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Chapter 3: The Second

Law of Thermodynamics

Spontaneous Processes
Entropy
The Carnot Heat Engine
The Second Law of Thermodynamics
The Third Law of Thermodynamics
Gibbs Free Energy
Gibbs and Helmholtz Energies and its
Applications

First Law vs Second Law


The First Law of Thermodynamics
- Energy can change from one form to
another but cannot be destroyed or
created
- Internal energy and enthalpy of a
reaction
(1st law of thermodynamics cannot
explain the direction of the process)
The Second Law of Thermodynamics
- Chemical processes tend to favor one
direction

Spontaneous Process
In terms of chemical reaction:
- We consider exothermic and endothermic
reactions,
- exothermic reaction seems to favor
spontaneity while endothermic reaction is not
Some spontaneous process (conversion of
diamond to graphite) maybe so slow that the
tendency never realized in practice.
Thus, in order to determine the spontaneity of a
reaction, we need another term called
ENTROPY (S)

Spontaneous Process
A reaction that does occur in a given set of
conditions spontaneous reaction
A reaction that does not occur under specified
conditions non-spontaneous reaction
Examples:
A waterfall runs downhill but never up,
spontaneously
Water freezes below 0C and ice melts
above 0C, spontaneously (at 1 atm)
Heat flows from hotter object to colder one,
but reverse never happens spontaneously
Iron exposed to water and oxygen forms
rust, but rust does not change back to iron
spontaneously

What determines
reaction of
spontaneous
change?

The Dispersal of Energy


Ball does not rise as high after
each bounce due inelastic
losses.
Kinetic energy of the balls
overall motion (energy of
thermal motion of its particles
and those of the floor that it
hits).
Direction of spontaneous
change: toward a state in which
a ball at rest with all its energy
dispersed into random thermal
motion of molecules and of the
atoms of the virtually infinite
floor.

Ball (system) bouncing


on a floor (surrounding).

An object does not spontaneously


become warmer than its surroundings.
It is impossible that the jostling of
randomly vibrating atoms in the
surrounding will lead to the localization
of thermal motion in the object.
Opposite change: the spreading of the
objects energy into the surroundings as
thermal motion is natural.

Entropy, S
Entropy is often described as a measure on how
disperse or spread out the energy of a system among
the different possible ways that a system can contain
energy
The GREATER the dispersal of energy the GREATER
the entropy of a system
A system that spread to lower microstates has lower
entropy
A system that spread to higher microstates has higher
entropy

Spontaneous Process
Consider a cup of hot coffee:
Has a certain amount of entropy due to the
dispersal among the various energy states of
water molecules (vibrate, rotate,etc.)
Various energy states/dispersal of energy
known as MICROSTATES
> microstates , > entropy
Microstates increase with temperature
(i.e. more vibration and more rotation of
molecules)

Spontaneous Process

Entropy and Microstates

Second Law and Entropy

Thermodynamic definition of entropy


Focus on the change of entropy, dS that occurs
as a result of process change
The thermodynamic definition of entropy is
based on expression
dqrev
dS
T
For a measurable change between to states i
and f,
dqrev
S
T
f
i

Thus, to calculate the difference in entropy


between any two states of a system, find
reversible path between them, integrate
the energy supplied as heat at each stage
of the path divided by the temperature at
which heating occurs.

Example:
Calculate the entropy change of a
sample of perfect gas when it expands
isothermally from a volume Vi to a
volume Vf.

Since T is constant, thus

Surroundings

Example:

Second Law Thermodynamics

Second Law Thermodynamics

Carnot heat engine/Carnot cycle

Efficiency of a heat engine


Efficiency () = work performed = l w l
heat adsorbed
qh
This shows the greater the work output for a given supply of
heat from the hot reservoir, the GREATER is the
EFFICIENCY of the engine.
Since the energy supplied as work by the engine is not same
to energy supplied as heat by the hot reservoir and returned
to the cold reservoir, the efficiency can be expresses in terms
of heat transaction alone,
= qh + qc = 1 + qc for qc < 0, rev = 1 - Tc
qh
qh
Th

From expression, The Second Law of


thermodynamics implies that all reversible
engines have the same efficiency regardless of
their construction (the relation between heat
transfer and temperature is independent of the
working material and true for any substance
involves in Carnot Cycle.

The Third Law


Thermodynamics

The Third Law

Third Law Thermodynamics

Third Law Thermodynamics

Entropy change

Entropy changes for specific


process

Entropy changes for specific


process
Phase transition
The degree of dispersal of matter and energy
changes when a substance freezes or boils
As a result of changes in the order with which the molecules
pack together and the extent to which the energy is localized
or dispersed

The transition is accompanied by a change in entropy


Consider a system and its surrounding at normal
transition temperature, Ttrs (the T at which 2 phases
are in equilibrium at 1 atm)

Entropy changes for specific


process
Tice (s)(0oC, 1atm) Twater(l)(0oC, 1atm)
Twater(l)(100oC, 1atm) Tvapour(g)(100oC, 1atm)
At Ttrs, any transfer of energy as heat between the
system and its surrounding is reversible because the
two phases are reversible

Therefore, the change in molar entropy of the


system is
trsS = trsH/Ttrs, at constant pressure q=trsH
trsH < 0, the phase transition is exothermic;
Freezing and condensation
trsH > 0 the phase transition is endothermic;
Melting and vaporisation

Entropy changes for specific


process

Gibbs Energy

Gibbs Energy