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General
Chemistry/Thermod
ynamics/Free Energy
< General Chemistry | Thermodynamics

Introduction
What's the point of entropy and enthalpy?
So far, you have studied equilibrium to tell
you how far a reaction occurs and kinetics
to tell you how fast a reaction occurs.
Thermodynamics can tell you if a reaction
will occur, and at what temperatures. It
may seem too obvious, but why does an
ice cube spontaneously melt when it is at
30 °C? Melting is endothermic, so it would
seem that the reverse reaction (freezing) is
favored. After all, reactions that release
heat are usually more favorable than those
that absorb heat.

The answer is free energy (also called

Gibbs Free Energy). The change in free
energy for a reaction ultimately determines
if it can occur spontaneously or not. Free
energy is a combination of entropy and
enthalpy, and when a reaction decreases
the free energy, it will occur
spontaneously.

The Equation
Free energy is defined by
. By measuring or
calculating the entropy change and
enthalpy change of a reaction, you can
determine the change in free energy.
Notice that free energy depends on
temperature as well. In this equation (as
with all other thermo equations) must
be an absolute temperature, measured in
Kelvin. So the freezing point of water is not
zero but rather 273 K. By using the Kelvin
temperature scale, all temperatures will be
greater than zero.

When you have solved for for a

particular reaction at a certain
temperature, you will find one of three
possible outcomes:

Reaction type Means...

exergonic the reaction occurs spontaneously.

the reaction is at equilibrium.

endergonic the reaction will not occur.

Equipped with this knowledge, you can

determine the temperature at which a
reaction will be at equilibrium (by setting G
to 0 and solving for T). If a reaction is
endergonic, it will not occur
spontaneously. However, at a different
temperature, the reaction might occur.
Also, the reverse reaction will have an
opposite value for G. For example, the
combustion of propane will have a large
negative value for its change in free
energy. The reverse reaction would have
the same large value, but positive. This
makes sense, knowing that propane does
not spontaneously precipitate from the
smokey exhaust of a grill.

Spontaneity

Let's return to the example of a melting ice

cube. At T = 273 K (0 °C) the processes of
freezing and melting are at equilibrium. ΔG
must equal zero. At higher temperatures,
the melting process occurs spontaneously,
so we can deduce that ΔH is positive and
ΔS is also positive. We already know that
melting is endothermic and increases
entropy, so it seems the free energy
equation works.

Between entropy and enthalpy, there can

be four possible outcomes:

Result

+ - always + never spontaneous

- + always - always spontaneous

+ + + for low T, and - for high T depends on T

- - - for low T, and + for high T depends on T

We can see that the melting of an ice cube

is spontaneous for high temperatures.
Relating Free Energy

Free energy is related to equilibrium, as we

have already seen. There is an equation
that will allow you to convert between
reaction free energy and the equilibrium
constant for a particular reaction at a
given temperature:

is the Universal Gas constant, and is

the natural logarithm. A scientific
calculator will have a [LN] to calculate
logarithms and a [e^] button to calculate
anti-logarithms.
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