Now we have discussed, and looked at, various factors affecting
the reactivity of a species, and which types of reagents attack
where, we can look at the variation of these factors from one structure
to another, and hope these factors also affect the course, and rate,
of a reaction.
Firstly, a basic tenet of chemistry is that systems tend towards
their lowest energy state.
Therefore, we might reasonably expect that the greater the difference
in energy betweenstarting material and products, the more
the equilibrium will favour the lower in energy. We can use
this idea to work out how much of a given starting material will
react, i.e. the extent of the reaction. The larger the arrow in
the diagram below, the bigger the energy gap, and the more the reaction
favours products over starting materials:
A brief look at the thermodynamics course in the physical
chemistry section is recommended if this material is unfamiliar.
For the purposes of a brief summary (this material is presented
in more depth in the physical chemistry section) we will now look
at some basic thermodynamics.
The energy change of a reaction ΔH
can be measured as the heat of the reaction. It is, however,
not adequate for measuring the difference in stability between
the reactants and products. This is essentially due to the
Second Law of Thermodynamics, which paraphrased states that: systems
tend towards maximum entropy (disorder). This leads us to
define the Gibb's free energy, so that we might consider the entropy
change of both the system and the surroundings in one. Hence
ΔG = ΔH - TΔS
This expression, it is found, relates the Gibb's energy
change to the extent of a reaction via:
ΔG = - RTlnK
Where K is the equilibrium constant, and is equal
to the concentration of products over the concentration of reactants.
The larger the value of K, the further the reaction has proceeded
to products. This equation makes intuitive sense, for if we
set ΔG = 0, we find that K = 1, which
corresponds to 50% products, and 50% reactants. In order for
a reaction to occur, ΔG < 0
Now we have a measure of the extent of a reaction,
we can work on finding an expression for the rate of a reaction.
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