PROPERTIES OF PURE SUBSTANCE

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 principal 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 as graphite or diamond in the solid
phase, and ice may exist in seven different phases at high pressure.
Note: 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 with 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 where a pure substance starts as a solid and is heated up at constant
pressure until it all becomes 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
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).

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 Fig. 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).
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 co-exist
together. On P-v or T-v diagrams, these triple-phase states form a line called the triple
line.

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 Table 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 50.13 154.80/(−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: 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. 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.
• If P < PTP , the solid phase can change directly to a vapor phase
• At P < PTP the pure substance cannot exist in the liquid phase. Normally (P > PTP)
the substance melts into a liquid and then evaporates.
• Matter (like CO2) which has a triple point above 1 atm sublimate under atmospheric
conditions (dry ice)
• 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.

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 Cengel book.

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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.
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= mtotal = mliquid + mvapor = 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. 4: The relative amounts of liquid and vapor phases (quality x) are used to calculate
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
Note: pressure and temperature are dependent in the saturated mixture region.

Fig.5: Quality defined only for saturated liquid-vapor mixture.

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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. 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 T or P)
• Higher internal energies (u > ug at a given T or P)
• Higher enthalpies (h > hg at a given T or P)

Note: If T >> Tcritical or P << Pcritical, then the vapor is called “gas” and can be
approximated as an “ideal gas”.

Compressed (or Sub-cooled) Liquid

The properties of a liquid are relatively independent of pressure (incompressible). In
general, a compressed liquid is characterized by:
• Higher pressures (P > Psat at a given T)
• Lower temperatures (T < Tsat at a given P)
• Lower specific volumes (v < vf at a given T or P)
• Lower internal energies (u < uf at a given T or P)
• Lower enthalpies (h < hf at a given T or P)
A general approximation is to treat compressed liquid as saturated liquid at the given
saturation temperature.
y ≈ y f @T

The property most affected by pressure is enthalpy. For enthalpy use the following
approximation:
h ≈ h f @ T + v f (P − Psat )
Note: Interpolation
Often the exact value of a required property cannot be found in property table. In such
occasions, linear interpolation should be used. That is to fit a line connecting the two
known points on either side of the desired value and then estimate the required value.
Assume that two known points are: (x1, y1) and (x2, y2) and we need to estimate the value
of y at point x. Using linear interpolation, we have:

where

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 Example
Determine the phase for each of the following water states using thermodynamics tables
and indicate the relative position in P-v and T-v diagrams.
a) 120°C and 500 kPa
b) 120°C and 0.5 m3/kg
Solution:
a) Enter Table A-4, Saturated Water - Temperature Table. The saturated pressure at
this temperature is 198.67 kPa, since P=500 kPa > 198.67 kPa, we have a
compressed liquid. We could also enter Table A-5, Saturated Water - Pressure
Table, with 500 kPa and found the saturation temperature as 151.83°C, since T =
120°C < 151.83°C, we have subcooled liquid.

b) Enter Table A-4 with 120°C and notice

0.001060 0.5 0.8913 /
So the state is a two phase mixture of liquid and vapor.

T °C P kPa

P = 500 kPa
a
500
a 198 T = 120C
120 P=198 kPa
b
b

v
v

Fig. 6: T-v and P-v diagrams for example 1.

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Example
A rigid vessel contains saturated vapor refrigerant R-134a at 20°C. Heat is transferred to
the system until the temperature reaches 40°C. What is the final pressure?
Solution:
Since the volume and the mass of the refrigerant do not change during this process, the
specific volume remains constant. From Table A-11, Saturated Refrigerant-134a –
Temperature Table, we have:
0.035969 /
Enter Table A-11 with 40°C, the saturated vapor specific volume reads vg@40C = 0.019952
< v2 = 0.035969 m3/kg, thus the final state is superheated vapor. Knowing temperature
and specific volume, we enter Table A-13, Superheated Refrigerant-134a, interpolating
between P = 0.6 and 0.7 MPa at T = 40°C, we find:
P2 = 0.658 MPa

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