The relaxation field for the general case of electrolyte mixtures

Quint, Jacques R.; Viallard, André

doi:10.1007/bf00650522

Cited by 56 publications

(27 citation statements)

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“…For small species, a procedure that has its origins in the work of Onsager and Fuoss 16 is frequently used in interpreting electrophoretic mobility 23, 33–35. This procedure has also been widely used in analyzing the electrical conductivity of fully dissociated and partially dissociated binary electrolytes 19–21, 36–40. In a recent analysis, this “small ion” approach was able to account for the electrical conductance of dilute fully dissociated metal chlorides, where the valence charge of the metal varied from +1 to +3 18.…”

Section: Methodsmentioning

confidence: 99%

Modeling the electrophoresis of oligolysines

2011

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CE is used to measure the electrophoretic mobility of low molecular mass oligo-L-lysines (n=1-8) in aqueous LiH₂PO₄ buffer, BGE, at pH 2.5 over a range of temperatures (25-50 °C) and ionic strengths (10-100 mM). Mobilities are corrected for Joule heating and under the conditions of the experiment, interaction of the peptides with the capillary walls can be ignored. A "coarse grained" bead modeling methodology (BMM) (H. Pei et al., J. Chromatogr. A 2009, 1216, 1908-1916) is used to model the mobilities. This model partially accounts for peptide conformation as well as the assumed form of its secondary structure. For highly charged oligolysines, it is necessary to properly account for the relaxation effect. In the present study, the BMM approach tends to overestimate oligolysine mobility and that effect tends to increase with increasing ionic strength and peptide length. It is proposed that association between the oligolysines and buffer components (H₂PO₄⁻ in this case) that go beyond classical electrostatic interactions are responsible for this discrepancy. A simple binding model is introduced that illustrates how this association can reconcile model and experiment.

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Section: Methodsmentioning

confidence: 99%

Modeling the electrophoresis of oligolysines

2011

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“…A£(N03-), Ku K2, Kpq +10, R) mit pq = 0,940 ± 0,004 3,0214 ± 0,0006 160,7 ± 0,6 4 1,880 ± 0,008 5,6545 ± 0,0011 150,4 + 0,6 5 2,820 ± 0,011 8,2037 ± 0,0016 145,5 ± 0,6 6 3,760 + 0,014 10,622 ± 0,002 141,2 ± 0,5 7 4,699 ± 0,018 13,037 + 0,002 138,7 ± 0,5 8 5,964 + 0,023 16,306 ± 0,003 136,7 ± 0,5 9 7,940 + 0,031 21,089 ± 0,004 132,5 ± 0,5 10 9,940 ± 0,039 25,089 ± 0,005 130,9 ± 0,5 11 11,93 ± 0,047 30,771 ± 0,006 128,9 + 0,5 12 13,91 ± 0,055 35,557 + 0,007 127,7 ± 0,5 [14]. Abbildung 1 zeigt die Verteilung der in Losung vorkommenden Teilchenarten in Prozent, bezogen auf die analytische Uranylnitratkonzentration.…”

Section: Einfiihrungunclassified

“…Die Komponenteniiberfuhrungszahlen werden gleichfalls mitgeteilt. [1,2] angewendet, die im Gegensatz zu Quint und Viallard [3,4] die Theorie der Gurney-Sphare mit in die Gleichung einbeziehen, was zum sogenannten ,neuen ModelP fiihrt. Beide sind auf Elektrolyte, die eine Vielzahl von Ionen mit beliebiger Ladungszahl enthalten, anwendbar und liefern sehr gute Ergebnisse [5].…”

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“…(2) sind der Literatur[1][2][3][4] zu entnehmen. Fur eine waBrige Uranylnitratlosung lassen sich folgende Assoziationsgleichgewichte aufstellen [10]: Weiterhin kann allgemein folgendes Hydrolysegleichgewicht formuliert werden: p UOl+ + qH20^[ (U02)p(OH)J<2*~* + qH + Eine groBe Zahl von Untersuchungen iiber das Hydrolyseverhalten von Uranylsalzlosungen sind in den letzten Jahren publiziert worden [11 Brought to you by | New York University Bobst Library Technical Service Authenticated Download Date | 6/12/15 6:16 AM trotz Anwendung unterschiedlicher MeBmethoden bei den weniger polymeren Hydrolyseprodukten weitgehend Ubereinstimmung zeigen.…”

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Untersuchungen des elektrischen Transportverhaltens wäßriger Uranylnitratlösungen bei 298,15 K mit Hilfe von Leitfähigkeitsmessungen

Bischoff¹

1983

Zeitschrift Für Physikalische Chemie

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Ionic conductance / Transport numbers / Behaviour of actinides in solutionIonic conductances were calculated by use of conductance measurements in a concentration range of 0.14 -10" 2 mol/1 to 0.2-10"4 mol/1 taking into account suitable hydrolysis equilibria and the limiting conductances of UO| + , (U02)2 (OH)2 + and U02OH+ were found to be 86 +2cm2 fl"1 mol"1, 110 ± 5cm2 fl"1 mol"1 and 52 ± 4cm2 Q'1 mol"1. Component transference numbers are also reported.

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“…The conductivities of unsymmetric electrolytes of any type can rigorously be treated only since 1978, after the appearance of the LeeWheaton [2,3] and the Quint-Viallard [4][5][6] conductivity equations.…”

Section: Introductionmentioning

confidence: 99%

Conductometric and UV–Visible Spectroscopic Studies on Association in Dilute Aqueous Solutions of Dq2Fe(CN)6

et al. 2015

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Electrical conductivities and electronic absorption spectra of Dq 2 Fe(CN) 6 (where Dq 2? is diquat, the N,N 0 -ethylene-2,2 0 -bipyridine cation) were measured in dilute solutions in water. Experimental data were interpreted in terms of a molecular model which includes the presence of 1:1 and 2:1 associates. Initially, electrical conductivities and absorption spectra were treated using the Quint-Viallard conductivity equations and modified Hemmes algorithm in a limited concentration range, when only minor 2:1 complex formation is expected. The thermodynamic association constant of the 1:1 complex (K 1 = 17,800 ± 1800 dm 3 Ámol -1 ) and the corresponding contact distance (r min = 5.31 ± 0.07 Å ) were evaluated from the spectral data. Analysis of the conductivity data resulted in K 1 = 16,500 ± 1500 dm 3 Ámol -1 (r min = 5.38 ± 0.07 Å ). Both contact distances were found to agree with the FeÁÁÁN distances in crystalline DqH 2 Fe(CN) 6 Á4H 2 O and Dq 2 Fe(CN) 6 Á6H 2 O. This agreement allowed us to use the same r min value to estimate the association constant of the 2:1 complex in accordance to the Fuoss-Krauss theory. Both K 1 and K 2 were used to calculate electrical conductivities and optical absorbancies in the concentration range up to 5 mmolÁdm -3 . Satisfactory agreement was achieved between calculated and experimental data.

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The relaxation field for the general case of electrolyte mixtures

Cited by 56 publications

References 6 publications

Modeling the electrophoresis of oligolysines

Modeling the electrophoresis of oligolysines

Untersuchungen des elektrischen Transportverhaltens wäßriger Uranylnitratlösungen bei 298,15 K mit Hilfe von Leitfähigkeitsmessungen

Conductometric and UV–Visible Spectroscopic Studies on Association in Dilute Aqueous Solutions of Dq2Fe(CN)6

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