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CHEMICAL KINETICS

1)

**Consider the reaction 2A + B
**

2C. 2)

Suppose that at a particular moment

during the reaction, rate of

disappearance of A is 0.076 M/s,

i) What is the rate of formation of C ?

ii) What is the rate of consumption of B ?

iii)What is the rate of the reaction ?

Given :

Rate of disappearance = 0.076 M/s

i)

To Find :

i) Rate of formation of C

ii) Rate of consumption of B

ii)

iii) Rate of reaction

Solution :

–d[A]

dt

= 0.076 M/s.

Rate of disappearance of A =

i) Rate of formation of C

=

+d[C]

dt

Rate of disappearance of A

= Rate of formation C

= 0.076 M/s.

ii) Rate of consumption of B =

–d[A]

dt

d[B]

= –2

=

dt

–d[B]

dt

∴

d[B ]

dt

= –

d[I– ]

dt

–

d[S2 O82 – ]

?

dt

?

d[SO 2–

4 ]

= 2.2 × 10–2 M/S

dt

To Find :

–

–d[I – ] d[S 2 O 2–

8 ] d[I 3 ]

,

,

dt

dt

dt

Solution :

d[SO 2–

4 ]

= 2.2 × 10–2 M/s

dt

∴

2[SO2–4] =

1 d[SO 2–

4 ]

2

dt

Rate of formation of SO 2–

4

1

× 2.2 × 10–2

2

= 1.1 × 10–2 M/s

=

1 –d[A]

2 dt

1 –d[C]

2 dt

–

d[I3– ]

at the same time ?

dt

Given :

= 0.038

–d[B]

=

dt

d[SO2–

4 ]

= 2.2 × 10–2 M/s.

dt

What are the values of

iii)

1 –d[A]

2 dt

–0.076

=

2

iii) Rate of reaction = –

=

–d[B]

dt

**Consider the reaction
**

3I(aq) + S2O2–

I–3(aq) + 2SO2–

8(aq)

4(aq)

At a particular time t,

i)

Rate of disappearance = –

=

1 –d[I – ]

3 dt

1 d[S2O2–

8 ]

2

dt

1

[0.076] = 0.038

2

Chemical Kinetics

24 = k[0.320)y .320 ) x y x y k2 ( 0..20 When the concentration of A and B is What is the rate constant and order of doubled the rate is doubled the reaction ? ∴ 2R = k[2[A]x][2[B]y] Thus.(ii) When the concentration of A is doubled 2(0...160 ) ( 0.160 0..160 ) x y x y k2 ( 0.160] k = 6. the rate law for the three cases can Solution : Let the rate law of the reaction be given be written as x y by 2(0.160] 0.05 0.488 2 ( 0.12 ) – = – ∴ ii) 1 d[ I ] 3 dt = 1.1 × 10–2M/s d[I – ] = 3.244) 2(0.3 0.06 ) = 2 ( 0.24 ) Consider the reaction 2C + D.(iii) rate is doubled Dividing equation (iii) by (ii) Chemical Kinetics . Find the rate law from the following data [B] /M ra te/Ms–1 [A] /M Write the rate law of reaction.(i) x y R = k[A]x[B]y 2(0.1 × 10–2M/s dt Rate of formation of [I–3] = iii) = ∴ 3) d[I 3– ] dt d[I3– ] dt = 1 d[SO 2– 4 ] 2 dt = 1.15 Solution : Let the rate of the reaction be given by 0..244 0..488]2 [0.160 0.488) 2(0...30 R = k[A]x[B]y 0..238] [0.12 ) ( 0.320 0.24) = k 2(0.. From the ∴ 2A + 2B following data.320 ) y ( 0.20 1..6 0.488 ) 2 ( 0..24 0...06 ) = = k2 ( 0.24 = k[0.160) . calculate the order and ∴ rate constant of the reaction. 0. ∴ –1 ∴ [B]0 /M r0 /Ms [A]0 /M 0.06 ) ∴ ∴ ∴ 4) k2 ( 0.12) = k 2(0.244 ) 2 ( 0.06) = k 2(0.160 ) 4 = 2x x = 2 Thus the order of reaction with respect to A is second order Rate = k [A]2 [B] Order of reaction : A is second order and B is first order Over all order of reaction is third order R = k[A]2 [B] 0.160 ) y 2 = 2y y = 1 Thus the order of reaction with respect to B is first order Dividing equation (i) by (ii) 2 ( 0.. 2 ∴ Rate of disappearance of [I–] 2 ( 0.160) .3 × 10–2M/s ∴ dt ] Rate of disappearance of [S2O2– 8 ∴ 2– 2– ∴ 1 d[SO 4 ] d[S 2 O 8 ] = – = 2 dt dt Rate of disappearance = – d[S 2 O 2– 8 ] = 1..6 0.244 ) 2 ( 0.244 0.1 × 10–2M/s 0.05 0.244 ) 2 ( 0.244)x 2(0.12 ( 0..30 M–2s–1 For the reaction 2A + 2B products.06 0.

If the concentration of A2 and B are halved.30 ) ∴ ∴ x = k 2 ( 0...16 × 10–2 M – = k[C2 H4Br2][I ] k[0..3)x 2(0..12M][0. What is the order of the reaction ? Write the rate law. Rate2 = Rate 1 8 y Chemical Kinetics .05 ) To Find : Rate constant (k) Solution : Rate of Reaction ∴ 1..04139 –2 – log 2.1 × 10–4 M/s Concentration of C2H4Br = 0.20) .1 × 10–4 M /s =? 1..20 ) 2 ( 0.1 × 10–4 /s 2.1 = 0. Given : Rate of reaction (R) = 1.05] 6) 0.05)y x y 2(1.. the rate increases by the factor of 2.20 ) y y 2 ( 0.1 × 10–4 M/s = ∴ ∴ 0.30 ) ∴ ∴ = ∴ ∴ ∴ 5) x y k 2 ( 0.12 M and 0..5.09 × 10–3 M–1 s–1 k = 5..18 M respectively..7070 ( ) = Al 1. A2 + B products. If the concentration of A is increased by a factor of 2..6) 2(0.18 – Rate = k[C2H4Br2][I ] 1.. Solution : A2 + B products Let the rate of reaction be x y Rate1 = k[A2] [B] If the concentration of A 2 and B are halved the new rate of reaction is x A B Rate2 = k 2 2 2 Also.6 ) 2 ( 0.0216M 2 1.5. the rate of the reaction decreases by the factor of 8. The rate of the reaction is found to be 1.1 × 10–4 M/s when the concentrations – of C2H4Br2 and I are 0.6 ) 2 ( 0. the rate law for three cases can be written as 2(0.15 = k[0.16 × 10–2 M = Al log 1. 3 ∴ 2R = k[A]x [B]y Thus.6 ) 2 ( 0..015] k = 10 M–1s–1 The rate law for the reaction – C2H4 + 2B C2H4Br2 + 3I – – – r + I3 is the rate = k[C2H4Br2][I ].1 × 10–3 M–1 s–1 Consider the reaction.3 ) 2 ( 0.15) = k 2(0.05 ) 4 = 4 y = 1 Thus the order of reaction with respect to B is first order Dividing equation (ii) by (i) 2 ( 0.1 × 10–4 / s 2.05)y ..15 ) ∴ k 2 ( 0.7070 × 10–2 –1 = 5.12 M – Concentration of I = 0.16 = 0.18M] k[0.15 = k[0.20) = k 2(0..05 ) x y x y k 2 ( 0.6)x 2(0. Calculate the rate constant of the reaction.(i) .0216M2 ] = k = k k = 2 = 2x x = 1 Thus the order of reaction with respect to A is first order Over all order of reaction is second order Rate = k[A] [B] ∴ Substituting the values 0.(ii) 2(0.09 × 10 × 10–2 = 5.3] [0.3344 × 10 1..(iii) Dividing equation (iii) by (ii) 2 ( 1.30) = k 2(0.1 × 10–4 M/s = ∴ 1..

5 [Rate1] x x ∴ ∴ ∴ Consider the reaction C+D products. What is the order of the reaction ? Write the rate law.5)x x = 1 A is first order reaction Substituting the value of x in (i) ∴ 1+y = 3 y = 3–1 y = 2. The rate of the reaction is tripled when concentration of D is tripled. = x y rate1 k [ C] [D] x+ y 1 1 = 2 2 x+y = 3 . Rate3 = k[(2.5)(A2)x][B]y Rate3 = 2. And Rate of reaction = k[C]2[D] . Solution : C+D products The rate law of the reaction is of the form x y Rate1 = k[C] [D] i) If the concentration of [C] is doubled the x y new rate of law is rate2 = k2[C] [D] ∴ ∴ ii) y k ( 2.5 )( A 2 ) [ B] = x y k [A 2 ] [ B] = ∴ ∴ ∴ ∴ x k2 [ C ] D y rate 2 Hence. (i) Also.5 ) [A 2 ] [ B ] x y k [A 2 ] [ B ] 2.5 = (2. 4 ∴ 7) Rate 2 Rate 1 = Rate 2 Rate 1 A B k 2 2 2 = y k[A 2 ]x [ B ] 1 8 x x y y x y 1 1 k [A 2 ] [ B] 2 2 = y k[A 2 ]x [ B] ∴ 1 = 2 1 8 3 ∴ ∴ ∴ x+ y Rate 3 Rate 1 = 2.... The rate of the reaction increases by a factor of 4 when concentration of C is doubled. If the concentration of D is tripled the new rate law is x y rate3 = k[C] [3[D] ] rate 3 = 3[Rate1] rate 3 kC x × 3y × D y Therefore rate = 1 kC x × D y rate3 rate1 = 3 3rate 1 rate 1 = 3 y y y = 1 Hence D is first order reaction..5 Rate 3 Rate 1 y x k ( 2. Order of Reaction is third order. ∴ B is second order reaction The overall reaction is third order. Rate = k[A2][B]2 ∴ ∴ Chemical Kinetics rate 2 = 2x rate1 ∴ But when C is doubled the reaction rate increases four times of rate1 is rate2 = 4(rate1) 4 = 2x x = 2 Hence C is of second order.

42 M–2 s–1 To Find : Rate (R) Formula : Rate = k[H][NO]2 Solution : Rate = k[H][NO]2 Rate = 0. What is the half life of the reaction ? Given : The reaction 2H2(g) + 2NO(g) 2H2O(g) + N2(g) is first +H2O C6H12O6 + C6H12O6 C12H22O11 order in H2 and second order in NO.025 M]2 ∴ Rate = 0. t = 38 minutes Calculate the rate when [H2] = 0. The rate constant of the reaction at a Sucrose Glucose Fructose certain temperature is 0.015 × (0.11439) k = 1.015 M Concentration of ClO2 = 0. Given : Rate of reaction = 4. Calculate the rate constant of the reaction.5950 = = = Rate = Al(5. 5 8) The reaction F2(g) + 2ClO2(g) 2FClO2(g) is first order in each of the reactants.42 × 0.75 × 10 –4 M 2 4.97 × 10–6 M/s 10) In acidic solution sucrose is converted to a mixture of glucose and fructose in pseudo first order reaction.75 × 10–4 M2 ∴ k = k = = 4.42 M–2 s–1 [0.88 × 10–4 M/s = k[0.015M][0.75 = 0.015 M Chemical Kinetics .000375 M2 ∴ 4.88 × 10 –4 M /s 3.3 M–1 S–1 9) Concentration of NO = 0.88 × 10–4 M/s when [F2] = 0.75 × 10 –4 = AL log 4.6232 Al log 42 +log 15 = 1.42 M –2 s –1 .935 × 105 × 10–11 3. The rate of the reaction is 4.25 M.025 M Rate constant (k) = 0.025 M.11439 = AL(0.025)2 = 42 × 10–2 × 15 × 10–3 × (25 × 10–3)2 = 42 × 15 × (25)2 × [10–2 × 10–3 × 10–6] = 42 × 15 × (25)2 × 10–11 ∴ = 1.13979 × 2 5.015 M][0.88 × 10–4 M/s = k 0.88 × 10–4 M/s Concentration of F2 = 0.025 M To Find : Rate constant (k) Formula : Rate of reaction = k[F2][ClO2 ] Solution : Rate of reaction = k[F2][ClO2 ] ∴ 4. [A]t = 8 mmol L–1 Given : To Find : H2 is first order = [H] Half life (t1/2) NO is second order = [NO]2 Concentration of H2 = 0.935 × 10–6 3.015 M and [ClO2 ] = 0...5950) × 10–11 3.88 × 10–4 M/s = k × 3. It has been found that the concentration of sucrose decreased from 20 mmol L –1 to 8 mmol L–1 in 38 minutes.68842 – log 3.88 × 10–4 3.015 M [A]0 = 20 mmol L–1 and [NO] = 0.025 M] ∴ 4.88 = 0.1760 × 10–11 +2 log 25 = 1.57403 0.

0969 t ∴ t = 2.303 log 10 2. After 12. [A ]0 2.0969 0.024278 min–1 ∴ 0.7 hours = 102 min ∴ [A]0 = 100 [A] t = 100 – 20 = 80 12) To Find : time (t) Formula : i) k = 0..9869 3.0068 = 2. k = t 1/2 ∴ 0.8325 1.3622 2.3485 1.5160 = Al(1. How long will it take for 20% of the reactant to disappear ? Given : t1/2 = 1.809 min t = 32.303 log 10 t [A ]t i) k = 0.303 × 0.5160) = 32.303 20 log 10 38 8 ∴ 0.25 t ∴ 0.0068 = 2.5 k = 38 k = 0.809 min The gaseous reaction A2 2A is first order in A2.06 log 2.693 t1 / 2 ii) k = [A ]0 2.693 t1 / 2 = 0. t1/2 = ∴ ∴ 11) The half life of a first order reaction is 1.0068 = [ 100] 2.024 = t 1/2 t 0.303 × 0.0068.693 Now.303 log 10 1.5 k = 0. How long will it take to decompose 90% of A2 ? What is the half life of the reaction ? Given : t = 12.303 log 10 t [A ]t ii) k = 2.0068 k = k = ii) 0.693 102 Solution : i) ∴ ∴ ∴ ∴ = 0.693 0.7 hours. 6 Solution : Formula : i) k = 0.303 log 10 t [ 80] 2.87 min.693 t ii) k = [A ]0 2.024 t1/2 = 28.303 × 969 × 10 –4 68 × 10 –4 = Al log 2.3 min At = 65 = 100 A0 .693 0.303 log 10 t [A ]t Chemical Kinetics = 2.303 log 10 t [A ]t [A ]0 2.3 minutes 65% of A2 remains undecomposed.303 = +log 969 = – log 68 = 0..

538 12.8 min = 19.01] Chemical Kinetics .8 × 10 –4 × 1200 ∴ = 2.693 0.8 × 10–4s–1 [A0 ] = 0.04 = 0.303 t = 0.0177 M ii) 6.303 2. 7 To Find : half life (t1/2) Formula : i) ii) k = k = [A]0 2.035 = 0.187 12.04 [A t ] 0.303 log 10 k = t [A]t 6. what is its molarity after 20 minutes ? How long will it take for 25% of the reactant to react ? Given : k = 6.04] [A t ] [0.3 0.035 = t ∴ Antilog (0.04 [A t ] 0.693 t1 2 ∴ A t = 0.303 log 10 t [A]t ∴ k = 2.035 ∴ t1 2 = ∴ t1 2 = 19.04] log 10 1200 [A t ] log [0.8 × 10–4s–1.303 log101.693 t1 2 0.8 ∴ At = ii) k ∴ ∴ i) ∴ ∴ ∴ ∴ ∴ ∴ k = = 0.035 t = 65. If the initial concentration of the reactant is 0.261 = 2.04 M.3545 = 2.8 × 10–4 = 2.303 100 log 10 12.693 t 1/2 Solution : k = [A]0 2.303 k = 0.04 2.261 2.3545) = 2.8 min 13) The rate constant of a first order reaction is 6.04 log 10 t 0.303 log 10 t [A]t 0. To Find : Molarity (M) time (t) Formula : ∴ 2..303 [0.03 [25% of 0.303 0..035 log k = t [A]t Time required for decomposition of 90%of A2 is Solution : A0 = 100 A t = 100 – 90 = 10 = i) 6.04 M t = 20 min = 20 × 60 = 1200 sec.303 [100] log 10 0.3 [A]0 2.303 0.035 = ×1 t ∴ 2.303 × 0.04] log [A ] t 0.035 = t [10] ∴ 0.3 65 ∴ k = 2.303 log10 10 0.8 × 10–4 [A]0 2.

5 h ? Given : k = 3.303 × 124 × 10–3 6.303 × 3521 × 10–1 3.4147) × 10–1 2598. = 1.836 min 259.01 = 0.8 1.8 × 10–4 = AL(1.12 × 10–3 = 2.303 log t [A]t Solution : log10 1.303 log10 1.5466 10 3.12 = Al log 10 2.3521 t 6.12 × 10–3 2..12 × 10 –3 2.303 [0.3622 + log 124 = 2.98 × 101 = 420 sec [A]0 2.3622 +log 3521 = 3.364 259.25] t ∴ 3.045 M At = 0.3333 t [∵ 0.303 = 0.6231 t Formula : ∴ 1 t = t = = 420 = 60 = 7 min = 7 min.8 × 10–4 t t t = = = = 2.02 M ii) To Find : i) t ii) [At] = 3.4556 × 10 1 = 0.12 = 0.333 2.303 × 0.3521 3.303 = 0.6231) × 10 = 41.02 M if the initial concentration of the reactant is 0.303 log 10 t [A]t .4941 3.303 × 0.5 hrs = 1.12 × 10–3 = 2.4147 t t = = = = Al (3.0934 10 2.02] ∴ 3.8 × 10 –4 × 101 = Al log 10 2.303 × 3521 × 10–4 3.12 × 10–3 = 2.045] log 10 t [0.8 × 10–4 t ∴ t k = [A]0 2.12 × 10 –3 2. 14) The rate constant of a certain first order reaction is 3.3521 [A]0 2..124 2.5 × 60 = 90 min k = Chemical Kinetics 2.303 × 0.8325 – log 10 6.12 × 10–3 min–1 ∴ A0 = 0.303 6.9088 × 10–1 – log 10 3.12 × 10–3 min–1 i) How many minute does it take for the reactant concentration to drop to 0.303 log t [A]t i) k = ∴ 3.03] 2.303 log10[2.04 – 0.303 × 0.045 M ? ii) What is the molarity of the reactant after 1. 8 ∴ ∴ ∴ ∴ 6.839 min.

.

.

9989 k1 × 1.4361 3010 × 10 × 2.314 Ea = 1. 11 = = = = = Al (0.73 × 10–5 log = k1 2.3622 +log 8.7394 1.05 × 10 = Al log 334.21 54.314 610 × 600 E a 313 – 303 2k 1 log10 = 2.303 × 8.303 × 8.6783 Chemical Kinetics . How many times larger is the rate constant at 610 K than the rate constant at 600 K ? Given : Ea = 334.314 334.05 = 0. Ea T2 – T1 k ∴ k2 = 2k1 log10 2 = 2.303 × 8.9198 4.9603 – log 1.7605 = Al 2.2820 × 10 4.314 Ea × 1.303 × 8.4 × 103 610 – 600 Solution : × 2.9198 = Al log 3010 = 3.303 = 0.3622 = 1.73 = 0..3010 × 2.30081) = = = = 1.5242 –4 +log 2.314 = 0.2820 +log 8.MAHESH TUTORIALS SCIENCE ∴ k2 k1 ∴ ∴ ∴ k2 k2 k2 18) .0211 –2 –1.kJ mol–1.4785 +log 2.7 × 10–5 × 1.05 × 10 –4 2.314 = 0.303R 313 × 303 334.314 0.4 = 2.4 × 10–5 Al (4.73 × 10–5 2.303R T1 T2 k1 To Find : Activation energy Ea Solution : Formula : k2 log10 = Ea T2 – T1 k2 k1 log10 = 2.9603 × 10–2 log 2.7394) 54878.05 × 10 –4 log102 = k2 2.314 ∴ Ea = –4 1. T2 = 610 K To Find : k1 Formula : What is the activation energy for a reaction whose rate constant doubles when temperature changes from 300C to 400 C ? Given : T1 = 300C = 303 K.4 kJ/mol = 334.9989 7.4 × 103 J/mol T1 = 600 K.9989 3.T2 = 400C = 313 K Rate constant doubles when temperature changes from 300C to 400C.878 × 103 kJ/mol 54.303 × 8.4 × 103 × 2.303 × 8.303R T1 T2 k1 334.878 J/mol 19) The activation energy for a certain reaction is 334.303 = 0.4 × 103 k1 = × 2.

.

5 × 105 Ea × 8. T2 = 400 k.7782 88 × 103 298 – T1 2.303R T1 T2 k2 = k1 Ea T2 – T1 2.314 600 × 400 = Ea ∴ ∴ ∴ log10 k2 = k1 Ea T2 – T1 2. log10 T1 = 600 k. Given : Rate1 = 8. at what temperature would this reaction have rate constant of 4 × 10–2 s–1 ? Given : k2 = 0.5 × 10 5 times the rate of the same reaction at 400 K.875061 0.5 × 105 (Rate1).7782 × 19. Solution : To Find : Ea log10 Formula : log10 Ea T2 – T1 k2 = 2.303 × 8.4352 × 10–4 = 5.24 0.298 log10 6 0.303 × 8.314 Jk–1 mol–1.5 + 5 log10 = Ea × 0.15 = 298 K Ea = 88 kJ mol–1 = 88 × 103 J mol–1 k1 = 4 × 10–2 s–1 To Find : Temperature (T2 ) Formula : The rate of a reaction at 600 K is 7.99 × 103 J/mol = 135 kJ/mol.303R T1 T2 k1 log10 7.5 × 10 5 k 1 k1 = Ea 600 – 400 2.303 × 8. Hence.333 × 10 –4 2.298 Chemical Kinetics .314 log10 7. The reaction occurs in the following steps : ∴ N 2O + H 2O i) H2 + 2NO ∴ ii) N 2O + H 2 N 2 + H 2O What is the role of N 2 O in the ∴ mechanism ? Identify the slow step..303R T1 T2 0.4352 × 10 –4 Ea = 134.MAHESH TUTORIALS SCIENCE .314 T1 . If the energy of activation of the reaction is 88 kJ mol–1 . N2 O + H 2O is a slow 24) log10 7. Calculate the energy of activation for the reaction.24 s–1 T2 = 250 C = 25 + 273.147 T1 . 13 ∴ The rate law for the reaction 2H2(g)+ 2NO(g) N2(g)+ 2H2O(g) is given by rate = k[H2] [NO]2.147 0.24 s –1 . H2 + 2NO step.4352 × 10–4 log10 7. The rate constant of a first order reaction at 25 0 C is 0. it is the reaction intermediate. Rate2 = 7.04 = 88 × 103 298 – T1 = 19.303R T1 T2 k1 ∴ Solution : ∴ log10 Ea T2 – T1 k2 = 2.147 88 × 10 3 298 – T1 T1 .5 + 5 × 1 = Ea × 0.298 88 × 103 = 19.298 298 – T1 = T1 . Solution : 2H2(g) + 2NO(g) N2(g)+2H2O(g) Rate = k[H2][NO]2 25) H2 + 2NO N2O + H2O 23) i) ii) N2O + H2 N2 + H2O N 2 O is formed in the first step and consumed in the second step.

2287) × 10–7 = T1 .303 = 0.314 = 0.7481 –4.6 × 10 M–1 s–1 = A A = 9707780.151 1.15K A 1. ∴ Given : T = 5000 C = 500 + 273. What is the frequency factor of the reaction if its energy of activation is 56 kJ mol–1.693 × 10–4 × 298 × = 0.6 × 103 M –1s–1 6067.6 × 103 A 1.1702 A = log10 1.2287 ∴ ∴ 1.298 log 7782 = 3.147 = 1.7481 log 56 – log 2.0504 T1 = ∴ log10 k –1 log10 ∴ ∴ 298 1.15 = 773 K.314 × 773.6 × 103 T1 = 283.363 × 1.6 × 103 M –1s–1 Antilog (3.6 × 103 26) Chemical Kinetics = 56000 A = log10 2.298 1.783 = log10 A 1..783 = log10 3.0504 × T1 = 0.8910 +log 19.314 Jk mol 298 – T1 Al (3.151 = 2.303 × 8. 14 ∴ 298 – T1 7782 × 19.298 – log 88 = 1.3622 Al × 103 +log 8.5779 3.71 × 106 M–1 s–1 3 .9198 +log 773.6 × 103 M–1 s–1.298 ∴ ∴ ∴ ∴ T1 = T1 298 – T1 298 – T1 298 298 = log10A – Ea 2. Ea = 56 kJ mol–1 ∴ = 56 × 103 J mol–1 To Find : Frequency Factor (A) ∴ Formula : k = Ae–Ea / RT ∴ E log10 k = log10A – a RT ∴ ∴ ) Al 4.6 × 103 M –1s–1 = 4.6 × 103 0.8882 4.1702 A × 103 = log10 = 1.9444 3.303RT A Ea = log10 K 2.147 × 10–4 × 10–3 = 88 T1 .MAHESH TUTORIALS SCIENCE .6 × 103 M–1 s–1.2821 298 – T1 5.693 × 10–4 298 – T1 = T1 .303 × 8.783) = A 1. k = 1.050 × T1 = 1.303RT k ( 56 × 103 Jmol –1 ( –1 2.8 M–1 s–1 = 9.0504 ) × 773.7 K The rate constant for a reaction at 5000 C is 1.1731 × 10–7 = ∴ Al T1 .303RT Solution : Ea A = log10 2.

6 × 10 13 s –1 7.8908 = log10 ∴ 7. T = 600 K To Find : Rate constant (k) Formula : A Ea = log10 K 2.303RT Solution : Ea A = log10 2.3622 = log 1.6 × 10 13 s –1 k = 1.314 +log 6 = 1.3802 13 = 0. If the frequency factor of the reaction is 1.0601 1.303 × 8.6 × 10 13 s –1 k = 1.. A = 1.9198 = 0.303 × 8.3201 ∴ ∴ ∴ k2 log10 = k1 ) 250 × 103 – 100 19.314 Jk mol ( 1.7781 240 × 103 11488.303R T1 T2 k2 k1 = ( t 1 / 2 )1 ( t 1 / 2 )2 1.303RT k ∴ 240 × 103 J mol –1 ( ) 2.6 × 1013 s–1.7768 × 10 20 = 2.7768 × 1020 k = 1.6 × 1013 = log ∴Al 10 k 1.6 × 10 13 s –1 k 13 –1 ∴ ∴ Antilog (20.057 × 10–8s–1 28) The half life of a first order reaction is 900 min at 820 K.6 × 1013 s–1.6 × 10 13 s –1 k = log10 1. 400 Chemical Kinetics . Estimate its half life at 720 K if the energy of activation of the reaction is 250 kJ mol–1 .314 Jk –1mol –1 × 600K log10 2400 2.8908) Solution : 3.MAHESH TUTORIALS SCIENCE .303 × 8. calculate its rate constant at 600 K.285 = log10 20.6 × 10 10 k = 0.303 +log 8. 15 27) A first order gas-phase reaction has an energy of activation of 240 kJ mol–1.6 × 10 s k log k2 k1 = 250 × 103 J mol –1 720 – 820 –1 –1 720 × 820 2.314 × 6 log 2400 Al – log 2.3802 –2. Given : (t1/2) = 900 min T1 = 820 K T2 = 720 K = 250 kJ mol–1 Ea = 250 × 103 J mol–1 To Find : k2 k1 Formula : i) log ii) i) k2 k1 = Ea T2 – T1 2. Given : E a = 240 kJ mol–1 = 240 × 103 J mol–1.147 590.6 × 1013 k = 3.

624 0.226] 1200 k3 = k3 k3 k3 = 1.2116) k1 [A0 ] = 0.1433 × 10 –3 = ( t 1 / 2 )2 6.MAHESH TUTORIALS SCIENCE . This implies that the reaction obeys the integrated rate equation of first order reaction.1458 = 5.446 0.624] 2.624 [At] = 0.2927 = 5. determine the ∴ order of the reaction and calculate its ∴ rate constant.303 log10 [A t ] t [A0 ] = 0.50 × 10–3 (t1/2) 2 = 1. To Find : Rate constant k .624] 2. 16 ∴ k2 log10 = 13056.616 × 10–4 s–1 iii) k3 = ii) k2 k1 = ( t 1 / 2 )1 ( t 1 / 2 )2 900 ∴ ∴ ∴ ∴ 29) 6.303 log [A t ] t [A0 ] = 0.2116 k1 ii) k2 = [A 0 ] 2..595 × 10–4 s–1 ∴ k2 log10 = – 2.624 [At] = 0.446] 600 k1 = k1 = 3.226 t = 1800 s 900 (t1/2) 2 = [0.303 log10 [A t ] t ∴ k2 = Antilog (– 2.6 65.318] 1200 30) The following results were obtained in the decomposition of H 2 O 2 in KI solution at 300C t/s 100 200 300 Volume of O2 collected/cm3 7.446 t = 600 s ∴ [0.399] Chemical Kinetics [0. Hence.9 19.876 [– 1.279 × 10–3 log [2. 0 t/s [A]/mol L –1 600 1200 0.6938 × 10–4] k1 ∴ ∴ k1 k1 = 3.318 t = 1200 s ∴ k2 = 6.4411 = 5.1433 × 10–3 (t1/2) 2 = 146.641 × 10–4 s–1 All the k values calculated at different time intervals are the same.624] 2.303 log [0. the reaction is a first order reaction.1433 × 10–3 k1 k2 = ∴ ∴ ∴ k2 k2 k2 = 1.0 ∞ Show that the reaction is first order. Calculate the rate constant of the reaction.7615] = 1.226 k1 = [A 0 ] 2.838 × 10–3 log [1.465 × 105min ∴ From the following data for the liquid phase reaction A B.279 × 10–3 × 0.919 × 10–3 log [1. 1800 Solution : We require to calculate the rate constant at different time intervals.318 0.3 13.838 × 10–3 × 0.303 log [0. i) [A 0 ] 2.624 [At] = 0.303 log [0.919 × 103 × 0.962] = 1.

1 ∴ ∴ k2 = 0.3 cm3.2 × 10–3 s–1 Since all the k values are constant.9% Let initial concentration. [At] = a – 99.7 k1 = 0.011515 log10 1. t = 300s Solution : k3 = Show that the time required for 99.02303 × 0.303 log10 [A t ] k Time taken for 99.303 log10 V – V t ∞ t i) Given : V t = 7.303 65.1265 k1 = 0.0 – 13.2 × 10–3 s–1 t 65. Hence.2 × 10–3 s–1 k1 = ∴ ∴ ∴ ii) Given : V t = 13.0 cm3 V t = Volume of O2 liberated at time t = amount of H 2O 2 decomposed at time t = x.0cm 3 log10 200 ( 65. [A0 ] = a Then final concentration.9% completion Let the time taken for 99.001a k 2.011515 × 0.303 65.303 log10 100 ( 65..0 log10 100 57.05173 k1 = 1. i) ) 2. t Solution : k1 = ∴ ∴ k2 = 1.6 cm 3 ( = ) a 2. [A0 ] = a Chemical Kinetics = ii) [A 0 ] 2.0 k2 = 0. 17 Formula : k = 2.303 a log10 t a–x k = V∞ 2.9 × a 100 = 0.303 a log10 t a–x Solution : 2H2O2 KI 2H2O(l)+ O2(g) V ∞ = Volume of O 2 liberated after the completion of reaction = a = 65.9 % completion of a first order reaction is three times the time required for 90 % completion.303 log 1000 .303 65.9% of a 99.. k = 1. (i) k Time taken for 90% completion Let the time taken for 90% completion of the reaction be t90% Let initial concentration..9% = 2. (a – x) = V∞ – Vt ∴ k = 2.10449 = [A 0 ] 2. Solution : For a first order reaction.2720 k2 = 0. it is a first order reaction.9 cm3 t = 200s Solution : k2 = 65.303 log10 k [A t ] .9 ) cm 3 ∴ ) 31) = 100s ( ( k = 1.3 ) cm 3 2.011515 log10 51.0 – 7.6 cm3.0cm 3 log10 300 65 – 19.02303 log10 1.001 a = a– t99.303 log10 0.9% completion of the reaction t99.0cm 3 2.MAHESH TUTORIALS SCIENCE .2 × 10–3 s–1 iii) Given : V t = 19.

303 log 10 k Dividing (i) by (ii).303 × 0.1a 2..65.303 log10 t p0 – pt when t = 200 s–1 . pt = (p0 – p) + p + p pt = p0 + p p = pt – p0 p0 – p = p0 – (pt – p0) = 2p0 – pt For first order reaction.65 log10 200 1. (ii) t 99.3 – 1 k = 2.303 × 0. the time required for 99.303 0. ∴ Total pressure/atm p0 2.55 atm Rate of the reactions is Rate = k [Reactant] = k [p of reactant] = 3. (CH3)2CHN = NCH(CH3)2(g) ∴ N2(g) + C6H14(g) estimate the rate of the reaction when total pressure is 0.65 atm To find : Rate of reaction k Solution : ( C H 3)2 (HN = NCH(CH 3)2 At t = 0 At t = t Chemical Kinetics p0 p0 – p ∴ N 2 +C 6H 14 0 p 0 p p0 2.303 0. 2. we get = = . pt = 1 t99. [At] = a – 90% of a 90 × a 100 = 0. Times/s After time.9% = 3 t90% Therefore. t. total pressure. 18 Then final concentration.1 atm p0 – p = 0.1 a = a– = t90% = ∴ 2.9% = 3 t 90% ∴ ∴ 32) 0 0.65 – 1 ∴ k = 2.0 k = p0 2.303 a log10 k 0.75 – p0 p = 0.75 atm.1667 200 k = 2.303 log10 2p 200 0 – pt ∴ k = 2.65 log10 200 2 × 0.303 0.9% completion is 3 ∴ times that required for 90% completion.65 200 1.75 atm p0 + p = 0.303 [A 0 ] log10 k [A t ] k = 2.3 k = 2.9% log 1000 3 = = 1 log 10 t 90% t 99.75 p = 0.13 × 10–3 atm s–1 k = . p0 = 0.3358 200 ∴ Given : Pt = 0.303 log10 2p0 – p t t ∴ From the following data for the ∴ decomposition of azoisopropane.303 log 102..87 × 10–3 s–1 When pt = 0.1 = 0.65 log10 200 0..MAHESH TUTORIALS SCIENCE .75 atm Po = 0.65 – 0. for a first order reaction.55 atm = 2.75 – 0.3358 200 k = 3.65 p = 0.87 × 10–3 s–1 × 0.

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