Practice Problem #2: acid-base equilibrium in solutions

Joy Al Haddad, Mohamad Soloh - B06-208

Theoretical introduction:
Salt hydrolysis is a reaction in which one of the ions from a salt reacts with water,
forming either an acidic or basic solution:

● Salts that are derived from the neutralization of a weak acid by a strong
base will always produce salt solutions that are basic.
● Salts that are derived from the neutralization of a strong acid by a weak
base will always produce salt solutions that are acidic.
● A salt that is derived from the reaction of a strong acid with a strong base
forms a solution that has a pH of 7.

In some cases, ions of a salt containing a weak electrolyte ion dissolved in water
can enter into exchange reactions with water molecules, forming weakly
dissociating compounds. In such cases talk about the hydrolysis of the salt - the
reaction of its metabolic decomposition by water. In fact, hydrolysis is the reverse
of the neutralization reaction. Due to the endothermic nature of this process, it
intensifies with heating. Hydrolysis occurs when the salt is formed by a weak acid
residue and a strong base cation (anion hydrolysis), a strong acid residue and a
weak base cation (cation hydrolysis), or a weak acid residue and a weak base
cation (hydrolysis by cation and anion) A quantitative characteristic of the depth
of hydrolysis is the hydrolysis constant. This value results from the equilibrium
constant of the hydrolysis reaction.
The degree of hydrolysis increases with dilution, and acidity changes most
for salts of weaker acids (similarly to bases). It is possible to shift the equilibrium
of the hydrolysis reaction towards products in accordance with the principle of Le
Chatelier in the following ways:
1) Increase temperature, since hydrolysis proceeds with heat absorption;
2) Decrease of concentration, since the degree of hydrolysis grows with dilution
of the solution;
3) Change pH, leveling the effect of hydrolysis.
 1) Hydrolysis of salts:
Experience 1.1. The reaction of the medium in solutions of various salts
a. In eight test tubes, add 5 ml of distilled water.
b. Add 5 drops of the following salts, into each test tube, respectively:
first, ammonium acetate 𝐶𝐻3𝐶𝑂𝑂𝑁𝐻4 ; in the second - aluminum
chloride 𝐴𝑙𝐶𝑙3 ; in the third, sodium carbonate 𝑁𝑎2𝐶𝑂3; in the fourth,
sodium chloride 𝑁𝑎𝐶𝑙 ; the fifth is zinc(II) chloride 𝑍𝑛𝐶𝑙2 ; in the sixth,
sodium acetate 𝐶𝐻3𝐶𝑂𝑂𝑁𝑎 ; in the seventh - ammonium carbonate
(𝑁𝐻4)2𝐶𝑂3, in the eighth - sodium sulfite 𝑁𝑎2𝑆𝑂3.
c. Add 3 drops of universal indicator in the resulting solutions.

Fig1-colors observed after dropping universal indicator

Results:
For tube n1: ammonium acetate 𝐶𝐻3𝐶𝑂𝑂𝑁𝐻4 is a salt of a weak acid and a weak
base. Both components are equally hydrolysed:
+ + −
𝑁𝐻4 + 𝐻2𝑂 ↔ 𝑁𝐻3 + 𝐻3𝑂 ; 𝐶𝐻3𝐶𝑂𝑂 + 𝐻2𝑂 ↔ 𝐶𝐻3𝐶𝑂𝑂𝐻 + 𝐻𝑂
𝐶𝐻3𝐶𝑂𝑂𝑁𝐻4 + 𝐻2𝑂 ↔ 𝑁𝐻4𝑂𝐻 + 𝐶𝐻3𝐶𝑂𝑂𝐻
Since both dissociation constants are almost equal we’ll end up by a pH=7.

For tube n2: Due to cation hydrolysis (which occurs when the acid produced is
strong and the base produced is weak then cation reacts with water to give an
acidic solution), the aqueous solution of aluminum chloride is acidic:
3+ + − −
𝐴𝑙 + 3𝐻2𝑂 ↔ 𝐴𝑙(𝑂𝐻)3 + 3𝐻 ; 𝐶𝑙 + 𝐻2𝑂 ↔ 𝐻𝐶𝑙 + 𝐻𝑂
𝐴𝑙𝐶𝑙3 + 3𝐻2𝑂 ↔ 𝐴𝑙(𝑂𝐻)3 + 3𝐻𝐶𝑙.

For tube n3: anionic hydrolysis (which occurs when the acid produced is weak
and the base produced is strong), so anion reacts with water to give a basic
+ 2− + −
solution: 2𝑁𝑎 + 𝐶𝑂3 + 2𝐻2𝑂 ↔ 2𝑁𝑎 + 2𝑂𝐻 + 𝐻2𝐶𝑂3 ;
𝑁𝑎2𝐶𝑂3 + 2𝐻2𝑂 ↔ 2𝑁𝑎𝑂𝐻 + 𝐻2𝐶𝑂3.

For tube n4: sodium chloride 𝑁𝑎𝐶𝑙 is a salt with strong acid and strong base so it
doesn’t undergo hydrolysis (neither ion is capable of hydrolyzing). A salt that is
derived from the reaction of a strong acid with a strong base forms a solution that
has a pH of 7.

For tube n5: the hydrolysis of a salt of strong acid and weak base results in a
acidic solution: 𝑍𝑛𝐶𝑙2 + 2𝐻2𝑂 ↔ 2𝐻𝐶𝑙 + 𝑍𝑛(𝑂𝐻)2

For tube n6: sodium acetate is the salt of a weak acid (acetic acid) and a strong
base (sodium hydroxide), any anion derived from a weak acid will be a weak
−
base: 𝐶𝐻3𝐶𝑂𝑂 + 𝐻2𝑂 ↔ 𝐶𝐻3𝐶𝑂𝑂𝐻 + 𝐻𝑂 ;
𝐶𝐻3𝐶𝑂𝑂𝑁𝑎 + 𝐻2𝑂 ↔ 𝐶𝐻3𝐶𝑂𝑂𝐻 + 𝑁𝑎𝑂𝐻

For tube n7: ammonium carbonate dissociates completely to form ammonium

cations and carbonate anions when dissolved in water, resulting in a basic
+ +
solution: 𝑁𝐻 4
+ 𝐻2𝑂 ↔ 𝑁𝐻3 + 𝐻3𝑂 (weak acid) ;
2− − −
𝐶𝑂 3
+ 𝐻2𝑂 ↔ 𝐻𝐶𝑂 3
+ 𝑂𝐻 (strong base)
+ 2−
(𝑁𝐻4)2𝐶𝑂3 + 𝐻2𝑂 ↔ 2𝑁𝐻 4
+ 𝐶𝑂 3

For tube n8: Sodium sulphite is a salt of a strong base and weak acid. So, its
aqueous solution is basic (pH>7):
2− − −
𝑆𝑂 3
+ 𝐻2𝑂 ↔ 𝐻𝑆𝑂 3
+ 𝑂𝐻 ; 𝑁𝑎2𝑆𝑂3 + 𝐻2𝑂 ↔ 𝑁𝑎𝑂𝐻 + 𝐻2𝑆𝑂3
The presence of excess hydroxide ions, formed by hydrolysis, is responsible for
the basic nature of the salt’s solution.

Fig2 - pH scale

Experience 1.2. Irreversible hydrolysis

a)
1. In a test tube add 5 drops of a 0.5 M solution of aluminum chloride and 1
ml of a solution of 0.1 M sodium acetate.
2. Gently heat the tube. Observe formation of precipitation of the basic
aluminum salt.
3. The molecular and ionic equation for the formation of aluminum acetate:
𝐴𝑙𝐶𝑙3 + 3𝐶𝐻3𝐶𝑂𝑂𝑁𝑎 → 𝐴𝑙(𝐶𝐻3𝐶𝑂𝑂)3 + 3𝑁𝑎𝐶𝑙 ;
3+ − + − 3+ − + −
𝐴𝑙 + 3𝐶𝑙 + 3𝑁𝑎 + 3𝐶𝐻3𝐶𝑂𝑂 = 𝐴𝑙 + 3𝐶𝐻3𝐶𝑂𝑂 + 3𝑁𝑎 + 3𝐶𝑙

fig3-formation of precipitation
Experience 1.3. Factors affecting the degree of hydrolysis
b) The effect of temperature on the degree of hydrolysis
1. In a test tube add 10 drops of sodium acetate and dissolve in 2 ml of
distilled water, and then add 2 drops of phenolphthalein to the solution.
2. Mark observation: before heating the color of the solution was transparent.
3. Gently heat the tube with the solution: the color of the obtained solution is
fuchsia. Which means that the hydrolysis equilibrium shifted again.

fig4-change in color before and after heating