Optical and gamma irradiation studies of morin in ethanol

Spectral studies of morin in aqueous ethanol and other alcohols have been carried out as a function of its concentration and that of ethanol, and the pH of aqueous buffer. The effect of gamma radiations on morin solution in ethanol was also studied as a function of dose in the range of 0.15–2.28 kGy and of morin concentration (10^–5–10^–4 mole·dm^–3). Morin concentration in ethanol solution showed a linear response for G values to a dose of 1.83 kGy. Molar absorption coefficients () for morin in ethanol have been estimated to be _260nm=2.28·10⁴ dm³·mol^–1·cm^–1 and _291nm=8.22·10³ dm³·mol^–1·cm^–1 for unirradiated and _{291 nm}=1.75·10⁴ dm³·mol^–1·cm^–1 for irradiated solutions to a dose of 1.83 kGy.     

IR-Spektralanalyse von Gl?sern des Systems TeO2?V2O5

Studies of glasses and their crystalline products in the TeO₂–V₂O₅ system were made in the 1400–400 cm^–1 range. A continuous shift of the V=O-band from 1020 cm^–1 to 940 cm^–1 was found in the glasses with decreasing concentration of V₂O₅, as well as a sharp decrease in the intensity at 830 cm^–1. On the basis of the results obtained, it is concluded that with increasing TeO₂ content, the structure of the glasses is changed, caused by the breaking of the V–O–V bonds and the formation of Te–O–Te bridges.The IR-spectrum of the 2TeO₂·V₂O₅ compound in both crystalline and vitreous states was studied for the first time. The behaviour of the absorption bands is related to the structure of the glasses studied.     

IR-Spektralanalyse von Gläsern des Systems TeO2−V2O5

Studies of glasses and their crystalline products in the TeO₂–V₂O₅ system were made in the 1400–400 cm^–1 range. A continuous shift of the V=O-band from 1020 cm^–1 to 940 cm^–1 was found in the glasses with decreasing concentration of V₂O₅, as well as a sharp decrease in the intensity at 830 cm^–1. On the basis of the results obtained, it is concluded that with increasing TeO₂ content, the structure of the glasses is changed, caused by the breaking of the V–O–V bonds and the formation of Te–O–Te bridges.The IR-spectrum of the 2TeO₂·V₂O₅ compound in both crystalline and vitreous states was studied for the first time. The behaviour of the absorption bands is related to the structure of the glasses studied.

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Mit 4 Abbildungen     

Diffuse reflectance spectra of iron(III) vanadates

The electronic spectra of solid iron(III) vanadates FeVO₄ and Fe₂V₄O₁₃ were investigated by the diffuse reflectance technique in the spectral range 12 500–50 000 cm⁻¹. The spectra of investigated vanadates contain 2–3 intensive CT bands in the UV region and two lowest energy d–d bands in the 12 000–22 000 cm⁻¹ range. The presence of the weak bands for FeVO₄ and Fe₂V₄O₁₃ at 16 500 cm⁻¹ and 20 500 cm⁻¹ points to the lattice deffects (oxygen deficiency and the presence of the V⁴⁺ ions) in the structure of investigated vanadates.     

Electromigration of carrier-free radionuclides

Dependences of La(III) overall ion mobilities on concentrations of ox^2– and tart^2– anions of oxalic and tartaric acid in aqueous solutions of 0.01 overall ionic strength and temperature 298.1 K were obtained by direct measurements of electromigration of carrierfree¹⁴⁰La-lanthanum(III). Concentration stability constants K_n and individual ion mobilities u _i ^o of oxalate and tartrate complexes of La(III) have been calculated for nitrate and perchlorate electrolytes, respectively: [La(ox)]⁺, lg K₁=5.63(9), u⁰[La(ox)]⁺=1.95(15)·10^–4 cm²·s^–1·V^–1; [la(ox)₂]^–, lg K₂=4.05(19) u⁰[La(ox)₂]^–=–1.76(20)·10^–4 cm²·s^–1·V^–1; [La(tart)]⁺, lg K₁=4.40(5), u⁰[La(tart)]⁺=+1.99(18)·10^–4 cm²·s^–1·V^–1.Results are compared with literature data. Additional, limiting individual La³⁺ ion mobility was calculated: =+6.9(1)·10^–4 cm²·s^–1·V^–1 for pure water at 298.1 K.     

Zur photometrischen Bestimmung kleiner Selenmengen

Summary Selenium(IV) or selenium(VI) is reduced in hydrochloric acid solution by means of chromium(II) to hydrogen selenide, which is passed into alkaline [Fe(CN)₆]^3– solution in a stream of nitrogen to be oxidized there to selenium(IV). 6 mol of [Fe]CN₆]^4– are formed per 1 mol of selenium. The latter reacts with iron(III) in the presence of 1,10-phenanthroline or bathophenanthroline-disulphonic acid to their Fe(II) complexes. The extinction coefficient for the determination of selenium is 68030 or 135700 1 · mol^–1 · cm^–1, respectively.     

IR-analysis of H-bonded H2O on the pure TiO2 surface

The surface state of optically pure polydisperse TiO₂ (anatase and rutile) was determined by infra-red (IR) spectroscopy analysis in the temperature range of 100–453 K. Anatase A300 spectrum, contrary to rutile R300 one, has a broad three-component absorption band with peaks at 1048, 1137 and 1222 cm⁻¹ in the spectral range of δ(Ti–O–H) deformation vibrations. For rutile R300 we observed a very weak band at 1047 cm⁻¹, and for the thermal treated rutile R900 these bands were not appeared at all. The analysis of temperature dependencies for the mentioned absorption bands revealed the spectral shift of 1222 cm⁻¹ band towards the high frequencies, when the temperature increased, but the spectral parameters of 1137 and 1048 cm⁻¹ bands remained the same. The temperature of 1222 cm⁻¹ band maximum shift was 373–393 K and correlated with DSC data. Obtained results allowed to assign 1222 cm⁻¹ band to the deformation vibrations of OH-groups, bounded to the surface adsorbed water molecules by weak hydrogen bonds (5 kcal/mol). During the temperature growth these molecules desorbed, which also resulted in the intensity decreasing of stretching OH-groups vibration IR-bands at 3420 cm⁻¹. The destruction and desorption of surface water complexes led to Ti–O–H bond strengthening. IR bands at 1137 and 1048 cm⁻¹ were attributed to the stronger bounded adsorbed water molecules, which are also characterized with stretching OH-groups vibration bands at 3200 cm⁻¹. These surface structure were additionally stabilized by hydrogen bonds with the neighbouring TiO₂ lattice anions and other OH-groups, and desorbed at higher temperatures.     

Electrochemical and Structural Characterisation of Dip-Coated Fe/Ti Oxide Films Prepared by the Sol-Gel Route

Thin solid films of mixed Fe/Ti oxide composition (Fe/Ti molar ratios: 0.5∶1, 1∶1, 1.5∶1) have been made from Fe(NO₃)₃ alcoholic solution to which Ti(OiPr)₄ was added. Films have been deposited by the dip-coating technique and heat-treated at 300°C and 500°C. Powders of Fe/Ti oxide heat-treated at 300°C are amorphous, while powders annealed at 500°C for 40 hours transformed to mixed rutile, pseudobrookite and hematite phases. The structure of the XRD amorphous films was identified with the help of near-normal reflection absorption (6°) (IRRA) and near-grazing incidence angle (NGIA) spectroscopy. NGIA FT-IR spectra of films are characterised with a single phonon mode appearing in the spectral range 600–950 cm⁻¹ which shifts with increasing Ti concentration from 675 cm⁻¹ (Fe₂O₃) to 904 cm⁻¹ (TiO₂) thus exhibiting one-mode behavior. Electrochemical investigations made with the help of cyclic voltammetry (CV) and chronocoulometry (CPC) performed in 0.01M LiOH and in 1M LiClO₄/propylene carbonate electrolytes revealed that films are able to uptake reversibly Li⁺ ions with a charge capacity (Q) per film thickness (d) in the range 0.1–0.26 mC/cm²nm and 0.06 mC/cm²nm, respectively. The temperature at which the films were prepared alters the rate of Li⁺ insertion which is faster for less compact films obtained at 300°C. In situ UV-VIS spectroelectrochemical measurements revealed that Fe/Ti oxide films bleached in the UV spectral region (300 nm<λ<450 nm) and colored in the VIS spectral region (450 nm<λ<800 nm), thus exhibiting mixed anodic and cathodic electrochromism.     

Infrared spectra (700–200 cm−1) and6Li/7Li and H2O/D2O isotope effects for four isotopically substituted lithium formate monohydrates

The infrared spectra, in the 700–200 cm^–1 region, have been reported for⁶LiHCO₂ · H₂O,⁶LiHCO₂ · D₂O,⁷LiHCO₂ · H₂O and⁷LiHCO₂ · D₂O and the observed fundamental bands have been discussed taking into account the⁶Li/⁷Li and H₂O/D₂O isotope wavenumber shifts on the fundamental vibrations.

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Infrarotspektren (700–200 cm^–1) und⁶Li/⁷Li- und H₂O/D₂O-Isotopeneffekte für vier isotopensubstituierte Lithiumformat-monohydrate

Zusammenfassung Die Infrarotspektren in der Region von 700–200 cm^–1 werden für⁶LiHCO₂ · H₂O,⁶LiHCO₂ · D₂O,⁷LiHCO₂ · H₂O und⁷LiHCO₂ · D₂O angegeben und die beobachteten Grundschwingungen zusammen mit den isotopischen Verschiebungen der Wellenzahlen diskutiert.

     

Spectrophotometric determination of iron after separation of its 9,10-phenanthrenequinone monoximate on microcrystalline naphthalene

A sensitive and selective spectrophotometric method has been developed for the determination of iron as Fe(II) or Fe(III) using 9,10-phenanthrenequinone monoxime (PQM) as the complexing agent. Fe(II) and Fe(III) react with PQM to form coloured water insoluble complexes which can be adsorbed on microcrystalline naphthalene in the pH ranges 3.7–6.2 and 2.0–8.4, respectively. The solid mass consisting of the metal complex and naphthalene is dissolved in DMF and the metal determined spectrophotometrically by measuring the absorbances Fe(II) at 745 nm and Fe(III) at 425 nm. Beer's law is obeyed over the concentration range 0.5–20.0 g of iron(II) and 20–170.0 g of Fe(III) in 10 ml of DMF solution. The molar absorptivities are 1.333 × 10⁴ 1 · mole^–1 · cm^–1 for Fe(II) and 2.428 × 10³1· mole^–1 · cm^–1 for Fe(III). The precision of determination is better than 1%. The interference of various ions has been studied and the method has been employed for the determination of iron in various standard reference alloys, bears, wines, ferrous gluconate, human hair and environmental samples.     

Struktur von Gläsern des Systems TeO2−VO2

Glasses from the TeO₂–VO₂ system and - and -crystalline modifications of TeO₂·VO₂ (TeVO₄) are studied by IR-spectroscopy in the 1400–400 cm^–1 range. Similarity is established in the area near 970 cm^–1 of the spectrum between TeVO₄ glass and the -form. The continuous shift of the band from 970 cm^–1 to 950 cm^–1 with increasing TeO₂ content in the glasses is connected with the indirect influence on the nonbridging V–O bond.It is shown that the local environment of the V in some glasses from TeO₂–VO₂ and TeO₂–V₂O₅ system is similar: VO₅ polyhedra.     

Cobalt(III) α-Dimethylglyoximates [Co(DH)2(Py)2]2SiF6 · 10H2O and [Co(DH)2(Thio)2]2SiF6 · 2H2O · C2H5OH: Synthesis and Structure

[Co(DH)₂(Py)₂]₂SiF₆ · 10H₂O and [Co(DH)₂(Thio)₂]₂SiF₆ · 2H₂O · C₂H₅OH complexes are synthesized and characterized by X-ray diffraction analysis. Two radicals of -glyoxime linked by hydrogen O–H···O bonds lie in the equatorial plane of the octahedral Co(III) complexes. Intramolecular (– and N–H···O) and intermolecular (O–H···F, O–H···O, N–H···F, N–H···O, N–H···S) interactions are discovered in the crystal. The influence of nonvalence interactions on the structures is discussed.     

Multinuclear macromolecule metal complexes 2. Preparation and characterization of Prussian blue and its analogs bonded to pofy(vinylamine hydrochloride)

Prussian blue and its analogs bonded to poly(vinylamine hydrochloride) (PVAm · HCl) containing Fe^II or Fe^III and M²⁺ (M=Fe, Co, Cu) in a 11 molar ratio were obtained by the reaction of [Fe(CN)₆] ^n– (n=3,4) with M²⁺ ion-PVAm · HCl mixture in aqueous solution. Under a limited polymer concentration (T_VAm/T_Fe over 10), these polymer complexes thus obtained were stable and soluble in water. By casting these solutions, colored films can be produced. The formation of Prussian blue and its analogs bonded to PVAm · HCl was also investigated by the Benesi-Hildebrand method. The molar extinction coefficients of intervalence charge transfer (Fe^IIFe^III, Co^IIFe^III, Fe^IICu^II) band for MFe(CN)₆]^(n–2)– bound to PVAm · HCl (M=Fe, Co, Cu) were found to be 10,100–9601 · mol^–1 · cm^–1 at 25 C. The formation constants were found to be in the range of 10⁷ to 10¹⁰ M^–1. The changes of enthalpy (H) and entropy (S) were found to be in the range of –10.4 to –22.5 kJ · mol^–1 and 5.7 to 52.9 J · K^–1 mol^–1 respectively, at 25C.     

Modeling of iron adsorption on HTTA-loaded polyurethane foam using Freundlich,Langmuir and D-R isotherm expressions

The sorption of Fe(III) at low pH range from 1 to 4.5 on open cell polyether type HTTA-loaded polyurethane foam has been carried out using batch technique. The optimum shaking time for 2.5· 10^–4M solution of Fe(III) was found to be 30 minutes. The concept of macropore and micropore nature of polyurethane foam sorbent offers unique advantages of adsorption. Freundlich and Langmuir adsorption isotherms are followed at low concentration range from 1·10^–4 to 3·10^–4M solution of Fe(III). The Freundlich constant (1/n=0.46±0.013 andK=9.16±1.39 mg·g^–1) and Langmuir isotherm constants(M=21.78 mg·g^–1 andb=88.41±9.731·g^–1) were established. The sorption mean free energyE=12.22±0.09 kJ·mol^–1 and loading capacityC _m =145.21±6.1 mg·g^–1 were evaluated using Dubinin-Radushkevich isotherm, which suggested that the adsorption mechanism was chemisorption.     

Monooctyl-α-(4-carboxyanilino)benzylphosphonic acid as a new reagent for extraction and separation of lead(II) and bismuth(III)

Monooctyl--(4-carboxyanilino)benzylphosphonic acid (H₂L) was investigated as a novel reagent for the extraction and separation of lead(II) and bismuth(III) from nitrate solutions. Stoichiometric ionization constants of H₂L in ethanol — water mixtures determined by potentiometric NaOH titration had values pK_a1 2.25 and pK_a2 4.33. Ethanol and chloroform solutions of H₂L followed Beer's law at 300 nm and 296 nm, molar absorptivities being 2.94·10⁴ mol^–1·l·cm^–1 and 2.85·10⁴ mol^–1·l·cm^–1, respectively. HNO₃ and HCl were also extracted into chloroform solutions containing H₂L. Bismuth(III) was quantitatively transferred into the chloroform H₂L solution at pH 1, and lead(II) at 3.5. The value of the separation factor D_Bi/D_Pb is 160 at pH 1.     

Microdetermination of bromate ions with antipyrine

Summary A spectrophotometric method for the micro-determination of bromate ions has been described. A red colored complex is obtained when 3 ml of 5% antipyrine, 3 ml of 60% perchloric acid and 1 ml of 0.1M sodium nitrite solution are added in a solution containing bromate ions. The maximum absorbance occurs at 525 nm. Beer's law is obeyed for solutions containing 25.0–140.0/ml of bromate ions. Sensitivity has been found to be 0.029g BrO₃ ^–/cm² for logI ₀/I=0.04 with a molar absorptivity of 2·10³ moles^–1, cm^–1. liter. As(III), Ce(IV), Fe(III), CrO₄ ^2–, Cr₂O₇ ^2–, and Cl^– interfere in the determination.

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Zusammenfassung Eine spektrophotometrische Methode zur Mikrobestimmung von Bromationen wurde beschrieben. Nach dem Zusatz von 3 ml 5%iger Antipyrinlösung, 3 ml 60% iger Perchlorsäure und lml 0,1 ·m Natriumnitrit zu einer bromathaltigen Lösung erhält man eine rot gefärbte Komplexverbindung. Deren Absorptionsmaximum liegt bei 525 nm. Lösungen mit 25,0 bis 140,0g Bromat/ml entsprechen dem Beerschen Gesetz. Die Empfindlichkeit der Reaktion beträgt 0,029g BrO₃ ^–/cm₂ für logI ₀/I=0,04 mit einer molaren Absorption von 2 · 10³ m^–1 · cm^–1 · 1. As(III), Ce(IV), Fe(III), CrO₄ ^2–, Cr²O₇ ^2– und Cl^– stören die Bestimmung.

     

Der Einfluß großer Salzkonzentrationen auf die Oxydationsreaktion von Fe(phen) 3 2+ mit Ce(IV) in Schwefelsäure

The influence of NaClO₄, NaCl and Na₂SO₄ on the oxidation of Fe(phen) ₃ ²⁺ by Ce(IV) was investigated by means of the stopped-flow method. At the concentrations range of NaClO₄ and NaCl 0.1–1.0M the rate constant values decrease from 1.03·10⁵ to 0.56·10⁵M^–1s^–1 and from 1.08·10⁵ to 0.81·10⁵M^–1s^–1 respectively.In varying concentrations of Na₂SO₄ solutions (0.05–0.35M) the rate constant values decrease from 1.05·10⁵M^–1s^–1 to 0.45·10⁵M^–1s^–1.Taking into account the negative salt effect the mechanism of the reaction progress is proposed.

     

IR spectroelectrochemical studies of Fe2V4O13, FeVO4 and InVO4 thin films obtained via sol-gel synthesis

In this paper we generalize the IR spectroscopic properties of M³⁺VO₄ (M=Fe, In) orthovanadate and Fe₂V₄O₁₃ films. The films were prepared using the sol-gel synthesis route from M³⁺ nitrates and vanadium oxoisopropoxide. The vibrational bands in the IR absorbance spectra of the films are classified in terms of terminal V-O stretching (1050–880 cm^–1), bridging V-O^...Fe and V^...O^...Fe stretching (880–550 cm^–1), mixed V-O-V deformations and Fe-O stretching (<550 cm^–1) modes. Ex situ IR spectra of films were measured after consecutive charging/discharging to various intercalation coefficients x and correlated to the current peaks in the cyclic voltammetry curves measured in 1 M LiClO₄/propylene carbonate electrolyte. We classified the ex situ IR spectra of charged/discharged films according to their vibrational band changes. The results reveal that, for small values of the intercalation coefficient, crystalline FeVO₄, InVO₄ and Fe₂V₄O₁₃ films exhibit a simultaneous decrease in the intensity of all IR bands while the band frequencies remain unaffected. For the higher intercalation levels, IR mode frequencies are shifted, signaling the presence of reduced vanadium. Further charging leads to an amorphization of the film structure, which was established from the similarity of the IR spectra of charged films with those of amorphous films prepared at lower annealing temperatures. The results confirm that ex situ IR spectroelectrochemical measurement is an effective way to assess the structural changes in films with different levels of intercalation. Electronic Publication     

Untersuchungen an Kristallhydraten anorganischer Salze, 8. Mitt. Interpretation der Schwingungsspektren vonM(BF4)2·6H2O fürM=Fe2+, Co2+, Ni2+

The infrared and Raman spectra were recorded in the range 4000–160 cm^–1 forM(BF₄)₂·6 H₂O whereM=Fe²⁺, Co²⁺, Ni²⁺. The spectroscopic data support the X-ray structural data in showing that in the crystal hydrates studied two kinds of hydrogen bonds are present: H₂O...H₂O and OH₂... F₄B^–. The energies and molecular force constants (f _OH and fH₂O) andr _OH for OH₂...F₄B^– were calculated for the three crystal hydrates. It was found that the bond OH₂... F₄B^– is comparatively weak, with mean energy 3.7–3.3 kcal/mol. Two types of water molecule with different structures are existing as the first are participating in H₂O...H–O–H...F₄B^– and the second in BF₄ ^–...H–O–H...F₄B^–.     

Influence of Packing of Radical Cations on the Conductivity of the New Molecular Semiconductor (Doet)2ReO4

A new molecular semiconductor, (Doet)₂ReO₄(Doet is (1,4-dioxanediyl-2,3-dithio)ethylenedithiotetrathiafulvalene), is synthesized and examined by X-ray diffraction analysis. The crystal structure of (Doet)₂ReO₄is formed by [Doet]^+1/2layers with isle [ReO₄]^–anions located between them. The Doet radical cations from the adjacent layers are linked by intermolecular hydrogen interactions of the O···H type.