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Chem Kinetics Notes
Chem Kinetics Notes
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.
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
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)
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
[ 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
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.
[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).
[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.
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.
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
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
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 :
* 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
3. Mass Four times the mass of the Eq ual to the mass of Mass less
proton electron
4 1.67 10 27
kg 9.11031 kg
4. Specific charge 3.2 1019 1.7 1011 Ckg 1 Uncharged and
q = 4.79 × 10 7 mass less
4 1.67 1027
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
Particles
emittted
1. 4n+2 Uranium series U 238 Pb 206 Natural 8 , 6
92 82
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 ye01
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
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 ax 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
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 ax
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
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.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.
1.9 104 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
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
(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.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.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.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.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
(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
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