The Liquid Junction Potential in Potentiometric Titrations. XII. The Calculation of Potentials for Emf Cells with Liquid Junctions, of the Type, AY vertical bar AY + A(2)MoO(4) + HY, Involving the Formation of Iso-Polymolybdates in the Range-log(10)[H(+)] <= 7, at [A(+)] = C mol.L(-1), Constant, and 25 degrees C
2011 (English)In: Journal of Solution Chemistry, ISSN 0095-9782, E-ISSN 1572-8927, Vol. 40, no 6, 989-1040 p.Article in journal (Refereed) Published
Equations are derived, in a general form, and valid in the range 0.5 <= C <= 3 mol.L(-1), for the calculation of the total potential anomalies (Delta E(H)) for emf cells where the formation of iso-polymolybdates takes place, according to the equilibria: pH(+) (h) + qMoO(4)(2-) (b) (sic) [(H(+))(p)(MoO(4)(2-))(q)](p-2q) (cpx(pq)) by measuring [H(+)] = h, in NaClO(4) ionic medium (A(+), Y(-)) at [Na(+)] = 3 mol.L(-1). The total cell emf (E(H)), can be defined as: E(H) = E(0H) + g log(10) h + g log(10) f(HTS2) + E(D) + E(Df) where: E(0H) is an experimental constant, E(D) + E(Df) = E(J), the classical liquid junction potential, and g log(10) f(JTS2) + E(D) + E(Df) = Delta E(H). Here, MoO(4)(2) is the central "metal ion", E(D) is the ideal diffusion potential (Hendersson equation), E(Df) is the contribution of the activity coefficients to E(D). f(HTS2) denotes the activity coefficient of the H(+) ions in the terminal solution TS2. The investigations of this system made by Sasaki and Sillen are critically analyzed. Some emf cells are supposed for the determination of the interaction coefficients involved. All calculations are valid at 25 degrees C. The revised equilibrium constants are presented in Table 14.
Place, publisher, year, edition, pages
2011. Vol. 40, no 6, 989-1040 p.
Iso-polymolybdates, Liquid junction potential, Ideal diffusion potential, Ionic activity factors, Specific interaction theory, Interaction coefficients, Total potential anomalies, Polyanions
IdentifiersURN: urn:nbn:se:kth:diva-37554DOI: 10.1007/s10953-011-9705-3ISI: 000293213700007ScopusID: 2-s2.0-80051801038OAI: oai:DiVA.org:kth-37554DiVA: diva2:434431
QC 201108152011-08-152011-08-152011-08-15Bibliographically approved