Diels-Alder reaction of furan with some dienophiles

The reaction of furan and maleic acid was carried out in several solvents. The endo-adduct was isolated and the structure established by its spectral properties and conversion into known compounds. The adducts of furan with fumaric acid, diethyl fumarate and diethyl maleate are reported.     

Solvent extraction and spectrophotometric determination of iron(II) with 2,2′-dipyridyl-2-quinolylhydrazone

2,2′-Dipyridyl-2-quinolylhydrazone (DPQH) was used for the spectrophotometric determination of trace amount of iron(II) after the extraction process. Iron(II) reacts with DPQH at pH 3.4–4.5 to form a water-insoluble 1:2 complex, which can be extracted with many kinds of organic solvent. The extracted species with benzene has absorption maxima at 473, 504, and 644 nm and obeyed Beer's law over the range 0–14 μg of iron at 504 nm and 0–33 μg at 644 nm. The molar absorptivities at 504 and 644 nm are 3.14 × 10⁴ and 1.30 × 10⁴M^?1 cm^?1, respectively. DPQH is one of the most sensitive reagents for iron(II) and trace amount of iron(II) can be determined in the presence of fairly large amounts of other ions. Possible equilibria involved in the extraction process were also studied.     

Thermodynamics of weak interactions: excess enthalpies and excess Gibbs free energies of mixing

Excess enthalpies of chloroform + n-hexane, bromoform + n-hexane, bromoform + pyridine and bromoform + benzene and excess Gibbs free energies of mixing for bromoform + pyridine, chloroform + pyridine, bromoform + n-hexane, chloroform + n-hexane and bromoform + benzene have been determined at 308.15 K and the same factors have been examined for Barker's theory to understand the magnitude and nature of various interactions between the components of these mixtures.     

Enthalpies of mixing of some aqueous electrolytes at 373.15 K

The enthalpies of mixing of a variety of aqueous electrolytes at an ionic strength of 1.000 mol·kg^?1 have been measured at 373.15 K. The mixtures studied were LiBr + KBr, NaBr + KBr, KBr + (C₄H₉)₄NBr, NaCl + Na₂SO₄, NaCl + MgCl₂, MgSO₄ + Na₂SO₄, MgCl₂ + MgSO₄, NaCl + MgSO₄, and MgCl₂ + Na₂SO₄. In contrast to most previous enthalpies of mixing of alkali halides, the mixtures with multivalent ions studied here often have large temperature dependences. The results for the mixtures involving MgSO₄ are consistent with a higher degree of ion pairing as the temperature increases. The present measurements, together with Gibbs energies of mixing at 298.15 K, allow the calculation of Gibbs energies of mixing at the higher temperature. This appears to be the most accurate and convenient method available for determining Gibbs energies of mixing at high temperatures.     

Spectrophotometric study of the copper(II)-2,2′-dipyridyl-2-pyridylhydrazone complex formation

The reaction of copper(II) ions with 2,2′-dipyridyl-2-pyridylhydrazone (DPPH) has been studied. Two copper complexes were found to be formed. One at pH 6.5 to 8.5 and the other at pH 11.9 to 12.6 with molecular extinction coefficients of 1.9 × 10⁴M^?1 · cm^?1 at the absorption maximum of 478 nm and 3.8 × 10⁴M^?1 · cm^?1 at 448 nm, respectively. A sensitive spectrophotometric procedure for the determination of copper at less than a 1-ppm level is proposed.     

Thermal decomposition kinetics of p-toluenesulphonamide and some of its n-halogeno and n-metal derivatives

The TG, DTG and DTA traces of p-toluene sulphonamide, chloramine-T, dichloramine-T, dibromamine-T and the Ag and Hg derivatives of p-toluene sulphonamide are given and interpreted. The kinetic parameters (energies and entropies of activation and pre-exponential factors) for the main decomposition stages have been calculated.     

Head-to-head polymers—I. The preparation and some properties of head-to-head polypropylene

Samples of head-to-head polypropylene have been prepared by the hydrogenation of two polydienes; 1,4-poly(2,4-hexadiene) and 1,4-poly(2,3-dimethyl-1,3-butadiene). Glass transition temperatures were found to be marginally lower than for conventional polypropylene suggesting that the head-to-head placements in the chain increased the polymer flexibility.     

Solvent extraction and spectrophotometric determination of palladium(II) with some nitrogen-containing heterocyclic hydrazones in the presence of chloride ions

Three terdentate hydrazones, all containing the 1-phthalazino grouping in the hydrazine moiety but differing in the heterocyclic substituent in the aldehyde moiety, have been used as analytical reagents for palladium(II), the optimal conditions for the extractive spectrophotometric determination of palladium(II) in the presence of chloride ions being deduced. These compounds are highly selective and sensitive reagents for palladium(II), since they are not extracted into chloroform from sulfuric acid solutions and do not react with other platinum group metals. The desirable spectral properties of the palladium(II) complex of benzothiazole-2-aldehyde-1-phthalazinohydrazone (BAPhH) have also been discussed with respect to preference of the C  N structural form in the heterocyclic ring on the aldehyde moiety of the ligand.     

Infrared spectroscopic properties of water molecules dissolved in some oxygen bases

The infrared spectra in the OH-stretching and HOH-bending regions of H₂O, and in the OH-stretching region of HDO dissolved in a number of ketones and ethers have been recorded. The number of component bands and their wavenumbers, halfwidths and intensities, as well as the total OH-stretching intensity in each solvent, have been interpreted in terms of a model for the types of hydrogen bonded solvent:water complexes formed in these systems.The effect of temperature on the spectra of H₂O in some of the ketones has been rationalized on the basis of the equilibrium existing between the different hydrogen bonded species present in solution.     

Calculation of polarization energies in some III–VII and IV–VI compounds with stereochemically active (ns)2-ions

The polarization energies of AB compounds, with A a monovalent or divalent cation with an (ns)²-lone pair and B an anion with a noble gas electronic configuration, have been calculated to investigate whether the stereochemical activity of the (ns)²-ion can be understood in an ionic picture. Computations have been performed applying the computer program EWALD. Formal ionic charges and partly estimated polarizabilities have been used. The polarization energy is shown to be predominantly due to cation polarization and may constitute an appreciable fraction of the total lattice energy. Hence, it can play a crucial role in the formation of structures, in which the (ns)²-ion is in a noncentrosymmetrical environment.     

Ferromagnetic resonance studies in some polycrystalline magnesium nickel ferrites

Ferromagnetic resonance measurements were carried out on various compositions of magnesium nickel ferrites prepared by various heat treatments. Corrections were applied for polycrystalline and size effects for calculating the g factor and linewidth. The variation of these parameters has been explained on the basis of the cation distribution in these compounds as obtained from magnetization data assuming a collinear model of spin distribution.     

Addition of lithium aluminium hydride to olefins catalyzed by zirconium tetrachloride: A convenient route to alkanes and 1-haloalkanes from 1-alkenes

Lithium aluminium hydride adds to olefins in the presence of zirconium tetrachloride under mild conditions. This facile reaction offers a convenient laboratory method for the hydrogenation of olefins or for the preparation of 1-haloalkanes from olefins in high yield. Unstrained internal olefins appear to be unreactive.     

The thermal stability of some pulping materials

The thermal stabilities of three annual plants (reed, kenaf and Glycyrrihiza glablra L.) are studied. Various types of pulps were prepared from reed stalks by employing the soda, kraft and soda-anthraquinone processes. Their thermal stabilities are reported.It is shown that the thermal stability measured thermogravimetrically depends, to some extent, on the amount of lignin remaining in the raw materials, i.e. the kappa number.The activation energy of the decomposition process and the decomposition temperatures of the pulps are also reported.     

Preparation and electronic spectra of some alkyl- and aryl(2,2′-bipyridine)platinum(II) complexes

A series of alkyl- and aryl-(2,2′-bipyridine)-platinum (II) complexes has been prepared by displacement of the diene ligand in the corresponding cyclooctadiene complexes with 2,2′-bipyridine. Dimethyl(1,10-phenanthroline)platinum(II) was prepared in an analogous way. The electronic spectra of the complexes contain metal to ligand charge transfer bands whose energy is dependent on the nature of the substituents on platinum and on the solvent. It is suggested that π-bonding is important in the phenyl—platinum bond.     

The electrical conductance of some molten car☐ylate mixtures

Data are presented for the electrical conductivities in the melt for lead(II) octadecanoate/lead(II) decanoate, lead(II) hexadecanoate/lead(II) decanoate, lead(II) hexadecanoate/zinc hexadecanoate and lead(II) hexadecanoate/cadmium hexadecanoate mixtures over their complete composition ranges. The electrical conductivities are measured as a function of temperature from just above the melting point to just below the decomposition point of the mixtures. The Arrhenius plots for the mixtures are linear in all cases and the activation energies are determined. While the activation energies for lead(II) octadecanoate/lead(II) decanoate and lead(II) hexadecanoate/lead(II) decanoate mixtures are mole fraction independent over the concentration range studied, rendering support to previous models advanced by other workers that the major charge carrier is the free metal cation, the other systems show no such simple behaviour. In these systems there are indications of deviations from ideal behaviour, suggesting that entropy and enthalpy of mixing might be important.