chemical physics of discharges - Argonne National Laboratory

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RESULTS 341 Composition Dependence Figure 6 shows typical "titration" curves for the different situations of interest. In every case a plot of HCN produced vs. methane added (both normalized to the "standard flow rate" of 0.0171 l(STP)/sec) divides cleanly into two renimes separated by a break to which we refer as the "equivalence point." To the left of the equivalence 1 point, the yield is simply dependent on methane feed rate but not on the power level. 1 Lines Of slope 1/3 and 2/3 are included on the graph to facilitate intercomparison in ' ) \ this region. Although the data are too scattered to draw firm conclusions, it is clear that the break quite generally occurs along the line correspondine to a slope of 113. In this region it is as though the nitrogen were somehow present in excess. To the right Of the break the HCN throughput is seen to depend only veakly on methane but, as is demonstrated below, is a strong and simple function of heat flow in the nitrogen before mixing. Excluding for the moment the (-1/4"; 0") data (Figure 6-d), the methane dependence on the right shows a real linear increase with methane flow rate in every case, but this slope is not found to be particularly reproducible since it is apt to change slightly when the apparatus is demounted and reassembled. Hence the scale has been chosen to emphasize the plateau-like character of the curve. Note that the data excepted may be explained by the fact that in this case the exit rather than the lentrant heat flow is regulated. Because of the small heat loss in this short section only a second order effect of this magnitude would be expected. Power Level Dependence To take account of the residual slope of the "titration" curves, intercomparison of power-level-dependence studies is done at the same methane flow rate corresponding to one half the "standard" flow whether it is an interpolated point taken from a full titration curve as shown in Figure 6 (filled points) or an isolated measurement (open points). The best line through the oid data (Figure 2) appears in Figures 7 through 9 as a reference to aid in intercomparison. Note that Figure 6-a should be exactly consistent with the older data of Figure 1 while the data of Figure 7-b should exactly reproduce Figure 2. The extent that they fail to do this is a fair measure of the nonreproducibility of this experiment when performed in different laboratories, with different equipment, vith the chemical analyses performed by different persons. In Figure 7-b data from two different 2" reactors are intermingled as shown. This is to be compared with the (0"; 8") data of Fieure 7-a. It is quite clear that within the experimental scatter it would indeed be difficult to improve the agreement. Now the heat leaving the 8" reactor for a given input is only about one half that leaving a 2" reactor for the same input, so that there can be no question but that the HCN production depends only on the heat flow at the point of mixing (or at the exit Of the head) and not at all on that at the exit of the reactor. Mixing Point Dependence Figure 8 demonstrates clearly that the ability of the nitrogen to make HCN does not persist d m the tube at its high initial level, but rather decays as the heat flowing in the gas decays. Shown are a particular set of (6"; 8") data plotted on the left - VB heat flow at the exit of the head, and on the right as a function of the heat flowing at the point of mixing, the 6" point. Hence that part of the earlier work indicating the existence of a "long-lived" reactive species is wrong. Leutner Reactor Data for the simulated Leutner reactor are shown in Fi&ure 9. Despite the fact that these data were taken at atmospheric pressure it is clear that the results are completely consistent with those of the other reactors. This atzrees with an observation made in the earlier work that there is but slight pressuke dependence for this reaction. .._ . _,.-. .. ., .... ..~. - ... '
* L 1 1 1 1 I I 1 1 I I I U - 0.10 1 / 6099 kw. (0";8") - 0.Q) - I / 0.09 0.m 0.07 u 6 0.06 X .e - 0.05 9 2 0.04 p 0.03 0.02 O.O1 0 L 342 - QW 1 1 1 1 1 .I - METHANE FLOW (hCHJC) - o '0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 a9 1.0 ' ATMOSPHERIC l/l I I I I 1 1 4770k~(-1/4";0") PRESSURE 1 - rn A . - - " - 1 1 1 1 1 ' 1 1 6. Typical titratiaa curre. for the cue notad. nomd.i;ml productim rate or HCR V. flow rat. or m e . DMII.~ liar. or ~iape i/3 .nd 2/3 ue inciw~~-?or referonce. 1 0 I 2 3 4 5 6 7 8 9 IO HEAT FLOll (kw) - Y 0.09 I 0.08 0.07 3 0.06 I '5 0.05 2 0.04 5) 0.03 0.02 0.01 1 - ! I ~
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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
Page 101 and 102:
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
Page 291 and 292: ? ~ MENBERSHIP IN THE DIVISION OF F
Page 293 and 294: 292 flow of the reactant gas stream
Page 295 and 296: 294 have suitable residence times i
Page 297 and 298: 0 E < h( E l! d K c 0 .- Y 0 t u t
Page 299 and 300: 298 yields of many chemical product
Page 301 and 302: - ;i Y . 15. Pressure lOmm 5 > 10-
Page 303 and 304: 302 the best and in many practical
Page 305 and 306: GENERATION AND MEASUREMENT OF AUDIO
Page 307 and 308: . The transformer secondary and the
Page 309 and 310: Vaccum-Tube Amplifier The mobile co
Page 311 and 312: 310 f = Power supply frequency in c
Page 313: FUFARCI! INSTITUTE OF TFYDLC UNIVER
Page 316 and 317: J # I / 4) I . . '8 r4 0 r( P
Page 318 and 319: 317 i Cuencb svsten w.nnar;itus use
Page 320 and 321: epcrte? the noss~kil.itv of nroduct
Page 322 and 323: 1' b t +
Page 324 and 325: 323 ....... - . . . . . . . . . . .
Page 326 and 327: 1 \ i I i , / / / 8 3 1 325 To205 +
Page 328 and 329: - .- - - . - - . . . - . 327 n + c
Page 330 and 331: ' POWER PLASMA GAS l e , ' I ! I I
Page 332 and 333: 331 f'ENI?AL PF'FCLCCFC Dernis, P.R
Page 334 and 335: i J 333 ; mosphere (as opposed to a
Page 336 and 337: ; it raised the question, still &?z
Page 338 and 339: p .I V I .= - - HCN/C(CALC. WITH C
Page 340 and 341: 1 1 339 atmospheric ressure and ach
Page 344 and 345: 0.09 0.08 0.07 9 0.06 2 U - .$ 0.05
Page 346 and 347: II \ to the Slot So that less of th
Page 348 and 349: i 4 2 HYDROCARBON-NITROGEN REACTION
Page 350 and 351: I 1 349 c M m ; a e, k M x
Page 352 and 353: 1.0 I - a. I n TEMPERATURE - OK Fig
Page 354 and 355: 353 the experimental results in the
Page 356 and 357: ,) 355 The ceaswed conversion cf ni
Page 358 and 359: 1 6 357 Freezing. 3jpotnesise thzf
Page 360 and 361: 359 \ Frozen Compositior: Calcillat
Page 362 and 363: I 1 \ 361 -. ne reaction proceecis
Page 364 and 365: \ 36 3 ' h, I 26. H. Purnell, Gas C
Page 366 and 367: In experiments on the direct conver
Page 368 and 369: 367 used as blnders, with different
Page 370 and 371: 369 ' i 1. REFERENCES Berber, John
Page 372 and 373: Distribution and yield rates of pro
Page 374 and 375: . . I . I 370 . . . . ., . . .. . .
Page 376 and 377: 4 372 090- > E w - m c N O - 0 z :
Page 378 and 379: A-Feed tank 6-Thermocracker GReceiv
Page 380 and 381: 80 \ 0 70 60 e 40 a U VI 9 30 20 10
Page 382 and 383: COAL DEASH& AND HIGH-PURITY COKE Wa
Page 384 and 385: 3Pn _. -. - L -J:,J.-;~~~L, ):as se
Page 386 and 387: S ~ l ~ o n~pg:ading r is the resul
Page 388 and 389: The range ~f temperatures and gener
Page 390 and 391: . .. 386 9 * - r. Y 2 .' d a f' r.
Page 392 and 393:
.) .L m 388 I
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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
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
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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
Page 424 and 425:
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
Page 434 and 435:
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
Page 446 and 447:
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
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
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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
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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
Page 472 and 473:
458 TABLE I. COMPOSI'IION OF GASEOU
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REFERENCES 1. C. Hirayama and D. A.
Page 476 and 477:
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
Page 492 and 493:
. 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
Page 500 and 501:
For pure polynuclcar arom.i;ic hydr
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- '-'. . ' . . 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
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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
Page 520 and 521:
The line broadening at 79OK of the
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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
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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
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
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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
Page 568 and 569:
__- ._ 562 Table I THERMAL AND PHYS
Page 570:
ln 4 I 0 4J v \ 1.0 0.8 0.6 L - 0.4
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