chemical physics of discharges - Argonne National Laboratory

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z 0 c a 60 2 40 0 2 U + 2 5 20 M 0 Figure 3 74 036 torr HzO 0 10 20 30 40 50 ION ENPRGY, E,I (volts) Effect of electric field on cluster composition. Ere equals voltage between repeller and ion source exit slit. Temperature of ion source 3OOC. Water pressure 0.36 torr. Experiments taken with 100 kev proton beam mass spectrometer. ! I II
75 Negative Ion Mass Spectra of Some Boron Hydrides D. F. Munro, J. E. Ahnell, and W. S. Koski: Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218 Abstract I , Questions of the role of negative boron hydride ions frequently arise in problems concerning energetics of electron impact processes, discharge tube reactions, and radiation chemistry. In view of the fact that the boron hydrides are electron deficient compounds, it might be expected that they are more prone to negative ion formation than hydrocarbons; however, very few studies of such ions have appeared in the literature. This paper gives some qualitative results obtained on boron hydride negative ions produced by electron bombardment of diborane, tetraborane, and pentaborane-9. A pulsed electron beam, a quadrupole mass analyzer, and an electron multiplier were used for this work. In diborane, the most inteise ions observed were BzH3- pd BHQ-. B*H-, Bz-, BH3-, BH2 , BH-, and B were also readily detectable. Similarly, the - negative ions observed in tetraborane - included the relatively high intensity B3H7 and lower intensities of BzHg-, B2H4 , BHI, ,,etc. In addition, indications were obtained for B4Hg . Similar results were obtained with pentaborane-9. Lover and varying intensities of BzH4-, B2H3 , B2H2 , Introduction For many years, mass spectroscopists have dealt almost exclusively with processes involving positive ions; ionization, fragmentation, and ion-molecule reactions. Recently, however, despite problems of low intensity, an increasing amount of work has been done on negative ions. A number of species have been character- ized,' and a few reactions have been studied.2s3 In addition, at least one investi- gation on the role of negative ions in flames has been carried out, using mass spectroscopic techniques. The boron hydrides are traditionally classified among the electron deficient compounds, and might well be expected to form negative ions. whennore, some work has been done with the boron hydrides in gaseous discharges and in radiationchemistry where these ions might conceivably play a role.5 Thus, it was of interest to us to study the negative ions of the boron hyhrides with the eventual hope of providing information to permit the evaluation of the role these ions might play in discharges and other associated phenomena. We have under construction in our laboratory a tandem mass spectrometer for the study of ion-molecule reactions. In the course of testing the first stage of the instrument, it became apparent that the spectrometer might be suited for the observation of negative ions. The ions from SF6 and 02 were detected with relative ease. It was decided to investigate vhat negative ions could be observed in the simpler boron hydrides; diborane, tetraborane, and pentaborane. Because the spectrometer is still in the construction stage, some of the re- finements normally found on conventional instnunents are lacking, so that the results obtained are necessarily of a qualitative nature. Nevertheless, it was felt that the observations were sufficiently interesting to warrant reporting. Experimental The important features of the basic experimental arrangement are shown diagremmatically in Fig. 1. The gas to be analyzed flows from a bulb at roan temperature into the ion source through a Granville-Phillips leak. The ion source, which is similar in design to one described by Von Zahn,6 has an electron beam energy
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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
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: 73 ' , radius might be expected bec
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
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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
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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
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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 ? .. . , ... .
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
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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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