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
+

ma!
"
"

Langmuir Eqaution:
1
st
set#up:
] 1
]
ma!
A K
A K
Q Q
L
L
+

2
nd
set#up:
[ ] A
"
K
1
" "
L
ma!

2
nd
set#up is t$e linearised form of langmuir equation: % = b & m ' !
Multi component system with langmuir:
[ ]
[ ]

1 n
n n ( L
i i ( L i ma!(
i
A K 1
A K "
"
t$erefore:
[ ]
[ ] [ ]
b b ( L a a ( L
a a ( L a ma!(
a
A K A K 1
A K "
"
+ +

)olume filling t$eor%:

b "
*
"
)
ma!
ads
ma!
ma! ( ads

+it$
,
*
)
-
1
1
)olume
cr

Adsorption for heterogeneous surfaces:
.otential t$eor% /.olan%i0:
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

'

,
_

n
o
ads
E
V V

e!p
A1$okola
2aitama
1
st
set#up:

'

,
_

n
o
ads
E
V V

e!p
t$erefore:
2 2
1
1
ln ln
,
_

,
_

E
V V
o
ads
2
nd
set#up is t$e linearised form of dubinin equation: % = b & m ' !
Variable What it is Units
Vads Load in volume
V
0
ore volume
Compression !ork
["]
E Adsorption energ# ["]
n $mpirical num%er
T R n V p
x p p
T p

,
_

ref
p
p
T R ln
2

,
_

E
ads
e V V

Q
V
ads

2
2
1
0 ln/ 0 ln/

,
_

E
V V
Linearised
ads
( )
1 3
3 3
1 3
/ 0
Interpolation
f f
f x f x x
x x

ma!
ma!
_
]
1 ]
1
]
]
1
L
L
L
L
Langmuir Isotherm
K A
Q Q
K A
Q
Q Q
K A
A P
slope
K

ma!
ma!
_
e!p
ln ln
.
ln
1
n
n
Ref
n
ads
ads
ads
Dubinin Isotherm
V V
E
V V
E
R T
P
slope
E
Q
V

_

' ;

,


_


,
_


,

T R
V p
n
4

T R
p
V
n
4

Molar Mass
& !aste gas 0'0() kg*mol
& +,( 0'0-. kg*mol
& /(, 0'00) kg*mol
& C,( 0'0.. kg*mol
& ethanol 0'0.- kg*mol
& C/. 0'00- kg*mol
& 1/2 0'003 kg*mol
& C(/- 0'02 kg*mol
AB!"#$%!&
5apour partial total
p 6 !
*
p p %
*

total
5apour
p
p
K
=7 8on ideal case
i
i
inert
l
inert
g
x
y
Y
Y
!
!

+
+

0 1 /
0 1 /
p
p
K
total
5apour

=7 9deal case
"apour i
p #
out i(
gas
inert out i(
liquid
inert in i(
gas
inert in i(
liquid
inert
: 8 ; 8 : 8 ; 8 + +

1 2
2 1
1 2
< p
< p
) )

=ur >mrec$nung des )olumens 5on i484 ?ur aktuellen <emperatur
1atm = 1(3-2@bar = 13-2@3.a = AB3<orr = AB3mm Cg = 1D(BEB lbFinc$
2
{ } [ ]
in in in
out in
K K Y Y
Y Y $
L
+


0 1 /
0 /
min
= Ger minimale Hliquid flo+I
Jalls keine Keladung am JlLssigkeitseintritt K $ L
min


:
out g
gas inert
g
solute
!
!
_

;
in
:
in g
gas inert
g
solute
!
!
_

;
out
l
sol"ent
g
solute
!
!

x
x

1
*
oder umgeke$rt

x
*
1
*
+

y
y
Y

1
*
auc$ $ier gilt
Y
Y
y
*
1
*
+

( ) ( ) K 1 K :
:
;
in
in
out
+

August Equation
T
%
A p ln
& R % #
V

A K
T & R
h
'
T & R
h
p
" "
1 1
ln
int

AB!"#$%!& '!!L%&(
sol"ent tot sol"ent
x ( (

agent mix solute agent solute sol"ent
x ( x ( x ( +

" agent
r ( Q

ent?ogene MNrme = 2assenfluO ' )erdampfungsent$alpie
5on $eat transfer kennen +ir auc$
ln

) A Q

aus der Antoine eq4

,
_

' T
%
A
partial
e p
er$Nlt man durc$ die folgende >mformung die
<emperatur:
T '
A p
%
partial

ln