chemical physics of discharges - Argonne National Laboratory

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446 The ultraviolet spectrum. for the benzene fraction was obtained by running differentially against pure benzene in isooctane. A broad absorption band with a maximum at 258 rnp is ascribed to the 1,3-cyclohexadiene. An additional absorption at 242 rryl and a tailing into the visible region with a broad maximum at 360-370 r y is also observed. These spectral features are consistent with those reported for fulvene, the non-aromatic isomer of benzene.15 Blair and Bryce-Smith found fulvene in the photochemical irradiation of benzene in what appears to be the first direct conversion of an aromatic hydrocarbon to a non-aromatic hydrocarbon. l6 Fulvene co-distilled with benzene, but could be separated from benzene using the 100 ft. squalane column (Figure 3). Fulvene prepared by the method of Meuche gave the same retention time and spectral features.I7 Additional evidence for assignment of the fulvene peak included its disappearance from the chromatogram after the sample was refluxed with maleic anhydride (color disappears ) or exposure to a free radical catalyst. The Diels-Alder reaction product with maleic anhydride was isolated and hydrolyzed to give the adduct, 7-methylene-5-norbornene -2, 3-dicarboxylic acid. The melting point and infrared data for this adduct were identical with the sample prepared using fulvene synthesized from cyclopentadiene and formaldehyde. l2 The formation of the 1,3,5-hexatrienyl diradical has been suggested as an intermediate in the photochemical decomposition'' and the radiofrequency discharge12 of benzene. Material isolated in the photochemical excitation gav.e a W spectrum similar to 1,3,5-hexatriene, but displaced by 7.5 mp and, more disturbing, the investigators were able to separate the material from benzene by fractional distillation. No experimental evidence was given in the radiofrequency study. In our work, 1,3,5-hexatriene could not be detected (less than 100 ppm) in the benzene fraction using the squalane column. No spectral evidence was noted in the ultraviolet although the region of in- terest is complicated by the presence of 1,3-cyclohexadiene. l9 The unidentified peak in the chromatogram (Figure 3) gives a negative test for an acetylenic hydrogen (ammoniacal cuprous chloride solution) and does not disappear after the sample is subjected to free radical catalysis for several hours. Thus, the open chain, acetylenic isomers of benzene, hexa-I, 3-diene-5-yne. 1,4-hexadiyne, 1,s-hexadiyne and l.S-hexadien-3-yne do not appear to account for this peak. The possibility of valence isomers of benzene such as bicyclo (2.2.0) hexa-2, 5-diene, "Dewar benzene", were excluded based on the observation that the peak was stable to prolonged heating at looo. The valence isomers would be expected to convert to benzene under such conditions. 2o TABLE 2 (a) Product Distribution in Dscharged Benzene Fraction Product Yield % Benzene Exposed 1.3 -Cyclohexadiene 0.03 1.4 -Cyclohexadiene 0.09 Fulvene 0 01 Cyclohexene 0.01 Unidentified 0.02 (a) Quantitative data obtained by GLC using squalane column and appropriate calibration standards. I I li \ \
I f I I " I I - 447 ~. Figure 3 Analysis of Benzene Fraction Column I00 f t a 0020 In ID Support-coated open Tubular with Squalane Liquid Phase Temp 45': Isothermal Biphenyl Fraction - Silicone GumRubber Column ERM$L TO 300.C AT 6OVYIN , ISOTHERMAL X)O* ' 185.C ' 300 4YIN 45 SEC -. Figure 4 I
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)i 1 reesonably complete and accura
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3 inquire about the component of ve
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4 I I 5 To find (t2)av, we assume t
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\ vnich, it is noted can be negativ
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I 7 than or smaller than the second
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i I i I I I ) ) i L , I I . INT1:OD
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13 field per electron is and per co
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. 11. 5. CharRe-Transfer and Ion-Mo
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17 In the followin:: sections much
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above. With that EIN, an estimate o
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21 region in w!iich large, nighlv l
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i ’ understanding: 23 (a) Electro
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Obviously, the secondary ion must h
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27 (22) Franklin, J. L., Munson, M.
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Tables 1-6 present examples of rela
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Table 8 Some Ions Formed by Process
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33 velocity of the reacting partn r
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35 must be added to the Langevin cr
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37 In our laboratory a microwave di
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+ . 4 . r 39 as well as N in a cor0
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ION-MOIECULE REACTION RATES MEASUFI
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43 excitntion 2onditions so that th
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45 In 2 like manner Fig. 3, showing
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47 Absorption Spectra of Transient
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50 maximum fiela. In this manner, a
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52 3 % %- %- 5- a- 7 h W P H 0 L v)
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References I I . A.B.Callear, J.A.G
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._ . _-.. - , , . . ,. . The Pyrex
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58 0 0 0 VI J > I cv . u H a
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.... . 0 2 e I / m 0 H F4 : 1
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\ 0.9 0.8 0.7 06 0.5 0.4 0.3 0.2 01
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65 ' cause of the reduction in the
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INTRODUCTION I' Attachment of polar
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I 69 EXPERIMENTAL The mass spectrom
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+ Figure 1 Mixed water and methanol
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73 ' , radius might be expected bec
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75 Negative Ion Mass Spectra of Som
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A b 1 1 I H I I I FILAMEN T CONTINU
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79 for positive and negative ions,
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51 out to answer some of the questi
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93 INTERACTIONS OF EXCITED SPECIES
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L 4 I*C z 0'2 = a, a U x I m 4 m 0
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I L I, ; > > E Fig. 3 I50 200 150 1
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I 300 r 1 - 200 i io ;' a cn I I. 0
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where DISCUSSION OF XESULTS PERTAIN
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93 where the bar indicates values c
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'I i 'I 0 2. 4 6 8 2 [ N]* x' I 0-2
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Fig. 14 IO 8 6 4F [NO] x IO-" (mole
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for chemiluminescent excitation in
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101 Chemiluminescent Reactions of E
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103 All gases were taken directly f
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10; He: + N2 -. 2He + h': (8) whi!?
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description for both diffusion and
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B. Ions and Electrons I Consider a
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' 112 axial diffusion through the d
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the tube walls occurs continuously
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E2R M ' $6"
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1. 2. 3. 4. 5. 6. 7. 8. 9- 10. u. -
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120 . Dlschorge zone Reactor zone 1
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122 In radiation chemistry the cust
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124 4. chemistry seem limited essen
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126 Conversion of Mixtures into Mor
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Hydrazine Synthesis in A Silent dle
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{;I . - . .. . - .., . . .. _- .. .
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1 \ \ \ , \ , \ \ Pmer hnrity K.W.
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. I operating fact that the sloGe i
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_- of ' . 8. - 7 6, Residence Time
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135 Ionic Reactions in Corona Disch
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GAS OUT GAS IN i.ho QUADRUPOLE MASS
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- + ( ~ ~ + 0 H ) ~ O ~ ( H~o)~H+ +
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144 i I , , , , . + 1- u 3c w Inu c
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146 SYNTHESIS OF ORGANIC COIGhTDS B
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mi5 a- dz CI n I a I n +4 - 0 -I- k
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0 z cu I I I
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I- I - t d m a .rl Y x c, t-' d k
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, 155 This result is significant in
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Compound Bond he rgy Li I 82 UBr 10
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, ”..’ 3or 25 - 5 20 - s 3 w Y
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I 161 THE GLOW DISCHARGE DEPOSITION
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Fig. 1 Process Apparatus -__l.ll__
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v) t- at- InIo Io0 t-Q) loo lcua O
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This study is only an approximation
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Mole Reaction Material ratio time e
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\ i (4) Effect of System Pressure T
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173 Pressure. Since pressure is a c
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175 Table VI X-RAY DATA OF DEPOSIT
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177 Another source of weakness is t
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179 PLATING IN A CORONA DISCHARGE R
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\ 3 , ,\ 110 v 60 CPS MANOMETER . F
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I i , \ I i & a - P Fig. 3 Reaction
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\ \' C 0 .d * d .- C U d 0) c( 1) L
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I i I . Q) I, s w 0 v) Y 0 a w W a
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I (b) Polarized Light Fig. 6 Cross
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i m v) Y C i! u o) 23 a a- + 191 m
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i, d C .d c c W Q ) 0 0 L1Y 0 000 0
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i e 4 0 wcr -4 4 al 0 0 0 c) cr 13:
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\ E ‘ 1 TIME FOR RUN 13-1 14-1 -
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199 a red heat in this cell using d
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\ , t j \ I, v) 2 Y . C 0 u m .I C
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203 VAPOR PHASE FORMATION OF NONCRY
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BELL JAR STANC TO VACUUM SYSTEM U T
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207 of the boron oxide film, the fi
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i I, 4 I.( Y I- * 0 i f i 3 0.t I I
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211 The Reacticn 3f Oxygen with Car
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2 E, W t- a Z 9 I- a 2 X 0 I50 too
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'i' 100 50 IC 21 5 2.0 2.5 SURFACE
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I- z W 0 w a a 100 80 60 40 20 215
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s., Literature Cited Berkley, C. ,
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7 h \ F 221 600°C and 1 atmosphere
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223 e I'
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R L ' -1 9mm O.D. 5mm I.D. 45mm 0.D
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Figure 5.- Paschen's law curves. 2-
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\ '? I The water-free product gases
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N I + 0" ON i I + 0 u / 0 0 I 0 cu
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- 233 SOME PROBLEMS OF THE KINETICS
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.. . :. ,. .I , . i ? .. . , ... .
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237 Table 2 Experimental Variables
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239 Zhbie I Eerccnt Consumption of
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241 Discussion The systematic varia
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I \ 1 243 FORMATION OF HYDROCARBONS
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h z - a o m a 20 T IME, minutes . F
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I 1 I I I I 0 I 2 3 4 5 TIME, minut
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The next five coluws in table 1 sho
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\ .\ t 251 Given the existence of t
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I L 253 Epple, R. P. and C. M. Apt.
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1 ' Fig. 1 Schematic of flow discha
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5' . ' I 1 257 co, with excess H2,
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1 1 1 moo 1400 1300 c V' I IPOO I I
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i 25i The Dlssocfatior of ToIuere V
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L ! , c PRODUCTS FROM A 28 MC. DISC
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'\ J ?. , .. . : PRODUCT FORMATION
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'9 / I '\ "1 BENZYL CATION AND RADI
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a
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271 tube serve? as the high voltare
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273 ion (1L.). Zxcitei-ion by colli
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Apparatus and Procedure 275 EXPERIM
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. 277 6. A freshly prepared sam le
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observed. The polystyrene (10% solu
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i i (12) c (11) (14) I 281 LITERATU
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FLOW- METER I ADDITIVE SUPPLY * ,28
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285 TABLE 2 Effect of Haloqenated A
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ANALYTICAL RESULTS Some evidence wa
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DISCUSSION 289 The salient features
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? ~ MENBERSHIP IN THE DIVISION OF F
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292 flow of the reactant gas stream
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294 have suitable residence times i
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0 E < h( E l! d K c 0 .- Y 0 t u t
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298 yields of many chemical product
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- ;i Y . 15. Pressure lOmm 5 > 10-
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302 the best and in many practical
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GENERATION AND MEASUREMENT OF AUDIO
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. The transformer secondary and the
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Vaccum-Tube Amplifier The mobile co
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310 f = Power supply frequency in c
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FUFARCI! INSTITUTE OF TFYDLC UNIVER
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J # I / 4) I . . '8 r4 0 r( P
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317 i Cuencb svsten w.nnar;itus use
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epcrte? the noss~kil.itv of nroduct
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1' b t +
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323 ....... - . . . . . . . . . . .
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1 \ i I i , / / / 8 3 1 325 To205 +
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- .- - - . - - . . . - . 327 n + c
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' POWER PLASMA GAS l e , ' I ! I I
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331 f'ENI?AL PF'FCLCCFC Dernis, P.R
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i J 333 ; mosphere (as opposed to a
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; it raised the question, still &?z
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p .I V I .= - - HCN/C(CALC. WITH C
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1 1 339 atmospheric ressure and ach
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RESULTS 341 Composition Dependence
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0.09 0.08 0.07 9 0.06 2 U - .$ 0.05
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II \ to the Slot So that less of th
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i 4 2 HYDROCARBON-NITROGEN REACTION
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I 1 349 c M m ; a e, k M x
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1.0 I - a. I n TEMPERATURE - OK Fig
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353 the experimental results in the
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,) 355 The ceaswed conversion cf ni
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1 6 357 Freezing. 3jpotnesise thzf
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359 \ Frozen Compositior: Calcillat
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I 1 \ 361 -. ne reaction proceecis
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\ 36 3 ' h, I 26. H. Purnell, Gas C
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In experiments on the direct conver
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367 used as blnders, with different
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369 ' i 1. REFERENCES Berber, John
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Distribution and yield rates of pro
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. . I . I 370 . . . . ., . . .. . .
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4 372 090- > E w - m c N O - 0 z :
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A-Feed tank 6-Thermocracker GReceiv
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80 \ 0 70 60 e 40 a U VI 9 30 20 10
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COAL DEASH& AND HIGH-PURITY COKE Wa
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3Pn _. -. - L -J:,J.-;~~~L, ):as se
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S ~ l ~ o n~pg:ading r is the resul
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The range ~f temperatures and gener
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. .. 386 9 * - r. Y 2 .' d a f' r.
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.) .L m 388 I
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TABLE 4 390 DELAYED COKING OF DEASH
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, ! I- on '---
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394 The present method is to keep t
Page 400 and 401: 396 ‘c erperature, while the pres
Page 402 and 403: 2, '! ! Proximate Analysis, wt $ Mo
Page 404 and 405: 0 IS 0 14 LL 9 013 e \ 3 b- m *- 01
Page 406 and 407: 402 HYDROGEN CYANIDE PRODUCED FROM
Page 408 and 409: 404 Before startup, the system is p
Page 410 and 411: 4 OL. ' , I. . TesCs. With.Coals .o
Page 412 and 413: Table 3.- Product Gas Analyses and
Page 414 and 415: 410 BIBLIOGRAPHY 1. American Public
Page 416 and 417: Figure 2. Enclosure surrounding hyd
Page 418 and 419: 0 0 f v) C 0 u m I z 2 c 2 r d J w
Page 420 and 421: 0. E c .4 7 .. .c . I ( - Low tempe
Page 422 and 423: 418 cual. A mjor aa\;antage or' the
Page 424 and 425: 420 Ir ?Y ? ? 9 9 9 pc rod n o c o
Page 426 and 427: 422 Table 3. Room-texperature M'dss
Page 428 and 429: 424 state, depending on the strengt
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
Page 442 and 443: ?-!??? 0 mv, Uh\OhIe . . . . eirlrl
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 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 480 and 481: 476 Instead a hydrogen deficient fi
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
Page 494 and 495: Xississippi (Sample GS). Stock solu
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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For pure polynuclcar arom.i;ic hydr
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- '-'. . ' . . values are listed in
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500 (1;) Ten, T. 17.: a;1d,Dic;
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- ~ Resistivity Czlculation 2: 1 j:
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504 o ' C 0s 2 0 v x i 8 2 0 ! P -
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506 i
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d 601 L P LL
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I I I I I I I I m W N W N 0 (D ? 0
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514 was heated under nitrogen in a
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The line broadening at 79OK of the
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13. 14. 15. 16. 17. 18. 19. 20. 21.
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W L, Z 6 m (1: 0 6 d j o 2 ' 1 0.0
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Coals 522 Studies of the 1600 cm-l
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L in ole i c a c id - 0' Two sample
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526 Table 1.- Ultimate analyses of
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528 6. Friedel, R. A., and H. Retco
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egeneration. The system can be seen
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532 and can be expressed in terms o
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534 in the vapor increases with inc
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NH3 NH3 NH3 NH3 Pyridine Pyridine P
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Mole Ratio of Test No. Quinoline to
Page 544 and 545:
IXPROFJCTION D; M. Mason Institute
Page 546 and 547:
-4:c~rciiny to recent studies o ;i4
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544 Table 1. LIGHT EMISSION OF Y"TR
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emission in a few cases may be by d
Page 552 and 553:
LITERATUR2 CITED i. C. -. .' * il.
Page 554 and 555:
co, CH,,OR 1 - OTHER ADDITIVE FRITT
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FRIT 'TED CO, CH,.OR 4 ___ OTHER AD
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340 350 300 400 4 50 500 600 700 80
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0 554 WITH COOLING (PLATE AT 40°C)
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5 56 then t = to when e = 0 2) the
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5 58 The surface heat transfer coef
Page 566 and 567:
Discussion and Results 560 Three br
Page 568 and 569:
__- ._ 562 Table I THERMAL AND PHYS
Page 570:
ln 4 I 0 4J v \ 1.0 0.8 0.6 L - 0.4
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