chemical physics of discharges - Argonne National Laboratory

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79 for positive and negative ions, approximate corrections can be made. At worst, the relative intensities throughout the whole, spectra are probably correct within 225%. Although reasonable precautions were taken to assure the purity of the sample in the diborane spectrum, peaks corresponding to B3H7 and B4Hg were observed. These could have arisen either from ion-molecule reactions, from pyrolysis of the diborane as the sample flowed into the source, or from impurities i7 the diborane. The latter is improbable, for in a positive ion spectrum of the same sample in the same spectrometer, the tetraborane peaks could be observed only with difficulty. It was estimated on the basis of the positive ion spectrum that the tetraborane impurity could be no greater than one part in five-hundred. In the negative ion spectrum the ?ea& corresponding to B3H7- and B2H3 were of almost equal intensity. It should be noted, however, that in comparing the diborane and tetraborane samples, it .was much easier to observe the negative ion peaks from tetraborane, which were larger by sbmbnut two orders of magnitude. There are several mechanisms by which negative ions can be formed. The tradi- tional processes are as follows: 1. Ion pair. formation: 2. Resonance attachment: XY + e -+ XY 3. Resonance attachment with dissociation: XY + e -- X + Y- XY + e -+ X+ +-Y- + e In addition,a process somewhat like the third mentioned above can be imagined, in which the neutral species is left in an excited state which in turn decays to an ion pair. Also, a negative ion may fragment, giving rise to a neutral species and a new negative ion. 4. Excited state decay: XYZ + e +. XY* + Z- 5. Fragmentation: XY- -+ X + Y- XY* -+ x+ + Y- + Using the above scheme, and assuming that the fragments most easily lost are BHg , BH3 , and hydrogens, most of the more intense peaks in the negative ion boron hydride spectra can be accounted for rather well in the following manner. Possible Modes of Fragmentation of Diborane The underlined peaks are the four most intense in the diborane mass spectrum. The other peaks come from loss of hydrogens, either singly or in pairs, from the above species. Possible Modes of Fragmentation of Tetraborane This scheme accounts for all of-the peaks with an observed intensity of greater than 1%, except for the B2H3 peak, whose intensity is 1.1%, and which could be due to a diborane impurity.
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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
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: A b 1 1 I H I I I FILAMEN T CONTINU
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
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{;I . - . .. . - .., . . .. _- .. .
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1 \ \ \ , \ , \ \ Pmer hnrity K.W.
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. I operating fact that the sloGe i
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_- of ' . 8. - 7 6, Residence Time
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135 Ionic Reactions in Corona Disch
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GAS OUT GAS IN i.ho QUADRUPOLE MASS
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- + ( ~ ~ + 0 H ) ~ O ~ ( H~o)~H+ +
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144 i I , , , , . + 1- u 3c w Inu c
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146 SYNTHESIS OF ORGANIC COIGhTDS B
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mi5 a- dz CI n I a I n +4 - 0 -I- k
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0 z cu I I I
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I- I - t d m a .rl Y x c, t-' d k
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, 155 This result is significant in
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Compound Bond he rgy Li I 82 UBr 10
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, ”..’ 3or 25 - 5 20 - s 3 w Y
Page 161 and 162:
I 161 THE GLOW DISCHARGE DEPOSITION
Page 163 and 164:
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
Page 169 and 170:
Mole Reaction Material ratio time e
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\ 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
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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:
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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 ? .. . , ... .
Page 237 and 238:
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
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
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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 +
Page 324 and 325:
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
Page 372 and 373:
Distribution and yield rates of pro
Page 374 and 375:
. . I . I 370 . . . . ., . . .. . .
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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 '---
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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
Page 408 and 409:
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
Page 430 and 431:
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. (
Page 438 and 439:
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
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
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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
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
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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
Page 538 and 539:
534 in the vapor increases with inc
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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
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-4:c~rciiny to recent studies o ;i4
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544 Table 1. LIGHT EMISSION OF Y"TR
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emission in a few cases may be by d
Page 552 and 553:
LITERATUR2 CITED i. C. -. .' * il.
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co, CH,,OR 1 - OTHER ADDITIVE FRITT
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FRIT 'TED CO, CH,.OR 4 ___ OTHER AD
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340 350 300 400 4 50 500 600 700 80
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0 554 WITH COOLING (PLATE AT 40°C)
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5 56 then t = to when e = 0 2) the
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5 58 The surface heat transfer coef
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Discussion and Results 560 Three br
Page 568 and 569:
__- ._ 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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