A simple McGowan specific volume correction for branching in hydrocarbons and its consequences for some other solvation parameter values

• Published in: Chemosphere (Oxford) 2011-08, Vol.84 (8), p.1102-1107
• Main Authors: van Noort, Paul C.M., Haftka, Joris J.H., Parsons, John R.
• Format: Article
• Language: English
• Subjects: acyclic alkanes; additives; Air; Alkanes; Alkanes - chemistry; amines; Applied sciences; Branched; Branching; Carbon; chemical bases; chromatography; Density; descriptors; energy; energy relationship lser; Ethers; Exact sciences and technology; fuels; hexadecane; Hydrocarbons - chemistry; isomers; LSER; Models, Chemical; octanol; organic-compounds; partition coefficients; Partitioning; Partitions; phase; Pollution; pp-LFER; prediction; solubility; Solvation; Solvents - chemistry; Specific volume; Substituent effects; surfactants; Vapor Pressure; water
• ISSN: 0045-6535; 1879-1298
• DOI: 10.1016/j.chemosphere.2011.04.042

► McGowan specific volumes can easily be corrected for buried atoms. ► No correction needed for buried sp 2 carbons. ► McGowan volumes when corrected lead to chemically more logical values for the A and B Abraham solvation parameters. Differences in molecular properties between linear and branched alkanes as well as between compounds with branched alkyl groups is of relevance due to the large number of branched isomers of environmentally relevant compounds (e.g. fuels, fuel additives, surfactants). For branched alkane vapor pressures, the McGowan specific volume is a poor predictor. Therefore, in this study a correction on the McGowan specific volume is derived in terms of the number of branches and the number of pairs of vicinal branches to improve the prediction of branched alkane vapor pressures. This branching correction also brought branched /alkane solvent accessible volumes, octanol/water partition coefficients, air/hexadecane partition coefficients, and aqueous solubilities as well as alkyl-branched substituted aliphatic hydrocarbon air/hexadecane partition coefficients more in line with corresponding linear hydrocarbon properties when compared on a McGowan specific volume basis. Even for air–hexadecane partition coefficients of substituted aliphatic hydrocarbons with substituents at non-terminal carbons, application of the branching correction to the carbon bearing the substituent caused these partition coefficients to be more in line with those for linear compounds. Values for the Abraham A and B solvation parameters for nonlinear aliphatic ethers, amines, and alcohols, recalculated using branching corrected McGowan specific volumes, turned out to be closer to chemical expectations based on linear aliphatic ether, amine and alcohol values compared to previously reported experimental values obtained using uncorrected McGowan specific volumes. A comparison of alkylbenzene and alkene partition coefficient estimates from two different linear solvation energy relations, one containing a McGowan specific volume term and one without such a term, suggests that no branching correction is needed for alkyl groups at sp 2 carbons. The main advantage of using branching corrected McGowan specific volumes is that the values of other solvation parameters become chemically more consistent.