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

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A. Discussion of selected references 621discussed here. The constants were obtained from distribution measurements atHF(aq) concentrations between 6 × 10 −5 and 10 −3 M and are listed in Table A.3.Krylov and coworkers [69KRY/KOM2, 69KRY/KOM4] could explain their data interms of the formation of PuF 3+ , and it was not necessary under these conditions toinclude a 1:2 complex in the model.Table A.3: Equilibrium constants referring to Reaction (A.34) as reported in[69KRY/KOM2] (HClO 4 )and[69KRY/KOM4] (HNO 3 ).Background electrolyte log ∗ 10 β 1 (A.34) log ∗ 10 β 1 (A.34)(I = 1M) (I = 2M)HClO 4 [69KRY/KOM2] (4.20 ± 0.08) (4.45 ± 0.03)HNO 3 [69KRY/KOM4] (4.04 ± 0.08) (3.78 ± 0.01)HNO 3 (corrected for the (4.66 ± 0.15) (4.64 ± 0.16)formation of PuNO 3+3 by this review)It is obvious that the constants are systematically lower in HNO 3 solutions[69KRY/KOM4] compared to HClO 4 solutions [69KRY/KOM2]. This is due to theformation of nitrate complexes of Pu 4+ . We use our selected constants to correctfor the formation of PuNO 3+3in nitrate media, log 10 β 1 (I = 1M) = (0.50 ± 0.16)and log 10 β 1 (I = 2M) = (0.49 ± 0.19). The corrected values, listed in the last rowof Table A.3, are then significantly higher than those measured in HClO 4 solutions.In particular, it is noted that the constant measured at I = 1M(HClO 4 ) differsconsiderably from the one determined in nitric acid solution and corrected for nitratecomplexation. We estimate that the formation of the 1:2 complex, PuF 2+2, should besignificant at the higher concentrations of HF(aq) used in these experiments. However,the possible influence of the 1:2 complex should also affect the values determinedin the HClO 4 solutions, and the lack of including the 1:2 complex can thereforenot explain the discrepancy. The constants measured in perchlorate media and thecorrected ones from nitrate media are used in the evaluation of the standard values,but the uncertainties in the logarithmic values are increased to ±0.30 in HClO 4 and to±0.40 in HNO 3 media to cover the systematic errors.[69KRY/KOM3]See comments under Krylov and Komarov [69KRY/KOM].[69KRY/KOM4]See comments under Krylov and Komarov [69KRY/KOM2].
622 A. Discussion of selected references[69MET/GUI]This is a solvent extraction study of the hydrolysis of Pu(IV) for an aqueous mediumof ionic strength 1.0 M (H/LiClO 4 ). No values for the hydrolysis constants are derivedin this paper.[69MOS]This publication is a compilation of stability constants of actinide complexes with variousligands. Values for nitrate, sulphate, carbonate and phosphate complexes, as determinedin previous work, published and unpublished, were reported together withthe author’s estimates. For the phosphate system, constants for Np(III) complexes withH 2 PO − 4were included, estimated on the basis of the results for Pu(III), Am(III) andCm(III) published in a later paper [71MOS4]Np 3+ + nH 2 PO − 4Å Np(H 2 PO 4 ) 3−nn(A.35)log 10 β n (A.35, n = 1, unreported temperature, I → 0) = 2.40log 10 β n (A.35, n = 2, unreported temperature, I → 0) = 3.73log 10 β n (A.35, n = 3, unreported temperature, I → 0) = 5.64log 10 β n (A.35, n = 4, unreported temperature, I → 0) = 6.2and estimates at I = 0 for the Pu(III) constants later reported in [71MOS4]:Pu 3+ + nH 2 PO − 4Å Pu(H 2 PO 4 ) 3−nn(A.36)log 10 β n (A.36, n = 1, unreported temperature, I → 0) = 2.39log 10 β n (A.36, n = 2, unreported temperature, I → 0) = 3.70log 10 β n (A.36, n = 3, unreported temperature, I → 0) = 5.63log 10 β n (A.36, n = 4, unreported temperature, I → 0) = 6.2Since the experimentally determined constants for the Pu(III) in [71MOS4] have beenrejected in the present review, the same holds for the corresponding Np(III) complexes.Moskvin includes also constants for complexes of Np(VI) with both H 2 PO − 4and HPO 2−4and for Pu(VI) with HPO 2−4, reported to have been obtained in a solventextraction study at an ionic strength 0.5 M.NpO 2+2+ H 2 PO − 4Å NpO 2 H 2 PO + 4(A.37)log 10 β(A.37, unreported temperature, I = 0.5M) = 1.70log 10 β(A.37, unreported temperature, I → 0) = 2.33NpO 2+2+ HPO 2−4Å NpO 2 HPO 4 (aq) (A.38)
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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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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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Page 596 and 597: 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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