Dissociation Constants (pKa) of Tertiary and Cyclic Amines: Structural and Temperature Dependences

The dissociation constants of the conjugate acids of 14 amines (diethylethanolamine, monoethanolamine, n-butyldiethanolamine, t-butyldiethanolamine, n,n-dimethylpropanolamine, methyl-diethanolamine, ethyldiethanolamine, monoethylethanolamine, n,n-dimethylisopropanolamine, triethanolamine, 4-methylpiperazine-1-amine, 3-morpholino propylamine, 4,2-hydroxylethylmorpholine, and triethylamine) were measured over a temperature range between 293.15 and 333.15 K using the potentiometric titration method. The change in standard state thermodynamic properties was derived from the van’t Hoff equation. The influence of the steric hindrance, number of −OH groups, and length of alkyl chain on the dissociation constants was identified. Of the studied amines, few sterically hindered derivatives of piperazine, a secondary amine monoethylethanolamine, and a tertiary amine n,n-dimethylpropanolamine have high pKa values but lower standard enthalpy than those of the benchmark amine, monoethanolamine (MEA), and thus were deeme...