chemical physics of discharges - Argonne National Laboratory

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295 '' that they can be sustained at higher pressures but on the other hand the detailed ,t economics still require'evaluation. The crossed discharge arrangement shown in Figure 2b comprises a low frequency discharge at right angles to one of high frequency. The discharge zone itself is said to be characterised by a low energy density and to result in unexpectedly high activation of the reactants and relatively high yields of the reaction products (3 ). These claims ha$-e not however been confirmed by recent work in these j laboratories in which methane was subjected to a crossed discharge at 31 mm.Hg pressure. The reactor consisted of a 15 mm. internal diameter glass: tube fitted i/ with two pairs of 3 mm.diameter stainless steel electrodes arranged at right angles. The percentage decomposition of methane was observed using a 0.91 Mc/s high frequency discharge, a 50 c/s low frequency discharge and combinations of high 1. and low frequency discharges simultaneously. Figure 4 shows some typical data plotted in the form'$ methane decomposed versus $ H.F. power for a series of runs at constant total power. The methane flowrate was constant throughout at 93 cc/ ' minute,at N.T.P. These results confirm the general trend whereby an increase in disch,arge power is accompanied by an increase in the percentage decomposition of the methane but on the other hand do not substantiate the claim made for the higher activating effect of the crossed discharge. Had this been the case, the curves shown in Figure 4 would have exhibited maxima whereas, in fact, the observed methane decomposition at constant total power increased steadily with increasing percentage pf H.F. power. In this particular case, there is therefore no advantage in the use of crossed discharges and the characteristics claimed by Cotton still lemain to be confirmed . - 4.0 Product Selectivity and Residence Time Considerations. In the simple plug flow reactor, the conversion (x) obtained is related to the residence time (f) by the expression: . . "where U, and r are the molal volume of the reacting mixture and the reaction rate respectively. If the reaction is one which can only take place under the influence i of an electrical discharge, then the residence time refers to the time spent by 1 the reactants in the discharge zone itself. If however subsequent reactions involv- ,;ng the primary reaction products are possible outside the discharge zone, these I $1. will usually proceed at a different rate and must be taken into account separately in analysing the overall performance of the reactor system. \ If the reaction rate (r) could be written in terms of the concentractions of the reactants and a rate constant (k) which in turn was dependent upon the discharge characteristics, then in principle it would be possible,to integrate the above 'I expression for any set of discharge conditions and compute the residence time for ! any desired con--ersion. In practice however this is seldom possible because the functional relationship between the reaction rate and the discharge characteristics '~ Dishcarge reactions are frequently complicated by reason of the interactions ) between the atomic, molecular, ionic and free radical species present. Moreover because of the wide range of species present, reactions are rarely simple in the sense that only one primary reaction product is produced. Competing parallel, consecutive and degradation reactions are often present, the net result of which is to produce a wide spectrum of reaction products. One of the key problems at the present time therefore is how to design reactors in which unwanted side reactions are reduced to a minimum. There is no clear-cut anawer to this p'roblem as yet, but an examination of some of the more elementary types of reactions such as those listed in Table I indicates a promising method,of approach.
0 E < h( E l! d K c 0 .- Y 0 t u t loo Po 300 100 Elrctron Energy, V Fig. 3. Typical Cross-Scction versus Electron Biergy Curves. High Frequency Power z. Fie.4. Effect of a Crossed Discharge on % Metha*$ l’)nro-ipnnition.
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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
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
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: 294 have suitable residence times i
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
Page 316 and 317: J # I / 4) I . . '8 r4 0 r( P
Page 318 and 319: 317 i Cuencb svsten w.nnar;itus use
Page 320 and 321: epcrte? the noss~kil.itv of nroduct
Page 322 and 323: 1' b t +
Page 324 and 325: 323 ....... - . . . . . . . . . . .
Page 326 and 327: 1 \ i I i , / / / 8 3 1 325 To205 +
Page 328 and 329: - .- - - . - - . . . - . 327 n + c
Page 330 and 331: ' POWER PLASMA GAS l e , ' I ! I I
Page 332 and 333: 331 f'ENI?AL PF'FCLCCFC Dernis, P.R
Page 334 and 335: i J 333 ; mosphere (as opposed to a
Page 336 and 337: ; it raised the question, still &?z
Page 338 and 339: p .I V I .= - - HCN/C(CALC. WITH C
Page 340 and 341: 1 1 339 atmospheric ressure and ach
Page 342 and 343: RESULTS 341 Composition Dependence
Page 344 and 345: 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
Page 544 and 545:
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
Page 552 and 553:
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
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
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Discussion and Results 560 Three br
Page 568 and 569:
__- ._ 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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