CHAPTER 6:

THERMODYNAMIC PROPERTIES
OF MIXTURES
CHAPTER 6: INTRODUCTION

The purpose of this chapter is to:

In this chapter focus is on mixtures: Some classes of properties

are examined: chemical potential, ideal solution, fugacity, partial
properties etc

1) Where chemical-engineering thermodynamics are often to systems wherein

composition is a primary variable.
2) In the chemical, petroleum, and pharmaceutical industries multicomponent
gases or liquids commonly undergo composition changes as the result of mixing
and separation processes, the transfer of species from one phase to another, or
chemical reaction.
3) Definition of a fundamental new property called the chemical potential, upon
which the principles of phase and chemical-reaction equilibrium depend.
4) This leads to the introduction of a new class of thermodynamic properties
known as partial properties.
6.2 FUNDAMENTAL PROPERTY RELATION

Equation (6.6) expresses the basic relation connecting the Gibbs energy to the
temperature and pressure in any closed system:

d(nG) = (nV)dP - (nS)dT (7.1)

For a more general case of a single-phase, open system material may pass into
and out of the system and 𝑛𝐺 becomes a function of the numbers of moles of the
chemical species present. It remains a function of T and P and we can therefore
write the functional relation:
(7.2)

Where 𝑛𝑖 is the number of moles of species 𝑖 and the total differential 𝑛𝐺 is then:

(7.3)

The summation is over all species present, and subscript 𝒏𝒋 indicates that all
mole numbers except the 𝒊𝒕𝒉 are held constant. The derivative in the final term is
given in its own symbol and name.
6.2 FUNDAMENTAL PROPERTY RELATION

By definition the chemical potential of species 𝒊 in the mixture is

(7.4)

(7.5)

(7.5)

(7.6)

Where 𝜇 is the chemical potential of species 𝑖

6.2 FUNDAMENTAL PROPERTY RELATION

(7.5)
(7.7)
6.3 CHEMICAL POTENTIAL AS A CRITERION FOR PHASE
EQUILIBRIA

(7.8)

α
α

The change in the total Gibbs energy of the two-phase system is the sum of the above
two equation for the separate phases. When equilibrium is achieved (P and T do not
change any more), it can be written:α

(7.9)
6.3 CHEMICAL POTENTIAL AS A CRITERION FOR PHASE
EQUILIBRIA

(7.10)

Hence in a two-phase mixture (system) the criterion for thermodynamic equilibrium is:
(7.11)

In general, multiple phases at the same T and P are in equilibrium when the chemical
potential of each species is the same in all phases.

(7.12)
6.4 PARTIAL PROPERTIES
6.4.1 DEFINITION

The definition of the chemical potential by as the mole-number derivative of 𝑛𝐺

suggests that other derivatives of this kind should prove useful in solution
Thermodynamics.
By definition, the partial molar property 𝑀𝑖 of species 𝑖 in solution is

(7.13)

It is sometimes called a response function, it is a measure of the response of total

property 𝑛𝑀 to the addition of an infinitesimal amount of species 𝑖 to a finite amount
of solution, at constant T and P. In summary the three kinds of properties used in
solution thermodynamics are distinguished using the following notation:
,V
, 𝑉𝑖
, 𝑉𝑖

The chemical potential and the partial molar Gibbs energy are identical, that is:
𝜇𝑖 ≡ 𝐺ഥ𝑖
(7.14)
6.4 PARTIAL PROPERTIES in BINARY SOLUTIONS
6.4.1 DEFINITION
6.4 PARTIAL PROPERTIES in BINARY SOLUTIONS
6.5 THE IDEAL GAS-MIXTURE MODEL
6.5 THE IDEAL GAS-MIXTURE MODEL
6.5 THE IDEAL GAS-MIXTURE MODEL
6.6 FUGACITY AND FUGACITY COEFFICIENT FOR
PURE SPECIES
6.6 FUGACITY AND FUGACITY COEFFICIENT FOR
PURE SPECIES
6.7 SUMMARY OF EQUATIONS FOR GIBBS ENERGY
AND RELATED PROPERTIES