CHAPTER 2

Thermodynamic Properties
of Pure Substance

ENGINEERING SCIENCE 14a ENGR. PAOLO ROMMEL P. SANCHEZ & ENGR. MA. CONCEPCION DUNGCA-IGNACIO
Engineering Thermodynamics Engineering Science Department, CEAT
and Heat Transfer University of the Philippines Los Baos
 CHAPTER 2
Thermodynamic Properties of Pure Substance

CHAPTER OUTLINE
Pure Substance
Phase Change Processes of a
Pure Substance
Property Diagrams for Phase-
Change Processes
State Principle
Property Table
 CHAPTER 2
Thermodynamic Properties of Pure Substance

CHAPTER OBJECTIVES
At the end of the chapter, the student
should be able to:

define a pure substance;

identify different phases, phase
changes and states of a pure
substance;
identify different property diagrams
and its components; and
use the property table in solving
thermodynamic problems.

3
Pure Substance
is one that has a homogeneous and
invariable chemical composition
throughout its extent
may exist in more than one phase,
but the chemical composition must
be the same in all phases
e.g. liquid water, a mixture of liquid
water and steam, mixture of ice and
liquid water
Sometimes, mixture of gases, such
as air, is considered a pure
substance as long as there is no
change of phase.
Phases of a Pure Substance
A Phase is a distinct molecular
arrangement separated by boundary
surfaces
Pure substances have the following
principal phases: solid, liquid and gas.
 Why do we need to study
properties and behavior of pure
substances?
 Examine a Steam Power Plant

A steam power plant will have the following processes:

1. Boiling water to produce steam in a steam generator;
2. Expansion in a turbine to a lower pressure;
3. Cooling in a condenser; and
4. Returning the liquid water to the boiler at a high pressure.
Examine a Steam Power Plant

We must know the water

properties to properly size
the equipment such as the
heat exchangers, turbine,
pump, and even the
amount of water needed
for energy transfer to
properly facilitate.
Phase Change Processes of a Pure Substance
Consider a piston-cylinder device containing liquid water
at 20C and 1 atm pressure.

Under these conditions, water

exists in the liquid phase

Compressed liquid/Subcooled liquid

- liquid is not about to vaporize
 Phase Change Processes of a Pure Substance

At 1 atm and 100 C, water exists as

liquid that is ready to vaporize

Saturated liquid
- liquid that is about to vaporize

As more heat is transferred, part of the

saturated liquid vaporizes

Saturated liquid vapor mixture

Liquid and vapor phases co-exist in
equilibrium
Phase Change Processes of a Pure Substance

Saturated Vapor
A vapor that is about to condense

Superheated Vapor
A vapor that is not about to condense
Some Notes From Phase Change
Phenomenon
1. Strictly speaking, the statement
water boils at 100C is not always
true.
2. If the pressure inside the cylinder
were raised to 500kPa by adding
weights on top of the piston,
water would start boiling at
151.8C.
3. Therefore, the temperature at
which water starts boiling depends
also on its pressure.
4. At point 2 to point 4, temperature
and pressure remained constant
but the specific volume increased.
Saturation Temperature and
Pressure

Saturation Temperature, Tsatn:

temperature at which
vaporization takes place at a
given pressure

Saturation Pressure, Psatn:

pressure at which vaporization
takes place at a given
temperature
Latent Heat
Latent heat is the amount of energy
absorbed or released during a phase-
change process.

Latent heat of fusion

amount of energy absorbed during melting
equivalent to the amount of energy
released during freezing
Latent heat of vaporization
amount of energy absorbed during
vaporization
equivalent to the amount of energy
released during condensation
 Property Diagrams for Phase-Change Processes

Pressure-Temperature Diagram

It was clear that Tsat

increases with Psat.
Other experiments
showed that melting
temperatures were
also dependent with
pressure and vice
versa.
From these
observation, a P-T
diagram, also know
as Phase Diagram,
was developed.
 Property Diagrams for Phase-Change Processes

Pressure-Temperature Diagram

In a phase diagram, all three phases are separated

from each other by three lines:
Sublimation line: separates the solid and vapor
regions
Vaporization line: separates the liquid and vapor
regions
Melting (or fusion) line: separates the solid and
liquid regions.

Note that the triple point in the phase diagram is

where all three phases coexist in equilibrium.
 Property Diagrams for Phase-Change Processes

Pressure-Specific Volume Diagram

isotherms
 Property Diagrams for Phase-Change Processes

Pressure-Specific Volume Diagram

The experiment also showed that Pressure is also
dependent on specific volume during the phase change
of a substance.
Each pair of specific volume and pressure can be
connected together forming the Saturation lines.
o Saturated Liquid Line: Separates compressed and saturated
liquid-vapor regions. Phase is only saturated liquid.
o Saturated Vapor Line: Separates superheated and saturated
liquid-vapor regions. Phase is only saturated vapor.
The area bounded by the saturation lines is the Wet or
Saturated Region where saturated liquid and vapor exist in
equilibrium.
 Property Diagrams for Phase-Change Processes

Pressure-Specific Volume Diagram

Joining the two saturation lines is the critical point
which is the point at which the saturated liquid and
saturated vapor states are identical (not distinct).
There are three critical properties: Critical Pressure
(Pcr), Critical Temperature (Tcr) and Critical Specific
Volume (vcr)
Note that the temperature decreases from left to
right in the compressed liquid and superheated-
vapor region while it remains constant along the
saturated region as shown by the isotherms.
 Property Diagrams for Phase-Change Processes

Pressure-Specific Volume Diagram

o P v Diagram of a
Substance that
Contracts on
Freezing:

o P v Diagram of a
Substance that
Expands on
Freezing:
 Property Diagrams for Phase-Change Processes

Temperature-Specific Volume Diagram

isobars
 Property Diagrams for Phase-Change Processes

Temperature-Specific Volume Diagram

The experiment also showed that Temperature is also

dependent on specific volume during the phase chane of a
substance.
A similar curve with P-v diagram except that pressure
increases from left to right in the compressed liquid and
superheated-vapor region while it also remains constant along
the saturated region as shown by the isobars.
For critical properties, 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.
 Property Diagrams for Phase-Change Processes

P-T-v Diagram

The three
diagrams can be
combine
together to form
the P-T-V
diagram.
Front View: P-v
diagram
Right-side View:
P-T diagram
Top View: T-v
diagram
Property Table

State Principle
Any two independent intensive
thermodynamic properties are sufficient
to describe the state of a system
containing a single pure substance.
From these two independent intensive
properties, other thermodynamic
properties can be determined from an
established list of properties.
Property Table

properties are frequently presented in

the form of tables
Use data tabulated based on T and P
o Compressed Liquid Tables
o Saturated Liquid-Vapor Tables
o Superheated Vapor Tables

P
Pressure
T
Temperature
v
Specific volume
u
Specific internal energy
h
Specific enthalpy A Combination Property
H = U + PV or h = u + Pv
s Specific entropy
 Property Table

1. Saturated liquid and Saturated

vapor
Subscript f = saturated liquid
g = saturated vapor
fg = difference between the
saturated vapor and
saturated liquid values
 Property Table

2. Saturated liquid-vapor mixture

during vaporization process, substance exists as part liquid and
part vapor
quality, x
 Property Table

3. Superheated vapor
a substance exists at the right of the saturated vapor line and at
temperature above the critical point temperature

characterized by:
Lower pressure
(P < Psatn at a given P)
Higher temperature
(T > Tsatn 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)
 Property Table

Superheated Vapor Example:

T= 90oC P=50 kPa

From the table at T= 90oC

P = 50 kPa < Psatn = 70.14 kPa

SUPERHEATED VAPOR
 Property Table

4. Compressed liquid/Subcooled Liquid

not commonly available
general approximation is to treat compressed liquid as
saturated liquid at a given temperature

characterized by:
Higher pressures
( P > Psatn at a given T)
Lower temperature
( T < Tsatn 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 )
 Property Table

Compressed Liquid Example:

T= 95oC P=100 kPa

From the table at T= 95oC

P = 100 kPa> Psatn = 84.55 kPa

COMPRESSED LIQUID
 End of Chapter 2

Thank you very much!

Prepare for a Quiz next meeting.
Reminder: Please photocopy your
thermodynamic table.