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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
16 FARRINGTON DANIELS * c) z x z C, ~ LIZ o o o ._ Do '_ X o ·- ~ 8 8 ~ ° o ° ~ ~ O CS, _ c' ~ ~ A tD ~ ¢ ¢ . _ ~ _ _ _ _ · 8 o ~ ~ ~ ~ oo ~ ~ ~ ~ ~ ~ ~ ~ o o o ~ ~ ~ ~ ~ ~ ~ ~ ~ o ,o o o o ~ o o CO ·g A ·= P: .= ¢ a, En En p; P EN E4 {;) c°~ ° e~ ~° 8 ~ ~ 0 C~ CO eo o o o cO O O ~0 d°4 Ub u:' ~ co ~ 1 1 C~ eH o o cO o o o o o ~ ~ o c~ CO e~ ~ ~ ~ ~ g c;~ e,:) cIC} o cO c'C) oo ~ ~ c~ O m v v ~ v E4 ~ . $ GO t3 0 ~ o o o ~ ' - · - ·GQ ~ o o o o R ~ O ~; O C) V C) Op~ CL) C) . _ ~ d O ,~ V ¢,, V ~ V ~ V ,;] V .0 V o ~ ~ ~ ~ ~ ~ ~ ¢ ¢ ¢ ¢ E~ C) p o P1 o
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QUANTUM YIELDS IN EXPERIMENTAL PHOTOCHEMISTRY 27 11 .= o O _ ~ ~ ~ ·- ~ ~ B.= ~ . - >, o oo ~ ~ B ,, ~v °° O O _ m; ~ R. ~ ~ t - 72 11 11 1I p4 ~D C~ ~ ~ (33 0 C C3 ~ ~ O ~ ~ ~ ~ ~ ~ CO C) ~ C) ¢ ¢ ¢ ~ _ U: O O ~ ~ oo ~ U: . . . . . . . . . O O O O O O O O O C~ CO U: a0 ~ O . . . . O ~ ~ O V U: C~ d~ eo CO O · · . . . O O O O O V O O 1 C~ C~ O di O O O O O - CO CC7 U: 0 ~ '~ °= '~ ~ 1 8 1 = =I 8 u°t 8 ~ ~ Ol ~ ° ~ O O CO ~ _ oo CO C~ CO C~ t d, e~ C!) d~ CO C~ <c, C~ ~ C~ , e~ ~ CO ~ _I CO CO _~ _ O" V o O O ~ O O O O O 0= ~ Z V ~ ~ ~ Z Z Z ~ ~ ~ ~ ~ ~ ~ V ~ ~ V ~ ~ ~ ' ' ° 2° ° 2 O _ ° ~ _ Z ~ ~ Z O Z Z Z Z Z ~
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Q~ FIELDS IN EXPERI~L PBOTOCBE~ISTRY ~1 ad ~ ~ ~ o == ~ ~ ~ .- . . . . . . . . 1 ^ . . o ~ d ~ o o ~ . ~ ~ o ~ ~ .~ o o C ~ o .s ~ .- ~ ~ ~ e I ~ : S: ~ !! j~ ~ 2~ /~ ~ o ~ ~ ~ I HI e
32 r 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. REFERENCES (l) AKEROYD AND NOURISH: J. Chem. soc. 1936, 890. (2) ALLMAND, CUNLIFFE, AND MADDISON: J. Chem. soc. 131,655 (19271. (3) ALLMAND AND STYLE: J. Chem. soc. 1930, 596,606. (4) ANDERSON, CRUMPLED, AND HAMMICE: J. Chem. soc. 1936, 1679. (5) BACER AND DANIELS: J. Am. Chem. soc. 66,378,2014 (1934~. (6) BAXTER AND DICKINSON: J. Am. Chem. soc. 61' 109 (1929~. (7) BECgMAN AND DICKINSON: J. Am. Chem. soc. B2, 124 (1930~. (8) (9) (10) (11) (12) (13) (14) (15) (16) BENTON AND CUNNINGHAM: J. Am. Chem. soc. 36, 2227 (1935~. BERTEOUD AND POPPET : Helv. Chim. Acta 17, 237 (1934~. BLACET, WELDING, AND ROOF: J. Am. Chem. soc. 69,2375 (1937~. BLACET AND ROOF: J. Am. Chem. soc. 68, 73 (1936~. BLACET AND ROOF: J. Am. Chem. soc. 68,278 (1936~. BLOCH AND NOURISH: J. Chem. soc. 1936,1638. BODENSTEIN AND KISTIAKOWSKY: z. physik. Chem. 116, 371 (1925~. BODENSTEIN AND LIENEWEG: z. physik. Chem. 119, 123 (1926~. BODENSTEIN AND LUTKEMEYER: z. physik. Chem. 114,208 (1925~; LEWIS AND RIDEAL: J. Am. Chem. soc. 48, 2555 (1926~. (17) BODENSTEIN AND WINTER: Sitzber. preuss. Akad. wise., p. 2 (1936~. (18) BONHOEFFER: z. Physik 13,94 (1923~. (19) BOOHER AND ROLLEFSON: J. Am. Chem. soc. 66, 2288 (1934~. (20) BOOK AND EGGERT: z. Elektrochem. 29,521 (1923~. (21) BOWEN AND HORTON: J. Chem. soc. 1936,1685. (22) CARRICO AND DICKINSON: J. Am. Chem. soc. 67, 1343 (1935~. (23) CHAPMAN: J. Am. Chem. soc. 67, 416 (1935~. (24) COEHN AND CORDES: z. physik. Chem. B9, 1 (1930~. (25) CRAGGS AND ALLMAND: J. Chem. soc. 1936, 241. (26) CRIST: J. Am. Chem. soc. 64,3939 (1932~. (27) DAMON AND DANIELS: J. Am. Chem. soc. 66,2363 (1933~. (28) DAVIS, JAHN, AND BURTON: J. Am. Chem. soc. 60,10 (1938~. (29) DERIGHT AND WI1G: J. Am. Chem. soc. 67,2411 (1935~. (30) DHAR AND BHARGAVA: J. Phys. Chem. 39,1231 (1935~. (31) DICKINSON AND CARRICO: J. Am. Chem. soc. 66, 1473 (1934~. (32) DICKINSON AND JEFFREYS: J. Am. Chem. soc. 62,4288 (1930~. (33) DICKINSON AND LEERMAKERS: J. Am. Chem. soc. 64,3852 (1932~. (34) DICKINSON AND RAVITZ: J. Am. Chem. soc. 62,4770 (1930~.
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