News (January 2021)

Our paper describing measurements of Tris buffer solubilities in various salt solutions, and measurements of water activities of aqueous Tris, has just been published. The citation and abstract are given further below.

Working Group members Simon Clegg, Andrew Dickson, and David Turner, and Jason Waters of NIST (USA), are currently working on a manuscript describing insights from an uncertainty analysis of the current best Pitzer speciation model of the Tris buffers used in seawater pH measurements. Also, associate member Frank Bastkowski of PTB (Germany) has begun Harned Cell measurements to characterise the thermodynamic properties of aqueous solutions containing dissolved equimolal TrisH+ and Tris in an NaCl medium. The results will be used to improve the speciation model of Tris buffer in artificial seawater (in which the major solute is NaCl).

P. Lodeiro, D. R. Turner, E. P. Achterberg, F. K. A. Gregson, J. P. Reid, and S. L. Clegg (2021) Solid-liquid equilibria in aqueous solutions of Tris, Tris-NaCl, Tris-TrisHCl, and Tris-(TrisH)2SO4 at temperatures from 5 to 45 oC. J. Chem. & Eng. Data 66, 437-455. (

Abstract: The substance Tris (or THAM, 2-amino-2-hydroxymethyl-1,3-propanediol) is used in the preparation of pH buffer solutions for applications in natural water chemistry, including seawater. The development of a chemical speciation model of buffer solutions containing Tris, TrisH+, and the major ions of seawater is desirable, so that the effects of changes in the composition and concentration of the medium on pH can be calculated. The Pitzer activity coefficient equations, commonly used in such speciation models, describe the thermodynamic properties of solutions in terms of interactions between dissolved ions and uncharged solute species. To determine some of these interactions, we have measured solubilities of Tris(s) in water and aqueous solutions of NaCl, TrisHCl, and (TrisH)2SO4 and the solubility of NaCl(s) in aqueous Tris(aq), from 5 to 45°C. We report measurements of the water activities of Tris solutions at 293.5 K to high supersaturation with respect to the solid. Using the Pitzer equations, we compare our results to literature data yielding stoichiometric dissociation constants of TrisH+ in aqueous NaCl, and to electromotive forces of cells containing dissolved Tris, TrisHCl, and NaCl. Values of parameters for the interactions of Tris with the ions TrisH+, Na+, and SO42- at 25°C are determined.