Chemical kinetics

71

3. CHEMICAL KINETICS

3.1. Formal kinetics of simple reactions

Kinetics is the study of the rates of chemical process in an effort to
understand what is influencing these rates. It helps to develop theories which can
be used to predict them.
The object of chemical kinetics is to study the rate and the mechanism of
chemical reactions. The chemical kinetics is looking for the evolution in time of the
systems which react. The time variation of a system which reacts is not determined
by the initial and the final state of the system, it depends on the way followed, that
means on the mechanism after which the chemical transformation takes place.
Let us consider a general chemical reaction:
v1 A1 + v2 A2 + ... + vi Ai + ... v1' A1' + v2' A2' + ... + v1' A1' + ...
The reaction rate can be defined with respect to any participant on the
reaction, reactant or products, as concentration variation in time.

vi =

1 dnA

vi dt

or vi' = +

1 dnA

vi' dt

'
i

[124]

where dnA represents the mole number in an elementary transformation.

i

The sign (-) or (+) reveals the decreasing of concentration of a reactant which is
consumed and respectively the increasing of concentration of the product which is
formed in the reaction.
If the concentration is expressed as mole numbers per unit volume, we
obtain specific rate:

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vi =

1 1 dnA
1 dc A

=
vi V dt
vi dt

vi' = +

1 1 dnA
1 dc A

=
+

vi' V dt
v1' dt

'
i

'
i

[125]

[126]

The main factors which influence the rate of reaction for a homogenous
system are: temperature, pressure and composition.
Based on experimental data Goldberg and Waage have established in 1867
that the reaction rate at a given temperature and pressure is depending on the active
mass which reacts. For a simple reaction, which takes place in one step (elemental
reaction) the rate is proportional to the product of reactant concentrations, raised to
a power:

vi =

dc A

dt

= kcAn c An c An ...c An
1

[127]

where k is the rate constant or the rate coefficient; it is independent on the

concentration but depends on the temperature. The rate constant is equal to the rate
for reactant concentration of 1 mol/L.

n1 , n2 ,..., ni represent partial orders with respect to each reactant

or the power at which the concentration is raised.
The sum of the partial orders gives the overall reaction order:

n = ni

[128]

The overall reaction order is an empirical dimension and it can take the
following values: integral numbers, ratios, or zero. It gives information on the
complexity of the reaction mechanism.
The overall order should not be confounded with the molecularity (i)
which indicates the number of molecules (particles) which interact in elemental
chemical act. The two dimensions are identical only in the case of elementary
reactions. However, generally ni i .

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73

3.1.1. Kinetic classification of chemical reactions

a) After the phase number of the system there are:
-

homogeneous reaction (one phase)

heterogeneous reaction (many phases).

The two types are different from kinetic point of view since they have
different reaction mechanisms and because of the external factors which can
influence the reaction rate. For example, in heterogeneous reactions it is possible to
have surface phenomena: adsorption, diffusion, etc., which can determine the
global rate for the reaction.

b) After molecule numbers which take part at the elemental chemical

process:
-

monomolecular reactions: N 2 O 5 N 2 O3 + O2

bimolecular reactions:

trimolecular reactions: 2 NO + O2 2 NO2

2 HI H 2 + I 2

The probability to meet simultaneously more than 3 molecules is almost

zero.

c) From kinetic point of view:

-

zero order rate law

(fractional) order rate law

first order rate law

second order rate law

third or more order rate law.

In the case of elemental reactions the overall order is equal to the

molecularity (for instance the first order rate law are monomolecular reactions,
second order rate law are bimolecular reactions, etc). The reduction or
degeneration of the overall order is happens when one of the reactants is in excess.

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GENERAL CHEMISTRY

d) After the complexity of the kinetic mechanism:

-

isolated reactions (simple or elementary)

complex reactions, classified as:

- opposite reactions
k1

H2 + I2

2 HI
k-1

2
v1 = k1c HI
;

v1 = k2cH cI

2
= k1cH cI
At equilibrium v1 = v-1 k1cHI

or
-

k2
c2
= K = HI
k1
cH cI

[129]

parallel (simultaneous) reactions

2KCl + 3O2
6KClO3
3KClO4 + KCl

successive reactions

N 2 O5 N 2 O3 + O2
N 2 O3 + N 2 O5 2 N 2 O4

3.1.2. First order reactions

In a first order kinetic law the reaction rate is proportional to the
concentration raised to the power 1 (hence first):
k
A
Products
1

v=

dc A
= kc A
dt

[130]

At a time t:

c A = c A0 x
where c A0 is initial concentration of A

[131]

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75

dc A = dx

[132]

dc A dx
=
= k1 (c A0 x )
dt
dt

[133]

The equation [133] represents the differential expression of the first order
rate
The constant k is depending on the reactant nature and on temperature.

[k ] =
1

1
time

By integration:
cA

c 0A

t
dc A
= k1 dt
cA
0

[134]

ln

c A0
= k1t
cA

[135a]

ln

c A0
= k1t
c A0 x

[135b]

c A0
= ek t
0
cA x

[136a]

c A0
= ek t
cA

[136b]

c A0 x = c A0 e k t

[137a]

c A = c A0 e k t

[137b]

The expressions [137a] and [137b] are the integrated expression of the first
rate law. Figure 17a presents the time evolution of the concentration of reactant.
Applying the logarithm operator on the equation [137b] one gets:

ln c A0 ln c A = kt

[138]

ln c A = ln c A0 kt

[139]

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GENERAL CHEMISTRY

The equation [139] is a line equation with the slope tg = k1 . In this way
it is possible to obtain kinetics parameters as rate constant or initial concentration
(the intercept) (figure 17b).
cA

c A0
ln (cA0 x)

ln c A0
c A = c A0 x

a) .b)
Figure 17. a) Exponential dependence of the reactant concentration (eq. [137])
b) Graphical representation of eq.[139]

Half life time, t1 / 2 , the time taken for the concentration of a reactant to
half its initial value

t1 / 2 c A = c A0 x =
ln

c A0
2

c A0
= k1t1 / 2
c A0
2

t1 / 2 =

ln 2
k1

[140]

For a first order reaction, the half life time of a reactant is independent of
its initial concentration.

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77

Examples
1. Calculate the rate constant and the half life time of a reaction

A Products (1st order) knowing that the initial concentration of the reactant
was 7.5 mol/L and after 20 min it decreases to 5 mol/L.

dc A
= kc A
dt
cA

c 0A

dc A
= kdt
cA

ln c A ln c A0 = kt
ln c A ln c A0
k=
t

k=

1
min

k = 0.02

t1 / 2 =

ln 7.5 ln 5
20

ln 2
= 34.2 min
0.02

2. Knowing that a radioactive substance has the half life time of 500 years
calculate the rate constant of its decomposition.

k=

ln 2
t1 / 2

k=

ln 2
500

k = 1.38 10 3 year 1

3. For the reaction A Products it is known that after 45 sec the reactant
concentration falls to half of its initial value. Determine the rate constant.

k1 =

ln 2
t1 / 2

k1 =

ln 2
45

k = 0.015 sec 1 .

3.1.3. Second order reactions

A + B Products
Examples: 2 HI

H2 + I2

N 2 + O2 2 NO

dc A
dt

dc B
dt

= k2 c AcB

[141]

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GENERAL CHEMISTRY

dc A
dt

d (c A0 x )
=
dt

dx
dt

[142]

dc B
dt

d (cb x )
=
dt

dx
dt

[143]

dx
dt

= k2 (c A0 x )(cB0 x )

[144]

The equation [144] represents the differential expression of the 2nd order
rate law.
By separating the variables and integretion:

cB0 (c A0 x )
1
ln
cA0 cB0 c A0 (cB0 x )

[145]

cB0 (c A0 x )
1 1
ln
t c A0 cB0 c A0 (cB0 x )

[146]

k 2t =
k2 =

ln

c A0 x
cB0 x

= k2 (c A0 cB0 )t + ln

ln

c A0
cB0

[147]

c A0 x
c B0 x
tg = k (c

ln

0
A

c B0

cA0
cB0
t

Figure 18. Graphical representation of eq.[147]

Particular case for only one reactant:

2 A Products
dx
2
= k (c A0 x )
dt
By integrating one gets:

[148]

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79

1
1
0
c x cA

[149a]

1
1
= kt + 0
c x
cA

[149b]

kt =

0
A

or
0
A

c A0 x =

c A0
1+ k 2 c A0 t

[150a]

or
2

k c0 t
x= 2 A 0
1 + k 2 c At

[150b]

cA
c

1
c x

0
A

0
A

tg = k

c x
0
A

1
c A0
t

a)

b)

Figure 19. a) Exponential dependence of the reactant concentration (eq. [150a])

c)

Graphical representation of eq.[149b]

The half life time for the second order reaction:

t1 / 2

11
1
1
= 0 0=
k2 c A c A k2c A0
2

t1 / 2 is reversely proportional to the initial concentration.

[k ] = time
2

conc 1 .

[151]

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Example
For

the

reaction

A+ B C + D

it

is

known

c A0 = 3mol / L and

cB0 = 2mol / L . After 10 min, 1 mole of A is consumed. Determine the rate constant
and the half life time for A.
Solution:

x = 1 mol A is consumed and 1 mol B is consumed. So:

A

t = 0 (initial)

t = 10 min

3-1

2-1

k2 =

c B0 (c A0 x )
1 1
ln
t c A0 c B0 c A0 (c B0 x )

k2 =

1
1
2 2

ln
10 3 2 3 1

k = 2.9 10 2

L
mol min

c A0
1
1
2
= 0
ln
k c A c B0 c A0 (c B0 x )
c B0

t1 / 2

cA x =

c A0
2

x=

c A0
= 1.5 mol/L
2

c B = 2 1.5 = 0.5 mol/L

t1 / 2 =

1
1
2

ln
2
2.9 10 3 2 2 0.5

t1 / 2 = 23.9 24 min

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81

3.1.4 Third order reactions and higher order reactions

Examples:

2 NO + O2 2 NO2

2 NO + Cl 2 2 NOCl
Generally:

A + B + C Products
dx
= k 3 (c A0 x )(c B0 x )(c c0 x )
dt

[152]

Particular case:
a) A = B = C

3 A Products
3
dx
= k 3 (c A0 x )
dt

[153]

After integration:

k3 =

1
1
1
02
0
2
2t (c A x ) c A

[k ] = time
3

[154]

conc 2

The half life time is:

t1 / 2 =

3
2kc A0

[155]

b) A + 2 B Pr oducts
2
dx
= k 3 (c A0 x )(c B0 2x )
dt

or k 3 =

2(2c A0 c B0 )
c A0 (c B0 2 x )
1
+
ln

t (2c A0 c B0 ) c B0 (c B0 2 x )
c B0 (c A0 x )

If the initial concentrations are in stoichiometric ratio ( c B0 = 2c A0 ) then:

[156]

[157]

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3
dx
2
= k 3 (c A0 x )(2c A0 2 x ) = k 3 4(c A0 x )
dt

[158]

By integration one gets:

k3 =

1 1
1
02
0
2
8t (c A x ) c A

[159]

c) A B C
k3 =

0
0
0
0
1
(c cC0 )ln 0cA + (cC0 cA0 )ln 0cB + (cA0 cB0 )ln 0cC
0
0
0 B
t (c c )(c cC )(c A cC )
cA x
cB x
cC x
0
A

0
B

0
B

[160]

nth order rate law

nA Products n 1
n
dx
= k n (c A0 x )
dt

kn =

[161]

1
1
1
+ 0 n 1
0
n 1
t (n 1) (c A x )
c A

t1n/ 2 =

2 n 1 1

[162]

[163]

(n 1)c A0 n1 k n

3.1.5 Determination of the reaction order

There are two kinds of methods for the determination of the reaction order:
-

integral methods

differential methods

A. Integral methods
A1 Verifying the integrated rate laws
The experimental data obtained by measuring the concentration of one
product or reactant at different time intervals are used to verify the supposed

Chemical kinetics

83

integrated rate laws supposed to obtain a constant rate which is not depending on
concentration. This is an analytical method and the constant rate will be the
average.
A graphical method is used, by verifying the linearity of the integrated rate
laws in corresponding coordinates for each rate law. The constant rate will be
calculated from the slope.

A2 Half life time method

For the reactions

nA

products

t1 / 2 = const a ( n 1)

[164]

By measuring the half life times for reaction starting from two different
initial concentrations of reactant one obtains:

t1' / 2 = const a '

( n 1)

t"1 / 2 = const a ''

( n 1)

[165]

By dividing the two relations to one another and applying the logarithmic
operator one gets:

ln

t '1 / 2
a"
= (n 1) ln
t"1 / 2
a'

t '1 / 2
t"1 / 2
n =1+
a"
ln
a'

[166]

ln

[167]

B. Differential methods
B1 Rates method

dc
n
= kci
dt

[168]

Measuring the rates at two concentrations corresponding to two different

times one obtains:

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dc1

n
v1 = dt = kc1

v = dc2 = kc n
2
2
dt

[169]

Dividing the two expressions and applying the logarithmic operator it gives
for n:

n=

ln v1 ln v 2
ln c1 ln c2

[170]

Figure 20. Graphical determination of the rates

From the graph (figure 20) it is possible to determine the rates:

dc1
dt
dc
tg 2 = v 2 = 2
dt
tg1 = v1 =

n=

ln tg 1 ln tg 2
ln c1 ln c 2

[171]

[172]

Due to the fact that the rate varies in time, being for a reactant, big at the
beginning of the reaction and decreasing in time, the precision of the rate
measurements at different times is not the same, why some errors may be
introduced.

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85

B2. Initial rate methods

For a series of initial concentrations, a plot of the logarithms of initial rates
against the logarithms of initial concentrations of the reactant should be a straight
line with a slope n. The intercept is equal to ln k (figure 21).

ln vi = ln k + n ln ci

( vi = kci )
n

[173]

ln vi
tg = n

ln k

ln ci
Figure 21. Determination of kinetics parameters

In order to obtain the initial rates several lines c=f(t) are plotted starting
from different initial concentrations (Figure 21). The initial rates are the slopes of
the tangent at t = 0.

tg 1 = v1
tg 2 = v 2
tg 3 = v3

Figure 22. Graphical determination of the initial rates

3.1.6. Temperature dependence of reaction rate

Experimentally it was observed that the rate increases when the
temperature is raised. For the reactions which take place with measurable rates at
room temperature it was observed that increasing the temperature by 10 degrees the
rate increases from 2 to 4 times. So the reactions have usually measurable rates in a
narrow range of temperature. If for 10 degrees the rate increasing is about 3 times,

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GENERAL CHEMISTRY

for 100 the rate will increase 310 times 105 times. That is why fast reactions at
some hundreds degrees practically stop at room temperatures. Similarly slow
reactions at room temperatures become explosive reactions at higher temperatures.
From experimental data, Svante Arrhenius (1889) established an
exponential dependence between the constant rate and temperature.

k = Ae

B
T

[174]

The equation [174] represents the Arrhenius equation where: A is a preexponential factor (frequency factor) and B =

Ea
where Ea activation energy and
R

R universal gas constant.

Taking logarithm of left and right hand side of Arrhenius equation one
obtains:
ln k = ln A

B
T

[175]

The plot of ln k against 1/T is a straight line with the slope equal to Ea/R
and the intercept equal to lnA (figure 23).
lnk

tg = B =

Ea
Ea
R

1
T
Figure 23. Graphical determination of activation energy

If the rate constant at two different temperatures is known then the

activation energy can be calculated. In that case one gets:

Chemical kinetics

87

k1
k2
Ea =
1 1

T2 T1
ln

[176]

The Arrhenius equation generally verifies the experimental data for the
practical needs of the majority of chemical reactions.
There are also some cases where some deviations from the exponential
dependence may appear. These cases are called Anti-Arrhenius reactions:
-

reactions in which the rate is decreasing when the temperature is

raised. Ex.: A reaction with pre-equilibrium, when dominant is the
effect of change with the temperature of the equilibrium constant;

some heterogeneous catalyzed reactions (enzymatic catalysis)

where there is an optimal temperature domain in which the rate is
maximum;

at chain branching reactions (explosions) the rate is depending on

temperature being discontinuous.

There are two theories in order to give a physical signification on the

Arrhenius parameters: the collision theory and the activated complex theory

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