Molecular precursors for the preparation of homogenous zirconia-silica materials by hydrolytic sol-gel process in organic media. Crystal structures of [Zr{OSi(O(t)Bu)3}4(H2O)2]·2H2O and [Ti(O(t)Bu){OSi(O(t)Bu)3}3

[Zr(OPr(i))(4)·Pr(i)OH] reacts with [HOSi(O(t)Bu)(3)] in anhydrous benzene in 1:1 and 1:2 molar ratios to afford alkoxy zirconosiloxane precursors of the types [Zr(OPr(i))(3){OSi(O(t)Bu)(3)}] (A) and [Zr(OPr(i))(2){OSi(O(t)Bu)(3)}(2)] (B), respectively. Further reactions of A or B with glycols in 1:1 molar ratio afforded six chemically modified precursors of the types [Zr(OPr(i))(OGO){OSi(O(t)Bu)(3)}] (1A-3A) and [Zr(OGO){OSi(O(t)Bu)(3)}(2)] (1B-3B), respectively [where G = (-CH(2)-)(2) (1A, 1B); (-CH(2)-)(3) (2A, 2B) and (-CH(2)CH(2)CH(CH(3)-)} (3A, 3B)]. The precursors A and B are viscous liquids, which solidify on ageing whereas the other products are all solids, soluble in common organic solvents. These were characterized by elemental analyses, molecular weight measurements, FAB mass, FTIR, (1)H, (13)C and (29)Si-NMR studies. Cryoscopic molecular weight measurements of all the products, as well as the FAB mass studies of 3A and 3B, indicate their monomeric nature. However, FAB mass spectrum of the solidified B suggests that it exists in dimeric form. Single crystal structure analysis of [Zr{OSi(O(t)Bu)(3)}(4)(H(2)O)(2)]·2H(2)O (3b) (R(fac) = 11.9%) as well as that of corresponding better quality crystals of [Ti(O(t)Bu){OSi(O(t)Bu)(3)}(3)] (4) (R(fac) = 5.97%) indicate the presence of a M-O-Si bond. TG analyses of 3A, B, and 3B indicate the formation of zirconia-silica materials of the type ZrO(2)·SiO(2) from 3A and ZrO(2)·2SiO(2) from B or 3B at low decomposition temperatures (≤200 °C). The desired homogenous nano-sized zirconia-silica materials [ZrO(2)·nSiO(2)] have been obtained easily from the precursors A and B as well as from the glycol modified precursors 3A and 3B by hydrolytic sol-gel process in organic media without using any acid or base catalyst, and these were characterized by powder XRD patterns, SEM images, EDX analyses and IR spectroscopy.     

Dosimetric evaluation of an indigenously developed 10 MeV industrial electron beam irradiator

The high dose rate electron beams are increasingly being used for radiation processing of various products worldwide. A comprehensive dosimetric evaluation of an in-house developed 10 MeV industrial electron beam irradiator was carried out in static as well as in dynamic mode of irradiations. Radiochromic B3 film and graphite calorimeter were used for dosimetric measurements. The dose rate from the electron beam was also calculated using the empirical relation prescribed in the ASTM report E2232-02. The measured electron beam profile indicates the dose rate variation within 8% in the irradiated product boxes. The most probable energy determined from the depth dose distribution in PMMA, Al and water was found in agreement with the intended energy of the electron beam. Measured dose rate using radiochromic film and graphite calorimeter were found in good agreement with each other and also found comparable with the theoretically estimated dose rates. Experimentally measured dose rates were considered for the trial irradiation of medical and industrial products. Dosimetric data obtained through this study confirms the suitability of the irradiator for routine radiation processing of various products.     

Pair diffusion, hydrodynamic interactions, and available volume in dense fluids

We calculate the pair diffusion coefficient D(r) as a function of the distance r between two hard sphere particles in a dense monodisperse fluid. The distance-dependent pair diffusion coefficient describes the hydrodynamic interactions between particles in a fluid that are central to theories of polymer and colloid dynamics. We determine D(r) from the propagators (Green's functions) of particle pairs obtained from molecular dynamics simulations. At distances exceeding ~3 molecular diameters, the calculated pair diffusion coefficients are in excellent agreement with predictions from exact macroscopic hydrodynamic theory for large Brownian particles suspended in a solvent bath, as well as the Oseen approximation. However, the asymptotic 1/r distance dependence of D(r) associated with hydrodynamic effects emerges only after the pair distance dynamics has been followed for relatively long times, indicating non-negligible memory effects in the pair diffusion at short times. Deviations of the calculated D(r) from the hydrodynamic models at short distances r reflect the underlying many-body fluid structure, and are found to be correlated to differences in the local available volume. The procedure used here to determine the pair diffusion coefficients can also be used for single-particle diffusion in confinement with spherical symmetry.     

FTIR and FT‐Raman spectra and density functional computations of the vibrational spectra,molecular geometry and atomic charges of the biomolecule: 5‐bromouracil

FTIR and FT‐Raman spectra of 5‐bromouracil in the powder form were recorded in the region 400–4000 cm⁻¹ and 50–4000 cm⁻¹, respectively. The observed wavenumbers were analysed and assigned to different normal modes of vibration of the molecule. Quantum chemical calculations were performed to support the assignments of the observed wavenumbers. The performance of the B3LYP hybrid density functional (DFT) method was compared with other methods. With the 6–31 G** and 6–311 + G(2d,p) basis sets, the calculated geometry, dipole moments and harmonic vibrations were determined. A comparison with the uracil molecule was made, and specific scale factors were deduced and employed in the predicted wavenumbers of 5‐bromouracil. The total atomic charges and thermodynamic parameters were calculated, and are discussed briefly. Structure and harmonic vibrations of 5‐bromouracil were also calculated in the presence of water within a simple model with one molecule. It is observed that the bromine atom at position 5 exhibits smaller inductive effects than the fluorine atom, producing a small distortion of the electrostatic potential around the ring and a reduction of the molecular dipole moment. Copyright © 2007 John Wiley & Sons, Ltd.     

Treatment feasibility of highly alkaline and highly radioactive liquid waste—a novel approach

Journal of Radioanalytical and Nuclear Chemistry - Typical Radioactive liquid waste with high alkalinity, high concentration of solvent degradation products along with high 134+137Cs content was...     

Selectivity enhancement in tritium isotope separation by multiple frequency multiple photon dissociation of the CTF3/CHF3 System

Isotope separation of tritium by multiple photon dissociation process in multiple frequency fields of a TEA-CO₂ laser is reported for the first time. A ten-fold improvement in the bulk selectivity was obtained in 8.5 Torr CTF₃/CHF₃ in the presence of buffer gas at room temperature using 9R(8) to 9R(14) CO₂ laser lines compared to single frequency excitation. Investigations of various process parameters such as exciting laser frequencies, pulse energy, sample and buffer gas pressure indicate that this is a promising technique for the separation of tritium.     

Spectrophotometric determination of Fe(III) with tiron in the presence of cationic surfactant and its application for the determination of iron in Al-alloys and Cu-based alloys

A sensitive Spectrophotometric method for the determination of iron with tiron and a cationic surfactant, cetylpyridinium chloride, at pH 5.6 is reported. The complex is extracted into a chloroform-propan-2-ol (41) mixture and shows maximum absorbance at 520 nm. Beer's law is obeyed in the range 1–14 g/ml with an average molar absorptivity of 15800 l mol^–1 cm^–1. The molar ratio as determined by Job's method for Fe:tiron:CPC is 143. Interferences by various ions are examined. Zr, Ti and Mo interfere heavily. The method is applied for the determination of iron in Al-based and Cu-based alloys, using appropriate masking agents.     

Infrared laser multiple photon dissociation of thiophene in gas phase

Infrared laser multiple photon excitation/dissociation of Thiophene (Th) was studied as a function of Th pressure, laser pulse energy, pulse duration and added buffer gas. While the excitation process was probed via optoacoustic technique, the stable reaction products were analyzed by IR spectroscopy and mass spectrometry. Although C₂H₂ and CH₃CCH were the major hydrocarbon products under all experimental conditions, the distribution of these, as well as higher hydrocarbons of lower yield, was found to be very much dependent upon the experimental conditions. The laser induced reaction under dielectric breakdown conditions with either high substrate pressure or laser energy produced significant amount of CS₂ and unidentified polymer as well. We propose a mechanism involving breakage of the C–S bond in Th to form an unstable 1,5-diradical which further decomposed via different channels. However, at higher substrate pressures, radical-Th reactions complicated the overall chemistry of the system. Evidences for collisional energy-pooling and rotational hole-filling were also obtained.     

Selective ir laser chemistry of CDF3 in natural fluoroform

Selective decomposition of CDF₃ at natural abundance level (150ppm) in fluoroform has been achieved by infra-red multiple-photon excitation at moderate substrate pressure using 100 ns FWHM CO₂ laser pulses. Effects of energy fluence, number of laser pulses, buffer gas pressure and substrate pressure on decomposition yield and bulk selectivity are reported and discussed.