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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
■
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
■
*
ASSOCIATED CONTENT
S Supporting Information
■
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
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■
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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