TOPIC 6.

2
CHEMICAL KINETICS

6.2
Rate Expression and
Reaction Mechanism

By: Merinda Sautel

Alameda Int’l Jr/Sr High School
Lakewood, CO
[email protected]
 ESSENTIAL IDEA
Rate expressions can only be determined empirically
and these limit possible reaction mechanisms. In
particular cases, such as a linear chain of elementary
reactions, no equilibria and only one significant
activation barrier, the rate equation is equivalent to the
slowest step of the reaction.
Principle of Occam’s razor – newer theories need to remain
as simple as possible while maximizing explanatory power.
The low probability of three molecule collisions means
stepwise reaction mechanisms are more likely.
 INTERNATIONAL-MINDEDNESS

The first catalyst used in industry was for the

production of sulfuric acid. Sulfuric acid
production closely mirrored a country’s
economic health for a long time. What are some
current indicators of a country’s economic
health?
 THEORY OF KNOWLEDGE

Reaction mechanism can be supported by

indirect evidence. What is the role of
empirical evidence in scientific theories? Can
we ever be certain in science?
 UNDERSTANDING/KEY IDEA
16.1.A
The order of a reaction can be
either integer or fractional in
nature. The order of a reaction can
describe, with respect to a reactant,
the number of particles taking part
in the rate-determining step.
 Distinguish between the terms rate
constant, overall order of reaction
and order of reaction with respect
to a particular reactant.
 DEFINITIONS

 The order of reaction with respect to a

particular reactant is the power to which its
concentration is raised in the rate equation.
 The overall order for the reaction is the sum
of all the individual orders for all reactants.
 The rate constant (k) is a constant for a
particular reaction at a specified
temperature.
 RATE LAW EXPRESSION
A+B PRODUCTS
The rate law can be written as follows:
R = k [A]m[B]n
where R is the rate
k is the rate constant
A and B are reactants
m and n are the experimentally found
orders of the reaction with respect to
each reactant
 2H2 + 2NO 2H2O + N2

 R = k [NO]2[H2]
 Notice that the coefficients in the equation
are not the exponents in the rate expression.
Please do not confuse this with equilibrium.
 This is a 2nd order rxn with respect to NO
and a 1st order rxn with respect to H2.
 The overall order is found by adding the
individual orders 2 + 1 = 3.
 UNDERSTANDING/KEY IDEA
16.1.B

The value of the rate constant (k) is

affected by temperature and its
units are determined from the
overall order of the reaction.
 UNITS OF THE RATE
CONSTANT (k)
 Zero order Rate = k k = units of rate
 = mol dm-3 s-1
 First order Rate = k[A] k = units of rate/units of conc
 = (mol dm-3 s-1)/(mol dm-3) = s-1
 Second order Rate = k[A]2 k = units of rate/(units of conc)2
 = (mol dm-3 s-1)/(mol dm-3)2 = mol-1dm3 s-1
 Third order Rate = k[A]3 k = units of rate/(units of conc)3
 = (mol dm-3 s-1)/(mol dm-3)3 = mol-2 dm6 s-1
 UNDERSTANDING/KEY IDEA
16.1.C

Rate equations can only be

determined experimentally.
 APPLICATION/SKILLS

Be able to deduce the rate

expression for an equation from
experimental data and solve
problems involving the rate
expression.
 DETERMINING THE EXPONENTS IN A
RATE LAW
 This must be done experimentally. NEVER assume
the exponents equal the coefficients in the balanced
equation.
 Factor by which Factor by which Order of
conc. is changed rate changes Reaction
2 No change 0
3 No change 0
2 2 = 21 1
3 3 = 31 1
4 4 = 41 1
2 4 = 22 2
3 9 = 32 2
4 16 = 42 2
2 8 = 23 3
3 27 = 33 3
4 64 = 43 3
 INITIAL RATES METHOD
Problem - Write the rate law, determine the value of
the rate constant, k, and the overall order for the
following reaction:

2 NO(g) + Cl2(g)  2 NOCl(g)

Experiment [NO] [Cl2] Rate

(mol/dm3) (mol/dm3) mol/dm3·s
1 0.250 0.250 1.43 x 10-6
2 0.500 0.250 5.72 x 10-6
3 0.250 0.500 2.86 x 10-6
4 0.500 0.500 11.4 x 10-6
OBSERVATIONS

 When given initial concentration data,

you want to look at each reactant
separately.
 Try to find 2 reactions where your
identified reactant is changing and the
other reactant(s) are constant.
 For example in rxns 1 and 2, [NO] is
changing and [Cl2] is constant.
 Part 1 – Determine the values for the exponents in the rate law:

R = k[NO]x[Cl2]y

Experiment [NO] [Cl2] Rate

(mol/dm3) (mol/dm3) mol/dm3·s
1 0.250 0.250 1.43 x 10-6
2 0.500 0.250 5.72 x 10-6
3 0.250 0.500 2.86 x 10-6
4 0.500 0.500 1.14 x 10-5

In experiment 1 and 2, [Cl2] is constant while [NO] doubles.

The rate quadruples, so the reaction is second order with respect to [NO]

 R = k[NO]2[Cl2]y
 Part 1 – Determine the values for the exponents in the rate law:

R = k[NO]2[Cl2]y
Experiment [NO] [Cl2] Rate
(mol/dm3) (mol/dm3) mol/dm3·s
1 0.250 0.250 1.43 x 10-6
2 0.500 0.250 5.72 x 10-6
3 0.250 0.500 2.86 x 10-6
4 0.500 0.500 1.14 x 10-5

In experiment 2 and 4, [NO] is constant while [Cl2] doubles.

The rate doubles, so the reaction is first order with respect to [Cl2].

 R = k[NO]2[Cl2]
 Part 2 – Determine the value for k, the rate constant, by using any set of
experimental data:

R = k[NO]2[Cl2]

Experiment [NO] [Cl2] Rate

(mol/dm3) (mol/dm3) mol/dm3·s
1 0.250 0.250 1.43 x 10-6

2
mol
6  mol   mol 
1.43 x 10  k  0.250   0.250 
Ls  L   L 

 1.43 x106   mol   L3  5 L 2

k    3 
 9.15 x 10
 0.2503
 L  s  mol  mol 2
s
 APPLICATION/SKILLS

Be able to sketch, identify and

analyze graphical representations
for zero, first and second order
reactions.
 GUIDANCE

Be familiar with concentration vs

time and rate vs concentration
graphs.
concentration ZERO-ORDER REACTION

time rate concentration

Rate = k[A]0
concentration FIRST-ORDER REACTION

time rate concentration

Rate = k[A]
HALF-LIFE

 If a reactant has a constant half-life,

then the reaction must be first order
with respect to that reactant.
 This is only true for 1st order reactions.

 The shorter the half-life, the faster the

reaction.
 Half-life (t1/2) is the time it takes for
half the concentration to decrease.
concentration SECOND-ORDER REACTION

time rate concentration

Rate = k[A]2
The concentration – time graph starts out steeper than the first order
and levels off more than first order.
concentration SUMMARY

time rate concentration

 UNDERSTANDING/KEY IDEA
16.1.D

Reactions may occur by more than

one step and the slowest step
determines the rate of reaction.
(rate determining step/RDS)
 APPLICATION/SKILLS

Evaluate proposed reaction

mechanisms to be consistent with
kinetic and stoichiometric data.
 Reaction Mechanism

The reaction mechanism is the series of

elementary steps by which a chemical reaction
occurs. It is a theory about the sequence of
events in the progression of reactants to
products.
The sum of the elementary steps must give
the overall balanced equation for the reaction
 Rate-Determining Step

In a multi-step reaction, the slowest step

is the rate-determining step. It therefore
determines the rate of the reaction.

The experimental rate law must agree

with the rate-determining step.
 Identifying the Rate-Determining
Step
For the reaction:
2H2(g) + 2NO(g)  N2(g) + 2H2O(g)
The experimental rate law is:
R = k[NO]2[H2]
Which step in the reaction mechanism is the rate-determining (slowest) step?

Step #1 H2(g) + 2NO(g)  N2O(g) + H2O(g)

Step #2 N2O(g) + H2(g)  N2(g) + H2O(g)

Step #1 agrees with the experimental rate law

 Identifying Intermediates
For the reaction:
2H2(g) + 2NO(g)  N2(g) + 2H2O(g)
Which species in the reaction mechanism are intermediates (do not
show up in the final, balanced equation?)

Step #1 H2(g) + 2NO(g)  N2O(g) + H2O(g)

Step #2 N2O(g) + H2(g)  N2(g) + H2O(g)

2H2(g) + 2NO(g)  N2(g) + 2H2O(g)

 N2O(g) is an intermediate
 GUIDANCE

Be able to use potential energy

level profiles to illustrate multi-step
reactions; showing the higher Ea in
the rate-determining step in the
profile.
www.chemguide.co.uk
The activation energy for the overall reaction is equal to
the activation energy of the rate determining step.
 GUIDANCE

You should be familiar with

reactions where the rate-
determining step is not always the
first step.
www.chemistry.msu.edu

Notice the second step is the rate determining

step since it has a higher activation energy.
 When the rate determining step is not the first
step in the mechanism, it is a bit more
complicated.
 The reactant concentrations depend upon
earlier steps so these earlier steps must be
taken into account.
 2NO(g) + O2(g) 2NO2(g)

Step #1 NO(g) + NO(g)  N2O2(g) fast

Step #2 N2O2(g) + O2(g)  2NO2(g) RDS (slow)
Overall 2NO(g) + O2(g) 2NO2(g)

So the rate equation is taken from step 2

Rate = k[N2O2][O2] but N2O2 is an intermediate whose
concentration is based on step 1 which is NO(g) + NO(g).
We then substitute back into the rate equation getting
Rate = k[NO]2[O2] which matches the coefficients in the
overall balanced equation thus meeting the requirements
for the mechanism.
 UNDERSTANDING/KEY IDEA
16.1.E

The molecularity of an elementary

step is the number of reactant
particles taking part in that step.
 The term molecularity is used in reference to an
elementary step to indicate the number of
reactant species involved.
 Unimolecular – one reactant species

 Bimolecular – two reactant species

 Termolecular – three reactant species

 The probability of more than two particles
colliding at the same time with sufficient energy
and correct orientation is extremely low.
 UNDERSTANDING/KEY IDEA
16.1.F

Catalysts alter a reaction

mechanism, introducing a step with
lower activation energy.
 GUIDANCE

Know that catalysts are involved in

the rate-determining step.
 Catalysts alter the reaction
mechanism by providing an alternate
pathway for the rate-determining step
with a lower activation energy.

Duch.sd57.bc.ca
 Citations

International Baccalaureate Organization. Chemistry Guide, First

assessment 2016. Updated 2015.
Brown, Catrin, and Mike Ford. Higher Level Chemistry. 2nd ed.
N.p.: Pearson Baccalaureate, 2014. Print.
ISBN 978 1 447 95975 5
eBook 978 1 447 95976 2
Owen, Steve et Al, Chemistry for the IB Diploma, 2nd ed Cambridge
University Press, 2014. Print.
ISBN 978-1-107-62270-8