chemical physics of discharges - Argonne National Laboratory

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238 The extensive literature of "active" nitrogen chemistry does not appear to I record any study of competition between organic substrates. This paper reports an investigation of consumption of hydrocarbon in the competition between an olefin, ethylene, and a paraffin, propane. Reaction probably went to completion under most, if not all, experimental conditions.* Consumption of hydrocarbon as a result of both primary attack by one or more components of "active" nitrogen and of secondary attack by reactive intermediates must be considered possible. Expcrimental Apparatus and metnods are described more completely elsewhere, 3'4. Active nitrogen was generated by electrodeless glow discharge supported by 2450MHz microwaves at a total pressure of 321 Torr. Transport rates were 230cm. sec.-l, 150p mole set.-' and 1.3t0.2~ mole set.-' for linear flow, N2 flow and N(4S) flow, respectively. !he latter was measured by nitric oxide "emission" titration.' Hydrocarbon substrate was introduced countercurrent3 into the active nitrogen stream at autogenous temperature (approx. 5G°C) acm. (.G87 sec.) downstream from the glow discharge. The gas stream psssed through liquid pitrogen traps 5Gcm. (.22,sec.) downstream from the substrate inlet. Amounts of recovered reactants were determined by gas chromato raphy on silica &el.4 Relative activities of 14Clabeled compounds were determined g by proportional counting of CO2 obtained by combustion of the gas chromatographically purified compounds in 02 over CuO at 450°. Propane and labeled ethylene were Matheson products. Cold ethylene was Phillips Research Grade. Data Table I smarizzs 2ercep.t consumption of ethylene consequent upon reaction of the pure substrate and three of its mixtures with propane with six different ratios of N(4S). Table I1 sunmarizes analogous data for propane. The data formixtures given in'the two Tables are derived from the same sets of experiments. Table I11 summarizes apparent relative specific rates of consumption, IlkCpH4/kC3H8tt. lhese ratios were calculated by means of e . 1, the expression which would be appropriate c ~ ~ ~ / ~ c logC(C2H4)J ~ H ~ I ~ (C,H4)tIq10gC(C,H8)o/(C~H8)tI ,(I) if the relative rates of consmption depended entirely on the bimolecular reaction of each of the substrates with the same reagent. Table IV summarizes molar radioactivities of recovered reactants or product ethane relative to that of reactant ethylene for the reaction of equimolar mixtures of 14C-labeled ethylene and ordinary propane.
239 Zhbie I Eerccnt Consumption of Ztcylene (Total Hydrocarbon) Average Percent Consumption (N)a Pure (C&4),/ (c3H8) e C2H4 nb 3.0 nb 110 n6 -0.33 nb 4 19 3 13 3 25' 10 - 2 24' 3 27 3 37+ 1c 51 6 1 3?+ 4 45 4 47X 16 56 9 21 3 45 2 59 1 - 730 2 112 7PX 3 87 3 93 10 90 7 , 116 9;o 2 - 93 7 84 3 a. b. a. b. Flow rate of N(4S) is l.3*O.& mole sec.-l throughout. Number of independent determinations averaged to give the tabulated figure. Table I1 Percent Consumption of Propane 41" 2 39 3 39 10 37 7 480 2 - 4 5 7 4 4 3 now rate of N(4S) is l.3?S10.2p mole set.-' throughout. Number of independent determinations averaged to give the tabulated figure. - 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
Page 187 and 188: I i I . Q) I, s w 0 v) Y 0 a w W a
Page 189 and 190: I (b) Polarized Light Fig. 6 Cross
Page 191 and 192: i m v) Y C i! u o) 23 a a- + 191 m
Page 193 and 194: i, d C .d c c W Q ) 0 0 L1Y 0 000 0
Page 195 and 196: i e 4 0 wcr -4 4 al 0 0 0 c) cr 13:
Page 197 and 198: \ E ‘ 1 TIME FOR RUN 13-1 14-1 -
Page 199 and 200: 199 a red heat in this cell using d
Page 201 and 202: \ , t j \ I, v) 2 Y . C 0 u m .I C
Page 203 and 204: 203 VAPOR PHASE FORMATION OF NONCRY
Page 205 and 206: BELL JAR STANC TO VACUUM SYSTEM U T
Page 207 and 208: 207 of the boron oxide film, the fi
Page 209 and 210: i I, 4 I.( Y I- * 0 i f i 3 0.t I I
Page 211 and 212: 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: 237 Table 2 Experimental Variables
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 and 264: L ! , c PRODUCTS FROM A 28 MC. DISC
Page 265 and 266: '\ J ?. , .. . : PRODUCT FORMATION
Page 267 and 268: '9 / I '\ "1 BENZYL CATION AND RADI
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Page 271 and 272: 271 tube serve? as the high voltare
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Page 275 and 276: Apparatus and Procedure 275 EXPERIM
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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
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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
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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
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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
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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
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476 Instead a hydrogen deficient fi
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i 478
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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
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. 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:
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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
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ln 4 I 0 4J v \ 1.0 0.8 0.6 L - 0.4
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