RATES OF

REACTIONS
Chemistry @ MBCC
Pre-University Arts & Sciences
Science 1

MODULE 2: KINETICS AND

EQUILIBRIA
TOPIC: RATES OF REACTION
1.1 Explain the concepts associated with
reaction rates

Chemical Reactions and Collision Theory

The following conditions MUST be met for a chemical
reaction to occur:
o Particles must collide
o Particles must collide with the correct orientation
o Particles must collide with a certain minimum
amount of energy (activation energy)
When all THREE conditions are met we refer to the
collision as an effective collision

The Collision Theory

Only collisions with enough
energy react to form
products
The energy of the system
changes as the reactants
approach each other
The minimum amount of
energy to make the reaction
proceed is called the
Activation Energy

The Collision Theory

Homework
Read up and make notes on:
Catalysis
Enzymes in industrial and
biological processes
Be able to provide examples

What does rate of reaction mean?

The speed of different chemical reactions varies
The speed of a reaction is called the rate of the reaction.
What is the rate of these reactions?
rusting

baking

explosion

slow

fast

very fast

Rate of a Reaction
is the frequency of effective
collisions we have in a given
time
tell us how fast the reaction is
going
is measured in change in
concentration per unit time for
e.g. mol dm-3 s-1 or M s-1

Progress of the Reaction

Reactions do not proceed at a steady rate
They start off at a certain speed, then get slower and slower until they
stop
There is reduced frequency of collisions between particles and so the
reaction slows down
As the reaction progresses, the concentration of reactants decreases

0%

25%
reactants
product

50%

75%

100%

percentage completion of reaction

Graphing rates of reaction

Reactant - product mixture

hydrogen produced (cm3)

Calculating rate of reaction from graphs

70
60
x

50

rate of reaction = y
x

40
30

20
10
0
0

10

20

30

40

50

time (seconds)
The gradient of the graph is equal to the initial rate of reaction
at that time
rate of reaction = 45 cm3 rate of reaction = 2.25 cm3/s
20 s

Measuring the Rates of Reactions

Experimentally, the rate of a
reaction is the slope (or gradient)
of a concentration vs. time graph
The rate of the reaction may be
measured in one of two ways,
either:
By measuring the rate at which
the product (B) is formed or
By measuring the rate at which
the reactant (A) is used up or
disappears

Measuring the rate of production

Measuring the rate of disappearance

The slope is negative because the reactants are disappearing with

time

Checkpoint
Are you able to do the following?
1. Explain the collision theory
2. Define activation energy
3. Explain what is meant by an effective collision
4. State what is meant by the rate of a reaction
5. Give the units of measurement for the rate of reaction

Calculating Rates of Rxns

Why do the rates differ, if they are measuring the rates at

the same time (between 300s and 400s)?

Calculating Rates of Rxns

MODULE 2: KINETICS AND EQUILIBRIA

TOPIC: RATES OF REACTION
1.2 Design and carry out suitable experiments for
studying the factors which affect rates of reactions

Measuring Rates Experimentally

Measuring the rate of a reaction means measuring the change in the amount
of a reactant or the amount of a product.
What can be measured to calculate the rate of reaction between magnesium
and hydrochloric acid?
magnesium

hydrochloric
magnesium
chloride
acid

hydrogen

The amount of hydrochloric acid used up (cm3/min)

The amount of magnesium chloride produced (g/min)
The amount of hydrogen product (cm3/min)

1. Measuring the rate of gas production

Mg(s) + HCl(aq) MgCl2(aq) + H2(g)
glass tube

conical
flask

rubber connecter

rubber bung
hydrochloric
acid
magnesium

gas syringe

2. The Titration Method

Eg.
Acid catalysed hydrolysis of an ester (ethyl acetate)
samples are removed from reaction vessel at regular intervals
the reaction is stopped or quenched (snapshot)
Q. How would you quench the reaction?
mixture analysed by titration concentration of ethanoic acid is
determined by titration
Q. What do you expect to observe as the concentration of acid is
measured over time? Explain your answer

3. Colourimetric Method
The time taken for the colour of the solution to appear or disappear is
measured

samples are removed from reaction vessel at regular intervals

What is the colour of aqueous iodine?
What do you expect to observe in the reaction vessel as the reaction
proceeds
mixture may also be analysed by titration concentration of remaining
aqueous iodine is determined by titration instead of using a
spectrophotometer

MODULE 2: KINETICS AND EQUILIBRIA

TOPIC: RATES OF REACTION
1.3 Construct rate equations of the form: rate = k [a] n[b]m limited
to simple cases involving zero, first and second order reactions

Rate Equation (or Rate Law)

We can write an expression or an equation to show the relationship between the
concentration of the reactants and the initial rate of reaction
For a general reaction A + B product we can write the general rate equation
as:

R=k[A]m[B]n
Where:

R = initial rate in mol dm-3 s-1

[A] = concentration of reactant A in mol dm-3 or M
[B] = concentration of reactant B in mol dm-3 or M

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

Order of a reaction w.r.t a reactant

shows the relationship between the concentrations of the
reactant species and the rate of a reaction
is the exponent to which the concentration of that species
is raised
indicates to what extent the rate of a reaction is affected
by the concentration of a particular reactant
must be determined experimentally
may be zero order, first order and second order

Order of a reaction
Zero order
implies that the rate of reaction is not affected by concentration
the rate does NOT change even if the concentration increases or decreases
First order
implies that the rate of reaction changes proportionally with the change in
concentration
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
if the concentration doubles, the rate quadruples; if the concentration triples, the
rate increases nine fold etc.

Overall first order reactions

A products

Rate = k[A]

Overall second order reactions

A + A products Rate = k[A]2
A+B products Rate = k[A][B]
Overall third order reactions
A+B+C products Rate = k[A][B][C]
A+B products
A products

Rate = k[A]2[B] or Rate = k[A][B]2

Rate = k[A]3

MODULE 2: KINETICS AND EQUILIBRIA

TOPIC: RATES OF REACTION
1.4 Deduce the order of reaction from appropriate
data

Determining the Order of a Reaction

For a given reaction where the rate law is given as:

R=k[A]m[B]n
m and n must be determined experimentally
Perform multiple trials all at the same temperature (k is affected by
temperature)
Vary only the concentration of the reactant you are investigating
(conc. of the other reactants are held constant)
Any change in the rate of reaction is due to the reactant that was
varied

Can you determine the order with respect to NO?

Rate Constant
The rate constant, k, is a proportionality constant for a given
reaction
It is dependent on temperature
The units for k depend on the order of the reaction
What are the units of k for:
A first order reaction?
A second order reaction?
A third order reaction?

Question
The initial rate of reaction between an ester A and aqueous sodium hydroxide was
measured in a series of experiments at a constant temperature. The data obtained are
shown below.
Experiment
1
2
3
4

Initial [NaOH]
(mol dm3)
0.040
0.040
0.060
0.120

Initial [A]
(mol dm3)
0.030
0.045
0.045
0.060

Initial rate
(mol dm3 s1)
4.0 104
6.0 104
9.0 104
to be calculated

a) Use the data in the table to deduce the order of reaction with respect to the ester A
b) Deduce the order of reaction with respect to NaOH
c) Deduce the value of k with the correct units
d) Hence calculate the initial rate of reaction in Experiment 4

MODULE 2: KINETICS AND EQUILIBRIA

TOPIC: RATES OF REACTION
1.5 Interpret concentration against time and concentration
against rate for zero and first order reactions

Concentration-time Graphs
We can deduce order of a reaction from concentration vs. time plots

Rate-concentration Graphs
We can deduce the order of a reaction from rate vs. concentration
plots

MODULE 2: KINETICS AND EQUILIBRIA

TOPIC: RATES OF REACTION

1.6 Perform calculations from rate data

Past Paper Question

The values of initial rates measured for the reaction below are recorded in the table
below:
Experiment

[S2O82-]

[I-]

Initial Rate Ms-1

0.15

0.25

1.4 x 10-5

0.15

0.5

5.6 x 10-5

0.075

0.5

2.8 x 10-5

0.075

0.25

7.0 x 10-6

a) Use the information from the table to deduce the rate equation and calculate the
overall order of the reaction [5 marks]
b) Calculate the:
i. Rate constant [2 mark]
ii. Initial rate when the concentration of both reagents are 0.12 M [1 mark]

Past Paper Question

Determine the rate law for the reaction between A2 and B2

MODULE 2: KINETICS AND EQUILIBRIA

TOPIC: RATES OF REACTION
1.7 Perform simple calculations using half-life data

Half Life
The time taken for the
concentration of a reactant to
reduce to half its value
First order reactions have
CONSTANT half lives eg.
decay of radioisotopes such as
carbon-14

What is the half life for the reaction below?

Determining Half Lives for 1st Order Reactions

For first order reactions:

REACTION
MECHANISMS

Reaction Mechanisms
Some reactions are too complicated to happen in one simple stage
Instead, the reaction may involve a series of small changes one after the
other
e.g. Overall reaction:

A2 + B2 C
may consist of several steps:
A2 A + A

(step 1)

B2 B+ B

(step 2)

2A + 2B C

(step 3)

Reaction Mechanisms
A reaction mechanism is the step by step sequence of elementary reactions
by which an overall chemical change occurs
An elementary reaction is the simplest step of the reaction mechanism and
may be classified by its molecularity:
The number of reactant particles involved in an elementary step is called
the molecularity
1. Unimolecular involves only one reactant
2. Bimolecular involves collision of two reactant molecules
3. Termolecular involves collision of three reactant molecules (rare)

Elementary Reactions

Unimolecular

Termolecular
Bimolecular

http://chemwiki.ucdavis.edu/Core/Physical_Chemistry/Kinetics/Rate_Laws/Reaction_Mechanisms/Elementary_Reactions

Reaction Mechanisms
One of the steps in the reaction sequence is the slowest step, known
as the rate determining step (rds)
The molecularity of a process tells how many molecules are
involved in the process
The rate law for an elementary step is written directly from that step

Multistep Mechanisms
In a multistep process, one of the steps will be slower than all others.
The overall reaction cannot occur faster than this slowest, ratedetermining step.
The rate of the overall reaction depends upon the rate of the slow
step

 The rate law for this reaction above is found experimentally to

be

Rate = k [NO2]2
CO is necessary for this reaction to occur, but notice that the
rate of the reaction does not depend on [CO] (i.e. [CO] does not
appear in the rate law
This suggests the reaction occurs in two steps

Rate Determining Step

A proposed mechanism for this reaction is

The NO3 intermediate is consumed in the second step

Since CO is not involved in the slow, rate-determining step,
it does not appear in the rate law

Rate Determining Step (RDS)

The rate of the RDS (or slow step) determines the overall
rate of the reaction
The rate law (or rate equation) is written from the RDS
The order for the RDS is the order of the overall reaction

Example
Consider the following reaction
2 NO2 + F2 2 NO2F
If the reaction follows the mechanism:
NO2 + F2 = NO2F + F (slow)
NO2 + F = NO2F (fast)
i. Which step is the RDS?
ii. Write an expression for the rate law
iii. What is the molecularity of the RDS?
iv. What is the overall order of the reaction?
http://www.science.uwaterloo.ca/~cchieh/cact/c123/elmntary.html

MODULE 2: KINETICS AND EQUILIBRIA

TOPIC: RATES OF REACTION
1.8 Explain the effect of temperature and catalysts on the rate of the
reaction using boltzmann distribution of energies (and of collision
frequency)

FACTORS AFFECTING
REACTION RATES
Concentration and Pressure
Temperature
Surface Area
Catalysts

Concentration of Reactants
Concentration is the number
of particles in a given volume
As the concentration of
reactants increases, so does
the probability that reactant
molecules will collide
More effective collisions
means increased rate of
reaction
Increasing the concentration,
increases the rate of reaction

Pressure
Increasing the pressure of a gas has
the same effect as increasing its
concentration
Increasing the pressure on a reaction
involving gases increases the rate of
reaction
Changing the pressure on a reaction
which involves only solids or liquids
has no effect on the rate
Increasing the pressure, increases
the rate of reaction

Surface Area
Surface area is the exposed
matter of a solid substance
By increasing surface area,
there are more collisions
per unit of time
Therefore, as the surface
area increases, so does the
rate of reaction
Mg(s) + 2 HCl(aq) MgCl2(aq) + H2(g)

MaxwellBoltzmann Distributions
(Effect of Temperature on Rate)
Temperature is defined as a measure
of the average kinetic energy of the
molecules in a sample
At any temperature there is a wide
distribution of kinetic energies
At higher temperatures, reactant
molecules have more kinetic
energy, move faster, and collide
more often and with greater energy

MaxwellBoltzmann Distributions
(Effect of Temperature on Rate)

Increasing the
temperature,
increases the rate of
reaction

As the temperature increases, the

curve flattens and broadens
Thus at higher temperatures, a
larger population of molecules has
higher energy
If the dotted line represents the
activation energy, as the
temperature increases, the fraction
of molecules that can overcome the
activation energy barrier also
increases (area under the curve)

MaxwellBoltzmann Distributions
(Effect of Catalyst on Rate)

Energy-Profile Diagram
(Effect of Catalyst on Rate)

A catalyst speeds up a reaction

by finding an alternate reaction
pathway or mechanism which
has a lower activation energy
Using a catalyst increases the
rate of reaction