Dynamics of molecular associates in methanol/water mixtures

Zhai, Yanqin; Luo, Peng; Waller, Jackson; Self, Jeffrey L.; Harriger, Leland W.; Z, Y.; Faraone, Antonio

doi:10.1039/d1cp04726d

Title: Dynamics of molecular associates in methanol/water mixtures

Journal Article · 22 December 2021 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/d1cp04726d · OSTI ID:1978762

^[1];

^[1]; Waller, Jackson ^[2];

^[3];

^[4];

^[1];

^[4]

University of Illinois at Urbana-Champaign, IL (United States)
North Carolina State University, Raleigh, NC (United States)
University of Texas, Austin, TX (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

The dynamics of molecular associates in a methanol/water mixture was investigated using quasielastic neutron scattering. By measuring the signal from four methanol/water samples differing only by their isotopic composition, the relative motion of the water to methanol molecules, i.e. their mutual dynamics, was determined at the nanoscale. The thus obtained nanoscopic mutual diffusion coefficient signals a significantly slower process than the single particle diffusion of either methanol or water in the system as well as their macroscopic mutual diffusion. The data do not provide any indication of microsegregation in this preeminent alcohol/water mixture; however, they do indicate the existence of long lived but dynamic molecular associates of water and methanol molecules. Our analysis of the structural relaxation shows that the lifetime of molecular association through hydrogen bonding determines the fact that viscosity of the mixtures at intermediate concentrations is higher than that of both pure components.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: University of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: National Institute of Standards and Technology (NIST); National Science Foundation (NSF); USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: SC0014084

OSTI ID:: 1978762

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 4 Vol. 24; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (71)

LINCS: A linear constraint solver for molecular simulations Hess, Berk; Bekker, Henk; Berendsen, Herman J. C. Journal of Computational Chemistry, Vol. 18, Issue 12 https://doi.org/10.1002/(SICI)1096-987X(199709)18:12<1463::AID-JCC4>3.0.CO;2-H	journal	September 1997
Settle: An analytical version of the SHAKE and RATTLE algorithm for rigid water models Miyamoto, Shuichi; Kollman, Peter A. Journal of Computational Chemistry, Vol. 13, Issue 8 https://doi.org/10.1002/jcc.540130805	journal	October 1992
Absolute measurements of the thermal conductivity of mixtures of alcohols with water Assael, M. J.; Charitidou, E.; Wakeham, W. A. International Journal of Thermophysics, Vol. 10, Issue 4 https://doi.org/10.1007/BF00514476	journal	July 1989
GROMACS: A message-passing parallel molecular dynamics implementation Berendsen, H. J. C.; van der Spoel, D.; van Drunen, R. Computer Physics Communications, Vol. 91, Issue 1-3 https://doi.org/10.1016/0010-4655(95)00042-E	journal	September 1995
The Disk Chopper Spectrometer at NIST: a new instrument for quasielastic neutron scattering studies Copley, J. R. D.; Cook, J. C. Chemical Physics, Vol. 292, Issue 2-3 https://doi.org/10.1016/S0301-0104(03)00124-1	journal	August 2003
Using polarization analysis to separate the coherent and incoherent scattering from protein samples Gaspar, Ana M.; Busch, Sebastian; Appavou, Marie-Sousai Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics, Vol. 1804, Issue 1 https://doi.org/10.1016/j.bbapap.2009.06.024	journal	January 2010
LiquidLib: A comprehensive toolbox for analyzing classical and ab initio molecular dynamics simulations of liquids and liquid-like matter with applications to neutron scattering experiments Walter, Nathan P.; Jaiswal, Abhishek; Cai, Zhikun Computer Physics Communications, Vol. 228 https://doi.org/10.1016/j.cpc.2018.03.005	journal	July 2018
Molecular dynamics simulations of aqueous solutions of short chain alcohols. Excess properties and the temperature of maximum density Pérez, Encarnación García; González-Salgado, Diego; Lomba, Enrique Fluid Phase Equilibria, Vol. 528 https://doi.org/10.1016/j.fluid.2020.112840	journal	January 2021
Hydrogen bonding in ethanol–water and trifluoroethanol–water mixtures studied by NMR and molecular dynamics simulation Matsugami, Masaru; Yamamoto, Ryohei; Kumai, Takashi Journal of Molecular Liquids, Vol. 217 https://doi.org/10.1016/j.molliq.2015.06.050	journal	May 2016
Glycerol Hydrogen-Bonding Network Dominates Structure and Collective Dynamics in a Deep Eutectic Solvent Faraone, A.; Wagle, D. V.; Baker, G. A. The Journal of Physical Chemistry B, Vol. 122, Issue 3 https://doi.org/10.1021/acs.jpcb.7b11224	journal	January 2018
Collective Mesoscale Dynamics of Liquid 1-Dodecanol Studied by Neutron Spin-Echo Spectroscopy with Isotopic Substitution and Molecular Dynamics Simulation Yamaguchi, Tsuyoshi; Faraone, Antonio; Nagao, Michihiro The Journal of Physical Chemistry B, Vol. 123, Issue 1 https://doi.org/10.1021/acs.jpcb.8b10299	journal	December 2018
Influence of Kosmotrope and Chaotrope Salts on Water Structural Relaxation Luo, Peng; Zhai, Yanqin; Senses, Erkan The Journal of Physical Chemistry Letters, Vol. 11, Issue 21 https://doi.org/10.1021/acs.jpclett.0c02619	journal	October 2020
The Nanostructure of Water-in-Salt Electrolytes Revisited: Effect of the Anion Size Horwitz, Gabriela; Härk, Eneli; Steinberg, Paula Y. ACS Nano, Vol. 15, Issue 7 https://doi.org/10.1021/acsnano.1c01737	journal	July 2021
Liquid Structure with Nano-Heterogeneity Promotes Cationic Transport in Concentrated Electrolytes Borodin, Oleg; Suo, Liumin; Gobet, Mallory ACS Nano, Vol. 11, Issue 10 https://doi.org/10.1021/acsnano.7b05664	journal	October 2017
Diffusion coefficients of methanol and water and the mutual diffusion coefficient in methanol-water solutions at 278 and 298 K Derlacki, Z. J.; Easteal, A. J.; Edge, A. V. J. The Journal of Physical Chemistry, Vol. 89, Issue 24 https://doi.org/10.1021/j100270a039	journal	November 1985
Prediction of velocity cross-correlation coefficients of binary liquid mixtures Bender, Thomas M.; Pecora, R. The Journal of Physical Chemistry, Vol. 93, Issue 6 https://doi.org/10.1021/j100343a073	journal	March 1989
The OPLS [optimized potentials for liquid simulations] potential functions for proteins, energy minimizations for crystals of cyclic peptides and crambin Jorgensen, William L.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 110, Issue 6 https://doi.org/10.1021/ja00214a001	journal	March 1988
Specific Heat Capacity at Constant Volume for Water, Methanol, and Their Mixtures at Temperatures from 300 K to 400 K and Pressures to 20 MPa Kuroki, Takahiro; Kagawa, Noboru; Endo, Harumi Journal of Chemical & Engineering Data, Vol. 46, Issue 5 https://doi.org/10.1021/je0002437	journal	July 2001
Excess isobaric heat capacities of water-n-alcohol mixtures Benson, George C.; D'Arcy, Patrick J. Journal of Chemical & Engineering Data, Vol. 27, Issue 4 https://doi.org/10.1021/je00030a021	journal	October 1982
Isochoric Heat Capacities of Alkanols and Their Aqueous Mixtures Kitajima, Hiroshi; Kagawa, Noboru; Endo, Harumi Journal of Chemical & Engineering Data, Vol. 48, Issue 6 https://doi.org/10.1021/je034101z	journal	October 2003
Densities and Viscosities of Methanol-Water Mixtures. Mikhail, S. Z.; Kimel, W. R. Journal of Chemical & Engineering Data, Vol. 6, Issue 4 https://doi.org/10.1021/je60011a015	journal	October 1961
Temperature Dependence of the Volumetric Properties of Binary and Ternary Mixtures of Water (1) + Methanol (2) + Ethanol (3) at Ambient Pressure (81.5 kPa) Zarei, Hossein A.; Jalili, F.; Assadi, S. Journal of Chemical & Engineering Data, Vol. 52, Issue 6 https://doi.org/10.1021/je700300y	journal	September 2007
Solution Dynamics in Aqueous Monohydric Alcohol Systems Price, William S.; Ide, Hiroyuki; Arata, Yoji The Journal of Physical Chemistry A, Vol. 107, Issue 24 https://doi.org/10.1021/jp027257z	journal	May 2003
Nanoscale Segregation in Room Temperature Ionic Liquids ^† Triolo, Alessandro; Russina, Olga; Bleif, Hans-Jurgen The Journal of Physical Chemistry B, Vol. 111, Issue 18 https://doi.org/10.1021/jp067705t	journal	May 2007
Hydrophobic Segregation, Phase Transitions and the Anomalous Thermodynamics of Water/Methanol Mixtures Pascal, Tod A.; Goddard, William A. The Journal of Physical Chemistry B, Vol. 116, Issue 47 https://doi.org/10.1021/jp309693d	journal	November 2012
Clustering Dynamics in Water/Methanol Mixtures: A Nuclear Magnetic Resonance Study at 205 K < T < 295 K Corsaro, Carmelo; Spooren, Jeroen; Branca, Caterina The Journal of Physical Chemistry B, Vol. 112, Issue 34 https://doi.org/10.1021/jp803456p	journal	August 2008
Dynamical Crossover and Breakdown of the Stokes−Einstein Relation in Confined Water and in Methanol-Diluted Bulk Water Mallamace, Francesco; Branca, Caterina; Corsaro, Carmelo The Journal of Physical Chemistry B, Vol. 114, Issue 5 https://doi.org/10.1021/jp910038j	journal	February 2010
Molecular segregation observed in a concentrated alcohol–water solution Dixit, S.; Crain, J.; Poon, W. C. K. Nature, Vol. 416, Issue 6883 https://doi.org/10.1038/416829a	journal	April 2002
Nanostructuration of ionic liquids: impact on the cation mobility. A multi-scale study Ferdeghini, Filippo; Berrod, Quentin; Zanotti, Jean-Marc Nanoscale, Vol. 9, Issue 5 https://doi.org/10.1039/C6NR07604A	journal	January 2017
Relevance of hydrogen bonded associates to the transport properties and nanoscale dynamics of liquid and supercooled 2-propanol Zhai, Yanqin; Luo, Peng; Nagao, Michihiro Physical Chemistry Chemical Physics, Vol. 23, Issue 12 https://doi.org/10.1039/D0CP05481J	journal	January 2021
Small-angle neutron scattering study of D ₂ O–alcohol solutions D'Arrigo, Giovanni; Teixeira, José J. Chem. Soc., Faraday Trans., Vol. 86, Issue 9 https://doi.org/10.1039/FT9908601503	journal	January 1990
The structural properties of alcohol–water mixtures Franks, F.; Ives, D. J. G. Q. Rev. Chem. Soc., Vol. 20, Issue 1 https://doi.org/10.1039/QR9662000001	journal	January 1966
Novel solvent properties of choline chloride/urea mixturesElectronic supplementary information (ESI) available: spectroscopic data. See http://www.rsc.org/suppdata/cc/b2/b210714g/ Abbott, Andrew P.; Capper, Glen; Davies, David L. Chemical Communications, Issue 1 https://doi.org/10.1039/b210714g	journal	November 2002
Mesoscale inhomogeneities in aqueous solutions of small amphiphilic molecules Subramanian, Deepa; Boughter, Christopher T.; Klauda, Jeffery B. Faraday Discussions, Vol. 167 https://doi.org/10.1039/c3fd00070b	journal	January 2013
Fluctuations and micro-heterogeneity in mixtures of complex liquids Perera, Aurélien; Kežić, Bernarda Faraday Discussions, Vol. 167 https://doi.org/10.1039/c3fd00072a	journal	January 2013
Solute interactions in dilute aqueous solutions. Part 1.—Microcalorimetric study of the hydrophobic interaction Franks, Felix; Pedley, Michael; Reid, David S. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, Issue 0 https://doi.org/10.1039/f19767200359	journal	January 1976
Solute interactions in dilute solutions. Part 2.—A statistical mechanical study of the hydrophobic interaction Clark, Alan H.; Franks, Felix; Pedley, Michael D. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0 https://doi.org/10.1039/f19777300290	journal	January 1977
Segregation in aqueous methanol enhanced by cooling and compression Dougan, L.; Hargreaves, R.; Bates, S. P. The Journal of Chemical Physics, Vol. 122, Issue 17 https://doi.org/10.1063/1.1888405	journal	May 2005
Kirkwood-Buff integrals of aqueous alcohol binary mixtures Perera, A.; Sokolić, F.; Almásy, L. The Journal of Chemical Physics, Vol. 124, Issue 12 https://doi.org/10.1063/1.2178787	journal	March 2006
Coherent dynamics of meta -toluidine investigated by quasielastic neutron scattering Faraone, Antonio; Hong, Kunlun; Kneller, Larry R. The Journal of Chemical Physics, Vol. 136, Issue 10 https://doi.org/10.1063/1.3691185	journal	March 2012
Interpretation of the unusual behavior of H ₂ O and D ₂ O at low temperatures: Tests of a percolation model Stanley, H. Eugene; Teixeira, J. The Journal of Chemical Physics, Vol. 73, Issue 7 https://doi.org/10.1063/1.440538	journal	October 1980
Comparison of simple potential functions for simulating liquid water Jorgensen, William L.; Chandrasekhar, Jayaraman; Madura, Jeffry D. The Journal of Chemical Physics, Vol. 79, Issue 2 https://doi.org/10.1063/1.445869	journal	July 1983
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Molecular dynamics with coupling to an external bath Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F. The Journal of Chemical Physics, Vol. 81, Issue 8 https://doi.org/10.1063/1.448118	journal	October 1984
A smooth particle mesh Ewald method Essmann, Ulrich; Perera, Lalith; Berkowitz, Max L. The Journal of Chemical Physics, Vol. 103, Issue 19 https://doi.org/10.1063/1.470117	journal	November 1995
A molecular dynamics study of the equation of state and the structure of supercooled aqueous solutions of methanol Corradini, Dario; Su, Zhiqiang; Stanley, H. Eugene The Journal of Chemical Physics, Vol. 137, Issue 18 https://doi.org/10.1063/1.4767060	journal	November 2012
Alcohol-induced drying of carbon nanotubes and its implications for alcohol/water separation: A molecular dynamics study Tian, Xingling; Yang, Zaixing; Zhou, Bo The Journal of Chemical Physics, Vol. 138, Issue 20 https://doi.org/10.1063/1.4807484	journal	May 2013
Low-temperature water dynamics in an aqueous methanol solution Bertrand, C. E.; Chiang, W. -S.; Tyagi, M. The Journal of Chemical Physics, Vol. 139, Issue 1 https://doi.org/10.1063/1.4812286	journal	July 2013
Dynamical properties of water-methanol solutions Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico The Journal of Chemical Physics, Vol. 144, Issue 6 https://doi.org/10.1063/1.4941414	journal	February 2016
Dynamic signature of molecular association in methanol Bertrand, C. E.; Self, J. L.; Copley, J. R. D. The Journal of Chemical Physics, Vol. 145, Issue 1 https://doi.org/10.1063/1.4954964	journal	July 2016
The microscopic structure of cold aqueous methanol mixtures Požar, Martina; Kerasidou, Ariadni; Lovrinčević, Bernarda The Journal of Chemical Physics, Vol. 145, Issue 14 https://doi.org/10.1063/1.4964487	journal	October 2016
Viscoelastic relaxations of high alcohols and alkanes: Effects of heterogeneous structure and translation-orientation coupling Yamaguchi, Tsuyoshi The Journal of Chemical Physics, Vol. 146, Issue 9 https://doi.org/10.1063/1.4977705	journal	March 2017
Nanoscopic length scale dependence of hydrogen bonded molecular associates’ dynamics in methanol Bertrand, C. E.; Self, J. L.; Copley, J. R. D. The Journal of Chemical Physics, Vol. 146, Issue 19 https://doi.org/10.1063/1.4983179	journal	May 2017
Analysis of shear viscosity and viscoelastic relaxation of liquid methanol based on molecular dynamics simulation and mode-coupling theory Yamaguchi, Tsuyoshi; Faraone, Antonio The Journal of Chemical Physics, Vol. 146, Issue 24 https://doi.org/10.1063/1.4990408	journal	June 2017
The Stokes-Einstein relation in water/methanol solutions Corsaro, C.; Fazio, E.; Mallamace, D. The Journal of Chemical Physics, Vol. 150, Issue 23 https://doi.org/10.1063/1.5096760	journal	June 2019
A molecular dynamics method for simulations in the canonical ensemble Nosé, Shūichi Molecular Physics, Vol. 52, Issue 2 https://doi.org/10.1080/00268978400101201	journal	June 1984
Dynamical structure factors for a fluid binary mixture in the hydrodynamic limit Bhatia, A. B.; Thornton, D. E.; March, N. H. Physics and Chemistry of Liquids, Vol. 4, Issue 2-3 https://doi.org/10.1080/00319107408084276	journal	January 1974
Viscosities of Binary and Ternary Mixtures of Water, Alcohol, Acetone, and Hexane Song, Shaoxian; Peng, Changsheng Journal of Dispersion Science and Technology, Vol. 29, Issue 10 https://doi.org/10.1080/01932690802313006	journal	October 2008
Structure of Binary Liquid Mixtures. I Ashcroft, N. W.; Langreth, David C. Physical Review, Vol. 156, Issue 3 https://doi.org/10.1103/PhysRev.156.685	journal	April 1967
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
Structural Aspects of the Electrical Resistivity of Binary Alloys Bhatia, A. B.; Thornton, D. E. Physical Review B, Vol. 2, Issue 8 https://doi.org/10.1103/PhysRevB.2.3004	journal	October 1970
Mutual diffusion in binary Ar-Kr mixtures and empirical diffusion models Zhou, Yanhua; Miller, Gregory H. Physical Review E, Vol. 53, Issue 2 https://doi.org/10.1103/PhysRevE.53.1587	journal	February 1996
Dynamical properties of water-methanol solutions studied by depolarized Rayleigh scattering Micali, Norberto; Trusso, Sebastiano; Vasi, Cirino Physical Review E, Vol. 54, Issue 2 https://doi.org/10.1103/PhysRevE.54.1720	journal	August 1996
Microstructure of neat alcohols Perera, Aurélien; Sokolić, Franjo; Zoranić, Larisa Physical Review E, Vol. 75, Issue 6 https://doi.org/10.1103/PhysRevE.75.060502	journal	June 2007
Hydration of methanol in aqueous solution Soper, A. K.; Finney, J. L. Physical Review Letters, Vol. 71, Issue 26 https://doi.org/10.1103/PhysRevLett.71.4346	journal	December 1993
Molecular Structure of Alcohol-Water Mixtures Guo, J. -H.; Luo, Y.; Augustsson, A. Physical Review Letters, Vol. 91, Issue 15 https://doi.org/10.1103/PhysRevLett.91.157401	journal	October 2003
Coherent structural relaxation of water from meso- to intermolecular scales measured using neutron spectroscopy with polarization analysis Arbe, Arantxa; Nilsen, Gøran J.; Stewart, J. Ross Physical Review Research, Vol. 2, Issue 2 https://doi.org/10.1103/PhysRevResearch.2.022015	journal	April 2020
Reduction and analysis of SANS and USANS data using IGOR Pro Kline, Steven R. Journal of Applied Crystallography, Vol. 39, Issue 6, p. 895-900 https://doi.org/10.1107/S0021889806035059	journal	November 2006
The 30 m Small-Angle Neutron Scattering Instruments at the National Institute of Standards and Technology Glinka, C. J.; Barker, J. G.; Hammouda, B. Journal of Applied Crystallography, Vol. 31, Issue 3, p. 430-445 https://doi.org/10.1107/S0021889897017020	journal	June 1998
Concentration fluctuations in water–methanol mixtures as studied by ultrasonic absorption Dale, William D. T.; Flavelle, Peter A.; Kruus, Peeter Canadian Journal of Chemistry, Vol. 54, Issue 3 https://doi.org/10.1139/v76-050	journal	February 1976
DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6 https://doi.org/10.6028/jres.114.025	journal	November 2009

Similar Records

Dynamic signature of molecular association in methanol

Journal Article · 2016 · Journal of Chemical Physics · OSTI ID:22675997

Bertrand, C. E.; Copley, J. R. D.; Self, J. L.

Relevance of hydrogen bonded associates to the transport properties and nanoscale dynamics of liquid and supercooled 2-propanol

Journal Article · 2021 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1851866

Zhai, Yanqin; Luo, Peng; Nagao, Michihiro; +6 more

Thermal diffusion in carbon tetrachloride-methanol and carbon tetrachloride-ethanol mixtures

Journal Article · 1983 · J. Phys. Chem.; (United States) · OSTI ID:6883267

Richard Ma, N Y.R.; Stanford, D; Beyerlein, A L

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS

Title: Dynamics of molecular associates in methanol/water mixtures

Citation Formats

References (71)

Similar Records

Related Subjects