Ionic molal conductivities, activity coefficients, and dissociation constants of HAsO42 − and H2AsO4− from 5 to 90 °C and ionic strengths from 0.001 up to 3 mol kg− 1 and applications in natural systems

Abstract

Arsenic is known to be one of the most toxic inorganic elements, causing worldwide environmental contamination. However, many fundamental properties related to aqueous arsenic species are not well known which will inhibit our ability to understand the geochemical behavior of arsenic (e.g. speciation, transport, and solubility). Here, the electrical conductivity of Na2HAsO4 solutions has been measured over the concentration range of 0.001–1molkg−1 and the temperature range of 5–90°C. Ionic strength and temperature-dependent equations were derived for the molal conductivity of HAsO42− and H2AsO4− aqueous ions. Combined with speciation calculations and the approach used by McCleskey et al. (2012b), these equations can be used to calculate the electrical conductivities of arsenic-rich waters having a large range of effective ionic strengths (0.001–3molkg−1) and temperatures (5–90°C). Individual ion activity coefficients for HAsO42− and H2AsO4− in the form of the Hückel equation were also derived using the mean salt method and the mean activity coefficients of K2HAsO4 (0.001–1molkg−1) and KH2AsO4 (0.001–1.3molkg−1). A check on these activity coefficients was made by calculating mean activity coefficients for Na2HAsO4 and NaH2AsO4 solutions and comparing them to measured values. At the same time Na-arsenate complexes were evaluated. The NaH2AsO40 ion pair is negligible in NaH2AsO4 solutions up to 1.3molkg−1. The NaHAsO4− ion pair is important in NaHAsO4 solutions >0.1molkg−1 and the formation constant of 100.69 was confirmed. The enthalpy, entropy, free energy and heat capacity for the second and third arsenic acid dissociation reactions were calculated from pH measurements. These properties have been incorporated into a widely used geochemical calculation code WATEQ4F and applied to natural arsenic waters. For arsenic spiked water samples from Yellowstone National Park, the mean difference between the calculated and measured conductivities have been improved from −18% to −1.0% with a standard deviation of 2.4% and the mean charge balances have been improved from 28% to 0.6% with a standard deviation of 1.5%.