947
Strongly Basic Systems. VII. The H,- Acidity Scale Keith Bowden, Alan Buckley, and Ross Stewart Contribution from the Department of Chemistry, University of British Columbia, Vancouver 8 , British Columbia, Canada. Received September 3, 1965 Abstract: An H2- scale has been established for four systems containing quaternary ammonium hydroxidewater, pyridine-water, sulfolane-water, and dimethyl sulfoxide-water. H2-= - log a H $Az-/fHA- and is a measure of the ability of a solvent to ionize an anionic acid. The 19 acids used to establish the scale were diphenylaminecarboxylic or -sulfonic acids or aminobenzoic acids containing nitro and other substituents. The acids (pK = 9.73) to 2-nitrodiphenylamine-2’-carboxylate varied in strength from 2,4,6-trinitrodiphenylamine-4’-sulfonate (pK = 20.64). The most basic system studied was 96.9 mole dimethyl sulfoxide containing 0.011 M(CH&N+OH-; it has an H2- value of 21.9. The Hz- scale appears to rise slightly less rapidly than the previously evaluated H- scale and this may be caused by the different solvation requirements of mono- and dianions. The carboxylate group, C 0 2 - ,is found to be acid strengthening when meta or para but strongly acid weakening when ortho.
P
revious papers in this series have described the establishment of a self-consistent H- scale for a number of solvent systems, based on the ionization of substituted anilines and diphenylamines. The acidity function, H-, describes the ability of a system to remove a proton from a neutral acid and is defined as follows.2 HA,H++A-
In a similar way the function Hz- describes the proton. removing properties of the system for anionic acids. HA-
H+ + A*-
Both H- and Hz- become identical with pH in the aqueous region. In strongly acid solution the functions Ho(for cationic acids) and H- (for neutral acids) are known to diverge,3r4 but the kinds of molecules used to establish the two scales are quite different and it is difficult to determine the extent to which the difference in charge type of the acids is responsib1e.j We have examined the effect of indicator charge type by constructing an Hz- scale using the systems aqueous pyridine, aqueous sulfolane, and aqueous dimethyl sulfoxide (DMSO), all containing 0.01 1 M (CH,),N+OH-, and the system water containing varying amounts of benzyltrimethylammonium hydroxide, using the simple Hammett stepwise technique. This was done by the simple expedient of adding carboxylate groups to the aniline and diphenylamine indicators thereby ensuring that in the strongly basic solutions used the ionizing acids are anionic (for example, see the following equation). (1) R. Stewart and J. P. O’Donnell, J. Am. Chem. SOC.,84, 493 (1962); Can. J. Chem., 42, 1681 (1964). (2) L. P. Hammett, “Physical Organic Chemistry,” McGraw-Hill Book Co., Inc., New York, N. Y., 1940, p 269; M. A. Paul and F. A. Long, Chem. Rev., 57, 1 (1957). (3) R. H. Boyd, J. Am. Chem. SOC.,83, 4288 (1961); J . Phys. Chem., 67, 737 (1963). (4) J. N . Phillips, Australian J. Chem., 14, 183 (1961). (5) Ho and H+ seem to be very close: see M. Isaks and H. H. Jaffe, J . Am. Chem. SOC.,86, 2209 (1964); M. W. Fuller and W. M. Schubert, ibid., 85, 108 (1963); J. C. D. Brand, W. C. Homing, and M. B. Thornley, J. Chem. SOC.,1374 (1952).
NHz
NH-
NO2
NO2
Results and Discussion All the amines used to construct the scale appeared to ionize by simple proton loss. Preliminary studies with aminophenolates, on the other hand, showed complicated spectral changes in solutions of low basicity, possibly because of zwitterion formation. The pK, values of the six indicators of strongest acidity were found directly using glycine buffers. The key indicators used in anchoring the system in the aqueous region and in bridging the pH and the Hzregions are 2,4,6-trinitro-4’-chlorodiphenylamine-2’carboxylic acid, 2,4,6-trinitrodiphenylamine-2’-carboxylic acid, and 4-chloro-2’,6’-dinitrodiphenylamine-4’carboxylic acid (indicators 4, 5 , and 6 ; Table I). The remaining indicator pK, values then are obtained by stepwise comparison. The mean pK, values then were used to set up the Ifz- acidity scale for the four systems studied. An interesting finding is the acid-strengthening effect of the meta andpara carboxylate substituents. Data on the ionization of di- and tricarboxylic acids suggest, after the appropriate statistical corrections are applied, that the carboxylate substituent has very little effect on the strength of a meta or para carboxyl group. Thus terephthalic acid has a pK2 of 4.34 at 20”with /.i= 0.1, whereas the pK of benzoic acid is 3.99 under the same conditiom4 The true pK2 of terephthalic acid is 0.3 unit (log 2 ) lower, however, because of the two sites for protonation of the dianion and the one site of proton loss in the monoanion. There is good evidence, however, for the carboxylate substituent exerting a definite acid-strengthening effect on the ionization of phenols. Thus the pK values of phenol, m-hydroxybenzoate ion, and p-hydroxybenzoate ion, are reported as 9.80, 9.61, and 8.99, respectively.6 Other determinations give similar result^.^!^ (6) A. V. Willi and J. F. Stocker, Helv. Chim. Acfa, 38, 1279 (1955); see also ref 7, p 364. (7) G. Kortum, M. Vogel, and I225":B. Linke, J. Prukt. Chem., 91,202 (1915)); 8,249-250' (245":H. Lindemann and W. Wessel, Ber.,58, 1221 (1925)); 9, 267-269"(>225":B. Linke, J. Prakt. Chem., 91, 202 (1915)); 10,194-195"(see footnote h); 11, 216-217' (214":T. Zincke, J. Prakt. Chem., 82, 17 (1910)); 12,272-273' (259-271': J. C.Clayton, G. F. Green, and B. A. Hems, J. Chem. Soc., 2467 (1951)); 13,268-269"(264":see ref 15); 14,282-283"(272-274': V. C. Barry, M. L. Conalty, and D. Twomey, Proc. Roy. Irish Acad., 55B 157 (1953); see Chem. Abstr., 48,1378 (1954)); 15,271-272' (268":M. G. C. Van Dorp, Rec. Trav. Chim. 23,301(1904)); 16,285-286"(285": see ref 18); 17,214-215"(211 see ref 17); 18,277-278'(278": M. T. Bogert and G. Scatchard,J. Am. Chem. Soc., 41,2502 (1919)); 19, 218-219' (219":F. Ullmann and W. Bader, Ann., 355,323 (1907)). Solvent is aqueous buffer of sufficient basicity to ionize the carboxyl group completely. c Solvent is 0.1 M sodium hydroxide solution. d Solvent is 0.011 M tetramethylammonium hydroxide in dimethyl O :
sulfoxide-water of just sufficient basicity to ionize the dianion completely. e Compound previously reported" but no physical constants given. Anal. Calcd for CI2H8N4OaS:C,37.51; H, 2.10. Found: C, 36.98; H, 2.22. f Compound not previously reported. Anal. Calcd for Cl3H7C1N4Os:C, 40.80;H, 1.84;C1, 9.27;N, 14.64. Found: C, 41.00; H, 1.96;C1, 9.20;N, 14.54. Compound not C,B46.24; : H, 2.39; N, 12.44. Found: Cy46.22;H, 2.44;N,12.18. Compound previously reported. Anal. Calcd for C I ~ H ~ C I N ~ O not previously reported. Anal. Calcd for C1aHsClN30e: C, 46.24;H, 2.39;N,12.44. Found: C,46.53;H, 2.57;N, 12.32. Table 111. H2- Values for Aqueous Benzyltrimethylammonium Hydroxide
Table 11. H2- Values for Aqueous Solutions of Dimethyl Sulfoxide (DMSO), Pyridine, and Sulfolane, all 0.011 M in Tetramethylammonium Hydroxide ~~~~~
~
Hydroxyl ion, M
~~~~
Mole
z nonaq component
1 .o 5.0 9.9 14.9 19.8 24.7 29.6 34.5 39.3 44.1 48.8 53.7 58.6 63.5 68.3 73.2 78.0 82.8 87.5 90.9 92.3 94.6 96.9
H2-
7
DMSO
12.04 12.32 12.70 13.24 13.85 14.34 14.84 15.39 15.77 16.18 16.59 16.96 17.32 17.70 18.18 18.48
-
Pyridine
12.03 12.29 12.47 12.77 13.15 13.76 14 04 14.34 14.65 15.69 U
Mole sulfolane
HZ-
1 .o 9.9 14.8 19.7 29.4 39.0 48.3 57.8 62.6 67.2 71.9 76.5 81.3 85.9 90.6 95.1
11.95 12.25 12.42 12.63 13.05 13.55 14.06 14.66 14.99 15.48 15.77 16.12 16.56 17.12 17.74 18.56
18.88
19.30 19.84 20.27 20.71 21.31 21.92
Further measurements in this system could not be made because of immiscibility of the base solution.
0.0114 0.0536 0.111 0.196 0.402 0.770 1.065 1.45 2.18 2.48
H2-
12.00 12.35 12.74 13.22 13.79 14.21 14.77 15.09 15.48 16.30
relevant details of the indicators are given in Table I, together with the analytical results for the previously unreported compounds. Acidity Measurements. The pK and H2-values were measured as has been previously reported.' A Bausch and Lomb Spectronic 502 spectrophotometer was used. The solvent dependence of the spectra over the ionization range was small and often the measurements could be made at a wavelength where the monoanion did not absorb. The ionizations of the indicators were all completely and instantaneously reversible. Only 3,5-dinitro-2-aminobenzoicacid at 450 mw) in slowly formed a new, nonreversible species (A, sulfolane-water-base and no measurements were made with this indicator in that solvent system. Overlap between each pair of adjacent indicators used to construct the scale was checked as previously described' and was found to be very satisfactory.
Acknowledgment. The financial support of the National Research Council of Canada is gratefully acknowledged,
Bowden, Buckley, Stewart
1 The Hz-Acidity Scale
