CHEMICAL KINTETICS

INTRODUCTION
Chemical kinetics is dealing with the rate of reactions and their mechanism. Different
substances react at different rates and it was observed that these reaction rates change if certain
conditions are changed. Summarizing these observations we find that the rate of a reaction
depends upon the relativities of the reacting substances, the presence of a catalyst, temperature,
the concentration of the reacting substances.
In this practical works, it will be investigated the influence of reactants concentration on
the reaction rate.
The concentration of the reacting substances.
Whether a reaction is inherently slow or inherently rapid, increasing in a reactant
concentration will increase its speed. As the concentration means the quantity of substance per
volume unit, increasing the number of molecules in a given volume means increasing their
concentration and collision number. As a general rule, the rate of any reaction increases when the
reactant concentration is increased.
To determine the speed of a reaction, we measure the time required for a certain quantity
of reactant to be used up, or for a certain quantity of product to be formed. The formation of
hydrogen iodine is a typical second order reaction: the rate is in fact directly proportional to both
hydrogen and iodine concentration. This proportionality relationship can be expressed in form of
a mathematical relationship by introducing the proportionality constant k:

rate k H 2 I 2
Let us consider a chemical reaction expressed by the generalized equation:

1 A1 2 A2 ........ 1' A1' 2' A2' ...........

(1)

'
where i and 1 are the stoechiometric coefficients and Ai and Ai are the compounds

participating in the reaction.

The rate of a homogenous reaction with respect to the ith component is given by:

 1 dni

(2)
V dt
where ni is the mole number of the ith component. If the volume does not change during the
v R ,i

reaction, the reaction rate may be written as follows:

v R ,i

dci
dt

(3)

In equations (2) and (3) the sign + is assigned to reaction products, for each

and the sign - to reactants for which

dni
0,
dt

dni
0, so that v R ,i 0 .
dt

For a certain reacting system, the reaction rate is a function of concentrations of the
compounds participating in the reaction and the temperature, i.e. v R f ci , T . The concrete
form of the function f ci , T depends on the reaction itself. For most reaction f ci , T is
factorizable, that is, it may be expressed as a product of two functions one depending only on
temperature and the other only on concentrations: f ci , T f 1 T f 2 ci . The function f1 T
designated with the letter k is called the rate constant. The function f 2 ci is a product of powers
of concentration, f 2 ci c1 1 c 2 2 ........ The power at which the concentration are raised are

called the partial order of reaction regarding the ith component. The reaction rate is written by
means of the kinetic equation:
1

v R k c1 c 2 c 3 .... c i ...

(4)

The kinetic parameters k and i may be obtained only through experimental

measurements. The reaction orders values may be integers or fractions, sometimes they may be
zero or negative. For simple reactions, the orders of reaction with respect to reactants have the
same values as the stoechiometric coefficients.
THE DETERMINATION OF REACTION PARTIAL ORDER
In this work, we shall investigate the reaction between sodium thiosulfate Na 2S2O3 and
sulfuric acid, H2SO4 in aqueous solution.
Na 2 S 2 O3 H 2 SO4 Na 2 SO4 SO2 H 2 O S

(5)

The reaction is easy to examine because colloid sulfur is obtained, which causes the
solution to become opaque. The reaction rate with respect to sulfur is:
c s
(6)
t
The quantity c s is a constant for a particular temperature; it corresponds to the
vR

concentration of sulfur which produces the precipitation. By dividing the equation (4) applied to
the chemical reaction (5) by c s , the following kinetic equation is obtained:
vR

1
1

kc Na1 2 S 2O3 c H22 SO4

t c S

(7)

The influence of the concentration of sodium thiosulfate on the reaction rate is examined
and the partial order of reaction with respect to this reactant is obtained. At constant temperature
and constant sulfuric acid concentration, equation (7) becomes:
vR'

1
k ' c Na1 2 S 2O3
t

(8)

where k

SO4
k cHH22SO
4

cs

is the apparent constant rate.

Applying the logarithm to the eq (8) we get:

lg

1
lg k n Na2 S 2O3 lg c Na2 S 2O3
t

(9)

INSTRUCTIONS
Instructions
Put in eight test-tubes the amount of solution indicated in the table below:
No. test
tube
1
2
3
4
5-8

Volume in ml
Na2S2O3
5
4
3
2

H2O

c rel
Na 2S 2 O 3

H2SO4
0
1
2
3

0
0
0
0
5 ml in every
test tube

rel
lg c Na
2 S 2 O3

Time,
s

lg

1
t

Mix the content of test tubes 1 and 5, stir the solution obtained in this way and measure
the time between the mixing and the precipitation of sulphur.
Do the same thing with the pairs of test tubes 2-6, 3-7 and 4-8, measuring the
corresponding times, t .
RESULTS AND CALCULUS

Fill the table using the relative concentration of sodium thiosulfate given by equation (9):
rel
c Na
S O
2

c Na S O
2

0
Na 2 S 2 O3

Plot the dependence lg

V Na S O
2

V Na S O V H O V H
2

(9)
2 SO4

1
rel
f ln c Na
. The slope of this straight line is 1 (see
2 S 2 O3
t

equation 8) while the origin ordinate represent the apparent constant rate k
RESULTS INTERPRETATION: It will be observed if the reaction is a simple or
complex one, and fast or slow reaction
Application:
1. Considering the trimolecular reaction: 2NO + O2 2NO2, calculate the constant rate
for the formation of NO2 at 0C, knowing that after reactioning of 0.16 mols O2 and
0.04 mols NO, the initial rate is 8.19 10-9 mol/ls. The reaction takes place in a vessel
of 0.5l.
2. In a monomolecular reaction A Products , at t =250C, the initial concentration
decrease at 25% in t =52 min. Calculate:
a) the constant rate
b) the time after the initial concentration decrease with 75%
c) the initial reaction rate, if the initial concentration of the reactant is 2.5 mol/Ls.