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NOTRE DAME
Chemical Kinetics
Definitions and laws:
1.
2.
3.
4.
5.
6.
7.
8.
9.
Rate of reaction and its units, average rate and instantaneous rate
Rate law or Rate expression
Rate constant definition and its units
Order of the reaction and molecularity of reaction
Half life
Elementary step in reaction and RDS step
Pseudo first order reaction
Activation energy
Factors effecting rate of reaction
Express the rate of the following reaction in terms of disappearance of hydrogen in the
reaction. 3H2(g)+N2(g)2NH3(g)
ii) The decomposition of NH3 on platinum surface is a zero order reaction. What are the rates of
production of N2 and H2 if k=2.510-4 mol L-1 s-1?
2. Rate law
i)
For the reaction, AB, the rate of reaction becomes twenty seven times when the
concentration of A is increased three times. What is the order of the reaction?
ii)
A reaction is of second order with respect to a reactant. Now is its rate affected if the
concentration of the reactant is (i) doubled (ii) reduced to half?
CHEMISTRY-XII
NOTRE DAME
iii)
A reaction is of first order in reactant A and of second order in reactant B. How is the rate of this
reaction affected when (i) the concentration of B as alone is increased to three times (ii) the
concentrations of A as well as B are doubled?
(i)
(ii)
(iii)
Initial [NO]
(M)
0.15
0.15
0.30
0.25
Initial [Cl2]
(m)
0.15
0.30
0.15
0.25
vi) Consider the reaction, 2A+B C+D. Following result were obtained in experiments designed
to study the rate of reaction.
Exp. No.
1.
2.
3.
Initial concentration
(mol L-1)
[D] (M/min)
0.10
0.20
0.40
0.10
0.20
0.40
1.510-3
3.010-3
6.010-3
(i)
(ii)
(iii)
CHEMISTRY-XII
NOTRE DAME
2A+BC+D
Exp.No
[A]
[B]
Initial rate of formation of D
1.
0.1 M
0.1 M
6.010-3M min-1
2.
0.3 M
0.2 M
7.210-3M min-1
3.
0.3 M
0.4 M
2.8810-2M min-1
4.
0.4 M
0.1 M
2.4010-2M min-1
Determine rate law and the rate constant for the reaction.
viii) The data given below is for the reaction,
S.No
N2O5(mol L-1)
1.
1.1310-2
2.
0.8410-2
3.
0.6210-2
Determine for this reaction,
(i)
Order of reaction
(ii)
Rate law
(iii)
Rate constant
2N2O5(g)4NO2(g)+O2(g)
Rate of disappearance of N2O5 (mol L-1 min-1)
3410-5
2510-5
1810-5
3. Order
i)
The reaction, A+3BC obeys the rate equation, rate=k*A+1/2[B]3/2. What is the order of reaction?
ii) For a reaction A+B P, the rate law is given by, r=k[A]1/2[B]2. What is the order of this reaction?
iii) Identify the reaction order from the following rate constant, k=2.310-5 L mol-1s-1.
iv) Identify giving reasons, the reaction order from each of the following rate constants:
(i)
k=2.310-5 L mol-1s-1
4. Rate constant for zero order reaction, Half life and relation between x and t.
i)
The rate constant for a zero order reaction in A is 0.0030 mol L-1 s-1. How long will it take for the
initial concentration of A to fall from 0.10 M to 0.075 M?
i)
CHEMISTRY-XII
NOTRE DAME
iii) The decomposition of a compound is found to follow a first order rate law. If it takes 15 min for
20% of original material to react, calculate
(i) Rate constant
(ii) The time at which 10% of the original material remains unreacted.
iv) Nitrogen pentoxide decomposes according to the equation. 2N2O5 (g) 4NO2 (g) +O2 (g). This
first order reaction was allowed to proceed at 400C and the data below were collected.
v) [N2O5] [M]
vi) Time(min)
vii) 0.400
viii) 0.00
ix) 0.289
x) 20.0
xi) 0.209
xii) 40.0
xiii) 0.151
xiv) 60.0
xv) 0.109
xvi) 80.0
CHEMISTRY-XII
NOTRE DAME
A first order decomposition reaction takes 40 min for 30% decomposition. Calculate its t1/2 value
-1
ii) Calculate the half life of a first order reaction whose rate constant is 200 s
4
iii) The half life for a first order reaction is 510 s. What percentage of the initial reactant will
react in 2 hours? Calculate.
iv) The half life for decay of radioactive 14C is 5730 yr. An archaeological artifact containing wood
had only 80% of the 14C found in a living tree. Estimate the age of the sample.
v)
Prove that the time required for the completion of of the first order is twice the time required
for the completion of half of the reaction
vi) The decomposition of phosphine, PH3 proceeds according to the following equation.
4PH3(g)P4(g)+6H2(g).
It is found that the reaction follows the following rate equation.
Rate=k[PH3]
The half life of PH3 is 37.9 s at 1200C.
(i) How much time is required for th of PH3 to decompose?
(ii) What fraction of the original sample of PH3 remains behind after 1 min?
vii) A first order reaction is 20% complete in 5 min. Calculate the time taken for the reaction to be
60% complete.
-1
viii) The rate constant for a first order reaction is 60 s . How much time it will take to reduce the
concentration of the reactant to 1/10th of its initial value?
ix) Hydrogen peroxide, H2O2(aq) decomposes to H2O(l) and O2(g) in a reaction that is of first order
in H2O2 and has a rate constant, k=1.0610-3 min-1.
(i)
(ii)
i)
In a pseudo first order hydrolysis of ester in water, the following results are obtained:
T(in seconds) 0
30
60
90
[Ester] M
0.55
0.31
0.17
0.85
(i) Calculate the average rate of reaction between the time interval 30 to 60 s.
(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester.
8. Arrhenius equation, relation between k1 and k2 and Graph log k vs 1/T
CHEMISTRY-XII
NOTRE DAME
i)
The first order rate constant for the decomposition of ethyl iodide by the reaction,
C2H5I(g)C2H4(g)+HI(g) at 600 K is 1.6010-5 s-1. Its energy of activation is 209 kJ/mol. Calculate
the rate constant of the reaction at 700 K.
ii) The rate of reaction becomes four times when the temperature changes from 300 K to 320 K.
Calculate the energy of activation of the reaction, assuming that it does not change with
temperature. (Given, R=8.314 J mol-1 K-1)
iii) For a decompositon reaction the value of rate constant k at two different temperatures are
given below:
k1=2.1510-8 L mol-1 s-1 at 650 K
k2=2.3910-7 L mol-1 s-1 at 700 K
Calculate the value of activation eneryg for this reaction. [R=8.314 J mol -1 K-1]
0
0
iv) The rate of a particualr reaction triples when temperature change from 50 C to 100 C. Calculate
the activation energy of the reaction. (Given, log 3=0.4771; R=8.314 J K-1 mol-1)
v) Rate constant k of a reaction varies with temperature T according to the equation.
log k log A
Ea 1
2.303R T
1
, a straight line with a
T
vii)