Mikrochim.

Acta 106, 327-337 (1992)

Mikrochimica Acta
9 by Springer-Verlag1992 Printed in Austria

Effect of the Solvent on the Equilibria of Acid-Base Indicators in Aprotic and Amphiprotic Solvents
Jos6 Barbosa*, Caries M. Bosch, and Victoria Sanz-Nebot Department of AnalyticalChemistry,Universityof Barcelona, E-08028 Barcelona,Spain
Abstract. The dissociation constants of a series of indicators in N,N-dimethyl-

formamide medium have been determined, and compared with those for the indicators in other aprotic solvents (dimethylsulphoxide and acetonitrile) and in some amphiprotic solvents (water, methanol, ethanol, propan-2-ol and tertbutanol). The effect of the solvent characteristics on the pK values have been t evaluated, and the pK + PTw-~s(H + ) values shown to be linearly correlated with the Dimroth and Reichardt E~ and acceptor number solvatochromic parameters.
Key words: indicators, dissociation constants, aprotic solvents, amphiprotic

solvents.

Indicators are often used to establish the acidity scale after the spectrophotometric determination of their dissociation constant [1, 2] and the indicator method has been used to measure acid dissociation constants of a variety of substances in many solvents [3-5]. We have studied the dissociation constants of indicators in various amphiprotic [6-8] and aprotic [9] solvents. In the present paper we report the dissociation constants of a series of indicators in N,N-dimethylformamide(DMF) medium and the relation of their pK values in the aprotic protophilic solvents D M F and dimethylsulphoxide (DMSO) to those in the aprotic protophobic solvent acetonitrile (AN) and in the amphiprotic solvents water, methanol (MeOH), ethanol (EtOH), propan-2-ol (iso-PrOH) and 2-methylpropan-2-ol (tert-BuOH). Its moderately high dielectric constant, e = 36.7 at 25~ [10] and aprotic nature make D M F particularly useful for acid-base studies and a wide range of organic reactions, as well as for studies of electrochemical reactions and coordination chemistry. Because of its greater hydrogen-bond accepting basicity, with a solvatochromic parameter fl = 0.69 [11], homoconjugation and heteroconjugation complexes occur to a lesser extent in D M F than in AN [4] with the result that the titration curves for D M F media are often normal in the buffer region [10]. * To whom correspondenceshould be addressed

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The Born model is inadequate to explain the influence of the solvent on the dissociation constant of indicators, and the solvatochromic solvent scales must be considered. For pure solvents the multiparametric equation of Kamlet et al. I-11] in its more complete form includes terms which measure the hydrogen-bonding proton donation (~) and proton acceptance (/~), the polarity 0z*), the polarizability (6) and the Hildebrand solubility parameter (4). Simpler scales have been defined with the Dimroth and Reichardt parameter E~ (30) [ 12] and the acceptor number AN [ 12]. In this work the relationships between the dissociation constants of the indicators in the media listed above, and the characteristics of the solvent media (l/e, AN, E~, z~*,~ and/~) have been examined.

Experimental
Apparatus
A Beckman DU-7 spectrophotometer with 1-cm path-length cells, and a Hewlett-Packard 9816 computer were used. For potentiometric titrations, a Crison Digilab 517 pH-meter equipped with a Radiometer G202B glass electrode [13] and a 0.01 M AgNO3 (DMF)/Ag reference electrode (with 0.1 M tetramethylammonium perchlorate in D M F serving as a double salt-bridge similar to that used by Kolthoff et al. [2] was used. This system of electrodes and salt-bridge (kept at 25~ was the best combination of all those tested; stable and reproducible potentials were obtained in 15 rain or less. The glass electrode was kept in D M F when not in use, as recommended by Kolthoff et al. [2]. The D M F solutions containing Ag + ions were colourless and clear when first prepared, but after about ten days became crimson and turbid, even though they were not exposed to light for more than 1 h during that period [14, 15]. To minimize possible decomposition of the reference electrode solution, quantities of perchloric acid were added [4]. All experiments were done under a purified nitrogen atmosphere.

Reagents
Analytical-reagent grade (or equivalent) chemicals were used throughout. A solution of hydrogen chloride in D M F was prepared. The indicators examined were Thymol Blue (TB), Bromocresol Green (BCG), Bromothymol Blue (BTB), m-Cresol Purple (MCP), Phenol Red (PR) and Azo Violet (AV).

Determination of the Standard Potential and Autoprotolysis Constant

The glass electrode was calibrated by titration of 0.005 M benzoic acid solution in D M F with 0.1 M tetrabutylammonium hydroxide. A value of pK = 12.27 for benzoic acid in D M F was taken as a standard reference value because there is excellent agreement about it [2, 4, 16, 17]. The pH values of the mixtures were calculated on the basis of partial dissociation of the acid and complete dissociation of the salt [-2]. Similar methods had been used by us for the calibration of the glass electrode in AN [9], iso-PrOH [-7] and tert-BuOH [8] media. The small quantity of alcohol introduced by the titrant does not significantly influence the chemical potential of species dissolved in D M F [18]. A computer program written in BASIC, ACETERISO [19], was used to calculate the standard potentials in acidic and basic medium. From these values, the autoprotolysis constant of the medium could be calculated. The average value obtained was pKap = 23.2 4- 0.3.

Solvent on the Equilibria of Acid-Base Indicators Procedure

329

The indicator solutions (approximately 10-5 M) were titrated with 0.1 M tetrabutylammonium hydroxide solution, in the presence of an appropriate acid to keep the solution buffered over the pH range of the colour change (hydrochloric and benzoic acid mixture for TB, salicylic acid for BCG, benzoic acid for BTB, hydrochloric acid and phenol mixture for MCP, acetic acid for PR and malonic acid for AV). The titrations were monitored by continuous simultaneous measurement of the absorbance and the electrode potential. The test solution was stirred with a stream of nitrogen and continuously circulated between the titration vessel and the spectrophotometer cell by means of a peristaltic pump. The temperature was 25 + 0.2~

Results and Discussion

The autoprotolysis constant pKap = 23.2 obtained for D M F defines the normal range ofpH in the solvent and also has an important bearing on acid-base titrations, where the greater the PKap value, the larger the "pH jump" at the equivalence point. Relationships between the autoprotolysis constants and other characteristics of water, MeOH, EtOH, iso-PrOH, tert-BuOH, DMSO, AN and D M F [7, 8, 20, 21], Table 1 [12], have been examined. Thus, pKap values have been plotted against l/e, AN, ENT,re*, ~, ft. For the solvents studied pKap is roughly correlated with E~, PKap = -28.1E~ + 40.1, r = 0.82.

The autoprotolysis constant is a composite function of the intrinsic acidic and basic strength of the solvent and its relative permittivity [20]. The fact that E~ is a measure of the polarity and polarizability of the solvent and its hydrogen bond donicity [12] suggests that these factors may be mainly responsible for the variations in pK,p. The indicators studied in D M F exhibit two kinds of dissociation equilibria: (1) AVI: H2I ~ H I - + H +, pK = pH - log YH, -- I~ 9

Table 1, pK,v, dielectric constant, solvatochromic parameters and pT~ws(H +) values for the solvents Solvent Water MeOH EtOH iso-PrOH tert-BuOH DMSO AN DMF pKap 14.00 16.70 19.10 22.00 28.50 32.90 33.60 23.21 e 78.54 32.63 24.30 18.30 10.90 46.00 36.00 36.70 E~ 1.000 0.762 0.654 0.546 0.389 0.444 0.460 0.404 7r* 1.09 0.60 0.54 0.48 0.41 1.00 0.75 0.88 a 1.17 0.93 0.83 0.76 0.68 0.00 0.19 0.00 fl 0.18 0.62 0.77 0.95 1.01 0.76 0.31 0.69 AN 54.8 41.5 37.9 33.6 27.1 19.3 18.9 16.0 PT~ws(H +) 0.0 - 1.8 - 1.9 -0.5 - 1.l 3.3 -8.1 2.5

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(2) BCG, AV2, BTB, MCP, PR, TB: H I - ~ 12- + H pK = pH + log(yur/y~ ) -- log([I2-]/[HI-]). The concentration of the basic and acid forms of the indicator, and hence the colour, is related to the pH and ionic strength of the system [8]. The effect of ionic strength is different for the two models and could be important at high ionic strengths for indicators of type 2. Because of the high dielectric constant of D M F the activity coefficients have less influence in it than in other solvents, such as tert-BuOH and iso-PrOH, and similar influence to that in AN. The pK values are calculated from the relationships above, the experimental pH values, and the activity coeffidients calculated by means of the Debye-Hiickel equation, log y = -Ax//I/(1 + B&~/~), where A = 1.594, B = 0.480 x 108 and h = 5 A [-223. The concentration ratio of the basic and acid forms of the indicator were determined from the complementary chromaticity co-ordinates [23-25] and spectrophotometrically [26]. The results of the two methods agree and are shown in Table 2. In the case of sulphophthalein indicators, the first protonation equilibrium is not visually perceptible and its dissociation constant is not determined, because it is of little analytical importance.
T a b l e 2. p K v a l u e s o f t h e i n d i c a t o r s (2-NP: 2 - n i t r o p h e n o l , 2 , 4 - D N P : 2 , 4 - d i n i t r o p h e n o l , 2 , 6 - D N 4 C 1 P : 2,6-dinitro-4-chlorophenol, n i t r o p h e n o l , PA: picric acid) Indicator BCG BTB MCP PR TB AV1 AV2 2-NP 2,4-DNP 2,6-DN4C1P 2,6-DNP 3,5-DNP 4-NP PA H20 4.7" 7.1 a 8.3 b 7.9 a 8.9" 12 b 7.2 a 4.0 b 3.0 a 3.6" 6.7 a 7.2" 0.35 b AN 18.80 22.3 a 26.5 b 25" 27.2 a 30.5 b 22.0 a 16.0 b 15.3 a 16.45 ~ 20.5 a 20.7 a 11.0 a DMF 9.06 12.96 15.16 15.37 15.24 9.15 13.52 12.19 e 6.33 f 4.70 f 5.77 f 11.30 f 12.64 f 1.16 f 11.0" 5.2 g 3.5" 4.9 h 10.6 a 11 a - 1.0" 11.2 g 3.8 g 14.60 j 5.35 j 12.45 j 4.02 j 7.9 g 15.88 j 13.3 j 13.7" 15.3 a 12.8 c 14.0 r 18.75 i 15.0 k 13.55 c 15.2 c DMSO 7.3 a 11.3" MeOH 9.8 g 12.4 r tert-BuOH 12.12 i 15.95 i iso-PrOH 9.66 k 13.34 k EtOH 10.65 r 13.2 c 2,6-DNP: 2,6-dinitrophenol, 3,5-DNP: 3,5-dinitrophenol, 4-NP: 4-

a V a l u e s f r o m ref. [ 1 ] b V a l u e s f r o m ref. [27] c V a l u e s f r o m ref. [28] d V a l u e s f r o m ref. I-9] e V a l u e s f r o m ref. [29] f V a l u e s f r o m ref. [2]

g V a l u e s f r o m ref. [4] h V a l u e s f r o m ref. [ 3 ] i V a l u e s f r o m ref. [8] J V a l u e s f r o m ref. [ 3 0 ] k V a l u e s f r o m ref. [ 7 ]

Solvent on the Equilibria of Acid-Base Indicators Table 3. Differences between pK of the indicators in different solvents Indicator BCG BTB MCP PR TB 2-NP 2,4-DNP 2, 6-DN4C1P 2,6-DNP 3, 5-DNP 2-NP PA ApKAN.DM F 9.74 9.34 11.34 9.63 11.96 9.81 9.67 10.60 10.68 9.20 8.06 9.40 z~pKDMF_DMSO ApKAN_DMSO 1.76 1.66 1.67 - 0.06 1.19 1.13 1.20 0.87 0.70 1.64 2.60 11.50 l 1.00 l 1.30 11.90 11.00 10.80 11.80 11.55 9.90 9.70 12.00 ApKDMF_H2 o 4.36 5.86 6.86 7.47 6.34 4.99 2.33 1.70 2.17 4.60 5.44 1.25

331

In Table 2, the pK values reported by other investigators for some indicators, which have very poor colour change in DMF, are also shown, along with the pK values of the indicators in water, AN, DMSO, MeOH, tert-BuOH, iso-PrOH and EtOH, some of which have been reported previously [7-9]. All the indicators studied are much weaker acids in D M F than in water. The factors contributing to the ApKDMv-H20values, Table 3, are illustrated by comparing the following equilibria [31], HAw + H 2 0 ~ H30~v + Aw and HADMF + HCO-N(CH3)2 ~ HCOH-N(CH3)~-DMF + ADMF, where the subscripts indicate solvation by water and DMF, respectively. Although the solvent influence is complex, taking into account the availability of D M F to solvate protons, the dominant factor must be the fact that the hydrogen-bond donating power of D M F is much lower than that of water [-12, 32]. Table 3 shows the differences in pK of the indicators studied, between AN and DMF, ApKAN.DMV;D M F and DMSO, ApKDMv_DMSO;AN and DMSO, ApKAN.DMSO. These differences are fairly constant and equal to 10.0 _+ 1.0, 1.3 _ 0.6 and 11.1 _+ 0.7 (mean __ standard deviation), respectively. For substances with intramolecular hydrogen bonding, ApK between AN and D M F or DMSO is different. The reason is that AN is too weak a base to break the intramolecular hydrogen bond and D M F and DMSO are strong enough bases to break it [2]. From the analytical viewpoint, it is of interest to mention that the ApK of indicators is of the same order of magnitude for the pairs of aprotic solvents, AN, D M F and DMSO, and quite different from that between water and an aprotic solvent, as shown in Table 3 for D M F as an example. The difference in the pK of the indicators (PKHI) in AN and D M F is expressed in terms of transfer activity coefficients by Eq. (1) [33], ANADMFpKH,= (PKm)AN -- (pKH,)DMF = P?kN-,DMF(H+) + PY~N-~DMF(I-)
-- p?~N~DMF(HI), (1)

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in which p = - l o g and 7t(i) is the transfer activity coefficient of the species i. The symbol 7 t is preferred to the alternative DMVYH,also a p p r o v e d b y IUPAC [31]. AN. 0 The transfer activity coefficient is closely related to AG~v-~s(i), the standard free energy of transfer of 1 mole of species i from water (W) to solvent S,
t log 7w-~s(i ) =

[AG~v_~s(i)]/2.303RT.

Equations similar to (1) can be derived for ApKDMF.DMSO and ApKAN.DMSO. The various extrathermodynamic assumptions which have been made to find transfer activity coefficients, have been discussed in a recent review [35]. In the present work the values log 7~V_~AN(H = 8.1, log 7W-~DMF(H = --2"5 and +) t +) log 7W_~DMso(H+) = --3.3, reported by Kolthoff and Chantooni [32] were used. ' These data are based on Parker's assumption that y'(AsPh,~) = 7t(BPh+), referred to as the tetraphenylborate assumption. This assumption with reference to water would appear to yield ,/'-values closer to the true value than other assumptions do t [36]. The PTw-.s( H + ) values [36] are shown in Table 1. There is no uniform agreement on the sign convention. In this work a value of log 7{V_.AN(H+) = 8.1 means that a solute giving a hydrogen-ion activity of 1 in acetonitrile would give an activity of 10 - s l in water. Therefore, a positive values of log 7w-.s indicate that t the solvent-solute interactions are greater for the solute in water than in the solvent. Thus the proton transfer activity coefficients between the aprotic solvents studied are py~N_,DMV(H = pT~,N_+W(H+) + py~WDMF(H+) = 10.6, and similarly +)
PYDMF+DMso(H ) = 0.8 a n d PTAN_.DMso(H ) ----- 11.4.
t + t +

Taking into account that the ApK values determined between these aprotic solvents are close to 10.6, 0.8 and 11.4, respectively, Table 3, the influence of the proton transfer activity coefficient on the differences in pK values of the indicators between AN and D M F , D M F and DMSO, AN and D M S O is important. Thus, assuming Eq. (1), the difference in pT'(I-) and pTt(HI) values is small between these three aprotic solvents. Also, since ApK of all the indicators was found to be approximately the same for a given pair of the three aprotic solvents studied, Table 3, the implication is that there is no difference in resolution of acid strength between the three solvents, D M F , AN and D M S O [37]. However, the ApK values of the indicators between an aprotic solvent such as D M F and water are not constant and differ from the PT~v_~DMF(H value. For anions with a localized charge, the hydrogen bonding in the amphiprotic solvents makes anion solvation much greater than in the aprotic solvents and there is a great effect of the nature of the solvent on pT'(I-) [32]. On the other hand, the effects of homoconjugation were encountered by Kolthoff [3] for acid-base systems in AN. It has been that the formation constant of the homoconjugate ion is of the order of 100 times greater in AN than in D M S O [1]. The reason is that the acid is not hydrogen-bonded in AN, which has a fl solvatochromic parameter value of 0.31, whereas D M S O (fl = 0.76) and also D M F (fl = 0.69) [12] are stronger hydrogen-bond acceptors than AN, so that the undissociated acids are more solvated and have less tendency to hydrogen-bond with anions. The relationships between the dissociation constant of the indicators in a particular solvent, Table 2, and different characteristics of the solvent medium have been examined, but plots of pK m values versus 1/e and the solvatochromic parameters re*, ~, fl, AN and ENr values show no zone of linearity.

Solvent on the Equilibria of Acid-Base Indicators

333

Traditional p K measurements reflect the degree of dissociation of a species in a given solvent, but a valid measure of the relative proton activity is not possible [38]. One of the main purposes of the studies dealing with the influence of solvents on acid-base equilibria is to obtain a solvent-independent acidity scale.

20
pK + pY

19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 O 10
r -i i i

[]

o o o

30

50
AN

20
D
pK + p'f

18 17 16 15 14 X

12 11 10 9 B 7 6 5 -

4~
3 2 1 0 I0 30 50

b Fig. 1. Plot of pK + pT~ws(H +) versus the solvatochromic parameter AN; a [] BTB + BCG, 9 PR, O PA, zx2,6-DN4C1P, x 3,5-DNP; b [] TB, + 2,4-DNP, ~ 2,6-DNP, zx4-NP, 2-NP

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J. Barbosa et al.

By referring the acid-base character of non-aqueous solvents to the same aqueous standard state, an "absolute" pH' scale is obtained which allows the acidity of aqueous solutions to be compared directly [39],
t pH' = p H s + PTw-~s(H q - ) .

20
pK + p~

19 18 17 16 15 14 13 12 11 10 9 8 7 B 5 4 3 2 fl 0
I I I I I ~ ]

0 ~ X +
+

~@

~
+ ~

4o

04

0.6

08
N

ET

20

pK + PY

19 1B 17 16 15 14 13 12 11 10 9 B ? 6 5 4 3 2 1 0 0

[] [] E3D

A []

0 4

06

E~

Fig. 2. Plot of pK + pT~ws(H +) versus the solvatochromic parameter E~. Symbols as in Fig. 1

Solvent on the Equilibriaof Acid-BaseIndicators

335

For a solvent S, the dissociation constants of a series of indicators in this solvent, pKs, were then translated to the absolute scale by the equation pK'
=

t pKs + PTw-.s( H + ).

It must be emphasized that each pK, value is valid only for the pH scale relevant to the specific pure solvent considered [40]. Values of pKs pertaining to different solvents would become physically comparable on an "intersolvental" pH scale with ultimate reference to the familiar pH scale in water, only if first converted into pK' values by the equation above. In Fig. 1 plots of the sum of pK and the proton transfer activity coefficient to the solvent [36] versus the hydrogen-bond acidity parameter AN [12] are shown for several indicators for which the relevant pK values are known. These plots show t that the pK + Ww~s(H + ) and AN values roughly form a line for each indicator studied. However, for evaluating solvent effects polarization must also be considt ered, and in Fig. 2 plots of pK + PVw-.s(H + ) values versus the solvatochromic parameter E~ are shown. The E~ parameter is a measure of the polarity-polarizability of the solvent and its hydrogen-bond donor acidity [12]. The excellent plots obtained for the substances studied show that a solvent-anion interaction, which decreases strongly as the charge on the anion becomes more delocalized [4], seems responsible for the change in the dissociation equilibrium constant with the proton transfer activity coefficient, which is a measure of the proton-solvent interactions. However, more data would be desirable before a firm conclusion can be reached. In this line a study with more solvents and many more dissociation constant values is being made. As can be seen from Fig. 2, if the pK values of a substance in different solvents are known, then its dissociation constant in another solvent can be approximately calculated. The proton transfer activity coefficient represents the acid end of the solventindependent pH' scale in each solvent S, with ultimate reference to the familiar

-I0

10

20

30
I

~H'

[
I

I I

/-/2o
Et OH iso - P r O H t - Bu OH Me OH

[
[ I
I I

DWSO DNF

l I
I

AN

H20
I f I

-10

10

20

30

oH I

Fig. 3. AbsolutepH' scalefor the solvents investigated

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J. Barbosa et al.

aqueous pH scale and physical comparability with it. The basic end of the pH' scale in any solvent is conventionally defined from its autoprotolysis constant [41]. This approach is utilized in Fig. 3 to compare, on the basis of this absolute pH' scale, the acid strength in the solvents considered. In Fig. 3 the acid and basic limits for all the solvents considered are indicated; the first were taken from the pT~v_.s(H+) values available in the literature [36] and the latter were taken from the pK,p values of the solvents considered J-7, 8, 20, 21]. Fig. 3 may be applied by taking into account the pK values indicated in Table 2 and their references. It is worth noting that an illustrative picture such as Fig. 3 is very useful for gaining insight into solvent effects on acid-base equilibria. Thus, it becomes possible to assess rapidly the shift in basicity of buffer solution caused by changes in the nature of the medium, as well as to estimate which indicator will give a sharp colour change in the equivalence range of visual acid-base titrations in non-aqueous solvents. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [-27] [28] [29] [30] [31] [32] I. M. Kolthoff, M. K. Chantooni, Jr., S. Bhowmik, J. Am. Chem. Soc. 1968, 90, 23. I. M. Kolthoff, M. K. Chantooni, Jr., H. Smagowski, Anal. Chem. 1970, 42, 1622. I. M. Kolthoff, Anal. Chem. 1974, 46, 1992. B. W. Clare, D. Cook, E. C. F. Ko, Y. C. Mac, A. J. Parker, J. Am. Chem. Soc. 1966, 88, 1911. G. Demange-Gu6rin, Talanta 1970, 17, 1075. J. Barbosa, D. Barr6n, E. Bosch, Analyst 1987, 112, 1717. J. Barbosa, E. Bosch, F. Su~trez, Analyst 1985, 110, 1473. J. Barbosa, E. Bosch, M. Ros6s, Analyst 1987, 112, 179. J. Barbosa, M. Ros6s, V. Sanz-Nebot, Talanta 1988, 35, 1013. I. M. Kolthoff, P. J. Elving (eds.), Treatise on Analytical Chemistry, Part 1, Vol. 2, 2rid Ed., Wiley-Interscience, New York, 1979. M. J. Kamlet, J. L. M. Abboud, M. H. Abraham, R. W. Taft, J. Org. Chem. 1983, 48, 2877. C. Reichardt, Solvent and Solvent Effects in Organic Chemistry, Verlag Chemic, Weinheim, 1988. J. Juillard, J. Chim. Phys. 1970, 67, 691. J. N. Butler, J. Phys. Chem. 1968, 72, 3288. A. V. Benedetti, C. S. Fugivara, M. Cilense, Anal. Lett. 1983, 16, 1357. J. Juillard, B. Loubinoux, C. R. Acad. Sci. Paris 1967, 264, 1680. A. Petrov, I. Umanskii, Zh. Fiz. Khim. 1967, 41, 1374. A.J. Parker, Aust. J. Chem. 1963, 16, 585. M. Ros6s, Colloquium Chemiometricum Mediterraneum, Barcelona, 1987. S. Rondinini, P. Longhi, P. R. Mussini, T. Mussini, Pure Appl. Chem. 1987, 59, 1693. J. Barbosa, D. Barr6n, J. E. Beneyto, V. Sanz-Nebot, J. Pharm. Biomed. Anal. 1988, 6, 709. J. Juillard, J. Chim. Phys. 1966, 63, 1190. C. Reilley, E. Smith, Anal. Chem. 1960, 32, 1233. H. Flaschka, Talanta 1961, 8, 342. J. Barbosa, C. M. Bosch, Talanta (submitted). A. Albert, E. P. Serjeant, The Determination of Ionization Constants, Chapman & Hall, London, 1974. I. M. Kolthoff, M. K. Chantooni, Jr., S. Bhowmik, Anal. Chem. 1967, 39, 315. I. M. Kolthoff, L. Sl Guss, J. Am. Chem. Soc. 1940, 62, 249. G. Demange-Gu6rin, Talanta 1970, 17, 1099. E. Bosch, C. Rfifols, M. Ros6s, Talanta 1989, 36, 1227. M. Tez6, R. Schaal, Bull. Soc. Chim. Fr. 1962, 29, 1372. I. M. Kolthoff, M. K. Chantooni, Jr., J. Phys. Chem. 1972, 76, 2024.

Solvent on the Equilibria of Acid-Base Indicators [33] [34] [35] [36] [37] [38] [39] [40] [41] M. K. Chantooni, Jr., I. M. Kolthoff, J. Phys. Chem. 1974, 78, 839. B. Tr6mi|lon, J. F. Coetzee, Pure Appl. Chem. 1978, 50, 587. Y. Marcus, Pure Appl. Chem. 1986, 58, 1721. Y. Marcus, Pure Appl. Chem. 1983, 55, 977. M. K. Chantooni, Jr., I. M. Kolthoff, J. Phys. Chem. 1973, 77, 527. O. Popovych, Anal. Chem. 1974, 46, 2009. P. Ugo, S. Daniele, G. A. Mazzochin, Anal. Chim. Acta 1988, 208, 207. T. Mussini, A. K. Covington, P. Longhi, S. Rondinini, Pure Appl. Chem. 1985, 57, 865. T. Mussini, F. Mazza, Electrochim. Acta 1987, 32, 855.

337

Received August 21, 1990.