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

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11.1 Neptunium nitrogen compounds and complexes 189the measurements of Np(g) pressure [97NAK/ARA], and data obtained for N 2 (g) pressuresover the two phase field Np(l) + NpN(cr) in the temperature range 2480-3100 K[66OLS/MUL], extrapolated to the appropriate lower temperatures. The Gibbs energyof formation of Np(g) was taken from this assessment (Section 6.2). The Gibbs energyof formation of NpN(cr), calculated from the above experimental results, lies betweenthose for PuN(cr) and UN(cr) [80POT/SPE], f G ◦ m (NpN, cr) = −(295900 − 89.88T) J·mol−1 (1690 − 2030 K)The values for the Gibbs energy of formation obtained from this equation are some3-7 % lower over the given temperature range than the values calculated from the assesseddata presented here.11.1.1.1.d The melting point of NpN(cr)Nitrogen pressures for the phase field Np(l) + NpN(cr) have been measured in thetemperature range 2480-3100 Klog 10 (p N2 (g)/bar) = 8.199 − 29.54 × 10 3 T −1 + 7.87 × 10 −18 T 5From these data an estimate was made of the congruent melting point at 9.87 barN 2 (g) of 3103 ± 30 K [66OLS/MUL].11.1.2 Neptunium azide complexesFormation constants (Table 11.2) for azido complexes of dioxoneptunium(V), NpO 2 (N 3 ) 1−nn (n = 1-5) at 25 ◦ C, I = 5 (mol · dm −3 ) have been reported[77CUI/MUS, 78MUS/MAR2], based on a spectroscopic study (970 to 1020 nm) atpH values between 6.2 and 9.4. Although the measurements were done at constantionic strength, the nature of the ionic medium was very different for different solutions,and the apparent values for the complexation constants undoubtedly were affected.The results of this work cannot be used to derive serviceable values for I =0,andtheexistence of the very weak higher complexes (especially n = 4,5) should be regardedas uncertain unless confirmed by other experiments.Table 11.2: Reported formation constants for azido complexes of dioxoneptunium(V)[78MUS/MAR2]NpO 2 (N 3 ) n1−nn log 10 K n log 10 β n1 1.08 1.082 0.77 1.853 0.38 2.234 −0.13 2.105 −0.70 1.40
190 11. Neptunium group 15 compounds and complexes11.1.3 Neptunium nitritesThe only data on neptunium nitrite complexes available to this review concern Np(V)complexes and originate from the same research group. The data are presented inTable 11.3 and refer to the reaction:NpO + 2 + NO− 2Å NpO 2 NO 2 (aq) (11.1)Rao et al. [79RAO/GUD] studied this system using solvent extraction with NaD-NNS at a total ionic strength of 2 M and obtained log 10 β(11.1, I = 2M, 298.15 K) =−(0.05 ± 0.05). The complex is weak, and substantial changes were therefore necessaryin the ionic medium in order obtain measurable effects. As shown in Appendix A,the changes made in the ionic medium can also explain satisfactorily the measuredeffects.Table 11.3: Experimental equilibrium data for the neptunium(V) nitrite system.Method Ionic medium t ( ◦ C) log 10 β ReferenceNpO + 2 + NO− 2Å NpO 2 NO 2 (aq)dis, DNNS 2 M NaClO 4 25 −(0.05±0.05) [79RAO/GUD]sp 2 M NaClO 4 ∼ 23 0.14 [78RAO/PAT]Rao and Patil [78RAO/PAT] studied the same system at the same ionic strength,but using spectrophotometry, in order to confirm the solvent extraction results. Theyobtained a slightly higher value of the constant, log 10 β(11.1, I = 2M, 296.15 K) =0.14, by measuring molar absorptivities at various ligand concentrations. No experimentaldata are reported in this study, hence no recalculation or error estimation waspossible. In view of the paucity of the available data, no selection is made in this reviewfor Np(V) nitrite complexes.11.1.4 Neptunium nitrates11.1.4.1 Aqueous neptunium nitrates11.1.4.1.a Aqueous Np(III) nitratesNo Np 3+ nitrate complexes have been identified.11.1.4.1.b Aqueous Np(IV) nitratesComplex formation in Np(IV) nitrate systems has been studied by several investigatorsand complexes formed according to the equilibria:Np 4+ + qNO − 3Å Np(NO 3 ) q 4−q(11.2)were proposed. The experimental equilibrium data have been summarised inTable 11.4. The distribution studies reported by Lahr and Knoch [70LAH/KNO]
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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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Page 254 and 255: dis 0.2 M NaClO 25 2.93 (3.42±1.0)
Page 256 and 257: sol 1 M NaCl 23 (2.06±0.13) [96RUN
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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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