Thermal properties of rare earth dodecaborides

We have measured heat capacity and thermal expansion of rare earth dodecaborides REB₁₂ (RE=Y, Tb-Tm, Lu). YB₁₂ and LuB₁₂ are diamagnetics whereas the other dodecaborides are ordered antiferromagnetically. The amplitude of the heat capacity discontinuity at the Néel temperature and the shape of the heat capacity variation in the critical region for all these antiferromagnetics are characteristics for amplitude-modulated magnetic structures. In the ordered state TbB₁₂ reveals two first-order phase transitions, most likely due to magnetic structure changes. The heat capacity of ErB₁₂ just below the Néel point shows an anomaly of unclear origin. From the Schottky contribution to the heat capacity we have determined crystal field parameters. They are completely different than that is estimated from Point Charge Model.     

Thermal decomposition of rare earth element enanthates

The conditions of formation of Y, La and lanthanide (from Ce(III) to Lu) enanthates were worked out, their composition and their solubilities in water at 291 K were determined, and the conditions of their thermal decomposition were studied. They were prepared as crystalline solids with general formula Ln(C₇H₁₃O₂)₃·nH₂O, wheren=2–10. On heating, they decompose in two or three steps. They first lose some water molecules and then decompose to the oxides directly (salts of Y and heavy lanthanides) or via the intermediate formation of Ln₂O₂CO₃ (salts of La, Pr, Nd, Sm and Eu). Only yttrium enanthate dihydrate loses 2 water molecules on heating to form an anhydrous complex, which decomposes directly to Y₂O₃. The temperatures of dehydration are similar for all complexes (323–343 K), while the temperatures of oxide formation vary irregularly from 823 K for CeO₂ to 1078 K for La₂O₃.     

Thermal decomposition of rare earth oxysulfides in air

The thermal decomposition of rare earth oxysulfides (excluding Sc, Ce and Pm) has been studied in air. The oxysulfides are oxidized to oxysulfates between 600 and 900 and the oxysulfate phase, which is unstable at higher temperatures, decomposes to oxide. The stability of the oxysulfate and its decomposition temperature decreases with decreasing radius of the rare earth ion. For the heavier rare earths the oxidation to oxysulfate takes place only partially before the decomposition to oxide begins.

---

Zusammenfassung Die thermische Zersetzung der Oxysulfide der seltenen Erden (mit Ausnahme von Sc, Ce und Pm) wurde in Luft untersucht. Die Oxysulfide werden zwischen 600 und 900 zu Oxysulfaten oxidiert und die Oxysulfatphase, welche bei höheren Temperaturen instabil ist, wird zu Oxid zersetzt. Die Stabilität des Oxysulfats und seine Zersetzungstemperatur nehmen mit abnehmendem Radius des seltenen Erden-Ions ab. Bei den schwereren seltenen Erden erfolgt die Oxysulfatbildung nur teilweise vor den Einsetzen des Abbaus zu Oxid.

---

- , Sc, m. 600 900° , , . - . - , .

     

Thermal decomposition of rare earth complexes withm-aminobenzoic acid

The conditions of thermal decomposition of the m-aminobenzoates of Y, La, Ce(III), Pr, Nd and Sm-Lu, Ln(C₆H₄NH₂COO)₃.nH₂O (n=4–6), have been studied.The hydrated compounds lose all molecules of crystallization water in one stage at 333–413 K. The anhydrous compounds are stable up to 570 K and are then decomposed exothermically to oxides.

---

Zusammenfassung Es wurden die Bedingungen für die thermische Zersetzung derm-Aminobenzoate Ln(C₆H₄NH₂COO)₃.nH₂O (n=4–6) von Y, La, Ce(III), Pr, Nd und Sm-Lu untersucht. Alle Verbindungen geben ihr Kristallwasser in einem Schritt bei einer Temperatur zwischen 333 und 413 K ab. Die wasserfreien Verbindungen sind bis 570 K stabil und zersetzen sich dann exotherm unter Entstehung von Oxiden.

     

Thermal and structural properties of rare earth exchanged zeolites

A series of rare earth zeolites of types X and Y were prepared by cation exchange. Thermal analysis curves (TG/DTA) were employed to estimate the structural changes in the zeolite framework. Analogous investigations were carried out by independent methods such as XRD and IR spectroscopy. The results indicate increased thermal stability on the replacement of sodium by rare earth. Partial replacement of rare earth by ammonium/hydrogen enhances the thermal stability. The type Y zeolites are more stable than those of X type.

---

Zusammenfassung Eine Reihe von Ionen der Seltenen Erdmetalle enthaltenden Zeolithen des Typs X und Y wurden durch Ionenaustausch hergestellt. Thermoanalytische Kurven (TG/DTA) wurden zur Beurteilung der strukturellen Veränderungen des Zeolithgitters herangezogen. Analoge Untersuchungen wurden mit unabhängigen Methoden (XRD und IR-Spektroskopie) ausgeführt. Es wurde festgestellt, daß ein Ersatz der Natriumionen durch Ionen der Seltenen Erdmetalle zu einer Erhöhung der thermischen Stabilität führt. Ein teilweiser Ersatz der Seltenen Erdmetallionen durch Ammonium-/Wasserstoffionen erhöht die thermische Stabilität. Zeolithe des Typs Y sind stabiler als die des X-Typs.

---

X . (/) . - . . . X .

---

---

NCL Communication No: 2186     

Determination of rare earths in selected rare earth matrices by spark source mass spectrometry

Three methods of preparing rare earth samples for mass spectrographic analysis are presented. Techniques for adding appropriate internal standards are described and relative sensitivity factors for rare earth impurities in rare earths, lanthanum, yttrium and scandium matrices are presented. Although indium has some value as an internal standard in rare earth samples, best analytical results are obtained when selected rare earths are used as internal standards.     

Thermal decomposition of rare earth complexes with o-aminobenzoic acid

The conditions of thermal decomposition of La, Ce(III), Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu anthranilates have been studied. The anhydrous La, Ce(III), Pr(III), Nd and Sm anthranilates decompose in one step directly to the oxides Ln₂O₃, CeO₂ or Pr₆O₁₁. The monoand dihydrated anthranilates of the remaining rare earths first lose crystallization water when heated, and then decompose exothermally to the oxides Ln₂O₃ or Tb₄O₇.

---

Zusammenfassung Die Bedingungen der thermischen Zersetzung der Anthranilate von La, Ce(III), Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb und Lu wurden untersucht. Die wasserfreien Anthranilate von La, Ce(III), Pr(III) und Nd zersetzen sich in einem Schritt direkt zu den Oxiden Ln₂O₃, CeO₂ und Pr₆O₁₁. Die ein oder zwei Kristallwasser enthaltenden Anthranilate der übrigen seltenen Erdmetalle werden beim Erhitzen zunächst dehydratisiert und danach exotherm zu den Oxiden Ln₂O₃ und Tb₄O₇ abgebaut.

---

, . , , Ln₂O₃, CeO₂ Pr₆O₁₁. - Ln₂O₃ Tb₄O₇.

     

Thermal decomposition of rare earth salicylates in air atmosphere

The conditions of decomposition of Y, La and lanthanide (from Ce(III) to Lu) salicylates have been studied. On heating, the hydrated salicylates of Y and lanthanides from Nd to Lu lose crystallization water in one step to yield the anhydrous salts. The anhydrous complexes of Y, La, Ce(III), Pr, Nd, Sm, Eu(III), Gd and Tb subsequently decompose in several steps to the oxides Ln₂O₃, CeO₂, Pr₆O₁₁ and Tb₄O₇. The anhydrous complexes of the remaining lanthanides decompose directly to the oxides Ln₂O₃.

---

Zusammenfassung Die Zersetzungsreaktionsbedingungen von Y-, La- und Lanthanid-(Ce(III) bis Lu) salizylaten wurden untersucht. Beim Erhitzen geben hydrierte Salizylate von Y und der Lanthanide Nd bis Lu Kristallwasser in einem Schritt ab und bilden wasserfreie Salze. Die wasserfreien Komplexe von Y, La, Ce(III), Pr, Nd, Sm, Eu(III), Gd und Tb zersetzen sich in mehreren Schritten und bilden die Oxide Ln₂O₃, CeO₂, Pr₆O₁₁ und Tb₄O₇. Die wasserfreien Komplexe der übrigen Lanthaniden zerfallen direkt in Ln₂O₃ Oxide.

---

, . , . , , , , , , , , Ln₂O₃, CeO₂, Pr₆O_{11 47}. Ln₂O₃.

     

Thermal decomposition of rare earth pyromucates in air atmosphere

The conditions of thermal decomposition of Y, La and lanthanide (from Ce(III) to Lu) pyromucates have been studied. On heating, these complexes decompose in various ways: La, Pr, Nd and Sm pyromucates in four stages, Ce, Eu, Gd, Dy, Ho and Er pyromucates in three stages, and Tm, Yb, Lu and Y pyromucates in two stages, the oxides finally being formed. The hydrated complexes (from La to Er) lose crystallization water to form anhydrous salts. The anhydrous complexes of La, Pr, Nd and Sm decompose to oxides through the intermediate formation of unstable oxypyromucates and Ln₂O₂CO₃, whereas the anhydrous complexes of Ce(III), Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu decompose to the oxides through the intermediate formation of oxypyromucates. The temperatures of dehydration and oxide formation change periodically with increasing atomic number in the lanthanide series.

---

Zusammenfassung Die Bedingungen der thermischen Zersetzung der Pyromucate von Y, La und den Lanthaniden (Ce(III) bis Lu) wurden untersucht. Beim Erhitzen zersetzen sich die Komplexe auf verschiedene Weise: die Pyromucate von La, Pr, Nd und Sm in 4 Schritten, die von Ce, Eu, Gd, Dy, Hod Er in 3 Schritten und die von Tm, Yb, Lu und Y in nur 2 Schritten. Endprodukte der Zersetzung sind die Oxide, Die hydratisierten Komplexe von La bis Er verlieren Kristallwasser unter Bildung der wasserfreien Salze. Die wasserfreien Komplexe von La, Pr, Nd und Sm zersetzen sich zu Oxiden über instabile Oxypyromucate und Ln₂O₂CO₃ als Zwischenprodukte, bei der Zersetzung der wasserfreien Komplexe von Ce(III), Eu, Gd, Dy, Ho, Er, Tm, Yb und Lu werden Oxypyromucate als Zwischenprodukte gebildet. Die Temperaturen der Dehydratisierung und Oxidbildung schwanken periodisch mit ansteigender Atomzahl in der Lanthanidenreihe.

---

, ( ) . : , , , , , , , — , , , — . , . , , Ln₂O₂CO₃. . .

     

Thermal decomposition of rare earth element suberates in air atmosphere

The condition of thermal decomposition of La, Ce(III), Pr(III), Nd, Sm, Eu(III), Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu suberates were studied. The suberates of Ce(III), Sm, Eu(III), Ho, Tm, Yb and Lu heated lose crystallization water. Anhydrous Sm and Eu(III) suberates decompose to oxides with intermediate formation Ln₂O₂CO₃, whereas suberates of other lanthanides decompose directly to oxides. Suberates of La, Pr(III), Nd, Gd, Tb, Dy and Er lose some water molecules and then decompose directly to oxides. Only La complex decomposes to La₂O₃ via the intermediate formation La₂O₂CO₃.

---

Zusammenfassung Es wurden die UmstÄnde der thermischen Zersetzung von La-, Ce(III)-, Pr(III)-, Nd-, Sm-, Eu(III)-, Gd-, Tb-, Dy-, Ho-, Er-, Tm-, Yb- und Lu-suberat untersucht. Bei Erhitzen verlieren Ce(III)-, Sm-, Eu(III)-, Ho-, Tm-, Yb- und Lu-suberat Kristallwasser. Wasserfreies Sm-bzw. Eu(III)-suberat zersetzt sich über das Zwischenprodukt der Zusammensetzung Ln₂O₂CO₃ zum Oxid, wÄhrend sich die Suberate der anderen Lanthanoide direkt zu den Oxiden zersetzen. La-, Pr(III)-, Nd-, Gd-, Tb-, Dy- und Er-suberat geben einige Moleküle Kristallwasser ab und zersetzen sich dann direkt zu den Oxiden. Nur der Lanthankomplex zersetzt sich zu La₂O₃ über das Zwischenprodukt La₂O₂CO₃.

     

Thermal decomposition of some rare earth metal cupferrates and neocupferrates

The thermal decomposition of the eupferrates and neocupferrates of europium, terbium, dysprosium, holmium, erbium, and ytterbium was studied on the thermobalance. The metal chelates possessed poor thermal stability as well as a pronounced tendency to Coprecipitate reagent. The minimum oxide level temperatures for the metal cupferrates were : Eu, 570°; Tb, 540°; Dy, 550°; Ho, 610°; Er, 550° and Yb, 520°. The minimum oxide level temperatures for the metal neocupferrates were: Eu, 560°; Tb 565°; Dy, 540°; Ho,445°; Er, 530°; and Yb, 485°.     

Thermal stability of several polyaniline/rare earth oxide composites

Polyaniline/rare earth oxide composites (PANI/La₂O₃ and PANI/Sm₂O₃) were synthesized by in situ polymerization at the presence of sulfosalicylic acid (as dopant). The composites obtained were characterized by Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The thermal stability of the composites was investigated by thermogravimetry (TG) and derivative thermogravimetry (DTG). The electrochemical performance of the composites was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results of FTIR, XRD, SEM, CV, and EIS show that the structure of composite has changed greatly when rare earth oxide content is >0.7 g (PANI/La₂O₃[w/w(92.7/7.3)] and PANI/Sm₂O₃[w/w(96.2/3.8)]) and the PANI in the composite has transformed into pernigraniline base (non-conducting state) from emeraldine base (conducting state). TG-DTG analysis indicates that the thermal stability of composite was higher than pure PANI, which is attributed to the interaction between PANI and rare earth oxide.     

Preparation, thermal stability and luminescence properties of selected rare earth oxycarbonates

A comparative TG and DTG study of the preparation and thermal stability of selected rare earth oxycarbonates, (REO)₂CO₃ (RE = La and Gd), shows that the ease of formation as well as the stability of these compounds decreases strongly with increasing atomic number of the host cation. According to X-ray powder diffraction analyses, the RE oxycarbonates obtained as decomposition products of acetate and carbonate hydrates belong to the tetragonal IA-type. UV- and dye laser-excited luminescence studies of Eu³⁺-doped (LaO)₂CO₃ and (GdO)₂CO₃ reveal the presence of two different sites for the host cation. One of the sites resembles closely that prevailing in the tetragonal RE oxysalts, i.e. oxyhalides, oxysulphates, oxymolybdates and oxynitrates. A crystal field analysis carried out on the ⁷F₁ and ⁷F₂ level schemes according to a C_2v site symmetry confirms this hypothesis.     

Thermal stability of several polyaniline/rare earth oxide composites III

Polyaniline/Nd₂O₃ (PANI/Nd₂O₃) composites were synthesized by in situ polymerization at the presence of sulfosalicylic acid (as dopant). The composites obtained were characterized by Fourier transform infrared spectra (FTIR) and X-ray diffraction (XRD). The thermal stability of the composites was investigated by thermogravimetry (TG) and derivative thermogravimetry (DTG). The electrochemical performance of the composites was investigated by cyclic voltammetry (CV). The results of FTIR, XRD, and CV show that the structure of composite has changed greatly when Nd₂O₃ content is ≥0.7 g and the PANI in the composite has transformed into pernigraniline base (non-conducting state) from emeraldine base (conducting state). TG–DTG analysis indicates that the thermal stability of PANI/Nd₂O₃ composites was higher than the pure PANI.     

Thermal properties of rare earth elements complexes with 1,3,5-benzenetricarboxylic acid

Summary Rare earth elements 1,3,5-benzenetricarboxylates were prepared as solids of the general formula Ln(C₉H₃O₆)·nH₂O, where n=6 for La-Dy and n=4 for Ho-Lu,Y. Their solubilities in water at 293 K are of the order 10^-4-10^-6 mol dm^-3. The IR spectra of the complexes indicate that the carboxylate groups are bridging and bidentate chelates. Hydrated 1,3,5-benzenetricarboxylates lose water molecules during heating in one step (La-Tb), two steps (Y, Ho-Tm) or three steps (Dy, Yb, Lu). The anhydrous complexes are stable up to 573-742 K and decompose to oxides (Ce-Lu) at higher temperatures.     

Thermoanalytical study on the reactions of selected rare earth oxides with ammonium halides

A comparative study has been made on the reactions of RE oxides (RE = Y, La, Gd and Lu) with ammonium bromide, and of yttrium oxide with ammonium halides NH₄X (X = F, Cl, Br and I) at different temperatures. Most of the reactions take place in three stages, with formation of two intermediate compounds, REX₃ · 3 NH₃ and REX₃ · 1.5 NH₃. The endothermic reactions begin between 200 and 300°C and the formation of the RE oxyhalide is completed between 340 and 470°C. These temperatures were observed to rise with the increasing atomic number of RE in the series LaOBrLuOBr, and of halide in the series YOFYOI.     

Thermal decomposition as a preparative route to anhydrous rare earth nitrates

Thermal decomposition of rare earth pentanitrato complexes has been studied by TG and DTA. M₂Ln(NO₃)₅·nH₂O (M=NH₄, Ln=La, Nd, Pr) decomposes in air through anhydrous (NH₄)₂Ln(NO₃)₅ to Ln(NO₃)₃, LnONO₃ and finally to Ln₂O₃ above 600°C. When M=K and Ln=La, the intermediate K₂La(NO₃)₅ is remarkably stable and KLaO₂is formed at 800°C. Except for Nd, the nonanitrato complex M₃Ln₂(NO₃)₉ was detected during the degradation process in both air and nitrogen but its stability range is too narrow to allow its preparative isolation as single phase. For comparison, the TG and DSC curves were recorded for La(NO₃)₃·6H₂O where La(NO₃)₃ and especially LaONO₃ appear as stable intermediates.

---

Zusammenfassung Mittels TG und DTA wurde die thermische Zersetzung der Pentanitratokomplexe von Seltenerden untersucht. Oberhalb 600°C zersetzt sich M₂Ln(NO₃)₅·nH₂O (M=NH₄, Ln=La, Nd, Pr) in Luft über die Zwischenstufen wasserfreies (NH₄)₂ Ln(NO₃)₅, Ln(NO₃)₃ und LnONO₃ zu Ln₂O₃. Mit M=K und Ln=La ist das Zwischenprodukt K₂ La(NO₃)₅ äußerst stabil und bei 800°C bildet sich KLaO₂. Mit Ausnahme von Nd konnten während der Abbauprozesse sowohl in Luft als auch in Stick-Stoff die Nonanitratokomplexe M₃Ln₂(NO₃)₉ beobachtet werden, deren Stabilitätsbereich jedoch für eine präparative Isolierung in Form einer einzigen Phase zu klein ist. Zum Vergleich wurden die TG- und DSC-Kurven von La(NO₃)₃·6H₂O aufgenommen, wobei sich La(NO₃)₃ und besonders LaONO₃ als stabile Zwischenprodukte erwiesen.

---

- . ₂Ln/NO_3/5·nH₂O/M=NH₄, Ln=La, Nd, Pr/ , Ln/NO_3/3, LnONO₃, 600° Ln₂O₃. = Ln=La K₂La/NO_3/5 800° KLaO₂. , , M₃Ln₂/NO_3/9, , . , LaONO₃ B .

     

Thermal and spectral studies of some rare earth chelates of chlorojuglone antibacterials

The metal chelates of juglone, 3-chlorojuglone and 2,3-dichlorqjuglone with trivalent lanthanum, cerium and praseodymium have been synthesised. The thermal, spectral and magnetic properties of these chelates were investigated to study the effect of substitution on the chelating ability of the ligand.     

Thermal and spectral properties of some anhydrous and hydrated rare earth hydrazinecarboxylates

The anhydrous rare earth hydrazinecarboxylates, Ln(N₂H₃COO)₃ where Ln=La, Ce, Pr, Nd or Sm and hydrated rare earth hydrazinecarboxylates, Ln(N₂H₃COO)₃(H₂O)₃ where Ln=La or Nd have been prepared and characterized by chemical analyses, infrared spectroscopy and thermal analyses (TG/DTA/DTG). The infrared spectra indicate that the hydrazinecarboxylate group in both the sets of complexes is coordinated in a bidentate (chelate) fashion with the N-N stretching frequency at 980-1000 cm^-1. The thermal analyses of all the complexes show multi-step decomposition. The final product in all the cases is invariably the respective metal oxide carbide, Ln₂O₂C₂, though there are some variations in the decomposition pattern. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal and spectral studies of rare earth element 3-methoxy-4-methylbenzonates

3-Methoxy-4-methylbenzoates of Y(III) and lanthanide(III) (La-Lu) were prepared as crystalline compounds with molar ratio of metal to organic ligand of 1.0:3.0 and general formula Ln(C₉H₉O₃)3·nH₂O, where n=2 for Y, La-Er and n=0 for Tm-Lu. IR spectra of the prepared complexes suggest that carboxylate groups are bidentate chelating. During heating dihydrated complexes lose crystallization water molecules in one (Y, La, Pr-Er) or two steps (Ce) and then all the anhydrous complexes decompose directly to oxides Ln₂O₃, CeO₂, Pr₆O₁₁ and Tb₄O₇.Vadim Mamleev is grateful to Region Nord-pas-de-Calais (France) for financial support and to laboratory PERF of ENSCL for its kind invitation to continue the joint work on thermal analysis.