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

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11.1 Neptunium nitrogen compounds and complexes 19511.1.4.1.d Aqueous Np(VI) nitratesThe experimental equilibrium data available in the literature for the reactionsNpO 2+2+ qNO − 3Å NpO 2 (NO 3 ) q 2−q(11.4)are collected in Table 11.6. There is no direct experimental (e.g., spectroscopic) evidencefor inner sphere Np(VI) nitrate complexation reported in the available literature.As discussed in Appendix A, the papers of Rykov and Yakovlev [66RYK/YAK], Lahrand Knoch [70LAH/KNO] and of Vasiliev, Andeichuk and Rykov [75VAS/AND] aresubject to various shortcomings that preclude use of values from these sources. TheTable 11.6: Experimental equilibrium data for the Np(VI) nitrate system.Method Ionic t log 10 β(I) (a) Referencemedium ( ◦ C)NpO 2+2 + NO − 3Å NpO 2 NO + 3sp, kin 2 M HClO 4 25 −0.4 [66RYK/YAK]dis, TOA 8 M HClO 4 20 −0.24 [70LAH/KNO]dis, TTA 4 M (Na,H)ClO 4 25 −(0.68 ± 0.06) [71DAN/CHI]−(0.68±0.20) (b)pot 4 M (Na,H)ClO 4 25 −(1.05 ± 0.14)pot 0.4 M HClO 4 25 −(0.98 ± 0.02) [70AL-/WAI2]−(0.98±0.50) (b)pot 0.5 M HClO 4 25 −(0.96 ± 0.02)−(0.96±0.50) (b)pot 0.6 M HClO 4 25 −(0.89 ± 0.02)−(0.89±0.50) (b)pot 0.8 M HClO 4 25 −(0.94 ± 0.02)−(0.94±0.50) (b)NpO 2+2 + 2NO − 3Å NpO 2 (NO 3 ) 2 (aq)pot 4 M (Na,H)ClO 4 25 −(1.23 ± 0.14) [71DAN/CHI]sp 0.1 - 23 M HNO 3 ? (4.74±0.04) (c) [75VAS/AND]< −2.06 (d)(a) Refers to the value reported for the reactions indicated, for the ionic medium andat the temperature given in the table.(b) Uncertainties estimated in this review.(c) Refers to the constant for the reaction which includes water molecules, that is:NpO 2 (H 2 O) 2+6+ 2NO − 3Å NpO 2 (NO 3 ) 2 (H 2 O) 6−x + xH 2 O. The value forthe constant corresponding to Equation (11.4), q = 2, has been calculated in thisreview.(d) Upper limit value of the constant estimated in this review by assuming only thefirst complex to form for nitrate ≤ 2 M and accounting for activity factor changeswhile substituting perchlorate ions with nitrate.various experimentally measured quantities may be expressed by accounting for both
196 11. Neptunium group 15 compounds and complexesactivity coefficient changes and complex formation, which in the case of distributionstudies have the following form:D 0D=γ NpO+ ·γ 22 ,ClO− 4 H + ,mixγ NpO+ ,mix·γ 2 ·(1 + β 1·[NO − 32 H + ,ClO − 4]·γ−1cpx1,mix + (11.5)β 2·[NO − 3]2·γ−1cpx2,mix + ...)Since all experiments have been performed at constant molar ionic strength, thelogarithm of the activity factor of an ion may be expressed as a linear function of nitrateconcentration. By taking the logarithm of Equation (11.5), the only way that thelogarithm of the left hand side can be expressed as a linear function of nitrate concentrationis if the expression inside parentheses is equal to one, i.e., the constants tend tozero. Similar expressions have been used in Appendix A in the case of potentiometricmeasurements (e.g., [70AL-/WAI2, 71DAN/CHI]). In most of the papers negligiblysmall constants will provide an adequate fit to the experimental data. At this time it isnot possible to select any constants for this system.It is concluded that the dioxoneptunium(VI) nitrate complexes are weak, as is alsothe case for the other actinides [92GRE/FUG] (see also Section 20.1.3.1). This makesit difficult to distinguish between complex formation and changes in the activity coefficientsof the species studied, caused by the large changes in the composition of theionic medium when substituting an inert anion (often perchlorate) by the ligand ion(nitrate). If a β 1 value for formation of NpO 2 NO + 3is required, the use of the first associationconstant recommended for the analogous uranium system [92GRE/FUG] willprobably not cause too large an error.11.1.4.2 Solid neptunium nitrates11.1.4.2.a Np(IV)The synthesis of Np(NO 3 ) 4·2H 2 O(s) was described by Laidler [66LAI]. No chemicalthermodynamic data were reported.11.1.4.2.b Np(V)The synthesis of NpO 2 NO 3·H 2 O(s) and of NpO(NO 3 ) 3·3H 2 O(s) were describedby Laidler [66LAI]. There is some question as to whether the second of thesecompounds was properly characterised and if the neptunium is actually Np(V). TheNpO 2 NO 3·H 2 O(s) of Laidler was prepared by drying a more hydrated salt undervacuum, and Grigor’ev et al [94GRI/CHA] have reported a crystal structure forNpO 2 NO 3·2.5H 2 O(s). No chemical thermodynamic data have been reported.11.1.4.2.cNp(VI)The synthesis of NpO 2 (NO 3 ) 2·6H 2 O(s) was described by Laidler [66LAI]. Brandand Cobble [70BRA/COB] carried out a limited set of measurements of thesolubility of this salt in water (reporting a saturation molality at (25 ± 0.2) ◦ Cof(2.95 ± 0.26)). From this, and activities from the corresponding uranium system
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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 264 and 265: (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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