Topic 2.3: Kinetics I

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2.3 (a) Factors affecting the rate of reaction

Task 2.3a Complete and extend the table below:

variable (factor) value high or low rate
     
     
     
     
     

2.3 (b) Explanations using collision theory
The collision theory is used to explain changes in reaction rate.  In a reaction between 2 gaseous substances A and B, a molecule of A must collide with a molecule of B before reaction can occur. The number of collisions in a given time, the collision frequency, controls the rate of reaction. The greater the collision frequency the greater the rate of reaction.  Not every collision leads to a reaction.  A reaction takes place during a collision if the molecules hit at the correct angle or orientation and if they have enough energy.  This amount of energy per mol of molecules is called the activation energy. The theory is extended to cover liquids and solids.
Temperature
Increasing the temperature increases the speed of the reacting particles and faster particles collide more often than slow ones. The increase in the number of collisions leads to an increase in the collision frequency and rate of reaction.  Increasing the temperature also gives the particles more energy so that they collide with more violence. Energetic particles have a better chance of their collisions leading to a reaction.
Concentration
The concentration of a substance, normally a solution, is the amount in a given volume.
concentration = amount {units = mol/dm3 or M}
                         volume
In a higher concentration solution there are more particles to react therefore there are more collisions and a higher collision frequency. As a reaction depends on collisions happening, a higher collision frequency leads to a faster reaction rate. If we were doing a reaction with acid and we double the number of acid particles, we double the number of collisions and therefore are likely to double the reaction rate.
Pressure
Increasing the pressure of a gas puts more gas molecules into a given volume.  There will be more collisions and a higher collision frequency leading to a higher rate of reaction.
Surface area
Surface area is controlled by the particle size of a solid.  A powder has a higher surface area than lumps and therefore a powder has more atoms or ions exposed on its surface in a position to react. More collisions take place between the ions or molecules in the surrounding liquid.  The collision frequency in increased and so is the rate of reaction. 
Task 2.3b Draw diagrams to show slow and fast reactions caused by changing the factors above.

2.3 (c) Maxwell-Bolzmann distribution

As the temperature is raised the average energy of the molecules increases. The proportion of molecules with the activation energy (see section under graph) is greater at higher temperatures.  A small increase in temperature gives a large increase in reaction rate.  Simulation of change in temperature requires Microsoft Excel (source www.chemit.co.uk )

2.3 (d) Activation energy
Activation energy is a measure of the energy needed, when molecules collide, to lead to a reaction.  The lower the activation energy the more molecules at a particular temperature will have enough energy to react when they collide.  As the temperature increases more molecules will have an amount of energy equal to or more than the activation energy.  At a high temperature more collisions therefore lead to reaction.

2.3 (e) Catalysts and activation energy
Catalysts alter the rate of a chemical reaction without being consumed in the reaction. (e.g. the catalyst may end up in the oxidation state it began with). A catalyst reduces the activation energy for a reaction by providing an alternative mechanism for the reaction.

Homogeneous catalysts can form intermediates which contain the catalyst but then decompose to form products.  For the reaction
A  -----> B + C                                  high activation energy
A + catalyst -----> A-catalyst             low activation energy
A-catalyst -----> B + C + catalyst       low activation energy

The catalyst may change oxidation state during the reaction see
http://www.wbateman.demon.co.uk/newsums/sum5.2/sum5.2.htm

Heterogeneous catalysts such as surface catalysts involve steps such as; diffusion to surface, adsorption on surface, reaction at surface, deadsorption from surface, diffusion from surface.
If two reactant molecules collide they may react if they have enough energy.  If they are brought together on the surface of a catalyst the activation energy may be lower so at a given temperature the reaction will be faster. 

The reaction profile for a catalysed and an uncatalysed reaction is shown below.

2.3 (f) Thermodynamic and kinetic stability
One system is thermodynamically stable with respect to a second one if the first one is lower than the second on an enthalpy level diagram.
e.g. Oxygen is energetically stable with respect to ozone.
ozone        (unstable)
               |
               |
oxygen    \/  (stable)
Even if a system is thermodynamically unstable and is expected to react to form a stable one the system may not react.  The system will not react if it is kinetically stable. This means that the reaction proceeds too slowly for any reaction to be seen. If kinetically unstable, a reaction is fast and observations can be made.  When a system is thermodynamically unstable but kinetically stable, the reaction is likely to be seen but only under favourable conditions.  Sugar and oxygen is a system like this with respect to carbon dioxide and water.  A bowl of sugar on the table does not react but if heated an exothermic reaction takes place.