Chapter I
Chemical kinetics
I.1 Definition
Chemical kinetics is a branch of physical chemistry which studies the
rates of reactions and the mechanisms by which one chemical species
is transformed into another.
This can be considered at two levels:
Macroscopic level: we study the transformation rate of a very large
number of molecules taken together, and we talk about formal kinetics.
Molecular level: we are interested in the rate of chemical processes at the
level of a molecule; this is the study of the reaction mechanism.
I.2 Relation between kinetics and thermodynamics:
When considering the study of a chemical transformation, two questions
come to mind:
** Can the reaction be realised or not, and what the maximum conversion
will be (transformation limit)?
** How fast will this happen?
Thermodynamics can answer the first question, kinetics the second.
I.3 rate of reaction::
Consider the following reaction :
aA + bB → cC + dD
the degree of advancement δ :
so
With : stoichiometric coefficient
Hence:
In the case of a homogeneous reaction, the degree of advancement
can be expressed per unit of reaction volume. And if the volume is
constant, the degree of advancement is expressed as a variation in the
molar concentration
the specific rate :
the absolute rate :
with : γi : stoichiometric coefficient of chemical species i
the reaction rate is the increase in the molar concentration of a product of a
reaction per time unit or the decrease in the molar concentration of a reactant
per time unit.
I.4 Conversion :
The conversion (or conversion rate) is the fraction of a reactant that
has been transformed.
The conversion XA of a chemical species A is :
with
n(A)0 : initial number of moles of species A
n(A) : number of moles at time t
I.5. Simple order reactions:
I.5.1. Rate, order of a reaction and molecularity :
Experimentally, it has been found that the reaction rate can be expressed
as a product:
With K: constant which depends only on T (this is the speed or rate
constant)
f: a function of concentration and independent of T
If we consider the following reaction : aA + bB → cC + dD
Then
whith r : specific rate K : rate constant
n : partial order / A m : partial order / B
The sum (n + m) is the global order of the reaction
Molecularity (M): is the number of chemical species participating in
the elementary chemical act.
I.5.2. . Vant'Hoff rule
Consider the réaction :
aA + bB → cC + dD
If the sum (S) of the stoichiometric coefficients (a + b) is equal to the
molecularity then n = a et m=b
Example :
1 H2 + 1 I2 → 2 HI
S=1+1=2
M=2
So
I.5.3. First-order reactions:
Reactions where the speed is proportional to the concentration of a single
reactant are called first-order reactions.
Consider the reaction:
at t = 0 a 0
at t ≠ 0 a-x x
This reaction has the following rate law:
Rat
erar
ate
at t = 0, x = 0 so C = - ln a and then :
the curve gives a straight line which passes through
the origin and has a slope equal to K (the unit of K is t-1)
Representation of ln(a/a-x) in function
of time (first order reaction)
Half-reaction time
The half-life or half-time, (t1/2), of a reaction is the time taken to
decrease the reactant concentration to one-half of its initial value.
at t1/2, x = a/2 so equation (II.1) becomes
Note that t1/2 does not depend on the initial concentration (a)
I.5.4. Second order reaction :
These are reactions where the rate is proportional to the product of the
concentration of two reactants or the square of the concentration of a
single reactant.
The first type a ≠ b :
Consider the following reaction with a ≠ b
A + B → P
at t = 0 a b 0
at t ≠ 0 a–x b–x x
then:
(I.1)
Given that :
So the integral of equation (I.1) gives :
(I.2)
at t = 0, x = 0, hence:
the equation (I.2) gives :
Plotting the curve as a function of time gives a
straight line which passes through the origin with a slope equal to the rate
constant K
Second type a = b:
Consider the following reaction where a = b, in which case the mixture
is equimolar
A + B → P
at t = 0 a b=a 0
at t ≠ 0 a–x a–x x
So :
(I.3)
The integral of this equation gives :
At t = 0, x = 0, hence :
So equation (I.3) gives :
(I.4)
By replacing t by t1/2 and x by a/2 in equation (I.4), we find :
In this case, t1/2 is inversely proportional to the initial concentration
I.5.5. Reaction of order n :
After integration we find:
This is the equation for the kinetics of a reaction of order n. It is valid
in the case of an equimolar mixture and n ≠ 1
By replacing t by t1/2 and x by a/2 we find
I.6. Influence of temperature on the reaction rate :
In general, a rise in température of 10°C multiplies the rate by a
factor between1,5 et 3. This factor is called thermal coefficient or
frequency factor (K0).
I.6.1. Emperical relation of Arrhénius (1889):
Inspired by Vant’Hoff, Arrhénius experimentally observed that the rate
constant (K) varies in fonction of temperature as follows:
Avec :
K : rate constant Ea : activation energy (cal/mol)
R : idial gas constant (cal/mol.K) T : temperature (°K)
The integral of this equation gives :
or :
This equation is called equation of Arrhénius
I.6.2. Experimental determination of the activation energy:
The linearization of Arrhénius equation gives :
This relation shows that ln K varies linearly with 1/T and the slope of
the straight line is proportional to the activation energy of the reation.
Example :
The decomposition of the nitrogen dioxide is a second-order reaction
2 NO2 → 2 NO + O2
The data of the rate constant of this reaction in function of temperature are
as follows:
T (K) 592 603 627 651,3 656
K (cm3/mol.s) 522 755 1700 4020 5030
To calculate the activation energy, we represente ln K in function of 1/T
9,0
y = -13643x + 29,263
Ea = -R.tgα
ln K R² = 0,9976
8,0
with R = 1,986 (cal/mol.K)
7,0 So
6,0 Ea = 27094,998 (cal/mol)
5,0
0,00150 0,00155 0,00160 0,00165 0,00170
1/T (K-1)
