Nitric oxide thermal oxidation

Fig. 5. NO formation in a hydrogen engine having spark at 17° before top-dead center (BTC) rpm, 2900 and compression ratio, 5.5 1, where A is nitric oxide B, backfire C, power and D, brake thermal efficiency, (a) Effect of equivalence ratio, ( ) and (b), effect of water induction at 0 = 0.625.

At the high temperatures found in MHD combustors, nitrogen oxides, NO, are formed primarily by gas-phase reactions, rather than from fuel-bound nitrogen. The principal constituent is nitric oxide [10102-43-9] NO, and the amount formed is generally limited by kinetics. Equilibrium values are reached only at very high temperatures. NO decomposes as the gas cools, at a rate which decreases with temperature. If the combustion gas cools too rapidly after the MHD channel the NO has insufficient time to decompose and excessive amounts can be released to the atmosphere. Below about 1800 K there is essentially no thermal decomposition of NO. 

Thermal or photo-induced decompositions of dialkyl peroxides in the presence of suitable substrates yield various products. For example, with nitric oxides, alkyl nitrites or nitrates are formed and, with carbon monoxide, Z fZ-alkyl esters are obtained (44) ... 

Physical properties of hexachloroethane are Hsted in Table 11. Hexachloroethane is thermally cracked in the gaseous phase at 400—500°C to give tetrachloroethylene, carbon tetrachloride, and chlorine (140). The thermal decomposition may occur by means of radical-chain mechanism involving -C,C1 -C1, or CCl radicals. The decomposition is inhibited by traces of nitric oxide. Powdered 2inc reacts violentiy with hexachloroethane in alcohoHc solutions to give the metal chloride and tetrachloroethylene aluminum gives a less violent reaction (141). Hexachloroethane is unreactive with aqueous alkali and acid at moderate temperatures. However, when heated with soHd caustic above 200°C or with alcohoHc alkaHs at 100°C, decomposition to oxaHc acid takes place. 

The advantages of thermal incineration are that it is simple in concept, has a wide application, and results in almost complete destruction of pollutants with no liquid or solid residue. Thermal incineration provides an opportunity for heat recovery and has low maintenance requirements and low capital cost. Thermal incineration units for small or moderate exhaust streams are generally compact and light. Such units can be installed on a roof when the plant area is limited. = The main disadvantage is the auxiliary fuel cost, which is partly offset with an efficient heat-recovery system. The formation of nitric oxides during the combustion processes must be reduced by control of excess air temperature, fuel supply, and combustion air distribution at the burner inlet, The formation of thermal NO increases dramatically above 980 Table 13.10)... 

Nitric oxide is the simplest thermally stable odd-electron molecule known and, accordingly, its electronic structure and reaction chemistry have been very extensively studied. The compound is an intermediate in the production of nitric acid and is prepared industrially by the catalytic oxidation of ammonia (p. 466). On the laboratory scale it can be synthesized from aqueous solution by the mild reduction of acidified nitrites with iodide or ferrocyanide or by the disproportionation of nitrous acid in the presence of dilute sulfuric acid ... 

Thermal Decomposition. The therm decompn was studied betw 380 and 430° and found to be homogeneous and apparently 1st order. The products were complex and included nitric oxide, methane, carbon monoxide, and w plus small amts of ethane, ethylene, and nitrous oxide (Ref 23)... 

The nitro compound is isomerized to the nitrite, which can decompose either photochemically or thermally to the 9-anthroxyl radical. This radical can then dimerize or add nitric oxide to the 10 position to form the nitrosoketone. Isomerization of the nitrosoketone yields the monooxime, which then yields anthraquinone photochemically in the presence of NO. 

Importantly, the purple color is completely restored upon recooling the solution. Thus, the thermal electron-transfer equilibrium depicted in equation (35) is completely reversible over multiple cooling/warming cycles. On the other hand, the isolation of the pure cation-radical salt in quantitative yield is readily achieved by in vacuo removal of the gaseous nitric oxide and precipitation of the MA+ BF4 salt with diethyl ether. This methodology has been employed for the isolation of a variety of organic cation radicals from aromatic, olefinic and heteroatom-centered donors.174 However, competitive donor/acceptor complexation complicates the isolation process in some cases.175... 

Recently, it has been reported that a novel calcination procedure relying on nitric oxide gas in lieu of air also results in smaller cobalt crystallites over silica supports.15 17 The idea is to use a less oxidative gas to prevent rapid decomposition of the nitrate precursor during thermal nitrate decomposition, which has been observed when 02 is present.17 As a result, the mobility of the precursor on the oxide carrier surface is hindered, resulting in a smaller average Co oxide cluster... 

SN P spontaneously releases N O both thermally and photochemically [61-65], but is quite stable in the dark and in aqueous in vitro physiological media [66]. This implies that absorption of heat and light energy induces electron transfer from the Fe2+ center to the N 0+ ligand, resulting in weakening of the Fe-N O bond and subsequent release of NO [65]. SNP also decomposes in an aqueous environment in the presence of biological reductants [65, 66] and some transition metal ions to produce nitric oxide. 

The increased importance of charge transfer in proceeding up the series of NO+ complexes with the enhanced donor strength of arenes that vary from benzene with IP = 9.23 eV to the electron-rich hexamethylbenzene (IP - 7.85 eV) has its chemical consequences with respect to thermal (adiabatic) electron transfer. Thus the benzene complex with Z = 0.52 is persistent in acetonitrile solution for long periods, provided the solution is protected from adventitious moisture and light. By contrast, the hexamethylbenzene complex with Z = 0.97 slowly liberates nitric oxide under... 

Nitrosothiols decompose photochemically and thermally to give the corresponding disulphides and nitric oxide18 23 14 24 (equation 6). In most cases the nitric oxide has not been identified as the primary product but rather as its oxidized form, nitrogen dioxide. 

The reaction in water at pH 7.4 has been much studied since the discovery of the importance of nitric oxide. The products are as for the thermal and photochemical reactions, except that the final product is nitrite ion. This is to be expected since nitric oxide in aerated water at pH 7.4 also yields quantitatively nitrite ion25, by it is believed the series of equations 7-9, which involves oxidation to nitrogen dioxide, further reaction to give dinitrogen trioxide which, in mildly alkaline solution, is hydrolysed to nitrite ion. Under anaerobic conditions it is possible to detect nitric oxide directly from the decomposition of nitrosothiols using a NO-probe electrode system26. Solutions of nitrosothiols both in... 

A method involving SPE was developed for the determination of ten A-nitroso amino acids in cured meat products. These compounds were derivatized with diazomethane followed by O-acylation of hydroxyl groups with acetic anhydride-pyridine reagent. The methyl esters and their acylated derivatives were separated by GC on a DB-5 fused silica capillary column and quantified with a TEA-CLD specific for the nitric oxide derived from the thermal denitrosation of nitrosamines recovery exceeded 75% at the 10 ppb level579. 

During combustion processes the molecular nitrogen in the combustion air and the fuel nitrogen that may be present in the fuel is converted into nitric oxide and some nitrogen dioxide4 when NO and residual O2 are cooled together. The NO formation is also controlled by (1) thermal NO, (2) prompt NO and (3) N2O to NO routes5-7. 

In the presence of various metal ions, 2-(fluoroenone)benzothiazoline has been found to rearrange to A-2-mercaptophenylenimine, while a free radical mechanism involving the homolysis of C-S and C-N bonds has been invoked to explain the formation of 3-phenyl-1,2,4-triazole derivatives from the thermal fragmentation and rearrangement of 2-(arylidenehydrazino)-4-(5//)-thiazolone derivatives. The cycloadducts (36) formed from the reaction of 3-diethylamino-4-(4-methoxyphenyl)-5-vinyl-isothiazole 1,1-dioxide (34) with nitric oxides or miinchnones (35) have been found to undergo pyrolytic transformation into a, jS-unsaturated nitriles (38) by way of pyrrole-isothiazoline 1,1-dioxide intermediates (37). 

V) Flame zone When the dark-zone reactions occur rapidly after an induction period, they produce a flame zone in which the final combustion products are formed and attain a state of thermal equiUbrium. When the pressure is low, below about 1 MPa, no flame zone is produced because the reduction of nitric oxide is too slow to produce nitrogen. 

In an atmosphere of nitric oxide, thermal decomposition produces barium nitrite, Ba(N02)2. Reactions with soluble metal sulfates or sulfuric acid yield barium sulfate. Many insoluble barium salts, such as the carbonate, oxalate and phosphate of the metal, are precipitated by similar double decomposition reactions. Ba(N03)2 is an oxidizer and reacts vigorously with common reducing agents. The solid powder, when mixed with many other metals such as aluminum or zinc in their finely divided form, or combined with alloys such as... 

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