Lecture 9

Thermodynamics of humid air

Part 1
Areas in energy technology where
thermodynamics of humid air is needed

• HVAC technology

• Drying processes

• Cooling towers and scrubbers (heat recovery from humid gas)

• Heat exhangers of humid air and flue gases

Components of dry and humid air

Dry air Humid air

O2 N2 CO2 Ar
O2 N2 CO2 Ar
Ne He H2O
Ne He
Mv = 0.018015kg/mol
Mda = 0.02896kg/mol  0.018kg/mol
 0.029kg/mol
v = vapor
da = dry air

A good approximation
xO2 = 21 Vol-% (mol-%)
xN2 = 79% Vol-% (mol-%)
Basic definitions
Both dry air and vapor are ideal gases

Absolute humidity (kgv/kgda)

mv
x
m da

Total pressure

ptot = pda + pv

Total density

tot = da + v

v
m
Note that the absolute humidity can also be x
 da
m
Sometimes absolute humidity is also called mixing ratio
Basic definitions
The dependence between vapor pressure and absolute humidity

m da mv
p da V  RT pvV  RT =>
M da Mv

p v M v p da M da mv M p pv
  x v v => x  0.622
mv m da m da M da p da p tot  p v

pda = ptot – pv

Mv/Mda = 0.02896/0.018 =0.622

Basic definitions
Relative humidity

pv
 '
,
p v (T)

where p 'v (T) is the saturated vapor pressure.

The influence of dry air is negligible on the saturated vapor pressure p’v(T) => we can use
the same values as in the steam tables.

An approximation equation for the saturated vapor pressure

 11.78(T  372.79) 
p 'v (T)  105 exp  , where T = temperature [K]
 T  43.15 

In some references, the relative humidity means: f = x/x’

THIS DEFINITION IS NOT USED IN THIS COURSE
The influence of dry air on the saturated
vapor pressure
System 1 System 2

Saturated air
Vapor (T, p = pv0) What is the influence of
vapor + dry air
(T, p = pda + pv) pda on pv when T is
constant?

Liquid (T, pv0 ) Liquid (T, p)

At equilibrium At equilibrium

μ liq (T, p)  μ v (T, p v )

μ liq,0 (T, p v0 )  μ v,0 (T, p v0 )
p
μ liq pv
μ v
μ liq,0 (T, p v0 )  
p v0
p
dp  μ v,0 (T, p v0 )  p p v dp v
v0

μ liq μ v
dp  dp v
p p v

pv0 represents the vapor pressure when dry air does not exists = pv’(T).
pv represents the vapor pressure when dry air exists.
The influence of dry air on the saturated
vapor pressure
μ liq μ v
Derivates of chemical potentials with respect to pressure  vliq  v v 
p p v

v liq dp da
v v dp v  v liq dp and considering dp  dp da  dp v  dp v 
v v  v liq

RT
v v  v liq and vv  
pv

vliq dp da dp v v liq dp da
dp v   
RT pv RT
pv
The influence of the air on the saturated
vapor pressure
pv p da
p v (T, pda ) v liq
dp v
p p v  
v liq dp da
 ln  pda  0 
RT p v0 (T) RT
v0 0

v 
p v (T, pda )  p v0 (T)exp liq pda  ,
 RT 

where vliq is in unit m3/mol

 M H 2O v'liq 
Usually vliq is given in unit m3/kg => p v (T, p da )  p v0 (T)exp p da 
 RT 

v’liq is the specific volume of liquid water in

unit m3/kg
The influence of dry air on the saturated
vapor pressure, example
Initial values

t = 20oC, pda = 9.97104 Pa v’liq = 0.001 m3/kg MH2O = 0.018 kg/mol

For pure vapor pv’(20oC) = 2337 Pa (tabulated value)

For the mixture of vapor and dry air

 M H 2 O v'liq   0.018  0.001 

p v (T, p da )  p v (T)exp p da   2337exp 99700  2338.7 Pa
 RT   8.314  293.15 

The difference is ca. 1.8 Pa => it is negligible

If pda = 9.97105 Pa => pv(T,pda) = 2354 Pa => we still can assume that pv(T,pda)  pv’(T)
Enthalpy of humid air
H = mdahda + mvhv = mdahda + xmdahv => hk = hda + xhv [kJ/kgda]

Both gases are ideal gases => hk only depends on the temperature

Zero/reference-points for dry air and water are:

Dry air: dry air at 0oC

Water: water in liquid form at 0oC

t
h da   c pda dt  c pda (t  0)  c pda t ,
0

where c pda is the average c p over the temperature range of 0...t.

t
h v  2501   c pdv dt  2501  c pdv (t - 0)  c pdv t  2501 ,
0

where c pdv is the average heat capacity of vapor over the temperature range of 0...t
and 2501 vaporization heat of water at 0o C [kJ/kg].

cp values for dry air and vapor are usually

given in unit kJ/(kgoC)
 Enthalpy of humid air
Substituting results of integration in the definition of the enthalpy =>

hk = cpdat + x(cpvt + 2501) [kJ/kgda]

NOTE!

Temperature t is always given in unit oC.

x is the absolute humidity and is given in unit kgv/kgda

cpda and cpv represent the average heat capacities over the temperature range of 0…t oC.

Heat capacities can be given in units kJ/(kgoC) or kJ/(kgK).

In most calculations, we only use the symbol h (not hk) for the humid air, if there is no risk for
any misunderstanding.
Example 1
The air temperature is 27oC, relative humidity 18% and total pressure 99800Pa.
What is the absolute humidity, enthalpy and density of the air?

pv’(27oC) = 3564 Pa

p v  p 'v (27o C)  0.18  3564  641.5 Pa

pv 641.5
x  0.622  0.622  0.004 kg/kg da
p tot  p v 99800  641.5

h = cpdat + x(cpvt + 2501) = 1.0027 + 0.004 (1.86 27 + 2501) = 37.3 kJ/kgda

p da M da p v M v (99800 - 641.5)  0.029 641.5  0.018

ρ  ρ da  ρ v      1.157 kg/m 3
RT RT 8.314  300.15 8.314  300.15
Mollier diagram, psychrometric chart,
i,x diagram (Salin Soininen perspective)

f = x/x’

 f IS NOT
THE RELATIVE
HUMIDITY

Saturation
curve
Mollier diagram
Dew point temperature (kastepiste)

What is the dew point temperature of the air?

pv’(20oC) = 2337 Pa
Air conditions
pv =  pv’(20oC) = 0.42337 = 935 Pa
t = 20oC
 = 40% Find a temperature where
ptot = 100kPa
pv’(t) = 935 Pa

From the steam table

pv’(6oC) = 934.9 Pa => tdp  6oC

Example 2

What is the dew point of the air?

Air conditions pv
x  0.622
p tot  p v
t = 23oC
x 0.007
x = 0.007kg/kgda  p v  p tot  99700  1110 Pa
p = 99.7 kPa 0.622  x 0.622  0.007

Find a temperature where

pv’(t) = 1110 Pa

pv’(8oC) = 1073Pa pv’(9oC) = 1148Pa

=> tdp  8.5oC