BITS Pilani
Pil i
Pilani Campus
L t
Lecture 3:
3 Ph
Phase behavior
b h i off pure substance
b t
Review
• State Postulate, Equilibrium surface, Process
• Thermal contact, thermal equilibrium, Zeroth law, and
temperature
• Equation of state, Thermometry
• Scales of temperature
• Pressure
• Phase behaviour of pure substance
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Pure Substance Phase Behavior
• Experiment with water at Constant Pressure: T-v behavior
• Saturation Temperature – temperature at which liquid and vapor coexist
at given P, ie., the boiling temperature
• Saturation Pressure – pressure at which liquid and vapor coexist at
given
i Y
Y, ie.,
i theth vapor pressure
• The saturation T of water at 0.1 MPa is 99.6º C, and vice versa
• At fixed pressure, the temperature does not change as long as the two
phases coexist
coexist. If heat is added
added, the relative amount of vapor increases
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Vapor Pressure
• The vapor pressure of a pure liquid increases with
increasing temperature
• The vapor pressure has a unique value at a given
temperature
• The vapor pressure curve terminates at a critical point
beyond which there is no distinction between liquid and
vapor
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T-v diagram for water
Horizontal line segment (tie-line) at each pressure connects a pair of
saturated liquid and saturated vapor phases in equilibrium.
g of this line segment
Length g decreases with increasing gp pressure ((and
temperature), and is of vanishing length at the critical point beyond which
there is no distinction between liquid and vapor
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T-v liquid-vapor equilibrium - water
As one moves from left to right in the saturation region at a given T and
P,, the relative amount of vapor
p grows
g at the expense
p of the liquid.
q
Quality x = mg/m, fraction of total mass present as vapor, varies from 0 to
1 along tie line
At any point on the line, v = (1-x)vf + xvg = vf + xvfgg where vf and vg are
the specific volumes of the liquid and vapor phases respectively, and vfg
= vg - vf
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Solid-Liquid Equilibrium
• If container has ice at 0.1 MPa and -20ºC, and heat is
transferred,
f system remains homogeneous, with small
change in v, till the temperature reaches 0ºC, at which
temperature the ice begins to melt. As further heat is added,
the temperature remains constant till all the ice melts.
• This is the melting temperature, and this depends on the
pressure When solid and liquid are in equilibrium
pressure. equilibrium, the solid
is said to be saturated.
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Sublimation, the Triple Point
• If we begin with ice at 0.260 kPa and -20ºC, and add heat,
the temperature rises till -10ºC,
ºC at which point, the solid
directly converts to vapour (sublimation). The temperature
remains constant till all the ice has sublimed
• If finallyy we start with ice at 0.6115 kPa and -20ºC,, and add
heat, the system remains homogeneous till the temperature
reaches 0
0.01
01ºC
C, at which point both liquid and vapour
appear. This is the triple point, the unique T and p at which
three
h phases
h off a pure substance
b can coexist
i at equilibrium
ilib i
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P-T Phase Diagram (Water)
Substance that expands upon freezing
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P-T Phase Diagram – CO2
Substance that expands upon melting
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P-T Phase Diagram - Water
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PvT Surfaces
What determines which phase is stable at a given P and T?
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T-v diagram for water
What about P-v diagram?
Compressed Superheated vapour
(sub-cooled)
liquid
Horizontal line segment (tie-line) at each pressure connects a pair of
saturated liquid and saturated vapor phases in equilibrium.
g of this line segment
Length g decreases with increasing gp pressure ((and
temperature), and is of vanishing length at the critical point beyond which
there is no distinction between liquid and vapor
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T-v liquid-vapor equilibrium - water
x = mg/m
V = Vf + Vg = mfvf + mgvg
v = (1 – x)vf + xvg
= vf + xvfg
As one moves from left to right in the saturation region at a given T and
P,, the relative amount of vapor
p grows
g at the expense
p of the liquid.
q
Quality x = mg/m, fraction of total mass present as vapor, varies from 0 to
1 along tie line
At any point on the line, v = (1-x)vf + xvg = vf + xvfgg where vf and vg are
the specific volumes of the liquid and vapor phases respectively, and vfg
= vg - vf
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Some terms
• Fusion (melting), Vaporization, and Sublimation, Triple
Point
• Liquid-Vapour Equilibrium -Saturated liquid and vapour,
Compressed (Sub-cooled) Liquid, Superheated Vapour,
Critical Point,, Supercritical
p region
g
• Solid – Liquid Equilibrium - Saturated solid and liquid
• Solid – Vapour Equilibrium - Saturated solid and vapour
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Thermodynamic tables
Engineering applications require the knowledge of the values of various
properties of commonly used substances in different states. While figures
are useful
useful, data are much more precisely presented in tables tables. Some of
the tables include:
• Critical constants – table A2
• Properties
P ti off selected
l t d solids
lid (A3) and d liliquids
id (A4)
(A4), and d id
ideall gases (A5)
• Properties of water - saturated liquid and vapour, organized according
to the temperature (B1.1), and pressure (B1.2). In these tables, apart
f
from the
th saturation
t ti temperature
t t andd pressure, theth values
l off specific
ifi
volume (v), internal energy (u), enthalpy (h), and entropy (s) of coexisting
liquid and vapour phases are given.
• Superheated
S h t d watert vapour (B1.3).
(B1 3) Th
The ttable
bl iis organized
i d accordingdi tto
the pressure. For each pressure, the values of v, u, h, and s are listed for
various temperatures starting from the saturation temperature.
• Compressed
C d ((sub-cooled)
b l d) liliquid
id (B1
(B1.4),
4) organized i d as above,
b b
butt ffor
various temperature values at and below saturation for various pressures
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Thermodynamic tables
• Properties of water – saturated solid and vapour (B1.5) organized by
temperature, as Table B1.1
• Tables
T bl similar
i il to those
h ffor water, b
but rather
h lless extensive,
i are given
i iin
B2 to B7 for other substances
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