Prediction of self-diffusion coefficient and shear viscosity of water and its binary mixtures with methanol and ethanol by molecular simulation.

Density, self-diffusion coefficient, and shear viscosity of pure liquid water are predicted for temperatures between 280 and 373 K by molecular dynamics simulation and the Green-Kubo method. Four different rigid nonpolarizable water models are assessed: SPC, SPC/E, TIP4P, and TIP4P/2005. The pressure dependence of the self-diffusion coefficient and the shear viscosity for pure liquid water is also calculated and the anomalous behavior of these properties is qualitatively well predicted. Furthermore, transport properties as well as excess volume and excess enthalpy of aqueous binary mixtures containing methanol or ethanol, based on the SPC/E and TIP4P/2005 water models, are calculated. Under the tested conditions, the TIP4P/2005 model gives the best quantitative and qualitative agreement with experiments for the regarded transport properties. The deviations from experimental data are of 5% to 15% for pure liquid water and 5% to 20% for the water + alcohol mixtures. Moreover, the center of mass power spectrum of water as well as the investigated mixtures are analyzed and the hydrogen-bonding structure is discussed for different states.

[1]  L. Nilsson,et al.  Structure and Dynamics of the TIP3P, SPC, and SPC/E Water Models at 298 K , 2001 .

[2]  J. D. Isdale,et al.  Shear viscosity of methanol and methanol + water mixtures under pressure , 1985 .

[3]  A. Laaksonen,et al.  Three-Dimensional Structure in Water−Methanol Mixtures , 1997 .

[4]  Hydration of methanol in water. A DFT-based molecular dynamics study , 2000, physics/0010040.

[5]  Shiro Maeda,et al.  Hydrophobic hydration of tert-butyl alcohol probed by NMR and IR , 2000 .

[6]  W. L. Jorgensen,et al.  Comparison of simple potential functions for simulating liquid water , 1983 .

[7]  C. Vega,et al.  Vapor-liquid equilibria from the triple point up to the critical point for the new generation of TIP4P-like models: TIP4P/Ew, TIP4P/2005, and TIP4P/ice. , 2006, The Journal of chemical physics.

[8]  C. Vega,et al.  Anomalies in water as obtained from computer simulations of the TIP4P/2005 model: density maxima, and density, isothermal compressibility and heat capacity minima , 2009, 0905.4009.

[9]  Y. Shindo,et al.  NMR and FT-IR Studies of Hydrogen Bonds in Ethanol-Water Mixtures , 1995 .

[10]  H. Berendsen,et al.  A systematic study of water models for molecular simulation: Derivation of water models optimized for use with a reaction field , 1998 .

[11]  R. Mills,et al.  Self-diffusion in normal and heavy water in the range 1-45.deg. , 1973 .

[12]  N. Matubayasi,et al.  A new high-temperature multinuclear-magnetic-resonance probe and the self-diffusion of light and heavy water in sub- and supercritical conditions. , 2005, The Journal of chemical physics.

[13]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[14]  Berend Smit,et al.  Are pressure fluctuation-based equilibrium methods really worse than nonequilibrium methods for calculating viscosities? , 2009, The Journal of chemical physics.

[15]  P. Cummings,et al.  The importance of polarizability in the modeling of solubility: quantifying the effect of solute polarizability on the solubility of small nonpolar solutes in popular models of water. , 2008, The Journal of chemical physics.

[16]  Yang Zhong,et al.  Thermodynamic and structural properties of methanol–water solutions using nonadditive interaction models , 2008, J. Comput. Chem..

[17]  A. G. Williamson,et al.  Isothermal liquid-vapor equilibriums for system methanol-water , 1976 .

[18]  S. Weerasinghe,et al.  A Kirkwood-Buff derived force field for methanol and aqueous methanol solutions. , 2005, The journal of physical chemistry. B.

[19]  Florian Müller-Plathe,et al.  An All-Atom Force Field for Liquid Ethanol–Properties of Ethanol–Water Mixtures , 1996 .

[20]  B. Smit,et al.  Molecular simulations of the vapour-liquid coexistence curve of methanol , 1995 .

[21]  R. Impey,et al.  On the infrared and raman spectra of water in the region 5–250 cm−1 , 1986 .

[22]  I. R. Mcdonald,et al.  Pair interactions and hydrogen-bond networks in models of liquid methanol , 1986 .

[23]  Hans Hasse,et al.  ms2: A molecular simulation tool for thermodynamic properties , 2011, Comput. Phys. Commun..

[24]  J. A. Larkin,et al.  Thermodynamic properties of aqueous non-electrolyte mixtures I. Excess enthalpy for water + ethanol at 298.15 to 383.15 K , 1975 .

[25]  J. Abascal,et al.  The shear viscosity of rigid water models. , 2010, The Journal of chemical physics.

[26]  I. Nezbeda,et al.  Excess properties of aqueous mixtures of methanol: Simulation versus experiment , 2006 .

[27]  H. Berendsen,et al.  Interaction Models for Water in Relation to Protein Hydration , 1981 .

[28]  H. Stanley,et al.  Clustering dynamics in water/methanol mixtures: a nuclear magnetic resonance study at 205 k , 2008, The journal of physical chemistry. B.

[29]  B. Hess.  Determining the shear viscosity of model liquids from molecular dynamics simulations , 2002 .

[30]  A. C. Hoffmann,et al.  Dynamic properties of water/alcohol mixtures studied by computer simulation , 2003 .

[31]  R. Kubo.  Statistical-Mechanical Theory of Irreversible Processes : I. General Theory and Simple Applications to Magnetic and Conduction Problems , 1957 .

[32]  M. Holz,et al.  Temperature-dependent self-diffusion coefficients of water and six selected molecular liquids for calibration in accurate 1H NMR PFG measurements , 2000 .

[33]  Michael W. Mahoney,et al.  Diffusion constant of the TIP5P model of liquid water , 2001 .

[34]  S. Assadi,et al.  Temperature Dependence of the Volumetric Properties of Binary and Ternary Mixtures of Water (1) + Methanol (2) + Ethanol (3) at Ambient Pressure (81.5 kPa) , 2007 .

[35]  A. Galindo,et al.  Prediction of binary intermolecular potential parameters for use in modelling fluid mixtures , 2008 .

[36]  M. Klein,et al.  The effects of pressure on structural and dynamical properties of associated liquids: Molecular dynamics calculations for the extended simple point charge model of water , 1997 .

[37]  Faraday Discuss , 1985 .

[38]  L. C. Freitas,et al.  Monte Carlo Study of Structural and Thermodynamic Properties of Liquid Chloroform Using a Five Site Model , 1997 .

[39]  H. Hasse,et al.  Henry’s law constants of methane, nitrogen, oxygen and carbon dioxide in ethanol from 273 to 498 K: Prediction from molecular simulation , 2005, 0904.4793.

[40]  K. R. Harris,et al.  Alcohol tracer diffusion, density, NMR and FTIR studies of aqueous ethanol and 2,2,2-trifluoroethanol solutions at 25°C , 1998 .

[41]  Simon Bates,et al.  Structure and dynamics of water in aqueous methanol , 2005 .

[42]  Amalendu Chandra,et al.  Dynamical properties of the soft sticky dipole model of water: Molecular dynamics simulations , 1999 .

[43]  H. Stanley,et al.  Slow dynamics of water under pressure , 1999, cond-mat/9901049.

[44]  H. Hasse,et al.  Prediction of transport properties by molecular simulation: methanol and ethanol and their mixture. , 2008, The journal of physical chemistry. B.

[45]  Kenneth R. Harris,et al.  Pressure and temperature dependence of the self diffusion coefficient of water and oxygen-18 water , 1980 .

[46]  M. Holz,et al.  Biological applications of scanning tunnelling microscopy , 1993 .

[47]  Kazimierz Krynicki,et al.  Pressure and temperature dependence of self-diffusion in water , 1978 .

[48]  Benoît Roux,et al.  Molecular dynamics study of hydration in ethanol-water mixtures using a polarizable force field. , 2005, The journal of physical chemistry. B.

[49]  Lang,et al.  Diffusion in supercooled water to 300 MPa. , 1987, Physical review letters.

[50]  J. Crain,et al.  Hydration of methanol in aqueous solutions: a Raman spectroscopic study , 2000 .

[51]  J. Martí,et al.  Hydrogen bonding influence on the intermolecular vibrational spectra of liquid methanol , 1995 .

[52]  K. Gubbins,et al.  Thermodynamic and structural properties of methanol-water mixtures: experiment, theory, and molecular simulation , 1993 .

[53]  A. J. Easteal,et al.  Diffusion coefficients of methanol and water and the mutual diffusion coefficient in methanol-water solutions at 278 and 298 K , 1985 .

[54]  T. Straatsma,et al.  THE MISSING TERM IN EFFECTIVE PAIR POTENTIALS , 1987 .

[55]  Melville S. Green,et al.  Markoff Random Processes and the Statistical Mechanics of Time‐Dependent Phenomena. II. Irreversible Processes in Fluids , 1954 .

[56]  J. Banavar,et al.  Computer Simulation of Liquids , 1988 .

[57]  T. Vlugt,et al.  Molecular dynamics simulation of self-diffusion and Maxwell-Stefan diffusion coefficients in liquid mixtures of methanol and water , 1999 .

[58]  Pablo G. Debenedetti,et al.  Relationship between structural order and the anomalies of liquid water , 2001, Nature.

[59]  William L. Jorgensen,et al.  Optimized intermolecular potential functions for liquid alcohols , 1986 .

[60]  G. Walrafen,et al.  Temperature dependence of the low‐ and high‐frequency Raman scattering from liquid water , 1986 .

[61]  Michael L. Klein,et al.  Molecular-dynamics simulation of aqueous mixtures : methanol, acetone, and ammonia , 1990 .

[62]  E. M.,et al.  Statistical Mechanics , 2021, Manual for Theoretical Chemistry.

[63]  B. Ladanyi,et al.  Computational study of structural and dynamical properties of formamide-water mixtures. , 2006, The Journal of chemical physics.

[64]  C. Vega,et al.  What ice can teach us about water interactions: a critical comparison of the performance of different water models. , 2009, Faraday discussions.

[65]  T. S. V. Erp,et al.  Ab initio molecular dynamics study of aqueous solvation of ethanol and ethylene , 2002, physics/0212007.

[66]  P. Cummings,et al.  Nonequilibrium molecular dynamics calculation of the shear viscosity of liquid water , 1988 .

[67]  Haiyan Liu,et al.  Molecular dynamics simulations of liquid methanol and methanol–water mixtures with polarizable models , 2006, J. Comput. Chem..

[68]  P. Kollman,et al.  Molecular dynamics free energy simulations: Influence of the truncation of long‐range nonbonded electrostatic interactions on free energy calculations of polar molecules , 1994 .

[69]  J. Slusher.  Shear viscosity and dielectric constant in aqueous isopropanol and aqueous acetonitrile , 2000 .

[70]  G. Voth,et al.  Flexible simple point-charge water model with improved liquid-state properties. , 2006, The Journal of chemical physics.

[71]  K. Heinzinger,et al.  Molecular dynamics investigation of the inter- and intramolecular motions in liquid methanol and methanol-water mixtures , 1991 .

[72]  J. Sperry,et al.  Water Relations of Plants and Soils , 1995 .

[73]  C. Hoheisel.  Transport properties of molecular liquids , 1994 .

[74]  Yigang Zhang,et al.  Equilibrium molecular dynamics calculation of the bulk viscosity of liquid water , 2001 .

[75]  C. Vega,et al.  A general purpose model for the condensed phases of water: TIP4P/2005. , 2005, The Journal of chemical physics.

[76]  Kenneth T. Gillen,et al.  Self‐Diffusion in Liquid Water to −31°C , 1972 .

[77]  Horace Traubel.  Collect , 1904 .

[78]  H. Stanley,et al.  Translational and rotational diffusion in stretched water , 2002, cond-mat/0201138.

[79]  B. Lu,et al.  Excess Thermodynamic Properties of Aqueous Alcohol Solutions. , 1965 .

[80]  J. D. Bernal,et al.  A Theory of Water and Ionic Solution, with Particular Reference to Hydrogen and Hydroxyl Ions , 1933 .

[81]  A. J. Easteal,et al.  Diaphragm cell for high-temperature diffusion measurements. Tracer Diffusion coefficients for water to 363 K , 1989 .

[82]  Elvira Guàrdia,et al.  Structure and Dynamics of Liquid Ethanol , 1997 .

[83]  Shoshana J. Wodak,et al.  Computer simulations of liquid water: treatment of long-range interactions , 1990 .

[84]  Hans Hasse,et al.  Hydrogen bonding of methanol in supercritical CO2: comparison between 1H NMR spectroscopic data and molecular simulation results. , 2007, The journal of physical chemistry. B.

[85]  S. Z. Mikhail,et al.  Densities and Viscosities of Methanol-Water Mixtures. , 1961 .

[86]  K. Nakanishi,et al.  Computer experiments of aqueous solutions. V. Monte Carlo calculation on the hydrophobic interaction in 5 mol % methanol solution , 1984 .

[87]  F. Dullien,et al.  Predictive equations for self‐diffusion in liquids: A different approach , 1972 .

[88]  W. Wagner,et al.  The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use , 2002 .

[89]  Joseph Kestin,et al.  Thermophysical properties of fluid D2O , 1984 .

[90]  J. Crain,et al.  Segregation in aqueous methanol enhanced by cooling and compression. , 2004, The Journal of chemical physics.

[91]  P. Gómez-Álvarez,et al.  Thermodynamics and structure of the {water + methanol} system viewed from three simple additive pair-wise intermolecular potentials based on the rigid molecule approximation , 2010 .

[92]  Elvira Guàrdia,et al.  Molecular dynamics simulation of liquid water along the coexistence curve: Hydrogen bonds and vibrational spectra , 1996 .

[93]  A. G. Williamson,et al.  Enthalpies of mixture of ethanol and water at 25.degree.C , 1967 .

[94]  David van der Spoel,et al.  The Origin of Layer Structure Artifacts in Simulations of Liquid Water. , 2006 .

[95]  M. Berkowitz,et al.  Structure and dynamics of high‐pressure TIP4P water , 1987 .

[96]  R. L. Kay,et al.  Solvent structure in aqueous mixtures. III. Ionic conductances in ethanol-water mixtures at 10 and 25°C , 1976 .

[97]  Infinite dilution activity coefficients in hydrogen-bonded mixtures via molecular dynamics: the water/methanol system , 1999 .

[98]  Bertrand Guillot,et al.  A reappraisal of what we have learnt during three decades of computer simulations on water , 2002 .

[99]  Michael L. Klein,et al.  Effective pair potentials and the properties of water , 1989 .

[100]  M. Schoen,et al.  The mutual diffusion coefficient D 12 in binary liquid model mixtures. Molecular dynamics calculations based on Lennard-Jones (12-6) potentials , 1984 .

[101]  Xiaoning Yang,et al.  Molecular dynamics simulation of ethanol/water mixtures for structure and diffusion properties , 2005 .

[102]  Rolf Lustig,et al.  Angle-average for the powers of the distance between two separated vectors , 1988 .

[103]  Wilfred F. van Gunsteren,et al.  The viscosity of SPC and SPC/E water at 277 and 300 K , 1993 .

[104]  Greg L. Hura,et al.  Development of an improved four-site water model for biomolecular simulations: TIP4P-Ew. , 2004, The Journal of chemical physics.

[105]  Yingchun Liu,et al.  On the mutual diffusion properties of ethanol-water mixtures. , 2006, The Journal of chemical physics.

[106]  Michael L. Klein,et al.  Shear viscosity of polar fluids: Molecular dynamics calculations of water , 1996 .

[107]  X. Daura,et al.  Derivation of an improved simple point charge model for liquid water: SPC/A and SPC/L , 2002 .

[108]  E. Hawlicka,et al.  Dynamic properties of the NaCl–methanol–water systems—MD simulation studies , 2000 .

[109]  Henry S. Frank,et al.  Free Volume and Entropy in Condensed Systems III. Entropy in Binary Liquid Mixtures; Partial Molal Entropy in Dilute Solutions; Structure and Thermodynamics in Aqueous Electrolytes , 1945 .

[110]  M. V. Leeuwen.  Prediction of the vapour-liquid coexistence curve of alkanols by molecular simulation , 1996 .

[111]  H. Eugene Stanley,et al.  Configurational entropy and diffusivity of supercooled water , 1999, Nature.

[112]  B. Kvamme.  Molecular dynamics simulations and integral equations studies of model systems for aqueous mixtures of small alcohols , 1997 .