Lauryl alcohol, esterification

The failure to fit the data over the complete conversion range from 0 to 100% to a third-order plot has sometimes been ascribed to failure of the assumption of equal functional group reactivity, but this is an invalid conclusion. The nonlinearities are not inherent characteristics of the polymerization reaction. Similar nonlinearities have been observed for nonpolymerization esterification reactions such as esterifications of lauryl alcohol with lauric or adipic acid and diethylene glycol with caproic acid [Flory, 1939 Fradet and Marechal, 1982b]. 

Flory [3, 48] found that the esterification reactions between model compounds on the one hand and polyfunctional reactants on the other are substantially identical. Thus the reaction of two monofunctional compounds (lauric acid, lauryl alcohol), of a bifunctional compound with a monofunctional one (adipic acid, lauryl alcohol) and two bifunctional compounds (adipic acid, decamethylene glycol) followed essentially third-order kinetics. In the absence of added strong-acid catalyst a second molecule of the carboxylic acid functions as catalyst. Thus when the concentrations (C) of the reacting groups are identical, the rate is given by ... 

In the presence of an added catalyst such as p-toluenesulphonic acid, simple esterification reactions and polyesterification reactions are second order [48]. Thus the kinetics of the catalysed reaction of lauric acid and lauryl alcohol in a medium of lauryl laurate closely parallels those of the polymer-forming reaction between adipic acid and 1,10-dodecanediol in a medium of polyester product. Second-order rate coefficients for the two reactions were [35], respectively, 45x10 equiv kg" sec and 16 X 10" equiv kg" sec . 

Nobel Prize winner Paul Flory studied the kinetics of several poly esterification reactions in a BR, on a laboratory scale. The experimental data of esterification of adipic acid with lauryl alcohol are given in the table below. Initial concentrations of the reactants were 1.0 mol/L. The reaction kinetics can be described with the rate expression... 

The following data were obtained for the uncatalyzed equimolar esterification (Hamann et al.,1968) of laiuyl alcohol (b = 0.200 mol) with lauric add (a = 0.200 mol) in lauryl laurate at 163°C. 

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