Chapter 3

Properties of Pure Substances

and Phase Change
 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.
• 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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 3–1 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.

Nitrogen and gaseous air are pure A mixture of liquid and gaseous water
substances. is a pure substance, but a mixture of
liquid and gaseous air is not.

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 3–2 Phases of a Pure Substance

The arrangement of atoms in different phases:

(a) molecules are at relatively fixed positions in a solid
(b) groups of molecules move about each other in the
liquid phase
(c) molecules move about at random in the gas phase..

The molecules in a solid are kept at

their positions by the large
springlike inter-molecular forces.

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 3–3 Phase-Change Processes of Pure
Substances 1

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

to vaporize

At 1 atm and 20°C, water exists in the

liquid phase (compressed liquid).

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 3–3 Phase-Change Processes of Pure
Substances 2

Saturated liquid: A liquid that is about to vaporize

At 1 atm pressure and 100°C, water exists

as a liquid that is ready to vaporize
(saturated liquid).

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 3–3 Phase-Change Processes of Pure
Substances 3

Saturated liquid–vapor mixture: The state at which the liquid and

vapor phases coexist in equilibrium.

As more heat is transferred, part of the

saturated liquid vaporizes (saturated
liquid–vapor mixture).

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 3–3 Phase-Change Processes of Pure
Substances 4

Saturated vapor: A vapor that is about to condense.

At 1 atm pressure, the temperature

remains constant at 100°C until the last
drop of liquid is vaporized (saturated
vapor).

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 3–3 Phase-Change Processes of Pure
Substances 5

Superheated vapor: A vapor that is not about to condense (that is not

a saturated vapor).

As more heat is transferred, the temperature of

the vapor starts to rise (superheated vapor).

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 3–3 Phase-Change Processes of Pure
Substances 6

T-v diagram for the heating process of water at constant pressure.

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 3–3 Phase-Change Processes of Pure
Substances 7

Saturation Temperature The liquid–vapor saturation curve of

a pure substance (numerical values
and Saturation Pressure are for water).
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.

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 3–3 Phase-Change Processes of Pure
Substances 8

Temperature T, °C Saturation pressure Psat, kPa

–10 0.260
–5 0.403
0 0.611
5 0.872
10 1.23
15 1.71
20 2.34
25 3.17
30 4.25
40 7.38
50 12.35
100 101.3 (1 atm)
150 475.8
200 1554
250 3973
300 8581

Saturation (or vapor) pressure of water at various temperatures

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 3–3 Phase-Change Processes of Pure
Substances 9

Latent heat: The amount of energy absorbed or Variation of the standard atmospheric
released during a phase-change process. pressure and the boiling (saturation)
Latent heat of fusion: The amount of energy temperature of water with altitude
absorbed during melting. It is equivalent to the
amount of energy released during freezing.
Elevation, Atmospheri Boiling
Latent heat of vaporization: The amount of m c pressure, temperature,
energy absorbed during vaporization and it is kPa °C
equivalent to the energy released during 0 101.33 100.0
condensation.The magnitudes of the latent heats
1,000 89.55 96.5
depend on the temperature or pressure at which
the phase change occurs. 2,000 79.50 93.3

At 1 atm pressure, the latent heat of fusion of 5,000 54.05 83.3

water is 334 kJ/kg and the latent heat of 10,000 26.50 66.3
vaporization is 2257 kJ/kg.
20,000 5.53 34.7
The atmospheric pressure, and thus the boiling
temperature of water, decreases with elevation.

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 3–3 Phase-Change Processes of Pure
Substances 10

Some Consequences of Tsat and Psat Dependence

The temperature of liquid nitrogen exposed to the atmosphere remains constant at

−196°C, and thus it maintains the test chamber at −196°C.

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 3–4 Property Diagrams for Phase-
Change Processes 1

T-v diagram of constant-pressure phase-change processes of a pure substance

at various pressures (numerical values are for water).

Critical point: The point at which the saturated liquid and saturated vapor states are identical.
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 3–4 Property Diagrams for Phase-
Change Processes 1

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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 3–4 Property Diagrams for Phase-
Change Processes 3

Property diagrams of a pure substance.

Saturated liquid line

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

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 3–4 Property Diagrams for Phase-
Change Processes 4

Property diagrams of a pure substance. The pressure in a piston–cylinder

device can be reduced by reducing the
weight of the piston.

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 3–4 Property Diagrams for Phase-
Change Processes 5

Extending the Diagrams to Include the Solid Phase

P-v diagrams of different substances.

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 3–4 Property Diagrams for Phase-
Change Processes 6

At triple-point pressure and temperature, a substance exists in three phases in

equilibrium.

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 3–4 Property Diagrams for Phase-
Change Processes 6

At triple-point pressure and temperature, a substance exists in three phases in

equilibrium.

For water,
Ttp = 0.01°C
Ptp = 0.6117 kPa
P-T diagram of pure substances.
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 3–4 Property Diagrams for Phase-
Change Processes 9

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.

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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 3–5 Property Tables 1

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.

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 3–5 Property Tables 3

Saturated Liquid and Saturated Vapor States

vf = specific volume of saturated liquid

vg = specific volume of saturated vapour
vfg = difference between vg and vf (that is
vfg = vg − vf )

Table A–4: Saturation properties of

water under temperature.
Table A–5: Saturation properties of
water under pressure.

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 3–5 Property Tables 2

Enthalpy—A Combination Property

h = u + Pv (kJ/kg)
H = U + PV ( kJ )

The combination u + Pv is often encountered in the analysis of control volumes.

Enthalpy of vaporization, (Latent heat of vaporization) hfg

The amount of energy needed to vaporize a unit mass of saturated liquid at a

given temperature or pressure.

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 3–5 Property Tables 5

Example:
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.

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 3–5 Property Tables 5

Example:
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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 3–5 Property Tables 6

Saturated Liquid–Vapor The relative amounts of liquid and

vapor phases in a saturated mixture
Mixture are specified by the quality x.
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.
mvapor
x=
mtotal
mtotal = mliquid + mvapor = m f + mg
Temperature and pressure are
dependent properties for a mixture.
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 3–5 Property Tables 8

Quality is related to the horizontal

distances on P-v and T-v diagrams.

𝑦avg = 𝑦𝑓 + 𝑥𝑦𝑓𝑔 , 𝑦 → 𝑣, 𝑢, or ℎ

y f  yavg  y g

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 3–5 Property Tables 5

Example:
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

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 3–5 Property Tables 5

Example:
An 80-L 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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 3–5 Property Tables 11

Superheated Vapor
Compared to saturated vapor, superheated vapor is characterized 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)

At a specified P, superheated vapor exists at a

higher h than the saturated vapor Example 3–7).

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 3–5 Property Tables 12

A partial listing of Table A–6.

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 3–5 Property Tables 13

Compressed liquid is characterized by

Compressed Liquid
Higher pressures (P > Psat at a given T)
The compressed liquid properties Lower temperatures (T < Tsat at a given P)
depend on temperature much Lower specific volumes (v < vf at a given P or T)
more strongly than they do on Lower internal energies (u < uf at a given P or T)
pressure. Lower enthalpies (h < hf at a given P or T)
y  y f @T y → v, u , or h
Schematic and T-u diagram for Example 3–8.

A more accurate relation for h

h  h f @ T + v f @ T ( P − Psat @ T )
(at low Temp. and Pressure)

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 3–5 Property Tables 14

A compressed liquid may be At a given P and T, a pure

approximated as a saturated liquid substance will exist as a
at the given temperature. compressed liquid if T < Tsat @ P.

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 3–5 Property Tables 5

Example:
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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 3–5 Property Tables 16

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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 3–6 The Ideal-Gas Equation of State 1

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.
T 
P = R 
v 
Pv = RT Ideal gas equation of state

R 8.31447 kJ/kmol  K
R = u (kJ / kg  K or kPa  m3/kg  K) 
M  8.31447 kPa  m 3
/kmol  K
0.0831447 bar  m3 /kmol  K
R: gas constant Ru = 
1.98588 Btu/lbmol  R
M: molar mass (kg/kmol) 10.7316 psia  ft 3 /lbmol  R

Ru: universal gas constant 1545.37 ft  lbf/lbmol  R
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 3–6 The Ideal-Gas Equation of State 2

Different substances have different gas constants.

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 3–6 The Ideal-Gas Equation of State 3

Mass = Molar mass  Mole number

m = MN (kg) Properties per unit mole are
denoted with a bar on the top.
Various expressions of ideal gas
equation
V = mv → PV = mRT
mR = ( MN ) R = NRu → PV = NRuT
V = N v → Pv = RuT

P1V1 P2V2 Ideal gas equation at two

=
T1 T2 states for a fixed mass

Real gases behave as an ideal gas

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

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 3–6 The Ideal-Gas Equation of State 4

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, 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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 3–6 The Ideal-Gas Equation of State 5

  v table − videal  

Percentage of error     100  involved in assuming steam to be an ideal gas, and
 v table  
the region where steam can be treated as an ideal gas with less than 1 percent error.

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 3–7 Compressibility Factor—a Measure
of Deviation from Ideal-Gas Behavior 1

Compressibility factor Z: A factor that accounts for the deviation of real

gases from ideal-gas behavior at a given temperature and pressure.

Pv
Z=
RT The compressibility factor is unity for ideal gases.
RT
videal = .
Pv = ZRT P

Z = 1 for ideal gases

v
Z = actual
videal

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 3–7 Compressibility Factor—a Measure
of Deviation from Ideal-Gas Behavior 2

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 (that is 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.

At very low pressures, all gases approach ideal-gas behavior (regardless of their
temperature).

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 3–7 Compressibility Factor—a Measure
of Deviation from Ideal-Gas Behavior 3

P Reduce T Reduced v actual Pseudo-reduced

PR = TR = v R =
Pcr pressure temperature RTcr / Pcr specific volume
Tcr
Comparison of Z factors for various gases.

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 3–7 Compressibility Factor—a Measure
of Deviation from Ideal-Gas Behavior 3

Gases deviate from the ideal-gas behavior the

most in the neighborhood of the critical point.
• 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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 3–5 Property Tables 5

Example:
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.

(Appendix A-15)

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 3–8 Other Equations Of State 1

The ideal-gas equation of state is very Several equations of state have

simple, but its range of applicability is been proposed throughout
limited. history.
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.

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 3–8 Other Equations Of State 7

Percentage of error involved in various • Complex equations represent the behavior

equations of state for nitrogen of substances reasonably well and are very
suitable for digital computer applications.

• For hand calculations, however, it is

suggested that the reader use the property
tables or the simpler equations of state for
convenience

  v table − v equation  
 % error =   100  .
  v table  
 

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 Summary

• Pure substance.
• Phases of a pure substance.
• Phase-change processes of pure substances.
• Property diagrams for phase change processes.
• Property tables.
• The ideal gas equation of state.
• Compressibility factor.
• Other equations of state.

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 End of Chapter 3

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