Chapter 12

Solution
Thermodynamics
Applications

Liquid Phase Properties from VLE

In a vapor which a gas mixture
and a liquid solution coexist in
vapor/liquid equilibrium,
For species i in vapor mixture,

f i v yiiv P
Similar for species i in solution,

f i l yiiv P

Fugacity

quid equilibrium, vapor is assumed

hence,
ig

i 1

f i l fi v yi P

Fugacity

acity of species i (in both the liquid

phases) is equal to the partial
f species i in the vapor phase.

f1 y1 P

f2 y2 P

In an ideal solution,

f i id xi f i

Activity coefficient

Defining the activity coefficient

(12.1)
(12.3)

Activity coefficient
Henrys law applies to a species as it
approaches infinite dilution in a binary
solution, and the Gibbs/Duhem equation
insures validity of the Lewis/Randall rule
for the other species as it approaches
purity.

Excess Gibbs Energy

(12.6)
(12.7)
(12.8)

Data Reduction

(12.11)
(12.12)

Thermodynamic Consistency

(12.13)

Thermodynamic Consistency
The right side of this equation is exactly the
quantity that Eq. (12.7), the Gibbs/Duhem
equation, requires to be zero for consistent
data. The residual on the left therefore
provides a direct measure of deviation from
the Gibbs/Duhem equation. The extent to
which a data set departs from consistency is
measured by the degree to which these
residuals fail to scatter about zero.

Example 12.1

(page 442)

VLE data for diethyl ketone(1)/n-hexane(2) at 65 oC

(338.15 K) as reported by Maripuri and Ratcliff, are
given in the first three columns of Table (12.4).
Reduce this set of data.

12.2 Models for the Excess

Gibbs Energy

(12.14)

(12.15a)
(12.15b)

12.2 Models for the Excess

Gibbs Energy

(12.17a)

(12.17b)

12.3 Property Changes of

Mixing
(12.25)

(12.26)
(12.27)
(12.28)

Example 12.2

(page 452)

The excess enthalpy (heat of mixing) for a liquid

mixture of species 1 and 2 at fixed T and P is
represented by the equation
where HE is in J/mol. Determine expressions for
and as functions of x1.

Example 12.3

(page 452)

Property changes of mixing and excess properties

are related. Show how Fig. 11.4 and 12.13 are
generated from correlated data for H(x) and GE(x).

12.4 Heat Effects of Mixing

Processes
(12.39)

Heats of Solution

where is the heat of solution on the basis of a mole

of solute.

Example 12.4
Calculate the heat of formation of LiCl in 12 mol of
H2O at 25oC (298 K).

Example 12.5
A single-effect evaporator operating at atmospheric
pressure concentrates at 15% (by mass) LiCl
solution to 40%. The feed enters the evaporator at
the rate of 2 kg/s at 25oC. The normal boiling point
of a 40% LiCl solution is about 132oC, and its
specific heat is estimated as 2.72 kJ/kg oC. What is
the heat transfer rate in the evaporator