灰化消解-极谱法测定油料中五个重金属元素

建立了灰化消解-极谱法测定油样中镉、铅、铜、镍、钴等5种微量重金属元素的含量.油料样品通过灰化法消解后,用极谱法在乙酸-乙酸盐缓冲溶液和磺基水杨酸-磷酸-氨水体系中测定5种重金属元素的含量.5种微量重金属元素的检出限为1.3×10-4～9.8×10-4 g·L-1,加标回收率为90%～106%,相对标准偏差为0.22%～3.16%.     

Ultra-stable Ni catalysts for methane reforming by carbon dioxide

Methane reforming by carbon dioxide has been studied over ultra-stable Ni catalysts. The catalyst was characterized by XRD, IR and TEM and temperature programmed hydrogenation. The nickel–magnesia solid solution catalyst containing low nickel has shown excellent stability (>3000 h) and no carbon deposition in the methane reforming by carbon dioxide. It was also found that the small nickel metal particle interaction with support surface is effective for the inhibition of carbon formation.     

Chelating Behaviour of Substituted 1-Benzoyl-4-Phenylthiosemicarbazide

The preparation and characterization of a series of new coordination compounds of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) containing o-methyl- or o-chlorobenzoyl-4-phenyl-3-thiosemicarbazide (HMBPT, HCBPT=HL) are reported. The reaction products were investigated by analyses, electrolytic conductance, magnetic susceptibility, reflectance and IR spectral studies. The IR spectra show that HMBPT and HCBPT coordinate with the metal ions via different coordination sites (NS and/or NO). The spectral data support the suggestion that the ligands form his-chelates with Ni(II) and Cu(II) of square planar stereochemistry and of general formulae ML₂·H₂O, where L is the uninegatively charged bidentate ligand. The Co(II) ion forms octahedral and tetrahedral structures with HMBPT and HCBPT, respectively. The ligand field parameters (D₄, B and β) for the Co(II) chelates were calculated using the averaged-ligand-field approximation. The influence of the benzene ring substituents (o-chloro or o-methyl) on the stereochemistry are discussed. Also, the formation of the complexes in solution was tested by the pH-metric method.     

The impact of flow injection on modern chemical analysis: has it fulfilled our expectations? And where are we going?

Presenting a condensation of the opening lecture of the 12th ICFIA conference, this communication presents a view of the impact that flow injection analysis (FIA) has had on modern analytical chemistry, evaluated both within the academic community and outside it, i.e. in “industry”. The ensuing developments of FIA, encompassing sequential injection analysis (SIA) and bead injection lab-on-valve (BI-LOV), are described and their individual features discussed. Finally, some recent results of the activities from the author’s own research group are briefly mentioned.     

Metallocycle synthesis accelerated by high pressure

Reaction of cis-[FeH₂(dmpe)₂](1) with diphenylbutadiyne results in an insertion into both of the iron-hydride bonds to form an iron metallocycle. Spectroscopic and crystallographic data of [Fe(PhHCC₂CHPh)(dmpe)₂] (3) show 1,4-diphenylbutatriene is symmetrically bound to the metal via the central double bond. The reaction to form the metallocyclic complex is greatly accelerated by application of external pressure. A 41% yield of (3) is isolated after two days at atmospheric pressure or after approximately 75 min at 800MPa.     

梅州农村饮用水重金属元素监测与分析

对梅州农村饮用水中的重金属元素进行了监测和分析，选择Fe，Mn，Zn，Cu，Ag，Pb，Cd七种元素为检测指标。从实验结果来看，Cu，Ag，Cd含量低，未超标；Fe，Mn，Zn，Pb有超标现象：按其危害程度，Pb，Mn的超标是急需解决的问题。     

CoSm(SeO3)2Cl,CuGd(SeO3)2Cl,MnSm(SeO3)2Cl,CuGd2(SeO3)4 und CuSm2(SeO3)4: Übergangsmetallhaltige Selenite von Samarium und Gadolinum

CoSm(SeO₃)₂Cl, CuGd(SeO₃)₂Cl, MnSm(SeO₃)₂Cl, CuGd₂(SeO₃)₄ and CuSm₂(SeO₃)₄: Transition Metal containing Selenites of Samarium and Gadolinum The reaction of CoCl₂, Sm₂O₃, and SeO₂ in evacuated silica ampoules lead to blue single crystals of CoSm(SeO₃)₂Cl (triclinic, , Z = 4, a = 712.3(1), b = 889.5(2), c = 1216.2(2) pm, α = 72.25(1)°, β = 71.27(1)°, γ = 72.08(1)°, R_all = 0.0586). If MnCl₂ is used in the reaction light pink single crystals of MnSm(SeO₃)₂Cl (triclinic, , Z = 2, a = 700.8(2), b = 724.1(2), c = 803.4(2) pm, α = 86.90(3)°, β = 71.57(3)°, γ = 64.33(3)°, R_all = 0.0875) are obtained. Green single crystals of CuGd₂(SeO₃)₂Cl (triclinic, , Z = 4, a = 704.3(4), b = 909.6(4), c = 1201.0(7) pm, α = 70.84(4)°, β = 73.01(4)°, γ = 70.69(4)°, R_all = 0.0450) form analogously in the reaction of CuCl₂ and Gd₂O₃ with SeO₂. CoSm(SeO₃)₂Cl contains [CoO₄Cl₂] octahedra, which are connected via one edge and one vertex to infinite chains. The Mn²⁺ ions in MnSm(SeO₃)₂Cl are also octahedrally coordinated by four oxygen and two chlorine ligands. The linkage of the polyhedra to chains occurs exclusively via edges. Both, the cobalt and the manganese compound show the Sm³⁺ ions in eight and ninefold coordination of oxygen atoms and chloride ions. In CuGd(SeO₃)₂Cl the Cu²⁺ ions are coordinated by three oxygen atoms and one Cl^— ion in a distorted square planar manner. One further Cl^— and one further oxygen ligand complete the [CuO₃Cl] units yielding significantly elongated octahedra. The latter are again connected to chains via two common edges. For the Gd³⁺ ions coordination numbers of ?8 + 1”? and nine were found. Single crystals of the deep blue selenites CuM₂(SeO₃)₄ (M = Sm/Gd, monoclinic, P2₁/c, a = 1050.4(3)/1051.0(2), b = 696.6(2)/693.5(1), c = 822.5(2)/818.5(2) pm, β = 110.48(2)°/110.53(2)°, R_all = 0.0341/0.0531) can be obtained from reactions of the oxides Sm₂O₃ and Gd₂O₃, respectively, with CuO and SeO₂. The crystal structure contains square planar [CuO₄] groups and irregular [MO₉] polyhedra.     

Spectrafluorimetric method for the rapid screening of toxic heavy metals in water samples

A fast and inexpensive sensitive screening test for recognising potential wastewater contamination by the presence of highly toxic heavy metals is described. The test is based on the reaction of the toxic heavy metals Hg(II), Cd(II), Pb(II) and Ag(I) with 6-mercaptopurine (6-MP) to produce highly fluorescent complexes.Optimum experimental conditions include a buffer of pH 7.2 (0.1 M citric acid/0.2 M Na₂HPO₄), a chelating reagent concentration of 6×10⁻⁴ M and the addition of 10⁻⁴ M of o-phenanthroline. The fluorescence emitted by the complexes was measured at 380 and 540 nm for excitation and emission wavelengths, respectively.Detection limits of 4, 3, 6 and 3 μg l⁻¹ were achieved for Hg, Cd, Pb and Ag. Relative standard deviation (R.S.D.) were between ±2 and ±6% of the fluorescence signals for five identical samples. Potential interference effects from other heavy metals (Zn, Mn, Co, Fe, Ni and Cu), which could affect the response of the proposed screening test was investigated. Results showed that none of these metals give rise to noticeable fluorescence signals under the above described experimental conditions.Finally, the capability of the proposed heavy metal screening test for the analysis of contaminated water samples is discussed.     

Effect of HF addition on the microwave-assisted acid-digestion for the determination of metals in coal by inductively coupled plasma-atomic emission spectrometry

The microwave-assisted acid-digestion for the determination of metals in coal by ICP-AES was investigated, especially focusing on the necessity of adding HF. By testing five certified reference materials, BCR-180, BCR-040, NIST-1632b, NIST-1632c, and SARM-20, it was found that the two-stage digestion without HF (HNO₃ + H₂O₂ was used) was very effective for the pretreatment of ICP-AES measurement. Both major metals (Al, Ca, Fe, and Mg) and minor or trace metals (Co, Cr, Cu, Mn, Ni, Pb, and Zn) in coal gave good recoveries for their certified or reference values. The possibility of ‘HF-memory effect’ was cancelled by the use of a set of vessels which had been never contacted with HF. Twenty-four Japanese standard coals (SS coals) were analyzed by the present method, and the concentrations of major metals measured by the present method provided very high accordance with those from the authentic JIS (Japanese Industrial Standard) method.     

New Possible Applications of Heavy Main-Group Elements in Organic Synthesis

Aside from elements of the 2nd row, and one element of the 3rd row of the periodic system—Si, P, S, and Se, respectively, whose organoelement groups such as Me₃Si and Ph₃P^⊕ have proven useful in numerous organic syntheses—other elements of the 3rd as well as 4th and 5th row (Ge, As, Sn, Sb, Te, Pb, Bi) can also be used as components of synthetically useful organoelement groups, the elements As, Sn, and Pb, in particular, offering certain advntages over the others. Some of these organoelement groups are suitable equivalents for Li- or halogen-substituents attached to carbon; they stabilize carbanionic centers (minimum of this effect at the 3rd-row elements), and owing to their suitability as leaving groups in β-eliminations, also open up interesting synthetic possibilities. The thermally unduced syn- and silica-gel induced anti-elimination of Ph₃Sn, Ph₂Sb, Ph₃Pb, together with β-OH, are novel. With the newly synthesized compounds Ph_nEl—Ch₂—Li (El = Sn, Pb, As, Sb, Bi) and other α- and β-lithiated R_nEl- and Ph₂As(O)-reagents such organoelement groups can be introduced into organic compounds and exploited in organic and organoelement synthesis.