CHEMICAL KINETICS.

Chemical kinetics.

Branch of chemistry which deals with the study of reaction rates, the factors which influence the rate of
reactions and the mechanisms by which the reactions proceed is called Chemical kinetics.

Rate of a chemical reaction.

It is the change in concentration of any one of the reactants or any one of the products per unit time.
𝐂𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐂𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧
Rate of reaction = 𝐓𝐢𝐦𝐞 𝐭𝐚𝐤𝐞𝐧

Consider the reaction A →B

𝐂𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐂𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐀 𝐂𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐂𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐁
Rate of reaction = 𝐓𝐢𝐦𝐞 𝐭𝐚𝐤𝐞𝐧
= 𝐓𝐢𝐦𝐞 𝐭𝐚𝐤𝐞𝐧

Unit of Rate is mol litre-1 s-1 Or mol litre-1 min-1

Or in general unit of rate is mol litre-1 time-1

∆[𝐱]
Average rate. ( ∆𝐭
)

The change in concentration of any one of the reactants or any one of the products per unit time over a
specified interval of time is called average rate.

Consider the reaction A→ B

𝐝𝐞𝐜𝐫𝐞𝐚𝐬𝐞 𝐢𝐧 𝐂𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐀 −∆[𝐀]
Average Rate of reaction = 𝐓𝐢𝐦𝐞 𝐢𝐧𝐭𝐞𝐫𝐯𝐚𝐥
= ∆𝐭

𝐢𝐧𝐜𝐫𝐞𝐚𝐬𝐞 𝐢𝐧 𝐂𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐁 +∆[𝐁]

Or Average Rate of reaction = 𝐓𝐢𝐦𝐞 𝐢𝐧𝐭𝐞𝐫𝐯𝐚𝐥
= ∆𝐭

Change in concentration of reactants is always negative and the rate of the reaction is always positive.
Therefore, a minus sign is put when rate is expressed in terms of conc. of reactants so that the rate
becomes positive.

Expression of Average Rate.

For a general reaction, aA+ bB →cC + dD.

∆[𝐱] −∆[𝐀] 1 −∆[𝐁] 1 +∆[𝐂] 1 +∆[𝐃] 1
Average rate, = x = x = x = x
∆𝐭 ∆𝐭 𝑎 ∆𝐭 𝑏 ∆𝐭 𝑐 ∆𝐭 𝑑

−∆[𝐀]
The term ∆𝐭
= rate of disappearance of A
−∆[𝐁]
∆𝐭
= rate of disappearance of B
+∆[𝐂]
∆𝐭
= rate of appearance of C.
+∆[𝐃]
∆𝐭
= rate of appearance of D
Rate of appearance of products or rate of disappearance of reactants may or may not be equal to the
rate of the reaction.
𝐑𝐚𝐭𝐞 𝐨𝐟 𝐚𝐩𝐩𝐞𝐚𝐫𝐚𝐧𝐜𝐞 𝐨𝐫 𝐝𝐢𝐬𝐚𝐩𝐩𝐞𝐚𝐫𝐚𝐧𝐜𝐞
Rate of reaction = 𝐒𝐭𝐨𝐢𝐜𝐡𝐢𝐨𝐦𝐞𝐭𝐫𝐢𝐜 𝐜𝐨𝐞𝐟𝐟𝐢𝐜𝐢𝐞𝐧𝐭

Question: Write expressions for average rate in terms of concentration of all the reactants and products
for the following reactions.

1. N2 + 3H2→ 2NH3
2. H2 + I2 → 2HI
3. 2N2O5→ 4NO2 + O2.
𝐝[𝐱]
INSTANTANEOUS RATE OF A REACTION ( )
𝐝𝐭

The rate of change of concentration of any one of the reactants or products at a particular instant of
time is called instantaneous rate of reaction.

For a general reaction of the type,

aA+ bB →cC + dD.

∆𝑥 𝑑𝑥
lim = 𝑑𝑡
∆𝑡→0 ∆𝑡

𝑑𝑥 −𝐝[𝐀] 1 −𝐝[𝐁] 1 +𝐝[𝐂] 1 +𝐝[𝐃] 1

Instantaneous rate, 𝑑𝑡 = 𝐝𝐭
x𝑎 = 𝐝𝐭
x𝑏 = 𝐝𝐭
x𝑐 = 𝐝𝐭
x𝑑

Determination of Average rate of a reaction.

The average rate of reaction can be determined by graphical method. A graph is plotted between the
concentration of reactant (or product) and time as shown above. The average rate of a reaction is
determined by noting the concentration of reactants at two different times t1 and t2. If x1 and x2 are the
concentrations in the time interval between t1 and t2, then,
𝑥2 − 𝑥1
average rate ate = - 𝑡2 −𝑡1

Determination of instantaneous rate of a reaction.

A graph is plotted between concentration of reactants and time. Instantaneous rate is
determined by drawing a tangent to the curve at a point corresponding to the given time. Thus, the
slope of the tangent gives the instantaneous rate of the reaction at that time.

𝑂𝐴
The ratio 𝑂𝐵 gives the slope of the tangent
𝑂𝐴
Instantaneous rate = 𝑂𝐵 = slope.

COLLISION THEORY OF REACTION RATE.

1. A chemical reaction takes place due to the collision among the reactant molecules
2. All collisions do not lead to product formation. Only a fraction of the total number of collisions
are effective and leads to the formation of products.
3. Only those collisions are effective in which the colliding molecules possess a certain minimum
amount of energy called threshold energy.
4. For effective collisions, the colliding molecules should also have proper orientation so that the
old bonds may break and new bonds are formed.

Effective collisions.

Molecular collisions which lead to the formation of products are called effective collisions.

Conditions for effective collisions

1. Only those collisions are effective in which the colliding molecules possess a certain minimum
amount of energy called threshold energy.
2. For effective collisions, the colliding molecules should also have proper orientation so that the
old bonds may break and new bonds are formed.

Threshold Energy

The minimum amount of energy that must be possessed by reacting molecules to undergo effective
collisions (or to form products) is called threshold energy

Activation Energy

The excess energy that the reactant molecules must acquire to undergo effective collisions/ to form
products/to cross the activation energy barrier/to form activated complex is called Activation Energy.

Activation energy = Threshold Energy – average energy of reactant molecules

Higher the activation energy lesser is the rate of the reaction.

Collision Frequency

The number of collisions that takes place per second per unit volume of reaction mixture.

Activated complex.

When two molecules having energy equal to or greater than threshold energy collide each other, they
attain an intermediate configuration before they change in to products. This intermediate configuration
corresponding to the maximum energy of the system is called activated complex.

Activated complexes have very high energy and are highly unstable and short lived. As soon as they are
formed, they immediately split in to the products.

Activation Energy Barrier Diagram

For Exo-Thermic Reactions For endo-thermic reactions

ER – Energy of reactants Ep – Energy of products ET – Threshold energy

ΔH = Change in enthalpy (energy absorbed or evolved) Ea(f) – Activation energy of forward

reaction. Ea(b) – Activation energy of backward reaction.

Factors which affect the reaction rate.

i) Nature of reactants. The reactions involving ionic and polar compounds are fast and those
involving covalent compounds are slow.
ii) Concentration of reactants. The rate of a reaction usually increases with increase in
concentration of reactants. This is due to increase in the number of molecular collisions.
iii) Temperature. The rate of a reaction usually increases exponentially with increase in
temperature. The rate becomes 2 to 3 times for each 10° rise in temperature.
 iv) Presence of Catalyst. A catalyst (positive) increases the rate of a reaction. It provides an
alternative path of lower activation energy and helps a larger number of molecules to cross
the activation energy barrier.
v) Surface area. The rate of a reaction increases with increase in surface area of the reactant.
Increase in surface area increases the number of collisions and consequently the rate of
reaction increases.

Dependence of reaction rate on concentration of reactants

Law of mass action.

At constant temperature, the rate of a chemical reaction is directly proportional to the product of active
masses of reactants, with each active mass term raised to the power equal to the stoichiometric
coefficient of that reactant in the chemical reaction.

For a general reaction, aA+ bB →cC + dD.

Rate α [A]a [B]b

Rate = k[A]a [B]b

Where k is a constant known as rate constant or specific reaction rate or velocity constant.

Rate constant.

Rate constant is the rate of the reaction when concentration of each of the reactant is taken as unity.

Rate = k[A] a [B] b

When [A]=1 and [B]=1

Then, k = rate.

Rate law or rate equation.

The mathematical expression which describes the experimentally observed dependence of reaction rate
on the molar concentration of reactants is called rate law expression or rate equation.

Consider the reaction, aA+ bB →cC + dD.

According to the law of mass action,

Rate = k[A]a [B]b

But rate law is, Rate = k[A] p [B] q

Where p and q are determined experimentally and p and q may or may not be equal to a and b
respectively.

Order of a reaction

The sum of the powers to which the molar concentration terms of reactants are raised in the rate law
expression is called order of the reaction.
 For the reaction, aA+ bB →cC + dD.

Rate law is, Rate = k[A] p [B] q

Order of the reaction = p + q

Order of the reaction w r.to A = p

Order of the reaction w r.to B = q

Over all order of the reaction = p + p

Example of First Order Reactions

1. Decomposition of N2O5
N2O5 → 2NO2 + ½ O2 Rate = k[N2O5]
2. Decomposition of H2O2
H2O2 → H2O + ½ O2 Rate = k[H2O2]
3. Decomposition of ammonium nitrite
NH4NO2 → N2 + 2H2O Rate = k[NH4NO2]
4. Decomposition of sulphuryl chloride
SO2Cl2 → SO2 + Cl2 Rate = k[SO2Cl2]

Examples of Second Order Reactions.

1. H2 + I2 → 2HI Rate = k[H2][I2]

2. 2NO2→ 2NO + O2 Rate= k[NO2]2
3. Alkaline hydrolysis of esters (Saponification).
CH3-COO-C2H5 + NaOH → CH3-COONa + C2H5-OH Rate = k[CH3-COO-C2H5][NaOH]

Examples of Third Order Reactions

1. 2NO + O2 → 2NO2 Rate = k[NO]2 [O2]

2. 2NO2 + Cl2 → 2NO2Cl Rate = k[NO2]2 [Cl2]

Examples of zero order reactions.

1. Photochemical combination of hydrogen and chlorine on the surface of water.

H2 + Cl2 → 2HCl Rate = k[H2]0 [Cl2]0 = k
2. Decomposition of ammonia at the surface of gold or platinum.
2NH3 → N2 + 3H2 Rate = k[NH3]0 = k

Examples of Fractional Order Reactions

1. H2 + Br2 → 2HBr Rate = k[H2]Br2] ½ Order = 1+ ½ = 1.5.

2. Dissociation of carbonyl chloride
COCl2→ CO + Cl2 Rate = k[COCl2] 3/2
3. Reaction between CO and Cl2
CO + Cl2 → COCl2 Rate = k[CO]2 [Cl2] ½ Order = 2 + ½ = 2.5.
Elementary Reactions.

The chemical reactions which occur only in one step are called elementary reactions.

Complex reactions.

The chemical reactions which occur in two or more steps are called complex reactions.

Rate determining step.

The slowest elementary step of a complex reaction is called rate determining step.

Molecularity of a reaction.

The number of reacting species (atoms, ions or molecules) which must collide simultaneously in order
to bring about a chemical reaction is called molecularity of the reaction.

Note.

• Molecularity of an elementary reaction is equal to the number of species (atoms molecules or

ions) involved in the balanced chemical equation.
• For complex reactions molecularity is given for elementary steps.
• The number of reacting species taking part in the rate determining step decides the rate of the
overall reaction.
• Thus, for complex reactions molecularity is the number of reacting species taking part in the
rate determining step of the reaction.
• Molecularity of the rate determining step is same as the order of the reaction.
• Reactions with molecularity equal to 3 or more are very rare.
• Molecularity is a theoretical concept and is obtained from the mechanism of the reaction.

Differences between Order and Molecularity.

Order Molecularity

1. The sum of the powers to which the
molar concentration terms of
reactants are raised in the rate law
expression is called order of the
reaction.
The number of reacting species (atoms, ions or
molecules) which must collide simultaneously in
order to bring about a chemical reaction is called
molecularity of the reaction.

2. Order can be integral, fractional, Molecularity can have only positive integral
zero, positive or negative values. It can never have zero, fractional or
negative values.

3. Order is an experimental quantity. Molecularity is a theoretical concept (It is

(It is derived from the rate law obtained from the mechanism of the reaction.)
equation obtained on the basis of
experimental observations)
Pseudo – unimolecular Reactions or Pseudo – First order reactions.

First order reactions having molecularity greater than one are called Pseudo – unimolecular or Pseudo –
First order reactions.

Or

The reactions which appear to be of higher order but under certain circumstances behave as first order
reactions are called pseudo - first order reactions or pseudo-unimolecular reactions.

A pseudo first order reaction Is obtained when one of the reactants is present in large excess. The
reactant present in large excess does not affect (or contribute to) the rate of the reaction.

Examples of Pseudo –First order reactions.

1. Acid hydrolysis of esters.

CH3-COO-C2H5+H2O (excess) → CH3-COOH + C2H5-OH
Rate = k[ CH3-COO-C2H5]
2. Acid hydrolysis of cane sugar (Inversion of cane sugar)
C12H22O11 + H2O (excess) → C6H12O6 + C6H12O6
Rate = k [C12H22O11]

Rate constant (k)

Rate constant is the rate of the reaction when concentration of each of the reactant is taken as unity.

Units of Rate Constant.

Consider a reaction, A → products. Let 'n’ be the order of this reaction.

Then, rate = k[A]n

𝑅𝑎𝑡𝑒
k= [𝐴]𝑛
= (mol L-1 s-1)/(mol L-1)n

Thus, unit of rate constant k is (mol L-1) 1-n s-1

1. For zero order reactions unit of k is mol L-1 s-1

2. For first order reactions unit of k is s-1 (min -1 or time -1)
3. For second order reactions unit of k is mol-1 L s-1 or L mol-1 s-1
4. For third order reactions unit of k is mol-2L2 s-1 or L2mol-2 s-1

Characteristics of Rate constant.

1. It is a characteristic constant for a particular reaction at a particular temperature.

2. The value of rate constant is independent of the initial concentration of reactants.
3. The value of rate constant, for a particular reaction, changes with the temperature.
4. Rate constant is a measure of rate of reaction. Greater the value of rate constant, greater is the
rate of the reaction. Smaller value of k indicates slower reactions.
5. Unit of rate constant depends on the order of the reaction.
Differences between Rate and Rate Constant.

Rate Rate constant

1. It is the change in concentration of It is the rate of the reaction when molar

a reactant or product per unit time. concentration of each of the reactant is unity.

2. Reaction rate depends upon the Rate constant does not depend upon the
concentration of the reactant. concentration of reactants.

3. Unit of Rate is mol L-1 s-1 Units of Rate constant is mol L-1) 1-n s-1
ie units of k depend upon the order of the
reaction(n).

Zero Order Reactions.

A reaction whose rate does not depend upon the concentration of any of the reactants and remains
constant throughout the course of the reaction is called a zero order of reaction.

Note.

• For zero reactions both rate and rate constant have same units ie. mol L-1 s-1 or mol-1 L time –1
• Rate of zero order reaction is independent of the concentration of reactants and remains constant
throughout the reaction.

Integrated Rate Law for Zero order reactions.

Consider a zero reaction, A → products.

Let [A]o be the initial concentration of A and [A] be the concentration after the time ‘t’.

Rate of the reaction at the time ‘t’ is given as,

-d[A]/ dt. α [A]0 = k [A]o = k

Or. -d[A] = k dt

On integration –[A] = kt + C. …………..1

Where C is integration constant.

When t = 0, [A] = [A]o, the initial concentration.

Substitute the value of t and [A] in equation 1, we get

[A]o = k x 0 + C
 Ie C = [A]o

Put the value C in equation 1.

–[A] = kt + [A]o

[A]o – [A] = kt
𝟏
k = [𝑨]𝒐 − [𝑨] … … … … . . 𝟐
𝒕

If initial concentration of A is ‘a’ and amount of A reacted in the time t is ‘x’, then the amount of A left
after time t is = a-x

[A]o = a, initial concentration

[A] = a-x , concentration or amount left after time t.

[A]o – [A] = x, amount reacted

Therefore, integral rate equation for zero order reactions can also be written as:
𝒙
k= ………………..𝟑
𝒕

FIRST ORDER REACTIONS

Reactions whose rate is directly proportional to the concentration of reactant are called first order
reactions.

For first order reactions, the rate is determined by the change of one concentration term only.

Ie , rate α concentration of reactant.

Integrated Rate Equation for First Order Reactions

Consider a first order reaction, A → products.

Let [A]o be the initial concentration of A and [A] be the concentration after the time ‘t’.

Rate of the reaction at the time ‘t’ is given as,

−𝑑[𝐴] −𝑑[𝐴] −𝑑[𝐴]
𝑑𝑡
α [A] Or 𝑑𝑡
= k [A] Or [𝐴]
= k dt

−𝑑[𝐴]
On integration. ∫ [𝐴]
= ∫ k dt

-loge[A] = kt + C …………………1

Where C is integration constant.

When t = 0, [A] = [A]o, the initial concentration.

Substitute the value of t and [A] in equation 1, we get

-loge[A]o = k x 0 + C

Ie C = -loge [A]o

Put the value C in equation 1.

–loge[A] = kt - loge[A]o

loge[A]o – loge[A] = kt
[𝐴]0
loge [𝐴]
= kt ……………………2

1 [𝐴]0
k= 𝑙𝑜𝑔𝑒
𝑡 [𝐴]

𝟐.𝟑𝟎𝟑 [𝑨𝒐]
k= 𝒍𝒐𝒈𝟏𝟎 ……………𝟑
Or 𝒕 [𝑨]

If initial concentration of A is ‘a’ and amount of A reacted in the time t is ‘x’, then the amount of A left
after time t is = a-x

[A]o = a, initial concentration

[A] = a-x , concentration or amount left after time t.

Therefore, integral rate equation for zero order reactions can also be written as:

𝟐.𝟑𝟎𝟑 𝒂
k= 𝒕
𝒍𝒐𝒈𝟏𝟎 [𝒂−𝒙] … … … … … … … 𝟒

******Exponential form of Integrated Rate Law for first order reactions

[𝐴]0
From equation2, loge = kt
[𝐴]

[𝐴]
𝑙𝑜𝑔𝑒 = -kt
[𝐴]𝑜

[𝐴]
[𝐴]𝑜
= e-kt

Or [A] = [A]o e-kt

HALF LIFE OF FIRST ORDER REACTIONS (t1/2)

The time taken for half of the reaction to get completed or the time taken for half of the reactant to
change in to products is called half life of a reaction.
 𝟐.𝟑𝟎𝟑 𝒂
k= 𝒕
𝐥𝐨𝐠 𝟏𝟎 [𝒂−𝒙]
𝒂 𝒂 𝒂
When t = t1/2, x= 𝟐
, (a-x) = a- 𝟐 = 𝟐

Put the value of t and x in the above equation.

𝟐.𝟑𝟎𝟑 𝒂
k= 𝒕𝟏
𝒍𝐨𝐠 𝟏𝟎 𝒂
[𝐚− ]
𝟐 𝟐

𝟐.𝟑𝟎𝟑
k= 𝒕𝟏
𝑙og 2
𝟐

𝟐.𝟑𝟎𝟑
k= 𝒕𝟏
x 0.3010
𝟐

𝟎.𝟔𝟗𝟑
k=
𝒕𝟏
𝟐

𝟎.𝟔𝟗𝟑
Or 𝒕𝟏 = ---------------5
𝟐
𝒌

This equation does not contain any concentration term. Therefore, half-life of a first order reaction is
independent of the initial concentration of the reactant. Whatever be the initial concentration of the
reactant, the time taken for half of the reactant to change into product (half life) is the same.

Amount left after ‘n' half lives.

𝟏 [𝑨] 𝟏
[A] = [A]o 𝟐𝒏 OR [𝑨]𝟎
= 𝟐𝒏

Where, [A]o = initial concentration

[A] = amount left after ‘n’ half lives

𝑻𝒐𝒕𝒂𝒍 𝒕𝒊𝒎𝒆 𝒕
n = number of half-lives = 𝑯𝒂𝒍𝒇 𝒍𝒊𝒇𝒆
= 𝒕𝟏
𝟐

Graphical Representation of First Order Reactions

1. log[A] vs time graph

Integrated rate equation can be written in the form of y = mx +c

−𝑘𝑡
log[A] = 2.303 + log [A]o

A plot of log(a-x) or log[A] vs time gives straight line graph with negative slope.
−𝐤
Slope = 𝟐.𝟑𝟎𝟑

Thus, this graph can be used to calculate the rate constant of a first order reaction.
 k = slope x (-2.303)

2. Rate vs concentration graph

For a first order reaction, rate is directly proportional to concentration of the reactant. Hence
plot of rate VS concentration is straight line with slope = k

𝒂 [𝑨𝒐] 𝐤
3. log𝒂−𝒙 vs time graph or 𝒍𝒐𝒈 [𝑨]
vs Time graph is a straight line with slope = 𝟐.𝟑𝟎𝟑
Characteristics of First Order Reactions.

1. Rate of a first order reaction is directly proportional to the concentration of the reactants.
2. The unit of rate constant of first order reaction is time -1 (s-1, min-1)
3. A plot of log [A] vs time is a straight line with slope= -k/2.303
4. Half-life of a first order reaction is independent of initial concentration of the reactant.
5. Time taken for the completion of any fraction of first order reaction is independent of initial
concentration of the reactant.
𝟐.𝟑𝟎𝟑 𝟏
𝒕𝟏 = log 𝟏
𝒏
𝒌 𝟏−
𝒏

𝟐.𝟑𝟎𝟑 𝒏
OR 𝒕𝟏 = log
𝒏
𝒌 𝒏−𝟏

******Experimental Methods to determine the Order of Reaction.

1. Integrated rate law Method. [Hit and Trial Method]

[𝐴]0− [𝐴] 𝑥
For zero order reaction, k = 𝑡
=𝑡
2.303 𝑎 2.303 [𝐴]
For first order reaction, k = 𝑡 log10 𝑎−𝑥 = 𝑡 log10 [𝐴]0 =
1 𝑥 1 1 1
For second order reaction, k = x = x [ - ]
𝑡 𝑎(𝑎−𝑥) 𝑡 𝑎−𝑥 𝑎

The concentration of reactant at different time interval is measured and the data thus obtained are
substituted into the integrated rate equation of different orders. The rate equation which gives a
constant value of rate constant gives the order of the reaction.

2. Graphical Method.

If a straight line graph is obtained on plotting rate against (conc.)n , the given reaction is of the order ‘n’
and the rate law is rate ∝ (conc.)n

For First order reaction, plot of rate vs conc. gives a straight line.

For second order reaction, plot of rate vs (conc.)2 gives straight line.

For third order reaction, plot of rate vs (conc.)3 gives straight line.
3. Half-life Method
1
In general, half-life, 𝒕𝟏 ∝ , Where a is initial concentration and n is order of the reaction.
𝟐
𝑎 𝑛−1
Starting with different initial concentration a1 and a2 for the same reaction, the half lives (𝒕𝟏 )1
𝟐
and (𝒕𝟏 )2 respectively are determined. The order of the reaction,
𝟐
𝒍𝒐𝒈(𝒕𝟏 )𝟏−𝐥𝐨𝐠(𝒕𝟏 )𝟐
𝟐 𝟐
n=1+ 𝒍𝒐𝒈𝒂𝟐− 𝒍𝒐𝒈𝒂𝟏

Plot of 𝒕𝟏 vs conc.
𝟐

For zero order reaction 𝒕𝟏 ∝ initial conc. For first order reaction 𝒕𝟏 is independent of conc.
𝟐 𝟐

1
For a second order reaction 𝒕𝟏 ∝ 𝑎 ie half-life is inversely proportional to initial conc.
𝟐

******Kinetic Study of some first order reactions.

1. Decomposition of N2O5
N2O5 → 2NO2 + ½ O2
Volume of oxygen collected at time t, Vt ∝ x
Volume of oxygen collected at infinite time, V∞ ∝ a
Therefore (V∞ - Vt ) ∝ a-x
2.303 𝑎
Hence k = 𝑡
log10 𝑎−𝑥 can be written as

𝟐.𝟑𝟎𝟑 𝑽
k= log10 ∞
𝒕 𝑽∞ −𝑽𝒕
2. Decomposition of H2O2
H2O2 → H2O + ½ O2
The kinetics of this reaction can be studied in two ways.
i) By measuring the volume of oxygen evolved at different time intervals.
𝟐.𝟑𝟎𝟑 𝑽∞
k= 𝒕
log10 𝑽 −𝑽
∞ 𝒕

ii) By titrating the reaction mixture with standard KMnO4 solution at regular time intervals.
The volume of KMnO4 used at a particular instant is proportional to the amount of H2O2
left (unused) in the solution.
Volume of KMnO4 used when t = 0, V0 ∝ a
Volume of KMnO4 used at the time t, Vt ∝ (a-x)
𝟐.𝟑𝟎𝟑 𝑽
Therefore, k = 𝒕
log10 𝑽𝟎
𝒕

iii) Hydrolysis of Esters in Acidic Medium.

𝑯𝑪𝒍
CH3-COO-C2H5+H2O (excess) → CH3-COOH + C2H5-OH

Kinetics of acid hydrolysis of esters is studied by titrating the reaction mixture with standard
alkali (NaOH) at regular time interval.

Vo ∝ Amount of mineral acid (HCl) used as catalyst.

Vt ∝ Amount of mineral acid + Amount of Acetic acid after time t

𝑉∞ ∝ Amount of mineral acid + Total amount acetic acid formed at the end of the reaction.
Therefore 𝑥 ∝ Vt – V0,

a ∝ 𝑉∞ − V0

(a-x) ∝ 𝑉∞ − Vt
𝟐.𝟑𝟎𝟑 𝑽∞ − V0
Therefore k= 𝒕
log10 𝑽∞ −𝑽𝒕

iv) Inversion of Cane Sugar (Acid hydrolysis of cane sugar)

𝐻𝐶𝑙
C12H22O11 + H2O (excess) → C6H12O6 + C6H12O6

Sucrose(+66.5°) glucose( +52.5)° Fructose(-92.3°)

(dextro) (laevo)

Change in optical rotation ∝ to the amount of sugar undergone hydrolysis.

r0 = optical rotation when t=0

rt = optical rotation when time = t

𝒓∞ = optical rotation when t=∞

 a ∝ r0 - 𝒓∞

𝑥 ∝ r0 - rt

a- 𝑥 ∝ rt - 𝒓∞
𝟐.𝟑𝟎𝟑 𝒓 −𝒓
Therefore, k = 𝒕
log10 rt𝟎 − 𝒓∞
∞

EFFECT OF TEMPERATURE ON THE RATE OF CHEMICAL REACTION.

In general, rate of chemical reaction increases with increase in temperature. On the other
hand, decrease in temperature decreases the rate of reaction.

Temperature Coefficient (μ)

It is defined as ‘the ratio of the rate constants of a reaction at two different temperatures
separated by 100C.’
𝐤(𝐭+𝟏𝟎)
Temperature Coefficient (μ) = 𝐤𝐭

Where, k t = rate constant of the reaction at t0C .

k (t+10) = rate constant of the same reaction at (t +10)0C

For most of the homogeneous reactions, the value of temperature coefficient lies between 2 and 3. This
means that, rate constant as well as rate of the reaction increases 2 to 3 times for every 100 rise in
temperature.

Explanation of effect of temperature on reaction rate.

According to collision theory, for an effective collision, the colliding molecules should possess energy
equal to or greater than threshold energy. At low temperature(T1) number of molecules possessing
energy greater than threshold energy is small. It is shown by the shaded area abcd. As the temperature
is increased from T1 to T2 , the number molecules having energy greater than threshold energy
increases. It is shown by the shaded area aefb. Thus, at higher temperatures more molecules are
capable of undergoing effective collisions. Consequently, rate of the reaction increases with rise in
temperature.

Rate and rate constant of a reaction increases exponentially with temperature.

Arrhenius Equation.
It gives a mathematical relation between rate constant, temperature and activation energy.

−𝑬𝒂
k = A. 𝒆 𝑹𝑻

k = Rate constant

A = Constant known as Arrhenius frequency factor

Ea = Activation energy

R = Universal gas constant.

T = temperature in K

Different forms of Arrhenius Equation.

−𝑬𝒂
1. k = A. 𝒆 𝑹𝑻
𝑬𝒂
2. 𝒍𝒐𝒈𝒆 k = 𝒍𝒐𝒈𝒆 A -
𝑹𝑻
𝑬𝒂
3. 𝒍𝒐𝒈𝟏𝟎 k = 𝒍𝒐𝒈𝟏𝟎 A -
𝟐.𝟑𝟎𝟑𝑹𝑻
𝒌 𝑬𝒂 𝟏 𝟏
4. 𝒍𝒐𝒈𝟏𝟎 𝒌𝟐 = [ - ]
𝟐.𝟑𝟎𝟑𝑹 𝑻𝟏 𝑻𝟐
𝟏

Calculation of Activation Energy.

1. Graphical Method.
𝟏
When log10k is plotted against 𝑻 , a straight-line graph with negative slope is obtained.
−𝑬𝒂
Slope = and Y- intercept is 𝒍𝒐𝒈𝟏𝟎 A
𝟐.𝟑𝟎𝟑𝑹
 Activation Energy = -2.303R x slope

2. Comparison Method.
For two different temperatures T1 and T2

𝒌 𝑬 𝟏 𝟏
𝒍𝒐𝒈𝟏𝟎 𝒌𝟐 = 𝟐.𝟑𝟎𝟑𝑹
𝒂
[𝑻 - 𝑻 ]
𝟏 𝟏 𝟐

𝒌𝟐 𝑬𝒂 𝑻 −𝑻
Or 𝒍𝒐𝒈𝟏𝟎 = [ 𝟐 𝟏]
𝒌𝟏 𝟐.𝟑𝟎𝟑𝑹 𝑻𝟏 𝑻𝟐

CATALYST.
A catalyst is a substance that alters (increases or decreases) the rate of a reaction and
remains unchanged in mass and chemical composition at the end of the reaction.
A positive catalyst increases and a negative catalyst decreases the rate of a reaction.
Function of a Catalyst.
A positive catalyst increases the rate of the reaction by lowering the activation energy
of the reaction. The catalyst combines with a reactant to form an activated complex of lower
activation energy. The activated complex combines with the other reactants (or decomposes)
to form products and the catalyst is regenerated. Thus in the presence of positive catalyst, the
reaction follows an alternative path of lower activation energy and forms an activated
complex of lower energy. Due to lower activation energy, a large number of molecules of
reactants are able to cross the activation energy barrier and consequently, the rate of the
reaction increases.
 For the reaction, A + B → AB
Ea represents activation energy in the
absence of catalyst.
In the presence of catalyst X, the
reaction may be represented as:
A + X → AX
AX + B → AB + X
Ea’ represents activation energy in the
presence of catalyst.
Ea’ < Ea.

Function of a negative Catalyst. (self-study).

Characteristics of Catalyst
1. The catalyst remains unchanged in mass and in chemical composition at the end of the
reaction.
2. Only a small quantity of catalyst is generally needed.
3. A catalyst cannot initiate a reaction. The function of a catalyst is only to alter the speed
of the reaction which is already occurring at a particular rate.
4. A catalyst does not alter the position of equilibrium in a reversible reaction.
5. The catalyst is generally specific in its action.
Mechanism of a Reaction.
The stepwise sequence of elementary reactions that convert reactants into products is
called mechanism of a reaction.
Prediction of Mechanism from Experimental Data.
Data usually available are 1) Rate law
2) Name of the reaction intermediate
3) Net chemical Reaction.
1. Usually slow step involves bond breaking and the formation of reaction intermediate.
2. From the rate law, reactants and products in slow step can be written.
3. Fast step involves the combination of reaction intermediate.
Question 1. For the reaction, H2O2 + 2H+ + 2I- → I2 + 2H2O, the rate law is found to be
Rate = k[H2O2][I-]. Postulate a mechanism for the reaction if OI- ions have been
detected as intermediate during the progress of the reaction.
 Ans. According to the given rate law, the reactants in the slow step are H2O2 and I-
and one of the products in slow step will be OI-, the intermediate. Therefore
slow step is:
𝑠𝑙𝑜𝑤
H2O2 + I- → OI- + H2O ------------------ 1
From the net equation, we can write the fast reaction which involves the
combination of OI-.
𝑓𝑎𝑠𝑡
2H+ + I- + OI- → I2 + H2O ------------------ 2
There fore the net reaction is eq(1) + eq(2)
H2O2 + 2H+ + 2I- → I2 + 2H2O
Question 2. NO2 reacts with F2 as follows. 2 NO2 + F2 → 2NO2F. The rate law of the reaction is
rate = k[NO2][ F2]. F atoms have been detected as the intermediate during the
progress of the reaction. Suggest a mechanism for the reaction.
𝑠𝑙𝑜𝑤
Ans. NO2 + F2 → NO2F + F
𝑓𝑎𝑠𝑡
NO2 + F → NO2F
Question 3. For the reaction NO2 + CO → NO + CO2, the rate law at 440K is : Rate = k [NO2]2.
Suggest a mechanism.
𝑠𝑙𝑜𝑤
Ans. 2NO2 → NO + NO3
𝑓𝑎𝑠𝑡
CO + NO3 → CO2 + NO2
Question 4. For the reaction, 2NO + 2H2 → N2 + 2H2O, the mechanism is given below.
𝑠𝑙𝑜𝑤
i) 2NO + H2 → N2 + H2O2
𝑓𝑎𝑠𝑡
ii) H2O2 + H2 → 2H2O
What is the predicted rate law and order of the reaction?
Ans. Rate law is; rate = k [NO]2 [H2]
Order = 2+1 = 3