Thermodynamic II

Lecture Lecture Tutorial Lap.

No. of 4 2 1
Hrs/Week

1
References:
1 – Thermodynamics, An Engineering Approach ,Yunus
Cengel and Michael A. boles. eighit edition ,2015
2 – Engineering Thermodynamics , SI units version ,
R.K.Rajput third edition 2007
3 – Fundamentals of Engineering Thermodynamics ,
Michael J. Moran and Howard N. Shapero ,fifth edition
,2006
4 – Applied Thermodynamics , Onkar singh, third
edition,2009

2
 Contents :

Subjects No. of lectures

1 – Properties of pure substances and
real gasses. 3 lectures
2 – Vapor and combined power cycles. 5 lectures
3 – Gas power cycles. 3 lectures
4 – Refrigeration cycles . 1 lecture

3
properties of pure substance
Pure substance refers to the “substance with
chemical homogeneity and constant chemical
composition.” H2O is a pure substance as it meets
both the above requirements. Any substance, which
undergoes a chemical reaction, cannot be pure
PROPERTIES AND IMPORTANT DEFINITIONS
Some of important terms used in discussion
ahead are given as under.
(a) Sensible heating: It refers to the heating of
substance in single phase. It causes rise in
temperature substance. In case of cooling in above
4
conditions it shall be called sensible cooling.
(b) Latent heating: It is the heating of substance for
causing its phase change without any change in it’s
temperature. If heat is extracted for causing phase
change without any change in its temperature it will
be called latent cooling.
(c) Normal boiling point: It is the temperature at
which vapour pressure equals to atmospheric
pressure and at this temperature phase change from
liquid to gas begins.
(d) Melting point: It is the temperature at which phase
change from solid to liquid takes place upon latent
heat.

5
(e) Saturation states: Saturation state of a
substance refers to the state at which its phase
transformation takes place without any change in
pressure and temperature. These can be saturated
solid state, saturated liquid state and saturated
vapour state. For example saturated vapour state
refers to the state of water at which its phase
changes to steam without varying pressure and
temperature.

6
 (f) Saturation pressure: It is the pressure at
which substance changes its phase for any
given temperature. Such as at any given
temperature water shall get converted into
steam at a definite pressure only, this pressure
is called saturation pressure corresponding to
given temperature. For water at 100°C the
saturation pressure is 1 atm pressure

7
(g) Saturation temperature: It refers to the
temperature at which substance changes its
phase for any given pressure. For water at 1 atm
pressure the saturation temperature is 100°C.
(h) Triple point: Triple point of a substance refers
to the state at which substance can coexist in
solid, liquid and gaseous phase in equilibrium. For
water it is 0.01°C i.e. at this temperature ice,
water and steam can coexist in equilibrium. Table
6.1 given below gives triple point data for number
of substances.
8
(i) Critical states: “Critical state refers to that
state of substance at which liquid and vapour
coexist in equilibrium.” In case of water at
22.12 MPa, and 374.15°C the water and vapour
coexist in equilibrium, thus it is the highest
pressure and temperature at which
distinguishable water and vapour exist
together. Data for critical state of many
substances is given in the table 6.1.
Specific volume at critical point for water is
0.00317 m /kg.
3

9
(j) Dryness fraction: It is the mass fraction of vapour in a
mixture of liquid and vapour at any point in liquid-vapour
mixture region. It is generally denoted by ‘x’. It is also
called quality of steam.

(k) Compressed liquid or subcooled liquid: Liquid at

temperature less than saturation temperature
corresponding to a given pressure is called compressed
liquid or subcooled liquid. Degree of subcooling is given by
the temperature difference between liquid temperature
and saturation of liquid at given pressure.
Degree of subcooling = Saturation temperature at given
pressure – Temperature of liquid.

10
(l) Superheated steam: Steam having
temperature more than the saturation
temperature corresponding to given pressure is
called superheated steam. Amount of
superheating is quantified by degree
of superheating. Degree of superheating is
given by difference between temperature of
steam and saturation temperature at given
pressure.
Degree of superheating = Temperature of steam
– Saturation temperature at given pressure.

11
12
Phases of a Pure Substance
There are three principle phases – solid, liquid and gas, but
a substance can have several other phases within the
principle phase. Examples include solid carbon (diamond
and graphite) and iron (three solid phases).
Nevertheless, thermodynamics deals with the primary
phases only.
Phase – Change Processes Of Pure Substances
1- Consider water at room temperature
(20°C) and normal atmospheric pressure
(1 atm) in a piston-cylinder device. The
water is in liquid phase, and it is called
compressed liquid or subcooled liquid
(not about to vaporize).
13
2- If we add heat to water, its temperature
will increase; let us say until 50°C. Due to
the increase in temperature, the specific
volume v will be increase. As a
consequence, the piston will move slightly
upward therefore maintaining constant
pressure (1 atm).

3- Now, if we continue to add heat to the

water, the temperature will increase
further until 100°C. At this point, any
additional addition of heat will vaporize
some water. This specific point where
water starts to vaporize is called saturated
liquid.
14 (Point 2)
4 - If we continue to add heat to water,
more and more vapor will be created,
while the temperature and the pressure
remain constant (T = 100°C and P = 1 atm).
The only property that changes is the
specific volume. These conditions will
remain the same until the last drop of
liquid is vaporized. At this point, the entire
cylinder is filled with vapor at 100°C. This
state is called saturated vapor (Point 4)

5 - The state between saturated liquid (only

liquid) and saturated vapor (only vapor)
where two phases exist is called saturated
liquid-vapor mixture. (Point 3)
15
 6 - After the saturated vapor phase, any addition of heat
will increase the temperature of the vapor, this state is
called superheated vapor (Point 5)

T-v diagram representing phase change for water at constant pressure

16
17
18
19
 Saturation Temperature and Saturation Pressure
• Recall that during a phase change, pressure and
temperature are not independent intensive properties.
As a consequence, the temperature at which water
starts boiling depends on the pressure. In other words,
water starts boiling at 100 ºC but only at 1 atm. At
different pressures, water boils at different
temperatures.
• At a given pressure, the temperature at which a pure
substance changes phase is called the saturation
temperature (Tsat).
• Likewise, at a given temperature, the pressure at which
a pure substance changes phase is called the saturation
pressure (Psat).
20
Property diagrams for phase change processes T-v
diagram
If we increase the pressure of water in the piston-cylinder
device, the process from compressed liquid to
superheated vapor will follow a path that looks like the
process for P = 1 atm, the only difference is that the of the
mixture region will be shorter.
Then, at a certain pressure, the mixture region will be
represented only by one point. This point is called the
critical point. It is defined as the point at which the
saturated liquid and saturated vapor states are identical.
At the critical point, the properties of a substance are
called critical properties (critical temperature (Tcr), critical
pressure (Pcr) and critical specific volume (vcr)).
21
Example
Water Pcr = 22.09 MPa
Air Pcr = 3.77 MPa
Tcr = 374.148°C = 647.298 K
Tcr = 132.5°C = 405.65 K
vcr = 0.003155 m3/kg
vcr = 0.0883 m3/kg

22
• If we connect all the points representing saturated liquid we
will obtain the saturated liquid line.
• If we connect all the points representing saturated vapor we
will obtain the saturated vapor line.
• The intersection of the two lines is the critical point.

T-v diagram and saturation lines.

23
P-v Diagram
If we consider the pressure-cylinder device, but with some weights
above the piston, if we remove the weights one by one to decrease
the pressure, and we allow a heat transfer to obtain an isothermal
process, we will obtain one of the curves of the P-v diagram.

24 P-v diagram
The P-v diagram can be extended to include the solid phase,
the solid liquid and the solid-vapor saturation regions.
• As some substances, as water, expand when they freeze, and the
rest (the majority) contracts during freezing process,
• we have two configurations for the P-v diagram with solid phase.

P-v diagram for a substance that contracts during freezing (left)

and for a substance that expends during freezing (right).
25
Triple point
Until now, we have defined the equilibrium between two phases.
However, under certain conditions, water can exist at the same
time as ice (solid), liquid and vapor. Theses conditions define the
so called triple point.
On a P-T diagram, these conditions are represented by a point.
Example
Water T = 0.01°C = 273.16 K and P = 0.6113 kPa
The P-T diagram is often called
the since all three phases are
separated by three lines.
Solid → vapor sublimation
)‫( التسامى‬
Solid → liquid
melting )‫(االنصهار‬
Liquid → vapor vaporization
)‫( التبخير‬
26 P-T diagram and the triple point.
27
STEAM TABLES AND MOLLIER DIAGRAM
Steam being pure substance has its unique and
constant properties at different pressures and
temperatures.
Therefore, thermodynamic properties can be
estimated once and tabulated for future use.
Steam table is a tabular presentation of properties
such as specific enthalpy, entropy, internal energy
and specific volume at different saturation
pressures and temperatures. Steam table may be
on pressure basis or on temperature basis.

28
The table on pressure basis has continuous variation of
pressure and corresponding to it : saturation
temperature (Tsat), enthalpy of saturated liquid (hf),
enthalpy of saturated vapour (hg), entropy of saturated
liquid (sf), entropy of saturated vapour (sg), specific
volume of saturated liquid (vf), specific volume of
saturated vapour (vg), internal energy of saturated liquid
(uf), internal energy of saturated vapour (ug) are given on
unit mass basis
• Similar to above the temperature based table which
gives continuous variation of temperature and
corresponding to it saturation pressure and other
properties as hf , hg, hfg, sf , sg, sfg, vf , vg, uf , ug and ufg
are given.
29
• Similarly, steam properties for superheated steam
are also estimated and tabulated at some discrete
pressures for varying degree of superheat. Super
heated steam table are available for getting enthalpy,
entropy, specific volume and internal energy
separately. Example of superheated steam table for
enthalpy is given here

30
31
 Mollier diagram is the enthalpy-entropy (h–s) diagram for
steam. This diagram is obtained on the basis of following
equation depending upon the phase transformation as discussed
earlier.
T ds = dh – v dp. (First and second law combined)

32 h–s diagram (Mollier diagram)

 Quality and Saturated Liquid-Vapor Mixture
Now, let’s review the constant pressure heat addition
process for water shown in above figure (pg 10). Since
state 3 is a mixture of saturated liquid and saturated
vapor, how do we locate it on the T-v diagram? To
establish the location of state 3 a new parameter called
the quality x is defined as:

33
The quality is zero for the saturated liquid and one for
the saturated vapor ( 0 ≤ x ≤ 1). The average specific
volume at any state 3 is given in terms of the quality as
follows. Consider a mixture of saturated liquid and
saturated vapor. The liquid has a mass mf and occupies
a volume Vf. The vapor has a mass mg and occupies a
volume Vg.

34
 Where:

35
Using the definition of the quality x

Then

Note, quantity 1- x is often given the name moisture. The

specific volume of the saturated mixture becomes

The form that we use most often is

36
It is noted that the value of any extensive property
per unit mass in the saturation region is calculated
from an equation having a form similar to that of the
above equation. Let Y be any extensive property and
let y be the corresponding intensive property, Y/m,
then

The term yfg is the difference between the saturated

vapor and the saturated liquid values of the property y;
y 37may be replaced by any of the variables v, u, h, or s.
We often use the above equation to determine the
quality x of a saturated liquid-vapor state.
The following application is called the Lever Rule:
The Lever Rule is illustrated in the following figures

38
How to Choose the Right Table
The correct table to use to find the thermodynamic
properties of a real substance can always be determined
by comparing the known state properties to the
properties in the saturation region. Given the temperature
or pressure and one other property from the group v, u, h,
and s, the following procedure is used. For example if the
pressure and specific volume are specified, three
questions are asked: For the given pressure

39
The answer to one of these questions must be yes.
If the answer to the first question is yes, the state is in the
compressed liquid region, and the compressed liquid
tables are used to find the properties of the state.

If the answer to the second question is yes, the state is in

the saturation region, and either the saturation
temperature table or the saturation pressure table is
used to find the properties. Then the quality is calculated
and is used to calculate the other properties, u, h, and s.

If the answer to the third question is yes, the state is in

the superheated region and the superheated tables are
used to find the other properties.
40
Some tables may not always give the internal energy.
When it is not listed, the internal energy is calculated
from the definition of the enthalpy as:
u=h- Pv

41
 Is Water Vapor an Ideal Gas?
• This question cannot be answered with a simple yes or no. The
error involved in treating water vapor as an ideal gas is
calculated and plotted in Fig. 3– 45.
• It is clear from this figure that at pressures below 10 kPa, water
vapor can be treated as an ideal gas, regardless of its
temperature, with negligible error (less than 0.1 percent). At
higher pressures, however, the ideal gas assumption yields
unacceptable errors, particularly in the vicinity of the critical
point and the saturated vapor line (over 100 percent).
• Therefore, in air-conditioning applications, the water vapor in
the air can be treated as an ideal gas with essentially no error
since the pressure of the water vapor is very low.
• In steam power plant applications, however, the pressures
involved are usually very high; therefore, ideal-gas relations
should not be used.
42
FIGURE 3–45 Percentage of error ([|vtable 2 videal|/vtable] 3 100) involved in
assuming steam to be an ideal gas, and the region where steam can
be treated as an ideal gas with lessthan 1 percent error.
43
 COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
• The ideal-gas equation is very simple and thus very convenient to
use.
• However, as illustrated in Fig. 3–45, gases deviate from ideal-gas
behavior significantly at states near the saturation region and the
critical point.
• This deviation from ideal-gas behavior at a given temperature and
pressure can accurately be accounted for by the introduction of a
correction factor called the compressibility factor Z defined as:
Z =P v/ RT Pv=ZRT

It can also be expressed as Z =V actual / V ideal

where v ideal =RT/P. Obviously, Z = 1 for ideal gases. For real
44
gases Z can be greater than or less than unity
Gases behave differently at a given
temperature and pressure, but they
behave very much the same at
temperatures and pressures normalized
with respect to their critical
temperatures and pressures. The
normalization is done as:

Here P is called the reduced pressure and T the

R R

reduced temperature.
The Z factor for all gases is approximately the same at
the same reduced pressure and temperature. This is
called the principle of corresponding states.
45
 FIGURE 3–47
Comparison of Z factors for various gases.
46
 FIGURE 3–48
At very low pressures, all gases
approach ideal-gas behavior
(regardless of the its
temperature).

FIGURE 3–49
Gases deviate from the ideal-gas
behavior the most in the
neighborhood of the critical
point.
47
OTHER EQUATIONS OF STATE
The ideal-gas equation of state is very simple, but its range of
applicability is limited. It is desirable to have equations of state
that represent the P-v-T behavior of substances accurately over a
larger region with no limitations

1. van der Waals Equation of State

where

2. Beattie-Bridgeman Equation of State

where
All five constant are determined from table 3-4a
48
3. Benedict-Webb-Rubin Equation of State

All eight constant are determined from table 3-4b

The accuracy of the van der Waals, Beattie-Bridgeman, and
Benedict-Webb-Rubin equations of state is illustrated in Fig.
3–56. It is apparent from this figure that the Benedict-
Webb-Rubin equation of state is usually the most accurate

50
51
Some questions
1- Is iced water a pure substance? Why?
2- What is the difference between saturated vapor and
superheated vapor?
3- Is there any difference between the intensive
properties of saturated vapor at a given temperature
and the vapor of a saturated mixture at the same
temperature?
4- Why are the temperature and pressure dependent
properties in the saturated mixture region?
5- Is it true that water boils at higher temperature at
higher pressure? Explain

52
6- What is the difference between the critical
point and the triple point?
7- Is it possible to have water vapor at -10oC?
8- A househusband is cooking beef stew for
his family in a pan that is (a) uncovered, (b)
covered with a light lid, and (c) covered with a
heavy lid. For which case will the cooking time
be the shortest? Why?

53