<Emphasis Type="Italic">Ab initio</Emphasis> Study of Al(III) Adsorption on Stepped 100 Surfaces of KDP Crystals

Crystals of potassium dihydrogen phosphate (KH₂PO₄, KDP) are grown in large scale for use as nonlinear material in laser components. Traces of trivalent metal impurities are often added to the supernatant to achieve habit control during crystal growth, selectively inhibiting the growth of the {100} face. Model systems representing AlPO₄-doped KDP {100} stepped surfaces are prepared and studied using ab initio quantum methods. Results of Hartree–Fock partial optimizations are presented, including estimated energies of ion pair binding to the steps. We find that the PO₄^3– ion takes a position not unlike that of a standard phosphate in the crystal lattice, while the aluminum atom is displaced far from a K⁺ ion position to establish coordinations with the PO₄^3– ion and to bind with another lattice-bound phosphate. Our optimized structures suggest that it is the formation of a fourth coordination of Al(III) to a third phosphate ion from solution, or perhaps from a nearby position in the lattice, that disrupts further deposition, pinning the steps.     

松毛虫性信息素微量成分鉴定方法的研究

采用气相色谱-质谱分析确认了顺-5-,反-7-十二碳二烯乙酸酯是思茅松毛虫性信息素腺体的主要成分（次要成分由于含量极微且受杂质干扰,未能获得全扫描质谱图）。利用高分辨率毛细管气相色谱分析了思茅松毛虫性信息素腺体提取物的酯基转移和乙酰化反应的衍生物,进一步确认了顺-5-,反-7-十二碳二烯醇是思茅松毛虫性信息素腺体中的微量成分。探讨了功能团相互转换微量化学反应法鉴定松毛虫性信息素腺体中微量成分功能团和立体构型的优点。强调了性信息素微量成分鉴定工作在昆虫化学通讯系统研究中的重要性。     

Determination of Lead, Chromium, Manganese and Zinc in Slurries of Botanical and Biological Samples by Electrothermal Atomic Absorption Spectrometry Using Tungsten-Containing Chemical Modifiers

Lead, Cr, Mn and Zn in slurries of botanic and biological samples were determined by electrothermal atomic absorption spectrometry (ETAAS) using W, Ir, NH₄H₂PO₄, W and NH₄H₂PO₄, Ir and NH₄H₂PO₄, W and Ir, and W + Ir + NH₄H₂PO₄ chemical modifiers in an 0.2% (v/v) Triton X-100 plus 0.2% (v/v) nitric acid mixture. Zeeman effect background correction was performed and platforms inserted into graphite tubes were used. Comprehensive comparative studies were carried out with respect to pyrolysis and atomization temperatures, atomization and background absorption profiles, characteristic masses, detection limits and accuracy of the determinations in the presence and absence of modifiers. The mixture of W + Ir + NH₄H₂PO₄ was found to be preferable for the determination of Pb, Cr, Mn and Zn in slurry samples. The pyrolysis temperatures of the analytes were increased up to 1250 °C for Pb, 1000 °C for Zn, 1400 °C for Cr and Mn by using W + Ir + NH₄H₂PO₄ with an 0.2% (v/v) Triton X-100 plus 0.2% (v/v) nitric acid mixture used as diluent solution. The optimum masses of the mixed modifier components were found to be 20 µg W + 4 µg Ir + 50 µg NH₄H₂PO₄. The characteristic masses of Pb, Cr, Mn and Zn obtained are 16.3, 5.6, 0.1 and 1.1 pg, respectively. The detection limits of Pb, Cr, Mn and Zn based on integrated absorbance for 0.5% (m v⁻¹) slurries were found to be 0.14, 0.06, 0.02 and 0.01 µg g⁻¹, respectively. The slurries of botanic and biological certified and standard reference materials were analyzed with and without the modifiers. Depending on the sample type, the percent recoveries increased from 63 up to 104% for analytes when using the proposed modifier mixture.     

Determination of Formation Regions of Titanium Phosphates; Determination of the Crystal Structure ofβ-Titanium Phosphate, Ti(PO4)(H2PO4), from Neutron Powder Data

The formation region of the various types of layered titanium hydrogen phosphate hydrates was investigated. The materials were prepared by hydrothermal methods, treating amorphous titanium phosphate with phosphoric acid (8 to 16M) in the temperature range 175 to 250°C. The materials obtained were:α-Ti(HPO₄)₂·H₂O,γ-Ti(PO₄)(H₂PO₄)·2H₂O, and its anhydrous formβ-Ti(PO₄)(H₂PO₄). The structure ofβ-Ti(PO₄)(H₂PO₄) has been determined by Rietveld powder refinement of high resolution neutron diffraction data. The structure is refined in the monoclinic space groupP2₁/n(No. 14). The unit cell parameters are:a=18.9503(4) Å,b=6.3127(1) Å,c=5.1391(1) Å,β=105.366(2)°;Z=4. The final agreement factors were:R_p=2.9% andR_wp=3.8%. The structure ofβ-Ti(PO₄)(H₂PO₄) is built from TiO₆octahedra linked together by tertiary phosphate (PO₄) and dihydrogen phosphate ((OH)₂PO₂) tetrahedra. The layers are held together by hydrogen bonds.     

Computer evaluation of gas chromatograms with wide dynamic range

Summary If the complete dynamic range of the flame ionisation detector (FID) amplifier signal is to be integrated during trace analysis, the computer used for this purpose must have an effective dynamic range of at least six decades. The detection limit for traces in the ppm range (parts per million), whilst the major component is simultaneosly integrated, is discussed using samples of pure styrene, propylene and vinyl chloride. The dynamic range can be increased by using minor components as internal markers, by a computer-controlled attenuator switch and by a splitter which produces an internal marker in the chromatogram. In this way, trace components around the ppm level can be determined with standard deviations of a few percent.     

The Standard Chemical-Thermodynamic Properties of Phosphorus and Some of its Key Compounds and Aqueous Species: An Evaluation of Differences between the Previous Recommendations of NBS/NIST and CODATA

The aqueous chemistry of phosphorus is dominated by P(V), which under typical environmental conditions (and depending on pH and concentration) can be present as the orthophosphate species H₃PO ₄ ⁰ (aq),H₂PO ₄ ^? (aq),HPO ₄ ^2? (aq) or PO ₄ ^3? (aq). Many divalent, trivalent and tetravalent metal ions form sparingly soluble orthophosphate phases that, depending on the solution pH and concentrations of phosphate and metal ions, can be solubility limiting phases. Geochemical and chemical engineering modeling of solubilities and speciation require comprehensive thermodynamic databases that include the standard thermodynamic properties for the aqueous species and solid compounds. The most widely used sources for standard thermodynamic properties are the NBS (now NIST) Tables (from 1982 and earlier, with a 1989 erratum) and the final CODATA evaluation (1989). However, a comparison of the reported enthalpies of formation and Gibbs energies of formation for key phosphate compounds and aqueous species, especially H₂PO ₄ ^? (aq) and HPO ₄ ^2? (aq), shows a systematic and nearly constant difference of 6.3 to 6.9 kJ?mol^?1 per phosphorus atom between these two evaluations. The existing literature contains numerous studies (including major data summaries) that are based on one or the other of these evaluations. In this report we examine and identify the origin of this difference and conclude that the CODATA evaluation is more reliable. Values of the standard entropies of the H₂PO ₄ ^? (aq) and HPO ₄ ^2? (aq) ions at 298.15 K and p?° =1 bar were re-examined in the light of more recent information and data not considered in the CODATA review, and a slightly different value of S _m ^o (H₂PO ₄ ^? , aq, 298.15 K) = (90.6±1.5) J?K^?1?mol^?1 was obtained.     

Non-random cation distribution in hexagonal Al0.5Ga0.5PO4

Based on powder X-ray diffraction and ³¹P Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) investigations of mixed phosphate Al_0.5Ga_0.5PO₄, prepared by co-precipitation method followed by annealing at 900 °C for 24 h, it is shown that Al_0.5Ga_0.5PO₄ phase crystallizes in hexagonal form with lattice parameter a=0.491(2) and c=1.106(4) nm. This hexagonal phase of Al_0.5Ga_0.5PO₄ is similar to that of pure GaPO₄. The ³¹P MAS NMR spectrum of the mixed phosphate sample consists of five peaks with systematic variation of their chemical shift values and is arising due to existence of P structural units having varying number of the Al³⁺/Ga³⁺ cations as the next nearest neighbors in the solid solution. Based on the intensity analysis of the component NMR spectra of Al_0.5Ga_0.5PO₄, it is inferred that the distribution of Al³⁺ and Ga³⁺ cations is non-random for the hexagonal Al_0.5Ga_0.5PO₄ sample although XRD patterns showed a well-defined solid solution formation.     

Coupled diffusion produced by hydrolysis of aqueous potassium phosphate

Conductimetric and diaphragm cell techniques have been used to measure diffusion of aqueous potassium phosphate solutions at 25°C from 0.01 to 0.10 mol-dm^–3 (M). A significant portion of the aqueous K₃PO₄ component diffuses as equimolar amounts of potassium hydrogen phosphate and potassium hydroxide produced by hydrolysis: K₃PO₄+H₂O=K₂HPO₄+KOH. Because OH^– diffuses more rapidly than HPO ₄ ^2– , the total flow of KOH exceeds the flow of K₂HPO₄. The extra flow of KOH constitutes coupled transport of a second solute component. Ternary diffusion coefficients that describe interacting flows of K₃PO₄ and KOH components are reported. At low concentrations where phosphate is strongly hydrolyzed, the molar flux of the KOH component produced by diffusion of K₃PO₄ is six times larger than the flux of the K₃PO₄ component. Binary diffusion coefficients for aqueous K₂HPO₄ solutions are also reported. It is shown that ternary transport coefficients for K₃PO₄ solutions can be estimated from the properties of binary solutions of K₂HPO₄ and KOH.     

Development and validation of a liquid chromatography method for analysis of colistin sulphate

Summary The peptide antibiotic Colistin has been successfully separated into more than thirty components on a YMC-Pack Pro, C-18 column with a mobile phase of acetonitrile—sodium sulphate (0.7% m/v)—phosphoric acid (6.8% v/v dilution of 85% m/m H₃PO₄)—water (21.5∶50∶5∶23.5) at 1.0 mL per min and detection at 215 nm. Baseline resolution of the major components, colistin A and B, and many minor components was obtained. Robustness was evaluated by performing a full-factorial design experiment. The method showed good selectivity, repeatability, linearity and sensitivity.     

Synthesis and crystallization of macroporous hydroxyapatite

Macroporous hydroxyapatite Ca₁₀(PO₄)₆(OH)₂ was synthesized using ordered polystyrene sphere templates that were impregnated with a calcium phosphate precursor solution which was allowed to solidify followed by sintering from 500 to 1000 °C in flowing oxygen to remove the polymer and crystallize the phosphates. Using a combination of diffraction and imaging the face-centered cubic macroporous framework was shown to have pore diameters of 0.8-0.9 μm and to be composed of hydroxyapatite (80-98 wt%) and X-ray diffraction amorphous material (14-55%), the proportions dependent on the duration and temperature of heat treatment. At lower sintering temperatures the HAp is calcium deficient. Ion exchange of calcium by cadmium demonstrated the potential of this material for hazardous waste remediation.     

The heat capacity and standard thermodynamic functions of Ni<Subscript>0.5</Subscript>Zr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> phosphate over the temperature range from <Emphasis Type="Italic">T</Emphasis> → 0 to 664 K

The temperature dependence of the heat capacity of crystalline nickel zirconium phosphate C°_p = f(T) was measured over the temperature range 6–664 K. The experimental data obtained were used to calculate the standard thermodynamic functions of Ni_0.5Zr₂(PO₄)₃ from T → 0 to 664 K. The standard entropy of phosphate formation from simple substances at 298.15 K was calculated from the absolute entropy of the compound. The data on the low-temperature heat capacity were used to determine the fractal dimension of Ni_0.5Zr₂(PO₄)₃ over the temperature range 30–50 K. Conclusions concerning the heterodynamic characteristics of the structure of Ni_0.5Zr₂(PO₄)₃ were drawn.     

K3Ga2(PO4)3 and Na3Ga(PO4)2

The structures of tripotassium digallium tris(phosphate), K₃Ga₂(PO₄)₃, and trisodium gallium bis(phosphate), Na₃Ga(PO₄)₂, have different irregular one‐dimensional alkali ion‐containing channels along the a axis of the orthorhombic and triclinic unit cells, respectively. The anionic subsystems consist of vortex‐linked PO₄ tetrahedra and GaO₄ tetrahedra or GaO₅ trigonal bipyramids in the first and second structure, respectively.     

Determination of seven plant nutritional elements in potassium dihydrogen phosphate fertilizer from northeastern China

Contents of seven plant nutritional elements in potassium dihydrogen phosphate fertilizer were determined by ICP-MS. Correlation coefficients of the detected elements changed between 0.9631 and 0.9999, the limits of detection range from 0.18 to 0.77 μg/L, and relative standard deviations range from 1.17% to 3.82% for all the elements, ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) is a good method to determine plant nutritional elements simultaneously. Data showed that brand 1 is a real KH₂PO₄ fertilizer, but P and K concentrations are obviously lower than the labeled value; another brand contained little KH₂PO₄, so this fertilizer is a false fertilizer. We can know that KH₂PO₄ fertilizers contain some other plant nutritional elements, such as B, Si and Zn, so KH₂PO₄ fertilizers not only provide K and P but also some trace elements.     

The thermodynamic properties of crystalline Sr<Subscript>0.5</Subscript>Zr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> phosphate from <Emphasis Type="Italic">T</Emphasis> → 0 to 665 K

The temperature dependence of the heat capacity of crystalline Sr_0.5Zr₂(PO₄)₃ phosphate was studied by precision adiabatic vacuum and dynamic scanning calorimetry over the temperature range 7–665 K. The low-temperature dependence of the heat capacity was analyzed using the Debye theory of the heat capacity of solids and its multifractal generalization, which allowed conclusions to be drawn about the heterodynamic characteristics of the structure. The experimental data obtained were used to calculate the standard thermodynamic functions of Sr_0.5Zr₂(PO₄)₃ from T → 0 to 665 K. The standard absolute entropy of Sr_0.5Zr₂(PO₄)₃ was in turn used to calculate the standard entropy of its formation from simple substances at 298.15 K.     

A dihydrogen phosphate anionic network as a host lattice for cations in 1‐methylpiperazine‐1,4‐diium bis(dihydrogen phosphate) and 2‐(pyridin‐2‐yl)pyridinium dihydrogen phosphate–orthophosphoric acid (1/1)

In the salt 1‐methylpiperazine‐1,4‐diium bis(dihydrogen phosphate), C₅H₁₃N₂²⁺·2H₂PO₄⁻, (I), and the solvated salt 2‐(pyridin‐2‐yl)pyridinium dihydrogen phosphate–orthophosphoric acid (1/1), C₁₀H₉N₂⁺·H₂PO₄⁻·H₃PO₄, (II), the formation of O—H...O and N—H...O hydrogen bonds between the dihydrogen phosphate (H₂PO₄⁻) anions and the cations constructs a three‐ and two‐dimensional anionic–cationic network, respectively. In (I), the self‐assembly of H₂PO₄⁻ anions forms a two‐dimensional pseudo‐honeycomb‐like supramolecular architecture along the (010) plane. 1‐Methylpiperazine‐1,4‐diium cations are trapped between the (010) anionic layers through three N—H...O hydrogen bonds. In solvated salt (II), the self‐assembly of H₂PO₄⁻ anions forms a two‐dimensional supramolecular architecture with open channels projecting along the [001] direction. The 2‐(pyridin‐2‐yl)pyridinium cations are trapped between the open channels by N—H...O and C—H...O hydrogen bonds. From a study of previously reported structures, dihydrogen phosphate anions show a supramolecular flexibility depending on the nature of the cations. The dihydrogen phosphate anion may be suitable for the design of the host lattice for host–guest supramolecular systems.     

Determination of peimine and peiminine in Bulbus Fritillariae Thunbergii by capillary electrophoresis by indirect UV detection using N-(1-naphthyl)ethylenediamine dihydrochloride as probe

A simple and inexpensive CE method was developed for the determination of peimine and peiminine. Because of the lack of an UV chromophore of peimine and peiminine, the detection method chosen was indirect UV detection, with N‐(1‐naphthyl)ethylenediamine dihydrochloride (NED) as the UV absorbing probe. It was thought that NED, a chromophoric ion, may form hydrogen bonding pairs with the analytes to cause significant changes in separation selectivity. Additionally, the hydrophobic interactions between analytes and the probe also play a crucial role in achieving a resolution between the two analytes. The analyses were carried out with a background electrolyte composed of 66% MeOH–ACN (1:1, v/v), 34% aqueous buffer containing 15 mM NaH₂PO₄, 2.5 mM NED, 4 mM H₃PO₄. MeOH–ACN mixtures used as organic modifiers can not only reduce the adsorption of NED to the capillary wall, but also decrease the baseline noise and drift. The method provided a linear response ranging from 5 to 200 μg/mL. The limits of detection (LODs) for peimine and peiminine were 3.9 and 4.1 μg/mL, respectively. The repeatabilities (n = 3) reached relative standard deviation values (RSDs) of 3.4 and 4.1% for the peak areas, 4.0 and 4.4% for the peak heights, and 0.29 and 0.30% for the migration time of peimine and peiminine, respectively. Regression equations revealed linear relationships (r = 0.9995–0.9996) between the peak area of each analyte and the concentration. The method developed was successfully applied to quantify peimine and peiminine in chloroform extracts of the ground Bulbus Fritillariae Thunbergii.     

Direct flame-photometric determination of calcium in soil and plant extracts,water and serum with special reference to sodium,potassium and phosphate interference

An investigation of the possibilities for the direct determination of calcium with a single-cell filter flame photometer, without preliminary separation as oxalate, led to the following conclusions:Calibration curves for 100 p.p.m. of calcium are rectilinear.Sodium causes an appreciable positive error.The error due to potassium interference is relatively much smaller than that due to sodium. Up to a certain concentration it is positive and increases with the concentration, then the emission seems to be gradually depressed and the error finally becomes negative.Phosphates cause a very significant negative error, which tends to be asymptotic. The “radiation buffer” method of correction is not practical here because the max. error is too high (—92.5%).Except for extreme cases, calcium can be determined by direct spraying, without preliminary separation as oxalate: (a) in drinking and irrigation water, correction being necessary only for sodium interference, (b) in soil extracts, correcting only for phosphate effects, (c) in normal blood sera, without clinically significant corrections at 1+3 dilution.Owing to the large variations in the contents of Na, K and PO₄^-3 in plants, calcium cannot be determined in plant-ash extracts without preliminary separation as oxalate. This applies also to abnormal sera, although there the variations in Na and PO₄^-3 content are not so large.     

Study of Some Tungsten-Containing Chemical Modifiers in Graphite-Furnace Atomic Absorption Spectrometry

Abstract

Several chemical modifiers based on tungsten have been evaluated: the individual modifiers W(VI) as WO₃ in aq. 0.2 M NH₃ and W(V) as W in H₂O₂ and the mixed modifiers W(VI)/NH₃ + Pd(II), W(V)/H₂O₂ + Pd(II), and W(V)/H₂O₂ + PO₄ ^3-. High efficiency of thermal stabilization for 18 analyte elements of high and moderate volatility has been demonstrated and possible mechanisms of stabilization are discussed.     

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.