Interaction between carbon dioxide and naphthalene: A molecular modeling approach

Abstract

The formation of a charge‐transfer complex between carbon dioxide and naphthalene was studied using a molecular modeling program, with the aim of studying the solubility of naphthalene in supercritical carbon dioxide. The orbitals involved in the formation of the complex were studied using MINDO/3 as the semi‐empirical method. A solvent cage was constructed, and the maximum number of carbon dioxide molecules to surround naphthalene was found to be 20. The heat of interaction of the complex was obtained using MINDO/3. © 1994 by John Wiley & Sons, Inc.

Partial Molar Volume and Solvation Structure of Naphthalene in Supercritical Carbon Dioxide: A Monte Carlo Simulation Study

“…This is to be expected since the experimental pressure is approximately halfway between the two simulation pressures. Although an eight-membered ring of CO 2 molecules with molecular axes perpendicular to the plane of the naphthalene molecule (see Figure of ref ) was found to be consistent with the experimental scattering data, the orientation was based upon a gas-phase cluster calculation without temperature effects, that is, at 0 K 6 Structure factors for the systems containing N naph = 0 (upper) and 4 (lower) naphthalenes at T = 308.38 K and p = 87.8 (solid lines) and 310.2 bar (dotted lines).…”

“…To improve SCF processes, it is of great technological importance to understand the microscopic details of the solvation mechanism of SCFs. Of great interest is whether the distribution of supercritical solvent molecules is relatively homogeneous on the microscopic scale or whether there is a pronounced clustering of solvent molecules around solutes. − In a pioneering study, Eckert and co-workers experimentally measured the partial molar volume at infinite dilution of naphthalene, C 10 H 8 , dissolved in sc-CO 2 at temperatures of 308.38 and 318.15 K and pressures ranging from 74.6 to 373.0 bar . They reported large, negative partial molar volumes near the critical pressure, that is, the system volume decreases substantially upon addition of solute molecules.…”

Proton affinities of polybenzenoid aromatic hydrocarbons and those with five-membered rings

“…As PAHs ab initio calculations are time consuming, only few low level calculations have been reported. 10,11 Finally, calculated PAs were compared with experimental values in the literature, 7 and newly determined after our method. 6 …”

Molecular Modeling Approach for Contrasting the Interaction of Ethane and Hexafluoroethane with Carbon Dioxide

“…Molecular modeling has become a useful tool for understanding the interaction of different molecules under controlled conditions, and a number of different types of computer simulations have been used to understand the solvent/solvent and solvent/solute interactions in supercritical carbon dioxide. Recently, molecular modeling calculations using MINDO/3, a semiempirical method, have been utilized to study the interaction of carbon dioxide with naphthalene, and evidence for the formation of a charge transfer complex was found and through ab initio calculations, the solubility of various organic compounds was found to depend on the total variance of the electrostatic potential on the molecular surface and on the molecular volume …”

“…Recently, molecular modeling calculations using MINDO/3, a semiempirical method, have been utilized to study the interaction of carbon dioxide with naphthalene, and evidence for the formation of a charge transfer complex was found. 12 Monte Carlo simulations have also been utilized to quantify the "structure" of the carbon dioxide molecules in condensed fluid phases, 13 and through ab initio calculations, the solubility of various organic compounds was found to depend on the total variance of the electrostatic potential on the molecular surface and on the molecular volume. 14 In an effort to pursue further the possible specific interactions between fluorinated compounds and carbon dioxide, ab initio calculations were performed comparing the interactions of two simple systems, ethane/carbon dioxide and hexafluoroethane/ carbon dioxide.…”