10/14/22

Common Ion Effect,

Buffers
&
Solubility Equilibria

Common Ion Effect

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The Common-Ion Effect

• 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.

• In order to explore the idea, consider a solution of acetic

acid:

HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2−(aq)

• If acetate ion (C2H3O2−) is added to the solution, Le

Châtelier says the equilibrium will shift to the left.

Class Exercise:
• Calculate the pH of a 0.30M solution of acetic acid
(HC2H3O2). Ka = 1.8 x 10-5.

• Calculate the pH of a solution made by adding 0.30 mol of

acetic acid and 0.30 mol of sodium acetate (NaC2H3O2) to
enough water to make 1.0 L of solution?

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Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid: Ka = 1.8 x 10-5).

CH3COOH (aq) ⇌ H+ (aq) + CH3COO- (aq)

common
CH3COONa (s) Na+ (aq) + CH3COO- (aq) ion

Consider a case where you have 0.3 M of CH3COOH (aq),

and then you add 0.3M CH3COONa (s)
CH3COOH H+ CH3COO-
0.3 0 0
-x +x +x
Add 0.3

0.3-x x 0.3+x

The dissociation of the weak acid HC2H3O2 decreases

when the strong electrolyte NaC2H3O2, which has an ion in
common with it, is added.

The presence of a common ion suppresses

the ionization of a weak acid or a weak base.

The extent of ionization of a weak electrolyte is decreased by adding to the

solution a strong electrolyte that has an ion in common with the weak
electrolyte.

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Class Exercise:
Calculate the fluoride ion concentration and pH of
a solution that is 0.20 M in HF and 0.10 M in HCl.

Ka for HF is 6.8 ´ 10−4.

[H3O+] [F−]
Ka = = 6.8 ´ 10-4
[HF]

HF(aq) + H2O(l) H3O+(aq) + F−(aq)

Because HCl, a strong acid, is also present,

the initial [H3O+] is not 0, but rather 0.10 M.

[HF], M [H3O+], M [F−], M

Initially 0.20 0.10 0

Change −x +x +x
At Equilibrium 0.20 − x » 0.20 0.10 + x » 0.10 x

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(0.10) (x)
6.8 ´ 10−4 = (0.20)
(0.20) (6.8 ´ 10−4)
x= (0.10)
x = 1.4 ´ 10−3

• Therefore, [F−] = x = 1.4 ´ 10−3 M

[H3O+] = 0.10 + x = 0.10 + 1.4 ´ 10−3 = 0.10 M

• So, pH = −log (0.10)

pH = 1.00
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Example
• Consider the following reaction:
• Cu(H2O)62+(aq) + 4Cl−(aq) ⇌ CuCl42−(aq) + 6H2O(ℓ) DH > 0
Blue green

• What will happen to the colour of the solution when ... (Write only more
blue, more green or remains the same)

• concentrated HCl is added

• a few NaCl crystals are added

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Buffered Solutions

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Buffered Solutions

• Solutions of a weak
conjugate acid-base pair.

• They are particularly

resistant to pH changes,
even when strong acid or
base is added.

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Composition and Action of Buffered Solutions

• A buffer resists changes in pH because it contains both an

acidic species to neutralize OH- ions and a basic species
to neutralize H+ ions.

• The acidic and basic species must not consume

themselves through neutralization.

• These requirements are met by using a weak conjugate

acid-base pair:

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If a small amount of hydroxide is added to an equimolar

solution of HF in NaF, for example, the HF reacts with
the OH− to make F− and water.

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If acid is added, the F− reacts to form HF and water.

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Calculating the pH of a Buffer

• Because conjugate acid-base pairs share a common ion,

we can use the same procedures to calculate the pH of a
buffer that were used for th common-ion effect.

• Consider the equilibrium constant expression for the

dissociation of a generic acid, HA:

HA + H2O H3O+ + A−

[H3O+] [A−]
Ka =
[HA]
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Rearranging slightly, this becomes

[A−]
Ka = [H3O+]
[HA]

Taking the negative log of both side, we get

[A−] base
−log Ka = −log [H3O+] + −log
[HA]
pKa pH
acid

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• So
[base]
pKa = pH − log
[acid]
• Rearranging, this becomes
[base]
pH = pKa + log
[acid]

• This is the Henderson–Hasselbalch equation.

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Henderson–Hasselbalch Equation
What is the pH of a buffer that is 0.12 M in lactic
acid, HC3H5O3, and 0.10 M in sodium lactate? Ka
for lactic acid is 1.4 ´ 10−4.

[base]
pH = pKa + log
[acid]
(0.10)
pH = −log (1.4 ´ 10−4) + log (0.12)
pH = 3.85 + (−0.08)

pH = 3.77
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Acid Base Titrations

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Acid-Base Titrations
• In this technique, an acid (or base)
solution of known concentration is
slowly added to a base (or acid)
solution of unknown concentration.

• A pH meter or indicators are used to

determine when the solution has
reached the equivalence point:

• The amount of acid equals that of

base.

Acid-Base Titrations
• From the start of the titration of a strong
acid with a strong base to near the
equivalence point, the pH goes up slowly.

• Just before (and after) the equivalence

point, the pH rises rapidly.

• At the equivalence
point, pH = 7.

• As more base is
added, the pH
again levels off.

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Acid-Base Titrations
• Titration of a Strong Base with
a Strong Acid.

Ø It looks like you “flipped

over” the strong acid being
titrated by a strong base.

Ø Start with a high pH (basic

solution); the pH = 7 at the
equivalence point; low pH
to end.

Acid-Base Titrations
• Titration of a Weak Acid with a Strong
Base

• Use Ka to find initial pH.

• Find the pH in the “buffer region” using

stoichiometry followed by the Henderson–
Hasselbalch equation.

• At the equivalence point the pH is >7. Use

the conjugate base of the weak acid to
determine the pH.

• As more base is added, the pH levels off.

This is exactly the same as for strong
acids.

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Ways That a Weak Acid Titration

Differs from a Strong Acid Titration

1) A solution of weak acid has a

higher initial pH than a strong
acid.

2) The pH change near the

equivalence point is smaller for
a weak acid. (This is at least
partly due to the buffer region.)

3) The pH at the equivalence point

is greater than 7 for a weak
acid.

Titrating with an Acid-Base Indicator

• Indicators are weak acids that have a different color
than their conjugate base form.
• Each indicator has its own pH range over which it
changes color.
• An indicator can be used to find the equivalence point
in a titration as long as it changes color in the small
volume change region where the pH rapidly changes.

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Titrating with an Acid-Base Indicator

Indicator Choice Can Be Critical!

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Solubility Equilibria

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Solubility Equilibria

• Because ionic compounds are strong electrolytes, they

dissociate completely to the extent that they dissolve.

• When an equilibrium equation is written, the solid is the

reactant and the ions in solution are the products.

• The equilibrium constant expression is called the

solubility-product constant. It is represented as Ksp.

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Solubility Product Constant Ksp

• Example 1:
BaSO4(s) ⇌ Ba2+(aq) + SO42–(aq)

• The equilibrium constant expression is

Ksp = [Ba2+][SO42-]

• Example 2:
Ba3(PO4)2(s) ⇌ 3 Ba2+(aq) + 2 PO43–(aq)

• The equilibrium constant expression is

Ksp = [Ba2+]3[PO43-]2

Solubility and Ksp

• Ksp is not the same as solubility.

• Solubility is the quantity of a substance that dissolves to form a

saturated solution.

• Common units for solubility:

o Grams per liter (g/L)
o Moles per liter (mol/L)

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Calculating Solubility from Ksp

• The Ksp for CaF2 is 3.9 × 10–11 at 25 °C. What is its molar
solubility?

• Follow the same format as before:

o CaF2(s) ⇌ Ca2+(aq) + 2 F–(aq)
CaF2(s) [Ca2+](M) [F–](M)

Initial concentration
(M) --- 0 0
Change in
concentration (M) --- +x +2x
Equilibrium
concentration (M) --- x 2x

"#$ = &'() * + ( = 3.9/10+22

Calculating Solubility from Ksp

4) Substitute the equilibrium concentration values from Appendix
D into the solubility-product equation:

3.9$10'(( = $ 2$ + = 4$ -
3.9$10'(( = 4$ -
3.9$10'(( 4$ -
= = 9.75$10'(+ = $ -
4 4
0 0
9.75$10'(+ = $ - = 2.14$10'1 2 = $

(If you want the answer in g/L, multiply by molar mass; this
would give 0.016 g/L.)

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Precipitation and Separation of Ions

• Calculate the reaction quotient, Q, and compare it to the

solubility product constant, Ksp.

o If Q = Ksp, the system is at equilibrium and the solution is

saturated.
o If Q < Ksp, more solid can dissolve, so no precipitate forms.
o If Q > Ksp, a precipitate will form.

Class Exercise

• Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol)

required 43.31 mL of KMnO4. What is the molar
concentration of the KMnO4 solution?

• The chemical reaction is

• 2MnO4- + 5C2O42- + 16H+ ⇌ 2Mn2+ + 10CO2 + 8H2O

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Example

• The solubility product of Fe(OH)2 is 8 x 10-16. Calculate the

solubility of Fe(OH)2 in
Ø moles/dm3

Ø g/L

Example
• Calculate the molar solubility of silver sulfide, Ag2S, given that
Ksp is 8 × 10–51 at 25°C.

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Example
• How many milliliters of 0.200M H2SO4 are required to react with 10.32
m! of 0.4042 M NaHCO3

H2SO4 (aq) + 2NaHCO3 (aq) → Na2SO4 (aq) + 2H2O (l) + 2CO2 (g)

Example
• Calculate the volume of 0.1250 M phosphoric acid solution necessary
to react with 50.0mL of 0.250M Mg(OH)2.

2H3PO4 + 3Mg(OH)2 Ò Mg3(PO4)2 + 6H2O

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Example
• How many milliliters of 0.200 M H2SO4 are required to react with 10.32 m!
of 0.4042 M NaHCO3

H2SO4 (aq) + 2NaHCO3 (aq) → Na2SO4 (aq) + H2O (l) + 2CO2

Example
• Oxalic acid reacts with the chromate ion in acidic solution as follows:

H2C2O4(aq) + 2 CrO42-(aq) + 10 H+ (aq)→ 6 CO(g) + 2 Cr3+(aq) + 8 H2O(!)

• 2.5683g of K2CrO4 was weighed out, dissolved and diluted to 500m! in a
volumetric flask. Calculate the molarity of the oxalic acid if a 25.00 m! aliquot of
this acid solution consumed 28.54 m! of the chromate solution.

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Example

• Calculate the volume of 0.1250 M phosphoric acid solution necessary

to react with 50.0m! of 0.250M Mg(OH)2.

2H3PO4 + 3Mg(OH)2 Ò Mg3(PO4)2 + 6H2O

Example

• Given that the Ksp of Ca3(PO4)2 = 1.3 x 10–32.

• Calculate the solubility of Ca3(PO4)2 in water in mol L–1

and g L–1.

• Calculate the molar solubility of Ca3(PO4)2 in 0.20 M

Na3PO4 solution.

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Example
• Will a precipitate occur if a 0.01 M Ag+ solution is
mixed with an equal volume of 0.01 M sulfuric acid?
Ksp (Ag2SO4) = 2 x 10–5 M3

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Example
• What is the solubility of Fe(OH)3 (Ksp = 6 x 10-38) in a
pH 10.5 aqueous solution?

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Example
• Lactic acid (C3H6O3), a monoprotic acid, is a waste
product that accumulates in muscle tissue during exertion,
leading to pain ("cramp") and a feeling of fatigue. In a
0.100 M aqueous solution, lactic acid is 3.7% dissociated.
If the equilibrium concentration of H+ ion is x mol L–1, write
the equilibrium expression for Ka in terms of x and thus
work out the equilibrium concentrations, the value of pH
and Ka for lactic acid.

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