chemical physics of discharges - Argonne National Laboratory

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94 deactivation. Hence, some species is produced in the discharge in addition to atomic nitrogen which is capable of rapidly deactivating N2(A3X$). This species persists for times long compared to T . '1 The results of these experiments indicate that 3everal unusual processes are occurring: (1) a high-order process destroying N2(A 1:) which involves atomic nitrogen; (2) a process utilizing species, created in a discharge other than atomic nigrogen, which removes N2(A3X$); and (3) a process involving atomic nitrogen and another species generated in the discharge which produces hi2 (A31i)'. These processes . are in addition to electron excitation and radiative destruction of N2(A3C$). Several eossible reaction schemes can be constructed which are consistent with our observations. However, without positive identification of all the species created in the discharge and the istermediaries necessarily involved in high-order processes, these reaction schemes are speculative. It seems best to postpone discussions of these until more experimental information is available. EXPERIMENTAL REACTIONS INVOLVING NO For experiments on the effect of NO on N2(A 3 Zh), three photomultipliers were installed downstream from the RF excitation bulb to observe chemiluminescence. One photomultiplier had an interference filter centered on the strong bands of N2 at 5800 A, a second (called the yellow detector) observed radiation at wave lengths longer than 5200 A, and a third (called the ultraviolet detector) observed emission between 3800 A and the pyrex cutoff. The first two photomultipliers are sensitive to the N2 first positive bands excited by recombination of atomic nitrogen and to the NO2 continuum excited by reactions of 0 with NO, while the ultraviolet photomultiplier is mainly sensitive to the NO, 6 bands excited in the association of atomic nitrogen and oxygen. These photomultipliers were calibrated by generating nitrogen atoms in the microwave discharge and titrating them with NO. It should be remembered that all emission observed in the downstream bulb is of chemiluminescent origin. RESULTS Figure 10 shows the decay rate when the exciting discharge is turned off from the 0,3 NO y band, and the 0,5 Vegard-Kaplan band as a function of atomic nitrogen added by the upstream microwave discharge. Figures 11 and 12 show the intensity of the 0,5 Vegard-Kaplan band, the 0,3 NO y band and the 0,6 NO 6 band in the discharge bulb as a function of the NO concentration that would have existed in the stream if no destruction of NO occurred. Also shown are the responses of the yellow photomultipler and the ultraviolet photomultiplier, both of which are located at the downstream bulb. Spectrometer scans of the discharge without adding NO and on the plateau of Figs. 11 and 12 are shown in Fig. 1. Figure 13 is a plot of the area intensity ratio of 0,3 NO y/0,5 Vegard-Kaplan bands as a function of NO added beyond the null and as a function of the relative response of the yellow phototube to the NO2 continuum. Figure 14 is similar to Fig- 13 but involves the 1,lO Vegard-Kaplan band and the 3,O NO y band. DISCUSSION The simultaneous decay of N2(A 3 Xu) + and Iys the intensity of the NO y bands, suggests that NO is excited in the process5 NO(X 2 ll) + N2(A32:) -f NO(A22+) + N2(X12) . 1 , i
'I i 'I 0 2. 4 6 8 2 [ N]* x' I 0-26 (otorns/crn3) " IO TB-- 45 2 5 22- 37 Fig. 10 The dependence of the rate of decay of N2(A 3 xu) + and NO(A 24- I ) as a function of the square of the atomic nitrogen concentration. IO0 80 GO 40 20 0 0 IO 20 30 40 50 '60 70 80 [NO] x IO-" (molecules/cm3) TO-452522-39 11 The dependence of emission intensities on NO concentration: a- the NO B bands, A - the N2 first positive bands, 0 - the NO2 continuum -- all excited in the downstream observation bulb; 0 - the 0,3 NO y band, A - the 0,6 NO 6 band, and 0- the 0,s Vegard-Kaplan band excited in the Tessla discharge bulb *
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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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Page 45 and 46: 45 In 2 like manner Fig. 3, showing
Page 47: 47 Absorption Spectra of Transient
Page 50 and 51: 50 maximum fiela. In this manner, a
Page 52 and 53: 52 3 % %- %- 5- a- 7 h W P H 0 L v)
Page 54 and 55: References I I . A.B.Callear, J.A.G
Page 56 and 57: ._ . _-.. - , , . . ,. . The Pyrex
Page 58 and 59: 58 0 0 0 VI J > I cv . u H a
Page 60: .... . 0 2 e I / m 0 H F4 : 1
Page 63 and 64: \ 0.9 0.8 0.7 06 0.5 0.4 0.3 0.2 01
Page 65 and 66: 65 ' cause of the reduction in the
Page 67 and 68: INTRODUCTION I' Attachment of polar
Page 69 and 70: I 69 EXPERIMENTAL The mass spectrom
Page 71 and 72: + Figure 1 Mixed water and methanol
Page 73 and 74: 73 ' , radius might be expected bec
Page 75 and 76: 75 Negative Ion Mass Spectra of Som
Page 77 and 78: A b 1 1 I H I I I FILAMEN T CONTINU
Page 79 and 80: 79 for positive and negative ions,
Page 81 and 82: 51 out to answer some of the questi
Page 83 and 84: 93 INTERACTIONS OF EXCITED SPECIES
Page 85 and 86: L 4 I*C z 0'2 = a, a U x I m 4 m 0
Page 87 and 88: I L I, ; > > E Fig. 3 I50 200 150 1
Page 89 and 90: I 300 r 1 - 200 i io ;' a cn I I. 0
Page 91 and 92: where DISCUSSION OF XESULTS PERTAIN
Page 93: 93 where the bar indicates values c
Page 97 and 98: Fig. 14 IO 8 6 4F [NO] x IO-" (mole
Page 99 and 100: for chemiluminescent excitation in
Page 101 and 102: 101 Chemiluminescent Reactions of E
Page 103 and 104: 103 All gases were taken directly f
Page 106 and 107: 10; He: + N2 -. 2He + h': (8) whi!?
Page 108 and 109: description for both diffusion and
Page 110 and 111: B. Ions and Electrons I Consider a
Page 112 and 113: ' 112 axial diffusion through the d
Page 114 and 115: the tube walls occurs continuously
Page 116 and 117: E2R M ' $6"
Page 118 and 119: 1. 2. 3. 4. 5. 6. 7. 8. 9- 10. u. -
Page 120 and 121: 120 . Dlschorge zone Reactor zone 1
Page 122 and 123: 122 In radiation chemistry the cust
Page 124 and 125: 124 4. chemistry seem limited essen
Page 126 and 127: 126 Conversion of Mixtures into Mor
Page 128 and 129: Hydrazine Synthesis in A Silent dle
Page 130 and 131: {;I . - . .. . - .., . . .. _- .. .
Page 132 and 133: 1 \ \ \ , \ , \ \ Pmer hnrity K.W.
Page 134 and 135: . I operating fact that the sloGe i
Page 136 and 137: _- of ' . 8. - 7 6, Residence Time
Page 138 and 139: 135 Ionic Reactions in Corona Disch
Page 140 and 141: GAS OUT GAS IN i.ho QUADRUPOLE MASS
Page 142 and 143: - + ( ~ ~ + 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
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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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