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CONTENT
1. INTRODUCTION AND BASIC CONCEPT . 03-9
2. KINETICS OF REACTION
10-17
67-82
7. HETEROGENEOUS REACTION
83-87
88-97
98-108
.. 109-120
121-133
134-171
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CHAPTER-1
INTRODUCTION AND BASIC CONCEPT
1. Every industrial chemical process is designed to produce economically a designed product from a variety
of starting material through a succession of treatment steps.
ri
d Ni
then
dt
1 d Ni
Moles of i formed
V dt
(Volume of fluid) (Time)
i.e., the number of moles of component i formed per unit time per unit volume (mol/dm3s). If species i is a
reactant, the numerical value of ri is a negative number (e.g. ri = -3mol/dm3s or ri = 3mol/dm3s)
If species i is a product, then ri= will be a positive number.
ri
1 dN i
V dt
ri
dC
d Ni d
(Ci ) i
dt V dt
dt
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dC
(b.) i
dt
dCi
dt
(c.)
1 dN i
V dt
1 dNi
(d.)
V dt
Ans. (c)
5. (i) Chemical reaction may be classified depending upon no. of phases involved as homogeneous and
heterogeneous reaction. Homogeneous reaction is one which takes place in only one phase. A heterogeneous
reaction is one which involves presence of more than one phases.
(ii) Reaction may be classified according to catalytic and non catalytic reaction.
(iii) Reaction may be classified on the basis of molecularity of reaction.
(iv) The reaction may be classified based upon the heating effect as exothermic and endothermic reaction.
(v) Reaction may be classified as reversible and irreversible reaction.
(vi) Reaction may be classified based upon the order of reaction.
6. Relative rates of reaction:
For the reaction:
aA bB cC dD
The relation between the rate of participants A, B, C, D in chemical reaction with their stoichiometric coefficient
is
rA rB rC rD
a
b
c
d
Also, if we compare
rA
rA rC
a
c
a
rc
c
Rate of disappearance of A =
a
(Rate of formation of C)
c
rA rB rC Relative Rates
1
2
3 of reaction
rA = rate of disappearance of A
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rC 3( rA )
Option (D) is correct
7. Many variable may affect the rate of a chemical reaction. In homogeneous system the temperature,
pressure and composition affect the rate of reaction.
In heterogeneous system factors that affect the rate of reaction are rate of mass transfer i.e., heat transfer
nature of catalyst if present.
Heterogeneous reactions involve more than one phase.
Rate of reaction is expressed in measure other than volume such as reaction surface area or catalyst weight.
ri' Number of moles of i formed per unit time per unit mass of catalyst (mol/s.g catalyst0
8. Rate law
An algebraic equation that relates the reaction rate and concentration
A B PRODUCTS
-rA k A (T ) f n (C A , CB )
or
rA k A C ACB
kA Rate constant/ specific reaction rate
Order of reaction (n) = +
For the reaction where all the stoichiometric coefficients are 1 e.g.
A+BC+D
k A kB kC kD k
Imp. Rate Laws Are determined by experimental observation.
If concentration is to be expressed in mol/l and time in hours, the value of rate constant would be
(a.) 0.12hr-1 (mol/L)-1
(b.) 0.012hr-1(mol/L)-1
(c.) 12hr-1(mol/L)-1
(d.) 1.2hr-1(mol/L)-1
Solution: 1L = 10cm3
1hr = 60min
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rA 0.02C A2
1 1
hr
10 60
mol
rA 0.02C A2 600
L hr
rA 12C A2 mol L1hr 1
Clearly k 12
unity of k
rA
C A2
molL1hr 1
mol 2 L2
unit of k mol 1L hr 1
k 12hr 1 (mol / L) 1
Option C is correct
Q.4. The rate of reaction for a gas phase reaction is expressed as
dp A
2.56 PA2 atm / hr
dt
dp A / dt
p A2
(b.) hr 1 (atm)3
(c.) hr 1atm
(d.) hr 1 (mol / L) 1
atm / hr
atm 1hr 1
2
atm
TYPES OF REACTIONS
9. (i) A homogeneous reaction is one which takes place in only one phase; i.e., all the reacting material and
products and catalyst (if any) will be present in a similar phases.
1
O2 ( g ) NO2 ( g )
2
A hetrogeneous reaction is one which involves the presence of more than one phase.
Example: NO( g )
1
V2 O5 ( s )
O 2 ( g )
SO3 ( g )
2
(ii) Catalytic reaction are those reaction which involves use of catalyst to enhance the rate of reaction.
Example:
SO2 ( g )
Example:
Ni
C 2 H 4 H 2
C2 H 6
Heat
Ethylene
Ethane
Non catalytic reactions are those reaction which does not involve use of catalyst.
1
NO O 2 NO 2
2
(iii) The reaction may be classified based upon the molecularity of a reaction i.e., based upon the number of
Example:
molecules that takes part in the reaction as unimolecular, bimolecular and trimolecular reaction.
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H 2 C CH 2
Decomposition
|
|
2C2 H 4
H 2 C CH 2
Example:
Example:
C2 H 4 H 2 O Heat
Dehydration
ethyl alcohol
(v) The reaction may be classified as reversible and irreversible reaction. Reversible reaction are those in
which forward and reverse reaction takes place simultaneously.
C2 H5OH CH3COOH
CH3 COOC2 H5 H 2 O
Irreversible reaction are those which can proceed only in one direction.
C 6 H 6 HNO 3 C 6 H 5 NO 2 H 2 O
(vi) The reaction may be classified as first order, second order and third order reaction.
First order reaction:
1
Decomposition
NO2 + O 2
Example: N 2 O5
2
Second order reaction: (Saponification of ester)
Example:
2 NO H 2 N 2 O H 2 O
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Series Reaction:
Parallel Reaction:
B
A
S
and
A B
C S
Competitive
Side by side
Type
Complicated Reaction:
A B C
C B D
Here reaction proceeds in parallel with respect to B but in series with respect to A, C and D.
Elementary and Non Elementary Reaction:
Consider a single reaction with stoichiometric equation A B C
According to rate law,
Rate of disappearance of A is given by
rA K C A C B
Such reaction in which the rate equation corresponds to a stoichiometric equation are called elementary
reaction.
When there is no direct corresponding rate and stoichiometry, then the reaction is called non-elementary
reaction.
The best example of a non-elementary reaction is that between hydrogen and bromine.
H 2 Br2 2 HBr
rHBr
K [H ][Br2 ] 2
1 2
[HBr]
K2 +
[Br2 ]
a+b+c+d=n
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Where K is rate constant. The rate constant K depends on the temperature. It increasees with temperature. K
is also called specific rate constant.
The units of K depends upon the units of time and concentration.
Suppose :
rA K CAn
mol
CA
lit.
mol
1 n
sec.
mol
K lit. n (sec) 1
lit.
mol
lit.
K (time) 1 (concentration)1 n
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1 dN A
kC A2 ( mol / L hr )
V dt
(b.) k = k
(c.) k = k (RT)2
(d.) k = k/RT
Solution:
dp A
k ' p A2
dt
d
(c A RT ) k ' c A2 ( RT ) 2
dt
dc
RT A k ' c A2 ( RT ) 2
dt
cA
pA
RT
dc A
k ' c A2 ( RT )
dt
rA k ' c A2 ( RT )
kc A2 k ' c A2 ( RT )
k k '( RT )
Option (A) is correct
FORWARD
kA
k A
During the course of a chemical reaction, the rate of a reaction decreases as the reaction proceeds
:::::::::::::::::::::::::SAMPLE PART::::::::::::::::::::::::::::::
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1. In homogeneous system, the possible factors that affect the rate of reaction are temperature, composition
and pressure.
Hence for homogeneous system we can write rate of reaction as a function of concentration and temperature.
mol
l. s
2. According to rate law rate of reaction is directly proportional to the reactant concentration. Rate law is also
called rate equation, kinetic expression.
3. Consider a irreversible reaction
a A b B ....... r R s S ..........
According to rate law we can write
A 2 D 2 2 AD
If the kinetic of reaction shows that reaction is non-elementary then we can postulate a series of elementary
steps.
2 A*
A 2
AD D*
A* D 2
AD
A* D*
[Initiation]
[Propagation]
(Intermediate) * Product
[Termination]
rA* 0
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For such reactions the temperature dependent term, the reaction rate constant has been found in practically all
cases.
(a) Temperature dependency from Arrhenius law:
From Arrhenius law rate constant K is given by:
K Ko e
E
RT
ln
r2
K
E 1
1
ln 2
r1
K1 R T1 T2
t E 1 1
ln 1
t2 R T1 T2
Unit of Ko = unit of K
Ko is not a function of temperature
Ko (also known as frequency factor) does not affect the temperature sensitivity of reaction
K (T2 ) H Rx
Also ln
K T R
1
1 1
T1 T2
Here K(T2) and K (T1) are equilibrium constant at T1 & T2 respectively & HRX is the heat of reaction
Also
d
E
(ln K )
dT
RT 2
(b.) cal/K
(c.) cal
(d.) K
E
cal mol 1
K
R cal mol 1 K 1
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(b.) 12.38Kcal/mol
(c.) 1.2Kcal/mol
(d.) 1238Kcal/mol
Solution:
ln
r2 E 1 1
r1 R T T2
R 1.987cal mol 1 K 1
r2 2r1
2r
E 1
1
ln 1
1
given a straight line with large slope for large E and small slope
T
for small E.
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K T2 e
E
RT
k E 1 1 1 T
ln 2 ln 2
k1 R T1 T2 2 T1
KTe
E
RT
k E 1 1
T
or ln 2 ln 2
k1 R T1 T2
T1
This equation describe the temperature dependency from Transition State Theory.
6. Difference between Collision Theory and Transition State Theory:
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1. Collision theory does not agree more closely with 1. Transition state theory agrees more closely with
experiments.
experiments.
2. Collision theory is based on Kinetic theory of 2. Transition state theory is based on statistical
gases.
mechanics.
3. Collision theory view that decomposition of 3. Transition state theory view that formation of
activated complex is very rapid.
4. Collision theory view that formation of activated 4. Transition state theory view that decomposition
of activated complex is slow and rate controlling.
5. K T 2 e
E
RT
5. K T e
E
RT
SOLVED EXAMPLE
1. The decomposition of N 2 O5 is postulated to occur by the following mechanism.
K1
*
N 2 O5
NO2 NO3
K2
K3
NO*3
NO* O 2
K4
NO* NO*3
2 NO2
K 3 [NO*3 ] K 3
K 4 [NO*3 ] K 4
(i)
(ii)
(iii)
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K1[N 2 O5 ]
K 2 [NO 2 ] 2 K 3
(iv)
dt
K 2 [NO 2 ] 2 K 3
K 2 [NO 2 ]
K1[N 2 O5 ] 1
K 2 [NO 2 ] 2 K 3
2. At 500 K the rate of a bimolecular reaction is ten times the rate at 400 K. Find the activation energy for this
reaction.
(a) From Arrhenius law
ln
r2
E 1
1
r1
R T2 T1
E
r
ln 2
r
R
1
1
1
T T
2
1
r2 10 r1
We have,
T1 400 K
T2 500 K
R = 1.987 cal/mol K
E 1
1
10 r1
ln
1.987 400 500
r
1
E = 9150 cal/mol K
(b) From Collision theory we know that
1
K T2 e
E
RT
r K o T 2 e
ln r
E
RT
1
E1
ln T 2 ln K o
RT
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E 1
2
ln T2 ln K o
R T2
1
ln r2
2
T
1
r2 E 1
ln ln 21
r1 R T1 T2
T2
1
1
T1 = 400 K,
T2 = 500 K
r2 10 r1
1
2
10
r
E
1
1
(500)
1
ln
ln
1
1.987 400 500
r
1
(400) 2
E = 8707 cal/mol
Ans.
3. On doubling the concentration reactant rate of reaction triples. Find the reaction order.
Solution:
Let
rA K CAn
C A2 2C A1
rA 2 K C An 2
we have
rA2 3 ( rA1 )
rA 2
rA1
rA 2
rA1
K C An 2
K C An 1
C An 2
C An 1
n
3( rA1 ) (2C A1 )
rA1
(C A1 ) n
3 2n
ln 3 = n ln 2
n 1.58 1.6
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Solution:
cm3 2 mol
mol
rA 0.005
CA 3 ,
cm cm3 min
mol . min
2
K = 0.005
cm3
mol . min
1 lit
(0.005 cm3 )
1000 cm3
K=
1 h
mol . min
60 min
lit
K = 3 104
mol. h
Value of K = 3 104
lit
Units of K =
mol h
5. The pyrolysis of ethane proceeds with an activation energy of about 75000 cal. How much faster is the
decomposition at 650C than at 500C ?
Solution:
C 2 H 6 P
E = 75000 cal/mol
Let K1 be the rate constant at T1 and K 2 be the rate constant at T2
T1 500 C 773K
T2 650 C 923K
1
K E1
ln 2
K1 R T1 T2
R = 1.987 cal/mol K
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K2
2838
K1
K 2 2838 K1
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