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., ~ - TABLE OF ISOTOPES OF pLuTo~M* Specific a Particle Activity Type of Energy Isotope Half Life (d/m/pg) Decay (MeV) Method of Preparation ~u232 PU23 3 ~u234 PU235 PU236 ~u237 ~u238 Pu 239 PU240 PU241 PU242 PU243 PU244 ~u245 PU246 36 min 20 min 9,0 hr 26 min -- -- .- -- 2.85 yr 1.18X 109 45.6 days -- 86.4 yr 3.88 X 107 24,360 yr 1.36 X 105 6,580 yr 5.00 x 105 0’270, 6.58 EC 98$ U235 + 100 MeV a particles ao.lye, 6.30 ~233 + 40 MeV D EC99+7’0 particles 067’0, 6.19 EC 9470 a3 x 10-37., 5.85 EC 99 + ~. c1 5.763 (69~o) 5.716 (317’0) ao. oo370, 5.36 (797’0) EC 99+% 5.65 (217’0) a 5.495 (72~0) 5.452 (28%) a 5.147 (737’0) 5.134 (1770) 5.096 (10~0) c1 5.162 (76%) 5.118 (24%) 13,0 y-r 2.57 X 108 a4 X 10-370, 4.89 ,B-99+7’O 3,79 x 105 8.65 X 103 w (Y 4.898 (767. ) 4.858 (2470) 4.98 hr -- P- --- 7.6X107 42.8 w- 10.6 hr -- 10.85 days -- (2 P- fl- --- --- --- U233, 235 + 40 MeV a particles Daughter of Cm238 U233, 235 + 20-30 MeV a particles ~235 + 40 MeV a particles Daughter Np23 6 Daughter Cm240 U235 + 40 MeV Qparticles ~238 + deuterons Dau hter Cm242 Pu2 $ 9 + high energy neutrons Np237 + neutrons U238 + neutrons ~238 + neutrons PU239 + neutrons Daughter of Cm244 U238 + neutrons Dau hter of Cm245 u23 i? + a particles U238 + neutrons Am241 + neutrons PU242 + neutrona PU244 + neutrons ~238 + neutrons (ther - % The data for this table were taken from the recent review of Hyde. 192 Tfiis work should be consulted for further details and references to the literature. 3
IV. CHEMISTRY OF PLUTONIUM OF SPECIAL INTEREST TO THE RADIOCHEMIST A.1 Preparation A. Metallic Plutonium Plutonium metal is most commonly prepare~8by the reduction ,of a halide by a more electropositive metal such as calcium. Connor has compared various combinations of halide and reducing metal and found that the only satisfactory reactions were PuF3, 164 PuF , and PuC13 reduced with Ca metal. Harmon and Reas and 0rth306 have discussed the conversion of Pu salts to metal on an industrial scale, while Anselin, et al.30 describe a method for the conversion on a gram scale. A.2 Physical Properties Pu is a typically silver-white appearing metal which has a number of peculiar physical properties. The metal undergoes a total of five allotropic modifications below the melting point, two of which have negative coefficients of thermal expansion. Table IV-1 summarizes the more important physical properties. A.3 Chemical Properties Pu is a very reactive metal. The potential for the couple Pu = PU*+ + e- is 2.03 volts, which places it between scandium (Se) and thorium (Th) in the EMF series of elements. Pu oxidizes more readily than does U, snd resembles cerium (Cc) in its reactions in air. Superficial oxidation of a freshly prepared surface occurs in a few hours in normal air. The oxide is more or less adherent, and in several days the oxidation reaction accelerates until finally the oxidation to PU02 is complete. However, the oxide coating protects the underlying metal in dry air. and the oxidation proceeds more slowly. Pu metal is attacked at elevated temperatures by most gases; Hz, N2, halogens, S02, etc. Pu metal dissolves easily and rapidly in moderately concentrated HC1 and other halogen acids. Pu forms intermetallic compounds with intermediate solid solutions with most metallic elements. However, simple eutectic mixtures are usually made with the group Va and VIa ‘“metals, and very little volubility in either the liquid or solid state is ex- : hibited by alkali and alkaline earth metals. The behavior of Pu toward various solutions is given in Table IV-2. -4-
Page 1 and 2: 1National Academy of Sciences Natio
Page 3 and 4: The Radiochemistry of Plutonium. Ge
Page 5 and 6: PREFACE This report has been prepar
Page 7 and 8: Procedures (Continued) CONTENTS (Co
Page 9: IL GENEWL REVDZWS OF THE RADIWHEMIS
Page 13 and 14: Solution TABLE IV-2. Behavior of PU
Page 15 and 16: * Compiled primarily from the revie
Page 17 and 18: TABLE IV-6. Oxidation-Reduction Rea
Page 19 and 20: c.. Pu(IV)+ Pu(VI) Reagents Solutio
Page 21 and 22: Concentration Equilibrium Constant
Page 23 and 24: PU+4 has approximately the same ten
Page 25 and 26: TABLE IV- 9. Ionic Potential of Plu
Page 27 and 28: TABLE IV- 11. Stabflity Conetants o
Page 29 and 30: TABLE IV- 12. Stability Constants o
Page 31 and 32: D. 1 Co-precipitation and Precipita
Page 33 and 34: is first oxidized to Pu(VI) with so
Page 35 and 36: oxygen in the ratio 1:3. If an exce
Page 37 and 38: the TBP cone entration. Solovkin 39
Page 39 and 40: D, l? D Ic n. 0 5 10 Concentration
Page 41 and 42: D 103 ~ ,.2 _ 10 I H ,0-1 ~ / P / P
Page 43 and 44: 100( I0( 1( D 1.( 0. 0.0 0.00 Nltrl
Page 45 and 46: Table IV- 16. (Continued) Extractan
Page 47 and 48: Table IV-16. (Continued) Extr actan
Page 49 and 50: In this equation, HA represents any
Page 51 and 52: X[N05] = [HN03] ‘( ~ ~[N03] = HN0
Page 53 and 54: Di-acidic compounds. Mono-2- ethylh
Page 55 and 56: A may be either a simple anion or t
Page 57 and 58: n 104 d Id 10 I 10-1 , a ,,81 0.1 M
Page 59 and 60: The fact that Pu(III) does not extr
Page 61 and 62:
Fig. 25. Extraction of elements as
Page 63 and 64:
TABLE IV- 19. Distribution Coeffici
Page 65 and 66:
10~ I ~ 0.01~ D 0.001 : 0,0001 . La
Page 67 and 68:
loi- 1“’’’’’’’”1
Page 69 and 70:
TABLE IV- 22. Extraction of Plutoni
Page 71 and 72:
m * Amideb N, N-Dihexylformamide N,
Page 73 and 74:
dependence on the TTA concentration
Page 75 and 76:
1.0 D 0.1 —--L~,20 HNOO; CO&NT R
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cupferron, followed by back extract
Page 79 and 80:
. more. Siekierski and Taube, 381 a
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TABLE IV- 27. Slope of the Dependen
Page 83 and 84:
polymerization of the resin to prov
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co ; n 1000L z - 100 z o ~ m oL x z
Page 87 and 88:
Volume distribution coefficient of
Page 89 and 90:
affinity of several ions was Th(IV)
Page 91 and 92:
95% of Pu(IV) was removed from a 0.
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2 d 1.0 I I I 1 I I 1 ,, , , I II r
Page 95 and 96:
X“ 104 , 1 1 1 1 1 .— .-. I Ioa
Page 97 and 98:
200 100 50 20 I O.10 ~ $ NPIX PUIIT
Page 99 and 100:
Fig. 54. Adsorption of the elements
Page 101 and 102:
Toribara et al. 403 used a liquid s
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V. DISSOLUTION OF PLUTON17JM SAMPLE
Page 105 and 106:
m m TABLE VI- 30. Source Preparatio
Page 107 and 108:
o 0 TAIIT.E VI-31. Techniques for M
Page 109 and 110:
Solvent extraction of Pu into a liq
Page 111 and 112:
TABLE VII-33. Basic Data for Critic
Page 113 and 114:
Procedure No. 6. 7. 8. 9a, 9b , Aut
Page 115 and 116:
Procedure 1. Determination of Pu in
Page 117 and 118:
(e) (f) (g) (h) Where C v E The pre
Page 119 and 120:
Procedure 2. Separation and determi
Page 121 and 122:
Procedure 3. Separation and determi
Page 123 and 124:
Procedure 4. Plutonium R. J. Morrow
Page 125 and 126:
Procedure 5. Plutonium D. C, Hoffma
Page 127 and 128:
Procedure m. Pipet tie samples (2~i
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Procedure 6. Separation of Plutoniu
Page 131 and 132:
Procedure 7. Determination of Pu (R
Page 133 and 134:
Procedure 8. Uranium and Plutonium
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15. Add 3 drops of HC1 and 1 drop o
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Procedure 9b. Separation of Plutoni
Page 139 and 140:
Procedure 11. Uranium and Plutonium
Page 141 and 142:
Procedure 12. Plutonium from Enviro
Page 143 and 144:
9. 10. 11. 12. 13. 14. 15. 16. 17.
Page 145 and 146:
10. 11. 12. 13. 14. 15. 16. 17. 16.
Page 147 and 148:
Procedure 14. Separation of Plutoni
Page 149 and 150:
Procedure 15. Separation of Pu befo
Page 151 and 152:
Procedure 16. Separation of Plutoni
Page 153 and 154:
Appendix (m) (n) (o) (P) Purificati
Page 155 and 156:
Procedure 17. Separation of Np and
Page 157 and 158:
Procedure 19. Determination of Plut
Page 159 and 160:
NOTE: Reporting Results Results are
Page 161 and 162:
Notes .. 1. 2. 3. The element prase
Page 163 and 164:
3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13
Page 165 and 166:
Procedure 22. Determination of Amer
Page 167 and 168:
concentrated nitric acid in a block
Page 169 and 170:
Preparation of Sample The 24-hr or
Page 171 and 172:
Page 173 and 174:
Page 175 and 176:
“The Actinide Elements” (McGraw
Page 177 and 178:
48. D. H. Boase, J. K. Foreman, and
Page 179 and 180:
108. 109. 110. 111. 112. 113, 114.
Page 181 and 182:
159. 160. 161. 162. 163. 164. 165.
Page 183 and 184:
217. W. E. Keder, J. Inorg. Nucl. C
Page 185 and 186:
279. 280. 281. 282. 283. 284. 285.
Page 187 and 188:
339. 340. 341. 342. 343. 344. 345.
Page 189 and 190:
397. 398. 399. 400. 401. 402. 403.
Page 191 and 192:
451. C. E. Honey, Jr., R. N. R. Mul
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