Comparative kinetic and thermodynamic study on the chlorination of V2O5 with CCl4, COCl2 and Cl2 |
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Authors: | I S Pap G Mink I Bertóti T Székely I Z Babievskaya E Karmazsin |
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Institution: | (1) Research Laboratory for Inorganic Chemistry of the Hungarian Academy of Sciences, P. O. Box 132, H-1502 Budapest, Hungary;(2) N. S. Kurnakov Insitute of General and Inorganic Chemistry, Academy of the Sciences of the USSR, Moscow, USSR;(3) Department of Applied Chemistry, Claude Bernard University, Lyon, France |
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Abstract: | The chlorination kinetics of pure vanadia was studied via isothermal thermogravimetric measurements, with CCl4, CoCl2 and Cl2 as chlorinating agents. At temperatures where chemical control was predominant, apparent activation energies of 77, 48 and 126 kJ: mol–1 were obtained for chlorination by CCl4, COCl4 and Cl2, respectively. For interpretation of the conversion vs. time curves in the whole conversion range, a non-uniform particle size distribution was assumed, where the reacting solid phase was considered to be composed of thin plates of different thicknesses. With this model, a fairly good correspondence was obtained between the measured and calculated kinetic curves. Selected thermodynamic calculation data on the V2O5 + CCl4, V2O5 + COCl2 and V2O5 + Cl2 systems are presented.
Zusammenfassung Mittels isothermen Thermogravimetriemessungen wurde die Kinetik der Chlorierung von reinem Vanadiumoxid mit CCl4, COCl2 und Cl2 als Chlorierungsmittel untersucht. Bei Temperaturen mit vorherrschender chemischer Kontrolle wurde für die Chlorierung mit CCl4, COCl2 bzw. Cl2 Bruttoaktivierungsenergien von 77, 48 bzw. 126 kJ/mol erhalten. Zur Interpretation der Konversion-Zeit-Diagramme im gesamten Conversionsbereich wurde eine nichteinheitliche Teilchengrösseverteilung angenommen, namentlich den Bestand der reagierenden Festphase aus dünnen Plättchen unterschiedlicher Dicke. Mit diesem Modell konnte eine recht gute Übereinstimmung zwischen errechneten und ermittelten kinetischen Kurven erhalten werden. Einige thermodynamische Rechenbeispiele für die Systeme V2O5 + CCl4, V2O5 + COCl2 und V2O5+Cl2 wurden gegeben.
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![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![zcy](/content/v1712u3v58410517/xxlarge1079.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![pcy](/content/v1712u3v58410517/xxlarge1087.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![zcy](/content/v1712u3v58410517/xxlarge1079.gif) ![mcy](/content/v1712u3v58410517/xxlarge1084.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) .![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![gcy](/content/v1712u3v58410517/xxlarge1075.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) , ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![kcy](/content/v1712u3v58410517/xxlarge1082.gif) ![tscy](/content/v1712u3v58410517/xxlarge1094.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![vcy](/content/v1712u3v58410517/xxlarge1074.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![fcy](/content/v1712u3v58410517/xxlarge1092.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![kcy](/content/v1712u3v58410517/xxlarge1082.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![pcy](/content/v1712u3v58410517/xxlarge1087.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![kcy](/content/v1712u3v58410517/xxlarge1082.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![vcy](/content/v1712u3v58410517/xxlarge1074.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![shchcy](/content/v1712u3v58410517/xxlarge1097.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) . ![ecy](/content/v1712u3v58410517/xxlarge1101.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![mcy](/content/v1712u3v58410517/xxlarge1084.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![bcy](/content/v1712u3v58410517/xxlarge1073.gif) ![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![pcy](/content/v1712u3v58410517/xxlarge1087.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![ucy](/content/v1712u3v58410517/xxlarge1091.gif) ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![zcy](/content/v1712u3v58410517/xxlarge1079.gif) ![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![jcy](/content/v1712u3v58410517/xxlarge1081.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![khcy](/content/v1712u3v58410517/xxlarge1093.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![shcy](/content/v1712u3v58410517/xxlarge1096.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![vcy](/content/v1712u3v58410517/xxlarge1074.gif) ![pcy](/content/v1712u3v58410517/xxlarge1087.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![zhcy](/content/v1712u3v58410517/xxlarge1078.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![zcy](/content/v1712u3v58410517/xxlarge1079.gif) ![mcy](/content/v1712u3v58410517/xxlarge1084.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) -![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![mcy](/content/v1712u3v58410517/xxlarge1084.gif) ![vcy](/content/v1712u3v58410517/xxlarge1074.gif) ![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![mcy](/content/v1712u3v58410517/xxlarge1084.gif) ![kcy](/content/v1712u3v58410517/xxlarge1082.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![kcy](/content/v1712u3v58410517/xxlarge1082.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![mcy](/content/v1712u3v58410517/xxlarge1084.gif) ![kcy](/content/v1712u3v58410517/xxlarge1082.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![vcy](/content/v1712u3v58410517/xxlarge1074.gif) ![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![mcy](/content/v1712u3v58410517/xxlarge1084.gif) . ![Pcy](/content/v1712u3v58410517/xxlarge1055.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![vcy](/content/v1712u3v58410517/xxlarge1074.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![vcy](/content/v1712u3v58410517/xxlarge1074.gif) ![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![rcy](/content/v1712u3v58410517/xxlarge1088.gif) ![mcy](/content/v1712u3v58410517/xxlarge1084.gif) ![ocy](/content/v1712u3v58410517/xxlarge1086.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![mcy](/content/v1712u3v58410517/xxlarge1084.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![chcy](/content/v1712u3v58410517/xxlarge1095.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![kcy](/content/v1712u3v58410517/xxlarge1082.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![acy](/content/v1712u3v58410517/xxlarge1072.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ncy](/content/v1712u3v58410517/xxlarge1085.gif) ![ycy](/content/v1712u3v58410517/xxlarge1099.gif) ![dcy](/content/v1712u3v58410517/xxlarge1076.gif) ![lcy](/content/v1712u3v58410517/xxlarge1083.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![icy](/content/v1712u3v58410517/xxlarge1080.gif) ![scy](/content/v1712u3v58410517/xxlarge1089.gif) ![tcy](/content/v1712u3v58410517/xxlarge1090.gif) ![iecy](/content/v1712u3v58410517/xxlarge1077.gif) V2O5+CCl4, V2O5+COCl2 V2O5+Cl2.
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