Applications of Aqueous

Equilibria

Dr. Sulaiman Al-Isaee

Department of Engineering
College of Applied Sciences
© 2018
The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance.
The presence of a common ion suppresses
the ionization of a weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid).
CH3COONa (s) Na+ (aq) + CH3COO- (aq)
common
ion
CH3COOH (aq) H+ (aq) + CH3COO- (aq)

NaCl CH3COOH
KCl CH3COONa
Acid dissociation
Solubility pH
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

A buffer solution has the ability to resist changes in pH upon

the addition of small amounts of either acid or base.
The effect of addition of acid or base to …

acid added base added

an unbuffered solution

acid added base added

or a buffered solution
4
How a Buffer Works: Le Chatelier’s Principle

CH3COOH(aq) + H2O(l) CH3COO–(aq) + H3O+(aq)

Added OH– reacts with Added H3O+ reacts with

CH3COOH, causing a shift to CH3COO–, causing a
the right. shift to the left.
 How a buffer works.
Buffer has more HA after Buffer has equal Buffer has more A- after
addition of H3O+. concentrations of A– and HA. addition of OH–.

H3O+ OH-

Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

H2O + CH3COOH ← H3O+ + CH3COO- CH3COOH + OH- → CH3COO- + H2O

Types of buffers
Generally buffers are of two types:
• Acidic buffers
• Basic buffers

Acidic Buffers:
An acidic buffer is a combination of a weak acid and its
salts with a strong conjugated base.
Examples:
CH3COOH/CH3COONa
H2CO3/NaHCO3
H3PO4/NaH2PO4
Types of buffers
Generally buffers are of two types:
• Acidic buffers
• Basic buffers

Basic Buffers:
A basic buffer is a combination of a weak base and its
salts with a strong conjugated acid.
Examples:
NH4OH/NH4Cl
NH3/(NH4)2CO3
 Which of the following are buffer systems? (a) KF/HF
(b) KCl/HCl, (c) Na2CO3/NaHCO3

(a) KF is a weak acid and F- is its conjugate base

buffer solution
(b) HCl is a strong acid
not a buffer solution
(c) CO32- is a weak base and HCO3- is it conjugate acid
buffer solution
3. A few drops of 0.10 M NaOH is added to a buffer solution at pH = 5.00.
The new pH could be:

A 4.98

B. 5.02

C. 8.05

D. 2.11
3. A few drops of 0.10 M NaOH is added to a buffer solution at pH = 5.00.
The new pH could be:

A 4.98

B. 5.02

C. 8.05

D. 2.11
 Acid–Base Titrations
• In a titration, a substance in a solution
of known concentration is reacted with
another substance in a solution of unknown
concentration.
• At this point, called the endpoint, the
reactants are in their stoichiometric ratio.
– The unknown solution is added slowly from an
instrument called a burette.
• A long glass tube with precise volume markings that allows
small additions of solution
• The titrant is the solution in the burette.
 Acid–Base Titrations
• In acid–base titrations, because both the reactant
and product solutions are colorless, a chemical is
added that changes color when the solution
undergoes large changes in acidity/alkalinity.
– The chemical is called an indicator.
• At the endpoint of an acid–base titration, the
number of moles of H+ equals the number of moles
of OH.
– This is also known as the equivalence point.
Acid–Base Titration
 Titration

• In this titration, NaOH is added to a dilute HCl solution. When

the NaOH and HCl reach stoichiometric proportions (the
equivalence point), the phenolphthalein indicator changes
color to pink.
Strong Acid-Strong Base Titrations
100%
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq) ionization!
OH- (aq) + H+ (aq) H2O (l) No equilibrium
Weak Acid-Strong Base Titrations
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
At equivalence point (pH > 7):
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)
Strong Acid-Weak Base Titrations
HCl (aq) + NH3 (aq) NH4Cl (aq)
H+ (aq) + NH3 (aq) NH4Cl (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)
 Which indicator(s) would you use for a titration of HNO2
with KOH ?

Weak acid titrated with strong base.

At equivalence point, will have conjugate base of weak acid.
At equivalence point, pH > 7
Use cresol red or phenolphthalein
 Solubility Equilibrium
• In saturated solutions dynamic equilibrium
exists between undissolved solids and ionic
species in solutions
• Solids continue to dissolve and ion-pairs
continue to form solids.
• The rate of dissolution process is equal to the
rate of precipitation.
 Solubility Product Constant
• General expression:
• MmXn(s) ⇄ mMn+(aq) + nXm-(aq)
• Solubility product, Ksp = [Mn+]m[Xm-]n
 Solubility and Solubility Products

Examples:
• AgCl(s) ⇌ Ag+(aq) + Cl-(aq)
• Ksp = [Ag+][Cl-] = 1.6 x 10-10
• If s is the solubility of AgCl, then:
• [Ag+] = s and [Cl-] = s
• Ksp = (s)(s) = s2 = 1.6 x 10-10
• s = 1.3 x 10-5 mol/L
 Solubility and Solubility Products

• Ag2CrO4(s) ⇌ 2Ag+(aq) + CrO42-(aq)

• Ksp = [Ag+]2[CrO42-] = 9.0 x 10-12
• If s is the solubility of Ag2CrO4, then:
• [Ag+] = 2s and [CrO42-] = s
• Ksp = (2s)2(s) = 4s3 = 9.0 x 10-12
• s = 1.3 x 10-4 mol/L
 Factors that affect solubility
• Temperature
– Solubility generally increases with temperature;
• Common ion effect
– Common ions reduce solubility
• pH of solution
– pH affects the solubility of ionic compounds in which the
anions are conjugate bases of weak acids;
• Formation of complex ion
– The formation of complex ion increases solubility
 Common Ion Effect

• Consider the following solubility equilibrium:

• AgCl(s) ⇌ Ag+(aq) + Cl-(aq); Ksp = 1.6 x 10-10;

• The solubility of AgCl is 1.3 x 10-5 mol/L at 25oC.

• If NaCl is added, equilibrium shifts left due to
increase in [Cl-] and some AgCl will precipitate out.
• For example, if [Cl-] = 1.0 x 10-2 M,
• Solubility of AgCl = (1.6 x 10-10)/(1.0 x 10-2)
• = 1.6 x 10-8 mol/L
 Effect of pH on Solubility
• Consider the following equilibrium:
Ag3PO4(s) ⇌ 3Ag+(aq) + PO43-(aq);

• If HNO3 is added, the following reaction occurs:

H3O+(aq) + PO43-(aq) ⇌ HPO42-(aq) + H2O
• This reaction reduces PO43- in solution, causing more
solid Ag3PO4 to dissolve.
• In general, the solubility of compounds such as
Ag3PO4, which anions are conjugate bases of weak
acids, increases as the pH is lowered by adding nitric
acid.
 Effect of pH on Solubility
• Consider the following equilibrium:
Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH-(aq);

• Increasing the pH means increasing [OH-] and

equilibrium will shift to the left, causing some of
Mg(OH)2 to precipitate out.
• If the pH is lowered, [OH-] decreases and equilibrium
shifts to the right, causing solid Mg(OH)2 to dissolve.
• The solubility of compounds of the type M(OH) n
decreases as pH is increased, and increases as pH is
decreased.
 Formation of Complex Ions on Solubility

• Many transition metals ions have strong affinity for

ligands to form complex ions.
• Ligands are molecules, such as H2O, NH3 and CO, or
anions, such as F-and CN-.
• Complex ions are soluble – thus, the formation of
complex ions increases solubility of slightly soluble
ionic compounds.
 Effect of complex ion formation on solubility
• Consider the following equilibria:
• AgCl(s) ⇌ Ag+(aq) + Cl-(aq); Ksp = 1.6 x 10-10
• Ag+(aq) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) ; Kf = 1.7 x 107

• Combining the two equations yields:

• AgCl(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl-(aq);
• Knet = Ksp x Kf = (1.6 x 10-10) x (1.7 x 107)
= 2.7 x 10-3
• Knet > Ksp implies that AgCl is more soluble in
aqueous NH3 than in water.
 Example1

• Calculate the solubility of AgCl in water and in 1.0 M

NH3 solution at 25oC.

• Solutions:
Solubility in water = (Ksp)
= (1.6 x 10-10) = 1.3 x 10-5 mol/L
 Example1

• Solubility of AgCl in 1.0 NH3:

• AgCl(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl-(aq)

• [Initial], M - 1.0 0.0 0.0
• [Change] - -2S +S +S
• [Equilm.] - (1 – 2S) S S


[Ag(NH 3 ) 2 ][ Cl - ] S2
K net    2.7 x 10 -3

[ NH 3 ]2 (1 - 2 S ) 2
 Example1
• Solubility of AgCl in 1.0 NH3 (continued):
S
 2.7 x 10 -3  0.052
(1 - 2 S )
• S = 0.052 – 0.104S;
• S = 0.052/1.104 = 0.047 mol/L
• AgCl is much more soluble in NH3 solution than in
water.
 Predicting Formation of Precipitate
• Qsp is ion product expressed in the same way as Ksp for a
particular system except that initial concentrations are
used instead of equilibrium concentrations.

• Qsp = Ksp  saturated solution, but no precipitate

• Qsp > Ksp  saturated solution, with precipitate
• Qsp < Ksp  unsaturated solution,
 Predicting Precipitation

• Consider the following case:

20.0 mL of 0.025 M Pb(NO3)2 is added to 30.0 mL of 0.10
M NaCl. Predict if precipitate of PbCl2 will form.
(Ksp for PbCl2 = 1.6 x 10-5)
 Predicting Precipitation

• Calculation:
• [Pb2+]0 = (20.0 mL x 0.025 M)/(50.0 mL) = 0.010 M
• [Cl-]0 = (30.0 mL x 0.10 M)/(50.0 mL) = 0.060 M
• Qsp = [Pb2+][Cl-]2 = (0.010 M)(0.060 M)2
• = 3.6 x 10-5
• Qsp > Ksp  precipitate of PbCl2 will form.