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Equilibrio de solubilidad
• Equilibrio dinámico en soluciones saturadas existe
entre solido no disuelto y las especies iónicas en
solución.
Ej: AgCl(s) ⇌ Ag+(aq) + Cl-(aq)
• Producto de solubilidad
Kps = [Mn+]m[Xm-]n
Solubilidad y Producto de Solubilidad
Ejemplos:
AgCl(s) ⇌ Ag+(aq) + Cl-(aq)
Kps = [Ag+][Cl-] = 1.6 x 10-10
• More Examples:
• Ca(IO3)2(s) ⇌ Ca2+(aq) + 2 IO3-(aq)
• Ksp = [Ca2+][IO3-]2 = 7.1 x 10-7
• More Examples:
• Ag3PO4(s) ⇌ 3Ag+(aq) + PO43-(aq)
• Ksp = [Ag+]3[PO43-] = 1.8 x 10-18
• More Examples:
• Ca3(PO4)2(s) ⇌ 3Ca2+(aq) + 2PO43-(aq)
• Ksp = [Ca2+]3[PO43-]2 = 1.3 x 10-32
• Solutions:
Solubility in water = (Kps)
= (1.6 x 10-10) = 1.3 x 10-5 mol/L
Solubilidad Exercicio #1
[ NH 3 ]2 (1 - 2 S ) 2
Solubility Exercise #1
• Solubility of AgCl in 1.0 NH3 (continued):
S
2.7 x 10-3 0.052
(1 - 2S )
S = 0.052 – 0.104S;
S = 0.052/1.104 = 0.047 mol/L
• AgCl is much more soluble in NH3 solution than in
water.
Predicción de la Formación de Precipitado
• Qps = Kps saturated solution, but no precipitate
• Qps > Kps saturated solution, with precipitate
• Qps < Kps unsaturated solution,
• Calculation:
• [Pb2+] = (20.0 mL x 0.025 M)/(50.0 mL) = 0.010 M
• [Cl-] = (30.0 mL x 0.10 M)/(50.0 mL) = 0.060 M
• Qps = [Pb2+][Cl-]2 = (0.010 M)(0.060 M)2
• = 3.6 x 10-5
• Qps > Kps precipitate of PbCl2 will form.
Aplicaciones prácticas del equilibrio de
Solubilidad
• Análisis Cualitativo
– Separación e identificación of cationes y/o aniones en
muestras desconocidas
2
[Cu(NH 3 ) 4 ]
Kf 1.1 x 1013
[Cu 2 ][ NH 3 ]4
Stepwise Formation of Complex Ion
• At molecular level, ligand molecules or ions combine with
metal ions in stepwise manner;
• Each step has its equilibrium and equilibrium constant;
• For example:
(1) Ag+(aq) + NH3(aq) ⇌ Ag(NH3)+(aq)
[Ag(NH 3 ) ]
K f1 2.1 x 10 3
[Ag ][NH 3 ]
[Ag(NH 3 ) ][NH 3 ]
Stepwise Formation of Complex Ion
Individual equilibrium steps:
(1) Ag+(aq) + NH3(aq) ⇌ Ag(NH3)+(aq); Kf1 = 2.1 x 103
[Ag ][NH 3 ]2
f1 f2
Stepwise complex ion formation for Cu(NH3)42+
Individual equilibrium steps:
1. Cu2+(aq) + NH3(aq) ⇌ Cu(NH3)2+(aq); K1 = 1.9 x 104
2. Cu(NH3)2+(aq) + NH3(aq) ⇌ Cu(NH3)22+(aq); K2 = 3.9 x 103
3. Cu(NH3)22+(aq) + NH3(aq) ⇌ Cu(NH3)32+(aq); K3 = 1.0 x 103
4. Cu(NH3)32+(aq) + NH3(aq) ⇌ Cu(NH3)42+(aq); K4 = 1.5 x 102
Combining equilibrium:
• Cu2+(aq) + 4NH3(aq) ⇌ Cu(NH3)42+(aq);
2
[Cu(NH 3 ) 4 ]
Kf
[Cu 2 ][NH 3 ]4
• Kf = K1 x K2 x K3 x K4 = 1.1 x 1013
Complex Ions and Solubility