Atkins’ Physical Chemistry 11th Edition

Peter Atkins
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FUNDAMENTAL CONSTANTS

Constant Symbol Value

Power of 10 Units
Speed of light c 2.997 924 58* 108
m s−1
Elementary charge e 1.602 176 565 10−19 C
Planck’s constant h 6.626 069 57 10−34
Js
ħ = h/2π 1.054 571 726 10−34 Js
Boltzmann’s constant k 1.380 6488 10−23
J K−1
Avogadro’s constant NA 6.022 141 29 1023 mol−1
Gas constant R = NAk 8.314 4621 J K−1 mol−1
Faraday’s constant F = NAe 9.648 533 65 104 C mol−1
Mass
Electron me 9.109 382 91 10−31 kg
Proton mp 1.672 621 777 10−27
kg
Neutron mn 1.674 927 351 10−27 kg
Atomic mass constant mu 1.660 538 921 10−27
kg
Vacuum permeability μ0 4π* 10−7 J s2 C−2 m−1
Vacuum permittivity ε0 = 1/μ0c2 8.854 187 817 10−12 J−1 C2 m−1
4πε0 1.112 650 056 10−10
J−1 C2 m−1
Bohr magneton μB = eħ/2me 9.274 009 68 10−24 J T−1
Nuclear magneton μN = eħ/2mp 5.050 783 53 10−27
J T−1
Proton magnetic moment µp 1.410 606 743 10−26 J T−1
g-Value of electron ge 2.002 319 304
Magnetogyric ratio
Electron γe = −gee/2me −1.001 159 652 1010 C kg−1
Proton γp = 2µp/ħ 2.675 222 004 108 C kg−1
Bohr radius a0 = 4πε0ħ /e me 2 2
5.291 772 109 10 −11
m
Rydberg constant R = m e4/8h3cε 2
∞ e 0
1.097 373 157 105 cm−1
hc R ∞ /e 13.605 692 53 eV
Fine-structure constant α = μ0e c/2h 2
7.297 352 5698 10−3

α−1 1.370 359 990 74 102

Stefan–Boltzmann constant σ = 2π5k4/15h3c2 5.670 373 10−8 W m−2 K−4
Standard acceleration of free fall g 9.806 65* m s−2
Gravitational constant G 6.673 84 10−11 N m2 kg−2

* Exact value. For current values of the constants, see the National Institute of Standards and Technology (NIST) website.
Atkins’
PHYSICAL CHEMISTRY
Eleventh edition

Peter Atkins
Fellow of Lincoln College,
University of Oxford,
Oxford, UK

Julio de Paula
Professor of Chemistry,
Lewis & Clark College,
Portland, Oregon, USA

James Keeler
Senior Lecturer in Chemistry and
Fellow of Selwyn College,
University of Cambridge,
Cambridge, UK

1
 3
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The moral rights of the author have been asserted
Eighth edition 2006
Ninth edition 2009
Tenth edition 2014
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contained in any third party website referenced in this work.

The cover image symbolizes the structure of the text, as a collection of Topics that merge into a unified whole. It also symbolizes
the fact that physical chemistry provides a basis for understanding chemical and physical change.
PREFACE
Our Physical Chemistry is continuously evolving in response
to users’ comments and our own imagination. The principal
change in this edition is the addition of a new co-author to the
team, and we are very pleased to welcome James Keeler of the
University of Cambridge. He is already an experienced author
and we are very happy to have him on board.
As always, we strive to make the text helpful to students
and usable by instructors. We developed the popular ‘Topic’
arrangement in the preceding edition, but have taken the
concept further in this edition and have replaced chapters by
Focuses. Although that is principally no more than a change of
name, it does signal that groups of Topics treat related groups
of concepts which might demand more than a single chapter
in a conventional arrangement. We know that many instruc-
tors welcome the flexibility that the Topic concept provides,
because it makes the material easy to rearrange or trim.
We also know that students welcome the Topic arrangement
as it makes processing of the material they cover less daunt-
ing and more focused. With them in mind we have developed
additional help with the manipulation of equations in the
form of annotations, and The chemist’s toolkits provide further
background at the point of use. As these Toolkits are often rel-
evant to more than one Topic, they also appear in consolidated
and enhanced form on the website. Some of the material pre-
viously carried in the ‘Mathematical backgrounds’ has been
used in this enhancement. The web also provides a number
of sections called A deeper look. As their name suggests, these
sections take the material in the text further than we consider
appropriate for the printed version but are there for students
and instructors who wish to extend their knowledge and see
the details of more advanced calculations.
Another major change is the replacement of the
‘Justifications’ that show how an equation is derived. Our in-
tention has been to maintain the separation of the equation
and its derivation so that review is made simple, but at the
same time to acknowledge that mathematics is an integral fea-
ture of learning. Thus, the text now sets up a question and the
How is that done? section that immediately follows develops
the relevant equation, which then flows into the following text.
The worked Examples are a crucially important part of the
learning experience. We have enhanced their presentation by
replacing the ‘Method’ by the more encouraging Collect your
thoughts, where with this small change we acknowledge that
different approaches are possible but that students welcome
guidance. The Brief illustrations remain: they are intended
simply to show how an equation is implemented and give a
sense of the order of magnitude of a property.
It is inevitable that in an evolving subject, and with evolv-
ing interests and approaches to teaching, some subjects wither
and die and are replaced by new growth. We listen carefully
to trends of this kind, and adjust our treatment accordingly.
The topical approach enables us to be more accommodating
of fading fashions because a Topic can so easily be omitted by
an instructor, but we have had to remove some subjects simply
to keep the bulk of the text manageable and have used the web
to maintain the comprehensive character of the text without
overburdening the presentation.
This book is a living, evolving text. As such, it depends very
much on input from users throughout the world, and we wel-
come your advice and comments.
PWA
JdeP
JK
vi 12 The properties of gases
USING THE BOOK
TO THE STUDENT
For this eleventh edition we have developed the range of
learning aids to suit your needs more closely than ever before.
In addition to the variety of features already present, we now
derive key equations in a helpful new way, through the How
is that done? sections, to emphasize how mathematics is an
interesting, essential, and integral feature of understanding
physical chemistry.
Innovative structure
Short Topics are grouped into Focus sections, making the
subject more accessible. Each Topic opens with a comment
on why it is important, a statement of its key idea, and a brief
summary of the background that you need to know.
Notes on good practice
Our ‘Notes on good practice’ will help you avoid making
common mistakes. Among other things, they encourage con-
formity to the international language of science by setting out
the conventions and procedures adopted by the International
Union of Pure and Applied Chemistry (IUPAC).
Resource section
The Resource section at the end of the book includes a table
of useful integrals, extensive tables of physical and chemical
data, and character tables. Short extracts of most of these
tables appear in the Topics themselves: they are there to give
you an idea of the typical values of the physical quantities
mentioned in the text.
Checklist of concepts
A checklist of key concepts is provided at the end of each
Topic, so that you can tick off the ones you have mastered.
TOPIC 2A Internal energy
For example, a closed system can expand and thereby raise a
weight in the surroundings; a closed system may also transfer
➤ Why do you need to know this material?
The First Law of thermodynamics is the foundation of the
energy to the surroundings if they are at a lower temperature.
An isolated system is a closed system that has neither me-
discussion of the role of energy in chemistry. Wherever the
generation or use of energy in physical transformations or
chemical reactions is of interest, lying in the background
chanical nor thermal contact with its surroundings.
are the concepts introduced by the First Law.
➤ What is the key idea? 2A.1 Work, heat, and energy
The total energy of an isolated system is constant.
➤ What do you need to know already?
Although thermodynamics deals with observations on bulk
systems, it is immeasurably enriched by understanding the
molecular origins of these observations.
This Topic makes use of the discussion of the properties of
gases (Topic 1A), particularly the perfect gas law. It builds
on the definition of work given in The chemist’s toolkit 6. (a) Operational definitions
The fundamental physical property in thermodynamics is
work: work is done to achieve motion against an opposing
For the purposes of thermodynamics, the universe is divided force (The chemist’s toolkit 6). A simple example is the process
into two parts, the system and its surroundings. The system is of raising a weight against the pull of gravity. A process does
the part of the world of interest. It may be a reaction vessel, an
engine, an electrochemical cell, a biological cell, and so on. The
work if in principle it can be harnessed to raise a weight some-
where in the surroundings. An example of doing work is the
surroundings comprise the region outside the system and are expansion of a gas that pushes out a piston: the motion of the
where measurements are made. The type of system depends piston can in principle be used to raise a weight. Another ex-
on the characteristics of the boundary that divides it from the ample is a chemical reaction in a cell, which leads to an electric
A note on good practice An allotrope is a particular molecular
form of an element (such as O2 and O3) and may be solid, liquid,
or gas. A polymorph is one of a number of solid phases of an ele-
ment or compound.
The number of phases in a system is denoted P. A gas, or a
gaseous mixture, is a single phase (P = 1), a crystal of a sub-
Contents
1 Common integrals 862
866
2 Units 864
868
3 Data 865
869
Checklist of concepts
☐ 1. The physical state of a sample of a substance, its physi-
cal condition, is defined by its physical properties.
☐ 2. Mechanical equilibrium is the condition of equality of
pressure on either side of a shared movable wall.
 Using the book vii

PRESENTING THE MATHEMATICS

How is that done?

You need to understand how an equation is derived from rea-
sonable assumptions and the details of the mathematical steps
involved. This is accomplished in the text through the new
‘How is that done?’ sections, which replace the Justifications of
earlier editions. Each one leads from an issue that arises in the
text, develops the necessary mathematics, and arrives at the
equation or conclusion that resolves the issue. These sections
maintain the separation of the equation and its derivation
so that you can find them easily for review, but at the same
time emphasize that mathematics is an essential feature of
physical chemistry.
How is that done? 4A.1 Deducing the phase rule
The argument that leads to the phase rule is most easily appre-
ciated by first thinking about the simpler case when only one
component is present and then generalizing the result to an
arbitrary number of components.
Step 1 Consider the case where only one component is present
When only one phase is present (P = 1), both p and T can be
varied independently, so F = 2. Now consider the case where
two phases α and β are in equilibrium (P = 2). If the phases
are in equilibrium at a given pressure and temperature, their
chemical potentials must be equal:

The chemist’s toolkits The chemist’s toolkit 2 Properties of bulk matter

The chemist’s toolkits, which are much more numerous in this
edition, are reminders of the key mathematical, physical, and
chemical concepts that you need to understand in order to
follow the text. They appear where they are first needed. Many
of these Toolkits are relevant to more than one Topic, and a
compilation of them, with enhancements in the form of more
information and brief illustrations, appears on the web site.
www.oup.com/uk/pchem11e/
The state of a bulk sample of matter is defined by specifying the
values of various properties. Among them are:
The mass, m, a measure of the quantity of matter present
(unit: kilogram, kg).
The volume, V, a measure of the quantity of space the sam-
ple occupies (unit: cubic metre, m3).
The amount of substance, n, a measure of the number of
specified entities (atoms, molecules, or formula units) pre-
sent (unit: mole, mol).

Annotated equations and equation labels

d(1/f )/dx = −(1/f 2)df/dx
We have annotated many equations to help you follow how Um(T) = Um(0) + NA 〈εV〉 used twice
they are developed. An annotation can take you across the 2 V
dN A 〈ε V 〉 d 1  θV  eθ /T
equals sign: it is a reminder of the substitution used, an CVV,m = = Rθ V = R   θ /T
dT dT eθ /T −1 V
T
  (e −1)2
V

approximation made, the terms that have been assumed

constant, an integral used, and so on. An annotation can By noting that eθ
V
/T
= (eθ
V
/2T 2
) , this expression can be rearranged
also be a reminder of the significance of an individual term into
in an expression. We sometimes colour a collection of num- 2 2
 θ V   e −θ /2T 
V

bers or symbols to show how they carry from one line to the CVV,m = Rf (T ) f (T ) =   
 T   1− e −θ /T 
V

next. Many of the equations are labelled to highlight their

significance. Vibrational contribution to CV,m (13E.3)

Checklists of equations
A handy checklist at the end of each topic summarizes the Checklist of equations
most important equations and the conditions under which
they apply. Don’t think, however, that you have to memorize Property Equation
every equation in these checklists. Gibbs energy of mixing ΔmixG = nRT(xA ln xA + xB ln xB)
Entropy of mixing ΔmixS = −nR(xA ln xA + xB ln xB)
viii Using the book
SET TING UP AND SOLVING PROBLEMS
Brief illustrations
A Brief illustration shows you how to use an equation or con-
cept that has just been introduced in the text. It shows you
how to use data and manipulate units correctly. It also helps
you to become familiar with the magnitudes of quantities.
Examples
Worked Examples are more detailed illustrations of the appli-
cation of the material, and typically require you to assemble
and deploy the relevant concepts and equations.
We suggest how you should collect your thoughts (that is a
new feature) and then proceed to a solution. All the worked
Examples are accompanied by Self-tests to enable you to test
your grasp of the material after working through our solution
as set out in the Example.
Discussion questions
Discussion questions appear at the end of every Focus, and are
organised by Topic. These questions are designed to encour-
age you to reflect on the material you have just read, to review
the key concepts, and sometimes to think about its implica-
tions and limitations.
Exercises and problems
Exercises and Problems are also provided at the end of every
Focus and organised by Topic. Exercises are designed as
relatively straightforward numerical tests; the Problems are
more challenging and typically involve constructing a more
detailed answer. The Exercises come in related pairs, with
final numerical answers available online for the ‘a’ questions.
Final numerical answers to the odd-numbered Problems are
also available online.
Integrated activities
At the end of every Focus you will find questions that span
several Topics. They are designed to help you use your knowl-
edge creatively in a variety of ways.
Brief illustration 3B.1
When the volume of any perfect gas is doubled at constant
temperature, Vf/Vi = 2, and hence the change in molar entropy
of the system is
ΔSm = (8.3145 J K−1 mol−1) × ln 2 = +5.76 J K−1 mol−1
Example 1A.1 Using the perfect gas law
In an industrial process, nitrogen gas is introduced into
a vessel of constant volume at a pressure of 100 atm and a
temperature of 300 K. The gas is then heated to 500 K. What
pressure would the gas then exert, assuming that it behaved
as a perfect gas?
Collect your thoughts The pressure is expected to be greater
on account of the increase in temperature. The perfect gas
FOCUS 3 The Second and Third Laws
Assume that all gases are perfect and that data refer to 298.15 K unless otherwise stated.
TOPIC 3A Entropy
Discussion questions
D3A.1 The evolution of life requires the organization of a very large number D3A.2 Discuss the significance of the terms ‘dispersal’ and ‘disorder’ in the
of molecules into biological cells. Does the formation of living organisms context of the Second Law.
violate the Second Law of thermodynamics? State your conclusion clearly and
D3A.3 Discuss the relationships between the various formulations of the
present detailed arguments to support it.
Second Law of thermodynamics.
Exercises
E3A.1(a) Consider a process in which the entropy of a system increases by gas of mass 14 g at 298 K doubles its volume in (a) an isothermal reversible
125 J K−1 and the entropy of the surroundings decreases by 125 J K−1. Is the
process spontaneous?
E3A.1(b) Consider a process in which the entropy of a system increases by
expansion, (b) an isothermal irreversible expansion against pex = 0, and (c) an
adiabatic reversible expansion.
E3A.4(b) Calculate the change in the entropies of the system and the
105 J K−1 and the entropy of the surroundings decreases by 95 J K−1. Is the
process spontaneous?
surroundings, and the total change in entropy, when the volume of a sample
of argon gas of mass 2.9 g at 298 K increases from 1.20 dm3 to 4.60 dm3 in (a)
an isothermal reversible expansion, (b) an isothermal irreversible expansion
E3A.2(a) Consider a process in which 100 kJ of energy is transferred reversibly
and isothermally as heat to a large block of copper. Calculate the change in
entropy of the block if the process takes place at (a) 0 °C, (b) 50 °C.
against pex = 0, and (c) an adiabatic reversible expansion.
E3A.5(a) In a certain ideal heat engine, 10.00 kJ of heat is withdrawn from the
E3A.2(b) Consider a process in which 250 kJ of energy is transferred reversibly
and isothermally as heat to a large block of lead. Calculate the change in
hot source at 273 K and 3.00 kJ of work is generated. What is the temperature
of cold sink?
entropy of the block if the process takes place at (a) 20 °C, (b) 100 °C. E3A.5(b) In an ideal heat engine the cold sink is at 0 °C. If 10.00 kJ of heat
E3A.3(a) Calculate the change in entropy of the gas when 15 g of carbon dioxide
gas are allowed to expand isothermally from 1.0 dm3 to 3.0 dm3 at 300 K.
is withdrawn from the hot source and 3.00 kJ of work is generated, at what
temperature is the hot source?
E3A.3(b) Calculate the change in entropy of the gas when 4.00 g of nitrogen is
3 3
allowed to expand isothermally from 500 cm to 750 cm at 300 K.
E3A.6(a) What is the efficiency of an ideal heat engine in which the hot source
is at 100 °C and the cold sink is at 10 °C?
E3A.6(b) An ideal heat engine has a hot source at 40 °C. At what temperature
E3A.4(a) Calculate the change in the entropies of the system and the
must the cold sink be if the efficiency is to be 10 per cent?
surroundings, and the total change in entropy, when a sample of nitrogen
Problems
P3A.1 A sample consisting of 1.00 mol of perfect gas molecules at 27 °C is transferred to or from the gas. (d) Explain why the work done is equal to the
expanded isothermally from an initial pressure of 3.00 atm to a final pressure difference between the heat extracted from the hot source and that deposited
of 1.00 atm in two ways: (a) reversibly, and (b) against a constant external in the cold sink. (e) Calculate the work done over the cycle and hence the
pressure of 1.00 atm. Evaluate q, w, ΔU, ΔH, ΔS, ΔSsurr, and ΔStot in each case. efficiency η. (f) Confirm that your answer agrees with the efficiency given by
eqn 3A.9 and that your values for the heat involved in the isothermal stages
P3A.2 A sample consisting of 0.10 mol of perfect gas molecules is held by a
are in accord with eqn 3A.6.
piston inside a cylinder such that the volume is 1.25 dm3; the external pressure
is constant at 1.00 bar and the temperature is maintained at 300 K by a P3A.4 The Carnot cycle is usually represented on a pressure−volume
thermostat. The piston is released so that the gas can expand. Calculate (a) the diagram (Fig. 3A.8), but the four stages can equally well be represented
volume of the gas when the expansion is complete; (b) the work done when on temperature−entropy diagram, in which the horizontal axis is entropy
the gas expands; (c) the heat absorbed by the system. Hence calculate ΔStot. and the vertical axis is temperature; draw such a diagram. Assume that the
P3A.3 Consider a Carnot cycle in which the working substance is 0.10 mol of
perfect gas molecules, the temperature of the hot source is 373 K, and that
temperature of the hot source is Th and that of the cold sink is Tc, and that the
volume of the working substance (the gas) expands from VA to VB in the first
isothermal stage. (a) By considering the entropy change of each stage, derive
of the cold sink is 273 K; the initial volume of gas is 1.00 dm3, which doubles
an expression for the area enclosed by the cycle in the temperature−entropy
over the course of the first isothermal stage. For the reversible adiabatic stages
diagram. (b) Derive an expression for the work done over the cycle. (Hint: The
it may be assumed that VT 3/2 = constant. (a) Calculate the volume of the gas
work done is the difference between the heat extracted from the hot source
after Stage 1 and after Stage 2 (Fig. 3A.8). (b) Calculate the volume of gas after
and that deposited in the cold sink; or use eqns 3A.7 and 3A.9) (c) Comment
Stage 3 by considering the reversible adiabatic compression from the starting
on the relation between your answers to (a) and (b).
point. (c) Hence, for each of the four stages of the cycle, calculate the heat
 Using the book ix

THERE IS A LOT OF ADDITIONAL MATERIAL ON THE WEB

IMPAC T 1 …ON ENVIRONMENTAL SCIENCE: A DEEPER LOOK 2 The fugacity

The gas laws and the weather
At various stages in the development of physical chemistry In this expression, f1 is the fugacity when the pressure is
it is necessary to switch from a consideration of ideal- p1 and f2 is the fugacity when the pressure is p2. That is,
The biggest sample of gas readily accessible to us is the 25 ized systems to real systems. In many cases it is desirable from eqn 3b,
atmosphere, a mixture of gases with the composition to preserve the form of the expressions that have been
derived for an idealized system. Then deviations from the
p2 f2
summarized in Table 1. The composition is maintained
moderately constant by diffusion and convection (winds,
20
idealized behaviour can be expressed most simply. For
∫ p1
Vm d p = RT ln
f1 (4a)
Altitude, h/km
particularly the local turbulence called eddies) but the 15 instance, the pressure-dependence of the molar Gibbs
For a perfect gas,
pressure and temperature vary with altitude and with energy of a perfect gas is
the local conditions, particularly in the troposphere (the 10
p2
 p  p2
‘sphere of change’), the layer extending up to about 11 km. Gm = G m + RT ln  −○−  ∫ Vperfect ,mdp = RT ln (4b)
−−
○
(1a)
p  p1 p1

‘Impact’ sections Group theory tables

‘Impact’ sections show how physical chemistry is applied in a
variety of modern contexts. They showcase physical chemistry
as an evolving subject. www.oup.com/uk/pchem11e/
A deeper look
These online sections take some of the material in the text
further and are there if you want to extend your knowledge
and see the details of some of the more advanced derivations
www.oup.com/uk/pchem11e/
Comprehensive group theory tables are available to download.
Molecular modelling problems
Files containing molecular modelling problems can be down-
loaded, designed for use with the Spartan Student™ software.
However they can also be completed using any modelling
software that allows Hartree–Fock, density functional, and
MP2 calculations. The site can be accessed at www.oup.com/
uk/pchem11e/.

TO THE INSTRUC TOR

We have designed the text to give you maximum flexibility in
the selection and sequence of Topics, while the grouping of
Topics into Focuses helps to maintain the unity of the subject.
Additional resources are:
Figures and tables from the book
Lecturers can find the artwork and tables from the book in
ready-to-download format. These may be used for lectures
without charge (but not for commercial purposes without
specific permission).
Key equations
Supplied in Word format so you can download and edit them.
Lecturer resources are available only to registered adopters of
the textbook. To register, simply visit www.oup.com/uk/pchem11e/
and follow the appropriate links.

SOLUTIONS MANUALS
Two solutions manuals have been written by Peter Bolgar, The Instructor’s Solutions Manual provides full solutions
Haydn Lloyd, Aimee North, Vladimiras Oleinikovas, Stephanie to the ‘b’ Exercises and to the even-numbered Problems
Smith, and James Keeler. (available to download online for registered adopters of the
The Student’s Solutions Manual (ISBN 9780198807773) book only).
provides full solutions to the ‘a’ Exercises and to the odd-
numbered Problems.
ABOUT THE AUTHORS

Peter Atkins is a fellow of Lincoln College, Oxford, and was Professor of Physical Chemistry in the
University of Oxford. He is the author of over seventy books for students and a general audience. His
texts are market leaders around the globe. A frequent lecturer in the United States and throughout the
world, he has held visiting professorships in France, Israel, Japan, China, Russia, and New Zealand.
He was the founding chairman of the Committee on Chemistry Education of the International Union
of Pure and Applied Chemistry and was a member of IUPAC’s Physical and Biophysical Chemistry
Division.

Photograph by Natasha
Ellis-Knight.

Julio de Paula is Professor of Chemistry at Lewis & Clark College. A native of Brazil, he received a
B.A. degree in chemistry from Rutgers, The State University of New Jersey, and a Ph.D. in biophysical
chemistry from Yale University. His research activities encompass the areas of molecular spectroscopy,
photochemistry, and nanoscience. He has taught courses in general chemistry, physical chemistry, bio-
physical chemistry, inorganic chemistry, instrumental analysis, environmental chemistry, and writ-
ing. Among his professional honours are a Christian and Mary Lindback Award for Distinguished
Teaching, a Henry Dreyfus Teacher-Scholar Award, and a Cottrell Scholar Award from the Research
Corporation for Science Advancement.

James Keeler is a Senior Lecturer in Chemistry at the University of Cambridge, and Walters Fellow in
Chemistry at Selwyn College, Cambridge. He took his first degree at the University of Oxford and con-
tinued there for doctoral research in nuclear magnetic resonance spectroscopy. Dr Keeler is Director of
Teaching for undergraduate chemistry, and teaches courses covering a range of topics in physical and
theoretical chemistry.

Photograph by Nathan Pitt,

©University of Cambridge.
ACKNOWLEDGEMENTS
A book as extensive as this could not have been written with-
out significant input from many individuals. We would like to
reiterate our thanks to the hundreds of people who contrib-
uted to the first ten editions. Many people gave their advice
based on the tenth edition, and others, including students,
reviewed the draft chapters for the eleventh edition as they
emerged. We wish to express our gratitude to the following
colleagues:
Andrew J. Alexander, University of Edinburgh
Stephen H. Ashworth, University of East Anglia
Mark Berg, University of South Carolina
Eric Bittner, University of Houston
Melanie Britton, University of Birmingham
Eleanor Campbell, University of Edinburgh
Andrew P. Doherty, Queen’s University of Belfast
Rob Evans, Aston University
J.G.E. Gardeniers, University of Twente
Ricardo Grau-Crespo, University of Reading
Alex Grushow, Rider University
Leonid Gurevich, Aalborg University
Ronald Haines, University of New South Wales
Patrick M. Hare, Northern Kentucky University
John Henry, University of Wolverhampton
Karl Jackson, Virginia Union University
Carey Johnson, University of Kansas
George Kaminski, Worcester Polytechnic Institute
Scott Kirkby, East Tennessee State University
Kathleen Knierim, University of Louisiana at Lafayette
Jeffry Madura, University of Pittsburgh
David H. Magers, Mississippi College
Kristy Mardis, Chicago State University
Paul Marshall, University of North Texas
Laura R. McCunn, Marshall University
Allan McKinley, University of Western Australia
Joshua Melko, University of North Florida
Yirong Mo, Western Michigan University
Gareth Morris, University of Manchester
Han J. Park, University of Tennessee at Chattanooga
Rajeev Prabhakar, University of Miami
Gavin Reid, University of Leeds
Chad Risko, University of Kentucky
Nessima Salhi, Uppsala University
Daniel Savin, University of Florida
Richard W. Schwenz, University of Northern Colorado
Douglas Strout, Alabama State University
Steven Tait, Indiana University
Jim Terner, Virginia Commonwealth University
Timothy Vaden, Rowan University
Alfredo Vargas, University of Sussex
Darren Walsh, University of Nottingham
Collin Wick, Louisiana Tech University
Shoujun Xu, University of Houston
Renwu Zhang , California State University
Wuzong Zhou, St Andrews University
We would also like to thank Michael Clugston for proofread-
ing the entire book, and Peter Bolgar, Haydn Lloyd, Aimee
North, Vladimiras Oleinikovas, Stephanie Smith, and James
Keeler for writing a brand new set of solutions. Last, but by
no means least, we acknowledge our two commissioning
­editors, Jonathan Crowe of Oxford University Press and Jason
Noe of OUP USA, and their teams for their assistance, advice,
­encouragement, and patience.
BRIEF CONTENTS

PROLOGUE 1 FOCUS 12 Magnetic resonance 487

FOCUS 1 The properties of gases 3 FOCUS 13 Statistical thermodynamics 531

FOCUS 2 The First Law 33 FOCUS 14 Molecular interactions 583

FOCUS 3 The Second and Third Laws 77 FOCUS 15 Solids 639

FOCUS 4 Physical transformations of pure FOCUS 16 Molecules in motion 689

substances 119
FOCUS 17 Chemical kinetics 721
FOCUS 5 Simple mixtures 141
FOCUS 18 Reaction dynamics 779
FOCUS 6 Chemical equilibrium 203
FOCUS 19 Processes at solid surfaces 823
FOCUS 7 Quantum theory 235
Resource section
FOCUS 8 Atomic structure and spectra 303 1 Common integrals 862
2 Units 864
FOCUS 9 Molecular structure 341 3 Data 865
4 Character tables 895

FOCUS 10 Molecular symmetry 387 Index899

FOCUS 11 Molecular spectroscopy 417

FULL CONTENTS

Conventionsxxv (a) Operational definitions 34

(b) The molecular interpretation of heat and work 36
List of tables xxvi
2A.2 The definition of internal energy 37
List of The chemist’s toolkitsxxviii
(a) Molecular interpretation of internal energy 37
List of material provided as A deeper lookxxix (b) The formulation of the First Law 38
List of Impactsxxx 2A.3 Expansion work 38
(a) The general expression for work 39
39
PROLOGUE Energy, temperature, (b) Expansion against constant pressure
(c) Reversible expansion 40
and chemistry 1
(d) Isothermal reversible expansion of a perfect gas 41
2A.4 Heat transactions 42
FOCUS 1 The properties of gases 3 (a) Calorimetry 42
(b) Heat capacity 43
TOPIC 1A The perfect gas 4
Checklist of concepts 45
1A.1 Variables of state 4
Checklist of equations 45
(a) Pressure 4
(b) Temperature 5
TOPIC 2B Enthalpy 46
1A.2 Equations of state 6
2B.1 The definition of enthalpy 46
(a) The empirical basis 7
(a) Enthalpy change and heat transfer 46
(b) Mixtures of gases 9
(b) Calorimetry 47
Checklist of concepts 10
2B.2 The variation of enthalpy with temperature 48
Checklist of equations 10 (a) Heat capacity at constant pressure 48
(b) The relation between heat capacities 49
TOPIC 1B The kinetic model 11
Checklist of concepts 50
1B.1 The model 11
Checklist of equations 50
(a) Pressure and molecular speeds 12
(b) The Maxwell–Boltzmann distribution of speeds 13
TOPIC 2C Thermochemistry 51
(c) Mean values 15
2C.1 Standard enthalpy changes 51
1B.2 Collisions 17
(a) Enthalpies of physical change 51
(a) The collision frequency 17
(b) Enthalpies of chemical change 52
(b) The mean free path 18
(c) Hess’s law 53
Checklist of concepts 18
2C.2 Standard enthalpies of formation 54
Checklist of equations 18
2C.3 The temperature dependence of reaction enthalpies 55

TOPIC 1C Real gases 19 2C.4 Experimental techniques 56

(a) Differential scanning calorimetry 56
1C.1 Deviations from perfect behaviour 19
(b) Isothermal titration calorimetry 57
(a) The compression factor 20
(b) Virial coefficients 20
Checklist of concepts 57
(c) Critical constants 22 Checklist of equations 58
1C.2 The van der Waals equation 23
TOPIC 2D State functions and exact differentials 59
(a) Formulation of the equation 23
2D.1 Exact and inexact differentials 59
(b) The features of the equation 24
(c) The principle of corresponding states 26 2D.2 Changes in internal energy 60
(a) General considerations 60
Checklist of concepts 27
(b) Changes in internal energy at constant pressure 62
Checklist of equations 27
2D.3 Changes in enthalpy 63
2D.4 The Joule–Thomson effect 64
FOCUS 2 The First Law 33 (a) The observation of the Joule–Thomson effect 64
(b) The molecular interpretation of the Joule–Thomson effect 65
TOPIC 2A Internal energy 34
Checklist of concepts 66
2A.1 Work, heat, and energy 34
Checklist of equations 66
xvi Full Contents

TOPIC 2E Adiabatic changes 67 3E.2 Properties of the Gibbs energy 106

(a) General considerations 106
2E.1 The change in temperature 67
(b) The variation of the Gibbs energy with temperature 108
2E.2 The change in pressure 68
(c) The variation of the Gibbs energy with pressure 108
Checklist of concepts 69
Checklist of concepts 110
Checklist of equations 69
Checklist of equations 110

FOCUS 3 The Second and Third Laws 77

FOCUS 4 Physical transformations of
TOPIC 3A Entropy 78 pure substances 119
3A.1 The Second Law 78
TOPIC 4A Phase diagrams of pure substances 120
3A.2 The definition of entropy 80
4A.1 The stabilities of phases 120
(a) The thermodynamic definition of entropy 80
(a) The number of phases 120
(b) The statistical definition of entropy 81
(b) Phase transitions 120
3A.3 The entropy as a state function 82 (c) Thermodynamic criteria of phase stability 121
(a) The Carnot cycle 82
4A.2 Phase boundaries 122
(b) The thermodynamic temperature 85
(a) Characteristic properties related to phase transitions 122
(c) The Clausius inequality 85
(b) The phase rule 123
Checklist of concepts 86
4A.3 Three representative phase diagrams 125
Checklist of equations 87 (a) Carbon dioxide 125
(b) Water 125
TOPIC 3B Entropy changes ­accompanying
(c) Helium 126
specific processes 88
Checklist of concepts 127
3B.1 Expansion 88
Checklist of equations 127
3B.2 Phase transitions 89
3B.3 Heating 90 TOPIC 4B Thermodynamic aspects of phase
3B.4 Composite processes 90 transitions 128
Checklist of concepts 91 4B.1 The dependence of stability on the conditions 128
Checklist of equations 91 (a) The temperature dependence of phase stability 128
(b) The response of melting to applied pressure 129
TOPIC 3C The measurement of entropy 92 (c) The vapour pressure of a liquid subjected to pressure 130
3C.1 The calorimetric measurement of entropy 92 4B.2 The location of phase boundaries 131
3C.2 The Third Law 93 (a) The slopes of the phase boundaries 131
(a) The Nernst heat theorem 93 (b) The solid–liquid boundary 132
(b) Third-Law entropies 94 (c) The liquid–vapour boundary 132
(c) The temperature dependence of reaction entropy 95 (d) The solid–vapour boundary 134
Checklist of concepts 96 Checklist of concepts 134
Checklist of equations 96 Checklist of equations 134

TOPIC 3D Concentrating on the system 97

3D.1 The Helmholtz and Gibbs energies 97
FOCUS 5 Simple mixtures 141
(a) Criteria of spontaneity 97 TOPIC 5A The thermodynamic description
(b) Some remarks on the Helmholtz energy 98 of mixtures 143
(c) Maximum work 98
5A.1 Partial molar quantities 143
(d) Some remarks on the Gibbs energy 99
(a) Partial molar volume 143
(e) Maximum non-expansion work 100
(b) Partial molar Gibbs energies 145
3D.2 Standard molar Gibbs energies 100 (c) The wider significance of the chemical potential 146
(a) Gibbs energies of formation 101 (d) The Gibbs–Duhem equation 146
(b) The Born equation 102
5A.2 The thermodynamics of mixing 147
Checklist of concepts 103 (a) The Gibbs energy of mixing of perfect gases 147
Checklist of equations 103 (b) Other thermodynamic mixing functions 149
5A.3 The chemical potentials of liquids 150
TOPIC 3E Combining the First and Second Laws 104 (a) Ideal solutions 150
3E.1 Properties of the internal energy 104 (b) Ideal–dilute solutions 152
(a) The Maxwell relations 104
Checklist of concepts 153
(b) The variation of internal energy with volume 106
Checklist of equations 154
 Full Contents xvii

TOPIC 5B The properties of solutions 155 FOCUS 6 Chemical equilibrium 203

5B.1 Liquid mixtures 155
TOPIC 6A The equilibrium constant 204
(a) Ideal solutions 155
6A.1 The Gibbs energy minimum 204
(b) Excess functions and regular solutions 156
(a) The reaction Gibbs energy 204
5B.2 Colligative properties 158
(b) Exergonic and endergonic reactions 205
(a) The common features of colligative properties 158
6A.2 The description of equilibrium 205
(b) The elevation of boiling point 159
(a) Perfect gas equilibria 205
(c) The depression of freezing point 161
(b) The general case of a reaction 206
(d) Solubility 161
(c) The relation between equilibrium constants 209
(e) Osmosis 162
(d) Molecular interpretation of the equilibrium constant 210
Checklist of concepts 164
Checklist of concepts 211
Checklist of equations 165
Checklist of equations 211
TOPIC 5C Phase diagrams of binary systems:
liquids 166 TOPIC 6B The response of equilibria to the
conditions 212
5C.1 Vapour pressure diagrams 166
6B.1 The response to pressure 212
5C.2 Temperature–composition diagrams 168
6B.2 The response to temperature 213
(a) The construction of the diagrams 168
(a) The van ’t Hoff equation 213
(b) The interpretation of the diagrams 169
(b) The value of K at different temperatures 215
5C.3 Distillation 170
Checklist of concepts 216
(a) Simple and fractional distillation 170
(b) Azeotropes 171 Checklist of equations 216
(c) Immiscible liquids 172
TOPIC 6C Electrochemical cells 217
5C.4 Liquid–liquid phase diagrams 172
6C.1 Half-reactions and electrodes 217
(a) Phase separation 172
(b) Critical solution temperatures 173 6C.2 Varieties of cells 218
(c) The distillation of partially miscible liquids 175 (a) Liquid junction potentials 218
(b) Notation 219
Checklist of concepts 176
6C.3 The cell potential 219
Checklist of equations 176
(a) The Nernst equation 219

TOPIC 5D Phase diagrams of binary systems: solids 177 (b) Cells at equilibrium 221

5D.1 Eutectics 177 6C.4 The determination of thermodynamic functions 221

5D.2 Reacting systems 178 Checklist of concepts 223
5D.3 Incongruent melting 179 Checklist of equations 223
Checklist of concepts 179
TOPIC 6D Electrode potentials 224
TOPIC 5E Phase diagrams of ternary systems 180 6D.1 Standard potentials 224
(a) The measurement procedure 225
5E.1 Triangular phase diagrams 180
(b) Combining measured values 226
5E.2 Ternary systems 181
6D.2 Applications of standard potentials 226
(a) Partially miscible liquids 181
(a) The electrochemical series 226
(b) Ternary solids 182
(b) The determination of activity coefficients 226
Checklist of concepts 182
(c) The determination of equilibrium constants 227

TOPIC 5F Activities 183 Checklist of concepts 227

5F.1 The solvent activity 183 Checklist of equations 228
5F.2 The solute activity 183
(a) Ideal–dilute solutions 184 FOCUS 7 Quantum theory 235
(b) Real solutes 184
(c) Activities in terms of molalities 185 TOPIC 7A The origins of quantum mechanics 237
5F.3 The activities of regular solutions 185 7A.1 Energy quantization 237
5F.4 The activities of ions 187 (a) Black-body radiation 237

(a) Mean activity coefficients 187 (b) Heat capacity 240

(b) The Debye–Hückel limiting law 187 (c) Atomic and molecular spectra 241

(c) Extensions of the limiting law 188 7A.2 Wave–particle duality 242
Checklist of concepts 189 (a) The particle character of electromagnetic radiation 242
(b) The wave character of particles 244
Checklist of equations 190
xviii Full Contents

Checklist of concepts 245 Checklist of concepts 290

Checklist of equations 245 Checklist of equations 290

TOPIC 7B Wavefunctions 246

7B.1 The Schrödinger equation 246 FOCUS 8 Atomic structure and spectra 303
7B.2 The Born interpretation 247 TOPIC 8A Hydrogenic atoms 304
(a) Normalization 248 8A.1 The structure of hydrogenic atoms 304
(b) Constraints on the wavefunction 249 (a) The separation of variables 304
(c) Quantization 250 (b) The radial solutions 305
Checklist of concepts 250 8A.2 Atomic orbitals and their energies 308
Checklist of equations 250 (a) The specification of orbitals 308
(b) The energy levels 308
TOPIC 7C Operators and observables 251 (c) Ionization energies 309
7C.1 Operators 251 (d) Shells and subshells 309
(a) Eigenvalue equations 251 (e) s Orbitals 310
(b) The construction of operators 252 (f) Radial distribution functions 311
(c) Hermitian operators 253 (g) p Orbitals 313
(d) Orthogonality 254 (h) d Orbitals 314
7C.2 Superpositions and expectation values 255 Checklist of concepts 314
7C.3 The uncertainty principle 257 Checklist of equations 315
7C.4 The postulates of quantum mechanics 259
Checklist of concepts 260 TOPIC 8B Many-electron atoms 316
Checklist of equations 260 8B.1 The orbital approximation 316
8B.2 The Pauli exclusion principle 317
TOPIC 7D Translational motion 261 (a) Spin 317
7D.1 Free motion in one dimension 261 (b) The Pauli principle 318

7D.2 Confined motion in one dimension 262 8B.3 The building-up principle 319
(a) The acceptable solutions 263 (a) Penetration and shielding 319
(b) The properties of the wavefunctions 264 (b) Hund’s rules 321
(c) The properties of the energy 265 (c) Atomic and ionic radii 323

7D.3 Confined motion in two and more dimensions 266 (d) Ionization energies and electron affinities 324

(a) Energy levels and wavefunctions 266 8B.4 Self-consistent field orbitals 325
(b) Degeneracy 267 Checklist of concepts 325
7D.4 Tunnelling 268 Checklist of equations 326
Checklist of concepts 271
Checklist of equations 272
TOPIC 8C Atomic spectra 327
8C.1 The spectra of hydrogenic atoms 327
TOPIC 7E Vibrational motion 273 8C.2 The spectra of many-electron atoms 328
7E.1 The harmonic oscillator 273 (a) Singlet and triplet terms 328
(a) The energy levels 274 (b) Spin–orbit coupling 329
(b) The wavefunctions 275 (c) Term symbols 332

7E.2 Properties of the harmonic oscillator 277 (d) Hund’s rules 335

(a) Mean values 277 (e) Selection rules 335

(b) Tunnelling 278 Checklist of concepts 336

Checklist of concepts 279 Checklist of equations 336
Checklist of equations 280

TOPIC 7F Rotational motion 281 FOCUS 9 Molecular structure 341

7F.1 Rotation in two dimensions 281 PROLOGUE The Born–Oppenheimer approximation 343
(a) The solutions of the Schrödinger equation 283
(b) Quantization of angular momentum 284
TOPIC 9A Valence-bond theory 344
9A.1 Diatomic molecules 344
7F.2 Rotation in three dimensions 285
(a) The wavefunctions and energy levels 285 9A.2 Resonance 346
(b) Angular momentum 288 9A.3 Polyatomic molecules 346
(c) The vector model 288 (a) Promotion 347
(b) Hybridization 347
 Full Contents xix

Checklist of concepts 350 (e) The cubic groups 393

Checklist of equations 350 (f) The full rotation group 394
10A.3 Some immediate consequences of symmetry 394
TOPIC 9B Molecular orbital theory: (a) Polarity 394
the hydrogen molecule-ion 351 (b) Chirality 395
9B.1 Linear combinations of atomic orbitals 351 Checklist of concepts 395
(a) The construction of linear combinations 351 Checklist of operations and elements 396
(b) Bonding orbitals 353
(c) Antibonding orbitals 354 TOPIC 10B Group theory 397
9B.2 Orbital notation 356 10B.1 The elements of group theory 397
Checklist of concepts 356 10B.2 Matrix representations 398
Checklist of equations 356 (a) Representatives of operations 398
(b) The representation of a group 399
TOPIC 9C Molecular orbital theory: homonuclear (c) Irreducible representations 400
diatomic molecules 357 (d) Characters 401
9C.1 Electron configurations 357 10B.3 Character tables 401
(a) σ Orbitals and π orbitals 357 (a) The symmetry species of atomic orbitals 402
(b) The overlap integral 359 (b) The symmetry species of linear combinations of orbitals 403
(c) Period 2 diatomic molecules 360 (c) Character tables and degeneracy 404
9C.2 Photoelectron spectroscopy 362 Checklist of concepts 405
Checklist of concepts 363 Checklist of equations 405
Checklist of equations 364
TOPIC 10C Applications of symmetry 406
TOPIC 9D Molecular orbital theory: ­heteronuclear 10C.1 Vanishing integrals 406
diatomic molecules 365 (a) Integrals of the product of functions 407
9D.1 Polar bonds and electronegativity 365 (b) Decomposition of a representation 408

9D.2 The variation principle 366 10C.2 Applications to molecular orbital theory 409
(a) The procedure 367 (a) Orbital overlap 409
(b) The features of the solutions 369 (b) Symmetry-adapted linear combinations 409

Checklist of concepts 370 10C.3 Selection rules 411

Checklist of equations 370 Checklist of concepts 411
Checklist of equations 411
TOPIC 9E Molecular orbital theory: ­polyatomic
molecules 371
9E.1 The Hückel approximation 371 FOCUS 11 Molecular spectroscopy 417
(a) An introduction to the method 371
TOPIC 11A General features of molecular
(b) The matrix formulation of the method 372
spectroscopy 419
9E.2 Applications 375
11A.1 The absorption and emission of radiation 420
(a) π-Electron binding energy 375
(a) Stimulated and spontaneous radiative processes 420
(b) Aromatic stability 376
(b) Selection rules and transition moments 421
9E.3 Computational chemistry 377 (c) The Beer–Lambert law 421
(a) Semi-empirical and ab initio methods 378
11A.2 Spectral linewidths 423
(b) Density functional theory 379
(a) Doppler broadening 423
(c) Graphical representations 379
(b) Lifetime broadening 425
Checklist of concepts 380
11A.3 Experimental techniques 425
Checklist of equations 380 (a) Sources of radiation 426
(b) Spectral analysis 426
FOCUS 10 Molecular symmetry 387 (c) Detectors 428
(d) Examples of spectrometers 428
TOPIC 10A Shape and symmetry 388
Checklist of concepts 429
10A.1 Symmetry operations and symmetry elements 388
Checklist of equations 429
10A.2 The symmetry classification of molecules 390
(a) The groups C1, Ci, and Cs 392
TOPIC 11B Rotational spectroscopy 430
(b) The groups Cn, Cnv, and Cnh 392
11B.1 Rotational energy levels 430
(c) The groups Dn, Dnh, and Dnd 393
(a) Spherical rotors 432
(d) The groups Sn 393
xx Full Contents

(b) Symmetric rotors 432 TOPIC 11G Decay of excited states 470
(c) Linear rotors 434
11G.1 Fluorescence and phosphorescence 470
(d) Centrifugal distortion 434
11G.2 Dissociation and predissociation 472
11B.2 Microwave spectroscopy 435
11G.3 Lasers 473
(a) Selection rules 435
Checklist of concepts 474
(b) The appearance of microwave spectra 436
11B.3 Rotational Raman spectroscopy 437
11B.4 Nuclear statistics and rotational states 439 FOCUS 12 Magnetic resonance 487
Checklist of concepts 441
TOPIC 12A General principles 488
Checklist of equations 441
12A.1 Nuclear magnetic resonance 488
(a) The energies of nuclei in magnetic fields 488
TOPIC 11C Vibrational spectroscopy of diatomic
(b) The NMR spectrometer 490
molecules 442
12A.2 Electron paramagnetic resonance 491
11C.1 Vibrational motion 442
(a) The energies of electrons in magnetic fields 491
11C.2 Infrared spectroscopy 443
(b) The EPR spectrometer 492
11C.3 Anharmonicity 444
Checklist of concepts 493
(a) The convergence of energy levels 444
Checklist of equations 493
(b) The Birge–Sponer plot 445
11C.4 Vibration–rotation spectra 446 ­TOPIC 12B Features of NMR spectra 494
(a) Spectral branches 447
12B.1 The chemical shift 494
(b) Combination differences 448
12B.2 The origin of shielding constants 496
11C.5 Vibrational Raman spectra 448
(a) The local contribution 496
Checklist of concepts 449 (b) Neighbouring group contributions 497
Checklist of equations 450 (c) The solvent contribution 498
12B.3 The fine structure 499
TOPIC 11D Vibrational spectroscopy of polyatomic (a) The appearance of the spectrum 499
molecules 451 (b) The magnitudes of coupling constants 501
11D.1 Normal modes 451 (c) The origin of spin–spin coupling 502
11D.2 Infrared absorption spectra 452 (d) Equivalent nuclei 503
11D.3 Vibrational Raman spectra 453 (e) Strongly coupled nuclei 504
Checklist of concepts 454 12B.4 Exchange processes 505
Checklist of equations 454 12B.5 Solid-state NMR 506
Checklist of concepts 507
TOPIC 11E Symmetry analysis of vibrational Checklist of equations 508
spectra 455
11E.1 Classification of normal modes according to symmetry 455 TOPIC 12C Pulse techniques in NMR 509
11E.2 Symmetry of vibrational wavefunctions 457 12C.1 The magnetization vector 509
(a) Infrared activity of normal modes 457 (a) The effect of the radiofrequency field 510
(b) Raman activity of normal modes 458 (b) Time- and frequency-domain signals 511
(c) The symmetry basis of the exclusion rule 458 12C.2 Spin relaxation 513
Checklist of concepts 458 (a) The mechanism of relaxation 513
(b) The measurement of T1 and T2 514
TOPIC 11F Electronic spectra 459 12C.3 Spin decoupling 515
11F.1 Diatomic molecules 459
12C.4 The nuclear Overhauser effect 516
(a) Term symbols 459
Checklist of concepts 518
(b) Selection rules 461
Checklist of equations 518
(c) Vibrational fine structure 462
(d) Rotational fine structure 465
TOPIC 12D Electron paramagnetic resonance 519
11F.2 Polyatomic molecules 466
12D.1 The g-value 519
(a) d-Metal complexes 467
12D.2 Hyperfine structure 520
(b) π* ← π and π* ← n transitions 468
(a) The effects of nuclear spin 520
Checklist of concepts 469
(b) The McConnell equation 521
Checklist of equations 469 (c) The origin of the hyperfine interaction 522
 Full Contents xxi

Checklist of concepts 523 (e) Residual entropies 565

Checklist of equations 523 Checklist of concepts 566
Checklist of equations 566

FOCUS 13 Statistical thermodynamics 531 TOPIC 13F Derived functions 567

TOPIC 13A The Boltzmann distribution 532 13F.1 The derivations 567
13A.1 Configurations and weights 532 13F.2 Equilibrium constants 570
(a) Instantaneous configurations 532 (a) The relation between K and the partition function 570
(b) The most probable distribution 533 (b) A dissociation equilibrium 570
(c) The values of the constants 535 (c) Contributions to the equilibrium constant 571

13A.2 The relative population of states 536 Checklist of concepts 573

Checklist of concepts 536 Checklist of equations 573
Checklist of equations 537

TOPIC 13B Molecular partition functions 538

FOCUS 14 Molecular interactions 583
13B.1 The significance of the partition function 538 TOPIC 14A The electric properties of molecules 585
13B.2 Contributions to the partition function 540 14A.1 Electric dipole moments 585
(a) The translational contribution 540 14A.2 Polarizabilities 587
(b) The rotational contribution 542 14A.3 Polarization 588
(c) The vibrational contribution 546 (a) The frequency dependence of the polarization 588
(d) The electronic contribution 547 (b) Molar polarization 590
Checklist of concepts 548 Checklist of concepts 592
Checklist of equations 548 Checklist of equations 592

TOPIC 13C Molecular energies 549 TOPIC 14B Interactions between ­molecules 593
13C.1 The basic equations 549 14B.1 The interactions of dipoles 593
13C.2 Contributions of the fundamental modes of motion 550 (a) Charge–dipole interactions 593
(a) The translational contribution 550 (b) Dipole–dipole interactions 594
(b) The rotational contribution 550 (c) Dipole–induced dipole interactions 597
(c) The vibrational contribution 551 (d) Induced dipole–induced dipole interactions 597
(d) The electronic contribution 552 14B.2 Hydrogen bonding 598
(e) The spin contribution 552
14B.3 The total interaction 599
Checklist of concepts 553 Checklist of concepts 601
Checklist of equations 553 Checklist of equations 601

TOPIC 13D The canonical ensemble 554 TOPIC 14C Liquids 602
13D.1 The concept of ensemble 554 14C.1 Molecular interactions in liquids 602
(a) Dominating configurations 555
(a) The radial distribution function 602
(b) Fluctuations from the most probable distribution 555
(b) The calculation of g(r) 603
13D.2 The mean energy of a system 556 (c) The thermodynamic properties of liquids 604
13D.3 Independent molecules revisited 556 14C.2 The liquid–vapour interface 605
13D.4 The variation of the energy with volume 557 (a) Surface tension 605
Checklist of concepts 558 (b) Curved surfaces 606
Checklist of equations 558 (c) Capillary action 606
14C.3 Surface films 608
TOPIC 13E The internal energy and the entropy 559 (a) Surface pressure 608
13E.1 The internal energy 559 (b) The thermodynamics of surface layers 609
(a) The calculation of internal energy 559 14C.4 Condensation 611
(b) Heat capacity 560 Checklist of concepts 612
13E.2 The entropy 561 Checklist of equations 612
(a) Entropy and the partition function 561
(b) The translational contribution 563 TOPIC 14D Macromolecules 613
(c) The rotational contribution 563 14D.1 Average molar masses 613
(d) The vibrational contribution 564
14D.2 The different levels of structure 614
xxii Full Contents

14D.3 Random coils 615 TOPIC 15D The mechanical properties of solids 666
(a) Measures of size 615 Checklist of concepts 667
(b) Constrained chains 618
Checklist of equations 668
(c) Partly rigid coils 618
14D.4 Mechanical properties 619 TOPIC 15E The electrical properties of solids 669
(a) Conformational entropy 619 15E.1 Metallic conductors 669
(b) Elastomers 620
15E.2 Insulators and semiconductors 670
14D.5 Thermal properties 621
15E.3 Superconductors 672
Checklist of concepts 622
Checklist of concepts 673
Checklist of equations 622
Checklist of equations 673

TOPIC 14E Self-assembly 623 TOPIC 15F The magnetic properties of solids 674
14E.1 Colloids 623
15F.1 Magnetic susceptibility 674
(a) Classification and preparation 623
15F.2 Permanent and induced magnetic moments 675
(b) Structure and stability 624
15F.3 Magnetic properties of superconductors 676
(c) The electrical double layer 624
Checklist of concepts 676
14E.2 Micelles and biological membranes 626
(a) The hydrophobic interaction 626 Checklist of equations 677
(b) Micelle formation 627
(c) Bilayers, vesicles, and membranes 628
TOPIC 15G The optical properties of solids 678
15G.1 Excitons 678
Checklist of concepts 630
15G.2 Metals and semiconductors 679
Checklist of equations 630
(a) Light absorption 679
(b) Light-emitting diodes and diode lasers 680
FOCUS 15 Solids 639 15G.3 Nonlinear optical phenomena 680

TOPIC 15A Crystal structure 641 Checklist of concepts 681

15A.1 Periodic crystal lattices 641

15A.2 The identification of lattice planes 643 FOCUS 16 Molecules in motion 689
(a) The Miller indices 643
(b) The separation of neighbouring planes 644
TOPIC 16A Transport properties of a
perfect gas 690
Checklist of concepts 645
16A.1 The phenomenological equations 690
Checklist of equations 645
16A.2 The transport parameters 692
TOPIC 15B Diffraction techniques 646 (a) The diffusion coefficient 693
(b) Thermal conductivity 694
15B.1 X-ray crystallography 646
(c) Viscosity 696
(a) X-ray diffraction 646
(d) Effusion 697
(b) Bragg’s law 648
(c) Scattering factors 649 Checklist of concepts 697
(d) The electron density 649 Checklist of equations 698
(e) The determination of structure 652
15B.2 Neutron and electron diffraction 654
TOPIC 16B Motion in liquids 699
16B.1 Experimental results 699
Checklist of concepts 655
(a) Liquid viscosity 699
Checklist of equations 655
(b) Electrolyte solutions 700

TOPIC 15C Bonding in solids 656 16B.2 The mobilities of ions 701
(a) The drift speed 701
15C.1 Metals 656
(b) Mobility and conductivity 703
(a) Close packing 656
(c) The Einstein relations 704
(b) Electronic structure of metals 658
15C.2 Ionic solids 660 Checklist of concepts 705
(a) Structure 660 Checklist of equations 705
(b) Energetics 661
FOCUS 16C Diffusion 706
15C.3 Covalent and molecular solids 663
16C.1 The thermodynamic view 706
Checklist of concepts 664
16C.2 The diffusion equation 708
Checklist of equations 665
(a) Simple diffusion 708
 Full Contents xxiii

(b) Diffusion with convection 710 (a) Stepwise polymerization 755

(c) Solutions of the diffusion equation 710 (b) Chain polymerization 756
16C.3 The statistical view 712 17F.3 Enzyme-catalysed reactions 758
Checklist of concepts 713 Checklist of concepts 761
Checklist of equations 714 Checklist of equations 761

TOPIC 17G Photochemistry 762

FOCUS 17 Chemical kinetics 721 17G.1 Photochemical processes 762
TOPIC 17A The rates of chemical reactions 723 17G.2 The primary quantum yield 763
17A.1 Monitoring the progress of a reaction 723 17G.3 Mechanism of decay of excited singlet states 764
(a) General considerations 723 17G.4 Quenching 765
(b) Special techniques 724 17G.5 Resonance energy transfer 767
17A.2 The rates of reactions 725 Checklist of concepts 768
(a) The definition of rate 725 Checklist of equations 768
(b) Rate laws and rate constants 726
(c) Reaction order 727
(d) The determination of the rate law 728 FOCUS 18 Reaction dynamics 779
Checklist of concepts 729 TOPIC 18A Collision theory 780
Checklist of equations 730 18A.1 Reactive encounters 780
(a) Collision rates in gases 781
TOPIC 17B Integrated rate laws 731
(b) The energy requirement 781
17B.1 Zeroth-order reactions 731
(c) The steric requirement 784
17B.2 First-order reactions 731
18A.2 The RRK model 785
17B.3 Second-order reactions 733
Checklist of concepts 786
Checklist of concepts 736
Checklist of equations 786
Checklist of equations 736
TOPIC 18B Diffusion-controlled ­reactions 787
TOPIC 17C Reactions approaching equilibrium 737 18B.1 Reactions in solution 787
17C.1 First-order reactions approaching equilibrium 737 (a) Classes of reaction 787
17C.2 Relaxation methods 738 (b) Diffusion and reaction 788
Checklist of concepts 740 18B.2 The material-balance equation 789
Checklist of equations 740 (a) The formulation of the equation 789
(b) Solutions of the equation 790
TOPIC 17D The Arrhenius equation 741 Checklist of concepts 790
17D.1 The temperature dependence of reaction rates 741 Checklist of equations 791
17D.2 The interpretation of the Arrhenius parameters 742
(a) A first look at the energy requirements of reactions 743 TOPIC 18C Transition-state theory 792
(b) The effect of a catalyst on the activation energy 744 18C.1 The Eyring equation 792
Checklist of concepts 745 (a) The formulation of the equation 792
Checklist of equations 745 (b) The rate of decay of the activated complex 793
(c) The concentration of the activated complex 793
TOPIC 17E Reaction mechanisms 746 (d) The rate constant 794
17E.1 Elementary reactions 746 18C.2 Thermodynamic aspects 795
17E.2 Consecutive elementary reactions 747 (a) Activation parameters 795

17E.3 The steady-state approximation 748 (b) Reactions between ions 797

17E.4 The rate-determining step 749 18C.3 The kinetic isotope effect 798
17E.5 Pre-equilibria 750 Checklist of concepts 800
17E.6 Kinetic and thermodynamic control of reactions 752 Checklist of equations 800
Checklist of concepts 752
TOPIC 18D The dynamics of molecular collisions 801
Checklist of equations 752
18D.1 Molecular beams 801
(a) Techniques 801
TOPIC 17F Examples of reaction mechanisms 753
(b) Experimental results 802
17F.1 Unimolecular reactions 753
18D.2 Reactive collisions 804
17F.2 Polymerization kinetics 754
(a) Probes of reactive collisions 804
xxiv Full Contents

(b) State-to-state reaction dynamics 804 (d) The Temkin and Freundlich isotherms 837
18D.3 Potential energy surfaces 805 19B.2 The rates of adsorption and desorption 837
18D.4 Some results from experiments and calculations 806 (a) The precursor state 837
(a) The direction of attack and separation 807 (b) Adsorption and desorption at the molecular level 838
(b) Attractive and repulsive surfaces 808 (c) Mobility on surfaces 839
(c) Quantum mechanical scattering theory 808 Checklist of concepts 840
Checklist of concepts 809 Checklist of equations 840
Checklist of equations 809
TOPIC 19C Heterogeneous catalysis 841
TOPIC 18E Electron transfer in ­homogeneous 19C.1 Mechanisms of heterogeneous catalysis 841
systems 810 (a) Unimolecular reactions 841
18E.1 The rate law 810 (b) The Langmuir–Hinshelwood mechanism 842

18E.2 The role of electron tunnelling 811 (c) The Eley–Rideal mechanism 843

18E.3 The rate constant 812 19C.2 Catalytic activity at surfaces 843

18E.4 Experimental tests of the theory 813 Checklist of concepts 844

Checklist of concepts 815 Checklist of equations 844

Checklist of equations 815

TOPIC 19D Processes at electrodes 845
19D.1 The electrode–solution interface 845
FOCUS 19 Processes at solid surfaces 823 19D.2 The current density at an electrode 846
(a) The Butler–Volmer equation 846
TOPIC 19A An introduction to solid surfaces 824
(b) Tafel plots 850
19A.1 Surface growth 824
19D.3 Voltammetry 850
19A.2 Physisorption and chemisorption 825
19D.4 Electrolysis 852
19A.3 Experimental techniques 826
19D.5 Working galvanic cells 853
(a) Microscopy 827
Checklist of concepts 854
(b) Ionization techniques 828
(c) Diffraction techniques 829 Checklist of equations 854
(d) Determination of the extent and rates of adsorption and desorption 830
Checklist of concepts 831 Resource section 861
Checklist of equations 831 1 Common integrals 862
TOPIC 19B Adsorption and desorption 832 2 Units 864
19B.1 Adsorption isotherms 832 3 Data 865
(a) The Langmuir isotherm 832 4 Character tables 895
(b) The isosteric enthalpy of adsorption 834
(c) The BET isotherm 835 Index899
CONVENTIONS

To avoid intermediate rounding errors, but to keep track of Blue terms are used when we want to identify a term in an
values in order to be aware of values and to spot numerical er- equation. An entire quotient, numerator/denominator, is col-
rors, we display intermediate results as n.nnn… and round the oured blue if the annotation refers to the entire term, not just
calculation only at the final step. to the numerator or denominator separately.
LIST OF TABLES
⦵
Table 1A.1 Pressure units 4 Table 5F.1 Ionic strength and molality, I = kb/b 188
Table 1B.1 The (molar) gas constant 14 Table 5F.2 Mean activity coefficients in water at 298 K 188
Table 1B.2 Collision cross-sections 17 Table 5F.3 Activities and standard states: a summary 189
Table 1C.1 Second virial coefficients, B/(cm3 mol−1) 21 Table 6C.1 Varieties of electrode 217
Table 1C.2 Critical constants of gases 23 Table 6D.1 Standard potentials at 298 K 224
Table 1C.3 van der Waals coefficients 23 Table 6D.2 The electrochemical series 227
Table 1C.4 Selected equations of state 25 Table 7E.1 The Hermite polynomials 275
Table 2A.1 Varieties of work 39 Table 7F.1 The spherical harmonics 286
Table 2B.1 Temperature variation of molar heat capacities, Table 8A.1 Hydrogenic radial wavefunctions 306
Cp,m/(J K−1 mol−1) = a + bT + c/T 2 49
Table 8B.1 Effective nuclear charge 320
Table 2C.1 Standard enthalpies of fusion and vaporization
Table 8B.2 Atomic radii of main-group elements, r/pm 323
at the transition temperature 52
Table 8B.3 Ionic radii, r/pm 324
Table 2C.2 Enthalpies of reaction and transition 52
Table 8B.4 First and second ionization energies 325
Table 2C.3 Standard enthalpies of formation and
combustion of organic compounds at 298 K 53 Table 8B.5 Electron affinities, E a/(kJ mol−1) 325
Table 2C.4 Standard enthalpies of formation of inorganic Table 9A.1 Some hybridization schemes 349
compounds at 298 K 54
Table 9C.1 Overlap integrals between hydrogenic orbitals 359
Table 2C.5 Standard enthalpies of formation of organic
Table 9C.2 Bond lengths 362
compounds at 298 K 54
Table 9C.3 Bond dissociation energies 362
Table 2D.1 Expansion coefficients (α) and isothermal
compressibilities (κT) at 298 K 62 Table 9D.1 Pauling electronegativities 366
Table 2D.2 Inversion temperatures (TI), normal freezing Table 10A.1 The notations for point groups 390
(Tf ) and boiling (Tb) points, and Joule–Thomson
Table 10B.1 The C2v character table 402
coefficients (μ) at 1 atm and 298 K 63
Table 10B.2 The C3v character table 402
Table 3B.1 Standard entropies of phase transitions,
⦵
Δtrs S /(J K−1 mol−1), at the corresponding normal Table 10B.3 The C4 character table 405
transition temperatures 89
Table 11B.1 Moments of inertia 431
Table 3B.2 The standard enthalpies and entropies of
Table 11C.1 Properties of diatomic molecules 447
­vaporization of liquids at their boiling
temperatures 89 Table 11F.1 Colour, frequency, and energy of light 459
Table 3C.1 Standard Third-Law entropies at 298 K 94 Table 11F.2 Absorption characteristics of some groups and
molecules 467
Table 3D.1 Standard Gibbs energies of formation at 298 K 101
Table 11G.1 Characteristics of laser radiation and their
Table 3E.1 The Maxwell relations 105
chemical applications 473
Table 5A.1 Henry’s law constants for gases in water
Table 12A.1 Nuclear constitution and the nuclear spin
at 298 K 153
quantum number 488
Table 5B.1 Freezing-point (Kf ) and boiling-point (Kb)
Table 12A.2 Nuclear spin properties 489
constants 160
 LIST OF TABLES xxvii

Table 12D.1 Hyperfine coupling constants for atoms, a/mT 522 Table 17B.2 Kinetic data for second-order reactions 733

Table 13B.1 Rotational temperatures of diatomic molecules 544 Table 17B.3 Integrated rate laws 735

Table 13B.2 Symmetry numbers of molecules 545 Table 17D.1 Arrhenius parameters 741

Table 13B.3 Vibrational temperatures of diatomic Table 17G.1 Examples of photochemical processes 762
molecules 547
Table 17G.2 Common photophysical processes 763
Table 14A.1 Dipole moments and polarizability volumes 585
Table 17G.3 Values of R0 for some donor–acceptor pairs 767
Table 14B.1 Interaction potential energies 597
Table 18A.1 Arrhenius parameters for gas-phase reactions 784
Table 14B.2 Lennard-Jones-(12,6) potential energy
Table 18B.1 Arrhenius parameters for solvolysis
parameters 600
reactions in solution 788
Table 14C.1 Surface tensions of liquids at 293 K 605
Table 19A.1 Maximum observed standard enthalpies of
Table 14E.1 Micelle shape and the surfactant parameter 628 ­physisorption at 298 K 825

Table 15A.1 The seven crystal systems 642 Table 19A.2 Standard enthalpies of chemisorption,
⦵
Δad H /(kJ mol−1), at 298 K 825
Table 15C.1 The crystal structures of some elements 657
Table 19C.1 Chemisorption abilities 844
Table 15C.2 Ionic radii, r/pm 661
Table 19D.1 Exchange-current densities and transfer
Table 15C.3 Madelung constants 662
coefficients at 298 K 849
Table 15C.4 Lattice enthalpies at 298 K, ΔHL/(kJ mol−1) 663
Table A.1 Some common units 864
Table 15F.1 Magnetic susceptibilities at 298 K 675
Table A.2 Common SI prefixes 864
Table 16A.1 Transport properties of gases at 1 atm 691
Table A.3 The SI base units 864
Table 16B.1 Viscosities of liquids at 298 K 699
Table A.4 A selection of derived units 864
Table 16B.2 Ionic mobilities in water at 298 K 702
Table 0.1 Physical properties of selected materials 866
Table 16B.3 Diffusion coefficients at 298 K, D/(10−9 m2 s −1) 704
Table 0.2 Masses and natural abundances of selected
Table 17B.1 Kinetic data for first-order reactions 732 nuclides 867
LIST OF THE CHEMIST’S TOOLKITS

Number Topic Title

1 1A Quantities and units 5
2 1A Properties of bulk matter 6
3 1B Momentum and force 11
4 1B Integration 14
5 1C Differentiation 22
6 2A Work and energy 35
7 2A The equipartition theorem 37
8 2A Electrical charge, current, power, and energy 43
9 2A Partial derivatives 44
10 3E Exact differentials 105
11 5A Measures of concentration 148
12 5B Series expansions 160
13 7A Electromagnetic radiation 237
14 7B Complex numbers 247
15 7C Integration by parts 254
16 7C Euler’s formula 256
17 7D Vectors 262
18 7E The classical harmonic oscillator 273
19 7F Cylindrical coordinates 281
20 7F Angular momentum 282
21 7F Spherical polar coordinates 286
22 8C The manipulation of vectors 330
23 9D Determinants 368
24 9E Matrices 373
25 9E Matrix methods for solving eigenvalue equations 375
26 11A Exponential and Gaussian functions 424
27 12B Dipolar magnetic fields 497
28 12C The Fourier transform 512
29 16B Electrostatics 702
30 17B Integration by the method of partial fractions 735
LIST OF MATERIAL PROVIDED AS
A DEEPER LOOK

Number Title
1 The Debye–Hückel theory
2 The fugacity
3 Separation of variables
4 The energy of the bonding molecular orbital of H2+
5 Rotational selection rules
6 Vibrational selection rules
7 The van der Waals equation of state
8 The electric dipole–dipole interaction
9 The virial and the virial equation of state
10 Establishing the relation between bulk and molecular properties
11 The random walk
12 The RRK model
13 The BET isotherm
LIST OF IMPAC TS

Number Focus Title

1 1 . . .on environmental science: The gas laws and the weather
2 1 . . .on astrophysics: The Sun as a ball of perfect gas
3 2 . . .on technology: Thermochemical aspects of fuels and foods
4 3 . . .on engineering: Refrigeration
5 3 . . .on materials science: Crystal defects
6 4 . . .on technology: Supercritical fluids
7 5 . . .on biology: Osmosis in physiology and biochemistry
8 5 . . .on materials science: Liquid crystals
9 6 . . .on biochemistry: Energy conversion in biological cells
10 6 . . .on chemical analysis: Species-selective electrodes
11 7 . . .on technology: Quantum computing
12 7 . . .on nanoscience: Quantum dots
13 8 . . .on astrophysics: The spectroscopy of stars
14 9 . . .on biochemistry: The reactivity of O2, N2, and NO
15 9 . . .on biochemistry: Computational studies of biomolecules
16 11 . . .on astrophysics: Rotational and vibrational spectroscopy of interstellar species
17 11 . . .on environmental science: Climate change
18 12 . . .on medicine: Magnetic resonance imaging
19 12 . . .on biochemistry and nanoscience: Spin probes
20 13 . . .on biochemistry: The helix–coil transition in polypeptides
21 14 . . .on biology: Biological macromolecules
22 14 . . .on medicine: Molecular recognition and drug design
23 15 . . .on biochemistry: Analysis of DNA by X-ray diffraction
24 15 . . .on nanoscience: Nanowires
25 16 . . .on biochemistry: Ion channels
26 17 . . .on biochemistry: Harvesting of light during plant photosynthesis
27 19 . . .on technology: Catalysis in the chemical industry
28 19 . . .on technology: Fuel cells
PROLOGUE Energy, temperature, and chemistry
Energy is a concept used throughout chemistry to discuss mo-
lecular structures, reactions, and many other processes. What
follows is an informal first look at the important features of
energy. Its precise definition and role will emerge throughout
the course of this text.
The transformation of energy from one form to another is
described by the laws of thermodynamics. They are applicable
to bulk matter, which consists of very large numbers of atoms
and molecules. The ‘First Law’ of thermodynamics is a state-
ment about the quantity of energy involved in a transforma-
tion; the ‘Second Law’ is a statement about the dispersal of that
energy (in a sense that will be explained).
To discuss the energy of individual atoms and molecules
that make up samples of bulk matter it is necessary to use
quantum mechanics. According to this theory, the energy as-
sociated with the motion of a particle is ‘quantized’, meaning
that the energy is restricted to certain values, rather than being
able to take on any value. Three different kinds of motion can
occur: translation (motion through space), rotation (change of
orientation), and vibration (the periodic stretching and bend-
ing of bonds). Figure 1 depicts the relative sizes and spacing of
the energy states associated with these different kinds of mo-
tion of typical molecules and compares them with the typi-
cal energies of electrons in atoms and molecules. The allowed
energies associated with translation are so close together in
normal-sized containers that they form a continuum. In con-
trast, the separation between the allowed electronic energy
states of atoms and molecules is very large.
The link between the energies of individual molecules and the
energy of bulk matter is provided by one of the most important
concepts in chemistry, the Boltzmann distribution. Bulk matter
Translation Rotation Vibration Electronic
0.01 1–10 100
Continuum
Figure 1 The relative energies of the allowed states of various
kinds of atomic and molecular motion.
consists of large numbers of molecules, each of which is in one of
its available energy states. The total number of molecules with a
particular energy due to translation, rotation, vibration, and its
electronic state is called the ‘population’ of that state. Most mole-
cules are found in the lowest energy state, and higher energy states
are occupied by progressively fewer molecules. The Boltzmann
distribution gives the population, Ni, of any energy state in terms
of the energy of the state, εi, and the absolute temperature, T:
Ni ∝ e−εi/kT
In this expression, k is Boltzmann’s constant (its value is
listed inside the front cover), a universal constant (in the sense
of having the same value for all forms of matter). Figure 2
shows the Boltzmann distribution for two temperatures: as
the temperature increases higher energy states are populated
at the expense of states lower in energy. According to the
Boltzmann distribution, the temperature is the single param-
eter that governs the spread of populations over the available
energy states, whatever their nature.
Allowed energy states
Energy
Population
(a) Low temperature
Allowed energy states
Energy
Population
(b) High temperature
Figure 2 The relative populations of states at (a) low, (b) high
temperature according to the Boltzmann distribution.
2 Prologue Energy, temperature, and chemistry
The Boltzmann distribution, as well as providing insight
into the significance of temperature, is central to understand-
ing much of chemistry. That most molecules occupy states of
low energy when the temperature is low accounts for the exist-
ence of compounds and the persistence of liquids and solids.
That highly excited energy levels become accessible at high
temperatures accounts for the possibility of reaction as one
substance acquires the ability to change into another. Both
features are explored in detail throughout the text.
You should keep in mind the Boltzmann distribution
(which is treated in greater depth later in the text) whenever
considering the interpretation of the properties of bulk matter
and the role of temperature. An understanding of the flow of
energy and how it is distributed according to the Boltzmann
distribution is the key to understanding thermodynamics,
structure, and change throughout chemistry.
FOCUS 1
The properties of gases
A gas is a form of matter that fills whatever container it oc-
cupies. This Focus establishes the properties of gases that are
used throughout the text.
1A The perfect gas
This Topic is an account of an idealized version of a gas, a ‘per-
fect gas’, and shows how its equation of state may be assembled
from the experimental observations summarized by Boyle’s
law, Charles’s law, and Avogadro’s principle.
1A.1 Variables of state; 1A.2 Equations of state
1B The kinetic model
A central feature of physical chemistry is its role in building
models of molecular behaviour that seek to explain observed
phenomena. A prime example of this procedure is the de-
velopment of a molecular model of a perfect gas in terms of
a collection of molecules (or atoms) in ceaseless, essentially
random motion. As well as accounting for the gas laws, this
model can be used to predict the average speed at which mol-
ecules move in a gas, and its dependence on temperature. In
combination with the Boltzmann distribution (see the text’s
Prologue), the model can also be used to predict the spread of
molecular speeds and its dependence on molecular mass and
temperature.
1B.1 The model; 1B.2 Collisions
1C Real gases
The perfect gas is a starting point for the discussion of prop-
erties of all gases, and its properties are invoked throughout
thermodynamics. However, actual gases, ‘real gases’, have
properties that differ from those of perfect gases, and it is nec-
essary to be able to interpret these deviations and build the ef-
fects of molecular attractions and repulsions into the model.
The discussion of real gases is another example of how initially
primitive models in physical chemistry are elaborated to take
into account more detailed observations.
1C.1 Deviations from perfect behaviour; 1C.2 The van der Waals
equation
Web resources What is an application
of this material?
The perfect gas law and the kinetic theory can be applied to
the study of phenomena confined to a reaction vessel or en-
compassing an entire planet or star. In Impact 1 the gas laws
are used in the discussion of meteorological phenomena—the
weather. Impact 2 examines how the kinetic model of gases
has a surprising application: to the discussion of dense stellar
media, such as the interior of the Sun.
TOPIC 1A The perfect gas

Table 1A.1 Pressure units*

➤ Why do you need to know this material?
Name Symbol Value
Equations related to perfect gases provide the basis for
pascal Pa 1 Pa = 1 N m−2, 1 kg m−1 s−2
the development of many relations in thermodynamics.
The perfect gas law is also a good first approximation for bar bar 1 bar = 105 Pa

accounting for the properties of real gases. atmosphere atm 1 atm = 101.325 kPa
torr Torr 1 Torr = (101 325/760) Pa = 133.32… Pa
➤ What is the key idea? millimetres of mercury mmHg 1 mmHg = 133.322… Pa
The perfect gas law, which is based on a series of empirical pounds per square inch psi 1 psi = 6.894 757… kPa
observations, is a limiting law that is obeyed increasingly
* Values in bold are exact.
well as the pressure of a gas tends to zero.

➤ What do you need to know already?
You need to know how to handle quantities and units in
calculations, as reviewed in The chemist’s toolkit 1. You also
of pressure, the pascal (Pa, 1 Pa = 1 N m−2), is introduced in
The chemist’s toolkit 1. Several other units are still widely used
(Table 1A.1). A pressure of 1 bar is the standard pressure for
reporting data; it is denoted p .
⦵

need to be aware of the concepts of pressure, volume,

amount of substance, and temperature, all reviewed in The
chemist’s toolkit 2.
The properties of gases were among the first to be established
quantitatively (largely during the seventeenth and eighteenth
centuries) when the technological requirements of travel in
balloons stimulated their investigation. These properties set
the stage for the development of the kinetic model of gases, as
discussed in Topic 1B.
If two gases are in separate containers that share a common
movable wall (Fig. 1A.1), the gas that has the higher pressure
will tend to compress (reduce the volume of) the gas that has
lower pressure. The pressure of the high-pressure gas will fall as
it expands and that of the low-pressure gas will rise as it is com-
pressed. There will come a stage when the two pressures are
equal and the wall has no further tendency to move. This con-
dition of equality of pressure on either side of a movable wall is
a state of mechanical equilibrium between the two gases. The
pressure of a gas is therefore an indication of whether a con-
tainer that contains the gas will be in mechanical equilibrium
with another gas with which it shares a movable wall.

(a) Movable
High wall Low
1A.1 Variables of state pressure pressure

The physical state of a sample of a substance, its physical con- (b)

Equal Equal
dition, is defined by its physical properties. Two samples of the
pressures pressures
same substance that have the same physical properties are in
the same state. The variables needed to specify the state of a
(c)
system are the amount of substance it contains, n, the volume Low High
it occupies, V, the pressure, p, and the temperature, T. pressure pressure

(a) Pressure
The origin of the force exerted by a gas is the incessant bat-
tering of the molecules on the walls of its container. The col-
lisions are so numerous that they exert an effectively steady
force, which is experienced as a steady pressure. The SI unit
Figure 1A.1 When a region of high pressure is separated from a
region of low pressure by a movable wall, the wall will be pushed
into one region or the other, as in (a) and (c). However, if the
two pressures are identical, the wall will not move (b). The latter
condition is one of mechanical equilibrium between the two
regions.

The chemist’s toolkit 1 Quantities and units
The result of a measurement is a physical quantity that is
reported as a numerical multiple of a unit:
physical quantity = numerical value × unit
It follows that units may be treated like algebraic quantities and
may be multiplied, divided, and cancelled. Thus, the expression
(physical quantity)/unit is the numerical value (a dimension-
less quantity) of the measurement in the specified units. For
instance, the mass m of an object could be reported as m = 2.5 kg
or m/kg = 2.5. In this instance the unit of mass is 1 kg, but it is
common to refer to the unit simply as kg (and likewise for other
units). See Table A.1 in the Resource section for a list of units.
Although it is good practice to use only SI units, there will be
occasions where accepted practice is so deeply rooted that physical
quantities are expressed using other, non-SI units. By international
convention, all physical quantities are represented by oblique
(sloping) letters (for instance, m for mass); units are given in
roman (upright) letters (for instance m for metre).
Units may be modified by a prefix that denotes a factor of a
power of 10. Among the most common SI prefixes are those
The pressure exerted by the atmosphere is measured with
a barometer. The original version of a barometer (which was
invented by Torricelli, a student of Galileo) was an inverted
tube of mercury sealed at the upper end. When the column of
mercury is in mechanical equilibrium with the atmosphere,
the pressure at its base is equal to that exerted by the atmos-
phere. It follows that the height of the mercury column is pro-
portional to the external pressure.
The pressure of a sample of gas inside a container is
measured by using a pressure gauge, which is a device with
properties that respond to the pressure. For instance, a
Bayard–Alpert pressure gauge is based on the ionization of
the molecules present in the gas and the resulting current of
ions is interpreted in terms of the pressure. In a capacitance
manometer, the deflection of a diaphragm relative to a fixed
electrode is monitored through its effect on the capacitance
of the arrangement. Certain semiconductors also respond to
pressure and are used as transducers in solid-state pressure
gauges.
(b) Temperature
The concept of temperature is introduced in The chemist’s
toolkit 2. In the early days of thermometry (and still in labora-
tory practice today), temperatures were related to the length
of a column of liquid, and the difference in lengths shown
when the thermometer was first in contact with melting ice
and then with boiling water was divided into 100 steps called
‘degrees’, the lower point being labelled 0. This procedure led
1A The perfect gas 5
listed in Table A.2 in the Resource section. Examples of the use
of these prefixes are:
1 nm = 10−9 m    1 ps = 10−12 s  1 µmol = 10−6 mol
Powers of units apply to the prefix as well as the unit they mod-
ify. For example, 1 cm3 = 1 (cm)3, and (10−2 m)3 = 10−6 m3. Note
that 1 cm3 does not mean 1 c(m3). When carrying out numerical
calculations, it is usually safest to write out the numerical value
of an observable in scientific notation (as n.nnn × 10n).
There are seven SI base units, which are listed in Table A.3
in the Resource section. All other physical quantities may be
expressed as combinations of these base units. Molar concen-
tration (more formally, but very rarely, amount of substance
concentration) for example, which is an amount of substance
divided by the volume it occupies, can be expressed using the
derived units of mol dm−3 as a combination of the base units for
amount of substance and length. A number of these derived
combinations of units have special names and symbols. For
example, force is reported in the derived unit newton, 1 N =
1 kg m s −2 (see Table A.4 in the Resource section).
to the Celsius scale of temperature. In this text, temperatures
on the Celsius scale are denoted θ (theta) and expressed in de-
grees Celsius (°C). However, because different liquids expand
to different extents, and do not always expand uniformly over
a given range, thermometers constructed from different mate-
rials showed different numerical values of the temperature be-
tween their fixed points. The pressure of a gas, however, can be
used to construct a perfect-gas temperature scale that is inde-
pendent of the identity of the gas. The perfect-gas scale turns
out to be identical to the thermodynamic temperature scale
(Topic 3A), so the latter term is used from now on to avoid a
proliferation of names.
On the thermodynamic temperature scale, temperatures
are denoted T and are normally reported in kelvins (K; not °K).
Thermodynamic and Celsius temperatures are related by the
exact expression
Celsius scale
T/K = θ/°C + 273.15 (1A.1)
[definition]
This relation is the current definition of the Celsius scale in
terms of the more fundamental Kelvin scale. It implies that a
difference in temperature of 1 °C is equivalent to a difference
of 1 K.
Brief illustration 1A.1
To express 25.00 °C as a temperature in kelvins, eqn 1A.1 is
used to write
T/K = (25.00 °C)/°C + 273.15 = 25.00 + 273.15 = 298.15
6 1 The properties of gases

The chemist’s toolkit 2 Properties of bulk matter

The state of a bulk sample of matter is defined by specifying the A sample of matter may be subjected to a pressure, p (unit: pascal,
values of various properties. Among them are: Pa; 1 Pa = 1 kg m−1 s−2), which is defined as the force, F, it is subjected
to, divided by the area, A, to which that force is applied. Although
The mass, m, a measure of the quantity of matter present
the pascal is the SI unit of pressure, it is also common to express
(unit: kilogram, kg).
pressure in bar (1 bar = 105 Pa) or atmospheres (1 atm = 101 325 Pa
The volume, V, a measure of the quantity of space the sam- exactly), both of which correspond to typical atmospheric pres-
ple occupies (unit: cubic metre, m3). sure. Because many physical properties depend on the pressure
The amount of substance, n, a measure of the number of acting on a sample, it is appropriate to select a certain value of the
specified entities (atoms, molecules, or formula units) pre- pressure to report their values. The standard pressure for report-
⦵
sent (unit: mole, mol). ing physical quantities is currently defined as p = 1 bar exactly.
To specify the state of a sample fully it is also necessary to give
The amount of substance, n (colloquially, ‘the number of
its temperature, T. The temperature is formally a property that
moles’), is a measure of the number of specified entities present
determines in which direction energy will flow as heat when
in the sample. ‘Amount of substance’ is the official name of the
two samples are placed in contact through thermally conduct-
quantity; it is commonly simplified to ‘chemical amount’ or
ing walls: energy flows from the sample with the higher tem-
simply ‘amount’. A mole is currently defined as the number of
perature to the sample with the lower temperature. The symbol
carbon atoms in exactly 12 g of carbon-12. (In 2011 the decision
T is used to denote the thermodynamic temperature which is
was taken to replace this definition, but the change has not yet,
an absolute scale with T = 0 as the lowest point. Temperatures
in 2018, been implemented.) The number of entities per mole is
above T = 0 are then most commonly expressed by using
called Avogadro’s constant, NA; the currently accepted value is
the Kelvin scale, in which the gradations of temperature are
6.022 × 1023 mol−1 (note that NA is a constant with units, not a
expressed in kelvins (K). The Kelvin scale is currently defined
pure number).
by setting the triple point of water (the temperature at which
The molar mass of a substance, M (units: formally kg mol−1
ice, liquid water, and water vapour are in mutual equilibrium)
but commonly g mol−1) is the mass per mole of its atoms, its
at exactly 273.16 K (as for certain other units, a decision has
molecules, or its formula units. The amount of substance of
been taken to revise this definition, but it has not yet, in 2018,
specified entities in a sample can readily be calculated from its
been implemented). The freezing point of water (the melting
mass, by noting that
point of ice) at 1 atm is then found experimentally to lie 0.01 K
m below the triple point, so the freezing point of water is 273.15 K.
n=     Amount of substance
M Suppose a sample is divided into smaller samples. If a property
of the original sample has a value that is equal to the sum of its val-
A note on good practice Be careful to distinguish atomic or
ues in all the smaller samples (as mass would), then it is said to be
molecular mass (the mass of a single atom or molecule; unit: kg)
extensive. Mass and volume are extensive properties. If a property
from molar mass (the mass per mole of atoms or molecules;
retains the same value as in the original sample for all the smaller
units: kg mol−1). Relative molecular masses of atoms and mol-
samples (as temperature would), then it is said to be intensive.
ecules, Mr = m/mu, where m is the mass of the atom or molecule
Temperature and pressure are intensive properties. Mass density,
and mu is the atomic mass constant (see inside front cover),
ρ = m/V, is also intensive because it would have the same value for
are still widely called ‘atomic weights’ and ‘molecular weights’
all the smaller samples and the original sample. All molar proper-
even though they are dimensionless quantities and not weights
ties, Xm = X/n, are intensive, whereas X and n are both extensive.
(‘weight’ is the gravitational force exerted on an object).

Note how the units (in this case, °C) are cancelled like num-
bers. This is the procedure called ‘quantity calculus’ in which
a physical quantity (such as the temperature) is the product
of a numerical value (25.00) and a unit (1 °C); see The chem-
ist’s toolkit 1. Multiplication of both sides by K then gives
T = 298.15 K.
A note on good practice The zero temperature on the thermody-
namic temperature scale is written T = 0, not T = 0 K. This scale
is absolute, and the lowest temperature is 0 regardless of the size
of the divisions on the scale (just as zero pressure is denoted
p = 0, regardless of the size of the units, such as bar or pascal).
However, it is appropriate to write 0 °C because the Celsius scale
is not absolute.
1A.2 Equations of state
Although in principle the state of a pure substance is specified
by giving the values of n, V, p, and T, it has been established
experimentally that it is sufficient to specify only three of these
variables since doing so fixes the value of the fourth variable.

That is, it is an experimental fact that each substance is de-
scribed by an equation of state, an equation that interrelates
these four variables.
The general form of an equation of state is
p = f(T,V,n) General form of an equation of state
This equation states that if the values of n, T, and V are known
for a particular substance, then the pressure has a fixed value.
Each substance is described by its own equation of state, but
the explicit form of the equation is known in only a few special
cases. One very important example is the equation of state of
a ‘perfect gas’, which has the form p = nRT/V, where R is a con-
stant independent of the identity of the gas.
The equation of state of a perfect gas was established by
combining a series of empirical laws.
(a) The empirical basis
The following individual gas laws should be familiar:
Boyle’s law:   pV = constant, at constant n, T
(1A.3a)
Charles’s law: V = constant × T, at constant n, p (1A.3b)
       p = constant × T, at constant n, V (1A.3c)
Avogadro’s principle:
        V = constant × n at constant p, T
Boyle’s and Charles’s laws are examples of a limiting law, a law
that is strictly true only in a certain limit, in this case p → 0.
For example, if it is found empirically that the volume of a sub-
stance fits an expression V = aT + bp + cp2, then in the limit
of p → 0, V = aT. Many relations that are strictly true only at
p = 0 are nevertheless reasonably reliable at normal pressures
(p ≈ 1 bar) and are used throughout chemistry.
Figure 1A.2 depicts the variation of the pressure of a sam-
ple of gas as the volume is changed. Each of the curves in the
Increasing
temperature, T
Pressure, p
0 0
0
Volume, V
Figure 1A.2 The pressure–volume dependence of a fixed amount
of perfect gas at different temperatures. Each curve is a hyperbola
(pV = constant) and is called an isotherm.
1A The perfect gas 7
Pressure, p
(1A.2) Increasing
temperature, T
Extrapolation
0
0
1/Volume, 1/V
Figure 1A.3 Straight lines are obtained when the pressure of a
perfect gas is plotted against 1/V at constant temperature. These
lines extrapolate to zero pressure at 1/V = 0.
graph corresponds to a single temperature and hence is called
an isotherm. According to Boyle’s law, the isotherms of gases
are hyperbolas (a curve obtained by plotting y against x with
xy = constant, or y = constant/x). An alternative depiction, a
plot of pressure against 1/volume, is shown in Fig. 1A.3. The
linear variation of volume with temperature summarized by
Charles’s law is illustrated in Fig. 1A.4. The lines in this illus-
tration are examples of isobars, or lines showing the variation
(1A.3d) of properties at constant pressure. Figure 1A.5 illustrates the
linear variation of pressure with temperature. The lines in this
diagram are isochores, or lines showing the variation of prop-
erties at constant volume.
A note on good practice To test the validity of a relation between
two quantities, it is best to plot them in such a way that they
should give a straight line, because deviations from a straight
line are much easier to detect than deviations from a curve. The
development of expressions that, when plotted, give a straight
line is a very important and common procedure in physical
chemistry.
Volume, V
Decreasing
pressure, p
Extrapolation
0
Temperature, T
Figure 1A.4 The variation of the volume of a fixed amount of a
perfect gas with the temperature at constant pressure. Note that
in each case the isobars extrapolate to zero volume at T = 0,
corresponding to θ = −273.15 °C.
8 1 The properties of gases

Surface

Pressure, p
Pressure, p

of possible
Decreasing
states
volume, V
Extrapolation

,T
re
tu
Volume, V ra
0 pe
m
0
Temperature, T Te
Figure 1A.6 A region of the p,V,T surface of a fixed amount of
Figure 1A.5 The pressure of a perfect gas also varies linearly with perfect gas. The points forming the surface represent the only
the temperature at constant volume, and extrapolates to zero at states of the gas that can exist.
T = 0 (−273.15 °C).

The empirical observations summarized by eqn 1A.3 can be

combined into a single expression:
Isotherm
pV = constant × nT Isobar

This expression is consistent with Boyle’s law (pV = constant) pV = constant

Pressure, p
when n and T are constant, with both forms of Charles’s law V∝T
Isochore
(p ∝ T, V ∝ T) when n and either V or p are held constant, and
with Avogadro’s principle (V ∝ n) when p and T are constant.
The constant of proportionality, which is found experimen-
p∝T
tally to be the same for all gases, is denoted R and called the
(molar) gas constant. The resulting expression ,T
re
tu
ra
Volume, V pe
pV = nRT Perfect gas law (1A.4) Te
m

is the perfect gas law (or perfect gas equation of state). It is the
approximate equation of state of any gas, and becomes in-
creasingly exact as the pressure of the gas approaches zero. A
gas that obeys eqn 1A.4 exactly under all conditions is called
a perfect gas (or ideal gas). A real gas, an actual gas, behaves
more like a perfect gas the lower the pressure, and is described
exactly by eqn 1A.4 in the limit of p → 0. The gas constant R
can be determined by evaluating R = pV/nT for a gas in the
limit of zero pressure (to guarantee that it is behaving per-
fectly).
A note on good practice Despite ‘ideal gas’ being the more
common term, ‘perfect gas’ is preferable. As explained in
Topic 5B, in an ‘ideal mixture’ of A and B, the AA, BB, and
AB interactions are all the same but not necessarily zero. In a
perfect gas, not only are the interactions all the same, they are
also zero.
The surface in Fig. 1A.6 is a plot of the pressure of a fixed
amount of perfect gas against its volume and thermodynamic
temperature as given by eqn 1A.4. The surface depicts the only
possible states of a perfect gas: the gas cannot exist in states
that do not correspond to points on the surface. The graphs
in Figs. 1A.2 and 1A.4 correspond to the sections through the
surface (Fig. 1A.7).
Figure 1A.7 Sections through the surface shown in Fig. 1A.6
at constant temperature give the isotherms shown in Fig. 1A.2.
Sections at constant pressure give the isobars shown in Fig. 1A.4.
Sections at constant volume give the isochores shown in Fig.
1A.5.
Example 1A.1
Using the perfect gas law
In an industrial process, nitrogen gas is introduced into
a vessel of constant volume at a pressure of 100 atm and a
temperature of 300 K. The gas is then heated to 500 K. What
pressure would the gas then exert, assuming that it behaved
as a perfect gas?
Collect your thoughts The pressure is expected to be greater
on account of the increase in temperature. The perfect gas
law in the form pV/nT = R implies that if the conditions are
changed from one set of values to another, then because pV/nT
is equal to a constant, the two sets of values are related by the
‘combined gas law’
p1V1 p2V2
= Combined gas law (1A.5)
n1T1 n2T2

This expression is easily rearranged to give the unknown
quantity (in this case p2) in terms of the known. The known
and unknown data are summarized as follows:
n p V T
Initial Same 100 atm Same 300 K
Final Same ? Same 500 K
The solution Cancellation of the volumes (because V1 = V2)
and amounts (because n1 = n2) on each side of the combined
gas law results in
p1 p2
=
T1 T2
which can be rearranged into
T2
p2 = ×p
T1 1
Substitution of the data then gives
500K
p2 = × (100 atm) = 167 atm
300K
Self-test 1A.1 What temperature would result in the same
sample exerting a pressure of 300 atm?
Answer: 900 K
The perfect gas law is of the greatest importance in physical
chemistry because it is used to derive a wide range of relations
that are used throughout thermodynamics. However, it is also
of considerable practical utility for calculating the properties
of a gas under a variety of conditions. For instance, the molar
volume, Vm = V/n, of a perfect gas under the conditions called
standard ambient temperature and pressure (SATP), which
means 298.15 K and 1 bar (i.e. exactly 105 Pa), is easily calculated
from Vm = RT/p to be 24.789 dm3 mol−1. An earlier definition,
standard temperature and pressure (STP), was 0 °C and 1 atm;
at STP, the molar volume of a perfect gas is 22.414 dm3 mol−1.
The molecular explanation of Boyle’s law is that if a sam-
ple of gas is compressed to half its volume, then twice as many
molecules strike the walls in a given period of time than be-
fore it was compressed. As a result, the average force exerted
on the walls is doubled. Hence, when the volume is halved the
pressure of the gas is doubled, and pV is a constant. Boyle’s law
applies to all gases regardless of their chemical identity (pro-
vided the pressure is low) because at low pressures the average
separation of molecules is so great that they exert no influence
on one another and hence travel independently. The molecu-
lar explanation of Charles’s law lies in the fact that raising the
temperature of a gas increases the average speed of its mol-
ecules. The molecules collide with the walls more frequently
and with greater impact. Therefore they exert a greater pres-
sure on the walls of the container. For a quantitative account
of these relations, see Topic 1B.
1A The perfect gas 9
(b) Mixtures of gases
When dealing with gaseous mixtures, it is often necessary
to know the contribution that each component makes to
the total pressure of the sample. The partial pressure, p J,
of a gas J in a mixture (any gas, not just a perfect gas), is
defined as
Partial pressure
pJ = x Jp [definition] (1A.6)
where x J is the mole fraction of the component J, the amount
of J expressed as a fraction of the total amount of molecules, n,
in the sample:
nJ Mole fraction
xJ = n = nA + nB +  (1A.7)
n [definition]
When no J molecules are present, x J = 0; when only J mole-
cules are present, x J = 1. It follows from the definition of x J that,
whatever the composition of the mixture, xA + x B + … = 1 and
therefore that the sum of the partial pressures is equal to the
total pressure:
pA + pB + … = (xA + x B + …)p = p (1A.8)
This relation is true for both real and perfect gases.
When all the gases are perfect, the partial pressure as de-
fined in eqn 1A.6 is also the pressure that each gas would exert
if it occupied the same container alone at the same tempera-
ture. The latter is the original meaning of ‘partial pressure’.
That identification was the basis of the original formulation of
Dalton’s law:
The pressure exerted by a mixture of gases is the
sum of the pressures that each one would exert
if it occupied the container alone.  Dalton’s law
This law is valid only for mixtures of perfect gases, so it is not
used to define partial pressure. Partial pressure is defined by
eqn 1A.6, which is valid for all gases.
Example 1A.2 Calculating partial pressures
The mass percentage composition of dry air at sea level is
approximately N2: 75.5; O2: 23.2; Ar: 1.3. What is the par-
tial pressure of each component when the total pressure is
1.20 atm?
Collect your thoughts Partial pressures are defined by eqn
1A.6. To use the equation, first calculate the mole fractions
of the components, by using eqn 1A.7 and the fact that the
amount of atoms or molecules J of molar mass MJ in a sample
of mass mJ is nJ = mJ/MJ. The mole fractions are independent of
the total mass of the sample, so choose the latter to be exactly
100 g (which makes the conversion from mass percentages
very easy). Thus, the mass of N2 present is 75.5 per cent of
100 g, which is 75.5 g.
10 1 The properties of gases

The solution The amounts of each type of atom or molecule The total is 3.45�����������������������������������������������
 ����������������������������������������������
mol. The mole fractions are obtained by divid-
present in 100 g of air are, in which the masses of N2, O2, and ing each of the above amounts by 3.45 mol and the partial
Ar are 75.5 g, 23.2 g, and 1.3 g, respectively, are pressures are then obtained by multiplying the mole fraction
by the total pressure (1.20 atm):
75.5 g 75.5
n(N 2 ) = = mol = 2.69mol N2 O2 Ar
28.02 g mol −1 28.02
Mole fraction: 0.780 0.210 0.0096
23.2 g 23.2 Partial pressure/atm: 0.936 0.252 0.012
n(O2 ) = −1 = mol = 0.725mol
32.00 g mol 32.00
Self-test 1A.2 When carbon dioxide is taken into account,
the mass percentages are 75.52 (N2), 23.15 (O2), 1.28 (Ar), and
1.3 g 1.3
n(Ar) = = mol = 0.033mol 0.046 (CO2). What are the partial pressures when the total
39.95 g mol −1 39.95
pressure is 0.900 atm?
Answer: 0.703, 0.189, 0.0084, and 0.00027 atm

Checklist of concepts
☐ 1. The physical state of a sample of a substance, its physi-
cal condition, is defined by its physical properties.
☐ 2. Mechanical equilibrium is the condition of equality of
pressure on either side of a shared movable wall.
☐ 3. An equation of state is an equation that interrelates the
variables that define the state of a substance.
☐ 4. Boyle’s and Charles’s laws are examples of a limiting
law, a law that is strictly true only in a certain limit, in
this case p → 0.
☐ 5. An isotherm is a line in a graph that corresponds to a
single temperature.
☐ 6. An isobar is a line in a graph that corresponds to a
single pressure.
☐ 7. An isochore is a line in a graph that corresponds to a
single volume.
☐ 8. A perfect gas is a gas that obeys the perfect gas law
under all conditions.
☐ 9. Dalton’s law states that the pressure exerted by a
mixture of (perfect) gases is the sum of the pressures
that each one would exert if it occupied the container
alone.

Checklist of equations
Property Equation Comment Equation number

Relation between temperature scales T/K = θ/°C + 273.15 273.15 is exact 1A.1
Perfect gas law pV = nRT Valid for real gases in the limit p → 0 1A.4
Partial pressure pJ = xJp Valid for all gases 1A.6
Mole fraction x J = nJ /n Definition 1A.7
n = nA + nB +
TOPIC 1B The kinetic model
➤ Why do you need to know this material?
This material illustrates an important skill in science: the
ability to extract quantitative information from a qualita-
tive model. Moreover, the model is used in the discussion
of the transport properties of gases (Topic 16A), reaction
rates in gases (Topic 18A), and catalysis (Topic 19C).
➤ What is the key idea?
A gas consists of molecules of negligible size in ceaseless
random motion and obeying the laws of classical mechan-
ics in their collisions.
➤ What do you need to know already?
You need to be aware of Newton’s second law of motion,
that the acceleration of a body is proportional to the force
acting on it, and the conservation of linear momentum
(The chemist’s toolkit 3).
The chemist’s toolkit 3 Momentum and force
The speed, v, of a body is defined as the rate of change of posi-
tion. The velocity, v, defines the direction of travel as well as
the rate of motion, and particles travelling at the same speed
but in different directions have different velocities. As shown
in Sketch 1, the velocity can be depicted as an arrow in the
direction of travel, its length being the speed v and its com-
ponents vx, vy, and vz along three perpendicular axes. These
components have a sign: vx = +5 m s −1, for instance, indicates
that a body is moving in the positive x-direction, whereas vx =
−5 m s −1 indicates that it is moving in the opposite direction.
The length of the arrow (the speed) is related to the components
by Pythagoras’ theorem: v 2 = vx2 + vy2 + vz2.
vz
v
⎝
⎨
length v
⎛
vx
vy
Sketch 1
In the kinetic theory of gases (which is sometimes called the
kinetic-molecular theory, KMT) it is assumed that the only
contribution to the energy of the gas is from the kinetic ener-
gies of the molecules. The kinetic model is one of the most re-
markable—and arguably most beautiful—models in physical
chemistry, for from a set of very slender assumptions, power-
ful quantitative conclusions can be reached.
1B.1 The model
The kinetic model is based on three assumptions:
1. The gas consists of molecules of mass m in ceaseless ran-
dom motion obeying the laws of classical mechanics.
2. The size of the molecules is negligible, in the sense that
their diameters are much smaller than the average dis-
tance travelled between collisions; they are ‘point-like’.
3. The molecules interact only through brief elastic collisions.
The concepts of classical mechanics are commonly expressed
in terms of the linear momentum, p, which is defined as
Linear momentum
p = mv 
[definition]
Momentum also mirrors velocity in having a sense of direction;
bodies of the same mass and moving at the same speed but in
different directions have different linear momenta.
Acceleration, a, is the rate of change of velocity. A body
accelerates if its speed changes. A body also accelerates if its
speed remains unchanged but its direction of motion changes.
According to Newton’s second law of motion, the acceleration
of a body of mass m is proportional to the force, F, acting on it:
F = ma Force
Because mv is the linear momentum and a is the rate of change
of velocity, ma is the rate of change of momentum. Therefore,
an alternative statement of Newton’s second law is that the force
is equal to the rate of change of momentum. Newton’s law indi-
cates that the acceleration occurs in the same direction as the
force acts. If, for an isolated system, no external force acts, then
there is no acceleration. This statement is the law of conserva-
tion of momentum: that the momentum of a body is constant
in the absence of a force acting on the body.
12 1 The properties of gases

An elastic collision is a collision in which the total transla- |vx Δt|

tional kinetic energy of the molecules is conserved.
Area, A

Will
(a) Pressure and molecular speeds Won’t

From the very economical assumptions of the kinetic model, it

is possible to derive an expression that relates the pressure and x
volume of a gas.
Volume = |vx Δt|A

How is that done? 1B.1 Using the kinetic model to derive Figure 1B.2 A molecule will reach the wall on the right within
an expression for the pressure of a gas an interval of time ∆t if it is within a distance vx∆t of the wall and
travelling to the right.
Consider the arrangement in Fig. 1B.1, and then follow these
steps.
At any instant, half the particles are moving to the right and
Step 1 Set up the calculation of the change in momentum half are moving to the left. Therefore, the average number of
When a particle of mass m that is travelling with a component collisions with the wall during the interval Δt is 12 nNA AvxΔt/V.
of velocity vx parallel to the x-axis collides with the wall on the The total momentum change in that interval is the product of
right and is reflected, its linear momentum changes from mvx this number and the change 2mvx:
before the collision to −mvx after the collision (when it is trav-
elling in the opposite direction). The x-component of momen- nN A Avx ∆ t
Momentum change = × 2mv x
tum therefore changes by 2mvx on each collision (the y- and 2V
M
z-components are unchanged). Many molecules collide with 
the wall in an interval Δt, and the total change of momentum nmN A Avx2 ∆ t nMAvx2 ∆ t
= =
is the product of the change in momentum of each molecule V V
multiplied by the number of molecules that reach the wall Step 3 Calculate the force
during the interval.
The rate of change of momentum, the change of momentum
Step 2 Calculate the change in momentum divided by the interval ∆t during which it occurs, is
Because a molecule with velocity component vx travels a
nMAvx2
distance vxΔt along the x-axis in an interval Δt, all the mol- Rate of change of momentum =
V
ecules within a distance vxΔt of the wall strike it if they are
travelling towards it (Fig. 1B.2). It follows that if the wall has According to Newton’s second law of motion this rate of
area A, then all the particles in a volume A × vxΔt reach the change of momentum is equal to the force.
wall (if they are travelling towards it). The number density of Step 4 Calculate the pressure
particles is nNA/V, where n is the total amount of molecules in
The pressure is this force (nMAvx2 /V ) divided by the area (A)
the container of volume V and NA is Avogadro’s constant. It
on which the impacts occur. The areas cancel, leaving
follows that the number of molecules in the volume AvxΔt is
(nNA/V) × AvxΔt. nM vx2
Pressure =
V
Not all the molecules travel with the same velocity, so the
mvx
Before detected pressure, p, is the average (denoted 〈…〉) of the quan-
collision
tity just calculated:

nM 〈vx2 〉
p=
V
–mvx
After The average values of vx2 , v 2y , and vz2 are all the same, and
collision 2 2
because v 2 = vx2 + v 2y + vz2 , it follows that 〈vx 〉 = 13 〈v 〉.
x At this stage it is useful to define the root-mean-square
speed, vrms, as the square root of the mean of the squares of
Figure 1B.1 The pressure of a gas arises from the impact of its the speeds, v, of the molecules. Therefore
molecules on the walls. In an elastic collision of a molecule with
a wall perpendicular to the x-axis, the x-component of velocity is Root-mean-square speed
vrms = 〈v 2 〉1/2 [definition] (1B.1)
reversed but the y- and z-components are unchanged.
 1B The kinetic model 13

The mean square speed in the expression for the pressure can The distribution factorizes into three terms as f(v) = f(vx) f(vy) f(vz)
therefore be written 〈vx2 〉 = 13 〈v 2 〉 = 13 vrms
2
to give and K = KxKyKz, with


2

2
(1B.2) f (vx ) = K x e − mvx /2 kT
 pV = nM v1
3 rms
Relation between pressure and volume
[KMT] and likewise for the other two coordinates.

This equation is one of the key results of the kinetic model. Step 2 Determine the constants K x, Ky, and Kz
If the root-mean-square speed of the molecules depends only To determine the constant K x, note that a molecule must have
on the temperature, then at constant temperature a velocity component somewhere in the range −∞ < vx < ∞, so
integration over the full range of possible values of vx must
pV = constant
give a total probability of 1:
which is the content of Boyle’s law. The task now is to show that ∞
the right-hand side of eqn 1B.2 is equal to nRT. ∫ −∞
f (vx )d vx = 1

(b)The Maxwell–Boltzmann distribution (See The chemist’s toolkit 4 for the principles of integration.)
Substitution of the expression for f(vx) then gives
of speeds
Integral G.1
In a gas the speeds of individual molecules span a wide    1/2
∞  2πkT 
1 = K x ∫ e − mvx /2 kT d vx = K x 
2
range, and the collisions in the gas ensure that their speeds −∞  m  
are ceaselessly changing. Before a collision, a molecule may
be travelling rapidly, but after a collision it may be acceler- Therefore, K x = (m/2πkT)1/2 and
ated to a higher speed, only to be slowed again by the next 1/2
 m  − mvx2 /2 kT
collision. To evaluate the root-mean-square speed it is nec- f (v x ) =  e
 2πkT 
(1B.3)
essary to know the fraction of molecules that have a given
speed at any instant. The fraction of molecules that have The expressions for f(vy) and f(vz) are analogous.
speeds in the range v to v + dv is proportional to the width Step 3 Write a preliminary expression for
of the range, and is written f(v)dv, where f(v) is called the f (vx ) f (v y ) f (vz )dvx dv y dvz
distribution of speeds. An expression for this distribution The probability that a molecule has a velocity in the range vx
can be found by recognizing that the energy of the mole- to vx + dvx, vy to vy + dvy, vz to vz + dvz, is
cules is entirely kinetic, and then using the Boltzmann dis-
tribution to describe how this energy is distributed over the − m ( v 2x +v 2y +v z2 )/2 kT
e 
 
molecules.  m 
3/2
2
− mvx2 /2 kT − mv y /2 kT − mvz2 /2 kT
f (vx ) f (v y ) f (vz )dvx dv y dvz =  e e e
 2πkT 
× dvx dv y dvz
How is that done? 1B.2 Deriving the distribution
3/2
 m  2
of speeds = e − mv /2 kT dvx dv y dvz
 2πkT 
The starting point for this derivation is the Boltzmann distri-
where v 2 = vx2 + v 2y + vz2.
bution (see the text’s Prologue).
Step 1 Write an expression for the distribution of the kinetic Step 3 Calculate the probability that a molecule has a speed in
energy the range v to v + dv
The Boltzmann distribution implies that the fraction of mole- To evaluate the probability that a molecule has a speed in the
cules with velocity components vx, vy, and vz is proportional to range v to v + dv regardless of direction, think of the three
an exponential function of their kinetic energy: f(v) = Ke−ε/kT, velocity components as defining three coordinates in ‘velocity
where K is a constant of proportionality. The kinetic energy is space’, with the same properties as ordinary space except
that the axes are labelled (vx , v y , vz ) instead of (x, y, z). Just as
ε = 12 mvx2 + 12 mv 2y + 12 mvz2 the volume element in ordinary space is dxdydz, so the volume
element in velocity space is dvx dv y dvz . The sum of all the vol-
Therefore, use the relation ax+y+z = axayaz to write ume elements in ordinary space that lie at a distance r from the
centre is the volume of a spherical shell of radius r and thickness
2 2 2 2 2 2
f (v ) = Ke − (mvx + mvy + mv z )/2 kT = Ke − mvx /2 kT e− mv y /2 kT e− mv z /2 kT  dr. That volume is the product of the surface area of the shell,
Another random document with
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pour sa besogne. On exige un haut niveau d’intelligence, et l’on ne
pardonne pas les défaillances. Par exemple : certain employé, en
congé à Londres, se trompa de train à Boulogne et, au lieu d’aller à
Paris, ce qu’il avait bien entendu eu l’intention de faire, se trouva à
une station appelée Kirk Kilissie, à l’ouest d’Andrinople, où il resta
quelques semaines. C’est une erreur qui aurait pu être commise par
n’importe qui, par une nuit sombre, après une traversée
tempêtueuse, mais les autorités n’en voulurent rien croire, et lorsque
je quittai l’Égypte elles étaient activement occupées à le passer à
tabac. Tout le monde est effroyablement comme il faut maintenant
au Soudan.
Il y a bien, bien longtemps, avant même que les Philippines
eussent été prises, un de mes amis fut réprimandé par un Député
anglais, d’abord pour le péché commis en versant du sang, parce
qu’il était par profession soldat, ensuite pour l’assassinat parce qu’il
avait combattu dans de grandes batailles, et enfin, chose la plus
importante de toutes, parce que lui et ses matamores avaient infligé
au contribuable anglais les dépenses occasionnées par le Soudan.
Mon ami expliqua que tout ce que le Soudan avait jamais coûté au
contribuable anglais était le prix d’environ une douzaine de drapeaux
anglais réglementaires — un pour chaque province. — Et c’est là, dit
triomphalement le Député, tout ce que cela vaudra jamais. Il
continua à se justifier, et le Soudan continua — aussi. Aujourd’hui il
a pris sa place en tant qu’un de ces miracles reconnus et avérés, qui
s’obtiennent, sans qu’on ait besoin d’emportement ni d’entêtes de
journaux, grâce à des hommes qui font la tâche la plus proche d’eux
et s’occupent rarement de leur propre réputation.
Tandis qu’il y a seize ans — moins même — le pays entier n’était
qu’un enfer affolant de meurtre, de torture, de prurit, où chaque
homme qui possédait une épée s’en servait jusqu’au moment où il
rencontrait un plus fort que lui et devenait esclave. C’était — ce sont
ceux qui s’en souviennent qui le disent, — une hystérie de sang et
de fanatisme, et de même qu’une femme hystérique est rappelée à
ses sens par un jet d’eau froide, de même à la bataille d’Omdurman
le pays fut ramené à la santé mentale par la mort appliquée sur une
échelle telle, que les meurtriers et les bourreaux auraient eu du mal,
même à l’extrême limite de leur débordement, à concevoir. En un
jour et une nuit tous ceux qui avaient du pouvoir et de l’autorité
furent exterminés et soumis si bien que, comme le dit la vieille
chanson, il ne resta plus de chef pour demander des nouvelles
d’aucun suivant. Tous ils avaient fait une dernière charge qui les
mena au Paradis. Ceux qui restaient s’attendaient à voir se
renouveler des massacres pareils à ceux auxquels ils avaient été
accoutumés, et lorsque ceux-ci ne vinrent point, ils dirent sans
recours : — Nous n’avons rien, nous ne sommes rien, voulez-vous
nous vendre comme esclaves chez les Égyptiens ? Ceux qui se
souviennent des anciens jours de la Reconstruction — véritable
épopée — disent qu’il ne restait plus rien sur quoi bâtir, même pas
d’épaves. Le savoir, la décence, les relations de famille, la propriété,
les titres, le sentiment de la possession : tout était parti. On leur
intima l’ordre de rester tranquilles et d’obéir ; et ils restèrent ébahis,
tâtonnant comme les foules ahuries après une explosion. Peu à peu
cependant ils furent nourris et soignés et disciplinés quelque peu ;
des tâches, dont ils n’espéraient jamais voir la fin leur furent
imposées, et ils furent presque par force physique poussés et
traînés le long des routes de l’existence même. Ils en vinrent à
comprendre bientôt qu’ils pourraient récolter ce qu’ils avaient semé
et qu’un homme, mieux, une femme, pourrait faire une marche d’une
journée avec deux chèvres et un lit indigène, et garder la vie et ses
biens saufs. Mais il fallait le leur enseigner comme on le ferait au
jardin d’enfants.
Et insensiblement, à mesure qu’ils se rendaient compte que
l’ordre nouveau était sûr, et que leurs anciens oppresseurs étaient
bien morts, on vit revenir non seulement des cultivateurs, des
artisans, des techniciens, mais des soldats d’aspect bizarre, portant
les cicatrices de vieilles blessures, et les généreuses fossettes que
la balle Martini-Henry avait coutume d’infliger — hommes de combat
à la recherche d’un nouvel emploi. Ils lambinaient par-ci par-là,
tantôt sur une jambe, tantôt sur l’autre, fiers ou amicaux avec
inquiétude, jusqu’à ce que quelque officier blanc vînt à passer tout
près. Lorsqu’il eut passé quatre ou cinq fois, l’homme brun et
l’homme blanc s’étant appréciés par le regard, la conversation, ainsi
qu’il paraît, s’engageait à peu près ainsi :
Officier (avec l’air de quelqu’un qui fait soudain une découverte). Dites
donc, vous là-bas, près de la hutte, qu’est-ce que vous voulez ?
Guerrier (prenant la position fixe, qui est compromise par un effort fait
pour saluer). Je suis un tel, de tel endroit.
Officier. J’entends, et alors ?
Guerrier (répétant le salut)… Et un soldat aussi.
Officier (parlant à l’horizon, sans s’adresser à personne en particulier).
Mais tous disent cela aujourd’hui.
Guerrier (tout à fait à haute voix). Mais il y a un homme dans un de
vos bataillons qui peut en fournir la preuve. C’est le petit-fils de
l’oncle de mon père.
Officier (confidentiellement, à ses souliers). L’Enfer est tout à fait
rempli de pareils petits-fils, de pareils oncles ; et comment puis-je
savoir si le soldat un tel dit la vérité au sujet de sa famille ? (fait mine
de partir).
Guerrier (enlevant rapidement les vêtements nécessaires). Peut-être.
Mais voici ce qui ne ment pas. Regardez ! J’ai reçu ceci, il y a dix,
douze ans, quand je n’étais que gamin, près de l’ancienne frontière.
Oui, Halfa. C’était une véritable balle Snider. Sentez-la ! Cette petite
blessure à la jambe je l’ai reçue dans la grande bataille qui mit fin à
tout l’année dernière. Mais je ne suis pas boiteux (Violents exercices des
jambes), pas le moins du monde boiteux. Voyez, je cours, je saute, je
donne des coups de pied, loué soit Allah !
Officier. Loué soit Allah. Et puis après ?
Guerrier (avec coquetterie). Et puis, je tire du fusil. Je ne suis pas
un lancier ordinaire. (Parlant finalement anglais.) Oui, sacré bonn ti’eur.
(Fait marcher la gâchette d’un Martini imaginaire).
Officier (sans broncher). Et puis ?
 Guerrier (avec indignation). Je suis venu ici, moi, après plusieurs
jours de marche, (changeant, et adoptant un ton de cajolerie d’enfant) est-ce
que tous les régiments sont pleins ?
A ce moment le parent, en uniforme, se découvrait
généralement, et si ses allures plaisaient à l’officier, encore un autre
« vieux soldat du Mahdi » venait s’ajouter à la machine qui se
fabriquait tout en roulant. Dans ces temps-là on traitait les affaires à
la lumière pure de la raison et avec une certaine audace élevée et
sainte.
On raconte une histoire de deux Sheiks, arrivée peu après le
commencement de la Reconstruction. L’un d’eux, Abdullah de la
Rivière, prudent et fils d’une esclave, fit profession de loyauté envers
les Anglais de très bonne heure, et se servait de cette loyauté
comme manteau pour voler des chameaux à un autre Sheik, Farid
du Désert, encore en guerre avec les Anglais, mais un parfait
gentilhomme, ce que n’était pas Abdullah. Naturellement, Farid fit à
son tour des raids sur les bêtes d’Abdullah ; Abdullah se plaignit aux
autorités, et toute la Frontière était en fermentation. A Farid dans
son camp de désert, accompagné d’un certain nombre de bêtes
appartenant à Abdullah vint, seul et sans armes, l’officier
responsable de la paix de ces régions. Après les compliments
échangés, car ils avaient eu des rapports ensemble auparavant : —
Vous vous êtes encore livré à des vols de bêtes dans le troupeau
d’Abdullah, dit l’officier anglais.
— Je vous crois ! fut la chaude réponse. Il vole mes bêtes et se
réfugie vivement sur votre territoire, où il sait que je ne puis
absolument pas le suivre, et quand j’essaie de rentrer tant soit peu
en possession de mon bien, il vient pleurer auprès de vous. C’est un
saligaud, un pur saligaud.
— Dans tous les cas il est loyal. Si seulement vous vouliez
consentir à vous soumettre et à être loyal aussi, vous seriez tous les
deux sur le même pied, et alors s’il vous volait quelque chose il en
verrait de dures !
 — Il n’oserait jamais voler sauf sous votre protection. Donnez-lui
ce qu’il aurait reçu au temps du Mahdi, une bonne raclée. Vous
savez qu’il le mérite, vous !
— Ce n’est guère permis, vous savez, cela. Il va falloir que vous
me laissiez ramener toutes ces bêtes qui lui appartiennent.
— Et si je refuse ?
— Alors il me faudra rentrer à cheval et ramasser tous mes
hommes pour vous faire la guerre.
— Mais qu’est-ce qui m’empêche de vous couper la gorge
pendant que vous êtes assis là ?
— D’abord le fait que vous n’êtes pas Abdullah, et…
— Voyez ! vous reconnaissez que c’est une crapule !
— Ensuite, le Gouvernement enverrait tout simplement un autre
officier ne comprenant pas vos façons d’agir, et alors ce serait la
guerre, pour de bon, et personne n’y gagnerait rien qu’Abdullah. Il
volerait vos chameaux et en aurait tout le crédit.
— C’est vrai, le coquin ! Que la vie est pénible pour un honnête
homme ! Or, vous admettez qu’Abdullah est un saligaud, alors
écoutez-moi et je vous dirai encore autre chose sur son compte. Il
était, etc. etc. il est etc. etc.
— Vous avez parfaitement raison, Sheik, mais ne voyez-vous pas
que je ne puis lui dire ce que je pense de lui, tant qu’il est loyal et
que vous, vous restez notre ennemi ? Eh bien, si vous, vous vous
soumettez, je vous promets que j’en dirai des miennes à Abdullah,
oui, en votre présence, et votre cœur s’en réjouira.
— Non ! Je ne veux point me soumettre ! Mais je vais vous dire
ce que je veux faire. Je vous accompagnerai demain comme votre
hôte, comprenez bien, à votre tente. Alors, envoyez chercher
Abdullah, et si j’estime que sa grosse figure a été suffisamment
noircie en ma présence, je verrai si je ne puis pas faire ma
soumission plus tard.
Ainsi fut convenu, et ils dormirent le reste de la nuit, côte à côte,
et dans la matinée ils rassemblèrent et rendirent toutes les bêtes
d’Abdullah. Le soir même, en présence de Farid, Abdullah reçut la
semonce la plus cinglante qu’il eût jamais entendue dans toute sa
vieille existence scélérate, et Farid du Désert rit et fit sa soumission
et — comme dans les contes — ils vécurent tous heureux dans la
suite.
Quelque part, dans les provinces plus proches, le vieux jeu
désordonné et violent doit persister encore, mais le vrai Soudan a
fini par adopter la civilisation du genre qui comporte le bungalow en
brique, et du genre Bougainville, et il existe une énorme école où les
jeunes gens sont dressés pour devenir ajusteurs, inspecteurs,
dessinateurs, et employés de télégraphe avec des appointements
fabuleux. En temps voulu ils oublieront combien il fallait de
précautions jadis à leurs aïeux, au temps du Mahdi, pour s’assurer
même une demi-ration pour leur ventre, alors, tout comme cela s’est
produit ailleurs.
Ils croiront honnêtement que ce sont eux qui ont originairement
créé, et qui ont maintenu depuis, la vie si facile où ils ont été placés
à un prix d’achat si élevé. Alors on les verra demander : « Une
extension du gouvernement local, le Soudan pour les Soudanais, »
et ainsi de suite, si bien qu’il faudra parcourir de nouveau le cycle
entier. C’est une dure loi, mais une vieille loi — Rome elle-même
mourut d’avoir eu à l’apprendre, de même que notre civilisation
occidentale pourra en mourir — que si vous donnez à qui que ce soit
quelque chose qu’il n’a pas péniblement gagné pour lui-même,
infailliblement vous faites de lui ou de ses descendants vos ennemis
avérés.
TABLE DES MATIÈRES

D’UN LIT DE MARÉE A L’AUTRE (1892).

En vue de Monadnock 9
A travers un Continent 24
La lisière de l’Orient 44
Nos hommes d’outre-mer 60
Tremblements de terre 74
Une demi-douzaine de tableaux 87
« Les Capitaines courageux » 98
Rien que d’un côté 111
Lettres d’un carnet d’hiver 125

LETTRES A LA FAMILLE (1908).

La route de Québec 147
Un peuple chez lui 160
Cités et Espaces 172
Journaux et Démocratie 186
Le Travail 200
Les villes fortunées 213
Des Montagnes et le Pacifique 228
 Une Conclusion 243

L’ÉGYPTE DES MAGICIENS (1913).

Voyage sur mer 257
Un Retour à l’Orient 270
Un Serpent du Vieux Nil 282
En remontant le fleuve 294
Potentats morts 308
La face du Désert 321
L’énigme d’Empire 332

ABBEVILLE. — IMPRIMERIE F. PAILLART.

 PAYOT & Cie, 106, Boulevard Saint-Germain, PARIS-VIe

RUDYARD KIPLING
LA GUERRE SUR MER
Préface de M. Étienne LAMY
Un vol. in-16 6 fr.
Rudyard Kipling a mené tour à tour sur des chalutiers, des destroyers et des
sous-marins, chacune des existences qui sont celles des hommes de la mer. De
là, des récits qui donnent une puissante impression de vie, de vérité et d’art où,
par cela même qu’il a subordonné la force de la matière à la force de l’esprit, les
actions humaines à un ordre surhumain, réside une beauté qui ne se trouve égale
en aucun autre livre de Kipling.
(La Revue des Deux Mondes).

Du Même
LES YEUX DE L’ASIE
Traduit de l’anglais par FIRMIN ROZ
Un vol. petit in-16 br. de la COLLECTION PETITE
ANTHOLOGIE 3 fr.
Relié satinette 7 fr.
… Quatre lettres supposées de soldats des Indes à leurs compatriotes. Beaux
sujets pour l’auteur de Kim ; tout y est, les hommes qu’il a tant observés, dont il
connaît si bien la langue, les usages, les passions, et la guerre qui éprouve les
caractères et confronte les civilisations. Venus du berceau du monde, les Hindous
portent sur l’occident de l’Europe, sur l’Angleterre, sur la France, le regard d’une
cordiale curiosité. Ils ne cessent de peser ce qu’ils voient et ce qu’ils savent, et ils
se répandent en propos d’une pompe touchante. C’est, mais plus grave et sur de
plus grands objets, le jeu de notre Montesquieu dans ses « Lettres persanes ».
(L’Action Française).
 H.-G. WELLS
M. BRITLING COMMENCE A VOIR
CLAIR
Un vol. in-16 6 fr.
Jamais le merveilleux talent du célèbre écrivain anglais ne s’est mieux affirmé
que dans ce roman qui a fait sensation tant en Angleterre qu’en Amérique, et qui
demeurera sans doute son chef-d’œuvre.
(La Revue Hebdomadaire).

Du Même

DIEU, L’INVISIBLE ROI

Traduction et Préface de M. BUTTS
Un vol. in-16 6 fr.
Dieu, l’invisible roi, nous offre la substance métaphysique de Wells ; nous y
suivons l’évolution de sa pensée. Il y expose avec force sa conception, de la
vérité, ses croyances qui reposent sur une foi ferme en un Dieu personnel avec
lequel il peut entrer en communion.
(La Revue des Deux Mondes).

Du Même

LA FLAMME IMMORTELLE
Traduction de M. BUTTS
Un vol. in-16 6 fr.
C’est à tous les éducateurs que l’auteur anglais dédie son volume
philosophique où il expose que l’humanité serait plus heureuse si on l’instruisait
mieux. Ce n’est pas dans une vie future qu’il faut escompter le bonheur. C’est de
lui-même, de sa flamme immortelle, que l’homme qui conçoit ce que pourrait être
le bonheur humain doit le tirer par un effort commun. Et c’est en façonnant
l’homme dans l’amour de ses semblables que les éducateurs pourront obtenir
cette belle œuvre.
(La France de l’Ouest).
 GRAND PRIX NOBEL DE LITTÉRATURE
CARL SPITTELER
MES PREMIERS SOUVENIRS
Un vol. in-16 6 fr.
Mes premiers souvenirs remontent à la première année de la vie de l’auteur
et s’arrêtent lorsqu’il est à peine âgé de quatre ans. On lira avec curiosité le récit
de ces émotions enfantines qui n’a rien d’une biographie. Ni le Roman d’un
enfant de Loti, ni les Souvenirs d’Enfance et de Jeunesse de Renan, ne peuvent
lui être comparés. C’est quelque chose de très neuf et de très original dans sa
conception.
(Le Mercure de France).

SOUMÉ TCHENG
SOUVENIRS D’ENFANCE ET DE
RÉVOLUTION
Édition française par B. VAN VORST
Un vol. in-16, avec 2 hors-texte 7 fr. 50
Soumé Tcheng est une incarnation charmante de l’âme moderne de la Chine.
L’intérêt particulier de ses souvenirs réside dans sa personnalité. Il est rare, en
effet, de rencontrer chez une femme d’une intelligence très haute, une énergie si
virile et un cœur si profondément humain.
(La Revue Mondiale).

JOHN GALSWORTHY
UN SAINT
Roman traduit de l’anglais par L.-P. ALAUX
Un vol. in-16 9 fr.
Ce livre a des parties admirables, des scènes d’une vérité psychologique dont
je ne crains pas de dire qu’elle n’a jamais été dépassée, ni peut-être même
atteinte, dans le roman anglais… Aucun des romanciers actuels n’a la hardiesse,
la vigueur à la fois cruelle et pitoyable de Galsworthy
la vigueur à la fois cruelle et pitoyable de Galsworthy.
André Bellessort.

Collection “Petite Anthologie”

Derniers volumes parus :

LES UPANISHADS
Morceaux choisis par P. SALET
Un vol. petit in-16 broché 4 fr.
Relié satinette 7 fr.
« Il n’y a pas d’étude aussi propre à élever l’esprit que celle des Upanishads.
Elle a été le réconfort de ma vie ; elle sera la consolation de ma mort. »
Schopenhauer.

LE LIVRE D’AMITIÉ
ANTHOLOGIE DE PENSÉES SUR L’AMITIÉ
RECUEILLIES ET PRÉCÉDÉES D’UN AVANT-PROPOS
PAR
MICHEL SERLANDES
Un vol. petit in-16 broché 3 fr.
Le Livre d’amitié unit à la variété d’une anthologie tous les avantages d’un
traité suivi, qui étudie ce sentiment délicat qu’est l’amitié dans ses variations les
plus fines, le pénètre dans ses recoins les plus cachés. Il sera pour tout ami un
conseiller sûr, un guide inséparable qui lui permettra de lire dans son cœur.

WOODROW WILSON
ÊTRE HUMAIN
SUIVI DE
QUAND UN HOMME SE TROUVE LUI-MÊME
Traduit par P. CHAVANNES
Un vol. petit in-16 broché 3 fr.
Un précieux guide de la vie moderne.
Un précieux guide de la vie moderne.
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