Lecture 6: CHE 316

Reaction Mechanisms
 The sequence of events that describes the actual process by which reactants become
products is called the reaction mechanism.
 Reactions may occur all at once or through several discrete (separate) steps.
 Each of this processes/step is known as an elementary reaction/step or elementary process.
 Each elementary step would have a hypothetical species which is too short lived to be
detected using instruments.
 This species is called an activated complex or the transition state.
 It is the transition states that involve the breaking of chemical bonds and the reforming of
other bonds to get product molecules.
 This process of bond breaking and formation is so fast that transition states have very short
half-lives.

Elementary Steps & Molecularity

Molecularity
 (b) It is a theoretical concept.
 (c) It cannot be zero.
 (d) It does not change with change in temperature and pressure.
a) Unimolecular: one molecule in the elementary step i.e. if only one reactant molecule is
involved in the step, then that step is said to occur in a unimolecular fashion.
O3  O2 + O (the decomposition or rearrangement of an energized molecule)
b) Bimolecular: two molecules in the elementary step i.e. involvement of two reactant molecules
in an elementary step.
2HI  H2 + I 2
CH3COOC2H5 + H2O = CH3COOH + C2H5OH hydrolysis of ester
c) Termolecular: three molecules in the elementary step i.e. these occur with three reactant
molecules - not impossible but extremely rare.

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Reaction Mechanisms and Net Reactions
 If we add up all the elementary steps in a proposed mechanism and simplify, that should
result in the net reaction. For example:
 In the reaction:
NO2(g) + CO(g)  NO(g) + CO2(g)
 The following reaction mechanism has been proposed:
1. NO2 + NO2  N2O 4 (slow step)
2. N2O4 + CO  NO + CO2 + NO2 (fast)
We can ask a number of things concerning the above mechanism.
1. What is the indicated rate-determining step of the reaction?
2. What is the molecularity of step 1 and step 2?
3. Verify that this mechanism will produce the correct product indicated in the net reaction.
4. What are the intermediates (if any) identified in the mechanism?
5. Propose a theoretical rate expression for this reaction.
Question 1: The slowest step in the mechanism is the rate determining step.
Question 2: The number of reactant molecules involved in the step is its molecularity. For step
1, it would be 2 and for step 2 it would be 2.
Question 3: By adding up all the reactants of the steps in the mechanism and all the products and
then simplifying by canceling any species that appear on both sides will give you the net
reaction.
1. NO2 + NO2  N2O4 (slow step)
2. N2O4 + CO  NO + CO2 + NO2 (fast step)
Net reaction → NO2 + NO2 + N2O4 + CO  N2O4 + NO + CO2 + NO2
= NO2 + CO  NO + CO2
Since the N 2O4 appears on both sides once and will cancel and the NO 2 appears twice on the left
and once on the right, one of the NO 2 molecules will cancel one on the other side.
Question 4: A species that is initially formed in one elementary step only to be consumed as a
reactant in a later step is called an intermediate. N 2O4 is produced in step 1 and consumed in
step 2 which makes it an intermediate in this mechanism.
Question 5: Rate = k[NO2][NO2] → from rate determining step.
= k[NO2]2 (Theoretical Rate Law Expression)

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Experimental Validation of Reaction Mechanisms
 Once a reaction mechanism has been proposed for a reaction process, the mechanism must
collect experimental verification.
 One way to do this is to determine the experimental Rate Law Expression in the manner that
we did with determining rate orders and then rate constants.
 This leads to a rate law expression that is based on experimental data.
 Comparing experimental rate law expression with the theoretical rate law expression found
based on a proposed reaction mechanism, if they are the same then, the reaction mechanism
is said to be validated by experimental results because it predicted the actual rate law
expression under experimental conditions.
 If the proposed reaction mechanism has the slow rate determining step which is not
preceded by a fast equilibrium step, then the theoretical rate expression based on the
mechanism is simply the expression that you would get when considering only the slow step.
Example: The Iodide ion catalyzed decomposition of Hydrogen Peroxide, H 2O2 is believed to
follows the following proposed reaction mechanism:
1. H2O2 (aq) + I- (aq)  H2O (l) + IO-(aq) (slow)
2. H2O2(aq) + IO-(aq)  H2 O (l) + O2 (g) + I - (fast)
(IO- is hypoiodite ion)
Determine the theoretical rate law expression based on the above mechanism.
 In order to determine the expression, we simply use the Rate Law and write an expression
using the reactants of the slow step only.
 The rate order would be equal to the coefficient of each reactant so that in this case:
Rate = k [H2O2][I -]
 If this matches the experimental rate law expression, then the mechanism would receive
support from the kinetic data.
 However, there are many reactions where a proposed reaction mechanism involves a fast
equilibrium step that occurs before the slow step.
 The equilibrium step would affect the slow step so it must be taken into consideration.

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Formulation of a Theoretical Rate Law Expression with an Equilibrium Step
 Some proposed reaction mechanisms have a fast step in equilibrium prior to the slow rate
determining step.
 Such mechanism must incorporate the equilibrium step into the theoretical rate law
expression formulated using the slow step.
 This is because the equilibrium occurs first will influence the concentrations of the reactants
in the slow rate determining step.
 This incorporation can be done by first using the Law of Chemical Equilibrium to determine
an equilibrium expression for that fast step and then find a species common to both
equilibrium expression and the rate law expression.
 Solve for that common species using the equilibrium expression and then substitute that
solution into the rate law expression and simplify for the final theoretical rate law expression.

For example:
 The following net reaction has an experimental rate law expression according to the
experimental data:
2NO(g) + Br2(g)  2NOBr (g) (Nitrosyl bromide)
 The experimental rate law expression was:
Rate = k [NO]2[Br2]
 We seek a reaction mechanism that is consistent with this rate law.
 One possibility is that the reaction occurs in a single termolecular step.
NO(g) + NO(g) + Br2  2NOBr (g): Rate = k [NO]2[Br2 ]
 This does not seem likely, however, because termolecular processes are so rare.
 An alternative mechanism;

k1
Step 1: NO(g) + Br2(g) NOBr2(g) (fast)
k2
Step 2: NOBr2(g) + NO(g) 2NOBr(g) (slow)

 The rate of the overall reaction governed by the rate law for step 2.
Rate = k2 [NOBr2][NO]
 But NOBr2 is an intermediate and can’t be a part of the overall rate expression.
 Intermediates are usually unstable molecules that have a low unknown concentration.

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 Fortunately, with some assumptions the concentration of NOBr2 can be expressed in terms of
the concentrations of NO and Br2 .
 After NOBr2 is formed, there can be two scenarios;
(1) React with NO to give NOBr or
(2) Decompose back apart to NO and Br2.
Since formation of NOBr is a slow process, it is more probable for NOBr 2 to decompose as the
reverse of step 1: We can then assume the first step achieves equilibrium with its forward and
reverse reactions.
 We assume that k1[NO][Br2] = k -1[NOBr2] using the equilibrium in step 1.
k1
 Solving for [NOBr2], we have [NOBr2] = [NO][Br2]
k 1
 Substituting this relationship into the rate law for the rate-determining step, we have
k1
Rate = k2 [NO][Br2][NO] = k[NO]2[Br2]
k 1
 This is consistent with the experimental rate law.
k 2 k1
 The experimental rate constant k is equal to; .
k 1
 This mechanism, which involves only unimolecular and bimolecular processes, is far more
probable than the single termolecular step.
 In general, whenever a fast step precedes a slow one, we can solve for the concentration of an
intermediate by assuming that equilibrium is established in the fast step.

Sample exercise
Show that the following mechanism for
2NO(g) + Br2(g)  2NOBr (g) also produces a rate law consistent with experimental law;
Rate = k[NO]2[Br2]
Given;
k1
Step 1: NO(g) + NO (g) → N2O2(g) (fast, equilibrium)

k2
Step 2: N2O2(g) + Br2(g) → 2NOBr(g) (slow)