02 Thermodynamics of Moist Air

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ESCI 340 - Cloud Physics and Precipitation Processes

Lesson 2 - Thermodynamics of Moist Air


Dr. DeCaria

References:
Glossary of Meteorology, 2nd ed., American Meteorological Society
A Short Course in Cloud Physics, 3rd ed., Rogers and Yau, Chs. 1 and 2

Humidity Variables
This section contains a review of the humidity variables used by meteorologists.
vapor pressure, e: The partial pressure of the water vapor in the atmosphere.
saturation vapor pressure, es : The vapor pressure at which liquid water and vapor would
be in equilibrium.
• Saturation vapor pressure is found from the Clausius-Clapeyron Equation,
  
Lv 1 1
es = e0 exp − (1)
Rv T0 T
where T0 = 273.15K, e0 = 611 Pa, Lv is the latent heat of vaporization, and
Rv is the specific gas constant for water vapor.
• The Clausius-Clapeyron equation gives the saturation vapor pressure over a flat
surface of pure liquid water.
• If the liquid contains impurities, or the interface between the liquid and vapor is
curved, corrections for the solute effect and curvature effect must be applied.
Relative Humidity, RH: Relative humidity is defined as the ratio of vapor pressure to
saturation vapor pressure, and is expressed as a percent.
e
RH = × 100% (2)
es
• Relative humidity is always defined in terms of a flat surface of pure liquid water.
• The World Meteorological Organization (WMO) uses an alternate definition of
relative humidity, which is the ratio of mixing ratio to saturation mixing ratio,
r
RH = × 100%. (3)
rs
The two definitions (2) and (3) are not identical, but are very close and are usually
considered to be interchangeable.
Saturation Ratio, S: The relative humidity expressed as a simple ratio rather than as a
percent. For example, if RH = 45% then S = 0.45.

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Absolute humidity, ρv : The mass of water vapor per volume of air. The relation between
vapor pressure and absolute humidity is given by the ideal gas law for pure water vapor,
(11).

Mixing ratio, r: The mass of water vapor per mass of dry air. Mixing ratio is related to
vapor pressure by
Rd e e
r= =ε , (4)
Rv p − e p−e
where Rd and Rv are the specific gas constants for dry air and water vapor respectively,
and p is the total air pressure.

Specific humidity, q: The mass of water vapor per total mass of air.

• Mixing ratio and specific humidity are related via


r
q= . (5)
1+r
• Mixing ratio and specific humidity are very close in value, and are often used
interchangeably.

Dewpoint, Td : The temperature to which air must be cooled at constant pressure and
specific humidity in order to reach 100% relative humidity.

• When the temperature is equal to the dewpoint temperature, the vapor pressure
is equal to the saturation vapor pressure. Thus, if dewpoint temperature is used
in the Clausius-Clapeyron equation the result is the vapor pressure,
  
Lv 1 1
e = e0 exp − .
Rv T0 Td

Ideal Gas Law


• The ideal gas law is
pV = nRT, (6)
where R is the universal gas constant, 8.3145 J mol−1 K−1 .

• Equation (6) is not the most convenient form for meteorology. Instead we use the form

p = ρR0 T (7)

where R0 is the specific gas constant, a unique constant for each individual gas
species.

– The specific gas constant is defined as

R0 = R/M, (8)

where M is the molar mass of the gas.

2
• The ideal gas law for dry air is
p = ρRd T (9)
where Rd is the specific gas constant for dry air, 287.1 J kg−1 K−1 .

• The ideal gas law can also be written in term of specific volume, α = 1/ρ,

pα = Rd T. (10)

• For pure water vapor the ideal gas law is

e = ρv Rv T (11)

where Rv is the specific gas constant for water vapor, 461.5 J kg−1 K−1 , and ρv is the
absolute humidity .

• For moist air, which is a mixture of dry air and water vapor, the ideal gas law is

p = ρRd T (1 − q + q/ε) (12)

where q is the specific humidity and ε = Rd /Rv .

• By defining the virtual temperature as

Tv = T (1 − q + q/ε) (13)

we can write (12) as


p = ρRd Tv . (14)

– Virtual temperature is simply a definition, allowing us to use the dry-air ideal gas
law for moist air by simply using the virtual temperature in place of the actual
temperature.
– Virtual temperature is not a measurable temperature. It must be calculated.
– Substituting for the value of ε allows equation (13) to be written as

Tv = T (1 + 0.61q). (15)

The First Law of Thermodynamics


• The First Law of Thermodynamics states that there are two ways to change the internal
energy, U of a system: 1) Add or remove heat, Q; 2) Via work, W , done on or by the
system.

• Mathematically it is stated as
dU = dQ + dW. (16)

• The variables U , W , and Q are extensive variables, meaning that they depend on
the mass of the system.

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• Dividing an extensive variable by mass results in an intensive variable that does not
depend on mass. We usually (but not always) add the word specific to such variables.
Dividing (16) by mass results in

du = dq + dw (17)

where u is internal energy per unit mass, also called specific internal energy ;
q is heat per unit mass 1

• For quasistatic processes the work can be expressed as dw = −pdα, and the First
Law becomes
du = dq − pdα (18)

– Note that for isochoric 2 processes that the change in internal energy is synony-
mous with heat.

• Using the product rule for differentiation, d(pα) = pdα + αdp, and (18) can be rear-
ranged as
dh = dq + αdp, (19)
where h = u + pα, and is the specific enthalpy .

– Note that for isobaric processes that the change in enthalpy is synonymous with
heat.

• For ideal gasses the specific internal energy is a function of temperature only, and can
be expressed as du = cv dT , where cv is the specific heat at constant volume.

• Also, for ideal gasses the specific enthalpy is a function of temperature only, and can
be expressed as dh = cp dT , where cp is the specific heat at constant pressure.

• Thus, for ideal gasses undergoing quasistatic processes the First Law of Thermody-
namics can be written as either

cv dT = dq − pdα (20)

or
cp dT = dq + αdp. (21)

• In meteorology the First Law of Thermodynamics is also called the thermodynamic


energy equation, and is one of the seven governing equations for the atmosphere.
1
We don’t call q specific heat because that term is reserved for another quantity.
2
Isochoric means constant volume.

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Potential Temperature
• Potential temperature, θ, is defined as the temperature an air parcel would have if
it were moved adiabatically to a reference pressure of p0 = 1000 mb.

– The equation for potential temperature is derived by starting with (21), setting
dq = 0 and and substituting for α from the ideal gas law. The result is
dT Rd dp
= . (22)
T cp p
Integrating (22) between temperatures T and θ, and between pressures p and p0 ,
Z θ Z p0
dT Rd dp
=
T T p cp p
yields the Poisson relation
 Rd /cp
p0
θ=T . (23)
p

– Potential temperature is conserved in adiabatic motion. This means that the dry
adiabats on a Skew-T diagram are also lines of constant potential temperature.

• Equivalent potential temperature, θe , is defined as the potential temperature the


air parcel would have if it were lifted pseudoadiabatically until all of the water vapor
were condensed, and the latent heat added to the parcel.

– Equivalent potential temperature is always greater than or equal to the potential


temperature.
– Equivalent potential temperature is conserved in reversible moist-adiabatic mo-
tion.

Dry-adiabatic Lapse Rate


• Adiabatic processes are those in which no heat is transferred (dq = 0), and are of
fundamental importance in atmospheric processes.

• As an air parcel rises adiabatically expands so that its pressure equilibrates to that of
the surrounding environment.

– The parcel does work as it expands, and therefore loses internal energy and its
temperature drops.

• The decrease in temperature with height can be found by starting with the first law
of thermodynamics. For an air parcel undergoing an adiabatic process the first law of
thermodynamics becomes
cp dT 0 = α0 dp0 , (24)

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where the primes indicate properties of the air parcel.
CAUTION!! Rogers and Yau use the prime symbol to denote properties
of the environment, while I and most other sources use the prime symbol
for properties of the air parcel. When comparing my equations with those
of the textbook you should keep this difference in mind.

– Dividing (24) by dz results in

dT 0 dp0
cp = α0 . (25)
dz dz
– The pressure of the air parcel, p0 is assumed to always be equal to the pressure of
the its environment, p.
– If the environment is assumed to be in hydrostatic balance, then
dp0 dp g
= =− ,
dz dz α
and (25) can be rearranged to

dT 0 α0 g
=− . (26)
dz α cp

• Equation (26) describes how the the temperature change with altitude of an unsatu-
0
rated air parcel lifted adiabatically. The ratio αα ≈ 1, and is therefore ignored.

• Since lapse rate is defined as − dT


dz
, we define the dry-adiabatic lapse rate as

dT g
Γd = − = , (27)
dz cp

which has a numerical value of Γd = 9.8◦ C km−1 .

– The specific heat actually depends in a very small way on the humidity content
of the air. This correction is small enough that it is usually ignored and so cp in
(27) is that for dry air.

• Even though Γd is called the dry-adiabatic lapse rate, it is appropriate for a moist air
parcel as long as the parcel remains unsaturated.

Lapse Rate of a Saturated Parcel


• If an air parcel is saturated, then as it rises and cools the relative humidity will exceed
100%.

– Any excess vapor will condense and release latent heat back into the parcel.
– The lapse rate in saturated ascent will be less than the dry-adiabatic lapse rate.

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• The value of the lapse rate in saturated ascent will depend on what assumptions are
made as to:

– whether or not the liquid water remains in the parcel for falls out immediately.
– whether or not the correction to the specific heat, cp v, for the water vapor is
included or ignored.

• The Glossary of Meteorology defines three different lapse rates for saturated ascent.

Reversible moist-adiabatic lapse rate: This assumes that any condensed liquid
remains with the air parcel. The specific heats of the dry air, water vapor, and
liquid water are all included.
Pseudoadiabatic lapse rate: This assumes that any condensed liquid immediately
leaves the parcel. The specific heat of water vapor is still explicitly included.
– Since the liquid water leaves the parcel, this process is irreversible.
Saturation-adiabatic lapse rate: This is the same as the pseudoadiabatic lapse rate
except is does not include the specific heat of the water vapor is ignored. This
process is also irreversible.

• Unfortunately, there is great inconsistency in the literature, and even in the Glossary
of Meteorology itself, regarding the above terms and definitions.

• For this class we will use the terms pseudoadiabatic, saturation-adiabatic, saturated-
adiabatic, and moist-adiabatic interchangeably.

– The good news is that the differences in numerical values between these different
lapse rates are all very small.

• The lapse rate for an ascending saturated air parcel is given by3
!
1 + LRvdrTs
Γs = Γd 2r , (28)
1 + RεLc
v s
d p T 2

where Lv is the latent heat of vaporization, rs is the saturation mixing ratio, and
ε = Rd /Rv .

• At colder temperatures, such as those found in the upper troposphere, the moisture
content of the air is very small, and there is little latent heating added to a rising air
parcel. Thus, in the upper troposphere the moist adiabatic lapse rate approaches the
dry adiabatic lapse rate.

3
Equation (28) assumes the liquid water has fallen from the parcel, and does not correct for the specific
heat of the water vapor. It is the same as Eq. (3.16) in Rogers and Yau, and that for the moist-adiabatic
lapse rate on p. 502 of The Glossary of Meteorology.

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