Evolution des dimensions des cristallites des phases initiale et finale au cours de la deshydratation mecanique: Cd(OH)2 →CdO + H2O

The grinding under constant temperature and vapour pressure of Cd(OH)₂ brings about rapid dehydration into CdO.The evolution v.s. grinding time of the half bredth of hydroxide and oxide X-ray diffraction lines shows three steps. The part of diminution in particle size or distortions of the structure but also of the mechanical dehydration in these modifications is discussed.The X-ray line profiles Fourier analysis shows that (i) whatever temperature and vapour pressure imposed during the grinding, the particles sizes of the oxide product by mechanical dehydration is close to that of the oxide obtained by thermal dehydration under vacuum. (ii) The distortions of the structure don't depend on the dehydration process, they are similar in the two types of oxide but they are influenced by the vapour pressure.     

Mechanochemical synthesis of rutile-type CrMO4 (M=V, Sb) and their solid solutions

Grinding a mixture of hydrous amorphous chromium oxide (Cr₂O₃·nH₂O), vanadium oxide (V₂O₅) and antimony oxide (Sb₂O₅) was conducted by using a planetary ball mill, to investigate their mechanochemical reactions to form chromium vanadium oxide (CrVO₄) and chromium antimony oxide (CrSbO₄). The synthesis reactions proceed with an increase in grinding periods of time. The ground samples consist of agglomerates with particle size of about ten nanometers. The synthesized CrVO₄ sample exhibits a rutile-type tetragonal crystal structure, which is a high pressure phase. Additionally, solid solutions, CrV_1−xSb_xO₄ (x=0∼1, Δx=0.25), have been synthesized mechanochemically from the mixtures of Cr₂O₃·nH₂O, V₂O₅ and Sb₂O₅.     

Rare earth trisoxalatocobaltates(III) a precursor for rare earth cobaltites(III)

Rare earth cobalties, LnCoO₃, can be conveniently prepared by the thermal decomposition of the precursor LnCo(C₂O₄)₃·nH₂O (La, Ce, n=9; Pr, Nd, n=8). CeCo(C₂O₄)₃·8H₂O, unlike the other oxalato compounds thermally decompose to a mixture of CeO₂ and Co₃O₄. Although LnCoO₃are formed from the precursors at a temperature lower than 800°C, thermal analysis of a mixture of La₂(C₂O₄)₃·10H₂O and CoC₂O₄·2H₂O at 900·C shows the residue containing mainly La₂O₃ and Co₃O₄ with a small amount of LaCoO₃.     

Rare earth phosphate powders RePO4·nH2O (Re=La,Ce or Y) II. Thermal behavior

The thermal behavior, thermostructural and morphological changes, of rare earth phosphate powders RePO₄·nH₂O (Re=La, Ce or Y) was investigated up to 1500°C using high temperature X-ray diffraction, FT-infrared and Raman spectroscopies and thermogravimetry coupled with differential thermal analysis. The hydration water of the compounds was zeolitic (for Re=La or Ce) or coordinated (for Re=Y) and was associated with a divariant or a monovariant equilibrium of dehydration, respectively. The high temperature anhydrous monoclinic phase LaPO₄ or CePO₄ formed irreversibly at about 750°C after the total dehydration of the hexagonal hydrated structure while the dehydration of the monoclinic YPO₄·2H₂O phase began from about 190°C with its simultaneous decomposition into tetragonal YPO₄. A polytrioxophosphate secondary minor phase Re(PO₃)₃ resulting from adsorbed H₃PO₄ was formed at 950°C and decomposed at 1350°C. The particle morphology did not change with the temperature but grain coalescence occurred below 1000°C.     

Synthesis and characterization of one- to three-dimensional compounds composed of paradodecatungstate-B cluster and transition metals as linkers

Three new extended frameworks built from paratungstate and transition metals have been synthesized and characterized. In the compound Na₈[{Cd (H₂O)₂}(H₂W₁₂O₄₂)]·32H₂O (1), two neighboring paratungstate-B ions [H₂W₁₂O₄₂]¹⁰⁻ are linked by [Cd(H₂O)₂]²⁺ units, leading to the formation of infinite one-dimensional (1D) anion chain [{Cd(H₂O)₂}(H₂W₁₂O₄₂)]_n⁸ⁿ⁻. The anion [{Co(H₂O)₃}{Co(H₂O)₄}(H₂W₁₂O₄₂)]_n⁶ⁿ⁻ of the compound Na₆[{Co(H₂O)₃}{Co(H₂O)₄}(H₂W₁₂O₄₂)]·29H₂O (2) shows a layer-like (2D) structure in which paratungstate-B units are linked by CoO₆ octahedra, while the anion [{Co(H₂O)₃}₃(H₂W₁₂O₄₂)]_n⁴ⁿ⁻ of the compound (H₃O⁺)₃[{Na(H₂O)₄}{Co(H₂O)₄}₃(H₂W₁₂O₄₂)]·24.5H₂O (3) is a three-dimensional (3D) anionic polymer that consists of paratungstate-B units linked by CoO₆ octahedra. Compound 3 can reversibly adsorb and desorb water molecules leading to the color reversibly change from pink to violet. The preliminary magnetic measurement and electrochemical properties of compounds are performed. The crystal structure of unexpected product Na₄[NiW₆O₂₄H₆]·13H₂O (4) is described here for the rare report of crystal structure information on the Anderson-type polyoxotungstate which has nickel as a heteroatom.     

Selective self-assembly synthesis of MnV2O6·4H2O with controlled morphologies and study on its thermal decomposition

The MnV₂O₆·4H₂O with rod-like morphologies was synthesized by solid-state reaction at low heat using MnSO₄·H₂O and NH₄VO₃ as raw materials. XRD analysis showed that MnV₂O₆·4H₂O was a compound with monoclinic structure. Magnetic characterization indicated that MnV₂O₆·4H₂O and its calcined products behaved weak magnetic properties. The thermal process of MnV₂O₆·4H₂O experienced three steps, which involves the dehydration of the two waters of crystallization at first, and then dehydration of other two waters of crystallization, and at last melting of MnV₂O₆. In the DSC curve, the three endothermic peaks were corresponding to the two steps thermal decomposition of MnV₂O₆·4H₂O and melting of MnV₂O₆, respectively. Based on the Kissinger equation, the average values of the activation energies associated with the thermal decomposition of MnV₂O₆·4H₂O were determined to be 55.27 and 98.30?kJ?mol^?1 for the first and second dehydration steps, respectively. Besides, the thermodynamic function of transition state complexes (??H ^??, ??G ^?? , and ??S ^?? ) of the decomposition reaction of MnV₂O₆·4H₂O were determined.     

Studies on rare earth trisoxalatochromates (III), rare earth chromates (V) and rare earth chromites (III)

Rare earth trisoxalatochromates (III), LnCr(C₂O₄)₃·nH₂O (n = 9 for La, and n = 8 for Ce, Pr and Nd) have been isolated and characterized by a number of physicochemical studies. These compounds (except for Ce) serve as precursors for the rare earth chromates (V) and chromites (III). LnCrO₄ may be obtained by heating LnCr(C₂O₄)₃·nH₂O at 520°C for 4 hr and LnCrO₃ at 900°C for a similar period. CeCr(C₂O₄)₃. 8H₂O decomposes to a mixture of CeO₂ and Cr₂O₃. The EPR spectra of LaCrO₄ are consistent with a tetrahedral geometry of the CrO₄ group. Although the unit cell of LaCrO₄ is monoclinic and of NdCrO₄ is tetragonal, compounds of composition La_1−xNd_xCrO₄ show the presence of only monoclinic phase for x up to 0.23. The electronic spectra of LnCrO₃ are compatible with the perovskite structure of these compounds.     

Polarographic reduction of aldehydes and ketones: Part XXIII. Electroreduction of 1-methylpyridiniumcarboxaldehydes

All three isomeric 1-methylpyridiniumcarboxaldehydes are present in aqueous solutions predominantly in the hydrated form (PyCH(OH)₂). At pH smaller than about 7, the protonated form of the free aldehyde is reduced in two one-electron steps following the sequence H⁺, e, H⁺, e. At pH greater than about 8 the free aldehydic form is reduced in two one-electron steps following the sequence, e, H⁺, e, H⁺. Up to pH about 10 the reducible species is formed by dehydration of PyCH(OH)₂, at higher pH by elimination of hydroxide ion from PyCH(OH)O⁻.The increase in polarographic reduction current between pH about 8 and 10 is due to a base-catalyzed dehydration, involving a rate-determining formation of PyCH(OH)O⁻. The polarographic dissociation curve (i₁ vs. pH) is in this case shifted to lower pH-values when compared with the conditional dissociation curve ([PyCH(OH)₂] vs. pH). Such behavior shows that the effective reduction of the conjugate base of an electroinactive acid (PyCH(OH)₂) occurs.The increase in polarographic reduction current at pH smaller than about 1 is due to an acid-catalyzed dehydration involving formation of PyCH(OH)(OH₂⁺). The rate of protonation governs the limiting current, since the increase in current with increasing acidity occurs in a region one to two acidity units higher than pK₁ values obtained spectrophotometrically, using acidity functions H_C(OH)2. The free carbonyl species produced by dehydration is reduced following a sequence H⁺, e, H⁺, e.     

Flexible 3D porous metal-organic framework exhibiting selective adsorption for H2O over organic solvents

A new flexible 3D porous metal-organic framework (MOF) with 1D open nanotube,[Co2(μ5-CTAI)(dpe)(H2O)2]n·6n(H2O)(1) (CTA=cyclohexane-1,2,4,5-tetracarboxylic acid,dpe=1,2-di(4-pyridyl) ethylene) has been prepared and structurally characterized.Meanwhile,each 1D nanotubes filled with 1D water chain with dimension of 13.711 × 12.275 2.Compound 1 represents a new example that collapse/deform upon dehydration/hydration and shows adsorb H 2 O selectively over organic solvents.     

Thermal dehydration of CeP<Subscript>3</Subscript>O<Subscript>9</Subscript>·3H<Subscript>2</Subscript>O by controlled rate thermal analysis

The aim of this work is to highlight the importance of controlling the residual water vapour pressure above the sample as well as the rate of the thermal decomposition during the thermal dehydration of cerium cyclotriphosphate trihydrate CeP₃O₉·3H₂O. For this reason, the dehydration of the titled compound was followed by both techniques: the constant rate thermal analysis at P _H2O = 5 hPa and the conventional TG-DTA in air.     

Dependence of kinetics of copper sulfate pentahydrate dehydration on water vapor pressure

The dependence of the growth rate v_g of nuclei during CuSO₄·5H₂O dehydration upon water vapor pressure P_H2O has been investigated. At small P_H2O (less than 1 Torr at 50°C), v_g falls rapidly with decreasing P_H2O, and simultaneously v_g anisotropy disappears. At P_H2O = 1–9 Torr, v_g for elliptic and round nuclei is constant and independent of P_H2O. The influence of initially keeping the samples in water vapor upon the kinetics of the following dehydration has been studied. Treatment by water vapor leads to slowing of dehydration and increasing its degree of transformation. On the basis of data obtained a kinetic interpretation of the Topley-Smith effect has been proposed.     

Preparation of LiZnPO4·H2O via a novel modified method and its non-isothermal kinetics and thermodynamics of thermal decomposition

The single phase ??-LiZnPO₄·H₂O was directly synthesized via solid-state reaction at room temperature using LiH₂PO₄·H₂O, ZnSO₄·7H₂O, and Na₂CO₃ as raw materials. XRD analysis showed that ??-LiZnPO₄·H₂O was a compound with orthorhombic structure. The thermal process of ??-LiZnPO₄·H₂O experienced two steps, which involved the dehydration of one crystal water molecule at first, and then the crystallization of LiZnPO₄. The DTA curve had the one endothermic peak and one exothermic peak, respectively, corresponding to dehydration of ??-LiZnPO₄·H₂O and crystallization of LiZnPO₄. Based on the iterative iso-conversional procedure, the average values of the activation energies associated with the thermal dehydration of ??-LiZnPO₄·H₂O, was determined to be 86.59?kJ?mol^?1. Dehydration of the crystal water molecule of ??-LiZnPO₄·H₂O is single-step reaction mechanism. A method of multiple rate iso-temperature was used to define the most probable mechanism g(??) of the dehydration step. The dehydration step is contracting cylinder model (g(??)?=?1?(1???)^1/2) and is controlled by phase boundary reaction mechanism. The pre-exponential factor A was obtained on the basis of E _a and g(??). Besides, the thermodynamic parameters (??S ^??, ??H ^??, and ??G ^??) of the dehydration reaction of ??-LiZnPO₄·H₂O were determined.     

Kinetics of the thermal dehydration of potassium titanium oxalate, K2TiO(C2O4)2·2H2O

The thermal dehydration reaction of potassium titanium oxalate, K₂TiO(C₂O₄)₂·2H₂O, has been studied by means of thermogravimetry (TG), differential thermal analysis (DTA), and differential scanning calorimetry (DSC) in nitrogen atmosphere at different heating rates. K₂TiO(C₂O₄)₂·2H₂O dehydrates in a single step through a practically irreversible process. The activation energy involved and its dependence on the conversion degree were estimated by evaluating the thermogravimetric data according to model-free methods, and values of activation energy were determined for the dehydration reaction. Activation energy values were also evaluated from DSC data using isoconversional methods. The complexity of the dehydration of K₂TiO(C₂O₄)₂·2H₂O is illustrated by the dependence of E on the extent of conversion, ?? (0.05??????????0.95).     

Studies on the Thermal Decomposition of Rare Earth Caproates

The thermal decomposition of rare earth caproates with general formula Ln(C₅H₁₁COO)₃ nH₂O, (where Ln=Y, La-Pr, n=l; Ln=Nd-Er, n=2; Ln=Tm-Lu, n=3) were studied in an air atmosphere. On heating, the hydrated caproates are dehydrated in one step and then the anhydrous complexes decompose to the oxides (Ln₂O₃, Pr₆O₁₁) with formation of the intermediate Ln₂O₂CO₃ (La, Pr-Gd) or directly to the oxides Ln₂O₃, CeO₂, Tb₄O₇(Y, Ce, Tb-Lu). Caproates of rare earth elements are liquefied during dehydration.     

Cobalt, nickel, and copper coordination compounds with 3-phenylpropenal benzoylhydrazone

3-Phenylpropenal benzoylhydrazone (HL) reacts with cobalt, nickel, and copper chlorides, nitrates, and acetates to give coordination compounds MX₂ · nH₂O [M = Co, Ni, Cu; X = Cl, NO₃, HL = C₆H₅CH=CHCH=NNHC(O)C₆H₅; n = 0, 2] and ML₂ · nH₂O (M = Co, Ni, Cu; n = 1–3). Complexes MALCI (M = Co, Ni, Cu) were obtained by these reactions in the presence of amines (A = C₅H₅N, 2-CH₃C₅H₄N, 3-CH₃C₅H₄N, 4-CH₃C₅H₄N). All the compounds have a monomeric structure. Azomethine (HL) in them behaves as a bidentate N,O-ligand. Thermolysis of the complexes involves the stages of dehydration (70–90°C), deaquation (145–155°C) or deamination (145–185°C), and complete thermal decomposition (330–490°C).     

Synthesis,crystal structures and spectroscopic studies of praseodymium(III) malonate complexes

Reactions of malonic acid (H₂mal) with PrCl₃·6H₂O afforded the known complex [Pr₂(mal)₃(H₂O)₆]_n (1), and compounds [Pr₂(mal)₃(H₂O)₆]_n·2nH₂O (2·2nH₂O), [PrCl(mal)(H₂O)₃]_n·0.5nH₂O (3·0.5nH₂O) and [Pr(mal)(Hmal)(H₂O)₃]_n·nH₂O (4·nH₂O) using various reaction ratios, reaction media (H₂O, MeOH) and pH values. Analogous reactions with CeCl₃·7H₂O afforded compounds [Ce₂(mal)₃(H₂O)₆]_n (5), [CeCl(mal)(H₂O)₃]_n·nH₂O (6·nH₂O) and [Ce(mal)(Hmal)(H₂O)₃]_n·nH₂O (7·nH₂O). Compounds 2·2nH₂O and 3·0.5nH₂O were characterized by X-ray crystallography, and 4–7 by microanalytical and spectroscopic data. The malonate(-2) ligand adopts three different coordination modes in the structures of 1–3, i.e., the μ₂-κO:κO′:κO″ and the μ₄-κ²O:κO′:κ²O″:κO? in 1 and 2 leading to a 3D network structure, and the μ₃-κ²O:κO′:κ²O″:κO? in 3 promoting an 1D structure. The thermal decomposition of 1 and 3·0.5nH₂O was monitored by TG/DTA and TG/DTG measurements. The structural features of 1–3 are discussed in terms of known malonato(-2) Ln^III and Ca^II complexes. The bioinorganic chemistry relevance of our results is discussed.     

Etude analytique par thermogravimetrie et analyse thermique differentielle du peroxyde de sodium hydrate et du peroxyde de sodium commercial

Thermogravimetry and differential thermal analysis were used to study hydrated sodium peroxide and the so-called anhydrous commercial product. Prolonged dehydration of the octahydrate under vacuum led to the partial formation of Na₂O₂-H₂O₂ compounds as well as the dihydrate and monohydrate The DTA curves for commercial sodium peroxide heated in air or other gases, showed the partial formation of Na₂O₂·2H₂O₂·nH₂O and of NaHCO₄·H₂O by the action of the gases on the NaO₂ contained in the Na₂O₂.     

Computer-aided study of oxygen absorption by water clusters. IR spectra of heteroclusters

Spectral characteristics of (H₂O)_n, (O₂)_m(H₂O)_n, and (O)_i(H₂O)_n cluster systems, where m≤2, i≤4, and 10 ≤ n ≤ 50, are studied with the molecular dynamics method using a flexible molecule model. The IR absorption spectra are changed substantially as a result of O₂ molecule dissociation, and in the presence of atomic oxygen in the clusters, the spectra are characterized by a deep minimum at 520 cm^?1. The absorption of oxygen causes a marked reduction in reflection coefficient R of monochromatic IR radiation. The number of peaks in the R(ω) spectra decreases to two in the case of molecular oxygen absorption and is no larger than four in the case of atomic oxygen absorption. The absorption of atomic oxygen by the clusters is also accompanied by a significant increase in the dissipation of energy accumulated by the clusters. This effect weakens when molecular oxygen is absorbed. An increase in atomic oxygen concentration in the clusters renders their radiation harder.     

Nanocomposites with the layered structure of V2O5 · nH2O xerogel

New layered nanocomposites of V₂O₅ · nH₂O xerogels with poly(vinyl alcohol) (PVA), pyrocatechol (PC), and hydroquinone (HQ) were synthesized with the compositions (C₂H₃)_0.32V₂O_4.90 · nH₂O, (C₆H₄)_xV₂O_4.60 · nH₂O, and (C₆H₄)_0.17V₂O_4.94 · nH₂O and the interlayer distances d ₀₀₁ = 11.73, 12.85, and 15.28 ± 0.05 Å, respectively. IR and Raman spectroscopy was used to analyze which structural changes occur in the V-O layers of the xerogel upon composite formation. X-ray photoelectron spectroscopy showed V⁴⁺ and V⁵⁺ ions in the layers with binding energies lower than in V₂O₅ · nH₂O. The electrical conductivity of the nanofilms and the thermal properties of the nanopowders were studied.     

Study of the thermal dehydration of Mn1/2Ca1/2(H2PO4)2.2H2O

The dehydration and condensation reactions taking place during the calcination of Mn_1/2Ca_1/2(H₂PO₄)₂.2H₂O has been followed by means of thermal analyses under quasi-isothermal-isobaric conditions. Isothermal calcination of starting binary dihydrogenphosphate has been also carried out in an electric oven at various temperatures. The reaction products obtained were analyzed by chromatography, IR-spectroscopy, X-ray diffraction analysis, and electron microscopy. The compositions of the calcinates were determined through extraction. The effect of the partial pressure of water vapour has been followed on course, of the condensation reactions and of the formation of the main product: binary cyclotetraphosphate (tetrametaphosphate) MnCaP₄O₁₂.

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Zusammenfassung Dehydratations- und Kondensationsreaktion während der Kalzinierung von Mn_1/2Ca_1/2(H₂PO₄)₂.2H₂O wurden unter quasi-isothermen-isobaren Bedingungen mittels Thermoanalyse untersucht. Die isotherme Kalzinierung der binären Dihydrogenphosphat-Ausgangssubstanz wurde bei verschiedenen Temperaturen auch in einem Elektroofen durchgefährt. Erhaltene Reaktionsprodukte wurden mittels Chromatographie, IR-Spektroskopie, Röntgendiffraktionsanalyse und Elektronenmikroskopie untersucht. Die Zusammensetzung der Kalzinierungsprodukte wurde über Auslaugen bestimmt. Weiterhin wurde der Einfluß des partiellen Druckes von Wasser auf den Verlauf der Kondensationsreaktionen und die Bildung des Hauptproduktes {binäres Cyclotetraphosphat (Tetramethaphosphat) MnCaP₄O₁₂} untersucht.