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CONSTRUCCION DE UN DIAGRAMA Ph-Potencial

1 Considerar las siguientes reacciones de equilibrio quimico del hierro:


_ ^0 (298.15
Energia libre de formacion de Gibbs
_ ^0 (298.15Kcal/mol
K)
_2 Componente [] (mol/L)
^(2+)
_2 -56.69 ^(3+) 0.000001
^+ 0 _2 0.000001
^ 0 () _3 1
Fe 0 _2 1
^(2+) 0 0.000001
-20.3 Fe 1
^(3+)
() _3 -2.53
_2 -161.93
-90.627
REACCION 1

A) Calcular la energia libre de Gibbs: ^0=^0 ^0

^0= 20.3 Kcal/mol


84935.2 J/mol
B) Calcular el valor potencial estandar del electrodo:
^0=(^0)/

^0= -0.44013805 V

C) Calcular el potencial de voltaje: =+2.303/Log [C][D]/


([][])

E= -0.6175559 V

D) Se construye el diagrama E/V


0 -0.61755591 Equilibr
1 -0.61755591
1.4
2 -0.61755591
3 -0.61755591 0.9
4 -0.61755591
5 -0.61755591 0.4
6 -0.61755591
7 -0.61755591 -0.1

E/V
8 -0.61755591
-0.6
9 -0.61755591
10 -0.61755591 -1.1
11 -0.61755591
12 -0.61755591 -1.6
0
13 -0.61755591
14 -0.61755591
R= 8.314472 J/K mol
T= 298 K

Equilibrio 1 en el diagrama pH-V del Fe-Agua


1.4

0.9

0.4

-0.1
E/V

-0.6

-1.1

-1.6
0 2 4 6 8 10 12 14
REACCION 2

A) Calcular la energia libre de Gibbs: ^0=^0 ^0

^0= -17.77 Kcal/mol


-74349.68 J/mol

^0=(^0)/
B) Calcular el valor potencial estandar del electrodo:

^0= 0.38528341 V

C) Calcular el potencial de voltaje: =+2.303/Log [C]


[D]/([][])

E= 0.38528341 V
0.77056681
D) Se construye el diagrama E/V
0 0.77056681 Equilibrio 2 en
1 0.77056681 0.
8
2 0.77056681 72
0.
3 0.77056681 64
0.
4 0.77056681 56
0.
5 0.77056681 48
0.
4

E/V
6 0.77056681 0.
32
7 0.77056681 0.
24
8 0.77056681 0.
16
9 0.77056681 0.
08
0.
10 0.77056681 0
0 2
11 0.77056681
12 0.77056681
13 0.77056681
14 0.77056681
1 Kcal= 4184 J
n= 2
F= 96487 C/mol

R= 8.314472 J/K mol


T= 298 K

Equilibrio 2 en el diagrama pH-V para Fe-Agua


8
0.
72
0.
64
0.
56
0.
48
0.
4
E/V

0.
32
0.
24
0.
16
0.
08
0.
0
0 2 4 6 8 10 12 14
pH
REACCION 3

A) Calcular la energia libre de Gibbs: ^0=^0 ^0

^0= -28.44 Kcal/mol


-118992.96 J/mol
^0=(^0)/
B) Calcular el valor potencial estandar del electrodo:

^0= 1.23325381

=+2.303/Log ([]^ []^)/([]^


C) Calcular el potencial de voltaje:
[]^ )

E= 1.584-0.1773pH

D) Se construye el diagrama E/V


0 1.584 Equilibrio
1 1.4067
2 1.2294 1.9
3 1.0521 1.4
4 0.8748 0.9
5 0.6975 0.4
6 0.5202

E/V
-0.1
7 0.3429
-0.6
8 0.1656
-1.1
9 -0.0117
-1.6
10 -0.189 0 2
11 -0.3663
12 -0.5436
13 -0.7209
14 -0.8982
1 Kcal= 4184 J
n= 1
F= 96487 C/mol

)/([]^ R= 8.314472 J/K mol


T= 298 K

Equilibrio 3 en el diagrama pH-V del Fe-Agua

1.9
1.4
0.9
0.4
E/V

-0.1
-0.6
-1.1
-1.6
0 2 4 6 8 10 12 14
pH
REACCION 4

=([(_3)]
A) La cte de equilibrio se expresa como: [^+ ]^3)/([ ^(3+) ] [_2 ]^3 )

=((_3)+3log^+)-(log ^(3+)+3_2 )

=3log( 10 ^(6))

10 ^(7.84)=1.445410^(8)

log(1. 445410 ^(8))=-7.839

7.839=3[]+6

7.839=3+6

=4.61

B) Se construye el diagrama E/V


4.61 1.6 Equilibrio 4 e
4.61 1.4
4.61 1.2 1.4
4.61 1
0.9
4.61 0.8
4.61 0.6 0.4

4.61 0.4 -0.1

E/V
4.61 0.2 -0.6
4.61 0
-1.1
4.61 -0.2
-1.6
4.61 -0.4
4 5
4.61 -0.6
4.61 -0.8
4.61 -1
4.61 -1.2
4.61 -1.4
4.61 -1.6
^(3+)+3_2 )

Equilibrio 4 en el diagrama pH-V del Fe-Agua

1.4

0.9

0.4

-0.1
E/V

-0.6

-1.1

-1.6
4 5 6 7 8 9 10
pH
REACCION 5

=([_2
A) La cte de equilibrio se expresa como: ] [^+ ]^3)/([ ^(2+) ] [_2 ]^2 )

=(_2)+3log^+)-(log ^(2+)+2_2 )

=log( 10 ^(6) )+3log( 10 ^(6))

10 ^(38.53)=2.63010^(32)

log(2. 63010 ^(32))=-31.58

31.58=6+3[]+6

31.58=3

=10.52

B) Se construye el diagrama E/V


10.52 1.6 Equilibrio 5
10.52 1.4 1.9
10.52 1.2
1.4
10.52 1
0.9
10.52 0.8
10.52 0.6 0.4

E/V
10.52 0.4 -0.1
10.52 0.2 -0.6
10.52 0
-1.1
10.52 -0.2
-1.6
10.52 -0.4
10
10.52 -0.6
10.52 -0.8
10.52 -1
10.52 -1.2
10.52 -1.4
10.52 -1.6
(2+)+2_2 )

Equilibrio 5 en el diagrama pH-V del Fe-Agua


1.9

1.4

0.9

0.4
E/V

-0.1

-0.6

-1.1

-1.6
10 10.5 11
pH
REACCION 6

A) Calcular la energia libre de Gibbs: ^0=^0 ^0

^0= -22.753 Kcal/mol


-95198.552 J/mol
^0=(^0)/
B) Calcular el valor potencial estandar del electrodo:

^0= 0.4933232 V

=+2.303/Log [C][D]/
C) Calcular el potencial de voltaje: ([][])

E= 0.316-0.0886pH

D) Se construye el diagrama E/V


0 0.316
1 0.2274 0.4
2 0.1388 0.2
3 0.0502 0
4 -0.0384
-0.2
5 -0.127

E/V
6 -0.2156 -0.4
7 -0.3042 -0.6
8 -0.3928 -0.8
9 -0.4814
-1
10 -0.57 0
11 -0.6586
12 -0.7472
13 -0.8358
14 -0.9244
1 Kcal= 4184 J
n= 2
F= 96487 C/mol

R= 8.314472 J/K mol


T= 298 K

Equilibrio 6 en el diagrama pH-V para el Fe-Agua


0.4

0.2

-0.2
E/V

-0.4

-0.6

-0.8

-1
0 2 4 6 8 10 12 14 16
pH
REACCION 7

A) Calcular la energia libre de Gibbs: ^0=^0 ^0


^0= 14.613 Kcal/mol
61140.792 J/mol
^0=(^0)/
B) Calcular el valor potencial estandar del electrodo:

^0= -0.6336687 V
=+2.303/Log [C][D]/
C) Calcular el potencial de voltaje: ([][])

E= -0.278833 V

D) Se construye el diagrama E/V


0 -0.278833 Equilibrio 7
1 -0.278833 1.
6
2 -0.278833 1.
2
3 -0.278833 8
0.
4 -0.278833 4
0.
5 -0.278833 0

E/V
6 -0.278833
.4
7 -0.278833 -0
.8
8 -0.278833 -0
9 -0.278833 .2
-1
10 -0.278833 .6
-1 0 2
11 -0.278833
12 -0.278833
13 -0.278833
14 -0.278833
1 Kcal= 4184 J
n= 1
F= 96487 C/mol

R= 8.314472 J/K mol


T= 298 K

Equilibrio 7 en el diagrama pH-V pra Fe-Agua


6
1.
2
1.
8
0.
4
0.
0
E/V

.4
-0
.8
-0
.2
-1
.6
-1 0 2 4 6 8 10 12 14
pH
DIAGRAMA DE POURBAIX PARA Fe-H2O
1.6

1.4
1.2

1
0.8

0.6

0.4
0.2

0
E/V

-0.2

-0.4
-0.6

-0.8
-1

-1.2

-1.4
-1.6
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

pH

PASIVACION

CORROSION

CORROSION

INMUNIDAD
REACCION 1
REACCION 2
REACCION 3
REACCION 4
REACCION 5
REACCION 6
REACCION 7

1 12 13 14

REACCIN 1
REACCIN 2
REACCIN 3
REACCIN 4
REACCIN 5
REACCIN 6
REACCIN 7

REACCION 1 REACCION 2 REACCION 3

CORROSION
REACCION 6 REACCION 7

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