Week 11

MASS TRANSFER
 MASS TRANSFER
Transfer of material either in the same phase or from phase to phase due
to concentration difference

molecular diffusion mass transfer

Transfer of individual molecules through a fluid by random, individual
movement

convective mass transfer

Transfer of material through a moving fluid or between two relatively
immiscible moving fluids

FKKKSA Bioprocess Eng. Dept

 FICKS LAW FOR MOLECULAR DIFFUSION
Molecules travel in straight lines from high-to-low concentration regions
Ficks law for a binary mixture of A and B:
dx
J*Az cDAB A
dz
c c A2
When c and DAB = constant, J*Az DAB A1
z -z 2 1

p p
For an ideal gas mixture, J*Az DAB A1 A2
RTz 2 - z1
where
J*Az = flux of A (kmol/s.m2)
c = concentration of A and B (kmol/m3)
xA = mole fraction of A in the mixture = cA/c
DAB = molecular diffusivity of molecule A in B (m2/s)
pA = partial pressure of molecule A in the mixture
FKKKSA Bioprocess Eng. Dept
 CONVECTIVE MASS-TRANSFER COEFFICIENT

Rate of convective mass transfer from a solid surface to the fluid flowing outside :

NA = kC(cL1 cLi)

where
NA = convective molar flux of A (kmol A/s.m2)
kC = mass transfer coefficient (m/s)
cL1 = bulk fluid concentration (kmol A/m3)
cLi = concentration in the fluid next to the surface of the solid (kmol A/m 3)
FKKKSA Bioprocess Eng. Dept
 STEADY-STATE MOLECULAR DIFFUSION IN GASES

Equimolar counterdiffusion equal and opposite movement of molecules

For a binary gas mixture of A and B:

* dc A *

dc B
J Az DAB J Bz D BA
dz dz

p A1 p A2
N A DAB
RTz 2 - z1

J*Az = - J*Bz

N A = - NB

DAB = DBA

FKKKSA Bioprocess Eng. Dept

 A DIFFUSING THROUGH STAGNANT NON-DIFFUSING B

In gases :
Evaporation of a pure liquid (A) at the bottom of a narrow tube where a large
amount of nondiffusing air (B) is passed over the top
Pp A1 p A2
N A DAB
RT z 2 - z1 p BM

p A1 p A2
pBM (P p )
ln A2

(P p )
A1

where
NA = convective molar flux of A (kmol A/s.m2)
DAB = molecular diffusivity of molecule A into B (m 2/s)
pA1 = partial pressure of A at point 1
R = gas constant
pBM = partial pressure of log mean of B (pBM P if pA1 P)
FKKKSA Bioprocess Eng. Dept
 DIFFUSION THROUGH A VARYING CROSS-
SECTIONAL AREA

Evaporation of a drop of liquid

Evaporation of a ball of napthalene
Pp A1 p A2
N A1 DAB
RT r1 p BM
If pA1 P) , pBM P
p A1 p A2
pBM
(P p )
ln A2

(P p )
A1

where
NA = convective molar flux of A (kmolA/s.m2)
DAB = molecular diffusivity of molecule A into B (m 2/s)
pA1 = partial pressure of A at point 1
R = gas constant
pBM = partial pressure of log mean of B
FKKKSA Bioprocess Eng. Dept
 DIFFUSION THROUGH A CONDUIT OF NON
UNIFORM CROSS-SECTIONAL AREA

where
r2 - r1
r z z z r1

2 1

FKKKSA Bioprocess Eng. Dept

 Tutorial Diffusion in Gas
6.2-2
6.2-3
6.2-9
Submit 13 May 2015
 PREDICTION OF DIFFUSIVITY FOR GASES
Fuller, Schettler & Giddings:
1
2
1 1
1.00 X10- 7 T1.75
M A M B
DAB
1 1 2
P A
3

B


3

1.75

T2 P1
DAB2 DAB1






T1

P2
where

DAB = molecular diffusivity of molecule A in B (m2/s)

MA = molecular weight of A (kg/kmol)
T = temperature (K)
P= absolute pressure (atm)
A = sum of structural volume increments of molecule A (Table 6.2-2)
FKKKSA Bioprocess Eng. Dept
 STEADY-STATE MOLECULAR DIFFUSION IN
LIQUIDS
Slower than in gases
Equimolar counterdiffusion NA = - N B DAB DBA
(c c A2 ) (x A1 x A2 )
N A DAB A1 z 2 - z1 D c
AB av z 2 - z1


c av 1 2 2
M av M M
1 2
Diffusion of A through stagnant, nondiffusing B:
(x A1 x A2 ) x A1 x A2

N A DABcav x
ln (1 x A2 )
BM
(z 2 - z1 )xBM

(1 x )
A1

For dilute solution, xBM 1& c essentially constant,

(c c A2 )
N A DAB A1 z 2 - z1
where
cA1 = concentration of A at point 1 = pA1/RT
xA1 = mole fraction of A at point 1
FKKKSA Bioprocess Eng. Dept
 PREDICTION OF DIFFUSIVITY FOR LIQUIDS
Flux of solute A in liquid : DAB c A1 c A2
NA z 1 z 2
Wilke-Chang (temp. range: 278 313):
DAB 1.173 X10 - 16
M B
1
2 T
B VA 0.6

T2 B1
DAB2 DAB1


T1 B2

where
DAB = molecular diffusivity of molecule A in B (m2/s)
MB = molecular weight of B (kg/kmol)
T = temperature (K)
= associated parameter of the solvent B (2.6 for water,1.9 for
methanol, 1.5 for ethanol , 1 for others)
VA = solute molar volume at its boiling point (Table 6.3-2)
B = viscosity of solvent B (Pa.s)
FKKKSA Bioprocess Eng. Dept
 PREDICTION OF DIFFUSIVITY OF
ELECTROLYTES IN LIQUIDS
Nerst-Haskell eq. for dilute, single-salt solutions at 25 oC:

1 n 1 n n
n


D AB
O

D 8.928 X10- 10 T
O

n n
AB

1 1



D
D

i
Diffusion coefficient of an individual ion i at 25 C: o Di 2.662 X10 -7
ni
D
O
(at25o C) T
D AB at other temperature:
o AB
334 w
where
DoAB = molecular diffusivity of molecule A in B (cm 2/s)
n+ , n- = the valence of the cation and anion, respectively
+ - = limiting ionic conductances in very dilute solutions (Table 6.3-3)
w= viscosity of water at the new temperature (cp)

FKKKSA Bioprocess Eng. Dept

 PREDICTION OF DIFFUSIVITY FOR
BIOLOGICAL SOLUTES
Small solutes (M 1000 & VA 0.5 ) Wilke-Chang:
1
DAB 1.173 2
X10 M
-16 T
B V 0.6
B A
6.4 D Large solutes (M 1000 & VA
0.5 ) :
D 9.96 x 10-16 T Approximate
(Eq.6.3-8) Stokes-Einstein
AB 1

B VA 3

-15
DAB 9.4 x 10 T 1 (Eq.6.4-1 Polson (spherical molecule)
B M A 3
Better
where
DAB = molecular diffusivity of molecule A in B (m2/s)
MA = molecular weight of A (kg/kmol)
T = temperature (K)
= associated parameter of the solvent B
(2.6 for water,1.9 for methanol, 1.5 for ethanol , 1 for others)
VA = solute molar volume at its boiling point (Table 6.3-2)
B = viscosity of solvent B (Pa.s)
FKKKSA Bioprocess Eng. Dept
 PREDICTION OF DIFFUSIVITY OF SMALL
SOLUTES IN PROTEIN SOLUTION
Flux of solute A in protein solution : Blockage effect
DAP c A1 c A2
NA
For unbinded solute :
z1 z2 Only blockage
DAP DAB (1-1.81 X10- 3cp )
:
For binded solute Blockage+Binding

% free A % bound A
DAP D AB (1 - 1.18 X10- 3 cp )
DP

100 100

where

DAP = diffusivity of A in protein (m2/s)

DAB = diffusivity of A in water
cP = concentration of protein (kg P/m3)
DP = diffusivity of protein alone in solution
FKKKSA Bioprocess Eng. Dept
 Tutorial 6.4-4
Diffusion of Uric Acid in Protein Solution and Binding
Uric acid (A) at 37 C is diffusing in an aqueous solution of
proteins (P) containing 8.2g protein/100mL solution. Uric acid
binds to the proteins and over the range of concentrations
present, 1.0g mol of acid binds to the proteins for every 3.0g mol
of total acid present in the solution. The diffusivity DAB of uric acid
in water is 1.21x10-5 cm2/s and Dp=0.091x10-5 cm2/s.
Assuming no binding, predict the ratio due only to DAP/ DAB
blockage effects (cp=82 kg/m3; ratio=0.85)
Assuming blockage plus binding effects, predict the ratio D AP/
DAB. Compare this value with the experimental value of 0.616.
(% Free=66.67%; %Bound=33.33%; ratio=
 MOLECULAR DIFFUSION IN BIOLOGICAL GELS

Flux of A = Flux of A through stagnant, nondiffusing B

(x A1 x A2 )
N A DABcav
(z 2 - z1 )xBM
x A1 x A2
xBM (1 x )
ln A2

(1 x A1 )

For dilute solution, xBM 1 & c essentially constant,

(c A1 c A2 )
N A DAB z 2 - z1
where

cA1 = concentration of A at point 1 = pA1/RT

xA1 = mole fraction of A at point 1

FKKKSA Bioprocess Eng. Dept

 Example 6.4-2 Diffusion of Urea in Agar
A tube or bridge of a gel solution of 1.05 wt % agar in water at 278K is
0.04 m long and connects two agitated solutions of urea in water. The
urea concentration in the first solution is 0.2g mol urea per liter solution
and is 0 in the other. Calculate the flux of urea in kg mol/s.m2 at steady
state.
Solution: First calculate xA1 agar

0.2 g mol urea in 1 L

1 L = 1000 ml = 1000 cm3 =1000 g
g mol water= 1000g/18 =55.5 mol xA1=0.003 xA2= 0

0.2mol
x A1 0.003
0.2mol 55.5mol
(c A1 c A2 ) (x A1 x A2 )
xA1 <<, so xBM 1.0, so: N A DAB z - z DABcav
2 1 (z - z )x
2 1 BM
 Tutorial: Diffusion in Liquid & Gel
6.4-2 Gel
6.4-4Protein
6.5-1Solid
6.5-5 Solid
Submission 25 May 2015
 MOLECULAR DIFFUSION IN SOLIDS

1. Diffusion follows Ficks law & independent of actual structure of solid

2. Diffusion in porous solids where actual structure and void channels are
important
Diffusion through a solid slab:
DAB (c A1 c A2 ) (c A1 c A2 )
Ficks law : NA
(z1 z 2 ) R diff.
(z1 z 2 )
R diff.
DAB
S(p A1 p A2 ) (p A1 p A2 )
N A DAB PM
22.414 (z 2 - z1 ) 22.414(z 2 - z1 )
where
cA1 = concentration of A at point 1 = pA1/RT
S = solubility of solute A in solid (m3 A (STP)/m3 solid.pA)
pM = permeability (m3 A (STP)/s.m2.atm/m) = DABS
FKKKSA Bioprocess Eng. Dept
 MOLECULAR DIFFUSION IN SOLIDS

Diffusion through a several slabs in series:

Ficks law :

(c A1 c A4 )
NA
R diff.

L1 L L
L1 L2 L3 R diff. 2 3
DAB1 DAB2 DAB3
(p A1 p A4 ) 1
NA
22.414 L1 L2 L3

PM1 PM2 PM3
where
L1 = width of solid 1
pM1 = permeability of solid 1
FKKKSA Bioprocess Eng. Dept
 MOLECULAR DIFFUSION IN SOLIDS

Diffusion through a cylinder:

Ficks law :

(c A1 c A2 )
NA
R diff.

cA r
cA ln r2
R diff. 1
2DABL
NA

where
r1 = inner radius
r2 = outer radius
L = length of cylinder

FKKKSA Bioprocess Eng. Dept

 MOLECULAR DIFFUSION IN POROUS SOLIDS

Pores or interconnected voids in the solid affect diffusion

Diffusion does not occur in the inert solid

Diffusion of liquids
For dilute solution : DAB (c A1 c A2 )
NA
(z1 z 2 )
Diffusion of gases
For large pores (Fickian-type diffusion) :

DAB (c A1 c A2 ) DAB (p A1 p A2 )
NA
(z1 z 2 ) RT(z 1 z 2 )
where
= open void fraction
= tortousity = correction factor for path longer than (z2 z1)
FKKKSA Bioprocess Eng. Dept
 MOLECULAR DIFFUSION IN SMALL PORES
Knudsen diffusion (molecule-wall collisions)
( > Dpore & NKn 10 ) D P(x A1 x A2 ) DKA (p A1 p A2 )
N A KA
RT(z 1 z 2 ) RT(z 1 z 2 )

Transition diffusion ( mixture of molecule-wall & molecule-molecule collisions)

( 0.01 NKn 10 )
D AB
1 x A2


DAB P D
No reaction : NA ln KA
RT(z 1 z 2 ) D AB
1 x
A1
D
where KA

= mean free path = average distance travelled by 2 molecules before collision

3.2 RT

NKn = Knudsen number = 1/2 P 2 M
2r
T
DKA = Knudsen diffusivity = 97 r

MA = flux ratio factor = 1 + NB/NA
FKKKSA Bioprocess Eng. Dept
 MOLECULAR DIFFUSION IN SMALL PORES

Transition diffusion ( mixture of molecule-wall & molecule-molecule collisions)

( 0.01 NKn 10 )
reaction (A B) at surface of catalyse at the end of pore :
D P(x A1 x A2 ) DNA (p A1 p A2 )
N A NA
RT(z 1 z 2 ) RT(z 1 z 2 )
or
DNA
P(x A1 x A2 ) DNA
(p A1 p A2 )
NA
RT(z 1 z 2 ) RT(z 1 z 2 )
where
DNA, DNA = simplified effective diffusivity

N NA 1 N NA
1
1 1 - x av
1 1
D AB DKA D AB DKA

FKKKSA Bioprocess Eng. Dept

 MOLECULAR DIFFUSION IN SMALL PORES

Molecular diffusion (molecule-molecule collision)

( Dpore & NKn 0.01 )

DAB P 1 x A2
NA ln
RT(z 1 z 2 ) 1 x
A1

where
= flux ratio factor = 1 + NB/NA
NA MA
Open system:
NB MB

Closed system: NA = - NB

FKKKSA Bioprocess Eng. Dept