Solvation of Dimethyl Succinate in a Sodium Hydroxide Aqueous Solution. A Computational Study

Journal Article · Thu May 07 04:00:00 EDT 2009 · Journal of Physical Chemistry B, 113(18):6473–6477

DOI:https://doi.org/10.1021/jp901950g· OSTI ID:963589

Sun, Xiuquan; Chang, Tsun-Mei; Cao, Yang; Niwayama, Satomi; Hase, William L; Dang, Liem X

Molecular dynamics simulations were carried out to study dimethyl-succinate/water/NaOH solutions. The potential of mean force method is used to determine the transport mechanism of a dimethyl-succinate (a diester) molecule across the aqueous/vapor interface. The computed number density profiles show a strong propensity for the diester molecules to congregate at the interface with the solubility of the diester increasing with increasing NaOH concentration. It is observed that the major contribution to the interfacial solvation free energy minimum is from van der Waals interactions. Thus, even at higher NaOH concentrations, the increasing electrostatic interaction between the diester and ions is not large enough to overcome the Lennard-Jones (LJ) interactions to favor the solvation of diester in bulk solutions. The calculated solvation free energies are found to be -2.6 ~ -3.5 kcal/mol in variant concentrations of NaOH aqueous solutions. These values are in qualitative agreement with the corresponding experimental measurements. The computed surface potential indicates that the contribution of diester molecules to the total surface potential is about 25%, with the major contribution from interfacial water molecules. This work was supported by the US Department of Energy (DOE) Office of Basic Energy Sciences, Chemical Sciences program. Pacific Northwest National Laboratory is operated by Battelle for DOE.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 963589
• Report Number(s): PNNL-SA-64356; KC0301020
• Journal Information: Journal of Physical Chemistry B, 113(18):6473–6477, Journal Name: Journal of Physical Chemistry B, 113(18):6473–6477 Journal Issue: 18 Vol. 113
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
AQUEOUS SOLUTIONS
CARBOXYLIC ACID ESTERS
ELECTROSTATICS
FREE ENERGY
MOLECULAR DYNAMICS METHOD
SODIUM HYDROXIDES
SOLUBILITY
SOLVATION
SURFACE POTENTIAL