Chapter 54 Activation energy Class Practice A54.

1 (a)
Energy

Ea

Reaction coordinate

(b) Activated complex (c) (Marked in the diagram) (d) It is an endothermic reaction because the energy of the reactants is lower than that of the products. Conversion of reactants to products needs an input of energy. A54.2 Arrhenius equation stated that log k = constant  By plotting a graph of log k against to

Ea . 2.3RT

1 , the slope of the line obtained should be equal T

Ea . 2.3R
0.627 0.00500 0.521 0.00333 0.469 0.00250 0.437 0.00200 0.414 0.00167 0.399 0.00143 0.388 0.00125

log k

1 (K1) T

By using the points (0.00143, 0.399) and (0.00500, 0.627) gives

 0.627  (  0.399 ) ! 63.87 0.00500  0.00143

Ea =63.87 2.3R

Ea = 63.87 v 2.3 v 8.31 J mol1 = 1220 J mol1 = 1.22 kJ mol1

0.001

0.002

0.003

0.004

0.005

1 T

(K

1

0.4

log k
0.5 0.6

A54.3 1. By substituting values of k1, k2, T1 and T2 into the Arrhenius equation and then solving for Ea. k1 = 8.38 v 104 k2 = 7.65 v 10
2

T1 = 673 K

T2 = 773 K Ea 1 1 log k1 log k2 = (  ) 2.3R T2 T1 log 8.38 v 104 log 7.65 v 102 = Solving for Ea = 195 kJ mol1
 Ea

Ea 1 1 ) (  2.3 v 8.31 773 673

2.

According to the Arrhenius equation, k = A e RT At 298 K, k298 = A e

 52 v10 3 8.31v 298

= A(7.59 v 1010) At 308 K, k308 = A e

 52v10 3 8.31v 308

= A(15.08 v 1010) Comparing the rate constants at 298 K and 308 K by dividing k308 by k298: k 308 A(15.08 v 10 10 ) ! ! 1.99 } 2.0 k 298 A(7.59 v 10 10 )

k308 = 2 v k298 The reaction rate increased by a factor very close to 2 for a 10 K rise in temperature from 298 K to 308 K. Small temperature changes are seen to have a pronounced influence on the rates of chemical reactions.

Chapter 54 Activation energy Chapter Exercise 1. 2. 3. 4. 5. 6. 7. Activation energy, activation energy low, slow Energy profile, coordinate, energy ctivated, omplex, ransition, tate, broken, formed less, negative greater, positive (a) kinetic (b) activation, Maxwell-Boltzmann distribution
 Ea

8. 9.

xponential, Arrhenius, A e RT , logA increase

Ea 2.3RT

10. ctivation energy, log k, 11. A 12. C 13. C 14. A 15. D 16. B 17. A 18. D 19. A 20. C 21. B 22. B 23. B

1 E , a 2. 3 R T

24. The formation of PbCl2 by route 1 would occur faster at room temperature. Route 1 involves the collision of two oppositely charged particles. Activation energy needed would be expected to be smaller. Route 2 requires quite a large amount of energy (activation energy) to overcome before PbCl2 is formed. This can be evident from the fact that energy is needed to break the ClCl bond. 25.

transition state

Energy

activation

products

Reaction coordinate

26.

T1

T2 > T1

Number of particles

T2 At a lower temperature, less particles have energy greater than Ea.

Kinetic energy

At a lower temperature, the number of particles having energy greater than Ea is decreased. Less particles have enough energy to collide effectively. As a result, the lower the temperature, the slower the reaction. Lower temperatures also decrease the average kinetic energy of the molecules, causing a decrease in the rate of reaction.

27. Arrhenius equation: log k = constant By plotting a graph of log k against equal to

Ea 2.3RT

1 , the slope of the line obtained should be T

Ea . 2.3R 1 (K1) T
2.7 v 103 2.1 v 10
3

log k 13.52 8.24

1.8 v 103 1.5 v 10 1.3 v 10

0 0.0015
3 3

5.54 3.08 1.11

0.0020 0.0025 0.0030

1 1 (K ) T

log k

2 4 6 8 10 12 14

16

By using the points (1.6 v 103, 4) and (2.1 v 103, 8), the slope= @

 8  (4) = 8000 2.1 v 10 3  1.6 v 10 3

Ea = 8000 2.3RT

Ea = 8000 v 2.3 v 8.314 J mol1 = 152 980 J mol1 = 152.98 kJ mol1 28. Taking the logarithm of Arrhenius equation, logk = logA

Ea 2.3RT
Ea 1 1 (  ) 2.3R T2 T1

So, logk1 logk2 =

where T1 = 473 K, k1= 1.32 v 102 dm3 mol1 s1 and when T2 = 548 K, k2 = 1.64 dm3 mol1 s1. log1.32 v 102 log1.64 = Ea = 138.4 kJ mol1 29. Taking the logarithm of Arrhenius equation,

Ea 1 1 ) (  2.3 v 8.314 548 473

log k = log A 

Ea 2.3RT
Ea 1 1 (  ) 2.3R T2 T1

So, log k1 log k2 =

where T1 = 700 + 273 K = 973 K, k1 = 1.62 v 103 dm3 mol1 s1 and T2 = 500 + 273 K = 773 K. Log 1.62 v 103 log k2 = 1 180 v 10 3 1 ) (  2.3 v 8.314 773 973 k2 = 5.09 v 106 dm3 mol1 s1

30. Taking the logarithm of Arrhenius equation, log k = log A 

Ea 2.3RT
Ea 1 1 (  ) 2.3R T2 T1

So, log k1 log k2 =

where T1 = 250 + 273 K = 523 K, k1 = 1.32 v 103 dm3 mol1 s1 and k2 = 0.233 dm3 mol1 s1. 1 140 v 10 3 1 ) (  Log 1.32 v 103 log 0.233 = 2.3 v 8.314 T2 523 T2 = 623 K = 350 rC 31. By applying the Arrhenius equation E 1 1 log k1 log k2 = a (  ) 2.3R T2 T1 If the rate constant of the reaction at 30 rC is k, the rate constant of the reaction at 100 rC is 4k. When k1 = k, k2 = 4k, T1 = 273 + 30 K = 303 K and T2 = 273 + 100 K = 373 K. By putting the data into the Arrhenius equation, log k log 4k =
Ea 1 1 (  ) 2.3 v 8.314 373 303

Ea = 18.59 kJ mol1