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

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12.1 Neptunium carbon compounds and complexes 283as the weighted mean of the uranium and neptunium corresponding valuesε ((UO2 ) 2 NpO 2 (CO 3 ) 6−6 ,Na+ )= (2ε ((UO2 ) 3 (CO 3 ) 6−6 ,Na+ ) + ε ((NpO 2 ) 3 (CO 3 ) 6−6 ,Na+ ))/3. Thenε(12.43) = (0.27 ± 0.77) kg·mol −1 is calculated and used to extrapolate the abovevalue, log 10 K(12.43, 3MNaClO 4 ) =−(10.0 ± 0.3) to zero ionic strength:Hence,log 10 K ◦ (12.43, 298.15K) =−(8.99 ± 2.69) r G ◦ m (12.43, 298.15K) = (51.29 ± 15.36) kJ·mol−1 f G ◦ m ((UO 2) 2 NpO 2 (CO 3 ) 6−6, 298.15K) = −(6174.31 ± 16.98) kJ·mol−1log 10 K ◦ (12.44, 298.15K) = (53.59 ± 2.70) and r G ◦ m (12.44, 298.15K) =−(305.87 ± 15.40) kJ·mol −1 are calculated for the equilibrium2UO 2+2+ NpO 2+2+ 6CO 2−3Å (UO 2 ) 2 NpO 2 (CO 3 ) 6−6(12.44)from the above selected values.12.1.3 Neptunium cyanide complexesFormation constants (log 10 β n = 2.90, 3.23, 4.81, 5.11 and 5.94, n=1-5) for cyano complexesof dioxoneptunium(V), NpO 2 (CN) 1−nn (n = 1-5) at 25 ◦ C, I =5(mol· dm −3 )have been reported [77CUI/MUS, 78MUS/MAR], based on a spectroscopic study (970to 1060 nm) at pH values between 6.2 and 9.4. Insoluble complex solids, tentativelyidentified as NaNpO 2 (CN) 2·xH 2 OandNpO 2 CN·yH 2 O were also found to form inconcentrated solutions of NaCN(aq), and solubilities in 2M NaCN (5M Na + (aq)) werereported. As discussed in Appendix A, although there is good evidence for complexformation, the results of this work cannot be used to derive serviceable values forI = 0, and the stoichiometries of the major complexes and solids need to be confirmedby other experiments.12.1.4 Neptunium thiocyanate complexes12.1.4.1 Aqueous Np(IV) thiocyanate complexesThe formation of thiocyanate complexes of Np(IV) has been studied by Rao et al.[78RAO/BAG2] using solvent extraction. This is a careful and comprehensive study(see discussion in Appendix A). The authors reported equilibrium constants for threereactions of the type:Np 4+ + q SCN − Å Np(SCN) 4−qq (12.45)Their results are summarized in Table 12.8.For extrapolation of the 1:1 and 1:2 data to I = 0, we use the ε values that wereused for the corresponding U(IV) system,
284 12. Neptunium group 14 compounds and complexesTable 12.8: Experimental equilibrium data for the neptunium(IV) thiocyanate system,pH = 0.Method Ionic medium t ( ◦ C) log 10 β q(a) log 10 β ◦(b) qNp 4+ + SCN − Å NpSCN 3+Referencedis-TTA 2 M (H, Na)ClO 4 10 (1.53 ± 0.01) [78RAO/BAG2]2M(H, Na)ClO 4 25 (1.49 ± 0.07) 3.03 (c)2M(H, Na)ClO 4 40 (1.40 ± 0.01)dis-DNNS 2 M (H, Na)ClO 4 25 (1.48 ± 0.06) 3.02 (c)Np 4+ + 2SCN − Å Np(SCN) 2+2dis-TTA 2 M (H, Na)ClO 4 10 (2.25 ± 0.03) [78RAO/BAG2]2M(H, Na)ClO 4 25 (2.06 ± 0.08) 4.02 (c)2M(H, Na)ClO 4 40 (2.13 ± 0.03)dis-DNNS 2 M (H, Na)ClO 4 25 (2.26 ± 0.05) 4.22 (c)Np 4+ + 3SCN − Å Np(SCN) + 3dis-TTA 2 M (H, Na)ClO 4 10 (2.61 ± 0.03) [78RAO/BAG2]2M(H, Na)ClO 4 25 (2.53 ± 0.02) 4.81 (c)2M(H, Na)ClO 4 40 (2.34 ± 0.04)dis-DNNS 2 M (H, Na)ClO 4 25 (2.50 ± 0.03) 4.78 (c)(a) log 10 β q refers to the equilibrium and the ionic strength given in the table.(b) log 10 βq ◦ is the corresponding value corrected to I = 0 at 298.15 K .(c) The uncertainties given by the authors do not include systematic errors and have therefore notbeen propagated to zero ionic strength.
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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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Page 264 and 265: (f) Values selected in this review
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Page 320: Part IVDiscussion of plutonium data
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Page 341 and 342: 316 16. Plutonium aqua ionsFigure 1
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334 17. Plutonium oxygen and hydrog
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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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