ENTROPY
ME 100
Thermodynamics
Entropy
• Entropy is an abstract concept like energy.
• It can be viewed as a measure of molecular disorder or molecular
randomness.
• As a system becomes more disordered, the positions of molecules
became less predictable and the entropy increases.
• In solid phase, molecules of substance continually oscillate about
their equilibrium positions, but they cannot move relative to each
other and their positions at any instant can be predicted with good
certainty.
• In gas phase, the molecules move about at random, collide with
each other, and change direction making it extremely difficult to
predict accurately the microscopic state of a system at any instant.
Associated with this molecular chaos is a high value of entropy.
WHAT IS ENTROPY?
Disorganized energy does not create much
useful effect, no matter how large it is.
Entropy in our daily lives may be
related to disorganization of
lifestyles, disorderliness of things,
and chaos within an organization.
The level of molecular
disorder (entropy) of a
substance increases as it
melts or evaporates.
The paddle-wheel work done on a
gas increases the level of disorder
(entropy) of the gas, and thus
energy is degraded during this
process.
• The paddle wheel work is converted into internal energy of the gas
(as evidenced with the increase in gas temperature), creating a
higher level of molecular disorder in the container.
• The work of the paddle is an organized energy which is converted to
a highly disorganized form of energy and cannot be converted back
to the paddle wheel as the rotational kinetic energy.
• Therefore, the energy is degraded during the process, the ability to
do work is reduced, molecular disorder is produced; and associated
with all this is an increases in entropy.
• Recall: the first law asserts that energy has quantity, that is, quantity of
energy is always preserved during an actual process
• The second law asserts that energy has quality as well as quantity, and
actual processes occur at the direction of decreasing quality of energy.
• In other words, quality is bound to decrease and this decrease in quality is
always accompanied by an increase in entropy. The second law leads to a
property, entropy.
• Consider the transfer of 10 kJ of energy
as heat from a hot medium to a cold one.
At the end of the process, we still have
the 10kJ but at a lower temperature and
thus at a lower quality.
• Heat, in essence, is a form of
disorganized energy and some
disorganization flows with heat. As a
result the entropy and the level of
molecular disorder and randomness of a
hot body decreases with the increase in During a heat transfer process, the net
the entropy and level of molecular entropy increases. (The increase in the
disorder of the cold body. entropy of the cold body more than offsets
the decrease in the entropy of the hot body.)
• The second law requires that the
increase in entropy of the cold body
be greater than the decrease in
entropy of the cold body and thus, the
net entropy of the combined system
(cold body and hot body) increase.
• To conclude, process occur only in
the direction of increased overall
entropy or molecular disorder.
• Entropy is an extensive property of a system.
S = total entropy (kJ)
s = specific entropy (kJ/kg)
• Entropy is defined as:
Formal
Q
dS definition
T int rev of entropy
• Entropy change can be determined by integrating the above
equation:
Q
2
S S 2 S1
1
T int rev
• To perform the integration, one needs to know the relation between
Q and T during the process. Often this relation is not available, so in
majority of the cases we have to rely on tabulated data for entropy.
• Note that entropy is a property and it has fixed values at fixed
states. Therefore ∆S between two states is the same no matter what
path, reversible or irreversible, is followed during a process.
• Also, note that the integral of δQ/T
gives us the value of entropy
change only if the integration is
carried out along an internally
reversible path between two states.
The integral of δQ/T along an
irreversible path is not a property
and in general different values will
be obtained.
• Therefore, even for irreversible
process, the ∆S should be
The entropy change between two
determined by carrying out this specified states is the same
integration along some convenient whether the process is reversible or
imaginary internally reversible path irreversible.
between specified states.
REVERSIBLE AND IRREVERSIBLE PROCESSES
Reversible process: A process that can be reversed without leaving any trace
on the surroundings. That is, both the system and surroundings are returned to
their initial states at the end of the reversed process.
Irreversible process: A process that is not reversible.
• It should be pointed out that a system can
be restored to its initial state following a
process, regardless of whether the
process is reversible or irreversible. But
for reversible process, this restoration is
made without leaving any change on the
surroundings.
• Reversible process actually do not occur
in nature. They are merely idealizations of
the actual process. Reversible process
can be approximated by actual device but
can never be achieved
• Why are we interested in reversible processes?
• (1) they are easy to analyze and (2) they serve as
idealized models (theoretical limits) to which actual
Two familiar
processes can be compared.
reversible processes.
Internally and Externally Reversible Processes
• A process is called internally reversible if no irreversibilities occur within the
boundary of the system during the process.
• A process is called externally reversible if no irreversibilities occur outside the
system boundaries during the process.
Example: Heat transfer between a reservoir and a system is an externally
reversible process if the outer surface of the system is at the temperature of the
reservoir.
Irreversibilities
• The factors that cause a process to be
irreversible are called irreversibilities.
• They include friction, unrestrained expansion,
mixing of two fluids, heat transfer across a finite
temperature difference, electric resistance,
inelastic deformation of solids, and chemical
reactions. Friction
• The presence of any of these effects renders a renders a
process irreversible. process
irreversible.
Irreversibilities
(a) Heat transfer through a Irreversible
temperature difference is compression and
irreversible, and (b) the reverse expansion processes.
process is impossible.
ENTROPY CHANGE OF PURE SUBSTANCES
Entropy is a property, and thus the
value of entropy of a system is fixed
once the state of the system is fixed.
Schematic of the T-s diagram for water.
The entropy of a pure substance Entropy change
is determined from the tables
(like other properties).
PROPERTY DIAGRAMS INVOLVING ENTROPY
On a T-S
diagram, the
area under the
process curve
represents the
heat transfer for
internally
reversible
processes.
For adiabatic steady-flow
devices, the vertical distance
∆h on an h-s diagram is a
measure of work, and the
horizontal distance ∆s is a
measure of irreversibilities.
Mollier diagram: The h-s diagram
THE T ds RELATIONS Can be
Q
2 evaluated by
Q
dS S S 2 S1 integrating δQ/T
T int rev 1
T int rev along some
imaginary
For Isothermal process (T=constant) internally
reversible path
2 between actual
1
S S 2 S1 ( Q)int rev states
T 1
But when temperature varies during the
Q process, we have to have a relation between
S (kJ/K) δQ and T to perform the integration.
T
Consider a closed system for internally reversible process:
the first T ds, or Gibbs equation
But,
the second T ds equation
The Tds relations are developed with an
internally reversible process where
entropy change between two states must
be evaluated along a reversible path.
However, the results obtained are valid
for both reversible and irreversible
processes since entropy is a property and
the change in property between two
states is independent of the type the
system undergoes.
The T ds relations are valid for
Differential changes
both reversible and irreversible
in entropy in terms
processes and for both closed
of other properties
and open systems.
ENTROPY CHANGE OF LIQUIDS AND SOLIDS
Liquids and solids can be
approximated as
incompressible substances
Since for liquids and solids since their specific volumes
remain nearly constant
during a process.
For and isentropic process of an incompressible substance
THE ENTROPY CHANGE OF IDEAL GASES
From the first T ds relation From the second T ds relation
There are three approaches in determining entropy change for ideal
gases:
1. Using constant specific heats (approximate analysis) from the
values in Table A-2a (at 300K). Performing the integration:
2. Using constant specific heats corresponding to the average value of the
temperatures of the initial and final states (approximate analysis).
So that performing the integration:
Under the constant-specific-
heat assumption, the specific
heat is assumed to be constant
at some average value.
3. By using the Cv and Cp as functions of temperature and performing the
integrations (variable specific heats-exact analysis). Values of Cp as function
of temperature are listed on Table A-2c.
For this purpose, we choose absolute zero
as the reference temperature and define a
function s° as: Obviously, s° is a
function of
temperature alone.
s° values for air are
listed in Table 17
Where: s2° is s° at T2
and s1° is s° at T1
The entropy of an ideal gas
depends on both T and P. The
function s represents only the
temperature-dependent part of
entropy.
Sample Problem
• Air is compressed from an initial state of 100 kPaa and 17⁰C to a
final state of 600 kPaa and 57 ⁰C. determine the entropy change of
air during the compression process by using : (a) constant specific
heat, and (b) average specific heats.
From Table A-2a
Cp of air = 1.005 kJ/kg-K
From Table A-2b, at Tavg. =310 K:
Cp of air = 1.006 kJ/kg-K
Ans. -0.3844 kJ/kg-K
Homework Problems (HW4)
1. A spherical balloon of 20 ft. in diameter is filled with hydrogen at
27⁰C and 200 kPa. Determine the mass of the hydrogen in the
balloon and its mole number.
2. A tank contains 0.5 m3 of helium at 27⁰C and 600 kPa. The tank is
connected by a valve to an evacuated tank with a capacity of 2300
liters. The valve is opened and the entire system is allowed to
reach thermal equilibrium with the surroundings, which are at 23
⁰C. Find the final equilibrium pressure of helium.
3. 0.25 kg of Argon fills a 0.1 m3 rigid vessel at 400 kPa. Heat is
transferred to the vessel until the pressure is 715 kPa. Calculate
the temperature change of Argon in ⁰C and K.
4. For a certain ideal gas, R=0.277 kJ/kg K and k=1.384. (a) What are
the value of Cp and Cv? (b) What mass of this gas would occupy
0.425 m3 at 517.11 kPa and 26.7 ⁰C? (c) If 31.65 kJ is transferred
to this gas at constant volume, what are the resulting temperature
and pressure?
5. A piston-cylinder device initially contains 2 kg of air at 150 kPa and
30 ⁰C. The mass of the piston is such that a pressure of 375 kPa is
required to move it. Heat is now transferred to the air until its
volume is 1.8 times the initial volume. Determine the work done by
the expanding air and the heat transferred to the air during this
process.
6. Air enters a pipe at 60 ⁰C and 200 kPa and leaves at 50 ⁰C and
150 kPa. It is estimated that heat is lost from the pipe in the amount
of 4.2 kJ per kg of air flowing in the pipe. The diameter ratio for the
pipe is D1/D2 = 1.75. Using constant specific heats for air,
determine the inlet and outlet velocities of air.
7. A mass of 1 kg of air contained in a cylinder at 1.5 MPa and 1000 K
expands in a reversible isothermal process to a volume 10 times
larger. Calculate the change of entropy of air.