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

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10.1 Neptunium sulphur compounds and complexes 181of [70AL-/WAI] are not used as no quantitative estimate of uncertainty could be madeand the estimate of error made by the reviewers appeared to be much larger than thosedetermined in other experiments. The weighted means of these two estimates yield therecommended values:log10 ∗ β◦ 2 (10.4, 298.15 K) = (0.74 ± 0.07)log 10 β2 ◦ (10.2, 298.15 K) = (4.70 ± 0.10)All other thermodynamic parameters can be calculated from those given above.10.1.2.1.c Np(V) sulphatesFive experimental studies describing the Np(V) sulphate complexes [79MOS/POZ,79RAO/GUD, 81PAT/RAM, 83HAL/OLI, 85INO/TOC2] have been reported(Table 10.3). In all cases only one complex was observed:NpO + 2 + SO2− 4Å NpO 2 SO − 4 . (10.5)Table 10.3:system.Experimentally determined formation constants in the Np(V) sulphateMethod I t( ◦ C) log 10 β 1 ReferenceNpO + 2 + SO2− 4Å NpO 2 SO − 4coprecipitation 1.5 M NH 4 Cl (20 ± 2) (1.04 ± 0.4) [79MOS/POZ]dis 2 M NaClO 4 25 (0.44 ± 0.09) [79RAO/GUD]recalc 2.2 m (0.45 ± 0.01)dis 8.5 M 25(?) 0.45 [81PAT/RAM]dis 0.52 m NaClO 4 5 −(0.43 ± 0.35) [83HAL/OLI]dis 1.05 m NaClO 4 5 −(0.18 ± 0.09) [83HAL/OLI]dis 2.2 m NaClO 4 5 −(0.04 ± 0.11) [83HAL/OLI]dis 0.52 m NaClO 4 25 −(0.10 ± 0.08) [83HAL/OLI]dis 1.05 m NaClO 4 25 (0.06 ± 0.04) [83HAL/OLI]dis 2.2 m NaClO 4 25 (0.19 ± 0.04) [83HAL/OLI]dis 0.52 m NaClO 4 45 (0.25 ± 0.03) [83HAL/OLI]dis 1.05 m NaClO 4 45 (0.34 ± 0.03) [83HAL/OLI]dis 2.2 m NaClO 4 45 (0.40 ± 0.05) [83HAL/OLI]dis 1 M NaClO 4 25 (0.76 ± 0.04) [85INO/TOC2]Selected value 0 m 25 (0.44 ± 0.27) This reviewOn the basis of the most reliable data at 25 ◦ C[79RAO/GUD] and[83HAL/OLI]the recommended value for the equilibrium constants for this reaction at standard stateis determined using the SIT model:log 10 β ◦ (10.5, 298.15 K) = (0.44 ± 0.27)
182 10. Neptunium group 16 compounds and complexesand ε(10.5) =−(0.37 ± 0.18)kg·mol −1 . The enthalpy of Reaction (10.5) can becalculated from the three independent series of experiments performed at three ionicstrengths by [83HAL/OLI]. The three estimates yield values of r Hm ◦ (10.5) = (28.8±1.6) kJ·mol −1 at 0.52 m, (22.0 ± 1.8) kJ·mol −1 at 1.05 m and (18.7 ± 0.2) kJ·mol −1 at2.2 m. The mean of these estimates yields the best value. The error was expanded toencompass the entire range of the three independent estimates. r Hm ◦ (10.5, 298.15 K) = (23.2 ± 7.2) kJ·mol−1The remaining thermodynamic parameters may be calculated from the selectedvalves.10.1.2.1.d Np(IV) sulphatesThere are seven reliable studies of the complexing Np(IV) sulphate system[54SUL/HIN, 62SYK/TAY, 63MUS, 66AHR/BRA, 73PAT/RAM, 73PAT/RAM2,76BAG/RAM]. In all but one case [62SYK/TAY], sufficient data have been given bythe authors to permit the redetermination of formation constants and uncertainties.The remaining six studies (Table 10.4) are used to determine the best values forthermodynamic parameters in this system.Table 10.4: Experimentally determined formation constants in the Np(IV) sulphatesystem (a) .Method I t( ◦ C) log 10 ∗ β q(c) ReferenceNp 4+ + SO 2−4Å NpSO 2+4sp 2 M NaClO 4 25 3.51 (d) [62SYK/TAY]Np 4+ + HSO − 4Å NpSO 2+4 + H +dis 2.2 m HClO 4 (10.2 ± 0.2) (2.47±0.09) [54SUL/HIN]recalc (2.38±0.06)dis 2.2 m HClO 4 (25.2 ± 0.2) (2.43±0.09) [54SUL/HIN]recalc (2.53±0.07)dis 2.2 m HClO 4 (35.3 ± 0.2) (2.40±0.09) [54SUL/HIN]recalc (2.58±0.05)sp 2 M NaClO 4 25 (2.43±0.05) (b) [62SYK/TAY]pol 3.5 m NaClO 4 (25 ± 0.2) (2.49±0.03) [63MUS]recalc (2.44±0.03)ix 4.6 m HClO 4 20 (2.70±0.04) [66AHR/BRA]recalc (2.65±0.05)recalc 25 (2.66±0.06)dis 2.2 m HClO 4 25 2.51 [73PAT/RAM2](Continued on next page)
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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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Page 230 and 231: cal 0.3-1.6 M Na 2 SO 4 25 r H m =
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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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12.1 Neptunium carbon compounds and
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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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