A.G.Kalinichev: Supercritical fluids

Supercritical fluids and their technological applications

Supercritical fluids are highly compressed gases at temperatures and pressures above the critical point. They combine properties of gases and liquids in a very intriguing manner. Due to the high compressibility of supercritical fluids, small changes in pressure can produce substantial changes in density which, in turn, affect diffusivity, viscosity, dielectric, and solvation properties of these fluids, thus dramatically influencing the kinetics and mechanisms of chemical reactions.

Supercritical water (Tc=647K=374^oC; Pc=221 atm) has recently become a subject of growing scientific interest because of emerging very promising environmentally friendly and energy efficient technologies. Under supercritical conditions water is able to dissolve many nonpolar organic compounds, including PCBs. At high enough pressures it is miscible in all proportions with both organic compounds and oxygen. Thus, these compounds can be oxidized in a homogeneous supercritical phase, with the further removal of products from solution by either dropping the pressure or by cooling. This constitutes the essence of many promising new technologies. For instance, supercritical water oxidation (SCWO) processes can successully degrade dioxin, PCBs, benzene, DDT, urea, cyanide, and dozens of other toxic substances, including chemical-warfare agents and solid-rocket propellants. Such processes are fast, offer greater than 99.99% destruction efficiency and, because they are closed systems, can control emissions much better than traditional incinerators. Homogeneous catalysis in the supercritical phase also offers many technological and environmental benefits.

I've been involed in the studies of supercritical aqueous fluids for many years, and they still remain one of the main topics of my research interests. While working in Russia, I organized a special seminar to discuss the problems of supercitical fluids and their thechnological applications. I also developed and maintained the web-site of this seminar for the Russian SCF research community.

Research papers

G.V.Bondarenko, Yu.E.Gorbaty, A.V.Okhulkov, A.G.Kalinichev (2006) Structure and hydrogen bonding in liquid and supercritical aqueous NaCl solutions at a pressure of 1000 bar and temperatures up to 500^oC: A comprehensive experimental and computational study. J.Phys.Chem.A, 110, 4042-4052.   [pdf 274kB]

G.V.Bondarenko, Yu.E.Gorbaty, A.G.Kalinichev, A.V.Okhulkov (2004) Complex study of liquid and supercritical aqueous solutions of electrolytes by methods of vibrational spectroscopy, x-ray diffraction, and molecular dynamics. In: Experimental Mineralogy: Some Results at the Turn of the Century, V.A.Zharikov, ed. Moscow, Nauka Publishing, v.2, pp.15-25 (in Russian).

G.V.Bondarenko, Yu.E.Gorbaty, A.G.Kalinichev, A.V.Okhulkov, V.K.Popov (2002) A comprehensive study of NaCl aqueous solution at a constant pressure of 1000 bar in the temperature range 20–500^oC. Chemical Engineering Transactions, 2(1), 79-85.

A.G.Kalinichev (2001) Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding. Reviews in Mineralogy and Geochemistry, 42, 83-129.   [pdf 775 kB]

A.G.Kalinichev, S.V.Churakov (2001) Thermodynamics and structure of molecular clusters in supercritical water. Fluid Phase Equilibria, 183, 271-278.   [pdf 119KB]

A.G.Kalinichev, S.V.Churakov (1999) Size and topology of molecular clusters in supercritical water: A molecular dynamics simulation. Chem.Phys.Lett., 302, 411-417.   [pdf 168KB]

A.G.Kalinichev, Yu.E.Gorbaty (1998) The role of hydrogen bonding in the structure and properties of hydrothermal fluids. In: Experimental and Theoretical Modeling of Mineral Formation Processes. Moscow, Nauka Publishing, pp.242-264 (in Russian).

V.S.Balitsky, L.V.Balitskaya, A.G.Kalinichev, E.A.Marina, H.Iwasaki, F.Iwasaki (1998) Silica transfer and beta-quartz crystal growth from supercritical aqueous fluids. J.Supercrit.Fluids, 13, 357-362.   [pdf 609KB]

A.G.Kalinichev (1998) Environmental and physical geochemistry on the INTERNET. Russian Environmental Science and Industry, 6/98, 32-36 (in Russian).

A.G.Kalinichev (1998) Supercritical water as a medium for a new generation of environmentally friendly and energy efficient technologies of the XXI century. Russian Environmental Science and Industry, 2/98, 12-16 (in Russian).

A.G.Kalinichev, J.D.Bass (1997) Hydrogen bonding in supercritical water. 2. Computer simulations. J.Phys.Chem.A, 101, 9720-9727.   [pdf 253KB]

Yu.E.Gorbaty, A.G.Kalinichev, G.V.Bondarenko (1997) Supercritical state and the structure of liquids. Priroda, 8, 78-89 (in Russian).

V.S.Balitsky, T.M.Bublikova, L.V.Balitskaya, A.G.Kalinichev (1996) Growth of high temperature beta-quartz from supercritical aqueous fluids. J.Crystal Growth, 162, 142-146.   [pdf 438KB]

Yu.E.Gorbaty, A.G.Kalinichev (1995) Hydrogen bonding in supercritical water. 1. Experimental results. J.Phys.Chem., 99, 5336-5340.   [pdf 622kB]

A.G.Kalinichev, K.Heinzinger (1995) Molecular dynamics of supercritical water: A computer simulation of vibrational spectra with the flexible BJH potential. Geochimica et Cosmochimica Acta, 59, 641-650.   [pdf 794KB]

A.G.Kalinichev, J.D.Bass (1995) Computer simulations of supercritical water over a wide range of densities. In: Physical Chemistry of Aqueous Systems. Meeting the Needs of Industry. Ed. by H.J.White Jr., J.V.Sengers, D.B.Neumann, J.C.Bellows. Begell House, New York, 245-252.

A.G.Kalinichev, J.D.Bass (1994) Hydrogen bonding in supercritical water: a Monte Carlo simulation. Chem.Phys.Lett., 231, 301-307.   [pdf 661KB]

A.G.Kalinichev (1993) Molecular dynamics and self-diffusion in supercritical water. Ber.Bunsenges.Phys.Chem., 97, 872-876.

A.G.Kalinichev, K.Heinzinger (1992) Computer Simulations of Aqueous Fluids at High Temperatures and Pressures. In: Thermodynamic Data: Systematics and Estimation, ed. by S.K.Saxena. Advances in Physical Geochemistry, 10,1-59.

A.G.Kalinichev (1992) Monte Carlo simulations of water under supercritical conditions. II. Convergence characteristics and the system size effects. Z.Naturforsch., 47a, 992-998.

A.G.Kalinichev (1991) Monte Carlo simulations of water under supercritical conditions. I.Thermodynamic and structural properties. Z.Naturforsch., 46a, 433-444.

A.G.Kalinichev (1991) Theoretical modeling of geochemical fluids under high-pressure, high-temperature conditions. High Pressure Research, 7, 378-380.

A.G.Kalinichev (1986) Monte Carlo study of the thermodynamics and structure of dense supercritical water. Intern.J.Thermophys., 7, 887-900.   [pdf 456kB]

A.G.Kalinichev (1985) A Monte Carlo study of dense supercritical water. High Temperature, 23, 544-548.

K.I.Shmulovich, V.A.Mazur, A.G.Kalinichev, L.I.Khodorevskaya (1980) P-V-T and component activity-concentration relations for systems of H2O-nonpolar gas type. Geochemistry International, 17(6), 18-31.

K.I.Shmulovich, V.M.Shmonov, V.A.Mazur, A.G.Kalinichev (1980) P-V-T and activity-concentration relations in the H2O-CO2 system (homogeneous solutions). Geochem. International, 17(6), 123-139.

I.V.Zakirov, A.G.Kalinichev (1980) Nonideal behavior of homogeneous gas mixtures as a function of the critical temperatures of the components. Proc.Russian Acad. Sci., (Doklady Akad. Nauk SSSR, Geochemistry), 253, 236-238.

Invited Talks and Seminars

"Phase separation of metamorphic fluids: Molecular dynamics modeling of a generalized system H2O-CO2-NaCl at high temperatures and pressures" - International School of Earth's Sciences, Odessa, Ukraine, August 2005.

"Molecular simulations of liquid and supercritical water: thermodynamics, structure,and hydrogen bonding" - Laboratory of Mathematical and Physical Modeling in Hydrodynamics, Institute for Problems in Mechanics, Russian Academy of Sciences, Moscow, Russia, May 30, 2003.

"Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding" - Mineralogical Society of America - Geochemical Society Short Course “Molecular Modeling Theory: and Applications in the Geosciences”, Roanoke, VA, May 2001.

"Hydrogen bond dynamics in supercritical water" - VIIth International Conference "Problems of solvation and complex formation in solutions", Ivanovo, Russia, June 1998.

"Computer simulations of the properties of supercritical water over a very wide range of temperatures and densities" - Center for Computational Chemistry of the Keldysh Institute of Applied Mathematics, Russian Academy of Sciences,, Moscow, Russia, January 21, 1998.

"Supercritical water as a medium for a new generation of environmentally friendly and energy efficient technologies of the XXI century" (opening lecture). Moscow Seminar on Supercritical Fluids Science and Technology, Moscow, November 1997.

"Structute and Hydrogen Bonding in Liquid and Supercritical Water: Experimental Studies and Computer Simulations" - EMLG Annual Meeting "Structure and Thermodynamics of Solvents and Solutions". Balatonfured, Hungary, September 1996.

Last updated: October 28, 2007

	Research papers
	G.V.Bondarenko, Yu.E.Gorbaty, A.V.Okhulkov, A.G.Kalinichev (2006) Structure and hydrogen bonding in liquid and supercritical aqueous NaCl solutions at a pressure of 1000 bar and temperatures up to 500^oC: A comprehensive experimental and computational study. J.Phys.Chem.A, 110, 4042-4052. [pdf 274kB]
	G.V.Bondarenko, Yu.E.Gorbaty, A.G.Kalinichev, A.V.Okhulkov (2004) Complex study of liquid and supercritical aqueous solutions of electrolytes by methods of vibrational spectroscopy, x-ray diffraction, and molecular dynamics. In: Experimental Mineralogy: Some Results at the Turn of the Century, V.A.Zharikov, ed. Moscow, Nauka Publishing, v.2, pp.15-25 (in Russian).
	G.V.Bondarenko, Yu.E.Gorbaty, A.G.Kalinichev, A.V.Okhulkov, V.K.Popov (2002) A comprehensive study of NaCl aqueous solution at a constant pressure of 1000 bar in the temperature range 20–500^oC. Chemical Engineering Transactions, 2(1), 79-85.
	A.G.Kalinichev (2001) Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding. Reviews in Mineralogy and Geochemistry, 42, 83-129. [pdf 775 kB]
	A.G.Kalinichev, S.V.Churakov (2001) Thermodynamics and structure of molecular clusters in supercritical water. Fluid Phase Equilibria, 183, 271-278. [pdf 119KB]
	A.G.Kalinichev, S.V.Churakov (1999) Size and topology of molecular clusters in supercritical water: A molecular dynamics simulation. Chem.Phys.Lett., 302, 411-417. [pdf 168KB]
	A.G.Kalinichev, Yu.E.Gorbaty (1998) The role of hydrogen bonding in the structure and properties of hydrothermal fluids. In: Experimental and Theoretical Modeling of Mineral Formation Processes. Moscow, Nauka Publishing, pp.242-264 (in Russian).
	V.S.Balitsky, L.V.Balitskaya, A.G.Kalinichev, E.A.Marina, H.Iwasaki, F.Iwasaki (1998) Silica transfer and beta-quartz crystal growth from supercritical aqueous fluids. J.Supercrit.Fluids, 13, 357-362. [pdf 609KB]
	A.G.Kalinichev (1998) Environmental and physical geochemistry on the INTERNET. Russian Environmental Science and Industry, 6/98, 32-36 (in Russian).
	A.G.Kalinichev (1998) Supercritical water as a medium for a new generation of environmentally friendly and energy efficient technologies of the XXI century. Russian Environmental Science and Industry, 2/98, 12-16 (in Russian).
	A.G.Kalinichev, J.D.Bass (1997) Hydrogen bonding in supercritical water. 2. Computer simulations. J.Phys.Chem.A, 101, 9720-9727. [pdf 253KB]
	Yu.E.Gorbaty, A.G.Kalinichev, G.V.Bondarenko (1997) Supercritical state and the structure of liquids. Priroda, 8, 78-89 (in Russian).
	V.S.Balitsky, T.M.Bublikova, L.V.Balitskaya, A.G.Kalinichev (1996) Growth of high temperature beta-quartz from supercritical aqueous fluids. J.Crystal Growth, 162, 142-146. [pdf 438KB]
	Yu.E.Gorbaty, A.G.Kalinichev (1995) Hydrogen bonding in supercritical water. 1. Experimental results. J.Phys.Chem., 99, 5336-5340. [pdf 622kB]
	A.G.Kalinichev, K.Heinzinger (1995) Molecular dynamics of supercritical water: A computer simulation of vibrational spectra with the flexible BJH potential. Geochimica et Cosmochimica Acta, 59, 641-650. [pdf 794KB]
	A.G.Kalinichev, J.D.Bass (1995) Computer simulations of supercritical water over a wide range of densities. In: Physical Chemistry of Aqueous Systems. Meeting the Needs of Industry. Ed. by H.J.White Jr., J.V.Sengers, D.B.Neumann, J.C.Bellows. Begell House, New York, 245-252.
	A.G.Kalinichev, J.D.Bass (1994) Hydrogen bonding in supercritical water: a Monte Carlo simulation. Chem.Phys.Lett., 231, 301-307. [pdf 661KB]
	A.G.Kalinichev (1993) Molecular dynamics and self-diffusion in supercritical water. Ber.Bunsenges.Phys.Chem., 97, 872-876.
	A.G.Kalinichev, K.Heinzinger (1992) Computer Simulations of Aqueous Fluids at High Temperatures and Pressures. In: Thermodynamic Data: Systematics and Estimation, ed. by S.K.Saxena. Advances in Physical Geochemistry, 10,1-59.
	A.G.Kalinichev (1992) Monte Carlo simulations of water under supercritical conditions. II. Convergence characteristics and the system size effects. Z.Naturforsch., 47a, 992-998.
	A.G.Kalinichev (1991) Monte Carlo simulations of water under supercritical conditions. I.Thermodynamic and structural properties. Z.Naturforsch., 46a, 433-444.
	A.G.Kalinichev (1991) Theoretical modeling of geochemical fluids under high-pressure, high-temperature conditions. High Pressure Research, 7, 378-380.
	A.G.Kalinichev (1986) Monte Carlo study of the thermodynamics and structure of dense supercritical water. Intern.J.Thermophys., 7, 887-900. [pdf 456kB]
	A.G.Kalinichev (1985) A Monte Carlo study of dense supercritical water. High Temperature, 23, 544-548.
	K.I.Shmulovich, V.A.Mazur, A.G.Kalinichev, L.I.Khodorevskaya (1980) P-V-T and component activity-concentration relations for systems of H2O-nonpolar gas type. Geochemistry International, 17(6), 18-31.
	K.I.Shmulovich, V.M.Shmonov, V.A.Mazur, A.G.Kalinichev (1980) P-V-T and activity-concentration relations in the H2O-CO2 system (homogeneous solutions). Geochem. International, 17(6), 123-139.
	I.V.Zakirov, A.G.Kalinichev (1980) Nonideal behavior of homogeneous gas mixtures as a function of the critical temperatures of the components. Proc.Russian Acad. Sci., (Doklady Akad. Nauk SSSR, Geochemistry), 253, 236-238.

	Invited Talks and Seminars
	"Phase separation of metamorphic fluids: Molecular dynamics modeling of a generalized system H2O-CO2-NaCl at high temperatures and pressures" - International School of Earth's Sciences, Odessa, Ukraine, August 2005.
	"Molecular simulations of liquid and supercritical water: thermodynamics, structure,and hydrogen bonding" - Laboratory of Mathematical and Physical Modeling in Hydrodynamics, Institute for Problems in Mechanics, Russian Academy of Sciences, Moscow, Russia, May 30, 2003.
	"Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding" - Mineralogical Society of America - Geochemical Society Short Course “Molecular Modeling Theory: and Applications in the Geosciences”, Roanoke, VA, May 2001.
	"Hydrogen bond dynamics in supercritical water" - VIIth International Conference "Problems of solvation and complex formation in solutions", Ivanovo, Russia, June 1998.
	"Computer simulations of the properties of supercritical water over a very wide range of temperatures and densities" - Center for Computational Chemistry of the Keldysh Institute of Applied Mathematics, Russian Academy of Sciences,, Moscow, Russia, January 21, 1998.
	"Supercritical water as a medium for a new generation of environmentally friendly and energy efficient technologies of the XXI century" (opening lecture). Moscow Seminar on Supercritical Fluids Science and Technology, Moscow, November 1997.
	"Structute and Hydrogen Bonding in Liquid and Supercritical Water: Experimental Studies and Computer Simulations" - EMLG Annual Meeting "Structure and Thermodynamics of Solvents and Solutions". Balatonfured, Hungary, September 1996.