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Fundamental aspects
Chemists would like to know the details of how chemical reactions occur on a
microscopic scale. Why do certain reactions take place, but others not? If a single molecule
undergoes some type of rearrangement, how are the old bonds broken and the new bonds
formed? Why are some reactions fast while others are slow and why do reaction rates
depend on temperature? A number of theories have been devised over the years in order to
provide answer to questions such as these. Theories in chemical kinetics are used to
explain:
how chemical reactions take place (on a molecular level)
how temperature and participants concentration affect on the reaction rate
One of these theories is known as collision theory. This theory assumes that, for a
reaction to occur, reactant particles must collide. Collisions are vital for chemical changes.
The rate of a reaction depends on the frequency of collisions between reacting particles.
The more frequent the collisions, the faster the rate of the reaction. For a reaction to occur,
still there is something more than simply collision. For example, in a mixture of H2 and I2 at
ordinary temperature and pressure, each molecule undergoes about 1010 collisions per
second. If every collision between H2 and I2 resulted in the formation of HI, the reaction
would be over in much less than a second. Instead, at room temperature the reaction
proceeds very slow. Only about one in every 1013 collisions produces a reaction.
What keeps the reaction from occurring more rapidly?
The above example tells us that only certain
fraction of the total collisions cause chemical
H
change and is called successful or effective
collisions. In order to be effective, colliding
Br
I
HC
particles must:
- collide with the proper orientation;
H
- possess a certain minimum amount of energy
(activation energy).
ineffective collision (a)
If the orientation of the colliding particles is
wrong, no reaction occurs. In the elementary act,
represented on the left, iodine atom replaces
H
bromine atom in CH3Br molecule (single
displacement). So, only the proper arrangements
HC
Br
I
of the reacting particles lead to the formation of
products. These two particles collide, but are not
H
orientated correctly and then no reaction will take
place (a), the reactants simply "bounce" off each
effective collision (b)
other. Second picture shows correct orientation of
CH3Br + I CH3I + Br
particles; hence reaction takes place (b).
The energy that particles have during collision
is also important factor that keeps the reaction from occurring more rapidly. Not all of the
molecules have the same kinetic energy, as shown in the figure below. This is important
because the kinetic energy molecules carry when they collide is the principal source of the
energy that must be invested in a reaction to get it started. At a given temperature, the
number of particles with very low and with very high energy is very small, but the number of
particles with average kinetic energy is the largest. However, particles must possess energy
above the average in order to interact with each other (they are called active molecule).
Potential energy, kJ
Vertical axis in the graph represents the potential energy of the two reactant molecules that
are far apart from each other (in the beginning) while the horizontal coordinate shows the
reaction path. In the course of this reaction, an oxygen atom is transferred from nitrogen
dioxide to carbon monoxide. In order for the reaction to occur, the oxygen atom in NO2 must
collide with the carbon atom in CO. Reaction won't occur if the oxygen end of the NO2
molecule collides with the same atom on CO. Nor will it occur if nitrogen atom on NO2
collides with the carbon atom on CO (figure).