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18.2 Aqueous plutonium group 17 (halogen) complexes 371and thusCp,m ◦ −1(PuOI, cr, 298.15 K) = (75.6 ± 10.0) J·K−1·mol18.2 Aqueous plutonium group 17 (halogen) complexes18.2.1 Aqueous plutonium fluoride complexes18.2.1.1 Aqueous Pu(III) fluoridesIn two studies from the same group [86MAH/SAW, 93SAW/MAH], data were reportedon fluoride complexation of Pu 3+ obtained by potentiometry using a fluoride ionselective electrode. In the later study [93SAW/MAH], the credibility of the earlierresult was questioned due to the evaluation method used then, which was unsuitableif higher complexes were present. The results of the recent study, however, are verysurprising as they suggest that the 1:3 complex, PuF 3 (aq), and other MF 3 (aq) complexesare by far more stable than the 1:1 and the 1:2 complexes. This is contrary tothe behaviour of Am(III) [92FUG/KHO, 95SIL/BID], and independent verification ofthe results of Sawant et al. [93SAW/MAH] is required. Appendix A contains a moredetailed discussion of this paper. No data are selected for the Pu(III) fluoride system.It is worth mentioning that the trivalent actinide ions exhibit a very similar complexationbehaviour, see for example [92FUG/KHO], which resembles that of the trivalentlanthanide ions, e.g. [86CHO, 92MIL]. Hence, the stability constants of the Pu(III) fluoridecomplexes are expected to be of magnitudes similar to those of other actinide(III)and lanthanide(III) fluoride complexes.18.2.1.2 Aqueous Pu(IV) fluoridesExperimental equilibrium data have been published for the following reactionsPu 4+ + qHF(aq) Å PuF 4−qq + qH + (18.8)Pu 4+ + qF − Å PuF 4−qq (18.9)Most experiments were carried out in strongly acidic solutions, and the relevantequilibrium is thus Reaction (18.8). The data reported in [90SAW/CHA2] are convertedto refer to Reaction (18.8) by taking the authors’ protonation constant of F − (cf.Appendix A). All reported constants are listed in Table 18.1.The values for log 10 ∗ β 1 are in good agreement, but an extrapolation to I = 0bylinear regression is not reasonable, because the available data refer to only two differentionic strength values. We use ε(9.4, q = 1) =−(0.12 ± 0.09) kg·mol −1 from thecorresponding Np(IV) system (the uncertainty increased by 0.05), cf. Section 9.2.1.2,
372 18. Plutonium group 17 (halogen) compounds and complexesTable 18.1: Experimental equilibrium data for the plutonium(IV) fluoride system.Method Ionic medium t ( ◦ C) log 10 ∗ β q(a) log 10 ∗ β ◦(a) qPu 4+ + HF(aq) Å PuF 3+ + H +Referencecix 2 M HClO 4 25 (4.45±0.30) (b) (5.59±0.36) [69KRY/KOM2]1MHClO 4 25 (4.20±0.30) (b) (5.31±0.31)cix 2 M HNO 3 25 (4.64±0.40) (b,c) (5.78±0.45) [69KRY/KOM4]1 M HNO 3 25 (4.66±0.40) (b,c) (5.77±0.41)dis 2 M HClO 4 25 (4.64±0.15) (b) (5.78±0.25) [76BAG/RAM]dis 2 M HClO 4 25 (4.64±0.20) (b) (5.78±0.28) [76BAG/RAM2]dis 2 M HClO 4 10 4.70 [77BAG/RAM]cou 1 M HClO 4 25 (4.66±0.20) (b) (5.77±0.22) [79CHI/TAL]dis 2 M HClO 4 25 (4.47±0.20) (b) (5.61±0.28) [84NAS/CLE]2MHClO 4 15 4.502MHClO 4 7.5 4.512MHClO 4 1 4.522M(Na,H)ClO 4 25 (4.36±0.20) (b) (5.50±0.28)ise-F − 1M(Na,H)ClO 4 23 4.66 (d) 5.76 [90SAW/CHA2]Pu 4+ + 2HF(aq) Å PuF 2+2+ 2H +dis 2 M HClO 4 25 (7.62±0.30) (b) (9.56±0.46) [76BAG/RAM]dis 2 M HClO 4 25 (7.61±0.40) (b) (9.57±0.52) [76BAG/RAM2]dis 2 M HClO 4 10 7.65 [77BAG/RAM]cou 1 M HClO 4 25 (7.32±0.40) (b) (9.19±0.43) [79CHI/TAL]dis 2 M HClO 4 25 (7.46±0.20) (b) (9.41±0.39) [84NAS/CLE]2MHClO 4 15 7.542MHClO 4 7.5 7.582MHClO 4 1 7.692M(Na,H)ClO 4 25 (7.35±0.20) (b) (9.30±0.39)ise-F − 1M(Na,H)ClO 4 25 8.87 (d) 9.90 [90SAW/CHA2]Pu 4+ + 3HF(aq) Å PuF + 3 + 3H+ise-F − 1MHClO 4 23 11.26 (d) 13.4 [90SAW/CHA2]Pu 4+ + 4HF(aq) Å PuF 4 (aq) + 4H +ise-F − 1MHClO 4 23 14.27 (d) 16.4 [90SAW/CHA2](a) Refers to the reactions indicated, the ionic strength and temperature given in the table.log ∗ 10 βq ◦ is in molal units, at I = 0 and 298.15 K.(b) Uncertainty estimated in this review (cf. Appendix A).(c) Corrected for the formation of NpNO 3+3 , cf. Appendix A.(d) The published values refer to Reaction (18.9) and have been converted to conform to thereactions of this table (cf. Appendix A).
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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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132 9. Neptunium group 17 (halogen)
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178 10. Neptunium group 16 compound
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Chapter 11Neptunium group 15compoun
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11.1 Neptunium nitrogen compounds a
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11.2 Neptunium phosphorus compounds
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11.2 Neptunium phosphorus compounds
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Chapter 12Neptunium group 14compoun
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12.1 Neptunium carbon compounds and
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cal 0.3-1.6 M Na 2 SO 4 25 r H m =
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vlt 0 25 (0.340±0.002) (k) [95OFF/
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sol K + ,CO 2−3 , 20 −(2.31±0.
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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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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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428 21. Plutonium group 14 compound
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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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