SPONTANEITY, ENTROPY AND FREE

ENERGY

The effect of changes in temperature, phase, number of particles and mixing of

particles on the entropy of a chemical system. [Qualitative treatment only.]

Predicting the sign (positive or negative) of the entropy change for a given
reaction
[Calculation of
for a reaction using standard entropies
is not
required.]

Standard Gibbs free energy of a reaction defined using

Calculations using the equation
The sign of
and its use in deducing whether a reaction is spontaneous.
The effect of temperature change on the spontaneity of a reaction.

ST

Law Thermodynamics

The first law of thermodynamics, the law of

conservation of energy states: Energy can be
neither created nor destroyed.
In other words, the energy of the universe is
constant.
Energy has been converted from one form to
another, but the same quantity of energy exists
before and after the process
How much energy is involved in the change? Does
energy flow into or out of the system? What form
does the energy finally assume, - or +?
But, it gives no info, why a particular process occurs
in a given direction or the speed of the process.

Spontaneity

To understand entropy and free energy, we need to understand

spontaneity
Spontaneity is related to 2nd law of thermodynamic
A process is said to be spontaneous if it occurs without outside
intervention
And it may be fast or slow
spontaneous in one direction only = irreversible
Some important spontaneity situations are such as:
A ball rolls down a hill but never spontaneously rolls back up the hill.
If exposed to air and moisture, steel rusts spontaneously. However, the iron
oxide in rust does not spontaneously change back to iron metal and oxygen
gas.
A gas fills its container uniformly. It never spontaneously collects at one end
of the container.
Heat flow always occurs from a hot object to a cooler one. The reverse
process never occurs spontaneously.
At temperatures below 0C, water spontaneously freezes, and at
temperatures above 0C, ice spontaneously melts.

Entropy
The characteristic common to all spontaneous processes is an
increase in a property called entropy, denoted by the symbol S.
The driving force for a spontaneous process is an increase in the entropy of
the universe.

Entropy, S, is a measure of the disorder (or randomness) in a

system.
In nature, any system in random motion tends to become more 'mixed up' or
disorderly as time passes;
i.e. nature tends towards maximum entropy in isolated systems
The system becomes energetically more stable when it becomes more disordered

Entropy = A measure of how energy and matter is spread out

(dispersed) among the atoms and molecules of a system and its
surroundings
The higher the randomness or disorder, the greater the entropy of
the system.
Entropy increases when the energy or matter spread out (disorder)

Diffusion A spontaneous
Change

2nd Law of Thermodynamics

The Second Law of Thermodynamics states that

the state of entropy of the entire universe, as an isolated system,
will always increase over time.

In other words:
For reversible processes:

S univ = S system + S surroundings = 0

For irreversible processes/spontaneous:

S univ = S system + S surroundings > 0

To predict whether a given process will be spontaneous, we must know

the sign of S univ,
If is positive, the entropy of the universe increases, and the process
is spontaneous in the direction written. feasible.
If is negative, the process is spontaneous in the opposite direction.
If is zero, the process has no tendency to occur, and the system is
at equilibrium.

Factors Affecting Entrophy

A) Change in Temperature
B) Change in Phase
C) Change in no of Particles
D) Mixing of Particles