MODULE I

PROPERTIES AND PROCESSES

OF A PURE SUBSTANCE

Lesson 1 Properties of Pure Substance

Lesson 2 Processes of Pure Substance

THELMA T. OBILLO, PME

FACULTY, MECHANICAL ENGINEERING
1ST SEMESTER SY 2020-2021

Module I
 2

MODULE I
PROPERTIES OF PURE SUBSTANCE

 INTRODUCTION

A substance that has a fixed chemical composition throughout is called a pure

substance. Water, nitrogen, helium, and carbon dioxide, for example, are all pure
substances. 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.
To quantify the changes in a thermodynamic system, we have to be able to
describe the substances which make up the system. The substance is characterized by
its properties. This module shows how this is done for two major behavioral classes of
substance covered in this course; phase-change fluids, and gases. As discussed under
section working fluids, the steam power plants run with the help of working fluid like
liquid/vapor. These working fluids are generally pure substances. Because the change
in properties of the working fluid i.e. pure substance operates the power plants, it is
necessary to study the properties of pure substance. This module is focused on the
properties and processes of a pure substance.

LEARNING OUTCOMES

After studying the module, you should be able to:

1. Define pure substance and describe the manners of phase changes of a pure
substance
2. Define and discuss the different phases of a pure substance
3. Identify thermodynamic properties of a pure substance
4. Determine properties of water using steam tables
5. Solve problems involving the properties of a pure substance

 DIRECTIONS/ MODULE ORGANIZER

There are two lessons in the module. Read each lesson carefully then answer
the exercises/activities to find out how much you have benefited from it. Work on
these exercises carefully and submit your output to your instructor.

In case you encounter difficulty, discuss this with your instructor during the
face-to-face meeting.

Good luck and happy reading!!!

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
 3

Lesson 1

 Properties of Pure Substance

Definition of Terms:

Pure Substance
- a working substance whose chemical composition remains the same even if
there is a change in phase
- a substance that has a fixed chemical composition throughout

Examples: water, nitrogen, helium, carbon dioxide

Saturation Temperature
Saturation temperature is the temperature at which liquids start to boil or the
temperature at which vapors begin to condense. The saturation temperature of a given
substance depends upon its existing pressure. It is directly proportional to the
pressure, i.e. it increases as the pressure is increased and decreases as the pressure
is decreased.
Examples:
a. Water boils at 100oC at atmospheric condition (101.325 kPa)
b. Water boils at 179.91oC at a pressure of 1000 kPa
c. Steam condenses at 311.06 oC at 10 MPa
d. Steam condenses at 39oC at 0.0070 MPa

Subcooled Liquid
A subcooled liquid is one which has a temperature lower than the saturation
temperature corresponding to the existing pressure.
Example:
Liquid water at 60oC and 101.325 kPa is a subcooled liquid. This is because from
the steam tables, the saturation temperature at 101.325 kPa is 100 oC. Since the
actual temperature of liquid water of 60oC is less than 100oC, therefore, it is a
subcooled liquid.

Compressed Liquid
A compressed liquid is one which has a pressure higher than the saturation
pressure corresponding to the existing temperature.

Question:
Is liquid water at 110 kPa and 1000C a compressed liquid?
From steam tales, Psat at 1000C = 101.325 kPa.

Comparing:
The actual liquid water pressure of 110 kPa is greater than P sat at 1000C.
Therefore, it is a compressed liquid.

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
 4

Saturated Liquid
A saturated liquid is a liquid at the saturations (saturation temperature or
saturation pressure), which has temperature equal to the boiling point corresponding
to the existing pressure. It is a pure liquid, i.e., it has no vapor content.
Examples:
a. Liquid water at 100oC and 101.325 kPa
b. Liquid water at 233.90oC and 3 MPa
c. Liquid water at 324.75oC and 12 MPa

Answers: From steam tables:

tsat  P101.325 kPa  100 C
tsat  P3 MPa  233.90 C
tsat  P12 MPa  324.75 C

Vapor
Vapor is the name given to a gaseous phase that is in contact with the liquid
phase, or that is in the vicinity of a state where some of it might be condensed,

Saturated Vapor
A saturated vapor is a vapor at the saturation conditions (saturation
temperature and saturation pressure). It is 100% vapor i.e., has no liquid or moisture
content.
Examples:
a. Steam (water vapor) at 100oC and 101.325 kPa
b. Steam at 212.42oC and 2 MPa
c. Steam at 352.37oC and 17 MPa

Superheated Vapor
A superheated vapor is a vapor having a temperature higher than the saturation
temperature corresponding to the existing pressure.
Examples:
a. Steam at 200oC and 101.325 kPa
200 C  tsat  P101.325 kPa  100 C 
b. Steam at 300oC and 5 MPa
300 C  tsat  P5 MPa  263.99 C 

Degrees of Superheat, oSH

The degrees of superheat is the difference between the actual temperature of
superheat vapor and the saturation temperature for the existing pressure.
In equation form:
o
SH=Actual superheat temperature – tsat at existing pressure

Example:
Determine the degrees of superheat of superheated steam at 200oC and
101.325 kPa.

From steam tables:

tsat at 101.325 kPa =100oC
o
SH = 200 oC – 100 oC = 100 oC

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
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Degrees Subcooled, oSB

The degrees subcooled of a subcooled liquid is the difference between the
saturation temperature for the given pressure and the actual subcooled liquid
temperature.
In equation form:
o
SB= tsat at given pressure - actual liquid temperature

Example:
Determine the degrees subcooled of liquid water at 90 oC and 101.325 kPa.
From steam tables:
tsat at 101.325 kPa =100oC
o
SH = 100 oC – 90 oC = 10 oC

Wet Vapor
A wet vapor is a combination of saturated vapor and saturated liquid.

Dryness Fraction or Quality, x

The quality of wet vapor or wet steam is the percent by weight that is saturated
vapor. A quality of zero (0) indicates 100% water while quantity of one (1) indicates
100% steam.

mass of vapor
x
total mass of mixture

Percent Moisture, y
The percent moisture of wet vapor is the percent by weight that is saturated
liquid.

Let m=mass of wet vapor

mg = mass of the saturated vapor content of wet vapor.
mf = mass of the saturated liquid content of wet vapor.
Then, m=mg+mf

Following the definitions of quality (x) and percent moisture (y),

mg
x  100
m
mf
y  100
m

For saturated liquid:

y = 100%
x = 0%
For saturated vapor:
x = 100%
y = 0%
For wet vapor:
0 < x < 100
0 < y < 100

But x + y = 100 in percent form

x + y = 1 in decimal form

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
 6

Latent Heat of Vaporization

The latent heat of vaporization of a pure substance is the amount of heat added
to/remove from the substance in order to convert it from saturated liquid/saturated
vapor to saturated vapor/saturated liquid with the temperature remaining constant.
It is inversely proportional to the temperature of pressure of the substance.

Example:
Determine the latent heat of vaporization of water at: (a) 100 oC, (b)
o
200 C, and (c) 300oC.
From steam tables:
(a) hfg at 100oC = 2257.0 kJ/kg
(b) hfg at 200oC = 1940.7 kJ/kg
(c) hfg at 300oC = 1404.9 kJ/kg

Critical Point
The critical point represents the highest pressure and highest temperature at
which liquid and vapor can coexist in equilibrium. The state of water at critical
conditions whether it is saturated liquid or saturated vapor is unknown. Hence, the
latent heat of vaporization of water at this condition is either zero or undefined.

Sensible Heat
Heat that causes change in temperature without a change in phase.
Examples:
a. Heat added in raising the temperature of steam from 100 oC at
101.325 kPa to 150oC.
b. Heat removed in lowering the temperature of water from 90 oC to
80oC.
Latent Heat
Heat that causes change in phase without a change in temperature.
Example:
Heat added in converting 1 kg of water at 100 oC and 101.325 kPa to 1
kg of steam at 100oC and 101.325 kPa.

Change of Phase at Constant Pressure

300C 7300C 1000C

(a) (b) (c)

Subcooled Liquid Subcooled Liquid Saturated Liquid

1000C 1000C 1200C

(d) (e) (f)

Saturated Liquid and Saturated Vapor
(Wet Vapor) Saturated Liquid Superheated Liquid

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
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Let the piston-cylinder arrangement contains subcooled liquid water at 30 0C

and 101.325 kPa (Fig. a). Then let heat be added continuously at constant pressure.
First, the water gets warmer. The addition of (sensible) heat causes an increased in
water temperature, say, from 300C to 700C (Fig. b). further addition of (sensible) heat
causes a further increased in water temperature until it reaches 100 0C, the boiling or
saturation temperature at 101. 325 kPa. Water at this point is at saturated liquid state
(Fig. c). Then as more (latent) heat is added to the now saturated liquid water causes
some of it to be converted to saturated vapor with the temperature remaining 100 0C.
Water is now a mixture of saturated liquid and saturated vapor. Hence, it is now in
wet vapor state (Fig. d). Further addition of (latent) heat causes the transformation
of the remaining saturated liquid water to saturated water vapor at 100 0C. Water is
now at the saturated vapor state (Fig. e). Finally, as more (sensible) heat is added to
the saturated water vapor at 1000C its temperature rises say until it reaches 1100C.
Water is now at the superheated vapor state (Fig. f).

Properties of Wet Steam

Subscripts Used/Symbols Used
f – represents properties of saturated liquid
g – represents properties of saturated vapor
fg – represents to a change by evaporation
v – specific volume, m3/kg
h – specific enthalpy, kJ/kg
s – specific entropy, kJ/kg.K
u – specific internal energy, kJ/kg

v = vf = vfg vfg = vg – vf
hg = hf + hgf hfg = hg – hf
sg = sf + sfg sfg = sg – sf
ug = u +ufg ufg = ug – uf

x y

v v
Fig. 1-3. Specific Volume of a Wet Mixture

v = Specific volume of its saturated liquid content + specific volume of its saturated
vapor content
v  yv f  xvg

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
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kg liquid m3 m3
yv f  
kg mixture kg liquid kg mixture
kg vapor m3 m3
xvg  
kg mixture kg vapor kg mixture

From v  yv f  xvg
But y  1 x
Then

v  1  x  v f  xvg x  1 y
v  v f  xv f  xvg v  yv f  1  y  vg
or
v  v f  x  vg  v f  v  yv f  vg  yvg
v  v f  xv fg v  vg  y  vg  v f 
v  vg  yv fg

Similarly,
h  h f  xh fg or h  hg  yh fg
s  s f  xs fg or s  sg  ys fg
u  u f  xu fg or u  u g  yu fg

NOTE:
At saturated conditions, p and t are dependent on one another and therefore,
are considered as one independent property. At superheated conditions, p and t are
independent from each other and therefore, are considered as two independent
properties.

Quality could not be more than 100% and per cent moisture could not be lower
than 0%.

xsf ysf

sf sfg

sg

Fig. 1-4 Specific Entropy of a Wet Mixture.

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
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Steam Tables

Steam tables are tables widely used by engineers and scientists in the design
and operation of equipment where steam is used as working substance in a
thermodynamic processes and cycles. It gives an idea about the phase of steam at
various temperature and pressure.

Mollier Chart or Mollier Diagram

Mollier diagram was developed by Richard Mollier (1863-1935) is a graphic

representation of the properties of steam in an enthalpy versus entropy coordinate.
This diagram is sometimes called the h-s diagram. It contains a series of constant
pressure lines (isobars), a series of constant temperature lines (isotherms), a series
of constant volume lines (isochors), a series of constant moisture or quality lines, and
series of constant superheated lines. The constant temperature lines coincide with
the constant pressure lines in the wet region (below saturated vapor line) but bend
toward the right away from the constant pressure lines in the superheat region.

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
 10

The p-v-T Relations

Figure 3.1 is the p–v–T surface of a substance such as water that expands on
freezing. Figure 3.2 is for a substance that contracts on freezing, and most substances
exhibit this characteristic. The coordinates of a point on the p–v–T surfaces represent
the values that pressure, specific volume, and temperature would assume when the
substance is at equilibrium.

There are regions on the p–v–T surfaces of Figs. 3.1 and 3.2 labeled solid,
liquid, and vapor. In these single-phase regions, the state is fixed by any two of the
properties: pressure, specific volume, and temperature, since all of these are
independent when there is a single-phase present. Located between the single-phase
regions are two-phase regions where two phases exist in equilibrium: liquid–vapor,
solid–liquid, and solid–vapor. Two phases can co-exist during changes in phase such as
vaporization, melting, and sublimation. Within the two-phase regions pressure and
temperature are not independent; one cannot be changed without changing the other.
In these regions the state cannot be fixed by temperature and pressure alone;
however, the state can be fixed by specific volume and either pressure or
temperature. Three phases can exist in equilibrium along the line labeled triple line.
A state at which a phase change begins or ends is called a saturation state. The dome-
shaped region composed of the two-phase liquid–vapor states is called the vapor
dome. The lines bordering the vapor dome are called saturated liquid and saturated
vapor lines. At the top of the dome, where the saturated liquid and saturated vapor
lines meet, is the critical point. The critical temperature Tc of a pure substance is
the maximum temperature at which liquid and vapor phases can coexist in equilibrium.

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
 11

The pressure at the critical point is called the critical pressure, pc. The specific
volume at this state is the critical specific volume.

THE PHASE DIAGRAM

If the p–v–T surface is projected onto the pressure–temperature plane, a

property diagram known as a phase diagram results. As illustrated by Figs. 3.1b and
3.2b, when the surface is projected in this way, the two-phase regions reduce to lines.
A point on any of these lines represents all two-phase mixtures at that particular
temperature and pressure.

The term saturation temperature designates the temperature at which a

phase change takes place at a given pressure, and this pressure is called the saturation
pressure for the given temperature. It is apparent from the phase diagrams that for
each saturation pressure there is a unique saturation temperature, and conversely.

The triple line of the three-dimensional p–v–T surface projects onto a point on
the phase diagram. This is called the triple point. Recall that the triple point of water
is used as a reference in defining temperature scales. By agreement, the temperature
assigned to the triple point of water is 273.16 K. The measured pressure at the triple
point of water is 0.6113 kPa.

The line representing the two-phase solid–liquid region on the phase diagram
slopes to the left for substances that expand on freezing and to the right for those
that contract. Al-though a single solid phase region is shown on the phase diagrams of
Figs. 3.1 and 3.2, solids can exist in different solid phases. For example, seven
different crystalline forms have been identified for water as a solid (ice).

p-V DIAGRAM

Projecting the p–v–T surface onto the pressure–specific volume plane results in
a p–v diagram, as shown by Figs. 3.1cand 3.2c. The figures are labeled with terms that
have already been introduced. When solving problems, a sketch of the p–v diagram is
frequently convenient. To facilitate the use of such a sketch, note the appearance of
constant-temperature lines (isotherms). By inspection of Figs. 3.1c and 3.2c, it can be
seen that for any specified temperature less than the critical temperature, pressure
remains constant as the two-phase liquid–vapor region is traversed, but in the single-
phase liquid and vapor regions the pressure decreases at fixed temperature as specific
volume increases. For temperatures greater than or equal to the critical temperature,
pressure decreases continuously at fixed temperature as specific volume in-creases.
There is no passage across the two-phase liquid–vapor region. The critical isotherm
passes through a point of inflection at the critical point and the slope is zero there.

T–v DIAGRAM

Projecting the liquid, two-phase liquid–vapor, and vapor regions of the p–v–T
surface on to the temperature–specific volume plane results in a T–v diagram as in Fig.
3.3. Since consistent patterns are revealed in the p–v–T behavior of all pure
substances, Fig. 3.3 showing a T–v diagram for water can be regarded as
representative.

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
 12

PHASE CHANGES

Liquid State

As the system is heated at constant pressure, the temperature increases

considerably while the specific volume increases slightly. Eventually, the system is
brought to the state represented by f on Fig. 3.3. This is the saturated liquid state
corresponding to the specified pressure. For water at 1.014 bar the saturation
temperature is 100C. The liquid states along the line segment l–f of Fig. 3.3 are
sometimes referred to as subcooled liquid states because the temperature at these
states is less than the saturation temperature at the given pressure. These states are
also referred to as compressed liquid states because the pressure at each state is
higher than the saturation pressure corresponding to the temperature at the state.
The names liquid, subcooled liquid, and compressed liquid are used interchangeably.

Two-phase, Liquid–vapor Mixture

When the system is

at the saturated liquid
state (state f of Fig. 3.3),
additional heat transfer at
fixed pressure results in
the formation of vapor
without any change in
temperature but with a
considerable increase in
specific volume. As shown
in Fig. 3.4b, the system would now consist of a two-phase liquid–vapor mixture. When
a mixture of liquid and vapor exists in equilibrium, the liquid phase is a saturated
liquid and the vapor phase is a saturated vapor. If the system is heated further until
the last bit of liquid has vaporized, it is brought to point g on Fig. 3.3, the saturated
vapor state. The intervening two-phase liquid–vapor mixture states can be
distinguished from one another by the quality, an intensive property.

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
 13

For a two-phase liquid–vapor mixture, the ratio of the mass of vapor present
to the total mass of the mixture is its quality, x.

mvapor
x
mliquid  mvapor

The value of the quality ranges from zero to unity: at saturated liquid states,
x=0, and at saturated vapor states, x=1.0. Although defined as a ratio, the quality is
frequently given as a percentage. Similar parameters can be defined for two-phase
solid–vapor and two-phase solid–liquid mixtures.

Vapor States

Let us return to a consideration of Figs. 3.3 and 3.4. When the system is at the
saturated vapor state (state g on Fig. 3.3), further heating at fixed pressure results in
increases in both temperature and specific volume. The condition of the system would
now be as shown in Fig. 3.4c. The state labeled s on Fig. 3.3 is representative of the
states that would be attained by further heating while keeping the pressure constant.
A state such as s is often referred to as a superheated vapor state because the system
would be at a temperature greater than the saturation temperature corresponding to
the given pressure.

Consider next the same thought experiment at the other constant pressures
labeled on Fig. 3.3, 10 MPa, 22.09 MPa, and 30 MPa. The first of these pressures is less
than the critical pressure of water, the second is the critical pressure, and the third
is greater than the critical pressure. As before, let the system initially contain a liquid
at 20C. First, let us study the system if it were heated slowly at 10 MPa. At this
pressure, vapor would format a higher temperature than in the previous example,
because the saturation pressure is higher (refer to Fig. 3.3). In addition, there would
be somewhat less of an increase in specific volume from saturated liquid to vapor, as
evidenced by the narrowing of the vapor dome. Apart from this, the general behavior
would be the same as before. Next, consider the behavior of the system where it
heated at the critical pressure, or higher. As seen by following the critical isobar on
Fig. 3.3, there would be no change in phase from liquid to vapor. At all states there
would be only one phase. Vaporization (and the inverse process of condensation) can
occur only when the pressure is less than the critical pressure. Thus, at states where
pressure is greater than the critical pressure, the terms liquid and vapor tend to lose
their significance. Still, for ease of reference to such states, we use the term liquid
when the temperature is less than the critical temperature and vapor when the
temperature is greater than the critical temperature.

MELTING AND SUBLIMATION

Vaporization - the phase change from liquid to vapor
Melting - the phase changes from solid to liquid
Sublimation - the phase changes from solid to vapor

To study these transitions, consider a system consisting of a unit mass of ice at

a temperature below the triple point temperature. Let us begin with the case where
the system is at state a of Fig. 3.5, 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 bon Fig.
3.5 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.

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
 14

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 con Fig. 3.5. Next, consider the case
where the system is initially at state a of Fig. 3.5, 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. 3.5. The case of vaporization discussed previously is shown on Fig. 3.5
by the line a”–b”–c”.

Figure 3.5 Phase diagram

for water (not to scale)

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering
 15

 LEARNING ACTIVITY

Learning Task No.01 (Properties of Pure Substance)

Part 1. Analyze the properties of pure substance using Steam Tables.

1. Determine the phase of steam, given the following conditions:
1.1 t=300oC, h=3063.2 kJ/kg
1.2 t=200oC, s=2.0032 kJ/kg-K
1.3 P=540 kPa, t=250oC
1.4 P=5200 kPa, v=43.22x10-3 m3/kg
1.5 P=8581 kPa, h=1344.0 kJ/kg
1.6 t=340oC, v=10.797x10-3 m3/kg
1.7 t=374.136oC, P=22090 kPa
1.8 t=360oC, u=2035 kJ/kg

Part 2. Problem Set

Solve the following problems. Round-off your answers to three decimal places.
1. Steam at a temperature of 250oC has a specific volume of 0.15436 m3/kg. What
are the pressure, specific internal energy, enthalpy, and entropy?
2. Steam has a quality of 95% quality at a temperature of 180 oC. Determine the
enthalpy and the specific volume of the steam.
3. A rigid vessel contains 2 kg of steam at 6.35 MPa and 375 oC. Determine its
enthalpy in kJ using steam tables only.
4. Steam at a temperature of 210oC has a specific entropy of 7.1167 kJ/kg.K.
Determine the pressure, internal energy, enthalpy and volume.

Module I Properties and Processes of Pure Substance THELMA T. OBILLO, PME

Faculty, Mechanical Engineering