Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

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3 APPARATUS 553.3.4 The production of "monochromatic" radiationMost quantitative photochemical studies are carried out using "monochromatic"radiation, since the wavelength very often affects the quantum yield (4) ofa reaction and the relative extents of the possible primary processes. Also, the useof monochromatic light allows the accurate determination of c$, the intensity ofthe radiation, and the fraction absorbed by the reacting medium. The use of differentmonochromatic sources will indicate whether there are any hot radicaleffects, since the excess energy available will vary.(a) LasersAn ideal monochromatic source is the laser or uvaser. There is little or no publishedwork on continuous photolysis using these sources although we must beon the threshold of this happening. Porter and Steinfeldl 48 have flash-photolysedphthalocyanine in the vapour phase using a Q-switched ruby laser. This emits at6943A, and 2-3 J are dissipated in 20 psec. Photolysis occurs because of a twophotonprocess.The unique properties of lasers are their coherence, monochromaticity and highintensity. However, as yet, the intensities of commercial lasers emitting radiationbelow 6000 A are very low. Their photochemical potential is reviewed by T ~rro'~~.An excellent account of the theoretical background has been given by Smith andS~rokin'~'. Also, Le~ine'~' has started a useful series on lasers. Both of thesereviews, however, are concerned solely with the spectroscopic potential of lasers.In another connection, stimulated emission from vibrationally excited HCl producedin reaction (16)H.+cI,-+Hc~*+H. (16)References pp. 104-111Fig. 44. A crystal quartz monochromator. See Calvert and Pitts' p. 725.
56 EXPERIMENTAL METHODS FOR SLOW REACTIONSTABLE 7APPROXIMATE WAVELENGTH LIMITS FOR TRANSMISSIONOF VARIOUS OPTICAL MATERIALS AND WATER NEARROOM TEMPERATUREMaterial Thickness (mm) 50 %Approximate 1 (A) for %transmission indicated30 %10 %Window glass (standard)Optical (white crown) glassPyrex (Corning 774)Corex D [Pyrex, Corning9-53 (9700)lCorex AVycor 790Vycor 791Quartz, crystalQuartz, clear fused(General Electric Co.)Suprasil (Englehard Industries, Inc.)Sapphire synthetic (Linde Air Products)Fluorite (CaF,), naturalCaF,, synthetic (Linde Air Products)Lithium fluoride (synthetic)Plexiglas (polymethylmethacrylate)Water (distilled)1 31603 330010 35201.8 32701 30602 31704 33001 27802 28804 30402.9 248021 21502 22304 23605 185010 193010 194010 17000.55 135010 157035 107010 14202.5 32205.0 338010.0 350020 188040 192080 2020312032303420320029703090319026702800292024302130217022501920181016801450127031003250342018601880194030703140330030902800297031002500267028102400> 25402120213021701860172016601425138012201150297031103260185018601880apart from being the first reported chemical laser, provides a means of determiningthe energy distribution among the degrees or freedom associated with this' 52and similar reactions'53.(b) MonochromatorsThe best way of isolating monochromatic radiation from a source emitting severallines is by means of a prism or diffraction grating monochromator. This
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COMPREHENSIVE CHEMICAL KINETICS
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P.O.ELSEVIER PUBLISHING COMPANY335
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Contributors to Volume 1L. BATTDepa
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XCONTENTS4.3 Gas chromatography ...
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XI1CONTENTS4.6 Magnetic measurement
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Chapter 2Experimental Methods for t
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114 EXPERIMENTAL METHODS FOR FAST R
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;,124 EXPERIMENTAL METHODS FOR FAST
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178 REFERENCES46 M. EIGEN AND L. DE
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Chapter 3Experimental Methods for t
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182 EXPERIMENTAL METHODS FOR HETERO
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~~~ ._190 EXPERIMENTAL METHODS FOR
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192 EXPERIMENT A L MET H 0 D S F 0
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206 EXPERXMENTAL METHODS FOR HETERO
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222 EXPERIMENT A L METHODS F 0 R HE
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230 EXPERIMENT A L METHOD s FOR HET
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242 EXPERIMENT A L ME TH 0 D S FOR
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248 EXPERIMENT A L METHOD s F o R H
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254 EXPERIMENTAL MET HODS FOR HETER
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258 EXPERIMENT A L METHODS F 0 R HE
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270 EXPERIMENTAL MET HODS FOR HE TE
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274 EXPERIMENT A L METHOD s FOR HE
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280 DETECTION AND ESTIMATION OF INT
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344 TREATMENT OF EXPERIMENTAL DATAf
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41 8 TREATMENT OF EXPERIMENTAL DATA
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IndexAabsorption cross section, che
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424 INDEXbenzyl chloride, matrix ph
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426 INDEXchlorine (contdj—, react
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428 INDEXdeuterium oxide, addition
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430 INDEXentropy change, in radical
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432 INDEXfrequency of oscillation,
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434 INDEXhydrogen atoms (contdj—,
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436 INDEXisotopes (contd.J—, use
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438 INDEXmethyl radicals, chain ter
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440 INDEXoctadiene, ESR determinati
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442 INDEXphotoelectric measurement,
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444 INDEXrad, definition of, 66radi
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446 INDEXSchmidt number, and mass t
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448 INDEXTtailing reducer, in gas c
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450 INDEXviscosity, and diffusion c
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