Preparation of adipic acid by oxidation of cyclohexanol and cyclohexanone with nitric acid: Part II. Reaction kinetics of the decomposition of 6-hydroxyimino-6-nitro hexanoic acid

✍ Scribed by W. J. van Asselt; D. W. van Krevelen

• Publisher: Elsevier Science
• Year: 2010
• Tongue: English
• Weight: 328 KB
• Volume: 82
• Category: Article
• ISSN: 0165-0513
• DOI: 10.1002/recl.19630820502

✦ Synopsis

Abstract

The stablest intermediate product formed in the oxidation of cyclohexanol and cyclohexanone is 6‐hydroxyimino‐6‐nitro hexanoic acid (nitrolic acid). In the temperature range investigated it yields over 90% of adipic acid and N~2~O. In addition, a small amount of a still unidentified by‐product is formed at low temperatures; upon heating, the latter gives also adipic acid.

The decomposition reaction appeared to be first‐order in nitrolic acid. Nitric acid greatly influences the reaction rate; in the range of concentrations up to 50% HNO~3~, the first‐order rate constant was found to be linearly dependent on the hydrogen‐ion activity. The activation energy of the reaction amounts about 24,000 cal/gmol.