Second-order reactions

Two of the same reactant (A) combine in a single elementary step.

A+A  P
2A  P
The reaction rate for this step can be written as:
−1 d [ A ] + d [ P ]
rate= =
2 dt dt
and the rate of loss of reactant A
d [A] 2
=−k [ A ][ A ] =−k [ A ]
dt
For reactions involving (A  products) that are second order with respect to A and second
order overall, the integrated rate equation is
d [A] 2 d [A]
=−k [ A ] → 2
=−kdt
dt [A]
Since we are interested in the change in concentration of A over a period of time, we
integrate between t=0 and t, the time of interest:
[ A ]t t
d [ A]
∫ =−k ∫ dt
[ [ A ]0 ] [ A ]2 0

We then obtain the integrated rate equation:

1 1
− =kt(second order )
[ A ] t [ A ]0
The half-life is given by [A]=1/2[A]0 at t = t1/2. Thus
1 1
− =k t 1/ 2
1
[A] [ A ]0
2 0
1
t 1/ 2= (second order ∈ A , second order ∈overall )
k [ A0]

Example:
For the reaction, 2HI → H2 + I2
the experimentally determined rate law is rate = k[HI]2
The order of the reaction is the exponent in the rate law.
Thus, this is a second order reaction.
Explain the mechanisms

A reaction mechanism is a step-by-step detailed description of a chemical reaction.

Each step in a mechanism is called an elementary process, which describes any
molecular event that significantly alters a molecules energy or geometry or produces a
new molecule. Two requirements of a reaction mechanism are that it must be:
- consistent with the stoichiometry of the overall reaction
- account for the experimentally determined rate law.
Rate laws are written for the elementary processes and combined into a rate law for the
overall reaction.
The coefficients for every given elementary step are equal to the reaction orders for that
step.
Based on the reaction mechanism, you can know whether the reaction is simple or
complex, and write the kinetic equation for each step. If the reaction is complex, it depends
on the slowest step, which is the kinetic equation of the reaction.
In many mechanisms, one step is much slower than the others. A reaction can never occur
faster than its slowest step. This slow step is called the rate-determining step. The speed
at which the slow step occurs limits the rate at which the overall reaction occurs.
One of the elementary processes may be the rate-determining step. When a single rate-
determining step cannot be identified, the mechanism can often be established by the
steadystate approximation.
The balanced equation for the overall reaction is equal to the sum of all the individual
steps, including any steps that might follow the rate-determining step.
However, The rate-law exponents do not necessarily match the coefficients of the overall
balanced equation.
For the general overall reaction aA + bB  cC + dD
The experimentally determined rate-law expression has the form rate = k[A] x[B]y
The values of x and y are related to the coefficients of the reactants in the slowest step,
influenced in some cases by earlier steps.
Example:
This is a mechanism of the reaction between gaseous iodine monochloride and gaseous
hydrogen produces iodine and hydrogen chloride as gaseous products.
H2(g) + 2 ICl(g)  I2(g) + 2HCl(g)
Let’s begin with a two-step mechanism:
(1) Slow: H2 + Icl  HI + HCl
(2) Fast: HI + ICl  I2 + HCl
Overall: H2 + 2 ICl  I2 + 2 HCl
This scheme seems plausible for two reasons:
(1) The sum of the two steps yields the experimentally observed overall reaction.
(2) As we have noted, unimolecular and bimolecular elementary processes are most
plausible, and each step in the above mechanism is bimolecular. Because each step is an
elementary process, we can write
rate [1] = k1[H2][ICl] and rate [2] = k2[HI][ICl]
Now, we can see that step (1) occurs slowly but step (2) occurs rapidly. This suggests that
HI is consumed in the second step just as fast as it is formed in the first. The first step is
the rate-determining step, and the rate of the overall reaction is governed just by the rate
at which HI is formed in this first step, that is, by rate (1). This explains why the observed
rate law for the net reaction is rate of reaction = k[H 2][ICl]. The proposed mechanism gives
a rate law that is in agreement with experiment, as it should if we have made a reasonable
proposal.
The species HI is called a reaction intermediate, and it does not appear in the
experimental rate law. In this case, the intermediate species is a wellknown stable
molecule. Often, when postulating mechanisms, we have to invoke less well-known and
less stable species; and in these instances, we have to rely on the chemical
reasonableness of the basic assumptions. The presence of a reaction intermediate leads
to a slightly more complicated reaction profile. We see that there are two transition states
and one reaction intermediate. The activation energy for the first step is greater than that
for the second step, which we would expect if the first step in the reaction mechanism is
the slowest. It is important to understand the difference between a transition state
(activated complex) and a reaction intermediate. The transition state represents the
highest energy structure involved in a reaction (or step in a mechanism). While transition
states exist only momentarily and can never be isolated, reaction intermediates can
sometimes be isolated. Transition states have partially formed bonds, whereas reaction
intermediates have fully formed bonds.
It is necessary to to distinguish among species that can appear in a reaction mechanism.
– Reactant: More is consumed than is formed.
– Product: More is formed than is consumed.
– Reaction intermediate: Formed in earlier steps, then consumed in an equal amount in
later steps.
– Catalyst: Consumed in earlier steps, then regenerated in an equal amount in later steps.
The experimentally determined reaction orders of reactants indicate the number of
molecules of those reactants involved in
– (1) the slow step only, if it occurs first, or
– (2) the slow step and any fast equilibrium steps preceding the slow step.