ASC 0305

CHEMISTRY II
CHEMICAL KINETIC
 LEARNING OUTCOMES

a. Explain and use the terms rate of reaction, rate

equation, order of reaction, rate constant, half- life and
activation energy.
b. Calculate order of a reaction by the initial rates
method.
c. Calculate rate constant from initial rates.
d. Write rate law of a reaction.
e. Deduce zero-, first-, and second-order reactions.
f. Calculate half-life for a first-order reaction
 LEARNING OUTCOMES CONT.

g. Define reaction mechanisms and identify the rate

determining step.
h. Explain the collision theory on the reaction rate.
i. Explain the effect of catalysts, concentration and
temperature on the rate of a reaction.
j. Explain the relationship between the rate
constants with activation energy and temperature
using Arrhenius’ equation
 Rate of Reaction
How to measure reaction rate?
What is reaction rate?
The rate of reaction can be observed by
Is the measure of how quick the reactants
watching the disappearance of a reactant
in a reaction change into the product of
or the appearance of a product over time
the reaction

Reactants will Product(s) will

decrease as increase as
reaction reaction
proceed proceed
Consider the hypothetical reaction,
Rate of Reaction
A(g) + B(g)  C(g) + D(g)

Rate = M/s
= Concentration
time

Note that the reaction does not go entirely to completion.

The concentrations of reactants are more than 0 and the concentrations of

products are less than 1.0 M
The decrease in concentration of a reactant per unit
time or the increase in concentration of a product per
unit time is known as the rate of reaction.
A(g) + B(g)  C(g) + D(g)
  ∆[ A ]
Rate   of  disappearance   of   A  = −  
∆t
  ∆[ B]
Rate   of  disappearance   of   B  = −  
∆t
  ∆[ C]
Rate   of  formation  of  C  = + 
∆t
  ∆[ D ]
Rate   of  formation  of   D  = + 
∆t
  ∆[ A ] ∆[ B ] ∆[ C] ∆[ D ]
Rate =  − = −   = +  = + 
∆t ∆t ∆t ∆t
 Rate of Reaction
For the following general reaction,

aA(g) + bB(g)  cC(g) + dD(g)

a moles of A react with b moles of B to form c moles

of C and d moles of D then the rate of the reaction is

  ∆[ A ] ∆[ B] ∆[ C] ∆[ D]
Rate   = − =  −   = +  = + 
a∆t b∆ t c∆ t d ∆t
Dinitrogen pentoxide

Negative [ ] symbolized for

because we concentration
are using up ∆ symbolized for ‘change in’
the reactant or the different
EXAMPLE 1.1

For the following reaction

2N2O5(g)  4NO2(g) + O2(g)
the rate of disappearance of N2O5 is 1.4 x 10-4 molL-1s-1.
What are the rate of formation of NO2 and O2?
 

rat
 Rate of Reaction EXPRESSION

The rate of a reaction can be expressed in three ways:

• The initial rate of reaction (t = 0; negative slope)

• The instantaneous rate of reaction (specific time interval)

• The average rate of reaction (over a time interval)

 Initial rate of reaction
The initial rate of the reaction corresponding to these
initial concentrations is calculated as follows:

  ∆[ reactant]
Initial   rate  =  −
∆t
Initial
   rate  
  0.036  −  0.050
Initial   rate  =  −  
200  −  0
− 4  −1
 
 =1.4  x  10 Ms
2N2O5(g)  4NO2(g) + O2(g)
 Instantaneous rate of reaction

2N2O5(g)  4NO2(g) + O2(g)

For the above reaction,

the instantaneous rate
at t = 400 s is

Instantaneous
    rate  
 Average rate of reaction

The average rate of a reaction over a time interval is

calculated by dividing the change in concentration
over that time period.

  [ reactant   at   t2 ] −[ reactant   at   t1 ]
Rate  = 
t 2 −   t1

The average rate of the reaction is not constant,

but changes with time.

The average rate steadily decreases as the reaction

proceeds.
The average rate of the reaction of N2O5 is shown in this
table

t2 (s) t1 (s) [N2O5]2 /M [N2O5]1 /M Average

rate/ M s-1
100 0 0.0435 0.0500 6.5 x 10-5
200 100 0.0380 0.0435 5.5 x 10-5
300 200 0.0330 0.0380 5.0 x 10-5
400 300 0.0290 0.0330 4.0 x 10-5
500 400 0.0260 0.029 3.0 x 10-5
600 500 0.0235 0.026 2.5 x 10-5
700 600 0.0215 0.0235 2.0 x 10-5
 Rate Law
The rate law is an expression indicating how the rate
depends on the concentrations of the reactants (and
catalysts).
aA(g) + bB(g)  cC(g) + dD(g)

  ∆[ A ] ∆[ B] ∆[ C] ∆[ D]
Rate   = − =  −   = +  = + 
a∆t b∆ t c∆ t d ∆t

The rate law is,

Rate = k[A]x[B]y

where k is the rate constant, x and y are order for A and B

respectively , and x + y is overall order of the reaction.
 Order of reaction

Order of a reaction cannot be deduced from the

coefficients of a balanced equation.
Order of a reaction can be determined from experiment
using initial rate method.

The reaction can be zero, first, second or third order.

 Zero Order of reaction

For reactions that are zero order reactions

A  Products

The rate equation is:

Rate = k[A]0 = k

This rate is independent of the concentration of

the
reactants.

Zero-order reactions have a constant rate.

 First Order of reaction

For the first order reaction, A  Products

The rate equation is: Rate = k[A]

The rate of reaction is proportional to the

concentration of A.

-If the initial concentration of A is doubled, the

initial rate of reaction is also doubled.
-If the initial concentration of A is halved the initial
rate of reaction is cut into half.
-If the reaction is proceeding twice as fast, the
amount of time required for the reaction to reach
equilibrium would be half the initial time.
 Second Order of reaction

For the second order reaction,

A  Products
Rate = k[A]2

The rate of reaction is proportional to the square of

the concentration of [A]2 ,

if the [A] is doubled the rate of the reaction will increase

by a factor of 4 (22 = 4).
If the [A] is halved the rate of the reaction will decrease by
a factor of 4 (1/2)2 = ¼.
 Second Order of reaction

Example:

The reaction between nitrogen dioxide and fluorine.

2NO2(g) + F2(g)  2NO2F(g)

Rate = k[NO2] [F2]

The reaction is first order for NO2, first order for F2 and
second order for overall reaction.
 Third Order of reaction

For the third order reaction,

A  Products,
Rate = k[A]3

Examples
Reaction between nitric oxide and oxygen
2NO(g) + O2(g)  2NO2(g)
Rate = k [NO]2 [O2]

The reaction is second order for NO and first order

for O2 and third order for overall reaction.
 Order of reaction
Double Quadruple Not affected

OVERALL ORDER:

First order with respect to A + First order with respect to B = Second order overall
 The reaction is second
Concentration of NO is double up The rate quadruple
order with respect to NO

Trial 1 VS Trial 3
Concentration of O2 double up The rate double The reaction is first order
with respect to O2
 Rate constant unit

If you know the rate constant (k), you know the OVERALL reactions order!!
EXAMPLE 1.2
The following table shows the initial rate at 25 oC for
the following reaction. What are the rate-law
expression and the specific rate-constant for this
reaction?

A(g) + B(g)  C(g)

Experiment Initial [A] Initial [B] Initial rate of

number (M) (M) formation of C (M/s)

1 0.10 0.10 4.0 x 10-4

2 0.20 0.30 8.0 x 10-4
3 0.10 0.20 4.0 x 10-4
The rate of the reaction is, Rate = k[A]x[B]y

We need to determine x and y in the equation.

Rate   𝟑 k (0.10 )x (0. 2 0 ) y 4 .0  x  10− 4

 
=  x y
=  −4
Rate  1 k (0.10 ) (0.10 ) 4.0  x   10
2y = 1
y = 0
x y −4
Rate  2 k (0.20 ) (0.30 ) 8.0  x   10
 
=  = 
Rate  1 k (0.10 ) (0.10 ) 4.0  x  10− 4
x y

(2x)(3y) = 2
x=1
 

The rate law is

Rate = k[A]1[B]0 = k[A]

The rate constant, k can be determined using data

from any experiment,

From experiment 1,

The rate law expression can be written as

Rate = k[A]
Rate = 4.0 x 10-3 s-1[A]
EXAMPLE 1.3
Use the following data to determine the rate-law
expression and the specific rate constant for the
reaction.
A(g) + B(g) + C(g)  D(g) + E(g)

Initial Initial Initial [C] Initial rate of

Experiment [A] (M) [B] (M) (M) formation of
Number D (M/s)

1 0.20 0.10 0.10 1.0 x 10-4

2 0.20 0.30 0.20 3.0 x 10-4

3 0.20 0.10 0.30 1.0 x 10-4
4 0.60 0.30 0.40 9.0 x 10-4
The rate of the reaction is
Rate = k[A]x[B]y[C]z

The value of x, y and z can be determined by

comparing the two set of experiments.
 
Rate   3 x y
=  k (0.20 ) (0. 10 ) ¿ ¿
Rate  1
3Z = 1
z=0
  Rate   2 x y
=  k (0.20 ) (0. 3 0 ) ¿ ¿
Rate  1
3y2z = 3
3y = 3
y=1
  Rate   4 x y
=  k (0. 6 0 ) (0. 3 0 ) ¿ ¿
Rate   2
3x2z = 3
3x = 3
x=1
Thus the rate law can be written as
Rate = k[A][B][C]0 = k[A][B]

This reaction is first order with respect to A, first order

with respect to B, and second order for overall
reaction.
Finally the rate constant, k can be determined using
data from any experiment.
  Rate
k  = 
[A ][B ]
From experiment 1,
  1.0  x  10− 4  M s− 1 −3 −1 − 1
k  =   = 5  x   10 M s
[ 0.20  M ] [0.10  M ]
The rate law expression can be written as
Rate = 5 x 10-3 M-1s-1[A][B]
 INTEGRATED Rate Law

The integrated rate equation relates time and

concentration for chemical reaction.

From the integrated rate equation we can

predict the amount of product that is
produced in a given amount of time.
 INTEGRATED Rate Law

Determination of Integrated Rate Equation

from Graphical Analysis
 INTEGRATED Rate Law

Zero order reaction

For the zero order reaction: aA  products

The rate equation is

 1 d[ A]
−
a dt ( ) 0
=  k [ A ]  =  k

 [A ] t

∫ d [ A ]  =  − ak ∫ dt
[A ] o 0
 The integrated rate equation for zero order
reactions is:

[A] = [A]0 – akt

where [A]0 is concentration of A (mol/L) at time t = 0,

[A] is concentration of A (mol/L) at time t, k is specific
rate constant, t is time elapsed since beginning of
reaction and a is number of mol of reactant.
 The plot of [A] versus time is a straight line with
k = - slope of the line

time required for half

Half-life, t1/2 of the reactant to be
consumed
  [A] = [A]0.

  [A]o = [A]o - kt1/2

  [ A ]o
t 1/2 = 
2k

Notice that, for zero-order reactions, the half-life

depends on the initial concentration of reactant and
the rate constant.
 INTEGRATED Rate Law

First order reaction

For the first order reaction:

aA  products

The rate equation is

 1 d[ A]
−
a dt( ) =  k [ A ]

 [A ] t
d[ A]
∫ [ A ]  = − ak ∫ dt
[A ] o 0
The integrated rate equation for first order reactions is:

ln[A]o – ln[A] = akt

where [A]0 is concentration of A (mol/L) at time t = 0, [A]

is concentration of A (mol/L) at time t, k is specific rate
constant, t is time elapsed since beginning of reaction
and a is number of mol of reactant.
 Half-life, t1/2
Solve the first order integrated rate equation for t.
  1 [ A]o
t  =  ln
ak [A ]
At time t = t1/2, the expression becomes:

The plot of ln[A] versus time is a straight line with

k = - slope of the line

The half-life of a first order reaction is independent of its

initial concentration of A.
EXAMPLE 1.4
For the following reaction

PCl5(g)  PCl3(g) + Cl2(g)

is first order in PCl5 with rate constant, k is 2.2 x 10-5

s-1 at 102 0C.
Calculate the half- life of PCl5.
How many second it will take for PCl5 to decompose
from 0.50 M to 0.15 M?

SOLUTION
The half-life
  0.693 0.693 4 
t 1/2  =   = = 3.15 x  10 s
ak −5
2.2  x 10  s −1
Time taken for PCl5 to decompose from 0.50 M to 0.15 M

ln[PCl5]o – ln[PCl5] = akt

ln0.50 – ln0.15 = 2.2 x 10-5t

t = 54726 s
Second order reactions

For reactions that are second order reactions

aA  Products

The rate equation is:

 
 
The integrated rate equation for second order reactions is:

1  1
−   =  akt
[ A ] [A] o

where [A]0 is concentration of A (mol/L) at time t=0, [A]

is concentration of A (mol/L) at time t, k is specific rate
constant, t is time elapsed since beginning of reaction
and a is number of mol of reactant.
 THE INTEGRATED RATE EQUATION
Half-life

At the half-life, t1/2

[A] = 1/2[A]0.

The plot of 1/[A] versus time is a straight

line with k = + slope of the line.

Note that the half-life of a second order reaction depends on

the initial concentration of A.
EXAMPLE 1.5
The following reaction

2NOCl(g)  2NO(g) + Cl2(g)

is second order in NOCl with rate constant, k is 2.8

x 10-5 M-1s-1 at 300K.

(a) Calculate the half- life of the reaction if the initial

concentration of NOCl is 1.0 M.

(b) What would the concentration of NOCl be after

(c) 60 minutes if if the initial concentration of NOCl

is 1.0 M.
The half-life of the reaction
  1 1
t 1/2  =  =  −5
=17857  s
ak [ A ] o 2  x  2.8  x  10 x  1.0
The concentration of NOCl after 60 minutes
 

 
[NOCl] = 0.83 M