Mickaël R. Simond

Dissociation Constants of Protonated Amines in Water at Temperatures from 293.15 K to 343.15 K

The dissociation constants of protonated 2-amino-1-ethanol (MEA), diethanol amine (DEA), triethanol amine (TEA), methyldiethanol amine (MDEA), 2-amino-2-methyl-1-propanol (AMP), 3-dimethylamino-1-propanol (DMAP), tris(hydromethyl)aminomethane (THAM), 2-[2-(dimethylamino)ethoxy]ethanol (DMAEOE) and, 1,2-bis(2-aminoethoxy)ethane (DiAEOE) were determined in the temperature range 293.15 to 343.15 K using a potentiometric titration method. The experimental technique was first validated using as reference the available literature data of MDEA. The dissociation enthalpies of amines were derived from their dissociation constants using the Van’t Hoff equation. Experimental dissociation constants and dissociation enthalpies were discussed in term of amine structure and compared with literature values when available.

Molecular Simulations of Primary Alkanolamines Using an Extendable Force Field

A classical force field is proposed for the molecular simulation of primary alkanolamines containing a NH(2)-C-C-OH backbone. A method is devised to take into account the polar (H-bonding) environment of the alkanolamines by calculating electrostatic charges in the presence of explicit solvent molecules. The force field does not use a universal set of charges, but is rather constructed by following a general method for obtaining specific charges for the different alkanolamines. The model is parameterized on the two simplest primary alkanolamines and then validated by calculating thermodynamic properties of five other molecules. Experimental liquid densities and enthalpies of vaporization are also reported in order to complete existing literature data. The predicted ability of the force field is evaluated by comparing the simulation results with experimental densities and enthalpies of vaporization. Densities are predicted with an uncertainty of 1.5 % and enthalpies of vaporization with an uncertainty of 1 kJ mol(-1). A decomposition of the interaction energy into electrostatic and repulsive-dispersive interactions and an analysis of hydrogen-bond statistics lead to a complex picture. Some terms of these interactions are related to the molecular structure in a clear way, others are not. The results provide insights into the structure-property relations that contribute to a better description of the thermodynamic properties of alkanolamines.

Protonation of alkanolamines and cyclic amines in water at temperatures from 293.15 to 373.15 K

Abstract The protonation properties of amines are of particular interest for the development of thermodynamic models representative of CO2 dissolution in aqueous solutions. This paper reports experimental equilibrium constants of protonation of alkanolamines (2-aminoethanol, 2,2′-iminodiethanol, 2-[bis(2-hydroxyethyl)amino]ethanol, 2-amino-2-methylpropan-1-ol, 2,2′-(methylimino)diethanol and cyclic amines (morpholine, 4-methylmorpholine, pyridine, 1-methyl-piperidine, 2-methyl-piperidine, 2,6-dimethylpiperidine). The equilibrium constants of protonation were determined by potentiometric technique up to 353.15 K and extrapolated up to 373.15 K using experimental enthalpies of protonation.

Interactions of Alkanolamines with Water: Excess Enthalpies and Hydrogen Bonding.

We report a transferable force field to describe the interactions of alkanolamines based on the N-C-C-O backbone with water, derived from a comparison with experimental excess enthalpies. This force field is tested on 2-aminoethan-1-ol (MEA), 2-amino-2-methylpropan-1-ol, 2-aminobutan-1-ol (ABU), and 1-aminopropan-2-ol. These alkanolamines are derivatives of MEA obtained by substitution with methyl and ethyl groups on the carbon atoms of the N-C-C-O backbone. A specific cross interaction site corresponding to the hydrogen bond between the hydroxyl group of the alkanolamine and the oxygen atom of water was introduced in order to reproduce quantitatively experimental excess enthalpies. The transferability of this specific site was assessed by predictions on alkanolamines that were not included in the parametrization data set. New data on enthalpy of mixing for ABU with water are reported, since they were not available in the literature. From the molecular simulations, several microscopic quantities of the alkanolamine-water mixtures were analyzed in order to improve our understanding of these systems. The structure of the solvation shells at varying compositions, statistics of hydrogen bonds, conformations, and energy decompositions served as bases for an interpretation of the molecular reasons underlying the behavior of the excess enthalpy. The prominent result is that water-water interactions play a major role in differentiating alkanolamine-water mixtures, which is a manifestation of the hydrophobic effect. Both the structural and energetic effects observed at the molecular level point to phenomena that have strong composition dependence, in particular, the interplay between the intramolecular hydrogen bond in the alkanolamine and the intermolecular hydrogen bonds with water.