Chem Kinetics Notes

CHEMICAL KINETICS
RATE OF REACTION
Rate of reaction is the rate of change of concentration of either reactant or product with time. Let a
reaction be represented as
Reactant (A)  Product (P)
If dx mole of reactant is transferred towards the product side in small time dt then the rate of reaction
is dx/dt.
For reactant rate of reaction   d[ A ]

dt
(– means decrease in concentration of the reactant)
For product rate of reaction   d[P]

dt
(+ means increase in concentration of the product)
Units of the Rate of Reaction :
Since concentration is usually expressed in moles/litre and the time is taken in seconds or minutes,
the unit of the rate of reaction is moles litre–1 sec–1 (mol L–1 s –1) or moles litre–1 min –1
(mol L–1 min–1).
In case of gaseous reactions, pressures are used in place of molar concentrations.
Measurement of the Rate of Reaction :
If concentration of one of the reactants is studied at different intervals of time and these values are
plotted against the corresponding times, a graph of the type shown in figure is obtained.
0.05
CON CENTRATION OF A REACTANT
A
0.04
(IN MOLES/LITRE)
0.03
0.02 x = 0.04 P
MOLE
0.01
B
0.00 O
5 10 15 20 25
TIME (IN MINUTES)
Chemical Kinetics [36]

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Calculation of the average rate of reaction :
To calculate the average rate of reaction between any two instants of time say t1 and t2, the
corresponding concentrations x1 and x2 are noted from the graph. Then
x 2  x1
Average rate of reaction =
t 2  t1
For example, from the (figure) between the time interval 5 to 15 minutes,
0.03  0.012 0.018
Average rate    0.0018 and mol L–1 min–1
15  5 10
If concentration of one of the products is plotted against time, the type of curve obtained and the
rate of reaction at any instant of time are calculated as shown in the figure.
CONCENTRATION OF REACTANT (MOL L )
0.05
-1
0.04
A
CONCENTRATION OF
x1
0.03 P
A PRODUCT
0.02 B
O
x2
0.01
O t1 t2
0.00
10 25 TIME
5 15 20
TIME (IN MINUTES)
Calculation of instantaneous rate of reaction :

To know the rate of the reaction at any time t, a tangent is drawn to the curve at the point
corresponding to that time figure and it is extended on either side so as to cut the axes, say at
the points A and B. then
Change in the concentration
Rate of reaction =
Time
x OA
= Slope of the tangent =
t OB
Thus the slope of the tangent gives the rate of reaction.
For example , from the (figure) in the present case, at time t = 10 minutes, x = 0.04 mole and
t = 20 minutes = 20  60 = 1200 seconds , therefore, rate of reaction at the end of
10 minutes will be 0.04/1200 = 3.33  10–5 mol L–1 s–1.
Ex.1 In a reaction the concentration of a reactant (A) changes from 0.200 mol litre–1 to 0.150 mol
litre–1 in 10 minutes. What is the average rate of reaction during this interval?
Sol. [A] = [A]final – [A]initial
= [0.150 – 0.200]
= – 0.050 mol litre–1
t = 10 minutes
 [ A ] 0.50
Average rate of reaction = = = 0.005 mol litre–1 min–1
t 10

Ex.2 Decomposition of N2O5 is expressed by the equation ,
N2O5  2NO2 + ½O2
If in a certaion time interval, rate of decomposition of N2O5 is 1.8× 10–3 mol litre–1 min–1, what will
be the rates of formation of NO2 and O2 during the same interval ?
Sol. The rate expression for the decomposition of N2O5 is
[ N 2 O 5 ] 1 [ NO 2 ] [O 2 ]
– = =2×
t 2 t t
[ NO 2 ] [ N 2 O 5 ]
So = 2 = 2 × 1.8 × 10–3
t t
= 3.6 × 10–3 mol litre–1 min–1
[O 2 ] 1 [ N 2 O 5 ] 1
and = = × 1.8 × 10–3
t 2 t 2
= 0.9 ×10–3 mol litre–1 min–1
[ N 2 O 5 ]
[Rate is always positive and hence = is taken positive.
t
Ex.3 If the decomposition of nitrogen (V) oxide 2N2O5  4NO2 + O2, following a first order kinetics.
(i) Calculate the rate constant for a 0.04 M solution, if the instantaneous rate is
1.4  10–6 mol L s–1.
(ii) Also calculate the rate of reaction when the concentration of N2O5 is 1.20 M.
(iii) What concentration of N2O5 would give a rate of 2.45  105 mol L–1s–1?
Sol. (i) As the given reaction is of first order, therefore,
Rate = k[N2O5]
rate 1.4  10 6
or k  [M = conc. in mol L–1]
[N 2 O5 ] 0.04
= 3.5  10–5s–1
(ii) Now if the concentration of N2O5 is 1.20 M, then
rate = k[N2O5]
= 3.5  10–5  1.20 = 4.2  10–5 mol L–1 s–1
(iii) To obtain concentration of N2O5 when the rate is 2.45  10–5 mol –1 s–1, we note that
Rate 2.45  10 5
[N2O5] =  = 0.7 mol L–1 or 0.7 M
k 3.5  10 5
Factors Affecting the Reaction Rate :
The rate of any particular reaction depends upon the following factors:
(i) Concentration of the reactants
(ii) Temperature
(iii) Presence of Catalyst
(iv) Surface area of the reactants
(v) Presence of light

ORDER OF REACTION :
It is defined as the sum of the exponents (powers) of the molar concentrations of the reaction components
in the experimentally determined rate equations.
If rate  [A]p [B]q [C]r
Rate = k [A]p [B]q [C]r
Order of reaction = p + q + r
The order w.r.t. A, B & C are p, q & r respectively.
For a "Reaction of nth order", the order of the reaction is n and the rate equation (or Rate law) is
rate  [A]n = k [A]n.
MOLECULARITY :
The number of reacting species (atoms, ions or molecules) taking part in an elementary reaction, which
must collide simultaneously in order to bring about a chemical reaction is called molecularity of a reaction.
The reaction can be unimolecular when one reacting species is involved, for example, decomposition of
ammonium nitrite.
NH4NO2  N2 + 2H2O
Bimolecular reactions involve collision between two species, for example, dissociation of hydrogen
iodine.
2HI  H2 + I2
Trimolecular or termolecular reactions involve simultaneous collision between three reacting species, for
example,
2NO + O2  2NO2
Molecularity of a reaction is :
(i) Always a whole number (not zero) and never a fraction.
(ii) The probability that more than three molecules can collide and react simultaneously is very small.
Hence, the molecularity greater than three is not observed.
Thus, from the above discussion we can conclude the following:
(a) Order of a reaction is an experimentally determined quantity. It can be zero and even a fraction
but molecularity cannot be zero or a non integer.
(b) Order is defined to elementary as well as complex reactions whereas molecularity is defined
only for elementary reactions. For complex reaction molecularity has no meaning.
(c) For an elementary reaction order and molecularity are same.
ZERO ORDER REACTIONS

Consider of general reaction.
nA  products
Rate = k [A]°
[A]t = [A]0 – kt.
Characteristics of zero order reactions:
(i) Concentration of reactant decreases linearly with time.
(ii) Units of k are mol l–1 time–1.
[A ]0
(iii) Time required for the 100% completion of reaction is
k

[ A ]0
(iv) t1/2 =
2k
(v) Zero order reaction must be complex reaction
(vi) Graph related with zero order reactions.
conc. conc. Rate t1/2

[P]
[A]
time time time a
Examples :
(i) h
H2(g) + Cl2 (g)  2HCl (g)
1
(ii) N2O(g) hot
 Pt .
 N2 (g) + O (g)
Surface 2 2
Mo or W
(iii) 2NH3 (g)   N2 + 3H2
surface
(iv) Enzyme catalysed reaction
Enzyme ( E )
Substrate(S)   
 product(P).
FIRST ORDER REACTIONS

Consider a general reaction.
nA  products
at time t = 0 concentration of A = a or [A]0
at time t = t concentration of A = (a – x) or [A]t
Rate  [A]
d[A ] dx
 = k [A] or = k(a – x)
dt dt
Exponential form of 1st order equation is [A]t = [A]0 e  kt

2.303 a
k= log .
t ax
Characteristics of First Order Reaction :
(i) Unit of rate constant is time–1.

0.693
(ii) t1/2 = (Half-life)
k
k
(iii) log (a – x) v/s t is a straight line with slope  .
2.303

(iv) Graph related with first order reactions.
conc. conc. Rate

[P]
[A]
time time time
t1/2 In [A]t
a t
Examples:
(i) Radioactive disintegration is a first order reaction.

H catalysed hydrolysis
(ii) C12H22O11 + H2O       C6H12O6 + C6H12O6.
Inversion
(glucose) (fructose)
(iii) Mineral acid catalyzed hydrolysis of esters.
(iv) Decomposition of H2O2 in aqueous solution.
SECOND ORDER REACTION :

(i) For the given reaction.
nA  products
dx
Differential rate equation = k(a – x )2
dt
1 x 1 1
Integrated rate equation k = . or kt =  .
t a (a  x ) ax a
Is the above rate constant w.r.t. reaction or disappearance.
(ii) For the given reaction.

A + B  products
at time t = 0 a b
at time t = t a–x b–x
dx
differential rate equation =k (a – x) (b – x).
dt
2.303 b( a  x )
Integrated rate equation k = log10
t (a  b ) a (b  x )
Characteristics of Second Order Reaction :

(i) Unit of rate constant L mol–1 time –1.
(ii) t1/2  a–1 (In general t1/2  a(1–n); n = order of reactions).
(iii) 2nd order reaction conforms to first order when one of the reactant is in excess.

t1/2
slope = k
1/[A]
1/[A]0
t 1/a
Examples:
(i) Saponification (hydrolysis of esters catalysed with alkali).
CH3COOC2H5 + NaOH  CH3COONa + C2H5OH
(ii) Hydrogenation of ethane C2H4+ H2 100
 C
 C2H6.
(iii) 2 O3  3 O2.
nth ORDER REACTION :

Consider the reaction
nA  Product
1  1 1 
kt = n  1  n 1
  n  1, n = order]
 a  x  a n 1 
1  2 n 1  1
.
t1/2 = k ( n  1)  n 1 
 a 
1/[A]
n–1 t1/2
slope = (n – 1)k
n–1
1/[A]0
t 1/a
n–1
METHODS OF DETERMINATION OF ORDER OF REACTIONS :

A few methods commonly used are given below :
1. Hit & Trial Method : It is method of using integrated rate equations, where the experimental
values of a, x & t are put into these equations. One which gives a constant value of k for different
sets of a, x & t correspond to the order of the reaction.
2. Graphical Method :
(i) A plot of log (a – x) versus 't' gives a straight line for the First order reaction.
(ii) A plot of (a – x)– (n–1) versus 't' gives a straight line for any reaction of the order n
except n = 1.
3. Half Life Method : The half life of nth order reaction is given by t1/2  1/an–1
By experimental observation of the dependence of half life on initial concentration we can determine
log( t1 / 2 ) 2  log( t1 / 2 )1
n, the order of reaction. n = 1 + .
log( a 0 )1  log(a 0 ) 2

4. Initial rate method. Initial rate method is used to determine the order or reaction in cases
where more than one reactant is used. It involves the determination of the order of different
reactants separately. A series of experiments are performed in which concentration of one particular
reactant is varied whereas conc. of other reactants are kept constant. In each experiment the
initial rate is determined from the plot of conc. vs. time, e.g., if conc. of A is doubled, and initial
rate of reaction is also doubled, order of reaction w.r.t A is 1.
CALCULATION OF FIRST ORDER RATE CONSTANT USING DIFFERENT PARAMETERS
(I) In terms of pressure
A(g)  B (g) + C(g)
2.303 P0
k= log
t 2 P0  PT
where
P0 = Initial partial pressure of A
PT = Total pressure of gaseous system at time 't'
(II) Decomposition of H2O2 in aqueous solution (In terms of volume of reagent KMnO4 required
in titration against H2O2 ).
H2O2  H2O + O2
2.303 V
k= log 0
t V1
where
V0 = Volume of KMnO4 required in titration of H2O2 sample taken initially
Vt = Volume of KMnO4 required in titration of same volume of H2O2 sample at time 't'.
(III) Acid catalysed hydrolysis of ester( In terms of volume of reagent NaOH required in titration)

CH3COOC2H5 + H2O H CH3COOH + C2H5OH
NaOH reacts with H+ and CH3COOH.
2.303  V  V0 
k= log 
t  V  Vt 
where
V0 = volume of NaOH required in titration when reacted with H+ (at start)
Vt = volume of NaOH required in titration when reacted with H+ and CH3COOH at time 't'.
V = volume of NaOH required in titration when reaction is completed
(IV) Inversion of cane sugar (In terms of angle of rotation)

H catalysed hydrolysis
C12H22O11 + H2O       C6H12O6 + C6H12O6.
Inversion
(glucose) (fructose)
2.303  r0  r 
k= log 
t  rt  r 
where
r0 = initial angle of rotation of the sample
rt = angle of rotation after time t
r= angle of rotation after completion of reaction

(V) Bacterial Growth:
1 ax
lnk=
t a
THRESHOLD ENERGY AND ACTIVATION ENERGY :
Threshold energy : For a reaction to take place the reacting molecules must colloid together, but
only those collisions, in which colliding molecules possess certain minimum energy
is called threshold energy (ET) or the total minimum energy that reacting species
must possess in order to undergo effective collision to form product molecules
is called threshold energy.
Activation energy : It is extra energy which must be possessed by reactant molecules so that collision
between reactant molecules is effective and leads to formation of product
molecules.
Ea Eb
ET = Threshold energy
Ea = Activation energy of forward reaction
Energy
Eb= activation energy of backward reaction ET
Reactants
P1 = Potential energy of reactants Product
P1 P2
P2 = Potential energy of products
Reaction Co-ordinates
Activated complex. It is formed between reacting molecules which is highly unstable and readily changes
into product.
Hreact. = Ea – Eb
INFLUENCE OF TEMPERATURE ON REACTION RATES :
Temperature coefficient :
The temperature coefficient of a chemical reaction is defined as the ratio of the reaction rates at two
temperatures differing by 10°C. Its value usually lies between 2 & 3.
k t 10
Temperature coefficient = .
kt
If no temperature is specified in T.C. then it can be taken as 25°C
Arrhenius Equation :
A quantitative relationship was proposed by Arrhenius
k = A. e–Ea/RT
where
k = rate constant ; A = frequency factor (or pre – exponential factor);
R = gas constant ; T = Temperature (kelvin) ; Ea =Activation energy.
k2 Ea  1 1 
log    
k1 2.303 R  T1 T2 
Graphical representations are :

RADIOACTIVITY :
* The phenomenon of spontaneous disintegration of nuclei of unstable atoms is defined as radioactivity.
* Generally it is exhibited by atoms with A>192 and Z>82
* It was discovered by Henry Becqurel
* Lead isotope is the stable end product of any natural radioactive series
* Radio activity is a nuclear process and not an atomic process
* Radioactivity is not associated with the electron configuration of the atom.
* If N is the number of radioactive nuclei present in a sample at a given instant of time, then the
rate of decay at that instant is proportional to N i.e.,
dN
  N
dt
* If N0 is the number of radioactive nuclei at time t = 0, then the number of radioactive nuclei at a
later time t is given by , N  N 0 e  t
* The nuclei of unstable atoms decay spontaneously emitting  , particles and rays
* Radioactivity remains unaffected due to the physical and chemical changes of the material.
* Radioactivity obeys the law of probability i.e it is uncertain that when a particular atom will decay.
CHARACTERISTICS OF ,  AND  RAYS
S.No Property  -Particles  -Particles  -rays

1. Nature and value Positive and double of the Negative and equal Uncharged
of charge charge of the proton to the charge of (Neutral)
19
electron 1.6 10 C
2. Nature of particle Doubly ionized helium atom (2 Electron (or) Electromagnetic

protons and 2 neutrons) positron waves
3. Mass Four times the mass of the Eq ual to the mass of Mass less
proton electron
4 1.67 10 27
kg  9.11031 kg
4. Specific charge 3.2 1019 1.7 1011 Ckg 1 Uncharged and
q = 4.79 × 10 7 mass less
4 1.67 1027
m
5. Explained by Tunnel effect Neutrino hypothesis Transitions of
nuclei into the
ground energy
level after  and
 decay
6. Effect of electric Deflected by electric and Deflected by electric Unaffected
and magnetic magnetic fields and magnetic fields
fields

7. Penetrating 1 100 10000
power
8. Ionizing power 100000 100 1
9. Velocity Less than the velocity of Approximately equal 3 108 m / s

light to the velocity of
7 7 1 light
1.4 10 m / s to 2.2 10 ms 
10. Mutual interaction Produce heat Produce heat Produce the
with matter phenomenon of
Photoelectric
effect, Compton
effect, Pair
production
SODDY-FAJAAN'S LAWS :
(a) During an  -decay, mass number decreases by 4 units and atomic number by 2 units.
  ray
X ZA   YZA24  E
Daughter nucleus will occupy two positions before that of parent nucleus, in periodic table.
(b) During  -decay mass number of the atom will not change and atomic number increases by 1 unit
  ray
X ZA   YZA1
Daughter nucleus will occupy one position on the right of that of parent nucleus in periodic table
(c) During  -decay, the mass number and atomic number of the nucleus remain unchanged
  ray
X ZA   YZA  E
(d) Emission of  -particle means loss of two protons and two neutrons
(e) Emission of  -particle means loss of an electron.
(f) Emission of a  -ray means no change in charge and mass, but only energy changes
ACTIVITY (A)
(a) The number of atoms of any material decaying per second is defined as the activity of that material.
(b) Its value depends on the quantity and nature of that material.
(c) Units of activity –
fundamental unit – disintegrations per second i.e., Bq
1Bq =1disintegration/s
(d) Practical units: curie and rutherford.
1 curie = 3.7  1010 disintegration/second:
1 Rutherford = 106 disintegrations/second.
(e) Formulae of activity
dN 0.693N A m
(i) A    ii  A   N  iii  A0   N 0  iv  A  A0e  t v A 
dt WT
where A0 = maximum initial activity; A= activity after time t,  =decay constant,
NA = Avogadro number , m = mass of material ,
W = atomic weight of material , T = half life of material

RADIOACTIVE SERIES :
If parent element is unstable then it will dissociate into daughter element & if this daughter element is still
unstable, then it will again dissociate into a new daughter element & process continuous till the formation
of a stable element. Series of element obtained from parent element to the finally stable non-radioactive
element is known as radioactive disintegration series.
(4n + 1) is artificial series & 4n, (4n + 2), (4n + 3) are natural series.
S.No Series Name of the Initial Final Nature of No of

series element element series &
Particles
emittted
1. 4n+2 Uranium series U 238 Pb 206 Natural 8 , 6 
92 82
2. 4n+3 Actinium series U 235 Pb 207 Natural 7 , 4 

92 82
3. 4n Thorium series Th 232 Pb 208 Natural 6 , 4 
90 82
4. 4n+1 Neptunium series Np 237 Bi 209 Artificial 7 , 4

93 83
TO CALCULATE NO OF A-PARTICLES AND B-PARTICLES EMITTED

1
X ZA 
 YZA1  x  y 
x: no of  -particles emitted y: no of  -particles emitted

1
X ZA 
 YZA1  xHe24  ye01
A  A1
1
A  A  4x x
4
 A  A1  1
1
Z  Z  2x  y 1
y  Z  Z  2x y   Z  Z 
 2 
eg : U 92238 
 Pb82206  xHe24  ye01
A  A1 238  206
x   8  particles
4 4
 A  A1  1  238  206 
y   Z  Z       92  82   16  10  6   particles
 2   2 

ISOTOPES, ISOBARS AND ISOTONES :
S.No Isotopes Isobars Isotones
1. The atoms of the same The atoms with mass The atoms with same
elements whose charge number same and charge neutron number but A and
number (Z) is same but mass number different are known Z are different are known
number is different are known as isobars. as isotones
as isotopes.
2. Chemical properties are same Chemical properties are Chemical properties are
different different
3. Number of electrons is same Number of electrons is Number of electrons is
different different
4. Occupy same place in periodic Occupy different places in Occupy different places in
table periodic table periodic table.
5. Example O16 ,8 O17 ,8 O18 H 3 and He3 Li 7 and Be8
8 1 2 3 4
1 H 1 ,1 H 2 ,1 H 3 6 C14 and 7 N 14 1 H 2 and 2 He3

10 Ne 20 ,10 Ne21 ,10 Ne22 8 O17 and 9 F 17 1 H 3 and 2 He 4
USES OF RADIOACTIVE ISOTOPES :

(a) In Medicine :
(i) For testing blood chromium-51
(ii) For testing blood circulation-Sodium-24
(iii) For detecting brain tumor-Radio mercury-203
(iv) For detecting fault in thyroid gland-Ratio iodine-131
(v) For cancer-Cobalt-60
(vi) For blood-Gold-189
(vii) For skin diseases-Phosphorous-31
(b) In Archaeology :
(i) For determining age of archaeological sample (Carbon dating) - C14
(ii) For determining age of meteorites - K 40
(iii) For determining age of earth-Land isotopes
(c) In Agriculture :
(i) For protecting potato crop from earthworm – Cobalt-60
(ii) For artificial rains AgI
(iii) As fertilizers-Phosphorous-32
(d) As tracers :
Very small quantity of radio isotopes present in a mixture is known as tracer . Tracer technique
is used for studying biochemical reactions in trees and animals.
(e) In industries :
(i) For detecting leakage in oil or water pipe lines.
(ii) For testing machine parts
(f) In research :
(i) In the study of carbon-nitrogen cycle.
(ii) For determining the age of planets

SOLVED EXAMPLES
Ex.1 The half time of first order decomposition of nitramide is 2.1 hour at 15°C.
NH2NO2(s)  N2O(g) + H2O(l)
If 6.2 g of NH2NO2 is allowed to decompose, calculate
(a) time taken for NH2NO2 to decompose 99% and
(b) volume of dry N2O produced at this point measured at STP.
Sol.
2.303 [A]0
For a first-order reaction, rate constant expression is k = log
t [A]t
6.2
Initial moles of nitramide =  0.1
62
2.303  2.1 0.1
t log  13.95 hours
0.693 0.001
Since, the decomposition is 99 %, so 99 % of the initial moles of NH2NO2 would be converted
to N2O.
0.1 99
Moles of N2O =
100
0.1 99  22.4
Volume of N2O at STP =  2.217 litre .
100
Ex.2 A drug becomes ineffective after 30 % decomposition. The original concentration of a sample
was 5mg/mL which becomes 4.2 mg/mL during 20 months. Assuming the decomposition of first
order , calculate the expiry time of the drug in months. What is the half life of the product?
2.303  a 
Sol. k = log  
t a  x 
2.303  5 
= log10  
20  4. 2 
= 0.00872 min–1
Expiry time 't' may be calculated as
2.303 a 2.303 100
k= log10 0.00872 = log10
t ax t 70
0.693
t = 40.9  41 months t1/2 = = 79.4 months
0.00872
Ex.3 A first order reaction is 20 % completed in 10 minutes. Calculate the time taken for the reaction to go
to 80 % completion.
Sol. Applying first order equation,
2.303 100 2.303 100
k= log10 = log10 = 0.0223 min–1
t (100  20) 10 80
Again applying first order equation,
2.303 100 2.303 100
t= log10 = log10 = 72.18
k (100  80) 0.0223 20

Ex.4 For decomposition of N2O5 in CCl4 solution at 320 K
2N2O5  4NO2 + O2
show that the reaction is of first order and also calculate the rate constant:
Time in minutes 10 15 20 25 
Volume of O2 evolved (in ml) 6.30 8.95 11.40 13.50 34.75
Sol.
If the reaction is of first order, it must obey the equation
2.303 a
k log
t (a  x)
In the above reaction, NO2 remains in solution and oxygen is liberated and collected at different
intervals of time.
Therefore , Vt  x V  a
Substituting these values in the first order equation
2.303 a 2.303 V
k log  log
t ax t V  Vt
2.303 V
Time Vt V – Vt k log
t V  Vt
2.303 34.75
10 6.30 34.75 – 6.30 = 28.45 k log  0.0198
10 28.45
2.303 34.75
15 8.95 34.75 – 8.95 = 25.80 k log  0.0198
15 25.80
2.303 34.75
20 11.40 34.75 – 11.40 = 23.35 k log  0.0198
200 23.35
2.303 34.75
25 13.50 34.75 – 13.50 = 21.25 k log  0.0198
25 21.25
Since the value of k comes out to be constant the reaction, therefore, is of first order. The average
value of rate constant is 0.0198 min–1.
Ex.5 From the following data show that the decomposition of an aqueous solution of hydrogen peroxide
is of first order :
Time (minutes) 0 10 20 30
V (ml) 46.1 29.8 19.6 12.3
where V is the volume of potassium permanganate solution in ml required to decompose a definite
volume of the peroxide solution.
Sol. It is evident from the given data that at zero time, titre value is proportional to the original concentration
of hydrogen peroxide, i.e., a. The titre value at any time t corresponds to undecomposed hydrogen
peroxide, i.e., (a – x).
Substituting the value in the equation
2.303 a
k1  log , we get
t ax
2.303 46.1
(i) k1  log  4.364  10 2
10 29.8
2.303 46.1
(ii) k1  log  4.276  10 2
20 19.6

2.303 46.1
(iii) k1  log  4.404  102
30 12.3
Since k1 comes out to be constant in the two cases, the reaction is a first order one with the average
value of three.
Ex.6 The rate of a reaction triple when temperature changes from 20ºC to 50ºC. Calculate energy of
activation for the reaction (R = 8.314 JK–1 mol–1).
Sol.
The Arrhenius equation is
k2 Ea  T2  T1 
log10 =  
k1 R  2.303  T1T2 
k2
Given = 3 ; R = 8.314 JK–1 mol–1; T1 = 20 + 273 = 293 K
k1
and T2 = 50 + 273 = 323 K
Substituting the given vlues in the Arrhenius equation,.
Ea  323  293 
log103 =
8.314  2.303  323  293 
2.303  8.314  323  293  0.477
Ea =
30
= 28811.8 J mol –1
= 28.8118 kJ mol–1
Ex.7 In Arrhenius equation for a certain reaction, the value of A and Ea (activation energy) are
4 × 1013 sec–1 and 98.6 kJ mol–1 respectively. At what temperature, the reaction will have specific rate
constant 1.1 × 10–3 sec–1 ?
Sol.
According to Arrhenius equation
 E / RT
k = Ae a
Ea
or logek = logeA – logee
RT
Ea
2.303 log10k = 2.303 log10A–
RT
98.6 103
or 2.303 log (1.1 × 10–3) = 2.303 log (4×1013)–
8.314  T
98.6  103
T= K = 311 K
8.314  2.303 16.56

Ex.8 The rate constant is giveny by Arrhenius equation
k = Ae  Ea /RT
Calculate the ratio of the catalysed and uncatalysed rate constant at 25ºC if the nergy of activation
of a catalysed reaxction is 162 kJ and for the uncatalysed reaction the value is 350 kJ.
Sol.
Let kca and kun be the rate constants for catalysed and uncatalysed reactions.
162  103
2.303 log10 kca = 2.303 log10A – ......(i)
RT
350 103
and 2.303 log 10un = 2.303 log10A– ......(ii)
RT
Substracting Eq. (ii) from Eq.(i)
k ca 103
log10 = (350 – 162)
k un 2.303RT
188  103
= = 32.95
2.303  8.314  298
k ca
= 8.88 × 1032
k un
Ex.9 At 407 K the rate constant of a chemical reaction is 9.5 × 10–5s–1 and at 420 K, the rate constant is
1.9 × 10–4s–1. Calculate the frequency factor of the reaction.
Sol.
The Arrhenius equation is,
k2 Ea  T2  T1 
log10 k =  
1 2.303  R  T1T2 
Given k1 = 9.5 × 10–5 s–1; k2 = 1.9 × 10–3 s–1;
R = 8.314 J mol–1K–1;
T1 = 407 K and T2 = 420 K
Substituting the values in Arrhenius equation.
1.9  104 Ea  420  407 
log10 =
9.5  10 5 2.303  8.314  420  407 
Ea = 75782.3 J mol–1
Ea
Applying now log k1 = log A – 2.303 RT
1
75782.3
log 9.5 ×10–5 = log A –
2.303  8.314  407
A 75782.3
or log 5 =
9.5  10 2.303  8.314  407
= 9.7246
A = 5.04 × 105 s–1

Ex.10 The energy of activation for a reaction is 100 kJ mol–1. Presence of a catalyst lowers the energy of
activation by 75%. What will be effect on rate of reaction at 20ºC, other things being equal ?
Sol.
The arrhenius equation is
k = Ae E a / RT
In absence of catalyst, k1 = Ae 100 / RT

In presence of catalyst, k2 = Ae–25/RT
k2 k2 75
So = e 75 / RT or 2.303 log k =
k1 1 RT
k2 75
or 2.303 log =
k1 8.314  10 3  293
k2 75
or log = 3
k1 8.314  10  293  2.303
k2
or = 2.34 × 1013
k1
As the things being equal in presence or absence of a catalyst,
k2 rate in presence of catalyst
=
k1 rate in absence of catalyst
r2 k2
13
i.e., r1 = k1 = 2.34 ×10

EXERCISE – I
Q.1 For a chemical reaction A B, it is found that the rate of reaction doubles when the concentration of A
increases to four times the original value. The order for this reaction is
(A) 2 (B) 1 (C) 1/2 (D) 1/4
dx
Q.2 For a reaction whose rate expression is = k[A]1/2 [B]3/2, the order of reaction will be
dt
(A) 1 (B) 1/2 (C) 3/2 (D) 2
dx
Q.3 For the gaseous reaction 2A + B  C + D, the differential rate law is = k[A].[B]. The volume of the
dt
1
container containing the reaction mixture is reduced to th of the original volume. The rate of reaction
4
will change by
1 1
(A) times (B) times (C) 16 times (D) 8 times
16 8
Q.4 The order of a chemical reaction can be
(A) zero (B) fractional (C) an integer (D) all of the above
Q.5 For a reaction 2A + B  D + E, the following mechanism has been proposed
A + B  C + D (slow)
A + C  E (fast)
The rate law expression is
(A) rate = k[A]2 [B] (B) rate = k[A] [B]
(C) rate = k[A] [C] (D) rate = k[A]2 [B] [C]
Q.6 In the presence of an acid, the initial concentration of cane sugar was reduced from 0.2 M to 0.1 M in 5
hours and then to 0.05 M in 10 hours. The reaction must be of
(A) zero order (B) first order (C) second order (D) fractional order
Q.7 Which of the following expressions is correct for a second order reaction?
(A) t1/2  C0 (B) t1/2  C0–1 (C) t1/2  C0–2 (D) t1/2  C00
Q.8 An increase in the concentration of reactants leads to a change in
(A) enthalpy of a reaction (B) activation energy
(C) collision frequency (D) threshold energy
Q.9 The minimum energy required for a reaction to take place is called
(A) internal energy (B) threshold energy
(C) activation energy (D) free energy
Q.10 The rate constant of a reaction increases with an increase in temperature because
(A) the activation energy increases
(B) the population of activated molecules increases
(C) the activation energy decreases
(D) the population of activated molecules decreases
Q.11 What will be the order of a reaction in which the rate increases by a factor of 4 if the concentration of
the reactants is doubled, and the rate increases by a factor of 9 if the concentration of the reactants is
made three times?
(A) zero order (B) first order (C) second order (D) third order

Q.12 The rate of reaction A + B  Products is given by the equation r = k[A].[B]. If B is taken in excess, the
order of the reaction will be
(A) 2 (B) 1 (C) 0 (D) unpredictable
Q.13 For an endothermic reaction where H represents the enthalpy of the reaction in kJ/mol, the minimum
value for the energy of activation will be
(A) less than H (B) zero (C) more than H (D) equal to H
Q.14 The half life of a first order reaction is 10 min. If the initial amount is 0.08 mols per litre and the concentration
at some instant is 0.01 mol per litre, then t is equal to
(A) 10 min. (B) 30 min. (C) 20 min. (D) 40 min.
Q.15 For a chemical reaction 2x + y  z, the rate of appearence of z is 0.05 mol L–1 per min. The rate of
disappearance of X is
(A) 0.05 mol L–1 per hour (B) 0.05 mol L–1 per min.
(C) 0.10 mol L–1 min–1 (D) 0.25 mol L–1 min–1
Q.16 In the reaction 2A + B  Products, the order with respect to A is 1 and with respect to B
is 2. If the concentration of A is doubled and that of B is halved, the rate of reaction
(A) will be doubled (B) will be halved
(C) will remains unaffected (D) will become four times
Q.17 The rate of reaction between A and B increases by a factor of 100 when the concentration of A is
changed from 0.1 mol L–1 to 1.0 mol L–1. The order of reaction with respect to A is
(A) 10 (B) 1 (C) 3 (D) 2
Q.18 Select the law that corresponds to the data given below for the following reaction
A + B  Products
[A] [B] Initial rate
1. 0.012...0.035......0.1
2. 0.024...0.070......0.8
3. 0.024...0.035......0.1
4. 0.012...0.070......0.8
(A) rate = k[B]3 (B) rate = k[B]4
(C) rate = k[A][B]3 (D) rate = k[A]2[B]2
Q.19 The conversion of A  B follows second order kinetics. If the concentration of A is doubled, the
formation of B increases by a factor of
(A) 1/4 (B) 2 (C) 1/2 (D) 4
Q.20 The rate of a reaction is doubled for every 10°C rise in temperature. The increase in the rate of reaction
when the temperature increases from 10°C to 100°C is
(A) 112 (B) 512 (C) 400 (D) 614
Q.21 For the reaction N2 + 3H2 2NH3, the rate of change of concentration for hydrogen
is –0.3  10 moles per second. The rate of change of concentration of ammonia is
–4
(A) –0.2  10–4 moles per second (B) 0.2  10–4 moles per second
(C) 0.1  10–4 moles per second (D) 0.3  10–4 moles per second

Q.22 A gaseous reaction
1
A2(g)  B(g) + C(g) shows an increase in pressure from 100 mm to 120 mm in 5 minutes. The rate
2
of disappearance of A2 is
(A) 4 mm min–1 (B) 8 mm min–1 (C) 16 mm min–1 (D) 2 mm min–1
Q.23 If the initial concentration is reduced to 1 th in a zero order reaction, the time taken for half the reaction
4
to complete
(A) remains the same (B) becomes 4 times
(C) becomes one-fourth (D) doubles
Q.24 A first order reaction is half completed in 45 minutes. How long will it take for 99.9% of the reaction to
be completed?
(A) 20 h (B) 10 h (C) 7.5 h (D) 5 h
Q.25 A first order reaction is 75% complete after 32 minutes. When was 50% of the reaction completed?
(A) 4 minutes (B) 8 minutes (C) 16 minutes (D) 32 minutes
Q.26 The rate constant for the reaction 2N2O5  4NO2 + O2 is 3.0  10–5 sec–1. If the rate is
2.40  10–5 mol litre–1 sec–1, the concentration of N2O5 is
(A) 1.4 (B) 1.2 (C) 0.04 (D) 0.8
Q.27 The activation energy of a reaction is 58.3 kJ mol–1. The ratio of rate constants at 305 and
300 K temperature is
(A) 1.25 (B) 1.50 (C) 1.75 (D) 2.0 approximately
1
Q.28 The half life for the reaction N2O5  2NO2 + O is 24 hrs at 30°C. If the reaction initiates with 10 g
2 2
of N2O5, how much amount will be left behind after a period of 96 hours?
(A) 1.25 g (B) 0.63 g (C) 1.77 g (D) 0.5 g
Q.29 The activation energy of a reaction is 58.3 kJ mol–1. The ratio of rate constants at 305 and
300 K temperature is
(A) 1.25 (B) 1.50 (C) 1.75 (D) 2.0 approximately
Q.30 Given that radioactive species decays according to exponential law N = N0e–t. The half-life of the
species is :
(A)  (B) 0 (C) /In 2 (D) (In 2)/
Q.31 Which of the following is an isotonic pair ?

40 40 39 40 40
(A) 19 K, 20
Ca (B) 19 K, 20
Ca (C) 18
Ar, 40
20
Ca (D) None of these
Q.32 The number of - and -particle emitted in the nuclear reaction 228 212 are :
90 Th  83 Bi
(A) 8, 1 (B) 4, 7 (C) 3, 7 (D) 4, 1

Q.33 For the reaction A + B  C; starting with different initial concentration of A and B, initial rate of
reaction were determined graphically in four experiments.
–1
S.No. [A]0/M (Initial conc.) [B]0/M (Initial conc.) rate/(M sec )
–3 –2 –3
1 1.6 × 10 5 × 10 10
–3 –2 –3
2 3.2 × 10 5 × 10 4 × 10
–3 –1 –3
3 1.6 × 10 10 2 × 10
–3 –1 –3
4 3.2 × 10 10 8 × 10
Rate law for reaction from above data is
(A) r = k[A]2 [B]2 (B) r = k[A]2 [B] (C) r = k[A] [B]2 (D) r = k[A] [B]
Q.34 For the reaction system 2NO (g) + O2 (g)  2NO2 (g) volume is suddenly reduced to half of its
value by increasing the pressure on it. If the reaction is first order with respect to O2 and second order
with respect to NO, the rate of reaction will
(A) increase to four times of its initial value (B) diminish to one-fourth of its initial value
(C) diminish to one-eight of its initial value (D) increase to eight times of its initial value
Q.35 For a hypothetical reaction,

A + 3B  P H = –2 x kJ/mole of A
& M  2Q + R H = + x kJ/mole of M
If these reactions are carried simultaneously in a reactor such that temperature is not changing. If rate of
disappearance of B is y M sec–1 then rate of formation (in M sec–1) of Q is :
2 3 4 3
(A) y (B) y (C) y (D) y
3 2 3 4
Q.36 75% of afirst order reaction is completed in 30 minutes. What is the time required for 93.75% of the
reaction (in minutes) ?
(A) 45 (B) 120 (C) 90 (D) 60
Q.37 For the reaction, 2NO + Br2  2NOBr; the following mechanism has been given,
NO + Br2 NOBr2
NOBr2 + NO slow   2NOBr
Hence, rate law is :
dx dx dx dx
(A) = [NO]2 [Br2] (B) = [NO][Br2] (C) = [NOBr2][NO] (D) = [Br2]2 [NO]
dt dt dt dt
Q.38 2N2O5  4NO2 + O2 ; If,

d[ N 2 O 5 ]
= k1 [N2O5]
dt
d[ NO 2 ]
= k2 [N2O5]
dt
d[O 2 ]
= k3 [N2O5]
dt
what is the relation between k1, k2 and k3 ?
(A) k1 = k2 = k3 (B) 2k1 = k2 = 4k3 (C) 2k1 = 4k2 = k3 (D) None of these

Q.39 Which one of the following notations shows the product incorrectly ?
242 243
(A) 96 Cm (, 2n ) 97 Bk (B) 10 13
5 B(, n ) 7 N
(C) 14 14
7 N ( n , p) 6 C
28
(D) 14 29
Si(d, n ) 15 P
Q.40 If half-life a substance is 5 years, then the total amount of substance left after 15 years, when initial
amount is 64 grams is :
(A) 16 grams (B) 2 grams (C) 32 grams (D) 8 grams
EXERCISE–II
Q.1 Units of rate constant for the first and zero order reactions in items of molarity, M units are respectively
[AIEEE 2002]
(A) sec–1, M sec–1 (B) sec–1, M (C) M sec–1 , sec–1 (D) M, sec–1
Q.2 The rate law for a reaction between the substances A and B is given by [AIEEE 2003]
Rate = k[A]n[B]m
one doubling the concentration of A and halving the concentration of B, the ratio of the new rate to the
earlier rate of the reaction will be as :
1
(A) (B) (m + n) (C) (n – m) (D) 2(n–m)
2( m  n )
Q.3 The rate reaction for the reaction [AIEEE 2004]
2A + B  C
is found to be rate k[A][B]
the correct statement is relation to this reaction is that the.
(A) unit of k must be s–1
(B) value of k is dependent of the initial cocentration of A and B
(C) rate of formation of C is twice the rate of disappearance of A
(D) t1/2 is a constant
Q.4 In a first order reaction, the concentration of the reactant decreases from 0.8 M to 0.4 M in 15 minutes.
The time taken for the concentration to change from 0.1 M to 0.025 M is : [AIEEE 2004]
(A) 30 min (B) 60 min (C) 7.5 min (D) 15 min
Q.5 Consider an endothermic reaction X  Y with the activation energies Eb and Ef for the backward and
forward reaction respectively. In general, [AIEEE 2005]
(A) Eb < Ef (B) Eb > Ef
(C) Eb = Ef (D) There is no definite relation because Eb and Ef
Q.6 A reaction involving two different reactants can never be : [AIEEE 2005]
(A) Unimolecular reaction (B) First order reaction
(C) Second order reaction (D) Bimolecular reaction
Q.7 Rate of a reaction can be expressed by Arrhenius equation as, k = Ae–E/RT. In this reaction, E represents
(A) The energy above which all the colliding molecules will react [AIEEE 2006]
(B) The energy below which colliding molecules will not react
(C) The total energy of the reacting molecules at a temperature T
(D) The fraction of molecules with energy greater than the activation energy of the reaction

Q.8 Consider the reaction, 2A + B  Products. When concentration of B alone was doubled, the half life
did not change. When the concentration of A alone was doubled, the rate increased by two times. The
unit of rate constant for this reaction is [AIEEE 2007]
(A) s–1 (B) L mol–1 s–1 (C) unitless (D) mol L–1 s–1
Q.9 The rate constnat for the reaction [JEE SCR 2000]
2N2O5  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
Q.10 If I is the intensity of absorbed light and C is the concentration of AB for the photochemical proces
AB + hv  AB*, the rate of formation of AB* is directly proportional to [JEE SCR 2001]
(A) C (B) I (C) I2 (D) CI
Q.11 Consider the chemical reaction, N2(g) + 3H2(g)  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 relationshiop
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
Q.12 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
Q.13 The reaction, X  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]
Q.14 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.
ANSWER KEY
EXERCISE–I
Q.1 C Q.2 D Q.3 C Q.4 D Q.5 B Q.6 B Q.7 B
Q.8 C Q.9 B Q.10 B Q.11 C Q.12 B Q.13 C Q.14 B
Q.15 C Q.16 B Q.17 D Q.18 A Q.19 D Q.20 B Q.21 B
Q.22 B Q.23 D Q.24 C Q.25 C Q.26 D Q.27 B Q.28 B
Q.29 B Q.30 D Q.31 B Q.32 D Q.33 B Q.34 D Q.35 C
Q.36 D Q.37 A Q.38 B Q.39 A Q.40 D
EXERCISE–II
Q.1 A Q.2 D Q.3 B Q.4 A Q.5 A Q.6 A Q.7 B
Q.8 A Q.9 D Q.10 B Q.11 A Q.12 C Q.13 C Q.14 D


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CHEMICAL KINETICS

For reactant rate of reaction   d[ A ]

For product rate of reaction   d[P]

TIME (IN MINUTES)

Chemical Kinetics [36]

Calculation of instantaneous rate of reaction :

Chemical Kinetics [37]

Chemical Kinetics [38]

ZERO ORDER REACTIONS

Chemical Kinetics [39]

conc. conc. Rate t1/2

FIRST ORDER REACTIONS

Exponential form of 1st order equation is [A]t = [A]0 e  kt

Characteristics of First Order Reaction :

(i) Unit of rate constant is time–1.

Chemical Kinetics [40]

conc. conc. Rate

SECOND ORDER REACTION :

(ii) For the given reaction.

Characteristics of Second Order Reaction :

Chemical Kinetics [41]

nth ORDER REACTION :

METHODS OF DETERMINATION OF ORDER OF REACTIONS :

Chemical Kinetics [42]

Chemical Kinetics [43]

Chemical Kinetics [44]

S.No Property  -Particles  -Particles  -rays

2. Nature of particle Doubly ionized helium atom (2 Electron (or) Electromagnetic

Chemical Kinetics [45]

8. Ionizing power 100000 100 1

9. Velocity Less than the velocity of Approximately equal 3 108 m / s

Chemical Kinetics [46]

S.No Series Name of the Initial Final Nature of No of

2. 4n+3 Actinium series U 235 Pb 207 Natural 7 , 4 

4. 4n+1 Neptunium series Np 237 Bi 209 Artificial 7 , 4

TO CALCULATE NO OF A-PARTICLES AND B-PARTICLES EMITTED

x: no of  -particles emitted y: no of  -particles emitted

Chemical Kinetics [47]

1 H 1 ,1 H 2 ,1 H 3 6 C14 and 7 N 14 1 H 2 and 2 He3

USES OF RADIOACTIVE ISOTOPES :

Chemical Kinetics [48]

Chemical Kinetics [49]

Chemical Kinetics [50]

Chemical Kinetics [51]

Chemical Kinetics [52]

In absence of catalyst, k1 = Ae 100 / RT

Chemical Kinetics [53]

Chemical Kinetics [54]

Chemical Kinetics [55]

Q.31 Which of the following is an isotonic pair ?

Chemical Kinetics [56]

Q.35 For a hypothetical reaction,

Q.38 2N2O5  4NO2 + O2 ; If,

Chemical Kinetics [57]

Chemical Kinetics [58]

Chemical Kinetics [59]

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