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Sb{sup III} - Sb{sup V} Exchange Reaction in Hydrochloric: Acid Solutions; Echange Sb{sup III}-Sb{sup V} dans des Solutions d'Acide Chlorhydrique; Reaktsiya obmena Sb(III) - Sb(V) v rastvorakh khloristovodorodnoj kisloty; Intercambio Sb{sup III}-Sb{sup V} en Soluciones de HCl

Conference:

Abstract

The exchange reaction of Sb{sup III} - Sb{sup V} in solutions of low HCl concentrations was studied using {sup 124}Sb as a tracer. The effects of HCl concentrations and chemical forms of antimony on the exchange rate were investigated. The HCl concentrations of the antimony solutions ((Sb{sup III}) =(Sb{sup V}) = 6.8 x 10{sup -4}M) were changed from 0.8 to 4.0M and the half-time for the exchange was measured by plotting log (1 - F) versus time t to calculate the exchange rate assuming the second-ordet reaction. It was found that the exchange rate was sharply increased with the increase of HCl concentrations (at 25 Degree-Sign C, from 0.8 to 2.0M) and at 2.0M HCl concentration the rate reached the maximum, from which the rate was decreased with the increase of HCl concentrations (at 25 Degree-Sign C, from 2.0 to 4.0M). Two sorts of Sb{sup V} species were used for our investigations, i.e. one was used directly after the dilution of 10M HCl Sb{sup V} solution with water and the other was used after 24 hours standing at room temperature from the dilution. (The Sb{sup III} species were also kept standing after preparation from 10M HCl Sb{sup III} solution.) In  More>>
Authors:
Kambara, T.; Yamaguchi, K.; Yasuba, S. [1] 
  1. Shizuoka University, Shizuoka City (Japan)
Publication Date:
Oct 15, 1965
Product Type:
Conference
Report Number:
IAEA-SM-64/9
Resource Relation:
Conference: Symposium on Exchange Reactions, Upton, NY (United States), 31 May - 4 Jun 1965; Other Information: 8 refs., 2 figs., 2 tabs.; Related Information: In: Exchange Reactions. Proceedings of the Symposium on Exchange Reactions| 430 p.
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACTIVATION ENERGY; ANTIMONY; ANTIMONY 124; BERYLLIUM 12; CONCENTRATION RATIO; DILUTION; HYDROCHLORIC ACID; HYDROGEN IONS; LITHIUM CHLORIDES; SPECTROPHOTOMETRY
OSTI ID:
22117357
Research Organizations:
International Atomic Energy Agency, Vienna (Austria)
Country of Origin:
IAEA
Language:
English
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA13M2441073978
Submitting Site:
INIS
Size:
page(s) 101-110
Announcement Date:
Aug 01, 2013

Conference:

Citation Formats

Kambara, T., Yamaguchi, K., and Yasuba, S. Sb{sup III} - Sb{sup V} Exchange Reaction in Hydrochloric: Acid Solutions; Echange Sb{sup III}-Sb{sup V} dans des Solutions d'Acide Chlorhydrique; Reaktsiya obmena Sb(III) - Sb(V) v rastvorakh khloristovodorodnoj kisloty; Intercambio Sb{sup III}-Sb{sup V} en Soluciones de HCl. IAEA: N. p., 1965. Web.
Kambara, T., Yamaguchi, K., & Yasuba, S. Sb{sup III} - Sb{sup V} Exchange Reaction in Hydrochloric: Acid Solutions; Echange Sb{sup III}-Sb{sup V} dans des Solutions d'Acide Chlorhydrique; Reaktsiya obmena Sb(III) - Sb(V) v rastvorakh khloristovodorodnoj kisloty; Intercambio Sb{sup III}-Sb{sup V} en Soluciones de HCl. IAEA.
Kambara, T., Yamaguchi, K., and Yasuba, S. 1965. "Sb{sup III} - Sb{sup V} Exchange Reaction in Hydrochloric: Acid Solutions; Echange Sb{sup III}-Sb{sup V} dans des Solutions d'Acide Chlorhydrique; Reaktsiya obmena Sb(III) - Sb(V) v rastvorakh khloristovodorodnoj kisloty; Intercambio Sb{sup III}-Sb{sup V} en Soluciones de HCl." IAEA.
@misc{etde_22117357,
title = {Sb{sup III} - Sb{sup V} Exchange Reaction in Hydrochloric: Acid Solutions; Echange Sb{sup III}-Sb{sup V} dans des Solutions d'Acide Chlorhydrique; Reaktsiya obmena Sb(III) - Sb(V) v rastvorakh khloristovodorodnoj kisloty; Intercambio Sb{sup III}-Sb{sup V} en Soluciones de HCl}
author = {Kambara, T., Yamaguchi, K., and Yasuba, S.}
abstractNote = {The exchange reaction of Sb{sup III} - Sb{sup V} in solutions of low HCl concentrations was studied using {sup 124}Sb as a tracer. The effects of HCl concentrations and chemical forms of antimony on the exchange rate were investigated. The HCl concentrations of the antimony solutions ((Sb{sup III}) =(Sb{sup V}) = 6.8 x 10{sup -4}M) were changed from 0.8 to 4.0M and the half-time for the exchange was measured by plotting log (1 - F) versus time t to calculate the exchange rate assuming the second-ordet reaction. It was found that the exchange rate was sharply increased with the increase of HCl concentrations (at 25 Degree-Sign C, from 0.8 to 2.0M) and at 2.0M HCl concentration the rate reached the maximum, from which the rate was decreased with the increase of HCl concentrations (at 25 Degree-Sign C, from 2.0 to 4.0M). Two sorts of Sb{sup V} species were used for our investigations, i.e. one was used directly after the dilution of 10M HCl Sb{sup V} solution with water and the other was used after 24 hours standing at room temperature from the dilution. (The Sb{sup III} species were also kept standing after preparation from 10M HCl Sb{sup III} solution.) In both cases the maximum rates were found to exist at 2.0M HCl concentration. The rate R{sub 1} for the former (directly after dilution) was 4.5 x 10{sup -6} mole litre{sup -1} min{sup -1} and the rate R{sub 2} for the latter (24 hours standing) was 1.2 x 10{sup -}{sub 6} mole litre. Also the activation energy for these cases was found to be 12.2 kcal/mole and 19.1 kcal/mole. By spectrophotometric studies, the Sb{sup V} species of the former type were found to be mainly consisting of SbCl{sup -}{sub 6} and the species of the latter type to be of SbCl{sub 4}(OH){sup -}{sub 2}, etc. Besides these facts the form of Sb{sup III} species was found to have no influence on the exchange rate. A much sharper increase of the exchange rate was observed when the HCl concentration of the antimony solution was fixed at 0.8M and the chloride concentration was increased to 3.0M by an addition of LiCl. It is noteworthy that an almost linear and sharp increase of the rate was observed until 2.0M chloride concentration. The above fact obtained at a constant hydrogen ion concentration suggests that the chloride atoms act as bridge formation atoms of the intermediate compound for the antimony exchange. To summarize these results, the existence of the maximum exchange rate at about 2.0M HCl concentration in a low HCl concentration region is thought to be well explained. (author) [French] En utilisant {sup 124}Sb comme radioindicateur, les auteurs ont etudie l'echange Sb{sup III} - Sb{sup V} dans des solutions diluees de HCl, notamment les effets de la concentration en HCl et de la forme chimique de l'antimoine sur la vitesse d'echange. Ils ont fait varier la concentration en HCl des solutions d'antimoine ((Sb{sup III}) =(Sb{sup V}) = 6.8 x 10{sup -4}M) de 0,8 a 4,0M et ils ont mesure le temps de demi-echange en tracant la courbe de log(1 - F) en fonction du temps t, en vue de calculer la vitesse d'echange, la reaction etant supposee du deuxieme ordre. Les auteurs ont constate que la vitesse d'echange augmentait fortement avec l'accroissement de la concentration en HCl (a 25 Degree-Sign C, de 0,8 a 2,0M); le maximum a ete atteint pour une concentration de 2,0M, apres quoi la vitesse a diminue avec l'augmentation de la concentration en HCl (a 25 Degree-Sign C, de 2,0 J 4,0M). Dans leurs recherches, les auteurs ont eu recours a deux Sb{sup V}; ils ont utilise le premier aussitot apres dilution dans l'eau d'une solution de Sb{sup V} dans HCl 10M, et la seconde apres avoir laisse reposer 24 heures a la temperature ambiante. (On a aussi laisse reposer les especes de Sb{sup III} apres les avoir preparees a partir d'une solution de Sb{sup III} dans HCl 10M). Dans les deux cas, les maximums ont ete atteints pour une concentration de 2,0M. Dans le premier cas (aussitot apres dilution), la vitesse R{sub 1} etait de 4,5 * 10{sup -6} mole * l{sup -1}; dans le deuxieme (apres 24 heures de repos), R{sub 2} etait de 1,2 * 10{sup -6} mole * l{sup -1} * min{sup -1}. L'energie d'activation etait respectivement de 12,2 kcal/mole et 19,1 kcal/mole. Les etudes spectrophotometriques ont permis d'etablir que les SbV du premier type etait constitues principalement par SbCl{sub 6}{sup -} et ceux du deuxieme type, par SbCl{sub 4}(OH){sub 2}{sup -}, etc. En dehors de ces faits, les auteurs n'ont releve aucune influence de la forme de Sb{sup III} sur la vitesse d'echange. Une augmentation beaucoup plus forte de la vitesse d'echange a ete observee lorsque la concentration en HCl de la solution d'antimoine etait 0,8M et la concentration en chlorure etait portee a 3.0M par addition de LiCl. Il est a noter qu'une augmentation forte et quasi lineaire de la vitesse a ete observee pour des concentrations en chlorure allant jusqu'a 2,0M. Etant donne que ce phenomene a ete observe pour une concentration constante en ions hydrogene, on peut penser que les atomes de chlorure interviennent comme atomes de pontage du compose intermediaire en vue de l'echange d'antimoine. (author) [Spanish] Empleando {sup 124}Sb como indicador, los autores estudiaron la reaccion de intercambio Sb{sup III} - Sb{sup V} en soluciones diluidas de HCl y en particular los efectos de la concentracion de HCl y de la forma quimica del Sb sobre la velocidad de intercambio. La concentracion de HCl de las soluciones de antimonio ((Sb{sup III}) =(Sb{sup V}) = 6.8 x 10{sup -4}M) se modifico entre 0,8 y 4,0M y el tiempo de semi-intercambio se midio trazando la curva representativa de log(1 - F) en funcion del tiempo t, con el fin de calcular la velocidad de intercambio suponiendo que se trata de una reaccion de segundo orden. Se comprobo que la velocidad de intercambio aumentaba netamente al elevar la concentracion de HCl (de 0,8 a 2,0M a 25 Degree-Sign C) y alcanzaba un valor maximo a 2,0M a partir del cual volvia a diminuir si la concentracion de HCl seguia aumentado (de 2,0 a 4, OM a 25 Degree-Sign C). Se emplearon en la investigacion dos especies SbV, Una de las cuales se utilizo inmediatamente despues de diluir con agua la solucion 10M de HCl; y la otra despues de dejarla reposar a temperatura ambiente durante 24 h contadas a partir de la dilucion. (La especie Sb{sup III} tambien se dejo en reposo despues de prepararla partiendo de la solucion de Sb{sup III} en HCl 10M. ) En ambos casos, los maximos se determinaron para una concentracion de HCl 2,0M. La velocidad Rj correspondiente a la primera (inmediatamente despues de la dilucion) fue 4,5 * 10{sup -6} mol * l{sup -1} min{sup -1}, la velocidad R{sub 2} de la segunda (al cabo de 24 h de reposo), 1,2 * 10{sup -6} mol * l{sup -1} min{sup -1}. Las energias de activacion fueron en estos casos 12,2 kcal/mol y 19,1 kcal/mol, respectivamente. Mediante estudios espectrofotometricos, se determino que la especie Sb{sup V} del primer tipo consistia principalmente en SbCl{sub 6}{sup -} y la del segundo tipo, en SbCl{sub 4}(OH){sub 2}{sup -}, etc. Fuera de estos hechos, no se observo ninguna influencia de la forma del Sb{sup III} sobre la velocidad de intercambio. Se comprobo un aumento mucho mas marcado de la velocidad de intercambio cuando la concentracion de HCl en la solucion de antimonio se fijo en 0,8M y la concentracion de cloruro se aumento hasta 3,0M agregando LiCl. Cabe destacar que se registro un aumento marcado y casi lineal de la velocidad hasta llegar una concentracion de cloruro igual a 2,0M. Este resultado, obtenido con una concentracion constante de iones hidrogeno, sugiere que los atomos de cloruro intervienen como puentes en el compuesto intermedia con miras al intercambio de antimonio. (author) [Russian] Izuchalas' reakcija obmena Sb{sup III} - Sb{sup V} v rastvorah s nizkoj koncentraciej HCl s primeneniem Sb{sup 124} v kachestve indikatora. Issledovany vlijanie koncentracii HCl i himicheskih form sur'my na skorost' obmena. Koncentracija HCl v rastvorah sur'my ((Sb{sup III}) = (Sb{sup V}) = 6,8 * 10{sup -4} M) menjalas' ot 0,8 do 4,0 M, i period poluobmena byl izmeren putem vyvedenija logarifma (1-F) po otnosheniju ko vremeni dlja rascheta skorosti obmena v predpolozhenii reakcii vtorogo porjadka. Bylo obnaruzheno, chto skorost' obmena rezko vozrastaet s vozrastaniem koncentracii HCl (pri 25 Degree-Sign S ot 0,8 do 2,0 M) i pri 2,0 M koncentracii HCl skorost' dostigaet maksimuma, posle kotorogo skorost' padaet s uvelicheniem koncentracii HCl (pri 25 Degree-Sign S ot 2,0 do 4,0 M). Pri issledovanijah byli ispol'zovany dve raznovidnosti Sbv, to est' odna byla ispol'zovana neposredstvenno posle razvedenija rastvora 10 M HCl Sbv vodoj i drugaja - posle 24 chasov otstaivanija pri komnatnoj temperature iz rastvora. V oboih sluchajah maksimal'nye sko- rosti byli obnaruzheny pri koncentracii 2,0 M HCl. Skorost' R{sub 1} dlja pervoj (neposred- stvenno posle razbavlenija) sostavila 4,5 * 10{sup -6} mol' litr{sup -1} min{sup -1}, i skorost' R{sub 2} dlja vtoroj (otstaivalas' v techenie 24 chasov) byla 1,2 * 10{sup -6} mol' litr{sup -1} min{sup -1} . Energija aktivacii dlja ukazannyh sluchaev ravnjalas' 12,2 kkal/mol' i 19,1 kkal/mol'. Pri pomoshhi spektrofoto- metricheskih issledovanij bylo obnaruzheno, chto raznovidnosti Sb{sup V} pervogo tipa sostojat glavnym obrazom,iz SbClg, a raznovidnosti vtorogo tipa - iz SbCl(OH){sup -}{sub 2} i t . d . Pomimo jetih faktov bylo obnaruzheno, chto forma raznovidnostej Sb{sup III} ne okazyvaet nikakogo vlijanija na skorost' obmena. Bolee rezkoe vozrastanie skorosti obmena otmechalos', kogda koncentracija HCl v ras- tvore sur'my byla 0,8 M, a koncentracija hlorida byla uvelichena do 3,0 M s dobavleniem LiCl. Primechatel'no, chto pochti linejnoe i rezkoe uvelichenie skorosti otmechalos' do kon- centracii hlorida 2,0 M. Jeti fakty, poluchennye pri postojannoj koncentracii vodorodnyh ionov, navodjat na mysl', chto atomy hlorida igrajut rol' mostikovyh atomov v obrazovanii promezhutochnyh soedinenij pri obmene sur'my. Summiruja vysheupomjanutye rezul'taty, mozhno skazat', chto sushhestvovanie maksimal'noj skorosti obmena pri koncentracii HCl okolo 2,0 M v oblasti nizkoj koncentracii HCl mozhet byt', po-vidimomu, prekrasno ob'jasneno. (author)}
place = {IAEA}
year = {1965}
month = {Oct}
}