1

12.11 Using the Arrhenius Equation

The activation energy, Ea, is one of the most important factors
affecting the rate of a reaction. This is seen in the Arrhenius
Equation where the rate constant of a reaction depends on E
a
.
Since
k = A e
-Ea/RT
then
ln k = ln (A e
-Ea/RT
)
It is a mathematical property that ln (ab) = ln a + ln b (see page A-6
of the text).
Because of this, if we let a = A, and b = e
-Ea/RT
, then
ln k = ln (A) + ln (e
-Ea/RT
)
It is also a mathematical property that ln (e
c
) = c. Because of this, if we
let c = (-E
a
/RT), then
ln k = ln (A) (E
a
/RT)
Calculating Ea
Method 1: Believe it or not, this is the equation for a straight line!
Let y = ln k
b = ln A
m = (-E
a
/R)
and x = 1/T
and you get y = mx + b, which is the classic general form for
a linear equation.
If we were to plot ln k versus 1/T
we would get a straight line where the slope = -Ea/R.
Therefore, Ea = - slope x (R) We can calculate Ea this way
2
Method 2 Another way to calculate Ea using the arrhenius equation is
from knowing two rate constants (k
1
and k
1
) measured at two
temperatures (T
1
and T
2
).
Note: The rate constant has changed because the temperature
has changed.
Let ln k
1
= ln (A) (E
a
/RT
1
) and ln k
2
= ln (A) (E
a
/RT
2
)
so ln k
2
ln k
1
= [ln (A) (E
a
/RT
2
)] [ln (A) (E
a
/RT
1
)]
Finally (after some math)
ln k
2
ln k
1
= ( E
a
/R) (1/T
2
1/T
1
) ..Eq. # 1
or
(ln k) = ( E
a
/R) (1/T)
Ea can then be calculated by rearranging Eq # 1
E
a
= -R [ (ln k
2
ln k
1
) / (1/T
2
1/T
1
) ]
Problem 12.16
Rate constants k
1
(at T
1
) and k
2
(at T
2
) for the decomposition of
gaseous dinitrogen pentaoxide are 3.7 x 10
-5
s
-1
at 25 C and 1.7 x 10
-3
s
-1
at 55 C.
2 N
2
O
5
(g) 4 NO
2
(g) + O
2
(g)
a) What is the activation energy of this reaction in kJ/mol?
Solution: use E
a
= -R [ (ln k
2
ln k
1
) / (1/T
2
1/T
1
) ] and note that
temperature must in units of K
Ans: done in class
b) What is the rate constant at 35 C?
Ans: done in class
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