secondary cells with lithium anodes and immobilized fused_salt

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I. Introduction 108. RE7IIEw OF ADVANCED INORGANIC OXIDIZFRS Edward W. Lawless and Robert J. Rowatt Midwest Research Institute, Kansas City, Missouri In this Faper the Froperties and chemistry of advanced inorganic oxidizers will be reviewed with emphasis on recent developments. The classes of compounds w i l l be limited to the cxyzen fluorides, the nitrogen fluorides, the nitrogen fluoride oxides, the halogen fluorides and the halogen fluoride oxides. In general, all %f the zompoucds described here are highly reactive, toxic materials, and very vola- tile exceat for ionic derivatives. The growth of chemistry involving 0-F, N-F and Cl-F comFounds has been remarkable: from about nil in 1946 to over 1030 today. 11. O.y:gen Fluorides and Derivatives The reported oxygen fluorides, their derivatives and some of their properties are summarized in Table I. Oxygen difluoride is the only binary compound of t?is tpe which 1s stable at room temperature, but 02F2 is stable below about -80% 3rd is -,e11 cheracteri-ed. A reasonably good understanding has been gained recently of the a?parent equilibrium system O4F2 e 202F. The existeice of O3F2 as a separate entity is in doubt, and the natures of the reported "O5F2" and "OgFg" are quite uncertain. Oxygen difluoride is comercially available, while the others are prepared by electrical discharge at low temceratures fron aporopriate O2-F2 mixtures. The ;tructures of OF2 and 02F2 have been determined and are compared in Figure 1 with those of related comnounds. The abnormally long 0-F distance and the greatly shortened 0-0 bond in 02F2 have led Linett to formulate its structure as zavirg an essentially four-electron 0-0 bond (as in 02 itself, 1.21 1 bond length) szd a one-electron 0-F bond (resonating between the two positions). Dioxygen difluoride can, therefore, readily dissociate at the 0-F bond t3 give F atoms and the stable 09 radical: az3 is an extremely energetic fluorinating agent. At low temperatures it is more reactive than fluorine itself and far more reactive than OF2. The latter compound begins to decompose near 23O0C and many of its reactions require activation by heat or light. The 02F- radical can be generated by ultraviolet radiation of liquid OF2, of 0F2-02, F2-02 or F2-N20 mixtures in a matrix, at 4'K, by the decomposition of 04F2 07 FSOpOOF, and in the reaction of CF4 with 02. The OF radical has never been detected in the gas or liquid phase despite an intensive search. The reactions o'f the oxygen fluorides are usually simple fluorinations, but oxygen addition by OF2 can occur especially in aqueous solution or i n reactions
I' 109. i TABLE I \ f OXYGEN FLUORIDES AND DERIVATIVES I Properties f ' cotmound MI', OC BP, 'C Decomp. Temp. -- I9F d I \\ '! w CF$( O)OF SF^ OF II020F c 103 OF FS0200F Observed in PI2 or Ar matrix at 4'R -- -223.8 -144.8 r~ 200 -249 liq. -248 g -163.5 -57 dec. -78 -865 -191 -80 ext -183 -825 -- -- -62.5 -86 -175 -167.3 -158.5 -21 -21.5 -35 -45.9 -15.9 -31.3 -50 (est) -15 (est) 0 -- -159 - tr, +84.2 -- -- tr -189 -- -226 -244.9, -36.2 +S?,? db, -291.5 qt +84.i ab of tr (CF3) +97.4 ab of qt ('3'2) -291.6 - tr of qt -- 19F chemical shift (ppm vs. CFC13=O) for fluorine of -OF group. Positions (cm-l) for 0-F stretching fundamental. Infrared 1028 1740, 929, 909, 880, 826, 461 1024, 628, 463 1519, 588 (04.F~) 1494, 484 (02F.) -- -- 1282, 1259, 1223, 1217, 945, 880, 679 1300, 1270, 1150, 950 qt -- 935, 888, 614, 585 1760, l300, 920, 810, 708 1298, 1049, 666 -- 1290, 1175, 955, 755, 725 1380, 1285, 1235, 1175, 740 ,
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Introduction 1. SECONDARY CELLS WIT
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I time curves at constant current d
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I 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11
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7. IV IV- Equivalent Weight, gr/ Eq
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1 3 9 SOYO FILLER,HQT PRESS Fig. 4.
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11. COAL PYROLYSIS USING LASER IRRA
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13. Macerals. Macerals from a singl
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i 1 I Photochemistry. A fundamental
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t P li. al ’ i ._ m LL
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' 19. PYROLYSIS OF COAL IN A MICROW
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I 21. In the third stage, the gas e
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.4 4 0 W 0 m .d m x .-( 0 x w M m s
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' 25. CONCLUSIONS The principal rea
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' .4 b s tract 28.
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30. the course of the experiment Ex
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d (Sulfur] dt m i trogenj dt 32. E
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34. Table 1, Properties of Feed Mat
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0 0 0 m 0 VI b N 0 c, VI N 0 v, N h
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- Literature Cited 38 1. Gordon, K
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40 z - B 30 w 6 20 yl w U 10 40. 10
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Z 0 In 80 CK W > 6 60- 0 I- 40- Z W
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44. 2.0 I 1.2 - 0 2 1.0- 0.8 i TIME
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- 2.81 1.NITROGEN 2. SULFUR 3. GASO
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48. The oil from the separator is v
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. 50 . Table I . Properties of Pitc
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52. Coke yield A - - - - 0 800 900
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FIGURE 8. 54. t 0.5 1 800 900 1,000
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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 86 and 87: , 86. Zeections of Cl30 and AsF5. M
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 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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