View PDF Version
 
DOI: 10.1039/A802521E (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 1973-1982

Thermodynamic nitration rates of aromatic compounds. Part 4. Temperature dependence in sulfuric acid of HNO3→NO2+ equilibrium, nitration rates and acidic properties of the solvent[hair space]†

(Note: The full text of this document is currently only available in the PDF Version )

Nunziata C. Marziano, Alberto Tomasin, Claudio Tortato and Jose’ M. Zaldivar

Abstract

The protonation–dehydration equilibrium of nitric acid (HNO3 + H+ ⇌ H2O + NO2+) has been studied in the range 80–94 wt% H2SO4 as a function of temperature and the variations of [NO2+]/[HNO3] ratios have been analysed to evaluate the dissociation constants (pKNO2+) and the enthalpy of dissociation of the process.

The nitration rates of some aromatic compounds, related both to the stoichiometric concentration of nitric acid (rate = k2obs[Ar][HNO3]) and to the effective concentration of electrophilic species (rate = k2°[Ar][NO2+]), have been investigated in the range 50–100 wt% H2SO4 and the dependence upon acidity and temperature of the different rate profiles is discussed.

Activation energies determined by k2obs and k2° nitration rates are reported. The k2° values are found to be independent of medium acidity and allow one to obtain consistent activation energies as expected for activated and deactivated aromatic substrates as well as for an encounter limited reaction.

Equilibria and rates in sulfuric acid have been analysed using the Mc activity coefficient functions whose values have been estimated over a range of temperature between 25 °C and 90 °C. The general trend observed in the acidic properties of the medium is reported. It is shown that the temperature has a small influence on the Mc function.

References

  1. P. B. D. De La Mare and J. H. Ridd, Aromatic Substitution, Nitration and Halogenation, Butterworths, London, 1959 Search PubMed.
  2. C. K. Ingold, Structure and Mechanism in Organic Chemistry, Cornell University Press, Ithaca, NY, 2nd edn., 1969 Search PubMed.
  3. G. Olah, Acc. Chem. Res., 1971, 4, 240 CrossRef CAS.
  4. J. H. Ridd, Acc. Chem. Res., 1971, 4, 248 CrossRef CAS.
  5. J. H. Ridd, Adv. Phys. Org. Chem., 1978, 16, 1 CAS.
  6. K. Schofield, Aromatic Nitration, Cambridge University Press, Cambridge, 1980 Search PubMed.
  7. G. A. Olah, R. Malhotra and S. C. Narang, Nitration. Methods and Mechanisms, VCH Publishers, NY, 1989 Search PubMed.
  8. H. Feuer and A. T. Nielsen, Nitro Compounds, Recent Advances in Synthesis and Chemistry, VCH Publishers, NY, 1990 Search PubMed.
  9. C. L. Coon, W. G. Blucher and M. E. Hill, J. Org. Chem., 1973, 38, 4243 CrossRef CAS.
  10. N. C. Marziano, C. Tortato and M. Sampoli, J. Chem. Soc., Perkin Trans. 2, 1991, 423 RSC.
  11. N. C. Marziano, P. Traverso, A. De Santis and M. Sampoli, J. Chem. Soc., Chem. Commun., 1978, 873 RSC.
  12. M. Sampoli, A. De Santis, N. C. Marziano, F. Pinna and A. Zingales, J. Phys. Chem., 1985, 89, 2864 CrossRef.
  13. D. S. Ross, K. F. Kulmann and R. J. Malhotra, J. Am. Chem. Soc., 1983, 105, 4299 CrossRef CAS.
  14. N. C. Marziano, A. Tomasin and M. Sampoli, J. Chem. Soc., Perkin Trans. 2, 1991, 1995 RSC.
  15. (a) N. C. Marziano, G. Cimino and R. Passerini, J. Chem. Soc., Perkin Trans. 2, 1973, 1915 RSC; (b) N. C. Marziano, P. Traverso, A. Tomasin and R. Passerini, J. Chem. Soc., Perkin Trans. 2, 1977, 309 RSC; (c) N. C. Marziano, A. Tomasin and P. Traverso, J. Chem. Soc., Perkin Trans. 2, 1981, 1070 RSC.
  16. (a) N. C. Marziano, A. Tomasin and C. Tortato, Org. React. (Tartu), 1996, 30, 29 Search PubMed; (b) N. C. Marziano, A. Tomasin and C. Tortato, Org. React. (Tartu), 1996, 30, 39 Search PubMed.
  17. N. C. Marziano, A. Tomasin, C. Tortato and P. Isandelli, unpublished results.
  18. J. M. Zaldivar, E. Molga, M. A. Alòs, H. Hernàndez and K. R. Westerterp, Chem. Eng. Process., 1996, 35, 91 CrossRef CAS.
  19. C. D. Johnson, A. R. Katrizky and S. A. Shapiro, J. Am. Chem. Soc., 1969, 91, 6654 CrossRef CAS.
  20. P. Tickle, A. G. Briggs and J. M. Wilson, J. Chem. Soc. (B), 1970, 65 RSC.
  21. S. A. Attiga and C. H. Rochester, J. Chem. Soc., Perkin Trans. 2, 1974, 1624 RSC.
  22. M. J. Cook, N. L. Dassanayake, C. D. Johnson, A. R. Katrizky and T. W. Toone, J. Am. Chem. Soc., 1975, 97, 760 CrossRef CAS.
  23. F. Young, L. F. Maranville and H. M. Smith, Structure of Electrolytic Solutions, ed. W. J. Hamer, Wiley, NY, 1959 Search PubMed.
  24. (a) N. G. Zarakhani, Russ. J. Phys. Chem., 1978, 52, 1129 Search PubMed; (b) N. G. Zarakhani, V. S. Markin and G. E. Zaikov, Russ. J. Phys. Chem., 1979, 53, 1304, 1306 Search PubMed.
  25. N. C. Marziano, unpublished work.
  26. N. C. Deno and R. Stein, J. Am. Chem. Soc., 1956, 78, 578 CrossRef CAS.
  27. R. G. Coombes, R. B. Moodie and K. Schofield, J. Chem. Soc. (B), 1968, 800 RSC.
  28. N. C. Marziano, A. Zingales and V. Ferlito, J. Org. Chem., 1977, 42, 2511 CrossRef CAS.
  29. M. I. Vinnik, Zh. Grabovskaya and L. N. Arzameskova, Russ. J. Phys. Chem., 1967, 41, 580 Search PubMed.
  30. N. C. Marziano, A. Tomasin and C. Tortato, J. Chem. Soc., Perkin Trans. 2, 1991, 1575 RSC.
  31. R. G. Coombes, D. H. Crout, J. G. Hoggett, R. B. Moodie and K. Schofield, J. Chem. Soc., Perkin Trans. 2, 1970, 347 RSC.
  32. T. G. Bonner, F. Bowyer and G. Williams, J. Chem. Soc., 1952, 3274 RSC.
  33. R. J. Gillespie and D. G. Norton, J. Chem. Soc., 1953, 971 RSC.
  34. R. G. Coombes, personal communication.
  35. (a) P. R. Cox and A. N. Strachan, Chem. Eng. Sci., 1972, 27, 457 CrossRef CAS; (b) G. F. Sheat and A. N. Strachan, Can. J. Chem., 1978, 56, 1280.
  36. (a) P. R. Cox and A. N. Strachan, Chem. Eng. Sci., 1971, 26, 1013 CrossRef CAS; (b) J. W. Chapman and A. N. Strachan, in Industrial and Laboratory Nitrations, eds. L. F. Albright and C. Hanson, ACS Symposium Series no. 22, Washington DC, 1976, 219 Search PubMed.
  37. S. R. Hartshorn, R. B. Moodie and K. Stead, J. Chem. Soc., Perkin Trans. 2, 1972, 127 RSC.
  38. L. P. Hammett, Physical Organic Chemistry, McGraw Hill, Kogakusha, Tokyo, 1970 Search PubMed.
  39. C. H. Rochester, Acidity Functions, Academic Press, London, 1970 Search PubMed.
  40. M. Liler, Reaction Mechanisms in Sulphuric Acid, Academic Press, London, 1971 Search PubMed.
  41. R. Stewart, The Proton in Chemistry, Academic Press, London, 1985 Search PubMed.
  42. G. A. Olah, G. K. Surya Prakash and J. Sommer, Superacids, Wiley, NY, 1985 Search PubMed.
  43. (a) F. Young, L. F. Maranville and H. M. Smith, Structure of Electrolytic Solutions, ed. W. J. Hamer, Wiley, NY, 1959 Search PubMed; (b) E. B. Robertson and H. B. Dunford, J. Am. Chem. Soc., 1964, 86, 5080 CrossRef CAS; (c) H. Chen and D. E. Irish, J. Phys. Chem., 1971, 75, 2672 CrossRef; (d) N. G. Zarakahani, N. B. Librovich and M. I. Vinnik, Zh. Fiz. Khim., 1971, 45, 1733 Search PubMed; (e) V. D. Maiorov and N. B. Librovich, Zh. Fiz. Khim., 1973, 47, 2298 Search PubMed; (f) N. B. Librovich and V. D. Maiorov, Izv. Akad. Nauk SSSR, Ser. Khim., 1977, 684 Search PubMed.
  44. J. Balej, F. Hanousek, M. Pisarcik and K. Sarka, J. Chem. Soc., Faraday Trans., 1984, 80, 521 RSC.
  45. N. C. Deno, J. J. Jaruzelski and A. Schriesheim, J. Am. Chem. Soc., 1955, 86, 3044 CrossRef.
  46. N. C. Marziano, C. Tortato, A. A. Sheikh-Osman, J. M. Riego and J. M. Zaldivar, Org. React. (Tartu), 1997, 31, 87 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.