CLCULO DE EQUILIBRIO EN CIDOS

POLIPRTICOS
 Los cidos poliprticos dbiles son aquellos que
donan ms de un protn en agua. Ejemplo:

H2CO3 H+ + HCO3- K1 = [H+] [HCO3-]=3.5 10-7

[H2CO3]

HCO3- H+ + CO32- K2 = [H+] [CO32-]=6.0 10-11

[HCO3-]

SIEMPRE. K1> K2> K3

 Calcule el pH de una solucin de acido H2A 10-2M
si K1 = 1.0x10-3 y K2= 1.0 x10-4
SOLUCIN:
Incgnitas: H2A , HA- , A2- , H+ , OH-
Los equilibrios que surgen son:
H2O H+ + OH- Kw= [H+] [OH-]= 10-14 (1)

H2A H+ + HA- K1= [H+] [AH-] =1.1x 10-3 (2)

[H2A]

HA- H+ + A2- K2= [H+] [A2-] =1.0 x10-4 (3)

[HA-]
 [H+] = [AH-] + 2 [A2-] + [OH-] (4)

Balance de masas para A:

CA= CH2A = [H2A] + [AH-] + [A2-] =10-2 (5)

0= [H2A ] = [H2A]_________
CH2A [H2A] + [HA-] + [A2-]

1 = [HA-] = __________[AH-]__________
CH2A [H2A] + [AH-] + [A2-]

2 = [ A2-] = [A2-]____________
CH2A [H2A] + [HA-] + [A2-]
 Expresamos c/termino en funcin de [H2A]

De (2): [HA-] = K1 [H2A]

[H+]

De (3): [A2-] = K2 [AH-] = K2 K1 [H2A]

[H+] [H+] [H+]

[A2-]= k1 k2 [H2A]
[H+]2

 0 = [H2 A]______________
[H2 A] + k1 [H2 A] + K1 K2 [H2 A]
[H+] [H+]2

0 = [H+ ] 2____ = [H2 A]

[H+] 2 + k1 [H+] + K1K2 CH2A

Anlogamente: 1 en funcin de HA-

2 En funcin de A2-
 Finalmente tenemos:

+ -
1 = k1 [H ]___= [HA ]
+ 2 +
[H ] + k1 [H ] + k1 K2 CH2 A

2-
2 = k1 K2_____= _[A ]
+ 2 +
[H ] + k1 [H ] + k1 K2 CH2 A
Luego en el equilibrio:

[H2 A] = 0 CH2 A
- +
[AH ] = 1 CH2 A conociendo [H ]
2-
[A ] = 2 CH2 A conoceremos las otras
- +
Ademas : [OH ] = kw/ [H ] concentraciones.
 reemplazamos en 4:
[H+] =1 CH2A + 2 2 CH2A + [OH-]

Iniciamos aproximaciones:

En una solucin acida [OH-] es pequeo

[H+] = 1 CH2A + 2 2 CH2A
Para valores pequeos de pH (alta [H+]):
1 >> 2
[H+] 1 CH2A
 [H+] = [H+] k1 _____. CH2A
[H+] 2 + k1 [H+] + k1 K2

Para valores bajos de pH:

[H+]2 >> k1[H+] +k1 K2

[H+] = [H+] k1 CH2A = _k1 CH2A

[H+] 2 [H+]
[H+]| = (k1 CH2A)1/2 Primera aproximacin
[H+]| =(1.0 x10-3 x 10-2)1/2 = 3.16 x 10-3 = 10-2.5 M

pH=2.50
 Segunda aproximacin: sustituimos [H+]| en la
ecuacin de 1 y 2
1 = k1 [H+]_______
([H+]|)2 + k1 [H+]| + k1 K2

1 = 10-3 X 10-2.5 __________________

(10-2.5)2 +10-3x10-2.5+10-3 x10-4

1 = 0,238
 2 = k1 K2_______
([H+]|)2 + k1 [H+]| + k1 K2

2 = 10-3 x 10-4 ________

(10-2.5)2 +10-3 x 10-2.5+10-3 x10-4

2 = 7.54 x10-3
 [H+]|| = 1 CH2A + 2 2 CH2A + Kw
[H+]|
[H+]|| =(0,238)(10-2 )+2(7,54 x10-3) (10-2)+ 10-14
10-2.5

[H+]|| = 2.53 x10-3 M, entonces el pH resulta:

pH =2.60
 Tercera aproximacin:
1 = 0.28
2= 0.011
[H+]||| = 3 x 10-3 M
pH = 2.52

podramos quedarnos con la primera

aproximacin

mas aproximaciones conducen a +0.02 pH.