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.
( )
∂PB
∂x1 T x1)xaz
1
)0 (1)
{
and
( )
∂ 2P B
∂x21 T x1 ) xaz
1
for a positive azetrope
< 0 (i.e. the bubbleP curve is concave)
( )
∂2PB
∂x21 T x1 ) xaz
1
for a negative azetrope
> 0 (i.e. the bubbleP curve is convex)
(2)
Step 1: Calculation of (∂PB/∂x1)T. In the socalled gamma
phi (γφ) approach, and assuming, for sake of simplicity, that
the vapor phase behaves as an ideal gas mixture, one has
( ) [( ) ] [( ) ]
∂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)
( )
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 Pcurve 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 wellknown 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 bubbleP curve is convex (in GibbsDuhem 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 bubbleP 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 bubbleP curve on an isothermal Pxy
diagram reaches a maximum (minimum). As a consequence,
the bubbleP curve is concave (convex). By noting PB, the The criterion of stability for a singlephase 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 wellknown equation:
1  P2γ2 ) 0
Ps1γaz s az
(11)
( ) [ ( ) ( )]
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
( ) [
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 GibbsDuhem 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 example1517 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 SaddlePoint
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 vaporliquid 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).
( )
intermediate boilingpoint 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 saddlepoint ∂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 bubbleP 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 bubbleP curve changes at the a diagram was plotted using the NRTL equation. The NRTL
saddlepoint azeotrope composition and an inflection point parameters were determined using available experimental data
appears. At the saddlepoint azeotrope, as for any azeotrope, at T ) 49.9 °C15 and the temperature at which the saddlepoint
the bubbleP curve has an horizontal tangent (another pos azeotrope appears (T ) 31.6 °C) was determined using these
sibility for the bubbleP 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 bubbleP 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
( )
curve on an isothermal phase diagram does not behave classi
cally. For example, if the bubbleP 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
( )
bubbleP 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.
tangent. This inflection point corresponds to a saddlepoint 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 singlephase
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