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  • 1
    ISSN: 1572-8927
    Keywords: Activity coefficients ; osmotic coefficients ; aqueous solution ; electrolytes ; liquid membranes ; membrane electrodes ; cadmium sulfate ; cobalt perchlorate ; cobalt sulfate ; nickel perchlorate ; nickel sulfate ; potassium sulfate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The activity coefficients of CdSO4 CoSO4, and NiSO4 are determined from the emf of liquid-membrane cells, like those described in the papers I–VI of this series. The activity coefficients of the auxiliary salts Co(ClO4)2, Ni(ClO4)2, and K2SO4, needed to eliminate the problem of extrapolation to infinite dilution of the 2–2 salts, are also measured. CdSO4 CoSO4 and NiSO4 in the dilute region deviate downward from the limiting law by a larger extent than believed in the past, thus creating the need for the activity coefficients to be recalculated and systematically lowered by 8–16%. The activity coefficients of Co(ClO4)2 and Ni(ClO4)2, too, need to be corrected by around –3%. For K2SO4, the original values, although scattered, were substantially correct. Pitzer's theory best-fit parameter, able to provide the activity and osmotic coefficients of the salts considered, are reported.
    Type of Medium: Electronic Resource
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  • 2
    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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  • 3
    ISSN: 1572-8927
    Keywords: Activity coefficients ; aqueous solution ; electrolytes ; manganese perchlorate ; manganese sulfate ; membrane electrodes ; Pitzer equations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The relative activity coefficients of MnSO4 and Mn(ClO4)2 were measured downto about 5×10−5 mol-kg−1 by means of cells with ion-exchange liquid membranes.The measurements at high dilution provide an answer to the age-old problem ofabsolute values of the activity coefficients for MnSO4. They also lead to acorrection of the activity coefficients for Mn(ClO4)2, whose literature values arefound to be biased by ca. 6.5%. Like other bivalent metal sulfates, MnSO4does not obey the Debye—Hückel law inasmuch as negative instead of positivedeviations from the limiting law are observed in the dilute regions. The possibilityfor this kind of behavior to denote ion association is discussed. The best-fitparameters of Pitzer's equation, able to provide accurate values of the activityand osmotic coefficients of the two salts for any concentration, are reported.
    Type of Medium: Electronic Resource
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