Sulphur compounds, organic

Organic sulphur compounds are volatile a few are soluble in water and are associated with bad odour. They are essentially studied in gaseous phase. But they can be present in wastewater because of their solubility in water-miscible solvents such as alcohols. In aqueous solution [17], they present a characteristic UV absorption (Fig. 65). 

Sulphur organic compounds are very sensitive to pH (Fig. 66). As the acidic form absorbs differently from the basic one, it is possible to calculate the pKa value of these compounds. The example of thiophenol is given, and the estimated pKa value is close to 6.2 (Fig. 66). 

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The fluids contained within petroleum accumulations are mixtures of organic compounds, which are mostly hydrocarbons (molecules composed of hydrogen and carbon atoms), but may also include sulphur, nitrogen, oxygen and metal compounds. This section will concentrate on the hydrocarbons, but will explain the significance of the other compounds in the processing of the fluids. 

There are a total of eighteen different hydrocarbon series, of which the most common constituents of crude oil have been presented - the alkanes, cycloalkanes, and the arenes. The more recent classifications of hydrocarbons are based on a division of the hydrocarbons in three main groups alkanes, naphthanes and aromatics, along with the organic compounds containing the non-hydrocarbon atoms of sulphur, nitrogen and oxygen. 

Sulphur trioxide is used on an industrial scale for sulphonating organic compounds. 

The method of hydrolysis depends on the nature of the product. It is usually sufficient to add dilute sulphuric acid to the ethereal solution and to shake thoroughly, when the magnesium enters the aqueous solution, whilst the organic compound remains in the ether. Alternatively, however, the ethereal solution may be poured on to ice and water, and then treated with dilute sulphuric acid. Should the product be affected by this acid, the hydrolysis can be carried out with an aqueous solution of ammonium chloride. In the following examples the hydrolysis is usually shown as a simple double decomposition... 

The Sodium Carbonate-Zinc Method for Detecting Nitrogen, Halogens and Sulphur in Organic Compounds. 

Zinc dust of good quality usually contains only negligible quantities of halogen and sulphur, and is nitrogen-free. A blank for these elements should, however, be made with every fresh batch of reagent prepared if perceptible traces of halogen or sulphur are present, a blank or control test must be performed side by side with that on the organic compound, and the results compared. 

This type of extraction depends upon the use of a reagent which reacts chemically with the compound to be extracted, and is generally employed either to remove small amounts of impurities in an organic compound or to separate the components of a mixture. Examples of such reagents include dilute (5 per cent.) aqueous sodium or potassium hydroxide solution, 5 or 10 per cent, sodium carbonate solution, saturated sodium bicarbonate solution (ca. 5 per cent.), dilute hydrochloric or sulphuric acid, and concentrated sulphuric acid. 

Upon fusion with caustic alkah (for experimental details, see Section IV,33,2) and acidification of the aqueous extract, hydrogen sulphide is evolved (detected by lead acetate paper). This test is given by aU organic compounds of divalent sulphur (RSH, R SR" and R SSR"). 

Qualitative analysis for the elements. This includes an examination of the effect of heat upon the substance—a test which inter alia will indicate the presence of inorganic elements—and quahtative analysis for nitrogen, halogens and sulphur and, if necessary, other inorganic elements. It is clear that the presence or absence of any or all of these elements would immediately exclude from consideration certain classes of organic compounds. 

Study of the solubility behaviour of the compound. A semi-quantitative study of the solubility of the substance in a hmited number of solvents (water, ether, dilute sodium hydroxide solution, dilute hydrochloric acid, sodium bicarbonate solution, concentrated sulphuric and phosphoric acid) will, if intelligently apphed, provide valuable information as to the presence or absence of certain classes of organic compounds. 

THE SODIUM CARBONATE - ZINC METHOD FOR THE DETECTION OF NITROGEN, SULPHUR AND HALOGENS IN ORGANIC COMPOUNDS... 

When an organic compound is heated with a mixture of zinc powder and sodium carbonate, the nitrogen and halogens are converted into sodium cyanide and sodium hahdes respectively, and the sulphur into zinc sulphide (insoluble in water). The sodium cyanide and sodium hahdes are extracted with water and detected as in Lassaigne s method, whilst the zinc sulphide in the residue is decomposed with dilute acid and the hydrogen sulphide is identified with sodium plumbite or lead acetate paper. The test for nitrogen is thus not affected by the presence of sulphur this constitutes an advantage of the method. 

In addition to water and ether, the following reagents are employed as solvents for the characterisation of organic compounds 5 per cent, aqueous solutions of hydrochloric acid and of sodium hydroxide, and also concentrated sulphuric acid. 

The UK Environment Agency deals with over 6000 oil pollution incidents each year. One estimate suggests tliat tlie cheiTtical industry contributes to 50% of all ah pollution witli proportions approximating to sulphur dioxide (36%), carbon dioxide (28%), nitrogen oxides (18%), carbon monoxide (14%) and black smoke (10%). Motor spirit refining is responsible for ca 26% of emissions of volatile organic compounds to the atmosphere. In 1996 there were over 20 000 reports of water pollution incidents with 155 successful prosecutions. 

Sulphur.—The presence of sulphur in organic compounds may be detected by heating the substance with a little metallic sodium or potassium. The alkaline sulphide, when dissolved in water, gives a violet colouration with a solution of sodium nitro-prusside. Heat a fragment of gelatine with a small piece of potassium in a test-tube until the bottom of the tube is red hot, and place it m a small beaker of water as described in the test for nitrogen (p. 2). Filter the liquid and add a few drops of sodium nitroprusside solution. 

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