Chemical Engineering Thermodynamics-II

Lecture-1 Introduction
(Thermodynamics & its applications)

Prof.Hitesh N. Panchal
Department of Chemical Engineering
FOT, D. D. University
Nadiad-387001
 Outline of presentation
 The Chemical Industry
 Introduction
 Macroscopic Vs Microscopic
 Basic concepts
 Laws of thermodynamics
 Course contents
 Text and Reference Books
 The Chemical Industry

 Raw Materials: Oil, Natural gas, Coal, biomass, rock salt,

sulphur, air etc.
 Major Fuels: LPG, gasoline, diesel, kerosene
 Bulk chemicals: Base chemicals(20)
Intermediates(300)
 Specialty chemicals:
made from bulk chemicals
Industrial Separation Processes
 Separation Processes Expensive?

 Most chemicals do not occur in their pure state in nature

 Separation processes contribute a major part to the cost of

manufacturing chemicals
 70% of the capital investment in the petroleum and petrochemical
industry is on equipment alone
 These equilibrium properties are required for the design of
separation operations (which count for 40-80% of investment of a
chemical plant)
 Introduction

 In basic thermodynamic course, we study relations between

states of a system that undergo certain processes.
 One can apply laws of thermodynamics to both reversible
and irreversible processes to get information about
 What is power requirement or power obtained
 What is the amount of heat absorbed or dissipated
 What is the value of an unknown property (such as temperature) of
the final (or initial state), etc.
 In this course, we use thermodynamics to obtain – composition of
a mixture when it attains equilibrium between coexisting phases
especially when the phases are non-ideal and mixtures are
multicomponent mixtures.
 Introduction(Contd.)

 Chemical Engineering deals with species chemically react to form

a desired product.
 Product must be separated from other by-products and unreacted
reactants.
 Generally separation methods involve contact or formation of
different phases through which one species of a mixture
preferentially segregates.
 Industries have to follow pollution board regulations, cleaning
contaminated environments also requires separation methodology.
 Thus, it is important to estimate the degree to which species
transfer into a different phase as function of processing conditions.
 Introduction(Contd.)

 The aim is to calculate how species distribute among phases

when more than one phase is present (coexist)
 These calculations are restricted to equilibrium systems
 Therefore, they give information on
 direction of the driving force for a given system (i.e., the
system will spontaneously move toward its equilibrium state)
but no information on rate at which it will reach equilibrium.
 Important aspects

 We deal with the processes

 Whether process feasible
 If feasible, how much energy needed
 What fraction of raw materials will be converted to products
 Time required to produce specified quantity of products
 Effect of physical properties on the extent to which the process
will proceed
 Available alternative processes and the best among them.
 Main purpose
 Criteria of equilibrium
 Designs and develops new processes or improve the existing
once
 Macroscopic Vs Microscopic

Macroscopic property Microscopic property

(Classical Thermodynamics) (Statistical Thermodynamics)
Structure of matter not Knowledge of structure of
considered matter essential
Only a few variables used to Large number of variables
describe state of matter under required for complete
consideration specification of state of matter
under consideration
Values of variables used to Variables used not measured
describe state easily measurable easily and precisely
 Basic concepts

System
Surroundings
Boundary
Types of system
Thermodynamic variable
Thermodynamic process
Types of process
Thermodynamic equilibrium
State function and path function
Intensive & extensive properties
 Basic concepts(Contd.)

 Extensive properties
 Volume, mass, amount (mole),
 energy, enthalpy, entropy, free energy, heat capacity
 Intensive properties
 Molar volume, density, molar
 mass, molarity, mole fraction,
 molality, specific heat capacity
 Basic concepts(Contd.)

 A general statement: The ratio of two extensive properties is

an intensive property.

 Density is an intensive property

 Volume (extensive property)/Mass (extensive property) =
Density (intensive property)
 Molarity is an intensive property
 Mole of the solute (extensive property) /Volume of solution
(extensive property)= Molarity (intensive property)
 Laws of Thermodynamics

 Thermodynamics is a science dealing with

 Energy and its transformation(1st Law)
 Entropy & Equilibrium Process(2nd and Zerothth Law)
 Entropy(3rd Law)
 All these four laws are based on the experimental observations
which can not be proved directly.
 Thermodynamic properties

 Measurable properties
 Pressure
 Temperature
 Non-measurable properties
 Entropy
 Internal energy
 Enthalpy
 Gibbs free energy
 Helmholtz free energy
 Course Contents

Unit 1: Systems of Variable Composition-Ideal behavior

 Introduction, Fundamental property relation.

 Property changes for mixing of an ideal gaseous mixtures and ideal
solution.
 The concept of chemical potential, Concept of equilibrium, Criterion of
phase equilibrium criterion in terms of chemical potential.
 Vapor-liquid equilibrium(VLE) model for ideal solution-Raoult’s law
and its applications
 VLE phase diagrams for binary mixtures-Pxy , Txy and xy diagrams.
 VLE calculations- Bubble point, Dew Point and Isothermal Flash
Calculation
 Course Contents(Contd.)

Unit 2: Systems of Variable Composition-Non-Ideal behavior

 Introduction, Concept of partial properties and determination of partial

properties.
 Concept of fugacity & fugacity coefficient, evaluation of fugacity
coefficient – for a pure component, for a mixture of gases & for liquids,
effect of temperature & pressure on fugacity & fugacity coefficient of a
pure component as well as a gaseous mixture
 Concept of activity & activity coefficient, Lewis – Randall rule &
Henry’s law, excess properties.
 Relationship between excess Gibbs free energy and activity coefficient.
 Determination of Activity coefficient from VLE data.
 Course Contents(Contd.)

Unit 3: Phase Equilibria at low to moderate pressure

 Phase rule, Duhem’s theorem, Gibb’s – Duhem equation.

 Phase diagrams for miscible systems, phase diagrams for
immiscible systems, phase diagrams for partially miscible systems,
testing of vapour – liquid equilibrium data.
 Excess Gibbs free energy models(Activity models) such as
Redlich-kister equation, Wohl’s equation,Van Laar equation,
Margule’s equation, Wilson equation, NRTL, UNIQUAC &
UNIFAC and evaluation of constants in these equations.
 P-x,y & T-x,y & x-y diagrams, Positive & negative deviations from
Raoult’s law.
 Course Contents(Contd.)

Unit 4: Solution Thermodynamics

 Methods for Vapor liquid equilibrium calculations

 VLE calculations at high pressures using K values.
 Thermodynamic consistency of VLE data.
 Fundamental Excess-property relation.
 Property changes of mixing process non-ideal solution.
 Heat effects of mixing processes.
 Equilibrium & stability.
 Course Contents(Contd.)

Unit 5: Chemical Reaction Equilibria

 Introduction, Criteria for chemical equilibrium.

 Concept of Equilibrium conversion (x), equilibrium constant
(k), effect of temperature & pressure on k, evaluation of
equilibrium constants by various methods.
 Evaluation of equilibrium conversion for gas phase reactions,
liquid phase reaction, heterogeneous reactions etc.
 Phase rule for chemically reacting systems.
 Course Contents(Contd.)

Unit 6: Introduction to Statistical Thermodynamics

 Introduction to Statistical thermodynamics and

probability theory.
 Different thermodynamic distributions like Boltzmann
distribution, Bose – Einstein distribution, Fermi – Dirac
distribution, corrected Boltzmann statistics.
 Laws of thermodynamics,Partition function, evaluation
of properties for monoatomic gases using partition
function.
 Text and Reference Books
Text Books:
 Smith, J. M.; Van Ness, H. C. Introduction to Chemical Engineering Thermodynamics;
Fourth Edition, McGraw Hill Book Company: Singapore, 1987.
 Sonntag, R. E. & Van Wylen, Gordon J. Fundamentals of Statistical Thermodynamics
 First Edition, John Wiley & Sons: United States of America, 1968.

Reference Books:
 Narayan, K. V. A Textbook of Chemical Engineering Thermodynamics; Second Edition,
PHI Learning Private Limited: Delhi, 2013.
 Rao,Y.V.C.Chemical Engineering Thermodynamics; First Edition, Universities Press
India Private Limited : Hyderabad,1997.
 Elliot, J.E.; Lira C.T. Introductory Chemical Engineering Thermodynamics; Second
Edition, Pearson Education publishing as Prentice Hall: South Africa, 2012.
 M. D. Koretsky, Engineering and Chemical Thermodynamics , Wiley India, 2004.
Thank you