Thermodynamics: Spontaneity, Entropy and Free Energy

Thermodynamics:
Spontaneity, Entropy
and Free Energy
Objectives
• Be able to define and use the concepts of free

energy change (ΔG) and entropy change (ΔS)
• Understand that enthalpy change alone is not

sufficient to explain spontaneous changes and
recognise the role of entropy
Thermodynamics
Thermodynamics studies how changes in energy, entropy

and temperature affect the spontaneity of a process or
chemical reaction.
Using thermodynamics we can predict the direction a

reaction will go, and also the driving force of a reaction or
system to go to equilibrium.
Spontaneity
A spontaneous process is one that occurs without outside
intervention. Examples include:
-
- a ball - ice melting
rolling at
downhill temperature
s above 0oC
- gases
expanding to fill
their container
- two
gases
mixing
Normally we expect exothermic process
to be spontaneous.
• Why? …
• Because matter would always fall to the
lower energy state
But some endothermic processes are also

spontaneous.
Examples:
NaCl(s)  NaCl (aq) ΔH= +3.9 kJ mol-1
Br2(l)  Br2 (g) ΔH = +15.438 kJ/mol
Spontaneity
There are three factors that combine to
predict spontaneity. They are:
1. Enthalpy Change ∆H
2. Temperature T
3. Entropy Change ∆S
These factors are combined in an
equation to give ∆Go, the
standard free energy change
(Gibbs free energy change),
∆Go = ∆Ho - T ∆So we will deal with this
next week
Entropy
Entropy, S, is a measure of randomness or disorder.
• More random the arrangement the higher the entropy
• Matter would prefer to be disorderly ( to have higher

entropy).
• This is because there are many ways (or positions)

that lead to disorder, but very few that lead to an
ordered state.
Low Entropy High
Low Entropy High Entropy
Entropy
Low Entropy High

Entropy
Low Entropy High
Entropy
Low Entropy High

Entropy
Factors that Affect Entropy
1. Entropy g
Entropy (J K-1
increases with
temperature. l
mol-1)
s
2. Entropy increases mpt bp
t (K)
Temperature
from
solids  liquids 
Gases
ΔSo and Mixtures
Mixtures have more entropy than pure

substances.
Total Entropy Change
• System
consists of reactants and products
• Surroundings
anything else ( water, air,
container) that can absorb or give
energy to the system
• Universe
made up of the system and the
surroundings
ΔStotal(universe) = ΔSsurroundings +
ΔSsystem +
Spontaneous
Calculating Entropy
Changes
For any chemical reaction,
∆S °system = Σn ∆S° products – Σn ∆S° reactants
units = J•mol-1 K-1
∆S °surroundings = - ∆H° reaction

T
∆S °total = ∆S° system + ∆S° surroundings

Worked Example
Determine the standard entropy change for the decomposition of one mole of
solid calcium carbonate, forming solid calcium oxide and carbon dioxide gas.
CaCO3(s) → CaO(s) + CO2 (g) S°(J/mol. K)
CaCO3 92.9
CaO 39.8
CO2 213.7
Δ Sosystem = Σ So products - Σ So reactants
Δ S°sys = [S° CaO(s)] + S° CO2(g)] – [ S° CaCO3(s)]
∆S°sys = 39.8 + 213.7 – 92.9
= +160.6 J/mol • K
Q2 (i) Calculate the standard enthalpy change for AgCl(s) dissolving in water.
AgCl(s) → Ag+(aq) + Cl–(aq)
Hence calculate ∆SØSURR at 298K for this reaction.
ΔHØRXN = [+105.6 + (-167.2)] – [-127.1] = + 65.5 kJ mol-1
∆SØSURR = -∆H = - 65500 = -219.8 J K-1 mol-1

T 298
(ii) Calculate ∆S SYS for silver chloride dissolving in water.
Ø
∆SØSYS = [72.7 + 56.5] – [96.2] = +33.0 J K-1 mol-1
(iii) Calculate ∆SØTOTAL for silver chloride dissolving in water at 298 K and comment
on the result of your calculation.
∆SøTOTAL = -219.8 + 33.0 = -186.8 J mol-1 K-1
 Not spontaneous i.e. not soluble
Substance Ag+(aq) Cl-(aq) AgCl(s)
ΔHfØ /kJ mol-1 +105.6 -167.2 -127.1
SØ /J K-1 mol-1 72.7 56.5 96.2

Predicting the Sign of ΔSo
of a System
1. Look for the physical states on reactant and
product side
KCl (s)  KCl (aq) + ΔSo
H2O (l)  H2O(g) + ΔSo
KCl (aq) → KCl (s) - ΔSo
If a substance goes from a more ordered phase

(solid) to a less ordered phase (liquid or gas), its
entropy increases.
Predicting the Sign of ΔSo
of a System
2.Compare the states of products versus
reactants.
2 KClO3(s)  2 KCl(s) + 3 O2(g) +ΔSo

6 CO2 (g) + 6H2O (g) C6H12O6 (s) + 6 O2 (g) -ΔSo
The production of a gaseous product from a solid

reactant indicates an increase in entropy.
.
Predicting the Sign of
ΔSo a System
3. If the physical state is similar then compare the
number of moles of products versus reactants.
N2(g) + 3 H2(g)  + 2NH3(g) - ΔSo

The production of fewer gaseous product means a
decrease in entropy value of the system, thus,
negative ΔSo.
Calculation of ∆Go
∆Go = ∆Ho - T∆So

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Thermodynamics:

• Be able to define and use the concepts of free

• Understand that enthalpy change alone is not

Thermodynamics studies how changes in energy, entropy

Using thermodynamics we can predict the direction a

But some endothermic processes are also

• More random the arrangement the higher the entropy

• Matter would prefer to be disorderly ( to have higher

• This is because there are many ways (or positions)

Low Entropy High

Low Entropy High

Mixtures have more entropy than pure

∆S °system = Σn ∆S° products – Σn ∆S° reactants

units = J•mol-1 K-1

∆S °surroundings = - ∆H° reaction

∆S °total = ∆S° system + ∆S° surroundings

Δ Sosystem = Σ So products - Σ So reactants

Δ S°sys = [S° CaO(s)] + S° CO2(g)] – [ S° CaCO3(s)]

∆S°sys = 39.8 + 213.7 – 92.9

∆SØSURR = -∆H = - 65500 = -219.8 J K-1 mol-1

∆SØSYS = [72.7 + 56.5] – [96.2] = +33.0 J K-1 mol-1

Substance Ag+(aq) Cl-(aq) AgCl(s)

ΔHfØ /kJ mol-1 +105.6 -167.2 -127.1

SØ /J K-1 mol-1 72.7 56.5 96.2

KCl (s)  KCl (aq) + ΔSo

H2O (l)  H2O(g) + ΔSo

KCl (aq) → KCl (s) - ΔSo

If a substance goes from a more ordered phase

2 KClO3(s)  2 KCl(s) + 3 O2(g) +ΔSo

The production of a gaseous product from a solid

N2(g) + 3 H2(g)  + 2NH3(g) - ΔSo

∆Go = ∆Ho - T∆So

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