Kinetics & Equlibria

1.

RATES OF REACTION

Concepts & Experiments Associated With Rates Of Reaction

Factors affecting the rate of a chemical reaction are:

Temperature
Concentration
Surface Area
Catalyst
Light

A chemical reaction is the result of collision of sufficient energy and proper orientation. The rate
can be expressed as the product of three factors:
Rate

Collision
Frequency

Energy
Factor

Probability Factor
(Orientation)

The collision frequency depends upon:

(a) How closely the particles are crowded together, i.e. concentration or pressure.
(b) How large they are and,
(c) How fast they are moving which depends on their weight and the temperature.
The probability factor depends on the geometry of the particles and the kind of reaction that is
taking place.
Energy factor depends upon temperature and the energy of activation, E act.

Energy

The minimum energy needed to make a reaction take place is called the Activation Energy, Eact.

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Kinetics & Equlibria

Figure 1.1
Graph
Showing
Energy Against
Reaction
Course.

Reactants

Products

Reaction Course
Cl.
H

CH3
HCl

+ CH3.

Br. + CH3 ----- H

Eact

= 16.8 KJ.

HBr + CH3.

Eact

= 72 KJ.

As can be seen above, Chlorine is far more reactive than Bromine.

A successful reaction depends also on proper orientation. For instance:
Figure 1.2
Diagrams
Showing
Successful
Reactions.

H
OH-

..

..

..

H
O ..

..

OH- + CH3I

C
H

I-

+
H

CH3OH + IThe collision may be successful, if the direction of

approach is correct, but the energy lies to the right as well.

P.E

CH .

+ HCl

3
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Appadu

Figure 1.3
Progress Of
Reactions.

Kinetics & Equlibria

Eact = 16.8 KJ

CH4

H = +4.2 KJ KJ

Prog
CH
+ HCl
3
ress
OF
Rea
ctio
ns

+ Cl
CH4. + Cl

Figure 1.4

P.E

Progress Of
Reaction
CH3.

+ HBr

Eact = 72 KJ
H = + 67.2 KJ

CH4 + Br.
CH4 + Br.

Prog
ress
OF
.
CHRea
+ HBr
3
ctio
ns

Surface Area
The smaller the size of reactivity particle, the greater is the total surface area exposed for reaction
and, consequently, the faster reaction
(a) Slow reaction Marble chips with dilute hydrochloric acid
CaCO3 (s)

+ 2HCl

CaCl2 + H2O + CO2 (g)

(b) Fast reaction Power CaCO3 + (dil) HCl

Others:

Mg (Ribbon) + HCl
Mg (Powder) + HCl

Slow
Fast

Concentration
An increase in concentration means there are more reactant molecules in a given volume. This
may lead to more frequent collisions and to a faster rate of reaction.

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Kinetics & Equlibria

When acid is added to sodium thiosulphate solution, a five colloidal solution of sulphur is
formed. If the reacting mixture is placed over a white paper with a mark, the mark soon
disappears after a certain time. With varying concentrations of either acid or thiosulphate the time
will vary.

Expt
Numb
er
1
2
3
4
5
6
7
8

Table 1.1
Relation Of
Volume To
Thiosulphate
Concentration.

Volume Of
Acid
(cm3)
50
50
50
50
50
50
50
50

Volume of
Thiosulphate
(cm3)
50
45
40
35
30
25
20
15

Volume
Of
Water
0
5
10
15
20
25
30
35

Time,
t
(s)

1/t

The volume of the thiosulphate is directly related to its concentration. The ratio of the reaction
depends on concentration of sodium thiosulphate. 1/t is a measure of the rate. A plot of 1/t against
volume of thiosulphate will show how concentration affects the rate.

Figure 1.5
Inverse Of Time
Against Volume.

1/t

Volume

Temperature
The rate of a chemical reaction is increased by increasing temperature of the reactants. Particles
move faster when temperature is raised. This means that:

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Kinetics & Equlibria

(a) Particles collide more frequently

(b) The collision are more energetic, i.e., more particles have energy greater than E act., as
a result the reaction rate is faster e.g.
Slow:
Fast:

Mg (Ribbon) + Cold HCl

1.0 M
Mg (Ribbon) + Hot HCl
1.0 M

H2 (g)
H2 (g)

At different temperatures the volume of the gas formed could be measured and volume plotted
against time.

Catalysts
Catalyst alters the rate of a chemical reaction. They lower the activation energy for a given
reaction ensuring that more are successful; enzymes are catalyst in biological systems. Many
industries use different types of inorganic catalyst.

Table 1.3
Some Functions And
Uses Of Catalysts In
Industries &
Biological Systems.

Industri
al
Process

HNO3
Producti
on

NH3
Producti
on

SO3
Producti
on

Hardeni
ng
Oils

Crackin
g
Oils

Catalyst

Pt / Rh

Fe

V Cpds.

Ni

Al2O3

Enzymes

Functions

Salivary Amylase

Found in saliva. Converts starch to maltose.

Catalyze

Decomposes peroxides, which would otherwise act as poisons.

Found in the liver.

Enzymes are specific, affected by pH and temperature.

Figure 1.6
P.E Required To
Use Reactants To
Eact (Without
ProduceCatalyst)
Products.

P.E

Table 1.2
Catalysts Used
In Industries.

Eact (With Catalyst)

Products

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Reactants

Hor =

Kinetics & Equlibria

A change of reactants to products has a lower Eact if a catalyst is used.

Example:
2H2O2
2KClO3

MnO2

2H2O + O2

MnO2

2KCl

+ 3O2

The volume of O2 (g) produced is plotted against time.

Figure 1.7
Apparatus Used
To Collect O2 (g)
For The
Catalytic
Decomposition
Of H2O2.

O2

Syringe

H2O2
MnO2

Volume (cm3)

Figure 1.8
Graph Showing
Volume Against
Time.

Time (s)
Time (s)

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Kinetics & Equlibria

Light
Photosynthesis and photography both involve light sensitive reaction. Chlorophyll, the green
pigment in leaves, absorbs radiation in the visible region of the electromagnetic spectrum and
uses this energy to synthesize chemicals and provide food for the plant.
6CO2

+ 6H2O

C6H12O6 (aq) + 6O2 (g)

H = + 2820 KJ mol-1

White silver chloride decomposes when exposed to sunlight

AgCl (s)

Ag (s) + Cl2 (g)

Reactions of halogens with alkanes:

Cl2
Cl.

Cl.

+ Cl. (radicals)

+ H2

HCl

+ H.

H. + Cl2

HCl

+ Cl.

CH4 + Cl2

CH3Cl + HCl
CH2Cl2 + HCl
CHCl3 + HCl
CCl4 + HCl

Ultraviolet radiation splits Cl2 (g) into free radicals.

Enzymes The Active Site

Lock & Key Theory
Enzymes are specific for substrates. The substrate must fit into the active site of the enzyme. This
fit is referred to as the lock ad key hypothesis. The very precise fit is the reason why enzymes are
so specific:
Salivary amylase to starch (substrate).
Pepsin to protein.
Lipase to fat, etc.
The bonding between enzyme and substrate may involve electrostatic attraction, hydrogen
bonding and van der Waals forces. The bond formed between the enzyme and the substrates
weaken the bond in the substrate which is to be broken and therefore catalyze the reaction.
Catalytic reaction is a surface phenomena.

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Kinetics & Equlibria

Figure 1.9
Substrate +
Enzyme
Products.

Substrate

Enzyme

Enzyme/ Substrate Complex

Starch + Salivary Amylase

Products Enzyme

Maltose + Salivary Amylase

Poisoning of Catalyst
It happens when a substance is absorbed strongly and prevents the catalyst from absorbing the
reactants e.g. lead poisoning in catalytic converters in vehicles, cyanide, carbon monoxide, etc.

Catalyst As A Surface Phenomenon In Industry

Examples
The formation of ethane from ethane and hydrogen, Ni being catalyst:
Ni

C2H4 (g) + H2 (g)

C2H6 (g)

Nickel is a transition element and has empty d orbitals. At particular sites on the surface of a
piece of Nickel, the atoms are arranged in such a way that the cloud of elections (from C 2H4)
can overlap with an empty d orbital.

H
C

..

..

d
Ni

Figure 1.10
Bonding Of Electrons
With Vacant d orbitals
in Nickel. Both Overlaps.

d
Ni

Active Site

d
Ni

The effectiveness of the catalyst is increased if it is powdered. This increases the surface area.
The ethane molecule is held to the surface where it reacts with hydrogen molecule.

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Kinetics & Equlibria

RATES
Rate constant is defined as the proportionality constant between the rate of a reaction and the
concentration of the species that appear in the rate law, raised to the approximate power.
Consider a reaction between x and y
X

+ Y

Products

Reaction Rate [X]m [Y]n = K (X) m (Y) n

The proportionality constant K is called the rate constant:
Reaction Rate
K

=
(X)m (Y)n

The equation is referred to the rate equation or rate expression. The reaction rate is the
instantaneous rate at which the concentration of the product in a reaction is changing divided by
the coefficient of that species in the balanced equation for the reaction.
Factors That Can Make A Reaction Take Place
The reaction must collide (concentration).
The reactions must have the right energy.
Other Factors That Can Change The Rate Are:

Temperature
Concentration
Surface Area
Catalyst.

The Effect Of Concentration On Rate

Change in Concentration, [ ]
Average Rate of Reaction

=
Change in time, t

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Kinetics & Equlibria

0.04
mol / dm-3

Figure 1.10
Graph Of
Concentration
Against Time.

0.0326
0.03
0.0249
0.02

0.01

50

100

150

200 Time (s)

[X]
Average Rate =
t
0.0326 0.0249
=
200 100
= 7.7 * 10-5 mol dm -3 s-1

Order Of A Reaction:
This is the power which the concentration of a species is raised in the rate expression (Law) for a
reaction:
For the hypothetical reaction:
Ax

+ By + Cz

Products

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Kinetics & Equlibria

It is found experimentally that the reaction rate can be expressed:

Reaction Rate = K [X]a [Y]b [Z]c
This is known as the rate equation or the reaction, k being the rate constant. The order of the
reaction with:
Respect to X = a
Respect to Y = b
Respect to Z = c, the overall order is the sum of the powers of the concentration in terms in
the rate equation, i.e. a + b + c.
Experiment show that the rates of most reaction can be related to the concentration of individual
reactants by an equation of the form:
Rate = k [X]n
n takes the value 0, 1, 2, and gives the order of the reaction.
When n = 0, the rate is Zero order with respect to X.
When n = 1, the reaction rate is 1st Order with respect to X.

Figure 1.11
Graph Of Reaction
Rate Against
Concentration.

Reaction Rate

When n = 2, the reaction rate is 2nd Order with respect to X.

2nd Order
1st Order

Zero Order

Concentration Of X
Example
A solution X, of concentration 0.20 mol dm-3 undergoes a first order reaction at an initial rate of
3.0 * 10-4 mol dm-3s-1. Find the rate constant
Solution
Initial Rate = K [X]1

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Kinetics & Equlibria

Initial Rate
[X]

3.0 x 10-4 mol dm-3 s-1

0.20 mol dm-3

1.5 * 10-3 s-1

K=

1.5 * 10-3 s-1 (time-1)

Example
A second order reaction takes place between x and y, which are both initially present at
concentration 0.20 mol dn -3. If the initial rate is 1.6 * 10-4mol dm-3 s-1, what is the rate constant?
Solution
Initial Rate = K [X] [Y]
k

Initial Rate
[X] [Y]

1.6 * 10-4 mol dm-3 s-1llllllllll

0.20 mol dm-3 * 0.20 mol dm-3

4.0 * 10-3 dm3 mol-1 s-1.

4.0 * 10-3 dm-3 mol-1 s-1.

ORDER OF REACTION FROM INITIAL RATE

In a reaction:
n

A +

Products

The rate of reaction = k [A]n [B]m

Where n and m are the orders of the reaction. Two experiments are usually taken at different
concentrations. Two experiments are usually taken at different concentrations for either, one
being held constant. Say [A] is initial concentration of A and Vo the initial rate.
Hence
(Vo) 1

k [A]n1 for run one

(Vo) 2

k [A]n2 for run two

The rations:
n

(Vo) 1

[A]1

Similarly

=
(Vo) 2

[A]2
m

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Kinetics & Equlibria

(Vo) 1

[B]1
=

(Vo) 2

[B]2

Example
Expt
Number
Run

Concentration
[A]
(mol dm-3)

Concentration
[B]
(mol dm-3)

1
2
3
4
5

0.50
0.50
0.50
1.00
2.00

1.0
2.0
3.0
3.0
3.0

Initial
Rate
(mol dm3
)
2.0
8.0
18.0
36.0
72.0

Example
To find the order of reaction with respect to A:
Solution
Compare runs 4 and 5 in which B is constant.
... Rate

[A]n

When [A] is doubled the reaction rate (initial rate) is doubled. The reaction is first order with
respect to A.
n

(Vo) 2

[A2]
=

(Vo) 1

[A1]

72

2.0

=
36

1.0

(2)1

(2) n

1 (First Order)

Example
To find the order of the reaction with respect to B:
Solution
Compare runs 1 and 2 in which [A] is constant.
Rate

[B] m

When [B] is doubled the rate is quadrupled. The reaction is second order with respect to B.

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Kinetics & Equlibria

(Vo) 2

[B]2
=

(Vo) 1

[B]1

8.0

2.0

=
2.0

1.0

(2)m

(2)2

(2)m

2 (Second Order)

Example
The rate equation for the reaction is:
Rate

k [A] [B]2

Order =

1 + 2 = 3 (Third)

Calculate the rate constant. Any one run can be taken, say, run 3.
18

k * 0.50 * (3.0)2

18

0.5 * 9.0

4.0 dm6 mol-2 s-1

Example
Bromine is formed by the reaction between bromate (V) ions and bromide ions and acid.
BrO3- (aq)

+ 5Br (aq) + 6H+ (aq)

3Br2 (aq) + 3H2O (l)

The results of some experiments on the reaction are shown below:

Expt

1
2
3
4

Concentration
(mol dm-3)

Initial Rate / mol

BrO-3
(dm-3 s-1)

BrO3-

Br

H-

0.10
0.10
0.20
0.20

0.10
0.30
0.10
0.10

0.10
0.10
0.10
0.20

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1.2 * 10-3
3.6 * 10-3
2.4 * 10-3
9.6 * 10-3

14

Kinetics & Equlibria

Write the rate law for the reaction, state the overall order of reaction and find the value of the rate
constant.
Solution
Rate
=
k [BrO3-]a [Br ]b [H-]c
To find a, b and c to obtain rate law.
To find the order of BrO3-:
Compare run 1 and 3 [Br ] and [H-] kept constant
Rate

k [BrO3-]a
2.4 * 10-3

0.20
=

1.2 * 10-3

0.10
(2)a

(2)1

1 (First Order)

To find the order of Br :

Compare run 1 and 2. [BrO3-] and [H-] kept constant.
Rate
0.30

=
b

k [Br ] b
3.6 * 10-3

=
1.2 * 10-3

0.10
(3)b

(3)1

1 (First Order)

To find the order of HCompare run 3 and 4. [BrO3] and [Br ] kept constant.
Rate
0.20

k [H-]c

9.6 * 10-3
=
2.4 * 10-3

1.10
(2)c

(2)c

(2)2

2 (Second Order)

... Rate Law

k [BrO3-] [Br ] [H-] 2

Overall order

=
=

1+1+2=4
4th Order

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Kinetics & Equlibria

Rate constant. Take any run, say run 1:

Rate

1.2 * 10-3

k [BrO3-] [Br-] [H-]2

k (0.1) (0.1) (0.1)2

1.2 * 10-3
k

=
1 * 10-4

Rate constant = 12 mol-3 dm9 s-1

Half Life

[ ]/ mol dm-3

All first order reactions have constant half life.

First Order Graph

0.500

t1 = t2

Figure 1.12
First Order Graph
Concentration
Against Time.

t3

0.250
0.125
0.625
t1

t2

t3

Time (s)

The time taken for the concentration to halve is constant. It takes the same time for the
concentration to fall from 0.50 mol dm-3 to 0.25 mol dm-3 as it takes it to fall from 0.25 mol dm-3
to 0.125 mol dm-3. This time is known as the half life.

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Kinetics & Equlibria

[ ] mol dm-3

Second Order Graph

Figure 1.13
Second Order
Graph
Concentration
Against Time.

t 1 < t2 < t 3

t1

t2

t3

Time (s)

The curve for 2nd order dips steeper and will have half life which gets successively larger.

Zero Order Graph

Figure 1.14
Zero Order Graph
Concentration
Against Time.

[]

Time (s)
Zero order with respect to concentration means the rate is unaffected by change in concentration.

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Kinetics & Equlibria

Rate Determining Step

When a reaction takes place in a number of steps, the rate of the reaction is determined by the rate
of the slowest step, i.e. the rate determining step.
The reaction between tert butyl bromide and hydroxide ions to yield tert butyl alcohol follows
first order kinetics, i.e. the rate is dependent on concentration of only one reactant tert butyl
bromide.
Figure 1.15
Rate Determining
Step.

CH3
CH3

CH3
Br + OH-

CH3

CH3

OH + Br -

CH3

Rate = k [RBr]

R = Alkyl Group

Mechanism (1)
CH3
CH3

CH3

CH3
C
(+)

CH3 + Br-

Br

Slow

CH3

CH3

CH3

C
(+)

CH3 + OH-

CH3

CH3

C
OH

CH3
Fast

The rate of the reaction is determined by the slow breaking of the C Br bond to form the
carbocation; once formed the carbocation reacts rapidly to form the product. The slow step does
not involve OH- and its rate does not depend on [OH-].
Mechanism (2)

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Kinetics & Equlibria

Reaction between propanone and iodine:

CH3COCH3 (aq)

+ I2 (aq)

CH3COCH2I (aq) + HI (aq)

Experimental Evidence is that:

Rate = k [CH3COCH3 (aq)]
Step One (1)
OH
CH3

O
CH2

Enol Form

CH3

C
Keto Form
Slow

OH
CH3

CH3

O
CH2 + I2

CH3

CH2I + HI

Fast
The first is that the Keto form of propanone changing into Enol form (tautomers) which are in
equilibrium. Once made, the Enol form reacts rapidly with iodine. Adding more iodine has no
effect on the rate because it cannot increases the rate at which the Enol is formed. However, if the
concentration of propanone is increased, the more Enol is formed and more products made. This
is why the rate depends in the concentration of propanone.

Boltzmann Distribution Curve

The effect of a rise in temperature on a reaction rate is more complicated than simply increasing
the average kinetic energy of the molecules. As the temperature changes the energy of the
molecules has a spread of values. This was investigated by C. Maxwell and L. Boltzmann. They
plotted the fraction of the total number of molecules which have energy x against the value of
molecular energy x. As the temperature rises, the slope of the Maxwell Boltzmann distribution
curve changes, but the area beneath the curve doesnt change and is proportional to the number of
molecules involved.

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Fractions Of Molecules With Energy x

Kinetics & Equlibria

T1

T3 > T2 > T1

Figure 1.16
Fractions of
Molecules with
Energy X

T2
1. Area beneath curves. DO NOT
change
2. Speed (most probably)
C > B > A

T3

M
Ea
ol
ec
ul
ar
Ea
En
er
gy
x

T1 Low temperature, very large fraction have energy close to the average energy.
T2 Wider spread of energies.
T3 High energy, the spread increases further.
The fraction of molecules at T3 in shaded area has energy Ea (Energy of activation). The most
probably speed is the maximum of the graph.

Number Of Molecules With Energy, E

Another View
Figure 1.17
No. of molecules
with Energy E

Boltzmann Distribution

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Kinetics & Equlibria

En
er
gy
,E
From the graph, few molecules reach the highest energy levels. The distribution is said to be the
most probably one. In symbols, the distribution says that if there are N A molecules with Energy
EA, then the number of molecules, NB with energy, EB is given by:
NB

NA exp (- E / kT)

Boltzmann Constant; 1.38 * 10-23 JK-1

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