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

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8.2 Crystalline and amorphous neptunium oxides and hydroxides 117Figure 8.2: Phase relations for the neptunium-oxygen system (from [87RIC/SAR],with permission).
118 8. Neptunium oxygen and hydrogen compounds and complexeshave used f H ◦ m (NpO 2(OH) 2 (cr)) to estimate the enthalpy of formation of the anhydrousoxide to be −1058 kJ·mol −1 , and they further estimated an oxygen pressureof 10 14 Pa would be required to stabilise the solid. Similarly, using values fromGrenthe et al. [92GRE/FUG] and f H ◦ m (NpO 2(OH) 2 (cr)) from the present review, f H ◦ m (NpO 3(cr)) = −(1068 ± 7) kJ·mol −1 , and if the difference in the entropiesof NpO 3 (cr) and NpO 2 (OH) 2 (cr) is approximately the same as for the correspondinguranium compounds, f G ◦ m (NpO 3(cr)) =−(990 ± 10) kJ·mol −1 . By comparisonwith the Gibbs energies of formation for Np 2 O 5 (cr) and NpO 2 (cr), it appears that synthesisof this anhydrous oxide from the lower oxides and oxygen gas is not feasibleat practical pressures (see also [77MAL]) and no thermodynamic data are selected forNpO 3 (cr) in the present review.8.2.3.2 Dioxoneptunium(VI) hydrated oxides and hydroxidesThe uranium(VI)-water system has been found to be quite complex [92GRE/FUG],and even with the sparse experimental data available it is evident that several differentsolids can be found in the corresponding neptunium(VI)-water system.A hydrated neptunium(VI) oxide or hydroxide can be synthesised bypassing ozone/oxygen mixtures through suspensions of NpO 2 OH(am) at 90 ◦ C[64BAG/LAI, 75BEL/IL’]. The solid produced by this method may also contain someNp(VII) [74CHA/MAT]. The resulting precipitate (which has an X-ray diffractionpattern similar to that of uranium trioxide dihydrate [64BAG/LAI]), when dried inair at 100 to 105 ◦ C, is converted to a solid that was reported [64BAG/LAI] tobeisostructural with β-UO 2 (OH) 2 (cr) (on the basis of the X-ray diffraction pattern).Infrared and proton magnetic resonance spectroscopic results [75BEL/IL’] addedevidence in favour of considering this compound to be a true hydroxide with no waterof hydration. However, Kato et al. [96KAT/KIM] have recently reported preparationof a neptunium trioxide monohydrate by neutralisation of an acidic solution ofNp(VI). Their solid has an X-ray diffraction pattern and an infrared spectrum thatdiffer markedly from those of the solid of Bagnall and Laidler [64BAG/LAI] ofthe same stoichiometry and from those of other hydrated solids reported previously[64BAG/LAI, 75BEL/IL’, 75CHA/MAT]. For the purposes of the present review,these two different solids with the same apparent stoichiometry are distinguishedby referring to the dried solid of Bagnall and Laidler as “NpO 2 (OH) 2 (cr)”, and tothe solid of Kato et al. as “NpO 3·H 2 O(cr)”. Chaikhorskii, Matuzenko and Leikina[75CHA/MAT] also reported formation of an amorphous solid, NpO 3· 4H 2 O(am),on storage of the dihydrate over water in a sealed vessel for 12-15 days at “roomtemperature”. It appears the Np(VI) hydrated oxides and hydroxides may be a fairlycomplicated system, amd more work remains to be done to clarify which compoundsare stable.Moskvin [71MOS3] reported the solubility of “NpO 2 (OH) 2 (s)” (at 20 ◦ C) as a functionof pH (I ≪ 0.1M, self medium with small amounts of an unidentified acid). Thissolid was apparently not well characterised, nor does it appear that the material was reexaminedafter equilibration with the aqueous solutions. However, it appears likely thatunder the stated experimental conditions the solid was primarily the hydrated hydrox-
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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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Page 110 and 111: Chapter 6Elemental neptunium6.1 Nep
Page 112 and 113: 6.1 Neptunium crystal and liquid 87
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Page 127 and 128: 102 7. Neptunium aqua ionsTable 7.4
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168 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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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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