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

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9.2 Aqueous neptunium group 17 (halogen) complexes 167value of log 10 β1 ◦ when recalculated to ionic strengths up to I = 5 m by using the selectedε value. The IAEA review [92FUG/KHO] selected log 10 β1 ◦ = (1.8±0.5),whichis compatible with the present selection. Giffaut [94GIF] recommended log 10 β1 ◦ =(1.45 ± 0.25) based on the same literature values.Table 9.6: Experimental equilibrium data for the neptunium(IV) chloride system.Method Ionic t log 10 β q(a)medium ( ◦ C)Np 4+ + Cl − Å NpCl 3+log 10 β ◦(a) qReferencered 1 M H(Cl,ClO 4 ) 25 −0.3 [58STR/PEE]sp 2 M Na(Cl,ClO 4 ) 25 −0.28 [62SYK/TAY]dis 0.5 M H(Cl,ClO 4 ) 20 (0.15±0.20) (b) [66SHI/NAZ]1MH(Cl,ClO 4 ) 20 −(0.04±0.20) (b)2MH(Cl,ClO 4 ) 20 (0.04±0.20) (b)dis 4 M (H,Na)(Cl,ClO 4 ) 25 −(0.11±0.30) (b) [71DAN/CHI]sp 9 M H(Cl,ClO 4 ) RT 2.12 [73BAR/MUR]dis 2 M H(Cl,ClO 4 ) 25 −(0.05 ± 0.05) [75PAT/RAM]dis 2 M H(Cl,ClO 4 ) 25 (0.00±0.20) (b,c) [75PAT/RAM][94GIF]cix 0.2 - 1 M HCl 25 0.34 [76SOU/SHA]Np 4+ + 2Cl − Å NpCl 2+2dis 1 M H(Cl,ClO 4 ) 20 −(0.25±0.30) (b) (1.9 ± 0.3) [66SHI/NAZ]2MH(Cl,ClO 4 ) 20 −(0.15±0.30) (b) (1.5 ± 0.4)dis 4 M (H,Na)(Cl,ClO 4 ) 25 −(0.10±0.50) (b) (0.0 ± 0.8) [71DAN/CHI]sp 9 M H(Cl,ClO 4 ) RT 3.04 [73BAR/MUR]dis 2 M H(Cl,ClO 4 ) 25 −(0.15 ± 0.06) [75PAT/RAM]dis 2 M H(Cl,ClO 4 ) 25 −(0.22±0.40) (b,c) (1.4 ± 0.4) [75PAT/RAM][94GIF]Np 4+ + 3Cl − Å NpCl + 3dis 1 M H(Cl,ClO 4 ) 20 −0.48 [66SHI/NAZ](a) Refers to the reactions indicated, the ionic strength and temperature given in the table. log 10 β ◦ qis in molal units, at I = 0 and 298.15 K.(b) Uncertainty estimated in this review (cf. Appendix A).(c) Result of a re-evaluation by Giffaut [94GIF] (cf. Appendix A [75PAT/RAM]).The Gibbs energy of formation is calculated using the selected values for Np 4+ andCl − . f G ◦ m (NpCl3+ , aq, 298.15 K) =−(631.6 ± 5.8) kJ·mol −1The 1:2 complex, NpCl 2+2, if it exits, is very weak. Some values have been reported,cf. Table 9.6. If we tentatively use ε(9.10, q = 2) =−(0.70 ± 0.12)kg·mol −1 as
168 9. Neptunium group 17 (halogen) compounds and complexesestimated from the value of the formation of UF 2+2, cf. [92GRE/FUG], Appendix B,the resulting log 10 β2 ◦ values, see Table 9.6, are not consistent. Giffaut [94GIF] giveslog 10 β2 ◦ (9.10, q = 2) = (2.4 ± 0.3), evaluated from the same literature data using anestimated ε =−(0.63 ± 0.23)kg·mol −1 . In order to obtain agreement between thefour extrapolated values, a slope of about ε(9.10, q = 2) =−0.2kg·mol −1 would benecessary. This is far from being consistent with the ε values of similar equilibria.The reported constants might well be artefacts due to medium changes, and we cannotselect any thermodynamic data for the formation of NpCl 2+2 .The 1:3 complex is very weak, see Appendix A [66SHI/NAZ, 71DAN/CHI]. If thiscomplex exists, it will only form at very high chloride concentrations.Figure 9.3: Comparison of selected and experimental data for the formation ofNpCl 3+ in mixed perchlorate/chloride media from [66SHI/NAZ] [71DAN/CHI] and[75PAT/RAM]. The solid line represents the prediction of (log 10 β 1 + 8D), andthe dotted lines are the limits of the uncertainty range obtained by propagating theresulting uncertainties at I = 0 back to I = 5m.Equilibrium: Np 4+ + Cl − Å NpCl 3+3.5log 10β 1+ 8 D3.02.52.01.51.00.5log 10β1o= 1.5 ± 0.3∆ε = -(0.15 ± 0.18)[66SHI/NAZ][75PAT/RAM][71DAN/CHI]0 1 2 3 4 5I m
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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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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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