2014/9/22

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.
Chapter 2 (Part 1) • Demonstrate the procedures for determining thermodynamic
PROPERTIES OF PURE properties of pure substances from tables of property data.

SUBSTANCES • 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.
Some notes and pictures are taken from
• Present some of the best-known equations of state.
Thermodynamics: An Engineering Approach, 6th Edition
Yunus A. Cengel, Michael A. Boles
McGraw-Hill, 2008

PURE SUBSTANCE PHASES OF A PURE SUBSTANCE

• 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 The molecules
in a solid are
pure substance (it has a uniform chemical composition ). kept at their
• A mixture of liquid and gaseous air is not a pure substance positions by the
large springlike
inter-molecular
forces.

Nitrogen and gaseous air are A mixture of liquid and gaseous

water is a pure substance, but a
pure substances.
mixture of liquid and gaseous air
is not.
The arrangement of atoms in different phases: (a) molecules are at relatively fixed
positions in a solid, (b) groups of molecules move about each other in the liquid
phase, and (c) molecules move about at random in the gas phase.
3 4

PHASE-CHANGE PROCESSES OF PURE SUBSTANCES

PHASE-CHANGE PROCESSES OF At 1 atm(≈1bar) and
PURE SUBSTANCE STATE 1
20°C, water exists in
the liquid phase
STATE 2
(compressed liquid).
• To demonstrate the basic principles involved
in phase-change process for pure substance,
water is taken as an example. At 1 atm pressure
and 100°C, water
exists as a liquid
• Consider a piston-cylinder device containing that is ready to
liquid water (H2O) vaporize
(saturated liquid).
-Given Pressure: 1 atm
• Compressed liquid (subcooled liquid): A substance that is not about
to vaporize.

• Saturated liquid: A liquid that is about to vaporize.

5 *Phase-change process from liquid to vapor is about to take place 6

1
 2014/9/22

PHASE-CHANGE PROCESSES OF PURE SUBSTANCES

PHASE-CHANGE PROCESSES OF PURE SUBSTANCES
STATE 3 STATE 4
STATE 5
As more heat is
transferred, the
temperature of the
vapor starts to rise
(superheated vapor).

As more heat is transferred,

part of the saturated liquid At 1 atm pressure, the
vaporizes (saturated liquid– temperature remains
vapor mixture). constant at 100°C until the
last drop of liquid is vaporized
(saturated vapor). • Superheated vapor: A vapor that is not about to condense (i.e., not a
saturated vapor).
• Saturated liquid–vapor mixture: The state at which the liquid and
vapor phases coexist in equilibrium.
8

• Saturated vapor: A vapor that is about to condense.

8

If the entire process described in the figure is reversed (state 5 to 1)
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.
Saturation Temperature and Saturation Pressure
• 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.

Saturated vapor

The liquid–vapor
saturation curve
of a pure
substance
Saturated liquid T-v diagram for the (numerical values
heating process of are for water).
water at constant
pressure.
9 10

Saturation Temperature and Saturation Pressure

Simple Questions:
• During a phase-change process, P and • The liquid that is about to vaporize is called ………………..
T are obviously dependent properties

𝑇𝑠𝑎𝑡 = 𝑓(𝑃𝑠𝑎𝑡 )
• A vapor that is about to condense is called …………………

• A curve of this kind is characteristic

of all pure substances • If the pressure of a substance is increased during a boiling process,
will the temperature also increase or will it remain constant? Why?
The liquid–vapor saturation curve of a pure
substance (numerical values are for water).

• The atmospheric pressure, and thus the boiling

temperature of water, decreases with elevation.

11 12

2
 2014/9/22

Quiz.. Revision on “Cooling Chamber/Bag”

1. A process during which the temperature remains constant is • Vacuum cooling-based on reducing the pressure to the saturation
called….. pressure at the desired low temperature (For example: 0oC)
2. A process during which the pressure remains constant is called….. • The heat of evaporation during evaporation process is absorbed
3. A process during which the specific volume remains constant is from the products lowering the product temperature
called…..
4. Is it possible to have water vapor at -10oC?
5. What is the difference between critical point and triple point?
6. Does quality have any meaning in the superheated vapor region?

The variation of the temperature of

fruits and vegetables with pressure
13 during vacuum cooling from 25°C 14
to 0°C.

Saturation Temperature and Saturation Pressure Some Consequences of

• Latent heat: The amount of Tsat and Psat Dependence
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.

melting vaporization
LIQUID WATER
ICE WATER VAPOR
freezing condensation

The temperature of liquid The variation of the temperature of

• Latent heat of vaporization: The amount of energy absorbed during nitrogen exposed to the fruits and vegetables with pressure
vaporization and it is equivalent to the energy released during atmosphere remains during vacuum cooling from 25°C
condensation. constant at 196°C, and to 0°C.
thus it maintains the test
• The magnitudes of the latent heats depend on the temperature or pressure chamber at 196°C.
at which the phase change occurs.
15 16

PROPERTY DIAGRAMS FOR PHASE- • saturated liquid line

• saturated vapor line
CHANGE PROCESSES
• The variations of properties during phase-change processes are best • compressed liquid region
studied and understood with the help of property diagrams such as the • superheated vapor region
T-v, P-v, and P-T diagrams for pure substances. • saturated liquid–vapor
mixture region (wet region)
• Critical point

T-v diagram of
constant-pressure
T-v diagram of a pure substance.
phase-change
processes of a pure At supercritical
substance at various Critical point: The point at
pressures (P > Pcr),
pressures which the saturated liquid
there is no distinct
(numerical values and saturated vapor states
phase-change
are for water). are identical.
17 (boiling) process. 18

3

P-v diagram of a pure substance.
• T constant lines have a downward trend
For the case of a substance that expands on
freezing:
P-v-T surface of a substance that
expands on freezing (like water).
*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.
The important of properties diagram
• We can show any process
that a system go through by
using the diagram.
• Example:
→1kg water is heated in
constant pressure from state 1
to state 2.
→Then the system is heated in
constant volume until state 3.
• The properties values can be
defined at each state
involved in the process
The pressure in a piston–cylinder
device can be reduced by
reducing the weight of the piston.
19
P-v diagram of a substance that
expands on freezing (such as water).
Vital consequence in nature
Example: Ice floats at the top
of rivers, lakes and oceans
21
3
2
1
23
2014/9/22
For the case of a substance that contracts on
freezing:
P-v diagram of a substance that
P-v-T surface of a substance contracts on freezing.
that contracts on freezing.
*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.
20
P-T Diagram or Phase Diagram
Sublimation: Passing from
the solid phase directly into
the vapor phase.
At low pressures (below
P-T diagram of pure substances.
the triple-point value),
-At triple point, all three phases coexist in equilibrium
solids evaporate without
melting first (sublimation). At triple-point pressure and
temperature, a substance exists in
three phases in equilibrium.
For water,
Ttp = 0.01°C
Ptp = 0.6117 kPa 22
PROPERTY TABLES
• Properties are frequently presented in the form of tables to reduce complexity.
• 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
-From the Greek word, means to heat
The combination u + Pv is frequently The product pressure 
encountered in the analysis of control volume (Pv) has energy
24
volumes. units.
4
 2014/9/22

Saturated Liquid and Saturated Vapor States

• Table A–4: Saturation properties of water, listed under temperature.
• Table A–5: Saturation properties of water, listed under pressure. Examples: Pressure of saturated
A partial list of Table A–4. liquid in a tank
A rigid tank contains 50kg of
saturated liquid water at 90oC.
Enthalpy of vaporization, hfg ( or Latent Determine the pressure in the tank
heat of vaporization): The amount of
energy needed to vaporize a unit mass of and the volume of the tank.
saturated liquid at a given temperature or
pressure.
*Caution: Determine the substance used (whether water or R134-a), to avoid
wrong selection of table

25 26

T-v diagram for the example

27 28

Example: Temperature of saturated

vapor in a piston-cylinder device

A piston cylinder device contains

0.06m3 of saturated water vapor at
350kPa pressure. Determine the
temperature and the mass of the
vapor inside the cylinder

29 30

5
 2014/9/22

Saturated Liquid–Vapor Mixture

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. -for internal energy and enthalpy:
→during vaporization, only the amount of saturated liquid changes, not its properties
→The same can be said about a saturated vapor

Quality is related to the horizontal

distances on P-v and T-v diagrams.

The relative SUMMARY:

The v value of a
amounts of saturated liquid– y v, u, or h.
liquid and vapor mixture lies
vapor phases between the vf and vg
in a saturated values at the
mixture are A two-phase system can be
treated as a homogeneous specified T or P.
specified by
the quality x. mixture for convenience.
31 32

Analysis:

PRESSURE AND VOLUME OF -Since two phases coexist in equilibrium, we have a saturated mixture

SATURATED MIXTURE

• A rigid tank contains 10kg of water at

90oC. If 8kg of the water is in the
liquid form and the rest is in the vapor
form, determine (a) the pressure in
the tank and (b) the volume of the
tank

33 T-v diagram for the example. 34

Superheated Vapor Example

In the region of superheated
Compared to saturated vapor,
vapor, temperature and
superheated vapor is characterized by
pressure are independent
properties.
• Determine the temperature of
water at a state of P=0.5MPa and
h=2890kJ/kg. Please show and
label the conditions/states of
At a specified
P, superheated
vapor exists at
water on P-v diagram with respect
a higher h than
the saturated
to saturation lines (Considering
vapor.
the process is isothermal)
A partial *Caution: Linear interpolation can be used when the properties could
listing of not be determined directly
Table A–6. 35 36

6
 2014/9/22

Compressed Liquid
Given P=0.5MPa and h=2890 kJ/kg
Compressed liquid is characterized by
In the absence of compressed liquid
-Refer to Table A-5, at 0.5MPa, hg= 2748.1 kJ/kg. data, a general approximation is as
since h> hg, it is superheated vapor. Based on Table A-6, the follows:
temperature is between 200 and 250oC. Then, by linear interpolation, y  v, u, or h
we get

T=216.3oC

-However, h is the most sensitive to

the variations in the pressure.
The compressed liquid -Thus, a more accurate relation for
properties depend on h at low to moderate pressures and
P-v Diagram??? temperature much more
strongly than they do on
pressure.
temperatures, is as follows:

37 38

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 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 reference 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.

39