title: Experimental determination of solvent-water partition coefficients and Abraham parameters for munition constituents.
abstract: There is concern about the environmental fate and effects of munition constituents (MCs). Polyparameter linear free energy relationships (pp-LFERs) that employ Abraham solute parameters can aid in evaluating the risk of MCs to the environment. However, poor predictions using pp-LFERs and ABSOLV estimated Abraham solute parameters are found for some key physico-chemical properties. In this work, the Abraham solute parameters are determined using experimental partition coefficients in various solvent-water systems. The compounds investigated include hexahydro-1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX), hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX), hexahydro-1,3-dinitroso-5- nitro-1,3,5-triazine (DNX), 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitrobenzene (TNB), and 4-nitroanisole. The solvents in the solvent-water systems are hexane, dichloromethane, trichloromethane, octanol, and toluene. The only available reported solvent-water partition coefficients are for octanol-water for some of the investigated compounds and they are in good agreement with the experimental measurements from this study. Solvent-water partition coefficients fitted using experimentally derived solute parameters from this study have significantly smaller root mean square errors (RMSE = 0.38) than predictions using ABSOLV estimated solute parameters (RMSE = 3.56) for the investigated compounds. Additionally, the predictions for various physico-chemical properties using the experimentally derived solute parameters agree with available literature reported values with prediction errors within 0.79 log units except for water solubility of RDX and HMX with errors of 1.48 and 2.16 log units respectively. However, predictions using ABSOLV estimated solute parameters have larger prediction errors of up to 7.68 log units. This large discrepancy is probably due to the missing R2NNO2 and R2NNO2 functional groups in the ABSOLV fragment database.
authors.affiliation: Department of Civil and Environmental Engineering, University of Delaware, Newark, 19716, DE, USA. Electronic address: yzliang@udel.edu.
authors.forename: Yuzhen
authors.initials: Y
authors.lastname: Liang
authors.affiliation: Department of Civil and Environmental Engineering, University of Delaware, Newark, 19716, DE, USA; Department of Architecture and Civil Engineering, City University of Hong Kong, Kowloon, Hong Kong; City University of Hong Kong, Shenzhen Research Institute, Shenzhen, 518057, China. Electronic address: tfdkuo@cityu.edu.hk.
authors.forename: Dave T F
authors.initials: DTF
authors.lastname: Kuo
authors.affiliation: Department of Civil and Environmental Engineering, University of Delaware, Newark, 19716, DE, USA. Electronic address: allen@udel.edu.
authors.forename: Herbert E
authors.initials: HE
authors.lastname: Allen
authors.affiliation: Department of Civil and Environmental Engineering, University of Delaware, Newark, 19716, DE, USA. Electronic address: dditoro@udel.edu.
authors.forename: Dominic M
authors.initials: DM
authors.lastname: Di Toro
mesh_terms: D000840:Anisoles / Q000737:chemistry; D008956:Models, Chemical; D000442:Octanols / Q000737:chemistry; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics; D014227:Triazines / Q000737:chemistry; D014301:Trinitrobenzenes / Q000737:chemistry; D014867:Water / Q000737:chemistry*
chemical_list: D000840:Anisoles; D000442:Octanols; D012997:Solvents; D014227:Triazines; D014301:Trinitrobenzenes; C508167:hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine; D014867:Water; C029222:sym-trinitrobenzene; C005306:4-nitroanisole; C009160:cyclonite
keywords: ABSOLV; Abraham parameter; HMX; LFER; Partitioning; RDX