chemical physics of discharges - Argonne National Laboratory

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1. 2. 3. 4. 5. 6. 7. 8. 9- 10. u. - 12. 13. 14. 15 * 16. 17 * 18. 19. 20. 21. 22. 23. 24. 25 * 26. 27 28. 29. 30. 118 REFERENCES Whittle, E., DOWS, D. A., and Pimentel, G.C., J. Chem. Phys. 22, 1943 (1954). Norman, I., and Porter, G., Nature 174, 508 (1954). Pimentel, G. C., in Fdnnation and Trapping of Free Radicals, (Academic Press, New York, 1960), p. 69. I Rice, F. J., and Freamo, M. J., J. Am. Chem. SOC. 73, 5529 (1951). Rice, F. J., and Freamo, M. J., J. Am. Chem. SOC. 15, 548 (1953). Goldenberg, H. M., Kleppner, D., and Ramsey, N. F., Phys. Rev. a, 530 (1961). Berg, H. C., and Kleppner, D,, Rev. Sci. Instr. z, 248 (1962). Shaw, T. M., in Formation and Trapping of Free Radicals, (Academic Press, New York, 1960), p. 47. Dickens, P. G., Linnett, J, W., and Palczewska, W., J. Catalysis &, 140 (1965). Evenson, K. M., and Burch, D. S., J. Chem. Phys. 9, 2450 (1966). Fehsenfeld, F. C., Schmeltekopf, A. Lo, and Ferguson, E. E., J. Chem. Phys. 44, 4537 (1966). Fehsenfeld, F. C., Ferguson, E. E., and Schmeltekopf, A. L., J. Chem. Phys. g, 1844 (1966). Wise, H., and Ablow, C. M., J. Chem. Phys. 2, 634 (1958). Wise, H., and Ablow, C. M., J. Chem. Phys. z, 10 (1963). Dickens, P. G., Schofield, D., and Walsh, J., Trans. Far. SOC. s, 1338 (1959). Schulz, W. R., Morgan, J. E., and Le Roy, D. and Schiff, H. J., Can. J. Chem. 40, 2413 (1962). I., J. Chem. Phys. 2, 2631 (1963). Tsu, K., and Boudart, M., Can. J. Chem. 2, 1239 (1961). Rony, P. R., "The Mathematics of Steady-State Diffusion and Flow Tubes. Factors Affecting Rate Measurements," 2nd Annual Chemical Engineering Symposium, Stanford, California, 1965. (Copies are available). Rony, P. R, I. & E. C. (to be submitted). Biondi, M. A., and Brown, S. C., Phys. Rev. a, 1700 (1949). Phelps, A. V., and Brown, S. C., Phys. Rev. 86, 102 (1952). Gray, E. P., and Kerr, D. E., Ann. Phys. lJ, 276 (1959). McDaniel, E. W., Col1isio.i Phenomena in Ionized Gases (John Wiley & Sons, Inc., New York, 1- Carslaw, H. S., and Jaeger, J. C., Conduction of Heat in Solids (Clarendon Press, Oxford, England, 1959), Section 8.3, p. 2l7. Jolly, W. L., "The Use of Electric Discharges in Chemical Synthesis," Lawrence Radiation Laboratory ~~~~-9591 (1960). (unpublished). Gould, R. F., Free Radicals in Inorganic Chemistry (her. Chem. SOC., Washington, D. C., 1962). Kondrat'ev, V. N., Chemical Kinetics of Gas Reactions (Addison-Wesley Publishing Company, Ind., Reading, Massachusetts, 1$4), p. 467. Kana'an, A. S., and Margrave, J. L., Advances in Inorganic Chemistry and Radiochemistry 6, (Academic Press, New York, 1964), p. 143. Hurt, W. B., J. Chem. Phys. 9, 3439 (1966).
L - 2 A = - R MI2 - L T = a+- R v R @=A D12 a2 D12 119 APPENDIX bt2 = 2D12(1 RYTl y'22 (surface phase) p2- p klR2 ' d 'I+ = c (gas phase) (gas phase) 2k R y = & V1 1 1 = u2+- 6'2 = n~(2n + 11 an M
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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
Page 63 and 64:
\ 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
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 and 94: 93 where the bar indicates values c
Page 95 and 96: 'I i 'I 0 2. 4 6 8 2 [ N]* x' I 0-2
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 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+ +
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 and 180:
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:
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
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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
Page 233 and 234:
- 233 SOME PROBLEMS OF THE KINETICS
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.. . :. ,. .I , . i ? .. . , ... .
Page 237 and 238:
237 Table 2 Experimental Variables
Page 239 and 240:
239 Zhbie I Eerccnt Consumption of
Page 241 and 242:
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
Page 253 and 254:
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
Page 261 and 262:
i 25i The Dlssocfatior of ToIuere V
Page 263 and 264:
L ! , c PRODUCTS FROM A 28 MC. DISC
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'\ J ?. , .. . : PRODUCT FORMATION
Page 267 and 268:
'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
Page 277 and 278:
. 277 6. A freshly prepared sam le
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observed. The polystyrene (10% solu
Page 281 and 282:
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
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
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294 have suitable residence times i
Page 297 and 298:
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
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. The transformer secondary and the
Page 309 and 310:
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
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
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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
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331 f'ENI?AL PF'FCLCCFC Dernis, P.R
Page 334 and 335:
i J 333 ; mosphere (as opposed to a
Page 336 and 337:
; it raised the question, still &?z
Page 338 and 339:
p .I V I .= - - HCN/C(CALC. WITH C
Page 340 and 341:
1 1 339 atmospheric ressure and ach
Page 342 and 343:
RESULTS 341 Composition Dependence
Page 344 and 345:
0.09 0.08 0.07 9 0.06 2 U - .$ 0.05
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II \ to the Slot So that less of th
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
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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
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
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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
Page 406 and 407:
402 HYDROGEN CYANIDE PRODUCED FROM
Page 408 and 409:
404 Before startup, the system is p
Page 410 and 411:
4 OL. ' , I. . TesCs. With.Coals .o
Page 412 and 413:
Table 3.- Product Gas Analyses and
Page 414 and 415:
410 BIBLIOGRAPHY 1. American Public
Page 416 and 417:
Figure 2. Enclosure surrounding hyd
Page 418 and 419:
0 0 f v) C 0 u m I z 2 c 2 r d J w
Page 420 and 421:
0. E c .4 7 .. .c . I ( - Low tempe
Page 422 and 423:
418 cual. A mjor aa\;antage or' the
Page 424 and 425:
420 Ir ?Y ? ? 9 9 9 pc rod n o c o
Page 426 and 427:
422 Table 3. Room-texperature M'dss
Page 428 and 429:
424 state, depending on the strengt
Page 430 and 431:
Table 4. Room-?;ergerature isomer s
Page 432 and 433:
I' 1.3 . /o 9 IO 9 6 a 425 F F 33 I
Page 434 and 435:
Brooks J.D. and Sternhell S. (1957)
Page 436 and 437:
(52) Gib3 T.C. and Greenwood N.N. (
Page 438 and 439:
434 transducer vas then introduced
Page 440 and 441:
436 yield is quite similar. The con
Page 442 and 443:
?-!??? 0 mv, Uh\OhIe . . . . eirlrl
Page 444 and 445:
4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 4
Page 446 and 447:
442 CHEMICAL REACTIONS IN A CORONA
Page 448 and 449:
helium 444 CORONA REACTOR SYSTEM Fi
Page 450 and 451:
446 The ultraviolet spectrum. for t
Page 452 and 453:
Biphenyl Fraction 448 The low molec
Page 454 and 455:
LUd The actual structural definitio
Page 456 and 457:
I I I I I In m 9 In 2 , I: r- In m
Page 458 and 459:
’. 454 Mechanism I The available
Page 460 and 461:
456 , , . The relatively low yield
Page 462 and 463:
458 h/lethylacetylene, allene and b
Page 464 and 465:
Introduction VAPOR PHASE DECOMPOSIT
Page 466 and 467:
462 more efficient hydrogenation. T
Page 468 and 469:
464 place in parallel with fragment
Page 470 and 471:
466 P rl 0, k 7 rnI rn al k a I hl
Page 472 and 473:
458 TABLE I. COMPOSI'IION OF GASEOU
Page 474 and 475:
REFERENCES 1. C. Hirayama and D. A.
Page 476 and 477:
i 472 Reciprocal Arc Enthalpy ,-> F
Page 478 and 479:
474 be pumped down without altering
Page 480 and 481:
476 Instead a hydrogen deficient fi
Page 482 and 483:
i 478
Page 484 and 485:
480 FATTY ACIDS AND n-ALKANES IN GR
Page 486 and 487:
482 TA5L,E 2. - Carbon number distr
Page 488 and 489:
6. 7. a. 9. 484 Lawlor, D. L., and
Page 490 and 491:
' I ' Sample No. 6 ' 12 IO 8 6 z 4
Page 492 and 493:
. 488 uiolecular weight of which ca
Page 494 and 495:
Xississippi (Sample GS). Stock solu
Page 496 and 497:
492 found at 5.7 and 4.9& for the W
Page 498 and 499:
494 mechanisms. However, the voltad
Page 500 and 501:
For pure polynuclcar arom.i;ic hydr
Page 502 and 503:
- '-'. . ' . . values are listed in
Page 504 and 505:
500 (1;) Ten, T. 17.: a;1d,Dic;
Page 506 and 507:
- ~ Resistivity Czlculation 2: 1 j:
Page 508 and 509:
504 o ' C 0s 2 0 v x i 8 2 0 ! P -
Page 510 and 511:
506 i
Page 512 and 513:
d 601 L P LL
Page 516 and 517:
I I I I I I I I m W N W N 0 (D ? 0
Page 518 and 519:
514 was heated under nitrogen in a
Page 520 and 521:
The line broadening at 79OK of the
Page 522 and 523:
13. 14. 15. 16. 17. 18. 19. 20. 21.
Page 524 and 525:
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
Page 530 and 531:
526 Table 1.- Ultimate analyses of
Page 532 and 533:
528 6. Friedel, R. A., and H. Retco
Page 534 and 535:
egeneration. The system can be seen
Page 536 and 537:
532 and can be expressed in terms o
Page 538 and 539:
534 in the vapor increases with inc
Page 540 and 541:
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
Page 550 and 551:
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
Page 556 and 557:
FRIT 'TED CO, CH,.OR 4 ___ OTHER AD
Page 558 and 559:
340 350 300 400 4 50 500 600 700 80
Page 560 and 561:
0 554 WITH COOLING (PLATE AT 40°C)
Page 562 and 563:
5 56 then t = to when e = 0 2) the
Page 564 and 565:
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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