17.2-17.

3 Spontaneous and
Nonspontaneous Processes - Entropy
 Spontaneous vs. Nonspontaneous Processes
• The AP Board now prefers the term thermodynamically
favored to substitute for spontaneous although saying
spontaneous will never lose points.

• In thermodynamics, we must predict spontaneity.

• A spontaneous process is one that does not require outside
intervention.
• The spontaneity of a reaction is the direction in which and extent to
which a chemical reaction proceeds. (NOT HOW FAST IT OCCURS)

• Predicting if a chemical process is thermodynamically

favored can be challenging. In order to do so we must:
– 1.) Develop a chemical potential that predicts the direction
of a chemical system.
– 2.) We must not confuse spontaneity with speed.
 Chemical Reactions that are
Not Thermodynamically Favored
• A nonspontaneous reaction can not be made
spontaneous by use of a catalyst…however, this
doesn’t mean nonspontaneous reactions are
impossible. Nonspontaneous reactions can be
made possible by coupling them with highly
spontaneous reactions.
– Example: Iron can be separated from its ore if external
energy , usually by means of another chemical reaction
that is spontaneous, is supplied.
 Entropy and the Second Law of
Thermodynamics
• Most thermodynamically favored processes are
exothermic, but some are endothermic.
– Examples:
• Ice melting at 0oC
• The evaporation of liquid water to gaseous water
• The dissolution of sodium chloride in water
– All three examples are endothermic processes and
still they are spontaneous.

• The reason that this is true is because the criterion for spontaneity is
the entropy of the universe.

• Entropy (S) – the disorder or randomness at the molecular level.

 Entropy
• Entropy (S) is the thermodynamically function that increases with the
number of energetically equivalent ways to arrange the components of a
system to achieve a particular state.

• S = k ln W (k is known as the Boltzmann constant (the gas constant divided

by Avogadro’s number: 1.38x10-23 J/K) W is the number of energetically
equivalent ways to arrange the components of a system). As W increases,
so does entropy!

• You will not be expected to know the equation above for the AP exam. You
are however expected to understand that as the randomness of a system
increases, so does entropy (S) and the value of entropy would be positive.
This is because Sfinal > Sinitial, So… ΔS is positive.

• For any spontaneous process, the entropy of the universe increases (ΔSuniv >
0)

• Entropy, like enthalpy, is a state function…it’s value depends only on the

state of the system, not on how the system arrived at that state.
 Let’s Try a Practice Problem!
Consider these three changes in the possible
distribution of 6 gaseous particles within three
interconnected boxes. Which change has a positive
ΔS?

a.) Less to more random

 Entropy Changes Associated with a Change in State

• Entropy increases when matter changes from a

solid to a liquid, and again from a liquid to a gas.

• Gases are more disordered than both solids and

liquids, and a gas has more energetically equivalent
configurations because it has more ways to
distribute its energy.

• Entropy also increases as the number of moles of

gas increases during a chemical reaction.
 Let’s Try Another!!!
Predict the sign of ΔS for each process:

a.) the boiling of water

b.) I2(g)  I2(s)
c.) CaCO3(s)  CaO(s) + CO2(g)

a.) ΔS is positive
b.) ΔS is negative
c.) ΔS is positive
17.2-17.3 pgs. 852-853 #’s 28 & 32
Read 17.4-17.5 pgs. 824-831