Nitrous oxide, reaction with mercury

In the oxidation of hydroxylamine by silver salts and mercurous salts, the nature of the reaction product apparently depends upon the extent to which catalysis participates in the total reaction. This is illustrated by some results obtained with mercurous nitrate as oxidizing agent. The reaction is strongly catalyzed by colloidal silver, and is likewise catalyzed by mercury. The reaction of 0.005 M mercurous nitrate with 0.04 M hydroxylamine at pH 4.85 proceeds rapidly without induction period. The mercury formed collects at the bottom of the vessel in the form of globules when no protective colloid is present, so the surface available for catalysis is small. Under these conditions the yield is largely nitrous oxide. Addition of colloidal silver accelerates the reaction and increases the yield of nitrogen. Some data are given in Table III. 

Before mercury-photosensitized decomposition of nitrous oxide could be used as a technique for generation of oxygen atoms, it was necessary to establish unambiguously the primary step in this reaction. Early investigation (70) could not distinguish with certainty between the two possible primary steps... 

H. G. de Claubry found that when nitroxylsulphonic acid is heated with mercury, there is formed mercuric sulphate, sulphur dioxide, nitric oxide, and nitrogen and G. Lunge said that when a soln. in cone, sulphuric acid is shaken with mercury, nitric oxide and sulphuric acid are quantitatively formed and F. Rasehig observed that the reaction is completely inhibited by mercury, possibly with the formation of hydroxynitrosylsulphonic acid. A. Graire found that the acid is not reduced further than nitric oxide by agitation with mercury but if sulphur dioxide is present, some nitrous oxide may be formed. J. W. Dobereiner found that a soln. of nitroxylsulphonic acid in cone, sulphuric acid oxidizes mercury copper, silver, Zinc, and iron, and the liquid is coloured red, violet-blue, or purple and J. J. Berzelius added that nitric oxide is at the same time evolved. J. W. Dobereiner... 

DIMETHYLNITROMETHANE (79-46-9) Forms explosive mixture with air (flash point 75°F/24°C). Violent reaction with strong oxidizers, chlorosulfonic acid, hydrocarbons, hydroxides calcium or potassium hydroxide, oleum. May explode on heating (burns even in absence of air), causing fast rise in pressure closed containers may explode. Decomposition is promoted by the presence of acids, amines, or bases. Forms heat-, friction-, or shock-sensitive explosive products with acids, amines, inorganic bases, mercury salts, nitrous acid, silver salts. The presence of metal oxides increases the explosive sensitivity of this compound. Incompatible with isocyanates, potassium hydride. Attacks some plastics, rubber, and coatings. 

CF2 CF2 < CF2 CF-CH CHMe < CF2 CF CH CH2 < CF2 CF-CF CF2 Approximate Arrhenius parameters have been obtained for the reaction of oxygen atoms ( F), from the mercury-sensitized decomposition of nitrous oxide, with the fluoroethylenes at two temperatures (25 and 150 °C) using the olefin CH2 C(CFs)Me as reference compound. All the fluoroethylenes appear less reactive than ethylene again with the exception of tetrafluoroethylene, reactivity being least for cis-l,2-di-fluoroethylene. The differences appear largely due to differences in activation energy, and the anomalous reactivity of tetrafluoroethylene is noteworthy. 

The reaction of oxygen atoms P), from the mercury-sensitized photolysis of nitrous oxide, with perfluorobuta-1,3-diene yields the compounds CXIF, ... 

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