Acid-Base Equilibria and

Reading Assignments:
Solubility Equilibria
Chapter 16 Chapter 16 in
R. Chang, Chemistry, 8th Ed., McGraw-Hill,
2005

Or Related topics in other textbooks.

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The common ion effect is the shift in equilibrium caused by the Consider mixture of salt NaA and weak acid HA.
addition of a compound having an ion in common with the NaA (s) Na+ (aq) + A- (aq)
dissolved substance. [H+][A-]
Ka =
HA (aq) H+ (aq) + A- (aq) [HA]

Ka [HA]
The presence of a common ion suppresses [H+] =
the ionization of a weak acid or a weak base. [A-] Henderson-Hasselbalch
[HA] equation
-log [H+] = -log Ka - log
[A-] [conjugate base]
pH = pKa + log
Consider mixture of CH3COONa (strong electrolyte) and [A-] [acid]
CH3COOH (weak acid). -log [H+] = -log Ka + log
[HA]
CH3COONa (s) Na+ (aq) + CH3COO- (aq) [A-]
common pH = pKa + log pKa = -log Ka
ion [HA]
CH3COOH (aq) H+ (aq) + CH3COO- (aq)

16.2 16.2
 What is the pH of a solution containing 0.30 M HCOOH A is a solution of:
and 0.52 M HCOOK?
1. A weak acid or a weak base and
Mixture of weak acid and conjugate base! 2. The salt of the weak acid or weak base
HCOOH (aq) H+ (aq) + HCOO- (aq) Both must be present!
Initial (M) A buffer solution has the ability to resist changes in pH upon
Change (M) the addition of small amounts of either acid or base.

Equilibrium (M) Consider an equal molar mixture of CH3COOH and CH3COONa

[HCOO-] Add strong acid
Common ion effect pH = pKa + log
[HCOOH] H+ (aq) + CH3COO- (aq) CH3COOH (aq)
0.30 – x ≈ 0.30
Add strong base
0.52 + x ≈ 0.52
OH- (aq) + CH3COOH (aq) CH3COO- (aq) + H2O (l)
HCOOH pKa = 3.77
16.2 16.3

Which of the following are buffer systems? (a) KF/HF Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
(b) KBr/HBr, (c) Na2CO3/NaHCO3 system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?

NH4+ (aq) H+ (aq) + NH3 (aq)

(a) KF is a weak acid and F- is its conjugate base
[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4+] [0.36]
(b) HBr is a strong acid
start (moles)
(c) CO32- is a weak base and HCO3- is it conjugate acid NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
end (moles)

final volume = 80.0 mL + 20.0 mL = 100 mL

0.028 0.025
[NH4+] = [NH3] =
0.10 0.10
16.3 16.3
 Maintaining the pH of Blood Titrations
In a titration a solution of accurately known concentration is
added gradually added to another solution of unknown
concentration until the chemical reaction between the two
solutions is complete.

– the point at which the reaction is complete

– substance that changes color at (or near) the
equivalence point

Slowly add base

to unknown acid
UNTIL
The indicator
changes color
16.3 (pink) 4.7

Strong Acid-Strong Base Titrations Weak Acid-Strong Base Titrations

NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq) CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
OH- (aq) + H+ (aq) H2O (l) CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
At equivalence point
0.10 M NaOH added to 25 mL of 0.10 M HCl
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

16.4 16.4
Strong Acid-Weak Base Titrations Exactly 100 mL of 0.10 M HNO2 are titrated with a 0.10 M
HCl (aq) + NH3 (aq) NH4Cl (aq) NaOH solution. What is the pH at the equivalence point ?
H+ (aq) + NH3 (aq) NH4Cl (aq) start (moles)
At equivalence point HNO2 (aq) + OH- (aq) NO2- (aq) + H2O (l)
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq) end (moles)
0.01
Final volume = 200 mL [NO2-] = = 0.05 M
0.200
NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Initial (M)
Change (M)
Equilibrium (M)
[OH-][HNO2] x2 pOH = 5.98
Kb = - = = 2.2 x 10-11
[NO2 ] 0.05-x
0.05 – x ≈ 0.05 x ≈ 1.05 x 10-6 = [OH-]
16.4

Acid-Base Indicators The titration curve of a strong acid with a strong base.
HIn (aq) H+
(aq) + In- (aq)
[HIn]
≥ 10 Color of acid (HIn) predominates
[In-]
[HIn]
≤ 10 Color of conjugate base (In-) predominates
[In-]

16.5 16.5
 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

16.5