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  • 1
    ISSN: 1572-8927
    Keywords: Activity coefficient ; emf ; Harned's equations ; hydrochloric acid ; indium chloride ; mixtures of electrolytes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Electromotive-force measurements of cells containing hydrochloric acid and indium chloride have been made to determine the variation of the log of the activity coefficient of hydrochloric acid with change in the amount of indium chloride in the solution. The simpler Harned equations have been used to fit the data. The quadratic terms in the Harned equations for the activity coefficients of HCl in the salt mixtures are required for a good fit of the 968 experimental emf data points at all the experimental ionic strengths and temperatures. The more convenient Pitzer ion-interaction treatment of the data will be reported in a separate publication which will include the values of the Pitzer parameters for pure InCl3(aq), and mixing parameters for H+−In+3 and H+−In+3−Cl−. A comprehensive investigation on the mixed electrolyte solutions at 11 different constant total ionic strengths ranging from 0.05 to 3.5 mol-kg−1 was made at 11 temperatures from 5 to 55°C using the cell without liquid junction of the type: Pt,H2(g, 1 atm)|HCl(m A)+InCl3(m B)+H2O|AgCl,AG (A).
    Type of Medium: Electronic Resource
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  • 2
    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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  • 3
    ISSN: 1572-8927
    Keywords: Activity coefficient ; emf ; Harned's equations ; hydrochloric acid ; gallium chloride ; electrolyte mixtures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Activity coefficients for HCl in HCl + GaCl3 + H2O at eleven different temperatures from 5 to 55°C have been determined at total experimental ionic strengths from 0.01 to 3.0 mol-kg−1 using a cell of the type: Pt; H2(g, 1 atm)|HCl (mA) + GaCl3(mB)|AgCl, Ag(A) The results for the 770 experimental emf data points have been used to determine the variation of the activity coefficients of HCl with the change in molality of GaCl3 in the solution. It is found that the linear form of Harned's rule is not obeyed for this system.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 29 (2000), S. 289-297 
    ISSN: 1572-8927
    Keywords: Activity coefficient ; emf ; hydrochloric acid ; gallium chloride ; Pitzer equations ; hydrolysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A comprehensive equation for the thermodynamic properties of the systemGaCl3-HCl-H2O at 25°C in the ion-interaction (Pitzer) equation form has been generatedon the basis of a recent and comprehensive array of electrochemical cellmeasurements of the HCl activity at total stoichiometric ionic strengths from 0.01 to 3.0mol-kg−1. Alternate equations with and without explicit consideration of thehydrolyzed product GaOH2+ as a separate species have been tested. Excellentagreement is obtained between the calculated and measured cell potentials forthe formulation, which includes GaOH2+ as an additional species. The effect offurther hydrolysis as well as that of complex formation has been found to benegligible. While a satisfactory set of Pitzer parameters has been found, it wasnot possible to obtain a unique thermodynamic representation for this systembecause of large uncertainties in the first hydrolysis constant of Ga(III) and becauseof redundancies and intrinsic correlations between some of the Pitzer parameters.
    Type of Medium: Electronic Resource
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  • 5
    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.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 3 (1974), S. 837-845 
    ISSN: 1572-8927
    Keywords: Activity coefficient ; ammonium chloride ; Harned's rule ; hydrochloric acid ; mixtures of electrolytes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Electromotive-force measurements of cells containing hydrochloric acid and ammonium chloride at constant total molality have been used to determine the variation of the logarithm of the activity coefficient of hydrochloric acid with change in the amount of ammonium chloride in the solution. The results are interpreted in the light of the recent work of Pitzer, and it is found that Harned's rule holds for both electrolytes.
    Type of Medium: Electronic Resource
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