Lecture 3: THERMODYNAMICS OF WATER VAPOR AND MOIST AIR

3.0 Introduction
Ideal gas situation does not include moisture. However, in the atmosphere, water exists in
various phases and this affect the ideal gas equations considerably. We discuss some of the
moisture variables in this section. The application of these moisture variables in analysis of
thermodynamic diagrams will be presented in lecture 4.

LECTURE OBJECTIVES
At the end of this lecture, you should be able to:
1. List and define Moisture variables
2. Discuss Phase diagram of water vapour
3. Derive the Clasius-clapyeron equation

3.1 Moisture variables

The amount moisture in the atmosphere is usually expressed in terms of moisture variables.
A number of quantities directly express or depend upon the amount of water vapor in the air. The
more important moisture variables are the following:

1. Vapour Pressure, e

When water vapour is the only gas present in a volume, the vapour pressure is the pressure of the
gas. In a mixture of air and water vapour, the pressure exerted by the H20 is the vapour pressure.

The amount of vapour that can remain gaseous is limited, the upper limit being represented by
saturation vapour pressure, es which is a function of temperature only.

2. Absolute Humidity, ρ

The absolute humidity is essentially the density of water vapor in the air. It increases with
increasing amount of water vapor and vice versa.

3. Mixing Ratio, w

This is defined as the ratio of the mass of water vapour present to the mass of dry air containing
the vapour. Thus
 M υ ρ vV ρ v e
w= = = =ε
M d ρ dV ρ d p−e
ρv and ρd are densities for vapor and dry air respectively while V is the volume for the mixture
also assumed to be the volume of each constituent if it a lone occupied the space. e is the vapor
pressure taken to be that due to the vapor while (p-e) pressure taken to be that of dry air. ε
=0.622
We make use of the fact that density in volume V is function of pressure to arrive at the above
expression

but P > > e, then

εe
w=
P

Saturating mixing ratio is given by

ε es
ws =
P
and is therefore a function of temperature and pressure. Because ws is a function of two
thermodynamic variables, lines of constant value of ws can be plotted on an α, -P diagram or any
diagram derived from it. Mixing ratio is expressed in practice as the number of grams of water
vapor per kilogram of dry air.

4. Specific Humidity, q

Specific humidity is defined as the ratio of mass of water vapour to the mass of moist air
containing the vapour. Thus

Mv P e
q= = v ≈ε
Mv + Md P P

As can be seen, specific humidity and mixing ratio are nearly equal and have same properties.

5. Relative Humidity, r

This is the ratio of the actual mixing ratio of a sample of air at a given temperature and pressure
to the saturation mixing ratio of the air at that temperature and pressure.

ω
r= × 100 , and is normally expressed as a percentage
ωs

6. Virtual Temperature, T*

This is the temperature at which dry air would have to be in order to have the same density as a
sample of moist air, assuming both have the same pressure.
  1+ w / ε 
T* = T  
 1+ w 

In lecture 1, we learnt that if T is replaced by T*, then equation of state for dry air may also be
used for moist air.
This is the temperature used in the equation of state when dealing with moist air. It is a function
of T and w.

7. Dew-Point Temperature, Td

This is defined as the temperature to which moist air must be cooled during a process in which P
and w remain constant, in order that it becomes just saturated with respect to water. At this
temperature, the mixing ratio of the air becomes its mixing ratio. Thus the mixing ratio lines on
any thermodynamic diagram can be used to determine dew points graphically. Similar concepts
apply for frost-point temperature, the latter being saturation with respect to ice which must be
achieved.

A meteorological process by which air can be brought to its dew point is radiational cooling of a
layer of air near the ground during the night. This is the primary process by which dew forms.

8. Wet-Bulb Temperature, Tw

This is the temperature to which air may be cooled by evaporating water into it at constant
pressure until it is saturated . The latent heat is thought of as coming from the air.

9. Lifting condensation level (LCL)

This is the level to which unsaturated air would have to be raised in a dry adiabatic expansion to
produce condensation. At the lifting condensation level (LCL), the mixing ratio becomes equal
to the saturation mixing ratio. On a thermodynamic diagram, this is the level at which the dry
adiabat through the initial pressure and temperature of the parcel intersects the saturation mixing
ratio line whose value of ws is equal to the initial mixing ratio of the parcel.
10. Wet bulb temperature Tw

This may be defined in two ways. The first definition is in terms of an isobaric process. It is the
temperature to which air may be cooled by evaporating water into it at constant pressure until it
is saturated. The latent heat is thought of as coming from the air. The mixing ratio, w, is not kept
constant in this definition making it different from the dew-point temperature.
The second definition is via an adiabatic process and is best described in terms of operations on a
diagram such as Stuve diagram. Hess, S.L. (1959). The temperature in this case will be adiabatic
wet-bult temperature.
A meteorological process by which air may be brought to its wet-bulb temperature is the
evaporation of falling rain into an initially unsaturated layer of air.

11. Wet bulb potential temperature θw

This is defined as the temperature to which air may be cooled by evaporating water into it at
constant pressure until it is saturated followed by pseudo-adiabatic compression to a pressure of
1000 mb. Each pseudoadiabat is characterized by one and only one value of θw, just as each such
line is characterized by a unique value of θe.

12. Equivalent Temperature, Te

The temperature a sample of air would have if all its latent heat were converted to sensible heat
by means of a pseudo-adiabatic expansion to low pressure and temperature followed by a dry
adiabatic compression to the original pressure.
The process is thought of to be comprised of the following steps:
• Saturated air rises and expands as surrounding pressure decreases

• Latent heat released as condensation products form and drop out

• The air becomes heavy and change direction i.e. begin to sink and the resulting
compression causes a rise in temperature.

• Heat cannot be used on the parcel as the water or ice formed and dropped out

• Parcel then warms dry-adiabatically

Lws

Mathematically, Te = Te
c pT
, where T is the original temperature of the parcel.

13. Equivalent potential temperature θe

This is the temperature a parcel of air will have if it were taken from its equivalent temperature
Te to a pressure of 1000 mb via a dry diabatic process.
Lws

Mathematically, θe = θ e
c pT

The corresponding properties of θe and θ w have been discussed. L is the latent heat of phase
change and the other parameters have the usual meaning.
3.2 Phase Digram of water
Isotherms of an ideal gas on a plot of specific volume versus pressure are rectangular hyperbolas.
However, physical conditions on our planet are such that water may exist in gaseous, liquid, and
solid phases. Whenever water vapor is sufficiently far from condensation or sublimation, it is
nearly ideal, so that its isotherms are also close approximations of hyperbolas.
The marked deviations from the ideal gas law during condensation are illustrated in Fig.3.1
below.

Figure 3.1: Phase diagram of water substance

On this diagram, Specific volume α is plotted against water substance pressure e. We allow e to
increase upward in this diagram since there is no need to make the pressure scale roughly
correspond with height in the atmosphere.

Now, on this diagram, consider a point marked A: Here all the water exists in vapor form.
From Boyle’s Law:
• Increase of e, means that α should decrease in accordance with the ideal gas law i.e. P α
= k (constant). The isotherm is nearly hyperbolic (line AB)

• On this line AB, a point B is eventually reached at which a slight increase of, e, will
result in a change of phase from vapor to liquid. In this state only an infinitesimally small
increment of pressure is needed to condense the entire vapor into liquid at a constant
temperature.

Change of phase which takes place at constant temperature starts at point B and is completed at
point C. The vapor pressure at B, eB and that at C, eC are practically equal, ie.e, eC ≅ eB (the
saturation vapor pressure). As the state of the sample moves from B to C the pressure remains
essentially constant, and the specific volume changes from that of the vapor at the given pressure
and temperature to that of the liquid at the same temperature and pressure which makes it highly
incompressible i.e. at C, the substance has all changed phase into liquid and increase in pressure
takes place at nearly constant α as shown by the sharp vertical change of the thick line from C.
Between B and C liquid and vapor coexist. To the right of B the sample is completely gaseous
while to the left of C, the sample is liquid.
Because it delineates those areas in which various phases may exist, the diagram is called a
phase diagram.

Saturation Vapour Pressure is the pressure at which vapor change phase to liquid.

Similarly if one follows the isotherm labeled “triple-state-isotherm”, a special situation is

encountered. As the vapor is compressed, an increase in vapor pressure implies that specific
volume α will decrease according to Boyle’s law. A point is eventually reached when vapor
changes to water and ice.

Equilibrium exists simultaneously between; vapor, water along the horizontal portion of this
isotherm. This condition occurs at a fixed temperature and pressure (specific state of the vapor).
This isotherm is referred to as the Triple State. For water, it occurs at pressure and temperature
of 6.11mb and 0.01°C respectively. For pressure and temperature below the triple state, liquid
does not occur and equilibrium exist between ice and vapor only.

Another special case is the isotherm which passes through the point D. To the right of D along
this isotherm only vapor can exist, while to the left of Donly liquid can exist. The differentiation
between liquid and vapor disappears. The point D is known as critical point. For water it exists
at pressure of 221bars and temperature of 374ºC.
The general significance of the critical point is that:
(i) Above critical point temperature you cannot liquefy a gas by cooling
(compression)
(ii) Above critical pressure you cannot liquefy a gas by cooling it

Therefore, liquefication takes place at temperatures and pressures below the critical values. In
addition, the specific volume α must lie in the proximity of the multiple-phase area. This
explains the great difference in behavior of the permanent atmospheric gases on the one hand
and water vapor on the other.
The permanent gases do not condense because their critical temperatures are much below those
in the atmosphere.

Water vapor does condense in the atmosphere because both its critical temperature and pressue
are above those ordinarily found in the atmosphere. In addition, there is often enough vapor
(sufficiently small specific volume) to allow the state to lie the multiple-phase portion of the α- e
diagram.

On the other hand, carbon dioxide gas (CO2) has critical temperature of 31°C and critical
pressure of 74 bars sufficiently high to permit condensation. However, the amount present in
the atmosphere is so small i.e. specific volume α is so high and hence its atmospheric state
always lies far to the right of the multiple-phase region. Thus CO2 never condenses naturally in
the atmosphere. On the other hand the planet Venus has much more CO2 in its atmosphere that it
is possible for condensation to take place there.

3.3 Clausius-Clapeyron equation

The Clausius-Clapeyron equation gives a relation between saturation vapor pressure, es, specific
volume α, and temperature T of a parcel of air. It is based upon the concept of entropy, relating
the saturation vapor pressure to the latent heat of a phase change. If a phase change occurs
reversibly, no alteration in the entropy of the system can occur except through the addition or
subtraction of heat
Thus if we consider the latent heat of phase change involved from phase 1 to phase 2 (L12);
where phase 1 could be liquid and phase 2 is vapor or vice-versa. The latent heat of phase
change is given by:

2 2
L12 =  dh =  Tdφ ....................................................................................(3.1)
1 1

For an isothermal change

2
L12 =  Tdφ = T (φ2 − φ1 ) , since T is constant
1

We now need to evaluate (φ2 − φ1 ) . In order to do this, we make use of the phase diagram shown
in figure 3.2:

e
Phase C
B Phase
1
2
A D

α
Figure 3.2: A cycle of phase changes of an α-e diagram

Consider a substance at point A where (es,T,α,) are coordinates of the substance at point A. If you
increase the temperature by ∆T so that the substance changes from A to B
→ Increase in es by ∆es and α1 by ∆α1 such that the coordinates at B becomes
(es + ∆es ), (T + ∆T ), (α 1 + ∆α 1 )
The transition from B to C is an isothermal change so that the substance exist in

Phase 2 at C so that the coordinates at C becomes ( es + ∆e s ; T + ∆T , α 2 + ∆α 2 )

From C to D, there is a change in temperature (decrease) by ∆T such that at D,the coordinates
become ( es , T , α 2 )

From D back to A is an isothermal change and the coordinates revert back to ( es , T , α 1 )

Since the substance is at equilibrium pressure during the cycle; the first law of thermodynamics
can be written as:

d h = cv d T + P d α

dh
dh = cv dT + es dα = Tdθ = dφ , the entropy
as
T
If we integrate around a closed cycle as the case in the figure above,

 Tdφ =  c dT + e dα ...................................................................................................(3.2)
v s

In which cv dT = 0

 Tdφ =  es dα ...........................................................................................................(3.3)
Using the diagram, the R.H.S of (3.3) is (α 2 − α 1 ) ∆e s

→  Tdφ = (α 2 − α 1 )∆e s ……………….....................................................(3.4)

(i) RHS = (α 2 − α 1 )e s , for equilibrium

(ii) RHS = (α 2 − α 1 )∆es when there is a change in es

To evaluate the L.H.S. of (3.3)

 d (Tφ ) =  Tdφ +  φ dT = 0 .................................................................(3.5)

as  d (Tφ ) = 0 is an exact differential

Hence  Tdφ = −  dT ……………........................................................... (3.6)

Let Φ1 = Entropy in phase 1

Φ2 = Entropy in phase 2
Expression (3.6) can be solved easily, by considering the transitions around the closed path A to
D and back to A, as follows:

from A → B = −  φ dT = −Φ 1 ∆T

from B → C = −  φ dT = 0

from C → D = −  φ dT = −Φ 2 • ∆T

from D → A = −  φ ∆T = 0

Hence by adding all the four transitions, (3.6) becomes

 Tdφ = −  φ dT =(φ2 − φ1 ) ∆T .............................................................................(3.7)

But from (3.5)  Tdφ = (α 2 − α 1 )∆es

∴ (φ 2 − φ1 )∆T = (α 2 − α 1 )∆es
de
φ 2 − φ1 = (α 2 − α 1 ) s (in the limiting process)......................................................(3.8)
dT

But L12 = dh = Tdφ

L12
→ dφ = = (Φ 2 − Φ 1 ) ................................................................................(3.9)
T
de
Substituting 3.9 into 3.8, L12 = T (α 2 − α 1 ) s
dT

de s de L12
Solving for → s = ……………................................ (3.10)
dT dT T (α 2 − α 1 )

Equation 3.10 is th Clausius-Clapeyeron equation

ACTIVITY 1
1. Show how specific humidity,q is related to the mixing ratio, w
2. What assumptions are used in deriving the Clausius-Clapeyeron formula?
3. Does vapor pressure and relative humidity mean the same thing?
 Self-assessment/ Revision questions
1. What does “virtual temperature” mean to you?
2. Differentiate between moisture, dry air and moist air.
3. Discuss the phase-diagram of water

Summary
In this lecture, the important moisture variables are described giving equations involved, where
applicable. There were relations noted between relative humidity, mixing ratio, and vapor pressure. Some
of these variables will be important in the discussion of thermodynamic diagrams.
The phase change of water in the atmosphere has also been discussed. This phase change form the basis
of an an equation that relates temperature, changes in specific volume, latent heat of phase change and
saturation vapor pressure.

REQUIRED READING
1. Hess, S. L., (1959): Introduction to theoretical Meteorology. FSU, Tallahassee, Florida State.
2. McIntosh D. H. and A.S. Thom (1972): Essentials of Meteorology. The Wykeham Science series