Chemical Engineering

Thermodynamics (CB206)

Chemical and Biochemical Engineering

Indian Institute of Technology Patna

Atanu K Metya
atanu.metya@iitp.ac.in
 Chemical Engineering Thermodynamics

Phase Equilibrium

• Phase rule:

• Vapor/Liquid Equilibrium
 Chemical Engineering Thermodynamics

Low-Pressure Vapor/Liquid Equilibrium

Pxy diagrams at constant T: (a) tetrahydrofuran(1)/carbon tetrachloride(2) at 30°C; (b)

chloroform(1)/tetrahydrofuran(2) at 30°C; (c) furan(1)/carbon tetrachloride(2) at 30°C; (d)
ethanol(1)/toluene(2) at 65°C. Dashed lines: Px relation for Raoult’s law.
 Chemical Engineering Thermodynamics

Low-Pressure Vapor/Liquid Equilibrium

Txy diagrams at 101.3 kPa: (a) tetrahydrofuran(1)/carbon tetrachloride(2); (b) chloroform

(1)/tetrahydrofuran(2); (c) furan(1)/carbon tetrachloride(2); (d) ethanol(1)/toluene(2).
 Chemical Engineering Thermodynamics

Low-Pressure Vapor/Liquid Equilibrium

yx curves at 101.3 kPa:

(a) tetrahydrofuran(1)/carbon tetrachloride(2)
(b) chloroform(1)/ tetrahydrofuran(2)
(c) furan(1)/ carbon tetrachloride(2)
(d) ethanol(1)/ toluene(2)
 Chemical Engineering Thermodynamics

Thermodynamic Formulations for

Vapor/Liquid Equilibrium
 Chemical Engineering Thermodynamics

Excess Gibbs Energy And Activity Coefficients

 Chemical Engineering Thermodynamics

• The fundamental excess-property relation

• The summability and Gibbs/Duhem equations

 Chemical Engineering Thermodynamics

• Gamma/Phi Formulation of VLE

 Chemical Engineering Thermodynamics

Raoult’s Law

Modified Raoult’s Law

"!! and "!" vs x1 relationships for a Composition dependence of liquid-phase
binary liquid solution at constant T fugacities for species i in a binary solution.
 Chemical Engineering Thermodynamics

Henry’s Law

Henry’s law is related to the Lewis/Randall rule

through the Gibbs/Duhem equation
 Chemical Engineering Thermodynamics

Assuming that carbonated water contains only CO2(1) and H2O(2),

determine the compositions of the vapor and liquid phases in a sealed can
of “soda” at 25°C if the pressure inside the can is 5 bar. The vapor pressure
of water at 25°C is 0.0317 bar.
 Chemical Engineering Thermodynamics

Chemical-Reaction Equilibria
 Chemical Engineering Thermodynamics

• Reaction Coordinate

ε is called the reaction coordinate

• Multireaction Stoichiometry
 Chemical Engineering Thermodynamics

The following reaction occurs in a system initially consisting of 2 mol CH4,

1 mol H2O, 1 mol CO, and 4 mol H2:
CH4 +H2O→CO+3H2
Determine expressions for the mole fractions yi as functions of ε.
 Chemical Engineering Thermodynamics

Consider a vessel that initially contains only n0 mol of water vapor. If

decomposition occurs according to the reaction
H2O → H2 + 1/2 O2
find expressions that relate the number of moles and the mole fraction of
each chemical species to the reaction coordinate ε.
 Chemical Engineering Thermodynamics

Consider a system in which the following reactions occur:

CH4 +H2O→CO+3H2 (1)
CH4 +2H2O→CO2 +4H2 (2)
where the numbers (1) and (2) indicate the value of j, the reaction index. If 2
mol CH4 and 3 mol H2O are initially present, determine expressions for the
yi as functions of ε1 and ε2.
 Chemical Engineering Thermodynamics

Equilibrium Criteria

• Equilibrium Criteria to Chemical

Reactions
 Chemical Engineering Thermodynamics

Standard Gibbs-energy Change and the Equilibrium Constant

• A criterion of chemical-reaction equilibrium

K is called the equilibrium constant for the reaction

ΔG° is called the standard Gibbs-energy change of reaction

Relation between the standard heat of reaction and the standard Gibbs-energy change
of reaction
 Chemical Engineering Thermodynamics

Phase Rule and Duhem’s Theorem for Reacting Systems

• The phase rule

• The phase rule for reacting systems

r: independent chemical reactions at
equilibrium within the system

• The more general form of the phase rule that results is:

s: special constraints