SECOND LAW OF THERMODYNAMICS

“The entropy of the universe increases in a spontaneous process and remains unchanged in an equilibrium process.”
Spontaneous Change
 one that occurs by itself without continuous outside assistance
 Water flowing over a waterfall
 Melting of ice cubes

Non-spontaneous Change
 processes that do not occur spontaneously. These processes will not continue to occur without outside intervention. They only
happen when an outside source of energy is introduced to drive them
 Moving up of water in falls
 Rolling drum up an inclined plane
Which of the following processes are non-spontaneous?
 Spreading of fragrance of perfume throughout a room
 Separation of N2 and O2 molecules in air
 Fixing of a broken watch
 Extraction of salt from seawater

ENTROPY

Entropy is simply a measure of how much the energy of the particles become more spread out in a process. It is also defined
as the thermodynamic quantity that expresses the degree of disorder in a system. If the system becomes less ordered, the entropy
increases. If the system becomes more ordered, the entropy decreases.

COMPARING ENTROPIES
A. Number of Possible Microstates. The greater the number of possible
microstates for a system, the higher the entropy. Microstate refers to the
arrangement of the energy of each molecule in the whole system at one instant.
It is directly related to the amount of the substance. Example, 100 g of metallic
copper has twice the entropy of 50 g at the same temperature.
B. Phases. Different phases have different entropies. Gases have higher entropy
than liquids and liquids have higher entropy than solids. The particles of gases
are more random than liquids and solids because they move freely in the bigger
spaces between them. When the phase of the substance is changed, there is
also a change in entropy. Entropy increases during these processes because
the particles become less ordered.
C. Temperature. The higher the temperature, the higher is the entropy. Entropy
increases as the temperature of a substance is raised because it corresponds to
the greater spread of kinetic energies.
D. Mixture vs Pure Solvent. Compared to a pure substance, in which all particles
are identical, the entropy of a mixture of two or more different particle types is
greater. This is because of the additional orientations and interactions that are
possible in a system comprised of nonidentical components.
E. Dissolved Substances vs. Precipitate. When a solid dissolve in a liquid such as
sodium chloride in water, the particles of the solid experience both a greater
freedom of motion and additional interactions with the solvent particles. This
corresponds to a more uniform dispersal of matter and energy. The process of
dissolution therefore involves an increase in entropy.
F. Presence of a Gas. The side of the equation with more moles of gas has a
higher total entropy. This is because a greater number of moles indicates a
greater number of gas particles and a greater number of arrangements of the
gas particles.
Examples. Which member of each pair do you expect to have a higher entropy?
A. solid phenol or liquid phenol
B. 1 mol of N2(g) mixed with 2 mol of O2(g) or 2 mol of NO2(g)
C. I2(s) or I2(g).
 D. block of copper at 20°C or at 40°C. E. diamond or graphite

CALCULATING ENTROPY
The symbol for entropy is S and the standard entropy of a substance is given by the symbol S∘, indicating that the
standard entropy is determined under standard conditions. Standard entropy is the entropy of a substance at 25°C and 1 atm
of pressure. The units for entropy are J/K • mol.
The entropy change for a reaction can be calculated by taking the difference between the total of the standard
entropy values of the products and those of the reactants:
ΔS∘rxn = Σ S∘(products)−Σ S∘(reactants)
Example. Calculate ΔSrxn for the following reaction:
1. N2(g)+3H2(g)→2NH3(g)
2. CaCO3(s)→CaO(s)+CO2(g)

Activity 6. Predict the entropy signs (positive/negative) and spontaneity (spontaneous /non-spontaneous ) of these
equations.
Reactions Entropy Spontaneity
signs (S/NS)
2NO2(g)N2O4(g) negative NS
C3H8(g) + 5O2(g)3CO2(g) + 4H2O(g)
Condensation of steam to liquid water
Sublimation of solid
2SO2 (g) + O2 (g)  2SO3 (g)
CO (g) + 2H2 (g)  CH3OH (g)
2H2 (g) + O2 (g) 2H2O (l)
N2 (g) + 3H2 (g) 2NH3 (g)
Ca(OH)2 (s)  Ca+2 (aq) + 2OH- (aq)
H2 (g)  2H (g)
2H2S (g) + 3O2 (g)  2H2O (l) + 2SO2 (g)
N2O4 (g)  2NO2 (g)
CO (g) + 2H2 (g)  CH3OH (l)
AgCl (g)  Ag+ (aq) + Cl- (aq)

GIBBS FREE ENERGY

 The amount of energy produced by a reaction that can be theoretically harnessed as work.
 calculates the amount of energy available in a system to do work
 allows you to determine whether a process is spontaneous or not
 uses the relationship between enthalpy and entropy in a system to determine the spontaneity of a process
The change in free energy, ΔG , is equal to the sum of the enthalpy plus the product of the temperature and entropy of the
system as shown in this equation: ∆G = ∆H - T∆S
If ΔG is positive, then the reaction is nonspontaneous ( meaning the input of external energy is necessary for the reaction to
occur) and if it is negative, then it is spontaneous (meaning, occurs without external energy input). If ΔG= 0, the system is at
equilibrium and there is no net change either in forward or reverse direction.
EXAMPLE.
1. Calculate ∆G at 290 K for this reaction:
2NO(g)+O2(g)→2NO2(g) Given: ∆H = -120 kJ ∆S = - 0.150 kJ/K
2. Consider the following reaction: N2O4 (g) → 2 NO2 (g) . The standard enthalpy of this reaction is 57.2 kJ and its standard entropy is
175.61 J/K. Find out the change of the Gibbs free energy at 25 °C in kJ. 4.87kJ, ns

Activity 7. Complete the table below.

∆G Spontaneity
Sample: NH4Cl (s)  NH3 (g) + HCl (g)
1. 2C (g) + H2 (g)  C2H2 (g)
2. SO2 + ½ O2  SO3

3. CaCO3  CaO +CO2

4. 2NO (g) + O2 (g)  2NO2 (g)

5. Ca (OH)2 (s) + 2HCl (g)  CaCl2 (s) + 2H2O (g)

Activity 8. Solve the following completely. Box your final answer.

1. Consider the following reaction: 2 C2H6 (g) → C4H10 (g) + H2 (g). The standard enthalpy of this reaction is 42.05 kJ and its
standard entropy is –18.28 J/K. Find out:
a) The change in the Gibbs free energy at 25 °C.
b) The change in the Gibbs free energy at 169 °C assuming that the enthalpy and the entropy do not change at this
temperature.

2. Consider the following reaction: PCl5 (g) → PCl3 (g) + Cl2 (g) . Calculate:
a) The change of enthalpy at 25 °C.
b) The change of entropy at 25 °C.
c) The change in the Gibbs free energy at 25 °C.
d) The change in the Gibbs free energy at 639 °C assuming that the enthalpy and the entropy do not change at this
temperature.

Enthalpies of formation (in kJ/mol at 25 °C, 1 atm):

∆Hf °(PCl5 (g)) = –374.9, ∆Hf °(PCl3 (g)) = –287
Standard entropies (in J/(mol·K) at 25 °C and 1 atm):
S°(PCl5 (g)) = 364.58, S°(PCl3 (g)) = 311.78, S°(Cl2 (g)) = 223.07