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Abstract  

Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 3-methylglutarates were prepared as solids with general formula MC6 H8 O4 n H2 O, where n =0–8. Their solubilities in water at 293 K were determined (7.010−2 −4.210−3 mol dm−3 ). The IR spectra were recorded and thermal decomposition in air was investigated. The IR spectra suggest that the carboxylate groups are mono- or bidentate. During heating the hydrated complexes lose some water molecules in one (Mn, Co, Ni, Cu) or two steps (Cd) and then mono- (Cu) or dihydrates (Mn, Co, Ni) decompose to oxides directly (Mn, Cu, Co) or with intermediate formation of free metals (Co, Ni). Anhydrous Zn(II) complex decomposes directly to the oxide ZnO.

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Abstract  

Conditions for the formation of rare earth element (Y, La–Lu) 3-methylglutarates were studied and their quantitative composition and solubilities in water at 293 K were determined (10–2 mol dm–3). The IR spectra of the prepared complexes with general formula Ln2(C6H8O4)3 nH2O (n=3–8) were recorded and their thermal decomposition in the air were investigated. During heating the hydrated 3-methylglutarates are dehydrated in one step and next anhydrous complexes decompose to oxides Ln2O3 with intermediate formation Ln2O2CO3 (Y, La, Nd–Gd) or directly to the oxides, Ln2O3, CeO2, Pr6O11 and Tb4O7 (Ce, Pr, Tb–Lu).

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The conditions of thermal decomposition of La, Ce(III), Pr(III), Nd, Sm(III), Eu, Gd, Tb(III), Dy, Ho, Er, Tm, Yb and Lu sebacates have been studied. When heated in air atmosphere, the sebacates of La and lanthanides with general formula Ln2(C10H16O4)3·nH2O, wheren=6−24, lose some crystallization water molecules in one or two steps at 323–343 K and are then dehydrated and decomposed simultaneously to the oxides Ln2O3, CeO2, Pr6O11 and Tb4O7. The oxides are formed over the range of temperature 783 K (CeO2)−1073 K (Nd2O3).

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The rare earth complexes with glycolic acid were prepared as crystalline solids with general formula [Ln(CH2OHCOO)3H2O]·nH2O, wheren=0 for La-Gd andn=2 for Y and Tb-Lu. During heating the monohydrates of La and Pr-Gd decomposed in two steps to Ln2O3 and Pr6O11, with intermediate formation of Ln2O2CO3; monohydrated Ce(III) glycolate decomposed directly to CeO2. The trihydrated glycolates of Y and Tb-Lu first lost two water molecules and the monohydrated complexes then decomposed to Ln2O3 and Tb4O7 through Ln2O2CO3.

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The conditions of thermal decomposition of La, Ce(III), Pr, Nd, Sm, Eu and Gd diglycolates have been studied. On heating, the diglycolates of Ce(III), Pr, Eu and Gd lose crystallization water and yield anhydrous salts, which are then transformed into oxides.

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The conditions of thermal decomposition of Y, La, Ce(III), Pr, Nd, Sm, and Gd aconitates have been studied. On heating, the aconitate of Ce(III) loses crystallization water to yield anhydrous salt, which then is transformed in to oxide CeO2. The aconitates of Y, Pr, Nd, Sm, Eu and Gd decompose in three stages. First, aconitates undergo dehydration to form the anhydrous salts, which next decompose to Ln2O2CO3. In the last one the thermal decomposition of Ln2O2CO3 to Ln2O3 is accompanied by endothermic effect. Dehydration of aconitate of La undergoes in two stages. The anhydrous complex decomposes to La2O2CO3; this subsequently decomposes to La2O3.

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The conditions of thermal decomposition of Tb(III), Dy, Ho, Er, Tm, Yb and Lu aconitates have been studied. On heating, the aconitates of heavy lanthanides lose crystallization water to yield anhydrous salts, which are then transformed into oxides. The aconitate of Tb(III) decomposes in two stages. First, the complex undergoes dehydration to form the anhydrous salt, which next decomposes directly to Tb4O7. The aconitates of Dy, Ho, Er, Tm, Yb and Lu decompose in three stages. On heating, the hydrated complexes lose crystallization water, yielding the anhydrous complexes; these subsequently decompose to Ln2O3 with intermediate formation of Ln2O2CO3.

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