Atmospheric Thermodynamics: Consiglio Nazionale Delle Ricerche - Istituto Di Scienze Dell'atmosfera e Del Clima Italy
Atmospheric Thermodynamics: Consiglio Nazionale Delle Ricerche - Istituto Di Scienze Dell'atmosfera e Del Clima Italy
Atmospheric Thermodynamics: Consiglio Nazionale Delle Ricerche - Istituto Di Scienze Dell'atmosfera e Del Clima Italy
Atmospheric Thermodynamics
Francesco Cairo
Consiglio Nazionale delle Ricerche Istituto di
Scienze dellAtmosfera e del Clima
Italy
1. Introduction
Thermodynamics deals with the transformations of the energy in a system and between the
system and its environment. Hence, it is involved in every atmospheric process, from the
large scale general circulation to the local transfer of radiative, sensible and latent heat
between the surface and the atmosphere and the microphysical processes producing clouds
and aerosol. Thus the topic is much too broad to find an exhaustive treatment within the
limits of a book chapter, whose main goal will be limited to give a broad overview of the
implications of thermodynamics in the atmospheric science and introduce some if its jargon.
The basic thermodynamic principles will not be reviewed here, while emphasis will be
placed on some topics that will find application to the interpretation of fundamental
atmospheric processes. An overview of the composition of air will be given, together with
an outline of its stratification in terms of temperature and water vapour profile. The ideal
gas law will be introduced, together with the concept of hydrostatic stability, temperature
lapse rate, scale height, and hydrostatic equation. The concept of an air parcel and its
enthalphy and free energy will be defined, together with the potential temperature concept
that will be related to the static stability of the atmosphere and connected to the BruntVaisala frequency.
Water phase changes play a pivotal role in the atmosphere and special attention will be
placed on these transformations. The concept of vapour pressure will be introduced together
with the Clausius-Clapeyron equation and moisture parameters will be defined. Adiabatic
transformation for the unsaturated and saturated case will be discussed with the help of
some aerological diagrams of common practice in Meteorology and the notion of neutral
buoyancy and free convection will be introduced and considered referring to an
exemplificative atmospheric sounding. There, the Convective Inhibition and Convective
Available Potential Energy will be introduced and examined. The last subchapter is devoted
to a brief overview of warm and cold clouds formation processes, with the aim to stimulate
the interest of reader toward more specialized texts, as some of those listed in the conclusion
and in the bibliography.
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wide range of conditions in the so called perfect gas approximation, are connected by an
equation of the form:
(1)
pV=mRT
where p is pressure (Pa), V is volume (m3), m is mass (kg), T is temperature (K) and R is the
specific gas constant, whose value depends on the gas. If we express the amount of substance
in terms of number of moles n=m/M where M is the gas molecular weight, we can rewrite (1)
as:
(2)
pV=nR*T
mol-1 K-1.
p= pi
(3)
piV=niR*T
(4)
We can still make use of (1) for a mixture of gases, provided we compute a specific gas
constant R as:
=
(5)
The atmosphere is composed by a mixture of gases, water substance in any of its three
physical states and solid or liquid suspended particles (aerosol). The main components of
dry atmospheric air are listed in Table 1.
Gas
Molar fraction
Mass fraction
Nitrogen (N2)
Oxygen (O2)
Argon (Ar)
Carbon dioxide (CO2)
0.7809
0.2095
0.0093
0.0003
0.7552
0.2315
0.0128
0.0005
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Atmospheric Thermodynamics
millionths, it is preferable to treat it separately from other air components, and consider the
atmosphere as a mixture of dry gases and water. In order to use a state equation of the form
(1) for moist air, we express a specific gas constant Rd by considering in (5) all gases but
water, and use in the state equation a virtual temperature Tv defined as the temperature that
dry air must have in order to have the same density of moist air at the same pressure. It can
be shown that
=
(6)
Where Mw and Md are respectively the water and dry air molecular weights. Tv takes into
account the smaller density of moist air, and so is always greater than the actual
temperature, although often only by few degrees.
2.1 Stratification
The atmosphere is under the action of a gravitational field, so at any given level the
downward force per unit area is due to the weight of all the air above. Although the air is
permanently in motion, we can often assume that the upward force acting on a slab of air at
any level, equals the downward gravitational force. This hydrostatic balance approximation
is valid under all but the most extreme meteorological conditions, since the vertical
acceleration of air parcels is generally much smaller than the gravitational one. Consider an
horizontal slab of air between z and z +z, of unit horizontal surface. If is the air density at
z, the downward force acting on this slab due to gravity is gz. Let p be the pressure at z,
and p+p the pressure at z+z. We consider as negative, since we know that pressure
decreases with height. The hydrostatic balance of forces along the vertical leads to:
(7)
(8)
leading to:
(9)
(10)
As we know that p()=0, (9) can be integrated if the air density profile is known.
Two useful concepts in atmospheric thermodynamic are the geopotential , an exact
differential defined as the work done against the gravitational field to raise 1 kg from 0 to z,
where the 0 level is often taken at sea level and, to set the constant of integration, (0)=0,
and the geopotential height Z=/g0, where g0 is a mean gravitational acceleration taken as
9,81 m/s.
We can rewrite (9) as:
Values of z and Z often differ by not more than some tens of metres.
We can make use of (1) and of the definition of virtual temperature to rewrite (10) and
formally integrate it between two levels to formally obtain the geopotential thickness of a
layer, as:
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(11)
The above equations can be integrated if we know the virtual temperature Tv as a function
of pressure, and many limiting cases can be envisaged, as those of constant vertical
temperature gradient. A very simplified case is for an isothermal atmosphere at a
temperature Tv=T0, when the integration of (11) gives:
=
(12)
Fig. 1. Temperature (dotted line), pressure (dashed line) and air density (solid line) for a
standard atmosphere.
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Atmospheric Thermodynamics
(13)
cpdT - vdp= q
(14)
holds for q=0, where cp and cv are respectively the specific heats at constant pressure and
constant volume, p and v are the specific pressure and volume, and q is the heat exchanged
with the surroundings. Integrating (13) and (14) and making use of the ideal gas state
equation, we get the Poissons equations:
= constant
(15)
Tp- = constant
(16)
Tv
-1
where =cp/cv =1.4 and =( -1)/ =R/cp 0.286, using a result of the kinetic theory for
diatomic gases. We can use (16) to define a new state variable that is conserved during an
adiabatic process, the potential temperature , which is the temperature the air parcel would
attain if compressed, or expanded, adiabatically to a reference pressure p0, taken for
convention as 1000 hPa.
=
(18)
Since the time scale of heat transfers, away from the planetary boundary layer and from
clouds is several days, and the timescale needed for an air parcel to adjust to environmental
pressure changes is much shorter, can be considered conserved along the air motion for
one week or more. The distribution of in the atmosphere is determined by the pressure
and temperature fields. In fig. 2 annual averages of constant potential temperature surfaces
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are depicted, versus pressure and latitude. These surfaces tend to be quasi-horizontal. An air
parcel initially on one surface tend to stay on that surface, even if the surface itself can vary
its position with time. At the ground level attains its maximum values at the equator,
decreasing toward the poles. This poleward decrease is common throughout the
troposphere, while above the tropopause, situated near 100 hPa in the tropics and 3-400 hPa
at medium and high latitudes, the behaviour is inverted.
cp dT + g dz=0
(20)
If the air parcel thermally interacts with its environment, the adiabatic condition no longer
holds and in (13) and (14) q 0. In such case, dividing (14) by T and using (1) we obtain:
ln ln
(21)
(22)
That clearly shows how the changes in potential temperature are directly related to the heat
exchanged by the system.
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Atmospheric Thermodynamics
(23)
If we introduce (22) in (23), we note how such expression, connecting potential temperature
to entropy, would contain only state variables. Hence equality must hold and we get:
ln
(24)
That directly relates changes in potential temperature with changes in entropy. We stress
the fact that in general an adiabatic process does not imply a conservation of entropy. A
classical textbook example is the adiabatic free expansion of a gas. However, in atmospheric
processes, adiabaticity not only implies the absence of heat exchange through the
boundaries of the system, but also absence of heat exchanges between parts of the system
itself (Landau et al., 1980), that is, no turbulent mixing, which is the principal source of
irreversibility. Hence, in the atmosphere, an adiabatic process always conserves entropy.
2.3 Stability
The vertical gradient of potential temperature determines the stratification of the air. Let us
differentiate (18) with respect to z:
=
(25)
By computing the differential of the logarithm, and applying (1) and (8), we get:
=
(26)
(27)
Now, consider a vertical displacement z of an air parcel of mass m and let and T be the
density and temperature of the parcel, and and T the density and temperature of the
surrounding. The restoring force acting on the parcel per unit mass will be:
=
=
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(28)
(29)
56
We can replace (T-T) with (d - ) z if we acknowledge the fact that the air parcel moves
adiabatically in an environment of lapse rate . The second order equation of motion (29)
can be solved in z and describes buoyancy oscillations with period 2/N where N is the
Brunt-Vaisala frequency:
=
(30)
It is clear from (30) that if the environment lapse rate is smaller than the adiabatic one, or
equivalently if the potential temperature vertical gradient is positive, N will be real and an
air parcel will oscillate around an equilibrium: if displaced upward, the air parcel will find
itself colder, hence heavier than the environment and will tend to fall back to its original
place; a similar reasoning applies to downward displacements. If the environment lapse rate
is greater than the adiabatic one, or equivalently if the potential temperature vertical
gradient is negative, N will be imaginary so the upward moving air parcel will be lighter
than the surrounding and will experience a net buoyancy force upward. The condition for
atmospheric stability can be inspected by looking at the vertical gradient of the potential
temperature: if increases with height, the atmosphere is stable and vertical motion is
discouraged, if decreases with height, vertical motion occurs. For average tropospheric
conditions, N 10-2 s-1 and the period of oscillation is some tens of minutes. For the more
stable stratosphere, N 10-1 s-1 and the period of oscillation is some minutes. This greater
stability of the stratosphere acts as a sort of damper for the weather disturbances, which are
confined in the troposphere.
(31)
Where u is its specific internal energy, v its specific volume and p its pressure in equilibrium
with the environment. We can think of h as a measure of the total energy of the system. It
includes both the internal energy required to create the system, and the amount of energy
required to make room for it in the environment, establishing its volume and balancing its
pressure against the environmental one. Note that this additional energy is not stored in the
system, but rather in its environment.
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Atmospheric Thermodynamics
The First law of thermodynamics can be set in a form where h is explicited as:
(32)
(33)
By combining (32), (33) and (8), and incorporating the definition of geopotential we get:
=
(34)
Which states that an air parcel moving adiabatically in an hydrostatic atmosphere conserves
the sum of its enthalpy and geopotential.
The specific Gibbs free energy is defined as:
=
= +
(35)
It represents the energy available for conversion into work under an isothermal-isobaric
process. Hence the criterion for thermodinamical equilibrium for a system at constant
pressure and temperature is that g attains a minimum.
For an heterogeneous system where multiple phases coexist, for the k-th species we define
its chemical potential k as the partial molar Gibbs function, and the equilibrium condition
states that the chemical potentials of all the species should be equal. The proof is
straightforward: consider a system where nv moles of vapour (v) and nl moles of liquid
water (l) coexist at pressure e and temperature T, and let G = nvv +nll be the Gibbs function
of the system. We know that for a virtual displacement from an equilibrium condition, dG >
0 must hold for any arbitrary dnv (which must be equal to dnl , whether its positive or
negative) hence, its coefficient must vanish and v = l .
Note that if evaporation occurs, the vapour pressure e changes by de at constant
temperature, and dv = vv de, dl = vl de where vv and vl are the volume occupied by a single
molecule in the vapour and the liquid phase. Since vv >> vl we may pose d(v - l) = vvde and,
using the state gas equation for a single molecule, d(v - l) = (kT/e) de. In the equilibrium,
v = l and e = es while in general:
(36)
holds. We will make use of this relationship we we will discuss the formation of clouds.
3.1 Saturation vapour pressure
The value of es strongly depends on temperature and increases rapidly with it. The
celebrated Clausius Clapeyron equation describes the changes of saturated water pressure
above a plane surface of liquid water. It can be derived by considering a liquid in
equilibrium with its saturated vapour undergoing a Carnot cycle (Fermi, 1956). We here
simply state the result as:
=
(37)
Retrieved under the assumption that the specific volume of the vapour phase is much
greater than that of the liquid phase. Lv is the latent heat, that is the heat required to convert
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a unit mass of substance from the liquid to the vapour phase without changing its
temperature. The latent heat itself depends on temperature at 1013 hPa and 0C is 2.5*106 J
kg-, - hence a number of numerical approximations to (37) have been derived. The World
Meteoreological Organization bases its recommendation on a paper by Goff (1957):
Log10 es 10.79574 1 273.16 / T 5.02800 Log 10 T / 273.16 +
(38)
Where T is expressed in K and es in hPa. Other formulations are used, based on direct
measurements of vapour pressures and theoretical calculation to extrapolate the formulae
down to low T values (Murray, 1967; Bolton, 1980; Hyland and Wexler, 1983; Sonntag, 1994;
Murphy and Koop, 2005) uncertainties at low temperatures become increasingly large and
the relative deviations within these formulations are of 6% at -60C and of 9% at -70.
An equation similar to (37) can be derived for the vapour pressure of water over ice esi. In
such a case, Lv is the latent heat required to convert a unit mass of water substance from ice
to vapour phase without changing its temperature. A number of numerical approximations
holds, as the Goff-Gratch equation, considered the reference equation for the vapor
pressure over ice over a region of -100C to 0C:
Log 10 esi 9.09718 273.16 / T 1 3.56654 Log 10 273.16 / T
0.876793 1 T / 273.16 Log 10 6.1071
(39)
with T in K and esi in hPa. Other equations have also been widely used (Murray, 1967;
Hyland and Wexler, 1983; Marti and Mauersberger, 1993; Murphy and Koop, 2005).
Water evaporates more readily than ice, that is es > esi everywhere (the difference is maxima
around -20C), so if liquid water and ice coexists below 0C, the ice phase will grow at the
expense of the liquid water.
3.2 Water vapour in the atmosphere
A number of moisture parameters can be formulated to express the amount of water
vapour in the atmosphere. The mixing ratio r is the ratio of the mass of the water vapour mv,
to the mass of dry air md, r=mv/md and is expressed in g/kg-1 or, for very small
concentrations as those encountered in the stratosphere, in parts per million in volume
(ppmv). At the surface, it typically ranges from 30-40 g/kg-1 at the tropics to less that 5
g/kg-1 at the poles; it decreases approximately exponentially with height with a scale height
of 3-4 km, to attain its minimum value at the tropopause, driest at the tropics where it can
get as low as a few ppmv. If we consider the ratio of mv to the total mass of air, we get the
specific humidity q as q = mv/(mv+md) =r/(1+r). The relative humidity RH compares the water
vapour pressure in an air parcel with the maximum water vapour it may sustain in
equilibrium at that temperature, that is RH = 100 e/es (expressed in percentages). The dew
point temperature Td is the temperature at which an air parcel with a water vapour pressure
e should be brought isobarically in order to become saturated with respect to a plane surface
of water. A similar definition holds for the frost point temperature Tf, when the saturation is
considered with respect to a plane surface of ice.
The wet-bulb temperature Tw is defined operationally as the temperature a thermometer
would attain if its glass bulb is covered with a moist cloth. In such a case the thermometer is
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59
cooled upon evaporation until the surrounding air is saturated: the heat required to
evaporate water is supplied by the surrounding air that is cooled. An evaporating droplet
will be at the wet-bulb temperature. It should be noted that if the surrounding air is initially
unsaturated, the process adds water to the air close to the thermometer, to become
saturated, hence it increases its mixing ratio r and in general T Tw Td, the equality holds
when the ambient air is already initially saturated.
3.2 Thermodynamics of the vertical motion
The saturation mixing ratio depends exponentially on temperature. Hence, due to the
decrease of ambient temperature with height, the saturation mixing ratio sharply decreases
with height as well.
Therefore the water pressure of an ascending moist parcel, despite the decrease of its
temperature at the dry adiabatic lapse rate, sooner or later will reach its saturation value at
a level named lifting condensation level (LCL), above which further lifting may produce
condensation and release of latent heat. This internal heating slows the rate of cooling of the
air parcel upon further lifting.
If the condensed water stays in the parcel, and heat transfer with the environment is
negligible, the process can be considered reversible that is, the heat internally added by
condensation could be subtracted by evaporation if the parcel starts descending - hence the
behaviour can still be considered adiabatic and we will term it a saturated adiabatic process. If
otherwise the condensate is removed, as instance by sedimentation or precipitation, the
process cannot be considered strictly adiabatic. However, the amount of heat at play in the
condensation process is often negligible compared to the internal energy of the air parcel
and the process can still be considered well approximated by a saturated adiabat, although
it should be more properly termed a pseudoadiabatic process.
Fig. 3. Vertical profiles of mixing ratio r and saturated mixing ratio rs for an ascending air
parcel below and above the lifting condensation level. (source: Salby M. L., Fundamentals of
Atmospheric Physics, Academic Press, New York.)
3.2.1 Pseudoadiabatic lapse rate
If within an air parcel of unit mass, water vapour condenses at a saturation mixing ratio rs, the
amount of latent heat released during the process will be -Lwdrs. This can be put into (34) to get:
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(40)
Dividing by cpdz and rearranging terms, we get the expression of the saturated adiabatic lapse
rate s:
=
(41)
Whose value depends on pressure and temperature and which is always smaller than d, as
should be expected since a saturated air parcel, since condensation releases latent heat, cools
more slowly upon lifting.
3.2.2 Equivalent potential temperature
If we pose q = - Lwdrs in (22) we get:
=
(42)
The approximate equality holds since dT/T << drs/rs and Lw/cp is approximately independent
of T. So (41) can be integrated to yield:
=
(43)
That defines the equivalent potential temperature e (Bolton, 1990) which is constant along a
pseudoadiabatic process, since during the condensation the reduction of rs and the increase
of act to compensate each other.
3.3 Stability for saturated air
We have seen for the case of dry air that if the environment lapse rate is smaller than the
adiabatic one, the atmosphere is stable: a restoring force exist for infinitesimal displacement
of an air parcel. The presence of moisture and the possibility of latent heat release upon
condensation complicates the description of stability.
If the air is saturated, it will cool upon lifting at the smaller saturated lapse rate s so in an
environment of lapse rate , for the saturated air parcel the cases < s , = s , > s
discriminates the absolutely stable, neutral and unstable conditions respectively. An
interesting case occurs when the environmental lapse rate lies between the dry adiabatic and
the saturated adiabatic, that is s < < d. In such a case, a moist unsaturated air parcel can
be lifted high enough to become saturated, since the decrease in its temperature due to
adiabatic cooling is offset by the faster decrease in water vapour saturation pressure, and
starts condensation at the LCL. Upon further lifting, the air parcel eventually get warmer
than its environment at a level termed Level of Free Convection (LFC) above which it will
develop a positive buoyancy fuelled by the continuous release of latent heat due to
condensation, as long as there is vapour to condense. This situation of conditional instability
is most common in the atmosphere, especially in the Tropics, where a forced finite uplifting
of moist air may eventually lead to spontaneous convection. Let us refer to figure 4 and
follow such process more closely. In the figure, which is one of the meteograms discussed
later in the chapter, pressure decreases vertically, while lines of constant temperature are
tilted 45 rightward, temperature decreasing going up and to the left.
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Atmospheric Thermodynamics
Fig. 4. Thick solid line represent the environment temperature profile. Thin solid line
represent the temperature of an ascending parcel initially at point A. Dotted area represent
CIN, shaded area represent CAPE.
The thick solid line represent the environment temperature profile. A moist air parcel
initially at rest at point A is lifted and cools at the adiabatic lapse rate d along the thin solid
line until it eventually get saturated at the Lifting Condensation Level at point D. During
this lifting, it gets colder than the environment. Upon further lifting, it cools at a slower rate
at the pseudoadiabatic lapse rate s along the thin dashed line until it reaches the Level of
Free Convection at point C, where it attains the temperature of the environment. If it gets
beyond that point, it will be warmer, hence lighter than the environment and will
experience a positive buoyancy force. This buoyancy will sustain the ascent of the air parcel
until all vapour condenses or until its temperature crosses again the profile of
environmental temperature at the Level of Neutral Buoyancy (LNB). Actually, since the air
parcel gets there with a positive vertical velocity, this level may be surpassed and the air
parcel may overshoot into a region where it experiences negative buoyancy, to eventually
get mixed there or splash back to the LNB. In practice, entrainment of environmental air into
the ascending air parcel often occurs, mitigates the buoyant forces, and the parcel generally
reaches below the LNB.
If we neglect such entrainment effects and consider the motion as adiabatic, the buoyancy
force is conservative and we can define a potential. Let and be respectively the
environment and air parcel density. From Archimedes principle, the buoyancy force on a
unit mass parcel can be expressed as in (29), and the increment of potential energy for a
displacement z will then be, by using (1) and (8):
=
(44)
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62
Referring to fig. 4, A(p) represent the shaded area between the environment and the air
parcel temperature profiles. An air parcel initially in A is bound inside a potential energy
well whose depth is proportional to the dotted area, and that is termed Convective Inhibition
(CIN). If forcedly raised to the level of free convection, it can ascent freely, with an available
potential energy given by the shaded area, termed CAPE (Convective Available Potential
Energy).
In absence of entrainment and frictional effects, all this potential energy will be converted
into kinetic energy, which will be maximum at the level of neutral buoyancy. CIN and
CAPE are measured in J/Kg and are indices of the atmospheric instability. The CAPE is the
maximum energy which can be released during the ascent of a parcel from its free buoyant
level to the top of the cloud. It measures the intensity of deep convection, the greater the
CAPE, the more vigorous the convection. Thunderstorms require large CAPE of more than
1000 Jkg-1.
CIN measures the amount of energy required to overcome the negatively buoyant energy
the environment exerts on the air parcel, the smaller, the more unstable the atmosphere,
and the easier to develop convection. So, in general, convection develops when CIN is small
and CAPE is large. We want to stress that some CIN is needed to build-up enough CAPE to
eventually fuel the convection, and some mechanical forcing is needed to overcome CIN.
This can be provided by cold front approaching, flow over obstacles, sea breeze.
CAPE is weaker for maritime than for continental tropical convection, but the onset of
convection is easier in the maritime case due to smaller CIN.
We have neglected entrainment of environment air, and detrainment from the air parcel ,
which generally tend to slow down convection. However, the parcels reaching the highest
altitude are generally coming from the region below the cloud without being too much
diluted.
Convectively generated clouds are not the only type of clouds. Low level stratiform clouds
and high altitude cirrus are a large part of cloud cover and play an important role in the
Earth radiative budget. However convection is responsible of the strongest precipitations,
especially in the Tropics, and hence of most of atmospheric heating by latent heat transfer.
So far we have discussed the stability behaviour for a single air parcel. There may be the
case that although the air parcel is stable within its layer, the layer as a whole may be
destabilized if lifted. Such case happen when a strong vertical stratification of water vapour
is present, so that the lower levels of the layer are much moister than the upper ones. If the
layer is lifted, its lower levels will reach saturation before the uppermost ones, and start
cooling at the slower pseudoadiabat rate, while the upper layers will still cool at the faster
adiabatic rate. Hence, the top part of the layer cools much more rapidly of the bottom part
and the lapse rate of the layer becomes unstable. This potential (or convective) instability is
frequently encountered in the lower leves in the Tropics, where there is a strong water
vapour vertical gradient.
It can be shown that condition for a layer to be potentially unstable is that its equivalent
potential temperature e decreases within the layer.
3.4 Tephigrams
To represent the vertical structure of the atmosphere and interpret its state, a number of
diagrams is commonly used. The most common are emagrams, Stve diagrams, skew T- log p
diagrams, and tephigrams.
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An emagram is basically a T-z plot where the vertical axis is log p instead of height z. But
since log p is linearly related to height in a dry, isothermal atmosphere, the vertical
coordinate is basically the geometric height.
In the Stve diagram the vertical coordinate is p(Rd/cp) and the horizontal coordinate is T: with
this axes choice, the dry adiabats are straight lines.
A skew T- log p diagram, like the emagram, has log p as vertical coordinate, but the isotherms
are slanted. Tephigrams look very similar to skew T diagrams if rotated by 45, have T as
horizontal and log as vertical coordinates so that isotherms are vertical and the isentropes
horizontal (hence tephi, a contraction of T and , where = cp log stands for the entropy).
Often, tephigrams are rotated by 45 so that the vertical axis corresponds to the vertical in
the atmosphere.
A tephigram is shown in figure 5: straight lines are isotherms (slope up and to the right) and
isentropes (up and to the left), isobars (lines of constant p) are quasi-horizontal lines, the
dashed lines sloping up and to the right are constant mixing ratio in g/kg, while
the curved solid bold lines sloping up and to the left are saturated adiabats.
Fig. 5. A tephigram. Starting from the surface, the red line depicts the evolution of the Dew
Point temperature, the black line depicts the evolution of the air parcel temperature, upon
uplifting. The two lines intersects at the LCL. The orange line depicts the saturated adiabat
crossing the LCL point, that defines the wet bulb temperature at the ground pressure
surface.
Two lines are commonly plotted on a tephigram the temperature and dew point, so the
state of an air parcel at a given pressure is defined by its temperature T and Td, that is its
water vapour content. We note that the knowledge of these parameters allows to retrieve all
the other humidity parameters: from the dew point and pressure we get the humidity
mixing ratio w; from the temperature and pressure we get the saturated mixing ratio ws,
and relative humidity may be derived from 100*w/ws, when w and ws are measured at the
same pressure.
When the air parcel is lifted, its temperature T follows the dry adiabatic lapse rate and its
dew point Td its constant vapour mixing ratio line - since the mixing ratio is conserved in
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unsaturated air - until the two meet a t the LCL where condensation may start to happen.
Further lifting follows the Saturated Adiabatic Lapse Rate. In Figure 5 we see an air parcel
initially at ground level, with a temperature of 30 and a Dew Point temperature of 0
(which as we can see by inspecting the diagram, corresponds to a mixing ratio of approx. 4
g/kg at ground level) is lifted adiabatically to 700 mB which is its LCL where the air parcel
temperature following the dry adiabats meets the air parcel dew point temperature
following the line of constant mixing ratio. Above 700 mB, the air parcel temperature
follows the pseudoadiabat. Figure 5 clearly depicts the Normands rule: The dry adiabatic
through the temperature, the mixing ratio line through the dew point, and the saturated
adiabatic through the wet bulb temperature, meet at the LCL. In fact, the saturated adiabat
that crosses the LCL is the same that intersect the surface isobar exactly at the wet bulb
temperature, that is the temperature a wetted thermometer placed at the surface would
attain by evaporating - at constant pressure - its water inside its environment until it gets
saturated.
Figure 6 reports two different temperature sounding: the black dotted line is the dew point
profile and is common to the two soundings, while the black solid line is an early morning
sounding, where we can see the effect of the nocturnal radiative cooling as a temperature
inversion in the lowermost layer of the atmosphere, between 1000 and 960 hPa. The state of
the atmosphere is such that an air parcel at the surface has to be forcedly lifted to 940 hP to
attain saturation at the LCL, and forcedly lifted to 600 hPa before gaining enough latent heat
of condensation to became warmer than the environment and positively buoyant at the LFB.
The temperature of such air parcel is shown as a grey solid line in the graph.
Fig. 6. A tephigram showing with the black and blue lines two different temperature
sounding, and with the grey and red lines two different temperature histories of an air
parcel initially at ground level, upon lifting. The dotted line is the common Td profile of the
two soundings.
The blue solid line is an afternoon sounding, when the surface has been radiatively heated
by the sun. An air parcel lifted from the ground will follow the red solid line, and find itself
immediately warmer than its environment and gaining positive buoyancy, further
increased by the release of latent heat starting at the LCL at 850 hPa. Notice however that a
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Atmospheric Thermodynamics
65
second inversion layer is present in the temperature sounding between 800 hPa and 750
hPa, such that the air parcel becomes colder than the environment, hence negatively
buoyant between 800 hPa and 700 hPa. If forcedly uplifted beyond this stable layer, it again
attains a positive buoyancy up to above 300 hPa.
As the tephigram is a graph of temperature against entropy, an area computed from these
variables has dimensions of energy. The area between the air parcel path is then linked to
the CIN and the CAPE. Referring to the early morning sounding, the area between the black
and the grey line between the surface and 600 hPa is the CIN, the area between 600 hPa and
400 hPa is the CAPE.
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by creating a droplet, work is done not only as expansion work, but also to form the
interface between the droplet and its environment, associated with the surface tension at the
surface of the droplet of area A. This originates from the cohesive forces among the liquid
molecules. In the interior of the droplet, each molecule is equally pulled in every direction
by neighbouring molecules, resulting in a null net force. The molecules at the surface do not
have other molecules on all sides of them and therefore are only pulled inwards, as if a force
acted on interface toward the interior of the droplet. This creates a sort of pressure directed
inward, against which work must be exerted to allow further expansion. This effect forces
liquid surfaces to contract to the minimal area.
Let be the energy required to form a droplet of unit surface; then, for the heterogeneous
system droplet-surroundings we may write, for an infinitesimal change of the droplet:
=
(46)
We note that dmv = - dml = - nldV where nl is the number density of molecules inside the
droplet. Considering an isothermal-isobaric process, we came to the conclusion that the
formation of a droplet of radius r results in a change of Gibbs free given by:
=4
(47)
Where we have used (36). Clearly, droplet formation is thermodynamically unfavoured for
e < es, as should be expected. If e > es, we are in supersaturated conditions, and the second
term can counterbalance the first to give a negative G.
Fig. 7. Variation of Gibbs free energy of a pure water droplet formed by homogeneous
nucleation, in a subsaturated (upper curve) and a supersaturated (lower curve)
environment, as a function of the droplet radius. The critical radius r0 is shown.
Figure 7 shows two curves of G as a function of the droplet radius r, for a subsaturated and
supersaturated environment. It is clear that below saturation every increase of the droplet
radius will lead to an increase of the free energy of the system, hence is thermodynamically
unfavourable and droplets will tend to evaporate. In the supersaturated case, on the
contrary, a critical value of the radius exists, such that droplets that grows by casual
collision among molecules beyond that value, will continue to grow: they are said to get
activated. The expression for such critical radius is given by the Kelvins formula:
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Atmospheric Thermodynamics
(48)
The greater e with respect to es, that is the degree of supersaturation, the smaller the radius
beyond which droplets become activated.
It can be shown from (48) that a droplet with a radius as small as 0.01 m would require a
supersaturation of 12% for getting activated. However, air is seldom more than a few
percent supersaturated, and the homogeneous nucleation process is thus unable to explain
the generation of clouds. Another process should be invoked: the heterogeneous nucleation.
This process exploit the ubiquitous presence in the atmosphere of particles of various nature
(Kaufman et al., 2002), some of which are soluble (hygroscopic) or wettable (hydrophilic)
and are called Cloud Condensation Nuclei (CCN). Water may form a thin film on wettable
particles, and if their dimension is beyond the critical radius, they form the nucleus of a
droplet that may grow in size. Soluble particles, like sodium chloride originating from sea
spray, in presence of moisture absorbs water and dissolve into it, forming a droplet of
solution. The saturation vapour pressure over a solution is smaller than over pure water,
and the fractional reduction is given by Raoults law:
=
(49)
= 1+
(50)
1+
(51)
Where e in the vapour pressure over pure water, and e is the vapour pressure over a
solution containing a mole fraction f (number of water moles divided by the total number of
moles) of pure water.
Let us consider a droplet of radius r that contains a mass m of a substance of molecular
weight Ms dissolved into i ions per molecule, such that the effective number of moles in the
solution is im/Ms . The number of water moles will be ((4/3)r3 - m)/Mw where and Mw are
the water density and molecular weight respectively. The water mole fraction f is:
=
Eq. (49) and (50) allows us to express the reduced value e of the saturation vapour pressure
for a droplet of solution. Using this result into (48) we can compute the saturation vapour
pressure in equilibrium with a droplet of solution of radius r:
=
The plot of supersaturation e/es -1 for two different values of m is shown in fig. 8, and is
named Khler curve.
Figure 8 clearly shows how the amount of supersaturation needed to sustain a droplet of
solution of radius r is much lower than what needed for a droplet of pure water, and it
decreases with the increase of solute concentration. Consider an environment
supersaturation of 0.2%. A droplet originated from condensation on a sphere of sodium
chloride of diameter 0.1 m can grow indefinitely along the blue curve, since the peak of the
curve is below the environment supersaturation; such droplet is activated. A droplet
originated from a smaller grain of sodium chloride of 0.05 m diameter will grow until
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Fig. 8. Kohler curves showing how the critical diameter and supersaturation are dependent
upon the amount of solute. It is assumed here that the solute is a perfect sphere of sodium
chloride (source: http://en.wikipedia.org/wiki/Khler_theory).
4.2 Condensation
The droplet that is able to pass over the peak of the Khler curve will continue to grow by
condensation. Let us consider a droplet of radius r at time t, in a supersaturated
environment whose water vapour density far from the droplet is v(), while the vapour
density in proximity of the droplet is v(r) . The droplet mass M will grow at the rate of mass
flux across a sphere of arbitrary radius centred on the droplet. Let D be the diffusion
coefficient, that is the amount of water vapour diffusing across a unit area through a unit
concentration gradient in unit time, and v(x) the water vapour density at a distance x > r
from the droplet. We will have:
=4
(52)
(53)
Since in steady conditions of mass flow this equation is independent of x, we can integrate it
for x between r and to get:
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Atmospheric Thermodynamics
Where we have used the ideal gas equation for water vapour. We should think of e(r) as
given by e in (49), but in fact we can approximate it with the saturation vapour pressure
over a plane surface es, and pose (e()-e(r))/e() roughly equal to the supersaturation
S=(e()-es)/es to came to:
=
(55)
This equation shows that the radius growth is inversely proportional to the radius itself, so
that the rate of growth will tend to slow down with time. In fact, condensation alone is too
slow to eventually produce rain droplets, and a different process should be invoked to
create droplet with radius greater than few tens of micrometers.
4.3 Collision and coalescence
The droplet of density l and volume V is suspended in air of density so that under the
effect of the gravitational field, three forces are acting on it: the gravity exerting a downward
force l Vg , the upward Archimedes buoyancy V and the drag force that for a sphere,
assumes the form of the Stokes drag 6 rv where is the viscosity of the air and v is the
steady state terminal fall speed of the droplet. In steady state, by equating those forces and
assuming the droplet density much greater than the air, we get an expression for the
terminal fall speed:
=
(56)
Such speed increases with the droplet dimension, so that bigger droplets will eventually
collide with the smaller ones, and may entrench them with a collection efficiency E
depending on their radius and other environmental parameters , as for instance the presence
of electric fields. The rate of increase of the radius r1 of a spherical collector drop due to
collision with water droplets in a cloud of liquid water content wl , that is is the mass density
of liquid water in the cloud, is given by:
=
(57)
Since v1 increases with r1, the process tends to speed up until the collector drops became
a rain drop and eventually pass through the cloud base, or split up to reinitiate the
process.
4.4 Nucleation of ice particles
A cloud above 0 is said a warm cloud and is entirely composed of water droplets. Water
droplet can still exists in cold clouds below 0, although in an unstable state, and are termed
supecooled. If a cold cloud contains both water droplets and ice, is said mixed cloud; if it
contains only ice, it is said glaciated.
For a droplet to freeze, a number of water molecules inside it should come together and
form an ice embryo that, if exceeds a critical size, would produce a decrease of the Gibbs free
energy of the system upon further growing, much alike the homogeneous condensation
from the vapour phase to form a droplet. This glaciations process is termed homogeneous
freezing, and below roughly -37 C is virtually certain to occur. Above that temperature, the
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critical dimensions of the ice embryo are several micrometers, and such process is not
favoured. However, the droplet can contain impurities, and some of them may promote
collection of water droplets into an ice-like structure to form a ice-like embryo with
dimension already beyond the critical size for glaciations. Such particles are termed ice nuclei
and the process they start is termed heterogeneous freezing. Such process can start not only
within the droplet, but also upon contact of the ice nucleus with the surface of the droplet
(contact nucleation) or directly by deposition of ice on it from the water vapour phase
(deposition nucleation). Good candidates to act as ice nuclei are those particle with molecular
structure close to the hexagonal ice crystallography. Some soil particles, some organics and
even some bacteria are effective nucleators, but only one out of 103-105 atmospheric particles
can act as an ice nucleus. Nevertheless ice particles are present in clouds in concentrations
which are orders of magnitude greater than the presence of ice nuclei. Hence, ice
multiplication processes must be at play, like breaking of ice particles upon collision, to
create ice splinterings that enhance the number of ice particles.
4.5 Growth of ice particles
Ice particles can grow from the vapour phase as in the case of water droplets. In a mixed
phase cloud below 0C, a much greater supersaturation is reached with respect to ice that
can reach several percents, than with respect to water, which hardly exceed 1%. Hence ice
particles grows faster than droplets and, since this deplete the vapour phase around them, it
may happen that around a growing ice particle, water droplets evaporate. Ice can form in a
variety of shapes, whose basic habits are determined by the temperature at which they
grow. Another process of growth in a mixed cloud is by riming, that is by collision with
supercooled droplets that freeze onto the ice particle. Such process is responsible of the
formation of hailstones.
A process effective in cold clouds is the aggregation of ice particles between themselves,
when they have different shapes and/or dimension, hence different fall speeds.
5. Conclusion
A brief overview of some topic of relevance in atmospheric thermodynamic has been
provided, but much had to remain out of the limits of this introduction, so the interested
reader is encouraged to further readings. For what concerns moist thermodynamics and
convection, the reader can refer to chapters in introductory atmospheric science textbooks
like the classical Wallace and Hobbs (2006), or Salby (1996). At a higher level of deepening
the classical reference is Iribarne and Godson (1973). For the reader who seeks a more
theoretical approach, Zdunkowski and Bott (2004) is a good challenge. Convection is
thoughtfully treated in Emmanuel (1994) while a sound review is given in the article of
Stevens (2005). For what concerns the microphysics of clouds, the reference book is
Pruppacher and Klett (1996). A number of seminal journal articles dealing with the
thermodynamics of the general circulation of the atmosphere can be cited: Goody (2003),
Pauluis and Held (2002), Renno and Ingersoll (2008), Pauluis et al. (2008) and references
therein. Finally, we would like to suggest the Bohren (2001) delightful book, for which a
scientific or mathematical background is not required, that explores topics in meteorology
and basic physics relevant to the atmosphere.
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Atmospheric Thermodynamics
71
6. References
Bohren, C. F., (2001), Clouds in a Glass of Beer: Simple Experiments in Atmospheric Physics, John
Wiley & Sons, Inc., New York.
Bolton, M.D., (1980), The computation of equivalent potential temperature, Mon. Wea. Rev.,
108, 1046-1053.
Emanuel, K., (1984), Atmospheric Convection, Oxford Univ. Press, New York.
Fermi, E., (1956), Thermodynamics, Dover Publications, London.
Goff, J. A., (1957), Saturation pressure of water on the new Kelvin temperature scale,
Transactions of the American society of heating and ventilating engineers, pp. 347-354,
meeting of the American Society of Heating and Ventilating Engineers, Murray
Bay, Quebec, Canada, 1957.
Goody, R. (2003), On the mechanical efficiency of deep, tropical convection, J. Atmos. Sci., 50,
2287-2832.
Hyland, R. W. & A. Wexler A., (1983), Formulations for the Thermodynamic Properties of
the saturated Phases of H2O from 173.15 K to 473.15 K, ASHRAE Trans., 89(2A),
500-519.
Iribarne J. V. & Godson W. L., (1981), Atmospheric Thermodynamics, Springer, London.
Kaufman Y. J., Tanr D. & O. Boucher, (2002), A satellite view of aerosol in the climate
system, Nature, 419, 215-223.
Landau L. D. & Lifshitz E. M., (1980), Statistical Physics, Plenum Press, New York.
Marti, J. & Mauersberger K., (1993), A survey and new measurements of ice vapor
pressure at temperatures between 170 and 250 K, Geophys. Res. Lett. , 20, 363366.
Murphy, D. M. & Koop T., (2005), Review of the vapour pressures of ice and supercooled
water for atmospheric applications, Quart. J. Royal Met. Soc., 131, 1539-1565.
Murray, F. W., (1967), On the computation of saturation vapor pressure, J. Appl. Meteorol., 6,
203-204, 1967.
Pauluis, O; & Held, I.M. (2002). Entropy budget of an atmosphere in radiative-convective
equilibrium. Part I: Maximum work and frictional dissipation, J. Atmos. Sci., 59, 140149.
Pauluis, O., Czaja A. & Korty R. (2008). The global atmospheric circulation on moist
isentropes, Science, 321, 1075-1078.
Pruppacher H. D. & Klett, J. D., (1996), Microphysics of clouds and precipitation, Springer,
London.
Renno, N. & Ingersoll, A. (1996). Natural convection as a heat engine: A theory for CAPE, J.
Atmos. Sci., 53, 572585.
Salby M. L., (1996), Fundamentals of Atmospheric Physics, Academic Press, New York.
Sonntag, D., (1994), Advancements in the field of hygrometry, Meteorol. Z., N. F., 3, 5166.
Stevens, B., (2005), Atmospheric moist convection, Annu. Rev. Earth. Planet. Sci., 33, 605643.
Wallace J.M & Hobbs P.V., (2006), Atmospheric Science: An Introductory Survey, Academic
Press, New York.
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Zdunkowski W. & Bott A., (2004), Thermodynamics of the Atmosphere: A Course in Theoretical
Meteorology, Cambridge University Press, Cambridge.
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