Kinetics of the formation of symmetrical wax esters from the corresponding alcohols with the use of hydrobromic acid and hydrogen peroxide

摘要

The primary aliphatic alcohols n-octanol, n-decanol, and n-dodecanol have been converted to their corresponding symmetrical esters by using HBr and H2O2 in the absence of a solvent. The reaction was carried out at 30, 40, and 50°C and at mole ratios of alcohol to HBr of 1∶0.1, 1∶0.2, 1∶0.3, and 1∶0.5. The rate of the reaction was found to increase with increase in the reaction temperature and concentration of HBr. The maximal conversion of n-octanol was 72% at 40°C and a mole ratio of n-octanol to HBr of 1∶0.5. The kinetics of the reaction have been established, and the reaction was found to be first-order with respect to alcohol and bromine concentration in the organic phase, and second-order with respect to both. The second-order rate constants for n-octanol, n-decanol, and n-dodecanol are 27.08, 32.58, and 37.42 mL mol−1 min−1, respectively, at 40°C. The activation energy for the esterification reaction of n-octanol was found to be 16.32 kcal mol−1.