Fluorine-oxygen system

A number of oxides of fluorine are known. Their preparation, properties, and reactions have been reviewed by Streng. A further description of them will not be given here. 

The photochemical decomposition of fluorine in the presence of O3 was studied by Staricco et al. between 0 and 20 °C using 3650 A radiation. The sole product of the reaction was O2. The quantum yield of O3 disappearance had an activation energy of 2.8 kcal.mole and was 4.6 x 10 independent of conditions at 20 °C. 

An alternative mechanism was also considered in which reaction (4 ) was the chain-propagating step and reaction (2 ) the chain-terminating step, viz. 

This mechanism was discarded because it required that the addition step (4 ) have a larger activation energy than the atom transfer step (2 ). 

Both mechanisms require the presence of FO radicals. McGrath and Norrish have since flash-photolyzed F2 in the presence of O3 and were unable to detect FO radicals by kinetic spectroscopy, probably because of the great reactivity of the radical. 

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Schmidt, 1967 Handling and Use of Fluorine and Fluorine-Oxygen Mixtures in Rocket Systems, SP-3037, Schmidt, H. W Harper, J. T Washington, NASA, 1967... 

Much of the discussion of oxygen flame calorimetry presented in section 7.3 is directly applicable to fluorine flame calorimetry. As in the case of bomb calorimetry, however, the special properties of fluorine combustion systems and problems associated with handling fluorine require a somewhat different experimental method [109,115,116]. Thus, for example, a metal burner should be used. Also, the fact that the mixing of many gases with F2 may lead to spontaneous ignition hinders the use of a premixed flame. Fluorine combustion calorimetry has been used to study the thermochemistry of important reactions, such as... 

Several reaction systems were discovered in which, in addition to fluorination, oxygenation also occurred. These include SF4 (60) N2F4, HNF2, and F2NCFO (246, 248) and M0F5 (35). In the following equations, the end products observed for the SF4-CIF3O reaction are underlined ... 

M. Kilpatrick L.L. Baker, Jr, A study of fast reactions in fuel-oxidant systems, FifthSymp Comb, Reinhold, NY, (1955) 26) S.A. Masier et al, Hypergolic ignition of light hydrocarbon fuels with fluorine-oxygen (FLOX) mixtures, ... 

These studies indicate that liquid ozone-fluorine mixtures are homogeneous and do not form a two-phase region as does the ozone-oxygen system. Mixtures of 30% ozone in fluorine require very few handling precautions over those observed with 100% liquid fluorine. 

In this sub-section it is proposed to deal first with effects of oxides of nitrogen in the oxidation of carbon monoxide, in a manner similar to that adopted for the hydrogen—oxygen system. Following this the reactions with fluorine, fluorine monoxide and sulphur dioxide will be considered. 

Schmidt, FI. W., and J. T. Harper. 1967. Handling and use of fluorine and fluorine-oxygen mixture in rocket systems. NASA SP-3037. Washington, DC National Aeronautics and Space Administration. 

For the 4FA-MMA system, the analogons situation also takes place in the case of fluorine-oxygen-containing (meth)acrylates (FOAA) copolymerisation (Table 8.8) [52, 73]. 

Oxygen, chlorine, and fluorine piping systems must be free of organic contaminants. Organic materials, particularly hydrocarbon greases and oils, react violently with these chemicals. 

Compare these two basis sets and note the differences between them for carbon, nitrogen, oxygen and fluorine (you can use GFPrinf or GHnput with a system containing these elements one example, fluoroacetamide, is illustrated at the left). What would you expect to be the advantages of the changes that you see ... 

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