Content
Chemical Engineering Thermodynamics I  Pure substance
Chapter 03 – PVT Behaviour of Fluids
Dr. Dipak Maity (DM)
Assistant Professor
Department of Chemical Engineering
Institute of Chemical Technology (ICT Mumbai – IOC),
Odisha Campus, Bhubaneswar -751013, Odisha, India
Email: dipakmaity@gmail.com
Pure Substance
A pure substance is one that has a fixed (uniform/invariable) chemical
composition throughout even though there is a change of phase.
 Example: Elements (Fe, Cu, He, N2), chemical compounds (water,
stainless steel, carbon dioxide)
 A pure substance (PS) does not have to be elements or compound.
A mixture can be pure substance if it is chemically homogeneous.
 A mixture of two or more phases is still a pure substance as long as
the chemical composition of all phases is same, like mixture of ice and
water (solid & liquid) or mixture of water and steam (liquid & gas).
Air is a mixture of several gases, but it is often considered to be a
pure substance because it has a uniform chemical composition.
 However, a mixture of liquid air and gaseous air is not a pure
substance since the composition of liquid air is different from the
composition of gaseous air.
This is due to different components in air condensing at different
temperatures at a specified pressure.
 Phase rule
 T-v Diagram
 P-v Diagram
 P-T Diagram
 Property Tables
 P-v-T Relations for Vapors (Gases)
 Compressibility Factor
Phases of a Pure Substance
A phase is defined as having a distinct molecular
arrangement/structure/properties that is homogenous throughout
and separated from the others by easily identifiable boundary/
surfaces.
 A pure substance may exist in different phases. There are three
principle phases: solid, liquid, and gas.
 A pure substance may have several phases within a principal
phase e.g. carbon may exist as graphite or diamond in the solid
phase.
• Homogeneous system consists of a “single phase” separated by
distinct boundaries from other phases, e.g. solid, liquid, vapour,
gas, mixture of air & water vapour, water plus nitric acid and
octane plus heptane.
• Heterogeneous system consists of two or more phases e.g.
water plus steam, ice plus water and water plus oil.
 Example of phases and pure substance
2P
Pure
Pure
substances
substances
1P 2P
3P
Not pure
substances
Pure
substances
1P 2P
Ex: How many phase-rule variables must be specified to fix the
thermodynamic state of each of the following systems?
(a) Liquid water in equilibrium with its vapor.
(b) Liquid water in equilibrium with a mixture of water vapor and N2
(c) A three-phase system of a saturated aqueous salt solution at its
boiling point with excess salt crystals present.
(a) N = 1 (The system contains a single chemical species)
π  = 2 (two phases – one liquid and one vapor)
F = N − π + 2  = 1 − 2 + 2 = 1
Temperature or pressure, but not both, may be specified for a system
(b) N = 2 (two chemical species – water and nitrogen)
π  = 2 (two phases – one liquid and one vapor)
F = N − π + 2  = 2 − 2 + 2 = 2
Now temperature and pressure may be independently varied
(c) N = 2 (two chemical species – water and salt)
π  = 3 (three phases – crystalline salt, saturated aqueous solution,
and vapor generated at the boiling point)
F = N − π + 2 = 1 Temperature or pressure independently varied
The Phase Rule
For a multiphase system at equilibrium, the number of independent
variables that must be arbitrarily fixed to establish its intensive state is
called the number of degrees of freedom of the system.
Gibbs Phase rule: F = N - π – r +2 (or C-P-r+2)
F: number of degrees of freedom of the thermodynamic system
(number of independently variables/intensive properties (e.g. P, T).
N: number of components (chemical species) present in the system
π = number of co-existing phases
r = number of independent reactions (occur between components)
For a non-reactive system: F = N – π + 2 (or C-P+2)
 For a single phase system of a pure component, F = 2 i.e. both P, T
may be varied.
 For a biphasic system of a pure component (liquid water & steam),
F = 1 i.e., either T or P may be varied.
 At triple point for one component, F = 0, i.e., fixed value of P and T
Phase – Change Processes of Pure Substances
Consider a process that a pure substance starts as liquid and is
heated up at constant pressure until it all becomes as gas.
 Depending on the prevailing pressure, the matter will pass
through various phase transformations.
1. Compressed/Sub-cooled liquid (not about to vaporize)
2. Saturated liquid (about to vaporize)
3. Saturated liquid-vapor mixture/Wet vapor (liquid & vapor coexist
in equilibrium)
4. Saturated vapor (about to condense)
5. Superheated vapor (not about to condense)
 Property (T-v) Diagrams for Phase Change Processes T-v diagram representing constant pressure phase changes
T (◦C) 1 atm B
Saturated
liquid Superheated
V vapor
C
L
Saturated
Saturated liquid- vapour
A vapour mixture

Liquid Compressed v (m3/kg) Vapor

liquid
Q Q If we increase the pressure of water in the piston-cylinder device,
Vapor
AL VB the process from compressed liquid to superheated vapor will follow
Liquid
Temperature rises Temperature rises a path that looks like the process for P = 1 atm
LV The only difference is that the width of the saturated liquid-
Small inc. in v Q Moderate inc. in v
Temp. constant saturated vapor mixture region will be shorter.
Constant pressure (Isothermal) Then, at a certain pressure, the mixture region will be represented
heat addition process
Large inc. in v only by one point (critical point).

Saturation or Vapor Dome

T-v Diagram
Isobars
Critical Point P2 = const > P1 The point where a phase begins, or ends is called a saturation point
T
Subcooled  If we connect all the points representing saturated liquid we will
liquid region P1 = const
obtain the saturated liquid line.
Superheated  If we connect all the points representing saturated vapor we will
T-v diagram Vapor region obtain the saturated vapor line.
 The intersection of the two lines is the critical point which defines
Saturated
Liquid-Vapor the maximum temperature
region  At the critical point the saturated liquid and saturated vapor states
are identical (not distinguishable). Above the critical temperature the
v liquid and vapor cannot co-exist at equilibrium.
The properties of a substance at the critical point, are called critical
liquid saturation line (first vapor saturation line (first properties (critical temperature (Tcr), critical pressure (Pcr) and critical
sign of vapor) → by joining sign of liquid) → by joining specific volume (vcr)).
saturation liquid states saturation vapor states The dome shaped two-phase region composed of liquid and vapor
(left of critical point) (right of critical point) is called the saturation or vapor dome.
 Saturation Temperature and Saturation Pressure Compressed (Subcooled) liquid & Superheated Vapor
T Psat(T*)
During a phase-change process, pressure and temperature are
P*
dependent properties, Tsat = f (Psat).
T*
 Compressed (Subcooled) liquid: T* < Tsat(P*) or P*>Psat(T*)
Tsat(P*) Liquid saturation line Liquid saturation line
Tsat(P*) P* isobar
Tsat(P*) P* isobar
v T* T*
(P*,T*) Psat(T*) isobar
Saturation Temperature, Tsat – At a given pressure, the temperature (P*,T*)
at which a pure substance starts boiling Superheated Vapor: Psat(T*) isobar
 Temperature where the P* isobar crosses the saturation line T* > Tsat(P*)
T* P* isobar
P*<< Psat(T*)
Saturation Pressure, Psat – At a given temperature, the pressure at (P*,T*)
Tsat(P*)
which a pure substance starts boiling
 Pressure where the T* isotherm crosses the saturation line Vapor saturation line

P-v diagram P-v Diagram

Isotherms (constant temperature lines)
Vapor Dome
If we remove the weights in the pressure-cylinder device one by one
to decrease the pressure, and allow a heat transfer to obtain an
isothermal process (T constant)
 We will obtain one of the curves of the P-v diagram.
 The general shape of a P-v diagram of a pure substance is very
similar to that of a T-v diagram
 The critical point defines the maximum pressure, i.e., above the
critical pressure a liquid and vapor cannot co-exist at equilibrium.
 Above the critical point isobars and isotherms do not pass through
the liquid-vapor region.
 The “triple point” is the point at which the liquid, solid, and vapor
phases can exist together.
 On P-v or T-v diagrams, these triple-phases states form a line
called the triple line.
 The states on the triple line of a substance have the same pressure
and temperature but different specific volumes.
 P substance that contracts P-T Diagram
during freezing (metals) P-T diagram is called the phase diagram since all three phases are
separated from each other by three lines.
F = C-P+2
P Between lines → F =2
Along Lines → F = 1
Triple point → F =0

v Solid → Liquid (melting/fusion line)

substance that expands Liquid → Vapor (vaporization line)
during freezing (water)
Solid → Vapor (sublimation line)
 Three lines meet at the triple point
T
If P>Ptp, pure substance melts into liquid & then evaporates
If P<Ptp, pure substance cannot exist in liquid phases
→ solid phase change directly to a vapor phase (sublimation)

Property Tables 1- Saturated Liquid-Vapor Mixture

Properties are frequently presented in the form of Property Tables
See TABLE A-4 and A-5 for saturated water (liquid-vapor) properties
(Steam Tables). T
How to analyze mass fraction in a mixture of saturated liquid and
Compressed Superheated
P vapor Table saturated vapor?
liquid Table
T P or T
T
Saturated liquid
Q -vapor Tables
v
 Tables contain the data of T, P, specific volume v, specific internal Saturated liquid

energy u, specific enthalpy h, and specific entropy s

 The subscript “f” is used for saturated liquid, “g” for saturated Saturated vapor
vapor and “fg” for difference between them
vf = specific vol. of saturated liquid v v
vg = specific vol. of saturated vapor
 Quality (x): mass fraction of vapor in saturated liquid-vapor
vfg = difference between vg and vf ( vfg = vg – vf)
mixture.
Consider a mixture mass m consists of the saturated liquid mass mf Similar type of equations for specific properties v, u, h, or s
and saturated vapor mass mg: m = mf + mg v = (1- x)vf + xv g  vav = vf + xv fg vfg = vg - vf
 The ratio of the mass of vapor to the mass of the total mixture is
called quality, x: u = (1- x)u f + xu g  u av = u f + xu fg u fg = u g - u f
mg mg m-m g m
x= = 1-x = = f h = (1- x)h f + xh g  h av = h f + xh fg h fg = h g - h f
mf + mg m m m
Note: 0 ≤ x≤ 1 s = (1- x)sf + xs g  sav = sf + xs fg s fg = s g - s f
at point L  x = 0 (saturated liquid line)
at point V  x = 1 (saturated vapor line) For any extensive property Y,
 The liquid has a mass mf and occupies a volume Vf yav = y f + x yfg yfg = (yg -yf )
 The vapor has a mass mg and occupies a volume Vg Note: saturated region is characterized
V = Vf +Vg but V = mv  Vf = m f vf , Vg = m g vg by: 0 ≤ x≤ 1  yf ≤ yav≤ yg

mf v f mg vg Lever Rule
mvav = m f vf + m g vg  vav = + vav -vf vg -vav
m m x= , 1-x =
vav = (1- x)vf + xv g  vav = vf + x(v g -v f ) or vf + xv fg vg -vf vg -vf

2- Superheated Vapor How to Choose the Right Table

See Table A-6 for superheated water vapor properties. Superheated
region is a single phase region (vapor only) which is characterized by:
Higher temperature (T > Tsat at a given P )
Lower pressure (P < Psat at a given T )
Higher specific volume, internal energy, enthalpy (v > vg ,
u > ug and h > hg at a given P or T)
 If T>> Tcr or P<<Pcr, then vapor can be approximated as “ideal gas”.
3- Compressed (or Sub-cooled) Liquid
See Table A-7 for compressed liquid water properties. Compressed region
is a single phase region (liquid only) which is characterized by:
Lower temperature (T < Tsat at a given P)
Higher pressure (P > Psat at a given T)
Lower specific volume, internal energy, enthalpy (v < vf, u < uf and
h < hf at a given P or T)
Compressed liquid approximated as saturated liquid at the given
temperature: y ≈ yf@T where y is v, u, or h.
To use a correct table, thermodynamic properties of a real substance
can always be compared to the properties in the saturation region.
Example: if pressure and specific volume are specified, then answer
of following questions at a given pressure:
is v < vf ?
is vf < v < vg ? only one answer is correct
is v > vg ?
 If v < vf then the state is compressed liquid region, and Table-A7 is
used to find the properties of the state.
If vf < v < vg then the state is saturated liquid-vapor region, and
Table-A4 or Table-A5 is used to find the properties. Then the quality
is calculated and is used to calculate the other properties, u, h, and s.
 If v > vg then the state is superheated vapor region and Table-A6
are used to find the other properties.

P-v-T Relations for Vapors (Gases)
Pv PV PV
= R (constant)  1 1 = 2 2 = mR = nMR
T T1 T2
since, mass (m) = number of moles (n) x molar mass (M)
Universal Gas Constant (Ru) for all gases
R u = MR = 8.314 kJ/kmol K (= N A k B )
Ideal gas law:
Pv = RT or PV = mRT =nMRT= nR u T or P = ρ RT
 An ideal gas is an imaginary substance. It is experimentally
observed that the ideal gas closely approximate the P-v-T behavior of
real gases at low densities.
 Many gases like air, nitrogen, oxygen, hydrogen, helium, argon,
neon, and CO2 can be treated as ideal gases with negligible error.
Water vapor and refrigerant vapor in refrigerators should not be
treated as ideal gases.
 Water vapor at pressures below 10 kPa (i.e. at low pressure) can
be treated as an ideal gas with negligible error (less than 0.1
percent), regardless of temperature.
The Ideal-Gas Equations of State
Any equation that relates pressure, temperature & specific volume
of a substance is called an equation of state
The simplest and best known equation of state for substances in
the gas phase is ideal-gas equation of state
The vapor phase of a substance is called a gas when it is above the
critical temperature or below critical pressure
 It is experimentally observed that the pressure of a gas is inversely
proportional to specific volume (P ∞1/v, Boyle’s law) and at a low
pressure, the volume of a gas is directly proportional to temperature
(v ∞T, Charles’ law)
T
P = R.  Pv =RT where R is the gas constant
v
This equation is ideal-gas equation of state (ideal gas relation) and
any gas obeys this relation (Pv = RT) is an ideal gas.
Ideal gas vs Real gas
An ideal gas is one which obeys Pv = RT equation
The assumption of ideal gas relation implies that:
 Particles take up negligible volume
 Intermolecular PE between particles is small (at low pressure
molecules are far apart so negligible PE)
 Particles act independent of one another (at high temp KE >> PE)
A real gas obviously does not obey the perfect/ideal gas equation
because
 the molecules have a finite size (however small it may be)
 they do exert forces among each other
 Molecules have KE associated with motion and PE associated
with mutual attraction/repulsion
 Compressibility chart (Z factor)
Compressibility Factor
Real gases deviate from ideal-gas behavior significantly at states
near the saturation region and the critical point.
 This deviation at given temperature and pressure can be
accounted by a correction factor called compressibility factor Z.
Pv v actual RT
Pv =ZRT  Z = = = 1 for ideal gases (videal = )
RT videal P
 For real gases Z can be greater than or less than unity. The farther
away Z is from unity, more the gas deviates from ideal-gas behavior.
 Gases behave differently at a given temperature and pressure, but
they behave very much the same at temperatures and pressures
normalized with respect to their critical temperatures/pressures
P T PR reduced pressure
PR = and TR = TR reduced temperature
P
cr Tcr
The Z factor for all gases is approximately the same at the same
reduced pressure (PR) and reduced temperature (TR).

The experimentally determined Z values are plotted against PR and

TR for several gases.
 By curve-fitting all the data, we obtain the generalized
compressibility chart that can be used for all gases.
From the compressibility chart, one can conclude:
 At very low pressure (PR <<1), the gases behave as an ideal gas
regardless of temperature
 At high temperature (TR>2), ideal gas behavior can be assumed
regardless of pressure (except when PR>> 1).
 The deviation of a gas from ideal-gas behavior is highest in the
vicinity of the critical point.
 Van der Waals intended to improve the ideal-gas equation of state
by including two of the effects not considered in the ideal-gas
model: the intermolecular attraction forces and the volume
occupied by the molecules themselves.
 Van der Waal’s equation: (P+a/v2)(v-b) = RT where constant a
and b represents attractive forces and finite volume of the molecule.