Abstract
The electrophoretic mobilities of a few halide isotopes in aqueous solution have been evaluated at 25 °C and infinite dilution by analyzing a combination of data obtained by capillary electrophoresis (CE) and conductance data extracted from the literature. The effect of the temperature on the electrophoretic mobility has been thoroughly re-investigated to give the following temperature dependence for the chloride ion at 25 °C: 1.565%/ °C in 5×10−3 mol⋅L−1 sodium chromate + 3×10−3 mol⋅L−1 sodium borate buffer. The precise determination of the electrophoretic mobility of chloride and bromide ions, including the evaluation of their associated uncertainties, has been performed from conductance data spanning over 75 years. The electrophoretic mobilities are found to be −(79.124±0.020)×10−9 m2⋅V−1⋅s−1 for Cl− and −(80.99±0.04)×10−9 m2⋅V−1⋅s−1 for Br−. Thanks to the precise determination of the temperature contribution and the re-evaluation of conductance data, the following values have been found for 35Cl−, 37Cl−, 79Br−, and 81Br− (in 10−9 m2⋅V−1⋅s−1): −(79.18±0.02), −(78.95±0.06), −(81.04±0.04), and −(80.94±0.04).
Similar content being viewed by others
References
Avdalovic, N., Pohl, C.A., Rocklin, R.D., Stillian, J.R.: Determination of cations and anions by capillary electrophoresis combined with suppressed conductivity detection. Anal. Chem. 65, 1470–1475 (1993)
Lucy, C.A., McDonald, T.L.: Separation of chloride isotopes by capillary electrophoresis based on the isotope effect on ion mobility. Anal. Chem. 67, 1074–1078 (1995)
Fritz, J.S.: Determination of inorganic anions and metal cations. In: Camilleri, P. (ed.) Capillary Electrophoresis: Theory and Practice, pp. 250–272. CRC Press, Boca Raton (1998)
Aupiais, J.: Personnal communication (1996)
Henley, W.H., Wilburn, R.T., Crouch, A.M., Jorgenson, J.W.: Flow counterbalanced capillary electrophoresis using packed capillary columns: resolution of enantiomers and isotopomers. Anal. Chem. 77, 7024–7031 (2005)
Gas, B., Coufal, P., Jaros, M., Muzikar, J., Jelinek, I.: Optimization of background electrolytes for capillary electrophoresis I. Mathematical and computational model. J. Chromatogr. A 905, 269–279 (2001)
Jaros, M., Hruska, V., Stedry, M., Zuskova, I., Gas, B.: Eigenmobilities in background electrolytes for capillary zone electrophoresis: IV. Computer program PeakMaster. Electrophoresis 25, 3080–3085 (2004)
Jaros, M., Vcelakova, K., Zuskova, I., Gas, B.: Optimization of background electrolytes for capillary electrophoresis: II. Computer simulation and comparison with experiments. Electrophoresis 23, 2667–2677 (2002)
Stedry, M., Jaros, M., Gas, B.: Eigenmobilities in background electrolytes for capillary zone electrophoresis—I. System eigenpeaks and resonance in systems with strong electrolytes. J. Chromatogr. A 960, 187–198 (2002)
Stedry, M., Jaros, M., Hruska, V., Gas, B.: Eigenmobilities in background electrolytes for capillary zone electrophoresis: III. Linear theory of electromigration. Electrophoresis 25, 3071–3079 (2004)
Onsager, L., Fuoss, R.M.: Irreversible processes in electrolytes. Diffusion, conductances, and viscous flow in arbitrary mixtures of strong electrolytes. J. Phys. Chem. 36, 2689–2778 (1932)
Evenhuis, C.J., Guijt, R.M., Macka, M., Marriott, P.J., Haddad, P.R.: Internal electrolyte temperatures for polymer and fused-silica capillaries used in capillary electrophoresis. Electrophoresis 26, 4333–4344 (2005)
Peterson, S.L., Nikolajsen, R.P.H., Mogensen, K.B., Kutter, J.P.: Effect of joule heating on efficiency performance for microchip-based capillary-based electrophoretic separation systems: a closer look. Electrophoresis 25, 253–269 (2004)
Philippini, V., Aupiais, J., Vercouter, T., Moulin, C.: Formation of CaSO4(aq) and CaSeO4(aq) studied as a function of ionic strength and temperature by CE. Electrophoresis 30, 3582–3590 (2009)
Harris, K.R., Woolf, L.A.: Correction to the article “Temperature and volume dependence of the viscosity of water and heavy water at low temperatures”. J. Chem. Eng. Data 49, 1851 (2004)
Harris, K.R., Woolf, L.A.: Temperature and volume dependence of the viscosity of water and heavy water at low temperatures. J. Chem. Eng. Data 49, 1064–1069 (2004)
Archer, D.G., Wang, P.: The dielectric constant of water and Debye-Hückel limiting law slopes. J. Phys. Chem. Ref. Data 19, 371–411 (1990)
Isono, T.: Density, viscosity, and electrolytic conductivity of concentrated aqueous electrolyte solutions at several temperatures. Alkaline-earth chlorides, LaCl3, Na2SO4, NaNO3, NaBr, KNO3, KBr, and Cd(NO3)2. J. Chem. Eng. Data 29, 45–52 (1984)
Jones, H.C., Jacobson, C.A.: The conductivity and ionization of electrolytes in aqueous solutions as conditioned by temperature, dilution, and hydrolysis. Am. Chem. J. 40, 355–410 (1908)
Hayashi, M.: Temperature-electrical conductivity relation of water for environmental monitoring and geophysical data inversion. Environ. Monit. Assess. 96, 119–128 (2004)
Benson, G.C., Gordon, A.R.: A reinvestigation of the conductance of aqueous solutions of potassium chloride, sodium chloride, and potassium bromide at temperatures from 15° to 45°C. J. Chem. Phys. 13, 473–474 (1945)
Gunning, H.E., Gordon, A.R.: The conductance and ionic mobilities for aqueous solutions of potassium and sodium chloride at temperatures from 15° to 45°C. J. Phys. Chem. 10, 126–131 (1942)
Robinson, R.A., Stokes, R.H.: The variation of equivalent conductance with concentration and temperature. J. Am. Chem. Soc. 76, 1991–1994 (1954)
Watkins, C., Jones, H.C.: Conductivity and dissociation of some rather unusual salts in aqueous solution. J. Am. Chem. Soc. 37, 2626–2636 (1915)
Gunning, H.E., Gordon, A.R.: The conductance of aqueous solutions of potassium bromide at temperatures from 15° to 45°C, and the limiting mobility of bromide ion. J. Phys. Chem. 11, 18–20 (1943)
Anderko, A., Lencka, M.M.: Computation of electrical conductivity of multicomponent aqueous systems in wide concentration and temperature ranges. Ind. Eng. Chem. Res. 36, 1932–1943 (1997)
Coplen, T.B., Böhlke, J.K., De Bièvre, P., Ding, T., Holden, N.E., Hopple, J.A., Krouse, H.R., Lamberty, A., Peiser, H.S., Révész, K., Rieder, S.E., Rosman, K.J.R., Roth, E., Taylor, P.D.P., Vocke, R.D. Jr., Xiao, Y.K.: Isotope-abundance variations of selected elements. Pure Appl. Chem. 74, 1987–2017 (2002)
Le Petit, G., Granier, G.: Spectrométrie Gamma Appliquée aux Échantillons de l’Environnement. TEC & DOC, Paris (2002)
Eggenkamp, H.G.M., Coleman, M.L.: The effect of aqueous diffusion on the fractionation of chlorine and bromine stable isotopes. Geochim. Cosmochim. Acta 73, 3539–3548 (2009)
Richter, F.M., Mendybaev, R.A., Christensen, J.N., Hutcheon, I.D., Williams, R.W., Sturchio, N.C., Beloso, A.D.J.: Kinetic isotopic fractionation during diffusion of ionic species in water. Geochim. Cosmochim. Acta 70, 277–289 (2006)
Grossman, P.D., Colburn, J.C.: Capillary Electrophoresis—Theory and Practice. Academic Press, San Diego (1992)
Peterson, N.J., Nikolajsen, R.P.H., Mogensen, K.B., Kutter, J.P.: Effect of joule heating on efficiency and performance for microchip-based and capillary-based electrophoretic separation systems: a closer look. Electrophoresis 25, 253–269 (2004)
Kosmulski, M.: Surface Charging and Points of Zero Charge. CRC Press, Boca Raton (2009)
Evenhuis, C.J., Guijt, R.M., Macka, M., Marriott, P.J., Haddad, P.R.: Temperature profiles and heat dissipation in capillary electrophoresis. Anal. Chem. 78, 2684–2693 (2006)
Evenhuis, C.J., Guijt, R.M., Macka, M., Marriott, P.J., Haddad, P.R.: Heat production and dissipation in capillary electrophoresis. In: Landers, J.P. (ed.) Handbook of Capillary and Microchip Electrophoresis and Associated Microtechniques, pp. 545–562. CRC Press, Boca Raton (2007)
De Laeter, J.R., Böhlke, J.K., De Bièvre, P., Hidaka, H., Peiser, H.S., Rosman, K.J.R., Taylor, P.D.P.: Atomic weights of the elements: review 2000. Pure Appl. Chem. 75, 683–800 (2003)
Marsh, K.N.: Recommended reference materials for realization of physicochemical properties. Pure Appl. Chem. 53, 1847–1862 (1981). Section: Permittivity
Ribeiro, A.C.F., Esteso, M.A., Lobo, V.M.M., Burrows, H.D., Amado, A.M., Amorim da Costa, A.M., Sobral, A.J.F.N., Azevedo, E.F.G., Ribeiro, M.A.F.: Mean distance of closest approach of ions: sodium salts in aqueous solutions. J. Mol. Liq. 128, 134–139 (2006)
Mohr, P.J., Taylor, B.N., Newell, D.B.: CODATA recommended values of the fundamental physical constants: 2006. National Institute of Standards and Technology, Gaithersburg (2007)
Weast, R.C., Astle, M.J., Veyer, W.H. (eds.): Handbook of Chemistry and Physics, 69th edn. CRC Press, Boca Raton (1988)
Hirokawa, T., Nishino, M., Aoki, N., Kiso, Y., Sawamoto, Y., Yagi, T., Akiyama, J.-I.: Table of isotachophoretic indices—I. Simulated qualitative and quantitative indices of 287 anionic substances in the range pH 3–10. J. Chromatogr. 271, D1–D106 (1983)
Owen, B.B., Zeldes, H.: The conductance of potassium chloride, potassium bromide and potassium iodide in aqueous solutions from 5 to 55°. J. Chem. Phys. 18, 1083–1085 (1950)
Hsia, K.-L., Fuoss, R.M.: Conductance of the alkali halides. XI. Cesium bromide and iodide in water at 25°. J. Am. Chem. Soc. 90, 3055–3060 (1968)
Treiner, C., Justice, J.C., Fuoss, R.M.: Conductance of the alkali halides. X. The limiting conductance of the cesium ion in water at 25°. J. Phys. Chem. 68, 3886–3887 (1964)
Wypych-Stasiewicz, A., Szejgis, A., Chmielewska, A., Bald, A.: Conductance studies of NaBPh4, NBu4I, NaI, NaCl, NaBr, NaClO4 and the limiting ionic conductance in water+propan-1-ol mixtures at 298.15 K. J. Mol. Liq. 130, 34–37 (2007)
Kay, R.L., Evans, D.F.: The effect of solvent structure on the mobility of symmetrical ions in aqueous solution. J. Phys. Chem. 70, 2325–2335 (1966)
Lange, J.: Zur Leitfähigkeit starker Elektrolyte. Z. Phys. Chem. A 188, 284–315 (1941)
Jones, G., Bickford, C.F.: The conductance of aqueous solutions as a function of the concentration. I. Potassium bromide and lanthanum chloride. J. Am. Chem. Soc. 56, 602–611 (1934)
Longsworth, L.G.: Transference numbers of aqueous solutions of some electrolytes at 25° by the moving boundary method. J. Am. Chem. Soc. 57, 1185–1191 (1935)
Swain, C.G., Evans, D.F.: Conductance of ions in light and heavy water at 25°. J. Am. Chem. Soc. 88, 383–390 (1966)
Ritson, D.M., Hasted, J.B.: Dilectric properties of aqueous ionic solutions. Part II. J. Chem. Phys. 16, 11–21 (1948)
Spedding, F.H., Yaffe, I.S.: Conductances, transference numbers and activity coefficients of aqueous solutions of some rare earth halides at 25°. J. Am. Chem. Soc. 74, 4751–4755 (1952)
Justice, J.C., Bury, R., Treiner, C.: Conductibilité des électrolytes symétriques. II. Bromure de césium dans des mélanges eau-dioxane et eau-tétrahydrofuranne à 25°C. J. Chim. Phys. 65, 1708–1722 (1968)
Lucy, C.A.: Factors affecting selectivity of inorganic anions in capillary electrophoresis. J. Chromatogr. A 850, 319–337 (1999)
Kaniansky, D., Masar, M., Marak, J., Bodor, R.: Capillary electrophoresis of inorganic anions. J. Chromatogr. A 834, 133–178 (1999)
Shedlovsky, T., Brown, A.S.: The electrolytic conductivity of alkaline earth chlorides in water at 25°. J. Am. Chem. Soc. 56, 1066–1071 (1934)
McInnes, D.A., Shedlovsky, T., Longsworth, L.G.: The limiting equivalent conductances of several univalent ions in water at 25°. J. Am. Chem. Soc. 54, 2758–2762 (1932)
Owen, B.B., Sweeton, F.H.: The conductance of hydrochloric acid in aqueous solutions from 5 to 65°. J. Am. Chem. Soc. 63, 2811–2817 (1941)
Strong, L.E., Pethybridge, A.D.: Aqueous iodic acid: conductance and thermodynamics. J. Solution Chem. 16, 841–855 (1987)
King, F., Spiro, M.: Transference numbers and phenomenological transport coefficients for concentrated aqueous hydrochloric acid solutions at 25 °C. J. Solution Chem. 12, 65–81 (1983)
Bianchi, H., Corti, H.R., Fernandez-Prini, R.: The conductivity of dilute aqueous solutions of magnesium chloride at 25°C. J. Solution Chem. 17, 1059–1065 (1988)
Chiu, Y.C., Fuoss, R.M.: Conductance of the alkali halides. XII. Sodium and potassium chlorides in water at 25°. J. Phys. Chem. 72, 4123–4129 (1968)
Weingärtner, H., Müller, K.J., Hertz, H.G., Edge, V.J., Mills, R.: Unusual behavior of transport coefficients in aqueous solutions of zinc chloride at 25°C. J. Phys. Chem. 88, 2173–2178 (1984)
Li, N.C.C., Brüll, W.: Conductivities studies. IV. The limiting ionic mobilities of several univalent ions at temperatures between 15 and 45°. J. Am. Chem. Soc. 64, 1635–1637 (1942)
Murr, B.L. Jr., Shiner, V.J. Jr.: Precise conductance measurements and the determination of rate data. J. Am. Chem. Soc. 84, 4672–4677 (1962)
Monica, M.D., Petrella, G., Sacco, A., Bufo, S.: Transference numbers in concentrated sodium chloride solutions. Electrochim. Acta 24, 1013–1017 (1979)
Carman, P.C.: Transport in concentrated solutions of 1:1 electrolytes. J. Phys. Chem. 73, 1095–1105 (1969)
Arevalo, A., Vivo, A., Esteso, M.A., Llorente, M.L.: Conductividades electroliticas en medios agua-etanol. II. Conductividad limite del NaCl a 25°C. An. Quím. 73, 195–199 (1977)
Justice, J.C.: Contribution à l’étude de la conductibilité des électrolytes symétriques en solutions diluées–I. J. Chim. Phys. 65, 353–367 (1968)
Davies, C.W.: The conductivity of potassium chloride solutions. J. Chem. Soc., 432–436 (1937)
Kok, W.: Capillary electrophoresis: Instrumentation and operation. Chromatographia 51, 89 (2000)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Aupiais, J. Electrophoretic Mobilities of the Isotopes of Chloride and Bromide Ions in Aqueous Solution at 25 °C and Infinite Dilution. J Solution Chem 40, 1629–1644 (2011). https://doi.org/10.1007/s10953-011-9734-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10953-011-9734-y