Chemical Engineering Thermodynamics
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1 Chemical Engineering Thermodynamics P Liquid P x 1 sat P 1 T sat T 2 T x 1 T x 1 T y 1 Liquid Vapour sat P 2 P x 1 P y 1 P y 1 Vapour sat T 1 x, y 1 1 x, y 1 1 Pradeep Ahuja
2 Contents CHEMICAL ENGINEERING THERMODYNAMICS i PRADEEP AHUJA Reader Department of Chemical Engineering and Technology Institute of Technology, Banaras Hindu University Varanasi New Delhi
3 CHEMICAL ENGINEERING THERMODYNAMICS Pradeep Ahuja 2009 by PHI Learning Private Limited, New Delhi. All rights reserved. No part of this book may be reproduced in any form, by mimeograph or any other means, without permission in writing from the publisher. ISBN The export rights of this book are vested solely with the publisher. Published by Asoke K. Ghosh, PHI Learning Private Limited, M-97, Connaught Circus, New Delhi and Printed by Baba Barkha Nath Printers, Bahadurgarh, Haryana
4 To All My Students
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6 Contents Preface Nomenclature xv xvii 1 Introduction Equilibrium State and Steady State Systems and Surroundings Processes Internally Reversible Process About Steam Tables Degrees of Freedom Total Volume and Molar/Specific Volume Dryness Fraction Extensive and Intensive Properties Non-flow and Flow Processes Work Done During Internally Reversible Non-flow Process State and Path Functions Useful Work Gauge and Vacuum Gauge Pressures Mechanical Energy of a Fluid T-V Diagram of a Pure Substance P-V Diagram of a Pure Substance P-T Diagram of a Pure Substance Boiling Point of Pure Substances Internal Energy and Enthalpy Heat Capacities Ideal Gases Incompressible Liquids and Solids 29 v
7 vi Contents 1.22 Enthalpy of Compressed Liquid Roots of Non-linear Equation 32 Summary 34 Exercises 35 2 Equations of State Virial Gas Equation of State Law of Corresponding States Acentric Factor Molar Volume Calculations Using Virial Equation of State Virial Equation of State for Binary Mixtures Virial Mixing Rules Pseudo-reduced Method Conclusions of Virial Equations of State Cubic Equations of State van der Waals Equation of State Redlich Kwong Equation of State Cubic Equations of State in Cubic Form Cubic Equations of State for Binary Mixtures 70 Summary 73 Exercises 74 3 The First Law and Its Applications Constant Pressure Process Constant Volume Process Constant Temperature Process Adiabatic Process Polytropic Process Steady Flow Process Work Done in a Flow Process Bernoulli s Equation Nozzles and Diffusers Turbines and Compressors Polytropic Flow Process Multi-Stage Compression with Intercooling Transient Flow Process Uniform Flow Process Charging Process Charging Process with Boundary Work Discharging Process 120 Summary 124 Exercises 125
8 Contents vii 4 The Second Law and Its Applications Carnot Cycle (P-V Diagram) Clausius Inequality Reversible and Irreversible Processes Second Law Statements Limitations of the First Law of Thermodynamics Case I Case II Case III Entropy Change of an Irreversible Process Reversible and Irreversible Expansion at Constant Temperature Irreversibility Due to Heat Transfer Over Increase of Entropy Principle Entropy Change of an Ideal Gas Entropy Change for Ideal Gas Undergoing Polytropic Process Entropy Change for Liquids and Solids Why Carnot Cycle is Reversible The Criteria of Equilibrium in Closed Systems Entropy Balance for Control Volumes Adiabatic Efficiency of Some Steady-flow Devices Compressors Pumps Turbines Nozzles Statistical Interpretation of Entropy 172 Summary 173 Exercises Exergy (Availability) Exergy of Heat First and Second Law Efficiency of a Heat Engine Reversible Useful Work of Non-flow Processes Exergy of Non-flow Processes Ú PdV Versus Reversible Work for Non-flow Processes Irreversibility of Non-flow Processes Reversible Useful Work of Non-flow Processes while Exchanging Heat with a Reservoir Reversible Work of Steady-flow Processes Irreversibility of Heat Exchangers 199 Summary 203 Exercises 204
9 viii Contents 6 Chemical Reactions Standard Enthalpy Change of Reaction Standard State Standard Enthalpy Change of Reaction and Heat Exchange with Surroundings Heat of Reaction in Case of Incomplete Conversion and Excess Reactants under Isothermal Conditions About Basic Elements and Molecules Standard Enthalpy Change of Reaction as a Function of Temperature Standard Entropy Change of Reaction as a Function of Temperature Standard Gibbs Free Energy Change of Reaction as a Function of Temperature Gas Phase Reactions Gas Solid Reactions 225 Summary 229 Exercises Thermodynamic Property Relations of Pure Substances Partial Derivatives and Associated Relations Maxwell Relations General Equation for du General Equation for dh General Equations for ds Volume Expansivity and Isothermal Compressibility General Equations for Heat Capacities The Joule Thomson Coefficient The Clapeyron Equation Application of Stability Criteria to Cubic EOS Residual Property Calculations of DH and DS Fugacity Fugacity of Superheated Steam, Saturated Steam and Compressed Liquid 275 Summary 279 Exercises Thermodynamic Cycles Carnot Cycle Rankine Cycle Coefficient of Performance Reversed Carnot Cycle Vapour-Compression Refrigeration Cycle 292
10 Contents ix 8.6 Ammonia-Absorption Refrigeration Cycle Simple Ammonia-Absorption Refrigeration Cycle Ammonia-Absorption Refrigeration Cycle with Analyzer and Heat Exchangers Linde Hampson Liquefaction Cycle Claude Liquefaction Cycle 302 Summary 308 Exercises General Residual Property Relations General Residual Enthalpy Relation for Z(T, P) Type EOS General Residual Internal Energy Relation for Z(T, P) Type EOS General Residual Entropy Relation for Z(T, P) Type EOS General Residual Gibbs Free Energy Relation for Z(T, P) Type EOS General Fugacity Relation for Z(T, P) Type EOS General Residual Internal Energy Relation for Z(T, V) Type EOS General Residual Enthalpy Relation for Z(T, V) Type EOS General Residual Entropy Relaton for Z(T, V) Type EOS General Residual Gibbs Free Energy Relation for Z(T, V) Type EOS General Fugacity Relation for Z(T, V) Type EOS 318 Summary Residual Properties by Equations of State Residual Property Relations for Z = 1 + BP 320 RT 10.2 Calculation of db for Virial Gas Equation of State 322 dt 10.3 Fugacity of Saturated and Compressed Liquid (Vapour Following Virial Gas Equation of State) Residual Property Relations for Z = 1 + B V Residual Internal Energy Relation for Z = 1 + B V Residual Enthalpy Relation for Z = 1 + B V Residual Entropy Relation for Z = 1 + B V Residual Gibbs Free Energy Relation for Z = 1 + B 325 V 10.5 Residual Property Relations for van der Waals Equation of State Residual Internal Energy Relation for van der Waals Equation of State 326
11 Chemical Engineering Thermodynamics 25% OFF Publisher : PHI Learning ISBN : Author : AHUJA, PRADEEP Type the URL : Get this ebook
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