DIAGRAMA DE POURBAIX Eh-pH

Pb Cl H2O

CONDICIONES.

T = 250C =2980K CI = 10-6 n ( mol/Kgr)

P = 1 Atm. R = 1,987 cal/ mol0K
F = 23065

FORMULAS A EMPLEAR

G 0.059
Eo E Eo Log K
nF n

A).- ESTABILIDAD DEL AGUA

1.- Lmite inferior:

2H+ + 2e = H2 G 25 O C E O 0

0.059 2 Log 1
0.059 1
E 0 Log
n
H
2
2 H
E = - 0.059 pH

E Ph
0 0
0.236 4
0.472 8
0.826 14

2.- Lmite Superior:

1 / 2 O2 2 H 2e H 2 O donde: G H 2 O 25 C -56678 cal/mol

O

EO
G

56.678 1,228 v
nF 2 23,065
0.059 1
E EO Log
n H 2

E 1,228 0.059 pH

E PH
1,228 0
0,933 5
0,638 10
0,402 14

1.- 3PbO2 4 H 4e Pb3 O 4 H 2 O

 G G Pb3O4 G H 2O 3G PbO2

G 143,787 56,678 3 51,841

G 44,942 Kcal

EO
G

44,842 0,4871
V
nF 4 23,065

0,059 1 0,059 1
E EO Log 0,4871 (4) Log
n H 4
4
H

E = 0.4871 0,059 pH

PH 6.9 9 11 13 14
E (v) 0.08 -0.04 -0.16 -0.28 -0.34

2.- Pb3 O 4 2 H 2e 3PbO H 2 O
G 3G PbO G H 2O G Pb3O4

G 3(45239) ( 56678) ( 143787 )

G 48608cal

EO
G

48606 1.05
nF 2(23065)
0, 059 1 0,059 1
E EO. Log 1.05 (2) Log
n H 2
2 H
E 1,05 0.059 pH

PH 6.9 9 11 13 14
E 0.64 0.519 0.4 0.280 0.22

3.- PbO + 2H+ + 2 e- = Pb + H2O

G G H 2O G PbO
G 56678 (45098)
G 11590 cal
0,059 ( 11590)
E 0,251
n 2(23069)
0,059 1
E EO Log 0,251 0,059 pH
n H
2

E 0,251 0,059 pH
 PH 0 4 8 11 14
E 0.251 0.015 -0.22 -0.398 -0575

4.- PbO2 + 4H+ + 2 e- = Pb+2 + 2 H2O

G 2G H 2O G Pb 2 G PbO2
G 2(56678) ( 5854) ( 51481)
G 67729

EO
G
Log

Pb 2
E

1, 486
0.059( 4)
Log
10 6
n H 4
2 H
E 1,486 0.118 Log
10 6
H
E 1,486 0,118 Log10 6 pH

E 2,176 0.118 pH

PH 0 4 8 11 14
E 2.176 1.7 1.2 0.88 0.52

5.- 2Pb3O4 + 8 H+ + 4 e- = Pb6(OH)8+4

G 430253 2(147787)
G 134679
G (134679)
EO 1,46v
nF 4(23065)

E EO
0,059
Log

Pb6 (OH ) 8 4
n H*
8

0,059 Pb6 (OH ) 8 4
E 1,46 (8) Log
4 H
E = 1,46 0,118 (Log 10-6 + pH) = 2,168 - 0,118 pH

PH 0 4 8 11 14
E 2.168 1.7 1.22 0.87 0.52

6.- 6 PbO + 2H2O + 44 H+ = Pb6(OH)8-4

 G G P b6 ( OH ) 4 6
8

G ( 430253) 6(
G 46369
G RT ln K G

46,369 1.987 ( 298

0,034 Log
Pb 6 (OH )
H
4

0,0344 Log 10 6
4
pH 1.51

7.- Pb6(OH)8 + 2 H+ = 6/4 Pb4(OH)4+4 +2 H2O

G 2G H 2 O 6 / 4G Pb ( OH ) 4 G Pb6 ( OH )8
8 4

G 56678 6 / 4(223802) (430253)

G 18806cal

G RTInK G RT (2,3) Log

Pb 4 (OH ) 4 4
Pb (OH ) H
6
4
8
2

10 6
-18806 = -1,287 (2,3) Log 6
pH
10

pH = 6.9

8.- ClO4- + 8 H+ + 8 e- = Cl- + 4 H2O

G = GCl - + 4 GH2O - GClO4-

G = -31384 + 4 (-56678) - (-2038)
G = -256058 cal.

E0 = -G = - (-256058) = 1.387 V
nF 8 (23065)

E = E0 0.059 log [ Cl - ] . = 1.3987 - 0.059 log 10-6 .

n [ClO4-] [H+]8 8 10-6 [H+]
E=1.387-0.059pH

PH 7 9 11 14
E 0.97 0.86 0.738 0.56

9.- ClO4- + H+ = HClO4

G = GHCl O4 - GClO4-
G = -2038 - (-2038)
G = 0
E0 = 0
PH=0

10.- HClO2 + 3H+ + 4e- = Cl- +2H2O

 G = G Cl - + GH2O - GHClO4
G = -31384 + 2 (-56678) (1393)
G = -146133 cal.

E0 = -G = - (-146133) = 1.584 V
nF 4 (23065)

E = E0 0.059 log [Cl-] = 1.584 - 0.059 log 10-6 .

n [H+]3 4 [H+]3
E=1.673-0.04425pH

PH 0 5 10 14
E 1.673 0.22 0.44 0.61

11.- ClO2- + 4H+ + 3e- = Clo + 2H2O

G = 2 GH2O - GClO2-
G = -2 (-56678) (1393)
G = -114749 cal.

E0 = -G = - (-114749) = 1.658 V
nF 3 (23065)

E = E0 0.059 log 1 = 1.658 - 0.059 log 10-6 .

n [H+]3 [ClO2-] 3 10-6[H+]3
E=1.658 - 0.059pH

PH 0 5 10 14
E 1.658 1.36 1.07 0.83

12.- ClO3- + 6H+ + 5e- = Clo + 3H2O

G = 3 GH2O - GClO3-
G = 3 (-56678) (-1886)
G = -168148 cal.

E0 = -G = - (-168148) = 1.458 V
nF 5 (23065)

E = E0 0.059 log 1 = 1.458 - 0.059 log 1 .

n [H+]3 [ClO3-] 5 10-6 [H+]3
E=1.3872 - 0.0708pH

PH 0 5 10 14
E 1.387 1.03 0.679 0.39

13.- PbO + 2Cl- + 2H+ =PbCl2 + H2O

G = GH2O + GPbCl - GPbO - 2GCl-

G = (-56678) + (-75077) (-45088) 2(- 31384)
G = -23899 cal.
 E0 = -G = - ( - 23899) = 0.518 V
nF 2 (23065)

E = E0 0.059 log 1 = 0.518 - 0.059 (2) log 1 .

n [H+]2 [Cl-]2 2 10-6 [H+]
E=0.164 - 0.059pH

PH 0 5 10 14
E 0.164 -0.131 -0.426 -0.662

14.- PbO2-2 + 2HCl + 2H+ = PbCl2 + 2H2O

G = 2GH2O + GPbCl 2 - GPbO2-- - 2GHCl
G = 2(-56678) + (-75077) (-51481) 2(- 21284)
G = -74184 cal.

E0 = -G = - ( -74184) = 1.608 V
nF 2 (23065)

E = E0 0.059 log 1 = 1.608 - 0.059 log 1 .

n [H+]2 [PbO2-2] 2 10-6 [H+]

E=1.519 - 0.0295pH

PH 0 5 10 14
E 1.519 1.37 1.224 1.106