CHEM0020 - Chemistry II

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4.0 CHEMICAL KINETIC

4.1 Introduction

Chemical kinetics is a quantitative research on rate of reaction and the

mechanism.

The kinetic researches are important as it helps us to get the optimum products at
an optimum stage and to know how rapidly chemical reactions occur.

From our everyday experience, some reactions are fast while others are slow.
Why do we find such differences? What are the factors that influence this
reaction?

In this chapter we will learn how to determine the rate of reactions and several
factors that disturbs the rate of reaction.

4.2 Rate of reactions

Rate of reaction is the speed of a reaction that occurs in a given interval time.

Let’s consider a simple reaction: A B. The rate of reaction can be written

in terms of disappearance of substance used and appearances of products.

In the equation above, A is the substance used and B is the substance produced.

The rate of disappearance: Rate = - d [A]

dt
* negative sign shows the disappearance.

The rate of appearance: Rate = + d [B]

dt
* positive sign shows the appearance.

In a reaction the rate of disappearance and the rate of appearance are the same.

Rate = - d [A] = +d [B]

dt dt

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In general, for reaction aA + bB cC + dD, the rate is given by

Rate = - 1 d[A] = - 1 d[B] =+1 d[C] = + 1 d[D]

a dt b dt c dt d dt

Example: 2HI H2 + I2

Rate = - 1 d[HI] = + d[H2] = + d[I2]

2 dt dt dt

Example 1:
The decomposition of dinitrogen pentoxide is as follows

2N2O5 (g) 4NO2 (g) + O2 (g)

a) Write the rate of disappearance of dinitrogen pentoxide.

b) If the rate of appearance of O2 is 0.5 x 102 mol dm-3 s-1, what is the rate of
disappearance of N2O5?

Answer:

a) R = -1 d[N2O5]
2 dt

b) R = +d[O2] = - 1 d[N2O5]
dt 2 dt

0.5 x 102 = - 1 d[N2O5]

2 dt

2 x 0.5 x 102 = -d[N2O5]

dt

d[N2O5] = -1.0 x 102 mol dm-3 s-1

dt

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4.3 The Rate law

At a constant temperature and pressure, the rate of reaction is proportional to the

concentration of reactant.

Rate [reactant].

In a reaction: aA + bB products, the rate = k [A]x[B]y, where x and y is the

power of the reactants concentration and k is the rate constant.

The x, y and k values must be determined experimentally. Then the rate of

reaction, rate = k [A]x[B]y.

Example 2:
The reaction of nitric oxide with hydrogen at 1280oC is

2NO (g) + 2H2 (g) N2 (g) + 2H2O (g)

From the following data collected at this temperature, determine the rate law and
calculate the rate constant.

Experiment [NO] [H2] Initial rate (M/s)

1 5.0 x 10-3 2.0 x 10-3 1.3 x 10-5
2 10.0 x 10-3 2.0 x 10-3 5.0 x 10-5
3 10.0 x 10-3 4.0 x 10-3 10.0 x 10-5

Answer:
We assume that the rate law is, rate = k [NO]x[H2]y
Compare the data for rate of reaction in experiment 1 and experiment 2.

Rate2 = k[10 x 10-3]x[2 x 10-3]y

Rate1 k[5 x 10-3]x[2 x 10-3]y

5.0 x 10-5 = [10.0 x 10-3]x

-3 x
1.3 x 10-5 [ 5.0 x 10 ]

3.8 = 2x
4 = 2x
22 = 2x
x = 2

OR log 3.8 = x log 2

x = log 3.8 / log 2 = 1.93 2 3
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Compare the data for rate of reaction in experiment 3 and experiment 2.

Rate3 = k[10 x 10-3]x[4 x 10-3]y

Rate2 k[10 x 10-3]x[2 x 10-3]y

10.0 x 10-5 = [4 x 10-3]y

5.0 x 10-5 [2 x 10-3]y

2 = 2y
21 = 2y
y = 1

OR log 2 = y log 2
y = log 2 / log 2 = 1

The rate law is given by; Rate = k [NO]2[H2]1.

The rate constant k can be calculated using the data from any one of the experiments.
Since
k = rate , data from experiment 2 gives us
2
[NO] [H2]

k = 5.0 x 10-5 Ms-1 = 2.5 x 102 M-2 s-1

(10 x 10-3 M)2 (2 x 10-3 M)

Exercise: The reaction of peroxydisulfate ion, S2O82- with iodide ion, I- is

S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)

Determine the rate of law and the rate constant. The data collected are as below.

Experiment [S2O82-] [I-] Initial rate (M/s)

1 0.080 0.034 2.2 x 10-4
2 0.080 0.017 1.1 x 10-4
3 0.160 0.017 2.2 x 10-4

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4.4 First-order reaction

A first-order reaction is a reaction where the total sum for the power of reactants
comes up to one.

In a first-order reaction of the type A product, the rate is

Rate = - d[A]
dt

From the rate law, we also know that

rate = k[A]

To obtain the units of k for this rate of law, we write

k = rate = M/s = 1/s or s-1

[A] M

Combining the first two rate law equations, we get

-d[A] = k[A]
dt

Using integration, we can show from the above rate law equations that

ln [A] = -kt
[Ao]

ln [A] - ln [Ao] = -kt

The equation can be rearranged as follows:

ln [A] = -kt + ln [Ao]

This equation has the form of the linear equation y = mx + c, in which m is the slope
of the line that is graph of the equation:

ln [A] = -kt + ln [Ao] .

y = mx + c

in the log form: log [A] = -kt/2.303 + log [Ao] .

y = mx + c
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Thus the plot of ln [A] versus t (or y versus x) gives a straight line with a slope of
–k (or m). This graphical analysis allows us to calculate the rate constant k. Figure
4.1 shows the characteristics of a first-order reaction.

[A] ln [A]

t t
(a) (b)

Figure 4.1: First-order reaction characteristic:

(a) Decrease of reactant concentration with time;
(b) Plot of the straight-line relationship to obtain the rate
constant. The slope of the line is equal to –k.

Example 3: the conversion of cyclopropane to propene in the gas phase is a first-order

reaction with a rate constant of 6.7 x 10-4 s-1 at 500oC.

CH 2
CH3 CH=CH2
CH2 CH 2

a) if the initial concentration of cyclopropane was 0.25 M, what is the concentration

after 8.8 min?
b) How long will it take for the concentration of cyclopropane to decrease from 0.25 M
to 0.15 M?

Answer:

a) ln [A] = -kt
[Ao]

ln [A] = -kt + ln [Ao]

= -(6.7 x 10-4 s-1) (8.8 min x 60s) + ln [0.25]

= -1.74

[A] = 0.176 M 6
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b) Using the same formula again,

ln [0.15] = -(6.7 x 10-4 s-1) t + ln [0.25]

t = ln [0.15] - ln [0.25]
-(6.7 x 10-4 s-1)

t = 762 s = 12.7 min.

Determine graphically the order and rate constant.

Decomposition of nitrogen pentoxide in carbon tetrachloride (CCl4) solvent at

45oC.

2N2O5 (CCl4) 4NO2 (g) + O2 (g)

The following table shows the variation of N2O5 concentration with time and the
corresponding ln [N2O5] values.

t (s) [N2O5] ln [N2O5]

0 0.91 -0.094
300 0.75 -0.29
600 0.64 -0.45
1200 0.44 -0.82
3000 0.16 -1.83

Plot ln [N2O5] versus t, a straight line obtained shows that the rate law is first
order. Next the rate constant is calculated from the slope.

Slope (m) = -1.50 – (-0.34)

(2430 – 400) s
= -5.7 x 10-4 s-1

Since m = -k, thus k = 5.7 x 10-4 s-1.

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Plot of ln [N2O5]

t(s)
-500 500 1500 2500 3500
0 -0.094
-0.29
-0.45
ln [N2O5]
-0.5
-0.82
-1
-1.5
-1.83
-2

Figure 4.2 Plot of ln [N2O5] versus time

For gas-phase reactions, replace the concentration terms with the pressure of the
gaseous reactant.

Using the ideal gas equation, we write

PV = nRT

Where, n = [A] = P
V RT

Substituting [A] = P/RT, in

ln [A] = -kt
[Ao]

we get,
ln P/RT = -kt
Po/RT

ln P = -kt
Po

ln P - ln Po = -kt

The equation can be rearranged as follows:

ln P = -kt + ln Po
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4.5 Second-order reaction

A second-order reaction is a reaction with total sum of power equals to two.

In a second-order reaction of the type A product, the rate is

Rate = - d[A]
dt

From the rate law, we also know that

Rate = k[A]2

To obtain the units of k for this rate of law, we write

k = rate = M/s = 1/M.s or M-1s-1

[A]2 M2

Combining the first two rate law equations, we get

-d[A] = k[A]2
dt

Using integration, we can show from the above rate law equations, that

1 - 1 = -kt
[Ao] [A]

1 = 1 + kt
[A] [Ao]

The equation can be rearranged as follows:

1/[A] = kt + 1/[Ao]

This equation has the form of the linear equation y = mx + c, in which m is the
slope of the line that is graph of the equation:

1/[A] = kt + 1/[Ao] .
y = mx + c

Thus the plot of 1/[A] versus t (or y versus x) gives a straight line with a slope of
k (or m). This graphical analysis allows us to calculate the rate constant k.
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Example 4:
Iodine atoms combine to form molecular iodine in the gas phase.

I (g) + I (g) I2 (g)

The reaction follows second order kinetics and has the rate constant 7.0 x 109 M-1s-1 at
23oC. If the initial concentration of I was 0.086 M, calculate the concentration after 2
min.

Answer:
1 = 1 + kt
[A] [Ao]

1 = 1 + (7 x 109 M-1s-1) (2 min x 60 s)

[A] 0.086M

[A] = 1.2 x 10-12 M

4.6 Factors that affect the rate of reaction

The rate of reaction depends on concentration, temperature, pressure, catalyst and

size of molecules.

4.6.1 Concentration

- When the concentration of reactant is added, the numbers of particles in the same
volume will increases.
- With the increasing of the particles, the collision between the particles will
increase giving a high rate of reaction.

4.6.2 Temperature

- An addition of 10oC increases the rate 2 times higher.

- At high temperatures, particles have more energy to move around and collide
with another particle.
- This also gives frequent collision between the particles that leads to high rate of
reaction.

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4.6.3 Pressure

- At high pressure, gaseous molecules are pushed closer.

- This will give more chances for the particles to collide among themselves.
- Frequent collision make the reaction occur faster, thus increasing the rate of
reaction.

4.6.4 Size of molecules

- Reactants with small size molecules (broad surface area) increase the rate of
reaction.
- For instance, powder zinc dissolves faster than the thick piece of zinc metal.

4.6.5 Catalyst

- A catalyst is a substance that increases the rate of a reaction without itself

being consumed.
- The catalyst is generally referred to substances that give a positive effect such as
an increase in the rate of reaction.
- It can’t be denied that there are some catalysts that can slow down a reaction.
- The effect of a catalyst is called catalysis.
- Catalyst provides an alternative route for a reaction with lower activation energy.
- Figure 4.3 shows the energy profile of catalyzed and uncatalyzed reactions.

The energy levels of reactants and products remain the same in catalyzed and
uncatalyzed reactions.

From this, we can conclude that the catalyst didn’t provide extra energy for
reactants, meanwhile there is an increase in the reaction rate.

In this case, catalyst functions only to lower down the activation of the reaction.

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E = Activation energy for the

uncatalyzed reaction

E’ = Activation energy for

the catalyzed reaction

H = Heat energy

Figure 4.3 Energy profiles of catalyzed and uncatalyzed reactions.

4.6.5.1 Types of catalyst

Catalyst can be grouped into two; heterogeneous catalyst and homogenous

catalyst.

Heterogeneous catalyst; the reactants and catalyst are in different phases.

Usually the catalyst is a solid and the reactants are either gases or liquids.

Example, the formation of NH3 from N2 and H2 uses iron, Fe as catalyst.

N2 (g) + 3H2 (g) 2NH3 (g)

Fe

Homogenous catalyst; the reactants and catalyst are dispersed in a single phase,
usually liquid.

Acid and base catalyses are the most important types of homogenous catalysis in
liquid solution.

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For example, the reaction of ethyl acetate with water to form acetic acid and
ethanol normally occurs too slowly to be measured.

However an acid (liquid) can catalyze the reaction. In the presence of

hydrochloric acid, the rate is faster.

CH3COOC2H5 (l) + 3H2O (l) CH3COOH (l) + C2H5OH (l)

HCl

4.6.5.2 Characteristic of catalyst

Catalyst does not change the equilibrium of a reaction, it only helps the reaction
to reach equilibrium faster.
Catalyst quickens the process by reducing the activation energy in the reactants.
Catalyst does not change chemically. However it might change physically.
A small amount of catalyst is sufficient to increase the rate.
Catalyst can be used repeatedly.
Catalysts are specific to the reaction. We need different catalyst according to the
reaction we need to conduct.

4.7 The Collision Theory

For a reaction between two particles to occur, an effective collision must take
place, meaning a collision that result in formation of product molecules.

The reaction rate is a measure of how frequently effective collision occurs.

There are many particles present in a container with the same volume. These
particles are more likely to collide.

However not all the collision results in reactions. The greater the number of
collisions, the higher the chance that some of them will be effective.

Addition to this we also have to consider the molecular orientation and molecular
kinetic energy.

4.7.1 Molecular orientation

When two reactants collide, their atoms must be correctly orientated for a reaction
to occur. Wrong orientation will cause the particles to bounce off each other.
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Example:

NO (g) + O3 (g) NO2 (g) + O2 (g)

a) b)
O O
N O O O N O
O O

O O

N O O O N O

O O

O
O O N O
N O
O O
O

Figure 4.4 The importance of molecular orientation

during collision. The collision shown in (a) will not
produce a reaction but that shown in (b) results in the
formation of NO2 and O2.

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4.7.2 Molecular kinetic energy

Even when the orientation of molecules is correct, few collisions do actually lead
to chemical change.

This is because in order to react, the molecules must collide with certain
minimum kinetic energy known as the activation energy.

If two slow-moving molecules collide, even if they are in the right orientation,
they will simply bounce apart as a result of the repulsion of their negative electron
clouds.

To meet with sufficient energy for bonds to be broken and reformed, the
molecules must be moving quickly.

An increase in temperature will increase the kinetic energy of the molecules and
so increase the rate of reaction, as greater portion of the molecules will have
sufficient energy to react.

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