UNIT – V

MIXTURES OF PERFECT GASES AND PSYCHROMETRY

To determine the properties of a mixture, we need to know the

composition of the mixture as well as the properties of the individual
components. There are two ways to describe the composition of a mixture
namely molar analysis and gravimetric analysis
Molar analysis: It specifies the number of moles of each component
Gravimetric analysis: It specifies the mass of each component
As per molar analysis the number of moles of a nonreacting mixture is
equal to the sum of the number of moles of its components.

,
As per gravimetric analysis the mass of a mixture is equal to the sum of
the masses of its components.

Apparent (or average) molar mass M

The molar mass of a mixture

Mass and mole fractions of a mixture are related by

The sum of the mass and mole fractions of a mixture is equal to 1.

P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND REAL GASES

An ideal gas is defined as a gas whose molecules are spaced far

apart so that the behavior of a molecule is not influenced by the presence
of other molecules. The real gases approximate this behavior closely
when they are at a low pressure or high temperature relative to their
critical-point values. The P-v-T behavior of an ideal gas is expressed by
the simple relation Pv=RT, which is called the ideal-gas equation of state.
The P-v-T behavior of real gases is expressed by more complex equations
of state or by Pv=ZRT, where Z is the compressibility factor. The
prediction of the P-v-T behavior of gas mixtures is usually based on two
models:

Dalton’s law of additive pressures: The pressure of a gas mixture is

equal to the sum of the pressures each gas would exert if it existed alone
at the mixture temperature and volume.

Amagat’s law of additive volumes: The volume of a gas mixture is

equal to the sum of the volumes each gas would occupy if it existed alone
at the mixture temperature and pressure.
Ideal-Gas Mixtures

Note that for an ideal-gas mixture, the mole fraction, the pressure
fraction, and the volume fraction of a component are identical. This
equation is only valid for ideal-gas mixtures as it is derived by assuming
ideal-gas behavior for the gas mixture and each of its components.

The quantity yiPm is called the partial pressure (identical to the

component pressure for ideal gases), and the quantity yiVm is called the
partial volume (identical to the component volume for ideal gases).

Real-Gas Mixtures

Zi is determined either at Tm and Vm, Dalton’s law) or at Tm and Pm

(Amagat’s law) for each individual gas.
 Amagat’s law involves the use of mixture pressure Pm, which
accounts for the influence of intermolecular forces between the molecules
of different gases.

Dalton’s law disregards the influence of dissimilar molecules in a

mixture on each other. As a result, it tends to underpredict the pressure of
a gas mixture for a given Vm and Tm.

Dalton’s law is more appropriate for gas mixtures at low pressures.

Amagat’s law is more appropriate at high pressures.

PSYCHROMETRY
Art of measuring moisture content in the air is called psychrometry.
Psychrometrics
Science of studying the thermodynamic properties of moist air is
called psychrometrics. The amount of moisture vapour in the air varies
quite significantly under different conditions. When the air is hot, it can
contain a large amount of moisture vapour, sometimes as much as 5% by
volume. When it is cold, its capacity to hold the moisture is reduced.
When the temperature of warm air begins to fall, the vapour also cools
and, if cooling continues, it will condense into tiny moisture droplets. In
the atmosphere this results in the formation of clouds and eventually rain.

Psychrometric Terms

Atmospheric air: It contains nitrogen, oxygen, carbon dioxide, water

vapour, other gases, and miscellaneous contaminants such as dust,
pollen, and smoke. This is the air we breathe and use for ventilation.
Dry air: It is the air that is free from the contaminants and water vapour.
By volume, dry air contains about 78 percent nitrogen, 21 percent
oxygen, and 1 percent other gases. Dry air is used as the reference in
psychrometry.
Moist air: Moist air is the mixture of dry air and water vapour. For practical
purposes, moist air and atmospheric air can be considered equal under
the range of conditions normally encountered.
Saturated air: It is the mixture of dry air and water vapour when the air
has diffused the maximum amount of water vapour in to it.
Dry Bulb Temperature (DBT): It is the temperature that we measure with a
standard thermometer that has no water on its surface. When people
refer to the temperature of the air, they are commonly referring to its dry
bulb temperature.
Wet bulb temperature (WBT): Wet bulb temperature is the temperature
associated with the moisture content of the air. Wet bulb temperature is
taken by the thermometer whose bulb is covered with a wet wick and
while measuring the temperature the water evaporates. Because of the
evaporative cooling effect, Wet bulb temperatures are always lower than
dry bulb temperatures and the only time that they will be the same is at
saturation (i.e. 100% relative humidity). The wet bulb temperature (WBT)
relates relative humidity to the dry bulb temperature. If the relative
humidity is low and the temperature is high, moisture will evaporate very
quickly so its cooling effect will be more significant than if the relative
humidity was already high, in which case the evaporation rate would be
much lower.
Dew point temperature (DPT): Dew point temperature is the temperature
at which water will begin to condense out of moist air. When air is cooled,
the relative humidity increases until saturation is reached and
condensation occurs. Condensation occurs on surfaces which are at or
below the dew point temperature. At dew point, dry bulb temperature and
wet bulb temperature are exactly the same.
Wet bulb depression: It is the difference between the dry bulb
temperature and wet bulb temperature at any point.
Dew point depression: It is the difference between dry bulb temperature
and dew point temperature.
Degree of saturation (μ): It is the ratio of actual mass of water vapour in a
unit mass of dry air to the mass of water vapour in the same mass of dry
air when it is saturated at the same temperature.
Specific Humidity (W): It is the mass of water vapour present in 1 kg of dry
air and is generally expressed in terms of gram per kg of dry air (g /kg of
dry air). It is also called as humidity ratio or humidity.

Absolute humidity: It is the mass of water vapour present in 1 m 3 of dry air

and is expressed in g / m3 of dry air. It is also expressed in grains per
cubic meter. Mathematically 1 kg of water vapour is equal to 15430
grains.
Relative humidity (ϕ): It is the ratio of actual mass of water vapour in a
given volume of moist air to the mass of water vapour in the same volume
of saturated air at the same temperature and pressure.
Psychrometer: It is the device used to measure the properties of moist air.
Specific Volume: Specific volume is the volume that a certain weight of air
occupies at a specific set of conditions. The specific volume of air is
basically the reciprocal of air density. As the temperature of the air
increases, its density will decrease as its molecules vibrate more and take
up more space (as per Boyle’s law). Thus, the specific volume will increase
with increasing temperature.
Vapour Pressure: Pressure results from the number of water vapour
molecules per cubic meter are called vapour pressure. When water
changes state from a liquid to a gas, as it does when it evaporates into
the air, the water molecules in the vapour expand. Just as air pressure is
directly related to the number of gas molecules per cubic meter of space,
vapour pressure is also directly related to the number of gas molecules
per cubic meter of space. Thus, greater the moisture vapour content of
air, the greater the vapour pressure.
Enthalpy: Enthalpy is the measure of heat energy in the air due to
sensible heat or latent heat or both. Sensible heat is the heat (energy) in
the air due to the temperature of the air and the latent heat is the heat
(energy) in the air due to the moisture of the air. The sum of the latent
energy and the sensible energy is called the enthalpy of air.
Enthalpy is expressed in kilojoules per kilogram (kJ/kg). Enthalpy is
useful in air heating and cooling applications. Air with same amount of
energy may either be dry hot air (high sensible heat) or cool moist air
(high latent heat).
Dalton’s Law of Partial Pressures
It states that “The total pressure exerted by the mixture of air and
water vapour is equal to the sum of the pressures, which each constituent
would exert, if it occupied the same space by itself”. Mathematically
barometric pressure of the mixture is given by
Pb = P a + P v
Pa = Partial pressure of dry air
Pv = Partial pressure of water vapour
Psychrometric Relations
Till now some psychrometric terms were discussed. These terms
have some relation between one another.
1. Humidity or Specific Humidity or humidity ratio (W): It is the mass of
water vapour present in 1 kg of dry air and is generally expressed in
terms of gram per kg of dry air (g /kg of dry air).
Let Pa, va, Ta, ma, and Ra are pressure, volume, absolute temperature,
mass and gas constant respectively for dry air.
Pv, vv, Tv, mv, and Rv are pressure, volume, absolute temperature, mass
and gas constant respectively for water vapour.
Assuming that the dry air and water vapour behave as perfect gases, then
we will have
Pa va = ma Ra Ta ----------------- (1)
And Pv vv = mv Rv Tv ------------------ (2)
va = vv and Ta = Tv = Td
From equations (i) and (ii) we have
P v m v Rv
=
P a ma Ra
 m v Ra Pv
Humidity ratio W= =
ma Rv Pa
Substituting Ra = 0.287 kJ /kg K for dry air and R v = 0.461 kJ / kg K for
water vapour in the above equation for humidity ratio, we have

0.287 P v 0.622 Pv 0.622 P v

W= = =
0.461 P a Pa Pb−P v
In case of saturated air, the humidity ratio is given by

0.287 Ps 0.622 Ps 0.622 P s

W s= = =
0.461 P a Pa Pb−P s

2. Degree of saturation (μ): It is the ratio of actual mass of water vapour in

a unit mass of dry air to the mass of water vapour in the same mass of dry
air when it is saturated at the same temperature.

[ ]
0.622 P v Ps
1−
μ=
W
= b =
[
P −P v Pv P b−Ps P v
=
W s 0.622 Ps P s Pb −P v Ps ] Pb
P
1− v
P b−Ps Pb

3. Relative humidity (ϕ): It is the ratio of actual mass of water vapour in a

given volume of moist air to the mass of water vapour in the same volume
of saturated air at the same temperature and pressure.
mv
ϕ=
ms
Let Pv, vv, Tv, mv, and Rv are pressure, volume, absolute temperature,
mass and gas constant respectively for water vapour.
Ps, vs, Ts, ms, and Rs are pressure, volume, absolute temperature, mass
and gas constant respectively for saturated air.
Application of ideal gas equation for water vapour and saturated water
vapour gives

P s vs = m s R s T s
And P v vv = m v R v T v
According to the definitions vs = vv, Ts = Tv and Rs = Rv = 0.461 kJ / kg K
Then the relative humidity is given by
m v Pv
ϕ= =
m s Ps
The relation between degree of saturation and relative humidity is given
by
μ
ϕ=
Ps
1− (1−μ )
Pb
4. Pressure of water vapour: Pressure of water vapour can be calculated
by an empirical relation called carrier’s equation. It is given by
( Pb−P w ) ( T d −T w )
Pv =P w −
1544−1.44 T w
Where,
Pw = Saturation pressure corresponding to wet bulb temperature
Pb = Barometric pressure
Td = Dry bulb temperature
Tw = Wet bulb temperature
5. Vapour Density or Absolute humidity: It is the mass of water vapour
present in 1 m3 of dry air.
Let
vv = Volume of water vapour in m3 / kg of dry air at its partial pressure.
vv = Volume of dry air in m3 / kg of dry air at its partial pressure.
ρv = Density of water vapour in kg / m3 corresponding to its partial
pressure and dry bulb temperature
ρa = Density of air in kg / m3 of dry air
We know that mass of water vapour
mv = v v ρ v
and mass of dry air ma = v a ρ a
mv v v ρv
The above equations give =
ma v a ρa

But vv = va, therefore humidity ratio is given by

m v ρv
W= =
ma ρa
And ρv = W ρa
We know that P a va = m a R a T d
Since va = 1 / ρa and ma = 1 kg, therefore
substituting these values in the above equation gives
1 Pa
Pa =Ra T d or ρa =
ρa RaT d
So the value of ρv becomes
Pa W ( Pb−P v )
ρ v =Wρa=W =
Ra T d RaT d
6. Enthalpy of moist air: The enthalpy of moist air is numerically equal to
the enthalpy of dry air plus enthalpy of water vapour associated with dry
air. Let us consider 1 kg of dry air
Enthalpy 1 kg of dry air ha = cpa Td
cpa = Specific heat of dry air.
Td = Dry bulb temperature of air.
Enthalpy of water vapour associated with water vapour associated
With 1 kg of dry air is given by
hv = W h s
hs = Enthalpy of water vapour per kg of dry air at dew point
temperature
If the moist air is superheated the enthalpy of moist air is given by
W cps (Td – Tdp)
cps = Specific heat of superheated water vapour = 1.9 kJ / kg.
(Td – Tdp) is called degree of super heat of water vapour.
Now total enthalpy of superheated water vapour is given by
h = cpa Td + W hs + W cps (Td – Tdp)
= cpa Td + W [hfdp + hfgdp + cps (Td – Tdp)]
= cpa Td + W [4.2Tdp + hfgdp + cps (Td – Tdp)]
If cps = 1.9 kJ / kg is substituted in the above equation we get
h = (cpa + W cps) Td + W [hfgdp + 2.3 Tdp]
But (cpa + W cps) is called humid specific heat and its general value
is 1.022 kJ /kg K. So the value of enthalpy of air becomes
h = 1.022 Td + W (hfgdp + 2.3 Tdp) kJ
Adiabatic Saturation Process

Adiabatic saturation process is the process in which the air is

saturated by evaporates the water without the addition of heat. The
temperature at which the air can be brought to saturation state
adiabatically by the evaporation of water into the flowing air is called
adiabatic saturation temperature.
The equipment used for adiabatic saturation process consists of an
insulated chamber containing adequate quantity of water. There is also an
arrangement for makeup water to flow in to the chamber.
The unsaturated air enters into the chamber with temperature t 1
and specific humidity W1. As the air passes through the chamber over a
long sheet of water low pressure is created on the surface of the water.
Due to low pressure created on the free surface of water the saturation
temperature of air is reduced and the water will evaporate. This vapour
formed on the free surface of water is carried by the air flows over it.
During this process the specific humidity of water rises from W 1 to W2.
Here in this process moisture is added to the air till it is saturated without
any addition of heat, so it is called as adiabatic saturation process.
Psychrometric Chart
It is the graphical representation of various properties of moist air. It
is useful in finding out the properties of air and eliminates lot of
calculations. The psychrometric chart is normally drawn for standard
atmospheric pressure of 760 mm of Hg or 1.0132 bar.
 It consists of various lines. Different lines in the psychrometric chart
are discussed below.
1. Dry bulb temperature lines: The dry bulb temperature lines are vertical
on the psychrometric chart, parallel to the ordinate and uniformly spaced.
Generally, the temperature range is from – 60C to 450C
2. Specific humidity lines: The specific humidity lines are horizontal lines,
parallel to the abscissa and uniformly spaced. Generally the moisture
content range of these lines is from 0 to 30 g / kg of dry air

3. Wet bulb temperature lines: Wet bulb temperature lines are inclined
straight lines and non-uniformly spaced. At any point on the saturation
line both dry bulb and wet bulb temperatures are equal. Values of wet
bulb temperatures are given along the saturation curve.

4. Dew point temperature lines: Dew point temperature lines are

horizontal, parallel to abscissa and are non-uniformly spaced. At any point
on the saturation curve the dry bulb and dew point temperatures are
equal. The dew point temperatures are marked along the saturation
curve.
 5. Relative humidity: The relative humidity lines are curved lines and
follow the saturation curve. These lines are drawn with values 10%, 20%,
30% ... up to 100%. The saturation curve represents 100% relative

humidity.
6. Enthalpy lines: The enthalpy lines are inclined straight lines and
uniformly spaced. These lines are parallel to the WBT lines and drawn up
to the saturation curve. Some of these lines coincide with the wet bulb
temperature lines also. The values of total enthalpy are given on a scale
above the saturation curve.
7. Specific volume lines: The specific volume lines are obliquely inclined
straight lines and uniformly spaced. These lines are drawn up to the
saturation curve. The values of volume lines are generally given at the
base of the chart.

8. Vapour pressure lines: The vapour pressure lines are horizontal and
uniformly spaced. These are not drawn on the main chart. But a scale
showing vapour pressure in mm of Hg is given on the extreme left side of
the chart.

Psychrometric Processes
The processes involved in air conditioning to vary the psychrometric
properties of air are called psychrometric processes. Basically there are
five different psychrometric processes.
1. Sensible Heating
2. Sensible Cooling
3. Humidification
4. Dehumidification
5. Mixing of two streams
 From these five processes we can get the combinations of processes
also. Now let us see how to represent the processes on the psychrometric
chart and how the properties of air changes during the processes.
Sensible Heating: The heating of air without any change in humidity is
known as sensible heating. Let air at temperature t da passes over a
heating coil of temperature tdc and comes out from the coil at t db. The
process of sensible heating on the psychrometric chart is shown by
horizontal line A-B extending from left to right.

The heat absorbed by the air during sensible heating is given by the
enthalpy difference (hb – ha). The specific humidity during the process
remains constant. Heat added during the process
q = (hb – ha) = cpa (tdb - tda) + W cps (tdb - tda)
= (cpa + W cps) (tdb - tda)
= cpm (tdb - tda)
Where
cpm = (cpa + W cps) is called humid specific heat and is equal to 1.022
Therefore heat added is equal to
q = 1.022 (tdb - tda) kJ/kg
Sensible Cooling: The cooling of air without any change in its specific
humidity is known as sensible cooling. Let air at temperature t da passes
over a heating coil of temperature t dc and comes out from the coil at t db.
The process of sensible cooling on the psychrometric chart is shown by
horizontal line A-B extending from right to left.
The heat rejected by the air during sensible heating is given by the
enthalpy difference (ha – hb). The specific humidity during the process
remains constant. Heat rejected during the process
q = (ha – hb) = cpa (tda - tdb) + W cps (tda - tdb)
= (cpa + W cps) (tda - tdb)
= cpm (tda - tdb)
Where
cpm = (cpa + W cps) is called humid specific heat and is equal to 1.022
Therefore heat rejected is equal to
q = 1.022 (tda - tdb) kJ/kg

Bypass factor of heating or cooling coil: It is evident that the temperature

of the air coming out of the apparatus will be less than the coil
temperature in case of heating and the temperature of the air coming out
of the apparatus is more than the temperature of coil in case of cooling.
Consider 1 kg of air passing over the cooling coil or heating coil
A little consideration will show that when air passes over the coil, some
of it (x kg) just by-passes unaffected while the remaining (1-x) kg comes
in to direct contact with the coil.
The amount of air that bypasses is called bypass factor
The bypass factor depends on the following factors.
1. The number of fins provided on a unit length
2. The number of rows in a coil in the direction of flow.
3. The velocity of flow of air
 The bypass factor of a cooling coil decreases with decrease in fin
spacing and increase in number of rows.
Let
tda = Temperature of the air at inlet
tdb = Temperature of the air at outlet
tdc = Temperature of the coil
x = Mass of air that is bypassed
(1-x) = Mass of air that is comes in to direct contact with coil
Balancing the enthalpies between inlet and outlet gives
x cpm tda + (1 – x) cpm tdc = cpm tda
It gives the value of x as
t dc−t db
x=
t dc−t da

t dc−t db
Or BPF=
t dc−t da

Similarly for the cooling coil the bypass factor is given by

t db−t dc
BPF=
t da−t dc