Spontaneity Entropy and Gives Free Energy

SPONTANEOUS CHANGE, ENTROPY AND
GIBBS FREE ENERGY

OBJECTIVES
• Predict the spontaneity of a process
based on entropy.
• Explain the second law of
thermodynamics and its significance.
• Use Gibbs’ free energy to determine
the direction of a reaction.
Will a
chemical
reaction
proceed or
not?
Spontaneous Reaction
- Chemical or biological reactions that take
place without the influence of any external
factor.
Nonspontaneous Reaction
- Chemical or biological reactions that
CANNOT take place without the influence of
any external factor.
Examples Of Spontaneous Reaction
Ball rolling downhill Iron rusts in the presence of air and

water
Gases expand to fill

Melting of ice their container
ENTROPY
• Entropy, S, is a thermodynamic quantity
that is a measure of the randomness or
disorder or the “available arrangements”
for the system or surroundings
• It refers to the number of ways the
energy of a system can be dispersed
through the motions of the particles
• The SI unit of entropy is joules per
Kelvin (J/K) and, like enthalpy, is a state
function.
ENTROPY
Molar entropy of the Molar entropy of the Molar entropy of the

solid state will be liquid state will be gaseous state will be
LOWEST INTERMEDIATE HIGHEST
Entropy, which is related to motion, is obviously dependent on

kinetic energy of the molecules at a given state.
https://www.slideshare.net/NicoleGala/chemical-thermodynamics-spontaneity-and-entropy
Rules in Predicting the Entropy of the
system:
1. If the reaction produces more gas

molecules than it consumes, ΔS° is
positive.
2. If the total number of gas molecules
diminishes, ΔS° is negative.
3. If there is no net change in the total
number of gas molecules, ΔS° may be
positive or negative, but will be relatively
small numerically.
SHILA#2A: Predict whether the entropy change
of the system in each of the following is positive
or negative.
• O2(g) —> 2O(g)
• N2 (g, 10 atm) —> N2 (g, 1atm)
• 6CO2(g) + 6H2O(g) —> C6H12O6(g) + 6O2(g)
• 2 H2(g) + O2(g) —> 2 H2O(l)
• NH4Cl(s) —> NH3(g) + HCl(g)

ENTROPY
Sample Problem:
One mole of water is vaporized at 100°C with the
absorption of 40.7 kJ of heat. What is the molar
entropy of vaporization?
Given:
T = 100°C + 273.15 = 373.15 K
ΔH/qrev = 40.7 kJ/mol = 40,700 J/mol
Solution:
𝐽
𝑞𝑟𝑒𝑣 40,700 𝑚𝑜𝑙 J
∆𝑆 = = = 109.07 mol . K
𝑇 373.15 𝐾
In EXOTHERMIC REACTIONS In ENDOTHERMIC REACTIONS
The heat released by the The disorder within the system
reaction increases the disorder increases sufficiently so that
of the surroundings while the the change in disorder of the
system is decreased, the large system is greater than the
amount of heat released to the decrease of the surroundings,
surroundings causes large then the total change in
increase in entropy resulting to a disorder can be positive and
net increase in entropy of the the reaction becomes
universe. spontaneous.
ENTROPY CHANGE OF REACTION
Sample Problem
• Calculate the change in entropy at standard
state in 25°C that accompanies the reaction:
C(s, graphite) + CO2(g) → 2CO(g)
Given: 5.740 J/mol.K 213.74 J/mol.K 197.67 J/mol.K
Asked: Entropy change of reaction
Solution:
∆𝑆° 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝐽 𝐽
= (2 𝑚𝑜𝑙 197.67 . 𝐾 − [(1 𝑚𝑜𝑙 5.740 .𝐾
𝑚𝑜𝑙 𝑚𝑜𝑙
𝐽
+ (1 𝑚𝑜𝑙 213.74 .𝐾 ]
𝑚𝑜𝑙
= 175.86 J/K
SHILA#2B
• Calculate the change in entropy at standard

state in 25°C that accompanies the reaction.
(Refer to the table on the standard entropy
values)
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
GIBBS FREE ENERGY and
CHEMICAL EQUILIBRIUM
SAMPLE PROBLEM
• Find ΔH, ΔS, and ΔG of the reaction. Is this reaction
exothermic and is it spontaneous?
Calculate entropy change:

ΔS° = ΣnS°(products) − ΣmS°(reactants)
= [ (1 mol) (240.5 J/mol.K) ] – [ (1 mol) (211
J/mol.K) + (1/2 mol) (205 J/mol.K)]
ΔS° = -73 J/K
Calculate enthalpy change:
ΔH° = Σ nΔHf° (products) – Σ mΔHf° (reactants)
= [(1 mol) (34 kJ/mol) ] – [ (1 mol) (90 kJ/mol) +
(1/2mol) (0 kJ/mol)]
ΔH° = - 56 kJ
Calculate Gibbs Free Energy change from above:

ΔG = ΔH – TΔS
= -56 kJ- [(298.15K) (-73 J/K)( 1kJ/1000 J)]
ΔG = - 34.24 kJ
Findings:
The reaction is exothermic at a ΔH = ( – )
It becomes more ordered (less gas) at a ΔS = (+)
It is spontaneous at 298.15 K at a ΔG = (–)
PERFORMANCE TASK #2
• You are told that a special chamber allows O2
to combine with N2 to form NO2 (nitrogen
dioxide). Using the reaction find ΔH, ΔS, and
ΔG of the reaction. Should you invest in an
engine that is said to burn air at room
temperature?

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SPONTANEOUS CHANGE, ENTROPY AND

GIBBS FREE ENERGY

Ball rolling downhill Iron rusts in the presence of air and

Gases expand to fill

Molar entropy of the Molar entropy of the Molar entropy of the

Entropy, which is related to motion, is obviously dependent on

1. If the reaction produces more gas

• N2 (g, 10 atm) —> N2 (g, 1atm)

• 6CO2(g) + 6H2O(g) —> C6H12O6(g) + 6O2(g)

• 2 H2(g) + O2(g) —> 2 H2O(l)

• NH4Cl(s) —> NH3(g) + HCl(g)

• Calculate the change in entropy at standard

Calculate entropy change:

Calculate Gibbs Free Energy change from above:

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