Adsorpuon

Adsorpuon
hyslsorpuon
lorces beLween Lhe adsorbenL and adsorbaLe are of a
physlcal naLure and Lhe adsorpuon ls relauvely weak.
lorces lnvolved are van der Waals forces
PeaL evolved when a mole of gas becomes physlsorbed ls
small, less Lhan 20 k!
Chemlsorpuon
Adsorbed molecules are held Lo Lhe surface by covalenL
forces.
PeaL evolved ln Lhls Lype of adsorpuon ls comparable
compared Lo LhaL evolved ln chemlcal bondlng, 100-300 k!
Chemlsorpuon
Surface ls covered by a slngle layer of adsorbed molecules.
unlmolecular layer
Chemlsorpuon ceases when a unlmolecular layer ls formed,
addluonal layers can form Lhrough physlsorpuon.
Chemlsorpuon oen umes need Lo sausfy an appreclable
acuvauon energy, so lL ls someumes called as AC1lvA1Lu
AuSC81lCn.
lnlual physlsorpuon happens before chemlsorpuon.
Solld surfaces are noL compleLely smooLh, Lherefore some
molecules would be adsorbed more sLrongly aL some slLes
compared Lo oLhers.

Adsorpuon lsoLherms
Lquauons LhaL relaLe Lhe amounL of a
subsLance auached Lo a surface Lo lLs
concenLrauon ln soluuon aL consLanL 1.
Langmulr lsoLherm
lreundllch lsoLherm
8L1 lsoLherm
Langmulr lsoLherm
All parLs of Lhe surface behave exacLly Lhe same way as
far as adsorpuon ls concerned.
AL equlllbrlum, leL
0 = fracuon of Lhe surface covered by adsorbed
molecules.
1-0 = fracuon of Lhe surface LhaL ls noL covered
1he raLe of adsorpuon ls dlrecLly proporuonal Lo
- ConcenLrauon [A] of Lhe molecules ln Lhe llquld or gas
phase.
-lracuon of surface LhaL remalns unoccupled.
8aLe of Adsorpuon:
!
"
a
= k
a
[A] 1#$
( )
1he raLe of desorpuon ls dlrecLly proporuonal
Lo Lhe number of molecules auached Lo Lhe
surface, whlch ls dlrecLly proporuonal Lo Lhe
fracuon of surface covered.
AL equlllbrlum, Lhe raLe of adsorpuon ls equal
Lo Lhe raLe of desorpuon.
!
"
d
= k
d
#
!
k
d
" = k
a
[A] 1#"
( )
1he rauo ka/kd ls an equlllbrlum consLanL, k
Solve for 0
!
"
1#"
=
k
a
k
d
[A]
!
"
1#"
= K[A]
!
" =
K[A]
1+ K[A]
loL 0 vs. [A]
AL sumclenLly low concenLrauons, we can neglecL
k[A] ln Lhe denomlnaLor.
AL very hlgh concenLrauons

1ake Lhe reclprocal of

!
1"# $
1
K[A]
!
" = K[A]
!
" =
K[A]
1+ K[A]
!
1
"
=1+
1
K[A]
Lxample
8enzene adsorbed on graphlLe ls found Lo
obey Lhe Langmulr lsoLherm Lo a good
approxlmauon. AL a pressure of 1.00 1orr Lhe
volume of benzene adsorbed on a sample of
graphlLe was found Lo be 4.2 mm
3
aL S1, aL
3.00 1orr lL was 8.3 mm
3
. Assume a benzene
molecule Lo occupy 30
2
and esumaLe Lhe
surface area of graphlLe.
Adsorpuon wlLh ulssoclauon
ln cerLaln cases Lhere ls evldence LhaL Lhe
process of adsorpuon ls accompanled by Lhe
dlssoclauon of Lhe molecule before lL
becomes auached Lo Lhe surface.
8eacuon ls beLween a gas molecule and Lwo
ad[acenL surface slLes.
8aLe of Adsorpuon:
8aLe of uesorpuon:
!
"
a
= k
a
[A] 1#$
( )
2
!
"
d
= k
d
#
2
AL equlllbrlum Lhe Lwo raLes are equal
Solvlng for 0 glves
1aklng Lhe reclprocal of boLh sldes

!
"
1#"
=
k
a
k
d
[A]
$
%
&
'
(
)
1
2
!
"
1#"
= K[A]
( )
1
2
!
" =
K
1/ 2
[A]
1/ 2
1+ K
1/ 2
[A]
1/ 2
!
1
"
=1+
1
1+ K
1/ 2
[A]
1/ 2
Compeuuve Adsorpuon
0
A
= fracuon of Lhe surface covered by
molecules of Lype A
0
8
= fracuon of Lhe surface covered by
molecules of Lype
lracuon of unoccupled slLes= 1 - 0
A
-0
8

lf boLh subsLances are adsorbed wlLhouL
dlssoclauon, Lhe raLes of adsorpuon are:
!
"
a
A
= k
a
A
[A] 1#$
A
#$
B
( )
"
a
B
= k
a
B
[B] 1#$
A
#$
B
( )
1he raLes of desorpuon are
lor A aL equlllbrlum Lhe raLes of adsorpuon
and desorpuon are equal
lor 8,
!
"
d
A
= k
d
A
#
A
"
d
B
= k
d
B
#
B
!
"
A
1#"
A
#"
B
= K
A
[A]
!
"
B
1#"
A
#"
B
= K
B
[B]
Solvlng Lhe Lwo equauons slmulLaneously,
!
"
A
=
K
A
[A]
1+ K
A
[A] + K
B
[B]
"
B
=
K
B
[B]
1+ K
A
[A] + K
B
[B]
lreundllch lsoLherm
nonldeal sysLems can someumes be ued Lo an
emplrlcal lsoLherm LhaL relaLes Lhe amounL of
subsLance adsorbed, x, Lo Lhe concenLrauon, c, vla Lhe
equauon:
Where k and n are emplrlcal consLanLs, and n ls usually
less Lhan 1.
AmounL adsorbed x, keeps lncreaslng as c lncreases.
l.e. no saLurauon of Lhe surface.
Surface heLerogenelLy and repulslve forces beLween
adsorbed molecules.
!
x = kc
n
8L1 lsoLherm
8runauer, Lmmeu, and 1eller
LxLenslon of Lhe Langmulr equauon Lo allow for
Lhe physlsorpuon of addluonal layers of adsorbed
molecules.
v ls Lhe volume of Lhe gas adsorbed aL pressure
, and v
0
Lhe volume LhaL can be adsorbed as a
monolayer,
0
ls Lhe saLurauon vapor pressure
!
PP
0
V P
0
" P
( )
=
1
V
0
K
+
P
V
0
Chemlcal 8eacuons on Surfaces
unlmolecular 8eacuons
SlmplesL Case: 8aLe ls proporuonal Lo 0


Someumes a subsLance oLher Lhan Lhe reacLanL ls
adsorbed on Lhe surface, LhaL leads Lo Lhe
reducuon of Lhe reacuon raLe. Suppose Lhe
surface also blnds nonreacung subsLance l
(lnhlblLor/polson)
!
v = k" =
kK[A]
1+ K[A]
!
" =
K[A]
1+ K[A] + K
i
[I]
!
v = k" =
kK[A]
1+ K[A] + K
i
[I]
8lmolecular 8eacuons
Langmulr-Plnshelwood Mechanlsm
1wo reacLanL molecules A and 8 are adsorbed on
nelghborlng slLes.
lormauon of an AcuvaLed Complex
lormauon of Lhe roducLs
1he raLe ls dlrecLly proporuonal Lo Lhe probablllLy LhaL
A and 8 are adsorbed on nelghborlng slLes
!
v = k"
A
"
B
=
kK
A
K
B
[A][B]
1+ K
A
[A] + K
B
[B]
( )
2
8lmolecular 8eacuons
Langmulr-8ldeal Mechanlsm
8eacuon occurs beLween a molecule LhaL ls noL
adsorbed (e.g., A) and an adsorbed molecule (e.g., 8)
Adsorpuon of A may occur buL Lhe adsorbed A does noL
reacL.
1he raLe ls proporuonal Lo Lhe concenLrauon of A and
Lo Lhe fracuon of surface covered by 8
!
" = k[A]#
B
=
kK
B
[A][B]
1+ K
A
[A] + K
B
[B]
roblem SeL: uue nexL meeung