Thermochemistry of hydrated rare earth orthophosphates |
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Authors: | I. Horváth I. A. Bondar L. P. Mezentseva |
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Affiliation: | (1) Institute of Inorganic Chemistry, Chemical Research Centre, Slovak Academy of Sciences, 842 36 Bratislava, Czechoslovakia;(2) Institute of Silicate Chemistry, Academy of Sciences of the USSR, 199 164 Leningrad, USSR |
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Abstract: | The hydrated rare earth orthophosphates LnPO4 ·xH2O (Ln=La-Dy) contain zeolitic water in the structural channels, which is released reversibly up to 300°. The thermal stabilities of the hydrates depend upon the nature of the Ln atom. The dehydration temperature decreases with decreasing ionic radiusr of Ln3+, according to the general equation =(r–a)/b (where is the DSC and/or DTG dehydration peak temperature, anda andb are empirical constants depending on the experimental conditions).The contracting-area rate equation was valid for linearization of the isothermal vs. time plots in the range 0; 0.65 . Kinetic values ofE, A, H+ and S+ were calculated and the kinetic stabilities of the hydrates are discussed.
Zusammenfassung Die hydratisierten Seltenerdiphosphate LnPO4·xH2O (Ln=La bis Dy) enthalten in Kanälen ihrer Struktur zeolithisches Wasser, das reversibel bis 300 °C abgegeben wird. Die thermische Stabilität der Hydrate hängt von der Natur des Ln ab. Die Entwässerungstemperatur sinkt mit abnehmendem Ionenradiusr der Ln3+-Ionen gemäss: =(r–a)/b (a undb sind empirische Konstanten, die von den experimentellen Bedingungen abhängen). Die isotherme Entwässerung lässt sich im Umsatzbereich 0 0,65 mit der Gleichung für kontrahierende Fläche (zweidimensionale Phasengrenzreaktion) beschreiben. Die kinetischen Grössen AktivierungsenergieE, -enthalpie H*, und -entropie S* wurden berechnet und die kinetische Stabilität der Hydrate wird diskutiert.
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![Delta](/content/fv316517m89q8x33/xxlarge916.gif) * ![icy](/content/fv316517m89q8x33/xxlarge1080.gif) S* ![ocy](/content/fv316517m89q8x33/xxlarge1086.gif) ![bcy](/content/fv316517m89q8x33/xxlarge1073.gif) ![scy](/content/fv316517m89q8x33/xxlarge1089.gif) ![ucy](/content/fv316517m89q8x33/xxlarge1091.gif) ![zhcy](/content/fv316517m89q8x33/xxlarge1078.gif) ![dcy](/content/fv316517m89q8x33/xxlarge1076.gif) ![iecy](/content/fv316517m89q8x33/xxlarge1077.gif) ![ncy](/content/fv316517m89q8x33/xxlarge1085.gif) ![kcy](/content/fv316517m89q8x33/xxlarge1082.gif) ![icy](/content/fv316517m89q8x33/xxlarge1080.gif) ![ncy](/content/fv316517m89q8x33/xxlarge1085.gif) ![iecy](/content/fv316517m89q8x33/xxlarge1077.gif) ![tcy](/content/fv316517m89q8x33/xxlarge1090.gif) ![icy](/content/fv316517m89q8x33/xxlarge1080.gif) ![chcy](/content/fv316517m89q8x33/xxlarge1095.gif) ![iecy](/content/fv316517m89q8x33/xxlarge1077.gif) ![kcy](/content/fv316517m89q8x33/xxlarge1082.gif) ![acy](/content/fv316517m89q8x33/xxlarge1072.gif) ![ucy](/content/fv316517m89q8x33/xxlarge1091.gif) ![scy](/content/fv316517m89q8x33/xxlarge1089.gif) ![tcy](/content/fv316517m89q8x33/xxlarge1090.gif) ![ocy](/content/fv316517m89q8x33/xxlarge1086.gif) ![jcy](/content/fv316517m89q8x33/xxlarge1081.gif) ![chcy](/content/fv316517m89q8x33/xxlarge1095.gif) ![icy](/content/fv316517m89q8x33/xxlarge1080.gif) ![vcy](/content/fv316517m89q8x33/xxlarge1074.gif) ![ocy](/content/fv316517m89q8x33/xxlarge1086.gif) ![scy](/content/fv316517m89q8x33/xxlarge1089.gif) ![tcy](/content/fv316517m89q8x33/xxlarge1090.gif) ![gcy](/content/fv316517m89q8x33/xxlarge1075.gif) ![icy](/content/fv316517m89q8x33/xxlarge1080.gif) ![dcy](/content/fv316517m89q8x33/xxlarge1076.gif) ![rcy](/content/fv316517m89q8x33/xxlarge1088.gif) ![acy](/content/fv316517m89q8x33/xxlarge1072.gif) ![tcy](/content/fv316517m89q8x33/xxlarge1090.gif) ![ocy](/content/fv316517m89q8x33/xxlarge1086.gif) .
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