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Title: Calculation of the standard molal thermodynamic properties of crystalline, liquid, and gas organic molecules at high temperatures and pressures
Author(s): Harold C. Helgeson, Christine E. Owens, Annette M. Knox, Laurent Richard
Annotation: Calculation of the thermodynamic properties of organic solids, liquids, and gases at high temperatures and pressures is a requisite for characterizing hydrothermal metastable equilibrium states involving these species and quantifying the chemical affinities of irreversible reactions of organic molecules in natural gas, crude oil, kerogen, and coal with minerals and organic, inorganic, and biomolecular aqueous species in interstitial waters in sedimentary basins. To facilitate calculations of this kind, coefficients for the Parameters From, Group Contributions (PFGC) equation of state have been compiled for a variety of groups in organic liquids and gases. In addition, molecular weights, critical temperatures and pressures, densities at 25°C and 1 bar, transition, melting, and boiling temperatures (Ttfr, T mfr , and Tvfr, respectively) and standard molal enthalpies of transition (ΔH°t,Pг), melting (ΔH°m,Pг), and vaporization (ΔH°Pг) of organic species at 1 bar (Pr) have been tabulated, together with an internally consistent and comprehensive set of standard molal Gibbs free energies and enthalpies of formation from the elements in their stable state at 298.15 К (Tr) and Pr (ΔG°f and ΔH°f, respectively). The critical compilation also includes standard molal entropies (S°) and volumes (V°) at Tr and Pr, and standard molal heat capacity power function coefficients to compute the standard molal thermodynamic properties of organic solids, liquids, and gases as a function of temperature at 1 bar. These properties and coefficients have been tabulated for more than 500 crystalline solids, liquids, and gases, and those for many more can be computed from the equations of state group additivity algorithms. The crystalline species correspond to normal alkanes (СnН2(n+1)) with carbon numbers (n, which is equal to the number of moles of carbon atoms in one mole of the species) ranging from 5 to 100, and 23 amino acids including glycine (C2H5NO2), alanine (C3H7NO2), valine (C5H11NO2), leucine (C6H13NO2), isoleucine (C6H13NO2), aspartic acid (C4H7NO4), glutamic acid (C5H9NO4), asparagine (C4H8N2O3), glutamine (C5H10N2O3), proline (C5H9NO2), phenylalanine (C9H11NO22), tryptophan (С11Н12Н2О2), methionine (C5H11SNO2), serine (C3H7NO3), threonine (C4H9NO3), cysteine (C3H7SNO2), tyrosine (С9Н13NO3), lysine (C6H14N2O2), lysine:HCl (C6H15N2O2C1), arginine (C6H14N4O2), arginine:HCl (C6H15N4O2C1), histidine (C6H9N3O2), and histidine:HCl (C6H10N3O2Cl). The data for the latter compounds permit calculation of the standard molal thermodynamic properties of protein unfolding in biogeochemical processes (Helge-son et al., 1998). The liquids and gases considered in the present study include normal alkanes (СnН2(n+1)) for carbon numbers ranging from 1 to 100, 2- Und 3-methylalkanes (СnН2(n+1)) for 4 ≤ n ≤ 20 and 6 ≤ n ≤ 20, respectively, 2,3-dimethylpentane (C7H16), 4-methylheptane (C8H18), cycloalkanes (CnH2n) for 3 ≤ n ≤ 8, methylated benzenes (СnН2(n-3)) for 7 ≤ n ≤ 12, normal alkylbenzenes (СnH2(n-3)) for 6 ≤ n ≤ 20, normal 1-alcohols (СnН2(n+1))О) for 1 ≤ n ≤ 20, ethylene glycol (C2H6O2), glycerol (C3H8O3), normal 1-alkanethiols (СnН2(n+1)S) for 1 ≤ n ≤ 20, normal carboxylic acids (СnН2nО2) for 2 ≤ n ≤ 20, and the following miscellaneous species: 2-thiabutane (C3H8S), thiophene (C4H4S), thiophenol (C6H6S), acetone (C3H6O), 2-butanone (C4H8O), ethyl acetate (C4H8O2), pyridine (C5H5N), 3-methylpyridine (C6H7N), and quinoline (C9H7N). One additional liquid (2-methylthiacyclopentane (C5H10S)) was also considered along with crystalline and gaseous carbazole (C12H9N). The thermodynamic data and equations summarized below can be used together with the standard molal thermodynamic properties of high molecular weight organic compounds (Richard and Helgeson, 1995, 1998a,b) and minerals, inorganic gases, and aqueous species, including biomolecules (Johnson et al., 1992; Shock, 1992a, 1994, 1995; Shock et al., 1997; Shock and Koretsky, 1993, 1995; Sassani and Shock, 1992, 1994; Schulte and Shock, 1993, 1995; Oelkers et al., 1995; Amend and Helgeson, 1997a,b,c, 1998; Sverjensky et al., 1997) to compute equilibrium constants and chemical affinities for a wide variety of organic-inorganic reactions in geochemical and biochemical processes at both high and low temperatures and pressures.
Bibliographical description: Calculation of the standard molal thermodynamic properties of crystalline, liquid, and gas organic molecules at high temperatures and pressures / Harold C. Helgeson, Christine E. Owens, Annette M. Knox, Laurent Richard. - Geochimica et Cosmochimica Acta, Vol. 62, No. 6, pp. 985-1081, 1998
Publication's type: статья
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