Radiation sensitized chain reactions. Aqueous nitrous oxide and methanol

In the region of pressure 0 to 500 mrn approximately to the equation the thermal decomposition of nitrous oxide conforms approximately to the equation k = an /1 + a'n + bn , where k is the form al first-order rate constant, — (1/n) d n /d t , n the initial concentration and a, a' and b are nearly constant. Above about 100 m m this expression approximates to k = A + bn , which holds up to several atmospheres. Fresh and more detailed experiments have once again disproved the suggestion that the first term in these expressions is due to a surface reaction. (In certain states of reaction vessels, made of a particular brand of silica, a surface reaction may appear but is immediately recognizable by special criteria, and can be eliminated.) Detailed study of the formation of nitric oxide in the course of the decomposition, and of the effect of inert gas upon this process, shows that side reactions involving oxygen atoms, chain reactions and catalysis by nitric oxide play only minor parts in determining the shape of the k-n curve. The form of this curve, which is an inherent character of the reaction N 2 O = N 2 + O, raises theoretical questions of considerable interest.

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Photosensitized Chain Reactions in Alkaline Solutions of Nitrous Oxide in 2-Propanol

Journal of the American Chemical Society ◽

10.1021/ja00982a004 ◽

1967 ◽

Vol 89 (6) ◽

pp. 1302-1307 ◽

Cited By ~ 5

Author(s):

Warren V. Sherman

Keyword(s):

Nitrous Oxide ◽

Alkaline Solutions ◽

Chain Reactions

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γ-Radiolysis of liquid 2-propanol. III. Chain reactions in alkaline solutions containing nitrous oxide

The Journal of Physical Chemistry ◽

10.1021/j100865a022 ◽

1967 ◽

Vol 71 (6) ◽

pp. 1695-1702 ◽

Cited By ~ 10

Author(s):

Warren V. Sherman

Keyword(s):

Nitrous Oxide ◽

Alkaline Solutions ◽

Chain Reactions

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Radiation-induced chain reactions in alkaline solutions of nitrous oxide in aliphatic alcohols

Chemical Communications (London) ◽

10.1039/c19660000250 ◽

1966 ◽

pp. 250

Author(s):

Warren V. Sherman

Keyword(s):

Nitrous Oxide ◽

Aliphatic Alcohols ◽

Alkaline Solutions ◽

Chain Reactions ◽

Radiation Induced

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The kinetics of the reaction between hydrogen and nitrous oxide.─I

Proceedings of the Royal Society of London. Series A, Containing Papers of a Mathematical and Physical Character ◽

10.1098/rspa.1933.0186 ◽

1933 ◽

Vol 142 (847) ◽

pp. 524-545 ◽

Cited By ~ 9

Keyword(s):

Nitrous Oxide ◽

Kinetic Method ◽

Gaseous Mixture ◽

Theoretical Treatment ◽

Chain Process ◽

Combustion Chemistry ◽

Chain Reactions ◽

Simple Molecules ◽

A Chain ◽

Kinetics Of

Until about five years ago, the theoretical treatment of the mechanism of the oxidation of simple molecules had been comparatively neglected. Prior to this, however, considerable progress had been made in the study of the kinetics of thermal and photochemical gas reactions. That knowledge has now been successfully applied and extended to solve some of the major problems in combustion chemistry, and thereby has given rise to the development of the theory of thermal chain reactions. Hitherto, the investigation of these reactions has been confined almost entirely to oxidations by molecular oxygen. It is known, however, that many gases ignite in:nitrous oxide at about the same temperature as they do in oxygen, and it might be anticipated that here, too, a chain process is in operation. The object of studying the interaction of hydrogen and nitrous oxide was to determine whether it is a chain reaction, and if so, to make a detailed analysis of its mechanism by the kinetic method. One of the first criteria in looking for the possibility of the propagation of chains in a gaseous mixture is that the reaction must be exothermic. This condition is amply fulfilled in the present instance, for 75 k. cal. are liberated per mole of water formed. Indeed, the reaction is even more exothermic than the formation of one mole of water from hydrogen and oxygen, when only 50 k. cal. are evolved. This greater exothermicity is due to the fact that 45 k. cal. required to dissociate 1 mole of N 2 O N 2 and O, whereas the production of 1 mole of O atoms from O 2 required about 60 k. cal.

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