Chapter 15: Application of Aqueous Equilibria

15.1 Solutions of Acids and Bases Containing a Common Ion

The common ion in a weak acid and base, such as HF and NH4Cl, is the anion (weak
acid) (F-) and cation (weak base) (NH4+)

For example NaF (s) ----- Na+ (aq) + F- (aq) (complete dissociation)

HF (aq) ----- H+ (aq) + F- (aq) (partially dissociation)

Dissociation constant Ka = [H+] [F-]/[HF]

NH4Cl (s) ---- NH4+ (aq) + Cl- (aq) (complete dissociation)

NH3 (aq) + H2O (l) ---- NH4+ (aq) + OH- (aq) (partially dissociation)

Dissociation constant Kb = [NH4+] [OH-]/[NH3]

Equilibrium Calculation Involving Weak Acids and Weak Bases plus a Common Ion:
Procedures similar to the calculation of pH of an acid or base

Example 15.1 Acidic solutions containing common ions (p682-683)

15.2 Buffer Solutions

Buffer solution: one that resists a change in its pH when either H+ or OH- ions are
added.

Buffer solutions: Weak acid + its salt such as HF + NaF

or weak base + its salt such as NH3 + NH4Cl

Applications: In a number of chemical reactions, including biological reactions, it is

desired to maintain certain pH.
Examples 15.2 and 15.3 pH of buffer solution and pH change in buffer solution (P684-
686).

How does Buffer solution work?

In a buffer solution (HA + NaA), what is going to occur when OH- ions are added?

OH- + HA ------ A- + H2O

OH- will be neutralized with HA and produce A-.

[H+] = Ka [HA]/[ A-] ----- depending on the ratio of [HA]/[A-]

15.3 Buffer Capacity

The buffer capacity of a buffered solution represents the amount of protons or
hydroxide ions (H+ or OH-) the buffer can absorb without a significant change in pH.

Henderson-Hasselbalch equation to estimate the equilibrium pH of buffer solution:

pH=pKa + log ([A-]/[HA])

for dissociation equation HA = A- + H+

Assume [HA]Equilibrium = [HA]0 initial

[A-]Equilibrium = [NaA]0 initial

Also equilibrium constant Ka = [A-]Equilibrium [H+]/[HA]Equilibrium

Therefore pH=pKa + log ([A-]/[HA])= pKa + log ([NaA]0/[[HA]0)

Example 15.7 Adding strong acid to a buffered solution II (P693-694)

Example 15.8 Preparing a buffer (p695-696)

15.4 Titrations and pH Curves
Titration: The use of a known concentration of acid (or base) to determine the
unknown concentration of a base (or acid).

Titration curve or pH curve: a plot of the pH of the solution being analyzed as a

function of the amount of titrated added.

OH- (aq) + H+(aq) -------- H2O(l)

Equivalent Point: The point where exactly enough OH- (or H+) is added to react all the
H+ (or OH-) originally present.

Indicator: a dye that will change color at the equivalent point of acid-base titration
a.) Strong acid-base titration, such as HCl and NaOH titration
b.) Titration of weak acid with strong base, such as acidic acid (HAc) and NaOH
c.) Titration of weak base with strong acid, such as NH3.H2O and HCl.

The calculation of pH or the equilibrium constant Ka or Kb involves two steps in case

b.) and case c.)

1.) A stoichiometry problem: the reaction of OH- (or H+) with weak acid (or weak
base) is assumed to run to completion, and the concentrations of the acid (or
base) remaining and the conjugate base (or acid) formed are determine.
2.) An equilibrium problem. The position of the waek acid (or the weak base)
equilibrium is determined, and the pH is calculated.

Example 15.9 Titration of a weak acid (p705-706)

Example 15.10 Calculation of Ka (p707-708)

15.5 Acid-Base Indicators (self-study)

15.6 Solubility Equilibrium and the Solubility Product

Precipitation reactions and the solubility rules discussed in Chapter 11.

Dissolving of solids in water is a reverse reaction of precipitation. For example,

CaF2 (s) dissolved in water, we have the following equilibrium reaction:

CaF2 (s) ------- Ca2+ (aq) + 2F- (aq)

Solubility product constant or solubility product Ksp = [Ca2+] [F-]2

For a more general precipitation reaction,

MαXβ (s) ----- α Mβ + (aq) + β Xα- (aq)

Ksp= [Mβ +]α [Xα-]β

Solubility: the concentration of solids dissolved in aqueous solution

Example 15.13 Calculating KSP from solubility (p719-720)

Example 15.14 Calculating solubility from Ksp (p720-721)
Common Ion Effect: Addition of ions in common to partially soluble compounds to
reduce its solubility.

For example AgCl (s) ------ Ag+(aq) + Cl- (aq)

By adding KCl to the solution, we incrase the concentration of the common ion Cl-
and will thus shift the equilibrium to the left.

Example 15.15 Solubility and Common Ions (p723-724)

15.7 Precipitation and Qualitative Analysis

Precipitation is a reverse process of dissolving of partially soluble solids

Ion Product (Q) —expression is similar to solubility product KSP but using initial
concentrations of ions rather than equilibrium concentrations of ions in KSP

For example CaF2 (s) ------- Ca2+ (aq) + 2F- (aq)

Q = [Ca2+]0 [F-]20

a.) If Q > KSP, precipitation coours and will continue until the concentrations are
reduced to the point that they satisfy KSP.
b.) If Q < KSP, no precipitation occurs.

Example 15.16 Determining precipitation conditions (p725-726)

Example 15.17 Precipitation (p726-727)