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Ind. Eng. Chem. Res.

2006, 45, 8217-8222 8217

Possible Existence of a Negative (Positive) Homogeneous Azeotrope When the


Binary Mixture Exhibits Positive (Negative) Deviations from Ideal Solution
Behavior (That is, When gE is Positive (Negative))
Jean-Noe1 l Jaubert* and Romain Privat
Institut National Polytechnique de Lorraine, Ecole Nationale Supérieure des Industries Chimiques, Laboratoire
de Thermodynamique des Milieux Polyphasés, 1 rue GrandVille, 54000 Nancy, France

The objective of this note is to give proof that the existence of a positive (or, respectively, negative)
homogeneous azeotrope is not linked to the sign (positive or negative) of the molar excess Gibbs energy
function (gE) but rather to the curvature of gE. We demonstrate that when gE is concave (or, respectively,
convex), a binary system may exhibit a positive (or, respectively, negative) azeotrope. Because a concave or
convex function may indifferently be positive or negative, when gE is positive (or, respectively, negative), a
binary system may exhibit a negative (or, respectively, positive) azeotrope.

Introduction an isobaric Txy diagram and by a maximum on the correspond-


ing isothermal Pxy diagram. Conversely, a negative azeotrope
In some excellent textbooks of thermodynamics,1-9 it is is simply a maximum boiling-point azeotrope that is character-
written that, when a binary system exhibits positive (negative) ized by a maximum on an isobaric Txy diagram and by a
deviations from ideal solution behavior (i.e., when gE is positive minimum on the corresponding isothermal Pxy diagram. We
(negative)), the system may not exhibit a negative (positive) see no reason to change these definitions, and they will be used
azeotrope. In other words, some authors make a direct link throughout this article.
between the adjective positive (negative) used to describe an
At this step, it is interesting to wonder why Lecat used the
azeotrope and the sign of the associated gE function. Here, we
adjectives “positive” and “negative” to characterize a homoge-
want to give proof that such a direct link may be incorrect.
Indeed, even when gE is positive (negative), a binary system neous azeotrope. Indeed, which property or which parameter is
may exhibit a negative (positive) azeotrope. However, a direct positive (negative) when a binary system exhibits an azeotrope?
link exists between the curvature of gE (concave or convex) To answer this question, one must carefully read the paper by
and the possible existence of a homogeneous azeotrope (positive Lecat.12 Doing so, we quickly realized that, in Lecat’s mind, a
or negative). In this note, it is demonstrated that when a binary positive function is, in fact, a concave function. Conversely, in
system exhibits a positive (negative) azeotrope, the curve gE vs Lecat’s mind, a negative mathematical function f(x) is not as
x1 is necessarily concave (convex) at the azeotropic composition, classically defined by mathematicians, a function for which f(x)
regardless of the sign of gE. < 0 for all x but a convex function (i.e., a function for which
As a conclusion, the following theorem is demonstrated: “for the second derivative f ′′(x) > 0). Because, in an isothermal
a binary system at the azeotropic composition, the bubble-P phase diagram, in the vicinity of a minimum (maximum)
curVe on an isothermal Pxy diagram has always the same boiling-point azeotrope, the bubble and the dew curves are
curVature (concaVe for a positiVe azeotrope and conVex for a necessarily concave (convex), Lecat decided to call such an
negatiVe azeotrope) as the gE Vs x1 function”. azeotrope a positive (negative) azeotrope. However, the correct
terminology should be a concave (convex) azeotrope. In his
paper, Lecat never defines a positive azeotrope as an azeotrope
Lecat’s Definition of a Homogeneous Positive (or for which gE > 0. As a conclusion, Lecat never defines any
Respectively Negative) Azeotrope property or any parameter effectively greater than zero (>0) or
less than zero (<0) in the vicinity of an azeotrope. Let us here
The term “azeotrope” was originally derived from the Greek,
recall that Lecat was obviously unable to use the thermodynamic
as reported by Wade and Merriman10 in 1911. The adjective
excess functions, because only in 1937 did Scatchard13 introduce
positive or negative that is used to describe a homogeneous
azeotrope was introduced by Maurice Lecat11 in 1926. More the idea of excess functions.
information may be found in the encyclopedia by François As stated in the Introduction, in some excellent textbooks of
Auguste Victor Grignard (winner of the 1912 Nobel prize in thermodynamics, it is written that when a binary system exhibits
Chemistry), in which Lecat wrote a chapter of 147 pages that positive (negative) deviations from ideal solution behavior (i.e.,
was devoted to the distillation.12 According to Lecat, an when gE is positive (negative)), the system may not exhibit a
azeotrope is called positive when a maximum occurs on an negative (positive) azeotrope. Here, we want to give proof that
isothermal Pxy diagram. Conversely, an azeotrope is called such an assertion is not correct. However, if we replace the
negative when a minimum occurs on an isothermal Pxy diagram. adjective positive (negative), by the adjective concave (convex),
In other words, a positive azeotrope is simply a minimum when we talk about the gE function the assertion becomes
boiling-point azeotrope that is characterized by a minimum on correct. It is indeed correct to say that when the gE function is
concave (convex), the system may not exhibit a negative
* To whom the correspondence should be addressed. Fax number: (positive) azeotrope. A proof of this theorem is given in the
+33 3 83 17 51 52. E-mail: jean-noel.jaubert@ensic.inpl-nancy.fr. next section.
10.1021/ie060874f CCC: $33.50 © 2006 American Chemical Society
Published on Web 10/27/2006
8218 Ind. Eng. Chem. Res., Vol. 45, No. 24, 2006

( )|
∂PB
∂x1 T x1)xaz
1
)0 (1)

{
and

( )|
∂ 2P B
∂x21 T x1 ) xaz
1
for a positive azetrope
< 0 (i.e. the bubble-P curve is concave)

( )|
∂2PB
∂x21 T x1 ) xaz
1
for a negative azetrope
> 0 (i.e. the bubble-P curve is convex)

(2)
Step 1: Calculation of (∂PB/∂x1)T. In the so-called gamma-
phi (γ-φ) approach, and assuming, for sake of simplicity, that
the vapor phase behaves as an ideal gas mixture, one has

PB(T,x1) ) Ps1(T)x1γ1(T,x1) + Ps2(T)x2γ2(T,x1) (3)

In the γ-φ approach, the activity coefficients (γ) are calculated


from a gE model. Because such gE models (Porter, Margules,
Van Laar, Redlich-Kister, Wohl, Wilson, NRTL, UNIQUAC,
UNIFAC, etc.) are not dependent on pressure, the resulting
activity coefficients are pressure-independent.
Differentiation of eq 3 leads to

( ) [( ) ] [( ) ]
∂PB
∂x1 T
) Ps1 x1
∂γ1
∂x1 T
+ γ1 + Ps2 x2
∂γ2
∂x1 T
- γ2 (4)

Moreover,

( ) ( )
∂γ1
∂x1 T
) γ1
∂ ln γ1
∂x1 T
(5a)

( ) ( )
∂γ2
∂x1 T
) γ2
∂ ln γ2
∂x1 T
(5b)

Thus, one has

Figure 1. Isothermal Pxy diagrams for two binary systems exhibiting a


homogeneous azeotrope. Panel (a) shows a positive homogeneous azeotrope ( )
∂PB
∂x1
) Ps1γ1 - Ps2γ2 + Ps1x1γ1 ( )
∂ ln γ1
∂x1
+

( )
T T
in a mixture of ethanol (1) and benzene (2) at 370 K. The azeotrope is
∂ ln γ2
merged with the maximum on the isothermal Pxy diagram. In the vicinity Ps2x2γ2 (6)
of the azeotrope, the bubble P-curve is concave (on this particular example, ∂x1 T
it is also concave, for all x1 ∈ [0,1]). Panel (b) shows a negative
homogeneous azeotrope in a mixture of acetone (1) and chloroform (2) at Moreover, the well-known activity coefficient form of the
320 K. The azeotrope is merged with the minimum on the isothermal Pxy
diagram. In the vicinity of the azeotrope, the bubble-P curve is convex (in Gibbs-Duhem equation is

( ) ( )
this particular example, it is also convex, for all x1 ∈ [0,1]).
∂ ln γ2 ∂ ln γ1
x2 ) -x1 (7)
∂x1 T ∂x1 T
Demonstration
Equation 6 becomes
In this section, the following theorem is demonstrated: “for

( ) ( )
a binary system, in the immediate vicinity of the azeotropic ∂PB ∂ ln γ1
composition, the bubble-P curve on an isothermal Pxy dia- ) Ps1γ1 - Ps2γ2 + x1 (Ps γ - Ps2γ2) (8)
∂x1 T ∂x1 T 1 1
gram has always the same curvature (concave for a positive
azeotrope and convex for a negative azeotrope) as the gE vs x1 i.e.,
function”.
It is obvious (see Figure 1) that when a binary system exhibits
a positive (negative) homogeneous azeotrope, at the azeotropic
composition (xaz 1 ) the bubble-P curve on an isothermal Pxy
diagram reaches a maximum (minimum). As a consequence,
the bubble-P curve is concave (convex). By noting PB, the The criterion of stability for a single-phase binary system
bubble pressure, it is thus possible to write can be written as14
Ind. Eng. Chem. Res., Vol. 45, No. 24, 2006 8219

( ) ∂ ln γ1
∂x1 T
>-
x
1
1
(10)
{∂2[gE/(RT)]
∂x12 } ( ) ( )
)
∂ ln γ1
∂x1
-
∂ ln γ2
∂x1

( ) ( )
T T T

1 ∂ ln γ1 1 ∂ ln γ2
Thus, the Γ(T,x1) function that appears in eq 9 clearly must be ) )- (18)
positive for the liquid phase to remain stable. x2 ∂x1 x1 ∂x1
T T
As a conclusion, when a binary system exhibits a homoge-
neous azeotrope, by combining eqs 1 and 9, one has the This equation, in combination with eq 14, yields
following well-known equation:

1 - P2γ2 ) 0
Ps1γaz s az
(11)

Step 2: Calculation of (∂2PB/∂x12)T. Starting with eq 9, a


simple differentiation gives

( ) [ ( ) ( )]
The vapor pressures, the mole fractions and the activity
∂2PB ∂γ1 ∂γ2 coefficients are all positive quantities. Moreover, we know, from
)Γ Ps1 - Ps2 + (Ps1γ1 - Ps2γ2)Γ′ (12)
∂x12 ∂x1 T ∂x1 T the stability condition, that Γ(T,x1) > 0. As a conclusion, the
T
terms

( )| { }|
with
∂2PB ∂2[gE/(RT)]
Γ′ ) ( )
∂Γ
∂x1 T
∂x12 T x1)x1az
and
∂x12 T x1)x1az

always have the same sign.


This equation, in combination with eqs 11 and 5, yields
Thus, eq 2 clearly indicates that, in the immediate vicinity

( )| [
of the azeotropic composition (x1 ) x1az), the curve gE vs x1 is

( )|
∂2PB ∂ ln γ1 necessarily concave for a positive azeotrope and necessarily
2
) Γ(T,xaz s az
1 ) P 1 γ1 - convex for a negative azeotrope. However, regardless of the
∂x1 ∂x1 T x1)x1az type of azeotrope, gE may be positive or negative. It is obvious

]
T x1)x1az
that when the curve gE vs x1 is concave (convex), the binary

( )|
Ps2γaz
2
∂ ln γ2
∂x1 T x1)x1az
(13)
system does not necessarily exhibit a positive (negative)
homogeneous azeotrope. A concave (convex) gE is a necessary
but not sufficient condition for a binary system to exhibit a
A new application of the Gibbs-Duhem equation (eq 7) gives homogeneous positive (negative) azeotrope.

( )|
Discussion and Example
∂2PB
) We believe that confusion has sometimes appeared in
∂x12 T x1)x1az textbooks of thermodynamics, because when an azeotropic

( )|
system exhibits positive (negative) deviations from ideal solution
1 ∂ ln γ1 behavior (i.e., when gE is positive (negative)), the curve gE vs
Γ(T,xaz 1 x2 + P2γ2 x1 ] (14)
[Ps1γaz az s az az
1) x1 generally is concave (convex). Under these conditions, it
xaz
2
∂x1
T x1)x1 az becomes identical to say gE positive (negative) or gE concave
(convex). The fact that, in Lecat’s mind, positive (negative)
Moreover, by definition, means concave (convex) also added to the confusion.
Example of the Existence of a Negative Homogeneous
gE Azeotrope for a Binary Mixture Exhibiting Positive Devia-
) x1 ln γ1 + x2 ln γ2 (15) tions from Ideal Solution Behavior. We know azeotropic
RT
binary systems for which the curvature of the function gE vs x1
changes with composition but without changing sign. A well-
Differentiation of eq 15 gives
known example15-17 is the pentafluoroethane (1)/ammonia (2)

{ } ( ) ( )
system. For this system, at T ) 49.9 °C, for all x1 values (0 <
∂[gE/(RT)] ∂ ln γ1 ∂ ln γ2 x1 < 1), gE is positive (see Figure 2), which means that this
) ln γ1 - ln γ2 + x1 + x2
∂x1 T ∂x1 T ∂x1 T system exhibits positive deviations from ideal solution behavior.
(16) However, for small values of x1, the curve gE vs x1 is concave.
When x1 increases, an inflection point appears and the curve
According to eq 7, the last two terms sum to zero; hence, gE vs x1 becomes convex. In the concave part, the system
exhibits a first azeotrope, which is necessarily a positive

{ }
azeotrope and in the convex part, the system exhibits a second
∂[gE/(RT)]
) ln γ1 - ln γ2 (17) azeotrope which is necessarily a negative azeotrope. Thus, for
∂x1 T this system, a negative azeotrope appears, although gE is
positive.
A second differentiation and a second application of the Gibbs- Application of the Proposed Theorem to a Saddle-Point
Duhem equation gives Azeotrope. Until now, we only mentioned the possible existence
8220 Ind. Eng. Chem. Res., Vol. 45, No. 24, 2006

Figure 2. Behavior of the pentafluoroethane (1)/ammonia (2) system at T ) 49.9 °C, using the NRTL equation fitted to vapor-liquid equilibrium (VLE)
data:15 (a) plot of gE/(RT), ln γ1, and ln γ2 vs x1, and (b) plot of the isothermal Pxy diagram (the dashed line is Raoult’s line and the filled circles are the
experimental VLE data).

of a positive (negative) azeotrope. However, binary systems may and


also exhibit what is either called a saddle-point azeotrope or an

( )|
intermediate boiling-point azeotrope. In such a point, as for any
azeotrope, the liquid and the vapor phase have the same ∂ 2P B
)0
composition. However, the boiling point of the azeotropic ∂x12 T x1)x1az
mixture lies midway between the boiling points of its individual
components. A saddle point azeotrope may appear for systems
According to the theorem established in this note, at the saddle-
that exhibit a double azeotrope when the two azeotropes merge
point azeotrope composition, one also has
into a single point (when the compositions of the two azeotropess

{ }|
one positive and one negativesbecome identical, the resulting
point is a saddle azeotrope). As a consequence, a saddle-point ∂2[gE/(RT)]
azeotrope has the properties of both a positive azeotrope and a )0
negative azeotrope. At this point (amalgamation of a positive ∂x12 T x1)x1az
and of a negative azeotrope), the bubble-P curve must be
simultaneously concave (which is a necessary condition for the and an inflection point necessarily exists at this composition in
existence of a positive azeotrope) and convex (necessary the curve gE vs x1. An example of such behavior is shown in
condition for the existence of a negative azeotrope). Conse- Figure 3 for the pentafluoroethane (1)/ammonia (2) system. Such
quently, the curvature of the bubble-P curve changes at the a diagram was plotted using the NRTL equation. The NRTL
saddle-point azeotrope composition and an inflection point parameters were determined using available experimental data
appears. At the saddle-point azeotrope, as for any azeotrope, at T ) 49.9 °C15 and the temperature at which the saddle-point
the bubble-P curve has an horizontal tangent (another pos- azeotrope appears (T ) 31.6 °C) was determined using these
sibility for the bubble-P curve to exhibit an inflection point parameters. Below T ) 31.6 °C, no true azeotropy occurs.
with an horizontal tangent is discussed in the Appendix at the
end of this note). From a mathematical point of view, a saddle Concluding Remarks
point azeotrope is thus characterized by In this note, we have given proof that, for a binary system in
the immediate vicinity of the azeotropic composition, the

( )|
∂PB bubble-P curve on an isothermal Pxy diagram always has the
)0 same curvature (concave for a positive azeotrope and convex
∂x1 T x1)x1az for a negative azeotrope) as the gE vs x1 function. At this step,
Ind. Eng. Chem. Res., Vol. 45, No. 24, 2006 8221

Figure 3. Isothermal Pxy diagram and corresponding gE/(RT) vs x1 curve


for the pentafluoroethane (1)/ammonia (2) system at T ) 31.6 °C. At this
temperature, the system exhibits a saddle-point azeotrope. Figure A1. (a) Liquid-liquid phase diagram TxR1 xβ1 for the methyl acetate
(1)/water (2) system, which has an upper critical solution temperature
we could wonder whether the bubble-P curve on an isothermal (UCST). (b) Isothermal Pxy diagram for the same system at T ) TUCS )
Pxy diagram always has the same curvature as the gE vs x1 381.15 K.
function for compositions different from the azeotropic com-
position. Our answer is simple: in most cases, this is true, but Given the conditions of eq 9 being
exceptions may exist. This means that, in most cases, when gE
is concave (convex), the bubble curve on an isothermal Pxy
diagram is also concave (convex). When an inflection point
exists on the bubble curve, it also generally exists on the gE vs
x1 plot. This concluding remark can help chemical engineers
who want to model binary systems for which the bubble-P and eq 12 being

( )
curve on an isothermal phase diagram does not behave classi-
cally. For example, if the bubble-P curve has several inflection ∂2PB
points, it is necessary to select a gE model that is mathematically ) Γ(T,x1)∆′(T,x1) + ∆(T,x1)Γ'(T,x1)
able to reproduce such behavior. To be concrete, the diethyl- ∂x12 T
amine (1)/methanol (2) system exhibits a negative azeotrope
with
1 ≈ 0.25) and an inflection point (x1
(xaz ≈ 0.7) on the
inflection

( )
bubble-P curve at T ) 75 °C. For such a binary system, gE
17
∂Γ
is negative and the curve gE vs x1 must be initially convex, to Γ′ )
∂x1 T
reproduce the negative azeotrope, and then concave, to repro-
duce the inflection point. Thus, gE is very similar to that
and
observed in Figure 2a, except that it has a negative value.

Appendix: Other Possibility for the Bubble-P Curve To


∆′ ) ( )
∂∆
∂x1 T
Exhibit an Inflection Point with a Horizontal Tangent
the following situations are observed.
In a previous section, we have seen that, at the saddle point (1) When ∆(T,x1) ) 0 (which is a necessary and sufficient
azeotrope composition, the bubble-P curve exhibited an condition for a binary system to exhibit a homogeneous
inflection point with a horizontal tangent. Here, we want to azeotrope) and, simultaneously, ∆′(T,x1) ) 0, it is obvious that
discuss another possibility for the bubble-P curve to exhibit (∂PB/∂x1)T ) 0 and simultaneously (∂2PB/∂x12)T ) 0. Thus, the
such behavior. bubble-P curve exhibits an inflection point with a horizontal
8222 Ind. Eng. Chem. Res., Vol. 45, No. 24, 2006

tangent. This inflection point corresponds to a saddle-point acknowledged for advising the authors so that the derivations
azeotrope (more details have been given in a previous section). included in this note seem sound to the reader.
(2) When Γ(T,x1) ) 0 (the stability criterion of a single-phase
binary system becomes zero) and, simultaneously, Γ′(T,x1) ) Literature Cited
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(4) Infelta, P. Introductory Thermodynamics, BrownWalker Press: Boca
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)
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Acknowledgment ReceiVed for reView July 7, 2006


Yannick Privat, author R.P.’s twin brother and holder of the ReVised manuscript receiVed September 21, 2006
Accepted October 2, 2006
agrégation in Mathematics (France’s top-level competitive
examination for the recruitment of teachers), is gratefully IE060874F