Acid-Base Equilibria

• Acid-Base Properties of Water

• Water is an amphoteric substance. It is a weak electrolyte and is a poor
conductor of electricity. However, it undergoes dissociation to a small extent:
H2O(l) ↔ H+(aq) + OH-(aq)
2 H2O(l) ↔ H3O+(aq) + OH-(aq)
• Which are the conjugate acid-base pairs?
• Autoionization of water
• The equilibrium constant expression for the autoionization of water is given by
[H+][OH-]
Kc =
[H2O]
• The concentration of water in aqueous solutions is considered constant.
Kc [H2O] = [H+][OH-]
Kw = [H+][OH-]
• Kw is the ion-product constant of water at a specific temperature. At 25°C, Kw
has a value of 1.0 x 10-14.
 Acid-Base Equilibria
Calculate the concentration of H+ in (a) a solution in which [OH-] is 0.010 M; (b) a
solution in which [OH-] is 1.8 x 10-9 M. (Unless otherwise stated, the temperature is
25°C.)
(a) Kw = [H+][OH-] (b) Kw = [H+][OH-]
Kw 1.0 x 10-14 Kw 1.0 x 10-14
H+ = -
= H+ = =
[OH ] 0.010 [OH-] 1.8 x 10-9

H+ = 1.0 x 10-12 M H+ = 5.6 x 10-6 M

Is this solution acidic or basic? Is this solution acidic or basic?

What is the pH and pOH of each of the solutions given above?

Recall: pH = -log [H+], pOH = -log [OH-]
Acid-Base Equilibria
• Relative strengths of acids and bases
• A strong acid completely transfers its
protons while its conjugate base has
negligible tendency to be protonated.

• A weak acid only partially dissociates and its

conjugate base is a weak base.

• A substance with negligible acidity (e.g.

CH4) has a conjugate base that is very
strong.
 Acid-Base Equilibria
• Strong acids and strong bases
HCl(aq) ↔ H+(aq) + Cl-(aq)
Kc = [H+][Cl-]
[HCl]
• Since HCl is a strong acid and dissociates almost completely in the solution,
[HCl] is almost zero. Therefore,
HCl(aq)  H+(aq) + Cl-(aq)
Kc = [H+][Cl-] ≈ ∞
[HCl]
• [H+] = [Cl-] = initial concentration of HCl before dissociation took place]
• The above trend goes for strong bases.

(a) Calculate the pH of 0.10 M HNO3

(b) Calculate the pH of 1.0 x 10-10 M HCl
(c) Calculate the pH of 0.0011 M Ca(OH)2
 Acid-Base Equilibria
• Weak acids
• Consider the ionization of a weak acid in water:

• Ka is the acid dissociation constant at a specific temperature.

• Just like in molecular equilibrium, an ICE table is used in solving acid-base

equilibrium problems.
 Acid-Base Equilibria
• Weak acids

• The following approximation can be used since Ka is very small:

 Acid-Base Equilibria
• Weak acids

• When can we do the approximation? The approximation is valid if the result is

5% of the initial concentration.

The pH of a 0.10 M solution of formic acid (HCOOH) is 2.39. What is the Ka of the
acid? (1.8 x 10-4)
 Acid-Base Equilibria
• Percent ionization
• Another measure of acid strength is percent ionization which has the formula:

• The extent of dissociation of a weak acid depends on

the initial concentration of the acid.
 Acid-Base Equilibria
• Weak bases and Base dissociation constant

What is the pH of a 0.26 M methylamine solution (Kb = 4.4 x 10-4)?

What is the value of Ka for the conjugate acid of methylamine?

• Acid-base properties of Salts

• A salt is one of the products of an acid-base reaction (aside from water).
• The cation of a salt is from a base and its anion is from an acid.
• Salt hydrolysis refers to the reaction of a cation or an anion of a salt, or both, with
water.
• Salts can be neutral, acidic, or basic depending on the strength of the acid and
base that reacted to form the salt.

• The conjugate base has a Kb value at a specific temperature. What is the value
of Kb for acetate anion?
 Acid-Base Equilibria
• Acid-base properties of Salts
• If a strong acid and a strong base react, the resulting salt is neutral.
• If a strong acid and a weak base react, the resulting salt is acidic.
• If a weak acid and a strong base react, the resulting salt is basic.
• If a weak acid and a weak base react, the pH of the resulting solution depends
on the Kb of the conjugate base and Ka of the conjugate acid.
 Acid-Base Equilibria
• Acid-base properties of Salts
Tell whether the following salts are neutral, acidic or basic:
(a) LiClO4
(b) Na3PO4
(c) NH4CN

Calculate the pH of a 0.24 M sodium formate solution (HCOONa).

Ka for HCOOH = 1.7 x 10-4

Calculate the pH of a 0.10 M NH4Cl solution. The Kb value for NH3 = 1.8 x 10-5.
 Buffers
• A buffer solution is a solution consisting of (1) a weak acid or base and (2) its salt;
both must be present. A buffer solution has the ability to resist changes in pH upon
addition of small amounts of either acid or base.

• An example of a buffer solution is made up acetic acid (CH3COOH) and acetate

anion (CH3COO-).
• If an acid is added to the system, the acetate ion will serve as a base to neutralize the
added acid:

• If a base is added to the system, the acetic acid will serve as the acid to neutralize
the added acid:

Which of the following are buffer systems? (a) KF/HF; (b) KBr/HBr;
(c) Na2CO3/NaHCO3