SALT HYDROLYSIS

A salt is any ionic substance other than acids, bases or peroxides

o Anything not containing H+1, OH-1, O2-2

A salt is formed by the reaction of an acid and a base

o HCl+ KOH  H2O + KCl
o 2H3PO4 + 3Ca(OH)2  6H2O + Ca3(PO4)2

the ions of many salts hydrolyze (react) with water once dissolved
this means that when the salt is dissolved in water, the IONS can as act
Brønsted acids and/or bases
when this happens, the water’s 1:1 ratio of [H+1]:[OH-1] is upset, resulting in
a change of water’s normal pH reading of 7

an example of a salt’s cation reacting with water:

NH4+1(aq) + H2O ↔ H3O+1(aq) + NH3(aq) (positive ion acts as an acid)

Ka expression must be used here!

An example of a salt’s anion reacting with water:

CO3-2(aq) + H2O ↔ HCO3-1(aq) + OH-1(aq) (negative ion acts as a base)

Kb expression must be used here!

Predicting if the cation hydrolyzes in water:

a) metals from group IA and IIA do NOT hydrolyze
b) non-metal ions usually hydrolyze

Predicting if the anion hydrolyzes in water:

a) find out what the conjugate acid would be
b) if the conjugate acid is a strong acid, there will be no reaction (strong
acids dissociate 100% into their ions)
A/ The Salt of a Strong Acid and a Strong Base:

eg) potassium chloride KCl(aq) = K+1(aq) + Cl-1(aq)

K+1(aq) + H2O  no reaction because K is a group IA metal

Cl-1(aq) + H2O HCl(aq) + OH-1(aq)

HCl is a strong acid therefore no reaction

Therefore the solution is neutral; pH = 7

B/ The Salt of a Weak Acid and a Strong Base:

eg) potassium fluoride KF(aq) = K+1(aq) + F-1(aq)

K+1(aq) + H2O  no reaction because K is a group IA metal

F-1(aq) + H2O HF(aq) + OH-1(aq)

HF is a weak acid Ka = 6.7*10-4

Therefore the solution is basic (anion acts as a base, increasing the [OH-1]; pH > 7

C/ The Salt of a Strong Acid and a Weak Base:

eg) C6H5NH2Cl(aq) = C6H5NH2+1(aq) + Cl-1(aq)

C6H5NH2+1(aq) + H2O  H3O+1(aq) + C6H5NH(aq)

Cl-1(aq) + H2O HCl(aq) + OH-1(aq)

HCl is a strong acid therefore no reaction

Therefore the solution is acidic (cation acts as an acid, increasing the [H+1]; pH < 7

D/ The Salt of a Weak Acid and a Weak Base:

If Ka = Kb, pH = 7
If Ka > Kb, pH < 7 not far from pH of 7 in any case
If Ka < Kb, pH > 7
Eg) What is the pH of a 0.25 mol/L solution of sodium fluoride?

NaF  Na+1 + F-1

0.25 0.25 0.25

Na+1 + H2O  no reaction (Group IA metal)

F-1 + H2O  HF + OH-1 (HF is a weak acid therefore reaction proceeds)

F-1 + H2O  HF + OH-1

I 0.25 0 0
Rx -x +x +x
E ≈0.25 x x

Kb = Kw/Ka pOH = -log [OH-1]

= 1*10-14/6.7*10-4 = -log(1.9*10-6)
= 1.5*10-11 = 5.7

Kb = [HF] [OH-1]/[ F-1] pH = 14-5.7

1.5*10-11 = (x)(x)/0.25 pH = 8.3 (basic)
x = 1.9*10-6 mol/L = [OH-1]

eg) Calculate the pH of a 0.5 mol/L aqueous solution of pyridinium chloride, C5H6NCl.

C5H6NCl  C5H6N+1 + Cl-1

0.5 0.5 0.5

C5H6N +1 + H2O  H3O+1 + C5H5N

Cl-1 + H2O  HCl + OH-1 (HCl is a strong acid therefore no reaction)

C5H6N +1 + H2O  H3O+1 + C5H5N

I 0.5 0 0
Rx -x +x +x
E ≈0.5 x x

Ka = [H3O+1] [C5H5N]/[C5H6N +1] pH = -log[H+1]

6.8*10-6 = (x)(x)/0.5 = -log(0.00184)
x = 1.84*10-3 mol/L = [H+1] = 2.73