Published October 1965
| Version v1
Book
Acceleration of the Uranium(IV)-(VI) Electron-Exchange Reaction by Hydrochloric Acid
Creators
- 1. Tokyo Institute of Technology, Tokyo (Japan)
- 2. Atomic Fuel Corporation, Tokyo (Japan)
Description
The homogeneous exchange reaction between natural uranium (IV) and depleted uranium (VI) has been studied in hydrochloric acid solution at 30°C, 50°C and 70°C. The exchange reaction was found to be catalysed by large concentrations of chloride, while inhibited by small concentrations of chloride. The increased rate above chloride is twelfth-order with respect to chloride concentration and fifth-order with respect to Cl-activity. The rates at 30°C were estimated as 0.046 x 10-5, 1.2 x 10-5 and 10 x 10-5 M min-1 for, BM, 8M and 10M hydrochloric acid, respectively, and the activation energies were 25, 25 and 24 kcal/mole. The exchange process can be explained by assuming the formation of highly reactive activated complexes containing uranium (IV), uranium (VI) and both bridging and non-bridging chloride ions. (author)
Abstract (French)
Les auteurs ont étudié l'échangehomogène entre l'uranium (IV) naturel et l'uranium (VI) appauvri dans une solution de HCl á des températures de 30, 50 et 70°C. Les auteurs ont constaté que l'échange est catalysé par de fortes concentrations et inhibé par de faibles concentrations en chlorure. L'augmentation de la vitesse lorsque la concentration en chlorure dépasse 6M est du douzième ordre par rapport à la concentration en chlorure et du cinquième ordre par rapport à l'activité du chlorure. On a estimé que les vitesse d'échange à 30°C sont respectivement de 0,046.10-5 , 1,2.10-5 et 10.10-5 M. min-1 pour HCl 6M, 8M et 10M. Les énergies d'activation étaient respectivement de 25, 25 et 24 kcal/mole. On peut expliquer le processus d'échange en admettant la formation de complexes activés fortement réactifs contenant de l'uranium (IV), de l'uranium (VI) et des ions chlorures qui, dans certains cas, forment pontage. (author)Abstract (Spanish)
Se ha estudiado el intercambio homogéneo entre el uranio (IV) natural y el uranio (VI) empobrecido en soluciones de HCl a 30°, 50° y 70°C. Se ha comprobado que el ion cloruro en concentraciones elevadas cataliza la reacción de intercambio, mientras que ésta resulta inhibida por el cloruro en concentraciones bajas. El aumento de velocidad, cuando la concentración de cloruro es superior a 6M es de orden 12 con respecto a la concentración de cloruro y de orden 5 con respecto a la actividad del cloruro. Se ha estimado que la velocidad de intercambio a 30°C es de 0.046 x 10-5, 1.2 x 10-5 and 10 x 10-5 M min-1 para HCl, 8M and 10M, respectivamente, y que las energías de activación son de 25, 25 y 24 kcal/mol. Este proceso de intercambio se puede explicar admitiendo la formación de complejos activados de alta capacidad de reacción que contienen uranio (IV), uranio (VI) e iones cloruro que, en algunos casos, forman puentes. (author)Abstract (Russian)
Reakcija gomogennogo obmena mezhdu prirodnym uranom (IV) i obednen- nym uranom (VI) izuchalas' v rastvore soljanoj kisloty pri 30, 50 i 70° S. Ustanovleno, chto reakcija obmena kataliziruetsja bol'shimi koncentracijami hlorida i oslabljaetsja malymi koncentracijami soljanoj kisloty . Povyshennaja skorost' reakcii v hlori- de moljarnost'ju svyshe 6 M sostavljala velichinu priblizitel'no dvenadcatogo porjadka pri nalichii koncentracii hlorida i velichinu pjatogo porjadka pri aktivnosti hlorida. Skorost' obmena pri 30 °S byla podschitana v razmere 0,046 * 10-5, 1,2 * 10-5 i 10 * 10-5M pin-1 dlja 6,8 i JuM soljanoj kisloty sootvetstvenno, i jenergiju aktivacii opredeljali v razmere 25, 25 i 24 kkall/mol. Jetot process obmena objasnjaetsja v predpolozhenii, chto imeet mesto obrazovanie vysoko reaktivnyh aktivirovannyh kompleksov, soderzhashhih uran (IV), uran (VI) i kak mostikovye, tak i ne mostikovye iony hlorida. (author)Additional details
Additional titles
- Original title (English)
- Accélération de l'Échange Uranium (IV) - Uranium (VI) par l'Acide Chlorhydrique; Uskorenie reaktsii obmena ehlektronov Urana (IV) - (VI) s pomoshch'yu solyanoj kisloty; Aceleracion del Intercambio Electronico Uranio (IV) - Uranio (VI) por el Acido Clohidrico
Publishing Information
- Publisher
- IAEA
- Imprint Place
- Vienna (International Atomic Energy Agency (IAEA))
- Imprint Title
- Exchange Reactions. Proceedings of the Symposium on Exchange Reactions
- Imprint Pagination
- 430 p.
- Series
- Proceedings Series
- Journal Page Range
- p. 121-131
- ISSN
- 0074-1884
Conference
- Title
- Symposium on Exchange Reactions
- Dates
- 31 May - 4 Jun 1965
- Place
- Upton, NY (United States)
INIS
- Country of Publication
- International Atomic Energy Agency (IAEA)
- Country of Input or Organization
- International Atomic Energy Agency (IAEA)
- INIS RN
- 44073980
- Subject category
- S37: INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY;
- Resource subtype / Literary indicator
- Conference
- Descriptors DEI
- ABUNDANCE; ACTIVATION ENERGY; CHLORIDES; CHLORINE IONS; CONCENTRATION RATIO; DEPLETED URANIUM; ELECTRON EXCHANGE; HYDROCHLORIC ACID; NATURAL URANIUM
- Descriptors DEC
- ACTINIDES; CHARGED PARTICLES; CHLORINE COMPOUNDS; DIMENSIONLESS NUMBERS; ELECTRON TRANSFER; ELEMENTS; ENERGY; HALIDES; HALOGEN COMPOUNDS; HYDROGEN COMPOUNDS; INORGANIC ACIDS; INORGANIC COMPOUNDS; IONS; METALS; URANIUM
Optional Information
- Notes
- 9 refs., 3 figs., 4 tabs.
- Secondary number(s)
- IAEA-SM--64/8