chemical physics of discharges - Argonne National Laboratory
chemical physics of discharges - Argonne National Laboratory chemical physics of discharges - Argonne National Laboratory
'603 ~---~ _-_- T_--r.- Figure 5 1000 900 800 700 650 E - TOLUENE F. BE NZENE G -SlVRENE i \
DISCUSSION 289 The salient features of the information presented above might be summarized as follows. In a mixture of organic vapor and nitrogen subjected to high-frequency, high-voltage, electrodeless discharge, the nitrogen, the organic compound and trace amounts of oxygen and water are activated and combine chemically to yield products of higher molecular weight than the starting materials. These proqucts condense on any solid surface available and may even undergo further chemical reaction within themselves and with more monomeric material which is not electrically activated. The chemical mechanism of this series of reactions must be complex, possibly produced by simple ionization through collision with a rapidly-moving electron followed by expulsion of two secondary electrons: N2 + e-+N2+ + 2e- or + RH + e---+RH + 2e- I' These are the products ordinarily found in mass spectrometry and on exposure to gamma or beta radiation. These activated cationic products may activate vinyl polymerization or undergo secondary reactions, u' yielding neutral free radicals or even anions, either of similar structure or in the form of fragments and combination or rearrange- 9 ment products. In the present case there exists the further possibility that reaction products become reactivated, since they are formed in the presence of the high-voltage field, and undergo further reaction. 1 The simplest mechanism to consider would be polymerization of the I vinyl monomers to long-chain products after initiation by some active c ,, species. The fact that non-vinyl compounds gave good yields may be ' explained through a mechanism involving some fragmentation of every 1 monomer molecule and combination of the fragments to products of higher molecular weight. The vinyl monomers could be reacting through this P* i non-vinyl mechanism also. The action of halogenated additives suggests that the yield of reactive intermediates is increased by some of them and that these intermediates increase the initiation of vinyl polymerization. There is not enough data to .establish this firmly. It may also be consid- ered that, by changing the dielectric constant of the gas mixture, the additive can increase the efficiency of energy transfer from the elec- tric field to the monomer. The other additives had little or no effect, indicating that the situation is not very similar to bulk or solution polymerizations by 5 free radical or ionic catalysis such as are now being actively studied by several laboratories (6,7). Certainly we do not have a simple vinyl polymerization. Otherwise some of the potential inhibitors would have shown an effect.
- Page 237 and 238: 237 Table 2 Experimental Variables
- Page 239 and 240: 239 Zhbie I Eerccnt Consumption of
- Page 241 and 242: 241 Discussion The systematic varia
- Page 243 and 244: I \ 1 243 FORMATION OF HYDROCARBONS
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- Page 281 and 282: i i (12) c (11) (14) I 281 LITERATU
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- Page 285 and 286: 285 TABLE 2 Effect of Haloqenated A
- Page 287: ANALYTICAL RESULTS Some evidence wa
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'603 ~---~ _-_- T_--r.-<br />
Figure 5<br />
1000 900 800 700 650<br />
E - TOLUENE<br />
F. BE NZENE<br />
G -SlVRENE<br />
i<br />
\
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