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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)
2
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
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
5
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?.
Thermodynamics equilibriums:
Thermal equilibrium.
Mechanical equilibrium.
Chemical equilibrium.
Physical equilibrium.
10
11
Of the three terms in the 1st law, only work has a precise definition
from mechanics:
+ =0
QA
QB
=
;
14
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.
15
16
Continuity equation:
At steady state:
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Energy balance, from first law, the change in total energy of the
universe is zero:
18
The net work term for a flow process includes both shaft work and
PV-work (flow work):