On precipitation effects of aluminum,lanthanum, iron (III), and thorium phosphates

Summary Typical precipitation curves of various metal phosphates have been obtained using the turbidimetric technique. The following systems have been investigated: Al(NO₃)₃-K₃PO₄, Al(NO₃)₃-KH₂PO₄, Al(NO₃)₃NaH₂PO₄, FeCl₃-K₃PO₄, FeCl₃-(NH₄)₂HPO₄, FeCl₃K₂HPO₄, FeCl₃-KH₂PO₄, FeCl₃-NaH₂PO₄, La(NO₃)₃K₃PO₄,La(NO₃)₃-K₂HPO₄,La(NO₃)₃-KH₂PO₄,La(NO₃)₃NaH₂PO₄ and Th(NO₃)₄-K₂HPO₄. Typical precipitation curves indicated concentration ranges of phosphate precipitation and of complex solubility.

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Zusammenfassung Typische F?llungskurven verschiedener Metallphosphate, die mittels Trübungsmessungen erhalten wurden, wurden graphisch dargestellt. Die folgenden Systeme wurden untersucht: Al(NO₃)₃-K₃PO₄,Al(NO₃)₃KH₂PO₄, Al(NO₃)₃-NaH₂PO₄, FeCl₃-K₃PO₄, FeCl₃(NH₄)₂HPO₄, FeCl₃-K₂HPO₄, FeCl₃-KH₂PO₄, FeCl₃NaH₂PO₄, La(NO₃)₃-K₃PO₄, La(NO₃)₃-K₂HPO₄, La(NO₃)₃-KH₂PO₄, La(NO₃)₃-NaH₂PO₄ und Th(NO₃)₄K₂HPO₄. Typische F?llungskurven zeigten Konzentrationsgebiete, in welchen die Metallphosphate gef?llt werden, sowie Konzentrationen, die zur Komplexbildung führten.

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Supported in part by the U.S. Army Research Office, Contract No. DA-ORD-10.     

Beiträge zum thermischen Verhalten und zur Kristallchemie von wasserfreien Phosphaten XXXII [1] Neue Orthophosphate des zweiwertigen Chroms — Mg3Cr3(PO4)4, Mg3, 75Cr2, 25(PO4)4, Ca3Cr3(PO4)4 und Ca2, 00Cr4, 00(PO4)4

Contributions on Crystal Chemistry and Thermal Behaviour of Anhydrous Phosphates. XXXII. New Orthophosphates of Divalent Chromium — Mg₃Cr₃(PO₄)₄, Mg_{3, 75}Cr_{2, 25}(PO₄)₄, Ca₃Cr₃(PO₄)₄ and Ca_{2, 00}Cr_{4, 00}(PO₄)₄ Solid state reactions via the gas phase led in the systems A₃(PO₄)₂ / Cr₃(PO₄)₂ (A = Mg, Ca) to the four new compounds Mg₃Cr₃(PO₄)₄ ( A ), Mg_3.75Cr_2.25(PO₄)₄ ( B ), Ca₃Cr₃(PO₄)₄ ( C ), and Ca_2.00Cr_4.00(PO₄)₄ ( D ). These were characterized by single crystal structure investigations [( A ): P2₁/n, Z = 1, a = 4.863(2) Å, b = 9.507(4) Å, c = 6.439(2) Å, β = 91.13(6)°, 1855 independend reflections, 63 parameters, R1 = 0.035, wR2 = 0.083; ( B ): P2₁/a, Z = 2, a = 6.427(2) Å, b = 9.363(2) Å, c = 10.051(3) Å, β = 106.16(3)°, 1687 indep. refl., 121 param., R1 = 0.032, wR2 = 0.085; ( C ): P‐1, Z = 2, a = 8.961(1) Å, b = 8.994(1) Å, c = 9.881(1) Å, α = 104.96(2)°, β = 106.03(2)°, γ = 110.19(2)°, 2908 indep. refl., 235 param., R1 = 0.036, wR2 = 0.111; ( D ): C2/c, Z = 4, a = 17.511(2) Å, b = 4.9933(6) Å, c = 16.825(2) Å, β = 117.95(1)°, 1506 indep. refl., 121 param., R1 = 0.034, wR2 = 0.098]. The crystal structures contain divalent chromium on various crystallographic sites, each showing a (4+n)‐coordination (n = 1, 2, 3). For the magnesium compounds and Ca_2.00Cr_4.00(PO₄)₄ a disorder of the divalent cations Mg²⁺/Cr²⁺ or Ca²⁺/Cr²⁺ is observed. Mg_3.75Cr_2.25(PO₄)₄ adopts a new structure type, while Mg₃Cr₃(PO₄)₄ is isotypic to Mg₃(PO₄)₂. Ca₃Cr₃(PO₄)₄ and Ca_2.00Cr_4.00(PO₄) ₄ are structurally very closely related and belong to the Ca₃Cu₃(PO₄)₄‐structure family. The orthophosphate Ca₉Cr(PO₄)₇, containing trivalent chromium, has been obtained besides C and D .     

Heat Conductivity of Zirconium and Alkali Metal (Na,Cs) Phosphates of the NaZr2(PO4)3 Family

The heat conductivity of porous Zr₃(PO₄)₄, NaZr₂(PO₄)₃, CsZr₂(PO₄)₃, and Na₅Zr(PO₄)₃ samples was studied in the range 298-673 K. The heat conductivity coefficients of the zero-porosity phosphates under study were calculated and prospects for their application were considered.     

The Oxidation of Heterogeneous Tl/Ni/P‐Alloys — Preparation and Crystal Structures of the Thallium Nickel Phosphates TlNi4(PO4)3, Tl4Ni7(PO4)6, and Tl2Ni4(P2O7)(PO4)2

Single crystals of the first anhydrous thallium nickel phosphates were prepared by reaction of heterogeneous Tl/Ni/P alloys with oxygen. TlNi₄(PO₄)₃ (pale‐yellow, orthorhombic, space group Cmc2₁, a = 6.441(2)Å, b = 16.410(4)Å, c = 9.624(2)Å, Z = 4) crystallizes with a structure closely related to that of NaNi₄(PO₄)₃. Tl₄Ni₇(PO₄)₆ (yellow‐brown, monoclinic, space group Cm, a = 10.711(1)Å, b = 14.275(2)Å, c = 6.688(2)Å, β = 103.50(2)°, Z = 8) is isotypic with Na₄Ni₇(PO₄)₆, and Tl₂Ni₄(P₂O₇)(PO₄)₂ (brown, monoclinic, space group C2/c, a = 10.389(2)Å, b = 13.888(16)Å, c = 18.198(3)Å, β = 103.1(2)°, Z = 8) adopts the K₂Ni₄(P₂O₇)(PO₄)₂ structure. Tl₂Ni₄(P₂O₇)(PO₄)₂ could also be prepared in nearly single phase form by reaction of Tl₂CO₃, NiO, and (NH₄)₂HPO₄.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Quantum chemical and spectroscopic analysis of calcium hydroxyapatite and related materials

Amorphous calcium hydroxyapatite was examined by vibrational spectroscopy (Raman and infra-red (IR)) and quantum chemical simulation techniques. The structures and vibrational (IR, Raman and inelastic neutron scattering) spectra of PO₄³⁻ ion, Ca₃(PO₄)₂, [Ca₃(PO₄)₂]₃, Ca₅(PO₄)₃OH, CaHPO₄, [CaHPO₄]₂, Ca₃(PO₄)₂·H₂O, Ca₃(PO₄)₂·2H₂O and Ca₃(PO₄)₂·3H₂O clusters were quantum chemically simulated at ab initio and semiempirical levels of approximation. A complete coordinate analysis of the vibrational spectra was performed. The comparison of the theoretically simulated spectra with the experimental ones allows to identify correctly the phase composition of the amorphous calcium hydroxyapatite and related materials. The shape of the bands in the IR spectra of the hydroxoapatite can be used in order to characterize the structural properties of the material, e.g., the PO₄³⁻ ion status, the degree of hydrolysis of the material and the presence of hydrolysis products.     

Thermochemical study of gaseous salts of oxygen-containing acids: XXI. Polymers of lithium,potassium, and cesium phosphates

Gas-phase reactions involving monomers and polymers of lithium, potassium, and cesium phosphates were studied. Standard enthalpies of formation and atomization of (MPO₃)₂, (MPO₃)₃, KCs(PO₃)₂, LiK(PO₃)₂, and (LiPO₃)₄ were determined.     

A Partial System LaPO4-Ca2P2O7-Ca(PO3)2-La(PO3)3

The system LaPO₄-Ca₂P₂O₇-Ca(PO₃)₂-La(PO₃)₃ was investigated by means of thermal and X-ray analyses. Three binary systems were found to occur in this region: LaPO₄-Ca(PO₃)₂,LaPO₄-Ca₄P₆O₁₉ and LaPO₄-CaLa(PO₃)₅. Their phase diagrams, and also that for the system LaPO₄-Ca₂P₂O₇- Ca(PO₃)₂-La(PO₃)₃, were obtained. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structure of orthophosphoric Acid-N,N-dimethylformamide complexes

Ab initio calculations weere used to obtain the characteristics of the most stable configurations of the (H₃PO₄)₂, DMFA-H₃PO₄, and DMFA-(H₃PO₄)₂ complexes in a vacuum. The changes in the geometric parameters in this series of complexes were analyzed and the energies of intermolecular interactions were estimated. The DMFA-(H₃PO₄)₂ complex was found to be most stable. It was established that the hydrogen bond between the DMFA and H₃PO₄ molecules is formed with the participation of both lone pairs of the oxygen atom of the DMFA molecule.     

Thermal stability and X-ray luminescent properties of cesium fluorophosphatozirconates

Crystalline cesium fluorophosphatozirconates (CFPZs) CsZr₂F₆PO₄ · 4H₂O, CsZrF₂PO₄ · 0.5H₂O, CsH₂Zr₂F₂(PO₄)₃ · 2H₂O, and amorphous Cs₂Zr₃OF₆(PO₄)₂ · 3H₂O were synthesized, and their thermal stability and luminescence ability were studied. The compositions of initial CsH₂Zr₂F₂(PO₄)₃ · 2H₂O and Cs₂Zr₃OF₆(PO₄)₂ · 3H₂O were refined. CsZr₂O_0.5F₅PO₄, CsHZr₂F(PO₄)₃, CsZr₂(PO₄)₃, and Cs₂Zr₃OF₆(PO₄)₂ crystalline intermediates, which are comparable with BaSO₄ and CaF₂ luminophors in the context of their X-ray luminescence intensity, were recognized by thermal analysis and X-ray powder diffraction under heating.     

Etude des equilibres solide-liquide des systems MIPO3Sm(PO3)3 (MI = Li,Na, Ag)

The M^IPO₃Sm(PO₃)₃(M^I = Li, Na, Ag) systems were studied. Differential thermal analysis and X-ray diffraction were used to investigate the liquidus and solidus relations. Three compounds LiSm(PO₃)₄, NaSm(PO₃)₄, and AgSm(PO₃)₄ were obtained which melt incongruently at 1248, 1143, and 1078 K, respectively. These compounds are isomorphous with their homologs LiLn(PO₃)₄, NaLn(PO₃)₄, AgLn(PO₃)₄ (Ln = Ce, La, Nd). They belong to the monoclinic system. The LiSm(PO₃)₄ unit cell parameters refined by least squares method are a = 16.43(3) Å, b = 7.16(1) Å, c = 9.65(3) Å, β = 125,9°(1), with the space group $\text{C2}\text{c}$ and Z = 4. NaSm(PO₃)₄ and AgSm(PO₃)₄ are isotypic; they cristallize in the $\text{P2}{}_1\text{c}$ space group, Z = 4; their unit cell parameters are, respectively, a = 12.18(1) Å, b = 13.05(1) Å, c = 7.25(5) Å, β = 126,53°(4), $\text{a = 12.25(1)}\text{A}\text{?}$, b = 13.06(1) Å, c = 7.201(9) Å, β = 126,57°(7). The ir spectra of the last two compounds indicate that these phosphates are chain phosphates.     

Meet the Cerium(IV) Phosphate Sisters: CeIV(OH)PO4 and CeIV2O(PO4)2

Two new cerium(IV) phosphates were obtained: cerium(IV) hydroxidophosphate, Ce(OH)PO₄, and cerium(IV) oxidophosphate, Ce₂O(PO₄)₂, which were shown to complement the classes of isostructural compounds M(OH)PO₄ and R₂O(PO₄)₂, where M=Th, U and R=Th, U, Np, Zr. Ce₂O(PO₄)₂ oxidophosphate is formed by elimination of H₂O from the crystal structure of Ce(OH)PO₄ during its thermal decomposition. The structures of Ce(OH)PO₄ and Ce₂O(PO₄)₂ are related to each other with the same Cmce space group and similar unit cell parameters (a=6.9691(3) Å, b=9.0655(4) Å, c=12.2214(4) Å, V=772.13(8) ų, Z=8; a=7.0220(4) Å, b=8.9894(5) Å, c=12.544(1) Å, V=791.8(1) ų, Z=4, respectively).     

IR study of the structure of rhombohedral zirconium and alkali metal orthophosphates

Zirconium orthophosphates with different alkali cations MZr₂(PO_{4 3}, M₂Zr(PO₄)₂, and M₅Zr(PO₄4)₃, where M is Na, K, Rb, Cs, were synthesized and studied by IR spectroscopy. X-ray diffraction, and ⁴⁰K radiometric analysis. It is confirmed that MZr₂(PO_{4 3} (M = Na, K, Rb, Cs) exist as rhombohedral phases crystallizing as NaZr₂(PO_{4 3}) (NZP) structures. For Na₅Zr(PO_{4 3} it is shown that an NZP phase with a monoclinic superstructure is formed as a result of statistical distribution of Na and Zr in the ZrO₆ octahedm and ordered distribution of sodium atoms in the interstices of the channels. Formation of K₂Zr(PO₄)₂ and K₅Zr(PO₄)₃ phases with NZP structures is shown to be possible. Translated from Zhumal Struktumoi Khimii, Vol. 41, No. 1, pp. 74-79, January-February, 2000.     

Etude du diagramme d’equilibre du systeme NaPO3−Pr(PO3)3

The NaPO₃?Pr(PO₃)₃ system was studied by microdifferential thermal analysis (DTA), IR and X-ray diffraction spectroscopies. The only new compound observed in the system is NaPr(PO₃)₄, which melts incongruently at 1149 K. A eutectic appears at 5% Pr(PO₃)₃ at 901 K. The new compound NaPr(PO₃)₄ was characterized by means of powder X-ray diffraction and IR absorption spectroscopy. NaPr(PO₃)₄ is a NaLa(PO₃)₄ isotype; it crystallizes in the monoclinic system P2₁/c witha=12.328(7),b=13.130(5),c=7.231(5) Å, β=126°, 18(5),Z=4,V=945 ?³.     

Ammoxidation of toluene on vanadyl polyphosphates-VO(PO3)2, 1. synthesis and characterization of the parent samples

Vanadyl polyphosphates with a P/V ratio=2 (crystalline α-VO(PO₃)₂ and β-VO(PO₃)₂ as well as amorphous VO(PO₃)₂) were synthesized, starting from usually prepared precursor VO(H₂PO₄)₂ but pursuing new methods using V₂O₅/H₃PO₄ as well as VOHPO₄·1/2 H₂O/H₃PO₄, too. The products were characterized by chemical analysis and X-ray diffractometry.In situ ESR spectroscopy was used as a tool to predict their catalytic activity in the ammoxidation reaction.     

Structure Cristalline du Trimétaphosphate d'Indium(III)

Crystal Structure of In (PO₃)₃ Indium(III) trimetaphosphate In(PO₃)₃ crystallizes in the monoclinic space group Ic with a = 10.876(2) Å, b = 19.581(2) Å, c = 9.658(2) Å, β = 97.77(1)° and Z = 12. The structure was refined to R = 0.027 utilizing 1171 independent reflections. The structure consists of infinite chains of [PO₄] tetrahedra sharing corners with each other. InO₆ octahedra connect parallel chains. Each oxygen atom is shared between two [PO₄] tetrahedra (in the infinite chains (PO₃)_n) or one [PO₄] tetrahedron and one [InO₆] octahedron. For the first type of oxygen atoms (O_M) the P? O distances are about 0.1 Å greater than the P? O distances of the second type of oxygen atoms (O_m). The [InO₆] groups are moderately distorted and the average In? O bond length for the three In³⁺ ions is 2.117 Å.     

Synthesis and catalytic activity of sodium-magnesium orthophosphates of different stoichiometry

This paper reports on the synthesis and characterization of various mixed orthophosphates [NaMgPO₄, Na₄Mg(PO₄)₂ and NaMg₄(PO₄)₃] obtained from freshly prepared Mg₃(PO₄)₂ gel by using various treatments. The solids exhibit excellent selectivity in the gas-phase conversion of cyclohexanol (CHOL) to cyclohexanone (CHONE).     

Studies on thermal stability of mixed metaphosphates KLa(PO3)4 and K2La(PO3)5

Within an investigation of the phase equilibria in the binary system La(PO₃)₂-KPO₃, the thermal behaviour of the mixed metaphosphates KLa(PO₃)₄ and K₂La(PO₃)₅ has been examined.

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Zusammenfassung Innerhalb einer Studie über Phasengleichgewichte im binären System La(PO₃)₃-KPO₃ wurde das Verhalten der Mischsalze KLa(PO₃)₄ und K₂La(PO₃)₅ in Hinsicht auf eine thermische Behandlung untersucht.

     

The system Y2O3−CaO−P2O5

The ternary system Y₂O₃?CaO?P₂O₅ has been examined by DTA, X-ray diffraction, IR and microscopic methods. Its phase diagram has been provided within the composition range YPO₄?Ca₃(PO₄)₂?P₂O₅. The occurrence of four mixed phosphates: Ca₃Y(PO₄)₃, CaYP₃O₁₀, CaY(PO₃)₅, Ca₂Y(PO₃)₇ has been discovered in the system. Basic X-ray data have been determined for these newly discovered compounds and several methods of their synthesis developed.     

Les systemes binaires AlPO4−M3PO4 (M=Li,Na, K)

The liquid-solid phase diagram of the binary systems AlPO₄?M₃PO₄(M=Li, Na, K) have been established. The additional compounds Na₃Al(PO₄)₂, Na₃Al₂(PO₄)₃ and K₃Al₂(PO₄)₃ have been found again. A new compound K₃Al(PO₄)₂ is observed. The melting point of Na₃PO₄ is 1545°C and K₃PO₄ does not melt up to 1700°C.