Chemical Kinetics

JEE (MAIN+ADVANCED)
Physical Chemistry
ENTHUSIAST COURSE
STUDY MATERIAL
Chemical Kinetics
English Medium
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® Chemical Kinetics
CHEMICAL KINETICS
1. INTRODUCTION
Chemical kinetics deals with the rates of chemical processes. Any chemical process may be broken
down into a sequence of one or more single-step processes known either as elementary processes,
elementary reactions, or elementary steps. Elementary reactions usually involve either a single
reactive collision between two molecules, which we refer to as a bimolecular step, or dissociation/
isomerisation of a single reactant molecule, which we refer to as a unimolecular step. Very rarely,
under conditions of extremely high pressure, a termolecular step may occur, which involves
simultaneous collision of three reactant molecules. An important point to recognise is that, many
reactions that are written as a single reaction equation, in actual fact, consist of a series of elementary
®
steps. This will become extremely important as we learn more about the theory of chemical reaction
rates.
As a general rule, elementary processes involve a transition between two atomic or molecular
states separated by a potential barrier. The potential barrier constitutes the activation energy of the
process, and determines the rate at which it occurs. When the barrier is low, the thermal energy of
the reactants will generally be high enough to surmount the barrier and move over to products, and
the reaction will be fast. However, when the barrier is high, only a few reactants will have sufficient
energy, and the reaction will be much slower. The presence of a potential barrier to reaction is also
the source of the temperature dependence of reaction rates.
The huge variety of chemical species, types of reaction, and the accompanying potential energy
surfaces involved means that the time scale over which chemical reactions occur covers many
orders of magnitude, from very slow reactions, such as iron rusting, to extremely fast reactions,
such as the electron transfer processes involved in many biological systems or the combustion
reactions occurring in flames.
A study into the kinetics of a chemical reaction is usually carried out with one or both of two main
node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
goals in mind :
(i) Analysis of the sequence of elementary steps giving rise to the overall reaction. i.e. the
reaction mechanism.
(ii) Determination of the absolute rate of the reaction and/or its individual elementary steps.
2. CLASSIFICATION OF REACTION
(i) There are certain reactions which are too slow. Ex. Rusting of Iron, weathering of rocks.
(ii) Instantaneous reactions i.e. too fast. Ex. Detonation of explosives, acid-base neutralization,
precipitation of AgCl by NaCl and AgNO3.
(iii) Neither too fast nor too slow. Ex. Combination of H2 and Cl2 in presence of light, hydrolysis
of ethyl acetate catalysed by acid, decomposition of Azomethane.
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3. Types of Rates of chemical reaction :

For a reaction R ¾¾® P ,
Total change in concentration |Dc| D[Reactant ] D[Product]

• Average rate = Total time taken
= = – =
Dt Dt Dt
• Instantaneous rate : Rate of reaction at a particular instant.
é|Dc|ù dc d[R] d[P]

Rinstantaneous = lim ê Dt ú = dt = – =
Dt ® 0 ë û dt dt
Instantaneous rate can be determined from slope of a tangent at time t on curve drawn for concentration
versus time.
®
3.1 Initial Rate : Instantaneous rate at ‘t = 0’ is called initial rate [Slope of tangent at t = 0].
[R] 0
Concentration [R]
–D[R] –(c2–c1)
rav = = (t –t )
c1 Dt 2 1
c2 –d[R]
rinst = = –slope
dt
t1 t2 t time
3.2 Reaction rates and stoichiometry :
We have seen that for stoichiometrically simple reactions of the type A ® B, the rate can be either
expressed in terms of the decrease in reactant concentration with time, –D[A]/Dt or the increase in
product concentration with time, D[B]/Dt. For more complex reactions, we must be careful in
writing the rate expressions. Consider for example, the reaction,
2 A ¾® B
Two moles of A disappear for each mole of B that forms – that is, the rate of disappearance of A
is twice as fast as the rate of appearance of B. We write the overall rate of reaction as either
1 D[A] D[B]
Rate = - =
2 Dt Dt
In general, for the reaction, aA + bB ¾® cC + dD

the rate is given by
1 D[A] 1 D[B] 1 D[C] 1 D[D]

Rate = - =- = =
a Dt b Dt c Dt d Dt
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Ex. For the reaction in terms : N2 + 3H2 ¾¾® 2NH3
d[N ]
Rate of reaction in terms of N2 = - dt 2 = rate of disappearance of N2
d[H2 ]
Rate of reaction in terms of H2 = - = rate of disappearance of H2
dt
d[NH 3 ]
Rate of reaction in terms of NH3 = = rate of appearance of NH3
dt
These rates are not all equal. Therefore, by convention, the rate of a reaction is defined as
d[N 2 ] 1 d[H2 ] 1 d[NH 3 ]
• Rate of reaction = - =- =
dt 3 dt 2 dt
®
Note: The value of rate of reaction is dependent on the stoichiometric coefficients used in the reaction while
the rate of increase or decrease in amount of any species will be fixed value under given conditions.
Ex.1 The following reaction was studied in a closed vessel
2N2O5(g) ¾¾® 4NO2(g) + O2(g)
It was found that the concentration of NO2 increases by 2.0 × 10–2 mol L–1 in five seconds.
Calculate.
(i) The rate of reaction
(ii) The rate of decrease of concentration of N2O5
1 d éëNO2 ùû
Sol. (i) Rate of reaction =
4 dt
d éNO2 ùû 2.0 ´ 10-2 mol L-1

But ë = = 4 × 10–3 mol L–1 s–1
dt 5s
1
Rate of reaction × 4 × 10–3 = 10–3 mol L–1 s–1
4
(ii) Rate of decrease of conc. of N2O5
d éN 2 O5 ùû 1 1 d éNO ù
=- ë = – × Rate of formation of NO2 = + ë 2 û
dt 2 2 dt
1
=+ × 4 × 10–3 = 2 × 10–3 mol L–1 s–1
2
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3.3 FACTORS AFFECTING RATE OF CHEMICAL REACTION

(i) Concentration (ii) Temperature
(iii) Nature of reactants and products (iv) Catalyst
(v) pH of the solution (vi) Dielectric constant of the medium.
(vii) Radiations / light (viii) Pressure
(ix) Electrical and magnetic field.
The first four factors generally affect rate of almost all reactions while other factors are specific to
some reactions only.
(i) Effect of concentration :
For most of the reactions, rate depends on concentration of reactants. So rate of reaction decreases
with passage of time, since concentration of reactants decreases .
®
Conc.
Time
(ii) Effect of temperature : Generally rate of reaction increases on increasing temperature.
(iii) Effect of nature of reactants and products :
(a) Physical state of reactants : Gaseous state > Liquid state > Solid state
(Decreasing order of rate of reaction)
Because collisions in gaseous systems are more effective than condensed systems (solid & liquid).
(b) Physical size of reactants : In heterogeneous reactions, as we decreases the particle size,
rate of reaction increases since surface area increases.
(c) Chemical nature of reactants :
• If more bonds are to be broken, the rate of reaction will be slow.
• Similarly if bond strength in reactants is more, rate of reaction will be slow.
(iv) Effect of Catalyst :
• Presence of catalyst or positive catalyst lowers down the activation energy hence increases the
rate of reaction.
• Presence of inhibitor or negative catalyst increases activation energy hence decreases the rate of
reaction.
3+
(v) Effect of pH of solution : Ex. [Fe(CN)6]4– ¾¾¾
(Tl )
® [Fe(CN)6]3–
This reaction takes place with appreciable rate in acidic medium, but does not take place in basic
medium.
(vi) Effect of dielectric constant of the medium : More is the dielectric constant of the medium
greater will be the rate of ionic reactions.
(vii) Effect of radiations / light : Radiations are useful for photochemical reactions.
(viii) Effect of pressure : Pressure is important factor for gaseous reactions.
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(ix) Effect of electrical & magnetic field : Electric and magnetic fields are rate determining factors if a
reaction involves polar species.
4. RATE LAW (DEPENDENCE OF RATE ON CONCENTRATION OF REACTANTS) :
The representation of rate of reaction in terms of the concentration of the reactants is called the rate
law. It can only be established by experiments.
Generally rate law expressions are not simple and these may differ for the same reaction on conditions
under which the reaction is being carried out. But for large number of reactions starting with pure
reactants we can obtain simple rate laws. For these reactions :
Rate µ (conc.)order
Rate = K (conc.)order This is the differential rate equation or rate expression.
Where K = Rate constant = specific reaction rate = rate of reaction when concentration is unity
®
unit of K = (conc)1– order time–1
Note:Value of K is a constant for a given reaction, depending only on temperature and catalyst use.
4.1 Order of reaction :
Let there be a reaction , m1A + m2B ¾® products.
Now, if on the basis of experiment, we find that
R µ [A]p [B]q
where p may or may not be equal to m1 and similarily q may or may not be equal to m2.
p is order of reaction with respect to reactant A and q is order of reaction with respect to reactant B
and (p + q) is overall order of the reaction.
Note:Order of a reaction can be ‘zero’, any whole number, fractional number or even be negative
with respect to a particular reactant.
v Examples showing different values of order of reactions :
Reaction Rate law Order

(i) 2N2O5 (g) ® 4NO2 (g) + O2 (g) R = K [N2O5]1 1

(ii) 5Br–(aq)+ BrO3–(aq)+6H+(aq) R=K[Br–][BrO3–][H+]2 1+1+2=4
®3Br2(l)+3H2O(l)
(iii) H2 (Para) ® H2 (ortho) R = K [H2 (Para) ]3/2 3/2

(iv) NO2(g) + CO(g) ® NO(g) + CO2(g) R = K [NO2]2 [CO]º 2+0=2
(v) 2O3 (g) ® 3O2 (g) R = K [O3]2 [O2]–1 2–1=1
(vi) H2 + Cl2 ¾¾® 2 HCl

hn
R = K [H2]º[Cl2]º 0+0=0
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The reaction (ii) does not take place in one single step. It is almost impossible for all the 12 molecules
of the reactants to be in a state of encounter simultaneously. Such a reaction is called
Complex reaction and takes places in a sequence of a number of Elementary reactions. For an
elementary reaction, the sum of stoichiometric coefficients of reactants = order of the reaction. But for
complex reactions, order is to be experimentally calculated.
4.2 Molecularity of reaction :
The number of molecules that react in an elementary step is the molecularity of the elementary reaction.
Molecularity is defined only for the elementary reactions and not for complex reactions. No elementary
reactions involving more than three molecules are known, because of very low probability of simultaneous
collision of more than three molecules.
The rate law for the elementary reaction
aA + bB ¾¾® Products, Rate = k[A]a[B]b ,
®
where a + b = 1, 2 or 3
For an elementary reaction, the orders in the rate law equal the coefficients of the reactants. It must be
noted that the order is defined for complex as well as elementary reactions and is always experimentally
calculated from the mechanism of the reaction, usually by the slowest step of the mechanism known as
rate determining step (RDS) of the reaction.
Comparision between molecularity and order of reaction

Molecularity of Reaction Order of Reaction
1 It is defined as the no. of molecules of 1 It is defined as the sum of the power of
reactant taking part in a chemical concentration terms that appear in rate law.
reaction. NH4NO2 ® N 2 + 2H2O.
NH4NO2 ® N 2 + 2H2O , Rate = k[NH4NO2] , order =1
molecularity = 1
2 It is always a whole number. 2 It may be zero, fractional or integer.
It can neither be zero nor fractional.
3 It is derived from RDS in the mechanism of 3 It is derived from rate expression.
reaction
4 It is theoretical value. 4 It is experimental value.
5 Reactions with molecularity > 3 are rare. 5 Reactions with order of reaction > 4 are also rare.
6 Molecularity is independent of pressure and 6 Order of reaction may depend upon pressure
temperature. and temperature.
5. INTEGRATED RATE LAW :

For a single reactant reaction where the chemical equation has the form
A ® products
and the rate law is assumed to be of the form
Rate = – d[A]/dt = k [A]m
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Where m is the order of the reaction with respect to substance A. Three important cases can be treated
: m = 0, m = 1, and m = 2. These are called zeroth order, first order, and second order, respectively.
5.1 Zero - order reaction :

For a reaction where the chemical equation has the form [A0]
A ® products
Concentration [A]
k = – slope of
and the rate law is assumed to be of the form the straight line
Rate = – d[A]/dt = k [A]0
ct t
- ò d[A] = k ò dt
c0 0
time
®
C0 - C t
k=
't'
or kt = C0 – Ct or Ct = C0 – kt
• Unit of K is same as that of Rate = mol lit–1 sec–1.
C0
• Time for completion =
k
• t1/2 (half life period)
C0
At t1/2 , Ct = ,
2
C0 C0
So kt1/2 = Þ t1/2 =
2 2k
\ t1/2 µ C0
v Examples of Zero order reactions :
Generally decomposition of gases on metal surfaces at high concentrations follow zero order kinetics as
rate depends on surface area of catalyst.
2PH3 (g) ¾¾
Ni
® 2 P(s) + 3H2(g) Rate = K [PH3]0
2HI (g) ¾¾
Au
® H2(g) + I2(g) Rate = K [HI]0
2NH3(g) ¾¾ ® N2(g) + 3H2(g) Rate = K [NH3]0

Pt
H2(g) + Cl2(g) ¾¾
hv
® 2 HCl(g) Rate = K [H2]0 [Cl2]0
v Graphs :
Zero order Zero order Zero order

Conc.[A]
Rate
t1/2
t Conc. Conc.
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Ex.2 For the zero order reaction : A ® P , K = 10–2 (mol/litre) sec–1 If initial concentration of A is
0.3M , then find concentration of A left at 10 sec.
(A) 0 M (B) 0.2 M (C) 0.1 M (D) 0.15 M
Sol. (B)
[A]t = [A]0 – Kt = 0.3 – 10–2 × 10 = 0.2 M
5.2 First order reaction :

Consider a first order reaction with single reactant.
A ¾¾® Products
t=0 a 0
t=t a–x
®
Rate = – d[A]/dt = k [A]1
dx dx
\ = k (a–x)1 or = kdt.
dt a-x
2.303 a 2.303 C0
• On solving k = log a - x = log C
t t t
Interval formula :
2.303 C Wilhemy formula :
log 0 2.303 C
K= t Ct C t = C0 e- kt k= log 1
(t 2 - t1 ) C2
• Unit of k = sec–1, min–1, etc.
• Half-life time (t1/2) :
2.303 2C0 2.303 log2 ln2 0.693
k = t log C Þ t1/2 = = =
1/ 2 0 k k k
\ Half-life period for a first order reaction is a constant quantity at given temperature.
• Examples of first order reactions :

(i) Decomposition of azoisopropane
CH3 CH3
D
CH – N = N – CH (g) ¾¾® N2(g) + C6H14(g)
CH3 CH3
(ii) Conversion of N–chloro acetanilide into p–chloroacetanilide

•• ¾¾®
HCl
Cl – N – C – CH3 H — N – C – CH3
O O
Cl
1
(iii) H2O2(aq.) ¾® H2O(l) + O (g)
2 2
(iv) NH4 NO2 ¾® 2H2O(g) + N2(g)
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(v) Radioactive decay
All radioactive decays always follow first order kinetics.
226 222
88 Ra ¾¾® 86 Rn + 2He4
• Graphs :
I order I order I order
t1/2
Log[A]
t Rate Conc. Conc.
t0.75
®
Ex.3 Calculate t for a first order reaction :
0.50
2.303 C0 2.303 C0 t3 / 4 log 4 2 log 2

Sol. k= t log = log Þ
t1 / 2
= log 2 = log 2 =2
3/4 1 t1 / 2 C0
C0
4 2
Ex.4 90% of a first order reaction was completed in 10 hours. When will 99.9% of the reaction
complete ?
2.303 a
Sol. K= log
t a? x
a = 100 , x = 90 , t = 10
2.303 100
So K= log
10 10
K = 2.303 × 10–1 hour–1

Now for 99.9% completion -
a = 100 and x = 99.9
2.303 100 2.303

t= log = -1
´ 3 = 30 hours
K 0.1 2.303 ´ 10
Ex.5 A first order reaction is 90% complete after 40 min. Calculate the half life of reaction.
Sol. a = 100, x = 90
2.303 a
K1 = log
t a-x
2.303 100
= log
40 10
2.303
= = 5.757 × 10–2 min–1
40
0.693 0.693
t1/2 = K = = 12.03 min.
1 5.757 ´ 10-2
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5.3.1 Second order reaction :

• Case : 1
A + A ¾® Products
a a
(a – x) (a –x)
dx
\ = k (a–x)2
dt
1 1 1 1
Þ – = kt or – = kt
(a - x) a Ct C0
• Unit of k = Lmol–1 sec–1
1
• Half life, t½= k.C
®
o
• Graphs :
II order II order II order

1
[A] t1/2
Rate
t (conc.)
2
1/conc.
5.3.2 Case : 2
A + B ¾® products.
a b 0
a–x b–x
Rate law
dx
= k (a – x) (b – x)
dt node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
x t
dx
ò0 (a - x) (b - x) = ò0 kdt
2.303 b(a - x)
k= log (no need to remember)
t(a - b) a(b - x)
where a ¹ b
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Ex.6 For a second order reaction in which both the reactants have equal initial concentration,
the time taken for 60% completion of reaction is 3000 second. What will be the time taken
for 20% of the reaction?
1 x
Sol. k2 =
t a (a - x )
Let a = 1,
1 x
k2 = t (1 - x )
1 æ 0.6 ö
= 3000 ç 1 - 0.6 ÷
è ø
1 0.6 1
= ´ =
®
3000 0.4 2000
So time for the 20% completion :
1 x
t = k a (a - x)
2
0.20
= 2000 ´ 0.80 = 500 sec.
5.4 Pseudo order reaction :
For, A + B ¾® Products
t=0 a b
t=t a–x b–x
Rate = K [A]n [B]m
If [B] = constant Þ [b – x] » constant
Rate = K' [A]n
when K' = K[B]n
• Case 1 :
If concentration of B is much greater than A, then [B] = Constant Þ [b – x] » Constant.
• Case 2 :
If B is a catalyst , then [B] = Constant Þ [b – x] » Constant.

• Case 3 :
If B is a solvent , then [B] = Constant Þ [b – x] » Constant.
5.4.1 PSEUDO FIRST ORDER REACTIONS :
A second order (or of higher order) reactions can be converted into a first order reaction if the other
reactant is taken in large excess. Such first order reactions are known as pseudo first order
reactions.
\ For A + B ¾® Products [Rate] = K [A]1 [B]1
2.303 b (a - x )
K = t (a - b) log a ( b - x ) (from 5.3.2)
Now if ‘B’ is taken in large excess b > > a.

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2.303 (a - x) 2.303 a
\ K = -bt log Þ K= log a - x
a bt
2.303 a 2.303 a
Þ K.b = log a - x Þ K¢ = log a - x
t t
K¢ is pseudo first order rate constant.

K¢ will have units of first order.
K will have units of second order.
v Table : Characteristics of Zero, First, Second and nth order reactions of the type A ¾¾® Products
Zero order First order Second order nth order
®
d[A]
d[A ] d[A] d[A] - = k[A]n
Differential Rate law – = k[A]° - = k[A] - = k[A]2 dt
dt dt dt
1 1 1 1
Integrated Rate law [A]t = [A]0 – kt In[A]t=–kt+In[A]0 = kt + [A] -
[A]t 0 [A t ]n -1 [A 0 ]n -1
= (n - 1) kt
1 1
Linear graph [A]t v/s t In [A] v/s t [A]
v/s t [A t ]n -1 v/s t
[A]0 0.693 1 1
Half-life t1/2 = t1/2 = t1/2 = k[A] t1 / 2 µ
2k k 0 [A 0 ]n -1
(depends on [A]0) (independent of [A]0) (depends on[A]0)
6 Methods to determine order of a reaction :

6.1 Initial rate method : node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
By comparison of different initial rates of a reaction by varying the concentration of one of the reactants
while others are kept constant.
r = k [A]a [B]b [C]c if [B] = constant and [C] = constant
then for two different initial concentrations of A we have
a
r01 æ [A ] ö
r01 = k [A0]1 a
r0 2 = k [A0]2 a
Þ =ç 01÷
r02 è [A 0 ]2 ø
log (r01 r02 )

or in log form we have a = log [A ] [A ]
( 0 1 0 2)
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6.2 Integrated rate law method :

It is method of hit and trial. By checking if the kinetic data (experimental data) best fits into a particular
integrated rate law, we determine the order. It can also be done graphically.
Ex.7 The rate of decomposition of N2O5 in CCl4 solution has been studied at 318 K and the
following results have been obtained :
t/min 0 135 342 683 1693

c/M 2.08 1.91 1.67 1.35 0.57
Find the order of the reaction and calculate its rate constant. What is the half-life period?
Sol. It can be shown that these data will not satisfy the integrated rate law of zero order. We now try
®
ln(c 0 / c)
integrated first order equation i.e., k = .
t
ln(c / c)
t / min c/M k= 0 min–1
t
0 2.08 6.32 × 10–4
135 1.91 6.30 × 10–4
339 1.68 6.32 × 10–4
683 1.35 6.32 × 10–4
1680 0.72 6.31 × 10–4
It can be seen that the value of k is almost constant for all the experimental results and hence it is
first order reaction with k = 6.31 × 10–4 min–1.
0.693
t1/2 = = 1.094 × 103 min–1
6.31 ´ 10-4 min -1
6.3 Method of half lives :

The half lives of each order is unique so by comparing half lives we can determine order for nth
1
order reaction t1/2 µ [A ]n -1 (Remember)
n -1
(t1 / 2 )1 [A '0 ]2
= (Remember)
(t1' / 2 )2 [A 0 ]1n -1
Ex.8 In a decomposition reaction, the reaction was found to be 50% complete in 210 seconds when
the initial pressure of the mixture was 200 mm. In a second experiment the time of half reaction
was 140 seconds when the initial pressure was 300 mm. Calculate the total order of the reaction.
1
Sol. For a nth order reaction t1/2 µ c n -1
0
n -1
210 æ 300 ö
= ç 200 ÷ Þn=2
140 è ø
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6.4 Ostwald’s isolation method :
This method is useful for reactions which involve a large number of reactants. In this method, the
concentration of all the reactants are taken in large excess except that of one, so if
Rate = k [A]a [B]b [C]c = k0 [A]a
Then value of ‘a’ can be calculated by previous methods and similarly ‘b’ and ‘c’ can also be
calculated.
6.5 Initial rate method :
For reaction : A + B ¾¾® Products
Initial rate, r0 = K.[A0]n [B0]m
®
Now, order with respect to A may be determined by comparing the initial rate of reaction at
different initial concentration of A but fixed initial concentration of B.
Ex.9 Consider the following data for the reaction :
A + B ¾¾® Products
Run Initial concentration Initial concentration Initial rate (mol s–1)
1 0.10 M 1.0 M 2.1 × 10–3
2. 0.20 M 1.0 M 8.4 × 10–3
3. 0.20 M 2.0 M 8.4 × 10–3
Determine the order of reaction with respect to A and with respect B and the over all order
of reaction.
Sol. The rate law may be expressed as :
Rate = k [A]p [B]q
Comparing experiments 2 and 3
(Rate)2 = k[0.2]p [1.0]q = 8.4 × 10–3 (1)
(Rate)3 = k[0.2]p [2.0]q = 8.4 × 10–3 (2) node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
Dividing equation (2) by (1)
(Rate)3 k[0.2]p [2.0]q 8.4 ´ 10-3

= =
(Rate)2 k[0.2]p [1.0]q 8.4 ´ 10-3
[2]q = [2]0
or q=0
Comparing experiments 1 and 2,
(Rate)2 = k[0.20]p [1.0]q = 8.4 × 10–3 (3)
(Rate)1 = k[0.10]p [1.0]q = 2.1 × 10–3 (4)
Dividing equation (3) by (4)
152 E
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(Rate)2 k[0.20]p [1.0]q 8.4 ´ 10 -3

= = =4
(Rate)1 k[0.10]p [1.0]q 2.1 ´ 10 -3
[2]p = [2]2 or p=2

so order with respect to A = 2
order with respect to B = 0
overall order = 2
7. APPLICATION OF FIRST ORDER REACTION
(Methods to monitor the progress of the reaction )

7.1 Case : 1
First order gaseous reaction :
®
Progress of gaseous reactions can be monitored by measuring total pressure at a fixed volume &
temperature. This method can be applied for those reactions also in which a gas is produced
because of decomposition of a solid or liquid. We can get an idea about the concentration of
reacting species at a particular time by measuring pressure.
The pressure data can be given in terms of
(i) Partial pressure of the reactant
(ii) Total pressure of the reaction system
(iii) Pressure at only some points of time.
Ex.10 Find the expression for K in terms of P0 , Pt and n. For the reaction
A(g) ¾® nB(g)
Sol. A(g) ¾® nB(g)
P0
PA = (P0 – x) nx
\ Pt (Total pressure at time ‘t’) = P0 – x + nx = P0 + (n – 1) x

Pt - P0
\ x=
n -1
Pt - P0 P n - Pt
\ PA = P 0 – = 0
n -1 n -1
nP0 - Pt
\ a µ p0 & (a – x) µ PA =
n -1
2.303 P0 (n - 1)
\ k= log (nP - P )
t 0 t
Final total pressure after infinite time = Pf = nP0

Do not remember the formula but derive it for each question.
E 153
JEE-Chemistry ALLEN
®
7.2 Case : 2
Volume measurement :
(i) By measuring the volume of product formed we can monitor the progress of reactions.
Ex.11 Study of a reaction whose progress is monitored by measuring the volume of a escaping gas.
D
NH4NO2(s) ¾¾® 2H2O(l) + N2(g)
Sol. Let, Vt be the volume of N2 collected at time ‘t’
V¥ = be the volume of N2 collected at the end of the reaction.
a µ V¥ and x µ Vt
®
(a – x) µ V¥ – Vt
2.303 V¥
\ k= log V - V
t ¥ t
(ii) By titration method : By measuring the volume of titrating agent we can monitor amount of
reactant remaining or amount of product formed at any time. It is the titre value . Here the
milliequivalent or millimoles are calculated using valence factors.
Ex.12 From the following data show that the decomposition of hydrogen peroxide in aqueous
solution is a first - order reaction. What is the value of the rate constant?
Time in minutes 0 10 20 30 40
Volume V in mL 25.0 20.0 15.7 12.5 9.6
Where V is the volume in mL of standard KMnO4 solution required to react with a definite
volume of hydrogen peroxide solution.
Sol. The equation for a first order reaction is, node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
D
2H2O2(l) ¾¾® 2H2O(l) + O2(g)
the volume of KMnO4 used, evidently corresponds to the undecomposed hydrogen peroxide.
Hence the volume of KMnO4 used, at zero time corresponds to the initial concentration a and the
volume used after time t, corresponds to (a – x) at that time. Inserting these values in the above
equation, we get
2.303 25
When t = 10 min. k1 = log 20.0 = 0.022318 min–1 = 0.000372 s–1
10
2.303 25
When t = 20 min. k1 = log = 0.023265 min–1 = 0.000387 s–1
20 15.7
154 E
ALLEN
2.303 25
When t = 30 min. k1 = 30 log 12.5 = 0.02311 min–1 = 0.000385 s–1
2.303 25
When t = 40 min. k1 = log = 0.023932 min–1 = 0.0003983 s–1
40 9.6
The constancy of k, shows that the decomposition of H2O2 in aqueous solution is a first order reaction.
The average value of the rate constant is 0.0003879 s–1 .
Ex.13 Study of acid hydrolysis of an ester.

+
CH3COOCH3 + H2 O ¾¾¾
H
(HCl)
® CH COOH + CH OH
3 3
(excess )
®
The progress of this reaction is monitored or determined by titrating the fixed volume of reaction
mixture at different time intervals against a standard solution of NaOH using phenolphthalein
as indicator. Find out rate constant of the reaction in terms of volume of NaOH consumed at
t = 0, V0 , at t = ¥, V¥ & at time t, Vt .
Sol. Let, V0 = Volume of NaOH used at t = 0 [this is exclusively for HCl.]
Vt = Volume of NaOH used at ‘t’
V¥ = Volume of NaOH used at t = ¥
a µ (V¥ – V0 )
(a – x) µ (V¥ – Vt)
x µ (Vt – V0)
2.303 V¥ - V0
k= log V - V
t ¥ t
7.3 Case : 3
Optical rotation measurement :
It is used for optically active sample. It is applicable if there is at least one optically active species
involved in chemical reaction.
• The optically active species may be present in reactant or product.
It is found that (r¥ - r0 ) µ a (a = concentration , x = amount consumed)

(r¥ - rt ) µ (a - x)
Where are r0 , rt , r¥ are angle of optical rotation at time t = 0, t = t and t = ¥.
2.303 r¥ - r0
k= log r - r (Remember)
t ¥ t
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JEE-Chemistry ALLEN
®
Ex.14 Study of hydrolysis of sucrose, progress of this reaction is monitored with the help of
polarimeter because a solution of sucrose is dextrorotatory and on hydrolysis, the mixture
of glucose and fructose obtained becomes laevorotatory. That’s why this reaction is also
known as inversion of cane sugar.
+
C12H22O11 + H2O ¾¾ ® C6H12O6 + C6H12O6
H
excess glucose fructose

Let the readings in the polarimeter be
t = 0 , q0 ; t = ‘t’, qt and at t = ¥ , q¥
Then calculate rate constant ‘k’ in terms of these readings.
Sol. The principle of the experiment is that change in the rotation is directly proportional to the amount of
®
sugar hydrolysed.
\ a µ ( q0 – q¥ ) ; (a – x) µ (qt – q¥) ; x µ (q0 – qt)
2.303 æ q0 - q ¥ ö
k= log ç q - q ÷
t è t ¥ ø
7.4 Case : 4
First order growth reaction :
For bacteria multiplication or virus growth use following concept
Consider a growth reaction,
Time Population (or colony)
0 a
t (a + x)
dx dx
= k (a + x) or (a + x)
= kdt
dt
On integration node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
loge (a + x) = kt + C at t = 0 ; x = 0 Þ C = loge a
a 2.303 æ a ö
kt = – loge (a + x) = – log10 ç (a + x) ÷
t è ø
2.303 æa +xö
k= log10 ç ÷
t è a ø
156 E
ALLEN
0.693
v Generation time : At t = generation time , x = a \ t=
K
8. SOME SPECIAL CASES :
8.1 FIRST ORDER PARALLEL OR COMPETING OR SIMULTANEOUS REACTIONS
k1 B
x
A
a–x–y k2 C
y
At t=0 [A] = a [B] = [C] = 0

(i) Differential rate law :
d[B] d[C]
= k1 [A] ; dt = k2 [A]
dt
®
- d[A] d[B] d[C] - d[A]
and, = + Þ = (k1 + k2 ) [A] = keff [A]
dt dt dt dt
keff = k1 + k2 = overall rate constant for the disappearance of 'A'
(ii) Integral rate law :
- k eff t - (k1 + k 2 ) t
[A]t = ae = ae
d[B] d[B] - (k1 + k 2 ) t

= k1 [A] Þ dt = k1a e
dt
æ ka ö
1 - (k + k ) t
[B] = ç k + k ÷ (1 – e 1 2 )
è 1 2 ø
2
é k a ù
- (k 1+ k2 )t
Similarly, [C] = ê k + k ú (1 – e )
ë 1 2û
(iii) Composition of product :

[B] k1
[C]
= k2
8.2 FIRST ORDER REVERSIBLE REACTION
A B
t=0 a 0
t=t a –x x
t = teq. a – xeq. xeq.
xeq. = eq conc. of product
d[A]
– = + kf [A] – kb[B]
dt
d[A]
At equilibrium = 0, kf[A] = k[B]
dt
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®
9. EFFECT OF TEMPERATURE ON RATE OF REACTION :

In early days the effect of temperature on reaction rate was expressed in terms of temperature coefficient
(m ) which was defined as the ratio of rate of reaction at two different temperature differing by 10ºC
(usually these temperatures were taken as 25ºC and 35ºC)
K T +10
T.C, m = K » 2 to 3 (for most of the reactions)
T
Note : Rate of reaction increases on increasing temperature (Generally ; T.C > 1)

k 40ºC
Ex.15 For a reaction T.C. = 2, Calculate k for this reaction. Assuming T.C remains constant.
25ºC
Dt
k2 15 3
Sol. = (T.C.)10
k1 = (2) 10
= (2) 2
= 8
®
But the method of temperature coefficient was not exact to explain the effect of temperature on reaction
rate. For that a new theory was evolved.
9.1 Collision theory of reaction rate :
It was developed by Max Trautz and William lewis. It gives insight in to the energetics and mechanistic
aspects of reactions.
It is based upon kinetic theory of gases.
According the this theory :
(i) A chemical reaction takes place due to the collision among reactant molecules. The number of
collisions taking place per second per unit volume of the reaction mixture is known as collision
frequency (Z).
(ii) Every collision does not bring a chemical change. The collision that actually produce the products
are effective collision. For a collision to be effective the following two barriers are to be cleared.
v Energy barrier : The minimum amount of absolute energy which the colliding molecules must possess
as to make the chemical reaction to occur is known as threshold energy.
• Reactant molecules having energy equal or greater than the threshold are called active molecules and
those having energy less than the threshold are called passive molecules.
• At a given temperature there exists a dynamic equilibrium between active and passive molecules. The
process of transformation from passive to active molecules being endothermic, increase of temperature
increases the number of active molecules and hence the reaction.
Passive molecules Active molecules, DH = +ve
• “The minimum amount of excess energy required by reactant molecules to participate in a reaction is
called activation energy (Ea)”.
158 E
ALLEN
CONCEPT OF ENERGY OF ACTIVATION (Ea) :

• The average extra amount of energy which the reactant molecules (having energy less than the threshold)
must acquire so that their mutual collision may lead to the breaking of bond(s) and hence the energy is
known as energy of activation of the reaction. It is denoted by the symbol Ea. Thus,
Ea = Threshold energy – Actual average energy of reactants
Ea is expressed in kcal mole–1 or kJ mole–1.
• The essence of Collision Theory of reaction rate is that there exists an energy barrier in the reaction path
between reactant(s) and product(s) and for reaction to occur, the reactant molecules must climb over
the top of the barrier which they do by collision. The existence of energy barrier and concept of Ea can
be understood from the following diagram.
®
Threshold enthalpy DH = Enthalpy change during the reaction (R ® P)
Ea1 Ea2 or energy Ea1 = Energy of activation of the forward reaction
Energy
Ea2 = Energy of activation of the backward reaction

Reactants
Product
Reaction coordinate
From the figure above it can be concluded that the minimum activation energy of any exothermic
reaction will be zero while minimum activation energy for any endothermic reaction will be equal
to DH.
Greater the height of energy barrier, greater will be the energy of activation and more slower will
be the reaction at a given temperature.
Activated complex Activated complex

Ea Ea
Energy
Energy
Products P
Reactants DH DH
R Reactants
Products
R
P
Progress of the reaction Progress of the reaction
Exothermic Endothermic
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JEE-Chemistry ALLEN
®
v Orientation barrier : Energy alone does not determine the effectiveness of the collision. The reacting
molecules must collide in proper direction to make collision effective. Following diagrams can explain
importance of suitable direction for collision.
Consider reaction : A2 + B2 ® 2AB
Head - on collision
Transition
®
Reactants state Product
approaching
A A
A A
A A
B B
Reactants B B
Transition B B
State Product
oblique collision
No reaction
Reactants node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
Transition
state No products
are formed
(iii) Rate of any chemical reaction = Collision frequency × fraction of the total number of effective
collision.
= Collision frequency × fraction of the total number of collision
in which K.E. of the colliding molecules equals to Ea or exceeds
over it × fraction of collision in proper orientation.
From Maxwellian distribution, it is found that fraction of molecules having excess energy greater than
threshold energy lead to the formation of product.
160 E
ALLEN
Fraction of T2 T2 > T1
molecule T1
E Ea
e - Ea / RT ® Represents fraction of molecules having K.E. greater than or equal to Ea.
Rate µ e - Ea / RT
Dependence of rate on temperature is due to dependence of k on temperature.
k µ e - Ea / RT
®
[Arrhenius equation]
k = Ae -Ea /RT
'A' is pre-exponential factor or frequency factor representing collisions taking place with proper
orientation. A and Ea are assumed to be independent of temperature.
lnA
Ea
lnk = ln A –
RT
–Ea
slope =
R
As T ® ¥ , K ® A
lnk
At temperature T1 , Rate constant = k1 1/T
At temperature T2 , Rate constant = k2
Ea EE k æ 1 1 ö
& lnk2 = lnA – RT Þ ln k = a ç T - T ÷
a 2
lnk1 = lnA –
RT1 2 1 R è 1 2 ø
9.2 REVERSIBLE REACTIONS

kf = Af e- E af / RT
kb = Ab e- E ab / RT
kf A f e - Eaf / RT æ Af ö
Keq = kb
= A b e - E ab / RT
= ç A ÷ e - (E af - Eab ) / RT
è bø
DH æA ö
f
ln Keq = – + ln ç A ÷
RT è b ø
lnKeq lnKeq
DH = +ve
DH
slope = – DH = +ve
R DH
slope = –
R
1/T 1/T
endothermic exothermic
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JEE-Chemistry ALLEN
®
Ex.16 For a reaction, temperature coefficient = 2, then calculate the activation energy (in kJ) of
the reaction.
K2
Sol. Given : Temperature coefficient = K = 2
1
T1 = 25 + 273 = 298 k
T2 = 35 + 273 = 308 k
K2 E a æ T2 - T1 ö
log = ç ÷
K1 2.303R è T1 T2 ø
Ea æ 10 ö
log2 = ´
2.303 ´ 8.314 çè 298 ´ 308 ÷ø
®
Ea = 52.31 kJ mol–1
1
Ex.17 For first order gaseous reaction, log k when plotted against , it give a straight the with a
T
slope of –8000. Calculate the activation energy of the reaction.

Sol. For an arrhenius equation k = Ae–Ea / RT
Ea 1
log k = log A - ´
2.303R T
1
when curve is plotted between log k and . A straight line is obtained and a slope of this curve
T
Ea
=-
2.303R
Ea
Then, = 8000
2.303R
or Ea = 8000 × 2.303 × 2 = 36848 calories

1
Ex.18 The slope of the plot of log k vs for a certain reaction was found to be – 5.4 × 103. node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
T
Calculate the energy of activation of the reaction. If the rate constant of the reaction is
1.155 × 10–2 sec–1 at 373 K , what is its frequency factor ?
-E
Sol. (a) Slope = 2.303 R = – 5.4 × 103
Ea = 5.4 × 103 × 2.303 × 1.987

= 24.624 cal mol–1
24.624
(b) K = Ae– E/RT ; log 1.155 × 10–2 = log A –
2.303 ´ 1.987 ´ 373
or A = 1.764 × 103 sec–1
162 E
ALLEN
10. CATALYST AND CATALYSIS :
A catalyst is a substance, which increases the rate of a reaction without itself being consumed at the end
of the reaction, and the phenomenon is called catalysis.
Thermal decomposition of KCIO3 is found to be accelerated by the presence of MnO2. Here MnO2
acts as a catalyst.
2KClO3 + [MnO2] ¾¾® 2KCl + 3O2 + [MnO2]
• MnO2 can be received in the same composition and mass at the end of the reaction.
• The word catalyst should not be used when the added substance reduces the rate of reaction. The
substance is then called inhibitor.
• Catalyst are generally foreign substances but sometimes one of the product may act as a catalyst and
®
such catalyst is called “auto catalyst” and the phenomena is called auto catalysis.
In the permanganate titration of oxalic acid initially there is slow discharge of the colour of permanganate
solution but afterwards the discharge of the colour become faster. This is due to the formation of
MnSO4 during the reaction which acts as a catalyst for the same reaction. Thus, MnSO4 is an
“auto catalyst” for this reaction. This is an example of auto catalyst.
2KMnO4 + 3H2SO4 + 5H2C2O2 ¾¾® K2SO4 + 8H2O + 10CO2 + MnSO4
10.1 General characteristics of catalyst :

• A catalyst does not initiate the reaction normally. It simply fastens it.
• Only a small amount of catalyst can catalyse the reaction.
• A catalyst does not alter the position of equilibrium i.e. magnitude of equilibrium constant and
hence DGº. It simply lowers the time needed to attain equilibrium. This means if a reversible
reaction in absence of catalyst completes to go to the extent of 75% till attainment of equilibrium,
and this state of equilibrium is attained in 20 minutes then in presence of a catalyst, the reaction
will still go to 75% of completion on the attainment of equilibrium but the time needed for this will
be less than 20 minutes.
P.E. Ea
E'a
HR
HP
Products
Reaction Coordinate
A catalyst drives the reaction through a low energy path and hence Ea is less. That is, the function
of the catalyst is to lower down the activation energy.
Ea = Energy of activation in absence of catalyst.
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JEE-Chemistry ALLEN
®
Ea' = Overall Energy of activation in presence of catalyst.

Ea – Ea' = Lowering of activation energy by catalyst.
Catalyzed pathway Uncatalyzed pathway

Potential energy
Potential energy
Ea Ea
Reactants Reactants
Products Products
Reaction progress Reaction progress

(a) (b)
®
10.2 Comparison of rates of reaction in presence and absence of catalyst :
If k and kcat be the rate constant of a reaction at a given temperature T , Ea and E’a are the activation
energies of the reaction in absence and presence of catalyst, respectively, the
k cat Ae - E ' a / RT
= = Ae(Ea - E 'a ) / RT
k Ae - Ea / RT
k cat
Since Ea – E’a is positive so kcat > k. the ratio gives the number of times the rate of reaction will
k
increase by the use of catalyst at a given temperature.

The rate of reaction in the presence of catalyst at any temperature T1 may be made equal to the rate of
reaction in absence of catalyst but for this sake we will have to raise the temperature. Let this temperature
E' E
or T = T
a a
be T2 = e - E ' / RT = e - E
a 1 a / RT2
1 2
11 CALCULATION OF RATE LAW / ORDER

11.1 When first step is rate determining step.
Ex.19 Calculate order and rate law of reaction -
2NO2 + F2 ¾® 2NO2F
with help of mechanism
NO2 + F2 ¾¾ ® NO2F + F (slow )
K1
I.
II. NO2 + F ¾¾
K2
® NO2F (fast )
Sol. According to RDS
Rate = k1 [NO2] [F2]
164 E
ALLEN
11.2 Equilibrium approach :
–
Ex.20 For the reaction , H+ + HNO2 + C6H5NH2 ¾¾®
Br
C6H5N2+ + 2H2O , the mechanism is ,
k1
H+ + HNO2 k2
H2 NO2+ (fast equilibrium step)
intermediate
H2NO2+ + Br – ¾¾
k3
® NOBr + H2O (slow)
NOBr– + C6H5NH2 ¾¾
k4
® C6H5N2+ + Br – + H2O (fast)
Derive the rate law expression for the reaction
Sol. r = k3 [Br–] [H2NO2+]
®
+
k1 [H2 NO2 ]
Keq = k = [H+ ][HNO ]
2 2
é k1 ù
[H2NO2+] = ê k ú [H+] [HNO2]
ë 2 û
k1 k 3
r = k [H+] [HNO2] [Br–].
2
Note : Rate law can have reactant product or catalyst concentration terms but not any intermediate
terms.
E 165
JEE-Chemistry ALLEN
®
MISCELLANEOUS PREVIOUS YEARS QUESTION

1. Which of the following statement(s) is (are) correct [JEE 1999]
(A) A plot of log Kp versus 1/T is linear
(B) A plot of log [X] versus time is linear for a first order reaction, X ¾® P
(C) A plot of log P versus 1/T is linear at constant volume.
(D) A plot of P versus 1/V is linear at constant temperature.
Ans. (A,B,D)
2. The rate constant for an isomerisation reaction A ® B is 4.5 × 10–3 min–1. If the initial concentration of
A is 1 M. Calculate the rate of the reaction after 1 h. [JEE 1999]
®
Ans. 3.435 × 10–3 M/min
Sol. r = k[A]
r = K[A]0 e–kt
–3 × 60
r = (4.5 × 10–3) e–4.5 × 10 M/min.
3. A hydrogenation reaction is carried out at 500 K. If the same reaction is carried out in the presence of
a catalyst at the same rate, the temperature required is 400 K. Calculate the activation energy of the
reaction if the catalyst lowers the activation barrier by 20 kJmol–1. [JEE 2000]
Ans. 100 kJmol–1
ær ö 1 æ Ea Ea ö
ln ç r ÷ = – R ç T - T ÷
2 2 1
Sol.
è ø2 è 2 1 ø
1 æ Ea1 - 20 Ea1 ö
ln (1) = - -
R çè 40 500 ÷ø
Ea1 = 100
4. The rate constant for the reaction [JEE SCR 2000]

2N2O5 ¾® 4NO2+O2
is 3.0 × 10–5 sec–1. if the rate is 2.4 × 10–5 mol litre–1 sec–1, then the concentration of N2O5
(in mol litre–1 ) is
(A) 1.4 (B) 1.2 (C) 0.004 (D) 0.8
Ans. (D)
Sol. r = k[N2O5]2
2.4 × 10–5 = 3 × 10–5[N2O5]2
166 E
ALLEN
5. If I is the intensity of absorbed light and C is the concentration of AB for the photochemical process :
AB + hv ¾® AB, the rate of formation of AB is directly proportional to [JEE SCR 2001]
(A) C (B) I (C) I2 (D) CI
Ans. (B)
Sol. For phot chemical reaction
rµI
6. The rate of a first order reaction is 0.04 mole litre–1 s–1 at 10 minutes and 0.03 mol litre–1 s–1 at
20 minutes after initiation. Find the half life of the reaction. [JEE 2001]
Ans. t1/2 = 24.14 min
®
æ ln 2 ö æ 0.04 ö
Sol. ç ÷ (20 – 10) = ln ç ÷
è t1/ 2 ø è 0.03 ø
7. Consider the chemical reaction, N2(g) + 3H2(g) ¾® 2NH3(g). The rate of this reaction can be expressed
in term of time derivative of concentration of N2(g), H2(g) or NH3 (g). Identify the correct relationship
amongst the rate expressions. [JEE SCR 2002]
(A) Rate = – d[N2]/dt = – 1/3 d[H2]/dt = 1/2d[NH3]/dt
(B) Rate = – d[N2]/dt = – 3 d[H2]/dt = 2d[NH3]/dt
(C) Rate = d[N2]/dt = 1/3 d[H2]/dt =1/2d[NH3]/dt
(D) Rate = – d[N2]/dt = – d[H2]/dt = d[NH3]/dt
Ans. (A)
-d[N 2 ] 1 d[H2 ] 1 d[NH3 ]

Sol. =- =
dt 3 dt 2 dt
8. In a first order reaction the concentration of reactant decreases from 800 mol/dm3 to 50 mol/dm3 in
2 × 104 sec. The rate constant of reaction in sec–1 is [JEE SCR 2003]
(A) 2 × 104 (B) 3.45 × 10–5
(C) 1.3486 × 10–4 (D) 2 × 10–4
Ans. (C)
æ 800 ö
Sol. K(2 × 104) = ln ç ÷
è 50 ø
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®
9. The reaction, X ¾® Product follows first order kinetics. In 40 minutes the concentration of X changes
from 0.1 M to 0.025 M. Then the rate of reaction when concentration of X is 0.01 M
(A) 1.73 × 10 –4 M min –1 (B) 3.47 × 10 –5 M min –1
(C) 3.47 × 10 –4 M min –1 (D) 1.73 × 10 –5 M min –1 [JEE SCR 2004]
Ans. (C)
æ 0.1 ö
Sol. K(40) = ln ç ÷
è 0.25 ø
ln 2
K=
20
r = K[X]
ln 2
®
= ´ 0.1
20
10. 2X(g) ¾® 3Y(g) + 2Z(g)
Time (in Min) 0 100 200
Partial pressure of X 800 400 200
(in mm of Hg)
Assuming ideal gas condition. Calculate
(a) Order of reaction
(b) Rate constant (KX)
(c) Time taken for 75% completion of reaction
(d) Total pressure when PX = 700 mm. [JEE 2005]
Ans. (a) 1, (b) 6.93 × 10–3 min–1 , (c) 200, (d) 950 mm
Sol. (a) As half life is constant so it will be of first order.
æ 800 ö
(b) Kx(100) = ln ç ÷
è 400 ø node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
æ ln 2 ö
(c) t = 75% = 2t50% = 2 ç ÷
è Kx ø
(d) 2X(g) ¾¾® 3Y(g) + 2Z(g)

3x
800 – x x
2
Here x = 100
3x
So PT = 800 + = 950
2
168 E
ALLEN
11. Which of the following statement is incorrect about order of reaction? [JEE 2005]
(A) Order of reaction is determined experimentally
(B) It is the sum of power of concentration terms in the rate law expression
(C) It does not necessarily depend on stoichiometric coefficients
(D) Order of the reaction can not have fractional value.
Ans. (D)
12. Consider a reaction aG + bH ® Products. When concentration of both the reactants G and H is
doubled, the rate increases by eight times. However, when concentration of G is doubled keeping the
concentration of H fixed, the rate is doubled. The overall order of the reaction is : [JEE 2006]
(A) 0 (B) 1 (C) 2 (D) 3
®
12. Ans.(D)
a a
r2 æ [G ]2 ö æ [H]2 ö
Sol. ç ÷ ç ÷
r1 è [G ]1 ø è [H]1 ø
8 = 2a . 2b .......(1)
2 = 2a .......(2)
a = 1, b = 2
13. Under the same reaction conditions, initial concentration of 1.386 mol dm–3 of a substance becomes
half in 40 seconds and 20 seconds through first order and zero order kinetics, respectively. Ratio
æ k1 ö
çç ÷÷ of the rate constants for first order (k1) and zero order (k0) of the reactions is [JEE 2008]
è k0 ø
(A) 0.5 mol–1 dm3 (B) 1.0 mol dm–3
(C) 1.5 mol dm–3 (D) 2.0 mol–1 dm3
Ans. (A)
ln 2
Sol. K1 =
40
1.386
K0 =
2 ´ 20
K1
= 0.5
K0
E 169
JEE-Chemistry ALLEN
®
14. Plots showing the variation of the rate constant (k) with temperature (T) are given below. The plot
that follows Arrhenius equation is – [JEE 2010]
k k k k
(A) (B) (C) (D)
T T T T
Ans. (A)
Sol.
®
T
15. The concentration of R in the reaction R ® P was measured as a function of time and the following
data is obtained :
[R] (molar) 1.0 0.75 0.40 0.10
t(min.) 0.0 0.05 0.12 0.18
The order of the reaction is. [JEE 2010]

Ans. Zero
Sol. By hit and trial method het reaction is zero order.
[A]0 - [A]1
K1 = t1
1 - 0.75
K1 = =5
0.05
[A]0 - [A]t2
K2 =
t2
1 - 0.4
K2 = =5
0.12
As K1 » K1 so reaction will be zero order reaction. node06\B0BC-BD\Kota\JEE(Advanced)\Enthuse\Chem\Module\Mod.#Solid, Liquid & CK-(PC)\Eng\03-Chemical Kinetics\01_Theory
170 E

Chemical Kinetics

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Chemical Kinetics

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JEE (MAIN+ADVANCED)

3. Types of Rates of chemical reaction :

Total change in concentration |Dc| D[Reactant ] D[Product]

• Instantaneous rate : Rate of reaction at a particular instant.

é|Dc|ù dc d[R] d[P]

In general, for the reaction, aA + bB ¾® cC + dD

1 D[A] 1 D[B] 1 D[C] 1 D[D]

Ex. For the reaction in terms : N2 + 3H2 ¾¾® 2NH3

2N2O5(g) ¾¾® 4NO2(g) + O2(g)

d éNO2 ùû 2.0 ´ 10-2 mol L-1

(ii) Rate of decrease of conc. of N2O5

3.3 FACTORS AFFECTING RATE OF CHEMICAL REACTION

Reaction Rate law Order

(i) 2N2O5 (g) ® 4NO2 (g) + O2 (g) R = K [N2O5]1 1

(iii) H2 (Para) ® H2 (ortho) R = K [H2 (Para) ]3/2 3/2

(vi) H2 + Cl2 ¾¾® 2 HCl

Comparision between molecularity and order of reaction

5. INTEGRATED RATE LAW :

Rate = – d[A]/dt = k [A]m

5.1 Zero - order reaction :

2NH3(g) ¾¾ ® N2(g) + 3H2(g) Rate = K [NH3]0

Zero order Zero order Zero order

[A]t = [A]0 – Kt = 0.3 – 10–2 × 10 = 0.2 M

5.2 First order reaction :

• Examples of first order reactions :

(ii) Conversion of N–chloro acetanilide into p–chloroacetanilide

I order I order I order

t Rate Conc. Conc.

2.303 C0 2.303 C0 t3 / 4 log 4 2 log 2

K = 2.303 × 10–1 hour–1

2.303 100 2.303

5.3.1 Second order reaction :

II order II order II order

If B is a catalyst , then [B] = Constant Þ [b – x] » Constant.

Now if ‘B’ is taken in large excess b > > a.

K¢ is pseudo first order rate constant.

Zero order First order Second order nth order

(depends on [A]0) (independent of [A]0) (depends on[A]0)

6 Methods to determine order of a reaction :

log (r01 r02 )

6.2 Integrated rate law method :

t/min 0 135 342 683 1693

6.3 Method of half lives :

6.4 Ostwald’s isolation method :

Rate = k [A]a [B]b [C]c = k0 [A]a

Dividing equation (2) by (1)

(Rate)3 k[0.2]p [2.0]q 8.4 ´ 10-3

(Rate)2 k[0.20]p [1.0]q 8.4 ´ 10 -3

[2]p = [2]2 or p=2

(Methods to monitor the progress of the reaction )

\ Pt (Total pressure at time ‘t’) = P0 – x + nx = P0 + (n – 1) x

Final total pressure after infinite time = Pf = nP0

Sol. Let, Vt be the volume of N2 collected at time ‘t’

V¥ = be the volume of N2 collected at the end of the reaction.

Ex.13 Study of acid hydrolysis of an ester.

It is found that (r¥ - r0 ) µ a (a = concentration , x = amount consumed)

Where are r0 , rt , r¥ are angle of optical rotation at time t = 0, t = t and t = ¥.

excess glucose fructose

At t=0 [A] = a [B] = [C] = 0

d[B] d[B] - (k1 + k 2 ) t

(iii) Composition of product :

8.2 FIRST ORDER REVERSIBLE REACTION

9. EFFECT OF TEMPERATURE ON RATE OF REACTION :

Note : Rate of reaction increases on increasing temperature (Generally ; T.C > 1)