scholarly journals Viscosity of Water +tert-Butyl Alcohol (2-Methyl-2-propanol) Mixtures at Low Temperatures and High Pressure

2009 ◽  
Vol 54 (6) ◽  
pp. 1961-1962 ◽  
Author(s):  
Kenneth R. Harris ◽  
Lawrence A. Woolf



1974 ◽  
Vol 52 (10) ◽  
pp. 1925-1933 ◽  
Author(s):  
Jay E. Taylor ◽  
John C. Weygandt

The high pressure (< 136 atm) and high temperature (< 250°) reactions of elemental oxygen with aqueous solutions of selected soluble alcohols, ketones, and acids have been examined in detail for the first time. Saturated acids and methyl alcohol are not oxidized under the imposed conditions. The end product for the oxidation of ketones and primary alcohols is mainly carbon dioxide at 200 °C; however, appreciable yields of acids are obtained at 250 °C. tert-Butyl alcohol and secondary alcohols form the corresponding ketones which are then further oxidized. Those alcohols and ketones which were studied quantitatively all exhibited second-order kinetics, first order in organic compound and first order in oxygen. The compounds are listed below in the order of decreasing rate at 200°, ΔH≠ in kcal/mol and ΔS≠ in entropy units are noted in parentheses: 2-butanone (16.0, −25) > tert-butyl alcohol (24.2, −9) > cyclopentanone (12.4, −36) > isobutyl alcohol (21.5, −17) > sec-butyl alcohol (23.9, −15) > n-butyl alcohol > (21.3, −22) > acetone (15.1, −37). The alcohols have both higher entropies and enthalpies of activation than the ketones. Two non-chain mechanisms are proposed. (I) A ketone equilibrates with its enol which oxidizes to a metastable oxygenated intermediate. At 250° the intermediate decomposes to an acid or at 200° it is further oxidized to carbon dioxide. (II) Alcohols oxidize by an initial bimolecular mechanism to the corresponding ketone or aldehyde which may then be oxidized further.



1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.



2021 ◽  
pp. 116913
Author(s):  
Márcio José da Silva ◽  
Diego Morais Chaves ◽  
Sukarno Olavo ferreira ◽  
Rene Chagas da Silva ◽  
Jose Balena Gabriel Filho ◽  
...  




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