chemical physics of discharges - Argonne National Laboratory

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helium 444 CORONA REACTOR SYSTEM Figure I condenser 400 mm threaded steel rod electrode 5/16"x 36" DETAIL OF CORONA REACTOR Figure 2 7740 Boroslltcote gloss dielectric, llmm OD thermocouple well ,1/4" copper tubing electrode and cooling coil Gap-4mm Internal volume -164 ml thermocouple well 24/40 ground gloas joinf 10 wet I \ \ '1 % I 1 F
Product 445 TABLE 1 Product Dstribution in the Corona Discharge of Benzene, 15KV Benzene insoluble polymer 0.7 Benzene soluble polymer (a) 6.0 Biphenyl 0.3 0-. m-, and p-Terphenyl Phenyl, benzyl substituted 0.1 cyclopentenes (b) 0.3 1,3-and 1,4-Cyclohexadiene 0.1 Fulvene 0.01 Acetylene 10 TOTAL 8.5 Yield-Per Cent Yield-Per Cent Radiofrequency@) Benzene Exposed of Product Mix Yield, Per Cent - 8.2 70.5 3.5 1.2 3.5 1.2 0.1 11.8 100.0 2.0 N.D. N.D. N.D. I,O 2.0 (f) 10.0 (a) Polymer fraction includes materials from 250 molecular weight and up. (b) Includes several phenyl and benzyl substituted cyclopentenes similar to biphenyl and o-terphenyl in vapor pressure. See discussion. (c) See reference No. 12. (d) N. D. -- not determined. (e) Benzene and toluene soluble polymer. (f) Acetylene l%, allene 1%. support-coated open tubular column with a squalane liquid phase and appropriate calibration standards (Figure 3). No significant change is noted in the cyclohexane content when compared with starting benzene. The increase in the methyl cyclopentane peak is ascribed 'to its higher vapor pressure thus affording some accumulation of this material in the benzene distillate and a concomitant depletion in the benzene feed stock. Cyclohexene is produced in very low yield, as expected, because of the degree of hydrogenation required during its short residence time in this single pass reactor. The reduction of benzene to the cyclohexadienes is interesting as 1,3-cyclohexadiene is therm'odynamically unstable with respect to benzene, cyclohexene and cyclohexane. l4 The synthesis of 1,3-cyclohexadiene under these conditions is analogous to the conversion of oxygen to ozone which also represents an energetically unfavorable process. The momentary energy input and the rapid removal of the activated species from the reaction zone affords this material. in low yield., As expected, the more stable 1,4-cyclohexadiene is produced in higher yeld (3/1). Additionally, 1,3-cyclohexadiene would be expected to polymerize at a rapid rate under these conditions. The thermodynamic instability of 1,3-cyclohexadiene is demonstrated by its gradual disappearance from the sample after a few days standing at room temperature. The yields of both the l,4-and 1,3-cyclohexadiene are somewhat higher than previously reported by Brown and Rippere. The yields reported by these workers after 24 hours exposure to a 15 KV'corona discharge in a counter-current hydrogen stream were 0.02 and 0.01 per cent respectively. The major variable in technique which likely accounts for this difference.in yields is the use of benzene vapor in our work, versus the hydrogenation of a thin liquid benzene film running down the annular dielectric sur- . face by Brown and Rippere.
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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 '---
Page 398 and 399: 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 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 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
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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
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IXPROFJCTION D; M. Mason Institute
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-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
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LITERATUR2 CITED i. C. -. .' * il.
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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
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Discussion and Results 560 Three br
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__- ._ 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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