Order of a reaction

Definition
The Order of Reaction refers to the power dependence of the rate on the concentration
of each reactant. Thus, for a first-order reaction, the rate is dependent on the
concentration of a single species. A second-order reaction refers to one whose rate is
dependent on the square of the concentration of a single reactant (e.g., in a homo-
dimerization reaction, A + A → A2) or the combined first-order dependence on the
concentrations of two different reactants (A + B → C). The order of reaction is an
experimentally determined parameter and can take on a fractional value. This is distinct
from the molecularity (or stoichiometry) of the reaction which is the theoretical integer
value of the number of molecules involved in the reaction. For simple one-step reactions,
the order and molecularityshould have the same value
First-order Reaction Rate Law
Differential Rate Law

Rate = – d[A]/dt = k [A]

Where,

R is the reaction rate

[A] is the concentration of the reactant A
k is the rate constant

Integrated Rate Law

[A] = [A]o exp (-kt)

Where,

[A]o is the concentration at time t = 0

[A] is the concentration at time t
Taking the natural logarithm on both sides.

ln [A] = ln [A]o – kt
Examples of First-order Reaction
Here are some examples of first-order chemical reactions.

1. Trimethyl bromomethane ((CH3)3CBr) reacts with sodium hydroxide (NaOH) to give trimethyl
methanol ((CH3)3COH) and sodium bromide (NaBr) [8].
(CH3)3CBr + NaOH → (CH3)3COH + NaBr
2. Decomposition of hydrogen peroxide (H2O2) into water (H2O) and oxygen (O2)
2 H2O2 (l) → H2O (l) + O2 (g)
3. Hydrolysis of methyl acetate (CH3COOCH3) in the presence of mineral acids
CH3COOCH3 (aq.) + H2O (l) → CH3COOH (aq.  + CH3OH (aq.)
The following table lists the differences between the zero, first, and second-order reactions [10].
Zero Order First Order Second Order

The reaction rate is

The reaction rate is The reaction rate is proportional to the
constant over time proportional to the second power of the
and independent of first power of the reactant’s concentration
the reactants’ reactant’s or product of two
Definition concentration concentration reactants’ concentration

Rate equation R = constant R = k [A] R = k [A]2 or R = k [A] [B]

Concentration [A] = kt [A] = [A]o exp (-kt) 1 / [A] = 1 / [A]o + kt

Half-life [A]o / 2k 0.693 / k 1 / k[A]o

Decomposition of Decomposition of Decomposition of

Example nitrous oxide hydrogen peroxide nitrogen dioxide
 Zero order reaction
If the rate of a reaction is independent of the concentration of reactants, then such a
reaction is called a zero-order reaction. The zero-order reaction can be defined as those
reactions in which rate is dependent on the zeroth power of concentration term of
reactant. The rate of reaction remains the same throughout the reaction in such a zero-
order reaction.

Some zero-order reaction examples are listed below:

A. Phtochemical reaction:

A photochemical reaction between the H2 and Cl2 in presence of light is an example of

zero-order reaction.

H2+Cl2→ 2HCl (in presence of light)

B. Decomposition of N2O

Decomposition of N2O in the presence of Pt- catalyst.

2N2O → 2N2 + O2

Zero order reaction integrated rate law

Let us consider a reaction,
A→ product
Rate=dx/dt ∝ [A]0
dx/dt=k[A]0
dx/dt=k
dx=kdt ……………………………………………………………….(1)
On integration of equation (1), we get,
∫dx=k∫dt
x=kt + c …………………………………………..(2)
where c is an integration constant whose value can be determined by using the initial
condition i.e. t=o and x=0, we get the value of c=0. Using this value, equation(2)
becomes
x=kt…………………………………………………………………(3)
This is the mathematical expression of the integrated rate law equation of zero-order
reaction.
Nitrous oxide will decompose exothermically into nitrogen and oxygen, at a temperature
of approximately 575 °C

2N2O→Δ,Ni 2N2(g)+O2(g)

This reaction in the presence of a hot platinum wire (which acts as a catalyst) is zero-
order, but it follows more conventional second order kinetics when carried out entirely in
the gas phase.

2N2O⟶2N2(g)+O2(g)

In this case, the N2O molecules that react are limited to those that have attached
themselves to the surface of the solid catalyst. Once all of the sites on the limited
surface of the catalyst have been occupied, additional gas-phase molecules must wait
until the decomposition of one of the adsorbed molecules frees up a surface site.
 Second-order Reaction
Second order reactions can be defined as chemical reactions wherein the sum of the exponents in
the corresponding rate law of the chemical reaction is equal to two. The rate of such a reaction can
be written either as r = k[A]2, or as r = k[A][B].

Identical Reactants
Two of the same reactant (A) combine in a single elementary step.
A+A⟶P
2A⟶P (2.8.1)(2.8.2)
The reaction rate for this step can be written as

Rate= −1/2× d[A]/dt = +d[P]/dt

and the rate of loss of reactant A

dA/dt=−k[A][A]=−k[A]2(2.8.3)

Where k is a second order rate constant with units of M-1 min-1 or M-1 s-1. Therefore, doubling
the concentration of reactant A will quadruple the rate of the reaction. In this particular case,
another reactant ( B ) could be present with A ; however, its concentration does not affect the
rate of the reaction, i.e., the reaction order with respect to B is zero, and we can express the rate
law as
2 0
v = k [A] [B]
Integration of Equation 2.8.3 yields
1/[A]=1/[A]0+kt (2.8.4)
which is easily rearranged into a form of the equation for a straight line and yields plots similar
to the one shown below
For reactions that follow Equation 2.8.1 or 2.8.2, the rate at which A decreases can be
expressed using the differential rate equation.
−d[A]dt=k[A]2(2.8.6)
The equation can then be rearranged:
d[A]/[A]2= −k dt (2.8.7)
Since we are interested in the change in concentration of A over a period of time, we integrate
between t=0 and t , the time of interest.

∫[A]t[A]o d[A]/[A]2=−k∫t0dt (2.8.8)

To solve this, we use the following rule of integration (power rule):
∫dx/x2 = −1/x + constant (2.8.9)
We then obtain the integrated rate equation.
1/[A]t−1/[A]o = kt (2.8.10)
Upon rearrangement of the integrated rate equation, we obtain an equation of the line:
1/[A]t = kt+1/[A]o(2.8.11)
The crucial part of this process is not understanding precisely how to derive the integrated rate
law equation, rather it is important to understand how the equation directly relates to the graph
which provides a linear relationship. In this case, and for all second order reactions, the linear
plot of 1/[A]t versus time will yield the graph below.
Example 13

At high temperatures, nitrogen dioxide decomposes to nitric oxide and oxygen.

2NO2(g)−→Δ2NO(g)+O2(g)

Experimental data for the reaction at 300°C and four initial concentrations of NO2 are
listed in the following table:

Determine the reaction order and the rate constant.

Experiment [NO2]0 (M) Initial Rate (M/s)

1 0.015 1.22 × 10−4

2 0.010 5.40 × 10−5

3 0.0080 3.46 × 10−5

4 0.0050 1.35 × 10−5

Given: balanced chemical equation, initial concentrations, and initial rates

Asked for: reaction order and rate constant

Strategy:

A. From the experiments, compare the changes in the initial reaction rates with the
corresponding changes in the initial concentrations. Determine whether the
changes are characteristic of zeroth-, first-, or second-order reactions.
B. Determine the appropriate rate law. Using this rate law and data from any
experiment, solve for the rate constant (k).

Solution

A We can determine the reaction order with respect to nitrogen dioxide by comparing
the changes in NO2 concentrations with the corresponding reaction rates. Comparing
Experiments 2 and 4, for example, shows that doubling the concentration quadruples
the reaction rate [(5.40 × 10−5) ÷ (1.35 × 10−5) = 4.0], which means that the reaction rate
is proportional to [NO2]2. Similarly, comparing Experiments 1 and 4 shows that tripling
the concentration increases the reaction rate by a factor of 9, again indicating that the
reaction rate is proportional to [NO2]2. This behavior is characteristic of a second-order
reaction.

B We have rate = k[NO2]2. We can calculate the rate constant (k) using data from any
experiment in the table. Selecting Experiment 2, for example, gives the following:

Rate= k[NO2]2
5.40×10−5 M/s= k(0.010M)2
0.54M−1⋅s−1= k

B. When the highly reactive species HO2 forms in the atmosphere, one important
reaction that then removes it from the atmosphere is as follows:

2HO2(g)→H2O2(g)+O2(g)

The kinetics of this reaction have been studied in the laboratory, and some initial rate
data at 25°C are listed in the following table:

Experiment [HO2]0 (M) Initial Rate (M/s)

1 1.1 × 10−8 1.7 × 10−7

 2 2.5 × 10−8 8.8 × 10−7

3 3.4 × 10−8 1.6 × 10−6

4 5.0 × 10−8 3.5 × 10−6

Determine the reaction order and the rate constant.

Answer second order in HO2; k = 1.4 × 109 M−1·s−1

Note

If a plot of reactant concentration versus time is not linear, but a plot of 1/reaction

concentration versus time is linear, then the reaction is second order.

Example 14
If a flask that initially contains 0.056 M NO2 is heated at 300°C, what will be the
concentration of NO2 after 1.0 h? How long will it take for the concentration of NO2 to
decrease to 10% of the initial concentration? Use the integrated rate law for a second-
order reaction (Equation 14.6.2) and the rate constant calculated above. (0.54M−1⋅s−1=
k)

Given: balanced chemical equation, rate constant, time interval, and initial concentration

Asked for: final concentration and time required to reach specified concentration

Strategy:

A. Given k, t, and [A]0, use the integrated rate law for a second-order reaction to
calculate [A].
B. Setting [A] equal to 1/10 of [A]0, use the same equation to solve for t.

Solution

A We know k and [NO2]0, and we are asked to determine [NO2] at t = 1 h (3600 s).
Substituting the appropriate values into Equation 14.4.9,

1/ [NO2]3600 =1/[NO2]0+kt
 =1/0.056 M+ [(0.54M−1⋅s−1) (3600 s)]
=2.0×103 M−1)

Thus [NO2]3600 = 5.1 × 10−4 M.

B In this case, we know k and [NO2]0, and we are asked to calculate at what time [NO2] =
0.1[NO2]0 = 0.1(0.056 M) = 0.0056 M. To do this, we solve Equation 14.6.214.6.2 for t,
using the concentrations given.

t=(1/[NO2])−(1/[NO2]0)/k
=(1/0.0056 M)−(1/0.056 M)0.54M−1⋅s−1
=3.0×102 s
=5.0 min
NO2 decomposes very rapidly; under these conditions, the reaction is 90% complete in
only 5.0 min.

Molecularity of a reaction
 What is the second-order rate law? (2 marks)

Ques. What is the order of the reaction whose rate constant has the same units as the
rate of reaction?
(ii) For a reaction A + H2O → B; Rate ∝ [A],
What is the order of this reaction? (CBSE 2017) (2 marks)

Ques. How can you tell if a graph is of the first or second order? (2 marks)

Ques. What is the second-order integrated rate law? (2 marks)

Ques. Define the rate of a reaction. (CBSE 2010) (2 marks)

Ques. What are the units of k for a second-order reaction? (2 marks)

Ques. Define the ‘activation energy’ of a reaction. (CBSE 2011) (2 marks)

Ques. If the reactant concentration changes from 0.08M to 0.04M in 10 minutes for
the second-order reaction. Calculate the time it takes for the reactant concentration to
reach 0.01M. (3 marks)

Ques. A reaction is of second order with respect to a reactant. How will the rate of
reaction be affected if the concentration of this reactant is
(i) doubled, (ii) reduced to half? (Delhi 2009)

Ques. Distinguish between the ‘rate expression’ and ‘rate constant’ of a

reaction. (CBSE 2011) (2 marks)

Ques. What do you understand by the rate law and rate constant of a reaction? Identify
the order of a reaction if the units of its rate constant are : (i) L-1 mol s-1 (ii) L mol-1 s-
1
 (CBSE 2011) (2 marks)

Ques. A reaction is of second order with respect to a reactant. How is its rate affected
if the concentration of the reactant is (i) doubled or (ii) reduced to half? (CBSE 2012)
(2 marks)

Ques. Write two differences between ‘order of reaction’ and ‘molecularity of reaction’.