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Clausius-Clapeyron Equation: Liquid Solid
Clausius-Clapeyron Equation: Liquid Solid
Clausius-Clapeyron Equation: Liquid Solid
p (mb)
C
221000
Liquid
Solid
1013
6.11 T
Vapor
Cloud drops first form when the vaporization equilibrium point is reached
(i.e., the air parcel becomes saturated)
https://www.slideshare.net/KLXun1/metr3210-clausiusclapeyron
Here we develop an equation that describes how the vaporization/condensation
equilibrium point changes as a function of pressure and temperature
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Outline:
Clausius-Clapeyron Equation
Basic Idea
Derivation
Applications
Equilibrium with respect to Ice
Applications
Thermodynamics M. D. Eastin
Review of Water Phases
Homogeneous Systems (single phase):
Solid
pv, Tv
1013
6.11 T
pv pw Vapor
Tv Tw
pw, Tw 0 100 374 T (C)
Thermodynamics M. D. Eastin
Review of Water Phases
Equilibrium Phase Changes:
Liquid C
pv pw Tv Tw 221,000
Tc =
374C
C B A Vapor
A B C Liquid
and T1
Solid Vapor T
6.11
Solid Tt =
and 0C
Vapor
Thermodynamics M. D. Eastin
Review of Latent Heats
Equilibrium Phase Changes:
L dQ constant
221,000
Tc =
L 374C
Vapor
From the forming or breaking of
molecular bonds that hold water L T1
molecules together in its different Solid T
6.11
phases L Tt =
Latent heats are weak function of 0C
temperature
V
Thermodynamics M. D. Eastin
Changes to Notation
Water vapor pressure:
We will now use (e) to represent the
pressure of water in its vapor phase Ideal Gas Law for Water Vapor
(called the vapor pressure)
Allows one to easily distinguish between p v v R v Tv
pressure of dry air (p) and the pressure
of water vapor (e)
e v R vT
Temperature subscripts:
We will drop all subscripts to water and
dry air temperatures since we will assume
the heterogeneous system is always in
equilibrium
T Tv Tw Ti
Thermodynamics M. D. Eastin
Changes to Notation
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
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Who are these people?
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Basic Idea:
p (mb)
Provides the mathematical relationship C
221000
(i.e., the equation) that describes any
equilibrium state of water as a function
of temperature and pressure. Liquid
Vapor
esw 0 100 374 T (C)
Liquid T
Sections of the P-V and P-T diagrams for
Liquid which the Clausius-Clapeyron equation
and is derived in the following slides
Vapor V
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Mathematical Derivation:
Isothermal process
Adiabatic process
Saturation vapor pressure
T2 T1
Volume
Temperature
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Mathematical Derivation:
Q1 WNET
T1 T1 - T2
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Mathematical Derivation:
Recall: Q1 WNET
During phase changes, Q = L
T1 T1 - T2
Since we are specifically working
with vaporization in this example,
Q1 L v Isothermal process
Adiabatic process
Volume
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Mathematical Derivation:
Recall: Q1 WNET
The net work is equivalent to the
area enclosed by the cycle:
T1 T1 - T2
WNET dV dp
The change in pressure is: Isothermal process
Adiabatic process
desw esw1 esw2
dV v w dm
esw2 T2
A D
Q2
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Mathematical Derivation:
We then make all the substitutions into our Carnot Cycle equation:
Q1 WNET L v v w dm desw
T1 T1 - T2 T dT
dT T v w
esw2
Clausius-Clapeyron Equation
for the equilibrium vapor pressure T2 T1
with respect to liquid water Temperature
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
General Form:
C
dp s l
221000
dT T
Liquid
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Application: Saturation vapor pressure for a given temperature
and using: esw v R v T [Ideal gas law for the water vapor]
We get: de sw lv dT
e sw R v T2
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:
e sw desw lv T dT
e s0 esw
Rv T0 T 2
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Application: Saturation vapor pressure for a given temperature
e sw desw lv T dT
e s0 esw
Rv T0 T 2
After integration we obtain:
esw lv 1 1
ln
es0 R v T0 T
After some algebra and substitution for es0 = 6.11 mb and T0 = 273.15 K we get:
lv 1 1
esw (mb) 6.11 exp
R v 273.15 T(K)
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Application: Saturation vapor pressure for a given temperature
lv 1 1
esw (mb) 6.11 exp
R v 273.15 T(K)
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:
5.09 ln T ( K )
6808
esw (mb) 6.11 exp 53.49
T (K )
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Application: Saturation vapor pressure for a given temperature
5.09 ln T ( K )
6808
esw (mb) 6.11 exp 53.49
T (K )
esw = 32 mb
esw = 1005 mb
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Application: Boiling Point of Water
desw lv
dT T v w
This equation describes the change in boiling point temperature (T) as a function
of atmospheric pressure when the saturated with respect to water (esw)
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Application: Boiling Point of Water
What would the boiling point temperature be on the top of Mount Mitchell
if the air pressure was 750mb?
T = 366.11 K
T = 93C (boiling point temperature on Mt. Mitchell)
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Equilibrium with respect to Ice:
p (mb)
We will know examine the equilibrium
C
vapor pressure for a heterogeneous 221000
system containing vapor and ice
Liquid
P
(mb) Solid
1013
Liquid C 6.11 T
Vapor
Vapor
esi
B A T V
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Equilibrium with respect to Ice:
p (mb)
Return to our general form of the
C
Clausius-Clapeyron equation 221000
de s l Liquid
dT T Solid
1013
Make the appropriate substitution for 6.11 T
the two phases (vapor and ice)
Vapor
desi ls
dT T v i 0 100 374 T (C)
Clausius-Clapeyron Equation
for the equilibrium vapor
pressure with respect to ice
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
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
ls 1 1
esi (mb) 6.11 exp
R v 273.15 T(K)
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:
0.555 ln T ( K )
6293
esi (mb) 6.11 exp 26.16
T (K )
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
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)
dp wi lf
dT T w i
This equation describes the change in melting point temperature (T) as a function
of pressure when liquid water is saturated with respect to ice (pwi)
Thermodynamics M. D. Eastin
Clausius-Clapeyron Equation
Summary:
Clausius-Clapeyron Equation
Basic Idea
Derivation
Applications
Equilibrium with respect to Ice
Applications
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.
Thermodynamics M. D. Eastin