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Chemical Thermodynamics of Thorium, Volume 11

image of Chemical Thermodynamics of Thorium, Volume 11

This volume is the eleventh in the OECD Nuclear Energy Agency (NEA) “Chemical Thermodynamics” series. It is based on a critical review of the thermodynamic properties of thorium, its solid compounds and aqueous complexes, initiated as part of the NEA Thermochemical Database Project Phase III (TDB III). The database system developed at the OECD/NEA Data Bank ensures consistency not only within the recommended data sets of thorium, but also amongst all the data sets published in the series. This volume will be of particular interest to scientists carrying out performance assessments of deep geological disposal sites for radioactive waste.

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Appendix B

Ionic strength corrections

Nuclear Energy Agency

Thermodynamic data always refer to a selected standard state. The definition given by IUPAC [1982LAF] is adopted in this review as outlined in Section II.3.1. According to this definition, the standard state for a solute B in a solution is a hypothetical solution, at the standard state pressure, in which 1 mB = m?? = 1 mol??kg?? , and in which the activity coefficient ??B is unity. However, for many reactions, measurements cannot be made accurately (or at all) in dilute solutions from which the necessary extrapolation to the standard state would be simple. This is invariably the case for reactions involving ions of high charge. Precise thermodynamic information for these systems can only be obtained in the presence of an inert electrolyte of sufficiently high concentration that ensures activity factors are reasonably constant throughout the measurements. This appendix describes and illustrates the method used in this review for the extrapolation of experimental equilibrium data to zero ionic strength. 

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