Clausius-Clapeyron Equation

p (mb)

Va
po

Liquid

riz
at i
on

Fusion

221000

Solid
1013
6.11
b
Su

lim

at

i on

Vapor

100

374

T (C)

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
Thermodynamics

M. D. Eastin

Clausius-Clapeyron Equation
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

Thermodynamics

M. D. Eastin

Review of Water Phases

Homogeneous Systems (single phase):
Gas Phase (water vapor):
Behaves like an ideal gas
Can apply the first and second laws

p v v R v Tv

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

dq c v dT pd

dq rev
ds
T
Thermodynamics

M. D. Eastin

Review of Water Phases

Heterogeneous Systems (multiple phases):

p (mb)

Liquid

Solid

pv, Tv

riz
at i
on

221000

Va
po

Equilibrium state
Saturation
Vaporization / Condensation
Does not behave like an ideal gas
Can apply the first and second laws

Equilibrium States for Water

(function of temperature and pressure)

Fusion

Liquid Water and Vapor:

1013
6.11

pv pw

b
Su

at
il m

ion

Vapor

Tv Tw
pw, Tw

Thermodynamics

100

374

T (C)

M. D. Eastin

Review of Water Phases

Equilibrium Phase Changes:
Vapor Liquid Water (Condensation):
Equilibrium state (saturation)
Does not behave like an ideal gas
Isobaric
Isothermal
Volume changes

Tv Tw

pv pw

P
(mb)

221,000

Liquid

C
A

C
Solid
6.11

B
Liquid
and
Vapor
Solid
and
Vapor

Tc =
374C

Vapor
T1
T
Tt =
0C

V
Thermodynamics

M. D. Eastin

Review of Latent Heats

Equilibrium Phase Changes:
Heat absorbed (or given away)
during an isobaric and isothermal
phase change

L dQ constant

P
(mb)

221,000

Liquid

C
Tc =
374C

From the forming or breaking of

molecular bonds that hold water
molecules together in its different
phases
Latent heats are weak function of
temperature

Vapor

Solid

T1
T

6.11
L

Tt =
0C

Values for lv, lf, and ls are given

in Table A.3 of the Appendix

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
(called the vapor pressure)
Allows one to easily distinguish between
pressure of dry air (p) and the pressure
of water vapor (e)
Temperature subscripts:

Ideal Gas Law for Water Vapor

p v v R v Tv
e v R vT

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
e

= vapor pressure (regular)

esw = saturation vapor pressure with respect to liquid water

esi = saturation vapor pressure with respect to ice

Thermodynamics

M. D. Eastin

Clausius-Clapeyron Equation
Who are these people?

Rudolf Clausius
1822-1888
German
Mathematician / Physicist

Benoit Paul Emile Clapeyron

1799-1864
French
Engineer / Physicist

Discovered the Second Law

Introduced the concept of entropy

Expanded on Carnots work

Thermodynamics

M. D. Eastin

Clausius-Clapeyron Equation

Solid
1013
6.11

P
(mb)

b
Su

Vapor

esw

lim

at

i on

Vapor

100

374

T (C)

Liquid
Liquid
and
Vapor

Thermodynamics

Liquid

riz
at i
on

Accounts for phase changes at each

equilibrium state (each temperature)

221000

Va
po

Provides the mathematical relationship

(i.e., the equation) that describes any
equilibrium state of water as a function
of temperature and pressure.

p (mb)

Fusion

Basic Idea:

Sections of the P-V and P-T diagrams for

which the Clausius-Clapeyron equation
is derived in the following slides

M. D. Eastin

Clausius-Clapeyron Equation
Mathematical Derivation:
Assumption:

Our system consists of liquid water in equilibrium with

water vapor (at saturation)

Isothermal process
Adiabatic process

esw1
esw2

Volume

T1
D

T2

Saturation vapor pressure

Saturation vapor pressure

We will return to the Carnot Cycle

B, C

esw1
esw2

A, D

T2

T1

Temperature

Thermodynamics

M. D. Eastin

Clausius-Clapeyron Equation
Mathematical Derivation:
Recall for the Carnot Cycle:

Q1 Q 2 T1 T2

Q1
T1
where: Q1 > 0 and Q2 < 0
If we re-arrange and substitute:

Saturation vapor pressure

WNET Q1 Q 2

Isothermal process
Adiabatic process

esw1

Q1

T1

WNET
esw2

Q2

T2

Volume

Q1 WNET

T1 T1 - T2
Thermodynamics

M. D. Eastin

Clausius-Clapeyron Equation
Mathematical Derivation:
Recall:

Q1 WNET

T1 T1 - T2

During phase changes, Q = L

Since we are specifically working
with vaporization in this example,

Q1 L v

T1 T
T1 T2 dT

Saturation vapor pressure

Also, let:

Isothermal process
Adiabatic process

esw1

Q1

T1

WNET
esw2

Q2

T2

Volume

Thermodynamics

M. D. Eastin

Clausius-Clapeyron Equation
Mathematical Derivation:
Recall:

Q1 WNET

T1 T1 - T2

The net work is equivalent to the

area enclosed by the cycle:

WNET dV dp
The change in pressure is:

The change in volume of our system at

each temperature (T1 and T2) is:

dV v w dm
where:

v = specific volume of vapor

w = specific volume of liquid

Saturation vapor pressure

de sw e sw1 e sw2

Isothermal process
Adiabatic process

esw1

Q1

T1

WNET
esw2

Q2

T2

Volume

dm = total mass converted from

vapor to liquid
Thermodynamics

M. D. Eastin

Clausius-Clapeyron Equation
Mathematical Derivation:
We then make all the substitutions into our Carnot Cycle equation:

L v v w dm de sw

T
dT

We can re-arrange and use the

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

de sw
lv

dT T v w
Clausius-Clapeyron Equation
for the equilibrium vapor pressure
with respect to liquid water
Thermodynamics

Saturation vapor pressure

Q1 WNET

T1 T1 - T2

B, C

esw1
esw2

A, D

T2

T1

Temperature

M. D. Eastin

Clausius-Clapeyron Equation
General Form:
Relates the equilibrium pressure
between two phases to the temperature
of the heterogeneous system

Equilibrium States for Water

(function of temperature and pressure)
p (mb)

T =
l =
dps =
saturation
dT =

between

Temperature of the system

Latent heat for given phase change
Change in system pressure at
Change in system temperature
= Change in specific volumes

riz
at i
on

Liquid

Va
po

where:

221000
Fusion

dp s
l

dT T

Solid
1013
6.11
b
Su

lim

at

i on

Vapor

the two phases

0

Thermodynamics

100

374

T (C)

M. D. Eastin

Clausius-Clapeyron Equation
Application: Saturation vapor pressure for a given temperature
Starting with:

de sw
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:

desw
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

e s0

Thermodynamics

desw
lv

e sw
Rv

dT
T0 T 2
T

M. D. Eastin

Clausius-Clapeyron Equation
Application: Saturation vapor pressure for a given temperature

e sw

e s0

de sw
l
v
e sw
Rv

dT
T0 T 2
T

After integration we obtain:

e sw
lv 1 1

ln

e s0 R v T0 T
After some algebra and substitution for es0 = 6.11 mb and T0 = 273.15 K we get:

lv
1
1

e sw (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

e sw (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:

6808
e sw (mb) 6.11 exp 53.49
5.09 lnT ( K )
T (K )

Thermodynamics

M. D. Eastin

Clausius-Clapeyron Equation
Application: Saturation vapor pressure for a given temperature

6808
e sw (mb) 6.11 exp 53.49
5.09 lnT ( K )
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

Thermodynamics

M. D. Eastin

Clausius-Clapeyron Equation
Application: Boiling Point of Water

de sw
lv

dT T v w
At typical atmospheric conditions near the boiling point:
T = 100C = 373 K
lv = 2.26 106 J kg-1
v = 1.673 m3 kg-1
w = 0.00104 m3 kg-1

de sw
36.21 mb K 1
dT

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?
From the previous slide
we know the boiling point
at ~1005 mb is 100C

de sw
36.21 mb K 1
dT

Let this be our reference point:

esw esw ref

36.21 mb K 1
T Tref

Tref = 100C = 373.15 K

esw-ref = 1005 mb
Let esw and T represent the
values on Mt. Mitchell:

esw esw ref

36.21

Tref

esw = 750 mb
T = 366.11 K
T = 93C
Thermodynamics

(boiling point temperature on Mt. Mitchell)

M. D. Eastin

Clausius-Clapeyron Equation
Equilibrium with respect to Ice:
p (mb)

Va
po

P
(mb)

Liquid

riz
at i
on

221000
Fusion

We will know examine the equilibrium

vapor pressure for a heterogeneous
system containing vapor and ice

Solid
1013
6.11

Liquid C

b
Su

lim

at

i on

Vapor

Vapor
Solid

Thermodynamics

374

T (C)

6.11

esi

100

M. D. Eastin

Clausius-Clapeyron Equation
Equilibrium with respect to Ice:
p (mb)

de si
ls

dT T v i

riz
at i
on

Liquid

Va
po

de s
l

dT T
Make the appropriate substitution for
the two phases (vapor and ice)

221000
Fusion

Return to our general form of the

Clausius-Clapeyron equation

Solid
1013
6.11
b
Su

lim

at

i on

Vapor

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

e si (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:

6293
e si (mb) 6.11 exp 26.16
0.555 lnT ( K )
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
At typical atmospheric conditions near the melting point:
T = 0C = 273 K
lf = 0.334 106 J kg-1
w = 1.00013 10-3 m3 kg-1
i = 1.0907 10-3 m3 kg-1

dp wi
135,038 mb K 1
dT

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:
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

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