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9.2 Aqueous neptunium group 17 (halogen) complexes 171Table 9.8: Experimental equilibrium data for the neptunium(VI) chloride system.Method Ionic medium t ( ◦ C) log 10 β (a) q log 10 βq◦(a)NpO 2+2 + Cl − Å NpO 2 Cl +Referencekin 3 M H(Cl,ClO 4 ) 0.0 0.21 (c) [55COH/SUL]3MH(Cl,ClO 4 ) 0.0 0.10 (d)3MH(Cl,ClO 4 ) 4.78 0.06 (c)3MH(Cl,ClO 4 ) 4.78 0.00 (d)3MH(Cl,ClO 4 ) 9.84 −0.06 (c)3MH(Cl,ClO 4 ) 9.84 −0.09 (d)3MH(Cl,ClO 4 ) 25 −(0.37±0.20) (b,d,e) (0.29±0.49)sp 2M Na(Cl,ClO 4 ) 25 −0.21 [62SYK/TAY]emf 0.3 M H(Cl,ClO 4 ) 25 −(0.32±0.40) (b) (0.26±0.40) [70AL-/WAI2]0.4 M H(Cl,ClO 4 ) 25 −(0.36±0.40) (b) (0.26±0.40)0.5 M H(Cl,ClO 4 ) 25 −(0.35±0.40) (b) (0.31±0.41)dis 4 M (H,Na)(Cl,ClO 4 ) 25 −(0.16±0.20) (b) (0.41±0.66) [71DAN/CHI]emf 4 M (H,Na)(Cl,ClO 4 ) 25 −(0.05±0.20) (b) (0.52±0.66) [74DAN/CHI]dis 2 M H(Cl,ClO 4 ) 25 −(0.04±0.20) (b) (0.68±0.35) [78BED/FID]NpO 2+2 + 2Cl − Å NpO 2 Cl 2 (aq)kin 3 M H(Cl,ClO 4 ) 0.0 −0.80 [55COH/SUL]3MH(Cl,ClO 4 ) 4.78 −0.743MH(Cl,ClO 4 ) 9.84 −0.703MH(Cl,ClO 4 ) 25 −(0.56±0.40) (b,e) −(0.7±0.8)dis 2 M H(Cl,ClO 4 ) 25 −(0.57±0.40) (b) −(0.2±0.6) [78BED/FID](a) Refers to the reactions indicated, the ionic medium and temperature given in the table. log 10 βq ◦ isin molal units, at I = 0 and 298.15 K.(b) Uncertainty estimated in this review.(c) Refers to the model containing only a 1:1 complex.(d) Refers to the model containing a both 1:1 and a 1:2 complex.(e) Extrapolated to 25 ◦ Cinthisreview(cf. Appendix A).9.2.3 Aqueous neptunium bromide complexes9.2.3.1 Aqueous Np(III) bromidesQuantitative information on bromide complexation of Np 3+ has only been publishedby Shiloh and Marcus [64SHI/MAR] in concentrated LiBr solutions of varying ionicstrength up to near 12 M. The authors gave formation constants for NpBr 2+ (log 10 β 1 =−(3.39 ± 0.06)) and NpBr + 2(log 10 β 2 =−(6.48 ± 0.05)). These very negative valuesfor the formation constants correspond to the complexation of only about 1% ofNp(III) at the highest bromide concentration used in the experiment, which was probablybarely detectable. Also, the ionic strength effects are expected to be considerableunder these conditions. An extrapolation to I = 0 is not possible due to the lack of
172 9. Neptunium group 17 (halogen) compounds and complexesgood estimates of ionic interactions, and no standard formation value can be selectedhere.9.2.3.2 Aqueous Np(IV) bromidesThe only experimental equilibrium data available on the reactionsNp 4+ + qBr − Å NpBr 4−qq (9.12)are from Raghavan, Ramakrishna and Patil [75RAG/RAM] atI = 2 M (HBr, HClO 4 )and 25 ◦ C. The reported constants are lower than those of the analogous uranium andplutonium complexes: log 10 β 1 (9.12, q = 1) =−(0.21±0.01) and log 10 β 2 (9.12, q =2) =−(0.57±0.03). The cause for the deviation could be experimental limitations, cf.comments in Appendix A. For the corresponding bromide complexes of Pu(IV) (Section18.2.3.2) andU(IV)[92GRE/FUG], as well as for the Np(IV) complexes NpCl 3+and NpI 3+ ,logK1 ◦ values between 1.25 and 1.8 are obtained, and the complexationconstant of NpBr 3+ is also expected to lie in the same range. However, on the weakbasis of the available experimental information, it is not possible to select any constantfor the Np(IV) bromide complexes.9.2.3.3 Aqueous Np(V) and Np(VI) bromidesNo aqueous species of the form NpO 2 Br 1−qqidentified.9.2.4 Aqueous neptunium iodine complexes9.2.4.1 Aqueous neptunium iodides9.2.4.1.a Aqueous Np(III) iodidesNo aqueous species of the form NpI 3−qq have been identified.or NpO 2 Br 2−qq , respectively, have been9.2.4.1.b Aqueous Np(IV) iodidesQuantitative information on iodide complexation of Np 4+ has been published by Kusumakumariet al. [79KUS/GAN] and Patil, Ramakrishna and Gudi [81PAT/RAM] onthe equilibriumNp 4+ + I − Å NpI 3+ . (9.13)The results are summarised in Table 9.9. The values originate all from Patil’sgroup and are from solvent extraction studies (see Appendix A). It should bementioned that the review paper [78PAT/RAM], which is cited in the IAEAreview [92FUG/KHO], reports two new values referring to unpublished work ofRao, Bagawde, Ramakrishna and Patil, and these values were published later in[79KUS/GAN]. Some of the papers contain little experimental details, but we can
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4VOLUMECHEMICALTHERMODYNAMICSCHEMIC
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CHEMICAL THERMODYNAMICSVol. 1. Chem
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Published under the imprint NORTH-H
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viPREFACEviewed several of the othe
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viiiACKNOWLEDGEMENTSand Whiteshell
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xFOREWORDsending comments on the TD
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xiiCONTENTSIII Discussion of neptun
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xivCONTENTS11.1.4.2 Solid neptunium
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CONTENTSxvii20.5.1 PuSb(cr) . . . .
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List of Tables2.1 Symbols and termi
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LIST OF TABLESxxi20.2 Experimental
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List of Figures2.1 Standard order o
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Part IIntroductory material1
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4 1. IntroductionInorganic Complexe
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6 1. Introductionlected, but form a
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Chapter 2Standards, Conventions, an
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2.1 Symbols, terminology and nomenc
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2.2 Units and conversion factors 23
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2.2 Units and conversion factors 25
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2.3 Standard and reference conditio
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2.3 Standard and reference conditio
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2.5 Uncertainty estimates 31Table 2
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2.7 Presentation of the selected da
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2.7 Presentation of the selected da
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Chapter 3Selected neptunium dataThi
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41Table 3.1: Selected thermodynamic
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43Table 3.1: (continued)Compound f
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49Table 3.2: (continued)SpeciesReac
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Chapter 4Selected plutonium dataThi
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61SpeciesPu(OH) 3 (cr)ReactionTable
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Chapter 5Selected auxiliary dataThi
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(footnotes continued)(p) Data from
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79Table 5.2: (continued)Species Rea
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81Table 5.2: (continued)Species Rea
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Chapter 6Elemental neptunium6.1 Nep
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6.1 Neptunium crystal and liquid 87
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6.2 Neptunium ideal monatomic gas 8
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92 7. Neptunium aqua ionsE ◦′ (
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94 7. Neptunium aqua ionsto the sta
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96 7. Neptunium aqua ions(∂ E ◦
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98 7. Neptunium aqua ionsnon-system
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100 7. Neptunium aqua ionsto the re
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102 7. Neptunium aqua ionsTable 7.4
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Chapter 8Neptunium oxygen andhydrog
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8.1 Aqueous neptunium hydroxide com
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8.2 Crystalline and amorphous neptu
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8.2 Crystalline and amorphous neptu
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12.1 Neptunium carbon compounds and
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sp 0.1 M NaCl 23 (4.68±0.03) [96RU
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dis 0.2 M NaClO 25 2.93 (3.42±1.0)
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sol 1 M NaCl 23 (2.06±0.13) [96RUN
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sol 0.15 M Na 2 CO 3 −(2.58±0.64
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sol 1 M NaClO 30 −(4.0±0.2) [93L
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sol 3 M NaClO 25 −(2.14±0.18)
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(f) Values selected in this review
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(V vs. SHE) (V vs. SHE) (V · K −
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(h) 1MK 2 CO 3 is written in Table
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2 3 r H m (5.0±2.0)log 10 β 2 MO
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290 13. Neptunium group 2 (alkaline
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292 14. Neptunium group 1 (alkali)
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Part IVDiscussion of plutonium data
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298 15. Elemental plutoniumTable 15
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300 15. Elemental plutoniumfrom 298
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302 16. Plutonium aqua ionsthe prop
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304 16. Plutonium aqua ions298.15 K
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306 16. Plutonium aqua ionsE ◦ =
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308 16. Plutonium aqua ionsSm ◦ (
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310 16. Plutonium aqua ionsstandard
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312 16. Plutonium aqua ions r H ◦
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314 16. Plutonium aqua ionsE ◦′
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316 16. Plutonium aqua ionsFigure 1
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318 17. Plutonium oxygen and hydrog
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1:1 pot RT 1 M NaClO 4 −5.71 [49K
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Chapter 18Plutonium group 17 (halog
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18.1 Plutonium halide compounds 347
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18.2 Aqueous plutonium group 17 (ha
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PuO 2+2+ 3F − Å PuO 2 F − (b)3
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390 19. Plutonium group 16 compound
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Chapter 20Plutonium group 15 compou
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20.1 Plutonium nitrogen compounds a
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Pu + NO 3Å PuNO 3sp 2 M HClO 4 20
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3 3 3dis, TTA 6 M (? HCl or HClO 4
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20.2 Plutonium phosphorus compounds
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20.2 Plutonium phosphorus compounds
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20.3 Solid plutonium phosphorus com
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20.4 Plutonium arsenic compounds 42
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20.6 The plutonium-bismuth system 4
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20.6 The plutonium-bismuth system 4
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446 22. Plutonium group 2 (alkaline
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Chapter 23Plutonium group 1 (alkali
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452 BIBLIOGRAPHY[47GIN/COR][48KRA/N
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454 BIBLIOGRAPHY[49MAG/LAC][49ROB][
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456 BIBLIOGRAPHY[51WES/EYR][51WES/W
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458 BIBLIOGRAPHY[55COH/SUL]Cohen, D
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460 BIBLIOGRAPHYmetals in connectio
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462 BIBLIOGRAPHY[59SHE/TIM][59STU][
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464 BIBLIOGRAPHY[61SCH][61STO/FRY][
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466 BIBLIOGRAPHY[63ROB/WAL] Roberts
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468 BIBLIOGRAPHY[64SIL/MAR][65CHO/K
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470 BIBLIOGRAPHY[66DAN/ORL][66FRO/K
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472 BIBLIOGRAPHY[67ERM/STA][67FRL/C
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474 BIBLIOGRAPHY[68KRU/SAV][68KRY/K
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476 BIBLIOGRAPHY[69KEN/LEA][69KRY/K
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478 BIBLIOGRAPHY[70HIN/COB][70KRO/G
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480 BIBLIOGRAPHY[71MOS][71MOS2][71M
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482 BIBLIOGRAPHY[72MET/GUI][72NIK/S
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484 BIBLIOGRAPHY[73PAT/RAM2][73PIT]
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486 BIBLIOGRAPHY[74SAV][74SIM/VOL][
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488 BIBLIOGRAPHY[75OSB/FLO][75PAT/R
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490 BIBLIOGRAPHY298.15 K”, J. Che
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492 BIBLIOGRAPHY[76VOL/VIS][77BAG/R
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494 BIBLIOGRAPHY[78HAL/LEE][78HUR][
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496 BIBLIOGRAPHYof plutonium(IV)”
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498 BIBLIOGRAPHYNa 0.6 NpO 2 (CO 3
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500 BIBLIOGRAPHY[81CHI/AKH][81CIA/F
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502 BIBLIOGRAPHY[81WOO][82ALC/ROB][
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504 BIBLIOGRAPHY[83ALL][83BES/LIN][
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506 BIBLIOGRAPHY[83SCH/GOR]Schmidt,
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508 BIBLIOGRAPHY[84LEM][84LIE/KIM][
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510 BIBLIOGRAPHY[85CÔM][85EIS/KIM]
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512 BIBLIOGRAPHY[85NEW/SUL][85RAI/R
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514 BIBLIOGRAPHY[86FAH][86FRE/KEL]F
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516 BIBLIOGRAPHY[87BEN][87BEN/HOF][
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518 BIBLIOGRAPHY[88HIR/LIE][88ITU][
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520 BIBLIOGRAPHYGeochim. Cosmochim.
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522 BIBLIOGRAPHY[90BEN][90CAP/VIT][
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524 BIBLIOGRAPHY254, 258, 258, 264,
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526 BIBLIOGRAPHY[91MEI][91NIT][91OK
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528 BIBLIOGRAPHYment”, Waste Mana
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530 BIBLIOGRAPHY[93ERI/NDA][93GIF/V
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532 BIBLIOGRAPHY[93TAY/LEM][93WEG/O
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534 BIBLIOGRAPHYpages 222, 223, 226
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536 BIBLIOGRAPHYK, gas-phase infrar
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538 BIBLIOGRAPHY[96ALL/VEI][96CAP/V
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540 BIBLIOGRAPHY[97CAP/VIT][97FEL/R
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542 BIBLIOGRAPHY[99RAI/HES2][99RAR/
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544 LIST OF CITED AUTHORSTable 23.1
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Appendix ADiscussion of selected re
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A. Discussion of selected reference
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5 −10.63±0.11 (g) −12.48±0.23
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dataarein1MNa + media, except as no
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Appendix BIonic strength correction
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B.1 The specific ion interaction eq
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B.2 Ion interaction coefficients ve
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B.3 Tables of ion interaction coeff
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Appendix CAssigned uncertainties
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C.2 Two or more independent source
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C.2 Two or more independent source
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C.3 Several data at different ionic
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C.3 Several data at different ionic
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C.4 Procedures for data handling 83
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C.4 Procedures for data handling 83
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Index837
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INDEX - GENERAL 839standard state p
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INDEX - NEPTUNIUM 841elemental nept
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INDEX - PLUTONIUM 843Index - pluton
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INDEX - PLUTONIUM 845monobismuthide
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