Hydrolysis of salts

A salt is produced when a base and acid neutralize each other. On this basis, four classes of salts are
possible:

1. a salt of a strong acid and a strong base (SA–SB);

2. a salt of a weak acid and a strong base (WA–SB);

3. a salt of a strong acid and a weak base (SA–WB);

4. a salt of a weak acid and a weak base (WA–WB).

Sodium chloride solution (made with pure water), is neutral with a pH of 7 at 25°C. This may lead us to
suppose that solutions of all ionic salts are neutral. In fact, only solutions of salts made from strong acids
and strong bases are always neutral. Solutions of other salts are usually either acidic or basic. The
reasons for this behaviour are that:

1. These salts react with the water producing a weak acid or a weak base. 2. Since the weak acid or weak
base is only partially ionized in water, formation of these molecules ties up hydroxide or hydronium
ions. 3. This produces unequal concentrations of hydronium and hydroxide ions, and the resulting
solution of salt is then acidic or basic. Reactions with water are called hydrolysis, and the reactions of a
salt with water are referred to as salt hydrolysis. We now look at one example of this effect.

Hydrolysis of a salt of a weak acid and a strong base Using sodium ethanoate (CH3COO,Na) as an
example, the ions present in an aqueous solution of this salt are

H2O CH3COO,Na(s) — CH3COO(aq) Na(aq) (from the salt) 2H2O(l) \=== \ H3O(aq) OH(aq) (from the
water) The potential products of any reaction between the ions in solution are NaOH (from the reaction
of Na(aq) and OH(aq)) and CH3COOH (from the reaction of CH3COO(aq) and H3O(aq)). The NaOH is fully
ionized in solution, but the ethanoic acid is only partially ionized. This means that [OH(aq)] [H3O(aq)]
and the solution is basic. Generalizing,

Solutions of salts of weak acids and strong bases are basic.

Consideration of the possible reactions in solutions of the other classes of salts leads to the conclusions
given in Table 16.3. ( chemistry third edition, Rob Lewis and Wynne Evans,295)
ACID-BASE PROPERTIES OF SALT SOLUTIONS

Up to now you've seen that cations of weak bases (such as NH4 +) are acidic, anions of weak acids (such
as CN-) are basic, anions of polyprotic acids (such as H2P04 -) are often acidic, and small, highly charged
metal cations (such as AI3+) are acidic. Therefore, when salts containing these ions dissolve in water, the
pH of the solution is affected. You can predict the relative acidity of a salt solution from the relative
ability of the cation and/or anion to react with water. Salts That Yield Neutral Solutions A salt consisting
of the anion of a strong acid and the cation of a strong base yields a neutral solution because the ions do
not react with water. To see why the ions don't react, let's consider the dissociation of the parent acid
and base. When a strong acid such as HN03 dissolves, complete dissociation takes place: HN03(1) +
H20(l) ---» N03 -(aq) + H30+(aq) H20 is a much stronger base than N03 -, so the reaction proceeds
essentially to completion. The same argument can be made for any strong acid: the anion of a strong
acid is a much weaker base than water. Therefore, a strong acid anion is hydrated, but nothing further
happens. Now consider the dissociation of a strong base, such as NaOH: H,O + _ NaOH(s) � Na (aq) +
OH (aq) When Na + enters water, it becomes hydrated but nothing further happens. The cations of all
strong bases behave this way. The anions of strong acids are the halide ions, except F-, and those of
strong oxoacids, such as N03 - and CI04 -. The cations of strong bases are those from Group l AO) and
Ca2+ , Sr2+, and B a2+ from Group 2A(2). Salts containing only these ions, such as NaCI and B a(N03h
yield neutral solutions because no reaction takes place between the ions and water. Salts That Yield
Acidic Solutions A salt consisting of the anion of a strong acid and the cation of a weak base yields an
acidic solution because the cation acts as a weak acid, and the anion does not react. For example, NH4Cl
produces an acidic solution because the NH4 + ion, the cation that forms from the weak base NH3, is a
weak acid, and the CIion, the anion of a strong acid, does not react: H,O + _ NH4CI(s) � NH4 (aq) + Cl
(aq) [dissolution and hydration] NH4 +(aq) + H20(I) � NH3(aq) + H30+(aq) [dissociation of weak acid] As
you saw earlier, small, highly charged metal ions make up another group of cations that yield H30+ in
solution. For example, Fe(N03h produces an acidic solution because the hydrated Fe 3+ ion acts as a
weak acid, whereas the N03 - ion, the anion of a strong acid, does not react: Fe(N03h(s) + 6H20(I) �
Fe(H20)6 3 +(aq) + 3N03 -(aq) [dissolution and hydration] Fe(H20)6 3 +(aq) + H20(l) ::::;::::=:::
Fe(H20)sOH 2 +(aq) + H3 0 +(aq) [dissociation of weak acid) A third group of salts that yield H30+ ions in
solutions consists of cations of strong bases and anions of polyprotic acids that still have one or more
ionizable protons. For example, NaH2P04 yields an acidic solution because Na + , the cation of a strong
base, does not react, while H2P04 -, the first anion of the weak polyprotic acid H3P04, is also a weak
acid: H,O + _ NaH2P04(S) � Na (aq) + H2P04 (aq) H2P04 -(aq) + H20(l) � HPO /-(aq) + H 3 0 +(aq) Salts
That Yield Basic Solutions [dissolution and hydration] [dissociation of weak acid] A salt consisting of the
anion of a weak acid and the cation of a strong base yields a basic solution in water because the anion
acts as a weak base, and the cation does not react. The anion of a weak acid accepts a proton from
water to yield OH- ion. Sodium acetate, for example, yields a basic solution because the Na+ ion, the
cation of a strong base, does not react with water, and the CH3COOion, the anion of the weak acid
CH3COOH, acts as a weak base: CH3COONa(s) � Na+(aq) + CH3COO -(aq) [dissolution and hydration]
CH3COO -(aq) + H20(l) ::::;::::=::: CH3COOH(aq) + OH -(aq) [reaction of weak base] Table 1 8.3 displays
the acid-base behavior of the various types of salts in water.
Salts of Weakly Acidic Cations and Weakly Basic Anions

The only salts left to consider are those consisting of a cation that acts as a weak acid and an anion that
acts as a weak base. In these cases, both ions react with water, so the overall acidity of the solution
depends on the relative acid strength (Ka) or base strength (Kb) of the separated ions. For example, will
an aqueous solution of ammonium cyanide, NH4CN, be acidic or basic? First, we write equations for any
reactions that occur between the separated ions and water. Ammonium ion is the conjugate acid of a
weak base, so it acts as a weak acid: NH4 +(aq) + H20(l) � NH3(aq) + H30+(aq) Cyanide ion is the anion
of the weak acid HCN and it acts as a weak base: CN-(aq) + H20(l) � HCN(aq) + OH-(aq) The reaction
that goes farther to the right will have the greater influence on the pH of the solution, so we must
compare the Ka of NH4 + with the Kb of CN-. But only molecular compounds are listed in Ka and Kb
tables, so we first have to calculate these values for the ions: 1 .0X lO- 1 4 -10 6 5 = S.7X IO 1 .7 X lO _ Kw
l .OX 10-1 4 -5 Kb of CN = Ka of HCN 6.2X lO- 10 = 1.6x iO The difference in magnitude of the equilibrium
constants (Kb = 3 X 1 04Ka) tells us that the acceptance of a proton from H20 by CN- proceeds much
further than the donation of a proton to H20 by NH4 +. In other words, because Kb of CN- > Ka of NH4 +,
the NH4CN solution is basic. (Principles of general chemistry, Silberberg, 603-606)

Salt is simply another name for ionic compound. When a salt dissolves in water, we assume that it
breaks up into its ions, which move about independently, at least in dilute solutions. Under certain
conditions, these ions can behave as acids or bases. In this section we explore such reactions.

Salts That Produce Neutral Solutions

Recall that the conjugate base of a strong acid has virtually no affinity for protons in water. This is why
strong acids completely dissociate in aqueous solution. Thus, when anions such as and are placed in
water, they do not combine with H and have no effect on the pH. Cations such as K and Na from strong
bases have no affinity for H, nor can they produce H, so they too have no effect on the pH of an aqueous
solution. Salts that consist of the cations of strong bases and the anions of strong acids have no effect on
[H] when dissolved in water. This means that aqueous solutions of salts such as KCl, NaCl, NaNO3, and
KNO3 are neutral (have a pH of 7).

Salts That Produce Basic Solutions

In an aqueous solution of sodium acetate (NaC2H3O2), the major species are What are the acid–base
properties of each component? The Na ion has neither acid nor base properties. The ion is the conjugate
base of acetic acid, a weak acid. This means that has a significant affinity for a proton and is a base.
Finally, water is a weakly amphoteric substance.

The pH of this solution will be determined by the ion. Since is a base, it will react with the best proton
donor available. In this case, water is the only source of protons, and the reaction between the acetate
ion and water is (14.7) Note that this reaction, which yields a base solution, involves a base reacting with
water to produce hydroxide ion and a conjugate acid. We have defined Kb as the equilibrium constant
for such a reaction. In this case, The value of Ka for acetic acid is well known But how can we obtain the
Kb value for the acetate ion? The answer lies in the relationships among Ka, Kb, and Kw. Note that when
the expression for Ka for acetic acid is multiplied by the expression for Kb for the acetate ion, the result
is Kw: This is a very important result. For any weak acid and its conjugate base, Thus, when either Ka or
Kb is known, the other can be calculated. For the acetate ion, This is the Kb value for the reaction
described by Equation (14.7). Note that it is obtained from the Ka value of the parent weak acid, in this
case acetic acid. The sodium acetate solution is an example of an important general case. For any salt
whose cation has neutral properties (such as Naor K) and whose anion is the conjugate base of a weak
acid, the aqueous solution will be basic. The Kb value for the anion can be obtained from the
relationship Equilibrium calculations of this type are illustrated in Sample Exercise 14.18. Salts as Weak
Bases Calculate the pH of a 0.30 M NaF solution. The Ka value for HF is . Solution The major species in
solution are Since HF is a weak acid, the F ion must have a significant affinity for protons, and the
dominant reaction will be which yields the Kb expression The value of Kb can be calculated from Kw and
the Ka value for HF (Chemistry, Seventh Edition, Zumdahl, 655)