Thermodynamics: An Engineering Approach

8th Edition in SI Units

Yunus A. Çengel, Michael A. Boles
McGraw-Hill, 2015

Copyright © 2015 The McGraw-Hill Education. Permission required for reproduction or display.
 Objectives
• Introduce the concept of a pure substance.
• Discuss the physics of phase-change processes.
• Illustrate the P-v, T-v, and P-T property diagrams and P-v-T
surfaces of pure substances.
• Demonstrate the procedures for determining thermodynamic
properties of pure substances from tables of property data.
• Describe the hypothetical substance “ideal gas” and the ideal-gas
equation of state.
• Apply the ideal-gas equation of state in the solution of typical
problems.
• Introduce the compressibility factor, which accounts for the
deviation of real gases from ideal-gas behavior.
• Present some of the best-known equations of state.

. 2
 Pure substance: A substance that has a fixed
chemical composition throughout.
 Air is a mixture of several gases, but it is
considered to be a pure substance.

3
 The molecules
in a solid are
kept at their
positions by the
large springlike
inter-molecular
forces.

4
Compressed liquid (subcooled Saturated liquid: A liquid that
liquid): A substance that it is not is about to vaporize
about to vaporize

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 Saturated vapor: A vapor that is about to condense.
 Saturated liquid–vapor mixture: The state at which the liquid and vapor
phases coexist in equilibrium.
 Superheated vapor: A vapor that is not about to condense (i.e., not a
saturated vapor).

At 1 atm pressure, the As more heat is

As more heat is transferred, temperature remains transferred, the
part of the saturated liquid constant at 100°C until the temperature of the
vaporizes (saturated liquid– last drop of liquid is vaporized vapor starts to rise
vapor mixture). (saturated vapor). (superheated vapor).
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If the entire process between state 1 and 5 is reversed by cooling the
water while maintaining the pressure at the same value, the water will
go back to state 1, retracing the same path, and in so doing, the
amount of heat released will exactly match the amount of heat added
during the heating process.

T-v diagram for the

heating process of
water at constant
pressure.
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The temperature at which water starts boiling depends on the pressure;
therefore, if the pressure is fixed, so is the boiling temperature.
Water boils at 100C at 1 atm pressure.
Saturation temperature Tsat: The temperature at
which a pure substance changes phase at a given
pressure.
Saturation pressure Psat: The pressure at which a
pure substance changes phase at a given
temperature.

The liquid–vapor
saturation curve
of a pure
substance
(numerical
values are for
water). 8
 Latent heat: The amount of energy
absorbed or released during a phase-
change process.
 Latent heat of fusion: The amount of
energy absorbed during melting. It is
equivalent to the amount of energy
released during freezing.
 Latent heat of vaporization: The
amount of energy absorbed during
vaporization and it is equivalent to
the energy released during
condensation.
 The magnitudes of the latent heats
depend on the temperature or
pressure at which the phase change
occurs.
 At 1 atm pressure, the latent heat of
fusion of water is 333.7 kJ/kg and the
latent heat of vaporization is 2256.5
kJ/kg.
 The atmospheric pressure, and thus
the boiling temperature of water,
decreases with elevation.
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 The variation of
the temperature
of fruits and
vegetables with
pressure during
vacuum cooling
from 25°C to 0°C.

In 1775, ice was made

by evacuating the air
space in a water tank. 10
The variations of properties during phase-change processes are best
studied and understood with the help of property diagrams such as the
T-v, P-v, and P-T diagrams for pure substances.

T-v diagram of
constant-pressure
phase-change
processes of a pure
substance at various
pressures
(numerical values
are for water). 11
 saturated liquid line
 saturated vapor line
 compressed liquid region
 superheated vapor region
 saturated liquid–vapor
mixture region (wet
region)

At supercritical pressures Critical point: The point

(P > Pcr), there is no at which the saturated
distinct phase-change liquid and saturated vapor
(boiling) process. states are identical. 12
13
 For water,
Ttp = 0.01°C
Ptp = 0.6117 kPa

At triple-point pressure
and temperature, a
substance exists in three
phases in equilibrium.

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 Phase Diagram
Sublimation:
Passing from the
solid phase directly
into the vapor phase.

At low pressures
(below the triple-point
value), solids
evaporate without
melting first
(sublimation).
P-T diagram of pure substances.
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The P-v-T surfaces present a great deal of information at once, but in a
thermodynamic analysis it is more convenient to work with two-dimensional
diagrams, such as the P-v and T-v diagrams.

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 For most substances, the relationships among thermodynamic properties are
too complex to be expressed by simple equations.
 Therefore, properties are frequently presented in the form of tables.
 Some thermodynamic properties can be measured easily, but others cannot
and are calculated by using the relations between them and measurable
properties.
 The results of these measurements and calculations are presented in tables
in a convenient format.

Enthalpy—A Combination Property

The
combination
u + Pv is
frequently
encountered
in the analysis
of control The product pressure 
volumes. volume has energy units. 17
A partial list of Table A–4.

 Table A–4: Saturation properties of

water under temperature.
 Table A–5: Saturation properties of
water under pressure.

Enthalpy of vaporization, hfg (Latent

heat of vaporization): The amount of
energy needed to vaporize a unit mass
of saturated liquid at a given
temperature or pressure.

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Examples: Saturated
liquid and saturated vapor
states of water on T-v and
P-v diagrams.

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Examples: Saturated liquid and saturated vapor states of
water on T-v and P-v diagrams.
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Quality, x : The ratio of the mass of vapor to the total mass of the mixture.
Quality is between 0 and 1 0: sat. liquid, 1: sat. vapor.
The properties of the saturated liquid are the same whether it exists alone or in
a mixture with saturated vapor.
Temperature and
pressure are dependent
properties for a mixture.

The relative
amounts of
liquid and
vapor phases
in a saturated
mixture are A two-phase system can be
specified by treated as a homogeneous
the quality x. mixture for convenience. 23
y v, u, or h.

24
Examples: Saturated liquid-vapor
mixture states on T-v and P-v diagrams. 25
Examples: Saturated liquid-vapor mixture states on T-
v and P-v diagrams.
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 Compared to saturated vapor,
superheated vapor is characterized by

In the region to the right of the At a specified

saturated vapor line and at P, superheated
temperatures above the critical vapor exists at
point temperature, a substance a higher h than
exists as superheated vapor. the saturated
In this region, temperature and vapor.
pressure are independent
properties.

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1) Complete this table for refrigerant-134a
T (oC) P(kPa) h (kJ/kg) x Phase description
a 600 180 b c
-10 d e 0.6 f
44 g h 1.0 i

1) A 1.8 m3 rigid tank contains steam at 220 oC. One third of the
volume is in the liquid phase and the rest is in the vapor form.
Determine a) the pressure of the steam, b) the quality of the
saturated mixture c) the density of the mixture

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A partial listing of Table A–6.

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Example 3-6
Determine the internal energy of water at
200kPa and 300oC.

Example 3-7
Determine the temperature of water at a state
of P=0.5 MPa and h = 2890 kJ/kg.

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The compressed liquid properties
depend on temperature much more Compressed liquid is characterized by
strongly than they do on pressure.
y → v, u, or h

A more accurate relation for h

A compressed liquid
may be approximated
as a saturated liquid at
the given temperature.

31
Example 3-8

Determine the internal energy of compressed

liquid water at 80oC and 5 Mpa, using
a) Data from the compressed liquid table
b) Saturated liquid data

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 The values of u, h, and s cannot be measured directly, and they are calculated
from measurable properties using the relations between properties.
 However, those relations give the changes in properties, not the values of
properties at specified states.
 Therefore, we need to choose a convenient reference state and assign a value of
zero for a convenient property or properties at that state.
 The referance state for water is 0.01°C and for R-134a is -40°C in tables.
 Some properties may have negative values as a result of the reference state
chosen.
 Sometimes different tables list different values for some properties at the same
state as a result of using a different reference state.
 However, In thermodynamics we are concerned with the changes in properties,
and the reference state chosen is of no consequence in calculations.

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Example 3-9
T (oC) P(kPa) u (kJ/kg) x Phase
a) 200 0.6
b) 125 1600
c) 1000 2950
d) 75 500
e) 850 0

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Exercise

T (oC) P(kPa) u (kJ/kg) Phase

a 400 1450 b

220 c d Saturated

vapor

190 2500 e f

g 4000 3040 h

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  Equation of state: Any equation that relates the pressure, temperature,
and specific volume of a substance.
 The simplest and best-known equation of state for substances in the
gas phase is the ideal-gas equation of state. This equation predicts the
P-v-T behavior of a gas quite accurately within some properly selected
region.
Ideal gas equation
of state

R: gas constant
M: molar mass (kg/kmol)
Ru: universal gas constant

Different substances have different

gas constants.
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Mass = Molar mass  Mole number

Ideal gas
equation at two
states for a fixed
mass

Various expressions
of ideal gas equation

Real gases behave as an ideal

gas at low densities (i.e., low
pressure, high temperature).
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Example 3-10
The gage pressure of an automobile tire is
measured to be 210 kPa before a trip and
220 kPa after a trip at a location where
atmospheric pressure is 95 kPa. Assuming
the volume of the tire remains constant and
the air temperature before the trip is 25 oC,
determine air temperature in the tire after the
trip.

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 At pressures below 10 kPa,
water vapor can be treated
as an ideal gas, regardless
of its temperature, with
negligible error (less than
0.1 percent).

 At higher pressures,
however, the ideal gas
assumption yields
unacceptable errors,
particularly in the vicinity of
the critical point and the
saturated vapor line.

39
Compressibility factor Z The farther away Z is from unity, the more the
A factor that accounts for gas deviates from ideal-gas behavior.
the deviation of real gases Gases behave as an ideal gas at low densities
from ideal-gas behavior at (i.e., low pressure, high temperature).
a given temperature and Question: What is the criteria for low pressure
pressure. and high temperature?
Answer: The pressure or temperature of a gas
is high or low relative to its critical temperature
or pressure.

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

Comparison of Z factors for various gases. 41

 Several equations have been proposed to
represent the P-v-T behavior of substances
accurately over a larger region with no
limitations.

Van der Waals Critical isotherm

Equation of State of a pure
substance has
an inflection
point at the
critical state.

This model includes two effects not considered

in the ideal-gas model: the intermolecular
attraction forces and the volume occupied by the
molecules themselves. The accuracy of the van
der Waals equation of state is often inadequate. 42
Beattie-Bridgeman Equation of State

The constants are given in

Table 3–4 for various
substances. It is known to be
reasonably accurate for
densities up to about 0.8cr.

Benedict-Webb-Rubin Equation of State

The constants are given in Table 3–4. This equation can handle substances
at densities up to about 2.5 cr.

Virial Equation of State

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

functions of temperature alone are called virial coefficients.
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Example 3-11
Determine the specific volume of refrigerant-134a at
1 Mpa and 50 oC, using
a) The ideal gas equation of state
b) The generalized compressibility chart

Example 3-12
Determine the pressure of water vapor at 350oC and
0.035262 m3/kg, using
a) The steam tables
b) The ideal gas equation
c) The generalized compressibility chart

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 3-78
Determine the specific volume of superheated
water vapor at 3.5 MPa and 450oC based on
 a) The ideal gas equation
 b) The generalized compressibility chart

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 Pure substance
 Phases of a pure substance
 Phase-change processes of pure substances
◦ Compressed liquid, Saturated liquid, Saturated vapor, Superheated vapor
◦ Saturation temperature and Saturation pressure
 Property diagrams for phase change processes
◦ The T-v diagram, The P-v diagram, The P-T diagram, The P-v-T surface
 Property tables
◦ Enthalpy
◦ Saturated liquid, saturated vapor, Saturated liquid vapor mixture,
Superheated vapor, compressed liquid
◦ Reference state and reference values
 The ideal gas equation of state
◦ Is water vapor an ideal gas?
 Compressibility factor
 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

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