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Laboratory Experiment

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A Simplified Undergraduate Laboratory Experiment To Evaluate the


Effect of the Ionic Strength on the Equilibrium Concentration
Quotient of the Bromcresol Green Dye
Hernán B. Rodríguez†,# and Martín Mirenda*,†,‡

Departamento de Química Inorgánica, Analítica y Química Física, #INQUIMAE, Facultad de Ciencias Exactas y Naturales,
Universidad de Buenos Aires, Ciudad Universitaria, Pab. II, C1428EHA, Buenos Aires, Argentina

Gerencia de Química, Centro Atómico Constituyentes, Comisión Nacional de Energía Atómica, Av. Gral. Paz 1499, 1650, San
Martín, Pcia. de Buenos Aires, Argentina
*
S Supporting Information

ABSTRACT: A modified laboratory experiment for undergraduate students is


presented to evaluate the effects of the ionic strength, I, on the equilibrium
concentration quotient, Kc, of the acid−base indicator bromcresol green (BCG).
The two-step deprotonation of the acidic form of the dye (sultone form), as it is
dissolved in water, yields suitable hydronium concentration in the solution to carry
out the experiment successfully and avoids the use of any buffer solution to fix the
hydronium concentration of the media. The 95% confidence interval for the slope
parameter (−2.08 ± 0.13), obtained from the linear fit of pKc versus √I/ (1 +
2.30·√I) plot, contains the theoretical value of −2.04 predicted by the Debye−
Hückel extended law. From the intercept, a value for the equilibrium dissociation
constant of BCG, pK = (4.91 ± 0.02), is obtained, showing a reasonable agreement
with literature data. The simplification makes it possible for students to complete the
experiment in the course of an ordinary 3-h laboratory session.
KEYWORDS: Upper-Division Undergraduate, Laboratory Instruction, Physical Chemistry, Hands-On Learning/Manipulatives,
Acids/Bases, Aqueous Solution Chemistry, Dyes/Pigments, Equilibrium, Thermodynamics, UV−Vis Spectroscopy

T he fact that the activities of the species involved in a


chemical equilibrium, at a fixed temperature, must be
quantitatively related through a mathematical constant is one of
iron(III)−thiocyanate equilibrium5,6 was proposed; unfortu-
nately, this experience is restricted to a narrow gap of high ionic
strengths due to the experimental conditions in which it takes
the most fundamental concepts used in chemistry. Generally, place. In a different context, experiments based on volumetric
this statement does not hold for the equilibrium concentration titration7 or spectrophotometric quantification8 of the ions in
quotient (Kc)the relation between analytical concentrations equilibrium with a solid have also been proposed. However, in
of reagents and productsbecause this relation changes, for these cases, the success of the experimental procedure requires
example, with the total concentration of the species present in the total absence of solid in the supernatant solution, an
the system. There are several examples in the literature related experimental condition that is not always easy to satisfy in an
to the experimental determination of Kc of aqueous electrolytes ordinary laboratory class. Finally, many experiments have been
and its dependence with the total ion concentration. For proposed9,10 in which the students must assume ad hoc the
instance, at the beginning of the last century, Harned and validity of the Debye−Hückel theory, without evaluating its
collaborators reported a series of electrochemical foundational applicability in the particular experimental conditions of the
works1 in which they quantified the effects of the electrolyte experiences.
concentration on the dissociation of hydrochloric2 and acetic3 In 1963, Richard W. Ramette reported an interesting
acids. Unfortunately, there are multiple factors that must be teaching laboratory experiment for the determination of Kc of
carefully controlled in these classical experiments in order to be an acid−base indicator, the bromcresol green dye (BCG), as a
implemented in teaching laboratories. The list includes the function of the ionic strength,11 probably inspired in techniques
proper cleaning, construction, and maintenance of the used in the past for the determination of Kc of common acid−
electrodes; the purity of the reagents; safety issues related to base indicators.12,13 Ramette’s experiment requires the use of
hydrogen handling; and extended temporal intervals to reach acetic/acetate buffer solutions to fix the proton concentration
adequate thermal equilibrium, to cite a few relevant examples. and literature data of Kc of the acetic acid at different ionic
Several experiments adapted for undergraduate-level labo- strengths14 to calculate the proton concentration in the media.
ratory have been reported in this Journal. Fourteen years ago
the evaluation of the effect of the ionic strength4 on the classical Published: June 15, 2012
© 2012 American Chemical Society and
Division of Chemical Education, Inc. 1201 dx.doi.org/10.1021/ed200733k | J. Chem. Educ. 2012, 89, 1201−1204
Journal of Chemical Education Laboratory Experiment

Moreover, the protocol involves several lengthy procedures that pressure is negligible in condensed phase). When temperature
would make the whole experiment unsuitable to be carried out is constant, a change in the ionic strength will affect the activity
out by a single student in a 3-h laboratory class. In the coefficients and will modify the activity coefficient quotient, Kγ,
experience, students need extended periods of time for the and the equilibrium concentration quotient, Kc. However, the
spectroscopic determination of Kc at each ionic strength from changes are such that the product between both quantities
titration of BCG solutions with acetic acid. should remain constant.
We present a simplified experiment for the evaluation of the Determination of Kc of BCG from Spectrophotometric
effects of the ionic strength on the Kc of BCG, in which the use Measurements
of buffer solutions can be safely avoided. The main goal of our
To determine Kc at different salt concentrations, the analytical
approach is to use the free-acid form of the dye (sultone form),
concentration of reagents and products can be determined from
which shows a two-step dissociation process as it is dissolved in
charge and mass balances as (see the Supporting Information
water. The first dissociation is strong, as is expected for a
for details):
sulfonic acid group, and is responsible for the dissolution of the
free-acid form of the dye in water, rendering the monoanionic [B2 −] = X B2−·c T (2)
form in solution. The second dissociation is weak and
represents the main equilibrium subject to analysis in the
experiment. The two-step dissociation process of the BCG dye [H3O+] = (1 + X B2−) ·c T (3)
is shown in Scheme 1.
[HB−] = (1 − X B2−)·c T (4)
Scheme 1. Two-Step Dissociation Process of Bromcresol
Green Dye in Water Solution where cT is the total analytical concentration of the dye in the
solution and XB2− is the fraction of the dye in the dianionic
form, calculated as15
A 616nm
X B2− = 2−
B
A 616nm (5)
2−
where A616nm and AB 616nm are the absorbance of the sample at
a given ionic strength and the absorbance of the pure alkaline
form of the dye, respectively, measured at 616 nm by using the
same total dye concentration. The expression is valid on the
basis that the absorbance of the monoanionic form of the dye is
negligible at 616 nm. More sophisticated methods that consider
the entire absorption spectra16,17 can be used in order to obtain
The experiment requires the recording of BCG absorption XB2−. However, excellent results were obtained by considering
spectra at different ionic strengths and the subsequent only the absorbance at 616 nm.
comparison with the spectra of the pure acidic and basic Placing eqs 2−5 into eq 1 leads to an expression to calculate
forms of the dye. As such, Kc is obtained for every salt Kc:
concentration by computing the calculated proton concen-
tration, obtained from charge and mass balances, and the ⎛ A ⎞
fraction of the dye in acidic and basic forms, obtained from ⎜1 + 616nm ⎟
⎝ A 616nm ⎠
B2 −
spectral analysis. With this procedure, Kc can be evaluated Kc = c
exclusively from experimental data recorded along the ⎛ A616nm
B2 − ⎞ T
⎜A − 1⎟
experience. ⎝ 616nm ⎠


(6)
THEORETICAL APPROACH Analysis of the Dependence of Kc with the Ionic Strength
Thermodynamics of Acid−Base BCG Equilibrium Using Debye−Hü ckel Theory
The studied equilibrium can be expressed as Two different expressions within the framework of the Debye−
− 2− + Hückel theory were used to analyze the dependence of pKc
HB (aq) + H 2O(aq) ⇄ B (aq) + H3O (aq) with the ionic strength for aqueous solutions at 25 °C (see the
where HB− and B2− represent the monoanionic and dianionic Supporting Information for details): (i) the limiting law, valid
forms of the dye, respectively. Because water activity is almost for very low ionic concentrations,
constant under the experimental conditions, the thermody-
namic equilibrium constant, K, can be expressed as pKc = pK − 2.04· I (7)

a B2−a H3O+ [B2 −]·[H3O+] γB2−·γH3O+ and (ii) the extended law, valid from low to moderate ionic
K= = · = KcK γ concentrations,
a HB− [HB−]·c0 γHB− (1)
where the symbol a represents the activities of each species ⎛ I ⎞
pKc = pK − 2.04·⎜ ⎟
involved in the equilibrium, the brackets denote the analytical ⎝ 1 + 2.30· I ⎠ (8)
molar concentrations, γ represents the corresponding activity
coefficients and c0 the standard concentration (1 mol L−1). The In the last expressions, I is the ionic strength expressed in mol
expression of K depends only on temperature (the effect of L−1.
1202 dx.doi.org/10.1021/ed200733k | J. Chem. Educ. 2012, 89, 1201−1204
Journal of Chemical Education


Laboratory Experiment

EXPERIMENTAL DETAILS An enhancement in the absorbance of the maximum at 616


Materials and Methods nm is clearly observed as the salt concentration increases. This
change can also be visually observed in the solution color
BCG (Aldrich, sultone form, dye purity ∼90%) was used as (Figure 2) and is consistent with the displacement of the
received. NaCl (Baker analyzed reagent, 99.9% purity) was
used as support electrolyte. Solutions were prepared using
freshly deionized water (18 MΩ cm) previously filtered in a
commercial Millipore Milli-Q system equipped with a filter of
0.22 μm pore size (MQ water). Solutions with the same dye
analytical concentration (2.03 × 10−5 mol L−1) and different
salt concentrations (from 0.002 to 0.2 mol L−1) were prepared,
including two samples without salt but acidified with HCl and
alkalinized with NaOH, to record the spectra of the pure acidic
and basic forms of the dye at the working concentration. Figure 2. Changes in color of BCG water solutions (dye concentration
Aqueous solutions were prepared 24 h before the students is 1.67 × 10−5 mol L−1): (a) acidic solution, [NaCl] = 0; (b) dye
conduct the laboratory experiments. The solids were dissolved solution, [NaCl] = 0; (c) [NaCl] = 0.39 × 10−2 mol L−1; (d) [NaCl] =
1.06 × 10−2 mol L−1; (e) [NaCl] = 7.74 × 10−2 mol L−1; (f) [NaCl] =
in hot, freshly deionized water (∼60 °C) and quickly
20.32 × 10−2 mol L−1; (g) basic solution, [NaCl] = 0.
transferred to bottles with caps to prevent the incorporation
of CO2 to the solutions. Dissolution of the dye is kinetically
slow and requires sonication. equilibrium position toward the product. As such, the shift in Kc
Students must record the absorption spectra of the solutions with the ionic strength denotes the diminishing of the activity
and then calculate Kc for the different salt concentrations as coefficients (eq 1), in particular the one corresponding to the
described in the theoretical approach section. A complete and dianionic form of the dye. Numerical data reflecting these
detailed description of the experimental procedures is available changes are listed in Table 1.
in the Supporting Information.


Table 1. Total NaCl Concentration, Fraction of the Dye in
HAZARDS the Dianionic Form, Calculated Hydronium Ion
Some care must be taken to prepare solutions of BCG from the Concentration, and pKc Values of BCG
solid reagent, as it can cause irritation in eyes and skin. [NaCl]/(10−2 mol L−1) XB2− [H3O+]/(10−5 mol L−1) pKc
Hydrochloric acid is corrosive and causes burns to all body 0 0.32 2.68 4.90
tissue. Sodium hydroxide is caustic; it causes burns to any area 0.19 0.36 2.76 4.81
of contact. No other significant hazards are foreseen.


0.39 0.36 2.76 4.81
0.58 0.37 2.78 4.79
RESULTS AND DISCUSSION 0.77 0.38 2.80 4.77
Absorption spectra of the dye at different ionic strengths, 0.96 0.39 2.82 4.74
obtained by students in a standard laboratory session in a 2.88 0.44 2.92 4.64
physical chemistry course, are shown in Figure 1. The spectra 4.76 0.45 2.94 4.62
7.79 0.48 3.00 4.56
9.68 0.50 3.05 4.52
19.35 0.53 3.11 4.46

As it can be seen in Figure 3, the experimental pKc values


plotted versus √I/(1 + 2.30·√I) show a linear behavior up to
ionic strengths of the order of ∼0.20 mol L−1, with a correlation
coefficient, R2 = 0.9921. The 95% confidence interval for the
slope parameter (−2.08 ± 0.13) contains the theoretical value
of −2.04 predicted by the extended law of Debye−Hückel (eq
8). From the intercept, a thermodynamic equilibrium constant,
pK = (4.91 ± 0.02), is obtained. This result agrees reasonably
well with those found in literature (4.9285 ± 0.0030)18 In
Figure 4, pKc experimental values are plotted as a function of
I1/2 together with those computed with the limiting and
Figure 1. Absorption spectra of BCG aqueous solutions at increasing extended laws of Debye−Hückel (eqs 7 and 8), using the pK
salt concentration (thin lines) and at acidic, HB−, and basic, B2‑, value obtained before. From these plots, the students can easily
conditions (thick lines). The trend of increasing ionic strength among
assess the quality of the predictions of the two laws.
the curves is indicated by color.
Identical results were obtained using KCl instead of NaCl to
adjust the ionic strength (data not shown). For electrolyte
of the acidic and basic forms of BCG are included in the same concentrations greater than 0.20 mol L−1, there are deviations
figure, showing absorption maxima at 444 and 616 nm, from the extended Debye−Hückel law that depend on the type
respectively. A clean isosbestic point at 507 nm is observed, of electrolyte used to regulate the ionic strength. Some time
suggesting that the recorded spectra are linear combinations of ago, Robinson and Biggs19 reported values for the ionization
the ones corresponding to the acidic and basic forms of the dye, constant of p-nitrophenol, obtained from spectrophotometric
stoichiometrically related through the studied equilibrium. measurements in four different buffer mixtures. They showed
1203 dx.doi.org/10.1021/ed200733k | J. Chem. Educ. 2012, 89, 1201−1204
Journal of Chemical Education Laboratory Experiment

only based on three fundamental concepts: mass and charge


conservation and Beer−Lambert law.
Another appealing feature of the experiment concerns the
possibility of working in a concentration regime well below the
threshold value above which the Debye−Hückel limiting law
ceases to be valid. Other experiments that rely on the use of
buffer solutions to fix the hydronium concentration cannot be
carried out at such low ionic strengths because the ionic
strength of the buffer alone imposes a minimum height.


*
ASSOCIATED CONTENT
S Supporting Information

Theoretical approach for instructors and students; instructor


notes (including CAS number of BCG and safety warnings);
written directions for students. This material is available via the
Internet at http://pubs.acs.org.


Figure 3. Experimental pKc as a function of [I1/2/(1 + 2.30I1/2)] (open
circles). The solid line corresponds to the linear fit of experimental
data up to ∼0.20 mol L−1 of ionic strength. AUTHOR INFORMATION
Corresponding Author
*E-mail: martinm@qi.fcen.uba.ar.
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
H.B.R. and M.M. have a post-doctoral fellowship from
CONICET. Discussions with Daniel Laria,́ Maria Laura Japas,
and Roberto Fernandez Prini are greatly acknowledged.

■ REFERENCES
(1) Harned, H. S. J. Am. Chem. Soc. 1920, 42, 1808−1832.
(2) Harned, H. S.; Brumbaugh, N. J. J. Am. Chem. Soc. 1922, 44,
2729−2748.
(3) Harned, H. S.; Ehlers, R. W. J. Am. Chem. Soc. 1933, 55, 652−
Figure 4. Experimental pKc values (open circles) and limiting (dashed 656.
line) and extended (solid line) Debye−Hückel laws predictions, as a (4) Cobb, C. L.; Love, G. A. J. Chem. Educ. 1998, 75, 90−92.
function of the root square of the ionic strength. (5) Stolzberg, R. J. J. Chem. Educ. 1999, 76, 640−641.
(6) Ramette, R. J. Chem. Educ. 1963, 40, 71−72.
(7) Corsaro, G. J. Chem. Educ. 1962, 39, 622−626.
(8) Green, D. B.; Rechtsteiner, G.; Honodel, A. J. Chem. Educ. 1996,
that, for ionic strengths higher than 0.12, the values of the 73, 789−792.
ionization constant depend not only on the type of buffer used (9) Tackett, S. L. J. Chem. Educ. 1969, 46, 857−858.
to adjust the pH of the solution, but also on the amount of acid (10) Lamb, R. E.; Natusch, D. F. S.; Ó Reilly, J. E.; Watkins, N. J.
and conjugate base present in each buffer solution. The analysis Chem. Educ. 1973, 50, 432−434.
of more sophisticated theoretical models describing the (11) Ramette, R. J. Chem. Educ. 1963, 40, 252−255.
behavior of ions in highly concentrated salt solutions are well (12) Kolthoff, I. M. J. Phys. Chem. 1930, 34, 1466−1483.
beyond the scope of this teaching laboratory experiment, so we (13) Biggs, A. I. Trans. Faraday Soc. 1954, 50, 800−802.
will restrict the present analysis to solutions with ionic strengths (14) Harned, H.; Hickey, F. C. J. Am. Chem. Soc. 1937, 59, 2303−
lower than 0.20 mol L−1. 2304.


(15) Patterson, G. S. J. Chem. Educ. 1999, 76, 395−398.
CONCLUSION (16) Yamaoka, K.; Takatsuki, M. Bull. Chem. Soc. Jpn. 1978, 51,
3182−3192.
A modified laboratory experiment for undergraduate students is (17) San Román, E.; González, M. C. J. Phys. Chem. 1989, 93, 3532−
presented including a simplified procedure to evaluate effects of 3536.
the ionic strength on the equilibrium concentration quotient of (18) Yamazaki, H.; Sperline, R. P.; Freiser, H. Anal. Chem. 1992, 64,
an acid−base indicator, the bromcresol green dye. The 2720−2725.
simplification involves the absence of buffer solutions to fix (19) Robinson, R. A.; Biggs, A. I. Trans. Faraday Soc. 1955, 51, 901−
the hydronium concentration of the media. Compared with 903.
those experiments that rely on the use of buffer solutions, the
present one has two important advantages: (i) the
simplification of the operational maneuvers that have to be
performed by the students, allowing an individual work that can
be carried out in the course of a typical laboratory class (∼3 h)
and (ii) a simplification of the didactic approach, as the
experimental determination of Kc at different ionic strengths is
1204 dx.doi.org/10.1021/ed200733k | J. Chem. Educ. 2012, 89, 1201−1204