chemical physics of discharges - Argonne National Laboratory

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,) 355 The ceaswed conversion cf ni;rsgc.n xa-ied from 3 psrcent at the lowest stoichionetry cocsidered, CFU.+/Id2 = j.1, 'io I niaximum of 70 percent at a methanerick, stc' -b.~lo:.-.ctr;, -;.. CH4/32 = 2j. Phis higii vaiuc of iiitrogen fixation is considerablj 1:: excess of prs-,.ioGsly reported nitrogen conversion levels observed in therclai piasna reactions. Prcsswe variaiions had no significant effect. Qpi?al Product Conpcsition. Tabie I, below, presents the composition of the prcd..ct stream produced under typicel conditions. Teble I Typical Product Composition Heactor Pressure - 3S0 torr Net Power Input - 3.5 kw Feed Rate Feed Composition InpLt (std cc/sec) (mole-percent) 97.6 1.2 1.2 - Total 42.8 100.0 Composition (mole-percent 1 (mole-percent, &-free) 90.5 2.0a 1.0 0.3 0.2 trace - - 57 29 9 5 - - 190 .0 100 :;cte e: Ccnpositioiis dcterzi:ied fri:n gas chrcmatogra:r,i; - + 10 percent. As wzs seen in Fig. h, Table I shcws that about l2 percent of :!,e nitrogel1 fed at tbls stoici:icnetry vas corlverted to hydrogen cyanide. Ilinety-nine percent of the ,?!ethane fed was convertei :o the gaseoiis prccl.icts hydrogen and acetylene and also
.. to an unmeasured small qusntity of solid product which deposited on the wall. The minor disperity between the nitrogen and carbon material balances indicates the small fraction of material lost from the reaction zone to deposition on the reactor walls. Nitrile Reactions Products of Reaction. Sdl quantities of nitriles could be continuously fed to the argon plasma by using the modified injection arrangement (described in the previous section). cooled probe was analyzed with no change in the gas chromatograph. Essentially Mixed plasma which was quenched by withdrawal through the water- , complete conversion of the lower molecular weight compounds , acetonitrile , CH3CN, and acrylonitrile, C&CHCN, was observed. A minor amount (-10 percent) of propionitrile, CH3C+CN, was observed in the quenched gas stream, perhaps due to a bypassing of the plasma core. Each of the nitriles produced the same reaction products, a repeat of those produced in the methape-nitrogen study. High concentrations of HCN, Q+, I@, and N;! were observed dong with the argon diluent. A 't ' complete quantitative chemical analysis of these nitrile runs has not, as yet, been performed. 1 DISCUSSION OF RESULTS Variance in the Conversion Percentage. Considerable variance in the f'raction of nitrogen converted was observed among repetitions of runs with constant stoichiometry, net power input, and pressure. The data points plotted in Fig. 4 include the maximum observed conversion levels for each stoichiometry. Sources of error in the experimental procedure which could have scattered the data darn from maximum conversion were : 1. 2. 3. Improper adjustment of r.f. supply controls so 88 to mismatch the supply and t plasma impedance, perhaps generating plasma irregularities Minor air leaks which would add additional nitrogen to the plaema to altec the stoichiometry from preset values Deposition of carbon or hydrocarbon material on the reactor walls or, the reverse, significant vaporization of carbon from the walls, to alter the pre-$ , set stoichiometry. I i Thermochemical Equilibrium Predictions. As described in the "Plasma Composi- tion" section, above, a full range of composition calculations were made assuming thermochemical equilibrium. These calculations predicted that the plasma composi- ' tion within the r.f. coil- would be dominated by atomic species for the specific power input used in this study. Perhaps the following additional consideration Of these theoretical predictions can elucidate the processes occurring during rapid ~ quench. 'I i ', I \ I \ \ l, < , \ \, i I i \ i c
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)i 1 reesonably complete and accura
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3 inquire about the component of ve
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4 I I 5 To find (t2)av, we assume t
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\ vnich, it is noted can be negativ
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I 7 than or smaller than the second
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i I i I I I ) ) i L , I I . INT1:OD
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13 field per electron is and per co
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. 11. 5. CharRe-Transfer and Ion-Mo
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17 In the followin:: sections much
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above. With that EIN, an estimate o
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21 region in w!iich large, nighlv l
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i ’ understanding: 23 (a) Electro
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Obviously, the secondary ion must h
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27 (22) Franklin, J. L., Munson, M.
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Tables 1-6 present examples of rela
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Table 8 Some Ions Formed by Process
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33 velocity of the reacting partn r
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35 must be added to the Langevin cr
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37 In our laboratory a microwave di
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+ . 4 . r 39 as well as N in a cor0
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ION-MOIECULE REACTION RATES MEASUFI
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43 excitntion 2onditions so that th
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45 In 2 like manner Fig. 3, showing
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47 Absorption Spectra of Transient
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50 maximum fiela. In this manner, a
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52 3 % %- %- 5- a- 7 h W P H 0 L v)
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References I I . A.B.Callear, J.A.G
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._ . _-.. - , , . . ,. . The Pyrex
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58 0 0 0 VI J > I cv . u H a
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.... . 0 2 e I / m 0 H F4 : 1
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\ 0.9 0.8 0.7 06 0.5 0.4 0.3 0.2 01
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65 ' cause of the reduction in the
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INTRODUCTION I' Attachment of polar
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I 69 EXPERIMENTAL The mass spectrom
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+ Figure 1 Mixed water and methanol
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73 ' , radius might be expected bec
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75 Negative Ion Mass Spectra of Som
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A b 1 1 I H I I I FILAMEN T CONTINU
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79 for positive and negative ions,
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51 out to answer some of the questi
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93 INTERACTIONS OF EXCITED SPECIES
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L 4 I*C z 0'2 = a, a U x I m 4 m 0
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I L I, ; > > E Fig. 3 I50 200 150 1
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I 300 r 1 - 200 i io ;' a cn I I. 0
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where DISCUSSION OF XESULTS PERTAIN
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93 where the bar indicates values c
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'I i 'I 0 2. 4 6 8 2 [ N]* x' I 0-2
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Fig. 14 IO 8 6 4F [NO] x IO-" (mole
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for chemiluminescent excitation in
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101 Chemiluminescent Reactions of E
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103 All gases were taken directly f
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10; He: + N2 -. 2He + h': (8) whi!?
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description for both diffusion and
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B. Ions and Electrons I Consider a
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' 112 axial diffusion through the d
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the tube walls occurs continuously
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E2R M ' $6"
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1. 2. 3. 4. 5. 6. 7. 8. 9- 10. u. -
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120 . Dlschorge zone Reactor zone 1
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122 In radiation chemistry the cust
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124 4. chemistry seem limited essen
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126 Conversion of Mixtures into Mor
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Hydrazine Synthesis in A Silent dle
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{;I . - . .. . - .., . . .. _- .. .
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1 \ \ \ , \ , \ \ Pmer hnrity K.W.
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. I operating fact that the sloGe i
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_- of ' . 8. - 7 6, Residence Time
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135 Ionic Reactions in Corona Disch
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GAS OUT GAS IN i.ho QUADRUPOLE MASS
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- + ( ~ ~ + 0 H ) ~ O ~ ( H~o)~H+ +
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144 i I , , , , . + 1- u 3c w Inu c
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146 SYNTHESIS OF ORGANIC COIGhTDS B
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mi5 a- dz CI n I a I n +4 - 0 -I- k
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0 z cu I I I
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I- I - t d m a .rl Y x c, t-' d k
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, 155 This result is significant in
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Compound Bond he rgy Li I 82 UBr 10
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, ”..’ 3or 25 - 5 20 - s 3 w Y
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I 161 THE GLOW DISCHARGE DEPOSITION
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Fig. 1 Process Apparatus -__l.ll__
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v) t- at- InIo Io0 t-Q) loo lcua O
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This study is only an approximation
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Mole Reaction Material ratio time e
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\ i (4) Effect of System Pressure T
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173 Pressure. Since pressure is a c
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175 Table VI X-RAY DATA OF DEPOSIT
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177 Another source of weakness is t
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179 PLATING IN A CORONA DISCHARGE R
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\ 3 , ,\ 110 v 60 CPS MANOMETER . F
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I i , \ I i & a - P Fig. 3 Reaction
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\ \' C 0 .d * d .- C U d 0) c( 1) L
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I i I . Q) I, s w 0 v) Y 0 a w W a
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I (b) Polarized Light Fig. 6 Cross
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i m v) Y C i! u o) 23 a a- + 191 m
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i, d C .d c c W Q ) 0 0 L1Y 0 000 0
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i e 4 0 wcr -4 4 al 0 0 0 c) cr 13:
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\ E ‘ 1 TIME FOR RUN 13-1 14-1 -
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199 a red heat in this cell using d
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\ , t j \ I, v) 2 Y . C 0 u m .I C
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203 VAPOR PHASE FORMATION OF NONCRY
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BELL JAR STANC TO VACUUM SYSTEM U T
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207 of the boron oxide film, the fi
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i I, 4 I.( Y I- * 0 i f i 3 0.t I I
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211 The Reacticn 3f Oxygen with Car
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2 E, W t- a Z 9 I- a 2 X 0 I50 too
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'i' 100 50 IC 21 5 2.0 2.5 SURFACE
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I- z W 0 w a a 100 80 60 40 20 215
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s., Literature Cited Berkley, C. ,
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7 h \ F 221 600°C and 1 atmosphere
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223 e I'
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R L ' -1 9mm O.D. 5mm I.D. 45mm 0.D
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Figure 5.- Paschen's law curves. 2-
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\ '? I The water-free product gases
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N I + 0" ON i I + 0 u / 0 0 I 0 cu
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- 233 SOME PROBLEMS OF THE KINETICS
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.. . :. ,. .I , . i ? .. . , ... .
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237 Table 2 Experimental Variables
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239 Zhbie I Eerccnt Consumption of
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241 Discussion The systematic varia
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I \ 1 243 FORMATION OF HYDROCARBONS
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h z - a o m a 20 T IME, minutes . F
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I 1 I I I I 0 I 2 3 4 5 TIME, minut
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The next five coluws in table 1 sho
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\ .\ t 251 Given the existence of t
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I L 253 Epple, R. P. and C. M. Apt.
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1 ' Fig. 1 Schematic of flow discha
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5' . ' I 1 257 co, with excess H2,
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1 1 1 moo 1400 1300 c V' I IPOO I I
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i 25i The Dlssocfatior of ToIuere V
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L ! , c PRODUCTS FROM A 28 MC. DISC
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'\ J ?. , .. . : PRODUCT FORMATION
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'9 / I '\ "1 BENZYL CATION AND RADI
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a
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271 tube serve? as the high voltare
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273 ion (1L.). Zxcitei-ion by colli
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Apparatus and Procedure 275 EXPERIM
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. 277 6. A freshly prepared sam le
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observed. The polystyrene (10% solu
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i i (12) c (11) (14) I 281 LITERATU
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FLOW- METER I ADDITIVE SUPPLY * ,28
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285 TABLE 2 Effect of Haloqenated A
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ANALYTICAL RESULTS Some evidence wa
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DISCUSSION 289 The salient features
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? ~ MENBERSHIP IN THE DIVISION OF F
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292 flow of the reactant gas stream
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294 have suitable residence times i
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0 E < h( E l! d K c 0 .- Y 0 t u t
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298 yields of many chemical product
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- ;i Y . 15. Pressure lOmm 5 > 10-
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302 the best and in many practical
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
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 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
Page 384 and 385: 3Pn _. -. - L -J:,J.-;~~~L, ):as se
Page 386 and 387: S ~ l ~ o n~pg:ading r is the resul
Page 388 and 389: The range ~f temperatures and gener
Page 390 and 391: . .. 386 9 * - r. Y 2 .' d a f' r.
Page 392 and 393: .) .L m 388 I
Page 394 and 395: TABLE 4 390 DELAYED COKING OF DEASH
Page 396 and 397: , ! I- on '---
Page 398 and 399: 394 The present method is to keep t
Page 400 and 401: 396 ‘c erperature, while the pres
Page 402 and 403: 2, '! ! Proximate Analysis, wt $ Mo
Page 404 and 405: 0 IS 0 14 LL 9 013 e \ 3 b- m *- 01
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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
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340 350 300 400 4 50 500 600 700 80
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0 554 WITH COOLING (PLATE AT 40°C)
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5 56 then t = to when e = 0 2) the
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5 58 The surface heat transfer coef
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Discussion and Results 560 Three br
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__- ._ 562 Table I THERMAL AND PHYS
Page 570:
ln 4 I 0 4J v \ 1.0 0.8 0.6 L - 0.4
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