Thermodynamics of Blends and Solutions

- equilibrium phase behavior of mixtures is controlled by Gibbs free energy ∆Gm, it is re-
lated to the enthalpy (heat) of mixing ∆Hm, and the entropy of mixing ∆Sm by the Gibbs-
Helmholtz equation

∆G m = ∆H m − T∆Sm (1)

- T ist the absolute temperature, criteria for phase stability of binary mixtures of composi-
tion φ at fixed temperature T and pressure p are

 ∂ 2 ∆G m 
∆G m < 0 ,   >0 (2)
 ∂φ 2 
  p, T

- plotting ∆Gm versus composition of the mixture can yield two simple cases as shown in
the next Figure

Figure:Gibbs free energy ∆Gm as a function of blend composition. (a) completely miscible.
(b) completely immiscible

1
- in case a) a homogeneous system with the volume fraction of component 2, φ2=a, is con-
sidered, this system has a Gibbs free energy represented by A, if this mixture would sepa-
rate into a component 2 rich and a component 2 poor phase with compositions φ2’ and
φ2’’, ∆Gm would be located on the dashed line between P and Q in the point B, the Gibbs
free energy of mixing for a phase separated mixture is then

∆G m = x ' ∆G 'm + x" ∆G"m (3)

- where x’ and x’’ are the volume fractions of the respective phases, the transition from A to
B leads to an increase in ∆Gm, thus a single phase system is stable and phase separation is
not favored
- the opposite case can be considered in b), changing the Gibbs free energy from A to B
lowers it, phase separation is favored and a two-phase system with compositions φ2’ and
φ2’’ is stable

- the situation becomes more complicated when the free energy function ∆Gm(φ2) is an in-
termediate case between complete miscibility or immiscibility as shown in the next Figure

Figure: Gibbs free energy ∆Gm as a function of blend composition for two different tempera-
tures (upper part) and the resulting phase diagram (lower part).

2
- as can be seen, the composition dependence of ∆Gm at the edges is identical with that of
the previous Figure a), i.e. in these composition ranges miscibility occurs, the Gibbs crite-
ria for phase stability Eq. (2) hold, in the center range of blend composition the system is
immiscible because ∆Gm has the same composition dependence as shown in the previous
Figure b),thus in a certain range of blend compositions a transition from miscibility to
immiscibility and vice versus occurs (see phase diagram in lower part), the binodal de-
fines the equilibrium composition of two coexisting phases and is given by the equality of
the chemical potentials µ of the respective components in each phase

µ1 ' = µ1" and µ 2 ' = µ 2 " (4)

or by the equivalent term

∆µ1 ' = ∆µ1" and ∆µ 2 ' = ∆µ 2 " (5)

the chemical potential is given by

 ∂∆G 
  ∝ ∆µ 2 (6)
 ∂φ 2  p, T

- it follows that the composition of the two coexisting phases is given by the common tan-
gent of the Gibbs free energy function as shown in the Figure, the comment tangent yields
the binodal (lower part of the Figure) that separates miscible and metastable area, the spi-
nodal separates metastable region and two-phase region and it is given by the inflection
points of the free energy function

 ∂ 2 ∆G m 
  =0 (7)
 ∂φ 2 
  p, T

- it can be seen that the binodal and spinodal match in the critical point which is then given
by

 ∂ 2 ∆G m   ∂ 3 ∆G m 
  =  =0 (8)
 ∂φ 2   ∂φ3 
  p, T   p, T

- several special cases derived for solution can be discussed for mixtures, ideal mixtures are
the most simple cases characterized by ∆Hm=0, the internal energy of mixing ∆Um is zero
and the volume change during mixing is zero ∆Vm=0, all quantities that differ from zero
(∆Gm, ∆Fm, and ∆Sm) derive from the change in entropy as for an irreversible process, i.e.
simply by the number of rearrangements of molecules in the mixing process, another im-
portant concept is that of regular solutions, the entropy of mixing is the same as for ideal
solutions but the enthalpy of mixing is not zero and a function of composition