PSYCHROMETRICS

Psychrometrics is the study of thermodynamics of moist air. This area is of great

interest in the field of air conditioning.

Consider a mixture of air and water vapor.1 These two components are
considered to be non-reacting, that is, the molecules of air and water do not combine with
each other, but rather stay separated. Both substances are considered to be ideal gases.
Each component behaves as if it is alone at the mixture pressure and temperature and can
roam throughout the whole volume.

Each component exerts what is called a partial pressure. The partial pressure is the
pressure that each component would exert if it were alone in the volume V at the mixture
temperature T. The sum of the partial pressures is the mixture pressure.

The partial pressure of component “i” can be evaluated using the ideal gas law:

ni R T
pi =
V

ni R T
pi V = ni = y
= i
p nR T n
V
where n = number of moles
y = mole fraction

and then pi = y i p
Mixing Process at Constant Composition

In this case we are considering that the proportion of each component is not
changed. To obtain a property for the mixture, just add the changes in the property you
are interested in for each component. For example, supposed we had an initial state
consisting of temperature T1 and pressure P1, and a final state consisting of temperature
T2 and pressure P2. Then the changes in internal energy, enthalpy, and entropy are given
by, respectively:

j
U 2 −U 1 = ∑ni[u i (T 2 ) −u i (T 1)]
i =1
1
Moran, M.J., and Shapiro, H.J., Fundamentals of Engineering Thermodynamics, Wiley, 2000, Chapter 12:
Ideal Gas Mixtures and Psychrometrics.

1
 j
H 2 − H 1 = ∑ni[ h i (T 2 ) − h i (T 1)]
i =1

S 2 − S 1 = ∑ni[s i (T 2 , pi 2 ) − s i (T 1 , pi1)]
j

i =1

where n is the number of moles of the mixture. These properties can be evaluated by
using tables or various software programs, including EES.

See Example 12.3 below, (Moran and Shapiro).

(This example does not include moist air but the procedure is the same, as they are ideal
gases.)

2
3
4
Note: Equation 12.36 is:
p2
∆ s i = s i ( T 2 ) − s i ( T 1) − R ln
p1
where the bar on top means on a molar basis (per mole).

Mixing of Ideal Gases

Now, let’s mix gases that are initially separate. This is irreversible (therefore
entropy is produced). Three things contribute to the irreversibility:

1. The gases are initially at different temperatures

2. The gases are initially at different pressures
3. The gases are distinguishable from each other

Any of these produces entropy when the gases are mixed.

5
Psychrometrics

Here we are going to mix dry air and water vapor to form “moist air”. We assume
that the dry air is “pure”; that is, it has no water or contaminants in it. The amount of
water in the air varies from 0 to a maximum. The maximum amount of water occurs at
saturation, which depends on the temperature and pressure of the mixture. The mixture
is said to be saturated when the partial pressure of the water vapor corresponds to the
saturation pressure of water at the mixture temperature. Saturated air is a mixture of dry
air and saturated water vapor.

There are several ways to describe the moisture content of moist air. These are
mainly definitions of terms that are used in the air conditioning industry.

The humidity ratio, ω, is the ratio of the mass of water vapor to that of dry air.
We can also express it in terms of partial pressures and molecular weights, as shown
below.
M v pv p
ω = mv = = 0.622 v
ma M a p a p − pv
where mv and ma are the masses and Mv and Ma are the molecular weights of the vapor
and air, respectively.

The degree of saturation, μ, is the ratio of air humidity ratio ω to the humidity ratio ωs of
saturated air at the same temperature and pressure.2

ω
µ=
ω s T,p

The relative humidity is defined as the mole fraction of water vapor, yv, to the mole
fraction yv,sat of saturated moist air at the same mixture temperature and pressure.

yν µ p
φ= = = v
yν , sat 1 − (1 − µ ) yν , sat p g
T,p T,p
(Because pv == yvp and pg = yv,satp)

2
American Society of Heating, Refrigeration, and Air Conditioning Engineers, ASHRAE Handbook, 1977
Fundamentals, 1978.

6
Evaluating enthalpy, internal energy and entropy

The values of H, U and S for moist air can be found by adding the contribution of
each component at the condition at which the component exists in the mixture. For
example,

H = H a + H v = m a h a + mv h v
or, alternatively, per unit mass of dry air,

H
= h a + ω hv
ma
These quantities are evaluated at the mixture temperature. Here we do not use the ideal
gas table values for water vapor (Table A-23) but instead use hv = hg(T) from the steam
tables to get more accurate results.

Dew Point

The dew point temperature, T’ or Tdp, is the temperature of moist air which is saturated
with the same humidity ratio, ω, as the mixture under consideration. That is,

ω s ( p, T dp) = ω
If we cooled a sample of moist air at constant pressure,3 the composition of the mixture
and the partial pressure of the water vapor would remain constant until the dew point
temperature was reached. Then, as the system temperature went below the dew point
temperature, some of the water would condense out of the mixture. In the final state we
would have some air, some water vapor, and some liquid water. The remaining water
vapor would be saturated, with the partial pressure equal to the saturation pressure at the
final temperature. The condensate would be saturated liquid at the final temperature.

3
Black, W.Z. and Hartley J.G., Thermodynamics, Harper Collins, 1995.

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Thermodynamic Wet-Bulb Temperature:

The dry bulb temperature is just the temperature of the mixture as measured by a
thermometer. The wet bulb temperature is explained below.

For any state of moist air, there exists a temperature, Twb, at which liquid (or
solid) water may be evaporated into the air to bring it to saturation at exactly this same
temperature and pressure.
In a constant pressure process, the humidity ratio is increased from ω to ωs
corresponding to saturation at Twb. The initial enthalpy h goes to hs,wb corresponding to
saturation at Twb. The weight of water added per pound of dry air is (ωs,wb – ω), which
adds energy (ωs,wb – ω)hw,wb where hw,wb is the specific enthalpy added at Twb. Thus, for an
adiabatic process,

h + ( ω s , w b − ω ) h w, w b = h s , w b
where ωs,wb , hw,wb, and hs,wb are functions of Twb for a given pressure.