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1.
The FT IR and FT Raman spectra of Co(en)3Al3P4O16 · 3H2O (compound I) and [NH4]3[Co(NH3)6]3[Al2(PO4)4]2 · 2H2O (compound II) are recorded and analysed based on the vibrations of Co(en)33+, Co(NH3)63+, NH4+, Al---O---P, PO3, PO2 and H2O. The observed splitting of bands indicate that the site symmetry and correlation field effects are appreciable in both the compounds. In compound I, the overtone of CH2 deformation Fermi resonates with its symmetric stretching vibration. The NH4 ion in compound II is not free to rotate in the crystalline lattice. Hydrogen bonding of different groups is also discussed.  相似文献   

2.
The thermal decomposition of tribochemically activated Al2(SO4)3·xH2O was studied by TG, DTA and EMF methods. For some of the intermediate solids, X-ray diffraction and IR-spectroscopy were applied to learn more about the reaction mechanism. Thermal and EMF studies confirmed that, even after mechanical activation of Al2(SO4)3·xH2O, Al2O(SO4)2 is formed as an intermediate. Isothermal kinetic experiments demonstrated that the thermochemical sulphurization of inactivated Al2(SO4)3·xH2O has an activation energy of 102.2 kJ·mol?1 in the temperature range 850–890 K. The activation energy for activated Al2(SO4)3·xH2O in the range 850–890 K is 55.0 kJ·mol?1. The time of thermal decomposition is almost halved when Al2(SO4)3·xH2O is activated mechanically. The results permit conclusions concerning the efficiency of the tribochemical activation of Al2(SO4)3·xH2O and the chemical and kinetic mechanisms of the desulphurization process.  相似文献   

3.
The thermal decomposition of [Co(NH3)6]2(C2O4)3·4H2O was studied under isothermal conditions in flowing air and argon. Dissociation of the above complex occurs in three stages. The kinetics of the particular stages thermal decomposition have been evaluated. The RN and/or AM models were selected as those best fitting the experimental TG curves. The activation energies,E, and lnA were calculated with a conventional procedure and by a new method suggested by Kogaet al. [10, 11]. Comparison of the results have showed that the Arrhenius parameters values estimated by the use of both methods are very close. The calculated activation energies were in air: 96 kJ mol–1 (R1.575, stage I); 101 kJ mol–1 (Ain1.725 stage II); 185 kJ mol–1 (A 2.9, stage III) and in argon: 66 kJ mol–1 (A 1.25, stage I); 87 kJ mol–1 (A 1.825, stage II); 133 kJ mol–1 (A 2.525, stage III).  相似文献   

4.
The structures of the oxyorthogermanate La2(GeO4)O and the apatite-structured La9.33(GeO4)6O2 have been refined from powder neutron diffraction data. La2(GeO4)O crystallizes in a monoclinic unit cell (P21/c) and is cation stoichiometric in contrast to previous reports. La9.33(GeO4)6O2 crystallizes in a hexagonal unit cell (P63/m) and the powder diffraction data show anisotropic peak broadening that is observed in electron diffraction patterns as incommensurate diffuse spots at hkq reciprocal planes (with q=1.6-1.7) and can be attributed to a correlated disorder in the “apatite channels”. This compound was doped up to a nominal composition close to M2La8(GeO4)6O2 with M=Ca, Sr, Ba. The dopant ions preferentially occupy the 4f sites as the number of La vacancies decreases. The measured ionic conductivity of La9.33(GeO4)6O2 is about 3 orders of magnitude larger than for La2(GeO4)O at high temperatures and decreases with increasing dopant content from the highest value of about 0.16 S cm−1 at 1160 K.  相似文献   

5.
On the refluxing ofM(II) oxalate (M=Mn, Co, Ni, Cu, Zn or Cd) and 2-ethanolamine in chloroform, the following complexes were obtained: MnC2O4·HOCH2CH2NH2·H2O, CoC2O4·2HOCH2CH2NH2, Ni2(C2O4)2·5HOCH2CH2NH2·3H2O, Cu2(C2O4)2·5HOCH2CH2NH2, Zn2(C2O4)2·5HOCH2CH2NH2·2H2O and Cd2(C2O4)2·HOCH2CH2NH2·2H2O. Following the reaction ofM(II) oxalate with 2-ethanolamine in the presence of ethanolammonium oxalate, a compound with the empirical formula ZnC2O4·HOCH2CH2NH2·2H2O1 was isolated. The complexes were identified by using elemental analysis, X-ray powder diffraction patterns, IR spectra, and thermogravimetric and differential thermal analysis. The IR spectra and X-ray powder diffraction patterns showed that the complexes obtained were not isostructural. Their thermal decompositions, in the temperature interval between 20 and about 900°C, also take place in different ways, mainly through the formation of different amine complexes. The DTA curves exhibit a number of thermal effects.  相似文献   

6.
The incorporation mechanism of Cs+ ions from CsNO3 into NH4Zr2(PO4)3 was studied on a mixture of CsNO3 and NH4Zr2(PO4)3 by powder X-ray diffraction analysis and by monitoring off-gases released from the mixture upon heating with a thermogravimetry analyzer connected to an infrared spectrometer. With increasing temperature, the decomposition of CsNO3 first started, followed by the conversion of NH4Zr2(PO4)3 to HZr2(PO4)3 with the release of NH3. At around 500°C, the Cs Zr2(PO4)3 phase started to appear as a result of the H+/Cs+ ion exchange. No Cs+ ion loss was observed at thermal treatment temperatures of 900°C and lower.  相似文献   

7.
Using the thermal decomposition of [Co(NH3)6]2(C2O4)3·4H2O as a basis, the paper presents results which show how computed values of kinetic parameters are influenced by experimental conditions (ambient atmosphere, sample mass, linear heating rate) when using the non-isothermal methods and the Coats-Redfern (CR) modified equation. It also illustrates the influence of the experimental methods i.e. non-isothermal and isothermal (conventional) methods and also a quasiisothermal-isobaric one which can be recognised as equivalent to Constant Rate Thermal Analysis (CRTA). The results obtained have confirmed the significant influence of the experimental parameters as well as that of the experimental method used on the estimated values of kinetic parameters. The correlation between activation energy (E) and sample mass (m) or heating rate (β) is generally of a linear nature:E=a+bx  相似文献   

8.
A new magnesium borate Mg2[B2O4(OH)2]·H2O has been synthesized by the method of phase transformation of double salt at hydrothermal condition and characterized by XRD, IR, TG and DSC. The enthalpy of solution of Mg2[B2O4(OH)2]·H2O in 0.9764 mol L–1 HCl was determined. With the incorporation of the enthalpies of solution of H3BO3 in HCl (aq), of MgO in (HCl+H3BO3) (aq), and the standard molar enthalpies of formation of MgO(s), H3BO3(s), and H2O(l), the standard molar enthalpy of formation of –(3185.78±1.91) kJ mol–1 of Mg2[B2O4(OH)2]·H2O was obtained.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

9.
The [Pt2(H2P2O5)4]4− ions in the ground and excited states and the excited-state complexes M-[Pt2(H2P2O5)4]3− and M2-[Pt2(H2P2O5)4]2− (M = Ag, Tl) were studied in solution with various density functional theory (DFT) functionals from Gaussian 09 and Amsterdam Density Functional (ADF) programs. Calculated results were compared with ultrafast X-ray solution scattering data. Time dependent DFT (TD-DFT) calculations with the B3PW91 functional and unrestricted open shell calculations with the mPBE functional produce good agreement with the experimental results. Compared to gas phase calculations, the surrounding solvent is found to play an important role to shorten the Pt-Pt and M-Pt (M = Ag, Tl) bond lengths, lowering the molecular orbital energies and influences the molecular orbital transitions upon excitation, which stabilizes the excited transient molecules in solution.  相似文献   

10.
The compound, (NH4)[VO(O2)2(NH3)], thermally decomposes to ammonium metavanadate, which then decomposes to vanadium pentoxide. Using a heating rate of 5 deg·min–1, the first decomposition step occurs between 74° and 102°C. The transformation degree dependence of the activation energy (-E) is shown to follow a decreasing convex form, indicating that the first decomposition step is a complex reaction with a change in the limiting stage of the reaction. Infrared spectra indicated that the decomposition proceeds via the gradual reduction of the ratio of the (NH4)2O to V2O5 units from the original 11 ratio in ammonium metavanadate, which may be written as (NH4)2O·V2O5, to V2O5.The assistance of Professor A. M. Heyns (University of Pretoria) and Professor K. L. Range (University of Regensburg) is gratefully acknowledged as well as the financial assistance of the University of Pretoria and the FRD.  相似文献   

11.
Fe2O(SO4)2 is a secondary product of the decomposition of FeSO4⋅H2O. Part I of this study presents results on the synthesis of Fe2O(SO4)2 in gaseous environment containing either low or high concentration of oxygen. In this paper the existence of differences between the structures of Fe2O(SO4)2 and Fe2(SO4)3 is proved on the basis of a detailed thermal study of Fe2O(SO4)2 upon dynamic heating (differential thermal analysis) and upon isothermal heating (thermal-analytic balance) in various gaseous environments as well as by presenting kinetic data on the processes of decomposition of both compounds. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

12.
The objectives of this study were to address uncertainties in the solubility product of (UO2)3(PO4)2⋅4H2O(c) and in the phosphate complexes of U(VI), and more importantly to develop needed thermodynamic data for the Pu(VI)-phosphate system in order to ascertain the extent to which U(VI) and Pu(VI) behave in an analogous fashion. Thus studies were conducted on (UO2)3(PO4)2⋅4H2O(c) and (PuO2)3(PO4)2⋅4H2O(am) solubilities for long-equilibration periods (up to 870 days) in a wide range of pH values (2.5 to 10.5) at fixed phosphate concentrations of 0.001 and 0.01 M, and in a range of phosphate concentrations (0.0001–1.0 M) at fixed pH values of about 3.5. A combination of techniques (XRD, DTA/TG, XAS, and thermodynamic analyses) was used to characterize the reaction products. The U(VI)-phosphate data for the most part agree closely with thermodynamic data presented in Guillaumont et al.,(1) although we cannot verify the existence of several U(VI) hydrolyses and phosphate species and we find the reported value for formation constant of UO2PO4 is in error by more than two orders of magnitude. A comprehensive thermodynamic model for (PuO2)3(PO4)2⋅4H2O(am) solubility in the H+-Na+-OH-Cl-H2PO4-HPO2−4-PO3−4-H2O system, previously unavailable, is presented and the data shows that the U(VI)-phosphate system is an excellent analog for the Pu(VI)-phosphate system.  相似文献   

13.
The two new compounds, Sr4Cu3(AsO4)2(AsO3OH)4·3H2O (1) and Ba2Cu4(AsO4)2(AsO3OH)3(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As2O5-H2O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å3, Z=4 for 1; space group P42/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å3, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu2+-(XO4)3− layers (X=P5+, As5+) linked by M cations (M=alkali, alkaline earth, Pb2+, or Ag+) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu2O8 centrosymmetric dimers crosslinked by As1φ4 tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu2O8 centrosymmetric dimers of CuO5 edge-sharing polyhedra, crosslinked by As1O4 tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.  相似文献   

14.
Gases released during the conversion of NH4Zr2(PO4)3 to HZr2(PO4)3 were identified using an apparatus in which gases released from a sample placed in a thermogravimetric analyzer were directly introduced to a gas cell of an IR spectrometer. Such acidic gases as N2O and NO were detected besides the basic NH3 gas, and their formation mechanism was discussed.This revised version was published online in November 2005 with corrections to the Cover Date.  相似文献   

15.
Two solid-state coordination compounds of rare earth metals with glycin, [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O melted at 342.90 K, while [ErY(Gly)6(H2O)4](ClO4)6·5H2O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol−1 and 53.9 J K−1 mol−1 for [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O, 1.82 kJ mol−1 and 5.5 J K−1 mol−1 for [ErY(Gly)6(H2O)4](ClO4)6·5H2O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed.  相似文献   

16.
Summary Single crystal X-ray data of the hydrothermally grown new phase Li2Cu3(SeO3)2(SeO4)2 were measured with a four-circle diffractometer up to sin /=0.81 Å–1 [I2/a,Z=4,V=1175.5 Å3,a=16.293(6),b=5.007(2),c=14.448(6) Å, = 94.21(1)°]. The structure was determined by direct and Fourier methods and refined toR=0.034,R w =0.027 for 2 086 independent reflections.Cu(1)[4+1]O5 forms a tetragonal pyramid, Cu(2)[4 + 2]O6 is a strongly elongated octahedron. The Li atom is surrounded by four O atoms forming a distorted tetrahedron. Se(IV)O3 and Se(VI)O4 groups are in accordance to literature, mean Se-O bond lengths are 1.714 and 1.644 Å.
Die Kristallstruktur von Li2Cu3(SeO3)2(SeO4)2
Zusammenfassung Einkristall-Röntgendaten der hydrothermal gezüchteten neuen Phase Li2Cu3(SeO3)2(SeO4)2 wurden mit einem Vierkreisdiffraktometer im Bereich bis zu sin /=0.81 Å–1 gemessen [I2/a,Z=4,V=1175.5 Å3,a=16.293(6),b=5.007(2),c=14.448(6) Å, =94.21(1)°]. Die Kristallstruktur wurde mittels direkter und Fourier-Methoden bestimmt und für 2 086 unabhängige Reflexe zuR=0.034,R w =0.027 verfeinert.Cu(1)[4+1]O5 bildet eine tetragonale Pyramide, Cu(2)[4+2]O6 ist ein stark verlängertes Oktaeder. Das Li-Atom ist von vier O-Atomen in Gestalt eines verzerrten Tetraeders umgeben. Die Se(IV)O3-und Se(VI)O4-Gruppen entsprechen der Literatur, die mittleren Se-O-Abstände betragen 1.714 und 1.644 Å.
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17.
Summary The atomic arrangements within the structures of NH4Ag2(AsS2)3 [a=9.557(2),b=7.414(2),c=16.29(1) Å; =91.30(5)°; space group P21/n;R(F)=0.042] and (NH4)5Ag16(AsS4)7 [a=64.49(6),b=6.471(2),c=12.806(4) Å; =95.47(5)°; space group Cc;R(F)=0.073] were determined from single crystal X-ray data. In these two compounds the coordination spheres of the Ag atoms are quite different. In NH4Ag2(AsS2)3, the Ag atoms exhibit a [2+2]- and a [3+1]-coordination to S atoms up to 3.3 Å and with Ag atom neighbours at 2.93 Å and 3.05 Å respectively. In (NH4)5Ag16(AsS4)7, the Ag atoms are — with one exception- [4] coordinated (Ag-S<3.3 Å) and the distances to further Ag atom neighbours are greater than 3.1 Å. NH4Ag2(AsS2)3 represents an ordered cyclo-thioarsenate(III) with three-membered As3S6 rings, (NH4)5Ag16(AsS4)7 a neso-thioarsenate(V) with two split Ag atom positions. Both compounds were synthesized under moderate hydrothermal conditions.
Synthesen und Kristallstrukturen von NH4Ag2(AsS2)3 und (NH4)5Ag16(AsS4)7 mit einer Diskussion über (NH4)Sx Polyeder
Zusammenfassung Die Atomanordnungen in den Strukturen von NH4Ag2(AsS2)3 [a=9.557(2),b=7.414(2),c=16.29(1) Å; =91.30(5)°; Raumgruppe P21/n;R(F)=0.042] und (NH4)5Ag16(AsS4)7 [a=64.49(6),b=6.471(2),c=12.806(4) Å; =95.47(5)°; Raumgruppe Cc;R(F)=0.073] wurden anhand von röntgenographischen Einkristalldaten bestimmt. In diesen beiden Verbindungen sind die Koordinationsverhältnisse um die Ag-Atome sehr unterschiedlich. In NH4Ag2(AsS2)3 besitzen die Ag-Atome bis 3.3 Å eine [2+2]- und [3+1]-Koordination durch S-Atome mit weiteren Ag-Atomen bei 2.93 Å und 3.05 Å. In (NH4)5Ag16(AsS4)7 sind die Ag-Atome mit einer Ausnahme [4]-koordiniert (Ag-S < 3.3 Å), und die Abstände zu weiteren Ag-Atomen sind größer als 3.1 Å. NH4Ag2(AsS2)3 stellt ein geordnetes Cyclothioarsenat(III) mit dreigliedrigen As3S6-Ringen dar, (NH4)5Ag16(AsS4)7 ein Nesothioarsenat (V) mit zwei aufgespaltenen Ag-Positionen. Beide Verbindungen wurden unter mäßigen Hydrothermalbedingungen synthetisiert.
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18.
The dehydration of Ca(H2PO4)2·H2O was examined with simultaneous DTA and TG. This dehydration permitted clearly the apparation of the following phases: Ca(H2PO4)2·0.5H2O, Ca(H2PO4)2, Ca3(HP2O7)2, Ca2HP3O10 et Ca(PO3)2. The reaction of Ca(H2PO4)2·H2O and CaSO4 was also examined with the same technics. It was found that the decomposition of CaSO4 takes place for relatively low temperature (between 600°C and 800°C).  相似文献   

19.
Basic tellurium nitrate crystallizes in the space group Pnma witha=14.607 (1),b=8.801 (1), andc=4.4633 (4) Å. Full-matrix least-squares refinement of automatic diffractometer data converged to a residualR=0.036 (R w =0.046) for 899 independent reflections. A detailed analysis of the structural data leads us to reformulate this compound as (Te2O4H)+(NO3) with a basic structural element consisting of a charged two-dimensional puckered Te2O4H+ network with discrete NO3 anions, an example of apositively-charged network structure.
Verfeinerung der Kristallstruktur von basischem Telluriumnitrat. Eine Umformulierung in (Te2O4H)+(NO3)
Zusammenfassung Basisches Telluriumnitrat kristallisiert in der Raumgruppe Pnma mita=14,607 (1),b=8,801 (1) undc=4,4633 (4) Å. Die verfeinernde Auswertung der Diffraktometerdaten konvergierte zuR=0,036 (R w =0.046) für 899 unabhängige Reflexe. Eine detaillierte Analyse der Strukturdaten führte zu einer Umformulierung dieser Verbindung als (Te2O4H)+(NO3), wobei die Basisstruktur aus einem geladenen, zweidimensionalen, gefalteten Te2O4H+ Netzwerk mit getrennten NO3 Anionen besteht. Es stellt dies ein Beispiel einerpositiv geladenen Netzstruktur dar.
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20.
Fluorine-19 and natural abundance 17O and 183W NMR spectroscopy were employed for the characterization of aqueous solutions of (NH4)2WO2F4 and (NH4)3WO3F3. Dissolution of the (NH4)2WO2F4 complex is accompanied by its partial acid hydrolysis to give the trans(mer)-dimer, [W2O5F6]4−, and unreacted cis-[WO2F4]2−. The cis(fac)-[W2O5F6]4− anion is the major soluble product resulting from the alkaline hydrolysis of (NH4)2WO2F4 along with the isolation of the solid (NH4)2WO3F2. In addition, the edge-bridging dimer, [W2O6F4]4−, and the cyclic trimer, [W3O9F6]6−, are also suggested as hydrolysis products. Decomposition of (NH4)3WO3F3 occurs in aqueous solution to give NH4WO3F.  相似文献   

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