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Mechanistic study of the oxidation of N-phenyldiethanolamine by bis(hydrogen periodato)argentate(III) complex anion

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Abstract

The kinetics of oxidation of phenyldiethanolamine (PEA) by a silver(III) complex anion, [Ag(HIO6)2]5−, has been studied in an aqueous alkaline medium by conventional spectrophotometry. The main oxidation product of PEA has been identified as formaldehyde. In the temperature range 20.0–40.0 °C , through analyzing influences of [OH−] and [IO −4 ]tot on the reaction, it is pseudo-first-order in Ag(III) disappearance with a rate expression: k obsd = (k 1 +  k 2[OH−]) K 1 K 2[PEA]/{f([OH−])[IO −4 ]tot + K 1 + K 1 K 2 [PEA]}, where k 1 =  (0.61 ± 0.02) × 10−2 s−1, k2 = (0.049 ± 0.002) M−1 s−1 at 25.0 °C and ionic strength of 0.30 M. Activation parameters associated with k 1 and k 2 have also been derived. A reaction mechanism is proposed involving two pre-equilibria, leading to formation of an Ag(III)-periodato-PEA ternary complex. The ternary complex undergoes a two-electron transfer from the coordination PEA to the metal center via two parallel pathways: one pathway is spontaneous and the other is assisted by a hydroxide ion.

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Authors and Affiliations

  1. College of Chemistry and Environmental Science, Hebei University, Baoding, Hebei Province, 071002, P.R. China

    Shigang Shen, Hongmei Shi, Hanwen Sun & Shuying Huo

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  1. Shigang Shen
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  2. Hongmei Shi
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  3. Hanwen Sun
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  4. Shuying Huo
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Correspondence to Shigang Shen.

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Shen, S., Shi, H., Sun, H. et al. Mechanistic study of the oxidation of N-phenyldiethanolamine by bis(hydrogen periodato)argentate(III) complex anion. Transition Met Chem 32, 167–171 (2007). https://doi.org/10.1007/s11243-006-0144-8

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  • DOI: https://doi.org/10.1007/s11243-006-0144-8

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