SECOND LAW OF THERMODYNAMICS………89–125 4.1 Limitations of the First Law of Thermodynamics……89 4.1.1 Direction of Change……89 4.1.2 Qualitative Difference between Heat and Work……90 4.2 General Statements of the Second Law of Thermodynamics……90 4.2.1 The Equivalence of the Kelvin and Clausius Statements……91 4.3 Entropy……92 4.3.1 Why the Concept of Entropy?……92Ĥ.3.2 Entropy and Heat……93 4.3.3 Entropy and Temperature……94 4.3.4 Entropy and the Nature of the Process……94 4.4 The Carnot Principle……95 4.4.1 Thermodynamic Temperature Scale……97 4.4.2 Ideal Gas as the Carnot Engine Working Substance……98 4.5 Entropy-A State Function……101 4.6 Calculation of Entropy Changes……103 4.6.1 Phase Change……103 4.6.2 Processes Involving Ideal Gases……103 4.6.3 Adiabatic Mixing Process……105 4.6.4 Isothermal Mixing of ideal Gases……106 4.6.5 Chemical Reactions……107 4.7 Clausius Inequality……108 4.8 Mathematical Statement of the Second Law of Thermodynamics……111 4.9 Entropy and Irreversibility……115 4.10 Statistical Explanation for Entropy……118 4.11 Third Law of Thermodynamics……118 Summary……120 Review Questions……121 Exercises……122 5. P-V-T BEHAVIOUR AND HEAT EFFECTS………49–88 3.1 P-V-T Behaviour of Pure Fluids……49 3.2 Equations of State and the Concept of Ideal Gas……51 3.3 Processes involving Ideal Gases……52 3.3.1 Constant Volume Process……52 3.3.2 Constant Pressure Process……53 3.3.3 Constant Temperature Process……54 3.3.4 Adiabatic Process……55 3.3.5 Polytropic Process……57 3.4 Equations of State for Real Gases……60 3.4.1 Limiting Conditions……61 3.4.2 van der Waals Equation……61 3.4.3 Redlich–Kwong Equation……63 3.4.4 Redlich–Kwong–Soave Equation……64 3.4.5 Peng–Robinson Equation……64 3.4.6 Benedict–Webb–Rubin Equation……64 3.4.7 Virial Equation……65 3.5 Compressibility Charts……67 3.5.1 Principle of Corresponding States……68 3.5.2 Generalised Compressibility Charts……69 3.6 Heat Effects accompanying Chemical Reactions……69 3.6.1 The Standard Heat of Reaction……69 3.6.2 The Standard Heat of Combustion……70 3.6.3 The Standard Heat of Formation……70 3.6.4 Hess’s Law of Constant Heat Summation……71 3.6.5 Effect of Temperature on Standard Heat of Reaction……72 3.6.6 Temperature of Reaction……77 Summary……79 Review Questions……80 Exercises……81 4. FIRST LAW OF THERMODYNAMICS………24–48 2.1 General Statements of First Law of Thermodynamics……24 2.2 First Law of Thermodynamics for Cyclic Process……25 2.3 Internal Energy……25 2.4 First Law of Thermodynamics for Non-flow Process……26 2.5 Enthalpy……31 2.6 First Law of Thermodynamics for Flow Process……34Ģ.7 Heat Capacity……40 Summary……44 Review Questions……44 Exercises……45 3. INTRODUCTION AND BASIC CONCEPTS………1–23 1.1 Scope and Limitations of Thermodynamics …… 1 1.2 Definitions and Fundamental Concepts……2 1.2.1 Systems and Processes……2 1.2.2 Homogeneous and Heterogeneous Systems……3 1.2.3 Closed and Open Systems……3 1.2.4 State and Properties……3 1.2.5 Intensive and Extensive Properties……4 1.2.6 State and Path Functions……4 1.3 Force, Pressure and Energy……5 1.3.1 Force……5 1.3.2 Pressure……5 1.3.3 Energy……6 1.4 Equilibrium State and the Phase Rule……10 1.4.1 Steady State……10 1.4.2 Equilibrium State……10 1.4.3 Phase Rule……11 1.5 Temperature and Zeroth Law of Thermodynamics……11 1.5.1 Zeroth Law……11 1.5.2 Temperature……11 1.5.3 Ideal Gas Temperature Scale……12 1.6 Heat Reservoirs and Heat Engines……14 1.6.1 Heat Reservoir……14 1.6.2 Heat Engine……14 1.6.3 Heat Pump……15 1.7 Reversible and Irreversible Processes……16 Summary……20 Review Questions……21 Exercises……22 2. Ltd., New Delhi-110020.Ĭontents Preface xiii Preface to the First Edition xv 1. Ghosh, PHI Learning Private Limited, Rimjhim House, 111, Patparganj Industrial Estate, Delhi-110092 and Printed by Mohan Makhijani at Rekha Printers Pvt. ISBN-978-8-2 The export rights of this book are vested solely with the publisher. No part of this book may be reproduced in any form, by mimeograph or any other means, without permission in writing from the publisher. © 2013 by PHI Learning Private Limited, Delhi. NARAYANAN Former Professor and Head Department of Chemical Engineering and Former Principal Government Engineering College Thrissur, KeralaĪ TEXTBOOK OF CHEMICAL ENGINEERING THERMODYNAMICS, Second Edition K.V.
A Textbook of Chemical Engineering Thermodynamics SECOND EDITION