Abstract
The rates of proton dissociation from the first excited state of aromatic alcohols (8-hydroxypyrene-1,3,6-trisulfonate and β-naphthol-6-sulfonate) were measured by steady-state fluorimetry in aqueous solutions as a function of urea concentration. The measured acid dissociation rate constants (k /* off ) of the probes were independent of urea concentration up to 3M. These results, together with the decrease of k /* off with salt and other additives, demonstrate that the changes in k /* off are not related unequivocally with the activity of water. A urea-H2O cluster of properties similar to pure water is proposed to account for the observed results.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
R. P. Bell inThe Proton in Chemistry 2nd ed., (Methuen, New York, 1973).
J. F. Ireland and P. A. H. Wyatt,Advances in Phys. Org. Chem.,12, 131 (1976); E. M. Kosower and D. Huppert,Ann. Rev. Phys. Chem. 37, 127 (1986).
G. W. Robinson, P. J. Thistlethwaite, and J. Lee,J. Phys. Chem. 90, 4224 (1986).
D. Huppert, E. Kolodney, M. Gutman, and E. Nachliel,J. Am. Chem. Soc. 104, 6949 (1982); S. G. Schulman, R. N. Kelley, and N. J Gonzales,Pure and Appl. Chem. 59, 655 (1987).
M. J. Politi and H. Chaimovich,J. Phys. Chem. 90, 282 (1986).
E. Bardez, B. T. Goughillon, E. Keh, and B. Valeur,J. Phys. Chem. 88, 1909 (1984).
O. Schales and S. S. Schales,J. Biol. Chem. 140, 879 (1941).
V. E. Bower and R. A. Robinson,J. Phys. Chem. 67, 1524 (1963).
R. A. Robinson and R. H. Stokes, inElectrolyte Solutions (Butterworths, London, 1959); H. S. Harned and B. B. Owen in,The Physical Chemistry of Electrolytic Solutions, 3rd ed., (Reinhold, New York, 1958).
Lange's Handbook of Chemistry, 12th edn., J. A. Dean, ed., (McGraw-Hill, New York, 1979).
H. S. Frank and F. Franks,J. Phys. Chem. 48, 4746 (1968); D. Eisenberg and W. Kauzmann, inThe Structure and Properties of Water (Oxford, London, 1969).
R. H. Stokes,Australian J. Chem. 20, 2087 (1967).
R. B. Cassel and N.-Y. Wen,J. Phys. Chem. 76, 1369 (1972).
T. S. Sarma and J. C. Ahluwalia,J. Phys. Chem. 76, 1366 (1972).
S. Subramanian, T. S. Sarma, D. Balasubramanian, and J. C. Ahluwalia,J. Phys. Chem. 75, 815 (1971).
J. H. Stern and P. M. Hubler,J. Phys. Chem. 88, 1680 (1984).
M. Bloemendal and G. Somsen,J. Am. Chem. 107, 3426 (1985).
H. Tanaka, K. Nakanishi, and H. Touhara,J. Chem. Phys. 82, 5184 (1985).
H. R. Bull and K. Breese,Arch. Biochem. Biophys. 139, 93 (1970).
K. Ueberreiter,Colloid and Polymer Sci. 260, 37 (1982) and references therein.
D. H. Huppert, A. Jagaraman, R. G. Maines Sr., D. W. Steyert, and P. M. Rentzepis,J. Chem. Phys. 81, 5596 (1984).
R. A. Horne and D. S. Johnson,J. Phys. Chem. 70, 2182 (1966).
R. A. Horne and R. A. Courant,J. Phys. Chem. 68, 1258 (1964).
K. K. Kundu and A. K. Das,J. Col. Chem. 8, 259 (1979).
M. Eigen, N. Kruse, G. Maass, and L. de Maeyer,Progress Reaction Kinetics 2, 285 (1962).
B. E. Conway, inModern Aspects of Electrochemistry, Vol. 13, J. O. M. Bockris and B. E. Conway eds., (Butterworths, London, 1962), Chap. 2.
B. E. Conway and D. F. Tessier,Int. J. Chem. Kinetics 13, 925 (1981).
T. Kishi, J. Tanaka, and T. Kouyama,Chem. Phys. Lett. 41, 497 (1976).
J. Lee, R. D. Griffin, and G. W. Robinson,J. Chem. Phys. 82, 4920 (1985).
S. Scheiner, R. Redfern, and M. M. Szczesniak,J. Phys. Chem. 89, 262 (1985); E. A. Hillenbrand and S. Scheiner,J. Am. Chem. Soc. 107, 7690 (1985); S. Scheiner,Acc. Chem. Res. 18, 174 (1985).
D. Huppert and E. Kolodney,Chem. Phys. 63, 401 (1981).
R. A. Moore, J. Lee, and G. W. Robinson,J. Phys. Chem. 89, 3648 (1985); J. Lee and G. N. Robinson,J. Chem. Phys. 81, 1203 (1984).
Th. Forster and S. Volker,Chem. Phys. Lett. 34, (1975).
M. Hauser, H.-P. Haar, and U. K. A. Klein,Ber. Bursenges. Physik. Chem. 81, 27 (1977).
H.-P. Haar, U. K. A. Klein, and M. Hauser,Chem. Phys. Lett. 58, 525 (1978).
R. Contreras and J. S. Gomez-Jeria,J. Phys. Chem. 88, 1905 (1984).
A. J. G. Strandjord, D. E. Smith, and P. F. Barbara,J. Phys. Chem. 89, 2355 (1985); A. J. G. Strandjord and P. F. Barbara,J. Phys. Chem. 89, 2362 (1985).
M. C. R. Symons,J. Chem. Res. 140 (1978).
H. J. E. Dobson,J. Chem. Soc. 127, 2866 (1925).
T. C. Chan and W. A. Van Hook,J. Solution Chem. 5, 107 (1976).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Politi, M.J., Chaimovich, H. Proton transfer in aqueous urea solutions. J Solution Chem 18, 1055–1067 (1989). https://doi.org/10.1007/BF00647263
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00647263