Discussion around the paradigm of ideal mixtures with emphasis

on the denition of the property changes on mixing

Romain Privat, Jean-No el Jaubert
n
Universite de Lorraine, E

cole Nationale Superieure des Industries Chimiques, Laboratoire Re actions et Genie des ProcedesUPR CNRS 3349, 1 rue Grandville, BP 20451,
Nancy cedex 9, France
H I G H L I G H T S
c Analysis and comparison of the various concepts of ideal mixtures.
c The mixing enthalpy can be different from the excess enthalpy.
c Volume change can be observed on the formation of an ideal mixture.
c Correct expressions of the ideal-mixture property change on mixing.
c Usefulness of the double-tangent construction when the gamma-phi approach is used.
a r t i c l e i n f o
Article history:
Received 20 January 2012
Received in revised form
15 July 2012
Accepted 21 July 2012
Available online 2 August 2012
Keywords:
Ideal mixture
Ideal solution
Ideal gaseous mixture
Ideal-mixture property changes on mixing
Double-tangent construction of coexisting
phases
Raoults law
a b s t r a c t
In this paper, the various concepts of ideal mixtures found in the open literature are analyzed and
compared. It is in particular shown that expressions conventionally admitted for the ideal-mixture
property changes on mixing are incorrect when the ideal mixture is obtained from pure components
which are not in the same aggregation state as the mixture. Among these properties, a special attention
is devoted to the ideal-mixture Gibbs energy change on mixing since it is used to determine the
equilibrium conditions. After explaining how to properly estimate this quantity, it is shown how to
correctly perform the double-tangent construction of coexisting phases for binary systems modeled
with the gamma-phi approach.
& 2012 Elsevier Ltd. All rights reserved.
1. Introduction
The concept of ideal mixture is widely accepted in chemical
engineering thermodynamics. The three following proposals
however show that some points still need to be claried.
Statement 1. About a century ago, the French chemist and
physicist Franc-ois Marie Raoult (18301901) published a simple
relation for vaporliquid equilibrium (VLE):
PUy
i
P
sat
i
TUx
i
1
generally known as Raoults law. P is the pressure, x
i
and y
i
are
respectively the mole fractions of component i in the liquid and
gas phases and P
sat
i
T is the vapor pressure of pure i at tempera-
ture T. It was experimentally found that this relation could be
applied under moderate pressure for very similar molecules, e.g.
for the systems tolueneethyl benzene, propanen-butane,
ethanolpropan-1-ol. Raoults law is thus the VLE condition
when the gas phase can be considered as a perfect-gas mixture
and when the liquid phase can be regarded as an ideal solution.
Statement 2. Gibbs (1873) demonstrated that by plotting at
constant temperature and pressure the molar Gibbs energy (g)
of a binary system vs. the molar composition, the existence of a
multiple tangent (typically a double tangent) was a necessary and
sufcient condition so that a stable multiphase (typically a two-
phase) equilibrium exists at this temperature and pressure.
As highlighted in the second part of this paper, the same
conclusion can be drawn by plotting the Gibbs energy change
on mixing (g
m
). This theorem, usually called the double-tangent
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Chemical Engineering Science
0009-2509/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2012.07.030
n
Corresponding author. Tel.: 33 3 83 17 50 81; fax: 33 3 83 17 51 52.
E-mail address: jean-noel.jaubert@univ-lorraine.fr (J.-N. Jaubert).
Chemical Engineering Science 82 (2012) 319333
construction of coexisting phases, established by Gibbs and used by
Van der Waals in his thesis can obviously not be questioned.
Statement 3. All well-known textbooks of thermodynamics state
that the Gibbs energy change on mixing for an ideal liquid binary
mixture (idl) and for a perfect-gas binary mixture (pgm) are
respectively given by:
g
m,idl
T,x RT

2
i 1
x
i
Ulnx
i
2
g
m,pgm
T,y RT

2
i 1
y
i
Ulny
i
3
Eq. (2) is even frequently used to dene an ideal solution.
Both g
m
functions in Eqs. (2) and (3) have exactly the same
mathematical form. As a consequence, by plotting g
m,idl
/(RT) vs. x
1
and g
m,pgm
/(RT) vs. y
1
, one obtains a unique curve which corre-
sponds to the superimposition of these two plots. This feature is
illustrated in Fig. 1.
It is clearly impossible to draw a double tangent on the
corresponding curve. Following Gibbss theorem (see Statement 2),
it thus can be argued that VLE cannot arise when an ideal liquid
phase is in equilibrium with a perfect-gas mixture what is in
straight contradiction with Raoults law previously mentioned, the
experimental truthfulness of which cannot be questioned.
We can thus conclude that the three previous proposals lead to
apparently-contradictory results. The goal of this article is thus to
clarify this apparent paradox.
2. Discussion around the paradigm of ideal mixtures
2.1. The ideal-mixture concept
Even though most real gases depart appreciably in their
behavior from the perfect-gas law, that equation is very valuable
both as an approximate representation of the properties of real
gases at low pressure and as a leading term in more complex
equations of state. In a somewhat similar manner, an ideal-
mixture equation should be useful both as an approximation to
the properties of many real mixtures and as a leading term for
more complex equations for mixture properties.
2.2. The ideal-mixture denition
A statistical reasoning allows demonstrating that the chemical
potential of a perfect gas i in a perfect-gas mixture (pgm) is given by:
g
pgm
i
T,P,y g
pg
i pure
T,PRTlny
i
4
where g
pg
i pure
T,P is the chemical potential of the pure perfect gas at
the same temperature T and pressure P as the pgm.
The ideal mixture, which may be either a gaseous or liquid
mixture, may be built in a similar manner. Following Lewis and
Randall (1961), we dene an ideal system as a multicomponent
system in which the chemical potentials of all the components
have the following form:
g
id
i
T,P,z g
same agg: state
as the mixture
i pure
T,PRTlnz
i
5
for all temperatures, pressures and compositions. The superscript
id stands for ideal mixture and g
same agg: state
as the mixture
i pure
T,P is the chemical
potential of pure i in the same state of aggregation as the considered
mixture.
Notes:
(1) by changing the overall composition of a binary system at
constant temperature and pressure, the mixture can go from
the liquid state to the gas state after crossing a vaporliquid
equilibrium (VLE) region. Following Prigogine and Defay
(1954), the mixture will be considered as ideal if (i) in the
liquid region the liquid phase is ideal, (ii) if in the gas domain
the gas phase is ideal and (iii) if in the two-phase region each
of the phases is ideal.
(2) it is not always simple to decide in which aggregation state a
mixture is. This is particularly true at high temperature and
pressure where the adjective uid is more appropriate than
liquid or gaseous. If at a given temperature and pressure,
regardless of the composition, the binary system is always in
a one-phase region, the chemical potential of pure i in Eq. (5)
is the chemical potential in its actual (stable) state at the
considered temperature and pressure.
For a component i in an ideal liquid mixture (idl), we thus can
write:
g
idl
i
T,P,x g
liquid
i pure
T,PRTlnx
i
6
where g
liquid
i pure
T,P represents the chemical potential of pure compo-
nent i in the liquid state. It is however very important to be aware
that this reference state may sometimes be a hypothetical, i.e.
unstable, state. It is indeed not scarce that the actual (stable) state
for the pure component at T and P is the gas state and not the liquid
state. This situation will be discussed in detail in a next section.
For a component i in an ideal gaseous mixture (idg), one obtains:
g
idg
i
T,P,y g
gas
i pure
T,PRTlny
i
7
where g
gas
i pure
T,P represents the chemical potential of pure compo-
nent i in the gaseous state. Once again, the reference state
g
gas
i pure
T,P may be a hypothetical state, i.e. a non-physically realiz-
able state. Indeed, the actual state for the pure component may be
liquid. By comparing Eqs. (4) and (7), it becomes obvious that a
perfect-gas mixture is a particular case of an ideal gaseous mixture.
Note: all binary mixtures behave as a perfect-gas mixture i.e. as
an ideal gaseous mixture when the pressure tends to zero. However,
all binary mixtures are obviously not ideal mixtures. Indeed, to be
qualied of ideal, each component of a multicomponent system
must obey Eq. (5) at all temperatures, pressures and compositions.
0.0 0.5 1.0
-0.5
0.0
x
1
& y
1
&
g
m,idl
g
m,pgm
RT RT
Fig. 1. Reduced Gibbs energy change on mixing for an ideal liquid binary mixture
(idl) and for a perfect-gas binary mixture (pgm) as dened by Eqs. (2) and (3).
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 320
Eq. (5) may also be written using the concept of fugacity. An
ideal mixture is thus a mixture in which we can write the fugacity
of each component in the form:
^
f
id
i
T,P,z z
i
Uf
same agg: state
as the mixture
i pure
T,P 8
where f
same agg: state
as the mixture
i pure
T,P is the fugacity of pure i at T and P. The
pure liquid is selected for an ideal liquid mixture and the pure gas
is selected for an ideal gaseous mixture even if these states are
hypothetical.
Introducing the fugacity coefcients, Eq. (8) writes:
^ j
id
i
T,P,z j
same agg: state
as the mixture
i pure
T,P 9
so that in an ideal mixture the fugacity coefcient of a component
i, ^ j
id
i
T,P,z, is the same as the fugacity coefcient of the pure
component taken at the same T and P and in the same aggregation
state as the ideal mixture. Following Michelsen and Mollerup
(2007), we could also state that in an ideal mixture, at a given T
and P, the fugacity coefcients ^ j
id
i
are composition independent.
In classical thermodynamics, the activity coefcient of a
component i in a homogeneous phase is dened by:
g
i
T,P,z
^ j
i
T,P,z
j
same agg: state
as the mixture
i pure
T,P
10
From Eq. (9), we can thus dene an ideal mixture as a mixture
in which the activity coefcients of all the components are unity:
g
id
i
T,P,z 1 11
As a corollary, we can state that in an ideal mixture, the
activity a
i
of each component, classically dened by:
a
i
T,P,z
^
f
i
T,P,z
f
same agg: state
as the mixture
i pure
T,P
z
i
Ug
i
T,P,z 12
is identical to the mole fraction z
i
of component i. We thus can
write:
a
id
i
T,P,z z
i
13
2.3. Contribution of statistical thermodynamics to the denition
of an ideal mixture
The question we now need to address is: do ideal mixtures
actually exist? The answer is given by the statistical thermodynamics
which allows demonstrating that Eqs. (5), (8), (9), (11) and (13) can
be obtained by assuming that molecules A and B are sufciently alike
from the point of view of the molecular interactions which they exert
on one another, and from the point of view of their shapes and sizes.
We thus can say that in ideal mixtures there are interactions but the
average energy of AB interactions in the mixture is the same as the
average energy of AA and BB interactions in the pure compounds.
On the other hand, let us recall that a perfect-gas mixture is an ideal
gaseous mixture in which not only are the interactions the same
(as in any ideal mixture), but they are also zero. The laws of ideal
mixtures are thus limiting laws which are obeyed more closely, the
greater the similarity with regard to size, shape and energy, between
the components. Ideal mixtures are thus useful both as an approx-
imation to the properties of many real mixtures and as a leading term
for more complex equations for mixture properties which was the
basis to dene them.
2.4. Raoults law
Let us consider an ideal liquid mixture in equilibrium with a
perfect-gas mixture; then:
g
idl
i
T,P,x g
pgm
i
T,P,y 14
From Eqs. (4) and (6), we thus obtain:
RTln
y
i
x
i
_ _
g
liquid
i pure
T,Pg
pg
i pure
T,P RTln
f
liquid
i pure
T,P
f
pg
i pure
T,P
_ _
15
From basic thermodynamics, we know that:
f
liquid
i pure
T,P P
sat
i
TUj
i pure
T,P
sat
i
T
_ _
Uexp
1
RT
_
P
P
sat
i
T
v
liquid
i pure
dP
_ _
f
pg
i pure
T,P P
_
_
_
16
The gas phase being a pgm, the pure gas at temperature T and
under its vapor pressure can be considered as perfect so that
j
i pure
T,P
sat
i
T 1. The difference between the total pressure P
and the vapor pressure being small, the Poynting factor value is
very close to 1. We thus can write: f
liquid
i pure
T,P P
sat
i
T.
Eq. (15) thus becomes:
PUy
i
P
sat
i
TUx
i
which is the well-known Raoults law. We can thus conclude that
the ideal-mixture denition given above is compatible with
Raoults law which was experimentally veried thousands of
times for binary systems in which the two molecules are of
closely similar chemical structure.
2.5. Partial molar properties m
id
i
of a component i in an ideal
mixture and molar properties m
id
of ideal mixtures
The knowledge of the chemical potential of a component i in
an ideal mixture (Eq. (5)) allows one to determine all the other
partial molar properties, noted m
id
i
hereafter.
We obtain:
v
id
i
T,P, v
same agg: state
as the mixture
i pure
T,P
s
id
i
T,P,z s
same agg: state
as the mixture
i pure
T,PRlnz
i
h
id
i
T,P, h
same agg: state
as the mixture
i pure
T,P
u
id
i
T,P, u
same agg: state
as the mixture
i pure
T,P
a
id
i
T,P,z a
same agg: state
as the mixture
i pure
T,PRTlnz
i
c
id
P,i
T,P, c
same agg: state
as the mixture
P,i pure
T,P
_

_
17
we can thus conclude that the partial molar volume, enthalpy,
internal energy, and constant pressure heat capacity of a component
i in an ideal mixture is equal to the molar property of pure
component i taken at the same temperature at the same pressure
and in the same aggregation state as the ideal mixture. Like the
fugacity coefcients ^ j
id
i
and the activity coefcients g
id
i
, at a given
T and P, such partial molar properties (v
id
i
, h
id
i
, u
id
i
, c
id
P,i
) are thus
independent of the ideal-mixture composition.
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 321
The molar properties m
id
of an ideal mixture containing p
components thus verify:
g
id
T,P,z

p
i 1
z
i
Ug
same agg: state
as the mixture
i pure
T,P RT

p
i 1
z
i
Ulnz
i
v
id
T,P,z

p
i 1
z
i
Uv
same agg: state
as the mixture
i pure
T,P
s
id
T,P,z

p
i 1
z
i
Us
same agg: state
as the mixture
i pure
T,PR

p
i 1
z
i
Ulnz
i
h
id
T,P,z

p
i 1
z
i
Uh
same agg: state
as the mixture
i pure
T,P
u
id
T,P,z

p
i 1
z
i
Uu
same agg: state
as the mixture
i pure
T,P
a
id
T,P,z

p
i 1
z
i
Ua
same agg: state
as the mixture
i pure
T,P RT

p
i 1
z
i
Ulnz
i
c
id
P
T,P,z

p
i 1
z
i
Uc
same agg: state
as the mixture
P,i pure
T,P
_

_
18
Equivalently, one can write the following equations which will
be discussed in Section 2.6.
v
id
T,P,z

p
i 1
z
i
Uv
same agg: state
as the mixture
i pure
T,P 0
h
id
T,P,z

p
i 1
z
i
Uh
same agg: state
as the mixture
i pure
T,P 0
u
id
T,P,z

p
i 1
z
i
Uu
same agg: state
as the mixture
i pure
T,P 0
c
id
P
T,P,z

p
i 1
z
i
Uc
same agg: state
as the mixture
P, i pure
T,P 0
_

_
and
s
id
T,P,z

p
i 1
z
i
Us
same agg: state
as the mixture
i pure
T,P R

p
i 1
z
i
Ulnz
i
a
id
T,P,z

p
i 1
z
i
Ua
same agg: state
as the mixture
i pure
T,P RT

p
i 1
z
i
Ulnz
i
g
id
T,P,z

p
i 1
z
i
Ug
same agg: state
as the mixture
i pure
T,P RT

p
i 1
z
i
Ulnz
i
_

_
19
2.6. Ideal-mixture property changes on mixing M
m,id
Confusion has often appeared in the mathematical expression
of these properties. They are indeed often mixed up with the
quantities dened in the left-hand side (lhs) of Eq. (19). It is thus
decided to make the point on their denition and usefulness.
2.6.1. Denition
The property change on mixing M
m
, of any extensive property
M, is by denition the difference between the property M of the
actual mixture and the sum of the properties of the pure
components which make it up, all at the same temperature and
pressure as the mixture. We here want to emphasize that such a
quantity is called change on mixing because it is the change that
would be measured if the mixing took place in a mixing device of
a laboratory. As an example (Sandler, 2006), the enthalpy change
on mixing can be measured using a calorimeter; two streams: one
of pure uid 1 and the second of pure uid 2, both at a
temperature T and at pressure P, enter a mixing device, and a
single mixed stream also at T and P leaves. Heat is added or
removed to maintain the temperature of the outlet stream. This
quantity of heat is by denition the enthalpy change on mixing.
This well-known example was selected to emphasize that all the
states are physically realizable: the obtained mixture (liquid,
gaseous or in the two-phase area) and the two pure uids (either
liquid or gaseous) are in their stable state at T and P.
We can thus dene the molar property change on mixing m
m
by the following equation:
m
m
mT,P,z
..
property of the stable
actual mixture

p
i 1
z
i
Um
stable
i pure
T,P 20
In the common case where the obtained mixture is in the one-
phase area (liquid or gaseous), we thus have:
m
m

p
i 1
z
i
U m
i
m
stable
i pure
T,P
_ _
21
where m
i
and z
i
respectively stand for the partial molar property
and the mole fraction of i in the stable obtained mixture.
In the particular case where the obtained mixture is in the
two-phase area, i.e. a phase a in equilibrium with a phase b [e.g.
VLE or liquidliquid equilibrium (LLE)], the following equation
applies:
m
m
t
a
Um
phasea
T,P,x
a
1s
a
Um
phase
b
T,P,x
b

..
mT,P,z

p
i 1
z
i
Um
stable
i pure
T,P
t
a
U

p
i 1
x
ia
U m
i,phasea
m
stable
i pure
T,P
_ _
..
m
m,phasea
1t
a
U

p
i 1
x
ib
U m
i,phase
b
m
stable
i pure
T,P
_ _
..
m
m,phase
b
22
where t
a
is the molar relative amount of phase a. x
ia
and x
ib
stand
for the mole fractions of i respectively in the a and b phases.
It is important to be aware that there is no link between the
aggregation state of the obtained mixture and the state of
aggregation of the pure uids. As shown in Fig. 2, by mixing
two pure components: two liquids or two gases or one liquid and
one gas, it is possible to obtain a liquid solution, a gas mixture or a
two-phase system (in vaporliquid or in liquidliquid equili-
brium). All the possible combinations are in fact observable.
Remark. None of the four binary systems shown in Fig. 2 can
be considered as ideal. The ideal-mixture properties are how-
ever introduced into the thermodynamic description of real
mixtures as convenient standards of normal behavior. It is indeed
always possible to divide a property of a real mixture (m
rm
) in two
parts: the ideal-mixture contribution (m
id
) and the excess con-
tribution (m
E
):
m
rm
m
id
m
E
23
In Eq. (23), the real mixture and the associated ideal mixture
have the same temperature, the same pressure, the same compo-
sition and are in the same aggregation state.
Such an equation also applies to the property changes on
mixing and we always can write:
m
m
m
m,id
m
E
24
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 322
we thus must be able to properly estimate the ideal-mixture
property changes on mixing (m
m,id
) even if the considered system
shows deviations from ideality.
Following the denition of a molar property change on mixing
given by Eq. (20), we dene the ideal-mixture property changes
on mixing by:
m
m,id
m
id
T,P,z

p
i 1
z
i
Um
stable
i pure
T,P 25
we however know that the molar properties (m
id
) in ideal
mixtures (gaseous or liquid) obey Eq. (18).
We thus obtain for the ideal-mixture property changes on
mixing:
g
m,id
T,P,z

p
i 1
z
i
U g
same agg: state
as the mixture
i pure
T,Pg
stable
i pure
T,P
_
_
_
_
RT

p
i 1
z
i
Ulnz
i
v
m,id
T,P,z

p
i 1
z
i
U v
same agg: state
as the mixture
i pure
T,Pv
stable
i pure
T,P
_
_
_
_
s
m,id
T,P,z

p
i 1
z
i
U s
same agg: state
as the mixture
i pure
T,Ps
stable
i pure
T,P
_
_
_
_
R

p
i 1
z
i
Ulnz
i
h
m,id
T,P,z

p
i 1
z
i
U h
same agg: state
as the mixture
i pure
T,Ph
stable
i pure
T,P
_
_
_
_
u
m,id
T,P,z

p
i 1
z
i
U u
same agg: state
as the mixture
i pure
T,Pu
stable
i pure
T,P
_
_
_
_
a
m,id
T,P,z

p
i 1
z
i
U a
same agg: state
as the mixture
i pure
T,Pa
stable
i pure
T,P
_
_
_
_
RT

p
i 1
z
i
Ulnz
i
c
m,id
P
T,P,z

p
i 1
z
i
U c
same agg: state
as the mixture
P,i pure
T,Pc
stable
P,i pure
T,P
_
_
_
_
_

_
26
Eq. (26) highlights that it can be wrong to state that:
J the ideal-mixture Gibbs energy change on mixing obeys
systematically Eqs. (2) and (3).
J there are no volume or enthalpy or internal energy or heat
capacity changes on the formation of an ideal mixture from its
pure components at the same temperature and pressure.
Although these statements are written in most of the chemical
engineering thermodynamics textbooks, they are only true when
the considered ideal mixture and the p pure components are all in
the same aggregation state (liquid or gas). However, an ideal
mixture can be obtained by mixing pure components in different
aggregation states [as stated above, the ideal-mixture concept can
also be used to model the properties of real mixtures through
Eq. (23) and in this case, the aggregation state of the hypothetical
ideal solution is often different from the aggregation state of the
pure components at the same temperature and pressure (see
Fig. 2)].
Let us take as an example, the mixing at t20 1C and P2 kPa
of 1 mol of toluene (1) and 9 mol of ethylbenzene (2), leading to a
liquid mixture the composition of which is x
1
0.1 and x
2
0.9
(see point A in Fig. 3a). This liquid mixture is a good example of an
ideal solution since the two molecules are more or less identical
from the point of view of the molecular interactions they exert on
one another, and from the point of view of their shapes and sizes.
To be convinced of this assertion, the molar excess enthalpy h
E
,
the ideal-mixture molar enthalpy change on mixing h
m,id
and the
molar enthalpy change on mixing h
m
have been calculated at
t20 1C and P2 kPa using the PengRobinson equation of state
(Peng and Robinson, 1976) and temperature-dependent k
ij
(Jaubert and Mutelet, 2004; Jaubert et al., 2010). As shown in
Figs. 3bd whatever the composition, h
E
is extremely close to zero
and as a consequence h
m,id
cannot be distinguished from h
m
by
eye. The studied system is thus doubtless with an excellent
approximation an ideal mixture. However in the considered
conditions, pure toluene is in the gaseous state P
sat
1
20 1C %
3 kPa and pure ethylbenzene is in the liquid state P
sat
2
20 1C %
1 kPa. As a consequence, the molar Gibbs energy change on
mixing is completely different from RTx
1
lnx
1
x
2
lnx
2
(see point A
in Fig. 5) and the molar enthalpy change on mixing is far from
zero (see point A in Fig. 3d); it is negative and close to x
1
UD
vap
H
1
(20 1C)E4 kJ mol
1
. On the contrary, the molar excess enthalpy
is only 0.0017 kJ mol
1
(see point A in Fig. 3b).
Similarly by mixing at t20 1C and P2 kPa, 9 mol of toluene
(1) and 1 mol of ethylbenzene (2), we obtain a gas mixture (see
point B in Fig. 3a) which can be considered as a perfect-gas
mixture that is a gaseous ideal mixture the composition of which
is y
1
0.9 and y
2
0.1. Once again: g
m
T,P,z aRTy
1
lny
1
y
2
lny
2

(see point B in Fig. 5) and h

m
(T,P,z)a0 (see point B in Fig. 3d).
In this case, the molar enthalpy change on mixing is positive and
close to y
2
UD
vap
H
2
(20 1C)E4 kJ mol
1
whereas the molar
excess enthalpy is as weak as 0.000014 kJ mol
1
(see point B in
Fig. 3b). More information on how Fig. 3 was calculated can be
found in Appendix A.
2.6.2. Calculation of the ideal-mixture Gibbs energy change
on mixing
The knowledge of the ideal-mixture Gibbs energy change on
mixing allows calculating all the other ideal-mixture property
changes on mixing and allows applying the double-tangent
construction of coexisting phases. Moreover, ideal-mixture prop-
erties are the starting point to estimate the properties of real
mixtures. The correct calculation of g
m,id
(T,P,z) is thus of the
highest importance. Starting from Eq. (26), we can write:
g
m,id
T,P,z RT

p
i 1
z
i
Uln
z
i
Uf
same agg: state
as the mixture
i pure
T,P
f
stable
i pure
T,P
_

_
_

_
27
Following Eq. (27), the mathematical expressions to be used to
calculate the ideal-mixture Gibbs energy change on mixing for a
binary liquid or gas phase are given here below [for clarity,
component 1 is the most volatile and component 2 is the heaviest
one so that P
sat
1
T4P
sat
2
T].
Remark. At low to moderate pressure f
liquid
i pure
T,P P
sat
i
T and
f
gas
i pure
T,P P so that Eq. (27) can generally be simplied as
shown below.
Case 1. The pressure is higher than the vapor pressure of
component 1 at the working temperature P4P
sat
1
T4P
sat
2
T.
In these conditions the stable state for the 2 pure components is
the liquid state and from Eq. (27):
g
m,id
liquid
T,P,z RTz
1
lnz
1
z
2
lnz
2

g
m,id
gas
T,P,z RT z
1
ln
z1Uf
gas
1 pure
T,P
f
liquid
1 pure
T,P
_ _
z
2
ln
z2Uf
gas
2 pure
T,P
f
liquid
2 pure
T,P
_ _ _ _
_

_
28; 29
At low to moderate pressure, one has:
g
m,id
gas
T,P,z RT z
1
ln
z
1
UP
P
sat
1
T
_ _
z
2
ln
z
2
UP
P
sat
2
T
_ _ _ _
30
Case 2. The pressure is between the two vapor pressures
P
sat
1
T4P4P
sat
2
T. In these conditions, the stable state for
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 323
component 1 is the gas state but the stable state for component 2
is the liquid state. From Eq. (27):
g
m,id
liquid
T,P,z RT z
1
ln
z
1
Uf
liquid
1 pure
T,P
f
gas
1 pure
T,P
_ _
z
2
lnz
2
_ _
g
m,id
gas
T,P,z RT z
1
lnz
1
z
2
ln
z
2
Uf
gas
2 pure
T,P
f
liquid
2 pure
T,P
_ _ _ _
_

_
31; 32
At low to moderate pressure, one has:
g
m,id
liquid
T,P,z RT z
1
ln
z
1
UP
sat
1
T
P
_ _
z
2
lnz
2
_ _
g
m,id
gas
T,P,z RT z
1
lnz
1
z
2
ln
z
2
UP
P
sat
2
T
_ _ _ _
_

_
33; 34
Case 3. The pressure is lower than the vapor pressure of compo-
nent 2 at the working temperature PoP
sat
2
ToP
sat
1
T. In these
conditions the stable state for the 2 pure components is the gas
state. From Eq. (27):
g
m,id
liquid
T,P,z RT z
1
ln
z
1
Uf
liquid
1 pure
T,P
f
gas
1 pure
T,P
_ _
z
2
ln
z
2
Uf
liquid
2 pure
T,P
f
gas
2 pure
T,P
_ _ _ _
g
m,id
gas
T,P,z RTz
1
lnz
1
z
2
lnz
2

_
35; 36
At low to moderate pressure, one has:
g
m,id
liquid
T,P,z RT z
1
ln
z
1
UP
sat
1
T
P
_ _
z
2
ln
z
2
UP
sat
2
T
P
_ _ _ _
37
Eqs. (28) and (36) are similar to Eqs. (2) and (3) and can be
found in any textbook of thermodynamics (Ahlstrom et al., 2010).
They are even often used to dene an ideal mixture. We however
believe that such a denition should be avoided because these
two equations only constitute a particular case of the mathema-
tical expression of g
m,id
(T,P,z). However, to our knowledge, no
thermodynamics textbook gives Eqs. (30), (33), (34) and (37).
In conclusion, this section clearly demonstrates that the ideal-
mixture Gibbs energy change on mixing obeys Eqs. (2) and (3)
(and consequently h
m,id
v
m,id
0) only when the two pure
components and the mixture are in the same aggregation state.
Such a situation never occurs when at a given temperature the
pressure is between the vapor pressures of the two pure compo-
nents. This region wherein VLE arises and wherein Raoults law
applies is however extremely important since the composition of
the two phases in equilibrium can be determined from the
knowledge of g
m,id
(T,P,z).
The mathematical expressions of the other ideal-mixture
property changes on mixing are given in Appendix B.
0.0 0.5 1.0
10.0
11.0
12.0
x
1
,y
1
P/kPa
L + L = V
V + V = V
L + L = L
L + V = V
L+ L = VLE
a
0.0 0.5 1.0
16.0
20.0
24.0
x
1
,y
1
P/kPa
V + V = L
L + V = L
V + V = VLE
L + V = VLE
b
c
0. 0.4 0.8
4.00
8.00
12.0
x
1
,y
1
P/kPa
L + L = LLE
L + V = LLE
3-phase line
d
x
1
,y
1
0.0 0.5 1.0
4.0
8.0
12.0
P/kPa
V + V= LLE
3-phase line
Fig. 2. Highlight of the various reachable aggregation states by mixing two pure components. (a) System cyclohexane (1)benzene (2) at 20 1C. (b) System acetone
(1)chloroform (2) at 20 1C. (c) System nitromethane (1)1,2-ethanediol (2) at 40 1C. (d) Binary system giving simultaneously rise to a negative azeotrope and a liquidliquid
equilibrium(such systems are so infrequent that it was preferred to show on a ctitious example that by mixing two pure gases a liquidliquid equilibriumcould be reached).
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 324
2.7. Pengs denition of an ideal mixture
Twenty years ago, in two interesting articles (Peng, 1989,
1990), Peng also noticed that Raoults law was not compatible
with the unique frequently used denition of the ideal-mixture
Gibbs energy change on mixing recalled hereafter:
g
m,id
T,z RTz
1
lnz
1
z
2
lnz
2
38
In this article, we decided to give up Eq. (38) and proof was
given that this equation could be incorrect (see Tables B1 and B2)
since it is only a particular case of the mathematical expression of
g
m,id
. As shown previously, our approach remains totally compa-
tible with Raoults law when an ideal liquid phase is in equili-
brium with a perfect-gas mixture. Peng made the opposite and
decided to dene an ideal mixture as a mixture for which Eq. (38)
is always true. In his approach, the chemical potentials of all the
components of an ideal mixture have thus the following form:
g
id
i
T,P,z g
stable
i pure
T,P RTlnz
i
39
where g
stable
i pure
T,P is the chemical potential of pure i in its
stable (actual) state at T and P [note that to switch from Pengs
denition to the denition we adopted here for ideal mixtures,
the term g
stable
i pure
T,P has to be replaced by g
same agg: state
as the mixture
T,P
i pure
]. Eq. (39)
may also be written using the concept of fugacity. According to
Peng, an ideal mixture is thus a mixture in which we can write the
fugacity of each component in the form:
^
f
id
i
T,P,z z
i
Uf
stable
i pure
T,P 40
where f
stable
i pure
T,P is the fugacity of pure i in its stable state at T and P.
From Eq. (39), we immediately always have:
v
m,id
T,P,z 0
s
m,id
T,P,z Rz
1
lnz
1
z
2
lnz
2

h
m,id
T,P,z 0
_

_
41
Using Pengs denition, there are thus never volume or
enthalpy changes on the formation of an ideal mixture from its
pure components at the same temperature and pressure.
Note: Eq. (41) is often written in many textbooks of thermody-
namics in which the ideal mixture is yet conventionally dened by
Eq. (5) and Appendix B was devoted to give proof that it could
be wrong.
It is noticeable that Pengs denition is equivalent to the conven-
tional denition of an ideal mixture when the pure components and
the mixture are all in the same aggregation state. However, in our
opinion, various arguments conict with Pengs approach:
J rstly, an ideal liquid phase (as dened by Peng) can never be
in equilibrium with an ideal gaseous phase (as dened by
Peng). Indeed, if in each phase, the chemical potentials follow
Eq. (39), the classical vaporliquid equilibrium condition:
g
liq
i
T,P,x g
gas
i
T,P,y 42
reduces to the trivial following equation:
x
i
y
i
43
We should thus conclude that the VLE relation between an ideal
liquid phase and an ideal gas phase (Eq. (43)) is no more Raoults
0.0 0.5 1.0
1.0
2.0
3.0
x
1
,y
1
P/kPa
A
B
C
D
L
V
t = 20 C
0.0 0.5 1.0
-10.0
0.0
10.0
z
1
h
m,id
(kJ
.
mol
1
)
A
B
L
V
Ideal liquid
solution for which
h 0
m,id
liquid
Ideal gaseous
mixture for which
h 0
m,id
gas
Ideal liquid solution in
equilibrium with an ideal
gaseous mixture
t = 20 C and P = 2 kPa
0.0 0.5 1.0
0.000
0.002
0.004
z
1
h
E
(kJ
.
mol
1
)
L
V
t = 20 C and P = 2 kPa

A
B
0.0 0.5 1.0
-10.0
0.0
10.0
z
1
h
m
(kJ
.
mol
1
)
A
B
L
V
t = 20 C and P = 2 kPa
Fig. 3. System toluene (1)ethylbenzene (2) which may be regarded as an ideal binary mixture because the two molecules are of closely similar chemical structure.
(a) Isothermal phase diagram at t20 1C. (b) h
E
vs. z
1
at t20 1C and P2 kPa. (c) h
m,id
vs. z
1
at t20 1C and P2 kPa. (d) h
m
vs. z
1
at t20 1C and P2 kPa.
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 325
law (Eq. (1)) but is instead a particular case of this law in which
P P
sat
1
P
sat
2
. As a consequence, the two-phase region at a given
temperature would be represented by a horizontal segment
covering the whole composition range. Such an isothermal
(P,x
1
,y
1
) phase diagram would stem from the attening of a
classical Raoults law phase diagram (as in Fig. 3a) in which the
two pure components would have the same vapor pressure (the
isothermal linear bubble-point curve would become horizontal
and would merge with the dew-point curve). Such phase
diagrams cannot exist for real binary systems. Indeed, the
condition P
sat
1
P
sat
2
at all temperatures implies that the two
molecules are so close each other that they are actually identical.
This ideal-mixture concept would not be anymore an approx-
imation to the properties of many real mixtures and we believe
that it would be really a pity for practicing engineers.
J Secondly, Peng loses the structural denition of an ideal
mixture issued from the statistical thermodynamics. Indeed a
mixture containing alike compounds from the point of view of
the molecular interactions which they exert on one another,
and from the point of view of their shapes and sizes could not
be qualied as ideal. Only mixtures containing rigorously
identical molecules could be called ideal. In other words an
ideal mixture would degenerate in a kind of pure compound. It
thus would be a poorly appropriate model to describe mixtures.
J Thirdly, by changing the classical denition of an ideal solution,
it would be necessary to change the values of the activity
coefcients collected in specialized books since many years.
Indeed in Pengs approach, the activity coefcients are dened
by:
g
i,Peng
T,P,z
^ j
i
T,P,z
j
stable
i pure
T,P
44
whereas in the conventional approach, they are dened by
Eq. (10). We thus can write:
g
i,Peng
T,P,z g
i,conventional
T,P,zU
f
same agg: state
as the mixture
i pure
T,P
f
stable
i pure
T,P
45
As an example, Table 1 gives for a conventionally dened ideal
mixture (obeying Eq. (5)) in which the conventional activity
coefcients are by denition unity, the values of the activity
coefcients obtained following Pengs approach. For convenience,
it is assumed that the pressure of the mixture is low to moderate.
This table shows once again that the two approaches become
identical when the pure components and the mixture are in the
same aggregation state [g
liquid
i,Peng
1 when P4P
sat
1
T4P
sat
2
T and
g
gas
i,Peng
1 when PoP
sat
2
ToP
sat
1
T]. More annoying, this table
puts in evidence that a binary mixture can never be considered as
ideal (employed in Pengs sense) for all temperatures, pressures
and compositions. Indeed by inspecting Table 1, which gives the
activity coefcient values for a mixture obeying Raoults law, it can
be concluded that in Pengs approach, such a mixture is only ideal:
at high pressure P4P
sat
1
T when the two pure components
and the mixture are in the liquid state and
at low pressure PoP
sat
2
T when the two pure components
and the mixture are in the gaseous state but becomes non-
ideal when VLE may exist P
sat
1
T4P4P
sat
2
T.
2.8. Epilogue
Our opinion is that Pengs papers have the great advantage to
highlight a serious weakness in the ideal-mixture concept even if
we do not subscribe to the solution he proposes. Peng spent many
years to develop the famous PengRobinson equation of state and
he can thus be qualied of expert in modeling uids with
equations of state. For him, no doubt that the property changes
on mixing must be dened as proposed in this paper by Eq. (20).
This is indeed the unique denition which guarantees that such
properties can be calculated from an equation of state (all the
considered states are physically realizable). Since in Pengs approach,
the ideal-mixture property changes on mixing obey Eqs. (38) and
(41), the excess properties (m
E
m
m
m
m,id
) can thus be easily
estimated from an equation of state. Such an approach is however
incompatible with Raoults law and with a statistical reasoning.
Following Peng, Fig. 1 would correspond to the correct situation
where an ideal-liquid mixture is in equilibrium with a perfect-gas
mixture and in accordance with his approach, Peng would conclude
that no vaporliquid equilibrium could exist for such systems. We
thus can say that Pengs approach is consistent.
This paper and Pengs theory both highlight that it is not
possible to nd an ideal-solution denition which would be
simultaneously compatible with:
1. a statistical reasoning,
2. Raoults law and
3. very simple expressions of the ideal-mixture property changes
on mixing.
Peng decided to give up the two rst points whereas we decided
to only give up the third one and to give the correct expressions of
m
m,id
. We indeed saw no reason to change the ideal-mixture
denition used worldwide and introduced by Lewis and Randall. It
is however important to be aware that since the classical denition
of an ideal solution (Eq. (5)) may refer for the pure components to a
non-stable state, it is not always possible to calculate with an
equation of state the ideal-mixture property changes on mixing and
thus the excess properties (the property changes on mixing are in
return always calculable). Such a situation could arise if the equation
of state did not have a volume-root corresponding, for the pure
component, to this non-stable state.
Remark. The derivation of mixing rules for cubic EoS by equating at
a reference pressure, the reduced excess Gibbs energy calculated from
the EoS noted g
E
EoS
with the reduced excess Gibbs energy
expressed from an activity-coefcient model, g
E
g
, is a well-known
application requiring the calculation of molar excess Gibbs energy of
the liquid phase from an EoS g
E
liquid,EoS
(Michelsen and Mollerup,
2007). When using the HuronVidal approach, an innite reference
pressure is taken. Under these conditions, any uid (mixture and pure
components) is a homogeneous liquid and it is thus always possible
to calculate g
E
liquid,EoS
(a liquid root the covolume always exists at
PN). However, when considering the MHV approach (Modied
HuronVidal), the reference pressure is zero and it is not always
possible to calculate g
E
liquid,EoS
since it is not always possible to nd a
liquid root for the pure components and the mixture at a given
temperature and pressure. This problem has clearly been already
identied as a shortcoming of the MHV approach and is a practical
illustration of the impossibility for the EoS to calculate excess
properties in some cases.
We here want to state that in many textbooks, the authors in fact
switch (and they do not seemaware to do it) fromPengs denition of
an ideal mixture (when they dene the ideal-mixture property
changes on mixing) to the classical denition used in this paper
when Raoults law is introduced. To remain consistent, such authors
in fact use the ideal-mixture concept in a restrictive way by
considering that an ideal mixture can always be obtained by the
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 326
mixing of pure components which are in the same aggregation state
as the mixture. With this restriction, the ideal-mixture enthalpy
change on mixing is obviously always equal to zero. In return, this
paper thus extends the ideal-mixture concept to mixtures obtained
by the mixing of pure components which are not necessarily in the
same aggregation state as the resulting mixture. This extension leads
to the conclusion that the ideal-mixture enthalpy (or volume) change
on mixing can be different from zero.
To conclude this section, we want to emphasize on an example
that the use of the traditional ideal-mixture concept [in which
h
m,id
(T,P,z)0] can lead to inconsistent results. Let us consider the
system tolueneethylbenzene at t20 1C and P2 kPa. We here
mix very similar molecules and such a mixture can thus be
considered, with a very good approximation, as ideal.
By computing the excess enthalpy with the following equa-
tion:
h
E
T,P,z hT,P,zh
id
T,P,z
hT,P,z z
1
Uh
same agg: state
as the mixture
1 pure
T,Pz
2
Uh
same agg: state
as the mixture
2 pure
T,P
_
_
_
_
46
results identical to those shown in Fig. 3b are going to be
obtained. Thus h
E
(T,P,z) values will be extremely small what is
consistent for an ideal mixture.
By computing the excess enthalpy with the following equa-
tion:
h
E
T,P,z h
m
T,P,zh
m,id
T,P,z 47
we should obviously obtain the same result. This is effectively
true if h
m,id
(T,P,z) is computed properly using Eq. (26) recalled
hereafter (see also Fig. 3c):
h
m,id
T,P,z z
1
U h
same agg: state
as the mixture
1 pure
T,Ph
stable
1 pure
T,P
_
_
_
_
z
2
U h
same agg: state
as the mixture
2 pure
T,Ph
stable
2 pure
T,P
_
_
_
_
48
however by setting arbitrarily that h
m,id
(T,P,z)0, we are going to
obtain for h
E
(T,P,z), the values shown in Fig. 3d. Such values are
far from zero and the considered mixture must be declared as
non-ideal. In conclusion by ignoring the fact that h
m,id
(T,P,z) can
be different from zero, the values of h
E
(T,P,z) estimated from
Eq. (47) become identical to those of h
m
(T,P,z) but are different
from those calculated by Eq. (46). Such a big confusion lead
several research groups (see e.g. Oscarson et al., 1996) to
introduce the concept of excess enthalpies of mixing when they
published heats of mixing measured in regions where VLE arises.
They indeed do not know if their measurements must be called
excess or mixing enthalpies and we perfectly understand their
questioning. We hope that this article will convince them to call
their next measurements mixing enthalpies.
3. Necessary and sufcient conditions to apply the Gibbs
double-tangent construction of coexisting phases
The Gibbs double-tangent construction of coexisting phases is
of the highest interest to determine the compositions of two
phases in equilibrium. This section is devoted to dene the
application range of this graphical approach which is often
described ambiguously.
From basic thermodynamics, it is well known that by plotting
at constant temperature and pressure, any molar property m of a
binary system vs. x
1
, and by adding the tangent line for a
composition z
1
, the tangent intercepts at x
1
1 and x
1
0 directly
give the values of the two molar partial properties: m
1
T,P,z
1
and
m
2
T,P,z
1
.
This graphical technique can be used to determine the composi-
tion of the coexisting phases by plotting g (the molar Gibbs energy)
as a function of x
1
at constant T and P. Indeed, for a binary system,
the equilibrium condition between two phases I and II writes:
g
1
T,P,z
1,I
g
1
T,P,z
1,II

g
2
T,P,z
1,I
g
2
T,P,z
1,II

_
49
As a consequence, the presence of a double tangent allows
dening two phases, the composition of which are z
1,I
and z
1,II
which satisfy Eq. (49). Let us however recall that Eq. (49) is a
necessary but not a sufcient condition to reach a stable equili-
brium. It means that the graphically determined compositions do
not necessarily correspond to a stable equilibrium. Strictly speaking:
if a unique double tangent can be drawn, it always highlights a
stable two-phase system. More generally, the existence of a
unique multiple tangent always highlights a stable multiphase
system.
if several multiple tangents (typically double tangents) exist
on a g vs. composition plot at a given temperature and
pressure, some can characterize non-stable multiphase sys-
tems but at least one of them denes a stable multiphase
system. In other words, the existence of a multiple tangent
associated to a non-stable two-phase system systematically
involves the existence of a multiple tangent associated to a
stable multiphase system. This instance is illustrated in Fig. 4
wherein the isothermal and isobaric reduced Gibbs energy of a
given binary system is represented. It appears that three
double tangents: (AB), (CD) and (EF) can be drawn. In the
present case, the double tangent (AB) which lowers the Gibbs
energy characterizes a stable equilibrium whereas equilibria
(CD) and (EF) are non-stable. Fig. 4 thus highlights that the
mere existence of a non-stable equilibrium, e.g. (CD), involves
the existence of the stable equilibrium (AB) explaining why
as written in Statement 2 (see the introduction) the exis-
tence of a multiple tangent is a necessary and sufcient
condition so that a stable equilibrium between several phases
of different compositions exists.
This technique can be applied to graphically determine any
kind of phase equilibrium. In the case of a LLE, the molar Gibbs
Table 1
Activity coefcients values issued from Pengs approach (g
i,Peng
) for a convention-
ally ideal mixture obeying Raoults law (g
i,conventional
1).
Pressure range g
i,Peng
P4P
sat
1
T4P
sat
2
T
g
liquid
1,Peng
1 g
liquid
2,Peng
1
Component 1 is liquid
Component 2 is liquid
The mixtureideal in the conventional senseis
in the liquid state
P
sat
1
T 4P4P
sat
2
T
g
liquid
1,Peng

P
sat
1
P
g
liquid
2,Peng
1
g
gas
1,Peng
1 g
gas
2,Peng

P
P
sat
2
Component 1 is gaseous
Component 2 is liquid
The mixtureideal in the conventional senseis
either in the liquid state or in the gaseous state
or in VLE
PoP
sat
2
T oP
sat
1
T
g
gas
1,Peng
1 g
gas
2,Peng
1
Component 1 is gaseous
Component 2 is gaseous
The mixtureideal in the conventional senseis
in the gaseous state
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 327
energy of the liquid phase assumed to be a single phase that is:
g
liquid
T,P,x

2
i 1
x
i
Ug
i,liquid
T,P,x 50
has to be plotted.
In the case of a VLE, the molar Gibbs energy of the one-phase
liquid postulated system (g
liquid
) and the molar Gibbs energy of
the one-phase gas postulated system:
g
gas
T,P,y

2
i 1
y
i
Ug
i,gas
T,P,y 51
are calculated. For a given value of the overall composition, only
the smallest value between g
liquid
and g
gas
which identies the
most stable homogeneous system needs to be plotted. The molar
Gibbs energy of the system is thus dened by:
g min g
liquid
,g
gas
_ _
52
When the two phases in equilibrium are not in the same aggrega-
tion state (e.g. a liquid phase in equilibrium with a gaseous phase), in
order a double tangent indicates the composition of the phases in
equilibrium, it is compulsory that the pure-component reference state
used to render the chemical potential of a component i is the same in
the two phases. Indeed, by doing so, one obtains for a VLE:
g
i,liquid
T,P,z g
ref :state
i pure
T,PRTln
^
f
i,liquid
T,P,z
f
ref :state
i pure
T,P
_ _
g
i,gas
T,P,z g
ref :state
i pure
T,P RTln
^
f
i,gas
T,P,z
f
ref :state
i pure
T,P
_ _
_

_
53
so that:
g
liquid
T,P,z

2
i 1
z
i
Ug
ref :state
i pure
T,P RT

2
i 1
z
i
Uln
^
f
i,liquid
T,P,z
f
ref :state
i pure
T,P
_
_
_
_
g
gas
T,P,z

2
i 1
z
i
Ug
ref :state
i pure
T,P RT

2
i 1
z
i
Uln
^
f
i,gas
T,P,z
f
ref :state
i pure
T,P
_
_
_
_
_

_
54
The lhs of Eqs. (54) are thus the molar Gibbs energy of each
phase (liquid or gas) translated by the same quantity. Such a
translation does not alter in any way the double-tangent construc-
tion of coexisting phases. The pure-component reference state can be
chosen freely and can for instance be the pure liquid, the pure gas,
the pure perfect gas or the stable (actual) state. Although any value
would be correct, it is convenient to arbitrarily assign a value of zero
to g
ref :state
i pure
T,P so that g can be easily dened by:
gT,P,z
RT

2
i 1
z
i
Uln
^
f
i
T,P,z
f
ref :state
i pure
T,P
_
_
_
_
55
The non-inuence of the pure component reference state on the
double-tangent construction of coexisting phases is illustrated in
Fig. 5 for the system toluene (1)ethylbenzene (2) at t20 1C and
P2 kPa. In such a gure, two different reference states were
selected:
if the chemical potentials of the pure perfect gases g
pg
i pure
at
system temperature and at unit pressure, are taken as refer-
ence and equal to zero, the reduced Gibbs energy of a
homogeneous system containing p components of mole frac-
tions z
i
is according to Eq. (55):
gT,P,z
RT

p
i 1
z
i
Uln
^
f
i
T,P,z 56
Assuming that the considered liquid phase is an ideal solution

^
f
i,liquid
T,P,x P
sat
i
Ux
i
and that the gas phase is a perfect-gas
mixture
^
f
i,gas
T,P,y PUy
i
, one has:
g
liquid
T,P,x
RT
x
1
Uln x
1
UP
sat
1
T
_
x
2
Uln x
2
UP
sat
2
T
_
g
gas
T,P,y
RT
y
1
Uln y
1
UP
_ _
y
2
Uln y
2
UP
_ _
_
_
_
57
If the chemical potentials of the pure components in their actual
(stable) state at systemtemperature and pressure g
stable
i pure
T,P are
taken as reference, i.e., equal to zero, one has following Eq. (55):
gT,P,z
RT

p
i 1
z
i
Uln
^
f
i
T,P,z
f
stable
i pure
T,P
_ _
58
However the chemical potential change on mixing of component i
is by denition: g
m
i
g
i
g
stable
i pure
T,P RTln
^
f
i
T,P,z=f
stable
i pure
T,P.
0.0 1.0
0.0
-0.1
z1
g/(RT)
A
B
C
D
E
F
Fig. 4. Application of the Gibbs double-tangent construction to nd coexisting
phases in the case where several double tangents exist on a g/(RT) vs. composition
plot at a xed temperature and pressure.
0.0 1.0
-0.5
0.0
0.5
x
1
,y
1
g
RT
The ref. state for each component
is the pure perfect gas at system
T and unit pressure.
liquid
vapor
double tangent
(tie line)
The ref. state is the pure component
in its actual (stable)
state at system T and P and g = g
m
.
L
L
V
V
x
L
= 0.47 y
V
= 0.72
g
gas
g
liquid
< g
liquid
g
gas
<
A
{gliquid, ggas} For all z
1
[0;1] g(homogeneous system) = min
B
Fig. 5. Application of the Gibbs double-tangent construction to nd coexisting
phases with emphasis on the inuence of the pure-component reference state:
pure perfect gas at system temperature and at unit pressure (1 bar, here) on the
upper curve and pure component in its stable state at system temperature and
pressure (lower curve). In this latter case: gg
m
. Example of the toluene
(1)ethylbenzene (2) binary system at t20 1C and P2 kPa. g
liquid
=RT and
g
gas
=RT are given by Eqs. (57) and (59).
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 328
With the considered reference state, we thus obtain: g/RTg
m
/RT.
Such a reference state is often chosen by researchers working with
equations of state (see for example the book by Michelsen and
Mollerup, 2007 or the paper by Baker et al., 1982). Both quantities
^
f
i
T,P,z and f
stable
i pure
T,P can indeed be calculated without efforts and g
is always zero when the composition is zero or one. For the studied
system which can be regarded as ideal and by remembering that in
the considered conditions, pure toluene is in the gaseous state and
pure ethylbenzene is in the liquid state, one obtains:
g
liquid
T,P,x
RT
x
1
ln
x
1
UP
sat
1
T
P
_ _
x
2
lnx
2
g
gas
T,P,y
RT
y
1
lny
1
y
2
ln
y
2
UP
P
sat
2
T
_ _
_

_
59
Expressions in Eq. (59) are obviously similar to the g
m,id
formulations given by Eqs. (33) and (34) and Fig. 5 highlights
on the selected system that this second reference state leads as
expected to the same liquid and gas phase compositions as the
rst one.
This second reference state leads us to conclude that Gibbss
theorem asserts that by plotting at constant temperature and
pressure the Gibbs energy change on mixing (g
m
) of a binary
system vs. the molar composition, the existence of a double
tangent is a necessary and sufcient condition so that an equili-
brium between two phases of different compositions exists at this
temperature and pressure which was the second statement of our
introduction.
Remark:
(1) In Fig. 5, the curves g vs. composition are concave upward
(i.e. convex) for all composition and there is thus no change in
concavity. Let us however recall that a change in concavity is
a prerequisite to represent a two-phase equilibrium only if
the two phases are in the same aggregation state (e.g. liquid
liquid equilibrium) and if the same model (e.g. the same
equation of state or the same activity coefcient model) is
applied to both phases.
(2) By coming back to Fig. 1, we should conclude that an ideal liquid
phase cannot be in VLE with an ideal gaseous mixture. This
assertion is obviously wrong. The reason does not come from an
incorrect use of the double-tangent construction of coexisting
phases but from an erroneous expression for g
m,id
. Eqs. (2) and
(3) never describe the ideal-solution Gibbs energy change on
mixing at a temperature and pressure where a VLE exists. In this
latter case, the correct mathematical expressions to be used are
given by Eqs. (33) and (34). We can also state that Eq. (2) is a
correct mathematical expression for the molar Gibbs energy of
an ideal liquid phase when the pure liquid is chosen as the pure-
component reference state to render the chemical potentials.
Symmetrically Eq. (3) is a correct mathematical expression for
the molar Gibbs energy of an ideal gaseous mixture when the
pure gas is chosen as the pure-component reference state to
render the chemical potentials. As previously explained, since
the pure-component reference state is different for the two
phases, the double-tangent construction cannot be applied with
such expressions.
(3) As previously explained, all well-known textbooks of thermo-
dynamics, by dening the ideal-mixture Gibbs energy change on
mixing by Eqs. (2) and (3) can obviously never apply the Gibbs
double-tangent construction of coexisting phases to vapor
liquid equilibrium. Unfortunately, the deep reason of why it
does not work is from our knowledge never explained thus
causing confusion for students and practicing engineers. How-
ever, in the same books, the graphical construction is exten-
sively used to determine with success LLE what reinforces the
confusion. The reason of this success is simple: to graphically
highlight a LLE, we only need to plot g
m
liquid
=RT vs. x
1
. Following
Eq. (2), all textbooks thus plot the following function:
G
m
liquid
RT
x
1
Ulnx
1
Ug
1
x
2
Ulnx
2
Ug
2
60
When the liquidliquid equilibrium is obtained by mixing two
pure liquids, then G
m
liquid
g
m
liquid
(the stable state is the pure
liquid state for the two components) and we nd back the
classical Gibbs criterion. A double tangent will thus give the
composition of the two liquid phases in equilibrium.
When a liquidliquid equilibrium is obtained by mixing a pure
liquid and a pure gas (or possibly two pure gases), Eq. (2) is not
the correct equation to calculate g
m,idl
(T,x) and Eq. (60) is not
the correct equation to express g
m
liquid
but a double tangent
on the curve G
m
liquid
=RT vs. x
1
(Eq. (60)) will allow to determine
the composition of the two liquid phases in equilibrium.
Indeed, in Eq. (60), the same pure-component reference state
here the pure liquid state is used to render the chemical
potential of a component i in the two liquid phases. In other
words, by improperly stating that G
m
liquid
(Eq. (60)) is the molar
Gibbs energy change on mixing of the liquid phase, the
graphical construction works.
4. Conclusion
The concept of ideal mixture is illustrated in thousands of books
and scientic publications and is widely used in chemical engineer-
ing thermodynamics. The aim of this paper was however to show
that some points on the properties of ideal mixtures needed to be
claried. From a practical point of view, we are convinced that an
ideal-mixture equation must be useful both as an approximation to
the properties of many real mixtures and as a leading term for more
complex equations for mixture properties. This is the reason why,
the structural denition of an ideal mixture is in our opinion the
most convenient: we will state that a binary mixture can be
considered as ideal if the two molecules A and B are sufciently
alike from the point of view of the molecular interactions which
they exert on one another, and from the point of view of their
shapes and sizes. Such ideal mixtures have many remarkable
properties. Among them, the simple mathematical expression of
the chemical potential of a component i in an ideal mixture given
by Eqs. (6) and (7) is certainly the most important.
In many textbooks of thermodynamics, an important miscon-
ception however arises during the denition of the property
change on mixing and the goal of this article was to give the
correct expressions of these quantities. The key point to under-
stand this mistake is to be aware that the pure-component states
which appear in Eqs. (6) and (7) can be non-physically realizable
states. Such a situation always occurs when at a given tempera-
ture, the pressure of the ideal mixture is between the vapor
pressures of the two pure components. In this pressure range
(where VLE necessarily arises), it is always observed volume and
enthalpy change on the formation of an ideal mixture from its pure
components at the same temperature and pressure. For the system
toluene (1)ethylbenzene (2) at t20 1C and P2 kPa, the heat
of mixing may be as high as 17.7 kJ mol
1
but the molar excess
enthalpy never exceeds 0.005 kJ mol
1
. Ideal mixtures have thus
in fact less remarkable properties than expected.
The knowledge of the correct mathematical expressions to
calculate ideal-mixture property changes on mixing as those given
in this article are extremely important for at least two reasons:
Ideal-mixture properties are the starting point to estimate the
properties of real mixtures. A non-correct estimation of the
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 329
ideal-mixture property changes on mixing, will inevitably lead
to a wrong estimation of the property changes on mixing of
real mixtures through Eq. (24).
The molar Gibbs energy change on mixing is a key property on
which the double-tangent construction of coexisting phases can
be applied. An incorrect estimation of g
m,id
(T,P,z), can thus lead to
unreliable and doubtful results like to state that an ideal liquid
mixture cannot be in VLE with a perfect-gas mixture.
To conclude, we can assert that by using the ideal-solution
concept, the chemical potential of a component i in a real (non-
ideal) liquid phase (rlp), always writes:
61
By denition of the partial molar Gibbs energy change on
mixing g
m
i
, the chemical potential of a component i in a real
(non-ideal) liquid phase (rlp), also always writes:
62
we however always can nd situations for which: g
liquid
i pure
T,P
ag
stable
i pure
T,P, and by consequence: g
m,id
i
aRTlnx
i
and g
m
i
aRTlna
i
which in return implies: v
m,id
i
a0 and h
m,id
i
a0 that is v
m
av
E
and
h
m
ah
E
.
Nomenclature
Latin letters
a molar Helmholtz energy
a
i
activity of component i
c
P
molar heat capacity at constant pressure
EoS equation of state
f
i
fugacity of pure component i
^
f
i
fugacity of component i in a mixture
g molar Gibbs energy
g=RT reduced Gibbs energy
h molar enthalpy
k
ij
binary interaction parameter involved in the classical
mixing rules of the PengRobinson EoS
lhs left hand side
P pressure
P
sat
i
T vapor pressure of pure component i at temperature T
R gas constant (8.314472 J mol
1
K
1
)
rhs right hand side
s molar entropy
T absolute temperature
u molar internal energy
v molar volume
x
i
mole fraction of component i in the liquid phase
y
i
mole fraction of component i in the gas phase
z
i
overall mole fraction of component i
z overall mole fraction vector
Greek letters
g
i
activity coefcient of component i in a mixture
j
i
fugacity coefcient of pure component i
^ j
i
fugacity coefcient of component i in a mixture
t
a
molar proportion of phase a
Subscripts and superscripts
E excess property
id ideal mixture
idg ideal gas mixture
idl ideal liquid mixture
m property change on mixing
pgm perfect-gas mixture
rlp real liquid phase
rm real mixture
Acknowledgements
The authors would like to thank Professors Michael L. Michel-
sen and Georgios M. Kontogeorgis from the Technical University
of Denmark warmly for the exciting discussions we had while
doing this research.
Appendix A. h
E
(T,P,z), h
m
(T,P,z) and h
m,id
(T,P,z) calculations
from an equation of state
We believe it is important to explain how Figs. 3bd were
calculated with the PengRobinson equation of state. Fig. 3a
highlights a vaporliquid equilibrium at t20 1C and P2 kPa:
the liquid phase composition is x
1
0.47 and the gas phase
composition is y
1
0.72.
(1) h
E
(T,P,z) calculation:
For z
1
o0.47, the mixture is thus liquid and the excess
enthalpy was calculated as:
h
E,liquid
T,P,z h
liquid
T,P,z
..
molar enthalpy of
the real liquid mixture
h
id,liquid
T,P,z
..
see Eq: 18
h
liquid
T,P,z z
1
Uh
liquid
1 pure
T,Pz
2
Uh
liquid
2 pure
T,P
_ _
A1
The stable state for component 1 is however gaseous and
h
liquid
1 pure
T,P was thus calculated with the smallest volume
(non-stable liquid root) when the equation of state was
solved for pure component 1.
For z
1
40.72, the mixture is gaseous and the excess enthalpy
was calculated as:
h
E,gas
T,P,z h
gas
T,P,z
..
molar enthalpy of
the real gas mixture
h
id,gas
T,P,z
..
see Eq: 18
h
gas
T,P,zz
1
Uh
gas
1 pure
T,Pz
2
Uh
gas
2 pure
T,P A2
The stable state for component 2 is however liquid and
h
gas
2 pure
T,P was thus calculated with the largest volume
(non-stable gas root) when the equation of state was solved
for pure component 2. A straight line was added in the two-
phase region (0.47rz
1
r0.72).
(2) h
m
(T,P,z) calculation:
Whatever the composition (z
1
o0.47 and z
1
40.72), the
enthalpy change on mixing (see Eq. (20)) was calculated as:
h
m
T,P,z hT,P,z
..
molar enthalpy
of the mixture
z
1
Uh
stable
1 pure
T,Pz
2
Uh
stable
2 pure
T,P
_ _
hT,P,z
..
molar enthalpy
of the mixture
z
1
Uh
gas
1 pure
T,Pz
2
Uh
liquid
2 pure
T,P
_ _
A3
and a straight line was added in the two-phase region.
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 330
(3) h
m,id
(T,P,z) calculation:
The ideal-mixture enthalpy change on mixing can obviously
be simply determined as: h
m,id
h
m
h
E
. A direct calculation
can also be performed following Eq. (26). At t20 1C and
P2 kPa, the stable states for component 1 and 2 are respec-
tively gaseous and liquid. For z
1
o0.47, the mixture is liquid
and h
m,id
(Eq. (26)) is thus given by:
h
m,id
T,P,z z
1
U h
liquid
1 pure
T,Ph
stable
1 pure
T,P
_ _
z
2
U h
liquid
2 pure
T,Ph
stable
2 pure
T,P
_ _
z
1
U h
liquid
1 pure
T,Ph
gaseous
1 pure
T,P
_ _
%z
1
UD
vap
H
1
201C A4
For z
1
40.72, the mixture is gaseous and h
m,id
(Eq. (26)) is
given by:
h
m,id
T,P,z z
1
U h
gaseous
1 pure
T,Ph
stable
1 pure
T,P
_ _
z
2
U h
gaseous
2 pure
T,Ph
stable
2 pure
T,P
_ _
z
2
U h
gaseous
2 pure
T,Ph
liquid
2 pure
T,P
_ _
%z
2
UD
vap
H
2
201C
A5
By the end, a straight line is added in the two-phase region
(0.47rz
1
r0.72).
Appendix B. Calculation of the ideal-mixture volume,
entropy, enthalpy, internal energy and constant pressure heat
capacity change on mixing.
The knowledge of the ideal-mixture Gibbs energy change on
mixing allows calculating the other ideal-mixture property
changes on mixing. Indeed, from basic thermodynamics, one has:
v
m,id

@g
m,id
@P
_ _
T,z
s
m,id

@g
m,id
@T
_ _
P,z
h
m,id
g
m,id
TUs
m,id
u
m,id
h
m,id
PUv
m,id
c
m,id
P

@h
m,id
@T
_ _
P,z
_

_
B1
For the three cases studied in Section 2.6.2 and for which the
ideal-mixture Gibbs energy change on mixing is respectively
given by Eqs. (28), (30), (33), (34), (36) and (37), the mathematical
expressions for the other property changes on mixing are sum-
marized in Tables B1 and B2. The derivative of the vapor pressure
with respect to temperature may be needed to calculate s
m,id
. It
however can be estimated from the ClausiusClapeyron equation:
dP
sat
i
=dT D
vap
S
i
=D
vap
V
i
. At low to moderate pressure, the volume
of vaporization veries:
D
vap
V
i
%
RT
P
sat
i
B2
Table B1
Mathematical expressions of the property changes on mixing for a binary liquid ideal mixture.
Case 1 g
m,id
liquid
T,P,x RTx
1
lnx
1
x
2
lnx
2
Eq: 28
P4P
sat
1
T 4P
sat
2
T v
m,id
liquid
T,P,x 0
s
m,id
liquid
T,P,x
g
m,id
liquid
T
Rx
1
lnx
1
x
2
lnx
2

h
m,id
liquid
T,P,x 0
u
m,id
liquid
T,P,x 0
c
m,id
P,liquid
T,P,x 0
Component 1 is liquid
Component 2 is liquid
The ideal mixture is liquid
Case 2
g
m,id
liquid
T,P,x RT x
1
ln
x1UP
sat
1
T
P
_ _
x
2
lnx
2
_ _
Eq: 33
P
sat
1
T 4P4P
sat
2
T
v
m,id
liquid
T,P,x x
1
RT
P
s
m,id
liquid
T,P,x
g
m,id
liquid
T
x
1
UDvapS
1
R x
1
ln
x
1
UP
sat
1
T
P
_ _

DvapS
1
R
_ _
x
2
lnx
2
_ _
h
m,id
liquid
T,P,x x
1
UDvapH
1
T
u
m,id
liquid
T,P,x x
1
U RTDvapH
1
_ _
c
m,id
P,liquid
T,P,x 0
Component 1 is gaseous
Component 2 is liquid
The ideal mixture is liquid
Case 3
g
m,id
liquid
T,P,x RT x
1
ln
x1UP
sat
1
T
P
_ _
x
2
ln
x2UP
sat
2
T
P
_ _ _ _
Eq: 37
PoP
sat
2
ToP
sat
1
T
Component 1 is gaseous
v
m,id
liquid
T,P,x x
1
RT
P
x
2
RT
P

RT
P
s
m,id
liquid
T,P,x
g
m,id
liquid
T
x
1
UDvapS
1
x
2
UDvapS
2
R x
1
ln
x
1
UP
sat
1
T
P
_ _

DvapS
1
R
_ _
x
2
ln
x
2
UP
sat
2
T
P
_ _

DvapS
2
R
_ _ _ _
h
m,id
liquid
T,P,x x
1
UDvapH
1
Tx
2
UDvapH
2
T
u
m,id
liquid
T,P,x x
1
U RTDvapH
1
_ _
x
2
U RTDvapH
2
_ _
c
m,id
P,liquid
T,P,x 0
Component 2 is gaseous
The ideal mixture is liquid
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 331
so that:
dP
sat
i
dT
%
D
vap
S
i
UP
sat
i
RT
B3
The derivative of the enthalpy of vaporization with respect to
temperature may be needed to calculate c
m,id
P
. However at low or
moderate pressure D
vap
H
i
can be considered as constant so that it
will be assumed that:
dD
vap
H
i
dT
0 B4
To sum up this appendix, Table B3 gives the partial molar
property changes on mixing for a component i in an ideal mixture
(liquid or gaseous) depending on either the actual state for this
component is liquid P4P
sat
i
T or gaseous PoP
sat
i
T. The twelve
equations found in the rst and forth column of Table B3 are usually
given in most of the textbooks of thermodynamics but to our
knowledge the twelve others (second and third columns of Table
B3) are given for the rst time in this paper.
References
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Table B2
Mathematical expressions of the property changes on mixing for a binary gaseous ideal mixture.
Case 1 g
m,id
gas
T,P,y RTy
1
lny
1
y
2
lny
2
Eq: 36
PoP
sat
2
ToP
sat
1
T v
m,id
gas
T,P,y 0
s
m,id
gas
T,P,y
g
m,id
gas
T
Ry
1
lny
1
y
2
lny
2

h
m,id
gas
T,P,y 0
u
m,id
gas
T,P,y 0
c
m,id
P,gas
T,P,y 0
Component 1 is gaseous
Component 2 is gaseous
The ideal mixture is gaseous
Case 2
g
m,id
gas
T,P,y RT y
1
lny
1
y
2
ln
y
2
UP
P
sat
2
T
_ _ _ _
Eq: 34
P
sat
1
T 4P4P
sat
2
T
Component 1 is gaseous
v
m,id
gas
T,P,y y
2
RT
P
s
m,id
gas
T,P,y
g
m,id
gas
T
y
2
UDvapS
2
R y
1
lny
1
y
2
ln
y
2
UP
P
sat
2
T
_ _

DvapS
2
R
_ _ _ _
h
m,id
gas
T,P,y y
2
UDvapH
2
T
u
m,id
gas
T,P,y y
2
U DvapH
2
RT
_ _
c
m,id
P,gas
T,P,y 0
Component 2 is liquid
The ideal mixture is gaseous
Case 3
g
m,id
gas
T,P,y RT y
1
ln
y
1
UP
P
sat
1
T
_ _
y
2
ln
y
2
UP
P
sat
2
T
_ _ _ _
Eq: 30
P4P
sat
1
T 4P
sat
2
T v
m,id
gas
T,P,y y
1
RT
P
y
2
RT
P

RT
P
s
m,id
gas
T,P,y
g
m,id
gas
T
y
1
UDvapS
1
y
2
UDvapS
2
R y
1
ln
y
1
UP
P
sat
1
T
_ _

DvapS
1
R
_ _
y
2
ln
y
2
UP
P
sat
2
T
_ _

DvapS
2
R
_ _ _ _
h
m,id
gas
T,P,y y
1
UDvapH
1
Ty
2
UDvapH
2
T
u
m,id
gas
T,P,y y
1
U DvapH
1
RT
_ _
y
2
U DvapH
2
RT
_ _
c
m,id
P,gas
T,P,y 0
Component 1 is liquid
Component 2 is liquid
The ideal mixture is gaseous
Table B3
Mathematical expressions of the ideal-mixture partial molar property changes on mixing.
P4P
sat
i
T (pure component i is liquid) PoP
sat
i
T (pure component i is gaseous)
g
m,id
i,liq
RTlnx
i g
m,id
i,gas
RTln
y
i
UP
P
sat
i
T
_ _
g
m,id
i,liq
RTln
xi UP
sat
i
T
P
_ _
g
m,id
i,gas
RTlny
i
v
m,id
i,liq
0 v
m,id
i,gas

RT
P
v
m,id
i,liq

RT
P
v
m,id
i,gas
0
s
m,id
i,liq
Rlnx
i s
m,id
i,gas
Rln
y
i
UP
P
sat
i
T
_ _
DvapS
i s
m,id
i,liq
Rln
xi UP
sat
i
T
P
_ _
DvapS
i
s
m,id
i,gas
Rlny
i
h
m,id
i,liq
0 h
m,id
i,gas
DvapH
i
h
m,id
i,liq
DvapH
i
h
m,id
i,gas
0
u
m,id
i,liq
0 u
m,id
i,gas
DvapH
i
RT u
m,id
i,liq
RTDvapH
i
u
m,id
i,gas
0
c
m,id
P,i,liq
0 c
m,id
P,i,gas
0 c
m,id
P,i,liq
0 c
m,id
P,i,gas
0
R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 332
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R. Privat, J.-N. Jaubert / Chemical Engineering Science 82 (2012) 319333 333