DSE Chem notes (Activation energy)

Chapter 52 – Activation energy

52.1 Activation energy and energy profile
- Molecules must collide with each other for a reaction to occur. However, not every collision is
effective.
- Effective collisions are collisions that result in chemical reaction.

Activation Energy (Ea)

Activation energy is the minimum energy required to start a chemical reaction.

- Energy is needed to __________ the chemical ________ within the molecules before they can
react.
- Hence, molecules must possess a certain minimum amount of energy so that they can react on
collision.

Energy profile
- An energy profile is a curve showing the relative energy levels of reactants, intermediates and
products.
- During a reaction, a transition state (or activated complex) is formed in which old bonds in the
reactant(s) are partially broken and new bonds in the product(s) are partially formed.
- The transition state is at the peak of the curve in an energy profile.

Exothermic reaction Endothermic reaction

- Activation energy, Ea, is the energy difference between the ____________ and the
_____________ __________.
- A high Ea corresponds to a slow reaction and a low Ea corresponds to a fast reaction.

Points to note:
On a chemical level, the bonds that hold the atoms of molecules together have potential energy. The fact that energy
can be released by the breakdown of certain chemical bonds implies that those bonds have potential energy. The type
of potential energy that exists within chemical bonds, and is released when those bonds are broken, is called chemical
energy.

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DSE Chem notes (Activation energy)

52.2 Effect of temperature on reaction rate

- Reaction rate always increases with increase in temperature.

Maxwell-Boltzmann distribution curve

- It shows the distribution of kinetic
__________ in a sample of gas
molecules.
- The area under the curve is equal to the
total number of molecules in the system.
- Only a ___________ proportion of
molecules have high kinetic energy.
- The shaded area represents the number of molecules having energy equal to or greater than
Ea .
- If Ea is lower, the number of molecules having energy equal to or greater than Ea will be
____________, and the reaction rate will be ____________.

Explaining effect of temperature rise on reaction rate

Number of molecules

Ea Kinetic Energy
- When temperature increases:
1. The average kinetic energy of molecules _____________.
2. The number of molecules having energy equal to or greater than the activation
energy increases greatly.
- At a higher temperature, a larger proportion of molecules can take part in _____________
collisions.
- ______________ of effective collision increases and hence reaction rate _____________ .
- In general, reaction rate ___________ with a 10 oC rise in temperature.

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DSE Chem notes (Activation energy)

52.3 Arrhenius equation

- Arrhenius equation shows the relationship between rate constant, activation energy and
temperature.
Ea
 Ea
k =Ae RT or log k = log A –
2.3 RT

where k is rate constant

A is a constant which includes factors like the frequency of collisions and their
orientation. (It varies slightly with temperature, although not much. It is often
taken as constant across small temperature ranges.)
e is the base of natural logarithm
Ea is activation energy (in J mol-1, not in kJ mol-1)
R is gas constant (8.31 J K-1 mol-1)
T is absolute temperature in Kelvin(oC + 273)

- Ea is a constant for a specific reaction. It does not change with temperature or concentration of
reactants.
- Rate constant is not affected by changes in concentration but it increases with increase in
temperature.
Ea

- The expression, e RT counts the fraction of the molecules present in a gas which have
energies equal to or in excess of activation energy at a particular temperature.

Determining Ea by graphical method

- Find values of rate constant k at different temperatures.

- Plot a graph of ________ (y-axis) against _______ (x-axis).
- Ea can be calculated from the slope of the straight line.

- For a hypothetical reaction

Rate = k [A]x [B]y

if concentrations of reactants are kept constant, rate k, hence log rate can replace log k in the
above graph.
- Initial rates are often represented as 1/time, hence log (1/time) is often plotted against 1/T in
order to find the Ea of a reaction.

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DSE Chem notes (Activation energy)

Determining Ea by numerical method

- Find values of rate constant k at two different temperatures.
Ea
log k1 = log A – ………………..(1)
2.3 RT1
Ea
log k2 = log A – ………………..(2)
2.3 RT2
Subtracting (1) from (2):
Ea 1 1
log k2 – log k1 = (  )
2.3 R T1 T2
k2 Ea 1 1
log = (  )
k1 2.3 R T1 T2

- Substituting the values of k1, k2, T1, T2 and R into the equation, Ea can be found.
(Rate constants k1 & k2, can be replaced by initial rates because they are directly proportional as
long as concentrations of reactants are kept constant.)
Work examples
1. At 300oC, the rate constant for a reaction is 2.41 x 10-10 s-1. At 400oC, the rate constant is 1.16
x10-6 s-1. Determine the activation energy for the reaction. (Given R = 8.31 J K-1 mol-1)

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DSE Chem notes (Activation energy)

2. The rate of a certain reaction is found to double when the reaction temperature rises from 398
K to 408 K. Calculate the activation energy of the reaction. (Given R = 8.31 J K-1 mol-1)

3. Consider a reaction with Ea = 52 kJ mol-1. What effect will it have on the reaction rate if the
reaction temperature is increased from 298 K to 308 K?
(Given R = 8.31 J K-1 mol-1)

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DSE Chem notes (Activation energy)

Using the Arrhenius equation Appendix

The effect of a change of temperature

You can use the Arrhenius equation to show the effect of a change of temperature on the rate
constant - and therefore on the rate of the reaction. If the rate constant doubles, for example, so also
will the rate of the reaction.

What happens if you increase the temperature by 10°C from, say, 20°C to 30°C (293 K to 303 K)?
The frequency factor, A, in the equation is approximately constant for such a small temperature
Ea

change. We need to look at how e RT changes - the fraction of molecules with energies equal to or
in excess of the activation energy.

Let's assume an activation energy of 50 kJ mol-1. In the equation, we have to write that as 50000 J
mol-1. The value of the gas constant, R, is 8.31 J K-1 mol-1.
At 20°C (293 K) the value of the fraction is:

By raising the temperature just a little bit (to 303 K), this increases:

You can see that the fraction of the molecules able to react has almost doubled by increasing the
temperature by 10°C. That causes the rate of reaction to almost double. This is the value in the
rule-of-thumb often used in simple rate of reaction work.

Note: This approximation (about the rate of a reaction doubling for a 10 degree rise in temperature) only works for
reactions with activation energies of about 50 kJ mol-1 fairly close to room temperature. Try to use the equation to
find out what happens if you increase the temperature from, say 1000 K to 1010 K. Work out the expression -(EA /
RT) and then use the ex button on your calculator to finish the job.

The rate constant goes on increasing as the temperature goes up, but the rate of increase falls off quite rapidly at
higher temperatures.

The effect of a catalyst

A catalyst will provide a route for the reaction with a lower activation energy. Suppose in the
presence of a catalyst that the activation energy falls to 25 kJ mol -1. Redoing the calculation at 293
K:

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DSE Chem notes (Activation energy)

If you compare that with the corresponding value where the activation energy was 50 kJ mol -1, you
will see that there has been a massive increase in the fraction of the molecules which are able to react.
There are almost 30000 times more molecules which can react in the presence of the catalyst
compared to having no catalyst (using our assumptions about the activation energies).
It's no wonder catalysts speed up reactions!

Note: If you read this carefully, you should notice that the reaction will be 30000 times faster. There may well be 30000
times more molecules which can react, but it is highly likely that the frequency factor will have changed in the
presence of the catalyst. And the rate constant k is just one factor in the rate equation. You won't just have the
original reactants present as before. The catalyst is bound to be involved in the slow step of the reaction, and a new
rate equation will have to include a term relating to the catalyst.
Nevertheless, the catalysed reaction is still going to be a lot faster than the uncatalysed one because of the huge
increase in sufficiently energetic molecules.

Other calculations involving the Arrhenius equation

Determining Ea by graphical method

Taking the log of both sides of The Arrhenius Equation yields the
following:
Ea
log k = log A –
2.3 RT

The Arrhenius Equation has the linear form y = mx + c. Graphing log k vs 1/T yields a straight line
with a slope of -Ea/2.3R and a y-intercept of log A., as shown in Figure 4.

Figure 4 Figure 5

As indicated in Figure 5, the reaction with a higher Ea has a steeper slope; the reaction rate is thus
very sensitive to temperature change. In contrast, the reaction with a lower Ea is less sensitive to a
temperature change.

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