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# UNIT III

SOLUTION THERMODYNAMICS
LESSON 12:
PARTIAL MOLAR PROPERTIES

Objectives:
 ∂(nM ) 

THERMODYNAMICS OF BIOLOGICAL SYSTEMS
· To define partial molar properties M ≡  (1.1)
 ∂ni 
i

· To understand the concepts of chemical potential and
fugacity this equation defines partial molar property of species i in
· Study ideal and non-ideal solutions solution, where the generic symbol i may stand for the partial
· Analyse and apply various composition models molar internal energy , the partial molar enthalpy, the partial
molar entropy ,the partial molar Gibbs energy ,etc.It is a
We have learnt that the applications of chemical-engineering
response function, representing the change of total property nM
thermodynamics are often to systems wherein composition is a
due to addition at constant T and P of a differential amount of
primary variable. In the chemical, petroleum, and pharmaceutical
species i to a finite amount of solution.Comparison of
industries multicomponent gases or liquids commonly
Equations written for the Gibbs energy show that the chemical
undergo composition changes as the result of mixing and
potential and the partial molar Gibbs energy are identical; i.e.,
separation processes, the transfer of species from one phase to
another, or chemical reaction. Because the properties of such µ i ≡ Gi (1.2)
systems depend strongly on composition as well as on Equations Relating Molar and Partial Molar
temperature and pressure, our purpose in this chapter is to Properties
develop the theoretical foundation for applications of thermo-
The definition of a partial molar property, Eq. (1.1), provides
dynamics to gas mixtures and liquid solutions.
the means for calculation of partial properties from solution-
The theory is introduced through derivation of a fundamental property data. Implicit in this definition is another, equally
property relation for homogeneous solutions of variable important, equation that allows the reverse, i.e., calculation of
composition. Convenience here suggests the definition of a solution properties from knowledge of the partial properties.
fundamental new property called the chemical potential, upon The derivation of this equation starts with the observation that
which the principles of phase and chemical-reaction equilibrium the thermodynamic properties of a homogeneous phase are
depend. This leads to the introduction of a new class of functions of temperature, pressure, and the numbers of moles
thermodynamic properties known as partial properties. The of the individual species which comprise the phase. Thus for
mathematical definition of these quantities allows them to be thermodynamic property M:
interpreted a properties of the individual species as they exist in
solution. For example, in a liquid solution of ethanol and water nM = Μ (T , P, n1 n 2. .......ni .....)
the two species have partial molar properties whose values are
somewhat different from the molar properties of pure ethanol The total differential of nM is:
and pure water at the same temperature and pressure.
 ∂(nM )  ∂(nM)  ∂(nM ) 
Property relations for mixtures of ideal gases are important as d (nM) = 
∂  dP +  ∂T  dT + ∑i ∂ni  P,T ,n dni
 P  T .n P,n
references in the treatment of real-gas mixtures, and they form
j

the basis for introduction of yet another important property, where subscript n indicates that all mole numbers are held
the fugacity. Related to the chemical potential, it is vital in the constant, and subscript nj that all mole numbers except nj are
formulation of both phase-and chemical-reaction-equilibrium held constant. Because the first two partial derivatives on the
relations. right are evaluated at constant n and because the partial deriva-
Finally, a new class of solution properties is introduced. Known tive of the last term is given by Eq. (1.1) this equation has the
as excess properties, they are based on an idealization of simpler form:
solution behavior called the ideal solution behavior called the  ∂M   ∂M 
ideal solution. Its role is like that of the ideal gas in that it d (nM) = n  ∂P  dP +n  ∂T  dT+ ∑iM i dni (1.3)
 T .x   P. x
serves as a reference for real-solution behavior. Of particular
interest is the excess Gibbs energy, a property which underlines Where subscript x denotes differentiation at constant composi-
the activity coefficient, introduced from a practical point of view tion.
in the preceding chapter. Since ni = xin
Partial Properties Dni = xi dn + n dxi
The definition of chemical potential as the mole number When dni is replaced by this expression, and d(nM) is replaced
derivative of nG suggests that other derivatives of this kind by the identity.
should prove useful in solution thermodynamics. d (nM) º n dM + M dn
Thus