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You are on page 1of 4

determination of Arrhenius

Activation Energy

Concepts

The key ideas required to understand this section are:

Concept Book page

Temperature 153

Rate of reaction 241

Rate constant 250

Activation energy 249

Arrhenius equation 252

Calculating the Arrhenius activation energy

In this section, we look at a graphical way of calculating the Arrhenius activation energy.

The Arrhenius equation was introduced in Box 14.2 on page 252 in the book, and the following

equation was derived:

In k = In A – (E) 1

- - (1)

(R) T

where:

k is the rate constant of a reaction at temperature T Kelvin. The units of k will depend upon the order of

the reaction;

A is a constant for a particular reaction with the same units as k;

E is the Arrhenius activation energy (in J mol

–1

) of the reaction. This is a constant and does not vary

with temperature.

R is the gas constant (8.3145 J mol

–1

K

–1

).

ln means log to the base e.

A plot of ln k against 1/T follows the form ‘y = mx’ and should be a straight line. The slope (gradient)

of the line is equal to –E/R from which E may be calculated.

1

2

Revision questions

1. To study the dramatic effect of high activation energies upon k values, recalculate the rate constants

shown in Table A14.1 for the hydrolysis of bromoethane (above) at 300 K and 350 K, but based upon a

hypothetical activation energy of 200 kJ mol

–1

. [Assume that the ‘A’ factor is unchanged at 4.30 X 10

11

mol

–1

dm

3

s

–1

].

2. The rate constant for the decomposition of nitrogen (V) oxide:

N

2

O

5

→ 4NO

2

+ O

2

was studied at six temperatures:

T K

300 5.76 x 10

–5

310 2.18 x 10

–4

320 7.61 x 10

–4

330 2.46 x 10

–3

340 7.41 x 10

–3

350 2.10 x 10

–2

Calculate E to three signiﬁcant ﬁgures.

Answers

1. To work out k at 300 K with E = 200 000 J mol–

1

:

k = Ae

-E/RT

=4.30 x 10

11

x e

-((200 000)/(8.3145 x 300))

=4.30 x 10

11

x e

-80.18

=6.47

3

x10

–24

mol

–1

dm3 s

–1

. A similar calculation is made at 350 K. The following table: compares the

rate constants for both the true and hypothetical activation energies and shows that doubling the

activation energy produces rate constants that are virtually zero.

k / mol

–1

dm

3

s

–1

T/K E = 89.6 kJ mol

–1

E = 200 kJ mol

–1

300 0.0001123 6.47 x 10

–24

350 0.01891 6.10 x 10

–19

These calculations are artiﬁcial in the sense that a named reaction has only one value of E.

Nevertheless, it is clear that reactions with roughly equal A factors but different activation energies will

have enormously different rate constants. Even slight differences in activation energy can produce very

different rate constants because the e–E/RT factor ampliﬁes any differences.

Comment

To put things into perspective, if the sodium hydroxide was in excess at [NaOH] = 0.25 mol dm

–3

, then

calculations show that the half-life of the bromoethane with E = 89.6 kJ mol

–1

is 6.9 hours at 300 K and

2.4 minutes at 350 K. This makes the reaction fast enough to investigate in an afternoon lab session!

On the other hand, if E had been 200 kJ mol

–1

for this reaction, the half-lives work out as 3 x10

17

years

(300 K) and 3 x 10

5

years (350 K). These incredibly long times conﬁrm that with E = 200 kJ mol

–1

, the

products are made at a negligible rate.

2. T/K k / s–1 ln k 1/T

300 5.76 x10

–5

–9.762 3.333 x 10

–3

310 2.18 x 10

–4

–8.431 3.226 x 10

–3

320 7.61 x 10

–4

–7.181 3.125 x 10

–

330 2.46 x 10

–3

–6.008 3.03 x 10

–3

340 7.41 x 10

–2

–4.905 2.941 x 10

–3

350 2.10 x 10

–2

–3.863 2.857 x 10

–3

Slope = –5.90/4.76 10–3 K–1 = 12390 K

–12390 K = –E/R.

and

E = (12380 K) (8.3145 J mol–1 K–1) = 103000 J mol–1.

Film Clip: Activation Energy: http://www.youtube.com/watch?v=VbIaK6PLrRM

© Rob Lewis and Wynne Evans, 2001, 2006, 2011, Chemistry, Palgrave Macmillan.

4

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