Chapter 2: Properties of Pure Substances

Pure Substance
A substance that has a fixed chemical composition throughout is called a pure
substance such as water, air, and nitrogen.
A pure substance does not have to be of a single element or compound. A mixture
of two or more phases of a pure substance is still a pure substance as long as the
chemical composition of all phases is the same.

Phases of a Pure Substance

A pure substance may exist in different phases. There are three principle phases’
solid, liquid, and gas.
A phase: is defined as having a distinct molecular arrangement that is
homogenous throughout and separated from others (if any) by easily identifiable
boundary surfaces.
A substance may have several phases within a principal phase, each with a
different molecular structure. For example, carbon may exist in as graphite or
diamond in the solid phase, and ice may exist in seven different phases at high
pressure.
Molecular bonds are the strongest in solids and the weakest in gases.
Solid: the molecules are arranged in a three-dimensional pattern (lattice)
throughout the solid. The molecules cannot move relative to each other; however,
they continually oscillate about their equilibrium position.
Liquid: the molecular spacing in liquid phase is not much different from that of the
solid phase (generally slightly higher), except the molecules are no longer at fixed
positions relative to each other.
Gas: the molecules are far apart from each other, and a molecular order does not
exist. Gas molecules move randomly, and continually collide each other and the
walls of the container they are in.
Molecules in the gas phase are at a considerably higher energy level than they are
in liquids or solid phases.

Phase-Change Processes of Pure Substances

Consider a process that a pure substance starts as solid and is heated up at
constant pressure until it all becomes as gas. Depending on the prevailing
pressure, the matter will pass through various phase transformations. At P0:
1. Solid
2. Mixed phase of liquid and solid

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3. Sub-cooled or compressed liquid (means it is not about to vaporize)
4. Wet vapor or saturated liquid-vapor mixture, the temperature will stop rising until
the liquid is completely vaporized.
5. Superheated vapor (a vapor that is not about to condense).

Fig. 2-1: T-V diagram for the heating process of a pure substance.
♦ At a given pressure, the temperature at which a pure substance starts boiling is
called the saturation temperature, Tsat.
♦ Likewise, at a given temperature, the pressure at which a pure substance starts
boiling is called the saturation pressure, Psat.
♦ During a phase-change process, pressure and temperature are dependent
properties, Tsat = f (Psat).
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♦ The critical point is the point at which the liquid and vapor phases are not
distinguishable
♦ The “triple point” is the point at which the liquid, solid, and vapor phases can
exist together. On P-v or T-v diagrams, these triple-phases states form a line
called the triple line.
Table 2-1: Critical and triple point for water and oxygen.

Critical Point Triple Point

P (atm) T (K /◦C) P (atm) T (K /◦C)

H2O 218 647.30/(374.14) 0.006 273.17 (0.01)

O2 50.136 154.80/(−118.36) 0.0015 54.16/(−219)

Vapor Dome
The general shape of a P-v diagram for a pure substance is very similar to that of a
T-v diagram.
P
critical point
SUPERHEATED
sat. vapor line VAPOR REGION

COMPRESSED
LIQUID
T2 = const. >T1
REGION
SATURATED
sat. LIQUID-VAPOR
liquid REGION T1 = const
line

Fig. 2-2: P-v diagram of a pure substance.

The P-T or Phase Change Diagram

This is called phase diagram since all three phases are separated from each other
by three lines. Most pure substances exhibit the same behavior.
♦ One exception is water. Water expands upon freezing.
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 Fig. 2-3: phase diagram of pure substances.
There are two ways that a substance can pass from solid phase to vapor phase i)
it melts first into a liquid and subsequently evaporates, ii) it evaporates directly
without melting (sublimation).
♦ the sublimation line separates the solid and the vapor.
♦ the vaporization line separates the liquid and vapor regions
♦ the melting or fusion line separates the solid and liquid.
♦ these three lines meet at the triple point.
ƒ if P<PTP , the solid phase can change directly to a vapor phase
ƒ at P<PTP the pure substance cannot exist in the liquid phase. Normally
(P>PTP ) the substance melts into a liquid and then evaporates.
ƒ matter (like CO2) which has a triple point above 1 atm sublimate under
atmospheric conditions (dry ice)
ƒ for water (as the most common working fluid) we are mainly interested
in the liquid and vapor regions. Hence, we are mostly interested in
boiling and condensation.

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Property Tables
For most substances, the relationships among thermodynamic properties are too
complex to be expressed by simple equations. Thus, properties are frequently
presented in the form of tables, see Table A-4.
The subscript “f” is used to denote properties of a saturated liquid and “g” for
saturated vapor. Another subscript, “fg”, denotes the difference between the
saturated vapor and saturated liquid values of the same property.
For example:
vf = specific volume of saturated liquid
vg = specific volume of saturated vapor
vfg = difference between vg and vf ( vfg = vg – vf)
Enthalpy: is a property defined as H = U + PV (kJ) or h = u + Pv (kJ/kg) (per mass
unit).
Enthalpy of vaporization (or latent heat): 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 increase, and becomes zero at the
critical point.

1- Saturated Liquid-Vapor Mixture

During vaporization, a mixture of part liquid part vapor exists. To analyze this
mixture, we need to know the proportions of the liquid and vapor in the mixture.
The ratio of the mass of vapor to the mass of the total mixture is called quality, x:
m vapor
x= m total = mliquid + m vapor = m f + m g
m total
Saturated liquid-vapor mixture is treated as a combination of two sub-systems (two
phases). The properties of the “mixture” are the average properties of the
saturated liquid-vapor mixture.
V = V f + Vg
mt v ave = m f v f + m g v g
m f = mt − m g → mt v ave = (mt − m g )v f + m g v g
dividing by m t
v ave = (1 − x )v f + xv g and x = m g / mt
v ave = v f + xv fg (m 3
/ kg )
or,
v ave − v f
x=
v fg

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 P critical point
or T

sat.
sat.
vapor
liquid
states
states
sat. vapor

sat. liquid

Fig. 2-4: The relative amounts of liquid and vapor phases (quality x) are used to
calculated the mixture properties.
Similarly,
u ave = u f + xu fg
have = h f + xh fg
Or in general, it can be summarized as yave = yf +x.yfg. Note that:
0 ≤ x ≤1
y f ≤ y ave ≤ y g

Remember: pressure and temperature are dependent in saturated mixture region.

Fig. 2.5: Quality defines only for saturated liquid-vapor mixture.

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Example 2-1: Saturated liquid-vapor mixture
A closed, rigid container of volume 0.5 m3 is placed on a hot plate. Initially the
container holds a two-phase mixture of saturated liquid water and saturated water
vapor at P1= 1 bar with a quality of 0.5. After heating, the pressure in the container
is P2=1.5 bar. Indicate the initial and final states on a T-v diagram, and determine:
a) the temperature, in °C, at each state.
b) the mass of vapor present at each state, in kg.
c) if heating continues, determine the pressure, in bar, when the container holds
only saturated vapor.
Solution:
Assumptions:
1. Water in the container is a closed system.
2. States 1, 2, and 3 are equilibrium states.
3. The volume of container remains constant.
Two independent properties are required to fix state 1 and 2. At the initial state, the
pressure and quality are known. Thus state 1 is known, as shown in the figure.
The specific volume at state 1 is found using the given quality:
v1 = v f 1 + x1 (v g1 − v f 1 )
From Table A - 5 at P = 1 bar
v1 = 0.001043 + 0.5 (1.694 − 0.001043) = 0.8475 m 3 / kg
At state 2, the pressure is known. Volume and mass remain constant during the
heating process within the container, so v2=v1. For P2= 1.5, Table A-5 gives vf2=
0.001053 and vg2=1.1593 m3/kg. Since
vf2 < v2 < vg2
State 2 must be in the two-phase region as well. Since state 1 and 2 are in the
two-phase liquid-vapor region, the temperatures correspond to the saturation
temperatures for the given. Table A-5:
T1 = 99.63 °C and T2 = 111.4 °C
To find the mass of water vapor present, we first find the total mass, m.
V 0 .5 m 3
m= = = 0.59kg
v 0.8475m 3 / kg
m g1 = x1 m = 0.5(0.59kg ) = 0.295kg

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 T

3
P2 = 1.5 bar
2

P1 = 1 bar

The mass of vapor at state 2 is found similarly using quality x2. From Table A-5, for
P2 = 1.5 bar, we have:
v −vf2
x2 =
vg 2 − v f 2
0.8475 − 0.001053
x2 = = 0.731
1.159 − 0.001053
mg 2 = 0.731 (0.59kg ) = 0.431 kg

If heating continued, state 3 would be on the saturated vapor line, as shown in on

the T-v diagram above. Thus, the pressure would be the corresponding saturation
pressure. Interpolating in Table A-5 at vg = 0.8475 m3 /kg, we get P3 = 2.11 bar.

2- Superheated Vapor
Superheated region is a single phase region (vapor only), temperature and
pressure are no longer dependent. See Table A-6 for superheated vapor
properties.
If T>> Tcritical or P<<Pcritical, then the vapor can be approximated as an “ideal gas”.

3- Compressed (or Sub-cooled) Liquid

The properties liquid are relatively independent of pressure (incompressible).
A general approximation is to treat compressed liquid as saturated liquid at the
given temperature.
y ≈ y f @T

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The property most affected by pressure is enthalpy. For enthalpy use the following
approximation:
h ≈ h f @ T + v f (P − Psat )

The Ideal-Gas Equation of State

Any equation that relates the pressure, temperature, and specific volume of a
substance is called an equation of state.
The simplest and best known equation of state for substances in the gas phase is
the ideal-gas equation of state.
Gas and vapor are often used as synonymous words. The vapor phase of a
substance is called a gas when it is above the critical temperature. Vapor usually
implies a gas that is not far from a state of condensation.
It is experimentally observed that at a low pressure the volume of a gas is
proportional to its temperature:
Pv = RT
Where R is the gas constant. The above equation is called the ideal-gas equation
of state (ideal gas relation). Since R is a constant, one can write:
P1v 1 P2 v 2
R= =
T1 T2
The constant R is different for each gas; see Table 2-3 in Cengel book.
Ru = 8.314 kJ / (kmol. K) is the universal gas constant, R = Ru /M.
The Molar mass, M: is defined as the mass of one mole of a substance (in gmole
or kgmol). The mass of a system is equal to the product of its molar mass M and
the mole number N:
m = MN (kg)
See Table A-1 for R and M for several substances.
An ideal gas is an imaginary substance that obeys the relation Pv = RT. It is
experimentally observed that the ideal gas closely approximate the P-v-T behavior
of real gases at low densities.
¾ in the range of practical interest, many familiar gases such as air, nitrogen,
oxygen, hydrogen, helium, argon, neon, and CO2 can be treated as ideal
gases with negligible error.
¾ water vapor (in general see Fig. 2-37 Cengel book), refrigerant vapor in
refrigerators should not be treated as ideal gases.
¾ water vapor at pressures below 10 kPa can be treated as an ideal gas,
regardless of temperature.

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Compressibility Factor
The assumption of ideal gas relation implies that:
¾ the gas particles take up negligible volume
¾ the intermolecular potential energy between particles is small
¾ particles act independent of one another
However, real gases deviate from ideal gas behavior. This deviation at given
temperature and pressure can be accurately accounted for by introduction of a
correction factor called the compressibility factor Z.
Pv
Z= or Pv = ZRT
RT
or Z = vactual / videal. Obviously, Z=1 for ideal gases.
Gases behave very much the same at temperatures and pressures normalized
with respect to their critical temperatures and pressures.
P T
PR = and TR =
Pcr Tcr
Here PR and TR are called the reduced pressure and temperature, respectively.
By curve-fitting all the data, the general compressibility chart is obtained which can
be used for all gases.

Fig. 2-6: Z factor, general compressibility chart.

Chapter 2, E&CE 309, Spring 2005.

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Majid Bahrami
From the Z chart, one can conclude:
¾ at very low pressure (PR <<1), the gases behave as an ideal gas regardless
of temperature
¾ at high temperatures (TR>2), ideal gas behavior can be assumed.
¾ the deviation is highest in the vicinity of the critical point.
Example 2-2: Ideal Gas
Determine the specific volume of R-134a at 1 MPa and 50°C, using (a) ideal gas
equation (b) the generalized compressibility chart. Compare the values obtained
with the actual value of 0.02171 m3/kg.
Solution:
From Table A-1, for R-134a, R = 0.0815 kPa.m3/(kg.K), Pcr = 4.067 MPa, and Tcr =
374.3 K
(a) Ideal gas equation of state

v=
RT
=
[ ]
0.0815 kPa.m 3 / (kg.K ) (323 K )
= 0.02632 m 3 / kg
P (1000 kPa )
Comparing with the tabulated value, using ideal gas equation one would get an
error of (0.02632-0.02171)/0.02171=0.212 or 21.2%.
(b) To determine the correction factor Z,
P 1MPa
PR = = = 0.246
Pcr 4.067 MPa
T 323K
TR = = = 0.863
Tcr 374.3K
From Fig. A-13, Z= 0.84. Thus,
v=Z videal = 0.84 (0.02632 m3/kg) =0.02211 m3/kg
The error is less than 2%.
Therefore, in the absence of exact tabulated data, the generalized compressibility
chart can be used with confidence.

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