Chapter 3

Properties of Pure
Substances

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 • 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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 • 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.

Figure 3–1 Figure 3–2

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

Figure 3–3 Figure 3–4

The molecules in a solid The arrangement of atoms in different phases:
are kept at their positions (a) molecules are at relatively fixed positions in
by the large springlike a solid, (b) groups of molecules move about each
inter-molecular forces. other in the liquid phase, and (c) molecules move
about at random in the gas phase..

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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
Figure 3–5
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

Figure 3–6
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.

Figure 3–7
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.

Figure 3–8
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).
Figure 3–9
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

If the entire process between state 1 and 5 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.

Figure 3–10
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 Figure 3–11

The liquid–vapor saturation curve of
and Saturation Pressure a pure substance (numerical values
The temperature at which water starts are for water).
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

Table 3–1: Saturation (or vapor) pressure of water at various temperatures

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

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 • 3–3 Phase-Change Processes of Pure
Substances 9

Latent heat: The amount of energy absorbed or Table 3–2: Variation of the standard
released during a phase-change process. atmospheric pressure and the boiling
Latent heat of fusion: The amount of energy (saturation) temperature of water with
absorbed during melting. It is equivalent to the altitude
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 2,000 79.50 93.3
the phase change occurs.
5,000 54.05 83.3
At 1 atm pressure, the latent heat of fusion of 10,000 26.50 66.3
water is 334 kJ/kg and the latent heat of
20,000 5.53 34.7
vaporization is 2257 kJ/kg.
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

Figure 3–12
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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 • 3–3 Phase-Change Processes of Pure
Substances 11

Figure 3–13
The variation of the temperature of fruits and vegetables with pressure during vacuum
cooling from 25°C to 0°C.

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 • 3–3 Phase-Change Processes of Pure
Substances 12

Figure 3–14
In 1775, ice was made by evacuating the airspace in a water tank.

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 • 3–4 Property Diagrams for Phase-
Change Processes 1

The variations of properties Figure 3–15

during phase-change processes T-v diagram of constant-pressure phase-
are best studied and understood change processes of a pure substance at
various pressures (numerical values are
with the help of property
for water).
diagrams such as the T-v, P-v,
and P-T diagrams for pure
v
substances.

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 • 3–4 Property Diagrams for Phase-
Change Processes 2

Critical point: The point at Figure 3–16

which the saturated liquid At supercritical pressures (P > Pcr), there is
and saturated vapor states no distinct phase-change (boiling) process.
are identical.

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 • 3–4 Property Diagrams for Phase-
Change Processes 3

Figure 3–17
Saturated liquid line
Property diagrams of a pure substance.
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

Figure 3–17 Figure 3–18

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

Figure 3–19
P-v diagrams of different substances.

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 • 3–4 Property Diagrams for Phase-
Change Processes 6

Figure 3–20
At triple-point pressure and temperature, a substance exists in three phases in
equilibrium.

For water,
Ttp = 0.01°C
Ptp = 0.6117 kPa

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 • 3–4 Property Diagrams for Phase-
Change Processes 7

Sublimation: Passing from the solid phase directly into the vapor phase.
Figure 3–21
At low pressures (below the triple-point value), solids evaporate without melting first
(sublimation).

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 • 3–4 Property Diagrams for Phase-
Change Processes 8

Phase Diagram
Figure 3–22
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.

Figure 3–23 Figure 3–24

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 2

Enthalpy—A Combination Property

h = u + Pv (kJ/kg)
H = U + PV ( kJ )
Figure 3–25
Figure 3–26
The combination u + Pv is often encountered The product pressure x
in the analysis of control volumes. volume has energy units.

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 • 3–5 Property Tables 3

Saturated Liquid and Saturated Vapor States

Figure 3–27
A partial list of Table A–4.
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 4

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.
It represents the amount of energy needed to vaporize a unit mass
of saturated liquid at a given temperature or pressure.
It decreases as the temperature or pressure increases and becomes
zero at the critical point.

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 • 3–5 Property Tables 5

Figure 3–28: Schematic and T-v diagram for Examples: Saturated liquid and
Example 3–1.
saturated vapor states of water on
T-v and P-v diagrams.

Figure 3–30: Schematic and P-v diagram for

Example 3–3.
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Figure 3–29: Schematic and P-v diagram for

Example 3–2.

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 • 3–5 Property Tables 6

Saturated Liquid–Vapor Figure 3–31

The relative amounts of liquid and
Mixture vapor phases in a saturated mixture
Quality, x: The ratio of the mass of vapor to are specified by the quality x.
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
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dependent properties for a mixture.

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 • 3–5 Property Tables 7

Figure 3–32
A two-phase system can be treated as a homogeneous mixture for convenience.

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 • 3–5 Property Tables 8

V  Vf  Vg Figure 3–33
V  mv  mt v avg  m f v f  mg v g Quality is related to the horizontal
m f  mt  mg  mt v avg   mt  mg  v f  mg v g
distances on P-v and T-v diagrams.

v avg   1  x  v f  xv g
vavg  v f  xv fg  m3 / kg 
mg
v fg  v g  v f x
mt
v avg  v f
x
v fg
uavg  u f  xu fg  kJ/kg 
havg  h f  xh fg  kJ/kg 
Yavg  y f  xy fg , y  v, u, or h
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 • 3–5 Property Tables 9

Figure 3–34
The v value of a saturated liquid– vapor mixture lies between the vf and vg values at the
specified T or P.

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 • 3–5 Property Tables 10

Examples: Saturated liquid-vapor mixture states on T-v and P-v

diagrams.
Figure 3–35 Figure 3–36
Schematic and T-v diagram for Schematic and P-v diagram for
Example 3–4. Example 3–5.

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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) Figure 3–39

Higher temperatures (T > Tsat at a given P) At a specified P, superheated
vapor exists at a higher h
Higher specific volumes (v > vg at a given P or T) than the saturated vapor
Higher internal energies (u > ug at a given P or T) Example 3–7).
Higher enthalpies (h > hg at a given P  or T)
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.

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 • 3–5 Property Tables 12

Figure 3–37
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
pressure. Lower internal energies (u < uf at a given P or T)
Lower enthalpies (h < hf at a given P or T)
y  y f @T y  v, u , or h Figure 3–41
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 

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 • 3–5 Property Tables 14

Figure 3–40
A compressed liquid may be approximated as a saturated liquid at the given
temperature.

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 • 3–5 Property Tables 15

Figure 3–42
At a given P and T, a pure substance will exist as a compressed liquid if T < Tsat @ P.

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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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 • 3–5 Property Tables 17

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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
8.31447 kJ/kmol  K
Ru 
R= (kJ / kg  K or kPa  m3/kg  K)
 8.31447 kPa  m 3
/kmol  K
M
0.0831447 bar  m3 /kmol  K
Ru  
R: gas constant 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

Figure 3–43
Different substances have different gas constants.

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 • 3–6 The Ideal-Gas Equation of State 3

Mass = Molar mass  Mole number Figure 3–44

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

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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

Figure 3–46
  v table  videal  
Percentage of error   v   100  involved in assuming steam to be an ideal gas, and
 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
Compressibility factor Z: A factor that accounts for the deviation of real
1

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

Pv Figure 3–47
Z The compressibility factor is unity for videal 
RT
.
RT P
ideal gases.
Pv  ZRT Z = 1 for ideal gases

v actual
Z
videal

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 • 3–7 Compressibility Factor—a
Measure of Deviation from Ideal-Gas
TheBehavior
farther away Z is from unity, the more the gas deviates from ideal-gas
2
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.
Figure 3–49
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
P Reduce
Behavior T Reduced v Pseudo-reduced
P  R T  v  3
R
actual

Pcr pressure R
Tcr temperature RTcr / Pcr specific volume

Figure 3–48
Comparison of Z factors for various gases.

Source: Gour-Jen Su, “Modified Law of Corresponding States,” Ind. Eng. Chem. (international ed.) 38 (19 46), p. 803.

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 • 3–7 Compressibility Factor—a
Measure of Deviation from Ideal-Gas
Behavior
Figure 3–50
Gases deviate from the ideal-gas
Figure 3–51
4
The compressibility factor can also
behavior the most in the neighborhood be determined from a knowledge
of the critical point. of PR and vR.

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 • 3–8 Other Equations Of State 1

The ideal-gas equation of state is very Figure 3–54

simple, but its range of applicability is
Several equations of state have
limited.
been proposed throughout
It is desirable to have equations of state history.
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 2

Van der Waals Equation of State

 a  Figure 3–55
2 
 P  v  b   RT Critical isotherm of a pure substance
 v 
has an inflection point at the critical
27 R 2T 2cr RT state.
a b  cr
64 Pcr 8 Pcr

This model includes two effects not

considered in the ideal-gas model:
• the intermolecular attraction forces.
• the volume occupied by the
molecules themselves.

The accuracy of the van der

Waals equation of state is often
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 • 3–8 Other Equations Of State 3

Beattie-Bridgeman Equation of State

RuT  c 
 A
P  2 1  3  v  B  2
v  vT  v

 a  b
A  A0 1   B  B0 1  
 v  v

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 ρcr .

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 • 3–8 Other Equations Of State 4

Benedict-Webb-Rubin Equation of State

RuT  C0  1 bRuT  a aa c     / v 2
P   B0 RuT  A0  2  2  3
 6  3 1  2  e
v  T v v v v T2  v 

The constants are given in Table 3–4.

This equation can handle substances at densities up to about 2.5ρcr .

Virial Equation of State

RT a  T  b  T  c  T  d  T 
P  2  3  4  5 ...
v v v v v

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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 • 3–8 Other Equations Of State 5

Table 3-4 Constants that appear in the Beattie-Bridgeman and the Benedict-Webb-
Rubin equations of state

Source: Gordon J. Van Wylen and Richard E. Sonntag, Fundamentals of Classical Thermodynamics, English/SI Version, 3rd ed. (New York: John Wiley & Sons, 1986), p. 46,
table 3.3.

Source: Kenneth Wark, Thermodynamics, 4th ed. (New York: McGraw-Hill, 1983), p. 815, table A-21M. Originally published in H. W. Cooper and J. C. Goldfrank,
Hydrocarbon Processing 46, no. 12 (1967), p. 141.

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 • 3–8 Other Equations Of State 6

Figure 3–56
Complex equations of state represent the P-v-T behavior of gases more accurately over
a wider range.

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 • 3–8 Other Equations Of State 7

Figure 3–57
Percentage of error involved in various equations of state for nitrogen
  v v  
 % error   table equation  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

©2019 McGraw-Hill Education.