The kinetics of the decarboxylation of malonic acid in normal alkanols

Autor:	Louis Watts Clark
Rok vydání:	1974
Předmět:	chemistry.chemical_classification Chemistry Decarboxylation Organic Chemistry Inorganic chemistry Enthalpy Alcohol Malonic acid Biochemistry Medicinal chemistry Inorganic Chemistry Solvent chemistry.chemical_compound Hydrocarbon Reaction rate constant Molecule Physical and Theoretical Chemistry
Zdroj:	International Journal of Chemical Kinetics. 6:713-724
ISSN:	1097-4601 0538-8066
DOI:	10.1002/kin.550060508
Popis:	Rate constants and activation parameters are reported for the decarboxylation of malonic acid in seven normal alkanols (butanol-l to decanol-l inclusive). It is found that the enthalpy of activation of the reaction is a linear function of the number of carbon atoms in the hydrocarbon chain of tthe solvent, expressed by the equation: ΔH≠ = –600n + 30,000, where n is thenumber of carbon atoms in the chain. Also an equation is developed relatingthe rate constant for the decarboxylation of malonic acid in normal alkanols to n (the number of carbon atoms in the chain): log K = 10.854283 – 0.3212674n + (131.136876n – 6556.5438)/T + log T. With the aid of this equation rate constants may be calulated for the decarboxylationof malonic acid in any alcohol at any temperature which agree with experimental values to within the limit of error of the experiments. A comparison of the data obtained in the present research for the decarboxylation of malonic acid in normal alkanols with previously reported data for the reaction in amines indicates that for reaction taking place in alcohols the transition state probably contains two molecules of solvent but only one for the reaction in amines.
Databáze:	OpenAIRE
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