Predicting the pH of Salt Solutions

To determine the pH of a salt solution, you need to consider whether the salt cations or
anions (or both) hydrolyze. Hydrolysis is a Brønsted acid-base reaction of an ion with
water to give excess H+ or OH–. All acidic or basic ions hydrolyze.

CATIONS
Most cations are acidic!!
Hydrolysis of acidic cations gives rise to H+ (also written as H3O+). Examples include:

(a) Amine-type cations such as NH4+, CH3NH3+, etc.

NH4+ + H2O NH3 + H3O+

CH3NH3+ + H2O CH3NH2 + H3O+

(b) Metal ions with a high charge to radius ratio such as H+, Be2+, Al+3, Cr+3, and Fe+3.

Here it is useful to think of a 2-step process:

(1) hydration (universal for ions)
Al+3 + 6 H2O Al(H2O)63+(aq)

(2) hydrolysis
Al(H2O)63+ + H2O Al(OH)(H2O)52+ + H3O+

The exceptions are neutral (no cations are basic!!) Neutral ions do not hydrolyze.
Examples of neutral cations are metal ions which are relatively large for their charge:

Li+, Na+, K+, Rb+, Cs+, Ba+2, Sr+2, Ca+2 (cations associated with the most basic
hydroxides)

ANIONS
Most anions are basic!!
Hydrolysis of a basic anions gives rise to OH–:

acetate: C2H3O2– + H2O HC2H3O2 + OH–

cyanide: CN– + H2O HCN + OH–

bicarbonate: HCO3– + H2O H2CO3 + OH– H2O + CO2(g) + OH–

Most of the exceptions are neutral. Neutral ions do not hydrolyze. They are all
conjugate bases of strong, or moderately strong, acids. The most common neutral
anions are

Cl–, Br–, I–, NO3–, ClO4–, and SO42–.

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A few anions are acidic. They typically contain hydrogen and are conjugate bases of
strong, or moderately strong, acids. Examples of acidic anions are HSO4– (conjugate to
H2SO4), HC2O4– (conjugate to H2C2O4 = oxalic acid), and HC4H4O6– (conjugate to
H2C4H4O6 = tartaric acid). They hydrolyze in water:

HSO4– + H2O SO42– + H3O+