chemical physics of discharges - Argonne National Laboratory

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(52) Gib3 T.C. and Greenwood N.N. (19%) The Fidssbauer spectm of the tetra- chloroferrate(I1) ion. >. (j;) Lang G. and Marshall W. (1966) M'dssbauer effect in some haerno~lo3in corzpounds. Proc. Phys. E. London 87, 3-34. (j3) t4atr.u- H.B., Sinha A.P.B. and Yagnik C.M. (L465) The M'dssbauer spectra of spinel oxides containing ferrous ion. S a State C=. & 401-403. (4G) Frank E. and Abeledo C.R. (1566) Mzssbauer effect in iron (111) dithiocar3amates. Inorg. z. & 1433-145>.
1133 REACTIONS OF COAL AND RElATED MATERIALS IN MICRWAVE DISCHARGES IN H2, H20 AND Ar Yuan C. Fu and Bernard D. Blaustein, U. S. Bureau of Mines, Pittsburgh Coal Research Center, . 4800 Forbes Avenue, Pittsburgh, Pennsylvania 15213 INTRODUCTION I Recent investigations on the reaction of carbon in a high frequency discharge have shown that it produces methane, acetylene and minor amounts of other hydrocarbons in the hydrogen dischar e,=/ but produces primarily an H2-CO mixture downstream from a water discharge.-/ 9 Similar vork with respect to coal, however, is almost non-existent except that carried out by Letort et a1.4/ and by Pinchin.'/ Though some work on coal in a plasma jer6-91 has been reported, the characteristic of those reactions is generally the thermal decomposition of coal by rapid heating to high temperatures in an inert atmosphere. In a microwave-generated discharge, hydrogen or water vapor can be excited or dissociated into atoms, ions and electrons at temperatures much lower than those attained in a plasm jet. The present study is concerned with the reactions of various coals, a polynuclear hydrocarbon, and graphite, in microwave discharges in H2, water vapor and Ar. The results are compared in terms of the product yield and distribution in each type of discharge. Differences observed between the reactions of the various coals and the other materials suggest that the amount and type of volatile material, carbon content, and the type of the carbonaceous material, as well as the type of the gas discharge, are all factors affecting the product yield and distribution. The difference between coal and graphite - . in their behavior toward water vapor in the microwave discharge is of particular interest. discharge, the graphite yields almost no hydrocarbons but only an H2 + CO mixture while the coal yields appreciable amounts of C2H2 and CH4 in addition to H2 + CO. Experiments using DzO and Ar.discharges ,indicate that the D20 and the water actually do participate in the reactions with coal to form hydrocarbons. It is also demon- strated that the C2H2 yield from coal in the hydrogen discharge can be drastically increased by condensing at a low temperature part of the primary products formed during the discharge reaction. ACKNOWLEDGEMENTS 1 , In the water The authors wish to thank Dr. Irving Wender for his valuable discussions, Gus Pantages for his technical assistance, A. C. Sharkey, Jr. and Janet Shultz for their mass spectrometric analyses, and John Queiser for his infrared analysis. EXPERIMENTAL The experiments were carried out in a static system 4th the discharge produced by a Raytheon microwave generator in the air-cooled Ophthos coaxial cavity at 2450Mcl sec. Chemical analyses and origins of the vitrains of the different coals used are given in table 1. All the vitrains were -200 mesh. Ultra purity spectroscopic graphite powder (325 mesh, United Carbon) and chrysene (c18H12) were used for comparison. As reactant gases, a 9.7:1 H2-Ar mixture, H20-Ar mixtures and Ar were used. The H2 and At were obtained from cylinders and passed through a liquid N2 trap prior to storage. The uater vapor was obtained from distilled water degassed in high vacuum. In the experimental procedure, a knom weight of graphite or coal powder was placed in a cylindrical Vycor tube (ID - 11 m, vol - 32 ml) and degassed in a high vacuum at an elevated temperature-(150°C for graphite and 100°C for coal) for a half to one hour to remwe the moisture and the air adsorbed on the carbon. ' A known pressure of the reactant gas or gas mixture measured by a Pace Engineering pressure
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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
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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 ? .. . , ... .
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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
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 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
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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
Page 528 and 529:
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
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
Page 548 and 549:
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.
Page 554 and 555:
co, CH,,OR 1 - OTHER ADDITIVE FRITT
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FRIT 'TED CO, CH,.OR 4 ___ OTHER AD
Page 558 and 559:
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
Page 566 and 567:
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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