Laboratory Experiment

pubs.acs.org/jchemeduc

The Acid−Base Titration of a Very Weak Acid: Boric Acid

M. Celeste C. Azevedo and Ana M. V. Cavaleiro*
Department of Chemistry and CICECO, University of Aveiro, 3810-193 Aveiro, Portugal
*
S Supporting Information

ABSTRACT: A laboratory experiment based on the titration of boric acid with strong
base in the presence of D-mannitol is described. Boric acid is a very weak acid and direct
titration with NaOH is not possible. An auxiliary reagent that contributes to the release
of protons in a known stoichiometry facilitates the acid−base titration. Students obtain
the potentiometric titration curves of boric acid with standard NaOH in the absence and
in the presence of different quantities of mannitol. The results are used for the
determination of boric acid concentration and for the discussion of the possibility of
performing the titration with a visual end-point determination, including the influence of
the quantity of mannitol in solution. The experiment was developed for an introductory
analytical chemistry course, but may be extended to an advanced analytical course with
the inclusion of a more detailed theoretical treatment. The experiment may be adapted
to general chemistry course as an example of a nontrivial titration.
KEYWORDS: Second-Year Undergraduate, Upper-Division Undergraduate, Analytical Chemistry, Laboratory Instruction,
Hands-On Learning/Manipulatives, Acids/Bases, Potentiometry, Titration/Volumetric Analysis

M uch has been published on the subject of acid−base

titrations and their educational use. In the past decade,
specifically, several articles and letters were published in this
Journal.1−12 From an analytical point of view, a titration is a
counting of the average number of analyte particles in solution
through the reaction with a known number of standard
particles.13 To be used in titrimetry, an acid−base reaction must
come close to completion and textbooks usually emphasized
that the technique cannot be applied to the accurate
determination of the concentration of very weak acids using
conventional equivalence point detection. The use of an
auxiliary reagent to make a titration feasible is not usually
discussed.
Several approaches may be envisaged for the use of this
titration in teaching laboratories. Students in introductory
laboratories may be introduced to the simple titration with a
visual acid−base indicator and to the principle of the use of the
auxiliary reagent to make a titration feasible. In more advanced
analytical courses, they may perform potentiometric titrations
and compare the titration curves obtained for the very weak
acid in the presence or absence of the auxiliary reagent, as
described in this article. Depending on the students’
preparation and learning objectives, the instructor may
introduce the notions of conditional and composite acid
ionization constants and other theoretical aspects, including
calculations and curve interpretation.

In this article, we propose laboratory experiments based on
the titration of a very weak acid (boric acid) with strong base,
performed with the help of an auxiliary reagent (D-mannitol,
Figure 1A, hereinafter referred to as mannitol) that contributes
to the release of protons in a known stoichiometric proportion.
Figure 1. Structures of (A) D-mannitol and (B) boron complexes with
polyalcohols.
© 2012 American Chemical Society and
Division of Chemical Education, Inc.
■
BACKGROUND
Boric Acid Behavior
Boric acid, H3BO3, is a white solid moderately soluble in water.
It is considered a very weak acid, with a tabulated ionization
constant around pKa = 9.2.14 Yet, boric acid does not react in
aqueous solution as a Bronsted acid, but instead, it behaves as a
Lewis acid, with formation of the tetrahedral B(OH)4− anion
(eq 1):
B(OH)3 + H2O ⇌ B(OH)4− + H+ Ka (1)
In dilute aqueous solutions, the monomeric B(OH)3 and
B(OH)4− species are almost exclusively found, whereas
polymeric species may form in more concentrated solutions.15
It is usually stated that boric acid can be transformed into a
relatively strong acid by the addition of organic compounds
Published: March 28, 2012
767 dx.doi.org/10.1021/ed200180j | J. Chem. Educ. 2012, 89, 767−770
Journal of Chemical Education Laboratory Experiment

with at least two hydroxyl groups, such as mannitol, sorbitol, [BL 2−]/[B−]T = (β2[H2L]2 )/(1 + β1[H2L]
glycerol, and others. In fact, boric acid reacts with diols and
other polyalcohols originating mainly anionic boron complexes + β2[H2L]2 ) (17)
with polyol/boron molar ratio of 1 and 2 (eqs 2 and 3): The relation between Ka* and Ka (eq 18) results from
−
B(OH)3 + H2L ⇌ B(OH)2 L + H2O + H + combining eqs 13 and 15:
(2)

− +
B(OH)3 + 2H2L ⇌ BL 2 + 3H2O + H (3)
where H2L is a diol or polyol. The corresponding structures are
presented in Figure 1B.
Many researchers considered the borate anion as the reactive
species, as represented in eqs 4 and 5, for which equilibrium
constants β1 and β2 are available.16,17 Formally, the formation of
these species may be considered a complexation where OH−
groups coordinated to B are substituted by the bidentate ligand
L2‑. It can be seen that eq 2 is the sum of eqs 1 and 4, whereas
eq 3 equals eq 1 plus eq 5.
B(OH)4− + H2L ⇌ B(OH)2 L− + 2H2O β1
(4)
B(OH)4− + 2H2L ⇌ BL 2− + 4H2O β2 (5)
− a new mass balance (CNa = [Na+], where CNa is the analytical
In the subsequent discussion, B(OH)3, B(OH)4 , and
B(OH)2L− are replaced by HB, B−, and BL− respectively. A
set of seven independent equations (and seven unknowns)
define the system formed by boric acid and a polyol in aqueous
solutions, assuming that only monomeric species are formed.
These comprise the expressions of the equilibrium constants
Ka, β1, β2, and Kw (eqs 6−9), boron and polyol mass balances
(eqs 10 and 11, respectively, where CB and CL are the respective
analytical concentrations), and the charge balance.12
Ka* = Ka(1 + β1[H2L] + β2[H2L]2 ) (18)
It can be seen that Ka* varies with the concentration of
uncombined polyol in solution. If the molar ratio CL/CB is
large, the mass balance (eq 11) simplifies to CL ≅ [H2L]. Thus
Ka* = Ka(1 + β1CL + β2CL 2) (18a)
is applicable when a large excess of polyol is present in solution.
The value of pKa* of boric acid in the presence of excess
mannitol, using pKa = 9.20,14 log β1 = 3, and log β2 = 5,16,17
falls in the range of 4 to 5 in an available range of mannitol
concentrations.
Titration of Boric Acid
Considering the titration of boric acid with NaOH, in the
presence of mannitol, the system is defined by a total of eight
equations. These are eqs 6−11 plus the charge balance 19, and
concentration of NaOH).
[H+] + [Na+] = [OH−] + [B−] + [BL−] + [BL 2−]
(19)
−
Taking in account the definition of [B ]T (eq 14), the mass
balance of boric acid (eq 10) and the charge balance (eq 19) in
solutions of boric acid, mannitol, and NaOH transform into eqs
20 and 21, respectively.

Ka = ([B−][H+])/[HB] CB = [HB] + [B−]T (20)

(6)

β1 = [BL−]/([B−][H2L]) [H+] + [Na+] = [OH−] + [B−]T (21)

β2 = [BL 2−]/([B−][H2L]2 )
K w = [H+][OH−]
CB = [HB] + [B−] + [BL−] + [BL 2−]
CL = [H2L] + [BL−]+ 2[BL 2−]
[H+] = [OH−] + [B−] + [BL−] + [BL 2−]
For the subsequent discussion, it is convenient to define a
composite acid ionization constant for boric acid, Ka* (eq 13),
where [B−]T is the total concentration of negatively charged
borate species, as defined in eq 14. Fractions relating the
concentration of each charged boron species to [B−]T may be
calculated using eqs 15−17.
Ka* = ([B−]T [H+])/[HB]
[B−]T = [B−] + [BL−] + [BL 2−]
[B−]/[B−]T = 1/(1 + β1[H2L] + β2[H2L]2 )
[BL−]/[B−]T = (β1[H2L])/(1 + β1[H2L] + β2[H2L]2 )
(7)
The set of eqs 9, 13, 20, and 21, corresponding to the system
(8) boric acid/NaOH/mannitol in aqueous solution, is identical to
that used for the study of the titration with NaOH of any weak
(9)
acid.18−20
The titration of boric acid with strong base in the presence of
(10)
mannitol usually takes place with CL/CB = 10−15.21 The pKa*
may vary slightly along the titration, depending on the extent of
(11)
the complexation. This does not prevent the feasibility of the
titration, which has been repeatedly demonstrated,21−25 but has
consequences if the calculation of the titration curve is
(12)
attempted. It is possible to deal with this variation using an
iterative calculation procedure, schematically presented in
Figure 2.
For a given point of the titration curve, the calculation starts
with the choice of a value for [H2L]0, usually [H2L]0 = CL,
which allows the determination of Ka* (eq 18a). Considering
the set of eqs 9, 13, 20, and 21, [B−]T, [HB], and pH are
calculated as usually done for a weak acid−strong base titration,
(13) following the procedure described in many textbooks.18−20
[B−], [BL−], and [BL2−] are obtained from [B−]T and eqs
(14) 15−17. Now, eq 11 is used to determine a value for [H2L] that
is compared with that assumed initially. If the values are similar,
(15) the initial assumption is taken as correct. If not, the obtained
[H2L] is used to start a new iterative cycle. The procedure may
be easily performed with the help of an Excel spreadsheet. The
comparison between a value obtained for [H2L] (e.g., [H2L]n)
(16) with that assumed to initiate the iterative cycle ([H2L]n−1) may
768 dx.doi.org/10.1021/ed200180j | J. Chem. Educ. 2012, 89, 767−770
Journal of Chemical Education
Figure 2. Iterative procedure to determine pH and the concentration
of the species in a solution of boric acid and mannitol in a titration
with strong base.
be done by visual inspection, but, in this case, the number of
iterations may increase as CL/CB diminishes and the method
was not applicable for C L/CB ≤ 1, because negative
concentration values appeared.
A better option is the use of the Excel Solver tool. In this
approach, the assumed [H2L] concentration is introduced. The
spreadsheet is prepared for the calculation of concentration of
the species. The Solver is asked to zero the function F = [H2L]n
− [H2L]n−1. No iterations are needed in most cases. More
information is presented in the Supporting Information. The
method just described was used to determine titration curves
and the value of pKa* along the titration of a 0.05 M boric acid
solution. Dilutions were neglected in these calculations. Figure
3 represents the variation of pKa* during the titration of boric
acid in the presence of mannitol for different X = CL/CB. It can
be seen that, for CL/CB ≥, 10 the variation of pKa* during the
course of titration is not very pronounced and that the average
value of pKa* is lower than 5. Thus, this condition seems
acceptable for the feasibility of a titration, but the solubility of
mannitol26 may limit the range of useful boron concentrations.
The results of these calculations also showed that [HB] and/or
[BL2−] were the predominant species during the titration of
solutions with CL/CB ≥ 5. In contrast, [B−] was always very
small.
■ EXPERIMENTAL PROCEDURE
The work proposed to the students consists in the
potentiometric titration of boric acid (∼0.05 M) with standard
NaOH 0.1 M (both prepared prior to the laboratory period) in
the absence and in the presence of different amounts of
mannitol (with CL/CB between 2 and 20). The students work
in pairs and, at the end, the results are pooled and discussed.
Each pair of students uses only one CL/CB ratio. The same
769
Laboratory Experiment
Figure 3. Variation of pKa* during the titration of boric acid (CB =
0.05 M) in the presence of mannitol, CL, (X = CL/CB) calculated with
the help of the iterative procedure represented in Figure 2 and pKa =
9.20,14 log β1 = 2.98, and log β2 = 4.98.17 CNa = concentration of
NaOH in solution. Dilutions were neglected in these calculations.
stock solution of boric acid is used by all groups. Solid mannitol
is dissolved in a 25 mL aliquot of the boric acid solution for the
preparation of the solution with the required CL/CB to be
titrated.
Each pair of students obtains the experimental potentio-
metric curve and determines the analyte concentration. The
procedure used may depend on the laboratory resources and
previous knowledge of the students and is not detailed here.
Also, students discuss the results obtained and assess the
possibility of performing the titration with a visual end-point
determination.
The experiment is intended for a laboratory period of 3 h. A
typical distribution of time is (i) 1 h for experimental work; (ii)
1 h for tracing of the curves, the determination of the end point,
and other calculations; and (iii) about 30−45 min for the
discussion.
■ HAZARDS
Caution is needed in handling the strong basic NaOH
solutions, and students should be aware of the necessary
precautions and safety instructions. Boric acid is hazardous in
case of skin or eye contact, of ingestion and of inhalation, and
presents reproductive toxicity.27 Students should avoid
exposure. In case of contact, immediately flush skin with
plenty of water. Mannitol is not considered dangerous.
■ RESULTS
Examples of potentiometric curves obtained in the exper-
imental conditions used are presented in Figure 4. Students are
asked to calculate the concentration of boric acid in the
solution provided. The volume of NaOH used to reach the
equivalence may be determined either visually or from the first
derivative curve.28
In the absence of mannitol (CL = 0; X = 0), the variation of
pH around the equivalence point is small, in accordance with
the small ionization constant of boric acid, precluding the use of
any visual indicator for this purpose. In contrast, curves
obtained with CL/CB = 10 (X = 10) or higher are typical of
acids that may be titrated with the help of visual indicators,
dx.doi.org/10.1021/ed200180j | J. Chem. Educ. 2012, 89, 767−770
Journal of Chemical Education
Figure 4. Experimental potentiometric curves in the titration of boric
acid (CB = 0.051 M, 25 mL,) with NaOH 0.100 M in the presence of
mannitol (different CL concentrations, X = CL/CB).
presenting a variation of at least 4 pH units near the
equivalence point.
It is easily deduced that at midtitration, when the volume of
NaOH used is half that of the equivalence point, [HB] = [B−]T
and pH = pKa*. Students may thus determine the value of pKa*
at midtitration, obtaining values between 4 and 5 for CL/CB ≥
10.
Students should be aware that pKa* may only be taken as
approximately constant during the titration when CL/CB is
large, specifically when CL ≅ [H2L] and Ka* = Ka (1 + β1CL +
β2CL2). Nevertheless, pooling of the results will show the
decrease of pKa* at midtitration with the increase of CL.
■
CONCLUSIONS
Acid−base titration in the presence of mannitol is a standard
method of analysis of boric acid in different media. The work
here described was developed with the aim of presenting the
students with a case study in which an acid−base titration is
made feasible by the use of an auxiliary reagent. The
determination of the potentiometric curves for different CL/
CB molar ratios shows the influence of this parameter in the
devising of the experimental procedure and, thus, leads to a
deeper understanding of titration methods referred in the
literature. The potentiometric titration curves have been
published and the students may compare their results with
those previously described in similar (or related) condi-
tions.22−24 It is also possible to calculate pKa* at midtitration
and observe its decrease with the increasing amount of
mannitol used. The calculation of titration curves, however, is
not recommended at most levels. The simple approach is
presented here for the sake of interested instructors. This work
may be used in analytical laboratories as it allows the discussion
of a nontrivial acid−base system and of the possibility of using
an auxiliary reagent to perform an uncommon titration.
Nevertheless, it may be adapted to general chemistry
laboratories and used namely to teach potentiometric titrations
■
ASSOCIATED CONTENT
* Supporting Information
S
Documentation containing the experimental procedure for the
students and instructor notes. This material is available via the
Internet at http://pubs.acs.org.
770
■
Laboratory Experiment
AUTHOR INFORMATION
Corresponding Author
*E-mail: anacavaleiro@ua.pt.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors wish to thank one of the reviewers, who suggested
the use of the Solver tool of the Excel worksheet.
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