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Chapter II

Reaction Rates
Chemical kinetics is the study of the reaction rates, how reaction rates
change under different conditions.
Chemical rate of reactions:
Chemical reactions require varying lengths of time for completion, depending
on the characteristics of the reactants and products and the conditions under
which the reaction takes place. Many reactions take few seconds, others take
more.
The study of the rate, or the speed, of a reaction has important applications.
For eg. In the manufacture of ammonia from nitrogen and hydrogen you want
to know the conditions that will help the reaction proceed in a commercially
length of time. Also we want to know if the NO gas will destroy the ozone in
the stratosphere faster than the ozone is produced. To answer these
questions we must have knowledge of the rates of reactions.
Reaction rate:
It is the increase in the amount (molar conc.) of product of a reaction per unit
time or the decrease of the amount (molar conc.) of the reactants per unit
time.
The rate of a reaction =

change of conc./ time

2 N 2O5 (g) 4 NO2(g) + O2 (g)


The rate of this reaction could be found by observing the increase in molar
conc. Of O2 produced.
Rate of formation of oxygen = [O2]/ t
* ( means the change in the conc., which can be obtained by subtracting the
initial value from the finial value).
The last equation gives the average rate over the interval t. if the time
interval is very short, the equation gives the instantaneous rate (rate at a
particular instant of time)
Also we can express the rate on terms of the decomposition of the reactant
N2O5.
Rate of decomposition of N2O5= - [N2O5]/ t

Negative sign indicate a decrease in conc. and to give a positive value for
the rate. Thus because [N2O5] decreases, [N2O5] is negative and (- [N2O5]/
t) is positive.

Fig. (1) The instantaneous rate of reaction.


The instantaneous rate is the value of [O 2]/ t for the tangent at a given
instant (the straight line that just touches the curve of concentration versus
time at a given point)

To calculate the average rate for the previous equation:


Time
0
600
1200
1800
2400
3000
3600
4200
4800

[O2]
0.0000
0.0021
0.0036
0.0048
0.0057
0.0063
0.0068
0.0072
0.0075

There is an increase in the conc. of oxygen during the decomposition of the


N2O5.When the time changes from 600s to 1200s (t = 600s), the O2 conc. by
0.0015 mol/L ([O2]).Therefore the average rate =[O2]/ t = (0.0015/600=
2.5x 10-6 mol/L.s). Later, during the time interval from 4200s to 4800s the
average rate = 5x 10-7 mol/L.s
The rate decreases as the reaction proceeds.

Note:
Rate of formation of oxygen = the rate of decomposition of N 2O5 as there
are 2 moles of N2O5 which decompose to only one mole of O2.
[O 2]/ t= -1/2 [ N2O5]/ t
Example:
Consider the reaction of nitrogen dioxide with fluorine to give nitryl fluoride.
2 NO2(g) + F2(g) 2 NO2F(g)
How is the rate of the formation of NO2F related to the rate of reaction of
fluorine?
Solution:
Rate of formation of NO2F = [NO2F]/ t
Rate of reaction of F2 = - [F2]/ t
Then divide each rate by corresponding coefficient and then equate them.
(1/2 ) [NO2F]/ t = - [F2]/ t
Example:
Calculate the average rate of decomposition of N2O5, by the reaction2 N2O5 (g)
4 NO2(g) + O2 (g)
During the time interval from t = 600 s to t= 1200 s. use the following data
Time
600s
1200s

[N2O5]
1.24x 10-2 M
0.93X10-2 M

Rate of decomposition of N2O5= - [N2O5]/ t


= - (0.93-1.24)X10 -2M/(1200-600)s
=5.2x10 -6 M/s
Iodide ion is oxidized by hypochlorite ion in basic solution.
Rate of decomposition of N2O5= - [N2O5]/ t
= - (0.93-1.24)X10 -2M/(1200-600)s
=5.2x10 -6 M/s

Iodide ion is oxidized by hypochlorite ion in basic solution.


I-(aq) + ClO-(aq) Cl-(aq) + IO-(aq)
In 1.00 M NaOH at 25 c, iodide ion concentration equal to the ClO concentration at different times was as follows:
Time
2.00 s
M
8.00 s
M
Factors affecting

[I-]
0.00169

Calculate the average rate of reaction of Iduring this time interval.

0.00101
reaction rates:

1-Concentration of reactants:
The rate of reaction increases as the concentration of reactant increases.
A piece of steel wool burns difficulty in air(20% O 2)but bursts in pure oxygen.
2- Concentration of catalyst:
A catalyst is a substance that increases the rate without being consumed in
the overall reaction. It doesn`t appear in the balanced chemical equation
but can be written over the arrow.
2H2O2(aq)

2H2O(l) + O2(g)

HBr acts as a catalyst to speed decomposition.


3- Temperature:
Reactions speed when temperature increases.
4- Surface area of a solid reactant or catalyst:
The surface of the solid react in the reaction affects the reaction rate. The
rate increases with increasing the surface area.
A wood fire burns faster if it is cut into smaller pieces.
The collision theory of reactivity:
e.g. CH=CH(g) + O2(g) CO2(g) + H2O(g)
Ethyne
Collision of ethyne and O2 can result in a reaction. However, only a few these
collisions result in a reaction. Not all collisions are effective.
*Effective collisions occur when the kinetic energy of the colliding molecules
provides sufficient energy for reaction.

a reaction can`t occur if the molecules do not collide (basis of collision


theory).
By increasing pressure of a gas, molecules are closer together and more
collisions will occur.
Increasing number of collisions and the reaction rate is faster.
Increasing the conc. of reactants in solutions. Also increases the rate of a
reaction (increasing effective collisions) (at constant temperature).
Increasing temperature will cause a wide distribution of energies and
therefore speeds of molecules.
The increased speed of molecules will lead to more molecules gaining
sufficient energy to react on collision.
Summary:
1) Molecules will react only when they collide.
2) Reactions will occur only if there is enough energy in collision.
3) Increased conc. of molecules, increases collisions increasing rate of
reaction.
4) Increased temperature, increases proportion of molecules with sufficient
energy to react increases reaction rate.