Skip to main content
SpringerLink
Log in

Photoelimination Reactions of Macromolecules

  • Conference paper
Photochemistry of Macromolecules

Abstract

At the present time, our understanding of macromolecular photochemistry is guided by the recognition that the overall photolysis reaction is attributed to a combination of mechanisms each of which would have to be studied independently for a proper understanding of the photoelimination process. Isolation of each mechanism is often experimentally difficult to achieve, and the need often arises for an analytical method which can predict and explain the behavior of complex photochemical systems. Our initial1 analytical description of the course of photoelimination reactions was concerned primarily with the rates of production and annihilation of electronically excited intermediates, rather than with the energy content and electronic configuration of the separate states. The basis for the earlier kinetic description was that the quantum yield of product formation, ØPC,2 is given by the summation equation,

$$ {{\text{ }\!\!\O\!\!\text{ }}_{\text{PC}}}\text{+}{{\text{ }\!\!\O\!\!\text{ }}_{\text{T}}}\text{+}{{\text{ }\!\!\O\!\!\text{ }}_{\text{I}}}\text{+}{{\text{ }\!\!\O\!\!\text{ }}_{\text{L}}}\text{+}{{\text{ }\!\!\O\!\!\text{ }}_{\text{REV}}}=1 $$

where ØT is the triplet yield, ØI is the singlet and triplet radia-tionless relaxation yield, ØL is the total luminescence yield, and ØREV represents relaxation via reversible processes yielding no net photochemical reaction. The magnitude of each of these competing processes and the yield for product formation could be readily estimated by the kinetic analysis.1

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 39.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 54.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. R. F. Reinisch and H. R. Gloria, A.C.S. Polymer Preprints, 9, 349 (1968).

    Google Scholar 

  2. J. G. Calvert and J. N. Pitts, Jr., “Photochemistry,” John Wiley & Sons, New York, N. Y., 1966,Chaps. 4, 6 and appendix.

    Google Scholar 

  3. R. M. Noyes, in “Progress in Reaction Kinetics,” G. Porter, ed., Vol. 1, Pergamon Press, N. Y. 1961, p. 129.

    Google Scholar 

  4. J. N. Murrell, “Theory of Electronic Spectra of Organic Molecules,” Methuen, London, 1965.

    Google Scholar 

  5. S. Glasstone, “Textbook of Physical Chemistry,” D. Van Nostrand Co., Inc., New York, N. Y., 1946, p. 204.

    Google Scholar 

  6. Private communication from E. M. Evleth.

    Google Scholar 

  7. A. Habersbergerova, “Ultraviolet and Visible Spectra of Electrons, Unstable Radicals and Ions.” English Translation in U.S.A.E.C. Facsimile Report No. UJV-1625.

    Google Scholar 

  8. M. Anbar and E. J. Hart, J. Phys. Chem. 69, 1244 (1965).

    Article  CAS  Google Scholar 

  9. F. H. Winslow, W. Matreyek, A. M. Trozzolo and R. H. Hansen, ACS Polymer Preprints 9, 377 (1968).

    CAS  Google Scholar 

  10. N. Grassie and N. A. Weir, J. Appl. Poly. Sci. 9, 975 (1965).

    Article  CAS  Google Scholar 

  11. W. C. Geddes, Rubber Chem. Technol. 40, 178 (1967), see also ref. 22.

    Google Scholar 

  12. R. F. Boyer, J. Phys. Colloid Chem. 51, 80 (1947).

    Article  CAS  Google Scholar 

  13. R. F. Reinisch, H. R. Gloria, and D. E. Wilson, ACS Polymer Preprints 7, 372, (1966).

    CAS  Google Scholar 

  14. R. F. Reinisch and H. R. Gloria, J. Solar Energy 12, 75 (1968).

    Article  Google Scholar 

  15. G. Herzberg, “Electronic Spectra of Polyatomic Molecules,” D. Van Nostrand Co., Inc., Princeton, N. J., 1967, p. 541.

    Google Scholar 

  16. D. F. Evans, J. Chem. Soc. (1960), 1735.

    Google Scholar 

  17. D. M. Golden, N. A. Gac, and S. W. Benson, Abstracts, 157th National Meeting, Amer. Chem. Soc. April, 1969.

    Google Scholar 

  18. K. W. Egger and S. W. Benson, J. Am. Chem. Soc. 88, 241 (1965).

    Article  Google Scholar 

  19. C. L. Currie and D. A. Ramsay, J. Chem. Phys. 45, 488 (1966).

    Article  CAS  Google Scholar 

  20. E. J. Burrel, Jr. and P. K. Battacharyya, J. Chem. Phys. 71, 774 (1967).

    Article  Google Scholar 

  21. D. M. Bodily and M. Dole, J. Chem. Phys. 45, 1428 (1966).

    Article  CAS  Google Scholar 

  22. A. F. Trottman-Dickenson in: Advances in Free Radical Chemistry, Vol. I, G. H. Williams, Ed., ( Logos ), London, 1965, p. 11.

    Google Scholar 

  23. R. F. Reinisch, H. R. Gloria, and G. M. Androes, to be published.

    Google Scholar 

  24. M. W. Hanna, et al. J. Chem. Phys. 37, 361 (1962).

    Article  CAS  Google Scholar 

  25. C. L. Gardner, J. Chem. Phys. 46, 2991, (1967).

    Article  CAS  Google Scholar 

  26. F. Sondheimer, et al. J. Am. Chem. Soc. 83, 1675 (1961).

    Article  CAS  Google Scholar 

  27. M. L. Poutsma, J. Org. Chem. 31, 4167 (1966).

    Article  CAS  Google Scholar 

  28. W. I. Bengough and I. K. Varma, Europ. Poly. J. 2, 49 (1966).

    Article  CAS  Google Scholar 

  29. D. E. Wilson and F. M. Hamaker, in “Thermal Analysis,” Vol. I, R. F. Schwenker and P. Garn, Eds., Academic Press, Inc., New York, N. Y., 1969.

    Google Scholar 

  30. S. Ohnishi, Y. Nakajima, and I. Nitta, J. Appt. Polymer Sci. 6, 629 (1962).

    Article  CAS  Google Scholar 

  31. E. J. Lawton and J. S. Balwit, J. Phys. Chem. 65, 815 (1961).

    Article  CAS  Google Scholar 

  32. H. H. Jaffe and M. Orchin, “Theory and Applications of Ultraviolet Spectroscopy,” John Wiley and Sons, Inc., New York, N. Y., 1962, p. 257

    Google Scholar 

  33. I. B. Berlman, “Handbook of Fluorescence Spectra of Aromatic Molecules,” Academic Press, New York, N. Y. 1965.

    Google Scholar 

  34. M, T. Vala, J. Haebig and S. A. Rice, J. Chem. Phys. 43, 886 (1965).

    Article  CAS  Google Scholar 

  35. V. E. Shashoua, J. Am. Chem. Soc. 82, 5506 (1960).

    Google Scholar 

  36. D. S. McLure, J. Chem. Phys. 17, 905 (1949).

    Article  Google Scholar 

  37. G. Porter and E. Strachan, Spectrochim. Acta 12, 299 (1958).

    Article  CAS  Google Scholar 

  38. P. M. Johnson and A. C. Albrecht, J. Chem. Phys. 48, 851, (1968).

    Article  CAS  Google Scholar 

  39. V. I. Stenberg in “Organic Photochemistry,” Vol. I, Marcel Dekker, New York, N. Y., 1967, p. 127.

    Google Scholar 

  40. L. Schutte and E. Havinga, Tetrahedron 23, 2281 (1967).

    Article  CAS  Google Scholar 

  41. J. C. Andersen and C. B. Reese, J. Chem, Soc. (1963), 1781.

    Google Scholar 

  42. H. Kobsa, J. Org. Chem. 27, 2293 (1962).

    Article  CAS  Google Scholar 

  43. P. Adams and J. L. Anderson, J. Am. Chem. Soc. 72, 5154 (1950).

    Article  CAS  Google Scholar 

  44. P. E. Stevenson, J. Mol. Spectry. 15, 220 (1965).

    Article  CAS  Google Scholar 

  45. G. Porter and E. Strachan, Trans. Faraday Soc. 54, 1595 (1958).

    Article  CAS  Google Scholar 

  46. S. P. McGlynn, T. Azumi and M. Kinoshita, “Molecular Spectroscopy of the Triplet State,” Prentice-Hall, Englewood Cliffs, N. J., 1969, p. 159.

    Google Scholar 

  47. J. I. Dunlop, Photochem. and Photobiol. 5, 227 (1966).

    Article  CAS  Google Scholar 

  48. D. B. Wetlaufer in “Advances in Protein Chemistry,” C. B. Anfinsen, et al., Vol. 17, Academic Press, New York, N. Y., 1962, p. 303.

    Google Scholar 

  49. W. J. McCarthy and J. D. Winefordner in “Fluorescence, Theory, Instrumentation and Practice,” G. G. Guilbault, ed., Marcel Dekker, Inc., New York, N. Y., 1967, p. 412.

    Google Scholar 

  50. R. A. Keller, in “Molecular Luminescence,” E. C. Lim, ed., W. A. Benjamin, N. Y., 1969, p. 453.

    Google Scholar 

  51. G. Dobson and L. I. Grossweiner, Rad. Res. 23, 290 (1964).

    Article  CAS  Google Scholar 

  52. L. Pauling, “Nature of the Chemical Bond,” Cornell University Press, Ithaca, N. Y., 1948, p. 204.

    Google Scholar 

  53. W. A. Gibbons, G. Porter and M. I. Savadatti, Nature 206, 1355 (1965).

    Article  CAS  Google Scholar 

  54. Yu. A. Vladimirov and E. E. Fesenko, Photochem. Photobiol. 8, 209 (1968).

    Article  CAS  Google Scholar 

  55. A. Maybeck and J. H. Windle, Photochem. Photobiol. 10, 1 (1969).

    Article  Google Scholar 

  56. K. Watanabe, J. Chem. Phys. 26, 542 (1957).

    Article  CAS  Google Scholar 

  57. W. Gordy, W. B. Ard and H. Shields, Proc. Nat. Acad. Sci. U.S. 41, 983 (1955).

    Article  CAS  Google Scholar 

  58. C. J. Seliskar, D. C. Turner et al., in “Molecular Luminescence,” E. C. Lim, ed., W. A. Benjamin, N. Y. 1969, p. 677.

    Google Scholar 

  59. L. I. Grossweiner and W. A. Mulac, Rad. Res., 10, 515 (1959).

    Article  CAS  Google Scholar 

  60. I. Fischer-Hjalmars and M. Sundbon, Acta Chem. Scand. 22, 607 (1968).

    Article  CAS  Google Scholar 

  61. H. B. Steen, Photochem. Photobiol. 9, 479 (1969).

    Article  CAS  Google Scholar 

  62. E. Yeargers and L. Augenstein, Biophys. J. 5, 690 (1965).

    Article  Google Scholar 

  63. Yu. A. Vladimirov and E. A. Burstein, Biofizika 5, 385 (1960).

    CAS  Google Scholar 

  64. W. C. Price and A. D. Walsh, Proc. Royal Soc. A191, 22 (1947).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Ames Research Center, NASA, Moffett Field, California, 94035, USA

    R. F. Reinisch, H. R. Gloria & G. M. Androes (National Research Council Associate)

Authors
  1. R. F. Reinisch
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. H. R. Gloria
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. G. M. Androes
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. NASA-Ames Research Center, Moffett Field, California, USA

    Ronald F. Reinisch

Rights and permissions

Reprints and permissions

Copyright information

© 1970 Plenum Press, New York

About this paper

Cite this paper

Reinisch, R.F., Gloria, H.R., Androes, G.M. (1970). Photoelimination Reactions of Macromolecules. In: Reinisch, R.F. (eds) Photochemistry of Macromolecules. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-8035-1_16

Download citation

  • DOI: https://doi.org/10.1007/978-1-4684-8035-1_16

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-1-4684-8037-5

  • Online ISBN: 978-1-4684-8035-1

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation