chemical physics of discharges - Argonne National Laboratory

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160 change in field through the corona, but very little change over the remaining distance to the opposing electrode. Most studies of corona discharges have been in inert gas systems, and have been generated at a point electrode. This study has been directed toivard the tletcrmination of the feasibility for depositing :1 coating, c.g., boron, on a suitablc substrate in :I corona discharge. A further object has becn to determine some of the critical pnramctcrs and a possible indication of the mechanism and characteristics of this technique for coating the substrate material. ; EXPERIMENTAL WORK A schematic diagram of the system used in this study is indicated in Fig. 1. The system pressure was controlled with a Cartesian Manostat GA (Manostat Corporation) and a Welch mechanical pump Model 1402 (W. M. Welch Manufacturing Company). The discharge was initiated and sustained with a 7,000/12,000 V Jefferson luminous tube outdoor-type transformer (Jefferson Electric Company) connected to GO-cps 110-V power source through a Variac variable transformer. To dcterrnine the effect of alternating and direct current, an RCA CR 212 half-wave recti- fier \vas added to the circuit. At the same time a resistance bridge, a current measuring rcsistor, and an ammeter were added to the circuit. A schematic of the circuit is presented in Fig. 2. The resistance bridge consisted of six 2-W 2-megohm resistors (R2) and one 2-\V 1,000-ohm resistor .(R1), all in series; the total voltage being 11,775 times the voltage across the 1,000-ohm resistor. The current measuring resistor ,was a 2-W 10.075-ohm resistor. The voltage measurements were made with a Hewlett-Packard Model 130B oscilloscope, and alternating current measurements were made with a Simpson Model 378 milliammeter. The reactants utilized in this study were hydrogen, helium, or argon, and boron tribromide. The hydrogen was passed through a ffDe-oxo'7 unit (Engelhard), through a drying column of magnesium perchlorate, and then through a flowmeter. After the flowmeter, the hydrogen was split into two streams, one of which was bubbled through the boron tribromide, and then recombined into one stream before entering the reaction chamber or cell. The temperature of the bubbler, and of the cell, was controlled by wrapping each (and the associated gas lines) with heating tape and controlling the power input with a Variac variable transformer. The system was maintained at or below atmospheric pressure for this study, with most of the data being obtained at 2 to 3 in. of mercury below atmospheric pressure. Tungsten wire was chosen as the substrate material, This wire was cleaned by passing it successively through a train consisting of concentrated nitric acid, a distilled water rinse, and an acetone rinse. Using the hydrogen-boron tribromide reactant system and 60-cps alternating current to develop n corona, approximately a dozen cell designs were tried. The cell design which 1 appears to be the most satisfactory is pictured in Fig. 3. This cell consists of a 2-in.long pyrex glass tube with a neoprene O-ring inside each end and wrapped with eight turns of 3-mil tungsten wire along the tube length such that the wire is parallel and concentric to the axis of the tube. The wire is 0.9 cm from the axis. This assembly is then inserted in a 5-in.-long pyrex glass tube 1.5-in. in diameter and supported such that the tubes are concentric. A tungsten wire lead is then extended out of the tube, and neoprene rubber stoppers inserted in each end. Each stopper has a capillary tube through its center such that there are approximately 3 in. between the capillaries, and the filament enters and leaves the cell through these capillaries. The reactants also enter (and leave) the cell i! through the stoppers. I 4 1 , I
\ 3 , ,\ 110 v 60 CPS MANOMETER . Fig. 1 Schematic of System Utilized for Plating in a Corona Discharge 7 300 TO 15 000 V TRANSFORMER VARIAC MILLIAMMETER Fig. 2 Schematic of Power Input and Measuring Circuit Used With the Corona I' Discharge Plating Apparatus i I I
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)i 1 reesonably complete and accura
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3 inquire about the component of ve
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4 I I 5 To find (t2)av, we assume t
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\ vnich, it is noted can be negativ
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I 7 than or smaller than the second
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i I i I I I ) ) i L , I I . INT1:OD
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13 field per electron is and per co
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. 11. 5. CharRe-Transfer and Ion-Mo
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17 In the followin:: sections much
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above. With that EIN, an estimate o
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21 region in w!iich large, nighlv l
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i ’ understanding: 23 (a) Electro
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Obviously, the secondary ion must h
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27 (22) Franklin, J. L., Munson, M.
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Tables 1-6 present examples of rela
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Table 8 Some Ions Formed by Process
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33 velocity of the reacting partn r
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35 must be added to the Langevin cr
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37 In our laboratory a microwave di
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+ . 4 . r 39 as well as N in a cor0
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ION-MOIECULE REACTION RATES MEASUFI
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43 excitntion 2onditions so that th
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45 In 2 like manner Fig. 3, showing
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47 Absorption Spectra of Transient
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50 maximum fiela. In this manner, a
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52 3 % %- %- 5- a- 7 h W P H 0 L v)
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References I I . A.B.Callear, J.A.G
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._ . _-.. - , , . . ,. . The Pyrex
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58 0 0 0 VI J > I cv . u H a
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.... . 0 2 e I / m 0 H F4 : 1
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\ 0.9 0.8 0.7 06 0.5 0.4 0.3 0.2 01
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65 ' cause of the reduction in the
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INTRODUCTION I' Attachment of polar
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I 69 EXPERIMENTAL The mass spectrom
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+ Figure 1 Mixed water and methanol
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73 ' , radius might be expected bec
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75 Negative Ion Mass Spectra of Som
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A b 1 1 I H I I I FILAMEN T CONTINU
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79 for positive and negative ions,
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51 out to answer some of the questi
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93 INTERACTIONS OF EXCITED SPECIES
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L 4 I*C z 0'2 = a, a U x I m 4 m 0
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I L I, ; > > E Fig. 3 I50 200 150 1
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I 300 r 1 - 200 i io ;' a cn I I. 0
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where DISCUSSION OF XESULTS PERTAIN
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93 where the bar indicates values c
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'I i 'I 0 2. 4 6 8 2 [ N]* x' I 0-2
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Fig. 14 IO 8 6 4F [NO] x IO-" (mole
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for chemiluminescent excitation in
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101 Chemiluminescent Reactions of E
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103 All gases were taken directly f
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10; He: + N2 -. 2He + h': (8) whi!?
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description for both diffusion and
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B. Ions and Electrons I Consider a
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' 112 axial diffusion through the d
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the tube walls occurs continuously
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E2R M ' $6"
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1. 2. 3. 4. 5. 6. 7. 8. 9- 10. u. -
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120 . Dlschorge zone Reactor zone 1
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122 In radiation chemistry the cust
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124 4. chemistry seem limited essen
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126 Conversion of Mixtures into Mor
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Hydrazine Synthesis in A Silent dle
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+ +
Page 144 and 145: 144 i I , , , , . + 1- u 3c w Inu c
Page 146 and 147: 146 SYNTHESIS OF ORGANIC COIGhTDS B
Page 148 and 149: mi5 a- dz CI n I a I n +4 - 0 -I- k
Page 150 and 151: 0 z cu I I I
Page 152: I- I - t d m a .rl Y x c, t-' d k
Page 155 and 156: , 155 This result is significant in
Page 157 and 158: Compound Bond he rgy Li I 82 UBr 10
Page 159 and 160: , ”..’ 3or 25 - 5 20 - s 3 w Y
Page 161 and 162: I 161 THE GLOW DISCHARGE DEPOSITION
Page 163 and 164: Fig. 1 Process Apparatus -__l.ll__
Page 165 and 166: v) t- at- InIo Io0 t-Q) loo lcua O
Page 167 and 168: This study is only an approximation
Page 169 and 170: Mole Reaction Material ratio time e
Page 171 and 172: \ i (4) Effect of System Pressure T
Page 173 and 174: 173 Pressure. Since pressure is a c
Page 175 and 176: 175 Table VI X-RAY DATA OF DEPOSIT
Page 177 and 178: 177 Another source of weakness is t
Page 179: 179 PLATING IN A CORONA DISCHARGE R
Page 183 and 184: I i , \ I i & a - P Fig. 3 Reaction
Page 185 and 186: \ \' C 0 .d * d .- C U d 0) c( 1) L
Page 187 and 188: I i I . Q) I, s w 0 v) Y 0 a w W a
Page 189 and 190: I (b) Polarized Light Fig. 6 Cross
Page 191 and 192: i m v) Y C i! u o) 23 a a- + 191 m
Page 193 and 194: i, d C .d c c W Q ) 0 0 L1Y 0 000 0
Page 195 and 196: i e 4 0 wcr -4 4 al 0 0 0 c) cr 13:
Page 197 and 198: \ E ‘ 1 TIME FOR RUN 13-1 14-1 -
Page 199 and 200: 199 a red heat in this cell using d
Page 201 and 202: \ , t j \ I, v) 2 Y . C 0 u m .I C
Page 203 and 204: 203 VAPOR PHASE FORMATION OF NONCRY
Page 205 and 206: BELL JAR STANC TO VACUUM SYSTEM U T
Page 207 and 208: 207 of the boron oxide film, the fi
Page 209 and 210: i I, 4 I.( Y I- * 0 i f i 3 0.t I I
Page 211 and 212: 211 The Reacticn 3f Oxygen with Car
Page 213 and 214: 2 E, W t- a Z 9 I- a 2 X 0 I50 too
Page 215 and 216: 'i' 100 50 IC 21 5 2.0 2.5 SURFACE
Page 217 and 218: I- z W 0 w a a 100 80 60 40 20 215
Page 219 and 220: s., Literature Cited Berkley, C. ,
Page 221 and 222: 7 h \ F 221 600°C and 1 atmosphere
Page 223 and 224: 223 e I'
Page 225 and 226: R L ' -1 9mm O.D. 5mm I.D. 45mm 0.D
Page 227 and 228: Figure 5.- Paschen's law curves. 2-
Page 229 and 230: \ '? I The water-free product gases
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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
Page 570:
ln 4 I 0 4J v \ 1.0 0.8 0.6 L - 0.4
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