Collision Theory in Chemistry

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OpenStax Chemistry 2e

We should not be surprised that atoms, molecules, or ions must before they can react with each other. Atoms must be close together to form chemical bonds. This simple premise is the basis for a very powerful theory that explains many observations regarding chemical kinetics, including factors affecting reaction rates.

Collision theory is based on the following postulates:

  1. The rate of a reaction is to the rate of reactant collisions.
  2. The reacting species must collide in an that allows contact between the atoms that will become
    bonded together in the product.
  3. The collision must occur with adequate to permit mutual penetration of the reacting species’ valence shells so that the electrons can rearrange and form new bonds (and new chemical species).

We can see the importance of the two physical factors noted in postulates 2 and 3, the orientation and energy of collisions, when we consider the reaction of carbon monoxide with oxygen.

Carbon monoxide is a pollutant produced by the combustion of . To reduce this pollutant, automobiles have that use a catalyst to carry out this reaction. It is also a side reaction of the combustion of gunpowder that results in muzzle flash for many firearms. If carbon monoxide and oxygen are present in sufficient amounts, the reaction will occur at high temperature and pressure.

Although there are many different possible orientations the two molecules can have relative to each other, consider the two presented in the picture below. In the first case, the oxygen side of the carbon monoxide molecule collides with the oxygen molecule. In the second case, the carbon side of the carbon monoxide molecule collides with the oxygen molecule. The second case is clearly more likely to result in the formation of carbon dioxide, which has a central carbon atom bonded to two oxygen atoms (O = C = O). This is a rather simple example of how important the orientation of the collision is in terms of creating the desired product of the reaction.

Illustrated are two collisions that might take place between carbon monoxide and oxygen molecules. The orientation of the colliding molecules partially determines whether a reaction between the two molecules will occur. Source: OpenStax Chemistry 2e

If the collision does take place with the correct orientation, there is still no guarantee that the reaction will proceed to form carbon dioxide. In addition to a proper orientation, the collision must also occur with sufficient energy to result in product formation. When reactant species collide with both proper orientation and adequate energy, they combine to form an unstable species called an or a . These species are very short lived and usually undetectable by most analytical instruments. In some cases, sophisticated spectral measurements have been used to observe transition states.

Collision theory explains why most reaction rates increase as concentrations increase. With an increase in the concentration of any reacting substance, the chances for collisions between molecules are increased because there are more molecules per unit of volume. More collisions mean a faster reaction rate, assuming the energy of the collisions is adequate.