Sulfur 344 Subject

The acids present in a given wine are determined by the grape variety, climate, presence of gray rot [Botrytis cinerea), yeasts, bacteria, and various treatments to which the wine may be subjected (sulfur dioxide, ascorbic acid, acidification, desacidifica-tion). There are at least 50 different acids in wine ranging in concentration from 1 or 2gl (tartaric, malic, succinic acids) to hundreds of mgl (citric, lactic, acetic acids) to tens of mgl (pyruvic, shikimic acids). However, tartaric, malic (depending on the MLF), acetic, and succinic acids constitute 80-90% of total complement of wine acids. 

The potential advantages of LPG concern essentially the environmental aspects. LPG s are simple mixtures of 3- and 4-carbon-atom hydrocarbons with few contaminants (very low sulfur content). LPG s contain no noxious additives such as lead and their exhaust emissions have little or no toxicity because aromatics are absent. This type of fuel also benefits often enough from a lower taxation. In spite of that, the use of LPG motor fuel remains static in France, if not on a slightly downward trend. There are several reasons for this situation little interest from automobile manufacturers, reluctance on the part of automobile customers, competition in the refining industry for other uses of and fractions, (alkylation, etherification, direct addition into the gasoline pool). However, in 1993 this subject seems to have received more interest (Hublin et al., 1993). 

The high C/H ratio for heavy fuels and their high levels of contaminants such as sulfur, water, and sediment, tend to reduce their NHV which can reach as low as 40,000 kJ/kg by comparison to the 42,500 kJ/kg for a conventional home-heating oil. This characteristic is not found in the specifications, but it is a main factor in price negotiations for fuels in terms of cost per ton. Therefore it is subject to frequent verification. 

The main justification for diesel fuel desulfurization is related to particulate emissions which are subject to very strict rules. Part of the sulfur is transformed first into SO3, then into hydrated sulfuric acid on the filter designed to collect the particulates. Figure 5.21 gives an estimate of the variation of the particulate weights as a function of sulfur content of diesel fuel for heavy vehicles. The effect is greater when the test cycle contains more high temperature operating phases which favor the transformation of SO2 to SO3. This is particularly noticeable in the standard cycle used in Europe (ECE R49). 

Type J thermocouples (Table 11.58) are one of the most common types of industrial thermocouples because of the relatively high Seebeck coefficient and low cost. They are recommended for use in the temperature range from 0 to 760°C (but never above 760°C due to an abrupt magnetic transformation that can cause decalibration even when returned to lower temperatures). Use is permitted in vacuum and in oxidizing, reducing, or inert atmospheres, with the exception of sulfurous atmospheres above 500°C. For extended use above 500°C, heavy-gauge wires are recommended. They are not recommended for subzero temperatures. These thermocouples are subject to poor conformance characteristics because of impurities in the iron. 

Although thiosulfate is one of the few reducing titrants not readily oxidized by contact with air, it is subject to a slow decomposition to bisulfite and elemental sulfur. When used over a period of several weeks, a solution of thiosulfate should be restandardized periodically. Several forms of bacteria are able to metabolize thiosulfate, which also can lead to a change in its concentration. This problem can be minimized by adding a preservative such as Hgl2 to the solution. 

Analytical and Test Methods. o-Nitrotoluene can be analyzed for purity and isomer content by infrared spectroscopy with an accuracy of about 1%. -Nitrotoluene content can be estimated by the decomposition of the isomeric toluene diazonium chlorides because the ortho and meta isomers decompose more readily than the para isomer. A colorimetric method for determining the content of the various isomers is based on the color which forms when the mononitrotoluenes are dissolved in sulfuric acid (45). From the absorption of the sulfuric acid solution at 436 and 305 nm, the ortho and para isomer content can be deterrnined, and the meta isomer can be obtained by difference. However, this and other colorimetric methods are subject to possible interferences from other aromatic nitro compounds. A titrimetric method, based on the reduction of the nitro group with titanium(III) sulfate or chloride, can be used to determine mononitrotoluenes (32). Chromatographic methods, eg, gas chromatography or high pressure Hquid chromatography, are well suited for the deterrnination of mononitrotoluenes as well as its individual isomers. Freezing points are used commonly as indicators of purity of the various isomers. 

In a typical isothermal process, 70% hydrogen peroxide is added to 98% sulfuric acid, and subjected to rapid stirring and efficient cooling, so that the temperature does not rise to above 15°C. If equimolar quantities of reactants are used, the product contains 42% H2SO and 10% H2O2. Although the reaction may seem simple, many of its features are critically important and it should only be attempted foUowiag advice from speciaUsts. 

Mitsubishi Chemical Industries, Ltd. practiced a Henkel II technology starting with toluene to produce benzoic acid. Reaction of benzoic acid with potassium hydroxide resulted in potassium benzoate, which was subjected to a disproportionation reaction to produce dipotassium terephthalate and benzene. Dipotassium terephthalate reacted with sulfuric acid, and the resulting terephthahc acid was recovered by filtration and drying (65,66). Here, dipotassium sulfate was the by-product. 

Sulfonic acids may be subjected to a variety of transformation conditions, as shown in Figure 2. Sulfonic acids can be used to produce sulfonic anhydrides by treatment with a dehydrating agent, such as thionyl chloride [7719-09-7J. This transformation is also accomphshed using phosphoms pentoxide [1314-56-3J. Sulfonic anhydrides, particulady aromatic sulfonic anhydrides, are often produced in situ during sulfonation with sulfur trioxide. Under dehydrating conditions, sulfonic acids react with substituted aromatic compounds to give sulfone derivatives. 

The H2S sulfanes are the subject of several reviews (129,133). Except for hydrogen sulfide these have no practical utiUty. Sodium tetrasulfide [12034-39-8] is available commercially as a 40 wt % aqueous solution and is used to dehair hides in taimeries, as an ore flotation agent, in the preparation of sulfur dyes (qv), and for metal sulfide finishes (see Leather Mineral recovery and processing). 

The sulfur nitrides have been the subject of several reviews (206—208). Although no commercial appHcations have as yet been developed for these compounds, some interest was stimulated by the discovery that polythiazyl, a polymeric sulfur nitride, (SN), with metallic luster, is electroconductive (see Inorganic highpolymers) (208,209). Other sulfur nitrides are unstable. Tetrasulfur nitride is explosive and shock-sensitive. 

Burning Pyrites. The burning of pyrite is considerably more difficult to control than the burning of sulfur, although many of the difficulties have been overcome ia mechanical pyrite burners. The pyrite is burned on multiple trays which are subject to mechanical raking. The theoretical maximum SO2 content is 16.2 wt %, and levels of 10—14 wt % are generally attained. As much as 13 wt % of the sulfur content of the pyrite can be converted to sulfur trioxide ia these burners. In most appHcations, the separation of dust is necessary when sulfur dioxide is made from pyrite. Several methods can be employed for this, but for many purposes the use of water-spray towers is the most satisfactory. The latter method also removes some of the sulfur... 

Chemical Properties. Anhydrous sodium dithionite is combustible and can decompose exothermically if subjected to moisture. Sulfur dioxide is given off violentiy if the dry salt is heated above 190°C. At room temperature, in the absence of oxygen, alkaline (pH 9—12) aqueous solutions of dithionite decompose slowly over a matter of days. Increased temperature dramatically increases the decomposition rate. A representation of the decomposition chemistry is as follows ... 

The stmcture of the sulfuri2ed vat dyes is uncertain but in the presence of amino or methyl groups, thia2o1e-ring formation is possible. Examples have been confined to the dyes whose intermediates have been subjected to the conventional sulfur or polysulfide bake (Tables 2—5). 

Sulfuric Acid Concentrators. Concentrators for increasing the strength of dilute sulfuric acid by removing water have been used since the early days of the industry. A two-volume text on this subject was pubHshed ia 1924 (135) more recent discussions of the subject are also available (32,136-141). 

Measurement and specification of nitrates or other nitrogen oxide compounds in sulfuric acid is a complex subject. The difficulty occurs because nitrogen oxides are usually present both as nitrous and nitric compounds, predominantiy in the nitrous form. Hence, analytical procedures specific for nitrates only do not give a complete analysis. 

AH vapors, including hotweH odors, are captured in a header system linked with the incineration air of a steam boiler or hot oil vaporizer. Drain seals avoid escape of odors from the sewer lines. This completely eliminates total reduced sulfur (TRS) emissions. The SO2 emissions are subject to local regulations. 

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