The Dielectric Constant of Water and Debye-Hückel Limiting Law Slopes

Abstract

Experimental values of the dielectric constant of water suggest that, for temperatures greater than 400 K, the integral in the Kirkwood dielectric-constant equation, which involves the intermolecular potential function, is a simpler function of temperature and pressure than of temperature and density. An equation has been fitted to values of this integral calculated from experimental values of the dielectric constant for temperatures from 238.15 K to 823.15 K and to pressures of approximately 500 MPa for temperatures greater than 273 K. The equation for E thus has explicit variables T, p, P and gives a good representation of the available experimental results. The quality of representation of the experimental results has been compared to that of previous correlations of the dielectric constant. The new equation is applicable through wider regions of imlepenuent variables than the previous equations and is capable of sufficient accuracy to provide values of Debye-Hiickel limiting law slopes which are as accurate as the experimental results allow. Values of Dehye-Hiickel limiting-law slopes are tabulated.

Standard state heat capacities of aqueous electrolytes and some related undissociated species

“…It follows that accurate values of C , , for %lute solutions can be obtained only from the results of extremely accurate measurements or from results of accurate measurements that lead reasonably directly to values of the difference represented by [C,(soln) -n Cps -1 in the numerator of eq. [13]. The twin calorimeters designed, built, and used by Randall, Rossini, Gucker, and a few others, as reviewed by Parker (2), provided data of this kind and permitted the evaluation of the first reasonably accurate values of C,,,O for aqueous electrolytes.…”

IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 1. Introduction, Be and Mg

“…Methods to calculate A / are given by Bradley and Pitzer, 25 and by Archer and Wang. 26 The latter scheme was used here. The difference between the two schemes is negligible for the conditions considered in this review.…”

Ion-induced nucleation in polar one-component fluids

“…This form reduces to the Clausius-Mossotti formula in the absence of a permanent dipole and tends to the Kirkwood formula (ε − 1)(2ε + 1)/ε = 4πngµ 2 /k B T for nonpolarizable molecules with permanent dipole moment 19 . Here g is the so-called Kirkwood correlation factor arising from the correlation between the molecular orientations due to nondipolar interactions (2−3 for liquid water), so g weakly depends on n as revealed in experiments 20 . In Fig.1 we plot ε as a function of n at T /T c = 0.675 (T = 437 K) and 0.928 (T = 600 K) below T c on the basis of the formula (2.7) using data of α m and gµ 2 for water in Ref.…”