Lecture 1.

Solution
Thermodynamics: Introduction
CH127 - MODULE 1
 Introduction
theoretical foundation for applications of thermodynamics to gas mixtures and
liquid solutions.
 Fundamental property relation - to open phases of variable composition
 Chemical potential - facilitates treatment of phase and chemical-reaction
equilibria. ∙
 Partial properties - distribute total mixture properties among individual
species
 Property relations for the ideal-gas-state mixture - provide the basis for
treatment of real-gas mixtures.
 Fugacity ~ chemical potential - mathematical formulation of both phase-
and chemical-reaction-equilibrium problems. ∙
 Excess properties (of solutions) & the ideal-solution model - which serves
as a reference for real-solution behavior
 1.1 Fundamental Property Relations
 for single-phase fluid systems of variable mass and composition.
 foundation upon which the structure of solution thermodynamics is built

 (10.2)

 For the special case of one mole of solution, n = 1 and

 (10.3)

 Gibbs energy - function of its canonical variables (T, P, : it serves as a generating function,
providing the means for the calculation of all other thermodynamic properties ~ it implicitly
represents complete property information.
 1.2 Chemical Potential and equilibria
 General criterion for chemical-reaction equilibrium in a single-phase closed PVT
system,
 Basis for the development of working equations (WEs) for the solution of
reaction-equilibrium problems

 With respect to (wrt) phase equilibrium:

for a closed nonreacting system consisting of two phases in equilibrium 
each individual phase is open to the other, and mass transfer between phases may
occur

(10.6)

Multiple phases at the same T and P = in equilibrium when the chemical potential
of each species is the same in all phases.
 Nature of Equilibrium
Equilibrium – no change occur in macroscopic properties of an isolated system
with time
-

Initial state – there is intimate

“Isolated system”
mixing (i.e., vapor and liquid and
hence, maximum disorder – with
increasing entropy, S
Characterized by P, V, T,
& N-1 ( number of species)

x = fraction in liquid phase

Application in
distillation, y = fraction in vapor phase
absorption, chemical
reaction
 1.3 Partial Properties
 Partial molar property, , of species in solution:

 (10.7)

 A response function - 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.
 M = solution specific property per unit mass (m) or mole (n)
 = specific properties of individual species “ i ” as they exist in the pure state (at T, P of sol’n)
 (10.8)
 A Rationale for Partial Properties
 a solution property represents a “whole,” i.e., the sum of its parts as represented by partial properties
of the constituent species

 = true mixture property

 Gibbs/Duhem : shows that the partial properties of species making up a solution are not
independent of one another;
1.4 THE IDEAL-GAS-STATE MIXTURE MODEL
 A partial molar property (other than volume) of a constituent species in an ideal-gas-state
mixture is equal to the corresponding molar property of the species in the pure ideal-gas state at
the mixture temperature but at a pressure equal to its partial pressure in the mixture.

Ideal-gas-state mixture model:

 Volume of molecules = zero volume t
 No interaction with other species in the mixture

Thermodynamic properties (other than molar volume) of the constituent species are
independent of one another, and each species has its own set of private properties.
 Partial Molar property of Ideal Gas in the Mixture
 equal to the corresponding molar property of the species in the pure ideal-gas state at the
mixture temperature but at a pressure equal to its partial pressure in the mixture.
 Other than volume:

 (10.21) Example
and other properties independent of pressure.

(Entropy of an Ideal gas depend on pressure: ,

(10.23)
Ideal gas Mixture Solution Properties
 1.5 The Phase Rule
Consider, non-reactive system under equilibrium:
π = no. of phases each containing N independent chemical species
F = degrees of freedom for the system, i.e., the number of intensive variables that may vary
independently of each other would be given by:

For the system of interest:

 Number of phase rule variables, PRV, (intensive variables)  T, P and (N-1) species mole fractions for
each of the  π phases)

PRV = 2 + (N-1) π

Number of independent phase rule equations, PRE, (relations connecting the phase rule variables)
PRE = (π – 1) N

Degrees of freedom = Total number of systemic intensive variables – number of independent equations relating all
the variables.

F = 2 + (N-1) π - (π – 1) N = 2 - π + N = no. of variable that may be independently fixed

PRE = follows from the fact that for each of the N species one may use the chemical potential equality relation
across all   phases,
 
= for each component there can be only  be ( π – 1 ) independent relations
Special case of Phase Rule:
For closed system:
Initial mass = fixed  both extensive state & intensive state of system are fixed and
state of system is completely determined. No. of extensive
variables
Characterized by: Total number of variables = 2 + (N-1) π + π = 2 + Nπ

PRV, No. of intensive variables

No. of phase equilibrium eqns.: = (π – 1) N + N = πN

No. of material balance eqn.
for each of the N species
PRE, independent equations
Total variables = (2 + Nπ) - πN
=2
 Gibbs-Duhem Theorem
For any closed system formed initially from given masses of a
number of chemical species, the equilibrium state is completely
determined when any two independent variables are fixed.
 The two independent variables: may be either intensive or
extensive.
 Number of independent intensive variables = given by the
phase rule
when F = 1, at least one extensive, and
when F = 0, both must be extensive
 Description of General VLE Behavior
To understand behavior of multicomponent system, consider a binary system:
The considerations for such a system may, in principle, be generalized to understand
the behavior of multi-component systems.
 
When N = 2,  F = 4 – π; if π = 2 phases ,
F = 4 – 2 = 2 , independent intensive variables
For Extractive distillation:
No. of phases, π = 2 liquid phases + 1 vapor phase = 3

hence, F = 2 + 2 - 3 = 1;

Let: Component 1 = more volatile component

Phase rule variables: T, P, y1 and x1.
For example at a given T, one may plot two curves, P vs. x1 (or in short P-x1)
and P vs. y1. 
Similarly, given P, one may plot T vs. x1 and T vs. y1. 
In addition if one fixes either x1 or y1one may plot P-T diagrams. The
combination of these diagrams lead to a 3-dimensional surface involving
pressure, temperature and phase compositions on the three axes.
 Phase Rule

 Phase Rule – for nonreacting systems

 Degrees of Freedom, F = number of variables that
maybe independently fixed to define the state of the
system
 Gibb’s Phase Rule
 The Gibbs phase rule is a very useful equation because it put precise
limits on the number of phases P that can be simultaneously in
equilibrium for a given number of components, C.

F=2+C−P (1)
Where:
 F= degrees of freedom
 P= number of phases
 C= no of components
 Gibbs Phase Rule

A single component phase diagram. On the right figure, the color represents
a molar extensive quantities (i.e., blue is a low value of V and red is a large
value of V ) that apply to each phase at that particular P and T.
Single Phase

 Consider a single-phase region: P = 1,

 F = 2 + C – P = 2 + 1 -1 = 2
 two variables (P and T) can be changed independently (i.e., pick
any dP and dT) and a single phase remains in equilibrium.
 Degrees of Freedom
Consider where two phases are in equilibrium:

F = 2 + C – P = 2 + 1- P = 1,

 only one degree of freedom – for the two phases to remain in

equilibrium,
 one variable can be changed freely (for instance, dP)
 the change in the other variable (i.e., dT) must depend on the
change of the free variables:
Three Phases

 Consider where three phases are in equilibrium then:

 F = 2 + C – P = 3 + = 0.

 There can be no change any variable that maintains

three phase equilibrium.
 Various Confusing Issues on Applications of F + P=
C+2
 Consider a pure liquid A in contact with the air.
 The degrees of freedom can be determined in several
equivalent ways.
 a. Consider the system composed of two components, C = 2,
the pure liquid A and air and restrict that the total pressure is 1
atm.
 (F + P = C + 2) → (F + P = C + 1).
 Therefore, F = 2 + 1- 2 + 1 = 1
 C=3
 b. Considering that the system consists of three
components: A, O2, N2 and
 has two additional restrictions:
1.) ΣP = 1
2.) = constant,
 then (F + P = C + 2) → (F + P = C + 0).
 F = 3 +0 - 2 = 1 as before.
c. Disregard the air:
C = 1, P = 2, and therefore, F = 1.

The liquid has an equilibrium vapor pressure which is a

function of temperature.

One can pick either the vapor pressure or the

temperature independently, but not both.
 Single Component Phase Equilibria
 When there is only one degree of freedom in a single component phase
diagram, it was shown above that there must be a relation between dP and dT
for the system to remain in two phase equilibrium. Such a relation can be
derived as follows:

Clausius Clapeyron Equation

 Behavior of G = µ at constant P as a function of T. Where
the curvature of G changes sign, the system is unstable. The
Considerations of the molar Gibbs liquid and vapor curves must be connected to each other
free energy on slices of the single and this is illustrated with the ”spiny-looking” curve with
component phase diagram along opposite curvature. The curve for solid is not connected to
lines of constant T and constant P the others.
Behavior of G = µ at
constant T as a
function of P

Example of single
component phase diagram
plotted with one derived
intensive variable.