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

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9.2 Aqueous neptunium group 17 (halogen) complexes 159Figure 9.1: Extrapolation to I = 0 of experimental data for the formation of NpF 3+using the specific ion interaction equation. The data refer to HClO 4 media andare taken from [66AHR/BRA], [69KRY/KOM], [69KRY/KOM3], [75PAT/RAM],[76BAG/RAM] and [76CHO/UNR]. The solid line represents the prediction of(log ∗ 10 β1 ◦ + 6D) using our selected data, and the dotted lines are the limits of theuncertainty range obtained by propagating the resulting uncertainties at I = 0 back toI = 5mol·kg −1 .Equilibrium: Np 4+ + HF(aq) Å NpF 3+ + H +6.8log 10 ∗ β 1ο= (5.78 ± 0.14)∆ε = −(0.12 ± 0.04)6.4log 10∗ β1 +6D65.65.2[69KRY/KOM3][76CHO/UNR][69KRY/KOM][76BAG/RAM][75PAT/RAM][66AHR/BRA]0 1 2 3 4 5I m
160 9. Neptunium group 17 (halogen) compounds and complexesε (NpF+3 ,ClO − 4 ) ≈ ε (UF+3 ,ClO − 4 ) = 0.1kg·mol −1 [92GRE/FUG], the resulting log ∗ 10 β3◦values are in better agreement. However, on the present basis we do not consider itpossible to make any selection for the formation constants of NpF + 3 and NpF 4(aq).The Gibbs energies of formation of NpF 3+ and NpF 2+2are calculated using theselected values for Np 4+ and F − . f G ◦ m (NpF3+ , aq, 298.15 K) = −(824.4 ± 5.7) kJ·mol −1 f G ◦ m (NpF2+ 2, aq, 298.15 K) = −(1144.4 ± 6.0) kJ·mol−1From the equilibrium constants of Choppin and Unrein [76CHO/UNR] at 10, 25and 40 ◦ C it is possible to extract an enthalpy of reaction: r H m (9.4, q = 1) =−(10.7 ± 2.0) kJ·mol −1 , cf. Appendix A. Assuming its dependence on the ionicstrength to be negligible, and combining it with the enthalpy of protonation of the fluorideion [92GRE/FUG], we obtain r Hm ◦ (9.5, q = 1, 298.15 K) = (1.5 ± 2.0) kJ·mol−1From this value we derive the enthalpy of formation and the entropy of NpF 3+ : f H ◦ m (NpF3+ , aq, 298.15 K) = −(889.9 ± 4.7) kJ·mol −1S ◦ m (NpF3+ , aq, 298.15 K) = −(264 ± 14) kJ·mol −19.2.1.3 Aqueous Np(V) fluoridesFluoride complexation has been studied in near-neutral solutions by severalauthors using spectrophotometric [78RAO/PAT], solvent extraction[79RAO/GUD, 84CHO/RAO, 85INO/TOC2] and potentiometric [85SAW/RIZ]techniques, cf. Table 9.4.NpO + 2 + qF− Å NpO 2 F 1−qq (9.6)Some authors (e.g. [70AL-/WAI]) reported that they could not observe the formationof any Np(V) fluoride complex. However, those investigations were carried outat high acidity, where the proton is too powerful a competitor for the fluoride ion.Np(V) fluoride complexation studies thus need to be carried out at moderate acidity tobe successful. The solvent extraction study of Rao et al. [79RAO/GUD] isthemostreliable one, because the oxidation state of Np(V) was checked spectroscopically bothat the beginning and at the end of the experiment. This was not done in the studiesof Choppin and Rao [84CHO/RAO] and of Inoue and Tochiyama [85INO/TOC2], butthis does not mean that the results must be in error. Sawant et al.[85SAW/RIZ]usedafluoride ion selective electrode and carefully tried to eliminate interfering side effectsby running a blank titration, cf. Appendix A. However, under their experimental conditions(low fluoride concentration and comparatively low pH), only very low averagecomplexation degrees could be reached, and their data are associated with a high uncertainty.The spectrophotometric determination of Rao and Patil [78RAO/PAT] lacks
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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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sol K + ,CO 2−3 , 20 −(2.31±0.
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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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