Phase Equilibria

Basic Concepts
Course Content
 Phase Equilibria: Basic Concepts
 Low / High Pressure Vapour Liquid Equilibria
 Stability of Thermodynamic Systems
 Liquid-Liquid Equilibria
 Vapor-Liquid-Liquid Equilibrium
 Solid-Liquid Equilibria
 Solid-Gas Equilibria
 Chemical Reaction Equilibria
 Thermodynamics of Electrolyte Systems
 Interfacial Thermodynamics
 Thermodynamics of Bio-systems
 Introduction to Molecular / Statistical Thermodynamics
Thermodynamic Equilibrium
 Annulment of all types of gradients within a system

 A combination of:

 Mechanical Equilibrium

 Thermal Equilibrium

 Chemical Equilibrium
Equilibrium and Rate Processes
 Why phase equilibria?

 Need for enrichment by separation in process operation: raw

material purification & product enrichment

 Need for at least two or more phases

 Why consider the equilibrium state?

 Phase equilibria: mathematical relationship between system

parameters across different phases: T, P and composition {xi, yi, zi…}

 Thermodynamics and Transport Phenomena

Types of Equilibrium for Mechanical
and Chemical Systems

Unstable Metastable Stable Equilibrium States

Types of Equilibrium for Mechanical and
Chemical Systems

Potential Energy and Gibbs Free Energy

Macroscopic vs Statistical Equilibrium
 Macroscopic: static (non-changing state parameters)

 Statistical: dynamic (microscopic fluctuations in local density and

molecular energy)

 Convergence between the two types of equilibrium

Macroscopic vs Statistical Equilibrium

 Convergence between the two types of equilibrium: heat and

mass flows)
Vapour Liquid Equilibria : Statistical
interpretation
Chemical Reaction Equilibrium:
Macroscopic and Statistical Interpretations
The Origins of Non-ideal Behaviour of Fluids
The Ideal Gas
 Molecules have no dimension
 Molecules do not interact: there is no intermolecular energy
 Ideal gas EOS: PV = RT
The Non-Ideal Gas
 Earliest correction: VdW EOS
The Non-Ideal Gas
 Generalized correlation: PV = ZRT
 Subsequent corrections: Soave-Redlich-Kwang; Peng-Robinson, etc
Intermolecular Forces:
The Origin of Non-ideality
 Existence of both attractive and repulsive intermolecular forces
 Macroscopic behavioural evidence? Phase change!
Intermolecular Forces
Attractive intermolecular forces are categorized into the following types:
• Hydrogen bonding
• van der Waals forces:
- Keesom force
- Debye force
- London dispersion force

• Ionic bonding
• Ion–induced dipole forces
• Ion–dipole forces
Intermolecular Forces and Energy
 Intermolecular repulsive force: overlap of electron clouds
(Born repulsion)
Ideal and Non-ideal Solutions
 Can a pure liquid be ideal (as a gas)?
 Ideal and non-ideal solutions
Ideal and Non-ideal System VLE
Other phase equilibria
Key Conclusions
 Macroscopic and statistical descriptions of equilibrium are
convergent

 Equilibrium considerations needed to obtain maximum

degree of separation and reaction

 Actual design of process systems determined both by

thermodynamics and transport phenomenon