EBT 239

Thermodynamics

The Second Law

Lecture by:
Jalilah Abd Jalil
Recall the First Law of
Thermodynamics

•When one form of energy is

converted to another, the total
energy is conserved.

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 However…..
• As we use energy, its quantity
remains constant, but its quality
degrades.

• Energy degradation is called entropy

increase.
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Example situation of energy
changes and degradation
• If a brick falls off a table and hits the floor, energy is
conserved;
• The initial potential energy of the brick is converted first
into kinetic energy, as the brick accelerates.
• And then into thermal energy, as it comes to rest on the
floor. The brick and floor are slightly warmer at the end
of this process.
• However, no machine has ever been invented that could
make use of this thermal energy to raise the brick back
up onto the table.
• Energy need to be provided to return the brick to its 4
initial state.
 Consider these situations…
A cup of hot coffee does
not get hotter in a cooler
room.

Transferring heat to a
paddle wheel will not
cause it to rotate.

These processes cannot

occur even though they
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are not in violation of
the first law.
 Does the First Law satisfy all the
processes occur?
• Obviously, the First Law does not
satisfy the processes that occur.
• If the only energy consideration were
the first law, there would never be
any energy shortages; we could just
recycle energy.
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The Second Law of Thermodynamics
says…

There is always net entropy

increase in real processes
(any spontaneous process)

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• The second law explains why we
cannot continually reuse energy, as
we reuse other resources, such as
copper, and why energy recycling is
not an effective response to energy
shortages.

Energy is degraded to less useful

forms as we use it! 8
Therefore…..

• A process must satisfy both the first

and second laws of thermodynamics
to proceed

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Furthermore….
• Many processes have a natural
direction or proceed in one direction

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SPONTANEOUS (Irreversible, one
direction) PROCESSES
• Gases always expand into a vacuum.
• Heat is always transferred from a hot body to a
cold body.
• In the presence of catalyst, molecular hydrogen
and molecular oxygen react to form water.

• The reverse process, non-spontaneous

processes, can only be accomplished by
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performing work on the system.
NON-SPONTANEOUS (Reversible)
PROCESSES
• A gas can be compressed to a smaller volume
by use of mechanical work.
• Heat can be transferred to a hot body from a
cold body by use of a refrigerator device.
• Water can be electrolyzed to molecular
hydrogen and molecular oxygen by use of
electrical work from a battery.
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REVERSIBLE AND IRREVERSIBLE PROCESSES

Reversible process:
A process that can be
reversed without leaving
any trace on the
surroundings.
Irreversible /
Spontaneous process:
A process that is not
reversible. Two familiar reversible processes

All the processes occurring in nature are 13

irreversible.
“What quantity that tells us
whether a chemical reaction
or a physical change can
occur spontaneously in an
isolated system??”

Entropy
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The factors that cause a process
to be irreversible
• Friction
• Unrestrained expansion,
• Mixing of two fluids
• Heat transfer across a finite
temperature difference
• Chemical reactions.

The presence of any of these effects renders a

process irreversible. 15
Friction renders a process
irreversible.

(a) Heat transfer through a

temperature difference
is irreversible

(b) The reverse process is

impossible.
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Major uses of the Second Law
1. The second law asserts that energy
has quality.
(The first law is concerned with the quantity
of energy from one form to another with no
regard to its quality.
The second law provides the necessary
means to determine the quality as well as
the degree of degradation of energy during
a process.) 17
2. The second law may be used to identify
the direction of processes (forward or
backward).
3. The second law of thermodynamics is
also used in determining the theoretical
limits for the performance of commonly
used engineering systems, such as heat
engines and refrigerators, as well as
predicting the degree of completion of
chemical reactions. 18
 ENTROPY
• A term coined by Rudolph Clausius
(1822-1888) designated by the symbol S.
• Measures the spontaneous dispersal of
energy: how much energy is spread out in
a process, or how widely spread out it
becomes — at a specific temperature.

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 The Thermodynamic
Definition of Entropy
Concentrates on the change in entropy
not its absolute value S
The definition of dS is based on the view
that a change in the extent of dispersal of
energy can be related to the energy
transferred as heat when a process occurs.
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• Entropy change = “energy dispersed”/T, or
qreversible/T , as in phase changes like melting or
vaporization where
ΔS = ΔHfusion/T or ΔHvaporization/T, respectively.)

• Thus, entropy has the units of energy unit per

Kelvin,[ J K-1]

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• For infinitesimal ( immeasurably small)
change in state
dS  dqrev / T

• For a finite change in state

dqrev
S  
T
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• Like total energy, E, and enthalpy, H,
entropy is a state function (describes the
equilibrium state of a system).
• Therefore,

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Statistical Definition of Entropy
Degree of disorder in a system
The entropy is calculated using a
formula proposed by Ludwiq
Boltzmann in 1896:

S = k ln W

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According to the Boltzman formula,
the entropy of a perfectly ordered
solid is zero since W = 1 (because
there is only one way to achieving
perfectly ordered sample)

The entropy of disorderly solid in

which each diatomic molecule can
adopt either of two orientations at
T=0 is greater than 0
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Entropy and the Second Law of a
System
• When a spontaneous change occurs in the system of
interest, the entropy change Stotal in the system plus the
surroundings is given by
Stotal =Ssys + Ssurr

• Second Law: all systems tend towards an increase in

the randomness of the system. In terms of entropy, the
total entropy of the universe always increases. Thus,
Stotal =Ssys + Ssurr  0
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 A system and its
surroundings form an
isolated system.

The entropy change of an

isolated system is the sum
of the entropy changes of
its components, and is
never less than zero.

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• When a spontaneous process occurs in
an isolated system, the entropy
increases.
• When a process occurs reversibly in an
isolated system, the entropy does not
change.
• For a finite change the three
possibilities are

S > 0 Irreversible (spontaneous) process

S = 0 Reversible process
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S < 0 Impossible process
Two Parts of The Second Law
1. There is a state function called the entropy
S that can be calculated from
dS  dqrev / T
2. The change in entropy in any process is
given by dS  dqirrev / T, where the > applies to a
spontaneous process (irreversible process)
and the equality applies to a reversible
process.
 This means that in order to calculate ∆S for a change in a
state , one must use a reversible process.
Remember this…
• Entropy is a nonconserved property,
and there is no such thing as the
conservation of entropy principle.
Entropy is conserved during the
idealized reversible processes only
and increases during all actual
processes.
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