Entropy

Reported to
DR\ Rana Gamal

Reported by \ Aisha Ahmed

ID \ 92020116

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Chemical and physical changes may be spontaneous or
nonspontaneous. The spontaneity of a process is driven
both by enthalpy change (a negative ∆H favoring the
forward reaction) but also by the increase in entropy, or
disorder of the system. A more disordered product is
more likely to form than a more ordered one. Most
exothermic processed such as fuel burning are
spontaneous, but a few endothermic processes such as
solution of sodium nitrite in water (ice pack) can also be
spontaneous. An important factor in the spontaneity of
a process is the increase in entropy (disorder) of the
system. A system at equilibrium does not undergo an
entropy change, because net change is not occurring.
Ex: The combustion of glucose is highly spontaneous
both because it is exothermic and because there is a
large increase in entropy. Try to imagine the reverse
reaction occurring spontaneously by the assembly of
glucose from carbon dioxide gas and water vapor. A
simple way to understand the entropy of a physical
spontaneous process is the distribution of gas molecules
between two connected flasks, starting with just one
gas molecule.

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Entropy Facts:

• Entropy units are joules/K · mol. For a specified amount of

substance, units are joules/K. Entropy values are generally
small, in the joule rather than kJ range.
• The entropy of a liquid is greater than that of a solid. The
entropy of a gas is always much greater than that of the
corresponding liquid.
• The entropy of any substance increases with increasing
temperature because greater molecular motion increases
disorder.
• If a change such as photosynthesis involves an entropy
decrease, there is a greater entropy increase elsewhere in
the universe.
• It is possible to assign an absolute entropy value to any
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substance, given the fact that a perfect crystal at absolute
zero has zero entropy. (Remember, there is no way to
determine absolute enthalpy.) The entropy of any substance
at a finite temperature will be greater then zero. Any sample
less ordered than a perfect crystal will have a positive
entropy.
• Standard Entropy is defined as the absolute entropy of a
substance at 25 ºC.

Entropy

Entropy is defined as a quantitative measure of disorder or

randomness in a system. The heat change, dq and the
temperature T are thermodynamic quantities. A
thermodynamic function whose change (dq/T) is
independent of the path of the system is called entropy
𝑑𝑆 = 𝑑𝑞 𝑇

1. Entropy is a state function whose magnitude depends only

on the parameters of the system and can be expressed in
terms of (P,V,T)

2. dS is a perfect differential. Its value depends only on the

initial and final states of the system

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3. Absorption of heat increases entropy of the system. In a
reversible adiabatic change dq=0, the entropy change is zero
4. For carnot cycle ∮ 𝑑𝑆 = 0

5. The net entropy change in a reversible process is zero,

∆𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = 0
In irreversible expansion ∆𝑆𝑢𝑛𝑖𝑣 = +𝑣𝑒 cyclic processes
∆𝑆𝑢𝑛𝑖𝑣 > 0

All natural process will take place in a direction in which the

entropy would increase. A thermodynamically irreversible
process is always accompanied by an increase in the entropy
of the system and its surroundings taken together while in a
thermodynamically reversible process, the entropy of the
system and its surroundings taken together remains constant.

Entropy change in isothermal and reversible expansion

of ideal gas:
In isothermal expansion of an ideal gas carried out
reversibly, there will be no change in internal energy, ∆U=0,
hence from the first law q = -W In such case, the work done
in the expansion of n moles of a gas from volume V1 to V2 at
constant temperature T is given by – 𝑊 = 𝑛𝑅𝑇𝑙𝑛( 𝑉2 𝑉1 )
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𝑞𝑟𝑒𝑣 = −𝑊 = 𝑛𝑅𝑇𝑙𝑛( 𝑉2 𝑉1 ) Produced with a Trial Version of
PDF Annotator - www.PDFAnnotator.com Hence 𝑑𝑆 = 𝑑𝑞 𝑇 =
1 𝑇 𝑛𝑅𝑇𝑙𝑛 ( 𝑉2 𝑉1 ) = 𝑛𝑅𝑙𝑛 ( 𝑉2 𝑉1 ) (Problem: 5 moles of
ideal gas expand reversibly from volume of 8 dm3 to 80 dm3
at a temperature of 27oC. Calculate the change in entropy)

Physical significance of Entropy:

1. Entropy as a measure of disorder of the system: All

spontaneous processes, such as flow of heat from hot end to
cold end, expansion of a gas in vacuum, diffusion of a solute
from a concentrayed to a dilute solution, are accompanied by
increase in disorder of the system. Spontaneous processes
are acoompanied by increase in entropy as well as increase in
disorder of the system. Thus entropy is regarded as a
measure of the disorder of a system.

2. Entropy as a measure of probability: All spontaneous

processes leads to increase in entropy. When a process is
spontaneous, that means a system undergoes a change from
less probable to a more probable state. It appears therefore
that there is a close relationship between entropy and

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thermodynamic probability W. This relationship was
expressed by S= k lnW (k is boltzman constant)

Work and free energy function:

The Helmholtz free energy or work function, A=U-TS For

Isothermal reversible change, ∆AT=∆U-T∆S = ∆U- q = Wmax
The work function A is a thermodynamic property of the
system. Its decrease gives the maximum amount of work
available during isothermal transformation. If the change is
not Isothermal, A=U-TS dA = du-TdS-SdT dA= dU-dq-SdT
dA= -PdV-SdT For Isochoric process, ( 𝐴 𝑑𝑇 )𝑉 = −𝑆
For isothermal process, ( 𝑑𝐴 𝑑𝑉 )𝑇 = −p

For isothermal reversible change

G = H-TS = U+PV-TS ∆G = ∆U+P∆V+V∆P-T∆S-S∆T ∆GP,T =

∆U+P∆V-T∆S = ∆U+P∆V+V∆P- q = P∆V –W P∆V is the

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mechanical work involved in the system itself during
transformation and W denotes the maximum output. So, W-
P∆V is the amount of work received for any external use,
exclusive of the mechanical work during transformation of
the system Gibbs free energy is a property whose decrease is
the measure of external work available is the measure of
external work available during the transformation of the
system G= H-TS G=U+PV-TS dG=Du+PdV+VdP-TdS-SdT in
reversible process, dU+PdV=TdS So, dG=VdP-SdT For an
isobaric process, ( 𝑑𝐺 𝑑𝑇 )𝑃 = −𝑆 For an isothermal process, (
𝑑𝐺 𝑑𝑃 )𝑇 = p

The Increase of Entropy Principle

Entropy change of a closed system during an irreversible

process is greater that the integral of δQ / T evaluated for the
process. In the limiting case of a reversible process, they
become equal. T Q dS   The entropy generated during a
process is called entropy generation, and is denoted by Sgen
Note that the entropy generation Sgen is always a positive
quantity or zero (reversible process). Its value depends on
the process, thus it is not a property of a system. The entropy

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of an isolated system during a process always increases, or in
the limiting case of a reversible process remains constant (it
never decreases). This is known as the increase of entropy
principle. The entropy change of a system or its
surroundings can be negative; but entropy generation
cannot. impossible process 0 reversible process 0 irreversible
process
1‐ A process must proceeds in the direction that complies
with the increase of entropy principle process that violates
this principle is impossible.
2‐ Entropy is a non‐conserved property, and there is no such
thing as the conservation of entropy. Therefore, the entropy
of universe is continuously increasing.
3‐ The performance of engineering systems is degraded by
the presence of irreversibility. The entropy generation is a
measure of the magnitudes of the irreversibilities present
during the process.

Entropy Balance

Entropy is a measure of molecular disorder or randomness of

a system, and the second law states that entropy can be

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created but it cannot be destroyed. The increase of entropy
principle is expressed as

Entropy change = Entropy transfer + Entropy generation

Ssystem = Stransfer + Sgen

This is called the entropy balance.

Entropy Change

The entropy balance is easier to apply that energy balance,

since unlike energy (which has many forms such as heat and
work) entropy has only one form. The entropy change for a
system during a process is:

Entropy change = Entropy at final state ‐ Entropy at initial

state

S(system_ = S(final) − S(initial Therefore)

the entropy change of a system is zero if the state of the
system does not change during the process. For example
entropy change of steady flow devices such as nozzles,
compressors, turbines, pumps, and heat exchangers is zero
during steady operation

Mechanisms of Entropy Transfer

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Entropy can be transferred to or from a system in two forms:
heat transfer and mass flow. Thus, the entropy transfer for
an adiabatic closed system is zero. Heat Transfer: heat is a
form of disorganized energy and some disorganization
(entropy) will flow with heat. Heat rejection is the only way
that the entropy of a fixed mass can be decreased. The ratio
of the heat transfer Q/ T (absolute temperature) at a location
is called entropy flow or entropy transfer
Since T (in Kelvin) is always positive, the direction of entropy
transfer is the same of the direction of heat transfer. When
two systems are in contact, the entropy transfer from
warmer system is equal to the entropy transfer to the colder
system since the boundary has no thickness and occupies no
volume. Note that work is entropy‐free, and no entropy is
transferred with work.

Mass Flow: mass contains entropy as well as energy, both

entropy and energy contents of a system are proportional to
the mass. When a mass in the amount of m enters or leaves a
system, entropy in the amount of ms (s is the specific
entropy) accompanies it.

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Entropy Balance for a Closed System

A closed system includes no mass flow across its boundaries,

and the entropy change is simply the difference between the
initial and final entropies of the system. The entropy change
of a closed system is due to the entropy transfer
accompanying heat transfer and the entropy generation
within the system boundaries:
Entropy change of the system = Entropy transfer with heat + Entropy
generation

Therefore, for an adiabatic closed system, we have:

ΔS(adiabatic) = S(gen)

For an internally reversible adiabatic process ΔS = 0, because

S(gen)= 0.

The total entropy generated during a process can be

determined by applying the entropy balance to an extended
system that includes both the system and its immediate
surroundings where external irreversibility might be
occurring.

Entropy Balance for a Control Volume

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In addition to methods discussed for closed system, the entropy can
be exchanged through mass flows across the boundaries of the
control volume.

Some remarks

Work is an organized form of energy, free of disorder or

randomness, thus free of entropy. Therefore, there is no
entropy associated with energy transfer as work.
The quantity of energy is always preserved during an actual
process, based on the first law, but the quality is bound to
decrease (the second law).

Processes can occur only in the direction of increased overall

entropy or molecular disorder. Thus, the entire universe is
getting more and more chaotic every day.

At absolute zero (0 K), molecules become completely

motionless, this represents a state of ultimate molecular
order (and minimum energy). Therefore, the entropy of a
pure crystalline substance at zero temperature is zero. That
is because; there is no uncertainty about the state of the
molecules at that instant. This statement is the third law of
thermodynamics.

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