Chemical

Kinetics,
Course No.
Chem-572,
M.Sc.(Chem.),
I year, II
Semester
Chapter 1: Elementary
Reaction Rate
Dr. Khalid Siraj, Assistant Professor
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Introduction
Chemical Kinetics constitutes to be an important topic in physical chemistry. It
concern itself with measurements of the rate of the reactions proceeding under a given
conditions of temperature, pressure and concentration. The study of this subject has been
highly useful in determining the factors which influence rates of reactions as well as in
understanding mechanisms of a number of chemical reactions. The experimental data led to
the development of modern theories of chemical reactivity of molecules. The study has also
been useful in working out conditions for getting maximum yields of several industrial
products.
Thermodynamics predicts that at room temperature hydrogen and oxygen react to
form water, all the reactants being essentially converted into the product. But when actually
carry out the experiment we find that the reaction takes place so slowly that unless we are
willing to wait indefinitely, practically no water results. On the other hand, experiments
shows that N
2
O
4
decomposes into NO
2
under atmospheric conditions almost instantaneously
even though G
o
, which is measure of spontaneity of a reaction, is far less for the
decomposition of N
2
O
4
than that for the reaction between hydrogen and oxygen to form
water. These two examples suggest that there is essentially no correlation between
thermodynamics instability and the rate of a chemical reaction. In fact, the rate of a reaction
depends upon structural and energetic factors which are not uniquely specified by
thermodynamic quantities such as the free energy change. Hence, chemical kinetics is a
technique complimentary to thermodynamics for studying a given reaction.
Experimental Determination of Rate
For the determination of rate of reaction at constant volume the concentration of a chosen
reactant or product is determined at various time intervals. The change in concentration C,
for a given time interval t (t
2
t
1
) is obtained. An average rate of reaction is then obtained
by calculating C/t. The smaller the value of t, the closer the value of the rate will be to
the real rate at time (t
1
+ t
2
)/2 because
The rate of reaction can also be obtained by plotting concentration of reactant or product
against time and measuring the slope of the curve (dc/dt) at the required time. The rate of
reaction obtained from such method is known as instantaneous rate. The concentration of the
reactant or product varies exponentially or linearly with time as shown in Figure below
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Figure: Concentration variation of the reactant/product with time.
For determination of the instantaneous rate at any point a, the slope of the curve is
determined. It may also be noted from above Fig. that if the concentration varies linearly with
time, the slope of the curve or rate of the reaction will remain same throughout the course of
reaction. However, if concentration of the reactant or product varies exponentially with time
the slope of the curve or the rate of reaction will be different at different time intervals. Thus,
it is not necessary that rate of reaction may always remain same throughout the course of
reaction. The reaction may proceed with a different rate in the initial stage and may have
different rate in the middle or near the end of the reaction.
In place of concentration of reactant or product any physical property, which is directly
related with concentration, such as viscosity, surface tension, refractive index, absorbance
etc. can be measured for the determination of the rate of reaction.
Chemical kinetics deal with the study of the rate of the reaction and the mechanism by
which they occur there are three types of reaction-
1. Fast reactions They proceed at very fast speed
2. Very slow Reaction They proceed at a very slow speed
3. Moderate Reaction They proceed at a moderate speed
Reaction Rate: The rate of a reaction is defined as the change in concentration of any
reactant and product per unit time. Let us consider a simple reaction.
A P
The concentration of A decreases and P is increase as time passes. So rate of the reaction tells
us to what speed the reaction occurs
Rate of reaction = Rate of disappearance of A = Rate of appearance of P
R = -d[A] / dt = d[P] / dt
e.g., aA + bB + cC lL + mM + pP

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Rate Constant or Velocity Constant: The rate of a reaction is directly proportional to the
reactant concentration, each concentration being raised to power.
nA Product
Rate [A]
n

Rate = k [A]
n

If [A] is equal to unity, then r = k. Thus, at a given temperature, the rate constant or
velocity constant of a reaction, in general, is equal to the rate of the reaction when the
concentration of the reactant is unity.
aA + bB + cB Product
Rate = k[A]
a
[B]
b
[c]
c

If [A] = [B] = [C] = 1, then r = k. Thus at a given temperature, the rate constant of a
reaction is equal to the rate of the reaction when the concentration of each of the reactants is
unity.
Order of a reaction: In chemical kinetic, the reactions are classified according of their order.
The order of a reaction is defined as the number of molecules whose concentrations
determine the rate of the chemical reaction at a given temperature. Alternatively, we may
define the order of a reaction as the sum of the powers to which the concentration terms are
raised in order to determine the rate of the reaction. Thus, a reaction is said to be of the first
order if its rate is given by the expression of the type: r = k[A]; of the second order if the
rate is given by the expression of the type: r = k[A]
2
; r = k[A][B] and of the third order if the
rate is given by the expression of the type: r = k[A]
3
; r = k[A][B]
2
; r = k[A]
2
[B]; r =
k[A][B][C] and so on. For a zero order reaction, the rate equation is written as r = k
0
. It is to
be noted that the order of a reaction is essentially an experimental quantity.
The order of a reaction may not be always be a whole number. It can be a fractional
quantity also. It is particularly so in heterogeneous reactions.
For a simple reaction nA + mB product
Rate = k [A]
n
[B]
m

The order of reaction = (m + n)
The order of the reaction is also defined as the number of molecules or atoms whose
concentration alters during a chemical reaction.
Unit of Rate Constants:
S.No Order of the Reaction Units of rate constant
1 Zero-order Mole / liter / second
2 First order s
-1

3 Second order Liter. Mole
-1
s
-1

4 Third order Liter
2
mole
-2
s
-1

5 N
th
order Liter
n-1
mole
1-n
s
-1

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Molecularity: It is theoretical value and without any experiment we can determine the
molecularity. It is defined as the number of molecules or atoms involved in the step leading
to the chemical reaction.
Suppose, if one molecule involve the reaction is said to be unimolecular-
N
2
O
5
(g) N
2
O
4
(g) + O
2
(g)
If two molecules
2HI
(g)
H
2
(g) + F
2
(g)
If these molecules-
2NO(g) + O
2
(g) 2NO
2
(g)
From the kinetic study of the reaction The order of the reaction involving the
decomposition of nitrogen pentoxide is 1, that of the reaction involving the dissociation of
hydrogen iodide is 2 and that of the reaction involving combination of nitric oxide and
oxygen is 3.
But this is not always the case; in several reactions the order is different from
molecularity. This is particularly so which one of the reactants is present in large excess. The
examples are hydrolysis of ethylacetate and inversion of cane sugar in aqueous solution.
CH
3
COOC
2
H
5
+ H
2
O CH
3
COOH + C
2
H
5
OH
C
12
H
22
O
11
+ H
2
O C
6
H
12
O
6
+ C
6
H
12
O
6

The molecularity of each reaction is 2. The order of each reaction, however, is 1. We know
from the experiment that the rate of the reaction varies directly as the concentration of ethyl
acetate in the first case and that of sucrose in the second case. The reason is that water is
present in such large excess that its concentration remains almost constant in the course of the
reaction in each case.
Differentiation between Order and molecularity:
S.No Order Molecularity
1 It may or may not have relation with
stoichiometric equation of reaction
Molecularity is calculated from a single
balanced equation
2 It refers to reaction as a whole irrespective
of number of steps involved.
It refers one single step of a reaction.
3 It may be whole number, fraction or zero. It is always whole number.
4 Depends on experimental determined rate
of overall reaction.
Depends on rate determining step.

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Factors Affecting the Rate of Reaction-
The rate of chemical reaction depends on many factors as:
1- Nature of reacting substances
The rate varies from one reaction to another depending on the physical state of the
reacting substances (gas, liquid or solid) and chemical constituent of them (ions, neutral
molecules or free radical).
2- Temperature
Chemical reactions are generally very sensitive to temperature. An increase in temperature
leads almost invariably to increase in reaction rate due to increasing in kinetic energy of
reaction.
3- Concentration of reactants
In general the greater concentration reactants lead to increase in reaction rate. According
to the dependence of reaction rate on concentration reactants, reaction order can be detected.
(Zero, first, second, third or other orders can be obtained).
4- Pressure
Rates of reactions in solution and unimolecular reactions in the gas phase are
dependent on pressure.
5- Catalysts
Some gas phase chain reactions have rates which are affected by the surface of the
reaction vessel. Heterogeneous catalysis (more than one phase) occurs when a surface
increases the rate of the reaction.
C
2
H
4
+H
2

Ni
C
2
H
6

Homogeneous catalysis (one phase)
The positive catalyst is called promoter, or sensitizers. While the substance decreases rate of
reaction is called negative catalysts or inhibitors.
Sometimes, the product accelerates the reaction rate, so it is called auto catalyst and other
time the product minimizes the rate, so it is called auto inhibitors.
6- Medium of reaction including change of solvent, permittivity, viscosity and ionic
strength can all affect the rates of reactions in solution
As change of solvent may alter the rate of reaction in solution
e.g. (1) C
2
H
5
I + (CH
3
)
2
N [C
2
H
5
N
+
(CH
3
)
2
] I
This reaction in nitro benzene is faster 1000 times than in cyclohexane medium e.g.(2)
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Trinitrobenzoic acid + NaOH/CaO (Sodalime) trinitrobenzene + CO
2

The rate of this reaction in different solvents as




7- Photochemical reactions occur under the influence of radiation. Conventional sources of
radiation, and modern flash and laser photolysis techniques, are both extensively used.
Integration of Rate Expressions
1. Zero order Reaction:
Examples are known of reactions in which the reactions in which the reaction rate is
not affected by changes in concentration of one or more reactants. These are called zero-order
reactions. In such reactions, the rate may be determined by some other limiting factor such as
the amount of catalyst used in a catalytic reaction or the intensity of light absorbed in a
photochemical reaction. Mathematically, for a zero-order reaction
A Products
r = - d[A] / dt = k

where k

is the rate constant. Rearranging,
dx /dt = k
Or dx = k dt
If at t = 0, the initial concentration and the concentration at t = t, then integration yields

} }
=
X
O
t
dt k dx
0

x - 0 = k. t
x = k. t
k = x/t zero order
The above integrated rate equation for a zero-order reaction.
Half life period: It is defined as the time required for the reaction to be half completed and is
denoted by the symbol, t. It can be related to the corresponding rate constant. If x = a / 2 at
t = t then,
k = x/t




Solvent Rate
H
2
O 3.33x 10
-6

Nitro benzene 4.07x10
-9

Toluene 1.62x 10
-7

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2. First order Reaction
Reaction in which the reaction rate is determined by the change of concentration of one
reactant only.
A Products
Initial conc. o 0
Conc. after time t o-x x
The rate of reaction is given by


On integration of above equation

} }
=

x t
dt k
x a
dx
0 0
) (

or
or, [-ln (a-x) + ln a] = k. t


Unit, since a / (a-x) is a dimensionless quantity
k = 1/sec or k = Sec
-1
Half-life for the first order reaction:
In order to characterize the rate at which a chemical reaction may proceed, it is customary to
introduce a convenient parameter called the half-life time of the reaction. It is defined as the
time required for the reaction to be half completed and is denoted by the symbol, t. It can
be related to the corresponding rate constant.
If x = a / 2 at t = t then
k = 2.303 / t log a / (a-a/2)
k = 2.303 / t log 2a/2a-a
k = 2.303/t log 2a/2a-a
k = 2.303/t log 2a/a
k = 2.303/t log 2 [log 2 = 0.301]
k = 2.303/t x 0.301

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which may actually give a little more insight into what is meant by half-life. This equation
demonstrates clearly that the concentration drops by a factor of two for every t
1/2
increment in
time.) For first order processes it is common to define a relaxation time, by

The relaxation time is relevant only to first order reactions, and is a fractional lifetime which
bears a very simple relation to the rate constant as a direct consequence of the exponential
behavior of first order reactions so that one can write the integrated form of the rate law as

is the time required for [A] to drop from [A]
o
to [A]
o
/e. Sometimes is called the "one over
e" time. Although the half-life is almost always used to describe the decay rate of radioactive
elements, it is common for chemists to talk about the rate of first order processes in chemistry
in terms of the relaxation time.

Figure shows half -lives time for first order reaction
Example 1. Shows that the thermal decomposition of N
2
O
5
, where P
o
= 348.4 mm. at t
o,
as
shown in equation. N
2
O
5

N
2
O
4
+ O
2
follows first order kinetics, and find
the rate constant
Time, min x, mm/ Hg (a-x), mm/Hg a / (a-x) ln a / (a-x) 10
4
k, s
-1

0 348.4 348.4 1 0 0
20 163.2 185.2 1.88 0.63 5.25
40 243.0 105.4 3.31 1.20 5.00
60 289.8 58.6 5.95 1.78 4.95
80 315.3 33.1 10.52 2.35 4.90
100 329.8 18.4 18.93 2.94 4.90
160 345.6 2.8 124.42 4.82 5.06
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y = 0.0005x - 0.0033
R
2
= 0.9996
0
2
4
6
0 2000 4000 6000 8000 10000 12000
Time, s
Fig.1 Plot of relation of ln ( a / a-x) vs. time in reaction of
N
2
O
5
N
2
O
5
+ 1/2 O
2
l
n

(
a

/

a
-
x
)

Example 2. Show that the thermal decomposition of azoisopropane to hexane and nitrogen
at T = 250
o
C follows first order kinetics, and find the rate constant
CH
3
CH
3

CH- N= N CH C
6
H
14
+ N
2

CH
3
CH
3


Time, s mm/ Hg x =P
T
P
i

mm/Hg
(P
i
-x), mm/Hg P
i
/ (P
i
-x) ln P
i
/ (P
i
-x) 10
3
k, s
-1

0 P
i
= 35.15 0 35.15 1 0 0
180 P
T
= 45.90 10.75 24.40 1.44 0.37 2.06
360 53.90 18.75 16.40 2.14 0.76 2.11
540 58.85 23.70 11.45 3.07 1.12 2.07
720 62.20 27.00 8.15 4.31 1.46 2.03
1020 65.55 30.40 4.75 7.40 2.00 1.96
y = 0.002x + 0.0264
R
2
= 0.9986
0
1
2
3
0 200 400 600 800 1000 1200
Time, s
Fig.2 Plot of ln (P
i
/ P
i
-x) vs. time in reaction of
asoisopropane hexane + nitrogen
l
n

(
P
i

/


P
i

-

x
)

Example 3. Show that the decomposition of N
2
O follows first order kinetics, and find the
rate constant and half-life.

100 61 37 10
Time/s 0 50 100 230

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Answer: We need to find log
e
[N
2
O] to log
e
[N
2
O]
t
versus t.
log
e
[N
2
O]
t
-2.30 -2.80 -3.30 -4.61
The graph of log
e
[N
2
O]
t
versus t is linear, therefore, reaction is first order.
Slope = -1 x 10
-2
s
-1
, hence k = -1 x 10
-2
s
-1
.

This value agrees with the value read directly from the experimental graph.
Example 4. Trichloroethanoic acid is readily decarboxylated in aqueous solution:
VolumeCO
2
/cm
3
2.25 8.30 14.89 31.14 40.04
Time/min 330 1200 2400 7760
Show the reaction to be first order, and calculate the time taken for the initial concentration of
CCl
3
COOH to fall by 25%.
Answer: Volume of CO
2
produced when reaction is complete [CCl
3
COOH]
o

Volume of CO
2
produced at time t [CCl
3
COOH]
reacted
[CCl
3
COOH]

left at time t = [CCl
3
COOH]
o
- [CCl
3
COOH]
reacted


Where v is the appropriate volume of CO
2

First order plot: log
e
[A]
t
= log
e
[A]
o
kt
The decrease in concentration of reactant volume of CO
2
evolved = constant x volume.
Hence plot log
e
( versus t.
v
t
/cm
3
2.25 8.30 14.89 31.14 40.04
/cm
3
37.79 31.74 25.15 8.90 0
log
e
3.632 3.458 3.225 2.186 -
time / min 330 1200 2400 7760
Plot of log
e
(40.04 v
t
) versus t is linear and reaction is first order.
Slope = 1.94 x 10
-4
min
-1
, therefore, k = 1.94 x 10
-4
min
-1

When 25% of CCl
3
COOH has reacted, 25% of the final amount of CO
2
will have been
formed, i.e., 10.01 cm
3
.
Therefore, at this time [CCl
3
COOH] (40.04 -10.01) cm
3
.
log
e
(40.04 10.01) = log
e
40.04 - 1.94 x 10
-4
t.
t = 1485 min.


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Radioactive Decay as a First Order Phenomenon
When a radioactive substance is separated from its parent and its activity is measured from
time to time, the rate of decay follows the law as
-dI/dt = I [1]
where I is activity at any time t and a constant called the radioactive disintegration constant
which is characteristic of the radioactive element irrespective of its physical condition or state
of chemical combination. This equation, on integration, gives
= 2.303/t log (I
o
/I) [2]
where I
o
in the initial activity, i.e., when t = 0.
Since the activity I is proportional to number of atoms that have not yet disintegrated,
we can use relation
= 2.303/t log (n
o
/n)

[3]
where n
o
and n are the number of atoms of radioactive substance at time t = 0 and at any time
t, respectively.
The above equation (3) suggests that there is a definite probability of an particular
atom disintegrating at a given moment and this is proportional to the number of atoms present
at that moment.
Half-life period gives the time t

which must elapse for the radioactivity to decay to
half its value at any instant and may be obtained by pulling n = n
o
.
Thus
Or t

= log 2/ = 0.693/ [4]
In time t

the activity is reduced to one-half of its initial value and, therefore, in n t

time,
the activity is decreased to (1 )
n
. Theoretically, therefore the activity never falls to zero.
Average-life period of any radioactive atom is length of time, which can exit before
the atom disintegrates and can be calculated as follows.
Since the activity is proportional to number of atoms, which have not disintegrated,
equation (1) may be written as
- dn/dt = n
Or -dn = n
o
e


t

dt ; n = n
o
e


t
[5]
The number of atoms disintegrating in the interval between t and t + dt is equal to dn. Since
dt is very small, dn may be taken as number of atom disintegrating at time t. The period of
average life is obtained by multiplying every possible life period t from zero to infinity, by
the number of atoms dn and then dividing the product by the total number of atoms n
o

present at the beginning of the time. Thus,
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[6]
Substituting the value of dn from equation (5) and ignoring the sign of dn, we have
[7]
[8]
The average-life of a radioactive atom is thus equal to the reciprocal of its radioactive
constant and is a measure of mean expectation of future life of the atoms present at any
instant.
Radioactive Equilibrium
The rate of decay of a given radioactive substance must also represent the rate at which its
disintegration product is being formed. The product will also disintegrate at a rate depending
on its amount present. This will be small initially, but will increase with time. Thus, in any
given series a state of equilibrium will eventually be reached, when the rate at which it itself
disintegrated. Mathematically, it can be represented as
dn1/dt = dn2/dt = dn3/dt [9]
where n
1
, n
2
, n
3
. represent the number of atoms of different radioactive elements in the
series present at equilibrium.
Again, since dn/dt = n, we may have

Or 1/ 2 = n2/n1.. [10]
Therefore, at radioactive equilibrium, the amount of different radio elements present
will be inversely proportional to their decay constant, or directly proportional to their half- or
average-life periods.
The time taken for the complete equilibrium to be established depends on the life
periods of elements involved. The longer the average life of any element, more slowly an
equilibrium with its product is reached.
Problem 1: The half-life of a radioactive substance
91
X is 20 years. Calculate the decay
constant. In how many years three quarters of the given amount of substance will disappear?
Solution:
1 year = 365 x 24 x 60 x 60 = 3.15 x 10
7
sec


Since decay follows first order kinetics, t

is independent of a i.e., initial concentrations. 50%

of substance decays in 20 years, next 50% of remaining i.e., 25% will decay in 20 years.
Therefore, 75% will decay in 40 years.
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Problem 2: A radioactive elements gives 2000 counts /min at a given time. After an hour the
counts were found to be 750/ min. what is the half-life of the element?
Solution: The decay constant





2. Second order Reaction
A second order is one in which the rate is determined by the variation in two
concentration terms. There are two types of second order reactions:
(i) 2A Products
(ii) A + B Products
Consider the (i) case. The initial concentration of A is a mole/litre and mole/litre of A
have transformed into products after a time t sec. Then the concentration will be (a-x)
mole / litre

or,

or,


On integration of the above equation
} }
=

x t
dt k
x a
dx
0 0
2
) (

(

}
) (
) 1 )( 1 (
) (
2
x a x a
dx

t k
x a
x
.
1
0
=
(

The above equation is required integrated expression for the rate constant of a second-order
reaction in which two molecules of the same reactant are involved in the reaction.
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The classic example of the above type of the second-order reaction is the gaseous
decomposition of hydrogen iodide.
2HI(g) H
2
(g) + I
2
(g)
The rate expression for this reaction is
r = - d[HI] / dt = k [HI]
2

The plot of r versus reactant concentration is shown in figure

Plot showing the slope for the concentration versus t graph.
The rate constants of second-order reactions in which the two reactants, although different,
have the same initial concentration, are also determined with help of above equation.
Second-order equation unit mol
-1-
Sec
-1
L
Half-life Period of second order:
If x = a/2, t = t , then


Example: Show that the following reaction follows second order kinetics, and find the rate
constant and first half-life.
10
3
[A]/mol dm
-3
7.36 3.68 2.45 1.47 1.23
Time/s 0 60 120 240 300
Answer: We need to find 1/[A]
t
to plot 1/[A] versus t
1/[A]/mol
-1
dm
3
136 272 408 680 813
The graph of 1/[A] versus t is linear, therefore, reaction is second order.
Slope = + 2.26 mol
-1
dm
3
s
-1
and k = + 2.26 mol
-1
dm
3
s
-1
.

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For the Case IInd
Suppose that initial conc. of A & B is a & b and after time t the conc. of A & B will be (a-x)
& (b-x)

This can be written as
where k is the second-order rate constant.

or
Resolving into partial fractions (assuming that a > b), we have

On integrating the above equation

dt k
x b x a
dx
t x
o
} }
=

0
) )( (






The above equation is the required integrated expression for the rate constant of a second-
order reaction. Here we assumed that a > b. If we had assumed that b > a, then the reader can
easily verify that

The plot of the equation versus t gives a straight line whose slope is equal to
the rate constant, k.
Example: Saponification of ethyl butyrate by Ba(OH)
2
at 25.
Time, s (a x ) (b x ) b(a-x) a(b-x) b(a-x)
a(b-x)
ln b(a-x)
a(b-x)
(1/ a-b) ln b(a-x)
a(b-x)
10
3
k,
lmol
1
s
-1

0 19.75 20.85 411.79 411.79 0
5 14.75 15.85 307.54 313.04 0.98 -0.2 0.018 3.6
17 9.40 10.50 196.00 207.38 0.95 -0.6 0.055 3.24
36 5.93 7.03 123.64 138.84 0.89 - 0.12 0.11 3.06
65 3.50 4.67 73.00 94.01 0.77 - 0.25 0.23 3.50
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia


y = 0.0032x - 0.0002
R
2
= 0.9985
0
0.05
0.1
0.15
0.2
0.25
0 10 20 30 40 50 60 70
Time, s
Fig.4 Plot of (1/ a-b) ln[ b(a-x ) / a(b-x)] vs. time in reaction of
saponif ication of ethyl butyrate by Ba(OH)
2
at 25
o
C.
(
1
/

a
-
b
)

l
n

b
(
a
-
x
)












a
(
b
-
x
)

Pseudo First Order Reactions
There are circumstances where a second order reaction might appear, in an experiment, to be
first order. That is when one of the reactants in the rate equation is present in great excess
over the other in the reaction mixture.
As an example, let's look again at the mixed second order rate law that we treated in the last
section.
] ][ [
] [
B A k
dt
A d
=
In the last section we had the rate law, with a reaction whose stoichiometry is,
2A + B P + etc (P = product). Sometimes [B]
o
>> [A]
o

For example, say we prepare the system such that,
[B]
o
= 2.0 M, and [A]
o
= 0.001 M.
Then, when the reaction has run to completion, (at time = infinity),
[B]
inf
= [B]
o
2 [A]
o
= 2.0 0.002 = 1.998 2.0.
So [B] is approximately constant throughout the entire reaction. Then the rate law becomes,

which is effectively a first order rate equation. This rate equation has the solution,

where the "effective" first order rate constant is k[B]
o
. You can actually solve this problem as
a mixed second order rate problem, as we did in the last section, but it is a lot more work.
Pseudo first order reactions are sometimes used to find the rate constant of a second order
reaction when one of your two components is very expensive and the other one is relatively
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

cheap. You can use an excess of the inexpensive reagent and use a small amount of the
expensive one. Notice that you can still obtain the second order rate constant by dividing the
effective first order rate constant by the concentration of the excess component.
Example: Hydrolysis of ethyl acetate in presence of H
+
ion catalysis
H
+

CH
3
COOC
2
H
5
+ H
2
O CH
3
COOH + C
2
H
5
OH
At various intervals of time, definite sample of mixture withdraw and titrate against standard
solution of NaOH.
Following data are depicted in table to specify pseudo first order reaction.
Time, hr V
t
(V
t
-V
o
) =x (V

- V
t
)= (a-x) (a / a-x) ln (a / a-x) k, hr
-1

0 V
o
= 11.10 0.00 4.30 1 0 0
12 V
t
= 11.78 0.68 3.62 1.18 0.17 0.014
24 12.28 1.18 3.12 1.38 0.32 0.013
48 13.13 2.03 2.27 1.89 0.64 0.013
72 13.69 2.59 1.71 2.51 0.92 0.013
96 14.07 2.79 1.33 3.23 1.17 0.012
V

= 15.40 a =4.30 0.00 - -
y = 0.0122x + 0.0224
R
2
= 0.9976
0
0.4
0.8
1.2
1.6
0 20 40 60 80 100 120
Time, hr
Fig.5 Plot of ln (a / a-x) va. time f or hydrolysis of ethyl acetate
in acidic medium, which exhibit pseudo f irst order reaction
l
n

(
a

/

a

-

x
)

3. Third-Order Reaction
Let us consider a third-order reaction of the type
3A Products
Let a be the initial concentration of A and x the amount of A that has reacted at time t so that
the amount of A remaining at time t is a x. The differential rate equation is
r = dx / dt = k (a x)
3

where k is third order rate constant. Separating the variables and integrating, we get

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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

Or
To determine the integration constant, C, we know that at t = 0, x = 0 so that C = a
2
.
Substituting in above equation transposing and solving for k, we get

When three different molecules react
A +B +C product
) )( )( ( x c x b x a k
dt
dx
=
By integration

When two initial concentration are equal, say a = b, 2A + C Product
kt
x c a
x a c
x a a
a c x
a c
=
(

) (
) (
ln
) (
) (
) (
1
2

Units of third order rate constant and t
1/2

k = 1 / time (conc.)
2
= conc.
2-
t
-1
= L
2
mol
-2
s
-1
sec ,
2
3
2
3
2
1
2
4
2
1
)
2
( 2
1
2
2 / 1
2 2 2 2
2
2 / 1
ka
t
a a a a
a
a
kt
=
= =

=

4. n
th
-Order Reaction
If a reaction takes place for which only one reactant is involved, a general rate law can be
written as

If the reaction is not first-order so that n is not equal to 1, integration of this equation gives

Or,

From this equation, it is easy to show that the half-life can be written as

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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

Or
|
|
.
|

\
|

=
=

1
1
2 / 1
2 / 1
1 1
1
2 / 1
1
1
1 2
) 1 (
1
1
1
1
2
1
1
)
2
( 1
1
n
n
n n
n
n
n
a n k
t
kt
a n a n
kt
a n
a
a n

In this case, n may have either a fraction or integer value.
Determination of order of a Reaction:
There are many ways to determine the order of reaction, which are as follows:
I. Half life period: In this method, the time (t ) required to complete half of the
reaction is determined and experiment repeated with different, but equal initial molecular
concentrations of the reactants. If half-life period is found to be:
(a) Proportional to initial concentration (a), the reaction is of zero order
(b) Independent of initial concentration (a), the reaction is of Ist order
(c) Inversely proportional to the initial concentration (a) of the reactants the reaction
is of second order
(d) Inversely proportional to the square of the initial concentration, that is of third
order.
If t and t

are the times for the half-life period with initial concentration a
1
and a
2

respectively, then order of reaction (n) is given by:

Taking logarithms, we get:


Since a
1
, a
2
t
1/2
and t
1/2
are known so order reaction (n) can be computed.
II. Graphical Method: In this method, for a particular experiment at different intervals
of time, if:
1) log (a-x) values on plotting against time (+) values gives a straight line, the reaction is
of first order.
2) 1/ (a-x) values on plotting against t values gives a straight line, the reaction is of
second order; and so on.
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

III. Integration Method: In this method, known and equimolar quantities of the reactants
are mixed and the progress of the reaction is determined by analyzing portion of the reaction
mixture after regular intervals of time. The experimental data thus obtained is substituted in
the various equations for reactions of first, second, third order, etc., turn by turn. The
equation which gives the most concordant constant value of the specific reaction rate (k)
corresponds to the correct order of the reaction. The method involve, the trial of one equation
after another, till the correct one is found -
k = 2.303/t log a/(a-x) [Ist order reactions]
k = 1/t. x/a (a-x) [IInd order reaction]
k = x (2a-x) / 2t.a
2
(a-x)
2
[For 3
rd
order reaction
IV. Ostwalds Isolation Method: This method is applicable, particularly in the case of
reactions in which there are two or more reactants. The method consists in performing a
series of experiments, in which all but one of the reactants are taken in large excess turn by
turn, so that it concentration does not very sensible during the course of the reaction. Then
order is determined with respect to isolated reactant (i.e., which is taken in small amount)in
each case. Evidently the order of reaction so determined is with respect to isolated reactant
only. The sum of the individual order, when each reactant is taken separately in small amount
is the overall order of reaction. E.g.
2FeCl
3
+ SnCl
2
2FeCl
2
+ SnCl
4

1) When FeCl
3
is taken in large excess, the velocity with respect to SnCl
2
is proportional
to the first power of concentration of SnCl
2
. On the other hand,
2) When SnCl
2
is taken in large excess, the velocity with respect to FeCl
3
is proportional
to the square of concentration of FeCl
3
. Hence, the order of the above reaction is 1+2
= 3, i.e. 3
rd
order reaction.
V. Logarithms Method (Differential or Variation method)
Suppose a reaction can be represented as
aA + bB Products
and that it follows a rate law that can be written in the form

If the reaction is carried out at two initial concentrations of A but with the initial
concentration of B kept constant, the ratio of the reaction rates will be given by

Taking the logarithms (either natural or common) of both sides of the equation gives
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia


Solving for n gives

Rate = k [reactant]
n
Taking log of both sides gives
log rate = log k + n log [reactant]
and a plot of log rate versus log[reactant] should be linear with gradient = n, and intercept =
log k. Hence n and k can be found.
For example, assume that
R
o
= k[A]
x
[B]
y
[C]
z

Run several experiments at different starting concentrations and measure R
o
in each case. We
can place the data in a table as follows:
[A]
o
[B]
o
[C]
o
R
o

0.010 0.10 0.20 0.04 for experiment number 1,
0.020 0.10 0.20 0.08 for experiment number 2,
0.010 0.20 0.20 0.16 for experiment number 3,
0.010 0.10 0.10 0.04 for experiment number 4
Compare the first and second experiments. We double [A]
o
and the rate doubles. It looks like
x = 1. Compare the first and third experiments. We double [B]
o
and the rate increases by a
factor of 4. It looks like y = 2. Notice that there is no change in the rate when we cut [C]
o
in
half so the rate must not depend on C. This says that z = 0.
Thus we determine that the rate = k[A]
1
[B]
2
[C]
0
.
We don't have to use simple whole number ratios for the concentrations, we can do it
algebraically. Take the ratio of the rates from two successive experiments,

To find the exponent of [A] make all the concentrations in the second experiment the same as
in the first experiment except [A]. This gives,

Take the logarithm of both sides to get,

and solve for x to get,

This process can be repeated for each of the components in turn.
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

Example
In reaction of NO with hydrogen the value of rate (-dp / dt) was found to be 1.5 mms
-1
for
initial pressure 359 mm, 0.25 mms
-1
for pressure 152 as pressure of H
2
was kept constant,
while when pressure of NO was kept, -dp / dt was 1.6 mms
-1
for H
2
at pressure 289 mm , 0.75
mms
-1
at pressure 147 mm.

1 . 1
147 log 289 log
75 . 0 log 6 . 1 log
07 . 2
152 log 359 log
25 . 0 log 5 . 1 log
log log
log log
2
1
2 1
2 1
=

=
=

|
.
|

\
|

|
.
|

\
|

=
n
n
P P
dt
dp
dt
dp
n

Order n = n
1
+ n
2
= 2.07 + 1.1 =317 3 (third order).
Experimental Methods of Measuring Reaction Rate:
These determine directly changes in concentrations of reactants and products with time, but
they may have the disadvantages of sampling and speed of analysis. When reaction is
sufficiently fast to result in significant reaction occurring during the time of sampling and
analysis, the rate of reaction is slowed down by reducing the temperature of the sample
drastically, called quenching; reaction rate generally decreases dramatically with decreasing
temperature. Alternatively, reaction can be stopped by adding a reagent which will react with
the remaining reactant. The amount of this added reagent can be found analytically, and this
gives a measure of the amount of reactant remaining at the time of addition.

Chemical Methods

These are mainly titration methods (volumetric or gravimetric) and they can be highly
accurate. They are generally reserved for simple reactions in solution where either only the
reactant or the product concentrations are being monitored. Here sampling errors and speed
of analysis are crucial. Chemical methods have been largely superseded by modern black box
techniques, though, in certain types of solution reaction, they can still be very useful.
Question: The catalysed decomposition of hydrogen peroxide, H
2
O
2
, is easily followed by
titrating 10 cm
3
samples with 0.0100 mol dm
-3
KMnO
4
at various times.
2H
2
O
2
(aq) 2H
2
O(l) + O
2
(g)
Vol. 0.01 mol dm
-3
KMnO
4
/cm
3
37.1 29.8 19.6 12.3 5
Time/min 5 10 20 30 50
5/2H
2
O
2
(aq) + MnO
4
-
(aq) + 3H
+
(aq) Mn
2+
(aq) + 5/2O
2
(g) + 4H
2
O(l)
1 mol MnO
4
-
reacts with 5/2 mol H
2
O
2

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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

Calculate the [H
2
O
2
] at the various times, and show that these lie on a smooth curve when
plotted against time.
Answer:
10
4
x number of mol MnO
4
-
used 3.71 2.98 1.96 1.23 0.50
10
4
x number of mol H
2
O
2
present 9.28 7.45 4.90 3.08 1.25
10
2
x [H
2
O
2
] / mol dm
-3
9.28 7.45 4.90 3.08 1.25
The graph of [H
2
O
2
] versus time is a smooth curve showing the progressive decrease in
reactant concentration with time.
Physical Methods
These use a physical property dependent on concentration and must be calibrated, but are still
much more convenient than chemical methods. Measurement can often be made in situ, and
analysis is often very rapid. Automatic recording gives a continuous trace. It is vital to make
measurements faster than reaction is occurring.
The following problems illustrate typical physical methods used in the past.
Pressure Changes in Gas Phase Reactions

Graph of [H
2
O
2
] versus time
Question: Which of the following reactions can be followed in this way and why?
1. CH
3
CHO(g) CH
4
(g) + CO(g)
2. Br
2
(g) + C
2
H
4
(g) C
2
H
4
Br
2
(g)
3. Cl
3
CCOOH(aq) CHCl
3
(aq) + CO
2
(g)
4. 2HI(g) H
2
(g) + I
2
(g)
5. (CH
3
CHO)
3
(g) 3CH
3
CHO(g)
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

Which reaction would give the largest change in total pressure and why? Suggest an
alternative method for reaction 3.
Answer. This method can be used for reactions which occur with an overall change in the
number of molecules in the gas phase and which consequently show a change in total
pressure with time.
pV = nRT and p n if V and T are constant
1. Gives an increase in the number of gaseous molecules: pressure increases.
2. Pressure decreases with time.
3. Pressure increases with time.
4. Pressure remains constant, so this method cannot be used.
5. Pressure increases.
Reaction 5 gives the greatest change in the number of molecules in the gas phase, and hence
the largest change in pressure.
In reaction 3, CO
2
is the only gaseous species present and the reaction could be followed by
measuring the volume of gas evolved at constant pressure with time
Chromatographic Techniques: liquidliquid and gasliquid chromatography (GLC)
When introduced, chromatographic techniques completely revolutionized analysis of
reaction mixtures and have proved particularly important for kinetic studies of complex
gaseous reactions. A complete revision of most gas phase reactions proved necessary,
because it was soon discovered that many intermediates and minor products had not been
detected previously, and a complete re-evaluation of gas phase mechanisms was essential.
Chromatography refers to the separation of the components in a sample by
distribution of these components between two phases, one of which is stationary and one of
which moves. This takes place in a column, and once the components have come off the
column, identification then takes place in a detector.
The main virtues of chromatographic techniques are versatility, accuracy, speed of
analysis and the ability to handle complex mixtures and separate the components accurately.
Only very small samples are required, and the technique can detect and measure very small
amounts e.g. 10
-10
mol or less. Analysis times are of the order of a few seconds for liquid
samples, and even shorter for gases. However, a lower limit around 10
-3
s makes the
technique unsuitable for species of shorter lifetime than this.
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

Chromatography is often linked to a spectroscopic technique for liquid mixtures and
to a mass spectrometer for gaseous mixtures. Chromatography separates the components; the
other technique identifies them and determines concentrations.
In G.C used the relation between time and peak area where from which we can study
the rate ( peak area concentration )
Peak area at time t = A
t
, Peak area at time 0 = A
0
, Peak area at time = A

Amount of reactant after t time = A
t
- A
0 =
x ,
Initial amount of reactant = A

- A
0
= a
Spectroscopic Techniques

Microwave, infrared, Raman, visible and UV spectra are all used extensively for
identification. In the gas phase these show sharp lines so that identification is easy. In
solution, the complexity of the spectra gives them sufficient features to make them
recognizably specific to the molecule in question
Concentration determination
Using Beers law, concentrations can be found from the change in intensity of the radiation
passed through the sample. The absorbance, A, of the sample at a given wavelength is
defined as

where I
0
is the incident intensity and I the final intensity. Beers law relates this absorbance
to the concentration of the species being monitored:

Where is the absorption coefficient for the molecule.
depends on the wave length and the identity of the molecule.
is the wavelength, d is the path-length and c is the concentration of the absorbing species.
Provided that and d are known, the concentration of absorbing species can be found. A
calibration graph of A versus c should be linear with slope and zero intercept.
Microwave, infra-red, Raman, visible and UV spectra are all used.
Special features of absorbance measurements
If the reaction being monitored is first order, i.e. has rate [reactant]
1
, or is being studied
under pseudo-first order conditions, the absorbance can be used directly, eliminating the need
to know the value of will show that such reactions can be quantified by plotting
loge[reactant] against time. Since absorbance [reactant], then log
e
absorbance can be
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

plotted directly against time without the need to convert absorbance to concentration using
Beers law.



Since is a constant in any given experiment, then is also a constant, and

A plot of versus time differs from a plot of versus time only in so far as it is
displaced up the y-axis by an amount equal to . The slope of the graph of log
e

absorbance versus time is the same as the slope of the graph of log
e
[reactant] versus time.
The slope of this latter graph gives the quantity which characterizes the reaction.

Graph of log
e
absorbance Vs time and log
e
[reactant] Vs time
Absorbance (A) Concentration of reactant
Absorbance at time 0 = A
0
, Absorbance at time t = A
t
, Absorbance at time = A

,
x = amount of product after time t = A
t
- A
0
,
a = initial amount of reactant = A - A
0
.
Special features of fluorescence intensity
Fluorescence is a special type of emission of radiation. In emission, a molecule is moving
from an excited state to a lower state, and the frequency of emission is a manifestation of the
energy change between the two states. When the excited molecules have been created by
absorption of radiation shone on the molecules, the resultant return to lower states is termed
fluorescence. The initial exciting radiation can either be a conventional source or a laser .The
fluorescence intensity is generally proportional to [reactant], so that

Where f is a constant of proportionality,
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia


and so again there is no need to convert to concentrations. This can be sometimes be
particularly useful, e.g. when laser-induced fluorescence is being used for monitoring
concentrations.

Graphs of log
e
[intensity of fluorescence], and log
e
[reactant] versus time
Question: In a 1.00 cm spectrophotometric cell, solutions of C
6
H
5
CH=CHCCl
2
in ethanol of
known concentration give the following values of the absorbance, A.
10
5
x conc. / mol dm
-3
0.446 0.812 1.335 1.711 2.105
A 0.080 0.145 0.240 0.305 0.378
Note that,

Divide both sides by 10
5
, and multiply both sides by mol dm
-3
. This gives

This is a standard way of presenting tabulated data, and it is necessary to be completely at
ease in performing the above manipulation.
It is also necessary to be careful when drawing graphs of tabulated data presented in this
manner, so as to get the powers of ten correct. Using Beers law, draw a calibration graph and
determine the value of

c .
The reaction of this substance with C
2
H
5
O
-
in ethanolic solution is followed
spectrophotometrically. The following results are found. Plot a graph of reactant
concentration against time.
Time/min

0 40 80 120 140
A 0.560 0.283 0.217 0.168 0.149
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

Answer: A graph of A versus c is a straight line through the origin. From the slope = 1.79 x
10
4
dm
3
mol
-1
cm
-1

This can be used to calculate the [reactant] corresponding to each absorbance, since A = cd.
Since d = 1 cm the following table can be drawn up:
Time/min

0 40 80 120 140
10
5
x conc. / mol dm
-3
3.13 1.58 1.21 0.939 0.832
Alternatively, values of the concentration corresponding to the measured absorbance can be
read off from the calibration curve.

Conductance Methods
As molar conductance inversely proportional with concentration. So, by time the conductance
have been changed and by this relation we can do kinetic
1 2
3
1

= = = A mol ohmCm
molCm
ohmCm
c
k

These are useful when studying reactions involving ions. Again this can be illustrated by a
problem
Question: Which of the following reactions can be studied in this way, and why?
1. (CH
3
)
3
CCl(aq) + H
2
O(l) (CH
3
)
3
COH(aq) + H
+
(aq) + Cl
-
(aq)
2. NH
4
+
(aq) + OCN
-
(aq) CO(NH
2
)
2
(aq)
3. H
3
O
+
(aq) OH
-
(aq) 2H
2
O(l)
4. CH
3
COOCH
3
(aq) + OH
-
(aq) CH
3
COO
-
(aq) + CH
3
OH(aq)
5. CH
3
COOH(aq) + H
2
O(l) CH
3
COO
-
(aq) + H
3
O
+
(aq)
Answer: Conductance changes are ideal for reactions involving ions.
1. Ions are produces, and the conductance rises with time.
2. Ions are removed, and the conductance decreases with time.
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Department of Chemistry, CNS, Jimma University, Jimma, Ethiopia

3. Ions are removed as reaction occurs, but this is very rapid reaction and special fast
techniques are needed. Ion-ion reactions are often very fast.
4. Here a highly conducting ion is replaced by a less conducting ion, and the conductance
will fall with time.
5. Ions are produced, but this is an ionization of an acid, and these are generally very fast
reactions and cannot be studied in this way.
pH and EMF Methods Using A glass Electrode Sensitive to H
3
O
+

Question. What types of reaction could be studied in this way?
Answer. In these methods a glass electrode sensitive to H
3
O
+
enables reactions which occur with
change in [H
3
O
+
] or a change in [OH
-
] to be followed with ease. A pH meter measures pH
directly, and a milli-voltmeter measures EMFs directly, and these are related to [H
3
O
+
], e.g.
- Br
2
(aq) + CH
3
COCOCH
3
(aq) + H
2
O(l) CH
3
COCH
2
Br(aq) + H
3
O
+
(aq) + Br
-
(aq)
Here H
3
O
+
(aq) is produced and the pH will decrease with time, with a corresponding change in
EMF
- CH
3
COOCH
3
(aq) + OH
-
(aq) CH
3
COO
-
(aq) + CH
3
OH(aq)
Since OH
-
(aq) is removed, [H
3
O
+
] will increase and the pH will decrease with time, with a
corresponding change in EMF and
- CH
3
COOCH
2
CH
3
(aq) + H
3
O
+
(aq) CH
3
COOH(aq) + CH
3
CH
2
OH(aq)
In the acid hydrolyses of esters H
3
O
+
(aq) is removed, and the pH increases with time, with a
corresponding change in EMF.