AIR-WATER MASS TRANSFER Chapter 4

CENTRAL AIR-WATER MASS TRANSFER PROCESSES

FIGURE 4.1 Outline of
central interfacial related
exchange and reactions of
volatile compounds
in the sewer atmosphere.

We need to focus on two aspects:

• Equilibrium 
• Kinetics   
THE IDEAL GAS LAW Example: at 273 K (0 °C) and 1
atm, 1 mole of ideal gas has a
The ideal gas law is the equation of state of a volume of:
hypothetical ideal gas. The ideal gas law is
often introduced in its common form: L  atm
1mol  0.082  273K
V= K  mol = 22.4 L
1atm
 TRACE QUANTITIES OF A IN AIR AND WATER
In air: In water:
Ideal gas: Molar weight of water (H2O): 18 g mol-1
22.4 L mol-1 at 0C and 1 atm.
c1 A c1 A c2 A c2 A
yA = = xA = =
1 / 22.4 0.0446 1000 / 18 55.56
Where:
c1A Molar concentration of A in air [mol L-1] Where
c2A Molar concentration of A in water [mol L-1]
THE COMPOSITION OF AIR
Gas % Partial pressure (atm) ppm
P = 1 atm
N2 78 pN2 = 0.78 780 000

O2 21 0.21 210 000

Ar 1 0.01 10 000

CO2 0.04 0.0004 400

VOLATILITY OF GASES (EQUILIBRIUM)
Henry’s law
pA = P ∙ yA = xA ∙ HA

where
pA partial pressure of A (Atm)
P total pressure (Atm)
yA concentration of A in the gas (mol mol-1)
xA concentration of A in liquid (mol mol-1)
HA Henry’s law constant for A (Atm)

HA is specific for individual gases “The concentration of a solute

HA can be found with many different units!!! gas in a solution is directly
Large HA → high volatility proportional to the partial
HA increases with temperature pressure of that gas above the
solution”
Low volatility

High volatility
ACID-BASE EQUILIBRIUM OF AQUEOUS H 2S
Ka1 and Ka2 determine the ratio between the
concentrations, C, at equilibrium:

CH + CHS − C H + CS 2 −
K a1 = Ka2 =
CH 2 S (aq) CHS −

Only the first equation is of importance in

natural waters. Rearranging the equation and
knowing that –log is abbreviated p yields:

CHS −
pH = pK a1 + log
CH 2 S (aq)
WATER–AIR EQUILIBRIUM FOR H 2S

“Only dissolved hydrogen sulfide, H2S(aq), can be emitted from the water phase to the gas phase. Thus,
the equilibrium concentration in the overlaying sewer atmosphere will be reduced with increasing pH.”
TWO-FILM THEORY (KINETICS)
Assumptions:
Transport is by diffusion through two
stagnant films. One in the liquid phase
and one in the gas.
No resistance against transport across
the interphase
Total resistance against transfer =
resistance in liquid film + resistance in
gas film
Equilibrium at the interphase (Henrys
law applies).
No accumulation in the two film layers
TWO-FILM THEORY (KINETICS)
We define:

J A  − K L ( x *A − x A )
where HA *
yA = xA
P

From insertion we come up with:

1 P 1
= +
Flux through gas film
K L k1 A H A k 2 A
J A = k1 A ( y Ai − y A )
HA Resistance in
… water film
J A = −k 2 A ( x Ai − x A ) > 250 atm (mol%) water film
< 1 atm (mol%) gas film
RESISTANCE AGAINST MASS TRANSFER
H2S and O2 behaves similarly

1PNOH

DMDS
BTALD
ACTN

MeSH
EtOH

CO2
CS2
H2S

O2
100
Fraction of resistance [%]

80

60
liquid phase
40 gasphase

20

0
0.0001 0.001 0.01 0.1 1 10 100
Henry’s constant [-]
PREDICTION OF REAERATION
EMPIRICAL MODELS FOR THE PREDICTING KLaO2
Overall Oxygen Transfer Coefficient KLa(20) in Gravity Sewers

Where,
Fr = u(g dm)−0.5 is the Froude number (–);
u is the mean velocity of flow (m s–1);
dm is the hydraulic mean depth (m);
s is the slope (m m–1).
DETERMINATION OF K L FOR OTHER GASES
For gases with resistance against transport • The diffusion coefficient of a gas can be
in the liquid film: related to its boiling point.
n • Ratio between diffusion coefficient for H2S
KL  DL  and O2 can this way be estimated in the
= 
K LO2  DLO2 

range 0.84 – 0.86.
• For most conditions n≈1.
Where • Therefore:
KL and KLO2 mass transport coefficient
K L,H2S
DL and DLO2 diffusion coefficient  0.84
K L ,O2
n exponent = 0.5 - 1
CALCULATION OF H 2S RELEASE
SEWER DROP STRUCTURES
REAERATION AT SEWER DROPS
REAERATION AT SEWER DROPS rO
SUMMARY
Wastewater that has been transported under anaerobic conditions contain various
volatile and potentially odorous gases; e.g., H2S, mercaptans and amines

Air-water mass transfer of volatile gases (e.g., H2S) can be estimated from models
derived for aeration

Different models exist for both steady uniform flow conditions and for drop-structures