PVT Behavior of Pure

Substances
Ms. N. DEEPA PRIYA
Assistant Professor
Department of Chemical Engineeringg
Kongu Engineering College
Perundurai, TN, India
P-T Diagram
• A typical P-T diagram showing the relationship between pressure and temperature of pure substance is shown below:
• Measurement of the vapor pressure of a pure solid at temperature up to its triple point and measurement of the vapor pressure of the pure liquid at
temperatures above triple point, lead to P Vs T curves shown by lines 1-2 and 2- C
• The third line 2-3 gives the solid-liquid equilibrium relationship
• The three curves represent the conditions P and T at which two phases, and thus are
boundaries for the single phase regions

Line 1-2 Line 2-3 Line 2-C

• Sublimation • Fusion Curve • Vaporization
Curve • Separates the Curve
• Separates the solid and liquid • Separates the
solid and gas regions liquid and gas
regions regions

• All the three lines meet at the triple point (0.010C, 0.0061 bar), where the
three phases coexist in equilibrium.
• According to the phase rule, the triple point is invariant (F=0).
• If the system exists along any path of the two-phase lines, it is univariant (F=1), whereas in the single-phase regions it is divariant (F=2)
• Although the fusion curve 2-3 continues upward indefinitely, the vaporization curve 2-C terminates at point C, the critical point.
Critical Pressure and Critical Temperature
• The pressure and temperature corresponding to this point (Critical Point) are known as the critical pressure PC and critical temperature TC respectively.
These are the highest pressure and temperature at which a pure substance can exist in vapor-liquid equilibrium.
Process Thermodynamics, 2
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Process Thermodynamics, 3
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Fluid region : Exist at higher temperatures and pressures; marked off by dashed lines
A phase is generally considered as liquid, if it can be vaporized by reduction in
pressure at constant temperature
A phase is considered as gas, if it can be condensed by reduction of temperature
at constant pressure
• Since neither process occur in the area of dashed lines, it is called „Fluid Region‟

• The gas region is sometimes divided into two parts; as shown by the dotted line in
fig.
A gas to the left of this line, which can be condensed either by compression at
constant temperature or by cooling at constant pressure, is called vapor
The region everywhere to the right of this line T>Tc, including the fluid region, is
termed „supercritical‟
• Paths such as the one from A to B is fig. lead from the liquid region to the gas region
without crossing a phase boundary. The transition from liquid to gas is gradual.
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Vapor Liquid Equilibrium
Process Thermodynamics, 6
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 PTxy diagram for vapor/liquid equilibrium

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• The under surface represents saturated-
vapor states, it is the P-T-y1 surface

• The upper surface represents saturated-

liquid states, it is the P-T-x1 surface

• These surfaces intersect along the lines

UBHC1 and KAC2, which represent the
vapor pressure vs T curves for pure
species 1 and 2

• The upper and under surface form a

continuous rounded surface across the
top of the diagram between C1 and C2,
the critical points of pure species
1 and 2
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• The critical points of the various
mixtures of the two species lie along a
line on a rounded edge of the surface
between C1 and C2
• The critical locus is defined by the
points at which vapor and liquid phases
in equilibrium become identical
• The region lying above the upper
surface is the subcooled-liquid region
• The region lying below the under
surface is the superheated-vapor region
• The interior space between the two
surfaces is the region of coexistence of
both liquid and vapor phases
Process Thermodynamics, 9
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• If one starts with a liquid at F and
reduces the pressure at constant
temperature and composition along a
vertical line FG, the first bubble of
vapor appears at point L, which lies on
the upper surface

• Thus L is the bubble point, and the

upper surface is the bubble point
surface
When heating a liquid consisting of two or more
components, the bubble point is the temperature where first
bubble of vapor is formed.

For single component the bubble point is the boiling point

of a liquid mixture at a given composition
Process Thermodynamics, 10
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• The state of the vapor bubble in
equilibrium with the liquid at L must be
represented by a point on the under
surface at a temperature and pressure of
L

• This point is indicated by the letter V

• Line VL is an example of a tie line,

which connects points representing
phase in equilibrium
A tie line is an isothermal (constant temperature) line
connecting the compositions of the two phases in a two
phase field. It is used to find the compositions of the
phases in the two phase field.
Process Thermodynamics, 11
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• As the pressure is further reduced along
the line FG, more and more liquid
vaporizes until at W the process is
complete
• Thus W lies on the under surface and
represents a state of saturated vapor
having the mixture composition
• Since W is the point at which the last
drops of liquid (dew) disappears, it is a
dew point, and the lower surface is the
dew point surface
• Continuous reduction of pressure merely
leads into the superheated region
The dew point is the point at which the first drop of
gaseous mixture begins to condense
Process Thermodynamics, 12
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
•A vertical plane
perpendicular to the
temperature axis is
outlined as ALBDEA

• The lines on this plane

represent P-x1-y1 phase
diagram at constant T

• If the lines from several

such planes are projected
on a single parallel plane, a
the P-x1-y1 diagram is
obtained
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• The one for Ta represents
the section indicated by
ALBDEA
• The temperature Tb lies
between the two pure
species critical
temperatures
• The temperature Td is
above critical temperatures
• The tie lines connecting
the phases in equilibrium
are horizontal, and the tie
line connecting identical
phases must therefore the
last such line to cut the
diagram
Process Thermodynamics, 14
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• A horizontal plane passed
through the P-T-
composition diagram
perpendicular to P axis is
identified by HIJKLH

• Viewed from the top, the

lines on this plane
represent a T-x1-y1
diagram

• When lines of several

pressures are projected on
a parallel plane, the T-X1-
Y1 diagram is obtained
Process Thermodynamics, 15
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• The third plane identified is the
vertical one perpendicular to the
composition axis indicated by
MNQRSLM
• When projected on a parallel
plane, the lines from several such
planes present a PT diagram
• In P-T diagram, lines UC1 and
KC2 are vapor-pressure curves for
the pure species
• Each interior loop represents the
P-T behavior of saturated liquid
and of saturated vapor for a
mixture of fixed composition
• For Pure species the critical point
is the highest temperature and
highest pressure at which vapor
and liquid phases coexist
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• To the left of the critical point C a reduction in
pressure along a line such as BD is
accompanied by vaporization of liquid from
bubble point to dew point

• If the original condition corresponds to point F,

a state of saturated vapor, liquefaction occurs
upon reduction of the pressure and reaches a
maximum at G, after which vaporization takes
place until the dew point is reached at H. This
phenomenon is called Retrograde
Condensation
Retrograde condensation occurs when gas in a tube is
compressed beyond the point of condensation with the effect
that the liquid evaporates again. This is opposite of
condensation : the so-called retrograde condensation
Process Thermodynamics, 17
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 • It is of considerable importance in the operation of certain deep natural
gas well where the pressure and temperature in the underground
formation are approximately the conditions represented by point F
• If one then maintains the pressure at the wellhead at a value near that
of point G, considerable liquefaction of the product stream is
accomplished along with the partial separation of the heavier species
of the mixture
• Within the underground formation itself, the pressure tends to drop as
the gas supply is depleted
• If not prevented, this leads to the formation of liquid phase and a
consequent reduction in the production of well
• Repressuring is therefore a common practice, lean gas(gas from which
the heavier species have been removed) is returned to the underground
reservoir maintained at elevated pressure
Process Thermodynamics, 18
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
Azeotropes
 • Azeotropes are a mixture of two of more liquids which cannot be
separated by simple distillation and the mixture behaves as a pure
liquid having a fixed boiling point. This happens as the composition of
the vapour phase and the liquid phase are the same.

• A Azeotrope or a constant boiling mixture is a mixture of two or more

liquids whose proportions cannot be altered by simple distillation

Process Thermodynamics, 20
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 • There are two types of solutions:
- Ideal Solutions which follows the Raoult's law
- Non Ideal Solutions which doesn't follows the Raoult's

Process Thermodynamics, 21
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• Within non-ideal solutions, some
solutions show positive deviation,
in which the intermolecular force
of attraction between the solute-
solute and solvent-solvent are
more stronger than solute-solvent
interaction

• Non ideal binary solution of two

liquids showing Positive
Deviation are known as
Minimum Boiling Azeotrope.

• For example a binary solution of

ethanol and water is consider a
Minimum Boiling Azeotrope
Process Thermodynamics, 22
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
• Within non-ideal solutions, some
solutions show negative deviation,
in which the intermolecular force of
attraction between the solute-solute
and solvent-solvent are weaker than
solute-solvent interaction

• Non ideal binary solution of two

liquids showing Negative
Deviation are known as Maximum
Boiling Azeotrope.

• For example a mixture of water and

nitric acid is consider a Maximum
Boiling Azeotrope
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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 Characteristics of Minimum Boiling Characteristics of Maximum Boiling
Azeotrope Azeotrope
• The boiling point of this azeotrope is lower • The boiling point of this azeotrope is higher than
than the boiling points of its constituents the boiling points of its constituents

• The interaction between the solvent-solvent • The interaction between the solvent-solvent and
and solute-solute molecules are stronger than solute-solute molecules are weaker than solvent-
solvent-solute molecules which results in their solute molecules which results in their high
low boiling point boiling point

• Volume of the solution is lower than the sum of • Volume of the solution is higher than the sum of
the individual volumes of the constituents the individual volumes of the constituents
because of low solute-solvent molecular because of high solute-solvent molecular
interaction. interaction

• Enthalpy of the mixture of its constituents is • Enthalpy of the mixture of its constituents is
positive negative

• 96% ethanol solution forms a minimum boiling • 68% nitric acid solution forms a maximum
azeotrope boiling azeotrope
Process Thermodynamics, 24
Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN
 Reference :
Smith J. M., Van Ness H. C. and Abbot M M., “Introduction to
Chemical Engineering Thermodynamics”, 7th Edition, McGraw Hill,
2005

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Ms.N.Deepa Priya , Department of Chemical Engineering, Kongu Engineering College, Perundurai, TN