Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

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3 APPARATUS 37intensity in the uv and visible regions. The high-pressure lamp tends to have lessradiation in the uv than the medium-pressure lamp but is a very intense sourceof radiation. In order to see how these lamps operate it is instructive to look atthe electronic transitions for mercury. The ground state configuration is (6s2)'S,.The selection rules for the electronic transitions of atoms (Russell-Saunders coupling)areAS = 0, AL = 0, 1, AJ = 0, +I but S = 0 ++ J = 0An = 0, 1, 2,. ..S is the total spin quantum number = s,+s,+s, . .., L is the total angular niomentumquantum number = Zl+Z2+Z3..., J is the vector sum S+L, and n isthe primary quantum number. The rule AS = 0 is obeyed fairly strictly for thelighter elements but breaks down for heavier elements. One may look at this assome mixing of the various states, i.e. the singlet and triplet states have partlytriplet and singlet characters, respectively. However, the selection rule is partlyreflected in the lifetime for the states due to the relationshipwhere E is the extinction coefficient. Hence E is a good deal less for singlet-triplet242ttSinglets I TripletsIonization potentalIIReferences pp. 104-111Fig. 27. Lower excited states of the mercury atom. From ref. 9.
38 EXPERIMENTAL METHODS FOR SLOW REACTIONSAFBIE2Fig. 28. Low-pressure mercury lamps; (a) from ref. 115, (b) from ref. 116, (c) from ref. 117.
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178 REFERENCES46 M. EIGEN AND L. DE
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182 EXPERIMENTAL METHODS FOR HETERO
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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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248 EXPERIMENT A L METHOD s F o R H
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254 EXPERIMENTAL MET HODS FOR HETER
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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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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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Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

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