Environmental Engineering Reference
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the Langmuir-Hinshelwood (L-H) model as described by Zhou and
Ray [40].
dC
dt
V
V
kKC
KC
(4.1)
r
b
L
r
s
rxn
1
R
s
where V L is the total volume of liquid treated (m 3 ), V R is the volume
of the reactor (m 3 ), (dC b /dt) is the observed rate (mol.m -3 .s -1 ), k r is the
reaction rate constant (mol.m -3 .s -1 ), K is the adsorption-desorption
equilibrium constant (m 3 .mol -1 ), C s is the concentration of the reactant
on the catalyst surface (mol.m -3 ) in equilibrium with the actual surface
concentration [40].
A Langmuir-type kinetic equation is more appropriate for photocata-
lyst slurry system; in case of immobilized system it is difficult to predict
the kinetics without knowing the pollutant concentration on photocatalyst
surface. Zhou and Ray [40] considered both external and internal mass-
transfer resistance for photocatalytic degradation of Eosin B on immobi-
lized TiO 2 surface to find out the true kinetic parameters. They found out
the intrinsic kinetic parameters from the following equation:
11
1
1
(4.2)
k
k
k
k
k
k
o
r
mint
,
mext
,
where k r is the first-order reaction rate constant (s -1 ), k m,ext is external
mass-transfer coefficient, and k is the specific surface area (m -1 ).
4.6.3
Effect of Solution pH
The pH of the solution significantly affects a photocatalytic process as it
occurs on the surface of the photocatalyst. Various surface properties of
photocatalyst such as: i) surface charge, and ii) band edge position, are
influenced by pH. Degussa P25 TiO 2 shows point of zero charge (pHzpc) at
pH 6.8, and thus in alkaline medium, the TiO 2 surface becomes negatively
charged. Therefore in alkaline pH, cationic dye (e.g., methylene blue) is
well adsorbed [40,41,42].
IV
IV
Ti
OH
HO
Ti
O
H O
2
IV
IV
Ti
OH
H
Ti
OH
2
Zhou and Ray [40] performed a kinetic study for photocatalytic degra-
dation of an anionic dye (Eosin B) with TiO 2 . The adsorption of Eosin B
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