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Thermodynamics for Engineers

This document discusses thermodynamic properties of liquid mixtures and vapor-liquid equilibrium. It contains the following key points: 1) In a vapor-liquid equilibrium, the fugacity of each species is equal in both the vapor and liquid phases. 2) The activity coefficient is defined to account for non-ideal behavior in liquid mixtures. 3) Excess properties like excess Gibbs energy can be modeled and related to mixing changes and non-ideal behavior. 4) Example problems are provided to demonstrate calculating heat effects of mixing and solving vapor-liquid equilibrium problems using correlated thermodynamic data.

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68 views20 pages

Thermodynamics for Engineers

This document discusses thermodynamic properties of liquid mixtures and vapor-liquid equilibrium. It contains the following key points: 1) In a vapor-liquid equilibrium, the fugacity of each species is equal in both the vapor and liquid phases. 2) The activity coefficient is defined to account for non-ideal behavior in liquid mixtures. 3) Excess properties like excess Gibbs energy can be modeled and related to mixing changes and non-ideal behavior. 4) Example problems are provided to demonstrate calculating heat effects of mixing and solving vapor-liquid equilibrium problems using correlated thermodynamic data.

Uploaded by

HakashiMirudo
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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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

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