30 Chapter 2 Symbolic Mathematics and Mathematical Functions

we can define a function to give a value for x as a function of y . We write

x = arcsin(y). (2.29)
This can be read as “x is the angle whose sine is y .” The arcsine function is also
called the inverse sine function, and another notation is also common:
x = sin−1 (y). (2.30)
The −1 superscript indicates an inverse function. It is not an exponent, even though
exponents are written in the same position. If you need to write the reciprocal of
sin(y), you should write [sin(y)]−1 to avoid confusion. It is probably better to use
the notation of Eq. (2.29) rather than that of Eq. (2.30) to avoid confusion.
From Fig. 2.2, you can see that there are many angles that have the same value
of the sine function. In order to make the arcsine in Eq. (2.29) or Eq. (2.30) into
a single-valued function, we must restrict the values of x that we consider. With
the arcsine function, these values are taken from −π/2 to +π/2 and are called the
principal values of the arcsine function. The other inverse trigonometric functions
such as the inverse cosine and inverse tangent are defined in the same way as the
arcsine function, and must also have principal values defined. The principal values
of the arctangent and arccosecant functions range from −π/2 to +π/2, the same as
with the arcsine. The principal values of the arccosine, arccotangent, and arcsecant
are taken from 0 to π .

EXERCISE 2.7 Sketch graphs of the arcsine function, the arccosine func-
tion, and the arctangent function. Include only the principal values.

Hyperbolic Trigonometric Functions

These functions are closely related to the exponential function. The hyperbolic
sine of x is denoted by sinh(x), and defined by
1
sinh(x) = (ex − e−x ). (2.31)
2
The hyperbolic cosine is denoted by cosh(x), and defined by
1 x
cosh(x) = e + e−x . (2.32)
2
The other hyperbolic trigonometric functions are the hyperbolic tangent, denoted
by tanh(x); the hyperbolic cotangent, denoted by coth(x); the hyperbolic secant,
denoted by sech(x ); and the hyperbolic cosecant, denoted by csch(x ). These func-
tions are given by the equations
sinh (x)
tanh(x) = (2.33)
cosh(x)
1
coth (x) = (2.34)
tanh (x)
1
sech(x) = (2.35)
cosh (x)
1
csch (x) = (2.36)
sinh (x)
 Section 2.4 Vectors and Coordinate Systems 31

Figure 2.5 The hyperbolic sine and cosine.

Figure 2.5 shows the hyperbolic sine and hyperbolic cosine for values of x from
0 to 3. Note that the values of the hyperbolic sin and the hyperbolic cosine do not
necessarily lie between −1 and 1 as do the values of the circular sine and cosine
functions and that both functions approach ex /2 for large values of x .

EXERCISE 2.8 Make a graph of tanh(x) and coth(x) on the same graph
for values of x ranging from 0 to 3.

EXERCISE 2.9 Find the value of each of the hyperbolic trigonometric

functions for x = 0 and x = π/2. Compare these values with the values
of the ordinary (circular) trigonometric functions for the same values of the
independent variable.

2.4 Vectors and Coordinate Systems

Quantities that have both magnitude and direction are called vectors. For exam-
ple, the position of an object can be represented by a vector, since the position
can be specified by giving the distance and the direction from a reference point
(an origin). A force is also a vector, since it is not completely specified until its
magnitude and direction are both given. Some other vectors that are important
in physical chemistry are the dipole moments of molecules, magnetic and electric
fields, angular momenta, and magnetic dipoles.
We will use a boldface letter to represent a vector. For example, the force on
an object is denoted by F. When you are writing by hand, there is no easy way to
write boldface letters, so you can use a letter with an arrow over it (e.g., F ) or you
can use a wavy underscore (e.g., F ), which is the typesetter’s symbol for boldface
∼
type.
32 Chapter 2 Symbolic Mathematics and Mathematical Functions

Figure 2.6 A position vector, ρ , in a plane, with plane polar coordinates and Cartesian coordi-
nates.

Vectors in Two Dimensions

Two-dimensional vectors include position vectors of objects that remain on a flat
surface. We represent this physical surface by a mathematical plane, which is a
map of the surface so that each location in the physical surface corresponds to a
point of the mathematical plane. We choose some point as an origin and pick some
line passing through the origin as our x axis. One end of this axis is designated as
the positive end. The line passing through the origin perpendicular to the x axis is
our y axis, and the end that is counterclockwise 90 ◦ from the positive end of the y
axis is its positive end. These axes are shown in Fig. 2.6. In this figure, the origin
is labeled as point O , and the location of some object is labeled as point P .
The directed line segment beginning at O and ending at P is the position vector
of the object. We denote the position vector in two dimensions by the boldface
Greek letter ρ . In the figure, we draw an arrowhead on the directed line segment to
make its direction clear.
The negative of a given vector is a vector of the same length directed in the
opposite direction. A vector and its negative have the same magnitude, as do all
the vectors of the same length pointing in any other directions. The magnitude of ρ
is denoted |ρ| or by ρ. It is a nonnegative quantity equal to the length of the vector
ρ . One way to specify the location of the point P is to give the magnitude of ρ and
the value of the angle φ between the positive end of the x axis and ρ , measured
counterclockwise from the axis. The variables ρ and φ are called the plane polar
coordinates of the point P . If we allow ρ to range from zero to ∞ and allow φ to
range from 0 to 2π radians, we can specify the location of any point in the plane.
There is another common way to specify the location of P . We draw two line
segments from P perpendicular to the axes, as shown in Fig. 2.6. The distance
from the origin to the intersection on the x axis is called x and is considered to
be positive if the intersection is on the positive half of the axis, and negative if
the intersection is on the negative half of the axis. The distance from the origin to
the intersection on the y axis is called y , and its sign is assigned in a similar way.
The variables x and y are the Cartesian coordinates of P .1 The point P can be
designated by its Cartesian coordinates within parentheses, as (x, y). The values
of x and y are also called theCartesian components of the position vector.
1 Cartesian coordinates are named for Rene DuPerron Descarte, 1596–1650, French mathematician, philoso-
pher, and natural scientist, who is famous (in part) for his statement, “I think, therefore I am.”
Section 2.4 Vectors and Coordinate Systems 33

Changing from plane polar coordinates to Cartesian coordinates is an example

of transformation of coordinates, and can be done by using the equations

x = ρ cos (φ) (2.37)

y = ρ sin (φ) (2.38)

EXERCISE 2.10 Show that Eqs. (2.37) and (2.38) are correct.

The coordinate transformation in the other direction is also possible. From the
theorem of Pythagorus, Eq. (2.21),

ρ= x 2 + y 2. (2.39)

From the definition of the tangent function, Eq. (2.3),

y
φ = arctan . (2.40)
x

However, since we want φ to range from 0 to 2π radians, we must specify this

range for the inverse tangent function, instead of using the principal value. If we
are using a calculator that is programmed to deliver the principal value, we must
decide in advance which quadrant φ lies in and be prepared to add π or 2π to the
calculator result if it lies in the wrong quadrant.

EXERCISE 2.11 (a) Find x and y if ρ = 6 and φ = π/6 radians.

(b) Find ρ and φ if x = 5 and y = 10.

A position vector is only one example of a vector. Anything, such as a force, a

velocity, or an acceleration, which has magnitude and direction, is a vector. Figure
2.6 is a map of physical space, and a distance in such a diagram is measured in
units of length, such as meters. Other kinds of vectors can also be represented
on vector diagrams by directed line segments. However, such a diagram is not a
map of physical space, and the length of a line segment representing a vector will
represent the magnitude of a force, or the magnitude of a velocity, or something
else. Position vectors ordinarily remain with their tails at the origin, but since other
vector diagrams do not necessarily represent a physical (geographical) space, we
will consider a vector to be unchanged if it is moved from one place in a vector
diagram to another, as long as its length and its direction do not change.

Vector Algebra in Two Dimensions

Figure 2.7 is a vector diagram in which two vectors, A and B, are shown. The sum
of the two vectors is obtained as follows: (1) Move the second vector so that its
tail coincides with the head of the first. (2) Draw the sum vector from the tail of
the first vector to the head of the second. The addition of vectors is commutative:
A + B is the same as B + A.
34 Chapter 2 Symbolic Mathematics and Mathematical Functions

Figure 2.7 Two vectors and their sum.

The components of A and B are defined in the same way as the components of
the position vector in Fig. 2.6. The x components are called Ax and Bx , and the y
components are called Ay and By . We can denote the vector A by its component in
x, y order inside parentheses, as (Ax , Ay ) Vector addition can be performed using
the components of the vectors. If the sum of A and B is called C,

C = A+B (2.41)
Cx = Ax + Bx (2.42)
Cy = Ay + By . (2.43)

EXAMPLE 2.2 Find the sum of the two vectors (2.5, 3) and (3.1, 4).

SOLUTION A + B = (5, 6, 7)

The difference of two vectors is the sum of the first vector and the negative of
the second. The negative of B is denoted by −B and is the vector with components
−Bx and −By . If the vector A − B is called D,

D = A−B (2.44)
Dx = Ax − Bx (2.45)
Dy = Ay − By . (2.46)

If the tail of the vector −B is placed at the head of the vector A, the vector D =
A − B has its tail at the tail of A and its head at the head of −B. The difference
D = A − B can also be represented by placing the tails of both A and B at the
same place and drawing the vector D with its tail at the head of B and its head at
the head of A.

EXERCISE 2.12 Draw vector diagrams and convince yourself that the
two schemes presented for the construction of D = A − B give the same result.
Section 2.4 Vectors and Coordinate Systems 35

If A is a vector and a is a scalar, the product of the scalar and the vector a A
has the components

(aA)x = aAx (2.47)

(aA)y = aAy (2.48)

If a is a positive scalar, the vector a A points in the same direction as A, and if a is

a negative scalar, the vector a A points in the opposite direction. The magnitude of
a A is equal to |a| |A| = |a|A.
The magnitude of a vector A in two dimensions is denoted by A or by |A|. It is
obtained in the same manner as the magnitude of a position vector:

A = |A | = A2x + A2y (2.49)

EXERCISE 2.13 The vector A has the components Ax = 2, Ay = 3. The

vector B has the components Bx = 3, By = 4. (a) Find |A| and |B|. (b) Find
the components and the magnitude of A + B. (c) Find the components and the
magnitude of A − B. (d) Find the components and the magnitude of 2A − B.

We next define the scalar product of two vectors, which is also called the dot
product because of the use of a dot to represent the operation. If A and B are two
vectors, and α is the angle between them, their scalar product is denoted by A · B
and given by
A · B = |A| |B| cos (α) . (2.50)
The result is a scalar, as the name implies.

EXERCISE 2.14
(a) Let |A| = 4.5, |B| = 6.0, and let the angle between them equal 30.0 ◦ .
Find A · B.
(b) Let |A| = 4.0, |B| = 2.0, and let the angle between them equal 45.0 ◦ .
Find A · B.
The following are properties of the scalar product:

1. If A and B are parallel, A · B is the product of the magnitudes of A and B.

2. The scalar product of A with itself is the square of the magnitude of A:

A · A = A2 = A2 = A2 = A2x + A2y .

3. If A and B are perpendicular to each other, A · B = 0. Such vectors are said to

be orthogonal to each other.
4. If A and B point in opposite directions (are antiparallel), A · B is the negative
of the product of the magnitudes of A and B.

A convenient way to represent vectors is by using unit vectors. We define i to

be a vector of unit length pointing in the direction of the positive end of the x axis,
and j to be a vector of unit length pointing in the direction of the positive end of
the y axis. These are shown in Fig. 2.8.
36 Chapter 2 Symbolic Mathematics and Mathematical Functions

Figure 2.8 A vector in terms of the unit vectors i and j.

A vector A is represented as

A = iAx + jAy . (2.51)

The first term on the right-hand side of this equation is a product of the component
Ax and a vector i, so it is a vector of length Ax pointing along the x axis, as shown
in Fig. 2.8. The other term is similarly a vector of length Ay pointing along the y
axis. The vector A is the vector sum shown in Fig. 2.8. A similar equation can be
written for another vector, B:

B = iBx + jBy . (2.52)

The scalar product A · B can be written

A · B = iAx + jAy · iBx + jBy

= i · iAx Bx + i · jAx By + j · iAy Bx + j · jAy By .

From the definitions of i and j and the definition of the scalar product,

i·i = j·j=1 (2.53)

i·j = j·i=0 (2.54)

so that
A · B = Ax Bx + Ay By (2.55)

EXAMPLE 2.3 Consider the following vectors: A = 2.5i + 4j and B = 3i − 5j.

(a) Find A · B. (b) Find |A| and |B| and use them to
find the angle between A and B.

SOLUTION A · B = (2.5)(3) + (4)(−5) = 7.5 − 20 = −12.5.

|A| = (6.25 + 16)1/2 = (22.25)1/2 = 4.717 . . .
|B| = (9 + 25)1/2 = (34)1/2 = 5.8309 . . .
A·B −12.5
cos (α) = = = −0.4545
|A| |B| (4.717)(5.831)
α = arccos (−0.4545) = 2.043 rad = 117.0 ◦
Section 2.4 Vectors and Coordinate Systems 37

EXERCISE 2.15 Consider two vectors A = (3.00)i − (4.00)j and B =

(1.00)i + (2.00)j.
(a) Draw a vector diagram of the two vectors.
(b) Find A · B and (2A) · (3B).
(c) Find the magnitude of A · B.
(d) Find the angle between A and B. Use the principal value of the arccosine,
so that an angle of less than π radians (180◦ ) results.

Vectors and Coordinate Systems in Three Dimensions

Figure 2.9 depicts the three-dimensional version of Cartesian coordinates. We de-
fine the x and y axes as before, and erect the z axis through the origin and perpen-
dicular to the x and y axes.
The axes are viewed from the first octant, lying between the positive ends of
the x , y , and z axes. The octants are numbered from 1 to 8, beginning with the
first octant in the upper front right part of the coordinate system and moving coun-
terclockwise around the upper part, and then moving to the lower front right part
(octant 5) and moving counterclockwise around the bottom part. A coordinate sys-
tem such as that shown is called a right-handed coordinate system. For such a
system, the thumb, index finger, and middle finger of the right hand can be aligned
with the positive ends of the x , y , and z axes, respectively. If the left hand must be
used for such an alignment, the coordinate system is called a left-handed coordi-
nate system.
The location of the point P is specified by x , y , and z, which are the Cartesian
coordinates of the point. These are the distances from the origin to the points on the
axes reached by moving perpendicularly from P to each axis. These coordinates
can be positive or negative. In the first octant, x, y,and z are all positive. In the
second octant, x is negative, but y and z are positive. The point P can be denoted
by its coordinates, as (x, y, z). The directed line segment from the origin to P is

Figure 2.9 Cartesian coordinates in three dimensions.

38 Chapter 2 Symbolic Mathematics and Mathematical Functions

Figure 2.10 A position vector in terms of the unit vectors i, j, and k.

the position vector of P , and is denoted by r. The Cartesian coordinates x , y , and

z are also called the Cartesian components of r. A vector can be represented by
the list of its components inside parentheses so that the position vector is denoted
by (x, y, z) and the vector A can be denoted by (Ax , Ay , Az ).
We can represent a three-dimensional vector by the use of unit vectors as we did
in two dimensions. In addition to the unit vectors i and j in the x and y directions,
we define k, a vector of unit length pointing in the direction of the positive end of
the z axis. Figure 2.10 shows these unit vectors and the position vector written as
r = ix + jy + kz. (2.56)
The magnitude of r of the vector r can be obtained from the theorem of
Pythagoras. In Fig. 2.10 you can see that r is the hypotenuse of a right trian-
gle with sides ρ and z, where ρ = x 2 + y 2 so that the square of the magnitude
of r is given by a three-dimensional version of the theorem of Pythagoras:

r 2 = ρ 2 + z2 = x 2 + y 2 + z2 (2.57)
or
r = |r | = x 2 + y 2 + z2 . (2.58)
The magnitude of any vector is analogous to the magnitude of the position vector.
If A is a vector with Cartesian components Ax , Ay , and Az , the magnitude of A is
given by

1/2
|A| = A = A2x + A2y + Az2 = A2x + Ay2 + Az2 . (2.59)

EXAMPLE 2.4 Find the magnitude of the vector A = (3.00, 4.00, 5.00).
Section 2.4 Vectors and Coordinate Systems 39

Figure 2.11 Spherical polar coordinates.

√
SOLUTION A= 3.002 + 4.002 + 5.002 = 50.00 = 7.07

Figure 2.11 shows the way in which spherical polar coordinates are used to
specify the location of the point P and the vector r from the origin to P . The
vector ρ in the x -y plane is also shown. The vector ρ is called the projection
of r into the x -y plane. Its head is reached from the head of r by moving to
the x -y plane in a direction perpendicular to the plane. The three spherical polar
coordinates are r , θ , and φ . The coordinate r is the magnitude of the vector r as in
Eq. (2.58), θ is the angle between the positive z axis and the position vector r, and
φ is the angle between the positive x axis and the vector ρ , as in two-dimensional
polar coordinates. The angle θ is allowed to range from 0 to π and the angle φ is
allowed to range from 0 to 2π . The distance r is allowed to range from 0 to ∞,
and these ranges allow the location of every point in the three-dimensional space
to be given.
The following equations and Eq. (2.58) can be used to transform from Cartesian
coordinates to spherical polar coordinates:

z
θ = arccos (2.60)
r

and
y
φ = arctan . (2.61)
x

Equation (2.61) is the same as Eq. (2.40).

The following equations can be used to transform from spherical polar coordi-
nates to Cartesian coordinates:
40 Chapter 2 Symbolic Mathematics and Mathematical Functions

x = r sin (θ ) cos (φ) (2.62)

y = r sin (θ) sin (φ) (2.63)

z = r cos (θ ) (2.64)

EXAMPLE 2.5 Find the spherical polar coordinates of the point whose Carte-
sian coordinates are (1.000, 1.000, 1.000).

SOLUTION
√
r = (1.000)2 − (1.000)2 − (1.000)2 = 3.000 = 1.732
1.000 π
φ = arctan = rad = 45◦
1.000 4
1.000
θ = arccos = 0.955 rad = 54.7◦
1.732

EXERCISE 2.16 Find the spherical polar coordinates of the point whose
Cartesian coordinates are (2, 3, 4).
The cylindrical polar coordinate system is another three-dimensional coordi-
nate system. It uses the variables ρ , φ , and z, already defined and shown in
Fig. 2.11. The equations needed to transform from Cartesian coordinates to cylin-
drical polar coordinates are Eqs. (2.39) and (2.40). The third coordinate, z, is the
same in both Cartesian and cylindrical polar coordinates. Equations (2.37) and
(2.38) are used for the reverse transformation.

EXAMPLE 2.6 Find the cylindrical polar coordinates of the point whose Carte-
sian coordinates are (1.000, −4.000, −2.000).

SOLUTION
√
ρ = (1.000)2 + (4.000)2 = 17.000 = 4.123
−4.000
φ = arctan = 4.957 radians = 284◦
1.000
z = −2.000.

EXERCISE 2.17 (a) Find the Cartesian coordinates of the point whose
cylindrical polar coordinates are ρ = 25.00, φ = 60.0◦ , z = 17.50
(b) Find the cylindrical polar coordinates of the point whose Cartesian coordi-
nates are (−2.000, −2.000, 3.000).