chemical physics of discharges - Argonne National Laboratory
chemical physics of discharges - Argonne National Laboratory chemical physics of discharges - Argonne National Laboratory
476 Instead a hydrogen deficient film was produced. The formation of a hydrogen deficient film from a parent molecule which has a high enough (H/C) ratio to form a hydrogen saturated film can be attributed to two factors. In the first instance, C1 preferentially appears in the gas phase as is indicated by the low percentage of C1 in the film, the absence of a significant C-C1 absorption peak in the infrared spectrum(Figure 3) and the presence of HC1 downstream from the discharge. The extension of this work to other functional groups is anticipated to determine if this is a general scheme. In the second instance, the tendency to form hydrogen in a microwave discharge is again noted in the case of methyl chloride as in the case of methane(Pigures la and lb). Apparently for hydrocarbons containing functional groups, the formation of hydrogen is favored even at the expense of the formation of a hydrogen deficient film. The formation of ethane observed as a product of the methyl chloride discharge could be due to the recombination of methyl radicals produced in the discharge. Films formed in various types of electrical discharges have not been extensively characterized. The recent work of Jesch et a1 (2) described the infrared analysis of a series of films produced from hydrocarbons in a glow discharge. Direct comparison between the present results and those of Jesch et a1 is not possible since two different types of electrical discharges were used. The type of discharge used dramatically alters the nature of both the gaseous and solid rearrangement products as indicated above The properties of the film produced from methyl chloride are similar to those reported previously(1) for the hydrogen deficient films formed from acetylene, benzene and naphthalene. The color of the methyl chloride f ilm was dark (brownish-black) characteristic of hydrogen deficient films in contrast to the light yellow methane film characteristic pf hydrogen saturated films. The high electron spin concentration of the methyl chloride film ibad also been oberved for the hydrogen deficient film from acetylene. The films produced from both methane and methyl chloride appear to be highly cross-linked as evidenced by the negligible solubility is liquids used as solvents for other polymeric systems. The methyl chloride film contains a greater number of free electrons than the methane film indicative of a significant number of unsaturated valences in the methyl chloride film. The methyl chloride film appears to be characterized by a greater degree of unsaturation than the methane film. Highly unsaturated polymeric systems have been found difficult to analyze by infrared spectroscopy* which has also been noted in the present results. Definitive NMR work would be helpful in elucidating the nature of these polymeric films. * private communication with Dr. Vernon Bell(NASA - Langley Research Center) Acknowledgements - The authors would like to acknowledge the help of Dr. R. E. Dessy in obtaining the ESR spectra and the experimental assistance of Mr. R. 0. McGuffin‘. REFERENCES (1). F. J. Vastola and J. P. Wightman, J. Appl. Chem., 14, 69 (1964). (2). K. Jesch, J. E. Bloor and P. L. Kronick, J. Poly. Sci. A-1, 4, 1487 (1966). (3). E. Swift, ‘r., R. L. Sung, J. Doyle and J. K. Stille, J. Org. Chem., a, 3114 (1965).
1 I I / 10000 Y 1 - I before di sc harge I discharge during Fig.la. Selected mass .spectra o ih a microwave 2 15 MAS SIC HA RGE RATIO eaks from Fig.1b. Selected peaks from Pmethane mass spectra of methyl discharge. chloride in a discharge. n
- Page 430 and 431: Table 4. Room-?;ergerature isomer s
- Page 432 and 433: I' 1.3 . /o 9 IO 9 6 a 425 F F 33 I
- Page 434 and 435: Brooks J.D. and Sternhell S. (1957)
- Page 436 and 437: (52) Gib3 T.C. and Greenwood N.N. (
- Page 438 and 439: 434 transducer vas then introduced
- Page 440 and 441: 436 yield is quite similar. The con
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- Page 444 and 445: 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 4
- Page 446 and 447: 442 CHEMICAL REACTIONS IN A CORONA
- Page 448 and 449: helium 444 CORONA REACTOR SYSTEM Fi
- Page 450 and 451: 446 The ultraviolet spectrum. for t
- Page 452 and 453: Biphenyl Fraction 448 The low molec
- Page 454 and 455: LUd The actual structural definitio
- Page 456 and 457: I I I I I In m 9 In 2 , I: r- In m
- Page 458 and 459: ’. 454 Mechanism I The available
- Page 460 and 461: 456 , , . The relatively low yield
- Page 462 and 463: 458 h/lethylacetylene, allene and b
- Page 464 and 465: Introduction VAPOR PHASE DECOMPOSIT
- Page 466 and 467: 462 more efficient hydrogenation. T
- Page 468 and 469: 464 place in parallel with fragment
- Page 470 and 471: 466 P rl 0, k 7 rnI rn al k a I hl
- Page 472 and 473: 458 TABLE I. COMPOSI'IION OF GASEOU
- Page 474 and 475: REFERENCES 1. C. Hirayama and D. A.
- Page 476 and 477: i 472 Reciprocal Arc Enthalpy ,-> F
- Page 478 and 479: 474 be pumped down without altering
- Page 482 and 483: i 478
- Page 484 and 485: 480 FATTY ACIDS AND n-ALKANES IN GR
- Page 486 and 487: 482 TA5L,E 2. - Carbon number distr
- Page 488 and 489: 6. 7. a. 9. 484 Lawlor, D. L., and
- Page 490 and 491: ' I ' Sample No. 6 ' 12 IO 8 6 z 4
- Page 492 and 493: . 488 uiolecular weight of which ca
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- Page 496 and 497: 492 found at 5.7 and 4.9& for the W
- Page 498 and 499: 494 mechanisms. However, the voltad
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- Page 504 and 505: 500 (1;) Ten, T. 17.: a;1d,Dic;
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- Page 520 and 521: The line broadening at 79OK of the
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1<br />
I<br />
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/ 10000<br />
Y<br />
1<br />
-<br />
I<br />
before<br />
di sc harge<br />
I discharge<br />
during<br />
Fig.la. Selected<br />
mass .spectra o<br />
ih a microwave<br />
2 15<br />
MAS SIC HA RGE RATIO<br />
eaks from Fig.1b. Selected peaks from<br />
Pmethane mass spectra <strong>of</strong> methyl<br />
discharge. chloride in a discharge.<br />
n
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