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Abstract:

The electrical conductivity of CsCl, KCl, Bu4NBr, and Bu 4NI was studied in stable and supercooled (metastable) sucrose and trehalose aqueous solutions over a wide viscosity range. The results indicate that large positive deviations from the Walden rule occur in these systems due to the higher tendency of the ions to move in water-rich regions, as previously observed for NaCl and MgCl2. The electrical molar conductivity viscosity dependence can be described with a fractional Walden rule (Ληα = constant), where α is a decoupling parameter which increases with ionic size and varies between 0.61 and 0.74 for all of the studied electrolytes. Using the electrical molar conductivity dependence of ion-ion interactions, an effective dielectric constant was calculated for a trehalose 39 wt% aqueous solution as a function of temperature. Above 278 K, the effective and the bulk solution dielectric constants are similar, but at lower temperatures, where the carbohydrate becomes less mobile than water, the effective dielectric constant approaches the dielectric constant of water. We also conclude that the solute-solvent dielectric friction contribution can be neglected, reinforcing the idea that the observed breakdown of the Walden rule is due to the existence of local microheterogeneities. The Walden plots for the studied ionic solutes show a decoupling similar to that found for the diffusion of water in the same solutions. © 2009 American Chemical Society.

Registro:

Documento: Artículo
Título:Fractional Walden rule for electrolytes in supercooled disaccharide aqueous solutions
Autor:Longinotti, M.P.; Corti, H.R.
Filiación:Gerencia de Química, Comisión Nacional de Energía Atómica, Av. General Paz 1499 (1650), San Martin, Buenos Aires, Argentina
Departamento de Química Inorgánica Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellon II, Ciudad Universitaria, (1428), Buenos Aires, Argentina
Departamento de Física de Materia Condensada, Comisión Nacional de Energía Atómica, Av. General Paz 1499 (1650), San Martin, Buenos Aires, Argentina
Instituto de Química Física de los Materiales, Medio Ambiente y Energia (INQUIMAE), Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón II, Ciudad Universitaria, (1428), Buenos Aires, Argentina
Palabras clave:Carbohydrates; Ceramic capacitors; Dielectric waveguides; Electric conductivity; Electrolytes; Ionization of liquids; Ions; Permittivity; Polysaccharides; Sodium chloride; Sugar (sucrose); Supercooling; Viscosity; Aqueous solutions; Bulk solutions; Dielectric constants; Dielectric friction; Diffusion of water; Effective dielectric constants; Electrical conductivity; Ion-ion interaction; Ionic sizes; Ionic solutes; Molar conductivities; Trehalose aqueous solutions; Solutions
Año:2009
Volumen:113
Número:16
Página de inicio:5500
Página de fin:5507
DOI: http://dx.doi.org/10.1021/jp810253s
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_v113_n16_p5500_Longinotti

Referencias:

  • Carpenter, J.F., Martin, B., Crowe, L.M., Crowe, J.H., (1987) Cryobiology, 24, pp. 455-464
  • Crowe, J.H., Leslie, S.B., Crowe, L.M., (1994) Cryobiology, 31, pp. 355-366
  • Crowe, J.H., Carpenter, J.F., Crowe, L.M., (1998) Annu. Rev. Physiol, 60, pp. 73-103
  • Carpenter, J.F., Hand, S.C., Crowe, L.M., Crowe, J.H., (1986) Arch. Biochem. Biophys, 250, pp. 505-512
  • Mazzobre, M.F., Buera, M.P., (1999) Biochim. Biophys. Ada, 1473, pp. 337-344
  • Miller, D.P., Anderson, R.E., de Pablo, J.J., (1998) Pharm. Res, 75, pp. 1215-1221
  • Mazzobre, M.F., Longinotti, M.P., Corti, H.R., Buera, M.P., (2001) Cryobiology, 43, pp. 199-210
  • Longinotti, M.P., Mazzobre, M.F., Buera, M.P., Corti, H.R., (2002) Phys. Chem. Chem. Phys, 4, pp. 533-540
  • Parker, R., Ring, S.G., (1995) Cryo-Letters, 16, pp. 197-207
  • Walden, P.Z., (1906) Phys. Chem, 55, pp. 207-246
  • Robinson, R.A., Stokes, R.H., (1955) Electrolyte Solutions, , Butterworths Sci. Pub, London
  • Green, W.H., (1908) J. Chem. Soc, Trans, 93, pp. 2049-2063
  • Stokes, J.M., Stokes, R.H., (1956) J. Phys. Chem, 60, pp. 217-220
  • Steel, B.J., Stokes, R.H., (1958) J. Phys. Chem, 62, pp. 450-452
  • Stokes, J.M., Stokes, R.H., (1958) J. Phys. Chem, 62, pp. 497-499
  • R. H. Stokes, The Structure of Electrolytic Solutions; Hammer W. J., Ed.; Wiley: New York, 1959; Treiner, C., Fuoss, R.M., (1965) J. Phys. Chem, 69, pp. 2576-2581
  • Bilz, W., Klemm, W.Z., (1926) Anorg. Allg. Chem, 152, pp. 267-294
  • Pugsley, F.A., Westmore, F.E., (1954) Can. J. Chem, 32, pp. 839-841
  • Miller, D.P., Conrad, P.B., Fucito, S., Corti, H.R., de Pablo, J.J., (2000) J. Phys. Chem. B, 104, pp. 10419-10425
  • Longinotti, M.P., Corti, H.R., (2004) J. Solution Chem, 33, pp. 1029-1038
  • Longinotti, M.P., Corti, H.R., (2007) Electrochem. Commun, 9, pp. 1444-1450
  • Champion, D., Hervet, H., Blond, G., Le Meste, M., Simatos, D., (1997) J. Phys Chem. B, 101, pp. 10674-10679
  • Corti, H.R., Frank, G.A., Marconi, M.C., (2008) J. Solution Chem, 37, pp. 1593-1608
  • Corti, H.R., Frank, G.A., Marconi, M.C., (2008) J. Phys. Chem. B, 112, pp. 12899-12906
  • Swallen, S.F., Bonvallet, P.A., McMahon, R.J., Ediger, M.D., (2003) Phys. Rev. Lett, 90, p. 015901
  • Mapes, M.K., Swallen, S.F., Ediger, M.D., (2006) J. Phys. Chem, 110, pp. 507-511
  • Blackburn, F.R., Wang, C.Y., Ediger, M.D., (1996) J. Phys. Chem, 700, pp. 18249-18257
  • Goldfarb, D.L., Longinotti, M.P., Corti, H.R., (2001) J. Solution Chem, 30, pp. 307-322
  • Barthel, J., Feuerlein, F., Neueder, R., Wachter, R., (1980) J. Solution Chem, 9, pp. 209-219
  • Barthel, J., Neueder, R., Feuerlein, F., Strasser, F., Iberl, L., (1983) J. Solution Chem, 12, pp. 449-471
  • Longinotti, M.P., Corti, H.R., (2008) J. Phys. Chem. Ref. Data, 37, pp. 1503-1515
  • Miller, D.P., de Pablo, J.J., Corti, H.R., (1997) Pharm. Res, 14, pp. 578-590
  • Elias, M.E., Elias, A.M., (1999) J. Mol. Liq, 83, pp. 303-310
  • Zhuo, K., Zhang, H., Wang, Y., Liu, Q., Wang, J., (2005) J. Chem. Eng. Data, 50, pp. 1589-1595
  • Chenlo, F., Moreira, R., Pereira, G., Ampudia, A., (2002) J. Food Eng, 54, pp. 347-352
  • Misra, V., Misra, V.P., (1977) Carbohyd. Res, 59, pp. 35-46
  • Lide, D.R., (1995) CRC Handbook of Chemistry and Physics, , 76th ed, CRC Press: Boca Raton, FL
  • Matsuoka, T., Okada, T., Murai, K., Koda, S., Nomura, H., (2002) J. Mol. Liq, 98-99, pp. 317-327
  • Bertolini, D., Cassettari, M., Salvetti, G., (1982) J. Chem. Phys, 76, pp. 3285-3290
  • Pancoast, H.M., Junk, W.R., (1980) Handbook of Sugars, , 2nd ed, AVI. Pub. Co: Westport, CT
  • Barthel, J., Schmeer, G., Gores, H.J., Feuerhein, F., (1983) Topics in current chemistry, , Ill; Springer: Heidelberg
  • Miao, W., Ding, Z., Bard, A.J., (2002) J. Phys. Chem. B, 706, pp. 1392-1398
  • Moore, A.W., Jorgenson, J.W., (1993) Anal. Chem, 65, pp. 3550-3560
  • Mustafa, M.B., Tripton, D.L., Russo, P.S., (1998) Macromolecules, 22, pp. 1500-1504
  • Mosier, B.P., Molho, J.J., Santiago, J.G., (2002) Exp. Fluids, 33, pp. 545-554
  • Mustafa, M.B., Tripton, D.L., Barkley, M.D., Russo, P.S., Blum, F.D., (1993) Macromolecules, 26, pp. 370-378
  • Zwanzig, R., (1970) J. Chem. Phys, 52, pp. 3625-3628
  • Hubbard, J., Onsager, L., (1977) J. Chem. Phys, 67, pp. 4850-4857
  • Wolynes, P.G., (1980) Annu. Rev. Phys. Chem, 31, pp. 345-376
  • Bagchi, B., Biswas, R., (1998) Ace. Chem. Res, 31, pp. 181-187
  • Rampp, M., Buttersack, C., Ludemman, H.D., (2000) Carbohyd. Res, 328, pp. 561-572
  • F. Mizuno, F.; Belieres, J.-P.; Kuwata, N.; Pradel, A.; Ribes, M.; Angell, C. A. J. Non-Crystal. Solid 2006, 352, 5147-5155; McLin, M.G., Angell, C.A., (1991) J. Phys. Chem, 95, pp. 9464-9469

Citas:

---------- APA ----------
Longinotti, M.P. & Corti, H.R. (2009) . Fractional Walden rule for electrolytes in supercooled disaccharide aqueous solutions. Journal of Physical Chemistry B, 113(16), 5500-5507.
http://dx.doi.org/10.1021/jp810253s
---------- CHICAGO ----------
Longinotti, M.P., Corti, H.R. "Fractional Walden rule for electrolytes in supercooled disaccharide aqueous solutions" . Journal of Physical Chemistry B 113, no. 16 (2009) : 5500-5507.
http://dx.doi.org/10.1021/jp810253s
---------- MLA ----------
Longinotti, M.P., Corti, H.R. "Fractional Walden rule for electrolytes in supercooled disaccharide aqueous solutions" . Journal of Physical Chemistry B, vol. 113, no. 16, 2009, pp. 5500-5507.
http://dx.doi.org/10.1021/jp810253s
---------- VANCOUVER ----------
Longinotti, M.P., Corti, H.R. Fractional Walden rule for electrolytes in supercooled disaccharide aqueous solutions. J Phys Chem B. 2009;113(16):5500-5507.
http://dx.doi.org/10.1021/jp810253s