Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

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2 THE SOLID-GAS INTERFACE 19320 30 40 50 60 70 80 90 100(n=52X10'2)3oo 'p 1 1 I 1 I 1 I I 1ni 52x1d2120x10'~ molecutes.cni2-5: 0.45n @ €0mole. cdmir? kca1.r;52~10'~ 0 - "Ol6'169 00094~10~~ 6586 0.31 60103 0.67 5.9120 2.02 5.8137 4.68 5.7b Ib 2'0 30 40 do $0 :o A0 do (njl2OXld4lmplngernent rate (15W(1032 rnotecutes. ctfi2min3Fig. 4. Net rate of adsorption as a function of impingement rate. Xe at TG = 300" K on tungsten- 80" K. Slope = sticking coefficient kA; intercept = evaporation rate = FF/A. From ref. 88.Fig. 5. Pressure cycle in flow system during adsorption on sample of unit area. Q,, amount ofgas added to cell during adsorption interval il--to; Q,, amount lost during desorption intervali2-tl; SE, exit speed; FA, rate of gas entry from reservoir. From ref. 88.References pp. 270-278
194 EXPERIMENT A L MET H o D s F o R HE T E R o GE NE o u s RE A c T I o N sIf desorption is complete before gas can leave the system, (i.e. Q, = 0), the gasdensity rises to a peak (N2-Nt) giving the amount of gas adsorbed directly.Such rapid heating is not essential for determining the amount adsorbed. Whenthe original steady state is restored N, = No, Qi = Q, and the shaded areas inFig. 5 must be equal. The identity of these two quantities serves as a convenientcheck on experiment.The ideal systems described are difficult to achieve in practice. In a real closedsystem adsorption occurs on the walls and gas is pumped by the pressure gauge.The walls may degass as the pressure falls, presenting a difficult problem. Thereforethe equation for a closed system is really represented by the equation for a flowsystem, where FA and S, now denote gas flow or pumping of any type other thanthat due to adsorption on the filament. Closed systems are also limited becausefor a given initial pressure, only a small range of surface concentrations can bemeasured. Fig. 6 shows a typical apparatus for adsorption measurements. Theflow into the adsorption cell is controlled by valve V, and the pumping rate can bealtered by adjusting the magnetically operated valve E. A much higher pressureis maintained in the gas reservoir B so that the admittance rate does not fallduring the experiment. In order to avoid pressure gradients, the gauge and filamentmust be brought close together, the limit being set by the need to shield thefilament from heat generated by the gauge and from stray electrons.The type of apparatus described can also be used for making desorption studies.Because the heating of the sample, to effect desorption, changes the temperatureof the flament, processes which occur at different temperatures can be recognised.6 1E111 IFig. 6. Flow system for adsorption studies, with independent control of entrance and exit speed.F, adsorption sample; I, ionisation gauge. Flow out of gas reservoir (B) and into cell controlledby valve VA; gas flow out of cell regulated by adjustable exit port E. From ref. 88.
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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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22 EXPERIMENTAL METHOD§ FOR SLOW R
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~~ ~36 EXPERIMENTAL METHODS FOR SLO
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100 EXPERIMENTAL METHODS FOR SLOW R
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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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244 EXPERIMENTAL 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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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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346 TREATMENT OF EXPERIMENTAL DATAp
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348 TREATMENT OF EXPERIMENTAL DATAg
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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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