Part 1: Thermodynamics

Unit 3
Properties of pure
substances
Subject: Thermodynamics and Fluid Mechanics
Lecturers: Fernando Cortés, Imanol Sarría, Eduardo
García
Objectives

• Introduce the concept of a pure substance.

• Illustrate the P-v, T-v, and P-T property diagrams and P-v-
T surfaces of pure substances.
• Demonstrate the procedures for determining pure
substances thermodynamic properties of from tables.
• 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.

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Contents

1. Pure substance.
2. Phases of a pure substance.
3. Phase-change of pure substances.
4. Property diagrams for phase-change processes.
5. Property tables.
6. The ideal-gas equation of state.
7. Compressibility factor - a measure of deviation from ideal-
gas behavior.

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1. 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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2. Phases of a pure substance

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3. 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.

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3. Phase-change processes of pure substances

• 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.

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3. Phase-change processes of pure substances

T-v diagram for the heating

process of water at constant
pressure. 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.

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3. Phase-change processes of pure substances

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.

The liquid–vapor saturation curve of a pure

substance (numerical values are for water).

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3. Phase-change processes of pure substances

∙ Saturation pressure Psat: The pressure at

which a pure substance changes phase at a
given temperature.

∙ Latent heat: The amount of energy a-

bsorbed 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.

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3. Phase-change processes of pure substances

∙ 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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3. Phase-change processes of pure substances

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.

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4. 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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4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES

∙ Saturated liquid line

∙ Saturated vapor line
∙ Compressed liquid region
∙ Superheated vapor region
∙ Saturated liquid–vapor mixture region
(wet region)

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 4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES

Critical point: The point at which the

saturated liquid and saturated vapor
states are identical.

At supercritical pressures (P > Pcr), there is

no distinct phase-change (boiling) process.

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 4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES

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4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES

Extending the Diagrams to Include the Solid Phase

For water:

Ttp = 0.01°C
Ptp = 0.6117 kPa

At triple-point pressure and temperature, a

substance exists in three phases in
equilibrium.

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4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES

P – V diagrams

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4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES

Sublimation: Passing from the solid phase directly into the vapor phase.

At low pressures (below the triple-point

value), solids evaporate without melting first
(sublimation).

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4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES
Phase Diagram

P-T diagram of pure substances

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4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES
The P-v-T surfaces present a great deal of information at once, but in a
thermodynamic analysis it is more convenient to work with two-dimensional
diagrams, such as the P-v and T-v diagrams.

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5. 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.

The product pressure 

volume has energy units.

The combination u + Pv is frequently

encountered in the analysis of control volumes.

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5. PROPERTY TABLES
Saturated Liquid and Saturated Vapor States
Table A–4: Saturation properties of water under temperature.
Table A–5: Saturation properties of water under pressure.

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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5. PROPERTY TABLES
Examples: Saturated liquid and saturated vapor states of water on T-v and P-v
diagrams.

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5. PROPERTY TABLES
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.

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5. PROPERTY TABLES

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

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5. PROPERTY TABLES

y v, u, or h

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5. PROPERTY TABLES

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5. PROPERTY TABLES
Examples: Saturated liquid-vapor mixture states on T-v and P-v
diagrams:

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5. PROPERTY TABLES
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.
In this region, temperature and pressure are
independent properties.

At a specified P, superheated vapor exists at a

higher h than the saturated vapor.

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5. PROPERTY TABLES
Compared to saturated vapor, superheated vapor is characterized by:

A partial listing of Table A–6.

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5. PROPERTY TABLES
Compressed Liquid

Compressed liquid is characterized by:

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5. PROPERTY TABLES
The compressed liquid properties depend on temperature much more
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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5. PROPERTY TABLES
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 as a result of the reference state chosen.
• Sometimes different tables list different values for some properties at the same state as a result
of using a different reference state.
• 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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5. PROPERTY TABLES

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6.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

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6.THE IDEAL-GAS EQUATION OF STATE

Different substances have different

gas constants.

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6.THE IDEAL-GAS EQUATION OF STATE

Ideal gas equation at two states for a fixed mass

Mass = Molar mass  Mole number

Various expressions of ideal gas equation

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6.THE IDEAL-GAS EQUATION OF STATE

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.

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6.THE IDEAL-GAS EQUATION OF STATE

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.

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7. COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR

Compressibility factor Z A factor that

accounts for the deviation of real
gases from ideal-gas behavior at a
given temperature and pressure.

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7. COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
The farther away Z is from unity, the more the gas deviates from ideal-gas
behavior.
Gases behave as an ideal gas at low densities (i.e., low pressure, high
temperature).
Question: What is the criteria for low 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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7. COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR

Reduced Reduced
pressure temperature

Pseudo-reduced
specific volume

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7. COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR

Z can also be determined from a

knowledge of PR and vR.

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7. COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
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

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