The vapour pressure of 1 m sodium chloride solution has been remeasured, and 0.5 m sodium chloride has been measured relative to water to obtain osmotic coefficients ' p from 125 to 270°C. The data obtained have been fitted, in conjunction with those previously obtained, to an extended Debye-Hiickel equation. Activity coefficients, relative partial molal enthalpies and relative partial molal heat capacities have been calculated at 1, 2 and 3 m over the temperature range 60-270°C.
The preparation and characterization of the iron(I1) complex of the hexadentate Schiff base ligand NN"'-bis-[cr-(2-pyridyl)benzylidene]triethylenetetramine are reported. Kinetic patterns and rate constants for aquation of this complex, and for its reactions with hydroxide, cyanide, and peroxodisulphate have been determined. Activation parameters for the reaction with cyanide, in aqueous solution, are AH: = 24.3 kcal/mole and AS: = + 1 cal/deg-mole.
Chloropentaamminecobalt(III) chloride, chloropentaamminerhodium(III) chloride and chloropentaammineiridium (III) chloride labelled with 3e Cl in the cation have been irradiated with thermal neutrons in a flux of 10 11 neutrons cm -2 sec -1 for ten hours. Study of the effects of the (η, γ) reaction has shown that, in the case of the cobalt and rhodium complexes, there is retention of the "CI in the cation, but in the case of the iridium complex about 90% of the Ir-M Cl bonds are broken whilst only one in 10 e iridium atoms are activated. The results are interpreted using a modification to the hot zone theory of HARBOTTLE and SUTIN. An attempt has been made to identify some of the species formed upon dissolution in water.
ZusammenfassungIm Kation mit 3e Cl markiertem Chloropentaamminkobalt(III)-chlorid, Chloropentaamminrhodium(III)chlorid und Chloropentaamminiridium(III)chlorid wurden mit thermischen Neutronen in einem Fluß von 10" Neutronen cm~2 sec -1 zehn Stunden lang bestrahlt. Die Untersuchung der Auswirkungen der (n, y)-Reaktion hat gezeigt, daß bei den Kobalt-und Rhodiumkomplexen eine Rückhaltung des 3e Cl im Kation eintritt, während beim Iridiumkomplex rund 90% der Ir-3e ClBindungen zerstört werden, wogegen nur eines von 10® Iridiumatomen aktiviert wird. Zur Interpretation der Ergebnisse dient eine Modifikation von HARBOTTLE und SUTINS Theorie der heißen Zonen. Es ist versucht worden, einige der bei Auflösung in Wasser gebildeten Arten zu identifizieren.
ResumeOn a irradie par neutrons thermiques sous un flux de 10" neutrons cm -2 s -1 pendant 10 heures les chlorures de chloropentamminocobalt(III), chloropentamminorhodium(III) et chloropentamminoiridium(III) dont les cations ont ete marques par 3e Cl. L'etude des effets obtenus par reaction (η, γ) a montre que pour les complexes du cobalt et du rhodium il y a une retention de 3e Cl dans le cation, alors que dans le cas du complexe de l'iridium quelques 90% des liaisons Ir-^Cl sont rompues, et seulement un atome sur 10® atomes d'iridium se trouve active. On explique ces resultats par une modification de la theorie de la zone chaude proposee par HARBOTTLE et SUTIN. On a essaye d'identifier quelques-unes des especes qui se sont formees apres dissolution dans l'eau.
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