Nitrogen-sulfur compounds formation

Formation of Nitrogen-Sulfur Compounds. Once HADS is formed, it can further react to form other nitrogen-sulfur compounds (Figure 1). Chang et al. (3) have published an extensive review article on the kinetics and mechanisms of important reactions involved. 

Similar to nitrogen compounds, electron-rich sulfur compounds, such as the sulfides, with the lone pair of electrons on the sulfur atom, are oxidized to sulfoxides and, further, to sulfones by the H202/titanosilicate sytem (218,232, 233). Table XXXI (232) illustrates typical conversions and product selectivities for various sulfides for the reactions catalyzed by TS-1. Bulky sulfides such as alkyl, phenyl sulfides are relatively unreactive because of their steric exclusion from the pores of TS-1. Diphenyl sulfide could not be oxidized at all. As the diffusivity and, hence, the conversion of the sulfide decreases, the further oxidation of the primary product (sulfoxide) becomes more competitive, leading to increased formation of the corresponding sulfone (Table XXXI) ... 

The presence of sulfur compounds in the combustion process can affect the nitrogen oxides, as well. Thus, it is important to study sulfur compound oxidation not only to find alternative or new means of controlling the emission of objectionable sulfur oxides, but also to understand their effect on the formation and concentration of other pollutants, especially NO,. ... 

If indeed S02 and S03 are effective in reducing the superequilibrium concentration of radicals in flames, sulfur compounds must play a role in NO formation from atmospheric nitrogen in flame systems. Since S02 and S03 form no matter what type of sulfur compound is added to combustion systems, these species should reduce the oxygen atom concentration and hence should inhibit NO formation. Wendt and Ekmann [46] have reported flame data that appear to substantiate this conclusion. 

Thermodynamic properties for explosion calculations are presented for major organic chemical compounds. The thermodynamic properties include enthalpy of formation, Gibbs free energy of formation, internal energy of formation and Helmholtz free energy of formation. The major chemicals include hydrocarbon, oxygen, nitrogen, sulfur, fluorine, chlorine, bromine, iodine and other compound types. 

An alternate and more controlled approach to the synthesis of phenothiazines involves sequential aromatic nucleophilic displacement reactions. This alternate scheme avoids the formation of the isomeric products that are sometimes observed to form from the sulfuration reaction when using substituted aryl rings. The first step in this sequence consists of the displacement of the activated chlorine in nitrobenzene (30-1) by the salt from orf/io-bromothiophenol (30-2) to give the thioether (30-3). The nitro group is then reduced to form aniline (30-4). Heating that compound in a solvent such as DMF leads to the internal displacement of bromine by amino nitrogen and the formation of the chlorophenothiazine (30-4). Alkylation of the anion from that intermediate with 3-chloro-l-dimethylaminopropane affords chlorpromazine (30-5) [31]. 

Studies of the formation, chemical composition, and properties of deposits have shown that they consist of partially oxidized organic material, including more or less nitrogen, sulfur, and phosphorus. Compounds of iron, silicon, calcium, and other metals are present in small quantity, together with substantial amounts of lead oxides, sulfates, and halides from combustion of the antiknock fluid. The effects of these deposits are both physical and chemical in nature they may physically interfere with lubrication, heat transfer, gas flow, operation of valves and spark plugs chemically, they may bring about corrosion and oxidation. 

In a hydrogen-rich flame, combustion of samples containing phosphorus and/or sulfur results in the formation of chemiluminescent species which emit light characteristic of the heteroatom introduced into the flame. Selection of an interference filter with a 394- or 526-nm bandpass allows selectivities for sulfur and phosphorus respectively. Recent work by Krost and co-workers (27) found that a 690-nm filter showed selectivity for some nitrogen-containing compounds. 

---