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Activation Energy and Reaction Profiles

The significance of activation energy


When gases or liquids are heated the particles gain kinetic
energy and move faster increasing the chance of collision between
reactant molecules and therefore the increased chance of a fruitful
collision (i.e. one resulting in product formation).
However! This is NOT the main reason for the increased reaction
speed on increasing the temperature of reactant molecules because
most molecular collisions do not result in chemical change.
Before any change takes place on collision, the colliding
molecules must have a minimum kinetic energy called
the activation energy.
o Its a sort of 'threshold' energy required before any bonds can
be broken i.e. before a reaction can take place.
Do not confuse activation energy with the overall energy change also
shown in the energy profile diagrams below, that is the overall energy
absorbed-taken in by the system (endothermic) or given out to the
surroundings (exothermic).
It does not matter whether the reaction is an exothermic or an
endothermic energy change (see the pair of reaction profile diagrams
below).
Higher temperature molecules in gases and liquids have a
greater average kinetic energy and so a greater proportion of
them will then have the required activation energy to react on
collision.
The increased chance of higher energy collisions greatly
increases the speed of the reaction because it greatly increases
the chance of a fruitful collision forming the reaction
products by bonds being broken in the reactants and new bonds
formed in the reaction products.
The activation energy 'hump' can be related to the process of bond
breaking and making

o Up the hump is endothermic, representing breaking bonds


(energy absorbed, needed to pull atoms apart),
o down the other side of the hump is exothermic,
representing bond formation (energy released, as atoms
become electronically more stable).
o The 'reaction profile' diagrams below illustrate the course or
progress of a reaction in terms of the energy changes taking
place.
o Do NOT confuse the activation energy with overall energy
change of the reaction (exothermic or endothermic) shown in
the 2nd and 3rd set of diagrams below.

ENERGY PROFILES for chemical reactions


1. Simple energy level diagrams for exothermic and
endothermic reactions NOT showing the activation energy

ENERGY PROFILES for chemical reactions


2. Energy level diagrams for exothermic and endothermic reactions
showing the activation energy 'hump' which must be overcome before
a chemical reaction can take place

3. Note that the effect of a catalyst is to lower the activation energy,


enabling the reaction to go faster BUT it does NOT affect the overall
energy change of the reaction. The catalyst provides a different pathway
for the reaction that needs less energy to initiate it but it does NOT change
the energy transfer value irrespective of whether it is an exothermic or an
endothermic reaction.

3b. Further examples of reaction progress profiles

Reaction profile
diagram

Relative comments on these ENERGY PROFILES for


chemical reactions

Very endothermic reaction with a big activation


energy.

Very exothermic reaction with a small activation


energy.

Moderately endothermic reaction with a moderately


high activation energy.

Moderately exothermic reaction with a moderately


high activation energy.
A small activation energy reaction with no net energy
change. This is theoretically possible if the total
energy absorbed by the reactants in bond breaking
equals the energy released by bonds forming in the
products.

Energy level diagram for an exothermic chemical


reaction without showing the activation energy.
It could also be seen as quite exothermic with a highly
unlikely zero activation energy, but reactions between
two ions of opposite charge usually has a very low
activation energy.
Energy level diagram for an endothermic chemical
reaction without showing the activation energy.
It could also be seen as quite endothermic with a zero
activation energy (highly unlikely, probably
impossible?).

4. Catalysts and Activation Energy


Catalysts increase the rate of a reaction by helping break
chemical bonds in reactant molecules.
This effectively means the activation energy is reduced (see
diagram 'humps' below).
Therefore at the same temperature, more reactant molecules have
enough kinetic energy to react compared to the uncatalysed
situation and so the reaction speeds up with the greater chance of a
'fruitful' collision.
o Note that a catalyst does NOT change the energy of the
molecules, it reduces the threshold kinetic energy needed
for a molecules to react.
o The overall energy change for a catalysed reaction is
identical to the energy change for the same uncatalysed
reaction.
Although a true catalyst does take part in the reaction, it does not
get used up and can be reused with more reactants, it may change
chemically on a temporary basis but would be reformed as the
reaction products also form.
However a solid catalyst might change physically permanently by
becoming more finely divided, especially if the reaction is exothermic.

Also note from the diagram that although the activation energy is
reduced, the overall exothermic or endothermic energy change
is the same for both the catalysed or uncatalysed reaction. The
catalyst might help break the bonds BUT it cannot change the actual
bond energies.

ENERGY PROFILES for chemical reactions


Combined reaction profiles for an uncatalysed and catalysed reaction.