PDF Microstates Entropy and Quanta An Introduction To Statistical Mechanics Don Koks Ebook Full Chapter

Microstates Entropy and Quanta An
Introduction to Statistical Mechanics

Don Koks
Visit to download the full and correct content document:
https://textbookfull.com/product/microstates-entropy-and-quanta-an-introduction-to-st
atistical-mechanics-don-koks/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...
Statistical mechanics : entropy, order parameters, and

complexity 2nd Edition Sethna
https://textbookfull.com/product/statistical-mechanics-entropy-
order-parameters-and-complexity-2nd-edition-sethna/
An Introduction to Statistical Mechanics and

Thermodynamics 2nd Edition Robert H. Swendsen
https://textbookfull.com/product/an-introduction-to-statistical-
mechanics-and-thermodynamics-2nd-edition-robert-h-swendsen/
Statistical Methods An Introduction to Basic

Statistical Concepts and Analysis 2nd Edition Cheryl
Ann Willard
https://textbookfull.com/product/statistical-methods-an-
introduction-to-basic-statistical-concepts-and-analysis-2nd-
edition-cheryl-ann-willard/
An Introduction To Statistical Learning With

Applications In R Gareth James
learning-with-applications-in-r-gareth-james/
Statistical Field Theory - An Introduction to Exactly
Solved Models in Statistical Physics 2nd Edition
Giuseppe Mussardo
https://textbookfull.com/product/statistical-field-theory-an-
introduction-to-exactly-solved-models-in-statistical-physics-2nd-
edition-giuseppe-mussardo/
An Introduction to Statistical Methods and Data

Analysis 7th Edition R. Lyman Ott
methods-and-data-analysis-7th-edition-r-lyman-ott/
Introduction to basic statistics 1 Don Ozisco
https://textbookfull.com/product/introduction-to-basic-
statistics-1-don-ozisco/
Non equilibrium statistical mechanics Prigogine
https://textbookfull.com/product/non-equilibrium-statistical-
mechanics-prigogine/
Introduction to Statistical Methods Design of

Experiments and Statistical Quality Control Dharmaraja
Selvamuthu
https://textbookfull.com/product/introduction-to-statistical-
methods-design-of-experiments-and-statistical-quality-control-
dharmaraja-selvamuthu/
Don Koks
Microstates,
Entropy and Quanta
An Introduction to Statistical Mechanics
Microstates, Entropy and Quanta
Don Koks
Microstates, Entropy
and Quanta
An Introduction to Statistical Mechanics
123
ISBN 978-3-030-02428-4 ISBN 978-3-030-02429-1 (eBook)
https://doi.org/10.1007/978-3-030-02429-1
Library of Congress Control Number: 2018960736
© Springer Nature Switzerland AG 2018

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt from
the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authors or the editors give a warranty, express or implied, with respect to the material contained herein or
for any errors or omissions that may have been made. The publisher remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
Cover art: Central to statistical mechanics is the idea of counting the states accessible to a system. When
these states exist within some continuous space, they cannot be counted. Instead, we “tile” the space into
cells, with each cell defining a state, and then we count those cells. The ball on the front cover is a
schematic of this tiling of the velocity space of a free particle that moves in three spatial dimensions. For
real particles, the cells are so much smaller than the size of the ball that, to all intents and purposes, the
ball is a smooth sphere. The number of cells can then easily be found from the sphere’s volume.
This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
For my ancestors, and all those
who have gone before.
Preface
Another book on introductory statistical mechanics? You might think that

a century-old subject would have nothing left unsaid; but that is perhaps
not the case. Unlike most other fields of physics, one can compare a dozen
books on statistical mechanics and find a dozen different approaches to the
discipline. At one extreme are authors who revel in arcane abstraction, but
whose books go mostly unread. At the other extreme are very readable books
that lack the mathematics to carry the reader very far beyond a set of physical
assumptions. Most readers are looking for something in between; but that
space is vast and subjective, with plenty of room for another book to aim
for the “Goldilocks Zone” of being just right. That’s why I wrote this book:
I think that the field of introductory statistical mechanics still has plenty of
scope for an author to try a different mix of mathematical exposition and
physical reasoning.
The physics part of this mix is a build of statistical mechanics from the
ground up, anchored to a bedrock of physical concepts. With this approach, I
hope to have revealed the necessity and importance of the subject’s core ideas,
such as entropy and temperature. The mathematics part of the mix has been
an emphasis on a strong logical reasoning that has a clean outline, yet avoids
the notational clutter and obscure discussions that are so often associated
with statistical mechanics, and which can make it so hard to learn.
Thus, beside the calculations of representative physical quantities, you
will find here various mathematical analyses that I believe are important to
physicists. Much of this mathematical foundation is given in the first chapter,
such as details of integrating the gaussian function, and the correct use of
infinitesimals, partial derivatives, and units of measurement. By the time
you reach that chapter’s end, you might be wondering whether you are really
reading a book on statistical mechanics after all. And yet, you will encounter
those topics time and again as you work through the rest of the book.
The choice of how and where to begin describing a subject is always highly
author dependent. The concepts that I introduce methodically, as needed,
vii
viii Preface
are sometimes merely postulated with a breezy stroke of the pen in books
that announce themselves as introductions. Postulatory approaches to other
subjects can certainly work well; for instance, I admire Feynman’s approach
to electromagnetism in his Lectures on Physics, since, although he postulates
Maxwell’s equations at the very start, we never lose sight of the physics
in his discussions. In contrast, I struggle to see any physics at all in some
postulatory approaches to statistical mechanics, which can so easily ignore
the difficult questions that interest physicists.
I commence the subject of statistical mechanics with an archetypal obser-
vation: why does a drop of ink placed in a bathtub disperse? Once dispersed,
might it ever re-assemble into a drop? This question showcases the impor-
tance of counting the number of ways in which a system’s constituents can
be arranged, and leads to statistical mechanics proper via its fundamental
postulate. That discussion demands knowledge of the concept of energy, a
concept that was useful and intriguing to early astronomers studying plane-
tary orbits, but whose wider application was not well understood in the early
days of thermodynamics, 150 years ago. With a more modern understanding
of energy (or perhaps “acceptance” is a better word, since we still don’t know
what it is—if, indeed, asking what it is has any meaning), we are in a good
position to write down the laws of thermodynamics. Then, we can explore
heat engines, chemical processes and equilibria, and heat flow. The flow of
heat is a stepping stone to appreciating diverse related areas, such as parti-
cle diffusion and, in fact, the signal processing performed in a modern radar
receiver.
But no system is ever truly isolated; and the question of how to analyse
a system in contact with the wider world brings us to the Boltzmann dis-
tribution, with examples in paramagnetism, atomic energy levels, molecular
and crystal heat capacities, and data-transmission theory. The Boltzmann
distribution also sheds light on the motion of gas particles. I use that theory
to explore an atmosphere, as well as the molecular details of viscosity and
thermal conductivity.
Quantum ideas then emerge, via Einstein’s and Debye’s theories of heat
capacity. The notion of fermions and bosons forms a springboard to the study
of electronic heat capacity, electrical conduction, thermal noise in electric
circuits, the spectra of light produced by hot bodies, some cosmology, the
greenhouse effect, and the modern technologies of light-emitting diodes and
the laser.
I have sprinkled the text with occasional short digressions, discussing top-
ics such as the factorial function in number theory, the energy–momentum
tensor in relativity, a little bit of signal processing, and decrying the short-
comings of modern analytical astronomy. Hopefully, these asides will only
enrich your interest without being a distraction.
Unlike some books on statistical mechanics, I have chosen to discuss a lot
of material before introducing the Boltzmann distribution. Thus, in those pre-
Boltzmann chapters, I invoke the equipartition theorem to approximate the
Preface ix
particles in an ideal gas of temperature T as each having, say, translational

energy 3/2 kT . Later, when studying the Boltzmann distribution, we learn that
only their average translational energy is 3/2 kT . Some authors will avoid this
initial simplification by introducing the Boltzmann distribution very early
on. But I think that using the simple approximation initially, and leaving
Boltzmann for later, is useful pedagogically.
A subject as old as statistical mechanics is bound to carry baggage picked
up along the way, created as a normal part of its development, when physicists
and chemists were searching for the best path through the new forest they had
discovered. The choice of what might best be discarded is a little subjective.
I have tended to minimise the use of phrases and topics that appear to be
generally confusing, unattractive, or not useful.
For example, I cannot imagine that the conventional vernacular that de-
scribes various flavours of ensemble, along with free energies, partition func-
tions, and Maxwell relations, does anything to attract new adherents to sta-
tistical mechanics. Pseudo wisdom that you can find in books on the subject,
such as “The trick to solving this problem is to use the grand canonical en-
semble”, is apt to give the impression that statistical mechanics is all about
finding the right trick using the right ensemble to get the right answer. The
language of ensembles is not especially deep, and after explaining what it
means and how it’s used, I tend to avoid it, because the “correct ensemble to
use” should be clear from the context being studied; it is not some arbitrary
choice that we make. Free energies have a range of uses in thermodynamics
(and I certainly use them in this book), but they are probably more relevant
to the history of the subject, when early physicists and chemists worked hard
to ascertain the nature of what was then a cutting-edge new quantity called
energy. Nowadays, we view free energies as useful combinations of more fun-
damental parameters such as energy, temperature, and entropy. I think that
the use of partition functions can be minimised in a book on introductory sta-
tistical mechanics: they are sufficient but not necessary to the field; and yet,
all too often, books seem to suggest that the partition function is the answer
to every problem. Lastly, Maxwell relations are a useful but straightforward
application of basic partial derivatives to thermodynamics, and that they
have a name at all is probably just historical. More generally, long parades
of partial derivatives and an endless swapping and tabulation of independent
variables appear in so many books on statistical mechanics. These relics of
history are best left to museums. No one really uses them!
One deliberate nuance in some of my numerical calculations should be ex-
plained: I tend not to choose nicely rounded versions of some parameters that
turn up again and again. For example, I use 298 kelvins for room tempera-
ture and 9.8 m/s2 for Earth’s gravity, instead of the simpler-looking rounded
values of 300 kelvins and 10 m/s2 . The reason here is that, when you see
“298” and “9.8” in a calculation, you will perhaps find it easier to digest the
various parameters quickly through recognising those quirky numbers at a
glance, as opposed to seeing the more generic-looking numbers 300 and 10.
x Preface
Also, whenever I have a quantity written in both non-bold and bold font in
one context—such as “a” and “a”—then a should be understood to be the
length of the vector a.
This book has benefitted from the contributions of my family, friends, and
colleagues—although, of course, I claim full ownership of my often-strong
opinions about physics in general. My undergraduate lecturers at Auckland
University, Graeme Putt and Paul Barker, provided my first instruction in
thermodynamics and statistical mechanics in the mid-1980s, and so laid out
the backbone for a later set of lectures of my own, which became this book.
All manner of details were donated by others. Brad Alexander gave me a
computer scientist’s view of entropy. Colin Andrew discussed scuba diving
and ocean pressure. Shayne Bennetts listened to my views on the principle
of detailed balance. Encouragement and some discussion of grammar came
from Ine Brummans. The modern puzzle that is liquid helium was spelled
out for me by Peter Mc Clintock. I discussed some ideas of presentation with
Steven Cohen. Occasional technical discussions took place with Scott Foster.
Roland Keir contributed his knowledge of physical chemistry. Harry Koks
informed me of some evolved wording in combinatorics, and Rudolf Koks
explained osmosis in humans. Mark Krieg improved my grammar. Hans Laue
discussed atmospheric temperature. Nadine Pesor helped me settle on the
use of some jargon. Robert Purvinskis was a sounding board on occasion.
Andy Rawlinson gave feedback on many ideas. Keith Stowe helped untangle
some knotty problems in the subject. Vivienne Wheaton prompted some early
deliberation on the Boltzmann distribution. The feedback of two anonymous
early referees certainly helped make a better final product. Springer’s proof
reader, Marc Beschler, gave a final and detailed burnish to my words. And the
entire text was much improved by the careful reading and many thoughtful
suggestions of Alice von Trojan.
Beyond that, I thank Springer’s Tom Spicer for having the confidence to
allow the project to go ahead, and Cindy Zitter for the details of making it
happen.
Adelaide, Australia Don Koks

August 2018
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
1 Preliminary Ideas of Counting, and Some Useful

Mathematics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 The Spreading of an Ink Drop . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.1 Identical-Classical Particles . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2 Wandering Gas Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 Fluctuations in the Binomial Distribution . . . . . . . . . . . . . . . . . 17
1.3.1 Expected Value and Standard Deviation of a Random
Variable . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.3.2 The Random Walk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.4 Gaussian Approximation of the Binomial Distribution . . . . . . . 25
1.5 Integrals of the Gaussian Function . . . . . . . . . . . . . . . . . . . . . . . . 30
1.5.1 Calculating the Error Function Numerically . . . . . . . . . 36
1.5.2 The 3-Dimensional Gaussian . . . . . . . . . . . . . . . . . . . . . . . 37
1.6 Increases and Infinitesimals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
1.6.1 Basis Vectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
1.6.2 The Probability Density . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
1.7 Exercising Care with Partial Derivatives . . . . . . . . . . . . . . . . . . . 53
1.8 Exact and Inexact Differentials . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
1.9 Numerical Notation, Units, and Dimensions . . . . . . . . . . . . . . . . 64
1.9.1 Units versus Dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . 67
1.9.2 Function Arguments Must Be Dimensionless . . . . . . . . . 75
1.9.3 Distinguishing Between an Entity and its Representation 80
2 Accessible States and the Fundamental Postulate of

Statistical Mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.1 States and Microstates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
xi
xii Contents
2.2 Energy Spacing of States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

2.3 Position–Momentum and Phase Space . . . . . . . . . . . . . . . . . . . . 91
2.4 Microstates Are Cells of Phase Space . . . . . . . . . . . . . . . . . . . . . 95
2.4.1 A System’s Quadratic Energy Terms . . . . . . . . . . . . . . . . 112
2.4.2 When Particles are Identical Classical . . . . . . . . . . . . . . . 114
2.5 The Density of States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
2.6 Ωtot for Massless Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
3 The Laws of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

3.1 The Concept of Energy for a Central Force . . . . . . . . . . . . . . . . 125
3.2 Force and Potential Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
3.3 Interaction Types and the Zeroth Law of Thermodynamics . . 136
3.4 The First Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . 138
3.4.1 Expressions for Quasi-Static Mechanical Work . . . . . . . 140
3.4.2 The dC Term and Chemical Potential . . . . . . . . . . . . . . 146
3.5 The Definition of Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.5.1 Accessible Microstates for Thermally Interacting
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
3.5.2 Temperature and the Equipartition Theorem . . . . . . . . 152
3.6 The Ideal Gas and Temperature Measurement . . . . . . . . . . . . . 154
3.6.1 Measuring Temperature: the Constant-Volume Gas
Thermometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
3.6.2 Temperature of Our Upper Atmosphere . . . . . . . . . . . . . 161
3.7 The Non-Ideal Gas and van der Waals’ Equation . . . . . . . . . . . 162
3.8 Entropy and the Second Law of Thermodynamics . . . . . . . . . . 167
3.8.1 Entropy of an Ideal Gas of Point Particles . . . . . . . . . . . 170
3.8.2 The Canonical Example of Entropy Growth . . . . . . . . . 171
3.8.3 Reversible and Cyclic Processes . . . . . . . . . . . . . . . . . . . . 174
3.8.4 The Use of Planck’s Constant for Quantifying Entropy 176
3.9 Can Temperature Be Negative? . . . . . . . . . . . . . . . . . . . . . . . . . . 177
3.10 Intensive and Extensive Variables, and the First Law . . . . . . . 181
3.11 A Non-Quasi-static Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
3.12 The Ideal-Gas Law from Entropy . . . . . . . . . . . . . . . . . . . . . . . . . 185
3.13 Relation of Entropy Increase to Interaction Direction . . . . . . . 187
3.14 Integrating the Total Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
3.14.1 Swapping the Roles of Conjugate Variables . . . . . . . . . . 193
3.14.2 Maxwell Relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
3.15 Excursus: Pressure and Temperature of a Star’s Interior . . . . . 200
Contents xiii
4 The First Law in Detail . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207

4.1 The First Term: Thermal Interaction . . . . . . . . . . . . . . . . . . . . . 207
4.1.1 The Third Law of Thermodynamics . . . . . . . . . . . . . . . . 216
4.1.2 Heat Flow and the Thermal Current Density . . . . . . . . 220
4.1.3 The Continuity Equation . . . . . . . . . . . . . . . . . . . . . . . . . . 224
4.1.4 The Heat Equation, or Diffusion Equation . . . . . . . . . . . 226
4.2 The Second Term: Mechanical Interaction . . . . . . . . . . . . . . . . . 233
4.2.1 Heat Engines and Reversibility . . . . . . . . . . . . . . . . . . . . . 233
4.2.2 The Joule–Thomson Process . . . . . . . . . . . . . . . . . . . . . . . 238
4.3 The Third Term: Diffusive Interaction . . . . . . . . . . . . . . . . . . . . . 247
4.3.1 Pressure and Density of the Atmosphere . . . . . . . . . . . . 247
4.3.2 Pressure and Density of the Ocean . . . . . . . . . . . . . . . . . 251
4.3.3 Pressure and Density from the Chemical Potential . . . . 255
4.3.4 Phase Transitions and the Clausius–Clapeyron
Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
4.3.5 Chemical Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
5 The Non-Isolated System: the Boltzmann Distribution . . . 275

5.1 The Boltzmann Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
5.1.1 The Exponential Atmosphere Again . . . . . . . . . . . . . . . . 278
5.2 Paramagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
5.3 Energy Levels, States, and Bands . . . . . . . . . . . . . . . . . . . . . . . . . 283
5.4 Hydrogen Energy Levels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
5.5 Excitation Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
5.6 Diatomic Gases and Heat Capacity . . . . . . . . . . . . . . . . . . . . . . . 291
5.6.1 Quantised Rotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
5.6.2 Quantised Vibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
5.7 Another Look at the Hydrogen Atom . . . . . . . . . . . . . . . . . . . . . 300
5.8 Equipartition for a System Contacting a Thermal Bath . . . . . 303
5.8.1 Fluctuation of the System’s Energy . . . . . . . . . . . . . . . . . 306
5.9 The Partition Function in Detail . . . . . . . . . . . . . . . . . . . . . . . . . 307
5.10 Entropy of a System Contacting a Thermal Bath . . . . . . . . . . . 312
5.11 The Brandeis Dice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
5.12 Entropy and Data Transmission . . . . . . . . . . . . . . . . . . . . . . . . . . 324
6 The Motion of Gas Particles, and Transport Processes . . . . 333

6.1 The Maxwell Velocity Distribution . . . . . . . . . . . . . . . . . . . . . . . . 338
6.1.1 Alternative Derivation of the Velocity Distribution . . . 342
6.2 The Maxwell Speed Distribution . . . . . . . . . . . . . . . . . . . . . . . . . 344
6.2.1 Alternative Derivation of the Speed Distribution . . . . . 345
xiv Contents
6.3 Representative Speeds of Gas Particles . . . . . . . . . . . . . . . . . . . . 346

6.4 Doppler Broadening of a Spectral Line . . . . . . . . . . . . . . . . . . . . 350
6.5 Temperature Gradient in a Weatherless Atmosphere . . . . . . . . 353
6.6 Gaseous Makeup of Planetary Atmospheres . . . . . . . . . . . . . . . . 358
6.7 Mean Free Path of Gas Particles . . . . . . . . . . . . . . . . . . . . . . . . . 365
6.7.1 Excursus: The Proof of (6.123) . . . . . . . . . . . . . . . . . . . . . 368
6.8 Viscosity and Mean Free Path . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
6.9 Thermal Conductivity and Mean Free Path . . . . . . . . . . . . . . . . 376
6.10 Excursus: The Energy–Momentum Tensor . . . . . . . . . . . . . . . . . 379
7 Introductory Quantum Statistics . . . . . . . . . . . . . . . . . . . . . . . . . 385

7.1 Einstein’s Model of Heat Capacity . . . . . . . . . . . . . . . . . . . . . . . . 385
7.2 A Refinement of Einstein’s Model of Heat Capacity . . . . . . . . . 389
7.3 Debye’s Model of Heat Capacity . . . . . . . . . . . . . . . . . . . . . . . . . . 394
7.4 Gibbs’ Paradox and Its Resolution . . . . . . . . . . . . . . . . . . . . . . . . 403
7.5 The Extent of a System’s Quantum Nature . . . . . . . . . . . . . . . . 405
7.5.1 Average de Broglie Wavelength . . . . . . . . . . . . . . . . . . . . 407
7.6 Fermions and Bosons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
7.7 Occupation Numbers of Fermion and Boson Gases . . . . . . . . . . 418
7.7.1 Calculating µ(T ) and n(E, T ) for Fermions . . . . . . . . . . 421
7.7.2 Calculating µ(T ) and n(E, T ) for Bosons . . . . . . . . . . . . 424
7.8 Low-Temperature Bosons and Liquid Helium . . . . . . . . . . . . . . . 426
7.9 Excursus: Particle Statistics from Counting Configurations . . 432
7.9.1 Fermi–Dirac and Bose–Einstein from Configurations . . 442
8 Fermion Statistics in Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445

8.1 Conduction Electrons’ Contribution to Heat Capacity . . . . . . . 445
8.1.1 A More Accurate Approximation of n(E, T ) . . . . . . . . . 454
8.2 Electrical Conductivity of Metals . . . . . . . . . . . . . . . . . . . . . . . . . 458
8.3 Thermal Conductivity of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . 465
8.3.1 The Lorenz Number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
8.4 Insulators and Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
8.5 Diodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
9 Boson Statistics in Blackbody Radiation . . . . . . . . . . . . . . . . . . 481

9.1 Spectrum of Radiation Inside an Oven . . . . . . . . . . . . . . . . . . . . 482
9.1.1 Mean “Extractable” Energy of an Oscillator, ε(f ) . . . . . 484
9.2 The One-Dimensional Oven: an Electrical Resistor . . . . . . . . . . 488
9.2.1 Calculating the Density of Wave States, g(f ) . . . . . . . . 489
Contents xv
9.2.2 Excursus: Thermal Noise in a Resistor, and Some

Communications Theory . . . . . . . . . . . . . . . . . . . . . . . . . . 496
9.3 The Three-Dimensional Oven . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
9.4 The End Product: Planck’s Law . . . . . . . . . . . . . . . . . . . . . . . . . . 506
9.4.1 Planck’s Law Expressed Using Wavelength . . . . . . . . . . 508
9.5 Total Energy of Radiation in the Oven . . . . . . . . . . . . . . . . . . . . 510
9.6 Letting the Radiation Escape the Oven . . . . . . . . . . . . . . . . . . . 511
9.7 Blackbody Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
9.7.1 The Large-Scale Universe Is a Very Cold Oven . . . . . . . 517
9.7.2 Total Power Emitted by a Black Body . . . . . . . . . . . . . . 520
9.8 The Greenhouse Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
9.9 Photon Absorption and Emission: the Laser . . . . . . . . . . . . . . . 525
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
List of Common Symbols
Chapter 1: Preliminary Ideas of Counting, and Some Useful Mathe-

matics
NA Avogadro’s number.
Cxn Number of combinations (selections) of x objects taken from
a total of n objects.
N (x; µ, σ 2 ) Normal distribution of x, with mean µ and variance σ 2 .
N (x; µ, P ) Multi-dimensional normal distribution of x, with mean µ and
covariance matrix P .
eq Basis vector for coordinate q.
uq Unit-length basis vector for coordinate q.
dx Infinitesimal, an “exact differential” of state variable x.
dA Infinitesimal, an “inexact differential” of quantity A that is not
a state variable.
λ(x) Linear mass density as a function of position x.
Mmol Molar mass.
[L]S Representation of L in system S.
Chapter 2: Accessible States and the Fundamental Postulate of Sta-

tistical Mechanics
D Number of internal variables in which a particle can store its
energy.
Ω(E) Number of microstates that each have energy E.
Ωtot (E) Total number of microstates that each have energy somewhere
in the range 0 to E.
ν Number of quadratic energy terms of a particle, meaning the
number of quadratic coordinates that describe the particle’s
energy. (In other texts, this is called the number of degrees of
xvii
xviii List of Common Symbols
freedom of the particle.) The particle need not be an atom; it

could be a molecule.
ic
Ωtot (E) Ωtot (E) for identical-classical particles.
g(E), g(f ) Density of states as functions of energy E and frequency f .
Chapter 3: The Laws of Thermodynamics
ur Unit-length radial vector.

b(r) A function describing the central force as a function of radial
distance r.
U Potential energy of a particle.
dQ Thermal energy put into a system.
dW Mechanical work performed on a system.
dC Energy brought into a system by incoming particles or envi-
ronmental changes.
E, p Electric field and electric dipole moment.
B, µ Magnetic field and magnetic dipole moment.
µ Chemical potential.
γi νi Ni /2, where νi is the number of quadratic energy terms (“de-
grees of freedom” in other texts) per particle in system i, and
Ni is the number of particles in system i.
N Number of particles.
n Number of moles.
E
bi Value of energy Ei at which Ω(Ei ) peaks.
dist
Ωtot Ωtot for distinguishable particles.
S dist Entropy of distinguishable particles.
S ic Entropy of identical-classical particles.
F Helmholtz energy.
G Gibbs energy.
H Enthalpy.
κ Coefficient of isothermal compressibility.
β Coefficient of thermal expansion.
Chapter 4: The Three Interactions of the First Law

CP , C V Heat capacities at constant pressure and volume.
C sp Specific heat capacity.
C mol Molar heat capacity.
List of Common Symbols xix
γ CP /CV , which also equals CPsp /CVsp and CPmol /CVmol .

µJT Joule–Thomson coefficient.
a, b Van der Waals parameters.
amol , bmol Van der Waals parameters for the molar form of van der Waals’
equation.
J Current density, also known as flux density.
κ Thermal conductivity.
(a, b) Angle between vectors a and b (between 0 and π).
I Heat current.
R Thermal resistance.
% Thermal resistivity.
%E Energy content per unit volume.
%m Mass per unit volume.
K Diffusion constant.
∗ Convolution operator.
% Mass per unit volume.
ν Number of particles per unit volume.
B Bulk modulus.
φ Ratio of salt particles to total number of salt and water par-
ticles.
Lmol mol
vap , Lfusion Molar latent heats of vaporisation and fusion.
Chapter 5: The Non-Isolated System: the Boltzmann Distribution

plevel n Probability that a system occupies any state at energy level n.
pstate n Probability that a system occupies a specific state n.
β 1/(kT ).
En , V n Energy and volume of a hydrogen atom at energy level n.
Z Partition function.
Te Excitation temperature of a system.
TR , T V Characteristic temperatures of the onsets of rotation and vi-
bration.
E Abbreviated version of E s , the mean energy of the system.
Chapter 6: The Motion of Gas Particles and Transport Processes

v, v Speed and velocity of a particle.
d3 v dvx dvy dvz .
xx List of Common Symbols
Nvel (v) d3 v Infinitesimal number of particles with velocities in the range

v to v + dv.
Nx (vx ) dvx Infinitesimal number of particles with x velocities in the range
vx to vx + dvx .
Nsp (v) dv Infinitesimal number of particles with speeds in the range v
to v + dv.
Ntot Total number of particles.
dΩtot Number of microstates in the energy range E to E + dE.
Nz (z, vz ) dz dvz Infinitesimal number of particles with heights in z to
z + dz, and z velocities in vz to vz + dvz .
Nsp (z, v) dz dv Infinitesimal number of particles with heights in z to z + dz,
and speeds in v to v + dv.
λ Mean free path.
ν Number of particles per unit volume.
σ Collision cross section.
η Coefficient of viscosity.
Chapter 7: Introductory Quantum Statistics
n The energy level of a one-dimensional oscillator, and also the

number of quantum particles per state, in which each state
denotes one dimension of oscillation of a single molecule in a
crystal.
E Mean energy of a crystal molecule (a quantised oscillator that
can oscillate in three dimensions). Eventually redefined to ex-
clude zero-point energy.
E 1D Mean energy of a one-dimensional quantised oscillator.
TE , T D Einstein and Debye temperatures.
n Occupation number of a crystal, the arithmetic mean of n: the
mean number of quantum particles present per 1D-oscillator
in the crystal. A function of temperature.
Etot Total energy of all oscillators in the crystal.
n(E, T ) Occupation number treated as a function of energy and tem-
perature: the mean number of quantum particles per state.
N Number of quantum particles with energies up to E.
λ De Broglie wavelength.
E Energy of a state, which that state “bestows” on each particle
occupying it.
pn Probability of n quantum particles being present in a state.
List of Common Symbols xxi
N Total number of quantum particles of all energies (in a later

section to N immediately above).
C A constant for a gas of massive particles, encoding spin, vol-
ume, and particle mass.
EF Fermi energy.
Tc Critical temperature of liquid helium.
N Total number of balls to be placed on shelves.
ni Number of balls on shelf i.
Chapter 8: Fermion Statistics in Metals

CVmol (electrons) Valence-electron contribution to a crystal’s molar heat ca-
pacity.
E Mean energy of one valence electron.
E Energy of one valence electron.
N Total number of valence electrons.
n(E, T ) Occupation number of valence electrons.
TF Fermi temperature of valence electrons.
vF Fermi speed of valence electrons.
α A number in the region of 1 or 2, modelling the characteristic
width of the fall-off of the Fermi–Dirac occupation number
with energy.
% Electrical resistivity.
Ne Number of electrons in a conduction band.
Various parameters are also defined in (8.65).
Chapter 9: Boson Statistics in Blackbody Radiation

%(f ) Spectral energy density as a function of frequency f .
ε(f ) Mean energy of a single oven-wall oscillator of frequency f .
λ0 Wavelength corresponding to the peak radiated power from a
black body.
σ Stefan–Boltzmann constant.
N Number of frequency-f photons produced by any process in a
laser.
List of Common Constants
Avogadro’s number NA 6.022 ×1023

(or 6.022 ×1023 mol−1 )
Boltzmann’s constant k 1.381×10−23 J/K
Gas constant R = NA k 8.314 J/K
(or J K−1 mol−1 )
Planck’s constant h 6.626 ×10−34 J s
~ = h/(2π) 1.0546 ×10−34 J s
Speed of light in vacuum c 2.998 ×108 m/s
Proton mass 1.67 ×10−27 kg

Electron mass 9.11 ×10−31 kg
Electron charge −e −1.602 ×10−19 C
Electron volt 1 eV = 1.602 ×10−19 J
Room temperature 298 K (25◦ C)

Ground temperature 288 K (15◦ C)
Air temperature 253 K (−20◦ C)
(mean atmospheric)
Mass of a generic air molecule 4.8 ×10−26 kg

Molar mass of air 29.0 g
Molar mass of sodium 23.0 g
Earth gravity 9.8 m/s2

Atmospheric pressure at sea level 101,325 Pa
Copper’s molar mass 63.5 g

Copper’s Fermi temperature 81,000 K
Number density of copper’s 8.47 ×1028 m−3
valence electrons
xxiii
Chapter 1
Preliminary Ideas of Counting, and Some
Useful Mathematics
In which we set the stage for counting the number of

ways in which a system can arrange itself, derive some
mathematical and statistical results that will be useful
later, examine the meaning of infinitesimals and
partial derivatives, and study how to use units
correctly and efficiently.
The modern subject of statistical mechanics is built on a single, simple idea:

that much of the physics and chemistry of many-particle systems can be de-
duced from ideas of counting and probability. Classical physics contains no
randomness, and yet a probabilistic description turns out to be very capable
of analysing systems composed of a large number of entities. This is not mys-
terious; after all, if we flip a coin a large number of times, we fully expect that
roughly half of the flips will yield heads, even though predicting the outcome
of each flip is so complex as to be effectively impossible. Physical systems that
can be analysed in a similar way are all around us, and they are too complex
to analyse from first principles using Newton’s laws. Historically, this idea of
representing large, complex systems by a small set of parameters gave rise
to thermodynamics, which relied on concepts such as pressure and temper-
ature. Although thermodynamics could analyse pressure by postulating the
existence of large numbers of moving atoms (or molecules), it was silent on
what lay behind temperature. Only with the advent of statistical mechanics
did we gain insight into this and many other areas relevant to large—and not
so large—systems. And, in a modern age, statistical mechanics has spawned
the field of quantum statistical mechanics, which explains the inner workings
of much of our modern technology.
To begin to investigate statistical mechanics, we must know something
about counting in the broader sense, and the purpose of this first chapter
is to present a set of useful tools to do that. Physicists are generally more
fascinated by the physical world than by counting combinations and per-
mutations, and so some of the calculations of this first chapter might come
across as a little arduous. But they lay a secure foundation on which sta-
tistical mechanics rests: this being the idea that the averaging that results
from combining many atoms to make up our world is what makes that world
predictable, despite our lack of knowledge of what each individual atom is
doing at any moment.
Along the way, we will investigate several other mathematical topics that
will come in handy in the chapters to follow.
© Springer Nature Switzerland AG 2018 1
D. Koks, Microstates, Entropy and Quanta,
https://doi.org/10.1007/978-3-030-02429-1_1
2 1 Preliminary Ideas of Counting, and Some Useful Mathematics
1.1 The Spreading of an Ink Drop
Imagine a billiards table on which you place a single ball. You give the ball
a particular initial velocity, parallel to the sides, so that it bounces back and
forth on a single line from one end to the other. In the absence of friction, it
will roll on this line forever, and its motion will be as simple and ordered as
it could possibly be.
Now add more balls, one by one, trying to arrange for some given motion
each time a ball is added. Although they continue to be governed by Newton’s
laws, the range of motions available to the balls becomes phenomenally larger
each time we put another ball on the table. It very quickly becomes clear that
the entire motion of the balls effectively becomes more and more random, even
though it is not random at all. When we replace the balls by, say, molecules
of water in a filled bathtub, the range of motions available to the molecules
becomes so large that it surpasses any test or theory that mathematicians
have devised to ascertain or even define randomness.
The ergodic assumption of classical mechanics postulates that as the num-
ber of particles in our system is increased, with their initial conditions always
arranged to be highly randomised, the system will tend more and more to
spend an equal amount of time in the vicinity of each arrangement of particles
that is allowed by the external constraint of fixed energy.
The essence of statistical mechanics can be seen at work when we carefully
place a drop of ink into a bathtub of pure water. Slowly but surely, the drop
spreads out. Suppose that the bathtub is made from an esoteric material that
insulates the mixture of water and ink from the wider world in every physical
way. This material prevents any heat from flowing between the outside world
and the water and ink. No vibration can pass through the material to or from
the outside world, and particles can neither be shed from the material nor
adhere to it. The energy of the water–ink mixture is thus a fixed quantity,
and the ergodic assumption applies. That is, if we wait long enough, the drop
will essentially reform at some time in the distant future; and, in fact, it will
eventually pass arbitrarily close to any configuration that we care to describe.
There will come a time when the spread of ink takes on the appearance of
Vermeer’s “Girl with a Pearl Earring”, the complete text of every book ever
written or yet to be written—and indeed, the same texts, but with one or
two or 3005 letters upside down—and every sculpture and picture ever made
or that will ever be made.
But we know from experience that this re-forming of the ink into a drop or
dispersing into the appearance of a Vermeer painting is not likely to happen
any time soon: we can be confident that no one has ever seen an ink drop form
spontaneously in a tub full of a water–ink mixture, or even a teaspoon full of
a water–ink mixture. Of course, the esoteric material that forms the tub walls
that we described above simply does not exist in Nature, and so no bathtub
is ever completely insulated from its environment. But this interaction with
1.1 The Spreading of an Ink Drop 3
2 14 5 3 1 9 14 82 23
n molecules of ink N molecules of water

Fig. 1.1 We can count distinguishable molecules of ink and water by systematically
laying them out along a line
the wider world does not affect the basic idea that only a comparatively few
arrangements of the water–ink molecules are recognisable to us as forming
any sort of pattern. So, as the ink molecules interact with the water molecules
and become dispersed, we ask the following question: in how many ways can
n molecules of ink be mixed with N molecules of water, while still retaining
the visual appearance of a distinct ink drop?
This question is not easily answered, because we must be clear about what
a drop is: need it have the same shape as the original drop? Must it be in
the same place? It’s sufficient for our purposes to count the total number of
molecular arrangements that put the ink drop in a chosen place with a chosen
shape in the tub, and we will ignore all molecular velocities. Although the
molecules’ arrangement is three dimensional, we can always construct a three-
dimensional grid in the bath, use it to pick the molecules out systematically,
and then lay them out along a line. Suppose we’ve done that for the ink
drop and water molecules in such a way for the chosen place and shape of
the drop, that the ink molecules all end up on the left end of the line, with
the water molecules continuing to the right. Suppose too that the ink and
water molecules are distinguishable, meaning we can label the ink molecules
1, 2, . . . , n and the water molecules 1, 2, . . . , N . The result is the arrangement
in Figure 1.1. The number of arrangements resembling the chosen drop will
then be the product of factorials, n! N!. The total number of ways in which
all n + N molecules can be laid out is (n + N )!. Let’s calculate the ratio r
of the total number of possible arrangements to the number of “ink drop”
arrangements, when n N :
total number of arrangements (n + N )!

r= =
number of ink-drop arrangements n! N!
(n + N )(n − 1 + N )(n − 2 + N ) . . . (1 + N )
N!

=
n!
N!

' N n /n! . (1.1)
We will approximate n! using Stirling’s rule:
n! ≈ nn e−n , (1.2)
and leave a proper discussion of that to Section 1.2. Then,

n
Nn Ne
r ≈ n −n = . (1.3)
n e n
The number of drops in the bathtub is (n + N )/n = 1 + N/n, so
N volume of tub 1000 mm × 600 mm × 500 mm

' ' ' 1.1 ×107 . (1.4)
n volume of a drop 3 × 3 × 3 mm3
What is the value of n? Assume that the molar mass and density of the ink
are the same as those of water: say, 18 g/mol and 1000 kg/m3 . Then, calling
on Avogadro’s number NA ' 6.022 ×1023 ,
mass of ink
n = NA × number of moles of ink = NA ×
molar mass of ink
volume of ink drop × density of ink
= NA ×
molar mass of ink
27 mm3 × 1000 kg/m3
= 6.022 ×1023 ×
18 g
−9
27 ×10 m3 × 1000 kg/m3
= 6.022 ×1023 ×
0.018 kg
20
' 9.0 ×10 . (1.5)
Placing these values of N/n and n into (1.3) gives

9.0 ×1020 21
r ' 1.1 ×107 × 2.718 ' 106.7 ×10 . (1.6)
We see here the staggeringly large number of ways in which ink can be spread
out, compared to its remaining in a drop form at the place we specified. The
21
number 106.7 ×10 certainly looks large, but how can we comprehend its true
21
size? Consider that if you voice 106.7 ×10 as (approximately) “one million
million million million. . . ” at a normal talking speed, you will be saying the
word “million” for the next 30 million million years. Alternatively, reflect
on the economy of the decimal system: when we represent the number “one
million” by a “1” followed by six zeroes, with each zero just 1 cm across, the
length of this string of zeroes will be six centimetres—a deceptively compact
and efficient scheme for representing the idea of one million things. In con-
21
trast, writing 106.7 ×10 in this decimal system gives a “1” followed by a
string of zeroes whose length is about 7100 light years. That’s not how big
21
106.7 ×10 is; rather, that’s just how long its decimal representation is when
written down. The number itself is inconceivably large.
21
Here is another way of picturing the size of 106.7 ×10 . Use (1.2) and some
21
numerical manipulation to write 106.7 ×10 as a factorial:
21
106.7 ×10 ≈ (3.3 ×1020 )! . (1.7)
1.1 The Spreading of an Ink Drop 5
We will be content to examine the size of the “slightly smaller” number 10 20!,
which we’ll do by shuffling cards. Consider that a deck of 3 cards can be
shuffled in 3! = 6 ways. This is not a large number of different arrangements
(permutations), of course, and certainly not large enough to form the basis of
any real card game.1 A deck of 4 cards can be shuffled in 4! = 24 ways—still
not large—but the number of ways in which a deck can be shuffled grows
quickly with its size. A deck of 10 cards can be shuffled in 10! = 3,628,800
ways, and if we count each of those arrangements at one count per second, the
job will take six weeks to complete. Counting the 11! possible arrangements
of 11 cards at the same speed will take over a year. With 12 cards, we’ll need
15 years of counting, and with 15 cards, the count will take over 41,000 years.
These times are shown in Table 1.1.
Suppose that to be more efficient, we enlist the entire world’s population,
with each person magically able to count one million arrangements per sec-
ond. Counting the possible arrangements of 15 cards in this way will take
0.2 milliseconds; 20 cards will take 6 minutes; 25 cards will take 70 years,
and 30 cards will take one thousand million years. What about a real deck
of 52 cards? Counting its possible arrangements in this way will require
3.7 × 1044 years. If you take a deck of cards and shuffle it well, you can
Table 1.1 Time required to count the possible arrangements of cards in a deck
Number Time for one person Time for world’s population
of cards to count arrangements to count arrangements, with
in deck at 1 count/second each person counting 106/second
3 6 seconds negligible
4 24 seconds
5 2 minutes
10 6 weeks
11 1.3 years
12 15 years
15 41,400 years 0.2 milliseconds
20 see −→ 6 minutes
25 70 years
30 1.2 thousand million years
52 3.7 × 1044 years
1000 2 × 102544 years
10,000 1035,636 years
21
1020 102 ×10 years
1
A welcome evolutionary change to the words “permutations” and “combinations” is
worth mentioning here. An effort is now being made in some high-school curricula to
de-mystify combinatorics by discarding the dry jargon of these terms. Permutations
are now being called “arrangements” (think of arranging flowers), and combinations
are now “selections” (think of selecting books for a library). I used “arrangements”
in some of the above discussion, but decided to retain the old words in other places,
since my use of them is a little peripheral to the main subject anyway.
be as good as completely certain that the arrangement you are holding has
never appeared in human history, and will never appear again.
This thought experiment has only taken us up to envisaging the size of 52!,
the number of permutations of a deck of 52 cards; we still need to work up to
1020!. The amount of time needed for the world’s population to count the 1020!
permutations of 1020 cards is simply unfathomable. We can write down the
21
number of years required (which is 102 ×10 , or 102,000,000,000,000,000,000,000 ,
1,956,570,552,000,000,000,000
more accurately 10 ), but we gain no real ground; we
21
end up only trying to gain a feel for a new number (102 ×10 years) that
21
looks just like the one we started with (r ' 106.7 ×10 ). No matter how we
write these numbers down, they have no meaning for us.
Enlisting more people with higher count rates does not help here. Sup-
pose we employ 10100 people, who each count 10100 permutations per second.
Counting the permutations of 1000 cards will take them 102360 years. For
21
10,000 cards: 1035,452 years. And for 1020 cards: 102 ×10 years, where the
single significant figure used here makes that number appear to equal that
in Table 1.1, but the two numbers of years are different. In the end, we have
gained nothing by switching the counting from the world’s population at one
million per second, to 10100 people counting 10100 per second.
The above discussion of ever-changing ink patterns in a bathtub assumed
the tub had no connection to the outside world. But a real bathtub does
interact with the outside world, and so we can never really treat the water–
ink mixture in isolation. The heat of the bathtub walls affects the liquid,
tending to keep the water and ink molecules maximally mixed. And, of course,
those walls interact with their environment, and so on outward, until we find
ourselves obliged to consider the universe as a whole. Such considerations
form part of the subject of quantum cosmology, which sits at the cutting edge
of modern physics.
1.1.1 Identical-Classical Particles
The particles above were distinguishable, and thus able to be counted. In

contrast, the case of truly identical particles is something else, because if real
identical particles are crowded together sufficiently densely, they behave quite
differently to distinguishable particles. We’ll study such identical particles in
Chapter 7, where we’ll give a meaning to “crowded together”. Particles that
are identical and are being treated as a set, but are not crowded together,
don’t have a conventional name. We will call them identical classical.
If we have 5 distinguishable particles—say, they are numbered—and we
wish to deal them into 5 numbered bins, then this can be done in 5! ways.
But if we have 5 identical-classical particles and wish to deal them into those
same bins, then this can be done in only one way. There is no notion here of
1.2 Wandering Gas Particles 7
being able to swap two particles: if we try to swap two particles, we accomplish
nothing: at a deep level, the final configuration is unchanged from the initial
configuration.
If the ink molecules are identical among themselves, and the water molecules
are identical among themselves, then both groups will certainly be identical
classical. In that case, the n! permutations of n ink molecules cannot be told
apart, and must be counted as a single configuration; and the same is true
for the N water molecules. In other words, our calculations above have over-
counted by factors of n! and N!. We conclude that the number of molecular
arrangements in which the ink can form a drop, or a Girl with a Pearl Ear-
ring, or anything else, is not n! N!, but simply 1: there is only a single way
in which a given configuration can exist if all of its particles are identical.
Of course, this idea of having over-counted by a total factor of n! N! also
applies to the case when the identical-classical particles are dispersed. There,
too, we must divide the number (n + N )! of distinguishable configurations
by n! N! to give the number of identical-classical configurations.
In summary, for the distinguishable molecules analysed in (1.1)–(1.6),
total number of configurations = (n + N )!

number of ink-drop configurations = n! N! . (1.8)
For the identical-classical case, we have
total number of configurations = (n + N )!/(n! N! )

number of ink-drop configurations = 1 . (1.9)
Thus, for both cases, the sought-after ratio is
total number of configurations (n + N )! (1.6) 21

r= = 106.7 ×10 .
number of ink-drop configurations n! N!
(1.10)
Although the numbers of configurations are reduced overall for identical-
classical particles, the ratio of the total number of configurations to the num-
21
ber of ink-blot configurations is unchanged, at r ' 106.7 ×10 .
1.2 Wandering Gas Particles
Central to statistical mechanics is the idea of counting the number of ways

in which some interesting and effectively isolated system can take on vari-
ous configurations. As we saw with the bath example above, counting these
configurations exactly is usually a difficult or even impossible task—and one
that’s not always completely well defined. Physicists must do the best they
can to get around such difficulties.
We will focus on calculating something more basic than the number of

configurations of an ink drop in water. Given a fixed number of gas particles
in a room, what is the chance of there being some specified number of those
particles in a specified part of the room? More interesting still: how proba-
ble are sizeable fluctuations around this number if the particles move about
randomly? It will turn out that for systems with large numbers of particles
such as we find in everyday life, even incredibly tiny fluctuations are very
improbable indeed. Perhaps, then, a view of the world that has randomness
at its heart can still be compatible with the fact that the world does not look
particularly random.
Figure 1.2 shows a room with imaginary partitions that divide it into four
parts. It contains a gas of 14 particles that are free to move about, effectively
randomly. We will take the particles to be distinguishable, meaning that,
to all intents and purposes, they have numbers written on them. At any
given moment, what is the chance that 3 particles will be found in part 1,
4 particles in part 2, and so on, as shown in the figure? We don’t care which
numbers are found where; we focus only on 3 particles being found in part 1,
4 particles in part 2, and so on. To begin to solve this problem, it’s easier to
think of dividing the room into just two parts. This is the job of the binomial
distribution. Given N distinguishable particles, place each of them randomly
into either of the two parts (usually called “bins” in combinatorial theory).
The chance of a particular particle being allocated to bin 1 is p1 , and the
chance of a particular particle being allocated to bin 2 is p2 = 1 − p1 . When
all N particles have been placed in the bins, we ask: what is the chance
P (n1 ) that n1 particles are found in bin 1 (and hence n2 = N − n1 particles
are found in bin 2), with no regard for the numbers that are written on them?
Focus first on a particular set of n1 particles ending up in bin 1: say, par-
ticles 1, 2, and 4. We are not concerned with the order of the particles here;
8 11
3
4
10
5
14 9
2 12
13
7
1
6
part 1 part 2 part 3 part 4
Fig. 1.2 Numbered particles are confined to a room in which they can move freely.
If we partition the room as shown, what is the chance that, at some given moment,
3 particles will be found in part 1, 4 particles in part 2, and so on?
1.2 Wandering Gas Particles 9
Bin 1 Bin 2
1 2 3 4 5 6 7
1 2 3 4 5 7 6 3! 4! rows, each
with the same
combination in
1 3 2 4 5 6 7 each bin
7! rows, each
with a different 1 3 2 4 5 7 6
permutation
1 2 4 3 5 6 7
3! 4! rows, each
1 2 4 3 5 7 6 with the same
combination in
each bin
etc.
Fig. 1.3 Counting combinations by the “trick” of counting permutations and then
correcting for the resultant over-counting
if particles 1, 2, 4 are found in bin 1, we don’t distinguish between referring

to them as “1, 2, 4” or “1, 4, 2” or “2, 1, 4”, etc. Recall that this set of three
numbers with no regard for their order is a combination of those numbers. If
we insist on a particular order, then that ordered set of numbers is a permu-
tation of those numbers. What, then, is the chance that the combination of
particles 1, 2, and 4 ends up in bin 1, with the rest in bin 2? We throw the
particles toward the bins one by one. The chance that particle 1 ends up in
the correct bin (bin 1) is p1 . The chance that particle 2 ends up in the correct
bin is also p1 , that particle 3 ends up in the correct bin (bin 2) is p2 , and so
on. Multiplying these probabilities then gives the chance that particles 1, 2,
and 4 end up in bin 1 and the rest in bin 2 as p31 p42 .
Clearly, the chance that a particular combination of n1 particles ends up
n n
in bin 1 and the remaining n2 particles in bin 2 is p1 1 p2 2 . To complete
our task of finding P (n1 ), we need only multiply this individual probability
by the total number of such possible combinations. We begin to do this by
writing down all possible combinations of 3 particles that can be found in
bin 1 and 4 particles in bin 2. In combinatorial theory, when you want to
count something, you start listing all possible configurations, and you will
often begin to see an efficient way to make this list without actually writing
it down fully. In our case, we will use a kind of “trick” of over-counting: we
will list all permutations, meaning that we will distinguish between “1, 2, 4”
and “1, 4, 2”, and so on. Later, we will correct for having listed too many
possibilities.
Figure 1.3 shows such a listing, with each number allocated a unique colour
to aid in the visualisation. With N = 7 particles in total, n1 = 3 of which must
Another random document with
no related content on Scribd:
Constant indulgence in alcohol did not pull him together as before; and although
previously he had been able to indulge in large quantities of alcohol, a very little
now affected him adversely.
The first epileptiform attack was in July, and in November he commenced to
have delusions, was restless, suspicious.
On admission to the asylum he showed marked cachexia. Weight, 8 stone 7
pounds; height, 5 feet 9 inches. There was present well-marked oral sepsis and
blue line.
Mental Condition.—Restlessness; disorientation; remitting delirious state;
periods of shouting coincident with colic, worse at night; auditory hallucinations.
Physical Condition.—Bilateral wrist-drop; extensor paralysis of the fingers; hand-
grip and gait impaired; reaction of degeneration of paralyzed muscles; coarse
tremors; fibrillary twitching; staccato articulation.
Sensory.—No definite change.
Reflexes.—Pupils normal. Sluggish reaction to light and accommodation.
Organic.—Deglutition difficult. Micturition and defæcation not under control.
Vaso-motor.—Tâche cérébrale marked.
Eye neuro-retinitis. Unequal amaurosis.
Heart.—Increased action, variable; alteration during exacerbations of colic.
Second sound in aortic area accentuated. High pressure, variable. Majority of
arteries thickened.
He suffered gradual mental change; the whole of the mental symptoms
increased in severity until the patient looked like the final stages of a case of
general paralysis. He died on December 1. Colic was present at intervals during
the whole time.
Post-mortem made the next day. Septic bronchitis. Hæmorrhage at the base of
epiglottis and left vocal cord.
Lungs.—Septic broncho-pneumonia.
Pericardium.—Small amount of fluid.
Heart.—Striated, bluish. Weight 11¹⁄₄ ounces.
Ventricles.—Slight hypertrophy of left ventricle.
Valves.—Competent.
Aorta.—Atheroma near its bifurcation.
Arteries.—All more or less thickened.
Peritoneum.—Retroperitoneal hæmorrhage in region outside pancreas.
Mesenteric glands enlarged, indurated, bluish on section.
Stomach.—Normal.
Intestines.—Vessels congested. Large bowel constricted at irregular intervals.
Cæcum.—Mucosa slate-coloured.
Colon.—Dark-greenish mass.
Liver.—Blue on section; pale yellow areas; soft in consistency. Weight, 47³⁄₄
ounces.
Spleen.—Normal.
Kidneys.—No fat. Cirrhotic, adherent, atrophic cortex, granular.
Muscles.—Generally dark in colour; wasted.
A very complete histological examination was made of the brain and spinal cord,
and throughout the particular changes noticed were proliferation of the glia, hyaline
thickening of the walls of the vessels, both arteries and veins, and presence of
congestion; and here and there rupture of the smallest vessels, causing miliary
microscopic hæmorrhages into the perivascular sheaths and the substance of the
brain. There was no infiltration with lymphocytes and plasma cells, as is found in
general paralysis. The neuroglia showed a formative hyperplasia resulting from
chronic irritation.
In the cortex there was neuroglia proliferation in the polymorpho layer and the
molecular layer. Changes were seen in the Betz cells, particularly in the Nissl
substance, with perinuclear chromatolysis, such as is generally found in chronic
peripheral neuritis, whether due to lead, alcohol, or other toxic causes.
There was no coarse atrophy or degeneration of the fibres of the cortex. Neither
the cerebellum nor the spinal cord at any of the levels examined showed fibre
atrophy or degeneration, except possibly a slight diffuse sclerosis in the crossed
pyramidal tracts of the lumbar region.
Microscopical examination was made of the heart, spleen, kidney, liver, lung,
and suprarenal gland. There was a general condition of angiosclerosis; in the liver
a fibrotic overgrowth around the vessels; in the kidneys well-marked interstitial
fibrosis.
A chemical examination of the brain was also conducted by the copper
potassium nitrite method, but no lead was found.
Excretory System.—A large number of observers have shown

that great stress is thrown on the kidney in the excretion of lead.
Discussion has taken place as to whether the effect is a primary
interstitial or a parenchymatous nephritis. Most observers are agreed
that the histological changes found in the kidneys of lead workers
have very little by which they may be differentiated from the effects
of alcohol.
Although the kidney suffers directly from the effect of circulating
lead, the amount of lead excreted by the kidney in chronic cases is
usually small, variable in quantity, and very rarely exceeds more than
5 milligrammes in the twenty-four hours.
The chemical estimations of the quantity of lead found in the
kidney of persons who have died of lead poisoning given by different
observers, vary exceedingly. Even in cases of definite lead
poisoning, where there can be no reasonable doubt as to the
diagnosis, many cases are on record where no lead at all has been
discovered in the kidney.
It is not acute nephritis which is seen in lead poisoning, but the
chronic cirrhotic variety. This probably takes a very long time to
develop; indeed, animals kept under the influence of lead for two
years show very little kidney destruction. It is quite possible that in
the kidney disease met with in lead-workers the combined effect of
alcohol with lead is really the causative factor. There is not sufficient
statistical evidence to make a definite statement on this point, and it
would only be possible by comparing the records of the autopsies of
a number of persons working in lead who do not die from lead
poisoning, and who were non-alcoholic, with a similar number of
persons who, in addition to their lead absorption, were alcoholic
subjects.
It is unusual to find blood in the urine, and the condition of the
kidney does not suggest that it would be present.
Gull and Sutton[42] have described arterio-capillary fibrosis in
which the intima of the larger vessels became greatly hypertrophied,
and many of the smaller vessels are practically destroyed by
obliterative arteritis. The production of arterio-sclerosis, with
attendant thickening of the vessel walls and with the various
symptoms commonly associated with arterio-sclerosis, were
regarded as secondary symptoms of lead poisoning. The action of
lead on the vessel walls themselves thus independently proved by a
large number of observers working at different aspects of the
problem suggests the pathological change in the vessels as the
common element in the cause of these diverse symptoms of lead
poisoning—colic, paralysis, mania. Generally speaking, however, the
attention of most has been rather focussed on the kidney and the
degenerative changes occurring in that organ due to the irritative
action of lead in the process of excretion than on the vessels
themselves.
Lead in the urine is by no means so common nor so definite a
symptom of lead poisoning as might be supposed, considering the
extreme manner in which the kidneys suffer in old-standing cases.
Of particular importance in this respect is the case referred to by
Zinn[43], where a woman aged thirty-three received 20 grammes of
lead acetate in error. After the first acute symptoms had passed off,
the case drifted on to one of chronic poisoning, with the usual
symptoms of colic, anæmia, and cachexia. During the whole period
of the disease, both acute and chronic stages, examinations of the
urine for lead were made, using the method of Fresenius Babo[44];
yet lead was only detected in the urine during the early stages, and
directly the acute symptoms had passed off no further lead could be
detected. This point is of some importance, particularly when taken
together with the experiments quoted by Blum[45], who, injecting
animals with lead iodide, was unable to recover lead from the urine.
The iodide only passed through the kidney, the lead being retained in
the body.
Jaksch[46] states very definitely that lead is not found in the urine
in chronic cases, but only in the acute cases, and then quite early.
With regard to the kidney two views are held—the one regarding
the disease of the kidney as primarily affecting the bloodvessels, and
the other as an initial parenchymatous change causing secondary
obstruction and alteration in the vessels themselves. There is
therefore much evidence to show that, whether the bloodvessels be
primarily or secondarily affected, almost all observers are in accord
in the opinion that at one time or another, either sooner or later, the
bloodvessels become affected through the action of lead.
Kobert[47] points out that in no case was distinct cirrhosis of the
kidney produced in experimental lead poisoning in animals;
inflammation certainly was to be seen, either interstitial or
parenchymatous, but apparently the poisoning had not progressed a
sufficient length of time for definite cirrhosis to be produced. On the
other hand, kidney changes have been found of various types, all of
which may be the precursors of the ultimate cirrhotic and fibroid
change occurring in the kidneys seen in chronic poisoning by lead as
well as in chronic alcoholism. Particular stress must be laid on the
fact that cirrhotic kidneys are so frequently the direct result of long-
continued alcoholic excess, and, from what has been demonstrated
in the experimental researches on predisposition to lead caused by
alcohol, the condition of cirrhosis of the kidney in a lead-worker is by
no means indicative of lead poisoning, as it may be an old alcoholic
effect long antedating that due to lead.
Oliver[48], Charcot[49], Gombault[50], Hoffer[51], and others, found a
certain amount of parenchymatous degeneration. Von Leyden[52],
however, was able to produce a granular condition of the kidney with
glomeruli shrunken and an arterio-capillary fibrosis. Gayler[53], on the
other hand, thinks that the arteritis of the smallest arteries is the
preliminary effect upon the kidney, whereas more recently Glibert[54]
published plates of the kidney showing definite sclerosis as well as
interstitial nephritis.
Cornil[55] and Brault[56] think the vessels are affected only
secondarily, and that parenchymatous changes are the primary
lesion. Hoffer[57], by feeding guinea-pigs with lead, produced very
definite obliterative arteritis. Klemperer[58] claims to have produced
inflammation and definite necrosis of portions of the kidney
substance.
The whole of the kidney is not necessarily affected. Only portions
of it may show changes, while Kleinenberger[59] notes that in chronic
lead poisoning, at the time of acute exacerbation of the disease,
granular casts as well as red blood-cells are found; and, further, that
in cutting through them crystallized masses are occasionally found,
consisting of urates, and sometimes containing lead.
Gayler[60] considers that the effect on the kidney commences in
the muscular coats of the smaller vessels, in which endarteritis
followed by obliterative arteritis is set up.
Practically all observers, therefore, are in agreement that the
kidney suffers to a very considerable extent in chronic poisoning,
and the majority of observers are also in agreement that the
bloodvessels themselves are the primary seat of the change.
Further, the presence of blood in the urine is exceedingly rare in
chronic lead poisoning, despite Kleinenberger’s[61] statement to the
contrary. It certainly may occur during a very acute attack, but we
have never seen this symptom.
Circulatory System.—Arterio-sclerosis occurring in lead-
workers has been known for some time, and the anæmia of
saturnism has been known for an even longer period. For some time
no definite type of anæmia was associated with lead cachexia, and
the anæmia was generally regarded as one arising from general
malnutrition. Here and there through the literature of the pathology of
lead poisoning are to be found remarks which suggest that the action
upon the bloodvessels may be a primary instead of a secondary
effect. Obliterative arteritis is described by Uhthoff[62], Pflueger[63],
Oeller[64], and Pal[65], and in other cases obliterative retinitis has
been considered to be associated with the action of the lead upon
the vessel walls.
Heubel[66], and later Rosenstein[67], found that, in dogs poisoned
with lead, definite cerebral anæmia was produced, due to vaso-
constriction, and consider it to be due to the direct action of lead
upon the intima of the vessel walls. Associated with such poisoning
were symptoms of eclampsia and uræmia, and the latter author
considers that the uræmia is due to vaso-constriction of the kidney
vessels.
Oliver[68] and others have also pointed out the alteration in the
pulse-rate associated with exacerbations of colic, and a number of
observers have noted that certain drugs, such as atropin and amyl
nitrite, which are known vaso-dilators, have a distinctly calming effect
upon the paroxysms of pain.
One or two other observers have actually noted the presence of
hæmorrhages in the lesions; thus, in the case quoted by Mott[69]
definite yielding of the vessel walls and signs of old hæmorrhage are
described amongst other lesions in the brain. Seifert[70] also
describes the presence of hæmorrhages amongst the ganglion cells
in the anterior columns of the cord, both in the case of persons who
have died of lead poisoning and animals to which lead had been
given experimentally. In addition, Sajous[71] describes a case of
paralysis of the superior laryngeal nerve, associated with
hæmorrhages, in the region of the abductor muscles of the larynx.
Mott’s case also showed this laryngeal hæmorrhage.
More recently Elschnig[72], in his observations upon the eye, has
determined a close association between vaso-motor affections,
constrictions, and dilatations, and various eye lesions, such as
amaurosis and amblyopia, occurring in lead poisoning.
Rambousek[73], in summing up Elschnig’s work, points out how much
his observations tend to bridge over the gap between the action of
lead upon the blood, the bloodvessels, and the nerves. He points out
that the eye is a peculiarly favourable organ for watching the effect of
a poison so insidious as lead. The bloodvessels, the nerves, and the
muscles, are all open to inspection and actual observation to a
degree not to be found in any other part of the body. Elschnig[74], in a
typical case of sudden lead amaurosis associated with acute lead
colic, found that very definite motor spasm of the vessels of the eye,
conjunctiva, and the retina, were associated with the amaurosis. He
argues from this that the action of lead is probably directly upon the
unstriped muscular fibre of the vessel walls; that such an action may,
and does, extend to the vessels of the eye muscles, producing
paralysis of the muscles of accommodation, and a dilatation of the
pupil, which may be observed in a large number of persons
employed in conditions subjecting them to lead absorption. Elschnig
further considers that the transitory amaurosis which is often
associated with lead poisoning may be due to vaso-motor
disturbances in the brain itself, as well as in the eye.
Still more recently, and due, no doubt, to a great extent to the work
of Elschnig, further attention has been drawn to the vascular system
in lead poisoning. Elschnig’s work has carried the question another
stage forward by showing the association of vaso-motor
disturbances with eye disease, whilst in this country Oliver[75]
pointed out the effect upon the pulse of abdominal colic.
At the beginning of the researches on this point described in the
next chapter, this clue running through the whole of the pathology of
lead poisoning was not appreciated. At the commencement of the
investigations there seemed to be no main general line of symptoms
or histological findings that could be adduced as characteristic of
lead poisoning; in fact, the initial experiments were performed, with
the object of examining the association of lung-absorbed lead
compounds as a possible cause of lead poisoning, as against the
entrance of lead by the alimentary canal; but as the experiments
proceeded it became clear that the stress of the initial intoxication
was undoubtedly falling upon the bloodvessels, and more particularly
upon the minuter bloodvessels, and less on the arterial side of the
capillaries (although the capillaries were to a large extent associated
with the process) than upon the venous radicles.
A general consideration of the pathology shows that lead causes
changes in the nervous system affecting both upper and lower
segments, degeneration of the ganglion cells in the cord and in the
brain, interstitial inflammation of the neuroglia, cortical degeneration,
distinct neuritis, both axial and peri-axial, of the peripheral nerves,
and also signs of change in the sympathetic nervous system in
chronic lead poisoning. Later work has, however, all tended to point
out that the chief and first effect of lead is upon the blood.
Moritz[76] first pointed out the presence of basophile granules in
the red blood-cells. The work was followed up by Emden[77],
Gravitz[78], Zinn[79], Otto[80], Silbert[81], and by Escherich[82]. All these
authors found basophilic erythrocytes in the blood associated with
blood-destruction, and Escherich in addition describes early changes
taking place in the intima of the bloodvessels associated with vaso-
constriction. The Italian author Mattirolo[83], as well as Marchet[84]
and Jores[85], came to a similar conclusion. Glibert of Brussels[86],
carrying the observations somewhat farther, and although working
with guinea-pigs, which normally show basophilic staining in their
blood-cells, was able to demonstrate one further point of
considerable value—namely, the increase in the viscosity of the
blood, with blood-corpuscles of greater toughness, elasticity, and
power to resist destruction when making films, than in normal blood.
There is thus very striking continuity in the observations of all the
various observers, despite the fact that at first sight their descriptions
may appear discordant. There seems no doubt that practically all
authors who have given attention to the subject are agreed that the
circulatory system, and primarily the blood circulating in the vessels,
is affected by lead, and, further, that the vessels themselves undergo
degeneration of various types, many of the cases examined showing
complete obliterative arteritis as the result of long-standing irritation.
Others describe no obliterative changes of this type in the vessels,
because attention was given mainly to the nervous system, where
the cells were found degenerated and showing chromatolysis. But,
on the other hand, careful observers, such as Mott, have noted the
presence, in passing, of these apparent yieldings of the vessels here
and there in the region of the degenerated nervous tissue. Again,
even the histological action of a drug such as amyl nitrite points to
involvement of the vaso-motor system. Perhaps this curious
association through all the described pathology and bloodvessel
infection would not appear so clear but for the more recent
investigations described in the following chapter.
REFERENCES.
[1] Kobert: Lehrbuch der Intoxikationen, 2te Aufl., 1906, p. 361.
[2] Oliver, Sir T.: Lead Poisoning. 1891.
[3] Dixon Mann: Forensic Medicine and Toxicology, p. 495.
[4] Stockvis: International Congress of Industrial Hygiene. Brussels, 1910.
[5] Ménétrier: Meillère’s Le Saturnisme, pp. 131-136.
[6] Kussmaul and Meyer: Deutsches Archiv für Klin. Med., ix., p. 283.
[7] Tanquerel: Traité des Maladies de Plomb, ou Saturnines. Paris, 1839.
[8] Bernard: Meillère’s Le Saturnisme, p. 155.
[9] Bokai: Trib. Med., June 11, 1891.
[10] Riegels: Kobert’s Lehrbuch der Intoxikationen, p. 363.
[11] Galvini: Rivista Clinica, fasc. iii., 1884.
[12] Tanquerel: Ibid.
[13] Pal and Mannaberg: Revue Générale de Villaret, Gaz. des Hôp., Fév.
16 and 19, 1903.
[14] Westphal: Archiv f. Phys. u. Nervenkr., 1874.
[15] Dejerine: Mém. de la Soc. de Biologie, 1879, et Exposé de Titres, p.
58, 1894.
[16] Eichhorst: Ueber Bleilähmung. Virchow’s Archiv, 1890, p. 217.
[17] Ramond: Maladies du Système Nerveux, t. xi. 1895, 1896.
[18] Marie and Babinski: Meillère’s Le Saturnisme, p. 193.
[19] Vulpian and Steiglitz: Archiv für Psych., 1892, xxiv., p. 1.
[20] Erb: Berl. Klin. Woch., 1884, p. 110.
[21] Hitzig: Studien über Bleiverg. Berlin, 1868.
[22] Boerwinkel: Virchow’s Archiv, Bd. cxx., 1890.
[23] Eichhorst: Ibid.
[24] Potain: Bull. Med., 1887.
[25] Vulpian: Maladies du Système Nerveux. 1879.
[26] Oppenheimer: Zur Kennt. der Exp. Bleiverg. Berlin, 1898.
[27] Oeller: Path. Anatom. der Bleilähmung. München, 1883.
[28] Steiglitz: Archiv für Psychiatrie, Bd. xxiv., 1892.
[29] Hitzig: Ibid.
[30] Westphal: Archiv für Psychiatrie, Bd. xix., 1888.
[31] Chvostek: Neurol. Centralblatt, 1897.
[32] Kolisko: Die Bekämpfung der Bleigefahr in der Industrie, von Leymann,
p. 21. 1908.
[33] Quensel: Archiv für Psychiatrie, Bd. xxxv., 1902.
[34] Nissl: Allgemeine Zeitschrift für Psychiatrie, Bd. xlv., 1892; Bd. iv. 1897.
[35] Berchthold: Die Bekämpfung der Bleigefahr in der Industrie, von
Leymann, p. 23. 1908.
[36] Sorgo: Wien. Med. Woch., 1900.
[37] Steiglitz: Archiv für Psychiatrie, Bd. xxiv., 1892.
[38] Prévost and Binet: Revue Médicale de la Suisse Romande, ii., 1889.
[39] Mott: Archives of Neurology and Psychiatry, vol. iv., p. 117.
[40] Glibert: Le Saturnisme Expérimental: Extrait des Rapports Ann. de
l’Insp. du Travail, 1906.
[41] Mott: Ibid.
[42] Gull and Sutton: Kobert’s Lehrbuch der Intoxikationen, 2te Aufl.,
1906, p. 370.
[43] Zinn: Berl. Med. Woch., 1899.
[44] Fresenius Babo: Liebig’s Annalen, vol. xlix., p. 287. 1844.
[45] Blum: Wien. Med. Woch., No. 13, 1904.
[46] Jaksch: Klinische Diagnostik.
[47] Kobert: Ibid., p. 369, and general Literature, p. 376.
[49] Charcot: Leçons sur les Maladies du Foie et des Reins. Paris, 1882.
[50] Gombault: Archiv für Physiologie, 1881.
[51] Hoffer: Dissertation, Freiburg, 1883.
[52] Von Leyden: Zeit. für Klin. Med., 1883.
[53] Gayler: Ziegler’s Beitr., ii., 1888.
[54] Glibert: Ibid.
[55] Cornil: Journal de l’anat. et physiol., No. 2, 1883.
[56] Brault: Loc. cit.
[57] Hoffer: Loc. cit.
[58] Klemperer: Kobert’s Lehrbuch der Intoxikationen, 2te Aufl., 1906, p.
370.
[59] Kleinenberger: Münch. Med. Woch., No. 8, 1904.
[60] Gayler: Loc. cit.
[61] Kleinenberger: Loc. cit.
[62] Uhthoff: Handbuch der Aug. Lief. Leipzig, 1901.
[63] Pflueger: Die Bekämpfung der Bleigefahr in der Industrie, von
Leymann, p. 21. 1908.
[64] Oeller: Ibid.
[65] Pal: Zentralbl. f. innere Med. Leipzig, 1903.
[66] Heubel: Path. und Symp. Chron. Bleiverg. Berlin, 1871.
[67] Rosenstein: Virchow’s Archiv. 1897.
[69] Mott: Ibid.
[70] Seifert: Berl. Klin. Woch., 1884.
[71] Sajous: Archiv für Laryng., iii., 1882.
[72] Elschnig: Wien. Med. Woch., 1898.
[73] Rambousek: Die Bekämpfung der Bleigefahr, von Leymann, p. 15.
1908.
[74] Elschnig: Loc. cit.
[76] Moritz: St. Petersb. Med. Woch., 1901.
[77] Emden: Die Bekämpfung der Bleigefahr, von Leymann, p. 19.
[78] Gravitz: Deutsche Med. Woch., No. 36. 1899.
[79] Zinn: Berl. Klin. Woch., 1899.
[80] Otto: Revue Méd., 1892.
[81] Silbert: Ibid.
[82] Escherich: Die Bekämpfung der Bleigefahr, von Leymann, p. 18.
[83] Mattirolo: Ibid., p. 19.
[84] Marchet: Ibid., p. 19.
[85] Jores: Ziegler’s Beitr., Bd. xxxi., 1902.
[86] Glibert: Ibid.
CHAPTER VI
PATHOLOGY—Continued[A]
[A] This chapter is the work entirely of one of us (K. W. G.)
It was thought that some light might be thrown on chronic

intoxication produced by lead salts if direct experiment were made
upon animals, resembling in the arrangement of such experiments,
as far as possible, the industrial conditions under which human
beings contract lead poisoning.
The animals chosen for the experiments were cats, as it is a fact
of common knowledge that it is impossible to keep cats in lead
works, particularly white-lead, because they rapidly become
poisoned if allowed to stray about the works. The same holds good
in the case of dogs.
From the statistics already given in Chapter IV., and from the
remarks in the chapter on Ætiology, there was no doubt whatever
that dust played a most important rôle in the production of industrial
lead poisoning. In attempting, therefore, to copy the industrial
conditions, it is essential to submit the animals experimented upon to
infection by means of air in which lead dust is suspended. A large
number of experiments have been carried out in the first place, by
myself[1], and later in conjunction with Dr. Goodbody[2], and another
series of experiments were also undertaken by myself[3]. Further
experiments are still in progress in this and other directions.
1. Breathing Experiments—First Series.—A. The animals
experimented upon were placed in a large closed chamber at one
end of which an electric fan was fitted in such a way that the air was
kept in constant motion. The lead dust was introduced by means of a
funnel through the roof in a definite quantity during timed intervals.
By means of an aspirating jar and a tube inserted into the side,
samples of air were withdrawn from time to time during the
experiments, and submitted to chemical analysis to determine the
quantity of lead circulating in the air. These samples were drawn off
at the level of the animals’ heads. Great care was taken to eliminate
any swallowing of dust by the animals during the experiments, by
protecting their coats from the dust and carefully brushing them at
the conclusion of each exposure.
Second Series.—B. In other experiments a chamber containing
two separate compartments was constructed, and lead dust
suspended in air was blown into the two compartments by means of
an electric fan situated outside. The apparatus was so arranged that
the draught of air from the fan passed through two separate boxes,
in which the lead compound under experiment was kept agitated by
means of small fans situated in the boxes and driven by a second
electric motor. In this way two different samples of lead were
experimented on at one and the same time, the air current driving in
the dust through the two boxes being equal on the two sides; the
quantity of dust was therefore directly proportional to the compound
used. Samples of the dusty air were aspirated off and subjected to
analysis, as in the first series. In this series of experiments the
animals were so arranged that only their heads projected into the
dust chamber during exposure.
2. Feeding Experiments.—Feeding experiments were carried
out by mixing a weighed dose of the lead compound experimented
with, and adding this to a small portion of the animal’s first feed in
the morning. It was found that unless the lead was well incorporated
with the animal’s food it would not take the lead in the dry form; and
in dealing with white lead and other dust, it was necessary to give
the compound in a similar form to that in which a man would obtain it
under industrial conditions, which of course precluded the use of a
solution.
The amount of lead given by the mouth as a control to the
inhalation experiments was from seven to ten times the dose which
could be taken by the animal during its exposure in the cage, and the
dose was given daily, and not every third day as in the inhalation
experiments. All the compounds used in the inhalation experiments
were given to animals by the mouth, the animals’ weights being
carefully noted.
In a further series of feeding experiments a soluble salt of lead
was added to the animals’ food (water or milk), the salt in this case
being the nitrate. The quantity added was much smaller than in the
dust experiments. 0·1 gramme was given daily.
3. Inoculation Experiments.—As a further control to both the
breathing and feeding experiments, the various lead compounds
similar to those used in the other experiments were inoculated into
animals. The insoluble salts gave some difficulty in the technique of
injection, but by using a large needle, and making the suspension of
the material in the syringe, the difficulty was overcome. The quantity
of material inoculated varied; it was calculated in fractions of a
gramme per kilogramme body weight, the quantity of fluid used
being the same in all cases—namely, 10 c.c.—and inoculations were
made subcutaneously and intramuscularly in the muscles of the back
after previous shaving. In only one case was localized inflammation
produced, and this was when the acetate was the salt employed.
None of the animals exhibited any signs of discomfort during the
experiments from the presence of lead dust in the air; once or twice
sneezing was noticed, but this was an uncommon occurrence. This
point is of practical importance, as the lead dust contained in the air
in white-lead and other factories is not of itself irritating to the
mucous membrane of the lung. The animals subjected to this form of
experiment were no doubt absorbing much larger doses of lead than
are persons engaged in the manufacture of lead compounds.
The only ascertainable difference in the ultimate pathological
lesions produced in animals, whether inhaling large quantities or
minimal quantities of dust, was the rate at which the poisoning took
place. In certain experiments it was found that the animals
maintained a kind of equilibrium, much as do workmen engaged in
dusty lead processes. It was found, moreover, that some animals
showed a certain amount of tolerance to the effect of lead dust, in
that their weights remained almost constant, but an increase in the
quantity of lead present in the air immediately produced progressive
diminution in the body weight; and as this diminution in the body
weight approached to one-third of the animal’s initial weight, so
symptoms of chronic poisoning supervened.
In addition to the animals inhaling lead dust over prolonged
periods, certain other inhalation experiments were made for the
determination of lead dust in the lung as opposed to the stomach. In
the inhalation experiments proper, where the animals were exposed
to inhalation every other day or every third day, for only an hour at a
time, the quantity of lead present in the air was not very large, and it
was thought essential to determine if, in exceedingly dusty
atmospheres, any appreciable amount of lead could be found in the
stomach. Ten animals were submitted to the inhalation of air heavily
charged with various types of lead dust. The animal was exposed to
the dust for an hour and a half to two hours; at the end of this time it
was anæsthetized, and when the respirations had ceased, and the
animal was dead, sulphuretted hydrogen was blown into the lung
and into the stomach. The animal was then rapidly dissected and
staining looked for. The tissues were further treated with acid and re-
exposed to sulphuretted hydrogen gas. In one animal only out of the
ten was any staining noticed in the stomach. In none of the others
was any such staining found, but very definite blackening was found
in the larynx, trachea, and macroscopically even in some of the
bronchioles. Sections of the lung were further submitted to
histological examination, and by means of micro-chemical tests with
chromic acid and with iodine, and also by comparing sections of the
experimental animals and animals which had not been subjected to
lead dust inhalations, a very much larger quantity of material was
found present in the lungs of the inhalation animals than in the
normal animal. The dust was situated in the alveoli and the alveolar
cells, and often in the lymphatics. On examining microscopically
sections of the lungs of those animals exposed to graduated
inhalation over extensive periods, a far larger number of blackened
granules, dust, pigment, and other substances, was found than in
similar sections of animals which were under normal conditions and
had not been exposed to lead dust, although it is true such animals
show a very fair proportion of carbon particles taken up by the lung
tissue.
A further important fact was noticeable in animals Nos. 21 and 22
(see p. 101), which had been exposed to a low solubility glaze such
as is used in the Potteries. Low solubility glaze is compounded with
lead frit—that is to say, a lead glaze (or lead silicate) which has been
finely ground. The particles of this substance are much larger than
those of ordinary white lead, and in addition they are much more
angular. Of three animals exposed to this glaze, one actually died of
pneumonia (acute), and the other two suffered from some bronchial
trouble, both of them showing distinct signs of pneumonic patches
and old and chronic inflammation when examined histologically;
whereas in none of the other animals exposed to white lead dust or
to the high solubility glaze, which contained white lead as opposed to
lead frit, no such pneumonic or fibroid changes were found. This
point is of some pathological importance.
The inhalation experiments also throw some light on the quantity
of lead necessary to produce poisoning. The animals in the
inhalation experiments were exposed for varying periods, and
constant estimations made of the lead present in the air. In a number
of instances samples were taken from the cage air during the whole
of the experiment, as rapidly as possible. The quantity of lead
floating in the air was found to increase as the experiment
progressed, although a large amount of the lead introduced was
caught on the side of the cage and deposited on the floor.
In the later experiments the method of taking the samples
continuously during the experiment was abandoned, and four
samples only were taken, and the average recorded. A simple
calculation will give the quantity of lead dust it would be possible for
an animal to inhale during the whole of this period of exposure. The
utmost tidal air in the case of a cat would be taken at 50 c.c. Taking
the average, about 0·27 gramme of lead was inhaled during the half-
hour of exposure.
Feeding Experiments.—Twelve feeding experiments of various
types are recorded. The method of experiment was as follows:
The compound under investigation was carefully weighed out each
day (0·5 to 1·0 gramme), the substance being some of the same
compound that was being made use of for inhalation experiments. In
the case of the white lead it was found essential to mix it with the
animals’ food; they were given white lead in a small amount of their
food, and no further food was given for some little time after the dose
of lead had been swallowed. Low and high solubility glazes were
also made use of for feeding, and as a further experiment alcohol
was given to the animals in addition to the previous course of lead
inhalation or feeding, and the exposure to lead continued after the
alcohol was given. In addition to high solubility glazes, white lead,
and flue dust, a soluble salt of lead was also used, in one series the
salt being the nitrate. 0·1 gramme was given daily; and it is these
two nitrate animals (46 and 47) which showed distinct differences
from the white lead and other feeding experiments. In one case the
lead was given mixed with water, in the other mixed with milk. The
animal which was fed with the nitrate dissolved in water developed
encephalopathy, whereas the one in which the substance was mixed
in milk exhibited no signs, though fed for a similar period. Both the
animals increased in weight, which is an unusual effect in
experimental lead poisoning. The question of the addition of milk,
which apparently prevented the absorption of lead, is of very
considerable importance, as it is highly probable, as has been
pointed out with regard to the precipitation of lead by means of
organic substances, that the albuminoid substances in the milk
precipitate the nitrate already in a state of solution; and it may be
argued from these experiments that mixing the white lead with the
food would tend to prevent the lead having a toxic or deleterious
effect, but even when the lead was given in the form of pills between
meals no poisonous effect was noticed. Further, the quantity of white
lead given was considerable, and it is highly questionable whether
the quantity of lead so taken would be dissolved by the gastric juice
excreted under normal circumstances in its entirety, as a very
considerable quantity would pass onwards through the pylorus
undissolved. Until the lead compound has become soluble it cannot
react with the albuminoid constituent of the food. Ordinary dry white
lead or litharge does not combine directly with albumin.
The majority of the experimental animals showed alteration in
weight. The most important point which is brought out by these
experiments, considering them from the point of view of inhalation, is
the enormous quantity of white lead the “feeding” animals swallowed
without producing any apparent symptoms. The quantities cited are
the amounts given per diem, whereas in the inhalation experiments
the animals were rarely exposed more than three days a week for an
hour at a time (see table, p. 101). The quantity of lead, therefore,
given by the gastro-intestinal canal was at least ten times as much,
in many cases fifteen or twenty times as much, as could be taken by
the other animals via the lung during inhalation, and yet these
animals showed little or no susceptibility to poisoning when fed with
white lead or other lead compounds, unless alcohol was given in
addition.
An examination of the stomach after death showed, in the case of
the alcoholic animals, distinct evidence of gastritis, and there is
some reason to suppose that in such animals a degree of
hyperacidity may have existed, thereby promoting the rate of solution
of the lead.
The increased susceptibility to lead poisoning through the agency
of alcohol is interesting. No. 6 received, in addition to its inhalations
or period of exposure in the dusty air, 50 c.c. of port wine per diem.
Symptoms of lead poisoning appeared a day sooner than in any
other animal, and if we eliminate this experiment, as the dust (flue
dust from blast-furnace) contained also arsenic and antimony, three
days sooner than the litharge animal, and twenty-five days sooner
than the other animals exposed to white lead dust. In addition, this
animal was the only one which actually died during the period of
experiment; all the other animals were killed at the end of two
months and submitted to histological examination; but the animal
which had received alcohol died with symptoms closely simulating
lead encephalopathy in man. The predisposing action of alcohol is
still further emphasized by the subsequent experiments with three
animals exposed to white lead dust; one was exposed thirty-seven
and the other thirty days before symptoms appeared, whereas when
alcohol was given poisoning was apparent within twelve days, and
after only four inhalations.
In the case of animals fed with white lead, one after eight months,
and the other a year and a half, showed no signs of lead poisoning
at all, while the weights remained constant. At the end of this time
alcohol (50 c.c. of port wine) was added to the animals’ diet, and one
month after the addition of alcohol to the diet, the dose of white lead
being continued constant, encephalopathy ensued. In a second case
the animal was started on alcohol in addition to the white lead. In a
month it was showing signs of slight paresis. Again, an animal fed on
a low-solubility frit consisting of ground-up lead silicate, showed no
ill-effects after receiving a daily dose of this compound. At the end of
this time alcohol was added to its diet, and six months later the
animal developed symptoms of cerebral involvement, which
continued at intervals until a fatal attack of encephalopathy at the
end of a year. There is thus definite evidence to show that the
addition of alcohol to the animal’s diet undoubtedly hastened and
determined the appearance of lead poisoning, and this, taken in
conjunction with the inhalation experiments previously cited, is very
strong evidence of the increased susceptibility to lead poisoning
produced by alcohol. This supersensitiveness to lead through the
medium of alcohol is a matter of clinical experience to most persons
who have had experience of industrial lead poisoning, particularly
those who have been engaged in the routine examination of persons
working in factories.
Inoculation Experiments.—In order to control both the feeding
and the inhalation experiments, and more particularly to obtain direct
information of the effect of lead upon the body tissues, resource was
had to the inoculation of the various lead compounds tested—
namely: (1) White lead, (2) litharge, (3) lead frit. These three
compounds are the three types of lead salt which are used in the
Potteries, whilst white lead and litharge are the compounds causing
industrial poisoning in the largest proportion of cases in other
industries. As a further control, the more soluble lead salts were also
made use of—namely, acetate, nitrate, and chloride—mainly for the
purpose of establishing some standard of poisoning both in rate and
dose.
Several rather unexpected results were derived from the
inoculation experiments, which will be referred to.
The method of inoculation was to suspend the lead compound to
be tested in normal saline solution or distilled water. The animal was
then shaved, and the lead compound inoculated into the muscles of
the back. The corrosive action of these lead salts was avoided by
using a considerable quantity of diluent.
Lead frit is a constituent of low-solubility glaze—that is to say, a
glaze which has not more than 5 per cent. soluble lead when
subjected to the standard test of exposing 1 gramme of the glaze to
a litre of 0·04 per cent. hydrochloric acid for an hour at room
temperature. The frit which was the constituent of this glaze is
produced by heating together litharge or lead and silica, the
production being a yellow, hard, glaze-like material looking very
much like sugar-candy. It is not by any means a compound of lead
and silica of simple composition, as different samples show a wide
variation in their lead content; whilst, in addition, the mode of its
formation closely resembles that of an alloy or amalgam, and allows
of the formation of a eutectic entangling in its meshes both of the
constituents of which it is formed, so that a certain amount of free
lead, in addition to the silicates of various descriptions, are present.
At the same time the compound is highly resistant to the action of
mineral acids, and, of course, much more insoluble and refractory
than white lead, litharge, or other lead oxides. The body fluids,
however, particularly the fluids in the subcutaneous and muscular
tissue, definitely exert some action upon this fritted lead, and it was
found experimentally that symptoms of poisoning could be produced
in the experimental animals when even small doses were
administered. A gramme of frit was inoculated, and in all but one
case the animals showed definite signs of lead poisoning, and in two
instances actually died with symptoms of encephalitis.
By washing the frit with distilled water, a slight diminution in the
poisonousness was found, but by washing the frit with two or three
changes of dilute acetic acid (3 per cent.), and then with distilled
water, no pathological results followed inoculation. Water-washing frit
alone definitely reduces the poisonous effect, but not to the same
extent as the preliminary washing with acetic acid. On the other
hand, washing with hot water had a much greater effect than cold-
water washing.
Further evidence given by the inoculation experiments shows the
relationship between the more soluble and the insoluble lead salts.
The dose of acetate required to kill an animal was about 0·1 gramme
of acetate per kilogramme body weight. On the other hand, 0·1
gramme of white lead produced no ill-effects, 0·5 gramme per
kilogramme body weight produced death in about two months. In
addition, those animals suffering from the more acute forms of

PDF Microstates Entropy and Quanta An Introduction To Statistical Mechanics Don Koks Ebook Full Chapter

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

PDF Microstates Entropy and Quanta An Introduction To Statistical Mechanics Don Koks Ebook Full Chapter

Uploaded by

Copyright:

Available Formats

Microstates Entropy and Quanta An

Introduction to Statistical Mechanics

Statistical mechanics : entropy, order parameters, and

An Introduction to Statistical Mechanics and

Statistical Methods An Introduction to Basic

An Introduction To Statistical Learning With

An Introduction to Statistical Methods and Data

Introduction to basic statistics 1 Don Ozisco

Non equilibrium statistical mechanics Prigogine

Introduction to Statistical Methods Design of

Library of Congress Control Number: 2018960736

© Springer Nature Switzerland AG 2018

Another book on introductory statistical mechanics? You might think that

particles in an ideal gas of temperature T as each having, say, translational

Adelaide, Australia Don Koks

1 Preliminary Ideas of Counting, and Some Useful

2 Accessible States and the Fundamental Postulate of

2.2 Energy Spacing of States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

3 The Laws of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

4 The First Law in Detail . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207

5 The Non-Isolated System: the Boltzmann Distribution . . . 275

6 The Motion of Gas Particles, and Transport Processes . . . . 333

6.3 Representative Speeds of Gas Particles . . . . . . . . . . . . . . . . . . . . 346

7 Introductory Quantum Statistics . . . . . . . . . . . . . . . . . . . . . . . . . 385

8 Fermion Statistics in Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445

9 Boson Statistics in Blackbody Radiation . . . . . . . . . . . . . . . . . . 481

9.2.2 Excursus: Thermal Noise in a Resistor, and Some

Chapter 1: Preliminary Ideas of Counting, and Some Useful Mathe-

Chapter 2: Accessible States and the Fundamental Postulate of Sta-

freedom of the particle.) The particle need not be an atom; it

Chapter 3: The Laws of Thermodynamics

ur Unit-length radial vector.

Chapter 4: The Three Interactions of the First Law

γ CP /CV , which also equals CPsp /CVsp and CPmol /CVmol .

Chapter 5: The Non-Isolated System: the Boltzmann Distribution

Chapter 6: The Motion of Gas Particles and Transport Processes

Nvel (v) d3 v Infinitesimal number of particles with velocities in the range

Chapter 7: Introductory Quantum Statistics

n The energy level of a one-dimensional oscillator, and also the

N Total number of quantum particles of all energies (in a later

Chapter 8: Fermion Statistics in Metals

Various parameters are also defined in (8.65).

Chapter 9: Boson Statistics in Blackbody Radiation

Avogadro’s number NA 6.022 ×1023

Proton mass 1.67 ×10−27 kg

Room temperature 298 K (25◦ C)

Mass of a generic air molecule 4.8 ×10−26 kg

Earth gravity 9.8 m/s2

Copper’s molar mass 63.5 g

In which we set the stage for counting the number of

The modern subject of statistical mechanics is built on a single, simple idea:

1.1 The Spreading of an Ink Drop

n molecules of ink N molecules of water

total number of arrangements (n + N )!

We will approximate n! using Stirling’s rule:

and leave a proper discussion of that to Section 1.2. Then,

The number of drops in the bathtub is (n + N )/n = 1 + N/n, so

N volume of tub 1000 mm × 600 mm × 500 mm

Placing these values of N/n and n into (1.3) gives

1.1.1 Identical-Classical Particles

The particles above were distinguishable, and thus able to be counted. In

total number of configurations = (n + N )!

For the identical-classical case, we have