3/28/2014

Chapter 9: POLYPROTIC
ACID-BASE EQUILIBRIA

Oxalic acid,
rhubarb and
rhubarb pie

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Understanding Polyprotic Species

Diprotic acids, H2A vs. Dibasic species, A2-

Can donate 2 H+
Can accept 2 H+
Ex. H2SO4, H2CO3 Ex. SO42-, CO32-

Triprotic acids, H3A vs. Tribasic species, A3-

Can donate 3 H+
Can accept 3 H+
Ex. H3PO4, Ex. PO43-
H3C6H5O7 (Citric acid) C6H5O73-

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Diprotic Acids and Bases

General formulas:

 H2A = fully acidic form

 HA- = intermediate form; amphoteric

 A2- = fully basic or fully deprotonated form

Equilibria involved: Diprotic Acids and Bases

Diprotic Acid, H2A

K a1→ - +
First dissociation: 
H 2 A + H 2O ←  HA + H3O

Second dissociation: -
K
a2 → -2 +

HA + H 2O ←  A + H3O
Dibasic species, A2-
K b1→
First hydrolysis: A 2- + H 2O ←
 -
 HA + OH
-

Kb2 →
Second hydrolysis: HA - + H 2O ←
  H 2 A + OH
-

Q. How do we calculate Kb1 and Kb2 from Ka values? 4

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Note that H2A and HA- species in the Ka1 expression both appear
in the Kb2 expression. Similarly, the conjugates HA- and A2- in the
Ka2 expression both appear in the Kb1 expression.

Thus,

Proof:
Ka1→ − +

H 2 A + H 2O ←  HA + H 3O
+ K
b2 →
HA− + H 2O ←
  H 2 A + OH
−

Kw→ + −

2 H 2O ← H 3O + OH Kw = Ka1 x Kb2

Polyprotic acids: Amino Acids

NOTE: - COOH group is much more acidic (higher Ka; first to

dissociate) than the –NH3+ group.
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Diprotic Acids
Example: Leucine, H2L

Fully protonated form = Fully dissociated

fully acidic, H2A+ form = fully basic, A-

Stepwise dissociation:

Start with the fully acidic form, H2A+ = H2L+

Dibasic Species

Stepwise hydrolysis of leucine:

Start with the fully basic form, A- = L-

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pH Calculations: Diprotic Acids and Bases

Problem: Find the pH and concentrations of H2SO3, HSO3- and

SO32- in each of the following solutions:
(a) 0.050 M H2SO3
(b) 0.050 M NaHSO3, and
(c) 0.050 M Na2SO3

Note that for diprotic acids and bases, there are 3 species in
solution (i.e. 3 unknowns: H2A, HA- and A2-) so we need 3
independent equations to solve the problem.

pH Calculation: Diprotic Acids and Bases

1. The fully acidic form, H2A

Approximation: In a solution of H2A (Ex. 0.050 M H2SO3),

the 2nd dissociation is usually negligible that H2A behaves
as a monoprotic acid. Also, [A2-] ≈ 0 M.

Calculation of pH and [species]

K a1→ − +

H 2 A + H 2O ←  HA + H 3O
Equil: F-x x x

x2
K a1 =
F−x
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Fully acidic form (H2A) – Cont.

Problem (a): Find the pH and [H2SO3], [HSO3-] and [SO32-]

in a 0.050 M H2SO3 solution. Ka1 = 1.23 x 10-2; Ka2 = 6.6 x 10-8

a1→ K − +

H 2 SO3 + H 2O ←  HSO3 + H 3O
Equil: 0.050-x x x

x2
K a1 = 1.23 x 10−2 = x cannot be ignored
(0.050 − x) since Ka1 isn’t too small

x 2 + 1.23 x 10−2 x − 6.15x10−4 Solve for x using

quadratic equation
x = 1.94 x 10−2 M = [ H 3O + ] = [ HSO3− ]

pH = 1.71 [ H 2 SO3 ] = 0.031M [ HSO3− ] = 1.9 x 10−2 M

0.050 M - x [ SO3−2 ] 0 M
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pH Calculations: Diprotic systems – Cont.

2. The fully basic form, A2-

Approximation: In a solution of A2- (Ex. 0.050 M Na2SO3),

the 2nd hydrolysis is usually negligible that A2- behaves
as a monobasic species. Also, [H2A] ≈ 0 M.

Calculation of pH and [species]

K
b1→
A2− + H 2O ←
 −
 HA + OH
−

Equil: F-y y y

y2 pOH = -log (y)

K b1 =
F−y pH = 14 - pOH

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Recall: Kb1 = Kw/Ka2

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Problem: Find the pH and concentrations of H2SO3, HSO3- and

SO32- in each of the following solutions: Ka1 = 1.23 x 10-2;
Ka2 = 6.6 x 10-8
(a) 0.050 M H2SO3 - DONE!
(b) 0.050 M NaHSO3, and

√ (c) 0.050 M Na2SO3

Answer: pH = 9.94; [H2SO3] ≈ 0 M; [SO32-] = 0.04991 M ≈ 0.050 M and [HSO3-] =

[OH-] = 8.7 x 10-5 M 15

pH Calculations: Diprotic systems – Cont.

3. The intermediate (amphoteric) form, HA-

HA- can act as an acid or a base
Q. What is the predominant species in a solution of HA-?

Compare Ka2 and Kb2 equilibria:

Ka 2
Dissociation: HA− + H 2O ←
 → A2− + H 3O +

Kb2
Hydrolysis: HA− + H 2O ←
 → H 2 A + OH −

HA- will dissociate/hydrolyze to form A2- and H2A

Approximation: [HA-] ≈ FHA- = FNaHA or FKHA 16

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The intermediate form, HA- (Cont.)

Calculation of pH and [species]

Where
K1= Ka1
K2 = Ka2
F = FHA-

pH = -log [H+]

Quick check: pH = ½ (pK1 + pK2)

Solve for [H2A] and [A2-] using [H+] above and K1 & K2
equilibria

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The intermediate form, HA- (Cont.)

Solving for [H2A] and [A2-]:

[ H + ][ HA− ]
K1 = K a1 =
[ H 2 A]

[ H + ][ HA− ]
Thus [ H 2 A] =
K1

K 2 [ HA− ]
2−
Likewise, [ A ] =
[H + ]
[ H + ][ A 2 − ]
From 2 nd dissociation : K2 = Ka2 =
[ HA− ]
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Problem: Find the pH and concentrations of H2SO3, HSO3- and

SO32- in each of the following solutions: Ka1 = 1.23 x 10-2;
(a) 0.050 M H2SO3 - DONE! Ka2 = 6.6 x 10-8
√(b) 0.050 M NaHSO3, and
(c) 0.050 M Na2SO3 – DONE!

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Answer: pH =4.59; [HSO3-] ≈ 0.050 M, [H2SO3] = 1.1 x 10-4 M; [SO32-] = 1.3 x 10-4 M

Triprotic Acids and Bases

Example: H3PO4; PO43-

a1→ K
Successive 
H 3 PO4 + H 2O ← − +
 H 2 PO4 + H 3O
dissociation:
a2 →
K −2
H 2 PO4 − + H 2O ←
  HPO4 + H 3O
+

a3 →
K
HPO4 2− + H 2O ←
 3−
 PO4 + H 3O
+

Successive b1→
K
hydrolysis: PO43− + H 2O ←
 −2
 HPO4 + OH
−

b2 →
K
HPO4 −2 + H 2O ←
 −
 H 2 PO4 + OH
−

K
b3 →
H 2 PO4 − + H 2O ←
  H 3 PO4 + OH
−
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Use handout on pH calculations involving

triprotic systems

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Treatment of triprotic systems

1. H3A is treated as monoprotic weak acid. Ka1 = K1.

2. H2A- is treated as the intermediate form of a diprotic acid.

3. HA2- is also treated as the intermediate form of a diprotic

acid. However, HA2- is “surrounded” by H2A- and A3-, so the
equil. constants to use are Ka2 (= K2) and Ka3 (= K3)

4. A3- is treated as monobasic. Kb1 = Kw/Ka3

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What is the major species at a given pH?

1. When pH < pK1, H2A predominates

2. When pH = pK1, [H2A] = [HA-]

3. When pK1 > pH < pK2, [HA-] predominates
4. When pH = pK2, [HA-] = [A2-]

5. When pH > pK2, [A2-] predominates

Q. Which of the species above predominate at pH 6.50?

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pH 4.00? pH 2.00? 2- -
Answer: A , HA , H2A

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