Polyprotic Acid-Base Equilibria

Clutch - 1st edition - Analytical Chemistry
9. Polyprotic Acid-Base Equilibria
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CONCEPT: DIPROTIC ACIDS
Diprotic acids and bases are compounds that can donate or accept _______ H+ ion.
For diprotic acids ________ their equations can be illustrated by:
Pr oducts
H2A (aq) + H2O (l) HA– (aq) + H3O+ (aq) K a1 = =
Reac tan ts
Pr oducts
HA– (aq) + H2O (l) A2– (aq) + H3O+ (aq) Ka2 = =
Reac tan ts
For diprotic bases ________ their equations can be illustrated by:
Pr oducts
A2– (aq) + H2O (aq) HA – (aq) + OH – (aq) K b1 = =
Reac tan ts
Pr oducts
HA – (aq) + H2O (aq) H2A (aq) + OH – (aq) K b2 = =
Reac tan ts
Based on these equations the relationship between the different forms of diprotic species are:
As a result of these equations for diprotic acids and bases the relationship between Ka and Kb will be:
K a1 ⋅ K b2 = K w K a 2 ⋅ K b1 = K w
When dealing with diprotic acids:
1) H2A can be treated as a monoprotic acid and we use ________ can be used to find pH.
2) HA – represents the intermediate form and we use ________ can be used to find pH.
3) A2– represents the basic form and we use ________ can be used to find pH.
Page 1
PRACTICE: DIPROTIC ACID CALCULATIONS 1
EXAMPLE 1: Sulfurous acid, H2SO3, represents a diprotic acid with a Ka1 = 1.6 x 10-2 and Ka2 = 4.6 x 10-5. Calculate the
pH and concentrations of H2SO3, HSO3– and SO32– when given 0.200 M H2SO3.
EXAMPLE 2: Determine the pH of 0.080 M Na2S. Hydrosulfuric acid, H2S, contains Ka1 = 1.0 x 10-7 and Ka2 = 9.1 x 10-8.
Page 2
PRACTICE: DIPROTIC ACID CALCULATIONS 2
EXAMPLE: If Ka1 = 4.46 x 10-7 and Ka2 = 4.69 x 10-11 for H2CO3 what is the pH for a 0.15 M solution of NaHCO3?
PRACTICE: An unknown diprotic acid has an initial concentration of 0.025 M. What is the pH of the solution if pka1 is 3.25
and pKa2 is 6.82?
Page 3
CONCEPT: POLYPROTIC ACIDS

Our understanding of diprotic acids and bases can be used to understand polyprotic acids and bases.
For polyprotic acids ________ their equations can be illustrated by:
Pr oducts
H3A (aq) + H2O (l) H2A– (aq) + H3O+ (aq) K a1 = =
Reac tan ts
Pr oducts
H2A– (aq) + H2O (l) HA2– (aq) + H3O+ (aq) Ka2 = =
Reac tan ts
Pr oducts
HA2– (aq) + H2O (l) A3– (aq) + H3O+ (aq) K a3 = =
Reac tan ts
For polyprotic bases ________ their equations can be illustrated by:
Pr oducts
A3– (aq) + H2O (l) HA2– (aq) + OH – (aq) K b1 = =
Reac tan ts
Pr oducts
HA2– (aq) + H2O (l) H2A – (aq) + OH – (aq) K b2 = Reac tan ts =
Pr oducts
H2A – (aq) + H2O (l) H3A (aq) + OH – (aq) K b3 = =
Reac tan ts
As a result of these equations for polyprotic acids and bases the relationship between Ka and Kb will be:
K a1 ⋅ K b3 = K w K a 2 ⋅ K b2 = K w K a3 ⋅ K b1 = K w
When dealing with polyprotic acids:
• H3A can be treated as a monoprotic acid and we use ________ can be used to find pH.
• A3– represents the basic form and we use ________ can be used to find pH.
H 2 A− K a1K a 2 [ ]0 + K a1K w HA 2− K a 2 K a3[ ]0 + K a 2 K w

[H + ] ≈ [H + ] ≈
K a1 + [ ]0 K a 2 + [ ]0
Page 4
PRACTICE: POLYPROTIC ACID CALCULATIONS 1
EXAMPLE 1: Calculate the equilibrium concentrations of H3PO4, H2PO4–, HPO42-, PO43-, and H3O+ for 0.35 M H3PO4.
Ka1 = 7.2 x 10-3, Ka2 = 6.3 x 10-8, and Ka3 = 4.2 x 10-13.
Page 5
PRACTICE: POLYPROTIC ACID CALCULATIONS 2

EXAMPLE 1: Determine the pH of 0.250 M sodium hydrogen phosphate, Na2HPO4. Phosphoric acid, H3PO4, contains Ka1 =
7.5 x 10-3, Ka2 = 6.2 x 10-8 and Ka3 = 4.2 x 10-13.
EXAMPLE 2: Determine the pH of 0.150 M citric acid, H3C6H5O7. It possesses Ka1 = 7.4 x 10-4, Ka2 = 1.7 x 10-5 and Ka3 =
4.0 x 10-7.
Page 6
CONCEPT: MONOPROTIC & DIPROTIC BUFFERS

A diprotic buffer can be approached in a way similar to monoprotic buffers. The key difference is that a diprotic acid has 2
pKa values.
For Monoprotic Buffers
Ka
HA A–
Acid Form Base Form
HClO + NaClO (aq) (conjugate base)

pH = pKa + log
Weak oxyacid Conjugate base
(weak acid)
(Has 1 less Hydrogen)
For Diprotic Buffers
Ka1 Ka2
H2A HA– A2–
Acid Form Intermediate Form Base Form
⎛ HA − ⎞ ⎛ A 2− ⎞
pH = pKa1 + log ⎜ ⎟ pH = pKa 2 + log ⎜ −⎟
⎝ H2A ⎠ ⎝ HA ⎠
−2
30.0 mL of 0.10 M Na 2SO3 Ka 2 = 6.4 x 10 −8
0.20 M H 2SO3 & 0.25 M NaHSO3 Ka1 = 1.6 x 10
20.0 mL of 0.20 M NaHSO3
Page 7
PRACTICE: MONOPROTIC & DIPROTIC BUFFERS CALCULATIONS 1

EXAMPLE 1: What is the pH of a solution consisting of 2.5 M potassium dihydrogen phosphite (KH2PO3) and 2.75 M
phosphorus acid (H3PO3)? Ka1 = 3.0 x 10-2 and Ka2 = 1.66 x 10-7.
EXAMPLE 2: Sulfurous acid, H2SO3, is a major component in the creation of commercial fertilizers. What is the buffer
component concentration ratio of a buffer that has a pH of 1.15? Ka1 = 1.39 x 10-2 and Ka2 = 6.73 x 10-8.
PRACTICE: Calculate the pH of a solution made by mixing 8.627 g of sodium butanoate in enough 0.452 M butanoic acid,
HC4H7O2, to make 250.0 mL of solution. Ka = 1.5 x 10-5.
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CONCEPT: POLYPROTIC BUFFERS

A triprotic buffer can be approached in a way similar to diprotic buffers. The key difference is that a triprotic acid has 3 pKa
values.
For Polyprotic Buffers
Ka1 Ka2 Ka3

H3A H2 A– HA2 – A3 –
Acid Form Intermediate 1 Intermediate 2 Base Form
⎛ H2A– ⎞ ⎛ HA 2– ⎞ ⎛ A 3– ⎞
pH = pKa1 + log ⎜ ⎟ pH = pKa 2 + log ⎜ –
⎟ pH = pKa 3 + log ⎜ 2– ⎟
⎝ H 3A ⎠ ⎝ H2A ⎠ ⎝ HA ⎠
0.10 M H 3C6 H 5O 7 Ka1 = 7.4 ×10 −4 0.25 moles Na 2 HC6 H 5O 7 Ka 2 = 1.7 ×10 −5 50.0 mL of 0.32 M Na 3C6 H 5O 7 Ka 3 = 4.0 ×10 −7
0.15 M NaH 2 C6 H 5O 7 0.17 moles NaH 2 C6 H 5O 7 60.0 mL of 0.25 M NaHC6 H 5O 7
Page 9
CONCEPT: PRINCIPAL SPECIES

The acid constant, Ka, of an acid tells us the numerical value that an acidic hydrogen can be removed.
For a monoprotic acid: When the pH < pka then [HA] is ________________ than [A-].
When the pH > pka then [HA] is ________________ than [A-].
• The relationship between pH and pKa can be furthered applied to diprotic and polyprotic acids.
EXAMPLE 1: What is the predominant form of the diprotic acid, methionine, at a pH equal to 4.18? Ka1 = 6.6 x 10-3 and Ka2
= 8.3 x 10-10.
EXAMPLE 2: What is the predominant form of histidine at a pH equal to 8.00? pKa1 = 1.6, pKa2 = 5.97 and pKa3 = 9.28.
EXAMPLE 3: What is the second most predominant form in the previous question?
Page 10
CONCEPT: ISOELECTRIC AND ISOIONIC POINT

Isoelectric or isoionic points represent the pH where a polyprotic acid doesn’t migrate to an electric field because it’s neutral.
R R R
H3N COOH H3N COO H2N COO
H H H
Below Isoelectric Point At Isoelectric Point Above Isoelectric Point
At the isoionic point the polyprotic acid exists as an intermediate and so we can utilize past equations to determine [H+].
Diprotic Acid Polyprotic Acid
H 2 A− HA 2−
K a1 K a 2 F + K a1 K w K a1K a 2 [ ]0 + K a1K w K a 2 K a3[ ]0 + K a 2 K w

[H + ] = [H + ] ≈ [H + ] ≈
K a1 + F K a1 + [ ]0 K a 2 + [ ]0
The isoelectric point is the pH where [H2A] = [A–] and therefore the average charge is equal to zero.
Diprotic Acid Polyprotic Acid
1 1 1
pH = (pK a1 +pK a 2 ) pH = (pK a1 +pK a 2 ) pH = (pK a 2 +pK a3 )
2 2 2
Page 11
PRACTICE: ISOELECTRIC AND ISOIONIC POINT CALCULATIONS 1

EXAMPLE 1: Calculate the isoelectric and isoionic pH of 0.025 M glutamine. pKa1 = 2.19, pKa2 = 9.00.
EXAMPLE 2: Draw the structures and charge of aspartic acid at pH = 9.82.
PRACTICE 1: Calculate the pI value for histidine. pKa1 (carboxyl group) = 1.60, pKa2 (ammonium group) = 9.28, pKa3 (R-
group) = 5.97.
PRACTICE 2: Calculate the pI value for gluatamic acid. pKa1 (carboxyl group) = 2.16, pKa2 (ammonium group) = 9.96, pKa3
(R-group) = 4.30.
Page 12

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Clutch - 1st edition - Analytical Chemistry

9. Polyprotic Acid-Base Equilibria

CONCEPT: DIPROTIC ACIDS

For diprotic acids ________ their equations can be illustrated by:

For diprotic bases ________ their equations can be illustrated by:

When dealing with diprotic acids:

PRACTICE: DIPROTIC ACID CALCULATIONS 1

PRACTICE: DIPROTIC ACID CALCULATIONS 2

CONCEPT: POLYPROTIC ACIDS

For polyprotic acids ________ their equations can be illustrated by:

For polyprotic bases ________ their equations can be illustrated by:

When dealing with polyprotic acids:

H 2 A− K a1K a 2 [ ]0 + K a1K w HA 2− K a 2 K a3[ ]0 + K a 2 K w

PRACTICE: POLYPROTIC ACID CALCULATIONS 1

PRACTICE: POLYPROTIC ACID CALCULATIONS 2

CONCEPT: MONOPROTIC & DIPROTIC BUFFERS

For Monoprotic Buffers

HClO + NaClO (aq) (conjugate base)

For Diprotic Buffers

PRACTICE: MONOPROTIC & DIPROTIC BUFFERS CALCULATIONS 1

CONCEPT: POLYPROTIC BUFFERS

For Polyprotic Buffers

Ka1 Ka2 Ka3

Acid Form Intermediate 1 Intermediate 2 Base Form

CONCEPT: PRINCIPAL SPECIES

When the pH > pka then [HA] is ________________ than [A-].

CONCEPT: ISOELECTRIC AND ISOIONIC POINT

H3N COOH H3N COO H2N COO

Diprotic Acid Polyprotic Acid

K a1 K a 2 F + K a1 K w K a1K a 2 [ ]0 + K a1K w K a 2 K a3[ ]0 + K a 2 K w

Diprotic Acid Polyprotic Acid

PRACTICE: ISOELECTRIC AND ISOIONIC POINT CALCULATIONS 1

EXAMPLE 2: Draw the structures and charge of aspartic acid at pH = 9.82.

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