Clausius-Clapeyron Equation: Liquid Solid

Clausius-Clapeyron Equation
p (mb)
C
221000
Liquid
Solid
1013
6.11 T
Vapor
0 100 374 T (C)
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
Outline:
Review of Water Phases

Review of Latent Heats
Changes to our Notation
Basic Idea
Derivation
Applications
Equilibrium with respect to Ice
Applications
Homogeneous Systems (single phase):
Gas Phase (water vapor):

Behaves like an ideal gas p v v R v Tv
Can apply the first and second laws
Liquid Phase (liquid water):

Does not behave like an ideal gas
Solid Phase (ice):

dq c v dT pd
dq rev
ds
T
Heterogeneous Systems (multiple phases):
Liquid Water and Vapor:

Equilibrium States for Water
Equilibrium state (function of temperature and pressure)
Saturation p (mb)
Vaporization / Condensation C
221000
Liquid
Solid
pv, Tv
1013
6.11 T
pv pw Vapor
Tv Tw
pw, Tw 0 100 374 T (C)
Equilibrium Phase Changes:
Vapor Liquid Water (Condensation):

Equilibrium state (saturation)
Isobaric
Isothermal P
Volume changes (mb)
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
Equilibrium Phase Changes:
Heat absorbed (or given away) P

(mb)
during an isobaric and isothermal
phase change
Liquid C
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
Values for lv, lf, and ls are given

in Table A.3 of the Appendix
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
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
e = vapor pressure (regular)

esw = saturation vapor pressure with respect to liquid water
esi = saturation vapor pressure with respect to ice
Who are these people?
Rudolf Clausius Benoit Paul Emile Clapeyron

1822-1888 1799-1864
German French
Mathematician / Physicist Engineer / Physicist
Discovered the Second Law Expanded on Carnots work

Introduced the concept of entropy
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
Accounts for phase changes at each Solid

equilibrium state (each temperature) 1013
6.11 T
P Vapor
(mb)
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
Mathematical Derivation:
Assumption: Our system consists of liquid water in equilibrium with

water vapor (at saturation)
We will return to the Carnot Cycle
Isothermal process
Adiabatic process
Saturation vapor pressure

B, C
esw1
B C
esw1 T1 A, D
esw2
esw2 T2
A D
T2 T1
Volume
Temperature
Recall for the Carnot Cycle:

Isothermal process
WNET Q1 Q 2 Adiabatic process

Q1 Q 2 T1 T2 Q1
esw1
B C
T1
Q1 T1 WNET
esw2 T2
A D
where: Q1 > 0 and Q2 < 0 Q2
If we re-arrange and substitute: Volume
Q1 WNET

T1 T1 - T2
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

Also, let:
T1 T B
Q1 C
esw1 T1
T1 T2 dT esw2
WNET
T2
A D
Q2
Volume
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

Q1
The change in volume of our system at B C
esw1 T1
each temperature (T1 and T2) is:
WNET
dV v w dm
esw2 T2
A D
Q2
where: v = specific volume of vapor

w = specific volume of liquid Volume
dm = total mass converted from
vapor to liquid
We then make all the substitutions into our Carnot Cycle equation:
Q1 WNET L v v w dm desw

T1 T1 - T2 T dT
We can re-arrange and use the

definition of specific latent heat of
vaporization (lv = Lv /dm) to obtain:

B, C
esw1
desw lv
A, D
dT T v w
esw2
for the equilibrium vapor pressure T2 T1
with respect to liquid water Temperature
General Form:
Relates the equilibrium pressure

between two phases to the temperature Equilibrium States for Water
of the heterogeneous system (function of temperature and pressure)
p (mb)
C
dp s l

221000
dT T
Liquid
where: T = Temperature of the system Solid

l = Latent heat for given phase change 1013
dps = Change in system pressure at saturation
6.11 T
dT = Change in system temperature
= Change in specific volumes between Vapor
the two phases
0 100 374 T (C)
Application: Saturation vapor pressure for a given temperature
Starting with: desw lv

dT T v w
Assume: v w [valid in the atmosphere]
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
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)
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 )

5.09 ln T ( K )
6808
esw (mb) 6.11 exp 53.49
T (K )
What is the saturation vapor pressure with respect to water at 25C?

T = 298.15 K
esw = 32 mb
What is the saturation vapor pressure with respect to water at 100C?

T = 373.15 K Boiling point
esw = 1005 mb
Application: Boiling Point of Water
desw lv

dT T v w
At typical atmospheric conditions near the boiling point:

T = 100C = 373 K
lv = 2.26 106 J kg-1 de sw
v = 1.673 m3 kg-1
36.21 mb K 1
dT
w = 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)
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 de sw

we know the boiling point
36.21 mb K 1
dT
at ~1005 mb is 100C
Let this be our reference point: e sw esw ref
36.21 mb K 1
Tref = 100C = 373.15 K T Tref
esw-ref = 1005 mb
esw eswref
Let esw and T represent the T Tref
values on Mt. Mitchell: 36.21
esw = 750 mb
T = 366.11 K
T = 93C (boiling point temperature on Mt. Mitchell)
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
Solid 0 100 374 T (C)

6.11 T
esi
B A T V
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)
for the equilibrium vapor
pressure with respect to ice
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 )
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
At typical atmospheric conditions near the melting point:

T = 0C = 273 K
lf = 0.334 106 J kg-1 dp wi
w = 1.00013 10-3 m3 kg-1
135,038 mb K 1
dT
i = 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 (pwi)
Summary:

Changes to our Notation
Basic Idea
Derivation
Applications
Equilibrium with respect to Ice
Applications
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.

Clausius-Clapeyron Equation: Liquid Solid

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Clausius-Clapeyron Equation

0 100 374 T (C)

Review of Water Phases

Changes to our Notation

Gas Phase (water vapor):

Liquid Phase (liquid water):

Solid Phase (ice):

Liquid Water and Vapor:

Vapor Liquid Water (Condensation):

Heat absorbed (or given away) P

Values for lv, lf, and ls are given

e = vapor pressure (regular)

Rudolf Clausius Benoit Paul Emile Clapeyron

Discovered the Second Law Expanded on Carnots work

Accounts for phase changes at each Solid

Assumption: Our system consists of liquid water in equilibrium with

We will return to the Carnot Cycle

Saturation vapor pressure

Recall for the Carnot Cycle:

WNET Q1 Q 2 Adiabatic process

Saturation vapor pressure

If we re-arrange and substitute: Volume

Saturation vapor pressure

Saturation vapor pressure

where: v = specific volume of vapor

We can re-arrange and use the

Saturation vapor pressure

Relates the equilibrium pressure

where: T = Temperature of the system Solid

0 100 374 T (C)

Starting with: desw lv

Assume: v w [valid in the atmosphere]

What is the saturation vapor pressure with respect to water at 25C?

What is the saturation vapor pressure with respect to water at 100C?

At typical atmospheric conditions near the boiling point:

From the previous slide de sw

Solid 0 100 374 T (C)

At typical atmospheric conditions near the melting point:

Review of Water Phases

Changes to our Notation

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