MEE 231

Basic Thermodynamics

Lecture 1: Properties of Pure Substances

Mostafa Rafid

Lecturer

Department of Mechanical Engineering

Shahjalal University of Science and Technology

Reference Books

• Thermodynamics – An Engineering Approach, Yunus A. Çengel, Michael A. Boles, Mehmet

Kanoğlu; McGraw Hill, 10th Edition (2023).

• Fundamentals of Engineering Thermodynamics, Michael J. Moran, Howard N. Shapiro,

Daisie D. Boettner, Margaret B. Bailey; John Wiley, 9th Edition (2018).

• Fundamentals of Thermodynamics, Claus Borgnakke, Richard E. Sonntag; John Wiley, 10th

Edition (2020).

2
What is Pure Substance?

• A substance that has a fixed chemical composition throughout is called a pure

substance.

• A mixture of various chemical elements or compounds also qualifies as a pure substance

as long as the mixture is homogeneous. Air, for example, is often considered to be a pure
substance because it has a uniform chemical composition.

• A mixture of two or more phases of a pure

substance is still a pure substance as long as
the chemical composition of all phases is the
same. A mixture of ice and liquid water, for
example. (a) (b) (c) (d)
Figure 1: (a)Nitrogen, (b) gaseous air, (c)
• A mixture of liquid air and gaseous air, a mixture of liquid and gaseous water - all
however, is not a pure substance, as different are pure substances, however, (d) a mixture
components in air condensing at different of liquid and gaseous air is not. [adapted
temperatures at a specified pressure. from Figure 3 - 1 & 3 – 2, Cengel, 10th Ed.]

3
Phase Change Processes of Pure Substances

• There are many practical situations where two phases of a pure substance coexist in
equilibrium.

− Water exists as a mixture of liquid and vapor in the boiler and the condenser of a steam
power plant.
− The refrigerant turns from liquid to vapor in the freezer of a refrigerator.

• All pure substances exhibit the same general behavior.

4
Compressed/Subcooled Liquid

• A piston–cylinder device containing liquid water at 20°C and 1 atm pressure (state 1,
Figure 2). Under these conditions, water exists in the liquid phase, and it is called a
compressed liquid, or a subcooled liquid, meaning that it is not about to vaporize.

• As the temperature rises, the liquid water expands slightly, and so its specific volume
increases. To accommodate this expansion, the piston moves up slightly. The pressure in
the cylinder remains constant at 1 atm during this process.

• Water is still a compressed liquid at this state since it has not started to
vaporize.

• What will happen if more heat is transferred, the temperature keeps rising
until it reaches 100°C?

Figure 2: At 1 atm and 20°C, water exists in the liquid phase (compressed liquid or
subcooled liquid). [adapted from Figure 3 – 5, Cengel, 10th Ed.]
5
Saturated Liquid

• Just at the moment when the temperature of the water reaches 100°C, water is still a
liquid, but any heat addition will cause some of the liquid to vaporize. That is, a phase-
change process from liquid to vapor is about to take place.

• A liquid that is about to vaporize is called a saturated liquid.

• Then again, what will happen if more heat is added right now?

Figure 3: At 1 atm pressure and 100°C, water exists as a liquid that is ready to
vaporize (saturated liquid). [adapted from Figure 3 – 6, Cengel, 10th Ed.]
6
Saturated Liquid-Vapor Mixture

• Once boiling starts, the temperature stops rising until the liquid is completely vaporized.
That is, the temperature will remain constant during the entire phase-change process if
the pressure is held constant.

• This can easily be verified by placing a thermometer into boiling pure water on top of a
stove. At sea level (P = 1 atm), the thermometer will always read 100°C if the pan is
uncovered or covered with a light lid.

• Midway about the vaporization line (state 3, Figure 4), the cylinder
contains equal amounts of liquid and vapor.

• During a boiling process, the only change we will observe is a large

increase in the volume and a steady decline in the liquid level as a
result of more liquid turning to vapor.

Figure 4: As more heat is transferred, part of the saturated liquid vaporizes

(saturated liquid–vapor mixture).[adapted from Figure 3 – 7, Cengel, 10th Ed.]
7
Saturated Vapor

• As we continue transferring heat, the vaporization process continues until the last drop of
liquid is vaporized (state 4, Figure 5). At this point, the entire cylinder is filled with vapor
that is on the borderline of the liquid phase.

• Any heat loss from this vapor will cause some of the vapor to condense (phase change
from vapor to liquid). A vapor that is about to condense is called a saturated vapor.

• A substance at states between 2 and 4 is referred to as a saturated liquid–

vapor mixture since the liquid and vapor phases coexist in equilibrium at these
states.

Figure 5: At 1 atm pressure, the temperature remains constant at 100°C until the last
drop of liquid is vaporized (saturated vapor).[adapted from Figure 3 – 8, Cengel, 10th
Ed.]
8
Superheated Vapor

• Once the phase-change process is completed, we are back to a single-phase region

again (this time vapor), and further transfer of heat results in an increase in both the
temperature and the specific volume (Figure 6).

• At state 5, the temperature of the vapor is 300°C; and if we transfer some heat from the
vapor, the temperature may drop somewhat but no condensation will take place as long
as the temperature remains above 100°C (for P = 1 atm).

• A vapor that is not about to condense (i.e., not a saturated vapor) is called a
superheated vapor.

Figure 6: As more heat is transferred, the temperature of the vapor starts to rise
(superheated vapor).[adapted from Figure 3 – 9, Cengel, 10th Ed.]

9
T – v Diagram for the Phase Change of Water

• This constant-pressure phase-change process is

illustrated on a T-v diagram in Figure 7.

• If the entire process described here is reversed by

cooling the water while maintaining the pressure at
the same value, the water will go back to state 1,
retracing the same path, and in so doing, the
amount of heat released will exactly match the
amount of heat added during the heating process.

• The statement “water boils at 100°C” is incorrect.

The correct statement is “water boils at 100°C at 1
atm pressure.”
Figure 7: T-v diagram for the heating
• So, how can we vary pressure in the same system? process of water at constant
pressure. [adapted from Figure 3 –
10, Cengel, 10th Ed.]
10
Saturation Temperature and Pressure
Table 1: Saturation Pressure of Water at Various Temperatures.
[adapted from Table 3 – 1, Cengel, 10th Ed.]

• The temperature at which water starts boiling depends on the

pressure; therefore, if the pressure is fixed, so is the boiling
temperature.

• 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.

• Saturation tables that list the saturation pressure against the

temperature (or the saturation temperature against the
pressure) are available for practically all substances.

11
Relation between Psat and Tsat

• During a phase-change process, pressure and temperature are

obviously dependent properties, and there is a definite relation
between them, that is, Psat = f(Tsat).

• A plot of Psat versus Tsat, such as the one given for water in Figure
8, is called a liquid–vapor saturation curve. A curve of this kind is
characteristic of all pure substances.

• It is clear from Figure 8 that Tsat increases with Psat. Thus, a

Figure 8: The liquid–
substance at higher pressures boils at higher temperatures.
vapor saturation curve of
a pure substance
(numerical values are for
water). [adapted from
Figure 3 – 11, Cengel,
10th Ed.]

12
Natural Phenomena Based on Psat and Tsat Dependence
Table 2: Standard
Atmospheric Pressure and
• Example 1: In the kitchen, higher boiling temperatures mean Boiling temperature of
shorter cooking times and energy savings. A beef stew, for Water at Various
example, may take 1 to 2 h to cook in a regular pan that Altitudes. [adapted from
operates at 1 atm pressure, but only 20 min in a pressure cooker Table 3 – 2, Cengel, 10th
Ed.]
operating at 3 atm absolute pressure (corresponding boiling
temperature: 134°C).

• Example 2: The atmospheric pressure, and thus the boiling

temperature of water, decreases with elevation. Therefore, it
takes longer to cook at higher altitudes than it does at sea level
(unless a pressure cooker is used). For example, the standard
atmospheric pressure at an elevation of 2000 m is 79.50 kPa,
which corresponds to a boiling temperature of 93.3°C as
opposed to 100°C at sea level (zero elevation).

• The variation of the boiling temperature of water with altitude

at standard atmospheric conditions is given in Table 2.
13
Practical Applications of Psat and Tsat Dependence

• The interdependence between saturation pressure and temperature allows us to control

the boiling temperature of a substance by simply controlling the pressure, and it has
numerous applications in practice. First, look into the following scenario closely.

• For a sealed can of liquid refrigerant-134a in a room at 25°C, if the lid is opened slowly
and some refrigerant is allowed to escape, the pressure in the can will start dropping until
it reaches the atmospheric pressure. Temperature dropping and even ice forming outside
the can will be noticed, eventually until the last drop of the refrigerant vaporizes as the
saturation temperature of refrigerant-134a is -26°C at 1 atm.

• Another aspect of this interesting physical phenomenon is that a liquid cannot vaporize
unless it absorbs energy in the amount of the latent heat of vaporization. Therefore, the
larger the rate of heat transfer, the higher the rate of vaporization.

• What will happen if the pressure is at 1 atm and the surrounding of the can is heavily
insulated?

14
Practical Applications of Psat and Tsat Dependence

• The boiling temperature of nitrogen at atmospheric pressure is -196°C. For this reason,
nitrogen is commonly used in low-temperature scientific studies and cryogenic
applications to maintain a test chamber at a constant temperature of -196°C.

• This is done by placing the test chamber into a liquid nitrogen bath that is open to the
atmosphere. Any heat transfer from the environment to the test section is absorbed by
the nitrogen, which evaporates isothermally and keeps the test chamber temperature
constant at -196°C.
• Liquid nitrogen is also used to burn off unwanted spots on the skin by
soaking a cotton swab in liquid nitrogen and wetting the target area.
As the nitrogen evaporates, it freezes the affected skin by rapidly
absorbing heat from it.

• Check out about the vacuum cooling and freezing from Cengel.
Figure 9: The temperature of liquid nitrogen exposed to the atmosphere
remains constant at -196°C, and thus it maintains the test chamber at -
196°C. [adapted from Figure 3 – 12, Cengel, 10th Ed.]
15
The T-v Diagram (Expanded)

• Let us add weights on top of the piston (like in Figure 10) until the pressure inside the
cylinder reaches 1 MPa. At this pressure, water has a somewhat smaller specific volume
than it does at 1 atm pressure.

• As heat is transferred to the water at this new pressure, the process follows a path that
looks very much like the process path at 1 atm pressure, as shown in Figure 11, but there
are some noticeable differences.

− First, water starts boiling at a much higher temperature (179.9°C) at this

pressure.

− Second, the specific volume of the saturated liquid is larger and the specific
volume of the saturated vapor is smaller than the corresponding values at 1
atm pressure. That is, the horizontal line that connects the saturated liquid and
saturated vapor states is much shorter.
Figure 10: We can vary the pressure inside the cylinder by adding or removing weights
on the piston-cylinder system.[adapted from Figure 3 – 18, Cengel, 10th Ed.]
16
The T-v Diagram (Expanded)

• As the pressure is increased further, this saturation line continues to shrink, as shown in
Figure 11, and it becomes a point when the pressure reaches 22.06 Mpa for the case of
water.

• This point is called the critical point, and it is

defined as the point at which the saturated
liquid and saturated vapor states are identical.

• The critical-point properties of water are Pcr =

22.06 MPa, Tcr = 373.95°C, and vcr = 0.003106
m3/kg.

• What happens beyond Pcr?

Figure 11: T-v diagram of constant-pressure phase-

change processes of a pure substance at various
pressures (numerical values are for water). [adapted
from Figure 3 – 15, Cengel, 10th Ed.]
17
The T-v Diagram (Expanded)

• At pressures above the critical pressure, there is no distinct phase-change process (Figure
12). With increasing temperature at a pressure beyond Pcr, eventually, the phase changes
to a new phase that resembles a vapor, but we can never tell when the change has
occurred.
• Above the critical state, there is no line that separates the
compressed liquid region and the superheated vapor region.

• However, it is customary to refer to the substance as superheated

vapor at temperatures above the critical temperature and as
compressed liquid at temperatures below the critical
temperature.

• Your question: What happens to the latent heat at or beyond Pcr?

− It becomes 0 (zero)! (Sorry about my answer in previous class!)
Figure 12: At supercritical pressures (P > Pcr), there is no distinct
phase-change (boiling) process. [adapted from Figure 3 – 16, Cengel,
10th Ed.]
18
 The T-v Diagram (Expanded)

• The saturated liquid states in Figure 11 can be connected by a line called the saturated
liquid line, and saturated vapor states in the same figure can be connected by another
line, called the saturated vapor line.

• These two lines meet at the critical point, forming a

dome as shown in Figure 13.

• The region to the left of the saturated liquid line is

called the compressed liquid region (or subcooled
liquid region), which is a single phase region.

• The region to the right of the saturated vapor line is

called the superheated vapor region, which is also a
single phase region.

• All the states that involve both phases in equilibrium

Figure 13: T-v diagram of a pure are located under the dome, called the saturated
substance.[adapted from Figure 3 – liquid–vapor mixture region, or the wet region.
17a, Cengel, 10th Ed.] 19
The P-v Diagram

• Consider again a piston–cylinder device that contains liquid water at 1 MPa and 150°C
(Figure 10). Water at this state exists as a compressed liquid. Now the weights on top of
the piston are removed one by one so that the pressure inside the cylinder decreases
gradually.

• The water is allowed to exchange heat with the surroundings so its temperature remains
constant.

• As the pressure decreases, the volume of the water increases slightly. When the
pressure reaches the saturation pressure value at the specified temperature
(0.4762 MPa), the water starts to boil. During this vaporization process, both the
temperature and the pressure remain constant, but the specific volume
increases.

Figure 10: We can vary the pressure inside the cylinder by adding or removing weights
on the piston-cylinder system.[adapted from Figure 3 – 18, Cengel, 10th Ed.]
20
The P-v Diagram

• Once the last drop of liquid is vaporized, further reduction in pressure results in a further
increase in specific volume.
• Notice that during the phase-change process,
we did not remove any weights. Doing so
would cause the pressure and therefore the
temperature to drop [since Tsat = f(Psat)], and
the process would no longer be isothermal.

• When the process is repeated for other

temperatures, similar paths are obtained for
the phase-change processes. Connecting the
saturated liquid and the saturated vapor states
by a curve, we obtain the P-v diagram of a
pure substance, as shown in Figure 14.

Figure 14: P-v diagram of a pure substance.[adapted

from Figure 3 – 17b, Cengel, 10th Ed.]
21
Extended P-v Diagram to Include the Solid Phase

• The diagrams can easily be extended to include the solid phase as well as the solid–
liquid and the solid–vapor saturation regions.

• Most substances contract during a solidification (i.e., freezing) process. Others, like water,
expand as they freeze.

• The P-v diagrams for both groups of substances

are given in Figure 15 and 16 (in the next page).

• These two diagrams differ only in the solid–liquid

saturation region.

Figure 15: P-v diagram of a substance that contracts on

freezing.[adapted from Figure 3 – 19a, Cengel, 10th Ed.]
22
Extended P-v Diagram to Include the Solid Phase

• If water contracted on freezing as most other substances do, the ice formed would be
heavier than the liquid water, and it would settle to the bottom of rivers, lakes, and
oceans instead of floating at the top. The sun’s rays would never reach these ice layers,
and the bottoms of many rivers, lakes, and oceans would be covered with ice at times,
seriously disrupting marine life.

• We are all familiar with two phases being in

equilibrium, but under some conditions all
three phases of a pure substance coexist in
equilibrium.

• On P-v or T-v diagrams, these triple-phase

states form a line called the triple line.

Figure 16: P-v diagram of a substance that expands on

freezing (such as water).[adapted from Figure 3 – 19b,
Cengel, 10th Ed.]
23
Triple Line and Triple Point

• The states on the triple line of a substance have the same pressure and temperature but
different specific volumes.

• The triple line appears as a point on the P-T diagrams (in Figure 19) and, therefore, is often
called the triple point.

• For water, the triple-point temperature and pressure are 0.01°C and 0.6117 kPa. That is, all
three phases of water coexist in equilibrium only if the temperature and pressure have
precisely these values.

• No substance can exist in the liquid phase in stable equilibrium at pressures

below the triple-point pressure. However, substances at high pressures can
exist in the liquid phase at temperatures below the triple-point temperature.

Figure 17: At triple-point pressure and temperature, a substance exists in

three phases in equilibrium.[adapted from Figure 3 – 20, Cengel, 10th Ed.]
24
Triple Line and Triple Point

• For example, water cannot exist in liquid form in equilibrium at atmospheric pressure at
temperatures below 0°C, but it can exist as a liquid at -20°C at 200 MPa pressure. Also,
ice exists at seven different solid phases at pressures above 100 MPa.

• There are two ways a substance can pass from the solid to the vapor phase: either it
melts first into a liquid and subsequently evaporates, or it evaporates directly without
melting first.

• The latter occurs at pressures below the triple-point value, since a pure substance cannot
exist in the liquid phase at those pressures (Figure 18).
• Passing from the solid phase directly into the vapor phase is called
sublimation. For substances that have a triple-point pressure above the
atmospheric pressure such as solid CO2 (dry ice), sublimation is the only way
to change from the solid to the vapor phase at atmospheric conditions.
Figure 18: At low pressures (below the triple point value), solids evaporate without
melting first (sublimation).[adapted from Figure 3 – 21, Cengel, 10th Ed.]
25
The P-T Diagram

• The diagram in Figure 19 is often

called the phase diagram since all
three phases are separated from
each other by three lines.

• These three lines meet at the triple

point, where all three phases
coexist in equilibrium.

Figure 19: P-T diagram of pure substances.

[adapted from Figure 3 – 22, Cengel, 10th
Ed.]
26
The P-T Diagram

• The vaporization line ends at the

critical point because no distinction
can be made between liquid and
vapor phases above the critical
point.

• Substances that expand and

contract on freezing differ only in
the melting line on the P-T diagram.

Figure 19: P-T diagram of pure substances.

[adapted from Figure 3 – 22, Cengel, 10th
Ed.]
27
 The P-v-T Surface

• The state of a simple compressible substance is fixed by any two independent, intensive
properties. Once the two appropriate properties are fixed, all the other properties
become dependent properties.
• Any equation with two
independent variables in
(a) (b)
the form z = z(x, y) represents
a surface in space, we can
represent the P-v-T behavior
of a substance as a surface
in space, as shown in Figures
20 and 21 (next page).
Figure 20: (a) P-v-T surface of a
substance that contracts on freezing,
(b) P-v-T surface of a substance that
expands on freezing (like water).
[adapted from Figure 3 – 23 & 3 – 24,
Cengel, 10th Ed.]

28
Gibb’s Phase Rule

• The number of degrees of freedom within a homogenous/heterogeneous mixture of

pure substances/mixtures is given by Gibb’s phase rule as,

𝑓 =𝐶 −𝑃+2
• f = number of degrees of freedom
• C = number of components (pure substances) in the mixture
• P = number of phases

• Case 1: A homogeneous (P = 1) pure substance (C =1) requires f = 1 − 1 + 2 = 2 intensive

properties to fix its state.

• Case 2: A homogeneous (P = 1) mixture of two pure substances (C = 2) requires f = 2 − 1

+ 2 = 3 intensive properties to fix its state.

• Case 3: A two-phase (P = 2) pure substance (C = 1) ⇒ f = 1 − 2 + 2 = 1: each phase

requires one intensive property to fix its state & one intensive property can be varied
independently.
29
Property Tables

• For most substances, the relationships among thermodynamic properties are too complex
to be expressed by simple equations.

• Therefore, properties are frequently presented in the form of tables.

• A separate table is prepared for each region of interest such as the superheated vapor,
compressed liquid, and saturated (mixture) regions.

30
Enthalpy

• In the analysis of certain types of processes, particularly in power

generation and refrigeration (Figure 21), we often encounter the
combination of properties u + Pv.

• For the sake of simplicity and convenience, this combination is

defined as a new property, enthalpy, and given the symbol h:
Figure 21: The
combination u + Pv
is often encountered
ℎ = 𝑢 + 𝑃𝑣 𝑘𝐽/𝑘𝑔 in the analysis of
control volumes.
[adapted from Figure
3 – 25, Cengel, 10th
𝑜𝑟, 𝐻 = 𝑈 + 𝑃𝑉 𝑘𝐽 Ed.]

31
 Saturated Liquid and Saturated Vapor States

• The properties of saturated liquid and saturated vapor (figure 13) for water are listed in
Tables A–4 and A–5 (Cengel, 10th Ed.).

• It is more convenient to use Table A–4 when

temperature is given and Table A–5 when pressure
is given.

• The subscript f is used to denote properties of a

saturated liquid and the subscript g to denote the
properties of saturated vapor. These symbols are
commonly used in thermodynamics and
originated from German.

• Another subscript commonly used is fg, which

denotes the difference between the saturated
vapor and saturated liquid values of the same
Figure 13: T-v diagram of a pure property.
substance.[adapted from Figure 3 –
17a, Cengel, 10th Ed.] 32
Saturated Liquid-Vapor Mixture

• During a vaporization process, a substance exists as a mixture of saturated liquid and

saturated vapor (Figure 22).

• To analyze this mixture properly, we need to know the proportions of the liquid and vapor
phases in the mixture. This is done by defining a new property called the quality, x as the
ratio of the mass of vapor to the total mass of the mixture:
𝑚𝑣𝑎𝑝𝑜𝑟
𝑥=
𝑚𝑡𝑜𝑡𝑎𝑙

Where, 𝑚𝑡𝑜𝑡𝑎𝑙 = 𝑚𝑙𝑖𝑞𝑢𝑖𝑑 + 𝑚𝑣𝑎𝑝𝑜𝑟 = 𝑚𝑓 + 𝑚𝑔

• Quality has significance for saturated mixtures only. It has no

meaning in the compressed liquid or superheated vapor
regions.
Figure 22: The relative amounts of liquid and vapor phases in a
saturated mixture are specified by the quality x.[adapted from
Figure 3 – 31, Cengel, 10th Ed.]
33
Miscellaneous Facts about Saturated Liquid-Vapor Mixture

• The quality of a system that consists of saturated liquid is 0 (or 0 percent), and the quality
of a system consisting of saturated vapor is 1 (or 100 percent).

• In saturated mixtures, quality can serve as one of the two independent intensive
properties needed to describe a state.

• The properties of the saturated liquid are the same whether it exists alone or in a mixture
with saturated vapor. During the vaporization process, only the amount of saturated liquid
changes, not its properties. The same can be said about a saturated vapor.

• A saturated mixture can be treated as a combination of two subsystems: the saturated

liquid and the saturated vapor.

34
Miscellaneous Facts about Saturated Liquid-Vapor Mixture

• The amount of mass for each phase is usually not known in a saturated liquid-vapor
mixture. Therefore, it is often more convenient to imagine that the two phases are mixed
well, forming a homogeneous mixture (Figure 23).

• Then the properties of this “mixture” will simply be the average properties of the saturated
liquid–vapor mixture under consideration.

• Consider a tank that contains a saturated liquid–vapor mixture. The volume occupied by
saturated liquid is Vf, and the volume occupied by saturated vapor is Vg. The total volume
V is the sum of the two:
𝑉 = 𝑉𝑓 + 𝑉𝑔

• Question: Derive the expression of the average specific

volume inside the saturated liquid-vapor mixture region.

Figure 23: A two-phase system can be treated as a homogeneous

mixture for convenience.[adapted from Figure 3 – 32, Cengel, 10th
Ed.]
35
Expression of Average Properties inside Wet Region

𝑉 = 𝑉𝑓 + 𝑉𝑔

⟹ 𝑚𝑡 𝑣𝑎𝑣𝑔 = 𝑚𝑓 𝑣𝑓 + 𝑚𝑔 𝑣𝑔 ∵ 𝑉 = 𝑚𝑣

⟹ 𝑚𝑡 𝑣𝑎𝑣𝑔 = 𝑚𝑡 − 𝑚𝑔 𝑣𝑓 + 𝑚𝑔 𝑣𝑔 ∵ 𝑚𝑡 = 𝑚𝑓 + 𝑚𝑔

• Dividing by mt yields,

𝑚𝑔
𝑣𝑎𝑣𝑔 = 1 − 𝑥 𝑣𝑓 + 𝑥𝑣𝑔 [∵ 𝑥 = ൗ𝑚𝑡 ]

• This relation can also be expressed as,

𝑣𝑎𝑣𝑔 = 𝑣𝑓 − 𝑥 𝑣𝑓 + 𝑥 𝑣𝑔 = 𝑣𝑓 + 𝑥 𝑣𝑔 − 𝑣𝑓

⟹ 𝑣𝑎𝑣𝑔 = 𝑣𝑓 + 𝑥 𝑣𝑓𝑔 (𝑚3 /𝑘𝑔) ∵ 𝑣𝑓𝑔 = 𝑣𝑔 − 𝑣𝑓

36
Expression of Average Properties inside Wet Region

• An alternative expression of quality can be obtained from the above equation,

𝑣𝑎𝑣𝑔 − 𝑣𝑓 𝑣𝑎𝑣𝑔 − 𝑣𝑓
𝑥= =
𝑣𝑓𝑔 𝑣𝑔 − 𝑣𝑓

• Based on this equation, quality can be related to the horizontal distances on a P-v or T-v
diagram (Figure 24).

• The analysis given above can be repeated for any other

properties, such as,

ℎ𝑎𝑣𝑔 = ℎ𝑓 + 𝑥 ℎ𝑓𝑔 (𝐾𝐽/𝑘𝑔)

𝑠𝑎𝑣𝑔 = 𝑠𝑓 + 𝑥 𝑠𝑓𝑔 (𝐾𝐽/𝑘𝑔. 𝐾)

Figure 24: Quality is related to the horizontal distances on P-v and

T-v diagrams.[adapted from Figure 3 – 33, Cengel, 10th Ed.]
37
Superheated Vapor

• In the region to the right of the saturated vapor line and at temperatures above the
critical point temperature, a substance exists as superheated vapor.

• Since the superheated region is a single-phase region (vapor phase only), temperature
and pressure are no longer dependent properties, and they can conveniently be used as
the two independent properties in the tables.

• The superheated vapor tables is given in Table A-6 (Cengel, 10th Ed.). In these tables, the
properties are listed against temperature for selected pressures starting with the saturated
vapor data.

38
Subcooled Liquid

• Properties of the subcooled water is given in Table A–7 (Cengel, 10th Ed.). The format of
Table A–7 is very much like the format of the superheated vapor tables.

• Subcooled liquid tables are not as commonly available. One reason for the lack of
compressed liquid data is the relative independence of compressed liquid properties with
pressure. Increasing the pressure 100 times often causes properties to change less than 1
percent.
• In the absence of compressed liquid data, a general
approximation is to treat compressed liquid as saturated
liquid at the given temperature (Figure 25).

• This is because the compressed liquid properties depend on

temperature much more strongly than they do on pressure.
Figure 25: A compressed liquid may be approximated as a saturated
liquid at the given temperature.[adapted from Figure 3 – 40, Cengel,
10th Ed.]
39
Subcooled Liquid

• Of all the thermophysical properties, the property whose value is most sensitive to
variations in the pressure is the enthalpy h.

• However, the error in h at low to moderate pressures and temperatures can be reduced
significantly by evaluating it from,

ℎ ≅ ℎ𝑓 @ 𝑇 + 𝑣𝑓 @ 𝑇 (𝑃 − 𝑃𝑠𝑎𝑡 @ 𝑇 )

• Note that this equation does not yield any significant improvement at moderate to high
temperatures and pressures, and it may even backfire and result in greater error due to
overcorrection at very high temperatures and pressures.

• To tackle this uncertainty, a new term degree of subcooling of a liquid at a given

temperature and pressure is defined, which is a measure of deviation of the liquid
temperature from the saturation temperature of the substance at the given pressure.

40
Degree of Subcooling

• The degree of subcooling of a subcooled liquid at a given temperature T and pressure P is

simply the difference between the saturation temperature of the substance at the given
pressure and the actual temperature. That is,

∆𝑇𝑠𝑢𝑏𝑐𝑜𝑜𝑙 = 𝑇𝑠𝑎𝑡 @ 𝑃 −𝑇

• For example, noting that the saturation temperature of water 1 atm pressure is 100°C, the
degree of subcooling of water at 20°C and 1 atm pressure is,

∆𝑇𝑠𝑢𝑏𝑐𝑜𝑜𝑙 = 𝑇𝑠𝑎𝑡 @ 𝑃 − 𝑇 = 100 − 20 = 80℃

• The degree of subcooling is of interest in engineering applications that involve cooling

below the saturation temperature, such as the condensers of refrigerators and power
plants.

41
Reference State and Reference Values

• The values of u, h, and s cannot be measured directly, and they are calculated from
measurable properties using the relations between thermodynamic properties.

• However, those relations give the changes in properties, not the values of properties at
specified states.

• Therefore, we need to choose a convenient reference state and assign a value of zero
for a convenient property or properties at that state.

• For water, the state of saturated liquid at 0.01°C is taken as the reference state, and the
internal energy and entropy are assigned zero values at that state. (See Table A-5 & A-8)

• Note that some properties may have negative values as a result of the reference state
chosen.

• In thermodynamics, we are concerned with the changes in properties only, and the
reference state chosen is of no consequence in calculations as long as we use values
from a single consistent set of tables or charts.
42
Mathematical Problem #1, #2 & #3

• Example 3 – 1 from Cengel, 10th Ed.

A rigid tank contains 50 kg of saturated liquid water at 90°C. Determine the pressure in the
tank and the volume of the tank.

• Example 3 – 3 from Cengel, 10th Ed.

A mass of 200 g of saturated liquid water is completely vaporized at a constant pressure of

100 kPa. Determine (a) the volume change and (b) the amount of energy transferred to the
water.

• Example 3 – 4 from Cengel, 10th Ed.

A rigid tank contains 10 kg of water at 92°C. If 8 kg of the water is in the liquid form and the
rest is in the vapor form, determine (a) the pressure in the tank and (b) the volume of the
tank.

43
Mathematical Problem #4, #5 & #6

• Example 3 – 5 from Cengel, 10th Ed.

An 80-L vessel contains 4 kg of refrigerant-134a at a pressure of 170 kPa. Determine (a) the
temperature, (b) the quality, (c) the enthalpy of the refrigerant, and (d) the volume
occupied by the vapor phase.

• Example 3 – 7 from Cengel, 10th Ed.

Determine the temperature of water at a state of P = 0.5 MPa and h = 2890 kJ/kg.

• Example 3 – 8 from Cengel, 10th Ed.

Determine the internal energy of compressed liquid water at 80°C and 5 MPa, using (a)
data from the compressed liquid table and (b) saturated liquid data. What is the error
involved in the second case?

44
Mathematical Problem #7

• Mathematical Problem of CT – 1, from last year (2020-21 Session)

A piston-cylinder device with a volume of 8 m3 contains 100 kg NH3 at 0.77 MPa. Now, heat
is transferred to the gas and the piston is adjusted so that the temperature and the pressure
of the gas reaches 95°C and 1.0 MPa, respectively.

With the scenario stated above, determine:

i. The initial and final state of the gas,

ii. The temperature and the enthalpy at the initial state
iii. The enthalpy and the specific volume at the final state
iv. The change of volume and the total amount of heat transferred to the gas to reach the
final state from the initial state.

45
Ideal Gas Equation of State

• Any equation that relates the pressure, temperature, and specific volume of a substance
is called an equation of state. Property relations that involve other properties of a
substance at equilibrium states are also referred to as equations of state.

• The simplest and best-known equation of state for substances in the gas phase is the
ideal-gas equation of state. This equation predicts the P-v-T behavior of a gas quite
accurately within some properly selected region.

• Gas and vapor are often used as synonymous words. The vapor phase of a substance is
customarily called a gas when it is above the critical temperature. Vapor usually implies a
gas that is not far from a state of condensation.

• Ideal Gas Equation of State can be written as,

𝑃𝑣 = 𝑅𝑇

Where, R is called the gas constant, which is different for each gas.
46
Ideal Gas Equation of State

• R can also be expressed as,

𝑅𝑢
𝑅= (𝑘𝐽/𝑘𝑔. 𝐾)
𝑀
Where, Ru is the universal gas constant and M is the molar mass (also called molecular
weight) of the gas.

• The constant Ru is the same for all substances, and its value is 8.31447 kJ/kmol.K.

• The mass of a system is equal to the product of its molar mass M and the mole number N,
that is,

𝑚 = 𝑀𝑁 (𝑘𝑔)

• Similarly, using the molar specific volume, 𝑣,ҧ which denotes the volume per unit mole of a
gas, the total volume of a gas can be expressed as,

𝑉 = 𝑁𝑣ҧ (𝑚3)
47
Ideal Gas Equation of State

• Therefore, the ideal gas equation of state can be derived and written as several
following forms,

𝑉
𝑃𝑣 = 𝑅𝑇 ⟹ 𝑃 = 𝑅𝑇 ⟹ 𝑃𝑉 = 𝑚𝑅𝑇
𝑚

𝑅𝑢
⟹ 𝑃𝑉 = 𝑀𝑁 𝑇 ⟹ 𝑃𝑉 = 𝑁𝑅𝑢 𝑇
𝑀

⟹ 𝑃 𝑁𝑣ҧ = 𝑁𝑅𝑢 𝑇 ⟹ 𝑃𝑣ҧ = 𝑅𝑢 𝑇

• An ideal gas is an imaginary substance that obeys the relation Pv = RT.

• It has been experimentally observed that the ideal-gas relation given closely
approximates the P-v-T behavior of real gases at low densities. At low pressures and high
temperatures, the density of a gas decreases, and the gas behaves as an ideal gas
under these conditions.
48
When to Use Ideal Gas Equation?

• In the range of practical interest, many familiar gases, including even heavier gases,
such as krypton can be treated as ideal gases with negligible error (often less than 1
percent).

• Dense gases such as water vapor in steam power plants and refrigerant vapor in
refrigerators, however, should not be treated as ideal gases. Instead, the property tables
should be used for these substances.

49
When to treat Water Vapor As An Ideal Gas?

• To treat water vapor as an ideal gas, the pressure at the area of application must be
taken into account.

• 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 (over 100 percent) and the saturated vapor
line.

• 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, the ideal-gas relation should not be used.

50
What is Low Pressure or High Temperature?

• The question arises that what exactly constitutes low pressure or high temperature?

• Is −100°C a low temperature? It definitely is for most substances but not for air. Air (or
nitrogen) can be treated as an ideal gas at this temperature and atmospheric pressure
with an error under 1 percent. Gases deviate from ideal-gas behavior significantly at
states near the saturation region and the critical point. As nitrogen is well over its critical
temperature (–147°C) and away from the saturation region at -100 °C, it shows similar
behavior as an ideal gas. At this temperature and pressure, however, most substances
would exist in the solid phase.

• Therefore, the pressure or temperature of a substance is high or low relative to its critical
temperature or pressure.

• 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.
51
Reduced Pressure, Temperature and Compressibility Factor

• The normalization is done as,

𝑃 𝑇
𝑃𝑅 = 𝑇𝑅 =
𝑃𝑐𝑟 𝑇𝑐𝑟

• Here PR is called the reduced pressure and TR the reduced temperature.

• The 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,
𝑃𝑣
𝑍= ⟹ 𝑃𝑣 = 𝑍𝑅𝑇
𝑅𝑇
𝑣𝑎𝑐𝑡𝑢𝑎𝑙
• It can also be expressed as, 𝑍=
𝑣𝑖𝑑𝑒𝑎𝑙

𝑅𝑇
Where, 𝑣𝑖𝑑𝑒𝑎𝑙 =
𝑃
52
Reduced Pressure, Temperature and Compressibility Factor

• 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.

• Obviously, Z = 1 for ideal gases. For real gases, Z can be greater than or less than unity
(Figure 26). The farther away Z is from unity, the more the gas deviates from ideal-gas
behavior.

• In figure 26, the experimentally determined Z values are plotted against PR and TR for
several gases. The gases seem to obey the principle of corresponding states reasonably
well. The graph in figure 26 is also known as the generalized compressibility chart.

53
The Generalized Compressibility Chart

Figure 26: Comparison of Z

factors for various
gases.[adapted from Figure 3 –
48, Cengel, 10th Ed.]
54
The Generalized Compressibility Chart

• The following observations can be made from the

generalized compressibility chart:

− At very low pressures (PR << 1), gases behave as ideal

gases regardless of temperature.
− At high temperatures (TR > 2), ideal-gas behavior can be
assumed with good accuracy regardless of pressure
(except when PR >> 1).
− The deviation of a gas from ideal-gas behavior is greatest
in the vicinity of the critical point (Figure 27). Figure 27: Gases deviate
from the ideal-gas behavior
the most in the neighborhood
of the critical
point.[adapted from Figure 3
– 50, Cengel, 10th Ed.]

55
Other Equations of State (EOS)

• 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. Such equations are naturally more
complicated. Several equations have been proposed for this purpose, a few of them are
as follows:

• Van der Waals Equation of State:

𝑎
𝑃+ 2 𝑣 − 𝑏 = 𝑅𝑇
𝑣

27𝑅2 𝑇𝑐𝑟 2 𝑅𝑇𝑐𝑟

Where, 𝑎= 𝑏=
64𝑃𝑐𝑟 8𝑃𝑐𝑟

• a → account for intermolecular forces of attraction.

• b → account for the volume occupied by gas molecules.

56
Other Equations of State (EOS)

• Redlich – Kwong Equation of State:

𝑅𝑇 𝑎
𝑃= −
𝑣 −𝑏 𝑣 𝑣+𝑏 𝑇

𝑅2 𝑇𝑐𝑟 2.5 𝑅𝑇𝑐

Where, 𝑎 = 0.42748 𝑏 = 0.08664
𝑃𝑐𝑟 𝑃𝑐

57
Other Equations of State (EOS)

• Beattie – Bridgeman Equation of State:

𝑅𝑢 𝑇 𝑐 𝐴
𝑃= 2 1 − 3 𝑣ҧ + 𝐵 − 2
𝑣ҧ 𝑣𝑇
ҧ 𝑣ҧ

𝑎 𝑏
Where, 𝐴 = 𝐴0 1− 𝐵 = 𝐵0 1−
𝑣ҧ 𝑣ҧ

• The Beattie-Bridgeman equation is known to be reasonably accurate for densities up to

about 0.8ρcr, where ρcr is the density of the substance at the critical point.

• The typical values of the constants of several substances are given in Table 1.

58
Other Equations of State (EOS)

Table 3: Typical constant values of the Beattie – Bridgeman Equation for a few common
substances. [adapted from Table 3 – 4 (a), Cengel, 10th Ed.]

59
Other Equations of State (EOS)

• Benedict – Webb – Rubin Equation of State:

𝑅𝑢 𝑇 𝐶0 1 𝑏𝑅𝑢 𝑇 − 𝑎 𝑎𝛼 𝑐 𝛾 − 𝛾2
𝑃= + 𝐵0 𝑅𝑢 𝑇 − 𝐴0 − 2 2 + 3
+ 6 + 3 2 1 + 2 𝑒 𝑣ത
𝑣ҧ 𝑇 𝑣ҧ 𝑣ҧ 𝑣ҧ 𝑣ҧ 𝑇 𝑣ҧ
• This equation can handle substances at densities up to about 2.5ρcr.

• The typical values of the constants of several substances are given in Table 2.
Table 4: Typical constant values of the Benedict – Webb – Rubin Equation for a few common
substances. [adapted from Table 3 – 4 (b), Cengel, 10th Ed.]

60
Other Equations of State (EOS)

• Virial Equation of State:

𝑅𝑇 𝑎(𝑇) 𝑏(𝑇) 𝑐(𝑇) 𝑑(𝑇)

𝑃= + 2 + 3 + 4 + 5 + ……………
𝑣 𝑣 𝑣 𝑣 𝑣

• This and similar equations are called the virial equations of state, and the coefficients
a(T), b(T), c(T), and so on, that are functions of temperature alone are called virial
coefficients.

• Obviously, as the pressure approaches zero, all the virial coefficients will vanish and the
equation will reduce to the ideal-gas equation of state.

• The P-v-T behavior of a substance can be represented accurately with the virial equation
of state over a wider range by including a sufficient number of terms.

• The equations of state discussed here are applicable to the gas phase of the substances
only, and thus should not be used for liquids or liquid–vapor mixtures.

61
 Applicability Criteria of the Equations of State (EOS)

Figure 28: Complex equations of state represent the P-v-T behavior of gases more accurately over a
wider range.[adapted from Figure 3 – 56, Cengel, 10th Ed.]
62
Mathematical Problem #8

• Example 1 from slides of Dr. Md. Zahurul Haq

Determine the specific volume of water at 20.0 MPa and 520°C using compressibility chart
and property table.

63
References and Resources

1. Thermodynamics – An Engineering Approach, Yunus A. Çengel, Michael A. Boles,

Mehmet Kanoğlu; McGraw Hill, 10th Edition (2023).
2. Slides from Dr. Md. Zahurul Haq, Professor, Department of Mechanical Engineering,
Bangladesh University of Engineering and Technology (BUET)

64