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

Example nitrous oxide hydrogen peroxide 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
v = k [A]2[B]0
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’.