11.

1: Understand the terms:

i) rate of reaction
ii) rate equation, rate= k[A]m[B]n, where m and n are 0, 1 or 2
iii) order with respect to a substance in a rate equation
iv) overall order of a reaction
v) rate constant
vi) half-life
vii) rate-determining step
vii) activation energy
ix) heterogeneous and homogeneous catalyst

i) rate of reaction: The rate of reaction or reaction rate is the speed at which
reactants are converted into products. It is often expressed in terms of either
the concentration (amount per unit volume) of a product that is formed in a unit
of time or the concentration of a reactant that is consumed in a unit of time.
Alternatively, it may be defined in terms of the amounts of the reactants
consumed or products formed in a unit of time.

ii) rate equation, rate= k[A]m[B]n, where m and n are 0, 1 or 2:

In general terms, for a reaction A + B products, the rate equation can be

written in the form: rate of reaction = k[A] [B]n
m

This expression of a chemical reaction called rate equation.

Here,
. [A] and [B] are the concentrations of the reactants
. m and n are the orders of the reaction
.the values of m and n can be 0, 1, 2, 3 or rarely higher
. when the value of m or n is 0 ,concentration term is ignored because any
number to the power of zero = 1.

This overall expression is called rate equation. Here, constant k is called rate
constant. Rate equations can only be determined from experimental data. They
cannot be found from the stoichiometric equation.

iii) order with respect to a substance in a rate equation & iv) overall order of a
reaction:

In order to find the rate equation we have to conduct a series of experiments.

Using reaction 3 as an example:
In order to find the rate equation we have to conduct a series of experiments.
Using reaction 3 as an example:

. first find how the concentration of H2(g) affects the rate by varying the
concentration of H2(g), while keeping the concentration of NO(g) constant.
. the results show that the rate is proportional to the concentration of hydrogen
(rate = k1[H2]).
. then find how the concentration of NO(g) affects the rate by varying the
concentration of NO(g) while keeping the concentration of H2(g) constant.
. the results show that the rate is proportional to the square of the concentration
of NO (rate = k2[NO]2).

Combining the two rate equations we get the overall rate equation: rate = k[H2]
[NO]2.

We say that this reaction is:

. first-order with respect to H2, as rate is proportional to [H2]1

. second-order with respect to NO, (as rate is proportional to [NO]2)
. third-order overall (as the sum of the powers is 1 + 2 = 3).

v) rate constant: If a reaction is taken, where the concentration of reactant is

directly proportional to the rate; we can write -

Where, k is the proportionality constant. This constant k is called rate constant.

Every reaction has its own particular rate equation and its own rates constant.
Rate constant will only change their value with a change in temperature.
Units of rate constant:

vi) half-life: Half-life, t1/2, is the time taken for the concentration of a reactant to
fall to half of its original value. Following graph shows how half-life is measured
for the cyclopropane to propene reaction. Following table shows the values of
the successive half-lives obtained from this graph.
It is visible that, the successive half-lives have values that are fairly close to each
other (17.0, 17.3, 16.7). The mean half-life is 17.0 minutes for this reaction. We
can distinguish order of reaction from successive half-lives.

Explanation:
. a zero-order reaction has successive half-lives which decrease with time.
. a first-order reaction has a half-life which is constant.
. second-order reactions have successive half-lives which increase with time.

vii) rate-determining step:

viii) activation energy:
The term Activation Energy was introduced in 1889 by Svante Arrhenius, a
Swedish scientist. It is defined as the least possible amount of energy (minimum)
which is required to start a reaction or the amount of energy available in a
chemical system for a reaction to take place.

It is denoted by Ea and it is expressed (unit) in kJ/mol.

Activation energy is not similar for all reactions. Activation energy of a reaction
can be shown as follows:

The activation energy of a chemical reaction is closely related to its rate.

Specifically, the higher the activation energy, the slower the chemical reaction will
be. This is because molecules can only complete the reaction once they have
reached the top of the activation energy barrier. The higher the barrier is, the
fewer molecules that will have enough energy to make it over at any given
moment. Increasing temperature and using catalyst this barrier can be over-
comed.
ix) heterogeneous and homogeneous catalyst:
Catalyst is a substance which increases the rate of a reaction by providing an
alternative route having lower activation energy; but at the end remain
unchanged in mass. Catalyst can be divided into two main classes- homogeneous
catalyst and heterogeneous catalyst.

. Homogeneous catalysis occurs when the catalyst is in the same phase as the
reaction mixture. For example: hydrogen ions catalyse the hydrolysis of esters.

In this reaction the reactants, products and catalyst are all in the aqueous phase.

. Heterogeneous catalysis occurs when the catalyst is in a different phase to the

reaction mixture. For example, the decomposition of aqueous hydrogen peroxide
catalysed by manganese(IV) oxide.

The manganese(IV) oxide is in the solid phase, whereas the hydrogen peroxide is
in aqueous solution.
11.2: Be able to calculate the half-life of a reaction, using data from a suitable
graph, and identify a reaction with a constant half-life as being first order.

Half-life, t1/2, is the time taken for the concentration of a reactant to fall to half of
its original value. Following graph shows how half-life is measured for the
cyclopropane to propene reaction. Following table shows the values of the
successive half-lives obtained from this graph.

It is visible that, the successive half-lives have values that are fairly close to each
other (17.0, 17.3, 16.7). The mean half-life is 17.0 minutes for this reaction. We
can distinguish order of reaction from successive half-lives.
Explanation from graph:

Here, in both case, the half time is equal , indicating 1st order reaction.
11.3: Be able to select and justify a suitable experimental technique to obtain
rate data for a given reaction, including:
i) titration
ii) colorimetry
iii) mass change
iv) volume of gas evolved
v) other suitable technique(s) for a given reaction.

i)
ii)

iii)
iv)

v) others technique:
11.4: Understand experiments that can be used to investigate reaction rates by:
i) an initial-rate method, carrying out separate experiments where different
initial concentrations of one reagent are used A ‘clock reaction’ is an acceptable
approximation of this method.
ii) a continuous monitoring method to generate data to enable concentration-
time or volume-time graphs to be plotted.

i)
ii)
11.5: Be able to deduce the order (0, 1 or 2) with respect to a substance in a rate
equation, using data from:
i) a concentration-time graph
ii) a rate-concentration graph
iii) an initial-rate method

i) The following figure shows the order can be distinguished between zero, first
and second-order reactions by plotting a graph of concentration against time.

For first- and second-order reactions, the graph is a curve. The curve for the
second-order reaction is much deeper than for a first-order reaction. It also
appears to have a relatively longer ‘tail’ as it levels off. We can also distinguish
between these two curves by determining successive half-lives of the reaction.

For a zero-order reaction, the graph is a descending straight line. The rate of
reaction is the slope (gradient) of the graph. The reaction proceeds at the same
rate whatever the concentration of the reactant.
In practical, in finding the order, some steps are followed. This process is called
continuous method. In this method, one reaction mixture is made up and samples
of the reaction mixture are withdrawn at regular time intervals. The reaction in
the sample is stopped. The concentration of the reactant is then determined by
an appropriate experimental technique, such as titration.

Decision:
. if the half-life has a constant value, then the reaction is the first order with
respect to the reactant.
. if the half- life doubles as the reaction proceeds , then the reaction is second
order.
. if the graph is a straight line with a negative gradient, then the rate of reaction is
constant no matter what the concentration of the reactant. In other words, the
reaction is zero order with respect to the reactant.

Example:

Here, 1st half-life, 2nd half-life, 3rd half-life all are 100, so this the example of 1st
order with respect to the concentration of the reactant plotted.
Summary:
ii) A graph of reaction rate against concentration tells us whether a reaction is
zero, first, second or third order with respect to a particular reagent (or overall). It
is very rare to obtain an order with respect to a particular reagent higher than
second order. Following figure shows the shapes of the graphs expected for
different orders of reaction.

. If he plot of reaction rate against concentration is a horizontal straight line and

the reaction rate does not change with concentration; then, this is a zero-order
reaction.
. If the plot of reaction rate against concentration is an inclined straight line going
through the origin and the rate is directly proportional to the concentration of the
reactants and also doubling the concentration reactant doubles the rate of
reaction; then, this is example of 1st order reaction.
. If the plot of reaction rate against concentration of reactant is an upwardly
curved line and also reaction rate is directly proportional to the square of the
concentration of the reactant, indicating the 2nd order reaction. This means that,
When the concentration of reactant doubles, the rate of reaction increases four-
fold. We can say:
Following graphs are used to express this:
iii)

For example:
11.6: Understand how to:
i) obtain data to calculate the order with respect to the reactants (and the
hydrogen ion) in the acid-catalysed iodination of propanone.
ii) use these data to make predictions about species involved in the rate-
determining step..
iii) deduce a possible mechanism for the reaction.

The following data obtained from various experiment.

So, overall mechanism:

CH3(OH) CH2 is fast and iodine molecules are not involved in the mechanism until
after the rate determining step. So the rate of reaction does not depend on the
concentration of iodine. Again, as the step two is the slow step; so, the rate
determining step is:
11.7: Be able to deduce the rate-determining step from a rate equation and vice
versa.

The rate-determining step can be derived from the rate equation, and also a rate
equation can be drawn from the rate-determining step.

Explanation:

Here, the rate equation saying that, the reaction is zero order with respect to H +
meant that H+ has no impact on the rate of reaction; and overall the reaction is an
example of 2nd order.

In mechanism 1, H+ present in the first step. If this were the mechanism, then the
reaction would be the 1st order with respect to H+.

In mechanism 2, one mole of CH3CHO and one mole of CN- in the first step and
this is consistent with the reaction being 1st order with respect to each reactant.
Also, H+ appears after the rate determining step , so is consistent with the
reaction being zero order with respect to H+.

So the rate determining step is to step 1.

11.8: Be able to deduce a reaction mechanism, using knowledge of the rate
equation and the stoichiometric equation for a reaction.

A reaction to take place, at first particles have to collide in the correct orientation
and with sufficient energy of products to be formed.

This is the general expectation for this reaction in which the reaction is 1 st order
with respect to each reactant and second order overall. The fact is that, here an
assumption has been made. The assumption is to – a single collision has been
taken place between these two reactant particles which is described as
‘elementary’. If it is known that the reaction is elementary, then the rate law can
be deduced directly from the stoichiometric equation. For example, the following
reaction known to be elementary.

So, a series of experiment is needed to get the rate equation.

This rate equation indicating that, the stoichiometric equation does not reflect
the rate equation all the time.
Using the knowledge, it can be said that, two rate determining steps might be
there.

Without not doing any further experiment it cannot be said what is the
mechanism of this reaction. Using the second one, the following mechanism can
be consistent with.

There is also might be a mechanism:

But, the existence of NO3 is not familiar with. So, this cannot be the mechanism.
11.9: Understand that knowledge of the rate equations for the hydrolysis of
halogenoalkanes can be used to provide evidence for SN1 and SN2 mechanisms
for tertiary and primary halogenoalkane hydrolysis.

For tertiary halogenoalke:

For primary halogenoalkane:

11.10: Be able to use calculations and graphical methods to find the activation
energy for a reaction from experimental data The Arrhenius equation will be
given if needed.

The following data is used to do this.

11.11: Understand the use of a solid (heterogeneous) catalyst for industrial
reactions, in the gas phase, in terms of providing a surface for the reaction.

Particular conditions of temperature and pressure are required to form ammonia

from nitrogen and hydrogen. The reaction is catalysed by iron. The catalyst works
by allowing hydrogen and nitrogen molecules to come close together on the
surface of the iron. They are then more likely to react. Figure 22.24 shows the five
steps in this heterogeneous catalysis.

i) Diffusion: nitrogen gas and hydrogen gas diffuse to the surface of the iron.

ii) Adsorption: the reactant molecules are chemically adsorbed onto the surface
of the iron. The bonds formed between the reactant molecules and the iron are: –
strong enough to weaken the covalent bonds within the nitrogen and hydrogen
molecules so the atoms can react with each other – weak enough to break and
allow the products to leave the surface. Here is the adsorption of hydrogen
molecule onto nickel surface.

iii) Reaction: the adsorbed nitrogen and hydrogen atoms react on the surface of
the iron to form ammonia.
iv) Desorption: the bonds between the ammonia and the surface of the iron
weaken and are eventually broken.
v) Diffusion: ammonia diffuses away from the surface of the iron.
All the steps can be depicted with following images: