O-H and O-D stretching vibrations in isotopically dilute HDO molecules in some solid hydrates

Vibrational frequencies v_OH and v_OD have been measured for isotopically-dilute HDO molecules in eleven solid hydrates at 90 K. The results have been used to prepare a plot of the ratio v_OH/v_OD versus v_OH. The ratios fall on a smooth curve and decrease with decreasing frequencies v_OH. The anharmonicity constants ω_ex_e have been estimated. They were found to increase with decreasing v_OH.     

Diode laser i.r. spectrum and rovibrational analysis of CF3Br in the ν2 + ν3 region

The gas phase i.r. spectrum of CF₃Br, with natural isotopic abundance, has been investigated in the ν₂+ ν₃ region near 1120 cm⁻¹ using a tunable diode laser spectrometer. The measurements have been carried out at low temperature (⋍ 200 K) to minimize the effects due to the “hot” band absorptions. The K structure of many P(J) and R(J) manifolds has been resolved and analyzed: the maximum J value reached for individual lines was 62 and 70 for CF₃⁷⁹Br and CF₃⁸¹Br, respectively. The identified transitions have been used in a least-squares fit to the energy expression up to the quartic terms and molecular parameters for the ν₂ + ν₃ combination have been obtained. Residual weak features due to “hot” bands of ν₃ and ν₆ have been assigned; the J structure has been analyzed by means of a polynomial procedure and spectroscopic constants for both the isotopomers have been derived.     

Synthesis and study of cesium-containing phosphates with a β-tridymite structure

Complex phosphates CsMg_{1 ? x} M _x PO₄ (M = Mn, Co, Cu, Zn), containing cesium and metals in the oxidation state +2, have been synthesized, and their structure and thermal behavior have been studied. Continuous solid solutions (0 ?? x ?? 1) of the ??-tridymite structure type are formed in the CsMg_{1 ? x} Mn _x PO₄, CsMg_{1 ? x} Co _x PO₄, and CsMg_{1 ? x} Zn _x PO₄ systems, whereas limited solid solutions (0 ?? x ?? 0.4) are formed in the CsMg_{1 ? x} Cu _x PO₄ system. Based on DTA data, phase transitions have been revealed in the cobalt-, copper-, and zinc-containing phosphates, and the orthorhombic or monoclinic crystal system has been identified. Unit cell parameters of the solid solutions have been calculated. Thermal expansion of the CsMPO₄ phosphates has been studied.     

Atoms state and interatomic interactions in perovskite-like oxides: XXXII. Formation of paramagnetic clusters in the La1−0.33x Ca0.33x Fe x Al1−x O3 and La1−0.33x Sr0.33x Fe x Al1−x O3 solid solutions

Calcium- and strontium-containing lanthanum orthoferrites have been studied using magnetic dilution method. It has been shown that the iron-atom clusters with competing ferro- and antiferromagnetic exchange interactions can exist. By using Mossbauer spectroscopy, Fe(IV) atoms have been found in the La_1?0.33x Ca_0.33x Fe_xAl_1?x O₃ solid solutions and Fe(III) atoms in two different surroundings have been found in the La_1?0.33x Sr_0.33x Fe _x Al_1?x O₃ solid solutions. The compositions of paramagnetic clusters stable at the infinite dilution have been proposed basing of the magnetic susceptibility and Mossbauer spectroscopy data.     

D-isotope-labelled n-butane cations in CF3CCl3 and in CF2ClCFCl2: Structure and reactions at low temperature

Cations of n-butane, n-butane-1,4-d₆, -d₄, -d₂ and n-butane-2,3-d4 produced by X-irradiation of CF₂ClCFCl₂ and CF₃CCl₃ 3 matrices containing 1–2 mole% of solute have been investigated by ESR spectroscopy. The measurements have been performed at 77–130 K. The results confirm that the two largest couplings are assigned to two protons on the methyl groups. Smaller couplings have been resolved in CF₃CCl₃ and assigned to specific H atoms. A geometry with a non-planar carbon skeleton is proposed. Partly deuterated methyl groups give rise to rotational isomers. Thermal and photoinduced decompositions producing 2-butyl radicals and 2-butane cations have been further studied.     

Thermal behaviors of N-pyrrolidine-N′-(2-chlorobenzoyl)thiourea and its Ni(II), Cu(II), and Co(III) complexes

The N-pyrrolidine-N??-(2-chlorobenzoyl)thiourea, HL, and their Ni(II), Cu(II), and Co(III) complexes (NiL₂, CuL₂, and CoL₃) have been synthesized and characterized. The thermal decomposition reactions of all the compounds have been investigated by DTA/TG combined systems. The mass spectroscopy technique has been used to identify the products during pyrolytic decomposition. The pyrolytic final products have been analyzed by X-ray powder diffraction method. After comparison of thermogravimetric and mass results of HL, NiL₂, CuL₂, and CoL₃, the decomposition mechanism of these compounds have been suggested. The thermal stability of the Ni(II) and Cu(II) complexes according to the thermogravimetric curves follows the sequence: NiL₂?<?CuL₂. The values of the activation energy, E _a, have been obtained using model-free (Kissenger?CAkahira?CSunose, KAS, Flyn?CWall?COzawa, FWO, and Isoconversional) methods for all decomposition stages. The E _a versus the extent of conversion, ??, plots show that the values of E _a varies as ??. Thirteen kinetic model equations have been tested for selecting correct reaction models. The optimized value of E _a and Arrhenius factor, A, have been obtained using the best model equation. The thermodynamic functions (??H*, ??S*, and ??G*) have been calculated using these values.     

The spectra and structure of sulphur-containing organic compounds—V. The vibrational spectra and conformations of p-RC6H4SO2CH2X sulphones

The i.r. and Raman spectra of p-RC₆H₄SO₂CH₂X (R = H, CH₃, Cl, Br; X = Cl, Br) sulphone liquid solutions and crystals have been investigated. The existence of a mixture of trans and gauche conformations in liquid and solution phases has been established. The temperature dependences of the i.r. spectra have been studied and the values of ΔH = H (gauche) - H(trans) determined. The molecular conformations in the crystal have been determined by the dichroism of polarized i.r. spectral bands. In the case of CH₃C₆H₄SO₂CH₂Br polymorphic crystal modifications, differing in molecular conformations, have been found. An interpretation of the vibrational spectra is given. See Part IV, A. B. REMizov, F. S. BILALOV and 1. S. POMINOV, Spectrochim Acta, in press.     

Determination of K shell X-ray intensity ratios for some heavy elements

The K shell X-ray intensity ratios K_α2/K_α1, K_β1,3/K_α1 and K_β2/K_α1 for 21 elements with 65⩽Z⩽92 have been measured using an incident photon energy of 123.6 keV. The X-rays have been measured with a Si(Li) semiconductor detector. K_β and K_α X-rays have been analyzed into the components K_β1,3 and K_β2 and K_α1 and K_α2, respectively, using a computer program. The experimental results were compared with the theoretical values of Scofield and available experimental results. All X-ray intensity ratios values have been plotted versus atomic number.     

Glass transition and crystallization kinetics analysis of Sb–Se–Ge chalcogenide glasses

Differential thermal analysis (DTA) has been employed to investigate the effect of Ge addition on the glass transition behavior and crystallization kinetics of Sb₁₀Se_90?xGe_x (x = 0, 19, 21, 23, 25, 27) alloys. The three characteristic temperatures viz. glass transition (T _g), crystallization (T _c), and melting (T _m) have been determined and found to vary with the heating rates and Ge content. Thermal stability and glass forming tendency have been evaluated in terms of ΔT (= T _c ? T _g) and reduced glass transition temperature. The activation energies for glass transition and crystallization have been used to analyze the nucleation and growth process. The activation energy analysis also determines the suitability of alloys to be used in switching applications. Results have been interpreted in terms of bond energies and structural transformations in the investigated alloys.     

Model calculations of the vibrations of bonded water molecules

Model calculations have been made of the vibrational frequencies and normal modes of a water molecule vibrating in a combined internal and external field. A constant internal force field has been used together with an external central force field from four or three nearest-neighbour atoms to the water molecule. These neighbour atoms have been arranged either tetrahedrally or trigonally around the water molecule. The external force field has been further restricted by the use of five possible site symmetries for the water molecule, C_2v, C₂, C_s(σ_xz, C_s(σ_yz) and C₁. A series of calculations have been made where the external force constants have been varied within the range 1—80 Nm^?1.The nine calculated normal modes can be divided into three groups: intra-molecular, rotational and translational vibrations. Among the rotational vibrations it is found that, in the tetrahedral environment, the rocking mode occurs at lower frequencies than the twisting and wagging modes, whereas the opposite occurs for the trigonal environment. Frequency ratios have been calculated using the isotopic species H₂O, D₂O, HDO and H,¹⁸O. The twisting and wagging modes have the vH₂O/vD₂O ratio in the range 1.35-3-1.41 and the rocking mode in the range 1.26—1.41.     

Integrated absorption intensities of haloethanes and halopropanes

The infrared absorption intensities of the chlorofluorocarbons C₂Cl_xF_y, (x + y = 6); the hydrofluorocarbons C₂H_xF_yH (x + y = 6); and a number of hydrochlorofluorocarbons, including some members of the propane series, have been measured. Absorption intensities have been obtained by integration over specified ranges of frequencies. The ranges used include the atmospheric window (1250t-833 cm⁻¹), 3500-450 cm⁻¹, 1300-700 cm⁻¹, and those for selected individual absorption bands. Comparisons of the results have been made with published work where available, and attention is drawn to possible sources of error in the measurement of band areas. The spectra of the halopropanes have been included for the range 3500-150 cm⁻¹. A preliminary study has been made of the relation between the number of fluorine atoms in the molecule and the intensity of absorption of the CF stretching vibrations.     

Flattened fullerenes

Quantum-chemical calculations of giant flattened fullerenes C _n (lentil-shaped) have been carried out. The topology, molecular and electronic structure of these fullerenes have been studied. Such molecules consist of two identical coronenoid fragments of a graphite layer, which are arranged one above the other, and a system of polycondensed five- and six-membered cycles, which form a side surface of the cluster. Polyhedral structures with isolated pentagons of three symmetry types (D _6h ,D _6d , andD _3h ) have been considered. The topology of these structures is described in terms of planar molecular graphs. Electronic structures of eleven flattened lentil-shaped C _n clusters (n = 72–216) have been studied in the π approximation. Most of the considered systems have closed or quasi-closed electron shells (according to Hückel) and rather large energy gaps separating the highest occupied and lowest unoccupied MO, which is indicative of their kinetic stability. Fragments of the potential energy surfaces of the C₇₂ and C₉₆ fullerenes have been studied by the MNDO, AM1, and MNDO/PM3 methods. For the C₉₆ cluster, two local energy minima, which correspond to the lentil-shaped isomers withD _6h andD _6d symmetry, have been determined. As a result of optimization of geometric parameters, it was found that all three methods give close values of heights (H = 6.7 Å) and diameters (D = 9.8 Å) for both isomers. The clusters change to quasi-two-dimensional systems (H«D) with increasing sizes of coronenoid fragments.     

Physical properties and electronic structure of TaC-HfC solid solutions

The results of investigations of the physical properties and electronic structure in the Hf _x Ta_1?x solid solutions have been generalized. The N ₃ X-ray emission spectra Ta in hafnium and tantalum carbides have been investigated for the first time. Peak locations and intensities have been compared with the results of calculations of the electron band structure of Hf _x Ta_1?x C alloys with x = 0, 0.25, 0.5, and 0.75. It has been found that the inversion of peak intensities with increasing hafnium concentration is due to a nonmontonic variation in the density of Ta 5d states in the valence band of these compounds.     

Spectroscopic studies on 3- and 5-formylsalicylic acids and their complexes with Fe(III)

The electronic absorption spectra of 3-formylsalicylic acid (3-fsa) and 5-formylsalicylic acid (5-fsa) have been studied in different pure and mixed solvents. From the pure solvent study, the Einstein transition probabilities (A_if and B_if), dipole moment (D_if), oscillator strength (F_if), life time (τ), and the molar extinction coefficient (?) of the absorption bands were determined. The hydrogen bonding and orientation energies between solute and solvent molecules have been investigated from the mixed solvent spectra. The equilibrium constants, pK_a1 and pK_a2, of the two acids have been determined spectrophotometrically and a new approximate method for pK_a1 determination is suggested. The complex formation between 3-fsa and 5-fsa and Fe³⁺ in solution has been investigated spectrophotometrically and the stoichiometric ratios of the two systems have been determined applying the continuous variation, mole-ratio and the slope ratio methods which all showed a 1:1 type of complexes.     

Thermodynamics of undecanolactone,tridecanolactone, and pentadecanolactone from 0 to 340 K

The heat capacities C_p^o of undercanolactone, tridecanolactone, and pentadecanolactone have been measured between 10 and 370 K in a vacuum adiabatic calorimetric cryostat within about 0.2 per cent. The temperatures and enthalpies of physical transitions have been also estimated. The enthalpies of combustion of the compounds have been measured in an isothermal calorimeter with an accuracy of 0.05 per cent. From the results the functions {H (T) ? H (0)}, S^o(T), and {G^o(T) ? H^o(0)} have been calculated over the range 0 to 340 K, and the values of ΔH_f^o, ΔG_f^o and ΔS_f^o have been evaluated at T = 298.15 K.     

Oxygen equilibrium pressure above V2O5−x and thermodynamic properties of this oxide system

Measurements of oxygen equilibrium pressure above the V₂O_5?x oxide system have been performed within the temperature range 575 to 615°C. The results have been used to determine the standard enthalpy and entropy in the reaction V₆O₁₃ + O₂ = 3 V₂O₅. The thermodynamic properties of the V₂O_5?x system (at x < 1) cited in the literature have been discussed for all the equilibria postulated.     

Diode laser spectra of cis-HONO near 850 cm−1 and trans-HONO near 1700 cm−1

Tunable diode laser spectra have been measured for the ν₄ band of cis-HONO near 850 cm^?1 and the ν₂ band of rans-HONO near 1700 cm^?1. The ν₄ band is completely unperturbed and 355 well-resolved transitions have been fit with a standard deviation of 0.0007 cm^?1. The ν₂ band appears to have some small perturbations, but about 190 transitions have been fit with a standard deviation of 0.0027 cm^?1. Rotational and centrifugal distortion constants are given for both bands.     

Subsolidus phase diagrams of the systems Cs2MoO4-R2(MoO4)3-Zr(MoO4)2, where R = Al, Sc, or In

The systems Cs₂MoO₄?R₂(MoO₄)₃?Zr(MoO₄)₂, where R = Al, Sc, or In, have been investigated in the subsolidus region by X-ray powder diffraction. Quasi-binary joins have been revealed, and triangulation has been carried out. Six new triple molybdates have been prepared with the component ratio equal to 1 : 1 : 1 (mol/mol) (S ₁) and 5 : 1 : 2 (S ₂). The crystal parameters for the 5 : 1 : 2 compounds have been determined, and the electrical properties of the 1 : 1 : 1 compounds have been investigated.     

On the unperturbed dimensions of polyisoprene chains

The characteristic ratio C_∞ = 〈r²〉 _o/nl² and its temperature coefficient dlnC_∞/dT for synthetic polyisoprenes with high cis 1,4 and trans 1,4 contents have been determined by various experimental methods, involving viscometric determinations. The θ-solvent dioxane at 31.2°C and benzene at temperatures in the range 25–45°C have been used with the cis isomer. Thermodynamic quantities required for the analysis in benzene, such as the reduced residual chemical potential χ and its temperature coefficient d_χ/dT, have been taken from the rigorous work of Eichinger and Flory, in which the equation-of-state theory was introduced. A large error has been found in the determination of the temperature coefficient in benzene, arising from the small values for ($\text{1}\text{2}\text{?}{}_{\mathrm{\chi }}$) and d_χ/dT. Selected θ-mixtures, toluene/n-propanol at various temperatures, have been employed with trans polyisoprene. Experimental values have been compared with those obtained from theoretical calculations carried out by authors since Mark in 1964. Reasonable agreement was found, especially for the trans isomer.     

Ab initio studies of the structures and force fields of ketenimine and related molecules

Theoretical equilibrium geometries for ketenimine, aminoacetylene and ethynol have been obtained using the MP3/6-31G** ab initio method. Empirical scaling factors have been introduced to estimate the rotational constants A_o, B_o and C_o. In addition the complete harmonic force fields for ketenimine, ketene and diazomethane have been computed, normal coordinate analyses have been performed and the quartic centrifugal distortion constants estimated.