CHEMICAL SCIENCES
This article presents a study on the complexation of copper (II) with 2,7-bis(azo-2-hydroxy-3-sulfo5-nitrobenzene)-1,8-dihydroxynaphthalene-3,6-disulphonosodium salt (R) in the presence of diphenylguanidine (DPG), triphenylguanidine (TPG) and non-ionic SAA Triton X-114 (TX-114), carried out by spectrophotometric method. The optimal conditions for the Cu-R complexation are established as follows: pH=3 with the maximum light absorption of the complex occurring at a wavelength of 538 nm. The yield of the Cu-R complex reaches a maximum at the R component concentration of 8·10-3 M, while the highest value for Cu-R-DPG complex is observed at concentrations of 8·10-5 and 1·10-3 M for the R and DPG components, respectively. The maximum of Cu-R-TFG is noted with concentrations of the R and TPG components comprising 8·10-5 and 8·10-4 M, respectively. The maximum yield of the Cu-R-TritonX-114 complex was obtained at a component concentration of 8·10-5 and 8·10-4 M, respectively. All complexes are formed immediately following the mixing of the component solutions and differ in stability. In the presence of a third component, the maximum absorption is observed at a wavelength of 512 nm (pH=1), 491 nm (pH=2) and 572 nm (pH=2) for the Cu-R-TX-114, Cu-R-DPG and Cu-R-TPG complex, respectively. The reaction ratio of components in the composition of homogeneous (Cu:R =1:2) and mixed ligand (Cu:R:X= 1:2:2) compounds is established. The interval of obedience to Beer's law equal to 0.12–2.32 mg/mL was determined for Cu-R complexes. For Cu-R-TX-114, Cu-RDPG and Cu-R-TPG, the determined interval comprised 0.07–2.32 mg/mL. The following values of stability constant for the complexes was established using the spectrophotometric method: 8.75±0.05 (Cu-R), 9.59±0.05 (Cu-R-TX-114), 9.85±0.05 (Cu-R-DPG) and 9.92±0.04 (Cu-R-TPG). The molar absorption coefficient of the complexes was determined as equal to 10400 (Cu-R), 15000 (Cu-R-TX-114), 15500 (Cu-R-DPG) and 16000 (Cu-R-TPG). The logKhyd= 7.5, lgKhyd= 12.7 and lgKhyd= 13.9 constants of the nickel ion hydrolysis were obtained. The coefficients of the calibration curve equation are determined by the method of least squares. Under optimal complexation conditions, Cu-R was titrated with a component solution (TritonX-114, DPG and TPG) using the conductometric method. The effect of impurity ions and masking substances was studied. The determination of copper (II) is practically unhindered by alkaline, alkaline-earth and some transition elements, such as Ca (II), Ba (II), Mn (II), Cr (III), Sn (IV), Ga (III), In (III) and Zr (IV). The proposed express technique is characterised by its high sensitivity and selectivity, as well as being applicable for the determination of copper in food cereals.
A new organic reagent, (E)-2-hydroxy-3-((2-hydroxybenzylidene) (amino) benzenesulphonic acid, was synthesised on the basis of salicylic aldehyde. The complexation of iron (III) with c (E)-2-hydroxy-3-(2- hydroxybenzylidene) (amino) benzenesulphonic acid (R) was studied both in the presence and absence of the following surface-active substances (SAA): cetylpyridinium chloride, cetyltrimethylammonium bromide and Triton X-114. Fe (III) was established as forming coloured mixed-ligand complexes with the reagent in the presence of third components. The optimal complexation conditions were determined for the Fe (III)-R binary complex (pH = 4, λmax = 353 nm), as well as for the multi-ligand complexes of Fe(III)-R-CPCl (pH = 3, λmax = 374 nm), Fe(III)-R-CPMABr (pH = 2, λmax = 392 nm) and Fe(III)-R-Triton X-114 (pH = 3, λmax = 385 nm). The proportion of reacting components in the composition of Fe(III)-R homogeneous ligand iron compounds was determined to be equal to 1:2. Mixed ligand compositions were 1:1:2, 1:1:1 and 1:2:1 for Fe (III)-R-CPCl, Fe(III)-R-CPMABr and Fe(III)-R-Triton X-114, respectively. The molar absorption coefficients and stability constants of Fe(III) complexes were determined. The molar coefficients of the complexes Fe(III)-R, Fe(III)-R-CPCl, Fe(III)-R-CPMABr and Fe(III)-R-Triton X-114 comprise 10,000, 16,250, 19,000 and 11,000, respectively. The intervals of obedience to Beer's law (μg/mL) were determined to range 0.448-2.24, 0.112-4.48, 0.12-4.48 and 0.224-2.24 for Fe(III)-R, Fe(III)-R-CPCl, Fe(III)-R-CPMABr and Fe(III)-R-Triton X-114, respectively. The effect of some ions and masking substances on the formation of binary and mixed-ligand complexes of Fe(III) was studied. The presence of a surfactant was demonstrated to significantly increase the selectivity of the reaction. A technique was developed for spectrophotometric determination of Fe(III) in beans, mushrooms and briar. The data obtained using the proposed method are in good agreement with the results of atomic absorption spectrometry. The proposed method for the determination of Fe(III) with (E)-2-hydroxy-3-(2-hydroxybenzylidene)(amino)benzenesulphonic acid in the presence of cetyltrimethylammonium bromide (CTMABr) is simple, rapid and provides reliable results.
PHYSICOCHEMICAL AND GENERAL BIOLOGY
The traditional approach to assessing the quality of nutrient bases involves a determination of amino nitrogen and acidity. The disadvantage of this approach consists in a lack of information, i.e. an inability to detect antibiotics, growth inhibitors and other undesirable compounds. In this regard, more modern and informative methods are required to control the technological process of preparing the nutritional basis and therefore the quality of the products obtained. The aim of this work was to study the physicochemical properties of nutrient bases made from sea and river fish and squid using new approaches (NMR spectroscopy). The following raw materials were used: herring (1), roach (2), pollock (3), squid (4). The raw materials were subjected to enzymatic hydrolysis by the pancreas (according to Hottinger). The qualitative composition of the organic component of hydrolysates (1–4) was determined by 1H, 13С and 15N NMR spectroscopy. All of the 1H NMR spectra had the same appearance, typical of mixtures of amino acids or amino acid sequences. In the high-field part (0.9–2.5 ppm), a set of multiplets was observed, characteristic of aliphatic fragments of molecules. Since most of the signals in the 1H NMR spectra partially overlap, a quantitative assessment of the composition of the organic component appears impossible. All four samples can be confirmed as being qualitatively similar without isolating the dominant compound. Analysis of 2D NMR spectra revealed the presence of the following free amino acids in mixtures of samples (1–4): alanine, valine, threonine, arginine, lysine, leucine, methionine, phenylalanine and glycine. The use of NMR spectroscopy demonstrated that any discrepancies in the component composition of hydrolysates (1–4) were insignificant, allowing manufacturers of nutrient media to choose the most affordable raw materials. The obtained data appear to be applicable for controlling the technological process of preparing the nutrient bases and determining the quality of the resulting products during storage.
CHEMICAL TECHNOLOGY
Oily wastes, along with the problem of their disposal, comprise an inevitable factor in the processing and storage of oil and oil-derived products. Contemporary disposal methods such as landfill and incineration entail secondary pollution of environmental objects. However, since oily wastes contain valuable hydrocarbons, the search for new ways to extract them for use as components of the target products of oil refineries is an urgent task. The object of the study comprised oily wastes derived from an oilwell product of the commercial production of the Angarsk Petrochemical Company. According to the existing scheme, this product is combined with other oil-containing streams and sent for rectification. Thus, in 2017, 1,200 tonnes of secondary oil product were sent to the conversion unit. The transportation and processing of such a quantity of substrates leads to the release into the environment of more than 2 tonnes of harmful substances per year. The results of qualitative and quantitative analysis showed that the high content of gasoline fractions – predominantly n-alkanes C5–С10 (more than 90% by weight) – in the hydrocarbon composition suggests the possibility of using the oilwell product as a component of motor gasolines without re-processing using the rectification method. However, the quality of the oilwell product, mainly in terms of water content and colour, is rather unstable. In order to select the preliminary preparation method for the oilwell product, tests of a bottom sample having a high water content (50% vol.) were carried out. It was established that sedimentation of the sample at a temperature of 22–23 °С for 4 hours leads to the effective separation of the water component. To reduce the influence of the colour factor of the oilwell product when adding it to motor gasolines, it is proposed to dilute it with other refinery by-products. The quality of laboratory samples of AI-92 and AI-80 gasolines obtained with the involvement of the prepared oilwell product complies with the requirements of GOST 32513. In order to scale the process of preparing the substation in order to use it as a component of motor fuels, Angarsk Petrochemical Company developed a simple, affordable technological scheme, based on mixing and separation processes using available equipment. The economic effect of the implementation of this measure will be about 3.7 million rubles per year. The proposed evaluation scheme and the method of separation of water-organic by-products for further use as a component of motor fuel are generic and can be applied to similar wastes from refineries and oil depots.
BRIEF COMMUNICATION
The formation of ion-exchange composite materials based on high molecular weight precursors appears to be an intensively developing area in the synthesis of proton-conducting membranes for fuel cells. In such membranes, proton transfer is often provided by functional polymers simultaneously containing sulphonic acid groups in their composition units along with fragments of vinyl derivatives of nitrogen-containing heterocyclic bases. Proton exchange activity in the latter is determined by the possibility of doping with inorganic acids. In the framework of this study, for the further formation of hybrid composite membranes under conditions of radical initiation, copolymers of sodium 4-styrene sulphonate (SSt) with 4-vinylpyridine (VP) and 1-vinylimidazole (VIM) were obtained. The monomodal nature of the turbidimetric titration curves for solutions of copolymerisation reaction products indicates the presence of true copolymers during the process of formation. The composition and structure of the copolymers were characterised using data from elemental analysis, as well as from IR and 13C NMR spectroscopy. Constants of the relative activity for the monomers and the microstructure parameters of the polymer chains are calculated according to the non-linear leastsquares method using the MathCAD package. The calculated copolymerisation constant values indicate a greater reactivity of SSt in comparison with nitrogen-containing monomers. The lengths of the monomer unit blocks depend on the composition of the initial mixture and vary over a wide range from 1 to 18. The possibility of varying the length of the unit blocks in the composition of the copolymers will affect the ion-conducting properties of hybrid composites formed on their basis. The stability of the copolymers to thermal oxidative degradation by heating in air was studied using the differential scanning calorimetry (DSC) method. The copolymers demonstrated significant thermo-oxidative stability. Decomposition temperatures were 350 °С and 400 °С for SSt-VIM and SSt-VP copolymers, respectively.
ISSN 2500-1558 (Online)