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Electrical Phenomena accompanying the Phase Change of Dilute KCl Solutions into Single Crystals of Ice

  • T. E. Osterkamp (a1) and A. H. Weber (a1)

Abstract

The Workman-Reynolds effect was investigated during the phase change of dilute (about 2 × 10-4 N) KCl solutions into single crystals of ice. The ice crystals were oriented with the c-axes either parallel or perpendicular to the growth direction. The solute distribution in the liquid phase. near the interface (within 10 mm), was obtained with a wire-type conductivity cell. For a crystal growth rate 8.8 μm/s the freezing potentials were + 10.0 V and + 6.0 V and the specific charge séparations were 1.3 ± 0 1 × 10-6 C/g of ice and 1 4 ± 0.1 × 10-6 C/g of ice for growth parallel and perpendicular. Respectively, to the c-axes of the ice crystals . The equilibrium solute distribution coefficient was found to be 4 × 10-3 for KCl solutions for both crystal orientations. An “apparent” (because of convection in the liquid phase) distribution coefficient ranged from 0.031- 0.074. The “apparent” diffusion coefficients ranged from 1.3–4.9 × 10-3 mm2/s and varied linearly with growth rate. The ionic distribution coefficients. K+ and K-, were approximately K+ - K- = - 2 × 10-5 and K+ + K - = 8 × 10-3 for the KCl solutions.

Résumé

L’effet Workman-Reynolds fut étudié Durant le changement de phase de solutions diluées (c 2 × 10-4 N) KCl dans des monocristaux de glace. Les cristaux de glace furent orientés avee les axes c soit parallèles, soit perpendiculaires à la direction de croissance. La distribution du solvent dans la phase liquid près de l’interface dans les 10 mm fut obtenue avee une cellule de conductivité à fil. Pour une vitesse de croissance du cristal de 8.8 μm/s, les potentiels de congélation furent de 10,0 V et + 6,0 V et les séparations de charge spécifique de 1.3 ± 0.1 × 10-6 C/g de glace et de 1.4 ± 0.1 × 10-6 C/g de glace pour la croissance parallèle ou perpendiculaire respectivement aux axes c des cristaux de glace. On trouvera le coefficient d’équilibre de distribution du solvent égal à 4 × 10-3 pour les solutions KCl pour les deux orientations du cristal. Un coefficient de distribution “apparent” (dû à la convection dans la phase liquide) s’étendait de 0,031 à 0,074. Les coefficients de diffusion “apparents” s’étendait de 1,3 à 4.9 × 10-3 mm2/s et variaient linéairement avee la vitesse de décroissance. Les coefficents de distribution d’ions, K+ - K- = - 2 × 10-5 et K+ + K- = 8 × 10-3 pour les solutions de KCl.

Zusammenfassung

Bei der Zustandsänderung von wässerigen (etwa 2 × 10-4 N) KCl-Lösungen in Einkristalle von Eis wurde der Workman-Reynolds-Effekt untersucht. Die Eiskristalle waren mit ihren c-Achsen entweder parallel oder senkrecht zur Wachstumsrichtung orientiert. Die Lösungsverteilung in der Flüssigkeit nahe der Grenzfläche (innerhalb 10 mm), wurde mit einem Draht-Leitungselement ermittelt, Für eine Kristallwachstumsgechwindigkeit von 8,8 μm/s betrugen die Gefrierpotentiale + 10,0 V und + 6,0 V und die spezifischen Ladungstrennungen 1,3 ± 0,1 × 10-6 C/g Eis und 1,4 ± 0,1 × 10-6 C/g Eis Für Wachstum jeweils parallel und senkrecht zu den c-Achsen der Eiskristalle. Der Verteilungskoeffizient der Lösung im Gleichgewicht wurde zu 4 × 10-3 Für KCl-Lösungen und beide Kristallorientierungen gefunden. Ein “scheinbarer” (infolge von Konvektion in der Flüssigkeit) Verteilungskoeffizient reichte von 0,031–0,074. Die “scheinbaren” Diffusionskoeffizienten reichten von 1,3-4,9 × 10-3 mm2/s und änderten sich linear mit der Wachstumsgeschwindigkeit. Die lonenverteilungskoeffizienten K+ - K-, waren annähernd K+ - K- = = - 2 × 10-5 und K+ + K- = 8 × 10-3 Für die KCl-Lösungen.

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References

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Electrical Phenomena accompanying the Phase Change of Dilute KCl Solutions into Single Crystals of Ice

  • T. E. Osterkamp (a1) and A. H. Weber (a1)

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