Oxidation, acetaldehyde nitric oxide

AMYL ETHYL KETONE (541-85-5) Forms explosive mixture with air (flash point 110°F/43°C). Violent reaction with strong oxidizers, acetaldehyde, nitric acid, perchloric acid. Incompatible with aldehydes, sulfuric acid, aliphatic amines. 

Oxidation. Acetaldehyde is readily oxidised with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product depends on the reaction conditions. Acetic acid [64-19-7] may be produced commercially by the Hquid-phase oxidation of acetaldehyde at 65°C using cobalt or manganese acetate dissolved in acetic acid as a catalyst (34). Liquid-phase oxidation in the presence of mixed acetates of copper and cobalt yields acetic anhydride [108-24-7] (35). Peroxyacetic acid or a perester is beheved to be the precursor in both syntheses. There are two commercial processes for the production of peracetic acid [79-21 -0]. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or osone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde (36). Peracetic acid can also be formed directiy by Hquid-phase oxidation at 5—50°C with a cobalt salt catalyst (37) (see Peroxides and peroxy compounds). Nitric acid oxidation of acetaldehyde yields glyoxal [107-22-2] (38,39). Oxidations of /)-xylene to terephthaHc acid [100-21-0] and of ethanol to acetic acid are activated by acetaldehyde (40,41). 

Other routes to acrylonitrile, none of which achieved large-scale commercial appHcation, are acetaldehyde and HCN (56), propionittile dehydrogenation (57,58), and propylene and nitric oxide (59,60) ... 

Other possible chemical synthesis routes for lactic acid include base-cataly2ed degradation of sugars oxidation of propylene glycol reaction of acetaldehyde, carbon monoxide, and water at elevated temperatures and pressures hydrolysis of chloropropionic acid (prepared by chlorination of propionic acid) nitric acid oxidation of propylene etc. None of these routes has led to a technically and economically viable process (6). 

Partial oxidation of natural gas or a fuel oil using oxygen may be used to form acetylene, ethylene (qv) and propylene (qv). The ethylene in turn may be partially oxidi2ed to form ethylene oxide (qv) via advantages (/) and (5). A few of the other chemicals produced using oxygen because of advantages (/) and (5) are vinyl acetate, vinyl chloride, perchloroethylene, acetaldehyde (qv), formaldehyde (qv), phthaHc anhydride, phenol (qv), alcohols, nitric acid (qv), and acryhc acid. 

Chloratodimercuriacetaldehyde. OHC.C( Hg),Hg0.ClO2, mw 525.70, colorl prisms. Can be prepd by treating an excess of mercuric oxide in an aq soln of chloric acid with an ale soln of acetaldehyde. It is an extremely sensitive expl of the initiating type, exploding even when shaken under liq (Refs 1 3) Nitratodimercuriacetaldehyde. OHC.C( Hg).HgO.N02, mw 504.26, N 2.78%, colorl prisms from ale. Can be prepd by adding an ale soln of acetaldehyde to an aq soln of mercuric nitrate, acidified with nitric acid. Nearly insol in w. Puffs off on heating with evolution of a yellow cloud and Hg (Refs 1,2 3)... 

DuPont has developed a process for the manufacture of glyoxylic acid by aerobic oxidation of glycolic acid (Fig. 2.33) mediated by whole cells of a recombinant methylotrophic yeast (Gavagnan et al, 1995). The glycolic acid raw material is readily available from the acid-catalysed carbonylation of formaldehyde. Traditionally, glyoxylic acid was produced by nitric acid oxidation of acetaldehyde or glyoxal, processes with high E factors, and more recently by ozonolysis of maleic anhydride. 

The first product of the oxidation of alcohol is acetaldehyde and an important end-product is fulminic add, which latter can, however, only be isolated if silver or mercury ions are present. With these ions it forms salts—fulminates—which are stable towards nitric add in them, it must be presumed, the linkage with the metal is homopolar and non-ionogenic, as in mercuric cyanide. The formation of fulminic acid takes place because the carbonyl group of the aldehyde confers reactivity on the adjacent methyl group which then forms a point of attack for the nitrous acid. The various stages in the process are indicated by the following formulae ... 

Alkanes n-butene, isopentane, isooctane Cydoalkanes t dohezane, methylcyclopentane Olefins (sometimes called alkenes ) ethylene, propylene, butene Cydoolefins ( clohezene Alkynes acetylene Aromatics toluene, i ene CHLORINATED HYDROCARBONS ALDEHYDES, RCHO formaldehyde, acetaldehyde KETONES, RCX R " acetone, methylethylketone NITRIC OXIDE, NO ... 

What is the initial source of the free radicals that are so important for oxidant development Calvert and McC igg attempted to answer this question by evaluating the many proposed reactions with their detailed chemical model. Although the actual importance of any particular source will depend on the concentration of pollutants assumed and the time of irradiation they found for a typical mixture (nitric oxide nitrogen dioxide rra/is-2-butene, formaldehyde acetaldehyde carbon monoxide water and methane) that the following reactions were the most important radical sources ... 

Chemical/Physical. The atmospheric oxidation of ethyl ether by OH radicals in the presence of nitric oxide yielded ethyl formate as the major product. Minor products included formaldehyde and nitrogen dioxide. In the absence of nitric oxide, the products were ethyl formate and acetaldehyde (Wallington andjapar, 1991). 

Photolytic. Sunlight irradiation of 2-methylphenol and nitrogen oxides in air yielded the following gas-phase products acetaldehyde, formaldehyde, pyruvic acid, peroxyacetyl nitrate, nitrocresols, and trace levels of nitric acid and methyl nitrate. Particulate phase products were also identified and these include 2-hydroxy-3-nitrotoluene, 2-hydroxy-5-nitrotoluene, 2-hydroxy-3,5-dinitrotoluene, and tentatively identified nitrocresol isomers (Grosjean, 1984). Absorbs UV light at a maximum wavelength of 270 nm (Dohnal and Fenclova, 1995). 

Irradiation of ///-xylene isomerizes to p-xylene (Calvert and Pitts, 1966). Glyoxal, methylglyoxal, and biacetyl were produced from the photooxidation of ///-xylene by OH radicals in air at 25 °C (Tuazon et al, 1986a). The photooxidation of ///-xylene in the presence of nitrogen oxides (NO and NO2) yielded small amounts of formaldehyde and a trace of acetaldehyde (Altshuller et al, 1970). ///-Tolualdehyde and nitric acid also were identified as photooxidation products of ///-xylene with nitrogen oxides (Altshuller, 1983). The rate constant for the reaction of ///-xylene and OH radicals at room temperature was 2.36 x 10 " cmVmolecule-sec (Hansen et al., 1975). A rate constant of 1.41 x 10" L/molecule-sec was reported for the reaction of ///-xylene with OH radicals in the gas phase (Darnall et ah, 1976). Similarly, a room temperature rate constant of 2.35 x 10"" cmVmolecule-sec was reported for the vapor-phase reaction of ///-xylene with OH radicals (Atkinson, 1985). At 25 °C, a rate constant of 2.22 x 10"" cm /molecule-sec was reported for the same reaction (Ohta and Ohyama, 1985). Phousongphouang and Arey (2002)... 

Nicotinic acid Nicotinic acid, pyridine-3-carboxylic acid (20.2.9) is synthesized industrially by heating a paraldehyde trimer of acetaldehyde, under pressure with ammonia, which leads to the formation of 2-methyl-5-ethylpyridine, followed by oxidation with nitric acid which gives the desired product [22-25]. 

Its vapor is green and burns with a violet flame sol in w, ale eth. Was first prepd in 1881 (Refs 1 2) by oxidizing acetaldehyde with nitric acid. This and ocher methods are described by Curme Johnston (Ref 4, pp 125-26)... 

It has been used as a solvent and as an intermediate in the manuf of chemicals used in the expl industry and of synthetic rubber (Ref 4). During WWII, acetal(as well as acetaldehyde) was used in Germany as hyper-gollic fuel in liquid rocket propellants in conjunction with red or white fuming nitric acid which served as an oxidizer. Acetal was later replaced by ca te ch o 1( Bren zc ate chin or Brenzol in Ger)(Ref 10)... 

Acetaldehyde(as well as acetal) was used during WWII in Germany as a hypergolic(qvO fuel in liquid rocket propellants in conjunction with oxidizers, red or white coned nitric acids. These fuels were later replaced by catechol(Brenzcatechol or Brenzol, in Ger)... 

Peracetic acid can also be formed directly by liquid-phase oxidation at 5 to 50°C with a cobalt salt catalyst. Nitric acid oxidation of acetaldehyde yields glyoxal and the oxidation of p-xylene to terephthalic acid and of ethanol to acetic acid is activated by acetaldehyde. 

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