- Proton Acidity and Chemical Reactivity in Molten Salt Hydrates
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Molten Ca(NO3)2*4H2O has been used as a model system for studies of proton acidity and chemical reactions (including ester hydrolyses and aromatic nitrations) in molten salt hydrates.Increases in proton acidity caused by addition of acidic hydrates such as AlCl3*6H2O and Cd(NO3)2*4H2O or of aqueous HNO3 can be quantified in terms of changes in Hammett acidity H0, but usually not by the downfield shifts observed in the NMR spectrum.The rates of hydrolysis of selected primary esters (e.g., n-octyl acetate) were found to be linearly dependent on nitric acid concentration, indicating that the acidity of these melts can be changed with little change in water activity.The measurement of kinetic parameters is complicated, however, by side reactions between the organic substrates and HNO2, NO2 (or NO2+) and other species originating from the nitrate ions in the melt.
- Franzyshen, S. K.,Schiavelli, M. D.,Stocker, K. D.,Ingram, M. D.
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p. 2684 - 2688
(2007/10/02)
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- Alkyl Nitrate Formation from the NOx-Air Photooxidations of C2-C8 n-Alkanes
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The yields of alkyl nitrates formed in the NOx-air photooxidations of the homologous series of n-alkanes from ethane through n-octane have been determined at 299 +/- 2 K and 735 torr total pressure for two different chemical systems.Alkyl peroxy radicals were generated by reaction of the n-alkanes with OH radicals (generated from the photolysis of methyl nitrite in air) or Cl atoms (from photolysis of Cl2 in air).The alkyl nitrate yields obtained from the two systems, corrected for secondary reactions, were in agreement within the experimental errors and increased monotonically with the carbon number of the n-alkane, from x-air photooxidations of the large n-alkanes.
- Atkinson, Roger,Aschmann, Sara M.,Carter, William P. L.,Winer, Arthur M.,Pitts, James N.
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p. 4563 - 4569
(2007/10/02)
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