Salt, Hydrolysis of Salts

SALT:

Neutralization product of acid base reactions.

Classification by their origin:

1. Arrhenius-type acid + base: NaOH + HCl = NaCl + H2O Brnsted-type base + acid: NH3 + HCl = NH4Cl Lewis-type acid + base reaction: AgCl + 2NH3 = [Ag(NH3)2]Cl

2.

3.

Classification by their composition:

a) Normal (neutral) salts: Salts as results of a stoichiometric neutralization reaction: 2NaOH + H2SO4 = Na2SO4 + 2H2O 3KOH + H3PO4 = K3PO4 + 3H2O

Classification by their composition:

b)

Acid salts: Salts formed by an incomplete neutralization of a polybasic acid. KOH + H3PO4 = KH2PO4 + H2O
2KOH + H3PO4 = K2HPO4 + 2H2O

NaOH + H2CO3 = NaHCO3 + H2O

Classification by their composition:

c) Base salts are products of a partial neutralization of a polyvalent (polyacidic) base. Bi(OH)3 + HNO3 = Bi(OH)2NO3 + H2O

d)

Mixed salts Salts formed in a reaction of a polyacidic base with two different acids (One cation, two different anions) Ca(OH)2 + HCl + HOCl = CaCl(OCl) + 2H2O

e)

Double salts: Composed of two different cations and one kind of anion K2SO4 + Al2(SO4)3 = 2KAl(SO4)2 (alum) When dissolved, they dissociate into all of their ionic components: KAl(SO4)2 = K+ + Al3+ + 2SO42-

or, e.g.: (NH4)2Fe(SO4)2 (Mohrs salt)

When dissolved in water:

(NH4)2Fe(SO4)2 = 2NH4+ + Fe2+ + 2SO42-

f)

Complex salts are coordination compounds composed of a non-dissociable complex ion and a dissociable counterion Salt with a complex cation: [Ag(NH3)2]Cl diamminesilver(l) chloride
when dissolved: [Ag(NH3)2]Cl = [Ag(NH3)2]+ + ClSalt with a complex anion:

Na3[Ag(S2O3)2] Sodium dithiosulphatoargentate (I)

In aqueous solution: Na3[Ag(S2O3)2] = 3Na+ + [Ag(S2O3)2]3-

Hydrolysis of Salts
Hydrolysis: an acid-base reaction between water and the ion(s) of the dissolved salt.

Preliminary consideration: 1. Water is neutral and amphoteric: H2O H+ + OH2. Dissolved salts exist in ionized form: NaCl Na+ + Cl-

3.

If any of the ions in solution has acid-base character, it will affect the self-ionization equilibrium of the solvent.

4.

Cations of strong bases have no acid-base character while those of weak bases are acidic.
K+ + H2O = N. R. NH4+ + H2O NH3 + H3O+

5.

Anions of strong acids have no acid-base character while those of weak asids are bases. SO42- + H2O = N. R. CN- + H2O HCN + OH-

Qualitative Aspects
1. No hydrolysis: Salts of strong acids and strong bases are neutral in solution. (NaCl, K2SO4, CaCl2.)

2.

Anion-hydrolysis: Salts of weak acids and strong bases are basic in solution.
Dissolution: KCN K+ + CNHydrolysis: CN- + H2O HCN + OH-

Qualitative Aspects
3. Cation-hydrolysis: Salts of strong acids and weak bases are acidic in solution.
Dissolution: NH4Cl NH4+ + ClHydrolysis: NH4+ + H2O NH3 + H3O+

4.

Cation-anion hydrolysis: Salts of weak acids and weak bases can be acidic, basic or neutral in solution, owing to the hydrolysis of both ions. The reaction depends on relative acid-base strengths.
Dissolution: NH4CN NH4+ + CNCation-Hydrolysis: NH4+ + H2O NH3 + H3O+ Anion-hydrolysis: CN- + H2O HCN + OH-

Quantitative Aspects
Two equilibria coexist in aqueous solutions of hydrolyzable salts.

1.

Self ionization of water:

H2O H+ + OHKw = [H+] [OH-]

2.

Hydrolysis of a cation (C+) or an anion (A-)

a) C+ + H2O COH + H+ K h(cation) = [H+] = [COH] [H+] [COH] Kw = [C+] [C+] [OH-] Kh[C+] and pH = - log Kw = K b Kh[C+]

Quantitative Aspects
2. Hydrolysis of a cation (C+) or an anion (A-)
b) A- + H2O HA + OH-

K h(anion) =

[HA] [OH-] = [A-]

[HA] Kw [A-] [H+]

Kw = K a

[OH-] =

Kh[A-]

and pH = 14- pOH