Chapter 1: Review Chapter

1.1 Entropy and the Clausius Inequality

The second law of thermodynamics leads to the definition of a new property called
entropy, a quantitative measure of microscopic disorder for a system. Entropy is a
measure of energy that is no longer available to perform useful work within the current
environment. Clausius inequality, Eq (1.1), is used to obtain the working definition of
entropy

δQ net
 T
0

δQ net
 T < 0
δQ net
 T = 0
δQ net
dS =
T
δQ net
 T
0 (1.1)

Here Q is the net heat added to the system, Qnet.

This equation is called the Clausius Inequality. Here the equality holds for the reversible
process and the inequality holds for the irreversible process.

1.2 Definition of Entropy

Let’s take another look at the quantity
δQ net
 T
0

δQ net
 T
= 0 for reversible process

Thus we conclude that the equality in the Clausius inequality holds for reversible cycles
and the inequality for the irreversible ones.

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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
To develop a relation for the definition of entropy, let us examine this last equation more
closely. Here we have a quantity whose cyclic integral is zero. Let us think for a moment
what kind of quantities can have this characteristic. We know that the cyclic integral of
work is not zero. (It is a good thing that it is not. Otherwise, heat engines that work on a
cycle such as steam power plants would produce zero net work.) Neither is the cyclic
integral of heat.
The cyclic integral of a property is zero. A quantity whose cyclic integral is zero
depends only on the state and not on the process path, thus it is a property. Therefore the
quantity (Qnet/T) rev must be a property. We call this property the entropy, S.
The entropy change occurring during a process is related to the heat transfer and the
temperature of the system. The entropy is given the symbol S (kJ/K), and the specific
entropy is s (kJ/(kg K)).
Consider the effect of heat transfer on entropy for the reversible case.
δQ net
dS = (1.2)
T
If
δQ net < 0, then dS < 0
δQ net > 0, then dS > 0
δQ net = 0, then dS = 0
The entropy change of the system will have the same sign as the heat transfer in a
reversible process. From the above, we see that for a reversible, adiabatic
process dS = 0 . The reversible, adiabatic process is called an isentropic process.
Entropy change is caused by heat transfer and irreversibilities. Heat transfer to a system
increases the entropy; heat transfer from a system decreases it. The effect of
irreversibilities is always to increase the entropy. In fact, a process in which the heat
transfer is out of the system may be so irreversible that the actual entropy change is
positive. Friction is one source of irreversibilities in a system. The performance of
engineering systems is degraded by the presence of irreversibilities, and entropy is a
measure of the magnitudes of the irreversibilities present during that process.

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1.3 Heat transfer as the area under T-S Curve
For the reversible process, dS equation implies that
δQ net
dS =  δQ net = TdS
T
The incremental heat transfer in a process is the product of the temperature and the
differential of the entropy, the differential area under the process curve plotted on the T-
S diagram.
2
δQ = 
1
TdS

1.4 Isothermal, Reversible Process

For an isothermal, reversible process the temperature is constant and the integral to find
the entropy change is readily performed. If the system has a constant temperature To, the
entropy change becomes
2 δQ net Q net
ΔS = S2 -S1 = 
1 T
=
To
(1.3)

For a process occurring over a varying temperature, the entropy change must be found
by integration over the process.
1.5 Adiabatic, Reversible (Isentropic) Process
For an adiabatic (no heat transfer) and reversible process, the entropy change is
ΔS = S2 -S1 = 0  S2  S1

S
or on a per unit mass basis s = ; s 2 -s1
m

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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
The adiabatic, reversible process is a constant entropy process and is called isentropic.
As will be shown later for an ideal gas, the adiabatic, reversible process is the same as
the polytropic process where the polytropic exponent n = k = Cp/Cv.

1.6 Tds Relations

Entropy is a property, and it can be expressed in terms of more familiar properties
(T,P,v) through the Tds relations. These relations come from the analysis of a reversible
closed system which does boundary work and has heat added. Writing the first law for
the closed system in differential form,
Qint rev
Wint rev, out

System used to find expressions for ds

δQ - δW = dU

δQrev = TdS

δWrev = PdV

TdS - PdV = dU
On a unit mass basis we obtain the first Tds equation, or Gibbs equation as

Tds = du + Pdv (1.4)

Recall that the enthalpy is related to the internal energy by h = u + Pv. Using this
relation in the above equation, the second Tds equation is

Tds = dh - vdP (1.5)

These last two relations have many uses in thermodynamics and serve as the starting
point in developing entropy-change relations for processes. The successful use of Tds
relations depends on the availability of property relations. Such relations do not exist in
an easily used form for a general pure substance but are available for incompressible
substances (liquids, solids) and ideal gases. So, for the general pure substance, such as
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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
water and the refrigerants, we must resort to property tables to find values of entropy and
entropy changes. The temperature-entropy and enthalpy-entropy diagrams for water are
shown below.

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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
The h-s diagram is called the Mollier Diagram, is an useful aid in solving steam power
plant problems.
Example 1.1:
Find the entropy and/or temperature of steam at the following states:
P T Region s kJ/(kg K)
5 MPa 120oC
1 MPa 50oC
1.5 MPa 400oC
40 kPa Quality, x=0.9
40 kPa 7.1794

Example 1.2
Determine the entropy change of water contained in a closed system as it changes phase
from saturated liquid to saturated vapour when the pressure is 0.1MPa and constant.
Why is the entropy change positive for this process?
System: The water contained in the system (a piston-cylinder device)

Steam

s
Property Relation: Steam Tables
Process and Process Diagram: Constant pressure (sketch the process relative to the
saturation lines)
Conservation Principles:
Using the definition of entropy change, the entropy change of the water per mass is
ΔS = S2 -S1 = Sg -Sf = Sfg
kJ
= 6.056
kg
The entropy change is positive because:

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Lecturer: E. W. RAMDE
The entropy-change and isentropic relations for a process can be summarized as
follows:
a. Pure substances:
Any process: Δs = s 2 -s1 [kJ/(kg-K)]

Isentropic process: s 2 = s1

b. Incompressible substances:
du P
ds = + dv
T T
The change in internal energy and volume for an incompressible substance is
du = cdT
dv = 0

The entropy change now becomes

c dT
ds = + 0
T
2
c (T)dT
Δs = 1 T
T2 (1.6)
= c av ln
T1

If the specific heat for the incompressible substance is constant, then the entropy change
T2
is, for any process: Δs = s 2 -s1 = cav ln [kJ/(kg-K)] (1.7)
T1

And for isentropic process: T2 = T1 (1.8)

c. Ideal gases: Constant specific heats (approximate treatment):

Any process: (can you fill in the steps?)

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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
 T2 v
Δs = s 2 -s1 = C v, av ln + R ln 2 [kJ/(kg-K)] (1.9)
T1 v1
and (can you fill in the steps?)

T2 P
Δs = s 2 -s1 = Cp, av ln - R ln 2 [kJ/(kg-K)] (1.10)
T1 P1

Or, on a unit-mole basis,

T2 v
Δs = s2 - s1 = C v, av ln + R u ln 2 [kJ/(kmol-K)]
T1 v1
and
T2 P
Δs = s2 - s1 = C p, av ln - R u ln 2 [kJ/(kmol-K)]
T1 P1

ISENTROPIC PROCESSES OF IDEAL GASES

Can you fill in the steps here?

 T2   P2  k-1
  =   (1.11)
 T1 s = const.  P1  k

k -1
 T2  v 
  = 1 (1.12)
 T1 s = const.  v 2 

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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
 k
 P2  v 
  = 1 (1.13)
 P1 s = const.  v 2 

For an isentropic process this last result looks like Pvk = constant which is the
polytropic process equation Pvn = constant with n = k = Cp/Cv.

1.7. Reversible Steady-flow Work: Isentropic steady flow through turbines,

pumps, and compressors
For a steady-flow device undergoing a reversible process, the first law (on a unit mass
basis) reduces to: δw rev = δq rev - dh - dke - dpe (1.14)

but δq rev = Tds which gives δw rev = Tds - dh - dke - dpe

Taking Eq(1.5) into account, we get δw = -vdP - dke - dpe (1.15)

Integrating over the process, this becomes
2
w rev =   vdP - ke - pe  kJ/kg  (1.16)
1

Neglecting changes in kinetic and potential energies, reversible work becomes

2
w rev =   vdP (1.17)
1

Based on the sign convention, this is the work done by the control volume. When work
is done on the control volume such as compressors or pumps, the reversible work going
into the control volume is
2  kJ 
w re v , in =  1
vdP + Δ ke + Δ pe  
 kg 
1.7.1 Turbine
Since the fluid pressure drops as the fluid flows through the turbine, dP < 0, and the
specific volume is always greater than zero, wrev, turbine > 0. To perform the integral, the
pressure-volume relation must be known for the process.
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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
1.7.2 Compressor and Pump
Since the fluid pressure rises as the fluid flows through the compressor or pump, dP > 0,
and the specific volume is always greater than zero, wrev, in > 0, or work is supplied to the
compressor or pump. To perform the integral, the pressure-volume relation must be
known for the process. The term compressor is usually applied to the compression of a
gas. The term pump is usually applied to increasing the pressure of a liquid.

Pumping an incompressible liquid

For an incompressible liquid, the specific volume is approximately constant.
2
w rev, in =  vdP + ke + pe
1

w rev, in = vP + ke + pe

For the steady-flow of an incompressible fluid through a device that involves no work
interactions (such as nozzles or a pipe section), the work term is zero, and the equation
above can be expressed as the well know Bernoulli Equation in fluid mechanics.
v (P2 - P1 ) + Δke + Δpe = 0

Minimizing the compressor work

2
w rev, in =  vdP
1

Practical way of minimizing w rev, in (compressor work) is to keep the specific volume of

the gas as small as possible during the compression work. For a gas v increases with
temperature. So maintaining the temperature of the gas as low as possible during
compression will also keep v low and hence w rev, in low. That implies cooling the gas as

it is compressed.
To better understand this, let’s compare work inputs for 3 kinds of processes:
- isentropic process (= constant entropy = reversible and adiabatic): No cooling
- polytropic process: involves some cooling
- isothermal process: involves maximum cooling

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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
We assume that the gas is ideal ( P V = R T ) with constant specific heats; we also
assume that all 3 processes are executed between some pressure levels ( P1 and P2 ) in a

reversible manner.
- Isentropic P v k = C  v = C1/k P -1/k
2 2
k R ( T2 - T1 )
w comp, in =  v dP   C1/k P -1/k dP which gives w comp, in = and taking
1 1
k -1
Eq (1.11) into account, we get:
 k-1

k R T1  2 P  k
w comp, in = - 1 (1.18)
k -1  P1  
 
- Polytropic process P v n = C  v = C1/n P -1/n

 n-1

n R T1  2 P  n
Integration yields w comp, in = - 1 (1.19)
n -1  P1  
 

P2
- Isothermal process P v = C , we get w comp, in = R T ln (1.20)
P1

P-v diagram of isentropic, polytropic, and isothermal compression processes

between the same pressure limits for an ideal gas.

P
Isentropic (n = k); no cooling
P2

Polytropic (1 < n < k); some cooling

Isothermal (n = 1); heavy cooling

P1

v
Compression works are the areas to the left of the various curves; and from the above
graph, compression work is minimal when isothermal, intermediate when polytropic and
maximum when isentropic.

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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
From the above discussion, cooling a gas during compression minimizes the work
required. Cooling could be done through the casing of the compressor but this is not
always practical. One practical method for achieving minimum compression work is
multistage compression with intercooling.

Multistage compression with intercooling

The gas is compressed in stages and cooled between each stage by passing it through a
heat exchanger called intercooler; ideally, the gas is cooled to the initial temperature at
each intercooler.
For a two-stage compressor, the gas is compressed from (P1, T1) to some intermediate
pressure Px it is then cooled back to T1 before being compressed to the final pressure P2.
The compression process can be modeled as polytropic ( P v n = C with 1< n < k ). The
work saved is clearly viewd in a P-v diagram.

P
Work saved
P2

Px
P
Intercooling
P1

The saved work input varies with the value of the intermediate pressure Px. What is the
value of Px under which this saved work is maximum?
 n-1
  n-1

n R T1   P  n
 n R T   P  n

w comp, in = x
-1  1 2
  - 1
n -1  P1   n -1  Px 
   
The variable here is Px. The value of Px for which the compression work is minimal is
determined by differentiating w comp, in with respect to Px and seting the resulting

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 1
Px P
expression equal to zero and solving for Px. It gives Px =  P1 P2  2 or = 2 which
P1 Px
means that the pressure ratio across each stage of the compressor must be the same or
compression work at each stage is the same.

1.8. Turbine, Compressor (Pump), and Nozzle Efficiencies

Most steady-flow devices operate under adiabatic conditions, and the ideal process for
these devices is the isentropic process. The parameter that describes how a device
approximates a corresponding isentropic device is called the isentropic or adiabatic
efficiency. It is defined for turbines, compressors, and nozzles as follows:

1.8.1 Turbine

The isentropic work is the maximum possible work output that the adiabatic turbine can
produce; therefore, the actual work is less than the isentropic work. Since efficiencies
are defined to be less than 1, the turbine isentropic efficiency is defined as

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Lecturer: E. W. RAMDE
 actual turbine work w
ηT   a
isentropic turbine work ws

h1 - h 2a
ηT 
h1 - h 2s
Well designed large turbines may have isentropic efficiencies above 90%. Small
turbines may have isentropic efficiencies below 70%.

1.8.2 Compressor and Pump

The isentropic work is the minimum possible work that the adiabatic compressor
requires; therefore, the actual work is greater than the isentropic work. Since
efficiencies are defined to be less than 1, the compressor isentropic efficiency is defined
as
isentropic compressor work w
ηc   s
actual compressor work wa

T1
P1
WC
T2
P2
Compressor
Or Pump

Isentropic compressor work w s

ηC = =
Actual compressor work wa

h 2s - h1
ηC 
h 2a - h1
Well designed compressors have isentropic efficiencies in the range from 75 to 85%.
Review the efficiency of a pump and an isothermal compressor on your own.

Nozzle:

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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE
The isentropic kinetic energy at the nozzle exit is the maximum possible kinetic energy
at the nozzle exit; therefore, the actual kinetic energy at the nozzle exit is less than the
isentropic value. Since efficiencies are defined to be less than 1, the nozzle isentropic
efficiency is defined as

T1
T2
P1
P2
V1
V2
Nozzle


Actual KE at nozzle exit V2a2 /2
ηN = = 
Isentropic KE at nozzle exit V2s2 /2

For steady-flow, no work, neglect potential energies, and neglect the inlet kinetic energy,
the conservation of energy for the nozzle is

V2a2
h1 = h 2a +
2
The nozzle efficiency is written as
h1 -h 2a
ηN 
h1 -h 2s
Nozzle efficiencies are typically above 90%, and nozzle efficiencies above 95% are not
uncommon.

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ME 365: Thermodynamics II
Lecturer: E. W. RAMDE