Sulphur solid-state

The hydrogensulphates (or bisulphates) containing the ion HSO4, are only known in the solid state for the alkali metals and ammonium. Sodium hydrogensulphate is formed when sodium chloride is treated with cold concentrated sulphuric acid ... 

These materials have been prepared by polymerisation of p-halothiophenoxide metal compounds both in the solid state and in solution. They have also been prepared by condensation of p-dichlorobenzene with elemental sulphur in the presence of sodium carbonate while the commercial polymers are said to be produced by the reaction of p-dichlorobenzene with sodium sulphide in a polar solvent. 

In 1968 DairOlio et al. published the first report of analogous electrosyntheses in other systems. They had observed the formation of brittle, filmlike pyrrole black on a Pt-electrode during the anodic oxidation of pyrrole in dilute sulphuric acid. Conductivity measurements carried out on the isolated solid state materials gave a value of 8 Scm . In addition, a strong ESR signal was evidence of a high number of unpaired spins. Earlier, in 1961, H. Lund had reported — in a virtually unobtainable publication — that PPy can be produced by electrochemical polymerization. 

Boron trifluoride, sulphur and disulphur dichlorides, phosphorus trichloride in the liquid state cause potassium to combust. The same is true for phosphorus pentachloride in the solid state. In the latter case the same accident happened with gaseous halide. The same is also true for the bromide analogues of these compounds. 

The reactions of the halide salts, in the solid state, with concentrated sulphuric acid vary in relation to the reducing power of the hydrogen halides produced. 

Fast, solid state, microwave-assisted, synthesis. A short history of reactions carried out in the solid state under the influence of microwaves was reported by Kniep (1993) who presented this technique as characteristic of a fast solid-state chemistry and described the preparation of CuInS2 by using a method first developed by Whittaker and Mingos (1992) and extended by Landry and Barron(1993). Copper, indium and sulphur (all powders between 100 and 300 mesh) in a molar ratio 1 1 2 were thoroughly mixed and loaded into a silica ampoule. This, sealed under vacuum, was placed in a domestic microwave oven and irradiated at 400 W and 2450 MHz. 

Air is able to enter and be maintained in a solid state because it is so strongly attracted by the acid sulphureous particles,... 

The periodates 0 the alkaline earths.—C. F. Rammelsberg13 obtained calcium metaperiodate, Ca(I04)2, by the action of periodic acid on a soln. of calcium hydroxide or dimesoperiodate, the solid separates on concentrating the acid soln. similarly, when a soln. of strontium carbonate in an excess of periodic acid is cone, in a desiccator, large, probably triclinic, crystals of hexahydrated strontium metaperiodate, Sr(I04)2.6H2O, are formed. They lose 12-36 per cent, of water when cone, over cone, sulphuric acid, and the remainder at 100°. This salt explodes when heated the aq. soln. has an acid reaction, and gives a precipitate when treated with ammonia. When the attempt is made to concentrate the soln. of barium metaperiodate, Ba(I04)2, prepared in a similar manner, the dimesoperiodate is deposited when the soln. is cone., so that the metaperiodate has not been isolated in a solid state. 

The methods which have been reported for preparation of ammonium disulphide, (NIL Sa, by the dissolution of the theoretical amount of sulphur in ammonium monosulphide, were specially studied by W. P. Bloxam6 in his memoir The sulphides and polysulphides of ammonium. He sealed up the calculated quantify of sulphur in a tube with a soln. of ammonium monosulphide. He noticed an evolution of gas occurred as the sulphur dissolved, a phenomenon which he thinks would not be observed if (NH4)2S were really the solute. W. P. Bloxam also failed to obtain the disulphide by passing through a hot tube the vapour of ammonium chloride and sulphur, and he finally concluded that up to the present ammonium disulphide has not been prepared either in the solid state or in soln. J. Fritzsche also failed to make the disulphide nearly 60 years earlier than W. P. Bloxam. B. de Fororand calculated that the heat of formation of the Unknown solid will prove to be>(N2,H8,S2)8oUd=(NH4)iiS23oUd+66-2 Cals. 

By rapidly cooling the fluid mixture it is possible to minimise the readjustment of the equilibrium and to attain a solid condition in which tire original proportions of the mixture are approximately retained in the solid state tire allotropic change is so very slow as to allow careful and fairly prolonged examination of the mixture. It is then found that, the normal mobile liquid constituent (S ) has given rise to crystalline sulphur, soluble in carbon disulphide, whereas the dark-coloured viscous constituent (S ) has produced an amorphous solid, insoluble in this solvent4 (see also p. 10). A rough analysis of molten sulphur in... 

Allotropy in the Solid State.—When molten sulphur is allowed to solidify, the modifications present give rise to corresponding solid forms, the liquid A-sulphur producing crystalline sulphur (rhombic, monoclinic or nacreous, according to the conditions), whilst the deep... 

As has already been mentioned, the behaviour of molten sulphur on crystallisation is of a complex nature and dependent largely on the previous temperatures, the rate of cooling and the temperature at which crystallisation begins.6 Occasionally crystallisation occurs in a rhythmic manner, giving rise to an annular appearance in the structure of the solid mass.7 The crystallisation of undercooled molten sulphur is stated... 

The solutions of these polysulphides are yellowish-brown, and on treatment with acid in the usual manner they yield hydrogen sulphide and a precipitate of sulphur. In many eases polysulphides of the alkali and alkaline earth metals have been isolated in the solid state the types M2S4 and M2S5 appear to be the most stable as a general rule.7... 

The compound is obtainable in the solid state by the addition of powdered tellurium to sulphur trioxide, when combination occurs with evolution of heat. Any excess of sulphur trioxide can be removed mechanically or by evaporation under reduced pressure.6... 

Examples of supramolecular association as a result of intermolecular organolead-sulphur interactions are rare and compounds such as Me3PbSMe and Pl PbSPh are monomeric in the solid state463. In contrast, triphenyllead pyridine-4-thiolate, d-Pl PbSCsFLjN464, is a chain polymer as a result of intermolecular N—Pb interactions. The cyclic dithiolate 2,2-diphenyl-l,3,2-dithiaplumbolane 177465 self-assembles in the solid state via intermolecular tin-sulphur interactions into a one-dimensional polymeric array. The intramolecular Pb—S bond lengths amount to 2.52(2) and 2.49(1) A and the intermolecular Pb—S distances are 3.55(2) A. 

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