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On the Dissociation of Methyl Orange: Spectrophotometric Investigation in Aqueous Solutions from 10 to 90 ∘C and Theoretical Evidence for Intramolecular Dihydrogen Bonding

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Abstract

The dissociation of methyl orange was investigated by spectrophotometry in aqueous solutions from 10 to 90 ∘C and by quantum chemical calculations. Combined chemometric and thermodynamic analyses of the spectrophotometric data were used to simultaneously extract the thermodynamic stabilities and the spectrophotometric attributes of the dominant methyl orange species in solutions containing less than 20.00 mmol-kg−1 perchloric acid and submillimolal concentrations of methyl orange. The analyses revealed the presence of only one monomeric deprotonated and one monomeric protonated species. The spectra did not reveal any evidence for the presence of tautomeric equilibria between the protonated azo and ammonium species in the experimental range studied. Thermodynamic analyses of the temperature-dependent dissociation constants showed the reactions to be endothermic and enthalpy driven with increasing acidity and increasing temperature.

All molar absorption coefficients in the 275–375 nm range can be adequately reproduced in the 10–90 ∘C range with a set of Gauss–Lorentz parameters and used to predict the absorption spectra for any desired condition. The dominant features of the spectrophotometric attributes of the methyl orange species could also be retrieved in Time Dependent–Density Functional Theory (TD–DFT) calculations. Topological analyses of the electron density also revealed the formation of a dihydrogen bond between the azo proton and an adjacent phenyl ring hydridic hydrogen which increases the stability of the azo molecules relative to the ammonium molecule.

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References

  1. J. Fan, X. Shen, and J. Wang, Anal. Chim. Acta 364, 275 (1998).

    Article  CAS  Google Scholar 

  2. C. L. De Ligny, H. Loriaux, and R. Ruiter, Recl. Trav. Chim. 80, 725 (1961).

    CAS  Google Scholar 

  3. A. G. Gonzalez, M. A. Herrador, and A. G. Asuero, Anal. Chim. 246, 429 (1991).

    Google Scholar 

  4. K. M. Tawarah and H. M. Abu-Shamleh, Dyes Pigments 16, 241 (1991).

    Article  CAS  Google Scholar 

  5. D. Kara and M. Alkan, Spectrochim. Acta A 56, 2753 (2000).

    CAS  Google Scholar 

  6. R. L. Reeves, J. Am. Chem. Soc. 88, 2240 (1966).

    Article  CAS  Google Scholar 

  7. I. M. Klotz, H. A. Fiess, J. Y. Chen Ho, and M. Mellody, J. Am. Chem. Soc. 76, 5136 (1954).

    CAS  Google Scholar 

  8. E. Sawicki, J. Org. Chem. 22, 365 (1957).

    CAS  Google Scholar 

  9. E. Sawicki, J. Org. Chem. 21, 605 (1956).

    CAS  Google Scholar 

  10. S.-J. Yeh and H. H. JaffÉ, J. Am. Chem. Soc. 81, 3283 (1959).

    CAS  Google Scholar 

  11. G. M. Badger, R. G. Buttery, and G. E. Lewis, J. Chem. Soc. 1888 (1954).

  12. M. T. Rogers, T. W. Campbell, and R. W. Maatman, J. Am. Chem. Soc. 73, 5122 (1951).

    CAS  Google Scholar 

  13. A. M. Sanchez, M. Barra, and R. H. de Rossi, J. Org. Chem. 64, 1604 (1999).

    CAS  Google Scholar 

  14. A. R. Hantzsch and A. Burawoy, Chem. Ber. 63, 1760 (1930).

    Google Scholar 

  15. J. del Nero, R. E. de Araujo, A. S. L. Gomes, C. P. de Melo, and C. B. de AraÚjo, J. Chem. Phys. 122, 104506 (2005).

    Google Scholar 

  16. E. Sawicki, J. Org. Chem. 22, 1084 (1957).

    CAS  Google Scholar 

  17. P. D. Bolton, J. Ellis, K. A. Fleming, and I. R. Lantzke, Aust. J. Chem. 26, 1005 (1973).

    Article  CAS  Google Scholar 

  18. M. E. Casida, C. Jamorski, K. C. Casida, and D. R. Salahub, J. Chem. Phys. 108, 4439 (1998).

    Article  CAS  Google Scholar 

  19. R. E. Stratmann, G. E. Scuseria, and M. J. Frisch, J. Chem. Phys. 109, 8218 (1998).

    Article  CAS  Google Scholar 

  20. R. Bauernschmitt and R. Ahlrichs, Chem. Phys. Lett. 256, 454 (1996).

    Article  CAS  Google Scholar 

  21. R. F. W. Bader, Atoms In Molecules: A Quantum Theory (Clarendon, Oxford, 1990).

    Google Scholar 

  22. A. D. Becke and K. E. Edgecombe, J. Chem. Phys. 92, 5397 (1990).

    CAS  Google Scholar 

  23. B. Silvi and A. Savin, Nature 371, 683 (1994).

    Article  CAS  Google Scholar 

  24. A. D. Becke, J. Chem. Phys. 98, 5648 (1993).

    CAS  Google Scholar 

  25. C. T. Lee, W. T. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988).

    CAS  Google Scholar 

  26. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, R. J. Cheeseman, V. G. Zakrzewski, J. A. Montgomery Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, P. Salvador, J. J. Dannenberg, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. X. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, and J. A. Pople, Gaussian 98, Rev. A.11.1 (Gaussian Inc., Pittsburgh, 2001).

    Google Scholar 

  27. MORPHY98, Program Written by P. L. A. Popelier with a Contribution from R. G. A. Bone (UMIST, Manchester, England, 1998).

  28. S. Noury, X. Krokidis, F. Fuster, and B. Silvi, Comput. Chem. 23, 597 (1999).

    Article  CAS  Google Scholar 

  29. J.-F. Boily and T. M. Seward, Geochim. Cosmochim. Acta, 69, 3773 (2005).

    CAS  Google Scholar 

  30. J.-F. Boily and T. M. Seward, J. Solution Chem. in press (2005).

  31. F. Quadrifoglio and V. Crescenzi, J. Colloid. Surf. Sci. 35, 447 (1971).

    Article  CAS  Google Scholar 

  32. H. C. Helgeson, D. H. Kirkham, and G. C. Flowers, Am. J. Sci. 281, 1249 (1981).

    Article  CAS  Google Scholar 

  33. W. L. Marshall and E. U. Franck, J. Phys. Chem. Ref. Data 10, 295 (1981).

    Article  CAS  Google Scholar 

  34. G. H. Golub and C. Reinsch, Numer. Math. 14, 403 (1970).

    Article  Google Scholar 

  35. E. R. Malinowski, Anal. Chim. 49, 612 (1977).

    CAS  Google Scholar 

  36. S. J. Hug and B. Sulzberger, Langmuir 10, 3587 (1994).

    Article  CAS  Google Scholar 

  37. A. N. Tikhonov and V. Y. Arsenin, Solutions of Ill-Posed Problems (Halsted, Washington, DC, 1977), p. 258.

    Google Scholar 

  38. P. R. Bevington and K. Robinson, Data Reduction and Error Analysis for the Physical Sciences, 2nd edn. (McGraw-Hill, New York, 1992), 328 p.

    Google Scholar 

  39. D. W. Marquardt, SIAM J. 11, 431 (1963).

    Google Scholar 

  40. The Mathworks, Inc. U.S. Patent No. 6,857, 118

  41. A. Theil and O. Petter, Z. Anorg. Chem. 137, 169 (1928).

    Google Scholar 

  42. M. Meloun Iraq J. Sci. 22, 163 (1981).

    CAS  Google Scholar 

  43. G. H. Jeffery, J. Mendham, and R. C. Denney. Vogel's Textbook of Quantitative Chemical Analysis, 5th edn. (Wiley, New York, 1991), pp. 668–670.

    Google Scholar 

  44. D. R. Lide, CRC Handbook of Chemistry and Physics, 75th edn. (CRC, Boca Raton, FL, 1995), pp. 8.17–8.18.

    Google Scholar 

  45. J. A. Dean, Lange's Handbook of Chemistry, 14th edn. (McGraw-Hill, New York, 1992), pp. 8.115–8.16.

    Google Scholar 

  46. J. Muirhead-Gould and J.E. Stuehr, J. Phys. Chem. 79, 2461 (1975).

    Article  CAS  Google Scholar 

  47. E. L. Shock, Am. J. Sci. 295, 496 (1995).

    Article  CAS  Google Scholar 

  48. L. E. Strong, T. G. Copeland, M. Darragh, and C. van Waes, J. Solution Chem. 9, 109 (1980).

    Article  CAS  Google Scholar 

  49. L. E. Strong, T. Kinney, and P. Fischer, J. Solution Chem. 8, 329 (1979).

    Article  CAS  Google Scholar 

  50. L. E. Strong, D. J. Blubaugh, and C. R. Canalli, J. Solution Chem. 11, 811 (1981).

    Google Scholar 

  51. R. L. Reeves, R. S. Kaiser, M. S. Maggio, E. A. Sylvestre, and W. H. Lawton, Can. J. Chem. 51, 628 (1973)

    CAS  Google Scholar 

  52. S. Miertus, E. Scrocco, and J. Tomasi, Chem. Phys. 55, 117 (1981).

    Article  CAS  Google Scholar 

  53. C. A. Jaska, A. J. Lough, and I. Manners, Inorg. Chem. 43, 1090 (2004).

    Article  CAS  Google Scholar 

  54. T. Ramnial, H. Jong, I. D. McKenzie, M. Jennins, and J. A. C. Clyburne, Chem. Commun. 1722 (2003).

  55. S. H. Park, A. J. Lough, G. P. A. Yap, and R. H. Rorris, J. Organometallic Chem. 609, 110 (2000).

    Article  CAS  Google Scholar 

  56. A. J. Lough, S. Park, R. Ramachandran, and R. H. Morris, J. Am. Chem. Soc. 116, 8356 (1994).

    Article  CAS  Google Scholar 

  57. D. G. Gusev, A. J. Lough, and R. H. Morris, J. Am. Chem. Soc. 120, 13138 (1998).

    Article  CAS  Google Scholar 

  58. D. Wu, Z.-R. Li, X.-Y. Hao, A. F. F. Jalbout, L. Adamowicz, R.-J. Li, and C.-C. Sun, J. Chem. Phys. 120, 1330 (2004).

    CAS  Google Scholar 

  59. R. Custelcean and J. E. Jackson, Chem. Rev. 101, 1963 (2001).

    Article  CAS  Google Scholar 

  60. I. Alkorta, J. Elguero, O. MÓ, M. Yáñ, and J. E. Del Bene, J. Phys. Chem. A. 106, 9325 (2002).

    Article  CAS  Google Scholar 

  61. W. Wagner and A. Kruse, Properties of Water and Steam (Springer-Verlag, Berlin, 1998), 354 p.

    Google Scholar 

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Authors and Affiliations

  1. Pacific Northwest National Laboratory, Richland, P.O. Box 999, 99352, WA

    Jean-François Boily

  2. Institute for Mineralogy and Petrology, Swiss Federal Institute of Technology (ETH) Zurich, Sonneggstr. 5, Zurich, CH-8092, Switzerland

    Terry M. Seward

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  1. Jean-François Boily
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  2. Terry M. Seward
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Correspondence to Jean-François Boily.

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Boily, JF., Seward, T.M. On the Dissociation of Methyl Orange: Spectrophotometric Investigation in Aqueous Solutions from 10 to 90 ∘C and Theoretical Evidence for Intramolecular Dihydrogen Bonding. J Solution Chem 34, 1387–1406 (2005). https://doi.org/10.1007/s10953-005-8514-y

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  • DOI: https://doi.org/10.1007/s10953-005-8514-y

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