School of Aygoda

KG, PRIMARY, SECONDARY & COLLEGE PREPARATORY

Academic Year 2012E.C
Tel, 011-440-43-78/79
Teacher name: Mrs. Heregewen
Grade: 11 Subject: - Chemistry 4th Quarter Lesson - 2

Concentration-Time Equation (Integrated Rate Law)

 Express the concentration of a reactant as a function of time.
1. Zero order reaction
A zero order reaction is a reaction whose rate of reaction does not depend on reactant concentration. For
the general reaction.
A Product
The zero order rate law

[A]t= kt + [A]o
Where [A]:- concentration of “A” at time (t)
[A]o:- concentration of “A” at zero time
[A]t= -Kt + [A]o Integrated rate equation for zero order reaction.
This is a linear equation in the graph with -k slope.

[A]o

[A]t

Slope= -x

Fig a plot of [A] versus t for a zero-order reaction.

1
Example:- the decomposition reaction 2N2O(g) 2N2(g) + O2(g) is a zero order reaction that occurs on a
hot platinum surface. The concentration of N2O reduced from 0.4M to 0.1M in 20 sec. find the rate
constant of the reaction.
Given
[A]o= 0.4M
[A]20sec.= 0.1M
t = 20 sec.
Required
K=?

Solution
[A]t = -kt + [A]o

=0.015M/s
2. First-order reaction
First order reaction is a reaction whose rate of reaction depends on the reactant concentration raised to the
first power.
A Product
The rate is

= k[A]
By using integration

∫ ∫ , ln[A]t – ln[A]o = -kt

ln[A]t = ln[A]o -kt is an integrated rate equation for first order reaction.

Or log[A]t= + log[A]o

2
log[A]t

(ln[A]t
Slope= -k

The graph of first order reaction

example: - The decomposition of hydrogen peroxide is first order in H2O2 and the
rate constant is 1.06*10-3min-1. If the initial concentration of H2O2 is 0.02M, what
is the concentration after exactly 100 minutes?
Given
K= 1.06*10-3/min
[A]o = 0.02M
t = 100 min.
Required [A]100min= ?
Solution
ln[A]t = ln[A]o -kt

log[A]t= + log[A]o

log[A]t= + log0.02

= + log2*10-2
=-
0.046 + log102 + log1010-2 +
=-0.046 + 0.3 -2
= -1.746
Log10 [A]t = -1.746
[A]t = 10-1.746= 0.0179 0.018M

3
 3. Second-order reactions
A second order reaction is a reaction whose rate depends either on the concentration of one reactant raised
to the second power or on the concentrations of two different reactants, each raised to the first power.
2A Product

Where = k[A] from the rate law r= k[A]2

Then =kt+ integration rate equation for second order

reaction.

Slope= k
𝐴𝑡

𝐴𝑜

The graph of versus time of second order reaction.

Example:- the decomposition of hydrogen iodide is second order reaction with rate constant K = 30
l/mol.min at 443 . Calculate the time required for the concentration of hydrogen iodide to fall 0.02M to
0.01 M at 443 .
Given
K= 30L/mol.min
[A]0 = 0.02M
[A]t = 0.01M
Required t=?
Solution

=kt+

( ) ( )
t= = = 1.67min

The Half life of a Reaction

The half-life of a reaction is the time required for the concentration of a reactant to decrease to half of its
initial concentration.

The half-life is the time it takes for the concentration of A to fall from [A]0 to [A]0, i.e [A] = [A]0

4
  The half-life of a reaction is designated by the symbol, t1/2
 the mathematical expression for the half-life of a first order reaction is determined by
substituting t= t1/2 and [A] = ½[A]0 in equation.

log

ln = or ln2=kt1/2

t1/2= = the half-life equation of first order reaction.

Note:- half-life of zero order and second order reaction is depend on initial concentration but first order
does not depend on initial concentration of the reactant.

Order Rate Concentration-time Equation of k Unit of “k” Half-life

equation equation equation
0
0 r=k[A] [A]t=-kt+[A]0 M/s
t1/2=
First r=k[A] log[A]t= + log[A]o s-1
t1/2=
Second r=k[A]2 ( ) M-1s-1
=kt+ t1/2=

Example:- the decomposition of N2O5 in CCl4 at 45 is first order reaction with k= 6.32*10-4/s. if the
initial concentration N2O5 is 0.4mol/L.
A. calculate t1/2
Given
K=6.32*10-4s-1
[A]0= 0.4mol/L
Required
t1/2= ?
Solution

t1/2= = = 0.1097*104sec = 1097 sec

B. find the concentration of N2O5 remaining after t1/2

log[A]t1/2= + log[A]o = +log0.4

= -0.301+(-0.398)= -0.699
[A]t1/2= 10-0.699 =0.199

5
Do exercise 4.8 on your text book page 240

Reaction Mechanism
Reaction mechanism is the sequence of bond making and bond breaking steps that occurs during
the conversion of reactants into products. Some reaction occur in a single step
Example:- NO + O3 NO2 + O2
Most chemical reaction however involve a sequence of steps
Example:- 2NH3+ OCl- N2H4 + Cl- + H2O
Step1:- NH3 + OCl- NH2Cl +OH-(fast reaction)
Step2:- NH2Cl + NH3 N2H+5 + Cl- (slow reaction)
Step3:- N2H+5 + OH- N2H4 + H2O (fast reaction)
Each of the steps in the reaction sequence is called an elementary reaction. Species that exist in
elementary reactions but not in the overall reaction are called intermediates
Example:- NH2Cl, OH- and N2H+5 are intermediators for the above reaction
There are two requirements for a possible reaction mechanism
I. It must be consistent with the stoichiometry of the overall reaction
II. It must agree with the experimentally determined rate law.

Molecularity of an Elementary Reaction

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 are called the molecularity of the
reaction. It is the number of reactant molecules taking part in a single step of the reaction.
Example:-
a) PCl5 PCl3 +Cl2 (unimolecular) – single molecule
b) 2HI H2 + I2 (bimolecular) – collision of two molecules
c) 2SO2 + O2 2SO3 (Termolecular) – collide of three molecules
d) 2NO + O3 NO2 + O2 (bimolecular)
e) 2CO + O2 2CO2 (Termolecular)
f) 2FeCl3 + SnCl2 SnCl2 + 2FeCl2 (Termolecular)

Characteristics of Elementary Processes

1) Elementary processes are either unimolecular, biomolecular or termolecular
2) The exponent of the concentration terms in the rate law for an elementary process are the
same as the stoichiometric coefficients in the balanced equation for the process.
3) Elementary process are reversible some many reach a condition of equilibrium in which a
rats of the forward and reverse process are equal.
4) Certain species are produced and consumed in the elementary process.
5) The rate determining step is slow reaction of elementary reaction.
Overall rate = the rate of the slowest step

6
Examples:- the reaction NO2(g) + CO(g) NO(g) + CO2(g) can be thought of as occurring in
two elementary steps:
Step1:- NO2 + NO2 NO + NO3 (slow step)
Step2:- NO3 + CO NO2 CO2 (fast step)
a) Identify the intermediate (s) NO3
b) Identify the rate determining step step 1
c) Determine the molecularity of this reaction Bimolecular.
Do exercise 4.9 on page 243, exercise 4.10 on page 245, review exercise from page 247-252 on your text
book