MEL140

Properties of pure substances

Pure substance
A pure substance has the same chemical composition
throughout.
Are the following confined in a fixed volume pure
substances:
Ice (single component, single phase)
A mixture of water and water vapor (single component, multiphase)
Air in gas phase (multi-component, single phase)
Oil in contact with water (multi-component single phase)
A gaseous mixture containing N2,O2,H2O, CO2 obtained from burning
kerosene (multicomponent, single phase)
Liquid air in contact with gaseous air (multicomponent, multiphase)
Objective: evaluating the properties for single component pure
substances existing in one or more phases (multiphase).

Y
Y
Y
N
Y
N

Alert: in chemistry a pure substance is defined such that it consists of one

component (chemical species) and therefore must be non-mixture. We follow a
different definition (see above) in engineering thermodynamics.

Phases
A region within matter with distinct molecular arrangement that is homogeneous
throughout that region which is separated from other regions (if any) by distinct
boundary surfaces. Physical properties (like density and refractive index) of each
phase is different.
The three principal phases:

Solid

Liquid

Gas

http://www.chem.purdue.edu/gchelp/atoms/states.html

Phase equilibrium
A system can be composed of
subsystems with different molecular
arrangements separated by phase
boundaries (phases).
Phase equilibrium prevails when no
transfer of mass happens between
phases.

The state postulate

A property is characteristic of the system such as specific volume
(v), temperature (T), pressure (P), (specific) internal energy (u).
A state is the condition of a system as determined by its properties.
A simple compressible system is a system whose only mode of
performing quasi-equilibrium work is through a change of its volume
against a pressure.
The state postulate: The state of a simple compressible system
consisting of a pure substance is completely specified by two
independent intensive properties.
The state postulate can be represented by an equation of state
such as f(p,v,T)=0 (or say g(p,v,u)=0). It is often convenient to
represent this functional relationship by
A surface in p,v,T (or u,p,v) space or more commonly its projections
on (p,v), (T,v) and (p,T) planes.
Tables of properties

The P-v diagram

Remove just enough heat

to keep temperature constant
as the volume is reduced.
It will be observed that except
during 2-3, pressure also
needs to be increased for
executing this process in a
quasi-equilibrium manner.
During 1-2 you 4-5 (not
during 2-3-4)

2
1

Shows isotherms on
P-v diagram

The critical state: recapitulation

At the critical state (Tc, Pc),
saturated liquid and
saturated vapor states are
identical (SLL intersects
SVL).
Increasing/decreasing
pressure at a given
temperature leads to
condensation/evaporation
only if a state lies below the
critical isotherm.

Phase change processes

Critical properties of common

fluids

Water/steam:

CP: 374o C (647.1 K), 22 Mpa (~more than 200 atm)

at which specific volume 0.003106 m3/kg (~three times less dense than @ STP)
BP at atmospheric pressure (101.325 kPa): 100 o C (1 atm)

Refrigerant 134a or R134a or

1,1,1,2-Tetrafluoroethane in your freeze:

CP: 101 C, 4 Mpa (~40 atmosphere)

BP at atmospheric pressure : -26 o C, 101.325 kPa (1 atm)
o

Nitrogen:

CP: -147o C, 3.4 MPa

BP at atmospheric pressure : -196o C

Carbon-dioxide:

CP: 31.05oC ,7.39 Mpa (CO2 is not a gas in Delhi for six months, i.e. Apr-Sept)
BP at atmospheric pressure: -78.5oC

Table A.1 (Tc,Pc,vc)

How far a state is away from critical point?
Curious facts:

Critical isotherm and the gas-vapor nomenclature

Supercritical fluidsT>Tcr and P>Pcr

Principle of corresponding states

(van der Waal, 1880)

of the substance, there is

Reduced temperature: Tr=T/TRegardless
c
a universal equation of state
Reduced pressure: Pr=P/Pc
connecting the reduced coReduced volume: vr=v/vc
ordinates. So, thermodynamic states

my equationofof different substances correspond.

Can be stated as:
state has a
v f (P ,T )
universal form
which can be
identified by its
predicted
behavior at
critical point
Other equation of
states might also be
given similar universal
forms by the same
procedure.
r

Principle of corresponding states

(van der Waal, 1880, continued)
Correspondence means the same reduced co-ordinates should
mean the sameness of a third reduced property such as reduced
volume.
Compressibility factor is an important reduced property given by:

PV
PV
Z
Z0 r r
RT
Tr

Z signifies departure from ideal gas behavior. More discussion on

significance in notes.
Principle of corresponding states: All fluids when compared at the
same Tr and Pr have the same Z and deviate from the ideal gas
behavior to about the same degree.
This principle is the basis of classifying systematizing organizing
and compacting experimental measurements on P, V and T.

Critical compressibility of real gases

Phase change processes

Some terminology
Compressed liquid or sub-cooled liquid:
Liquid which is not about to vaporize
(State 1)
Saturated liquid: liquid which is about to
vaporize (State 2)
Saturated vapor: vapor which is about to
condense (State 4)
Saturated liquid-vapor mixture: a mixture
of saturated liquid and saturated vapor
(State 3)
Superheated vapor: vapor that is not
about to condense (State 5)

Phase change processes

Compressed/
subcooled liquid

Saturated vapor

Saturated
liquid

Superheated
vapor

Saturated
liquid vapor
mixture

Latent heat
The energy absorbed by a system during a phase
change process at a given pressure/temperature is
called latent heat.
Latent heat of fusion (melting)
Latent heat of vaporization (boiling)

Latent heat goes to change the molecular potential

energy; in-fact temperature, a measure of molecular
kinetic energy remains constant during a phase
change process.

Saturation temperature, saturation

pressure and saturation curve
Phase change processes (e.g. saturated liquid
boiling to saturated vapor) under a given pressure (
saturation pressure or Psat) take place at a given
temperature
( saturation temperature or Tsat).
Therefore Psat=f (Tsat). A plot of this function is the
saturation curve

Saturation curve for water

Property diagram for phase change

processes: the T-v diagram.
234

Construct at
different pressures

The critical point

The state (point) at which

the saturated liquid and
the saturated vapor states ar
identical.

For water

The T-v diagram: saturated liquid

line and the saturated vapor line

Shows isobars
on T-v diagram

Saturated liquid and saturated vapor lines meet at the critical point.

The P-v diagram

Remove weights
to change pressure
during 1-2, 4-5 (not
during 2-3-4)
Shows isotherms on
P-v diagram

Extending the P-v diagram to

include solid phase
a solid at temperature lower
than melting point
b solid begins melting
c solid completely melted
d liquid begins to vaporize
e liquid completely vaporized
a

e
P-v diagram of a
substance which
contracts on
freezing (most
except water)

Extending the P-v diagram to

include solid phase
a ice at -10oC, 1 atm
Saturated liquid lines
Saturated
solid line
LIQUID

a c b d
SOLID

b ice begins melting

(0oC), 1 atm
c ice completely melted
(0oC), 1 atm
d water begins to vaporize
(100oC), 1 atm
e water completely
vaporized (100oC), 1 atm
P-v diagram of a
substance which
expands on freezing
(e.g. water)

The triple line

The states where all three phases coexist in equilibrium lie on a straight
line on the P-V or T-v diagram known
as a triple line.
All the triple states appear as a
point on the p-T diagram and the
corresponding (T,v) is called a triple
point.
Triple point of water: (0oC, 0.61 kPa)

The P-T diagram (phase

diagram)

The P-v-T surface

For substances which

contract on freezing

For substances which

expand on freezing (such as
water).

Enthalpy: a combination
property
Enthalpy (h):
h=u+pv
Enthalpy is useful for studying processes
(such as vaporization, heat transfer)
taking place at constant pressure and
processes that involve flow work

Objective
Evaluate properties of states
corresponding to:
saturated liquid and saturated vapor
saturated liquid-vapor mixtures
superheated vapor
compressed/sub-cooled liquid

Saturated liquid and saturated

vapor

Specified

Subscript f represents
saturated liquid
state
Subscript g represents
saturated vapor
state
Subscript i represents
saturated solid state.
Propertyfg=PropertygPropertyf

=vg-vf represents
volume change on
vaporization
hfg = =hg-hf represents
the latent heat or
enthalpy of vaporization.

From Table A-4

e.g. v
fg

Saturated liquid and saturated

vapor

Saturated states lie on the

curve f(Psat, Tsat)=0 and can
therefore be specified by
specifying either Psat, or Tsat

Table A-4 for water:

(Psat,vf,vg,vfg,uf,ug,

ufg,hf,hg,hfg,sf,sg,sfg) listed
against Tsat

Table A-5 for water:

(Tsat,vf,vg,vfg,uf,ug,

ufg,hf,hg,hfg,sf,sg,sfg)
listed against Psat

From Table A-4

Same data in Tables A-4

and A-5

Saturated liquid and saturated

vapor
Subscript f represents
saturated liquid
state
Subscript g represents
saturated vapor
state
Propertyfg=PropertygPropertyf
=vg-vf represents
volume change on
vaporization
hfg = =hg-hf represents
the latent heat or
enthalpy of vaporization

From Table A-4

e.g. v
fg

Saturated liquid-vapor
mixtures
Refer to same Tables A-4 and A-5.
The proportion of saturated vapor in the
mixture is indicated by a new property
quality or dryness fraction:
mg
mass of saturated vapor
x

total mass of the mixture m f mg

The average value of a specific extensive
property y (such as v,u,h) etc. for the mixture
can be calculated from

y y f xy fg

Saturated liquid-vapor
mixtures
Refer to same Tables A-4 and A-5.
The proportion of saturated vapor in the mixture is indicated by a
new property quality or dryness fraction:

mg
mass of saturated vapor
x

total mass of the mixture m f mg

x=0 for saturated liquid

0<x<1 for saturated liquid-vapor mixture
x=1 for saturated vapor
x is undefined for compressed liquid and superheated vapor
The average value of a specific extensive property y (such as
v,u,h) etc. for the mixture can be calculated from

y y f xy fg

Superheated vapor
At least two properties need to be given to
specify the state according to state
postulate
Usually either T or P and another property
is given:
At a superheated state:

P<Psat @ given T
T> Tsat @ P
v>v @ P/T
u>ug @ P/T
h>hg @ P/T
g

Visit Table A-6 for water

Properties of pure
substances (continued)
MEL140

Compressed liquid
At a compressed liquid state
P>Psat @ given T
T<Tsat @ given P
v<vf @ given P/T
u<uf @ given P/T
h<hf @ given P/T

Usually compressed liquid tables are

not available except Table A-7 for
water at P> 0.5 MPa

Approximately evaluating properties

at the compressed liquid state
For a compressed liquid, properties are
weakly dependent on p.
Treat compressed liquid as a saturated
liquid at the given temperature.
Evaluate:

v'vf@T
u'uf@T
h'hf?
Usually better approximation for h is:
h=u+pv'uf+pvf=hf-psatvf+pvf =hf+(p-psat)vf using
v'vf and u'uf@T and hf=(uf+ psatvf).

P [kPa]

Evaluate compressed liquid v at (T,p)

SteamNBS

105

SteamNBS

104

10

P [kPa]

103

104

100C

102
101

10
At given
T,
v is not
10
8x10
10
sensitive
to p.

10C

-1

-4

10

102

3x10-3

-3

v [m /kg]

100C

101
0

10

10-1
8x10-4

If no v is tabulated at given (P,T)

find vf@T=Tsat using saturation
table (Table A.4 for water)

10C

10-2

10-1

100
3

v [m /kg]

101

102

103

Determining the state

(summary)
Saturated liquid-vapor
mixture
(A.4,A.5 for water)

Compressed/subcooled liquid
(A.7, A.4 if not A.7 for water)

Superheated vapor
(A.6 for water)

P=Psat(T)

P>Psat @ T

P<Psat@T

T=Tsat(P)

T<Tsat @ P

T>Tsat@T

vf<v<vg

v<vf@P/T

v>vg@T

uf<u<ug

u<uf@P/T

u>ug@P/T

hf<h<hg

h<hf@P/T

h>hg@P/T

x=(y-yf)/yfg where
y=v/u/h
(0<x<1)

x undefined

x undefined