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Example text

Further difficulties in the interpretation of the Grunwald-Winstein m values arise because the solvent itself could almost certainly be involved in the mechanism of the standard reaction. 78. 0,ethanollwater 90, 80, 70, 50, 30, 0% increasing Y ; U, methanollwater 100, 90, 70, 50, 30% increasing Y 38 Chapter 2 of change in solvent required to estimate rn. The first problem was recognised by Bentley and Schleyer3' who suggested that nucleophilic assistance to dissociation occurs in the original standard reaction, as well as a complication due to an elimination reaction.

Similar arguments show that the Brransted p for a proton transfer reaction is the same as the Leffler a for that reaction. The principle of microscopic reversibility*' dictates that the reverse Chapter 2 30 step of a general acid-catalysed reaction" is general base catalysed. There is a simple relationship between values of the Brmnsted coefficients a and p for the forward and reverse reactions respectively, and this may be derived using the example of enolisation of acetone (Equation 36). The equilibrium constant for the formation of enolate ion is given by the so that the Brarnsted relationships equation Keg= kA/kHA (= KaHs/KaHA) (Equations 37 and 38) may be combined.

3 Equation ( 5 ) governs the combined inductive, steric (9 and resonance (R) effects on the rate of a Equations (6) and (7) can be written for baseand acid-catalysed hydrolysis using methyl (Me) as the standard substit uent. 48 in order that o* values approximate to the corresponding Hammett o constants. 48 is the difference between the Hammett p values for base- and acid-catalysed hydrolysis of ethyl benzoates. Thus: Reasonable assumptions necessary for the Taft analysis are: That the additivity expressed by Equation ( 5 ) is valid.

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Angular Scattering of Electrons in Hydrogen and Helium by Harnwell G. P.


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