Notes on Kinetics

Activation Energy
What is Activation Energy?

Chemical reactions ordinarily occur as a result of collisions between reacting particles.

Consider the reaction:

CO(g) + NO2(g) ----> CO2(g) + NO(g)

rate = k(conc CO)(conc NO2(g)

• doubling the concentration of CO, holding NO2 constant, the number of collisions
in a given time doubles.
• doubling the concentration of NO2, holding CO constant, has the same effect.

In general, the number of collisions per unit time is directly proportional to the
concentration of CO or NO2.

The fact that the rate is directly proportional to these concentrations implies that reaction
occurs as a direct result of collisions between CO and NO2 molecules.

NOT EVERY COLLISION LEADS TO

REACTION!!!!!
It is possible to calculate the rate at which molecules collide with each other by using the
kinetic theory.

Consider a mixture of CO and NO2 at 700 K and a concentration of 0.10 mol/L

• every molecule would collide with about a billion other molecules in one second!
• if every collision resulted in a reaction, then the whole mixture would be reacted
in a fraction of a second.
• the actual reaction takes about 20 seconds.

In order for collisions to be effective, there must be considerable force in the colllisions.
The slower moving molecules do not have enough kinetic energy to react when they
collide...they bounce off one another and retain their identity.

Only those molecules moving at high speed have enough energy for collisions to result in
a reaction.

Every reaction requires a certain minimum energy for the reaction to occur--it is called
activation energy, Ea, and is expressed in kJ.

The CO + NO2 mixture from above has an Ea = 134 kJ. This means that the colliding
molecules must have a total KE of 134 kJ/mol if they are to react.
SO, what are the properties of the activation energy, Ea?

• it is a positive quantity, Ea>0

• it depends upon the nature of the reaction. "Fast" reactions usually have a small
Ea; those with a large Ea usually proceed slowly.
• it is independent of temperature and concentrations.

Activated Complex-an intermediate species that is an unstable, high energy species

that must be formed before the reaction can occur.

The ... stands for partial bonds. The O-N bond has been partially broken and the
C-O bond has started to form.

• forward reaction exothermic (∆ H<0), Ea is smaller than Ea1

• forward reaction endothermic (∆ H>0), Ea is larger than Ea1
• if ∆ H = +200 kJ, then Ea = Ea1 + ∆ H = Ea1 + 200 kJ