Lesson 5

Entropy and Free Energy

The Central Science, 12th ed, 2013

Prentice-Hall International
Brown, T.L., Lemay, H.E., and Burnsten
 Lesson Outline

A. Entropy and Entropy Changes in the System

and Surroundings
B. Predicting the Spontaneity
 Review
Thermodynamics: the science of heat and work
Thermochemistry: the relationship between chemical
reactions and energy changes
Energy (E) The capacity to do work or to transfer heat.
Work (w) The energy expended to move an object against an
opposing force.
w=Fxd
Heat (q) Derived from the movements of atoms and
molecules (including vibrations and rotations).
Enthalpy (H) Enthalpy is the heat absorbed (or released) by a
system during a constant-pressure process.
 Laws of Thermodynamics
0th Law of Thermodynamics
If A is in thermal equilibrium with B, and B is in thermal
equilibrium with C, then C is also in thermal equilibrium with A.
1st Law of Thermodynamics
Energy of the universe is constant (conserved). ΔE = q + w q =
heat absorbed by the system, w = work done on the system
2nd Law of Thermodynamics
In a spontaneous process, the entropy of the universe increases.
ΔSuniverse = ΔSsys + ΔSsurr > 0 (if spontaneous)
3rd Law of Thermodynamics
The entropy of a pure crystalline substance at absolute zero is
zero: S(0 K) = 0.
 Spontaneous Process
• Thermodynamics is concerned with the question:
can a reaction occur?
• First Law of Thermodynamics: energy is conserved.
• Any process that occurs without outside
intervention is spontaneous.
• When two eggs are dropped they spontaneously
break.
• The reverse reaction is not spontaneous.
• We can conclude that a spontaneous process has a
direction.
Spontaneous Reaction
• A process that is spontaneous in one
direction is not spontaneous in the opposite
direction.
• The direction of a spontaneous process
can depend on temperature:

• Ice turning to water is spontaneous at T >

0C, Water turning to ice is spontaneous at
T < 0C.
 Reversible Processes

Reversible process: the system changes in such a way

that the system and surroundings can be put back in their
original states by exactly reversing the process.
 Irreversible Process

• Irreversible processes cannot be undone by exactly

reversing the change to the system.
• Spontaneous processes are irreversible.
 Entropy
• Entropy is a measure of the randomness or
disorderliness of a system.
• Spontaneous reactions proceed to lower energy or
higher entropy.
• In ice, the molecules are very well ordered
because of the H-bonds.
• Therefore, ice has a low entropy.
 Entropy
• There is a balance between energy and entropy
considerations.
• When an ionic solid is placed in water two things happen:
–the water organizes into hydrates about the ions (so the entropy
decreases), and
–the ions in the crystal dissociate (the hydrated ions are less ordered
than the crystal, so the entropy increases).
 Entropy
• Generally, when an increase in entropy in one
process is associated with a decrease in entropy in
another, the increase in entropy dominates.
• Entropy is a state function.
• For a system, S = Sfinal - Sinitial.
• If S > 0 the randomness increases, if S < 0 the
order increases.
 Entropy
• For a process occurring at constant temperature (an
isothermal process), the change in entropy is equal
to the heat that would be transferred if the process
were reversible divided by the absolute
temperature:
 The Second Law of
Thermodynamics
• The second law of thermodynamics explains why
spontaneous processes have a direction.
• Suniv = Ssys + Ssurr: the change in entropy of the universe
is the sum of the change in entropy of the system and the
change in entropy of the surroundings.
• For reversible processes:
ΔSuniv = ΔSsystem + ΔSsurroundings = 0
• For irreversible processes:
ΔSuniv = Δssystem + ΔSsurroundings > 0
• For any spontaneous process, the entropy of the universe
increases: (ΔSuniv >0)
• Entropy is not conserved: Suniv is increasing.
 The Molecular
Interpretation of Entropy
• A gas is less ordered than a liquid that is less
ordered than a solid.
• Any process that increases the number of gas
molecules leads to an increase in entropy.
• When NO(g) reacts with O2(g) to form NO2(g), the
total number of gas molecules decreases, and the
entropy decreases.
The Molecular Interpretation
of Entropy
The Molecular Interpretation
of Entropy
• There are three atomic modes of motion:
– translation (the moving of a molecule from one point in
space to another),
– vibration (the shortening and lengthening of bonds,
including the change in bond angles),
– rotation (the spinning of a molecule about some axis).
The Molecular Interpretation
of Entropy
• Energy is required to get a molecule to translate, vibrate or
rotate.
• The more energy stored in translation, vibration and
rotation, the greater the degrees of freedom and the higher
the entropy.
• In a perfect crystal at 0 K there is no translation, rotation or
vibration of molecules. Therefore, this is a state of perfect
order.
The Molecular Interpretation
of Entropy
• Third Law of Thermodynamics: the entropy of a
perfect crystal at 0 K is zero.
• Entropy changes dramatically at a phase change.
• As we heat a substance from absolute zero, the
entropy must increase.
• If there are two different solid state forms of a
substance, then the entropy increases at the solid
state phase change.
Enthalpy and Enthalpies of
Reaction
The Molecular Interpretation
of Entropy
• Boiling corresponds to a much greater change in
entropy than melting.
• Entropy will increase when
–liquids or solutions are formed from solids,
–gases are formed from solids or liquids,
–the number of gas molecules increase,
–the temperature is increased.
Entropy Changes in Chemical
Reactions
• Absolute entropy can be determined from
complicated measurements.
• Standard molar entropy, S: entropy of a substance
in its standard state. Similar in concept to H.
• Units: J/mol-K. Note units of H: kJ/mol.
• Standard molar entropies of elements are not zero.
• For a chemical reaction which produces n moles of
products from m moles of reactants:
S  =  nS (products) −  mS (reactants)
Properties of Enthalpy
Entropy Equations
Entropy Change in the
Universe
 Gibbs Free Energy
• For a spontaneous reaction the entropy of the
universe must increase.
• Reactions with large negative H values are
spontaneous.
• How to we balance S and H to predict whether
a reaction is spontaneous?
• Gibbs free energy, G, of a state is
G = H − TS
• For a process occurring at constant temperature
G = H − TS
 Gibbs Free Energy
• There are three important conditions:
–If G < 0 then the forward reaction is spontaneous.
–If G = 0 then reaction is at equilibrium and no net reaction will occur.
–If G > 0 then the forward reaction is not spontaneous. If G > 0, work must
be supplied from the surroundings to drive the reaction.
• For a reaction the free energy of the reactants decreases to a
minimum (equilibrium) and then increases to the free energy
of the products.
 Gibbs Free Energy
Standard Free-Energy Changes
We can tabulate standard free-energies of formation, Gf (c.f.
standard enthalpies of formation).
Standard states are: pure solid, pure liquid, 1 atm (gas), 1 M
concentration (solution), and G = 0 for elements.
G for a process is given by

G =  nG f (products) −  mG f (reactants)

The quantity G for a reaction tells us whether a mixture of
substances will spontaneously react to produce more reactants
(G > 0) or products (G < 0).
 Free Energy and
Temperature
• Focus on G = H - TS:
–If H < 0 and S > 0, then G is always negative.
–If H > 0 and S < 0, then G is always positive. (That
is, the reverse of 1.)
–If H < 0 and S < 0, then G is negative at low
temperatures.
–If H > 0 and S > 0, then G is negative at high
temperatures.
• Even though a reaction has a negative G it may occur too
slowly to be observed.
Free Energy and
Temperature