16.

2 Reaction Mechanism

Simple reactions occur in only one step but more complex reactions can involve two or more. The
sum of these steps is called the reaction mechanism. Most produce an intermediate product that
reacts further until it reaches the final product

The intermediate will not necessarily react with each of the reactants, so only changing the
concentrations of those reactants involved in the rate determining step will affect the overall rate
of the reaction.

For example:
2A + B → C

reaction mechanism

Step 1 2A → A2 (slowest step)

intermediate

Step 2 A2 + B → C

Intermediate A2 reacts only with reactant B

Each step in the reaction mechanism will has a different activation energy. The slowest step in a
reaction mechanism will determine the overall rate of the reaction. This step is called the rate
determining step, RDS. This step has the highest activation energy. Only those reactants involved
in the rate determining step or the reaction before it can affect the overall rate of the reaction.

In a reaction involving two steps, there will be two activation energies, one for each step. The rate
determining step has the largest activation energy and will be the slowest because a greater
amount of time is required before all the reactant molecules have energy, E ≥ activation energy, Ea.

In the graph above step one in the reaction would be the rate determining step because it has the
highest activation energy.
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In practice this makes it difficult to predict a single rate expression for a chemical reaction because
nearly all reactions have more than one step. To really understand how a chemical reaction occurs
chemists usually predict a number of different possible reaction mechanisms. A reaction
mechanism is defined as a sequence of reaction steps that most likely shows how individual atoms,
molecules or ions (species) take part when the reactants are converted into products. Further
experiments can be carried out to eliminate the least likely mechanisms. The final proposed
mechanism however is not proof that the reaction takes place this way but it does provide chemists
with a likely mechanism that can be compared with an experimentally determined rate expression
to see if there is a match.

The process of predicting a reaction mechanism is very difficult and requires considerable
understanding of reaction kinetics. IB Chemistry only touches on it briefly by looking at how the
experimentally determined rate expression relates to one and two step mechanisms.

In a reaction mechanism:
• The reaction in each step is written without the state symbols
• The sum of the steps in the reaction mechanism must give the overall balanced equation for
the reaction.
• The rate determining step is the slowest step.
• The rate expression (rate equation) for a reaction is deduced from a proposed reaction
mechanism and its rate determining step.
• The rate expression for the slowest step must agree with the rate expression for the overall
reaction.

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Example 1

Consider the following reaction. In the stratosphere ozone is formed and destroyed naturally in the
presence of a UV light catalyst. This ozone acts as a shield protecting the earth from absorbing 99%
of the sun’s harmful UV-B radiation. Ozone depleting substances created by human are increasing
the rate at which ozone is being destroyed, exposing us to increasing amounts of harmful UV-B
radiation. The following mechanism is most likely for the natural destruction of ozone.

Step 1 O3 + UVlight → O2 + O⋅ slow

Step 2 O⋅ + O3 → 2 O2 fast

Experimental rate data shows that step 1 the slowest. The overall reaction for ozone destruction
can be found by adding the two reactions and canceling out species common to both sides of the
equation.

O3 + UVlight → O2 + O⋅

O⋅ + O3 → 2 O2

Overall 2 O3(g) → 3 O2(g)

The molecularity of a reaction refers to the number of reactant species (ions, atoms, molecules)
that must collide with the correct geometry (orientation) and with E ≥ Ea for a reaction to occur. The
reactants can be the same or different. Each step in a reaction mechanism has its own
molecularity however, in most cases the molecularity refers to the slowest, rate determining step.
There are two types of reactions, unimolecular and bimolecular. Termolecular (3 molecules) or
tetramolecular (4 molecules) reactions are not statistically probable because it is unlikely that three
or more reactants will collide with one another at the same time, in the correct orientation and
with an E ≥ Ea in order to bring about a reaction.

In this mechanism step 1 is unimolecular because one ozone molecule decomposes.

O3 + UVlight → O2 + O

Step 2 is a bimolecular because two molecules (one oxygen atom and one ozone molecule) collide.
O + O2 → O3
The rate expression for each step in the mechanism is the rate constant multiplied by the reactants
raised to their stoichiometric power. NOTE: This is different to how an experimental rate
expression is determined where a series of different experiments are carried using different initial
concentrations of reactants.

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In step 1 O3 + UVlight → O2 + O slow

Rate expression from mechanism: Rate = k [O3]1. The reaction is first order

In Step 2 O + O3 → 2 O2 fast

Rate expression from mechanism: Rate = k [ O]1 [O3]1. The reaction is second order

Since the overall rate of the reaction is controlled by the slowest step in the mechanism only those
reactants involved in the rate determining step or the reaction before it can affect the overall rate
of the reaction. The overall rate must match the rate of this step. This means that the overall
reaction must be first order with respect to the [O3] and unimolecular. The rate expression for the
overall reaction is therefore R = k [O3]1

In bimolecular reactions when two reactants particles collide with energy ≥ Ea, they initially form a
transition state at an energy maximum. An activated complex forms at this transition state. An
activated complex is a combination of the two reacting molecules that can either go on to form
products or fall apart unchanged. Because energy of the transition state is high the lifetime of the
activated complex is short. The activated complex does not appear in the reaction mechanism, the
overall chemical equation or the rate expression.

Example 2
The reaction between bromoethane and dilute sodium hydroxide
C2H5Br + OH- → C2H5OH + Br-
involves the formation of the following activated complex at the transition state

C2H5Br + OH- → → C2H5OH + Br-

Activated complex

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An intermediate occurs at a potential energy minimum. Intermediates can be identified in the
reaction mechanism because they are formed in one step and then used as a reactant in the next
step. Intermediates do not appear in the overall equation for the reaction because they get
cancelled out when steps are summed or in the rate expression for each step.

For example the reaction between 2-bromo-2-methylpropane and dilute sodium hydroxide has a
two step reaction mechanism involving the formation of the intermediate, C(CH3)3+.

Step 1 C(CH3)3Br → C(CH3)3+ + Br- Slow, RDS

Step 2 C(CH3)3+ + OH- → C(CH3)3OH Fast

Overall C(CH3)3Br + OH- → C(CH3)3OH + Br-

Notice how the intermediate is formed step 1 and then used as a reactant in step 2.

Example 3
Dinitrogen oxide decomposes according to the following equation.

2 N2O(g) → 2 N2(g) + O2(g)

Experimental results show that the reaction is bimolecular and first order with respect to the
dinitrogen oxide. Therefore the rate expression is Rate = k [N2O]1

How can we go about proposing a reaction mechanism for this reaction? Firstly,
since the reaction is bimolecular, the slowest rate determining step must involve two
molecules. One possible reaction might be:

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N2O(g) + N2O(g) → N4O2(g) slow

The second step, has to be a faster step and could be

N4O2(g) → 2 N2(g) + O2(g) fast

Since one of the criteria for a reaction mechanism is that the sum of the steps must give the overall
reaction, we can add the steps to see if they match the overall reaction.

N2O(g) + N2O(g) → N4O2(g)

N4O2(g) → 2 N2(g) + O2(g)

2 N2O(g) → 2 N2(g) + O2(g)

Example 4
The experimentally determined rate expression and proposed reaction mechanism for the reaction
between nitrogen dioxide and carbon monoxide is given below.

Experimentally determined Rate = k [NO2]2

Step 1 NO2(g) + NO2(g) → NO3(g) + NO(g)

Step 2 NO3(g) + CO(g) → NO2(g) + CO2(g)

The sum of the steps in the reaction mechanism add to give the overall equation

NO2(g) + NO2(g) → NO3(g) + NO(g)

NO3(g) + CO(g) → NO2(g) + CO2(g)

NO2(g) + CO(g) → NO(g) + CO2(g)

NO3 is the intermediate. Notice how it is formed in one step and then consumed the next step.

Remember that the rate expression for each step in the mechanism is the rate constant
multiplied by the sum of the reactants raised to their stoichiometric power. Since the rate
expression for the rate determining step in the mechanism must agree with the
experimentally determined rate expression the first step must be the rate determining
step. This is because the overall reaction is second order with respect to the [NO2]
and there are two molecules of NO2 in step 1.

CO is not in the rate expression and therefore the rate of the reaction must be zero order
with respect to the CO, or in other words the rate of this reaction is independent of the CO

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concentration. This means is that CO can’t be involved in the rate determining step.

Step 1 NO2 + NO2 → NO3 + NO Slowest step (RDS)

Rate = k [NO2]2
bimolecular

Step 2 NO3 + CO → NO2 + CO2 Fastest step

Rate = k [NO3]1[CO]1
Rate = k [NO2]2[CO]1

The rate of the overall reaction is determined by the rate of the RDS. The concentration of the
intermediate NO3 formed in the RDS depends on the concentration of NO2 to start with. Since NO3
is consumed in step two, the rate of step 2 will depend on the NO3 concentration. Since the NO3
concentration depends on the NO2 concentration, the two NO2 molecules in step 1 can be
substituted for the NO3 molecule in the rate expression for step 2. The reaction is bimolecular
because two molecules are involved in rate determining step.

To decide if a proposed reaction mechanism is likely the following check list can be used:
1. Do all elementary steps involve only one or two molecules, or three if the rate expression
indicates a termolecular reaction.
2. Is there a step with a rate expression matching the experimentally determined rate
expression.
3. Do the equations for the elementary steps add to give the correct overall equation.

Questions

1. (N01) The reaction between NO2 and CO gives NO and CO2 and is thought to occur by the
following mechanism.

Step 1 NO2(g) + NO2(g) → NO3(g) + NO(g) Slow

Step 2 NO3(g) + CO(g) → NO2(g) + CO2(g) Fast

What is the rate equation?

A. Rate = k [NO2][CO]
B. Rate = k [NO3][CO]
C. Rate = k [NO2]2[CO]
D. Rate = k [NO2]2

2. (M03/H) Which step in a multi-step reaction is the rate determining step?

A. The first step
B. The last step
C. The step with the lowest activation energy
D. The step with the highest activation energy

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3. State the molecularity of the following reactions
a) NO2 + NO2 → NO + NO3
b) Br2 → Br + Br
c) 2 NO + 2 H2 → N2 + 2H2O
Explain which reaction is unlikely to occur

4. (M05) The following reaction

2 N2O5(g) → 4 NO2(g) + O2(g)
is described as first order with respect to the N2O5.
a) Write the rate expression for the reaction. [1]
b) One possible mechanism for this reaction is given below
N2O5(g) → NO2(g) + NO3(g) Step 1
N2O5(g) + NO3(g) → 2 NO2(g) + O2(g) Step 2
Describe the rate expression that would result if the rate determining step in the
mechanism is
(i) Step 1 [1]
(ii) Step 2 [2]
Outline your reasoning
c) Explain what is meant by the term half-life for this reaction. [1]
d) State what is characteristic about the half life of a first order reaction. [1]

5. Consider the following reaction and its rate expression determined by experiment.

(CH3)3CBr + OH- → (CH3)3COH + Br- Rate = k [(CH3)3CBr]1

The following reaction mechanism was proposed.

Step 1 (CH3)3CBr → (CH3)3C+ + Br-

Step 2 (CH3)3C+ + OH- → (CH3)3COH

Identify the rate determining step. Explain the evidence.

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6. The reaction below is for the acid (H+) catalyzed addition of iodine to propanone.

CH3COCH3 + I2 + H + → CH3COCH2I + HI

[ CH3COCH3 ] [ I2 ] [ H+ ] Rate
Solution
(mol dm-3) (mol dm-3) (mol dm-3) (mol dm-3s-1)
1 0.2 0.008 1 4 x 10-6
2 0.4 0.008 1 8 x 10-6
3 0.6 0.008 1 1.2 x 10-5
4 0.4 0.004 1 8 x 10-6
5 0.4 0.002 1 8 x 10-6
6 0.2 0.008 2 8 x 10-6
7 0.2 0.008 4 1.6 x 10-5

The proposed reaction mechanism is

Step 1 CH3COCH3 + H+ → CH3C(OH)CH2

Step 2 CH3C(OH)CH2 + I2 → CH3COCH2I + HI

a) Determine the rate expression for the reaction

b) Identify the intermediate
c) Write the rate expression for each step
d) Identify the slowest step
e) State the molecularity of the reaction.
f) Propanone belongs to the homologous series of ketone. What are the characteristics of the
members of a homologous series?
g) Draw the structure formula for butanone.
h) Iodine is a diatomic element. Write the symbol formula for the six other diatomic elements.

7. The reaction between NO2 and CO produces NO and CO2 and is thought to occur by the
following mechanism

Step 1 NO2 + NO2 → NO3 + NO Slow

Step 2 NO3 + CO → NO2 + CO2 Fast

a) Write the rate expression for each step.

b) Predict the overall rate expression.
c) State the molecularity of the reaction
d) Identify the intermediate
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 e) Write and overall equation for the reaction.
f) Define a rate determining step
g) Draw the Lewis structures for CO2 and CO. Using VSEPR theory state and explain the
shape of CO2.

8. The difficulty with relying on a rate expression to describe the relationship between the
concentration of the reactants and the rate of the reaction is that nearly all reactions have
more than one step. To understand how a chemical reaction occurs chemists use reasoning
to predict a number of different possible reaction mechanisms. Using the experimentally
determined rate expression deductive reasoning is used to deduce the slowest and fastest
steps and from there a logical conclusion, a set of possible reactions and a rate expression
for each step can be made. Further experiments can be carried out if needed to eliminate
the least likely mechanisms. The final proposed mechanism however is not proof that the
reaction takes place this way but it does provide chemists with a reaction pathway that can
be compared with the experimentally determined rate expression to see if there is a match.
If there is agreement the more certain the proposed mechanism is. If there is no
agreement, then this provides evidence to disprove the mechanism. Even though chemists
can never be entirely certain of the exact steps in a reaction mechanism these uncertainties
do not prevent them from continuing the search for the most probable mechanism. Instead
it reinforces the fact that scientific knowledge can be both simultaneously certain and
tentative helping chemists remain open to new ideas, new theories and new knowledge.
Why are we more likely to believe a proposed reaction mechanism when it is in agreement
with the rate expression?

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16.2 Reaction Mechanism ANSWERS

1. (N01) D rate equation needs to consistent with slowest RDS because

this step determines the overall rate of the reaction.

2. (M03) D the slowest step has the highest Ea.

3. a) bimolecular – two molecules reacting

b) unimolecular – one molecule reacting
c) tetramolecular – 4 molecules reacting
c) is unlikely to occur because it is not probably that all four reactant molecules can collide
with the correct geometry (orientation)

4. (M05)
a) Rate = k [N2O5]1 ; The reaction is determined from experiment and found
to be first order
b) (i) Rate = k [N2O5]1
rate constant, k multiplied by the sum of the reactants raised to their
stoichiometric power.
(ii) Rate = k [N2O5]2 ;
Rate = k [N2O5]1 [NO3]1 but [NO3] depends on [N2O5] in the first step. The
concentration of NO3 formed in the RDS depends on the concentration of
N2O5 to start with. Since NO3 is consumed in step two, the rate of step 2 will
depend on the NO3 concentration. Therefore since the NO3 concentration
depends on the N2O5 concentration, N2O5 from step 1 can be substituted for
NO3 in the rate expression for step 2)

c) time taken for the concentration of N2O5 to reach half its initial value;
d) the half life is constant ;

5. Step 1 ;
Because the hydroxide ions, OH- are not in the rate expression the overall rate of the
reaction is not affected by the [OH-]. Therefore OH- can’t appear in the rate determining
step, so the rate determining step must be the first step.

OH- ions must be zero order, it doesn’t matter how their concentration changes it doesn’t
affect the rate. OH- therefore must be involved in some step.

Also the order of reaction matches the number of molecules (one (CH3)3CBr) in the rate
determining step.
Step 1 (CH3)3CBr → (CH3)3C+ + Br- Slowest step, RDS
k [(CH3)3CBr]1

One molecule involved

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6.
a) Rate = k [CH3COCH3]1 [I2]0 [H+]1 ;

Expt 1 & 2 First order, when the concentration doubles the rate doubles
[ CH3COCH3]order = rate
2order = 2
21 = 2

Expt 4 & 5 Zero order, when the concentration quarters the rate stays the same
[ I2]order = rate
¼ order = 1
¼0 = 1

Expt 6 & 7 First order, when the concentration doubles the rate doubles
[ H+]order = rate
2 order = 2
21 = 2

b) CH3C(OH)CH3 is the intermediate ;

It appears as a product in step 1 and then is used up in step two. It also cancels out
when the mechanisms are added.

c)
CH3COCH3 + H+ → CH3C(OH)CH2 R = k [CH3COCH3]1 [H+]1

CH3C(OH)CH3 + I2 → CH3COCH2I + HI R = k [CH3C(OH)CH3]1 [I2]1

d) The overall rate expression it must agree with the rate expression of the rate determining
step. Therefore the rate determining step must be the first step in the mechanism. Because
the rate was zero order with respect to the iodine, the rate of the reaction was independent
of the iodine concentration. Therefore iodine can’t be involved in the rate determining
step.

Step 1: CH3COCH3 + H+ → CH3C(OH)CH2 Slowest step

e) The reaction is bimolecular because two molecules (propanone and hydrogen ions) are
involved in the rate determining step.

f) Same general formula ;

differ by a CH2 group ;

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g) Correct structural formula of butanone ;

h) H2, N2, O2, F2, Cl2, Br2 ;

7.
a) Step 1 R = k [NO2]2 ;
Step 2 R = k [NO3 ]1 [CO]1 ;

b) R = k [NO2]2 ;

c) bimolecular ;

d) NO3 ;

e) NO2(g) + CO(g) → NO(g) + CO2(g)

f) slowest step in a reaction mechanism with the highest activation energy

g) correct Lewis structure for CO2

linear ;
two negative change centers / regions of bonding electrons ;
no lone / non bonding pairs of electrons ;
Bonding electrons repel each other equally in order to minimize the repulsion between
them ;

Correct Lewis structure for CO ;

8. Since a reaction mechanism is a theoretical prediction of the steps involved in a reaction,

the more evidence to support the prediction (especially if it is empirical – comes from an
experiment) the more likely we are to trust it.

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