CHEMICAL ENGINEERING

THERMODYNAMICS (CHE 301)

LECTURER
DR. O. J. ODEJOBI
08060790337
[email protected]
Lecture 1: General Concepts
Function of Thermodynamics
• “It is the function of thermodynamics to relate those properties of a
system required for practical or theoretical purposes to the
parameters that are mostly readily measured , and thus to provide
the maximum return of information for any investment in
experiment” – H. C. Van Ness.
Classical and Chemical Engineering Thermodynamics
• Classical Thermodynamics
• First/Second laws, essentially energy balance over a process, heat-
work, work-heat conversion device.
• PVT behavior, thermodynamics variables
Lecture 1: General Concepts
• Phase and Reaction Equilibria
• Application to Chemical Engineering Problems: work requirement and
heat effect in mixing and separation processes.
Thermodynamics of Pure Species
• Generic thermodynamics deals with properties estimates of pure
species. For example, steam tables for energy balance can be readily
used.
• Example
Lecture 1: General Concepts
Steam Flows through a pipe with a small pin hole
where the steam leakage occurs at the rate of
0.005kg/s at 1 bar
• What is the temperature of the leaking steam?
• In this case we are dealing with pure species
• Use steam Table, T= 518.47 K
• Will anything condense?
• Assuming we have mixture of chemical species
Lecture 1: General Concepts
Thermodynamics of Mixtures

• Gas Mixture: 85% CH4, 7% C2, 4% C3, 2% C4, 1% C5, 0.6% C6, 0.4% C7.
• What is the temperature T? Will anything Condense?
• The Calculation is no more straight forward!
Lecture 1: General Concepts
• 50 cm3 H2O + 50 cm3 C2H5OH mixture, final volume < 100 cm3
• Isopropanol + Methyl Ketone ΔV > 0
• Freezing point of water + Ethylene glycol < Freezing point of either
• Freezing point of C6H6 + C6F6 > Freezing point of either
• C6H6 : 278.7K; C6F6 : 278.1, Equi-molar: 297K
• Chemical industries deals with virtually infinite numbers of species
and their mixtures.
Thermodynamics and Reactions
• Blast furnace

• Gas leaving chimney contains considerable amount of ,

carrying away unutilized heat.
• Can we increase the conversion?
• Longer contact time: Furnace as long as 30 m were made in
England.
• Reaction is equilibrium limited (No improvement achieved)
• Enormous sum of money was wasted which could have been
prevented provided the laws of thermodynamics were
applied.
Role of Thermodynamics in Chemical
Engineering
• The two laws provide
1. constraints and inter-conversions between heat and work;
2. Basis for establishing state of pure substances and their mixtures;
3. Direction in which they move when stimulated by external force.
• Typical applications
1. Phase equilibrium (separation of components from mixtures)
2. Reaction equilibrium (ultimate extent of reaction)
• Play supervisory role.
• Necessary in design of equilibrium controlled operations.
• In design of rate controlled separations.
1. It sets the boundaries (driving force)
2. Processes are often treated as departure from equilibrium.
Feasibility of a Process
• For a process to be feasible, it must
1. obey the thermodynamics constraints.
2. operates at a reasonable rate so that the size of the equipment will be economical.
• Any process design usually involves a feasibility study before detailed design.
Engineering Aspect
• Measured variables: T, P, V, x (or y) and change in energy;
• Other variables like G, S, Fugacity, Activity Coefficient, etc are all “created” to
find easy solutions to thermodynamic problems in abstract domain;
• Thermodynamic in abstract domain is more or less solved using scientific
approach;
• Challenge lies in transforming the solution from abstract to practical domain
(engineering).
Course Objectives
• Provide undergraduate students with fundamental Engineering
Thermodynamics;
• Demonstrate the application of the fundamental concepts to a wide variety
of processes occurring in Chemical Engineering;
• Develop skills necessary to make appropriate assumption in specific
Chemical Engineering problems.
Expected outcomes
• Formulate and manipulate the thermodynamic treatment of processes;
• Formulate and analyse specific Chemical Engineering problems using
fundamental concepts;
• Select appropriate approximation for practical problem solving;
• Understand the implications of approximations on the efficiency and
accuracy of the solution.
Necessary Prior Knowledge
• Mass and Energy Balances;
• Differential and Integral Calculus;
• Spreadsheet software for simple calculations/graphing (MS Excel);
• Software for simple algebraic problems such as finding roots of
polynomial, solving simultaneous non-linear algebraic equations etc
(Octave/Matlab(R))
Learning Strategy
• Prepare to solve many problems per week;
• Practice as many problems from the textbook on the topic as you can;
• DO NOT randomly pick and equation from the textbook to solve problem;
• Understand where a particular equation coms from and the underling
assumption.
Books
• Introduction to Chemical Engineering Thermodynamics, J. M. Smith,
H. C. van Ness, M. M. Abott, Adapted by B. I. Bhatt (7th Ed.), Tata
McGraw Hill Pvt. Ltd (2004).
• Chemical Engineering Thermodymamics, YCU Rao (2nd Ed.)
Universities Press (1997).
• Introductory Chemical Engineering Throemodynamics, J. R. Elliot and
C. T. Lira (2nd Ed.), Pearson Education India Pvt. Ltd (2013).