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OCR for page 15
A TABLE OF QUANTUM YIELDS IN EXPERIMENTAL
PHOTOCHEMISTRY1
FARRINGTON DANIELS
Department of Chemistry, University of Wisconsin, Madison, Wisconsin
Received May 25, 1988
In the early development of quantitative photochemistry it was believed
by some that the Einstein relation would apply in many cases not only to
the primary process of photoexcitations but to the overall reaction as well.
Quantum yields were summarized with the purpose of testing this hypoth-
esis. Any hope of simplicity in chemical kinetics disappeared long ago,
and the present table has been assembled not to emphasize the almost
universal occurrence of secondary efl ects which follow the primary process
of quantum absorption, but to record the experimental facts of photo-
chemistry in the simplest possible manner. The primary excitation is
usually followed by rearrangements and degradation of the energy as
heat, by reverse or competing reactions which make the overall quantum
yield less than unity, or by continuing reactions which produce a chain
and give a value greater than unity. Sometimes it is possible to study
these factors from the magnitude of the quantum yield and its response
to influences such as temperature, wave length, concentration, and chemi-
cal reagents.
The amount of chemical reaction produced by the absorption of radia-
tion will change with the duration of exposure, the intensity of the light,
the thickness and condition of the absorbing material, and other factors.
The fundamental simple relation between light and chemical action, how-
ever, is the quantum yield A, i.e., the number of molecules of substance
reacting for each quantum of radiation, or photon, absorbed. When this
is known the extent of the chemical reaction produced by the absorption
of a given amount of light is easily calculated.
In table 1 are summarized the findings of most of the quantitative
photochemical researches in which the results are expressed in terms of
quantum yields. Many excellent researches are not included, simply
because the results were not given in these terms. Photochemistry has
been greatly stimulated by hypotheses in chemical kinetics, and the
testing of these hypotheses has been the chief aim in many cases. For
~ Contribution No. 2 to the Third Report of the Committee on Photochemistry,
National Research Council.
15
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FARRINGTON DANIELS
these purposes it is often unnecessary to express the results in absolute
units (quantum yields).
In many cases the quantum yield varies with temperature, concentra-
tion, and intensity. Particularly in chain reactions the quantum yield
may vary considerably with slight changes in the reacting system and
with traces of impurities. Special conditions, such as concentration, are
given in the last column of table 1. When the temperature is not given
it may usually be taken as room temperature (about 20°C.~. Parentheses
around a quantum yield indicate a lesser degree of accuracy. When there
is uncertainty regarding A, the original article should be consulted.
The references are given in parentheses in the last column and include
references to earlier investigations.
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(8)
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QUANTUM YIELDS IN EXPERIMENTAL PHOTOCHEMISTRY 33
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(75) LEIGHTON AND STEINER: J. Am. Chem. Soc. 68, 1823 (1936~.
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(77) LIND AND LIVINGSTON: J. Am. Chem. Soc. 64, 94 (1932~.
(78) LIND AND LIVINGSTON: J. Am. Chem. Soc. 66, 1036 (1933~.
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(83) MEYERS AND BECKMAN: J. Am. Chem. Soc. 67, 89 (1935~.
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(85) MONTGOMERY AND ROLLEFSON: J. Am. Chem. Soc. 66, 4025 (1933~.
34
FARRINGTON DANIELS
(86) MULLER AND SCHUMACHER: Z. PhYSik. Chem. B36, 285 (1937~.
(87) NEWLING, STAVELY, AND MOEEWYN-HUGHES: TranS. FaradaY SOC. 29, 1155
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(88) NORRISH: J. Chem. SOC. 1927, 761; 1929, 1158, 1611.
(89) NORRISH, CRONE, AND SALTMARSH: J. Chem. SOC. 1934, 1456 (1934~.
(90) NORRISH, CRONE, AND SALTMARSH: J. Chem. SOC., 1933, 1533.
(91) NORRISH AND KIRKBRIDE: J. Chem. SOC. 1932, 1518.
(92) NORTON: J. Am. Chem. SOC. 66, 2294 (1934~.
(93) NOYES: J. Chem. PhYS. 5, 807 (1937~.
(94) OGG, LEIGHTON, AND BERGSTROM: J. Am. Chem. SOC. 66, 1754 (1933~.
(95) OGG, LEIGHTON, AND BERGSTROM: J. Am. Chem. SOC. 66, 318 (1934~.
(96) PATAT AND KOCH: Z. E1ektrOChem. 41, 494 (1935~.
(97) QURESHI AND TAKIR: J. PhYS. Chem. 36, 2670 (1932~.
(98) RABINOWITSCH: Z. PhYSik. Chem. B19, 190 (1932~.
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(100) ROSS AND KISTIAKOWSKY: J. Am. Chem. SOC. 66, 1112 (1934~.
(101) RUDBERG: Z. PhYSik 24, 247 (1924~.
(102) SCHUMACHER: Z. PhYSik. Chem. 129, 261 (1927~.
(103) SCHUMACHER AND BERG~§ANN: Z. PhYSik. Chem. B13, 269 (1931~.
(104) SCHUMACHER AND TOWNSEND: Z. PhYSik. Chem. B20, 375 (19331.
(105) SCHUMACHER AND WOLFF: Z. PhYSik. Chem. B26, 161 (1934~.
(106) SCHUMACHER AND WOLFF: Z. physik. Chem. B26, 453 (1934~.
(107) SIMMONS AND BECKMAN: J. Am. Chem. SOC. 68, 454 (1936~.
(108) SMAKULA: Z. PhYSik. Chem. B26, 90 (1934~.
(109) SMITH AND KISTIAKOWSKY: J. Am. Chem. SOC. 67, 835 (1935~.
(110) SMITH, NOYES, AND HART: J. Am. Chem. SOC. 65, 4444 (1933~.
(111) SPENCE AND WILD: Proc. LeedS Phil. Lit. SOC., Sci. SeCt. 3, 141 (1936~.
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(114) STEWART AND WIEDENBAUM: J. Am. Chem. SOC. 67, 1702 (1935~.
(115) THOMPSON AND LINNETT: J. Chem. SOC. 1936, 1452.
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(118) VAUGHN AND NOYES: J. Am. Chem. SOC. 62, 559 (1930~.
(119) VESPER AND ROLLEFSON: J. Am. Chem. SOC. 66, 1455 (1934~.
(120) VILLARS: J. Am. Chem. SOC. 49, 326 (1927).
(121) VRANECK: Z. E1ektrOChem. 23, 336 (1917~.
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(125) WARBURG AND RUMP: Z. PhYSik 47, 305 (1928).
(126) WELGE AND BECKMAN: J. Am. Chem. SOC. 68, 2462 (1936).
(127) WENNER AND BECKMAN: J. Am. Chem. SOC. 64, 2787 (1932~.
(128) WEIGERT: NatUrWiSSenSChaften 16, 124 (1927~.
(129) WEIZMANN, BERGMANN, AND HIRSHBERG: J. Am. Chem. SOC. 68, 1675 (1936)
(130) WEST AND GINSBURG: J. Am. Chem. SOC. 66, 2626 (1934~.
(131) WEST AND ROLLEFSON: J. Am. Chem. SOC. 68, 2140 (1936~.
(132) WEST AND SCHLESINGER: J. Am. Chem. SOC. 60, 961 (1938~.
(133) WI1G: J. Am. Chem. SOC. 57, 1559 (1935).
(134) WILLARD AND DANIEI~S: J. Am. Chem. SOC. 67, 2240 (1935~.
(135) WINKI.ER: Trans. Faraday Soc. 31, 761 (1935).
(136) ZIMMER: Z. PhYSik. Chem. B23, 239 (1933~.
