Sulphur compounds, oxidation

Oxides of sulphur and other sulphur compounds Oxides of nitrogen and other nitrogen compounds Oxides of carbon... 

Oxidation of a sulphur compound with concentrated nitric acid yields sulphuric acid or a sulphate, which can be tested for with barium chloride. This can be used to estimate the sulphur. 

Note. (1) Most sulphur compounds are completely oxidised if the tube is heated under the conditions described for the estimation of halogens. Sul-phonic acids and sulphones are more difficult to oxidise completely and the tube should be slowly heated to 300 and maintained at this temperature for at least 6 hours. The oxidation may be facilitated by adding a few crystals of sodium or potassium bromide to the organic material in the small tube, so that bromine shall be present to intensify the oxidation during the heating. 

Another method for slowing oxidation of rubber adhesives is to add a compound which destroys the hydroperoxides formed in step 3, before they can decompose into radicals and start the degradation of new polymer chains. These materials are called hydroperoxide decomposers, preventive antioxidants or secondary antioxidants. Phosphites (phosphite esters, organophosphite chelators, dibasic lead phosphite) and sulphides (i.e. thiopropionate esters, metal dithiolates) are typical secondary antioxidants. Phosphite esters decompose hydroperoxides to yield phosphates and alcohols. Sulphur compounds, however, decompose hydroperoxides catalytically. 

Metal deactivator To form inactive protective films on metal surfaces which otherwise might catalyse oxidation and corrosion reactions Trialkyl and triaryl phosphites, organic dihydroxyphosphines, some active sulphur compounds, diamines in lubricating greases, mercaptobenzothiazole and phosphites... 

K. From Organic Sulphur Compounds of Higher Oxidation State.. . . 279... 

Mincing, cooking and maturing expose meat products to oxidative stress for a long time so that antioxidants added for lipid protection are slowly destroyed on storage. Onion juice is a powerful antioxidant in meat products, more efficient than garlic juice. Lipid hydroperoxides are reduced to inactive hydroxyl derivatives by reaction with sulphur compounds present in those juices. 

Technically important dyes are salicylic acid derivatives that function as chrome mordant dyes for wool. Thus Cl Mordant Blue 1 (6.187) is made by the aldehyde synthesis from 2,6-dichlorobenzaldehyde and 2-hydroxy-3-methylbenzoic (o-cresotinic) acid in concentrated sulphuric acid. Oxidation of the leuco base is achieved by the addition of sodium nitrite. On wool the product, which is isolated as the sodium salt, is a dull maroon colour, changing to a bright blue on treatment with a chromium salt. Some dyes of this type, such as Cl Mordant Violet 1 (6.188), also contain a basic group. This compound is also prepared by the aldehyde route. 

Kelly DP. 1968. Biochemistry of oxidation of inorganic sulphur compounds by microorganisms. Aust 1 Sci 31 165-73. 

Kelly DP. 1988. Oxidation of sulphur compounds. Soc Gen Microbiol Symposium 42 65-98. 

The principle of fluidised bed combustion with simultaneous desulphurisation is based on the thermal decomposition of limestone carbonates to yield oxides which then react with the sulphur oxide products of combustion of both inorganic and organic sulphur compounds in the hydrocarbon fuel. 

Metals tarnish when their surface atoms react with gaseous substances in the air. Oxygen is a highly reactive element, as we saw in the previous chapter, and it combines with iron to form the ruddy oxide compound we recognize as rust. Copper reacts with oxygen and carbon dioxide to form a greenish patina of copper carbonate. Silver resists the advances of oxygen but will slowly combine with sulphur compounds in the air to form black silver sulphide. 

Understanding the storage capacity of the metal oxide material and the N02 adsorption rate is therefore also very important. Furthermore, oxides of sulphur in the exhaust gas, formed from combustion of sulphur compounds in the fuel (or lubricant oil), are stored in a similar manner. Since sulphates are thermodynamically more stable than the corresponding nitrate, this results in a reduction in the NOx storage capacity of the LNT. 

Since sulphur compounds are important in the off-flavour of UHT milk, attempts to improve its flavour have focused on reducing the concentration of these, e.g. by adding thiosulphonates, thiosulphates or cystine (which react with mercaptans) or sulphydryl oxidase, an indigenous milk enzyme (which oxidizes sulphydryls to disulphides Chapter 8). 

Formation.—Sulphuric acid is commonly produced in the oxidation of sulphur compounds less rich in oxygen ... 

A solution of tellurium-selenium sesquioxide, TeSe03, has been described (p. 357). A basic tellvmum selenate, 2Te02.Se03, analogous to the foregoing sulphur compound, is obtainable from tellurium oxide and selenic acid.4... 

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