Lesson 5B – Titration of Polyfunctional Acids and Bases

Polyfunctional acids/bases The principal equilibrium in this case is the dissociation of

- contains 2 or 3 acidic or basic groups which normally HA- (NaHA) into A2- (Na2A).
differ in strength and as a consequence, exhibit two or [H3 O+ ][P2− ]
HP- + H2O ⇌ H3O+ + P2- Ka2 = [HP−]
= 3.91 × 10−6
more end points in neutralization titration.
- example: (1) The Phosphoric Acid System and (2) The [HP-] ≈ CHA− = 0.0500 M; [P2-] ≈ CA2− = 0.150 M
Carbon dioxide/Carbonic Acid System CHA− (3.91 ×10−6 )(0.0500 M)
[H3 O+ ] = K a2 = = 1.30 x 10-6 M
CA2− 0.150 M
The Phosphoric System
pH = - log (1.30 x 10-6) = 5.88 or
CA2− 0.150 M
pH = pKa + log C = - log (3.91 x 10-6) + log 0.0500 M = 5.88
HA−

Calculation of the pH of Solutions of NaHA

NaHA – is the convention used to describe the salt that have both
where Ka₁ > Ka₂ > Ka₃ (true for other polyprotic acid). acidic and basic properties—that is, salt that are
amphiprotic.

The Carbon dioxide/Carbonic Acid System – formed during neutralization titration of polyfunctional
acids and bases: e.g. NaOH + H2A ⇌ NaHA + H2O
– the solution could be acidic because of:

or basic because of:

– applying the systematic method for solving multiple

equilibria gives an approximate value of H3O+ for NaHA:

Two buffer systems prepared from a weak dibasic acid and its
salt:
1. free acid H2A and its conjugate base NaHA
2. acid NaHA and its conjugate base Na2A
Example 7: Calculate the hydronium ion concentration and the
pH for a buffer solution that is 2.00 M in phosphoric acid and 1.50
M in potassium dihydrogen phosphate.
The principal equilibrium in this solution is the dissociation of
H3PO4.
– Frequently, the ratio CNaHA/Ka1 (in the denominator) is
much larger than unity and Ka2CNaHA (in the
denominator) is considerably greater than Kw. With this,
the equation simplifies to
Example 9: Calculate the hydronium concentration of a 1.00x10-3
M NaH2PO4 solution.
Na2HPO4 is an amphiprotic salt NaHA so the equation 5 applies.
Equilibria that contains HPO42- are:

We assume that the dissociation of H2PO4- is negligible.

[H3PO4] ≈ CH3PO4 = 2.00 M; [H2PO4-] ≈ 𝐶H2PO4− = 1.50 M

Plugging in the Ka values into the equation gives:
CHA (7.11 ×10−3 )(2.00 M)
[H3 O+ ] = K a = = 9.48 x 10-3 M (4.5×10
−13
)(1.00×10
−3
)+1.00×10
−14
CNaA 1.50 M
[H3 O+ ] = √ −3 −8 = 8.1 x 10-10 M
1+(1.00×10 )(6.32×10 )
pH = - log (9.48 x 10-3) = 2.02 or
CNaA 1.50 M
pH = pKa + log = - log (7.11 x 10-3) + log 2.00 M = 2.02 Exercise 9: Find the hydronium concentration of a 0.0100 M
CHA
NaH2PO4 solution.
Example 8: Calculate the hydronium concentration and the pH
of a buffer that is 0.0500 M in potassium hydrogen phthalate Exercise 10: Calculate the hydronium ion concentration of a
(KHP) and 0.150 M in potassium phthalate (K2P). 0.100 M NaHCO₃ solution.
Titration Curve of Polyfunctional Acid 𝑥2
Hence, K a1 = = 1.3 × 10−2
0.1000 M – x
Compounds with 2 or more acid functional groups yield Because Ka1 for maleic acid is large, the quadratic equation must
multiple end points. be solved. When we do so, we obtain
Computation techniques described in Lesson 6a applies if [H3O+] = 3.01 x 10-2
the ration Ka1/Ka2 is greater than 103. pH = - log (3.01 x 10-2) = 1.52
Consider the titration curve:
pH at the 1st buffer region (Ex. after 5.00-mL NaOH is added):

Pertinent equilibria:
[H3 O+][HA− ]
H2A + H2O ⇌ H3O+ + HA- K a1 = [H2 A]
= 1.3 × 10−2
[H3 O+ ][A2− ]
HA- + H2O ⇌ H3O+ + A2- K a2 = [HA− ]
= 5.9 × 10−7

Mass-balance equations:
[H2A] = CH2A - [H3O+] + [-OH]
[HA-] = CHA− + [H3O+] - [-OH]
For this system, generation of H3O+ is relatively large and -OH is
approximately very small because the Ka1 for maleic acid is large.
Hence,
(25.00 mL)(0.100 M) − (5.00 mL)(0.100 M)
CH2 A = = 0.06667 M
(25.00 + 5.00) mL
(5.00 mL)(0.100 M)
CNaHA = = 0.01667 M
Different types of calculation to get the pH: (25.00 + 5.00) mL
Principal Influencer of pH in the Calculation [H2A] = 0.06667 - [H3O+]
Point/Region
Solution of H3O+ [HA-] = 0.01667 + [H3O+]
Point A Dissociation of a weak acid with Ka1 Ka1 becomes
(initial pH) Ka1 expression [H3 O+ ]{0.01667 + [H3 O+ ]}
buffer solution of weak acid K a1 = = 1.3 × 10−2
Ka1 0.06667 + [H3 O+ ]
Region B H2A and its conjugate base
expression Solving the quadratic equation gives
NaHA
Point C (1st [H3O+] = 1.81 x 10-2
Only amphiprotic salt, NaHA Eqn 4
equiv. point) pH = - log (1.81 x 10-2) = 1.74
2nd buffer system consisting of a
Additional points in the first buffer region can be computed in a
Region D weak acid HA- and its conjugate Eqn 3
base Na2A similar way.
Point E (2nd From [-OH]
Only conjugate base, Na2A pH at the 1st equivalence point (after 25.0 mL NaOH is added):
equiv. point) of Kb2
From [-OH] At this point, all H2A is converted to NaHA which the only
Region F Only excess titrant, NaOH
using Kw
component in the solution,
(25.00 mL)(0.100 M)
Example 10: Construct a curve for the titration of 25.00 mL of CNaHA = = 0.05000 M
(25.00 + 25.00) mL
0.1000 M maleic acid, HOOC-CH=CH-COOH, with 0.1000 M
NaOH. Ka1 = 1.3 x 10-2; Ka2 = 5.9 x 10-7

pH at Initial point: −7 −14

(5.9 × 10 ) (0.05000) + 1.00 × 10
The system at this point is treated as if it contained a single [H3O+ ] = √ −2
1 + (0.05000)(1.3 × 10 )
monoprotic acid
[H3 O+ ][HA− ] = 7.80 x 10-5
H2A + H2O ⇌ H3O+ + HA- K a1 = = 1.3 × 10−2
[H2 A] pH = - log (7.80 x 10-5) = 4.11
0.100 - x +x +x
Mass-balance equations: [H3O+] = [HA-] pH at the 2nd buffer region (Ex. after 25.50 mL of NaOH is added):

CH3PO4 = [H2 A] + [HA− ]= 0.1000 M At this point, the dissociation of weak acid HA- predominates in
[H2A] = 0.1000 M – [HA-] the solution.
[H3 O+ ][A2− ]
= 0.1000 M – x HA- + H2O ⇌ H3O+ + A2- K a2 = [HA− ]
= 5.9 × 10−7
 CNa2 A An excel file that contains the calculation of each point in the
Eqn 3, pH = pKa + log , can now be applied.
CNaHA
titration curve of maleic acid with NaOH will be given together
To find CNa2A, keep in mind that the total mole of the added titrant with this handout.
will be neutralized by the mole of the acid in the initial solution:
(mole of OH− added) − (mole of original acid)
CNa2 A = Titration Curve of Polyfunctional Base
total volume of the sol′n
(25.50 mL)(0.100 M) − (25.00 mL)(0.100 M) It involves the same principle described for polyfunctional
CNa2 A = = 9.901 × 10−4 M
(25.00 + 25.50) mL acid.
To determine CNaHA, remember that HA- is at its maximum amount To illustrate, consider the titration of a sodium carbonate
when the 1st equivalence point is achieved. Beyond this point, with HCl
some of its portion is consumed because it is used to neutralize
further addition of NaOH.
(mole of HA− formed)−{(mole of OH− added)−(mole of original acid)}
CNaHA =
total volume of the sol′n
(25.00 mL)(0.100 M) − {(25.50)(0.100) − (25.00)(0.100)}
CNaHA =
(25.00 + 25.50) mL

= 0.04851 M
Different types of calculation to get the pH:
Hence,
Point/ Principal Influencer of pH in the Calculation
CNa2 A 9.901×10−4
pH = pKa + log = - log (5.9 x 10-7) + log = 4.54 Region Solution of H3O+
CNaHA 0.04851
Point A Kb1
Reaction of CO32- with H2O
(initial pH) expression
pH at the 2nd equivalence point (after add’n of 50.00 mL NaOH): buffer solution of weak base CO32- Kb1 or Ka2
Region B
and its conjugate acid HCO3- expression
All HA- is converted to A2- which reacts with water to form OH-,
Point C (1st
A2- + H2O ⇌ OH- + HA- Only amphiprotic salt, NaHCO3 Eqn 4
equiv. point)
0.03333 - x +x +x 2nd buffer system consisting of a
Kb2 or Ka1
(50.00 mL)(0.100 M) − (25.00 mL)(0.100 M) Region D weak base HCO3- and its conjugate
CNa2 A = = 0.03333 M expression
(25.00 + 50.00) mL acid CO2 dissolved in H2O
Mass-balance equations: [OH-] = [HA-] Point E (2nd NaCl and CO2 treated as H2CO3 with Ka1
equiv. point) Ka1 expression
[A2-] = CNa2 A - [OH-] ≈ 0.0333 Region F Only excess titrant, HCl Excess HCl
Because A2- is a weak base, Kb1 is used in this system to calculate
for the pH: Exercise 11: Using the excel, construct a curve for the titration of
[OH−][HA−] Kw 1.00×10−14
25.00-mL 0.1000 M sodium carbonate with 0.1000 M HCl.
K b1 = [A2− ]
= = = 1.6949 × 10−8
Ka2 5.9×10−7

[x][x]
= 1.6949 × 10−8 Titration curve of Amphiprotic Species
[0.03333]

[OH-] = x = √(1.6949 × 10−8 )(0.03333) = 2.3768 x 10-5 If either of the acidic or basic character of an amphiprotic
species predominates then titration with a strong acid or a
pH = 14.00 – log (2.3768 x 10-5) = 9.38
strong base may be feasible.
pH beyond the 2nd equivalence point (Ex. after additional of 51.00 Example:
mL NaOH): • For NaH2PO4 solution, the principal equilibria are:
H2PO4- + H2O ⇌ H3O+ + HPO42- Ka2 = 6.32 x 10-8
Keep in mind that NaOH added into the solution is neutralized by
H2PO4- + H2O ⇌ -OH + H3PO4 Kb3 = 1.41 x 10-12
the two types of acid—H2A and HA- which requires 50.00 mL of
NaOH. Thus, the excess volume of the titrant is only 1.00 mL. Kb3 is too small to permit titration of H2PO4- with an acid, but
(1.00 mL)(0.100 M) Ka2 is large enough for titration of the ion with a standard
COH− = = 1.333 × 10−3 M
(25.00 + 50.00) mL base solution.
pOH = - log (1.333 x 10-3) = 2.88 • For Na2HPO4 solution, the principal equilibria are:
pH = 14.00 – pOH = 11.12 HPO42- + H2O ⇌ H3O+ + PO43- Ka3 = 4.5 x 10-13
HPO42- + H2O ⇌ -OH + H2PO4- Kb3 = 1.58 x 10-7
Note: Within approximately 0.1 mL of the equivalence points,
The magnitude of constants indicates that HPO42- can be
there are other conditions that are needed to be considered.
titrated with standard acid but not with standard base.
Prepared by:

Mary-Ann A. Landiao, RCh, MSc

Faculty, Chemistry Dept.

Helpful YouTube tutorials

Polyprotic Acids
https://www.youtube.com/watch?v=69JT2mD9MUg

Polyprotic Acid Titrations

https://www.youtube.com/watch?v=cOuqLXezSS0&t=32s