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EXPERIMENTAL TECHNIQUE IN PHOTOCHEMISTRY FARRINGTON DANIE1LS Department of Chemistry, University of Wisconsin, Madison, Wisconsin Received May 25, 1958 Ten years ago, when G. S. Forbes (12) wrote the first report of the Com- mittee on Photochemistry of the National Research Council, most of the principles of experimental photochemistry had been enunciated, but quan- titative photochemical measurements had just begun. Since that time a few new techniques have been invented and old ones have been improved; over a hundred quantitative researches have given us the amount of chemical action produced and the amount of radiation of restricted Waite length used. It is gratifying that workers in difl Brent laboratories are now able to check each other's results when the working conditions are the same. The production of monochromatic light, the measurement of the energy absorbed and the chemical reaction produced, and the determination of the nature of the spectrum are the chief problems of the experimental photochemist. Because the monochromatic light is of reduced intensity, the first problem has led to the development of semi-micro methods of analysis. It is not the purpose of this report to give a complete description of the methods used in photochemical investigations' for they may be found in the first report of this Committee (12) and elsewhere (10, 11, 15), or to include a bibliography of researches that have been published on this subject. It is planned merely to build on the first report giving trends of the past dec- ade in experimental photochemistry, to record advances in technique, and to refer to a few selected researches where further details and additional references may be found. LIGHT SOURCES Arcs The quartz mercur~vapor arc lamp is the almost universal standard for photochemical investigations when monochromatic light is necessary. It can be used, however, for only a few selected wave lengths extending from 2000 A to 10,000 A. Several types of arc lamps are commercially avail- able. ~ Contribution No. 1 to the Third Report of the Committee on Photochemistry, National Research Council. 3 .
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4 FARRINGTON DANIELS A small 80-watt lamp which operates on alternating current with a trans- former has been put on the market recently at a low price. It is about 4 mm. by 20 mm. and is suitable for many photochemical experiments. Intense light, for illuminating monochromator slits or small cells, is best supplied by capillary lamps (9, 21), in which the light is concentrated in a small region. These lamps are so inexpensive that one can afford to run them at a heavy overload, even though their life is short. At these over- loads, up to a kilowatt in 10 cubic millimeters of space, the lamps must be water-cooled. For the line at 2537 A. a high-voltage lamp filled with mercury vapor and argon and neon is particularly suitable (32, 45~. It operates on alternating current at about 6000 volts. Eighty-eight per cent of all the radiation is Riven off at this wave length all the.other lines being quite weak. ~ . ~ , _ Arc lamps of other metals comparable in intensity and practicality with the mercury lamp have long been needed. Sodium arc lamps in glass are now available ("Sodium Lab-arc") and are useful for many purposes, but the demands for high intensities in photochemical work are hardly met by them. Neon lamps are also available in convenient form for producing red light, but it is difficult to obtain a highly concentrated radiation from a small area of these lamps. Quartz capillary lamps of cadmium, zinc, thallium, bismuth, and lead can be made to give light at several different lines which is practically as intense as that of the capillary mercury lamp. These lamps (25) are troublesome to make and operate, however, and the intensity falls off because of the formation of an inner coating of silicate; moreover they break when the current is turned off. Tungsten filament lamps are used when continuous light is needed in the red or throughout the visible spectrum. Concentrated filaments are pre- ferred. The intensity of the lamps may be increased considerably by operating them for short times at voltages considerably above their rated voltage. Steadiness of a lamp can be achieved through the use of storage batter- ies, storage batteries floated across a dynamo, an isolated dynamo, or a dynamo operated by a 'synchronous motor. Voltage regulators are avail- able operating with electron tubes or with a ballast coil of iron wire in series with the lamp. Sparks For the shorter ultraviolet in the region of 2000 \. and below, spark dis- charges between electrodes of aluminum, magnesium, and zinc are used (13, 26~. Several types have been described. It is possible, though troublesome, to obtain from-them intensities equal to those of the mercury
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EXPERIMENTAL TECHNIQUE IN PHOTOCHEMISTRY 5 lamp. Large transformers up to 10,000 volts and 5 kilowatts have been used together with large condensers. A blast of cooling air is directed against the spark. The noise and oxide dust are seriously annoying. Large discs of metal rotating at right angles may be used to confine the arc to one position and yet give constantly replaced surfaces (50~. PRODUCTION OF MONOCHROMATIC LIGHT Filters Filters are the cheapest and most convenient means for restricting the radiation to a narrow range of frequencies. A complete assortment of glass filters is available with which the various lines of mercury, helium, or hydrogen can be isolated (19~. A filter of chlorine and bromine gas in quartz is used for filtering out the longer ultraviolet and leaving the 2536 A. line of mercury. Acetic acid cuts off all radiation below 2300 A. Additional filters for specific purposes can be made from solids, liquids, and solutions, the absorption characteris- tics of which can be found in the literature (11, 18, 27~. An excellent set of laboratory filters for the mercury lamp has been as- sembled by Bowen (5~. The infrared radiation is practically completely absorbed by 4 cm. or more of a 1 per cent aqueous solution of copper sulfate (6~. The Christiansen filter (11) consists of a mass of particles of glass or quartz in a bath of liquid having the same refractive index at a given wave length, but a different dispersion. Particles of crown glass (1 to 2 mm. in size) are immersed in a mixture of carbon disulfide and benzene of such a composition that it will have the same refractive index at 5000 A., for example. A beam of light of this wave length will pass through, but light of all other wave lengths will be dispersed. A different composition will pass light of a different wave length. Close temperature control is essen- tial and the range of wave lengths transmitted is not as narrow as might be desired, but the filter can be adjusted to any wave length and the loss of energy in the transmitted light is not great. Monochromators Monochromators, their requirements, and their limitations, have been described by Forbes (12~. Large aperture and short focus are desirable for photochemical work (16, 22) in order to conserve as much energy as possible. Glass and quartz prisms are commonly used, but large hollow prisms filled with a liquid are satisfactory. Ethyl cinnamate is an excel- lent liquid for this purpose on account of its high refractive index and its ability to withstand photochemical decomposition. Water is used some- times, but its refractive index is comparatively low. These liquid prisms
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FARRINGTON DANIELS give lines which are slightly distorted unless the prisms are thermostated with great care, but they are satisfactory for most photochemical work and they are comparatively inexpensive. A large monochromator using a water prism has been described by Harrison (20~. A double monochromator, in which the light from the exit slit of the first one passes into the entrance slit of the second, is much more elective than a single one in giving monochromatic light of great purity. Obviously the intensity is decreased. A double monochromator making use of ethyl cinnamate prisms is on the market. In the focal isolation method the light of different wave lengths is sepa- rated by refraction with a lens instead of a prism. The light of short wave length is brought to a focus closer to the lens and passes through a small hole in a plate, while the longer rays are stopped. The apparatus is simpler to construct and in the short ultraviolet it is probably more effective. It has been used in several investigations making use of spark emission in the ultraviolet (23, 50~. This method has been compared critically with the monochromator method (23~. When mirrors are used, as with the Wadsworth mounting for a mono- chromator, the sputtering of a clean glass surface with aluminum or other vapor in a vacuum is found to be superior to the ordinary silvering process. MEASUREMENT OF RADIATION Thermopiles are usually the simplest and best instruments for measuring the intensity of radiation. Bismuth-silver, copper-constantan, andtel- lurium-platinum are among the combinations of metals which have been used, each being soldered to a thin, blackened metal receiver. High sensitivity is not a very important characteristic of a thermopile, because the limiting factor in photochemical measurement is more likely to be the accuracy of the chemical analysis. The thermopile should be absolutely reproducible, with little drifting of the zero point. The theory and practice of thermopile construction have been discussed critically by Leighton and Leighton (32~. The construction of a small thermopile has been described by Beckmann and Dickinson (1~. The ordinary linear thermopile is smaller than the chemical reaction cell behind which it is placed, and it is necessary to move the thermopile over the whole area in order to obtain an average value. Large-area thermopiles which do their own integrating are simpler for photochemical investigations. The thermocouples, thoroughly protected with glyptal lacquer, are attached with de Khotinsky cement to the back of a blackened receiver 10 by 40 mm. in area. High sensitivity galvanometers of the d'Arsonval type, giving deflec- tions at 1 meter of 5 to 10 mm. per microvolt, are sufficiently sensitive. Galvanometers of the Paaschen type are more sensitive but more trouble-
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EXPERIMENTAL TECHNIQUE IN PHOTOCHEMISTRY some. If necessary the sensitivity can be pushed to the theoretical limit of 10-~° volt imposed by the Brownian motion of the electrons (28), by amplification with two galvanometers. A beam of light from the first galvanometer hits a thermopile or photoelectric cell connected to a second galvanometer, and the system is so arranged that the deflection of the second galvanometer is directly proportional to that of the first (36~. Calibration The energy of radiation is now determined in nearly all photochemical investigations by means of the standard carbon-filament lamps obtainable from the U. S. Bureau of Standards (7, 10~. Calibration of a thermopile and galvanometer is quickly and easily accomplished, and absolute values are reliable to within about 2 per cent. As secondary standard, the uranyl oxalate actinometer (30) is widely used. It is desirable to cross check all photochemical measurements with this simple actinometer. A solution 0.05 molar in oxalic acid and 0.01 molar in uranyl sulfate is titrated with potassium permanganate. The following quantum yields (molecules reacting per quantum) apply at 25°C.: Wave length (A.) 2550 2650 3000 3130 3660 4060 4350 Quantum yield 0.60 0.58 0.57 0.56 0.49 0.56 0.58 When the light is feeble the length of exposure may become impracti- cally long, but more sensitive actinometers such as the mercuric oxalate actinometer, which depend on chain reactions, are not sufficiently repro- ducible or reliable for quantitative measurements. Photoelectric cells Photoelectric cells and electron tube amplifiers are easy to use and are much more sensitive than thermopiles, but they are selective and one must be sure that they give responses which are directly proportional to the intensity at the particular wave length used. They should be calibrated against a thermopile at each wave length. In the study of ultraviolet radiation of extremely low intensity, Geiger counters are used in which a photoelectric surface emits electrons into a gas space between charged electrodes. A system of electron tubes ampli- fies greatly the ionization current produced each time that a photoelectron is shot out. REACTION CELLS A satisfactory photochemical cell should have clear windows with no distortion of light, and the light should fill practically the whole cell. Practices vary, but when a good thermopile is placed immediately behind the cell it is usually preferable to have the depth of the cell and the concen-
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I've FARRINGTON DANIELS tration such that a measurable part of the light is transmitted past the cell. When all the light is absorbed within the cell the calculations are somewhat simplified, but then the intensity at the front and back of the cell varies from full intensity to zero, a fact which may cause uncertainties if the intensity of the light affects the quantum yield. When a dark reaction is involved the correction factor may become too large if there is such a large excess of material as to absorb all the light. Glass or quartz cells are conveniently made by fusing polished discs into tubing of just the right size. Both windows should be at right angles to the path of the light. Flasks or tubes can be used for approximate work when the light energy is measured with an actinometer in the cell. The cell should be so designed that nearly all of the contents of the cell are in the path of the light. Rectangular or trapezoidal cells are pre- ferred, and they can be made to order either in quartz or in Pyrex. Stirring is usually unnecessary in gaseous reactions, but it may be neces- sary for liquid reactions, particularly if a dark reaction is involved or if the reaction is influenced by intensity of light or concentration of material. Stirring should be omitted only in case experiments show that it is not necessary under the conditions of the experiment. CHEMICAL ANALYSIS The requirements for monochromatic light reduce the energy intensity to such an extent that micro or semi-micro methods of analysis are often necessary. One of the most successful micromethods for gas analysis has been developed by Blacet and Leighton (2, 3, 4), using a small bead of solid absorbent,—phosphorus for oxygen, phosphorus pentoxide for water, silver oxide for carbon monoxide, and copper oxide and potassium hydroxide for hydrogen, and other absorbents. Only 0.25 to 1 cc. of gas is needed for a complete determination. More micromethods are needed, particularly for complex organic com- pounds. The removal of gas for analysis offers a problem, particularly when the gas is at reduced pressure. Toepler pumps, which utilize the filling and emptying of a mercury reservoir, are often used (43~. Sometimes the gas is pumped out and frozen in a small tube surrounded with liquid air. Boiling points and freezing points are always useful in identification. Ti- tration methods of precision such as iodimetry find frequent use. Electro- titrations have been developed to a point which makes possible increased accuracy in the study of some photochemical reactions. Conductance methods are applicable sometimes (47~. In gaseous reactions pressure change has been the most common method for following the course of a reaction. Obviously the method is applicable
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EXPERIMENTAL TECHNIQUE IN PHOTOCHEMISTRY ;' 9 only when there is a change in the number of molecules and when the stoi- chiometrical reaction is known to be fairly simple. The pressure is usually followed in a constant-volume cell through a flexible diaphragm of glass or quartz. Many different types are available (8, 42~. The application of Beer's law to the determination of the chemical change is receiving increasing application. The absorption of light con- stitutes one of the simplest methods of analysis and is particularly desirable because it does not disturb the reacting system nor demand the removal of samples. Frequently the same thermopile measurements may be used for the determination of both energy absorption and chemical change. If Beer's law applies, the concentration at any time can be calculated directly from the absorption coefficient, or interpolation may be made on a logarith- mic graph. Even when Beer's law does not apply, graphical interpolation on an experimentally determined logarithmic graph will give the concen- tration. Thermopile-galvanometer readings may be summed up over long periods of time to give both energy absorbed and chemical change produced (24~. The analysis by absorption of light may be applied not only in the case of the light used in the photochemical reaction but to any other wave length. For example, the production of iodine or chlorine in a photolysis by ultra- violet light can be followed by the absorption of light in the visible. It must be proved experimentally that the materials actually absorbing the light are directly involved in the reaction. For example, Vesper and Rol- lefson (48) showed that earlier calculations involving the chlorination of monobromotrichloromethane were erroneous because it had been assumed that chlorine was the only substance absorbing the light, whereas in reality it was being absorbed by a bromine-chlorine compound having an entirely different absorption spectrum. Analysis by infrared absorption has been very accurate and successful in the case of the nitrogen oxides (49) and carbon dioxide (34~. Direct analysis with a calorimeter is often possible, and the increasing use of the photoelectric calorimeter will certainly find further application in photochemical investigations. HIGH AND LOW TEMPERATURES Most photochemical investigations have been limited to temperatures in the neighborhood of room temperature. Data over a wide range of temperature are needed. Particularly with the new interest in free-radical chain reactions it is desirable to obtain quantum yields and chain lengths at high temperatures,- at 300° to 400°C., for example (29, 35~. Special techniques have been developed. It is a good plan to have the thermopile back of the heated reaction chamber completely immersed in water to prevent radiations from the heated walls striking the thermopile.
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10 FARRINGTON DANIELS Low temperature halogenations have been carried out in "freon" sur- rounded by dry ice (14~. ABSORPTION SPECTRA Intelligent planning of a photochemical investigation demands first a full knowledge of the regions in which light is absorbed. essential for this purpose. Much can be learned from absorption spectra concerning the primary photoprocess. The existence or non-existence of fine structure in the spec- trum is often sufficient to decide between different photochemical mecha- nisms. Grating spectrographs give the greatest dispersion, but prism spec- trographs of the best type are often adequate. The fine structure of the spectrum of acetone vapor offers an illustration (38, 39~. The more complex organic compounds and substances in the liquid phase are not likely to show fine structure, but a complete knowledge of the vari- ous absorption bands is helpful. Sometimes the finer details of the spec- trum can be brought out by lowering the temperature of the absorbing sub- stances with dry ice or liquid air. Absorption spectra can be mapped in the usual way by splitting the beam of light into two paths, passing one through the absorbing material and reducing the intensity of the other until the two become equal. On a photographic plate the two are matched. Again the amount of absorption can be determined by the density of the lines or regions on the photo- graphic plate as measured with a photoelectric cell or thermopile. Ex- cellent recording apparatus is available for giving in full detail the in- tensity of absorption throughout the spectrum. An important new development is the adaptation of the photoelectric cell to the direct determination of the percentage absorption in the different parts of the spectrum (53~. Quantitative absorption measurements on chlorophyll have been obtained by this means (52) without the uncertainty of the photographic plate. In some ways this method is less expensive and more direct than the photographic method. The emission spectra of fluorescent materials may give information re- garding the photomechanisms. Since the light is weak, large apertures and long exposures are necessary with a photographic plate. Quantita- tive measurements of the energy emitted in fluorescence may be made with Spectrograms are the photoelectric cell (53~. For the light needed in making absorption spectra tungsten filaments are suitable down to about 3600 A., but the intensity is low at the shorter wave lengths. Quartz windows may be attached to the glass bulbs sur- rounding the filament. The iron arc gives many lines throughout the whole spectrum and is widely used in absorption spectra, but it is obviously unsuited for studying fine structure.
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EXPERIMENTAL TECHNIQUE IN PHOTOCHEMISTRY ~ 1 Improvements have been made in continuous sources of light in the ultra- violet. The spectrum of molecular hydrogen is most commonly used. Vessels are so arranged that an intense electrical discharge is passed through hydrogen at a low pressure in a tube which allows recombination of the atoms by collision with a metallic surface. An efficient tube calf simple design has been described by Munch (37~. Isotopic tracers The new techniques by which atoms can be traced through chemical reactions by means of radioactivity or abnormal (isotopic) atomic weights are destined to settle many problems of photochemistry. To date only a few experiments of this type are on record. Taylor and Jungers (46) mixed deuterium with ammonia and mercury vapor and subjected the mixture to illumination with the resonance radia- tion at 2536 A. Deuterium entered the ammonia under the influence of the radiation, and the results showed that the low quantum yield obtained in the photolysis of ammonia is due to the recombination of hydrogen atoms and the NH2 radicals formed by the photochemical reaction. Leighton and Mortensen (33) used radioactive lead in their study of the mechanism of the photolysis of lead tetramethyl. Free radicals Many photochemical reactions are now believed to involve the produc- tion of free radicals as a first step. There is a great deal of indirect evi- dence and some direct evidence for this theory. A test has been applied, for example, in the photolysis of acetone, in which removal of al lead or antimony mirror is used to support the view that free methyl radicals are produced in the photolysis (40, 44~. The existence of OH and other free radicals in the electrical discharge has been proved by characteristic absorption bands (17~. One of the most complete researches on absorption has given experi- mental proof of the production of iodine atoms when iodine molecules are illuminated. Rabinowitch (41) has described a delicately balanced color- imeter, with an amplifying circuit of electron tubes, which measures with great accuracy the change in absorption produced by a photochemical reaction. The conversion of ortho-para hydrogen has been used also as a test for the independent existence of free radicals containing an odd number of electrons (51~. REMARKS Quantitative methods for measuring photochemical reactions are now well established, but more intense sources of monochromatic light are
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12 FARRINGTON DANIELS needed. Also, the further development of the spectroscopy of polyatomic molecules will lead to advances in photochemistry. Improvements are needed in methods for the analysis of the complex products of photochemi- cal reactions. Special care must be exercised in certain reactions to remove impurities such as oxygen and moisture, which sometimes affect the reac- tion. Interesting developments are to be expected in photochemical stud- ies at high and low temperatures, and at low gas pressures. Greater accuracy in determining quantum yields is useless unless the conditions of temperature, pressure or concentration, and light intensity are clearly defined. REFERENCES (1) BECKMANN AND DICKINSON: J. Am. Chem. sac. 62, 126 (1930~. (2) BLACET AND LEIGHTON: Ind. Eng. Chem., Anal. Ed. 3, 266 (1931~. (3) BLACET AND MACDONALD: Ind. Eng. Chem., Anal. Ed. 6, 334 (1934~. (4) BLACET, MACDONALD, AND LEIGHTON: Ind. Eng. Chem., Anal. Ed. 6, 272 (1933). (5) BOWEN: J. Chem. soc. 1936, 76. (6) COBLENTZ: Burl Standards Bull. 9, 110 (1913~. (7) COBLENTZ: Burl Standards Bull. ll, 87 (1915~. (8) DANIELS: J. Am. Chem. sac. 60, 1115 (1928~. (9) DANIELS AND HEIDT: J. Am. Chem. soc. 64, 2381 (1932~. 10) DANIELS, MATHEWS, AND WILLIAMS: Experimental Physical Chemistry, Chap. xxx. McGraw-Hill BOOk CO., Inc., New York (1934~. 1l) DUGGAR: Biological Effects Of Radiation, Chaps. IV and VII. McGraw-Hill BOOk CO., InC., New York (1936~. 12) FORBES : J. PhYS. Chem. 32, 485 (1928). 13) FORBES AND BRACKETT: J. Am. Chem. sac. 63, 3973 (1931~. 14) FORBES AND NELSON: J. Am. Chem. sac. 68, 182 (1936~. 15) FORSYTHE: Measurement Of Radiant Energy. McGraw-Hill Book co.' InC., New York (1937~. 16) FORSYTHE AND BARNES: Rev. Sci. Instruments 4, 289 (1933~. 17) FROST AND OLDENBERG: J. Chem. Phys. 4,642 (1936~. 18) GIBSON : J. Optical sac. Am. 13, 267 (1926~. 19) Glass Color Filters, Corning Glass Works, Corning, New York. 20) HARRISON: Rev. Sci. Instruments 6, 149 (1933~. 21) HARRISON AND FORBES: J. Am. Chem. soc. 47, 2449 (1925~. 22) HEIDT AND DANIELS: J. Am. Chem. soc. 64, 2384 (1932~. 23) HEIDT AND FORBES: Rev. Sci. Instruments 6, 253 (1934~. 24) HOFFMAN: J. Am. Chem. sac. 66,1894 (1934~. 25) HOFFMAN AND DANIELS: J. Am. Chem. sac. 64, 4226 (1932~. 26) HOWE AND NOYES: J. Am. Chem. soc. 68, 1405 (1936~. 27) International Critical Tables, Vol. V, p. 271; VO1. VII, P. 160. McGraw-Hill Book Co., Inc., New York (1929 and 1930~. 28) ISING: Phil. Mag. 1, 827 (1926) . 29) LEERMAKERS: J. Am. Chem. soc. 66, 1537 (1934~. 30) LEIGHTON AND FORBES: J. Am. Chem. soc. 6a, 3139 (1930~. 31) LEIGHTON AND LEIGHTON: J. Phys. Chem. 36, 1882 (1932~. 32) LEIGHTON AND LEIGHTON: J. Chem. Education 12, 139 (1935~. 33) LEIGHTON AND MORTENSEN: J. Am. Chem. soc. 68, 448 (19361.
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EXPERIMENTAL TECHNIQUE IN PHOTOCHEMISTRY ~3 (34) MCALLISTER: P1ant PhYSiO1. 12, 213 (1937~. (35) MITCHELL AND HINSHEDWOOD: Proc. Roy. Soc. (LOndOn) A169, 32 (1937~. (36) MOLL: Z. PhYSik 34, 3 (1925~. (37) MUNCH: J. Am. Chem. Soc. 67, 1863 (1935~. (38) NORRISH, CRONE, AND SALTMARSH: J. Chem. Soc. 1934, 1456. (39) NOYES, D1:rNCAN, AND MANNING: J. Chem. Phys. 2, 717 (1934~. (40) PANETH AND HOFEDITZ: Ber. 62, 1335 (1929~. (41) RABINOWITCH: Trans. Faraday Soc. 32, 547 (1936~. (42) RAMSPERGER AND TOLMAN: J. Am. Chem. Soc. 96, 6 (1930~. (43) REILLY AND RAE: Physico-Chemical Methods, p. 72. D. Van Nostrand Co., New York (1933~. (44) RICE AND RICE: The Aliphatic Free Radicals. The Johns Hopkins Press, Baltimore (1935~. (45) TAYLOR: J. Chem. Phys. 2, 377 (1934~. (46) TAYLOR AND JUNGERS: J. Chem. Phys. a, 452 (1934~. (47) VAIDJA: Proc. Roy. Soc. (London) A129, 299 (1930~. (48) VESPER AND ROLLEFSON: J. Am. Chem. Soc. 66, 620, 1455 (1934~. (49) WARBURG AND LEITHADSER: Ann. Physik 28, 313 (1909~. (50) WI1G AND KISTIAKOWSKY: J. Am. Chem. Soc. 64, 1807 (1932~. (51) WEST: J. Am. Chem. Soc. 67, 1931 (1935). (52) ZSCHEILE: J. Phys. Chem. 38, 95 (1934~. (53) ZSCHEILE, HOGNESS, AND YODNG: J. Phys. Chem. 38, 1 (1934~. .
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Representative terms from entire chapter: