Chemical Kinetics: Zero Order

Reaction
 Zero Order Reactions

• Examples of zero order reactions

• Characteristics of zero order reaction
• Half-time or half-life period of a zero order
reaction
• A reaction is said to be of zero order if its rate is
independent of the concentration of the reactants,
i.e., the rate is proportional to the zeroth power of
the concentration of the reactants.
• For the reaction
• A → products
• To be of zero order,
 d[A] = -kdt
• Integrating both sides
[A] = – k t + C.....(i)
• where, C is the constant of integration
• At t = 0, the concentration of the reactant A = [A] 0, where
[A]0 is initial concentration of the reactant.

• Substituting in equation (i)

[R]0 = –k × 0 + C
[R]0 = C
• Substituting the value of C in the equation (i)
[A] = -kt + [A]0 ….. (ii)
• Comparing equation (ii) with equation of a straight line.
y = mx + c
• If we plot [A] against t, we get a straight line with
slope = –k and intercept equal to [A]0.

• Some photochemical reaction and a few

heterogeneous reactions are zero-order reactants.
Such reactions are not common.
 Examples of Zero Order Reactions
• Photochemical reaction between hydrogen and chlorine:
H2(g) Cl2(g) → 2HCl(g)
• This photochemical reaction is zero-order reaction. The
reaction is studied by placing H2 and Cl2 gases over water.
• The rate of reaction is studied by nothing the rate at
which water rises in the vessel due to dissociation of HCl
formed.
• The rate of rise of water is the same as the rate of
disappearance of H2 and Cl2, i.e., the concentration of the
gases phase will not change with time, although the
quantities will change.
Decomposition of N2O on hot platinum surface

N2O → N2 + 1/2O2
Rate [N2O]0 = k[N2O]0 = k
d[N2O]/dt = k
 Decomposition of NH3 in presence of
molybdenum or tungsten is a zero-order reaction

• 2NH3 N2 + 3H2
• The surface of the catalyst is almost completely
covered by NH3 molecules. T
• he adsorption of gas on the surface cannot change
by increasing the pressure or concentration of NH3.
• Thus, the concentration of gas phase remains
constant although the product is formed. Therefore,
this reaction zero order kinetics.
 Other examples of zero order are:

• Iodations of acetone in presence of H+ ions.

CH3COCH + I2 ICH2COCH3 + HI
• The rate equation of this reaction does not
include [I2] factor, i.e.,
-dx/dt = k[CH3 COCH3 ][H+]
 Characteristics of Zero Order Reaction
• The concentration of reactant decreases linearly with
time.[A]t = [A]0 - kt

• The time required for the reaction to be complete,

i.e., time at which [A] is zero.
•
tcompletion = [A]0/k = (Initial concentration)/(Rate
constant)

• The units of k are mol L-1 time-1.

Half-Time or Half-Life Period of a Zero Order Reaction

• The half-time of a reaction is defined as the time

required to reduce the concentration of the
reactant to half of its initial value. It is denoted by
the symbol t1/2. Thus,
• For zero order reaction, we know that
• [A] = -kt + [A]0,

• At half life of reaction, t = t½ & [A] = [A]o/2

• So
 Molecularity and Order of Reaction

• Molecularity of reaction
• Order of reaction
• Pseudo-order reaction
• The main differences between Molecularity
and order of reaction
 Molecularity of Reaction
• A chemical reaction that takes place in one and only one
step i.e., all that occurs in a single step is called
elementary reaction while a chemical reaction occurring
in the sequence of two or more steps is called
complicated reaction.
• The sequence of steps through which a complicated
reaction takes place is called reaction – mechanism. Each
step in a mechanism is an elementary step reaction.
• The molecularity of an elementary reaction is defined as
the minimum number of molecules, atoms or ions of the
reactants(s) required for the reaction to occur and is
equal to the sum of the stoichiometric coefficients of the
reactants in the chemical equation of the reaction.
• In general, molecularity of simple reactions is
equal to the sum of the number of molecules
of reactants involved in the balanced
stoichiometric equation.
• or
• The molecularity of a reaction is the number of
reactant molecules taking part in a single step
of the reaction.
• e.g.,
 Chemical Reaction Molecularity
PCl5 → PCl3 + Cl2 Unimolecular
2HI → H2 + I2 Bimolecular
2SO2 + O2 → 2SO3 Trimolecular
NO + O3 → NO2 + O2 Bimolecular
2CO + O2 → 2CO2 Trimolecular
2FeCl3 + SnCl2 → SnCl2 + 2FeCl2 Trimolecular
• The minimum number of reacting particles
(molecules, atoms or ions) that come together or
collide in a rate determining step to form product
or products is called the molecularity of a reaction.
• For example, decomposition of H2O2 takes place in
the following two steps:
Decomposition of H2O2.

Overall Reaction H2O2 → H2O + 1/2O2

Step 1: H2O2 → H2O + [O] Slow

Step 2: [O] + [O] → O2 Fast
 Molecularity…
• The slowest step is rate-determining. Thus
from step 1, reaction appears to be
unimolecular.
• There are some chemical reactions whose
molecularity appears to be more than three from
stoichiometric equations, e.g.
• 4HBr + O2 → 2H2O + 2Br2
• 2MNI4- + 16H+ + 5C2 O42- → 2Mn2+ + 10CO2 + 8H2O
• In the first reaction molecularity seems to be '5'
and in the second reaction molecularity seems to
be '23'. Such reactions involve two or more steps;
each step has its own molecularity not greater
than three, e.g., in first reaction.
 HBr + O2 → HOOBr

HOOBr + HBr → 2HOBr

[HOBr + HBr → H2O + Br2]

• Molecularity of each of the above steps is 2.

• Reaction between Br- and H2O2 in acidic medium:
• The overall reaction is
• 2Br- + H2O2 + 2H+ → Br2 + 2H2O
• The proposed mechanism is
 2Br- + H2O2 + 2H+ → Br2 + 2H2O

Step 1: 2Br- + H2O2 + H+ → HOBr + H2O Slow

Step 2: HOBr + H+ + Br- → Br2 + H2O Fast

• The reaction is trimolecular

• (b) Reaction between NO2 and F2:
• The overall reaction is
• 2NO2 + F2 → 2NO2F
• The proposed mechanism is
 2NO2 + F2 → 2NO2F

Step 1: NO2 + F2 → NO2 + F Slow

Step 2: NO2 + F → NO2F Fast

• The reaction is bimolecular.

• Reactions of higher molecularity (molecularity >
3) are rare.
• This is because a reaction takes place by collision
between reactant molecules and as number of
reactant molecules i.e. molecularity increases the
chance of their coming together and colliding
 Order of Reaction

• The mathematical expression showing the

dependence of rate on the concentration(s) of
reactant(s) is known as rate-law or rate-
expression of the reaction and sum of the indices
(powers) of the concentration terms appearing in
the rate law as observed experimentally is called
order of reaction. To understand what is order of
reaction, consider the reaction
2NO(g) + 2H2(g) → N2(g) + 2H2O (g)
• Kinetic experiment carried out at 1100 K upon this
reaction has shown following rate data.

Expt. No. [NO] (mole dm )–3 [H2] (mole dm –3

) Rate (mole dm s
–3 –1
)
1. 5 x 10–3 2.5 x 10–3 3 x 10–5
2. 1.0 10–2 2.5 10–3 1.2 x 10–4
3. 1.0 x 10–2 5.0 x 10–3 2.4 x 10–4
 Order…
• From the Expt. No.1 and 2, it is evident that rate increases
4 fold when concentration of NO is doubled keeping the
concentration of H2 constant i.e.
• Rate [NO]2 when [H2] is constant again from Expt. No.2
and 3, it is evident that when concentration of H2 is
doubled keeping the concentration of NO constant, the
rate is just doubled i.e.
• Rate [H2] when [NO] is constant
• From Expt. (1) and Expt. (3), the rate increases 8-fold when
concentrations of both NO and H2 are doubled
simultaneously i.e.
• Rate [NO]2 [H2]
 Order…
• This is the rate-law of reaction as observed
experimentally. In the rate law, the power of nitric
oxide concentration is 2 while that of hydrogen
concentration is 1. So, order of reaction w.r.t. NO is 2
and that w.r.t. H2 is 1 and overall order is 2 + 1 i.e. 3.
• Note that the experimental rate law is not
consistent with the stoichiometric coefficient of
H2 in the chemical equation for the reaction. This
fact immediately suggests that the reaction is
complicated and it does not occur in single step as
written. In order to explain the rate law, following
mechanism has been proposed.
 Order…
NO + NO N2O2 (fast and reversible)
N2O2 + H2 → N2O + H­2O (slow)
N2O + H2 → N2 + H2O (fast)
• Let us see how this mechanism corresponds to the rate
law as found experimentally and mentioned above.
• The step II being the slowest step is the rate-determining
step. Thus, rate of overall reaction or rate of formation of
N2, will be equal to the rate of step II or rate of formation
of H2O. So, we have according to Law of Mass Action.
• Rate of overall reaction = Rate of step II = k [N2O2] [H2]
 Order…
• The step II being the slowest step is the rate-
determining step. Thus, rate of overall reaction or rate
of formation of N2, will be equal to the rate of step II or
rate of formation of H2O. So, we have according to Law
of Mass Action.
• Rate of overall reaction = Rate of step II = k [N2O2] [H2]
• Where k = rate constant of step II.
• N2O2 being intermediate for the overall reaction, its
concentration has to be evaluated in terms of the
concentration(s) of reactant(s) and this can be done by
applying Law of Mass Action upon the equilibrium of
Step I. Thus,
 Order…

• where KC = equilibrium constant of Step II. Putting this

value of concentration of N2O2 in the above rate
expression, we get
• Rate reaction = k×Kc× [NO]2 [H2]
• or Rate of reaction = k1[NO]2 [H2]
• Rate of reaction [NO]2 [H2]
• Where k×Kc = k1 = another constant, rate constant of
overall reaction.
 Order…

• Note that from the knowledge of any two out of k, K c and k1,
the rest one may be calculated.
• We are again turning to our topic “order”. In general, if rate
law of a reaction represented by the equation.
• aA + bB → Products
• is experimentally found to be as follows:
• Rate [A]m [B]n
• Then
• order w.r.t. A = m
• order w.r.t. B = n
• overall order = m + n
 order

• It is to be noted that ‘m’ may or may not be equal

to ‘a’ and similarly ‘n’ may or may not be equal to
‘b’. m and n are experimental quantities and their
values which really depend on the reaction-
mechanism and experimental condition, may not
be predicted by just seeing the chemical equation
of the reaction. Reactions with same kind of
chemical equations may differ in their rate laws
and hence order. An example of this is as follows.
Reactions Rate Law Order
2N2O5 → 4NO2 + O2 Rate [N2O5] 1
2NO2 → N2O2 +O2 Rate [NO2]2 2
 Order…
• Order of reaction may also be defined as follows:
Number of molecules of the reactant(s) whose concentration
changes during the chemical change is called order of
reaction.
• For example, the reaction
CH3COOC2H5 + H2O CH3COOH + C2H5OH is a bimolecular
reaction but its order is ‘one’. This is because during the reaction
only the concentration of ester decreases with time.
• The concentration of water in the reaction mixture (usually a
dilute aqueous solution of ester mixed with dilute aqueous acid)
being in large excess as compared to ester, does not decrease
appreciably or measurably during the reaction.
• The first order behaviour of this reaction can be derived in the
following way.
• Applying Law of Mass Action upon the above reaction.
Rate [CH3COOC2H5] [H2O]
or Rate = k[CH3COOC2H5] [H2O]
• Where k is the rate constant of the above bimolecular reaction.
• Since concentration of water remains practically constant. So,
• K[H2O] = k1 = another constant or observed rate constant of the
reaction.
• So, Rate = k1 [CH3COOC2H5]
• This is first-order kinetics i.e. order in respect of ester is ‘1’ and that in
respect of water is ‘zero’.
• The reaction is an example of pseudounimolecular (or pseudo first
order).
• Thus, a second order reaction conforms to the first order if out of the
reactants one is present in large excess and the reaction is called
pseudounimolecular.
Suppose we have a reaction: 2A + B → Products
With rate law; Rate µ [A]2 [B] (order = 2 + 1 = 3)
It B is taken in large excess as compared to A, their reaction will
obey the kinetics.
Rate [A]2 (Q [B] is constant)
So, Order w.r.t. A = 2; Order w.r.t. B = 0 and Overall order = 2
If A is taken in large excess as compound to B then reaction will
obey the kinetics.
Rate [B] (Q [A] is constant)
So, Order w.r.t. A = 0, Order w.r.t. B = 1 and Overall order = 1
•If both A and B are taken in large excess, can
you say what will be the order?
•Some of you may tell that order will be zero. This is
absolutely wrong.
When both A and B are in large excess, then there
will be appreciable damage in the concentrations
of both of them and hence order will be ‘3’.
•Reactions are classified on the basis of order as an,
first, second, third order etc. according as their
order equal to 0, 1, 2and 3 etc. respectively
 Some typical linear plots for the reactions of different orders:

• Plots rate vs concentrations [Rate = k(conc.)n]

• From the study of the kinetics of many simple
reactions, it is observed that for a large number of
reactions, the molecularity and order are the same.
 Some examples are given below to justify
this point.
• Dissociation of N2O5.
N 2O 5 → N 2O 4 + O 2
Order = 1, Molecularity = 1
• Dissociation of H2O2.
H2O2 → H2O + 1/2O2
Order = 1, Molecularity = 1
• Dissociation of HI,
2HI → H2 + I2
Order = 2, Molecularity = 1
• Formation of NO2.
2NO + O2 → 2NO2
Order = 3, Moelcularity =3
 Pseudo- Order Reactions

• Reactions whose actual order is different from

that expected using rate law expression are
called pseudo-order reactions; e.g.,
• RCl + H2O → ROH + HCl
• Expected rate law:
• Rate = k[RCl] [H2O] Expected order = 1+1 =2
• Actual rate law:
• Rate = k'[RCl]; Actual order = 1
• Water is taken in excess; therefore, its
concentration may be taken constant.
• The reaction is, therefore, pseudo first order.
• Similarly, the acid catalysed hydrolysis of ester,
viz.,
RCOR' + H2O ↔ RCOOH + R'OH
• follow first order kinetics:
Rate = k[RCOOR']
• It is also a pseudo-first order reaction.
The Main differences between Molecularity and Order of Reaction

Moleculariy Order of Reaction

It is the total number of It is the sum of powers of
reacting species (molecules, molar concentration of the
atoms or ions) which bring reacting species in the rate
the chemical change. equation of the reaction.
It is always a whole number. It may be a whole number,
zero, fractional,
It is a theoretical concept. It is experimentally
determined.
It is meaningful only for
simple reactions or individual It is meant for the reaction
steps of a complex reaction. and not for its individual steps
It is meaningless for overall
complex reaction.