Shefali Ainkar

Assistant Professor
PG Department of Chemistry
Parvatibai Chowgule College of Arts & Science
Email: ssa019@chowgules.ac.in
▪ Introduction
▪ Types of titration curves
▪ Determining the pka values for amino acid
▪ Polyfunctional acids and bases
▪ Buffer solutions involving polyprotic acids.
▪ Calculations of the pH of solutions of NaHA
▪ Titration curves for polyfunctional acids
▪ Titration curves of amphiprotic species
▪ Review questions
▪ References
▪ An acid–base titration involves a neutralization reaction in
which an acid is reacted with an equivalent amount of base.
▪ By constructing a titration curve, we can easily explain how the
end points of these titrations can be detected.
▪ The end point signals the completion of the reaction.
▪ A titration curve is constructed by plotting the pH of the solution
as a function of the volume of titrant added.
▪ The titrant is always a strong acid or a strong base. The analyte
may be either a strong base or acid or a weak base or acid.
A. Strong acid versus strong base B. Strong base versus strong acid

Figure 1: Titration curve for Strong acid Figure 2: Titration curve for Strong base
versus strong base versus strong acid
Source: Christian, G. D. (2015) pp 283 Source: Christian, G. D. (2015) pp 285
C. Weak acid versus strong base D. Weak base versus strong acid

Figure 3: Titration curve for weak acid Figure 4: Titration curve for weak base
versus Strong base versus Strong acid
Source: Christian, G. D. (2015) pp 291 Source: Christian, G. D. (2015) pp 295
▪ Amino acids contain both acidic and basic groups.
▪ It acts as zwitter ion in aqueous solutions in which the amine
group acquires a proton and becomes positively charged while
the carboxyl group having lost a proton becomes negatively
charged.
▪ Since zwitter ion has both acidic and basic character, two pKs
can be determined.
▪ The pk for deprotonation of the protonated amine group can be
determined by adding base while the pK for protonating the
carboxyl group can be determined by adding acid.
Figure 5: Titration curve of alanine with acid
and base
Source: F. Holler, S. C. (2014) pp 340
▪ They have two or more acidic or basic functional groups.
▪ Example of polyfunctional acid is phosphoric acid (H3PO4).
- { H3PO4, H2PO4 -, HPO4 2-}
- They exhibit multiple end points in a neutralization titration.
▪ Ka1, Ka2, … Ka1 > Ka2
▪ For bases Kb1, Kb2, ..
▪ Diagram
▪ Consider a solution of HA dissolved in water.
▪ Diagram
▪ Diagram
▪ Diagram
▪ Diagram
▪ Write a charge-balance equation for an aqueous solution that
contains NaCl, Ba(ClO4)2 and Al2(SO4)3.Write the chemical
reactions
▪ Diagram
▪ Diagram
▪ Two buffer systems can be prepared from a weak dibasic acid
and its salt.
▪ The first consists of free acid H2A and its conjugate base NaHA,
and the second makes use of the acid NaHA and its conjugate
base NA2A.
▪ The pH of the NaHA/Na2A system is higher than that of the
H2A/NaHA system because the acid dissociation constant for HĀ
is always less than that for H2A.
▪ For a buffer prepared from H2A and NaHA, the dissociation of HĀ
to yield A² ̄ can usually be neglected so that the calculation is
based only on the first dissociation.
▪ For a buffer prepared from NaHA and Na2A the second
dissociation usually predominates and the equilibrium

can be neglected.
▪ The concentrations of H2A is negligible compared with that of HA ̄
or A² ̄ .
▪ The hydronium ion concentrations can then be calculated from the
second dissociation constant by the techniques for a simple buffer
solution.
▪ Consider 1 mol of NaOH is added to a solution containing 1 mol
of the acid H2A, 1 mol of NaHA is formed.
The pH of this solution is determined by two equilibria
established between HA ̄ and water.

and
 Titration curve of diprotic acid H2A with
dissociation constant ka1 = 1 x 10 -3 and
ka2 = 1 x 10 -7
Ratio of ka1/ka2 > 1000

Figure 6: Titration curve of H2A with NaOH

Source: F. Holler, S. C. (2014) pp 360
Sodium hydrogen carbonate is the principle species present at the
first equivalence point.

With the addition of more acid, a new buffer consisting of sodium

hydrogen carbonate and carbonic acid is formed. Figure 6: Titration curve of Na2CO3
with HCl
The second equivalence point the solution consists of CO2 aq Source: F. Holler, S. C. (2014) pp 370
(carbonic acid) and sodium chloride.

After the second equivalance point, there is excess of acid HCl.

1. Calculate the pH at 0, 10.0, 25.0, 50.0, and 60.0mL titrant in the titration
of 50.0mL of 0.100 M acetic acid with 0.100 M NaOH.
2. Calculate the pH at 0, 10, 90, 100, and 110% titration (% of the
equivalence point volume) for the titration of 50.0mL of 0.100 M HCl with
0.100 M NaOH.
3. Write a note on Phosphoric acid system.
4. Sketch the four types of titration curves.
5. Write a note on polyfunctional acid-base titration curves.
Christian, G. D. (2015). Acid-Base titrations. In Analytical Chemistry
(Sixth ed., pp. 281-312). Delhi: Wiley India Pvt. Ltd.

F. Holler, S. C. (2014). Acid-Base Titrations. In Skoog and West`s

Fundamental of Analytical Chemistry (9th ed., pp. 323-379). Delhi:
Cengage Learning.