Chapter 2

Engineering
Thermodynamics__________________________________________________________ _ AAiT
Chapter 2
Properties of Pure Substance
2.1 Pure substance
A substance that has a fixed chemical composition throughout is called a pure substance.
Example: - Water, nitrogen, air, helium, carbon dioxide etc
Pure substance may exist in different phases, but the chemical compositions is the same. For
example water made up of two atoms of hydrogen and one atom oxygen. It will have the same
composition when in ice, liquid and vapor forms.
2.2 Fixing the state of a simple pure substance

The number of properties required to fix the state of a system is given by the state postulates. The
state postulate for a simple pure substance state that, equilibrium state can be determined by
specifying any two independent intensive properties.
Phase of pure substances

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. 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.
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Engineering Thermodynamics__________________________________________________________ _ AAiT
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.
A phase is identified as having a distinct molecular arrangement that is homogenous throughout

and separated from the others by easily identifiable boundary surface.
Under different conditions a substance may appear in different phases. The three principal phases
are solid, liquid and gas.
Considering water, it can be exist as
 Pure solid phase (ice)

 Pure liquid phase
 Pure vapor phase (steam)
It can also exist as an equilibrium mixture of different phase.
Phase-change processes of pure substances

Consider the piston-cylinder device containing liquid water at 20 C and 1atm.
Under these conditions, water exists in the liquid phase, and it is called a
compressed liquid, or a sub cooled liquid.
As the temperature rises, the liquid water expands slightly, and so its specific
volume increases.
Figure 2.1 At 1 atm and 20°C, water exists in the liquid phase (compressed liquid).
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At this point water 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 about to vaporize is called saturated liquid.
Figure 2.2 At 1 atm pressure and 100°C, water exists as a liquid that is ready to vaporize
(saturated liquid).
Once boiling starts, the temperature stops rising until the liquid is
completely vaporized (it is a constant phase - change process at p-
constant).
During this process the only thing is change in volume.
At this stage liquid and vapor phase coexist in equilibrium and it is

called saturated liquid-vapor mixture.
Figure 2.3 As more heat is transferred, part of the saturated liquid vaporizes (saturated liquid–
vapor mixture).
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).
The vapor that is about to condense is called a saturated vapor.
Figure 2.4 At 1 atm pressure, the temperature remains constant at 100°C until the last drop of
liquid is vaporized (saturated vapor).
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At this stage the phase-change process is completed is completed, we back to

a single-phase region (vapor).
Further transfer of heat will result in an increase in both the temperature and
the specific volume.
A vapor that is not about to condense (i.e. not a saturated vapor) is called a
superheated vapor.
Figure 2.5 As more heat is transferred, the temperature of the vapor starts
to rise (superheated vapor).
The above process is shown on a T-V diagram at constant pressure.
Figure 2.6 T- diagram for the heating process of water at constant pressure
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. 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.
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Table 2.1 Saturation (boiling) pressure of water at various temperatures
The amount of energy absorbed or released during a phase-change process is called the latent heat.
The amount of energy absorbed during vaporization is called the latent heat of vaporization and
it is equivalent to the energy released during condensation. The amount of energy absorbed during
melting is called the latent heat of fusion and it is equivalent to the amount of energy released
during freezing.
During a phase-change process, pressure and temperature are obviously dependent properties
T f P
Figure 2.7 The liquid vapor saturation curve of a pure substance
2.3 P-V-T diagram

The variation of properties during phase-change process are best studies and understood with the
help of property diagram. These diagrams can be three dimensional representations as (P-V-T)
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surface diagram or two dimensional representations as T-P, P-V and T-V diagrams which are
determined experimentally.
Figure 2.8 P–V–T surface and projections for a substance that expands on freezing. (a) Three-
dimensional view. (b) Phase diagram. (c) p–v diagram.
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Figure 2.9 P–V–T surface and projections for a substance that contracts on freezing. (a) Three-
dimensional view. (b) Phase diagram. (c) p–v diagram.
2.4 The T-V diagram

Experimental result tells us, as the pressure is increased further, the saturation line of the process
will continue to get shorter and it will become a point. This point is called the critical point of the
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substance and it may be defined as the point at which the saturated liquid saturated vapor states
are identical.
Figure 2.10 T-v diagram of constant-pressure phase-change processes of a pure substance at

various pressures (numerical values are for water).
At pressures above the critical pressure, there is not a distinct phase-change process. 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 has 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.
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Figure 2.11 T-V diagram of a pure substance.
The P-V diagram

It is the same as T-V diagram but the T-constant line on this diagram have a down ward trend
Figure 2.12 P-V diagram of a pure substance.
The P-T diagram

This diagram is often called the phase diagram since all three phases are separated from each other
by three lines.
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Figure 2.13 P-T diagram of pure substances.
Melting and Sublimation

Although the phase change from liquid to vapor (vaporization) is the one of principal interest in
this book chapter, it is also instructive to consider the phase changes from solid to liquid (melting)
and from solid to vapor (sublimation). To study these transitions, consider a system consisting of
a unit mass of ice at a temperature below the triple point temperature.
Figure 2.14 Phase diagram for water
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Let us begin with the case where the system is at state a of Fig. 2.14, where the pressure is greater
than the triple point pressure. Suppose the system is slowly heated while maintaining the pressure
constant and uniform throughout. The temperature increases with heating until point b on Fig. 2.14
is attained. At this state the ice is a saturated solid. Additional heat transfer at fixed pressure results
in the formation of liquid without any change in temperature. As the system is heated further, the
ice continues to melt until eventually the last bit melts, and the system contains only saturated
liquid. During the melting process the temperature and pressure remain constant. For most
substances, the specific volume increases during melting, but for water the specific volume of the
liquid is less than the specific volume of the solid. Further heating at fixed pressure results in an
increase in temperature as the system is brought to point c on Fig. 2.14. Next, consider the case
where the system is initially at state a of Fig. 2.14, where the pressure is less than the triple point
pressure. In this case, if the system is heated at constant pressure it passes through the two-phase
solid–vapor region into the vapor region along the line a  b  c shown on Fig. 2.14. The case of
vaporization discussed previously is shown on Fig. 2.14 by the line a  b  c .
2.4 Thermodynamic tables

Thermodynamic properties of substance are usually given in tabular form to facilitate calculation.
Among them saturated, superheated steam and compressed liquid are the most frequently used
properties.
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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 (x) as the ratio of the mass of vapor to the total mass of the mixture:
mvapor
x (2.1)
mtotal
Where mtotal  mliquid  mvapor  m f  mg (2.2)
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). In saturated mixtures, quality can serve as one of the two independent intensive
properties needed to describe a state. Note that the properties of the saturated liquid are the same
whether it exists alone or in a mixture with saturated vapor. During the vaporization process,
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only the amount of saturated liquid changes, not its properties. The same can be said about a
saturated vapor.
Figure 2.15 Liquid and vapor phases in a saturated mixture

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. (The subscript f is used to denote saturated liquid and the subscript g is used to denote
saturated vapor).
V  V f  Vg (2.3)
But V  mv
mtot vavr  m f v f  mg vg (2.4)
But m f  mtot  mg
mtot vavr  ( mtot  mg )v f  mg vg (2.5)
Dividing by mtot
vavr  (1  x )v f  xvg (2.6)
Since x = mg /mt and vfg is the difference between vg and vf (that is, vfg = vg - vf ). This relation can
also be expressed as
vavg  v f  xv fg (m3/kg) (2.7)

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Solving for quality, we obtain

vavg  v f
x (2.8)
v fg
The above equation also holds true for other properties
Internal energy: u  u f  xu fg (2.9)
Enthalpy: h  h f  xh fg (2.10)
Entropy: s  s f  xs fg (2.11)
Saturated Liquid and Saturated Vapor States

The properties of saturated liquid and saturated vapor for water are listed in Thermodynamics
tables
Figure 2.16 A partial list of Thermodynamic Table
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Superheated steam table

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. 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.
We have super heated steam table, where T and P are given and the other properties can be
tabulated (can be directed read from table).
Figure 2.17 Super heated region in graph and table form
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 P or T)
Higher internal energies (u > ug at a given P or T)
Higher enthalpies (h > hg at a given P or T)
Compressed liquid table
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Here again, the properties are given without subscripts. Pressure and temperature need to be known
to use these tables. Compressed liquid tables are not as commonly available this is because the
compressed liquid properties depend on temperature much more strongly than they do on pressure.
In the absence of compressed liquid data, a general approximation is to treat compressed liquid
as saturated liquid at the given temperature.
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 P or T)
Lower internal energies (u < uf at a given P or T)
Lower enthalpies (h < hf at a given P or T)
Figure 2.18 Compressed liquid region
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
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following procedure is used. 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  vg ?
Is vg  v ?
The answer to one of these questions must be yes. 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. 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. 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.
2.5 Equation of State

The relationship among the state variables, temperature, pressure, and specific volume is called
the equation of state.
Property relations that involve other properties of a substance at equilibrium states are also referred
to as equations of state. There are several equations of state, some simple and others very complex.
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.
Based on our experience in chemistry and physics we recall that the combination of Boyle’s and
Charles’ laws for gases at low pressure result in the equation of state for the ideal gas as
T 
P  R  (2.12)
v
It is given by:
Pv  RT , PV  mRT  nMRT (2.13)
Where:
P =Absolute Pressure, KPa
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V =Volume, m3
T =Absolute Temperature, K
R =Gas Constant. KJ/Kg∙K
M =Molecular Weight, Kg/Kmol
n =Number of Mole
The constant of proportionality R is called the gas constant. Equation (2.12) is called the ideal-
gas equation of state, or simply the ideal-gas relation, and a gas that obeys this relation is called
an ideal gas.
The gas constant R is different for each gas and is determined from
Ru
R (kJ / kg .K ) (2.14)
M
Where Ru is the universal gas constant and M is the molar mass (also called molecular weight)
of the gas. The constant Ru is the same for all substances, and its value is8.314KJ/Kmol∙K
m  nM (2.15)
The ideal-gas equation of state can be written in several different forms
V  mv  PV  mRT (2.16)
mR  (MN ) R  NRu  PV  NRuT (2.17)
V  Nv  Pv  RuT (2.18)
By writing Eq. 2.16 twice for a fixed mass and simplifying, the properties of an ideal gas at two
different states are related to each other by
PV PV
1 1
 2 2 (2.19)
T1 T2
Air, nitrogen, oxygen, hydrogen, helium, argon etc can be treated as ideal gases.
Compressibility factor (measure of deviation from ideal gas)

The ideal-gas equation is very simple and thus very convenient to use. However, gases deviate
from ideal-gas behavior significantly at states near the saturation region and the critical point. This
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
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PV  ZRT (2.20)
Z = 1 for ideal gases. For real gases Z can be greater than or less than unity. The Z factor is
approximately the same for all gases at the same reduced temperature and reduced pressure. This
is known as the principle of corresponding states.
P T
PR  and TR  (2.21)
Pcr Tcr
Where:
PR=reduced pressure
Pcr=critical pressure
T=actual pressure
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Figure 2 19 Comparison of Z factor for various gases
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Figure 2.20 Simple fluid compressibility chart
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Engineering

2.2 Fixing the state of a simple pure substance

Phase of pure substances

A phase is identified as having a distinct molecular arrangement that is homogenous throughout

Considering water, it can be exist as

 Pure solid phase (ice)

It can also exist as an equilibrium mixture of different phase.

Phase-change processes of pure substances

A liquid about to vaporize is called saturated liquid.

During this process the only thing is change in volume.

At this stage liquid and vapor phase coexist in equilibrium and it is

The vapor that is about to condense is called a saturated vapor.

At this stage the phase-change process is completed is completed, we back to

Table 2.1 Saturation (boiling) pressure of water at various temperatures

Figure 2.7 The liquid vapor saturation curve of a pure substance

2.3 P-V-T diagram

2.4 The T-V diagram

Figure 2.10 T-v diagram of constant-pressure phase-change processes of a pure substance at

Figure 2.11 T-V diagram of a pure substance.

The P-V diagram

Figure 2.12 P-V diagram of a pure substance.

The P-T diagram

Figure 2.13 P-T diagram of pure substances.

Melting and Sublimation

Figure 2.14 Phase diagram for water

2.4 Thermodynamic tables

Saturated liquid-vapor mixture

Where mtotal  mliquid  mvapor  m f  mg (2.2)

Figure 2.15 Liquid and vapor phases in a saturated mixture

mtot vavr  ( mtot  mg )v f  mg vg (2.5)

vavr  (1  x )v f  xvg (2.6)

vavg  v f  xv fg (m3/kg) (2.7)

Solving for quality, we obtain

The above equation also holds true for other properties

Internal energy: u  u f  xu fg (2.9)

Saturated Liquid and Saturated Vapor States

Figure 2.16 A partial list of Thermodynamic Table

Superheated steam table

Figure 2.17 Super heated region in graph and table form

Compared to saturated vapor, superheated vapor is characterized by

Compressed liquid table

In general, a compressed liquid is characterized by

Figure 2.18 Compressed liquid region

How to Choose the Right Table

2.5 Equation of State

P =Absolute Pressure, KPa

R =Gas Constant. KJ/Kg∙K

M =Molecular Weight, Kg/Kmol

Compressibility factor (measure of deviation from ideal gas)

Figure 2 19 Comparison of Z factor for various gases

Figure 2.20 Simple fluid compressibility chart

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