taken from Prof. John Parson's website at The Ohio State Univ.

http://www.chemistry.ohio-state.edu/~parson/

Mathematical Review for Physical Chemistry

Outline:
1. Integration
(a) Important Integrals
(b) Tricks for evaluating integrals
2. Derivatives
(a) Important derivatives
(b) Tricks
3. Expansions
4. Partial Derivatives
(a) Denition
(b) An example
(c) Important relationships
5. Exact and inexact dierentials
6. Properties of Logs
7. Review of Trigonometry

1 Integration:
1.1 Integrals you should know:
1.1.1 Integrals involving x n

Z
ax dx = n +a 1 x
n n+1
(1)
Z
a dx = a ln x (2)
Z ax a
x dx
n
= (n 1)x n 1
(3)

1.1.2 Integrals involving sin,cos and e x

Z 1 cos(ax)
sin(ax) dx = (4)
Z a
cos(ax) dx = a1 sin(ax) (5)
Z
e dx = a1 e
ax ax
(6)

1
1.2 Tricks for evaluating integrals:
When an integral is more complicated than the ones shown above, integral tables are often
helpful. However, often the integral you are trying to solve and the ones in the tables do
not look the same and you may need to apply some manipulations to get them into the
\standard" form. Tricks that you may nd helpful are described below:
1.2.1 Break the integral into steps
Z1 Z 0 Z1
1
F (x) dx = 1
F (x) dx + 0
F (x) dx (7)
Z Z Z1
= F (x) dx + F (x) dx + F (x) dx (8)
a b

1 a b

1.2.2 Change the dummy variable

Since the result of an integration is independent of the variable over which the integration
is carried out, it can be treated as a dummy variable, e.g. the result does not depend
on what label it is given. It can be called x, u or Harry and the result will not change.
Mathematically:
Z Z
F (x) dx = F (u) du (9)
b b

x=a u=a

1.2.3 Change of variables

If u = kx, then x = u=k,

dx du = 1 du
dx = du (10)
Z Z
k 
1
F (x) dx = k F uk du (11)
b kb

x=a u=ka

1.2.4 Switching the limits of integration

Switching the limits of integration changes the sign of the integral:
Z Z
F (x) dx = F (x) dx (12)
b a

x=a x=b

1.2.5 Integration by parts

Z Z
u(x) dvdx(x) dx = u(x)v(x)j v(x) dudx(x) dx (13)
b b
b
x=a
x=a x=a

2
1.2.6 Other tricks
If the integrand contains sin's or cos's, you may nd it necessary to utilize one or more of
the trig identities reviewed below. If the integrand is even [F (x) = F ( x)] then
Z Z
F (x) dx = 2 F (x) dx (14)
a a

a 0

If the integrand is odd [F (x) = F ( x)]

Z
F (x) dx = 0 (15)
a

2 Derivatives
2.1 Ones you should know:
du n

= nu n 1
du (16)
dx dx
de u

= e du u
(17)
dx dx
d ln x 1
= x (18)
dx
d sin x = cos x (19)
dx
d cos x = sin x (20)
dx
2.2 Special relationships:
Chain rule:
d[F (u(x))] = dF du (21)
dx du dx
Derivative of a product:
d(uv) = du v + u dv (22)
dx dx dx
Derivative of a ratio:    
d(u=v) = v du
u dv

dx
dx

v 2
dx
(23)

3 Series Expansions of Functions

The rst derivative of a function provides its slope, the second its curvature. This means
that if we are interested in the behavior of a function near a specic point then a good
approximation is obtained by using a second order polynomial:
F (x)  A(x a) + B (x a) + C 2
(24)
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Where A = F 00 (a)=2, B = F 0(a) and C = F (a). At x = a the relationship is exact, while at
points near a the relationship provides a reasonable approximation to F (x), the size of the
error will depend on the size of the deviation of the function from being strictly quadratic
[the importance of higher order terms in the expansion]. This idea becomes important in
physical chemistry when one wants to study deviations from ideal behavior, for example,
the behavior of gases near zero pressure (the ideal gas limit).
In general, the series expansion of a function can be written as:
X F( j)
(a) (x a)
F (x) = j!
j
(25)
j

where F (a) represents the jth derivative of F (x) evaluated at x = a. Some particularly
(j )

useful expansions (all about x = 0) and the values of x for which they converge are given
below:

e = 1 + x + x2! + : : : + xn! + : : : ; [all x]

2 n
x
(26)
ln(1 + x) = x x2 + x3 : : : ( 1) xn : : : ; [x < 1]
2 3 n
n 2
(27)
1 = 1 x + x + : : : + ( 1) x + : : : ; [x < 1]
2 n n 2
(28)
1+x
1
1 x = 1 + x + x + : : : + x + : : : ; [x < 1] (29)
2 n 2

1
(1 x) = 1 + 2x + 3x + : : : + (n + 1)x + : : : ; [x < 1] (30)
3 n 2
2

p
1 + x = 1 + x2 x8 + 16
x + : : : ; [x < 1]
2 3
2
(31)
sin x = x x6 + 120
x : : : ; [all x]
3 5
(32)
cos x = 1 x2 + 24
x : : : ; [all x]
2 4
(33)

4 Partial Derivatives
4.1 Denitions:
If a function depends on two or more variables, f (x; y), then the partial derivative expresses
the dependence of f on one of the variables when all other variables are held constant.
Mathematically the partial derivative of f with respect to x at constant y is represented
by:
!
@f (34)
@x y

By analogy to the one-dimensional denition of the dierential of z(x):

4
 dz dx
dz = dx (35)
The dierential of z(x; y) is given by:
! !
@z dx + @z dy
dz(x; y) = @x (36)
@y y x

or more generally,
! !
@z
dz(x ; x ; : : : ; x ) = @x dx + : : : + @x@z dx (37)
1 2 n 1 n
1
2 n x ;:::;x 1 2 n 1 n
x ;x ;:::;x

 says that if x is changed by a innitesimal amount

Physically, the relationship of Eq. (36)
dx, the corresponding value of dz is dx and if y is changed by an innitesimal amount
@z
@x
 
y

dy, the corresponding change in z is given by dy. If both x and y are changed by
@z
@y

dierential amounts then the change in z will be given by the sum of the individual changes,
x

assuming dz is an exact dierential (see the following section). For an exact dierential,
the order of dierentiation does not matter:
" ! # 2 ! 3
@ @z = 4 @ @z 5 (38)
@x @y @y @x
x y y
x

which means the second derivative of z(x; y) can be expressed unambiguously by

@z  @z 2 2
(39)
@x@y @y@x
4.2 An Example:
z(x;!y) = x + 4x y + 12xy + 7y
3 2 2 3

@z = 3x + 8xy + 12y
2 2

@x
! y

@z = 4x + 24xy + 21y
2 2

2
@y 3 x
!
4 @ @z 5 = 8x + 24y
@y @x y
" ! # x

@ @z = 8x + 24y
@x @y x y

5
4.3 Important relationships
If f can be written as a function of either fx; yg where these variables are functions of
fu; vg so that:

x = x(u; v)
y = y(u; v)
by the chain rule [Eq. (21)],
! ! ! ! !
@f = @f @x + @f @y (40)
@u v
@x y
@u @y v x
@u v

NOTE the variables appear in specic pairs - for example, derivatives with respect to x are
taken at constant y and derivatives with respect to u are taken at constant v. This general
relationship simplies to some important relationships
4.3.1 u = x and v = z
! ! ! ! !
@f = @f @x + @f @y
@x @x @x @y @x
z
! y
! ! z x z

= @f + @f @y (41)
@x @y
y
@x x z

 
since @x
@x z
=1
4.3.2 u = x, v = z and f = z
! ! ! !
@z = @z + @z @y
@x @x @y @x
! z
! y
! x z

@z = @z @y (42)
@x y
@y x
@x z

 
since @z
@x z
= 0. Using the relationship:
!
@z 
1 (43)
@x y
@x
@z
y

Eq. (42) can be rewritten as:

! ! !
1 = @x
@z
@z
@y
@y
@x (44)
y x z

6
5 Exact and Inexact Dierentials
Functions, like U or H , have the property that their value depends only on the state of the
system and not how it arrived at that state. These functions are called state functions and
change in their values resulting from a change in the state of the system depends only on
the starting and ending points, but not how they arrived there. The dierentials of these
functions are called exact dierentials. Mathematically this means that the dierential of
a state function f (x; y) is given by:
! !
df = @f
@x dx + @f dy
@y (45)
y x

= M (x; y)dx + N (x; y)dy (46)

Eq. (38) says that:
! !
@M = @N (47)
@y x
@x y

which is often taken as the denition of exactness. Dierentials for which this relationship
does not hold, or where the changes depend on the path are called inexact dierentials and
are represented by df . Examples of inexact dierentials in thermodynamics are dq and dw
since the work done on a system or the heat absorbed by the system depend on the path
the system takes to get from its initial to nal state.

6 Properties of Logs:
log(a) + log(b) = log(ab) (48)
log(a) log(b) = log(a=b) (49)
log(a)
n
= n log(a) (50)
ln(a) = ln(10) log (a) = 2:303 log (a)
10 10 (51)

7
7 Review of Trigonometry
sin(a + b) sin(a) cos(b) + sin(b) cos(a)
= (52)
sin(a b) sin(a) cos(b) sin(b) cos(a)
= (53)
cos(a + b) cos(a) cos(b) sin(a) sin(b)
= (54)
cos(a b) cos(a) cos(b) + sin(a) sin(b)
= (55)
cos(2a) cos (a) sin (a) = 2 cos (a) 1 = 1 2 sin (a)
= 2 2 2 2
(56)
sin(2a) 2 sin(a) cos(a)
= (57)
cos (a)
2
1 (cos(2a) + 1)
= (58)
2
sin (a) = 12 (1 cos(2a))
2
(59)