ME 211 Syllabus Update:

1. Introduction, Basic Principles. Concept and

definition
2. Pure Substances
3. Work and Heat
4. First Law of Thermodynamics
5. The First Law Analysis for a Control Volume
6. The Second Law of Thermodynamics
7. Entropy
8. Second Law Analysis for a Control Volume
Chapter 1-
 Chapter 7: Entropy
a) The Inequality of Clausius
b) Entropy of a Pure Substance
c) Entropy Change in Reversible Engine
d) Entropy Change of a Control Mass During an
Irreversible Process
e) Entropy Generation
f) Principle of Increase Entropy
g) Entropy Change of an Ideal Gas
h) The Reversible Polytropic Process for an Ideal
Gas Chapter 1-
 In 2nd Law of Thermodynamics
•We are dealt only with the thermodynamic
cycle
•We are concerned with processes rather than
cycles
• Combustion processes in an automobile engine
• Cooling of coffee
• Chemical processes that takes place in our
bodies

Chapter 1-
Topic 7:

Entropy

Chapter 1-
 Entropy
• The second law of thermodynamics leads to
the definition of a new property called
entropy.
• Entropy can be viewed as a measure of
molecular disorder, or molecular
randomness.
• As a system becomes more disordered, the
positions of the molecules become less
predictable and the entropy increases.

Chapter 1-
Fig. 1: Entropy of a substance (level of disorder) increases when it
melts from solid phase to liquid. Ssolid < Sliquid< Sgas
Chapter 1-
 The Clausius Inequality
• The first law
– is simply an energy balance.
• However, the second law
– leads to an inequality; an irreversible process
• is less efficient than a reversible process.
– Another important inequality in
thermodynamics is the Clausius inequality:

Chapter 1-
 Clausius Inequality
• The cyclic integral of TQ is always less than
or equal to zero.
• This inequality is valid for all cycles,
reversible or irreversible.
• The symbol  is used to indicate that the
integration is to be performed over the
entire cycle.
• Any heat flow to or from a system can be
considered to consist of differential amounts
of heat.
Chapter 1-
 Clausius Inequality
Q
• The cyclic integral of T can be viewed as
the sum of all these differential amounts of
heat divided by the temperature at the
boundary.
• For internally reversible cycles, it can be
shown that:

Chapter 1-
 Clausius inequality
• forms
– basis for the definition of a new property called
entropy.
• As can be seen in the equation,
– for an internally reversible process the cyclic
integral of δQ / T is zero.
• A quantity whose cyclic integral is zero
– depends on the state only and
– not the process path, and thus it is a property.

Chapter 1-
 Reversible heat engine
• For a reversible heat engine operating
between a high-temperature reservoir at TH
and a low-temperature reservoir at TL.

Chapter 1-
 Irreversible heat engine
• For an irreversible heat engine operating
between the same reservoirs:
• From the Carnot first principle, we have
(Wnet )irrev  (Wnet )rev
• Therefore, (QL )irrev  (QL )rev and (Q L )irrev = (Q L )rev + Q diff
where (Q )  0
diff

 Q  Q H (Q L )irrev Q H (Q L )rev Q diff

  T irrev = TH − TL = TH − TL − TL
= − Q diff 0
TL Chapter 1-
 Entropy
• Clausius in 1865 realized that he discovered
a new property and he called it entropy:

• Entropy per unit mass is designated by s

(kJ/kg.K).
• The entropy change of a system during a
process can be calculated:

Chapter 1-
• To perform this integral,
– one needs to know the relation between Q and
T during the process.
• Note that the cyclic integral of δQ / T
– will give us the entropy change only if the
integration carried out along an internally
reversible path between two states.
• For irreversible processes,
– we may imagine a reversible process between
the two states (initial and final) and calculate
the entropy change (since entropy is a
property). Chapter 1-
Chapter 1-
 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).
Chapter 1-
 Some remarks: (Cont.)
• 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.
Chapter 1-
 Some remarks: (End)
• That is because; there is no uncertainty about the state
of the molecules at that instant. This statement is the
third law of thermodynamics.
• Since there is a reference for entropy
(absolute zero),
– entropy is an absolute property.
– The entropy measured with respect to absolute
zero is called absolute entropy.

Chapter 1-
 The Increase in Entropy
 Q 
  T  irrev  0
2  Q  1  Q 
1
 
 T  A ,irrev
+ 2
  0
 T  rev
 Q 
1
S1 − S2 =   
2
 T  rev
 Q  (no irreversibility occur
S = S 2 − S1  12   within the boundaries of

 T  irrev the system during the

process)

The entropy change of a closed system during an

irreversible process is greater than the integral of For an adiabatic process, Q = 0
Q
T
evaluated for that process.
(S)adiabatic  0
2  Q  Q
S     or dS 
1
 T  T Chapter 1-
 Process involved in entropy
• The two diagrams used most extensively in
the second‐law analysis
– are the T‐s and h‐s diagrams.
• For an internally reversible process, one can
write:

Chapter 1-
Fig. 2: On a T‐s diagram, the area under an internally reversible
process presents the heat transfer for the process.
Chapter 1-
• For an internally reversible isothermal
process, we have:

• In a T‐s diagram,
– an isentropic process is represented by a
vertical line.
• An isentropic process
– is a process in which entropy remains constant.
As a result an isentropic process involves no
heat transfer.
• Therefore:
– Isentropic process (s2 = s1) = Reversible + Adiabatic
Chapter 1-
 Evaluation of Entropy Change
• The differential form of the conservation of
energy for a closed system (fixed mass) for
an internally reversible process is:

• Where,

• Thus,

• Or, per unit mass

This is called the first Gibbs equation. Chapter 1-

• From the definition of enthalpy, h = u + Pv,
one can find:

• Eliminating du from the first Gibbs

equation, one finds the second Gibbs
equation:

Chapter 1-
• Explicit relations for differential changes in
entropy can be obtained from Gibbs
equations:

• To calculate the entropy change, we must

know the relationship between du or dh and
temperature.
Chapter 1-
 Enthalpy-Entropy Diagram
(Mollier Diagram )
• Richard Mollier (1863 – 1935 ) - Germany

Chapter 1-
 Calculation of the Entropy for
Saturated Mixture
• Using thermodynamic tables to find sf, sg
and/or sfg for the following:

Chapter 1-
 Calculation of the Entropy for
Superheated Vapor
• Given two properties or the state, such as
temperature and pressure, use the
thermodynamic tables.

• Example:
– Svapor = S @ 10kpa and 100 degree C

Chapter 1-
 Calculation of the Entropy for
Compressed Liquid
• In the absence of compressed liquid data for
a property s ≈ sf@T

Chapter 1-
Expressions for Entropy of an
Ideal Gas

Chapter 1-
 Entropy Change of Solids and
Liquids
• Solids and liquids can be assumed as
incompressible substances since their
volumes remains essentially constant during
a process.
• Thus, the first Gibbs equation becomes:

Chapter 1-
• Assuming an averaged value for specific
heat, one obtains:

• Note that the entropy change of an

incompressible substance is only a function
of temperature.
• Therefore, for an isentropic process where
s2 = s1, one can find:
Chapter 1-
 Entropy Change of Ideal Gas
• The entropy change of an ideal gas can be
obtained, by substituting du = cv dT and P
= RT/v into Gibbs equation.

Chapter 1-
• Assuming averaged values for specific
heats, one obtains:

Chapter 1-
• For isentropic processes of ideal gases, the
following relationships can be found by
setting ds = 0,

• Since R = cp – cv, k = cp / cv, and thus R /

cv = k – 1. Chapter 1-
• In a similar manner, one finds:

• These equations can be expressed in the

following compact forms:

• The specific ratio k, varies with

temperature, and in isentropic relations
above an average k value should be used.
Chapter 1-
 Sample Problem No. 1
• One kilogram of ammonia in a
piston/cylinder at 50°C, 1000 kPa is
expanded in a reversible isothermal process
to 100 kPa. Find the work and heat transfer
for this process.

Chapter 1-
Solution to Sample Problem No. 1

Chapter 1-
 Sample Problem No. 2
• A large slab of concrete, 5 × 8 × 0.3 m, is
used as a thermal storage mass in a solar-
heated house. If the slab cools overnight
from 23°C to 18°C in an 18°C house, what
is the net entropy change associated with
this process?

Chapter 1-
Solution to Sample Problem No. 2

Chapter 1-
 Sample Problem No. 3
• A cylinder/piston contains 1 kg methane gas
at 100 kPa, 20°C. The gas is compressed
reversibly to a pressure of 800 kPa.
Calculate the work required if the process is
a) Adiabatic
b) Isothermal
c) Polytropic, with exponent n = 1.15

Chapter 1-
Solution to Sample Problem No. 3

Chapter 1-
 Sample Problem No. 4

• A cylinder containing R-134a at 10oC and

150 kPa has an initial volume of 20 L. A
piston compresses the R-134a in a
reversible, isothermal process until it
reaches the saturated vapor state. Calculate
the required work and heat transfer to
accomplish this process.

Chapter 1-
Solution to Sample Problem No. 4

Chapter 1-
Assignment (submit next meeting)
• Steam enters a turbine with a pressure of 30 bar, a
temperature of 400°C, and a velocity of 160 m/s.
Saturated vapor at 100°C exits with a velocity of
100 m/s. At steady state, the turbine develops
work equal to 540 kJ per kg of steam flowing
through the turbine. Heat transfer between the
turbine and its surroundings occurs at an average
outer surface temperature of 350 K. Determine
the rate at which entropy is produced within the
turbine per kg of steam flowing, in kJ/kg.K.
Neglect the change in potential energy between
inlet and exit.
Chapter 1-
 Solution Approach
1. Draw a diagram to represent the system showing
control mass/volume of interest.
2. Write out what you are required to solve for (this
is so you don’t forget to answer everything the
question is asking for)
3. Prepare a data table
4. State your assumptions (you may have to add to
your list of assumptions as you proceed in the
problem)
5. Calculations

Chapter 1-