Abstract
In this review we describe some recent experimental development in the field of intermolecular proton transfer. It was observed, several decades ago, that upon excitation, aromatic amines and alcohols become more acidic in aqueous solutions. Excitation of aqueous solution of these compounds by picosecond laser pulses results in proton transfer from the excited compound to the solvent. The proton transfer rates of some of these compounds was determined by time resolved fluorescence techniques. The measured time constants vary from a few tenths of a picosecond to several tenths of a nanosecond. The proton transfer process creates an ion pair which reversibly recombines on a very short time scale. Picosecond time resolved fluorescence measurements were able to reveal this phenomenon. Detailed kinetic analysis showed that geminate recombination is very efficient and most of the ion pairs recombine within a few hundred picosecond. The geminate recombination process is time dependent and is governed by diffusion and Coulombic attraction. Finally we describe a method for light induced proton concentration jump. Intense short laser pulses can generate enough protons as to cause an observable reduction in the bulk ph. a relaxation kinetics analysis is carried out in order to follow the time evolution of the proton concentration.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Bell, R.P. 1973. “The Proton in Chemistry”, 2nd edn., Chapman and Hall, London, 310 pp.
Caldin, E.F. and Gold, V. 1975. “Proton-transfer Reactions”, Chapman and Hall, London, 448 pp.
Schulman, E.F. 1977. “Fluorescence and Phosphorescence Spectroscopy”, Pergamon Press, New York.
Ireland, J.F. and Wyatt, P.A.H. 1976. Adv. Phys. Org. Chem. 12: 131 – 221.
Gutman, M. 1984. Methods of Biochemical Analysis 30: 1 – 103.
Grunwald, E., Ralph, E.K. 1971. Acct. Chem. Res, 4: 107.
Eigen, M. 1964. Angew. Chem. Int. Ed. Eng. 3:1.
Weller, A. 1961. Prog. Reaction Kinetics 1: 189.
Forster, T. 1949. Naturwissenschaften 36: 186.
Forster, T. 1950. Z. Elektrochem. 54: 42.
Campillo, A. J., Clark, J.H., Shapiro, S.L., Winn, K.R. 1978. In Proceedings of the First International Conference on Picosecond Phenomena, eds. Shank, C.V., Ippen, E.P. and Shapiro, S.L. Berlin: Springer-Verlag, Berlin.
Smith, K.K., Huppert, D., Gutman, M., Kaufmann, K.J. 1979. Chem. Phys. Lett. 64: 522 – 27.
Weller, A. 1958. Z. Physik. Chem. N.F. 15: 438.
Weller, A. 1952. Z. Elektrochem. 256: 662.
Demjaschkewitch, A.B., Zaitsev, -N.K., Kuzmin, M.G. 1978. Chem. Phys. Lett. 55: 80.
Gafni, A., Modlin, R.L., Brand, L. 1976. 80: 898.
Huppert, D., Jayaraman, A., Maines, R.G., Steyert, D.W., Rentzepis, P.M. 1984. J. Chem. Phys. 81: 5596 – 5600.
Haar, H.P., Klein, U.K.A. and Hauser, M. 1978. Chem. Phys. Lett. 58: 525.
Gutman, M. and Huppert, D. 1979. J. Biochem. Biophys. Methods 1: 9.
Weller, A. 1958. Z. Physics Chem. 17: 14.
Onsager L. 1934. J. Chem. Phys. 2: 599.
Hong, K.M. and Noolandi, J. 1978. J. Chem, Phys. 68: 5162.
Pines, E. and Huppert, D. 1983. J. Phys. Chem. 87: 4471 – 78.
Gutman, M., Nachliel, E., Gershon, E., Giniger, R., and Pines, E. 1983. J. Am. Chem. Soc. 105: 2210 – 2216.
Gutman, M..and Huppert, D. 1981. J. Am. Chem. Soc. 103: 3709 – 13.
Pines, E., Huppert, D. 1985. Chem. Phys. Lett. 116: 295.
Gutman, M., Huppert, D., Pines, E., Nachliel, E. 1981. Biochimica et Biophysica Acta 642: 15 – 26.
Politi, M.J., Fendler, J.H. 1984. J. Am. Chem. Soc. 106: 265.
Bardez, E., Goguillon, B.T., Keh, E., Valeav, B. 1984. 88: 1909.
Gutman, M., Nachliel, E., Gershon, E., Giniger, R. 1983. Eur. J. Biochem. 134: 63 – 69.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1986 D. Reidel Publishing Company
About this chapter
Cite this chapter
Huppert, D., Pines, E. (1986). Intermolecular Proton Transfer. In: Rentzepis, P.M., Capellos, C. (eds) Advances in Chemical Reaction Dynamics. NATO ASI Series, vol 184. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4734-4_11
Download citation
DOI: https://doi.org/10.1007/978-94-009-4734-4_11
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-8604-2
Online ISBN: 978-94-009-4734-4
eBook Packages: Springer Book Archive