The kinetics of the decarboxylation of malonic acid in normal alkanols

✍ Scribed by Louis Watts Clark

• Publisher: John Wiley and Sons
• Year: 1974
• Tongue: English
• Weight: 496 KB
• Volume: 6
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550060508

✦ Synopsis

Abstract

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: Δ__H__^≠^ = –600__n__ + 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 – 0.3212674__n__ + (131.136876__n__ – 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.