Polyprotic Acids

A monoprotic acid is a molecule that is capable of

donating only a single proton to an acceptor molecule.
A polyprotic acid is a molecule capable of donating two
or more protons to acceptor molecule(s).
H2SO4(aq) + H2O() H3O+(aq) + HSO4-(aq)
strong acid
HSO4-(aq) + H2O() H3O+(aq) + SO42-(aq)
weak acid
HSO4-(aq) is amphoteric, it can act as a proton donor or
acceptor.

Weak Polyprotic Acids

H2CO3(aq) + H2O() H3O+(aq) + HCO3-(aq)
Ka1 = [H3O+][HCO3-] / [H2CO3]
HCO3-(aq) + H2O() H3O+(aq) + CO32-(aq)
Ka2 = [H3O+][CO32-] / [HCO3-]
The [H3O+] in the two ionization equilibria are one in the
same.
Successive ionization constants usually decrease by a
factor of ~104 to 106. The negative charge left behind
by the loss of a proton causes the next proton to be
more tightly bound, such that each step in the
ionization of a polyprotic acid occurs to a much lesser
extent than the previous step.

Weak Polyprotic Acids

The exact calculation of simultaneous equilibria can be
complex.
However, the solution to the simultaneous equilibria
simplifies considerably if . . .
The original concentration is not too small and
Ka1 and Ka2 differ by more than a factor of 100,
which is generally the case.

Diprotic Acid with K1 >> K2

H2A + H2O H3O+ + HAHA- + H2O H3O+ + A2(1) K1 > 100K2
(2) Solution contains mainly H2A with a
little HA(3) Second equilibrium can be ignored
(4) Calculate pH from the expression
for K1
K1 = [H3O+][HA-] / [H2A]

Diprotic Acid with K1 >> K2

Calculate the pH of a 0.15 M solution of

malonic acid (pK1 = 2.85 and pK2 = 5.66)
K1 > 100K2 but K1 is large enough that [H2A] C
H2 A

H2A + H2O H3O+ + HAAt equilibrium (1) [HA-] = [H3O+]

(2) [H2A] = C H2A - [H3O+]

K1 = [H3O+][HA-] / [H2A] = [H3O+]2 / 0.15 [H3O+]

Solve the quadratic equation giving [H3O+] = 1.38
x 10-2
pH = 1.86

Half Salt of a Diprotic Acid

NaHA Na+ + HAH2A + H2O H3O+ + HA- (1)
HA- + H2O H3O+ + A2- (2)
Both equlibria effect [HA-]
(1) HA- is removed in (1) and converted to [H 2A]
(2) HA- is converted in (2) to A 2Mass balance [A2-] = [H3O+] + [H2A] (eliminate HA-)
From K2 = [H3O+][A2-] / [HA-] [A2-] = K2[HA-] / [H3O+]
Substitute for [A2-] in the mass balance
K2[HA-] / [H3O+] = [H3O+] + [H2A] (3)

Half Salt of a Diprotic Acid

Contd
From K = [H O ] [HA ] / [H A]
1

[H2A] = [H3O+] [HA-] / K1

Substitute for [H2A] in (3)
[H3O+] + ([H3O+] [HA-] / K1) = K2[HA-] / [H3O+]
Multiply through by [H3O+]K1 and rearrange
[H3O+]2(K1 + [HA-]) = K1 K2[HA-]
[H3O+]2 = K1 K2[HA-] / (K1 + [HA-]) (formal solution)
Notice: for typical situations [HA-] >> K1
K1 + [HA-] [HA-]
then [H3O+]2 = K1 K2

pH =(1/2)(pK1 + pK2)

Salt of a Diprotic Acid

Na2A 2 Na+ + A2H2A + H2O H3O+ + HA- (1)
HA- + H2O H3O+ + A2- (2)
The solution contains HA- and A2- with little H2A
Equilibrium (1) is not important and pH can be calculated from (2)

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 )

2.2 x 10-6 = [H3O+][0.05] / [0.15]

[H3O+] = 6.6 x 10-6 and pH = 5.18

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

The R group is different for all of the amino acids, it can

be nonpolar, polar, acidic or basic.
11

Amino Acids

Diprotic Acids and Bases

The zwitterionic form of an amino acid (molecule with
both positive and negative charges) is that found in
solution at neutral pH because the carboxyl group is
more acidic than the ammonium group.
The charge state of both groups depends upon the pH,
both can be protonated or deprotonated.
The structures and acid dissociation constants of the
common amino acids are summarized in Table 9-1.

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

HL + H2O H2L+ + OH-

Kb2

Recall the relationship between Ka and Kb for polyprotic

acids and bases
Ka1 Kb2 = Kw
and
Ka2 Kb1 = Kw
For most diprotic acids, Ka1 >> Ka2 and it can be
approximated as a monoprotic acid with Ka = Ka1.
14

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+

Ka1 = K1 = 4.47 x 10-3

HL + H2O L- + H3O+

Ka2 = K2 = 1.67 x 10-10

Ka1 =[HL][H3O+]/[H2L+] = x2/(0.100-x) = 4.47 x 10-3

x2 + 4.47 x 10-3 x 4.47 x 10-4 = 0
x = 1.90 x 10-2 M
pH = 1.721
[HL] = [H3O+] = 1.90 x 10-2 M
[H2L+] = {0.100 1.90 x 10-2} M = 0.081 M
[L-] = Ka2[HL]/[H3O+] = 1.67 x 10-10

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-

Kb1 = Kw/Ka2 = 5.99 x 10-5

HL + H2O H2L+ + OH-

Kb2 = Kw/Ka1 = 2.24 x 10-12

Kb1 =[HL][OH-]/[L-] = x2/(0.100-x) = 5.99 x 10-5

x2 + 5.99 x 10-5 x 5.99 x 10-6 = 0
x = 2.42 x 10-3 M
pOH = 2.616 pH = 11.384
[HL] = [OH-] = 2.42 x 10-3 M
[L-] = {0.100 2.42 x 10-3} M = 0.098 M
[H2L+] = Kb2[HL]/[OH-] = 2.24 x 10-12

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

HL + H2O H2L+ + OH-

Kb = 2.24 x 10-12

Ka = [L-][H+]/[HL] = 1.67 x 10-10

(1)

Kb = [H2L+][OH-]/[HL] = 2.24 x 10-12

(2)

Kw = [H+][OH-] = 1.00 x10-14

(3)

charge balance [H+] + [H2L+] = [OH-] + [L-]

(4)

mass balance

(5)

0.100 = [H2L+] + [HL] + [L-]

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

Triprotic Acids and Bases

Polyprotic acid dissociation equilibria
H3A + H2O H2A- + H3O+

Ka1 = K1

H2A- + H2O HA2- + H3O+

Ka2 = K2

HA2- + H2O A3- + H3O+

Ka3 = K3

Polyprotic base hydrolysis equilibria

A3- + H2O HA2- + OH-

Kb1 = Kw/Ka3

HA2- + H2O H2A- + OH-

Kb2 = Kw/Ka2

H2A- + H2O H3A + OH-

Kb3 = Kw/Ka1
22

Triprotic Acids and Bases

1. H3A is treated like a monoprotic weak acid with
Ka = K 1
2. H2A- is treated as the intermediate form of a diprotic
acid
[H3O+] {(K1K2C + K1Kw)/(K1 + C)}
3.

HA2- is also treated as the intermediate form of a

diprotic acid, but now we use K2 and K3
[H3O+] {(K2K3C + K2Kw)/(K2 + C)}

4. A3- is treated as monobasic species with

Kb = Kb1 = Kw/Ka3

23

Dominant Species for a Triprotic

Acid

Which is the Principal Species

The principal species in solution at a given pH can be
determined by comparing the pKa(s) of the species to
the pH.
For every 1 unit difference the ratio of the acid to its
conjugate base differ by a factor of 10.
At pH > pKa the conjugate base will dominate
At pH < pKa, the acid will dominate.
pH = pKa + log [A-]/[HA]
The analogous argument applies to polyprotic systems,
but all pKas must be considered.
25

Species in Solution for a Monoprotic Acid

HA + H2O H3O+ + AMass Balance CHA = [A-] + [HA]
Ka = [H3O+][A-] / [HA]
Ka = [H3O+](CHA - [HA]) / [HA] (substitute for [A-])
[HA] = CHA [H3O+]/{[H3O+] + Ka} (rearrange for [HA])
HA = fraction of all species containing A that is HA
HA = [HA]/{[HA] + [A-]} = [HA]/CHA
= [H3O+]/{[H3O+] + Ka}
A = fraction of all species containing A that is AA- = [A-]/{[HA] + [A-]} = [A-]/CA= Ka/{[H3O+] + Ka}
Each species given as an expression that contains only pH
and an equilibrium constant

Fractional composition
diagram for a
monoprotic
acid with pKa = 5

Species in Solution for a Diprotic

Acid

Fraction of species containing A present as H2A

H2A = [H2A]/CH2A
= [H3O+]2/{[H3O+]2 + K1[H3O+] + K1K2}
Fraction of species containing A present as HAHA- = [HA-]/C
= K1[H3O+]/{[H3O+]2 + K1[H3O+] + K1K2}
Fraction of species containing A present as HAA2- = [A2-]/C
= K1K2/{[H3O+]2 + K1[H3O+] + K1K2}
28

Fractional composition
diagram for a diprotic acid
Low pH H2A dominates

Intermediate pH HA- dominate

High pH A2- 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

Titration of Strong Acid w/ Strong Base

Titration Reaction:
H3O+(aq) + OH-(aq) 2 H2O( )
Region 1: Before the Equivalence Point
pH is determined by excess acid in solution not yet
neutralized
Region 2: At the Equivalence Point
pH is determined by the autoionization of H2O
pH = 7.00 for titration of strong acid with strong
base.
Region 3: After the Equivalence Point
pH is determined by excess titrant (base) added to the
solution
33

Titration of Strong Acid with Strong Base

Region 3:
After the equivalence point

pH

Inflection point
dpH2/dV2=0

Region 2:
At the equivalence point

Region 1:
Before the equivalence point
Vbase
34

Titration of a Strong Base with a Strong Acid

Region 1
Before the equivalence point

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

= (0.100M)(100.mL) x (20.0-5.00)mL/20.0mL /105mL

= 0.0714 M
pH = -log[H+] = -log(0.0714) = 1.15

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

Titration of Weak Acid with Strong Base

Titration Reaction:
HA (aq) + OH- (aq) A-(aq) + H2O( )
Reaction goes to completion as strong base is added.
Region 1:Before Base is Added
pH is determined by the equilibrium for the weak acid.
HA + H2O H3O+ + AKa = [H3O+][A-]/[HA]
39

Titration of Weak Acid with Strong Base

Region 2: Before the Equivalence Point
The Henderson-Hasselbach equation is used to
determine the pH because the solution is a buffer (HA
and A-) are present.
pH = pKa + log{[A-]/[HA]}
Region 3: At the Equivalence Point
All of the acid has been converted to its conjugated
base.
pH is determined by the equilibrium for the conjugate
base
A- + H2O HA + OHKb = Kw/Ka = [HA][OH-]/[A-]

40

Titration of Weak Acid with Strong Base

Region 4: After the Equivalence Point
pH is determined by the excess titrant (OH-, base)
added to the solution.

41

Titration of Weak Acid with Strong Base

Region 4:
Region 3:

Region 2:
Region 1:
42

CHAPTER 10: Figure 10.2

Example:
Consider the titration of 50.0 mL of 0.200 M acetic acid (HOAc) with 0.250 M
NaOH.
HOAc

pKa = 4.76

a. Determine the volume of NaOH that must be added to reach equivalence.

moles acid = moles base
MacidVacid = MbaseVbase
Vbase = MacidVacid / Mbase
= (0.200M)(50.0mL)/(0.250M)
= 40.0 mL

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

c. Determine the pH after 10.0 mL of titrant (NaOH) have been added.

The Henderson-Hasselbach equation is used to determine the pH because the
solution is a buffer (HA and A-) are present.
pH = pKa + log{[A-]/[HA]}
Titration Reaction:

HA

Relative initial quantities

Relative final quantities

+ 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

Kb = [HA][OH-]/[A-] = Kw/Ka = {1.00x10-14/1.74x10-5} = 5.75 x10-10

= y2/0.111-y y2/0.111 assume y << 0.111
y = [HA] = [OH-] = 7.99 x 10-6 M
pH = -log[H3O+] = -log Kw/Kb = -log (1.00x10-14/7.99x10-6) = 8.90

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

e. Determine the pH after 50.0 mL of titrant (NaOH) have been added.

pH is determined by the excess titrant (NaOH) added to the solution.
Vexcess base = Vbase Ve = 50.0 40.0 = 10.0 mL
MnewVnew = M1V1 (excess base)
[OH-] = 0.250 x 10.0 / 100.0
= 0.0250 M
pH = -log[H+] = -log{Kw/[OH-]}
pH = -log (1.00x10-14/0.0250) = 12.40
47

Titration of Weak Base with Strong Acid

Titration Reaction:
B (aq) + H3O+(aq) BH+(aq) + H2O( )
Reaction goes to completion as strong acid is added.
Region 1: Before Acid is Added
pH is determined by the equilibrium for the weak base.
B + H2O BH+ + OHKb = [BH+][OH-]/[B]
48

Titration of Weak Base with Strong Acid

Region 2: Before the Equivalence Point
The Henderson-Hasselbach equation is used to
determine the pH because the solution is a buffer (B
and BH+) are present.
pH = pKa (for BH+) + log{[B]/[BH+]}
Region 3: At the Equivalence Point
All of the base has been converted to its conjugated acid.
pH is determined by the equilibrium for the conjugate acid
BH+ + H2O B + H3O+
Ka =Kw/Kb = [B][H3O+]/[BH+]
49

Titration of Weak Base with Strong Acid

Region 4: After the Equivalence Point
pH is determined by the excess titrant (H3O+, acid)
added to the solution.

50

Titrations in Diprotic Systems

Titration curve of 10.0 mL of
0.100 M base with 0.100 M HCl
(a) pKb1=4.00, pKb2=9.00
(b) pKb1=6.15, pKb2=10.85

pH too low
no sharp break

Blurred End Points

Sometimes it can be quite difficult to determine the end
points of titrations in systems with two or more titration
reactions.
BH22+ is such a strong acid (or equivalently BH+ is
too weak a base) that the titration reaction (H3O+ +
BH+ BH22+ + H2O) doesnt go to completion as
strong acid is added.
Or the equivalence points are either too closely
spaced (as expected for proteins with many titration
reactions possible).

Finding the End Point with a pH Electrode

The endpoint is the point at which . . .
The slope dpH/dV is the greatest
The second derivative d2pH/dV2 = 0.
By plotting pH/V, the endpoint of the titration can be
found as the maximum in the plot.

pH

Vbase

Finding the End Point with Indicators

An indicator is a weak acid or weak base whose
protonated and neutral form have different colors
HIn H+ + InColor 1

Color 2

To be useful it must be possible to distinguish between color 1 and 2 in a mixture

Most indicators are monoprotic acid and only undergo

one color change, thymol blue is a diprotic acid.

Transition range for an

Indicator
Indicators change color over a pH range and
not at a single pH. The transition range of an
indicator depends on the ability of the
observer to detect subtle color changes
Transition range pH = pKa 1
Corresponds to a 1:10 parts change in color
as a minimal observation limit
HIn H+ + InKa = [H+][In-] [In-]
1 or 10
[HIn]
[HIn]
10
1

Acid-Base Indicators
Thymol Blue (pK1 = 1.7, pK2 = 8.9)
H2T + H2O HT- + H3O+

pH = pK1 + log{[HT-]/[H2T]}

HT- + H2O T2- + H3O+

pH = pK2 + log{[T2-]/[HT-]}

H2T (red at pH < 1.7)

at pH = 1.7

[H2T] = [HT-]

orange

HT- (yellow for 1.7 < pH < 8.9)

at pH = 8.9

[HT-] = [T2-]

T2- (blue at pH > 8.9)

Transition range pK 1

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