POTENTIOMETRIC STUDY OF KINETICS AND MECHANISM FORMATION OF SILVER NANOPARTICLES STABILIZED BY SYNTHETIC FULVATES

Silver nanoparticles are actively studied due to their unique properties and wide use in various fields. In this study, silver nanoparticles were obtained by reacting Ag+ ions with synthetic fulvic acids derived from quercetin. Synthetic fulvic acids perform a dual function: a reducer of silver ions and a stabilizer of the formed nanoparticles The presence of silver nanoparticles in the solution is confirmed by the presence of a maximum in the absorption spectrum at 400 nm, which is due to the phenomenon of surface plasmon resonance. The parameters of the crystal lattice were established using the X‑ray diffraction method. The average nanoparticle size calculated by the Scherrer formula is 28 nm. The kinetics and mechanism formation of silver nanoparticles were studied by potentiometry, which allows direct and continuous control of the consumption of silver ions in the synthesis process. It is established that the mechanism of the process depends on the pH of the medium. In particular, at high pH values of the reaction medium there is a heterogeneous mechanism, while at low – homogeneous. The heterogeneous mechanism of formation of silver nanoparticles is characterized by the presence of three stages, in particular: 1) formation of Ag2O microparticles after mixing reagents, 2) reduction of Ag+ ions by synthetic fulvic acids from quercetin on the surface of formed Ag2O microparticles, which are heterogeneous nucleation centers. 3) reduction of Ag+ ions from solution on the surface of silver nanoparticles after complete dissolution of Ag2O microparticles (this process is described by first-order kinetics by Ag+). Activation parameters for different stages of silver nanoparticle formation using quercetin fulvic acids were calculated. A potentiometric study of the influence of the degree of aeration of the medium on the kinetics of changes in the pAg system was performed.

REDOX PROCESSES IN THE REACTIONS OF N-ARYLSULFONYL-1,4-NAPHTНOQUINONЕIMINES WITH CERTAIN NUCLEOPHILES

Quinone-hydroquinone pairs are prototypes of organic redox systems, and studies of the electrochemical behavior of these compounds are of great interest for research. Electrochemical behavior associated with the equilibrium of electron-proton transfer provides information about the molecular structure and environment of the process. Apart from chemical aspects, quinones play an important role in the biochemistry of living cells. Quinone derivatives, used as drugs for several types of human cancers, have been found to have their biological activity related to their redox behavior. Quinoneimines-aminophenols form similar pairs. In nucleophilic addition reactions of N‑substituted p-quinoneimines, parallel redox processes are often observed, and the higher the redox potential of quinoneimine, the greater the likelihood of such processes. Naphthoquinoneimines with aromatic amines and acylhydrazines follow the scheme of 1,4-addition, but as reaction products are oxidized products -4-arylsulfonylamido‑2-arylamino(2-aroylamino)-1,4-naphthoquinoneimines. The oxidant may be the original naphthoquinoneimine and oxygen. Studies have shown that oxygen in the reaction of 1,4-naphthoquinoneimines with acylhydrazines is the only oxidant that oxidizes the product of 1,4-addition, as evidenced by the study of redox potentials. Both oxidized and reduced form of the compounds, as naphthoquinoneimine and the corresponding aminonaphthol, are used to determine the redox potential by direct potentiometry. Due to the instability of the reduced form in the case of the pair naphthoquinoneimine-aminonaphthol, we used only the reduced form, which is oxidized in the cell by oxygen. The redox potential of the naphthoquinoneimine-aminonaphthol galvanic pair was determined as the average value between the potential Emax, which was established in the system upon complete oxidation of the starting substance, that is, when only naphthoquinone imine remains in the system, and the potential Emin, which was registered at the beginning of the process in the system with the reduced form – the corresponding aminonaphthol. This is the method of direct potentiometry in the variant of the middle potential.

MIXED-LIGAND HETEROMETALLIC COMPLEXES OF Ge(IV)-M2+ (Mn, Fe, Co, Ni, Zn) WITH 1,3-DIAMINO-2-HYDROXYPROPANE N,N,N',N'-TETRAACETIC ACID

There have been developed a novel synthetic method that allowed to obtain raw of mixed-ligand heterometallic binuclear complexes of Ge(IV)-M2+ (Mn, Fe, Co, Ni, Zn) with 1,3-diamino‑2-hydroxypropane N, N, N’, N’-tetraacetic acid (H5hpdta). Compounds have been characterized by the set of methods: elemental analysis, thermogravimetry, IR‑spectroscopy, spectrum of diffuse reflection, magnetic suspensibility. According to the elemental analysis, the molar ratio Ge: M: H5hpdta: bipy= 1:1:1:1 in the obtained compounds 1‑5 corresponds to the formula [(H2O)(OH)Ge(m-hpdta)M(bipy)]·nН2О (M=Mn n=3 (1), Fe n=2 (2), Co n=4 (3), Ni n=4 (4), Zn n=3 (5). Complexes have yellow (1), red (2), orange (3), violet (4) and pink (5) colors and are stable on air. Compounds 1‑5 exist in the form of crystal hydrates, that contain certain amount of water molecules, that are eliminated into the gas phase while heating in the wide range of temperatures (t=80‑250 °C), which is accompanied with the low-temperature endothermic effect. This indicates the presence of a system of stable hydrogen bonds in their crystal structure. Analysis of the IR‑spectra 1‑5 revealed that form and coordination of ligands is similar. Deprotonation of all carboxylic groups in the ligands (H5hpdta) and their bonding to germanium and d-metal is confirmed with the absence in the IR‑spectra 1‑5 absorption bands characteristic for the free СООН H5hpdta (1716 сm‑1) and nas(СОО-) і ns(СОО-) bands. Disappearance of the ν(С-OН)-1210 сm‑1 and appearance of the ν(С-O)alk., νas(Ge-O-M), νs(Ge-O- M) absorption band indicates that OH‑group of H5hpdta is deprotonated and performs bridging function. 2,2`-bipyridine bidentatly coordinates to the d-metal, binds to the O, N‑atoms of hpdta5- ligand and reaches coordination number 6. The last ligand plays the bringing role between Ge-dmetal, shows itself as ditopic, octadentate in total. According to the magnetic moments of 3, 4 and their diffuse reflection spectra, polyhedrons of Co (II), Ni (II) are octahedrons, which are realized due to the bidentate coordination of bipyridine and four bonds with nitrogen and oxygen of hpdta5-. Structure of heterometallic binuclear complexes 1‑5 is similar. Ligand hpdta5- shows itself as octadentate ditopic, all carboxylate groups monodentatly coordinate to metals, oxygen atom of the deprotonated OH‑group performs the bridging function.

SORPTION OF ERYTHROSINE ONTO SILICA GEL MODIFIED BY CETYLPYRIDINIUM BROMIDE

In the current paper, adsorbent based on silica gel L 40/100 modified with cetylpyridinium bromide was obtained. The presence of cetylpyridinium cations on the silica gel surface was confirmed by the diffuse reflectance infrared fourier transform spectroscopy method. The sorption conditions of erythrosine from dilute aqueous solutions with the proposed sorbent were studied and optimized. It is shown that the use of modified silica gel allows efficient (>95%) extraction of erythrosine from aqueous solutions. Under optimal sorption conditions (pH 7, sorbent dosage 0.1 g and sorption time is 15 min), the sorption capacity of modified erythrosine sorbents was determined. It is shown that, with increasing temperature, a change in the isotherm type from the H‑type to the L‑type is observed. This change can be explained by the aggregation of erythrosin in solution, which is a competitive sorption process. It was shown that adsorption isotherms were well described by the Langmuir equation. Thermodynamic studies have made it possible to establish the spontaneous sorption. The desorption of erythrosine from the surface of silica gel modified with cetylpyridinium bromide was studied. It is shown that when using solutions of sulfuric acid, sodium hydroxide and distilled water, desorption does not occur. It was shown that the most effective eluent is solution of sodium dodecylsulfate in alkaline medium, and desorption of erythrosine occurs due to the destruction of ion pairs of dye anions with cetylpyridinium cations fixed on the surface. The data obtained can then be used to develop a test system for determination of erythrosine via corresponding colorimetric scales or for quantitative solid phase extraction and adsorption-spectroscopic quantification of erythrosine in some real samples.

SYNTHESIS AND CHARACTERIZATION OF COORDINATION COMPOUNDS OF 3d-METAL MALEATES WITH THIOSEMICARBAZIDE

Complexes of copper(II), nickel(II), cobalt(III), and zinc(II) maleates with thiosemicarbazide were synthesized. The resulting compounds were characterized by the elemental analysis data, infrared spectroscopy, diffuse reflectance spectroscopy, and thermogravimetry.

LANTHANIDE COMPLEXES WITH REGIOISOMERS OF CHLORO-SUBSTITUTED TETRAPHENYLPORPHYRIN

Several isomeric complexes of Yb (III) and Lu(III) with H2tpp and its tetrachloro-substituted derivatives were synthesized. Symmetrical ortho-, meta- and para-positioning of four heavy atoms allows to study their effect on emission features of complexes. Obtained results show the rise of 4f-luminescence effectiveness in the row ortho-meta-para isomers.

WATER ROLE IN THE GASES CHEMOSORPORATION PROCESSES BY SORPTION-ACTIVE MATERIALS

The work summarizes the literature data on the hydration and chemisorption of toxic gases by polymeric sorption-active materials. The mechanisms of absorption by granular and fibrous ion-exchange and impregnated materials and the state of adsorbed water have been studied using various research methods (gravimetric, sorption-thermochemical, derivatographic, IR spectroscopic). The regularities of the hydration processes of granular strongly acidic sulfonic cationexchangers of the brands KU‑2 and KU‑23 (macroporous analogue), fibrous strongly acidic sulfonic cation- exchanger VION KS‑3, fibrous weakly acid carboxylic cation exchanger VION KN‑1 in various ionic forms are considered. Among the anion exchangers, the hydration of granular strongly basic anion- exchangers of the brand AV‑17, granular weakly basic anionexchangers of the brands AN‑25 (AN‑251 macroporous analogue) and ANKB‑35, fibrous strongly basic anion- exchangers of the brands FIBAN A‑6 and FIBAN A‑12, fibrous medium basic anion- exchangers of the brands CM‑2, fibrous weakly basic anion- exchangers of the brands CM-A1, VION AN‑1, VION AN‑3, FIBAN A‑5, FIBAN A‑11 and FIBAN AK‑22 are considered. It has been established that, by nature, the bond with the active centers of water is derided into a «bound» and a ordiner – «free». The first one is a monolayer and the nearest bonded with the ion of the ball; the other is the osmotic swelling water. It has been shown that for the effective absorption of most toxic gases and vapors (SO2, HCl, Cl2, SiF4, HF, NO2, NH3, аміни, COCl2, O3), it is necessary to have «free» water, which is not only a diffusion medium in which mass transfer proceeds, but also is a direct participant in chemisorption.

NEW ACID-BASIC INDICATORS: RESEARCH USING A SMARTPHONE

Modern cameras, desktop scanners, smartphones allow not only registering an image, but also determining its color characteristics. That allows us to quickly, objectively and automatically determine the color characteristics of colored samples in acid-base titration, because there is a significant error at visually determining the pH range of the color transition. In analytical chemistry the characteristics of acid-base indicators are very important, in particular their pH transition interval. But the disadvantage of most indicators is the wide range of color transition: from 1 to 3 pH units. The aim of this work is to find new acid-base indicators that change color in an alkaline environment and have a narrow pH range of the color transition. We have developed the apparatus and technique of convenient and highprecision simultaneous determination of the pH of the medium and the color of the acidbase indicators. In acid-base titration the PH measurements were performed with a combined glass electrode AD1131 by рН-meter AD1000. The color transition was determined with help of a smartphone with the subsequent processing of the results by computer software. The color characteristics were measured for each channel of the RGB model in the range from 0 to 255. Our apparatus is small and mobile, and allows us simultaneously to measure the pH of the medium and accurately to determine the color characteristics. As a result, we can construct graphical dependencies of color on pH for each channel of the RGB model. We found the N-arylsulfonyl-2-aroylamido-1,4-benzo(naphto)quinone monoimines and 2,5-dibenzoylamido-1,4-benzoquinone are good acid-base indicators. They “work” in the pH range from 8.82 to 11.35 and have a very narrow color transition interval from 0.10 to 0.61. Solutions of these compounds in an alkaline medium have bright intense colors due to formation of mesomeric ions. That allows using of these indicators in the titration of weak acids with strong bases and vice versa by the method of neutralization.

COMPARATIVE CHARACTERISTICS OF COATINGS WITH SiO AND GeO ON LEUCOSAPPHIRE

The reasons for the sharp difference in the adhesion of multilayer coatings containing SiO or GeO together with Ge on a leucosapphire (Al2O3) plate have been established. It should be mentioned that Silicon(II) and Germanium(II) oxides are quite stable in the gaseous state and, contrary, are metastable in condensed state; at high temperature they disproportionate into ultra-dispersed composites of amorphous nature. A comparison is made of the surface properties of ultramicroscopic droplets formed on solid surfaces – a substrate or the previous layer – upon condensation of SiO, GeO, or Ge vapors on leucosapphire. A qualitative assessment of the ratio of the corresponding contact angles of wetting by the indicated melts, formed at the first moment of contact, has been carried out. In assessing the surface tension of SiO and GeO melts (or Si – SiO2 and Ge – GeO2 composites), we proceeded from the corresponding values for SiO2 and GeO2, which are 296 and 248 mJ/m2 near the crystallization temperatures. On this basis, it was established that the smallest value of the contact angle, and hence the best wetting, is observed for the GeO melt (somewhat less for the SiO melt) on the solid surface of Al2O3 or Ge; the solid surface of SiO or GeO (especially, the first of them) with molten germanium should be much weaker wetted. Hence, it follows that thin-film multilayer coatings obtained from Ge and GeO on a leucosapphire substrate should have a significantly higher climatic resistance due to higher adhesion compared to multilayer coatings from SiO and Ge. Indeed, a multilayer coating containing SiO on a leucosapphire substrate with a large surface can withstand storage in air for no more than 2–3 months and begins to peel off; at the same time, the GeO coating remains intact after 4 years of storage. Thus, the GeO film-forming material is a promising one for use in multilayer coatings such as cut-off filters in interference optics of the near and mid-IR spectral ranges.

EQUILIBRIA PROCESSES IN AQUEOUS SOLUTIONS OF K2CrO4 – HNO3 – KNO3 – H2O AND K2Cr2O7 – NaOH – KNO3 – H2O SYSTEMS

The equilibria processes in aqueous solutions of CrO42– – H+ – H2O and Cr2O72– – OH– – H2O systems were studied by pH‑potentiometric titration, mathematical modeling and UV–Vis. spectroscopy. It was established that in the CrO42– – H+ – H2O systems with acidity ZН = ν(H+)/ν(Cr(VI)) = 0–2.5 the processes of dichromate and hydrochromate anion formation and hydrolytic conversion of dichromate to hydrochromate take place, for which the logarithms of the equilibrium concentration constants were calculated by the quasi-Newton method (CLINP 2.1 software; 95 % confidence probability). The calculated values of the logarithms of the concentration equilibrium constants lgKC reliably agree with the literature data. The calculated lgKC were used to build of chromium(VI) anions distribution diagrams depending on ZH, and ZOH in solutions. For the first time, by the Pitzer method the thermodynamic equilibria constants of hydrochromate HCrO4– (lgK10 = 6,94), the dichromate anion Cr2O72– (lgK20 = 15,49) formation processes from the CrO4 2– and H+ ions, and the logarithm of equilibrium constant of the interconversion of the dichromate anion to the hydrochromate anion (lgK30 = –1,61) were calculated. Mathematical modeling and UV–Vis. spectroscopy show that the composition of anions in Cr2O72– – OH– – H2O solutions with alkality ZOH = ν(OH–)/ν(Cr(VI)) = 0–2.5 is identical to CrO42– – H+ – H2O systems. It is established that the experimental dependencies pH = f(Z) for the Cr2O72– – OH– – H2O system can be reliably reproduced by hydrolysis reactions of dichromate anion to hydrochromate anion and by subsequent neutralization to chromate anion with equilibrium constants calculated for processes in CrO42– – H+ – H2O solutions with same ionic strengths. The quantitative composition of chromium(VI) solutions was confirmed qualitatively by UV–Vis. spectroscopy.