Министерство науки и высшего образования Российской Федерации Российское химическое общество им.Д.И.Менделеева Секция по химической термодинамике и термохимии Научного совета РАН по физической химии Сибирское Отделение Российской Академии Наук Институт неорганической химии им.А.В.Николаева СО РАН

This work describes the formation of the ionic composition of the sorption layer during the concentration of copper-lead and pyrite-copper-zinc ore. The thermodynamics of the sorption layer of a sulfhydryl collector (sodium diisobutyl thiophosphate and potassium butyl xanthate) on the surface of chalcocite under various conditions of its oxidation has been studied using pH- and redoxometry. The nature of the change in the chalcocite electrode potential depending on the type of modifier and storage device, as well as on pH, has been experimentally clarified. The differences in the collective action of a one-component accumulator and a mixture of flotation reagents were revealed based on the thermodynamics analysis of the flotation process reactions. In addition, the optimal conditions for the flotation were determined. It was found that the quality of the concentrate is mainly influenced by two factors, such as the pulp redox potential and the pH of the medium. Mathematical equations of the optimal reagent and hydrodynamic enrichment regimes with the maximum dissolution of ore minerals in solutions of flotation reagents were modeled.

One of the most critical tasks of modern energy is accumulating thermal energy due to the inefficient use of thermal energy during the underloading of power systems in which heat-accumulating materials are used. Therefore the paper studies the effect of alternating electric current on the heat-accumulating properties in a mixture based on Na2SO4·10H2O. It is established that the AC effect leads to an increase in the melt crystallization temperature of Na2SO4·10H2O and Na2S2O3·5H2O and also contributes to the return of heat. The selection of the treatment mode of the Na2SO4·10H2O–Na2S2O3·5H2O (50: 1 wt.) mixture by the AC was carried out. It was shown that the latent heat of melting of 329 kJ/kg is achieved at 500000 Hz frequency.

This paper is devoted to obtaining a zeolite-containing sorbent based on metallurgical waste — slag. The synthesis of zeolite adsorbent from ash and slag was carried out by hydrochemical and thermal treatment. The initial object and the obtained material were characterized using following methods: Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive analysis, X-ray phase analysis, titrimetry. The way of converting solid-phase waste into a beneficial product has been demonstrated. The study results showed that the surface of the obtained material is saturated with functional groups (hydroxy-, carboxy-, lactone), which predetermine the ability to bind metal ions during adsorption. The adsorption capacity of the product has been estimated for iodine and methylene blue. A thermodynamic analysis of the process of sorption of copper (II) ions from an aqueous solution has been conducted. It has identified that the sorbent can also be used for the adsorptive concentration of ions of rare-earth elements by the example of lanthanum and erbium. Laboratory testing of the possible use of the sorbent to purify industrial water was carried out using the example of wastewater from a chromium plating shop

The thermodynamic stability of slag wastes was investigated based on the provisions on the energy density of minerals. The elemental and phase composition of slag waste was determined. It was shown that the composition of the sample includes aluminosilicates of calcium, aluminotitanate of magnesium and iron oxide. The physical and chemical parameters of thermochemical reactions that are occurring at high temperatures up to 1000 K were calculated. It was found that the value of the dissolution rate changes according to the parabolic law with decreasing reaction surface under the influence of temperature, which indicates the formation of a porous structure and the concentration inhibition of the leaching process. The calculated values of the energy density of minerals are consistent with the derivatographic analysis's data of the slag sample.

The main category of materials wear in the process of transport, residential premises operation is a temperature difference between external and internal, a high gradient and cyclic changes in the temperature regime lead to changes in the materials structure and an increase in energy consumption.Therefore, an urgent problem along with the development of heat-storage materials which make it possible to reduce significantly the heat loss to the environment is the matrix modification through the introduction of various additives. The aim of this investigation is the establishing of adding sodium tellurate and sodium selenate to sodium thiosulfate pentahydrate influence on the heat-storage properties of the obtained mixtures. The behavior of sodium selenate and sodium tellurate in the composition of the mixture with sodium thiosulfate crystalline hydrate was studied by the conductivity method. The changes in the activity coefficients of sodium selenate, the contribution of sodium selenate to the heat content of the mixture with sodium thiosulfate pentahydrate were calculated. Also, the changes in the activity coefficients and association degrees of sodium tellurate - sodium thiosulphate pentahydrate mixtures (1:50) were calculated, according to which the complex formation process is exothermic, heat storage process is electrostatic in nature. Consequently, the stability of the associates is decreased with increasing temperature. It was also found that the mixture cooling to T=298 K releases into the environment up to 100 kJ/kg of heat. The temperature of transition to the active state is 353 K. As a result of the studies, optimal warming temperature T=348 K, stabilizing effect of tellurate ion on sodium thiosulfate with water molecules associates were found, which together allows the energy coming to the system accumulation, its release during cooling with subsequent.

The problem of the polymetallic ores enrichment containing of copper, lead, zinc and other nonferrous metals minerals' consists in the disclosure of splices, the separation of small-grained particles of one mineral from another mineral or waste rock. The purpose of this paper is studying the flotation reagents behavior in the suspension composition while ore enrichment according to the collectively selective scheme.The elemental analysis of copper-lead ore samples is carried out. The flotation tests on the FML-1 flotation machine were carried out, the volume of the working chamber was 0.25 L, and the T-92 was used as the foaming agent. The decomposition with concentrated nitric and hydrochloric acids mixture's was applied to carry the ore samples and enrichment products to the solute state. The results of copper-lead ore enrichment the use of sodium oleate in the main flotation are presented. The material balance of copper-lead ore flotation process both for the main and control flotation and for the clean-up operations according to the collectively selective scheme (for the solid component) was calculated. It is shown that the addition of two clean-up operations to the scheme, with sodium dibutyl dithiothiophosphate as the main reagent, makes it possible to increase the lead and copper concentration in selective concentrates by 3 times. Based on the results of the material balance, the separation potentials and separation capacities of the main, reference and two clean-up flotations were calculated. The negative dynamics of the change in the separation potential from the initial stage of enrichment to the final one indicates the increase in the minerals separation complexity. The presence of the separation potential extremes relative to the metal concentration in the ore indicates a difference in the oxygen-containing and phosphorus-containing collectors reactivity. It has been established that the value of separating power serves as a quantitative measure of the applied flotation agents selectivity. Thus, the efficiency of the proposed enrichment scheme was evaluated based on separation criteria.

The article shows the efficient use of natural apatite ore in purification of mining industrial wastewaters from heavy metal ions. The determination of adsorption constants, calculation of thermodynamic parameters at various pH of the medium were carried out. It was established that the sorbent based on apatite ore may be used in ecological and technological aims in water conditioning and water treatment.

The problem of water pollution with heavy metals is considered to be relevant, so currently the use of water-soluble polymers in waste water treatment is acceptable from an environmental point of view. In this regard, the aim is to study the physical and chemical properties of the interpolymer complex of polyvinyl alcohol polyacrylamide and their application in waste water treatment systems. The viscosimetry method was used for assess the complexing ability. The activation of metal complexes' binding processes was used by the electric alternating current. The mathematical models describing viscous flow of polymer mixtures under the influence of external factors to the system of M-PVA-PAA were obtained. The complex formation process of transition metals' ions with polymers in the composition of interpolymer complexes was investigated. The physical-chemical characteristics of the interpolymer complexes formation in the system of the PVA-PAA were determined. It is established that the effect of an alternating current of varying frequency results in an increase in complexing ability of polyacrylamide in the mixtures with polyvinyl alcohol and to reduction of Cr(VI). The optimum parameters of extraction of nickel (II) and chromium (VI) ions in a multicomponent system "M-mixture of polymers" were determined. It was shown that a mixture of PAA-PVA may be used in the purification of the Cr(VI) ion, and the adding this mixture into the nickel containing waste water reduces the concentration of heavy metal ions to 0.07%.

Temperature dependences of the heat capacity of cobalt manganites NdM 2 I CoMnO 5 (M I = Li, Na, and K) are studied by means of dynamic calorimetry in the range of 298.15−673 K. It is found that λ-shaped effects are observed on the C p ° ~ f ( T ) curve of cobalt manganites, due probably to second order phase transitions. Based on the experimental data, equations for the temperature dependences of the heat capacity of cobalt manganite are derived with allowance for the temperatures of phase transitions. The values of thermodynamic functions Н °( T )– Н °(298.15), S °( T ), and Ф хх ( T ) are calculated.

The evaluation the thermal stability of sorbents based on modified active carbons coals from coniferous wood has been carried out in this paper. Sorbents have been obtained by carbonization the wastes of coniferous wood modified with H3PO4 and NaOH and water treatment. It is shown that the porous material was formed during the carbonization of samples with additions of H3PO4 and NaOH at a temperature of 600 degrees C. The values of the activation energy were calculated from the kinetic data of thermal destruction by the Piloyan method, it was shown that the thermal destruction occurs in the diffusive regime. The values of the rate constants of solid-phase reactions by the models of Yander, Gistling-Brownstein, Zhuravlev and Krieger-Ziegler were also calculated.

This article presents the results of studies of the complexation of copper (II) ions with a mixture of oxyhydryl and sulfhydryl flotation agents in aqueous solutions with the formation of poorly soluble compounds. The dissociation constants of flotation agents were determined by the conductometric titration method. It is assumed that associates are formed among themselves as a result of the interaction of flotation agents. Analysis of the data of pK(a) of associates shows that for different associates, one of the components will have proton-donor and the other will have proton-acceptor properties. It is shown that oleic acid is strong (pK(a) 4.86), and diisooctyl-dithiophosphoric acid is weak in the associate of sodium diisooctyl dithiophosphate- sodium oleate, and the dissociation constant of this associate will be determined by the amount of sodium oleate. As a result of the interaction of copper (II) ions with a mixture of oxyhydryl and sulfhydryl flotation agents, poorly soluble compounds are formed, K-sp ranges from 23 to 34. Based on the studies, it has been shown that associates of sulfur- and oxygen-containing surfactants form with copper (II) ions the poorly soluble mixed-ligand complex compounds, and the degree of binding of copper (II) ions to the poorly soluble compounds is 99.99 %.

This article discusses the results of FT-IR spectroscopy, X-ray diffraction, and sorption properties of activated carbons from dry pine cones common in relation to of Cd (II), Pb (II), Hg (I, II) ions. The results indicate the higher efficiency of the sorbent that is based on softwood followed by modification for wastewater treatment from toxic heavy metals such as lead, cadmium and mercury with purity from 90 % to 99 %.

Using ceramic technology, we synthesized cobalt manganites with the composition (LaM2CoMnO6)-Co-II (M-II Mg, Ca, Sr, Ba) from oxides of lanthanum (III), cobalt (II), manganese (III) and carbonate of alkali-earth metals. X-ray powder diffraction study and indexing established that the cobalt-manganites crystallize in the cubic system with the following lattice parameters: LaMg2CoMnO6 - a = 16,761 +/- 0,062 angstrom, V-0 = 4708,69 +/- 0,019 angstrom(3), Z = 6, V-0 (el.cell) = 787,78 +/- 0,03 angstrom(3), rho(x-ray). = 5,78, rho(pycn). = 5,84 +/- 0,10 g/cm(3); LaCa2CoMnO6 - a = 16,650 +/- 0,026 angstrom, V-0 = 4609,11 +/- 0,06 angstrom(3), Z = 6, V-0 (el.cell) = 768,19 +/- 0,01 angstrom(3), rho(x-ray). = 5,63, rho(pycn). = 5,56 +/- 0,10 g/cm(3); LaSr2CoMnO6 - a = 16,711 +/- 0,034 angstrom, V-0 = 4666,59 +/- 0,09 angstrom(3), Z = 6, V-0 (el.cell) = 777,77 +/- 0,02 angstrom(3), rho(x-ray).= 6,44, rho(pycn). = 6,37 +/- 0,11 g/cm(3); LaB(a)2CoMnO(6) - a = 16,840 +/- 0,030 angstrom(3), V-0 = 4775,58 +/- 0,09 angstrom(3), Z = 6, V-0 (el.cell) = 795,3 +/- 0,02 angstrom(3), rho(x-ray). = 7,09, rho(pycn). = 6,95 +/- 0,09 g/cm(3). The new indicator electrodes through carbon paste modified cobalt-manganite (LaM2CoMnO6)-Co-II (M-II - Mg, Ca, Sr, Ba) were created. The main characteristics of the electrode (the slope of the electrode function, selectivity factor and response time) of carbon-paste ion-selective electrodes were determined. It is seen that in the case of all four electrodes are showing an ion exchange function. It is shown that carbon-paste electrodes were characterized by satisfactory stability of stationary potential when used in direct potentiometry.

The kinetic and thermodynamic parameters of the sorption process for mixtures of oxy-hydryl and sulf-hydryl collectors on the Ayak-Kodzhan deposit ore samples were determined in this paper. An analysis of sorption isotherms oxy-hydryls and sulfhydryls howed a tendency to the formation of the adsorption layer is not the entire surface of the particles. Preferably in the micropores (macro and mesopores), energy interaction << adsorbate-adsorbent >> is defined as the structure of the adsorbent and adsorbate structure (sulfur- and oxygen-collectors), and hence, value of parachor and molear volume.

Synthesis of N-2-(2-hydroxybenzoyl) hydrazino-carbonotioilbenzamide was carried out. Structure of synthesized compound was identified using IR-, NMR-spectroscopy. Complex formation ability of N-2-(2-hydroxybenzoyl)hydrazino-carbonotioilbenzamide to the La3+, Y3+, Nd3+ ions in aqueous-organic medium in the temperature range 298-318 K at the constant ionic strength (0.1 M NaNO3) was investigated by pH-metric methods. Complex formation of lanthanum (III) ions in water-dioxane solvent is accompanied by heat generation and is characterized by positive values of entropy change. Complexes of neodymium (III) and yttrium (III) ions with N-2-(2-hydroxybenzoyl) hydrazino-carbonotioilbenzamide were stabilized by solvent.