Volumetric Properties

of Pure Substances

System:
• Region enclosed by specified boundaries,
which may be imaginary, either fixed or
moving.
Surrounding:
• Region all about or around the system
Thermodynamic Systems:
• Closed System: no exchange of mass with
surroundings.
• Open System: there is a flow of mass across
the boundaries.
• Isolated System: neither mass nor energy
cross its boundaries.

The working substance:

Fluid: substance that exists as a continuum
characterized by low resistance to
flow and the tendency to assume the
shape of its container.
Pure Substance:
• One that has a homogeneous and
invariable chemical composition.
Incompressible Substance:
• Substances whose surface effects, magnetic
effects, and electrical effects are insignificant, but
changes in volume are very important.

1
 Properties and State
Properties: Descriptive characteristics that
express the behavior of the system
• Intensive Properties
• Extensive Properties
• Specific Properties

State: „ Condition as identified through

the properties of the substance;
„ Defined by particular values of
any two independent properties.

Phases:
• Solid
• Liquid
• Vapor or gas

Melting (fusion): solid to liquid

Freezing (solidification): liquid to solid
Boiling (Vaporization): liquid to gas
Condensation: vapor to liquid
Sublimation: solid to gas or vice- versa

Vapor-
Vapor-Liquid-
Liquid-Solid Phase
Equilibrium in a Pure Substance

Saturation Temperature:
Temperature: the temperature at
which the liquid will start to boil or the
temperature at which the vapor will begin to
condense at a given pressure or the
temperature at which vaporization (or
condensation) takes place at a given pressure
(saturation pressure)

H2O vapor H2O vapor

Liquid H2O Liquid H2O

2
Saturated Liquid:
Liquid: Substance existing as liquid at
the saturation temperature and pressure

Subcooled Liquid:
Liquid: Temperature of liquid is lower
than the saturation temperature for the existing
pressure;
: Temperature is lower than the
saturation temperature for a given pressure

Compressed Liquid:
Liquid: Temperature of liquid is lower
than the saturation temperature for the existing
pressure;
: Pressure is greater than the
saturation pressure for a given temperature

Quality (x):
(x): Ratio of the mass of vapor to the
total mass pertained to substance
existing as part liquid and part vapor at
the saturation temperature
Saturated Vapor:
Vapor: Substance existing as vapor at
the saturation temperature

Superheated Vapor:
Vapor: Vapor at a temperature
greater than the saturation temperature
: (superheated steam)
Wet mixture / wet steam:
steam: a combination of
saturated vapor and saturated liquid

% moisture: Percentage by mass that is liquid

Critical point: The saturated liquid and
saturated vapor states are identical.
Triple point: State in which all three phases
are in equilibrium
Allotropic transformation: A transition from
one solid phase to another
Heat of fusion: Amount of heat to change the
solid to a liquid, or vice versa, to
freeze the liquid at constant pressure
Latent heat: Heat for evaporation of a saturated
liquid into a saturated vapor, or vice
versa at constant pressure

3
 Property Diagrams
Saturation Temperature - Saturation Pressure

T
Vapor pressure curve of a pure substance

Saturated Liquid and Saturated Vapor States

Critical
P point
Saturated
liquid line Saturated
vapor
Vfg Line

Vf Vg V
Vf = specific volume of saturated liquid
Vg = specific volume of saturated vapor
Vfg = difference between Vf and Vg (Vfg = Vg − Vf)

Saturated liquid-vapor mixture

Critical
P point
Saturated
liquid line Saturated
(x = 0) vapor
Saturated Line
mixture (x = 1)
0<x<0

V
The calculation of the properties of a saturated
mixture involves the quality, x.

4
 Superheated Vapor
T

Saturated
vapor P Superheated Superheat region
line is a single-phase
vapor region (vapor
phase only)
T and P are
H independent
Hg
Hp>Hg
Superheat vapor is characterized by:
Lower pressure (P < Psatd at a given T)
Higher temperature (T > Tsatd at a given P)
Higher specific volumes (V > Vg at a given P or T)
Higher internal energy (U > Ug at a given P or T)
Higher enthalpy (H > Hg at a given P or T)

Compressed Liquid
In the absence of compressed liquid data, a general
approximation is to treat compressed liquid as saturated
liquid at the given temperature.

Given: P and T
V ≅ Vf @ T H ≅ Hf @ T U ≅ Uf @ T

Compressed liquid is characterized by

Higher pressure (P > Psatd at a given T)
Lower temperature (T < Tsatd at a given P)
Lower specific volumes (V < Vsatd at a given P or T)
Lower internal energy (U < Usatd at a given P or T)
Lower enthalpy (H < Hf at a given P or T)

P-V Diagram
P Critical
C point
Superheated
Compressed
Liquid Region

vapor region

Saturated
A liquid-vapor
region B

V
Curve AC – saturated liquid line
Curve BC – saturated vapor line

5
 Critical
P point

Liquid
Solid + Liquid
Vapor
Solid

Liquid + Vapor

Solid + Vapor

V
P-V diagram of a substance that contracts on freezing.
Solid + Liquid

P Critical
point
Liquid

Vapor
Solid

Liquid + Vapor

Triple Line
Solid + Vapor

V
P-V diagram of a substance that expands on freezing.

P-V Diagram
• The boiling temperature of a pure substance increases
with pressure. Vf and Vg also change with pressure.
• The normal boiling temperature of a pure substance is
the temperature at which it boils under P = 1 atm.
• series of isobars can be plotted on a T-V diagram. If the
locus of all saturated liquid and vapor states are
connected, a dome enclosing the region of two phases
(liquid+vapor) results
• Each pure substance has one isobar that becomes
horizontal (flat) at only one point. This point coincides
with the top of the two-phase dome.
• When we include solids, we have an additional single
phase region (solid) and two additional two-phase
regions (solid+vapor) and (solid+liquid).

6
 T T-V Diagram
Critical
point T, °C
Liquid P=1 atm
200
Vapor e
c
100
b d
20 a

V a-b : compressed liquid

Saturated Saturated
b-d : saturated mixture
liquid vapor d-e : superheated vapor

T-V Diagram
• The T-V diagram contains three single phase regions (liquid,
vapor, supercritical fluid), a two-phase (liquid+vapor) region,
and two important curves - the saturated liquid and saturated
vapor curves. The number of regions and curves will
increase when we consider solids.
• The saturated liquid and vapor curves meet at the critical
point, which represents the highest temperature and pressure
in which vapor and liquid phases can coexist.
• The single phase liquid region is also called subcooled liquid
because, at a given pressure, temperature will be below the
boiling temperature.
• The single phase vapor region is also called superheated
vapor because, at a given pressure, temperature will always
be above the boiling temperature.

P-T Diagram
Substances Substances
that expand that contract
P
on freezing on freezing

Melting Critical
point
LIQUID

SOLID Vaporization

VAPOR
Triple
Sublimation point

7
 P-T Diagram
• The triple line connects a solid, liquid and vapor state that coexist at
the same temperature and pressure. For a pure substance there will
be only one such line on the PVT surface.
• On the PT projection, two-phase regions collapse to curves.
• There is a one-to-one relationship between pressure and
temperature in two-phase regions. In the solid-vapor region, the
temperature at a given pressure is called the sublimation
temperature. In the solid-liquid region it is called the melting
temperature.
• The vapor pressure curve, melting curve, and sublimation curve
give the one-to-one relationship between pressure and temperature
in the vapor-liquid, solid-liquid and solid-vapor regions respectively.
• In the vapor-liquid region at a particular pressure, the temperature is
called the boiling temperature. At a particular temperature, the
pressure is called the vapor pressure.

P-V-T Diagram

Critical
Solid-Liquid

point
Liquid
Solid

P
Ga
s

Liquid-
Tri Vapor
p le
Li n V a p o
Soli e r
d-V
apo
r
V
T
Substance that contracts on freezing.

Critical
point
Liquid
Solid

P
Ga

Trip
s

le L
ine
V ap
o r
Solid-Vapor
V
T
Substance that expands on freezing.

8
 The Phase Rule
• Applicable only to systems in equilibrium
• Gibb’s phase rule
F=2−π−N
Where: F = number of degree of freedom
= the number of independent properties
that must be specified to determine all
the intensive properties of each phase
of the system.
π = the number of phase that can exist in
the system.
* phase – homogeneous quantity of the system
N = number of component in the system