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  • 1
    ISSN: 1572-8927
    Keywords: Activity coefficients ; osmotic coefficients ; aqueous solution ; electrolytes ; liquid membranes ; membrane electrodes ; multicharged electrolytes ; hexacyanocobaltate (III) salts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The activity coefficients of K3[Co(CN)6], Mg3[Co(CN)6]2, and Ca3[Co(CN)6]2,are examined. The results highlight close similarity with the correspondinghexacyanoferrate (III) salts. On dilution, K3[Co(CN)6], like K3[Fe(CN)6], approachesthe limiting law from the upper side, while Mg3[Co(CN)6]2 and Ca3[Co(CN)6]2tend to the limiting law from the opposite side, like Mg3[Fe(CN)6]2,Ca3[Fe(CN)6]2, Sr3[Fe(CN)6]2, and Ba3[Fe(CN)6]2. Both kinds of behavior agreewith theory for a model of hard spheres bearing electric charges +1 and −3 or+2 and −3, respectively. The paramater values of the Pitzer equation for activityand osmotic coefficients are reported.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-8927
    Keywords: Activity coefficients ; aqueous solution ; emf ; membrane electrodes ; barium hexacyanoferrate (III) ; calcium hexacyanoferrate (III) ; magnesium hexacyanoferrate (III) ; strontium hexacyanoferrate (III)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The relative mean activity coefficients of the M3[Fe(CN)6]2 salts, M=Mg, Ca, Sr, Ba, are measured down to about 5×10−6 mol-kg−1 using the liquid membrane cell method. In the dilute region these salts display negative instead of positive deviations from the limiting law, contrary to Debye-Hückel's theory predictions. An indirect method based on auxiliary emf measurements in MCl2, K3Fe(CN)6 and KCl, rather than a theory-assisted direct extrapolation to zero of the relative activity coefficients, is used to identify the actual values of the activity coefficients. The data are compared with Mayer's theory, ion-pair theory and numerical integration of the Poisson-Boltzmann equation. Best-fit coefficients of Pitzer's equation which meet the activity coefficients of the M3[Fe(CN)6]2 salts to be reproduced, are reported.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1572-8927
    Keywords: Activity coefficients ; aqueous solution ; electrolytes ; ion hydration ; membrane electrodes ; Ianthanum hexacyanoferrate (III) ; potassium hexacyanoferrate (III) ; Ianthanum chloride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The activity coefficients of LaCl3, K3Fe(CN)6, and LaFe(CN)6 were measured down to about 1×10−4, 3×10−5, and 2×10−5 mol-kg−1 respectively, by means of cells with ion-exchange liquid membranes. In the diluted region, the trend of lanthanum chloride agrees with the Debye-Huckel theory and corroborates earlier findings in the literature relevant to more concentrated solutions, with minor systematic corrections of the γ± values. K3Fe(CN)6 attains (rather than tends to attain) the Debye-Huckel limiting slope at≈1×10−3 mol-kg−1, and lanthanum ferricyanide in the diluted region shows negative deviations from the limiting law, similar to the ones predicted for large-sized, highly-charged ions in the diluted region by Bjerrum's, IPBE, and Mayer's theories. The behavior of LaCl3 in the concentrated solutions proves that lanthanum ion drags along with it into the membrane many molecules of water which were then found to be twelve. Pitzer's theory best-fit coefficients that meet the experimental curves to be reproduced satisfactorily are reported.
    Type of Medium: Electronic Resource
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