Titrations of polyprotic acids:

Polyprotic acids and Ka values:

H3PO4 + H2O
H3O+ + H2PO4H2PO4- + H2O
H3O+ + HPO42H3O+ + PO43HPO42- + H2O
__________________________________
3H3O+ + PO43-

H3PO4 + 3H2O

K a1

[ H 3 O + ] H 2 PO4
=
= 7.11x10 3
[H 3 PO4 ]

Ka2

[ H 3O + ] HPO42
8
=
=
6
.
32
x
10
H 2 PO4

Ka1=7.11x10-3
Ka2=6.32x10-8
Ka3=4.5x10-13
Ka1Ka2Ka3

[ H 3O + ] PO43
K a3 =
= 4.5 x1013
2
HPO4

When consecutive equilibria are added, the Ka values

are multiplied:
H3PO4 + 2H2O
2H3O+ + HPO42[ H 3O + ]2 HPO42
K a1 K a 2 =
= 4.49 x10 10
[H 3 PO4 ]

H3PO4 + 3H2O
K a1 K a 2 K a 3

3H3O+ + PO43-

[ H 3O + ]3 PO43
=
= 2.0 x10 22
[H 3 PO4 ]

Titrations of polyprotic acids:

multiple endpoints observable when Ka,n/Ka,n+1>103

Titration curve of a weak diprotic acid H2A:

1. pH before titration
2. pH before first equiv. point
3. pH at first equiv. pt.
4. pH between equiv. pts.
5. pH at second equiv. pt.
6. pH after second equiv. pt.

H2A + H2O
HA- + H2O

H3O+ + HAH3O+ + A2-

Ka1
Ka2

1. pH prior to titration:
for a strong diprotic acid, same as strong acid
for a weak diprotic acid,
if Ka1 > 103 Ka2, second equilibrium makes little
contribution
assuming autoprotolysis contributes little
+

[ H ] K a1CH 2 A or

2.

K a1 + K a21 + 4 K a C H 2 A
[H ] =
2
+

pH prior to first equiv. pt., 1st buffer region

1st buffer region, both H2A and HA- present
if Ka1 > 103 Ka2, second equilibrium makes little
contribution, pH calculated like a normal buffer
solution
half way to equivalence, CH2A = CHA-

[H+] = Ka1

3.

pH at first equiv. pt.

solution is like that of a salt of a diprotic acid
(e.g., NaHA)

[H ] =
+

[
[

]
]

K a 2 HA + K w
1 + HA K a1

If it can be assumed that [HA-] CNaHA

[H ]
+

K a 2C NaHA + K w
1 + C NaHA K a1

[ ]

+
If CNaHAKa1 > 10-13 and CNaHA/Ka1 > 100, H K a1K a 2

4.

pH in 2nd buffer region

2nd buffer region, both HA- and A2- present
if Ka1 > 103 Ka2, first equilibrium makes little
contribution, pH calculated like a normal buffer
solution
half way to equivalence, CHA- = CA2-

[H+] = Ka2

5.

pH at the second equivalence point

Like a salt of A2-, main equilibrium is
A2- + H2O

OH- + HA-

][

Kw
OH HA
K b1 =
=
Ka2
A 2

[ ]

[OH ] K b1C A2

or a more sophisticated relationship, if necessary

6.

pH beyond 2nd equiv. pt.

treated like the addition of strong base to water

Two common types of titration curves are used to

determine equivalence points for any kind of titration:
sigmoidal curves and linear-segment curve:
linear segment curve

Depends upon difference in instrument response

between reactants and products. Intersection of
response lines before and after equivalence point
determined location of equivalence point. Data
typically collected far from equivalence point.

E.g. titration leading to complex formation

Analyte
+ Reagent

Complex
lo response
hi response
lo response

Analyte
+
lo response

Reagent

lo response

Complex
hi response

Sigmoidal curve

Plot(s) of p-function of analyte (e.g., pH or pOH)

versus reagent volume. Careful measurements made
near the equivalence point.
Acid-base titrations usually make use of this
approach. Reagent solutions are almost always a
standardized solution of a strong acid or strong base
because they give sharper end points than do weak
acids or bases.

Identifying equivalence points:

1.

titration with indicators (sigmoidal curve)

2.

titration with linear-segment curve

3.

titration monitored with a pH meter

4.

Gran plot (see feature 14-5, text)

Titration monitored with a pH meter:

1st derivative shows point of greatest slope eq. pt.

2nd derivative indicates inflection point eq. pt.

A bit about indicators:

Characteristics of analytically useful chemical
reactions:
1.
2.
3.

Reactants and products are easily distinguished

The reaction provides useful information
The reaction proceeds at high rates/efficiencies

most acids and their conjugate bases are

transparent to visible radiation
pH indicators are exceptions, proton transfer
reactions involving indicators meet the criteria for an
analytically useful reaction

pH transition range for an indicator:

[H3O+] + [In-]

HIn + H2O

[H O ][In ]
=
+

Ka

[HIn]

[ H 3O]+ = K a

[HIn]

[In ]

color changes at ratios

and

[HIn]/In-] = 0.1
[HIn]/[In-] = 10.0

cannot be discerned by eye

Hence, useful range for a pH indicator is:

pH = pKa1

Note: concentration of indicator must be minimized

to avoid introduction of systematic error