Low-temperature decomposition of methanol on Au nanoclusters supported on a thin film of Al2O3/NiAl100

With a variety of surface probe techniques, we investigated low-temperature decomposition of methanol on Au nanoclusters formed by vapor deposition onto an ordered Al(2)O(3)/NiAl(100) thin film. Upon adsorption of methanol on the Au clusters (with mean diameter 1.5-3.8 nm and height 0.45-0.85 nm) at 110 K, some of the adsorbed methanol dehydrogenates directly into carbon monoxide (CO); the produced hydrogen atoms (H) begin to desorb near 125 K whereas most of the CO desorbs above 240 K. The reaction exhibits a significant dependence on the Au coverage: the produced CO increases in quantity with the Au coverage, reaches a maximum at about 1.0-1.5 ML Au, whereas decreases with further increase of the Au coverage. The coverage-dependence is rationalized partly by an altered number of reactive sites associated with low-coordinated Au in the clusters. At least two kinds of reactive sites for the low-temperature decomposition are distinguished through distinct C-O stretching frequencies (2050 cm(-1) and 2092 cm(-1)) while the produced CO co-adsorbs with H and methanol.     

Aging of Fe−Al thin film multilayers

Multilayers constituted by very thin films of Fe and Al, deposited by thermal evaporation and magnetron sputtering techniques and then aged in air at temperatures in the 300–400 K range for times up to 200 h, were analyzed by means of XRD, CEMS, XPS and AES measurements. Fe(Al) solid solutions form during evaporation because of interdiffusion phenomena at the Fe–Al interfaces, while Al undergoes oxidation during sputtering deposition and, consequently, the multilayers are constituted by Fe intercalated with Al₂O₃ films. Aging treatments in oxidizing environments induce no significant modification in sputtered multilayers while, on the contrary, the evaporated multilayers show the effects of both interdiffusion and oxidation phenomena.     

Polyaniline-silica doped with oxalic acid as a novel extractor phase in thin film solid-phase microextraction for determination of hormones in urine

In this study, different polyanilines were synthesized and evaluated for the determination of three hormones, including 17-β-estradiol, 17-α-ethinylestradiol, and estrone, in urine using a novel methodology based on thin film solid-phase microextraction technique, employing the sampling well plate system. The extractor phases, designated as polyaniline doped with hydrochloric acid, polyaniline doped with oxalic acid, polyaniline-silica doped with hydrochloric acid, and polyaniline-silica doped with oxalic acid, were characterized by electrical conductivity measurements, scanning electron microscopy, and Fourier transform infrared spectroscopy. The optimized extraction conditions were composed of 1.5 mL of urine and pH adjusted to 10, with no need to dilute sample and the desorption step, 300 μL of acetonitrile was used. The calibration curves were performed in the sample matrix, with detection and quantification limits ranged from 0.30 to 3.03 μg L⁻¹ and from 1.0 to 10.0 μg L⁻¹, respectively, with r ≥ 0.9969. The relative recoveries ranged from 71% to 115%, and intraday precision showed values ≤12% and interday ≤20%. The applicability of the method was successfully evaluated, and six urine samples from female volunteers were analyzed. The analytes were not detected or were below the limits of quantification in these samples.     

草酸电还原制取乙醛酸的研究

研究了由草酸电解还原制备乙醛酸时，温度、草酸纯度、电解时间、电极状态和电解产物对电流效率和产率的影响。实验发现，除温度和原料纯度是重要的影响因素外，电极表面的有机物吸附和电解产物－乙醛酸的浓度具有更大的影响。     

Transesterification of oxalic acid esters

Conclusions Transesterification of some lower oxalate esters with alcohols in the presence of acidic or basic catalysts gave the corresponding higher esters in good yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1102–1105, May, 1968.     

Cation-exchange in oxalic acid-nitric acid media

Summary The adsorption behaviour of 16 elements on the strongly acidic cation-exchange resin AG 50W, X-8 has been examined in mixed oxalic-nitric acid media. The distribution coefficients are presented as a function of nitric acid concentration (0.13.0 M) in 0.05 M oxalic acid solution. There are marked differences in adsorbability between terand quadrivalent metal and bivalent metal groups. The system can be applied to the multielement analysis of manganese nodules for iron, zinc, copper, cobalt, manganese and nickel, coupled with chromatographic elution of bivalent metals with mineral acid-organic solvent mixtures. The versatility of the system is also demonstrated by the analysis of a biological standard reference material, pepperbush, of NIES for the same six elements. The results are in good agreement with the certified values (NIES: National Institute for Environmental Studies, Japan Environment Agency).

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Kationenaustausch in Oxalsäure-Salpetersäure-LösungAnalytische Anwendung zur Bestimmung von sechs Spurenelementen in Manganknollen und Pflanzenmaterial

Zusammenfassung Das Adsorptionsverhalten von 16 Elementen an dem stark sauren Kationenaustauscher AG 50W, X-8 wurde in Oxalsäure-Salpetersäure-Gemischen untersucht. Die Verteilungskoeffizienten werden angegeben als Funktion der Salpetersäurekonzentration (0,13,0 M) in 0,05 M Oxalsäure. Die Adsorbierbarkeit der drei- und viersowie zweiwertigen Metallionen weist deutliche Unterschiede auf. Das Verfahren kann zur Multielementanalyse von Manganknollen auf Fe, Zn, Cu, Co, Mn und Ni angewendet werden. Die Elution der zweiwertigen Metallionen erfolgt mit Gemischen von Mineralsäuren und organischen Lösungsmitteln. Die Vielseitigkeit der Methode wird durch die Analyse eines biologischen Referenzmaterials (Pepperbush, NIES) demonstriert. Die Ergebnisse stimmten mit den zertifizierten Werten gut überein.

     

Decomposition of oxalic acid with nitric acid

Oxalic acid or oxalate is widely used as a precipitant and a detergent in the field of nuclear energy. The present work aimed at developing a method of decomposing oxalic acid with HNO₃ in the presence of Mn²⁺ ion. The use of Mn²⁺ ion as low as 10^?3 mol/l facilitated the complete decomposition of oxalic acid, and the acidity of the resulting solution became as low as 0.1 eq/1 under the optimum conditions. The decomposition of oxalic acid is a first order reaction and proceeds at temperatures above 80°C; the activation energy of the reaction is 18.6 kcal/mol. This decomposition method is applicable to the dissolution of an oxalate precipitate.     

On the decarboxylation of oxalic acid in solutions

The first-order kinetics and hydrogen kinetic isotope effect of the decarboxylation of oxalic acid in acetophenone were studied in the temperature range of 109.6°–150.0°C. The rate constants, activation parameters, and hydrogen kinetic isotope effect were calculated. Detailed comparison and discussion of the results were made with the data reported in the literature. Kinetic isotope effects and solvent effects on rates should be considered similar in mechanistic and/or theoretical studies in the sense that kinetic isotope effects result from a small perturbation of the reaction coordinate, while the solvent effect causes a general overall variation on the potential energy surface (thereby resulting in a change in the reaction coordinate).     

Interactions of oxalic acid and ice on Cu surface

The interactions between oxalic acid (C 2H 2O 4) and H 2O on a polycrystalline Cu surface have been investigated by reflection-absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) methods. The desorption of H 2O and C 2H 2O 4 was studied; we found that the ice desorption temperature increases with the ice-film thickness. Desorption of the C 2H 2O 4 layer involves a structural modification and sublimation. The H 2O/C 2H 2O 4 and C 2H 2O 4/H 2O interfaces and the codeposited C 2H 2O 4+H 2O were prepared on the Cu surface by varying deposition sequences of gaseous C 2H 2O 4 and H 2O at 155 K. We found that the interaction between ice and C 2H 2O 4 does not lead to the H 2O-induced deprotonation of C 2H 2O 4 in a temperature range 155-283 K. However, H-bonding interactions between H 2O and C 2H 2O 4 can lead to the formation of a metastable oxalic acid-ice complex in the C 2H 2O 4/H 2O and C 2H 2O 4+H 2O systems during the TPD process. Desorption of H 2O from the C 2H 2O 4/H 2O/Cu system is suggested to involve the diffusion of H 2O through the top C 2H 2O 4 layer. H 2O desorption is followed by a rearrangement of C 2H 2O 4 to form a C 2H 2O 4 adlayer on Cu in the C 2H 2O 4+H 2O system. These experimental findings suggest that C 2H 2O 4 is not ionized on snow and ice in the polar boundary layer and at upper tropospheric temperatures ( approximately 240 K).     

Infrared matrix-isolation spectra of monomeric oxalic acid

Infrared spectra of monomeric oxalic acid-h₂, -hd and -d₂ have been observed using neon matrix-isolation spectroscopy. In addition, spectra of oxalic acid-h₂, vapor were obtained using a heated absorption cell with a 10 m pathlength. All IR active fundamentals are assigned for oxalic acid-h₂, and -d₂, except the low frequency torsion. The spectra are interpreted in terms of the C_2h intramolecularly hydrogen bonded model. Two vibrational assignments are discussed; one involves a very large intensity for the v₈ + v₁₁ (COH torsion) combination band of oxalic acid-h₂. Tentative values for several Raman active fundamentals of oxalic acid-h₂ are suggested using possible combination bands. Few fundamentals of oxalic acid-hd correlating with the Raman modes of the symmetric monomers could be observed. A force constant analysis of the by secular block is presented.     

The influence of the oxide film on the current in AlAl oxide—fatty acid monolayer—metal junctions

For Al-Al oxide-fatty acid monolayer-Pb (or Al) junctions, a broad peak is found in the d In (I/V)/dV versus V curves at | V | ≈ 80 mV. The observation can be shown to arise from the oxide film and is tentatively interpreted in terms of impurity-assisted tunnelling in the highly-contaminated Al oxide film.     

氧化锌薄膜的可控浸润性研究

采用一步电沉积的方法在导电玻璃基底上制备了具有粗糙表面的氧 化锌薄膜．用SEM和XPS表征了薄膜的表面形貌和化学组成,用接触角测定仪 测定接触角以评估薄膜的浸润性．结果显示,薄膜表面布满了无序生长的花瓣状 的微晶,形成疏松的结构．薄膜与水的接触角为133．2°,呈现了疏水的性质．通 过紫外光照射的方法可以使其由疏水性薄膜转化为亲水性薄膜,接触角降低到 4．8°。     

Spectrophotometric determination of oxalic acid in presence of glyoxylic acid and chloride

Glyoxylic acid gives a yellow 1:1 complex, [FeCHOCOO]²⁺ with iron(III). The dissociation contant, measured by two spectrophotometric methods, is K = 9.7 ± 1 mol l^?1. Oxalic acid gives two complexes with iron(III) which absorb in the same range around 400 nm. With appropriate precautions and corrections, oxalic acid concentrations of about 10^?1–10^?2 M can be determined in the presence of glyoxylic acid and chloride.     

A novel molecularly imprinted polymer thin film as biosensor for uric acid

A novel amine-imide type conducting polymer, denoted as poly(PD-BCD), was molecularly imprinted on an indium-tin oxide (ITO) glass, with uric acid (UA) as the template and without any functional monomer. Intending to improve the imprinting efficiency, the polymer content was varied from 0.3 to 0.9 wt% during the preparation of the molecularly imprinted polymer (MIP), thereby varying the thickness of the polymer film; the content of UA as the template was maintained to be the same for all the films. The sensitivities of the thus prepared MIP electrodes were calculated to be more than 3-fold, compared to those of the corresponding non-MIP (NMIP) electrodes, which were obtained through the same method, however, without adding UA during their preparation. A polymer content of 0.6 wt% rendered the best performing MIP electrode, as judged by the imprinting efficiency and sensitivity of the electrode for UA. A linear relationship between steady-state currents and UA concentrations from 0 to 1.125 mM was obtained for both types of the sensors. The sensitivities of the MIP and the NMIP electrodes made with 0.6 wt% of polymer were calculated to be 24.72 and 6.63 μA mM⁻¹ cm⁻², respectively. The limit of detection (LOD) for this MIP was found to be 0.3 μM at a signal to noise ratio (S/N) of 3. This MIP electrode was used as a biosensor for the detection of UA in the presence of ascorbic acid (AA) in a sample containing these species in the same concentrations as those in a human serum. The selectivity of MIP electrode is higher than that of NMIP electrode, and the values are 28.76 and 8.85, respectively. The results are substantiated by using cyclic voltammetry (CV), linear sweep voltammetry, amperometry, and scanning electron microscopy.     

Influence of the adsorption on the oxidation of oxalic acid on a gold electrode in acid media

Summary The influence of an adsorption process on the oxidation of oxalic acid on a gold electrode has been analysed. To disclose this influence, different supporting electrolytes have been used with different adsorption of the anion (SO ₄ ^2– , NO ₃ ^– and ClO ₄ ^– ). Moreover, it has been studied the modifications produced in the oxidation process by the presence of some species in solution with a strong adsorption (halides), but at low concentration levels.

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Der Einfluß der Adsorption auf die Oxidation von Oxalsäure an der Goldelektrode in saurem Medium

Zusammenfassung Um den Einfluß der Adsorption auf die Oxidation von Oxalsäure an der Goldelektrode in saurem Medium zu untersuchen, wurden Support-Elektrolyten mit verschiedener Anionenadsorption verwendet (SO ₄ ^2– , NO ₃ ^– und ClO ₄ ^– ). Außerdem wurden Modifikationen des Oxidationsprozesses in der Gegenwart von stark adsorbierten Spezies, diese allerdings in geringen Konzentrationen, untersucht (Halogenide).

     

Thermal analysis of hydroxyapatite with adsorbed oxalic acid

Journal of Thermal Analysis and Calorimetry - The specific adsorption of oxalic acid ions at the hydroxyapatite interface was investigated by means of the radioisotope method (14C) as a function of...     

Synthesis of oligoesters from oxalic acid and glycerol

A new synthesis for the polycondensation of oxalic acid and glycerol was used. Polycondensation was carried out in the presence of compounds that do not dissolve oxalic acid and glycerol, but form an azeotropic mixture with water below 100°C. Anhydrous oxalic acid and oxalic acid dihydrate was used for the synthesis of oligoesters. The decarboxylation proceeds parallel with polycondensation of oxalic acid and glycerol was investigated. Decarboxylation of carboxyl groups of glycerol monooxalate was found to be accelerated by the arrangement of primary and secondary hydroxyl groups in the glycerol molecule in the 1,2 position.     

Regularities of electrolytic dissociation of oxalic acid homologues

Using a method proposed earlier by the authors, the degrees of dissociation in individual steps (including the “partial” degrees of dissociation in the second steps) and the concentrations of ionized and nonionized forms in dilute (0.1–10 mM) solutions are calculated for eight homologues of oxalic acids, namely, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, and sebacic. Simple empirical equations general for this series were proposed for approximate calculating the first and the second degrees of dissociation and the pH in dilute solutions of these acids.