Chemistry: Atoms First

Fourth Edition
Julia Burdge and Jason Overby

Chapter 18
Acid–Base Equilibria
and Solubility
Equilibria

© 2021 McGraw Hill. All rights reserved. Authorized only for instructor use in the classroom. No reproduction or
further distribution permitted without the prior written consent of McGraw Hill.
Chapter 18 Acid–Base Equilibria and Solubility Equilibria 1

18.1 The Common Ion Effect

18.2 Buffer Solutions
Calculating the pH of a Buffer
Preparing a Buffer Solution with as Specific pH
18.3 Acid–Base Titrations
Strong Acid–Strong Base Titrations
Weak Acid–Strong Base Titrations
Strong Acid–Weak Base Titrations
Acid–Base Indicators
18.4 Solubility Equilibria
Solubility Product Expression and Ksp
Calculations Involving Ksp and Solubility
Predicting Precipitation Reactions

© McGraw Hill
Chapter 18 Acid–Base Equilibria and Solubility Equilibria 2

18.5 Factors Affecting Solubility

The Common Ion Effect
pH
Complex Ion Formation
18.6 Separation of Ions Using Differences in Solubility
Fractional Precipitation
Qualitative Analysis of Metal Ions in Solution

© McGraw Hill
18.1 The Common Ion Effect

Common Ion Effect:

• until now – mainly dealt with single solute in solution
• now deal with 2 solutes
• when the added ion that is in common with already dissolved
species, you shift the equilibrium
- common ion effect
Example: 1.0 L of 0.10 M solution of CH3COOH
CH3COOH(aq) ⇌ H+(aq) + CH3COO–(aq)

add 0.050 mol of CH3COONa

H2O
CH3COONa(aq) Na+(aq) + CH3COO–(aq)
Equilibrium is driven toward reactant addition
CH3COOH(aq) H+(aq) + CH3COO–(aq)
More CH3COOH(aq) is form and less H+(aq) in solution
18.1 The Common Ion Effect

Determine pH of 1.0 L of 0.10 M solution of CH3COOH

K a = 1.8x10 −5 CH3COOH(aq) ⇌ H+(aq) + CH3COO–(aq)

Initial concentration (M) 0.10 0 0

Change in concentration (M) –x +x +x

Equilibrium concentration (M) 0.10 – x x x

[CH3COO − ][H+ ] x2 x2
Ka = = ≈ = 1.8 x 10 −5
[CH3COOH] 0.10 − x 0.10

[H+] = 1.34 ´ 10–3 M; pH = 2.87

The Common Ion Effect

Determine the pH at 25°C of a solution prepared by adding 0.050 mole of sodium

acetate to 1.0 L of 0.10-M acetic acid. (Assume that the addition of sodium
acetate does not change the volume of the solution.)

K a = 1.8x10 −5 CH3COOH(aq) ⇌ H+(aq) + CH3COO–(aq)

Initial concentration (M) 0.10 0 0.050

Change in concentration (M) –x +x +x

Equilibrium concentration (M) 0.10 – x x 0.050 + x

[CH3COO − ][H+ ] ( x )(0.050 + x ) ( x )(0.050 )

Ka = = ≈ = 1.8 x 10 −5
[CH3COOH] 0.10 − x 0.10

[H+] = 3.6 ´ 10–5 M; pH = 4.44

2.87 < 4.44
18.1 The Common Ion Effect
Presence of common ion shifts equilibrium to left
- suppresses ionization of weak electrolyte (acid)
CH3COOH(aq) ⇌ H+(aq) + CH3COO–(aq)

important points:
1. ignored water autoionization
2. will reach same point if we:
- add acetate to acetic acid solution
- add acetic acid to acetate solution
- add acetic acid and acetate to water

To above reaction, addition of which compound will result in

common ion effect?
CH3COOLi HCOOLi HCl
18.2 Buffer Solutions

No new concepts—just new application

Buffers important:
- pH of blood must be maintained between 7.38 and 7.42
- if varies outside of that è YOU DIE

Buffer = Solution that contains weak acid and its conjugate base OR
= Solution that contains weak base and its conjugate acid
= Solutes present in comparable amounts
HC2H3O2 and NaC2H3O2 (acetate buffer)
H2CO3 and HCO3– (carbonate buffer)
NH4Cl and NH3 (ammonium buffer)
18.2 Buffer Solutions

Buffer resists changes in pH

= on addition of small amount of acid
= on addition of small amount of base
Can handle as a common-ion problem

How buffer works: HA and A– in solution (equilibrium)

-- add strong acid: H+ + A– ® HA (A– neutralizes)
-- add strong base:HA + OH– ® A– + H2O (HA neutralizes)
Calculating the pH of a Buffer

Calculate the pH of a buffer that contains 1.0 M acetic acid and 1.0
M sodium acetate [Ka (HC2H3O2) = 1.8 × 10–5].
CH3COOH(aq) ⇌ H+(aq) + CH3COO–(aq)

Initial concentration (M) 1.0 0 1.0

Change in concentration (M) –x +x +x

Equilibrium concentration (M) 1.0 – x x 1.0 + x

Ka = [(x)(1.0 + x)]/(1.0 – x) = 1.8 × 10–5

Use approximation method,
x = [H+] = 1.8 × 10–5 M; pH = 4.74
Calculating the pH of a Buffer
HA ⇄ H+ + A-
[H+ ][A − ] [HA] [A − ]
[H+] = Ka pH = pK a + log
Ka =
[HA] rearrange –
[A ] -log both side [HA]

[conjugate base]
pH = pK a + log
[weak acid]
Henderson-Hasselbach Equation

Important points:
1. “x” is small, so can use initial [ ] for HA and A–
2. since it’s a ratio, can use M or moles
3. dilution won’t change [A–]/[HA], so pH won’t change

For a weak base/conjugate acid buffer:

[conjugate acid]
pOH = pKb + log
[weak base]
Calculating the pH of a Buffer
What is the pH of NH3/NH4+ buffer (0.12 mol NH3, 0.095 mol NH4Cl)?
[Kb (NH3) = 1.8 x 10–5]
!"#$%&'() '*+,
pOH = pKb + log
-)'. /'0)
1.134 5"6 78!"
pOH = -log(1.8×10 ) + log 1.9: 5"6 78
–5
#

pOH = 4.64
pH = 14.00 - 4.64 = 9.36
Can we use the other equation(for acid) to calculate for pH directly?
!"#$%&'() /'0)
pH = pKa + log -)'. '*+,
!"#$%&'() /'0)
pH = p(Kw/Kb) + log -)'. '*+,
1.9: 5"6 78#
pH = -log(1.0×10–14 /1.8×10–5) + log1.134 5"6 78"
!
pH = 9.36
Calculating the pH of a Buffer
What happens when you add acid or base to buffer?

1. Begin with 1.00 L of acetate buffer:

1.00 M HC2H3O2 and 1.00 M NaC2H3O2

[A − ]
pH = pK a + log when [HA] = [A–]
[HA]
log ([A–]/[HA])
log(1) = 0 è pH = pKa

pH = pKa = –log (1.8 x 10–5) = 4.74

Calculating the pH of a Buffer
What happens when you add acid to buffer?
1. Begin with 1.00 L of acetate buffer:
1.00 M HC2H3O2 and 1.00 M NaC2H3O2
2. Add 0.10 mol of HCl: should be neutralized by the base in buffer
Before rxn 1.0 mol 0.10 mol 1.0 mol
C2H3O2– + H+ ® HC2H3O2
After rxn 0.9 mol 0 mol 1.1 mol
ICE table method Henderson-Hasselbach Equation
[H ++][C H O –] –
[H 22H33O22–]
][C [C
[C22HH33OO22–]]
Ka
Ka== pH
[HC pH ==pKa
pKa++log
log
[HC2HH3OO2]]
2 3 2
[HC
[HC2HH3OO2]]
2 3 2

[H++][0.9] (0.9)
–5 [H ][0.9] (0.9)
1.8x10 –5
1.8x10 == ==4.74 + log
4.74 + log
[1.1]
[1.1] (1.1)
(1.1)
+ –5
[H 2.2x10–5MM
[H+]]==2.2x10 ==4.65
4.65
pH
pH ==4.66
4.66 Original buffer pH is 4.74
Calculating the pH of a Buffer
What happens when you add base to buffer?
1. Begin with 1.00 L of acetate buffer:
1.00 M HC2H3O2 and 1.00 M NaC2H3O2
2. If added 0.10 mol of NaOH: neutralized by the acid in buffer
Before rxn 1.0 mol 0.10 mol 1.0 mol
HC2H3O2 + OH– ® C2H3O2– + H2O
After rxn 0.9 mol 0 mol 1.1 mol

pH = 4.74 + log(1.1/0.9) = 4.83

Original buffer pH is 4.74

Calculating the pH of a Buffer

1.00 L of acetate buffer:

1.00 M HC2H3O2 and 1.00 M NaC2H3O2

change in pH with addition of acid or base to buffer is small:

-- addition of 0.10 mol H+ to bufferè pH=4.74 to pH=4.65
-- addition of 0.10 mol H+ to waterè pH=7.00 to pH=1.00

-- addition of 0.10 mol OH– to bufferè pH=4.74 to pH=4.83

-- addition of 0.10 mol OH– to waterè pH=7.00 to pH=13.00
Buffer Range and Capacity
Buffer capacity = how much acid or base can be added before a buffer
can no longer buffer the pH.
Determined by identity of buffer components and their concentrations.
Buffers are most effective (maximum buffering capacity) when [HA] =
[A–]; when [HA] and [A–] differ by more than a factor of 10, no longer
a reasonable buffer.
[>$ ]
[A<] When [HA] = [A–], log [@>] = log 1 = 0
pH = pK ; + log
[HA] and pH = pKa, buffer is most effective
[>$ ] 9
1 When [HA] = 10[A–], log [@>] = log 91 = −1
pH = pK ; + log
10 and pH = pKa−1
[>$ ]
10 When 10[HA] = [A–], log [@>] = log 10 = 1
pH = pK ; + log
1 and pH = pKa+1
Buffer Range and Capacity

Acceptable range (effective range) of pH for buffer is

pH = pK ; ± 1

Weak Acid Ka pKa

HF 7.1×10-4 3.15
HNO2 4.5×10-4 3.35
HCOOH 1.7×10-4 3.77
C6H5COOH 6.5×10-5 4.19
CH3COOH 1.8×10-5 4.74
HCN 4.9×10-10 9.31
C6H5OH 1.3×10-10 9.89

[HA] and [A–] need to be at least 10× greater than added [H+] or
[OH–] in order to keep pH from changing significantly
Buffer Range and Capacity
Which of the following buffers has the best buffer capacity,
assuming same volume of solutions?

0.7 M HF and 0.4 M F-

0.7 M HF and 0.7 M F-

0.0007 M HF and 0.0007 M F-

Preparing a Buffer Solution with a Specific pH

To make a buffer with a specific pH:

1) Pick a weak acid whose pKa is close to the desired pH.

2) Substitute the pH and pKa into the equation below to obtain the
necessary [conjugate base]/[weak acid] ratio.

pH = pKa + log[A–]/[HA]

Acceptable range (effective range) of pH for buffer is

pH = pK ; ± 1
Worked Example 18.3 Weak Acid Ka pKa
HF 7.1×10-4 3.15
Select a proper weak acid from the table at right, and
HNO2 4.5×10-4 3.35
describe how you would prepare a buffer with a pH of 9.50. HCOOH 1.7×10-4 3.77
pH = pKa + log[A–]/[HA] C6H5COOH 6.5×10-5 4.19

pH = pK ; ± 1 CH3COOH 1.8×10-5 4.74

HCN 4.9×10-10 9.31
Solution Two of the acids listed have pKa values
C6H5OH 1.3×10-10 9.89
in the desired range: hydrocyanic acid (HCN, pKa =
9.31) and phenol (C6H5OH, pKa = 9.89).

9.50 = 9.89 + log[C6H5O−]/[C6H5OH]

9.50 – 9.89 = log[C6H5O−]/[C6H5OH] = –0.39

[C6H5O−]/[C6H5OH] = 10−0.39 = 0.41

Solution Therefore, the ratio of [C6H5O−] to [C6H5OH] must be 0.41 to 1. One

way to achieve this would be to dissolve 0.41 mole of C6H5ONa and 1.00 mole of
C6H5OH in 1.00 L of water.
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