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Reaction Kinetic
Introduction
11.0.0
11.1.0
Rate of Reaction
C h angeconcentration of t h e substance
Time taken for t h e c h ange
The reaction rate decreases with time. It never remains uniform during
different time periods. It decreases continuously till the reaction
ceases. The units of rate constant are mol dm -3 s -1.
3
Rate of reaction =
moles dm
Seconds
-3
-1
Consider a reaction:
A+B C+D
20
kx1x1 =
cC + dD
1
d
dx
dt
=-
1 d[A]
a dt
=+
1
c
d [B]
dt
d [C ]
dt
1
c
=+
d [D]
dt
11.1.1
11.1.2
20
Rate Constant
1.
The
proportionality
constant in rate law equation
which relates concentration to
the rate of reaction is called
2. It depends on concentration of rate constant of reaction.
reactants,
surface
area
of 2. It is independent of the
reactants,
temperature
and concentration of the reactant.
presence of catalyst. The reaction 3. Its units depend upon the
takes place in one phase.
order of reaction and differ
3. The mechanism involves the according to order of reaction.
formation of an intermediate
substance.
Q.2: Defne Velocity Constant or specifc constant of a reaction?
Ans: Velocity Constant or specific constant of a chemical reaction is the
rate of reaction when the concentrations of the reactants are unity.
Under the given condition, k remains constant but it changes with
temperature.
Consider a reaction:
aA + bB cC + dD
Rate of reaction = k [A]a [B]b
Let
So Rate of reaction = k x 1a x 1b = k
Q.3: What is meant by Rate law?
Ans: The equation which describes the rate of a chemical reaction is
called rate law. The rate of a chemical reaction is directly proportional
to the product of concentrations of reactants each raised to some
power. Consider the following reaction.
aA + bB cC + dD . Rate of reaction [A]a [B]b. This equation is
called rate law.
Order of Reaction
11.1.3
20
(CH3)3 C OH + HBr
Excess
Rate = K [(CH3)3 CBr]
Q.7: What are 2nd order reactions? Explain with an example?
Ans: E.g. Oxidation of NO: Oxidation of NO with ozone is the first
order with respect to O3. The sum of all the exponents which are raised
to the concentration of the reactants according to the balanced
chemical equation gives the order of reaction i.e. 2. So the overall order
of reaction is two.
NO
(g)
+ O3
(g)
NO2
(g)
+ O2
(g)
[C]
T
mol dm3
s
In the case of 2nd order of reaction, the rate equation for 2 nd order
reaction will be as
Rate = k [A] [B] k =
mol dm
3
(3).(mol dm )
mol dm3 s1
= mol-1
dm3 s-1
Q.9: What are 3rd order reactions? Explain with an example?
Ans: Consider the following reaction
2FeCl3 + 6 KI 2 FeI2 +6 KCl + I2
The reaction involve 8 reactant molecules but experimentally it has
found to be 3rd order reaction. Actually this reaction involves 2 steps in
its mechanism. First step is called slow step and second step is known
as fast step. As slowest step is called rate determining step. And order
20
Slow
Fast
2KCl +2I2
-1
-1
11.1.4
1
2
initial
1
a
n1
concentration
of
reactants.
Thus,
knowing
the
initial
20
=
(iv)
[t 1 ]
2
a
2
1
a0
, since
[t 1 ]
2
[t ]
1
2
1
1
a
; since
[t ]
1
2
1
ka
0.693
k
(iii)
[t 1 ]
t1
2
]3
1
a2
;since
t1
2
]3
1.5
ka2
11.1.5
20
(g)
+ CO
(g)
NO
(g)
+ CO2 (g)
Rate = k [NO2]2.
NO2
(g)
+ NO2
In fast way:
NO3
(g)
+ CO
(g)
Net reaction:
NO2
(g)
+ CO
(g)
(g)
NO3
NO2
NO
(g)
(g)
(g)
+ NO
(g)
+ CO2
(g)
+ CO2
(g)
.
.
20
11.2.0
11.2.1
Physical M ethods
Physical
the
Methods
with
complete
20
11.2.2
(l)
+ H2O
(l)
CH3COOH
(l)
+ C2H5OH
(l)
11.3
20
Ans:
Enthalpy change of reaction
11.4
Q.1: Write down the methods for fnding the order of reaction?
Ans: The methods for finding the order of reaction are following:
(i): Method of hit and trail
Method
(iv): Half-Life Method
(iii): Differential
20
Halflife m ethod
1
n1
1
n1
a1
and
[t2
t1
t2
1
n1 . Then by dividing
a2
a2
= [a1 ]
n-1
, by taking log
t1
a2
on both sides, log [ t 2 ] =n-1 log [ a 1 ]
t1
]
t2
n= 1+ log a 2
[ ]
a1
[
11.4.2
Finally
Q.1: Discuss the method of large excess for fnding the order of
reaction?
Ans: In this method one of the reactant is taken in very small amount
as compared to the other reactants. The active mass of substance in
large excess remains constant throughout and the order becomes
pseudo. The order of reaction is totally depended on the substance
which is taken in small quantity because small change in
concentration of that substance which is taken in small
quantity is more effective on the rate of reaction. E.g.
Hydrolysis of tertiary butyl bromide: In this reaction H2O is solvent
and taken in large quantity so its concentration remains constant. And
rate of reaction is only dependent on the concentration of tertiary-butyl
20
(CH3)3 C OH + HBr
Excess
Rate = K [(CH3)3 CBr]
Factors Aff ecting the rate of Reaction
(V.Im p)
11.5
20
11.5.6
- Ea / RT
ln k = ln A + lne
- Ea / RT
Ea
ln k = ln A + [ RT ]
- Ea / RT
lne, As lne= 1
So, ln k =
Ea
]
+ ln A,
RT
Ea
RT
by 2.303)
(or)
log k =
E a
2.303 R
] []
1
T
+ log A
20
mx + c
[]
1
T
E a
2.303 R
E a
2.303 R
or
So
Activation
the
Ans: The reaction occur due to collisions among the molecules, but
every collision does not lead to a reaction. For a collision to be a fruitful
(effective), the molecules must possess the activation energy and they
must be properly oriented. Since all the molecules do not possess the
same energy. A fraction of molecules may have less energy than the
average energy and cannot attain the activation energy and are not
properly oriented. Therefore, all the collisions are not fruitful.
CATALYSIS (V.Im p L.Q + S.Q )
11.6
and
20
11.6.1
Ni(s)
CH3
__
CH3 (g)
Characteristics of a Catalyst
2NH3 (g)
20
11.6.2
11.6.3
Invertase
C6H12O6 + C6H12O6
O
||
e.g.(2) NH2 CNH2 + H2O
Urease
2NH3 + CO2
(Urea)
Q.3: What are controlling factor on the action of Enzyme?
Ans: The activity of the enzyme is controlled by the pH and
temperature. The pH of the medium controls the rates of the enzyme
catalyzed reactions and the rate passes through a maximum at a
particular pH, known as optimum pH. The enzyme activity is lowers or
decreases at other value of pH. Thus, many enzymes of the body
function best at pH of about 7.4, the pH of the blood and body fluids.
Enzyme catalytic reactions have rates at an optimum temperature. The
rate of an enzyme catalyzed reaction is increased with rise of
temperature but up to a certain point. There after the enzyme is
denatured (destroyed). For example, the optimum temperature of
enzyme reactions occurring in human body is 37 oC (98.60 F).
Characteristic of Enzym e
Catalysis
11.6.4
20
H = E
20
Written by
Mudasir Majeed
Ph.D Scholar (Applied Chemistry)
Email: mudasir_ jhang@yahoo.com
Quaid-e-Azam College of Science &
Commerce,Gojra
20