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PU13 PU(103)3 PU(103)4 PU02 PU(OH)3 PU(OH)4 PU02(OH)2 PU peroxide MPU(S04)2> M=Na, K, Rb, CS, NH4 PU(S04)2 M4Pu(S04)4, M=K, Rb, NH4 P;(N03)4 M2Pu(N03),6, M=K, Rb, POP04 PU(HP04)2. XH20 PU2H(P04)3. yH20 PU3(P04)4. ZH20 Put, PU2C3 PUOC03 K6[pu(co3)510 mH20 K4[Pu(C03)41. mH20 K12 [ pu(co3)d omH20 M4[Pu02(C03)3] , M=K, HPUFe(c~)6° xH20 PuFe(CN)6 Pu3[Fe(CN)6] 4. XH20 (Pu02)3[Fe@’)6] 2“ ‘H20 PU2(C204)3 .xH20 PU(C204)2 “6H20 PU02(C204)-3H20 NaPu02(C2H302)2 Cs, T1 NH4 TABLE IV-3 (Cont. ) s. H20 s. HN03, i. H2S04-K103, excess mo3 s. HN03, decomposed in H2S03 s. slowly in boiling mineral acids; reaction speeded by fusion with NaHS04 or HF added to HN03; solubilit y is more cliff icult if ignited above 500° s. mineral acid s. mineral acid s. mineral acid, Ksp = 1.8 X. 10-23 s, cone. HN03, H2S04 i. M2S04-H2S04, S. H20 alcohol s. H20, i. alcohol s. H20, i. alcohol s. H O, colloidal Pu forms in aque 3us soln. s. HN03, ether, acetone i. cone. HTJ03, ‘. H20’ ‘il acid S. hot cone. mineral acid; s1. S. H3P04, NaOH; i. HC2H302 i. mineral acid - H3P04 s. HC1, H2S04, i. cold cone HN03 S. hot cone. HN03-NaF2 i. H20, s1. s. cold mineral acids i. alcohol :: ~:::$a:~co,, d. s. H20, i. HC1 i. HC1 i. HC1 i. HC1 i. H20, s. minersl acid; s1. S. K2C204. (NH4)2C204 Reference 264 i. H2Cl, s. H2S04, HN03, HC104 s1- s. acid-K2C204, NH2C 204 minimum s. in 1.5 ~ HN03 - 0.025 M ‘2c204 264 S. mineral acid; s1. s, acid – ‘2C 2°4 s1. s. hot H20, s. acid 7
* Compiled primarily from the reviews of Cunningham and Faugeras and Heuberger Unless otherwise ** The following specified, the data are taken abbreviations are used: from these reviews. s. soluble i. insoluble S1. s. slightly soluble cone. concentrated dil. dilute C.1 Oxidation States C. Plutonium Ions in Solution Plutonium in aqueous solution exists in the +3, +4, +5, or +6 oxidation states, resembling both uranium (U), neptunium (Np) and americillm (Am) in this respect, The formal oxidation potential diagrams for Pu in acid and basic solution are taken from Latimer. 2’0 ACID SOLUTION BASIC SOLUTION Pu ~ ~(oH1 o 95 - PU(OH)4 u PU020H = PU02(OH)2 3 -0.51 Formal oxidation potentials for Pu couples in various 1 ~ solutions are shown in Table IV-.4. The displacements of the potentials are due to the complex-forming tendencies of the anions with Pu. TABLE PJ-4. Formal Potentials for Pu Couples in Various 1 ~ Solutions PU(III)-PU(IV) Pu(IW)-PU(VI) Pu(fII)-Pu(VI) Pu(v) -PU(VI) HC104 -0.982 -1.043 -1.023 -0.92 HC1 -0.970 -1.052 -1.024 -0.912 HN03 -0.92 -1.05 -1.04 ------ H2S04 -0.74 -1.2- 1.4 ------ ------ The lower oxidation states become more stable in the actinide series from U to Am, and correspondingly the higher oxidation states become more difficult to attain. This effect is illustrated in Table IV-5, which shows the free energies of formation of various actinide ions. 128
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 and 10: IL GENEWL REVDZWS OF THE RADIWHEMIS
Page 11 and 12: IV. CHEMISTRY OF PLUTONIUM OF SPECI
Page 13: Solution TABLE IV-2. Behavior of PU
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
Page 77 and 78:
cupferron, followed by back extract
Page 79 and 80:
. more. Siekierski and Taube, 381 a
Page 81 and 82:
TABLE IV- 27. Slope of the Dependen
Page 83 and 84:
polymerization of the resin to prov
Page 85 and 86:
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.
Page 93 and 94:
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
Page 103 and 104:
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
Page 129 and 130:
Procedure 6. Separation of Plutoniu
Page 131 and 132:
Procedure 7. Determination of Pu (R
Page 133 and 134:
Procedure 8. Uranium and Plutonium
Page 135 and 136:
15. Add 3 drops of HC1 and 1 drop o
Page 137 and 138:
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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