Unit 1 Mod 2 Rates of Reaction page 1 of

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RATES OF REACTION

Change in the product or reactants with respect to time

Collision theory

1. For a reaction to occur, particles MUST collide

2. Particles must collide with at least a certain minimum amount of
energy (activation energy)
3. Particles must collide with the correct orientation

All three conditions can be collectively called EFFECTIVE

COLLISIONS

Factors that affect the rate of a reaction:

● Temperature/ light
● Surface Area
● Concentration/ Pressure
● Presence of a Catalyst

Rate of reactions are generally measured in mol dm -3 s-1

Rate equation
A rate equation shows the effect of concentration of the reactants to the
initial rate of reaction.

For a general reaction A + B 🡪 product

general rate equation 🡺 initial rate =k[A]m[B]n

initial rate = rate of reaction at the beginning of the reaction

k = rate constant
m = order of reaction with respect to reactant A
n = order of reaction with respect to reactant B
total order of reaction = m + n

Orders of reaction (shows how the initial rate is affected by any one
particular reactant)
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Zero order implies that the rate of reaction is not affected by concentration. i.e.
the rate does NOT change even if the concentration increases or decreases.
First order implies that the rate of reaction increases proportionally with the
change in concentration. e.g. if concentration of a reactant doubles, the rate
ALSO DOUBLES, if the concentration triples, the rate ALSO TRIPLES etc
Second order implies that the rate of reaction increases with the SQUARE of
the change in concentration i.e. if the concentration doubles, the rate
QUADRUPLES, if the concentration triples, the rate increase NINE FOLD.

You also need to know both zero AND first order reactions using
concentration vs time graphs.

Lk,+-Sample calculation on determining orders of reaction, the value and

units of the rate constant and the initial rate of a reaction
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The following results were obtained for a reaction between A and B
Expt # Concentration /mol dm-3 Initial rate /
mol dm-3 s-1
[A] [B]
1 0.5 1 2
2 0.5 2 8
3 0.5 3 18
4 1 3 36
5 2 3 72
6 2 4 ?

a) To find the order of reaction with respect to B, you would

Compare expt # 1 and 2 as [A] is constant and [B] varies

Method 1

Order of Reaction = Initial Rate 2

Initial Rate1
n
Conc. B at Rate 2 = Initial Rate 2
Conc. B at Rate 1 Initial Rate1

2 n
=8
1 2

2n = 4
n = log 4
log 2
n=2

Method 2

As [B] doubles, the initial rate increases 4 fold, therefore rate increase
with the SQUARE of the change in concentration i.e. 2nd order therefore
n=2

b) To find the order of reaction with respect to A, you would

Compare expt # 4 and 5, [B] is constant and [A] varies

Method 1
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Order of Reaction = Initial Rate 5
Initial Rate 4
m
Conc. A at Rate 5 = Initial Rate 5
Conc. A at Rate 4 Initial Rate 4

2 m
= 72
1 36

2m = 2

m = log 2
log 2
m=1

Method 2

As [A] doubles, initial rate doubles, therefore it is a proportional change,

which means 1st order i.e. m = 1

Therefore: Total/ Overall order of reaction = 2 + 1 = 3

c) Calculation of rate constant k

You can use ANY expt # from 1 to 5 e.g. expt #3

Specific rate equation: Initial rate = k [A] 1[B]2

For expt #3 🡺 18 = k [0.5]1[3]2

18 =k=4
0.5 x 9

d) Calculate the units for the rate constant

mol /dm3 or mol dm-3

mol1 x mol1 = mol2

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dm-3 x dm-3 = dm-6

To determine the units of k 🡺 mol dm-3 s-1 = k x mol dm-3 x (mol dm-3)2

mol dm-3 s-1 = k x mol dm-3 x mol2x dm-6

mol dm-3 s-1 = k x mol3 dm-9

mol dm-3 s-1 = k

mol3 dm-9

Therefore units of k = mol-2 dm6 s-1

Standard way = dm6 mol-2 s-1

e) Determination of the rate for experiment #6

R =4 [ 2]1[4]2
R = 128 moldm-3s-1

Checkpoint A

a) What is the order of reaction with respect to:-

i) A2 [1] ii) B2 [1]

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iii) The overall order of the reaction [1]

…………………………………….

b) Write the rate equation for the reaction [1]

…………………………………………………….

c) Calculate the value of the rate constant and its units [2]

d) If an experiment was conducted with the [A] as 0.4 and the [B] as 0.3,
calculate the initial rate of the reaction. [1]

……………………………………………………………

Rate determining step and reaction mechanism

All chemical reactions occur as a series of small steps from beginning to

end. Reaction mechanisms can only be determined experimentally.
All mechanisms have a rate determining step which is the slowest step
in the reaction. Rate determining steps (RDS) would have an order of
either 1 or 2. The FAST step in any reaction mechanism would have an
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order of zero.

Example Calculate the orders of reaction with respect to A and B,

determine the rate equation and propose a mechanism consistent with
the kinetics.

order wrt A = 1 order wrt B = 0

rate equation 🡺 initial rate = k[A][B]0 🡺 initial rate = k[A]
proposed mechanism
A2 🡪 2A (slow) 2A + B2 🡪 2AB (fast)

CHECKPOINT B

a) Use the data on the left to determine the order of reaction with respect
to i) S2O82- and ii ) I-
b) The total order of reaction
c) the rate equation for the reaction

Half-life
The time taken for a reaction to go to half completion, it is called the
half-life. First order reactions have CONSTANT half lives.
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equation (1) kt = ln (A0 / A) The decay of
equation (2) kt1/2 = 0.693 radioactive isotopes is
a first order reaction
k = rate constant
t = time
A0 = initial concentration or original percentage (usually 100%)
A = current concentration or current percentage
t1/2 = time of half life

Sample calculation of half life

The half life of radium is 1590 years. How long will it take for a sample
of radium to decay to 10% of its original radioactivity?

This means t1/2 = 1590

First using equation (2)
kt1/2 = 0.693 🡺 k x 1590 = 0.693 🡺 k = 4.36 x 10-4 year-1
Then using equation (1)
4.36 x 10-4 x t = ln (100/10) 🡺 t = 5280 years

Checkpoint C

1. Calculate the percentage of radioactivity remaining after 280 years if

its half-life is 28 years (will show this one in class)

2. A sample decays by 50% in 45 minutes. What is the half life of the

sample?

3. An isotope of caesium has a half -life of 30 years).  If 4.2 mg of

cesium-137 disintegrates over a period of 90 years, how many mg of
cesium-137 would remain?

Effect of temperature and catalysts on rate of reaction

Maxwell-Boltzman distribution curve

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The effect on temperature

The effect of a catalyst

Very few molecules have a very

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