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  • 1
    ISSN: 1572-8927
    Keywords: Activity coefficients ; osmotic coefficients ; aqueous electrolytes ; elevated temperatures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It was found over a wide concentration and temperature range that differences between osmotic coefficients of a given electrolyte and a standard electrolyte, φ - φst , can be approximated by a linear relation. Sodium chloride, calcium chloride and sodium sulfate were chosen as standard electrolytes for 1:1, 2:1 and 1:2 electrolytes, respectively. Special numerical procedures were developed for the prediction and estimation of activity and osmotic coefficients at elevated temperatures based on data at two temperatures or on data at room temperature only. Reasonable agreement was found between activity coefficients estimated by the present procedure and those correlated by Pitzer's and Meissner's equations.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-8927
    Keywords: Activity coefficients ; electrolyte mixtures ; Harned coefficient ; Pitzer's equations ; ionic interactions ; hydrochloric acid ; manganous chloride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Activity coefficients of hydrochloric acid in mixed solutions of manganous chloride at twelve ionic strengths, from 0.1 to 5.0 mole-kg−1, were obtained from emf measurements of cells without liquid junction at five temperatures from 5 to 45°C. The data were interpreted in terms of the simple and convenient Pitzer treatment. Activity coefficients for manganous chloride in the mixtures were also derived using Pitzer's equations. Hydrochloric acid follows Harned's rule fromI=0.1 to 3.0 mole-kg−1, as concluded by Downes, whereas quadratic terms are warranted fromI=3.5 to 5.0 mole-kg−1. Contrary to Downes' conclusion, Harned's rule clearly does not hold true for manganous chloride at most ionic strengths.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1572-8927
    Keywords: Activity coefficients ; emf ; hydrochloric acid ; magnesium chloride ; Pitzer's equations ; Harned interaction coefficients ; Brönsted-Guggenheim parameters ; Higher-order electrostatic effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Electromotive-force measurements have been made on HCl−MgCl2−H2O mixtures at 5, 15, 25, 35 and 45°C at eleven different ionic strengths from 0.1–5.0 mol-kg −1 . The results are interpreted in terms of the simple Harned's equations, as well as the more complicated Pitzer ion-component treatment of multicomponent electrolyte mixtures. Activity coefficients for HCl in the salt mixtures obey Harned's rule up to and including I=5.0. For the salt in the acid mixtures, Harned's rule holds true up to and including I=0.5. The contribution of higher-order electrostatic terms (Eθ and E'θ) in the Pitzer equations is important for accurate evaluations of unlike cation-cation interactions (θH,Mg), and cation-anion-cation interactions (ΨH,Mg,Cl). The values ofSθH,Mg and ΨH,Mg,Cl (determined with Eθ and E'θ), θH,Mg and ΨH,Mg,Cl (determined without Eθ and E'θ), as well as the trace activity coefficients of HCl, γ tr A , in solutions of MgCl2 (where ionic strength fraction of the salt,y B = 1) at all the experimental temperatures and ionic strengths, are reported. Results of this study are compared with those for similar systems. At I=0.1 and 25°C, the results of the Brönsted-Guggenheim specific interaction theory are discussed briefly.
    Type of Medium: Electronic Resource
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