Chapter (16)

Dynamics of Chemical Processes

➢ Chemical kinetics deals with the rate of reactions.
➢ A reaction to occur, a collision must occur; the collision must be
of sufficient energy to break the necessary bonds.
➢ Rates of chemical reactions depend on the nature of the
reactants, the temperature, the presence of a catalyst, and
concentration.
16.1. Rate of a reaction – change in concentration of reactants or
products per unit time
A (reactant) → B (product)
➢ every reaction has a rate and unique in respect of chemical
kinetic study.
➢ Reaction time – the time interval required for a chemical change
to complete.
➢ In kinetic, the concentrations of reactant and product – mol/dm3
➢ as the reaction proceeds, the concentration of the
reactants decrease, the rate of change of concentration
decreases
➢ Rate , d(reactant)/dt=change in concentration per unit
time
➢ The rate of the reaction is defined as change in
concentration of reactants or products per unit time.
 amounts of reactants consumed
➢ Rate of reaction = dC / dt =
time interval
= moles/dm3/ sec

➢ -dC/dt where –ve sign indicates a decrease of concentration

of reactant A.

➢ +dC/dt where +ve sign indicated an increase of

concentration of products during the reaction.
example 1 – Ammonia and oxygen react at high temperature
forming nitric oxide and water. If the rate of formation of
nitric oxide is 2.4x10−3 mol/dm3/sec. Calculate the rate of
disappearance of ammonia and the rate of formation of water.
➢ 4 NH3 (g) + 5O2 (g) → 4 NO (g) + 6H2O (g)
➢ rate of reaction = − 1/4 d[NH3]/dt = −1/5d[O2]/dt = +1/4 d[NO]/dt = + 1/6
d[H2O]/dt

➢ rate of disappearance of NH3 = rate of appearance of NO

= 2.4x10−3 mol/dm3/sec
¼ d[NH3]/dt = ¼ d[NO]/dt = 2.4x10−3 mol/dm3/sec
➢ +1/6 d[H2O]/dt = + ¼ d[NO]/dt
2.4x10−3
d[H2O]/dt = x 6 = 3.6x10−3 mol/dm3/sec
4
example 2 – For a reaction 2A + 3B → C + 4D, the rate of the reaction with respect to
A, i.e., d[A]/dt = 0.0024 mol/dm3/sec.
Calculate the rates with respect to B, C and D.
➢ rate of reaction (dC/dt) = − ½ d[A]/dt = −1/3 d[B]/dt =
+ d[C]/dt = + ¼ d[D]/dt
d[A]/dt = 0.0024 mol/dm3/sec
(i) 1/2d[A]/dt = 1/3d[B]/dt
d[B]/dt = 3/2d[A]/dt =3/2 (0.0024)
= 0.0036 moles/dm3/sec
(ii) 1/2d[A]/dt = d[C]/dt
d[C]/dt = 1/2d[A]/dt = 1/2 (0.0024)
= 0.0012 moles/dm3/sec
(iii) 1/2d[A]/dt =1/4d[D]/dt
d[D]/dt = 4/2d[A]/dt = 2 (0.0024)
= 0.0048 moles/dm3/sec
16.2. Types of Chemical Reactions
➢ The types of reactions are (i) ionic reactions and (ii) molecular reactions
➢ (i) ionic reaction – a reaction taking place between oppositely charge ions
Na+ Cl− + Ag+ NO3- → AgCl + Na+ NO3-
➢ The ionic reactions are spontaneous and rates are faster.
➢ Their rates of reactions cannot be measured by ordinary techniques.

➢ (ii) molecular reaction – a reaction taking place between the molecules.

CH3COOCH3 + H2O → CH3COOH + CH3O
➢ The rates of reactions of these molecular reactions can be easily measured.
➢ A molecular chemical reaction involves breaking of bonds in reacting molecules
and formation of new bonds in product molecules.
➢ The number and nature of bonds are different in different substances, the rates of
chemical reactions differ a lot from one another.
16.3. Rate Law of a Reaction

➢ There are two forms of a rate law for chemical kinetics: differential
rate law and integrated rate law.
➢ The differential rate law relates the rate of reaction to the
concentrations of the various species in the system.
➢ The differential rate law can take on many different forms, especially
for complicated chemical reactions, but most chemical reactions obey
one of the three differential rate laws.
➢ Each rate law contains a constant, k, called the rate constant.
➢ A rate law of a reaction is a mathematical expression relating the
rate of a reaction to the concentration of either reactants or
products.
➢ k (rate constant) – the proportionality constant in the rate law equation that
describes the relationship between the rate of a step in a chemical reaction.

➢ Differential rate laws or differential rate equations – the concentration dependence

rate equations.
➢ Eg, CH3COOCH3 + H2O → CH3COOH + CH3OH
➢ The rate law for the reaction is , dC/dt α [CH3COOCH3][H2O]
= k[CH3COOCH3][H2O]

➢ eg. consider the case of hydrolysis of cane sugar which is a single step molecular
reaction at particular temperature.

C12H22O11 + H2O → C6H12O6 + C6H12O6

rate of reaction = dC/dt α [C12H22O11 ] [H2O]
dC/dt = k [C12H22O11 ] [H2O]
dC/dt = rate of reaction, k = rate constant
[ ] = concentration (mol/dm3)
➢ The rate law may be theoretically determined from the
rate determining step (slow step) of the reaction
mechanism.
➢ Chemical reactions require a number of steps to
break bonds and form news ones.
➢ These steps are called the reaction mechanism.
➢ An elementary process is also called an elementary
step or elementary reaction.
➢ The equation in an elementary step represents the
reaction at the molecular level, not the overall
reaction.
➢ Based on the numbers of molecules involved in the elementary
step, there are three kinds of elementary steps: uni-molecular
step, bimolecular step, and tri-molecular step.
➢ When a molecule or ion decomposes by itself, an elementary
step – A uni-molecular step or process. a uni-molecular step is
always a first order reaction.
➢ eg. O3 → O2 + O Rate = k [O3]
A → B + C + D Rate = k [A]
➢ A bimolecular process involves two reacting molecules or ions.
The rates of these steps are second order reaction .
➢ eg. NO + O3 → NO2 + O2 Rate = k [NO] [O3]
A + A → B + C Rate = k [A]2
A + B → X + Y Rate = k [A] [B]
➢ the rate equation = an expression for the rate or velocity of the
rate determining step of a molecular reaction.
➢ A tri-moleular process which involves the collision of
three molecules.

➢ eg. O + O2 + N2 → O3 + N2 Rate = k [O] [O2] [N2]

A + A + A → products Rate = k [A]3
A + A + B → products Rate = k [A]2[B]
A + B + C → products Rate = k [A][B][C]

➢ Three molecules collide at an instant is rare, but

occasionally these are some of the ways reactions take
place.
➢ Elementary processes are chemical reaction progresses
leading to an overall reactions. Such a collection is called a
reaction mechanism. In a mechanism, elementary steps
proceed at various speeds. The slowest step is the rate
determining step.

➢ The concept of rate law in chemical kinetics, it is reasonable

to classify the molecular reactions into two types:

➢ 1. single-step molecular reactions

➢ 2. multi-step molecular reactions.
16.3.1. Single Step Molecular Reaction
➢ In a single step molecular process, the stoichiometric or
balances chemical equation itself is the slow step which is
the rate determining step of the reaction and is related to the
rate equation.
➢ eg. CH3COOCH3 + H2O → CH3COOH + CH3OH

➢ The rate law of the reaction is

dC/dt α [CH3COOCH3 ] [H2O]
= k [CH3COOCH3 ] [H2O]
16.3. 2. Multi-step Molecular Reaction
➢ In multi-step molecular reaction, only one of the step is slow
while the other are fast. It is this slow step which determines the
rate of the reaction.
➢ eg. N2O5 → N2O4 + ½ O2 ↑
The above reaction takes place as follows
N2 O 5 → N 2 O 4 + O (1) (slow)
O + O → O2 (2) (fast)
Equation (1) is the slow and the rate determining step of the
reaction
dC/dt α [N2O5] or dC/dt = k [N2O5]
dC/dt = − d [N2O5] /dt = d[N2O4 ]/dt = 2 d[O2]/dt
➢ dC/dt = rate of the reaction, K= velocity constant of the reaction
at constant temperature.
➢ The slowest step limits the rate of the reaction.
Example 1. If the reaction, 2 NO2 + F2 → 2NO2F, follow the
mechanism,
i. NO2 + F2 → NO2F + F (slow)
ii. NO2 + F → NO2F (fast)
What is the rate law?
Answer – Step i is the rate determining step, the rate law is
rate law = dC/dt = - ½ d[NO2]/dt = -d[F2]/dt = k [NO2] [F2]
Order of the reaction = 2.
Example 2. For the reaction, H2 + Br2 → 2HBr, the following
mechanism has been proposed
i. Br2 ↔ 2Br (both directions are fast)
ii. Br + H2 → HBr + H (slow)
iii. H + Br2 → HBr + Br (fast)
Drive the rate law that is consistent with this mechanism.
Answer –rate of reaction = -d[H2]/dt = -d[Br2]/dt =
+ ½ d[HBr]/dt
rate law = dC/dt = ½ d[HBr] = k2 [Br][H2]
rate k1 [Br2] = k−1 [Br]2
[Br] = (k1/ k−1)1/2 [Br2]1/2
rate law = k2 [Br][H2]
= k2 (k1/ k−1)1/2 [Br2]1/2[H2]
order of the reaction = 1/2 +1 = 3/2
The overall reaction order is 3/2, 1 with respect to [H2]
and ½ with respect to [Br2].
(k1/ k−1) is often written as k, and it is called the
equilibrium constant for the reversible elementary steps.
16.4.Factors Affecting the Rate of Reaction
.1. Concentration of Reactants
➢ The concentration of reactants – important role in chemical
kinetics.
➢ By increasing the amount of reactants, the rate of reaction is
increased.
➢ An increase in concentration of reactants increases the number of
molecules.
➢ For a general reaction,
aA + bB → dC + dD
➢ The rate of reaction depends upon the concentration of the
reactants.
➢ Rate of reaction 𝛼 [concentration] = k[A]a [B]b
.2. Temperature
- The rates of most chemical reactions increases as the
temperature rises because temperature does not affect
concentration very much, the rate constant must increase
with increasing temperature.
➢ As the temperature increases the velocity of molecules
increases which results in the increase in the frequency of
collision.
➢ The rise in temperature raises the kinetic energy of each
molecule.
➢ An increase of every 10 °𝐾(10°C) in temperature, the
fraction of molecule possessing activation energy becomes
double.
➢ As a result the number of effective collision is also double,
the rate is doubled.
.3. Presence of a catalyst
- Catalyst – a substance which controls the rate of reaction without itself
undergoing permanent chemical change.
➢ two types – positive catalyst and negative catalyst
➢ Positive catalyst – increases the rate of reaction by lowering the energy
of activation. In the presence of a positive catalyst, the greater fraction of
the total molecules will posses lower energy activation and collided
successfully in a short period of time, there by increasing the rate of
reaction. ( by providing an alternative path to the reaction or by the
formation of a transition intermediate compound having low energy of
activation )
➢ Negative catalyst or inhibitor – retards the rate of reaction. A negative
catalyst does not lower the energy of activation rather they are combined
with reactant molecule thus decreasing the number of colliding reactants
molecules. This decreases the effective collisions, and rate of reaction
➢ In order to react, the colliding molecules must have a total
kinetic energy equal to or greater than some minimum value.
The minimum energy required to initiate a chemical reaction is
called the activation energy, Ea. The value of Ea varies within
reactions.
➢ The energy barrier between the starting molecule and the
highest energy along the reaction pathway is the activation
energy, Ea.
➢ the particular arrangement of atoms at the top of the barrier –
the activated complex or transition state
➢If the conversion of A to B is exothermic, the product has lower
energy than reactant. The energy change, E, has no effect on the
rate of the reaction.
➢The rate depends on the magnitude of Ea; generally lower the
Ea is, the faster the reaction rate.
➢A molecule might acquire enough energy to overcome the
energy barrier and be converted to B.
➢At the higher temperature a much greater fraction of the
molecules has kinetic energy greater than Ea, which leads to a
much greater rate of reaction.
➢Collision must occur not only with sufficient energy but also
with suitable orientation in order to cause reaction.
eg. Cl + NOCl → NO + Cl2
.4. Surface Area of the Reactants
➢ In heterogeneous reaction, the rate of reaction
depends on the surface area of solid reactant.
➢ Greater the surface area, higher the rate of reaction.
➢ By increasing the surface area of the reactant, the
rate of reaction increases due to greater contact
between individual particles and also due to the fact
that of the surface molecules reacts more quickly.
➢ eg. finely divided calcium carbonate reacts more
quickly with HCl than calcium carbonate chips.
. 5. The Collision Model
➢ Reaction rates are affected both by the concentration of
reactants and by temperature.
➢ Both of these effects are provided by the collision model of
chemical kinetics.
➢ The central idea of the collision model is that molecules
must collide to react.
➢ As the concentration of reactant molecules increase, the
number of collisions increase, leading to an increase in
reaction rate.
➢ From the kinetic molecular theory of gases, increasing the
temperature increases the molecular velocities. As
molecules move faster, they collide harder (with more
energy) and more frequently, increasing reaction rate.
➢ Arrhenius suggested that molecules must possess a certain
minimum amount of energy in order to react. According to
the collision model, this energy comes from the kinetic
energies of the colliding molecules.
➢ If molecules are moving too slowly, with too little energy,
they merely bounce off one another without changing.
6. The Arrhenius Equation
➢ Arrhenius equation ; k = A e−Ea/RT
➢ Ea = the activation energy, T = absolute temperature (K)
R = gas constant (8.314 J/mol/K)
➢ A = Arrhenius constant = frequency factor is related to the
frequency of collision and the provability that collisions are
favorably oriented for reaction.
➢ the magnitude of Ea increases, k becomes smaller. The
reaction rates decrease as the energy barrier increases.
𝐄𝐚
➢ ln k = − + ln A
𝐑𝐓
➢ This equation – the form of a straight line; it predicts that a
graph of ln k versus 1/T will be a line with a slope equal to
Ea /R and a intercept equal to ln A.
➢ At different temperatures, T1 and T2, a reaction has rate
constants k1 and k2.
Ea
➢ ln k1 = − + ln A ---- (1)
RT1
Ea
➢ ln k2 = − + ln A ----(2)
RT2
Ea Ea
➢ Eqn (1) − (2) ln k1 − ln k2 = (− + ln A) − (− + ln A)
RT1 RT2
𝑬𝒂
➢ ln k1/ k2 = ( 1/T2 − 1/ T1 ) ( Ea can be determined )
𝐑
 Example: A rate of a reaction for a chemical process is
investigated at two different temperatures. The rate constant of
a reaction at 25°C is 1.55 x 10−4 s−1. At 50°C the rate constant
of a reaction is 3.88 x 10−4 s−1 . Based on these data, what is
the energy of activation for the chemical process expressed in
J/mol? ( R = 8.314 J/mol K )
T1 = 25°C + 273 = 298 K T2 = 50°C + 273 = 323 K
k1 = 1.55 x 10−4 s−1 k2 = 3.88 x 10−4 s−1
𝑬𝒂
ln k1/ k2 = ( 1/T2 − 1/ T1 )
𝐑
1.55 x 10−4 𝐸𝑎
ln = ( 1/323 − 1/298 )
3.88 x 10−4 8.314
Ea = 2.934 x 104 J/mol
16.5.Order of a Reaction
➢ A rate equation or Rate law – an equation of the relationship between
concentration of the reactants and reaction rate
α A + β B + γ C → x X + y Y + ....
rate law, rate = k [A]α [B]β [C]γ
k = rate constant of the reaction at constant T , α , β ,γ = integers
order of reaction = α + β +γ
order of reaction = the sum of the individual powers of species
(A , B, C )
➢ If the power β is one, the reaction is 1st order with respect to B. If α
= 0 and γ = 1, it means that the reaction is zero order with respect to A
and 1st order with respect to C.
the overall order = 0 + 1 + 1 = 2
➢ order of reaction = the number of reacting molecules whose
concentration change during the rate determining step of the reaction.
 16.5.1.For a single step reaction, n A → m B + C
rate law, rate = dC/dt = k [A]n order of reaction = n
➢ eg. CH3COOCH3 + H2O → CH3COOH + CH3OH
➢ the rate law of the reaction is
dC/dt α [CH3COOCH3 ] [H2O]
= k [CH3COOCH3 ] [H2O] (order of reaction = 2)
➢ if water is taken excess, the rate law of the reaction is
dC/dt α [CH3COOCH3 ]
= k [CH3COOCH3 ] ( order of reaction = 1 )
 16.6.2. For multi-step reaction, the slowest step is the rate
determining step.
➢ eg. 2N2O5 → 2N2O4 + ½ O2 ↑
➢ The above reaction takes place as follows
➢ N2O5 → N2O4 + ½ O2 (1) (slow)
➢ O + O → O2 (2) (fast)
➢ Equation (1) is the slow and the rate determining step of the
reaction.
➢ the rate law,
dC/dt α [N2O5]
dC/dt = k [N2O5] (order of reaction = 1 )
 16.6.3. Zero order reaction -
If the change in concentration in large excess of reactants
do not affect the rate of the reaction ( constant rate ), this
reaction is zero order reaction.
dC/dt = k [reactant]0
eg. decomposition of HI and NH3 on the surfaces of gold
and tungsten respectively are zero order reactions.
dC/dt = k[HI]0 dC/dt = k[NH3]0
 16.7. Different Types Order of Reactions
1. 1.First order Reaction – Reactions in which the rate varies
with concentration of a single species, and the change in
concentration is exponential . The stoichiometric coefficient is
1.
A plot of ln (concentration) vs. time or log (concentration )
vs. time is linear .
eg. radioactive decay and most enzyme mechanisms
contain intermediate reactions that are first order.
2. Second order Reaction (Class I) – Reactions in which the
rate varies with concentration of a single species, but the
stoichitric coefficient is 2. the rate varies with the
reciprocal of the concentration so that a plot of
1/(concentration) vs. time is linear.
3. Second Order Reactions (Class II) – Reactions in which
the rate varies with the concentration of two substrates,
each of which has a stoichiometric coefficient of 1. A plot
of ln ( conc: A/conc: B ) vs. time is linear.
4. Higher Order Reactions – Reactions in which more than
two species are involved, or one species reacts with
stoichiometric coefficient >2. Many different classes, of
which the simplest involves single species with
stoichiometric coefficient >2.
5. Zero order Reactions – Reactions do not depend on the
concentration of reactants. Many reactions in biochemistry
appear to occur a rate independent of the substrate
concentration, because this reaction is enzyme-catalysted
reaction and the rate is determined by the concentration of
enzyme, the substrate is in excess, the rate is saturated.
16.8. Molecularity of a Reaction – the number of reacting
molecules taking part in a rate determining step of a reaction.
(i) for a single step reaction as given, the molecularity is two.
CH3COOCH3 + H2O → CH3COOH + CH3OH
(ii) for a multi-step reaction, the decomposition of N2O5 is
two steps.
eg. 2N2O5 → 2 N2O4 + O2 ↑
The above reaction takes place as follows
N2O5 → N2O4 + ½ O2 (1) (slow)
O + O → O2 (2) (fast)
Equation (1) is the slow and the rate determining step of
the reaction and there is only one reacting molecule, the
molecularity is one.
 16.9. Pseudo-molecular Reaction – A reaction whose
molecularity is two or more but whose order is one.
eg. C12H22O11 + H2O → C6H12O6 + C6H12O6
rate of reaction = dC/dt α [C12H22O11 ] [H2O]
dC/dt = k [C12H22O11 ] [H2O]
➢ Water is in large excess and its concentration does not
change during the process, experimental data indicates that
it is a single step process and is found to be first order.
rate of reaction = dC/dt α [C12H22O11 ]
dC/dt = k [C12H22O11 ]
This reaction is a bimolecular reaction (one molecule of
C12H22O11 and one molecule of H2O) but it is first order
reaction. It is pseudo-molecular reaction.
 1. First order reaction - eg. A → product
rate law − d[A]/dt = k [A]
2. Second order reaction –
eg. 2B → product rate law --- rate = k [B]2
A + B → product rate law --- rate = k [A][B]
3. Third order reaction –
eg. 3 B → product rate law --- rate = k [B]3
2 A + B → product rate law --- rate = k [A]2 [B]
A + B + C → product rate law --- rate = k [A][B][C]
 16.11.Integrated Forms of Rate Law
1. 16.11.1. First Order Reactions
➢ If the number of reacting molecule whose concentration
changes in the rate determining step reaction is one, it is
called first order reaction.
➢ eg. A → product
➢ rate law ---- rate = -d[A]/dt = k1[A]1
-d[A]/dt = k1[A]
𝑑[𝐴]
= − k1 dt
[𝐴]
[𝐴] 𝑑[𝐴] 𝑡=𝑡
‫]𝐴[ 𝐴 ׬‬ = ‫=𝑡׬‬0 − k1 dt
0
[𝐴]
ln = − k1t
𝐴0
 [𝐴]
= e− k1t
𝐴0
[A] = [A]0 e− k1t
[A] = (a-x) = final concentration of reactant at time = t
[A]0 = (a) = initial concentration of reactant at time = 0
k1 = the rate constant
ln [A] = − k1t + ln [A]0 or ln (a-x) = − k1t + ln a
A plot of ln [A] vs. time is a straight line. slpoe = − k
A plot of log [A] vs. time is a straight line. slope = − k/2.303
 eg. A → product
rate law ---- rate = − d[A]/dt = k1[A] = k1 a
where k1= the first order rate constant for the forward
reaction
a = the initial concentration of the reactant (mol/dm3)
-d[A]/dt = the disappearance rate of reactant
-d[A]/dt = k1 a
d[A]
- = k1 dt
a
if the concentration of A after a time lapse t seconds fall (a-x)
(or) t = t, conc: of A = (a – x)
d[A]
-‫׬‬ = ‫ ׬‬k1 dt
(a −𝑥)
-ln (a – x) = k1 t + C ------- (1)
 t = 0, conc: of A = a
C = -ln a
eq: (1) becomes − ln (a – x) = k1 t − ln a
k1 t = ln a − ln (a – x)
a
k1 t = ln
(a −x)
2.303 a
k1 = log
t (a −x)
the exponential form (a – x) = a e− k1t
rate law = dC/dt = k1 (a –x)
A plot of ln (a – x) vs. time is a straight line. slpoe = − k
A plot of log (a – x) vs. time is a straight line.slope = − k/2.303
Characteristics of first order reaction
(1)Half- life of first order reaction
- independent of its initial concentration
a
t = t ½ , (a – x) =
2
a
= a e − k1 t ½
2
½ = e − k1 t ½
ln ½ = − k1 t ½
ln 2 = k1 t ½
ln 2 0.693
k1 = = unit of k = (time)−1
t½ t½
(2) k of a first order reaction is independent of the initial
concentration unit.
(1)Half- life of first order reaction
- independent of its initial concentration
ln [A] = -kt1/2 + ln [A]0 , [A] = [A]0/2 , t = t1/2
ln [A]0 / 2 = - kt1/2 + ln [A]0
ln [A]0 /2 - ln [A]0 = t1/2
-k
ln [A]0/2 /[A]0 = t1/2
-k
ln (1/2) = t1/2
-k
-o.693/ -k = t1/2 , t 1/2 = 0.693/ k
Example The half-life for a first order reaction is 100 seconds.
calculate the rate constant and determine what fraction will
have reacted after 250 seconds.
t1/2 = 0.693 / k
k = 0.693 / 100 = 6.93 x 10 −3 s −1
a
ln = k1 t = 6.93 x 10 −3 x 250
(a −x)
a
= 5.6548
(a −x)
1
if a = 1, = 5.6548
(1−x)
5.6548 −1
x= = 0.8232
5.6548
% of reacted species = 82.32 %
 16.11.2. Second order reactions
The number of the reacting molecules whose concentration changes in the rate determining
step of the reaction is two, it is called second order reaction.
Class I
2 A → products
initial (t = 0) a 0
remain (t = t) (a – x) x
− d[A]/dt = k2 [A]2 = k2 (a – x)2
d[A]
− = k2 dt
(a – x)2
d[A]
Integrating both sides of the equation, ‫ ׬‬− = ‫ ׬‬k2 dt
(a – x)2
1
= k2 t + C ------ (1)
(a −x)
when t = 0, x = 0 or (a – x) = a,
1
C=
(a )
1 1
C is substituted in equation (1), (1) becomes = k2 t +
(a −x) (a )
1 1 a − (a −x) x
k2 t = − = =
(a −x) (a ) a (a −x ) a (a −x )
𝒙
k2 =
𝐚 𝐚 −𝐱 𝐭
 Half - life for the second order reaction
a
t = t ½ , (a – x) = x = = 0.5 a
2
𝟎.𝟓 𝐚
k2 t ½ =
𝐚 𝐚 −𝟎.𝟓𝐚
𝟎.𝟓 𝟏
t½ = =
𝟎.𝟓𝐚 k2 k2 𝐚
(1) t ½ depends on initial concentration .
(2) unit of k2 = mol−1 dm3 s−1 = M−1 s−1
(3) the integrated rate equation shows that a plot of 1/[a -x] vs. time
gives a straight line for a second order, class I reaction and
intercept at 1/[a]

Characteristics of second order reaction

(1) k2 is inversely proportional to the initial concentration,
(2) k2 varies inversely as the multiple unit of initial concentration, a
Class II
A + B → product
initial (t = 0) a b 0
reacted x x x
remain (t = t) (a – x) (b – x) x
d[A] d[B] d[P]
rate law − = − = = k2 [A] [B]
dt dt dt
d[P] dx
= = k2 (a – x) (b – x)
dt dt
dx
= k2 dt
(a – x) (b – x)
dx
‫׬‬ = ‫ ׬‬k2 dt
(a – x) (b – x)
by partial fraction method,
if a > b,
−1 a b
[ ln − ln ] = k2 t
(a −b) (a −x) (b −x)
 1 (a −x) (b −x)
[ ln − ln ] = k2 t
(a −b) a b
1 b(a −x)
[ ln ] = k2 t
(a −b) a (b −x)
𝟏 𝐛 (𝐚 −𝐱)
k2 = ln
𝐭 (𝐚 −𝐛) 𝐚 (𝐛 −𝐱)
𝟐.𝟑𝟎𝟑 𝐛 (𝐚 −𝐱)
k2 = log
𝐭 (𝐚 −𝐛) 𝐚 (𝐛 −𝐱)
Determination for nth order reaction
dC
= kn (a – x)n
dt
dC
= kn dt
(a – x)n
dC
‫( ׬‬a – x)n = ‫ ׬‬kn dt
1 1
= kn t + C
(n −1) (a – x)n−1
1 1
if t = 0, x = 0 C=
(n −1) (a)n−1
1 1 1
kn = │ − │
t (n −1) (a – x)n−1 (a)n−1
 Determination of the order of reaction
1. Integration method
the amount of reactants consumed after different intervals of
time is found out by analysis and the data is substituted for 1st, 2nd,
or the nth order reaction.
the order of the reaction is obtained by the rate constant k of the
reaction for any order reaction.
st 2.303 a
1 order k = log
t (a −x)
1 x
2nd order k=
t a a −x
2. Half-change method ( Half period reaction method )
it is shown that the time required to complete half of the reaction
is independent of initial concentration for 1st order reaction and is
inversely proportional to the concentration for 2nd order reaction.
1 (t ½)1 a1 n – 1
t½ α = │ │
(a1)n−1 (t ½)2 a2
 3. Ostwald’s isolation method
If the number of reactants are more than two, Ostwald’s isolation method
can be adopted to determine the order of reaction. the experiments are carried
out by talking all reactants except one in excess, is said to be isolated.
dC/dt = k [A]n [B]m order of reaction = n + m

4. Graphical method
i. rate law dC/dt = k [a –x]n n = order of the reaction
The rate of reaction, dC/dt, is obtained from the
concentration –time graph for same values of t.
The rate of reaction is then plotted as function of different
powers of (a – x). The power required for obtaining a linear
graph gives the order of reaction.
ii. In case of first order reaction, a straight line graph is obtained by
plotting log (a – x) against time.
5. Van’t Hoff’s differential method
dC1
for concentration C1, = k C1n
dt
dC2
for concentration C2, = k C2n
dt
C
d 1
C1 n
C = │ C2│
dt
d 2
dt
dC1 dC2
log − log = n [ log C1 − log C2 ]
dt dt
C1 − log dC2
log ddt dt
n=
log C1 − log C2
 Complex Reaction Kinetics
1. Reversible reaction
A ↔ B
eg. ester hydrolysis and conversion of ammonium thiocyanate
into urea
A ↔ B+C
eg. decomposition of alkyl ammonium halides into 3° amine
and RX
decomposition of PCl5 into PCl3 & Cl2
A + B↔ C
eg. formation of NH3 from N2 & H2
 2. Consecutive reactions
A → B → C
eg. saponification of esters of dibasic acids with alkali

3. Parallel reactions ( Competitive reactions)

B
A
C
eg. chlorination of methane, nitration of phenol

4. chain reactions
A → C
C + λ → Pr + C
eg. reaction of H2 & Cl2 in the sun light
 1. The half-life of 222Rn is 3.8 days. A sample of 222Rn is
allowed to decay for 15.2 days and after this time, 5.6 mmol
remained. What is the initial quantity of 222Rn?
t ½ = 3.8 days k = ? a – x = 5.6 mmol a =?

2. For the reaction: A + B → C + D, the reaction rate

halves when the concentration of A halves ( B is in excess ),
and when A is in excess, the reaction rate is unaffected by
changes in the concentration of B. What is the rate law for this
reaction?