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Chapter 17 Notes

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I. Common Ion Effect

A. Definition: The common ion effect occurs when the addition of an ion already present in a solution

causes a shift in the equilibrium position of a reaction.

B. Formula: Qsp = [C]^c [D]^d / [A]^a [B]^b, where [A], [B], [C], and [D] are the molar concentrations of

the reactants and products.

C. Examples:

Calculate the solubility of PbCl2 in a 0.010 M NaCl solution. The Ksp for PbCl2 is 1.6 x 10^-5.

1. Solution: The presence of Na+ ions from NaCl will cause the solubility of PbCl2 to decrease

due to the common ion effect. The solubility of PbCl2 can be calculated using the formula:

Ksp = [Pb2+][Cl-]^2 = (x)(2x)^2 = 4x^3 = 1.6 x 10^-5, where x is the molar solubility of PbCl2.

Solving for x, we get x = 0.0020 M. Therefore, the solubility of PbCl2 in a 0.010 M NaCl

solution is 0.0020 M.

Calculate the molar solubility of Ag2CrO4 in a solution that contains 0.10 M K2CrO4 and 0.10 M

AgNO3. The Ksp for Ag2CrO4 is 1.1 x 10^-12.

2. Solution: The presence of CrO42- ions from K2CrO4 and Ag+ ions from AgNO3 will cause the

solubility of Ag2CrO4 to decrease due to the common ion effect. The molar solubility of

Ag2CrO4 can be calculated using the formula: Ksp = [Ag+]^2 [CrO42-] = (x)^2(0.10 - x) = 1.1 x
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10^-12. Solving for x, we get x = 1.0 x 10^-6 M. Therefore, the molar solubility of Ag2CrO4 in

the solution is 1.0 x 10^-6 M.

II. Buffers

A. Definition: Buffers are solutions that resist changes in pH when small amounts of acid or base are

added.

B. Henderson-Hasselbalch equation: pH = pKa + log [A-] / [HA], where pKa is the acid dissociation

constant, [A-] is the concentration of the conjugate base, and [HA] is the concentration of the

weak acid.

C. Examples:

Calculate the pH of a buffer solution that contains 0.10 M acetic acid (CH3COOH) and 0.10 M

sodium acetate (CH3COO-). The Ka for acetic acid is 1.8 x 10^-5.

1. Solution: The pH of the buffer solution can be calculated using the Henderson-Hasselbalch

equation: pH = pKa + log [A-] / [HA] = -log(1.8 x 10^-5) + log(0.10 / 0.10) = 4.74. Therefore, the

pH of the buffer solution is 4.74.

2. Calculate the pH of a buffer solution that contains 0.15 M NH3 and 0.10 M NH4Cl. The

Solution: NH3 is a weak base and NH4Cl is its conjugate acid. The NH3 will react with the H+ ions in

the solution to form NH4+ ions and water, while the NH4+ ions will react with OH- ions in the

solution to form NH3 and water. The reaction can be represented as follows:

NH3 + H2O ⇌ NH4+ + OH-

NH4+ + H2O ⇌ NH3 + H3O+

The pH of the buffer solution can be calculated using the Henderson-Hasselbalch equation: pH =

pKa + log [A-] / [HA] = pKa + log (base/acid). Since NH3 is the base and NH4+ is the acid, we

can calculate the pKa using the Kb for NH3: Kb = Kw/Ka = 1.0 x 10^-14 / 1.8 x 10^-5 = 5.6 x
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10^-10. Therefore, pKa = -log(5.6 x 10^-10) = 9.25. Substituting the values into the

Henderson-Hasselbalch equation, we get:

pH = 9.25 + log (0.15/0.10) = 9.32.

Therefore, the pH of the buffer solution is 9.32.

III. Acid-Base Titrations

A. Definition: Acid-base titration is a method used to determine the concentration of an unknown

acid or base by reacting it with a standard solution of known concentration.

B. Formula: M1V1 = M2V2, where M1 is the concentration of the acid or base being titrated, V1 is the

volume of the acid or base being titrated, M2 is the concentration of the standard solution,

and V2 is the volume of the standard solution required to reach the equivalence point.

C. Examples:

A 25.00 mL sample of HCl solution of unknown concentration is titrated with 0.1000 M NaOH. It

takes 33.60 mL of the NaOH solution to reach the equivalence point. Calculate the

concentration of the HCl solution.

Solution: Using the formula M1V1 = M2V2, we can calculate the concentration of the HCl solution as

follows:

M1 = M2V2 / V1 = (0.1000 M)(33.60 mL) / 25.00 mL = 0.134 M.

1. Therefore, the concentration of the HCl solution is 0.134 M.

A 50.00 mL sample of 0.150 M H2SO4 solution is titrated with 0.100 M NaOH solution. Calculate the

pH at the equivalence point.

Solution: The balanced equation for the reaction is:

H2SO4 + 2 NaOH → Na2SO4 + 2 H2O

At the equivalence point, the number of moles of NaOH added will be equal to the number of moles

of H2SO4 present in the solution. Therefore, we can calculate the concentration of H2SO4 as

follows:

M H2SO4 = (0.100 M) (V NaOH) / V H2SO4, where V NaOH is the volume of NaOH required to reach

the equivalence point and V H2SO4 is the volume of the H2SO4 solution titrated.

V NaOH = 2 V H2SO4, since 2 moles of NaOH react with 1 mole of H2SO4.

Substituting the values, we get:

2. M H2SO4 = (0.100 M) ((2 V H2SO4) / V H2SO4 = 0.200 M.

At the equivalence point, the solution will be neutral and the pH will be 7.

IV. Solubility Equilibrium

A. Definition: Solubility equilibrium is a dynamic equilibrium between a sparingly soluble salt and its

ions in a solution at a given temperature.

B. Formula: Ksp = [A+]m [B-]n, where A and B represent the ions in the salt, m and n are the

coefficients of the ions in the balanced equation, and [A+] and [B-] are the ion concentrations

in the solution at equilibrium.

C. Examples:

The solubility product of AgCl is 1.8 x 10^-10 at 25°C. Calculate the solubility of AgCl in water.

Solution: The solubility product expression for AgCl is:

AgCl ⇌ Ag+ + Cl-

Ksp = [Ag+] [Cl-]

Since the molar solubility of AgCl is equal to the concentration of Ag+ and Cl- ions at equilibrium, we

can substitute [AgCl] for both [Ag+] and [Cl-] in the Ksp expression:

Ksp = [AgCl]^2 = (s)^2

Solving for s, we get:

s = sqrt(Ksp) = sqrt(1.8 x 10^-10) = 1.34 x 10^-5 M

1. Therefore, the solubility of AgCl in water is 1.34 x 10^-5 M.

The solubility of PbF2 in water is 1.1 x 10^-4 M at 25°C. Calculate the value of Ksp for PbF2.

Solution: The solubility product expression for PbF2 is:

PbF2 ⇌ Pb2+ + 2 F-

Ksp = [Pb2+] [F-]^2

Since the solubility of PbF2 is 1.1 x 10^-4 M, the concentration of Pb2+ is also 1.1 x 10^-4 M, and the

concentration of F- is 2.2 x 10^-4 M (since there are two F- ions for each PbF2 molecule).

Substituting the values, we get:

Ksp = (1.1 x 10^-4 M) (2.2 x 10^-4 M)^2 = 5.3 x 10^-9

2. Therefore, the value of Ksp for PbF2 is 5.3 x 10^-9.

V. Common Ion Effect

A. Definition: Common ion effect is the shift in equilibrium position of a weak acid or base due to the

addition of a common ion that is already present in the solution.

B. Formula: The formula for the common ion effect can be derived from the equilibrium constant

expression of the weak acid or base:

Ka = [H+][A-] / [HA]

If a common ion (A-) is added to the solution, the equilibrium will shift to the left, resulting in a

decrease in the ionization of the weak acid (HA) and a decrease in the concentration of H+

ions in the solution.

C. Examples:
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Calculate the pH of a 0.10 M solution of acetic acid (Ka = 1.8 x 10^-5) after the addition of 0.05 M

sodium acetate.

1. Solution: The addition of sodium acetate will introduce acetate ions (A-) into the solution,

which will react with the acetic acid to form the conjugate base. The reaction will shift the

equilibrium to the left and decrease the concentration of H+ ions in the solution. The

equation for the reaction is:

CH3COOH + NaCH3COO ⇌ CH3COO- + H2O + Na+

The initial concentration of acetic acid is 0.10 M, and the initial concentration of acetate ions is 0 M.

After the addition of sodium acetate, the concentration of acetate ions becomes 0.05 M, and

the concentration of acetic acid decreases by an amount equal to the concentration of

acetate ions that react with it, which is also 0.05 M. Therefore, the equilibrium

concentrations of acetic acid, acetate ions, and H+ ions are:

[CH3COOH] = 0.10 M - 0.05 M = 0.05 M

[CH3COO-] = 0.05 M

[H+] = sqrt(Ka [CH3COOH] / [CH3COO- + CH3COOH]) = sqrt(1.8 x 10^-5 x 0.05 / 0.10) = 1.5 x 10^-3 M

Therefore, the pH of the solution is:

pH = -log[H+] = -log(1.5 x 10^-3) = 2.82

VI. Acid-Base Titrations

A. Definition: An acid-base titration is a laboratory technique used to determine the concentration of

an acid or base by reacting it with a solution of known concentration (standard solution) of

the opposite type.

B. Formula: The formula used in acid-base titrations is:

MaVa = MbVb, where Ma and Va are the molarity and volume of the acid, Mb and Vb are the molarity

and volume of the base, respectively. The equation is based on the principle of stoichiometry,

where the moles of acid are equal to the moles of base at the equivalence point.

C. Examples:

Calculate the concentration of a 25.0 mL solution of HCl that is titrated with 0.100 M NaOH solution.

If it takes 35.0 mL of NaOH to reach the equivalence point, what is the concentration of HCl?

Solution: At the equivalence point, the moles of acid (HCl) are equal to the moles of base (NaOH).

The equation for the reaction is:

HCl + NaOH → NaCl + H2O

Since the reaction is 1:1, the molarity of HCl can be calculated using the formula:

MaVa = MbVb

(0.100 M) (35.0 mL) = Ma (25.0 mL)

Ma = (0.100 M) (35.0 mL) / (25.0 mL) = 0.140 M

1. Therefore, the concentration of the HCl solution is 0.140 M.

A 50.0 mL sample of 0.100 M H2SO4 is titrated with 0.100 M NaOH solution. What is the pH of the

solution after the addition of 25.0 mL of NaOH?

Solution: The balanced equation for the reaction is:

H2SO4 + 2 NaOH → Na2SO4 + 2 H2O

2. At the equivalence point, all of the H2SO4 will have reacted with the NaOH, and the solution

will contain only Na2SO4 and water. However, the addition of 25.0 mL of NaOH is not enough

to reach the equivalence point, since the amount of H2SO4 present is twice the

concentration of NaOH. Therefore, we need to use the formula for calculating the

concentration of excess acid (or base) in the solution after the addition of the titrant:
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n(H2SO4) = C(H2SO4) x V(H2SO4) = (0.100 M) x (50.0 mL / 1000 mL) = 0.005 mol

n(NaOH) = C(NaOH) x V(NaOH) = (0.100 M) x (25.0 mL / 1000 mL) = 0.0025 mol

Since H2SO4 and NaOH react in a 1:2 ratio, the amount of NaOH needed to react with all of the

H2SO4 is:

n(NaOH) = 0.5 x n(H2SO4) = 0.0025 mol

Therefore, the amount of excess NaOH in the solution is:

n(excess NaOH) = n(titrant) - n(NaOH) = 0.0025 mol

The volume of the solution is:

V = V(H2SO4) + V(NaOH) = 50.0 mL + 25.0 mL = 75.0 mL

The concentration of excess NaOH is:

C(excess NaOH) = n(excess NaOH) / V = 0.0025 mol / (75.0 mL / 1000 mL) = 0.033 M

Since NaOH is a strong base, it completely dissociates in water to form OH- ions. Therefore, the

concentration of OH- ions in the solution is equal to the concentration of excess NaOH:

[OH-] = C(excess NaOH) = 0.033 M

The concentration of H+ ions can be calculated using the equation for the ion product constant of

water:

Kw = [H+][OH-] = 1.0 x 10^-14

[H+] = Kw / [OH-] = 1.0 x 10^-14 / 0.033 = 3.0 x 10^-13 M

Therefore, the pH of the solution is:

pH = -log[H+] = -log(3.0 x 10^-13) = 12.52