,CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
and by
CRC Press
2 Park Square, Milton Park, Abingdon, Oxon OX14 4RN
© 2020 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Printed on acid-free paper
International Standard Book Number-13: 978-0-367-23116-3 (Paperback)
International Standard Book Number-13: 978-0-367-23147-7 (Hardback)
Tis book contains information obtained from authentic and highly regarded sources. Reasonable eforts have been made to publish reliable data and informa-
tion, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. Te authors and publishers have
attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has
not been obtained. If any copyright material has not been acknowledged, please write and let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechani-
cal, or other means, now known or hereafter invented, including photocopying, microflming, and recording, or in any information storage or retrieval system,
without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright.com/) or contact the
Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-proft organization that provides licenses
and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks and are used only for identifcation and explanation without intent
to infringe.
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
,Contents
Preface ........................................................................................................................................................................................................................................................................... vii
Author..............................................................................................................................................................................................................................................................................ix
WORKBOOK
PART 1: Gases and Gas Laws ................................................................................................................................................3
Key Points – Gas Laws .............................................................................................................................................................................................................3
Law of Corresponding States ............................................................................................................................................................................................. 4
Example Problems .................................................................................................................................................................................................................... 4
Key Points – Mixtures of Gases .......................................................................................................................................................................................... 7
Example Problems .................................................................................................................................................................................................................... 7
PART 2: The First Law of Thermodynamics: Work (PV) and Heat, as ∆U and ∆H........................................................... 11
Key Points – The First Law .................................................................................................................................................................................................. 11
Example Problems ..................................................................................................................................................................................................................12
Adiabatic Processes ................................................................................................................................................................................................................14
Example Problems ..................................................................................................................................................................................................................14
Key Points – Calorimetry .....................................................................................................................................................................................................15
Example Problems ..................................................................................................................................................................................................................16
Key Points – Hess’s Law Calculation for ∆H.............................................................................................................................................................17
Example Problems ..................................................................................................................................................................................................................17
Key Points – Indirect Methods for ∆H Determination ......................................................................................................................................17
Example Problems ..................................................................................................................................................................................................................18
Key Points – Using Cyclic Diagrams for ∆H ............................................................................................................................................................19
Example Problems ..................................................................................................................................................................................................................19
Key Points – Temperature Dependence of ∆H .....................................................................................................................................................20
Example Problems ..................................................................................................................................................................................................................21
PART 3: Second and Third Law of Thermodynamics, ∆S ................................................................................................25
Key Points – The Second Law ..........................................................................................................................................................................................25
Example Problems ..................................................................................................................................................................................................................27
Key Points – Real Gases and Entropy ...........................................................................................................................................................................33
PART 4: Free Energy (∆G), Helmholtz Energy (∆A), and Phase Equilibrium ..................................................................35
Key Points – Gibbs and Helmholtz Free Energy ...................................................................................................................................................35
Example Problems ..................................................................................................................................................................................................................37
Key Points – The Chemical Potential and Phase Diagrams ............................................................................................................................43
Example Problems ..................................................................................................................................................................................................................43
Key Points – The Chemical Potential of Real Gases and Fugacity ..............................................................................................................46
Example Problems ..................................................................................................................................................................................................................47
PART 5: Free Energy (∆G) of Mixing, Binary Liquid Mixtures, Colligative Properties, and Activity ...........................49
Key Points – Free Energy of Mixing ..............................................................................................................................................................................49
Example Problems ..................................................................................................................................................................................................................49
v
, vi Contents
Key Points – ∆G and Two-Component Liquid Mixtures..................................................................................................................................50
Key Points – Real Solutions and Excess Thermodynamic Functions for Mixtures ...........................................................................51
Example Problems ..................................................................................................................................................................................................................52
Key Points – Vapor Pressure, Raoult’s Law, and Henry’s Law for Mixtures ............................................................................................57
Key Points – Henry’s Law for Binary Mixtures.........................................................................................................................................................58
Key Points – Liquid–Vapor Phase Diagrams ............................................................................................................................................................59
Lever Rule Liquid Vapor Diagrams .........................................................................................................................................................................60
Key Points – Non-Ideal or Regular Solutions: Azeotropes ..............................................................................................................................60
Key Points – Activity and Activity Coefcients for Mixtures..........................................................................................................................61
Example Problems ..................................................................................................................................................................................................................61
Key Points – Colligative Properties................................................................................................................................................................................67
Example Problems ..................................................................................................................................................................................................................68
Key Points – Activity Coefcients in Colligative Properties for Real Solutions ...................................................................................71
Example Problems ..................................................................................................................................................................................................................72
Key Points – Henry’s Law and Saturated Solutions of Solute B in A .........................................................................................................73
Example Problems ..................................................................................................................................................................................................................74
PART 6: Free Energy, Equilibrium Constants, and Electromotive Force .......................................................................77
Key Points – Free Energy and Chemical Reactions .............................................................................................................................................77
Example Problems ..................................................................................................................................................................................................................78
Key Points – Ionic Strength, Activity Coefcients, and Efect on Equilibria .........................................................................................82
Example Problems ..................................................................................................................................................................................................................83
Key Points – Electrochemistry, Equilibrium, and Activities............................................................................................................................ 84
Example Problems ..................................................................................................................................................................................................................86
Electrochemistry and Equilibrium in Biochemical Redox Reactions .......................................................................................................87
Example Problems ..................................................................................................................................................................................................................88
Key Points – Thermodynamics of Redox Reactions: ∆S° and ∆H°...........................................................................................................90
Example Problems ..................................................................................................................................................................................................................90
Mean Ionic Activity and Redox Reactions ................................................................................................................................................................91
Example Problems ..................................................................................................................................................................................................................92
FINAL ANSWERS
Answers to Example Problems..........................................................................................................................................95
Final Answers and Hints ......................................................................................................................................................................................................95
Part 1: Gases and Gas Laws .........................................................................................................................................................................................95
Part 2: First Law of Thermodynamics – Work (PV), Heat, ∆U and ∆H...............................................................................................96
Part 3: Second and Third Laws – Entropy .......................................................................................................................................................100
Part 4: Free Energy (∆G), Helmholtz Energy (∆A), and Phase Equilibrium .................................................................................. 103
Part 5: Free Energy (∆G) of Mixing, Binary Liquid Mixtures, Colligative Properties, and Activity ..................................109
Part 6: Free Energy (∆G), Equilibrium, and Electrochemistry ...............................................................................................................119
Index .................................................................................................................................................................................. 127
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
and by
CRC Press
2 Park Square, Milton Park, Abingdon, Oxon OX14 4RN
© 2020 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Printed on acid-free paper
International Standard Book Number-13: 978-0-367-23116-3 (Paperback)
International Standard Book Number-13: 978-0-367-23147-7 (Hardback)
Tis book contains information obtained from authentic and highly regarded sources. Reasonable eforts have been made to publish reliable data and informa-
tion, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. Te authors and publishers have
attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has
not been obtained. If any copyright material has not been acknowledged, please write and let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechani-
cal, or other means, now known or hereafter invented, including photocopying, microflming, and recording, or in any information storage or retrieval system,
without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright.com/) or contact the
Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-proft organization that provides licenses
and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks and are used only for identifcation and explanation without intent
to infringe.
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
,Contents
Preface ........................................................................................................................................................................................................................................................................... vii
Author..............................................................................................................................................................................................................................................................................ix
WORKBOOK
PART 1: Gases and Gas Laws ................................................................................................................................................3
Key Points – Gas Laws .............................................................................................................................................................................................................3
Law of Corresponding States ............................................................................................................................................................................................. 4
Example Problems .................................................................................................................................................................................................................... 4
Key Points – Mixtures of Gases .......................................................................................................................................................................................... 7
Example Problems .................................................................................................................................................................................................................... 7
PART 2: The First Law of Thermodynamics: Work (PV) and Heat, as ∆U and ∆H........................................................... 11
Key Points – The First Law .................................................................................................................................................................................................. 11
Example Problems ..................................................................................................................................................................................................................12
Adiabatic Processes ................................................................................................................................................................................................................14
Example Problems ..................................................................................................................................................................................................................14
Key Points – Calorimetry .....................................................................................................................................................................................................15
Example Problems ..................................................................................................................................................................................................................16
Key Points – Hess’s Law Calculation for ∆H.............................................................................................................................................................17
Example Problems ..................................................................................................................................................................................................................17
Key Points – Indirect Methods for ∆H Determination ......................................................................................................................................17
Example Problems ..................................................................................................................................................................................................................18
Key Points – Using Cyclic Diagrams for ∆H ............................................................................................................................................................19
Example Problems ..................................................................................................................................................................................................................19
Key Points – Temperature Dependence of ∆H .....................................................................................................................................................20
Example Problems ..................................................................................................................................................................................................................21
PART 3: Second and Third Law of Thermodynamics, ∆S ................................................................................................25
Key Points – The Second Law ..........................................................................................................................................................................................25
Example Problems ..................................................................................................................................................................................................................27
Key Points – Real Gases and Entropy ...........................................................................................................................................................................33
PART 4: Free Energy (∆G), Helmholtz Energy (∆A), and Phase Equilibrium ..................................................................35
Key Points – Gibbs and Helmholtz Free Energy ...................................................................................................................................................35
Example Problems ..................................................................................................................................................................................................................37
Key Points – The Chemical Potential and Phase Diagrams ............................................................................................................................43
Example Problems ..................................................................................................................................................................................................................43
Key Points – The Chemical Potential of Real Gases and Fugacity ..............................................................................................................46
Example Problems ..................................................................................................................................................................................................................47
PART 5: Free Energy (∆G) of Mixing, Binary Liquid Mixtures, Colligative Properties, and Activity ...........................49
Key Points – Free Energy of Mixing ..............................................................................................................................................................................49
Example Problems ..................................................................................................................................................................................................................49
v
, vi Contents
Key Points – ∆G and Two-Component Liquid Mixtures..................................................................................................................................50
Key Points – Real Solutions and Excess Thermodynamic Functions for Mixtures ...........................................................................51
Example Problems ..................................................................................................................................................................................................................52
Key Points – Vapor Pressure, Raoult’s Law, and Henry’s Law for Mixtures ............................................................................................57
Key Points – Henry’s Law for Binary Mixtures.........................................................................................................................................................58
Key Points – Liquid–Vapor Phase Diagrams ............................................................................................................................................................59
Lever Rule Liquid Vapor Diagrams .........................................................................................................................................................................60
Key Points – Non-Ideal or Regular Solutions: Azeotropes ..............................................................................................................................60
Key Points – Activity and Activity Coefcients for Mixtures..........................................................................................................................61
Example Problems ..................................................................................................................................................................................................................61
Key Points – Colligative Properties................................................................................................................................................................................67
Example Problems ..................................................................................................................................................................................................................68
Key Points – Activity Coefcients in Colligative Properties for Real Solutions ...................................................................................71
Example Problems ..................................................................................................................................................................................................................72
Key Points – Henry’s Law and Saturated Solutions of Solute B in A .........................................................................................................73
Example Problems ..................................................................................................................................................................................................................74
PART 6: Free Energy, Equilibrium Constants, and Electromotive Force .......................................................................77
Key Points – Free Energy and Chemical Reactions .............................................................................................................................................77
Example Problems ..................................................................................................................................................................................................................78
Key Points – Ionic Strength, Activity Coefcients, and Efect on Equilibria .........................................................................................82
Example Problems ..................................................................................................................................................................................................................83
Key Points – Electrochemistry, Equilibrium, and Activities............................................................................................................................ 84
Example Problems ..................................................................................................................................................................................................................86
Electrochemistry and Equilibrium in Biochemical Redox Reactions .......................................................................................................87
Example Problems ..................................................................................................................................................................................................................88
Key Points – Thermodynamics of Redox Reactions: ∆S° and ∆H°...........................................................................................................90
Example Problems ..................................................................................................................................................................................................................90
Mean Ionic Activity and Redox Reactions ................................................................................................................................................................91
Example Problems ..................................................................................................................................................................................................................92
FINAL ANSWERS
Answers to Example Problems..........................................................................................................................................95
Final Answers and Hints ......................................................................................................................................................................................................95
Part 1: Gases and Gas Laws .........................................................................................................................................................................................95
Part 2: First Law of Thermodynamics – Work (PV), Heat, ∆U and ∆H...............................................................................................96
Part 3: Second and Third Laws – Entropy .......................................................................................................................................................100
Part 4: Free Energy (∆G), Helmholtz Energy (∆A), and Phase Equilibrium .................................................................................. 103
Part 5: Free Energy (∆G) of Mixing, Binary Liquid Mixtures, Colligative Properties, and Activity ..................................109
Part 6: Free Energy (∆G), Equilibrium, and Electrochemistry ...............................................................................................................119
Index .................................................................................................................................................................................. 127
