chemical thermodynamics of neptunium and plutonium - U.S. ...

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PuO 2+2+ 3F − Å PuO 2 F − (b)3cix 1 M HClO 4 25 (6.08±0.07) [68KRY/KOM2]2MHClO 4 25 (5.52±0.12)ise-F − 0.1 M NaClO 4 21 9.01 [85SAW/CHA]1MNaClO 4 21 7.73(a) log ∗ 10 β q refers to Reaction (18.10) and results from measurements in acidic solutions.(b) log 10 β q refers to Reaction (18.11) and results from measurements in mildly acidic or neutral solutions.(c) log 10 βq ◦ refers to Reaction (18.11). The experimental data have been corrected to I = 0 in the present review and, when necessary, converted torefer to Reaction (18.11) by using the selected protonation constant of fluoride ion.(d) Uncertainty estimated in this review.18.2 Aqueous plutonium group 17 (halogen) complexes 377
378 18. Plutonium group 17 (halogen) compounds and complexesSawant et al. [85SAW/CHA] also reported formation constants for the 1:3 complex,NpO 2 F − 3. Again, these constants reported for I = 0.1 MandI = 1 M are notcompatible with the specific ion interaction coefficients in Appendix B. For the correspondingU(VI) system we have ε(18.11, q = 3) =−0.52 kg·mol −1 [92GRE/FUG],and by using this value to correct the data of [85SAW/CHA] toI = 0 we obtainlog 10 β3 ◦ (18.11, q = 3) = 9.6 and 8.4 for the experiments carried out at I = 0.1 Mand I = 1 M, respectively. In order to obtain consistent log 10 β3 ◦ values from thetwo determinations, we would have to use ε =+0.8 kg·mol −1 , and this would beincompatible with the commonly observed ionic strength dependence of comparableequilibria. The formation of NpO 2 F − 3needs closer examination, and no selection ismade at this time.The Gibbs energy of formation values are derived from the above selected constantsusing the selected f G ◦ m values for PuO2+2and F − . f G ◦ m (PuO 2F + , aq, 298.15 K) = −(1069.9 ± 3.1) kJ·mol −1 f G ◦ m (PuO 2F 2 , aq, 298.15 K) = −(1366.8 ± 4.1) kJ·mol −118.2.2 Aqueous plutonium chlorine complexes18.2.2.1 Aqueous plutonium chlorides18.2.2.1.a Aqueous Pu(III) chloridesQuantitative information on chloride complexation of Pu 3+ according to the equilibriaPu 3+ + qCl − Å PuClq 3−q(18.12)has been published by Ward and Welch [56WAR/WEL], Martin and White[58MAR/WHI] and Shiloh and Marcus [64SHI/MAR], and is summarised inTable 18.3. The study of Ward and Welch [56WAR/WEL] was carried out at ionicstrengths of 0.207, 0.5 and 1.0 M, respectively (cf. Appendix A). The formationconstant reported by Martin and White [58MAR/WHI] is not the result of anindependent measurement, but rather the result of an extrapolation of Ward andWelch’s [56WAR/WEL] value at I = 0.207 M (HCl) using the Davies equation.This value was used to derive the enthalpy of Reaction (18.12, q = 1) (see AppendixA and discussion below). The data of Ward and Welch [56WAR/WEL] reportedat “room temperature”, which Martin and White [58MAR/WHI] reported as 21 ◦ C, arethus corrected to t = 25 ◦ C(cf. Appendix A), using the enthalpy of reaction selectedbelow. Shiloh and Marcus [64SHI/MAR] used very high and variable ionic strengthsin their spectrophotometry experiments. These values cannot be used to select a formationconstant at I = 0. Giffaut [94GIF] noted that spectrophotometry is not a suitablemethod to study chloride complexation of Pu 3+ , due to the very small changes in theabsorption spectrum up to a chloride concentration of 4 M. It is probable that thiscomplexation could equally well be described as activity effects. The number of availableformation constants is insufficient for a linear extrapolation to I = 0. We adopt
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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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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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