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Notes on Chemistry Chapter # 11

Reaction Kinetic

Chapter # 11 Reaction Kinetics

Introduction

11.0.0

Q.1: What is Chemical Kinetics?


Ans: The branch of chemistry which deals with the study of reaction
rates, factors affecting the reaction rates and mechanism of chemical
reaction is called Chemical Kinetics.
Q.2: What are types of reactions on the baises of rate of
reaction?
Ans: There are three types of reactions on the bases of rate of reaction
that are given as follows:
1). Fast Reactions: Those reactions which occurred instantaneously
(with in a fraction of seconds) are called fast reactions. E.g.
Precipitation of AgCl.
2). Moderate Reactions: Those reactions which occurred at
moderate rate are called moderate reactions. E.g. Hydrolysis of ester,
Fermentation of Milk.
3). Slow Reactions: Those reactions which take a much longer time
(months or years) are called slow reactions. E.g. Rusting of Iron,
Formation of fossil fuel
Q3. What is chemical kinetics? How do you compare chemical
kinetics with chemical equilibrium and thermodynamics? (Ex
Q.4)
Ans: Chemical thermodynamics can be used:
(i) To predict whether or not a reaction will proceed to the right, as
written.
(ii) To predict the extent to which a reaction will proceed before
reaching a condition of equilibrium.
(iii)To enable the amount of energy theoretically required by or
released during reactions to be calculated,
Thermodynamics cab tells us where the position of equilibrium lies
between the reactants and the products. It enables us to calculate the
equilibrium constants. It has the following limitations.
(i) It can only predict where possibility of a reaction but not its success.
(ii) It cannot tell us about the rate at which a reaction will occur. It is
because time is not a thermodynamic variable.
(iii) It provides no information about the mechanism of the reaction.
This is because the change in any state function is path independent.
Chemical kinetics can be used:
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Reaction Kinetic
(i) To determine the rate of reaction, that is the rate at which products
are formed or the rate at which reactions are used up in the reaction.
(ii) To understand the factors that affects the rate of a reaction.
(iii) To find the mechanism of a reaction.
Example: When gaseous H2 and O2 are mixed, thermodynamics tell us
that H2O should be formed, since H2O is more energetically stable than
H2 and O2. It is a well known fact that at room temperature, a mixture
of H2 and O2 will not produce H2O. However, if the mixture is sparked,
water is produced with explosive violence, thereby proving the
prediction of thermodynamics. However, it does not give any indication
of how fast the reaction will proceed.

11.1.0

Rate of Reaction

Q.1: What is meant by rate of reaction and give its units?


Ans: The rate of a reaction is defined as the change in concentration of
a reactant or a product per unit time taken for the change.
Rate of reaction =

C h angeconcentration of t h e substance
Time taken for t h e c h ange

The reaction rate decreases with time. It never remains uniform during
different time periods. It decreases continuously till the reaction
ceases. The units of rate constant are mol dm -3 s -1.
3

Rate of reaction =

moles dm
Seconds

Rate of reaction = mol dm

-3

-1

Q.2 Rate of a chemical reaction is an ever changing parameter


under the given conditions. Comment? (Ex.Q.8.i)
Ans: According to law of mass action, the rate of chemical reaction is
directly proportional to the product of active masses of reactants. In
the beginning when the reaction proceeds, its rate is very fast, while it
becomes slow, somewhere in the middle and very slow at the end. The
reason is that rate of reaction actually depends upon concentration of
active masses as concentration decreases every moment, in result rate
also decreases every moment and becomes zero at the end of reaction.
Q.3: The reaction rate decreases every moment but rate
constant k of the reaction is a constant quantity under given
condition. Justify it? (Ex.Q.8.ii)
The reaction rate decreases every moment since the concentration
of reactants decreases every moment. But the rate constant is the rate
of the reaction when the concentration of each reactant is taken as
unity.
Ans:

Consider a reaction:

A+B C+D

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Notes on Chemistry Chapter # 11


Reaction Kinetic
Rate = k [A] [B]
When the concentration of each reactant is taken as unity;
i.e., 1 mol dm-3. Then,

Rate = k [A] [B]

kx1x1 =

Thus, rate constant k of reaction is constant is constant quantity


under the given condition.
Q.4: Why the rate of a chemical reaction with respect to
product is written with a positive sign, but with respect to
reactants is written with a negative sign. Explain it with
reference to the following hypothetical reaction? (Ex Q.5)
aA + bB

cC + dD

Ans: The rate at which reaction proceeds can be expressed in terms of


the rate at which one of the reactant disappears or one of the products
formed.
Rate of Reaction

1
d

dx
dt

=-

1 d[A]
a dt

=+

1
c

d [B]
dt

d [C ]
dt

1
c

=+

d [D]
dt

The rate of chemical reaction with respect to reactants is written with a


negative sign because the concentrations of reactants decrease with
passage of time, since they are consumed during the reaction. The rate
with respect to products is written with positive sign because the
concentration of products increases with time, since they are formed
during the reaction.

Instantaneous & Average


Rate

11.1.1

Q.1: Differentiate between Instantaneous and Average rate of


reaction? Is it true that the instantaneous rate of a reaction at
the beginning of the reaction is greater than average rate and
becomes far less than the average rate near the completion of
reaction? (Ex Q.6)
Ans: The rate of reaction between two specific time intervals is called
the average rate of reaction. The rate of reaction at any one
instant during the interval is called the instantaneous rate.
The average rate and instantaneous rate are equal for only one instant
in any time interval. At first, the instantaneous rate is higher than the
average rate. At the end of interval the instantaneous rate becomes
lower than the average rate. The average rate will be equal to the
instantaneous rate when the time interval approaches to zero and that
time reaction will ne ceased or attain equilibrium state.

Specifc Rate Constant or Velocity


Constant

11.1.2

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Reaction Kinetic
Q.1: Differentiate between Rate of reaction and Rate
Constant? (Ex Q.7.i)
Rate of reaction

Rate Constant

1.The change in concentration


of a reactant or product per unit
time is called the rate of
reaction.

1.
The
proportionality
constant in rate law equation
which relates concentration to
the rate of reaction is called
2. It depends on concentration of rate constant of reaction.
reactants,
surface
area
of 2. It is independent of the
reactants,
temperature
and concentration of the reactant.
presence of catalyst. The reaction 3. Its units depend upon the
takes place in one phase.
order of reaction and differ
3. The mechanism involves the according to order of reaction.
formation of an intermediate
substance.
Q.2: Defne Velocity Constant or specifc constant of a reaction?
Ans: Velocity Constant or specific constant of a chemical reaction is the
rate of reaction when the concentrations of the reactants are unity.
Under the given condition, k remains constant but it changes with
temperature.
Consider a reaction:

aA + bB cC + dD
Rate of reaction = k [A]a [B]b

Let

[A] = 1 mol dm-3 and [B] = 1 mol dm-3

So Rate of reaction = k x 1a x 1b = k
Q.3: What is meant by Rate law?
Ans: The equation which describes the rate of a chemical reaction is
called rate law. The rate of a chemical reaction is directly proportional
to the product of concentrations of reactants each raised to some
power. Consider the following reaction.
aA + bB cC + dD . Rate of reaction [A]a [B]b. This equation is
called rate law.

Order of Reaction

11.1.3

Q.1: Defne and explain Order of Reaction?


Ans: The order of reaction may be defined as the number of reacting
molecules, whose concentrations alter as a result of the chemical
change. It is given by the sum of all the exponents (which are equal
coefficients as represented in balanced chemical equation) of the
concentrations terms in the rate law expression of the reaction is called
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Reaction Kinetic
order of reaction. The sum of the exponents in the rate equation may
or may not be same as in a balanced equation. It is determined
experimentally. The chemical reactions are classified as zero, first,
Pseudo first, second, third order and fractional order as well.
Consider a reaction: aA + bB cC + dD,

Rate = k [A]a [B]b

So the overall order of reaction is (a + b).


Q.2: When the reaction becomes zero order? OR. What is a zero
order reaction?
Ans: The reaction becomes zero order when it is entirely independent
of the concentration of reactant molecules. Photochemical reactions
are usually zero order. E.g. Photosynthesis etc. It occurs in plants in the
presence of chlorophyll and light.
Reaction is given as:

6CO2 + 6H2O C6H12O6 + 6O2

Q.3: Defne Ist order of reaction with the help of an example?


Ans: Example : Consider the decomposition of nitrogen pentaoxide.
2N2O5 (g) 2N2O4 (g) + O2 (g) Order of reaction is always determined
experimentally. Experimentally determined rate equation for this
reaction is as follows,
Rate = k [N2O5]1
Experimentally this reaction is first order with respect to the
concentration of N2O5, since the exponent to which the concentration of
N2O5 in the rate equation is raised is 1. Thus, the sum of all the
exponents to which the concentrations in the rate equation are raised
is called the order of reaction.
Q.4: The sum of the coefficients of a balanced equation is not
necessarily important to give the order of a reaction. Justify It?
(Ex.Q.8.vi)
Ans: The sum of the exponents to which the concentration terms in the
rate law are raised to express the observed rate of reaction is called
The order of reaction. The rate law, i.e. the order of reaction is
determined experimentally. The sum of the exponents in the rate law
equation may or may not be the same as in a balanced equation is not
necessarily important to give the order of reaction. E.g.
2N2O5 (g) 2N2O4 (g) + O2 (g)
According to the balanced equation
it is 2nd order reaction. But experimentally determined rate equation for
this reaction is as follows, Rate = k [N2O5]1. So it is first order reaction
instead of 2nd order reaction.
Q.5: The order of a reaction is obtained from the rate
expression of a reaction and the rate expression is obtained
from the experiment. Justify it? (Ex.Q.8.vii)
Ans: There is no simple relationship between the overall reaction and
the rate law expression. A reaction may consist of several elementary
steps (reactants) and the rate law expression is the combined result of

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Notes on Chemistry Chapter # 11


Reaction Kinetic
these steps. That is why we cannot predict the rate law expression
from balance equation. It must be determined experimentally.
Q.6: What are pseudo 1st order reactions? Explain with
example?
Ans: When one of reactant is taken in large excess or quantity its
concentration is considered as constant and the order becomes
pseudo. E.g. Hydrolysis of tertiary butyl bromide: In this reaction
water is solvent and taken in large quantity. So the concentration of
H2O is remaining constant. And rate of reaction is only dependent on
the concentration of tertiary-butyl bromide. So experimentally reaction
is considered as pseudo 1st order.
(CH3)3 CBr + H2O

(CH3)3 C OH + HBr

Excess
Rate = K [(CH3)3 CBr]
Q.7: What are 2nd order reactions? Explain with an example?
Ans: E.g. Oxidation of NO: Oxidation of NO with ozone is the first
order with respect to O3. The sum of all the exponents which are raised
to the concentration of the reactants according to the balanced
chemical equation gives the order of reaction i.e. 2. So the overall order
of reaction is two.
NO

(g)

+ O3

(g)

NO2

(g)

+ O2

(g)

Rate = k [NO] 1 [O3]1.


Q.8: The units of rate constant of second order reaction is
dm3 mol-1 s-1 , but the unit of rate of reaction is mol dm -3 s-1.
Justify it? (Ex.Q.8.v)
Ans: Rate =

[C]
T

mol dm3
s

= mol dm-3 s-1.

In the case of 2nd order of reaction, the rate equation for 2 nd order
reaction will be as
Rate = k [A] [B] k =

Unit of Rate constant


[ A ] [B]

mol dm
3
(3).(mol dm )
mol dm3 s1

= mol-1

dm3 s-1
Q.9: What are 3rd order reactions? Explain with an example?
Ans: Consider the following reaction
2FeCl3 + 6 KI 2 FeI2 +6 KCl + I2
The reaction involve 8 reactant molecules but experimentally it has
found to be 3rd order reaction. Actually this reaction involves 2 steps in
its mechanism. First step is called slow step and second step is known
as fast step. As slowest step is called rate determining step. And order

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Reaction Kinetic
of reaction is depends on the no of molecules which are involved in
slow step. Mechanism of this reaction is given as
1st Step: FeCl3 + 2KI

Slow

2FeI2 +2KCl + 2Cl

2nd Step: 2KI + 2Cl

Fast

2KCl +2I2

-1

-1

Q.10: What is meant by fractional order reactions? Explain with


an example?
Ans: Formation of CCl4: Formation of CCl4 with chloroform is a fractional
order reaction. CHCl3 + Cl2 CCl4 + HCl
Experimentally determined rate equation is Rate is [CHCl3]1 [Cl2]1/2.
As for as it is fractional order reaction because only one atom of
chlorine is involved so its half concentration is considered in rate law.
Sum of exponents = 1.00 + 0.5 = 1.5.

11.1.4

Half Life Period

Q.1: Defne half-life period of a reaction. Give example?


Ans: Half life period of a reaction is the time required to convert 50%
of reactants into products e.g. The half-life period for the
decomposition of N2O5 at 45OC is 24.0 minutes. For first order reaction,
half life period is independent of the initial concentration of reactants.
Q.2: 50% of a hydrogen frst order reaction completes in one
hour. The remaining 50% needs more than one hour to convert
itself into products. Why? (Ex.Q.8.iii)
Ans: The half-life period for the first order reaction is the time required
to convert 50% of the reactants into products. The half life for this first
order reaction is one hour. It means in one hour (one half-life) the
concentration of reactants decreases 50% and 50% will be left behind.
At the end of second half-life period, which occurs at 2 hours, the
concentration have decreased by one-half again from 50% to

1
2

50% = 25%. It means 75% of the reaction is completed in 2 hours and


87.5% will be completed in 3 hours and so on. Thus, the remaining 50%
needs more than one hour to convert itself into product.
Q.3: What type of information is obtained for the order of
reaction from half-period of that reaction?
Ans: The half-life period of any order of reaction is inversely
proportional to the initial concentration raised to the power one less
than the order of that reaction.
t
1
[ ]
2

initial

1
a

n1

. Here n is the number of order and a is the

concentration

of

reactants.

Thus,

knowing

the

initial

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Reaction Kinetic
concentration of reactants and half-life period of a reaction, then order
of that reaction can be determined. The concept of half-life period is
widely used in describing radioactive decay.
The half-period for the disintegration of a radioactive substance is
independent of the amount of that substance. The half-life period, for
the frst order reaction is independent of the initial concentration;
for second order of reaction the half-life period is inversely
proportional to the initial concentration of reactants. For a third order
reaction, half-life is inversely proportional to the square of initial
concentration of reactants.
Q.4: How the half-life period of chemical reactions is related
with the initial concentrations of the reactants for frst, second
and third order reactions?
Ans: Since, the values of the rate constants of different orders are
different, so their half-life period would be different for different order
reactions.
(i)
(ii)

For zero order reaction


For first order reaction

For second order reaction

=
(iv)

[t 1 ]
2

a
2

1
a0

, since

[t 1 ]
2

[t ]
1
2

1
1
a

; since

[t ]
1
2

1
ka

For third order reaction

0.693
k

(iii)

[t 1 ]

t1
2

]3

1
a2

;since

t1
2

]3

1.5
ka2

Q.5: The radioactive decay is always a frst order reaction.


Explain? (Ex.Q.8.iv)
Ans: The half-life of a radioactive nucleus is the time required for half
of any given quantity of a substance to react. The half-life of a radio-life
of a radioactive nucleus is independent of the amount of the sample.
For a first order reaction, the half-life is also independent of the initial
concentration of reactants; therefore, the radioactive decay is always a
first order reaction.

Rate Determ ining Step

11.1.5

Q.1: Defne Rate Determining Step with a reaction?

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Reaction Kinetic
Ans: If a reaction occurs in several steps, one of the steps is the
slowest. The rate of this step determines the overall rate of reaction.
This slowest step is called the Rate
Determining Step/Rate limiting Step.
Consider a reaction: NO2 (g) + CO (g) NO (g) + CO2 (g). The rate law for
this reaction is found to be as,
Rate = k [NO2]2
Q.2: Find rate law equation for the reaction?
NO2

(g)

+ CO

(g)

NO

(g)

+ CO2 (g)

Rate = k [NO2]2.

What information does this equation show? OR The rate


determining step of a reaction is found out from the
mechanism of that reaction. Explain it with few examples? (Ex.
Q.11)
Ans: Information: The rate law equation shows that the rate of
reaction is independent of the concentrations of CO. This reaction
appears to proceed in two elementary steps, each which is Bimolecular. The equation shows that two molecules of NO 2 are involved
in rate determining step (Slowest step). The mechanism of this reaction
is which is obtained experimentally is as follows:
In Slow way:

NO2

(g)

+ NO2

In fast way:

NO3

(g)

+ CO

(g)

Net reaction:

NO2

(g)

+ CO

(g)

(g)

NO3

NO2

NO

(g)
(g)

(g)

+ NO

(g)

+ CO2

(g)

+ CO2

(g)

.
.

So rate of reaction is only dependent on the two molecules of NO 2


which involves in the slow step . So the rate law for this reaction is Rate
= k [NO2]2. So the rate determining step of a reaction is found out from
the mechanism of that reaction not calculated from overall balanced
chemical equation.
Q.3: What is meant by Rate Determining Step?
Ans: The slowest step in the reaction mechanism is called Rate
Determining Step. The order of reaction is always calculated from the
sum of exponents which are raised to the concentration of molecules
involved in this slow step only.
Q.4: Write down a short note on The Reaction Intermediate?
Ans: The first step is the rate determining step and NO 3 which does not
appear in the balanced equation is called The Reaction Intermediate.
The Reaction Intermediate has a temporary existence and it is unstable
relative to the reactants and the products.
Q.5: What is meant by the term Elementary Step?
Ans: An Elementary Step is a process that occurs in a single event,
the order is given by the coefficients in the balanced equation for the
step.

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Reaction Kinetic
Q.6: What is a Reaction Mechanism?
Ans: A Reaction Mechanism is a series of elementary steps that
describe how an overall reaction occurs and explains the
experimentally determined rate law.
Q.7: How the mechanism of a chemical reaction can help to
point out the rate determining step?
Ans: A Chemical reaction that occurs by mechanism involves more
than one elementary step. Often one of the steps is much slower than
the others. The overall rate of a reaction cannot exceed the rate of the
slowest elementary step of its mechanism. Because the slow step limits
the overall rate, it is called the rate determining step. Thus, the
mechanism of a chemical reaction can help to point out the rate
determining step.
Q.8: Differentiate b/w Fast step and the rate determining step?
(Ex.Q.7.iii)
Ans:
Fast Step

Rate Determining Step

1. A relatively rapid step of the 1. The slowest step of the


reaction mechanism is called fast reaction mechanism is called rate
step.
determining step.
2. The overall rate of reaction is 2. The rate of this step determines
independent if this step.
the overall rate of reaction.

3. The number of molecules of 3. The number of molecules of


each reactant taking part in this each reactant taking part in this
step does not appear in the rate step appears in the rate equation.
equation.
Note: Remember that except the slow step, all other steps of the
reaction mechanism are normally faster steps. The terms slow and fast
are relative. They do not necessarily imply that the reaction itself is
slow or fast.
Determ ination of the Rate of a Chem ical
Reaction

11.2.0

Q.1: How the higher temperatures increase the rate of chemical


reaction? (or) How does the increase of temperature increase
the rate of a chemical of a chemical reaction?
Ans: As the temperature is increased, the added heat goes to increase
the fraction of the molecules with high kinetic energies, while the
fraction with low kinetic energies accordingly drops, thus raising the
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Notes on Chemistry Chapter # 11


Reaction Kinetic
average kinetic energy of molecules. So, there happens a distribution
of kinetic energies. Thus, the number of effective collisions increases
and hence rate increases.
Q.2: A reaction obeys the following rate low: Rate = k [A] [B] 2
(a) If [A] changes, will the rate change? Will the rate constant
change? Explain.
(b) What are the reaction orders for A and B? What is the
overall reaction order?
Ans: (a) If [A] changes, the rate will change, but the rate constant, k,
will remain the same. In the rate law, rate of reaction is the dependent
variable and reactant concentration are independent variables. The
rate constant, k, is the proportionality constant that does not change
unless the temperature changes.
(b) The reaction is first order in A, a second order in B, and third orders
overall.

11.2.1

Physical M ethods

Q.1: Defne Physical Methods with only names?


Ans: In the Physical Methods, A curve has to be plotted. The nature of
the curve may be rising for products and falling for reactants.
The Physical Methods are five that are following:
(i) Spectrometry
(ii) Electrical Conductivity Method (iii)
Dilatometric Method
(iv) Refractrometric Method

(v) Optical Rotation Method

Q.2: Write down


explanation?

Physical

the

Methods

with

complete

Ans: The physical methods are five that are following:


(i): Spectrometry: This method is applicable if a reactant or a product
absorbs ultraviolet, visible or infrared radiation. The rate of reaction
can be measured by measuring the amount of radiation absorbed by
some species of spectrometer.
(ii): Electrical Conductivity Method: The rate of a reaction
involving ions can be studied by electrical conductivity method. The
conductivity of such a solution depends upon the rate of change of
concentration of the reacting ions or the ions formed during the
reaction. The conductivity will be proportional to the rate of change in
the concentration of such ions.
(iii): Dilatometric Method: This method is useful for those reactions,
which involve small volume changes in solution; the volume change
is directly proportional to the extent of reaction.

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Reaction Kinetic
(iv): Refractrometric Method: This method is applicable to reactions
in solutions, where there are changes in refractive indices of the
substances taking part in the chemical reactions.
(v): Optical Rotation Method: In this method, the angle through
which plane polarized light is rotated by the reacting mixture is
measured by a polarimeter. The extent of rotation determines the
concentration of optically active substance, If any of the species in the
reaction mixture is optically active, then this method can be following
to find out the rate of reaction.

11.2.2

Chem ical M ethod

Q.1: Defne Chemical Method in Short term?


Ans: This is particularly suitable for reactions in solution. In this
method, we do the chemical analysis of a reaction or a product. E.g. the
acid hydrolysis of an ester (ethyl acetate) in the presence of a small
amount of an acid is one of the best examples.
CH3COOC2H5

(l)

+ H2O

(l)

CH3COOH

(l)

+ C2H5OH

(l)

This reaction occurred in the presence of H + (Acid or Acidic catalyst).


Energy of Activation (E a )
Vip.Long.Q

11.3

Q.1: Defne Activation Energy and Activated Complex or


Transition State?
Ans: The minimum amount of energy required for an effective collision
is called Activation Energy. The minimum amount of energy required
to initiate a reaction is called Activation Energy (Ea). The value of
Ea varies from reaction to reaction.
Activated Complex is an unstable combination of all the atoms
involved in the reaction that can break up to form products. The
particular arrangement of atoms at the top of the barrier is called the
Activated Complex. It is a short lived species and decomposes into
the product immediately. It has a short existence. Thats why it is called
Transition State or Intermediate state.
Q.2: Differentiate b/w effective and ineffective collision?
Ans: When a chemical reaction starts the molecule of reactants collide
with each other and must form a homogeneous mixture with each
other. The collision may be effective or ineffective; it depends upon the
energy of colliding molecules or particles. A collision is considered to be
effective if it gives rise to products and it will be ineffective if it not
gives the required product and the colliding molecules will just bounce
back and not convert in to the products.
Q.3: How number of effective collisions is related to Energy of
molecules?
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Reaction Kinetic
Ans: Molecules involving in the ineffective collision does not have
sufficient amount of energy to make ones collision effective, in which
result products are produced. So they required more energy to make
their collision effective. This minimum amount of energy which is
required for an effective collision is called Activation Energy. As the
energy of molecules increases by increasing the temperature the
number of effective collisions also increases.
Q.4: The collision frequency and the orientation of molecules
are necessary conditions for determining the proper rate of
reaction. Justify the statement?
Or. What conditions are
necessary for a reaction occur on the basis of collision theory?
(Ex.Q.14)
Ans: (1): The reactant molecules must collide with each other.
(2): The reactant molecules must possess activation energy, E a or
greater than Ea.
(3): The reactant molecules must be properly oriented.
Q.5: Two reactions have identical values for E a. Does this
ensure that they will have the same rate constant if run at the
same temperature? Explain it?
Ans: No. The value of A in Arrhenius Equation related to frequency
and effectiveness of collisions, can be different for each reaction and
k is proportional to A.
Q.6: What is relationship b/w Activation Energy (E a) and
Activated Complex?
Ans: Activation Energy appears as a potential energy hill b/w reactants
and products. Only the molecules collide with a kinetic energy greater
than Ea, will be able to climb the hill (activated complex) and form
products. And those molecules collide with a kinetic energy less than E a
will be unable to climb the hill (activated complex) and fall back
chemically unchanged. Finally it can say that greater the
activation energy slower will be the rate of reaction and vice
versa.
Q.7: Defne heat of reaction? Discuss it with respect to
Exothermic and Endothermic reactions?
Ans: heat of reaction is equal to the difference in potential energy of
reactants and products. OR Energy in the form of heat is either
absorbed or released during a chemical reaction is called heat of
reaction.
Exothermic Reactions: Those chemical reactions in which heat is
released from the system to surrounding are called exothermic
reactions. Its mean energy of reactants is higher than products so
energy is released when reaction moves in forward direction. Negative
sign of enthalpy changes H= -ive shows energy is released.

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Reaction Kinetic
Endothermic Reactions: Those chemical reactions in which heat is
absorbed from the surrounding to system are called endothermic
reactions. Its mean energy of reactants has lower energy than
products so a continuous source is needed to complete a reaction.
Positive sign of enthalpy changes H= +ive shows energy is
absorbed.
Q.8: Discuss the activation energy for forward and backward
reaction?
Ans: The activation energy for forward and backward reaction is
different. As forward reactions (Irreversible) are mostly exothermic and
backward reactions (Reversible) are mostly endothermic reactions. So
for exothermic reactions the energy of activation of forward
(Irreversible) reaction is less than that of backward reaction. Because in
exothermic reactions reactants have already high energies than
products. So during this reaction energy is released. While in
endothermic reactions energy of activation of backward (Reversible)
reaction is high than that of forward reaction. Because in endothermic
reactions reactants have low energy than products. So a continuous
source of energy is required to move a reaction.
Q.9: Differentiate b/w Enthalpy change of reaction and energy
of activation of reaction? (Ex Q.7.iv)

Ans:
Enthalpy change of reaction

Energy of activation of reaction

1. The heat change when the


reaction is carried out at constant
pressure is called enthalpy change
of reaction.

1. The minimum amount of


energy, in addition to the average
kinetic energy. Which the reactant
molecules must have for effective
collisions is called activation
energy of reaction.

2. It is the amount of heat evolved 2. It is the minimum amount of


or consumed in the course of energy required to initiate a
reaction.
reaction.
3. It is given the symbol, H.

Finding the O rder of Reaction

11.4

3. It is given the symbol, Ea.

Q.1: Write down the methods for fnding the order of reaction?
Ans: The methods for finding the order of reaction are following:
(i): Method of hit and trail
Method
(iv): Half-Life Method

(ii): Graphical Method

(iii): Differential

(v): Method of large excess

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Notes on Chemistry Chapter # 11


Reaction Kinetic
11.4.1

Halflife m ethod

Q.1: Describe Halflife method for fnding the order of reaction?


(Ex.Q.9)
Ans: The half-life period of any order of reaction is inversely
proportional to the initial concentration raised to the power one less
than the order of that reaction.
t
1
[ ]
2

1
n1

. Here n is the number of order and a is the

initial concentration of reactants. Thus, knowing the initial


concentration of reactants and half-life period of a reaction, then order
of that reaction can be determined. Lets us perform a reaction with
different concentration a1 and a2 and their half life time will be t 1 and t2
respectively. [t1

1
n1
a1

and

[t2

both relations we get following relations

t1
t2

1
n1 . Then by dividing
a2

a2
= [a1 ]

n-1

, by taking log

t1
a2
on both sides, log [ t 2 ] =n-1 log [ a 1 ]

t1
]
t2
n= 1+ log a 2
[ ]
a1
[

M ethod of Large Excess

11.4.2

Finally

Q.1: Discuss the method of large excess for fnding the order of
reaction?
Ans: In this method one of the reactant is taken in very small amount
as compared to the other reactants. The active mass of substance in
large excess remains constant throughout and the order becomes
pseudo. The order of reaction is totally depended on the substance
which is taken in small quantity because small change in
concentration of that substance which is taken in small
quantity is more effective on the rate of reaction. E.g.
Hydrolysis of tertiary butyl bromide: In this reaction H2O is solvent
and taken in large quantity so its concentration remains constant. And
rate of reaction is only dependent on the concentration of tertiary-butyl

20

Notes on Chemistry Chapter # 11


Reaction Kinetic
bromide due to its small amount or concentration. So experimentally
reaction is considered as pseudo 1st order.
(CH3)3 CBr + H2O

(CH3)3 C OH + HBr

Excess
Rate = K [(CH3)3 CBr]
Factors Aff ecting the rate of Reaction
(V.Im p)

11.5

Long.Q: Discuss the factors which influence the rates of


chemical reactions? (Ex.Q.12)
S.Q.1: Discuss the effect of Nature of reactants on the rate of
reaction?
Ans: Rate of reaction depends on the Nature of reactants substances.
Actually chemical activity of substances depends upon their electronic
configuration in their outer most orbitals. As the elements of IA group
has only one electron in their valence shell so they can easily lose it
and becomes more reactive (less stable) with water as compared to IIA
group elements because they have two electrons in their valence shell
and becomes less reactive (more stable) due to completion of their
duplet so they cannot easily lose electrons.
Q.2: What is effect of concentration of reactants affect on the
rate of reaction?
Ans: Effect of concentration of reactants is explained on the basis of
collision theory of reactants. The rate of reaction depends upon the
number of collisions b/w the reacting molecules. So greater the
concentration of reactants, greater the collisions and greater will be the
rate of reaction. E.g. combustion that occurs slowly in air (21 %
Oxygen) will occur more rapidly in pure oxygen.
Q.3: Describe how surface area affects on the rate of reaction?
Ans: The increased surface area of reaction increases the possibilities
of atoms and molecules of reactants to come in contact with each other
and rate increase e.g. Al foil reacts with NaOH moderately when
warmed but powered Al reacts rapidly with cold NaOH and H 2 is
evolved. 2Al + 2NaOH + 6H2O 2NaAl (OH)4 + 3H2
Q.4: How presence of light affects the rate of reaction?
Ans: In some reactions the rate of reaction also depends on the light
concentration. As light is a form of energy because it consists on
photons (small packets of energy). In the presence of light rate of
reaction increased. E.g. Reaction b/w H2 and Cl2 at ordinary pressure is
negligible in darkness, slow in daylight but it becomes explosive in
sunlight. Similarly light is vital in photosynthesis.
Q.5: How number of effective collisions or rate is related to
temperature or Energy of molecules?

20

Notes on Chemistry Chapter # 11


Reaction Kinetic
Ans: Molecules involving in the reactions are first colliding with each
other and form a homogeneous mixture. Some molecules which have
high kinetic energy than Ea their collision is more effective and
converts them into products easily. While molecules involving in
ineffective collision does not have sufficient amount of energy to make
ones collision effective, as a result required products are produced. So
they required more energy to make their collision effective. This
minimum amount of energy which is required for an effective collision
is called Activation Energy. As the energy of molecules increases by
increasing the temperature the number of effective collisions also
increases and rate of reaction increases.
Arrhenius Equation (V.im p
Long Q)

11.5.6

Q.1: What is an Arrhenius Equation?


Ans: The mathematical equation, which expresses the dependence of
the rate constant on temperature is called the Arrhenius Equation.
The rate constant k for reaction varies with temperature. According
to Arrhenius Equation k = Ae -Ea / RT Hence k is exponentially
related to activation energy, Ea and absolute temperature, T. R is
the gas constant and e is the base of natural logarithms. The factor
A is called Arrhenius Constant and it depends upon the collision
frequency of the reacting molecules.
Q.2: How does Arrhenius equation help us to calculate the
energy of activation of a reaction? (Ex Q.15)
The Arrhenius Equation, which expresses the dependence of the rate
constant on temperature, is:
k = Ae
ln k = ln Ae

- Ea / RT

, (Taking Natural logarithms on both sides)

ln k = ln A + lne

- Ea / RT

Ea
ln k = ln A + [ RT ]

- Ea / RT

lne, As lne= 1
So, ln k =

Ea
]
+ ln A,
RT

To convert the natural logarithms into

logarithms to the base 10 multiply log term by a constant 2.303,


2.303 log k =

Ea
RT

+ 2.303 log A (Divide the whole term

by 2.303)
(or)

log k =

E a
2.303 R

] []

1
T

+ log A

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Notes on Chemistry Chapter # 11


Reaction Kinetic

(Variable) (Slope) (Variable) (Intercept)


y

mx + c

(straight line equation)

When a graph is plotted between

[]

obtained. The slope of this line is

1
T

the activation energy. Hence Slope =

against log k, a straight line is

E a
2.303 R

from which we can obtain

E a
2.303 R

or

So

Activation

Energy) Ea = -slope x 2.303 R


Q.3: The reaction happens due to collisions among
molecules, but all the collisions are not fruitful. Justify it?

the

Ans: The reaction occur due to collisions among the molecules, but
every collision does not lead to a reaction. For a collision to be a fruitful
(effective), the molecules must possess the activation energy and they
must be properly oriented. Since all the molecules do not possess the
same energy. A fraction of molecules may have less energy than the
average energy and cannot attain the activation energy and are not
properly oriented. Therefore, all the collisions are not fruitful.
CATALYSIS (V.Im p L.Q + S.Q )

11.6

Q.1: What is Catalysis?


Ans: A substance that alters the rate of a chemical reaction, but
remains chemically unchanged at the end of the reaction. The process
or phenomenon which takes place in the presence of a catalyst is called
catalysis. A catalyst usually lowers the overall activation energy for a
reaction by providing a completely different mechanism for the
reaction. KClO3 decomposes much more rapidly in the presence of a
small amount of MnO4. In same way HCl is oxidized to Cl2 in the
presence of CuCl2.
Q.2: Differentiate between Homogeneous Catalysis
Heterogeneous Catalysis? (Ex Q.7.ii) (Ex Q.16,i,ii)

and

Ans: Homogeneous Catalysis: (1). A process in which catalyst


and reactant substances are present in the same phase and
homogeneous throughout is called a Homogeneous Catalysis. (2).
This reaction takes place in one phase. The catalyst is uniformly
distributed and is itself in the same phase. (3).The mechanism involves
the formation of an intermediate substance. E.g. Esters are hydrolyzed
in the presence of H 2SO4. Both the reactants and catalyst are in the
solution state or phase.
CH3COOC2H5 (l) + H2O (l)

H3O+ (l) CH3COOH (l) + C2H5OH (l)

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Notes on Chemistry Chapter # 11


Reaction Kinetic
Heterogeneous Catalysis: (1). A process in which catalyst and
reactant substances are present in the different phase is called
Heterogeneous catalysis. (2). In this process catalyst is usually as a
solid in contact with either gaseous reactants or with reactants in a
liquid phase. (3).The reaction takes place at a phase boundary. The
gaseous molecules react at the surface of the solid catalyst. (4). The
mechanism involves adsorption. Molecules are bound to active sites
on a solid. E.g. Hydrogenation of unsaturated organic compound is
catalyzed by divided Ni, Pd or Pt.

11.6.1

Ni(s)

CH3

__

CH3 (g)

Characteristics of a Catalyst

E.g. CH2 = CH2 (g) + H2 (g)

Q.1: Give four Characteristics of a Catalyst?


Ans: (i): A catalyst remains unchanged in mass and chemical
composition at the end of a reaction.
(ii): A catalyst cannot start a reaction which is not thermodynamically
feasible.
(iii): A catalyst is specific in its action.
(iv): A catalyst is more effective, when it is present in a finely divided
form.
Q.2: Briefly describe the following with examples: (Ex. Q.17)
Q.2 (i) Change of physical state of a catalyst at the end of
reaction?
Ans: There may be change in physical state such as the particle size or
change in the colour of the catalyst at the end of reaction. For example,
granular MnO2 used as a catalyst in the thermal decomposition of KClO 3
is left as fine powder at the end of reaction.
Q.2: (ii) A very small amount of a catalyst may prove sufficient
to carry out a reaction?
Ans: Since a catalyst is not used up in the reaction, a very small
amount of catalyst is required. It can catalyses the reaction over and
over again. Sometimes a trace of a metal catalyst is required to affect
very large amount of reactants. For example, 1 mg of fine platinum
powder can convert 2.5 dm3 of H2 and 1.25 dm3 of O2 to water. Dry HCl
and NH3 combine in the presence of trace of moisture to give dense
white fume of NH4Cl.
Q.2: (iii) A fnely divided catalyst may prove more effective?
Ans: A catalyst is more effective when it is present in a finely divided
form than it is used in bulk. With the increase of fine subdivision, the
free surface area is increased. As a result, the active sites on the
surface are increased. Consequently, the activity of the catalyst is also
20

Notes on Chemistry Chapter # 11


Reaction Kinetic
enhanced. For example, a lump of platinum will have much less
catalytic activity than colloidal platinum. Finely divided nickel is a
better catalyst than lumps of solid nickel.
Q.2: (iv) Equilibrium constant of a reversible reaction is not
changed in the presence of a catalyst?
Ans: A catalyst for the forward reaction is also a catalyst for the
reverse reaction. A catalyst speeds up the rate of both the forward and
reverse reactions equally. So the equilibrium constant (k = Constant)
for the reaction remains the same. A catalyst helps the equilibrium to e
established earlier. For example, the reaction of N 2 and H2 to from NH3
is very slow. In the presence of the catalyst (Iron), the equilibrium is
reached much sooner but the percentage yield remains unchanged.
N2 (g) + 3H2 (g) ( s)

2NH3 (g)

Q.3: What is meant by poisoning of catalyst? Give two


examples of catalytic poisoning? (Ex Q.16,v)
Ans: Catalytic poisoning occurs due to the presence of trace amount of
foreign substances, which render them ineffective. Such substances are
called Poisons. The poisoning of a catalyst may be temporary or
permanent. In permanent poisoning, the poison reacts chemically with
the catalyst. The compound of Sulphur and Arsenic behave as poison to
many metallic catalysts. E.g.(1). Arsenic present as impurity in contact
process for the manufacture of Sulphuric Acid makes the Pt inert. E.g.
(2) In the same way the presence of CO as an impurity with the
Hydrogen decreases the catalytic activity of catalyst in the Habers
process for the manufacturing of Ammonia.
Q.4: How does a Catalyst increase the rate of reaction?
Ans: The Catalyst increases the rate by changing the mechanism of
the reaction so as to decrease the energy of activation. Decreasing the
energy of activation the fractions of molecules that react thus increase
the rate constant and so a catalyst increases the rate of reaction.
Q.5: A catalyst is specifc in its action. Give reason?
Ans: When a particular catalyst works for one reaction it may not
necessarily works for one reaction it may not necessarily work for
another reaction. If different catalysts are used for the same reaction,
then product may change. For example, formic acid is decomposed, by
Al2O3 to H2O and CO while in the presence of Cu catalyst it decomposes
to H2 and CO2. Thus, a catalyst is specific in its action.
Q.6: What is effect of temperature on catalyst?
Ans: Some catalysts are physically changed by a change in
temperature and hence their power will be decreased e.g. colloidal
catalysts like Pt may be coagulated with rise in temperature.

20

Notes on Chemistry Chapter # 11


Reaction Kinetic
Activation of Catalyst

11.6.2

Q.1: What is a promoter or activator or Positive


Catalyst(Activation of Catalyst)? Or Differentiate between
positive and negative catalyst? (Ex Q.16,iii)
Ans: A substance which promotes (increase) the activity of a catalyst is
called a Promoter/Activator/Positive catalyst. It is also called
Catalyst for Catalyst. E.g.(1) The Catalyst activity of Ni can be
increased by using Cu and Te for the hydrogenation of vegetable oil.
E.g.(2) In the manufacture of ammonia by Habers process small
amount of Al2O3 or Cr2O3 increase the efficiency of iron (Fe) catalyst. A
catalyst which retards or slowdowns the rate of a reaction is called a
negative catalyst and the process is called Negative Catalysis. For
example, (TEL) Tetraethyl lead {(C2H5)4 Pb} is added to petrol,
because it saves the petrol from ignition.
Q.2: What is Negative Catalyst. Explain with an example?
Ans: A catalyst which retards or slowdowns the rate of a reaction is
called a negative catalyst and the process is called Negative
Catalysis. For example, (TEL) Tetraethyl lead {(C2H5)4 Pb} is added
to petrol, because it saves the petrol from ignition.
Q.3: What is Auto-Catalyst. Give an example? Or Differentiate
between auto catalysis and promoter? (Ex Q.16,iv)
Ans: In some reactions, a product formed acts as a catalyst. This is
called Auto-Catalyst. The phenomenon is called Auto-Catalysis. For
example, when copper is allowed to react with Nitric Acid, the reaction
is slow in the beginning. It gains the speed gradually and finally
becomes very fast. This is due to the formation of Nitrous Acid during
the reaction, which accelerates the process. So Nitrous Acid is known
as Auto-Catalyst.
Enzym e Catalysis (V.im p)

11.6.3

Q.1: What are Enzymes? Defne enzyme catalysis? (Ex Q.16,vi


& Ex. Q.18)
Ans: Enzymes are the complex protein molecules and catalyze the
organic reactions in the living cells. And those reactions in which
enzymes are used as catalyst are called as enzyme catalysis. The
enzyme molecules are a protein chain that tends to fold into a roughly
spherical form with an active site at which the substrate molecules
binds and the catalyst takes place. The substrate molecule, S, fits into
the active site on the enzyme molecule, E, just as a key fits into a lock,
forming an enzyme-substrate complex, ES, which yield the products , P,
immediately
E + S ES E + P
20

Notes on Chemistry Chapter # 11


Reaction Kinetic
Q.2: How enzymes catalyze Biological Reaction?
Ans: Enzymes are the complex protein molecules and catalyze the
Biological reactions in the living cells. Living organisms operate
efficiently in a very narrow temperature range: the role of enzymes as
homogeneous catalysts that speed up desirable reactions without
heating for Biological systems. Enzymes are highly specific, each
enzyme acting only on a specific substance. (1)The enzyme
Invertase, which is present in the digestive fluid of the small intestine,
catalyzes reaction of sucrose with water to form the glucose and
fructose. (2). In the same way Urea undergoes hydrolysis into NH3 and
CO2 in the presence of enzyme Urease.
e.g (1). C12H22O11

Invertase

C6H12O6 + C6H12O6

O
||
e.g.(2) NH2 CNH2 + H2O

Urease
2NH3 + CO2

(Urea)
Q.3: What are controlling factor on the action of Enzyme?
Ans: The activity of the enzyme is controlled by the pH and
temperature. The pH of the medium controls the rates of the enzyme
catalyzed reactions and the rate passes through a maximum at a
particular pH, known as optimum pH. The enzyme activity is lowers or
decreases at other value of pH. Thus, many enzymes of the body
function best at pH of about 7.4, the pH of the blood and body fluids.
Enzyme catalytic reactions have rates at an optimum temperature. The
rate of an enzyme catalyzed reaction is increased with rise of
temperature but up to a certain point. There after the enzyme is
denatured (destroyed). For example, the optimum temperature of
enzyme reactions occurring in human body is 37 oC (98.60 F).
Characteristic of Enzym e
Catalysis

11.6.4

Q.1: Give the four Characteristics of Enzymes? (Ex.Q.18)


Ans: (1): Enzymes are the most efficient catalysts and they lower the
energy of activation of a reaction.
(2): Enzymes catalysis is highly specific.
(3): Enzyme catalytic reactions have the maximum rates at an
optimum temperature and optimum pH.
(4): The activity of enzyme catalyst is inhibited by a poison.
Q.2: How does the activity of an enzyme is destroyed?
Ans: The activity of an enzyme is destroyed if some molecules in the
solution is able to bind strongly to the active site and block the entry of
the substance. Such substances are called Enzymes Inhibitors.

20

Notes on Chemistry Chapter # 11


Reaction Kinetic
H = E + P x 0 = E

H = E

20

Notes on Chemistry Chapter # 11


Reaction Kinetic

(Some Imp Short Questions from Past


Papers)
1.
2.
3.
4.
5.
6.
7.

Justify that the radioactive decay is always first order reaction?


Define and explain with example Ist, 2nd, 3rd, fractional or Pseudo order of Reaction?
Define activation energy and activated complex?
Diff b/w Homogeneous and heterogeneous catalysis?
Give the basic conditions for occurring a reaction according a collision theory?
What is meant by Catalyst activator and catalyst poisoning?
The order of reaction is obtained from rate expression of a reaction and the rate expression is obtained from
the experiment. Justify it?
8. The sum of coefficients of a balanced chemical equation is not necessarily important to give the order of
reaction. Justify it?
9. What are the names of controlling factors on the action of enzymes?
10. Define half life of reaction? Give example?
11. Explain auto catalysis.
12. Explain specific rate constant
13. A very small amount of a catalyst may prove sufficient to carry out a reaction. How?
14. A catalyst is specific in its action. How?
15. A finely divided catalyst is more effective. Why?

(Some Imp Long Questions from Past


Papers)
1. Define order of a reaction and explain how half life method helps to
determined order of a reaction?
2. Write a note on collision theory? Discuss it wrt Activation Energy?
3. Discuss the different factors which influence the rate of chemical reaction?
4. Explain the effect of temperature on rate of reaction by Arrhenius
equation?
5. Derive Arrhenius equation? How it is helpful for determination of activation energy of
reaction?
6. Write a note on Catalysis? Discuss its types with suitable examples?
7. Write any four characteristics of a catalyst or Enzymes Catalysis?

Written by

Mudasir Majeed
Ph.D Scholar (Applied Chemistry)
Email: mudasir_ jhang@yahoo.com
Quaid-e-Azam College of Science &
Commerce,Gojra

20