EAT 231 : THERMODYNAMICS

CHAPTER 3
Properties of Pure Substances

By: Dr. Sara Yasina

Yusuf
 Course Outcome

CO1: Ability to determine pure

substance behaviour and its
properties at any given states
 Chapter Outline
1. Pure substances
2. Phase-change processes of pure
substances
3. Property diagrams for phase-change
processes
4. Property tables
5. The ideal-gas equation of state
6. Compressibility factor
7. Other equation of state
 Pure Substance
Pure substance: A substance that is
homogenous and has a fixed chemical
composition throughout.
Air is a mixture of several gases, but it is
considered to be a pure substance
 The molecules in a solid are kept at their positions by
the large spring-like inter-molecular forces.
In a solid, the attractive and repulsive forces between
the molecules tend to maintain them at relatively
constant distances from each other
 In this picture of a geyser in
Yellowstone National Park,
water is present as steam
from the geyser, as liquid
water in the pools, as snow
on the ground, and as ice.

Is the carbon dioxide (CO2) in a fire extinguisher a pure

substance?

Is the natural gas in a tank a pure substance?

Do the water and ice in a glass constitute a pure substance?

Is the compressed air in a tank a pure substance?

Phase-change Processes
of Pure Substances
Saturation Temperature: temperature at
which vaporization takes place at a given
pressure - Saturation Pressure

Constant-pressure change from liquid to vapor phase for a pure

substance
Phase-change Processes
of Pure Substances
Saturated liquid: A liquid that is about to vaporize;
exists as liquid at the saturation P and T
Compressed liquid (subcooled liquid): A
substance that it is not about to vaporize.

At 1 atm and 20C, water

exists in the liquid phase
(compressed liquid).

At 1 atm pressure and

100C, water exists as a
liquid that is ready to
vaporize (saturated
liquid).
 Saturated vapor: A vapor that is about to condense.
Saturated liquidvapor mixture: The state at which
the liquid and vapor phases coexist in equilibrium.
Superheated vapor: A vapor that is not about to
condense (i.e., not a saturated vapor).

As more heat is transferred,
part of the saturated liquid
vaporizes (saturated liquid
vapor mixture).
As more heat is
At 1 atm pressure, the transferred, the
temperature remains constant at temperature of the vapor
100C until the last drop of liquid starts to rise
is vaporized (saturated vapor). (superheated vapor).
If the entire process between state 1 and 5 described
in the figure 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.
T-v diagram for the
heating process of
water at constant
pressure.
Saturated Temperature and Saturated Pressure
The temperature at which water starts
boiling depends on the pressure;
therefore, if the pressure is fixed, so is
the boiling temperature.
Water boils at 100C 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.
The liquidvapor saturation curve
of a pure substance (numerical
values are for water).
 Latent heat: The amount of energy absorbed
or released during a phase-change process.
Latent heat of fusion: The amount of energy
absorbed during melting. It is equivalent to the
amount of energy released during freezing.
Latent heat of vaporization: The amount of
energy absorbed during vaporization and it is
equivalent to the energy released during
condensation.
The magnitudes of the latent heats depend on
the temperature or pressure at which the phase
change occurs.
At 1 atm pressure, the latent heat of fusion of
water is 333.7 kJ/kg and the latent heat of

Tsat f Psat
vaporization is 2256.5 kJ/kg.
The atmospheric pressure, and thus the boiling
temperature of water, decreases with elevation.
Some Consequences of Tsat and Psat Dependence

The variation of the

text temperature of
fruits and
vegetables with
pressure during
vacuum cooling
from 25C to 0C.

In 1775, ice was made by

evacuating the air space in
a water tank.
 Property Diagrams for
Phase-Change Processes
The variations of properties
during phase-change processes
are best studied and understood
with the help of property
diagrams such as the T-v, P-v,
and P-T diagrams for pure
substances.

T-v diagram of
constant-pressure
phase-change
processes of a pure
substance at various
pressures (numerical
values are for water).
 Phase-change Processes
of Pure Substances

T = 311.10C

T = 179.90C

d vapor
erheate
T = 99.60C Sup

T = 200C
 The T-v Diagram
saturated liquid line
saturated vapor line
compressed liquid region
text superheated vapor region
saturated liquidvapor
mixture region (wet region)

At supercritical
Critical point: The point pressures (P > Pcr), there
at which the saturated is no distinct phase-
liquid and saturated vapor change (boiling)
states are identical. process.
The P-v Diagram
Extending the Diagrams to Include the Solid Phase

text For water,

Ttp = 0.01C
Ptp = 0.6117 kPa

At triple-point pressure
and temperature, a
substance exists in
three phases in
equilibrium.
 Sublimation:
The P-T Diagram Passing from the
solid phase directly
into the vapor phase.
text

At low pressures
(below the triple-point
value), solids
evaporate without
melting first
(sublimation).
P-T diagram of pure substances.
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.
Nomenclature
A pure substance is a substance which is composed
of a single chemical species.
To specify the state of a pure substance two
independent and intensive properties are required.

1. If the temperature of the helium inside a balloon is

17oC, can its specific volume be determined?
2. If the temperature and the total volume (V, not
specific volume v) of the oxygen inside the tank are
known, can we determine the pressure of the
cylinder (i.e., does P = P(T,V))?
3. If the pressure of CO2 is smaller than Psat at a given
T, what is the phase?
CO2 phase diagram
 Property Tables
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.
 Enthalpy A combination Property

The product pressure

volume has energy units.
The combination u + Pv is
frequently encountered in
the analysis of control
volumes.
 Saturated Liquid and Saturated Vapor States
Table A4: Saturation properties of water
under temperature.
A partial list of Table A4. Table A5: Saturation properties of water
under pressure.
The subscript fg used in Tables A-4 and A-5
refers to the difference between the
saturated vapor value and the saturated
liquid value region

Enthalpy of vaporization, hfg (Latent heat of

vaporization): 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.
 Examples 3-1:
A rigid tank contains 50 kg of saturated liquid
water at 900C. Determine the pressure in the tank
and the volume of the tank.
Solution:
Saturation condition exists in the tank, thus the
pressure must be the saturation pressure at 900C.
P Psat @ 900 C 70.183 kPa
The specific volume of the saturated
liquid at at 900C.
v f @ 900 C 0.001036 m 3 / kg
Total volume of the tank:

Fig. 3-29

V mv 50 kg 0.001036 m 3 / kg
Schematic T- diagram 0.0518 m 3
 Examples 3-2:
A piston-cylinder device contains 0.06 m3 of saturated
water vapor at 350 kPa pressure. Determine the
temperature and the mass of the vapor inside the
cylinder.
Solution:
Saturation condition exists in the tank, thus the
temperature must be the saturation temperature at this
pressure T T 138.860 C
sat @ 350 kPa

Fig. 3-30 The specific volume of the saturated

Schematic P-v
diagram vapor at 350 kPa:
vg @ 350 kPa 0.52422 m 3 / kg
Total volume of the tank:
V mv
V 0.06 m 3
m 3
0.114 kg
v 0.52422 m / kg
 Examples 3-3:
A mass of 200 g of saturated liquid water is completely
vaporized at a constant pressure of 100 kPa.
Determine a) the volume change and b) the amount of
energy transferred to the water.
Solution:
Fig. 3-31
Schematic P-v Saturation condition exists in the tank, thus the
diagram temperature must be the saturation temperature at this
pressure fg vg v f 1.6941 0.001043
1.6931 m 3 kg
Thus,

V mv fg 0.2kg 1.6931 m 3 / kg 0.336 m 3
b)
mh fg 0.2kg 2257.5 kJ kg 451.5 kJ
 Saturated Liquid Vapor Mixture
Quality, x : The ratio of the mass of vapor to 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.
Temperature and pressure are
dependent properties for a mixture.

The relative
amounts of
liquid and
vapor phases
in a saturated
mixture are
specified by the A two-phase system can be treated
quality x. as a homogeneous mixture for
convenience.
 masssaturated vapor mg
x
masstotal m f mg

We note that the total volume V is

V V f Vg mv m f v f mg v g
m m f mg mf v f mg v g
V mv , V f m f v f , Vg mg v g v
m m

Recall the definition of quality x mg mg

x
Then m m f mg
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
 y v, u, or h.
y yf
x
y fg

The Lever Rule is illustrated in the following figures.

 Examples 3-4:
A rigid tank contains 10 kg of water at 900C. If 8 kg of
the water is in liquid form and the rest is in the vapor
form, determine: a) the pressure in the tank and b) the
volume of the tank.
Solution:
The 2 phases, saturated liquid-vapor mixture
coexist in equilibrium, pressure must be the
saturation pressure at given temperature
Thus, PP 0 70.183 kPa
sat @ 90 C

V V f Vg m f v f m g f g

8 kg 0.001036 m 3 / kg 2 kg 2.3593 m 3 / kg
4.73 m 3

Average speific volume and total volume:

mg
Fig. 3-36 x ; v v f vg
Schematic T- diagram mtotal
 Examples 3-4:
An 80-L vessel contains 4 kg of refrigerant-134a at a pressure
of 160 kPa. Determine a) the temperature, b) the quality, c) the
enthalpy, and d) the volume occupied by the vapor phase
Solution:
At this point we did not know whether the
refrigerant is in the compressed liquid,
saturated mixture or superheated region.
So, need to compare v with vf and vg.
V 0.080 m 3
v 0.02 m 3 kg
m 4 kg
v f 0.0007437 m 3 kg ; v g 0.12348 m 3 kg ;
T Tsat @160 kPa 15.600 C
b) quality: v vf
x 0.157
v fg

Fig. 3-37 c) enthalpy, h = hf + xhfg

Schematic P- diagram
d) volume, V = mgvg =0.0775 m3
 Superheated Vapor

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.
Compared to saturated vapor, superheated
vapor is characterized by
 A partial
listing of
Table A6.

At a specified
P, superheated
vapor exists at
a higher h than
the saturated
vapor.
Examples 3-6:
Determine the internal energy of water at 200 kPa and 3000C

Solution:
At 200 kPa, Tsat = 120.10C, so T > Tsat
Since the water is in the superheated vapor region, so the
internal energy is determined from the superheated vapor
table (Table A-6).

Examples 3-6:
Determine the temperature of water at a state of P = 0.5 MPa
and h = 2890 kJ/kg

Solution:
At 0.5 MPa, hg = 2748 kJ/kg, so h > hg
Interpolate T between 200 and 2500C
 Compressed Liquid
The compressed liquid properties depend on
temperature much more strongly than they do on
pressure. y v, u, or h

A more accurate relation for h

A compressed
liquid may be
approximated as Compressed liquid is characterized by
a saturated liquid
at the given
temperature.
Examples 3-8:
Determine the internal energy of compressed liquid water at
800C and 5 Mpa using data from:
a) Compressed liquid table
b) Saturated liquid data

And the error involved?

Solution:
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 0.01C and for R-134a is -40C 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.
 How to choose the right table?
The correct table to use to find the
thermodynamic properties of a real substance
can always be determined by comparing the
known state properties to the properties in the
saturation region.
Given the temperature or pressure and one
other property from the group v, u, h, and s, the
following procedure is used.
Some tables may not always give the internal
energy. When it is not listed, the internal
energy is calculated from the definition of the
enthalpy as
u h Pv
 For example if the pressure and specific volume are
specified, three questions are asked: For the given
pressure,
Is v v f ?
Is v f v v g ?
Is v g v ?
a. If the answer to the first question is yes, the state is in
the compressed liquid region, and the compressed
liquid tables are used to find the properties of the state.

b. If the answer to the second question is yes, the state is

in the saturation region, and either the saturation
temperature table or the saturation pressure table is
used to find the properties. Then the quality is
calculated and is used to calculate the other properties,
u, h, and s.

c. If the answer to the third question is yes, the state is in

the superheated region and the superheated tables
are used to find the other properties.
Example:
Determine the enthalpy of 1.5 kg of water contained in a
volume of 1.2 m3 at 200 kPa.

Solution
a. calculate the specific volume. Volume 12. m3 m3
v 0.8
mass 15
. kg kg
Using Table A-5 at P = 200 kPa,
vf = 0.001061 m3/kg , vg = 0.8858 m3/kg
b. Now:
Is v v f ?
Is v f v v g ?
Is v g v ?
We see that the state is in the two-phase or saturation
region. So we must find the quality x first.

v v f x (v g v f )
 v vf
x
vg v f
0.8 0.001061

0.8858 0.001061
0.903 (What does this mean?)

Then,

h h f x h fg
504.7 (0.903)(2201.6)
kJ
2492.7
kg
The Ideal-Gas Equation of State
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.
Ideal gas
equation of state

R: gas constant
Different substances
have different gas M: molar mass (kg/kmol)
constants. Ru: universal gas constant
 Mass = Molar mass Mole number

Ideal gas equation at two

states for a fixed mass

Various
expressions of
ideal gas
equation
Real gases behave as an ideal gas at low
densities (i.e., low pressure, high temperature).

Properties per unit mole are

denoted with a bar on the top.
 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, however, 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.
Percentage of error ([|vtable - videal|/vtable] 100) involved in assuming steam to be
an ideal gas, and the region where steam can be treated as an ideal gas with
less than 1 percent error.
Compressibility Factor A Measure of
Deviation from Ideal-Gas Behavior
The farther away Z is from unity, the more the gas
deviates from ideal-gas behavior.
Gases behave as an ideal gas at low densities
(i.e., 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.
Compressibility factor Z
A factor that accounts for the deviation of real
gases from ideal-gas behavior at a given
temperature and pressure.

49
 Reduced Reduced
pressure temperature
Pseudo-reduced Z can also be determined from
specific volume a knowledge of PR and vR.

Comparison of Z factors for various gases.

Examples 3-11:
Determine the specific volume of refrigerant-134a at 1MPa
and 500C, using
a) The ideal-gas equation of state and
b) The generalized compressibility chart. Compare the
values obtained to the actual value of 0.021796 m 3/kg
and determine the error involved in each case

Solution:
Table A-1 (pg 904) R 0.0815 kPa m 3 kg K
Pcr 4.059 MPa
Tcr 374.2 K

RT
c) Ideal-gas v 0.026325 m 3 / kg
P
d) Compressibility factor,
compressibility chart Fig A-15 (pg 928), find PR and TR
 Other Equations of State
Several equations have been proposed to
represent the P-v-T behavior of substances
accurately over a larger region with no limitations.

52
 Van der Waals Equation of State

This model includes two effects not considered in

the ideal-gas model: the intermolecular attraction
forces and the volume occupied by the
molecules themselves. The accuracy of the van
der Waals equation of state is often inadequate.

Critical isotherm of a pure

substance has an inflection
point at the critical state.
Beattie-Bridgeman Equation of State

The constants are given in Table 34 for various

substances. It is known to be reasonably accurate
for densities up to about 0.8cr.
 Benedict-Webb-Rubin Equation of State

RuT C0 1 bRuT a a c 2
P B0 RuT A0 2 2 6 3 2 1 2 e
T 3
T

The constants are given in Table 34. This equation can handle
substances at densities up to about 2.5 cr.

Virial Equation of State

The coefficients a(T), b(T), c(T), and so on, that are

functions of temperature alone are called virial coefficients.
 Complex equations of
state represent the P-v-
T behavior of gases
more accurately over a
Percentage of error involved in various equations of wider range.
state for nitrogen
(% error = [(|vtable - vequation|)/vtable] 100).