3. Determine the activation energy and the frequency factor from the following data.

T (⁰C) 0 100
k
(1/min) 0.001 0.05

a. Use the Arrhenius theory

b. Transition state theory
c. %difference between the time activation energies in a and b
d. Calculate the value of k at 1000⁰C using a and b. What is the %difference between the
two k at this temperature?

Solution:
a.
k (1/min) 0.001 0.05 T (⁰C) 0 100
lnk -6.9078 -2.9957 (1/T) x 10-3 3.6609 2.6799

lnk = lnko – EA 1_
R T
By linear regression:
m= - 3987.8695
m= – EA = - EA = mR = -3987.8695
R
EA = 33,155.1470 kJ/mol

lnk = lnko – EA 1_
R T
-6.9078 = lnko – 33,155.147 _ 1____
8.314 273.15

ko = 2190.2234 /min

b. ln k = lnkO’’ – EACT 1_
T R T

ln k2 _ T1 = EACT T2-T1
k1 T2 8.314 T1T2

ln 0.05 273.15 = EACT 373.15 – 273.15

0.001 373.15 8.314 (273.15)(373.15)

EACT= 30.5074 kJ/mol

ln k = lnkO’’ – EACT 1_
T R T
ln 0.001 = lnkO’’ - 30507.3754 1____
273.15 8.314 273.15

kO’’ = 2.4989

c. %difference = (33.1551 – 30.5074) x 100 = 7.9858%

33.1551

d. T2= 1000⁰C =1273.15K

T1= 0⁰C = 273.15K
k1 = 0.001/min , 0.05/min

k (min) k2 0.001 T (⁰C) 1273.15 273.15

lnk -6.9078 1/T 7.8545 x 10-4 3.6601 x 10 -3

lnk = lnko – EA 1_
R T

ln k2 _ = EACT T2-T1
k1 R T1T2
ln k2 __ = 33155.1470 1273.15 – 273.15_
0.001 8.314 (273.15) (1273.15)

k2= 95.5374/min

By Transition State Theory

ln k2 _ T1 = EACT T2-T1
k1 T2 R T1T2

ln __ k _ 273.15 = 30507.3754 1273.15 – 273.15_

0.001 1273.15 8.314 (273.15)(1273.15)

k2= 178.2112/min

%difference = 178.2112 – 95.5374 x 100

178.2112

%difference = 46.3909%

4. Calculate the activation energy for the decomposition of benzene diazonium chloride to
give chlorobenzene and nitrogen. Use the following information:
T(K) 313 319 323 328 333
k(s-1) 0.00043 0.00103 0.0018 0.00355 0.00717
Solution:
T(K) 313 319 323 328 333
(1/T) x 10-3 3.1949 3.1348 3.0960 3.0488 3.0030

lnk = lnkO - EA _ 1_
R T
By linear regression:
m= -14,611.3538
m= -EA/R
-EA= mR
-EA= (-14,611.3538)(8.314 J/mol)
-EA= -121,478.7955 J/mol

EA= 121.4788 kJ/mol