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

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A. Discussion of selected references 679c) Np(V)/Np(III) redox potentialThe value of β3,Np(III) ◦ /β◦ 3,Np(V)(11.2 ± 1.8) can be calculated from the two measurementsof Fedoseev, Peretrukhin and Krot, and this should lead to a more satisfactoryvalue for β3,Np(III) ◦ because the major uncertainties (the values of the liquid junctionand estimated stability of the limiting complex of Np(IV)) cancel. Using the valuelog 10 β3 ◦ = 5.50 for Np(V) from the present review, log 10 β◦ 3= 16.7 for the Np(III)carbonate complex is calculated. This compares well with the value (15.2±0.6) for theformation constant of the corresponding americium complex [95SIL/BID], and withlog 10 β3 ◦ (15.49 ± 2.51) based on the Np(IV/III) couple in carbonate solutions (cf. Section12.1.2.1.5).d) Pu formal potentialsPotentiometric measurements of the irreversible formal potential of the Pu(IV)/Pu(III)couple in 1 M K 2 CO 3 were reported. The formal potential is −(0.495 ± 0.030) V vs.SHE and has a variation with temperature of −0.63 mV/ ◦ C. On the basis of theseresults the Gibbs energy of oxidation was found to be 47.7 kJ·mol −1 and the entropyof reaction to be −60.8 J·K −1·mol−1 . These values appear reliable but due to the absenceof independent information concerning the stoichiometry of the Pu(III) limitingcomplex, the irreversibility of the formal potential and the lack of information concerningthe ionic strength dependence of the stability of the limiting and precursor Pu(IV)complexes, this value cannot be used to determine the nature and stability of the Pu(III)carbonate complex(es). A reduction potential was reported for the Pu(V)/Pu(IV) couple(+0.6 V), but no details were given concerning the experiments giving rise to this value,and it differs significantly from other reported values.[79KUS/GAN]This is a summary of earlier work of this research group and a short presentation ofnew results from solvent extraction studies. The constants reported for the formation ofNpI 3+ were obtained from extraction studies using HTTA and HDNNS (dinonylnaphthalenesulphonicacid): β 1 = 0.8 (HTTA) and 1.3 (HDNNS). The aqueous solutioncontained 1 M H + and had an ionic strength of 2 M (probably using perchlorate asbackground anion as was done in earlier studies), and the experiments were carried outat 25 ◦ C. Formation constants of iodide complexes of Th(IV) were also reported, as wellas of oxalate complexes of Th(IV), Np(IV) and Pu(IV), of nitrite complexes of Am(III),Cm(III), of nitrate complexes of Np(IV), and of thiocyanide complexes of Tm(III). Althoughthe experimental details are not given in this paper, it can be assumed that theextraction studies were carried out at the same level of care as the earlier studies of thisgroup, e.g., [75PAT/RAM, 76BAG/RAM2]. We therefore accept the following valueswith our estimated uncertainties: log 10 β 1 (NpI 3+ , I = 2M) =−(0.10 ± 0.30) (fromthe HTTA experiment) and (0.11 ± 0.30) (from the HDNNS experiment).The values reported for the association constants of Np 4+ with nitrate (β 1 = 3.4,β 2 = 4.8, at I = 6 M) are new. However, because the measurements were carriedout at such a high ionic strength, and few experimental details were provided, thesereported values are not accepted in the present review.
680 A. Discussion of selected referencesIn addition, the first complexation constants of Np(V) complexes with nitrate,chloride, sulphate, thiocyanide, iodate, fluoride, nitrite and acetate were presented. Theextraction data are reported in the source study [79RAO/GUD], and they are discussedunder that entry below. Table 7 of [79KUS/GAN] contains, for iodate, fluoride andnitrite as ligand, three additional values for β 1 , put in parentheses and reported to bethe results of spectrophotometric measurements. These measurements are reportedin [78RAO/PAT] and are discussed under that entry above. Note that the figures in[79KUS/GAN] seem to be incorrectly placed: the figure placed at figure caption 14(a)appears to be Figure 14(b), the one placed at figure caption 14(b) looks like Figure 15,and the one placed at figure caption 15 in fact seems to be Figure 14(a).[79MOS/POZ]The comments in this entry also refer to the [78MOS/POZ] entry. Apparently theexperiments and the tabulated results (including typographical errors) are identical.For some experiments, more detail is given in the earlier reference.The authors give stability constants for the Np(V) and Pu(V) complexes with anumber of inorganic and organic ligands based on a method involving co-precipitationof the free actinide cations with amorphous Fe(OH) 3 at 20 ± 2 ◦ C in pH = 8.5 solutionsof NH 4 Cl. Experimental data describing the stability of the species in Table A.8 iseither tabulated or plotted in [78MOS/POZ]or[79MOS/POZ].Table A.8: Stability constants of Np(V) and Pu(V) complexes with various ligands asgiven in [78MOS/POZ]and[79MOS/POZ].Composition Ionic medium Ligand logβ(±2σ )of the complex (M NH 4 (Cl,L)) concentration(M)NpO + 2PuO + 2MO 2 SO − 3 1.0 0.1 − 0.28 (1.50 ± 0.05)MO 2 (SO 3 ) 3−21.0 (3.01 ± 0.4)MO 2 SO − 4 ∼ 1.5 0.15 − 0.6 (1.04 ± 0.4)MO 2 HCO 3 (aq) (c) 0.25 0.05 − 0.13 (2.15 ± 0.05)MO 2 (HCO 3 ) − 2 (c) 0.25 0.01 − 0.13 (3.66±0.10) (a) (1.90±0.10)MO 2 (HPO 4 ) − 1.0 (b) 0.05 − 0.34 (2.90 ± 0.11) (2.39±0.04)MO 2 (PO 4 ) 2− 1.0 (b) 0.05 − 0.30 (5.78 ± 0.25)(a) Result given in [78MOS/POZ] only.(b) Given, presumably incorrectly, as 0.1 M in the papers.(c) The stoiochiometry of this species was not confirmed, and this review considers that the numericalvalue of the corresponding stability constant is in contradiction with later experimental work.The wide range of ligand concentration means that there are ionic medium effectsinfluencing the precision of all of these determinations, particularly in the case of thebicarbonate and SO 2−4experiments. This is a problem common to many experiments
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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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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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Page 654 and 655: 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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