Effect of temperature on the molar conductivity of aqueous solutions of sodium and calcium fullerenehexamalonates, Th-C66(COONa)12 and Th-C66((COO)2Ca)6

Electrical conductivity measurements on aqueous solutions of the sodium and calcium salts of fullerenehexamalonic acid, C66(COONa)12 and C66((COO)2Ca)6, were carried out at four temperatures: 5, 15, 25 and 35°C, and in the concentration range from about 0.04 to 0.0001 mol (COO−) dm−3. Few measurements were also performed at 25°C on mixed solutions of C66(COONa)12 and C66((COO)2Ca)6. The limiting equivalent conductivities of the fullerenehexamalonate anion were estimated: Λ0[1//12C66(COO−)12] = 68.9, 91.4, 115.4 and 137.2 Ω−1 cm2 mol−1, respectively, at the temperatures of our measurements. Walden's product for the fullerenehexamalonate anion is practically independent of the temperature and is close to the theoretical value predicted by the Stokes' law. Following the idea of association of counterions with the macroion we estimated the values of the molar conductivity of the fullerene macroion constituent and its transport number, assuming for the fraction of apparently free counterions the theoretical values based on the solution of the Poisson–Boltzmann equation for the spherical cell model. A reasonable concentration dependence of these properties has been observed.

[1]  J. Škerjanc,et al.  Water-Soluble Fullerenes. 2. Sodium Fullerenehexamalonate Th-C66(COONa)12, a Highly Asymmetric Electrolyte , 2000 .

[2]  J. Škerjanc Water-soluble fullerene electrolytes. Electrostatic contribution to thermodynamic functions , 1999 .

[3]  J. Škerjanc,et al.  Water-Soluble Fullerenes. 1. Fullerenehexamalonic Acid Th-C66(COOH)12, an Intermediate Spherical Electrolyte , 1998 .

[4]  K. Kogej,et al.  Transport phenomena and ion binding in poly(styrenesulfonate) solutions containing mixtures of two counter ions differing in charge and size , 1996 .

[5]  K. Kogej,et al.  TRANSPORT PHENOMENA AND ION BINDING IN POLY(STYRENESULFONATE) SOLUTIONS CONTAINING MIXTURES OF TWO MONOVALENT COUNTERIONS , 1995 .

[6]  Olivier Bernard,et al.  Conductance in electrolyte solutions using the mean spherical approximation , 1992 .

[7]  R. Varoqui,et al.  Electrical and mass transport in salt-free polyelectrolyte solutions , 1973 .

[8]  T. Kurucsev,et al.  Ion binding from conductance and transference measurements in salt-free aqueous polyelectrolyte solutions , 1966 .

[9]  J. L. Jackson,et al.  Potential and Effective Diffusion Constant in a Polyelectrolyte Solution , 1963 .

[10]  J. L. Jackson,et al.  Effective Diffusion Constant in a Polyelectrolyte Solution , 1963 .

[11]  J. L. Jackson,et al.  On the Self‐Diffusion of Ions in a Polyelectrolyte Solution , 1962 .

[12]  F. T. Wall,et al.  Electrolytic Properties of Aqueous Solutions of Polyacrylic Acid and Sodium Hydroxide. I. Transference Experiments Using Radioactive Sodium1 , 1950 .