CHEMICAL ENGINEERING THERMODYNAMICS-II

(ChE – 304)

Dr. Muhammad Asif Akhtar

imasif@uet.edu.pk
Solution Thermodynamics: Theory
 Compositions
• Real system usually contains a mixture of fluid.
• Develop the theoretical foundation for
applications of thermodynamics to gas mixtures
and liquid solutions
• Introducing
– chemical potential
– partial properties
– fugacity
– ideal solution
The Gibbs energy is expressed as a
function of its canonical variables.
Chemical potential and phase equilibria

• Consider a closed system consisting of two phases

in equilibrium:

Mass balance:
Multiple phases at the same T and P are in
equilibrium when chemical potential of
each species is the same in all phases.
 Partial properties
• Define the partial molar property of species i:
Solution properties, M
Partial properties,
Pure-species properties, Mi
 and

Calculation of mixture
properties from partial
properties
The Gibbs/Duhem equation
 Partial properties in binary solution
• For binary system

Const. P and T, using Gibbs/Duhem equation

The need arises in a laboratory for 2000 cm 3 of an
antifreeze solution consisting of 30 mol-% methanol
in water. What volumes of pure methanol and of
pure water at 25°C must be mixed to form the 2000
cm3 of antifreeze at 25°C? The partial and pure
molar volumes are given.
The need arises in a laboratory for 2000 cm3 of an antifreeze solution consisting of 30
mol-% methanol in water. What volumes of pure methanol and of pure water at 25°C
must be mixed to form the 2000 cm3 of antifreeze at 25°C? The partial and pure molar
volumes are given.
The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is:

Determine expressions for and as functions of x1, numerical values for the
pure-species enthalpies H1 and H2, and numerical values for the partial enthalpies at
infinite dilution and
 Open Book Quiz Test # 1
Solve the following problem and submit the solution in Time Allowed: 35 min
hard form. Also, email the solution @
asifakhtar5121414@gmail.com
Subject of email: Registration No-Open Book Quiz 1
Note: No discussion is allowed.
Reference Material: Please consult J.M.Smith, H. C. Van Ness
and M. M. Abbott; “Introduction to Chemical Engineering
Thermodynamics” to solve the given problem.
Relations among partial properties

• Maxwell relation:
 Ideal-gas mixture
• Gibbs’s theorem
– A partial molar property (other than volume) of a
constituent species in an ideal-gas mixture is equal to
the corresponding molar property of the species as a
pure ideal gas at the mixture temperature but at a
pressure equal to its partial pressure in the mixture.
For those independent of pressure, e.g.,

For those depend on pressure, e.g.,

or

From integration of
Fugacity and fugacity coefficient
• Chemical potential:

– provides fundamental criterion for phase equilibria

– however, the Gibbs energy, hence μi, is defined in
relation to the internal energy and entropy - (absolute
values are unknown).
• Fugacity:
– a quantity that takes the place of P.
With units of pressure
Residual Gibbs energy Fugacity coefficient
 VLE for pure species
• Saturated vapor:
• Saturated liquid:

VLE

For a pure species coexisting liquid and vapor phases are in equilibrium when
they have the same temperature, pressure, fugacity and fugacity coefficient.
 Fugacity of a pure liquid
• The fugacity of pure species i as a compressed
liquid:

Since Vi is a weak function of P

• Calculate fugacity of a pure gas at 500 K and 30
bar.
• Suppose a pure liquid is in equilibrium with the
gas at 500 K and 30 bar, calculate the liquid
fugacity.
• Calculate the liquid fugacity at at 500 K and 60
bar.

Data:
Vil = 25 cm3/mol, Z Between 0 and 30 bar
Zi = 1-0.01P
 Fugacity coefficient from the virial
E.O.S
• The virial equation:

– the mixture second virial coefficient B:

– for a binary mixture:
• n mol of gas mixture:
 Similarly:

For multicomponent gas mixture, the general form:

where
Determine the fugacity coefficients for nitrogen and methane in N2(1)/CH4(2)
mixture at 200K and 30 bar if the mixture contains 40 mol-% N2.
 Generalized correlations for the
fugacity coefficient

For pure gas

or
with

For pure gas

Table E1:E4 or Table E13:E16

Estimate a value for the fugacity of 1-butene vapor at 200°C and 70 bar.

and

Table E15 and E16

For gas mixture:

Empirical interaction parameter

Prausnitz et al. 1986

 Excess properties
• The mathematical formalism of excess properties
is analogous to that of the residual properties:

– where M represents the molar (or unit-mass) value of

any extensive thermodynamic property (e.g., V, U, H,
S, G, etc.)
– Similarly, we have:

The fundamental excess-property relation