DAY TWENTY TWO

Chemical
Kinetics
Learning & Revision for the Day
u Rate of a Reaction u Integrated Rate Equations u Arrhenius Equation
u Molecularity and Half-life u Activation Energy
u Order of Reaction u Zero Order Reaction u Collision Theory
u First Order Reaction

The feasibility of a reaction can be predicted with the help of thermodynamic principle but it
does not deal with the rate at which chemical reaction occurs. The branch of chemistry which
deals with the study of rate of reactions, factor affecting the rate of reaction and mechanism of
the reaction is known as chemical kinetics.

Rate of a Reaction
The rate (or speed or velocity) of a reaction is the rate of change of concentration of reactants
or products in unit time.
A → B
It can be defined in two ways:
∆[ A] ∆[B]
(i) Average rate of reaction, can be represented as rav = – =+
∆t ∆t
The units of rate of a reaction are mol L−1 s −1 or mol L−1 min −1 .
(ii) Instantaneous rate of reaction (rinst ) can be calculated from rav in the limit ∆t → 0 and
represented as
d[ A] d[B]
rinst = – =
dt dt
In general for a reaction, aA + bB → cC + dD
1 d[ A ] 1 d[B] 1 d[C] 1 d[D]
Rate = – =– =+ =+
a dt b dt c dt d dt
NOTE The negative sign in the rate of a reaction, indicates that the concentration of reactants decreases
(disappearance of reactants) with time, while the positive sign indicates that the concentration of
products increases (formation of products) with time.
Factors Affecting the Rate of a Reaction l In case of simple reactions, known as elementary
reactions, the molecularity is simply the sum of
The factors which affect the rate of reaction are as follows: molecules of different reactants as represented by
(i) Concentration of reactants An increase in concentration balanced equation,
of reactants, brings more frequent collisions between the e.g.
reacting molecules. That increases the rate of reaction.
(i) Unimolecular reaction N2O 4 (g) → 2NO2 (g)
(ii) Nature of reactants The nature of bonds in a molecule
(ii) Bimolecular reaction 2HI(g) → H2 (g) + I2 (g)
influences the rate of reaction at which it changes into
products. (iii) Trimolecular reaction 2NO(g) + O2 (g) → 2NO2 (g)
(iii) Temperature Reaction rates are normally favoured by l In case of complex reactions, i.e. the reactions involving
increase of temperature. Increase in temperature causes a more than one step, the rate determining step is slowest
greater fraction of the molecules to have an energy at least step. The atoms, molecules or ions participating in this
equal to the threshold energy. step decide the molecularity,
(iv) Presence of catalyst Presence of catalyst increases the e.g. HBrO3 + 6HI → HBr + 3H2O + 3I2
rate of reaction by lowering the energy barrier. This reaction takes place through following steps:
(v) Surface area of reactants The rate of reaction increases as Slow
the surface area of the reactants increases. HBrO3 + HI → HBrO2 + HIO (Rate determining step)
(vi) Presence of light Reaction rate normally becomes faster in Fast
HBrO2 + 4HI → HBr + 2H2O + 2I2
presence of light.
Fast
HIO + HI → H2O + I2
Rate Law and Specific Rate Constant Hence, two molecules participate in slowest step, the
l According to law of mass action, the rate of a chemical reaction is of bimolecular type.
reaction is directly proportional to the product of
effective concentrations of reacting species, each raised to Order of Reaction
a suitable power, may or may not be equal to the It is defined as the sum of the coefficients (or powers) of the
respective stoichiometric coefficients. reacting species that are involved in the rate law expression
For a general reaction, for the reaction. For the reaction, aA + bB → cC + dD
aA + bB → Products; Rate = k [ A]a[B]b dx
Rate law (rate equation) is given as : = k [ A]α [B] β
− d [R] dt
= k [ A]a [B]b Overall order of reaction = α + β
dt
The above equation is called differential rate equation It can only be determined by experiments. It may be whole
and k is rate constant or velocity constant or specific number, fraction, zero or negative.
reaction rate.
l The above expression is called rate law as it describes the Integrated Rate Equations
functional dependence of the reaction rate upon
concentration of various reactants. Rate law cannot be
and Half-life
deduced from balanced equation. It is obtained l The differential rate equation is integrated to get a
experimentally. reaction between directly measured experimental data, i.e.
concentrations at different time and rate constant. The
l Unit of k in terms of concentration, Rate = k [ A]x
obtained equation are known as integrated rate equation.
mol
Unit of concentration = l Half-life time period is the time required to reduce the
Ls concentration of the reactant to half of its initial value.
x
 mol The integrated rate equations and half life period are
∴ Rate = k  
 Ls  different for the reactions of different orders. These are
given below for zero and first order reactions.
∴ Unit of k = (mol)1 − x ⋅ Lx − 1 −1
s
where, x = order of reaction
Zero Order Reaction
In these reactions, in which the concentration of
Molecularity l

reactants do not change with time and the concentration

l It is defined as the number of ions or molecules or atoms rates remain constant throughout.
taking part in an elementary process of the reaction
[Ct ] – [C0 ]
mechanism. It is always a whole number and can never k =–
be zero, negative or fractional. t
 where, C0 = initial concentration of the reactant Comparative Study of Zero and First Order Reactions
Ct = concentration of the reactant at any time t
Rate law Expression for Half-life
l Half-life period for these reaction is equal to, Reaction Order
equation rate constant period
C0 [ A0] − [ A]
, t 1 /2 ∝ C0
t 1 /2 = A → product 0 Rate = k k= t1 / 2 =
[ A0 ]
2k t 2k
where, k = rate constant, t 1 /2 = half-life period. A 
A → product 1 Rate = k [A] k=
2.303
log  0  t1 / 2 =
0.693
l Units of rate constant and rate of reaction are same, i.e. t  A k
mol L−1 s −1 .
2A → product 2 Rate = k[ A]2 1 1 1 t1 / 2 ∝
1
k=  − 
t  A A0  [ A0 ]
First Order Reaction
l In these are reactions, the reaction rate is determined by
the change of one concentration term of the reactant only, Effect of Temperature on
k=
2 . 303
log
a Rate of Reactions
t (a – x) l It has been found that for a chemical reaction with rise
where, t = time, a = initial concentration in temperature by 10°, the rate constant is nearly get
k = rate constant, doubled.
(a–x) = concentration of a after time ‘t’ l The effect of temperature is usually expressed in terms of
l Half-life period of these reactions is, temperature coefficient which is defined as the ratio of
0.693 two rate constants differing by a temperature of 10 K.
t 1 /2 = , t 1 /2 = half-life period l The value of temperature coefficient for most of the
k
reactions lies between 2 to 3.
l Rate equation for first order gas phase reactions
K + 10
2 . 303 p0 Temperature coefficient (n) = t =2
k = log Kt
t p0 − pt
where, p0 = initial pressure Arrhenius Equation
pt = pressure after time t .
kA kB Arrhenius equation is purely an empirical equation that gives
In a sequence of reactions, A   → B  → C. a reasonably good representation of temperature dependence
[B] is maximum when, of the rate constant.
2 . 303 k  When log k is plotted against 1 / T, we get a straight line which
t = log10  A  is represented by Arrhenius equation as
(k A − k B )  kB 
k = Ae − E a / RT
NOTE For reaction, 2A → B
ln k = ln A − E a/ RT
Rate = k [ A]2 , i.e. the reaction follows second order rate Ea
kinetics and the half-life of second order is equals to, log k = log A −
1 2 . 303 RT
tl / 2 =
k[ A o] The intercept of this line is equal to log A and slope is equal to
Sometimes, the rate of reaction decreases as the Ea
l
− . Therefore, E a = −2.303 R × Slope
concentration of one of the constituent is increased. 2.303 R
These reaction are called negative order reactions. e.g.
transformation of ozone into oxygen, –5.0
2O3 → 3O2 –6.0 –Ea
–7.0 Slope =
1 d [O ]2
Rate = − [O3 ] = K 3 = K [O3 ]2 [O2 ]−1 log k –8.0 2.303 R
2 dt [O2 ]
–9.0 Ea = – 2.303 × R × Slope
l When one of the reactants is present in large excess, the –10.0
second order reaction confirms to the first order and is –11.0
called pseudo unimolecular reaction. –12.0
e.g. Hydrolysis of ester in acidic medium –13.0
H + /H O 1.3 1.4 1.5 1.6
CH3COOC2 H5  
2
→ CH3COOH + C2 H5OH
1/T
This is also known as pseudo first order reaction.
A plot between log k and 1/T
Rate = k [Ester]
 Ea
Activation Energy ln k2 = ln A −
RT2
…(ii)
l It is the minimum additional energy required by the
molecule to attain threshold energy. Subtracting the Eq. (i) from Eq. (ii), we get
E  E  E E
l It is constant for a particular reaction. ln k2 − ln k1 = − a −  − a  = a − a
RT2  RT1  RT1 RT2
l It does not depend on temperature, volume, pressure etc.,
but gets affected by the presence of catalyst. k2 E a  1 1  E a T2 − T1 
ln =  − =  
l Catalyst increases the rate of reaction by providing k1 R T1 T2  R  T1T2 
alternative path of lower activation energy to the
k2 E a  T2 − T1 
reactants. log =   [Here, T2 > T1 ]
k1 2 . 303 R  T1T2 
A → B; ∆H < 0, i.e. exothermic reaction
This relation is used when rate constants at two different
Reaction
path with temperatures are given.
Reaction path
catalyst d log k E
without catalyst = a2
Potential energy

Energy of l This reaction is also written as

activation dT RT
Reactants Energy of without
activation
with catalyst catalyst
Collision Theory
Products According to collision theory, the reactant molecule are
assumed to be hard spheres and reaction is postulated to
occur when molecules collide with each other.
Reaction coordinate
l The collisions among the reacting species which results
Effect of catalyst on activation energy
in the products are known as the effective collisions.
l Enzyme catalysed reaction are faster than the metal l The species taking part in the chemical reaction must
catalysed reaction because they have lower activation have a certain minimum energy known as threshold
energy. Threshold energy is independent of temperature, energy (E ° ).
but E a shows temperature dependence. l Threshold energy = activation energy (E a)
+ average energy of molecules.
Calculation of Activation Energy l If we assume that the rate of reaction is equal to rate of
collisions per unit volume or per unit time multiplied by
l Activation energy can be calculated by knowing the rate fraction of collisions then the rate constant is given by the
constants at two different temperatures, assuming that E a expression.
and A remains constant.
k = Z ABe − E a / RT
l Taking log both the sides in Arrhenius equation, we get
E where, Z AB = collision frequency factor of reactants A and B
ln k = ln A − a l When steric factor is considered the rate of reaction is
RT
Now, if the values of rate constant at temperatures T1 and given as:
T2 are k1 and k2 respectively then Rate = PZ ABe − E a / RT
E where, P is probability or steric factor.
ln k1 = ln A − a …(i)
RT1
DAY TWENTY TWO CHMICAL KINETICS 233

DAY PRACTICE SESSION 1

FOUNDATION QUESTIONS EXERCISE

1 For the reaction, 2A + B → Products; the active mass 7 Given, the hypothetical reaction mechanism
of B is kept constant, and that of A is doubled. The rate I II III
A → B → C → D → E and the rate as
IV

of reaction will be
Species formed Rate of its formation
(a) decrease 4 times
B 0.002 mol/h per mole of A
(b) decrease 2 times
(c) increase 4 times C 0.030 mol/h per mole of B
(d) increase 2 times D 0.011 mol/h per mole of C
2 In a reaction A + B → product, rate is doubled when E 0.420 mol/h per mole of D
the concentration of B is doubled, and rate increases by The rate determining step is
a factor of 8 when the concentrations of both the (a) step I (b) step II (c) step III (d) step IV
reactants (A and B) are doubled. Rate law for the
8 For the reaction, H 2 (g ) + Br2 (g ) → 2HBr(g )
reaction can be written as ª CBSE-AIPMT 2012
the experimental data suggest, rate = k [H 2 ] [Br2 ]1/ 2
(a) Rate = k[A] [B]2 The molecularity and order of the reaction respectively are
(b) Rate = k[A]2 [B]2 1
(a) 1, (b) 1, 1
(c) Rate = k[A] [B] 2
3 3 3
(d) Rate = k[A]2 [B] (c) , (d) 2 ,
2 2 2
3 For the reaction, N 2 + 3H 2 q 2NH 3 the rate of
9 What is the order of a reaction which has following rate
change of concentration for hydrogen is 0.3 × 10 −4 Ms −1.
expression? rate = k[ A]3/ 2 [B]−1
The rate of change of concentration of ammonia is 3 1
(a) −0.2 × 10−4 (b) 0.2 × 10−4 (a) (b) (c) 0 (d) None of these
2 2
(c) 0.1 × 10−4 (d) 0.3 × 10−4
10 Mechanism of a hypothetical reaction X 2 + Y2 → 2XY
4 For the reaction, N2 + 3H2 → 2NH3, if
is given below
d [NH3 ] − d [H2 ]
= 2 × 10−4 mol L−1s −1, the value of (i) X 2 q X + X (fast) (ii) X + Y 2 → XY + Y (slow)
dt dt
would be ª CBSE AIPMT 2009 (iii) X + Y → XY (fast)
(a) 3 × 10−4 mol L−1 s −1 (b) 4 × 10−4 mol L−1 s −1 The overall order of the reaction will be ª NEET 2017
(c) 6 × 10−4 mol L−1 s −1 (d) 1 × 10−4 mol L−1 s −1 (a) 1 (b) 2 (c) 0 (d) 1.5

5 For the reaction, A + B → products, it is observed that 11 Which one of the following statements for the order of a
reaction is incorrect? ª CBSE-AIPMT 2011
I. On doubling the initial concentration of A only, the
rate of reaction is also doubled. (a) Order is not influenced by stoichiometric coefficient of
the reactants
II. On doubling the initial concentrations of both A
(b) Order of reaction is sum of power to the concentration
and B, there is a change by a factor of 8 in the rate
terms of reactants to express the rate of reaction
of the reaction.
(c) Order of reaction is always whole number
The rate of this reaction is, given by ª CBSE AIPMT 2009 (d) Order can be determined only experimentally
(a) rate =k[A]2 [B]
(b) rate =k[A][B]2
12 For a reaction between A and B, the initial rate of reaction
(c) rate = k[A]2 [B]2 is measured for various initial concentrations of A and B.
(d) rate = k[A][B] The data provided are
6 The rate law for the chemical reaction [A] [B] Initial reaction rate
2NO 2Cl → 2NO 2 + Cl 2 is (1) 0.20 M 0.30 M 5 × 10 −5
rate = k [NO 2Cl]. The rate determining step is (2) 0.20 M 0.10 M 5 × 10 −5
(a) 2NO 2Cl → 2NO 2 + 2Cl (3) 0.40 M 0.05 M 1 × 10 −4
(b) NO 2 +Cl 2 → NO 2Cl + Cl
The overall order of the reaction is
(c) NO 2Cl +Cl → NO 2 + Cl 2 (a) one (b) two
(d) 2NO 2Cl → 2NO 2 + Cl 2 (c) two and half (d) three
13 If a certain reaction is first order with respect to A, 22 After how many seconds will the concentration of the
second order with respect to B and zero order with reactant in a first order reaction be halved, if the rate
respect to C then what is the order of reaction? constant is 1.155 × 10 −3 s −1?
(a) First (b) Second (c) Third (d) Zero (a) 600 (b) 100 (c) 60 (d) 10
23 The concentration of reactant X decreases from 0.1 M to
14 When initial concentration of a reactant is doubled in a
0.005 M in 40 min. If the reaction follows first order
reaction, its half-life period is not affected. The order of
kinetics, the rate of reaction when concentration of X is
the reaction is ª CBSE-AIPMT 2014 0.01 M will be
(a) zero (b) first (a) 1.73 × 10−4 M min −1 (b ) 3.47 × 10−4 M min −1
(c) second (c) 3.47 × 10−5 M min −1 (d) 7.50 × 10−4 M min −1
(d) more than zero but less than first
24 The rate of first order reaction is
15 When initial concentration of the reactant is doubled, the
1.5 × 10 −2 mol L−1 min −1 at 0.5 M concentration of the
half-life period of a zero order reaction ª NEET 2018
reactant. The half-life of the reaction is
(a) is tripled (b) is doubled
(a) 0.383 min (b) 23.1 min (c) 8.73 min (d) 7.53 min
(c) is halved (d) remains unchanged
25 The rate constant of a zero order reaction is
16 For a reaction a A → x P , when [ A] = 2.2 mM, the rate 0.2 mol dm −3 h −1. If the concentration of the reactant after
was found to be 2.4 m Ms −1. 30 min is 0.05 mol dm −3. Then, its initial concentration
On reducing concentration of A to half, the rate changes would be
to 0.6 m Ms −1. The order of reaction with respect to A is (a) 0.01 mol dm − 3 (b) 0.15 mol dm − 3
(a) 1.5 (b) 2.0 (c) 2.5 (d) 3.0 (c) 0.25 mol dm − 3 (d) 4 .00 mol dm − 3

17 In the reaction, 2N 2O 5 → 4NO 2 + O 2 , 26 The half-life period for zero order reaction
A → Product; is 100 min. How long will it take in 80%
initial pressure is 500 atm and rate constant k is
completion?
3.38 × 10−5s −1. After 10 min, the final pressure of N 2O 5 is
(a) 80 min (b) 160 min
(a) 490 atm (b) 250 atm (c) 480 atm (d) 420 atm (c) 100 min (d) 200 min
18 Sucrose decomposes in acid solution into glucose and 27 The value of rate constant of a pseudo first order reaction
fructose according to the first order rate law, with (a) depends on the concentration of reactants present in
t1/ 2 = 3. 00 h. What fraction of sample of sucrose remains small amount
after 8 h? (b) depends on the concentration of reactants present in
(a) 1.023 M (b) 0.8725 M excess
(c) 0.023 M (d) 0.1576 M (c) is independent of the concentration of reactants
19 Half-life period of a first order reaction is 1386s. The (d)depends only on temperature
specific rate constant of the reaction is ª CBSE-AIPMT 2009 28 Which of the following statements is in accordance with
−3 −1 −2 −1 collision theory?
(a) 5.0 × 10 s (b) 0.5 × 10 s
(c) 0.5 × 10−3 s −1 (d) 5.0 × 10−3 s −1 (i) Rate is directly proportional to collision frequency.
20 The correct difference between first and second- order (ii) Rate depends upon orientation of atoms.
reactions is that ª NEET 2018 (iii) Temperature determines the rate.
(a) Only (iii) (b) (i) and (ii) (c) (ii) and (iii) (d) All of these
(a) a first-order reaction can be catalysed; a second-order
reaction cannot be catalysed 29 When we increase temperature, the rate of reaction
(b) the half-life of a first-order reaction does not depend on increase because of
[A]0 ; the half-life of a second-order reaction does (a) more number of collisions
depend on [A]0 (b) decrease in mean free path
(c) the rate of a first-order reaction does not depend on (c) more number of energetic collisions
reactant concentrations; the rate of a second-order (d) less number of energetic collisions
reaction does depend on reactant concentrations 30 In a zero order reaction for every10° rise of temperature,
(d) the rate of a first-order reaction does depend on the rate is doubled. If the temperature is increased from
reactant concentrations; the rate of a second order 10° C to 100°C, the rate of the reaction will become
reaction does not depend on reactant concentrations ª CBSE-AIPMT 2012
21 For a first order reaction, the concentration changes from (a) 256 times (b) 512 times (c) 64 times (d) 128 times
0.8 to 0.4 in 15 min. The time taken for the concentration 31 The temperature coefficient of most of the reactions lies
to change from 0.1 M to 0.025 M is between
(a) 30 min (b) 15 min (c) 7.5 min (d) 60 min (a) 1 and 3 (b) 2 and 3 (c) 1 and 4 (d) 2 and 4
32 The activation energy of a reaction is 9 kcal/mol. The (d) The energy of activation of forward reaction is equal to
increase in the rate constant when its temperature is the sum of heat of reaction and the energy of activation
raised from 295 to 300 K is approximately of backward reaction
(a) 10% (b) 50% (c) 100% (d) 29% 36 The rate constant is doubled when temperature increases
33 What is the activation energy for a reaction if its rate from 27° C to 37° C. Activation energy in kJ is
doubles when temperature is raised from 20°C to 35°C? (a) 34 (b) 54
(R = 8.314 J−1 K −1) ª NEET 2013 (c) 100 (d) 53
(a) 269 kJ mol −1 (b) 34.7 kJ mol −1 37 A reaction having equal energies of activation for forward
(c) 15.1 kJ mol −1 (d) 342 kJ mol −1 and reverse reaction has ª NEET 2013
34 The activation energy of a reaction can be determined (a) ∆ G = 0 (b) ∆ H = 0
(c) ∆ H = ∆ G = ∆ S = 0 (d) ∆ S = 0
from the slope of which of the following graphs?
ª CBSE-AIPMT 2015 38 For the two gaseous reactions, following data are given
(a) ln k vsT (b)
ln k
vsT (c) ln k vs
1
(d)
T
vs
1 A → B; k1 = 1010 e −20, 000/T
T T ln k T
C → D; k 2 = 1012 e −24, 606/T
35 For a reversible reaction, A q B, which one of the the temperature at which k1 becomes equal to k 2 is
following statements is wrong from the given energy (a) 400 K (b) 1000 K (c) 800 K (d) 1500 K
profile diagram? 39 In the presence of a catalyst, activation energy of a
(a) Activation energy of forward reaction is greater than reaction lowered by 2 kcal at 27°C. Hence, rate will be
backward reaction (a) 20 times
(b) The forward reaction is endothermic (b) 28 times
(c) The threshold energy is less than that of activation (c) 14 times
energy (d) remain the same

DAY PRACTICE SESSION 2

PROGRESSIVE QUESTIONS EXERCISE

1 A drop of solution (volume = 0.05 mL) contains 4 In the complex reaction,
60.0 × 10 −7mol of H + . If the rate of disappearance of H + is N2 + 3H2 s 2NH3
6.0 × 10 5 mol / Ls, how long time will it take for H + to  dx  −3 −1
  = 1 × 10 M [N2 ][H2 ] –1 × 10 M [NH3 ]
2 –3 3 2
disappear from the drop?  dt 
(a) 8 .0 × 10−8 s (b) 2.0 × 10−8 s [N2 ] [H2 ]3  dx 
= 10−5 M −2, if   is
(c) 6.0 × 10−6 s (d) 2.0 × 10−2 s [NH3 ]2  dt 
∆ [N2O5 ] (a) 0 (b) 1 × 105 (c) 1 × 10−5 (d) 1 × 10−3
2 2N2O5 → 4NO2 + O2, If – = k1[N2O5 ],
∆t 5 The reaction 2NO(g) + O2(g ) → 2NO2(g ) is of first
∆ [NO2 ] ∆ [O2 ] order. If volume of reaction vessel is reduced to1 / 3, the
= k 2[N2O5 ], = k 3[N2O5 ], then
∆t ∆t rate of reaction would be
(a) k1 = k2 = k3 (b) 2k1 = k2 = 4k3 (a) 1 / 3 times (b) 2 / 3 times (c) 3 times (d) 6 times
(c) 2k1 = 4k2 = k3 (d) None of these 6 At a certain temperature, the first order rate constant, k1 is
3 For the reaction, A(g ) + 2B(g ) → C(g ) + D(g ) ; found to be smaller than the second order rate constant,
dx k 2. If the energy of activation, E 1 of the first order reaction
= k [ A ] [B ]2 is greater than energy of activation, E 2 of the second
dt
Initial pressure of A and B are respectively 0.60 atm and order reaction then with increase in temperature
0.80 atm. At a time when pressure of C is 0.20 atm, rate (a) k1 will increase faster than k2 , but always will remain less
of the reaction, relative to the initial value is than k2
1 1 (b) k2 will increase faster than k1
(a) (b)
6 48 (c) k1 will increase faster than k2 and becomes equal to k2
1 1
(c) (d) (d) k1 will increase faster than k2 and becomes greater
4 24
than k2
 7 The rate law for a reaction between the substances A 11 Rate constant k varies with temperature as given by
and B is given by rate = k [ A ]n [B ]m . On doubling, the equation
concentration of A and halving the concentration of B, 2000 K
log k (min−1) = 5 −
the ratio of the new rate to the earlier rate of the reaction T
will be as Consider the following about this equation.
1 I. Pre-exponential factor is 105 .
(a) m +n
(b) (m + n)
2 II. Ea is 9.212 kcal.
−m)
(c) (n − m) (d) 2 (n III. Variation of log k with 1 / T is linear.
8 The rate constant for the reaction, Select the correct statement.
1
N2O5(g ) → 2NO2(g ) + O2(g ) (a) I, II and III (b) Both I and III
2 (c) Both II and III (d) Both I and II
is 2.3 × 10−2 s −1. Which equation given below describes
12 For a chemical reaction, A → products, it is found that
the change of [N2O5 ] with time?
the rate increases by a factor of 6.25, when the
([N2O5 ]0 and [N2O5 ]t corresponds to the concentration of
concentration of A is increased by a factor of 2.5. The
N2O5 initially and at time t)
order of reaction with respect to A is
(a) [N2O5 ]t = [N2O5 ]0 + kt (a) 2 (b) 0.5 (c) 1 (d) 2.5
(b) [N2O5 ]0 = log [N2O5 ]t + kt 13 A reactant (X ) forms two products
(c) log[N2O5 ]t = log [N2O5 ]0 + kt X → Y , Activation energy Ea1 , rate constant, = k1
[N2O5 ]0 X → Z , Activation energy Ea2 , rate constant, k2
(d) In = kt If, Ea2 = 2Ea1 , then k1 with k2 will be related as
[N2O5 ]t
−Ea 2 −Ea 2

9 For a zero order reaction, the rate constant is equals to (a) k1 = 2k2e RT (b) k2 = k1, e RT

−1 −Ea1 −Ea1
0.025 ms for the disappearance of A. What will be the
(c) k2 = k1e RT (d) k1 = Ak2e RT
concentration of A after 15s, if the initial concentration is
0.50 M? 14 For a first order reaction, the plot of log k against 1 /T is a
(a) 0.375 M (b) 0.125 M straight line. The slope of the line is equal to
(c) 0.060 M (d) 0.50 M 2.303 −Ea −Ea −Ea
(a) − (b) (c) (d)
EaR 2.303R R 2.303
10 t1/ 4 can be taken as the time taken for the concentration
3 15 The half-life of the reaction;
of a reactant to drop to th of its initial value. If the rate
4 1
N 2O 5 → 2NO + O 2 ; is 2.4 h.
constant for a first order reaction is k, the t1/ 4 can be 2
written as Starting with 10.8 g of N 2O 5 . How much oxygen will be
(a) 0.75/k (b) 0.69/k obtained after period of 9 . 6 h ?
(c) 0.29/k (d) 0.10/k (a) 1.5 L (b) 3.36 L (c) 1.05 L (d) 0.07 L

ANSWERS
SESSION 1 1 (c) 2 (d) 3 (b) 4 (a) 5 (b) 6 (d) 7 (a) 8 (d) 9 (b) 10 (d)
11 (c) 12 (a) 13 (c) 14 (b) 15 (b) 16 (b) 17 (a) 18 (d) 19 (c) 20 (b)
21 (a) 22 (a) 23 (d) 24 (b) 25 (b) 26 (b) 27 (b) 28 (d) 29 (c) 30 (b)
31 (b) 32 (d) 33 (b) 34 (c) 35 (c) 36 (d) 37 (b) 38 (b) 39 (b)

1 (b) 2 (b) 3 (a) 4 (a) 5 (c) 6 (a) 7 (d) 8 (d) 9 (b) 10 (c)
SESSION 2 11 (a) 12 (a) 13 (c) 14 (b) 15 (c)
DAY TWENTY TWO CHEMICAL KINETICS 237

Hints and Explanations

SESSION 1 =+
1 d [NH3 ] Now, from equation. (i), i.e.
2 dt [ X ]2
1 2 A + B → products 1 d [H2 ] 1 d [NH3 ] X 2 → 2 X [fast] ; keq =
or − =+ [ X2 ]
It is a third order reaction. 3 dt 2 dt
Rate of reaction, r1 = k[ A]2 [B] d [H2 ] 3 [ X ] = {keq [ X 2 ]}1/ 2 …(ii)
− = × 2 × 10 mol L−1s −1
−4
dt 2
If the concentration of A become Now, substitute the value of [ X ] from Eq.
= 3 × 10−4 mol L−1s −1 (ii) in Eq. (i), we get
double then the rate will be
r2 = k[2 A]2 [B] 5 For the reaction, Rate (r ) = k1(keq )1/ 2 [ X 2 ]1/ 2 [Y2 ]
r2 = 4k[ A]2 [B] A + B → Products = k[ X 2 ]1/ 2 [Y2 ]
On doubling the initial concentration 1 3
r2 = 4r1 ∴ Order of reaction = + 1 = = 15
.
of A only, the rate of the reaction is 2 2
2 Let the order of reaction with respect to also doubled, therefore
A and B is x and y respectively, So the Rate ∝ [ A]1 …(i) 11 Order of reaction may be zero, whole
rate law can be given as number or fraction number. Thus,
Let initial rate law is
R = k[ A]x [B]y . ..(i) statement ‘C’ is incorrect.
Rate = k[ A][B]y …(ii)
When the concentration of only B is 12 If the order of reaction w.r.t A is n and the
doubled, the rate is doubled , so If concentration of A and B both are
order of reaction w.r.t B is m, rate law
doubled, the rate gets changed by a
R1 = k[ A]x [2 B]y = 2 R ...(ii) becomes
factor of 8.
Rate = k[ A]n [B]m
If concentration of both the reactants A 8 × rate = k[2 A][2 B]y …(iii)
and B are doubled the rate increases From Eq. (i),
[Q Rate ∝ [ A]1 ]
by a factor of 8, so 5 ×10−5 = [0.20]n [0.30]m ...(i)
R ′ ′ = k[2 A] x [2 B] y = 8 R ...(iii) Dividing Eq. (iii) by Eq. (ii), we get
From Eq. (ii),
⇒ k2 x2 y [ A]x [B]y = 8R ...(iv) 8 = 2 × 2y ⇒ 4 = 2y
5 ×10−5 = [0.20]n [0.10]m ...(ii)
(2 ) = (2 )y
2
⇒ y=2
From Eqs. (i) and (ii), we get From Eq. (iii),
2 R [ A]x [2 B]y Hence, rate law is, rate = k [ A][B]2
⇒ = , 2 = 2y ⇒ y = 1 1 ×10−4 = [0.40]n [0.05]m
R [ A]x [B]y 6 Rate = k[NO 2Cl] 10 ×10−5 = [0.40]n [0.05]m ...(iii)
From Eqs. (i) and (iv), we get Hence, rate determining step is From Eqs. (i) and (ii),
8R 2 x2 y [ A]x [B]y
⇒ = or 8 = 2 x2 y 2NO2 Cl → 2NO 2 + 2Cl 5 ×10−5
n m
=
R [ A]x [B]y 0.20   0.30 
5 ×10−5  0.20   0.10 
Substitution of the value of y gives, 7 The slowest step is the rate
8 = 2 x21, 4 = 2 x ⇒ (2 )2 = (2 ) x determining step. Formation of B 1 = (3)m ⇒ (3)0 = (3)m ⇒ m = 0
⇒ x=2 (i.e. step I) is the slowest step, therefore From Eqs. (ii) and (iii),
step I is the rate determining step. 5 ×10−5
Substitution of the value of x and y in n m
=
0.20   0.10 
 0.40   0.05 
Eq. (i) gives,
8 For the reaction, 10 × 10−5
R = k[ A]2 [B] H2 (g ) + Br2 (g ) → 2HBr (g ) n 0
1  1
=   × 
0.10 

3 N2 + 3H2 q 2NH3 Rate of reaction = k[H2 ] [Br2 ]1/ 2 2  2   0.05 
d [H2 ] n 1 n
1  1
= − 0.3 × 10−4 Ms −1 Molecularity of reaction = 1 + 1 = 2 =   ⇒   =   ⇒ n = 1
− 1 1
⇒
dt
1 3 2 2 2 2
1 d [H2 ] 1 d [NH3 ] Order of reaction = 1 + =
Rate = − =+ 2 2 Overall order of the reaction
3 dt 2 dt
= n + m = 1+ 0= 1
=
d [NH3 ]
=−
2 d [H2 ] 9 Rate = k [ A]3 / 2 [B]−1
dx
dt 3 dt 13 Rate law, = k[ A ]1[ B]2 [C ]0
3 1
2 Order of reaction = + (−1) = = 0.5 dt
= − × (0.3 × 10 ) = 0.2 × 10−4
−4
2 2
3 = k[ A]1[B]2
10 We know that, slowest step is the rate Hence, overall order of reaction
4 For the reaction,
N2 + 3H2 → 2NH3 determining step. = 1 + 2 = 3.
d [N2 ] 1 d [H2 ] ∴Rater (r ) = k1[ X ] [Y2 ] …(i)
Rate = − =−
dt 3 dt
14 For a zero order reaction, t 1/ 2 is directly ∴
500
= antilog (0.00880) = 1.02 22 Rate constant k = 1.155 × 10−3 s −1
pt 2.303 a
proportional to the initial concentration k= log
of the reaction, pt =
500
= 490 atm t ( a − x)
[R ]0 t 1/ 2 ∝ [R ] 0 1.02  Here, a = a, (a − x) = a 
 
For a first order reaction, 18 For first order reactions,  2
2.303 [R ] 0 0.693 0.693 2.303 a
k= log k= = t 1/ 2 = log
t [R ] t 1/ 2 (3.0 h) k a/2
[R ] 0 2.303 [ A]0 2.303
at t 1/ 2 , [R ] = t = log = log 2
2 k [ A] 1.155 × 10−3
[ A]0 k ×t 2.303
So, the above equation becomes
or log = = × 0.3010
2.303 [R ]0 [ A] 2.303 1.155 × 10−3
k= log
t 1/ 2 [R ]0 / 2 [ A]0 0.693 (8 h) 0.693 × 103
log = × = 0.8024 = = 600 s
2.303 2.303 [ A] 3h 2.303 1.155
t 1/ 2 = = log 2 = × .3010
k k [ A]0 Alternatively,
= Antilog (0.8024) = 6.345
0.693 [ A] 0.6093 0.693
t 1/ 2 = t 1/ 2 = =
k [ A]0 1M k 1.155 × 10−3
[ A]0 = 1 M; [ A] = =
i.e. half-life period is independent of 6.345 6.345 = 600 s
initial concentration of a reactant.
= 01576
. M
[R ]0 2.303 A
15 For zero order reaction, t 1/ 2 = After 8 h, sucrose left = 0.1576 M 23 k = log 0
2k t A
where, [R ]0 = Initial concentration of 19 Specific rate constant, 2.303 0.1
0.693 0.693 = log = 0.075
the reactant. k= = = 0.5 × 10−3 s −1 40 0.005
k = Rate constant. t 1/ 2 1386
∴ Rate of reaction = k [ X ]
Thus, t 1/ 2 for zero order reaction is 20 For first order reactions, the rate of = 0.075 × 0.01= 7.50 × 10−4 M min−1.
directly proportional to the initial reaction is proportional to the first
24 Q Rate, 
dx 
concentration of the reactant. power of the concentration of the  = k[ A]
 dt 
t 1/ 2 ∝ [R ]0 reactant .
∴ 1.5 × 10−2 = k × 0.5
∴For zero order reaction, when the For, A → B
concentration of reactant is doubled, 1.5 ×10−2
Rate = −
d[ A]
= k[ A] k=
the half-life (t 1/ 2 ) will also get doubled. 0.5
dt
16 aA → xP [where, k = constant] = 3 × 10−2 min −1
Rate of reaction = k [ A]a 0.693 For a first order reaction,
Half-life (t 1/ 2 ) =
When [ A 1 ] = 2 .2 mM, r1 = 2 .4 m Ms −1 k Half-life period,
∴Rate of first order reaction depends 0.693 0.693
2 .2 t 1/ 2 = =
When [ A 2 ] = mM, r2 = 0.6 m Ms −1 upon reactant concentrations and half
2 k 3 × 10−2
life does not depend upon initial
r1 k[ A 1 ]a a
2.4  2.2  concentration of reactant, [ A]0 . = 23.1min
= or =  or
r2 k[ A 2 ]a 0.6  1.1  For second order reactions, the rate 25 For zero order reaction,
4 = (2 )a of reaction is proportional to the 30
x = kt = 0.2 mol dm−3h−1 × h
second power of the concentration of 60
∴ a =2 the reactant.
∴ Order of reaction is 2. = 0.1 mol dm−3
For, 2 A → B Rate = k[ A]2
Concentration = 0.05 mol dm−3
17 From the unit of rate constant (i.e. s −1), 1
Half-life (t 1/ 2 ) = Hence, initial concentration
it is clear that the reaction is of first k[ A]0
order. = 0.1 + 0.05 = 0.15mol dm−3
∴ Rate of second order reaction
2N2O 5 → 4NO 2 + O 2 26 For zero order reaction,
depends upon reactant concentration
Hence, for first order reaction, and half life also does depend on [ A]0 . a a a
k= = =
2.303 p 2 t 1/ 2 2 × 100 200
k= log 0 21 Order = 1
t pt
Concentration changes from 0.8 M to When 80% completion take place,
−5 2.303 500 x a 0.80 a
∴ 3.38 × 10 = log 0.4 M (50%) in 15 min, thus half-life is k= =
10 × 60 pt 15 min. A change from 0.1 M to 0.025 t 200 t
M is 75% and for first order reaction
or log
500
= 0.00880 t = 200 × 0.8 = 160 min
pt T75 = 2 × T50 = 2 × 15 = 30 min
 2k Ea
27 Rate constant of pseudo 1st order 34 By Arrhenius equation 2.303 log =
reaction only depends on the k = Ae − Ea / RT k 8.314 × 10−3
310 − 300 
× 
concentration of reactants present in
where, Ea = energy of activation 
excess.  310 × 300 
Like, RCl + H2O → ROH + HCl Applying log on both the side,
Ea 10
E 2.303 log2 = ×
Rate = k [RCl] [H2O] ln k = ln A − a …(i) 8.314 × 10−3 93000
RT
Actual rate law, Rate = k [RCl] Ea
or log k = −
Ea
+ log A …(ii) 2.303 × 0.3010 =
28 According to collision theory, 2.303 RT 8.314 × 10−3
(i) The reaction rate depends on 10
This equation is of the form of ×
collision frequency and effective 93000
y = mx + c, i.e. the equation of a
collisions. For a molecule to have straight line. Thus, if a plot of log k vs 2.303 × 0.3010 × 8.314 × 10 −3
Ea =
effective collisions it should fulfill 1 10
is a straight line, the validity of the
two conditions; proper orientation T × 93000
and sufficient energy. equation of confirmed. Ea = 53.363 kJ ~
–– 53 kJ
(ii) Greater the temperature, greater Ea
Slope of the line = − 37 ∆ H =(Ea ) forward − (Ea ) backward = 0; ∆H = 0
will be the collision rate. 2.303R
reaction reaction
29 Rate of reaction increases with Thus, measuring the slope of the line,
increase in temperature because the the value of Ea can be calculated. 38 Given, k1 = 1010 e −20, 000 / T
number of energetic collision increases. k2 = 1012 e −24, 606 / T
30 For 10° rise in temperature, n = 1 Slope = –
Ea k1 = k2
In k R 10 −20 ,000 /T
so, rate = 2 = 2 = 2
n 1 10 e = 1012 e −24, 606 / T
−20, 000 24, 606
+
When temperature is increased from e T T = 102
10°C to 100°C, change in temperature
1/T 4, 606
= 100 − 10 = 90°C, i.e. n = 9
e T = 102
So, rate = 2 9 = 512 times 35
Threshold On taking log both sides,
Alternate method, with every 10° rise
4606
energy (Et) = log102
(Energy of reactant)

in temperature rate becomes double,

 100 − 10  2.303T
r′  
 
so =2 10
= 2 9 = 512 times 2log10 × T =
4606
r E'a (energy of 2.303
31 Temperature coefficient is the ratio of Ea EP product) 4606 4606
T= = = 1000 K
two velocity constant having the B (energy of 2.303 × 2 4.606
∆E
difference of 10°C. For most of the ER the reaction) 39 Arrhenius equation is
reaction, the value of temperature A
k = Ae − Ea / RT
coefficient lies between 2 and 3. Reaction coordinate
In the presence of catalyst,
k2 Ea  T2 − T1 
32 log =   where, Ea = activation energy of rate constant k ′ = Ae − Ea ′ / RT
k1 2.303R  TT
1 2  forward reaction
Eq. (ii)/Eq. (i), we get
k2 9000  300 − 295  Ea ′ = activation energy of backward
log =   k′ ′
k1 2.303 × 2  295 × 300  reaction = e( Ea / Ea )/ RT
k
k2 k2 The above energy profile diagram
log = 0.1103 = 1.288 
 2000 

k1 k1 shows that Ea > E ′a k′  2 × 300 
=e = e 3. 33
k2 = 1.288 k1 The potential energy of the product is k
greater than that of the reactant, so [Q Ea − Ea ′ = 2000 cal (given)]
i.e. increase by 28.8%. the reaction is endothermic.
Q On taking log both sides,
k2 Ea  1 1  Ea = E ′ a + ∆ E k′
33 log =  −  log =
3.33
k1 2 .303 R  T1 T2  Et = Ea or Et > E ′a k 2.303
log 2 k′
36 We know, = antilog 1.446
=
Ea  1 − 1  k
Given, T1 = 27 + 273 = 300 K k1 = k
2 .303 × 8.314  293 308  = 27.92 ≈ 28
T2 = 37 + 273 = 310 K k2 = 2 k
R = 8.314 × 10 kJ −3 We know that, rate (R ) ∝ k
Ea 15 R ′ k′
0.3 = × ∴ = = 28
2.303 × 8.314 293 × 308 k2 Ea  T2 − T1 
2.303 log =   R k
Ea = 347 k1 R  T1 × T2 
. kJ/mol or R ′ = 28 R
 d [ln k ] E Ea
SESSION 2 6 = a2 log10 k = log10 A −
dt RT 2.303 RT
6.0 × 10−7mol
1 [H+ ] = = 1.2 × 10−2 M As Ea increases, rate constant,k also I. log10 A = 5,
5.0 × 10−5 L increases so k1 will increase faster
dx dx A = 105 , true
rate = or dt = than k2 but always will remain less
Ea
dt rate than k2 . II. = 2000
1.2 × 10 −2
M 2.303 R
= = 2.0 × 10−8 s 7 Rate becomes xy times, if
6.0 × 105 m / s concentration is made x times of a Ea = 2000 × 2.303 × 0.002 kcal
reactant giving yth order reaction. = 9.212 kcal, true
2 Based on the given reaction,
1 ∆[N2O 5 ] 1 ∆[NO 2 ] ∆[O 2 ] Rate = k[ A]n [B]m III. Equation represents straight line,
− = = Concentration of A is doubled hence
2 ∆t 4 ∆t ∆t hence true,
k1 k2 x = 2, y = n and rate becomes = 2 n
[N2O 5 ] = [N2O 5 ] = k3 [N2O 5 ] times.
12 Rate, R = k [ A]m or 6.25R = k [2.5 A]m
2 4
Concentration of B is halved, hence ∴ 6.25 = (2.5)m or (2.5)2 = (2.5)m
∴ 2 k1 = k2 = 4k3 1
x = and y = m and rate becomes ∴ m=2
3   = k(0.60)(0.80)2 = 0.384 k
dx 2
The order of reaction with respect to A is 2.
 dt  0 m
=  
1
A(g ) + 2 B(g ) → C(g ) + D(g ) 2
times. 13 Q k ∝ e − Ea / RT (Arrhenius equation)
− Ea
m − Ea1 / RT
0.60 0.80 0 0 or k = Ae RT k1 = Ae
Net rate becomes = (2 )n  
1
times
( 0.60 − x) ( 0.80 − 2x) x x 2 − Ea2
x = 0.2 atm = (2 )n − m times and k2 = Ae RT but, Ea 2 = 2 Ea1
∴ [ A] = 0.4 atm −1 −2 Ea1 − Ea1 − Ea1
8 From the unit of rate constant (s ). It is
[B] = 0.4 ∴ k2 = Ae RT = Ae RT ⋅e RT
clear that the reaction is of first order.
∴  dx  = k(0.4)(0.4)2 = 0.064 k − Ea1
  For a first order reaction,
 dt  t [N O ] k2 = k1e RT
1 a
k = loge ⇒ kt = loge 2 5 0
∴  dx   dx  = 0.064k = 1 a− x − Ea
    t [N2O5 ]t
14 log k = log A ×
1
 dt  t  dt  0 0.384k 6
dx 2.303 R T
kf 9 = k = 0.025 ms −1
4 N2 + 3H2 s 2NH3 dt Ea
kb Slope =
x 2.303R
or = k = 0.025 ms −1
 dx  = k [N ][H ]3 − k [NH ]2 log k
  t
 dt  net f 2 2 b 3
x = 15 × 0.025 = 0.375 M
[NH3 ]2
k Thus, [ A] = 0.50 − 0.375 = 0125 1/T
Also, 3
= f . M
[N2 ][H2 ] k 1
b
10 A → Product 15 N2O 5 → 2NO + O 2
[N2 ][H2 ]3 k 1 × 10−3 Initially a 0
2
or = b = 10.8
[NH3 ]2 kf 1 × 102 After time, t (a − x) x Moles of N2O 5 = = 0.1
 a a 108
= 1 × 10−5
After, t1 / 4 a − 
 4 4 9.6
Number of half-lives = n = =4
 dx  = 1 × 102 M−3 × 10−5 [NH ]2 − 1 For the first order kinetics, 2.4
 
 dt  3 n 4
 a  . ×   = (0.1) ×   =
2.303 1 1 01
.
×10−3 [NH3 ]2 k= log   N t = 01
t  a − x 2 2 16
Thus,   = 0
dx
0.1
 dt  2.303 a Moles of N2O 5 left =
∴ k = log 16
t 1/ 4 3a
5 2NO(g ) + O 2 → 2NO 2 (g ) Moles of N2O 5 changed to product
4
When the volume of vessel changes 0.1 1.5
4 = 0.1 − =
1 2.303 log 16 16
into , then concentration of reactant 3 = 0.29
3 t 1/ 4 = 1.5
k k Volume of O 2 formed = × 22.4
becomes three times. The rate of 2 × 16
2000 K
reaction for first order reaction is 11 log k (min−1 ) = 5 − = 1.05 L
directly proportional to concentration, T
Therefore, rate of reaction will
increases three times.