Recapitulando

-cálculo de pH-
Tipo de sustancia en solución Concentración de protones o hidróxido
4° Seminario Teórico-Práctico
CHA + C HA
2
+ 4  Kw | [H3O+] = CHA
HA + H2O A- + H3O+ [ H 3O + ] =
2
Ácido-Base II: Ácidos y Bases Polipróticos, − Ka + Ka 2 + 4  Ka  Ca
HA + H2O A- + H3O+ [ H 3O + ] =
2
Grado de Disociación y Ionización NaOH OH- + Na+ C NaOH + C NaOH
2
+ 4  Kw | [OH-] = CNaOH
[OH − ] =
2
Anfolitos B + H2O BH+ + OH- − Kb + Kb 2 + 4  Kb  Cb
[OH − ] =
2
− Kb + Kb 2 + 4  Kb  Cs
A- + H2O HA + OH- −
[OH ] =
2
BH+ + H2O B + H3O+ − Ka + Ka 2 + 4  Ka  Cs
[ H 3O + ] =
2

Tener en cuenta: - Concentración analítica, fuerza (K de equilibrio)

- Ecuaciones fundamentales (balances en solución)
2

ÁCIDOS POLIPRÓTICOS Tratamiento de sistemas tripróticos para el cálculo

[ H 2 A− ]  [ H 3O + ] de pH
H3A + H2O H2A- + H3O+ Ka1 =
[ H 3 A]
H3A Si Ka1 > 10 x Ka2 Se trata como ácido débil
2−
[ HA ]  [ H 3O + ]
H2A- + H2O HA2- + H3O+ Ka2 = monoprótico
[ H 2 A− ]
HA2- + H2O A3- + H3O+ [ A3− ]  [ H 3O + ] H2A- Ka1  Ka2  C + Ka1  K w
Ka3 = Anfolito [ H 3O + ] =
[ HA2− ] Ka1 + C
H2O + H2O OH- + H3O+
Ka2  Ka3  C + Ka2  K w
Kw = 1,0 x 10-14 = [OH-] x [H3O+] HA2- Anfolito [ H 3O + ] =
Ka2 + C

Balance de masa: Ca = [H3A] + [H2A-] + [HA2-] + [A3-]

A3- Si Kb1 > 10 x Kb2 Se trata como base débil
Balance de cargas: [H3O+] = [H2A-] +2 [HA2-] + 3 [A3-] + [OH-] Kw monofuncional
Kb1 =
Ka3
Calcular el pH de una solución de H3PO4 0,100 M.
Ka1: 1,1 x 10-2 Ka2: 7,5 x 10-8 Ka3: 4,8 x 10-13 Ka1: 1,1 x 10-2 >> 10 x Ka2 = 7,5 x 10-7
Balance de masa: Ca = [H3PO4] + [H2PO4-] + [HPO42-] + [PO43-]
[ H PO − ]  [ H 3O + ]
H3PO4 + H2O H2PO4 - + H3O+ Ka1 = 2 4
[ H 3 PO4 ] Balance de cargas:
[ HPO42− ]  [ H 3O + ] [H3O+] = [H2PO4-] + 2 [HPO42-] + 3 [PO43-] + [OH-]
H2PO4 - + H2O HPO42- + H3O+ Ka2 =
[ H 2 PO4− ]
HPO42- + H2O PO43- + H3O+ [ PO43− ]  [ H 3O + ] − Ka1 + Ka1 + 4  Ka1  Ca
2
Ka3 = +
[ HPO42− ] [ H 3O ] = = 0.0281 M pH = 1,55
2
H2O + H2O OH- + H3O+
Kw = 1,0 x 10-14 = [OH-] x [H3O+] Verificación de desprecios: ✓
Balance de masa: Ca = [H3PO4] + [H2PO4-] + [HPO42-] + [PO43-] [OH − ] = 3,56 10−13 M << 10% de [H2PO4-]: 2,81x10-3 M

Balance de cargas: [H3O+] = [H2PO4-] + 2 [HPO42-] + 3 [PO43-] + [OH-] [HPO42-] = 7,5 x 10-8 M, << 10% de [H2PO4-]: 2,81x10-3 M
considero [H2PO4-] = [H3O+]

Calcular el pH de una solución de Na3PO4 0,100 M

Ka1: 1,1 x 10-2 Ka2: 7,5 x 10-8 Ka3: 4,8 x 10-13 Balance de masa: C = [H3PO4] + [H2PO4-] + [HPO42-] + [PO43-]
C x 3 = [Na+]
Na3PO4 3 Na+ + PO43- Balance de cargas:
[ HPO42− ]  [OH − ] Kw [H3O+] + [Na+] = [OH-] + 3 x [PO43-] + 2 x [HPO42-] + [H2PO4-]
PO43- + H2O HPO42- + OH Kb1 = =
[ PO43− ] Ka3 Reemplazando [PO43-] en BQ a partir del BM:
− −
[ H PO ]  [OH ] Kw
HPO42- + H2O H2PO4- + OH- Kb2 = 2 4 2− = [H3O+] + 3 x [H3PO4] + 2 x [H2PO4-] + [HPO42-] = [OH-]
[ HPO4 ] Ka2
[ H PO ]  [OH − ] Kw − Kb1 + Kb1 + 4  Kb1  C
2

H2PO4- + H2O H3PO4 + OH- Kb3 = 3 4 − = −

[OH ] = = 0,0364 M
[ H 2 PO4 ] Ka1 2

H2O + H2O OH- + H3O+ Kw = 1,0 x 10-14 = [OH-] x [H3O+] pOH = 1,44 pH = 12,56

Kb1: 2,1 x 10-2 > 10 x Kb2 : 10 x 1,3 x 10-7

Verificación de desprecios: ✓
 BASES POLIFUNCIONALES Tratamiento de sistemas bifuncionales para el
cálculo de pH
[OH − ]  [ BH + ]
B + H2O BH+ + OH- Kb1 = B Si Kb1 > 10 x Kb2 Se trata como base débil
[ B]
monofuncional
[OH − ]  [ BH 22+ ]
BH+ + H2O BH22+ + OH- Kb2 = Ka1  Ka2  C + Ka1  K w
[ BH + ] BH+ Anfolito [ H 3O + ] =
Ka1 + C
H2O + H2O OH- + H3O+ Kw
Kw Ka2 =
Ka1 = Kb1
Kw = 1,0 x 10-14 = [OH-] x [H3O+] Kb 2

BH22+ Si Ka1 > 10 x Ka2 Se trata como ácido débil

Balance de masa: Cb = [B] + [BH+] +[BH22+]
monoprótico
Balance de cargas: [OH-] = [BH+] + 2 [BH22+] + [H3O+]

Calcular el pH de una solución de etilendiamina 0,0100 M

Ka1: 1,4 x 10-7 Ka2:1,17 x 10-10 − Kb1 + Kb1 + 4  Kb1  C
2
−
[OH ] = = 8,8310−4 M
B: NH2-CH2-CH2-NH2 2
pOH = 3,05 pH = 10,95
[OH − ]  [ BH + ]
B + H2O BH+ + OH- Kb1 = = 8,55 10−5
[ B]
Verificación de desprecios: ✓
− 2+
[OH ]  [ BH ]
BH+ + H2O BH22++ OH- Kb2 = +
= 7,110−8
2
[H3O+] = 1,13 x 10-11 M << 10 % de [BH+]: 8,83 x 10-5 M
[ BH ]
H2O + H2O OH- + H3O+ Kw = 1,0 x 10-14 = [OH-] x [H3O+]
2 x [BH22+] = 2 x 7,10 x 10-8 M << 10% de [BH+]: 8,83 x 10-5 M
Kb1: 8,55 x 10-5 > 10 x Kb2 : 7,1 x 10-7
Balance de masa: C = [B] + [BH+] +[BH22+]
Balance de cargas: [OH-] = [BH+] + 2 x [BH22+] + [H3O+]
Calcular el pH de una solución de BH2Cl2 0,0100 M. Ka1: 1,4 x 10-7 Ka2:1,17 x 10-10
BH22+: NH3+-CH2-CH2-NH3+
− Ka1 + Ka1 + 4  Ka1  C
2
+
BH2Cl2 BH22+ + 2 Cl- [ H 3O ] =
+ + 2
[ H 3O ]  [ BH ]
BH22+ + H2O BH+ + H3O+ Ka1 =
[ BH 22+ ] − 1,4 10−7 + (1,4 10−7 ) 2 + 4 1,4 10−7  0,0100
[ H 3O + ] = = 3,7510−5 M
2
[ H 3O + ]  [ B]
BH+ + H2O B + H3O+ Ka2 =
[ BH + ]
pH = 4,43
H2O + H2O OH- + H3O+ Kw = 1,0 x 10-14 = [OH-] x [H3O+]
Verificación de desprecios: ✓
Ka1 > 10 x Ka2
Balance de masa: Ca = [B] + [BH+] +[BH22+] C x 2 = [Cl-]
[ H 3O + ] = Ka1  C = 3,76 10−5 M
Balance de cargas: [OH-] + [Cl-] = [H3O+] + [BH+] + 2 x [BH22+]
pH = 4,43
Combinando BM y BQ: [OH-] + 2 x [B] + [BH+] = [H3O+]

1  [ H 3O + ]
Grado de disociación en ácidos débiles polifuncionales Ka1 =  2  [ H 3O + ]
0 Ka2 =
[ H A− ]  [ H 3O + ] 1  3  [ H 3O + ]
H3A + H2O H2A- + H3O+ Ka1 = 2 Ka3 =
[ H 3 A] 2
2−
[ HA ]  [ H 3O + ] Ka1  α0 Ka2  Ka1  α0 Ka3  Ka2  Ka1  α0
H2A- + H2O HA2- + H3O+ Ka2 = 1 = α0 + + +
[ H 2 A− ] [H3O + ] [H3O + ] 2 [H3O + ] 3
HA2- + H2O A3- + H3O+ [ A3− ]  [ H 3O + ] [H3O + ] 3
Ka3 = α0 =
[ HA2− ] [H3O + ] 3 + Ka1  [H3O + ] 2 + Ka1  Ka2  [H3O + ] + Ka1  Ka2  Ka3

[ H 2 A− ] [ HA2− ] [ A3− ] Ka1  [H3O + ] 2

[ H A] α1 =
0 = 3 1 = 2 = 3 = [H3O + ] 3 + Ka1  [H3O + ] 2 + Ka1  Ka2  [H3O + ] + Ka1  Ka2  Ka3
Ca Ca Ca Ca
Ka1  Ka2  [H3O + ]
− 2− 3− α2 =
Ca [ H 3 A] [ H 2 A ] [ HA ] [ A ] [H3O + ] 3 + Ka1  [H3O + ] 2 + Ka1  Ka2  [H3O + ] + Ka1  Ka2  Ka3
= + + +
Ca Ca Ca Ca Ca Ka1  Ka2  Ka3
α3 = +
[H3O ] + Ka1  [H3O ] + Ka1  Ka2  [H3O + ] + Ka1  Ka2  Ka3
3 + 2

1 = 0 + 1 + 2 + 3
 Fracción de concentración de especies de ácidos débiles dipróticos
1  [ H 3O + ]  2  [ H 3O + ]
Ka1 = Ka2 =
[ HA− ]  [ H 3O + ] 0 1
H2A + H2O HA-+ H3O+ Ka1 =
[ H 2 A]
2−
[ A ]  [ H 3O + ] Ka1  α0 Ka2  Ka1  α0
HA- + H2O A2- + H3O+ Ka2 = 1 = α0 + +
[ HA− ] [H3O + ] [H3O + ] 2
[ H 2 A] [ HA− ] [ A2− ]
0 = 1 =  2 = [H3O + ] 2
C C C α0 =
[H3O + ] 2 + Ka1  [H3O + ] + Ka1  Ka2
C [ H 2 A] [ HA− ] [ A2− ] Ka1  [H3O + ]
= + + α1 =
C C C C [H3O + ] 2 + Ka1  [H3O + ] + Ka1  Ka2

Ka1  Ka2
α2 =
1 = 0 + 1 + 2 +
[H3O ] + Ka1  [H3O + ] + Ka1  Ka2
2

Fracción de concentración de especies de bases débiles difuncionales Ka1  Ka2

α0 = +
[H3O ] + Ka1  [H3O + ] + Ka1  Ka2
2
[OH − ]  [ BH + ]
B + H2O BH+ + OH- Kb1 =
[ B] [OH − ]2
α0 =
[OH − ]  [ BH 22+ ] [OH − ] 2 + Kb1  [OH − ] + Kb1  Kb2
BH+ + H2O BH22+ + OH- Kb2 =
[ BH + ]
Ka1  [H3O + ]
α1 =
[ B] [ BH + ] 2+
[ BH 2 ] [H3O + ] 2 + Ka1  [H3O + ] + Ka1  Ka2
0 = 1 = 2 =
C C C
[H3O + ] 2
C [ B] [ BH + ] [ BH 22+ ] α2 =
= + + [H3O + ] 2 + Ka1  [H3O + ] + Ka1  Ka2
C C C C
1 = 0 + 1 + 2
 Fracción de las especies de ácido cítrico en función de pH
Fracción de las especies de H3PO4 en función de pH

pH=pKa2=7,12
pH=pKa1=1,96 pH=pKa2=4,77
pH=pKa1=3,13
pH=pKa3=12,32

pH=pKa3=6,40

ANFOLITOS I
Fracción de las especies de etilendiamina en función de pH
NaHCO3 Na+ + HCO3-
HCO3- + H2O H2CO3 + OH-
HCO3- H+ + CO32-
pH=pKa1=6,85 pH=pKa2=9,92
BM: Cs = [Na+]
[ B] Cs = [CO32-] + [HCO3-] + [H2CO3]
0 =
Cb
BQ: [OH-] + 2[CO32-] + [HCO3-] + = [H+] + [Na+]
+
[ BH ]
1 = [OH-] + 2[CO32-] + Cs - [CO32-] - [H2CO3] = [H+] + Cs
Cb
Reordenando y cancelando:
[ BH 22+ ]
2 = [OH-] + [CO32-] - [H2CO3] = [H+]
Cb
[H+] + [H2CO3] = [OH-] + [CO32-]
 ANFOLITOS II Cálculo de pH de soluciones de sales de ácidos y bases débiles
Ejemplo: formiato de amonio

Generalmente: Cs = [HCO3-] se obtiene la siguiente ecuación:

Cuando se cumple que Cs >> Ka1 y (Ka2x Cs) >>Kw la expresión se

reduce a:

Para ir cerrando la clase de hoy…

28

KaBH+ = Kw/KbB