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Публикация

Название: Calculation of the standard molal thermodynamic properties of crystalline, liquid, and gas organic molecules at high temperatures and pressures

Автор(ы): Harold C. Helgeson, Christine E. Owens, Annette M. Knox, Laurent Richard

Аннотация: 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 (T_tfr, T _mfr , and T_vfr, respectively) and standard molal enthalpies of transition (ΔH°_t,Pг), melting (ΔH°_m,Pг), and vaporization (ΔH°_Pг) of organic species at 1 bar (P_r) 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 (T_r) and P_r (ΔG°_f and ΔH°_f, respectively). The critical compilation also includes standard molal entropies (S°) and volumes (V°) at T_r and P_r, 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 (С_nН_2(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 (С_nН_2(n+1)) for carbon numbers ranging from 1 to 100, 2- Und 3-methylalkanes (С_nН_2(n+1)) for 4 ≤ n ≤ 20 and 6 ≤ n ≤ 20, respectively, 2,3-dimethylpentane (C₇H₁₆), 4-methylheptane (C₈H₁₈), cycloalkanes (C_nH_2n) for 3 ≤ n ≤ 8, methylated benzenes (С_nН_2(n-3)) for 7 ≤ n ≤ 12, normal alkylbenzenes (С_nH_2(n-3)) for 6 ≤ n ≤ 20, normal 1-alcohols (С_nН_2(n+1))О) for 1 ≤ n ≤ 20, ethylene glycol (C₂H₆O₂), glycerol (C₃H₈O₃), normal 1-alkanethiols (С_nН_2(n+1)S) for 1 ≤ n ≤ 20, normal carboxylic acids (С_nН_2nО₂) 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.

Библиографическое описание: 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

Тип публикации: статья

Загрузить документ HELGESON_ET_AL_1998.pdf (13.33 Mb)

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