Experimental and theoretical enthalpies of formation of glycine-based sulfate/bisulfate amino acid ionic liquids.

ABSTRACT

The experimental and theoretical enthalpies of formation of several structural-similar glycine-based sulfate/bisulfate amino acid ionic liquids including glycine sulfate (Gly(2)SO(4), 1), glycine bisulfate (GlyHSO(4), 2), N,N-dimethylglycine sulfate ([DMGly](2)SO(4), 3), N,N-dimethylglycine bisulfate ([DMGly]HSO(4), 4), N,N-dimethylglycine methyl ester sulfate ([DMGlyC(1)](2)SO(4), 5), N,N-dimethylglycine methyl ester bisulfate ([DMGlyC(1)]HSO(4), 6), N,N,N-trimethylglycine methyl ester sulfate ([TMGlyC(1)](2)SO(4), 7), and N,N,N-trimethylglycine methyl ester bisulfate ([TMGlyC(1)]HSO(4), 8) were studied. Their experimental enthalpies of formation were obtained from the corresponding energies of combustion determined by the bomb calorimetry method. The enthalpies of formation of these amino acid ionic liquids are in the range from -1406 kJ mol(-1) to -1128 kJ mol(-1). Systematic theoretical study on these amino acid ionic liquids were performed by quantum chemistry calculation using the Gaussian03 suite of programs. The geometric optimization and the frequency analyses are carried out using the B3LYP method with the 6-31+G** basis set. Their calculated enthalpies of formation were derived from the single point energies carried out with the HF/6-31+G**, B3LYP/6-31+G**, B3LYP/6-311++G**, and MP2/6-311++G** level of theory, respectively. The relevance of experimental and calculated enthalpies of formation was studied. The calculated enthalpies of formation are in good agreement with their experimental data in less than 3% error.