1.

Define the Second Law of

Thermodynamics.

2. Define the Third Law of Thermodynamics.

3. Illustrate applications of both of these laws.

4. Determine Standard Entropies of Reaction

using relevant data.
 Spontaneous processes
 The second law of thermodynamics explains why
chemical processes tend to favour one direction.
 A reaction that does occur under the specified set of
conditions is said to be spontaneous and vice versa.
 Egs of spontaneous processes that we observe each day
 Spontaneous processes
 These examples show that processes that occur
spontaneously in one direction cannot, under the
same conditions, also occur spontaneously in the
opposite direction.

 HOW CAN THERMODYNAMICS HELP US TO

PREDICT WHETHER A PROCESS WILL OCCUR
SPONTANEOUSLY?
 Predictor of Spontaneity
 Assuming that spontaneous processes occur to
decrease the energy of a system; that is, exothermic
reactions are spontaneous. ∆H = -ve
 Indeed, a large number of exothermic reactions are
spontaneous.
 E.g. CH4)g) + 2O2(g) → CO2(g) + 2H2O(l)∆H0 = -890.4 kJ
 However, a number of spontaneous reactions are
endothermic.
 E.g. H2O(s) → H2O (l) ∆H0 = 6.01kJ
 Predictor of Spontaneity
 A better assumption therefore is that exothermicity
favours the spontaneity of a reaction but does not
guarantee it.

 In order to predict spontaneity of a process we need to

know the changes in enthalpy AND entropy of the
system
 What is Entropy
 Entropy (represented by the symbol S) is a direct
measure of the randomness /disorder of a system
therefore Ssolid < Sliquid << Sgas

 An ordered state has a low probability of occurring and

hence, a small entropy

 However, a disordered state will have a high

probability of occurring and hence a high entropy
 Disorder and probability
 If you were to offload bricks from a wheel-barrow,
which picture would it more likely look like?

 Disorder is more probable than order!

 The Second Law of
Thermodynamics
 The Second Law of Thermodynamics is considered to
be the most fundamental law of science.

 CP Snow once wrote: “Not knowing the

Second Law of Thermodynamics is like never
having read a work of Shakespeare.”
Definition of the Second Law of
Thermodynamics
 The Second law of Thermodynamics is an
expression of the universal law of increasing
entropy.

 It states that the entropy of an isolated

system which is not in equilibrium will tend
to increase in a spontaneous process over
time, approaching a maximum value at
equilibrium.
The Second Law of Thermodynamics has
many versions
 In terms of entropy, it states that in a system, a
process that occurs will tend to increase the total
entropy of the universe.

 Clausius' version states that heat generally cannot

spontaneously flow from a material at lower
temperature to a material at higher temperature.

 Kelvin's version states that it is impossible to

convert heat completely into work, some must be
transferred into a lower-energy reservoir.
An Equation for The Second Law of
Thermodynamics

ΔSuniverse = ΔSsystem + ΔSsurroundings

 For a spontaneous process to occur:
ΔSuniverse = ΔSsystem + ΔSsurroundings > 0

 and at equilibrium
ΔSuniverse = ΔSsystem + ΔSsurroundings = 0
Spontaneous change ALWAYS moves
toward higher entropy!
Hence:

ΔSuniverse = ΔSsystem + ΔSsurroundings ≥ 0

Take an air conditioner, for example
 It cools the air in the room, thus
decreasing the entropy of the air.

 However, the heat used in

operating the air conditioner
always makes a bigger
contribution to the entropy of the
surroundings than the decrease in
entropy of the air.

 Thus the TOTAL entropy of the

universe INCREASES!
Applications of the Second Law of
Thermodynamics
 This law can explain from the simple, such as how you heat
the water and make hot coffee or why the hot coffee in your
mug gets cooled to the not so simple, e.g. the expansion of
the cosmos or how an engine works.

 Donald Haynie once said: “Any theory claiming to

describe how organisms originate and continue to exist
by natural causes must be compatible with the first and
second laws of thermodynamics.”
Standard Entropy change of
Reaction
ΔS°reaction = ∑ΔS°products - ∑ΔS°reactants

 Consider the following reaction:

aA + bB → cC + dD

Hence ΔS°reaction = (cS°C + dS°D) – (aS°A + bS°B)

EXAMPLE:
 N2(g) + 3H2(g) → 2NH3(g)
 S°H2 = 131 J/Kmol
 S°NH3 = 193 J/kmol
 S°N2 = 192 J/Kmol

 What is the ΔS°reaction?

 Now ΔS°reaction = [2 x 193] – [192 + (3 x 131)]

= -199J/K.mol
 Third Law of Thermodynamics
 The entropy of a substance approaches zero
as its temperature approaches absolute zero.

OR
 The entropy of a perfect crystalline
substance is zero at the absolute zero of
temperature.
 How is this possible?
 Absolute zero is 0K (-273.15 °C).

 At absolute zero, the particles in a substance has

minimum motion.

 Hence, the particles are in a PERFECTLY ORDERED

state.

 Thus, if there is NO disorder then the entropy is

ZERO.