Kinetics L1

Topic 11 - Kinetics
• What makes “superglue” bond instantly

while Elmer’s glue does not?
• What factors determine how quickly food
spoils?
• Why do “glow sticks” last longer when
stored in the freezer?
• How do catalytic converters remove various
pollutants from car exhaust?
DNA:
Why do chemists study reaction rates

(kinetics)???
 Intriguing
 Industry
 Reaction mechanism
DNA:
Define each of the chemical terms on your worksheet and stick into your
exercise book. Write in pencil if you are not sure.
Rate of reaction Half-life

Rate equation Rate-determining
Order with respect to a Activation energy
substance
Overall order Heterogeneous and homogeneous catalyst
Rate constant
Term Definition
Rate of reaction
Rate equation
Order with respect to a substance
Overall order
Rate equation
Half-life
Rate-determining
Activation energy
Heterogeneous and homogeneous

catalyst
Rate of a Reaction
The rate of a reaction is the speed at which the amount of
reactants decreases or the amount of products increases
change in concentration, volume or mass

rate of reaction =
time
There are two ways to measure the rate of a reaction:
 Measure the rate at which a reactant is used up
 Measure the rate at which a product is formed

The collision Factors affecting
theory of rate of reaction
reactivity
 Particles have to collide with a  Temperature

minimum amount of energy, called
 Concentration/pressure
the activation energy.
 The collisions with energy greater  Surface area
or equal to the activation energy are  catalyst

called successful collisions.
Rate of a Reaction
The rate of a chemical reaction varies throughout a reaction:
 starts high and then decreases
 when all the reactants have been used up, the rate has
dropped to zero
A?
B?
If g
giv as
en
of f
Measuring Rates of Reactions
Inverted measuring cylinder Gas syringe

If g
giv as
Measuring Rates of Reactions en
of f
Before
reaction
Gas escapes through the

cotton wool
During
reaction
Alows gas to escape, but
avoids splashes
No useful if the gas released is

sulphur dioxide as it will
dissolve in the solution.
If
the
re
in is a c
col
Measuring Rates of Reactions ou hang
r e
 Colorimetr
y
colorimeter
 Titrimetric analysis
• Small portions (aliquots) removed

from reaction mixture at regular
intervals
• Reagent added to quench (stop) the

reaction (alternatively, an ice bath is
used)
• The quenched aliquots are titrated to

find concentration
 Conductimetric analysis
• The number and type of ions in a
solution affect its electrical
conductivity.
• As a reaction takes place in solution,

the ionic balance changes and the
resulting change in conductivity can
be used to measure the rate of the
reaction
About last
lesson…

To measure the rate of reaction we need to work out how much reactant has been
used up or how much product has been produced.
Example of reaction Means of following the reaction

1.
CaCO3 + 2HCl  CaCl2 + H2O + measure volume of gas evolved over time

2.
CO2

measure change in mass over time

3.
CH3CO2C2H5 + H2O  CH3COOH + measure concentration of acid by

C2H5OH sampling at set time intervals and

4. titration
CH3COCH3 + I2  CH3COCH2I + HI measure

change in colour over time with a

5. colorimeter
2KI + H2O2 + 2H  I2 + 2H2O
+
use iodine clock technique or use
colorimeter
Rate equation, rate constant and order of reaction
A+B C+D
order of reaction
with respect to A
rate = k [A]m
[B]n order of reaction
rate of reaction rate constant with respect to B
(at a particular temperature)
NB the orders of reaction are determined by

experiment
Think…
• [] stands for concentration of species
high
• a fast reaction has a _______________ value of k
low
• a slow reaction has a _______________ value of k
Orders of reaction
Order Example Effect on rate Proportionality of rate to
concentration
rate = k Stays the same Not proportional to concentration
zero
([A]0 = 1, does
appear in the rate
equation)
Doubles Proportional to concentration
first rate = k [A]1
second rate = [A]2 Increases by 4x Proportional to square of concentration
The order of a reaction with respect to a chemical is found

from experimental data
(you cannot work it out from the stoichiometric equation)
Overall order of reaction
Add up the individual orders e.g. m+n
zero
m+n = 0 we describe the reaction as _________________ order.
first
second order.
m+n = 2 we describe the reaction as _________________
third
Units & the rate constant
change in
mol dm-3
rate of reaction =
concentration
time
s
Units of rate of reaction are mol dm-3 s-1
The unit for the rate constant changes

according to the rate equation
according to the rate equetion
 Units of k – zero order
rate = k [A]0 k= rate

N.B.
[A]0 =1
Unit of k mol dm-3 s-1

 Units of k – first order
rate mol dm-3 s-1

rate = k [A] 1
k=
[A] mol dm-3
So k has the units of rate s-1

 Units of k – second order
rate mol dm-3 s-1

rate = k [A] 2
k=
[A]2] mol2 dm-6
So k has the units of rate mol-1 dm3 s-1

Units & the rate constant extension

 Units of k – third order

Practice time 
1. Rate = k [N2][H2] 2nd order; mol-1 dm3 s-1
1st order; s-1

2. Rate = k [CH3COOH]
0 order; mol dm-3 s-1

3. Rate = k [CH3CH3]0
4. Rate = k [C2H4][Cl2]2 3rd order - mol-2 dm6 s-1

Rate constant & temperature
A+B C+ D
RATE = k [A]m [B]n
 Orders of reaction do not change with temperature.
 Rate constant changes with temperature. Increasing the

temperature increases the rate of reaction. If concentrations are
kept constant as rate increases k must also increase.
Similarly as catalyst increase rate, k must increase as

well
Experiments that can be used to investigate reaction rates
I) Initial-rate method
(consists of carrying out separate experiments where different
initial concentrations of one reagent are used) (`clock reaction´)
II) Continuous monitoring method

(consists of generating data to enable concentration-time or
volume-time graphs to be plotted)
Experiments that can be used to investigate reaction rates
I) Initial-rate method
(consists of carrying out separate experiments where different
initial concentrations of one reagent are used) (`clock reaction
´)
For NO2 using the second and third sets of data…
• The concentration of NO2 increases from 0.050 mol dm-3 to 0.100 mol
dm-3 – i.e. doubles
• The rate of reaction increases from 2.24 x 10-4 mol dm-3 s-1 to 4.48 x 10-4
mol dm-3 s-1 – i.e. doubles
• Therefore the rate of reaction is first order with respect to NO2

For CO using the first and second sets of data…
• The concentration of CO increases from 0.050 mol dm-3 to 0.100 mol

dm-3 – i.e. doubles
• The rate of reaction increases from 1.12 x 10-4 mol dm-3 s-1 to 2.24 x 10-
4 mol dm-3 s-1 – i.e. doubles
• Therefore the rate of reaction is first order with respect to CO
Rate equation
 rate of reaction is first order with respect to NO2
 rate of reaction is first order with respect to CO
rate = k [NO2][CO]

Overall the reaction is second order
Rate equation can only be determined experimentally!

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Topic 11 - Kinetics

• What makes “superglue” bond instantly

Why do chemists study reaction rates

Rate of reaction Half-life

Heterogeneous and homogeneous

change in concentration, volume or mass

There are two ways to measure the rate of a reaction:

 Measure the rate at which a reactant is used up

 Measure the rate at which a product is formed

 Particles have to collide with a  Temperature

 The collisions with energy greater  Surface area

or equal to the activation energy are  catalyst

Inverted measuring cylinder Gas syringe

Gas escapes through the

No useful if the gas released is

• Small portions (aliquots) removed

• Reagent added to quench (stop) the

• The quenched aliquots are titrated to

• As a reaction takes place in solution,

Measuring Rates of Reactions

Example of reaction Means of following the reaction

C2H5OH sampling at set time intervals and

NB the orders of reaction are determined by

• [] stands for concentration of species

The order of a reaction with respect to a chemical is found

Units of rate of reaction are mol dm-3 s-1

The unit for the rate constant changes

 Units of k – zero order

rate = k [A]0 k= rate

Unit of k mol dm-3 s-1

 Units of k – first order

rate mol dm-3 s-1

So k has the units of rate s-1

 Units of k – second order

rate mol dm-3 s-1

So k has the units of rate mol-1 dm3 s-1

The unit for the rate constant changes

 Units of k – third order

1. Rate = k [N2][H2] 2nd order; mol-1 dm3 s-1

1st order; s-1

0 order; mol dm-3 s-1

4. Rate = k [C2H4][Cl2]2 3rd order - mol-2 dm6 s-1

RATE = k [A]m [B]n

 Orders of reaction do not change with temperature.

 Rate constant changes with temperature. Increasing the

Similarly as catalyst increase rate, k must increase as

II) Continuous monitoring method

Experiments that can be used to investigate reaction rates

• Therefore the rate of reaction is first order with respect to NO2

• The concentration of CO increases from 0.050 mol dm-3 to 0.100 mol

 rate of reaction is first order with respect to CO

Rate equation can only be determined experimentally!

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