200 Chem.

Educator 2005, 10, 200–203

The Effect of Structure on the Behavior of Polyprotic Weak Acids in

Alkalimetric Titrations

Débora Cassoli de Souza, Andréa Boldarini Couto, and Eduardo Almeida Neves*

Departamento de Química da Universidade Federal de São Carlos. Via Washington Luís Km 235, CEP 13565-
905, São Carlos, S.P., edneves@dq.ufscar.br
Received August 5, 2004. Accepted February 1, 2005.

Abstract: The alkalimetric titrations of polyprotic acids provide an interesting didactic discussion for students in
analytical chemistry classes. There is a marked decrease in the stepwise ionization constant, normally in the 104
to 105 order-of-magnitude range (e.g., phosphoric acid), due to a progressive increase in the anionic negative
charge. With citric acid and some diprotic organic acids, the distance between the carboxylic groups markedly
affects the pKn differences, which causes overlapping of the neutralization curves for the intermediate steps. The
length of the carbon chain in diprotic acids, for instance, that of oxalic (two carbon atoms) and adipic acid (six
carbon atoms) causes a regular decrease in the value of pK2 over pK1. Other interesting pK differences occur in
compounds with cis–trans isomers, such as fumaric and maleic acid.

Introduction Solutions of 0.1 to 0.2 mol L–1 sodium hydroxide, carbonate

Volumetric methods involving titrations of polyprotic acids
with strong bases (e.g., NaOH) provide for interesting
discussions with students during analytical chemistry classes
[1–3]. It is important to point out the differences in the
stepwise ionization constants and how they affect the
definition of the intermediate stoichiometric points, which can
be clearly seen from potentiometric titration curves. It is well
known that the stepwise ionization of polyprotic acids exhibits
a continuous decrease in the magnitude of its ionization
constants, Kn, and an increase in the corresponding pKn values.
Normally a 104 to 105 difference in the stepwise Kn is found in
many of the tables available for polyprotic acids [1–4], which
creates a favorable condition for obtaining well-defined
neutralization steps during titration of the acids [1–3]. Smaller
than 104 differences in Kn yield titration curves showing
overlap of the intermediate neutralization steps; thus, the
recommendation is that the last Kn should not be smaller than
the 10–7 or 10–8 order-of-magnitude range in order to guarantee
reliable endpoint detection.
In some diprotic organic acids, the length of the carbon
chain affects the stepwise ionization constants, causing
progressively smaller differences in the ionization constants.
The present article discusses this effect and gives some
examples of the effect of structure on the magnitude of the
available ionization constants.
Experimental
All reagents were of analytical reagent (A R) quality
(Merck, Mallinckrodt, or Carlo Erba). Solutions of citric acid
and the others organic acids were prepared by directly
weighing the solid chemicals needed to prepare an 0.05 mol
L–1 solution. A 0.05 mol L–1 phosphoric acid solution was
prepared by diluting 3.5 mL of the concentrated acid (85%) to
1 liter.
Distilled water used to prepare all solutions was bubbled
with nitrogen before use to remove traces of carbon dioxide.
free, were prepared by diluting a concentrated solution (50%
NaOH) and standardizing with potassium hydrogen phthalate
using phenolphthalein as the end-point indicator [1–3].
The glass electrode was calibrated with 0.0500 mol L–1
potassium hydrogen phthalate (pH = 4.01) and 0.0100 mol L–1
hydrated sodium borate (pH = 9.18) buffers [1–3]. The acids in
solution were potentiometrically titrated with 0.2136 mol L–1
sodium hydroxide using a Digimed glass electrode combined
with a calomel reference electrode saturated with potassium
chloride. An Orion model EA-940 potentiometer was used for
pH and potential measurements. The Origin 6.0 program was
used to plot the pH and potentiometric data.
Two laboratory experiments for students are presented and it
is recommended that they be completed in sequence.
Discussions with the students are helpful in creating a better
understanding of the principles involved for the generated
titration curves. The definition of the intermediate steps for
neutralization of the two triprotic acids and the estimated pH of
the defined stoichiometric points are examples of information
that should be discussed.
Experiment 1. Pipet 25 mL of 0.05 mol L–1 phosphoric acid
into a 75-to-100-mL beaker. Titrate this solution with 0.10 mol
L–1 standard sodium hydroxide solution, recording the pH
versus the volume of sodium hydroxide titrant added in mL.
The titrant should be added in fixed increments. Use a
magnetic stirrer and a previously calibrated glass electrode for
pH measurements. If necessary, add distilled water to cover the
electrode bulb and give contact with its salt bridge. Wait a few
seconds to get stable pH measurements at each addition.
Initiate the titration with increments of 0.5 mL of the titrant
and reduce the increment to 0.2 mL at the vicinity of the first
potential jump, that is, in the 3 to 6 pH range. Return to 0.5-
mL increments until reaching the region of the second pH
jump (between 7.5 and 10.5, where increments of 0.2 mL
should again be used. Continue until reaching pH 11.5 using
0.5-mL increments. Analysis of the Data. Plot pH versus
sodium hydroxide volume (VOH) with a computer-assisted
graphics program, such as Origin 6.0, and observe the clear

© 2005 The Chemical Educator, S1430-4171(05)03909-4, Published on Web 05/27/2005, 10.1333/s00897050909a, 1030200en.pdf
The Effect of Structure on the Behavior of Polyprotic Weak Acids Chem. Educator, Vol. 10, No. 3, 2005 201

(a) Find in the derivative plot the VOH1 and VOH2 values
14 corresponding to the two stoichiometric points. Of course,
VOH2 is virtually twice VOH1 within some small
12
experimental error because they refer to the neutralization
10 of two monoprotic acids.
2. Find the pH at both stoichiometric points. The pH should
8 be close to (pK1 + pK2)/2 and (pK2 + pK3)/2, which
pH
6
correspond to the solutions of the H2PO4– and HPO42–
ions, respectively, at the each equivalent point.
4 3. Find the pH corresponding to VOH1/2 on the normal
titration curve. This is an estimation of pK1, because at
2
this point, a molar ratio of 1:1 for [H2PO4–]/[H3PO4] is
0
achieved.
0 5 10 15 20 25 30 4. The pH corresponding to the intermediate volume
Volume NaOH / mL between VOH1 and VOH2 refers to the 1:1 ratio of
[HPO42–]/[H2PO4–]. It is an estimation of pK2.
Figure 1. Potentiometric titration curve for phosphoric acid. 5. Observe that only two stoichiometric points were found.
This is a consequence of a very low K3, which is very
much less than 10–7.
Experiment 2. An 25-mL aliquot of an 0.05 mol L–1 citric
acid solution is potentiometrically titrated with 0.1 mol L–1
NaOH in conditions similar to those in Experiment 1 (see
Figure 2). Use increments of 0.5 mL of the titrant until
reaching the vicinity of pH 7.5. Decrease the increments in the
region of the potentiometric jump that occurs in a pH range of
7.5 to 10.5. Return to 0.5-mL increments until reaching the
vicinity of pH 11.5.
Analysis of the Data. Plot the titration data to obtain the
normal titration curve and the corresponding derivative curve.
Consider the following points for discussion:
1. The pH increases regularly along the titration curve due
Figure 2. Potentiometric titration curve for citric acid. continuous formation of citrate buffers until reaching only
one stoichiometric point (see Figure 2). This single point
16 corresponds to the quantitative neutralization of the three
hydrogen ions of the citric acid without definition of the
intermediate neutralization steps.
V1 2. The derivative curve built with all the experimental points
shows only one well-defined stoichiometric point, which
V2
14
is a consequence of small differences in the pKn data.
3. If another, higher-definition derivative curve is plotted
∆pH/∆V using pH/VOH data up to pH 6, which excludes the
potentiometric jump, the plot shows two poorly defined
stoichiometric points corresponding to the neutralization
of one and two hydrogen ions of the citric acid (see Figure
12 3). This is a consequence of overlapping of the
neutralization data obtained during the intermediate steps.
4. Compare the behavior of citric acid with that of
2 4 6 8 10 12 14 phosphoric acid with regard to the pH at the endpoints and
the definition of step size. Consider, for instance, the fact
VolumeNaOH / mL
that only two hydrogen ions of phosphoric acid are used
Figure 3. The two intermediate stoichiometric points in the for analytical purposes in comparison with the total
titration of citric acid, visible only in derivative form using a neutralization of the three hydrogens of citric acid with
high-sensitivity plot. only one single potentiometric jump.
separation of the two potentiometric jumps (see Figure 1). Two
Results and Discussion
well-defined peaks in the derivative curve of ∆pH/∆VOH versus
VOH can be seen, which define two stoichiometric points: VOH1 Phosphoric acid is a typical example of a triprotic acid that
and VOH2, which correspond to the neutralization of H3PO4 to shows a decrease of 105 orders of magnitude going from the
form the ions H2PO4– and HPO42–, respectively. This derivative first to the third ionization constant [1–4]. A qualitative
curve is similar to that of maleic acid Consider the following explanation for this observation is the increase in the negative
points for discussion: charge density in the coordinating center of the hydrogen ions
during the stepwise ionization. In fact, the first ionization step
© 2005 The Chemical Educator, S1430-4171(05)03909-4, Published on Web 05/27/2005, 10.1333/s00897050909a, 1030200en.pdf
202 Chem. Educator, Vol. 10, No. 3, 2005 Neves et al.

Table 1. pK Data for Some Diprotic Organic Acids reveal the intermediate steps, as shown in Figure 2. The reason
Acid Formula pK1 pK2 ∆pK for this phenomena is very close pKn values for citric acid [1]:
oxalic acid C2H2O4 1.25 4.27 3.02 pK1 = 3.128, pK2 = 4.761, and pK3 = 6.396, because of the
malonic acid C3H4O4 2.85 5.70 2.85 distance between the carboxylic acid groups. The charge
succinic acid C4H6O4 4.21 5.64 1.43 density for each carboxylic anion, R-COO–, has only a very
L-malic acid, 1 OH C4H6O5 3.46 5.10 1.64 small effect on the subsequent ionization of the other, more
D-tartaric acid, 2 OH C4H6O6 3.04 4.37 1.33 distant carboxylic groups.
adipic acid C6H8O4 4.42 5.42 1.00 The endpoint in the alkaline region, at a pH of about 9.7, is
maleic acid (cis) C4H4O4 1.92 6.27 4.35 consistent with the hydrolysis constant, 10–14/K3, which is 2.49
fumaric acid (trans) C4H4O4 3.02 4.48 1.46 × 10–8 mol L–1. For the intermediate stoichiometric points
corresponding to VOH1 and VOH2, the corresponding pH1 and
pH2 data can be calculated to be 3.94 and 5.58, respectively, a
5 difference of only 1.64 pH units, smaller than that observed for
the intermediate stoichiometric points of phosphoric acid,
which is 5.2 pH units. This causes poor definition of the
4
intermediate steps, inadequate for analytical purposes. Only if
improved plotting sensitivity is used, as shown in Figure 3 for
3 the derivative curves taken in the intermediate titration region,
∆pH / ∆V

does some evidence of the first and second neutralization steps

2 for citric acid appear. Of course, only the third neutralization
1
0 in order to compare the effect of the increase in carbon chain
0 5 10 15 20 25 30
VolumeNaOH / mL
Figure 4. Derivative curve of the potentiometric titration data for
maleic acid.
is favored in a neutral species, such as H3PO4; the second
constant decreases due to the single negatively charged H2PO4–
ion; the third ionization is much more affected because it
occurs from the double negatively charged HPO42– ion. The
concept of ionic potential, the ratio of the ionic charge to the
ionic radius, provides much information about acidity as
formerly discussed by Cartledge [5] and also considered in an
excellent chapter of Moeler’s Inorganic Chemistry textbook
[6].
A comparison of the potentiometric titrations of citric and
phosphoric acids is interesting, and two experiments for
students have been presented here. Both involve triprotic acids,
but they differ markedly in their sodium hydroxide titration
curves with sodium hydroxide as shown in Figures 1 and 2.
Phosphoric acid has the following pKn values: pK1 = 2.148, pK2
= 7.198, and pK3 = 12.375 [1], from which two intermediate
stoichiometric points [2, 3] can be estimated from (pK1 +
pK2)/2, corresponding to pH = 4.67 for the stoichiometric
titrant volume VOH1 and (pK2 + pK3)/2 = 9.79 for the
stoichiometric titrant volume VOH2. A marked difference of
5.12 pH units exists between these two stoichiometric points
(activity coefficients not considered). In fact, Figure 1 shows
two well-defined neutralization steps from the potentiometric
titration with sodium hydroxide solution, as expected.
Detecting the neutralization of the third hydrogen (from
HPO42–) is not feasible because of the very small magnitude of
K3, 4.21 x 10–13 mol L–1, which yields a very high hydrolysis
constant (KW/K3 where KW is the ionic product of water, 1.00 x
10–14 mol L–1).
For citric acid, the three hydrogens can be titrated, but only
one endpoint is found in the titration curve, which does not
step is used for analytical purposes because the high
potentiometric jump causes buffering failure in the vicinity of
the third endpoint when OH– ions are in excess.
Table 1 presents the pK data for some diprotic organic acids
length on the ionization of the acidic groups caused by the
distance separating them.
Oxalic acid, with two carbons and two close acid groups,
has a 3.01 pH unit difference between pK1 and pK2. This
difference decreases regularly to 1.00 pH unit for adipic acid
(6 carbons). Also, observe that significant differences in pKn
values are observed among the C4 acids, succinic, malic, and
tartaric, because of the absence or presence of one or two OH
groups with their inductive or hyperconjugation effects on the
change density in the carboxylic groups. This affects
ionization. The ∆pK values, however, remain at the same level,
1.3–1.4, for these C4 organic acids. This means that the
ionization of the first carboxyl group is affecting the ionization
of the second group similarly to its effect on the first group, the
distance between them being about the same.
The isomeric acids with a carbon double bond, maleic and
fumaric, exhibit an interesting effect in addition of to that of π
bonding. The ionization of the hydrogen at the trans position of
fumaric acid shows a smaller difference, only 1.46, between
pKs because there is a larger distance between the carboxylic
groups. This is similar to the other C4 organic acids in Table 1.
Conversely, a larger difference in pK, 4.35, is observed for
maleic acid. The proximity of the two carboxylic groups at the
cis position is responsible for a relatively high negative charge
density exerted by the first ionized group on the second one,
lowering its ionization. The derivative potentiometric curve for
the titration of maleic acid shows two well-defined
stoichiometric points (Figure 4), similar to those of phosphoric
acid, and only one peak is found for fumaric acid, which
behaves like citric acid.
For comparison, Figures 5 and 6 show the distribution
diagrams for both acids as calculated from the formation
constants β1 = 1/K2 and β2 = 1/K2K1, on the basis of the widely
used Fronaeus–Leden function [7–9], which is used to treat
chemical equilibrium data for complex formation. Because of a
higher ∆pK and the contribution of the H2X, HX–, and X2–
species to the pH, the maleic acid system shows smaller

© 2005 The Chemical Educator, S1430-4171(05)03909-4, Published on Web 05/27/2005, 10.1333/s00897050909a, 1030200en.pdf
The Effect of Structure on the Behavior of Polyprotic Weak Acids Chem. Educator, Vol. 10, No. 3, 2005 203

overlapping of these species as compared with a similar plot

100
2-
for fumaric acid.
-
HX X
80 References and Notes
1. Jeffery, G. H.; Bassett, J.; Mendham, J.; Denney, R. C. Vogel’s
60
HOOC COOH Textbook of Quantitative Chemical Analysis, 5th ed.; Longman
% species

C C
H H
Scientific & Technical: New York, 1989.
40 2. Christian, D. G. Analytical Chemistry, 4th ed.; Wiley & Sons: New
York, 1986.
H2X
20 3. Skoog, D. A.; West, D. M.; Holler, F. G.; Crouch, S. R. Analytical
Chemistry, 7th ed.; Saunders College Publishing: New York, 2000.
4. Martell, A. E.; Smith, R. M.; Motekaitis; Nist: Critically Selected
0
Stability Constants of Metal Complexes Database; Texas A&M
University: College Station, TX, 1997.
2 3 4 5 6 7 8 9 10
5. (a) Cartledge, G. H.; J. Amer .Chem. Soc. 1928, 50, 2855, 2863;
pH
Cartledge, G. H.; J. Amer .Chem. Soc. 1930, 52, 3076.
Figure 5. Percent distribution of species in maleic acid versus pH. 6. Moeller, T. Inorganic Chemistry—An Advanced Textbook, 2nd ed.,
Wiley & Sons: New York, 1965.
7. Butler, J. N.; Ionic Equilibrium—A Mathematical Approach;
100 Addison-Wesley: Boston, MA, 1964.
8. Rossotti, F. J. C.; Rossotti, H. The Determination of Stability
80 HX
- 2-
X Constants and Other Equilibrium Constants in Solution, McGraw-
Hill: New York, 1961.
H2X 9. Neves, E. A.; Gutz, I.; Tavares, R. J. Electroanal. Chem. 1984, 179,
60
91.
% species

HOOC H
C C
40
H C OOH

20

2 3 4 5 6 7 8 9 10
pH

Figure 6. Percent distribution of species in fumaric acid versus pH.

© 2005 The Chemical Educator, S1430-4171(05)03909-4, Published on Web 05/27/2005, 10.1333/s00897050909a, 1030200en.pdf