Roger Nix (Queen Mary, University of London) - 6.

1
CHAPTER 6 : CALCULUS

Differentiation

Introduction to Differentiation

Calculus is a branch of mathematics which concerns itself with change. Irrespective of whether
it is the change of concentration in a chemical reaction or the change of slope of a graph, calculus
provides the necessary techniques.

Consider a simple example, the graph of y = x
2
.

0
2
4
6
8
10
-1 0 1 2 3
x
y
Fig.1
Tangent at x = 2
y = x
2

At any given point the slope of the curve will be given by the slope of the tangent at that point (the
tangent is the straight line which just coincides with the curve at the point of concern as illustrated
for x = 2). From an inspection of the figure above, it is clear that the value of the slope for this
function is always changing with the value of x.

The slope can also be measured by assuming the curve to be made up of very large number of very
short straight lines. Any one such straight line can be imagined as the hypotenuse of a right angled
triangle as shown in Fig.2 below, the other two sides being small increments along the x and y axes,
x and y respectively.

Fig.2









y
x
x
y y
(x,y)
(x +x ,y +y)
Roger Nix (Queen Mary, University of London) - 6.2
The slope of the hypotenuse (the dotted line), given by
x
y

, is then approximately equal to the slope

of the tangent at x .

As y = x
2
then, for this particular example, it must be the case that :

y + y = ( x + x)
2

y + y = x
2
+ 2x x + (x)
2


Subtracting y ( = x
2
) from both sides gives:

y = 2x x + (x)
2


It is now necessary to imagine that the triangle in Fig.2 becomes smaller and smaller so that y , x
and the hypotenuse become indefinitely small. This process will lead, in the limit, to the slope of the
hypotenuse in Fig.2 being exactly equal to the slope of the tangent at point x . Under these
circumstances, when x is very small then (x)
2
can be neglected. When this limit is approached it
is usual to write y and x as dy and dx.

So y = 2x x can be written as dy = 2x dx

and the slope of the tangent at x is : x
dx
dy
2 =

We can generalise this approach to consider a curve representing the function y = x
n
.
Then:

y + dy = ( x + dx)
n


Noting

+ = +
x
dx
x dx x 1 ) (

n
n
x
dx
x dy y

+ = + 1 ) (

+ + = ..... . 1
x
dx
n x
n
(from the Binomial expansion - see 5.11)

The higher terms involving (dx)
2
, (dx)
3
etc. (represented by ..... ) may be ignored because dx is so very
small. Thus:

dx nx x
x
dx
nx x
x
dx
n x dy y
n n n n n 1
. 1 ) (

+ = + =

+ = +
dx nx dy
n 1
=

1
=
n
nx
dx
dy


or to put it another way :
1
) (

=
n n
nx x
dx
d
i.e. the derivative of the function x
n
is n x
n1

Roger Nix (Queen Mary, University of London) - 6.3
This then is a general equation for differentiating x raised to any power. Note that if a preceding
constant k , had been included in the above calculations it would still be present in the answer, i.e.

If y = k x
n
then
1
) (

=
n n
knx kx
dx
d


Special cases :
1. if n = 1 , as in y = k x , then k
dx
dy
= - the slope of a straight line is a constant.
2. if n = 0 , as in y = k , then 0 =
dx
dy
- the function corresponds to a horizontal straight line
with zero slope.



Standard Derivatives

You should aim to remember the following standard derivatives - in the following table, the symbol k
is used to represent a constant.

Function Derivative

y = k 0 ) ( = constant
dx
d

y = k f(x) )) ( ( )) ( ( x f
dx
d
k x f k
dx
d
=
y = f(x) + g(x) )) ( ( )) ( ( )) ( ) ( ( x g
dx
d
x f
dx
d
x g x f
dx
d
+ = +
y = x
n 1
) (

=
n n
nx x
dx
d

y = e
x

x x
e e
dx
d
= ) (
y = ln x
x
x
dx
d 1
) (ln =
y = sin x x x
dx
d
cos ) (sin =
y = cos x x x
dx
d
sin ) (cos =
Roger Nix (Queen Mary, University of London) - 6.4
Derivatives of More Complex Functions

situation often arises when rather more complicated functions have to be differentiated. There are
various procedures for dealing with these situations, which reduce the problem to the point where we
can use the standard derivatives given on the preceding page.


Differentiation by Substitution (Chain Rule)

This method is used for functions such as, for example, exp (kx) or sin
2
[ sin
2
is the usual way of
writing (sin )
2
]. Thus:

i) y = exp (kx) ; let u = kx then y = exp (u) and k
dx
du
=

y = exp (u) ) exp(u
du
dy
=

We now make use of the Chain Rule relationship :
dx
du
du
dy
dx
dy
=

k u
dx
dy
= ) exp(
) exp(kx k
dx
dy
=

ii) y = sin
2
; let u = sin then y = u
2
and

cos =
d
du


y = u
2
u
du
dy
2 =

Again using the Chain Rule :
d
du
du
dy
d
dy
=

cos 2 = u
d
dy

cos sin 2 =
d
dy



Roger Nix (Queen Mary, University of London) - 6.5
Differentiation of Products (Product Rule)

Another common situation is to find that it is necessary to differentiate the product of two simpler
functions. Let the simpler functions be denoted by u and v , then y = u.v . Consider now small
increments to each function, so that
(y + dy) = (u + du) (v + dv)
y + dy = u.v + v.du + u.dv + du.dv
Subtraction of y (= u.v) from each side, and neglecting the product, du.dv, of two very small terms
du and dv yields
dy = v.du + u.dv
If the small change in each of the functions arises from a small change, dx , in the variable x then

dx
dv
u
dx
du
v
dx
dy
. . + = i.e.
dx
dv
u
dx
du
v
dx
uv d
. .
) (
+ = ( Product Rule )



Differentiation of Quotients (Quotient Rule)

Suppose
v
u
y = i.e. y = u v
1


Using the product rule :

dx
du
v v
dx
d
u
dx
dy
1 1
) (

+ =
Using the method of substitution :

dx
dv
v
dx
dv
v
dv
d
v
dx
d
. ). ( ) (
2 1 1
= =
Combining the two previous results gives :

dx
du
v
v
dx
dv
v
u
dx
du
v dx
dv
v
u
dx
dy
2 2 2
1
+ = + =

2
v
dx
dv
u
dx
du
v
dx
dy

= ( Quotient Rule )



Roger Nix (Queen Mary, University of London) - 6.6
Second Derivatives
The second derivative, denoted by
2
2
dx
y d
, is obtained by differentiating the first derivative, i.e.

=
dx
dy
dx
d
dx
y d
2
2


Example
If y = x
2
then x
dx
dy
2 = and
2 ) 2 (
2
2
= = x
dx
d
dx
y d




Partial Derivatives

Partial derivatives are obtained by differentiating with respect to one variable whilst treating all other
independent variables as constants,

For example, suppose z = xy + y
2
then

y y
x
z
x
z
y
= + =

0 . 1 ( y is treated as a constant)
y x y x
y
z
y
z
x
2 2 1 . + = + =

( x is treated as a constant)
Note the use of a curly for the partial derivative.

Partial derivatives occur frequently in thermodynamics e.g. the heat capacity at constant pressure, C
P
,
is the (partial) derivative of enthalpy with respect to temperature at constant pressure, i.e.
P
P
T
H
C

=

Roger Nix (Queen Mary, University of London) - 6.7
Chemical Applications of Differentiation : Kinetics

The ideas of calculus which have been introduced in the preceding sections find one of their most
important applications in the study of the rates at which chemical reactions proceed. A brief
introduction to this topic, that of chemical reaction kinetics, follows.

Representation of Reaction Rates

Suppose we have a reaction between two species, A and B , of the type :

a A + b B Products

where a and b are the stoichiometric coefficients.

The rate of a reaction is a measure of the rate of change of the concentration (or partial pressure in the
gas phase) of one of the reactants or products.

e.g.
dt
dc
Rate
A
= or
dt
Products d
Rate
] [
=

Note that if the reaction proceeds in the indicated direction then the concentration of species A ,
denoted by c
A
or [A] , will decrease over time, whereas the concentration of products will increase
over time - consequently
dt
dc
A
will be negative whereas
dt
Products d ] [
will be a positive quantity.

In general, the rate may depend on the concentration of any or all of the various substances present. A
rate expression relates the rate to the concentrations of the reactants (and in some cases also to the
products). Often a simple algebraic representation is possible, for example

m
B
n
A
A
c c k
dt
dc
=
where n and m are integers. The reaction is then said to be of order n with respect to substance A
and of order m with respect to substance B.

k is the rate constant (or rate coefficient), so called because it is independent of concentration.
However, k does depend on temperature, i.e. its value varies when the temperature is changed.

Note that different symbols have been used for the order of reaction n with respect to A and m with
respect to B, and for the number of moles a of A which react with b moles in the stoichiometry of the
reaction. This is because kinetic order and stoichiometry are not, in general, the same.

Roger Nix (Queen Mary, University of London) - 6.8
Maxima and Minima

The function
3
2
3
2 3
x
x x y + = plotted below has a maximum at x = 1, y = 1.3333 and a minimum at
x = 3, y = 0.
0
1
2
0 1 2 3 4
x
y
dy/dx = 0
dy/dx = 0
dy/dx < 0
dy/dx > 0
dy/dx > 0

At both the maximum and the minimum the slope is zero and 0 =
dx
dy
.
Thus the positions of maxima and minima (turning points), if present, can always be found by
differentiating a function and equating the result to zero.

Example

3
2
3
2 3
x
x x y + =
2
4 3 x x
dx
dy
+ =
At a turning point 0 =
dx
dy

0 4 3
2
= + x x

0 ) 3 )( 1 ( = x x

i.e. turning points occur at x = 1 and x = 3

One can distinguish between a maximum and a minimum by noting the trend of
dx
dy
in the region of
the turning point.

1. Consider, the maximum (at x = 1 ) in the above example.
when x < 1, the slope,
dx
dy
, is positive
when x > 1 (but less than 3 ), the slope,
dx
dy
, is negative.
Thus in the region of the maximum
dx
dy
is decreasing as x increases.
Roger Nix (Queen Mary, University of London) - 6.9
Consequently the derivative of the slope,
dx
dy
, with respect to x is negative,
i.e. the second derivative,
2
2
dx
y d
, must be negative.

Check:
x x x
dx
d
dx
y d
2 4 ) 4 3 (
2
2
2
+ = + =

At x = 1 , 2 ) 1 2 ( 4
2
2
= + =
dx
y d


2. Consider, the minimum (at x = 3 ) in the above example.
when x < 3 (but greater than 1), the slope,
dx
dy
, is negative
when x > 3, the slope,
dx
dy
, is positive.
Thus in the region of the maximum
dx
dy
is increasing as x increases. Consequently the second
derivative,
2
2
dx
y d
, must be positive.
Check:
x x x
dx
d
dx
y d
2 4 ) 4 3 (
2
2
2
+ = + =

At x = 3 , 2 ) 3 2 ( 4
2
2
+ = + =
dx
y d

If both
dx
dy
and
2
2
dx
y d
are zero at a given point on a curve, that point is said to be a horizontal point
of inflexion. An example of such a point is the point x = 1, y = 3 on the curve 6 8
4
+ = x x y , as
shown below.
0
2
4
6
8
0 1 2
x
y
dy/dx = 0
d
2
y/dx
2
= 0
dy/dx > 0
dy/dx > 0
d
2
y/dx
2
< 0
d
2
y/dx
2
> 0

Roger Nix (Queen Mary, University of London) - 6.10
Summary :

dx
dy

2
2
dx
y d

Minimum 0 +ve
Maximum 0 ve
Pt. of Inflexion 0 0


These mathematical techniques are widely used in chemistry since one often wishes to predict the
conditions under which some quantity has a maximum or minimum value, e.g., the attainment of
thermodynamic equilibrium may correspond, under different conditions, to the maximisation of the
entropy or to the minimisation of the free energy of the system.

Roger Nix (Queen Mary, University of London) - 6.11
Integration

Integration can be considered as both

1. the inverse (reverse) operation to differentiation, and
2. a method for determining the area under a plotted function.


Integration as the Inverse of Differentiation

If ) ( )) ( ( x f x f
dx
d
= then C x f dx x f + =

) ( ) (

where C is the so-called constant of integration.



e.g. C x dx x + =

2
. 2


The constant of integration arises because any function of the form (x
2
+ constant ) will yield 2x
upon differentiation so there is ambiguity when it comes to considering the reverse operation.

This type of integral where there is an ill-defined constant of integration is known as an indefinite
integral.


From our study of differentiation we know:


1
) (

=
n n
nx x
dx
d

+ =

C x dx nx
n n 1


and


n
n
x
n
x
dx
d
=

+
+
1
1
C
n
x
dx x
n
n
+
+
=

+
1
1


The relationship in the box is the standard form for the integration of x
n
: it works for all values of n
except 1 , a special case to be considered later.

We can use this same approach to derive a set of standard integrals as listed on the next page.
Differentiation
Integration
Roger Nix (Queen Mary, University of London) - 6.12
Standard Indefinite Integrals

You should aim to remember the following standard integrals - in the following table, the symbol k is
used to represent a constant.


Function Integral

y = k f(x) dx x f k dx x f k . ) ( ). (

=
y = f(x) + g(x)

+ = + dx x g dx x f dx x g x f ). ( ). ( )). ( ) ( (
y = x
n
C
n
x
dx x
n
n
+
+
=
+

1
1
(provided n 1 )
y = e
x
C e dx e
x x
+ =

x
y
1
= C x dx
x
+ =

ln .
1

y = sin x C x dx x + =

cos . sin
y = cos x C x dx x + =

sin . cos



Roger Nix (Queen Mary, University of London) - 6.13
Definite Integrals and Integration as a Method of Determining Areas

The following integral is an example of a definite integral.

) ( ) ( ) ) ( ( ) ) ( ( ). (
1 2 1 2
2
1
x f x f C x f C x f dx x f
x x
x x
= + + =

=
=


The integration is now carried out between two limits: x
1
is the lower limit, x
2
is the upper limit.

This type of integral calculation is commonly abbreviated in the following fashion:

[ ] ) ( ) ( ) ( ). (
1 2
2
1
2
1
x f x f x f dx x f
x
x
x
x
= =

Graphically the integral is equal to the area between the curve (formed by plotting f(x) against x ) and
the x-axis, between the limits x = x
1
and x = x
2
.

Example
What is the area under the curve y = x
2
+ 1 between x = 0 and x = 2 ?

Area , A =

+
2
0
2
). 1 ( dx x
= [ ]
2
0
3
3
1
x x +

= (
8
/
3
+ 2) (0 + 0)

=
14
/
3
= 4.667 (to 3 d.p.)



More Complex Integrals

As with differentiation, there are standard approaches which may be used to handle more complex
functions.

1. Integration by Substitution

This method may be used when the function to be integrated consists of a product of two parts, where
one part is the differential of the other.

Example

dx x x . cos sin
Note that cos x is the derivative of sin x , so this product meets the requirement for this approach.
y
x
y = x
2
+ 1
2 0
A
Roger Nix (Queen Mary, University of London) - 6.14

Let u = sin x

x
dx
du
cos =
dx x du . cos =

Hence

dx x x . cos sin =

du u.
= C u +
2
2
1

= C x +
2
2
1
sin


2. Integration by the Method of Partial Fractions

This method may be used when the function consists of a fraction, and the denominator of this fraction
is a polynomial which may be factorized.

Example
I =

dx
x x 4
8
3


The fraction requiring integration may be split into a series of partial fractions (see 1.11):

) 2 )( 2 ( ) 4 ( 4
2 3
+ = = x x x x x x x


2
1
2
1 2
) 2 )( 2 (
8
4
8
3

+
+
+

=
+
=
x x x x x x x x


Consequently,

I =


+
+
+

dx
x
dx
x
dx
x
.
2
1
.
2
1
.
2

= C x x x + + + + ) 2 ln( ) 2 ln( ln 2
= C x x x + + + +

) 2 ln( ) 2 ln( ln
2

= C
x
x x
+

+
2
) 2 )( 2 (
ln
= C
x
x
+

2
2
) 4 (
ln

Roger Nix (Queen Mary, University of London) - 6.15
Chemical Applications of Integration

1. Reaction Kinetics - Integrated Rate Expressions

We can now derive and apply the concentration-time relationships for reactions exhibiting zero-order,
first-order and second-order kinetics.

(a) Zero-order

Chemical reaction : A Products

Rate expression : k k
dt
d
= =

0
[A]
[A]


Integration : dt k d . [A] =



= dt k d . [A] .

[A] = kt + C

If [A] = [A]
o
when t = 0 , then

[A]
o
= 0 + C C = [A]
o


Hence,
[A] = [A]
o
kt

Thus the concentration of the reactant decreases linearly with time in a zero-order reaction.

To test for zero-order kinetics, plot [A] against time, t ; if the graph is linear over a time
corresponding to several half-lives then the reaction is zero-order and the rate constant, k , can be
evaluated from the slope of the graph (which is equal to k ). The units of k will be those of
(concentration / time), e.g. mol dm
3
s
1
.










[A]
Time , t
ZERO ORDER
[A] = [A]
o
k t

slope = k
[A]
o

0
0
Roger Nix (Queen Mary, University of London) - 6.16
(b) First order

Chemical reaction : A Products

Rate expression : [A] [A]
[A]
1
k k
dt
d
= =

Integration : dt k
d
.
[A]
[A]
=

= dt k d . [A] .
] A [
1


ln [A] = kt + C

If [A] = [A]
o
when t = 0 , then

1n [A]
o
= 0 + C C = 1n [A]
o


Hence,
ln [A] = kt + 1n [A]
o


ln [A] 1n [A]
o
= kt

kt =

0
] A [
] A [
ln or [A] = [A]
o
e
kt

In a first-order reaction, the natural logarithm of the concentration of the reactant decreases linearly
with time, and the concentration itself falls exponentially with time.














To test for first-order kinetics, plot ln [A] against t ; if the graph is linear over a time
corresponding to several half-lives then the reaction is first-order and the rate constant, k , can be
evaluated from the slope of the graph (which is equal to k ). Note than the units of k are (time)
1
.
[A]
Time , t
FIRST ORDER
[A] = [A]
o
e
k t


[A]
o

0
0
Roger Nix (Queen Mary, University of London) - 6.17














2. Beer-Lambert Absorption Law

This law lies at the heart of quantitative spectroscopy since it describes how, in an overall way,
radiation is absorbed by matter. It is assumed that when radiation, of initial intensity I passes through
a thin slice of matter of thickness dx, then the small amount absorbed, dI , is a certain fraction of the
orginal intensity, provided dx is sufficiently small. Expressed mathematically, this means that:

dI = k.I.dx

where k is a constant depending upon the material and the wavelength. dI is negative because I is
decreasing as x increases.

The equation can be arranged to give: dx k
I
dI
=
and then integrated to give:

= = dx k dx k
I
dI


In this case the integration can be carried out between definite limits. These limits are the initial
values of I and x , I
o
, and 0 respectively, and the final values of I and x, i.e. I
d
and d , where I
d
is the
intensity of light emerging from a sample of macroscopic thickness d . As noted previously, these
limits are written at the bottom and top of the integral sign and the subsequent working is set out as
shown below.



=
d I
I
dx k
I
dI
d
o
0
[ ] [ ]
d I
I
x k I
d
o
0
ln =

) 0 ( ln ln = d k I I
o d


kd
I
I
o
d
=

ln or kd
I
I
d
o
=

ln
ln [A]
Time , t
FIRST ORDER
ln [A] = ln [A]
o
k t

slope = k
ln [A]
o

0
0
Roger Nix (Queen Mary, University of London) - 6.18
In solution k is related to two properties of the absorbing species: the molar absorption coefficient
(extinction coefficient) and c the concentration. As much spectroscopy is carried out in solution the
Beer-Lambert law is therefore often expressed in the form:
d c
I
I
o
d
. . ln =

Note on units - the right hand side is a logarithm and has no units. By convention, c is usually given
in units of mol dm
3
(= mol L
1
) and d is the length of the sample cell in cm . The units of are
therefore typically L mol
1
cm
1
.

3. Radioactive Decay

It is found that the rate of radioactive decay is proportional to the amount of radioactive material
present thus

N
dt
dN
cay Rate of de = =

where N is the number of radioactive atoms present at any time t and is the decay constant.
Note -
dt
dN
is negative since nuclei are decaying and their number decreasing.

Rearrangement yields : dt
N
dN
= , and integration gives


= dt
N
dN


If N
o
atoms were present at the beginning (i.e. at t = 0) and N after time t - then, with limits, the
integration yields:

[ ] [ ]
t N
N
t N
o
0
ln =

) 0 ( ln ln = t N N
o


t
N
N
o
=

ln or t
N
N
o
=

ln or N = N
o
e
t


A special case is when N = N
o
, i.e. when the number of atoms has been reduced to half its initial
value. The time taken for this to happen is known as the half-life (

). In this case


2 1
2
1
ln =

o
o
N
N
693 . 0 2 ln
2 1
= =

Thus the decay constant can be found if the half-life is known.