A Study of Ammonium Mono-, Di- and Triphosphate Heterogeneous Systems in View of Their Use as Liquid Fertilizers

Abstract

Ammonium phoaphates belong among principal compounds of rnulticomponent liquid fertilizers and thus this study has been directed toward agrochernical application. The system NH₄H₂PO₄-(NH₄) ₂H₂PO₄- (NH₄)₂H₂P₂O_7- (NH₄)₃ H₂P₃O₁₀- (NH₄) ₃PO₄-(NH₄)₄) ₄P₂O₇-(NH₄)₅P₃O₁₀-H₂O was studied in which the pH of saturated solutions varies from 5 to 8. The solubility was studied in the partial pseudoternary systems. The experimental temperatures were selected immediately above the corresponding cryohydratic points, from 0 to -8 °C, The results were discussed using a computer. The procedure used makes it possible to find a smoothing equation for each branch of the solubility diagram at issue. Simultaneously, a set of coefficienta Q related to the ideality of the respective solutions was found, From practical point of view, it can be seen from the results obtained that the highest concentrations of agrochemically effective components(nitrogen and phosphorus pentaoxide) are attained in saturated solutions containing triphosphate with a nutritional value of more than 50%.     

IR and Raman spectra of two layered aluminium phosphates Co(en)3Al3P4O16 · 3H2O and [NH4]3[Co(NH3)6]3[Al2(PO4)4]2 · 2H2O

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.     

Syntheses and structures of two new lithium-heptamolybdates

The synthesis, crystal structures, IR, UV–vis, ⁷Li NMR spectra, electrochemical investigations, and conductivity studies of two new lithium-heptamolybdates, (NH₄)₄[Li₂(H₂O)₇][Mo₇O₂₄]·H₂O (1) and (NH₄)₃[Li₃(H₂O)₄(μ₆-Mo₇O₂₄)]·2H₂O (2), are reported. In 1 the (NH₄)⁺ and [Li₂(H₂O)₇]²⁺, cations are charge balanced by the heptamolybdate anion. In 2, the [Mo₇O₂₄]^6? anion is coordinated to three unique Li⁺ ions via a μ₆-hexadentate-binding mode resulting in the formation of a two-dimensional (2-D) [Li₃(H₂O)₄(μ₆-Mo₇O₂₄)]^3? anionic complex, charge neutralized by three (NH₄)⁺ ions. The cations, anions, and the lattice water molecules in 1 and 2 are linked by weak H-bonding interactions.     

Studies of layered uranium (VI) compounds. VI. Ionic conductivities and thermal stabilities of MUO2PO4 · nH2O,where M = H,Li,Na,K,NH4 or 12Ca, and where n is between 0 and 4

We have measured the ionic conductivities of pressed pellets of the layered compounds MUO₂PO₄ · nH₂O, and correlated the results with TGA data. The conductivities (in ohm^?1 m^?1), at temperatures increasing with decreasing water content over the range 20 to 200°C, were approximately as follows: Li⁺4H₂O, 10^?4; Li⁺, Na⁺, K⁺, and NH₄⁺3H₂O, 10^?4, 10^?2, 10^?4, and 10^?4; H⁺, Li⁺, and Na⁺1.5H₂O, 10^?2, 10^?4, and 10^?4; Na⁺1H₂O, 10^?5; H⁺, K⁺, and NH₄⁺0.5H₂O, all 10^?5; and H⁺, Li⁺, Na⁺, K⁺, NH⁺₄, and $\text{1}\text{2}\text{Ca}{}^{\mathrm{2+}}\text{}\text{OH}{}_2\text{O}$, 10^?5, 10^?5, 10^?4, 10^?5, 10^?5, and 10^?6. A ring mechanism is proposed to account for the high conductivity found in NaUO₂PO₄ · 3.1H₂O. The accurate TGA data showed that most of the hydrates had water vacancies of the Schottky type, and should be represented as MUO₂PO₄(A ? x)H₂O, where x can be between 0 and 0.3.     

Microwave synthesis,structure, and properties of molybdophosphate compounds

Two compounds of disphosphopentamolybdate(VI) with the formulae (C₄H₁₄N₂O)₃- [P₂Mo₅O₂₃]?·?3H₂O (1) and (C₄H₁₄N₂O)₅(NH₄)₂[P₂Mo₅O₂₃]₂?·?5H₂O (2) have been synthesized by a simple, fast and efficient microwave method, and their crystal structures and spectroscopic properties have been studied. The heteropoly anion [P₂Mo₅O₂₃]^6? has a known structure built of five MoO₆ octahedra and two PO₄ tetrahedra. The MoO₆ octahedra form a pentagonal ring by sharing four edges and one corner and the PO₄ tetrahedra are attached to one side of the ring by three oxygen atoms. The most interesting feature of compound 1 is its extensive framework based on a one-dimensional zigzag chain. In compound 2, a more extensive and complicated framework of hydrogen bonds joins the anions, organic cations and water molecules together.     

Complexation of the [Rh(NH3)5H2O]3+ ion in aqueous solutions of H3PO4 based on 31P NMR data

The kinetics of the reaction between the [Rh(NH₃)₅H₂O]³⁺ ion and H₃PO₄ was studied by ³¹P NMR at 323?C343 K (E _a = 100.9 ± 0.3 kJ/mol, lnA = 35.7 ± 0.1). An empirical dependence of the ³¹P chemical shift on the equilibrium pH was found. The acid dissociation constants of the coordinated H₂PO ₄ ^? (3.9) and H PO ₄ ^2? ions (9.1) were estimated. The chemical shifts of the [Rh(NH₃)₅H₂PO₄]²⁺, [Rh(NH₃)₅HPO₄]⁺, and [Rh(NH₃)₅PO₄]⁰ complex ions were 8.38 ± 0.03, 10.76 ± 0.05, and 13.63 ± 0.05 ppm, respectively.     

Synthesis and Crystal Structure of Two Decavanadates Cluster Metal Complexes: [Co(H2O)6]2[H2V10O28]·6H2O and (NH4)2[Ca(H2O)7]2[V10O28]

Two new decavanadate metal complexes, [Co(H₂O)₆]₂[H₂V₁₀O₂₈]·6H₂O (1) and (NH₄)₂[Ca(H₂O)₇]₂[V₁₀O₂₈] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO₃ solution with an aqueous solution of CoCl₂·6H₂O were used for generating 1 and aqueous CaCl₂·2H₂O and NH₄VO₃ solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H₂O)₆]²⁺ cations, [H₂V₁₀O₂₈]⁴⁻ anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H₂O)₇]²⁺ cations, ammonium NH₄ ⁺ and [V₁₀O₂₈]⁶⁻ anion. For compound 2, the distorted pentagonal bipyramid [Ca(H₂O)₇]²⁺ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.     

Synthesis and Properties of Inorganic Triphosphate Crystal Hydrates

Abstract

The polycrystalline samples and single crystals of crystal hydrates of inorganic triphosphates with ring-like and chain-like anion structured were synthesized: lithium and sodium cyclotriphosphates, sodium and ammonium chain triphosphates, and double salts of chain triphosphoric acid (ammonium-potassium, ammonium-magnesium, ammonium-manganese). The crystallization field of the double salt of variable composition (NH₄,K)₃H₂P₃O₁₀ ·xH₂O (NH₄ :K=0.23–3.60; x=0.8–1.5) from aqueous solutions was established. Synthesis of Na₅P₃O₁₀ · 6D₂O crystals has been performed by the interaction of the high temperature form Na₅P₃O₁₀ (I) with D₂0. At 20°C and relative humidity RH < 70–80% the (NH₄) ₅P₃O₁₀·2H₂O crystals lose their transparency and generate different crystalline products depending on RH value: (NH₄)₅P₃O₁₀ at RH=0% or (NH₄)₅P_{3 10} · H₂O at RH=32%. The (NH₄) ₅P₃ O₁₀ · H₂O crystals are stable at RH < 60–70%, at RH=80% they absorb water and transform into (NH₄) ₅P₃O₁₀ · 2H₂0. In the latter case a characteristic picture is registered: on active sites situated on the (NH₄) ₅P₃O₁₀ · H₂O crystal face the appearance and epitaxial growth of (NH₄) ₅P₃O₁₀ · H₂O crystals is observed. For some single crystals the character of dehydration localization has been shown to correlate with space arrangement of phosphate groups in crystal structure. On the basis of the obtained results a model of dehydration front propagation in crystals has been suggested.     

Syntheses and X-Ray Crystal Structures of Novel Oxonium Ion-12-Crown-4 Complexes Isolated From Liquid Clathrate Media

Abstract

The reactions of Mo(CO)₆ and W(CO)₆ with HCl_(g) in the presence of 12-crown-4 and H₂O have been investigated in toluene. For both reactions, two products were isolated, depending on the oxidation of the metal center. For molybdenum, the Mo^III species, [H₃O⁺ · 12-crown-4]₃[Mo₂Cl₉ ^3-], 1, was obtained from the liquid clathrate layer in the reaction mixture. Upon air oxidation of the reaction mixture, the Mo^v complex, [H₇O₃ ^? · H₄O₂ ⁺ · (12-crown-4)₂][MoOCl₄(H₂O)^?]₂, 2, rapidly formed. For tungsten, the W^II species, [(H₅O₂ ⁺)₂ · 12-crown-4][W(CO)₄Cl^? ₃]₂, 3, deposited from the liquid clathrate layer which upon oxidation formed the W^v complex, [H₃O⁺· 12-crown-4][WOCl₄(H₂O)^?], 4. These reactions were promoted by UV radiation and formed liquid clathrates almost immediately upon reaction. X-ray crystal structures were performed on each compound. Complexes 1 and 4 have H₃O⁺ oxonium ions involved in complex hydrogen bonded arrays with the 12-crown-4 acceptor molecules. The H₅O₂ ⁺ oxonium ions in 2 and 3 contain extremely short O…O separations, equivalent to the shortest O-H…O bonds known. Also isolated in complex 2 was the H₇O₃ ⁺ oxonium ion which contains an unusual linear O…O…O core.     

Hydrothermal Synthesis and Structure of Two New Mo(V)-Oxide Phosphates

Two new members of Mo(V) phosphates were synthesized by hydrothermal methods. (enH₂)(enH)[NaMo₁₂O₂₄(OH)₆(HPO₄)₂(H₂PO₄)₆]·(en)₄·20H₂O(1)(en=H₂ NCH₂CH₂NH₂)[HAD-H₂]₂[HAD-H]₂[Zn₃Mo₁₂O₂₄(OH)₆(PO₄)₂(HPO₄)₆]·6H₂O (2) (HAD=H₂N(CH₂)₆NH₂). Compound 1 crystallized in the space group P2(1)/n, a=15.93120(10) Å, b=15.8946(2) Å, c=17.0665(2) Å, V=4316.02(8), =92.9060(10)°, Z=2. Compound 2 crystallized in the space group P(–1) with a=12.3726(3) Å, b=14.1948(3) Å, c=14.2310(4) Å, =72.7100(10), =65.0230(10), =69.5600(10)°, Z=2089.70(9) ų, and Z=1. The structure of 1 consists of sandwich-shaped cluster anion [Na{Mo^V ₆O₁₂(OH)₃(HPO₄)(H₂PO₄)₃}₂]^3– ({Na(Mo ^V ₆ ) ₂ }) held together via intermolecular hydrogen-bonding contacts. For the compound 2, the sandwich-shaped clusters Zn[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂ ({Zn(Mo ^V ₆ ) ₂} are linked by tetrahedrally-coordinated zinc into layers. Organic cations ([H₃N(CH₂)₆NH₃]²⁺ and [H₃N(CH₂)₆NH₂]⁺) are filled in the spaces between lamellas. The layers are held together by a hydrogen-bonded network, which involves the terminal phosphate P-OH groups, as well as organic cations and several waters of solvation.     

Molybdenum Bisphosphonates with Cr(III) or Mn(III) Ions

The synthesis of Mo^VI bisphosphonates (BPs) complexes in the presence of a heterometallic element has been studied. Two different BPs have been used, the alendronate ligand, [O₃PC(C₃H₆NH₃)(O)PO₃]^4? (Ale) and a new BP derivative with a pyridine ring linked to the amino group, [O₃PC(C₃H₆NH₂CH₂C₅H₄N)(O)PO₃]^4? (AlePy). Three compounds have been isolated, a tetranuclear Mo^VI complex with Cr^III ions, (NH₄)₅[(Mo₂O₆)₂(O₃PC(C₃H₆NH₃)(O)PO₃)₂Cr]·11H₂O (Mo₄(Ale)₂Cr), its Mn^III analogue, (NH₄)_4.5Na_0.5[(Mo₂O₆)₂(O₃PC(C₃H₆NH₃)(O)PO₃)₂Mn]·9H₂O (Mo₄(Ale)₂Mn), and a cocrystal of two polyoxomolybdates, (NH₄)₁₀Na₃[(Mo₂O₆)₂(O₃PC(C₃H₆NH₂CH₂C₅H₄N)(O)PO₃)₂Cr]₂[CrMo₆(OH)₆O₁₈]·37H₂O ([Mo₄(AlePy)₂Cr]₂[CrMo₆]). In this latter compound an Anderson-type POM [CrMo₆(OH)₆O₁₈]^3? is sandwiched between two tetranuclear Mo^VI complexes with AlePy ligands. The protonated triply bridging oxygen atoms bound to the central Cr^III ion of the Anderson anion develop strong hydrogen bonding interactions with the oxygen atoms of the bisphosphonate complexes. The UV–Vis spectra confirm the coexistence in solution of both POMs. Cyclic voltammetry experiments have been performed, showing the reduction of the Mo centers. In strong contrast with the reported Mo^VI BP systems, the presence of trivalent cations in close proximity to the Mo^VI centers dramatically impact the potential solid-state photochromic properties of these compounds.     

Testing the retardancy effect of various inorganic chemicals on smoldering combustion of Pinus halepensis needles

The fire retarding performance of 28 different inorganic chemical substances was tested by measuring the relative particle fire hazard properties of Pinus halepensis needles treated with these chemicals. The tests were performed using a new method, based on a specifically designed apparatus for monitoring the forest species temperature, under precisely controlled temperature and static air atmosphere conditions. The relative ignition and smoldering combustion properties determined were: the ignition delay time, the combustion rate, the heat content and the mass residue of forest samples. The key elements for the effectiveness of fire retardants were the delay of ignition and the reduction of heat and combustion rate. The chemicals examined were: Cu, Fe, Al₂O₃, Fe₂O₃, SiO₂·H₂O, NaHCO₃, KI, KBr, KCl, NaCl, CaCO₃, MnSO₄·5H₂O, CuSO₄·5H₂O, MgCl₂·6H₂O, Na₂B₄O₇·10H₂O, Na₂HPO₄, Na₂CO₃, Na₂SiO₃, ZnSO₄·7H₂O, Zn₃(PO₄)₂·2H₂O, NH₄Br, NH₄Cl, NH₄HCO₃, (NH₄)₂CO₃, NH₄H₂PO₄ (MAP), (NH₄)₂SO₄ (AS), (NH₄)₂HPO₄ (DAP) and a commercial retardant containing both DAP and AS. Among them the best performance was exhibited by ammoniac phosphates, followed by ammoniac sulfates and silica.     

Two new open framework cobalt phosphates: NaCo3(OH)(PO4)2.1/4H2O and Na(NH4)Co2(PO4)2.H2O

Two new cobalt phosphates, NaCo₃(OH)(PO₄)₂.1/4H₂O (1) and Na(NH₄)Co₂(PO₄)₂.H₂O (2) have been synthesized hydrothermally and characterized by single crystal X-ray diffraction methods, vibrational (IR and Raman) spectroscopy, thermogravimetric analysis and magnetic measurements. The structure of 1 is a new framework type while 2 is an example of a chiral cobalt phosphate. Both phases contain channels in which the Na⁺, NH₄⁺ cations and H₂O molecules are located.     

Non-isothermal kinetics of thermal decomposition of NH<Subscript>4</Subscript>ZrH(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>·H<Subscript>2</Subscript>O

Nanocrystalline NH₄ZrH(PO₄)₂·H₂O was synthesized by solid-state reaction at low heat using ZrOCl₂·8H₂O and (NH₄)₂HPO₄ as raw materials. X-ray powder diffraction analysis showed that NH₄ZrH(PO₄)₂·H₂O was a layered compound with an interlayer distance of 1.148 nm. The thermal decomposition of NH₄ZrH(PO₄)₂·H₂O experienced four steps, which involves the dehydration of the crystal water molecule, deamination, intramolecular dehydration of the protonated phosphate groups, and the formation of orthorhombic ZrP₂O₇. In the DTA curve, the three endothermic peaks and an exothermic peak, respectively, corresponding to the first three steps' mass losses of NH₄ZrH(PO₄)₂·H₂O and crystallization of ZrP₂O₇ were observed. Based on Flynn–Wall–Ozawa equation and Kissinger equation, the average values of the activation energies associated with the NH₄ZrH(PO₄)₂·H₂O thermal decomposition and crystallization of ZrP₂O₇ were determined to be 56.720 ± 13.1, 106.55 ± 6.28, 129.25 ± 4.32, and 521.90 kJ mol⁻¹, respectively. Dehydration of the crystal water of NH₄ZrH(PO₄)₂·H₂O could be due to multi-step reaction mechanisms: deamination of NH₄ZrH(PO₄)₂ and intramolecular dehydration of the protonated phosphate groups from Zr(HPO₄)₂ are simple reaction mechanisms.     

Polyoxomolybdates functionalized with aminomethylene phosphonate

A new organic-inorganic hybrid Strandberg-type polyoxomolybdate derivative [(n-C₄H₉)₄N]₂[(NH₂CH₂PO₃)₂Mo₅O₁₅] · (CH₃NHCH₃)₂ · H₂O (I) has been synthesized and structurally characterized by elemental analysis, IR spectrum, UV spectrum, TG analysis, cyclic voltammetry, and single-crystal X-ray diffraction. The hybrid polyoxoanion [(NH₂CH₂PO₃)₂Mo₅O₁₅]²⁻ consists of a ring-shaped {Mo₅O₂₁} cluster with two [NH₂CH₂PO₃]⁻ groups incorporating into the opposite sides of the ring. The UV spectrum studied at different times reveals that I remains stable in CH₃CN-H₂O solvents (volume ratio = 1 : 2) for one day, and the electrochemical measurement indicates that I can exist in a pH range of 4.12–4.72.     

K3[Fe3.26V0.74(OH)O(PO4)4(H2O)2]·2H2O: a synthetic leucophosphite

A new iron(III)/vanadium(III) phosphate, K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O (1), has been obtained by hydrothermal synthesis and characterized by single crystal X-ray diffraction, Scanning electron microscopy–energy dispersive X-ray spectroscopy, Inductively coupled plasma atomic emission spectroscopy (ICP), thermogravimetric analysis, and FTIR spectroscopy. Single crystal X-ray diffraction reveals a 3D open framework (monoclinic, space group P2₁/n, a?=?9.6391(7)?Å, b?=?9.8063(7)?Å, c?=?9.7268(7)?Å, β?=?100.71(1)°, and V?=?903.38(11)?ų). This structure presents Fe^III and V^III in a 4.4?:?1?M ratio with the metal ions in two different crystallographic sites. Both metallic centers have distorted octahedral environments, linked by PO₄ tetrahedra, forming channels along the a-axis. The asymmetric unit of K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O presents a {M₄(OH)O(PO₄)₄(H₂O)₂}^3? anionic entity, charge balanced by three K⁺, which are located within the channels. It is also possible to distinguish M₄O₂ units whose M^III polyhedra are linked by vertex and edges.     

Study of the trivalent elements polyphosphates by thermal analysis

Mechanisms of formation of polyphosphates Me^III(PO₃)₃, where M ^III=La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Sc, Fe, Ga, Al and Cr has been simulated by thermal analysis technique. Me^III oxides and ammonium dibasic phosphate (NH₄)₂HPO₄ were used as starting materials. For M ^III=La-Lu, Y and Fe three main stages were observed: 1. elimination of water and ammonia leading to the formation of ammonium tripolyphosphate (NH₄)₅P₃O₁₀; 2. reaction of the latter with Me₂^IIIO₃ and formation of acidic polyphosphates Me^IIIH₂P₃O₁₀ or their isomers Me^III(PO₃)₃·H₂O; 3. final loss of water and formation of Me^III(PO₃)₃. For Me ^III=Sc and Ga the second stage is prolonged and the polyphosphates form at higher temperatures. Aluminum and chromium polyphosphates are unstable. It is suggested that thermal behavior of the compounds is determined by Me^III ionic radii.     

Reactions of cisplatin hydrolytes, cis-[Pt(15NH3)2(H2O) 2]2+, with N-acetyl-L-cysteine

The reaction of cis-[Pt(¹⁵NH₃)2(H₂O) ₂] ²⁺ (3) with N-acetylcysteine [H₃accys] was investigated in aqueous solution. In this reaction, the ammine in the platinum complex formed was liberated. A mono-dentate sulfur-boundplatinum(II) product cis-[Pt(¹⁵NH₃)₂(H₂O)(H2accys-S)]⁺ (7) and six-membered che-late ring complex cis-[Pt(¹⁵NH₃)₂ (Haccys-S,O)] (8) were formed in solution. The dinuclear sulfur-bridged complex 9, giving a broad peak in ¹⁵N NMR, was also observed, but only present in very tiny amounts. The mass spectrometry (ES-MS) was undertaken from this re action, and the product detected was only the dinuclear sulfur bridged platinum species and species related to it by ammine loss.     

Sur L'Existence d'un Intermediaire Reactionnel Entre Phosphate et Pyrophosphate Acide de Potassium: Cas de K2H8(PO4)2P2O7

On the Existence of Intermediate Reaction Products of Potassium Hydrogen Phosphate and Diphosphate: K₂H₈(PO₄)₂P₂O₇ The crystal structure of K₂H₈(PO₄)₂P₂O₇ has been determined from diffractometer data obtained using MoKα radiation. The space group is Pca2₁ with a = 9.364(2), b = 7.458(2) and c = 19.560(2) Å, V = 1 366.0 ų; d_m = 2.17(1) g/cm³. Z = 4 · μ(MoKα) = 12.47 cm^?1. The structure was solved by direct methods. The crystal structure was refined to R = 0.025 for 416 independent reflexions. Two kinds of PO₄ exist and the mean value of P? O is 1.55(2) Å for one and 1.53(2) Å for the other. In P₂O₇ the angle P? O? P is 135(1)°. The distances P? O of bridge are 1.59(2) and 1.57(2) Å the mean value of P? O in terminals ? PO₃ is 1.51(2) Å. The coordination numbers of the potassium ions are nine and eight. K₂H₈(PO₄)₂P₂O₇, compound with mixed anion PO₄/P₂O₇ may be considered as reactional intermediary between acid orthophosphate and pyrophosphate.