Simultaneous differential pulse-polarographic determination of CS2 and COS gases and its application in the analysis of dithiocarbamate fungicide residues in foods

The differential pulse-polarographic (DPP) determination of both CS₂ and COS gases, after their absorption in a methanolic piperidine reagent and the subsequent application of this technique to the residue analysis of dithiocarbamate fungicides is described. Rectilinear calibration curves for both CS₂ and COS in the respective regions of 1.5–9.2 and 2.1–12.6 μmol/l were obtained. The DPP method has been successfully applied to the determination of thiram residues on apples after a hot acid hydrolysis of the fruits.     

Simultaneous UV-spectrophotometric determination of CS2 and COS using the piperidine, pyrrolidine, ethylenediamine or morpholine reagent

Summary The success of a spectrophotometric method for the determination of dithiocarbamate or tetramethylthiuram disulphide (thiram) fungicide residues based on the quantification of the evolved CS₂ after an acid hydrolysis of the fungicide depends on the sensitivity and selectivity of the CS₂ absorbing reagent. In the present study piperidine, pyrrolidine, ethylenediamine and morpholine and their corresponding optimum reaction conditions with CS₂ and COS were spectrophotometrically investigated for their suitability as CS₂ and COS absorbing reagents. The CS₂-amine and COS-amine adducts, formed after the absorption of the CS₂ and COS gases in an alcoholic amine, exhibit different UV-absorption spectra which facilitated the quantification of both CS₂ and COS. The sensitivity of the amines to CS₂ and COS and the stability of the CS₂-amine and COS-amine adducts were found to be dependent on the reaction time between the CS₂ and COS with the amine, the concentration and the temperature of the alcoholic amine reagent. Under optimized conditions, ethylenediamine, pyrrolidine and morpholine proved to be equally sensitive to both CS₂ and COS just as the previously reported piperidine. Furthermore, the sensitivity of piperidine to COS was improved. The sensitivity optimized amine reagents, dissolved in methanol instead of ethanol and with detection limits for both CS₂ and COS down to 0.3 g/ml, should provide new and cheaper means in the residue analysis of dithiocarbamate and tetramethylthiuram disulphide (thiram) fungicides based on the evolved CS₂ and COS after an acid hydrolysis.     

Oxidation of S and SO by O2 in high-temperature pyrolysis and photolysis reaction systems

The reaction of S atoms with O₂ was studied behind reflected shock waves applying atomic resonance absorption spectroscopy (ARAS) for concentration measurements of S and O atoms. S atoms were generated either by laser-flash photolysis (LFP) of CS₂ or by the high-temperature pyrolysis of COS, respectively. The concentrations of O₂ in the mixtures ranged between 50 ppm and 400 ppm, and those of the S precursors, CS₂ and COS, between 5 and 25 ppm. The rate coefficient of the reaction was determined from the observed decay of the S absorption signals for temperatures 1220 K ? T ? 3460 K. The measured O-atom concentration profiles in COS/O₂/Ar reaction systems were evaluated, using simplified kinetic mechanism, to verify the given rate coefficient k₅. In experiments with the highest value of the [O₂]/[COS] ratio the measured O-atom concentrations were found to be sensitive to the reaction: The fitting of the calculated O-atom profiles to the measured ones results in mean value of: which is to be valid for the temperature range 2570 K ? T ? 2980 K. A first-order analysis of the observed S absorption decay in LFP shock wave experiments on CS₂/Ar gas mixtures resulted in a rate coefficient of the background reaction (R4): for temperatures 1260 K ? T ? 1820 K. © 1995 John Wiley & Sons, Inc.     

A shock tube study of the reaction S + H2 ⇌ SH + H in pyrolysis and photolysis systems

Atomic resonance absorption spectroscopy (ARAS) was applied to measure S atoms, behind shock waves in COS/H₂ pyrolysis or CS₂/H₂ photolysis systems. Both the pyrolysis of COS and the photolysis CS₂ was used to generate the S atoms, which subsequently reacts with H₂ via the reaction: The photolysis experiments were designed to provide clear first-order conditions for reaction (R3); i.e., the H₂ concentration exceeds that of S by at least a factor of 100. The S atom profiles obtained during pyrolysis of highly diluted COS/H₂/Ar mixtures were analyzed by computer simulations based on a simplified reaction mechanism using the rate coefficient k₃ as a fitting parameter. Both groups of experiments covered the temperature range of 1257 K ? T ? 3137 K and lead to a rate coefficient of: . © 1995 John Wiley & Sons, Inc.     

Equilibrium and kinetics of proton transfer from thiocarboxylic acids to γ-collidine

NMR and IR spectroscopy have been used in studying the equilibrium in the reaction of proton transfer from thiocarboxylic acids RCOSH [R=CH₃ (a), C₆H₅ (b) or CH₂Cl (c)] to -collidine (d), and also the kinetics of CH/NH proton exchange between protonated -collidine and excess RCOSH. For compoundsa and b, partial protonation of the -collidine is observed; and for compound c, complete protonation. The heat of reaction of proton transfer with the participation of binary acidamine associates is 30 (a) and 45 (b) kJ/mole. The rate of proton exchange decreases and the activation energy E increases with increasing acidity of the RCOSH [E=44 (b) and 88 (c) kJ/mole] and with increasing basicity of the amine (E_d < E_TEA), which, in accordance with the orders of reaction that were found for the exchanged components, is due to a mechanism in which the slow stage is proton transfer in the ion pair NH⁺...^–SOCR. The thiocarboxylate ion of c is unstable; and after splitting out Cl^–, it forms the compounds Cl(CH₂COS)₂ ^– and (CH₂COS)₂.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 2, pp. 187–194, March–April, 1985.     

[Re(η2-CS3)4]3−, a new trithiocarbonate-containing rhenium(V) dodecahedral anion

The mononuclear complex (NMe₄)₃[Re(²-CS₃)₄] has been prepared by adding CS₂ to ReS^– ₄ in a mixture of MeOH and NH₃. During the reaction, Re^VII is reduced to Re^V, the measured diamagnetism (X = –3.04 × 10^–4cm³mol^–1) of the complex showing that the two added electrons are coupled. (NMe₄)₃[Re(²-CS₃)₄] crystallizes in the space group Fddd, a = 11.985(4) Å, b = 23.001(11) Å, c = 47.463(19) Å, V = 13085(9) ų. The reaction of CS₂ results in the formation of trithiocarbonates bonded to the rhenium in a dodecahedral geometry.     

Kinetics and mechanism of the decomposition of CS2, OCS,and SCl2 in a radiofrequency pulse discharge

The identification of transient species in r.f. discharges and measurement of rate coefficients for their reactions contributes to the understanding of the complex mechanisms in r.f. plasma chemistry. Using kinetic spectroscopy in conjunction with a short-duration r.f. pulse to investigate the decomposition of CS₂, OCS, and SCl₂ at low pressure, it has been shown that the predominant primary dissociation steps are CS₂CS+S, OCSCO+S(¹D), and SCl₂S+Cl+Cl. With OCS the most important subsequent steps involved the formation and removal of S₂: S(¹D)+OCSCO+S₂(a¹), S₂(a¹)+MS₂(X³)+M, (13), and 2S₂+MS₄+M(15). Taking the previously published value of k₁₂, computer simulation gave the rate coefficient values k₁₃=6.4±2.4×10⁸ mol^–1 dm³ s^–1 and k₁₅=1.8±0.5×10¹³ mol^–2 dm⁶ s^–1 at 295±3 K.     

Anomalous behavior of radioiodine: Solvent extraction from acidic solution

Anomalous behavior of radioiodine was found in solvent extraction. Iodine was extracted into CS₂ from acidic solution over a wide range of iodine concentration. The distribution ratio was obtained by measuring the -rays from iodine-131. The ratio drastically changed at about 10^–5 mol l^–1. The change is readily explained by the kinetic behavior of radioiodine.     

Spectrophotometric determination of nitrite and nitrate in doped potassium chloride crystals

Summary KCl crystals, doped in the melt with KNO₂ or KNO₃, contain both NO₂ ^– and NO₃ ^– ions. Spectrophotometric methods are described for the determination of the admixture concentration after dissolving the crystals. Nitrite is determined by colorimetry of an azo dye formed in methanol-water-HCl medium from p-nitroaniline and -naphthylamine. The absorption is proportional to the nitrite concentration in the range of 5 · 10^–6 to 5 · 10^–5 M NO₂ ^– UV absorption measurement is employed for the spectrophotometric determination of nitrate, Beer's law being obeyed between 3 · 10^–5 and 3 · 10^–4 M NO₃ ^– at 220 nm. Here, nitrite is removed by adding sulfamic acid, and correction is made for chloride. Some results on nitrite- and nitrate-doped crystals are given.

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Zusammenfassung KCl-Kristalle mit zur Schmelze zugesetztem KNO₂ oder KNO₃ enthalten sowohl NO₂ ^–- wie NO₃ ^–-Ionen. Spektrophotometrische Methoden werden beschrieben zur Bestimmung des Gehaltes dieser Zusätze nach Lösen der Kristalle. Nitrit wird bestimmt durch Colorimetrieren einer Azoverbindung aus p-Nitranilin und -Naphthylamin in einem Methylalkohol-Wasser-Salzsäure-Gemisch. Die Absorption ist dem Nitritgehalt von 5 · 10^–6 bis 5 · 10^–5 m NO₂ ^– proportional. Die UV-Absorption wird zur spektrophotometrischen Bestimmung des Nitrats verwendet. Das Beersche Gesetz ist hier zwischen 3 · 10^–5 und 3 · 10^–4 m NO₃ ^– gÜltig (bei 220 nm). Nitrit wird dabei durch Zusatz von Sulfaminsäure entfernt, und es wird fÜr Chloride korrigiert. Einige Ergebnisse an Kristallen mit Nitrit- bzw. Nitratzusatz werden angefÜhrt.

     

Gas Hydrate Frameworks of Allen's Polyhedra. 2. Frameworks on 3–6 and 3–5–6 Nets

The structure of two classes of water molecule frameworks built up of 5¹²(D), 5¹²6²(T), 5¹²6³(P), and 5¹²6⁴(H) polyhedra is discussed. Polyhedral layers can be distinguished in the frameworks. The centers of the polyhedra belonging to a layer are at the nodes of planar networks consisting of triangular, pentagonal, and hexagonal meshes. The structure of one network determines exclusively the topology of the entire framework. Frameworks on 3–6 nets can be constructed of two types of polyhedral blocks: D₃T₂P₂and D₂T₆. Frameworks on 3–5–6 nets might include both specific blocks and the blocks involved in the frameworks on 3–5 and 3–6 nets. The paper analyzes the structure of frameworks on the nets built as a series of rows, each of these rows being constructed of pentagons or hexagons exclusively. These frameworks are described by the formula (D₃T₂P₂) _x (D₄H₂) _y (D₂T₆) _z , where x 1, y 0, and z 0 (x, y, and z are integers). Since all known frameworks of Allen's polyhedra satisfy this formula, they can be constructed of fragments of gas hydrate lattices with the CS1, CS2, and HS1 structures because they are derivatives of these key structures. Similar frameworks can be constructed of other tetrahedral particles (C, Si, SiO₂, etc.).     

Neutron activation analysis of refractory compounds

Instrumental neutron activation techniques for the determination of 26–36 impurities in MoSi₂, WSi₂, TiB₂, NbB₂, TiC, NbC and SiC with detection limit of 0.1–0.000001 ppm in the range of contents of 100–0.001 ppm have been developed. The determination of this large number of elements was achieved with using complex conditions of irradiation, including varying neutron energy and choosing optimal time parameters. The contents of short-lived radionuclides also have been determined. Self-shielding and disturbance of neutron flux, absorption of -rays were taken into account both with the help of literature data and preliminarily obtained experimental results.     

Reactions of superoxide anion radical with antioxidants and their use in voltammetry

Kinetic parameters were calculated for the electrochemical reduction of oxygen at a glassy-carbon electrode with the generation of superoxide radical anions in a 0.05 M solution of (C₂H₅)₄NI in dimethylformamide in the presence of fat-soluble antioxidants, retinol and -tocopherol. A procedure based on the protonation of the radical anion with antioxidant molecules is proposed for the voltammetric determination of antioxidants to determine milligram amounts of retinol and -tocopherol in model solutions (RSD = 1–2%). The calibration graphs for retinol and -tocopherol are linear in the concentration ranges 9.7 × 10^–5–2.3 × 10^–3 and 6.2 × 10^–4–3.1 × 10^–3 M, respectively. The detection limits for retinol and -tocopherol are 4.8 × 10^–5 and 4.1 × 10 ^–4 M, respectively. The procedure was applied to the determination of the active component (retinol and -tocopherol) in pharmaceuticals.Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 1, 2005, pp. 56–59.Original Russian Text Copyright © 2005 by Ziyatdinova, Gilmetdinova, Budnikov.     

Extraktions-Flammenabsorptionsbestimmung von Spurenverunreinigungen in Salzen

Zusammenfassung Spurenverunreinigungen von Fe, Cu, Pb, Ni, Co, Cd, Zn wurden in KH₂PO₄, KNa-Tartrat, BaCl₂, CaCl₂, Citronensäure, Li₂CO₃, Na₂CO₃, K₂CO₃, BaCO₃ und CaCO₃ durch Flammenatomabsorption nach Extraktionsanreicherung mit Diethylammonium-N,N-diethyldithiocarbamat/MIBK bestimmt. Der Einfluß der Salz-matrix auf die Extraktion und Bestimmung der Elementspuren wurde untersucht. Die Methode erlaubt die Bestimmung von 5 · 10^–6–5 · 10^–7% der Elemente mit guter Präzision und Richtigkeit (rel. Standardabweichung 2–7%).

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Extraction flame atomic-absorption determination of microtraces in salts

Summary The trace content of Fe, Cu, Pb, Ni, Co, Cd, Zn in KH₂PO₄, KNa-tartrate, BaCl₂, CaCl₂, citric acid, Li₂CO₃, Na₂CO₃, K₂CO₃, BaCO₃ and CaCO₃ is determined by flame atomic-absorption spectrometry after preceding preconcentration of the traces using the extraction system diethylammonium-N,N-diethyldithiocarbamate/ MIBK. The influence of the salt matrix on the extraction and determination of the traces was investigated. The method permits the determination of 5·10^–6–5·10^–7% of the elements with good precision and accuracy (relative standard deviation 2–7%).

     

Electrochemical Properties and Analytical Applications of Keggin-type Phosphomolybdic Anions in Electrostatically Linked 2-Aminoethanethiol Self-Assembled Monolayers

A composite film containing a heteropolyanion was prepared on a 2-aminoethanethiol (AT) self-assembled monolayer film-modified gold electrode by attaching the Keggin-type phosphomolybdic anion. The surface structures and electrochemical properties of the composite films were characterized by using ATR-FTIR, AC impedance, cyclic voltammetry and chronocoulometry. FTIR studies indicated that there was some electrostatic interaction between Pmo₁₂O₄₂^7– and surface NH₃⁺. Three reversible redox couples were observed in 1.0molL^–1 H₂SO₄ in the potential range of 0–0.7V for the composite film modified electrode, which were attributed to two-electron and two-proton electrochemical processes of PMo₁₂O₄₂^7–. The diffusion coefficient is determined to be 2.04×10^–7cm²s^–1. The composite film shows good catalytic activities for the reduction of nitrite (NO₂^–) in acidic solution and the catalytic mechanisms are described. The modified electrode provides a linear response for NO₂^– in the concentration range of 1.0×10^–4 to 1.0×10^–7molL^–1 by differential pulse adsorptive stripping voltammetry with a correlation coefficient of 0.9965. The detection limit (three times the signal blank/slope) was 2.0×10^–8molL^–1. The modified electrode was used for the determination of NO₂^– in wastewater.     

Extraction and spectrophotometric determination of uranium in phosphate fertilizers

An extraction and spectrophotometric method for determination of trace amounts of uranium in phosphate fertilizers is described. It is based on the extraction of uranium with trioctylphosphine oxide in benzene and the spectrophotometric determination of uranium with Arsenazo III in buffer-alcoholic medium. The maximum absorbance occurs at 655 nm with a molar absorptivity of 1.2·10⁴ l·mol^–1·cm^–1. Beer's law is obeyed over the range 0.6–15.0 g·ml^–1 of uranium(VI). The proposed method has been applied successfully to the analysis of phosphate fertilizers with phosphate concentrations of 45% P₂O₅.     

Ion-pair adsorption film colorimetry of iron (III) in water samples and human serum

The anionic chelate of iron(III)-2,2-dihydroxyazobenzene (H₂L), [FeL₂]^–, formed 1 1 ion-pair with crystal violet cation (CV⁺), CV⁺ [FeL₂]^–, and was adsorbed on a surface of transparent polyvinyl chloride (PVC) film plasticized with di-n-octyl phthalate. Enrichment of the blue violet species of the ion-pair onto the transparent PVC film has enabled a highly sensitive and simple method for the determination of iron(III). The detection limits are 1 × 10^–8 mol dm^–3 (0.6 ppb) by spectrophotometry at 592 nm, and 4 × 10^–8 mol dm^–3 (2 ppb) by visual colorimetry. The method has been successfully applied to the determination of iron in water samples and human serum. No preparatory procedures for the separation of serum protein and other coexisting substances are required, since ion-pair adsorption process provides a new method to prevent interference of serum matrix.     

Molecular complex of C60 fullerene with an organic π-donor,bis(methylenedithiotetrathiafulvalene): synthesis,crystal structures,and properties

A new molecular complex based on [60]fullerene, namely, (BMDT-TTF)·C₆₀·2CS₂ (1) (where BMDT-TTF is bis(methylenedithiotetrathiafulvalene)) was synthesized. The molecular and crystal structures of 1 were established by X-ray diffraction analysis. Complex 1 has a layered structure, layers of C₆₀ molecules alternating with those formed by BMDT-TTF molecules and CS₂ molecules located between them. In complex 1, there are short contacts between C₆₀ and the donor molecules, which results in a changed BMDT-TTF geometry. The donor molecules in 1 form in addition short S...S contacts. The data of IR spectroscopy indicate that the charge transfer to the fullerene molecule is insignificant if at all present. The conductivity of a single crystal of 1 measured at 20 °C using a four-contact method is 2·10^–5 ( cm)^–1.     

Simultaneous measurements of formaldehyde and ozone in air by annular denuder-HPLC techniques

Summary A denuder sampling method combined with HPLC analysis for the simultaneous determination of formaldehyde and ozone in ambient air is described. It is based on the reactions of CH₂O and O₃ with 2,4-dinitrophenylhydrazine (DNPH) and 4-allyl-2-methoxyphenol (eugenol)_respectively, both acting as coatings of two annular denuders connected in series. Formaldehyde released from the ozonolysis of eugenol is quantitatively collected on a third downstream DNPH-coated denuder. The two DNPH denuders are then extracted and analyzed as hydrazone derivative by HPLC with UV absorbance detection.The stoichiometric factor of the eugenol-ozone reaction was found to be 2.0±0.1 moles of O₃ per mole of CH₂O. The limits of detection are 0.8gm^–3 CH₂O and 3gm^–3 O₃ for 100l air sampled, corresponding to 1-h sampling at 1.7l min^–1.     

Rapid radiochemical separation and determination of chlorine,bromine and iodine in water samples using ion exchange

On the basis of tracer experiments, a simple and rapid radiochemical separation method for simultaneous determination of I^–, Br^– and Cl^– in one aliquot of a water sample (only 2–4 ml) has been developed. The method is based on short irradiation of the water sample and separation of the halogens using sequential ion exchange columns filled with Dowex 1×8, 100–200 mesh anionic resin prepared in I^–/I₂, Br^–/Br₂ and Cl^– form. After washing the columns with an appropriate volume of 2% NaCl solution, the resins were transferred to vials and activities of the isolated radionuclides¹²⁸I,⁸²Br and³⁸Cl measured together with standards in a well type or on a coaxial Ge detector connected to a Canberra 90 multichannel analyzer. Besides high chemical yields, from the -spectra of the isolated radionuclides, it is evident that high decontamination fac-The paper was presented at the MTAA-8, Vienna, September 1991.     

Spectrophotometric determination of 1-naphthylamine in urine with pentacyanonitrosylmanganate (II)

A new Spectrophotometric method is proposed for the determination of 1-naphthylamine (R), based on its reaction with Mn(CN)₅NO^2– to form Mn(CN)₅NH₂R^3– and measurement of the absorbance at 472 nm. In aqueous medium the molar absorptivity of the manganese complex is maximum ( = 8.0 × 10³1 · mole^–1 ·cm^–1) in the pH range 5.0–10.0, the colour develops more rapidly at pH 10.0. The absorptivity is increased by a factor of 3.5 if the complex is extracted as an ion-associate into chloroform. The extraction efficiency is 99.2% for a single-step extraction, and a concentration factor of 5 can also be achieved. Linearity of response extends over the range 0.04–1.4 gmg/ml 1-naphthylamine, the coefficient of variation being 1.4% at the 0.29 g/ml level (n = 6). The detection and determination limits are 0.005 and 0.018 g/ml, respectively. The method is selective enough to allow the determination of 1-naphthylamine in the presence of considerable amounts of other amines, such as aminophenols and phenylenediamines. Results obtained in the determination of 1-naphthylamine in human urine were very satisfactory.