Graphite rod atomization and atomic fluorescence for the simultaneous determination of silver and copper in jet engine oils

S-Methyldithizone(5-methylmercapto-1,5-diphenylformazan) reacts with the chlorides of copper(II), mercury(II) and phenylmercury(II) to give the 1:1 chelates [CuCl(MeDz), HgCl(MeDz) and C₆H₅Hg(MeDz)] and with nickel(II) and palladium(II) to give the 1:2 chelates, M(MeDz)₂. All these complexes are intensely coloured in chloroform solution. No complexes are formed from cobalt(II), manganese(II) or zinc(II) or from the nitrates or acetates of copper and mercury. Coordination increases the reactivity of the sulphur atom in dithizone. Whereas dithizone is unaffected by methyl iodide, nickel dithizonate, Ni(HDz)₂, gives Ni-(MeDz)₂ when heated with methyl iodide in ethanol in the presence of sodium acetate; palladium dithizonate behaves similarly. The 1:1 adduct of nickel dithizonate with 2,2'-bipyridyl gave only Ni(MeDz)₂ on treatment with methyl iodide, and this complex would not form an adduct with bipyridyl. On standing in the light, Ni(MeDz)₂ reacted photochemically to give the yellow isomer of S-methyl-dithizone.     

A sensitive optical element for mercury(II)

A transparent polymethacrylate matrix modified with copper dithizonate was used to determine mercury(II). Optimum conditions for modifying the polymethacrylate matrix with copper dithizonate were found, and its reaction with mercury(II) in model solutions was studied.     

Plasticized open-cell polyurethane foam as a universal matrix for organic reagents in trace element preconcentration : Part II. Collection of mercury traces on dithizone and diethyldithiocarbamate foams

The analytical suitability of zinc dithizonate foam for the collection and preconcentration of traces of mercury(II) has been examined. The effect of pH, plasticizer and chelating agent concentration on the collection rate of mercury has been critically investigated. The capacity for mercury(II) of a TBP-plasticized zinc dithizonate foam at pH 6 is 23.4 μeq g^?1. The effect of plasticizer on the rate of recovery of mercury with sodium thiosulphate solution is also discussed. The preparation of zinc diethyldithiocarbonate foam is described. Traces of mercury(II) can also be collected rapidly and quantitavely by this foam.     

Photochromism of silver(I) and mercury(II) dithizonates : Effect of excess of free ligand on the return to ground state and effect of silver(I) dithizonate on the return of mercury(II) dithizonate

The energy of photons producing highest yield in the photochromic excitation of both silver(I) and mercury(II) dithizonate is shown to be centered around 520 nm. The effect of silver(I) dithizonate on the return of the excited form of mercury(II) dithizonate to the ground state is described. The accelerating effect of the silver complex is interpreted by an empirical kinetic model that takes into consideration the concurrent excitation and relaxation of both complexes. As observed in the photochromism of mercury(II) dithizonate, the presence of excess of ligand proportionally hastens the relaxation of silver(I) dithizonate to the ground state.     

Potentials of thermal lens spectroscopy for polymethacrylate optical sensors

The sensitivity of the earlier proposed procedures for the determination of iron(II, III) with 1,10-phenanthroline, silver(I) with dithizone, mercury with copper(II) dithizonate, copper(II) with lead diethyldithiocarbamate, and ascorbic acid with 2,6-dichlorophenolindophenol using polymethacrylate optical sensitive elements for solid phase spectrophotometry is enhanced through the use of thermal lens spectrometry as the most sensitive method of molecular absorption spectroscopy. The limits of detection for all photometric reactions in the polymethacrylate matrix are reduced by an order of magnitude (to 10 nM) without substantial changes in the experimental conditions.     

Simple semiquantitative determination of trace metal ions by use of reagent gel columns-I: determination of mercury with dithizone gel

Mercury(II) at the sub-ppm level was determined by using a column packed with gel beads containing dithizone stabilized as the zinc complex. The beads turned from pink to green when the acidified sample solution was passed through the column. If the solution contained mercury (II), the colour of the gel beads turned to orange owing to the formation of mercury dithizonate. The length of the coloured zone was proportional to the amount of mercury in the sample. With 0.01% dithizone gel, as little as 0.1 ppm of mercury(II) could be determined in a 20-ml sample at a flow-rate of 1 ml/min.     

Liquid chromatographic determination of chelates of cobalt (II), copper (II) and iron (II) with 2-thiophonaldehyde-4-phenyl-3-thiosemicarbazone

Summary A new chelating reagent 2-thiophenaldehyde-4-phenyl-3-thiosemicarbazone (TAPT) has been examined for high performance liquid chromatographic (HPLC) separations of cobalt (II), copper(II) and iron (II) or cobalt (II), nickel (II), iron (II), copper (II) and mercury (II) as metal chelates on a C₁₈, 5μm column (250×4 mm i.d.) The chelates were eluted isocratically with methanol: acetonitrile: water containing sodium acetate and tetrabutylammonium bromide (TBA), and detected at 254 nm. A solvent extraction procedure was developed for simultaneous determination of the metals with detection limits within 0.02–2.5 μ g.mL⁻¹. The method was applied to the determination of copper, cobalt and iron in natural waters.     

An electsochemical study of copper(II) nitrate and perchlorate in n,n-dimethylformamide

Polarographic, cyclic voltammetric and controlled-potential coulometric studies of copper(II) nitrate and perchlorate in dimethylformamide are reported. Copper(II) in copper(II) perchlorate solutions is directly reduced in a 2e step to copper metal at platinum electrodes and to a copper amalgam at mercury electrodes. Copper(II) in the presence of nitrate forms a complex of composition Cu(N0₃)₂ in DMF; the dissociation constant, measured polarographically, is 9 × lO^-5. The copper(II) nitrate complex is electrochemically reduced in two steps consisting of a reversible dissociation of the complex followed by direct reduction of copper(II) ion to copper(0). The diffusion coefficients of copper(II) ion and the copper(II) nitrate complex are 4.91 × lO^-6 cm² s^-1 and 4.33 × 10^-6 cm² s^-1, respectively.     

Equilibrium and Kinetic Aspects of Hg(II) Extraction from Natural Waters with Diphenylthiocarbazone

A diphenylthiocarbazone (dithizone) based liquid-liquid extraction method of general utility is proposed for small-scale Hg(II) extraction from natural waters. The quantitative aspects related to the extraction are studied in terms of distribution of mercury dithizonate in carbon tetrachloride-water system at 293 K (20±1°C). Various distribution constants related to the reagent and the complex formed are evaluated. The equilibrium and kinetic studies of extraction and complex formation are analytically based on atomic absorption and colorimetric methods. Local natural waters were subjected to the proposed method for Hg(II) removal. The method is found to be capable of removing above 98% mercury in a single-step extraction under the conditions evaluated in terms of matrix pH, equilibration time and amount of reagent.     

Spectrophotometric determination of selenium with dithizone

Microgram amounts of selenium(IV) are determined by measuring the decrease in absorbance of dithizone in carbon tetrachloride solution at 620 nm. Relative standard deviations for samples containing 0.20 and 1.00 μg of selenium(IV) are 0.6% and 0.4%, respectively. Of several metals tested only copper (at the 1.0-μg level) and iron (at the 100-μg level) interfere but high concentrations of nitric or perchloric acid cause low results. A reinvestigation of the reaction of selenium(IV) with dithizone suggests a formula Se(HDz)₄ for the dithizonate.     

Ion-sensitive behaviour of silver sulphide-based solid-state copper(II) and iodide electrodes in partially aqueous systems

The response of copper(II)- and iodide-selective electrodes was evaluated in various water-organic solvent mixtures. The copper(II) electrode showed an almost Nernstian behaviour in mixtures with ethylene glycol, tert-butanol, propanol, ethanol and methanol. The experimental slopes in buffered water-acetonitrile mixtures were linear but super-Nernstian. The response of this electrode in mixtures with p-dioxane was neither Nernstian nor linear. The interference of mercury(II) in the direct potentiometric titration of copper(II) with EDTA in solution containing acetonitrile was studied. The behaviour of silver sulphide-based iodide electrode hydrophobized by PTFE in mixtures with ethanol, methanol and p-dioxane was poorer than in water. The potential response of the iodide electrode with a homogeneous membrane (Ag₂S + AgI) was satisfactory even after prolonged soaking in p-dioxane.     

Bubble extraction as a preconcentration step in trace elemental analysis: a preliminary study

Summary Surface active properties of dithizone and mercury(II) dithizonate have been analyzed by means of a laboratory apparatus for bubble extraction in view of utilizing it as a preconcentration device. Dependence of extraction efficiency on various parameters has been analyzed. Particularly, the dependence on concentration has been discussed in terms of adsorption isotherm and compared with that of a typical surface-active dye (crystal violet). It has been found that quantitative recovery ( 90%) of mercury, as mercury(II) dithizonate, is obtained from solutions of sufficiently low concentration ( 0.3 g/l).

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Fraktionierextraktion als Anreicherungsstufe in der Spurenelementanalyse. Eine vorläufige Untersuchung

     

Spectrophotometric determination of traces of platinum in palladium with dithizone after matrix precipitation as a compound with ammonia and iodide

Palladium is precipitated with ammonia and iodide; platinum remains in solution and is completely extracted with dithizone in carbon tetrachloride. The precipitated palladium compound is shown to be Pd(NH₃)₂I₂ by thermogravimetry and by determinations of ammonia and iodide. To separate small amounts of palladium from platinum in the dithizone extract, the resistance of platinum dithizonate to oxidizig agents is utilized; platinum dithizonate is converted to an oxidized form which is easily reduced to the initial form. The separation and spectrophotometric procedure enable about 1 × 10^?3% platinum to be quantified in palladium(II) chloride with good precision and accuracy.     

Microdetermination of mercury using silver and copper ion selective electrodes with silver-dithiooxamide and copper-diethyldithiocarbamate loaded polyurethane foams

Summary Microdetermination of Mercury Using Silver and Copper Ion Selective Electrodes with Silver-Dithiooxamide and Copper-Diethyldithiocarbamate Loaded Polyurethane Foams Low levels of mercury(II) are determined by passing their aqueous solutions at pH 1–3 through a column containing silver-dithiooxamide or copper-diethyldithiocarbamate loaded polyurethane foam, followed by monitoring the silver(I) and copper(II) ions released in the effluent with the solid state silver and copper ion selective electrodes, respectively. The rate of the exchange reactions is fast (<3 min) and the efficiency of displacing silver(I) and copper(II) ions is high (>98%). The calibration plots show slopes of 59 and 29 mV/concentration decade of mercury on using the silver and copper sensors, respectively. Determination of 20 ng/ml to 200/ml of mercury(II) in aqueous solutions shows an average recovery of 98.4% and a mean standard deviation of 2%. Many cations and anions do not interfere. Some organomercury compounds are similarly determined after a prior decomposition in an oxygen-filled flask. Results with an average recovery of 98.4% (mean standard deviation 1.9%) are obtained with 10 structurally different mercury compounds.     

Sensitive Spectrophotometric Determination of Copper(II) in the Presence of Manganese

Abstract

This paper recommends a simple and convenient procedure for the determination of copper(II) in the presence of large amounts of manganese. An aqueous solution of hydroxylamine hydrochloride and diluted sulphuric acid was used for dissolution and reduction of MnO₂. The copper(II) was complexed with an ethanolic 0.05% PAN solution in the pH range of 2 - 3 in aqueous medium. The absorbances of copper-PAN complexes are measured at 550 nm where molar absorptivity is 2.10 L.mol^?1.cm^?1.

The complex obeys Beer's Law from 0.1 to 4 ppm. of copper. Manganese(II) up to 1000 ppm. doesn't interfere. The method is sensitive and reproducible.

It has been applied to the analysis of samples containing 0.01 to 5% of copper on manganese dioxide catalysts.     

Studies on complexes of 4-(2-thiazolyl)thiosemicarbazide with some bivalent metal ions

Summary The 4-(2-thiazolyl)thiosemicarbazide HTTSC, reacts with metal ions to yield two types of complex M(HTTSC)₂ Cl₂ [M=cobalt(II), nickel(II) copper(II), cadmium(II), or mercury(II)] and [M(TTSC)₂] [M=cobalt(II), nickel(II) or copper(II)]. These complexes have been characterized by elemental analyses and studied by magnetic and spectroscopic techniques. Tetrahedral coordination around cadmium(II) and mercury(II), square planar geometry around cobalt(II) and nickel(II) in [Co(TTSC)₂] and [Ni(HTTSC)₂]Cl₂, respectively, and octahedral stereochemistry for the remaining complexes is proposed.     

Comparative study of copper(II) and cadmium(II) salts as catalytic reagents in the determination of mercury by continuous-microflow cold vapour atomic absorption spectrometry

A continuous-microflow method with cold vapour atomic absorption spectrometric detection was used for the determination of mercury. A comparison of copper(II) and cadmium(II) salts as catalytic reagents is described in detail It was found that in the presence of at least 80 mg 1^?1 of copper(II) salt a similar signal was obtained for both inorganic mercury [mercury(II) chloride]and organic mercury [methylmercury(II) chloride]. With a cadmium(II) salt at least 100 mg 1^?1 were required.     

Radiometric determination of submicrogram amounts of mercury

A radiometric method for the determination of submicrogram amounts of mercury (down to 5 x 10(-10)g ml ) is described. The method is based on the exchange reaction between mercury and silver-110m dithizonate. Only palladium, gold, silver, and large amounts of copper and bismuth interfere in the determination, and must be removed.     

Photochromic long‐chain organomercury(II) dithizonate complexes in the azomethine series

The synthesis and characterization of a series­of 4 ‐ (4′‐ n ‐alkoxybenzylideneimino)phenyl‐­mercury<?tw=97.2%>(II) dithizonates, [C_nH_2n+1OC₆H₄CH­NC₆H₄Hg<?tw>(Hdptc)] (H₂dptc = 1,5‐diphenylthiocarbazone = dithizone; n = 1, 4, 12, 14 or 18), is described. The intermediate long‐chain organomercury(II) acetates were obtained by condensation of 4‐aminophenylmercury(II) acetate with the appropriate 4‐n‐alkoxybenzaldehydes. The thermal behaviour of the complexes was studied by polarized optical microscopy and differential scanning calorimetry but revealed no mesophases. All of the complexes, however, were reversibly photochromic (yellow ⇌ blue) upon irradiation of chloroform solutions with visible light, and the half‐lives of the metastable blue forms were substantially increased relative to that of the parent mercury(II) bis(dithizonate). The compounds were not photochromic in the solid state. Copyright © 2000 John Wiley & Sons, Ltd.     

Novel mercury(II) complexes of meso-tetraphenylporphyrin and N-methylporphyrins

Treatment of meso-tetraphenylporphyrin, H₂TPP, with just over one equivalent of mercury(II) acetate in methylene chloride-THF gives mercury(II) meso-tetraphenylporphyrin, HgTPP. With excess of mercury(II) acetate, H₂TPP and HgTPP afford a novel dimetallic mononuclear porphyrin, AcOHgTPPHgOAc. In contrast, HgTPP reacts with mercury(II) chloride to give the chloro-analogue, ClHgTPPHgCl, but there is no reaction between H₂TPP and mercury(II) chloride. Demetallation of HgTPP in methylene chloride containing small amounts of hydrogen chloride proceeds via the dimetallic compound, ClHgTPPHgCl, to give free base HTPP. The reaction rate is dependent upon acid concentration suggesting that the rate determining step is protonation, but dilution causes no decrease in the rate; a mechanism which invokes the intermediacy of monohydrogen-meso-tetraphenylporphyrinatomercury(II) chloride, H(TPP)HgCl, in the formation of ClHgTPPHgCl and in its subsequent decomposition into H₂TPP, is proposed.N-Methylporphyrins react with mercury(II) acetate in methylene chloride-tetrahydrofuran to give the corresponding N-methylporphyrinatomercury(II) acetates, Me(P)HgOAc.