Chapter 15

Titration curves for complex

acid/base system
 Goal of this chapter
• To learn the nature of polyfunctional acid/base
dissociation.
• To learn stoichiometric calculation in titrating a
diprotic acid.
• To learn the nature of titration curve of titrating a
diprotic acid with a strong base.
• To learn the effect of dissociation constants on
titration curve of polyfunctional acid/base.
• To learn the change of α values during the
titration of a polyfunctional acid/base.
 Mixed solution of a strong acid and
a weak acid
• Conditions for determine the concentrations of a strong acid and a
weak acid in a single solution:
- the concentration of the two acid is in the same order of magnitude.
- the dissociation constant of the weak acid is 10-12 < Ka < 10-3.
• The titration curve with a strong base (NaOH) as a titrant:
- The first part of the titration curve is similar to the titration curve of a
strong acid.
- Near the end of consuming all the strong acid, the dissociation of
the weak acid make significant contribution to [H3O+] in the solution
- At the equivalence point of titrating the strong acid:
1 1 cHA Suppose the initial molarity of the strong
=
pH pKa − log
2 2 2 acid equals the molarity of the titrant.
- After completely consumed the strong acid, the titration curve is
similar to the curve of titrating the weak acid with a strong base.
Typical titration curves of strong
acid/weak acid solution

Titration curves for the

titration of strong
acid/weak acid mixture
with 0.1000 M NaOH.
Each titration is on 25.00
mL of a solution that is
0.1200 M in HCl and
0.0800 M in HA
 Polyfunctional Acids
+ [ H + ][ H 2 PO4− ]
H3PO4 H +H2PO4- K a1 = = 7.11×10 −3
[ H 3 PO4 ]
This image cannot currently be displayed.

- + [ H + ][ HPO4−2 ]
H2PO4 H +HPO4-2 K a2 = = 6.32 × 10 −8

[ H 2 PO4− ]
This image cannot currently be displayed.

[ H + ][ PO4−3 ] −13
HPO4-2 H++PO4-3 K a3 = = 4 . 5 × 10
[ HPO4− 2 ]

• Features of polyfunctional acids

- Usually, Ka1 >>Ka2>>Ka3 (H3PO4 above as an example
(H2CO3, Ka1 = 4.45 x 10-7; Ka2 = 4.69 x 10-11).
- pH value of such systems can be calculated with
systematic strategy.
- Simplify assumptions can be used when the successive
equilibrium constant is differ by a factor >103.
e.g.: calculating pH value in titrating a
diprotic acid with a strong base
• When the polyprotic acid has
well separated pKa values, each step
can be treated individually.

• Example – Consider the titration of 40.00

mL of 0.100 M H2SO3 (Ka1 = 1.4*10-2,
Ka2 = 6.5*10-8) with 0.100 M NaOH.

• Ka1/Ka2 = 2.1 x 105 >103.

 Titrating process:
a), 0.00 mL of 0.100 M NaOH added

• The solution consists only of 0.050 M H2SO3

Reaction: H2SO3 + H2O ⇔ H3O+ + HSO3-

Orig.Conc. 0.100 0 0
Equil.Conc 0.100-[H3O+] [H3O+] [H3O+]

From Ka1 expression:

1.4*10-2 = [H3O+]2/(0.100 – [H3O+])
[H3O+] = 6.2*10-2, pH = 1.21
 Titrating process:
b). 15.00 mL NaOH added
• Calculate the mol OH- added and initial moles of
H2SO3.

Initial mol H2SO3 = 40.00 mL * 0.100 M = 4.00 mmol

Added mol OH- = 15.00 mL * 0.100 M = 1.50 mmol

Excess mol H2SO3 = 4.00 – 1.50 mmol = 2.50 mmol

[H2SO3] = 2.50 mmol / 55.00 mL = 4.54*10-2 M

• Must realize that this is a buffer system (why?).

Titrating process:
b). 15.00 mL NaOH added
-----Continued
• From an MBE consideration:
initial mol H2SO3 = mol H2SO3 left + mol HSO3- formed
4.00 mmol = mol H2SO3 + mol HSO3- = 2.50 + x
x = 1.50 mmol
[HSO3-] = 1.50 mmol / 55.00 mL = 2.72*10-2
Ka1 = 1.4*10-2 = [H3O+][HSO3-] / [H2SO3]
1.4*10-2 = [H3O+] x 2.72*10-2 / 4.54*10-2
note that volumes of solution cancel
[H3O+] = 2.33*10-2
pH = 1.6
 Titrating process:
c), 40.00 mL of 0.100 M NaOH added

• Initial mol H2SO3 = 40.00 mL * 0.100 M = 4.00 mmol

• Added mol OH- = 40.00 mL * 0.100 M = 4.00 mmol

• This is the first equivalence point.

[HSO3-] = 4.00 mmol / 80.00 mL = 0.0500 M
HSO3- + H2O SO32- + H3O+ &
H3O+ + HSO3- H2SO3 + H2O
Titrating process:
c), 40.00 mL of 0.100 M NaOH added
---Continued
p405, equation 15-15

Ka1Ka 2[HSO3- ] + Ka1Kw

[ H 3O + ] ≈
Ka1 + [HSO3- ]
-2 -8 -2 -14
1.4*10 x6.5*10 x0.0500+1.4*10 x10
[ H 3O + ] ≈
1.4*10-2 + 0.0500
[H3O+] = 2.67*10-5
pH = 4.57
Or use a simplified equation:
pH = ½(pKa1 + pKa2) = 4.52
Titrating process:
d). 55.00mL NaOH added
• We have HSO3- and SO32-, which constitutes
another buffer system.

• Initial mols HSO3- = 4.00 mmol

• Mols OH- beyond 1st eq. pt.

= (55.00 – 40.00) mL * 0.100 M = 1.50 mmol

• mols HSO3- = 4.00 – 1.50 mmol = 2.50 mmol

• [HSO3-] = 2.50 mmol / 95.00 mL = 2.63*10-2 M

Titrating process:
d). 55.00mL NaOH added
-----Continued
• MBE
4.00 mmol = [HSO3-] + [SO32-] = 2.50 + x
x = 1.50 mmol
[SO32-] = 1.50 / 95.00 mL = 1.58*10-2
Ka2 = 6.5*10-8 = [H3O+][SO32-] / [HSO3-]
= [H3O+]x1.58*10-2 / 2.63*10-2
[H3O+] = 1.08*10-7
pH = 6.96
Titrating process:
e), 80.00 mL NaOH solution added
• Initial mol H2SO3 = 40.00 mL * 0.100 M = 4.00 mmol
Added mol OH- = 80.00 mL * 0.100 M = 8.00 mmol
• This is the second eq. pt.
Sole species CSO32- = 4.00 mmol / 120.00 mL = 0.0333 M
Diss. React SO32- + H2O = HSO3- + OH-
Init. Conc. 0.0333 0 0
Conc. Change -[OH-] +[OH-] +[OH-]
Kb = Kw/Ka2 = 1.00*10-14 / 6.5*10-8 = 1.54 x 10-7
• A weak base,
[OH − ] =
= KbCSO 3 2− 1.54*10−7 *0.033 = 7.15*10-5
pOH = 4.14
pH = 9.86
Titrating process:
f) 85.00 mL of 0.100 M NaOH added

• We are 5.00 mL beyond the 2nd eq. pt.

• Excess [OH-] = 5.00 mL * 0.100 M = 0.500 mmol

• [OH-] = 0.500 mmol / 125.00 mL = 4.00*10-3 M

• pH = 11.6
 Summary

Point Vol titrant pH

A 0.00mL 1.21 excess H2SO3
B 15.00 1.6 1st buffer region
C 40.00 4.52 1st equivalence point
D 55.00 6.96 2nd buffer region
E 80.00 9.86 2nd equivalence point
F 85.00 11.6 excess OH
 Features of titration curves of
diprotic Acids
• Point A: Treat the system as if it contained a
single monoprotic acid. (Ka1>>Ka2)
• Region B: Treat the system as if a simple buffer
solution consisting of the H2A and NaHA.
• Point C: Use equation: [ H + ] = K a K a
1 2

• Region D: The second buffer solution

consisting of the HA- and Na2A.
Kw
• Point E: Use equation: Kb =
Ka2
• Region F: The excess NaOH dominated the pH.
Effect of dissociation constants on
titration of polyfunctional acids
The fractional composition of a polyprotic
acid solution as a function of pH
--- A diprotic acid solution as an example
• Dissociation equilibria in solution
H 2 M + H 2O ⇔ HM − + H 3O +
HM − + H 2O ⇔ M 2− + H 3O +

• The relationship of α-factors with pH value of the solution

cT = [ H 2 M ] + [ HM − ] + [ M 2− ]
[H 2M ] [ H 3O + ]2
=α0 =
cT [ H 3O + ]2 + Ka1[ H 3O + ] + Ka1Ka 2
[ HM − ] Ka1[ H 3O + ]
=α1 =
cT [ H 3O + ]2 + Ka1[ H 3O + ] + Ka1Ka 2
[ M 2− ] Ka1Ka 2
α2 =
=
cT [ H 3O + ]2 + Ka1[ H 3O + ] + Ka1Ka 2
The relationship of α-factor with the pH
value of a polyfunctional acid solution
A titration curve for titrating a polyfunctional
base solution with a strong acid
Sodium carbonate reacts with hydrochloric acid in two steps...
Step 1 Na2CO3 + HCl ——> NaHCO3 + NaCl
Step 2 NaHCO3 + HCl ——> NaCl + H2O + CO2
Overall Na2CO3 + 2HCl ——> 2NaCl + H2O + CO2

There are two sharp pH changes

First rapid pH change around pH = 8.5

due to the formation of NaHCO3 .
Can be detected using phenolphthalein

Second rapid pH change around pH = 4

due to the formation of acidic CO2 .
Can be detected using methyl orange.