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Abstract:

The diffusion of ferrocene methanol in supercooled glycerol-water mixtures has been measured over a wide viscosity range, which allowed analyzing the composition dependence of the Stokes-Einstein breakdown (diffusion-viscosity decoupling). The observed decoupling exhibits a common behavior for all studied compositions (glycerol mass fractions between 0.7 and 0.9), determined by the reduced temperature (T/Tg) of the mixtures. This result differs from that reported previously for the diffusion of glycerol in its aqueous solutions, where the reduced temperature for the decoupling decreases with increasing water content. We conclude that the contradictory results are only apparent, and they can be explained by the use of inconsistent extrapolated values of the viscosity of the glycerol-water mixtures in the supercooled region. (Figure Presented). © 2014 American Chemical Society.

Registro:

Documento: Artículo
Título:Diffusion-viscosity decoupling in supercooled glycerol aqueous solutions
Autor:Trejo González, J.A.; Longinotti, M.P.; Corti, H.R.
Filiación:Instituto de Quimica Fisica de Los Materiales, Medio Ambiente Y Energia (INQUIMAE-CONICET), Facultad de Ciencias Exactas Y Naturales, Universidad de Buenos Aires, Buenos Aires, 1428, Argentina
Departamento de Física de la Materia Condensada, Comisión Nacional de Energía Atómica, Av. General Paz 1499, San Martín, Buenos Aires, 1650, Argentina
Palabras clave:Diffusion; Mixtures; Organometallics; Solutions; Supercooling; Viscosity; Composition dependence; Ferrocenes; Glycerol-water mixtures; Mass fraction; Supercooled regions; Glycerol
Año:2015
Volumen:119
Número:1
Página de inicio:257
Página de fin:262
DOI: http://dx.doi.org/10.1021/jp509055v
Título revista:Journal of Physical Chemistry B
Título revista abreviado:J Phys Chem B
ISSN:15206106
CODEN:JPCBF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15206106_v119_n1_p257_TrejoGonzalez

Referencias:

  • Anderson, P.W., Through the glass lightly (1995) Science, 267, pp. 1615-1616
  • Debenedetti, P.G., (1996) Metastable Liquids: Concepts and Principles, , Princeton University Press: Princeton, NJ
  • Einstein, A., (1956) Investigation on the Theory of Brownian Motion, , Dover: New York
  • Rössler, E., Indications for a change of diffusion mechanism in supercooled liquids (1990) Phys. Rev. Lett., 65, pp. 1595-1598
  • Heuberger, G., Sillescu, H., Size dependence of tracer diffusion in supercooled liquids (1996) J. Phys. Chem., 100, pp. 15255-15260
  • Blackburn, F.R., Cicerone, M.T., Hietpas, G., Wagner, P.A., Ediger, M.D., Cooperative motion in fragile liquids near the glass transition: Probe reorientation in o-terphenyl and polystyrene (1994) J. Non-Cryst. Solids, 172-174, pp. 256-264
  • Ediger, M.D., Can density or entropy fluctuation explain enhanced translational diffusion in glass-forming liquids? (1998) J. Non-Cryst. Solids, 235-237, pp. 10-18
  • Chang, I., Fujara, F., Geil, B., Heuberger, G., Mangel, T., Silescu, H., Translational and rotational molecular motion in supercooled liquids studied by NMR and forced Rayleigh scattering (1994) J. Non-Cryst. Solids, 172-174, pp. 248-255
  • Cicerone, M.T., Blackburn, F.R., Ediger, M.D., How do molecules move near T g?. Molecular rotation of six probes in oterphenyl across 14 decades in time (1995) J. Chem. Phys., 102, pp. 471-4799
  • Le Meste, M., Voilley, A.J., Influence of hydration on rotational diffusivity of solutes in model systems (1988) J. Phys. Chem., 92, pp. 1612-1616
  • Matthiesen, J., Scott Smith, R., Kay, B.D., Mixing It Up: Measuring Diffusion in Supercooled Liquid Solutions of Methanol and Ethanol at Temperatures near the Glass Transition (2011) J. Phys. Chem. Lett., 2, pp. 557-561
  • Stanley, H.E., Buldyrev, S.V., Campolat, M., Mishima, O., Sadr-Lahijany, M.R., Scala, A., Starr, F.W., The puzzling behavior of water at very low temperature (2000) Phys. Chem. Chem. Phys., 2, pp. 1551-1558
  • Champion, D., Hevert, H., Blond, G., Le Meste, M., Simatos, D., Translational diffusion in sucrose solutions in the vicinity of their glass transition temperature (1997) J. Phys. Chem. B, 101, pp. 10674-10679
  • Rampp, M., Buttersack, C., Lüdemann, H.-D., c,T-Dependence of the viscosity and the self-diffusion coefficients in some aqueous carbohydrate solutions (2000) Carbohydr. Res., 328, pp. 561-572
  • Corti, H.R., Frank, G.A., Marconi, M.C., Diffusion-viscosity decoupling in supercooled aqueous trehalose solutions (2008) J. Phys. Chem. B, 112, pp. 12899-12906
  • Longinotti, M.P., Corti, H.R., Diffusion of ferrocene methanol in super-cooled aqueous solutions using cylindrical micro- electrodes (2007) Electrochem. Commun., 9, pp. 1444-1450
  • Miller, D.P., Fucito, S., De Pablo, J.J., Corti, H.R., Electrical conductivity of supercooled aqueous mixtures of trehalose with sodium chloride (2000) J. Phys. Chem. B, 104, pp. 10419-10425
  • Longinotti, M.P., Corti, H.R., Fractional Walden rule for electrolytes in supercooled disaccharide aqueous solutions (2009) J. Phys. Chem. B, 113, pp. 5500-5507
  • Chen, B., Sigmund, E.E., Halperin, W.P., Stokes-Einstein relation in supercooled aqueous solutions of glycerol (2006) Phys. Rev. Lett., 96, p. 145502
  • Kivelson, S.A., Zhao, X., Kivelson, D., Fisher, T.M., Knobler, C.M., Frustation-limited clusters in liquids (1994) J. Chem. Phys., 101, pp. 2391-2397
  • Tarjus, G., Kivelson, D., Breakdown of the Stokes-Einstein relation in supercooled liquids (1995) J. Chem. Phys., 103, pp. 3071-3073
  • Jung, Y., Garrahan, J.P., Chandler, D., Excitation lines and the breakdown of Stokes-Einstein relations in supercooled liquids (2004) Phys. Rev. E, 69, p. 061205
  • Carslaw, H.S., Jaeger, J.C., (1959) Conduction of Heat in Solids, 2nd Ed., pp. 334-336. , Oxford University Press
  • Szabo, A., Cope, D.K., Tallman, D.E., Kovach, P.M., Wightman, R.M., Chrono- amperometric current at hemicylinder and band microelectrodes: Theory and experiment (1987) J. Electroanal. Chem., 217, pp. 417-423
  • Moorcroft, M.J., Lawrence, N.S., Coles, B.A., Compton, R.C., Trevani, L.N., High temperature electrochemical studies using a channel flow cell heated by radio frequency radiation (2001) J. Electroanal. Chem., 506, pp. 28-33
  • Trejo, J.A., Longinotti, M.P., Corti, H.R., Viscosity of supercooled aqueous glycerol solutions, validity of the Stokes-Einstein relationship, and implications for cryopreservation (2012) Cryobiology, 65, pp. 159-162
  • Avramov, I., Milchev, A., Effect of disorder on diffusion and viscosity in condensed systems (1988) J. Non-Cryst. Solids, 104, pp. 253-260
  • Avramov, I., Viscosity in disordered media (2005) J. Non-Cryst. Solids, 351, pp. 3163-3173
  • Longinotti, M.P., Trejo, J.A., Corti, H.R., Concentration and temperature dependence of the viscosity of polyol aqueous solutions (2014) Cryobiology, 69, pp. 84-90
  • Chang, I., Silescu, H., Heterogeneity at the glass transition: Translational and rotational self-diffusion (1997) J. Phys. Chem. B, 101, pp. 8794-8801
  • Kruk, D., Meier, R., Rössler, E.A., Translational and rotational diffusion of glycerol by means of field cycling 1H NMR relaxometry (2011) J. Phys. Chem. B, 115, pp. 951-957
  • Takusagawa, F., Koetzle, T.F., A neutron diffraction study of the crystal structure of ferrocene (1979) Acta Crystallogr., Sect. B, 35, pp. 1074-1081
  • Heuberger, G., Sillescu, H., Size dependence of tracer diffusion in supercooled liquids (1996) J. Phys. Chem., 100, pp. 15255-15260
  • Rajian, J.R., Quitevis, E.L., Translational diffusion in sucrose benzoate near the glass transition: Probe size dependence in the breakdown of the Stokes-Einstein equation (2007) J. Chem. Phys., 126, p. 224506
  • Xia, X., Wolynes, P.G., Diffusion and the mesoscopic hydrodynamics of supercooled liquids (2001) J. Phys. Chem. B, 105, pp. 6570-6573
  • Banarjee, D., Bhat, S.V., Vitrification, relaxation and free volumen in glicerol-water binary liquid mixture: Spin probe ESR studies (2009) J. Non-Cryst. Solids, 355, pp. 2433-2438
  • Debye, P., (1929) Polar Molecules, , Dover: New York
  • Murata, K., Tanaka, H., Liquid-liquid transition without macroscopic phase separation in a water-glycerol mixture (2012) Nat. Mater., 11, pp. 436-443
  • Lombardo, T.G., Debenedetti, P.G., Stillinger, F.H., Computational probes of molecular motion in the Lewis-Wahnström model for ortho-terphenyl (2006) J. Chem. Phys., 125, p. 174507
  • Chong, S.-H., Kob, W., Coupling and decoupling between translational and rotational dynamics in a supercooled molecular liquid (2009) Phys. Rev. Lett., 102, p. 025702

Citas:

---------- APA ----------
Trejo González, J.A., Longinotti, M.P. & Corti, H.R. (2015) . Diffusion-viscosity decoupling in supercooled glycerol aqueous solutions. Journal of Physical Chemistry B, 119(1), 257-262.
http://dx.doi.org/10.1021/jp509055v
---------- CHICAGO ----------
Trejo González, J.A., Longinotti, M.P., Corti, H.R. "Diffusion-viscosity decoupling in supercooled glycerol aqueous solutions" . Journal of Physical Chemistry B 119, no. 1 (2015) : 257-262.
http://dx.doi.org/10.1021/jp509055v
---------- MLA ----------
Trejo González, J.A., Longinotti, M.P., Corti, H.R. "Diffusion-viscosity decoupling in supercooled glycerol aqueous solutions" . Journal of Physical Chemistry B, vol. 119, no. 1, 2015, pp. 257-262.
http://dx.doi.org/10.1021/jp509055v
---------- VANCOUVER ----------
Trejo González, J.A., Longinotti, M.P., Corti, H.R. Diffusion-viscosity decoupling in supercooled glycerol aqueous solutions. J Phys Chem B. 2015;119(1):257-262.
http://dx.doi.org/10.1021/jp509055v