secondary cells with lithium anodes and immobilized fused_salt

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, 86. Zeections of Cl30 and AsF5. Measured iuantities of C120 (117 cc, 5.22 anoles) and A s F 5 - W , 3.79 mmoles) were seperately condensed into the reactor (glass or Teflon tubes) at -195O. The temperature wes changed to -78’ and it wes ojserved that the nixed reactants gradually developed a dark red color. Pun?ing on the mixture after e few hours at -78’ resulted in the recovery of sone of the starting materials and much C12. Subsequent werning of the reaction to arbient temperature gave additiowl small amounts of enseous materials End a white solid. Little or no -196O non-condenseble qases were observed throughout the reection. In all, 111 cc of volatile products were obtained. Infrared and p s chromatographic analysis indicated these products to be a mixture of AsF (17.5 cc, 0.78 5 mole) and C12 (93.5 cc, 4.17 mmoles) with e trace of C102 and no C1 0. The observed reactant-product ratio of C1 0:AsF :C1 was 5.00:2.86:4.01. Similar 2 5 reaction ratios were obtained when C1 0 WRS use$ as the excess reagent. The solid product showed two infrared bcn& 1280 cm” (m, doublet) and 690 to 700 cm-’ (8. broad). Based on the observed stoichi netry of the reaction and the known infrered frequencies of C1-06 and AaF 7 compounds, it appeared . the solid night be principally C102AsF6. w8s prepared. \ Accordingly, en authentic sample PreparRtion of C103AsF . Chloryl fluoride (lil cc, 4.96 molaa) and AsFg (63.7 cc, 2.04 rnmol*were seperately condensed intc a Teflon ampoule at -196O. After 1 hour at room tempersture, the unreacted gases were removed snd meqsured (48.0 cc, 2.14 mnoles). An infrared spectrum showed only CC102. The white solid product had an infrered spectrum identical to that of the solid from the C120-AsF reaction. In addition, both solids fumed in air and exploded on contac? with water. Powder X-ray patterns of both sclids were obtained and were identical. relative intensities are given ir. Table 1. The observed spacings and Reaction of C10 .AsF5 and NO2. Weiahed amcunts of C102AsF6 and excess NO? PRS were reactedLfor 1 hour at 0’. WRS ac.”,ieved but in poor yield; 20;6 for the solid from the C1 2 0 renction nnd 3516 for the z3lii from the FC102 reaction. The exr,ected displacement’ of C102 . , .. -------------_-_---_------------------ (5) V. H. hyen md 3. C. lieale, Advances in Chemistry Series, No. 54, kerican Cherical Society, Wsshincton, D. C., 1966, p. 223. (6) E. A. aobinson, Can. J. Chem., fi, 3021 (1963). (7) B. Peacock end D. Sharp, J. Chem. Soc.,_1766 (1959). (8) H. Scbeisser and ’d. Fink, Anaew. Chem., a, 780 (1957).
, 87. TABU 1 X-RAY POWDER DIF'FRACTION DATA FOR C1O2bF6 d. 51 Relative Intensity d. A Relative Intensity 7.50 70 2.30 10 5.55 5.10 30 30 ?.OR 7.05 60 60 4.40 70 1 e95 40 4.02 40 1.87 10 3.65 3.57 100 90 1 .a4 1 .a0 10 10 ?.&9 10 1.76 10 3.07 2.87 2.76 2.69 50 - 'lo - z ' lo 10 c 10 1.70 1.59 1.55 1.57 20 15 10 10 2.54 - fiepetion of PF5C12 and Cl10. A 1:1 mixture of PF C1 and Cl2O was 7 2 alloded to V ~ X T to room tempewture at which point pn infrared spectrum was tr.ken. ?!.e only infrared absorbinq material prePent WRS POF,. None of the PF7Cl , 8 strong intrnred absorber,. remined. ?he by-prdduct C12 was reveeled by its color when frozen. Wo non-voletile solids were observed. ' .';< . I e., Zesults wid Discussion The reaction bf C1 0 with AsF does cot give the odd molec,de ClOAsF 5 but Fives instep< %'hp szlt C1O2AsF2. Further, the reaction.eppesrs to follow the stoichiometry shown in equetion 1: 5Cl2O + 3AsF 5 2C102AsF6 + 4C12 + AsOF, (1) The resction stoichiometry does not appar to be de2endent on the experi- mente1 reactant mtios. The formation of C10 AsF w2s confirmed by preparing an quthentic sazgle find compering their X-ray2pateerns. FC102 + AsF5 _3 C102AsF6 (2) - In the reaction of C1 0 with AsF5, the evciution of C1 apparently involyes 2 2 r~ch more com?lcx process thqn 2 sicple C1-0 bond rupture. The equation reaortedl for this procesc st -50' is s5own in equation 3: C120*AsF 5 C10AsF5 + 1/2 Clp (3) We would prefer to propose an initial step thet infers an ionization of C1 0, i.e., sn ionic comnlex is obtpined, perhaps ClO+AsF C1-: 2 5 Cl20 + AsF5 __* CIOAsFSCl (4) The oxidfition of the C10+ species could then proceed with ad3itional C1 0: 2 Cl20 + C10AsF5C1 __+ C1O2AsF5C1 + C12 This step (aqustion 4) should not be considered unusual inasmuch as other chlorine oxi4es are capsble of redox (e.g., C102 gives some C1206 on photolysis9) - (5)
Page 1 and 2:
Introduction 1. SECONDARY CELLS WIT
Page 3 and 4:
I time curves at constant current d
Page 5 and 6:
I 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11
Page 7 and 8:
7. IV IV- Equivalent Weight, gr/ Eq
Page 9 and 10:
1 3 9 SOYO FILLER,HQT PRESS Fig. 4.
Page 11 and 12:
11. COAL PYROLYSIS USING LASER IRRA
Page 13 and 14:
13. Macerals. Macerals from a singl
Page 15 and 16:
i 1 I Photochemistry. A fundamental
Page 17 and 18:
t P li. al ’ i ._ m LL
Page 19 and 20:
' 19. PYROLYSIS OF COAL IN A MICROW
Page 21 and 22:
I 21. In the third stage, the gas e
Page 23 and 24:
.4 4 0 W 0 m .d m x .-( 0 x w M m s
Page 25 and 26:
' 25. CONCLUSIONS The principal rea
Page 28 and 29:
' .4 b s tract 28.
Page 30 and 31:
30. the course of the experiment Ex
Page 32 and 33:
d (Sulfur] dt m i trogenj dt 32. E
Page 34 and 35:
34. Table 1, Properties of Feed Mat
Page 36 and 37: 0 0 0 m 0 VI b N 0 c, VI N 0 v, N h
Page 38 and 39: - Literature Cited 38 1. Gordon, K
Page 40 and 41: 40 z - B 30 w 6 20 yl w U 10 40. 10
Page 42 and 43: Z 0 In 80 CK W > 6 60- 0 I- 40- Z W
Page 44 and 45: 44. 2.0 I 1.2 - 0 2 1.0- 0.8 i TIME
Page 46 and 47: - 2.81 1.NITROGEN 2. SULFUR 3. GASO
Page 48 and 49: 48. The oil from the separator is v
Page 50 and 51: . 50 . Table I . Properties of Pitc
Page 52 and 53: 52. Coke yield A - - - - 0 800 900
Page 54 and 55: FIGURE 8. 54. t 0.5 1 800 900 1,000
Page 56 and 57: Introduction 56. FLUORODINITROETUNO
Page 58 and 59: chloride extractant without other h
Page 60 and 61: 60. identified (Reference 7) as the
Page 62 and 63: 62. to FEFO -e quite high (80 to 85
Page 64 and 65: 64. RECENT CHEMISTRY OF THE OXYGEN
Page 66 and 67: polymers for the conventional fuel
Page 68 and 69: 68. In summary, two general methods
Page 70 and 71: 70. Table XI1 Differential Thermal
Page 72 and 73: vapor Pressure (psia) Figure 4. Vap
Page 74 and 75: C H -0-C-NHF, - 2 5 II 0 74. H 9304
Page 76 and 77: 76. The infrared spectrum is descri
Page 78 and 79: , 78. PREPARATION AND POLYMERIZATIO
Page 80 and 81: . .- . - ..... . . I ,caving the re
Page 82 and 83: If it ~ 3 ~ o~t 7 s Y'2t the therm1
Page 84 and 85: Chlorine Fentafluaride T q D OC 252
Page 88 and 89: aa . - The rrost difficult rctionel
Page 90 and 91: 90. DENSITY, VISCOSITY AND SURFACE
Page 92 and 93: 92. If it is assumed that the syste
Page 94 and 95: 94. After condensation of oxidizer
Page 96 and 97: Stirring Solenoid LHe 7. Cryostat 9
Page 98 and 99: Introduction 98. RFACTIONS OF OxYcm
Page 100 and 101: , Acknowledgement 100. This work wa
Page 102 and 103: 102. volume and then by pumping to
Page 104 and 105: 104. The x-ray powder pattern (Tabl
Page 106 and 107: Irredie tion Time, mi&) 106. Table
Page 108 and 109: I. Introduction 108. RE7IIEw OF ADV
Page 110 and 111: 1.40 w F O/) 103-4O 'F 110. /H 0 21
Page 112 and 113: !P, "c -- -2118.5 -195 -172 -16.1 .
Page 114 and 115: 114. weaker than those in NF02. The
Page 116 and 117: Compound C102F ~ 1 , 0 ~ -146 ~ 116
Page 118 and 119: 118. fom such salts as cS+m8- have
Page 120 and 121: 120. DETONABILITY TESTING AT NONAMB
Page 122 and 123: I 122. top) is closed with caps whi
Page 124 and 125: 124. five pieces of MDF, each 20.00
Page 126 and 127: 126. auxiliary equipment. For conve
Page 128 and 129: 128. reliability. Details of most o
Page 130 and 131: 130. The time required for the deto
Page 132 and 133: 132. Fig. 2 Typical Witness Plate
Page 134 and 135: I ll 134. L, ALUMINUM 011+ ‘7 I-
Page 136:
W (3 3 a (3 W m 3 0 v) W E k- / W 3
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