1.

Rate of a Chemical Reaction

The rate of a reaction can be defined as the change in concentration of a reactant or
a product in unit time.
1.1 Average Rate
The rate of reaction measured over a definite time interval is called average rate of a
reaction. Consider a hypothetical reaction,
R→P

∗20l
Average rate of reaction = (Decrease in concentration of R) (Time taken) = [ΔR]Δt
Or
Average rate of reaction = (Increase in concentration of P) (Time taken) = [ΔP]Δt
1.2 Instantaneous Rate
Rate of change of concentration of any one of the reactants or products at that
particular instant of time is called instantaneous rate.
As
Δt→0
or
rinst = −d[R]dt = d[P]dt
Important: Rate of a reaction is always positive. Since, [R] is a negative quantity (as
concentration of reactants is decreasing), it is multiplied with –1 to make the rate of
the reaction a positive quantity.
1.3 Units of Rate of a Reaction
Units of rate are concentration time –1

e.g. mol L-1s -1; atm s-1 (for gaseous reactions)

1.4 Overall Rate of a Reaction
When there are several reactants and products the individual rates of the various
components may differ as they would depend on the stoichiometric coefficients.

For a reaction,
A + 2B →3C + 4D
Rate of disappearance of B = 2 × Rate of disappearance of A (2:1)
Rate of formation of C = 3 × Rate of disappearance of A
(3:1)
Rate of formation of D = 4 × Rate of disappearance of A
(4:1)
To define a unique value for the overall rate of the reaction we divide the individual
rates by the respective coefficients and equate their signs.
Overall Rate = - A / t = (-1/2) B/ t = ( + 1/3) C/ t
= ( + 1/4) D / t

2. Dependence of Rate nn Concentration

Factors Influencing Rate of a Reaction
concentration of reactants (pressure in case of gases),
temperature and
Catalyst.

Dependence on Concentration:
2.1 Rate Law
Consider a general reaction
aA + bB →cC + dD
The rate expression for this reaction is

Rate ∝ [A]x [B]y

where exponents x and y may or may not be equal to the stoichiometric coefficients
(a and b) of the reactants.

Rate=k⋅[A]x⋅[B]y
−d[R]/dt=k[A]x [B]y
Above equation is known as differential rate equation, k is a proportionality constant
called rate constant.
Rate law is the expression in which reaction rate is given in terms of molar
concentration of reactants with each term raised to some power, which may or may
not be same as the stoichiometric coefficient of the reacting species in a balanced
chemical equation.
Important
Rate law for any reaction cannot be predicted by merely looking at the balanced
chemical equation, i.e., theoretically but must be determined experimentally.
2NO(g)+O2(g)→ 2NO2(g)

Rate=k⋅[NO]2⋅[O2]
CHCl3+Cl2→CCl4+HCl

Rate=k⋅[CHCl3]2⋅[Cl2]12
2.2 Order of a Reaction
aA + bB →cC + dD
Rate=k[A]x[B]y
Sum of these exponents, i.e., x + y gives the overall order of a reaction where x and
y represent the order with respect to the reactants A and B respectively. Hence, the
sum of powers of the concentration of the reactants in the rate law expression is
called the order of that chemical reaction.
Order of a reaction can be 0, 1, 2, 3 and even a fraction.
2.3 Units of Rate Constant
Rate=k[A]x[B]y
k=Rate[A]x[B]y=concentrationtime×1(concentration)n

3. Integrated Rate Equations

3.1 Zero Order Reaction
The rate of the reaction is proportional to zero power of the concentration of
reactants.
R→P

Rate = - [dR]dt=kR∘
Consider the reaction,
R→P
Rate=−d[R]dt = k[R]0
Rate=−d[R]dt = k×1
d[R] =− kdt
Integrating both sides
[R]=− kt+I
where, I is the constant of integration.
At t = 0, the concentration of the reactant R = [R] , where [R] is initial concentration
0 0

of the reactant.
Substituting in equation
[R]0 = - k x 0 + I
[R]0 = I
Substituting the value of I in the equation
[R] = -kt + [R]0
k=([R]0)−([R])t
Example:
The decomposition of gaseous ammonia on a hot platinum surface at high pressure.
2NH3(g)→Pt catalyst1130 KN2(g)+3H2(g)
Rate = k[NH3]0
= k
Thermal decomposition of HI on gold surface

3.2 First order

The rate of the reaction is proportional to the first power of the concentration of the
reactant R.
Rate = - d[R]dt
=k[R]
R→P
Rate = - d[R]dt=k[R]
- d[R][R]=kdt
Integrating this equation, we get
ln [R] = -kt + I ........ (1)
Again, I is the constant of integration and its value can be determined easily.
When t = 0, R = [R]0,where [R]0 is the initial concentration of the reactant.
Therefore, equation can be written as
ln [R]0 = - k x 0 + I
ln [R]0 = I
Substituting the value of I in equation
ln [R] = -kt + ln [R]0 ......... (2)
Rearranging this equation

ln⁡[R][R]0=−kt
Or
k=1tln⁡[R]0[R]⋯⋯(3)
At time t from equation (2)
1

ln [R]1 = -kt1 + ln [R]0

At time t 2

ln [R]2 = -kt2 + ln [R]0

where, [R]1and [R]2are the concentrations of the reactants at time t1 and t2
respectively.
Subtracting
ln [R]1- ln[R]2 = - kt1 - (-kt2)
ln [R]1[R]2=k(t2 - t1)
k=1(t2 - t1)ln [R]1[R]2
Comparing equation (2) with y = mx + c, if we plot In [R] against t, we get a straight
line with slope = –k and intercept equal to ln [R]
0

The first order rate equation (3) can also be written in the form

k=2.303tlog⁡[R]0[R]

log⁡[R]0[R]=kt2.303
3.3 Half-Life of a Reaction
The half-life of a reaction is the time in which the concentration of a reactant is
reduced to one half of its initial concentration.
Represented as: t1/2
For a zero order reaction, rate constant is given by equation.
k=[R]0−[R]tt
At t=t1/2, [R] = 12[R]0
The rate constant at t1/2 becomes
k=[R]0−[R]02t1/2
t1/2=[R]02k
For the first order reaction,

k=2.303tlog⁡[R]0[R]
At half time, [R]=[R]02
So, the above equation becomes

k=2.303t1/2log⁡[R]0[R]/2
Or t1/2=2.303klog⁡2
t1/2=2.303k×0.301
t1/2=0.693k

3.4 Pseudo First Order Reactions

Reactions which are not truly of the first order but under certain conditions become
reactions of the first order. e.g.
CH3COOC2H5 + H2O →H+CH3COOH + C2H5OH
Rate = k [CH3COOC2H5][H2O]
The concentration of water does not get altered much during the course of the
reaction. So, in the rate equation the term [H2O] can be taken as constant.
Rate = k[CH3 COOC2H5 ] ;where kn = k [H2O]
Cane Sugar/Glucose/Fructose: H C H O H O C H O C H O
Rate = k [C12H22O11]
3.5 Practical Analysis of First Order Reactions
 Case - 1:
In gaseous phase reactions we prefer to measure the pressure of the gases
or volume. For example the following reactions :
For a first order gas phase reaction of the type:
A(g)→ B(g) + C(g)
Let pi be the initial pressure of A and p the total pressure at time ‘t’.
t

Integrated rate equation for such a reaction can be derived as:

Total pressure pt = pA + pB + pC (pressure units) pA , pB and pC are the
partial pressures of A, B and C, respectively. If x atm be the decrease in
pressure of A at time t and one mole each of B and C is being formed, the
increase in pressure of B and C will also be x atm each.
A(g)→ B(g) + C(g)
At t = 0 pi atm 0 atm 0 atm
At time t (pi - x) atm x atm x atm
where, pi is the initial pressure at time t = 0.
pt = (pi - x) + x + x = pi + x
x = (pt - pi )
pA = pi - x = pi - (pt - pi)
 = 2pi - pt

k=(2.303t)(log⁡pipA)

=(2.303t)(log⁡pi(2pi−pi))
For a first order gas phase reaction of the type :
A(s)→ B(s) + C(g)
The data given to us is:
If we have to find the expression for k or verify that its a first order reaction
then we will use the expression for k:

ln⁡aa−x=kt
But we don’t know the values for a or a – x but we can find the above ratio by
relating the given data with concentration values.

For gases, P ∝ number of moles

A(s) → B(s) + C(g)
t=0 a 0 0
t=t a−x x x
t=∞ 0 a a
Now we can write;

Pt ∝x

P∞∝a

P∞ - Pt ∝a - x
a/(a - x) = P∞ /(P∞ - Pt )
Now we can substitute this into the expression for k.

k = (1/t)ln⁡[P∞/(P∞− Pt)]
The above expression can be used to evaluate the value of k from the
pressure data and also verify that the reaction is of first order by checking 2-3
data points. In the above analysis the expression would have been same for
the following reactions as well as the constants will cancel out.
A(s)→ B(s) + 2C(g)
And the results will be same if the similar data is given in terms of volume.
A(s)→2B(g) + C(g)
 Case 2:
If one of reactants is titrated with a red/ox reagent:
Suppose we have a reaction of the type:
 A→B+C
And suppose we detect the amount of A left by titrating it with some reagent
and volume of that reagent reacting with the left over A is given at different
time intervals:
Now the volume of the reagent will be proportional to the moles of A present.
Therefore:

V0 ∝ a

Vt ∝ a − x
We can evaluate k:

kt=ln⁡(V0/Vt)
If the same reagent reacts with all the reactants and products:

V0 ∝ a

Vt ∝ a + x

2V0 − Vt ∝ a − x
kt = ln (V0 /2V0 − Vt )
3.6 Practical Methods of Determining Order of a Reaction
I. Initial Rate Data Method:
We take different set of initial concentration and measure the initial rate. Then
by keeping the concentration of one of the reactants constant and varying the
other one we can study the effect on the rate and hence find out the order.
II. Logarithmic Data Method:
For any order, be it fractional or integral, if we plot log (rate) vs log
(concentration) graph it will always be a straight line for the reactions of the
type:
A→products
Rate, r = k[A]n
log r = log k + n log [A]
We can take various data points and convert them to log values and plot
them. We will obtain a straight line after curve-fitting with slope n and intercept
log k. And hence we can find out the order and rate constant from the graph.
III. Half Life Method:
If we take various concentrations of reactant and measure half life for all of
them then we can find out the order of the reaction by mere observation or
with the help of some calculations.
t1/2=[A]01−n
 If simple observation is not possible then we can calculate the order of the
reaction by taking two data points and using log for calculating n.
IV. By integrated rate Equations:
If we have simple data of concentration and time we can use the integrated
rate equations to find out the order. For this we will have to try and fit the data
into the equation at various intervals and calculate the value of rate constants.
If the values come out to be the same in all intervals then the data fits into the
equation taken and we will know the order. For example, we have the
following data:
Time: 0 t1 t2 t3 ....... t
Conc: A0 A1 A2 A3 .......At
And if we assume that it can be of first order then we will calculate the values
of k at minimum three data points by using the equation for first order:
(1/t) ln (A0/At) = k
Let these values be k1, k2 and k3. If k1=k2=k3 then it means that this data fits
into the above equation hence the order is 1. If it doesn’t we will have to try
other equations as well.
V. Isolation Method:
In this method we try and eliminate one of the two reactants from the rate
equation by taking it in excess. What happens is when the amount of a
reactant is in excess its effect on the rate becomes marginal or negligible and
then we can vary the concentration of the other reactant and observe its effect
on rate and find out the order.

4. Molecularity And Mechanism

4.1 Molecularity
The number of reacting species (atoms, ions or molecules) taking part in an
elementary reaction, which must collide simultaneously in order to bring about a
chemical reaction is called molecularity of a reaction.
Classification of reactions on the basis of Molecularity:
Unimolecular Reactions: when one reacting species is involved, for example,
decomposition of ammonium nitrite.
NH4NO2→N2 + 2H2O

Bimolecular Reactions: involve simultaneous collision between two species, for

example, dissociation of hydrogen iodide.
2HI→H2 + I2
 Trimolecular or Termolecular Reactions: involve simultaneous collision between
three reacting species, for example,
2NO + O2→2NO2
Reactions with molecularity greater than three are very rare.
4.2 Mechanism
The reactions taking place in one step are called elementary reactions. When a
sequence of elementary reactions (called mechanism) gives us the products, the
reactions are called complex reactions. The different steps in which the complex
reaction takes place is called the mechanism of the reaction.

Rate Determining Step:

The overall rate of the reaction is controlled by the slowest step in a reaction called
the rate determining step. A complex reaction can be represented as a series of
elementary steps.
For example
2NO2(g) + F2(g)→2NO2F(g)
Experimentally, Rate of reaction = k[NO2][F2]
Probable Mechanism:
Step-1:
NO2 + NO2→NO + NO3 (slow)
Step-2:
NO3 + CO→NO2 + CO2(fast)
Slow step: bimolecular
Hence, a bimolecular reaction.

Reaction Intermediates: There are some species which are formed during the
course of the reaction but do not appear in the overall reaction. They are called
reaction intermediates.
e.g. NO in the above example.
3

Distintion Between Order and Molecularity of a Reaction

Order
1. Order is the sum of the powers of the concentration of the reactants in the
rate law expression.
2. It can be zero and even a fraction.
 3. It is applicable to elementary as well as complex reactions.
4. It can be determined experimentally only and cannot be calculated.
5. For complex reaction, order is given by the slowest step.
Molecularity
1. Molecularity is the number of reacting species taking part in an elementary
reaction, which must collide simultaneously in order to bring about a chemical
reaction.
2. It cannot be zero or a non integer.
3. It is applicable only for elementary reactions. For complex reaction
molecularity has no meaning.
4. It can be calculated by simply adding the molecules of the slowest step.
5. Generally, molecularity of the slowest step is same as the order of the overall
reaction.

5. Temperature Dependence
5.1 Activation Energy
According to collision theory, a reaction takes place because the reactant molecules
collide with each other. The minimum energy which the colliding molecules must
have in order that the collision between them may be effective is called threshold
energy. The minimum extra amount of energy absorbed by the reactant molecules
so that their energy becomes equal to threshold value is called activation energy.

Threshold energy = Activation energy + Energy possessed by the reactants

Less is the activation energy, faster is the reaction. In order that the reactants may
change into products, they have to cross an energy barrier (corresponding to
threshold energy). Reactant molecules absorb energy and form an intermediate
called activated complex which immediately dissociates to form the products.
(images will be uploaded soon)
5.2 Temperature Dependence of the Rate of a Reaction
For a chemical reaction with rise in temperature by 10°, the rate constant is nearly
doubled. Temperature coefficient = (Rate constant at T + 10 ) / (Rate constant at T )
0 0

Explanation:
At a particular temperature, if fractions of molecules are plotted versus
corresponding kinetic energies, a graph of the type shown is obtained. The peak of
the curve represents the kinetic energy possessed by the maximum fraction of
molecules and is called most probable kinetic energy.
(images will be uploaded soon)
With Increase in Temperature:
(i) Maximum of the curve moves to the higher energy value i.e., most probable
kinetic energy increases
(ii) the curve spreads to the right i.e., there is a greater proportion of molecules with
much higher energies.
The area under the curve remains constant since total probability must be one at all
times. At (t + 10), the area showing the fraction of molecules having energy equal to
or greater than activation energy gets doubled leading to doubling the rate of a
reaction.

Arrhenius Equation
Quantatively, the temperature dependence of the rate of a chemical reaction can be
explained by Arrhenius equation

k=Ae−EaRT

where A is the Arrhenius factor or the frequency factor or pre-exponential factor. R is

gas constant and Ea is activation energy measured in joules/mole. The factor
e−EaRT corresponds to the fraction of molecules that have kinetic energy greater
than Ea. Thus, it has been found from Arrhenius equation that increasing the
temperature or decreasing the activation energy will result in an increase in the rate
of the reaction and an exponential increase in the rate constant. Taking natural
logarithm of both sides of equation

ln⁡k=ln⁡Ae−EaRT
Solving the equation further:

ln⁡k=ln⁡(A)+ln⁡(e−EaRT)

ln⁡k=ln⁡(A)+(−EaRT)=ln⁡(A)−(EaR)(1T)

The plot of ln⁡k vs 1T gives a straight line with slope

The logarithmic version of the Arrhenius equation for a chemical reaction at two
distinct temperatures T1 and T2, with corresponding rate constants k1 and k2, is:

ln⁡k1=ln⁡(A)−EaRT1
ln⁡k2=ln⁡(A)−EaRT2
Therefore, the entire equation can be simplified as follows:

ln⁡k1k2=−EaR(1T1−1T2)

6. Effect of Catalyst

A catalyst is a substance which alters the rate of a reaction without itself undergoing
any permanent chemical change.

Action of the catalyst

According to intermediate complex theory, reactants first combine with catalyst to
form intermediate complex which then decomposes to form the products and
regenerating the catalyst.

Effect of Catalyst on Activation Energy

Catalyst provides an alternate pathway by reducing the activation energy between
reactants and products and hence lowering the potential energy barrier.

Important Characteristics of Catalyst:

A small amount of the catalyst can catalyse a large amount of reactants.

A catalyst does not alter Gibbs energy, G of a reaction.

It catalyses the spontaneous reactions but does not catalyse non-spontaneous

reactions.

A catalyst does not change the equilibrium constant of a reaction rather, it helps in
attaining the equilibrium faster.

7. Collision Theory Of Chemical Reactions

According to this theory, the reactant molecules are assumed to be hard spheres
and reaction is postulated to occur when molecules collide with each other. Rate of
reaction depends on the number of effective collisions which in turn depends on:
(i) Energy Factor: Colliding molecules must have energy more than threshold
energy.
(ii) Steric or Probability Factor (P): Colliding molecules must have proper
orientations at the time of collision.

Class 12 Chemistry Chapters 3 Formulas and Concepts

1. Integrated rate law equation for zero order reaction
k = [R] [R]/t
o

Where k is the rate constant and [R] is the initial molar concentration.

2. t = [R] /2k
1/2 o

t is the half-life period of zero-order reaction.

1/2

3. Integrated Rate LEquation for First OReaction

k = 2.303/k log [R]/[R]
Where k is the rate constant, [R] is the initial molar concentration, and [R] is the final
concentration at a time 't'.

4. Half-life period (t ) for the First-order Reaction:

1/2

t = 0.693/k
1/2

5. Arrhenius Equation
k=Ae-E /RT a

Where 'A' is the frequency factor, Ea is the energy of activation, R is the universal
gas constant and T is the absolute temperature.