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RATE EQUATIONS AND REACTION MECHANISMS



1. Reaction mechanism: A
series of steps which are proposed to explain how the reactants change to the
products.

2. A proposed mechanism must
agree with:
(i) The balanced equation i.e.
when the steps are added together they should give the overall
equation/reaction in terms of reactants and products.
(ii) The mechanism must agree
with the reaction kinetics or the rate expression.
3. In most mechanisms there is
one slow or rate determining step and one or more fast steps which do not
affect the rate. The slow rate-determining step can be derived form the
rate expression. The partial order of any species appearing in the mechanism
after the rate determining step will be zero order confirming it has no effect
on the rate.






Mechanism for the hydrolysis of halogenoalkanes
There are two possible mechanisms for the hydrolysis of halogenoalkanes.
The chemical equation does not give any information about the mechanism of the
reaction.
The mechanism can be deduced by finding the order of reaction with respect to each
reactant.
Only substances involved in (or before) the rate-determining step appear in the rate
equation.
2

The order with respect to a reactant indicates the number of that particles of that
reactant involved in the rate-determining step.

Examples: S
N
1 and S
N
2 mechanisms of the hydrolysis of halogenoalkanes

(a) S
N
1 mechanism (Nucleophilic
substitution Unimolecular)
The term unimolecular indicates that there is only one species involved in the slow
rate determining step.
Consider the reaction between 2-bromo-2-methylpropane, (CH
3
)
3
CBr, a tertiary
halogenoalkane and OH
-
from aqueous sodium hydroxide solution:

(CH
3
)
3
CBr + OH
-
(CH
3
)
3
COH + Br
-


Rate = k [ halogenoalkane]

The reaction is FIRST order with respect to (CH
3
)
3
CBr and zero order with respect
to the OH
-
. Only (CH
3
)
3
CBr is taking part in the slow rate determining step of the
reaction. The OH
-
are involved in a relatively fast step following the rate determining
step and do not affect the rate.
Energy profile diagram for a two-step reaction


3

The activation energy fort he production of the
intermediate is greater than the activation
energy fort he intermediate going to the
products. This means that the first step is
rate-determining step.

The second activation energy is
greater, so the second step is the
rate determining step.
(Unstable) Intermediate product: formed in the slow rate determining step which
then reacts further to form the products.
Reactions which involve a single intermediate are ususally referred to as two-step
reactions.
Note that each step has its own transition state and activation energy.
(b) S
N
2 mechanism: (Nucleophilic substitution Bimolecular)

The term bimolecular refers to the molecularity of the reaction i.e. the number of
species involved in the slow rate-determining step.

Consider the reaction between bromoethane, CH
3
CH
2
Br, a primary halogenoalkane and
hydroxide ions, OH
-
from aqueous sodium hydroxide solution:

CH
3
CH
2
Br + OH
-
CH
3
CH
2
OH + Br
-


Rate = k [CH
3
CH
2
Br] [OH
-
]

The reaction is FIRST order with respect to both CH
3
CH
2
Br and + OH
-
. Both of
these species must be taking part in the slow rate-determining step of the reaction.
The reaction must happen by a straightforward collision between them.













Energy profile diagram for a one step reaction
4




Transition step: This often represents a condition where old bonds are half broken
and new ones are half formed. This transition state breaks down directly to the final
products without forming a more stable intermediate, which could then be involved in
a futher step.

There is one transition state for each step. The transition state is formed when
reacting particles have required activation energy E
A
. The activation energy is the
difference in energy between the reactants and the transition state.

(c) While the mechanisms
proposed for the alkaline hydrolysis of primary and tertiary halogenoalkanes are
consistent with the experimentally determined orders of reaction and the
overall equation for the reaction, the reaction between propanone and iodine is
not clear.



Propanone will react with iodine in the presence of acid as follows:

CH
3
COCH
3
(aq) + I
2
(aq) CH
3
COCH
2
I (aq) + HI(aq)

Experiments are performed to deduce the order with respect to each reactant.
The relative concentrations are shown below.

Experiment
No.
[CH
3
COCH
3
] [I
2
] [H
+
] Relative rate
H
+
5

1 1 1 1 2
2 1 2 1 2
3 2 1 1 4
4 1 1 2 4

Deduce the order of reaction with respect to each of the substances given in
the table and give the rate equation for the reaction.












A suggested mechanism is as follows:



Propanone will react with iodine in the presence of alkali as follows:
6


CH
3
COCH
3
(aq) + I
2
(aq) CH
3
COCH
2
I (aq) + HI(aq)

Experiments performed to deduce the orders with respect to each reactant
reveal that the reaction first order with respect to propanone, zero order with
respect to iodine and first order with respect to hydroxide ions, which do not
even appear in the equation.



The rate equation for this reaction therefore is:

Rate = k [CH
3
COCH
3
] [OH
-
]

A likely explanation for the mechanism of this reaction is that iodine enters
after the rate-determining step.

A suggested mechanism is as follows:

Step 1: the base removes a proton from a CH
3
group, which is the rate
determining step.

CH
3
COCH
3
+ OH
-
CH
3
COCH
2
-
+ H
2
O

Step 2: the lone pair of electrons on the C
-
of the carbanion forms a bond with
an iodine atom in I
2
and I
2
bond breaks.

CH
3
COCH
2
-
+ I
2
CH
3
COCH
2
I + I
-

Since the reaction is first order with respect to both propanone and hydroxide ions
and zero order with respect to iodine, the first step must be the rate determining
step. This fact can be confirmed by carrying out the same reaction but using bromine
or chlorine instead of iodine, where it is found that the overall rate of reaction is the
same.



Second or subsequent step is rate determining
OH
-

7

If the second or a subsequent step is rate determining, the derivation of the overall
rate equation is more complex.

Consider the reaction:
A + 2b + C D + E
Step 1 is a rapid step that is reversible:
A + B Int
where Int is an intermediate
Step 2 is the slowest step and hence is rate determining:
Int +B X
Step 3 is faster than step 2:
C + X D + E
The overall rate is determined by the rate of the slowest step 2:
Overall rate = rate of step 2 = k[B] [Int]






Examples:
Finding the slowest step in the reaction mechanism

The rate expression for the reaction:
2A (g) + 3B (g) C (g) + 2D (g)

is found to be Rate = k [A]
2
[B]
8


(a) Does this reaction have a mechanism?
Yes, because if there were no reaction mechanism, the rate expression of the given reaction
would be:
Rate = k [A]
2
[B]
3


But, the given rate expression is different from the rate expression we find. In that case
the reaction has a mechanism.

b) If it has a mechanism, write the slowest step.
Rate = k [A]
2
[B]
So, 2A + B products.



Finding the rate expression of a reaction
The mechanism proposed for the reaction:

2 ICl + H
2
2 HCl + I
2
is as follows:
(I) H
2
+ ICl HI + HCl (slow)
(II) HI + ICl HCl + I
2
(fast)

a) Which step is the rate-determining step?
Step I
b) What is the rate expression for this reaction?

Rate = k [H
2
] [ICl]
The rate expression can be written form the rate-determining step directly. The rate of the
reaction is directly proportional to the concentration of the reactants of the rate-
determining step.

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c) If the concentrations of H
2
and ICl are doubled, how many times will the rate of the
reaction change?
Increase by factor 4
(Because the rate of reaction is directly proportional to the both of the
concentrations of H
2
and ICl.


d) If the concentrations of HI and HCl are tripled, how many times will the rate change?
HI and HCl do not appear on the rate equation, so they do not cause any change.

Finding the rate-determining step
The rate equation for the reaction:
2NO (g) + Cl
2
(g) 2 NOCl (g)
is found to be Rate = k [NO]
2
[Cl
2
]
which of the following mechanisms will likely belong to this reaction?
A. 2NO (g) N
2
O
2
(slow)
N
2
O
2
(g) + Cl
2
(g) 2 NOCl (g) (fast)

B. Cl
2
(g) 2Cl (slow)
NO (g) + Cl (g) NOCl (g) (fast)

C. NO (g) + NO (g) + Cl
2
(g) 2 NOCl (g)

Answer: C




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Finding the rate expression

The reaction,
2A + B + K L + F + 120 kJ

has a mechanism with three steps.
The first two steps of the mechanism are as follows:
2A + B C + D (fast)
C + E K + L (fast)

a) Deduce the rate expression for the reaction.
The sum of the reactions in the mechanism gives the net (overall) reaction. Therefore,
the slowest step which is not given can be found by subtracting the given steps from
the net equation.
2A + B + K L + F (overall reaction)
-2A + B -C + D (fast)
-C + E -K + L (fast)
____________________________________________
K - E - K - D + F or
2K + D F + E which is the slowest step.
Therefore,
Rate = k [K]
2
[D]
b) How many times does the rate increase when the concentration of K and D are
tripled?
The rate of reaction is directly proportional to [K]
2
[D]
If only [K] is tripled, the rate increases 3
2
= 9 times
If only [D] is tripled, the rate increases 3 times
If both are tripled, the rate = (3)
2
x (3) = 27 times.
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THE ARRHENIUS EQUATION
The Arrhenius equation gives the relationship between the rate constant, k; the
temperature, T (in Kelvin) and the activation energy E
A
which is the minimum
energy that the reacting particles should have to collide to start the reaction.

The Arrhenius equation:
k = A e
E
A
/RT

where: k = The rate constant (determined at various temperatures)
T = Temperature of reaction in kelvin.
E
A
= Activation energy
R = Gas constant
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A = The Arrhenius constant which depends on
Using the Arrhenius equation
Taking natural logs (ln) on both sides, we obtain a more important form of the
expression:








(a) The effect of a change of temperature
The fraction of the molecules able to collide successfully almost doubles by
increasing the temperature by 10
0
C. This causes the rate of reaction to almost
double. This is the value in the rule-of-thumb often used in simple rate of reaction
work.
(b) The effect of a catalyst
A catalyst will provide a route for the reaction with a lower activation energy. As
a result, there is a massive increase in the fraction of the molecules which are
able to collide successfully, so the rate of reaction increases.

The rate constant is determined at a number of temperatures

The rate constant (ln k) is plotted against 1/T and from the graph a value for the
activation energy E
A
can be found.


ln k

ln A

1/T/K
-1


lnk = lnA E
A
/RT
13

Note: Since gradient is negative, E
A
is always positive. Units of E
A
are kJ mol
-1

Study question
The second-order rate constant for the reaction of 1-bromopropane with
aqueous hydroxide ions was measured as a function of temperature.

CH
3
CH
2
CH
2
Br (aq) + OH
-
(aq) CH
3
CH
2
CH
2
OH (aq) + Br
-
(aq)

The results are shown in the table below:

Tempertaure /K 1/T/K
-1
k/mol dm
-3
s
-1
lnk
298 1.4 X 10
-4

308 3.0 X 10
-4

318 6.8 X 10
-4

328 1.4 X 10
-3


Plot a graph of lnk against 1/T. Measure the gradient of the line and hence
calculate the activation energy of the reaction.

2. The activation energy of the oxidation in acid solution of iodide ions by iodate(V)
ions can be found by experiment:
Place 25 cm
3
of a solution of potassium iodate(V) in a beaker and add 5 drops
of starch solution.

Place 25 cm
3
of a solution of potassium iodide and 5 cm
3
of a solution of sodium
thiosulfate in another beaker.


Mix the two solutions, start a stop clock immediately and stir with a
thermometer. Read and record the temperature of the mixture.

Record the time when the solution turns intense blue.


Repeat the experiment with the same volumes of the solutions but at a higher
temperature.

Repeat the experiment at two more different temperatures.
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(a) Write the ionic equation for the formation of the iodine.



(b) Write the ionic equation for the reaction of iodine with thiosulfate ions.



When all the sodium thiosulfate has been used up, the next iodine that is
produced forms an intense blue colour with starch.
The results are shown in the table below.
Time/s 1/Time/s
-1
ln(1/Time) Temperature/K 1/Temp./K
-1
135 298
46 313
14 333

Complete the table and then plot a graph of ln(1/Time) on the y-axis against 1/T on
the x-axis. Measure the gradient of the line and evaluate the activation energy. You
may measure that the gradient of this line is the same as that of lnk against 1/T.
Activation energy and types of catalysts
Catalysts can be divided into two types:
- Homogeneous catalysts
- Heterogeneous catalysts
Homogeneous catalysts
A homogeneous catalyst is in the same phase as the reactants, usually the gas phase
or in solution.
The rate of reaction depends on the concentrations of the catalyst and one of the
reactants. An example is the oxidation of iodide ions by persulfate ions.

2I
-
(aq) + S
2
O
8
2-
(aq) I
2
(aq) + 2SO
4
2-
(aq)
This is a slow reaction because it requires two negative ions to collide. The reaction is
catalysed by iron () ions. The catalysed, route is oxidation of iodide ions by iron()
15

ions, followed by reduction of persulfate ions by iron () ions and the regeneration of
the catalyst of iron() ions:
2Fe
3+
(aq) + 2I
-
(aq) I
2
(aq) + 2Fe
2+
(aq)
2Fe
2+
(aq) + S
2
O
8
2-
(aq) 2Fe
3+
(aq) + 2SO
4
2-
(aq)


Heterogeneous catalysts
A heterogeneous catalyst is in a different phase from the reactants. Many industrial
processes use this type of catalyst; they have the advantage that the catalyst can be
separated from the equilibrium mixture by simple physical means. For example, in the
Haber process the solid iron catalyst catalyses the reaction between two gases,
hydrogen and nitrogen.
Heterogeneous catalysts are frequently transition metals- for example iron, platinum
and nickel.
The catalyst has active sites on its surface that rapidly become saturated by
reactants, which are then slowly converted into products. These leave the metal
surface, thus allowing more of the reactant to be adsorbed. This means that the rate
of a reaction is not altered by an increase in pressure of the gaseous reactants.








Exercise:
The second-order rate constant for the reaction of 1-bromopropane with aqueous hydroxide
ions was measured as a function of temperature.

16

CH
3
CH
2
CH
2
Br (aq) + OH
-
(aq) CH
3
CH
2
CH
2
OH (aq) + Br
-
(aq)

The results are shown in the table below:
Temperature/
0
C Temp/K 1/T /K
-1
k (mol
-1
dm
3
s
-1
) ln k
25 298 0.00336 1.4 x 10
-4
- 8.9
35 308 0.00325 3.0 x 10
-4
- 8.1
45 318 0.00314 6.8x 10
-4
-7.3
55 328 0.00306 1.4 x 10
-3
-6.6

Measure the slope (gradient) of the line and hence calculate the E
a
.

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