2.

Equilibrium data for gas-vapour mixtures (typically air/water) (Humidity Charts)

These show thermodynamic data for gas-vapour mixtures e.g., air-water; air-organic. The “gas
component” (very often air) is assumed to be inert and non-condensable, whereas the vapour is
often in equilibrium with its (pure) liquid phase. A variety of data are summarised on a single
humidity diagram (Psychrometric chart), giving a sometimes-complex appearance!!

• e.g., for air/water at a total pressure of 1 bar.

2.1 Humidity
The amount of vapour that can be present in a gas phase increases with temperature as the
partial pressure of the substance increases. The shape of Pvap vs. T curve is typically described
by the familiar Antoine equation.

B
ln p vap= A −
T +C

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Rather than describing the amount/concentration of vapour present in terms of a partial
pressure, it is more common to introduce the concept of humidity, H. It is defined as the
moisture content of a gas (by mass).

mass of vapour (kg) p vap M v

H≡ =
mass of vapour-free gas (kg) M g ( P − p vap )
(2.1)

M v and M g are the RMM of the vapour and gas, respectively. “Vapour-free gas” is also referred
to as “bone-dry” gas.
On humidity charts, all quantities are normalised to 1 kg of bone-dry gas in the mixture (and
not 1 kg of the mixture itself (i.e., they are specified on a vapour-free basis).

2.1.1 Saturation humidity, H*

When the gas-vapour mixture is in equilibrium with the liquid p vap = p* and H = H * . H* is a
function of temperature (the dry bulb, i.e., actual, or normal) as shown by the chart.

pv* M v
H* =
M g ( P − pv* )

Example: For air/water, the saturated humidity at 30 oC is 0.0272 kg/kg

2.1.2 Relative (or percentage) humidity, H R

This is the ratio of the actual humidity t the value of H* at the same temperature and pressure.

H
HR = x 100% 2.2
H*

Relative humidity lines may also be shown on the humidity chart. They have roughly the same
shape as the saturation curve and are marked with the %humidity e.g., 90%, 80%, etc.
Example: Air/water at 30 oC and a humidity of 0.015 kg/kg has a relative humidity of 56%.

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2.2 Enthalpy of gas/vapour mixture and humid heat
The enthalpy of the mixture of humidity H:
h = enthalpy of 1 kg bone-dry gas + enthalpy of H kg vapour.

(
h CPgas (T − T0 ) + H CPvap (T − T0 ) + λ
= ) 2.3

where λ is the enthalpy of vaporisation (J/kg)

[note on baseline of enthalpy values: the enthalpy of the condensable species is taken to be zero
at the reference temperature T 0 ].

Hence: h = s (T − T0 ) + H λ 2.4

Where s is defined as the humid heat, i.e., the effective specific heat capacity of this gas/vapour
mixture.

(
s ≡ CPgas + HCPvap ) 2.5

Note: s is not a constant as it is a function of H

Enthalpies of gas/vapour mixtures are read from the chart using the “lines of constant enthalpy”.
These lines (dotted) run at an angle to the principal axes.

Example: The enthalpy of air/water at 45 oC and humidity of 0.029 kg/kg is 120 kJ/kg.

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What is the origin of these lines of constant enthalpy also known as adiabatic saturation lines?
Consider the mixing of some gas-vapour mixture with some more liquid and allow the system
to come to equilibrium in an adiabatic system.

Mass of liquid added = H 3 -H 1 kg per kg bone dry gas in the system.

Enthalpy balance (per kg bone dry gas in the system):

h3 =h1 + ( H 3 − H1 ) C L (T2 − T0 )

(the second term is the enthalpy of the added liquid). Substitute for h 3 and h 1 , using equation
2.4

s (T3 − T0 ) + H 3λ = s (T1 − T0 ) + H1λ + ( H 3 − H1 ) C L (T2 − T0 )

− ( H 3 − H1 ) {λ + C L (T2 − T0 )}
s (T3 − T1 ) =

Assume that C (T2 − T0 ) << λ ,

L

H 3 − H1 s
= − 2.6
T3 − T1 λ

s
This is an adiabatic saturation line relating H and T and has slope − .
λ
Hence, as more liquid is added, the humidity increases, but the temperature falls because of the
use of some of the enthalpy in the system to vaporise the added liquid adiabatically. As more
and more liquid is added the system eventually becomes saturated as we reach the saturation
line.
The temperature and humidity at which this occurs are known as the adiabatic saturation
temperature TS and adiabatic saturation humidity HS and can be determined as follows:

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Example: Air/water at 40 oC and a humidity of 0.01 kg/kg has an adiabatic saturation
temperature and an adiabatic saturation humidity of 22.5 oC and 0.0174 kg/kg, respectively.

2.3 Dew-point temperature

When a gas/vapour mixture is cooled, the vapour will eventually start to condense, and droplets
of liquid (dew) appear. The first drop of liquid appears at the dew point temperature TD, i.e., at
TD, H = H *

Example: Air/water at 40 oC and a humidity of 0.01 kg/kg has a dew point temperature of ~13.5
o
C.

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2.4 Wet-bulb temperature
It is a well-known observation that wet material exposed to a current of gas takes up a
temperature, the wet bulb temperature TW, that is lower that the gas temperature, T. This is
because some of the liquid evaporates from the surface of the material and enthalpy of
vaporisation needs to be supplied to drive this process. This enthalpy is provided from the
surroundings because of heat transfer driven by the temperature gradient (T-TW).
Consider a wet-bulb thermometer, i.e., a regular thermometer with a piece of wet material
covering the bulb/sensor.

• Assume equilibrium at the interface and gas is in contact with the water surface.
This is an example of a system in which there is simultaneous heat (to supply enthalpy of
vaporisation) and mass transfer (vaporisation water):

Rate of heat transfer per unit area of cloth:

=q U (T − T W ) J m-2s-1

where U is the overall heat transfer coefficient. This heat transfer causes some of the liquid to
evaporate:

Rate of mass transfer per unit area (in mass terms):

=N w M v k g ( c*g − cg ) kg m-2 s-1

where k g is the mass transfer coefficient (m/s), c g is the molar concentration of the vapour in
*
the gas, and cg is the saturated value at the surface of the material.

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 p
Hence, using the ideal gas law, i.e., cg = ,
RT

=N w kg
RT
( p − p)
Mv W

where p is the partial pressure of the vapour and pW is the partial pressure of the vapour at the
surface of the material (i.e., the saturated vapour pressure at temperature TW).

Mv p M p
=
But from §2.1, H ≈ v for p << P, i.e. for dilute vapour
M g ( P − p) M g P

MgP
and thus, p = H , i.e. the partial pressure of the vapour can be related to the humidity of
Mv
the system

(H H ) ρ kg ( H W − H )
PM g
∴=
N w kg W
−=
RT

=
i.e. (
Nw k † H W − H ) 2.7

where k = ρ k g is a mass transfer coefficient (units: kg/m2s) appropriate for use with a humidity
†

( )
difference driving force H − H . Note: ρ = mass density (kg/m3).
W

At steady state, the heat supplied = the heat used for vaporisation

q = λ Nw

the mass transfer rate x the enthalpy of vaporisation per unit mass.

U (T − =
T W ) λρ k g ( H W − H )

HW − H U
= − 2.8
T −T
W
λρ k g

This is the equation of the line of constant wet bulb temperature and shows how the wet-bulb
temperature, TW, and the wet-bulb humidity, HW, are related to T and H. TW and HW can be found
by going up the wet-bulb line until it hits the saturation curve. The values of H and T obtained
at this intersection are the wet bulb humidity and wet bulb temperatures, respectively. The wet
bulb lines (solid) often have their respective wet bulb temperatures written on them. For the
air/water system only, these lines (solid) appear to run parallel to the adiabatic saturation lines.

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Example: For air/water at 31 oC and a humidity of 0.010 kg/kg, the wet bulb temperature is 20
o
C and the wet bulb humidity is 0.0148 kg/kg

Measurements of the dry bulb (normal) temperature and the wet bulb temperature enable the
humidity of the system to be determined. The greater the difference in the readings, the drier
the gas is. If the readings are identical, the gas is saturated with vapour.

Example:
Measurements of an air/water system indicated a dry bulb temperature of 40 oC and a wet bulb
temperature of 20 oC; what is the humidity?

Ans: 0.0064 kg/kg (a relative humidity of ~14%).

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2.5 Relationship between slopes of the adiabatic saturation line and the wet-bulb line.
Assume the j-factor analogy is applicable, i.e.
2/3
St  Sc 
St Pr= St ′Sc
2/3 2/3
⇒ =  
St ′  Pr 
2/3
U kg U St  Sc 
Using the definitions, St = and St ′ = ⇒ =s = s 
ρ us u ρ kg St ′  Pr 
2/3
U s  Sc 
Then, − =−  
ρ kg λ  λ  Pr 

  Slope of adiabatic
Slope of the wet bulb line saturaton line

Sc
For an air/water system, ≈ 1 and hence for this system only, the two lines have the same
Pr
slope as can be seen from the air/water humidity diagram, where the lines can be seem to be
straight and parallel. Under these circumstances

U = sρ kg

i.e., there is a strict relationship between the heat ad mass transfer coefficients for air/water
mixtures.

Note: this diagram includes yet two more parameters, namely:

(1) the variation of the latent heat of vaporisation with temperature
(2) the variation of the humid heat (s) with humidity

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