CHAPTER 11

PROPERTIES of PURE SUBSTANCES

Objectives
1. Introduce the concept of a pure substance.

2. Illustrate the p- and T- property diagrams of a pure substance.

3. Demonstrate the procedures for determining the thermodynamic

properties of pure substances from tables of property data.

4. Develop the ability to use the tables of properties on the computer.

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 The properties of materials are the building blocks of thermodynamics. These
properties are interrelated. Properties are point functions.

REVIEW of FAMILIAR PROPERTIES

1. Density (ρ)
2. Mass (m)
3. Weight (W)
4. Specific Weight (γ)
5. Pressure (p)
6. Temperature (T)
7. Volume (V)
8. Specific Volume ()
9. Total Internal Energy (U)
10. Specific Internal Energy or Internal Energy (u)
11. Total Enthalpy (H)
12. Specific Enthalpy (h)
13. Total Entropy (S)
14. Specific Entropy (s)

INTRODUCTION
A pure substance is one that has a homogeneous and invariable chemical
composition. It may exist in more than one phase, but the chemical composition is the
same in all phases. Thus, liquid water, a mixture of liquid water and water vapor
(steam), and a mixture of ice and liquid water are all pure substances – every phase
has the same chemical composition, that is, H2O.

In this chapter, discussion is concentrated on the use of the tables of properties

for pure substances for states in the compressed-liquid, liquid-vapor saturation, and
superheated-vapor regions. In most instances separate tables are provided for each
of the three regions. Even though the specific applications are restricted to water, the
principles involved apply equally well to any other pure substance.

Properties and the behavior of substances are very important for the studies
of devices and thermodynamic systems. The steam power plant shown in Fig 8-1 uses
water as the working substance. Water vapor (steam) is made by boiling water at
high pressure in the steam generator (boiler) followed by expansion in the turbine to
a lower pressure, cooling in the condenser, and returning it to the boiler by a pump
that raises the pressure. We must know the properties of water to properly size
equipment such as the burners or heat exchangers, the turbine, and the pump for the
desired transfer of energy and the flow of water. As water is transformed from liquid
to vapor, we need to know the temperature for the given pressure, and we must know
the density or specific volume so that the piping can be properly dimensioned for the
flow. If the pipes are too small, the expansion creates excessive velocities, leading to
pressure losses and increased friction, and thus demanding a larger pump and
reducing the turbine’s work output. This is just one example of complete
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thermodynamic systems in which a substance goes through several processes
involving changes in its thermodynamic state and therefore its properties.

CHANGES OF PHASE AT CONSTANT PRESSURE

Compressed
Liquid Region

Superheated
Vapor Region

Liquid-Vapor Saturation
Region

Fig 11-1

Figure 11-1 is the graph of plotting the temperature as a function of volume

following a constant pressure process. Starting at room conditions (state A), heating
the liquid water will make its temperature goes up and the volume expands slightly,
as indicated in the figure (state A to state B). As state B is reached, the liquid water
will start to boil at temperature of 99.6oC, which is called saturated liquid. This means
that it is at the highest temperature at which, for this pressure, it can remain liquid. If
more heat is added, some of the liquid changes to vapor, and a mixture of vapor and
liquid occurs between state B and state C, and eventually reaches state C. At state C,
all the water exists as a saturated vapor. Further heating will produce vapor at higher
temperatures in states called superheated vapor, where the temperature is higher
than the saturation temperature for the given pressure. The difference between a
given temperature and the saturation temperature for the same pressure is called the
degree of superheat.

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 For higher pressures, the saturation temperature is higher, like 179.9oC at
state F for a pressure of 1 MPa, and so forth. At the critical pressure of 22.09 MPa,
heating proceeds from state M to state N to state O in a smooth transition from a liquid
state to a vapor state without undergoing the constant temperature vaporization
(boiling) process. The states in which the saturation temperature is reached for the
liquid (B, F, J) are saturated liquid states forming the saturated liquid line. Similarly,
the states along the other border of the two-phase region (N, K, G, C) are saturated
vapor states forming the saturated vapor line.

Fig 11-2

Figure 11-2 is the corresponding p- diagram of figure 11-1. This diagram will
be particularly useful for finding the work done during a process. Note that for a
simple pure substance, the state is defined by two independent properties. To
understand the significance of the term independent property, consider the
saturated-liquid and saturated-vapor states of a pure substance. These two states
have the same pressure and the same temperature, but they are definitely not the
same state. In a saturation state, therefore, pressure and temperature are not
independent properties. Two independent properties, such as pressure and specific
volume or pressure and quality, are required to specify a saturation state of a pure
substance.

Saturation temperature designates the temperature at which vaporization

takes place at a given pressure. It is also commonly known as the boiling temperature.
When a liquid has a pressure higher than the saturation pressure for a given
temperature, the state is a compressed liquid. Consider the same state but compare it
to the saturated liquid state at the same pressure, the temperature is lower than the
saturation temperature; thus, the state is a subcooled liquid. For these liquid states,
the term compressed liquid is used in the remainder of the course.

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PHASE AT CONSTANT PRESSURE

Fig 11-3
Consider the p- diagram of figure 11-3 in which a constant pressure line is
plotted at 1.014 bars. The corresponding saturation temperature of this pressure is
100oC. Point 1 denotes a compressed-liquid state since its temperature is less than
that of the saturation temperature corresponding to 1.014 bars (t < tsat). Point 2 is a
saturated liquid state. Point 3 is a saturated vapor state. Point 4 indicates a
superheated vapor state since its temperature is greater than that of the saturation
temperature corresponding to 1.014 bars (t > tsat).

THE TWO-PHASE STATES

Fig 11-4

Consider the T- diagram of figure 11-4. By convention, the subscript f is used
to designate a property of a saturated liquid and the subscript g is used to designate
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a property of a saturated vapor. All the liquid present is at state f with specific volume
f, and all the vapor present is at state g with specific volume g. The total volume is
the sum of the liquid volume and the vapor volume, or

V = Vliq + Vvap = mliq f + mvap g (11-1)

The average specific volume  of the system is

V mliq mvap
= = f + g
m m m

 = (1‒ x)f + x g (11-2)

In terms of quality (x)

mvap
x=
m

Using the definition

fg = g ‒ f
Then

 = f + x fg (11-3)

The quality can be determined as

 ‒ f
x=
fg

Similarly, for the other properties

u = uf + x ufg (11-4)

u ‒ uf
x=
ufg

h = hf + x hfg (11-5)

h ‒ hf
x=
hfg

s = sf + x sfg (11-6)

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 s ‒ sf
x=
sfg

Example 11.1
Find the specific volume for a saturated mixture of water at 200oC and a quality
of 70%.

Solution:
From Table 1 (values in bracket are taken from CATT2),
f = 1.157 x 10-3 m3/kg [1.156 x 10-3 m3/kg]
g = 0.12736 m3/kg [0.1274 m3/kg]

Using equation 11-2,

 = (1‒ x)f + x g

= (1 − 0.7)(0.001157) + (0.7)(0.12736)

= 0.0895 m3/kg

TABLES OF THERMODYNAMIC PROPERTIES

Tables of thermodynamic properties of many substances are available, and in
general, all these tables have the same form. In this chapter we will refer to the steam
tables. Steam tables are most important for any thermodynamic calculations where
properties of steam are used. Steam tables was selected because steam is used
extensively in power plants and industrial processes. Once the steam tables are
understood, other thermodynamic tables can be readily used.

Several different versions of steam tables have been published over the years.
This chapter will utilize the Steam Tables by Keenan, Keyes, Hill, and Moore,
published in 1969 and 1978. The liquid-vapor saturation region presented in Table 1
is based according to the values of temperature (T). Similarly, the liquid-vapor
saturation region presented in Table 2 is based according to the values of pressure
(p). The superheated-vapor and the compressed-liquid regions are shown in Table 3
and Table 4, respectively. Critical region is displayed in Table 5.

Table 1 lists the values of saturation pressure, specific volume of saturated

liquid (f) and specific volume of saturated vapor (g) corresponding to saturation
temperature. The table also includes the values of internal energy of saturated liquid
(uf) and internal energy of saturated vapor (ug), enthalpy of saturated liquid (hf) and
enthalpy of saturated vapor (hg), entropy of saturated liquid (sf) and entropy of
saturated vapor (sg).

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 Table 2 is similar to Table 1 except that all values are listed corresponding to
saturation pressure.

Superheated vapor is a state wherein a pressure is lower than the saturation

pressure for a given temperature or has a higher temperature when compared to the
saturated state at the same pressure. Table 3 can be used to find the properties of
superheated water vapor corresponding to saturation pressure and superheated
temperature. In this table, group of data are displayed for several pressures
corresponding to temperatures. Data are arranged for the properties beginning with
specific volume, internal energy, enthalpy, and entropy.

Conversely, compressed liquid is a state wherein a pressure is higher than the

saturation pressure for a given temperature or has a lower temperature when
compared to the saturated state at the same pressure. Table 4 can be used to find the
properties of compressed liquid for water. The set-up is the same as of Table 3.

Example 11.2
Determine the phase for each of the following water states using the Steam
Tables and indicate the relative position in the p– and T– diagrams.
a) 120oC, 500 kPa
b) 120oC, 0.5 m3/kg

Solution:
a) Using Table 1 (values in bracket are taken from CATT2)
At 120oC, the saturation pressure is 198.53 kPa [198.5 kPa]. Since p > psat
then the state is compressed liquid. See point a of figure 11-5.

Or using Table 2 (values in bracket are taken from CATT2)

At 500 kPa, the saturation temperature is 151.86oC [151.9oC]. Since t < tsat
then the state is compressed liquid.

b) Using Table 1 (values in bracket are taken from CATT2)

At 120oC
f = 0.00106 m3/kg [0.00106 m3/kg]
g = 0.8919 m3/kg [0.8919 m3/kg]

Since f <  < g , then the state is at two phase mixture of liquid and
vapor. See point b of figure 11-5.

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 Fig 11-5

Example 11.3
Determine the enthalpy and specific volume of steam at 500 kPa and 300oC.

Solution:

Using Table 3 (values in bracket are taken from CATT2), the properties can be
determined in superheated region because the temperature of steam, 300oC,
is greater than the saturated steam temperature, 151.86oC, corresponding to
500 kPa. Proceed to the 500 kPa columns and find a temperature of 300oC. At
this line, the values of h and  are 3064.2 kJ/kg [3064 kJ/kg] and 0.5226 m3/kg
[0.5226 m3/kg], respectively.

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Example 11.4
Find the enthalpy and specific volume of steam at 250 kPa and x = 50%.

Solution:

Using Table 2 (values in bracket are taken from CATT2), determine the
saturated liquid and saturated vapor values for the enthalpy and specific
volume at 250 kPa.
hf = 535.37 kJ/kg [535.3 kJ/kg]
hfg = 2181.5 kJ/kg
hg = 2716.9 kJ/kg [2717 kJ/kg]

f = 0.001067 m3 /kg [0.001067 m3/kg]

g = 0.7187 m3 /kg [0.7187 m3/kg]

h = hf + x hfg
= 535.37 + (0.5)(2181.5)
= 1626.12 kJ/kg

 = (1‒ x)f + x g
= (1 − 0.5)(0.001067) + (0.5)(0.7187)
= 0.35988 m3 /kg

COMPUTER-AIDED THERMODYNAMICS TABLES

Computer-Aided Thermodynamic Tables 2 (CATT2) provide a means to access
various thermodynamic tables normally found in text or reference books. There is no
need to interpolate values from a table. Simply enter a property value you want to

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evaluate, and let the computer do the work. The latest version is CATT3. The good
thing here is the software is a Windows application, so it is more user friendly. As a
state is selected and the properties are computed, a thin crosshair set of lines
indicates the state in the p-, T-, or T-s diagrams so that this can be seen with a
visual impression of the state’s location.

The CATT2 screen is divided into an upper and lower section. The upper
section displays the values last evaluated and, in some cases, a graphical
representation of those values. The lower section contains a spreadsheet-like log of
all previous values evaluated for a particular substance. The sections are separated
by a draggable bar, which allows you to view more or less of each section.

You can evaluate all the tables using one of four predefined sets of units. You
can select units prior to performing any calculations, using Change Units from the
menu or clicking the Units button. The tables are grouped as follows:

 Water
 Refrigerants
 Cryogenics
 Air
 Ideal Gases
 Compressibility
 Psychrometric Chart

You can access each group by clicking on the corresponding tabs, at the bottom
of the display, or by selecting the group from the Tables menu.

REVIEW PROBLEMS
1. Determine the following properties for water:
a)  in cubic meters per kilogram at x = 1.0, p = 150 kPa
b) u in kilojoules per kilogram at T = 150oC, x = 0.5
c) h in kilojoules per kilogram at T = 440oC, p = 20 MPa
d) h in kilojoules per kilogram at p = 0.9 MPa, saturated liquid

2. State the phase or phases of water that may exist at the given states:
a) T = 215oC, p = 2.0 MPa
b) T = 215oC, p = 2.2 MPa
c) T = 240oC, x = 0.4
d) T = 260oC,  = 0.40 m3/kg
e) p = 30 kPa, T = 75oC
f) p = 50 kPa,  = 2 m3/kg

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3. A tank contains 1 kg of liquid water and 0.1 kg of water vapor at 200oC. Determine the
following properties:
a) The quality of the water
b) The total volume of the container
c) The volume occupied by the liquid
d) The pressure of the water
[ans: b) 0.01389 m3]

4. A container with a volume of 4 m3 is filled with water at a pressure of 0.30 MPa and a
temperature of 500oC. Determine the mass of the water in the container.
[ans: 3.37 kg]

5. Complete this table for water.

T (oC) p (kPa)  (m3/kg) Phase Description
50 4.16
200 Saturated vapor
250 400
110 600

6. Complete this table for water.

T (oC) p (kPa) h (kJ/kg) x Phase Description
200 0.7
140 1800
950 0.0
80 500
800 3162.2

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