chemical physics of discharges - Argonne National Laboratory

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254 A summary of the products formed in the R. F. powered dfscharge is presented in figure L. It should Fe noted that these results am normalized to exclude recovered tolmne, non-oondensatle cases and polymeric materials which in combination accounted for 3 to 6 of the oripinal toluene vapor. The formation of Substantial amounts of dimer biaryls; bibenzyl, diphenylmethane and biphenyl is of prticulqr signifiance since, as noted above, the formation of only trace amounts of dlmer bisryls vas observed in the microwsve discharqe. Additional experiments -re condmted in which a helium carrier gas was uaed, and no substantial difference in the nature and amounts of products formed was noted. The chanp in product ratios, therefore, appears to reflect a change In mechanism vhich results frm the use of an R. F. povered discharee. The products formed jn this study, in particular the large amounts of biaqls, indicate that free radicals am the major intennediatee leadlne to the formation of products. The compounds fonned can be readily explained by the series of radical combination and hydrown sbstraotion reactions involving benzyl, phenyl and methyl radicals which are outlined in fieurn 5. It should be noted that minor, but definite amounts of the three xJrlene isomers -re fomed In the radiofrequancy discharee. The trace amounts of these isomers which were formed from the dlssociation of toluene raper in a microwave powered discharge hss previously been used aq an a ament against the presence of methyl radlcals in the mlcrowave discharp. (3f As is shovn in figure 6, however, it has been demonstrated that methyl radlcals mact vith toluene wp r with 3 hundred fold preference for the side chafn rathe- than the rinc positions.~4) It is, therefore, entirely co~slstent with the presence of methyl radicals In the R. F. disoharee that msctfon should take place predominantly vith the toluene slde chain to fonn ethylbenzene rather than with the rlng positiona to yield xylene isomers, although the formation of small amounts of qlene should be anticipated. Experiments in which speoifically labeled deuteriotoluene was passed through the R.F. disoharee afforded additional experimental data which supported the importance of radioal intermediates. The producte formed from the labeled toluene were collected, separated by chromatoyraphio techniques, and the distribution of the deuterium label determined by infrared and nuclear magnetic resonance epctroscopy and mass spctmmetry. The slde chain of the recovered ethylbenzene was found to be heavily deuterated. The partisl pass spectrum of the recovered ethylbenzene compared to the mass speotrm of un-deuterated raterfal is shevn in figure 7. The parent peak of the recovemd material is five mass units higher than the corresponding peak in the un-deuterated material, and deronstrates the incluslon of five deuterium atoms in the molecule. The bene pak of the unlabeled ethylbenzene molecule resulte from a P-15 cleawae correspondinp to the lam of a methyl group. In the spectrum of the reoovemd saterial, the base peak results from P-18 cleavaae and clearly demonotrataa the rethyl group of the side chain to be fully deuterated. This molecule preswmbly forms from the combination of C7H5D2 radical vith a CD3 radical. The distribution of the deuterium label in the benzyl frapent can be demonstrated by considerlnc the WR epectrm of the recovered bibenzyl. In figure 8, the 100 VC. proton rapetic ma30nance spectrum of un-deutered bibenzyl and that of the mcovered material ere compared. Ria important to note that the 5:2 ratio of aromatic to sethylene protons observed in the non-deutereted material vould also be observed with the prtjally deutemted nolecule if the deuterium label vere uniformly distrituted. The ematly reduced methylene proton peak in the spectrum of the remwred material, however, clearly demonetrates that the label remains localiced fn the e!de chain of the hnayl fragment, and is not distributed throughout the ring. This result is entfrely consistent vlth the presence of fme radical interlpsdiatee in the discharge slnce, as io show in fim 9, it has been demonstrated that the un=ioniced benzyl radical does not undergo any type of rearrangement vhkb t in the randomlzatlon of a label, such as the fornation of the tropyliw z%a?eg By contrast, the benzyl cation doee maergo an immediate arranqement to 1ltm lon, which vould result in uniform distribution of the deuterium labl. Since this is not observed, the benzyl catien can be ruled out as a tr?8
'\ J ?. , .. . : PRODUCT FORMATION REACTIONS Figure 5 REACTION OF METHYL RADtCALS WITH TRITIATED TOLUENE RELATIVE RATE CONSTANTS AT 85' 6- 0.76 m- 0.26 P- c Ha- I .oo 156 X.V. BEREZIN, et.a\., ZHUR. OBSCHE\ KH\W.> 3p,4093 (1960). C.A., a, 27153 b. Figure 6
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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
Page 101 and 102:
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
Page 213 and 214: 2 E, W t- a Z 9 I- a 2 X 0 I50 too
Page 215 and 216: 'i' 100 50 IC 21 5 2.0 2.5 SURFACE
Page 217 and 218: I- z W 0 w a a 100 80 60 40 20 215
Page 219 and 220: s., Literature Cited Berkley, C. ,
Page 221 and 222: 7 h \ F 221 600°C and 1 atmosphere
Page 223 and 224: 223 e I'
Page 225 and 226: R L ' -1 9mm O.D. 5mm I.D. 45mm 0.D
Page 227 and 228: Figure 5.- Paschen's law curves. 2-
Page 229 and 230: \ '? I The water-free product gases
Page 231 and 232: N I + 0" ON i I + 0 u / 0 0 I 0 cu
Page 233 and 234: - 233 SOME PROBLEMS OF THE KINETICS
Page 235 and 236: .. . :. ,. .I , . i ? .. . , ... .
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
Page 245 and 246: h z - a o m a 20 T IME, minutes . F
Page 247 and 248: I 1 I I I I 0 I 2 3 4 5 TIME, minut
Page 249 and 250: The next five coluws in table 1 sho
Page 251 and 252: \ .\ t 251 Given the existence of t
Page 253 and 254: I L 253 Epple, R. P. and C. M. Apt.
Page 255 and 256: 1 ' Fig. 1 Schematic of flow discha
Page 257 and 258: 5' . ' I 1 257 co, with excess H2,
Page 259 and 260: 1 1 1 moo 1400 1300 c V' I IPOO I I
Page 261 and 262: i 25i The Dlssocfatior of ToIuere V
Page 263: L ! , c PRODUCTS FROM A 28 MC. DISC
Page 267 and 268: '9 / I '\ "1 BENZYL CATION AND RADI
Page 269 and 270: a
Page 271 and 272: 271 tube serve? as the high voltare
Page 273 and 274: 273 ion (1L.). Zxcitei-ion by colli
Page 275 and 276: Apparatus and Procedure 275 EXPERIM
Page 277 and 278: . 277 6. A freshly prepared sam le
Page 279 and 280: observed. The polystyrene (10% solu
Page 281 and 282: i i (12) c (11) (14) I 281 LITERATU
Page 283 and 284: FLOW- METER I ADDITIVE SUPPLY * ,28
Page 285 and 286: 285 TABLE 2 Effect of Haloqenated A
Page 287 and 288: ANALYTICAL RESULTS Some evidence wa
Page 289 and 290: DISCUSSION 289 The salient features
Page 291 and 292: ? ~ MENBERSHIP IN THE DIVISION OF F
Page 293 and 294: 292 flow of the reactant gas stream
Page 295 and 296: 294 have suitable residence times i
Page 297 and 298: 0 E < h( E l! d K c 0 .- Y 0 t u t
Page 299 and 300: 298 yields of many chemical product
Page 301 and 302: - ;i Y . 15. Pressure lOmm 5 > 10-
Page 303 and 304: 302 the best and in many practical
Page 305 and 306: GENERATION AND MEASUREMENT OF AUDIO
Page 307 and 308: . The transformer secondary and the
Page 309 and 310: Vaccum-Tube Amplifier The mobile co
Page 311 and 312: 310 f = Power supply frequency in c
Page 313: 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
Page 372 and 373:
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
Page 396 and 397:
, ! I- on '---
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394 The present method is to keep t
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396 ‘c erperature, while the pres
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2, '! ! Proximate Analysis, wt $ Mo
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0 IS 0 14 LL 9 013 e \ 3 b- m *- 01
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402 HYDROGEN CYANIDE PRODUCED FROM
Page 408 and 409:
404 Before startup, the system is p
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4 OL. ' , I. . TesCs. With.Coals .o
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Table 3.- Product Gas Analyses and
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410 BIBLIOGRAPHY 1. American Public
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Figure 2. Enclosure surrounding hyd
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0 0 f v) C 0 u m I z 2 c 2 r d J w
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0. E c .4 7 .. .c . I ( - Low tempe
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418 cual. A mjor aa\;antage or' the
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420 Ir ?Y ? ? 9 9 9 pc rod n o c o
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422 Table 3. Room-texperature M'dss
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424 state, depending on the strengt
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Table 4. Room-?;ergerature isomer s
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I' 1.3 . /o 9 IO 9 6 a 425 F F 33 I
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Brooks J.D. and Sternhell S. (1957)
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(52) Gib3 T.C. and Greenwood N.N. (
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434 transducer vas then introduced
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436 yield is quite similar. The con
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?-!??? 0 mv, Uh\OhIe . . . . eirlrl
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4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 4
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442 CHEMICAL REACTIONS IN A CORONA
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helium 444 CORONA REACTOR SYSTEM Fi
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446 The ultraviolet spectrum. for t
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Biphenyl Fraction 448 The low molec
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LUd The actual structural definitio
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I I I I I In m 9 In 2 , I: r- In m
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’. 454 Mechanism I The available
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456 , , . The relatively low yield
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458 h/lethylacetylene, allene and b
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Introduction VAPOR PHASE DECOMPOSIT
Page 466 and 467:
462 more efficient hydrogenation. T
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464 place in parallel with fragment
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466 P rl 0, k 7 rnI rn al k a I hl
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458 TABLE I. COMPOSI'IION OF GASEOU
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REFERENCES 1. C. Hirayama and D. A.
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i 472 Reciprocal Arc Enthalpy ,-> F
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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
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482 TA5L,E 2. - Carbon number distr
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6. 7. a. 9. 484 Lawlor, D. L., and
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' I ' Sample No. 6 ' 12 IO 8 6 z 4
Page 492 and 493:
. 488 uiolecular weight of which ca
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Xississippi (Sample GS). Stock solu
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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:
Page 508 and 509:
504 o ' C 0s 2 0 v x i 8 2 0 ! P -
Page 510 and 511:
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
Page 518 and 519:
514 was heated under nitrogen in a
Page 520 and 521:
The line broadening at 79OK of the
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13. 14. 15. 16. 17. 18. 19. 20. 21.
Page 524 and 525:
W L, Z 6 m (1: 0 6 d j o 2 ' 1 0.0
Page 526 and 527:
Coals 522 Studies of the 1600 cm-l
Page 528 and 529:
L in ole i c a c id - 0' Two sample
Page 530 and 531:
526 Table 1.- Ultimate analyses of
Page 532 and 533:
528 6. Friedel, R. A., and H. Retco
Page 534 and 535:
egeneration. The system can be seen
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532 and can be expressed in terms o
Page 538 and 539:
534 in the vapor increases with inc
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NH3 NH3 NH3 NH3 Pyridine Pyridine P
Page 542 and 543:
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
Page 548 and 549:
544 Table 1. LIGHT EMISSION OF Y"TR
Page 550 and 551:
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
Page 556 and 557:
FRIT 'TED CO, CH,.OR 4 ___ OTHER AD
Page 558 and 559:
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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