Sulphur modifications

Dissolve two or three of the crystals in chloroform on a watch glass, and after evaporation of the solvent, examine the shape of the newly formed crystals. What structure of the molecules corresponds to the obtained sulphur modifications ... 

The i.r. and Raman spectra of solid cyclododecasulphur have been reported55 and the spectra compared with those of other sulphur modifications. In all the sulphur modifications the bond-stretching modes give rise to bands at frequencies above 390 cm-1 the strong Raman line at 128 cm-1 is, however, especially characteristic for St2 since S6, S7, S8, and show no Raman lines in this region. 

The Element.— Two reviews on the properties of elemental sulphur have been published. The first deals with new allotropic forms of sulphur as prepared by the reaction of polysulphides with either SaCla or SCla, the structures of Se, S7, Sg, Sg, Sio, Sii, Sxa, and Sig, and polysulphides up to S . The second reviews sulphur modifications sulphur rings containing heteroatoms and the structures of sulphur molecular ions, melts, and vapours. 

Molisch s test A general test for carbohydrates. The carbohydrate is dissolved in water, alcoholic 1-naphthol added, and concentrated sulphuric acid poured down the side of the tube. A deep violet ring is formed at the junction of the liquids. A modification, the rapid furfural test , is used to distinguish between glucose and fructose. A mixture of the sugar, 1-naphthol, and concentrated hydrochloric acid is boiled. With fructose and saccharides containing fructose a violet colour is produced immediately the solution boils. With glucose the appearance of the colour is slower. 

Like sulphur, selenium exists in a number of allotropic forms. These include both crystalline, rhombic and monoclinic modifications... 

The following is a modification of the process described and gives quite satisfactory results. Wash the crude mixture of benzonitrile and dibromopentane with sodium carbonate solution until the latter remains alkaline, and then with water. Distil it under reduced pressure and collect the fraction boiling up to 120°/18 mm. Dissolve this in twice its volume of light petroleum, b.p. 40-60°, which has previously been shaken with small volumes of concentrated sulphuric acid until the acid remains colourless. Shake the solution with 6 per cent, of its volume of concentrated sulphuric acid, allow to settle, and run ofi the sulphuric acid layer repeat the extraction until the acid is colourless or almost colourless. Wash successively with water, sodium carbonate solution and water, dry over anhydrous calcium chloride or calcium sulphate, and distil off the solvent. Distil the residue under diminished pressure and collect the 1 6-dibromopentane at 98- 100°/13 mm. 

It has been tentatively suggested that one mechanism underlies the Willgerodt reaction and the Kindler modification of it. A labile intermediate is first formed which has a carbon—carbon bond in the side chain. The scheme is indicated below it postulates a series of steps involving the addition of ammonia or amine (R = H or alkyl), elimination of water, re addition and eUmination of ammonia or amine until the unsaturation appears at the end of the chain then an irreversible oxidation between sulphur and the nitrogen compound may occur to produce a thioamide. 

The first methacrylic esters were prepared by dehydration of hydroxyisobutyric esters, prohibitively expensive starting points for commercial synthesis. In 1932 J. W. C. Crawford discovered a new route to the monomer using cheap and readily available chemicals—acetone, hydrocyanic acid, methanol and sulphuric acid— and it is his process which has been used, with minor modifications, throughout the world. Sheet poly(methyl methacrylate) became prominent during World War II for aircraft glazing, a use predicted by Hill in his early patents, and since then has found other applications in many fields. 

During emulsion polymerization, a high conversion of monomer to polymer produces cross-linked rubber which is insoluble. To obtain a high conversion in the polymerization reaction and a processable polymer, suitable polymer modification should be made. The use of sulphur moieties allows this goal to be reached [2]. Sulphur-modified polychloroprenes contain di- and polysulphide sequences in the polymer chains. After the polymerization reaches the desired degree, reaction is stopped by adding thiuram disulphide ... 

A alight modification consists in using a mixture of 10 c.c. concentrated sulphuric acid aud fi c.c. concentrated uitric acid, the ultilo acid being added last to ibc mixture of sulphuric acid and bcnxaldehyde. 

The sulphuric acid, used to acidulate before distillation, may be advantageously replaced by phosphoric acid. This modification, whilst in many cases not absolutely essential, is desirable on account of the fact that sulphuric acid is liable to become reduced by certain constituents of oils, particularly of old oils, which frequently contain substances of a resinous nature. In such cases the volatile acid products of the reduction pass over along with the true acids of the oil undergoing examination. 

The Karl Fischer procedure has now been simplified and the accuracy improved by modification to a coulometric method (Chapter 14). In this procedure the sample under test is added to a pyridine-methanol solution containing sulphur dioxide and a soluble iodide. Upon electrolysis, iodine is liberated at the anode and reactions (a) and (b) then follow the end point is detected by a pair of electrodes which function as a biamperometric detection system and indicate the presence of free iodine. Since one mole of iodine reacts with one mole of water it follows that 1 mg of water is equivalent to 10.71 coulombs. 

RSRP [Richards sulphur recovery process] A proposed modification of the Claus process in which liquid sulfur is used to cool the catalyst bed. Developed jointly by the Alberta Energy Company and the Hudson s Bay Oil Gas Company, but not reported to have been commercialized. 

The starting point for the 5-fluoropentanecarboxylic esters was cyclohexanone, which was oxidized to 5-hydroxypentane-carboxylic acid by a modification of Robinson and Smith s method.3 This was then converted into the bromo acid by means of hydrogen bromide and sulphuric acid.4... 

The same reaction can be applied, not only to the aromatic parent substances, the hydrocarbons, but also to all their derivatives, such as phenols, amines, aldehydes, acids, and so on. The nitration does not, however, always proceed with the same ease, and therefore the most favourable experimental conditions must be determined for each substance. If a substance is very easily nitrated it may be done with nitric acid sufficiently diluted with water, or else the substance to be nitrated is dissolved in a resistant solvent and is then treated with nitric acid. Glacial acetic acid is frequently used as the solvent. Substances which are less easily nitrated are dissolved in concentrated or fuming nitric acid. If the nitration proceeds with difficulty the elimination of water is facilitated by the addition of concentrated sulphuric acid to ordinary or fuming nitric acid. When nitration is carried out in sulphuric acid solution, potassium or sodium nitrate is sometimes used instead of nitric acid. The methods of nitration described may be still further modified in two ways 1, the temperature or, 2, the amount of nitric acid used, may be varied. Thus nitration can be carried out at the temperature of a freezing mixture, at that of ice, at that of cold water, at a gentle heat, or, finally, at the boiling point. Moreover, we can either employ an excess of nitric acid or the theoretical amount. Small scale preliminary experiments will indicate which of these numerous modifications may be expected to yield the best results. Since nitro-compounds are usually insoluble or sparingly soluble in water they can be precipitated from the nitration mixture by dilution with water. 

The colour reaction of cholesterol and cholesterol esters with acetic anhydride and concentrated sulphuric acid provides the basis of the method attributed to Liebermann and Burchard. This reaction in not entirely specific for cholesterol or its esters because other sterols will also react. In its original form the reagent consists of acetic anhydride, concentrated sulphuric acid and glacial acetic acid and the intensity of the green colour is affected by the proportions of the reagents and the amount of water present. It is possible to achieve an increase in sensitivity if the reagent contains ferric ions. Various modifications of reagent composition have been used and some methods are fluorimetric. 

The use of maleic anhydride as a compatiblizer between wood particles and bisphenol A-based polyesters resins has been investigated (Han etal., 1991). In this study, the MA was added directly to the composition of woody matrix filler and resin rather than by pre-modification of the wood. It was found that composite properties were improved by addition of MA, probably due to esterification of the wood occurring during the kneading process. The modification of sawdust using maleic anhydride has been performed in order to provide a compatible filler for polyester resins (Marcovich etal., 1996). Modification was performed at room temperature using a solution of maleic anhydride in acetone, in some cases catalysed with sulphuric acid. It was claimed that bonding occurred under these mild conditions from IR spectroscopic evidence only. 

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