An Introduction to

Chemical Thermodynamics
 An Introduction to
Chemical Thermodynamics

G. Koper

Department of Chemical Engineering

Faculty of Applied Sciences
Delft University of Technology

VSSD
­c VSSD
First edition 2007
Second edition 2008; corrected 2009

Published by VSSD
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NUR 952

Key words: chemical thermodynamics

Preface

After being asked to teach the first year Chemical Thermodynamics course for the newly
developed Molecular Science and Technology education at the Delft University of Tech-
nology, I first conducted a small survey of what was being taught at other Dutch universi-
ties and what the experiences were. The answers were surprising: many of my colleagues
responded that Chemical Thermodynamics was not very popular amongst the students,
the results were usually not very good and many universities were contemplating whether
the course should be removed from the curriculum.
Consulting the text books being used, it occurred to me that chemistry was not at the
forefront. All start with the behavior of gases, then proceed to introduce work and heat
transfer after which the First and Second Law are discussed, basically from a mechanical
point of view. Only in later chapters, chemical topics are discussed. At that point, one
may imagine, chemistry students will have lost interest!
After this the idea was born to develop a completely new course in Chemical Thermo-
dynamics where chemistry would be the central issue. This was frequently discussed with
colleagues and one brought a paper to my attention that dealt with the primary role of the
Gibbs energy1 . This was a good starting point as it put what I consider the most important
aspect of Chemical Thermodynamics up front: the prediction whether processes can run
spontaneously or not2 .
The second issue was to proceed to Work and Efficiency without an emphasis on
mechanics or heat engines. Both topics do not belong to the scope of chemistry students.
The obvious alternative is the fuel cell. As a device, it contains all aspects of Chemical
Thermodynamics that are necessary without the need to discuss in detail what is done
with the delivered work. Unfortunately, there is some confusion in the literature about the
efficiency of fuel cells: some claim it can be over 100% and others find it remarkable that
the efficiency is higher than the Carnot efficiency. Both issues are discussed in detail by
Lutz and coworkers3 .
As always, an idea is not really new! At some point I found a booklet by Guggen-
1 G. Job and F. Herrmann, Chemical potential – a quantity in search of recognition, Eur J Phys 27 (2006)

353-371
2 F.J. Gerhartl, The A B
 C of Chemical Thermodynamics, J Chem Ed 71 (1994) 539 - 548
3 A.E. Lutz, R.S. Larson, and J.O. Keller, Thermodynamic comparison of fuel cells to the Carnot cycle, Int J

Hyd Energy 27 (2002) 1103 - 1111.

v
vi An introduction to chemical thermodynamics

heim4 . Guggenheim is relatively outspoken on the way Chemical Thermodynamics is to

be taught. He starts the preface with

Anyone thoroughly familiar with thermodynamics can write an advanced

treatise on the subject. It seems to be immeasurably more difficult to write an
elementary introduction to chemical thermodynamics. Attempts at this differ
only in the degree of their failure. The greatest difficulty is self-imposed by
the authors. They have not troubled to ask themselves what they mean by ‘el-
ementary’, still less what they ought to mean. In the worst type of exposition,
‘elementary’ means telling the reader untruths on the plea that an untruth is
easier to understand than the truth. This is a blatant fallacy (Guggenheim,
Education in Chemistry, 1966, 3 (2) 105). The more intelligent the student
the sooner he will discover that something is wrong and the more severe will
be the mental shock.
I know exactly what I mean by an elementary introduction to chemical ther-
modynamics. The one and only object to teach the student how the direction
of chemical reactions and how the equilibrium condition for balanced reac-
tions can be determined from calorimetry and related measurements.

He then continues to explain how the topic should be worked out and he claims that at no
place it is necessary to introduce “untruths”. The booklet is no longer for sale, except at
second hand bookshops.
The first part of the book is therefore wholly devoted to processes, mostly chemical.
It discusses how to predict spontaneity using tabulated information, how to evaluate the
maximum work from a process and what efficiency is achievable. For this, only the Gibbs
energy and the enthalpy are needed. In the last chapter of this part, the concept of entropy
is introduced as the difference between the Gibbs energy, that predicts the maximum
work, and the enthalpy, that manages the entropy balance.
The second part of the book is devoted to chemical and physical equilibria. An attempt
is made to expose the universality of the various relations that exist for equilibria and
their relation with the Gibbs energy. Ideal mixing relations and ideal solution relations
are constantly being used as a simplified approach to the real situation. In the last chapter
of this part, the deviations from ideality are assessed and the magnitude of the fugacity
and activity coefficients is critically discussed.
The course is not only to be given to chemistry students but also chemical engineering
students. They need to know more about processes and their efficiencies. Most textbooks
deal with efficiency in some way, but it remains unclear why the thermodynamic efficien-
cies are not realized in practice. There is usually a vague discussion of irreversibility but
no connection is made to energy dissipation in relation to the efficiency of a process. An
exception is the book by Kondepudi and Prigogine5 that does cover the thermodynamics
4 E.A. Guggenheim, Elements of Chemical Thermodynamics, The Royal Institute of Chemistry, London,

1966.
5 D. Kondepudi and I. Prigogine, Modern Thermodynamics : From Heat Engines to Dissipative Structures,

John Wiley & Sons, 1998.

 Preface vii

of irreversible processes. Therefore the last part of the book is devoted to distributed pro-
cesses. In the first chapter some important aspects of formal thermodynamics are covered.
In particular the role of entropy to identify equilibrium and stability is discussed. The sec-
ond chapter of this part continues this discussion and introduces the concept of internal
entropy production. To discuss these two issues, systems are subdivided into two parts
that are not necessarily in equilibrium: the system is inhomogeneous. The final chapter
of this part explains how fully inhomogeneous and flowing systems can be dealt with.
The development of this course was interesting and I hope that students appreciate it.
There was one problem: no textbook is available that deals with Chemical Thermody-
namics in this way. Also, many of the exercises are not suited for this treatment. This is
the reason for writing this book. Exercises are being made available electronically.
Finally, I thank all who have helped me writing this book and the Technical University
of Delft for their support. Last but not least I thank my wife and children for their patience:
they had to suffer my absentmindedness while working to finish this book.

Ger Koper
Leiden, 4 June 2007.

Preface to the second edition

Many corrections have been made to the text of the first edition and I thank students and
colleagues for pointing these out to me. In some places also some additional material has
been inserted. I realize that a text as this will probably never be flawless and I therefore
invite anyone to look for possible errors and make them known to me.
The book is now used by myself for a course in Chemical Thermodynamics for three
courses: Molecular Science and Technology, Life Science and Technology, and Applied
Earth Sciences of the Technical University in Delft. After being asked to give a more
advanced course in chemical thermodynamics for the Life Science and Technology stu-
dents, I decided to add three chapters dealing with macromolecular systems. The topics
dealt with in these chapters are relatively modern. Appropriate references to the relevant
literature are made. An effort has been made to present this material from a few unifying
concepts in order to demonstrate the analogy between the various treatments in the current
literature. Also, the relation to colloid science - even though dealing more with particles
than with macromolecules - is being discussed.
Over time, more and more exercises are being made. It will take some more time
though to have these neatly organized in an electronic format. Until that time, an old
collection is all that is currently available upon request from the publisher.

Ger Koper
Leiden, 25 August 2008.
Contents

Preface v

I Processes in Chemistry and Biochemistry 1

1 Overview 2
1.1 Zeroth law: thermal equilibrium . . . . . . . . . . . . . . . . . . . . . . 2
1.1.1 Thermometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 First law: energy conservation . . . . . . . . . . . . . . . . . . . . . . . 5
1.3 Second law: Gibbs energy . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1 Available work . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.4 Third law: absolute zero . . . . . . . . . . . . . . . . . . . . . . . . . . 11

2 Spontaneity of processes 13
2.1 Gibbs energy predicts spontaneity . . . . . . . . . . . . . . . . . . . . . 13
2.2 Gibbs energy calculations . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.2.1 Temperature dependence . . . . . . . . . . . . . . . . . . . . . . 15
2.2.2 Pressure dependence . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2.3 Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3 Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

3 Available work 25
3.1 Spontaneous processes . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.2 Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.2.1 Black powder . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.2.2 Hydrogen fuel cell . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.2.3 Muscle power . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.3 Measurement of Gibbs energy . . . . . . . . . . . . . . . . . . . . . . . 31
3.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.4.1 Gibbs energy is a state function . . . . . . . . . . . . . . . . . . 32
3.4.2 dG 
SdT  V d p  ∑ j μ j dn j . . . . . . . . . . . . . . . . . . 33
3.4.3 Chemical potential of ideal mixtures . . . . . . . . . . . . . . . . 34
3.4.4 2nd law of thermodynamics . . . . . . . . . . . . . . . . . . . . 34

viii
 Contents ix

4 Energy conservation 36
4.1 Calorimetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.1.1 Caloric equivalent of electrical energy . . . . . . . . . . . . . . . 36
4.1.2 Caloric equivalent of a combustion reaction . . . . . . . . . . . . 37
4.1.3 Caloric equivalent of radiation . . . . . . . . . . . . . . . . . . . 38
4.1.4 Caloric equivalent of mechanical work . . . . . . . . . . . . . . . 39
4.2 First law of thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . 39
4.3 Enthalpy calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.3.1 Temperature dependence . . . . . . . . . . . . . . . . . . . . . . 41
4.3.2 Pressure dependence . . . . . . . . . . . . . . . . . . . . . . . . 42
4.4 Hess’ law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.5 Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.5.1 Methane combustion . . . . . . . . . . . . . . . . . . . . . . . . 43
4.5.2 Nitrogen conversion . . . . . . . . . . . . . . . . . . . . . . . . 44

5 Efficiency and entropy 46

5.1 Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
5.1.1 Spontaneous processes . . . . . . . . . . . . . . . . . . . . . . . 46
5.1.2 Driven processes . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5.2 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
5.2.1 Gibbs-Helmholtz equation . . . . . . . . . . . . . . . . . . . . . 50
5.2.2 Clausius’ inequality . . . . . . . . . . . . . . . . . . . . . . . . 51
5.2.3 Molecular picture . . . . . . . . . . . . . . . . . . . . . . . . . . 52

II Chemical and Physical Equilibria 55

6 General aspects of equilibria 56
6.1 Chemical equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
6.1.1 Gibbs reaction energy . . . . . . . . . . . . . . . . . . . . . . . 56
6.1.2 Van ’t Hoff’s law . . . . . . . . . . . . . . . . . . . . . . . . . . 61
6.1.3 Example: esterification reaction towards ethyl acetate . . . . . . . 62
6.2 Phase equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
6.2.1 Trouton’s rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.2.2 Phase boundaries . . . . . . . . . . . . . . . . . . . . . . . . . . 66

7 Phase equilibria of pure substances 70

7.1 Phase transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
7.1.1 Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
7.1.2 Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
7.1.3 Order of phase transitions . . . . . . . . . . . . . . . . . . . . . 71
7.2 Phase diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.2.1 Phase diagram of CO2 . . . . . . . . . . . . . . . . . . . . . . . 73
7.2.2 Phase diagram of H2 O . . . . . . . . . . . . . . . . . . . . . . . 76
x An introduction to chemical thermodynamics

7.2.3 Phase diagram of carbon . . . . . . . . . . . . . . . . . . . . . . 77

7.3 Equations of state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7.3.1 Van der Waals equation of state . . . . . . . . . . . . . . . . . . 78

8 Capillary phenomena and adsorption 82

8.1 Surface free energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
8.1.1 Young’s law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
8.1.2 Laplace’s law . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
8.1.3 Kelvin’s law . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
8.2 Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
8.2.1 Reversibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

9 Phase equilibria of mixtures 91

9.1 Vapor-liquid equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
9.1.1 Dalton’s law . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
9.1.2 Raoult’s law . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
9.1.3 Pxy-diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
9.1.4 Txy-diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
9.2 Liquid-liquid equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
9.3 Solid-liquid equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98

10 Mixtures and colligative properties 101

10.1 Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
10.1.1 Gaseous mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . 101
10.1.2 Vapor-Liquid mixtures . . . . . . . . . . . . . . . . . . . . . . . 102
10.1.3 Entropy and enthalpy of ideal mixing . . . . . . . . . . . . . . . 103
10.2 Molecular picture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
10.2.1 Entropy of mixing . . . . . . . . . . . . . . . . . . . . . . . . . 103
10.2.2 Enthalpy of mixing . . . . . . . . . . . . . . . . . . . . . . . . . 105
10.2.3 Regular solutions . . . . . . . . . . . . . . . . . . . . . . . . . . 106
10.2.4 Dilute solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
10.2.5 Non-ideal mixing . . . . . . . . . . . . . . . . . . . . . . . . . . 107
10.3 Colligative properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
10.3.1 Transition temperature shifts . . . . . . . . . . . . . . . . . . . . 108
10.3.2 Osmotic pressure . . . . . . . . . . . . . . . . . . . . . . . . . . 109
10.3.3 Non-ideal behavior . . . . . . . . . . . . . . . . . . . . . . . . . 111

11 Non-ideal mixtures 112

11.1 Gaseous mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
11.2 Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
11.2.1 Dilute solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
11.2.2 Regular solutions . . . . . . . . . . . . . . . . . . . . . . . . . . 114
11.3 Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
11.3.1 Dissociation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
 Contents xi

11.3.2 Electroneutrality . . . . . . . . . . . . . . . . . . . . . . . . . . 116

11.3.3 Debye-Hückel theory . . . . . . . . . . . . . . . . . . . . . . . . 116

III Distributed Processes 119

12 Fundamentals of chemical thermodynamics 120
12.1 Laws of thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . 120
12.1.1 Extensivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
12.1.2 Internal energy . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
12.1.3 The entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
12.1.4 Internal heat exchange . . . . . . . . . . . . . . . . . . . . . . . 123
12.1.5 Heat and work exchange . . . . . . . . . . . . . . . . . . . . . . 124
12.1.6 Heat and material exchange . . . . . . . . . . . . . . . . . . . . 125
12.2 Legendre transforms . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
12.2.1 Internal energy to enthalpy . . . . . . . . . . . . . . . . . . . . . 125
12.2.2 Internal energy to Helmholtz energy . . . . . . . . . . . . . . . . 127
12.2.3 Enthalpy to Gibbs energy . . . . . . . . . . . . . . . . . . . . . . 128
12.2.4 Grand potential . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
12.3 Euler’s theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
12.3.1 Partial molar quantities . . . . . . . . . . . . . . . . . . . . . . . 130
12.3.2 Gibbs’ phase rule . . . . . . . . . . . . . . . . . . . . . . . . . . 131
12.4 Cauchy’s integral theorem . . . . . . . . . . . . . . . . . . . . . . . . . 132
12.4.1 Maxwell relations . . . . . . . . . . . . . . . . . . . . . . . . . . 133

13 Irreversible processes 134

13.1 Entropy production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
13.1.1 Equalization of temperature . . . . . . . . . . . . . . . . . . . . 135
13.1.2 (Irreversible) Expansion . . . . . . . . . . . . . . . . . . . . . . 136
13.1.3 Chemical reactions . . . . . . . . . . . . . . . . . . . . . . . . . 137
13.2 Thermodynamic efficiency . . . . . . . . . . . . . . . . . . . . . . . . . 140
13.2.1 Maximum efficiency . . . . . . . . . . . . . . . . . . . . . . . . 142

14 Flow processes 144

14.1 Fluid element . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
14.2 Local equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
14.3 Balance equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
14.3.1 Mass balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
14.3.2 Energy balance . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
14.3.3 Momentum balance . . . . . . . . . . . . . . . . . . . . . . . . . 150
14.3.4 Entropy balance . . . . . . . . . . . . . . . . . . . . . . . . . . 150
xii An introduction to chemical thermodynamics

IV Macromolecular Systems 151

15 Macromolecular solutions 152
15.1 Protein phase behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
15.2 Virial expansion of osmotic pressure . . . . . . . . . . . . . . . . . . . . 153
15.2.1 Second virial coefficient . . . . . . . . . . . . . . . . . . . . . . 154
15.2.2 Stability condition . . . . . . . . . . . . . . . . . . . . . . . . . 158
15.3 Experimental determination of second virial coefficients . . . . . . . . . 158
15.3.1 Colligative properties . . . . . . . . . . . . . . . . . . . . . . . . 158
15.3.2 External fields . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
15.4 Osmotic stress . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164

16 Macromolecular binding equilibria 167

16.1 The binding polynomial . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
16.1.1 Poly (ethylene imine): an example . . . . . . . . . . . . . . . . . 169
16.2 Analysis of binding isotherms . . . . . . . . . . . . . . . . . . . . . . . 173
16.2.1 Potentiometric titration . . . . . . . . . . . . . . . . . . . . . . . 173
16.2.2 Graphical methods . . . . . . . . . . . . . . . . . . . . . . . . . 175
16.2.3 Isothermal titration calorimetry . . . . . . . . . . . . . . . . . . 179
16.3 Cooperativity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
16.4 Multidentate binding . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185

17 Membranes 187
17.1 Dialysis membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
17.1.1 Concentration equalization . . . . . . . . . . . . . . . . . . . . . 188
17.1.2 Osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
17.1.3 Binding equilibria . . . . . . . . . . . . . . . . . . . . . . . . . 192
17.1.4 Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
17.2 Biological membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . 196

Index 199
 Part I

Processes in Chemistry and

Biochemistry
Chapter 1

Overview

The core of chemical thermodynamics is captured in four Laws of Thermodynamics that

in essence summarize the experimental findings in this field over the past hundreds of
years. Most of the times only the First Law on energy conservation and the Second Law
on the direction of processes are named. But the Zeroth Law is important as well as it tells
us how to think about thermal equilibrium. The Third Law is often neglected because at
first glance it appears to be only of theoretical importance. But it does provide our best
definition of the absolute temperature scale and as such it is sufficiently important to be
mentioned as well.

1.1 Zeroth law: thermal equilibrium

The object of study in thermodynamic analysis is called system. This could be a chemical
reactor but also a beaker glass filled with a solution of various chemicals. Everything
outside the system is called surroundings. To surroundings of the beaker glass is rather
well defined, but it may prove to be more difficult to describe for the chemical reactor.
The best way to proceed is to define the boundaries of the system that are necessarily also
the boundaries of the surroundings. The system may exchange matter and energy through
these boundaries with its surroundings in which case the boundaries are open. When
it is possible for a system to exchange matter or energy with its environment, thermal
equilibrium is achieved when the flows between the system and its environment have
come to an end or, more exactly, when the flows balance so that there is no net transfer.
Consider now two systems that share their surroundings. The question whether the
two are in thermal equilibrium with each other is one that is often important in thermo-
dynamic analysis. When both system boundaries are open to the environment, one would
expect this to be the case when the flows between the systems and the environment have
ceased.
But not all systems are arranged in such a way that they can exchange matter or energy
either between themselves or through the surroundings. This is the case when they have
boundaries that are effectively closed to flow of matter and energy. Still, two such isolated
systems can be in thermal equilibrium with one another and in order to determine this we
use a third system. The Zeroth Law effectively makes the relation thermal equilibrium an
associative one as it states that two systems are in thermal equilibrium when they both are
in thermal equilibrium equilibrium with a third. The Zeroth Law hence provides for the
legalization of the thermometer as a means to verify thermal equilibrium!

2
 1. Overview 3

Figure 1.1 Principle of the thermoscope.

1.1.1 Thermometry
The oldest system with which temperatures were measured is the thermoscope, see fig-
ure 1.1. It consists of a glass bulb connected with a tube. To operate, the bulb is first
heated up to the maximum temperature that needs to be measured. Subsequently, the tube
is put in a vessel with liquid, such as water, and the bulb is allowed to equilibrate with the
environment. The water will come up into the tube until a certain height. The thermo-
scope is ready to measure and can be brought into thermal contact with another system.
The difference in height of the liquid column when equilibrated with the system and the
height when equilibrated with the environment is a measure of the temperature difference
between the system and the environment.

The above described phenomenon derives from what we now know as the Ideal Gas
Law

pVm RT (1.1)

which relates the pressure p measured in Pascal with the temperature T measured in
Kelvin. The molar volume is the amount of volume one mole of the entrapped gas, air
in this case, occupies and can be found by dividing the volume of the system by the
amount of moles of gas in the volume, i.e. Vm V n. The dimension of molar volume
is m3 /mol. The proportionality constant R 8314 J/(K mol) is the gas constant.
The temperature difference between system and environment is then proportional to
the pressure difference due to the hydrostatic pressure of the liquid column of length
h as

ΔT ∝ h

A major drawback of the thermoscope is that the range of temperatures that can be mea-
sured with the instrument is rather limited. The Constant Volume Gas Thermometer does
not have this drawback, see figure 1.2. It has a reservoir for the liquid of which the level
can be adjusted such that under all circumstances the volume inside the measuring bulb
Chapter 2

Spontaneity of processes

Some substances have a natural tendency to change, such as the rusting of iron, the spread-
ing of perfume in a room, or the melting of ice. Other processes only occur after a little
initial push, such as the burning of natural gas. All these phenomena are termed “spon-
taneous processes” because they take place without continuous external help. One of the
great achievements of thermodynamics is that it provides a method to predict this natural
tendency for any process that might be conceived.

2.1 Gibbs energy predicts spontaneity

The method is based on a quantity called the Gibbs energy. The difference in Gibbs energy

between one state, A, and another state, B, given by ΔG GB GA , determines whether
the process can go spontaneously from A to B or not. There are three possibilities:

G A  GB : the process can go from state A to state B.

G A GB : no process can go, possibly equilibrium.

G A  GB : the process can go from state B to state A but not in the opposite direc-
tion.

The Gibbs energy of a substance depends on its nature and state of aggregation and on
conditions such as pressure, temperature and for solutes on concentration. The unit of
the Gibbs energy is the Joule and since it is proportional to the amount of substance, it is
frequently given in Joule/mol; it is then formally called the molar Gibbs energy, a term
that often is assumed implicitly. As an illustration, consider figure 2.1 which is a plot1
of the difference in Gibbs energy, as a function of pressure and temperature, between the
native state and the unfolded state of the protein Staphylococcal nuclease (Snase) which is
a small protein of about 17.5 kDa containing 149 amino acids. In the pressure-temperature
regime where ΔG  0 the protein unfolds.
Whether a process will indeed go or not can not be determined by chemical thermo-
dynamics as it depends on the friction that a process finds on its path. This friction can
sometimes be very strong, in the sense that a process is actually blocked from occurrence.
This is for instance the case when two vessels with liquid at different temperatures are
isolated from one another. Even though the Gibbs energy difference between them would
favor an equilibration process, it will never happen unless the vessels get thermally con-
nected. At other times, the rate at which the process occurs is merely limited as is the
case when two vessels containing gas at different pressures are connected by a very tiny
1 Picture adapted, with permission, from I. Daniel, P. Oger, and R Winter, Rev Chem Soc 35 (2006) 858 -
875.

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