The Second Law of

Thermodynamics

Heat will spontaneously flow from something

hotter to something colder, but it won’t flow
from something colder to something hotter.
Spontaneous Processes

Spontaneous processes are those that can

proceed without any outside intervention.
Processes that are spontaneous in one
direction are nonspontaneous in the reverse
direction.
Reversible Processes

The system changes in such a way that the

system and surroundings can be put back in
their original states by exactly reversing the
process.
 Irreversible Processes

Irreversible processes cannot be undone by exactly reversing

the change to the system.
All Spontaneous processes are irreversible.
Is often described as the inherent disorder of a
system – The more disordered the system, the
higher its entropy.
 Entropy is measure of
randomness/chaosness.

Total entropy of the system and its

surroundings increases in the course
of a spontaneous change.
 Entropy on the Molecular Scale

Implications:

• more particles
-> more states -> more entropy
• higher T
-> more energy states -> more entropy
• less structure (gas vs solid)
-> more states -> more entropy
 The Second Law of
Thermodynamics

Heat will spontaneously flow from something

hotter to something colder, but it won’t flow
from something colder to something hotter.
 The Second Law of
Thermodynamics

In its broader significance the second law acknowledges that

processes proceed in a certain direction but not in the opposite
direction.
 The Second Law of
Thermodynamics

Heat will not flow from a colder body to a hotter body unless
some other process (which does work) is also involved.
Entropy in a system

Entropy in the universe

Entropy in a system

Entropy in the universe

Order to Disorder

Natural processes tend to move toward a state of

greater disorder.
 Significance of the Second Law

o Helps explain everything that happens in the physical world.

o It can help determine which reaction will favor the
formation of the desired products to obtain better economic
yield.
 Sample Problem

Show quantitatively, that the process for dissolving NaCl in

water at 25°C has a positive entropy change value, S°universe.
NaCl(s) → NaCl(aq)

Given:
S°NaCl(s) = 72.1 J/mol K
S°NaCl(aq) = 115.5 J/mol K
Hf°NaCl(s) = -411.1 kJ/mol
Hf°NaCl(aq) = -407.3 kJ/mol
T = 25°C
 Second Law of
Thermodynamics
 The entropy of the universe increases in a
spontaneous process and remains unchanged
in an equilibrium process
 The Second Law of
Thermodynamics

The entropy of the universe does not change for reversible

processes and increases for spontaneous processes.

ΔS universe =ΔSsystem + ΔSsurroundings

Process tends not to occur; equilibrium is attained (ideal):

Irreversible (real, spontaneous):

Reverse process occurs spontaneously

∆S univ = ∆S sytem + ∆S surrounding < 0
 Calculating Entropy Changes in
the System
 ∆S°rxn = Σn S° (products) - ΣmS° (reactants)
where m and n are the stoichiometric coefficients in
the reaction
Ex: Calculate ∆S° of the given reaction
H2 (g) + I2(s) HI (g)
Where: SH2 = 130.6 J/K-mol
S I2 = 116.7 J/K-mol
SHI = 206.3 J/K-mol
 General rules in predicting whether an
entropy change is negative or positive

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. !
 Predict whether the entropy change of the system in
each of the following is positive or negative.
 O 2(g) —> 2O(g)
 N 2 (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)
Calculating th Entropy change
in the surrounding, ∆Ssur

∆Ssur -∆ Hsys
T
 Calculate the ∆S sys and ∆Ssurr of the synthesis of
ammonia.

N2(g) + 3 H2 (g) 2 NH3 (g) ∆H°rxn=-92.6 kJ

 S°N2 = 192 J/K-mol
 S° H2 =131 J/K-mol
 S° NH3 = 193 J/K-mol
 Third Law of Thermodynamics

 “the entropy of a perfect crystalline

substance is zero at the absolute zero of
temperature”
 At absolute zero (T = 0 K= -273.15 oC), the
entropy of a perfect crystal is 0.
 As the temperature increases, the freedom of
motion increases. The entropy of any
substance at a temperature above 0 K is
greater than zero.
 A solid like glass with imperfections built
into it will not have entropy = 0 even at 0 K
because it is not a perfect crystal and still has
some randomness left in it.
 Gibbs Free Energy, G

 Another thermodynamic function used in

order to express the spontaneity of a reaction
more directly
 Energy available to do useful work
∆G = ∆ H - T ∆ S
 Sample Problem

 The old camera flash bulb used Mg metal

sealed in a bulb with oxygen. The reaction
is:
 Mg + ½ O2 —> MgO
 S° J/K mol: 32.7 205.0 26.9
ΔHf° kJ/mol: 0 0 -601.2
 Ozone (O3) in the atmosphere can react with
Ozone (O3) in(NO):
nitric oxide the atmosphere can react
         O3(g) + with nitric
NO(g)
oxide
—> NO2(g) + O2(g).
 O3(g) + NO(g) —> NO2(g) + O2(g)
Calculate the G for this reaction at 25°C
(H =-199KJ/mol, S = -4.1 J/K-mol
 ΔSuniv ΔG ΔSuniv Reaction
 + - Increase Spontaneous
 0 0 Stay the same No change at
equilibrium
 - + Decrease Not spontaneous,
 Sample Problem

 Given: ΔH°= +177kJ and ΔS°= +285J/K

for the reaction
 NH4Cl(s) —> NH3 (g) + HCl (g)
 Find the ΔG° at 25°C and ΔG at 500 °C. At
what temperature will the reaction will occur