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The Preparation and Thermodynamics of Europium Dicarbide; Preparation et Thermodynamique du Bicarbure d'Europium; Poluchenie i termodinamicheskie svojstva dikarbida evropiya; Preparacion y Termodinamica del Dicarburo de Europio

Abstract

Europium dicarbide has been prepared by the reaction of europium metal and graphite in a stainless steel bomb. Chemical analysis indicates an average composition of the product of EuC{sub 1.87{+-}0.07}. X-ray powder diffraction analysis shows the compound to be of body-centred tetragonal symmetry, space group D{sup 17}{sub 4}n-14/mm , with lattice parameters: a{sub 0} = 4.045 A; c{sub 0} = 6.645 A. Vapour phase chromatographic analysis indicates that 98% of the gaseous product of acid hydrolysis of europium dicarbide is the hydrocarbon acetylene. These analytical data, together with the lattice parameters, indicate that europium dicarbide resembles alkaline earth dicarbides more than it resembles the other lanthanon dicarbides. The vaporization of europium dicarbide over the temperature range 1130 to 1600 Degree-Sign K was investigated by the Knudsen effusion method. The effusate was either collected and analysed chemically or observed with a time-of-flight mass spectrometer. Thedata presented here are based predominantly on the massspectro- metric observations since they yielded more reproducible data than the collection technique. Gaseous europium dicarbide and europium, in concentrations of 1 and 99%respectively, were found in the effusate. Instrument limitations prevented determination of the concentration of the gaseous dicarbide as a function of temperature. Calibration of the mass  More>>
Authors:
Gebelt, R. E.; [1]  Eick, H. A. [2] 
  1. Oklahoma State University, Stillwater, OK (United States)
  2. Michigan State University, East Lansing, MI (United States)
Publication Date:
Jan 15, 1966
Product Type:
Conference
Report Number:
IAEA-SM-66/58
Resource Relation:
Conference: Symposium on Thermodynamics with Emphasis on Nuclear Materials and Atomic Transport in Solids, Vienna (Austria), 22-27 Jul 1965; Other Information: 26 refs., 5 tabs., 7 figs.; Related Information: In: Thermodynamics. Vol. I. Proceedings of the Symposium on Thermodynamics with Emphasis on Nuclear Materials and Atomic Transport in Solids| 539 p.
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETYLENE; ACID HYDROLYSIS; CALIBRATION; CHEMICAL ANALYSIS; CHROMATOGRAPHY; CONCENTRATION RATIO; DISSOCIATION; EUROPIUM; EUROPIUM CARBIDES; FORMATION HEAT; FREE ENERGY; GRAPHITE; KNUDSEN FLOW; LATTICE PARAMETERS; LEAST SQUARE FIT; SPACE GROUPS; STAINLESS STEELS; TEMPERATURE DEPENDENCE; TEMPERATURE RANGE 1000-4000 K; THERMODYNAMICS; TIME-OF-FLIGHT MASS SPECTROMETERS; VAPORIZATION HEAT; X-RAY DIFFRACTION
OSTI ID:
22117337
Research Organizations:
International Atomic Energy Agency, Vienna (Austria); International Union of Pure and Applied Chemistry, Commission on Thermodynamics and Thermochemistry, Research Triangle Park, NC (United States)
Country of Origin:
IAEA
Language:
English
Contract Number:
Contract COO-716-0013
Other Identifying Numbers:
Other: ISSN 0074-1884; TRN: XA13M2383073958
Submitting Site:
INIS
Size:
page(s) 291-308
Announcement Date:
Aug 01, 2013

Citation Formats

Gebelt, R. E., and Eick, H. A. The Preparation and Thermodynamics of Europium Dicarbide; Preparation et Thermodynamique du Bicarbure d'Europium; Poluchenie i termodinamicheskie svojstva dikarbida evropiya; Preparacion y Termodinamica del Dicarburo de Europio. IAEA: N. p., 1966. Web.
Gebelt, R. E., & Eick, H. A. The Preparation and Thermodynamics of Europium Dicarbide; Preparation et Thermodynamique du Bicarbure d'Europium; Poluchenie i termodinamicheskie svojstva dikarbida evropiya; Preparacion y Termodinamica del Dicarburo de Europio. IAEA.
Gebelt, R. E., and Eick, H. A. 1966. "The Preparation and Thermodynamics of Europium Dicarbide; Preparation et Thermodynamique du Bicarbure d'Europium; Poluchenie i termodinamicheskie svojstva dikarbida evropiya; Preparacion y Termodinamica del Dicarburo de Europio." IAEA.
@misc{etde_22117337,
title = {The Preparation and Thermodynamics of Europium Dicarbide; Preparation et Thermodynamique du Bicarbure d'Europium; Poluchenie i termodinamicheskie svojstva dikarbida evropiya; Preparacion y Termodinamica del Dicarburo de Europio}
author = {Gebelt, R. E., and Eick, H. A.}
abstractNote = {Europium dicarbide has been prepared by the reaction of europium metal and graphite in a stainless steel bomb. Chemical analysis indicates an average composition of the product of EuC{sub 1.87{+-}0.07}. X-ray powder diffraction analysis shows the compound to be of body-centred tetragonal symmetry, space group D{sup 17}{sub 4}n-14/mm , with lattice parameters: a{sub 0} = 4.045 A; c{sub 0} = 6.645 A. Vapour phase chromatographic analysis indicates that 98% of the gaseous product of acid hydrolysis of europium dicarbide is the hydrocarbon acetylene. These analytical data, together with the lattice parameters, indicate that europium dicarbide resembles alkaline earth dicarbides more than it resembles the other lanthanon dicarbides. The vaporization of europium dicarbide over the temperature range 1130 to 1600 Degree-Sign K was investigated by the Knudsen effusion method. The effusate was either collected and analysed chemically or observed with a time-of-flight mass spectrometer. Thedata presented here are based predominantly on the massspectro- metric observations since they yielded more reproducible data than the collection technique. Gaseous europium dicarbide and europium, in concentrations of 1 and 99%respectively, were found in the effusate. Instrument limitations prevented determination of the concentration of the gaseous dicarbide as a function of temperature. Calibration of the mass spectrometer with silver permitted the calculation of the pressures corresponding to the observed ion intensities. An empirical equation was fitted to the data for europium by the method of least squares. From the second law of thermodynamics the following values were calculated for the reaction: EuC{sub 2} Rightwards-Harpoon-Over-Leftwards-Harpoon Eu(g) + 2C (graphite); {Delta}H{sup 0}{sub 298} = 51.09{+-}1.42kcal/mole; {Delta}H{sup 0}{sub 298} = 18.43 {+-} 1.75 e.u. Values of the free energy function for EuC{sub 2}(s) were estimated and combined with published data to yield for the same reaction, from the third law of thermodynamics, the value of {Delta}H{sup 0}{sub 298} = 51.22 {+-} 0.80 kcal/mole. The enthalpies obtained for the dissociation reaction were combined with published data on the enthalpy of vaporization of europium to yield for the standard enthalpy of formation of EuC{sub 2} the value {Delta}H{sub f(298)} = -9.17 {+-} 1.15 kcal/mole. (author) [French] Les auteurs ont prepare du bicarbure d'europium par reaction entre l'europium metallique et le graphite dans une bombe en acier inoxydable. L'analyse chimique indique EuC{sub 1.87{+-}0.07} comme composition moyenne du produit. D'apres l'analyse au moyen de la diffraction des rayons X par les poudres, le compose presente une symetrie quadratique centree (groupe spatial de Schoenflies D{sup 17}{sub 4}n-14/mm) avec les parametres de reseau a{sub 0} = 4.045 A; c{sub 0} = 6.645 A. Il ressort de l'analyse chromatographique de la phase vapeur que 98% du produit gazeux de l'hydrolyse acide du bicarbure d'europium sont constitues par de l'acetylene. Les resultats de ces operations d'analyse et les parametres de reseau indiquent que le bicarbure d'europium presente plus d'analogie avec les bicarbures des metaux alcalino-terreux qu'avec les bicarbures des autres lanthanides. Les auteurs ont etudie, par la methode d'effusion de Knudsen, la vaporisation du bicarbure d'europium dans l'intervalle de temperature compris entre 1130 et 1600 Degree-Sign K. L'effusat a ete rassemble et analyse chimiquement ou observe a l'aide d'un spectrometre de masse a temps de vol. Les valeurs- donnees dans le memoire se fondent avant tout sur les observations faites au moyen de cet appareil; en effet, ces observations fournissent des valeurs plus aisement reproductibles que la methode du rassemblement. Il a ete constate que l'effusat contenait du bicarbure d'europium et de l'europium gazeux, dont les concentrations etaient respectivement de 1 et 99%. Les limitations dues a l'appareil n'ont pas permis de determiner la concentration du bicarbure gazeux en fonction de la temperature. Apres avoir etalonne le spectrometre de masse au moyen de l'argent, il a ete possible de calculer les pressions correspondant aux intensites ioniques observees. Une equation empirique a ete ajustee aux donnees relatives a l'europium par la methode des moindres carres. En appliquant le deuxieme principe de la thermodynamique a la reaction, on a calcule les valeurs suivantes: EuC{sub 2} Rightwards-Harpoon-Over-Leftwards-Harpoon Eu(g) + 2C (graphite); {Delta}H{sup 0}{sub 298} = 51.09{+-}1.42kcal/mole; {Delta}H{sup 0}{sub 298} = 18.43 {+-} 1.75 e.u. Les auteurs ont determine des valeurs estimees de la fonction d'energie libre pour EuC{sub 2}(s) et les ont combinees avec les donnees publiees; ils ont ainsi obtenu pour la meme reaction, en se fondant sur le troisieme principe de thermodynamique, la valeur {Delta}H{sup 0}{sub 298} = 51.22 {+-} 0.80 kcal/mole. Ils ont combine les enthalpies obtenues pour la reaction de dissociation avec les donnees publiees sur l'enthalpie de vaporisation de l'europium et ont ainsi obtenu la valeur ci-apres pour Venthalpie type de la formation de EuC{sub 2} : {Delta}H{sub f(298)} = -9.17 {+-} 1.15 kcal/ mole. (author) [Spanish] Se preparo dicarburo de europio por reaccion entre europio metalico y grafito, en una bomba de acero inoxidable. Los analisis quimicos indican que la composicion media del producto puede representarse por la formula EuC{sub 1.87{+-}0.07}. El examen mediante difraccion de rayos X por polvos muestra que el compuesto posee una simetria tetragonal centrada en el cuerpo (grupo espacial D{sup 17}{sub 4}n-14/mmm) con parametros del reticulado a{sub 0} = 4.045 A; c{sub 0} = 6.645 A. El analisis cromato- grafico en fase vapor indica que el 98% del producto gaseoso proveniente de la hidrolisis acida del dicarburo de europio esta formado por acetileno. Estos datos analiticos, juntamente con los parametros del reticulado, indican que el dicarburo de europio se asemeja mas a los dicarburos de elementos alcalinoterreos que a los de lantanidos. Empleando el metodo de efusion de Knudsen, se estudio la vaporizacion del dicarburo de europio en el intervalo de temperaturas 1130 - 1600 Degree-Sign K. El producto efundido se recogio y se analizo quimicamente, o bien se observo con un espectrometro de masas por el metodo del tiempo de vuelo. Los resultados presentados en la memoria se basan fundamentalmente en las observaciones efectuadas con este ultimo aparato, pues los datos suministrados son mas reproducibles que los obtenidos con la tecnica de recoleccion. En el producto efundido se hallo dicarburo de europio y europio gaseosos, en concentraciones de 1 y 99% respectivamente. Las limitaciones del instrumental impidieron determinar la concentracion del dicarburo gaseoso en funcion de la temperatura. La calibracion del espectrometro de masas con plata permitio calcular las presiones correspondientes a las intensidades ionicas observadas. Una ecuacion empirica fue adaptada a los datos del europio usando el metodo de los cuadrados minimos. Partiendo del segundo principio de la termodinamica se obtuvieron los siguientes valores para la reaccion EuC{sub 2} Rightwards-Harpoon-Over-Leftwards-Harpoon Eu(g) + 2C (graphite); {Delta}H{sup 0}{sub 298} = 51.09{+-}1.42kcal/mole; {Delta}H{sup 0}{sub 298} = 18.43 {+-} 1.75 e.u. Se estimaron los valores correspondientes a la funcion de energia libre para el EuC{sub 2} (s) y se combinaron con los datos publicados alcanzando para la misma reaccion y aplicando el tercer principio de la termodinamica, el valor {Delta}H{sup 0}{sub 298} = 51.22 {+-} 0.80 kcal/mol. Las entalpias obtenidas para la reaccion de disociacion se combinaron con los datos publicados sobre la entalpia de vaporizacion del europio, obteniendose para la entalpia tipo de formacion del EuC{sub 2} el valor {Delta}H{sub f(298)} = -9.17 {+-} 1.15 kcal/mole. (author) [Russian] Dikarbid evropija poluchen v rezul'tate reakcii metallicheskogo evropija i grafita v bombe iz nerzhavejushhej stali. Dannye himicheskogo analiza ukazyvajut, chto srednij sostav produkta sostavljaet EuC{sub 1.87{+-}0.07}. Rezul'taty analiza rentgenogramm tipa Debaja-IIl errera svidetel'stvujut o nalichii ob{sup e}mno-centrirovannoj tetragonal'noj simmetrii v strukture soedinenija i prostranstvennoj gruppy D{sup 17}{sub 4}n-14/mm s parametrami reshetki: a{sub 0} = 4.045 A; c{sub 0} = 6.645 A. Dannye hromatograficheskogo analiza fazy para ukazyvajut na to, chto devjanosto vosem' procentov gazoobraznogo produkta kislotnogo gidroliza dikarbida evropija sostavljaet uglevodorod, acetilen. Jeti dannye analiza vmeste s parametrami reshetki svidetel'stvujut o tom, chto dikarbid evropija pohozh na dikarbidy shhelochnyh zemel' bol'she, chem na drugie dikarbidy lantanonov. Process vyparivanija dikarbida evropija v diapazone temperatur 1130 Degree-Sign - 1 600 Degree-Sign K izuchalsja metodom jeffuzii Knudsena. Jeffuzat libo sobiralsja i analizirovalsja himicheskim putem, libo izuchalsja s pomoshh'ju mass-spektrometra po vremeni proleta. Predstavlennye zdes' dannye osnovany glavnym obrazom na rezul'tatah nabljudenij s pomoshh'ju mass-spektrometra, poskol'ku jeti rezul'taty priveli k oblucheniju bolee vosproizvodimyh dannyh, chem pri metode sbora. V jeffuzate obnaruzheny gazoobraznye dikarbid evropija i evropij v koncentracijah sootvetstvenno 1 i 99%. Vozmozhnosti priborov ne pozvolili opredelit' koncentraciju gazoobraznogo dikarbida kak funkciju temperatury. Kalibrovanie mass-spektrometra serebrom dalo vozmozhnost' rasschitat' davlenija, sootvetstvujushhie otmechennoj intensivnosti ionov. Jempiricheskoe uravnenie sootvetstvovalo dannym po evropiju, poluchennym metodom naimen'shih kvadratov . Na osnovanii vtorogo zakona termodinamiki EuC{sub 2} Rightwards-Harpoon-Over-Leftwards-Harpoon Eu(g) + 2C (graphite) byli vychisleny sledujushhie dannye: {Delta}H{sup 0}{sub 298} = 51.09{+-}1.42kcal/mole; {Delta}H{sup 0}{sub 298} = 18.43 {+-} 1.75 e.u. Znachenija funkcii svobodnoj jenergii dlja EuC{sub 2} (S) rasschityvalis' i ispol'zovalis' vmeste s opublikovannymi dannymi s cel'ju poluchenija dlja jetoj reakcii iz tret'ego za{sup k}ona termodinamiki sledujushhej velichiny : {Delta}H{sup 0}{sub 298} = 51.22 {+-} 0.80 kkal/mol'. Dannye po jental'pijam, poluchennye dlja sluchaja reakcii dissociacii, uvjazyvalis' s opublikovannymi dannymi po jental'pii processa vyparivanija evropija s cel'ju poluchenija dlja standartnoj jental'pii pri obrazovanija EiS{sub 2} velichiny: {Delta}H{sub f(298)} = -9.17 {+-} 1.15 kkal/mol'. (author)}
place = {IAEA}
year = {1966}
month = {Jan}
}