STK 1102 Chemical Kinetics

LU1 Basic Terms and Concepts

• Introduction
• Types and Rate of Reaction
• Factor affecting reaction rates
• Rate Law and Rate Constant
• Order of reaction
• Molecularity of reaction
• Basic kinetic laws (zero,1st, 2nd, 3rd order)
 What is Kinetics ?
Kinetics is the study of the speed at which chemical
and physical processes take place.

Chemical kinetics deals with trying to answer the

following questions:

1. At what rate does a chemical reaction undergo

change under a given set of conditions ?
2. What effect will a change in conditions have on
the rate at which a chemical change occurs?
3. What information is available as to HOW the
chemical reaction occurs ?
 Types of Reaction
Two groups of chemical reactions - homogenous and
heterogeneous.
Homogeneous - reaction occurs in one phase only and
the system is uniform throughout.
E.g. H2 (g) + I2(g)  2HI(g)
HCl(l)
CH3COOCH3(l) + H2O(l)  CH3COOH(l) + CH3OH(l)
Heterogeneous - reaction on the surface of a catalyst or
the walls of a container; the mixture is not uniform
throughout.
tungsten
 N2(g) + 3H2(g)
2NH3(g) alumina
C2H5OH(l)  C2H4 (g) + H2O(l)
 Types of Reaction Rates
There are two types of reaction rates:
1. Instantaneous Rates
2. Average Rates

Instantaneous Rates - the change in product formation

at a moment in time.

A plot of product concentration vs. time shows a curve with

the tangent slope at any place on that curve gives the
instantaneous rate at that moment in time.

tan  = slope = side opposite/side adjacent = y/x

 Types of Reaction Rates

Average rate - the difference in the concentration

of product or reactant divided by the the difference
in the time.

Av. Rate = ([product]final - [product]initial)/(tfinal - tinitial)

Av. Rate = - ([reactant]final - [reactant]initial)/(tfinal - tinitial)

 Definitions of Rate

• Rate of Consumption of a reactant is -d[R]/dt

• Rate of Formation of a product is d[P]/dt
 Rate of Reaction
The rate of reaction is defined as the no. of molecules
of a given species reacting per unit time.
It shows how the concentration of the reactants or
products changes with time.
200°C
Example: CO + NO2  CO2 + NO
The rate of this reaction may be expressed in terms of
change in the concentration of reactants or products.

Rate = -d[reactant]/dt = -d[CO]/dt = -d[NO2]/dt

The minus sign makes the rate a positive quantity.

 Rate of Reaction
The rate can also be expressed in terms of change
in the concentration of products.

Rate = + d[product]/dt = + d[CO2]/dt = + d[NO]/dt

The plus sign is associated with product because

its concentration increases.
 Rate of Reaction
• Consider a reaction of the form
A + 2B  3C + D
• B is consumed twice as fast as A; C is formed thrice
as fast as D
• Only one numerical value is used to represent the
whole reaction.
Rate of reaction, r = d[D]/dt = 1/3 d[C]/dt

= - d[A]/dt = -½ d[B]/dt
 Rate of Reaction
Example: 2HI(g)  H2(g) + I2(g)
The rate of consumption of HI is double the rate of
formation of H2 or I2.

International convention:
[reactant or product]
Rate of reaction, r = —————————————
Appropriate stoichiometric factor
Time derivative of [substance]
= ——————————————
Appropriate stoichiometric factor
= - ½ d[HI]/dt = d[H2]/dt = d[I2]/dt
 Reaction Rates
Example: N2(g) + 3H2(g)  2 NH3(g)

The rate of this reaction expresses how fast the

reactants N2 and H2 disappear and how fast the
product NH3 forms.

Rate = -d[N2]/dt = -1/3d[H2]/dt = + 1/2d[NH3]/dt

The negative signs indicate [N2] and [H2] decrease.

The positive sign indicates [NH3] increase with time.

 Reaction Rates
Example:

• The rate of consumption of CH3 radicals in the reaction 2

CH3(g)  CH3CH3(g) was reported as 1.2 mol L-1 s-1 under a
certain set of conditions. What is the rate of formation of
CH3CH3(g)?

• There is 1 mol CH3CH3 formed for every 2 mol CH3

consumed.

• Therefore the rate of formation of CH3CH3 is half the rate of

consumption of CH3, or 0.6 mol L-1 s-1
Factor Affecting Reaction Rates

1. Nature of the reactants

2. Concentration of reactants

3. Surface area of the reactants

4. Temperature

5. Nature of catalyst, if present.

 Nature of Reactants

Reactions between polar ionic molecules are rapid

Example: Ag+ + Cl-  AgCl (s)

Electron transfer reactions take longer time than ionic

reactions.
Example: Fe2+ + Ce4+  Ce3+ + Fe3+

Complex reactions are slow in nature

Example: Mg2+ + C2O42-  MgC2O4(s)
 Concentration of Reactants
Raising the concentration of a reactant increases
the reaction rate.

For a reaction A  Product, rate is doubled when

[A] is doubled.

[Reactant]  => No. of particles/volume 

=> Effective collision rate of molecule 

=> Higher rate of reaction.

 Surface area of the Reactants

In heterogeneous reaction, the rate of reaction

depends on the area of contact between the phases.

The rate of reaction is proportional to the surface area.

Particle size of reactant 

=> surface area 

=> rate of reaction .

 Rate Laws
• A rate law is an equation expressing the rate of a reaction
in terms of the molar concentrations of the species
involved in the reaction.

• The rate is often found to be proportional to the molar

concentrations of the reactants raised to a simple power.

• These powers are the orders of the reaction.

• For the rate expression, Rate = k[A]m[B]n;

then the reaction is m order in A, n order in B, and m+n
order overall.
 Rate Laws
Basic Rate Expression
Consider the following reaction:
aA + bB  Products

The rate expression is:

Rate = k [A]m[B]n

where k = rate constant

m = rate order in respect to A
n = rate order in respect to B
The TOTAL Order of the reaction is m + n.
 Rate Laws
At constant temperature, the rate of a reaction is a
function of the concentration of reactants or products.

The rate law for a reaction cannot be determined from

the balanced chemical equation for the reaction. It can be
determined only by experiment.

The rate law provides concise expressions for the course

of reaction, helps in calculating reaction times, yields,
and optimum conditions.
 Rate Laws

Example:

• The reaction between the amino acid tyrosine

(Tyr) and iodine obeys the rate law: r
= k[Tyr][I2] Classify it by order.

• From the powers in the rate expression, (1 and 1),

the reaction is first order in Tyr, first order in I2,
and second order overall.
 Rate Constant

The rate constant of a chemical reaction is a measure

of the rate of reaction when all the reactants are at unit
concentrations.

Rate = k x (function of concentration of reactant)

If concentrations are equal to unity,

 Rate of reaction = k where k is rate constant or

rate coefficient.
 Rate Constant
Rate constant, k depends on the nature of reaction
and temperature. => k increases with temperature.
The rate constant is a characteristic of a chemical
reaction - a numerical measure of how fast a reaction
can occur.
If moles per liter is used, units for the rate constant
mole per liter
————————
(s)(moles per liter)n
where n is the total order of reaction.
First order, unit of k is s-1;
2nd order, unit of k is liter mol-1s-1.
Balanced Equations & Rate Expression

H2(g) + I2(g)  2HI(g) Rate = k[H2][I2]

2 N2O5(g)  4 NO2(g) + 2H2O(g) Rate = k[N2O5]1

2 NOCl(g)  2 NO (g) + Cl2 (g) Rate = k[NOCl]2

CHCl3(g) + Cl2(g)  CCl4(g) + HCl(g)

Rate = k[CHCl3][Cl]1/2
 Elementary Reactions
• An elementary reaction is one whose mechanism of
occurrence is just what is written in the reaction
equation.

• Elementary reactions involve only one or two

molecules.

Example: H + Br2  HBr + Br

• This equation signifies that an H atom attacks a Br2

molecule and produces an HBr molecule and a Br atom.
 Molecularity vs. Order
Terms that seem to conflict

1. MOLECULARITY: represents the stoichiometric

values used to balance the chemical equation.

2. KINETIC ORDER: represents values determined

experimentally and cannot, in general deduced from
the coefficients of the balanced equation.
 Molecularity vs. Order
• The molecularity of a reaction refers to a particular
elementary reaction which is postulated as part of a
proposed mechanism.

• The order of a reaction is an empirical quantity

which follows from an experimentally-determined
rate law.

• For an elementary reaction, the rate law can be

written down from its chemical equation.
 Molecularity
• The molecularity of an elementary reaction is the
number of molecules coming together to react.
• Elementary reactions may be
– unimolecular, in which a single molecule
shakes itself apart or into a new arrangement of
its atoms
– bimolecular, in which two molecules collide
and undergo some changes.
 Writing Rate Laws for
Elementary Reactions
• The reaction H + Br2  HBr + Br is bimolecular. Its
rate law is r = k [H][Br2]
• Bimolecular reactions are second order. (But it is NOT the
case that second-order reactions are necessarily bimolecular, unless
they are elementary reactions.)
• Unimolecular reactions are first order.
• For a reaction such as ka kb .
A I P
d[A]/dt = - ka[A]
d[I]/dt = ka[A] - kb[I]
d[P]/dt = kb[I]
 Order of Reaction
Consider a general reaction
aA + bB + cC  pP + qQ + ….

Rate = k [A]x[B]y[C]z
The order of reaction is defined as the sum of the
powers to which the concentration terms are raised
in the rate-law equation.

The total order of reaction = x + y + z

 Order of Reaction
Example: The decomposition of hydrogen peroxide
H2O2  H2O + 1/2 O2
Rate Law: -d[H2O2]/dt = k[H2O2]

First order reaction since the concentration

term is raised to the power of unity.

Example:
2 CH3CHO  2 CH4 + 2 CO
Rate Law: -d[CH3CHO]/dt = k[CH3CHO]2

Second order reaction

 Order of Reaction
Example: The reaction 2 NO + O2  2 NO2

Rate Law: -d[NO]/dt = k[NO]2[O2]

Second order with respect to NO and First

order with respect to O2.

The overall reaction is thus of the Third order.

 Order of Reaction
It is very seldom that reactions of order > 3 exist.

But there are reactions in which order of reaction may

be zero or fractional.
450°C
Example: CH3CHO  CH4 + CO

Rate expression: -d[CH3CHO]/dt = k[CH3CHO]3/2

The overall reaction is of the order of 3/2.

Zero order reaction - reaction which is independent

of concentration of reactions.
 Effect of Concentration on Rate
Consider the reaction between nitric oxide and oxygen

2 NO(g) + O2(g)  2 NO2(g)

Rate = k [NO]m [O2]n

Experimentally m =2, n =1;

The reaction is 2nd order in [NO]; 1st order in [O2]
or 3rd order overall.

But what does this really mean ?

 Effect of Concentration on Rate
Rate = k [NO]m[O2]n

If [NO] is held constant in 2 experiments while

[O2] is doubled from c to 2c (Isolation Method).

The rate law predicts that the rate will double.

Rate (exp 2) k[NO]2 [2c]

————— = —————— = 2
Rate (exp 1) k[NO]2 [c]

If [O2] is doubled, the rate will double (first order).

 Effect of Concentration on Rate

Rate = k [NO]m[O2]n

If [O2] is held constant in 2 experiments while

[NO] is doubled from c to 2c (Isolation Method)

=> the rate law predicts that the rate will quadruple.

Rate (exp 2) k [2c]2 [O2]

————— = —————— = 22 = 4
Rate (exp 1) k [c]2 [O2]

The fact that the reaction is second order in NO

=> the rate is proportional to the square of [NO]
 Effect of Concentration on Rate
(General Rules – Isolation Method)

If the concentration of one reagent doubles while the

other reagent concentration is unchanged, and the rate is:

Unchanged - the order is ZERO with respect to the

changing reactant.
Doubled - the order is FIRST with respect to the
changing reactant.
Quadrupled - the order is SECOND with respect to the
changing reactant.
 Determining the Rate Law
Isolation Method
• The method of isolation puts all but one reactant
in such large excess that the concentration is
essentially zero.
• The order determined for the remaining reactant is
then a pseudo-order for the reaction.
• The various pseudo-orders can be put together to
give the overall order.
 Determining the Rate Law
Exercise

Consider the reaction: CO + NO2  CO2 + NO

[CO] M 0.10 0.20 0.30 0.10 0.20 0.30

[NO2]M 0.10 0.10 0.10 0.20 0.20 0.20
Rate M/s 0.005 0.010 0.015 0.010 0.020 0.030

What is the rate of the reaction with respect to both

CO and NO2 ?
 Determining the Rate Law
Methods of Initial Rates

The method of initial rates measures the rate at the

beginning of a reaction for several different initial
concentrations of reactant.
 Determining the Rate Law
Method of Initial Rates
Example
The initial rate of a reaction depended on the concentration of a
substance J as follows.
[J]0/(10-3 M) 5.0 8.2 17 30
r0/(10-7 M s-1) 3.6 9.6 41 130
Find the order of the reaction with respect to J and the rate
constant.
r0 = k[J]0n, so log r0 = n log [J]0 + log k
log [J]0 0.70 0.91 1.23 1.48
log r0 0.56 0.98 1.61 2.11
log r0 goes up twice as fast as log [J]0, so n = 2 and
log k = 0.56-2(0.70) = -0.84; k = 0.15 M-1s-1
 Integrated Rate Laws
The concentration of a reactant, A, as a function of time,
can be equated to the rate law, r = k[A]n or
- dA/dt = k[A]n
Zero Order Kinetics
A reaction of zero order is represented as A  B
where A and B are the reactant and product respectively.

-d[A]/dt = k[A]0 = k or -d[A] = - kdt

Integrating between [A]0 and [A] and between 0 and t,

[A]t - [A]0 = - kt ----- (1), and rearranging

[A]0 - [A]t = kt ------- (2)

 Zero Order Kinetics
A Zero Order reaction is one whose rate does
not depend on the concentration of the reactants.
i.e. Rate = k.
Rearranging equation (2) into the
following form:

[A] [A] = -kt + [A]0 ---- (3)

A plot of [A] vs. Time gives

a straight line for zero order
reactions.
Time
 Zero Order Kinetics
Ways to Determine if a reaction is Zero Order

(1) Solve equation (2) for the rate constant k

k = ([A]0 - [A])/t

Insert [A] at various times, t. If the value of the rate

constant , k is constant, then the reaction is ZERO
ORDER.

The units for a zero order rate constant are

moles/liter-time (e.g. moles/liter-sec)
 Zero Order Kinetics
Ways to determine if a reaction is Zero Order

(2) Half-Life Method:

The time for a reaction to go half-way is defined
by: t = t1/2; [A] = [A]0/2

Equation (2) becomes:

[A]0 - [A]0/2 = kt1/2

Solving for t1/2 : t1/2 = [A]0/2k

The Half-Life is directly proportional to the initial

concentration of reactant.
Characteristics of Zero Order Kinetics
1. The dimension of specific rate constant is
concentration/time, i.e. mol l-1 s-1
2. The product concentration is directly proportional
to the time.
=> plot of product (x) vs time (t) for such a reaction
would give a straight line passing through the origin,
and the gradient is the rate constant
3. The half-life of the zero order reaction is proportional
to the initial concentration of reactant.
When x = a/2, t = t1/2 => a/2 = k0t1/2 => t1/2  a
where a is the initial concentration of the reactant.
 Examples of Zero Order Reaction
Some heterogeneous reactions of zero order occurring
on surfaces are:
hot Pt wire
2 N2O  2 N2 + O2
tungsten
2 NH3  N2 + 3H2
gold
2 HI  H2 + I2
The reaction occurs only on the surface of the catalyst.
When the surface is saturated, the amount of absorbed
gas is constant
=> increase in pressure cannot change the surface conc.
=> reaction rate is independent of [reactant].
 Examples of Zero Order Reaction
In reactions between two or more substances,
the rate may have a zero order dependence upon
the concentration of one of them.

Example: CH3COCH3 + I2  ICH2COCH3 + HI

Rate = -d[I2]/dt = k[CH3COCH3 ]

The reaction is first order in acetone, but zero order

in iodine.

The rate may be measured by monitoring the decrease

in [I2].
 First Order Kinetics

Many reactions follow First Order Kinetics.

The general reaction is: A  Products

Rate = - d[A]/dt = k[A]1

Rearranging the equation:

-d[A]/[A] = kdt ----- (1)

continue...
 First Order Kinetics
- d[A]/[A] = kdt ----- (1)

Taking equation (1) between the limits of [A] = [A]0

at t = 0 and [A] = [A] at t = t {integrate between limits}

ln [A] - ln [A]0 = - kt

Rearranging and combine the log terms:

ln([A]0/[A]) = kt -------- (1A)

 First Order Kinetics
Ways to determine if a Reaction is First Order (1)

Rearranging equation 1A,

ln [A] = -kt + ln [A]0 ------- (3)
y = mx + c

ln [A] A plot of ln[A] vs time

gives a straight line for
First Order Reactions

time
 First Order Kinetics
Ways to determine if a Reaction is First Order (2)

ln([A]0/[A]) = kt -------- (1A)

Solve this equation for the rate constant k;

k = (1/t)ln ([A]0 / [A]) ------- (2)

Insert [A] at various time t. If the value of rate

constant k is constant, then the reaction is FIRST order.

The units for a First Order Rate constant are 1/time

(e.g. sec-1).
 First Order Kinetics
Ways to determine if a Reaction is First Order (3)

Half-Life Method: the time required for 1/2 of

reactant to react.

At t = t1/2, equation (1A) becomes:

ln([A]0/{ln[A]0/2}) = kt1/2

Solving for t1/2: t1/2 = ln 2/ k = 0.693/k

Half-life is INDEPENDENT of the initial concentration !

 First Order Kinetics
Rate = - d[A]/dt = k[A]1

An example of a first order reaction is the

decomposition of nitrogen pentoxide.

2 N2O5(g)  4 NO2(g) + O2(g)

Rate = -d[N2O5]/dt = k[N2O5]1

Note: Kinetic Order and Molecularity are not

the same in this example.
 First Order Kinetics
Examples of First Order Processes

1. All nuclear process follow First Order Kinetics

a. U238  Th 232 + 
b. C14  N14 + 

2. Decomposition Reactions:

H2C2O4  CO2 + HCOOH

Rate = k[H2C2O4]1
 Pseudo First Order Reactions
Some reactions which obey the 1st order kinetics
but involve more than one species in the rate-
determining step.
They involve a solvent molecule or a catalyst as
one of the reacting species.
1. Hydrolysis of methyl acetate
H+
CH3COOCH3 + H2O  CH3COOH + CH3OH

2. Inversion of sucrose
H+
C12H22O11 + H2O  C6H12O6 + C6H12O6
 Pseudo First Order Reactions
In these cases, water is present in large excess,
=> its concentration virtually remains constant
during the course of reaction.
=> the rate of reaction depends on [CH3COOCH3]
or sucrose.

-d[CH3COOCH3]/dt = k1[CH3COOCH3][H2O]
Since [H2O] = b is constant.
 -d[A]/dt = k1[A].b
Upon integration, a new rate constant can be defined
k = b.k1 = 1/t (ln[A]0/[A])
 Second Order Kinetics

Many Reactions such as: 2 HI  H2 + I2

are second order kinetics.

The general format for such reactions is:

2A  Products

Rate = k [A]2 ----- (1)

Second Order Kinetics

Rate = -d[A]/dt = k [A]2

Rearranging: -d[A]/[A]2 = k dt

Integration from [A] =[A]0 at t =0 to

[A] = [A] at t = t

1/[A] - 1/[A]0 = kt ------ (2)

 Second Order Kinetics
Ways to Determine if a Reaction is Second Order (1)

Rearranging: 1/[A] - 1/[A]0 = kt

1/[A] = kt + 1/[A]0

1/[A]
A plot of 1/[A] vs. Time
gives a straight line with a
slope = k.

Time
 Second Order Kinetics
Ways to Determine if a Reaction is Second Order (2)
1/[A] - 1/[A]0 = kt ------ (2)
Solving for k from equation (2)
k = (1/t){1/[A] - 1/[A]0} ------(2A)

Insert [A] at various time t. If the value of rate constant,

k is constant, then the reaction is SECOND ORDER.

The units for a Second Order Reaction are

1/(Moles/liter)(time) or Liters/mole-time
 Second Order Kinetics
Ways to Determine if a Reaction is Second Order (3)

Half-Life Method: the time required for half of

reactant to react.
At t = t1/2, [A] = [A]0/2
Substituting into: 1/[A] - 1/[A]0 = kt ------ (2)

1/([A]0/2) - 1/[A]0 = kt1/2

Solving for t1/2: t1/2 = 1/k[A]0

The half-life for a second order reaction is inversely

 Second Order Kinetics
Characteristics of Second Order Kinetics

1. The unit for a second order rate constant are

(molar concentration x time)-1 or 1 mol-1s-1.

2. A plot of 1/[A] vs. time gives a straight line

with a slope = k.

3. The half-life for a second order reaction is

inversely proportional to the first power of initial
concentration.
Examples of Second Order Reactions
1. Saponification of an ester is a 2nd order reaction.
CH3COOC2H5 + OH-  CH3COO- + C2H5OH

2. Reaction between ethylene bromide and potassium

iodide in 99% methanol.
C2H4Br2 + 3KI  C2H4 + 2KBr + KI3

3. Reaction between potassium persulphate and

potassium iodide in aqueous medium
K2S2O8 + 2KI  2K2SO4 + I2
 Higher Order Kinetics
Third and higher order reactions are quite rare.
This is due to the fact that the probability of a collision
between three molecules having sufficient energy is
very small compared with bimolecular collision.

Fractional Order of Kinetics

A reaction is said to be of fractional orders if the rate
of reaction is proportional to the fractional powers of
concentration of the reactants.
 Summary

Summary of kinetic relationships for orders 0,1,and 2

Order Rate Law Integrated Form Units of k t1/2

0 R=k [A]=-kt + [A]0 M.s-1 [A]0/2k

1 R = k[A] ln[A]=-kt + ln[A]0 s-1 0.693/k

2 R = k[A]2 1/[A] = kt + 1/[A]0 M-1.s-1 1/k[A]0