CHEMCIAL KINETICS

Introduction: From our knowledge of chemical equilibrium constant for a reversible reaction
more it goes in the forward direction before attaining the equilibrium state. If the value of
equilibrium constant in very large, we infer that the reaction is almost irreversible because it
will go for almost completion.
Similarly from the study of thermodynamics we know that a reaction will go spontaneously in
the direction for which change in free energy (G) is negative.
But both the above areas of study are unable to tell us that in how much time a reaction will be
complete, up to what extent. In nut shell, the TIME element is missing in chemical equilibrium
as well as in thermodynamics. This deficiency is covered by a branch of physical chemistry
known as Chemical Kinetics or Chemical Dynamics.
In this chapter we shall be studying the following subtitles as per our level and course of study.
I. Rates of chemical reactions and rate constant
II. Order of reactions
III. Temperature dependence of rate constant (Arrhenius Equation)
IV. Some complications in first order reactions
So our first article for study is
RATES OF CHEMICAL REACTIONS AND RATE CONSTANTS
From rate point of view, chemical reactions can be classified into following three categories:
i. Fast reactions: If you add some AgNO
3
to NaCl solution, a white precipitate of AgCl
according to following reaction
(aq.)
3
NaNO
whiteppt,
AgCl
(aq.)
NaCl
(aq.)
3
AgNO + +
is obtained within twinkling of eye. The above is an example of ionic reaction and most
of the ionic reactions to determine occur with such a fast rate that it is impossible to
determine the change in the concentration of any or all the reactants in a convenient
time period. We shall be excluding such fast reactions from the domain of our study. Of
course, it does not mean that chemistry is incompetent to deal with such reactions. We
do have sophisticated methods like stopped flow techniques, flash photolysis using
lasers etc. for the study of such reactions, but their study is beyond the level and the
course we are presently concerned with.
ii. Moderate reactions: If you add few drops of solution of KMnO
4
to an aqueous solution
of oxalic acid, the purple (or pink of solution is very dilute) colour of KMnO
4
disappears
slowly. It may take few minutes for the solution to become colourless.
This is a redox reaction which can be represented by the following equation:
16H + 2MnO + 5C O 2Mn + 10CO + 8H O
This can be considered as a slow reaction, but if we repeat the above experiment by
replacing oxalic acid with an acidified solution of ferrous Ammonium Sulphate
(FeSO
4
. (NH
4
)
2
SO
4
. 6H
2
O) the solution becomes colorless within no time. The reaction is
8H + MnO + 5Fe Mn + 5Fe + 4H O and can be considered an example
of moderately slow reaction.
At the beginners level, chemical kinetics deals with such moderate to slow reactions.
iii. Very slow reactions: If we mix 2 volumes of Hydrogen with 1 volume of oxygen gas at
ordinary temperature and pressure, then under these conditions of temperature and
pressure, even in the years, we shall not be able to mark any significant change in their
concentrations.
Therefore the reaction:
(l) 2 2(g) 2(g)
O H O
2
1
H + is an example of very-very slow
reaction. But if we raise the temperature, add some suitable catalyst or send an electric
spark in the above gaseous mixture, we find appearance of some water droplets. What
does it mean? It means the rate of a reaction can be affected by some factors like
pressure, temperature, catalyst etc. We have to study all these factors in detail in this
chapter, but let us first of all study the rate of reaction itself.
Rate of reaction: It is defined as the rate of change of concentration of reactants or products
of a chemical reaction per unit time.
Unit of rate of reaction:
Time
ion Concentrat
= mol
1
L
1
sec

or mole
3
dm
1
sec

[1
3
dm=1L]
But sometimes in case of a gaseous reaction, concentration is replaced by pressure (measured
in atmosphere) then the unit of rate becomes atm sec
-1
.
TYPE OF RATES OF REACTIONS
1) There are following three ways in which rate of a reaction can expressed.
Average rate: It is defined as:
Average rate =
t) ( change in that taken time Total
c) ( substance a of ion concentrat in the change Total
A
A
=
(

=
=

seconds) in (usually time t
L mol in ion concentrat c wehre
t
c
1
If the substance under consideration is a reactant, then with the passage of time its
concentration will decrease and therefore its rate of reaction will also be decreasing.
Hence for a reactant
average rate =
t
c

Obviously, if we are measuring concentration change for a product them with respect to
product
average rate =
t
c
+
In general average rate = average rate =
t
c

2) Instantaneous Rate: As the name suggests, it is rate of reaction at a particular instant

(similarly it can be at a particular concentration also)
This can be achieved by using calculus as:
dt
dc
t
c
0 t
Lt
=

Where dc means a very-very small (infinitesimal) change in concentration and dt is

the corresponding infinitesimal change in time. Thus if a graph be plotted between the
concentration versus time for a reactant, then it will be a curve as shown in the
following figure. Now if we want to know the instantaneous rate at any time say t.
Then a tangent must be drawn on the curve at time s, the slope of this tangent will give
us the instantaneous rate at time s. Similarly instantaneous rate at any particular
concentration c can also be determined.
Instantaneous rate is very widely used term in chemical kinetics; hence its little more
elaboration will be useful.
For this let us consider a reaction:
A+B C+D
then instantaneous rate (v) for this reaction at a particular time t will be:
v =
dt
d[D]
dt
d[C]
dt
d[B]
dt
d[A]
+ = + = =
since stoichiometric coefficients of all the reactants and products are same hence all the
four rates are numerically same.
But if we consider the reaction say: 2A B+C, then
v =
dt
d[C]
dt
d[B]
dt
d[A]
2
1
+ = + =
It is so, because the rate of disappearance of A is twice the rate of appearance of B as
well as that of C.
Therefore for the example: N
2
+3H
2
2NH
3
v =
dt
] d[NH
2
1
dt
] d[H
3
1
dt
] d[N
3 2 2
+ = =
It is also useful to understand that some time we write instantaneous rate as
dt
dx
. It is
because if we consider a reactant A.
A product
if A concentration at t = 0: a
concentration at.
time t: (a- )
Then instantaneous rate of A at time t will be given by
dt
d
) (a
dt
d
dt
d[A] x
x = =
On the basis of above discussion we come to the following conclusions:
(a) Instantaneous rate of a reaction can be determined by measuring the change in
concentration of any of the reactants or products but to have same numerical value
applicable to all, that rate must be divided by the stoichiometric coefficient of that
reactant or product in the given balanced chemical equation for the reaction under
consideration.
(b) The numerical value of v is always (+)ve whether we measure the concentration
change of a reactant or product. However for distinction purpose a negative sign in put
before the rate for reactant.
(c) The unit of rate as we have already seen will be mol L
-1
sec
-1
or in general cone. x
time
-1
3) Initial Rate (v): It is defined as the instantaneous rate at t=0 time. Therefore in order to
determined initial rate we will have to carefully draw a tangent at t=0 on the curve
plotted between concentration and time, as shown below:
MEASUREMENT OF REACTION RATE:
As we have already seen, reaction rate can be determined by measuring the change in
concentration of any of the reactants or products at constant temperature. If a reaction
involves more than one reactants then it is better to select that reactant whose concentration
change can be measured accurately and conveniently. Concentration change can be
determined by any of the following methods, depending upon the nature of the reactant or
product selected for this purpose:
i. By volumetric or gravimetric analysis.
ii. By measuring the change in the pressure of a gas because partial pressure of a gas is
proportional to its concentration.
iii. By measuring changes in those physical properties which depend on concentration.
Such physical properties are refractive index, specific volume, absorbance, specific
rotation, conductance, viscosity etc.
Specific reaction rate or rate constant
We have already read in the chapter of chemical equilibrium that according to law of mass
action: rate of a reaction is proportional to the product of active masses of the reactant.
Hence if we consider the following reaction:
m
1
A + m
2
B n
1
C+n
2
D
then reaction rate [A]
m1
[B]
m2
or reaction rate = k [A]
m
1
[B]
m
2
This constant of proportionality k is called specific reaction rate or simply rate constant
specific reaction rate is defined as the rate of a reaction at constant temperature when the
concentration of each reactant is unit.
Remember: k does not depend on the concentration it depends only on temperature.
Therefore if we consider a specific example say H
2
+ I
2
2HI
then ] [I ] [H k' '
dt
] d[I
dt
] d[H
2 2
2 2
= =
Such type of expressions which give mathematical relation between rate of reaction and
concentration are called rate expressions or simply rate law.
Therefore for the reaction
H
2
+I
2
2HI
Rate = k [H
2
] [I
2
] becomes a rate law for this. According to this relation if we double the
concentration of H
2
or I
2
at constant temperature then the rate of reaction must be doubled or
if we double the concentration of both then rate must become four times the old.
In fact it is erroneous to predict rate law from the balanced chemical equation for the reaction.
Rate law for any reaction is in fact an experimentally determined quantity. For example if we
consider the following reaction:
2N
2
O
5
4NO
2
+O
2
then merely on the basis of this equation, one may write a rate law as:
rate = k[N
2
O
5
]
2
. But this is wrong. Because according to this if we double the
concentration of N
2
O
5
then rate must become four times, while actually it becomes double
only.
Hence its correct rate law becomes
Therefore if we represent a reaction by its balanced chemical equation such as:
m
1
A + m
2
B n
1
C+n
2
D
and experimentally we determined that rate follows the following expression:
rate = k [A]
p
[B]
q
-------------- (1)
Where p & q may or may not be equal to m
1
& m
2
respectively, then the above equation (1)
becomes rate law and the sum of the powers on the concentration terms is called overall
ORDER OF REACTION. We shall have a detailed discussion of the term order of reaction, soon,
but before that let us discuss a important thing that is:
Units and significance of rate constant k
In general for any reaction we can write rate law (on the basis of experiments) as:
Rate = k [concentration] order
k = rate [concentration]
-order
or k =
order -
1
tion) (Concentra
Time
tion) (Concentra
or k =
1 order - 1
Time x tion) (Concentra

further since concentration = mol L
-1
k = (mol)
(1-order)
(L)
(order-1)
x Time
-1
As time is usually expressed in terms of seconds hence the unit of k will be
k = (mol)
(1-order)
(L)
(order-1)
sec
-1
Therefore for a
1. Zero order reaction: k will be in terms of (mol)
(1-order)
sec
-1
i.e. same as the unit of rate of
Rate = k [N
2
O
5
]
reaction.
2. First order reaction: k will be in terms of sec
-1
or time
-1
in general
3. Second order reaction: k will be in terms of (mol)
(1-order)
sec
-1
and so on.
Let us now understand the significance of k.
Suppose for the reaction
2N
2
O
5
4NO
2
+O
2
; where the rate law is found to be rate = k[N
2
O
5
]
1
so that it is a first order reaction, the experimental value of k at some constant temperature
comes out to be 0.1 sec
-1
. What does it mean?
It means that if initial concentration (at t=0) of N
2
O
5
is 1 mol L
-1
then its concentration after the
first second will remain 10% less of the original value i.e. 0.9 mol L
-1
. Then in the next second it
will be 10% less of 0.9 mol L
-1
i.e. 0.81 mol L
-1
, as shown in the following table.
Time (sec.) Concentration of N
2
O
5
(mol L
-1
)
t=0 1.0
1 0.9
2 0.81
3 0.729
4 0.6561
5 0.59049 and so on.
Another significance of k is this that white comparing two or more reactions of same order; we
can say that more is the value of k faster is the reaction.
Factors Influencing Rate of Reaction
i. Nature of reactants: In chemical reactions, the bonds in the reactants are broken and
new bonds are formed to form the products. Obviously the rate of reaction must
depend on the nature of these bonds. Thats why ionic reactions are faster than
molecular reactions. Even among the molecular reaction some are faster than the other
depending upon the strengths of covalent bonds involved. For example the reaction
H
2
+I
2
is slower than H
2
+Br
2
and H
2
+Cl
2
reactions. The last two are examples of chain
reactions which are otherwise also fast reactions. Similarly most of the organic reactions
are slower than the inorganic reactions. In some heterogeneous reactions, the physical
state of the reactant also affects the rate of reaction for example saw dust burns much
faster than a piece of wood, sometimes even the rate of mixing of the reactants also
affect the rate of reaction. For example if a layer of KI be formed in a watch glass and
then add few drops of Pb(NO
3
)
2
on it, reaction does not seem to go but as soon as we
stir them the reaction goes ahead to form PbI
2
.
ii. Concentration of reactants: It is the most important factor affecting rate of reaction.
According to law of mass action rate of reaction for a substance is proportional to its
active mass i.e. its molar concentration. Thus more is the concentration more must be
the rate of reaction. But to be more accurate, we must know the order of reaction also.
Thats why for a first order reaction, doubling the concentration of reactant, doubles the
rate of reaction, but it becomes four times in care of a second order reaction and eight
times in case of a third order reaction. Of course, rate of reaction for a zero order
reaction does not depend on the concentration and remains constant at constant
temperature.
iii. Temperature Normally rate of reaction increase with the rise in temperature. For
example if we add KMnO
4
drops to ice cold oxalic acid solutions, the purple color
disappears very slowly but with hot oxalic acid soon it disappears quickly. This is
expressed in terms of temperature coefficient of the reaction such that:
temperature coefficient =
t
10) (t
k
k
+
2 to 3.
It means for every 10
o
C rise in temperature, rate of reaction increases two to three times. A
more accurate result of effect of temperature is given by Arrhenius equation which we shall in
detail later on in the chapter.
iv. Catalyst: Those substances which enhance the rate of reaction but themselves remain
unaffected at the end of the reaction are called catalyst or positive catalyst, but those
which retard the reaction are called negative catalyst or inhibitors. For example addition
of a little MnO
2
, increase the rate of decomposition of KClO
3
.
v. pH of the solution: Reactions occurring in aqueous medium are generally affected by pH
of the solution. For example Tl(III) oxidizes [Fe(CN)
6
]
4-
in acid medium (pH<7.0) but
cannot do so in alkaline (pH>7.0) medium. Similarly reaction of HCN on a carbonyl group
to form cyanohydrins occurs with substantial rate at pH 10.0 but not in strong basic or
strong acid medium.
vi. Nature of the medium: Specially for the reactions occurring in liquid phase, it is found
that dielectric constant of the medium affects the rate of reaction. For example when
the reaction between bromophenol blue (an acid-base indicator) and OH
-
ions is carried
out in the different mixtures of water and alcohols, it is found that as the dielectric
constant of the medium increases, the rate of reaction also increases. Similarly in
gaseous reactions pressure also plays on important role like concentration.
vii. Radiation effect: Some reactions do not occur in dark but occurs with large rate in the
presence of light or some specific radiations. For example the reaction between H
2
and
Cl
2
takes place in presence of white light or ultraviolet radiations. Similarly, we know
that photosynthesis in the plants takes place in presence of sunlight i.e.
6CO
2
+ 6H
2
O + hv C
6
H
12
O
6
+ O
2
viii. Electric and magnetic field: This becomes applicable to some typical reactions involving
isotopes.
Now with this much of background we are in a position to understand our next article of this
chapter which is:
(II) ORDER OF REACTION
While studying the specific reaction rate or rate constant (k) we have come across a term rate
law or rate expression which gives a mathematical relation between rate of reaction and
concentrations of the reactants involved.
Such expressions can never be formulated by simply examining the balanced chemical equation
of the reaction under consideration. It is always formulated with the help of experimental
observations. For example for the reaction:
2 N
2
O
5
4NO
2
+O
2
It is experimentally found that rate of reaction is proportional to the concentration of N
2
O
5
.
Hence Rate = k[N
2
O
5
]
Note that stoichiometric coefficient of N
2
O
5
in the balanced equation is two but the power of
concentration of N
2
O
5
in the rate law is only one. We will say that order of the above reaction is
one.
Therefore order of a reaction is defined as the sum of the powers (exponents) on the
concentration terms in the experimentally determined rate law of the reaction is called its
order of reaction.
Thus for the reaction
H
2
+ I
2
2HI, the rate law is found to be: Rate =
dt
] d[H
2
= k [H
2
][I
2
]
Hence, we say that this reaction is first order with respect to H
2
and also first order with respect
to I
2
but its overall order is two.
Similarly for the reaction:
2NO + O
2
2NO
2
the experimental rate law is rate = k [NO]
2
[O
2
]
1
. Therefore it is second order
with respect to NO, first order with respect to O
2
but its overall order is 2+1=3.
Remember order of reaction is a very important characteristic of the given reaction hence it is
essential to keep the following points in mind while studying order.
a. Order of reaction is always an experimental quantity: We can never predict its value for
a reaction by simply considering its balanced chemical equation. For example consider
the following two reactions:
2 N
2
O
5
4 NO
2
+O
2
and
2 NO
2
2NO+O
2
Although stoichiometric coefficients of reactant in both is two yet the former is a first
order and later is a second order reaction.
b. Generally, most of the reactions are found to be of first or second order, two reactions
are found to be of third order but higher order reactions are highly improbable. Why
this is so? We will certainly get its answer but wait for some time. Also there are some
zero order reactions for example the photochemical reaction between H
2
and Cl
2
i.e.
(g)
2HCl
hv
(g)
2
Cl
(g)
2
H +
With rate law as: rate = k [H
2
]
o
[Cl
2
]
o
= constant
At the same time one should not desire this conclusion that orders of reaction not always a
whole number value. No, order of reaction can be fractional also for example for the reaction
H
2(para)
H
2(ortho)
; the rate law found is : rate = k [H
2(para)
]
3/2
(*Ortho H2 means nuclear spins of both H atoms are but for Para they are anti-parallel)
and for the reaction
CHCl
3
+ Cl
2
CCl
4
+ HCl
the rate law is: rate = k[CHCl
3
][Cl
2
]
1/2
so that overall order is 1.5.
Even the order of a reaction with respect to one of the products is negative also.
For example for the reaction
2O
3
3O
2
the rate law found is: rate = k [O
3
]
2
[O
2
]
-1
Well! As per our syllabus, we shall have a detailed study of zero and first order reactions but
before that it is necessary to understand some more terms like molecularity of the reaction,
how does it differ from the order? And also how order is related to mechanism of the reaction?
Molecularity of Reaction:
To understand this term let us consider the oxidation of HBr by O
2
at 500
o
C. This reaction
occurs in the following three steps which we may call elementary steps:
HBr + O
2
HOOBr
HOOBr + HBr 2HOBr
HOBr + HBr H
2
O + Br
2
x [2]
_______________________________Add.
4 HBr + O
2
2H
2
O + 2Br
2
Now here we see that in each step there one two molecules undergoing collisions. Therefore
the molecularity of each step or elementary step in two. Though it appears from the
stoichiometry of the total reaction that the total molecularity must be fire, but this will be a
wrong conclusion because the probability of collision of 4 molecules of HBr and one molecule
of O
2
at a time is very-very small. Therefore it is useless or irrelevant to talk of total molecularity
of a reaction. In fact, it is always for that elementary step which we are discussing. Hence
molecularity of a step can be defined as:
It is equal to the number of those molecules or atoms or radicals whose collision is a must for
the occurrence of the step.
Therefore it must be clearly understood that order of a reaction is always related to the whole
of the reaction and for that we must formulate its mechanism consisting of some elementary
steps. But molecularity is a term individually applicable to each elementary step.
The significance of elementary steps, we shall learn soon under the heading-mechanism of
reaction but before that let us conclude with some points giving difference between the order
and molecularity as shown in the following table.
Table
Difference between order and molecularity
Order of reaction Molecularity
1. It is related to the whole of the reaction It is related to the specific
elementary step.
2. It is an experimentally determined quantity It is not experimental. It is
simply an imagination for the
step.
3. Order can be whole number, zero, fractional
or even negative It is always a whole number
quantity
Sometimes reactions are classified as
Unimolecular for ex:
O
3
O
2
+ O
N
2
O
5
NO
2
+ NO
3
etc.
Bimoleculas for ex:
NO + NO
3
2NO
2
CH
4
+ Cl CH
3
+ HCl etc.
Trimolecular for example:
2NO + Br
2
2NOBr
NO + N
2
+ O NO
2
+ N
2
etc.
But some reactions are also known as pseudo molecular reactions. To understand this term let
us consider the following reaction: (hydrolysis of ester)
CH
3
COOC
2
H
5
+ H
2
O CH
3
COOH + C
2
H
5
OH
(excess)
In this reaction water is taken in excess, hence the change in its concentration will be negligible
as compared to its total concentration. In other words, the concentration of water (or any
substance taken in excess in general) can be taken to be constant. Therefore rate of reaction
will depend only on the concentration of ester, so that its rate low becomes:
Rate = k [CH
3
COOC
2
H
5
]
Hence the order of reaction is one, but the molecularity is two. Such reactions are called
pseudo unimolecular reactions. In this manner there can be other pseudo molecular reactions
also.
Let us now discuss a very important article
Order and Mechanism of reactions:
For the occurrence of a chemical reaction, it is supposed that it takes place by collisions
of reactant particles which may be atoms, molecules radicals or ions. Because of this collision,
the chemical bonds are rearranged to form the products.
Now a reaction may be completed within a single step for example:
NO + O
3
NO
2
+ O
2
or H
2
+ I
2
2HI
So, here we can very safely say that every instant one molecule of H
2
is colliding with one
molecule of I
2
to form two molecules of HI. This is in agreement with its experimentally
determined rate law which is rate = k [H
2
] [I
2
]
But if we consider a reaction, say 2FeCl
3
+ 6KI 2FeI
2
+ 6KCl + I
2
, then one may think of
collisions of two molecules of FeCl
3
with 6 molecules of KI, every instant to form the products.
But look here, how much improbable it is? We know that even the collisions of 4 particles at
time is almost impossible then how can we think of collisions of 8 particles and that too such
that 2 are of one type and 6 of other type?
This can be compared with a situation that in a crowded street, 2 cars and 6 bikes are
undergoing collisions every time. Though we cannot rule out such an accident to occur yet its
probability is very-very law. Therefore even if we consider the collisions of 2 molecules of FeCl
3
and 6 molecules of KI responsible for the occurrence of above reaction then on account of very-
very law probability, the rate of this reaction must be very-very small. But contrary to that this
reaction occurs with a measurable velocity. What does it mean?
It means this reaction must not take place in one single step but it must occur in some steps
which we may call elementary steps. Then the question arises that how to devise these steps!
This problem can be solved by first finding out its order experimentally. For this particular
reaction the experiments have given the rate law as:
Rate = k [FeCl
3
] [KI]
2
[ Total order = 2+1=3]
It means we can think of this reaction going on in some elementary steps such that one of those
steps must involve the collision of one molecules of FeCl
3
and two molecules of KI.
With this view we can proceed to propose that this reaction may occur in the following two
steps.
FeCl
3
+ 2KI FeI
2
+ 2KCl + Cl -------- (i)
and 2KI + 2Cl 2KCl + I
2
-------- (ii)
Now the next question arises that from which of the above elementary steps, the order of
reaction emerges out. Obviously it must be the step (i) because the experimental rate law is in
perfect agreement with that. Such an elementary step from which order can be deduced
directly or indirectly is called Rate Determining Step (RDS) and it is supposed to be the slowest
moving step. You may further raise a question that why, the slowest moving step must be the
RDS? This can be understood with the help of following logical example.
Suppose that there is a platoon or group of 20 soldiers such that they have to run from one
place to another with their maximum efficiency (naturally they will not run with the same
speed). And our task is to find out the velocity of the platoon, not the velocity of individual
soldier.