The Raman OH stretching bands of liquid water

In this work, from the discussion on water structure and clusters, it can be deduced that the OH stretching vibration is closely related to local hydrogen-bonded network for a water molecule, and different OH vibrations can be assigned to OH groups engaged in various hydrogen bonding. At ambient condition, the main local hydrogen bonding for a molecule can be classified as DDAA (double donor–double acceptor), DDA (double donor–single acceptor), DAA (single donor–double acceptor) and DA (single donor–single acceptor) and free OH vibrations. As for water at 290 K and 0.1 MPa pressure, the OH stretching region of the Raman spectrum can be deconvoluted into five sub-bands, which are located at 3014, 3226, 3432, 3572, and 3636 cm⁻¹, and can be assigned to ν_DAA-OH, ν_DDAA-OH, ν_DA-OH, ν_DDA-OH, and free OH₂ symmetric stretching vibrations, respectively.     

Infrared diode laser spectroscopy of the ν = 2 band of AlF

A vibrational–rotational spectrum of the ν = 2 transitions of a high-temperature molecule AlF was observed between 1490 and 1586 cm⁻¹ with a diode laser spectrometer. Measurements were made on the ν = 3–1, 4–2, 5–3 and 8–6 bands at a temperature of 900 °C. Measured spectral lines were fitted to effective band constants ν₀, B_ν and D_ν for each band. Present measurements were made with only one Pb-salt laser diode. Physical significance of the effective band constants is discussed.     

Electronic donor-acceptor interactions of anthracene with a dehydroxylated surface of silica gel and aerosil

The ability of a dehydroxylated surface of silica gel and aerosil to enter into donor-acceptor interactions with poly-acenes was demonstrated by methods of steadystate and kinetic spectrofluorometry. The anthracene molecule forms EDA complexes with electron-acceptor sites of silica gel and aerosil in the ground state (charge-transfer complex, CTC) and the excited state (exciplex). At a degree of coverage of the silica gel and aerosil surfaces by polyacene molecules of 10^–1–10^–3% of a monolayer, energetic and structural inhomogeneity of the OH groups of silica gel appears. Silica gel possesses stronger electron acceptor sites; the electron-acceptor sites of aerosil are more accessible to EDA interactions and more monotypic. Vacancy defects of the SiO₂ matrix are suggested as accepting sites.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 6, pp. 693–698, November–December, 1986.     

Chromium(III) Hydroxide Solubility in The Aqueous Na+-OH?-H2PO?4-HPO2?4-PO3?4-H2O System: A Thermodynamic Model

Chromium(III)-phosphate reactions are expected to be important in managing high-level radioactive wastes stored in tanks at many DOE sites. Extensive studies on the solubility of amorphous Cr(III) solids in a wide range of pH (2.8–14) and phosphate concentrations (10^–4 to 1.0 m) at room temperature (22±2)°C were carried out to obtain reliable thermodynamic data for important Cr(III)-phosphate reactions. A combination of techniques (XRD, XANES, EXAFS, Raman spectroscopy, total chemical composition, and thermodynamic analyses of solubility data) was used to characterize solid and aqueous species. Contrary to the data recently reported in the literature,⁽¹⁾ only a limited number of aqueous species [Cr(OH)₃H₂PO^–₄, Cr(OH)₃(H₂PO₄)^2–₂), and Cr(OH)₃HPO^2–₄] with up to about four orders of magnitude lower values for the formation constants of these species are required to explain Cr(III)-phosphate reactions in a wide range of pH and phosphate concentrations. The log K^o values of reactions involving these species [Cr(OH)₃(aq)+H₂PO^–₄⇌Cr(OH)₃H₂PO^–₄; Cr(OH)₃(aq)+2H₂PO^–₄⇌Cr(OH)₃(H₂PO₄)^2–₂; Cr(OH)₃(aq)+HPO^2–₄⇌Cr(OH)₃HPO^2–₄] were found to be 2.78±0.3, 3.48±0.3, and 1.97±0.3, respectively.     

Palladized aluminum electrode covered by Prussian blue film as an effective transducer for electrocatalytic oxidation and hydrodynamic amperometry of N-acetyl-cysteine and glutathione

The mediated oxidation of N-acetyl cysteine (NAC) and glutathione (GL) at the palladized aluminum electrode modified by Prussian blue film (PB/Pd–Al) is described. The catalytic activity of PB/Pd–Al was explored in terms of Fe^III[Fe^III(CN)₆]/Fe^III[Fe^II(CN)₆]¹⁻ system by taking advantage of the metallic palladium layer inserted between PB film and Al, as an electron-transfer bridge. The best mediated oxidation of NAC and GL on the PB/Pd–Al electrode was achieved in 0.5 M KNO₃ + 0.2 M potassium acetate of pH 2. The mechanism and kinetics of the catalytic oxidation reactions of the both compounds were monitored by cyclic voltammetry and chronoamperometry. The charge transfer-rate limiting step as well as overall oxidation reaction of NAC or GL is found to be a one-electron abstraction. The values of transfer coefficients α, catalytic rate constant k and diffusion coefficient D are 0.5, 3.2 × 10² M⁻¹ s⁻¹ and 2.45 × 10⁻⁵ cm² s⁻¹ for NAC and 0.5, 2.1 × 10² M⁻¹ s⁻¹ and 3.7 × 10⁻⁵ cm² s⁻¹ for GL, respectively. The modifying layers on the Pd–Al substrate have reproducible behavior and a high level of stability in the electrolyte solutions. The modified electrode is exploited for hydrodynamic amperometry of NAC and GL. The amperometric calibration graph is linear in concentration ranges 2 × 10⁻⁶–40 × 10⁻⁶ for NAC and 5 × 10⁻⁷–18 × 10⁻⁶ M for GL and the detection limits are 5.4 × 10⁻⁷ and 4.6 × 10⁻⁷ M, respectively.     

Potential-dependent chemisorption of carbon monoxide on platinum electrodes: new insight from quantum-chemical calculations combined with vibrational spectroscopy

Density functional theory (DFT) using the finite cluster approach is utilized to compute binding energies, bond geometries, and vibrational properties of carbon monoxide adsorbed on Pt(111) as a function of the external interfacial field, focusing attention on the metal–CO bond itself. Comparison with electrode potential-dependent frequencies for the metal–CO (ν_M–CO) as well as the much-studied intramolecular C---O (ν_CO) vibration, as measured by in-situ Raman and infrared spectroscopy, facilitate their interpretation in terms of metal-chemisorbate bonding for this archetypal electrochemical system. Decomposing the calculated metal–CO binding energy and vibrational frequencies into individual orbital and steric repulsion components enables the role of such quantum-chemical interactions to the field- (and hence potential-) dependent bonding to be assessed. No simple relationship between the field(F)-dependent binding energies and the ν_M–CO frequencies is evident. While the DFT ν_M–CO–F slopes are negative at positive and small–moderate negative fields, reflecting the prevailing influence of back-donation, a ν_M–CO–F maximum is obtained at larger negative fields for atop CO, and a plateau for hollow-site CO. This Stark-tuning behavior reflects largely offsetting field-dependent contributions from π and σ surface bonding, and can also be rationalized on the basis of changes in the electrostatic component of ν_M–CO from increasing M–CO charge polarization. A rough correlation between the field-dependent ν_M–CO frequencies and the corresponding bond distances, r_M–CO, is observed for hollow and atop CO in that r_M–CO shortens towards less positive fields, but becomes near-constant at moderate–large negative fields. A more quantitative correlation between the field-dependent C---O frequencies and bond lengths is also evident. In harmony with earlier findings (and unlike the ν_M–CO–F behavior), the ν_CO–F dependence is due chiefly to changes in the back-donation bonding component. The overall vibrational frequency-field behavior predicted by DFT is also in semi-quantitative concordance with experimental potential-dependent spectra.     

Electrocatalytic response of carbohydrates at copper-alloy electrodes

The voltammetric responses observed for carbohydrates and polyalcohols at 0.60 V in 0.10 M NaOH are significantly larger at preanodized CuMn (95:5) electrodes as compared to preanodized pure Cu electrodes. Apparent values for the number of electrons transferred (n_app) and the corresponding values of heterogeneous rate constants (k_app) are estimated for selected reactants from the slopes and intercepts, respectively, of Koutecký–Levich plots of background-corrected voltammetric currents obtained at CuMn and Cu rotated disk electrodes (RDEs). Values of n_app (and k_app) for sorbitol and glucose are 11.8 (9.2×10⁻³ cm s⁻¹) and 11.7 (8.0×10⁻³ cm s⁻¹), respectively, at a CuMn RDE. These are compared to the values 10.4 (1.8×10⁻³ cm s⁻¹) and 9.6 (2.0×10⁻³ cm s⁻¹) for sorbitol and glucose, respectively, at a Cu RDE. The larger sensitivities observed at the CuMn RDE in comparison to the Cu RDE are concluded to be the beneficial result of larger k_app values at the alloy electrode. Furthermore, the larger k_app values are speculated to result from enhanced preadsorption of the reactant species at Mn(IV) sites in the preanodized CuMn surface. In flow-injection measurements, the peak signals obtained for successive injections of glucose using a CuMn electrode (0.60 V vs. SCE) were quite stable with a standard deviation of 1.5%. However, large day-to-day variations (±15%) observed in the average peak signals are attributed to the temperature sensitivities of the k_app value and the diffusion coefficient for glucose.     

Pulse radiolysis study of ion-species effects on the solvated electron in alkylammonium ionic liquids

The spectra and kinetic behavior of solvated electrons (e_sol⁻) in alkyl ammonium ionic liquids (ILs), i.e. N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI), N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMMA-BF₄), N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI), N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13-TFSI), N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13-TFSI), and N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P14-TFSI) were investigated by the pulse radiolysis method. The e_sol⁻ in each of the ammonium ILs has an absorption peak at 1100 nm, with molar absorption coefficients of 1.5–2.3×10⁴ dm³ mol⁻¹ cm⁻¹. The e_sol⁻ decayed by first order with a rate constant of 1.4–6.4×10⁶ s⁻¹. The reaction rate constant of the solvated electron with pyrene (Py) was 1.5–3.5×10⁸ dm³ mol⁻¹ s⁻¹ in the various ILs. These values were about one order of magnitude higher than the diffusion-controlled limits calculated from measured viscosities. The radiolytic yields (G-value) of the e_sol⁻ were 0.8–1.7×10⁻⁷ mol J⁻¹. The formation rate constant of e_sol⁻ in DEMMA-TFSI was 3.9×10¹⁰ s⁻¹. The dry electron (e_dry⁻) in DEMMA-TFSI reacts with Py with a rate constant of 7.9×10¹¹ dm³ mol⁻¹ s⁻¹, three orders of magnitude higher than that of the e_sol⁻ reactions. The G-value of the e_sol⁻ in the picosecond time region is 1.2×10⁻⁷ mol J⁻¹. The capture of e_dry⁻ by scavengers was found to be very fast in ILs.     

β-Lactam antibiotics. Spectroscopy and molecular orbital (MO) calculations: Part I: IR studies of complexation in penicillin-transition metal ion systems and semi-empirical PM3 calculations on simple model compounds

IR studies were preformed to determine possible transition metal ion binding sites of penicillin. the observed changes in spectral position and shape of characteristic IR bands of cloxacillin in the presence of transition metal ions (both in solutions and in the solid state) indicate formation of M–L complexes with engagement of –COO⁻ and/or –CONH– functional groups. The small shift of ν_C=O towards higher frequencies rules out direct M–L interaction via β-lactam carbonyl. PM3 calculations on simple model compounds (substituted formamide, cyclic ketones, lactams and substituted monocyclic β-lactams) have been performed. All structures were fully optimized and the calculated bond lengths, angles, heats of formation and C=O stretching frequencies were discussed to determine the β-lactam binding sites and to explain its susceptibility towards nucleophilic attack (hydrolysis in vitro) and biological activity. The relative changes of calculated values were critically compared with available experimental data and same correlation between structural parameters and in vivo activity was shown.     

Oxidative degradation of non-ionic surfactant (TritonX-100) by chromium(VI)

Degradation of polyoxyethylene chain of non-ionic surfactant (TritonX-100) by chromium(VI) has been studied spectrophotometrically under different experimental conditions. The reaction rate bears a first-order dependence on the [Cr(VI)] under pseudo-first-order conditions, [TritonX-100]  [Cr(VI)] in presence of 1.16 mol dm⁻³ perchloric acid. The observed rate constant (k_obs) was 3.3 × 10⁻⁴ to 3.5 × 10⁻⁴ s⁻¹ and the half-life (t_1/2) was 33–35 min for chromium(VI). The effects of total [TritonX-100] and [H⁺] on the reaction rate were determined. Reducing nature of non-ionic TritonX-100 surfactant is found to be due to the presence of –OH group in the polyoxyethylene chain. It was observed that monomeric and non-ionic micelles of TritonX-100 were oxidized by chromium(VI). When [TritonX-100] was less than its critical micelle concentration (cmc) the k_obs values increased from 0.76 × 10⁻⁴ to 1.5 × 10⁻⁴ s⁻¹. As the [TritonX-100] was greater than the cmc, the k_obs values increases from 2.1 × 10⁻⁴ to 8.2 × 10⁻⁴ s⁻¹ in presence of constant [HClO₄] (1.16 mol dm⁻³) at 40 °C. A comparison was made of the oxidative degradation rates of TritonX-100 with different metal ion oxidants. The order of the effectiveness of different oxidants was as follows: permanganate > diperiodatoargentate(III) > chromium(VI) > cerium(IV).     

Spectrophotometric study of acid-base equilibria of 4-(2-benzothiazolylazo)resorcinol and 4-(2-benzothiazolylazo)salicylic acid in water-organic solvent media

The visible absorption spectra of 4-(2-benzothiazolylazo)resorcinol (BTAR) and 4-(2-benzothiazolylazo)salicylic acid (BTAS) have been recorded in water-organic solvent mixtures in the pH range 0.5–12.0. The organic solvents used are methanol, ethanol,n-propanol, iso-propanol, acetone, dioxane and dimethyl formamide. The spectral changes have been explained in terms of shifts in equilibria among different molecular and ionic species of BTAR and BTAS existing in solution. The pK _a values corresponding to the different ionization steps have been determined at 25°C and I=0.1M (KNO₃) by graphic analysis of the absorbance-pH curves. The results obtained are discussed in terms of the molecular structure of the reagents and the nature of the organic co-solvent used.     

Towards the understanding of the spectroscopic behaviour of the C–H oscillator in C–HO hydrogen bonds: the effect of solvent polarity

The effect of solvent polarity versus specific C–HO contacts on the vibrational νC–H mode is studied using CHCl₃ as a model system. Ab initio SCI–PCM calculations show that the overall shift of the νC–H band, sometimes ascribed to the C–HO hydrogen bonding, can in fact be explained by the electrostatic interaction with a dielectric environment. The presence of a new νC–H band – assigned to the C–HO bonded forms – remains as the most reliable evidence of C–HO hydrogen bonding.     

Evaluation of a chloramine-T-selective electrode for catalytic titration of silver and mercury(II) based on iodide-catalyzed chloramine-T reactions

Semiautomatic methods are described for the catalytic titrimetric determination of microamounts of silver and mercury(II) using a chloramine-T-selective electrode as monitor. The methods are based on the inhibitory effect of Ag(I) and Hg(II) on the iodide-catalyzed chloramine-T-arsenite and chloramine-T-H₂O₂ reactions. Microamounts of silver in the range 0.2–200 μg (1 × 10⁻⁷−1 × 10⁻⁴ M) and of mercury(II) in the range 0.1–200 μg (2.5 × 10⁻⁸−5 × 10⁻⁵ M) were determined using the chloramine-T-As(III) indicator reaction. Mercury(II) in the range 4–2000 μg (1 × 10⁻⁶−5 × 10⁻⁴ M) was also determined using the chloramine-T-H₂O₂ indicator reaction. The accuracy and precision were in the range 0.1–1%.     

Spectrophotometric and spectroscopic studies of complexation of 8-hydroxyquinoline with π acceptor metadinitrobenzene in different polar solvents

The complexation of electron donor–acceptor complexes of 8-hydroxyquinoline (8HQ) and metadinitrobenzene (MNB) have been studied spectrophotometrically and thermodynamically in different polar solvent at room temperature. A new absorption band due to charge transfer (CT) transition is observed in the visible region. A new theoretical model has been developed which take into account the interaction between electronic subsystem of 8HQ and MNB. The results indicate the extent of charge transfer complexes (CTCs) formation to be more in less polar solvents. Stoichiometry of the complex was found to be 1:1 by straight line method and ¹H NMR between donor and acceptor at the maximum absorption bands. Ionization potential (I_D) and resonance energy (R_N) were determined from the CT transition energy in different solvents. The formation constants of the complexes were determined in different polar solvents from which ΔG° formation of the complexes was estimated and also extinction coefficient of the charge transfer complex (CTC) was calculated. Oscillator strength, transition dipole strengths and maximum wavelength of the CTC (λ_CT) in various solvents and IR spectra of the CTC have also been discussed. It has been observed that all parameters described above changed with change in polarity and concentration of donor.     

Investigations of molecular interactions in propionic acid–N,N-dimethyl formamide binary system—FTIR study

FTIR spectra of propionic acid (PA), N,N-dimethyl formamide (DMF) and its binary mixtures with varying molefractions of the PA were recorded in the region 500–3500 cm⁻¹, to investigate the formation of hydrogen bonded complexes in a mixed system. The observed features in ν(CO), δ(OC–N) and ν_as(CN) of DMF, ν(CO) and ν(CO) of PA have been explained in terms of the hydrogen bonding interactions between DMF and PA and dipole–dipole interaction. The intrinsic bandwidth for the vibrational modes ν_as(CN) and ν(CO) has been elucidated using Bondarev and Mardaeva model.     

In situ study of diffusion and interaction of water and electrolyte solution in polyacrylonitrile (PAN) membrane using FTIR and two-dimensional correlation analysis

In the study, the diffusion process of water and CaCl₂ aqueous solution in polyacrylonitrile (PAN) membrane have been investigated using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and two-dimensional (2D) correlation analysis. In 2D ATR-FTIR spectra, the water ν(OH) band in PAN membrane during both water and CaCl₂ solution diffusion is split into three separate bands. However, the OH band appearing from bound water which forms hydrogen-bonding of CaCl₂ solution diffusion has a considerably lower wavenumber than that of pure water diffusion, which is due to association between Ca²⁺ ions and the CN groups in PAN. The sequential orders of the intensity changes for water and CaCl₂ solution diffusion in the region of ν(OH) and ν(CN) bands reveal the diffusion process and interaction of water and electrolyte in PAN membrane. That is, in the process of water diffusion in PAN membrane, water molecules first interact with –CN group in PAN to form weak hydrogen bond, then the moderate hydrogen-bonding interactions start gradually, and finally, the strong hydrogen-bonding interactions may be formed. When CaCl₂ solution diffuses in PAN membrane, the CN groups in PAN first associate with Ca²⁺ ions and then interact with water molecules to form hydrogen bond that grows gradually from weak to strong. Furthermore, the results are validated further by band fitting to calculate the ratio of each component band area and the proportion of component band to ν(OH) water band.     

Sensitive, selective spectrophotometric determination of phenols with periodic acid

A new spectrophotometric determination of phenols with periodic acid has been developed. The colored product of phenol periodic acid reaction has a λ_max 380 nm. The determination of phenol, pyrocatechol, α-naphthol, β-naphthol, quinol, p-cresol, m-cresol, 8-quinolinol, resorcinol, phloroglucinol, and gallic acid has been done. The effects of possible variables e.g., temperature, reagent, pH buffers have been studied. A study of interferences is made. Mechanism of the reaction is discussed.     

Synthesis and NMR spectra of the hydroxyundecahydro-closo-dodecaborate [B12H11OH]2− and its acylated derivatives

Tetrabutylammonium hydroxyundecahydro-closo-dodecaborate was obtained in high yield via [B₁₂H₁₁NMP]^–(NMP =N-methylpyrrolidone) by the modified method. [B_i2H₁₁OH]^2– is easily acylated by aromatic acyl chlorides to give novel compounds [B₁₂H₁₁OCOAr]^2– in high yields. All the compounds were characterized by standard and special NMR methods.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 722–725, March, 1996.     

Mittlere Schwingungsamplituden der Hexachloro- und Hexabromo-Anionen einiger Lanthanide

Mean amplitudes of vibration for various octahedral complex compounds of the typeLnCl₆ ^3– andLnBr₆ ^3– (withLn=Nd, Eu, Gd, Dy, Er, and Yb) have been calculated, at different temperatures, using known spectroscopic data. The results are briefly discussed and it is found that theLn–Cl andLn–Br amplitude values are highly characteristic.

     

Supramolecular fullerene/porphyrin charge transfer interaction studied by absorption spectrophotometric method

A detailed UV–Vis spectrometric and thermodynamic studies were done to look insight into the nature of molecular interactions of the electron donor–acceptor complexes of C₆₀ and C₇₀ with 5,10,15,20-tetrakis(octadecyloxyphenyl)-21H,23H-porphyrin (1) in chloroform and toluene. Charge transfer (CT) absorption bands were located in the visible region and vertical ionization potential of 1 was determined utilizing CT transition energy. Low values of oscillator and transition dipole strengths suggested that the complexes were almost of neutral character in ground states. The high binding constant value for the C₇₀–1 complex indicated high selectivity of 1 molecule towards C₇₀. Experimental as well as theoretically determined of enthalpies of formation value substantiated the trend in K values for fullerene–1 complexes.