chemical physics of discharges - Argonne National Laboratory

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0 0 AI r 0 z a rc) I Z c. * I 0 z 0 W (3 E a I 0 m 5 z 0 K LL 0 Z z - a 3NllVA - N- u? AI- . . 0 *a -0 C cu- 3N13031 ((IlJVdNVlS lVNL131NI) 3NINOIH13H I 3NllSA3 -a -0 . . AI- i i f
, 155 This result is significant in the context of chemical evolution. It has generally been thought, that amino acids had first to be synthesized and then cmdensed together into a polymer. The synthesis of a polypeptide in an electric discharge experiment reveals that such a sequence of r-actions may not have been necessary. If a suitable condensation agent is present the polymer appears to be formed as sson as the acids are s-ynthesized. In our case, the condensation agent is probably hydr-gen cyanide. The presence of 18$ hydrogen cyanide in the reaction mixture combined with the fact that in previous experiments we have beeh able to condense bases and sugars with cyanide support this hypothesis. The different experlments that have been described so far reveal that impor- 1 tant biclogical molecules can be synthesized by the use of a form of energy which existed -n the primitive earth. These conditions may be considered to be genuinely abiotic since the materials used are the constituents of the presumed prinitive , earth atmosphere, the conditions are aqueous, and the form of enera is on2 that is likely to have sccurred on the earth before the appearance of life. \ References > 1. S. L. Miller and H. C. Urey, Science ', a, 245 (1959) 2. R. Beutner, Life's Beginning on The Earth, Williams and Wilkins, Baltimore, 1938 3. S. L. Miller, J. Am. Chem. SOC. a, 2351 (1955) 4. S. L. Miller, Bichim. et Biophys. Acta 23, 480 (1957) 5. C. Ponnqperuva and F. Woeller, Nature m3, 272 (1964) 6. C. Ponnamperuma and K. Pering, Nature 2- 979 (1966) 7. W. A. Allen and C. Ponnamperuma, Currents in Modern Biology (in press) (1967) I 8. R. Sanchez, J. Ferris, and L. E. Orgel, Science 153, 72 (1966) . TAELE I SOURCE - Ultraviolet light ( 2500 i) Electric discharges Radio activity Volcanoes TABLF: I1 High Arc Total hours of current flow 1- 5 Electrode voltage Cell current (m. amp) $ L ss CHq/h End prsducts ($) Ethane Propane Ethene Pr=pene Acetylene 1400 4.0 6.6 32 2 32 27 -- ENERGY (in cal em+ p-1) 570 4 0.8 0.13 Low Arc 40 2500 0.5 1.1 20 5.2 2.4 1.9 42.5 Semi -Corona 48 9400 0.3 0.6 58. a 36.8 1.5 0.6 0.0
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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
Page 103 and 104: 103 All gases were taken directly f
Page 106 and 107: 10; He: + N2 -. 2He + h': (8) whi!?
Page 108 and 109: description for both diffusion and
Page 110 and 111: B. Ions and Electrons I Consider a
Page 112 and 113: ' 112 axial diffusion through the d
Page 114 and 115: the tube walls occurs continuously
Page 116 and 117: E2R M ' $6"
Page 118 and 119: 1. 2. 3. 4. 5. 6. 7. 8. 9- 10. u. -
Page 120 and 121: 120 . Dlschorge zone Reactor zone 1
Page 122 and 123: 122 In radiation chemistry the cust
Page 124 and 125: 124 4. chemistry seem limited essen
Page 126 and 127: 126 Conversion of Mixtures into Mor
Page 128 and 129: Hydrazine Synthesis in A Silent dle
Page 130 and 131: {;I . - . .. . - .., . . .. _- .. .
Page 132 and 133: 1 \ \ \ , \ , \ \ Pmer hnrity K.W.
Page 134 and 135: . I operating fact that the sloGe i
Page 136 and 137: _- of ' . 8. - 7 6, Residence Time
Page 138 and 139: 135 Ionic Reactions in Corona Disch
Page 140 and 141: GAS OUT GAS IN i.ho QUADRUPOLE MASS
Page 142 and 143: - + ( ~ ~ + 0 H ) ~ O ~ ( H~o)~H+ +
Page 144 and 145: 144 i I , , , , . + 1- u 3c w Inu c
Page 146 and 147: 146 SYNTHESIS OF ORGANIC COIGhTDS B
Page 148 and 149: mi5 a- dz CI n I a I n +4 - 0 -I- k
Page 150 and 151: 0 z cu I I I
Page 152: I- I - t d m a .rl Y x c, t-' d k
Page 157 and 158: Compound Bond he rgy Li I 82 UBr 10
Page 159 and 160: , ”..’ 3or 25 - 5 20 - s 3 w Y
Page 161 and 162: I 161 THE GLOW DISCHARGE DEPOSITION
Page 163 and 164: Fig. 1 Process Apparatus -__l.ll__
Page 165 and 166: v) t- at- InIo Io0 t-Q) loo lcua O
Page 167 and 168: This study is only an approximation
Page 169 and 170: Mole Reaction Material ratio time e
Page 171 and 172: \ i (4) Effect of System Pressure T
Page 173 and 174: 173 Pressure. Since pressure is a c
Page 175 and 176: 175 Table VI X-RAY DATA OF DEPOSIT
Page 177 and 178: 177 Another source of weakness is t
Page 179 and 180: 179 PLATING IN A CORONA DISCHARGE R
Page 181 and 182: \ 3 , ,\ 110 v 60 CPS MANOMETER . F
Page 183 and 184: I i , \ I i & a - P Fig. 3 Reaction
Page 185 and 186: \ \' C 0 .d * d .- C U d 0) c( 1) L
Page 187 and 188: I i I . Q) I, s w 0 v) Y 0 a w W a
Page 189 and 190: I (b) Polarized Light Fig. 6 Cross
Page 191 and 192: i m v) Y C i! u o) 23 a a- + 191 m
Page 193 and 194: i, d C .d c c W Q ) 0 0 L1Y 0 000 0
Page 195 and 196: i e 4 0 wcr -4 4 al 0 0 0 c) cr 13:
Page 197 and 198: \ E ‘ 1 TIME FOR RUN 13-1 14-1 -
Page 199 and 200: 199 a red heat in this cell using d
Page 201 and 202: \ , 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
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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
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
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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
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544 Table 1. LIGHT EMISSION OF Y"TR
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emission in a few cases may be by d
Page 552 and 553:
LITERATUR2 CITED i. C. -. .' * il.
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co, CH,,OR 1 - OTHER ADDITIVE FRITT
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FRIT 'TED CO, CH,.OR 4 ___ OTHER AD
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340 350 300 400 4 50 500 600 700 80
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0 554 WITH COOLING (PLATE AT 40°C)
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5 56 then t = to when e = 0 2) the
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5 58 The surface heat transfer coef
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Discussion and Results 560 Three br
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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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