2

2
2
2
Ea
Galaxy Group of Science
Ea
2Marks:25
2
R
RT -
Subject:12th-Che Date:17/09/18
Chapter:1 2 chemical kinetics Time:01H:00M
2 Ea
RT
2
[A] Answer the following questions : [Each carries 1 mark]
2 [02]
Ea -Ea
\
21. Mention the mathematical
RT RT form of instantaneous rate for the reaction R ® P.
2
22. What isK meant by collision theory ? Explain.
Ea é ù
K followingê ú
[B] Answer the R ë questions
û : [Each carries 2 marks] [06]
-D[R] D[P] -d[R] d[P]
2
Dt
21. Give information Dt of Pseudo firstdt order
dt reaction in brief.
K Ea é ù
ê ú
ë
2. ExplainK: Half lifeR (Half û
reaction time) method to determine order of reaction.

23. Reaction at normal temperature is n1A + n2B = n3C + n4D Write down step of rate of
2 reaction.
2
[C] Answer the following questions : [Each carries 3 marks] [09]
2
21. [R]
2 What is Molecularity ? Explain with example.
2
22. Explain : Threshold Energy.
D[A]
t Dt
23. ExplainK: Endothermic and Exothermic
2 t µ reactions by drawing graphs of potential energy and reaction
2 co-ordinates. D [ B]
2 Dt t
[D] Answer the following questions : [Each carries 4 marks] [08]
2
2
2
21. Describe the D[C] t µ
method to determine
2 [R] instantaneous rate.
2 Dt
2. Write important points of collision theory.
2 D[D] t µ
2 n–1
2 D t
2
2
2
2
2 D[A] D[ B] D[C] D[D]
2
2
2 D t ¾® D t D t Dt
2
2
2
2
2 ¾®
2 –1 d[B]
2 –1 d[A]
2 dt dt
2
2
2 d[A ] ¾®
2 dt
2 d[ B]
2
2 dt ®
2
2
2
2
2
2 -
2
¾®
2
2
2
® ®
2
-
2
2
2 ®
2
2
2
< ___ >
2 ®
2
 Answer Key
Marks:25 Subject:12th-Che Date:17/09/18
Chapter:1 2 chemical kinetics Time:01H:00M

Section [ A ] : 1 Marks Questions

No Ans Chap Sec Que PageNo BookType

RA
1 - Chap 1 (Part 2) C 5 Kumar
2 - Chap 1 (Part 2) C 14 Kumar

ND
Section [ B ] : 2 Marks Questions

No Ans Chap Sec Que PageNo BookType

KE
1 - Chap 1 (Part 2) A 12 Kumar
2 - Chap 1 (Part 2) A 15 Kumar
3 - Chap 1 (Part 2) A 27 Kumar

N
Section [ C ] : 3 Marks Questions
HA
No Ans Chap Sec Que PageNo BookType
1 - Chap 1 (Part 2) A 8 Kumar
AS

2 - Chap 1 (Part 2) A 17 Kumar

3 - Chap 1 (Part 2) A 19 Kumar
AK

Section [ D ] : 4 Marks Questions

No Ans Chap Sec Que PageNo BookType

PR

1 - Chap 1 (Part 2) A 3 Kumar

2 - Chap 1 (Part 2) A 18 Kumar
AR
M
KU

Kumar Prakashan Kendra Welcome To Future M:91-7359 662200

 2
2 Ea Paper Solution
2
2Marks:25 R Subject:12th-Che Date:17/09/18
2Chapter:1
2
Ea 2 chemical kinetics Time:01H:00M
R ®
[A] Answer the following questions : [Each carries 1 mark] [02]
1. Mention the mathematical form of instantaneous rate for the reaction R ® P.
-D[R] D[P] -d[R] d[P]
2 rav = = OR r int = =

RA
Dt Dt dt dt
2. What is meant by collision theory ? Explain.
-D[R] D[P] -d[R] d[P]
22
Dt is depend
Collision Dt on activation
dt energy
dt and collision of molecule in proper direction.

ND
[B] Answer the following questions : [Each carries 2 marks] [06]
2
1. Give information of Pseudo first order reaction in brief.
2 Some reactions are of first order with reference to two different reactants. e.g. the rate of

KE
2
a reaction = K [A] [B].
2 Suppose the concentration of reactant A is less in comparison to concentration of reactant
22 B; Viz. [A] = 0.01 M and [B] = 55.55 M (Molarity of water), then concentration of water

N
during the reaction decreases to 55.55 – 0.01 = 55.54 M, which can be taken almost as
2
2
55.5 M, because 0.01 M can be neglected.
2 t
HA
2 K
Thus, even when the reaction is completed, the concentration of water does not change
2 appreciably.
2
22 t
2 That Kis if it c an be taken as constant then the rate = K 0 [A] can be written where
22 K0 = K[B] will be constant.
AS

22 Now, this reaction will act as first order reaction.

22
22 Such reactions are called Pseudo first order reactions.
AK

22
2 The hydrolysis of methyl acetate in presence of H + gives methanol and ethanoic acid
2
2 respectively.
2
2 CH3 COOCH3 + H2 O CH3 OH + CH3 COOH
2
PR

2
2 In this reaction as seen above, the concentration of water remains almost constant and so
2
this reaction will be considered of first order but this reaction is not really first order
22
reaction, because both the reactants are consumed in this reaction and the exponents of
2
AR

their concentration are 1.

22
2 Hence, this reaction should be 1 + 1 = 2, second order reaction.
2
2
22 But considering cocentration of water as constant, it becomes first order reaction and it is
M

experimentally proved.
2 Such reaction is called Pseudo first order reaction.
KU

2. Explain : Half life (Half reaction time) method to determine order of reaction.
2
2 The half life or half reaction time method is very simple.
2
2 1
2 The time required to have initial concentration [R] 0 to be exactly half. i.e. [R]0 is called
2 2
2 half life period and it can be determined.
22 The order of reaction can be obtained from following relations. [R]
2
2 For zero order reaction t 1 µ [R] 0
2 2
2 For first order reaction t 1 is independent of initial concentration.
2 t 2µ
[R] -
KumarForPrakashan[ R]t Kendra t µ Welcome1 To Future M:91-7359 662200
22 secondt order reaction
t 1
[R]
2 0
22
1
 2 The order of reaction can be obtained from following relations.

2 For zero order reaction t 1 µ [R] 0 // Page:2 //

2
2 For first order reaction t 1 is independent of initial concentration.
2
1
2 For second order reaction t 1 µ
2
[R]0
1
2 Hence, for n th order reaction t 1 µ
2 [R]0n–1

2 Which is Half life method equation.

RA
3. Reaction at normal temperature is n1A + n2B = n3C + n4D Write down step of rate of
reaction.
2 n1 A + n2 B = n3 C + n4 D

ND
D[A]
rav of A = –
Dt
2
D[ B]
rav of B = D – [A]
Dt

KE
Dt
(–) sign indicate decrease in concentration
D[ B]
D[C]
rav of C = Dt
Dt
D[D]

N
rav of D =D[C]
Dt
Dt
HA
Rate of reaction is directly proportional to concentration of reactant.
D[D]
1 D[A] Dt 1 D[ B] 1 D[C] 1 D[D]
– n = –n = n = n
1 Dt 2 Dt 3 D t 4 Dt
2 Law of Velocity : “Rate of reaction is shown by form of concentration of reactant is called
AS

D[A] D[ B] D[C] D[D]

law of velocity.” Dt
Dt Dt Dt
2 –1 d[A] –1 d[B]
= – = K[A]x [B]y
AK

n1 dt n 2 dt
d[A ]
–1 d[A]= Rate –1 of reaction
d[B] when concentration [A] of A.
dt
dt dt
2 d[A d[ B]
PR

= Rate of reaction when [B] is concentration of B.

dt]
dt
2 K = Rate of reaction constant.
d[ B]
[C] Answer
dt the following questions : [Each carries 3 marks] [09]
AR

1. What is Molecularity ? Explain with example.

2 The second important term in addition to order of reaction is the molecularity.

® ®
M

2 It can be defined for an elementary reaction.

22 There is no meaning of molecularity for complex reaction.
22 The definition ® of molecurity for an elementary ® reaction can be given as below :
KU

22 “The number of atoms, ions or molecules of the reactant that take part in the reaction and
2 ®
2 which experience collision with each other, so that the reaction results, it is called
2 molecularity of the reaction.”
22 If one molecule ® is®associated in the reaction it is called monomolecular (unimolecular)
reaction.
22 K a [H ] [Br
e.g. Decomposition of ]ammonium nitrite
+ K b® [HBr / Br2 ]
NH4 NO 2 ¾® N 2 + 2H 2 O
22 In bimolecular
K [Hreaction
] [Br ] two molecules have collision with each other. e.g. decomposition
¾® a iodide.
2 of + K b [HBr / Br2 ]
hydrogen
2 2HI ¾® H 2 + I 2
Kumar
2 In Prakashan
termolecular Kendra [Br2 ]
Welcome
reaction three molecules To Future
collide with one another M:91-7359
e.g. reaction 662200
of nitric
2 ¾®
oxide with dioxygen
2 2NO + O2 ¾® 2NO 2
2 If one molecule is associated in the reaction it is called monomolecular (unimolecular)
2 reaction.
// Page:3 //
2 e.g. Decomposition of ammonium nitrite
NH4 NO 2 ¾® N 2 + 2H 2 O
2 Ea
2 In bimolecular reaction two molecules have collision with each other. e.g. decomposition
RT
of hydrogen iodide.
2HI ¾® H 2 + I 2Ea Ea
2 In termolecular RT reaction
RT three molecules collide with one another e.g. reaction of nitric
oxide with dioxygen
EaE -Ea
\
2NO + O2 ¾® RT 2NO a
RT2 RT
2 The possibility of collision of three or more molecules with one another and to result in
Ea
the reaction is less. -Ea

RA
\ K é ù
2 E
The molecularity RT
a ê more RTthan three is not seen.
K ú
2 R ë of reactions
Hence, the orders û and molecularities of bimolecular, trimolecular elementary
é
K areEa same.
reaction ù
ê é úû formù HI.

ND
2 H2 and K KI combine
R ëEa and
2 ê ú
H2 + I 2K¾® 2HI R ë û
2 In this,
K one Emolecule é of ù hydrogen and one molecule of iodine is used and so its
2
is 1R + êë 1 = 2. úû
a
molecularity
K

KE
2 i.e., it is a bimolecular reaction.
22 Looking to the order of the reaction, the exponents of H 2 and I 2 are 1 and 1.
2 Hence, the order of reaction will be 1 + 1 = 2. Thus, the order of reaction and molecularity
are same i.e. 2.

N
2 For monomolecular reaction, the order of reaction will be one at high pressure or
concentration but at lower pressure or concentration the order will be 2.
HA
2. Explain : Threshold Energy.
2 If the value of R is taken in K cal or K joule then the value of Ea will be also in K cal or
AS

K joule.
22 From the value of intercept, the value of log A will be obtained and constant A can be
determind.
AK

22 Arrhenius equation shows that rate constant increases expontially with temperature.
2 It is also noted in addition to this, that by increasing temperature from 300 to 310 K, the
2 kinetic energy increases only by 3% because it is proportional to temperature.
PR

22 In addition to this, for most of the reactions the rates have almost doubled be increase in
temperature by 10 K.
22 The explanation for this can be given that must be some pushing energy or threshold
energy required for the reaction of molecules in the fig. (a) this is shown.
AR

22 The graph of the fraction of the molecules which experience collision possessing different
kinetic energy is plotted.
M
KU

Fig. (a)
2 It is apparent from this, that the average relative kinetic energy increases as expected but
KumarthePrakashan
number of Kendra
molecules. (fig.Welcome To shown
(a) portion Future shaded) whichM:91-7359 662200
possesses threshold
relative kinetic energy.
2 It shows increases of E*. Thus, the activation energy E and such kinetic energy (E*) can be
 // Page:4 //
2 Fig. (a)
2 It is apparent from this, that the average relative kinetic energy increases as expected but
the number of molecules.- (fig. (a) portion shown shaded) which possesses threshold
relative kinetic energy.
2 It shows increases of E*. Thus, the activation energy E a and such kinetic energy (E*) can be
22 shown by following relation :
Ea = NA · E* where, N A = Avogadro number
2
-

RA
Intercept = ln A

2 –Ea
slope =
R

ND
2

KE
1
T

N
[Fig. (b) Plot between log K and 1/T] HA
2 In Arrhanius equation the parameter A is called pre-exponential factor or frequency factor.
2 Ea is called energy of activation.
2 Both of these factors are known as Arrhenius factors.
1
AS

2 To determine their values a graph of log K versus is plotted and from the values of the
T
slope, Ea can be determined.

3. Explain : Endothermic and Exothermic reactions by drawing graphs of potential energy and reaction
AK

co-ordinates.
2 When molecules come nearer to each other, the changes in energy that take place can be
studied.
PR

2 When the molecules come nearer to each other, the distance between them is decreasing and
their potential energy increases.
2 Such molecules combine with each other and a short lived complex molecule is produced.
22 It possesses maximum potential energy. This short lived molecule is known as activated
AR

complex.
22 This activated complex possesses very weak bonds.
2 They break due to their oscillation motion. Hence, product or original reactant is obtained.
M

22 As the molecules of resultant product go away from each other, their potential energy
2 decreases.
KU

2 There can be two options for this :

2 (1) If the minimum potential energy of reactants is less than that of product then the
2 reaction will be endothermic.
2 (2) If the minimum potential energy of reactants is more than potential energy of product
then the reaction will be exothermic.
22 Thus, in endothermic reaction, the potential energy of products is more than potential
energy of reactants.

2Kumar Prakashan Kendra Welcome To Future M:91-7359 662200

 // Page:5 //
2 Hence, Hp – Hr = DH will have positive value. In exothermic reactopm the potential energy
of product is less than the total potential energy of reaction. Hence the value of
Hp – Hr = DH will be negative which can be shown by fig. (a) and fig. (b).

Potential energy

RA
Potential energy

ND
KE
Reaction co-ordinate Reaction co-ordinate
Fig. (a) Endothermic reaction Fig. (b) Exothermic reaction

N
2 The energy of activation is the difference between potential energy of reactant molecules
and activated complex.
HA
2 In the above figure if the activation energy of reverse reaction is E'a and activation energy
of forward reaction is Ea then DH = Ea – E'a
2 Now, if E a > E' a the value of DH obtained will be positive and so the reaction will be
AS

endothermic.
2 If E a < E' a then the value of DH obtained will be negative and the reaction will be
exothermic.
AK

[D] Answer the following questions : [Each carries 4 marks] [08]

1. Describe the method to determine instantaneous rate.

PR

2 The progress of chemical reaction is studied as a function of measuring concentration of

reactants or prod ucts and fo r gaseo us react ions measuring pressure instead o f
2 concentration.
2 i.e. at some definite intervals of time the concentration of any one of the reactants or
AR

products can be measured.

22 It can be assumed from the study of general reactions, the proportion (volume) of reactant
or product is taken then there is not much change in the total proportion or the
M

2 concentration remains almost same or remains constant.

2 For this volume of reactant is taken. During the progress of the reaction it is noted that with
KU

increase in time the concentration of reactents will decrease and the concentrations of
2 products will increase.
2 Hence, the concentration of reactant or product is determined with suitable method of
measurement at definite intervals of time.
22 Suppose, in a reaction one mole of reactant (R) produces one mole of product (P).
2 In the initial concentration of R and P, the decrease and increase remain same respectively.
22 Only the magnitude will change. If the graph of concentration versus time is plotted then,
2 the graph obtained will be as shown in fig. 1.
2
Product (P)
centration

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Reactant (R)
2 In the initial concentration of R and P, the decrease and increase remain same respectively.
2 Only the magnitude will change. If the graph of concentration versus time is plotted then,
// Page:6 //
the graph obtained will be as shown in fig. 1.

Product (P)
Concentration

Reactant (R)

Time
2 Fig. 1 : Change in concentration of reactant and product with time.

RA
2 Suppose, at time t1 , the concentrations of reactant and product are [R]1 and [P]1 respectively
and at any other time t2 , their concentrations are [R]2 and [P]2 respectively, then Dt = t2 – t1
a n d
D[R] = [R] 2 – [R]1 and D[P] = [P] 2 – [P]1 , where D[P] and D[R] are the changes in concentration

ND
of product and reactant respectively.
2 The average rate of reaction rav can be expressed as follows :
D[R] D[P]

KE
rav = – = + ...(1)
Dt Dt
2 There is decrease in concentration of reactant and so it is expressed with negative (–) sign
and there is increase in concentration of product and so it possesses positive (+) sign which
is generally not mentioned.

N
2 The negative sign is only for mathematical significance.
2 It is apparent from the equation (1) that the unit of average rate is concentration time–1, viz
HA
molar second–1, molar minute–1, molar day–1 , molar year–1 .
2 To determine the speed of any vehicle, average speed is considered because there is
increase and decrease in the speed of the vehicle.
AS

2 Hence, the values determined at any definite time will be different viz.
2 If there is disturbance of traffic then it will be slow and the speed will decrease, but if the
road is without traffic, the vehicle will go faster.
AK

2 This is difficult to determine.

2 Hence, all these are integrated and the average is determined and we use it in practice.
PR

inst
+ slope
Concentration of products
Concentration of reactant

AR
M

inst – slope
KU

Time Time

2 It is clear from the fig. (a) that the rate of reaction decreases rapidly in the beginning and
becomes less with the increase in time.
2 The instantaneous rate (r inst) changes with the change in instantaneous speed so the
instantaneous rate (r inst) is changing.
2 The instantantaneous rate (rinst) at any instant of time (t) has definite value.
2 The instantaneous rate can be expressed mathematically as follows :
Kumar Prakashan Kendra Welcome To Future M:91-7359 662200
D[R] D[P]
rav = – =
Dt Dt
 2 It is clear from the fig. (a) that the//
rate of reaction
Page:7 // decreases rapidly in the beginning and
becomes less with the increase in time.
2 The instantaneous rate (r inst) changes with the change in instantaneous speed so the
instantaneous rate (r inst) is changing.
2 The instantantaneous rate (rinst) at any instant of time (t) has definite value.
2 The instantaneous rate can be expressed mathematically as follows :
D[R] D[P]
rav = – =
Dt Dt
OR
d[R]

RA
d[P]
rinst = – = ...(2)
dt dt

(when Dt ® 0)

ND
2 To determine intantantaneous rate, at any time (t) in the graph, showing concentration of

reactant versus time a tangent [fig. (a) and (b)] is drawn.

KE
2 The slope of the tangent of the curve is equal to the instantaneous rate at that time.

d[R]
\ rinst = – slope (for R) = –
dt

N
d[P]
rinst = + slope (for P) =
dt
HA
2. Write important points of collision theory.

2 The theory of collilsion for chemical reaction was developed by Max Trauz and William
Lewis in 1916-1918.
AS

22 This principle deals with the energetic and mechanistic matter of the reaction.
2 It is based on the kinetic energy of gases.
22
AK

According to this theory, it is supposed that the molecules are hard spheres and the
2 reaction occurs only when these molecules collide with each other.
22 In chemical reaction, the number of collision per second per unit volume is called collision
frequency (Z).
PR

2
2 Suppose any bimolecular reaction is as follows :
A + B ® Product
2
2 The rate of reaction can be shown as below :
AR

®
E
2 - a RT
Rate = Z AB e ...(1)
2 Where, Z AB -is the collision frequency of reactants, A and B whose energy is equal to or
M

more than activation energy.

2
KU

E
- a RT
2 This equation when compared with Arrhenius equation K = A e it can be said that
Arrhenius constant A is related to collision frequency Z AB . -
2
2 The values of rate constant of reactions having atomic species or simple molecules can be
determined accurately using equation (1).
2
2 But there is notable deviation for complex molecules.
2 The reason for this is that all the collisions, do not result into products.
2
2 Those collisions in which molecules collide with sufficient kinetic energy (which is called
2
threshold energy) and proper direction, then bonds of the reactants break and new bonds
2 are formed resulting into products.
Kumar Prakashan Kendra Welcome To Future M:91-7359 662200
2 Such collisions are called effective or fruitful collisions.
2 If we take as an example the preparation of methanol from bromomethane the molecules
2 But there is notable deviation for complex molecules.
2
// Page:8 //
The reason for this is that all the collisions, do not result into products.
2 Those collisions in which molecules collide with sufficient kinetic energy (which is called
threshold energy) and proper direction, then bonds of the reactants break and new bonds
are formed resulting into products.
2 Such collisions are called effective or fruitful collisions.
2 If we take as an example the preparation of methanol from bromomethane the molecules
are oriented as shown below.
2 The reactant molecules having proper orientation lead to bond formation, where as

RA
improper direction makes them collide but do not result into product.
CH3 Br + OH– ® CH3 OH + Br–

Proper

ND
Product obtained

KE
Product is not obtained

2 For effective collision, another parameter is added which is called steric factor or

N
probability factor which takes into consideration the collision from proper direction.
Ea
Hence, Rate = PZ AB e - ...(2)
RT
HA
where, P = probability factor
2 Thus, according to the collision theory, the combinations of activation energy and
collision of morecules from proper direction are required for effective collision.
AS

2 Hence, the following points can be concluded :

(1) The collisions between the reactants is essential.
(2) There must be certain minimum energy (threshold energy) for the reactant
AK

experiencing collision.
(3) The collision of the reactant molecules should be in proper direction (orientations).
(4) The reactant experiencing fruitful collision are converted to products.
PR
AR
M
KU

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2
2