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8
Fe(OH)
2
+
/Fe(OH)
2
6
Cu
2+
/Cu
+
4
CuCl
+
/CuCl
2
Fe(OH)
2+
/Fe(OH)
+
0
VO
2
+
/VO(OH)
+
-2
-4
Fe
3+
/Fe
2+
-6
-
20
-
15
-
10
-
5
0
log KAB
FIGURE 5.17
Marcus free energy relationships for the oxidation of several ions of envi-
ronmental interest. (From Wehrli, B. 1990. In: W. Stumm (Ed.),
Aquatic Chemical Kinetics
,
pp. 311-336. NewYork, NY: John Wiley & Sons, Inc.)
TABLE 5.7
A Summary of LFERs in Environmental Engineering
Type
Application
Special Feature
Kinetic Rate Constants
Brönsted
Acid and base catalysis, hydrolysis,
association, and dissociation
reactions
log
k
a
or
k
b
related to log
K
a
or
K
b
Hammet
σ
p
- and
m
-substituted aromatic
hydrolysis, enzyme catalysis
Substituent effects on organic reactions
Taft
σ
∗
Hydrolysis and other reactions for
aliphatic compounds
Steric effects on substituents
Marcus
Electron transfer (OS), metal ion
auto-oxidations
log
k
AB
related to log
K
AB
Equilibrium Partition Constants
C
i
−
K
ow
log
C
i
related to log
K
ow
Aqueous solubility
K
oc
−
K
ow
Soil-water partition constant
log
K
oc
related to log
K
ow
K
BW
−
K
ow
Bioconcentration factor
log
K
BW
related to log
K
ow
K
mic
−
K
ow
Solute solubility in surfactant
micelles
log
K
mic
related to log
K
ow
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