Applied

Thermodynamics
ChE-251
Lecture-6
Hafiz Mudaser Ahmad
[email protected]
Department of Chemical Engineering
University of Engineering & Technology Lahore

2025-02-27 1
Properties of Pure Substances
 Objectives
• Introduce the concept of a pure substance.
• Discuss the physics of phase-change processes.
• Illustrate the P-v, T-v, and P-T property diagrams and P-v-T
surfaces of pure substances.
• Demonstrate the procedures for determining thermodynamic
properties of pure substances from tables of property data.
• Describe the hypothetical substance “ideal gas” and the ideal-
gas equation of state.
• Apply the ideal-gas equation of state in the solution of typical
problems.
• Introduce the compressibility factor, which accounts for the
deviation of real gases from ideal-gas behavior.
• Present some of the best-known equations of state.
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PURE SUBSTANCE
• Pure substance: A substance that has a fixed chemical
composition throughout.
• Air is a mixture of several gases, but it is considered to be a
pure substance.

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PHASES OF A PURE SUBSTANCE

The molecules
in a solid are
kept at their
positions by the
large springlike
inter-molecular
forces.
In a solid, the
attractive and
repulsive forces
between the
molecules tend
to maintain them
at relatively
constant
distances from
each other.

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PHASE-CHANGE PROCESSES OF PURE SUBSTANCES

• Compressed liquid (subcooled liquid): A substance that it is not

about to vaporize.
• Saturated liquid: A liquid that is about to vaporize.

At 1 atm and 20°C,

water exists in the
liquid phase
(compressed liquid).

At 1 atm pressure
and 100°C, water
exists as a liquid
that is ready to
vaporize (saturated
liquid).
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• Saturated vapor: A vapor that is about to condense.
• Saturated liquid–vapor mixture: The state at which the liquid and vapor
phases coexist in equilibrium.
• Superheated vapor: A vapor that is not about to condense (i.e., not a
saturated vapor).

At 1 atm pressure, the As more heat is

As more heat is transferred, temperature remains constant transferred, the
part of the saturated liquid at 100°C until the last drop of temperature of the
vaporizes (saturated liquid– liquid is vaporized (saturated vapor starts to rise
vapor mixture). vapor). (superheated vapor).
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If the entire process between state 1 and 5 described in the figure 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.

T-v diagram for the

heating process of
water at constant
pressure.
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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.
• Water boils at 100C at 1 atm pressure.
• Saturation temperature Tsat: The temperature at which a pure substance changes
phase at a given pressure.
• Saturation pressure Psat: The pressure at which a pure substance changes phase
at a given temperature.

The liquid–vapor
saturation curve
of a pure
substance
(numerical
values are for
water).
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• Latent heat: The amount of energy absorbed
or released during a phase-change process.
• Latent heat of fusion: The amount of energy
absorbed during melting. It is equivalent to
the amount of energy released during
freezing.
• Latent heat of vaporization: The amount of
energy absorbed during vaporization and it is
equivalent to the energy released during
condensation.
• The magnitudes of the latent heats depend
on the temperature or pressure at which the
phase change occurs.
• At 1 atm pressure, the latent heat of fusion of
water is 333.7 kJ/kg and the latent heat of
vaporization is 2256.5 kJ/kg.
• The atmospheric pressure, and thus the
boiling temperature of water, decreases with
elevation.

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Some Consequences of Tsat and
Psat Dependence
The variation of
the temperature
of fruits and
vegetables with
pressure during
vacuum cooling
from 25°C to 0°C.

In 1775, ice was made by

evacuating the air space
in a water tank. 12
 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 such as the T-v, P-v, and P-T diagrams
for pure substances.

T-v diagram of
constant-pressure
phase-change
processes of a pure
substance at various
pressures (numerical
values are for water).
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• saturated liquid line
• saturated vapor line
• compressed liquid region
• superheated vapor region
• saturated liquid–vapor mixture
region (wet region)

At supercritical
Critical point: The point at
pressures (P > Pcr),
which the saturated liquid
there is no distinct
and saturated vapor states
phase-change (boiling)
are identical.
process. 14
15
Sublimation: Passing Phase Diagram
from the solid phase
directly into the vapor
phase.

At low pressures
(below the triple-point
value), solids evaporate
without melting first
P-T diagram of pure substances.
(sublimation).

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 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.
• Some thermodynamic properties can be measured easily, but others cannot and are
calculated by using the relations between them and measurable properties.
• The results of these measurements and calculations are presented in tables in a
convenient format.

Enthalpy—A Combination Property

The
combination
u + Pv is
frequently
encountered in
the analysis of The product pressure 
control volume has energy units.
volumes. 17
 Saturated Liquid and Saturated Vapor States
• Table A–4: Saturation properties of water under temperature.
• Table A–5: Saturation properties of water under pressure.

A partial list of Table A–4.

Enthalpy of vaporization, hfg (Latent

heat of vaporization): The amount of
energy needed to vaporize a unit mass of
saturated liquid at a given temperature
or pressure.

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Example 1

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Example 2

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Example 3

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Saturated Liquid–Vapor Mixture
Quality, x : The ratio of the mass of vapor to the total mass of the mixture. Quality
is between 0 and 1 0: sat. liquid, 1: sat. vapor.
The properties of the saturated liquid are the same whether it exists alone or in a
mixture with saturated vapor.
Temperature and
pressure are dependent
properties for a mixture.

The relative
amounts of
liquid and
vapor phases
in a saturated
mixture are A two-phase system can be
specified by treated as a homogeneous
the quality x. mixture for convenience.
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y v, u, or h.

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Example 4

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Example 5

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In the region to the right of the Superheated Vapor
saturated vapor line and at
temperatures above the critical Compared to saturated vapor,
point temperature, a substance superheated vapor is characterized by
exists as superheated vapor.
In this region, temperature and
pressure are independent
properties.

At a specified
P, superheated
vapor exists at
a higher h than
the saturated
vapor.

A partial
listing of
Table A–6. 39
Example 6

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Example 7

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The compressed liquid properties Compressed Liquid
depend on temperature much more Compressed liquid is characterized by
strongly than they do on pressure.

y → v, u, or h

A more accurate relation for h

A compressed liquid may

be approximated as a
saturated liquid at the
given temperature.

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Example 8

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 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 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.
• The reference state for water is 0.01°C and for R-134a is -40°C in tables.
• Some properties may have negative values because of the reference state
chosen.
• However, In thermodynamics we are concerned with the changes in properties,
and the reference state chosen is of no consequence in calculations.

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THE IDEAL-GAS EQUATION OF STATE
• Equation of state: Any equation that relates the pressure, temperature, and
specific volume of a substance.
• 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.

Ideal gas equation

of state

R: gas constant
M: molar mass (kg/kmol)
Ru: universal gas constant

Different substances have different

gas constants.
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Mass = Molar mass  Mole number Ideal gas equation at two
states for a fixed mass

Various expressions of
ideal gas equation

Real gases behave as an ideal gas at low densities

(i.e., low pressure, high temperature).

Properties per unit mole are

denoted with a bar on the top. 52
Is Water Vapor an Ideal Gas?
• 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.
• In air-conditioning applications, the
water vapor in the air can be treated
as an ideal gas. Why?
• In steam power plant applications,
however, the pressures involved are
usually very high; therefore, ideal-gas
relations should not be used.

Percentage of error ([|vtable - videal|/vtable] 100) involved in assuming

steam to be an ideal gas, and the region where steam can be
treated as an ideal gas with less than 1 percent error. 53
COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
Compressibility factor Z A The farther away Z is from unity, the more the gas
factor that accounts for the deviates from ideal-gas behavior.
deviation of real gases from Gases behave as an ideal gas at low densities (i.e.,
ideal-gas behavior at a low pressure, high temperature).
given temperature and Question: What is the criteria for low pressure
pressure. and high temperature?
Answer: The pressure or temperature of a gas is
high or low relative to its critical temperature or
pressure.

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 Reduced Reduced
pressure temperature
Pseudo-reduced Z can also be determined from a
specific volume knowledge of PR and vR.

Comparison of Z factors for various gases. 55

OTHER EQUATIONS OF
STATE
Several equations have been proposed to
represent the P-v-T behavior of substances
accurately over a larger region with no
limitations.

Van der Waals

Equation of State Critical
isotherm of a
pure substance
has an inflection
point at the
critical state.

This model includes two effects not considered in

the ideal-gas model: the intermolecular attraction
forces and the volume occupied by the molecules
themselves. The accuracy of the van der Waals
equation of state is often inadequate. 56
Beattie-Bridgeman Equation of State

The constants are given in

Table 3–4 for various
substances. It is known to be
reasonably accurate for
densities up to about 0.8cr.

Benedict-Webb-Rubin Equation of State

The constants are given in Table 3–4. This equation can handle substances at
densities up to about 2.5 cr.

Virial Equation of State

The coefficients a(T), b(T), c(T), and so on, that are functions
of temperature alone are called virial coefficients.
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 Complex equations of
state represent the P-v-T
behavior of gases more
accurately over a wider
Percentage of error involved in various equations of range.
state for nitrogen
(% error = [(|vtable - vequation|)/vtable] 100).
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Summary
• Pure substance
• Phases of a pure substance
• Phase-change processes of pure substances
• Compressed liquid, Saturated liquid, Saturated vapor, Superheated vapor
• Saturation temperature and Saturation pressure
• Property diagrams for phase change processes
• The T-v diagram, The P-v diagram, The P-T diagram, The P-v-T surface
• Property tables
• Enthalpy
• Saturated liquid, saturated vapor, Saturated liquid vapor mixture, Superheated vapor,
compressed liquid
• Reference state and reference values
• The ideal gas equation of state
• Is water vapor an ideal gas?
• Compressibility factor
• Other equations of state
• van der Waals Equation of State, Beattie-Bridgeman Equation of State
• Benedict-Webb-Rubin Equation of State, Virial Equation of State

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Example 9

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Example 10

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Example 11

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Example 12

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Example 13

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