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Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Cloud drops first form when the vaporization equilibrium point is reached
(i.e., the air parcel becomes saturated)
Here we develop an equation that describes how the vaporization/condensation
equilibrium point changes as a function of pressure and temperature
T
C
T (ºC)
p (mb)
3741000
6.11
1013
221000
Liquid
Vapor
Solid
Thermodynamics M. D. Eastin
Outline:
Review of Water Phases
Review of Latent Heats
Changes to our Notation
Clausius-Clapeyron Equation
Basic Idea
Derivation
Applications
Equilibrium with respect to Ice
Applications
Clausius-Clapeyron Equation
Thermodynamics M. D. Eastin
Homogeneous Systems (single phase):
Gas Phase (water vapor):
• Behaves like an ideal gas
• Can apply the first and second laws
Liquid Phase (liquid water):
• Does not behave like an ideal gas
• Can apply the first and second laws
Solid Phase (ice):
• Does not behave like an ideal gas
• Can apply the first and second laws
Review of Water Phases
pd dTcdq v
T
dqds rev
vvvv TRρp
Thermodynamics M. D. Eastin
Heterogeneous Systems (multiple phases):
Liquid Water and Vapor:
• Equilibrium state
• Saturation
• Vaporization / Condensation
• Does not behave like an ideal gas
• Can apply the first and second laws
Review of Water Phases
pw, Tw
pv, Tv
wv pp
wv TT
T
C
T (ºC)
p (mb)
3741000
6.11
1013
221000
Liquid
Vapor
Solid
Equilibrium States for Water
(function of temperature and pressure)
Thermodynamics M. D. Eastin
Equilibrium Phase Changes:
Vapor → Liquid Water (Condensation):
• Equilibrium state (saturation)
• Does not behave like an ideal gas
• Isobaric
• Isothermal
• Volume changes
Review of Water Phases
wv pp wv TT C
V
P
(mb)
Vapor
Solid
Tt =
0ºC
Liquid
Liquid
and
Vapor
Solid
and
Vapor
Tc =
374ºC
T1
6.11
221,000
T
B AC
A B C
Thermodynamics M. D. Eastin
Equilibrium Phase Changes:
• Heat absorbed (or given away)
during an isobaric and isothermal
phase change
• From the forming or breaking of
molecular bonds that hold water
molecules together in its different
phases
• Latent heats are a weak function of
temperature
Review of Latent Heats
constantdQ L C
V
P
(mb)
Vapor
Solid
Tt =
0ºC
Liquid
Tc =
374ºC
T1
6.11
221,000
T
L
L
L
Values for lv, lf, and ls are given
in Table A.3 of the Appendix
Thermodynamics M. D. Eastin
Water vapor pressure:
• We will now use (e) to represent the
pressure of water in its vapor phase
(called the vapor pressure)
• Allows one to easily distinguish between
pressure of dry air (p) and the pressure
of water vapor (e)
Temperature subscripts:
• We will drop all subscripts to water and
dry air temperatures since we will assume
the heterogeneous system is always in
equilibrium
Changes to Notation
vvvv TRρp
iwv TTT T
TRρe vv
Ideal Gas Law for Water Vapor
Thermodynamics M. D. Eastin
Water vapor pressure at Saturation:
• Since the equilibrium (saturation) states are very important, we need to
distinguish regular vapor pressure from the equilibrium vapor pressures
e = vapor pressure (regular)
esw = saturation vapor pressure with respect to liquid water
esi = saturation vapor pressure with respect to ice
Changes to Notation
Thermodynamics M. D. Eastin
Who are these people?
Clausius-Clapeyron Equation
Benoit Paul Emile Clapeyron
1799-1864
French
Engineer / Physicist
Expanded on Carnot’s work
Rudolf Clausius
1822-1888
German
Mathematician / Physicist
“Discovered” the Second Law
Introduced the concept of entropy
Thermodynamics M. D. Eastin
Basic Idea:
• Provides the mathematical relationship
(i.e., the equation) that describes any
equilibrium state of water as a function
of temperature and pressure.
• Accounts for phase changes at each
equilibrium state (each temperature)
Clausius-Clapeyron Equation
T
C
T (ºC)
es (mb)
3741000
6.11
1013
221000
Liquid
Vapor
Solid
V
es
(mb)
Vapor
Liquid
Liquid
and
Vapor
T
esw
Sections of the P-V and P-T diagrams for
which the Clausius-Clapeyron equation
is derived in the following slides
Thermodynamics M. D. Eastin
Mathematical Derivation:
Assumption: Our system consists of liquid water in equilibrium with
water vapor (at saturation)
• We will return to the Carnot Cycle…
Clausius-Clapeyron Equation
Temperature
T2 T1
esw1
esw2
Sa
tura
tio
n v
ap
or
pre
ss
ure
A, D
B, C
Volume
T2
T1esw1
esw2
Sa
tura
tio
n v
ap
or
pre
ss
ure
A D
B C
Isothermal process
Adiabatic process
Thermodynamics M. D. Eastin
Mathematical Derivation:
• Recall for the Carnot Cycle:
• If we re-arrange and substitute:
Clausius-Clapeyron Equation
21NET QQW
1
21
1
21
T
TT
Q
where: Q1 > 0 and Q2 < 0
21
NET
1
1
T-T
W
T
Q
Volume
T2
T1esw1
esw2
Sa
tura
tio
n v
ap
or
pre
ss
ure
A D
B C
Isothermal process
Adiabatic process
WNET
Q1
Q2
Thermodynamics M. D. Eastin
Volume
T2
T1esw1
esw2
Sa
tura
tio
n v
ap
or
pre
ss
ure
A D
B C
Isothermal process
Adiabatic process
WNET
Q1
Q2
Mathematical Derivation:
Recall:
• During phase changes, Q = L
• Since we are specifically working
with vaporization in this example,
• Also, let:
Clausius-Clapeyron Equation
21
NET
1
1
T-T
W
T
Q
v1 LQ
TT1
dTTT 21
Thermodynamics M. D. Eastin
Mathematical Derivation:
Recall:
• The net work is equivalent to the
area enclosed by the cycle:
• The change in pressure is:
• The change in volume of our system at
each temperature (T1 and T2) is:
where: αv = specific volume of vapor
αw = specific volume of liquid
dm = total mass converted from
vapor to liquid
Clausius-Clapeyron Equation
dmααdV wv
sw2sw1sw eede
21
NET
1
1
T-T
W
T
Q
dpdVWNET
Volume
T2
T1esw1
esw2
Sa
tura
tio
n v
ap
or
pre
ss
ure
A D
B C
Isothermal process
Adiabatic process
WNET
Q1
Q2
Thermodynamics M. D. Eastin
Mathematical Derivation:
• We then make all the substitutions into our Carnot Cycle equation:
• We can re-arrange and use the
definition of specific latent heat of
vaporization (lv = Lv /dm) to obtain:
Clausius-Clapeyron Equation
for the equilibrium vapor pressure
with respect to liquid water
Clausius-Clapeyron Equation
21
NET
1
1
T-T
W
T
Q
dT
dedmαα
T
L swwvv
wv
vsw
ααT
l
dT
de
Temperature
T2 T1
esw1
esw2
Sa
tura
tio
n v
ap
or
pre
ss
ure
A, D
B, C
Thermodynamics M. D. Eastin
General Form:
• Relates the equilibrium pressure
between two phases to the temperature
of the heterogeneous system
where: T = Temperature of the system
lx = Latent heat for given phase change
desx = Change in system pressure at saturation
dT = Change in system temperature
Δα = Change in specific volumes between
the two phases
Clausius-Clapeyron Equation
TΔdT
desx xl
T
C
T (ºC)
es (mb)
3741000
6.11
1013
221000
Liquid
Vapor
Solid
Equilibrium States for Water
(function of temperature and pressure)
Thermodynamics M. D. Eastin
Application: Saturation vapor pressure for a given temperature
Starting with:
Assume: [valid in the atmosphere]
and using: [Ideal gas law for the water vapor]
We get:
If we integrate this from some reference point (e.g. the triple point: es0, T0) to some
arbitrary point (esw, T) along the curve assuming lv is constant:
Clausius-Clapeyron Equation
wv αα
TRαe vvsw
2
v
v
sw
sw
T
dT
R
l
e
de
wv
vsw
ααT
l
dT
de
T
T 2
v
ve
esw
sw
0
sw
s0 T
dT
Re
de l
Thermodynamics M. D. Eastin
Application: Saturation vapor pressure for a given temperature
After integration we obtain:
After some algebra and substitution for es0 = 6.11 mb and T0 = 273.15 K we get:
Clausius-Clapeyron Equation
T
T 2
v
ve
esw
sw
0
sw
s0 T
dT
R
l
e
de
T
1
T
1
R
l
e
eln
0v
v
s0
sw
T(K)
1
273.15
1
R
l(mb)e
v
vsw exp11.6
Thermodynamics M. D. Eastin
Application: Saturation vapor pressure for a given temperature
A more accurate form of the above equation can be obtained when we do not
assume lv is constant (recall lv is a function of temperature). See your book for
the derivation of this more accurate form:
Clausius-Clapeyron Equation
T(K)
1
273.15
1
R
l(mb)e
v
vsw exp11.6
)(ln09.5
)(
680849.53exp11.6 KT
KT(mb)esw
Thermodynamics M. D. Eastin
Application: Saturation vapor pressure for a given temperature
What is the saturation vapor pressure with respect to water at 25ºC?
T = 298.15 K
esw = 32 mb
What is the saturation vapor pressure with respect to water at 100ºC?
T = 373.15 K Boiling point temperature
(near sea level)
esw = 1005 mb
Clausius-Clapeyron Equation
T(K)
1
273.15
1
R
l(mb)e
v
vsw exp11.6
Thermodynamics M. D. Eastin
Application: Boiling Point of Water
At typical atmospheric conditions near the boiling point:
T = 100ºC = 373 K
lv = 2.26 ×106 J kg-1
αv = 1.673 m3 kg-1
αw = 0.00104 m3 kg-1
This equation describes the change in boiling point temperature (T) as a function
of atmospheric pressure when the saturated with respect to water (esw)
Clausius-Clapeyron Equation
wv
vsw
ααT
l
dT
de
1sw Kmb36.21dT
de
Thermodynamics M. D. Eastin
Application: Boiling Point of Water
What would the boiling point temperature be on the top of Mount Mitchell
if the air pressure was 750mb?
• From the previous slide
we know the boiling point
at ~1005 mb is 100ºC
• Let this be our reference point:
Tref = 100ºC = 373.15 K
esw-ref = 1005 mb
• Let esw and T represent the
values on Mt. Mitchell:
esw = 750 mb
T = 366.11 K
T = 93ºC (boiling point temperature on Mt. Mitchell)
Clausius-Clapeyron Equation
1
ref
refswswKmb36.21
TT
ee
ref
refswswT
36.21
eeT
1sw Kmb36.21dT
de
Thermodynamics M. D. Eastin
Equilibrium with respect to Ice:
• We will know examine the equilibrium
vapor pressure for a heterogeneous
system containing vapor and ice
Clausius-Clapeyron Equation
T
C
T (ºC)
es (mb)
3741000
6.11
1013
221000
Liquid
Vapor
Solid
C
V
es
(mb)
Vapor
Solid
Liquid
T
6.11 T
ABesi
Thermodynamics M. D. Eastin
Equilibrium with respect to Ice:
• Return to our “general form” of the
Clausius-Clapeyron equation
• Make the appropriate substitution for
the two phases (vapor and ice)
Clausius-Clapeyron Equation
for the equilibrium vapor
pressure with respect to ice
Clausius-Clapeyron Equation
T
C
T (ºC)
es (mb)
3741000
6.11
1013
221000
Liquid
Vapor
Solid
TdT
desx xl
iv
ssi
ααT
l
dT
de
Thermodynamics M. D. Eastin
Application: Saturation vapor pressure of ice for a given temperature
Following the same logic as before, we can derive the following equation for
saturation with respect to ice
A more accurate form of the above equation can be obtained when we do not
assume ls is constant (recall ls is a function of temperature). See your book for
the derivation of this more accurate form:
Clausius-Clapeyron Equation
T(K)
1
273.15
1
R
l(mb)e
v
ssi exp11.6
)(ln555.0
)(
629316.26exp11.6 KT
KT(mb)esi
Thermodynamics M. D. Eastin
Application: Melting Point of Water
• Return to the “general form” of the Clausius-Clapeyron equation and make the
appropriate substitutions for our two phases (liquid water and ice)
At typical atmospheric conditions near the melting point:
T = 0ºC = 273 K
lf = 0.334 ×106 J kg-1
αw = 1.00013 × 10-3 m3 kg-1
αi = 1.0907 × 10-3 m3 kg-1
This equation describes the change in melting point temperature (T) as a function
of pressure when liquid water is saturated with respect to ice (ewi)
Clausius-Clapeyron Equation
iw
fwi
ααT
l
dT
de
1wi Kmb135,038dT
de
Thermodynamics M. D. Eastin
Summary:
• Review of Water Phases
• Review of Latent Heats
• Changes to our Notation
• Clausius-Clapeyron Equation
• Basic Idea
• Derivation
• Applications
• Equilibrium with respect to Ice
• Applications
Clausius-Clapeyron Equation
Thermodynamics M. D. Eastin
References
Petty, G. W., 2008: A First Course in Atmospheric Thermodynamics, Sundog Publishing, 336 pp.
Tsonis, A. A., 2007: An Introduction to Atmospheric Thermodynamics, Cambridge Press, 197 pp.
Wallace, J. M., and P. V. Hobbs, 1977: Atmospheric Science: An Introductory Survey, Academic Press, New York, 467 pp.
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