Bahir Dar University

Bahir Dar Institute of Technology

Engineering Thermodynamics (Meng 3081)

For Industrial Engineering

Chapter 3: Pure Substances

 Outlines
 Properties of Pure Substances
 Equilibrium mixture of vapor-liquid-phase and Phase
Diagrams
 Independent properties of pure substances
 Thermodynamic property tables
 Equation of state
 Properties of pure substances
 A substance that has a fixed chemical composition throughout is called a
pure substance.

 A pure substance is one that is uniform and invariable in chemical

composition.

 A pure substance can exist in more than one phase, but its chemical
composition must be the same in each phase.
 A pure substance does not have to be of a single chemical
element or compound, however. A mixture of various
chemical elements or compounds also qualifies as a pure
substance as long as the mixture is homogeneous.

 Air, for example, is a mixture of

several gases, but it is often
considered to be a pure substance
because it has a uniform chemical
composition (Fig. 3–1).
 • 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
(Fig. 3–2).
A mixture of ice and liquid water,
for example, is a pure substance
because both phases have the same
chemical composition(H2O).
A mixture of liquid air and gaseous air, however, is not a
pure substance since the composition of liquid air is different
from the composition of gaseous air, and thus the mixture is
no longer chemically homogeneous. This is due to different
components in air condensing at different temperatures at a
specified pressure.

Similarly, a mixture of oil and water is not a pure substance.

Since oil is not soluble in water, it will collect on top of the
water, forming two chemically dissimilar regions.
 Phases of a pure substance
The molecules in a solid are arranged in a three-
dimensional pattern. the molecules in a solid cannot
move relative to each other, they continually oscillate
about their equilibrium positions.

The molecular spacing in the liquid phase is not much

different from that of the solid phase, except the
molecules are no longer at fixed positions relative to
each other and they can rotate and translate freely.

In the gas phase, the molecules are far apart from each other, and a molecular
order is nonexistent. Gas molecules move about at random, continually colliding
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 the liquid or solid
phases.
Equilibrium Mixture of Vapor Liquid phase and Phase diagrams

• Phase-change processes of pure substances

 There are many practical situations where two phases of a pure substance
coexist in equilibrium.
 Water exists as a mixture of liquid and vapor in the boiler and the
condenser of a steam power plant.
 Even though many home owners consider the freezing of water in
underground pipes as the most important phase-change process, attention
in this section is focused on the liquid and vapor phases and their mixture.
 As a familiar substance, water is used to demonstrate the basic principles
involved. Remember, however, that all pure substances exhibit the same
general behavior.
 Compressed Liquid or a subcooled liquid

At 1 atm and 20°C, water exists in the liquid phase.

A substance that is not about to vaporize is

called compressed Liquid/subcooled liquid.
Note: all pure substances exhibit the same general
behavior.
 Saturated Liquid
 As more heat is transferred, the
temperature keeps rising until it reaches
100°C. At this point water is still a liquid,
but any heat addition will cause some of
the liquid to vaporize. That is, a phase
change process from liquid to vapor is
about to take place.
 A liquid that is about to vaporize is called
Saturated Liquid
 Saturated Vapor

Once boiling starts, the temperature

stops rising until the liquid is completely
vaporized. That is, the temperature will
remain constant during the entire phase-
change process if the pressure is held
constant.

Midway about the vaporization line, the cylinder contains

equal amounts of liquid and vapor (mixture).
 As we continue transferring heat, the vaporization
process continues until the last drop of liquid is
vaporized (state 4).

 At this point, the entire cylinder is filled with vapor

that is on the borderline of the liquid phase. Any
heat loss from this vapor will cause some of the
vapor to condense (phase change from vapor to
liquid)

 A vapor that is about to condense is called

Saturated Vapor
 Saturated Liquid Vapor Mixture
 A substance at states between 2 and 4 is referred to as
a saturated liquid–vapor mixture since the liquid and
vapor phases coexist in equilibrium at these states.
 Superheated Vapor
 Further transfer of heat results in an increase in
both the temperature and the specific volume.
 At state 5, the temperature of the vapor is, let us
say, 300°C; and if we transfer some heat from
the vapor, the temperature may drop somewhat
but no condensation will take place as long as
the temperature remains above 100°C (for P 1
atm).
 A vapor that is not about to condense (i.e., not a saturated vapor) is
called superheated vapor.
 Saturation Temperature and Saturation Pressure
 Mostly we say “water boils at 100°C”, which is incorrect
statement.
 At a given pressure, the temperature at which a pure substance
changes phase is called the saturation temperature Tsat.
 Likewise, at a given temperature, the pressure at which a pure
substance changes phase is called the saturation pressure Psat.
 The correct statement is “water boils at 100°C at 1 atm
pressure.”
 At a pressure of 101.325 kPa, Tsat is 99.97°C.
 Conversely, at a temperature of 99.97°C, Psat is 101.325 kPa. (At
100.00°C, Psat is 101.42 kPa)
 Latent Heat
 The amount of energy absorbed or released during a phase-change
process is called the latent heat.
 More specifically, the amount of energy absorbed during melting is
called the latent heat of fusion and is equivalent to the amount of
energy released during freezing. Similarly, the amount of energy
absorbed during vaporization is called the latent heat of vaporization
and 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 vaporization is 2256.5 kJ/kg.
• During a phase-change process, pressure and temperature are obviously
dependent properties, and there is a definite relation between them, that is,
Tsat = f (Psat)

• A plot of Tsat versus Psat, such as the one given for water in is called a liquid–
vapor saturation curve. A curve of this kind is similar in characteristic of all
pure substances.
• It is clear from Fig. 3–12 that Tsat increases with Psat.
• Thus, a substance at higher pressures boils at higher temperatures .
• In the kitchen, higher boiling temperatures mean shorter cooking times and
energy savings. A beef stew, for example, may take 1 to 2 h to cook in a regular
pan that operates at 1 atm pressure, but only 20 min in a pressure cooker
operating at 3 atm absolute pressure (corresponding boiling temperature: 134°C).
• The atmospheric pressure, and thus the boiling temperature of water,
decreases with elevation.
• Therefore, it takes longer to cook at higher altitudes than it does at sea level
(unless a pressure cooker is used). For example, the standard atmospheric
pressure at an elevation of 2000 m is 79.50 kPa, which corresponds to a boiling
temperature of 93.3°C as opposed to 100°C at sea level (zero elevation).
Some Consequences of Tsat and Psat Dependence
We can control the boiling temperature of a substance by simply
con-trolling the pressure, and it has numerous applications in
practice.
• N2 test chamber in superconductivity, cryogenics
• Vacuum cooling for leafy vegetable storage
• Vacuum freezing
• Package icing
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.
 The T-v Diagram
• The phase-change process of water at 1 atm pressure was described in detail
in the last section and plotted on a T-v diagram.
• Now let us repeat this process at different pressures to develop the T-v
diagram.
• Let us add weights on top of the piston until the pressure inside the cylinder
reaches 1 MPa.
• At this pressure, water has a somewhat smaller specific volume than it does
at 1 atm pressure. As heat is transferred to the water at this new pressure, the
process follows a path that looks very much like the process path at 1 atm
pressure, as shown in Fig. 3–16, but there are some noticeable differences. d
 First, water starts boiling at a much higher temperature (179.9°C) at
this pressure.
 Second, the specific volume of the saturated liquid is larger and the
specific volume of the saturated vapor is smaller than the
corresponding values at 1 atm pressure.

That is, the horizontal line that connects the saturated
liquid and saturated vapor states is much shorter.
 As the pressure is increased further, this saturation line continues to
shrink and it becomes a point when the pressure reaches 22.06 MPa
for the case of water.

This point is called the critical

point, and it is defined as the
point at which the saturated
liquid and saturated vapor
states are identical.
 The temperature, pressure, and specific volume of a substance at the critical
point are called, respectively, the critical temperature Tcr, critical pressure
Pcr, and critical specific volume vcr. The critical-point properties of
water are Pcr 22.06 MPa, Tcr 373.95°C, and vcr 0.003106 m /kg.3

 At pressures above the critical pressure, there is not a distinct phase change
process (Fig. 3–17).

 Instead, the specific volume of the

substance continually increases, and at
all times there is only one phase
present. Eventually, it resembles a
vapor, but we can never tell when the
change occurred.
• Above the critical state, there is no line that separates the
compressed liquid region and the superheated vapor region.
• However, it is customary to refer to the substance as superheated
vapor at temperatures above the critical temperature and as
compressed liquid at temperatures below the critical temperature.
• The saturated liquid states can be connected by a line called the
saturated liquid line, and saturated vapor states in the same
figure can be connected by another line, called the saturated
vapor line.
• These two lines meet at the critical point, forming a dome.
• All the compressed liquid states are located in the region to the
left of the saturated liquid line, called the compressed liquid
region.

• All the superheated vapor states are located to the right of the
saturated vapor line, called the superheated vapor region. In
these two regions, the substance exists in a single phase, a
liquid or a vapor.

• All the states that involve both phases in equilibrium are

located under the dome, called the saturated liquid–vapor
mixture region, or the wet region.
 The P-v Diagram
• The general shape of the P-v diagram of a pure substance is very much like
the T-v diagram, but the T constant lines on this diagram have a downward
trend.
• Consider again a piston–cylinder device that contains liquid water at 1
MPa and 150°C. Water at this state exists as a compressed liquid. Now the
weights on top of the piston are removed one by one so that the pressure
inside the cylinder decreases gradually.
• The water is allowed to exchange
heat with the surroundings so its
temperature remains constant.
 As the pressure decreases, the volume of the water increases slightly.
 When the pressure reaches the saturation-pressure value at the specified
temperature (0.4762 MPa), the water starts to boil.
 During this vaporization process, both the temperature and the pressure
remain constant, but the specific volume increases. Once the last drop of
liquid is vaporized, further reduction in pressure results in a further increase in
specific volume.
 Notice that during the phase-change process, we did not remove any weights.
Doing so would cause the pressure and therefore the temperature to drop
[since Tsat = f (Psat)], and the process would no longer be isothermal.
 When the process is repeated for other temperatures, similar paths are
obtained for the phase-change processes. Connecting the saturated liquid
and the saturated vapor states by a curve, we obtain the P-v diagram of a
pure substance.
Extending the Diagrams to Include the Solid Phase
• These diagrams can easily be extended to include the solid phase as well as the
solid–liquid and the solid–vapor saturation regions.
• Most substances contract during a solidification (i.e., freezing) process.
Others, like water, expand as they freeze.
• We are all familiar with two phases being in equilibrium, but under some
conditions all three phases of a pure substance coexist in equilibrium.
• On P-v or T-v diagrams, these triple-phase states form a line called the triple
line. The triple line of a substance have the same pressure and temperature but
different specific volumes. The triple line appears as a point on the P-T
diagrams and, therefore, is often called the triple point. For water, the triple-
point temperature and pressure are 0.01°C and 0.6117 kPa, respectively.
 Water

For Substances contract while freezing For Substances expand while freezing

At triple point
(0.01°C and 0.6117
kPa) 3 phases of
water coexist
together
The P-T diagram
• This diagram is often called the phase diagram since all three phases are
separated from each other by three lines.
• No substance can exist in the liquid phase The P-v-T surface
in stable equilibrium at pressures below
the triple-point pressure. There are two
ways a substance can pass from the solid Contract
to vapor phase: either it melts first into a
liquid and subsequently evaporates, or it
evaporates directly without melting first.
• Passing from the solid phase directly into
the vapor phase is called sublimation. For
substances that have a triple-point pressure
above the atmospheric pressure such as
Expand
solid CO2(dry ice), sublimation is the only
way to change from the solid to vapor
phase at atmospheric conditions.
 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.
Note: Total energy of a system in two groups:
Macroscopic and microscopic.
Internal Energy: The sum of all the microscopic forms
of energy is called the total internal energy of a system and
is denoted by U.
Enthalpy:
 In the analysis of certain types of processes (control volumes), particularly
in power generation and refrigeration, we frequently encounter the
combination of properties u and Pv. The pressure-volume term expresses
the work required to establish the system's physical dimensions, i.e. to
make room for it by displacing its surroundings.
 For the sake of simplicity and convenience, this combination is defined as a
new property, enthalpy, and given the symbol h:
 Saturated Liquid and Saturated Vapor States
The subscript f is used to denote
properties of a saturated liquid,
and the subscript g to denote the
properties of saturated vapor.
fg, denotes the difference between
the saturated vapor and saturated liquid
values of the same property. For example
 The quantity hfg is called the enthalpy of
vaporization (or latent heat of vaporization).
 It 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 increases and becomes zero
at the critical point.
 Saturated Liquid–Vapor Mixture
During a vaporization process, a
substance exists as part liquid and part
vapor. That is, it is a mixture of saturated
liquid and saturated vapor. To analyze
this mixture properly, we need to know
the proportions of the liquid and vapor
phases in the mixture. This is done by
defining a new property called the
Quality.
 Quality has significance for saturated mixtures only. It has no meaning
in the compressed liquid or superheated vapor regions. Its value is
between 0 and 1.
 The quality of a system that consists of saturated liquid is 0 (or 0
percent), and the quality of a system consisting of saturated vapor is 1
(or 100 percent).
 A saturated mixture can be treated as a combination of two subsystems:
the saturated liquid and the saturated vapor. However, the amount of mass
for each phase is usually not known. Therefore, it is often more convenient
to imagine that the two phases are mixed well, forming a homogeneous
mixture.
 Then the properties of this “mixture” will simply be the average
properties of the saturated liquid–vapor mixture under consideration.
Here is how it is done.
Consider a tank that contains a saturated liquid–vapor mixture. The
volume occupied by saturated liquid is Vf, and the volume occupied
by saturated vapor is Vg. The total volume V is the sum of the two.
Based on this equation, quality can be related to the horizontal
distances on a P-v or T-v diagram. At a given temperature or
pressure, the numerator of Eq. 3–5 is the distance between the
actual state and the saturated liquid state, and the denominator is
the length of the entire horizontal line that connects the saturated
liquid and saturated vapor states. A state of 50 percent quality lies
in the middle of this horizontal line.
 • The analysis given above can be repeated for
internal energy and enthalpy with the following
results:

All the results are of the same format, and they can be
summarized in a single equation as
• where y is v, u, or h. The subscript “avg” (for “average”) is
usually dropped for simplicity.
• The values of the average properties of the mixtures are
always between the values of the saturated liquid and the
saturated vapor properties .

That is,
 Superheated Vapor
• Since the superheated region is
a single-phase region (vapor
phase only), temperature and
pressure are no longer
dependent properties and they
can conveniently be used as the
two independent properties in
the tables.
 Compressed Liquid

• Compressed liquid tables are not commonly available.

• One reason for the lack of compressed liquid data is the
relative independence of compressed liquid properties
from pressure.
• Variation of properties of compressed liquid with
pressure is very mild. Increasing the pressure 100 times
often causes properties to change less than 1 percent.
• In the absence of compressed liquid data, a general
approximation is to treat compressed liquid as saturated
liquid at the given temperature.
• This is because the compressed liquid properties depend on
temperature much more strongly than they do on pressure.
Thus,
• Where y is v, u, or h. Of these three properties, the
property whose value is most sensitive to variations in the
pressure is the enthalpy h.
• Although the above approximation results in negligible
error in v and u, the error in h may reach undesirable levels.
• However, the error in h at low to moderate pressures and
temperatures can be reduced significantly by evaluating it
from
 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
thermodynamic properties. 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.
• For water, the state of saturated liquid at 0.01°C is taken as the
reference state, and the internal energy and entropy are assigned
zero values at that state.
• However, in thermodynamics concerned with the changes in
properties, and the reference state chosen is of no consequence in
calculations.
 The Ideal-gas Equation Of State
• Property tables provide very accurate information about the
properties, but they are bulky and vulnerable to typographical errors.
A more practical and desirable approach would be to have some
simple relations among the properties that are sufficiently general
and accurate. Any equation that relates the pressure, temperature, and
specific volume (other properties) of a substance is called an
equation of state. Among many, 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 customarily called a gas when it is above the
critical temperature. Vapor usually implies a gas that is not far from a
state of condensation.
• P and v are inversely proportional (Boyle), and T and v are directly
proportional at low pressures(Charles and Gay-Lussac).
→ Ideal-gas equation of state
, Ru is universal gas constant=
R is called the gas constant, P is P abs and T is Tabs(K), M is molar mass/molecular weight
• Molar mass is the mass of one mole of a substance in grams.
N is mole number

is the molar specific volume

• An ideal gas is an imaginary substance that obeys the relation Pv=RT.

• Dense gases such as water vapor in steam power plants and refrigerant
vapor in refrigerators, however, should not be treated as ideal gases.
Instead, the property tables should be used for these substances. At
pressures below 10 kPa (in air-conditioning applications), water vapor can
be treated as an ideal gas, regardless of its temperature, with negligible
error (less than 0.1 percent).
Compressibility Factor—a Measure Of Deviation From Ideal-gas
Behavior:
Gases deviate from ideal-gas behavior significantly at states near the saturation
region and the critical point. The deviation from ideal-gas behavior at a given
temperature and pressure can accurately be accounted for by the introduction
of a correction factor called the compressibility factor Z defined as:
• Gases follow the ideal-gas equation at low P
and high T0 relative to critical point
• Gases behave differently at given T and P,
but they behave very much the same at
temperatures and pressures normalized with
respect to their Tcr and Pcr. Example air at -
100oC N2 at -100oC are ideal.
• PR is called the reduced pressure and TR the
reduced temperature. The Z factor for all
gases is approximately the same at the same
reduced pressure and temperature.

When P,v or T,v are given instead of P,T

Pseudo-reduced specific volume is used.
Chart: Principle of corresponding states
Reading Ass.
Other equations of state
Van der Waals Equation of State
Beattie-Bridgeman Equation of State
Benedict-Webb-Rubin Equation of State
Virial Equation of state