The force field of carbon suboxide

The complete force field for carbon suboxide has been evaluated. The optimum geometry, stretching and interaction force constants are obtained from a combination of the CNDO/force molecular orbital method and the compliance constant formalism.     

Low temperature fluorination of sulphur compounds with elemental fluorine

Low temperature fluorination technique is adopted for fluorination of the following sulphur compounds in freon-11 medium (1) Sulphur dioxide (2) Thionyl chloride (3) Sulphuryl chloride (4) Tetrasulphur tetra nitride and (5) Sulphur bromide. All the compounds undergo oxidative fluorination to give rise to sulphur-fluorine compounds except sulphuryl chloride which resists fluorination. Sulphuryl chloride thus behaves as a good solvent medium for fluorination of other reactive compounds like elemental sulphur. Details of the experimental procedures adopted and the identification of the products will be presented.     

In situ prepared polypyrrole for low humidity QCM sensor and related theoretical calculation

In situ preparation of polypyrrole (Ppy) by photo-polymerization coated on a quartz crystal microbalance (QCM) as a low humidity sensor was reported. Different concentrations of Ppy films say 0 wt.% (as blank), 0.1, 1, and 10 wt.% were investigated to measure humidity concentrations between 14.7 and 5412.5 ppm_v. The adsorption/desorption behavior was also examined at humidity concentration 510.2 ppm_v. The sensitivities of 0, 0.1 and 1 wt.% Ppy films at 51.5 ppm_v were 0.143, 0.219 and 0.427, respectively. For 1 wt.% Ppy, the highest sensitivity was obtained. The slope and correlation coefficients (R²) for 1 wt.% Ppy at the ranges of 14.7–898.6 ppm_v were 0.0646 and 0.9909, respectively. A series of molecular simulations have been carried out to calculate bond energy for the water molecule interaction with Ppy, which was found to be 3 kcal/mol indicating the existence of hydrogen bonding during the sorption process. Based on Langmuir isotherm adsorption assumption, for 0.1 and 1 wt.% Ppy films, the association constants were 2606.30 and 5792.98, respectively. This larger association constant for 1 wt.% Ppy film explains higher sensitivity.     

Separation of thorium from rare earths

Summary A method for separation of thorium from rare earths in monazite based on the difference of stability of EDTA complexes towards oxine is described.     

Spectroscopic investigations of Nd(3+)-doped alkali chloroborophosphate glasses

Optical absorption spectra were studied in wavelength region 400-900 nm for the Nd(3+)-doped alkali (R = Li, Na and K) chloroborophosphate glasses at room temperature. The energy level scheme of the 4f(3) electron configuration was deduced from the observed energy level data using a parametrized Hamiltonian (H(F1)) model which includes 20 free-ion interaction parameters. Reasonable correlation was obtained between the experimental and calculated energy levels. The Judd-Ofelt model for the intensity analysis of induced electric dipole transitions has been applied to the measured oscillator strengths of the absorption bands to determine the three phenomenological intensity parameters Omega(2), Omega(4) and Omega(6) for each glass. Using these parameters, the total radiative transition rates (A(T)), non-radiative relaxation rates (W(NR)), branching ratios (beta(R)), integrated cross-sections for the stimulated emission (Sigma), excited state emission intensities (f(ESE)) and excited state absorption intensities (f(ESA)) have been theoretically calculated for certain excited Nd(3+) fluorescent levels. From the results obtained, the conclusion is made about the possibility of using these glasses as laser media.     

Chemical ionization and collisional activation spectra of α,β-unsaturated nitriles

A study of the chemical ionization (CI) and collisional activation (CA) spectra of a number of α, β-unsaturated nitriles has revealed that the even-electron ions such as [MH]⁺ and [MNH₄]⁺ produced under chemical ionization undergo decomposition by radical losses also. This results in the formation of M ⁺˙ ions from both [MH]⁺ and [MNH₄]⁺ ions. In the halogenated molecules losses of X˙ and HX compete with losses of H˙ and HCN. Elimination of X˙ from [MH]⁺ is highly favoured in the bromoderivative. The dinitriles undergo a substitution reaction in which one of the CN groups is replaced with a hydrogen radical and the resulting mononitrile is ionized leading to [M ? CN + 2H]⁺ under CI(CH₄) or [M ? CN + H + NH₄] and [M ? CN + H + N₂H₇]⁺ under CI(NH₃) conditions.     

Microdetermination of silver(I) and iodide ions with a pyridinol azo dye: A spectrophotometric method

A simple, rapid, sensitive, and selective method for the spectrophotometric microdetermination of silver(I) using ammonium(2′,3′-dihydroxy pyridyl-4′-azo)benzene-4-arsonate (DHP-4A), a water soluble pyridinol azo dye is proposed. The red colored 1:1 (metal to ligand) complex formed has molar extinction coefficient (ε) 2.95 × 10⁴ 1 mol⁻¹ cm⁻¹ and absorbs maximum at 535 nm, in highly alkaline medium. Beer's law is obeyed up to 3.36 ppm and Sandell's sensitivity (for an absorbance 0.001) is 0.0037 μg of Ag(I)/cm². The silver(I)-(DHP-4A) complex has also been used in the microdetermination of iodide ions using ligand exchange reaction. The optimum concentration range of iodide ions which can reproducibly be determined is 1.27–37.9 μg/10 ml.     

The Instability of Permanganate in orthophosphoric acid

Solutions of potassium permanganate in concentrated phosphoric acid (above 50%) are found to be unstable. The oxidation state of manganese is reduced from (VII) to (III) and oxygen is evolved during this process. The extent of decomposition of permanganate is found to be dependent on the concentration of the acid.     

2-jet production in polarised\vec p\vec pcollisions

Following recent interest in the subject of polarisation phenomena, we discuss the cross-sections and polarisation asymmetry in 2-jet production in polarised proton-polarised proton ( ) scattering. We set up a complete set of parametrisations for the proton spin-dependent parton densities and use them to demonstrate that this cross-section is dominated by gluonic terms. Hence, a measurement of the asymmetry in such processes will provide information on the gluon spin-dependent density. We further show that a factorisation of the hadronic cross-section a la Combridge and Maxwell's work in unpolarised 2-jet production also applies to the spin-dependent case. Hence, the cross-section can be written in terms of a genericpolarised parton density, which can then be measured in the process.