chemical physics of discharges - Argonne National Laboratory

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I I I I I I I I m W N W N 0 (D ? 0 2 0 2 0 0 0 0 D N IO ,
, 513 THE ELECTRON SPIN RESONANCE SPECTRA OF CELLULOSE CHARS TREATED WITH HALOGENS* Evidence for Donor-Acceptor Complexes in Coals and Chars R.M. Elofson and K.F. Schulz Research Counci I of AI berta Edmonton, Alberta INTRODUCTION Coals and low- and medium-temperature chars have been shown to be paramagnetic by bulk magnetic susceptibility measurementsl,2fr3 and by electron spin resonance studies4r5t6. If due care is taken to eliminate errors, reasonable agreement in the estimate of the number of unpaired electrons present can be obtained'. While there is agreement on the existence of paramagnetic centres in these materials, the origin and nature of these free radicals is not understood8,"10,'?,12. It is the purpose of this article to present new evidence to suggest that these unpaired electrons arise from donor-acceptor forces present in these materials. One way of studying the nature of free radicols is by observing the behavior of the electron spin resonance signals when the substrate is treated with adsorbed gases and other reagents. Early workers in the field found that poramagnetic gases such as oxygen affected only the spin- lattice relaxation times of chars prepared at from 300" to 5OOOC. For chars prepared in the 550' to 800" temperature range, however, reversible line broadening occurred with an apparent decrease in free radical concentration at higher oxygen pressures. Removal of oxygen restored the original signal, which indicated that the phenomenon was due to physical and not chemical processes. Halogens were at first found to have no effect on coals and chars and the oxygen effect was attributed to spin broadening due to the paramagnetism of the oxygen molecules. Similar results to oxygen were obtained with nitric oxide. In 1963 Wynne-Jone~~~ and co-workers found that e.s.r. signals in chars obtained by heating polyvinylidene chloride (saran) were affected by adsorption of halogens. These workers noted that IBr, ICI, I, Br, and C12 caused partial or complete reduction in spin concentration at constant line width. The original signal was not restored by outgassing in vacuo at room temperature but could be partially restored by reheating the specimen at 100°C in vacuo. Since, as mentioned above, no halogen effect had been obtained on coals or more common chars, these authors attributed the susceptibility to halogens of these saran chars to a high degree of porosity. Reinvestigation of the interaction of a series of cellulose chars with iodine, bromine and hydrogen iodide in this laboratory has shown pronounced effects on the electron spin resonance of some of these materials. EXPERIMENTAL &llulose chars were prepared by fint charring cellulose powder (Whatman Cellulose Powder, Standard Grade) in an autoclave at 195"-2OO0C under nitrogen. Subsequently this char * Contribution No. 360 from the Research Council of Alberta, Edmonton, Alberta.
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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
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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
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 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
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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
Page 570:
ln 4 I 0 4J v \ 1.0 0.8 0.6 L - 0.4
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