Matches in SemOpenAlex for { <https://semopenalex.org/work/W1964792413> ?p ?o ?g. }
Showing items 1 to 58 of
58
with 100 items per page.
- W1964792413 endingPage "289" @default.
- W1964792413 startingPage "283" @default.
- W1964792413 abstract "Abstract The oxidation of formic acid to carbon dioxide and water in acetic acid-lithium acetate solution with palladium(II) catalysts was studied. The reaction was carried out in the presence of cupric salts and oxygen to reoxidize elementary palladium: (1) HCOOH + Pd(II) → C02 + Pd0 + 2H+; (2) Pd0 + Cu(II) → Cu(I) + Pd(II); (3) 2Cu(I) + 2H + + 1 2 O 2 → 2 Cu(II) + H 2 O . Under conditions in which the reaction represented by Eq. (1) was rate-determining the reaction rate was directly proportional to formic acid, palladium(II) concentration and approximately directly proportional to lithium acetate concentration. With excess lithium acetate the rate expression became zero order in acetate: −d[ HCOOH ] dt = k [ Pd(II)] [HCOOH] and k was found to be 0.12 1 mole(su−1) sec(−1) at 112 °C. From the variation of k with temperature, values of ΔH ‡ = 22 kcal mole −1 and ΔS DG = −6 cal mole −1 deg −1 were calculated. The deuterium isotope effect for DCOOH was determined to be k[ H ] k[ D ] = 2.0 at 112 °C . A mechanism is proposed in which the rate-limiting step is the decomposition of a palladium(II)-formate complex. This complex decomposes either via a two-electron transfer from the coordinated formate ion coupled with proton loss, or via a palladium(II) hydride complex which then decomposes rapidly. Similar mechanisms had been proposed by other authors for the oxidation of formic acid with thallium(III), mercury(II), and mercury(I)." @default.
- W1964792413 created "2016-06-24" @default.
- W1964792413 creator A5002424122 @default.
- W1964792413 date "1969-03-01" @default.
- W1964792413 modified "2023-09-26" @default.
- W1964792413 title "Palladium(II)-catalyzed oxidation of formic acid in acetic acid solution*1" @default.
- W1964792413 cites W1409897175 @default.
- W1964792413 cites W1984965026 @default.
- W1964792413 cites W2049304847 @default.
- W1964792413 cites W2087325513 @default.
- W1964792413 cites W2324684798 @default.
- W1964792413 cites W2329060468 @default.
- W1964792413 cites W2333202324 @default.
- W1964792413 cites W324317825 @default.
- W1964792413 doi "https://doi.org/10.1016/0021-9517(69)90402-3" @default.
- W1964792413 hasPublicationYear "1969" @default.
- W1964792413 type Work @default.
- W1964792413 sameAs 1964792413 @default.
- W1964792413 citedByCount "16" @default.
- W1964792413 countsByYear W19647924132016 @default.
- W1964792413 countsByYear W19647924132023 @default.
- W1964792413 crossrefType "journal-article" @default.
- W1964792413 hasAuthorship W1964792413A5002424122 @default.
- W1964792413 hasConcept C161790260 @default.
- W1964792413 hasConcept C178790620 @default.
- W1964792413 hasConcept C179104552 @default.
- W1964792413 hasConcept C185592680 @default.
- W1964792413 hasConcept C2776673659 @default.
- W1964792413 hasConcept C2777379063 @default.
- W1964792413 hasConcept C502130503 @default.
- W1964792413 hasConceptScore W1964792413C161790260 @default.
- W1964792413 hasConceptScore W1964792413C178790620 @default.
- W1964792413 hasConceptScore W1964792413C179104552 @default.
- W1964792413 hasConceptScore W1964792413C185592680 @default.
- W1964792413 hasConceptScore W1964792413C2776673659 @default.
- W1964792413 hasConceptScore W1964792413C2777379063 @default.
- W1964792413 hasConceptScore W1964792413C502130503 @default.
- W1964792413 hasIssue "3" @default.
- W1964792413 hasLocation W19647924131 @default.
- W1964792413 hasOpenAccess W1964792413 @default.
- W1964792413 hasPrimaryLocation W19647924131 @default.
- W1964792413 hasRelatedWork W1987143962 @default.
- W1964792413 hasRelatedWork W1998388877 @default.
- W1964792413 hasRelatedWork W1999602177 @default.
- W1964792413 hasRelatedWork W2007720516 @default.
- W1964792413 hasRelatedWork W2016326302 @default.
- W1964792413 hasRelatedWork W2055740898 @default.
- W1964792413 hasRelatedWork W2084578167 @default.
- W1964792413 hasRelatedWork W2170326120 @default.
- W1964792413 hasRelatedWork W2404647648 @default.
- W1964792413 hasRelatedWork W3146713903 @default.
- W1964792413 hasVolume "13" @default.
- W1964792413 isParatext "false" @default.
- W1964792413 isRetracted "false" @default.
- W1964792413 magId "1964792413" @default.
- W1964792413 workType "article" @default.