chemical physics of discharges - Argonne National Laboratory

More documents

Recommendations

Info

244 RESULTS Figure 1 shows the results of experiments made at initial gas pressure of 12 + 1 torr in 36-cm long by 11-mm I D reactors. The percent of carbon present in the product as C2Hp and as CH4 + C2H2 is plotted vs. reaction time. Figure 2 shows the percent of carbon present in the product as CH4 for the same runs. Water, C02. and occasionally slight traces of other hydrocarbons, were also present in the product. times of 30-120 seconds. Figure 3 shows the results of experimentslmade at initial gas pressures of 50 t 3 torr in 20-cm long by 11-mm ID reactors, Here, the percent of carbon present as CH4 + C2H2 is at a m3ximum of 24-25); for reaction times of 3-4 minutes. There is considerable scatter In the data; the dashed curves are intended to show only the general trend. The conversion of CO to CHq + C2H2 reaches a maximum of 17-18% for reaction These data show that conversion of CO to hydrocarbons in the discharge under these conditions is Limited. The composition of the gases in the reactor approaches a stationary state, for reaction times of the order of 0.5 to 3 minutes, depending upon the pressure. Because of the geometry of the reactors, and the volume of a reactor relative to the volume occupied by the discharge, the time required to reach the stationary state appears to be longer than is actually so, due to the relatively long times required for diffusion of gases into and out of the discharge. (The 36-cm long reactors were used for the runs made at 12 torr; for the runs mede at 50 torr, the shorter 20-cm long reactors were used. Preliminary experiments showed that the conversion of CO to CH4 + C2H2 at 50 torr in 36-cm long reactors was essentially the same as for the 20-cm long reactors, but took 1-2 minutes longer to achieve mximm conversions.) High yields of gaseous hydrocarbons from H2 + CO have now been shown to occur in low-frequency (50 Hzll and 60 H Z / ) discharges, radiofrequency (2-110 MHz)?/ and microwave (2450 MHz) discharges. However, in all of these cases, the reaction does not appear to be an extremely rapid one, such as is the case for dissociation of diatomic molecules in a discharge, for instance. For reaction times longer than those needed to reach maximum conversions, the conversions appear to decrease. This is probably due to some polymer fomtion, but not enough to show up as a 10% decrease in the analytically determined C/Ar ratio. Several runs at 12 torr (not plotted) of 5 minutes duration, and some longer runs, including one at 50 torr for 10 minutes, gave values of the C/Ar ratio more than 10% below the initial value of the ratio, and this was considered evidence of polymer formation. Here, also, the yields of CH4 and C2H2 were lover. Conversions of CO could be increased by removing reaction products ae they forrmd, by having a cold trap surround the bottom 5 cm of the reactor before and during the time that the discharge was maintained at a distance of 10 cm from the bottom. The discharge is localized and extends over a distance of about 2 cm. As shown in table 1, the conversion of CO increased markedly and the product distribution changed. Values for the C/Ar ratio indicated that polymers were not formed. Also, there is no indication that the product distribution is any different in the presence of Ar than in its absence. The first three columns in the table are for the 3- minute runs shovn in figures 1 and 2. When the discharge was maintained for 3 minutes’ or longer, with Dry Ice (-78O) surrounding the end of the reactor, the percent Of carbon present in the final product as CHq is 51%; C2H2, 17%; CzRg, la. At this temperature, the only reaction product frozen out is H20. Apparently, the removal of this is sufficient to increase the convereion of CO to hydrocarbons to approxi- mately 78%. I I /J
h z - a o m a 20 T IME, minutes . Fiqure 1.- Formation of hydrocarbons from H2+ CO in microwave- generated discharge: acetylene 0, acetylene + methane 0. Initial gas pressure = 1251 torr. 11-30-66 L-9694
Page 1 and 2:
)i 1 reesonably complete and accura
Page 3 and 4:
3 inquire about the component of ve
Page 5 and 6:
4 I I 5 To find (t2)av, we assume t
Page 7 and 8:
\ vnich, it is noted can be negativ
Page 9 and 10:
I 7 than or smaller than the second
Page 11 and 12:
i I i I I I ) ) i L , I I . INT1:OD
Page 13 and 14:
13 field per electron is and per co
Page 15 and 16:
. 11. 5. CharRe-Transfer and Ion-Mo
Page 17 and 18:
17 In the followin:: sections much
Page 19 and 20:
above. With that EIN, an estimate o
Page 21 and 22:
21 region in w!iich large, nighlv l
Page 23 and 24:
i ’ understanding: 23 (a) Electro
Page 25 and 26:
Obviously, the secondary ion must h
Page 27 and 28:
27 (22) Franklin, J. L., Munson, M.
Page 29 and 30:
Tables 1-6 present examples of rela
Page 31 and 32:
Table 8 Some Ions Formed by Process
Page 33 and 34:
33 velocity of the reacting partn r
Page 35 and 36:
35 must be added to the Langevin cr
Page 37 and 38:
37 In our laboratory a microwave di
Page 39 and 40:
+ . 4 . r 39 as well as N in a cor0
Page 41 and 42:
ION-MOIECULE REACTION RATES MEASUFI
Page 43 and 44:
43 excitntion 2onditions so that th
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 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 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+ +
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
Page 181 and 182:
\ 3 , ,\ 110 v 60 CPS MANOMETER . F
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
Page 231 and 232: N I + 0" ON i I + 0 u / 0 0 I 0 cu
Page 233 and 234: - 233 SOME PROBLEMS OF THE KINETICS
Page 235 and 236: .. . :. ,. .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
Page 243: I \ 1 243 FORMATION OF HYDROCARBONS
Page 247 and 248: I 1 I I I I 0 I 2 3 4 5 TIME, minut
Page 249 and 250: The next five coluws in table 1 sho
Page 251 and 252: \ .\ t 251 Given the existence of t
Page 253 and 254: I L 253 Epple, R. P. and C. M. Apt.
Page 255 and 256: 1 ' Fig. 1 Schematic of flow discha
Page 257 and 258: 5' . ' I 1 257 co, with excess H2,
Page 259 and 260: 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
Page 265 and 266: '\ J ?. , .. . : PRODUCT FORMATION
Page 267 and 268: '9 / I '\ "1 BENZYL CATION AND RADI
Page 269 and 270: a
Page 271 and 272: 271 tube serve? as the high voltare
Page 273 and 274: 273 ion (1L.). Zxcitei-ion by colli
Page 275 and 276: Apparatus and Procedure 275 EXPERIM
Page 277 and 278: . 277 6. A freshly prepared sam le
Page 279 and 280: observed. The polystyrene (10% solu
Page 281 and 282: i i (12) c (11) (14) I 281 LITERATU
Page 283 and 284: FLOW- METER I ADDITIVE SUPPLY * ,28
Page 285 and 286: 285 TABLE 2 Effect of Haloqenated A
Page 287 and 288: ANALYTICAL RESULTS Some evidence wa
Page 289 and 290: DISCUSSION 289 The salient features
Page 291 and 292: ? ~ MENBERSHIP IN THE DIVISION OF F
Page 293 and 294: 292 flow of the reactant gas stream
Page 295 and 296:
294 have suitable residence times i
Page 297 and 298:
0 E < h( E l! d K c 0 .- Y 0 t u t
Page 299 and 300:
298 yields of many chemical product
Page 301 and 302:
- ;i Y . 15. Pressure lOmm 5 > 10-
Page 303 and 304:
302 the best and in many practical
Page 305 and 306:
GENERATION AND MEASUREMENT OF AUDIO
Page 307 and 308:
. The transformer secondary and the
Page 309 and 310:
Vaccum-Tube Amplifier The mobile co
Page 311 and 312:
310 f = Power supply frequency in c
Page 313:
FUFARCI! INSTITUTE OF TFYDLC UNIVER
Page 316 and 317:
J # I / 4) I . . '8 r4 0 r( P
Page 318 and 319:
317 i Cuencb svsten w.nnar;itus use
Page 320 and 321:
epcrte? the noss~kil.itv of nroduct
Page 322 and 323:
1' b t +
Page 324 and 325:
323 ....... - . . . . . . . . . . .
Page 326 and 327:
1 \ i I i , / / / 8 3 1 325 To205 +
Page 328 and 329:
- .- - - . - - . . . - . 327 n + c
Page 330 and 331:
' POWER PLASMA GAS l e , ' I ! I I
Page 332 and 333:
331 f'ENI?AL PF'FCLCCFC Dernis, P.R
Page 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 356 and 357:
,) 355 The ceaswed conversion cf ni
Page 358 and 359:
1 6 357 Freezing. 3jpotnesise thzf
Page 360 and 361:
359 \ Frozen Compositior: Calcillat
Page 362 and 363:
I 1 \ 361 -. ne reaction proceecis
Page 364 and 365:
\ 36 3 ' h, I 26. H. Purnell, Gas C
Page 366 and 367:
In experiments on the direct conver
Page 368 and 369:
367 used as blnders, with different
Page 370 and 371:
369 ' i 1. REFERENCES Berber, John
Page 372 and 373:
Distribution and yield rates of pro
Page 374 and 375:
. . I . I 370 . . . . ., . . .. . .
Page 376 and 377:
4 372 090- > E w - m c N O - 0 z :
Page 378 and 379:
A-Feed tank 6-Thermocracker GReceiv
Page 380 and 381:
80 \ 0 70 60 e 40 a U VI 9 30 20 10
Page 382 and 383:
COAL DEASH& AND HIGH-PURITY COKE Wa
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
show all

chemical physics of discharges - Argonne National Laboratory

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?