Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

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4 ANALYSIS 97lysis. However, Maccoll et a1.321 have applied it in the investigation of the gasphaseracemisation of 2-chloro-octane during HCl elimination, to check the ideaof a polar transition state.D - ( +) -CsH 1, C11L2-+c2L-(-)-C8H17dlC~HL~+HC~If a, and a, are the rotations at a time t and zero, respectively, then k2 is determinedfrom equation (0')a,/ao = exp -(kl +2k,),(0')k, is separately determined from pressure measurements.4.5.3 Conductance measurementsThese have been used for a few studies of ionic reactions in solution, for example,the classical work on the saponification of esters.Some gases may be determined by dissolution in an appropriate solution followedby conductance measurements. Carbon dioxideSZZ and hydrogen chloride3'have' been determined this way be dissolving in barium hydroxide solution andwater respectively. HQ may be estimated with precision in amounts as low as0.1-1 pmole. This method has been used to determine HCl in molecular beamreactions of hydrogen atoms with CCI,, Cl,, etc.4.5.4 Thermal conductivityZH situ thermal conductivity measurements have been used to determine324 theextent of the equilibrium in reaction (62)N204 2N02 (62)over the temperature range 32-90" C. The conversion of hydrogen and carbonmonoxide to methanol has also been followed in this wayJz5. The use of thermalconductivity in GLC and GSC analysis has already been referred to.4.5.5 CalorimetryThe rate of very exothermic reactions, such as oxidation and combustion pro-References pp. 104-111
98 EXPERIMENTAL METHODS FOR SLOW REACTIONSry-ReactantentryMcLeodgauges .IIThermostatting JacketVacuum JacketMoveable detector\Fixed detectorFig. 68. Isothermal calorimeter. From ref. 328.cesses, may be followed by measuring the heat evolved. For gas-phase reactionsthe change in resistance of a thin metal wire may be measured as a function oftime. The wire is enclosed in a thin Pyrex or silica1 sleeve and suspended in theRV. Van~eC~’~ has shown that the change in temperature may be related to thechange in pressure for several oxidation reactions.The combination of atoms or radicals liberates a considerable amount of heatdue simply to the energy of bond formation. At low pressures this will take placeheterogeneously. Hence this presents a method of detecting free radicals or atoms
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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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4 EXPERIMENTAL METHODS FOR SLOW REA
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8EXPERIMENTAL METHODS FOR SLOW REAC
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Reaction Furnace CircuitI10 EXPERIM
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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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194 EXPERIMENT A L MET H o D s F o
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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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236 EXPERIMENT A L METHOD s FOR HE
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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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266 EXPERIMENT A L MET H o D s F o
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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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Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

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