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K a K a2 1.80 10 10
K b K b2 2.13 10 12
Step 6: Solve:
[HL][H ]2
[HL]K 2 [H ]2 Kw 0
K1
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
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
Step 6: Solve:
K 2 K1F K1Kw
[H ]
K1 F
Calculate a pH:
Summary of results:
[L-] [H2L+] two equilibriums proceed equally even though Ka>Kb
Nearly all leucine remained as 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
K 2 K1F
[H ]
F
Cancel F:
[H ] K2 K1
Take the -log:
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
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
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
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-]
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 ]