Chapter 11

Polyprotic
Acids
and
Bases

Ch11-1 CHEM 3369

 Polyprotic Acid-Base Systems
ØPolyprotic acids are those that can donate more than one
acidic proton.
Ø Polyprotic bases are those that can accept
more than one acidic proton.
A few examples:

Phosphoric acid

Ch11-2 CHEM 3369

 11-1 Amino Acids Are Polyprotic
Ø Amino acids—building blocks of proteins—have an acidic
carboxyl group, a basic amino group, and a variable substituent
(R) in the structure:

(a molecule with positive and negative charges)

ü −NH2 is more basic than −COOH, and the acidic proton resides
on N of −NH2 instead of on O of −COO−
ü At low pH, both −NH3+ and −COO− are protonated
ü At high pH, neither group is protonated
ü The R group may also have acidic or basic properties
Ch11-3 CHEM 3369
 EXAMPLE Amino Acid Cysteine Has 3 Acidic Protons
Ka1 (or K1) refers to Amphiprotic forms H+
Acidic form the acidic species
with the most protons
H+

This is a triprotic
acid with successive
dissociation constants
Ka1, Ka2, Ka3
H+
This is cysteine,
a molecule with
no net charge
(Zwitterion)

This is a triprotic
base with successive
Basic form hydrolysis constants
Kb1 = Kw/Ka3
Kb1 refers to the Kb2 = Kw/Ka2
Cysteine basic species with Kb3 = Kw/Ka1
no acidic protons
Ch11-4 CHEM 3369
 TABLE 11-1 Acid dissociation constants of 20 common amino acidsa,b

Ch11-5 CHEM 3369

 TABLE 11-1 Acid dissociation constants of 20 common amino acidsa,b

Ch11-6 CHEM 3369

 Proteins Are Polyprotic Acids and Bases
Ø Proteins are polymers made of amino acids (or residues):

Amino acids
(residues)

– 2H2O
Backbone chain (Amino
Rigid unit Rigid unit acid sequence specifies
3-D structure)

Polypeptide
(A long polypeptide
is called a protein)
N-terminal C-terminal
residue residue
Peptide
(amide) R-groups could be acidic, basic,
bond or neutral (form side chains)
There is considerable freedom of rotation
about single bonds joining the amide groups

Ch11-7 CHEM 3369

 Protein 3-D Structure and Function
Ø Proteins have biological functions such as structural support, catalysis of
biochemical reactions, immune response to foreign substances, transport of
molecules and ions across membranes, and control of genetic expression.
Ø For example: Myoglobin, whose function is to store O2 in muscle tissue, has a
compact 3-D structure. Of the 153 amino acids in whale myoglobin, 35 have
basic side groups and 23 are acidic.
Flat iron(II)-porphyrin
complex that can bind
Heme O2, CO, and other
group small molecules
(Active site)
Heme
group

C-terminal
residue

(a) (b)
N-terminal
Overall dimensions: residue Figure 11-4 (a) Space-filling
~ 45 35 25 Å model. (b) Amino acid backbone.
Ch11-8 CHEM 3369
 Separating Proteins
Ø At high pH, most proteins loose so many
protons that they acquire an overall
negative charge
Ø At low pH, most proteins gain so many
protons that they acquire an overall
positive charge
Ø At some intermediate pH, called the
isoelectric pH (or isoelectric point) each
protein has exactly zero net charge
Ø Thus, proteins can be separated from
each other by subjecting a mixture of
proteins to a strong electric field in a
medium design to have a pH gradient
Ø This protein separation technique is
called isoelectric focusing (see Box 11-2) Gel
1 23 4 5 6 7
Ch11-9 CHEM 3369
 11-2 Finding the pH in Diprotic Systems
ØConsider the amino acid leucine, designated HL:
will dissociate some will hardly dissociate
pKa1 = 2.328 pKa2 = 9.744

pKb2 = 11.672 pKb1 = 4.256

H 2L + HL L−
will hardly hydrolize will hydrolize some
Leucine

ØEquilibrium reactions:

Diprotic acid: H2L+ ⇌ HL + H+ Ka1 = K1 ≡ 4.70´10–3

HL ⇌ L− + H+ Ka2 = K2 ≡ 1.80´10–10

Diprotic base: L− + H2O ⇌ HL + OH− Kb1 = 5.55´10–5

HL + H2O ⇌ H2L+ + OH− Kb2 = 2.13´10–12

Ch11-10 CHEM 3369

STRATEGY (a) The Acidic Form, H2L+ (H2A and BH2+ in general)

A salt such as leucine hydrochloride contains the protonated

species H2L+, which can dissociate twice in water
Ø Treat H2L+ and any diprotic acid (H2A, BH22+) as monoprotic
weak acids with Ka = K1 ( K1 >> K2 and, as a source of protons,
the dissociation of HL is negligible relative to that of H2L+)

Ø Thus, to find the pH we set up and solve the equation:

x2
H2L+ ⇌ HL + H+ K1 = –––––
F – x x x F – x

where [HL] = [H+] = x, [H2L+] = F − x,

and F is the formal concentration of H2L+ (= 0.0500 M of leucine
hydrochloride in our example)
Ch11-14 CHEM 3369
STRATEGY (a) The Acidic Form, H2L+ (H2A and BH2+ in general)
will dissociate some will hardly dissociate
Ka1 = 4.70´10–3 Ka2 = 1.80´10–10
pKa1 = 2.328 pKa2 = 9.744

Kb2 = 2.13´10–12 Kb1 = 5.55´10–5

H2 L+ pKb2 = 11.672 HL pKb1 = 4.256 L−
Leucine
will hardly hydrolize will hydrolize some

A salt such as leucine hydrochloride contains the protonated

species H2L+, which can dissociate twice in water
Ø Treat H2L+ and any diprotic acid (H2A, BH22+) as monoprotic
weak acids with Ka = K1 ( K1 >> K2 and, as a source of protons,
the dissociation of HL is negligible relative to that of H2L+)

Ch11-15 CHEM 3369

SOLUTION (a) The Acidic Form, H2L+ (H2A and BH2+ in general)

H2L+ ⇌ HL + H+ K1 = 10–pK1 = 4.70 10–3

0.0500 – x x x
[H+][HL] x2 x2
K1 = –––––––– = ––––– = –––––––––– = 4.70 10–3
[H2L] F – x 0.0500 – x
Ø Use quadratic equation to get x:
[HL] = [H+] = x = 1.32 10–2 M
pH = – log x = 1.88
[H2L+] = F − x = 3.68 10–2 M
Ø The concentration of L− can be found from K2 equilibrium:
K2 [H+][L−] K2[HL]
HL ⇌ L− + H+ K2 = –––––––– ⟹ [L ] = –––––––
−
[HL] [H+]
(1.80 10–10)(1.32 10–2)
–10 M (= K )
[L−] = –––––––––––––––––––––– = 1.80 10 2
(1.32 10 )–2

Ch11-16 CHEM 3369

STRATEGY (b) The Basic Form, L− (A2− and B in general)
will dissociate some will hardly dissociate
Ka1 = 4.70´10–3 Ka2 = 1.80´10–10
pKa1 = 2.328 pKa2 = 9.744

Kb2 = 2.13´10–12 Kb1 = 5.55´10–5

H2 L+ pKb2 = 11.672 HL pKb1 = 4.256 L−
Leucine
will hardly hydrolize will hydrolize some

A salt such as sodium leucinate contains the fully basic species

L−, which can hydrolyze twice in water
Ø Treat L− and any diprotic base (A2−, B) as monoprotic weak
base with Kb = Kb1 = Kw/Ka2 (Kb1 >> Kb2 and the reaction of HL
with water is negligible relative to that of L−)

Ch11-17 CHEM 3369

STRATEGY (b) The Basic Form, L− (A2− and B in general)

A salt such as sodium leucinate contains the fully basic species

L−, which can hydrolyze twice in water

Ø Treat L− and any diprotic base (A2−, B) as monoprotic weak

base with Kb = Kb1 = Kw/Ka2 (Kb1 >> Kb2 and the reaction of HL
with water is negligible relative to that of L−)

Ø Thus, to find the pH we set up and solve the equation:

x2
L− + H2O ⇌ HL + OH− Kb1 = Kw/Ka2 = –––––
F – x x x F – x

where [HL] = [OH−] = x, [H+] = Kw/x, [L−] = F − x,

and F is the formal concentration of L− (= 0.0500 M of sodium
leucinate in our example)
Ch11-18 CHEM 3369
SOLUTION (b) The Basic Form, L− (A2− and B in general)

L− + H2O ⇌ HL + OH− Kb1 = Kw/Ka2 = 5.55 10–5

0.0500 – x x x
[HL][OH−] x2 x2
Kb1 = ––––––––– = ––––– = –––––––––– = 5.55 10–5
[L−] F – x 0.0500 – x
Ø Use quadratic equation to get x:
[HL] = [OH−] = x = 1.64 10–3 M
pOH = – log x = 2.79 ⟹ pH = 14.00 − pOH = 11.21
[L−] = F − x = 4.84 10–2 M
Ø The concentration of H2L+ can be found from Kb2 equilibrium:
Kb2 [H2L+][OH−] [H2L+] x
HL + H2O ⇌ H2L+ + OH− Kb2 = ––––––––––– = ––––––––
[HL] x

[H2L+] = Kb2 = 2.13 10–12 M

Ch11-19 CHEM 3369
STRATEGY (c) The Amphiprotic Form, HL (HA− and BH+ in general)
An aqueous solution of leucine contains HL, an amphiprotic
species that can both donate and accept protons in water:
HL ⇌ H+ + L− Ka = Ka2 = 1.80´10–10
HL + H2O ⇌ H2L+ + OH− Kb = Kb2 = 2.13´10–12

Ø Ka2 > Kb2 and we expect the solution of leucine to be acidic.

Ø But, we cannot ignore the hydrolysis of HL, even if Ka2 >> Kb2,
because H+ produced from dissociation of HL reacts with OH− from
hydrolysis of HL, thereby driving the hydrolysis of HL to the right.

Ø Treat HL and any amphiprotic species of diprotic acids (HA−

and BH+) as intermediates:
pH ≈ ½(pK1 + pK2)
where K1 and K2 are their acid dissociation constants (Ka1 and Ka2).
Ch11-21 CHEM 3369
SOLUTION (c) The Amphiprotic Form, HL (HA− and BH+ in general)
Ø GOOD TO MEMORIZE IT: The pH of the intermediate form of
any diprotic acid is close to midway between the pKa1 and pKa2
values, regardless of the formal concentration.
So, for leucine: pH ≈ ½(pK1 + pK2)
pH ≈ ½(2.328 + 9.744) = 6.036
or [H+] = 10–pH = 10–6.036 = 9.20 10–7 M
Ø The concentration of H2L+ and L− can be found from K1 and K2
equilibria, respectively, using [HL] = 0.0500 M:
[H+][HL] (9.20 10–7)(0.0500)
–6 M
[H2L+] = ––––––––– = ––––––––––––––––––– = 9.79 10
K1 4.70 10–3

K2[HL] (1.80 10–10)(0.0500)

–6 M
[L−] = ––––––– = ––––––––––––––––––– = 9.78 10
[H+] 9.20 10–7
Ch11-22 CHEM 3369
 Summary of Polyprotic Acid Calculations
−H+ −H+
Diprotic systems: H2A HA− A2−
p K1 p K2

ü Threat H2A and BH22+ as monoprotic weak acids

ü Treat A2– and B as monoprotic weak bases
ü Treat HA– and BH+ as intermediates: pH ≈ ½(pK1 + pK2)

−H+ −H+ −H+

Triprotic systems: H3A H2A− HA2− A3−
p K1 p K2 p K3

ü Threat H3A as monoprotic weak acid

ü Treat A3– as monoprotic weak base
ü Treat H2A– as intermediate: pH ≈ ½(pK1 + pK2)
ü Treat HA2– as intermediate: pH ≈ ½(pK2 + pK3)
Ch11-23 CHEM 3369
 11-3 Principal Species
in
Polyprotic Systems

Ch11-24 CHEM 3369

 11-3 Principal Species: Monoprotic Systems

EXAMPLE Estimate (a) the predominant form and (b) the

composition for benzoic acid in an aqueous solution at pH 8.00.
−H+
HA A−
p Ka
More More
acidic pH basic STRATEGY Draw a Box Diagram
Predominant Ø We know that at pH = pKa = 4.20,
form
there is a 1:1 mixture of benzoic acid
(HA) and benzoate ion (A−), i.e.,
Benzoic acid
pKa = 4.20 [HA] = [A−], because
pH = pKa pH
[HA] = [A–] 8.00 pH = pKa + log ([A−]/[HA])
pH = pKa + log (1) = pKa
pH Major species
Ø We also know that the benzoate
< pKa HA ion will be the predominant species
> pKa A− because the solution pH (= 8.00) is
above the pKa (= 4.20) value.
Ch11-26 CHEM 3369
 SOLUTION (a) Estimating the dominant form at pH 8.00

At pH = 8.00, the quotient [A−]/[HA] will be:

log ([A−]/[HA]) = pH − pKa = 8.00 − 4.20 = 3.80

log ([A−]/[HA]) = 103.80 » 6310 = 6310 : 1
There is ~6310 times more A– than HA

(b) Estimating benzoic acid composition at pH 8.00

The fraction (α) of each species can then be found from:

α(A−) 6310
———— = ——— 99.98% is in the form PhCOO−
α(HA) 1
ß

0.02% is in the form PhCOOH

α(HA) + α(A−) = 1
Ch11-28 CHEM 3369
 EXAMPLE Principal Species —Which One and How Much?
Ø (a) What is the predominant form of ammonia in the solution
at pH 7.00? (b) Approximately, how much is in this form?

STRATEGY NH3 + H2O ⇌ NH4+ + OH−

base acid
Ø In Appendix B, we can find pKa = 9.24 for the ammonium ion
(NH4+, the conjugate acid of ammonia, NH3).
More acidic pH More basic

NH4+ NH3

Below pH 9.24, NH4+ will At pH = pKa = 9.24

be the predominant form [NH4+] = [NH3]
pH 7.00

Ch11-30 CHEM 3369

 SOLUTION (a) Estimating the dominant form at pH 7.00
Ø Because pH = 7.00 is 2.24 pH units below pKa (= 9.24), the
quotient [NH3]/[NH4+] will be:
log ([NH3]/[NH4+]) = pH − pKa = 7.00 − 9.24 = –2.24
log ([NH3]/[NH4+]) = 10−2.24 = 0.00575 ≈ 1 : 174
There is ~174 times more NH4+ than NH3

(b) Estimating the composition of NH3(aq) at pH 7.00

Ø The fraction (α) of each species can then be found from:

α(NH3) 1
————–– = ——— ~99.4% is in the form NH4+
α(NH4+) 174
ß

~0.06% is in the form NH3

α(NH3) + α(NH4+) = 1
Ch11-32 CHEM 3369
 11-3 Principal Species: Diprotic Systems
EXAMPLE Estimate (a) the predominant form and (b) the
composition for fumaric acid in an aqueous solution at pH 4.00.
STRATEGY Draw a Box Diagram

pK1 = 3.02 −H+ −H+

pK2 = 4.48 H2A HA− A2−
p K1 p K2
Fumaric acid More More
acidic pH basic
(trans-butenedioic acid)
Predominant
form

pH = pK1
[H2A] = [HA–]
pH = pK2
[HA–] = [A2–]

Ch11-34 CHEM 3369

 11-3 Principal Species: Diprotic Systems
EXAMPLE Estimate (a) the predominant form and (b) the
composition for fumaric acid in an aqueous solution at pH 4.00.
STRATEGY Draw a Box Diagram
pK1 = 3.02 −H+ −H+
pK2 = 4.48 H2A HA− A2−
p K1 p K2
Fumaric acid More More
acidic pH basic
(trans-butenedioic acid)
Predominant
form
pH Major species
< pK1 H 2A
pK1 < pH < pK2 HA−
> pK2 A2− pH = pK1
[H2A] = [HA–]
pH = pK2
[HA–] = [A2–]

Ch11-35 CHEM 3369

 11-3 Principal Species: Diprotic Systems
EXAMPLE Estimate (a) the predominant form and (b) the
composition for fumaric acid in an aqueous solution at pH 4.00.
STRATEGY Draw a Box Diagram
pK1 = 3.02 −H+ −H+
pK2 = 4.48 H2A HA− A2−
p K1 p K2
Fumaric acid More More
acidic pH basic
(trans-butenedioic acid)
Predominant
form
pH Major species
< pK1 H 2A
pK1 < pH < pK2 HA− pH = ½(pK1 + pK2)
pH
> pK2 A2− [H2A] = [A2−] pH = pK = 3.02 4.00
1
[H2A] = [HA–]
We know that the hydrogen fumarate ions pH = pK2 = 4.48
(HA ) are dominant at pH = 4.00 because the
− [HA –] = [A2–]

solution pH is between pK1 (= 3.02) and pK2 (= 4.48).

Ch11-36 CHEM 3369
 SOLUTION (a) Estimating the dominant form at pH 4.00

Ø Because pH = 4.00 is 0.98 pH units above pK1 (= 3.02), the

quotient [HA−]/[H2A] will be:
log ([HA−]/[H2A]) = pH − pK1 = 4.00 − 3.02 = 0.98
log ([HA−]/[H2A]) = 100.98 = 9.55 ≈ 10 : 1
There is ~10 times more HA– than H2A

Ø Because pH = 4.00 is 0.48 pH units below pK2 (= 4.48), the

quotient [A2−]/[HA−] will be:
log ([A2−]/[HA−]) = pH − pK2 = 4.00 − 4.48 = − 0.48
log ([A2−]/[HA−]) = 10–0.48 = 0.33 ≈ 1 : 3
There is ~3 times more HA– than A2–

Ch11-38 CHEM 3369

 (b) Estimating fumaric acid composition at pH 4.00
At pH = 4.00, the approximate fractions (α) of H2A, HA−, and A2−
will therefore be:
α(HA−) 10 α(H2A) + α(HA−) + α(A2−) = 1
————— = ——
α(H2A) 1
pH = 4
α(A2−) 1
————— = ——
α(HA−) 3

ß
≈ 8% H2A
≈ 70% HA−
≈ 22% A2−
Figure 11-1 Fractional composition diagram for fumaric acid.
Ch11-39 CHEM 3369
 11-3 Principal Species: Triprotic Systems
EXAMPLE (a) What are the principal and second most abundant
forms of arginine at pH 10.0?
(b) Approximately what fractions are in these forms?
H+

H+
+NH
2

+NH
2

H+

Ch11-40 CHEM 3369

 11-3 Principal Species: Triprotic Systems
EXAMPLE (a) What are the principal and second most abundant
forms of arginine at pH 10.0? (b) Approximately what fractions
are in these forms? pH Major species
< pK1 H 3A
pK1 < pH < pK2 H 2A −
pK2 < pH < pK3 HA2−
> pK3 A3−

+NH
2

+NH
2

Ch11-41 CHEM 3369

STRATEGY Draw a box diagram showing the major species:
−H+ −H+ −H+
H3Arg2+ H2Arg+ HArg Arg−
p K1 p K2 p K3
H3A 1.82 H2A− 8.99 HA2− 12.1 A3−

More acidic pH More basic

Ch11-42 CHEM 3369

STRATEGY Draw a box diagram showing the major species:
−H+ −H+ −H+
H3Arg2+ H2Arg+ HArg Arg−
p K1 p K2 p K3
1.82 8.99 12.1

More acidic pH More basic

pH = pK1 pH = pK2 pH = pK3

[H3A] = [H2A–] [H2A–] = [HA2–] [HA2–] = [A3–]

Ch11-43 CHEM 3369

STRATEGY Draw a box diagram showing the major species:

−H+ −H+ −H+

H3Arg2+ H2Arg+ HArg Arg−
p K1 p K2 p K3
1.82 8.99 12.1

More acidic pH More basic

pH ≈ ½(pK1 + pK2) pH ≈ ½(pK2 + pK3)

[H3A] = [HA2–] [H2A–] = [A3–]

pH = pK1 pH = pK2 pH = pK3

[H3A] = [H2A–] [H2A–] = [HA2–] [HA2–] = [A3–]

Ch11-44 CHEM 3369

STRATEGY Draw a box diagram showing the major species:
−H+ −H+ −H+
H3Arg2+ H2Arg+ HArg Arg−
p K2 p K3
H2A− 8.99 HA2− 12.1
2nd most Principal
More acidic abundant pH form More basic

pH 10.00

pH = pK2 = 8.99 pH = pK3 = 12.1

Ø We know that HArg (arginine) will be dominant at pH = 10.0 because the
solution pH is between pK2 (= 8.99) and pK3 (= 12.1).

Ø We predict that H2Arg+ will be the second most abundant species at pH =

10.0 because the solution pH is closer to pK2 (= 8.99) than pK3 (= 12.1)
Ch11-45 CHEM 3369
SOLUTION (a) Estimating the dominant forms at pH 10.00

Ø Because pH = 10.00 is 1.01 pH units above pK2 (= 8.99), the

quotient [HArg]/[H2Arg+] will be:

log ([HArg]/[H2Arg+]) = pH − pK2 = 10.00 − 8.99 = 1.01

log ([HArg]/[H2Arg+]) = 101.01 = 10.2 ≈ 10 : 1
There is ~10 times more HArg than H2Arg+

Ø Because pH = 10.0 is 2.1 pH units below pK3 (= 12.1), the

quotient [Arg−]/[HArg] will be:
log ([Arg−]/[HArg]) = pH − pK3 = 10.0 − 12.1 = − 2.1
log ([Arg−]/[HArg]) = 10–2.1 = 0.00794 ≈ 1 : 130
There is ~130 times more HArg than Arg–

Ch11-47 CHEM 3369

 SOLUTION (b) Estimating the composition at pH 10.00

Ø At pH = 10.0, the approximate fractions (α) of HArg and H2Arg+

(two most abundant species) will therefore be:

α(HArg) 10
—————— = —— ~90% is in the form HArg
α(H2Arg+) 1

ß
~10% is in the form H2Arg+
α(HArg) + α(H2Arg+) = 1

Ch11-48 CHEM 3369

 EXAMPLE More on Polyprotic Systems
Ø In the pH range 1.82 (= pK1) to 8.99 = pK2), amphiprotic H2Arg+
is the principal form of arginine. Which is the second
prominent species at (a) pH 6.00 and (b) pH 5.00?
ü We know that the pH of pure H2Arg+ ≈ ½(pK1 + pK2) = 5.40
5.40
pH pH
More acidic 1.82 8.99 More basic

H3Arg2+ H2Arg+ HArg

1.82 8.99
p K1 p K2

At pH 5.40
[H3Arg2+] = [HArg]

Ch11-49 CHEM 3369

 EXAMPLE More on Polyprotic Systems
Ø In the pH range 1.82 (= pK1) to 8.99 = pK2), amphiprotic H2Arg+
is the principal form of arginine. Which is the second
prominent species at (a) pH 6.00 and (b) pH 5.00?
ü We know that the pH of pure H2Arg+ ≈ ½(pK1 + pK2) = 5.40
5.40
pH pH
More acidic 1.82 8.99 More basic

H3Arg2+ H2Arg+ HArg

1.82 8.99
p K1 p K2

pH 5.00 pH 6.00
Below pH 5.40 Above pH 5.40
(and above pK1), (and below pK2),
At pH 5.40
H3Arg2+ is the 2nd HArg is the 2nd most
[H3Arg2+] = [HArg]
most important species important species

Ch11-51 CHEM 3369

 11-4 Titrations in
Polyprotic Systems

Ch11-53 CHEM 3369

 pH of Diprotic Buffers
Ø Treat the same way as a buffer made from monoprotic acid
Buffer pair 1
But, there are two buffer −H+ −H+
pairs in diprotic systems: H2A HA− A2−
p K1 p K2
Buffer pair 2

Ø Hence, two Henderson-Hasselbalch equations apply:

ü Use pK1, if [H2A] and [HA−] known: Both equations are
pH = pK1 + log ([HA−] / [H2A]) always true and
either can be used,
depending on which
ü Use pK2, if [HA−] and [A2−] known:
set of concentrations
pH = pK2 + log ([A2−] / [HA−]) you happen to know.

Ch11-60 CHEM 3369

 EXAMPLE Preparing a Diprotic Buffer
Ø What is the pH of a solution prepared by dissolving 1.00 g of potassium
hydrogen phthalate (KHP, FW = 204.223) and 1.00 g of disodium phthalate
(Na2P, FW = 210.097) in 100.0 mL of water.

KHP ® K+ + HP− Na2P ® 2Na+ + P2−

Buffer pair 2
Ø Because we know the quotient [P2−]/[HP−], use pK2:

[P2−] 1/210.097
pH = pK2 + log ——— = 5.408 + log ————— = 5.94
[HP−] 1/204.223

NOTE: If only KHP dissolved, pH ≈ ½(pK1 + pK2) ≈ ½(2.950 + 5.408) ≈ 4.18,

regardless of KHP concentration (see Example on p. 242).
Ch11-62 CHEM 3369
 11-4 Titration of Diprotic Acid H2A with OH−
Ø In a titration of a diprotic acid H2A, two OH− ions are required to
react with the two H+ ions of each H2A acid molecule:
Buffer pair 1
[HA−]
(1) H2A + OH− ⟶ HA− + H2O pH = pK1 + log ––––––
[H2A]
pKa in Henderson-Hasselbalch equation
always refers to acid in denominator
[A2−]
(2) HA− + OH− ⟶ A2− + H2O pH = pK2 + log ––––––
[HA−]
Buffer pair 2
Ø Four species influence pH: (1) weak diprotic acid H2A; (2) strong
base OH−; (3) conjugate base HA− of weak diprotic acid H2A; and
(4) conjugate diprotic base A2− of weak acid HA−.
Ø Two equivalence volumes: (1) Ve1 and (2) Ve2 = 2Ve1 (always!)
Ch11-63 CHEM 3369
 Figure 11-2 Titration Curves for Polyprotic Acids
Figure 11-2 shows calculated pH curves for 50.0 mL each of three different
0.0200 M diprotic acids, H2A, titrated with 0.100 M OH–.
Some features of the curves are:
• There are two equivalence points and two
buffer regions.
• The same amount of OH # is required to
convert H2A to HA# and HA# to A%# .
• The pH at the midpoint of each buffer region
is the pKa of that acidic species.
• The pH at Ve1 is different, because their Ka2
is different.
• The pH at Ve2 is different, because their Kb1 =
Kw/Ka2 is different.
• Only the middle curve shows two obvious,
steep equivalence points. When the pK
values are to close together or when the pK
values are too low or too high, there may not
be a distinct break at each equivalence Lower curve: pK1 = 4 and pK2 = 6
point. Middle curve: pK1 = 4 and pK2 = 8
Upper curve: pK1 = 4 and pK2 = 10
Ch11-64 CHEM 3369
 POINT A Before OH– Is Added: Weak Acid H2A
Figure 11-2 shows calculated pH curves for
Initial point: Has the pH of the weak 50.0 mL each of three different 0.0200 M
acid H2A, which is treated as mono- diprotic acids, H2A, titrated with 0.100 M OH–.
protic acid with pKa = pK1 and formal
concentration F.
x2
H2A ⇌ HA– + H+ Ka = ––––
F – x x x F – x

x2
–––––––––– = 10–4.00
0.0200 – x
x = 1.37 10–3 M
pH = – log (x) = 2.86
Point A has the same pH in all cases, because Lower curve: pK1 = 4 and pK2 = 6
all three acids have the same pK1 (= 4.00) Middle curve: pK1 = 4 and pK2 = 8
Upper curve: pK1 = 4 and pK2 = 10
and the same formal concentration F
(0.0200 M).
Ch11-66 CHEM 3369
 POINT B Buffer Containing H2A + HA–

Half-way to Ve1: Has the pH of a 1:1

mixture of H2A:HA–, which is treated
as monoprotic acid with pKa = pK1 and
formal concentration F.
[HA−]
pH = pK1 + log –––––
[H2A]

pH = pK1 + log 1 = pK1 = 4.00

Lower curve: pK1 = 4 and pK2 = 6

Middle curve: pK1 = 4 and pK2 = 8
Upper curve: pK1 = 4 and pK2 = 10

Because all three acids have the same pK1 (= 4.00), the pH at Ve1/2
point is the same in all three cases.
Ch11-68 CHEM 3369
POINT C Intermediate Form HA–

At Ve1, the 1st equivalence point: All

H2A has been converted into HA–, the
intermediate form of a diprotic acid.

pH ≈ ½(pK1 + pK2)

pH ≈ ½(pK1 + pK2) =
5.00 at C
6.00 at C’
7.00 at C”
Lower curve: pK1 = 4 and pK2 = 6
Middle curve: pK1 = 4 and pK2 = 8
Upper curve: pK1 = 4 and pK2 = 10

The three acids have the same pK1 (= 4.00), but different values of
pK2. Therefore, the pH at Ve1 point is different in all three cases.
Ch11-70 CHEM 3369
 POINT D Buffer Containing HA– + A2–

Lower curve: pK1 = 4 and pK2 = 6

Middle curve: pK1 = 4 and pK2 = 8
Upper curve: pK1 = 4 and pK2 = 10

Ch11-71 CHEM 3369

 POINT D Buffer Containing HA– + A2–

Half-way from Ve1 to Ve2: Half of the

HA– has been converted into A2–. The
pH is treated as a monoprotic buffer
with pKa = pK2 and [HA–] = [A2–].
[A2–]
pH = pK2 + log –––––
[HA–]

pH = pK2 + log 1
6.00 at D
= pK2 8.00 at D’ Lower curve: pK1 = 4 and pK2 = 6
10.00 at D” Middle curve: pK1 = 4 and pK2 = 8
Upper curve: pK1 = 4 and pK2 = 10

The pH at points D, D’, and D” is equal to the pK2 of each of the three acids.

Ch11-72 CHEM 3369

POINT E Weak Base A2–
At Ve2 = 2Ve1, the 2nd equivalence
point: All of the acid has been converted
into A2–, a weak base with concentration
F’. We find the pH by treating A2– as
monoprotic base with Kb1 = Kw/Ka2:
x 2
A2– + H2O ⇌ HA– + OH– Kb1 = ––––
F’ – x x x F’ – x

F’ = (0.0200)(50.0/70.0) = 0.0143 M

x2 10–6.00 at E
–––––––––– = 10–8.00 at E’ Lower curve: pK1 = 4 and pK2 = 6
0.0143 – x 10–10.00 at E” Middle curve: pK1 = 4 and pK2 = 8
Upper curve: pK1 = 4 and pK2 = 10
x = 1.20 10–5 M at E 9.08 at E
x = 1.19 10–4 M at E’ = [OH–] pH = − log (Kw/ x) = 10.08 at E’
x = 1.15 10–3 M at E” 11.06 at E”
The pH is different for the three acids, because Kb1 is different for all three.
Ch11-74 CHEM 3369
 Figure 11-2 Titration Curves for Polyprotic Acids
Before Ve1: Past Ve1:
[HA−] [A2−]
pH = pK1 + log ––––– pH = pK2 + log –––––
[H2A] [HA−]
Past Ve2:
excess OH−
Half-way from
Ve1 to Ve2:
pH = pK2
At V2e = 2Ve1: weak
base A2− problem
Half-way to Ve1: Kb1 = x2/(F’ – x)
pH = pK1

At Ve1: HA– inter-

Initial point: weak
acid H2A problem mediate form
+OH− +OH−
H 2A HA − A2− pH ≈ ½(pK1 + pK2)
K1 = x2/(F – x) p K1 p K2

Ch11-75 CHEM 3369