtures. Adapted from ref 20.

1364 Journal of Chemical Education • Vol. 77 No. 10 October 2000 • JChemEd.chem.wisc.edu


Figs. 1 and 2) and the relation
H Em(1)S Em(1) =
( y1 y 2 p) [B (dB /dT )p – T(dB /dT
2 E E E
)p2 ]
it follows that S Em(1)
and H Em(1)
have the same sign. Thus when
mixing is endothermic, the excess entropy is positive (owing to
a net increase in volume) and vice versa. Positive excess enthal-
pies occur when components are ill matched with respect to the
forces that dominate interactions between like components.
An instance of this situation is C2H5OH/C6H12, which has a
relatively large excess enthalpy: H Em( p°) = 182 ± 9 J mol
1 at
363.2 K (13).
A smaller excess enthalpy is observed for CHCl3/C6H12,
with H Em( p°) = 17.5 ± 1.4 J mol
1 at 353.2 K (15a). It would
seem that CHCl3/C6H6 ought to behave similarly, but here the
enthalpy of mixing is exothermic: H Em( p°) =
40.9 ± 2.0 J mol
1
at 353.2 K (15a). Indeed, in spite of the resemblance be-
tween the hydrocarbons (their enthalpy of mixing is less than
0.5 J mol
1 at 363 K (22)), H Em and S Em are both positive
for the first system and both negative for the second. Calculated
values of H Em(1) and S Em(1) for equimolar mixtures are reported
in Table 2. Although the magnitudes of S Em(1) appear to be
negligible, those of T S Em(1), which are the apt comparison to
H Em(1), are not. Their comparable sizes indicate that enthalpy
and entropy effects make roughly equal contributions to
deviations from ideality. Interestingly, for nearly a dozen gas
mixtures of the type polar molecule/cyclohexane or benzene,
the excess enthalpy is markedly less endothermic with benzene
than with cyclohexane (23). It is conjectured that this is due
to formation of a charge transfer complex involving the π
system in benzene, which is, of course, not possible with
cyclohexane (15a). This specific interaction compensates for
the mismatch in intermolecular forces that predominate
between the pure components.
It is a simple matter to derive an expression for the ex-
cess molar volume (which is also the molar volume of mix-
ing ∆ mixVm) for slightly imperfect gas mixtures:
V Em(1) = (∂G Em(1)/∂p)T, y1 = y1 y 2 B E
For systems with BE > 0 (weaker 1–2 interactions), the excess
molar volume is positive, and vice versa for BE < 0. Of course,
zero excess molar volume does not necessarily imply an absence
of molecular interactions. Together with the data in Table 1,
eq 23 predicts that acetonitrile and n-butane will expand by
about 450 cm3 mol
1 when equal amounts are combined at
373 K and constant pressure. The mixture CH3OH/(CH3)3N
may be expected to show striking negative changes in V Em,
but unfortunately corroborative volumetric data are not
available. It is at first puzzling that V Em(1) is independent of
pressure. However, the relative change in volume on mixing
does depend on pressure, because the higher the pressure at
which mixing occurs, the lower the initial volume of the system.
Measured values of V Em may depend on pressure, and the next
level of approximation introduces a term proportional to p.
Like the excess enthalpy, the excess volume for CO2/C2H6
near the critical region is not perfectly parabolic, attaining a
maximum value of V Em ≈ 33 cm3 mol
1 a little below yCO2 =
0.5 (20). Note that for this system, H Em and V Em have the
same sign, which is physically reasonable. In fact, by the same
argument used to show that H Em(1)S Em(1) > 0, it is also true that
H Em(1)V Em(1) > 0. Thus for slightly imperfect gas mixtures, excess
entropy, enthalpy, and volume are all positive or all negative.
JChemEd.chem.wisc.edu • Vol. 77 No. 10 October 2000 • Journal of Chemical Education
Research: Science and Education
In light of the preceding discussion, under what condi-
tions do two slightly imperfect gases form an ideal mixture?
(22)
Using the criterion that for an ideal mixture G Em(1) = 0, eq 19
requires that at least one of the factors y1 (or y 2), BE, or p
must be zero, provided the remaining two are finite. That is,
the mixture should be very dilute in one component or the
temperature very high or the pressure very low, where the
precise meaning of “very” depends on the particular system.
All these conditions minimize interactions between unlike
molecules. When the mixture is ideal, the excess volume will
be found to be zero. However, this statement is limited to
slightly imperfect gases, because V Em(1) is independent of
pressure. More generally, for a gas mixture to be ideal at any
given composition and temperature, the excess volume must
be zero throughout the pressure range [0, p] (1):
p
G Em p,T, y 1 = V Em p′,T, y 1 dp′ (24)
0
Acknowledgment
I thank Robert J. Olsen for a critical reading of this
manuscript.
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