Active research, tools,

and techniques
Through learning about the instruments and methods of modern physical
chemistry and meeting researchers at work today, students gain an
appreciation for the practical applications of this science to many fields.

Tools of the Trade sections

highlight the design and
operation of commonly used
experimental apparatuses and
how they relate to the principles
discussed in the chapter.

Biosketches highlight a diverse

array of contemporary scientists and
engineers and their current research
relating to physical chemistry.
Conceptual Insight and Mathematical
Precision in a Real World Context
A discrete summary of the prerequisite mathematics and
physics adds flexibility and convenience by incorporating
the necessary math tools in a single chapter.

Chapter A provides a comprehensive summary

of the physical laws and mathematical tools used
to develop the principles of physical chemistry.
The distinctive use of color in the text’s mathematical narrative allows
students to identify important equation elements (such as the partition
function) even as they take on different mathematical forms.

Thoughtful color-coding in key

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to follow the development of complex
derivations as well as recognize
common mathematical elements that
appear in the representation of different
physical situations.

Derivations Demystified
Derivations are made transparent and
comprehensible to students without sacrifice
of mathematical rigor. Colored annotations
provide crucial help to students by explaining
important steps in key derivations.

Summaries spell out the essential results

of difficult derivations, making it easier to
accommodate the needs of different courses,
the preferences of different instructors, and the
study and review habits of different students.
Supporting students’ quest
for deeper understanding
With numerous worked examples, robust review support, a wealth of end-of-chapter
problems, and a solutions manual written by the text’s author, students have everything
they need to master the basics of physical chemistry.

Worked Examples provide students

with context of the problem, clearly
describe the parameters of the
problem, and walk students step-by-
step toward the solution.

End-of-chapter materials bring

A comprehensive online solutions manual,
students full circle, helping them
written by author Andrew Cooksy, is filled with
assess their grasp of current
unique solution sets emphasizing qualitative
chapter concepts and synthesize
results to help students move beyond the
information from prior chapters.
math to a deeper conceptual understanding.
 for Students
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PART I PART II PART III
EXTRAPOLATING NON-REACTIVE REACTIVE
FROM MOLECULAR MACROSCOPIC SYSTEMS
TO MACROSCOPIC SYSTEMS
SYSTEMS

A Introduction: Tools
from Math and
Physics
GOAL Why Are We Here?
he goal of this textbook is a concise and elegant exposition of the
theoretical framework that forms the basis for all modern chemistry. To
accomplish this, we are going to draw regularly on your knowledge of
algebra, geometry, calculus, mechanics, electromagnetism, and chemistry.
Physical chemistry is both rewarding and challenging in this way.
Mathematics of several varieties is our most valuable tool, and in this
text we shall be interested in it only as a tool. It is not necessary, for

integral 1 ln x dx, but it will help if you know that an algebraic solution
example, that you remember how to derive the algebraic solution to the

exists and how to use it (because with it we will obtain a useful equation
for difusion).his chapter is a summary of the math and physics that
serve as our starting point as we explore the theory of chemistry. If you
are embarking on this course, you may wish to review any of the following
topics that appear alarmingly unfamiliar at irst glance.

A.1 Mathematics
Algebra and Units
Basic Formula Manipulations
he use of algebra in this text is similar to its use in introductory physics
and chemistry courses. We will routinely encounter the basic manipula-
tions of variables in equations, especially to solve for one unknown in
terms of several known constants. A tough example would be to solve for
nB in the equation

TB = TB⬘ c d
VT - VA - nBR>C CBB

VT - VA⬘
3
4 CHAPTER A Introduction: Tools from Math and Physics

he key is to see that a solution must be available, because the variable we are
solving for appears in only one place, and a series of operations will allow us to
isolate it on one side of the equation. Once we recognize that, then we can
methodically undo the operations on one side of the equation to leave nB: divide
both sides by TB⬘, take the logarithm of both sides to bring nB down to earth from
the exponent, and inally divide both sides by the factor that leaves nB alone on
one side of the equation. hose steps eventually bring us to

ln a b
TB

ln a b
CB TB⬘
nB = - .
R VT - VA
VT - VA⬘
One issue that makes the algebra something of a challenge is the notation. To put
it mildly, we will use a lot of algebraic symbols. In fact, with the exception of “O,”
which looks too much like a zero, we use the entire Roman alphabet at least twice,
and most of the Greek.1 he symbols have been chosen in hopes of an optimal com-
bination of (a) preventing the same symbol from appearing with diferent meanings
in the same chapter, (b) adherence to the conventional usage in the scientiic litera-
ture, and (c) clarity of meaning. Unfortunately, these three aims cannot always be
satisied simultaneously. Physical chemistry is a synthesis of work done by pioneers
in mathematics, physics, and chemistry, oten without any intention that the results
would one day become integrated into a general theory of chemistry. We bring
together many ields that evolved independently, and the way these ields it together
is one of the joys of this course. Admittedly, the complexity of the notation is not.
he text provides guides to the notation used in long derivations and sample
calculations to show how the notation is used. Please be aware, however, that no
textbook gimmick can substitute for the reader’s understanding of the parame-
ters represented by these symbols. If you recognize the diference between the
fundamental charge e and the base of the natural logarithm e, you are in no
danger of confusing the two, even though they are both represented by the
letter “e,” sometimes appearing in the same equation.

Unit Analysis and Reasonable Answers

One of the most helpful tools for checking algebra and for keeping these many
symbols under control is unit analysis. If a problem asks you to solve for the
value of some variable ⌼, and you’re not certain what units you will get in the
end, then it’s likely that the meaning of ⌼ has not been made entirely clear. In
many cases, including viscosities and wavefunctions, the units are not obvious
from the variable’s deinition in words but are easily determined from an impor-
tant equation in which the variable appears. Quick: how do you write the units
for pressure in terms of mass and distance and time? If you recall the deinition
of the pressure as force per unit area
F
P =
A

1If the lower case Greek letter upsilon (y) didn’t look so much like an italic “v” (v), there are at least

two places it would have been used. It’s bad enough that v and the Greek nu (n) are so similar and
sometimes appear in the same equation.
 A.1 Mathematics 5

and know that force has units of mass times acceleration, then pressure must
have units of
force mass * speed/time mass * distance/time2
= =
distance2 distance2 distance2
mass
= = kg m - 1 s - 2. (A.1)
distance * time2
It will not be worthwhile to attempt a problem before understanding the
variables involved.
Unit analysis is also a useful guard against algebraic mistakes. An error in
setting up an algebraic solution oten changes the units of the answer, and a
check of the answer’s units will show the mistake. his does not protect
against many other mistakes, however, such as dividing instead of multiplying
by 1010 to convert a length from meters to angstroms. In such cases, there is
no replacement for knowing what range of values is appropriate for the
quantity. Recognizing a reasonable value for a particular variable is primarily
a matter of familiarity with some typical parameters. he values given in
Table A.1 are meant only to give common orders of magnitude for various
quantities. Answers difering by factors of 10 from these may be possible, but
not common.

TABLE A.1 Some typical values for parameters in chemical problems. hese are meant
only as a rough guide to expected values under typical conditions.

Parameter Value (in typical units)

chemical bond length 1.5 Å
chemical bond energy 400 kJ mol - 1
molecular speed 200 m s - 1
mass density (solid or liquid) 1 g cm - 3

EXAMPLE A.1 Unreasonable Answers

PROBLEM Unit analysis and recognition of a reasonable value can prevent errors such as those that resulted
in the following answers. Identify the problem with these results for the requested quantity:
Quantity Wrong answer
the density of NaCl(s) 1.3 # 10 - 24 g cm - 3
the density of NaCl(s) 3.3 # 107 g cm - 1
bond length of CsI 12.3 m
speed of a molecule 4.55 # 1011 m s - 1
momentum of electron 5 # 10 - 10 m s - 1

SOLUTION Each of those examples gives an answer of entirely the wrong magnitude (which could arise
from using the wrong conversion factor, the wrong units, or both).
6 CHAPTER A Introduction: Tools from Math and Physics

Quantity Wrong answer Why unreasonable

the density of NaCl(s) 1.3 # 10 - 24 g cm - 3 too small
the density of NaCl(s) 3.3 # 107 g cm - 1 wrong units
bond length of CsI 12.3 m too big
speed of a molecule 4.55 # 1011 m s - 1 too big (greater than speed of light)
momentum of electron 5 # 10 - 10 m s - 1 wrong units

In many problems, the units themselves require some algebraic manipulation

because several units are products of other units. For example, the unit of
pressure, 1 kg m - 1 s - 2, obtained in Eq. A.1, is called the “pascal.” We shall also
encounter an equation
Z2mee4
En = - ,
2(4pe0)2n2U2
in which En has units of energy, Z and n are unitless, me has units of mass, e has
units of charge, e0 has units of charge2 energy-1 distance -1, and U has units
of energy * time. he units on each side of the equation must be identical,
and this we can show by substituting in the appropriate units for mass, charge,
and energy:
(kg)(C)4
1J = 1 2 -1 -1 2
(C J m ) (J s)2
(kg)(C)4
= 1
C4 s2/m2
= 1 kg m2 s - 2 = 1 J. (A.2)
his may be a good place to remind you about that bothersome factor of 4pe0
and some other aspects of the SI units convention.

SI Units
he accepted standard for units in the scientiic literature is the Système
International (SI), based on the meter, kilogram, second, coulomb, kelvin,
mole, and candela.2 It is acceptable SI practice to use combinations of these
units and to convert up or down by factors of 1000. So, for example, the SI unit
of force should have units of (mass * acceleration), or kg m s - 2 , a unit
commonly called the newton and abbreviated N. Energy has units of force *
distance, so the SI unit is kg m2 s - 2 , also called the joule and abbreviated J. But
the joule is inconveniently small for measuring, say, the energy released in a
chemical reaction, so one could use the kilojoule (10 3 J) and remain true to the
SI standard. We’ll give special attention to energy units shortly.
A practical advantage of a single system for all physical units is that—if
you’re careful—the units take care of themselves. Allowing for the factors of
1000, if all the quantities on one side of an equation are in SI units, the value

2Ifyou don’t recall the candela, that’s understandable. It’s the unit of luminous intensity, and with
that, makes its last appearance in this text.
 A.1 Mathematics 7

on the other side will also be in SI units. If an object of mass 2.0 kg rests
on a table, subject to the gravitational acceleration of 9.8 m s - 2 , then I
can calculate the force it exerts on the table by multiplying the mass and
the acceleration,
F = ma = (2.0 kg)(9.8 m s - 2) = 20 N,
and I can be certain that the inal value is in SI units for force, namely newtons.
Standardization of units takes time, however, and you can be certain that the
chemical data you encounter in your career will not adhere to one standard.
One formerly common set of units, now widely discouraged, is the Gaussian or
CGS system, similar to SI except that it replaces the meter, kilogram, and
coulomb with the centimeter, gram, and electrostatic unit, respectively. Another
convention, now on the rise, is the set of atomic units, for which all units are
expressed as combinations of fundamental physical constants such as the electron
mass me and the elementary charge e.
he SI system, while having some features convenient to engineering,
sufers from one inconvenience in our applications: elementary calculations
that include electric charges or magnetic ields require the use of constants
called the permeability m0 and permittivity e0 of free space. Although these
constants originally appeared with a physical meaning attached, for our
purposes they are merely conversion factors. In particular, the factor 4pe0
converts SI units of coulomb squared to units of energy times distance, J # m.
For example, the energy of repulsion between two electrons at a separation of
d = 1.0 # 10 - 10 m is
e2 (1.602 # 10 - 19 C)2
= = 2.306 # 10 - 18 J. (A.3)
4pe0d (1.113 # 10 - 10 C2 J - 1 m - 1)(1.0 # 10 - 10 m)
In contrast, the atomic and CGS units fold this conversion into the deinition
of the charge, and the factor of 4pe0 would not appear in the calculation. For
all equations in this text involving the forces between charged particles, we
conform to the standards of the day and use SI units and the associated
factor of 4pe0 .
In other cases, however, we will not adhere strictly to the SI standard. Even
allowing for factors of 1000, I don’t know any chemists who express molecular
dipole moments in coulomb meters, a unit too large for its purpose by 30 orders
of magnitude (not even preixes like “micro-” and “nano-” are enough to save it).
he conventional unit remains the debye, which is derived from CGS units
(adjusted by 18 orders of magnitude, it must be said) and just the right size for
measuring typical bond dipoles. he angstrom (Å) also remains in wide use in
chemistry because it is a metric unit (1 Å = 10 - 10 m) that falls within a factor
of 2 of almost any chemical bond length.
Of all the physical parameters, energy has the greatest diversity in commonly
used scientiic units. here are several ways to express energy, even ater
excluding all sorts of nonmetric energy units (such as the British thermal unit,
kilowatt-hour, foot-pound, ton of TNT, and—most beloved of chemists—the
calorie). Other conventions appear when discussing the interaction of radiation
with matter, for which it is common to quantify energy in terms of the frequency
(s - 1) or reciprocal wavelength (cm - 1) of the radiation. Under the proper
assumptions, it may also be informative to convert an energy to a corresponding
8 CHAPTER A Introduction: Tools from Math and Physics

temperature, in units of kelvin. Typical laboratory samples of a compound have

numbers of molecules in the range of 1020 or more, and molecular energies are
therefore oten given in terms of the energy per mole of the compound (e.g.,
kJ mol - 1). hese cases will be explained as they appear, and they are summarized
in the conversion table for energies on this textbook’s back endpapers.
Once these non-SI units are introduced, please make sure you are comfortable
with the algebra needed to convert from one set of units to another. his one
skill, mundane as it may seem, will likely be demanded of you in any career in
science or engineering. Famous and costly accidents have occurred because this
routine procedure was not given its due attention.3

Complex Numbers
Complex numbers are composed of a real number and an imaginary number
added together. For our purposes, a complex number serves as a sort of two-
dimensional number; the imaginary part contains data on a measurement
distinct from the data given by the real part. For example, a sinusoidal wave that
varies in time may be described by a complex number in which the real part
gives the shape of the wave at the current time and the imaginary part describes
what the wave will look like a short time later.

i K 2- 1. (he symbol “K” is used throughout this text to indicate a deinition,

he imaginary part of any complex number is a real number multiplied by

as opposed to the “=” symbol, used for equalities that can be proved mathemati-
cally.) his relationship between i and - 1 allows the imaginary part of a complex
number to inluence the real-number results of an algebraic operation. For
example, if a and b are both real numbers, then a + ib is complex, with a the
real part and ib the imaginary part. he complex conjugate of a + ib, written
(a + ib)* , is equal to a - ib, and the product of any number with its complex
conjugate is a real number:
(a + ib)(a - ib) = a2 - iba + iba - i2b2 = a2 + b2. (A.4)
Notice that the value of b—even though it was contained entirely in the imagi-
nary parts of the two original complex numbers—contributes to the value of the
real number quantity that results from this operation.
Many of the mathematical functions in the text are complex, but multiplica-
tion by the complex conjugate yields a real function, which can correspond
directly to a measurable property. For that reason, we oten judge the validity of
the functions by whether we can integrate over the product f *f . In this text,
a well-behaved function f is single-valued, inite at all points, and yields a inite
value when f *f is integrated over all points in space. To be very well-behaved,
the function and its derivatives should also be continuous functions, but we will
use a few functions that are naughty in this regard.

3A prominent example is the loss in 1999 of the unmanned Mars Climate Orbiter, a probe that
entered the Martian atmosphere too low and burned up because engineers were sending course
correction data calculated using forces in pounds to an on-board system that was designed to
accept the data in newtons.
 A.1 Mathematics 9

EXAMPLE A.2 Complex Conjugates

PROBLEM Write the complex conjugate f * for each of the following expressions f and show that the value
*
of f f is real.
1. 5 + 5i
2. - x>i
3. cos x - i sin x
SOLUTION
1. f * = 5 - 5i
f *f = (5 + 5i)(5 - 5i) = 25 + 25 = 50
2. First we would like to put this in the form a + ib, so we multiply by ii to bring the factor of i into the
numerator:

a b = -
x i ix
f = - =.
i i -1
he real part of this function is zero, but for any complex conjugate, we change the sign on the imaginary
term: f * = - ix
f *f = (ix)(- ix) = - i2x2 = x2
3. f * = cos x + i sin x
f *f = cos2 x - i2 sin2 x = cos2 x + sin2 x = 1

Trigonometry
Elementary results from trigonometry play an important role in our equations of
motion, and therefore you should know the deinitions of the sine, cosine, and
tangent functions (and their inverses) as signed ratios of the lengths of the sides
of a right triangle. Using the triangle drawn in Fig. A.1, with sides of length y, x,
and r, we would deine these functions as follows:
y 1 r
sin f K csc f K =
r sin f y
x 1 r
cos f K sec f K = (A.5)
r cos f x
y 1 x
tan f K cot f K = r
y
x tan f y
ⴰ ⴰ
he sign is important. If f lies between 90 and 270 , then the x value becomes ϕ
negative, so cos f and sec f would be less than zero. Similarly, sin f and csc f are
x
negative for f between 180 ⴰ and 360 ⴰ .
Please also make sure you are comfortable using the trigonometric identities ▲ FIGURE A.1 Right triangle
listed in Table A.2. hese are algebraic manipulations that may allow us to used to deine trigonometric
simplify equations or to isolate an unknown variable. functions of the angle F.
 10 CHAPTER A Introduction: Tools from Math and Physics

TABLE A.2 Selected trigonometric identities.

sin2 x + cos2 x = 1 sec2 x - tan2 x = 1

sin(x { y) = sin x cos y { cos x sin y cos(x { y) = cos x cos y | sin x sin y
sin x sin y = [cos(x - y) - cos(x + y)]>2 cos x cos y = [cos(x + y) + cos(x - y)]>2
sin x cos y = [sin(x + y) + sin(x - y)]>2
sin 2x = 2 sin x cos x cos 2x = 2 cos2 x - 1

Coordinate Systems
Mathematical functions are described by their variables, but we have some
choice in deciding what those variables are. Rather than deining the function

which f(y) = y2 >4.

f(x) = x2 as written, we could deine it in terms of a new variable y = 2x, for

For functions that represent distributions in three-dimensional space, there

are two common choices of variables: the Cartesian coordinates, (x, y, z); and
the spherical polar coordinates, (r, u, f). he Cartesian coordinates can each
vary from -⬁ to + ⬁. he polar coordinates lie in the ranges
0 … r 6 ⬁ 0 … u 6 p 0 … f 6 2p,
ⴰ
where p radians is equal to 180 , and the radian is the ratio of a circle’s circum-
ference to its diameter. Usually when we move between the two systems, we will
take the angle u as measured in any direction from the positive half of the z axis,
and the angle f as the angle measured parallel to the xy plane from the positive
x axis towards the positive y axis. he distance r is always measured in any direc-
tion from the origin. hese deinitions are illustrated in Fig. A.2.
he Cartesian and spherical polar coordinate systems satisfy the fundamental
requirements for a complete coordinate system in three-dimensional space—
namely, that every point in space can be represented by some set of values for
these coordinates, and every set of coordinates corresponds to only one point
in space. Although the Cartesian coordinate representation of a single point may
z be easier for us to visualize than the representation in spherical coordinates,
functions that have a lot of angular symmetry can be written and manipulated
much more easily in spherical coordinates than in Cartesian coordinates.
Converting between Cartesian and spherical coordinates is straightforward
θ but oten tedious. he most crucial conversions between Cartesian and
r
spherical coordinates have been done for us by someone else, and we should
not be too shy to take advantage of all that hard work. Should it be necessary to
x
y convert between the two systems for a particular application, the following
equations can be used:
x = r sin u cos f r = (x2 + y2 + z2)1>2

u = arccosa b
ϕ

z
x y = r sin u sin f (A.6)
r

f = arctan a b
▲ FIGURE A.2 he relation
y
between spherical polar and z = r cos u
Cartesian coordinates. x
 A.1 Mathematics 11

he most important conversion we will need is between the volume elements,

abbreviated dt, that appear in all integrals. he volume element is so named
because its integral, evaluated over some three-dimensional region, is the volume
enclosed by that region. For an integral over three-dimensional space, the
volume element is
dt K dx dy dz = r2 dr sin u du df. (A.7)
Although this equation is not obvious at irst glance, we can observe easily that dt
has units of volume as promised. For the Cartesian volume element, dx dy dz is the
volume of a cube with sides of length dx, dy, and dz and has units of volume. he
only spherical coordinate with units of distance, r, appears three times in the spher-
ical volume element: twice in r2 and once in dr (which has the same units as r),
giving units of distance3 or volume. he remaining terms, sin u du df, are unitless.

EXAMPLE A.3 Cartesian and Polar Coordinates

PROBLEM Convert the following Cartesian expression into spherical coordinates and the spherical polar
expression into Cartesian coordinates.
2 2 2 2
f(x, y, z) = z e - (x + y + z )>a
g(r, u, f) = (3 cos2 u - 1)tan f

f(r, u, f) = (r cos u) e - r >a

SOLUTION We can directly substitute using the expressions in Eqs. A.6:
2 2

g(x, y, z) = c 3 a b - 1 d tan c arctan d

z 2 y
r x

= c 3a b -1 d
z 2 y
r x

Linear Algebra
Linear algebra is so named because it grew out of methods for solving systems of
linear equations. For our purposes, it is the branch of mathematics that describes
how to perform arithmetic and algebra using vectors and matrices.

Vectors
Formally, a vector is a set of two or more variable values, but our use of the term
will be restricted to Euclidean vectors, which are governed by the following
deinitions and rules:
1. A vector has direction, which can be speciied by assuming one of the end-
points to be the origin and giving the coordinates of the other endpoint.
As an example, the vector (1, 0, 0) has one end at the origin and the other
end at x = 1 on the x axis.
S S
2. A vector A = (Ax, Ay, Az) has a length or magnitude, indicated 兩 A 兩 or
simply A, where
兩 A 兩 K A = 2A2x + A2y + A2z .
S
(A.8)
12 CHAPTER A Introduction: Tools from Math and Physics

S S
3. he dot product of two vectors A = (Ax, Ay, Az) and B = (Bx, By, Bz)
is a scalar quantity (not a vector) given by
S#S
A B K A x Bx + Ay By + Az Bz . (A.9)
S
4. he dot product of A and a unit vector (vector of length one) parallel to
S S S S
B is called the projection of A onto B ; this is oten evaluated with B
chosen to be one of the coordinate axes, such as
S#n
A z = Az ,
S
where zn K (0, 0, 1). his quantity gives the extent that the vector A
stretches along the z direction, and is oten called the z component
S
of A .
5. he cross product of two vectors is also a vector, given by
S S
A * B K (Ay Bz - Az By, Az Bx - Ax Bz , Ax By - Ay Bx). (A.10)
S S S
he cross product A * B is always perpendicular to the vectors A
S
and B .
S S
6. he vector sum of A and B is given by
S S
A + B = (Ax + Bx, Ay + By, Az + Bz) (A.11)
and is a vector with maximum magnitude A + B (if the two vectors point
in exactly the same direction) and minimum magnitude 兩 A - B 兩 (if they
point in exactly opposite directions).

Matrices
Although we will use vectors to represent physical quantities, such as position
and angular momentum, to a mathematician a vector is any set of expressions
that depend on some index. For example, the position vector S r is the set of
coordinate values ri, where r1 = x, r2 = y, and r3 = z. In that example, the
index i lets us pick out one part of the vector. A matrix is a set of values or
functions that depend on at least two diferent (and usually independent) indices.
We will not encounter many matrices in this text, but there are a few places
where they allow you to go one step farther in calculating important physical
quantities in chemistry.
As an example, we may write the matrix R of values rirj for each i and j from
1 to 3:

R = ° r2r1 r2r2 r2r3 ¢ = ° yx y2 yz ¢.

r1r1 r1r2 r1r3 x2 xy xz

r3r1 r3r2 r3r3 zx zy z2

his matrix gives all the possible combinations of x, y, and z with x, y, and z.
he matrix R would be one short way to represent all the terms that would arise
from expanding (x + y + z)2:
(x + y + z)2 = x2 + y2 + z2 + 2xy + 2yz + 2xz .
It would also represent them in such a way that we could pick out any one of
those terms—any single matrix element Ri j—by itself from the values of the
two indices, as for example R13 = r1 r3 = xz.
 A.1 Mathematics 13

here is an algebra for matrices. We can multiply a matrix by a constant:

ca b = a b .
f cf
(A.12)
g cg
S S
ing to the formula Bi = g j Ri j Aj. For example, the product of any 2 * 2 matrix
We can also multiply a matrix and a vector A , obtaining a new vector B accord-

and a 2-coordinate vector is given by

a ba b = a b.
r s f rf + sg
(A.13)
t u g tf + ug
he product is a new vector. he multiplication just shown forms the basis for
one of the most common applications of matrices in physics: changing a vector
from one form to another. For example, start with the vector (a, b, c) where a, b,
and c are constants giving the length of the vector along the x, y, and z axes,
respectively. Now carry out the following multiplication:

° 0 0 1 ¢ ° b ¢ = ° c ¢.
0 1 0 a b

1 0 0 c a
he result is a new vector with the same magnitude but pointing in a diferent
direction, where a is now the length of the vector along the z axis instead of the
x axis, and so on. he vector has been rotated by 90⬚ around all three coordinate
axes. What would be an awkward operation to carry out using trigonometry
becomes relatively straightforward when we use matrix algebra. his example
also illustrates how we can use a matrix to represent mathematically a real
physical process, in this case the rotation of an object in space.
A second common application of matrix algebra is to solve a set of equations
of the form
h11ax + h12by = cax
h21ax + h22by = cby. (A.14)

Here, the hi j’s can be any coeicients, ax and by together form a vector in the
xy plane, and c is some unknown constant that we want to ind. Using our
rules of matrix multiplication, these equations can be written as a single matrix
equation:

a b a b = ca b .
h11 h12 ax ax
(A.15)
h21 h22 by by

a b by a b on the let, we get a b multiplied by a constant c on

Equation A.15 is an example of an eigenvalue equation, because ater multiplying
ax h11 h12 ax
by h21 h22 by
the right. (he eigenvalue equation is discussed in more detail in Section 2.1 of
the Quantum Mechanics volume.) We can solve for the values of c that make
Eq. A.15 true by a convenient feature of matrix algebra.
Say, for example, that we want to ind the values of c that solve the two equations
2ax + by = cax
ax = cby
14 CHAPTER A Introduction: Tools from Math and Physics

for any given values of a and b. hen, the matrix elements hij have the values:

a b = a b.
h11 h12 2 1
h21 h22 1 0
hen we ind the values of c by diagonalizing the matrix. First, subtract the
unknown value c from each value hii (these are the diagonal elements of the matrix):

a b.
2- c 1
1 0- c
Next, take the determinant of the matrix and set it equal to zero. he determinant
is an algebraic combination of all the elements in a square matrix, with the
following formulas for 2 * 2 and 3 * 3 matrices:

` ` = ru - st
r s
(A.16)
t u

†u v w† = r` ` + s` ` + t` ` = rvz + swx + tuy - rwy - suz - tvx .

r s t
vw w u u v
y z z x x y
x y z (A.17)
Using the 2 * 2 case, the determinant we need to set to zero in our example is

` ` = (2 - c)(- c) - (1)(1) = c2 - 2c - 1 = 0 .
2- c 1
1 -c

c = 3 2 { 24 + 4 4 = 1 { 22.
Solving for c with the quadratic formula, we obtain two solutions:
1
2
here are two valid solutions to Eq. A.15, corresponding to the + and - signs.

2ax + by = (1 { 22)ax
To show that they are solutions, substitute each result for c in Eqs. A.14:

ax + (0)by = (1 { 22) by
h11ax + h12by = cax

ax = (1 { 22)by
h21ax + h22by = cby

2(1 { 22)by + by = (1 { 22)2by

solve for ax

(3 { 2 22)by = (3 { 2 22)by .
replace ax

he same method can be used to solve any number of related equations

simultaneously, boiling the problem down to a single step: diagonalizing the
matrix. Consequently, matrix diagonalization routines comprise a key element
in computer programs designed to solve problems and simulate processes in
virtually every realm of chemistry and physics.

Differential and Integral Calculus

If, like many of your classmates, you enjoyed everything about organic
chemistry except its neglect of your calculus skills, rest assured that we won’t
make the same mistake in physical chemistry. Much of the problem-solving
ahead of us involves taking a process that we understand on a tiny scale and
expanding that description to a larger scale. hat tiny-scale understanding will
oten be phrased mathematically using derivatives, which are an idealized
version of how a property—such as electron position or chemical
 A.1 Mathematics 15

concentration—changes over a small step. Change makes everything

interesting: how the colors of the leaves change with time, how the climate
changes the closer we get to the coast, and how the taste of ice cream changes
with the amount of vanilla added. For another example, we describe the
interactions between particles in terms of the forces they exert on one another.
Force is proportional to an acceleration, and acceleration is the derivative of
the velocity with respect to time. A force describes where a particle is going to
move right now. If we want to see a bigger picture, we can undo the derivative
with integration and extract from the force law an idea of where the particle
will be at diferent times. he force itself is a derivative (with respect to
distance) of the energy, and integrating the force over distances can tell us how
the energy of a system varies at diferent locations.
Another form of this extension from small scale to large scale requires us to
calculate sums and averages—which are convenient ways to describe huge
systems—from functions too detailed to bear patiently. For example, an under-
standing of the small-scale interaction between molecules and gravity leads us to
predict that air is denser near sea level than at high altitudes. A clever equation
even tells us how the air density varies with altitude. By integrating this equation
over all altitudes, we can ind the total amount of air present and drop all the
information about the detailed interactions. It is this general approach of
extrapolating from small to large that makes a journeyman command of calculus
essential for the text.

Derivatives
Solutions to some standard derivatives appear in Table A.3. It does not hurt to
know how to obtain derivatives and integrals, but we will be treating these
aspects of calculus as just another kind of algebra. In other words, one may
replace the derivative or integral expression by the correct algebraic expression,
with the appropriate substitutions. his will suice for almost all the calculus we
encounter in the text.
When a function depends on more than one variable, then the derivative of
the function with respect to one variable generally depends on the other variables
as well. As one example, suppose that we have a variable P that depends on three
other variables n, T, and V , and a constant R, such that
nRT
P = .
V

TABLE A.3 Solutions to selected derivatives.

dxc = cx c - 1dx (c 0) d(cx) = cdx

1
d ln x = dx dex = exdx
x
d sin x = cos x dx d cos x = - sin x dx
d[f (x) + g(x)] = d[f (x)] + d[g (x)] d[f (x)g (x)] = f (x)d[g (x)] + g (x)d[f (x)]
f (x)d[g (x)] - g (x)d[f (x)]
d[f (x)>g (x)] =
g (x)2
16 CHAPTER A Introduction: Tools from Math and Physics

hen the derivative of P is related to the derivatives of the three variables, because
small changes in n, in T, and in V will each contribute to the overall change in P.
In general, derivatives of multivariable functions require knowing how all the
variables depend on each other. In these instances, we will use the partial
derivative, represented by the symbol 0, which is simply the derivative of the
function with respect to one variable treating all the other variables as though
they are constants. he expression

a b
0P
0V n,T
represents the partial derivative of P with respect to V , treating n and T as
though they were constants, just like R. Using the partial derivative, the total
derivative of P may be written as a sum over the derivatives of the variables:

dP = a b dn + a b dT + a b dV =
0P 0P 0P RT nR nRT
dn + dT - dV.
0n T,V 0T n,V 0V n,T V V V2
(A.18)
In the third partial derivative, for example, the variables n and T are treated as
constants and factored out of the derivative. Hence the partial derivative
simpliies to

a b = a b = nRT a b = -
0P 0(nRT>V) 0(1>V) nRT
. (A.19)
0V n,T 0V n,T 0V n,T V2
Table A.4 contains some useful relations involving partial derivatives.

Analytical Integrals
Please make sure that you understand the following terminology regarding
integrals:

the expression 1a f(x) dx. he integration of f (x) in this case is only carried
1. A deinite integral is evaluated between limits, the quantities a and b in
b

out from x = a to x = b.
2. When the limits are not speciied, the integral is an indeinite integral.
he derivative of a constant C is zero. herefore, when we take the
derivative of a function f (x) = g (x) + C, all the information about

TABLE A.4 Relations involving partial derivatives.

a b a b
0x 0y
reciprocal rule = 1
0y 0x

= a b dx+ a b dy
z z

0z 0z
slope rule dz(x, y)
0x 0y

a b = -a b a b
y x

0x 0x 0z
cyclic rule
0y 0z 0y

a b = a b a b
z y x

0x 0x 0w
chain rule
0y 0w 0y

a b = a b +a b a b
z z z

0x 0x 0x 0w
0y z 0y w 0w y 0y z
 A.1 Mathematics 17

TABLE A.5Solutions to selected integrals. In these equations, a and b are constants, n is a

whole number, and C is the constant of integration.

1
L L
xndx = xn + 1 + C adx = a(x + C)
n+1
1
Lx L
dx = ln x + C ex dx = ex + C

= - ln a b + C
1
L L x(a + bx)
dx a + bx
ln x dx = x ln x - x + C
a x

L L
sin x dx = - cos x + C cos x dx = sin x + C

sin (2ax) sin (2ax)

L L
x x
sin2 (ax) dx = - + C cos2 (ax) dx = + + C
2 4a 2 4a

= x0a = b - a
b

L L L La
b
[f (x) + g (x)]dx = f (x) dx + g (x) dx dx

a b
⬁ ⬁
1 p 1/2
L0 L0
n! 2
xne-ax dx = n+1 e-ax dx =
a 2 a

a b
⬁ ⬁
1 1 p 1/2
L0 L0
2 2
xe-ax dx = x2 e-ax dx =
2a 4 a3
[1 # 3 # 5 c(2n - 1)] 2p
⬁ ⬁

L0 L0
2 n! 2
x2n + 1 e-ax dx = x2n e-ax dx =
2an + 1 2n + 1 an + (1/2)

- e-as a
s n
n!sn - i
L0
n!
xn e-ax dx =
an + 1 i=0 a
i+1
(n - i)!

the value of C is lost. When we undo the derivative by taking the integral,
we add an unknown constant of integration to the integrated expression.
Omit this constant when solving deinite integrals, because the limits of
integration will determine its value.
3. he function being integrated is the integrand, and it is multiplied by the
incremental change along the coordinates, called the volume element.
Most of the algebraic solutions to integrals that we need appear in Table A.5.

EXAMPLE A.4 Analytical Integration

PROBLEM Evaluate the numerical value for each of the following expressions.
4

L1 x
dx
1.
⬁

L0
2. e - 2x dx
p>3

L0
2
3. (3 cos u - 1) sin u du