Activation energy

– The Arrhenius equation

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Activation energy

 Example: Assume that the following reaction takes place in a single step:

 Reaction mechanism:

Transition state

Before reaction After reaction

2
Activation energy

 Example: Assume that the following reaction takes place in a single step:

Potential energy
 Potential energy level profile:

+
+

Transition Reaction
Before After
state extent

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The Arrhenius equation

 Example: Assume the following is a gas phase reaction:

 Assume the rate law:

 Rate constant as a function of temperature:

The
Arrh
e ni u s
equ
atio
n

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The Arrhenius equation

 Rate constant as a function of temperature:

 Arrhenius constant (or frequency factor or preexponential factor) :

Depends on the frequency of collisions per time unit with correct
orientation

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The Arrhenius equation

 Example: Reaction between iodomethane and hydroxide ions:

 Only collisions with correct orientation may be succesfull
Potential
energy

The hydroxide ion must

attack iodomethane from
”behind” (opposite the
iodine atom)
+
+
Transition Reaction
Before After
state extent

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The Arrhenius equation

 Rate constant as a function of temperature :

 Temperature dependent factor : Depends on the frequency of collisions

per time unit with necessary kinetic energy

7
The Arrhenius equation

 Model of a gas at two temperatures:

Low temperature Higher temperature

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The Arrhenius equation

 Maxwell-Boltzmann distribution of gas molecules:

Distribution of speed for

oxygen molecules at three
different temperatures

The frequency of molecules

with kinetic energy above at
temperature is:

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The Arrhenius equation

 Svante Arrhenius found the equation for gas phase reactions in 1889:

 It’s often a good approximation for nongaseous reaction mixtures

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The Arrhenius equation

 Using natural logarithm:

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The Arrhenius equation

 Arrhenius plot:

 Activation energy can be calculated

from gradient of line:
𝐸a
𝑚= −
𝑅

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The Arrhenius equation

 Example: Decomposition of dinitrogen pentoxide:

T k
K s‒1
273
 The reaction is a first order reaction 298
308
 Rate constant measured at different 318
temperatures: 328
338

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The Arrhenius equation

 Arrhenius plot:
T k 1/T
ln k
K s‒1 K‒1
273 0,00366 -14,06
298 0,00336 -10,27
308 0,00325 -8,91
318 0,00314 -7,60
328 0,00305 -6,54
338 0,00296 -5,32

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The Arrhenius equation

 Arrhenius plot:
ARRHENIUS PLOT
0.00
0.00300 0.00310 0.00320 0.00330 0.00340 0.00350 0.00360 0.00370
-2.00

-4.00

-6.00 f(x) = − 12355.7277923614 x + 31.2023924812762

R² = 0.999836793389173
ln k

-8.00

-10.00

-12.00

-14.00

-16.00

1/T / K‒1

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The Arrhenius equation

 Activation energy calculated from the

gradient: ARRHENIUS PLOT
0.00
0.00300 0.00320 0.00340 0.00360 0.00380
-2.00

-4.00

-6.00 f(x) = − 12355.7277923614 x + 31.2023924812762

R² = 0.999836793389173

ln k
-8.00

-10.00

-12.00

-14.00

-16.00

1/T / K‒1

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The Arrhenius equation

 Arrhenius plot:

 Using formula of gradient:

𝐸a
𝑚= −
( 1
𝑇1 )
, ln 𝑘 1 𝑅

( 1
𝑇2
, ln 𝑘2
)
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The Arrhenius equation

 Some activation energies:

Reaction Reaction

Catalase

Gold
Platinum

Tungsten

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Exercises

 Please solve
 Exercise 26-29 at page 304 in Higher Level Chemistry

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