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pH =(1/2)(pK1 + pK2)
K2 = [H3O+][A2-] / [HA-]
Calculate the pH of a solution containing hydrogen malonate
[HA-] =
0.15 M and malonate [A2-] = 0.05 M (K2 = 2.2 x 10-6 )
Diprotic Buffers
Prepared from the diprotic acid and the
half salt
of the same diprotic acid
pH = pK1 + log [HA-] / [H2A]
Prepared from the half salt and fully
substituted
salt of the same diprotic acid
pH = pK2 + log [A2-] / [HA-]
Amino Acids
The amino acids are the building blocks of proteins and
are examples of diprotic acids (or triprotic acids).
O
H2N CH
O
OH
R
neutral form
H3N
CH
R
zwitterionic form
Amino Acids
13
Amino Acids
Amino acids can be thought of as diprotic acids (and
triprotic acids if the side chain is acidic or basic).
H2L+ + H2O HL + H3O+
Ka1 = K1
HL + H2O L- + H3O+
Ka2 = K2
L- + H2O HL + OH-
Kb1
Kb2
Example:
Calculate the pH of a 0.100 M H2L+ solution (made by dissolving H2L+Cl- in
solution, for L=glycine).
H2L+ + H2O HL + H3O+
HL + H2O L- + H3O+
15
Example:
Calculate the pH of a 0.100 M L- solution (made by dissolving NaL in solution, for
L=glycine).
L- + H2O HL + OH-
16
Amino Acids
The situation is not so simple if we start out with the
intermediate form of the diprotic acid or base, HL.
Both equilibria must be considered simultaneously. The
problem simplifies somewhat because HL acts as both
a weak acid and a weak base and thus will exist
primarily in the HL form and can often be
approximated as the initial concentration of HL.
HL + H2O L- + H3O+
HL + H2O H2L+ + OH-
Ka = 1.67 x 10-10
Kb = 2.24 x 10-12
17
Example:
Calculate the pH of a 0.100 M HL solution.
HL + H2O L- + H3O+
Ka = 1.67 x 10-10
Kb = 2.24 x 10-12
(1)
(2)
(3)
(4)
mass balance
(5)
18
Example:
Calculate the pH of a 0.100 M HL solution.
Solving equation (2) for [H2L+] gives . . .
[H2L+] = Kb[HL]/[OH-] = Kb[HL][H3O+]/Kw
Solving equation (1) for [L-] gives . . .
[L-] = Ka[HL]/[H3O+]
Substituting both of these into equation (4) gives . . .
[H3O+] + Kb[HL][H3O+]/Kw = Kw/[H3O+] + Ka[HL]/[H3O+]
Solving for [H3O+] gives . . .
{1 + Kb[HL]/Kw}[H3O+]2 = Kw + Ka[HL]
[H3O+] = ({Kw + Ka[HL]}/{1 + Kb[HL]/Kw})
19
Example:
Calculate the pH of a 0.100 M HL solution.
The major species will be HL so this can be approximated by the initial
concentration, 0.100 M
[H3O+] ({Kw + 0.100Ka}/{1 + 0.100Kb/Kw})
= ({1.00 x 10-14 +0.100(1.67 x 10-10)}
{1 + 0.100(2.24 x 10-12/1.00 x 10-14)})
= 8.45 x 10-7 M
pH = -log[H3O+] = 6.07
20
Example:
Calculate the pH of a 0.100 M HL solution.
[L-] = Ka[HL]/[H3O+] = (1.67 x 10-10)(0.100)/(8.45 x 10-7)
= 1.98 x 10-5 M
[H2L+] = Kb[HL][H3O+]/Kw
= (2.24 x 10-12)(0.100)(8.45 x 10-7)/1.00 x 10-14)
= 1.89 x 10-5 M
The approximation that [HL] = 0.100 M was a good one because the
concentrations of L- and H2L+ are both << 0.100 M.
21
Ka1 = K1
Ka2 = K2
Ka3 = K3
Kb1 = Kw/Ka3
Kb2 = Kw/Ka2
Kb3 = Kw/Ka1
22
23
Fractional composition
diagram for a
monoprotic
acid with pKa = 5
Fractional composition
diagram for a diprotic acid
Low pH H2A dominates
Titration Reactions
A volumetric analysis is any procedure in which the
volume of reagent needed to react with analyte is
determined.
In a titration, small increments of a reagent solution (the
titrant) are added to an analyte solution until their
reaction is complete.
From the quantity of titrant required, the unknown quantity
of analyte present can be determined.
Titration Reactions
Requirements for a titration reaction . . .
1. The reaction must have a large equilibrium
constant.
2. The titration reaction must proceed rapidly.
Common types of titration reactions
3. acid-base
4. oxidation-reduction
5. complex formation
6. precipitation
Acid-Base Titrations
A titration curve is a graph showing how the pH changes
as titrant is added.
Reaction goes to completion as titrant is added.
1. It exhibits a rapid change in pH near the
equivalence point.
2. At the equivalence point
The slope dpH/dV
The second derivative d2pH/dV2 = 0
(an inflection point).
32
pH
Inflection point
dpH2/dV2=0
Region 2:
At the equivalence point
Region 1:
Before the equivalence point
Vbase
34
Region 2
At the equivalence point
Region 3
After the equivalence point
Example:
Consider the titration of 100 mL of 0.100 M HCl with 0.500 M NaOH.
a. Determine the volume of NaOH that must be added to reach equivalence.
moles acid = moles base
MacidVacid = MbaseVbase
Vbase = MacidVacid / Mbase
= (0.100M)(100mL)/(0.500M)
= 20.0 mL
36
Example:
Consider the titration of 100 mL of 0.100 M HCl with 0.500 M NaOH.
b. Determine the pH after 5.00 mL of NaOH have been added.
pH is determined by the amount of excess acid still present.
MnewVnew = M1 V1 x (% remaining)
[H+] x 105 = 0.100 x 100 mL x (Ve-Vbase)/Ve
37
Example:
Consider the titration of 100. mL of 0.100 M HCl with 0.500 M NaOH.
d. Determine the pH after 25.0 mL of NaOH have been added.
pH is determined by the excess amount of titrant (NaOH) that has been added.
Vexcess base = Vbase - Ve = 25.0 20.0 = 5.0 mL
MnewVnew = M1V1 (excess base)
[OH-] x 125 = 0.500 x 5.0 mL
=0.500 x 5.0 / 125
= 0.020 M
pH = -log[H+] = -log{Kw/[OH-]} = -log{1.00x10-14/0.020}
= 12.30
38
40
41
Region 4:
Region 3:
Region 2:
Region 1:
42
Example:
Consider the titration of 50.0 mL of 0.200 M acetic acid (HOAc) with 0.250 M
NaOH.
HOAc
pKa = 4.76
44
Example:
Consider the titration of 50.0 mL of 0.200 M acetic acid (HOAc) with 0.250 M
NaOH.
HOAc
pKa = 4.76
HA
+ OH- A- + H2O
10 of 40 (equivalence point)
= 4.76 + log ( / )
= 4.76 + log(0.25/0.75) = 4.28
45
Example:
Consider the titration of 50.0 mL of 0.200 M acetic acid (HOAc) with 0.250 M
NaOH. HOAc
pKa = 4.76
d. Determine the pH after 40.0 mL of titrant (NaOH) have been added.
This is the equivalence point. All of the acid has been converted to its conjugate
base, pH is determined by the equilibrium for the conjugate base
A- + H2O
0.200(50/90)-y
OH- + HA
Kb = [OH-][HA]/[A-]
Dilution factor
Ka = 10
-4.76
46
Example:
Consider the titration of 50.0 mL of 0.200 M acetic acid (HOAc) with 0.250 M
NaOH.
HOAc
pKa = 4.76
50
pH too low
no sharp break
pH
Vbase
Color 2
Acid-Base Indicators
Thymol Blue (pK1 = 1.7, pK2 = 8.9)
H2T + H2O HT- + H3O+
pH = pK1 + log{[HT-]/[H2T]}
pH = pK2 + log{[T2-]/[HT-]}
[H2T] = [HT-]
orange
[HT-] = [T2-]
green
Choosing an Indicator
An indicator whose transition range overlaps the
steepest part of the titration curve as closely as
possible will allow the most accurate determination of
the end point.
The difference between the observed end point (color
change) and the true equivalence point is called the
indicator error indicator error.
Indicators are also acids (bases) and therefore react
with the titrant and influence the indicator error.
Choosing an Indicator
Both indicators could be used for this titration, but bromocresol purple would
lead to a slightly smaller indicator error because the color transitions at a pH
closer to the equivalence pH