Re-evaluation of Activity Coefficients in Dilute Aqueous Hydrobromic and Hydriodic Acid Solutions at Temperatures from 0 to 60 °C

• Published in: Journal of solution chemistry 2013, Vol.42 (1), p.190-210
• Main Authors: Partanen, Jaakko I., Makkonen, Esko K., Vahteristo, Kari P.
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Condensed Matter Physics; Geochemistry; Industrial Chemistry/Chemical Engineering; Inorganic Chemistry; Oceanography; Physical Chemistry
• ISSN: 0095-9782; 1572-8927
• DOI: 10.1007/s10953-012-9941-1

Simple two-parameter Hückel equations can be used for the calculation of the activity coefficients in aqueous hydrobromic and hydriodic acid solutions at temperatures from 0 to 60 °C and from 0 to 50 °C, respectively, at least up to a molality of 0.5 mol·kg −1 . The data measured by Macaskill and Bates (J. Solution Chem. 12:607–619, 1983) at 25 °C and those measured by Hetzer et al. (J. Phys. Chem. 68:1929–1933, 1964) at various temperatures on galvanic cells without a liquid junction were used in the parameter estimations for the hydrogen bromide (HBr) and hydrogen iodide (HI) solutions, respectively. The latter data consist of sets from 0 to 50 °C at intervals of 5 °C. The parameter values for HBr solutions were also tested using the numerous galvanic cell points from the other three data sets existing in the literature for hydrobromic acid solutions and covering wide range of temperatures from 0 to 60 °C. It was observed in the parameter estimations and tests that all of the estimated parameters are independent of the temperature. The recommended parameter values were additionally tested using the isopiestic data of Macaskill and Bates (see the citation above) and those of Harned and Robinson (Trans. Faraday Soc. 37:302–307, 1941) for dilute HBr and HI solutions at 25 °C, respectively. In more concentrated solutions up to a HBr molality of 4.5 mol·kg −1 and up to a HI molality of 3.0 mol·kg −1 , an extended Hückel equation was used, which contains an additional quadratic term with respect to the molality. The parameters for the extended Hückel equations were determined from these isopiestic data and tested using these data and the existing galvanic cell data. The activity and osmotic coefficients calculated from the resulting equations are recommended in the present study for the more concentrated solutions. The recommended values are compared to the activity values reported in several previous tabulations.