IMIS

The substance Tris (or THAM, 2-amino-2-hydroxymethyl-1,3-propanediol, CAS 77–86-1), and its protonated form TrisH⁺, is used in the preparation of pH buffer solutions for applications in seawater chemistry. The development of an acid-base chemical speciation model of buffer solutions containing Tris, TrisH⁺, and the major ions of seawater is desirable so that: (i) the effects of changes in the composition of the medium on pH can be calculated; (ii) pH on the free (ameasure of [H⁺]) and total (a measure of ([H⁺] + [HSO ₄⁻])) scales can be interconverted; (iii) approximations inherent in the definition of the total pH scale can bequantified; (iv) electrode pairs such as H⁺/Cl⁻ and H ⁺/Na⁺ can more easily be calibrated for the measurement of pH. As a first step towards these goals we have extended the Pitzer-based speciation model of Waters and Millero (Mar. Chem. 149, 8–22, 2013) for artificial seawater to include Tris and TrisH⁺, at 25 °C. Estimates of the variances and covariances of the additional interaction parameters were obtained by Monte Carlo simulation . This enables the total uncertainty of any model-calculated quantity (e.g., pH, speciation) to be estimated, as well as the individual contributions of all interaction parameters and equilibrium constants . This is important for model development, because it allows the key interactions to be identified. The model was tested against measured EMFs of cells containing Tris buffer in artificial seawater at 25 °C, and the mean deviation was found to be 0.13 ± 0.070 mV for salinities 20 to 40. Total variances for calculated electromotive forces of the buffer solutions are dominated by contributions from just a few interaction parameters, making it likely that the model can readily be improved. The model was used to quantify the difference between variousdefinitions of total pH and –log₁₀([H⁺] + [HSO ₄⁻]) in Tris buffer solutions at 25 °C, for the first time (item (iii) above). The results suggest that the total pH scale can readily be extended to low salinities using the established approach for substituting TrisH⁺ for Na⁺ in the buffer solutions, especially if the speciation model is used to quantify the effect on pH of the substitution. The relationships between electromotive force (EMF), and pH on the total scale, with buffer molality in artificial seawater atconstant salinity are shown to be linear above about 0.01 to 0.02 mol kg ⁻¹ buffer molality. The pH of Tris buffers containing ratios of TrisH⁺ to Tris that vary from unity can be calculated very simply. Technical aspects of the total pH scale, such as the extrapolation of pH to zero buffer (at constant salinity), are clarified. Recommendations are made for further work to extend the model to the temperature range 0–45 °C, and improve accuracy, so that requirements (i) to (iv) above can be fully met.