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81.
Some sulphur-containing ligands have been shown to inhibit the Hg(II)-catalysed substitution of p-nitrosodiphenylamine (p-NDA) for cyanide in hexacyanoferrate(II), by binding the mercury(II). This effect is used for determination of microamounts of cysteine, thioglycollic acid and thiosulphate. The reactions are followed spectrophotometrically at 640 nm (lambda(max) of [Fe(CN)(5).p-NDA](3-)). The determination range depends on the amount of mercury(II) added and the stability of the Hg(II)-ligand complex. Under specified conditions, the detection limits are: thioglycollic acid 1 x 10(-7)M, cysteine 1 x 10(-6)M and thiosulphate 4 x 10(-7)M. 相似文献
82.
Geraldine S.P. Ritchie Alan M. Posner Ian M. Ritchie 《Journal of Electroanalytical Chemistry》1981,123(2):397-407
Variation of the lifetime of a mercury drop with potential was used to determine the pzc of mercury in the presence of soil humic acids and their aluminium complexes. In all cases there was an overall net shift in the pzc in the cathodic direction. Variation in the extent of the shift with pH and concentration indicated greater adsorption of negatively charged species. The shift was smaller in the presence of aluminium humates, probably due to a decrease in the negative charge of the humic acid molecules after complexing. The use of electroanalytical techniques for metal speciation studies in soils and natural water, if humic materials are known to be present, might therefore be limited. 相似文献
83.
T-2 toxin and diacetoxyscirpenol (DAS), two trichothecene mycotoxins containing one hydroxy group, have been volatilized by induction heating, revolatilized, and analyzed by gas chromatography (GC) and/or GC mass spectroscopy. Seventy to eighty percent of DAS was recovered by this system; 60–70% T-2 toxin was recovered. When the hydroxy group is derivatized by acetate, 90–100% recovery is obtained. Other trichothecenes of the macrocyclic ester type (e.g., Roridan A) were also tried. Ten to twenty percent of the macrocyclic ester was obtained without derivatization. 相似文献
84.
Anodic stripping voltammetry at a glassy carbon disc electrode covered by a thin mercury film was adapted for use in a flow-through cell. The resulting system is characterized by extreme simplicity of set-up and operation, high sensitivity and excellent precision and stability. Its performance was tested via the determination of hydrated or labile complex ions of heavy metal ions in sea water, using short (2–10 min) deposition periods. The dependence of the stripping peak charge on metal ion concentration, length of deposition period, solution flow rate and other variables was examined and the reliability of the results obtained were evaluated under conditions resembling continuous monitoring. 相似文献
85.
Robert G. Behrens 《Journal of organometallic chemistry》1976,121(3):C63-C65
The results of low temperature heat capacity studies on Mn2(CO)10(s) and Re2(CO)10(s) are compared with literature reports. It is shown that the values of vaporization enthalpies and entropies correspond with those of the low temperature stable phase. 相似文献
86.
The cyclic sulfones1,2, and3 are lithiated in benzene with n-butyllithium. Lithiation is demonstrated to lead to α-mono, α,α′-di and/or α,α-di and α,α,α′ trimetallation. The lithiated sulfones are chlorinated with hexachloroethane (HCE). Some mechanistic aspects of the reaction of the lithiosulfones with vicinal dihalides are discussed. 相似文献
87.
Solubilities and the solvolytic behaviour of various inorganic compounds, Lewis acids and bases in fused monobromoacetic acid at 60 ± 0.5°C are discussed. Ionic compounds are fairly soluble, iodides and thiocyanates being comparatively more soluble than chlorides and bromides. Tetraalkyl ammonium halides are highly soluble in this solvent. Conductometric and spectroscopic studies of various Lewis acids and bases in fused monobromoacetic acid indicate their solvolytic behaviour and their subsequent ionization. The solvolyses products BBr3·CH2BrCOOH and SbCl5·CH2BrCOOH have been observed to be the strongest Bronsted acids. Auto-ionization of this solvent has been supported by acid/base titrations. 相似文献
88.
Crystals of Li0.33 MoO3 (blue), Rb0.23MoO3 (blue) and Cs0.31MoO3 (red) were grown by electrolysis from MoO3M2MoO4 melts (M =alkali metal) with composition 70–77 mole% MoO3. Melts richer in M2MoO4 produced MoO2 only. Correlation is made between bronze formation and the coordination of Mo in the melt and in the equilibrium solid phase M2Mo4O13. Li0.33MoO3 and Cs0.31MoO3 are semiconductors with high-temperature-range activation energies 0.16 and 0.12 eV. Rb0.23MoO3 has an electrical behavior similar to that of blue KxMoO3 with a semiconductor-metal transition at (170 ± 5) K. ESR spectra observed in Li0.33MoO3 and Rb0.23MoO3 single crystals at 4.2 K show extensive delocalization of the 4d1 electron associated with Mo(V) centers. Attempts to grow molybdenum bronzes containing Ca or Y were unsuccessful. 相似文献
89.
The open circuit dissolution of ionic metal oxides in mineral acids is modelled assuming that the rate is controlled by the transfer of metal ions in hydrolytic equilibrium with bulk metal ions, from the metal oxide surface to the Stern plane. The site-binding model of the double layer metal oxide/electrolyte solution is used to obtain the pH dependence of surface and Stern potentials. The nature of the active sites is discussed and their surface concentration is assumed to be proportional to suface charge σ0. Again, the site-binding model is used to detemine the pH dependence of σ0. It is thus shown that the rate order in cH+ is essentially defined by the potential dependence of the charge transfer process, for oxides with points of zero charge near neutrality that dissolve in mildly or strongly acidic solutions. The role of surface complexation is also discussed in terms of the site-binding model and the difficulties in interpreting dissolution experiments under constant external applied potential are discussed in terms of the complexity of the semiconductor oxide/electrolyte solution interfacial region in magnetite.An experimental study of the open circuit dissolution of magnetite in sulfuric acid is presented and interpreted according to the proposed model.The reductive dissolution of magnetite is modelled by extension of the Valverde-Wagner model of oxide dissolution. Experimental results are presented to demonstrate that the reductive dissolution rate of magnetite in ferrous containing solutions is controlled by the rate of electron transfer from adsorbed Fe(II) to Fe(III) surface states of magnetite. 相似文献
90.
The number of complex species in solution may be determined by a computer-assisted factor analysis of a set of potentiometric titration curves, by finding the rank of the normalized data matrix. An application of the program SPECIES is demonstrated for some examples of titration data. The method is limited in that it can discriminate only between species with differing degrees of polymerization. 相似文献