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Chemical Kinetics

Questions were asked regularly in all the years Mostly questions came from ‘Kinetics of first order reactions and temperature effect on rates of reactions’ Easy and average type questions were asked in last four years. With little practice any question of JEE level can be solved Focus on (i) First order kinetics (ii) Radio activity and (iii) Temperature effect on rates of reactions

**Characteristics of First Order Reaction: The integrated rate expression for first order reaction. k = ln
**

A ( g ) → P0 P0 − x

1 t [A 0 ] [A]

**In terms of Pressure the integrated rate expression for first order reaction
**

At time = 0 At time = t B(g) + C(g) 0 0 x x

Is, k = In

1 t

P0 2P0 − Pt

Unit of Rate constant: (time)-1

General unit: (mole/litre)1-n time-1 n = order of a reaction. Time required for the completion of same fraction of initial concentration is independent of initial concentration. Half life period: Time period in which half of the reaction is completed is known as half - life period. t½ =

λ=

0.693 . k

**The radioactive disintegration follows first order kinetics, thus for any radioactive disintegration
**

2.303 a log t a−x

λ = disintegration constant

**Half-Life of a nth order Reaction: ⇒
**

(2n −1 − 1) = kt1/ 2 (Order n ≠ 1) (n − 1) [A 0 ]n −1

Therefore for a nth order reaction, the half life is inversely related to the initial concentration raised to the power of (n – 1). Arrhenius Equation: In 1889, Arrhenius suggested a simple relationship between the rate constant k for a reaction and the temperature T. i) k = Ae-Ea/RT ii) log k = log A −

Ea 2.303RT

ǁǁǁ͘ƐĂŬƐŚŝĞĚƵĐĂƚŝŽŶ͘ĐŽŵ

A first order reaction is 50% completed in 20 minutes at 27°C and in 5 min at 47°C. 2. It is obvious that … (1) [A]0 = [A] + [B] + [C] The concentration of ‘B’ at any time is given by k1 [B] = [ A ]0 k − k {exp(− k1t ) − exp(− k 2 t )} 1 2 … (2) k / k -k 2 k 2 1 Maximum Concentration of B: [B]max = [A] 2 0k 1 k1 1 ln Time taken to reach [B]max is tmax = k1 − k 2 k2 ( ) … (3) …(4) Model Questions 1. it is possible to determine the individual rate constant k1 and k2.ǁǁǁ͘ƐĂŬƐŚŝĞĚƵĐĂƚŝŽŶ͘ĐŽŵ 1 2 a 2 iii) log k = 1 2. Consider the following first order competing reactions: K1 K2 and Y X → A + B → C+D If 50% of the reaction of X was completed when 96% of the reaction of Y was completed. the concentrations of A. ln [ A ]0 = kt = (k1 + k 2 )t [ A ]t Since the rate of formation of products B and C are given by The ratio of concentrations of B and C at any instant will be given by [B] k1 = [C] k 2 Hence. Consecutive or Sequential Reactions Consider the following consecutive reaction: k2 k1 C A → B → Let the initial concentration of A be [A]0 and let after time t.06 (B) 0.14 kJ/mol (C) 11.85 kJ/mol (B) 55. Equation (i) can be integrated to get the integrate rate expression. [B] and [C]. B and C be [A].1 (D) 4. the ratio of their rate constants (k2/k1) is (A) 4. respectively.65 1 D 2.97 kJ/mol (D) 6.215 (C) 1.303R T1T2 k E T −T Kinetics of Some Complex Reactions: 1.(i) The first-order rate constant k is the sum of the two rate constants k1 and k2 of the two side reactions. The energy of activation of the reaction is (A) 43. Side or Concurrent Elementary Reactions K2 K1 C ← A →B The differential rate expressions for the above two reactions are r1 = d[B] = k1 [ A ] dt r2 = d[C] = k 2 [A] dt The overall-rate of disappearance of A is given as r1 + r2 = − d[ A ] = (k1 + k 2 )[ A ] = k[ A ] dt ----.65 kJ/mol 2 B ǁǁǁ͘ƐĂŬƐŚŝĞĚƵĐĂƚŝŽŶ͘ĐŽŵ . if the ratio of B and C is determined at any instant (or at the end of the experiment) and k1 + k2 is determined from the kinetic study.

A fresh sample contains the nuclides of B to be eight time that of A. Two radioactive nuclides A and B have half lives of 50 min and 10 min respectively.ǁǁǁ͘ƐĂŬƐŚŝĞĚƵĐĂƚŝŽŶ͘ĐŽŵ 3. How much time should elapse so that the number of nuclides of A becomes double of B (A) 30 (B) 40 (C) 50 (D) None C 3 ǁǁǁ͘ƐĂŬƐŚŝĞĚƵĐĂƚŝŽŶ͘ĐŽŵ .

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