Adsorption

Dynamic equilibrium (langmuir theory) for homogenous surfaces:

Rate of adsorption:
[ ] ( ) 1 A k r
ads ads
2
nd
order reaction
Rate of desorption:

des des
k r
1
st
order reaction
Equilibrium if rate desorption = rate adsorption
[ ] ( ) 1 A k k
ads des
des
ads
L
k
k
t tan cons _ langmuir K
] A [ K 1
] A [ K
L
L
+

max
Q
Q

Langmuir Eqaution:
1
st
set-up:
] A [ K 1
] A [ K
Q Q
L
L
max
+

2
nd
set-up:
[ ] A
Q
K
1
Q Q
L
max

2
nd
set-up is the linearised form of langmuir equation: y = b + m * x
Multi component system with langmuir:
[ ]
[ ]

1 n
n n , L
i i , L i max,
i
A K 1
A K Q
Q
therefore:
[ ]
[ ] [ ]
b b , L a a , L
a a , L a max,
a
A K A K 1
A K Q
Q
+ +

Volume filling theory:

b Q
~
Q
V
max
ads
max
max , ads

with

~
V
3
1
1
Volume
cr

Adsorption for heterogeneous surfaces:
Potential theory (Polanyi):

'

,
_

n
o
ads
E
V V

exp
Variable What it is
r Rate of sorption
k Rate constant
[A] Concentration in opposing phase
Degree of covered places
KL Langmuir constant
Q Load on surface
Variable What it is Units
Vads Load in volume
V
0
Pore volume
Compression work
[J]
E Adsorption energy [J]
n Empirical number
1
st
set-up:

'

,
_

n
o
ads
E
V V

exp
therefore:
2 2
1
1
ln ln
,
_

,
_

E
V V
o
ads
2
nd
set-up is the linearised form of dubinin equation: y = b + m * x
ABSORPTION
vapour partial total
p x
~
p p y
~

total
vapour
p
p
K
=> Non ideal case
i
i
inert
l
inert
g
x
y
Y X
X Y
N
N

+
+

) 1 (
) 1 (
p
p
K
total
vapour

=> Ideal case

vapour i
p H
out i,
gas
inert out i,
liquid
inert in i,
gas
inert in i,
liquid
inert
Y N X N Y N X N + +

1 2
2 1
1 2
T p
T p
V V

Zur Umrechnung des Volumens von i.N. zur aktuellen Temperatur
1atm = 1,0325bar = 103250Pa = 760Torr = 760mm Hg = 14,696 lb/inch
2
{ } [ ]
in in in
out in
X K K Y Y
Y Y G
L
+


) 1 (
) (
min
= Der minimale liquid flow
Falls keine Beladung am Flssigkeitseintritt K G L
min


Y
out g
gas inert
g
solute
N
N
_

X
in
Y
in g
gas inert
g
solute
N
N
_

X
out
l
solvent
g
solute
N
N

x
x
X

1
~
oder umgekehrt
X
X
x
~
1
~
+

y
y
Y

1
~
auch hier gilt
Y
Y
y
~
1
~
+

( ) ( ) K 1 K Y
Y
X
in
in
out
+

August Equation
T
B
A p ln
Z R B H
V

A B
T Z R
h
C
T Z R
h
p
v v
1 1
ln
int

ABSORPTION COOLING
solvent tot solvent
x M M

agent mix solute agent solute solvent
x M x M x M +

v agent
r M Q

entzogene Wrme = Massenflu * Verdampfungsenthalpie
von heat transfer kennen wir auch
ln

k A Q

aus der Antoine eq.

,
_

C T
B
A
partial
e p
erhlt man durch die folgende Umformung die
Temperatur:
T C
A p
B
partial

ln