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Definition: - It is a branch of physical chemistry which deals with:

1. The study of speeds or rates of chemical reactions.


2. The factors which influence the rate of chemical reactions and
3. the mechanism through which the reactants pass into the products

Chemical Reaction: - The process involving the breaking and making and reshuffling a of chemical bonds
is known as chemical reaction. A chemical reaction should fulfill the following conditions:

1. Reading molecules should collide together at the same time.


2. Reacting molecules should possess the minimum energy (Threshold energy) to initiate the
molecular rearrangement.
3. The reacting molecules must be in proper orientation i.e. there should be a proper molecular
alignment among the reaction molecules.

Rate of reaction: - The rate of chemical reaction means the speed with which the reactants change into
products. It is generally expressed as the decrease in concentration of reactants or increase in
concentration of products per unit time. Thus the rate of a chemical reaction may be defined as the
change in the concentration of nay one of the reactants or products per unit time.

Since the rate of reaction depends upon the molar concentrations of the reactants which generally keep
one decreasing with the passage of time (while concentrations of the products keep on increasing)
therefore the rate of reaction is expressed either as the average rate of reaction or instantaneous rate
of reaction.

Average or Reaction:- This is the approximate way of expressing the rate of reaction and is defined as
the rate of change of concentration per unit time. I t is calculated by dividing the total change in
concentration of any one of reactant or product by the total time taken to do so. Thus

Average rate of reaction =

The rate calculated in this way cannot be exact (but approximate) because it is assumed that the
rate would be constant for the whole spam of time for which it is calculated. But on the contrary the
rate of reaction is not constant but varies with time, since rate of reaction changes at every moment
(due to change in concentration of reactants), Therefore, it is more appropriate to express the rate
of reaction as instantaneous rate which is defined as under

Instantaneous rate of reaction: - It is defined as the decrease in concentration of any one of the
reactants or increase in concentration of any one of the products at a particular instant of time.

If c is the concentration of nay reactant and x is the concentration of any product formed at any
time t, then rate of reaction is given by
[] []
= =

[] []
= =

Where square brackets represents the molar concentrations (moles/litre) of the reactants and
products. The ve sign indicate the decrease in concentration of reactants and +ve sign indicate the
increase in the concentration f products. When time interval is made infinitesimally small (dt)
then change in concentration is represented by dx (very small) change in concentration) and the

expression becomes dx/dt i.e. average rate approaches instantaneous rate.

For a general reaction

+ +
The rate of reaction is expresses as
1 [] 1 [] 1 [] 1 []
= = = =

Expressions for rates of some reactions are as follows:

I) 2 + 32 23

[2 ] 1 [2 ] 1 [3 ]
=
= 3
= +2

II) 22 5 22 4 + 2

1 [2 5 ] 1 [2 4 ] [2 ]
= = = +
2 2

III) + 3 2 + 2
[] [3 ] [2 ] [2 ]
= = = =

IV) 2 + 2 2
[2 ] [2 ] 1 []
=
=
=2

V) 5 3 + 2
[5 ] [2 ] [2 ]
= = + =

Units of rate of reaction:-

Since concentration is expressed in moles/litre and time expressed in second or minutes, therefore
the unit of the rate of reaction are moles litre -1 sec-1 or moles litre-1min-1.

In case of gaseous reaction pressure is used in place is expressed in atmospheres therefore the units
of the rate of reaction will be Atmp. Sec-1 or Atmp. Min-1.

Factors affecting the rate of reaction:- the rate of any particular reaction depends upon the
following factors:
1. Concentration of the reactants:- Since the concentration of the reactants is maximum at the
start of the reaction and , therefore the rate of change of concentration is also maximum. As
the concentration of the reactants decrease, t brings about e corresponding decrease in the rate
of reaction. This means that the rate of a reaction is directly proportional to the concentration
of the reactants. For example the rate of burning of wood depends upon the concentration of
oxygen. A piece of wood burns slowly in air but burns rapidly in pure oxygen. Also, the rusting of
iron accelerates during rainy seasons because of high concentration of water.
2. Presence of Catalyst:- A Catalyst is substance which influence the rate of reaction without
undergoing any permanent chemical change in itself. Many reactions proceed at an increased
rate by the presence of certain catalyst. For example, a mixture of H2 and O2 does not react at
room temperature. However, in the presence of a catalyst such as finely divide platinum, the
reactions become quite vigorous. In case of reversible reactions, a catalyst helps to attain to
equilibrium quickly without disturbing the state of equilibrium.
3. Temperature:- The rate of reaction increases with increase of temperature. In most of the cases,
the rate of reaction becomes nearly double for every 10 rise of temperature. In some cases,
reactions do not takes place at room temperature but take place at high temperature. In general
, an increase in the temperature increases the rate of almost all chemical reactions, on the other
hand, a decrease in temperature decrease the rate.
4. Nature of reactants and products. Rates of reactions are influenced by the nature of reactants
and products. A chemical reaction involves the breaking of bonds in reaction and formation of
new bonds in products. The reactivity of a substance can, therefore, be related to the ease with
which he specific bonds are broken or formed and the number of such bonds involved. For
example the oxidation of nitric oxide to Nitrogen dioxide takes place fast while oxidization of
carbon monoxide to carbon dioxide takes place slowly.
5.
2() + 2 () 22 () Fast

2() + 2 () 22 () Slow

In these two reactions the reaction species appear to be very similar to each other. Still
they differ in reaction rates because energy of activation is low in case of NO and high in case of
CO.
6. Surface Area:- The larger the surface area of the reactant, the faster is rate of reaction. I have
been observed that if one of the reactants in a solid, then the rate of reaction depends upon the
state of sub-division of the solid. This face is supported by the general observation that finely
divided solid reacts faster than massive substance. For example a log of wood burns slowly but if
it is cut into smaller wooden chips , the burning takes

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And may or may not be equal p ad q ( the values of p and q are determined experimentally and cannot
be deduced from balanced equation, p+q represents the order of the reaction). However, in on
elementary reaction p and q may be equal to a and b.
On the other hand, the law of mass action gives the rate expression on the basis of overall balanced
equation for the reaction e.g. in the following reaction. XXXXXXXXXXXXX the rate expression on the
basis of law of amass action is

Rate = K[NO2]2 [F2]

While as the rate of this reaction as found experimentally is proportional to the product of single
concentration term NO2 and F2 and therefore according to rate law

Rate = K[NO2] [F2]

Where K is a constant called velocity constant or rate constant or specific reaction rate.

If the concentration o f all the reacting species is taken as unity , then

Rate = k

Hence, rate constant may be defined as the rate of reaction when concentration of each reactant is
taken as unity. It is for this reason that rate constant is also called as specific reaction rate.

Molecularity:- The number of reacting atoms, ions or molecules that colloid simultaneously with another
to bring about a chemical reaction in a single actual step is called Molecularity of the reaction. However
Molecularity cannot be zero, negative or factional and also Molecularity beyond three has no
significance.

If a reaction involves the decomposition of only one species, the reaction is called as unimolecular
reaction e.g.

XXXXXX

If the reaction involves the collision of two species, the reaction is called as bimolecular reaction

XXXXX

If three species take part in collision leading to the formation of products, the reaction is called as
termolecular or tri molecular reaction e.g.

XXXXXX

All above reactions are simple or one step reactions and are known as elementary reactions. The
Molecularity of such reactions is equal to the number o molecules of the reactants taking part in a
chemical reaction i. e. the sum of the molecules of the reactants is balanced chemical equation.
However, the simultaneous collisions between more than three atoms, ions or molecules are usually
uncommon and therefore, for most of the reactions the Molecularity does not exceed there.

Order of reaction:- It is not always possible that the concentration of all the reactants which participate
in chemical reaction (step) can determine the rate of reaction. But only those reacting species whose
concentrations get altered during a chemical change can determine the rate of that reaction. The
dependence of reaction rates on concentration is expressed in terms of order of reaction which is
determined experimentally and is defined as , the total number of atoms, molecules or ions whose
concentration actually alters during a chemical reaction.

For a general reaction, it is defined as the sum of the powers to which the concentration of pressure
terms are raised in the rate low expression to express the observed ate of reaction.

Consider a general reaction.

XXXXXX

If the rate law expression for this reaction is

XXXXXX

Then the order of above equation if equal to (p+q). The values of p and q are determined
experimentally and have no relation to the stoichiometric coefficients a and b of the balanced
chemical equation. Order of reaction with respect o A is P and that with reapect to B is q and overall
order of the reaction is (p+q). if (p+q) =1 , the reaction is said to be first order reaction. If (p+q) =2 or 2,
the reaction is called second order or third order reaction respectively. So, the order of reaction can be
negative, zero, fractional first, second, third or higher some common examples of reactions of different
orders are as under

1. Decomposition of Nitrogen pentoxide (N2O5)


2. XXXXXX

Experimentally it is found that,

Rate of reaction =K[N2O5] ; order 1

i.e. the rate of the reaction depends on only one concentration terms, therefore the reaction is said to
be of first order.

2. Reaction between H2 and I2

1. XXXXXX
2. XXXXXX
3. XXXXXX
4. XXXXXX
5. XXXXXX
6. XXXXXX

Therefore, order with respect to O3 is 2 and with respect to O2 -1 (negative).

So, it is an example of negative order reaction.

Pseudo First order Reaction


The reactions which are not truly of first order but under certain conditions follow first order Kinetics
are called Pseudo First order Kinetics e.g. Consider the acidic hydrolysis of

1. XXXXXX

The Molecularity of the reaction is two because it involves two reacting species viz ethyl-acetate and
water. However the concentration of ethyl-acetate changes. During the reaction while water is present
in such as large excess that its concentration remains practically unchanged. Therefore the rate of the
reaction as determined experimentally depends only on the concentration of ethyl-acetate and hence
the order of reaction is one

Similarly acidic hydrolysis of sucrose (inversion of cane sugar) is a pseudo first order reaction whose
Molecularity is two but order is one. As XXXXXX

Units of rate Constants for reaction of different orders:-

Units of rate constant:- the rate constant K has different units for reactions having different orders. IN
general, then its of rate constant for the reaction of nth order are

1. XXXXXX


K= []
or K= ()

1 1
K= ( 1 )
or K = ( 1 )1

mol l-1sec-1 or K = (mol l-1)1-n

And for gaseous reactants of nth order, units of rate constant,

K = atmp. Sec-1 or K = (Atmp)1-n sec -1

i) For Zero order reactions:


Rate = K[A]o
K = mol l-1 sec-1.
Thus, units of k for zero order reactions are same as that of rate of a reaction i.e. mol l-1 sec-1
ii) For First Order Reaction
Rate = K[A]
K = sec-1
Thus, unit of rate constant of first order reaction are sec-1
iii) For Second order reaction
Rate = K[A]2
K = 1 / mol l-1sec
Thus, units of rate constant of second order reaction are l.mol-1sec-1
iv) For Third order reaction
Rate = K[A]3
K = 1/ mol2 l-2 sec
Thus, units of rate constant of third order reaction are l2 mol-2 sec -1

Integrated Rate Expression of Zero Order


A reaction is said to be of zero order of its rate is independent of the concentrations of reactants i.e. in
these reactions the concentration of reactants do not change with time, hence the rate of reaction
remains constant throughout.
Consider the general reaction.

A ----------> Products
If it is a reaction of zero order.
Rate = -d[A] = K[A]o = K
dt
or d[A] = -kdt
Integrating both sides, we get
[A] = -kt + I -------------------------> (i)
Where I is a constant of integration at, t=0, [A] = [A]o

, [A]o = I
Substituting this value of I in equation (i), we get
[A] = -kt + [A]o -------------------------------> (ii)

Or kt = [A]o -[A]

Or k = 1/t { [A]o - [A] } -----------------------------> (iii)

Any reaction of zero order must obey equation (ii). As it is an equation of a straight line (y = mn+c), the
plot of [A] versus t will be a straight line with slope = -k and intercept on the concentrations axis =[A]o as
shown in fig.

Plot at page no. 17 here

Plot of [A] verses t for reactions of Zero order


Also, as rate is independent of concentration, plot of rate verses concentration will be a straight line
parallel to concentration axis.

Plot at page no. 17 here

Plot of Rate versus concentration for reactions of zero order.

Half-life period: Half-life Period (t ) is the time in which half of the substance has reacted. This implies
that when [A] = [A]o /2 , t = t .
Substituting these values in equation (iii), we get
1 []
t = { [A]o - 2
}

= [Ao] / 2k.

i.e. t = [A]o / 2k

The half-life period of a zero reaction is directly proportional to initial concentration i.e. t x [A]o.
Hence a plot of t versus [A]o will be a straight line passing through the origin and slope = k.

Plot at page 18 Here..

(Plot of Half life (t ) versus initial concentration for a zero order reaction )

Integrated rate expression of first order reaction: -

A reaction is said to be of the first order if the rate of the reaction depends upon one concentration
term only.
Let us consider the simple reaction viz
A ---------------------------------> Products
Suppose we start with A moles per liter of the reactant A. After time t, suppose x moles per litre of it
have decomposed. Therefore, the concentration of A after time t = (a-x) moles per litre. Then according
to law of mass action.
Rate of reaction x (a-x)

i.e.
x (a-x)

or
= k (a-x) ------------------> (i)

Where k is called the rate of constant or the specific reaction rate for the reaction of the first order.
The expression for the rate constant k may be derived as follows:
Equation (i) may be rewritten in the form

= -------------------> (ii)

Integration equation (ii), we get




= .

i.e. ln (a-x) = kt + I ------------------------------> (iii)


Where I is constant of integration. At the beginning, when t =0, n=0 (as no substance has decomposed at
the start of reaction)
Putting these values in equation (III), we get
-ln(a-0) = k+0 +I
Or ln a = I ---------------------> (iv)
Substituting this value of I in equation (iii), we get

-ln(a-x)= kt+(lna)
Or kt =ln*a/a-x (v).
Or k = 2.303/T*log*a/a-x (vi)
Equation (vi) is sometimes written in another form which is obtained as follows;
If the initial concentration is [A]o and the concentration after time t is [A], then
Putting a [A]o and (a-x)=[A] ,equation (iv) becomes

K = 2.303/t*log*[A}o/[A].(vii)
Further putting a =[A]o and (a-x)=[A] in equation (v), we get
Kt = ln[A]o/[A]
Which can be written in the exponent form as
[A]o/[A]=ekt or [A]/[A]o

Graphical Method:-
Equation (vii) may be written as

[]
= = log[] = log[]
2.303 []

Or log[A] = -2.303 + log[] ----------------------------------------> (ix)

This is the equation of a straight line (y=mx+c). This if log[A] or log(a-x) values are plotted against time t
the graph obtained should be a straight line if the reaction is of the first order. The intercept made on
the y-axis would be log[Ao] and the scope of the line would be equal to (-k/2-303)
i.e. Slope =
from this, the value of K can be calculated

Half life period ;-

The time taken for any fraction of the reaction to be completed is independent of the intitial
concentration
Since, k= 2.303 /k log a/a-x ----------->(x)

When half of the reaction is completed x = a/2. Representing the time taken for half of the reaction ot
be completed by t1/2, equation (x) becomes

Thus a does not appear in this equation so that t1/2 is independent of a.

Temperature Dependence of the Rate of Reaction


Or
Effect of temperature on rate constant Arrhenius equation

Temperature has a great effect on the rate of a reaction. For most of the reactions, the rate of the
reaction becomes double or more for every 10o rise of temperature. This effect is usually expressed in
terms of temperature coefficient which is expressed by the following expressions:
+10 308
Temperature coefficient =
= 298

For most of the reactions temperature coefficient lies between 2 and 3. The ratio of rate constants
differing by 10o rise of temperature (preferably for 298 k and 308k) is known as temperature coefficient
of the reactions
The most satisfactory method for expressing the influence of temperature on reaction velocity was
studied by svante Arrhenius in 1889 and proposed the following postulates: -
1) During a chemical reaction molecules collide with each other but every collision is not effective.
2) The active molecules undergo effective collisions, hence lead to product formation. (the
remaining molecules are called passive molecules). There is equilibrium between active and
passive molecules. When temperature is increased the equilibrium is shifted to right).
Passive molecules active molecules
3) In order to get effective collisions, the energy of colliding molecules should be greater than
activation energy. To deduce a quantitative relationship between the rate constant and
temperature, he proposed an equation called Arrhenius equation which is as follows

K = A. e-Ea/RT
Where K = rate constant
R= gas constant
A= frequency factor or Arrhenius factor or pre exponential factor and is related to binary collisions per
second per litre.
Ea = Energy of activation

e-Ea/RT = Botzman factor which gives the fraction of molecules having energy equal to or greater than the
activation energy Ea.
From the Arrhenius equation is clear that the rate of reaction increases exponentially with the increase
in temperature.

Calculation of energy o f Activation (Ea):-


The energy of activation (Ea) is an important quantity and as the value of Ea increases, the value of K
decreases and therefore, the rate of reaction decreases. Using the above equation the value of Ea can
be calculated as

K = A. e-Ea/RT

Taking Logarithm,

Lnk = lnA -

Dividing both sides by 2.303, we get


Log K = log A - 2.303
Calculation of energy of activation of two different temperatures
If K1 and K2 are the rate constants at two different temperatures T1 and T2 respectively, then the above
equation becomes


Log K1 = log A - 2.3031 --------------------------> (i)

Log K2 = log A - --------------------------> (ii)
2.3032

Subtracting equation (i) from (ii), we have


Log k2 log k1 =
2.3031 2.3032
2 1 1
Log 1 = 2.303 [1 2
]

2 21
Log = [ ]
1 2.303 12

Thus knowing the value of rate constant k1 and k2 at two different temperatures t1 and t2, the value of
Ea can be calculated. Alternatively, knowing the rate constant at any one temperature. its value at
another temperature can be calculated provided the value of Ea is known for that reaction. When log k

is plotted against 1/t , we get a straight line whose intercept is equal to logA and slope is equal to 2.303


Therefore slope =
2.3031

Activation Energy (Ea)


According to collision theory of reactions the reacting molecules should collide with one another for a
reaction to occur. Out of the total number of collisions only those collisions result in the formation of
product which possess energy equal to or more than the certain minimum energy called threshold
energy. Collisions of the reacting molecules possessing energy less than threshold energy are ineffective
and do not result in the formation of products. It means that there exists a potential energy barrier
between the reactant and products which need to be crossed before which need to be crossed before
reactant can change into products and energy (threshold energy) is required to cross this barriers.
Usually al reacting molecules do not possess this energy in ground state. Thus some extra surplus or
bonus energy has to be supplied to reactants in order to make their energy equal to threshold energy.
This extra energy is called activation energy and is defined as the minimum extra energy cover (over
and above the average energy of reactants) required by the reactants to undergo a chemical change is
knowns as activation energy. It is denoted by Ea. In other words, it is equivalent to the difference
between the threshold energy for the reaction and the average kinetic energy of the reacting molecules.
Ea = Eth - Er
(activation Energy) (Threshold Energy) (Average K.E of Reactants)

The minimum amount of energy which the colliding molecules of reactant should possess to break the
bonds Is known as threshold energy. It is denoted by Eth.

The activation energy depends upon the nature of the chemical bonds which are joins to break. It is
independent of the initial and final energy constant of the reacting species (i.e. regardless of the fact
that a reaction is exothermic or endothermic) but depends upon mechanism or path followed by
reaction.
Each reaction has a definite value of Ea and this decides the fraction of total collisions which are
effective. If the activation energy for reaction is low, large number of molecules can have this energy
and the fraction of effective collisions will be large. The reactions will proceed at high rate. On the other
hand, if the activation energy is high, the fraction of effective collisions will be small and the reaction
may be quite slow.
, (. ) + = (. )

Where (. ) = Activation energy for forward reaction


(. ) = Activation energy Backward Reaction.

Collisions Theory of Chemical Reactions: -


It was proposed by Max. Trautz and William Lewis in 1916-18. It is based upon kinetic theory of gases.
According to this theory, it is assumed that the reactant molecules are hard spheres and reactions
between them occurs only when they colloid with each other. The number of collisions taking
Place per second unit volume of the reaction mixture is known as collision frequency Z. The value of
collision frequency is generally very high e.g. at ordinary temperature and pressure in the gaseous
system the collision system the collision frequency for binary collision is of the order of 1025 to 1028.
However, all the collisions are not effective but the collisions which actually produce the products are
called effective collisions. For producing effective collisions, molecules must have got sufficient energy
and proper orientation at the time of collision to overcome the two barriers.
a) Energy Barrier: - for breaking the chemical bonds, reacting molecules should possess the
sufficient energy which the colliding molecules of reactant should possess to break the bonds is
known as threshold energy the means that only those collisions whose energies are greater than
threshold energy can form the products.
b) Orientation barrier:- The reacting molecules should have proper orientation in order to break
the old bonds at the time of collision. The reactants, not possessing the threshold energy or
proper orientation do not products. E.g. let us consider the effect of orientation on the
dimerization of NO2 into N2O4 as follows
So the proper orientation of reactants leads to the bond formation whereas, improper orientation
simply makes them to bounce back and products are not formed.
Thus the collisions in which colliding molecules do not possess the minimum energy that is threshold
energy for effective collisions or proper orientation do not form products. In other words, the colliding
species rebound unchanged in such cases. Therefore, it follows that only a small fraction of collisions is
effective.
Thus the main points in the collision theory are:
i) For a reaction to occur these must be collisions between the reacting species.
ii) Only a certain fraction of the total number of collisions is effective in forming the products
iii) For effective collisions, the molecules should possess sufficient energy as well as
orientation. The fraction of effective collisions under ordinary conditions may vary from
nearly zero o about one for ordinary reactions.
Thus the rate of reaction is proportional to
a) The number of collisions per second per unit volume (collision frequency, z) between the
reacting species.
b) The fractions of effective collisions (properly oriented and possessing sufficient energy)


I.e. Rate = =

Limitations of collision theory


Though collision theory is able to explain the results of a number of reactions, yet it does not
give satisfactory results in some cases. This is because it assumes atoms or molecules to be hard
spheres and does not take into account their structural aspects some other theories like
transition state theory etc. have been put forward to explain the reaction rates.

Different between order & Molecularity of reactions

Orders Molecularity
1) It is the sum of the exponents of 1) It is the number of molecules of
molar concentration of reactant reactants taking part in a single step
given by equation of chemical reaction
2) It may or may not have relation with 2) It is calculated for reaction
stoichiometric equation for reaction. mechanism.
3) It depends on experimentally 3) It depends upon the rate
determined rate for the overall determining step of the reaction (in
reaction. the reaction)
4) It may be a whole number or 4) It is always whole number
fraction 5) It is a theoretical concept and can be
5) It is determined experimentally and calculated by adding the molecules
cannot be obtained from the of the slowest (rate determining)
balanced chemical equation step of reaction.
6) It can have all types of values i.e. 6) Its vale can never be zero and values
negative, zero and positive. more than three are least possible.