地质流体状态方程

段振豪; 刘荣; 孙睿

Volume 29 Issue 6

Jun. 2004

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DUAN Zhen-hao, LIU Rong, SUN Rui, 2004. Modeling Geological Fluids to High Temperatures and Pressures. Earth Science, 29(6): 716-732.

Citation:

DUAN Zhen-hao, LIU Rong, SUN Rui, 2004. Modeling Geological Fluids to High Temperatures and Pressures. Earth Science, 29(6): 716-732.

DUAN Zhen-hao, LIU Rong, SUN Rui, 2004. Modeling Geological Fluids to High Temperatures and Pressures. Earth Science, 29(6): 716-732.

Citation:

DUAN Zhen-hao, LIU Rong, SUN Rui, 2004. Modeling Geological Fluids to High Temperatures and Pressures. Earth Science, 29(6): 716-732.

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Modeling Geological Fluids to High Temperatures and Pressures

DUAN Zhen-hao^{1, 2, 3
,},
LIU Rong³,
SUN Rui^{1, 3}

1.
Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
2.
Department of Chemistry, University of California, San Diego, CA 92093, USA
3.
Faculty of Earth Resources, China University of Geosciences, Wuhan 430074, China

Received Date: 2004-08-31
Publish Date: 2004-11-25

Abstract

Abstract

Methodsfor predicting the thermodynamic properties of natural fluids over a large range of concentration, temperature and pressure are presented. With careful choice of phenomenology and parameterization, predictions can be made with accuracies similar to the experimental data.Resultspresented for the NaCl-CO₂-CH₄-H₂O system suggest that these modeling methods can be used to extrapolate experimental measurements to high pressure and temperature regions difficult to access by experimental methods. For species such as CH₄ and CO₂, which are nonpolar and weakly interacting, a corresponding states representation yields results that are highly accurate and depend on only two temperature and pressure independent parameters. Predictions with such models of fluid/fluid coexistence at high temperature and pressures are within experimental accuracy. The role of molecular dynamics and Monte Carlo simulations in developing thermodynamic representations of natural system are discussed. For closed shell and nonpolar systems, simulation results agree very well with experimental data. Polar systems (H₂O) at sufficiently high temperatures are also well described. On the other hand, the simulations for polar systems at low temperatures yield results only in qualitative agreement with data. Efforts to improve simulation methods for these systems are in progress.
- natural fluid,
- thermodynamic model,
- physical chemistry properties,
- equation of state,
- molecular dynamics simulation

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References(56)

References

Allen, M., Tildesley, D., 1987. Computer simulation of liquids. Oxford University Press.

Al-Sahhaf, T., 1990. Vapor-liquid equilibria for the ternary system N₂+CO₂+CH₄ at 230 and 250 K. Fluid Phase Equilibria, 55: 159-172. doi: 10.1016/0378-3812(90)85010-8

Al-Sahhaf, T., Kidnay, A., Sloan, E., 1983. Liquid+vapor equilibrium in the N₂+CO₂+CH₄ system. Ind. Eng. Chem. Fundam. , 22: 372-380. doi: 10.1021/i100012a004

Anderko, A., Pitzer, K., 1993. Equation of state representation of phase equilibria and volumetric properties of the system NaCl-H₂O above 573 K. Geochim. Cosmochim. Acta, 57: 1657-1680. doi: 10.1016/0016-7037(93)90105-6

Arshadi, M., Yamdagni, R., Kebarle, P., 1970. Hydration of halide negative ions in the gas phase. Ⅱ. Comparison of hydration energies for the alkali positive and halide negative ions. J. Phys. Chem. , 74: 1475-1482. doi: 10.1021/j100702a014

Belonoshko, A., Saxena, S., 1992. A unified equation of state for fluids of C-H-O-N-S-Ar composition and their mixtures up to very high temperatures and pressures. Geochim. Cosmochim. Acta, 56: 3611-3626. doi: 10.1016/0016-7037(92)90157-E

Belonoshko, A., Shi, P.F., Saxena, S., 1992. Superfluid: A Fortran-77 Program for calculation of Gibbs free energy and volume of C-H-O-N-S-Ar mixtures. Compu. Geosci. , 18: 1267-1269. doi: 10.1016/0098-3004(92)90044-R

Berendsen, H., Postma, J., Gunsteren, W.V., et al., 1981. Intermolecular forces. Reidel, Dordrecht, 331.

Bowers, T.S., Helgeson, H.C., 1983. Calculation of the thermodynamic and geochemical consequences of nonideal mixing in the system H₂O-CO₂-NaCl on phase relations in geologic systems: Equation of state for H₂O-CO₂-NaCl fluids at high pressures and temperatures. Geochim. Cosmochim. Acta, 47: 1247-1275. doi: 10.1016/0016-7037(83)90066-2

Burnham, C., Holloway, J., Davis, N., 1969. The specific volume of water in the range 1 000 to 8 900 bars, 20 to 900 ℃. Amer. J. Sci. , 267-A: 70-95.

Car, R., Parrinello, M., 1985. Unified approach for molecular dynamics and density-functional theory. Phys. Rev. Lett. , 55: 2471. doi: 10.1103/PhysRevLett.55.2471

Constantino, M., 1991. Supercritical phase separation in H₂O-N₂ mixtures. J. Phys. Chem. , 95: 9034-9036. doi: 10.1021/j100176a004

D'Ans, J., Bartels, J., Bruggencate, P., et al., 1967. Thermodynamiche eigenschaften von wasser and wasserdapf(International Skeleton Table). Landolt-Bornstein, 534-535.

Dawe, R., Snowdon, P.N., 1974. Experimental high pressure enthalpies of N₂(g)and CO₂(g)in the range 273.15 to 373.15 K. J. Chem. Thermody. , 6: 293-301. doi: 10.1016/0021-9614(74)90183-9

Deffet, L., Ficks, F., 1965. Advanced thermodynamical properties. Technical Report 107, Symposium on Thermodynamical Properties. Purdue University, Lafayette, Indiana.

Dimitrelis, D., Prausnitz, J., 1986. Comparison of two hardsphere reference systems for perturbation theories for mixtures. Fluid Phase Equilibria, 31: 1-21. doi: 10.1016/S0378-3812(86)87028-5

Din, F., 1961. Thermodynamic functions of gases. Butterworths, London.

Duan, Z., Möller, N., Weare, J., 1992a. An equation of state for the CH₄-CO₂-H₂O system: Ⅰ. Pure systems from 0 to 1 000℃ and from 0 to 8 000 bar. Geochim. Cosmochim. Acta, 56: 2605-2617. doi: 10.1016/0016-7037(92)90347-L

Duan, Z., Möller, N., Weare, J., 1992b. An equation of state for the CH₄-CO₂-H₂O system: Ⅱ. Mixtures from 50 to 1 000℃ and from 0 to 1 000 bar. Geochim. Cosmochim. Acta, 56: 2619-2631. doi: 10.1016/0016-7037(92)90348-M

Duan, Z., Möller, N., Weare, J., 1992c. Molecular dynamics simulation of PVT properties of geological fluids and a general equation of state for nonpolar and weakly polar gases up to 2 000 K and 20 000 bar. Geochim. Cosmochim. Acta, 56: 3839-3845. doi: 10.1016/0016-7037(92)90175-I

Duan, Z., Möller, N., Weare, J., 1995a. Equation of state for the NaCl-H₂O-CO₂ system: Prediction of phase equilibria and volumetric properties. Geochim. Cosmochim. Acta, 59: 2869-2882. doi: 10.1016/0016-7037(95)00182-4

Duan, Z., Möller, N., Weare, J., 1995b. Molecular dynamics simulation of water properties using RWK² potential: From clusters to bulk water. Geochim. Cosmochi. Acta, 59: 3273-3283. doi: 10.1016/0016-7037(95)00216-M

Duan, Z., Möller, N., Weare, J., 1996. A general equation of state for supercritical fluid mixtures and molecular dynamics simulation of mixture PVTX properties. Geochim. Cosmochim. Acta, 60(7): 1209-1216. doi: 10.1016/0016-7037(96)00004-X

Duan, Z., Möller, N., Weare, J., 2000. Accurate prediction of thermodynamic properties of fluids in the system H₂O-CO₂-CH₄-N₂ up to 2 000 K and 100 kbar from a corresponding states/one fluid equation of state. Geochim. Cosmochim. Acta, 64: 1069-1075. doi: 10.1016/S0016-7037(99)00368-3

Dzidic, I., Kebarle, P., 1970. Hydration of the alkali ions in the gas phase, enthalpy and entropies of reactions m + (H₂O)_n-1+H₂O= m+(H₂O)_n. J. Phys. Chem. , 74: 1466-1474. doi: 10.1021/j100702a013

Francesconi, A.Z., Kristische. K., 1978. Phasengleichgewiche and PVT-daten im system methanol-methan bis 3 kbar and 240℃ (Ph. D. ). Univ. Fridericiana Karlsruhe, Germany.

Franck, E.U., Todheide, K., 1959. Thermische eigenschaften uberkristischer mischungen von kohlen-dioxyd and wasser bis zu 750 ℃ and 2 000 bar. Z. Phys. Chem. (Neue Folge), 22: 232-245. doi: 10.1524/zpch.1959.22.3_4.232

Frantz, J., Popp, R., Hoering, T., 1992. The compositional limits of fluid immiscibility in the system H₂O-NaCl-CO₂ as determined with the use of synthetic fluid inclusions in conjunction with mass spectrometry. Chem. Geol. , 98: 237-255. doi: 10.1016/0009-2541(92)90187-A

Frost, D., Wood, B., 1997. Experimental measurements of the properties of H₂O-CO₂ mixtures at high pressures and temperatures. Geochim. Cosmochim. Acta, 61: 3301-3309. doi: 10.1016/S0016-7037(97)00168-3

Gehrig, M., 1980. Phasengleichgewichte and PVT-daten ternarer mischungen aus wasser, kohlen-dioxide and Natriumchlorid bis 3 kbar and 550℃. University of Karlsrube.

Haar, L., Gallagher, J., Kell, G., 1984. NBS/NRC steam tables, thermodynamic and transport properties and computer programs for vapor and liquid states of water in SI units. Hemisphere Publishing Co., Washington D.C. .

Harvie, C.E., Möller, N., Weare, J.H., 1984. The prediction of mineral solubilities in natural waters: The Na-K-Mg-Ca-H-Cl-SO₄-OH-HCO₃-CO₃-CO₂-H₂O system to high ionic strengths at 25℃. Geochim. Cosmochim. Acta, 48: 723-751. doi: 10.1016/0016-7037(84)90098-X

Johnson, E., 1992. An assessment of the accuracy of isochore location techniques for H₂O-CO₂-NaCl fluids at granulite facies pressure-temperature conditions. Geochim. Cosmochim. Acta, 56: 295-302. doi: 10.1016/0016-7037(92)90134-5

Krader, T., 1985. Phasengleichgewichte and kritische kurven des systems H₂O-CH₄-NaCl bis 250 MPa and 800 K. Institute for Physical Chemistry, Univ. Karlsrule.

Krader, T., Frank, E., 1987. The ternary systems H₂O-CH₄-NaCl and H₂O-CH₄-CaCl₂ to 800 K and 250 bar. Ber. Bunsenges. Phys. Chem. , 91: 627-634. doi: 10.1002/bbpc.19870910610

Lamb, W., Popp, R., Boockoff, L., 1996. The determination of phase relations in the CH₄-H₂O-NaCl system at 1 kbar, 400 to 600-degrees-cusing synthetic fluid inclusions. Geochim. Cosmochim. Acta, 60: 1885-1897. doi: 10.1016/0016-7037(96)00070-1

Marx, D., Sprik, M., Parrinello, M., 1997. Abinitio molecular dynamics of ion solvation: The case of Be²⁺ in water. Chemical Physical Letters, 273: 360-366. doi: 10.1016/S0009-2614(97)00618-0

McQuarrie, D.A., 1976. Statistical Mechanics. Harper & Row, New York.

Millero, F., 1970. The apparent and partial volume of aqueous chloride solutions at various temperatures. J. Phys. Chem., 74: 356-362. doi: 10.1021/j100697a022

Mills, R., Liebenberg, D., Bronson, J., 1975. Sound velocity and the equation of state of N₂ to 22 kbar. J. Chem. Phys. , 63: 1198-1204. doi: 10.1063/1.431457

Peng, D., Robinson, D., 1976. A new two constant equation of state. Ind. Chem. Eng. Data, 15: 59-64.

Pettitt, B., Rossky, P., 1986. Alkali halides in water: Ion-solvent correlations and ion-ion potentials of mean force at infinite dilution. J. Chem. Phys. , 84: 5836-5839. doi: 10.1063/1.449894

Pitzer, K., 1987. Thermodynamic model for aqueous solutions of liquid-like density. In: Reviews in Minerology. Book Crafters, Inc., 97-142.

Pitzer, K.S., Peiper, J.C., 1984. Thermodynamic properties of aqueous sodium chloride solutions. J. Phys. Chem. Ref. Data, 13: 1-105. doi: 10.1063/1.555709

Ree, F., 1986. Supercritical fluid phase separation: Implications for detonation properties of condensed explosives. J. Chem. Phys. , 84: 5845-5856. doi: 10.1063/1.449895

Reimers, J., Watts, R., Klein, M., 1982. Intermolecular potential functions and the properties of water. Chem. Phys. , 64: 95-114. doi: 10.1016/0301-0104(82)85006-4

Saul, A., Wagner, W., 1989. A fundamental equation for water covering the range from melting to 1 273 K at pressures up to 25 000 MPa. J. Phys. Chem. Data, 18: 1537-1563. doi: 10.1063/1.555836

Sterner, S., Bodnar, R., 1991. Synthetic fluid inclusions. X: Experimental determination of P-V-T-x properties in the CO₂-H₂O system to 6 kb and 700 ℃. Amer. J. Sci. , 291: 1-54. doi: 10.2475/ajs.291.1.1

Sultanov, R., Skripka, V., 1971. Moisture content of methane at high temperatures and pressures. Cazovaia Promyshlennost, 16: 54-57.

Sun, R., Duan, Z., 2003. A new equation of state and Fortran 77 Program to calculate vapor-liquid phase equilibria of CH₄-H₂O system at low temperatures. Computers & Geosciences, 29: 1291-1299.

Todheide, K., Franck, E., 1963. Das zweiphasengebiet and die kritische kurve in system kohlendioxide-wasser bis zu drucken von 3 500 bar. Z. Phys. Chem. (Neue Folge), 37: 387-401. doi: 10.1524/zpch.1963.37.5_6.387

Tsiklis, D., Linshits, L., 1967. Molar volumes and thermodynamic properties of methane at high pressures and temperatures. Dokl. Akad. Nauk SSSR, 176: 423-425.

VanHinsberg, M., Verbrugge, R., Schouten, J., 1993. Hightemperature and high-pressure experiments on H₂O-N₂. Fluid Phase Equil. , 88: 115-121. doi: 10.1016/0378-3812(93)87105-A

Walas, M., 1985. Phase equilibria in chemical engineering. Butterworths, London.

Welsch, H., 1973. Die system xenon-wasser and methan-wasser bei holen drucken und temperaturen. Univ. Karlsruhe.

Zhang, Y., Frantz, J., 1987. Determination of the homogenization temperatures and densities of super-critical fluids in the system NaCl-KCl-CaCl₂-H₂O using synthetic fluid inclusions. Chemical Geology, 64: 335-350. doi: 10.1016/0009-2541(87)90012-X

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