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 r o d uc e.
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p r o du ce.
d o n o t re
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20 Molecular Physical Chemistry for Engineers

r o duc e.
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P 202

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viii Contents

̈
3.3 Solving the Schr odinger Equation
r o du e.
Chapter 5. Statistical Mechanics—
cApplications
for a Particle Moving Freely in One Fundamental
n o t r ep
Ideas and 183
Dimension 87 o n l y o
, dIntroduction
n a l us e 5.1
- 2 4 183
3.4 The Born Interpretationrsofothe
P e Meaning
0 2 8
-0Probability and Statistics 186
05.2
of the Wavefunction, ψ 90 2
5.3 Statistical Occupation of Energy
3.5 Normalization of Wavefunctions 91
Levels 195
3.6 Return to the Free Particle in One
5.4 The Boltzmann Distribution
Dimension 93
Function 205
5.5 Ensembles, Ensemble Averages, and produce.
3.7 Using Wavefunctions to Calculate
Expectation Values 95
o n ot re
e o n ,d
Partition Functions ly210
3.8 The Uncertainty Principle 102
5.6 Then
o s
al u Partition
Molecular - 24 216
Function
8
3.9 Summary 106 e r s 02 0
P5.7 Connecting the2Molecular - 0 Partition
Problems 107
Function to the Internal Energy,
U , for a System of Noninteracting
Chapter 4. Application of Quantum Theory Molecules 221
to the Energetics of Electrons, Atoms, and 5.8 . Connection of the Molecular Partition
r o d u c e Function to the Entropy of a System of
Molecules 111
n o t re p
4.1 Introduction o nly,
111 d o Noninteracting Molecules 223
l u se -24
Pe
4.2 onaParticle
rsThe 0- 0 8
in an Infinite-Walled
0 2 5.9 Calculating the Partition Function
2
One-Dimensional Box 111 for Various Quantized States in
4.3 The Particle in a Finite One-Dimensional Molecules 229
Square Well 121 5.10 Applications of the Partition Function
4.4 Quantum Mechanical Tunneling to Chemical Thermodynamics
Through a Barrier 125 Problems 247
r o du c e.
4.5 Particle in a Two- and Three- 5.11 The
o n o t rep
Configuration Integral 268
, d
only5.12 Entropy
Dimensional Box 131
n a l u s e - 2 4 and the Third Law of
Perso134
4.6 The Harmonic Oscillator 20205.13 -08Thermodynamics 277
4.7 The Rigid Rotor 148 Summary 283
4.8 Observing Vibrations and Rotations of Problems 284
Molecules by Spectroscopy 158
4.9 Infrared Spectroscopy of a Diatomic
Molecule 159
pr o duce.
Chapter 6. The Kinetic Theory n ofot re
4.10 Infrared Spectroscopy of Polyatomic
o nly, d o
Molecules 168 Gases 293
nal u s e -24
P e r s o 20 - 0 8
4.11 Electronic Excitations in 6.1 Introduction 293 20
Molecules 173 6.2 Deviations from the Ideal Gas Law 296
4.12 Summary 177 6.3 Molecular Energies and Speeds of
Problems 178 Molecules 299
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Contents ix

6.4 The Maxwell–Boltzmann Distribution

u c e .
7.8 Adsorption and Reactions on
of Molecular Speeds 301
o t r ep
Surfacesrod388
n Summary 418
do7.9
Problems 340
l u seonly,
ers o n a 24
0-08-Problems 418
P 202
Chapter 7. Chemical Kinetics and the
Rates of Chemical Reactions in Gases Chapter 8. Engineering Applications of
and on Surfaces 347 Molecular Modeling 429
7.1 Introduction 347 8.1 Introduction 429
r o duc e.
7.2 Collision Theory—Reactive 8.2 Quantum Mechanical Modeling
o n ot rep 437
431
Hard-Sphere Molecules 347
s e o n ly, d
8.3 Statistical Mechanical Modeling
7.3 Comparison of Experimental Results for
r s n
8.4
o l u Studies 441
aCase - 08 - 24
Bimolecular Chemical Reactions in the e
P 8.5 Summary20460 2 0
Gas Phase 353 Problems 461
7.4 Transition State Theory of Chemical
Reaction Rates 354 Selected Answers 465
7.5 Connection of Transition State Theory .
to Collision Theory 359t reprodu
ce References 467
l y, d o no State
l u se on
7.6 Expression of the Transition
a
Person Theory 0 8-24
Along -Thermodynamic
2 0 Lines of Index 469
2 0
Reasoning 361
7.7 The Chemical Processes at Work in
Chemical Reactions 365

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p r o du ce.
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P e 202 0

o du ce. Preface
o t rep r
d o n
u s e o nly,
al -24
Person 20 2 0- 08

This book is designed as a one-semester undergraduate course for engi-

neers and materials scientists who need to understand physical chem-
istry. It responds to current trends in teaching this subject with a distinct
r o duc e.
emphasis on the behavior of matter from the molecular viewpoint. The not rep
o n l y, do
book is focused on engineering students at the junior u
n a l e
orssenior level
- 24
e r s o 0 - 0 8
who have a background in beginning chemistry P and
202
physics and in
beginning thermodynamics. A background in calculus and differential
equations is assumed.
The products and processes that today’s engineers and materials sci-
entists create are increasingly based on concepts at the molecular level.
This is true for “hard” materials such
pr o d
as u ce.
semiconductors, alloys, ceram-
o not r e
o n l y, d
ics, and polymer nanocomposites. It is also true for “soft” materials in
a
areasl uofsebiocompatibility,
- 2 4biochemical engineering, and drug design.
r s o n - 0 8
020
Pe Traditional2macroscopic thermodynamics and empirical equations of
state often fail for nanoengineered materials and processes.
After a brief introductory review of basic thermodynamic functions,
the book addresses only three core areas of physical chemistry: quantum
chemistry, statistical mechanics, and kinetics. These areas form one core
r o d u c e.
of modern physical chemistry and are closely linked rwith
o n o t ep each other
and with thermodynamics. A final chapter
o n d with case histories of
ly,deals
n s e
al uto solve engineering - 24problems. The uni-
s
the use of molecular modeling
e r o 0 - 0 8
P core areas and their
fication of the three 202extension to some engineering
applications may often be lost in physical chemistry courses aimed at
students in the applied sciences, which are based on gigantic physical
chemistry treatises.
We believe that the communication of concepts in physical sci-
pr o duce.
ence is often done best through the use of illustrations. Particularly in
o not re
on l y, d
molecular-based sciences, the behavior of molecules can be
l u s e illustrated
in pictorial form with great effectiveness in e a
rson Thus, this 2 0 - is 8-24
0
P teaching. 20 book
filled with drawings of molecular behavior, which illustrate the central
concepts. xi
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xii Preface

We wish to thank our wives, Kerin N. Yates and Linda

u c e . Riding John-
son, for enduring the years associated
o t r ep
with rothed writing of this book.
o n l y
Without their firm encouragement, do nand sacrifice, the book would never
o n a l u se 8 -24
P es
have rreached completion.
2 0 2 0 -
JTY 0 acknowledges with thanks the provision
of a sabbatical leave from the University of Pittsburgh, which made the
writing possible, and the full support of the project by Dean N. J. Cooper.
JTY wishes to thank the Department of Chemistry at the University of
Virginia for its grand hospitality in providing peace and quiet, as well as
numerous important discussions about science and the book. In partic- uce.
t r ep r od
ular, Professor Ian Harrison has been a strong supporter ofnthe
, d o o writing
efforts in many ways. The accurate and u s o n l y
e secretarial
rapid work by Mrs.
r s o n a l - 0 8- 24thanks as
P
Margaret A. Augenstein, secretarye to JTY, is
202 0
recognized with
a key resource for successfully producing this book. JKJ wishes to thank
many colleagues at the University of Pittsburgh and the National En-
ergy Technology Laboratory for helpful discussions and encouragement
of this work. We gratefully acknowledge the help of Giovanni Garbe-
roglio, who made many
p r o d u ce. and helpful suggestions, Oleg Byl for
insightful
d
careful o n o t re of the problems and help with the figures, Matthew
checking
ly,
al use onLaBrosse - 24 Prashant Kumar for carefully checking the manuscript,
and
Person 202and- 0 8
0 G otz ̈ Veser for suggestions on Chapter 7. JKJ thanks Roger Crack-
nell (Shell), David Frurip (Dow Chemical), Joseph Golab (B.P. America),
Michael Golombok (Shell), and Peter Gordon (ExxonMobil) for helpful
discussions on Chapter 8. We thank Professor Robert Enick for early dis-
cussions about the need for this book. We are grateful to John Murdzek
r o d u c e. and Christine
for his very skilled copyediting, and torJennifer
o n o t ep Uhlich
Taylor for their talentedn
s e o ly, d work. Finally, we thank Bruce Arm-
production
o
brustersand
e r n al uEllis at University
Jane
0 - 0 8 - 4
2Science Books for their guidance and
P
encouragement throughout2 0 2 the entire process.

JOHN T. YATES, JR. J. KARL JOHNSON

R.K. Mellon Professor, Emeritus William Kepler Whiteford Professor
Department of Chemistry Department of Chemical and
pr o duce.
University of Pittsburgh
d o n ot re
Petroleum Engineering
Pittsburgh, PA 15260
u s e o nly,
University of Pittsburgh
and
al -24
Pittsburgh, PA 15260
Person
Professor, Department of Chemistry
20
and 2 0 - 08
Fellow—Shannon Center for NETL Faculty Fellow
Advanced Studies National Energy Technology
University of Virginia Laboratory
Charlottesville,VA 22904 Pittsburgh, PA 15236
 r o d uc e.
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p r o du ce.
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20 Molecular Physical Chemistry for Engineers

r o duc e.
o n ot rep
s e o nly, d
e r s o n al u 0 - 08 - 24
P 202

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pr o duce.
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p r o du ce.
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s e o nly, d
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P 202

pr o d uce.
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r o du c e.
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e r s o n al u 0- 08 - 24
P 202

pr o duce.
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t r ep rodu c e . CHAPTER 1
, do n o
se o n l y
Brief Review o nof
a l uSome 08 -24
Pers 20 2 0 -
Elementary Thermodynamics—
The Thermodynamic Functions
r o duc e.
o n ot rep
s e o nly, d
e r s o n al u 0 - 08 - 24
P 202
1.1 Introduction
Thermodynamics historically forms the central basis for the early de-
velopment of physical chemistry. Thermodynamics does not postulate
the presence of atoms and molecules
p r o d
in uce. but deals with the flow
matter,
of heat and work ,todand o n ot re
from thermodynamic systems. Four laws of
o nl y
sthee zeroth, first,
s o n a l
nature,u - 0 8 - 2 4 and third laws of thermodynamics, con-
second
r 2020 basis for thermodynamic reasoning, and these laws
Pe stitute the essential
are empirically based upon experimental measurements.
Engineers use thermodynamics to understand and predict the be-
havior of heat engines, refrigerators, chemical and biochemical reac-
tors, plasma-based technologies useful in semiconductor processing,
r o du c e.
electrochemical cells, and many other technologicallyruseful
o n o t ep devices.
Thermodynamics cannot predict the actual
o n d
ly, magnitudes of the physical
lu s e
isaconcerned,
it n - 4 with changes in
2only
properties with which
e r s o 08
but deals
0-
these properties.PEquilibrium thermodynamics202 also does not apply to
the rate of change of the properties of a system.
In this chapter a brief review concerned with the invention of the ba-
sic thermodynamic functions is presented. It is not our goal to present
a larger treatment of thermodynamics here. The thermodynamic func-
pr o duce.
tions are used to describe various changes in thermodynamic systems,
o not re
on l y, d
and a few examples of the use of the functions for calculating
a l u s ethermody-
-24
namic information are given. In addition, examples
Personof the derivation
20 2 0 - 0
of 8
a few representative thermodynamic relationships will be shown. The
zeroth, first and second laws of thermodynamics will also be discussed 1
 r o d uc e.
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P e 202 0
2 Chapter 1. Brief Review of Some Elementary Thermodynamics

briefly, leaving the third law for later. We will show that
u c e . each of these
od These properties
first three laws give rise to a thermodynamic
o t r ep rproperty.
l y, n entropy, and are associated with
do and
are temperature, internal
u o n energy,
se second laws,
rs o n a l - 08 4
-2respectively.
the zeroth,
Pe first, and
0 2 0
In this chapter we2define the widely used thermodynamic functions,
which will form a focal point for our establishment of a new and deeper
level of understanding of thermodynamics in later chapters. In the chap-
ters to follow, the physical properties of single atoms and molecules
will be molded into these thermodynamic functions. This approach will uce.
t r ep r od
yield the absolute magnitudes of the thermodynamic functions,
l y, d o no some-
thing that thermodynamics by itself cannot u s n
edo.o This is done by using
n a l 08 - 2 4
Perso of atomic
a quantum mechanical understanding 20-molecular
20and behav-
ior, coupled with statistical methods for treating the behavior of large
numbers of particles. This powerful approach is often called statisti-
cal thermodynamics. Using statistical thermodynamics, the thermody-
namic functions may often be calculated with an accuracy that cannot be
r o
achieved through experiment.
p d u ce. This connection between the properties
o n re
otmolecules
o nl y d
of ,atoms and and the thermodynamic properties of materials
al use constitutes - 2 4one of the shining examples in the development and appli-
Person - 0 8
0 of physical chemistry to both chemistry and applied engineering
202cation
areas. You will be introduced to some of the most exciting and important
twentieth-century developments in our revolutionary thinking about
the physical nature of the universe.

r o du c e.
1.2 Thermodynamic Systems o n o t rep
s e o n ly, d
e r s o n al u system must
A thermodynamic
0- 08be-2 4 before one can proceed to un-
defined
P
derstand 20
its behavior. 2 closed and open systems are considered in
Both
the study of thermodynamics. The boundary of a closed system allows
the passage of energy in the form of heat and work to or from the system
and its surroundings, but mass does not flow across the boundary. The
boundary can be defined mathematically or as a physical boundary, and
pr o duce.
the boundary may move when, for example, a gas expands in o
o n re
a tcylinder
behind a moving piston. The boundary mayehave o nany d
ly, shape. An exam-
u s
onal would be 8 -24 where,
Perssystem
ple of a closed thermodynamic
20 2 - 0
a0refrigerator
as heat and work flow across the boundary, no refrigerant escapes to the
surroundings.
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1.3 The Zeroth Law of Thermodynamics: Temperature 3

Boundary Heat
p r o du ce.
d o n o t re
u s e o nly,
al -24
Person Closed system
20 2 0- 08

Surroundings Work

r o duc e.
o n ot rep
Mass
s e o nly, d
Open system
e r s o n al u Mass 0-08-24
P 202

Heat

r o d uce.
Figure 1.1. Closed and open thermodynamic systems.
p
l y, do not re
e o n
r s o n al us - 0 8 -24contains
Pe 20
An open 2 0
system also boundaries that transmit heat and
work to or from the surroundings, but the open system boundary can
also transmit mass as, for example, in a chemical reactor where reactants
flow into the system and products flow out. A distillation column is
another example of an open system where material flows in and out of
r o du c ein.
n o t p
the system. The two types of systems are illustrated schematically
resystems.
on ly, d
Figure 1.1. Most of our discussions will deal o
with closed
n a l u s e - 24
e r s o 0- 08
P 202
1.3 The Zeroth Law of Thermodynamics: Temperature
Consider two systems that are individually at equilibrium (i.e., the sys-
tems are not changing as time passes), but are at different temperatures.
When these systems are placed into thermal contact, our experience tells
pr o duce.
us that heat will flow from the warmer system to the cooler system un-
o not re
on l y, d
a l u s e
til the two systems reach the same temperature. When the temperature
n systems will2have -24
P rsotwo
has become equalized, equilibrium betweenethe 0 - 08
20
been achieved and heat will cease to flow. Temperature is a thermody-
namic property, or a thermodynamic state function, of a system and
 r o d uc e.
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P e 202 0
4 Chapter 1. Brief Review of Some Elementary Thermodynamics

the temperature governs the direction of flow of heat between

d u c e . different
thermodynamic systems in contact with
o t r ep
eachroother.
o n l y , do n states that when two systems are
The zeroth law of thermodynamics
at thers o n a l use as a-0 8 4 each is at the same tempera-
-2system,
P e same temperature
2 0 third
20another way, if we have three systems, A, B, and
ture as the other. Stated
C, and if A is in thermal equilibrium with C, and B is in thermal equilib-
rium with C, then systems A and B must also be in thermal equilibrium.
The zeroth law is an expression of our observation of the behavior of
macroscopic systems in thermal contact with each other that “speak” to uce.
t r e p r od
each other through the flow of heat across a common boundary
l y, d o no until the
thermodynamic property of each system, u s
called n
e o temperature, becomes
n a l - 2 4
equalized. It is interestingP rsothat all other20
toenote 20-08
thermodynamic proper-
ties of a system, such as pressure or volume or density, are generally not
equalized when thermal equilibrium has been achieved between dif-
ferent systems. It is also interesting that in thermodynamics we do not
need to understand the behavior of moving atoms and molecules when
considering heat andro
p d u
heat ce. Thermodynamics has no need to recog-
flow.
nize d o
the n o t re of the fundamental particles of which substances are
behavior
se ly,
oncomposed.
o n al u 8 -24
Pers 2020-0
1.4 The First Law of Thermodynamics:
The Internal Energy, U
The internal energy, U , is a thermodynamic property
o du c . is character-
ethat
istic of a thermodynamic system. n o
Thet r
rep U is also called a ther-
property
o n ly,and o
d its value will depend upon other state
n e
modynamic statesvariable
al atu temperature, - 24 and the mass of the system. For
e r s o 0 - 0 8
variables
P such
202 pressure,
a single pure substance existing in a single phase (solid, liquid, or gas)
at rest and in the absence of surface effects, strong magnetic, electrical
and gravitational fields, and in the absence of mechanical forces such
as shear in a solid, the value of U is determined by only the number of
moles in the system, n, and two independent state variables. Thus,
t r epr oduce.
′′do n o
U, (n, T , V). (1.1)
Un=ly
ore o
′
U = U(n, p , T) or U = U (n, p , V)us
al -24
Person 20 2 0 - 0 8
The variables that specify the state of a system are classified as exten-
sive or intensive variables. Extensive variables are proportional to the
 r o d uc e.
l y, do not rep
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r s o n al - 0 8- 24
P e 202 0
1.4 The First Law of Thermodynamics: The Internal Energy, U 5

mass of the system. Volume is an extensive variable. Intensive variables.

p r o d u ce
are independent of the mass of the system. Temperature
d o n o t re and pressure

u s e o
are intensive variables. Extensive variables nly, may be converted to inten-
l 8-24 variable by the
ersonathe value20of2the
sive variables by dividing
P 0-0extensive
mass or by a quantity proportional to the mass, such as the number
of moles. The molar volume (m3/mol) is an intensive variable, as is the
density.
We may convert extensive variables, such as U and V , into intensive
variables Um and Vm commonly used in chemical thermodynamics by
r o duc e.
dividing by the number of moles contained in the system, n. Thus, not rep
Um = U/n, Vm = V/n, and so forth. The quantity Um is called o n l y, do
s o n a l use the molar
- 08- 24
internal energy.
′ ′′
P e r 202 0
The various functions U , U ,orU are particular equations of state
for the thermodynamic system, and are analogous to another equation
of state that we recognize for an ideal gas, p = RT/Vm , where R is the gas
constant. Just as the pressure of an ideal gas is determined by adjusting
r o d
only T and Vm , so also only two independent
p u ce. intensive state variables
specify the system’s d o n
molar o t re Um . It is amazing to contemplate
internal,
se o ly,
nconsisting
s o n a
that l ausystem
- 0 8 - 2 4 Avogadro’s number of moving molecules
of
r
Pe can have its2molar 020 internal energy exactly determined by adjusting only
two independent state variables, which are macroscopically controlled
in the laboratory.
Figure 1.2 shows a closed system containing a pure substance in a
particular phase where a differential quantity of heat, δq , and a differen-
r o d u c e.
tial quantity of work, δw, pass across the boundary to cause
o n o t repthe internal
energy to change by dU from an initial
s e o n y, d U0, to a final value, U1.
lvalue,
The internal energy ofsthe
e r o n al u changes0according
system
- 0 8 - 24 to the first law of
thermodynamics, 02 conservation. Formally, the
Pwhich is a law of 2energy
first law of thermodynamics may be written as

dU = δq + δw . (1.2)
pr o duce.
d o n ot re
Here the convention is to measure the heat and work from
s e o
the ly,
nview-
son l u
theasystem - 0 8-24
Perinto
point of the system (i.e., heat or work flowing 2 0
is positive
20
in sign). During the flow of heat and work, if we could measure the inter-
nal energy change, dU, of the system internally by means of an “internal
 r o d uc e.
l y, do not rep
use o n
r s o n al - 0 8- 24
P e 202 0
6 Chapter 1. Brief Review of Some Elementary Thermodynamics

p r o du ce.
U ly, do n
ot re
l u s e on
1
4
r s o n aδ q
- 08 - 2 dU
Pe 2020dU

U0

δw

r o duc e.
Figure 1.2. Heat and work flow to change the
o n ot rep
internal energy, U .
s e o nly, d
e r s o n al u 0 - 08 - 24
P 202
energy meter,” we would find that the change would be as shown in
the schematic in Figure 1.2. The differential quantities, δq and δw,are

d uc e .
called inexact differentials, which means that they cannot be directly
integrated since
o t r e prodepend
they upon the pathway employed in causing
l y n
do in state related to dU. On the other hand, the quantity dU
, change
use o nthe
al -24differential, and it may be integrated between two states of
Person 2 -
is an
0 0 8
exact
20 the system independent of the pathway connecting the two states. The
integrated value, U , depends only upon the limits of the integration,
between the initial and final states of the system.
The exact differential function for the molar internal energy, dUm ,
may be used in differential equations based on u
r o d c e. 1.1 of the
Equations
following form:
l y, do not rep
u s e o n
n a l ( )
- 2 4 ( )
Perso dUm 2 = 02∂U0m-08dp + ∂Um
dT (1.3)
∂p T ∂T p
( ) ( )
∂Um ∂Um
dUm = dp + dVm (1.4)
∂p Vm ∂Vm p
( ) ( )
p r o duce.
dUm =
∂Um
dT +
∂Um e
dVm, .do not r(1.5)
∂T oTnl
y sem
∂V
V
al u -24
Person
m

2 0 - 08
Additional useful
20
relationships involving partial derivatives of
thermodynamic functions originate from differential equations of the
 r o d uc e.
l y, do not rep
use o n
r s o n al - 0 8- 24
P e 202 0
1.5 Some Forms of Work 7

form shown in Equations 1.3–1.5, where here Equation 1.3 is used as an.
p r o du ce
example:
d o no t re
e o+n l y,
a l u s , 8-24
Person m
=
dU Mdp
20 2NdT
0 - 0 (1.6)

where
( ) ( )
∂M = ∂N
, (1.7)
∂T ∂p
p T
r o duc e.
since o n ot rep
[ ) ] l use on
ly, d p
[ ( ) ] ( 4
ermsona, 8-2
ext

∂ ∂Um = ∂ P∂U 0 2 0
2 (1.8)- 0
∂T ∂p T p ∂p ∂T p T

and the order of differentiation is immaterial. Useful solutions to ther-

modynamics problems often hinge on the recognition of relationships
like those in Equations 1.3–1.7. Anro
p d uce.will be given later in con-
example
d o
nection with the Maxwell n o t re
relationships, which have far-reaching conse-
o nl y,
e thermodynamics.
dV
al usin
quences -24
Person 2020-0
8
1.5 Some Forms of Work System

A number of forms of work may be done upon a thermodynamic system

and this flow of work will contribute to the change in the internal energy,
r o du c e.
U , of the system. A common form of work involves
n o t p expansion
rethe
o n o
ly,thed presence of an external
or contraction of the system’s volume
n u s e
alillustrates
in
- 24 the expansion of Figure 1.3. Expansion work—
e r s o 0 - 0 8
applied pressure. Figure
P 1.3
202 schematically
the system against a constant applied external pressure, p ext,inan 3D system.
idealized cylinder containing a frictionless piston. As the piston rises,
the system loses energy as work is done in the surroundings, and the
differential change in the work for volume change, dV ,is

pr o duce.
δw =−p extdV . (1.9)
d o n ot re
u s e o nly,
al -24
Personare either 2consumed
In chemical processes where gaseous substances
0 20 - 0 8
or formed, expansion work is important as one factor in governing the
flow of energy to or from the reactor.
 r o d uc e.
l y, do not rep
use o n
r s o n al - 0 8- 24
P e 202 0
8 Chapter 1. Brief Review of Some Elementary Thermodynamics

A second form of work that one might consider in.particular ther-

dA
p r o d u cofea film, as shown
modynamic problems accompanies the
d o n o t re
stretching
o
schematically in Figure
s e ly, for an idealized film supported on a rec-
n1.4
u
nal and stretched 8 4
-a2movable
P ersoframe
tangular
2 0 2 0 - 0
by light weight bar of length,
, which is wetted by the film. Here, the differential work for the area
f =γ Film
change, dA, is given by

δw = γdA, (1.10)

r o duc e.
where γ is the surface tension or surface energy of the filmnin
o o t repof
units
Figure 1.4. Film stretching −
Nm 1. The force exerted on the film is fu= γ o
e , d work will
nlypositive
work—2D system.
o n l s
apositive , and
8- 24
be done on the system whenP e r s
dA is 202
and 0
the- 0
film increases in
surface area. Hence as the surface area increases, the work being done
on the film increases its surface energy, γA. This is just opposite to the
sign of the work for an increase in volume of a gas against an applied
pressure. In the formation of bubbles in a liquid in an engineering
p r
process, considerationso d u cethe. work being done to stretch the bubble
of
o n o e growth is of importance in governing the energy
t rbubble
ly, d
surface during
al use onbalance,- as4are considerations about the increase in the volume of the
2
Person 0 - 0
202bubble,
8 which involves gas expansion work. The sign of the work for
the two physical processes during bubble growth is opposite.
These two examples illustrate only two forms of work encountered in
thermodynamics. Other forms of work can involve the electrical charg-
ing of a cell or capacitor, the stretching of a spring, or the magnetization
r o du c e.
of a substance.
o n otrep
only, d
n a l u s e - 24
e r s o
P The Internal2Energy,02 0 - 08
1.6 U , in a Constant-Volume
Change in State
The internal energy state function, U , is naturally connected to thermo-
dynamic changes that occur at constant volume. Consider a thermody-
p r o duce.
namic system containing a single-phase substance which, because
do n ot reof a
rigid boundary, remains at constant volume asoheat,
u s e nly, δqV , is absorbed.
Under these conditions,
Pe rsonal 2020 -08-24
p ext dV = 0 = δw , (1.11)
 r o d uc e.
l y, do not rep
use o n
r s o n al - 0 8- 24
P e 202 0
1.6 The Internal Energy, U , in a Constant-Volume Change in State 9

and by the first law,

p r o d u ce.
dU = δqV = CnVly d o n o t re
e o ,
dT , (1.12)
r s o n a l us - 0 8 -2for4 the system. If we
where CV is thePe
constant 20
volume heat 2 0
capacity
know the value of CV , and we can measure dT , we have in our hands the
internal energy meter for this change in state, as schematically shown
earlier in Figure 1.2.
In order to proceed logically in studying a thermodynamic change
r o duc e.
in state, it is convenient to be able to write the change in state in a
o n ot rep
, d
only V , 4
convention that clearly specifies exactly what is occurring within the
l u s e
system. Let us consider one such state change at
P e r sona
constant volume,
2 0 20 - 1 8-2
0
written by convention as shown in Equation 1.13:

n moles N2( g ) [V1, 293 K] → n moles N2( g ) [V1 , 294 K]. (1.13)

Our standard method of writing the change

o d u c e . in state involves spec-
o
ifying for the initial andnfinal t r e pr the quantity of the substance, the
states
e
identitysof o
then ly, do its phase, and two independent state variables,
substance,
r s o n a l uin this particular
- 0 8 4
-2example
Pe which
2 0 2 0 are the volume and the temperature.
The specification of only these variables completely defines each sys-
tem and each system may be produced with exactly the same properties
in any laboratory by adjusting the parameters (V and T ) employed in
Equation 1.13 to the same values. It is advisable in all thermodynamic
problems involving a change in state to first write out the change
r o du c ein.
o n o t reinpstate shown
state in the format shown in Equation 1.13. The
s e o n ly, d of nitrogen gas from
change

e r s o n al u
in Equation 1.13 involves changing the temperature
0- 0 8 - 24
293 K to 294 K, P keeping the volume 2 02 V1 in the numerical exam-
constant.
ple shown below corresponds to a pressure of 1 bar at 293 K. The heat
flow in a constant-volume process is a measure of the internal energy
change.
The change in molar internal energy of the system for N2 (g) is
pr o duce.
given by
o not re
∫
on l y, d
Q V = 294 l −u1s e
a
JsKonmol 1K 0-08-24
= ∼ −1 ×
U m
n 293
CV ,m dT = 20.816
P e r 202
= 20.816 J mol− 1 , (1.14)
 r o d uc e.
l y, do not rep
use o n
r s o n al - 0 8- 24
P e 202 0
10 Chapter 1. Brief Review of Some Elementary Thermodynamics

d u c e .
where Q V is the total heat transferred to the system at constant volume
o t
and CV ,m (obtained from the NIST Chemistryr e p roWebBook, webbook.nist
l y o n
, daccuracy)
.gov) is considered (to
u s e o nhigh to be constant over this small
P nal
e ofotemperature.
rangers
2 0
Over - 08
larger 4
-2temperature ranges, CV ,m must be
2 0
considered as a function of T , and the integration must be performed
using this function.
This is a very simple change in state, but other more complex changes
in state, such as the complete combustion of a substance in a constant-
volume oxygen bomb calorimeter, also naturally involve changes in uce.
t r epr od
molar internal energy, U m , since the heat effect is measurednat
, d o o constant
n l y
volume.
s o n al use o - 08- 24
P e r 2020
1.7 The Enthalpy, H , in a Constant-Pressure Process
The enthalpy function is defined as a particular combination of three
other state variables:
pr o d uce.
l y, d o not re H U + pV .
≡ (1.15)
u se o n
o n al 0 8-24
Pers 2 0 -
20 (The triple equal sign, ≡ , means that a fundamental definition is being
written.)
By considering a differential change, dH, we may write

dH = dU + pdV + Vdp = δq + δw + pdV + Vdp. (1.16)

odu c e .
t r ep r
If only expansion work occurs,
l y, d o noδw pdV, and if the pressure is
then =−
n
e oEquation 1.16
=u0sand
s o n a
constant, Vdp l - 08 - 2 4becomes
Per 2020 = =
dH δqp Cp dT , (1.17)

where Cp is the constant-pressure heat capacity of the system. The heat

flow for a constant-pressure process is therefore a measure of the en-
thalpy change.
p r o duce.
o n o
Let us consider now a process very similar to that discussed in e
t rEqua-
o d
nlyat,constant pressure,
tion 1.13, except now the change in state u
l s
willeoccur
-24
p 1, rather than at constantP ersona
volume. 20 2 0 - 08
n moles N2( g ) [p 1 , 293 K] → n moles N2( g ) [p 1, 294 K]. (1.18)
 r o d uc e.
l y, do not rep
use o n
r s o n al - 0 8- 24
P e 202 0
1.7 The Enthalpy, H , in a Constant-Pressure Process 11

For this change in state, where p 1 = 1.000 bar, the change in molar.
p r o du ce
enthalpy is given by t re
d o no
e on l y,
∫ on a l u s 8 -24
Pe
Qp r s 294
2∼0 2 0 - 0 −1
= = −1 × 1K
H m Cp ,m dT= 29.171 J K mol
n 293

= 29.171 J mol− 1 , (1.19)

r o duc e.
where Q p is the total heat transferred to the system at constant pres- not rep
o n l y, do
sure and Cp ,m (obtained from the NIST Chemistry WebBook)
s o n a l use is consid-
- 08- 24
ered to be constant over the small rangePof ertemperature.
202
If we 0
know
the value of Cp ,m, we have in our hands an enthalpy meter for this
change in state, analogous to the internal energy meter of Figure 1.2.
Integration over wider temperature ranges will require the recognition
of the temperature-dependent function, Cp ,m. The enthalpy change is
equivalent to the heat flow for a o
pr d uce.
constant-pressure process, and the
enthalpy function, Hdmo, was r e
notdevised to relate to constant-pressure ther-
e n l y,
oprocesses
o a l u s
modynamic
n 8- 2
of 4many types, just as the internal energy, Um ,
r s 0 - 0
Pe was devised20for2constant-volume processes. Engineers use the enthalpy
function for heat flow calculations for chemical reactions that occur at
constant pressure, often at atmospheric pressure.
Now let us compare the Vm = constant and the p = constant warm-
ing processes. Figure 1.5 schematically illustrates the two changes in
o d u c e .
state. In the constant-volume case, there is no expansion
o t rep∫ r
work, but in
the constant pressure case, the expansion ∫nly, d
worko n
is ∫w =− pdV. For
l us=− o
e pdVm =− 4
an ideal gas, pVm = RTo
er s n a
, and w/n
- 0 8 - 2 RdT =−RT =
− 8.314 J mol− 1 Pfor T = 1 K. Looking 202at0 the two examples from the
point of view of the heat flow, the difference in heat flow = H m −
−
U m = (Qp − Q V )/n = (Cp ,m − CV ,m)(1 K) = (29.171 − 20.816)J mol 1=
− ∼
8.355 J mol 1 = RT . The small difference between the actual and ideal
gas values is due to the nonideality of the nitrogen gas at these condi-
pr o duce.
tions. The value of H m − U m is just the extra energy in the form of
o not re
on l y, d
heat input that is required to produce the negative work (i.e,
a l u s e the work
-24
ejected by the system in the constant-pressure rson The nitrogen
Peprocess). 20 2 0 -
gas0 8
comes to the same temperature and internal energy, U , by means of the
two processes. We have just shown by means of a numerical example
Another random document with
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darted into the tunnel with the waves lapping at my heels, and
followed Kahikatea.
When I reached the marble cave I stood and surveyed the scene
before me with feelings of regret, dismay, and despair. A great slab
of stone had slid down in the grooves that I had noticed on each side
of the opening, and the place was closed even to the moon and
stars; but what called up all my grief afresh was a thing of which I
had been convinced ever since I left the cave to find Hinauri. The
marble statue no longer stood in the centre of the cave with its arms
outstretched. There, on the floor, broken and shattered, were the
fragments of the lovely image which Miriam Grey, as a sculptress,
had hewn out of the sacred stone; and there, a little beyond, lying
upon a soft Maori mat, was the still cold form of the lovely spirit
which she, as a mother, had led out of the distant past.
As I made my way among the fragments, I picked up the golden
circlet, and, bending down, gently placed it upon Hinauri’s brow. At
once the prophecy came to my mind—the prophecy she had read
after solemnly identifying herself with the statue: “Thou, Hia, shalt
return at the dawn of a new age, but ere the sun shall have shone
twice upon this, thy crown, thou shalt withdraw into the sky.”
Kahikatea was in the recess of the inner cave, holding in his hand
the rope by which he had descended.
“I will go first,” he said; “then I will let the rope down a little so that
you can make a double loop for her, and I will draw her up. After that
I’ll let the rope down again for you. But wrap her in the mat,
Warnock, and fasten the rope securely.”
He began to climb as he gave these directions, but he was
scarcely five feet from the ground when the strands broke far up
above and he fell heavily, the whole of the rope rattling down into the
cave about us.
“Must have frayed on the edge of the rock,” he said, struggling to
his feet. “Well, I suppose there’s nothing to do now, my friend, but sit
down here quietly and wait for the end, for the water will be here
presently, and there’s no other outlet. Certainly we might float up, but
for my part I don’t think it’s worth while.”
So weary of life was I that I was tempted to agree with him; but I
chanced to glance round the cave before I spoke, and my eye fell on
the grotesque wooden gods grinning at our hopelessness as they
nursed their stomachs serenely. A sudden idea struck me: why not
make a raft of these wooden deities, and so float up on the rising
flood? I mentioned my idea to Kahikatea, and he greeted it with a
half-smile. Such a slight thing changes the course of mortals, and I
believe it was the mere happiness of this idea that led us to combat
what was at that time a great temptation to leave our bodies with that
of the one we both loved, and go out into the starry sky with Zun to
find her.
With a spontaneous movement we sprang up and set to work. I
remembered that in the Place-of-Many-Chambers there was a deep
gulf to fill, and consequently it would be some time before the water
reached us.
So we took Tiki, the Progenitor of Mankind, and Tangaroa, the sea
god, and Tawhirimatea, the god of storms, and Tanemahutu, and
Rongomatane, and several others, and, laying them side by side on
the floor of the cave, lashed them together with the rope. There was
a store of torches in this as in all the other centres of the temple, and
we set several going to light us in our work.
At length it was finished, and we laid the dead upon soft mats in
the centre. I also placed on our raft the remainder of the torches, and
an axe I found among the weapons. Then we sat and waited,
Kahikatea at Hinauri’s head and I at her feet, both bearing torches in
our hands. In time the water flooded in with gurgling sounds, and we
rose on our raft of gods up through the opening in the roof of the
mountain. When we had mounted some fifty feet I looked up
between the dark crags that still towered above us and saw the stars
in an indigo sky. Slowly we floated up with our fair burden until, upon
a crag above us, we saw the silver moonlight glistening. In a few
minutes we reached that crag, and found we were on the broad
summit of the mountain temple, the twin peaks rising one on each
side of us, their snowy summits standing up like sentinel spirits as
the moonlight touched them in the clear, cold silence of the sky.
The raft now floated into a small oblong basin, and as the water
rose in this I saw that it would flow out through an aperture beyond.
Here, then, was our highest point. I stepped out on to the roof of the
mountain temple. Kahikatea followed, and together we lifted our raft
of gods with its burden out on to the rough rocks. As we did this the
water escaped at the other end of the oblong basin, and I advanced
with my torch to see what became of it. Beyond the aperture its
surface shone in the moonlight, making a loop like a silver
horseshoe; then it disappeared again into the rock at a spot not very
far from where it issued.
I looked up at the southern peak, and then at Kahikatea, who
stood beside me. “Yes,” he said, interpreting my thought, “there is a
large lake up there. I came across it in my wanderings. It is no doubt
the source of all this water.”
“The crystal lake that stands against the sky,” I said, slowly
repeating Hinauri’s own words; “is there a way to it?” I glanced
towards the raft as I spoke, and my voice was lowered almost to a
whisper.
“Yes, there is a tunnel,” he replied softly. “Come! our raft is now a
bier. Let us carry out her wish.”
So we severed Tiki, the Progenitor of Mankind, and Tanemahutu,
the strong god of light, from the others, and, using them as a bier,
passed up through a narrow but lofty tunnel in the direction of the
Southern peak. After we had ascended some hundreds of feet by a
fairly steep incline, we came out on the margin of a large circular
lake held in by towering crags against the side of the peak. The clear
waters were still and pure, as befitted that high solitude, and in the
crystal depths were reflected the lights of Heaven. We descended to
the shelving, sandy shore, and set our burden down in the shadows.
Then, by mutual understanding, we went back and carried up the
rest of the gods and the pinehearts and the axe. And Kahikatea
himself hewed the gods in pieces to supply the wood for the funeral
pyre.
I cannot linger over that last sad scene by the silent lake. I cannot
write of Kahikatea’s last kiss of farewell on those pure maiden lips. I
stood apart, bareheaded beneath the moon and stars, gazing my
last upon the serene white face as, with hands crossed upon her
bosom, and her shrouding hair drawn over
 “WITH HANDS CROSSED UPON HER BOSOM, AND HER
SHROUDING HAIR DRAWN OVER HER LIKE THE CURTAINS OF THE
NIGHT, HINAURI LAY UPON THE PYRE.”

her like the curtains of the night, Hinauri lay upon the pyre. Then the
pinehearts blazed up, the bones of the gods crackled and hissed,
and soon the form of the one we had loved and lost was enveloped
in a clear, glowing pyramid of flame, which burned up to heaven like
the light of a great lamp set in a spot well sheltered from the wind.
*****
I recall but dimly our leaving that crystal lake against the sky, and,
in the grey light of dawn, reaching the Table Land below by ways
difficult and dangerous. Suffice it to say that the ‘way of the spider’
by which Kahikatea had scaled that mountain was such that no man
who valued his life would attempt it. How we passed in safety is a
matter that I can only account for by the fact that we did not value
our lives at all.
The yellow, rolling plain was deserted when we passed across it,
and none greeted us from the wharés dotted about here and there.
We stopped nowhere until we reached the further end of the Table
Land, and there we turned to gaze for the last time on the mountain
wall that shut out half the eastern sky. It was a grand and solemn
tomb of things forgotten; stupendous, majestic, threatening in its
gloom. But on the snowy peaks above there rested a flush of sunrise
—a rosy pink which touched them with a pure and radiant glory as
they stood against a background of white rifted clouds. Though the
giants’ temple, with beetling brows, frowned darkly at us, it seemed
as if the rosy peaks were showing the sun which path Hinauri, the
Daughter of the Dawn, had taken.
A day’s march brought us to the place below the great cliff in the
hillside, where we had seen the water spout up in a fountain, and
where, subsequently, I had found my hat which had fallen into the
abyss. The channel was dry, and the pool from which it issued had
sunk several feet. I conjectured that if that underground stream could
be followed, the explorer would come up against the great round
stone, stopping the water’s flow somewhere in the bowels of the
earth.
Two days’ march brought us to Kahikatea’s hut, where he put a
few papers together, and announced his intention of journeying with
me as far as Wakatu, and thence taking a boat for the north, and
finally for England. When he informed me of this I looked at him
inquiringly. He saw the question in my eyes, and said:
“Friend! my dreams have ended sadly, but the strange madness
that drew me to this solitude was, I know now, full of hidden method.
You heard what she said: ‘Hasten on the world.’ Warnock! if ever a
man tried, by putting his shoulder to the wheel of time, to hasten the
dawn of a brighter age, I am going to try. She told me many things
that you did not hear and that I cannot tell you—things throwing light
on the world’s failure in the past to grasp its opportunities—plans to
pave the way for an inborn greatness of a coming generation. When
you think of me, Warnock, think of me as one who is toiling
incessantly with dull, heavy foundation stones at the bidding of a
voice which to him is the sweetest thing in all the world.”
At Wakatu we found Grey and his wife, and together we helped
one another through the story of Hinauri’s death. The Man-who-had-
forgotten heard it as a thing far off; it touched him like the sadness of
a dream, for eighteen years were struck from his life, and he
remembered neither his own daughter nor the Daughter of the
Dawn. But Miriam’s grief, the grief of such a mother for such a child,
was beyond words. For many weeks after Kahikatea’s departure she
lingered between life and death in Wakatu, and it was not until three
months after the events narrated in the foregoing pages that I told
Grey all I knew about his forgotten years, and sailed with them both
to the Sounds—to the home and the garden where I had first met
Crystal Grey. In due time they went home to claim the property,
which, as I have somewhere stated, had been left to Miriam. I
remained behind to take care of the old place until they returned a
year later, when they refused to let me go.

Here, then, in the rustic retreat beneath the nut-trees, where the
sweet influence of Crystal Grey seems to linger round me, I have
spent the summer days in writing these pages. Now it is finished,
and again I recall the words of my aged friend the chief and tohunga,
Te Makawawa:
“O Son, the word of our ancient law is death to any who reveals
the secrets that are hidden in the Brow of Ruatapu. The secret of
Hinauri, the Daughter of the Dawn, the mystery of the Vile Tohungas
of the Pit, the traditions of far time preserved in the heart of the great
Rock—all, everything, is a death-blow returning on the head of him
who reveals it. Yet, O Son of the Great Ocean of Kiwa, I, who was
once the guardian priest of the temple of Hia and the hereditary
curser of the Vile Ones of the Abyss of Huo, now show these things
to you, for I am weary of climbing the snows of Ruahine, and long for
rest and Tane’s living waters. The great Tohungas of the Earth have
taught me in my sleep with words like the voice of the wind in the
forest trees: ‘O tohunga of the Great Rock, the mystery of Hinauri is
not for the Maori unless thou tell it first to the Sons of the Sea, but
know that if thou tell it thou must die.’ Therefore, Son, I show it to
you, for what though I fear the eye of the fierce Ngaraki, I fear not
death. Friend! perchance, when I have descended by the sacred
Pohutukawa root, you, too, will tire of life and tell this thing to your
brethren; ‘but know that if thou tell it thou must die.’ ”
I am content that it should be so. Last night I dreamed that I
wandered astray in the forest, and that is an omen that no Maori
could misinterpret. Perchance it is the shadow cast before a
welcome event, in terms of the Maori lore so dear to my heart. And
now as I write, another and more striking omen is vouchsafed me in
the same quaint terms. A ray from the golden sun of the autumn
evening slants through the broken screen of yellowing leaves and
falls upon the woodwork of my rough table placed against the hazel
stems. Suddenly a little green lizard runs from a bundle of papers I
have but lately lifted from the ground and placed on the corner of the
table. It reaches the sunlight and pauses, moving its head strangely
in the air. In another moment its bright little eyes meet mine, and for
some seconds it remains motionless. A cloud comes before the sun,
the ray fades, and the little creature wriggles off the table on to the
ground, where I hear its faint rustle among the leaves. Well I know
this is a call to Reinga, thence to the living waters of Tane, and
thence to the bright Beyond—a summons, clear and sweet, to the
Living Waters of Tane, where mortals fling off their garments of clay,
and, plunging deep, renew their strength. Oh! let it be soon. How
often have I longed, with the great chief who now clings to Life in the
Light, to throw my body headforemost into the jaws of Darkness, that
I, with him, may gain the sparkling stars, and look into her eyes once
more!

THE END OF WANAKI’S NARRATIVE.

 CONCLUSION.
(A letter from Aké Aké Rangitane, the son of Ngaraki, to the
Editor.28)

O Friend of the Maori Race,—These are my last words

to you, for while you remain here among the chills of winter, I
go to the land which laughs beneath the southern sun. My
experience of the will of the Great Tohungas of the Earth
teaches me that it will be obeyed concerning the record of
Wanaki. When you have done my bidding and the book is
made, then you will remain at peace. I send to you with this a
letter that has been given to me by the Pakeha Kahikatea. Set
it at the end of Wanaki’s record, but do not write the Pakeha’s
other name, for it may be that he has the spirit of one of the
Great Tohungas of the Earth whose names are tapu. When
your task is done, fear not that the fate of Wanaki will overtake
you. Now I go, but you remain. Follow me not with your
thoughts. When I see the book that is made the love of my
heart will flow towards you like a mountain stream. There is
no Maori word to tell of “gratitude,” but, O Pakeha, in the
Maori heart there are feelings which cannot be hidden behind
a word. My letter to you is ended. Farewell.

A letter from Miriam Grey to Sir… Bart.,… St. James’

Chambers, London.

Dear Kahikatea,—It is with feelings of deep regret that I

write to tell you of the death of our dear friend Wanaki. The
circumstances of his end were very strange. It was a night
when a thunderstorm was brewing, and Wanaki, instead of
going to bed, put on his mackintosh and went out to look at
the storm. But it did not break till near midnight, and then
there was only a single vivid flash, followed by a peal of
thunder directly overhead. In the morning, finding our dear
friend’s room unoccupied, we searched the garden and the
plantations, and at length discovered him lying dead on the
grass at the foot of one of the great bluegums. That he had
been struck by lightning while standing with his back to the
tree was evident, for the grass where he had stood was burnt,
and his watch chain was fused. But the strange thing that I
have to tell you is this: On the trunk of the tree against which
Wanaki had been standing, the lightning had left a mark which
is evidently a duplicate tracery of the course the electric fluid
took through his body, but at the same time—this is no
woman’s fancy—I recognised it as an exact picture on a small
scale of the principal ways of the ancient temple, from the
marble cave to the foundations. I say again, this is not my
fancy, for if anyone could recognise the diagrammatic
representation of the spiral tunnels and spaces of that ancient
place it would surely be myself. Is this another instance of the
strange magic of that terrible priesthood of the ages, which
has now left its sign to show that Wanaki has suffered the
penalty for revealing the secrets of their temple, or is it
capable of a simpler explanation? Is it possible that the
lightning followed some occult line of least resistance through
that temple of the ages—that mysterious epitome of the
universe, the human body, and left the track of its passage
burnt in on the tree behind? But I cannot do more than merely
suggest the mystery of this exact correspondence, for both
my husband and myself are heartbroken at the loss of our
dear friend, the story of whose snow-white hair and gentle,
weary face, you already know.
I will not write more now except to add, as ever, that my
heart is with you in your work—with you as constantly as my
thoughts are with her whom we love, and as earnestly as my
prayers are with those of all women who stand in the “Brow of
Ruatapu” and raise their arms of longing to the heaven where
greatness waits to be revealed on earth.

Yours sincerely,
MIRIAM GREY.
THE END.
 ENDNOTES.
1 karakia] Philosophical and meditative hymns used as
incantations.—Editor.
2 pa] A pa is a fortified village, a stronghold.
3 Kahikatea… my friend the Forest Tree] The Maoris regard the
Kahikatea, or white pine, with much poetical feeling.—Editor.
4 rangatira] Gentleman.
5 the green lizard that will summon me to Reinga] The Maori

believes that when the little green lizard looks at him meaningly it is
a summons for him to depart for the spirit world within three days.—
Editor.
6 tiki] An ornament of jade fashioned in the image of Tiki, the first
man, and worn round the neck.—Editor.
7 white-winged taniwhas] The taniwha of the Maoris is a mythical
monster of the deep. When they first saw the Pakehas’ ships they
set them down as taniwhas.—Editor.
8 kohutukutu] The wild fuchsia—the only deciduous native tree.—
Editor.
9 wharekura] An ancient Temple of Mysteries.—Editor.
10 Zun the Terrible] Wanaki has a note here to the effect that,
although the Maori’s pronunciation of this name was ‘Tunu,’ he
prefers to preserve it in what he avers was its original form, viz.,
‘Zun.’—Editor.
11 matakite] Clairvoyant.
12 tapu] Sacred.
13 its spirit had fled beyond Wai Ora Tane] The bourne from which
no traveller returns.—Editor.
14 matakite] A seer—a clairvoyant.—Editor.
15 mana] Power, prestige.—Editor.
 16 kumara] The kumara is a kind of sweet potato.
17 Taranaki glowed… thundering Tongariro] According to ancient

legend Tongariro and Taranaki, standing together, were rival

volcanoes for the hand of a smaller mountain near by, named
Pihanga. They fought, hurling great rocks at each other, until at last
Taranaki withdrew to the seashore, where he now stands.
18 Whaka ariki] A battle-cry.
19 heitiki] A small image of polished jade, held very sacred.
20 waiariki] A warm spring.
21 taepo] Devil—the hobgoblin of the night.—Editor.
22 weka] The Maori hen—a rare ventriloquist.
23 Makutu] Bewitchment.
24 crying ‘Utu! Utu!’] Utu is payment, compensation for injury.—

Editor.
25 marae] The open space.
26 utu] Payment, compensation—an eye for an eye.
27 Upokokohua!] “Boil your head.” All Maori curses relate to
cooking or giving in cookery, to boiling or being boiled.—Editor.
28 This letter, with its enclosure from Miriam Grey to Kahikatea,
reached me just as the task of editing this work was finished.—
Editor.
 TRANSCRIBER’S NOTES.
The Hodder & Stoughton edition (London, n.d.) was consulted for
most of the changes listed below.
Minor spelling variances (e.g. lovelight/love-light, nut-trees/nut
trees, etc.), the inconsistent italicization of foreign words, and
redundant footnotes (matakite, utu) have been preserved.
Plain text edition only: note markers are given in [square] brackets.

Alterations to the text:

Convert footnotes to endnotes.
Punctuation: quotation mark pairings/nestings, missing commas,
etc.
[Chapter IV]
Change (“Tanawha lives there,” he said, “it is tapu. The Maori) to
Taniwha.
[Chapter XII]
“Arrived at a village on the coast line near Hokitiki” to Hokitika.
[Chapter XIII]
“An easel and pallette reclined against the hedge” to palette.
[Chapter XXI]
“the narrowing gulf could be seen the giant’s window” to giants’.
[Chapter XXIII]
“descend the marble steps when his controlled emotions brake
loose” to broke.
[Chapter XXV]
“Yet it semed a trifle strange to me that he should not” to seemed.

[End of text]
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