chemical physics of discharges - Argonne National Laboratory

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i J 333 ; mosphere (as opposed to about 1 torr) and at an average temperature tventy times as high on the absolute scale as room temperature, vhere the bulk of active nitrogen experiments have been performed. Finally, in the plasma jet the carbonaceous species reacting is evidentially not methane. That is, the products other than HCN are acetylene and higher acetylenes vith various degrees of saturation. These are the same products that would form if the jet vere, say, argon. It has b been shown elsevhere(7) that the precursors for these products form rapidly compared I / (7) M. P. Freeman and J. F. Skrivau, A.1.Ch.E. (Am. Inst. Chem. Engrs.) J., g, 450 (1962). I > ,' to the time for mixing of the methane vith the jet. I ,' There is no question that the plasma Jet provides a difficult environment in which to do "good vork" in the usual sense. The enonnous temperature gradients and consequent inhomogeneities are generally thought of as being a sort of physical chemical bar sinister. On the other hand, perhaps because of their extreme magnitude, the i effects due to the temperature gradients are found to be sufficiently reproducible to allow systematic investigation of the jet as a whole, vhich in its hotter parts re- ' presents in a steady state flow situation a chemically unique environment found only / in high intensity arc devices. As ccsnpensation for tackling this difficult environment, the investigator need not vork with trace quantities, but instead vith partial pressures and relative conversions at least tvo orders of magnitude higher than those I encountered in active nitrogen research. ) The vork reported here represents a systematic continuation of a study performed some t ime ago.(8) The procedure followed then 8s nov is to add methane through an an- I * (8) M. P. Freeman, "The Nature and Quantitative Determination of the Reactive $' 5 / ' Species In A Nitrogen Plasma Jet," presented at the 147th Natl. Meeting, Amer. Chem. SOC., April 5-10, 1964, Philadelphia, Penn. 4 calibrated flov rate and a measured heat flow). It has been shovn that under these \ condition xing is very rapid, as is the drop in temperature deflncd from average nular slot to a confined nitrogen jet of precisely deflned average enthalpy (i.e., a enthalpy. 17Y Aiter about one millisecond the resulting flow of high temperature species t/ is further chilled by the entrainment of cold product gas (the fastest of several \ quench methods investigated on the basis of its efficacy in quenching the ammonia decomposition reaction)(T) and the flov of HCN in the product gas is chemically de- f termined. Except as noted, the data are taken at 350 2 20 torr chamber pressure as 1 this pressure is found to reduce the formation of solid product to an insigniflcant ) level. As the methane is added at various flw rates the corresponding rate of production of HCN is noted. { ' Just 88 in e.g., Winkler's work vith active nitrogen, a plateau is observed vhich seem to indicate that some active species is indeed being titrated (Figure 1). Of utmost interest in'the older study vas the provocatively simple dependence of the plateau level on jet power level (Figure 2). Because this may in turn be shown to correlate with the rate of production of ions in the arc !
335 I I I I I I I I 1 1 0.12 - - - - y 0.08 - 1. Y .t - - 0 0 0 -O- - I I I I I I 0 0.2 0.4 %CH4/G 0.6 0.8 1 .O ?
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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
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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
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
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 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
Page 346 and 347: II \ to the Slot So that less of th
Page 348 and 349: i 4 2 HYDROCARBON-NITROGEN REACTION
Page 350 and 351: I 1 349 c M m ; a e, k M x
Page 352 and 353: 1.0 I - a. I n TEMPERATURE - OK Fig
Page 354 and 355: 353 the experimental results in the
Page 356 and 357: ,) 355 The ceaswed conversion cf ni
Page 358 and 359: 1 6 357 Freezing. 3jpotnesise thzf
Page 360 and 361: 359 \ Frozen Compositior: Calcillat
Page 362 and 363: I 1 \ 361 -. ne reaction proceecis
Page 364 and 365: \ 36 3 ' h, I 26. H. Purnell, Gas C
Page 366 and 367: In experiments on the direct conver
Page 368 and 369: 367 used as blnders, with different
Page 370 and 371: 369 ' i 1. REFERENCES Berber, John
Page 372 and 373: Distribution and yield rates of pro
Page 374 and 375: . . I . I 370 . . . . ., . . .. . .
Page 376 and 377: 4 372 090- > E w - m c N O - 0 z :
Page 378 and 379: A-Feed tank 6-Thermocracker GReceiv
Page 380 and 381: 80 \ 0 70 60 e 40 a U VI 9 30 20 10
Page 382 and 383: 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
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 -
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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
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
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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
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
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emission in a few cases may be by d
Page 552 and 553:
LITERATUR2 CITED i. C. -. .' * il.
Page 554 and 555:
co, CH,,OR 1 - OTHER ADDITIVE FRITT
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FRIT 'TED CO, CH,.OR 4 ___ OTHER AD
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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