Topic 2:

Thermodynamics
(Part II)
Entropy and Free Energy
Spontaneity of Reaction
 Recall
o Calorimetric method: Q= mcT
o Hesss Law of Heat Summation: (book
keeping in Chemistry)
Single-step reaction Multi-step reaction
A
D H1 A
B H2
B
C H3

C
D H4

A
D H1 A
D H2+ H3 + H4

H1= H2+ H3 + H4
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 Learning Objectives
o Differentiate between spontaneous and non
spontaneous reactions.
o Define entropy and its relationship towards
spontaneity of reaction.
o Predict spontaneity of a reaction using
o Sign of entropy change, S
o Gibbs Free Energy Change, G

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Can you unboil an egg?
What is a spontaneous process?
o A spontaneous process is a physical or
chemical change that occurs with no outside
intervention.
o Raw egg
Hard boiled egg (spontaneous)
o Hard boiled egg
Raw egg (non spontaneous)

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 Rusting as spontaneous process
4Fe(s) + 3O2(g)
2Fe2O3(s) H=-1625 kJ
o Iron object when left
outdoors in moist air
will rust slowly
according to the
equation.
o It is spontaneous as no
(or very little help)
outside help is needed
for it to happen.
o Does spontaneous
mean fast and
instantaneous?
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Combustion as spontaneous process
o Combustion of methane is spontaneous once it is
ignited:
CH4(g) + 2O2(g)
CO2(g) + 2H2O(l) H = 891 kJ

o Is the reverse reaction spontaneous?

CO2(g) + 2H2O(l)
CH4(g) + 2O2(g) H = 891 kJ

o The reverse reaction is not spontaneous as it is an

endothermic reaction.

So can we conclude that all endothermic reactions

are non spontaneous?

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Wait
o Ice melts at room temperature.
H2O(s)
H2O(l) H=6.10 kJ
o Melting is a spontaneous process at room
temperature, but it is an endothermic reaction.
o So endothermic reaction can be spontaneous
given right conditions.
o Spontaneity of reaction is not depend on
enthalpy change of reaction only.

What actually governs the spontaneity of reaction?

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 What is entropy?
o A measure of the disorder or randomness of
the particles that make up a system.
o The tendency towards disorder or
randomness is summarized in Second law of
thermodynamics:

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 Example 1:
o A hot frying pan cools down when it is
taken off the kitchen stove.
o Its thermal energy ("heat") flows out to
the cooler room air. The opposite
never happen.

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 Example 2:
o Rocks roll down the mountain.
o high potential energy spread out, but
the reverse

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Example 3: Messing a room

Randomness increases,
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Entropy, S increases
 Charles Law and absolute
temperature scale
o Published by Joseph Louis Gay-Lussac in
1802 based on the unpublished works done
by Jacques Charles.
o At constant pressure, the volume of a fixed
mass of gas is directly proportional to the
absolute temperature.

V T, when P = constant

306853 Chemistry II (March 2013) 13

 Gay-Lussacs experiment

A gas expands or contracts by approximately 1/273 of its

volume at 0C for every C that the temperature rise or
falls.
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Thermodynamics 3rd Law
o Result of the experiment also showed that if
a substances were cooled to -273C, its
volume would theoretically be zero (perfect
crystalline state).
o 0 K (-273C) is called absolute zero.
o Thermodynamics 3rd Law states that the
entropy of a substances at absolute zero is
equivalent to zero.
o i.e. S = 0 JK-1 at 0 K.

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 It does make sense that:
o When solid changes to liquid or liquid to gas.

o Entropy, S increases from:

Perfect crystalline solid liquid gas
0 K <Tsolid (K) < TLiquid (K)< Tgas (K)
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Predict spontaneity using S
o Reaction is most likely to be
spontaneous when Suniverse> 0
(positive)
o Suniverse= Ssystem+ Ssurroundings

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 Ssystem
o S = S S
system products reactants
o If S > S
products , then S
reactants >0. system
o The entropy of system increases, the
randomness increases.(The system
becomes more disordered)

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 Predict the sign of Ssystem
Equation Ssystem
1. H2O(l)
H2O(g) +ve
2. CO2(g)
CO2(aq) ve
3. 2SO3(g)
2SO2(g) + O2(g) +ve
4. NaCl(s)
Na+(aq) + Cl-(aq) +ve

o Which process is likely to be spontaneous?

o Does it guarantee the spontaneity of
reaction if Ssystem is positive?
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 Entropy Changes in the
Ssurr):
Surroundings (
heat
o If exothermic, system surroundings,
motion of molecules , disorder , Ssurr
heat
o If endothermic, system surroundings,
motion of molecules , disorder , Ssurr
o Therefore Ssurr Hsys.
o Ssurr for a given amount of heat also
depends on T. If T , Ssurr and vice versa.
o Hence, 1 H ( J )
S Surrounding ( J K ) =
T (K )
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 Suniverse= Ssystem+ Ssurroundings
o For a reaction to be spontaneous, S surroundings
must be positive too.
o S =
surroundings


o For exothermic reaction (H=ve), heat
energy is released to surroundings, the
temperature of surroundings increases,
hence,
Ssurroundings>O

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22
 A quick summary
A reaction is A reaction is non
spontaneous at all spontaneous at any
temperatures if its temperatures if its

exothermic endothermic
(H <0 ) (H >0)
and and
increase in decrease in
entropy in system. entropy in system
(Ssystem>0) (Ssystem <0)
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What if.

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 Example 1:
N2(g) + 3H2(g)
2NH3(g)
Given:
H = 91.8 kJ (exothermic)
Ssystem = 197 J/K (decrease in entropy)

Is this reaction a spontaneous process?

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Derivation of the Gibbs Equation
o We understand that:
Suniverse= Ssystem+ Ssurroundings
o By substitutingS Surrounding =
H
T
H sys
And, Suniv = S sys
T
o Rearrange by multiplying T for both side:
TS univ = H sys TS sys
o Let G=-TS univ:

Gsystem= Hsystem TSsystem

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 Gibbs Free Energy, G
o Energy that is available to do work.
(useful energy).
o Gsystem= Hsystem TSsystem
o T (temperature in Kelvin) is the key
to determine spontaneity of
reaction.

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 Gsystem= Hsystem TSsystem

G Spontaneity
G <0 (-ve) reaction is spontaneous

G > 0 (+ve) non spontaneous

G = 0 reaction is at equilibrium.

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 Example 1:
N2(g) + 3H2(g)
2NH3(g)
Given
H0system = 91.8 kJ (exothermic)
S0system = 197 J/K (decrease in entropy)

If this reaction a spontaneous process at

(a) 298 K (b) 600K ?

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 Solution (a): at 298K
Gsystem
0
= H system
0
TS system
0

1000 J
= (91.8kJ ) (298K )(197 J / K )
1kJ
= 91800 J + 58700 J
= 33100 J
Since the free energy change, G
<0, it is a spontaneous process at
room temperature ,298K.

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 Solution (b): at 600K
Gsystem
0
= H system
0
TS system
0

1000 J
= (91.8kJ ) (600 K )(197 J / K )
1kJ
= 91800 J + 118200 J
= 26400 J
Since the free energy change, G >0, it is a
non spontaneous process at 600K.

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 What about G = 0?
o This means the reaction is at equilibrium.
equilibrium
o What is the temperature the reaction
reaches equilibrium?
Gsystem
0
= H system
0
TS system
0

1000 J
0 = (91.8kJ ) (T )(197 J / K )
1kJ
91800 J
T=
197 J / K
= 466 K
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 Summary:
o All spontaneous reactions involves increase in S .
universe
o Reaction will be spontaneous at all temperature if it is
exothermic and Ssystem is positive.
o Reaction will be non spontaneous at any temperature if
it is endothermic and Ssystem is negative.
o G in predicting spontaneity of reaction.
Gsystem= Hsystem TSsystem
o Limitation: a reaction maybe spontaneous, but it does
not tell how long it takes for the reaction to occur.

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 Practice Questions
(Summative Question for Thermodynamics)

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Meals Ready to Eat (MREs)

o MREs, Meals Ready to Eat, was first introduced during DESERT

STORM, 1991, to provide hot military meals for US soldiers.
Self -heating meals have a shelf life of 2 years and heat in
approximately 15 minutes.
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 How it works?
o Self-heating meals are composed of a tray of food
sealed within a patented bag.
o This bag contains a water pouch and a special heater
pad.
o The heater pad is composed of a supercorroding alloy
made of magnesium and iron mixed with sodium
chloride in a porous matrix.
o A string is attached to the water pouch, which when
pulled, releases water onto the heater pad. The pad
heats up as it reacts with the water.

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 How it works?
o Steam and heat released during the reaction heat
the meal in 10 to 15 minutes.
o The overall reaction within the heater pad is as
follows:
Mg (s) + 2 H2O (l) Mg(OH)2 (s) + H2 (g)
o This reactions does not normally occur according to
the activity series, however in the presence of iron,
magnesium will corrode or react with water
generating heat.

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 Problem 1:
o Self-heating meals can heat 300.0 g of
water from 4.0 C to 76.0 C in 12
minutes. Determine the amount of heat
energy gained by the water and released
by the heater pad.
(Given specific heat capacity of water =
4.18J/g.0C)

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 Problem 2:
Substance Hf(kJ/mol) S (J/Kmol)
Mg (s) 0 32.68
H2O (l) -285.83 69.91
Mg(OH)2 (s) -924.54 63.18
H2 (g) 0 130.68

Calculate the enthalpy of reaction for the reaction

of a heater pad.
Mg (s) + 2 H2O (l) Mg(OH)2 (s) + H2 (g)

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 Problem 3:
Substance Hf(kJ/mol) S(J/Kmol)
Mg (s) 0 32.68
H2O (l) -285.83 69.91
Mg(OH)2 (s) -924.54 63.18
H2 (g) 0 130.68

Calculate the entropy of the reaction and

predict if the system is becoming more
ordered or disordered.

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 Problem 4:

Calculate the free energy of the system

at 25C and explain if the reaction is
spontaneous or nonspontaneous at 25
0C.

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 Answers:

1. Q =90 288 J
2. H = -352.88 kJ
0

3. S = 21.36 J/K, more disordered.

0

4. G =359 25 J
0

As G0 < 0, this reaction is

spontaneous at room temperature.

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