5/1/2012

Lecture Presentation

Chapter 17 Additional Aspects of Aqueous Equilibria

2012 Pearson Education, Inc.

John D. Bookstaver St. Charles Community College Cottleville, MO

The Common-Ion Effect

Consider a solution of acetic acid:
CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO(aq)

If acetate ion is added to the solution, Le Chtelier says the equilibrium will shift to the left.

Aqueous Equilibria 2012 Pearson Education, Inc.

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The Common-Ion Effect

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.

Aqueous Equilibria 2012 Pearson Education, Inc.

The Common-Ion Effect

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 6.8 104.

Ka =

[H3O+] [F] = 6.8 104 [HF]

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The Common-Ion Effect

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 Initially Change At equilibrium
Aqueous Equilibria 2012 Pearson Education, Inc.

[H3O+], M 0.10

[F], M 0

0.20

The Common-Ion Effect

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 Initially Change At equilibrium
Aqueous Equilibria 2012 Pearson Education, Inc.

[H3O+], M 0.10 +x

[F], M 0 +x

0.20 x

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The Common-Ion Effect

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 Initially Change At equilibrium 0.20 x 0.20 x 0.20 [H3O+], M 0.10 +x 0.10 + x 0.10 [F], M 0 +x x
Aqueous Equilibria 2012 Pearson Education, Inc.

The Common-Ion Effect

6.8 104 = (0.10) (x) (0.20)

(0.20) (6.8 104) =x (0.10) 1.4 103 = x

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The Common-Ion Effect

Therefore, [F] = x = 1.4 103 [H3O+] = 0.10 + x = 0.10 + 1.4 103 = 0.10 M So, pH = log (0.10) pH = 1.00
2012 Pearson Education, Inc.

Aqueous Equilibria

Sample Exercise 17.1 Calculating the pH When a Common Ion is Involved What is the pH of a solution made by adding 0.30 mol of acetic acid and 0.30 mol of sodium acetate to enough water to make 1.0 L of solution?

Chemistry, The Central Science, 12th Edition Theodore L. Brown; H. Eugene LeMay, Jr.; Bruce E. Bursten; Catherine J. Murphy; and Patrick Woodward

2012 Pearson Education, Inc.

5/1/2012

Sample Exercise 17.1 Calculating the pH When a Common Ion is Involved

Practice Exercise Calculate the pH of a solution containing 0.085 M nitrous acid (HNO2,Ka = 4.5 104) and 0.10 M potassium nitrite (KNO2). Answer: 3.42

Chemistry, The Central Science, 12th Edition Theodore L. Brown; H. Eugene LeMay, Jr.; Bruce E. Bursten; Catherine J. Murphy; and Patrick Woodward

2012 Pearson Education, Inc.

Sample Exercise 17.2 Calculating Ion Concentrations When a Common Ion is Involved

Practice Exercise Calculate the formate ion concentration and pH of a solution that is 0.050 M in formic acid (HCOOH, Ka = 1.8 104) and 0.10 M in HNO3. Answer: [HCOO] = 9.0 105, pH = 1.00

Chemistry, The Central Science, 12th Edition Theodore L. Brown; H. Eugene LeMay, Jr.; Bruce E. Bursten; Catherine J. Murphy; and Patrick Woodward

2012 Pearson Education, Inc.

5/1/2012

Buffers
Buffers are solutions of a weak conjugate acidbase pair. They are particularly resistant to pH changes, even when strong acid or base is added.
Aqueous Equilibria 2012 Pearson Education, Inc.

Buffers

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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Aqueous Equilibria

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Buffers

Similarly, if acid is added, the F reacts with it to form HF and water.

Aqueous Equilibria 2012 Pearson Education, Inc.

Buffer Calculations
Consider the equilibrium constant expression for the dissociation of a generic acid, HA: HA + H2O
Ka =

H3O+ + A
[H3O+] [A] [HA]
Aqueous Equilibria 2012 Pearson Education, Inc.

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

Taking the negative log of both side, we get

log Ka = log
pKa pH acid
2012 Pearson Education, Inc. Aqueous Equilibria

[H3O+]

[A] + log [HA]

base

Buffer Calculations
So pKa = pH log [base] [acid] [base] [acid]

Rearranging, this becomes pH = pKa + log

This is the HendersonHasselbalch equation.

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HendersonHasselbalch Equation
What is the pH of a buffer that is 0.12 M in lactic acid, CH3CH(OH)COOH, and 0.10 M in sodium lactate? Ka for lactic acid is 1.4 104.

Aqueous Equilibria 2012 Pearson Education, Inc.

HendersonHasselbalch Equation
pH = pKa + log [base] [acid] (0.10) (0.12)

pH = log (1.4 104) + log pH = 3.85 + (0.08) pH = 3.77

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Sample Exercise 17.3 Calculating the pH of a Buffer

Practice Exercise Calculate the pH of a buffer composed of 0.12 M benzoic acid and 0.20 M sodium benzoate. (Refer to Appendix D.) Answer: 4.42

Chemistry, The Central Science, 12th Edition Theodore L. Brown; H. Eugene LeMay, Jr.; Bruce E. Bursten; Catherine J. Murphy; and Patrick Woodward

2012 Pearson Education, Inc.

Sample Exercise 17.4 Preparing a Buffer

How many moles of NH4Cl must be added to 2.0 L of 0.10 M NH3 to form a buffer whose pH is 9.00? (Assume that the addition of NH4Cl does not change the volume of the solution.)

Chemistry, The Central Science, 12th Edition Theodore L. Brown; H. Eugene LeMay, Jr.; Bruce E. Bursten; Catherine J. Murphy; and Patrick Woodward

2012 Pearson Education, Inc.

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Sample Exercise 17.4 Preparing a Buffer

Practice Exercise Calculate the concentration of sodium benzoate that must be present in a 0.20 M solution of benzoic acid (C6H5COOH) to produce a pH of 4.00. Answer: 0.13 M

Chemistry, The Central Science, 12th Edition Theodore L. Brown; H. Eugene LeMay, Jr.; Bruce E. Bursten; Catherine J. Murphy; and Patrick Woodward

2012 Pearson Education, Inc.

pH Range
The pH range is the range of pH values over which a buffer system works effectively. It is best to choose an acid with a pKa close to the desired pH.

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When Strong Acids or Bases Are Added to a Buffer

When strong acids or bases are added to a buffer, it is safe to assume that all of the strong acid or base is consumed in the reaction.

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Addition of Strong Acid or Base to a Buffer

1. Determine how the neutralization reaction affects the amounts of the weak acid and its conjugate base in solution. 2. Use the HendersonHasselbalch equation to determine the new pH of the solution.

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Calculating pH Changes in Buffers

A buffer is made by adding 0.300 mol HC2H3O2 and 0.300 mol NaC2H3O2 to enough water to make 1.00 L of solution. The pH of the buffer is 4.74. Calculate the pH of this solution after 0.020 mol of NaOH is added.

Aqueous Equilibria 2012 Pearson Education, Inc.

Calculating pH Changes in Buffers

Before the reaction, since mol HC2H3O2 = mol C2H3O2 pH = pKa = log (1.8 105) = 4.74

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Calculating pH Changes in Buffers

The 0.020 mol NaOH will react with 0.020 mol of the acetic acid: HC2H3O2(aq) + OH(aq) C2H3O2(aq) + H2O(l)
HC2H3O2 Before reaction After reaction 0.300 mol C2H3O2 0.300 mol OH 0.020 mol

Aqueous Equilibria 2012 Pearson Education, Inc.

Calculating pH Changes in Buffers

The 0.020 mol NaOH will react with 0.020 mol of the acetic acid: HC2H3O2(aq) + OH(aq) C2H3O2(aq) + H2O(l)
HC2H3O2 Before reaction After reaction 0.300 mol 0.280 mol C2H3O2 0.300 mol 0.320 mol OH 0.020 mol 0.000 mol

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Calculating pH Changes in Buffers

Now use the HendersonHasselbalch equation to calculate the new pH:

pH = 4.74 + log pH = 4.74 + 0.06 pH = 4.80

(0.320) (0.200)

Aqueous Equilibria 2012 Pearson Education, Inc.

Sample Exercise 17.5 Calculating pH Changes in Buffers

Practice Exercise Determine (a) the pH of the original buffer described in Sample Exercise 17.5 after the addition of 0.020 mol HCl and (b) the pH of the solution that would result from the addition of 0.020 mol HCl to 1.000 L of pure water. Answers: (a) 4.68, (b) 1.70

Chemistry, The Central Science, 12th Edition Theodore L. Brown; H. Eugene LeMay, Jr.; Bruce E. Bursten; Catherine J. Murphy; and Patrick Woodward

2012 Pearson Education, Inc.

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GOOD LUCK!

Aqueous Equilibria

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