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Equilibrium H/H fractionations in organic molecules. II: Linear alkanes, alkenes, ketones, carboxylic acids, esters, alcohols and ethers
Authors:Ying Wang  Alex L Sessions  Robert J Nielsen  William A Goddard III
Institution:aDivision of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA;bMaterials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA
Abstract:Equilibrium 2H/1H fractionation factors (αeq) for various H positions in alkanes, alkenes, ketones, carboxylic acids, esters, alcohols, and ethers were calculated between 0 and 100 °C using vibrational frequencies from ab initio QM calculations (B3LYP/6-311G**). Results were then corrected using a temperature-dependent linear calibration curve based on experimental data for Hα in ketones (Wang et al., 2009). The total uncertainty in reported αeq values is estimated at 10–20‰. The effects of functional groups were found to increase the value of αeq for H next to electron-donating groups, e.g. single bondOR, single bondOH or single bondO(Cdouble bond; length as m-dashO)R, and to decrease the value of αeq for H next to electron-withdrawing groups, e.g. single bond(Cdouble bond; length as m-dashO)R or single bond(Cdouble bond; length as m-dashO)OR. Smaller but significant functional group effects are also observed for Hβ and sometimes Hγ. By summing over individual H positions, we estimate the equilibrium fractionation relative to water to be −90‰ to −70‰ for n-alkanes and around −100‰ for pristane and phytane. The temperature dependence of these fractionations is very weak between 0 and 100 °C. Our estimates of αeq agree well with field data for thermally mature hydrocarbons (δ2H values between −80‰ and −110‰ relative to water). Therefore the observed δ2H increase of individual hydrocarbons and the disappearance of the biosynthetic δ2H offset between n-alkyl and linear isoprenoid lipids during maturation of organic matter can be confidently attributed to H exchange towards an equilibrium state. Our results also indicate that many n-alkyl lipids are biosynthesized with δ2H values that are close to equilibrium with water. In these cases, constant down-core δ2H values for n-alkyl lipids cannot be reliably used to infer a lack of isotopic exchange.
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