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

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12.1 Neptunium carbon compounds and complexes 281Figure 12.8: Comparison of values of K(12.40). Plotted values are from publisheddata for NaClO 4 media, re-evaluated in the present review and corrected to I=0. Theline, log 10 K ◦ =−(3.54 ± 0.73) is calculated using the K s,3 (12.37) andK s,3 (12.41)values selected in the present review. Any effects related to water of hydration havebeen neglected. Data for other media are also shown ((a)K 2 CO 3 and (b)(NH 4 ) 2 CO 3 ;see legend). On the x axis, m = m K +,m Na + or m NH+ .4ORJ . R ± ORJ . R>*5(52%@>/(0%21(&581@>9,692/@ D>026@ E P PRONJ
282 12. Neptunium group 14 compounds and complexesselected for standard conditions because: (a) the solid phases were undoubtedly changingduring the solubility measurements, and (b) the ion interaction coefficients, ε,could not be accurately estimated for solutions containing cations other than Na + asthe predominant cation, especially for reactions involving the highly charged limitingcomplex.12.1.2.2.3 Np(IV) Solid phases equilibrated with carbonate / bicarbonateaqueous solutionsNp(IV) solubility in neutral media is 10 −(8.3±0.3) mol·dm −3 (Section 8.1.4) andwasinterpreted in terms of the equilibriumNpO 2 (am, hyd) Å Np(OH) 4 (aq) (12.42)[85RAI/RYA]. Hence, in these conditions, no carbonate solid phase containingNp(IV) was formed. In more concentrated alkali metal carbonate media, the solubility[71MOS2, 77SAI/UEN, 93LI/KAT, 99RAI/HES] increased as a result of Np(CO 3 ) 4−4and Np(CO 3 ) 6−5formation [95VIT]. This is undoubtedly limited by some new solidphase or phases[77SAI/UEN, 95VIT], possibly including alkali metal cations andNp(CO 3 ) 5−6anions. No thermodynamic data could be estimated for these possiblesolid phases.12.1.2.3 Mixed actinide carbonate complexesValues for the equilibrium constants for formation of complexes of the type(UO 2 ) 2 NpO 2 (CO 3 ) 6−6according to the reactionNpO 2 (CO 3 ) 4−3+ 2UO 2 (CO 3 ) 4−3Å (12.43)(UO 2 ) 2 NpO 2 (CO 3 ) 6−6+ 3CO 2−3have been discussed previously in this series of reviews [92GRE/FUG, 95GRE/PUI].The assessed values were log 10 K ◦ = −(9.4 ± 1.3) for the Np equilibrium, and−(8.2±1.3) for the plutonium equilibrium (also cf. Section 21.1.2.1.1.e). These selectionswere based on Grenthe, Riglet and Vitorge’s spectrophotometric determinationfor the neptunium containing species log 10 K(12.43, 3MNaClO 4 ) =−(10.0 ± 0.2)[86GRE/RIG, 90RIG]. This work is also accepted in the present review, butwith an increased uncertainty, equal to the uncertainty assigned in the reevaluationfor the pure Np(VI) trinuclear complex. The earlier work used thesame ionic strength corrections for all the formation constants of complexesof the type (UO 2 ) 2 MO 2 (CO 3 ) 6−6(M = U, Np, Pu). This correction, usingε = (0.16 ± 0.36) kg·mol −1 [95GRE/PUI], was only measured for the pure uraniumtrinuclear complex (M=U). Instead of −(9.4 ± 1.3), log 10 K ◦ (12.43) =−(9.2 ± 1.3)is calculated for formation constant of the mixed U-Np trinuclear carbonate complex,using ε = (0.49 ± 0.50) kg·mol −1 estimated in the present review for the pureneptunium trinuclear complex. This review estimatesε ((UO2 ) 2 NpO 2 (CO 3 ) 6−6 ,Na+ )= (0.09 ± 0.71) kg·mol−1
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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)
Page 256 and 257: sol 1 M NaCl 23 (2.06±0.13) [96RUN
Page 258 and 259: sol 0.15 M Na 2 CO 3 −(2.58±0.64
Page 260 and 261: sol 1 M NaClO 30 −(4.0±0.2) [93L
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Page 264 and 265: (f) Values selected in this review
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Page 315 and 316: 290 13. Neptunium group 2 (alkaline
Page 317 and 318: 292 14. Neptunium group 1 (alkali)
Page 320: Part IVDiscussion of plutonium data
Page 323 and 324: 298 15. Elemental plutoniumTable 15
Page 325 and 326: 300 15. Elemental plutoniumfrom 298
Page 327 and 328: 302 16. Plutonium aqua ionsthe prop
Page 329 and 330: 304 16. Plutonium aqua ions298.15 K
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Page 341 and 342: 316 16. Plutonium aqua ionsFigure 1
Page 343 and 344: 318 17. Plutonium oxygen and hydrog
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332 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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