CHAPTER II

Properties of Pure Substances

ABE 11
Thermodynamics and Heat Transfer

REYNOLD M. CAOILI, PhD

Mariano Marcos State University
College of Engineering
Department of Agricultural and
Biosystems Engineering
OUTLINE
A. The Pure Substance
B. The P-v-T Surface
C. The Liquid-Vapor Region
D. Steam Tables
E. The Ideal Gas Equation of State
F. Equation of State for a Nonideal Gas
Learning Objectives
At the end of the chapter, the student must be able to:
• define a pure substance
• explain the the phase change phenomenon of a pure
substance
• understand the nomenclature of the P-v-T, P-v, T-v, and P-T
diagrams
• use the equation of quality of mixture to characterize the
relative concentrations of saturated liquid-vapor mixture
condition
• determine the values of thermodynamics properties using the
steam and material properties tables and figures
• solve problems using different forms of ideal-gas equation of
state
• solve problems using the different nonideal gas equations of
state
 A. The Pure Substance

We define a

• Pure substance is a material with homogeneous

and invariable chemical composition.

• Homogeneous substance is a substance that has

uniform thermodynamic properties throughout
 A. The Pure Substance

To elaborate,
• Pure substances can have multiple phases: an
ice-water mixture is still a pure substance.

• An air-steam mixture is not a pure substance.

• Air, being composed of a mixture of N2, O2, and

other gases, is formally not a pure substance.
However, experience shows that we can often
treat air as a pure substance with little error.
B. The P-v-T Surface

It is well known that a pure substance can exist in

three (3) different major phases:
• Solid
• Liquid
• Gas
B. The P-v-T Surface
Phase Change of Pure Substances
ex. Water at 1 atm of pressure

Not about to evaporate

T=25oC Heat added T
Compressed liquid
phase

T=100oC About to evaporate

Heat added evaporation starts
Saturated liquid phase

T=100oC Heat added continues evap.

Saturated
T unchanged
vapor
Wet steam or
Saturated Saturated liquid-vapor mixture
liquid
B. The P-v-T Surface

Phase Change of Pure Substances

(continuation)
ex. Water at 1 atm of pressure
T=100oC All liquid evaporated
(about to condense)
Heat removed condensation
Saturated vapor phase

T=110oC Not about to condense

Heat added T
Superheated vapor phase
B. The P-v-T Surface
• Let us consider an experiment in which we boil water.
Ordinary water boiling is shown in Fig. 2.1.
• However, this ordinary experiment has constraints which
are too loose.
• Most importantly, the mass of water leaks into the
atmosphere; thus, the water vapor and the air become a
mixture and no longer a pure substance.

Figure 2.1. Water boiling isobarically in an open environment

 B. The P-v-T Surface
• Let us instead consider a more controlled piston-cylinder
arrangement (Figure 2.2).
• Inside the cylinder, we begin with pure liquid water at T = 20 oC.
• The piston is free to move in the cylinder, but it is tightly sealed, so
no water can escape.
• On the other side of the piston is a constant pressure atmosphere,
which we take to be at P = 100 kPa = 0.1 MPa = 105 Pa = 1 bar.

Figure 2.2. Sketch of experiment in which heat is added isobarically to water

in a closed piston-cylinder arrangement
 B. The P-v-T Surface
• We slowly add heat to the cylinder, and observe a variety of
interesting phenomena.
o The pressure remains at a constant value of 100 kPa. This is an
isobaric process.
o The total volume increases slightly as heat is added to the
liquid.

Figure 2.2. Sketch of experiment in which heat is added isobarically to water

in a closed piston-cylinder arrangement
B. The P-v-T Surface
o The temperature of the liquid increases significantly as heat is
added to the liquid.
o At a special value of temperature, observed to be T = 99.62 ◦C,
we have all liquid, but cannot add any more heat and retain all
liquid. We will call this state the saturated liquid state. We call T
= 99.62 ◦C the saturation temperature at P = 100 kPa.

Figure 2.2. Sketch of experiment in which heat is added isobarically to water

in a closed piston-cylinder arrangement
B. The P-v-T Surface
o As we continue to add heat:
 The temperature remains constant (this is isothermal now as
well as isobaric).
 The total volume continues to increase.
 We notice two phases present: liquid and vapor, with a
distinct phase boundary.

Figure 2.2. Sketch of experiment in which heat is added isobarically to water

in a closed piston-cylinder arrangement
B. The P-v-T Surface
 The liquid is dense relative to the vapor. That is 𝜌f > 𝜌g,
where f denotes fluid or liquid and g denotes gas or vapor.
Thus, vg > vf .
 As more heat is added, more vapor appears, all while P = 100
kPa and T = 99.62 oC.
 At a certain volume, we have all vapor and no liquid, still at
P = 100 kPa, T = 99.62 oC. We call this state the saturated
vapor state.
B. The P-v-T Surface
o As heat is added, we find both the temperature and the
volume rise, with the pressure remaining constant. The
water remains in the all vapor state.

Figure 2.2. Sketch of experiment in which heat is added isobarically to water

in a closed piston-cylinder arrangement
 B. The P-v-T Surface
• We have just boiled water

• We sketch this process in

the temperature-specific
volume plane or the T − v
plane (Figure 2.3)

• Note that the mass m of

the water is constant in
this problem, so the
extensive V is strictly
proportional to specific
volume, v = V/m. Figure 2.3. Isobar in the T − v plane for our thought
experiment in which heat is added isobarically
to water in a piston-cylinder arrangement.
 B. The P-v-T Surface
• We next repeat this experiment at lower pressure (such
as might exist on a mountain top) and at a higher
pressure (such as might exist in a valley below sea level).

• For moderate pressures, we find qualitatively the exact

same type of behavior. The liquid gets hotter, turns into
vapor isothermally, and then the vapor gets hotter as the
heat is added.
 B. The P-v-T Surface
• However, we note the following important facts:
o The saturation temperature (that is the boiling point)
increases as pressure increases, as long as the
pressure increase is not too high.
o As pressure increases vf becomes closer to vg.
o Above a critical pressure, P = Pc = 22.089 MPa, there
is no phase change observed.
o At the critical pressure, the temperature takes on a
critical temperature of Tc = 374.14 oC. At the critical
pressure and temperature, the specific volume takes
the value vf = vg = vc = 0.003155 m3/kg.
 B. The P-v-T Surface
• We see how the boiling
point changes with pressure
by plotting the saturation
pressure as a function of
saturation temperature in
the T − P plane in Figure 2.4.
• This is the so-called vapor
pressure curve.
• Here, we focus on liquid-
vapor mixtures and keep T
high enough to prevent
freezing.
• Note the curve terminates Figure 2.4. Saturation pressure versus
abruptly at the critical point. saturation temperature sketch
 B. The P-v-T Surface
We adopt the following nomenclature:

• saturated liquid: the material is at Tsat and is all liquid.

• saturated vapor: the material is at Tsat and is all vapor.
• compressed (subcooled) liquid: the material is liquid
with T < Tsat
• superheated vapor: the material is vapor with T > Tsat
• two-phase mixture: the material is composed of co-
existing liquid and vapor with both at Tsat
 B. The P-v-T Surface
• The data obtained in an actual
experiment could be presented as
a three-dimensional surface with
P = P (v,T) .

• Figure 2.4 shows a qualitative Figure 2.4. P-V-T surface for a substance
that contracts upon freezing
rendering of a substance that
contracts on freezing.

• For a substance that expands on

freezing, the solid-liquid surface
would be at a smaller specific
volume than for the solid surface.
Figure 2.5. P-V-T surface for a substance
that expands upon freezing
 B. The P-v-T Surface
• The regions where only one phase
exists are labeled solid, liquid, and
vapor.

• Where two phases exist

Figure 2.4. P-V-T surface for a substance
simultaneously the regions are that contracts upon freezing
labeled solid-liquid , solid-vapor ,
and liquid-vapor .

• Along the triple line, a line of

constant temperature and pressure,
all three phases coexist.

Figure 2.5. P-V-T surface for a substance

that expands upon freezing
 B. The P-v-T Surface
• The P-v-T surface may be projected unto the P-v plane, the T-v plane, and
the P-T plane, thus obtaining the P-v, T-v, and P-T diagrams (Figure 2.6)
• Again, distortions are made so that the various regions are displayed.
Note that when the triple line of Figures 2.4 and 25 are viewed parallel to
the v axis it appears to be a point, hence the name triple point.
• A constant pressure line is shown on the T-v diagram and a constant
temperature line on the P-v diagram.

Figure 2.6. The P-v, T-v, and P-T diagrams

 C. The Liquid-Vapor Region
• At any state (T, v) between saturated points f
and g , shown in Figure 2-7, liquid and vapor
exist as a mixture in equilibrium.

• Then for a state of the system represented by

(T ,v) the total volume of the mixture (V) is
the sum of the volume occupied by the liquid
(Vf)and that occupied by the vapor (Vg),
𝑽 = 𝑽 𝒇 + 𝑽𝒈 Eq. 2.0
Figure 2.7. A T-v diagram
But, 𝑉 = 𝑚𝑣
showing the saturated liquid
𝑉𝑓 = 𝑚𝑓 𝑣𝑓
and saturated vapor points
𝑉𝑔 = 𝑚𝑔 𝑣𝑔
So,
𝒎𝒗 = 𝒎𝒇 𝒗𝒇 + 𝒎𝒈 𝒗𝒈 Eq. 2.1

where:
m = total mass of the system v = total specific volume
mf = amount of mass in the liquid phase vf = specific volume of saturated liquid
mg = amount of mass in the vapor phase vg = specific volume of saturated vapor
 C. The Liquid-Vapor Region
• For two-phase mixtures, we define a new property to
characterize the relative concentrations of liquid and vapor. We
define the
Quality (x) of the mixture as the ratio of the mass of the
saturated vapor to the total mass of mixture
𝒎𝒈
𝒙= Eq. 2.2
𝒎

We can also take the total mass to be the sum of

the liquid and vapor masses:
𝒎 = 𝒎𝒇 + 𝒎𝒈 Eq. 2.3

so
𝒎𝒈
𝒙= Eq. 2.4
𝒎𝒇 + 𝒎𝒈
 C. The Liquid-Vapor Region
QUALITY, x (2 phase condition)
Saturated liquid-vapor mixture condition
mvapor x is a thermodynamic property
x exists only in the liquid-vapor mixture
mliquid region

There are two important limits to remember:

• x = 0: corresponds to mg = 0. This is the all liquid limit.
• x = 1: corresponds to mg = m . This is the all gas limit.

We must have
𝟎≤𝒙≤𝟏
(wet) (dry)
100% liquid 100% vapor
C. The Liquid-Vapor Region
Recognizing that 𝒎 = 𝒎𝒇 + 𝒎𝒈 Eq. 2.3

we may write 𝒎𝒗 = 𝒎𝒇 𝒗𝒇 + 𝒎𝒈 𝒗𝒈 Eq. 2.1

using our definitions of quality as

𝒗 = 𝒗𝒇 + 𝒙(𝒗𝒈 − 𝒗𝒇 ) Eq. 2.5

because the difference (denoted by 𝒗𝒇𝒈 ) in saturated vapor and

saturated liquid values frequently appears in calculations , that is
𝒗𝒇𝒈 = 𝒗𝒈 − 𝒗𝒇 Eq. 2.6

Thus, eq. 2.5 is

𝒗 = 𝒗𝒇 + 𝒙𝒗𝒇𝒈 Eq. 2.7
Derivation of eq. 2.5
V  V f  Vg
m  m f  mg
V  mv , V f  m f v f , Vg  mg v g
mv  m f v f  mg v g
mf v f mg v g
v 
m m
Recall the definition of quality x
mg mg
x 
m m f  mg
Then
mf m  mg
  1 x
m m
Note, quantity 1- x is often given the name moisture. The specific volume of the saturated
mixture becomes
v  (1  x )v f  xv g

v  v f  x (v g  v f ) Eq. 2.5 28
C. The Liquid-Vapor Region
Note:

• The percentage liquid by mass in a mixture is

%𝒎𝒇 = 𝟏𝟎𝟎(𝟏 − 𝒙) Eq. 2.8

and

• The percentage vapor by mass in a mixture is

%𝒎𝒈 = 𝟏𝟎𝟎𝒙 Eq. 2.9

D. Steam Tables
Tabulations have been made for many substances of the
thermodynamic properties P , v, and T
• Table C-1 gives the properties of saturated water as a function
of saturation temperature
• Table C-2 gives properties of saturated water as a function of
saturation pressure
o The information contained in the two tables is essentially the
same, the choice being a matter of convenience.
o We should note, however, that in the mixture region pressure
and temperature are dependent.
o Thus to establish the state of a mixture, if we specify the
pressure, we need to specify a property other than
temperature.
o Conversely, if we specify temperature, we must specify a
property other than pressure.
D. Steam Tables
• Table C-3 lists the properties of superheated water vapor.

o To establish the state of a simple substance in the

superheated region, it is necessary to specify two
properties.

o While any two may be used, the most common procedure

is to use pressure and temperature. Thus, properties such
as v are given in terms of the set of independent
properties P and T .
D. Steam Tables
• Table C-4 lists data pertaining to compressed liquid.
o At a given temperature the specific volume of a liquid is
essentially independent of the pressure.
 For example, for a temperature of 100°C in Table C-1, the
specific volume vf of liquid is 0.001044 m3/kg at a pressure of
100 kPa, whereas at a pressure of 10 MPa the specific volume
is 0.001038 m3/kg, less than a 1 percent decrease in specific
volume.

o Thus it is common in calculations to assume that the

specific volume of a compressed liquid is equal to the
specific volume of the saturated liquid at the same
temperature.
o Note, however, that the specific volume of saturated
liquid increases significantly with temperature, especially
at higher temperatures.
D. Steam Tables
• Table C-5 gives the properties of a saturated solid and a
saturated vapor for an equilibrium condition.

o Note that the value of the specific volume of ice is

relatively insensitive to temperature and pressure for the
saturated-solid line.

o Also, it has a greater value (almost 10 percent greater)

than the minimum value on the saturated-liquid line.
D. Steam Tables
Example 1.
Determine the volume change when 1 kg of saturated water is
completely vaporized at a pressure of (a) 1 kPa, (b) 100 kPa, and (c) 10000 kPa.

Given: mf = 1 kg

Required: a. volume change, vfg when P = 1 kPa

b. volume change, vfg when P = 100kPa
c. volume change, vfg when P = 10000kPa
Solution:
Using eq. 2.6 𝒗𝒇𝒈 = 𝒗𝒈 − 𝒗𝒇
(Table C-2 provides the necessary values. Note that P is given in MPa)

a) when P = 1 kPa = 0.001 MPa; vg = 129.2 m3/kg and vf = 0.001 m3/kg

vfg = 129.2 – 0.001 = 129.199 m3/kg
b) when P = 100 kPa = 0.1 MPa; vg = 1.694 m3/kg and vf = 0.001 m3/kg
vfg = 1.694 – 0.001 = 1.693 m3/kg
c) when P = 10000 kPa = 10 MPa; vg = 0.01803 m3/kg and vf = 0.001452 m3/kg
vfg = 0,01803 – 0.001 452= 0.016578 m3/kg
D. Steam Tables
Example 1.
Determine the volume change when 1 kg of saturated water is
completely vaporized at a pressure of (a) 1 kPa, (b) 100 kPa, and (c) 10000 kPa.

Given: mf = 1 kg

Required: a. volume change, vfg when P = 1 kPa

b. volume change, vfg when P = 100kPa
c. volume change, vfg when P = 10000kPa
Solution:
Using eq. 2.6 𝒗𝒇𝒈 = 𝒗𝒈 − 𝒗𝒇
(Table C-2 provides the necessary values. Note that P is given in MPa)

a) when P = 1 kPa = 0.001 MPa; vg = 129.2 m3/kg and vf = 0.001 m3/kg

vfg = 129.2 – 0.001 = 129.199 m3/kg
b) when P = 100 kPa = 0.1 MPa; vg = 1.694 m3/kg and vf = 0.001 m3/kg
vfg = 1.694 – 0.001 = 1.693 m3/kg
c) when P = 10000 kPa = 10 MPa; vg = 0.01803 m3/kg and vf = 0.001452 m3/kg
vfg = 0,01803 – 0.001 452= 0.016578 m3/kg
D. Steam Tables
Example 2.
Four kg of water is placed in an enclosed volume of 1m3. Heat is added
until the temperature is 150°C. Find (a) the pressure, (b) the mass of vapor, and
(c) the volume of the vapor.

Given: mf = 4 kg V = 1 m3 T = 150oC

Required: a. pressure, P
b. mass of vapor, vg
c. volume of vapor, Vg
Solution:

Table C-1 is used.

• The volume of 4 kg of saturated vapor at 150oC is

Vg = vgmg where: vg = 0.3928 m3/kg (from Table C-1)
Vg = 0.3928 m3/kg (4 kg)
Vg = 1.5712 m3 (since the given volume =1m3 is less than this, we
assume the state to be in the quality region)
D. Steam Tables
Solution:

a) At T = 150oC, using Table C-1 in the quality region the pressure is P = 0.4758 MPa
b) Solving mg
𝒎𝒈
from 𝒙= 𝒎
𝒎𝒈 = 𝒎𝒙
where: m = 4 kg
x = ? From 𝒗 = 𝒗𝒇 + 𝒙(𝒗𝒈 − 𝒗𝒇 )
𝑣;𝑣𝑓
x=𝑣
𝑔 ;𝑣𝑓
𝑽 𝟏 𝒎𝟑
where: v = = = 0.25 𝑚3/𝑘𝑔
𝒎 𝟒 𝒌𝒈
vf = 0.001090 m3/kg (from Table C-1)
vg = 0.3928 m3/kg (from Table C-1)
0.25;0.001090
x=
0.3928;0.001090
x = 0.6354
𝑚𝑔 = 4 𝑘𝑔 (0.6354)
𝑚𝑔 = 2.5416 𝑘𝑔
D. Steam Tables
Solution:

b) Solving Vg

𝑽𝒈 = 𝒗 𝒈 𝒎 𝒈
where: vg = 0.3928 m3/kg (from Table C-1)
𝑚𝑔 = 2.5416 𝑘𝑔

𝑚3
𝑉𝑔 = 0.3928 (2.5416 𝑘𝑔)
𝑘𝑔

𝑉𝑔 = 0.9983 𝑚3

Note that in mixtures where the quality is not very close to zero the vapor phase
occupies most of the volume. In this example, with a quality of 63.54 percent it
occupies 99.83 percent of the volume.
D. Steam Tables
Example 3.
Four kg of water is heated at a pressure of 220 kPa to produce a
mixture with quality x = 0.8. Determine the final volume occupied by the
mixture.

Given: mf = 4 kg P = 220 kPa x = 0.8

Required: Final Volume, V

Solution:

Solving the final volume, V

V = mv
where: m = 4 kg
v =?
v = vf + x (vg – vf)
use Table C-2 to determine the values of vf and
vg when P = 220 kPa = 0.22 MPa
D. Steam Tables
use Table C-2 to determine the values of vg and vf at P = 220 kPa = 0.22 MPa
by linearly interpolate between 0.20 MPa and 0.30 MPa.

0.20 0.8857 0.20 0.001061

0.22 vg 0.22 vf
0.30 0.6058 0.30 0.001073

vg = 0.8297 m3/kg vf = 0.001063 m3/kg

So, v = vf + x (vg – vf)

v = 0.001063 + 0.8 (0.8297 – 0.001063)
v = 0.6640 m3/kg

Therefore, the total volume occupied by 4 kg is

V = mv
V = 4 kg (0.6640 m3/kg)
V = 2.656 m3
D. Steam Tables
Example 4.
Two Ib of water is contained in a constant-pressure container held at
540 psia. Heat is added until the temperature reaches 700 OF. Determine the
final volume of the container.

Given: mf = 2 lbm P = 540 psia T = 700 OF (superheated)

constant-pressure container

Required: Final Volume of container, V

Solution:

Solving the final volume, V

V = mv
where: m = 2 lb
v =?
use Table C-3E to determine the values of v at P=540 psia
and T = 700 OF
D. Steam Tables
Solving the final volume, V
V = mv
where: m = 2 lb
v =?
use Table C-3E to determine the values of v at T = 700 OF
and P=540 psia
by linear interpolation between P=500 psia and P=600 psia
500 1.3040
540 v
600 1.0727

v = 1.2115 ft3/lbm
Therefore,

V = 2 lb (1.2115 ft3/lbm)
V = 2.423 ft3
E. The Ideal-Gas Equation of State
When the vapor of a substance has relatively low density,
the pressure, specific volume, and temperature are
related by the simple equation

𝑷𝒗 = 𝑹𝑻
where R is a constant for a particular gas and is called the gas
constant. This equation is an equation of state in that it relates the
state properties P, v, and T ; any gas for which this equation is valid
is called an ideal gas or a perfect gas.

Note that when using the ideal-gas equation the pressure

and temperature must be expressed as absolute
quantities.
E. The Ideal-Gas Equation of State
The gas constant R is related to a universal gas constant 𝑹, which
has the same value for all gases, by the relationship
𝑹
𝑹=
𝑴
where:

• The value of is 𝑹 is
𝑹 = 8.314 kJ/( kmol - K) = 1545 ft-lbf/( lbmol- OR )= 287 J/kg K
• M is the molar mass, values of which are tabulated in Table B-2
and Table B-3.
• The mole is that quantity of a substance (i.e., that number of
atoms or molecules) having a mass which, measured in grams, is
numerically equal to the atomic or molecular weight of the
substance.
E. The Ideal-Gas Equation of State
• In the SI system it is convenient to use instead the kilomole
(kmol), which amounts to x kilograms of a substance of
molecular weight x.
For instance, 1 kmol of carbon is a mass of 12 kg
(exactly); 1 kmol of molecular oxygen is 32 kg (very
nearly). Stated otherwise, M = 12 kg/ kmol for C, and
M = 32 kg/ kmol for O2.
• In the English system one uses the pound-mole (Ibmol); for O2,
M = 32 lbm/lbmol.

• For air M is 28.97 kg/kmol(28.97 Ibm/lbmol), so that for air R is

0.287 kJ/kg - K (53.3 ft-lbf/lbm- OR), a value used extensively in
calculations involving air.
E. The Ideal-Gas Equation of State
Other forms of the ideal-gas equation

𝑷𝑽 = 𝒎𝑹𝑻 𝑷 = 𝝆𝑹𝑻 𝑷𝑽 = 𝒏𝑹𝑻

where n is the number of moles

• Care must be taken in using this simple convenient equation of

state. A low-density 𝝆 can be experienced by either having a
low pressure or a high temperature.

• For air the ideal-gas equation is surprisingly accurate for a wide

range of temperatures and pressures; less than 1 percent error
is encountered for pressures as high as 3000 kPa at room
temperature, or for temperatures as low as - 130°C at
atmospheric pressure.
 E. The Ideal-Gas Equation of State
The compressibility factor Z helps us in determining whether or
not the ideal-gas equation should be used. It is defined as
𝑷𝒗
𝒁=
𝑹𝑻

and is displayed in Figure 2-8

for nitrogen. Since air is
composed mainly of nitrogen,
this figure is acceptable for
air also. If Z = 1, or very
nearly 1, the ideal-gas
equation can be used. If Z is
not approximately 1 , then
the above equation may be
used.
Figure 2.8
E. The Ideal-Gas Equation of State
The compressibility factor can be determined for any gas by using
a generalized compressibility chart presented in Fig. H-1 in the
appendix. In the generalized chart the reduced pressure PR and
reduced temperature TR must be used. They are calculated from
𝑷 𝑻
𝑷𝑹 = 𝑻𝑹 =
𝑷𝒄 𝑻𝒄

where Pc and Tc are critical-point pressure and temperature,

respectively, of Table B-3.
E. The Ideal-Gas Equation of State
Example 5
An automobile tire with a volume of 0.6 m3 is inflated to a gage
pressure of 200 kPa. Calculate the mass of air in the tire if the temperature is
20°C.

Given: V = 0.6 m3 Pgage = 200 kPa

Required: mass of tire if T = 20°C

Solution
• Air is assumed to be an ideal gas at the conditions of this example. In the
ideal-gas equation, PV = mRT, we use absolute pressure and absolute
temperature. Thus, using Patm = 100 kPa,
P = 200 + 100 = 300 kPa and T = 20 + 273 = 293 K
also, for air R = 0.287 kJ/kg K = 287 J/kg K = 287 Nm/kg K
The mass is then calculated to be
𝑁
𝑃𝑉 (300000 )(0.6 𝑚3)
𝑚2
𝑚= 𝑅𝑇
= 𝑁.𝑚 = 2.14 𝑘𝑔
(287 )(293 𝐾)
𝑘𝑔 𝐾
F. Equation of State for a Nonideal Gas
• There are many equations of state that have been
recommended for use to account for nonideal-gas
behavior.
• Such behavior occurs where the pressure is relatively high
(> 4 MPa for many gases) or when the temperature is near
the saturation temperature.
• There are no acceptable criteria that can be used to
determine if the ideal-gas equation can be used or if the
nonideal-gas equations of this section must be used.
• Usually a problem is stated in such a way that it is obvious
that nonideal-gas effects must be included; otherwise a
problem is solved assuming an ideal gas.
F. Equation of State for a Nonideal Gas
van der Waals equation of state
The van der Waals equation of state is intended to
account for the volume occupied by the gas molecules and
for the attractive forces between molecules. It is
𝑹𝑻 𝒂
𝑷 = 𝒗;𝒃 − 𝒗𝟐

where the constants a and b are related to the critical-point

data of Table B-3 by
𝟐𝟕𝑹𝟐 𝑻𝒄 𝟐 𝑹𝑻𝒄
𝒂= 𝒃=
𝟔𝟒𝑷𝒄 𝟖𝑷𝒄

These constants are also presented in Table B-8 to simplify

calculations.
F. Equation of State for a Nonideal Gas
Redlich-Kwong equation of state
An improved equation is the Redlich-Kwong equation
of state as
𝑹𝑻 𝒂
𝑷= 𝒗;𝒃
− 𝒗(𝒗:𝒃) 𝑻

where the constants are given by

𝑹𝟐 𝑻𝒄 𝟐.𝟓 𝑹𝑻𝒄
𝒂= 𝟎. 𝟒𝟐𝟕𝟓 𝑷 𝒃= 𝟎. 𝟎𝟖𝟔𝟕 𝑷
𝒄 𝒄

and are included in Table B-8 .

F. Equation of State for a Nonideal Gas
virial equation of state
A virial equation of state presents the product Pv as a
series expansion. The most common expansion is

𝑹𝑻 𝑩(𝑻) 𝑪(𝑻)
𝑷= + + 𝒗𝟑 +⋯
𝒗 𝒗𝟐

where interest is focused on B ( T ) since it represents the

first-order correction to the ideal gas law. The functions B(T),
C(T), etc., must be specified for the particular gas.
F. Equation of State for a Nonideal Gas
Example 6
Calculate the pressure of steam at a temperature of 500°C
and a density of 24 kg/m3 using (a) the ideal-gas equation, (b)the
van der Waals equation, (c) the Redlich-Kwong equation, (d) the
compressibility factor, and (e) the steam table.

Given: T = 500°C 𝜌 = 24 kg/m3

Required: Pressure of steam using

a) the ideal-gas equation,
b) the van der Waals equation,
c) the Redlich-Kwong equation,
d) the compressibility factor, and
e) the steam table.
F. Equation of State for a Nonideal Gas
Given: T = 500°C 𝜌 = 24 kg/m3

Solution
a) solving P using the ideal-gas equation
𝑷 = 𝝆𝑹𝑻
where: 𝜌 = 24 kg/m3
R = for steam is found in Table B-2
R = 0.4615 kJ/kg K
T = 500 +273 = 773 K

𝑘𝑔 𝑘𝐽 1𝑘𝑁𝑚 1𝑘𝑃𝑎
𝑃 = 24 3 0.4615 773𝐾
𝑚 𝑘𝑔𝐾 𝑘𝐽 𝑘𝑁/𝑚2

𝑷 = 8561.75 kPa
 F. Equation of State for a Nonideal Gas
Given: T = 500°C 𝜌 = 24 kg/m3
Solution
b) solving P using the van der Waals equation
𝑹𝑻 𝒂
𝑷 = 𝒗;𝒃 − 𝒗𝟐 where: R = 0.4615 kJ/kg K (from Table B-2)
T = 500 +273 = 773 K
1 1
𝑣 = 𝜌 = 𝑘𝑔
24
𝑚3
a and b for water is found in Table B-8
a = 1.703 kPa m6/kg2
b = 0.00169 m3/kg
𝑘𝐽 1𝑘𝑁𝑚 1𝑘𝑃𝑎
0.4615 (773𝐾)( )( ) 𝑘𝑃𝑎 𝑚6
𝑘𝑔𝐾 𝑘𝐽 𝑘𝑁 1.703
𝑚 2 𝑘𝑔2
𝑃= −
1 𝑚3 1 2
− 0.00169 ( )
𝑘𝑔 𝑘𝑔 𝑘𝑔
24 𝑚3 24 𝑚3

𝑷 = 7942.7 kPa
 F. Equation of State for a Nonideal Gas
Given: T = 500°C 𝜌 = 24 kg/m3
Solution
c) solving P using the Redlich-Kwong equation
𝑹𝑻 𝒂
𝑷 = 𝒗;𝒃 − where: R = 0.4615 kJ/kg K (from Table B-2)
𝒗(𝒗:𝒃) 𝑻
T = 500 +273 = 773 K
1 1
𝑣 = 𝜌 = 𝑘𝑔
24
𝑚3
a and b for water is found in Table B-8
a = 43.9 kPa m6 K1/2/kg2
b = 0.00117 m3/kg
𝑘𝐽 1𝑘𝑁𝑚 1𝑘𝑃𝑎
0.4615 (773𝐾)( )( ) 𝑘𝑃𝑎 𝑚 6 𝐾1/2
𝑘𝑔𝐾 𝑘𝐽 𝑘𝑁 43.9
𝑚2 𝑘𝑔2
𝑃= −
1 𝑚3 1 1 𝑚3
− 0.00117 ( + 0.00117 )( 773𝐾)
𝑘𝑔 𝑘𝑔 𝑘𝑔 𝑘𝑔 𝑘𝑔
24 𝑚3 24 𝑚3 24 𝑚3

𝑷 = 7934.0 kPa
 F. Equation of State for a Nonideal Gas
Given: T = 500°C 𝜌 = 24 kg/m3

Solution
d) solving P using the compressibility factor
• The compressibility factor is found from the generalized compressibility chart of Fig. H-
1 in the appendix
• To use the chart we must know the reduced temperature and pressure:
𝑻
𝑻𝑹 = 𝑻 where: T = 500 + 273 = 773 K
𝒄
Tc = critical temperature of water (Table B-3)
Tc = 647.4 K
773 𝐾
𝑇𝑅 = 647.4 𝐾

𝑻𝑹 = 𝟏. 𝟏𝟗

𝑷
𝑷𝑹 = 𝑷 where: P = 8000 kPa (used the anticipated pressure from a, b, c)
𝒄
Pc = critical pressure of water (Table B-3)
Pc = 22.1 MPa = 22100 kPa
8000 𝑘𝑃𝑎
𝑃𝑅 = 22100 𝑘𝑃𝑎

𝑷𝑹 = 𝟎. 𝟑𝟔𝟐
 F. Equation of State for a Nonideal Gas
Given: T = 500°C 𝜌 = 24 kg/m3

Solution
d) solving P using the compressibility factor
• The compressibility factor is found from the generalized compressibility chart of Fig. H-
1 in the appendix
• the reduced temperature and pressure:
𝑻𝑹 = 𝟏. 𝟏𝟗 𝑷𝑹 = 𝟎. 𝟑𝟔𝟐

From Fig. H-1

Z = 0.93 (approximately)

𝑷𝒗
From 𝒁=
𝑹𝑻

𝑘𝐽 1𝑘𝑁𝑚 1𝑘𝑃𝑎
0.93 (0.4615𝑘𝑔𝐾)(773 𝐾)( 𝑘𝐽 )( 𝑘𝑁 )
𝒁𝑹𝑻 2
𝑚
𝑷= = 1
𝒗
𝑘𝑔
24𝑚3
𝑷 = 7962.4 kPa
 F. Equation of State for a Nonideal Gas
Given: T = 500°C 𝜌 = 24 kg/m3
Solution
e) solving P using the steam table
• The steam table provides the most precise value for the
pressure.

• Using Table C-3 at T = 500°C and v = 1/24 = 0.0417 m3/kg,

we find

P = 8 MPa = 8000 kPa

.
 F. Equation of State for a Nonideal Gas

Summary:
P (kPa) Error (%)
ideal-gas equation 8561.8 7.02
van der Waals equation 7942.7 0.72
Redlich-Kwong equation 7934.0 0.82
compressibility factor 7962.4 0.47
steam table 8000.0

• Note the steam table provides the most precise value for the
pressure.
• The ideal-gas law has an error of 7.02 percent, and the error of
each of the other three equations is less than 1 percent.
G. References

Powers, Joseph M. 2019. Lecture Notes on

Thermodynamics. Department of Aerospace
and Mechanical Engineering, University of
Notre Dame Notre Dame, Indiana 46556-
5637. USA.

Potter, M.C. & C.W. Somerton. 1993. Schaum’s

Outline of Theory and Problems of
Thermodynamics for Engineers. McGraw-Hill
Book Co.
For more information contact:

REYNOLD M. CAOILI, PhD

Mariano Marcos State University
College of Engineering
Department of Agricultural and
Biosystems Engineering

email address:
rmcaoili@mmsu.edu.ph
reynoldmcaoili@yahoo.com

FB Account Name:
Reynold M. Caoili

Contact Number:
(+63) 09356852107