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2006 | 4 | 1 | 56-67
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Protonation acidity constants for benzotoluidides in sulfuric acid solutions

Treść / Zawartość
Warianty tytułu
Języki publikacji
EN
Abstrakty
EN
The protonation of o-, m-and p-benzotoluidide in sulfuric acid solutions is studied by UV spectroscopy in the 190–350 nm region. Principal component analysis is applied to estimate the contributions of the effect of protonation and the medium effect. For the substances studied in this work, the first principal component (PC) captures about 98 % of the variance and the second PC ∼100 % of the cumulative percentage variance in the 210–350 nm region. The same spectral region is used for calculation of the ionization ratio from the coefficients of the first PC and mole fractions of the base and its conjugate acid. Using these data and Hammett's equation (pK BH + = H X + log I), the pK BH + values for the protonation reaction are obtained. The dissociation constants as well as the solvent parameters m* (∼0.43) and ϕ (∼0.60) are calculated using the Excess Acidity Method (-pK BH += 2.28–2.30) and the Bunnett-Olsen Method (-pK BH += 2.24–2.28). The probable sites of protonation are discussed.
Wydawca

Czasopismo
Rocznik
Tom
4
Numer
1
Strony
56-67
Opis fizyczny
Daty
wydano
2006-03-01
online
2006-03-01
Twórcy
  • Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Sts. Cyril & Methodius University, 1001, Skopje, Republic of Macedonia, goranst@iunona.pmf.ukim.edu.mk
  • Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Sts. Cyril & Methodius University, 1001, Skopje, Republic of Macedonia, frosa@iunona.pmf.ukim.edu.mk
Bibliografia
  • [1] J.T. Edward and S.C. Wong: “Ionization of Carbonyl Compouns in Sulfuric Acid. Correction for Medium Effects by Characteristic Vector Analysis”, J. Am. Chem. Soc., Vol. 99, (1977), pp. 4229–4232. http://dx.doi.org/10.1021/ja00455a003[Crossref]
  • [2] R.A. Cox and K. Yates: “Medium effects in protonation equilibrium studies. Accurate acidity constants using the excess acidity method”, Can. J. Chem., Vol. 59, (1981), pp. 1560–1567. http://dx.doi.org/10.1139/v81-230[Crossref]
  • [3] R.A. Cox, L.M. Druet, A.E. Klausner, T.A. Modro, P. Wan and K. Yates: “Protonation acidity constants for some benzamides, acetamides, and lactams”, Can. J. Chem., Vol. 59, (1981), pp. 1568–1573. http://dx.doi.org/10.1139/v81-231[Crossref]
  • [4] G. Stojković and B. Andonovski: “UV Study of the Protonation of Benzamide and N-phenylbenzamide in Sulfuric Acid Media”, In: Proceedings, 3rd Aegan Analytical Chemistry Days, Polihnitos, Lesvos, Greece, University of Athens, Athens, (2002), pp. 498–501.
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  • [10] R.I. Zalewski: “Adaptation of Characteristic Vector Analysis and Titration Curve Analysis for calculations of p K BH + from Ultraviolet-Visible Spectral Data”, J. Chem. Soc. Perkin Trans. II, (1979), pp. 1637-1639. [Crossref]
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  • [17] I. Kuzmanovski: “Chemometrics and more”, In: Proceedings, XVIII Congress of Chemists and Technologists of Macedonia, Ohrid, Macedonia, The Society of Chemists and Technologists of Macedonia, Skopje, (2004), pp. 209.
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  • [21] R.A. Cox and K. Yates: “Excess acidities. A generalized method for the determination of basicities in aqueous acid mixtures”, J. Am. Chem. Soc., Vol. 100, (1978), pp. 3861–3867. http://dx.doi.org/10.1021/ja00480a033[Crossref]
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Typ dokumentu
Bibliografia
Identyfikatory
Identyfikator YADDA
bwmeta1.element.-psjd-doi-10_1007_s11532-005-0004-y
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