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February 2, 2018 | Chemistry | By admin | 0 Comments

By R.C. Arridge, P.J. Barham, M. Kawaguchi, J. Kolarik, A. Takuhashi

ISBN-10: 3540116400

ISBN-13: 9783540116400

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Petit and Bessiere have studied the redox behavior of iodine in HOTFA containing Et 4 NC10 4 or NaOTFA by voltammetry using glassy carbon and rotating shiny platinum indicator electrodes. 149 They showed that iodine is directly reduced to iodide, with no intermediate triodide formation, but that iodide cannot be oxidized electrochemically in dry HOTFA to which a small amount of anhydride has been added. Iodine is shown to be oxidized to the + I state I 2 + 2HOTFA + 2C10 4 - - 2e" -> 2IOTFA + 2HC10 4 (44) 38 JOHN B.

For these reasons solvolytic displacement reactions proceed predominantly by the SN1 mechanism. The solvent is more "limiting" in this sense241 than formic or acetic acids which impart an SN2 character to the solvolysis. Bentley et al242 have measured the relative nucleophilicities for various media based on the 42 JOHN B. MILNE solvolysis of methyl tosylate. They find that HOTFA has a nucleophilicity comparable to that of fluorosulfuric acid, HS0 3 F, but much lower than that of formic and acetic acids.

Hara and Cady152 determined the approximate solubilities for a variety of salts and these are given in Table XII. Noteworthy for their exceptionally low solubility in HOTFA compared to water are the dipositive metal sulfates and sodium and zinc perchlorates. 4 Reproduced with permission of Academic Press. 2 1. 1 g/100 g CF 3 COOH Halogenides: CaF 2 , PbF 2 , MnF 2 , FeF 3 , AgCl, ZnCl2, A1C13, PbCl2, HgCl2 Perchlorates: Na, K, Zn Periodates: Na, K Sulfates: Be, Mg, Ca, Ba, Zn, Ni, Co, Fe(II), Cu(II) Others: Ce 2 (C 2 0 4 ) 3 9H 2 0, BaS 2 0 6 2 H 2 0 a Reproduced with permission of the American Chemical Society from Hara and Cady.

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Behavior Of Macromolecules by R.C. Arridge, P.J. Barham, M. Kawaguchi, J. Kolarik, A. Takuhashi


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