DEPARTMENT OF ENGINEERING SCIENCE

COLLEGE OF ENGINEERING AND AGRO-INDUSTRIAL TECHNOLOGY

UNIVERSITY OF THE PHILIPPINES LOS BAÑOS

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ENGINEERING THERMODYNAMICS AND HEAT TRANSFER
Chapter 2
Thermodynamic Properties of Pure Substance

2.1 Introduction

Most of the time, thermodynamic systems such as refrigeration systems and gasoline engines
rely on a specific pure substance to operate. To be able to design and analyze these types of systems,
it is important that we understand how to not just measure, but also solve for the thermodynamic
properties of this working fluid given other easily measurable properties.

In the previous chapter, we established what thermodynamic properties are, as well as how we
can use them to define the state of a system. We have also learned that changing these thermodynamic
properties using what is called a process, also changes the state of the system. Now, we will learn the
different methods engineers use to determine these thermodynamic properties.

Pure Substance
A pure substance is one that has a homogeneous and invariable chemical composition
throughout its extent. It can exist in more than one phase (i.e. solid, liquid, gas) but as long as its
chemical composition is the same in all the phases, it is a pure substance. Some common examples are
liquid water, steam, ice, or any mixture of the three.

2.2 Objectives
At the end of this chapter the student should be able to:

• define the state postulate;

• define the following terms:
• intensive properties
• extensive properties
• define pure substance and its phases;
• discuss the phase change processes of a pure substance;
• define the following terms;
• saturation temperature and pressure
• latent heat of vaporization and fusion
• critical temperature and pressure
• critical point
• triple point
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 • discuss the kinds of property diagrams;
• discuss the thermodynamic property tables; and
• define the following terms:
• compressed liquid/sub cooled liquid
• saturated liquid
• saturated liquid-vapor mixture
• saturated vapor
• superheated vapor
• enthalpy

2.3 The State Postulate

As mentioned in the previous chapter, the state of a system is described by its properties. In
order however to determine the state of the system, you need at least two thermodynamic properties,
as seen in our x-y graph shown in chapter 1.1. It is not possible to identify a point in a graph knowing
just one coordinate.

This concept is summarized by the state postulate:

Any two independent intensive thermodynamic properties are sufficient to describe the
state of a system containing a single pure substance.

Figure 2.1 State postulate

This concept is significant because this means that with knowing just two thermodynamic
properties of a pure substance, we can be sure that it is of a specific state, and thus would allow us to
determine all its other thermodynamic properties. The rest of this chapter will be devoted to the
methods of determining the thermodynamic properties of pure substances by applying the state
postulate.

2.4 Pure Substance and Its Phases

Before demonstrating the methods of determining thermodynamic properties of pure

substances, it is important to understand what pure substances are, it’s different phases, and it’s
different property diagrams.

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 A substance that has a fixed chemical composition throughout is called pure substance. Some
examples of pure substance are water, helium and nitrogen. It may exist in more than one phase,
as long as the chemical composition is the same. For example, a mixture of liquid water and water
vapor or, a mixture of ice and liquid water are both pure substances since every phase has the same
chemical composition.

Phase is any homogenous part of a system which is physically distinct and is separated from
other parts of the system by distinct bounding surfaces. It is also defined as any distinct molecular
arrangement separated by boundary surfaces. The three principal phases are solid, liquid and gas.

Figure 2.2. The three principal phases of a pure substance

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2.5 Phase Change Processes of a Pure Substance

Consider a piston-cylinder device containing liquid water at 20˚C

and 1 atm pressure. Under these conditions, water exists in the liquid
phase, and it is called a compressed liquid, or a sub cooled liquid,
meaning that it is not about to vaporize. Heat is now transferred to the
water until its temperature rises to, say, 40 oC. As the temperature rises,
the liquid water expands slightly, and so its specific volume increases. To
accommodate this expansion, the piston will move slightly. The pressure
in the cylinder remains constant 1 atm during this process since it
depends on the outside barometric pressure and the weight of the piston, Figure 2.3.
both of which are constant. Water is still a compressed liquid at this At 1 atm and 20oC, water
state since it has not started to vaporize. exists in the liquid phase
(compressed liquid)

As more heat is transferred, the temperature will keep rising until

it reaches 100 o C (state 2, Figure 2.5). 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.

Figure 2.4.
At 1 atm and 100oC, water
exists in the liquid that is
ready to vaporize
(saturated liquid)

Once boiling starts, the temperature will stop 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.
Figure 2.5.
During boiling process, the only change we will observe is a large increase
As more heat is
in the volume and a steady decline in the liquid level as a result of more
transferred, part of the
liquid turning to vapor.
saturated liquid vaporizes
(saturated liquid-vapor
mixture)

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 Midway about the vaporization line (state 3, Figure 2.6), the
cylinder contains equal amounts of liquid and vapor. As we continue
transferring heat, the vaporization process will continue until the last drop
of liquid is vaporized (state 4, Figure 2.7). At this point, the entire cylinder
is filled with vapor will cause some of the vapor to condense (phase
change from vapor to liquid). A vapor that is about to condense is called
saturate vapor. Therefore, state 4 is saturate vapor state. A substance as Figure 2.7.
states between 4 and 4 is often referred to as a saturated liquid-vapor As more heat is
mixture since the liquid and vapor phases coexist in equilibrium at these transferred, the
states. temperature of the vapor
starts to rise (superheated
vapor)
Once the phase-change process is completed, we are back to a
single-phase region again (this time vapor), and further transfer of heat
will result in an increase in both the temperature and the specific volume
(Figure 2.8). At the state 5, the temperature of the vapor is, let us say, 300
oC; 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 oC ( for P = 1 atm). A vapor that is not
about to condense 9 i.e. not a saturated vapor) is called a superheated
vapor. Therefore, water at state 5 is a superheated vapor.

Figure 2.6.
At 1 atm pressure, the
temperature remains
constant at 100 C until
o

the last drop of liquid is

vaporized (saturated
vapor)

This constant-pressure phase change process as described is illustrated on a T-v diagram in

Figure. 2.8
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 .

Figure 2.8 T-v diagram for the heating process of water at constant pressure

Important terms:

Saturation temperature is the temperature at which vaporization takes place

at a given pressure.

Saturation pressure is the pressure at which vaporization takes place at a given

temperature

Latent heat is the amount of energy absorbed or released during a phase-

change process.

Sensible heat is the amount of energy absorbed or released when there is no

phase-change process

Latent heat of fusion is the amount of energy absorbed during melting or the
equivalent to the amount of energy released during freezing.

Latent heat of vaporization is the amount of energy absorbed during

vaporization or the equivalent to the amount of energy released during
condensation.

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2.6 Property Diagrams for Phase-Change Processes

Property diagrams are x-y plots showing the behavior of the pure substance in terms of phase-
change, with the x and y axes as a combination of thermodynamic properties. A combination of two
properties will identify a point on the x-y graph, which will be the state of the system. The location of
the point will determine which phase the state currently is experiencing.

These diagrams are useful tools in interpreting the current state of a pure substance, as well as
how changing the thermodynamic properties affect the state of the pure substance. Multiple states can
be present in a single chart which are connected by a path, which according to chapter 1, represents
the process that the pure substance experienced.

T-V Diagram

X – axis = specific volume

Y – axis = temperature

As shown in the Figure 2.10, the T-v diagram is composed of isobars (dashed lines) or constant
pressure lines. The saturated liquid states in the figure below 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 saturated vapor line. Any point located along these lines are in either the saturated liquid
state or the saturated vapor state. These two lines meet at the critical point, forming a curve as shown
in figure 2.10. All the compressed liquid states are in the region to the left of the saturated liquid line,
called the compressed liquid region. All the superheated vapor states are located at the right of the
saturated vapor line, called 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 curve, called the saturated liquid-vapor region.

Figure 2.10. The T-V diagram

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P-V Diagram

The general shape of the P-v diagram of a pure substance is very much like the T-v diagram and
the isotherms or the constant temperature lines on this diagram have a downward trend, as shown in
Figure 2.11.

Figure 2.11. The P-V diagram

P-T Diagram

The Figure 2.12 shows the P-T diagram, also known as phase diagram. It shows the three phases
of a pure substance separated in three lines. The sublimation line separates solid from vapor regions,
the vaporization line separates the liquid and vapor regions, and the melting (or fusion) line separates
the solid and liquid regions. These three lines meet at the triple point , where all three phases coexist
in equilibrium. The vaporization line ends at the critical point because no distinction can be made
between liquid and vapor phases above the critical point.

Substance that expand and contract on freezing differ only in the melting line on the P-T
diagram.

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 Figure 2.12. The P-T diagram

2.7 Sample Problems

In these problems, we will learn how to use these diagrams to help us visualize what the pure
substance experiences during a given process.

Example 2.1

Illustrate a liquid-vapor mixture in a rigid tank is heated so as to pass through the critical point on
separate P-v and T-v diagrams.

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Example 2.2

Illustrate a saturated vapor in a rigid container is heated until the pressure doubles on separate P-v
and T-v diagrams.

Example 2.3

Illustrate a saturated vapor is condensed to a saturated liquid at the same temperature on separate T-
v and P-v diagrams.

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Example 2.4

Illustrate a superheated vapor is cooled in a rigid container until it becomes a saturated vapor on
separate T-v and P-v diagrams.

2.8 Thermodynamic Property Tables

Thermodynamic properties are frequently presented in the form of tables. Some properties can
be measured easily, but others cannot and are calculated by applying the state postulate and using the
relations between them and measurable properties.
For each substance, the thermodynamic properties are listed in more than one table. There is a
prepared separate table for each region of interest such as superheated vapor, compressed liquid, and
saturated (mixture) regions. The following notations are used for each thermodynamic property listed
in the tables:

P – Pressure
T – Temperature
v – Specific volume
u – Specific internal energy
h – Specific enthalpy
A Combination Property (associated with the second law of thermodynamics
H = U + PV or h = u + Pv
s – Specific entropy
Thermodynamic tables are constructed in such a way where each column represents a
thermodynamic property, while each row represent a specific state, of which each thermodynamic
property is known. For example, in the figure below (Figure 2.13), once I determine that the pure
substance has a temperature of 90˚C and pressure 70.13 kPa, I can be sure that the specific volume of
the pure substance is 0.001036 m3/kg if it is in the saturated liquid phase of 2.361 m3/kg of in the
saturated vapor phase.

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States of a Pure Substance

Saturated liquid and Saturated vapor states

The properties of saturated liquid and
saturated vapor for water are listed in
thermodynamic tables (see Appendices). The
subscript f is used to dente properties of a
saturated liquid and subscript g to denote the
properties of saturated vapor. Another subscript
commonly used fg, which denotes the difference
between the saturated vapor and saturated liquid
values of the same property. For example,
 f = specific volume of saturated liquid
 g = specific volume of saturated vapor
 fg = difference between  g and  f

Below is an example of a section of a

saturated-liquid vapor table, showing columns for
temperature, saturated pressure, and specific Figure 2.13 Section of a saturated liquid-
volume. vapor mixture table
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 the properties of this mixture, there is a
need to know first 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.

mass of vapor mg
x= =
total mass of the mixture m f + mg

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 the 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, only the amount of
saturated liquid changes, not its properties. The same can be said about a saturated vapor.

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 Saturated vapor

vg vx

Saturated
liquid-vapor
mixture
Saturated liquid
Figure 2.14. A two-phase system can be treated as a homogenous mixture for convenience.
vf
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 homogenous mixture
(Figure 2.14). 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:

V = V f + Vg (m ) 3

V = mv → mv = m f v f + mg vg
mtotal = m f + mg
dividing by mtotal yields,
 m   m 
v =  f v f +  g vg
 mtotal   mtotal 
mg mf
where x = 1− x =
mtotal mtotal

The relation can be exp ressed as,

v = (1 − x )v f + xvg where v fg = vg − v f

v = v f + xvfg  m3 
 kg 

solving for the quality, we obtain

v −v
x= f
v fg

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 The analysis given above can be repeated for internal energy and enthalpy with the following
results:

u = u f + xufg  kJ 
 kg 
h = h f + xhfg  kJ 
 kg 
s = s f + xsfg  kJ 
 kg K 
 
Superheated vapor
At the right of the saturated vapor line and at temperature above the critical point temperature,
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.

In superheated vapor tables (see Appendices), the properties are listed against temperature for
selected pressures starting with the saturated vapor data. The saturation temperature is given in
parentheses following the pressure value.

Superheated vapor is characterized by:

Lower pressure (P < Psat’n at a given P)

Higher temperature (T > Tsat’n at a given T)
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 / Subcooled Liquid

Compressed liquid tables are not commonly available. Its format is very much like the
superheated vapor tables.

In the absence of the compressed liquid table, the general approximation is to treat compressed
liquid as saturated liquid at a given temperature. This is because the compressed liquid properties
depend on temperature much more strongly than they do on pressure.

In general, a compressed liquid is characterized by:

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 Higher pressures (P > Psat’n at a given T)
Lower temperature (T < Tsat’n at a given P)
Lower specific volume (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)

Additional Sample Problems:

Taken from Thermodynamics an Engineering Approach by Cengel – 5th edition

Sample Problem 2.5 (Saturated Liquid or SL)

A rigid tank contains 50 kg of saturated liquid water at 90°C.

Determine the pressure in the tank and the volume of the tank.

Solution: A rigid tank contains saturated liquid water. The

pressure and volume of the tank are to be determined.

Analysis Since saturation conditions exist in the tank, the pressure

must be the saturation pressure at 90 °C:

𝑃 = 𝑃𝑠𝑎𝑡@90𝐶 = 70.183 (Table A-4)

The specific volume of the saturated liquid at 90°C is

𝑣 = 𝑣𝑓@90𝐶 = 0.001036 𝑚3 /𝑘𝑔 (Table A-4)

Then the total volume of the tank becomes

𝑚3
𝑣 = 𝑚𝑣 = (50 𝑘𝑔) (0.001036 ) = 0.0518 𝑚3
𝑘𝑔

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Sample Problem 2.6 (Saturated Vapor or SV)

A piston–cylinder device contains 2 ft3 of saturated water vapor at

50-psia pressure. Determine the temperature and the mass of the
vapor inside the cylinder.

Solution: A cylinder contains saturated water vapor. The

temperature and the mass of vapor are to be determined.

Analysis: Since the cylinder contains saturated vapor at 50 psia, the

temperature inside must be the saturation temperature at this
pressure:

𝑇 = 𝑇𝑠𝑎𝑡@50𝑝𝑠𝑖𝑎 = 280.99˚𝐹 (Table A-5E)

The specific volume of the saturated vapor at 50 psia is

𝑣 = 𝑣𝑔@50𝑝𝑠𝑖𝑎 = 8.5175 𝑓𝑡 3 /𝑙𝑏𝑚 (Table A-5E)

Then the mass of water vapor inside the cylinder becomes

𝑉 2𝑓𝑡 3
𝑚= = = 0.235 𝑙𝑏𝑚
𝑣 8.5175𝑓𝑡 3 /𝑙𝑏𝑚

Sample Problem 2.7 (Saturated Liquid-Vapor Mixture or SLV)

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 of the refrigerant, and (d) the
volume occupied by the vapor phase.

Solution A vessel is filled with refrigerant-134a. Some

properties of the refrigerant are to be determined.

Analysis (a) At this point we do not know whether the

refrigerant is in the compressed liquid, superheated vapor,
or saturated mixture region. This can be determined by
comparing a suitable property to the saturated liquid and
saturated vapor values. From the information given, we can
determine the specific volume:

𝑉 0.080𝑚3 𝑚3
𝑣= = = 0.02
𝑚 4𝑘𝑔 𝑘𝑔

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At 160 kPa, we read using Table A-12:

𝑚3
𝑣𝑓 = 0.0007437
𝑘𝑔

𝑚3
𝑣𝑔 = 0.12348
𝑘𝑔

Obviously, vf < v < vg, and the refrigerant is in the saturated mixture region. Thus, the temperature
must be the saturation temperature at the specified pressure:

𝑇 = 𝑇𝑠𝑎𝑡@160𝑘𝑃𝑎 = −15.60˚𝐶

(b) Quality can be determined from

𝑣 − 𝑣𝑓𝑔 0.02 − 0.0007437
𝑥= = = 0.157
𝑣𝑓𝑔 0.012348 − 0.0007437

(c) At 160 kPa, we also read from Table A–12 that hf 31.21 kJ/kg and hfg 209.90 kJ/kg. Then,

ℎ = ℎ𝑓𝑔 + 𝑥ℎ𝑓𝑔
𝑘𝐽 𝑘𝐽
ℎ = 31.32 + (0.157) (209.90 )
𝑘𝑔 𝑘𝑔
ℎ = 64.2 𝑘𝐽/𝑘𝑔

(d) The mass of the vapor is

𝑚𝑔 = 𝑥𝑚𝑡 = (0.157)(4𝑘𝑔) = 0.628 𝑘𝑔

The rest of the volume (2.5 L) is occupied by the liquid.

𝑚3
𝑉𝑔 = 𝑚𝑔 𝑣𝑔 = (0.628 𝑘𝑔)(0.628 𝑘𝑔) (0.12348 ) = 0.0775 𝑚3
𝑘𝑔

The rest of the volume (2.5L) is occupied by the liquid.

Sample Problem 2.8 (Superheated vapor or SHV)

Determine the temperature of water at a state of P = 0.5 MPa and

h = 2890 kJ/kg.

Solution: The temperature of water at a specified state is to be

determined.

Analysis: At 0.5 MPa, the enthalpy of saturated water vapor is hg =

2748.1 kJ/kg. Since h > hg, we have superheated vapor. Under 0.5
MPa in Table A–6 we read

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 h,
T, ˚C
KJ/kg

200 2855.8

250 2961.0

Obviously, the temperature is between 200 and 250°C. By linear interpolation it is determined to be:
2855.8 − 2890 200 − 𝑇
=
2961 − 2855.8 250 − 200
T = 216.3°C

Sample Problem 2.9 (Compressed Liquid or CL)

Determine the internal energy of compressed liquid water at

80˚C and 5 MPa, using (a) data from the compressed liquid water
table and (b) saturated-liquid water data. What is the error
involved in the second case?

Solution: The exact and approximate values of the internal

energy of liquid water are to be determined.

Analysis: at 80˚C, the saturation pressure of water is 47.416 kPa,

and since 5 MPa > Psat, we obviously have compressed liquid.

(a) From the compressed liquid table (Table A-7)

𝑃 = 5 𝑀𝑃𝑎
} 𝑢 = 333.82 𝑘𝐽/𝑘𝑔
𝑇 = 80˚𝐶
(b) From the saturation table (Table A-4), we read
𝑢 ~ 𝑢𝑓@80𝐶 = 334.97 𝑘𝐽/𝑘𝑔

The error involved is around 0.34% only.

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2.9 Practice Problems

1. Complete the table below. Support your answers by adequate quantifiable reason (solutions,
premised, and conclusion) and by citing the table wherein you obtained the values.

Answers:

a) 2.3392 kPa k) 0.00104 m3/kg

b) 47.734 m3/kg l) 162 kJ/kg
c) 2111.7 kJ/kg m) 165 kJ/kg
d) 0.83 n) Not applicable
e) SLV o) Compressed liquid
f) 431 kPa p) 32.2 C
g) 2646 kJ/kg q) 0.000848 m3/kg
h) 2860 kJ/kg r) 96.1 kJ/kg
i) Not applicable s) 96.8 kJ.kg
j) SHV t) Saturated Liquid

Guide Questions

a) Why use property diagrams in understanding phase-change processes?

b) True or False. For water, as the pressure increases, the boiling point also increases.
c) True or False. The critical point is the point at which the liquid and vapor phase are
not distinguishable.
d) True or False. It is possible to have water vapor at -10oC.
e) Give an explanation why there is a lack of compressible liquid data.

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 REFERENCES

SONNTAG, R.E. and C. Borgnakke. 2007. Introduction to Engineering Thermodynamics.

John and Wiley Sons, Inc.

VAN WYLEN, G. J.; R. E. Sonntag & C. Borgnakke. 1994. Fundamentals of Classical

Thermodynamics, 4th ed. John Wiley & Sons.

CENGEL, C. A.; M. A. Boles. 1989. Thermodynamics and Engineering Approach, 1st ed.
MacGraw-Hill, Inc.

FAIRES, V. M. and C. M. Simmang. Thermodynamics, 6th ed.

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