H2O
En medio Acido
Oxidacin:
++ 4 e
2 H 2 O O2 +4 H
E= 1.23
V
Reduccin:
H 2
++2 e
2 H
E= 0.00V
En medio Bsico
Oxidacin:
O2+ 2 H 2 O+ 4 e
4OH
E= 0.401
V
Reduccin:
H 2+ 2O H
2 H 2 O+2 e
E=
-0.83V
+
H
y el PH.
- En medio Acido
Oxidacin:
++ 4 e
2 H 2 O O2 +4 H
E= 1.23
V
+
H
P O2
0.0591
E=E 0 +
log
4
+
H
[ 4 ]
0.0591
log
4
0.0591
E=E 0 +
log P O2 +
4
+
H
[ ]
4 0.0591
log
4
0.0591
0
E=E +
log P O2 +
4
+
H
[ ]
0.0591 log
0.0591
0
E=E +
log P O2 +
4
H2O
O2
Reduccin:
+
H
2
[ P H 2 ]
0.0591
log
2
0
E=E +
+
H
0.0591
[ 2 ]
log P H 2
2
0.0591
log
2
0
E=E +
+
H
0.0591
[ ]
log P H 2
2
2 0.0591
log
2
E=E0 +
+
H
[ ] [ 0.0295 log P H 2 ]
0.0591 log
0
E=E +
0
H2
H
P H 2 =1 atm
PO2 =1atm
H2 O
O2
H2
H
H2 O
O2
=1.230.06 PH [ z]
=0.0591 PH [ y ]
=1.230.06 PH
H2
H
=0.0591 PH
Cuando :
P=1 atm y
T =25 C=298 K
ECUACIONES:
H2 O
O2
H2
H
=1.230.06 PH [ z]
=0.0591 PH [ y ]
Presin: 1atm
T =25C
Eh(Volts)
1.6
1.4
Acido y
Oxidante
Bsico y
Oxidante
O2
1.2
1.0
0.8
0.6
0.4
0.2
H2O
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
Acido y
Reductor
+
Basico y
Reductor
-1.2
2
10
12
14
pH
(I)
+++2 e
Fe F e
(II)
+++ +e
++ F e
Fe
(III)
+ +e
+++3 H 2 O Fe ( OH )3+ 3 H
F e
(IV)
+
++++3 H 2 O Fe ( OH )3+ 3 H
F e
(V)
+
+ 3 H
+++2 H 2 O HFe O2
Fe
(VI)
++2 e
+3 H
Fe+2 H 2 O HFeO2
(VII)
+ H 2 O Fe ( OH )3 + e
HFe O2
G(298.15 K)
H2O
Kcal/mol
O2
0.000
+
H
0.000
0.000
-56.690
Fe
0.000
++
Fe
-20.300
+++
F e
-2.530
Fe ( OH )3
-161.930
HFe O 2
-90.627
Fe
2++2 e
F e
a) Hallamos
G =G productosG reactivos
G =0[ 20.300+ 0 ]
G =20.300
Kcal
mol
E =
G
nF
Kcal
J
4184
mol
Kcal
C
2 96487
mol
20.300
E =
E =0.4401 v
2+
Fe
++
e
Fe
2.303
RT
E=E 0 +
log
nF
F
++
Fe
0.0591
E=0.4401+
log
2
E=0.617 v
Fe
2++2 e
F e
Potencial:
E=0.617 v
10
12
1.2
1.2
0.8
0.8
0.4
0.4
0.0
0.0
-0.4
-0.4
++
Fe
Fe
-0.8
-0.8
-1.2
-1.2
2
pH
10
12
E (v)
Reaccin:
+++ +e
++ F e
Fe
a) Hallamos
G =G productosG reactivos
G =20.300[ 2.530 ]
G =17.77
Kcal
mol
E =
G
nF
Kcal
J
4184
mol
Kcal
C
2 96487
mol
17.770
E =
E =0.7705 v
++
Fe
+++
F e
+++
Fe
++
e
F
0 2.303 RT
E=E +
log
nF
E=0.7705 v +
0.0591
log [ 1 ]
2
E=0.7705 v +0 v
E=E =0.7705 v
Reaccin:
++
F e
++++ e
F e
Potencial:
E=0.7705 v
10
12
1.2
1.2
+++
Fe
0.8
0.8
0.4
0.4
0.0
0.0
-0.4
-0.4
-0.8
-0.8
-1.2
-1.2
2
pH
+++3 H 2 O
F e
++e
Fe ( OH )3 +3 H
a) Hallamos
G =G productosG reactivos
10
12
E (v)
Fe
Kcal
mol
E =
G
nF
Kcal
J
4184
mol
Kcal
C
1 96487
mol
28.440
E =
E =1.200 v
[ H 2 O ]=
1 mol
L
[ Fe ( OH )3 ]=
1 mol
L
++
Fe
+
H
++
Fe
3
[ H2 O]
[ Fe ( OH )3 ]
0 2.303 RT
E=E +
log
nF
+
H
++
F e
0.0591(3)
E=1.200 v+
log
1
+
H
Reaccin:
+++3 H 2 O
F e
++e
Fe ( OH )3 +3 H
Potencial:
E=1.55460.1773 pH
10
12
1.2
1.2
+++
Fe
0.8
0.8
Fe(OH)3
++
Fe
0.4
0.0
0.0
-0.4
-0.4
-0.8
-0.8
-1.2
-1.2
2
pH
10
12
E (v)
0.4
+
3++3 H 2 O Fe (OH )3 +3 H
F e
La constante de equilibrio
+
H
3+
F e
[ Fe ( OH )3 ]
K=
G =RT ln K
+
H
3+
F e
[ Fe (OH )3 ]
log K=log
+
H
3+
F e
3
log [ H 2 O ]
[ Fe ( OH )3 ] +log
log K =log
7.84
K=10
+
H
+++
F e
3 log [ H 2 O ]
Fe
(
OH
)
[
3 ] +3 log
log K =log
+++
Fe
3 log [ H 2 O ]
(
)
[ Fe OH 3 ] +3 (pH ) log
log ( 10
7.84
)=log
3+
F e
3 log [ H 2 O ]
(
)
[ Fe OH 3 ]3 ( pH )log
7.84=log
Como:
[ Fe ( OH )3 ]= [ H 2 O ]=
1 mol
L
+++=10
F e
pH=4. 61
1 mol
L
Reaccin:
Potencial:
+
3++3 H 2 O Fe (OH )3 +3 H
F e
pH =4. 61
1.2
+++
Fe
10
12
1.2
Fe(OH)3
10
10
0.4
0.4
0.0
0.0
++
Fe
-0.4
-0.4
-0.8
-0.8
-1.2
-1.2
Fe
2
pH
+
+ 3 H
+++2 H 2 O HFe O2
Fe
La constante de equilibrio
31.58
K=10
10
12
E (v)
HFe O 2
+
H
2+
F e
K=
G =RT ln K
G =2.303 RT log K
HFeO2
+
H
2+
F e
log K=log
HFe O2
+
H
++
F e
2
log [ H 2 O ]
31.58
log 10
=log
HFe O2
+
H
++
F e
2 log [ H 2 O ]
31.58=log
HFe O2
++
F e
2 log [ H 2 O ]
31.58=log
Como:
HFe O 2
++
F e
[ H 2 O ]=
mol
L
31.58=63 pH (6 )0
31.58=3 pH
pH=10.53
Reaccin:
Potencial:
+
+ 3 H
+++2 H 2 O HFe O2
F e
pH=10.53
10
12
1.2
1.2
0.8
0.8
0.4
0.4
0.0
0.0
-0.4
++
Fe
HFeO 2
-0.4
-0.8
-0.8
-1.2
-1.2
2
pH
++2 e
+3 H
Fe+2 H 2 O HFeO2
EN forma de reduccin:
Fe+2 H 2 O
++ 2e
+3 H
HFe O2
a) Hallamos
10
12
E (v)
G =G productosG reactivos
Kcal
mol
E =
G
nF
Kcal
J
4184
mol
Kcal
C
2 96487
mol
22.753
E =
E =0.493 v
+
H
++
Fe
3
[ H2 O]
[ Fe ( OH )3 ]
2.303
RT
E=E 0 +
log
nF
[ Fe ( OH )3 ]=
1 mol
L
HFe O 2
+
H
HFe O2
E=0.493+3(0.0295) log
E=0.493+0.0885 (pH ) +00295 log [ 106 ]
E=0.490.0885 pH +(0.177)
E=0.3160.0885 pH
Reaccin:
Potencial:
Fe+2 H 2 O
++ 2e
+3 H
HFe O2
E=0.3160.0885 pH
10
12
1.2
1.2
0.8
0.8
0.4
0.4
0.0
0.0
-0.4
HFeO 2
-0.4
-0.8
-0.8
-1.2
-1.2
2
pH
+ H 2 O Fe ( OH )3 + e
HFe O2
EN forma de reduccin:
10
12
E (v)
+ H 2 O
HFe O2
Fe (OH )3 +e
a) Hallamos
G =G productosG reactivos
G =[90.62756.690] [161.93 ]
G =14.613
Kcal
mol
E =
G
nF
Kcal
J
4184
mol
Kcal
C
1 96487
mol
14.613
E =
E =0.634 v
c) De la ecuacin de Nernst
HFe O2
[ H 2 O]
Fe
(
OH
)3 ]
[
2.303
RT
E=E 0 +
log
nF
HFe O2
HFe O 2
E=0.634(0.0591) log
E=0.279 v
Reaccin:
Potencial:
+ H 2 O
HFe O2
Fe (OH )3 +e
E=0.279 v
10
12
1.2
1.2
0.8
0.8
0.4
0.4
0.0
Fe(OH)3
0.0
HFeO 2
-0.4
-0.4
-0.8
-0.8
-1.2
-1.2
2
10
pH
(I)
+++2 e
Fe F e
(II)
+++ +e
++ F e
Fe
12
E (v)
(III)
+ +e
+++3 H 2 O Fe ( OH )3+ 3 H
F e
K=107.84
(IV)
+
++++3 H 2 O Fe ( OH )3+ 3 H
F e
K=1031.58
(V)
+
+ 3 H
+++2 H 2 O HFe O2
Fe
(VI)
++2 e
+3 H
Fe+2 H 2 O HFeO2
(VII)
+ H 2 O Fe ( OH )3 + e
HFe O2
1.2
0.8
+++
Fe
10
12
(IV)
1.2
Fe(OH)3
(II)
0.8
(III)
0.4
0.4
Fe++
0.0
-0.4
0.0
(VII)
(V)
(I)
-0.8
HFeO2
(VI)
Fe
-1.2
- -0.4
-0.8
-1.2
2
pH
10
12
E (v)