ISSN:
0001-1541
Keywords:
Chemistry
;
Chemical Engineering
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Process Engineering, Biotechnology, Nutrition Technology
Notes:
Cosolvents offer a sensitive tool to tailor equilibria, rates or yields of chemical reactions in supercritical fluid solvents. The tautomeric equilibrium of a Schiff base was chosen as a model system, and small amounts of protic cosolvents shift the position of tautomeric equilibria. The equilibrium was tuned from essentially one tautomer to another by modifying the solvent of pure SCF ethane with less than 2 mol % hexafluoroisopropanol cosolvent. The equilibrium constant was a function of cosolvent concentration and mixture density. A chemical-physical model of equilibrium constants deviates from the measured values in the near-critical region, which may have been caused by local composition enhancement of cosolvent around the Schiff base. Decrease in the degree of hydrogen bonding with pressure or density affects the keto-enol equilibria by decreasing the amount of the keto formation. Thus, solution density, as well as the degree of hydrogen bonding, is manipulated to tune the position of tautomeric equilibria.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/aic.690430224
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