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Quantum Chemistry
ENGEL
A visual, conceptual and contemporary approach to the fascinating
field of Physical Chemistry guides students through core concepts
with visual narratives and connections to cutting-edge applications and Spectroscopy 4e
PHYSICAL CHEMISTRY Quantum

and research.
The fourth edition of Quantum Chemistry & Spectroscopy includes

many changes to the presentation and content at both a global and
chapter level. These updates have been made to enhance the student
learning experience and update the discussion of research areas.
MasteringTM Chemistry, with a new enhanced Pearson eText, has

Thomas Engel
been significantly expanded to include a wealth of new end-of-chapter
problems from the 4th edition, new self-guided, adaptive Dynamic
Study Modules with wrong answer feedback and remediation, and
the new Pearson eText which is mobile friendly.
Chemistry and Spectroscopy 4e

Please visit us at www.pearson.com for more information.
To order any of our products, contact our customer service
department at (800) 824-7799, or (201) 767-5021 outside of
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PHYSICAL CHEMISTRY
Quantum Chemistry
and Spectroscopy
FOURTH EDITION
Thomas Engel
University of Washington
Chapter 15, “Computational Chemistry,”

was contributed by
Warren Hehre
CEO, Wavefunction, Inc.
Chapter 17, “Nuclear Magnetic Resonance Spectroscopy,”

was coauthored by
Alex Angerhofer
University of Florida
A01_ENGE4590_04_SE_FM_i-xvi.indd 1 30/11/17 9:51 AM

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Library of Congress Cataloging-in-Publication Data
Names: Engel, Thomas, 1942- author. | Hehre, Warren, author. | Angerhofer,

Alex, 1957- author. | Engel, Thomas, 1942- Physical chemistry.
Title: Physical chemistry, quantum chemistry, and spectroscopy / Thomas Engel
(University of Washington), Warren Hehre (CEO, Wavefunction, Inc.), Alex
Angerhofer (University of Florida).
Description: Fourth edition. | New York : Pearson Education, Inc., [2019] |
Chapter 15, Computational chemistry, was contributed by Warren Hehre, CEO,
Wavefunction, Inc. Chapter 17, Nuclear magnetic resonance spectroscopy,
was contributed by Alex Angerhofer, University of Florida. | Previous
edition: Physical chemistry / Thomas Engel (Boston : Pearson, 2013). |
Includes index.
Identifiers: LCCN 2017046193 | ISBN 9780134804590
Subjects: LCSH: Chemistry, Physical and theoretical--Textbooks. | Quantum
chemistry--Textbooks. | Spectrum analysis--Textbooks.
Classification: LCC QD453.3 .E55 2019 | DDC 541/.28--dc23
LC record available at https://lccn.loc.gov/2017046193
1 17
ISBN 10: 0-13-480459-7; ISBN 13: 978-0-13-480459-0 (Student edition)

ISBN 10: 0-13-481394-4; ISBN 13: 978-0-13-481394-3 (Books A La Carte edition)

To Walter and Juliane,
my first teachers,
and to Gloria,
Alex,
Gabrielle, and Amelie.

Brief Contents
QUANTUM CHEMISTRY AND SPECTROSCOPY
1 From Classical to Quantum Mechanics 19 11 Quantum States for Many-Electron Atoms

and Atomic Spectroscopy 257
2 The Schrödinger Equation 45
12 The Chemical Bond in Diatomic
3 The Quantum-Mechanical Postulates 67
Molecules 285
4 Applying Quantum-Mechanical Principles
13 Molecular Structure and Energy Levels
to Simple Systems 77
for Polyatomic Molecules 315
5 Applying the Particle in the Box Model
14 Electronic Spectroscopy 349
to Real-World Topics 95
15 Computational Chemistry 377
6 Commuting and Noncommuting Operators
and the Surprising Consequences of 16 Molecular Symmetry and an Introduction
Entanglement 119 to Group Theory 439
7 A Quantum-Mechanical Model for the 17 Nuclear Magnetic Resonance

Vibration and Rotation of Molecules 143 Spectroscopy 467
8 Vibrational and Rotational Spectroscopy APPENDIX A Point Group Character Tables 513
of Diatomic Molecules 171
Credits 521
9 The Hydrogen Atom 209
Index 523
10 Many-Electron Atoms 233
iv

Detailed Contents
QUANTUM CHEMISTRY AND SPECTROSCOPY
Preface ix 3.2 Every Observable Has a Corresponding

Operator 69
Math Essential 1 Units, Significant Figures, and 3.3 The Result of an Individual Measurement 69
Solving End of Chapter Problems 3.4 The Expectation Value 70
Math Essential 2 Differentiation and Integration 3.5 The Evolution in Time of a Quantum-Mechanical
System 73
Math Essential 3 Partial Derivatives
Math Essential 4 Infinite Series 4 Applying Quantum-Mechanical

Principles to Simple Systems 77
1 From Classical to Quantum 4.1 The Free Particle 77
Mechanics 19 4.2 The Case of the Particle in a One-Dimensional
1.1 Why Study Quantum Mechanics? 19 Box 79
1.2 Quantum Mechanics Arose out of the Interplay 4.3 Two- and Three-Dimensional Boxes 83
of Experiments and Theory 20 4.4 Using the Postulates to Understand the Particle
1.3 Blackbody Radiation 21 in the Box and Vice Versa 84
1.4 The Photoelectric Effect 22
1.5 Particles Exhibit Wave-Like Behavior 24 5 Applying the Particle in the Box
1.6 Diffraction by a Double Slit 26 Model to Real-World Topics 95
1.7 Atomic Spectra and the Bohr Model of the 5.1 The Particle in the Finite Depth Box 95
Hydrogen Atom 29 5.2 Differences in Overlap between Core and Valence
Math Essential 5 Differential Equations Electrons 96
5.3 Pi Electrons in Conjugated Molecules Can Be
Math Essential 6 Complex Numbers and Functions Treated as Moving Freely in a Box 97
5.4 Understanding Conductors, Insulators,
2 The Schrödinger Equation 45
and Semiconductors Using the Particle in a
2.1 What Determines If a System Needs to Be Box Model 98
Described Using Quantum Mechanics? 45 5.5 Traveling Waves and Potential Energy
2.2 Classical Waves and the Nondispersive Wave Barriers 100
Equation 49 5.6 Tunneling through a Barrier 103
2.3 Quantum-Mechanical Waves and the Schrödinger 5.7 The Scanning Tunneling Microscope
Equation 54 and the Atomic Force Microscope 104
2.4 Solving the Schrödinger Equation: Operators, 5.8 Tunneling in Chemical Reactions 109
Observables, Eigenfunctions, and Eigenvalues 55
5.9 Quantum Wells and Quantum Dots 110
2.5 The Eigenfunctions of a Quantum-Mechanical
Operator Are Orthogonal 57
2.6 The Eigenfunctions of a Quantum-Mechanical
6 Commuting and Noncommuting
Operator Form a Complete Set 59 Operators and the Surprising
2.7 Summarizing the New Concepts 61 Consequences of
Entanglement 119
3 The Quantum-Mechanical 6.1 Commutation Relations 119
Postulates 67 6.2 The Stern–Gerlach Experiment 121
3.1 The Physical Meaning Associated with the Wave 6.3 The Heisenberg Uncertainty Principle 124
Function is Probability 67
v

vi CONTENTS
6.4 The Heisenberg Uncertainty Principle Expressed 9.5 The Radial Probability Distribution Function 219
in Terms of Standard Deviations 128 9.6 Validity of the Shell Model of an Atom 224
6.5 A Thought Experiment Using a Particle
in a Three-Dimensional Box 130 Math Essential 9 Working with Determinants
6.6 Entangled States, Teleportation, and Quantum
Computers 132 10 Many-Electron Atoms 233
10.1 Helium: The Smallest Many-Electron Atom 233
Math Essential 7 Vectors 10.2 Introducing Electron Spin 235
10.3 Wave Functions Must Reflect the
Math Essential 8 Polar and Spherical Coordinates Indistinguishability of Electrons 236
7 A Quantum-Mechanical Model 10.4 Using the Variational Method to Solve the
Schrödinger Equation 239
for the Vibration and Rotation
10.5 The Hartree–Fock Self-Consistent Field
of Molecules 143 Model 240
7.1 The Classical Harmonic Oscillator 143 10.6 Understanding Trends in the Periodic Table
7.2 Angular Motion and the Classical Rigid Rotor 147 from Hartree–Fock Calculations 247
7.3 The Quantum-Mechanical Harmonic
Oscillator 149 11 Quantum States for Many-
7.4 Quantum-Mechanical Rotation in Two Electron Atoms and Atomic
Dimensions 154
Spectroscopy 257
7.5 Quantum-Mechanical Rotation in Three
Dimensions 157 11.1 Good Quantum Numbers, Terms, Levels,
and States 257
7.6 Quantization of Angular Momentum 159
11.2 The Energy of a Configuration Depends on Both
7.7 Spherical Harmonic Functions 161
Orbital and Spin Angular Momentum 259
7.8 Spatial Quantization 164
11.3 Spin–Orbit Coupling Splits a Term into
Levels 266
8 Vibrational and Rotational 11.4 The Essentials of Atomic Spectroscopy 267
Spectroscopy of Diatomic 11.5 Analytical Techniques Based on Atomic
Molecules 171 Spectroscopy 269
8.1 An Introduction to Spectroscopy 171 11.6 The Doppler Effect 272
8.2 Absorption, Spontaneous Emission, 11.7 The Helium–Neon Laser 273
and Stimulated Emission 174 11.8 Auger Electron Spectroscopy and X-Ray
8.3 An Introduction to Vibrational Photoelectron Spectroscopy 277
Spectroscopy 175
8.4 The Origin of Selection Rules 178 12 The Chemical Bond in Diatomic
8.5 Infrared Absorption Spectroscopy 180 Molecules 285
8.6 Rotational Spectroscopy 184 12.1 Generating Molecular Orbitals from Atomic
8.7 Fourier Transform Infrared Spectroscopy 190 Orbitals 285
8.8 Raman Spectroscopy 194 12.2 The Simplest One-Electron Molecule: H2+ 289
8.9 How Does the Transition Rate between States 12.3 Energy Corresponding to the H2+ Molecular Wave
Depend on Frequency? 196 Functions cg and cu 291
12.4 A Closer Look at the H2+ Molecular Wave
9 The Hydrogen Atom 209 Functions cg and cu 294
12.5 Homonuclear Diatomic Molecules 297
9.1 Formulating the Schrödinger Equation 209
12.6 Electronic Structure of Many-Electron
9.2 Solving the Schrödinger Equation for the
Molecules 299
Hydrogen Atom 210
12.7 Bond Order, Bond Energy, and Bond Length 302
9.3 Eigenvalues and Eigenfunctions for the Total
Energy 211 12.8 Heteronuclear Diatomic Molecules 304
9.4 Hydrogen Atom Orbitals 217 12.9 The Molecular Electrostatic Potential 307

CONTENTS vii
13 Molecular Structure and 15.3 Hartree–Fock Molecular Orbital Theory: A Direct

Descendant of the Schrödinger Equation 382
Energy Levels for Polyatomic
15.4 Properties of Limiting Hartree–Fock Models 384
Molecules 315 15.5 Theoretical Models and Theoretical Model
13.1 Lewis Structures and the VSEPR Model 315 Chemistry 389
13.2 Describing Localized Bonds Using Hybridization 15.6 Moving Beyond Hartree–Fock Theory 390
for Methane, Ethene, and Ethyne 318 15.7 Gaussian Basis Sets 395
13.3 Constructing Hybrid Orbitals for Nonequivalent 15.8 Selection of a Theoretical Model 398
Ligands 321
15.9 Graphical Models 412
13.4 Using Hybridization to Describe Chemical
Bonding 324 15.10 Conclusion 420
13.5 Predicting Molecular Structure Using
Math Essential 10 Working with Matrices
Qualitative Molecular Orbital Theory 326
13.6 How Different Are Localized and Delocalized 16 Molecular Symmetry and an
Bonding Models? 329
Introduction to Group Theory 439
13.7 Molecular Structure and Energy Levels from
Computational Chemistry 332 16.1 Symmetry Elements, Symmetry Operations,
and Point Groups 439
13.8 Qualitative Molecular Orbital Theory for
Conjugated and Aromatic Molecules: 16.2 Assigning Molecules to Point Groups 441
The Hückel Model 334 16.3 The H2O Molecule and the C2v Point Group 443
13.9 From Molecules to Solids 340 16.4 Representations of Symmetry Operators, Bases
13.10 Making Semiconductors Conductive at Room for Representations, and the Character Table 448
Temperature 342 16.5 The Dimension of a Representation 450
16.6 Using the C2v Representations to Construct
14 Electronic Spectroscopy 349 Molecular Orbitals for H2O 454
14.1 The Energy of Electronic Transitions 349 16.7 Symmetries of the Normal Modes of Vibration
of Molecules 456
14.2 Molecular Term Symbols 350
16.8 Selection Rules and Infrared versus Raman
14.3 Transitions between Electronic States Activity 460
of Diatomic Molecules 353
16.9 Using the Projection Operator Method to
14.4 The Vibrational Fine Structure of Electronic Generate MOs That Are Bases for Irreducible
Transitions in Diatomic Molecules 354 Representations 461
14.5 UV-Visible Light Absorption in Polyatomic
Molecules 356
17 Nuclear Magnetic Resonance
14.6 Transitions among the Ground and Excited
States 359 Spectroscopy 467
14.7 Singlet–Singlet Transitions: Absorption 17.1 Intrinsic Nuclear Angular Momentum
and Fluorescence 360 and Magnetic Moment 467
14.8 Intersystem Crossing and Phosphorescence 361 17.2 The Nuclear Zeeman Effect 470
14.9 Fluorescence Spectroscopy and Analytical 17.3 The Chemical Shift 473
Chemistry 362 17.4 Spin–Spin Coupling and Multiplet Splittings 476
14.10 Ultraviolet Photoelectron Spectroscopy 363 17.5 Spin Dynamics 484
14.11 Single-Molecule Spectroscopy 365 17.6 Pulsed NMR Spectroscopy 491
14.12 Fluorescent Resonance Energy Transfer 366 17.7 Two-Dimensional NMR 498
Assigning + and - to g Terms of Diatomic

14.13 Linear and Circular Dichroism 368 17.8 Solid-State NMR 503
14.14 17.9 Dynamic Nuclear Polarization 505
Molecules 371 17.10 Magnetic Resonance Imaging 507
15 Computational Chemistry 377 APPENDIX A Point Group Character Tables 513

15.1 The Promise of Computational Chemistry 377 Credits 521
15.2 Potential Energy Surfaces 378 Index 523

About the Author
THOMAS ENGEL taught chemistry at the University of Washington for more than
20 years, where he is currently professor emeritus of chemistry. Professor Engel
received his bachelor’s and master’s degrees in chemistry from the Johns Hopkins
University and his Ph.D. in chemistry from the University of Chicago. He then spent
11 years as a researcher in Germany and Switzerland, during which time he received
the Dr. rer. nat. habil. degree from the Ludwig Maximilians University in Munich. In
1980, he left the IBM research laboratory in Zurich to become a faculty member at
the University of Washington.
Professor Engel has published more than 80 articles and book chapters in the area
of surface chemistry. He has received the Surface Chemistry or Colloids Award from
the American Chemical Society and a Senior Humboldt Research Award from the
Alexander von Humboldt Foundation. Other than this textbook, his current primary sci-
ence interests are in energy policy and energy conservation. He serves on the citizen’s
advisory board of his local electrical utility, and his energy-efficient house could be
heated in winter using only a hand-held hair dryer. He currently drives a hybrid vehicle
and plans to transition to an electric vehicle soon to further reduce his carbon footprint.
viii

Preface
The fourth edition of Quantum Chemistry and Spectroscopy includes many changes to
the presentation and content at both a global and chapter level. These updates have been
made to enhance the student learning experience and update the discussion of research
areas. At the global level, changes that readers will see throughout the textbook include:
• Review of relevant mathematics skills. One of the primary reasons that students
experience physical chemistry as a challenging course is that they find it difficult to
transfer skills previously acquired in a mathematics course to their physical chemis-
try course. To address this issue, contents of the third edition Math Supplement have
been expanded and split into 11 two- to five-page Math Essentials, which are insert-
ed at appropriate places throughout this book, as well as in the companion volume
Thermodynamics, Statistical Thermodynamics, and Kinetics, just before the math
skills are required. Our intent in doing so is to provide “just-in-time” math help and
to enable students to refresh math skills specifically needed in the following chapter.
• Concept and Connection. A new Concept and Connection feature has been
added to each chapter to present students with a quick visual summary of the most
important ideas within the chapter. In each chapter, approximately 10–15 of the
most important concepts and/or connections are highlighted in the margins.
• End-of-Chapter Problems. Numerical Problems are now organized by section
number within chapters to make it easier for instructors to create assignments for
specific parts of each chapter. Furthermore, a number of new Conceptual Questions
and Numerical Problems have been added to the book. Numerical Problems from
the previous edition have been revised.
• Introductory chapter materials. Introductory paragraphs of all chapters have
been replaced by a set of three questions plus responses to those questions. This new
feature makes the importance of the chapter clear to students at the outset.
• Figures. All figures have been revised to improve clarity. Also, for many figures
additional annotation has been included to help tie concepts to the visual program.
• Key Equations. An end-of-chapter table that summarizes Key Equations has been
added to allow students to focus on the most important of the many equations in
each chapter. Equations in this table are set in red type where they appear in the
body of the chapter.
• Further Reading. A section on Further Reading has been added to each chapter
to provide references for students and instructors who would like a deeper under-
standing of various aspects of the chapter material.
• Guided Practice and Interactivity
TM
° Mastering Chemistry, with a new enhanced eBook, has been significantly
expanded to include a wealth of new end-of-chapter problems from the fourth
edition, new self-guided, adaptive Dynamic Study Modules with wrong answer
feedback and remediation, and the new Pearson eBook, which is mobile friendly.
Students who solve homework problems using MasteringTM Chemistry obtain
immediate feedback, which greatly enhances learning associated with solving
homework problems. This platform can also be used for pre-class reading quiz-
zes linked directly to the eText that are useful in ensuring students remain cur-
rent in their studies and in flipping the classroom.
° NEW! Pearson eText, optimized for mobile gives students access to their
textbook anytime, anywhere.
■
Pearson eText mobile app offers offline access and can be downloaded for
most iOS and Android phones/tablets from the Apple App Store or Google Play
■
Configurable reading settings, including resizable type and night-reading mode
■
Instructor and student note-taking, highlighting, bookmarking, and search
functionalities
ix

x PREFACE
° NEW! 66 Dynamic Study Modules help students study effectively on their own
by continuously assessing their activity and performance in real time.
° Students complete a set of questions with a unique answer format that also asks
them to indicate their confidence level. Questions repeat until the student can
answer them all correctly and confidently. These are available as graded assign-
ments prior to class and are accessible on smartphones, tablets, and computers.
° Topics include key math skills, as well as a refresher of general chemistry concepts
such as understanding matter, chemical reactions, and the periodic table and
atomic structure. Topics can be added or removed to match your coverage.
In terms of chapter and section content, many changes were made. The most significant
of these changes are:
• Chapter 17, on nuclear magnetic resonance (NMR), has been completely rewritten
and expanded with the significant contribution of co-author Alex Angerhofer. This
chapter now covers the nuclear Overhauser effect and dynamic nuclear polarization,
and presents an extensive discussion of how two-dimensional NMR techniques are
used to determine the structure of macromolecules in solution.
• Section 5.4 has been revised and expanded to better explain conduction in solids.
• Section 6.6 has been extensively revised to take advances in quantum computing
into account.
• Section 8.4, on the origin of selection rules, has been revised and expanded to
enhance student learning.
• Sections 14.5, 14.7, and 14.10 have been extensively revised and reformulated to
relate electronic transitions to molecular orbitals of the initial and final states.
• Section 14.12 has been revised to reflect advances in the application of FRET to
problems of chemical interest.
For those not familiar with the third edition of Quantum Chemistry and Spectroscopy, our
approach to teaching physical chemistry begins with our target audience, undergraduate
students majoring in chemistry, biochemistry, and chemical engineering, as well as many
students majoring in the atmospheric sciences and the biological sciences. The following
objectives outline our approach to teaching physical chemistry.
• Focus on teaching core concepts. The central principles of physical chemistry
are explored by focusing on core ideas and then extending these ideas to a variety
of problems. The goal is to build a solid foundation of student understanding in a
limited number of areas rather than to provide a condensed encyclopedia of physical
chemistry. We believe this approach teaches students how to learn and enables them
to apply their newly acquired skills to master related fields.
• Illustrate the relevance of physical chemistry to the world around us. Physical
chemistry becomes more relevant to a student if it is connected to the world around
us. Therefore, example problems and specific topics are tied together to help the
student develop this connection. For example, topics such as scanning tunneling
microscopy, quantum dots, and quantum computing are discussed and illustrated
with examples from the recent chemistry literature. Every attempt is made to con-
nect fundamental ideas to applications that could be of interest to the student.
• Link the macroscopic and atomic-level worlds. The manifestation of quantum
mechanics in the macroscopic world is illustrated by discussions of the band struc-
ture of solids, atomic force microscopy, quantum mechanical calculations of ther-
modynamic state functions, and NMR imaging.
• Present exciting new science in the field of physical chemistry. Physical chem-
istry lies at the forefront of many emerging areas of modern chemical research.
Heterogeneous catalysis has benefited greatly from mechanistic studies carried
out using the techniques of modern surface science. Quantum computing, using
the principles of superposition and entanglement, is on the verge of being a viable
technology. The role of physical chemistry in these and other emerging areas is
highlighted throughout the text.

PREFACE xi
• Provide a versatile online homework program with tutorials. Students who

submit homework problems using MasteringTM Chemistry obtain immediate feed-
back, a feature that greatly enhances learning. Also, tutorials with wrong answer
feedback offer students a self-paced learning environment.
• Use web-based simulations to illustrate the concepts being explored and avoid
math overload. Mathematics is central to physical chemistry; however, the math-
ematics can distract the student from “seeing” the underlying concepts. To circum-
vent this problem, web-based simulations have been incorporated as end-of-chapter
problems in several chapters so that the student can focus on the science and avoid
a math overload. These web-based simulations can also be used by instructors dur-
ing lecture. An important feature of the simulations is that each problem has been
designed as an assignable exercise with a printable answer sheet that the student can
submit to the instructor. Simulations, animations, and homework problem work-
sheets can be accessed at www.pearsonhighered.com/advchemistry.
Effective use of Quantum Chemistry and Spectroscopy does not require proceeding
sequentially through the chapters or including all sections. Some topics are discussed
in supplemental sections, which can be omitted if they are not viewed as essential to
the course. Also, many sections are sufficiently self-contained that they can be readily
omitted if they do not serve the needs of the instructor and students. This textbook is
constructed to be flexible to your needs. I welcome the comments of both students and
instructors on how the material was used and how the presentation can be improved.
Thomas Engel
University of Washington
ACKNOWLEDGMENTS
Many individuals have helped me to bring the text into its current form. Students have
provided me with feedback directly and through the questions they have asked, which has
helped me to understand how they learn. Many colleagues, including Peter Armentrout,
Doug Doren, Gary Drobny, Alex Engel, Graeme Henkelman, Lewis Johnson, Tom
Pratum, Bill Reinhardt, Peter Rosky, George Schatz, Michael Schick, Gabrielle Varani,
and especially Wes Borden and Bruce Robinson, have been invaluable in advising me.
I am also fortunate to have access to some end-of-chapter problems that were originally
presented in Physical Chemistry, 3rd edition, by Joseph H. Noggle and in Physical
Chemistry, 3rd edition, by Gilbert W. Castellan. The reviewers, who are listed sepa-
rately, have made many suggestions for improvement, for which I am very grateful.
All those involved in the production process have helped to make this book a reality
through their efforts. Special thanks are due to Jim Smith, who guided the first edition,
to the current editor Jeanne Zalesky, to the developmental editor Spencer Cotkin, and to
Jennifer Hart and Beth Sweeten at Pearson, who have led the production process.

xii PREFACE
4TH EDITION MANUSCRIPT REVIEWERS

David Coker, George Papadantonakis,
Boston University University of Illinois, Chicago
Yingbin Ge, Stefan Stoll,
Central Washington University University of Washington
Eric Gislason, Liliya Yatsunyk,
University of Illinois, Chicago Swarthmore College
Nathan Hammer,
University of Mississippi
4TH EDITION ACCURACY REVIEWERS

Garry Crosson, Andrea Munro,
University of Dayton Pacific Lutheran University
Benjamin Huddle,
Roanoke College
4TH EDITION PRESCRIPTIVE REVIEWERS

Joseph Alia, Richard Mabbs,
University of Minnesota, Morris Washington University, St. Louis
Herbert Axelrod, Vicki Moravec,
California State University, Fullerton Trine University
Timothy Brewer, Andrew Petit,
Eastern Michigan University California State University, Fullerton
Paul Cooper, Richard Schwenz,
George Mason University University of Northern Colorado
Bridget DePrince, Ronald Terry,
Florida State University Western Illinois University
Patrick Fleming, Dunwei Wang,
California State University, East Bay Boston College
Gerard Harbison,
University of Nebraska, Lincoln
PREVIOUS EDITION REVIEWERS

Alexander Angerhofer, Cynthia Hartzell,
University of Florida Northern Arizona University
Clayton Baum, Geoffrey Hutchinson,
Florida Institute of Technology University of Pittsburgh
Martha Bruch, John M. Jean,
State University of New York Regis University
at Oswego Martina Kaledin,
David L. Cedeño, Kennesaw State University
Illinois State University George Kaminski,
Rosemarie Chinni, Worcester Polytechnic Institute
Alvernia College Daniel Lawson,
Allen Clabo, University of Michigan, Dearborn
Francis Marion University William Lester,
Lorrie Comeford, University of California, Berkeley
Salem State College Dmitrii E. Makarov,
Stephen Cooke, University of Texas at Austin
University of North Texas Herve Marand,
Douglas English, Virginia Polytechnic Institute and
University of Maryland, College Park State University
Sophya Garashchuk, Thomas Mason,
University of South Carolina University of California, Los Angeles
Leon Gerber, Jennifer Mihalik,
St. John’s University University of Wisconsin, Oshkosh
Nathan Hammer, Enrique Peacock-López,
The University of Mississippi Williams College

A Visual, Conceptual, and Contemporary
Approach to Physical Chemistry

A Visual, Conceptual, and Contemporary
Approach to Physical Chemistry
NEW! Math Essentials provide a review of

relevant math skills, offer “just in time” math
help, and enable students to refresh math skills
specifically needed in the chapter that follows.
UPDATED! Introductory paragraphs of all chapters

have been replaced by a set of three questions plus
responses to those questions making the relevance
of the chapter clear at the outset.
C H A P T E R
6
Commuting and 6.1
6.2
Commutation Relations
The Stern–Gerlach Experiment
Noncommuting Operators 6.3 The Heisenberg Uncertainty

Principle
and the Surprising

6.4 (Supplemental Section) The
Heisenberg Uncertainty Principle
Expressed in Terms of Standard
Consequences of 6.5
Deviations
(Supplemental Section)
Entanglement
A Thought Experiment Using a
Particle in a Three-Dimensional
Box
6.6 (Supplemental Section)
Entangled States, Teleportation,
and Quantum Computers
WHY is this material important?
The measurement process is different for a quantum-mechanical system than for a
classical system. For a classical system, all observables can be measured simultane-
ously, and the precision and accuracy of the measurement is limited only by the
instruments used to make the measurement. For a quantum-mechanical system, some
observables can be measured simultaneously and exactly, whereas an uncertainty
relation limits the degree to which other observables can be known simultaneously
and exactly.
WHAT are the most important concepts and results?

Measurements carried out on a system in a superposition state change the state of the
system. Two observables can be measured simultaneously and exactly only if their
corresponding operators commute. Two particles can be entangled, after which their
properties are no longer independent of one another. Entanglement is the basis of both
teleportation and quantum computing.
WHAT would be helpful for you to review for this chapter?

It would be helpful to review the material on operators in Chapter 2.
NEW! Concept and Connection features
6.1 COMMUTATION RELATIONS in each chapter present students with quick
In classical mechanics, a system can in principle be described completely. For instance,
the position, momentum, kinetic energy, and potential energy of a mass falling in a
Concept
visual summaries of the core concepts within
gravitational field can be determined simultaneously at any point on its trajectory. The
uncertainty in the measurements is only limited by the capabilities of the measurement
technique. The values of all of these observables (and many more) can be known simul-
For a quantum mechanical system,
it is not generally the case that the the chapter, highlighting key take aways and
values of all observables can be
providing students with an easy way to review
taneously. This is not generally true for a quantum-mechanical system. In the quantum
world, in some cases two observables can be known simultaneously with high accuracy. known simultaneously.
However, in other cases, two observables have a fundamental uncertainty that cannot be
eliminated through any measurement techniques. Nevertheless, as will be shown later,
105
the material.
UPDATED! All figures have been

Figure 8.15
revised to improve clarity and for
P
A P–V–T phase diagram for a substance
m Solid
P that expands upon melting. The indi-
many figures, additional annotation Critical
Solid–Liquid
cated processes are discussed in the text.
has been included to help tie concepts point

Liquid
f
to the visual program.
uid
Solid Critical
T
Liq
Gas point
m
a q Liq
l k 0 Ga uid
g s
Liquid So
id
lid Gas
Critical
Solid–Liqu
–G
Triple point f as
point Solid
d
Pressure
b c Liq
Ga uid e
a s
Tri
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p le as
p Lin
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T1 tur
era
mp
Te

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178 CHAPTER 6 Chemical Equilibrium
178 CHAPTER 6 Chemical Equilibrium

Figure 6.8 N(g) 1 3H(g)
Enthalpy diagram for the reaction
mechanism in the synthesis of ammonia.
314 3 103 J
Figure 6.8 N(g) 1 3H(g)
See Equations (6.91) through (6.95). The
successive steps in the reaction proceed NH(g) 1 2H(g)
Enthalpy diagram for the reaction from left to right in the diagram.
mechanism in the synthesis of ammonia.
See Equations (6.91) through (6.95). The 314 3 103 J 1124 3 103 J
390 3 103 J

NH2(g) 1 H(g)
from left to right in the diagram.

466 3 103 J
390 3 103 J
1124 3 103 J 1
2 N2(g) 1 3
2 H2(g) 245.9 3 103 J
NH3(g)
NH2(g) 1 H(g)
Progress of reaction
synthesis reaction, such a route is a heterogeneous catalytic reaction, using iron as a

catalyst. The mechanism for this path between reactants and products is
466 3 103 J
N21g2 + □ S N21a2 (6.96)
N21a2 + □ S 2N1a2 (6.97)
1
2 N2(g) 1 3
2 H2(g) 245.9 3 103 J H21g2 + 2□ S 2H1a2 (6.98)
NH3(g) N1a2 + H1a2 S NH1a2 + □ (6.99)
NH1a2 + H1a2 S NH21a2 + □ (6.100)
Progress of reaction NH21a2 + H1a2 S NH31a2 + □ (6.101)
NH31a2 S NH31g2 + □ (6.102)
synthesis reaction, such a route is a heterogeneous catalytic reaction, using iron as a The symbol □ denotes an ensemble of neighboring Fe atoms, also called surface sites, which
are capable of forming a chemical bond with the indicated entities. The designation (a)
catalyst. The mechanism for this path between reactants and products is indicates that the chemical species is adsorbed (chemically bonded) to a surface site.
The enthalpy change for the overall reaction N21g2 + 3>2 H21g2 S NH31g2 is
N21g2 + □ S N21a2 (6.96) the same for the mechanisms in Equations (6.91) through (6.95) and (6.96) through
(6.102) because H is a state function. This is a characteristic of a catalytic reaction. A
catalyst can affect the rate of the forward and backward reaction but not the position
N21a2 + □ S 2N1a2 (6.97) of equilibrium in a reaction system. The enthalpy diagram in Figure 6.9 shows that the
H21g2 + 2□ S 2H1a2 (6.98) Homogeneous gas-phase reactions

N(g) 1 3H(g)
N1a2 + H1a2 S NH1a2 + □ (6.99) 314 3 103 J
NH1a2 + H1a2 S NH21a2 + □

NH(g) 1 2H(g)
(6.100)
1124 3 103 J 390 3 103 J
NH21a2 + H1a2 S NH31a2 + □ (6.101) Figure 6.9
Enthalpy diagram for the homogeneous
NH (g) 1 H(g)
2
gas-phase and heterogeneous catalytic

NH31a2 S NH31g2 + □ (6.102) reactions for the ammonia synthesis
1 3
2 N2(g) 1 2 H2(g) 466 3 103 J
NH3(g)
reaction. The activation barriers for the 0

individual steps in the surface reaction 245.9 3 103 J
The symbol □ denotes an ensemble of neighboring Fe atoms, also called surface sites, which are shown. The successive steps in the Progress of reaction
Heterogeneous catalytic reactions
are capable of forming a chemical bond with the indicated entities. The designation (a) reaction proceed from left to right in the
diagram. See the reference to G. Ertl in
NH2(a) 1 H(a)
indicates that the chemical species is adsorbed (chemically bonded) to a surface site. Further Reading for more details. 1 3
2 N2(a) 1 2 H2(a) NH3(g)
245.9 3 103 J
Adapted from G. Ertl, Catalysis NH3(a)
The enthalpy change for the overall reaction N21g2 + 3>2 H21g2 S NH31g2 is Reviews—Science and Engineering Rate-limiting step NH(a) 1 2H(a)
N(a) 1 3H(a)
the same for the mechanisms in Equations (6.91) through (6.95) and (6.96) through 21 (1980): 201–223.

of equilibrium in a reaction system. The enthalpy diagram in Figure 6.9 shows that the M06_ENGE4583_04_SE_C06_147-188.indd 178 02/08/17 5:31 PM
Homogeneous gas-phase reactions

N(g) 1 3H(g)
314 3 103 J
NH(g) 1 2H(g)
1124 3 10 3J 390 3 103 J

Figure 6.9
2 NH (g) 1 H(g)
gas-phase and heterogeneous catalytic NH3(g)
1 3
2 N2(g) 1 2 H2(g) 466 3 103 J
reactions for the ammonia synthesis
are shown. The successive steps in the Progress of reaction
reaction proceed from left to right in the Heterogeneous catalytic reactions
diagram. See the reference to G. Ertl in 178 CHAPTER 6 Chemical Equilibrium
NH2(a) 1 H(a) 245.9 3 103 J
Further Reading for more details. 1 3
2 N2(a) 1 2 H2(a) NH3(g)
Adapted from G. Ertl, Catalysis NH3(a) Figure 6.8 N(g) 1 3H(g)
Rate-limiting step NH(a) 1 2H(a) Enthalpy diagram for the reaction
Reviews—Science and Engineering
21 (1980): 201–223. N(a) 1 3H(a) mechanism in the synthesis of ammonia.
See Equations (6.91) through (6.95). The 314 3 103 J
from left to right in the diagram.
390 3 103 J
1124 3 103 J
NH2(g) 1 H(g)
M06_ENGE4583_04_SE_C06_147-188.indd 178 02/08/17 5:31 PM
466 3 103 J
1
2 N2(g) 1 3
2 H2(g) 245.9 3 103 J
NH3(g)
Progress of reaction
synthesis reaction, such a route is a heterogeneous catalytic reaction, using iron as a

catalyst. The mechanism for this path between reactants and products is
N21g2 + □ S N21a2 (6.96)

N21a2 + □ S 2N1a2 (6.97)
H21g2 + 2□ S 2H1a2 (6.98)
N1a2 + H1a2 S NH1a2 + □ (6.99)
NH1a2 + H1a2 S NH21a2 + □ (6.100)
NH21a2 + H1a2 S NH31a2 + □ (6.101)
NH31a2 S NH31g2 + □ (6.102)
The symbol □ denotes an ensemble of neighboring Fe atoms, also called surface sites, which
are capable of forming a chemical bond with the indicated entities. The designation (a)
indicates that the chemical species is adsorbed (chemically bonded) to a surface site.
The enthalpy change for the overall reaction N21g2 + 3>2 H21g2 S NH31g2 is
the same for the mechanisms in Equations (6.91) through (6.95) and (6.96) through
of equilibrium in a reaction system. The enthalpy diagram in Figure 6.9 shows that the
Homogeneous gas-phase reactions

N(g) 1 3H(g)
314 3 103 J
NH(g) 1 2H(g)
1124 3 103 J 390 3 103 J

Figure 6.9
NH (g) 1 H(g)
2
gas-phase and heterogeneous catalytic NH3(g)
1
2 N2(g) 1 2 H2(g)
3
reactions for the ammonia synthesis 466 3 103 J
are shown. The successive steps in the Progress of reaction
reaction proceed from left to right in the Heterogeneous catalytic reactions
diagram. See the reference to G. Ertl in
NH2(a) 1 H(a) 245.9 3 103 J
Further Reading for more details. 1 3
2 N2(a) 1 2 H2(a) NH3(g)
Adapted from G. Ertl, Catalysis NH3(a)
Rate-limiting step NH(a) 1 2H(a)
Reviews—Science and Engineering
21 (1980): 201–223. N(a) 1 3H(a)
M06_ENGE4583_04_SE_C06_147-188.indd 178 02/08/17 5:31 PM

MATH ESSENTIAL 1:
Units, Significant Figures, and
Solving End of Chapter Problems
ME1.1 UNITS
ME1.1 Units
ME1.2 Uncertainty and Significant
Figures
Quantities of interest in physical chemistry such as pressure, volume, or temperature
are characterized by their magnitude and their units. In this textbook, we use the SI ME1.3 Solving End-of-Chapter
(from the French Le Système international d'unités) system of units. All physical quan- Problems
tities can be defined in terms of the seven base units listed in Table ME1.1. For more
details, see http://physics.nist.gov/cuu/Units/units.html. The definition of temperature
is based on the coexistence of the solid, gaseous, and liquid phases of water at a pres-
sure of 1 bar.
TABLE ME1.1 Base SI Units

Base Unit Unit Definition of Unit
Unit of length meter (m) The meter is the length of the path traveled by light in vacuum during a time
interval of 1>299,792,458 of a second.
Unit of mass kilogram (kg) The kilogram is the unit of mass; it is equal to the mass of the platinum iridium
international prototype of the kilogram kept at the International Bureau of
Weights and Measures.
Unit of time second (s) The second is the duration of 9,192,631,770 periods of the radiation corre-
sponding to the transition between the two hyperfine levels of the ground state
of the cesium 133 atom.
Unit of electric current ampere (A) The ampere is the constant current that, if maintained in two straight parallel
conductors of infinite length, is of negligible circular cross section, and if placed
1 meter apart in a vacuum would produce between these conductors a force
equal to 2 * 10-7 kg m s-2 per meter of length. In this definition, 2 is an
exact number.
Unit of thermodynamic kelvin (K) The Kelvin is the unit of thermodynamic temperature. It is the fraction
temperature 1>273.16 of the thermodynamic temperature of the triple point of water.
Unit of amount of substance mole (mol) The mole is the amount of substance of a system that contains as many elemen-
tary entities as there are atoms in 0.012 kilogram of carbon 12 where 0.012 is
an exact number. When the mole is used, the elementary entities must be speci-
fied and may be atoms, molecules, ions, electrons, other particles, or specified
groups of such particles.
Unit of luminous intensity candela (cd) The candela is the luminous intensity, in a given direction, of a source that
emits monochromatic radiation of frequency 540. * 1012 hertz and that has a
radiant intensity in that direction of 1>683 watt per steradian.
Quantities of interest other than the seven base quantities can be expressed in terms
of the units meter, kilogram, second, ampere, kelvin, mole, and candela. The most im-
portant of these derived units, some of which have special names as indicated, are listed
in Table ME1.2. A more inclusive list of derived units can be found at http://physics
.nist.gov/cuu/Units/units.html.
M01_ENGE4590_04_SE_ME1_001-004.indd 1 28/09/17 2:10 PM

2 MATH ESSENTIAL 1 Units, Significant Figures, and Solving End of Chapter Problems
TABLE ME1.2 Derived Units

Unit Definition Relation to Base Units Special Name Abbreviation
2
Area Size of a surface m m2
Volume Amount of three-dimensional space an object m3 m3
occupies
Velocity Measure of the rate of motion m s-1 m s-1
Acceleration Rate of change of velocity m s-2 m s-2
-1
Linear Product of mass and linear velocity of an object kg m s kg m s-1
momentum
Angular Product of the moment of inertia of a body kg m2 s-1 kg m2 s-1
momentum about an axis and its angular velocity with
respect to the same axis
Force Any interaction that, when unopposed, will kg m s-2 newton N
change the motion of an object
Pressure Force acting per unit area kg m-1 s-2 pascal Pa
N m-2
Work Product of force on an object and movement kg m2 s-2 joule J
along the direction of the force
Kinetic energy Energy an object possesses because of its kg m2 s-2 joule J
motion
Potential energy Energy an object possesses because of its kg m2 s-2 joule J
position or condition
Power Rate at which energy is produced or kg m2 s-3 watt W
consumed
Mass density Mass per unit volume kg m-3 kg m-3
Radian Angle at the center of a circle whose arc is m>m = 1 m>m = 1
equal in length to the radius
Steradian Angle at the center of a sphere subtended by m2 >m2 = 1 m2 >m2 = 1
a part of the surface equal in area to the square
of the radius
Frequency Number of repeat units of a wave per unit time s-1 hertz Hz
Electrical charge Physical property of matter that causes it to As coulomb C
experience an electrostatic force
Electrical potential Work done in moving a unit positive charge kg m2 s-3 >A volt V
from infinity to that point W>A
Electrical resistance Ratio of the voltage to the electric current that kg m2 s-3 >A2 W>A2 ohm Ω
flows through a conductive material
If SI units are used throughout the calculation of a quantity, the result will have
SI units. For example, consider a unit analysis of the electrostatic force between two
charges:
q1q2 C2 A2 s2
F = = =
8pe0r 2 8p * kg -1s4A2 m-3 * m2 8p * kg -1s4A2 m-3 * m2
1 1
= kg m s-2 = N
8p 8p
Therefore, in carrying out a calculation, it is only necessary to make sure that all quan-
tities are expressed in SI units rather than carrying out a detailed unit analysis of the
entire calculation.

ME1.3 Solving End-of-Chapter Problems 3
ME1.2 UNCERTAINTY AND SIGNIFICANT

FIGURES
In carrying out a calculation, it is important to take into account the uncertainty of
the individual quantities that go into the calculation. The uncertainty is indicated by
the number of significant figures. For example, the mass 1.356 g has four significant
figures. The mass 0.003 g has one significant figure, and the mass 0.01200 g has four
significant figures. By convention, the uncertainty of a number is {1 in the rightmost
digit. A zero at the end of a number that is not to the right of a decimal point is not
significant. For example, 150 has two significant figures, but 150. has three significant
figures. Some numbers are exact and have no uncertainty. For example, 1.00 * 106
has three significant figures because the 10 and 6 are exact numbers. By definition, the
mass of one atom of 12C is exactly 12 atomic mass units.
If a calculation involves quantities with a different number of significant figures,
the following rules regarding the number of significant figures in the result apply:
• In addition and subtraction, the result has the number of digits to the right of the
decimal point corresponding to the number that has the smallest number of dig-
its to the right of the decimal point. For example 101 + 24.56 = 126 and
0.523 + 0.10 = 0.62.
• In multiplication or division, the result has the number of significant figures cor-
responding to the number with the smallest number of significant figures. For
example, 3.0 * 16.00 = 48 and 0.05 * 100. = 5.
It is good practice to carry forward a sufficiently large number of significant figures in
different parts of the calculation and to round off to the appropriate number of signifi-
cant figures at the end.
ME1.3 SOLVING END-OF-CHAPTER PROBLEMS

Because calculations in physical chemistry often involve multiple inputs, it is useful to
carry out calculations in a manner that they can be reviewed and easily corrected. For
example, the input and output for the calculation of the pressure exerted by gaseous
benzene with a molar volume of 2.00 L at a temperature of 595 K using the Redlich–
RT a 1
Kwong equation of state P = - in Mathematica is shown
Vm - b 2T Vm1Vm + b2
below. The statement in the first line clears the previous values of all listed quantities,
and the semicolon after each input value suppresses its appearance in the output.
In[36]:= Clear[r, t, vm, a, b, prk]
r = 8.314 * 10^ -2;
t = 595;
vm = 2.00;
a = 452;
b = .08271;
rt a 1
prk = -
vm - b 2t vm(vm + b)
out[42]= 21.3526
Invoking the rules for significant figures, the final answer is P = 21.4 bar.
The same problem can be solved using Microsoft Excel as shown in the following
table.
A B C D E F
1 R T Vm a b =((A2*B2)/(C2-E2))-(D2/SQRT(B2))*(1/(C2*(C2+E2)))
2 0.08314 595 2 452 0.08271 21.35257941

This page intentionally left blank
MATH ESSENTIAL 2:
Differentiation and Integration
Differential and integral calculus is used extensively in physical chemistry. In this unit ME2.1 The Definition and Properties
we review the most relevant aspects of calculus needed to understand the chapter dis- of a Function
cussions and to solve the end-of-chapter problems. ME2.2 The First Derivative
of a Function
ME2.1 THE DEFINITION AND PROPERTIES

ME2.3 The Chain Rule
ME2.4 The Sum and Product Rules
OF A FUNCTION ME2.5 The Reciprocal Rule and the
Quotient Rule
A function ƒ is a rule that generates a value y from the value of a variable x. Mathemati-
cally, we write this as y = ƒ1x2. The set of values x over which ƒ is defined is the do- ME2.6 Higher-Order Derivatives:
main of the function. Single-valued functions have a single value of y for a given value Maxima, Minima, and
of x. Most functions that we will deal with in physical chemistry are single valued. Inflection Points
However, inverse trigonometric functions and 1 are examples of common functions ME2.7 Definite and Indefinite
that are multivalued. A function is continuous if it satisfies these three conditions: Integrals
ƒ1x2 is defined at a
lim ƒ1x2 exists
xSa
lim ƒ1x2 = ƒ1a2 (ME2.1)
xSa
ME2.2 THE FIRST DERIVATIVE OF A FUNCTION

The first derivative of a function has as its physical interpretation the slope of the func- f(x)
tion evaluated at the point of interest. In order for the first derivative to exist at a f(x)5x2 20
point a, the function must be continuous at x = a, and the slope of the function at
x = a must be the same when approaching a from x 6 a and x 7 a. For example, the
10
slope of the function y = x 2 at the point x = 1.5 is indicated by the line tangent to the
curve shown in Figure ME2.1.
Mathematically, the first derivative of a function ƒ1x2 is denoted dƒ1x2>dx. It is
24 22 2 4 x
defined by
dƒ1x2 ƒ1x + h2 - ƒ1x2
= lim (ME2.2) 210
dx hS0 h
The symbol ƒ′1x2 is often used in place of dƒ1x2>dx. For the function of interest,
Figure ME2.1
dƒ1x2 1x + h22 - 1x22 2hx + h2 The function y = x2 plotted as a func-
= lim = lim = lim 2x + h = 2x (ME2.3)
dx hS0 h hS0 h hS0 tion of x. The dashed line is the tangent to
the curve at x = 1.5.
In order for dƒ1x2>dx to be defined over an interval in x, ƒ1x2 must be continuous over
the interval. Next, we present rules for differentiating simple functions. Some of these
functions and their derivatives are as follows:
d1ax n2
= anx n - 1, where a is a constant and n is any real number (ME2.4)
dx
d1aex2
= aex, where a is a constant (ME2.5)
dx
d ln x 1
= (ME2.6)
dx x
5

6 MATH ESSENTIAL 2 Differentiation and Integration
d1a sin x2
= a cos x, where a is a constant (ME2.7)
dx
d1a cos x2
= -a sin x, where a is a constant (ME2.8)
dx
ME2.3 THE CHAIN RULE

In this section, we deal with the differentiation of more complicated functions. Suppose
that y = ƒ1u2 and u = g1x2. From the previous section, we know how to calculate
dƒ1u2>du. But how do we calculate dƒ1u2>dx? The answer to this question is stated as
the chain rule:
dƒ1u2 dƒ1u2 du
= (ME2.9)
dx du dx
Several examples illustrating the chain rule follow:
d sin13x2 d sin13x2 d13x2

= = 3 cos13x2 (ME2.10)
dx d13x2 dx
d ln1x 22 d ln1x 22 d1x 22 2x 2

= = 2 = (ME2.11)
dx d1x 22 dx x x
1 -4 1 -4 1
d ax + b d ax + b d ax + b
x x x 1 -5 1
= = -4 ax + b a1 - 2 b (ME2.12)
dx 1 dx x x
d ax + b
x
d exp1ax 22 d exp1ax 22 d1ax 22

= = 2ax exp1ax 22, where a is a constant (ME2.13)
dx d1ax 22 dx
Additional examples of use of the chain rule include:
d 1 23x 4>3 2 >dx = 14>3223x 1>3 (ME2.14)
d 1 5e322x 2 >dx = 1522e322x (ME2.15)
d14 sin kx2

= 4k cos x, where k is a constant
dx
d 1 23 cos 2px 2
= -223p sin 2px (ME2.16)
dx
ME2.4 THE SUM AND PRODUCT RULES

Two useful rules in evaluating the derivative of a function that is itself the sum or prod-
uct of two functions are as follows:
d3 ƒ1x2 + g1x24 dƒ1x2 dg1x2
= + (ME2.17)
dx dx dx
For example,
d1x 3 + sin x2 dx 3 d sin x
= + = 3x 2 + cos x (ME2.18)
dx dx dx

ME2.6 Higher-Order Derivatives: Maxima, Minima, and Inflection Points 7
d3 ƒ1x2g1x24 dƒ1x2 dg1x2

= g1x2 + ƒ1x2 (ME2.19)
dx dx dx
For example,
d3 sin1x2 cos1x2 4 d sin1x2 d cos1x2
= cos1x2 + sin1x2
dx dx dx
= cos2 x - sin2 x (ME2.20)
ME2.5 THE RECIPROCAL RULE

AND THE QUOTIENT RULE
How is the first derivative calculated if the function to be differentiated does not have a
simple form such as those listed in the preceding section? In many cases, the derivative
is found by using the product rule and the quotient rule given by
1
da b
ƒ1x2 1 dƒ1x2
= - 2
(ME2.21)
dx 3 ƒ1x24 dx
For example,
1
da b
sin x 1 d sin x -cos x
= - 2 = (ME2.22)
dx sin x dx sin2 x
ƒ1x2 dƒ1x2 dg1x2
dc d g1x2 - ƒ1x2
g1x2 dx dx
= 2
(ME2.23)
dx 3 g1x24
For example,
x2
da b
sin x 2x sin x - x 2 cos x
= (ME2.24)
dx sin2 x
ME2.6 HIGHER-ORDER DERIVATIVES: MAXIMA,

MINIMA, AND INFLECTION POINTS
A function ƒ1x2 can have higher-order derivatives in addition to the first derivative.
The second derivative of a function is the slope of a graph of the slope of the function
versus the variable. In order for the second derivative to exist, the first derivative must
be continuous at the point of interest. Mathematically,
d 2ƒ1x2 d dƒ1x2
2
= a b (ME2.25)
dx dx dx
For example,
d 2 exp1ax 22 d d exp1ax 22 d3 2ax exp1ax 224

= c d =
dx 2 dx dx dx
= 2a exp1ax 22 + 4a2x 2 exp1ax 22, where a is a constant (ME2.26)
The symbol ƒ″1x2 is often used in place of d 2ƒ1x2>dx 2. If a function ƒ1x2 has a
concave upward shape 1∪2 at the point of interest, its first derivative is increasing with
x and therefore ƒ″1x2 7 0. If a function ƒ1x2 has a concave downward shape 1¨2 at the
point of interest, ƒ″1x2 6 0.

4 f(x) The second derivative is useful in identifying where a function has its minimum or
maximum value within a range of the variable, as shown next. Because the first deriva-
2 tive is zero at a local maximum or minimum, dƒ1x2>dx = 0 at the values xmax and xmin.
f(x)5x225x Consider the function ƒ1x2 = x 3 - 5x shown in Figure ME2.2 over the range
-2.5 … x … 2.5.
22 21 1 2 x
By taking the derivative of this function and setting it equal to zero, we find the
22 minima and maxima of this function in the range
d1x 3 - 5x2 5
24 = 3x 2 - 5 = 0, which has the solutions x = { = 1.291
dx A3
Figure ME2.2
ƒ1 x2 = x3 − 5x plotted as a function The maxima and minima can also be determined by graphing the derivative and finding
of x. Note that it has a maximum and a the zero crossings, as shown in Figure ME2.3.
minimum in the range shown. Graphing the function clearly shows that the function has one maximum and one
minimum in the range specified. Which criterion can be used to distinguish between
these extrema if the function is not graphed? The sign of the second derivative, evalu-
f(x) ated at the point for which the first derivative is zero, can be used to distinguish
f(x)53x225 between a maximum and a minimum:
10
d 2ƒ1x2 d dƒ1x2
2
= c d 6 0 for a maximum
dx dx dx
5
d 2ƒ1x2 d dƒ1x2
2
= c d 7 0 for a minimum (ME2.27)
x dx dx dx
22 21 1 2
We return to the function graphed earlier and calculate the second derivative:
25
d 21x 3 - 5x2 d d1x 3 - 5x2 d13x 2 - 52
Figure ME2.3
= c d = = 6x (ME2.28)
dx 2 dx dx dx
The first derivative of the function
shown in the previous figure as a By evaluating
function of x.
d 2ƒ1x2 5
2
at x = { = {1.291 (ME2.29)
dx A3
7.5 f(x)
we see that x = 1.291 corresponds to the minimum, and x = -1.291 corresponds to
5.0 the maximum.
2.5 If a function has an inflection point in the interval of interest, then
x
dƒ1x2 d 2ƒ1x2
22 21 1 2 = 0 and = 0 (ME2.30)
22.5 dx dx 2
25.0 An example for an inflection point is x = 0 for ƒ1x2 = x 3. A graph of this function in
f(x)5x3
the interval -2 … x … 2 is shown in Figure ME2.4. In this case,
27.5
dx 3 d 21x 32
Figure ME2.4 = 3x 2 = 0 at x = 0 and = 6x = 0 at x = 0 (ME2.31)
ƒ1 x2 = x3 plotted as a function of x.
dx dx 2
The value of x at which the tangent to the
curve is horizontal is called an inflection
point.
ME2.7 DEFINITE AND INDEFINITE INTEGRALS
In many areas of physical chemistry, the property of interest is the integral of a function
over an interval in the variable of interest. For example, the work done in expanding an
ideal gas from the initial volume Vi to the final volume Vƒ is the integral of the external
pressure Pext over the volume
xƒ Vƒ
Lxi LVi
w = - Pexternal Adx = - Pexternal dV (ME2.32)
Equation ME2.13 defines a definite integral in which the lower and upper limits of in-
tegration are given. Geometrically, the integral of a function over an interval is the area

ME2.7 Definite and Indefinite Integrals 9
under the curve describing the function. For example, the integral 1-2.31x 3 - 5x2dx
2.3
4 f(x)
is the sum of the areas of the individual rectangles in Figure ME2.5 in the limit within
which the width of the rectangles approaches zero. If the rectangles lie below the zero f(x)5x325x 2
line, the incremental area is negative; if the rectangles lie above the zero line, the incre-
mental area is positive. In this case, the total area is zero because the total negative area
22 21 1 2 x
equals the total positive area.
The integral can also be understood as an antiderivative. From this point of view, 22
the integral symbol is defined by the relation
24
dƒ1x2
L dx
ƒ1x2 = dx (ME2.33)
Figure ME2.5
The integral of a function over a given
and the function that appears under the integral sign is called the integrand. Interpreting range corresponds to the area under
the integral in terms of area, we evaluate a definite integral, and the interval over which the curve. The area under the curve
the integration occurs is specified. The interval is not specified for an indefinite integral. is shown approximately by the green
The geometrical interpretation is often useful in obtaining the value of a definite in- rectangles.
tegral from experimental data when the functional form of the integrand is not known.
The value of the indefinite integral 1 1x 3 - 5x2dx is that function which, when differ-
For our purposes, the interpretation of the integral as an antiderivative is more useful.
entiated, gives the integrand. Using the rules for differentiation discussed earlier, you
can verify that
x4 5x 2
L
1x 3 - 5x2dx = - + C (ME2.34)
4 2
Note the constant that appears in the evaluation of every indefinite integral. By
differentiating the function obtained upon integration, you should convince yourself
that any constant will lead to the same integrand. In contrast, a definite integral has no
constant of integration. If we evaluate the definite integral
2.3
x4 5x 2 x4 5x 2
L
1x 3 - 5x2dx = a - + Cb - a - + Cb (ME2.35)
4 2 x = 2.3 4 2 x = -2.3
-2.3
is an even function of x, and 1-2.31x 3 - 5x2dx = 0, just as we saw in the geometric

we see that the constant of integration cancels. The function obtained upon integration
2.3
interpretation of the integral.

Some indefinite integrals are encountered so often by students of physical chem-
istry that they become second nature and are recalled at will. These integrals are
directly related to the derivatives discussed in Sections ME2.2–ME2.5 and include the
following:
L
dƒ1x2 = ƒ1x2 + C
xn + 1
L
x ndx = + C
n + 1
L x
dx
= ln x + C (ME2.36)
eax
L
eax = + C, where a is a constant (ME2.37)
a
L
sin x dx = -cos x + C (ME2.38)
L
cos x dx = sin x + C (ME2.39)

Although students will no doubt be able to recall the most commonly used inte-
grals, the primary tool for the physical chemist in evaluating integrals is a good set of
integral tables. Some commonly encountered integrals are listed below. The first group
presents indefinite integrals.
L
1
1sin ax2dx = - cos ax + C (ME2.40)
a
L
1
1cos ax2dx = sin ax + C (ME2.41)
a
L
1 1
1sin 2 ax2dx = x - sin 2ax + C (ME2.42)
2 4a
L
1 1
1cos2 ax2dx = x + sin 2ax + C (ME2.43)
2 4a
x2
L
cos 2bx x sin 2bx
x sin2 bxdx = - - + C (ME2.44)
4 8b2 4b
x2
L
cos 2bx x sin 2bx
x cos2 bxdx = + + + C (ME2.45)
4 8b2 4b
L
1 3 1 1 1
1x 2 sin2 ax2dx = x - a x2 - b sin 2ax - x cos 2ax + C
6 4a 8a3 4a2
(ME2.46)
L
1 3 1 1 1
1x 2 cos2 ax2dx = x + a x2 - b sin 2ax + x cos 2ax + C
6 4a 8a 3
4a2
(ME2.47)
L
3 cos ax cos 3ax
1sin3 ax2dx = - + + C (ME2.48)
4a 12a
1a2x 2 - 22cos ax
L
2x sin ax
1x 2 sin ax2dx = + + C (ME2.49)
a3 a2
1a2x 2 - 22sin ax
L
2x cos ax
1x 2 cos ax2dx = + + C (ME2.50)
a 3
a2
x meax
L aL
m
x meaxdx = - x m - 1eaxdx + C (ME2.51)
a
eax eax eax

Lx m - 1 L xm - 1
1 a
m dx = - + dx + C (ME2.52)
m - 1 xm - 1
e-ar 2 2
L
r 2e-ardr = - 1a r + 2ar + 22 + C (ME2.53)
a3
The following group includes definite integrals.
a a
L L
npx mpx npx mpx a
sin a b * sin a b dx = cos a b * cos a b dx = dmn
a a a a 2
0 0
where dmn is one if m = n and 0 if m ≠ n (ME2.54)

a
L
npx npx
c sin a b d * c cos a b d dx = 0 (ME2.55)
a a
0
M02_ENGE4590_04_SE_ME2_005-012.indd 10 25/10/17 9:37 AM

ME2.7 Definite and Indefinite Integrals 11
p p
L L
2 p
sin mx dx = cos2 mx dx = (ME2.56)
2
0 0
∞ ∞
L 2x L 2x
sin x cos x p
dx = dx = (ME2.57)
A2
0 0
∞
L
n!
x ne-axdx = n+1
1a 7 0, n positive integer2 (ME2.58)
a
0
1#3#5# # # 12n - 12
∞
L
2 p
x 2ne-ax dx = n+1 n
1a 7 0, n positive integer2 (ME2.59)
2 a Aa
0
∞
L
2 n!
x 2n + 1e-ax dx = 1a 7 0, n positive integer2 (ME2.60)
2 an + 1
0
∞
p 1>2
L
2
e-ax dx = a b (ME2.61)
4a
0
Commercially available software such as Mathematica™, Maple™, Matlab™, and

MathCad™ can evaluate both definite and indefinite integrals.
M02_ENGE4590_04_SE_ME2_005-012.indd 11 25/10/17 9:37 AM

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saccharin from the medicine chest, so long as they lasted. The milk
often curdled in boiling, owing to the vessels it had been brought in
not having been cleaned since the milking the night before, and we
were compelled to eat the solid curds with a spoon. We served out
an allowance of beads to the men every day, with which they bought
milk, fat, and occasionally meat.
El Hakim heard that many years before, the sheep and goats of
the Rendili, with the exception of Lubo’s, which were camped in
another place at the time, had been swept away by a pestilence. In
such cases the custom of the tribe appears to be that the owner of
the surviving flocks must give the others sufficient animals to enable
them to recommence breeding; but he has the right to take them
back, together with their progeny, provided that his own needs
require it. Old Lubo, therefore, was practically the owner of all the
vast flocks of the Rendili, which could only be numbered by
hundreds of thousands. The confidence between the animals and
their owners was very noteworthy, even the sheep allowing
themselves to be handled freely for milking, and for purposes of
examination. They are of the fat-tailed variety, some of the tails
weighing as much as thirty pounds. This fat tail is another object
lesson of the way nature provides her creatures against all
emergencies. The Rendili sheep in times of plenty develop and store
a large reserve of nourishment in the fat of their ponderous tails, so
that when, as often happens, their pasturage becomes exhausted
through want of rain or other causes, they have a store to draw
upon, sufficient for their needs for a considerable period. Another
store of fat is also formed, in the case of the Rendili sheep, in a large
pouch or dewlap under the throat, and also on the breast-bone,
where the fat is often a couple of inches in thickness.
As an instance of the ignorance and denseness of the average
Swahili, as regards anything outside his own particular sphere, I will
mention a little incident which occurred one day. El Hakim sent
Jumbi and three or four men with a supply of cloth and beads to buy
sheep at a Rendili village. He was instructed to buy “soben,” i.e.
ewes, in good condition. He returned next day with a dozen or so of
the raggedest scarecrows that the Rendili had been able to rake out.
El Hakim reprimanded him, and asked why he had not obtained
better animals, as those he had brought had no fat tails at all, but
merely shrivelled-up skin. Jumbi answered that it was true that the
Rendili had brought sheep with much fatter tails to him, but he had
rejected them, their tails being so large that he thought the sheep
would not be able to travel!
The Rendili own donkeys, but not so many as the Burkeneji. They
also own horses, which the Burkeneji do not, and which they
probably procure from the Borana, who are reported to own vast
numbers of them. The Borana are a very powerful and numerous
tribe living in north-east Galla-land. They are fierce fighters, and it
was formerly quite the correct thing for any warrior among the
Rendili who yearned for distinction to lead a raiding party against the
Borana, who as often returned the compliment.
The Borana fight with two short, broad-bladed spears, while for
defensive purposes they carry a small round shield made from the
skin of the hump of the oryx. They wear cloth—a small cloth round
the loins and a larger one thrown over the shoulders completing their
costume. They possess large numbers of cattle, sheep, and goats,
and vast herds of half-wild horses. They are a sullen, inhospitable
people, very unwilling to receive strangers. They, like the Rendili and
Burkeneji, wear sandals, the thorny acacia, so plentifully distributed
thereabouts, being even too much for the naked feet of savages.
The Rendili ride their horses with a saddle something like the
native Somali saddle. It is made of wood, covered with sheepskin,
and is fastened by a girth knotted to rings in the saddle. The stirrups
are similar to those of the Somali, consisting merely of two iron rings,
into which the rider thrusts his big toe, his sandals having been
previously removed. A breast-plate and crupper are used to keep the
saddle in place. They use a very crude iron bit, of a particularly cruel
form, attached to strips of undressed leather which do duty for reins.
The Rendili are among the most persistent beggars that I have
ever met with. The Egyptian beggar, with his oft-reiterated
“backshish,” is hard to beat, but the average Rendili could easily give
him long odds and a beating. It grew to be quite a fashionable
amusement with them to come down to our camp, often some hours’
journey, and spend the day in begging for small articles. When El
Hakim, who slept outside his tent, awoke in the morning, he would
find a number of them squatted round his bed, and as soon as he
opened his eyes a murmur of “Mate serutia?” (Is there no brass
wire?) greeted him. He would answer “Mate! mate!” (No! no!) and
retreat hurriedly to the interior of the tent. But it was of no use; a
moment later he would be again approached by his questioners, who
would softly inquire, “Mate serutia?” having apparently forgotten his
emphatic negative to the same inquiry five minutes before. Again El
Hakim would answer, “Mate serutia!” (There is no brass wire!). So,
gazing reproachfully at him, his tormenters would leave him and
come to me.
The same succession of beseeching inquiry and stony refusal
would be gone through, and when they were convinced that I was as
hard-hearted as El Hakim, they would leave me and try George. He
also was adamant; but they were not discouraged. Back they would
go to El Hakim, and repeat the whole performance.
This happened every hour of every day during the whole period of
our sojourn among them; it almost drove us frantic on occasions. To
do them justice, the cry was sometimes varied; sometimes it was
“Mate serutia?” and other times “Mate tumbao?” (tobacco), of which
they are inordinately fond, probably because they can obtain it only
on the rare occasions when they come in contact with the Wa’embe,
and the Reshiat at the north end of the “Basso Norok” (Lake
Rudolph).
Lubo himself often sat for hours in front of the temporary hut of
palm leaves we had erected as a council house, begging for a few
beads or a small piece of brass wire. We ridiculed him once, saying
that we were surprised that he, who was such a wealthy man, should
beg for a few beads. He was amazed!
“Is it not good to give?” he said.
“Well, then, why do you not give us something?” we inquired.
“You have never asked me!” he answered simply.
If we had been a wealthy exploring caravan, rich enough to have
bestowed munificent gifts on the Rendili on our arrival, doubtless
their value, or near it, would have been returned to us in kind, but we
could not then have been certain of getting what we needed, as the
return gift might have consisted of camels or some other commodity
which we did not require, and which we would be unable, from the
nature of the case, to refuse. We preferred, therefore, the slower and
more sordid process of bartering for what we wanted. We had, of
course, bestowed presents on arrival, but nothing large enough to
warrant the gift of perhaps half a dozen camels in return.
Their begging was at times particularly aggravating; for instance,
after a hot and weary morning passed in trade “shauries” and
discussions with the various elders respecting presents to be given
and received. Having lunched on a quart of milk or so, we would
retire for a smoke and a siesta. Just as we were dropping off into a
delicious doze, a dusky countenance would be thrust into the hut,
and a gentle voice would softly utter, “Mate serutia?” accompanied
by a touching smile and insinuatingly outstretched paw. At such
times language failed us, and we could only glare. But glaring did not
seem to have any effect; the intruder did not mind it in the least, so
the services of Ramathani had to be requisitioned, and as he led the
culprit gently away, we would compose ourselves once more to
sleep to the accompaniment of the plaintive murmur of “Mate serutia”
sandwiched between the voluble remonstrances of our faithful
henchman.
But five minutes later, the whole performance would be repeated!
The Rendili villages consist of low, flat-topped huts constructed of
bush and reeds arranged in a circle a hundred yards or so in
diameter. In the centre they construct a circular enclosure for their
flocks. Outside the whole a strong thorn “boma” is built, with
generally two gateways on opposite sides, which are closed at night.
In consequence of the great reduction in their numbers by small-pox,
most of the villages were very short handed. Women and little
children acted as shepherds in place of the now extinct warriors,
whose duty it had been before the scourge removed them. So much
was this the case that in some villages the inhabitants, even when
reinforced by the women and children, were still too few to be able to
drive all their animals to water daily. They were therefore reduced to
the expedient of driving their sheep and goats down one day, and
the camels the next, and so on alternately.
Their household utensils were few, and simple in construction.
Their milk-vessels were either of wood, hollowed and shaped, or of
plaited string, made watertight with gum. Some of the vessels of
plaited string were further strengthened by a covering of raw hide
stitched with gut. They were made in all sizes, ranging from a tiny
measure holding scarcely a pint to large vessels holding two or three
gallons. They also construct a rude spoon from plaited string. They
possess a few gourds, doubtless obtained by barter from other
tribes. They use the bladders of animals for the purpose of holding
fat, and for other purposes, such as satchels and bags.
The pack-saddles for their camels and donkeys are made of
wickerwork. They are very light and strong, and answer the purpose
admirably. The donkey pack-saddle consists of two elongated oval
frames of bent wickerwork laced with strips of hide in a similar
manner to the gut in a tennis racquet. These frames are then
connected with two broad bands, which are fastened to their lower
edges and pass over the donkey’s back. The forage or household
effects, or whatever has to be carried, is packed on the donkey,
being kept from slipping by the frames, which are then tied with
cords on their upper edges, one to the other, thus making the
package complete and snug.
Their weapons consist of spears, shields, and bows and arrows.
The spears are very light, and do not look at all dangerous. The
blade is of the usual laurel-leaf shape, common to the Suk, Turkana,
and Kamasia tribes, though one or two of Somali pattern are
occasionally seen.
Their shields are also of the shape peculiar to the Suk and
Turkana. Made of buffalo-hide, they are of a very narrow oblong
shape, with a peculiar curve when seen in profile. They are
ornamented with a tuft of feathers at the top. They are now usually
constructed of ox-hide, as, since the rinderpest, the buffalo is very
scarce, and a buffalo shield is valued accordingly. There are also a
few of the wickerwork shields of the Reshiat in use among them.
Their bows differ in shape from those of the A’kikuyu and
Wa’kamba, in that they are turned forward at the ends, in a similar
manner to the conventional Cupid’s bow. So far as I could ascertain,
their arrows are not poisoned.
They do not use clubs as weapons; at least, I saw none that could
be used as such. The only club they carried consisted of the kernel
of the doum nut fastened on to the end of a slight stick some
eighteen inches in length, a hole being bored longitudinally through
the nut, and the stick inserted. The kernel was in many cases
ornamented with small coloured beads, which were inlaid when it
was new and comparatively soft, the whole then finished off by being
covered with a thin layer of gum.
That the reports of the powers of the Rendili in warfare were not
devoid of foundation was borne out in a striking manner by facts
which came under our observation. Many of our visitors showed livid
scars on the left forearm and breast. Inquiry revealed the fact that
the warriors who wished to be accounted brave in warfare dispensed
with their shields altogether, receiving on their left forearm those
spear-thrusts they were unable to avoid. This is, as far as I know, a
unique characteristic among African savages, though I am open to
correction on that point. The fact that the Rendili, besides attacking
the Borana, have also successfully raided the Wa’embe and the
A’kikuyu of north-east Kenia speaks well for their courage and
enterprise. Most of the elders we met showed great scars on the
arms, breasts, and thighs—relics of spear-thrusts received in the
sanguinary conflicts of their hot-blooded youth. The tribe now shows
only the merest traces of its former greatness, depending mainly on
the Burkeneji for protection from outside interference, though they
are still by no means to be despised.
The Burkeneji, noting the ravages of the small-pox on their once
all-powerful neighbours, were not slow in profiting by the lesson.
When the scourge appeared, they sent their young men away to
separate camps, and so preserved them. They were able to do so
without inconvenience, as they did not own such numbers of animals
as the Rendili, who would not send their youths away, as they
wanted them to look after their flocks and herds—a short-sighted
policy which cost them very dearly.
Now, the Burkeneji were perfectly willing to protect the Rendili, but
in return they considered that they ought to be allowed the right to
help themselves from the Rendili flocks whenever they felt so
disposed; and to do them justice they fully acted up to this idea,
without fear of reprisals. It seemed to me a very peculiar state of
affairs. The two tribes lived together, that is, their villages were
intermingled, and they travelled together; yet the Burkeneji
constantly raided the Rendili, and though the Rendili did not seem to
like it, they never openly resented the depredations.
Old Lubo once complained to us that he had been raided during
the afternoon—as a matter of fact, the raid took place not five
minutes’ walk from our camp—and a few score of sheep and two
women had been looted from him. We inquired why he made no
attempt to recapture them. He opened his eyes widely at the novelty
of the idea.
“We do not fight between friends,” he said.
Notwithstanding their fighting qualities, both the Rendili and
Burkeneji were very anxious about the Masai. They seemed to live in
dread of them. We were frequently asked if we had seen any Masai
on our march up, and whether we thought they were coming to the
Waso Nyiro. Large parties of Masai “elmoran” (warriors) had
occasionally attempted to raid the Rendili, but were almost always
unsuccessful, the principal reason being the inaccessibility of the
country and the nomadic habits of the tribe.
On the march the Masai elmoran carries next to nothing in the way
of provisions, trusting to find cattle on the road, which he can use for
food, after massacring the owners. Thompson describes the
ceremony of the departure of a Masai war-party thus—
“For a month they devoted themselves to an indispensable,
though revolting preparation. This consisted in their retiring in small
parties to the forest, and there gorging themselves with beef. This
they did under the belief that they were storing up a supply of muscle
and ferocity of the most pronounced type. This strange process
being finished and the day fixed on, the women of the krall went out
before sunrise, with grass dipped in the cream of cow’s milk. Then
they danced, and invoked N’gai for a favourable issue to the
enterprise, after which they threw the grass in the direction of the
enemy. The young men spent several hours at their devotions,
howling out in the most ludicrous street-singer fashion, ‘Aman N’gai-
ai! Aman M’baratien!’ (We pray to God! We pray to M’baratien!).
Previous to this, however, a party had been sent to the chief ‘lybon’
of the Masai—M’baratien—to seek advice as to the time of their
start, and to procure medicines to make them successful. On their
return the party mustered and set off!”
MASAI ELMORAN IN WAR ARRAY.

It will be seen that under these conditions it was a very difficult
matter to successfully raid a tribe like the Rendili, to reach whom
they had to cross uninhabited and desolate country for ten days or
more, and generally to arrive at their prospective victims’ camping-
ground starved and emaciated with their rapid and difficult march, to
find that the Rendili had withdrawn with all their flocks and herds still
further into the depths of the wilderness. Weakened by want of food,
and fatigued almost beyond endurance, there would be nothing for
the war-party but to retrace their steps, it being quite hopeless to
attempt to find the Rendili in the desert, in which they were quite at
home. So, sadder and wiser, the crestfallen elmoran would return,
many dropping by the way from hunger and exhaustion, till a pitiful
remnant of the once proud and arrogant war-party would totter
home, to rest and recuperate before starting on another raid on the
A’kikuyu, where the prizes, if few in number, did not entail so much
inconvenience in the collection.
CHAPTER XIV.
THE SEARCH FOR LORIAN.
Exchanging presents with the Rendili—El Hakim bitten by a scorpion

—We start for Lorian without guides—Zebra—Desolate character
of the country—Difficulties with rhinoceros—Unwillingness of our
men to proceed—We reach the limit of Mr. Chanler’s journey—No
signs of Lorian.
The climate was still all that could be desired. The heat in the
daytime was terrific, but the air was so dry that it was quite bearable.
No dew fell at night, and sleeping in the open was, in consequence,
an unmixed pleasure. Our camp was about 1200 feet above sea-
level, and the temperature during the day could not have been much
less than 120° Fahr., which dropped at night to from 85° to 90° Fahr.
I made several short trips into the surrounding country in search of
fresh meat, but except a solitary grantei or wallerei at intervals, the
country was devoid of game. The flocks and herds of the Rendili
roamed so far afield in search of pasture that all the game within a
day’s march had been driven away. The guinea-fowl were very wild,
and I found my 20-bore was unable to deal with them, as it would not
kill far enough. Also we considered it unwise to do any shooting in
the near vicinity of the Rendili or Burkeneji villages, as the women
and children, being unaccustomed to firearms, were very much
frightened by the explosions, and it might possibly have proved a
cause of friction, which we of course wished to avoid.
About ten miles away to the north-east was the “Marisi-al-
lugwazambo,” or Zambo Plateau. It was of a most imposing-looking
formation, its sides being as steep and clean cut as if they had been
shaped with a knife. The sandy plain extended right up to the base of
the plateau, which rose fully 500 feet above the level of the
surrounding country. The plateau was composed chiefly of gneiss
rock, with large blocks of lava liberally sprinkled on its surface and
sides. It is about twenty-five miles long, with an average breadth of
five miles.
A few days after our arrival Lubo came into camp with a present of
fifteen sheep. In return we gave him some coils of brass and iron
wire and about thirty yards of marduf, with which he professed
himself very pleased.
In and around our camp there were large numbers of centipedes
and scorpions, and it was quite exciting sometimes when a
centipede was discovered snugly ensconced in the blankets, just as
one was going to turn in. El Hakim, while turning over some pieces
of cloth, when making up Lubo’s present, was stung in the hand by a
large scorpion. It was pure white in colour, and consequently lay
unnoticed among the folds of the cloth. His arm soon became very
painful, the armpit and chest being immediately affected. Before the
pain became too severe, however, I injected a solution of morphia
with a hypodermic syringe, which relieved him greatly. The following
morning the pain had almost entirely subsided, and in a couple of
days no further ill effects were noticeable.
In the course of conversation with some of the Rendili elders, we
were surprised to hear that Lorian was only two days’ march distant.
We were very much surprised, as Mr. Chanler made it at least forty-
five miles’ march over extremely difficult country, beyond the furthest
eastern spur of the Zambo Plateau, which itself lay some fifteen to
twenty miles distant from our camp. We expressed our incredulity,
but we were assured that the Rendili could reach it in two days. We
concluded, therefore, that, making every allowance for characteristic
Rendili exaggeration, Lorian was much nearer than we had thought,
and we had half decided to make an attempt to reach it, when a
statement by the assembled Rendili to the effect that there were
“plenty of elephants down there,” clinched the matter. We asked for
guides, and as Lubo promised that they should be forthcoming, we
made our preparations for a journey to the mysterious Lorian.
The next day, as no guides had put in an appearance, El Hakim
and George went over to Lubo’s village, to find out the reason for the
delay. Lubo, excusing himself, said that he was looking for guides,
but so far he had not got hold of any one who knew the way. Two
more days passed, but still no guides were forthcoming. Lubo was
full of excuses and promises, but as far as he was concerned the
matter was allowed to drop. Eventually we determined to make the
journey without guides. We could always follow the river, which of
course would be a more tedious journey, but there seemed no other
way out of the difficulty.
On August 30th, therefore, we made a start, taking with us only a
dozen men, and leaving Jumbi and the bulk of the men in charge of
our camp, with instructions to continue buying sheep. The tents were
left behind with most of our other impedimenta, as we intended
travelling as lightly as possible. We took with us merely a blanket or
two, the necessary culinary utensils, my camera, some spare
ammunition, and a change of clothing apiece.
On leaving camp we skirted the north bank of the Waso Nyiro for
some miles, deviously threading our way among the palm trees. It
was a glorious excursion, this tramp through the cool dark glades
beneath the palms, where the remnants of the bright sunshine which
filtered through the leafy canopy overhead gave the scene the
appearance of the interior of a vast cathedral dimly illuminated by
rays of sunshine through stained glass windows. The effect was
heightened by the occasional glimpses between the palm trunks of
the smooth shining surface of the river, over which numbers of
brilliantly coloured kingfishers darted to and fro like the falling
fragments of a shattered rainbow.
Presently we emerged on the river-bank at a likely looking spot for
a crossing. As we did so, a sliding, slipping sound, followed by a dull
splash, warned us of the presence of crocodiles, and an examination
of the bank showed us that three or four of the loathsome reptiles
had been basking in the sun at that very spot. The tracks were,
however, those of comparatively small ones, probably not more than
six or eight feet long. Across the river several others of about the
same size, as yet unaware of our presence, were basking on the
sandbanks. The noise made by the porters soon roused them, and
they also disappeared, with a wriggle and a flop, beneath the swirling
stream. The river not being very deep, scarcely four feet at the
deepest part, we entered the water and waded across, the men
shouting and splashing with great vigour, while casting many a
sidelong glance at the turbid current. Once across, our search for
Lorian had commenced in good earnest, and setting our faces to the
eastward, we strode forward on a course parallel to the south bank
of the river.
An hour later we saw a herd of zebra, and George and I, after a
long and careful stalk, secured four. They were in prime condition,
and very plump, yet, strange to say, the country appeared to produce
nothing more nourishing than occasional clumps of coarse grass, or
rather straw, as it was burnt yellow by the fierce rays of the sun.
These four zebras were a veritable windfall, as they not only enabled
the men who accompanied us to lay in a few days’ supply for our
journey down the river, but by sending a messenger back to Jumbi
he was enabled to send for the remainder, which was sufficient to
feed the men remaining in camp for some days.
We camped on the river-bank, which we had some difficulty in
regaining, having to cut our way with knives and axes through the
densely interlaced bush and creepers which fringed the water’s
edge. The weather was delightful, though the heat in the open was
terrific, this camp being situated within one degree of the equator,
and not more than one thousand two hundred feet above sea-level.
On starting the following morning we found that the river curved
away to the northward, rounding the easterly spur of the Zambo
Plateau. As we proceeded, the luxuriant tropical vegetation gave
way to scattered acacias and patches of burnt-up elephant grass.
The soil underfoot also changed in character, the rocky outcrops and
boulders of quartz and gneiss almost entirely disappearing. In their
place were vast stretches of smooth shining sand, alternated with
patches of loose brown earth, as soft and crumbly as starch, which
made travelling a matter of great toil and difficulty. Game was very
plentiful. I shot a grantei during the morning, and when we halted for
lunch I secured three water-buck.
After we had eaten and rested awhile we resumed the march. The
aspect of the country grew worse and worse. The brown crumbling
soil gave way under our feet; it seemed so rotten that it was unable
to bear our weight, and at every step we sank into it over our knees,
our passage raising a brown impalpable dust which choked our
eyes, ears, and nostrils in a most uncomfortable and disconcerting
manner. The mules suffered even more than ourselves. It was
impossible to ride them, as at every stride they sank up to their
hocks in the rotten earth, and floundered about in a most pitiful and
distressing manner. The sand, which seemed so smooth and firm on
the surface, was also honeycombed underneath by some agency or
other. I had a nasty fall from this cause during the afternoon’s march.
I was riding the big mule, when the sand suddenly collapsed under
her forefeet and she went down on her chest, afterwards rolling over
on my leg, pinning me to the ground. In her struggles she kicked me
in the side several times, inflicting severe bruises. Ramathani
secured her head, and I was pulled from under her, feeling badly
shaken and very faint. The mule then broke away and raced across
country, kicking her heels in the air in delighted freedom. She was
not caught for over an hour, during which I had to stumble along in
the burning sun as best I could, with my head spinning like a top,
and my temper considerably above the boiling-point. We concluded
a weary march by sundown, and again camped under the palms on
the river-bank.
These palms formed a home for large troops of baboons and little
monkeys, who chattered unceasingly. After our meagre meal of fried
meat we retired. The moon was in the first quarter and shed a little
light after the sun had set, and we laid back in our blankets and,
gazing up at the palms, spent an hour or so in desultory
conversation, or perhaps discussing our route for the morrow. As the
sun set the night-birds appeared, and tuned up, preparatory to their
usual concert, lasting from sunset to sunrise. One bird in particular
went regularly up and down the scale, starting from D, and mounting
by leaps and bounds over a couple of octaves, descended again.
This performance was repeated with maddening insistency during
the greater part of the night.
At sunrise on the morning of September 1st we were again on the
road. We saw several herds of water-buck on the banks of the Waso
Nyiro, but they were very shy and most difficult to approach. The
river ran in a direction almost due north. The further we followed it to
the north and east the scarcer became the vegetation. Rhinoceros
became once more unpleasantly numerous, and during that
morning’s march we dodged several who at one time bade fair to
disperse our little company. I suppose that they have their uses,
though they are inconvenient at times. I know of nothing better for
livening up the monotony of an otherwise uninteresting march, than
a crusty old rhino who has just been roused from a refreshing nap. A
lion does not create half so much excitement. El Hakim and George
had to bestir themselves on one occasion during the morning, in
order to prevent accident. It was in this wise. I was marching ahead,
and contemplating as I went the manifold beauties of nature. A few
yards behind me rode in silence El Hakim and George, also
contemplating the beauties of nature—or were they thinking of the
approach of lunch time? Anyhow, we were some few hundred yards
ahead of the men when an agonized yell from Ramathani, who was
in the rear, caused us to look round. There, not forty yards away,
were two rhinoceros, a mother and a half-grown young one, coming
straight for us with speedy but noiseless footsteps. I instantly took up
a strategic position on the opposite side of an adjacent bush, and
became an interested spectator, taking the precaution, however, to
slip a cartridge into my rifle in case it should be needed. El Hakim
and George dismounted with such rapidity that they almost seemed
to fall off. Letting go the mules, who dashed away at full speed, they
also selected a bush from which to view the procession, both of them
being unarmed. The rhinos were by that time hardly half a dozen
yards behind them, and scarcely had they slipped behind their
respective bushes when the brutes charged right between us and
went on. Not twenty seconds could have elapsed from the time
Ramathani’s warning shout reached us to the time the rhinos
passed, but to us it seemed nearer twenty minutes. I give this
instance—one of many—to show how pleasantly one is kept on the
qui vive in the districts where the rhinoceros abounds, be the
landscape ever so monotonous, or the march ever so weary.
After a march lasting from sunrise till ten o’clock in the forenoon
we halted for breakfast, or lunch, as we variously called our first
meal, according to the time of day at which we made our halt. The
continuous meat diet was getting very monotonous and unpalatable,
chiefly owing to the absence of sufficient fat for cooking purposes.
Our tobacco, of which, owing to some inadvertence on our departure
from the Rendili camp, we had brought only a very small supply,
gave out on this day, and we were thus deprived of another solace in
the midst of the trials and difficulties of the journey.
After we had breakfasted we made our simple preparations for
resuming the march, but to our dismay we found that the mules had
disappeared. The man in charge of them while they were grazing
had carelessly let them wander, and they were not to be found. We
eventually discovered their tracks leading back over the path we had
traversed in the morning, and we immediately sent some of the men
in chase. They returned in an hour with the refractory animals, and
we set off once more on our journey down the river. We saw
immense herds of game on the road, including giraffe, buffalo,
rhinoceros, grantei, and water-buck, and now and again we passed
old elephant and lion tracks.
To the south and east the shining desert extended away to the
horizon, with only a few thorny acacias to relieve the general
appearance of sameness. Troops of baboons squatted on the sand
or skipped about like children at play, their hoarse barks being
interpreted by our little puppy as a challenge, which, however, he
wisely declined to accept. At sundown we camped under a clump of
palms, and turned in early, thoroughly tired out. For myself, during
the whole of our journey to Lorian and back, I slept in paragraphs, so
to speak, waking at intervals all through the night, a result
contributed to in no small degree by the up-and-down-the-scale-two-
octaves bird I have already mentioned.
The following day we were on our way again at sunrise. An hour
afterwards we entered the most desolate region it had so far been
our ill luck to traverse. Trees and palms disappeared, and their place
was taken by coarse dry elephant grass eight or ten feet in height.
The country bore unmistakable signs of having been under water not
so very many seasons before. It was pitted in every direction by
elephant, rhinoceros, and hippopotamus tracks, which must have
been made when the earth was very soft, as they averaged from a
foot to eighteen inches in depth. These caused us great
inconvenience, as, being hidden by the long grass, we stumbled in
and out of them in a most unpleasant way, jarring our teeth and our
tempers with great frequency. In our endeavours to find some sort of
a path we lost the river, leaving it as we thought on our extreme left,
and in searching for it, to our intense surprise, we walked nearly into
it. It was flowing between perfectly perpendicular banks about six
feet in height, and in a direction at right angles to its course at the
commencement of the morning’s march. It was now little more than a
large ditch, and required to be followed very carefully, as there were
no trees on the banks to mark its position. This immense dried
swamp is called by Mr. Chanler the Kirrimar Plain. Personally I am of
opinion that in wet seasons, or after a series of wet seasons, that
portion of it immediately adjoining the river forms part of a swamp or
chain of swamps, to which the name Lorian is given. My reasons for
this supposition are given in the next chapter.
We followed the river very carefully, as, in the event of its taking a
sudden curve, we should have been absolutely lost, and in that case
must inevitably have perished. Indeed, the men were already very
frightened, and grumbled openly. They declared that we had got to
the end of the world, and had much better turn back before worse
befell us. The presence of numbers of rhinoceros had very much
frightened them. We encountered over thirty of them on one march;
and quite half a dozen times had to warily circumnavigate some
ungainly member of the species who was grazing directly in our
path. We paid no attention to this display of insubordination on the
part of the men, but pushed on, every obstacle to our progress only
serving to encourage us still more to persevere in our effort to reach
the much-desired goal. The heat on this open plain was tremendous;
it must have been above 120° Fahr. We were only a matter of about
800 feet above sea-level, and consequently encountered the full
force of the vertical rays of the equatorial sun.
At midday we halted, and, creeping under a bush for shelter, ate
our frugal meal of broiled meat, lying at full length on the ground.
During the meal a whisper of “ungruwe” (pig) from Ramathani
brought El Hakim to his feet. Seizing his rifle, he stepped outside and
shot an old boar, who, with two or three sows, was quietly feeding
about fifty yards away, utterly oblivious of our presence. His flesh
was tough and tasteless, not in the least resembling pork.
Several of the men came to us during the halt, to inquire how
much further we were going, as they thought that we had got into the
country of the “Afreets” (devils), and it would be advisable to go no
further. We assured them that two or three days at most would see
us at the end of our journey. The country looked so desolate and
barren that I do not wonder its appearance worked on the
superstitious minds of our men. We laughed at them, but they were
only half reassured. We started again, and continued to follow the
river, which was now not more than ten yards wide. Large crocodiles
swarmed on every mud-bank, some of them immense brutes, even
El Hakim declaring that he had never seen larger. One ugly reptile
which started up and plunged into the water at our approach, must
have been fully twenty feet long or more. El Hakim appropriately
called him “the father of all crocodiles.” This loathsome reptile, with
its blunt and massive snout and immense scaly body, reminded me
of the “Mugger” of the ford, in one of Kipling’s stories. The largest
crocodiles were dark-brown in colour, but there were multitudes of
smaller ones, some bright green and others bright yellow, two of
which I shot during the afternoon. When we camped that evening we
built huge fires between ourselves and the water, in order to prevent
the possibility of any of our party being seized during the night by the
hideous reptiles.
The following day was merely a repetition of the previous one. We
advanced through the same dried-up swamp, with its innumerable
pits, hidden by the same coarse grass and reeds. If anything, the
landscape seemed to have acquired an added tinge of desolation.
Rhino were a drug in the market, owing to the increased supply, but
zebra and grantei stock advanced several points during the day. We
followed the river very closely, not only because it was our only
guide, but because the hippopotamus, which abound in this portion
of the Waso Nyiro, had, in wandering from pool to pool, trodden a
rough path on the crest of the perpendicular bank of the river, which
made walking much easier than if we had forced our way across the
plain in endeavouring to cut across curves in the river-bed, though it
necessitated a longer walk. This path was also a favourite sleeping-
place for wandering rhinoceros, and on several occasions we walked
almost on to them, as they were hidden by the tall grass. A shout
generally brought the sleeping brute to his feet with a snort and a
stamp, and he would scurry away over the plain the picture of
indignant reproach.
During the march a slight misunderstanding between El Hakim
and myself came very near to landing us both in an extremely
perilous position. One rhino we came up with did not wake so easily,
and as he lay right across the path, we had to shift him by some
means. Standing fifteen or twenty yards away, we shouted, but he
did not move; so El Hakim stole softly up to within three or four yards
of him, and, stooping, he broke off clods of earth from the edge of
the river-bank and threw them at the sleeping beast, just as a small
boy might chivvy a cat with stones. Even that did not move him, so I
stole softly up to El Hakim with his ·577, which I handed to him.
Instead of taking it, he seized my small-bore rifle, and I, thinking he
meant me to try my luck with his, proceeded to cock it; but while I
was doing so El Hakim let drive at the brute’s head with my rifle. If he
had warned me of his intention, I should have told him that my ·303
shot very high at short range, but he fired before I could do so, and
missed its brain altogether, only drilling a clean hole through the ear.
Up jumped the rhino and faced us. I waited for El Hakim to fire again,
while he, it afterwards appeared, waited for me to put in a shot with
the heavier weapon. The rhino, meanwhile, made a rush at us, and
we were both prepared to slip over the bank into the river and
chance the crocodiles, when the brute changed its mind, and,
swerving aside, galloped away across the plain. Mutual explanations
ensued, and we proceeded on our momentarily interrupted journey.
In cold print it would seem as if we had both betrayed some
indecision, but the reader must bear in mind the fact that from the
time El Hakim fired the shot from my ·303 to the time the rhino
swerved and galloped away, an observer could not have counted
more than four or five seconds.
The river still diminished very much in volume, as a large amount
of water must of necessity be absorbed by the surrounding dry
country, while the loss by evaporation must be enormous. According
to our calculations we should now have been almost in sight of
Lorian, having travelled quite sixty-five miles down the river from our
Rendili camp.
On reaching a pool situated in a bend of the river, we came upon a
school of hippopotamus wallowing in the mud at the water’s edge.
We hid ourselves on the bank about ten yards away, and watched
them for some time, as one very rarely has a chance of seeing them,
unobserved, at such close quarters. Presently one of them rose,
and, climbing the bank, walked slowly towards us, grazing as it
came. El Hakim sat down—his favourite position for a shot—and
dropped it dead with a bullet through the neck. At the sound of the
report a terrific splash from the pool announced the alarm of the
other members of the school, and with one accord they dived to the
bottom, whence they reappeared at intervals to breathe,
accompanied by much blowing and snorting. With shouts of joy our
men instantly pounced upon the fallen hippopotamus, its meat being
greatly esteemed by them as food. We also were badly in need of
fat, which the dead animal supplied in great abundance. On cutting it
open we found layers of rich yellow fat, a couple of inches thick,
between the skin and the body. Great fires were at once lit, and for
the next hour or two the spot resembled the deck of a whaler when
the blubber is being boiled down. The men got a plentiful supply of
fat for themselves, and, after an hour’s boiling and rendering, we
also obtained two buckets of rich fat congealed to the consistency of
butter, which it resembled in colour.
At this stage the men again wished to turn back, but as we could
not have been very far from Lorian, we thought it would be a pity to
give up the search; so we announced our intention of proceeding, a
decision which they received with every sign of discontent and even
terror.
At one o’clock in the afternoon, having disposed of the remains of
the hippo, we once more made our way down-stream. Just before
sunset we sighted the immense sycamore tree which marked the

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Physical chemistry ; Quantum

Chemistry and Spectroscopy (What's

Physical chemistry 3rd Edition Engel Thomas Engel

Physical chemistry: thermodynamics, statistical

Physical chemistry quantum chemistry and molecular

Chemistry³ Introducing inorganic organic and physical

Atkins’ Physical Chemistry Peter Atkins

Numerical Problems in Physical Chemistry P Bahadur

Microreactors in Organic Chemistry and Catalysis Thomas

Beginning Chemistry 4th Edition Goldberg

PHYSICAL CHEMISTRY Quantum

The fourth edition of Quantum Chemistry & Spectroscopy includes

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Chapter 15, “Computational Chemistry,”

Chapter 17, “Nuclear Magnetic Resonance Spectroscopy,”

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Library of Congress Cataloging-in-Publication Data

Names: Engel, Thomas, 1942- author. | Hehre, Warren, author. | Angerhofer,

ISBN 10: 0-13-480459-7; ISBN 13: 978-0-13-480459-0 (Student edition)

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1 From Classical to Quantum Mechanics 19 11 Quantum States for Many-Electron Atoms

7 A Quantum-Mechanical Model for the 17 Nuclear Magnetic Resonance

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Preface ix 3.2 Every Observable Has a Corresponding

Math Essential 4 Infinite Series 4 Applying Quantum-Mechanical

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13 Molecular Structure and 15.3 Hartree–Fock Molecular Orbital Theory: A Direct

Assigning + and - to g Terms of Diatomic

15 Computational Chemistry 377 APPENDIX A Point Group Character Tables 513

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NEW! Math Essentials provide a review of

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178 CHAPTER 6 Chemical Equilibrium

178 CHAPTER 6 Chemical Equilibrium

successive steps in the reaction proceed NH(g) 1 2H(g)

from left to right in the diagram.

synthesis reaction, such a route is a heterogeneous catalytic reaction, using iron as a

H21g2 + 2□ S 2H1a2 (6.98) Homogeneous gas-phase reactions

NH1a2 + H1a2 S NH21a2 + □

gas-phase and heterogeneous catalytic