Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

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3 MASS SPECTROMETRY 303Gas samplingsystemIonsourceCapacity 1pickupI analyzer [Fig. 8. Block diagram of mass spectrometer employing a chopped beam technique.investigation of metastable, electronically excited oxygen molecules, Oz('A,), asdescribed earlier9*.Molecular beam formation from flames at 1 atmosphere has been discussed.Greene et aI.'ozs lo' used several slits together with differential pumping betweenthe stages. Typical dimensions of the apertures and pressures used by these workersare given in Table 1: the apparatus to which they refer is shown in Fig. 9.Schiff and his colleagues have used, inter alia, mass spectrometric methods tostudy atom reactions in discharge flow systems: reactions of atomic oxygeng9~"',nitrogen'. '6 log and hydrogen7 have been investigated so far by Schiffs group.The basic apparatus used is described in detail in ref. 109. A sampling leak, consistingof a 20 x 20 p cylindrical hole in a pyrex thimble, was fixed in a positionrelatively far downstream in the flow tube. One reactant, usually atoms diluted bytheir molecular precursor, flowed down this tube, and the second reactant couldbe admitted to the flow tube through an inlet jet whose position in the main tubewas adjustable. Since distance in a flow experimknt corresponds to time of reaction,the mass spectrometer leak samples the reaction mixture at various reaction times,and rates of atom reactions can be calculated from the experimental data. Theapparatus has been used to study the reactions N+03, N+NO, 0+03, O+NOZ'O9, H+NOz, H+037, O+02+Oz117, together with investigations of theReferences pp. 336-342
304 DETECTION AND ESTIMATION OF INTERMEDIATESElectron beamwectrometerslitsMass SPeCtrOmetera4 (collimating slit)-a3(collimattng slit 1a, (sampling orifice)Fig. 9. Sampling device for flames burning at one atmosphere.TABLE 1OPERATING CONDITIONS OF APPARATUS SHOWN IN FIo. 9(a) DimensionsFigure reference Physical size (mm) Distance from electronbeam (mm)0.25 (diameter)0.25 (diameter)0.50X 90.75 x 12400394344113(b) PressuresChamberPressure (torr)Source 7x10;Stage 1lo-'Stage 2 3 x 10-5Stage 33 x lo4Ion source 10-1
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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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12 EXPERIMENTAL METHODS FOR SLOW RE
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Chapter 2Experimental Methods for t
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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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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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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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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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