Open Access Published by De Gruyter Open Access

Volume 12 Issue 2

February 2014

Issue of Open Chemistry

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Open Access November 27, 2013

Oxygen decorating at the one ring and at the N-mouth of (10, 0) aluminum nitride nanotube: A DFT investigation

Ahmad Seif, Lila Torkashavand, Fatemeh Mohammadi

Page range: 131-139

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Abstract

We have investigated oxygen decorating in the (10, 0) aluminum nitride nanotube (AlNNT) by density functional theory. Band gaps, total (TDOS) and partial (PDOS) densities of state and chemical-shielding isotropic (CSI) and chemical-shielding anisotropic (CSA) have been calculated or determined in three models of the investigated (10, 0) AlNNT: pristine (model.0), O-decorating at the one ring in the middle of AlNNT (Model.1) and O-decorating at the nitrogen mouth of AlNNT (Model.2). The results indicated that the dipole moment does not detect the significant effects of dopant whereas TDOS, PDOS and band gap energies detect notable effects. The CSI and CSA values for the Al and N atoms-contributed to the Al-O bonds or those atoms close to the decorated region, in both models of O-decorated AlNNTs are changed.

Open Access November 27, 2013

Physical-chemical transformations in the system V2O5/(NH4)2Mo2O7 under hydrothermal conditions

Svitlana Khalameida, Volodymyr Sydorchuk, Roman Leboda, Jadwiga Skubiszewska-Zięba, Valery Zazhigalov

Page range: 140-152

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Abstract

Modified compositions in the system V2O5/(NH4)2Mo2O7 have been prepared by means of mechanochemical, hydrothermal, microwave and ultrasonic treatments in aqueous medium. Chemical and phase transformations occurring on the stages of modification and following calcinations have been studied with the help of XRD, DTA-TG, FTIR and UV-Vis spectroscopy, nitrogen adsorption, and SEM. It has been established that precursors of catalytically active phases possessing meso-macroporous structure have been formed during modification. The comparison of the properties of compositions prepared via different methods has been carried out. Particularly, precursors modified via various procedures possess different morphology.

Open Access November 27, 2013

DFT calculation and assignment of vibrational spectra of aryl and alkyl chlorophosphates

Viktor Anishchenko, Vladimir Rybachenko, Konstantin Chotiy, Andrey Redko

Page range: 153-163

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Abstract

DFT calculations of vibrational spectra of chlorophosphates using wide range of basis sets and hybrid functionals were performed. Good agreement between calculated and experimental vibrational spectra was reached by the combination of non-empirical functional PBE0 with both middle and large basis sets. The frequencies of the stretching vibrations of the phosphate group calculated using semi-empirical functional B3LYP for all basis sets deviate significantly from the experimental values. The number of polarization functions on heavy atoms was shown to be a key factor for the calculation of vibrational frequencies of organophosphates. The importance of consideration of all the stable rotamers for a complete assignment of fundamental modes was shown.

Open Access November 27, 2013

Application of Box-Behnken design with response surface methodology for modeling and optimizing ultrasonic oxidation of arsenite with H2O2

Pengpeng Qiu, Mingcan Cui, Kyounglim Kang, Beomguk Park, Yonggyu Son, Eunkyung Khim, Min Jang, Jeehyeong Khim

Page range: 164-172

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Abstract

A combined ultrasound (US)/H2O2 process was used to oxidize arsenite to arsenate, yielding a synergistic effect value of 1.26. This showed that the combined process could be an effective method of oxidizing arsenite, instead of using either ultrasonic or H2O2 oxidation processes. This combined process was successfully modeled and optimized using a Box-Behnken design with response surface methodology (RSM). The effects of the US power density, the initial concentration of arsenite, and the H2O2 concentration on the sonochemical oxidation efficiency of arsenite were investigated. Analysis of variance indicated that the proposed quadratic model successfully interpreted the experimental data with coefficients of determination of R 2 = 0.95 and adjusted R 2 = 0.91. Through this model, we can predict and control the oxidation efficiency under different conditions. Furthermore, the optimal conditions for the oxidation of arsenite were found to be a US power density of 233.26 W L−1, an initial arsenite concentration of 0.5 mg L−1, and an H2O2 concentration of 74.29 mg L−1. The predicted oxidation efficiency obtained from the RSM under the optimal conditions was 88.95%. A confirmation test of the optimal conditions verified the validity of the model, yielding an oxidation efficiency of 90.1%.

Open Access November 27, 2013

Silica synthesis by the sol-gel method and its use in the preparation of multifunctional biocomposites

Łukasz Klapiszewski, Michał Królak, Teofil Jesionowski

Page range: 173-184

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Abstract

This study focuses on the optimization process of silica synthesis using the sol-gel method while applying a statistical design of experiments which was based on a multilevel mathematical model. The product obtained in the process of optimized synthesis, characterized by the best dispersive and morphological parameters, was used for the preparation of organic/inorganic composites. The organic precursor was Kraft lignin, a high-molecular natural polymer. Synthesis of silica/lignin biocomposites was carried out by three proposed methods. The physicochemical properties and dispersive-morphological properties of each product were determined using the following available methods: Scanning Electron Microscopy — SEM, Non-Invasive Back-Scattering — NIBS, Fourier Transform Infrared Spectroscopy — FT-IR, Thermogravimetric analysis — TG and others. The electrokinetic and thermal properties of the biocomposites sufficed to be applied for example, as a cheap and biodegradable polymer filler. Further areas of application of these composites were sought, especially in electrochemistry as the advanced electrode materials.

Open Access November 27, 2013

Application of NRTL activity coefficient model to describe the kinetics of gas adsorption

Krzysztof Nieszporek, Tomasz Banach, Przemywslaw Podkościelny

Page range: 185-193

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Abstract

The Non-Random Two-Liquid activity coefficient model is applied to describe the kinetics of pure gas adsorption on energetically heterogeneous solid surfaces. The surface energetic heterogeneity has been represented by the Gaussian-like function of the adsorption energy distribution. Two different kinetic isotherms have been presented. One of them, determined by using the statistical rate theory, has been critically discussed. The applicability of the presented approach has been demonstrated by a quantitative analysis of two sets of experimental data previously reported in the literature.

Open Access November 27, 2013

Determination of iron by Z-GFAAS and the influence of short-term precision and long-term precision

Jens Andersen

Page range: 194-205

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Abstract

A detailed method validation of graphite-furnace atomic absorption spectrometry (GFAAS) with Zeeman background correction was performed. The aim is to perform a detailed investigation of short-term precision as opposed to long-term precision. It was suggested that release of graphite flakes into the light path during measurement significantly influenced the performance of the method. It was found that significant deviations with respect to the certified values were frequent and an estimate of reliable uncertainties was obtained only after a high number of repetitions. Uncertainty of Interlaboratory testing was evaluated as a method to estimate uncertainties that are comparable to uncertainties that were obtained by Interlaboratory testing and to uncertainties predicted by the Horwitz curve. To a large extent, the uncertainty in measurement that was predicted by pooled calibrations corresponded to the uncertainties that were obtained from multiple determinations of unknowns. It was thus proposed that a large proportion of the difference in uncertainty in measurement between laboratories could be explained by properties of the different detectors. In order to support accuracy, it is suggested that a higher level of uncertainty should be accepted in analytical investigations.

Open Access November 27, 2013

Promoted ternary CuO-ZrO2-Al2O3 catalysts for methanol synthesis

Paweł Mierczynski, Piotr Kaczorowski, Agnieszka Ura, Waldemar Maniukiewicz, Marcin Zaborowski, Radoslaw Ciesielski, Adam Kedziora, Tomasz Maniecki

Page range: 206-212

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Abstract

Ternary CuO-ZrO2-Al2O3 catalysts promoted by palladium or gold were prepared and tested in CO hydrogenation reaction at 260°C under elevated pressure (4.8 MPa). The promotion effect of palladium or gold addition on the physicochemical and catalytical properties of CuO-ZrO2-Al2O3 catalysts in methanol synthesis (MS) was studied. The catalysts were characterized by BET, XRD, TPR-H2, TPD-NH3 methods. The BET results showed that the ternary system CuO-ZrO2-Al2O3 had the largest specific surface area, cumulative pore volume and average pore size in comparison with the promoted catalysts. The yield of methanol can be given through the following sequence: 5%Pd/CuO-ZrO2-Al2O3 > CuO-ZrO2-Al2O3 > 2%Au/CuO-ZrO2-Al2O3. We also found that the presence of gold or palladium on catalyst surface has strong influence on the reaction selectivity. The high selectivity of gold doped ternary catalyst is explained by the gold-oxide interface sites created on the catalyst surface and the acidity of those systems. The higher selectivity to methanol in the case of the palladium catalyst is explained by the spillover effect between Pd and CuO.

Open Access November 27, 2013

Influence of temperature on the reduction kinetics of Bi(III) ion in the presence of cystine in chlorate (VII) solutions of decreased water activity

Agnieszka Nosal-Wiercińska

Page range: 213-219

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Abstract

The results of the kinetic measurements of Bi(III) electroreduction on a mercury electrode in 1–8 mol dm−3 chlorate (VII) solutions and in the presence of cystine demonstrate a dependence of the process on the temperature. The applied electrochemical techniques (DC polarography, cyclic and SWV voltammetry) allowed for the determination of the kinetic and thermodynamic parameters and their correlation with water activity. The catalytic activity of cystine was confirmed by the decrease in overall enthalpies of activation. The changes in the values of ΔH ≠ and ΔS 0 for Bi(III) electroreduction in the presence of cystine with the increase of chlorate (VII) concentration showed that the mechanism is different in solutions with low water activity as compared to those with high water activity. Probably it is connected with a different structure of the activated complexes (Bi-Hg(SR)2), mediating electron transfer.

Open Access November 27, 2013

The synthesis, structure and physical properties of lanthanide(III) complexes with nicotinic acid

Nuša Hojnik, Matjaž Kristl, Amalija Golobič, Zvonko Jagličić, Miha Drofenik

Page range: 220-226

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Abstract

This article reports the synthesis of novel, rare-earth coordination complexes with nicotinic acid. Three compounds with the general formula Ln2[(C5H4NCOO)6(H2O)4] (Ln = Yb, 1; Ln = Gd, 2; Ln = Nd, 3) were prepared from relatively cheap and readily available reactants. Their compositions and structure were characterized by IR spectroscopy and single-crystal X-ray diffraction. The magnetic and thermogravimetric properties were also studied. The complexes consist of centrosymetric, dimeric molecules having all six nicotinato ligands coordinated with the central atom in the bidentate mode. The coordination environment of the Ln3+ for all three compounds is 8. Here we describe the crystal structure of Yb and Gd complexes with nicotinic acid.

Open Access November 27, 2013

The crystal structure of Sm4Ni11In20 and its relation to other indium-rich compounds

Yuriy Tyvanchuk, Volodymyr Svitlyk, Mykola Pustovoychenko, Yaroslav Kalychak

Page range: 227-232

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Abstract

Polycrystalline Sm4Ni11In20 was obtained by arc-melting of metal ingots. A subsequent high temperature treatment was used for single crystal growth. The Sm4Ni11In20 crystal structure (U4Ni11Ga20 type; C2/m, a = 22.5457(3) Å, b = 4.34929(5) Å, c = 16.5479(2) Å, β = 124.592(2)°, R1 = 0.0358, wR2 = 0.0934) was determined by single crystal synchrotron radiation X-ray diffraction from 2014 independent reflections with I > 2σ(I). Sm4Ni11In20 extends the R 4Ni11In20 (R = Y, Gd, Tb, Dy, Ho) series of phases. The R 4Ni11In20 and RNi3In6 (LaNi3In6 type; R = La, Ce, Pr, Nd, Eu) series have similar compositions. Their structures share similar fragments; in particular the rare earth atom coordination polyhedra are pentagonal prisms with additional atoms.

Open Access November 27, 2013

Adsorption studies and release of selected dyes from functionalized mesoporous MCM-41 silica

Dawid Lewandowski, Anna Olejnik, Grzegorz Schroeder

Page range: 233-241

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Abstract

Functionalized mesoporous MCM-41 silica was subjected to adsorption and release studies of encapsulated guest molecules of three chosen dyes. These mesoporous systems were composed of three different capping reagents introduced by grafting method on the silica surface to control the release of dye molecules at two different pH values. The amounts of dyes adsorbed on the silica surface were measured using ultraviolet-visible (UV-VIS) spectrophotometry. The efficiency of grafting was calculated on the basis of differential thermal analysis (TG) results and elemental analysis. The release profiles were determined for all obtained systems using USP Dissolution Apparatus 2. Adsorption of the two azo dyes used was the most efficient after the positively charged functionalization and lower after functionalization with neutral and negatively charged capping reagents, while the phthalocyanine dye adsorption was almost functionalization-independent. Grafting efficiency was the highest for neutral capping reagent and much lower for electrically charged molecules of other reagents. Release studies showed clearly that desorption was pH-dependent for azo dyes and pH independent for Alcian Blue. The adsorption and release seem to be connected with the electrical charge of all constituents of these systems. Results obtained can be used for further analysis of different electrically charged molecules.

Open Access November 27, 2013

Ultrafiltration of oil-in-water emulsion by using ceramic membrane: Taguchi experimental design approach

Jania Milić, Irena Petrinić, Andreja Goršek, Marjana Simonič

Page range: 242-249

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Abstract

In this study, a Taguchi experimental design methodology was used to determine the importance of process parameters influencing the ultrafiltration (UF) of oil-in-water emulsions. Four parameters including pH (5–11), oil concentration (φ) (0.5–3% (v/v)), temperature (T) (25–45°C) and trans-membrane pressure (TMP) (1–5 bar) were studied at three levels. The highest flux was used as optimization criterion. In order to reduce the number of experiments, a Taguchi method was applied. Analysis of variance (ANOVA) was used to determine the most significant parameters affecting the optimization criterion. Filtration experiments were performed in a cross-flow operation at a total recycle condition in a laboratory-scale plant. The ceramic UF membrane with a pore size of 50 nm was employed in a tubular module with an active area of 0,418 m2. We used water-soluble cutting oil mixed with water as a model oil-in-water emulsion. During the experiment, the drop size and zeta potential distributions were evaluated. The optimum conditions for UF providing the highest flux were found at TMP = 5 bar, pH = 7, and φ = 0.5 v/v%. The pH of emulsion had the highest impact on COD retention. The results of this study could be used as a guideline for operating UF systems with ceramic membranes at optimal conditions.

Open Access November 27, 2013

Copper-cobalt ferrites as catalysts for methanol decomposition

Nikolay Velinov, Kremena Koleva, Tanya Tsoncheva, Daniela Paneva, Elina Manova, Krassimir Tenchev, Boris Kunev, Izabela Genova, Ivan Mitov

Page range: 250-259

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Abstract

Copper-cobalt ferrites with composition Cu1−xCoxFe2O4, where x= 0.2 and 0.8 were prepared by thermal treatment of co-precipitated precursor. The obtained materials were characterized by TG-DSC, XRD, Transmission and Conversion Electron Mössbauer spectroscopy and temperature programmed reduction with hydrogen. The catalytic properties of ferrites were tested in methanol decomposition to CO and hydrogen.

Open Access November 27, 2013

Effect of oxidation of nitride coatings on corrosion properties of Ti-6Al-4V alloy in 0.9% NaCl at 40°C

Iryna Pohrelyuk, Oleh Tkachuk, Roman Proskurnyak

Page range: 260-265

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Abstract

The corrosion properties of Ti-6Al-4V alloy with oxidized thermodiffusion nitride coatings were investigated in isotonic 0.9% solution of NaCl at temperature of 40°C. It was shown that modification of nitride coatings by oxygen leads to a deterioration of the protective properties of nitrided surface of Ti-6Al-4V alloy. The protective properties of the alloy with nitride coatings modified by oxygen are determined by the composition of formed surface oxynitride film.

Open Access November 27, 2013

Cooligomerization of dominant monomers of C9 fraction of liquid pyrolysis products: comparison of heterogeneous catalytic approach with common methods

Taras Voronchak, Irena Nykulyshyn, Zorian Pikh, Anna Rypka, Zoriana Gnativ

Page range: 266-280

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Abstract

Cooligomerization of liquid products of the C9 fraction of diesel fuel pyrolysis to produce cooligomers of wide application is suggested to be carried out with silica-alumina catalysts, among which the activated bentonite clay seems to be optimal. Cooligomerization of the mixture simulating the C9 fraction composition was studied to compare the suggested heterogeneous catalytic method with other methods of cooligomers production. Different methods have been compared in terms of yield of cooligomers and their properties, namely molecular weight and its distribution, density, unsaturation and colour. The ratio of monomer units in cooligomer has been determined and the monomers conversion degrees have been calculated for different cooligomerization methods. Reasons of structure and composition differences of cooligomers obtained by different methods are suggested.

Open Access November 27, 2013

Erratum to: “Current uses and trends in catalytic isomerization, alkylation and etherification processes to improve gasoline quality”

José Hidalgo, Michal Zbuzek, Radek Černý, Petr Jíša

Page range: 281-281

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Abstract

The original version of the article was published in Cent. Eur. J. Chem. 12(1) (2014) pp. 1–13. Unfortunately, the original version of this article contains some mistakes in the text: The caption of Figure 7. A fixed bed unit converted to the UOP Par-Isom Process™Par Isom Process should be written as Par-Isom Process™everywhere in the text LCC should be written as LLC

About this journal

Open Chemistry is a peer-reviewed open access journal that publishes original research, reviews, and communications in the fields of chemistry in an ongoing way. Our central goal is to provide a hub for researchers working across all subjects to present their discoveries, and to be a forum for the discussion of the important issues in the field.

Aims and Scope

Open Chemistry aims to publish high quality research in the following areas:

Biological Chemistry/Biochemistry including bioanalytical chemistry, biochemistry and biological chemistry, biophysics and chemical physics in biology

Analytical Chemistry including electrochemistry, environmental chemistry, spectroscopy
Physical Chemistry including catalysis, chemical kinetics and reactivity, chemical physics, computational chemistry, chemometrics and QSAR, hydrogen technologies, hydrogen storage, nanochemistry, photochemistry, physical chemistry and physical organic chemistry, radiochemistry and nuclear chemistry, supramolecular chemistry, surface chemistry and colloids, theoretical chemistry, thermodynamics
Inorganic Chemistry including coordination chemistry, crystallography, materials and solid- state chemistry
Organic Chemistry including macromolecules and polymers, natural product chemistry, organic chemistry, organometallic chemistry, phytochemistry
Interference with other sciences including clinical chemistry, marine chemistry, medicinal chemistry, pharmaceutical chemistry

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In order to sustain the publishing process, each article accepted for publication in Open Chemistry is subject to an Article Processing Charge of €1200. This fee is used to cover the costs of the peer-review process, professional typesetting and copyediting, as well as online hosting, long-term preservation, and extensive promotion to potential readers. There is no submission fee. Information regarding payment of the charge will be provided following acceptance for publication. For more information please go to Article Processing Charges

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