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Kinetics (Rates)

Kinetics or rates just means how fast a reaction occurs.

Collision Theory
For a reaction to occur, the reactant particles must collide with each other. But not all collisions lead to a
reaction.

The particles must collide with a minimum energy for the reaction to occur: the activation energy. The
phrase successful collisions is often used to describe this.

Oxygen and nitrogen are constantly colliding in the air but no reaction takes place as the reactants dont
have enough energy. But, for example, when in a car engine, a spark provides the energy for a reaction
to occur i.e. there is enough energy to overcome the activation energy.

When answering questions later on in the topic, always keep this collision theory in mind.

Activation Energy

An exothermic reaction is shown in the reaction profile diagram below. The activation energy is
represented by the EA symbol.

The activation energy is like a barrier to the reaction. The reactant particles must have enough energy
to get to the top of the hill. The higher this peak in the curve, the higher the activation energy.

Reactants EA
Energy s H
Product
s

Reaction Pathway

Note the reaction enthalpy, H, the difference in energy between the reactants and products.

Factors affecting rate

There are 5 factors that affect the rate: temperature, concentration, pressure, surface area and
catalysts.
Temperature

If the temperature is increased, the kinetic energy of the particles is increased. Therefore, the particles
move faster and collide with each other more often. The result is that there is likely to be more
successful collisions i.e. collisions with enough energy to overcome the activation energy.

more successful collisions = a faster rate

Concentration

If the concentration is increased, the particles will be closer together, leading to more collisions. More
collisions increases the chance of successful collisions and therefore an increase in the rate.

Pressure

Is the same principle as for concentration but for gases. To increase the pressure the container/flask is
usually reduced in size.

Surface area

Collisions take place on the surface of the reactants. If the surface area is increased, then there are more
surfaces for collisions to occur, increasing the chances of successful collisions.

This usually means comparing a large lump of a solid with a powder of the same compound.

the powder has a larger surface area and therefore a faster rate

Catalyst

Using a catalyst increases the reaction rate. A very common exam question is to ask how a catalyst does
this.

a catalyst provides an alternative pathway for the reaction at a lower activation energy

This means that the reaction with a catalyst proceeds by a different mechanism to that of the
uncatalysed reaction. The route the catalyst uses is at a lower activation energy.

Calculating the rate

Rate = the change in something measureable such as volume, mass, concentration/the change in time.
Concentration is the most common example used in the A-level syllabus.

From the experiments carried out, a graph of concentration versus time can be drawn:

The rate at any point on the graph is found by calculating the gradient. This means a tangent to the curve
must be drawn to get the gradient.

Initial rate is often used. This is the steepest part of the curve i.e. at time = o

Alternatively: rate = 1/time

More Curves

Another common scenario could be to plot a graph of volume of gas produced versus time.

The steepness of the curve initially indicates the rate i.e. a steep curve = faster rate.

Where the curve finishes indicates how much of a substance was used, usually in comparison to another
curve on the graph.

Maxwell Boltzmann Distributions

Below is an example of a Maxwell Boltzmann distribution for a gas. Not all particles in a gas have the
same energy and the curve shows the variation or spread in these energies at a particular temperature.

It can be thought of as a probability curve. Most molecules are likely to have an energy somewhere in
the middle. And less molecules are likely to have extremely high or low energies.

On the vertical axis is the number of molecules and on the horizontal axis is kinetic energy:
Number Most molecules have
of molecules this energy

Orange section:
number of
EA molecules with
energy greater than
EA

Energy

The peak of the curve shows the most probable energy. This is NOT the same as the average energy.

The average energy will be at a point somewhere to the right of the most probable energy.

The area under the curve is the total number of molecules.

The curve goes through the origin as no molecules can have zero energy.

On the x-axis at the far right, the curve never crosses the axis as there is no upper limit to the
molecules energies.

The activation energy tends to be quite far to the right. The little orange section shows the number of
molecules with energies greater than the activation energy i.e. those that have enough energy to react.

Increase the temperature

Questions quite often ask you to draw or explain what is going on with the Maxwell Boltzmann curve at
different temperatures.

The main thing to realise here is that the shape of the curve changes but the number of molecules
remains constant when the temperature is changed.

As the temperature is increased, ALL the particles gain energy. Therefore, the curve shifts to the right
and flattens out a bit.

The curve does not show temperature. It shows the affect of temperature on the energies. Students
often draw a steeper curve when the temperature is increased, but that makes no sense as it implies
that the energies are decreasing!
Extra
molecules
above EA

Number of
molecules

Energy

The important part of the distribution is the right hand side. T2 is a higher temperature than T1, and the
diagram shows the extra number of molecules with energies above the activation energy.

more molecules with energies above the EA means more chance of successful collisions

Catalysts

As was mentioned earlier, the affect of a catalyst is to lower the activation energy of a reaction and
hence speed it up

This can also be shown on a Boltzmann distribution. The diagram below shows the original activation
energy (furthest to the right) without a catalyst.

Number of
Molecules

Energy
The orange area shows the number of molecules above the activation energy that will react without the
catalyst.

When the catalyst is added, the activation energy becomes lower and the green area shows the extra
number of molecules now above the activation energy. Therefore there is an increase in the rate.

Reaction Profile Diagrams

Examiners sometimes ask you to draw the reaction profile diagram when a catalyst is added. Be careful
not to get the Maxwell Boltzmann distribution mixed up with reaction profiles.

You should be familiar with reaction profiles already from the enthalpy topic. Below is an example of
adding a catalyst to an exothermic reaction:

EA without catalyst

EA with catalyst
Energy

Reaction Pathway

Heterogeneous catalysts

the catalyst and reactants are in different states

Most reactions use this type of catalyst. For example, the Haber process uses an iron catalyst when
making ammonia. When the catalyst and reactants are in different states, they can be easily separated by
filtration.

The catalyst provides a surface on which the reaction can take place

The reactant molecules are adsorbed (bonded) on to the surface. The surface has little grooves on it
called sites, to which the reactants attach themselves. The reactant bonds are weakened, a reaction
occurs and then the products desorb (leave).

There are also homogeneous catalysts, which just means that the catalyst and reactants are in the same
state. For example, enzymes in the body. But they shouldnt ask about this.