Polyprotic Acid-Base Equilibria

Diprotic Acids and Bases

3.) General Process to Determine pH

Intermediate Form (HL)
- More complicated HL is both an acid and base

K a K a2 1.80 10 10
K b K b2 2.13 10 12

Amphiprotic can both donate and accept a proton

Since Ka > Kb, expect solution to be acidic

- Can not ignore base equilibrium

Need to use Systematic Treatment of Equilibrium

Polyprotic Acid-Base Equilibria

Diprotic Acids and Bases

3.) General Process to Determine pH

Intermediate Form (HL)

Step 1: Pertinent reactions:

K1 K b2
K2 K b1

Step 2: Charge Balance:

[H ] [H2 L ] [L- ] [OH - ]
Step 3: Mass Balance:
F [ HL] [ H 2 L ] [ L- ]
Step 4: Equilibrium constant expression (one for each reaction):
[L- ][H ] [HL][H ] [H2 L ][OH - ] K [HL][OH - ]
K2 K1 K b1 b2
[HL] [H2 L ] [HL] [L ]
 Polyprotic Acid-Base Equilibria
Diprotic Acids and Bases

3.) General Process to Determine pH

Intermediate Form (HL)

Step 6: Solve:

Substitute Acid Equilibrium Equations into charge balance:

[HL][H ] [L- ] [HL]K 2 [OH - ] Kw
- -
[H2 L ] [L ] [H ] [OH ] 0 [H2 L ]
K1 [H ] [H ]

All Terms are [HL][H ] [HL]K 2 Kw

related to [H+] [ H ] 0
K1 [H ] [H ]
Multiply by [H+]

[HL][H ]2
[HL]K 2 [H ]2 Kw 0
K1

Polyprotic Acid-Base Equilibria

Diprotic Acids and Bases

3.) General Process to Determine pH

Intermediate Form (HL)

Step 6: Solve:

[HL][H ]2
[HL]K 2 [H ]2 Kw 0
K1
Factor out [H+]2:

[HL]
[H ]2 1 K 2 [HL] Kw
K1
Rearrange:

K 2 [HL] Kw
[H ] 2
[HL]
1
K1
 Polyprotic Acid-Base Equilibria
Diprotic Acids and Bases

3.) General Process to Determine pH

Intermediate Form (HL)

Step 6: Solve:
K 2 [HL] Kw
[H ] 2
[HL]
1
K1
Multiply by K1 and take square-root:

K 2 K1 [HL] K1Kw
[H ]
K1 [HL]
Assume [HL]=F, minimal dissociation:
(K1 & K2 are small)

K 2 K1F K1Kw
[H ]
K1 F

Polyprotic Acid-Base Equilibria

Diprotic Acids and Bases

3.) General Process to Determine pH

Intermediate Form (HL)

Step 6: Solve:
K 2 K1F K1Kw
[H ]
K1 F
Calculate a pH:

( 4.70 x10 3 )( 1.80 x10 10 )( 0.0500 ) ( 4.70 x10 3 )( 1.0 x10 14 )

[H ]
4.70 x10 3 0.0500

8.80 x10 7 M pH 6.06

 Polyprotic Acid-Base Equilibria
Diprotic Acids and Bases

3.) General Process to Determine pH

Intermediate Form (HL)

Step 7: Validate Assumptions

Assume [HL]=F=0.0500M, minimal dissociation (K1 & K2 are small).

Calculate [L-] & [H2L+] from K1 & K2:

[HL][H ] ( 0.0500 )( 8.80 x10 7 )

[H2 L ] 3
9.36 x10 6
K1 4.70 x10

[HL]K 2 ( 0.0500 )( 1.80 x10 10 )

[L ]
-

7
1.02 x10 5
[H ] 8.80 x10

[HL]=0.0500M >> 9.36x10-6 [H2L+] & 1.02x10-5 [L-] Assumption Valid

Polyprotic Acid-Base Equilibria

Diprotic Acids and Bases

3.) General Process to Determine pH

Intermediate Form (HL)

Summary of results:
[L-] [H2L+] two equilibriums proceed equally even though Ka>Kb
Nearly all leucine remained as HL

Solution pH [H+] (M) [H2L+] (M) [HL] (M) [L-] (M)

Acid form 0.0500 M H2A 1.88 1.32x10-2 3.68x10-2 1.32x10-2 1.80x10-10
Intermediate form 0.0500 M HA- 6.06 8.80x10-7 9.36x10-6 5.00x10-2 1.02x10-5
Basic form 0.0500 M HA2- 11.21 6.08x10-12 2.13x10-12 1.64x10-3 4.84x10-2

Range of pHs and concentrations for three different forms

 Polyprotic Acid-Base Equilibria
Diprotic Acids and Bases

3.) General Process to Determine pH

Simplified Calculation for the Intermediate Form (HL)

K 2 K1F K1Kw
[H ]
K1 F
Assume K2F >> Kw:

K 2 K1F
[H ]
K1 F
Assume K1<< F:

K 2 K1F
[H ]
F

Polyprotic Acid-Base Equilibria

Diprotic Acids and Bases

3.) General Process to Determine pH

Simplified Calculation for the Intermediate Form (HL)

K 2 K1F
[H ]
F

Cancel F:

[H ] K2 K1
Take the -log:

- log[H ] 2 ( log K1 log K2 )

1

pH of intermediate form of a
Independent of concentration: pH ( pK1 pK2 )
1 diprotic acid is close to midway
2
between pK1 and pK2
 Polyprotic Acid-Base Equilibria

Polyprotic Acids and Bases

1.) Extend Treatment of Diprotic Acids and Bases to Polyprotic Systems

Rules for triprotic system

1. H3A is treated as a monoprotic acid, Ka = K1

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

K 2 K1F K1Kw
[H ]
K1 F
3. HA2- is also treated similarly as an intermediate form of a diprotic acid
a. Surrounded by H2A- and A3-
b. Use K2 & K3, instead of K1 & K2

K 2 K 3 F K 2 Kw
[H ]
K2 F

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

Polyprotic Acid-Base Equilibria

Isoelectric and Isoionic pH

1.) Isoionic point is the pH obtained when the pure, neutral polyprotic acid
HA is dissolved in water
Neutral zwitterion
Only ions are H2A+, A-, H+ and OH-
- Concentrations are not equal to each other

K1K 2 F K1Kw
Isoionic point: [H ] pH obtained by simply
K1 F dissolving alanine

Remember: Net Charge of Solution is Always Zero!

 Polyprotic Acid-Base Equilibria

Isoelectric and Isoionic pH

2.) Isoelectric point is the pH at which the average charge of the polyprotic
acid is 0
pH at which [H2A+] = [A-]
- Always some A- and H2A+ in equilibrium with HA
Most of molecule is in uncharged HA form

To go from isoionic point (all HA) to isoelectric point, add acid to decrease [A -]
and increase [H2A+] until equal
- pK1 < pK2 isoionic point is acidic excess [A-]

Remember: Net Charge of Solution is Always Zero!

Polyprotic Acid-Base Equilibria

Isoelectric and Isoionic pH

2.) Isoelectric point is the pH at which the average charge of the polyprotic
acid is 0
isoelectric point: [A-] = [H2A+]

[HA][H ] [ A- ]
K 2 [HA]
[H2 A ]
K1 [H ]

[HA][H ] K 2 [HA]

[H ] K1K 2
K1 [H ]

Isoelectric point: pH 2 ( pK1 pK2 )

1