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1.
The branch of physical chemistry which deals with the rate at which the chemical reactions occur, the mechanism by which the
chemical reactions take place and the influence of various factors such as concentration, temperature, pressure, catayst, etc. on the
reaction rats, is called the chemical kinetics.
On the basis of rates, the chemical reactions are broadly divided into three categories.
1.1 Very fast or instantaneous reactions: These reactions take about
impossible to determine the rates of these reactions. Some such examples are:
1.2 Very slow reactions: It is also difficult to study the kinetics of such reactions as their competion takes days, months or years.
Some examples are:
i) Reaction between hydrogen and oxygen at room temperature
2 H 2 O2 2 H 2 O+O 2
2 N 2 O5 2 N 2 O4 + O2
Rate=
The rate measured over a long time interval is called average rate and the rate measured for an infinitesimally small time interval is
called instantaneous rate. For a reaction,
n1 A +n2 B m1 C+
1 d [ A ] 1 d [B ] 1 d [C] 1 d [D ]
=
=
=
m2 D , the instantaneous rate may be expressed as r inst =
n1 dt
n2 dt
m1 dt
m 2 dt
Here negative sign shows that concentration of reactant decreases with the time.
2.1 Experimental determination of instantaneous rate of reaction: A curve is plotted betweeen concentration and time. A tangent is
drawn to the curve at the point corresponding to time interval t. The slopw of this tangent gives the instantaneous rate of reaction.
Instantaneous rate of reaction = Slope of curve =
Sinc the concentrations of the reactants keep on decreasing with time, the rate of reaction correspondingly decreases with time.
w/ M n
=
V
V
Where w = mass of substance in grams and M is the molecular mass in grams, n is the number of moles and V is the volume in
litres.
RATE CONSTANT
A B.
dx
dx
C A =kC A
dt
dt
Where k is a proportionally constant, called velocity constant or rate constant or specific reaction rate.
At a fixed temperature, if
Rate=
C A =1, then
dx
=k
dt
(i)
aA+ bB product
a
A [b]
dx
Rate=
dt
( )
Rate=K [ A ]a [ B]b
When
.(ii)
[ A ] =[ B ] =1 mol/litre , then
Rate=k
2 Hl H 2 +l 2
(Unimolecular)
(Bimolecular)
2 SO 2 +O2 2 SO 3
(Trimolecular)
NO+O2 NO 2+O 2
2CO 2 +O2 2CO 2
(Bimolecular)
(Trimolecular)
(Trimolecular)
The minimum number of reacting particles (molecules, atoms or ions) that come together or collide in rate determining step to form
product or products is called the molecularity of a reaction.
1
H 2 O 2 H 2 O+ O2
2
Step 1: H 2 O2 H 2 O+[O]
(Overall reaction)
(Slow)
Step 2: [ O ] +[O]O2
(Fast)
The slowest step is rate-determining step. Thus from step 1, reaction appears to be unimolecuar important
Important
i) Molecularity is a theoretical concept.
ii) Molecularity cannot be zero, ve, fractional, infinite and imaginary
iii) Molecularity normally not be greater than three because more than three molecules rarely collide with each other.
3.3 Rate Law or Rate Equation: The determination of the rate la expression of a complex reactions is not an easy task. Its
determination requires,
i) Information about the number of moles of reactants consumed during the reaction.
ii) A knowledge of the intermediates produced during the reaction and ho much they accumulate during the early period of reaction.
iii) The rate data to be supplemented by different techniques so that the certain elementary steps are verified to the maximum.
In complex reactions thus the rate expression written on the basis of the overa balanced equation has no significance at all. It merely
represents a theoretical expression. The true rate expression for such complex reactions can be evaluated on the basis of the
experimental data ony. For example, in the reaction between NO2 and F2 to yield nitrosyl fluoride (NO2F), i.e.
2 NO 2 ( g )+ F 2 ( g ) 2 NO 2 F ( g)
the rate expression on the basis of law of Mass Action is
NO 2
F
[ 2 ]
rate=k
Experimentally, it has been observed that the rate of this reaction is proportional to the product of single concentration term of NO 2
and F2. Thus, exprimental rate of the reaction or the actua rate of reaction is given as
NO
F
[ 2].
[ 2]
rate=k
A mathematical expression that gives the true rate of a reaction in terms of concentration of the reactants, which actually infuence the
rate, is cale Rate Law.
3.4 Rate Controlling Step: As pointed out that the complex reaction proceeds through more than one steps. Let us now understand that
which of these steps can be used to write the rate expression. Out of various steps of the reaction the slowest step will decide the rate
of overall reaction because the reaction cannot take place faster than the slowest step. Thus, the sowest step of the complex reaction is
caed the Rate Controlling Step or Rate Determining Step. A few examples given below will illustrate the above point (s) more easily:
Reactions Involving Slow Steps
Therma decomposition of nitrous oxide
2 N 2 O 2 N 2+ O 2
On the basis of experimental data it is observed that the rate of this reaction depends on the single power of concentration of
N 2 O slow step N 2 +O
Thus, the rate law expession for the reaction can be written as
Rat=k [ N 2 O ]
The above postulated mechanism is consistent with the rate law expression.
3.5 Order of a reaction: Thus, the order of reaction is defined as the sum of the powers to which the concentration terms are raised in
the rate law expression. The power of the concentration of a particular reactant in the rate law is called the order of the reaction with
respect to that reactant.
Thus, if the rate of reaction
Rat=
dx
q
r
p
=K [ A ] [ B ] [ C ]
dt
1
N 2 O5 ( g ) 2 NO2 ( g )+ O2 ( g)
2
Rate=k [ N 2 O 5]
Order = 1
ii) Reaction of second order
Decomposition of nitrogen peroxide
2 NO 2 2 NO +O 2
NO 2 2
Rate=k
Order=2
2 NO +O2 2 NO 2
2
Rate=k [ NO ] [ O 2 ]
Order=3
iv) Reaction of Fractional order
Decomposition of acetaldehyde is a fractional order reaction
CH 3 CHO CH 4 +CO
CH
CHO
3
Rate=k
3
Order= 1.5
2
v) Zero-order reaction
A number of zero order reactions are known in which the rate of the reaction is independent of the concentration of the reactants.
For example,
The rate decomposition of ammonia at the surface of metals like gold, platinum etc,, is zero order reaction.
2 NH 3 Platinum N 2+ 3 H 2
It has been observed that the rate of the reaction is independent of the concentration of ammonia.
0
NH 3 Rat =k
dx
i. e . Rate=
=k
dt
order = 0
3.6 Pseudo-order reactions: Reactions whose actual order is different from that expected using rate law expression is called pseudoorder reactions,
i) Hydrolysis of esters
'
'
RCOOR + H 2 O RCOOH + R OH
C
follow first order kinetics: Rate=k [ 12 H 22 O 11 ]
3.7
MOLECULARITY
1. It is the total number of reacting species (molecules, atoms or
ions) which bring the chemical change.
2. It is always a whole number.
3. It is a theoretical concept.
4. It is meaningful only for simple reactions or individual steps of
a complex reaction. It is meaningless for overall complex
reaction.
ORDER OF REACTION
1. It is the sum of powers of molar concentration of the reacting
species in the rate law equation of the reaction.
2. It may be a whole number, zero, fractional, positive or negative
3. It is determined experimentally.
4. It is meant for the reaction and not for its individual steps.
mol/litre
n1
litre
sec =
mol
1
n1
]
[ ]
1
unit of concentration
time1
n1
sec 1
Order of reaction
Zero order
Units
1
mol L time
1st order
time1
2nd order
mol1 Ltime 1
3rd order
mol2 L2 time 1
nth order
mol2 L2 time 1
nth order
L mol
dx
o
=k [ A ] =k
dt
Some photochemical reactions and a few heterogeneous reactions are zero-order reactions.
Examples:
i) Photchemical reaction between hydrogen and chlorine:
This photochemical reaction is zero-order reaction. The reaction is studied by placing H2 and Cl2 gases over water.
ii) Decomposition of N2O on hot platinum surface :
N 2 O N 2+1 /2 O2
N2
0
Rate [ N 2 O ] =k [ ]o =k
Or
N
d [ 2 O]
=k
dt
2 NH 3 [ Mo ] N 2 +3 H 2
[ A ] t= [ A ]0 kt
ii) The time required for the reaction to complete, i.e., time at which
iii) The units of k are
[A]
is zero.
t completion=
[ A ]0 Initial concentration
k
mol L1 time 1
Rate constant
dx
=k (ax)
dt
Or
dx
=kdt
(ax)
dx
(ax) =k dt
log e ( ax )=kt +c
Or
a
=kt
(ax )
2.303
a
log 10
t
( ax )
The following two important conclusion are drawn from this equation:
i) A change in concentration unit will not change the numerical value of k.
So ,k =
k=
2.303
na
log 10
t
n (ax)
2.303
a
log 10
t
( ax )
ii) The time taken for the completion of same fraction of change is independent of initial concentration.
x=0.5 at=t t / 2
So,
Or
k=
2.303
log 10
t 1 /2
t 1 /2 =
a
2.303
0.693
=
log 10 2=
0.5 a
t 1 /2
t 1 /2
0.693
k
This time t in which the initial concentration becomes hal is termed as hal life period. Half life period of a first order reaction is
independent of the initial concentration of the reactant.
When the log of the concentration of the reactant at various intervals of time is plotted against the time intervals, a straight line is
obtained.
4.2.1 Examples of first order reactions
ii)
2 NO 2 2 NO +O 2
ii)
k=
2.303
a
1
1
1
log 10
, for first order reactions ; k =
, for second order reaction ;
t
t
(ax )
(ax) a
k=
1
1
1
2 , for third order reactions .
2
2 t (ax) a
ii) Graphical method: A graphical method basd on the respective rate laws can also be used. If the plot of log (ax) versus t is a
straight line, the reaction follows first order. If the plot of
1
(ax)
the
1
plot of (ax)2
1
for a reaction of nth order, a graph o (ax)n1
The reactants first combine to form an intrmediate X which is in equilibrium with the reactants (as rate constants k 1 and k2 are quite
large). The intermediate X then decomposes slowly to form the products so that equilibrium concentration of X remains almost
undisturbed. The rate of reaction is given by the rat of decomposition of the intermediate. Thus we have
Eqm . const , K =
k
[X]
, K= 1
k2
[ A] [ B ]
Rate of reaction=k 3 [ X ] =k 3 K [ A ][ B ] =
k 3k 1
[ A ] [ B ] =k 0 [ A ] [ B ]
k2
Thus, the reaction is of second order and the rate expression involves all the constants.
6. PARALLEL REACTIONS
When a single reactant gives two or more than two products with different rate constants is known as parallel reaction. This type o
reaction generally occurs in organic chemistry.
Let us consider reactant A breaks into two products B and C with rat constants K1 min1. Let a, b th initial concntration o A, x and y be
the concentration of B and C respectively after time t.
at time t = 0
at time t = t
i) Considering,
a
a (x+y)
A B
Rate of disappearance of A = rate of appearance of B
Or
d [ A]1 d [B ]
=
=K 1 [ A ]
dt
dt
ii) Considering,
A C
d [ A ] II d [C]
=
=K 2 [ A ]
dt
dt
K
( 1+ K 2)[ A ]
Net rate of disapparance of
d [ A ]
A=
=K 1 [ A ] + K 2 [ A ] =
dt
Or
K
( 1+ K 2) [ A]
d [ A ]
=
dt
at time t = 0
a( x + y + z)
at time t = t
then we can write as,
K=
2.303
a
log
, K=K 1 + K 2 + K 3
t
a( x + y + z )
Let us consider a reaction when there are two successive stages of the first order i.e, A decomposes to B, which further decomposes to
C.
A k1 B k 2C
Rate of disappearanc A ,
Rate of disappearance of B,
d[A]
d [ B]
K 1 [ A ] =rate o formation of B=
dt
dt
d [ B]
d [C]
=K 2 [ B ]=rate o ormationof C=
dt
dt
.(i)
.(ii)
d (B)
=K 1 [ A ] K 2 [ B ]
dt
Rate=
dx
= collision frequency x fraction of effective collisions = z x f
dt
Simiarly in a heterogeneous system collision is not so effective as in homogeneous system. Thus, reactions in liquid phase or solution
phase will be faster in comparison to heterogeneus conditions when same concentration of the reactants are taken.
ii) Physical size of the reactants : Among the solids, rate increases with decrease in particle size. In powdered state rate of reaction is
maximum because in powdered state, surface area is maximum.
iii) Chemical nature of reactants : Consider the following two reactions:
.(i)
.(ii)
The first reaction is faster than the second because in the first reaction only
A + B C+ D , Rate=k [ A ] [B ]
Rate of the above reaction decreases with the
Passage of time because the reactants A and B
Will decreases as time passes on
Let us consider the following reversible reaction
A + B C+ D
k f [ A ] [ B]
k b [ C ] [ D]
Q10=Temperature coefficient=
k t+ 10
kt
9. ARRHENIUS EQUATION
(frequency factor),
At two temperatures
Ea =energy of activation
T 1 and T 2 , taking log of Arrhenius
Equation, we get
And
log e k 1=log e A
Ea
RT 1
.(i)
log e k 2=log e A
Ea
RT 2
.(ii)
Subtracting Eg. (ii) from Eq. (i) and converting the og to the base 10, we get
[
[
]
]
log10
k1
E a T 2T 1
=
k 2 2.303 R T 1 T 2
log 10
k2
Ea
T 2T 1
=
k 1 2.303 R T 1 T 2
log 10 k=log 10 A
Ea
1
y=m x +c
2.303 R T
[]
T , then k= Ae =A .
i) Presence of a positive catalyst: The function of a positive catalyst is to lower down the activation energy. The greater the decrease in
the activation energy caused by the catalyst, higher will be the reaction rate. In the presence of a catalyst, th reaction follows a path of
lower activation energy. Under this condition, a large number of reacting molecules are able to cross over the energy barrier and thus
the rate of reaction increases.
ii) Presence of negative catalyst: A negative catalyst increases the activation energy of reaction by forming a new intermediate of high
energy, i.e., by changing the reaction mechanism.
Due to increases activation energy, some acitve molecules become inactive, therefore, rate of reaction decreases.
10. PHOTOSENSITIZER
It is substance which when added to a reaction mixture helps to initiate the photochemical reaction without undergoing any chamical
change itself. This phenomenon is known as photosensitization e.g., chlorophyll acts as photosensitizer in the photosynthesis.
Hg+ hv Hg
Different photochemical reactions have different values of quantum efficiency depending upon their mechanisms. For example,
photosynthesis of HBr has low value of
11. FAST REACTIONS The reaction which take place in just a fraction of a second to complete are called fast reactions. The kinetics
10
10
10
of fast reactions are expressed in milli seconds ( 3 s ), micro seconds (6 s) , nano seconds (9 s) and pico
10
seconds (12 s) . The rates of fast reactions can be studied by spectrophotometric techniques based on light absorption and
emission i.e., change in the intensity of the colour of the reaction mixture. Some other techniques based on laser, magnetic properties
and electrical conductances are also being used.
EXAMPLES
EXAMPLE:1 The following data are for the reaction
A + B products
Conc. Of A (M)
Conc. of B (M)
0.1
0.2
0.5
0.5
0.1
0.2
0.1
0.5
mol L
1
(
1 s )
Initial Rate
4.0 104
1.6 103
1.0 102
1.0 102
EXAMPLE:4 A substance reacts according to first order kinetics and rate constant for the reaction is
2 1
1 10 s . If its
initial
concentration is 1 M,
A. What is initial rate?
B. What is rate after 1 minute?
EXAMPLE:5 A first order reaction takes 69.3 minutes for 50% completion. How much time will be needed for 80% completion?
EXAMPLE:6 In order to study the kinetics of the reaction
A solution
initially 0.12 in ethylene oxide and 0.007574 M in perchoric acid was prepared and the progress of the reaction was followed
diatometricaly. The following data were obtained at 200C.
T(min.)
30
60
135
300
Dilatometer
18.48
18.05
17.62
16.71
15.22
12.29
Determine the order of the reaction with respect to ethylene oxide and evaluate the specific rate constant.
EXAMPLE:7 The rate constant for the first order decomposition of a certain reaction is given by the equation
1.25 10
(1)=14.34
T
k
Calculate
A. the energy of activation,
B. the rate constant at 500 K.
C. at what temperature will its half life period be 256 minutes?
EXAMPLE:8 Compounds A and B react to form C and D in a reaction that was found to be second-order overall and secondorder in A. The rate constant at 300C is 0.622 L mol1 min1. What is the haf-life of A when
4.10 10
M. of A is mixed
with excess B?
EXAMPLE:9 The rate constant for the decomposition of a certain substanc is
1 1
1.38 10 M s
R=8.314 10
0
1 1
50
C
at
. Evaluate the Arrhenius parameters of the reaction ( 3 kJ mol k )
EXAMPLE:10 The rate constant for the first order decomposition of ethylene oxide into CH 4 and CO may be described by
log 10 k ( s1 )=14.34
1.25 10 K
T
sec1
Caculate the reactin ate as well as rate of change of concentration of A, B and D.
EXAMPLE:12 The reaction;
litre
in 5 seconds. Calculate (a) rate of appearance of NO2, (b) rate of reaction and (c) rate of disappearance of N2O5.
EXAMPLE:13 For ;
(excess)
A. rate expression
B. units of rate and rate constant
C. effect on rate if concentration A is doubled and of B is tripled.
NH
d [ 3]
,
then write the rate expression in terms of concentration of
dt
NH 3 is
O2 . NO and H O
2
EXAMPLE:15 The specific rate constant for the decomposition of formic acid is
specific ratae constant at 458 K if the energy of activation is
2.37 10 4 calmol1
EXAMPLE:16 Derive the order of reaction for decomposition of H2O2 from the following data.
Time in minutes 10
Volume of
15
O2 given by H 2 O2
15
20
6.30
8.95
25
11.40
13.5
13.75
EXAMPLE:17 In a pseudo first order hydrolysis of ester in water the following results were obtaining t/s
t/s
0
30
60
90
[Ester]M
0.55
0.31
0.17
0.085
i) Calculate the average rate of reaction between the time interval 30 to 60 seconds
ii) Calculate the pseudo first order rate constant for the hydrolysis of ester.
EXAMPLE:18 A substance undergoes first order decomposition. The decomposition follows two paralel first order reactions as:
The percentage distribution of B an C are:
A. 80% B and 20% C
B. 20% B and 80% C
C. 76.83% B and 23.17% C
D. 23.27% B and 76.83% C
RT
E a /
EXAMPLE 19 For reaction A B , the rate constant k = A e and for the reaction P Q , the rate constant
1
1
1
k 2= A 2 eEa / RT
2
If
8
10
A 1=10 , A2=10 Ea =600, Ea =1200, then the temperature at which k 1=k 2 is
1
A. 600 K
C.
600
K
4.606
B.
300 4.606 K
D.
4.606
K
6 00
A.
C.
1 k
2 a2
2k
a
a2
B. 2 k
D.
a
2k
EXAMPL:21 The rate constants for two parallel reactions were found to be
C. 100.0 KJ mol1
EXAMPLE:22
D. 65.0 KJ mol1
2 N 2 O5 4 NO2 +O2
The above reaction is first order and takes 24 min for 75% decomposition of N 2O5. At the end of one hour after the start of the
reaction, the amount of oxide left is
A. nil
C.
B.
D.
EXAMPLE:23 A certain reaction proceeds in a sequence of three elementary steps with the rate constant K 1, K2 and K3. If the
1 /2
[ ]
K1
reaction is
A.
C.
[ ]
[ ]
1 E1
+E3
2 E2
E
E3 1
E2
B.
1 /2
D.
E3 +
E 3+ E 1
E2
1
[ E +E ]
2 1 2
EXAMPLE:24. the reaction between NO and Br2 takes place into two steps
NO+Br 2
i.
NOBr 2+ NO K 3 2 NOBr
ii)
if
K 1 > K 2 > K 3 , then the rate law of the overal eaction, 2 NO + Br2 2 NOBr can be given by
Br
A.
2
r=K [ NO ]
C.
B.
r=k [ NO ] [Br 2 ]
Br 2 2
D. r= [ NO ]
EXAMPLE:25. Reaction A follows first order kinetics and reaction B follows second order kinetics. It their half lives are equal,
the ratio of their reaction rates at the start of reaction is
A.
R1 K1
R2 K2
C.
R1 2 K1
=
R2 K2 a
B.
D.
R1 K1
=
R2 K2 a
R2 K1
=
R1 K2 a
1
T
EXAMPLE:28. A radioactive substance decays 20% in 10 minutes. If at the start there are
20
5 10
N 2 O 4(g ) 2 NO 2 (g ) .
C.
12 10 atmmin
B.
D.
1
N 2 O5 , N 2 O5 N 2 O 4 + O2 , are 3.46 1054.87 103 at 25 0 C and 650 C respectively.
2
B.
D.
EXAMPLE:31 In a reaction between A and B, the initial rate of reaction was measured for different initial concentrations of A
and B as given below:
A/M
0.20
0.20
0.40
B/M
0.30
0.10
0.05
r 0 / Ms1
5.07 10
5.07 10
7.6 10
B.
C.
D.
EXAMPLE:32 How much faster woud a raction proceed at 250C than at 0oC if the activation energy is 65 kJ:
A. 2 times
B. 16 times
C. 11 times
D. 6 times.
III. MULTIPLE CHOICE QUESTIONS (with more than one correct choice)
EXAMPLE:33 Arrhenius equation may be represented as
A.
A Ea
=
K RT
Ea
log
A=log
k
+
C.
2.303 RT
B.
dk Ea
=
dT
RT
( )
Ea
k
log
=
D.
RT
A
1e
(kt)
A. the degree of dissociation is equal to
t 75 =3 t 1 /2
D. The pre-exponential factor in Arrhenius equation has the dimension of time T1.
E
( a/ RT 2 )
B.
(d / dt ) K=+
E/ RT
(d
/dt)
K=( 2)
A.
C.
(d /dt )K=( E/ RT )
D.
K= AeE / RT
a
A +2 B C is3
H 2 ( g ) + I 2 ( g ) 2 Hl ;
d [ H 2]
=K b [ Hl]2 for backward reaction and
dt
d [ H2]
=K f [ H 2 ] [ I 2 ]
dt
[ H 2 ]=0 for H 2+ I 2 2 Hl
M Product
N Product
A.
B.
K
2O3 3 O 2 ; therate=
K [reactant]
B. B
D. D
B n
dX
=k [ A]m
dt
Reason (R): The rate of the reaction does not depend upon the concentration of C.
A. A
B. B
C. C
D. D
EXAMPLE:47 Assertion (A): According to steady state hyothesis, in a multistep reaction, the change in concentration with time for
reactive intermediates is zero
Reason (R): The intermediates are so reactive that after a brief initia period thir concentrations rise rom zero to a small value and
remains constant for most of the duration of the reaction.
A. A
B. B
C. C
D. D
EXAMPLE:48 Assertion (A): For each ten degree rise of temperature the speciic rate constant is nearly doubled.
Reason (R): Energy-wise distribution of molecules in a gas is an experiment function of temperature.
A. A
B. B
C. C
D. D
V. COLUMN MATCHING
EXAMPLE:49 Match the following
Column I
Column II
Reactions
Experimental Methods
A.
2 N 2 O5 ( g ) 4 NO 2 ( g ) +O2 ( g)
+
H
B.
CH 3 COO H 2 H 5 ( aq ) + H 2 O
CH 3 COOH ( aq ) +C 2 H 5 OH (aq)
C.
C6 H 5 N =NCl ( aq ) C 6 H 5 Cl ( l ) + N 2 ( g)
alkali
+
H
D.
C12 H 22 O11 ( aq ) + H 2 O
C6 H 12 O6 ( aq ) +C 6 H 12 O6 ( aq)
Glucose
fructose
EXAMPLE:50
and T
C0 = initial concentration of reactant; C = Concentration of reactant at any time t; k = rate constant Match
the following:
Column I
A. C Vs t (abscissa) for zero order
B. log C Vs t (abscissa) for first order
C.
Column II
P. Unity
Q. Zero
D. In
R. k
S. k/2.303
TRUE/FALSE
EXAMPLE:51. The rate constant of most of the ionic reactions do not increase with increase in temperature
EXAMPLE:52. The rate of endothermic reaction increases with increasing temperature
EXAMPLE:53. The reaction has rate
1/ 3
K [ A ] [B ]
. It is an elementary process.
0.001 kg hr 1 . The rate of conversion of H2 under these conditions is..kg hr1. The rate of conversion of H2 under
these conditions is..kg hr1
EXAMPLE:63. The rate of reaction is.when the activation energy is small.