Chapter - 2

Thermodynamic Properties of Pure substance

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Learning objectives
• By the end of this chapter you will be able to:
• Define pure substance and phase of a pure substance.
• Explain phase change process using property diagrams.
• Use steam table to get property values at different regions of phase change
process.
• Differentiate ideal gases from real gases.
• Used ideal gas equation of state to determine unknown properties.
• Explain the advantages and disadvantages of ideal gas equation of state and
other equations of states.

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What is pure substance?
• A substance that has a fixed chemical composition throughout is
called a pure substance.
• Chemical elements and compounds are pure substances.
• A mixture of various chemical elements or compounds also qualifies as a pure
substance as long as the mixture is homogeneous.
• 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 liquid and gaseous water is a

pure substance, but a mixture of liquid and
gaseous air is not.
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Phases of a pure substance
• A phase is identified as having a distinct molecular arrangement
that is homogeneous throughout and separated from the others by
easily identifiable boundary surfaces.
• The two phases of H2O in iced water represent a good example of this.
• There are three principal phases; solid, liquid, and gas.
• A substance may have several phases within a principal phase, each
with a different molecular structure.
• For example, Carbon, may exist as graphite or diamond in the solid phase.
• Helium has two liquid phases.
• Iron has three solid phases.
• Ice may exist at seven different phases at high pressures.

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 Phase of a pure substance

Solids Liquids Gases

• Strong intermolecular bonds • weakest intermolecular

• Molecules closely packed and • groups of molecules forces
arranged in a lattice. move about each other. • No molecular order exist.
• Molecules oscillate about • Intermolecular forces are • Collusion is the only mode of
equilibrium position. weaker than solids but interaction.
• Oscillation velocity increase stronger than gases. • Are relatively at higher
with temperature. energy level.

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Phase change process
• 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.
• As a familiar substance, water is used to demonstrate the basic
principles involved.
• Remember, however, that all pure substances exhibit the same
general behavior.

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 Phase change process
Compressed liquid / Subcooled liquid

1 • Water exist in liquid form and

when a slight amount of heat is
added, the water wont vaporise.
• As the temperature rises, the
liquid water expands slightly, and
so its specific volume increases.
• As more heat is transferred, the
temperature keeps rising until it
reaches 100°C
At 1 atm and 20°C, water exists
in the liquid phase (compressed
liquid) 7
 Phase change process
Saturated Liquid

2 • At this point 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.

At 1 atm pressure and 100°C, water

exists as a liquid that is ready to
vaporize (saturated liquid). 8
 Phase change process
Saturated Liquid-Vapor mixture

3 • Once boiling starts, the

temperature stops rising until the
liquid is completely vaporized.
• 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.
As more heat is transferred, part of
the saturated liquid vaporizes
(saturated liquid–vapor mixture) 9
 Phase change process
Saturated Vapor

4 • At this point all the liquid is

converted in to vapor at
atmospheric pressure and 100°C.
• If a slight heat is lost then the
vapor will start condensing.
• A vapor that is about to
condense is called a saturated
vapor.

At 1 atm pressure, the temperature

remains constant at 100°C until the last
drop of liquid is vaporized (saturated vapor) 10
 Phase change process
Superheated Vapor

5 • 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.
• A vapor that is not about to
condense (i.e., not a saturated
vapor) is called a superheated
vapor.
As more heat is transferred, the
temperature of the vapor starts to
rise (superheated vapor) 11
Fig. T-v diagram of a constant pressure heating process of water
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latent heat
• It is the amount of energy absorbed or released during a phase-
change process.
• latent heat of fusion: energy absorbed during melting / energy
released during freezing.
• latent heat of vaporization: energy absorbed during vaporization
/energy released during condensation.
• The magnitudes of the latent heats depend on the temperature or
pressure at which the phase change occurs.

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Saturation temperature and saturation
pressure
• 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.
• at a given temperature, the pressure at which a pure substance
changes phase is called the saturation pressure Psat.

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Saturation temperature and saturation
pressure
• Tsat increases with Psat. Thus, a substance at
higher pressures boils at higher temperatures.

The liquid–vapor saturation curve of a pure substance

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Consequences of Tsat and Psat Dependence
• It allows us to control the boiling temperature of a substance by
simply controlling the pressure. Example;

• In science studies such as superconductivity

and cryogenic application.
• The boiling temperature of nitrogen at
atmospheric pressure is −196°C
• 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.
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Consequences of Tsat and Psat Dependence
• vacuum cooling

• Based on reducing the pressure of the

sealed cooling chamber to the
saturation pressure at the desired low
temperature and evaporating some
water from the products to be cooled.
• Its expensive and fast cooling which is
more desirable for products with
larger surface area to mass ratio like
lettuce and spinach.
Vacuum freezing 17
Property diagrams for phase-change
processes
• The variations of properties during phase-change processes are best
studied and understood with the help of property diagrams.
The T-v Diagram
• Adding weight on top of the piston
rises the pressure which is
accompanied by :
• State 1: smaller specific volume
• State 2: elevated saturation
temperature and increased
specific volume
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The T-v Diagram
• State 3: shorter line connecting the saturated states.
• State 4: lesser specific volume.
• State 5: lesser specific volume for the same temperature value.
• As we keep increasing the pressure the line connecting the saturated
liquid and saturated vapor shorten and become a point; which is
called critical point.
• At critical point the saturated liquid and saturated vapor are identical.
• At critical point we have critical properties; such as critical pressure,
critical temperature, critical specific volume etc…

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The T-v Diagram
• At supercritical pressures (P > Pcr), there is
no distinct phase-change (boiling) process.
• there is no line that separates the compressed
liquid region and the superheated vapor region.
• Its considered as superheated vapor at
temperatures above critical temperature and
compressed liquid at temperatures lower than
critical temperature.
• A saturation dome is formed connecting all
the saturated liquid and saturated vapor
points .
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The T-v Diagram

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The P-v Diagram
• Its much like that of T-v diagram except the constant
temperature line has a downward trend.
• Consider a compressed liquid at 1 MPa and 150℃.
• As mass is removed gradually the pressure reduced.
• To keep the temperature constant, the water exchange
heat with the environment.
• When the pressure reaches 0.4762MPa, the water starts
vaporizing. At this point we stop removing weight.
• During vaporization both pressure and temperature are
constant.
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The P-v Diagram

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The P-v Diagram
• It can be extended to include the solid phase.
• 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.
• 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 and, therefore, is often
called the triple point.
• For water, the triple-point temperature and pressure are 0.01°C and 0.6117
kPa, respectively.

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The P-v Diagram

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The P-v Diagram
• At triple point all the three phases coexist in equilibrium.
• No substance can exist in the liquid phase in stable equilibrium at
• 𝑃 < 𝑃𝑡𝑝 for all substances and
• 𝑇 < 𝑇𝑡𝑝 for substance that contract during freeing.
• substances at high pressures can exist in the liquid phase at
temperatures below the triple-point temperature.
• 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.
• Passing from the solid phase directly into the vapor phase is called
sublimation.
• occurs at pressures below the triple point value, since a pure substance cannot
exist in the liquid phase at those pressures.

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The P-T Diagram
• This diagram is often called the phase diagram since all three phases
are separated from each other by three lines.
• The sublimation line separates the solid and vapor regions.
• The vaporization line separates the liquid and vapor regions and
• The melting (or fusion) line separates the solid and liquid regions.
• These three lines meet at the triple point, where all three phases coexist in
equilibrium.
• 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.

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The P-v-T Surface
• we can represent the P-v-T behavior of a substance as a surface in
space.
• Here T and v may be viewed as the independent variables (the base)
and P as the dependent variable (the height).
• All the points on the surface represent equilibrium states. All states
along the path of a quasi-equilibrium process lie on the P-v-T surface
since such a process must pass through equilibrium states.
• All the two-dimensional diagrams we have discussed so far are merely
projections of this three-dimensional surface onto the appropriate
planes
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P-v-T surface of a substance that P-v-T surface of a substance that
contracts on freezing. expands on freezing (like water).

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Property tables
• the relationships among thermodynamic properties are too complex
to be expressed by simple equations.
• Some properties can be measured and others can be calculated and
found by some relations.
• The results of these measurements and calculations are presented in
tables in a convenient format.
• the steam tables are used to demonstrate the use of thermodynamic
property tables.
• Before we get into the discussion of property tables, we define a new
property called enthalpy.

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Enthalpy
• It’s a combination property, most often in
analysis of certain types of process (in power
generation and refrigeration) we encounter
with internal energy (u) and Pv.
• Grouping them simplifies the equation and the
summation of the two is called enthalpy (h).
ℎ = 𝑢 + 𝑃𝑣 (kJ/kg)

H = 𝑈 + 𝑃𝑉 (kJ)

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Saturated Liquid and Saturated Vapor States
• The subscript f is used to denote
properties of a saturated liquid and the
subscript g to denote the properties of
saturated vapor.
• The subscript commonly used is fg, which
denotes the difference between the
saturated vapor and saturated liquid
values of the same property.
• 𝑣𝑓 = specific volume of saturated liquid
• 𝑣𝑔 = specific volume of saturated vapor
• 𝑣𝑓𝑔 = 𝑣𝑔 − 𝑣𝑓
• ℎ𝑓𝑔 represent the enthalpy of
vaporization / latent heat of vaporization 33
Saturated Liquid and Saturated Vapor States
• Examples
1. 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.
2. 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.

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Saturated Liquid–Vapor Mixture
• 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= where; 𝑚𝑡𝑜𝑡𝑎𝑙 = 𝑚𝑣𝑎𝑝𝑜𝑟 + 𝑚𝑙𝑖𝑞𝑢𝑖𝑑
𝑚𝑡𝑜𝑡𝑎𝑙
• Quality has significance for saturated mixtures only.
• Its value is between 0 (saturated liquid) and 1 (saturated vapor).
• A saturated mixture can be treated as a combination of two
subsystems.

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Saturated Liquid–Vapor Mixture
• 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:

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Saturated Liquid–Vapor Mixture
• For others also

More generally
Where y can be; u , h, or v

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Saturated Liquid–Vapor Mixture
• Example:
1. A rigid tank contains 10 kg of water at 90°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.
2. A 0.08 m3 vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa.
Determine (a) the temperature, (b) the quality, (c) the enthalpy of the
refrigerant, and (d) the volume occupied by the vapor phase.

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Superheated Vapor
• We have superheated region to the right side of saturated vapor line
and also above critical temperature.
• Since we have single phase temperature and pressure are
independent.
• Compered to saturated vapor, this region is characterised by:
• Lower pressures (P < Psat at a given T )
• Higher temperatures (T > Tsat at a given P)
• Higher specific volumes (v > vg at a given P or T)
• Higher internal energies (u > ug at a given P or T )
• Higher enthalpies (h > hg at a given P or T)

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Superheated Vapor
• Example :
1. Determine the temperature of water at a state of P = 0.5 MPa and h
= 2890 kJ/kg.

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Compressed Liquid
• Compressed liquid tables are not as commonly available.
• They are very much like the format of the superheated vapor tables.
• Variation of properties of compressed liquid with pressure is very
mild.
• In the absence of compressed liquid data, a general approximation is
to treat compressed liquid as saturated liquid at the given
temperature.
• 𝑦 ≅ 𝑦𝑓@𝑇 where y is v, h, u
• Form the three; v, u and h, enthalpy (h) is sensitive to pressure
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Compressed Liquid
• Instead of taking hf for low to moderate pressures and temperatures,
• ℎ ≅ ℎ𝑓@𝑇 + 𝑣@𝑇 𝑃 − 𝑃𝑠𝑎𝑡@𝑇
• In general, a compressed liquid is characterized by;
• Higher pressures (P > Psat at a given T )
• Lower temperatures (T < Tsat at a given P)
• Lower specific volumes (v < vf at a given P or T)
• Lower internal energies (u < uf at a given P or T )
• Lower enthalpies (h < hf at a given P or T )

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Compressed Liquid
• Example:
1. 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?

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Reference state and reference values
• The properties u, h and s can not be measured directly and obtained
by property relations.
• But the property relations give the change in properties (u, h and s)
not their values at a point.
• 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 example for water the state of saturated liquid at 0.01℃ is taken as
reference state and at this state (𝑢 = ℎ = 𝑠 = 0)
• For refrigerant 134a the reference state is saturated liquid at −40℃.
• some properties may have negative values as a result of the reference state
chosen.

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Example

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The ideal gas equation of state
• Property tables give accurate information about properties of a
system but they are bulky and prone to typographic error.
• It is desirable to have some relation among properties which is
general and accurate.
• Any equation that relates the pressure, temperature, and specific
volume of a substance is called an equation 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.

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The ideal gas equation of state
• The ideal gas equation of state is given by;
𝑃𝑣 = 𝑅𝑇
• Where : P is the absolute pressure in (KPa)
• v is the specific volume in (m3/kg)
• T is absolute temperature in (K)
• R is a gas constant in (kJ/kg.K)
• R is different for different gases and its obtained by:
𝑅𝑢
𝑅=
𝑀
Where Ru is the universal gas constant and M is the molar mass

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The ideal gas equation of state
• molar mass M can simply be defined as the mass of one mole.
• For example; when we say the molar mass of nitrogen is 28, it simply means
the mass of 1 kmol of nitrogen is 28 kg; or 1gmol of nitrogen is 28 g.
• The mass of a system is equal to the product of its molar mass M and
the mole number N;
• 𝑚 = 𝑁𝑀 (Kg)
• The ideal-gas equation of state can be written in several different
forms:
• 𝑃𝑉 = 𝑚𝑅𝑇
• 𝑃𝑉 = 𝑁𝑅𝑢 𝑇
• 𝑃𝑣ҧ = 𝑅𝑢 𝑇

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The ideal gas equation of state
• For a fixed mass writing the ideal gas equation twice at two states :
𝑃1 𝑉1 𝑃2 𝑉2
• =
𝑇1 𝑇2
• An ideal gas is an imaginary substance that obeys the ideal gas
relation.
• Real gases behave as ideal gas at lower density, i.e at lower pressure
and higher temperature.
• Dense gases such as water vapor in steam power plants and
refrigerant vapor in refrigerators, however, should not be treated as
ideal gases, instead property tables are used.
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At lower pressures below 10 kPa water
vapour can be treated as an ideal gas
regardless of temperature with
negligible error.

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The ideal gas equation of state
• Example:
1. The gage pressure of an automobile tire is measured to be 210 kPa
before a trip and 220 kPa after the trip at a location where the
atmospheric pressure is 95 kPa. Assuming the volume of the tire
remains constant and the air temperature before the trip is 25°C,
determine air temperature in the tire after the trip.

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Compressibility factor Z
• 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.
𝑃𝑣
• 𝑍= ------------------------ 𝑃𝑣 = 𝑍𝑅𝑇
𝑅𝑇
• It can be also expressed as
𝑣 𝑅𝑇
• 𝑍 = 𝑎𝑐𝑡𝑢𝑎𝑙 ; where is ; 𝑣𝑖𝑑𝑒𝑎𝑙 =
𝑣𝑖𝑑𝑒𝑎𝑙 𝑃

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Compressibility factor Z
• Gases behave very much the same at temperatures and pressures
normalized with respect to their critical temperatures and pressures
called reduced temperature and reduced pressure respectively.
𝑇
• Reduced temperature : 𝑇𝑅 =
𝑇𝑐𝑟
𝑃
• Reduced pressure: 𝑃𝑅 =
𝑃𝑐𝑟

• 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.

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54
Compressibility factor Z
• 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.

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Compressibility factor Z
• When T and v or P and v are given instead of T and P the generalized
compressibility chart can still be used to determine the third property
(pseudo-reduced specific volume vR)
𝑣𝑎𝑐𝑡𝑢𝑎𝑙
• 𝑣𝑅 = 𝑅𝑇𝑐𝑟
ൗ𝑃𝑐𝑟

• Lines of constant vR are also added to the compressibility charts, and

this enables one to determine T or P.

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57
58
• Example:
1. Determine the specific volume of refrigerant-134a at 1 MPa and
50°C, using (a) the ideal-gas equation of state and (b) the
generalized compressibility chart. Compare the values obtained to
the actual value of 0.021796 m3/kg and determine the error
involved in each case.

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Other Equations of State
• Ideal gas equation of state is simple but with limited rage of
application.
• 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 has been
proposed.

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van der Waals Equation of State
• Van der Waals equation improves the ideal gas equation by
considering the effects of intermolecular attraction forces and volume
occupied by the molecules themselves.
𝑎
• 𝑃+ 𝑣 − 𝑏 = 𝑅𝑇
𝑣2
• The two constants a and b are determined at critical point of the substance,
𝑎
where the intermolecular force is accounted by the term 2 and that of
𝑣
volume occupied by molecules by 𝑏
• As the pressure increases, the volume occupied by the molecules becomes an
increasingly significant part of the total volume

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van der Waals Equation of State
• The two constants are determined from the critical isotherm line;
which is horizontal at critical point, so

• Performing the differentiation and eliminating 𝑣𝑐𝑟

• Its desirable to express the constants a and b over wide range

instead of single point.

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Beattie-Bridgeman Equation of State
• equation of state based on five experimentally determined constants.
It is expressed as

• Where

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

densities up to about 0.8ρcr.
• The constants appearing in this equation are given in Table 3–4 for various
substances.

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Beattie-Bridgeman Equation of State

64
Benedict-Webb-Rubin Equation of State
• Extended version of Beattie-Bridgeman, have 8 constants.

• The values of the constants appearing in this equation are given in

Table 3–4.
• This equation can handle substances at densities up to about 2.5ρcr.

65
Virial Equation of State
• The equation of state of a substance can also be expressed in a series
form

• coefficients a(T), b(T), c(T), and so on, that are functions of temperature alone
are called virial coefficients.
• These coefficients can be determined experimentally or theoretically from
statistical mechanics.
• As pressure approaches zero, all the viral coefficients vanish and we remain
with the ideal gas equation.

66
• van der Waals: 2 constants. Accurate over a limited range.
• Beattie-Bridgeman: 5 constants. Accurate for ρ ≤ 0.8ρcr
• Benedict-Webb-Rubin: 8 constants. Accurate for ρ ≤ 2.5ρcr
• Strobridge: 16 constants. More suitable for computer calculations.
• Virial: may vary. Accuracy depends on the number of terms used.

67
• Example:
1. Predict the pressure of nitrogen gas at T = 175 K and v = 0.00375 m3 /kg
on the basis of (a) the ideal-gas equation of state, (b) the van der Waals
equation of state, (c) the Beattie-Bridgeman equation of state, and (d)
the Benedict-Webb-Rubin equation of state. Compare the values
obtained to the experimentally determined value of 10,000 kPa.

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