Chemical Engineering

Thermodynamics
Yang, Yanhui

Textbooks

Prescribed text:
Smith JM, Van Ness HC and Abbott MM, "Introduction of Chemical
Engineering Thermodynamics McGraw Hill, 7th Edition (2001). (7th
Edition in SI units is available)

References:
S. I. Sandler, Chemical and Engineering Thermodynamics, 2nd,
Edition, Wiley, (2001)
J.R. Elliot and C.T. Lira, Introductory Chemical Engineering,
Thermodynamics, 1st edition, Prentice Hall PTR, (1999)
Rogers G F C and Mayhew Y R Thermodynamic and Transport,
Properties of Fluids (SI Units) 5th Edition, Oxford Basil Blackwell
(1995)
Handbook of Chemistry and Physics, 81st Edition, Lied, D.R. Ed.; CRC
Press: Boca Raton (2000/2001)
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Organization
Instructors:
Dr. Yanhui Yang (N1.2-B1-18)
yhyang@ntu.edu.sg
Office #: +65 6316 8940
Lectures:
Wednesday 9:30-11:30, LT22
Tutorials:
Thursday 11:30-1:30, TR20
Thursday 2:30-4:30, CBE-SR3
Friday 12:30-2:30, TR20

Assessment

Final examination: ~60%

Midterm examination: ~40%

Contents
Review of fundamentals and thermodynamics laws
Concepts, 0th, 1st, 2nd, and 3rd law, reversibility, entropy, etc.
Refrigeration and liquefaction
Reverse Carnot cycle- Carnot refrigeration cycle, the vapor
compression cycle, general methods of liquefaction, industrial
liquefaction processes
PVT relationships, thermodynamics properties, property
relations
Equation of state, PVT relationships for pure substances,
residual properties, evaluation of residual properties, chemical
potential, fugacity
Fundamental thermodynamic property relations
Property relations, properties of homogeneous fluids of constant
composition, properties of homogeneous fluids of variable
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composition

Contents (cont.)
Solution Thermodynamics: Theory
Equilibrium criteria, thermodynamics of mixtures, partial molar
quantities, ideal gas mixtures, ideal solutions, non-ideal
mixtures, ideal phase equilibrium
Solution Thermodynamics: Application
Excess properties and activity coefficients, models for excess
properties, margules model, van Laar model, heat effects of
mixing processes
Chemical Reaction Equilibrium
Criteria for chemical equilibrium with reactions, standard states
and heat of reaction, equilibrium compositions

Introduction
Application of chemical engineering thermodynamics:
Analysis of processes and process equipment using basic laws of
thermodynamics and property relations of thermodynamics
Work production and work requirement processes and process
equipment.
Heat (energy) requirement of the processing units.
Equilibrium distribution/composition in physical unit operations
(problems involving phase equilibrium).
Equilibrium conversion/composition in chemical reactor (problems
involving chemical reaction equilibrium).
Energy conversion: conversion of heat to work by power cycles;
heating and refrigeration.
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Introduction
Limitations of chemical engineering thermodynamics:
Laws of thermodynamics are laws of nature and cannot be proven.
General property relations derived from basic laws are complex and
may contain unknown parameters that needed to be determined
independently.
Some basic thermodynamics properties are conceptual properties
and cannot be measured by any physical means.
Chemical engineering thermodynamics answers the questions how
far?, but not how fast? and how?.

0th law of thermodynamics

Thermodynamics equilibriums:

Thermal equilibrium.
Mechanical equilibrium.
Chemical equilibrium.
Physical equilibrium.

0th law of thermodynamics is a generalized principle of thermal

equilibrium among bodies, or thermodynamic systems in contact.
It states that if two systems are in thermal equilibrium with a third
system, they are also in thermal equilibrium with each other.
0th law is more fundamental than the 1st law but it was discovered
after the other three.

1st law of thermodynamics

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1st law of thermodynamics

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1st law of thermodynamics

Of the three terms in the 1st law, only work has a precise definition
from mechanics:

, F refers to generalized force, while dL means

generalized displacement on extensive variable
In this module, we are interested in the pressure-volume work,

Negative sign is necessary when dV0, dW0 (surroundings does

work on system. When dV0, dW0, system does work
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1st law of thermodynamics

Heat is all the remaining modes of energy transfer that cannot be

expressed as work. There turn out to be microscopic work interactions
that allow energy exchange between the system and its surroundings.
Consider two systems separated by a diathermal wall. Total system is
isolated and the wall is rigid. A and B undergo an interaction that causes
a change in their properties.
A
B
By 1st law:

+ =0
QA
QB
=
;

When 0, we say energy is transferred from A to B in the form of

heat.
Intuitively we know that if A is hotter than B, molecules in A are moving
faster than B and there are collisions between A and B which transfer
momentum from A to B, Net result of many such collisions is heat
transfer.
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1st law of thermodynamics

Sign convention for heat, Q

Heat is transferred into the system, Q is positive.
Heat is transferred out of the system, Q is negative.
Sign convention for work, W
Work is done upon the system by the surroundings, W is
positive.
Work is done by the system on the surroundings, W is negative.

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1st law of thermodynamics

Example
Hold a piece of ice in your hand until it melts

Solution A
System: You; surroundings: Ice + the rest of the universe
q < 0: Heat flows out of the system (you) into the ice.
Solution B
System: Ice; surroundings: You + the rest of the universe
q > 0: Heat flows into the system (ice) from you.

You can see that the answer changes depending upon how you
define the system, but the physical reality is exactly the same, but
both solutions A and B are correct. It doesnt matter how you define
the system as long as you are consistent.

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1st law of thermodynamics

First law for open systems
System: fluid showing in the piping network between inlet (position
1) and outlet (position 2)

rate of mass accumulation within the control volume.

rate of energy accumulation within the control volume.

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1st law of thermodynamics

Mass balance: from law of mass conservation

Continuity equation:
At steady state:
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1st law of thermodynamics

Energy balance, from first law, the change in total energy of the
universe is zero:

Change in total energy of the system neglecting other forms of

energy:

Change in total energy of the surroundings:

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1st law of thermodynamics

The net work term for a flow process includes both shaft work and
PV-work (flow work):

Based on energy conservation:

Based on definition of enthalpy: H=U+PV

Neglecting kinetic and potential energy change

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