Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

See also
Krishna & Wesselingh
Chem. Eng. Sci.
52(6) 1997 861-911
Preliminary version – 13.12.2017

Mass transfer in
multi-component mixtures

Ron Zevenhoven
Åbo Akademi University
Thermal and Flow Engineering Laboratory
tel. 3223 ; ron.zevenhoven@abo.fi

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 1/60

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

1 ”Old-school” mass transfer

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 2/60

 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Mass Transfer as you have learned it

Ji : flux of species i with respect to the mixture

dci ci
Ji  D Fick’s
dz ci  ci  ci
law ci
ci Di
Ji  Di  ki ci ki 
z z
 
diffusivity mass transfer z
coefficient
phases α, β

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Diffusion with Drift

Ni : flux with respect to an interface

flux of mixture
differential equation Ni  Di dci  Nxi N   Ni
dz i

difference equation Ni  ki ci  Nx i  ki si ci

 
diffusion drift Stefan or drift
flux flux correction
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Classic - in gases dc1

J1   D1
gas: c1  c2  c  constant dz
dc
fluxes with respect to mixture J 2   D2 2
dz
+
d c1  c 2 
J1  J 2  0   D
only one binary D, dz
which is independent
of composition D

0 1 x1

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Three gases (1)

ideal gases, 100 kPa, 298 K

A N2, H2 N2, CO2 B

beginning: x N2  0.46 x N2  0.52

x H2  0.54 x CO2  0.48

Question: Does N2 transfer

(a) from A to B? (b) from B to A?
(c) not at all? (d) or does it do (a), (b) and (c)?
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

0.6
N2
A Three gases (2)
0.5
mole fraction xi

B
0.4 reverse
0.6 diffusion
H2
0.4
A B
0.2 B A
CO2 time
0.0
h
0 10 20

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Two cations cation

permeable
membrane

high low
concentration H+ Na+ concentration

Cl- Cl-

1 H+ moves rapidly H+ 2 excess +charge

so Na+ can move and electrical field
against its
concentration gradient! Na+ 3
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Two gases in a porous plug (1)

He
298 K
100 kPa
Ar
298 K
100 kPa
NHe  3 NAr
!
MAr
MHe

friction (He / plug) < friction (Ar / plug)

the plug, matrix or

membrane is a
(pseudo)component

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Two gases in a porous plug (2)

He Ar
298 K 298 K NHe  NAr
100 kPa 101 kPa (for example)

p
main reason:
viscous flow
retards He,
accelerates Ar
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

2 Driving forces

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 11/60

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Gravity - a simple potential

the potential difference is the work required
to change the condition of the weight
1m
Δz here:   mg z  9.81 J ( 9.81 Nm)

1kg or, per mole  i  Mi g z

the driving force is the negative

potential gradient: d
1kg Fi   i  Mi g
dz
Fi the force is downwards
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Chemical potential
xi  i
chemical potential
mixture
i  const p,T   RT lnai
ai   i xi
work required:
change in the activity activity coefficient
chemical
potential
i  const  p,T 
pure i i  i  i  RT lnai
(one mole)

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

 in an ideal solution
chemical potential
 i  const ( p,T )  RT ln x i
in an ideal solution

p 
in an ideal gas  i  const ( p,T )  RT ln i 
p
partial
pressure

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 14/60

 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Momentum balance
forces  F

momentum ‘in’ momentum ‘out’

 (m v ) in  (m v ) out

change of d ( mv )
  (m
 v )in   ( m
 v )out   F
momentum dt

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 15/60

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Moving through each other

z z  dz
H2 CO2
(1) (2)

species
u2 u1
velocities

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 16/60

 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Forces on hydrogen (1)

z z  dz
 driving dp  friction
  1    p1p2 (u2  u1)
 force  dz  force 
p1A z p1A zdz

area volume
A Adz
dp
Force balance :   pp  (u  u  ) force per volume Note:
dz often x2 ≈ 1
p RT dp and u2 = 0
with c1  1 gives   RTp  (u  u  ) force per mole
RT p dz
Gases:
Driving force F1  RTp  (u  u  )  ζ,  x  (u  u  ) u ~ 10-2 m/s
RT RT Liquids:
with friction coefficient ζ,     ζ , u ~10-4 m/s
D,  D ,
december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 17/60

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Driving force (per mole of i)

di d lnai RT dai RT dxi

Fi    RT  
dz dz ai dz xi dz
for a given T and p in ideal solutions
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Maxwell-Stefan equation
driving force Fi  i, j x j ui  u j 
on i j i

friction coefficient mole fraction (diffusive)

between i and j of j species velocities

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Film theory, thickness of films

two thin, one dimensional ‘films’ next to gases
the phase boundary z  104 m

liquids
5
z  10 m

in a solid particle
z
eddies & ‘film’:
phase d
large scale boundary
no eddies z  107104 m d
convection z 
10
membrane
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Difference form of force

i  lnai RT ai RT xi

Fi    RT  
z z ai z xi z
for a given T and p in ideal
solutions

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 21/60

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Approximation
1 a 
exact ln 1 
+1
RT  a1 
approximate
0 a1 a1  a1

0 2 a1 a1 0.5a1  a1 
a1
-1
‘approximate’ works out better
-2 in difference equations

 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Forces in a
glass of beer z  105 m
growing
bubble
of CO2
x1  0.003
x1  0.001
mole fraction
of CO2
Note:
u2 = 0 RT dx 1 RT  x 1
F1   
x 1 dz x1 z

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Example (3.1 from book)

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 24/60

 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Example (3.1 from book): answer

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 25/60

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

3 Friction

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 26/60

 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Friction coefficients of spheres

coefficient of a single sphere
1,2 = A  32d1  3  1012 Nmol1 ms1
1

A  6  1023
spheres ‘1’
molecules mol-1
liquid ‘2’

F1

using:
Stokes Law

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Diffusion and friction coefficients

RT RT
Ð12,  1,2 
1,2 Ð1,2
each others ‘inverse’
we use both

RT 8.314 300 9 m
2
Ð1,2    10
A32d1 6 1023 10 103  0.4 109  s
Maxwell-Stefan diffusivity of large
molecules in dilute liquids (not gases)
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

One equation missing

2 components: 1 relative velocity
1 independent equation
3 components: 2 relative velocities
2 independent equations
n components: n - 1 relative velocities
n - 1 independent equations

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Bootstrap (1)
only
relative
velocities

bootstrap Fi    i , j x j (u i  u j )
j i

‘floating’ transport
relations: have to be
‘tied’ to surroundings
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Bootstraps (2)
N2 N2 Ar
H2 CO2 He

no net volume flow plug does not move

H+ Na+ membrane does not move

Cl- Cl- (almost) no charge
transfer

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 31/60

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Fluxes
in practical problems we use fluxes:

Ni  ui ci  ui cxi

flux form of MS-equation:

Fi cxi  i , j cxi x j (ui  u j )
j
Fi / V ; xi = ci / c
fi  i , j ( x j Ni  xi N j )
j

force on i per unit volume of mixture

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 32/60
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

From differential to difference

x1 RT da1 RT
a1 u1
binary:   x2 u1  u 2 
a1 dz Ð1,2
x1 infinitesimal da
 1  x2 1
u  u 2 
x1
layer a1 Ð1,2 dz 
a1
  finite layer a u  u 2 
 1  x2 1 k1,2 
Ð1,2
positive (approximate) a1 k1,2 z
direction

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Average velocity
film

ci
average concentration ci
0
 
ui species velocity
(depends on position in film)

ui species velocity at the

0 average composition

positive velocity
december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 34/60
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Differences with fluxes

a1 1 c x1
  x2 (u1  u2 ) 
a1 k1,2 c

a1 1
 x1  ( x2N1  x1N2 )
a1 k1,2c

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 35/60

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Multicomponent equations

using velocities using fluxes

 ai (u  u j ) ai (x N  x N )
   xj i  xi  j i i j
ai j i ki, j ai j i ki , j c

for ideal  xi

solutions

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 36/60

 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Transfer 100

coefficients gases
 101 m s1
10-2
Ði , j ki , j in pores
ki , j 
z m s1
10-4 liquids
 104 m s1

in pores
10-6

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Temperature effects
MS-equation
Fi  ζj
i, j x j (ui  u j )  (thermal diffusion terms)
small
driving
force
 d  RT dxi
Fi   i   
 dz T xi dz
difference at constant
form: temperature changes are not
RT xi very important
Fi  
xi z average film
temperature
december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 38/60
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

4 Binary examples

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 39/60

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

drops on a tray Stripping

gas: trace of NH3 (1)
- dilute
bulk of N2 (2)
transport x 2N1  x1N 2
  x1 
relation k1,2c

x2  1 N2  0
bootstrap
x1
flux N1  k1,2c x1
x1
0
  ..as you already knew..
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Stripping - concentrated

x1
x1  0.5
k1,2c
x1 N1   x1  2 k1,2c x1
x2

0
 

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Vaporising droplet
heat

benzene (1), volatile

toluene (2)

y1  K1x1
x1 vapour removed
x1 by convection
x2 y  K x N1 y1
x2
2 2 2
bootstrap:  
N2 y 2
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Fluxes from vaporising droplet

x2N1  x1N2 x1N2  x2N1
 x1   x2 
k1,2c k1,2c

N1 k1,2c k1,2c
 N1   x1 N2   x2
N2 x2  x1  x1  x2 

example   2 x1  x2  0.5

N1  4 k1,2c x1 N2    2 k1,2c x2

Δx1 < 0
Δx2 > 0 Stefan (drift) corrections

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Carbon gasification
O2  2 C  2 CO both components are moving
and have a high concentration
k1,2  102 ms1 c  10 mol m3
C
bootstrap:
1.0 N2  2 N1
O2 (1)
0.6
0.4
CO(2)
0.0 calculate N1 and N2
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Fluxes in gasification
N2  2 N1
x 2 N1  x 1N 2  x 2  2 x 1 N1
 x 1  
k1,2c k1,2c
k1,2c 10  2  10
N1   x 1     0.6 
x 2  2 x1 0.7  2  0.3

N 1  0.046 exact : 0.047  mol m  2 s  1

N 2   0 .092 exact : 0 .094  mol m  2 s 1

almost the same

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Binary distillation
transport relation
x1 heptane (2) x N x N
x2  x1  2 1 1 2
k12,c
x1
N1  N2
x2 hexane (1) bootstrap
(equimolar exchange)
N1
 x1 
 x1  x2 N1
N2 k1,2c
0
  N1  k1,2c x1 N2  k1,2c x2
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Some bootstraps
1 membrane stagnant uM  0
2 bulk stagnant (absorption) N2  0
3 trace stagnant (polarisation) u1  0
4 equimolar exchange (distillation) N1  N2  0
5 interface determined (vaporisation) N1 y1

N2 y 2
6 reaction stoichiometry N1 N2

1 2

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

5 Ternary examples

december 2017 Åbo Akademi - Biskopsgatan 8, 20500 Åbo TRP RZ 48/60

 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Ternary - per mole of i

d1 forces
  1,2 x2 u1  u2   1,3 x3 u1  u3 
dz per mole of ‘1’
d
 2  2,1x1u2  u1  2,3 x3 u2  u3  forces
dz per mole of ‘2’

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Ternary - per mole of mixture

d1 
 x1  1,2 x1x2 u1  u2   1,3 x1x3 u1  u3  
dz forces per

d2 mole of
 x2  2,1x1x2 u2  u1  2,3 x2 x3 u2  u3 
dz  mixture

these should 2,1  1,2 Ð2,1  Ð1,2 k2,1  k1,2

cancel:
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

More momponents

binary
x2N1  x1N2 x3N1  x1N3
 x1  
k1,2c k1,3c
x1N2  x2N1 x3N2  x2N3
 x2  
k2,1c k2,3c
ternary

quaternary

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Condensor cooling water vapour

Mix: NH3+H2O + H2

liquid
NH3 (1) and H2O (2)
condense on a tube
0.6
H2 (3) does not condense H2O
k1,2  1 103 ms1 0.4
k1,3  k2,3  3  103 ms1 NH3
0.2
find the velocities H2
in the gas film 0.0
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Condenser (2)
transport (MS) relations:
0 . 4N1  0 . 3 N 2 0 . 3N1  0 . 4 N 3
NH3 :  0.2  
(1 10  3 )30 (3  10  3 )30
0 .4N 2  0 .3N1 0 .3N 2  0 .3N 3
H2O : 0 .4  
(1 10  3 )30 (3  10  3 )30
bootstrap N3  0
three linear equations, three unknowns
2 1
N1  0.015 N2  0.045 mol m s
exact solutions: N1  0.013 N2  0.049 mol m2 s1

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Condenser (3)
mixture velocity
H2O moves down its gradient H2 O

NH3 dragged against its gradient NH3

H2 does not move at all H2
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Ternary distillation (1)

1 ethanol 3 water vapour liquid
2 a trace of butanol

large friction between 1 and 2 0.63

1
k1,2  8  102 ms1 0.53
0.45
k1,3  k2,3  20  102 m s-1 3
0.35
bootstrap: equimolar exchange
u1y1  u2 y 2  u3 y 3  0
0.02 2 0.02
in which direction does 2 move?

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Butanol - which direction?

y 2 y 2
2
0.022 u2  3.75  10
0.018
0.020 .  102
0.020 u2  158
0.0214
0.022 0.0186 no motion
0.018 u2  0.81 102
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Ammonia reaction
N2  3 H2  2NH3 transport relations:

H2 (2) x2N1  x1N2 x3N1  x1N3

 x1  
k1,2c k1,3c
N2 (1)
x1N2  x2N1 x3N2  x2N3
 x2  
NH3(3) k1,2c k2,3c
x1N3  x3N1 x2N3  x3N2
 x3  
  k1,3c k2,3c

catalytic N1 N2 N3
bootstrap:  
surface 1 3 2

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

When is: 3 = 2?
a ternary can be approximated as a binary when
x1 u u u u u1  ueff
  x2 1 2  x3 1 3  xeff
x1 k12, k1,3 k1,eff
 Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

1 one friction term dominates:

x2 x u u xeff  x3
 3  x3 1 3
k12, k13, k13, k1,eff  k13,
(example: mobile species in many membranes)
2 equal velocity of two species:
x x  xeff  x2 x3 
u2  u3   2  3  u1  u2    
 k12, k1,3  k1,eff  k1,2 k1,3 
(example: Na+ and Cl- in water)
3 equal diffusivities (‘1’ in m- and p-xylene) xeff  x2  x3
 x  x u   x2u2  x3u3  x2u2  x3u3
k1,2  k1,3  2 3 1 ueff 
k1,2 x 2  x3

Transport processes 424522

Multi-component mass transfer

using transparancies that accompany ”Mass Transfer in Multicomponent mixtures”
by J.A. Wesselingh & R. Krishna, Delft University Press (2000)

Effective binary in a reactive system

simplifying transport equation of N2 in ammonia formation:
eliminate N2 and N3 with N2  3 N1 N3  2 N1
1 x  3x1 x3  2x1
N1  k1,eff c x1 with  2 
k1,eff k1,2 k1,3

similarly for H2 and NH3

If all fluxes Ni are related via the same reaction stoichiometry

→ pseudo - binary