ρL ρL

y yo
t 1−x A 2 1−x A 2
( y− y o ) =
2 C T M A D AB ln
1−x A 1
+
( )
2 C T M A D AB ln
1−x A 1 ( )
t
Sketch ( y− y o ) against y result the following figure:
ρL
1−x A 2

Slope: s =
2 C T M A D AB ln
( 1−x A 1 )
ρL
1−x A 2

→ DAB =
2 C T M A s ln
( 1−x A 1 ) …(*)

From the figure: s = 0.031 ks/mm2

xA2 = 0 , xA1 = 37.6/101.3 = 0.37

CT = 1/V

P1 V 1 P2 V 2
=
T1 T2 but P1 = P2
V 1T2 321 y (mm)
→ V2 = T 1 = 22.4 273
= 26.34 m3/kmol
→ CT = 1/26.34 = 0.038 kmol/m3 , MA = 154 Substitute the above parameters in the Eq. (*)

1540
1−0
2×0 . 038×154×0 . 031×ln
→ DAB = 1−0 . 37 = 9.12×10-6 m2/s
Mass transfer theories
Interface

NA
1. The two films theory (Whitman, 1923)
CA or pA Liquid
This assumes: (1) steady state mass transfer. Ci
dc Gas Pi CA
N A=−D AB A
i.e. dy
…..(1)
(2) resistance to mass transfer lies in two films on both sides of the interface.
δ1 δ2
δ1 C Ai P Ai
D AB D AB
N A∫ dy=−D AB ∫ dc A=− ∫ P A ⇒ N A= ( P A −P i )
→Eq.1: 0 CA RT PA RT δ1 (in gas phase)
l
AB
D
N A= ( C i−C A )
Also: δ2 (in liquid phase)
It can rewrite the above equations in the general form:

NA = kg ∆P in gas phase
NA = kl ∆C in liquid phase
1 1
Note: ∆C = NA. k , V = I.R , OR NA = k. ∆C , I = V. R
2. The penetration theory (Higbie, 1935)

∂C A ∂2 C A
=D AB
This assumes: (1) unsteady state diffusion i.e. ∂t ∂ y2
……(2)
(2) There are clumps of solute molecules arrive at the interface. Some penetrate
interface and more away, others mix back again with the bulk of the original
phase.

The solution of equation (2) for this case:

∂C A ∂2 C A
=D AB Gas
∂t ∂ y2 interface
Liquid

I.C. : At t = 0 ; CA = CAo= 0

B.C.(1) : At y = 0 ; CA = Ci
CA=CAo=0
B.C.(2) : At y = ∞ ; CA = CAo = 0 y=0 y=∞
CA=CAi
D AB
This gives the final solution:
N A=
√ πt
(Ci −C A )
For the liquid side

3. Surface Renewal theory (Danckwerts, 1951)

4. The film-penetration theory (Toor & Marchello, 1958)

Gas-Liquid mass transfer

(e.g. gas absorption, stripping and transfer of oxygen from air bubble to liquid broth fermentation)

The mole flux of A through the gas boundary layer is

NA = kg (CAg - CAgi) or NA = kg (PA- PAi) …….(1)
and mole flux of A through the liquid boundary layer is

NA = kl (CAli – CAl) ……..(2)

Now define the over all mass transfer coefficient

¿
NA = KG (PA- P A ) …(3) used when the resistance to
transfer in the gas phase
is larger than in the liquid phase
And
¿
NA = KL ( C Al - CAl) …(4) used when the resistance to transfer in the liquid phase
is larger than in the gas phase
¿
And Henry’s law PAi = H.CAli and P A = H.C
Al
 ¿
From (1) & (3) kg (PA- PAi) = KG (PA- P A ) Or from Eqn 3:
¿
1 P A −P A
=
( P A − HC A )+ P A −P A KG NA →
¿
1 1 ( P A −P A ) 1 l i i
= ⋅ = ⋅
K G k g ( P A − P A ) kg ( P A −P Ai ) ¿
1 P A −P A +P Ai −P Ai
i =
( P A −P A )− HC Al + HC A KG NA
1 i ¿

=
kg
⋅
( PA −PA ) P*A = H.CAl , PAi = H.CAli
i 1 P −H . C Al + H . C Ali −P Ai
( P A −P A )+ H ( C Ali −C Al ) = A
1 i → KG NA
= ⋅{ }
kg ( PA−PA ) P A −P Ai H (C Ali −C Al )
i
+
= NA NA
1 ( C Ali −C Al ) 1 1 H
= ⋅{1+ H } = +
kg ( P A −P A ) → K G k g kl
i
And
¿ ¿

but from eqs 1 & 2 1 C Al −C Al C Al −C Al +C Ali −C Ali

= =
KL NA NA
P A / H−C Al +C Ali −P Ai / H
1 1 kg =
= ⋅{1+ H } NA
KG kg kl P A−P Ai C Ali −C Al
= +
1 1 H H.NA NA
= +
K G k g kl

1 1 1
= +
Similarly
K L H⋅k g k l

kg = gas film mass transfer coefficient (m/s) or (kmol/kN.s)

kl = liquid film mass transfer coefficient (m/s)
KG = over all mass transfer coefficient on gas basis (kmol/kN.s)
KL = over all mass transfer coefficient on liquid basis (m/s)
CAg = concentration of A in the bulk gas (kmol/m3)
CAl = concentration of A in the bulk liquid (kmol/m3)
CAgi = concentration of A at the interface of the gas side (kmol/m3)
CAli = concentration of A at the interface of the liquid side (kmol/m3)
H = Henry’s constant (find from tables)
C¿Al = saturation concentration (maximum possible concentration or called solubility of gas in liquid)
PA = partial pressure of component A (N/m2)
¿
P A = vapor pressure of component A (N/m2)

Note: CAgi and CAli are difficult to measure so Eqns. 3 & 4 are commonly used.

Liquid-Liquid mass transfer (e.g. liq.-liq. Extraction)

The mole flux of A in each liquid phase can be obtained as follows: interface

NA1 = kl1 (CA1 – CA1i) ………(1) NA

CA1
Liquid2
NA2 = kl2 (CA2i – CA2) ………(2) CA1iCA2i
Liquid1
kl1 = liquid phase mass transfer coefficient in liquid1 CA2
kl2 = liquid phase mass transfer coefficient in liquid2

Film of liquid1
Film of liquid2
CAi is the concentration of A at the interface and it is difficult to measure it, so assume steady state transport
and no accumulation of A at the interface. i.e.

NA1 = NA2 = NA

Assume no resistance to mass transfer at the interface and the phases are in equilibrium:
CA C¿A 1 C A 1
i1
m= = = ¿
CA CA C A2
i2 2 ……..(3)
m = equilibrium constant (distribution coefficient or partition coefficient)

From (1) , (2) & (3)

1 1 m
= +
K L1 k l1 k l2
And
1 1 1
= +
K L2 mk l 1 k l2

KL1 = over all liquid phase mass transfer coefficient based on liquid 1 (m/s)
KL2 = over all liquid phase mass transfer coefficient based on liquid 2 (m/s)
And
N A=K L1 ( C A 1 −C ¿A 1 )

N A=K L2 ( C¿A 2−C A 2 )

C¿Al = conc. of A in liq.1 which would be in eqlm. with C in liq. 2

A2

Liquid – Solid mass transfer

(e.g. Catalytic reaction, Leaching, Adsorption of molecules onto surface, Crystallization)

From liquid to solid transfer NA = kl (CAo – CAi)

¿
From solid to liquid transfer NA = KL ( C A – CAo)
[if the surface is non porous the transfer is up to surface] Liq-solid interface

CAo = concentration of A in the bulk liquid (Kmol/m3 ) CAo CAi

CAi = concentration of A at the interface ″ ″

¿
C A = saturation concentration of A
″ ″
Liq
film
Oxygen uptake in the cell culture
 ¿
N¯A
= kl a ( C Al - CAl )

a: interfacial specific surface area (m2/m3).

N¯A
: mass transfer rate per unit volume (kmol/m3s).
CAl: O2 conc. in the broth
¿
C Al : O conc. in the broth in eqlm. with gas phase (kmol/m3)
2
¿
C
( Al - C ): concentration difference driving force for mass transfer
Al
¿
( C Al - CAl) in large scale (e.g. >10 m3 ) is expressed in logarithmic mean conc. difference
¿ ¿
(C −C ) −(C Al −C Al )i
(C Al−C Al ) m= Al ¿ Al o
¿
(C −C Al ) o
ln Al¿
(C Al −C Al )i

Subscript i & o represent the gas inlet and outlet ends of the vessel, respectively.

O2 solubility in aqueous solution ≈ 10 ppm in ambient temp. & press.

For yeast population with ρ = 109 cell/ml, O2 content must be replaced about 12 times/min to keep up with
cellular O2 demand.

The factors affecting cellular O2 demand:

1. Cell species (complex morphology

lead to lower transfer rate)
2. Culture growth phase
3. Nature of carbon source [rate of O2 are
higher when glucose is used than other carbon
containing substrate (lactose or sucrose)]
4. O2 conc. in liq.

Specific O2 uptake rate:

Rate of O2 consumption per cell is qo (g/g.s):

Q o = qo x

Qo: O2 uptake per volume (g/l.s)

x: cell conc. (g/l)

The steps for transfer of O2 from gas bubble to cell in fermenter