Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

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4 SPECTRAL LINE-BROADENING 147(b) The intermediate region-at the coalescence point (c) the exchange broadeningis generally greatest. This corresponds to the condition r6 N 1, andA procedure often used to evaluate z is to estimate the temperature at which thelines coalesce6’. The disadvantage of this method is that the coalescence point isusually not very sharply defined.(c)“Fast” exchange-the single line sharpens. This approximation is given byz8
148 EXPERIMENTAL METHODS FOR FAST REACTIONSFig. 16. Proton resonance spectrum of pure dry ethanol (cf. ref. 64).species present in water (e.g., OH-, H,O). The exchange lifetime has been determinedfrom the temperature dependence of the c~alescence~~.The addition of a small amount of hydrochloric acid or caustic soda to pureethanol leads also to a sharpening of the OH-peak and the corresponding simplificationin the methylene band. Again, exchange of the hydroxyl proton is the causebut this time several reactions of the typeEtOH +A Z? EtO- -k AH +are involved. A comparison of the shape of the CH,-band with the theoretical curveshas led to the evaluation of the overall first order rate coefficient for the exchange byall of these reactiod4. This is divided into two components, associated with thosereactions involving water and those involving only the derivatives of ethanol. Thefrrst of these may be evaluated from the simple H2 O/EtOH exchange, and, by followingthe variations of the component first order rate coefficients with c,+ or cOH-,the second order rate coefficients for many of the individual steps have been evaluated.A third interesting observation is that in pure dry ethanol the chemical shift ofthe hydroxyl proton relative to the methylene group decreases as the temperatureis raked. This has been interpreted in the following way. In ethanol it is known thatthe hydroxyl protons are involved in hydrogen-bonding to the oxygen atoms ofother ethanol moleculesand it is reasonable that an H-bonded and a non-H-bondedproton will be subject to different magnetic shielding. If the exchange between thesetwo states is fast, the proton resonance corresponds to the average shielding forthe two states. As the temperature is altered, the proportions of ethanol moleculeshydrogen-bonded will also change, and so the resonance frequency will be temperature-dependent.This explanation is confirmed by the observation of a similareffect when a non-H-bonding solvent (e.g., chloroform) is added. Many similar“hydrogen-bond shifts” have been observed, and it is sometimes possible to obtainthe lifetime of the H-bonded state, or at least to indicate its limits6’.2. One of the surest ways of reducing the nuclear magnetic relaxation time for aspecies is to introduce aparamagnetic ion into its vicinity. The NMR spectra of aqueous
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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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Reaction Furnace CircuitI10 EXPERIM
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198 EXPERIMENTAL METHODS FOR HETERO
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202 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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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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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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