3 1.6 360 5320 1.42 brighter luminescence
Mills [1b] reports, giving no experimental details, that injecting crude phosphine into a current of natural gas (i.e. CH
) at a level insufficient to cause ignition produces a bright green luminescent “flame”; but there was plenty of smoke, a characteristic smell, and the color did not match what was expected, according to the eye-witnesses. We notice, however, that under different condition (relative and absolute amounts of the gases, temperature and humidity, etc.) smoke and smell could be not
present; or even – if present - they might have gone unnoticed. Furthermore, under condition of feeble light, the human eye cannot easily discriminate between colours.
might well be a likely explanation for this elusive phenomenon; given the right conditions, the suitable range of concentrations of the appropriate gases for which it takes could possibly be found also in nature,
generating a will-o'-the-wisp.
Of course, this or other speculations could be confirmed or disproved by generating a chemiluminescent gas by biological fermentation processes, or - even better - by capturing a real willo'-the-wisp.
is involved in the generation of the willo'-the wisp, there is no need for hunting it during the night. Will-o'-the wisp may occur even during the daytime, when its appearence will be invisible because of the stronger light. Also, PH
might be present in lower concentration than those required for the phenomenon to arise; nevertheless, its detection in the presence of decaying organic matter (most easily in cemeteries) might provide an indirect evidence
Consequently, we are planning the monitoring of air samples from graveyards, marshes, etc. using a very sensitive PH
detector, a portable Draeger Xam-7000. [7 and Fig. 3] The first few trials in the cemetry of Pavia, at night and during the day [Fig. 4], gave until now negative results; but the the hunting season is always open.
Acknowledgments
We thank: Prof. M.Oddone and C. Herborg (University of Pavia) for hospitality;
Dr M. Benzo (Osmotech) for Draeger Xam-7000 and
F. Ramaccini for helpful suggestions.
References
[ 1 ]
a)
Will-o'-the-wisp - Wikipedia, the free encyclopedia (may 2007)
b) A. A. Mills, Will-o'-the-wisp. Chem. Brit., 69-72, Feb. 1980, and refs cited therein.
c) A. A. Mills, Will-o'-the-wisp revisited. Weather, 55, 239-241 (2000)
[ 2 ]
W. H. Perkin, J. Chem. Soc. 1899, 75, 600.
[ 3 ]
a) Angew. Chem. Int. Ed. Engl. 1993, 32, 5, 761-763
b) Naturwissenschaften, 80 (1993), 78-80
[ 4 ]
a) D. Harris, M. Chou, T. Cool, Experiments concerning phosphorus chemiluminescence. J. Chim. Phys., 82, (8), 1985,
3502-3515 (PH3 and N2O and at 666 Torr)
b) J. Chem. Soc. Faraday Trans. I, 1983, 79, 527-542 (PH3 + O3 at reduced press.)
c) J. Phys. Cem., 1984, 88, 5569-5574 (ab initio calc.)
d) J. Chem. Soc. Faraday Trans. I, 1984, 80, 285-295 (idem)
e) Anal. Chem. 1983, 65, 1665-1668 (PH3 + O3 at atm.press)
f) Proc. Roy. Soc. A, 302, 243-252 (1968) (PH3 and atomic O)
[ 5 ]
M Trautz, W. Gabler, Ueber Zunddrucke von Phosphingemischen. Z. Anorg. allgem. Chem., 180, 321 354 (1921)
See also:
H. J. van de Stadt, Zeitschr. Physik. Chem., 12, 322-332 (1893).
H. G. Emeleus . A Spectroscopic study of the Combustione of Phosporus Trioxide and of Hydrogen Phosphide. J. Chem.
Soc.1362-1368, (1925)
[ 6 ]
a) E. Fluck, the Chemistry of Phosphine. Top. Curr. Chem., vol 35.
b) J.W.Mellor, A Comprehensive Treatise on Inorganic and Theorethical Chemistry, Vol. VIII, 802-821
c) Inorg. Synth., vol. IX, 56-59.
[ 7 ]
a)
Drgerwerk AG
pd_x_am7000.jsp
b)
http://www.afcintl.com/pdf/xam7000.pdf
Further Chemiluminescence Bibliography:
Adam, W. and G. Cilento Eds. "Chemical and Biological Generation of Excited States"; Academic Press; New York, 1982.
Barnett, N. and R. Evans, "Luminescence: Overview" in Encyclopedia of
Analytical Science, pp 2733-2749; Academic Press, Orlando, FL, 1995.
Birks, J.W. Ed. "Chemiluminescence and Photochemical Reaction Detection in Chromatography"; VCH Publishers; New York, 1989.
Burr, J.G. "Chemi-and Bioluminescence"; Marcel Dekker; New York, 1985.
Campbell, A.K. "Chemiluminescence: Principles and Applications in Biology and Medicine"; VCH, Ellis Horwood Ltd.; New York, 1988.
DeLuca, M.A. and W. D. McElroy, Eds. "Bioluminescence and Chemiluminescence. Part B; Academic Press; Orlando, FL, 1986.
Fontijn, A. Ed. "Gas-phase Chemiluminescence and Chemi-ionization"; Elsevier; New York, 1985.
Gundermann, K.-D. "Chemiluminescence in Organic Chemistry", in Series called Reactivity and Structure: Concepts in Organic Chemistry, Volume 23; Springer-Verlag; Berlin, 1987.
Lewis, S.W.; D. Price; and P.J. Worsfold, Flow Injection Assays with Chemiluminescence and Bioluminescence Detection - A Review. Journal of
Bioluminescence and Chemiluminescence, 1993, 8(4), 183-199.
McGown, L.B, and I.M Warner, Molecular Fluorescence, Phosphorescence, and Chemiluminescence Spectrometry; Analytical Chemistry, 1990, 62(12), 255R.
Nieman, T. "Chemiluminescence: Theory and Instrumentation, Overview", in Encyclopedia of Analytical Science, pp 608-613; Academic Press, Orlando, FL, 1995.
Nieman, T. "Chemiluminescence: Techniques, Liquid-Phase Chemiluminescence", in Encyclopedia of Analytical Science, pp 613-621; Academic Press, Orlando, FL, 1995.
Pringle, M.J. "Analytical Applications of Chemiluminescence"; in Recent Advances in Clinical Chemistry, Vol 30, pp. 89-183, 1993, Academic Press; New York, 1993.
Schreiner, R.; M. E. Testen; B.Z. Shakhashiri; G.E. Dirren; and L. G. Williams "Chemiluminescence"; Chapter 2 in multivolume set called Chemical Demonstrations, B. Z. Shakhashiri, Ed., Vol. 1; University of Wisconsin Press, Madison,WI, 1983, pp. 125-204.
Smith, P.E.; K. Johnston; D.M. Reason; and G.M Bodner, A Multicolored Luminescence Demonstration, Journal of Chemical Education, 1992, 69(10), 827-828.
Stiles, D.A., A.C. Calokerinos, and A. Townshend, "Flame Chemiluminescence Analysis by Molecular Emission Cavity Detection"; Wiley; Chichester, New York, 1994.
Van Dyke, K. "Bioluminescence and Chemiluminescence : Instruments and Applications"; CRC Press, Boca Raton, FL,1985.
Warner, I. M. and L.B. McGown, Molecular Fluorescence, Phosphorescence, and Chemiluminescence Spectrometry, Analytical Chemistry, 1992, 64(12), 343R.
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