Synthesis of N,N-diethyl-N-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}amine via in situ diazotisation and coupling in supercritical carbon dioxide

The synthesis of azo dyes via a conventional aqueous-based diazotisation and coupling reaction requires the use of relatively high concentrations of mineral acids, which leads to high electrolyte concentrations in wastewater. Reported in this paper is an environmentally benign one-pot method for the synthesis of a nonionic azo dye, N,N -diethyl- N -{4-[( E )-(4-nitrophenyl)diazenyl]phenyl}amine, in supercritical carbon dioxide without using a mineral acid. The product yield increased significantly with temperature, with 91% theoretical yield afforded at 80 °C. The pressure of the system had little influence on product yield.     

Measurement of Gibbs energies of formation of CoF2 and MnF2 using a new composite dispersed solid electrolyte

Gibbs energies of formation of CoF₂ and MnF₂ have been measured in the temperature range from 700 to 1100 K using Al₂O₃-dispersed CaF₂ solid electrolyte and Ni+NiF₂ as the reference electrode. The dispersed solid electrolyte has higher conductivity than pure CaF₂ thus permitting accurate measurements at lower temperatures. However, to prevent reaction between Al₂O₃ in the solid electrolyte and NiF₂ (or CoF₂) at the electrode, the dispersed solid electrolyte was coated with pure CaF₂, thus creating a composite structure. The free energies of formation of CoF₂ and MnF₂ are (± 1700) J mol⁻¹; {fx37-1} The third law analysis gives the enthalpy of formation of solid CoF₂ as ΔH° (298·15 K) = −672·69 (± 0·1) kJ mol⁻¹, which compares with a value of −671·5 (± 4) kJ mol⁻¹ given in Janaf tables. For solid MnF₂, ΔH°(298·15 K) = − 854·97 (± 0·13) kJ mol⁻¹, which is significantly different from a value of −803·3 kJ mol⁻¹ given in the compilation by Barinet al.     

Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

N.m.r. line shape-relaxation correlation analysis of bitumen and oil sands

The first results of the analysis of bitumen and oil sands using the recently developed n.m.r. spingrouping technique are presented. The n.m.r. relaxation experiments were carried out on bitumen, and on natural and dried oil sands samples. The results indicate that the spin-grouping can resolve and quantify several components of the samples studied. The bitumen and bitumen fraction of the oil sands are resolved according to their spin-spin relaxation times into three major groups: solid-like (rigid), solid-like (mobile) and semi-liquid. The water in the oil sands exists in two different environments. Tentatively one environment is assigned to be the bridges between the sand grains, while the other is assigned to be the clay surface. One can conclude that with spin grouping of complex mixtures the decomposition (in which components are resolved according to their dynamic state) is possible. The accuracy of such resolution is of the order of a few per cent.     

Steric requirements for coal swelling by amine bases

A set of six coals ranging in rank from lignite to hvA bituminous was swollen with a series of alkyl-substituted pyridines and a smaller set of 4-alkylanilines. The size and branching of the alkyl groups was varied and the effect of this variation on the dissolution of the amines in the coal and the resulting coal swelling was measured volumetrically. In a few cases, substituents which hindered the amine nitrogen were studied. The lignite and subbituminous coal have a much higher tolerance to branched, bulky groups than do the bituminous coals. The presence of tertiary groups in a solute strongly inhibits their dissolution in bituminous coals. Bituminous coals behave as if extensive parallel packing of structures occurs. Often, they can accept very large planar groups but have a low capacity for branched groups.     

Kinetics of hydantoin formation

The reaction of lignite in a slagging gasifier produces reactants which in turn form 5,5-dimethylhydantoin (DMH) as a major constituent in the condensate water. Variations in plant operating conditions made it impossible to accurately study the kinetics of formation of DMH in the actual gasifier water, and thus a model system was chosen. The reaction of acetone cyanohydrin in the presence of excess ammonium carbonate at concentrations approaching those obtained in the condensate water were studied at 50,70, and 90 °C. Secondorder kinetics were obeyed, and the pseudo second-order rate constants at the respective temperatures were 1.86, 3.6, and 4.62 dm³ mol^{? 1} h^{? 1}. Independent variation of the concentration of either acetone, cyanide, ammonia or carbonate gave results consistent with the interpretation that the formation of DMH is first order in all reactants: rate of formation of DMH = k[acetone][HCN][NH₃][CO₂]. The pseudo second-order rate constant is a complex rate constant including several rapid equilibria. A mechanism consistent with the kinetic data is presented.     

Effect of polymerization conditions on the melt rheological properties of vinyl chloride–vinyl acetate copolymers

Mathematical models have been developed which predict the composition, molecular weight, and melt rheological properties for vinyl chloride/vinyl acetate copolymers of inherent viscosity range 0.4–0.7 dL/g and bound vinyl acetate levels of 3.8–17.4%. The effect of polymer long chain branching on the viscous/elastic moduli ratio is discussed as well as the comparison of Tinius–Olsen melt index measurements vs. mechanical spectrometer results. The reactivity ratio for vinyl chloride/vinyl acetate comonomer pairs was remeasured and found to be significantly different from literature values.     

Particle structure of PVC based on cellulosic suspension system. III. Effect of monomer refluxing

The effects of monomer refluxing on both resin properties and reactor fouling of suspension PVC have been studied in a laboratory-scale 14-L reactor. Process control equations were developed which related the particle properties to the reflux condenser operation by controlling the parameters of (1) the time at which refluxing is begun and (2) the rate profile of heat removal from the condenser. An operating envelope has been developed for laboratory scale operations which optimizes the cycle time of polymerization while minimizing the adverse effects on particle properties. These operating conditions may have application to production scale operations when the proper scaling factors are employed.     

Contacting modes and behaviour classification of gas—solid and other two-phase suspensions

An attempt is made to extend schemes for classifying the behaviour of gas—solid contacting modes and other two-phase systems. The regime diagram approach of Reh (1971) is modified and extended to cover the operating regions of common reactors and contactors where a gas flows upwards through a bed of solids including fixed and moving packed beds, conventional fluidized beds, circulating beds, spouted beds, and pneumatically conveyed suspensions. New boundaries are proposed between groups A and B and between groups B and D of the Geldart (1972, 1973) powder classification scheme. These boundaries reflect more recent data and allow the classification scheme to be used for gases other than air and for temperatures and pressures other than atmospheric.