CALCULUS REVIEW

(Version 2001)

I. INTRODUCTION
If physical chemistry lecture and/or p-chem lab are going to be difficult for you, it will
probably be due to problems with math (calculus) and not due to problems with the chemistry.
Most of you have just finished organic chemistry. In that course you used chemical rules
to rearrange (chemical reactions) symbols (carbon, hydrogen, etc.). In physical chemistry, we are
going to use the rules of calculus to help us rearrange physical property symbols (pressure,
volume, temperature, entropy, etc.). In organic chemistry your goal was to understand chemical
reactions (predict reaction products and reaction sequences). In physical chemistry, we will use
calculus to help us calculate and understand the physical properties of chemical systems.
In first semester p-chem, the calculus that we will use is a fairly straight forward application of differentiation and integration. It is very important that you are comfortable with the basic
mechanics and physical significance of differentiation and integration.

II. DERIVATIVE NOTATION

There are two common notations used to indicate derivatives. Consider the equation
y = 11 + 7x - 4x3. I am sure you recognized that the first derivative is 7 - 12x2 and the second
derivative is -24x. Some of you would say that:
y1 = 7 - 12x2

and

y2 = -24x.

Others would use the notation:

dy
dx

7 12x 2

and

d 2y
dx 2

24x.

Most of the time we will use the second method for denoting derivatives. The term dy is known
as the differential of y and dx is the differential of x.

III. PHYSICAL SIGNIFICANCE OF FIRST DERIVATIVES

The most common physical interpretation of a derivative is as the slope of a curve. If y is
known as a function of x (i.e., y = f(x)), then dy/dx is the slope of the curve obtained when y is
plotted versus x.

Consider the equation, y = 6x + 3. Do you recognize this as the equation of a straight line
with a slope of 6 and a y intercept of 3 at x = 0? The general form of the straight line equation is
usually given as y = mx + b (m= slope and b = the intercept) or y = a + bx ( b= slope and a =
intercept).
For the equation, y = 6x + 3, dy/dx = 6. This means that a plot of y versus x for this
equation will have a slope of 6. In fact, for a linear function, such as this one, the slope is
constant and is independent of where on the graph you determine it.
Now consider the equation y = 3 + 2x + 6x2 , dy/dx = 2 + 12x. The derivative, dy/dx, is
still the slope of a graph of y versus x, but for this function the graph is not linear and the slope
depends on where on the curve it is measured. If you determine the slope at x = 0, dy/dx = 2, but
if you determine the slope at x = 2, dy/dx = 26. In all cases dy/dx is the slope of a graph. For
linear functions, the slope is constant and for non linear functions the slope depends on the value
of the independent variable.
IV. DIFFERENTIAL EQUATIONS
Differential equations are mathematical equations which contain a derivative. Such
equations play a very important role in physical chemistry. Differential equations are often the
starting point in mathematical derivations that lead to better understanding of the physical
properties of chemical systems. Most of the differential equations that we will encounter in
physical chemistry will eventually be used to calculate a particular physical property. In order to
make the calculation, the differential equation must first be integrated.
During the course of both semesters of physical chemistry you will encounter two types of
differential equations. The first type will be very common during the first semester. In this type
of differential equation all the relationships (called equations of state) are known and integration is
usually easy to accomplish. For example, consider the following differential equation and
equation of state. When one mol (n=1) of an ideal gas undergoes an adiabatic expansion against a
constant pressure, the following differential equation is developed.
dT
dV

(1)

Cv

For 1 mol of an ideal gas, PV=RT

Cv = heat capacity = constant for ideal gases
To integrate an equation in this form, we must first separate the two differentials (dT and dV).
Equation 1 would thus be rewritten as:
C v dT

P dV

(2)

Once the differentials have been separated, everything that depends on T is collected on the dT
side and everything that is a function of V is collected on the dV side. Constants can be collected
wherever it is convenient. Looking at Equation 2, Cv is a constant, but P is a variable. Therefore, we must convert P into a function which contains only V, T and/or constants. The equation
of state will do this. From the equation of state for one mol of an ideal gas,

RT
V

Inserting this into Equation 2 gives:

RTdV

CvdT

Rearrangement of variables gives:

CvdT
T

RdV
V

Integration over the limits T1 , V1 to T2 , V2 gives equation 3.

T2

T1

CvdT
T

Cv ln

T2
T1

V2

V1

RdV
V

R ln

V2
V1

R ln

V1
V2

(3)

Remember -- in order to evaluate any integral of the general form:

P Q R dx

P, Q and R must either be constants or they must be able to be rewritten in terms of the differential variable, in this example that would be the variable x. Another way of saying this is to
remember that in an integral everything under the integral sign must either be a constant or be in
terms of the same variable as the differential. That is why in the integration which produced
Equation 3, the variable T had to be moved to the side containing the differential dT and the
variable V had to be with the differential, dV.

V. PHYSICAL SIGNIFICANCE OF DEFINITE INTEGRALS

The most common interpretation of the result of a definite integral is that the result of the
integration represents a summation. For example, consider the definite integral
50

f(x) dx
Result

10

Result, the numerical value of the integral, is the sum of an infinite number of rectangles F(x)
high and dx wide. Since a height, (F(x), times a width, dx, is an area, the value of the integral
given above can be interpreted as the area between x = 10 and x = 50 under the curve produced
when F(x) is plotted versus x.
Consider the following integral.
50

R T dV
P V

17

10

If :

R = .0821 Liters x Atm

K x mol
T = 298K
V = Liters
(a) What are the units on the result?
(b) What are the units on the limits?
(c) What must be plotted on the y axis and what must be plotted on the x axis to give the
curve which has an area of 17?
(d) Sketch the curve from V = 5 to V = 60 and indicate the area calculated by the integral.

VI. APPENDICES
Appendices A and B contain most of the differentiation and integration formulas that you will
need to be able to apply. Please become very familiar (memorize) with these fundamental
formulas.

VII. DIFFERENTIATION PRACTICE

Find the indicated derivative(s) of each of the following functions.
a) y = 8x3 + 6

Find dy/dx and d2y/dx2

b) y = (1 - x2)1/2

Find dy/dx

c) y = x4e2x

Find dy/dx

d) y = A sin V Cos V

Find dy/dV

A = Constant

e) 3 = 2A Sin (nx)
L

Find d3/dx

A, n, & L = constants

f) y = x3(1 - ex)-1/2

Find dy/dx

g) ln k = -G
RT

Find d(ln k)/dT

h) PV = nRT

Find dV/dP and d2P/dV2

i) H = A + BT + CT2 + DT3

Find dH/dT

A, B, C & D = constants

j) (P + 1/V3 )V =K

Find dV/dP

When K = constant

G, R = constants
n, R & T = constant

VIII. INTEGRATION PRACTICE

Evaluate each of the following indefinite integrals.
4x 2 dx

a)

b)

dx
Px3

c)

P dV

Where PV = nRT. For this problem n,R & T as constants

R T dP
P

e)

x dx
x 2 1

f)

dx
P (x 4) (x3)

g)

d)

A
T2

Where R & T = constants

 B  C  DT ) dT
T

A, B C & D are constants

Evaluate each of the following definite integrals.

V2

h)

PV

P dV

Where PV=nRT and n,R,T = constants

P2

i)

dP
P P
P1

T2

H dT
2

PT R T
1

H, R = constants

T2

H
(a  bT  c2 )dT

j)

K2

k)

P
K

T2

dln K

sin2(

P
0

Ea

PT RT 2

dT

Ea and R = constants

l)

a, b and c = constants

T1

x
) dx
a

a = constant

IX. OTHER TOPICS TO REVIEW

a)

How to take second derivatives

b)

The difference between explicit and implicit differentiation.

c)

How to use differentiation to locate maximum, minimum and inflection points.

d)

Integration by parts.

e)

Integration by partial fractions (Question VIII-f)

f)

Trigonometric substitutions (Question VIII-l)

g)

Independent and dependent variable(s).

Appendix A
Fundamental Integration formulas

Appendix B