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Chemical Thermodynamics
Theory and Applications
Chemical Thermodynamics
Theory and Applications
W. John Rankin
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 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-13 978-0-367-22247-5 (Hardback)
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Library of Congress Cataloging-in-Publication Data
Names: Rankin, W. J., author.

Title: Chemical thermodynamics : theory and applications / authored by W.J.
Rankin.
Description: First edition. | Boca Raton, FL : CRC Press/Taylor & Francis
Group, 2019. | Includes bibliographical references and index. | Summary:
“This book develops the theory of chemical thermodynamics from first principles, demonstrates its relevance across sci-
entific and engineering disciplines, and shows how thermodynamics can be used as a practical tool for understanding
natural phenomenon and developing and improving technologies and products. Concepts such as internal energy, enthalpy,
entropy, and Gibbs energy are explained using ideas and experiences familiar to students and arealistic examples are given
so the usefulness and pervasiveness of thermodynamics becomes apparent. The worked examples illustrate key ideas and
demonstrate important types of calculations, and the problems at the end of chapters are designed to reinforce important
concepts and show the broad range of applications. Most can be solved using digitized data from open access databases
and a spreadsheet. Answers are provided for the numerical problems. A particular theme of the book is the calculation of
the equilibrium composition of systems, both reactive and non-reactive, and this includes the principles of Gibbs energy
minimization. The overall approach leads to the intelligent use of thermodynamic software packages but, while these are
discussed and their use demonstrated, they are not the focus of the book, the aim being to provide the necessary founda-
tions. Another unique aspect is the inclusion of three applications chapters: heat and energy aspects of processing; the
thermodynamics of metal production and recycling; and applications of electrochemistry. This book is aimed primarily
at students of chemistry, chemical engineering, applied science, materials science and metallurgy, though it will be also
useful for students undertaking courses in geology and environmental science”-- Provided by publisher.
Identifiers: LCCN 2019026322 (print) | LCCN 2019026323 (ebook) | ISBN
9780367222475 (hardback ; acid-free paper) | ISBN 9780429277252 (ebook)
Subjects: LCSH: Thermochemistry. | Thermodynamics.
Classification: LCC QD511 .R28 2019 (print) | LCC QD511 (ebook) | DDC
541/.36--dc23
LC record available at https://lccn.loc.gov/2019026322
LC ebook record available at https://lccn.loc.gov/2019026323
Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com
and the CRC Press Web site at

http://www.crcpress.com
Contents
Preface............................................................................................................................................ xiii
A note to students............................................................................................................................. xv
Author.............................................................................................................................................xvii
Units.................................................................................................................................................xix
Nomenclature...................................................................................................................................xxi
Constants....................................................................................................................................... xxiii
Chapter 1 An overview of thermodynamics..................................................................................1

Scope��1
Learning objectives....................................................................................................... 1
1.1 What is thermodynamics?.................................................................................. 1
1.2 A brief history....................................................................................................2
1.3 The laws of thermodynamics.............................................................................3
Chapter 2 Fundamental concepts...................................................................................................5

Scope��5
Learning objectives....................................................................................................... 5
2.1 Introduction........................................................................................................ 5
2.2 Substances and the states of matter.................................................................... 5
2.2.1 Amount of substance.............................................................................7
2.3 Systems............................................................................................................... 8
2.3.1 Composition of systems....................................................................... 10
2.3.2 Macroscopic and microscopic properties............................................ 13
2.3.3 The concept of equilibrium................................................................. 13
2.4 Processes.......................................................................................................... 14
2.5 State functions and path functions................................................................... 16
Summary........................................................................................................... 17
2.5.1 The standard state............................................................................... 18
2.6 Energy, work, heat and temperature................................................................. 19
2.6.1 Energy and work................................................................................. 19
2.6.2 Heat.....................................................................................................20
2.6.3 Temperature.........................................................................................20
Problems...................................................................................................................... 22
Chapter 3 Gases...........................................................................................................................25
Scope�� 25
Learning objectives.....................................................................................................25
3.1 Introduction......................................................................................................25
3.2 Gas pressure.....................................................................................................25
3.3 Ideal gases........................................................................................................26
3.3.1 Avogadro’s law and Avogadro’s constant............................................26
3.3.2 The combined gas law......................................................................... 27
3.3.3 The ideal gas law................................................................................. 27
3.3.4 Gas mixtures.......................................................................................28
v
vi Contents
3.4 Real gases......................................................................................................... 29

3.4.1 The p - V - T relationship................................................................... 29
3.4.2 Compressibility................................................................................... 31
3.4.3 Equations of state for real gases.......................................................... 32
Problems...................................................................................................................... 33
Chapter 4 The first law................................................................................................................. 35

Scope��35
Learning objectives..................................................................................................... 35
4.1 Introduction...................................................................................................... 35
4.2 The first law...................................................................................................... 35
4.2.1 Internal energy.................................................................................... 36
4.2.2 Mathematical statement of the first law.............................................. 37
4.3 Enthalpy............................................................................................................40
4.3.1 The nature of enthalpy........................................................................ 41
4.4 The enthalpy of mixing.................................................................................... 41
4.5 The enthalpy of phase changes......................................................................... 42
4.6 Heat capacity.................................................................................................... 43
4.7 The enthalpy of substances............................................................................... 45
4.7.1 Variation of enthalpy with temperature..............................................46
4.7.2 Enthalpy increments............................................................................ 47
4.8 The enthalpy of formation................................................................................ 49
4.9 The enthalpy of reaction................................................................................... 51
4.10 Experimental determination of heat capacity and enthalpy............................. 54
Problems...................................................................................................................... 55
Chapter 5 Sources of thermodynamic data for substances.......................................................... 59

Scope��59
5.1 Introduction...................................................................................................... 59
5.2 Compilations of thermodynamic data.............................................................. 59
5.2.1 The reference state..............................................................................60
5.2.2 The NIST−JANAF, NBS and US Geological Survey tables...............60
5.2.3 The FREED software program........................................................... 63
5.2.4 Barin’s thermochemical tables............................................................ 63
5.3 Thermochemical software programs................................................................ 63
Problems......................................................................................................................66
Chapter 6 Some applications of the first law............................................................................... 67

Scope��67
6.1 Introduction...................................................................................................... 67
6.2 Heating and cooling of substances................................................................... 68
6.3 Energy balances................................................................................................ 70
6.4 Adiabatic temperature of reaction.................................................................... 75
6.5 Heat utilisation in furnaces.............................................................................. 77
Problems...................................................................................................................... 78
Contents vii
Chapter 7 The second and third laws........................................................................................... 81

Scope��81
7.1 Introduction...................................................................................................... 81
7.2 Entropy and the second law ............................................................................. 82
7.2.1 The nature of entropy.......................................................................... 82
Summary...........................................................................................................84
7.2.2 Broad implications of the first and second laws..................................84
7.2.3 Alternative statements of the second law............................................ 85
7.3 The entropy of mixing...................................................................................... 87
7.3.1 The mixing of ideal gases................................................................... 87
7.3.2 The general equation for mixing......................................................... 89
7.4 The entropy of phase changes..........................................................................90
7.5 The third law and the entropy of substances....................................................92
7.6 The entropy of formation and entropy of reaction........................................... 95
7.7 Entropy as a criterion of spontaneity................................................................ 98
7.8 Experimental determination of entropy........................................................... 98
Problems...................................................................................................................... 98
Chapter 8 Gibbs and Helmholtz energies.................................................................................. 103

Scope�� 103
Learning objectives................................................................................................... 103
8.1 Introduction.................................................................................................... 103
8.2 Combined statement of the first and second laws.......................................... 104
8.3 Helmholtz and Gibbs energies........................................................................ 105
Summary......................................................................................................... 106
8.3.1 The criteria for spontaneity............................................................... 106
8.3.2 The Gibbs−Helmholtz equation........................................................ 107
8.4 The Gibbs energy of phase changes............................................................... 108
8.5 The Gibbs energy of mixing.......................................................................... 108
8.6 The Gibbs energy of substances..................................................................... 109
8.7 The Gibbs energy of formation...................................................................... 111
8.8 The Gibbs energy of reaction......................................................................... 113
8.9 The use of Gibbs energy to study reactions................................................... 117
8.9.1 The importance of kinetics............................................................... 119
Summary......................................................................................................... 120
8.10 Experimental determination of Gibbs energy................................................ 120
Problems.................................................................................................................... 120
Chapter 9 Solutions.................................................................................................................... 123

9.1 Introduction.................................................................................................... 123
9.2 Types of solutions........................................................................................... 124
9.2.1 Aqueous solutions............................................................................. 124
9.2.2 Organic solutions............................................................................... 124
9.2.3 Molten solutions................................................................................ 124
9.2.4 Solid solutions................................................................................... 125
9.3 Integral and partial quantities........................................................................ 126
viii Contents
9.3.1 Relative partial and integral quantities............................................. 128

9.3.2 Calculating partial quantities from integral quantities..................... 129
9.3.3 The Gibbs−Duhem equation............................................................. 131
9.4 Gas mixtures.................................................................................................. 132
9.4.1 Ideal gas mixtures............................................................................. 132
9.4.2 Non-ideal gas mixtures..................................................................... 136
9.5 Liquid and solid solutions............................................................................... 138
9.5.1 The concept of activity...................................................................... 139
9.5.2 Pure substance standard state............................................................ 141
9.5.3 The infinitely dilute standard state.................................................... 142
9.5.4 Conversion between standard states.................................................. 145
9.5.5 The Gibbs–Duhem equation............................................................. 147
9.6 Properties of solutions.................................................................................... 148
9.6.1 Ideal solutions.................................................................................... 149
9.6.2 Non-ideal solutions............................................................................ 151
9.6.3 Excess molar quantities..................................................................... 152
9.7 Experimental measurement of activities........................................................ 153
9.8 Sources of activity data.................................................................................. 153
Problems.................................................................................................................... 154
Chapter 10 Reactive systems – single reactions.......................................................................... 157

Scope�� 157
10.1 Introduction.................................................................................................... 157
10.2 The feasibility of chemical reactions.............................................................. 158
10.3 The equilibrium constant............................................................................... 160
10.4 Choice of standard state................................................................................. 166
Summary......................................................................................................... 168
10.5 The effect of temperature, pressure and concentration on equilibrium......... 168
10.5.1 The effect of temperature.................................................................. 169
10.5.2 The effect of pressure........................................................................ 169
10.5.3 The effect of composition.................................................................. 169
10.6 The equilibrium composition of a system...................................................... 170
10.6.1 Single reactions................................................................................. 170
Single phase reactions....................................................................... 171
Heterogeneous reactions................................................................... 172
10.6.2 Multiple reactions within a system.................................................... 174
Problems.................................................................................................................... 174
Chapter 11 Gibbs energy applications to metal production......................................................... 179

Scope�� 179
11.1 Introduction.................................................................................................... 179
11.2 Stability of oxides........................................................................................... 180
11.3 Reduction reactions........................................................................................ 182
11.3.1 Reduction using carbon..................................................................... 183
11.3.2 Reduction with carbon monoxide and hydrogen............................... 184
11.3.3 Reduction using another metal.......................................................... 190
Contents ix
11.4 Oxidation reactions......................................................................................... 191

11.5 Metal production strategy............................................................................... 192
Problems.................................................................................................................... 194
Chapter 12 Electrolyte solutions.................................................................................................. 195

Scope�� 195
12.1 Introduction.................................................................................................... 195
12.2 Aqueous solutions........................................................................................... 195
12.3 Enthalpy, Gibbs energy and entropy of ions in aqueous solutions................. 197
12.3.1 Sources of thermodynamic data for aqueous solutions.....................200
12.4 Activities in electrolyte solutions...................................................................202
12.4.1 The unit activity coefficient approximation...................................... 203
12.4.2 Mean ionic activity............................................................................205
12.4.3 Activity of the electrolyte..................................................................206
12.4.4 Multiple electrolytes in solution........................................................208
12.5 The activity of ions.........................................................................................209
12.6 Partial dissociation......................................................................................... 214
12.6.1 Degree of dissociation....................................................................... 215
12.7 The pH scale................................................................................................... 215
Problems.................................................................................................................... 218
Chapter 13 Phase equilibria: non-reactive systems..................................................................... 221

Scope�� 221
13.1 Introduction.................................................................................................... 221
13.2 Equilibrium in multi-phase systems............................................................... 222
13.3 The phase rule................................................................................................ 222
13.4 One-component systems.................................................................................224
13.4.1 An example of a p–T diagram: carbon.............................................. 225
13.4.2 Stability of phases – The Clapyron and Clausius−Clapyron
equations............................................................................................ 226
The solid−liquid boundary: melting point......................................... 228
The liquid−gas boundary: vapour pressure and boiling point........... 229
The solid−gas boundary: sublimation temperature........................... 231
13.4.3 The effect of external pressure on vapour pressure.......................... 231
13.5 Two-component systems................................................................................ 232
13.5.1 Solid−liquid, solid−solid and liquid−liquid systems......................... 233
13.5.2 Interpreting phase diagrams.............................................................. 234
13.5.3 Liquid−vapour systems..................................................................... 238
Miscible liquids................................................................................. 238
Immiscible liquids............................................................................. 241
13.6 Thermodynamic basis of phase diagrams...................................................... 241
13.7 Determination of phase diagrams.................................................................. 245
13.8 Partitioning of components between phases ................................................. 247
Problems....................................................................................................................248
Further Reading......................................................................................................... 250
x Contents
Chapter 14 Phase equilibria: reactive systems............................................................................. 251

Scope�� 251
14.1 Introduction.................................................................................................... 251
14.2 The phase rule for reactive systems................................................................ 251
14.3 Phase stability diagrams ................................................................................ 257
14.4 The distribution of elements between phases................................................. 258
14.4.1 Solvent extraction..............................................................................260
14.4.2 Distribution of elements in gas–slag–metal systems........................ 262
Problems....................................................................................................................264
Chapter 15 Complex equilibria.................................................................................................... 267

Scope�� 267
15.1 Introduction.................................................................................................... 267
15.2 The stoichiometric approach.......................................................................... 267
15.3 Gibbs energy minimisation............................................................................ 270
15.4 Commercial software to perform Gibbs energy minimisation...................... 274
Problems.................................................................................................................... 277
Further Reading......................................................................................................... 278
Chapter 16 Electrochemistry....................................................................................................... 279

Scope�� 279
16.1 Introduction.................................................................................................... 279
16.2 Definitions of Ampere, Coulomb and Volt..................................................... 279
16.3 Electrochemical reactions..............................................................................280
16.3.1 An example of an electrochemical reaction...................................... 281
16.4 Conductors and conduction............................................................................ 282
16.5 Electrochemical cells...................................................................................... 283
16.5.1 Contact potential............................................................................... 285
16.5.2 Half-cell and cell reactions............................................................... 285
16.5.3 Gibbs energy of cell reactions........................................................... 286
16.5.4 Electrode potentials........................................................................... 287
16.5.5 Types of electrochemical cells.......................................................... 290
Electrolytic cells................................................................................ 290
Galvanic cells.................................................................................... 292
16.5.6 Kinetic effects................................................................................... 297
16.5.7 Total cell potential and Ohmic heating............................................. 298
16.5.8 The laws of electrolysis..................................................................... 299
16.6 Phase stability diagrams.................................................................................300
16.7 The use of galvanic cells to measure thermodynamic properties.................. 301
Problems....................................................................................................................302
Chapter 17 Some applications of electrochemistry..................................................................... 305

Scope�� 305
17.1 Electrolysis..................................................................................................... 305
Contents xi
17.1.1 Electrowinning of metals.................................................................. 305

17.1.2 Manufacture of chlorine....................................................................307
17.1.3 Electrorefining...................................................................................307
17.1.4 Electroplating....................................................................................308
17.1.5 Anodising..........................................................................................308
17.1.6 Energy required for electrolytic processes........................................308
17.2 Cementation....................................................................................................309
17.3 Corrosion........................................................................................................ 310
17.4 Batteries.......................................................................................................... 310
17.5 Fuel cells......................................................................................................... 311
Answers to problems..................................................................................................................... 313
Index............................................................................................................................................... 317
Preface
This book is aimed primarily at students of chemistry, chemical engineering, applied science, mate-
rials science and metallurgy, though it will be useful also for students undertaking courses in geol-
ogy and environmental science.
My aim has been to produce a book that rigorously develops the theory of thermodynamics and
demonstrates its relevance across scientific and engineering disciplines and to show that thermo-
dynamics, far from being an esoteric and abstract discipline, is a practical tool for understanding
natural phenomenon and developing and improving technologies and products. The author has been
a user of thermodynamics in process development applications, an experimental thermodynamicist
and teacher of the subject for over 30 years, and it is hoped that some of this experience is reflected
in the content, style and approach adopted. It is likely students will have previously encountered
elementary aspects of thermodynamics in other subjects, but this book assumes no prior exposure
to the subject. Only a basic knowledge of calculus is assumed.
Many textbooks of thermodynamics follow the historical development of the discipline. Many
also concentrate on the mathematical aspects of the subject and inadequately link these to real
phenomena and processes. In more applied texts, the approach often is to identify the key equations
and show how to use them to perform routine calculations with little theoretical understanding.
None of these approaches is ideal. At one extreme, thermodynamics becomes almost a branch of
applied mathematics; at the other, it becomes little more than teaching the student to pick the right
equation for a particular calculation. In both cases, the fundamental principles of thermodynamics,
its over-arching relevance and the inherent beauty of the subject, are either obscured by detail or
not revealed at all.
Thermodynamics has been revolutionised over the past several decades by the conversion of
thermodynamic data into digitised formats amenable to manipulation using spreadsheets and by the
development of software products for performing thermodynamic calculations. This requires newer
ways of presenting the subject. This book adopts a modern approach.
• Abstract concepts such as internal energy, enthalpy, entropy, Gibbs energy, etc., are
explained using ideas and experiences that are familiar to students so that these have real
meaning.
• Mathematical concepts are developed fully, and intermediate steps are shown so students
can easily follow the logical development of the subject but without overwhelming the
student with mathematics.
• Realistic and familiar examples are given so the usefulness and pervasiveness of thermo-
dynamics become apparent. Worked examples are designed to illustrate important ideas
and demonstrate important types of calculations.
• Modern forms of data, including databases, are used.
• The problems provided at the ends of chapters are designed to reinforce important con-
cepts and/or to show the broad range of applications of thermodynamics. Most can be
solved using digitised data and a spreadsheet. Answers are provided for most of the numer-
ical problems.
• The overall approach adopted leads naturally to the intelligent use of thermodynamic soft-
ware packages.
• SI units and IUPAC nomenclature are used throughout.
Many thermodynamic computational software products are available. These are largely black boxes
which produce solutions to a range of thermodynamic problems. These have great power and are
very useful when used by skilled practitioners. Indeed, practitioners now routinely use these, and the
xiii
xiv Preface
tedious hand calculations, still so frequently used in undergraduate courses, are never performed in
practice today. However, when users have little theoretical understanding of thermodynamics, these
products often produce results which are either wrong or which are misinterpreted. It is important
that students are aware of these packages and their capabilities, and these are discussed in this book,
but I believe they should have a complementary role in introductory courses of thermodynamics and
not be the focus of the course.
Many modern texts are overloaded with detail and extraneous information which, even if inter-
esting, makes it difficult for the student to identify the key messages and points. This book is pur-
posely succinct, focussed and easy to read. Each chapter starts with a brief statement of the scope
and the key learning objectives. The text of each chapter begins with an introductory paragraph to
set the context, and key points and key equations are emphasised in the text.
The applications chapters (Chapters 6, 11 and 17) are more extensive than in most introductory
books, and the examples have been chosen to show the wide-ranging applications of thermodynam-
ics. These chapters could be omitted for less applied courses (or only a few examples selected).
Many people, directly and indirectly, have made this book possible. Dr Anil K. Biswas first
introduced me as an undergraduate student at the University of Queensland to the wonders of ther-
modynamics. Many colleagues over the subsequent years helped sustain my interest and enthusiasm
for the subject. More recently, Drs R. J. Sinclair, D. E. Langberg, D. R. Swinbourne, G. Senanayake
and J. B. See read drafts of some or all of the chapters and gave useful feedback. David Langberg
also worked many of the chapter problems. All errors in the text of course are mine alone. Finally, I
wish to express my gratitude to Marsha Rankin for her support and for enduring my preoccupation
during the writing of the book over an extensive period.
A note to students
It’s been said that the first time we are exposed to thermodynamics we don’t understand very much
of it; the second time we think we understand it all; the third time we realise we don’t understand
it at all. This is not meant to put you off the study of thermodynamics but simply to emphasise that
some thermodynamic concepts are difficult to fully comprehend; indeed, most practitioners and
teachers continue to develop new insights into thermodynamics throughout their working lives.
Hopefully, this book will lead some of you onto that path.
HOW TO USE THIS BOOK

For each chapter, the following steps might be found useful.
• Read the chapter scope and introductory paragraph to understand the aim of the chapter.
• Scan the chapter to get an idea of the contents – this includes understanding the structure
of the chapter, the main headings and terms.
• Read the chapter from beginning to end with a view to understanding it fully – this may
require rereading all or parts of the chapter.
• Review the learning objectives at the beginning of the chapter.
• Attempt some or all of the problems.
TACKLING THE PROBLEMS

The problems aim to reinforce the learnings of the chapter and illustrate some ways thermodynam-
ics can be applied to real situations. A systematic approach to solving the problems involves the
following steps:
• Understand what the question requires and decide the calculation procedure.
• Identify and list any required assumptions.
• Collect the necessary data and enter them into a spreadsheet. Use of a spreadsheet rather
than a calculator to perform calculations makes it easy to alter/correct equations, change
input values, etc.
• Convert all the data to SI units (if not already in SI units). All calculations should be done
in SI units – this makes life so much easier than trying to use mixed units!
• Perform the necessary calculations. If you have performed all the calculations in SI units,
the answer will also be in SI units.
• Finally, try to assess the reasonableness of the answer and select the appropriate number
of significant figures.
xv
4 Chemical Thermodynamics
isolated system* is constant; energy can be transformed from one form to another but cannot be
created or destroyed.
The second law. The second law of thermodynamics tells about the direction in which natural
processes occur and allows answers to questions such as:
• Will a system change from State 1 to State 2 under given conditions? If not, how can the
conditions be altered in order to make the change occur?
• Under what conditions will the system change from State 1 to State 2 spontaneously, that
is, without any external help?
The second law deals only with the feasibility of change, not with the rate of change. The study of
rate of change (kinetics) is not the domain of thermodynamics.
The third law. The third law of thermodynamics states that there is an absolute zero of tempera-
ture (−273.15°C), though in practice it can never be achieved. At this temperature, systems have
their greatest order at the molecular level. The third law is used in the evaluation of a quantity called
entropy.
These four laws lead directly to the definition of a number of important thermodynamic quanti-
ties, as briefly discussed below.
From the first law, since energy cannot be created or destroyed the energy within a system, its
internal energy, U (or total energy or intrinsic energy), must increase or decrease if the system takes
in or gives out energy, respectively. In a closed system,† there are two ways in which this energy
exchange can take place: Through work done on or by the system and through heat transfer to or
from the system. Because many processes of interest are open to the atmosphere, it is convenient
to focus on the exchange of thermal energy that occurs at constant pressure. This property is called
enthalpy, H. Working with enthalpy rather than internal energy has the advantage that it bypasses
the need to keep track of the work that is done whenever the volume of a system changes through
expansion or contraction.
A spontaneous change in a system is one that occurs naturally, without any external energy. The
direction of such a change is determined by the natural tendency of matter and energy to disperse
in a random manner. The measure of this dispersal is called the entropy, S. The second law of
thermodynamics states that in an isolated system undergoing a spontaneous change the entropy of
the system always increases. This law accounts for changes in an entirely general way, whatever
the process might be and regardless of whether physical or chemical transformations are involved.
The criterion for spontaneity of a process is that the total entropy of the universe must increase.
To apply this to the common case of a closed system, rather than an isolated system, it is necessary
to establish the entropy change both in the system and in its surroundings. When the process occurs
at constant temperature and pressure, it is possible to express the entropy change of the surround-
ings in terms of the change in the system’s enthalpy. In this way, the overall entropy change of the
system plus its surroundings brought about by a process can be described in terms of the properties
of the system alone (H, S and T). This combined measure of the total entropy change from the per-
spective of the system alone is called the Gibbs energy, G, of the system. At constant temperature
and pressure, every chemical reaction and every physical process that occurs of its own accord (that
is, without the input of external energy) is driven by a lowering of the Gibbs energy.
We explore these and other concepts in greater detail in the remainder of this book and show how
they are used to understand, predict and control physico-chemical processes.
* An isolated system is one that has a boundary that prevents the transfer of both matter and energy; no matter or energy is
exchanged with its surroundings.
† A closed system is one that allows the exchange of energy but not matter with its surroundings.
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evidences of the public debt, and by authority of law $10,575,738 was
redeemed by the issue of certificates of funded stock, bearing interest
at from 6 to 7 per cent. per annum, redeemable at any time after
1824.
“During the years 1812–13 the sum of $2,984,747 of the old 6 per
cent. and deferred stocks were refunded into new 6 per cent. stock
redeemable in twelve years; and by an act approved March 31, 1814,
Congress having authorized a settlement of the ‘Yazoo claims’ by an
issue of non-interest-bearing stock, payable out of the first receipts
from the sale of public lands in the Mississippi territory, $4,282,037
was issued for this purpose. On the 24th of February, 1815, Secretary
Dallas reported to Congress that the public debt had been increased,
in consequence of the war with Great Britain, $68,783,122, a large
portion of which was due and unpaid, while another considerable
proportion was fast becoming due. These unpaid or accruing
demands were in part for temporary loans, and the balance for
Treasury notes either due or maturing daily. To provide for their
payment a new loan for the full amount needed was authorized by
act of March 3, 1815, and six per cent. stock redeemable in fifteen
years, was issued in the sum of $12,288,148. This stock was sold at
from 95 per cent. to par, and was nearly all redeemed in 1820 by
purchases made by the Commissioners of the Sinking Fund.
“The Government became a stockholder in the second Bank of the
United States, to the amount of 70,000 shares, under the act of
incorporation, approved April 10, 1816. The capital stock was limited
to $35,000,000, divided into 350,000 shares of $100 each. The
Government subscription was paid by the issue of 5 per cent. stock to
the amount of $7,000,000, redeemable at the pleasure of the
Government. This was a profitable investment for the United States,
as in addition to $1,500,000 which the bank paid as a bonus for its
charter, the net receipts over and above disbursements amounted to
$4,993,167. The available funds in the Treasury on the 1st of
January, 1820, were less than $250,000, and the estimated
deficiency for the year amounted to nearly $4,000,000. This state of
affairs was owing partly to the disastrous effects of the commercial
crisis of 1819, heavy payments for the redemption of the public debt,
continued through a series of years, and large outstanding claims,
amounting to over $30,000,000, resulting from the late war with
Great Britain. To meet the emergency, a loan was authorized by act
of May 15, 1820, and $999,999.13 was borrowed at 5 per cent.,
redeemable in twelve years, and $2,000,000 at 6 per cent.,
reimbursable at pleasure, this latter stock realizing a premium of 2
per cent. By act of March 3, 1821, 5 per cent. stock amounting to
$4,735,276 was issued at a premium of over 5½ per cent., and the
proceeds used in payment of the principal and interest of the public
debt falling due within the year.
“An effort was made in 1822 to refund a portion of the 6 per cent.
war loans of 1812–14 into 5 per cents., but only $56,705 could be
obtained. Two years later the Government was more successful, and,
under the act of May 26, 1824, 6 per cent. stock of 1813 to the
amount of $4,454,728 was exchanged for new stock bearing 4½ per
cent. interest, redeemable in 1833–34. During the same year
$5,000,000 was borrowed at 4½ per cent. to provide for the
payment of the awards made by the Commissioners under the treaty
with Spain of February 22, 1819, and a like amount, at the same rate
of interest, to be applied in paying off that part of the 6 per cent.
stock of 1812 redeemable the following year. The act of March 3,
1825, authorized a loan of $12,000,000, at 4½ per cent. interest, the
money borrowed to be applied in paying off prior loans, but only
$1,539,336 was exchanged for an equal amount of 6 per cent. stock
of 1813.
“In the year 1836 the United States was, for the first time in the
history of the country, practically out of debt. Secretary Woodbury,
in his report of December 8, 1836, estimated the amount of public
debt still outstanding at about $328,582, and this remained unpaid
solely because payment had not been demanded, ample funds to
meet it having been deposited in the United States Bank and loan
offices. The debt outstanding consisted mainly of unclaimed interest
and dividends, of claims for services and supplies during the
Revolution, and of old Treasury notes, and it is supposed that
payment of these had not been asked for solely because the evidences
of the debt had been lost or destroyed. The estimates showed the
probability of a surplus of at least $14,000,000 in the Treasury at the
close of the year 1836, and this estimate proved to be far below the
truth. In this favorable condition of the public finances, Congress
adopted the extraordinary resolution of depositing the surplus over
$5,000,000 with the several States, and under the act of June 23,
1836, surplus revenue amounting to $28,101,644.91 was so
deposited.
“In 1837, however, the state of the country had changed. The
‘flush’ times of 1835 and 1836 had been succeeded by extraordinary
depression, which ultimately produced a panic. In May most of the
banks suspended specie payments. The sales of public lands, and the
duties on the importations of foreign goods, which had helped to
swell the balance in the Treasury to over $42,000,000, had fallen off
enormously. Even on the goods that were imported it was difficult to
collect the duties, for the law compelled them to be paid in specie,
and specie was hard to obtain. It had become impossible not only to
pay the fourth installment of the surplus at the end of 1836 to the
several States, but even to meet the current expenses of the
Government from its ordinary revenues. In this emergency the
Secretary of the Treasury suggested that contingent authority be
given the President to cause the issue of Treasury notes. This
measure was generally supported on the ground of absolute
necessity, as there was a large deficit already existing, and this was
likely to increase from the condition of the country at that time. The
measure was opposed, however, by some who thought that greater
economy in expenditures would relieve the Treasury, while others
denounced it as an attempt “to start a Treasury bank.”
“However, an act was approved October 12, 1837, authorizing an
issue of $10,000,000 in Treasury notes in denominations not less
than fifty dollars, redeemable in one year from date, with interest at
rates fixed by the Secretary, not exceeding 6 per cent. These notes, as
usual, were receivable in payment of all duties and taxes levied by the
United States, and in payment for public lands. Prior to 1846, the
issue of notes of this character amounted to $47,002,900, bearing
interest at rates varying from one tenth of one per cent. to 6 per cent.
To provide in part for their redemption, authority was granted for
the negotiation of several loans, and $21,021,094 was borrowed for
this purpose, bonds being issued for a like sum, bearing interest at
from 5 to 6 per cent., redeemable at specified dates. These bonds
were sold at from 2½ per cent. discount to 3¾ per cent. premium,
and redeemed at from par to 19¼ per cent. advance.
“War with Mexico was declared May 13, 1846, and in order to
provide against a deficiency a further issue of $10,000,000 in
Treasury notes was authorized by act of July 22, 1846, under the
same limitations and restrictions as were contained in the act of
October, 1837, except that the authority given was to expire at the
end of one year from the passage of the act. The sum of $7,687,800
was issued in Treasury notes, and six per cent. bonds having ten
years to run were issued under the same act to the amount of
$4,999,149. These were sold at a small advance, and redeemed at
various rates from par to eighteen and two-thirds per cent. premium.
“The expenses incurred on account of the war with Mexico were
much greater than the original estimates, and the failure to provide
additional revenues sufficient to meet the increased demands made a
new loan necessary, as well as an additional issue of notes, which had
now become a popular method of obtaining funds. Under the
authority granted by act of January 28, 1847, Treasury notes to the
amount of $26,122,100 were issued at par, redeemable one and two
years from date, with interest at from 5– ⅖ to 6 per cent. More
money still being needed, a 6 per cent. loan, having twenty years to
run, was placed upon the market, under the authority of the same
act, and bonds to the amount of $28,230,350 were sold at various
rates, ranging from par to 2 per cent. premium. Of this stock the sum
of $18,815,100 was redeemed at an advance of from 1½ to 21¼ per
cent., the premium paid (exclusive of commissions) amounting to
$3,466,107. Under the act of March 31, 1848, 6 per cent. bonds,
running twenty years, were issued to the amount of $16,000,000,
and sold at a premium ranging from 3 to 4.05 per cent. This loan was
made for the same purpose as the preceding one, and $7,091,658
was redeemed by purchase at an advance ranging from 8 to 22.46
per cent., the premium paid amounting to $1,251,258.
“The widespread depression of trade and commerce which
occurred in 1857 was severely felt by the Government, as well as by
the people, and so great was the decrease in the revenues from
customs that it became absolutely necessary to provide the Treasury
with additional means for meeting the demands upon it. Treasury
notes were considered as preferable to a new loan, and by the act of
December 23, 1857, a new issue was authorized for such an amount
as the exigencies of the public service might require, but not to
exceed at any one time $20,000,000. These notes were receivable in
payment for all debts due the United States, including customs, and
were issued at various rates of interest, ranging from 3 to 6 per cent.,
to the amount of $52,778,900, redeemable one year from date, the
interest to cease at the expiration of sixty days’ notice after maturity.
In May, 1858, the Secretary of the Treasury informed Congress that,
owing to the appropriations having been increased by legislation
nearly $10,000,000 over the estimates, while the customs revenue
had fallen off to a like amount, it would be necessary to provide some
means to meet the deficit. In these circumstances, a new loan was
authorized by act of June 14, 1858, and 5 per cent. bonds amounting
to $20,000,000, redeemable in fifteen years, were sold at an average
premium of over 3½ per cent. Under the act of December 17, 1873,
$13,957,000 in bonds of the loan of 1881, and $260,000 in bonds of
a loan of 1907, were issued in exchange for a like amount of bonds of
this loan.
“The act of June 22, 1860, authorized the President to borrow
$21,000,000 on the credit of the United States, the money to be used
only in the redemption of Treasury notes, and to replace any amount
of such notes in the Treasury which should have been paid in for
public dues. Only $7,022,000 was borrowed at 5 per cent. interest,
the certificates selling at from par to 1.45 per cent. premium. The
failure to realize the whole loan was caused by the political troubles
which culminated in the civil war. In September, bids were invited
for $10,000,000, and the whole amount offered was speedily taken.
It soon became evident, however, that war was inevitable, and a
commercial crisis ensued, during which a portion of the bidders
forfeited their deposits, and the balance of the loan was withdrawn
from the market. Authority was granted by the act of December 17,
1860, for a new issue of Treasury notes, redeemable in one year from
date, but not to exceed $10,000,000 at any one time, with interest at
such rates as might be offered by the lowest responsible bidders after
advertisement. An unsuccessful attempt was made to pledge the
receipts from the sale of public lands specifically for their
redemption. The whole amount of notes issued under this act was
$10,010,900, of which $4,840,000 bore interest at 12 per cent.
Additional offers followed, ranging from 15 to 36 per cent., but the
Treasury declined to accept them.
“Up to this period of our national existence the obtaining of the
money necessary for carrying on the Government and the
preservation inviolate of the public credit had been comparatively an
easy task. The people of the several States had contributed in
proportion to their financial resources; and a strict adherence to the
fundamental maxim laid down by Hamilton had been maintained by
a judicious system of taxation to an extent amply sufficient to
provide for the redemption of all our national securities as they
became due. But the time had come when we were no longer a united
people, and the means required for defraying the ordinary expenses
of the Government were almost immediately curtailed and
jeopardized by the attitude of the States which attempted to secede.
The confusion which followed the inauguration of the administration
of President Lincoln demonstrated the necessity of providing
unusual resources without delay. A system of internal revenue
taxation was introduced, and the tariff adjusted with a view to
increased revenues from customs. As the Government had not only
to exist and pay its way, but also to provide for an army and navy
constantly increasing in numbers and equipment, new and
extraordinary methods were resorted to for the purpose of securing
the money which must be had in order to preserve the integrity of the
nation. Among these were the issue of its own circulating medium in
the form of United States notes[37] and circulating notes,[38] for the
redemption of which the faith of the nation was solemnly pledged.
New loans were authorized to an amount never before known in our
history, and the success of our armies was assured by the
determination manifested by the people themselves to sustain the
Government at all hazards. A brief review of the loan transactions
during the period covered by the war is all that can be attempted
within the limited space afforded this article. The first war loan may
be considered as having been negotiated under the authority of an
act approved February 8, 1861. The credit of the Government at this
time was very low, and a loan of $18,415,000, having twenty years to
run, with 6 per cent. interest, could only be negotiated at a discount
of $2,019,776.10, or at an average rate of $89.03 per one hundred
dollars. From this time to June 30, 1865, Government securities of
various descriptions were issued under authority of law to the
amount of $3,888,686,575, including the several issues of bonds,
Treasury notes, seven-thirties, legal tenders and fractional currency.
The whole amount issued under the same authority to June 30,
1880, was $7,137,646,836, divided as follows:
Six per cent. bonds $1,130,279,000

Five per cent. bonds 196,118,300
Temporary loan certificates 969,992,250
Seven thirty notes 716,099,247
Treasury notes and certificates of indebtedness 1,074,713,132
Old demand notes, legal tenders, coin certificates and
fractional currency 3,050,444,907
Total $7,137,646,836
“This increase may be readily accounted for by the continued issue

of legal tenders, compound interest notes, fractional currency and
coin certificates, together with a large amount of bonds issued in
order to raise the money necessary to pay for military supplies, and
other forms of indebtedness growing out of the war. The rebellion
was practically at an end in May, 1865, yet the large amount of
money required for immediate use in the payment and disbandment
of our enormous armies necessitated the still further negotiation of
loans under the several acts of Congress then in force, and it was not
until after the 31st of August, 1865, that our national debt began to
decrease. At that time the total indebtedness, exclusive of the “old
funded and unfunded debt” of the Revolution, and of cash in the
Treasury, amounted to $2,844,646,626.56. The course of our
financial legislation since that date has been constantly toward a
reduction of the interest, as well as the principal of the public debt.
“By an act approved March 3, 1865, a loan of $600,000,000 was
authorized upon similar terms as had been granted for previous
loans, with the exception that nothing authorized by this act should
be made a legal tender, or be issued in smaller denominations than
fifty dollars. The rate of interest was limited to 6 per cent. in coin, or
7.3 per cent. in currency, the bonds issued to be redeemable in not
less than five, nor more than forty, years. Authority was also given
for the conversion of Treasury notes or other interest-bearing
obligations into bonds of this loan. An amendment to this act was
passed April 12, 1866, authorizing the Secretary of the Treasury, at
his discretion, to receive any Treasury notes or other obligations
issued under any act of Congress, whether bearing interest or not, in
exchange for any description of bonds authorized by the original act;
and also to dispose of any such bonds, either in the United States or
elsewhere, to such an amount, in such manner, and at such rates as
he might deem advisable, for lawful money, Treasury notes,
certificates of indebtedness, certificates of deposit, or other
representatives of value, which had been or might be issued under
any act of Congress; the proceeds to be used only for retiring
Treasury notes or other national obligations, provided the public
debt was not increased thereby. As this was the first important
measure presented to Congress since the close of the war tending to
place our securities upon a firm basis, the action of Congress in
relation to it was looked forward to with a great deal of interest. The
discussion took a wide range, in which the whole financial
administration of the Government during the war was reviewed at
length. After a long and exciting debate the bill finally passed, and
was approved by the President. Under the authority of these two
acts, 6 per cent, bonds to the amount of $958,483,550 have been
issued to date. These bonds were disposed of at an aggregate
premium of $21,522,074, and under the acts of July 14, 1870, and
January 20, 1871, the same bonds to the amount of $725,582,400
have been refunded into other bonds bearing a lower rate of interest.
The success of these several loans was remarkable, every exertion
being used to provide for their general distribution among the
people.
“In 1867 the first issue of 6 per cent. bonds, known as five-
twenties, authorized by the act of Feb. 25, 1862, became redeemable,
and the question of refunding them and other issues at a lower rate
of interest had been discussed by the Secretary of the Treasury in his
annual reports, but the agitation of the question as to the kinds of
money in which the various obligations of the Government should be
paid, had so excited the apprehension of investors as to prevent the
execution of any refunding scheme.
“The act to strengthen the public credit was passed March 18,
1869, and its effect was such as secured to the public the strongest
assurances that the interest and principal of the public debt
outstanding at that time would be paid in coin, according to the
terms of the bonds issued, without any abatement.
“On the 12th of January, 1870, a bill authorizing the refunding and
consolidation of the national debt was introduced in the Senate, and
extensively debated in both Houses for several months, during which
the financial system pursued by the Government during the war was
freely reviewed. The adoption of the proposed measure resulted in an
entire revolution of the refunding system, under which the public
debt of the United States at that time was provided for, by the
transmission of a large amount of debt to a succeeding generation.
The effect of this attempt at refunding the major portion of the public
debt was far more successful than any similar effort on the part of
any Government, so far as known.
“The act authorizing refunding certificates convertible into 4 per
cent. bonds, approved February 26, 1879, was merely intended for
the benefit of parties of limited means, and was simply a
continuation of the refunding scheme authorized by previous
legislation.
“The period covered precludes any attempt toward reviewing the
operation by which the immediate predecessor of the present
Secretary reduced the interest on some six hundred millions of 5 and
6 per cent. bonds to 3½ per cent. It is safe to say, however, that
under the administration of the present Secretary there will be no
deviation from the original law laid down by Hamilton.”
James A. Garfield.
James A. Garfield and Chester A. Arthur were publicly inaugurated

President and Vice-President of the United States March 4, 1881.
President Garfield in his inaugural address promised full and
equal protection of the Constitution and the laws for the negro,
advocated universal education as a safeguard of suffrage, and
recommended such an adjustment of our monetary system “that the
purchasing power of every coined dollar will be exactly equal to its
debt-paying power in all the markets of the world.” The national debt
should be refunded at a lower rate of interest, without compelling the
withdrawal of the National Bank notes, polygamy should be
prohibited, and civil service regulated by law.
An extra session of the Senate was opened March 4. On the 5th,
the following cabinet nominations were made and confirmed:
Secretary of State, James G. Blaine, of Maine; Secretary of the
Treasury, William Windom, of Minnesota; Secretary of the Navy,
William H. Hunt, of Louisiana; Secretary of War, Robert T. Lincoln,
of Illinois; Attorney-General, Wayne MacVeagh, of Pennsylvania;
Postmaster-General, Thomas L. James, of New York; Secretary of the
Interior, Samuel J. Kirkwood, of Iowa.
In this extra session of the Senate Vice-President Arthur had to
employ the casting vote on all questions where the parties divided,
and he invariably cast it on the side of the Republicans. The evenness
of the parties caused a dead-lock on the question of organization, for
when David Davis, of Illinois, voted with the Democrats, the
Republicans had not enough even with the Vice-President, and he
was not, therefore, called upon to decide a question of that kind. The
Republicans desired new and Republican officers; the Democrats
desired to retain the old and Democratic ones.
Republican Factions.
President Garfield, March 23d, sent in a large number of

nominations, among which was that of William H. Robertson, the
leader of the Blaine wing of the Republican party in New York, to be
Collector of Customs. He had previously sent in five names for
prominent places in New York, at the suggestion of Senator
Conkling, who had been invited by President Garfield to name his
friends. At this interview it was stated that Garfield casually
intimated that he would make no immediate change in the New York
Collectorship, and both factions seemed satisfied to allow Gen’l
Edwin A. Merritt to retain that place for a time at least. There were
loud protests, however, at the first and early selection of the friends
of Senator Conkling to five important places, and these protests were
heeded by the President. With a view to meet them, and, doubtless,
to quiet the spirit of faction rapidly developing between the Grant
and anti-Grant elements of the party in New York, the name of Judge
Robertson was sent in for the Collectorship. He had battled against
the unit rule at Chicago, disavowed the instructions of his State
Convention to vote for Grant, and led the Blaine delegates from that
State while Blaine was in the field, and when withdrawn went to
Garfield. Senator Conkling now sought to confirm his friends, and
hold back his enemy from confirmation; but these tactics induced
Garfield to withdraw the nomination of Conkling’s friends, and in
this way Judge Robertson’s name was alone presented for a time.
Against this course Vice-President Arthur and Senators Conkling and
Platt remonstrated in a letter to the President, but he remained firm.
Senator Conkling, under the plea of “the privilege of the Senate,”—a
courtesy and custom which leaves to the Senators of a State the right
to say who shall be confirmed or rejected from their respective States
if of the same party—now sought to defeat Robertson. In this battle
he had arrayed against him the influence of his great rival, Mr.
Blaine, and it is presumed the whole power of the administration. He
lost, and the morning following the secret vote, May 17th, 1881, his
own and the resignation of Senator Platt were read. These
resignations caused great excitement throughout the entire country.
They were prepared without consultation with any one—even Vice-
President Arthur, the intimate friend of both, not knowing anything
of the movement until the letters were opened at the chair where he
presided. Logan and Cameron—Conkling’s colleagues in the great
Chicago battle—were equally unadvised. The resignations were
forwarded to Gov. Cornell, of New York, who, by all permissible
delays, sought to have them reconsidered and withdrawn, but both
Senators were firm. The Senate confirmed Judge Robertson for
Collector, and General Merritt as Consul-General at London, May
18th, President Garfield having wisely renewed the Conkling list of
appointees, most of whom declined under the changed condition of
affairs.
These events more widely separated the factions in New York—one
wing calling itself “Stalwart,” the other “Half-Breed,” a term of
contempt flung at the Independents by Conkling. Elections must
follow to fill the vacancies, the New York Legislature being in
session. These vacancies gave the Democrats for the time control of
the United States Senate, but they thought it unwise to pursue an
advantage which would compel them to show their hands for or
against one or other of the opposing Republican factions. The extra
session of the Senate adjourned May 20th.
The New York Legislature began balloting for successors to
Senators Conkling and Platt on the 31st of May. The majority of the
Republicans (Independents or “Half-breeds”) supported Chauncey
M. Depew as the successor of Platt for the long term, and William A.
Wheeler as the successor of Conkling for the short term, a few
supporting Cornell. The minority (Stalwarts) renominated Messrs.
Conkling and Platt. The Democrats nominated Francis Kernan for
the long term, and John C. Jacobs for the short term; and, on his
withdrawal, Clarkson N. Potter. The contest lasted until July 22, and
resulted in a compromise on Warner A. Miller as Platt’s successor,
and Elbridge G. Lapham as Conkling’s successor. In Book VII., our
Tabulated History of Politics, we give a correct table of the ballots.
These show at a single glance the earnestness and length of the
contest.
The factious feelings engendered thereby were carried into the Fall
nominations for the Legislature, and as a result the Democrats
obtained control, which in part they subsequently lost by the refusal
of the Tammany Democrats to support their nominees for presiding
officers. This Democratic division caused a long and tiresome dead-
lock in the Legislature of New York. It was broken in the House by a
promise on the part of the Democratic candidate for Speaker to favor
the Tammany men with a just distribution of the committees—a
promise which was not satisfactorily carried out, and as a result the
Tammany forces of the Senate joined hands with the Republicans.
The Republican State ticket would also have been lost in the Fall of
1881, but for the interposition of President Arthur, who quickly
succeeded in uniting the warring factions. This work was so well
done, that all save one name on the ticket (Gen’l Husted) succeeded.
The same factious spirit was manifested in Pennsylvania in the
election of U. S. Senator in the winter of 1881, the two wings taking
the names of “Regulars” and “Independents.” The division occurred
before the New York battle, and it is traceable not alone to the bitter
nominating contest at Chicago, but to the administration of
President Hayes and the experiment of civil service reform.
Administrations which are not decided and firm upon political
issues, invariably divide their parties, and while these divisions are
not always to be deplored, and sometimes lead to good results, the
fact that undecided administrations divide the parties which they
represent, ever remains. The examples are plain: Van Buren’s,
Tyler’s, Fillmore’s, Buchanan’s, and Hayes’. The latter’s indecision
was more excusable than that of any of his predecessors. The
inexorable firmness of Grant caused the most bitter partisan
assaults, and despite all his efforts to sustain the “carpet-bag
governments” of the South, they became unpopular and were rapidly
supplanted. As they disappeared, Democratic representation from
the South increased, and this increase continued during the
administration of Hayes—the greatest gains being at times when he
showed the greatest desire to conciliate the South. Yet his
administration did the party good, in this, that while at first dividing,
it finally cemented through the conviction that experiments of that
kind with a proud Southern people were as a rule unavailing. The
reopening of the avenues of trade and other natural causes,
apparently uncultivated, have accomplished in this direction much
more than any political effort.
In Pennsylvania a successor to U. S. Senator Wm. A. Wallace was
to be chosen. Henry W. Oliver, Jr., received the nomination of the
Republican caucus, the friends of Galusha A. Grow refusing to enter
after a count had been made, and declaring in a written paper that
they would not participate in any caucus, and would independently
manifest their choice in the Legislature. The following is the first vote
in joint Convention:
OLIVER.
Senate 20
House 75
Total 95
GROW.
Senate 12
House 44
Total 56
BREWSTER.
Senate
House 1
Total 1
M’VEAGH.
Senate
House 1
Total 1
WALLACE.
Senate 16
House 77
Total 93
AGNEW.
Senate 1
House
Total 1
BAIRD.
Senate
House 1
Total 1
Whole number of votes cast, 248; necessary to a choice, 125.

On the 17th of January the two factions issued opposing addresses.
From these we quote the leading ideas, which divided the factions.
The “Regulars” said:
“Henry W. Oliver, jr., of Allegheny county, was nominated on the
third ballot, receiving 79 of the 95 votes present. Under the rules of
all parties known to the present or past history of our country, a
majority of those participating should have been sufficient; but such
was the desire for party harmony and for absolute fairness, that a
majority of all the Republican members of the Senate and House was
required to nominate. The effect of this was to give those remaining
out a negative voice in the proceedings, the extent of any privilege
given them in regular legislative sessions by the Constitution. In no
other caucus or convention has the minority ever found such high
consideration, and we believe there remains no just cause of
complaint against the result. Even captious faultfinding can find no
place upon which to hang a sensible objection. Mr. Oliver was,
therefore, fairly nominated by the only body to which is delegated
the power of nomination and by methods which were more than just,
which, from every standpoint, must be regarded as generous; and in
view of these things, how can we, your Senators and Representatives,
in fairness withhold our support from him in open sessions; rather
how can we ever abandon a claim established by the rules regulating
the government of all parties, accepted by all as just, and which are
in exact harmony with that fundamental principle of our
Government which proclaims the right of the majority to rule? To do
otherwise is to confess the injustice and the failure of that principle—
something we are not prepared to do. It would blot the titles to our
own positions. There is not a Senator or member who does not owe
his nomination and election to the same great principle. To profit by
its acceptance in our own cases and to deny it to Mr. Oliver would be
an exhibition of selfishness too flagrant for our taste. To
acknowledge the right to revolt when no unfairness can be truthfully
alleged and when more than a majority have in the interest of
harmony been required to govern, would be a travesty upon every
American notion and upon that sense of manliness which yields
when fairly beaten.”
The “Independent” address said:
“First. We recognize a public sentiment which demands that in the
selection of a United States Senator we have regard to that dignity of
the office to be filled, its important duties and functions, and the
qualifications of the individual with reference thereto. This
sentiment is, we understand, that there are other and higher
qualifications for this distinguished position than business
experience and success, and reckons among these the
accomplishments of the scholar, the acquirements of the student, the
mature wisdom of experience and a reasonable familiarity with
public affairs. It desires that Pennsylvania shall be distinguished
among her sister Commonwealths, not only by her populous cities,
her prosperous communities, her vast material wealth and
diversified industries and resources, but that in the wisdom, sagacity
and statesmanship of her representative she shall occupy a
corresponding rank and influence. To meet this public expectation
and demand we are and have at all times been willing to subordinate
our personal preferences, all local considerations and factional
differences, and unite with our colleagues in the selection of a
candidate in whom are combined at least some of these important
and essential qualifications. It was only when it became apparent
that the party caucus was to be used to defeat this popular desire and
to coerce a nomination which is conspicuously lacking in the very
essentials which were demanded, that we determined to absent
ourselves from it. * * *
“Second, Having declined to enter the caucus, we adhere to our
determination to defeat, if possible, its nominee, but only by the
election of a citizen of unquestioned fidelity to the principles of the
Republican party. In declaring our independency from the caucus
domination we do not forget our allegiance to the party whose
chosen representatives we are. The only result of our policy is the
transfer of the contest from the caucus to the joint convention of the
two houses. There will be afforded an opportunity for the expression
of individual preferences and honorable rivalry for an honorable
distinction. If the choice shall fall upon one not of approved loyalty
and merit, the fault will not be ours.”
After a long contest both of the leading candidates withdrew, and
quickly the Regulars substituted General James A. Beaver, the
Independent Congressman, Thomas M. Bayne. On these names the
dead-lock remained unbroken. Without material change the
balloting continued till February 17th, when both Republican
factions agreed to appoint conference committees of twelve each,
with a view to selecting by a three-fourths vote a compromise
candidate. The following were the respective committees: For the
Independents: Senators Davis, Bradford; Lee, Venango; Stewart,
Franklin; Lawrence, Washington; Representatives Wolfe, Union;
Silverthorne, Erie; Mapes, Venango; McKee, Philadelphia; Slack,
Allegheny; Stubs, Chester; Niles, Tioga; and Derickson, Crawford.
For the Regulars: Senators Greer, Butler; Herr, Dauphin; Smith,
Philadelphia; Keefer, Schuylkill; Cooper, Delaware; Representatives
Pollock, Philadelphia; Moore, Allegheny; Marshall, Huntingdon;
Hill, Indiana; Eshleman. Lancaster; Thomson, Armstrong; and
Billingsley, Washington.
The joint convention held daily sessions and balloted without
result until February 22d, when John I. Mitchell, of Tioga,
Congressman from the 16th district, was unanimously agreed upon
as a compromise candidate. He was nominated by a full Republican
caucus on the morning of February 23d, and elected on the first
ballot in joint convention on that day, the vote standing: Mitchell,
150; Wallace, 92; MacVeagh, 1; Brewster, 1.
The spirit of this contest continued until fall. Senator Davies, a
friend of Mr. Grow, was a prominent candidate for the Republican
nomination for State Treasurer. He was beaten by General Silas M.
Baily, and Davies and his friends cordially made Baily’s nomination
unanimous. Charles S. Wolfe, himself the winter before a candidate
for United States Senator, was dissatisfied. He suddenly raised the
Independent flag, in a telegram to the Philadelphia Press, and as he
announced was “the nominee of a convention of one” for State
Treasurer. After a canvass of remarkable energy on the part of Mr.
Wolfe, General Baily was elected, without suffering materially from
the division. Mr. Wolfe obtained nearly 50,000 votes, but as almost
half of them were Democratic, the result was, as stated, not seriously
affected.
The Independents in Pennsylvania, however, were subdivided into
two wings, known as the Continental and the Wolfe men—the former
having met since the election last fall, (State Senator John Stewart,
chairman) and proclaimed themselves willing and determined to
abide all Republican nominations fairly made, and to advocate
“reform within the party lines.” These gentlemen supported Gen.
Baily and largely contributed to his success, and as a rule they regard
with disfavor equal to that of the Regulars, what is known as the
Wolfe movement. These divisions have not extended to other States,
nor have they yet assumed the shape of third parties unless Mr.
Wolfe’s individual canvass can be thus classed. Up to this writing
(March 10, 1882,) neither wing has taken issue with President Arthur
or his appointments, though there were some temporary indications
of this when Attorney General MacVeagh, of Pennsylvania, persisted
in having his resignation accepted. President Arthur refused to
accept, on the ground that he desired MacVeagh’s services in the
prosecution of the Star Route cases, and Mr. MacVeagh withdrew for
personal and other reasons not yet fully explained. In this game of
political fence the position of the President was greatly strengthened.
Singularly enough, in the only two States where factious divisions
have been recently manifested in the Republican ranks, they effected
almost if not quite as seriously the Democratic party. There can be
but one deduction drawn from this, to wit:—That a number in both
of the great parties, were for the time at least, weary of their
allegiance. It is possible that nothing short of some great issue will
restore the old partisan unity, and partisan unity in a Republic,
where there are but two great parties, is not to be deplored if relieved
of other than mere political differences. The existence of but two
great parties, comparatively free from factions, denotes government
health; where divisions are numerous and manifest increasing
growth and stubbornness, there is grave danger to Republican
institutions. We need not, however, philosophize when Mexico and
the South American Republics are so near.

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Chemical Thermodynamics-Theory and

Applications 1st Edition W.J. Rankin

Chemical thermodynamics for process simulation Gmehling

Chemical Thermodynamics in Materials Science Taishi

Experimental Thermodynamics Volume X Non equilibrium

Thermodynamics: Principles Characterizing Physical and

Film and the Afterlife 1st Edition David Rankin.

Biomolecular Thermodynamics: From Theory to Application

Thermodynamics Concepts and Applications 2nd Edition

Chemical Reactions: Basic Theory and Computing 1st

© 2020 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13 978-0-367-22247-5 (Hardback)

Library of Congress Cataloging-in-Publication Data

Names: Rankin, W. J., author.

Visit the Taylor & Francis Web site at

and the CRC Press Web site at

Chapter 1 An overview of thermodynamics..................................................................................1

Chapter 2 Fundamental concepts...................................................................................................5

3.4 Real gases......................................................................................................... 29

Chapter 4 The first law................................................................................................................. 35

Chapter 5 Sources of thermodynamic data for substances.......................................................... 59

Chapter 6 Some applications of the first law............................................................................... 67

Chapter 7 The second and third laws........................................................................................... 81

Chapter 8 Gibbs and Helmholtz energies.................................................................................. 103

Chapter 9 Solutions.................................................................................................................... 123

9.3.1 Relative partial and integral quantities............................................. 128

Chapter 10 Reactive systems – single reactions.......................................................................... 157

Chapter 11 Gibbs energy applications to metal production......................................................... 179

11.4 Oxidation reactions......................................................................................... 191

Chapter 12 Electrolyte solutions.................................................................................................. 195

Chapter 13 Phase equilibria: non-reactive systems..................................................................... 221

Chapter 14 Phase equilibria: reactive systems............................................................................. 251

Chapter 15 Complex equilibria.................................................................................................... 267

Chapter 16 Electrochemistry....................................................................................................... 279

Chapter 17 Some applications of electrochemistry..................................................................... 305

17.1.1 Electrowinning of metals.................................................................. 305

HOW TO USE THIS BOOK

TACKLING THE PROBLEMS

Six per cent. bonds $1,130,279,000

“This increase may be readily accounted for by the continued issue

James A. Garfield and Chester A. Arthur were publicly inaugurated

President Garfield, March 23d, sent in a large number of

Whole number of votes cast, 248; necessary to a choice, 125.

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