Spontaneous

Change, Entropy,
and Free Energy
Objectives:
 Predict the spontaneity of a process based
on entropy.
 Explain the second law of
thermodynamics.
 Use Gibbs’ free energy to determine the
direction of a reaction.
 Spontaneous Reaction
A reaction that does
occur under the
given set of
conditions without
any interruptions.
 Nonspontaneous Reaction
If the reaction does
not occur under
specified
conditions.
 A waterfall runs downhill.

A. Spontaneous

B. Nonspontaneous
 A lump of sugar dissolves in a cup of hot
coffee.
A. Spontaneous

B. Nonspontaneous
A lump of sugar
spontaneously dissolves in
a cup of coffee, but
dissolved sugar does not
spontaneously reappear in
its original form.
 Heat flows from colder object to hotter
one.
A. Spontaneous

B. Nonspontaneous
Heat flows from a
hotter object to a
colder one, but
reverse never happens
spontaneously.
 Gathering of all the molecules into one
bulb flasked.
A. Spontaneous
B. Nonspontaneous
 The spreading of gas molecules into an
evacuated bulb is an spontaneous process, but
the reverse process is not spontaneous.
 Iron exposed to water and oxygen forms
rust.
A. Spontaneous

B. Nonspontaneous
Iron exposed to water and
oxygen forms rust, but rust
does not spontaneously
change back to iron.
A piece of sodium metal reacts
violently with water to form
sodium hydroxide and hydrogen
gas.
Hydrogen gas does not
react with sodium
hydroxide to form water
and sodium.
 Entropy, S
 Is a thermodynamic quantity.
 It is used to measure how spread out or
dispersed the energy of a system is.
 It is used to described if the process is
spontaneous and can occur in a defined
direction or nonspontaneous and will occur in
the reversed direction.
 Entropy, S
 It is considered as a state function. it only
depends on the initial and final states of a
system.
 It is also a measure of how random or
disorder the system is.
∆S = Sfinal – Sinitial
Processes that lead to an increase in entropy
of the system:

a. Melting
b. Vaporization
c. Dissolving
d. Heating
Process Order Disorder
Melting Solid Liquid
 Process Order Disorder
Vaporization Liquid Vapor
 Process Order Disorder
Dissolving Solute Solution
Process Order Disorder
Heating System @ T1 System @ T2 (T2  T1)
How will you predict when entropy is positive or
negative?
 Entropy is positive when it underwent melting,
evaporation, and sublimation.
 If a reaction produces more gas molecules than it
consumes ΔS0 is positive.

 If there is no net change in the total number of gas

molecules then ΔS0 may be positive or negative but
will be relatively small numerically.
How will you predict when entropy is positive or
negative?
 Entropy may be negative when the chemical
substances underwent deposition, solidification, and
condensation.
 If the total number of gas diminishes ΔS0 is
negative.
Determine the entropy of a system for each of
the following processes.
1. A solid melts. - Positive
2. A liquid freezes. - Negative
3. A vapor converted to a solid. - Negative
4. A vapor condenses to a liquid. - Negative
5. A solid sublimes. - Positive
Determine the entropy of a system for each of
the following processes.
6. 2H2(g) + O2(g) → 2H2O(l) - Negative
7. NH4Cl(s) → NH3(g) + HCl(g) - Positive
8. H2(g) + Br2(g) → 2HBr(g) - Positive
9. CaCO3(s) → CaO(s) + CO2(g) - Positive
10. H2(g) + Cl2 → 2HCl - Positive
The Second Law of Thermodynamics

States that the state of entropy of the entire

universe, as an isolated system, will always
increase over time.
The Second Law of Thermodynamics

States that the changes in the entropy in

the universe can never be negative.
The Second Law of Thermodynamics
 Calculating Entropy Changes in the System:
Standard Entropy of Reaction, ΔS°rxn
Suppose that the system is represented by the
following reaction:
aA + bB → cC + dD
ΔS°rxn = ΣnS°(products) - ΣmS°(reactants)

ΔS°rxn = [cSo(C)+dSo(D)] ‒ [aSo(A)+bSo(B)]

Sample Problem 1:
For a general reaction:
H2(g) + I2(s) → 2HI(g)

Substance H2(g) I2(s) HI(g)

S0 (J/K•mol) 130.6 116.7 206.3
Sample Problem 1:
Solution:
ΔS° = ΣnS°(products) - ΣmS°(reactants)
= [(2)SoHI] – [(1)SoH2+(1)SoI2]
= [(2) (206.3)] – [(1) (130.6) + (1) (116.7)]
= [412.6] – [247.3]
ΔS° = +165.3 J/K•mol
Sample Problem 2:
For a general reaction:
CaCO3(s) → CO2(g) + CaO(s)

Substance CaCO3(s) CO2 (g) CaO(s)

S0 (J/K•mol) 92.9 213.6 39.8
Sample Problem 3:
For a general reaction
4KClO3(s) → 3KClO4(s) + KCl(s)

Substance KClO3(s) KClO4(s) KCl(s)

S0 (J/K•mol) 142.97 151.0 82.68
 Gibbs Free Energy, S
Another thermodynamic property that is
used to predict whether the reaction or
process will be spontaneous or
nonspontaneous.
 Gibbs Free Energy, S
Is defined as:
G = H – TS

The change in free energy (ΔG) of a system

for a constant-temperature process is
ΔG = ΔH - TΔS
Conditions for spontaneity and equilibrium at constant
temperature and pressure in terms of ΔG:
Example:
Calcium oxide (CaO), also called quicklime, is a
extremely valuable inorganic substance used in
steelmaking, production of calcium metal, the paper
industry, water treatment, and pollution control. It is
prepared by decomposing limestone (CaCO3) in a kiln
at a high temperature:

CaCo3(s) CaO(s) + CO2(g)

Sample Problem 1:
CaCo3(s) CaO(s) + CO2(g)

Substance CaCO3(s) CaO(s) CO2(g)

ΔH0f (kJ/mol) -1206.9 -635.6 -393.5

First we have to calculate ΔH0 and ΔS0 for the

reaction at 250C.
Solve for ΔH0
Solution:
∆H⁰rxn = ΣΔH0f(products) – ΣΔH0f(reactants)
= [c(H0fC)+d(H0fD] – [a(H0fA)+b(H0fB)]
= [(-635.6kJ/mol)+(-393.5 J/mol]–[(-1206.9kJ/mol)]
ΔH0rxn = 177.8 kJ/mol
Sample Problem 1:
CaCo3(s) CaO(s) + CO2(g)

Substance CaCO3(s) CaO(s) CO2(g)

ΔS0 (J/K•mol) 92.9 39.8 213.6

First we have to calculate ΔH0 and ΔS0 for the

reaction at 250C.
Solve for ΔS0
Solution:
ΔS° = ΣnS°(products) - ΣmS°(reactants)
= [So(CaO)+S0(CO2)] – [S0(CaCO3)]
= [(39.8J/K•mol)+(213.6J/K•mol]-[(92.9J/K•mol)
ΔS° = 160.5 J/K•mol
Solve for ΔG
Solution:
ΔG° = ΔH - TΔS
= 177.8 kJ/mol – (298K)(160.5J/K•mol)
= 177.8 kJ/mol – 47.83 kJ/mol
ΔG° = 129.97 kJ/mol or 130 kJ/mol
Sample Problem 2:
CaCo3(s) CaO(s) + CO2(g)

Substance CaCO3(s) CaO(s) CO2(g)

ΔH0f (kJ/mol) -1206.9 -635.6 -393.5

First we have to calculate ΔH0 and ΔS0 for the

reaction at 8400C.
Sample Problem 3:
The old camera flash bulb used Mg metal sealed in a bulb
with oxygen. The reaction is:
Mg + ½ O2 → MgO
Substance CaCO3(s) CaO(s) CO2(g)
ΔH0f (kJ/mol) 0 0 -601.2
ΔS0 (J/K•mol) 32.7 205.0 26.9
Sample Problem 3:
Mg + ½ O2 → MgO
Substance CaCO3(s) CaO(s) CO2(g)
ΔH0f (kJ/mol) 0 0 -601.2
ΔS0 (J/K•mol) 32.7 205.0 26.9

Calculate ΔH0, ΔS0, and ΔG for the reaction

at 250C.
 Thank you!
Presented by:
Cassandra C. Dorado