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19.1 Plutonium sulphur compounds and complexes 395Table 19.3: Best values for the stability constants of the Pu(IV)-SO 2−4complexes reevaluatedby the reviewers.Reference log 10 ∗ β I m log 10 ∗ β ◦ t( ◦ C)Pu 4+ + HSO − 4Å PuSO 2+4 + H +[73PAT/RAM] (2.84±0.06) (a) 2.2 (HClO 4 ) 10(2.72±0.05) (a) 2.2 (HClO 4 ) 40[73PAT/RAM2] (2.76±0.03) 2.2 (HClO 4 ) (4.89±0.27) 25(2.68±0.06) 2.2 (HClO 4 ) (4.81±0.27) 25[74FAR/PEA] (2.75±0.02) 2.2 (HClO 4 ) (4.88±0.26) 25[76BAG/RAM] (2.73±0.18) 2.2 (HClO 4 ) (4.86±0.32) 25(2.80±0.13) 2.2 (HClO 4 ) (4.93±0.29) 25[76BAG/RAM2] (3.00±0.17) 2.2 (HClO 4 ) (5.13±0.31) 25(2.95±0.14) 2.2 (HClO 4 ) (5.08±0.30) 25[77BAG/RAM] (2.71±0.03) (a) 2.2 (HClO 4 ) 10(2.88±0.07) (a) 2.2 (HClO 4 ) 10[83NAS/CLE] (2.45±0.07) (a) 2.2 (H,Na)ClO 4 0(2.58±0.04) (a) 2.2 (H,Na)ClO 4 10(2.76±0.03) 2.2 (H,Na)ClO 4 (4.89±0.27) 25(2.85±0.05) (a) 2.2 (H,Na)ClO 4 35Best Value (2.75±0.01) 2.2 (4.91±0.22) 25Pu 4+ + 2HSO − 4Å Pu(SO 4 ) 2 (aq) + 2H +[73PAT/RAM] (4.33±0.05) (a) 2.2 (HClO 4 ) 10(4.39±0.03) (a) 2.2 (HClO 4 ) 40[73PAT/RAM2] (4.35±0.02) 2.2 (HClO 4 ) (7.08±0.18) 25(4.51±0.02) 2.2 (HClO 4 ) (7.24±0.18) 25[74FAR/PEA] (4.43±0.03) 2.2 (HClO 4 ) (7.16±0.18) 25[76BAG/RAM] (4.66±0.07) 2.2 (HClO 4 ) (7.39±0.19) 25(4.47±0.08) 2.2 (HClO 4 ) (7.20±0.19) 25(Continued on next page)
396 19. Plutonium group 16 compounds and complexesTable 19.3: (continued)Reference log 10 ∗ β I m log 10 ∗ β ◦ t( ◦ C)[76BAG/RAM2] (4.59±0.11) 2.2 (HClO 4 ) (7.32±0.21) 25(4.45±0.11) 2.2 (HClO 4 ) (7.18±0.21) 25[77BAG/RAM] (4.58±0.01) (a) 2.2 (HClO 4 ) 10(4.38±0.05) (a) 2.2 (HClO 4 ) 10[83NAS/CLE] (4.10±0.09) (a) 2.2 (H,Na)ClO 4 0(4.06±0.07) (a) 2.2 (H,Na)ClO 4 10(4.13±0.07) 2.2 (H,Na)ClO 4 (6.86±0.19) 25(4.11±0.08) (a) 2.2 (H,Na)ClO 4 35Best Value (4.43±0.01) 2.2 (7.18±0.32) 25(a) Used to calculate r H ◦ m only.The most reliable value of log ∗ 10 β ◦ (I)(19.5) atI = 2.2 m is the weighted averageof the results at 25 ◦ C reported in Table 19.3: (4.43 ± 0.01). Based on theionic interaction parameters determined for the analogous U(IV) complex (ε(19.5) =−(0.46 ± 0.08) kg·mol −1 ;[92GRE/FUG]), this value can be extrapolated to standardstate: log10 ∗β◦∗2(19.5) = (7.18 ± 0.32). Caution is advised in the use of log10 β◦ 2 (19.5)outside of the range of H + concentration (1-2 M) in which it was determined. Thereare four independent sets of equilibrium constants determined in identical experimentsover a range of temperatures from which to estimate r Hm ◦ (19.4) and rHm ◦ (19.5):[73PAT/RAM] (including results of [76PAT/RAM]), two from [77BAG/RAM] (includingthe results of [76BAG/RAM] and[76BAG/RAM2]), and [83NAS/CLE]. The fourdeterminations yield r Hm ◦ (19.4) =−(7.1±1.7), (2.4±3.5), (7.2±3.0), and (18.6±1.2) kJ·mol −1 and r Hm ◦ (19.5) = (3.1 ± 1.8), (8.6 ± 1.4), (7.5 ± 2.3), and (1.5 ±3.4) kJ·mol −1 . The unweighted average of these results is indistinguishable from 0( r Hm ◦ (19.4) = (5.3 ± 21.3) kJ·mol−1 and r Hm ◦ (19.5) = (5.2 ± 6.8) kJ·mol−1 ).Aswe have no basis to eliminate any of these experimental results, we recommend no bestvalue, and advise caution in the determination of fundamental thermodynamic propertiesfrom the temperature variation of log ∗10 β 1(19.4) and log ∗10 β 2(19.5) in this system.19.1.1.1.d Pu(III) sulphatesThere are four experimental data sets concerning the Pu(III)-sulphate system(Table 19.4). Although Pu(III)-bisulphate complexes have been postulated(Pu(HSO 4 ) + 2 ,andPu(SO 4)(HSO 4 )(aq); [67NAI/RAO], [83NAS/CLE2]), the resultsare interpreted by this review as consistent with the equilibria:Pu 3+ + HSO − 4Å PuSO + 4 + H+ (19.6)
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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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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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