Consequetive or Sequential Reaction: Chemical Kinetics
Consequetive or Sequential Reaction: Chemical Kinetics
Consequetive or Sequential Reaction: Chemical Kinetics
A Typical Example : In many cases, the product formed in one of the elementary
reactions acts as the reactant for some other elementary reaction. One of the examples of
consecutive reactions involves the following steps.
k1 k1
A B C
Let the initial concentration of A be [A]0 and let after time t, the concentrations of A, B and C
be [A], [B] and [C], respectively. It is obvious that
[A]0 = [A] + [B] + [C] ....…(1)
Differential Rate Law : The differential rate expressions are
d[A]
k1[A] ....…(2)
dt
d[B]
k1[A] k1 [B] ....…(3)
dt
d[C]
k1 [B] ....…(4)
dt
On integrating equation (2), we get
[A] [A]0 e k1t ....…(5)
Substituting [A] from equation (5) into equation (3), we get
d[B]
k1[A]0 e k1t k1 [B]
dt
d[B]
k1 [B] k1[A]0 e k1t
dt
Integrated Rate Law : Multiplying the above expression throughout by exp (k1t), we
get
d[B]
k1 [B]e k1 t k1[A]0 e (k1 k1 )t
dt
The left side of the above expression is equal to d([B]e k1 t ) / dt. Hence, the above expression
can written as , d{[B]e k1 t } k1[A]0 e (k1 k1 )t dt
Integrating the above expression with [B] = 0 at t = 0, we get
e (k1 k1 )t 1
[B]ek t k1[A]0
(k1 k1 ) k1 k1
e k1t e k1 t
[B] k1[A]0
(k1 k1 ) k1 k1
k1 k1t k t
[B] k1[A]0 {e e 1 } ....…(6)
k1 k1
Substituting equations (5) and (6) in equation (1), we get
k 1 k1 t k t
[A]0 [A]0 e k1t [A]0 (e e 1 ) [C]
k1 k1
1
or [C] [A]0 1 (k1e k1t k1e k1 t ) ....…(7)
k1 k1
Figure (1) Illustrates the general appearance of the variations of concentrations of A, B and C
CHEMICAL KINETICS 28
[C]
Concentration
[B]
[A]
Time
Fig. 1: Typical variations of concentration of A, B
and C during the progress of the reaction
A ? B ? C. The actual variations on the
values of k1 and k.
In general concentration of A decreases exponentially, the concentration of B initially increases
upto a maximum and then decreases thereafter, and the concentration of C increases steadily
until it reaches its final value [A]0, when all A has changed into C.
Maximum Concentration of B : Equation (6) is
k1 k1t k t
[B] [A]0 {e e 1 } ....…(6)
k1 k1
At the maximum concentration of B, we have
d[B]
0
dt
Hence, differentiating equation (6) with respect to t, we get
d[B] k1 k t k t
[A]0 {k1e 1 k1e 1 } ....…(8)
dt k
1 1 k
Equating equation (8) to zero, we get
k1e k1t max k1e k1 t max 0
k1
or e(k1 k1 )t max
k1
k
or ln 1 (k1 k1 )t max
k1
1 k
or t max ln 1 ....…(9)
k1 k1 k1
substituting equation (9) in equation (6), we get
k1 /(k1 k1 )
k
[B]max [A]0 1 ....…(10)
k1
CHEMICAL KINETICS 29
Catalyst
Berzelius used the term catalyst for the first time for the substances which accelerate the rate
of chemical reaction. Now the term catalyst has been used for the foreign substances which
influence the rate of a reaction and the phenomenon is known as catalysis. Usually two terms
are used for catalysis :
Positive Catalysis : The phenomenon in which presence of catalyst accelerates the
rate of reaction.
Negative catalysis : The phenomenon in which presence of catalyst retards the rate of
reaction. Such substances are also known as inhibitors or negative catalyst.
Characteristics Of Catalyst
(i) A catalyst remains unchanged chemically at the end of reaction, however its physical state
may change. e.g. MnO2 used as catalyst in granular form for the decomposition of KClO3, is
left in powder form at the end of reaction.
(ii) A catalyst never initiate a chemical reaction . It simply influences the rate of reaction.
Exception : combination of H2 and Cl2 takes place only when moisture (catalyst) is present.
(iii) A small quantity of catalyst is sufficient to influence the rate of reaction e.g. 1 g atom of
Platinum is sufficient to catalyse 108 litre of H2O2 decomposition.
(iv) A catalyst does not influence the equilibrium constant of reaction. It simply helps in attaining
equilibrium earlier. It alters the rate of forward & backward reactions equally.
(v) A catalyst normally does not alter the nature of products in a reaction. However some exceptions
are found to this characteristic.
AlCl Cu
(a) HCOOH 3 H2O + CO, HCOOH H2 + CO2
Ni ZnO
(b) CO + 3H2 CH4 + H2O, CO + 2H2 CH3OH
Cr2O3
Cu
CO + H2 HCHO
It may therefore be concluded that in some cases nature of products formed depends upon the
presence and nature of catalyst used.
(vi) A catalyst does not make reaction more exothermic
(vii) Catalyst’s activity is more or less specific : A catalyst for one reaction is not necessary to
catalyse the another reaction.
Type of catalyst
1. Homogeneous catalysis : The reaction in which catalyst and the reactants have same
phase. It includes two types.
(a) Gaseous phase catalysis : When reactants and catalyst are in gaseous phase
e.g. chamber process for H2SO4.
2SO2(g) + O2(g) NO
2SO3(g)
catalyst
(b) Solution phase catalysis : The reactions in which catalyst and reactants are
in solution phase or liquid phase of miscible nature.
H
RCOOR ( l) H 2 O ( l) RCOOH R OH
ester
2. Heterogeneous catalysis : The reactions in which catalyst and reactants form
phase 2.
Reactant : Liquid
(a) Solid-liquid catalysis : Immiscible
Catalyst : Solid
MnO
2H2O2(l) 2(s )
Catalyst
2H2O + O2
CHEMICAL KINETICS 30
Reactant : Liquid
(b) Liquid-Liquid catalysis :: Immiscible
Catalyst : Liquid
Hg( l )
2H2O2(l)
catalyst 2H2O + O2
Reactant : gases
(c) Solid-gas catalysis : Immiscible
Catalyst : solid
Two aspects of solid catalyst are more significant, one is activity and the other is selectivity.
Activity is the ability of catalyst to accelerate chemical reactions; the degree of acceleration
can be as high as 1010 times in certain reactions. Selectivity is the ability of catalyst to direct
reaction to yield particular reaction (excluding others). For example , n-heptane selectivity
gives toluene in presence of Pt catalyst . Similarly ,
CH3 – CH = CH2 + O2 give CH2 = CHCHO selectivity over Bismuth molybdate catalyst .
Arrhenius Theory
In 1889 Arrhenius recognised the temperature dependence of rates or rate constant. He has
given an emperical relation which can be written as
E / RT
k = Ae a ....… (1)
k is the rate constant (of any order other than zero order), A is the pre-exponential factor,
Ea is the activation energy, R is the universal gas constant and T is the absolute temperature.
Activation energy (Ea) is the minimum energy required by a reactant at a certain temperature
to undergo transformation into product . Arrhenius clearly assumed that reactions occur
because of collisions between atoms and molecules of the reactant.
He assumed the activation energy to be the least value of energy which the colliding
molecules must possess for the collision to yield a product. If we plot graph between
activation energy and progress of a reaction (expressed as reaction co-ordinate),we get a
graph as shown in figure .
T.S.
(Ea)f
E (Ea)b
R H
P
Reaction Co-ordinate
The difference between the energies of the reactant and the transition state (TS) is called (Ea)f.
H = (Ea)f – (Ea)b
A , the pre-exponential factor or the frequency factor or the Arrhenius constant is the number
of effective collisions occurring per unit time. Effective collision is the number of collisions
occurring per unit time in which orientation of the colliding molecules is proper. e Ea / RT gives
the fraction of the effective collision that have the sufficient activation energy. Therefore the
product of A and e E a / RT gives the number of collisions per unit time that forms the product
and is called its number of productive collisions which is the rate constant, k.
For all practical calculations , we shall assume that Ea and A are temperature independent.
Both A and Ea are characteristics of the reaction.
CHEMICAL KINETICS 31
Determination of A and Ea
First Method :
Taking log of both sides of equation (1)
Ea
ln k = ln A –
RT
Ea
Converting (natural log) to common log , log k = log A –
2.303 RT
If log k is plotted against 1/T, a straight line is obtained which is shown as below:
Ea
The slope of this line is given by slope =
2.303 R
Thus, knowing the slope, the Ea can be easily calculated. The intercept of the line will give the
value of log A.
Second Method :
The logarithmic form of Arrhenius equation is rearranged as
Ea
ln k = – + ln A
RT
Differentiating with respect to temperature, we get :
log k
1/T
d ln k Ea
=
dT RT 2
Integrating with in the limits of temperature T1 and T2, we get
k2 T2 Ea
k1
d ln k
T1 RT 2
dT
k 2 Ea 1 1
ln
k1 R T1 T2
k2 Ea 1 1
or log k 2.303 R T T ..… (2)
1 1 2
Where k1 and k2 are rate constants at temperatures T1 & T2 respectively. Thus, knowing these
values Ea can be calculated. When the value of Ea is known, the value of A can be calculated by
substituting its value in equation k = Ae E a / RT . In equation (2), the value of R has to be inserted
in the same unit in which Ea is desired.
CHEMICAL KINETICS 32
Temperature Coefficient : “Temperature coefficient of a chemical reaction is defined
as the ratio of rate constants of a reaction at two temperatures differing by 10C”.
k T+10
Temperature coefficient = » 2 to 3
kT
where kT is the rate constant at temperature TK and kT+10 is the rate constant at
temperature (T+10) K. This ratio generally falls between 2 and 3 which means for most of the
chemical reactions, the rate becomes two or three folds for every 10C rise in temperature.
Example 19 :
The rate of a reaction triple when temperature changes from 20ºC to 50ºC.
Calculate energy of activation for the reaction (R = 8.314 JK–1 mol–1).
Solution :
The Arrhenius equation is
k2 Ea T2 T1
log10 =
k1 R 2.303 T1T2
k2
Given = 3 ; R = 8.314 JK–1 mol–1; T1 = 20 + 273 = 293 K
k1
and T2 = 50 + 273 = 323 K
Substituting the given vlues in the Arrhenius equation,.
Ea 323 293
log103 =
8.314 2.303 323 293
2.303 8.314 323 293 0.477
Ea =
30
= 28811.8 J mol –1
= 28.8118 kJ mol–1
Example 20 :
In Arrhenius equation for a certain reaction, the value of A and Ea (activation
energy) are 4 × 1013 sec–1 and 98.6 kJ mol–1 respectively. At what temperature, the
reaction will have specific rate constant 1.1 × 10–3 sec–1 ?
Solution :
According to Arrhenius equation
E / RT
k = Ae a
Ea
or logek = logeA – logee
RT
Ea
2.303 log10k = 2.303 log10A–
RT
CHEMICAL KINETICS 33
98.6 103
or 2.303 log (1.1 × 10–3) = 2.303 log (4×1013)–
8.314 T
98.6 103
T= K = 311 K
8.314 2.303 16.56
Example 21 :
The rate constant is giveny by Arrhenius equation
k = Ae Ea /RT
Calculate the ratio of the catalysed and uncatalysed rate constant at 25ºC if the
nergy of activation of a catalysed reaxction is 162 kJ and for the uncatalysed reaction
the value is 350 kJ.
Solution :
Let kca and kun be the rate constants for catalysed and uncatalysed reactions.
162 103
2.303 log10 kca = 2.303 log10A – ......(i)
RT
350 103
and 2.303 log 10un = 2.303 log10A– ......(ii)
RT
Substracting Eq. (ii) from Eq.(i)
k ca 103
log10 = (350 – 162)
k un 2.303RT
188 103
= = 32.95
2.303 8.314 298
k ca
= 8.88 × 1032
k un
Example 22 :
At 407 K the rate constant of a chemical reaction is 9.5 × 10–5 s–1 and at 420 K, the rate
constant is 1.9 × 10–4s–1. Calculate the frequency factor of the reaction.
Solution :
The Arrhenius equation is,
k2 Ea T2 T1
log10 k =
1 2.303 R T1T2
Given k1 = 9.5 × 10–5 s–1; k2 = 1.9 × 10–3 s–1;
R = 8.314 J mol–1K–1;
T1 = 407 K and T2 = 420 K
Substituting the values in Arrhenius equation.
1.9 104 Ea 420 407
log10 =
9.5 105 2.303 8.314 420 407
Ea = 75782.3 J mol–1
CHEMICAL KINETICS 34
Ea
Applying now log k1 = log A – 2.303 RT
1
75782.3
log 9.5 ×10–5 = log A –
2.303 8.314 407
A 75782.3
or log 5 =
9.5 10 2.303 8.314 407
= 9.7246
A = 5.04 × 105 s–1
Example 23 :
The energy of activation for a reaction is 100 kJ mol–1. Presence of a catalyst lowers
the energy of activation by 75%. What will be effect on rate of reaction at 20ºC, other
things being equal ?
Solution :
The arrhenius equation is
k = Ae E a / RT
k2 75
or 2.303 log =
k1 8.314 103 293
k2 75
or log =
k1 8.314 103 293 2.303
k2
or = 2.34 × 1013
k1
As the things being equal in presence or absence of a catalyst,
k2 rate in presence of catalyst
=
k1 rate in absence of catalyst
r2 k2
i.e., r1 = k1 = 2.34 ×10
13
CHEMICAL KINETICS 35
Pressure Change Method :
Example 24 :
The following rate data was obtained for the first order thermal decomposition
of SO2Cl2(g) at a constant volume .
SO2Cl2(g) SO2(g) + Cl2(g)
Exp. Time (sec–1) Total pressure (atm)
1. 0 0.5
2 100 0.6
Calculate the reaction rate when total pressure is 0.65 atmosphere.
Solution :
Let us say that the pressure of SO2Cl2 decreases by x atm, then the increase of pressure of
SO2 and Cl2 = x atm each. [Q 1 mole of SO2Cl2 decomposes to give 1 mole of SO2 and 1
mole of Cl2].
SO2Cl2(g) SO2(g) + Cl 2(g)
Pressure at t = 0 0.5 atm 0 0
Pressure at t, (0.5 – x) atm x atm x atm
Since total pressure PT = PSO2Cl2 PSO2 PCl2
= (0.5 – x) + x + x
PT = 0.5 + x or x = PT – 0.5
Hence PSO2Cl2 = 0.5 – (PT – 0.5)
= 0.5 – PT + 0.5 = 1.0 – PT
Since , at t = 100 sec, PT = 0.6 atm
PSO2Cl2 = 1.0 – 0.6 =0.4 atm
(a) Evaluation of k
2.303 Initial pressure
k= log
t Pressure at time t
2.303 0.5 2.303 2.303
= log log1.25 = 0.0969 = 2.23 10–3 sec–1
100 0.4 100 100
(b) Rate at PT = 0.65 atm
PSO2Cl2 at total pressure of 0.65 atm = 1.0 – 0.65 = 0.35 atm
CHEMICAL KINETICS 36
Rate = k[N2O5] = 2.23 10 0.35 = 7.8 10 atm sec
–3 –4 –1
Example 25 :
For a homogeneous gaseous phase reaction: 2A 3B + C, the initial pressure of
reactant was P° while pressure at time ‘t’ was P. Find the pressure after time 2t.
Assume I order reaction.
Solution : 2A 3B + C
Initial Pressure P° 0 0
Pressure at t = t P° – 2a 3a a
Pressure at t = 2t P° – 2x 3x x
Given P° – 2a + 3a + a = P ....… (1)
P° + 2a = P
Now for I order reaction at time t
2.303 Po 2.303 Po
K= log log ....… (2)
t P o 2a t 2P o P
Let total pressure at t = 2t be A, then P° – 2x + 3x + x = A or P° + 2x = A
2.303 Po 2.303 Po
K= log o log o ....… (3)
2t P 2x 2t 2P A
1/ 2
2.303 Po
K= log o ....… (4)
t 2P A
By equations (2) and (4)
2
Po Po
o o
2P P 2P A
[2P° – A] . P° = [2P° – P]2
P°. A = 2 (P°)2 – (2P° – P)2
(2Po P)2
A = 2P° – .
Po
Example 26 :
The decomposition of Cl2O7 at 400 K in the gas phase to Cl2 and O2 is of I order.
After 55 sec at 400 K, the pressure of Cl2O7 falls from 0.062 to 0.044 atm. Calculate :
(a) The rate constant.
(b) Pressure of Cl2O7 after 100 sec.
Solution : Cl2O7 Cl2 + 72 O 2
Mole at t = 0 a 0 0
Mole at t = 55 sec. (a – x) x 7x/2
(a) Since Pressure of Cl2O7 is given and therefore,
a 0.062
(a – x) 0.044
2.303 0.062
Q K= log10
t 0.044
K = 6.23 10 sec–1.
–3
d[ A] d[ B]
4. For the reaction 2A + B C + D, – = k[A]2 [B]. The expression for will
dt dt
be:
(A) K[A]2 [B] (B) 1/2K[A]2[B] (C) K[A]2[2B] (D) K[2A]2[B]
dC dn dP
5. Which is correct relation in between , and where C, n, P, represents concentration,
dt dt dt
mole and pressure terms for gaseous phase reactant A(g) product.
dC 1 dn 1 dP dC dn dP
(A) – =– =– (B) = =–
dt V dt RT dt dt dt dt
dC RT dn dP
(C) = =– (D) All
dt V dt dt
6. When ammonia is treated with O2 at elevated temperatures, the rate of disappearance of
ammonia is found to be 3.5 × 10–2 mol dm–3 s–1 during a measured time interval. Calculate the
rate of appearance of nitric oxide and water.
7. The following reaction was carried out at 44ºC
N2O5 2NO2 + ½ O2
The concentration of NO2 is 6.0 × 10–3 M after 10 minutes of the start of the reaction.
Calculate the rate of production of NO2 over the first ten minutes of the reaction.
8. The oxidation of iodide ion by arsenic acid, H3AsO4, is described by the balance equation :
3I– (aq) + H3AsO4 (aq) + 2H+ (aq) I3– (aq) + H3AsO3 (aq) + H2O (l)
(a) If – [I–] / t = 4.8 × 10–4 M/s, what is the value of [I3–] /t during the same time
interval ?
(b) What is the average rate of consumption of H+ during that time interval ?
9. In a reaction, the rate expression is, rate = K[A] [B]2/3 [C]0, the order of reaciton is :
(A) 1 (B) 2 (C) 5/3 (D) Zero
CHEMICAL KINETICS 38
10. For the reaction, H2(g + Br2(g) = 2HBr(g), the reaction rate = K [H2] [Br2]1/2. Which statement
is true about this reaction :
(A) The reaction is of second order (B) Molecularity of the reaction is 3/2
(C) The unit of K is sec –1
(D) Molecularity of the reacion is 2
11. The dimensions of the rate constant of a sceond order reaction involves :
(A) Neither time nor concentration (B) Time and concentration
(C) Time and square of concentration (D) Only time
12. The rate constant for a reaction is 10.8 × 10–5 mol litre–1 sec–1. The rection obeys :
(A) First order (B) Zero order (C) Second order (D) Half order
13. Which statement about the order of reaction is correct ?
(A) The order of reaction must be a positive integer
(B) A second order reaction is also bimolecular
(C) The order of reaction increases with increasing temperature.
(D) The order of reaction can only be determined by experiment
14. The rate of the reaction A + B + C P is given by :
d[ A]
r= = k [A]1/2 [B]1/2 [C]1/4. The order of the reaction is:
dt
The reaction is :
(A) 1 (B) 2 (C) 1/2 (D) 5/4
15. Bromomethane is converted to methanol in an alkaline solution :
CH3Br(aq) + OH– (aq) CH3OH(aq) + Br– (aq)
The reaction is first order in each reactant.
(a) Write the rate law.
(b) How does reaction rate change if the OH– concentration is decreased by factor of 5 ?
(c) What is the change in rate if the concentrations of both reactants are doubled ?
16. The oxidation of Br – by BrO3– in acidic solution is described by the equation
5Br– (aq) + BrO3– (aq) + 6H+ (aq) 3Br2(aq) + 3H2O(l)
The reaction is first order in Br –, first order in BrO3–, and second order in H+.
(a) Write the rate law
(b) What is the overall reaction order ?
(c) How does the reaction rate change if the H+ concentration is tripled ?
(d) What is the change in rate if the concentrations of both Br– and BrO3– are halved ?
17. For the reaction : 2A + B2 + C A2B + BC , the rate law expression has been determined
experimentally to be R = k [A]2 [C] with , k = 3.0 × 10–4 M–2 min–1.
(i) Determine the initial rate of the reaction, started with concentration
[A] = 0.1 M, [B2] =0.35 M & [C] = 0.25 M
(ii) What is the effect on rate of reaction and rate constant on changing the volume to
1/4th of initial value.
18. For the reaction 2NO + Cl2 2 NOCl, it is found that doubling the concentration of both
reactants increases the rate by the factor of 8 , but doubling the Cl2 concentration alone,
only doubles the rate What is the order of the reaction with respect to NO and Cl2 ?
19. For the reaction , 2A + B + C A2B + C
the rate = k[A] [B]2 with k = 2.0 × 10–6 M–2 s–1. Calculate the initial rate of the reaction when
[A] = 0.1 M, [B] = 0.2 M and [C] = 0.8 M.
CHEMICAL KINETICS 39
20. If the pressure of gaseous reactant is changed by 3 times the rate of reaction changes by
5.2 times. Determine
(i) order of reaction (ii) unit of rate constant
(iii) effect on rate of reaction if volume of container is reduced to 1 th of the original
16
8. For the elementary step, (CH3)3.CBr(aq) (CH3)3 C+(aq) + Br¯ (aq) the molecularity is:
(A) Zero (B) 1 (C) 2 (D) cannot ascertained
9. Following mechanism has been proposed for a reaction ,
2 A + B D + E
A + B C + D ........ (slow)
A + C E ...... (fast)
The rate law expression for the reaction is:
(A) r = K[A]2[B] (B) r = K [A] [B] (C) r = K[A]2 (D) r = K[A] [C]
CHEMICAL KINETICS 40
given :
17. Initial rate data at 25ºC are listed in the table for reaction , A2 + B2 2AB
Experiment [A2]0 (m/l) [B2]0 (m/l) Initial rate
No. (m/l/s)
1 1.5 × 10–3 3.2 × 10–4 8.1 × 10–8
2 4.5 × 10–3 9.6 × 10–4 6.56 × 10–6
3 3 × 10–3 1.6 × 10–4 3.24 × 10–7
1. Show that for a first order reaction , R P the concentration of product can be
represented as a function of time by , [P] = at + bt2 + ct3 + ------ and express a , b and c in
terms of [R]0 and K.
2. (i) Substance A decomposes by the first order reaction. Starting initially with
[A] = 2.00 M, after 200 minutes [A] = 0.25 M. For this reaction what is t1/2 and k ?
(ii) A first order reaction is 40 % complete after 8 min. How long will it take before it is
90 % complete ? What is the value of the rate constant ?
CHEMICAL KINETICS 42
(iii) For a certain reaction it takes 20 minutes for the initial concentrations of 34.8 mol L–1 to
become 17.4 mol L–1 and another 20 minutes to become 8.7 mol L–1. Calculate the rate
constant of the reaction.
(iv) For a first order reaction in which k = 5.48 × 10–1 sec–1. Find : (a) t1/3 (b) t2/3
3. Show that for a first order reaction
(i) t25% = 0.415t1/2 (ii) t87.5% = 3t1/2 (iii) t90% = 3.33 t1/2
(iv) t99% = 6.66t1/2 (v) t99.9% = 10t1/2 (vi) t99% = 2t90%
(vii) t99.9% = 3t90%
4. The solution of H2O2 of normality 0.73 is catalytically decomposed. What will be the
concentration at the end of 45 minute, assuming the decomposition to follow first order rate
law if half life is 15 minute ?
5. The change , A B shows I order :
(a) How will the rate of reaction change when the concentration of A is tripled ?
(b) What will be the change in half life period in doing so ?
6. The virus prepared in a chemical bath shows inactivation process obeying I order. Calculate
the rate constant for the viral inactivation if in the beginning 1.5% of the virus is inactivated
per minute. Also calculate the time required for its ,
(a) 50 % inactivation (b) 80 % inactivation.
7. Show that for I order reaction , the time required for 99.9 % decomposition of the reaction
is ten folds to the time required for half of the reaction .
8. The time required for 20 % completion for a reaction is 10 minute for I order reaction.
Calculate :
(a) specific reaction rate. (b) Time required for 75 % completion
9. The half life for a I order reaction A Product, is 10 minute. What % of A remains after
(i) 1/2 hour (ii) 2/3 hour (iii) 1 hour
10. The reaction SO2Cl2 SO2 + Cl2 obeys I order kinetics with rate const. 3.2 × 10–5 sec–1
at 320 ºC . What % of SO2Cl2 will be decomposed on heating gas for 90 minute ?
11. For the first order reaction , A B, shown in the figure, what is the significance of the
point at which the two curves cross each other. How is the slopes of the two curves be
related at this point ?
Concentration
Time
12. A first order gaseous reactions has K = 1.5 × 10–6 sec–1 at 200 ºC . If the reaction is
allowed to run for 10 hour, what percentage of initial concentration would have changed into
products. What is the half life period of reaction ?
13. Thermal decomposition of a compound is of first order. If 50 % sample of the compound is
decomposed in 120 minute, how long will it take for 90 % of the compound to decompose ?
14. A substance is reduced to one third of its original concentration in 100 minute. Calculate the
time in which it will be reduced to one ninth of its original value. Assume I order .
CHEMICAL KINETICS 43
15. For the decomposition of N2O5, the rate constant is 6.2 × 10–4 sec–1 at 45ºC. It begins with
one mole of N2O5 in a litre flask, how long would it take for 20% N2O5 to decompose and
how long for 50 % ?
16. In the decomposition of oxalic acid following data were obtained:
Time in minute 0 300 600
Pressure in mm 22.0 17.0 13.4
Determine the rate constant K and half life period, if reaction obeys I order kinetics.
17. Decomposition of N2O5(g) into NO2(g) and O2(g) is a first order reaction. If the initial
concentration of N2O5(g), i.e., [N2O5]0 is 0.030 mol litre–1, what will be its concentration
after 30 minute? Rate constant of reaction is 1.35 × 10–4 sec–1.
18. For a homogeneous gaseous reaction , A B + C + D, the initial pressure was P0 while
pressure after time t was P. Derive an expression for rate constant K in terms of P0, P and
t. assume I order reaction.
19. Acetone on heating gives CO and other hydrocarbons at 600°C. The reaction obeys I order
kinetics w.r.t. acetone concentration. The half life period is 81 sec. Calculate the time in which
acetone taken in a container at 600 ºC reduces its pressure from 0.5 atm to 0.4 atm.
20. Dimethyl ether gaseous phase decomposition is :
CH3OCH3 CH4 + H2 + CO at 750 K having rate constant 6.72 × 10–3 min–1. Calculate
the time in which initial pressure of 400 mm in closed container becomes 750 mm.
21. The decomposition of Cl2O7 at 400 K in gaseous phase to Cl2 and O2 is of I order reaction.
After 55 sec at 400 K, the pressure of reaction mixture increase from 0.62 to 1.88 atm.
Calculate the rate constant of reaction. Also calculate the pressure of reaction mixture after
100 second.
22. In the vapour phase decomposition of ethylene oxide, C2H4O CH4 + CO at 414.5ºC,
the initial pressure and the pressure after 5 minute were 116.51 mm and 122.56 mm of Hg
respectively. If the reaction follows I order kinetics, what must be the pressure after 12 minutes?
23. Calculate the partial pressures of reactants and products , when azomethane decomposes at
an initial pressure of 200 mm for 30 minute according to (CH3)2 N2 C2H6 + N2. The rete
constant is 2.5 ×10–4 sec–1.
24. Rate constant of a first order reaction A B is 6.93 ×10–2 minute. If initial concentration of
reactant is 1 M . Then calculate :
(i) Initial rate (ii) Rate after 600 seconds
(iii) Rate after 75 % of the reaction is completed
(iv) Rate after 30 minutes.
25. In a first order reaction concentration of reactant decreases from 10 M to 2.5 M in 500
seconds . Calcualte :
(i) t1/2 of the reaction
(ii) rate of reaction when concentration is 5 M.
26. Rate constant of a first order reaction is 10–3 sec. Calculate time in seconds when concentration
is changing from :
(i) 2 M to 0.25 M (ii) 16 M to 1 M
(iii) 6.4 M to 1.6 M (iv) 4 M to 0.125 M
CHEMICAL KINETICS 44
18. (a) 2 and 1 (b) r = K[Cl2]1[NO]2 (c) 8 litre2 mol–2sec–1 (d) 0.256 mol litre–1sec–1
19. 211 torr, 13.57 min 20. Zero order
2.303 2P0
16. 8.6× 10–4 sec; 13.43 minute 17. 0.023 mol/L 18. K = log10 3P P
t 0
19. 26 sec 20. 85.64 21. 1.58 ×10 , 233 atm
–2
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