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

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A. Discussion of selected references 741Table A.19: Np(V) carbonate complexation constants deduced from the spectrophotometricmeasurements reported in [90RIG]. K i = [NpO 2 (CO 3 ) (1−2i)i]/([NpO 2 (CO 3 ) (3−2i)(i−1) ][CO2− 3]). The equilibrium constants deduced from only a part ofthe experimental data [90RIG] are italicised to stress that they were not used in selectionof values in the present review.Ionic media log 10 K 1 log 10 K 2 log 10 K 3series 7 and 8 0 −(0.98 ± 0.15)series4to6 0 (1.51 ± 0.15) −(0.86 ± 0.15)values finally 0 (4.7 ± 0.2) (1.51 ± 0.15) −(0.86 ± 0.15)proposed in [90RIG]this review 0.12 Na 2 CO 3 (1.4 ± 0.3)this review 0.17 Na 2 CO 3 (1.0 ± 0.28)series 1 0.5 NaClO 4 (4.30 ± 0.10)series 2 0.5 NaClO 4 4.41 3.35series 1 and 2 0.5 NaClO 4 4.75 3.71this review, data 0.18 Na 2 CO 3 (0.90 ± 0.2)from series 7 and 8values finally 0.5 NaClO 4 (4.3 ± 0.1) (2.23 ± 0.07) (1.37 ± 0.07)proposed in [90RIG]this review 0.5 NaClO 4 (4.41 ± 0.1) (2.1 ± 0.6) (1.13 ± 0.2)series 7 and 8 1 Na 2 CO 3 (1.60 ± 0.07)series4to6 1 NaClO 4 (2.38 ± 0.07) (1.86 ± 0.07)values finally 1 NaClO 4 (4.3 ± 0.2) (2.38 ± 0.07) (1.86 ± 0.07)proposed in [90RIG]this review 1 NaClO 4 (1.48 ± 0.2)series 7 and 8 2 Na 2 CO 3 (2.05 ± 0.07)series4to6 2 NaClO 4 (2.54 ± 0.07) (2.47 ± 0.07)values finally 2 NaClO 4 (4.6 ± 0.3) (2.54 ± 0.07) (2.47 ± 0.07)proposed in [90RIG]this review 2 (1.96 ± 0.2)values finally 3 NaClO 4 (2.9 ± 0.2)proposed in [90RIG]
742 A. Discussion of selected referencesof NpO + 2 and NpO 2(CO 3 ) 3−2, and has an intermediate molar absorptivity, so qualitativeinterpretation (prior to curve fitting or to help in interpretation of the results) is notpossible. Riglet noted that these problems did not cause difficulties in the study of theinfluence of ionic strength on the shift of the curves of absorbance vs.log 10 [CO 2−3 ] (todetermine values of ε 2 and ε 3 ), and her reported values are indeed in fair agreementwith the values determined in the present review from other published data (a graphicalrecalculation led to ε 3 =−(0.08 ± 0.05) kg·mol −1 ). However, these data are notused in the selection of thermodynamic parameters in the present review. An attemptby Riglet to fit all her spectrophotometric and solubility results within the uncertaintiesof the measurements was unsuccessful, and she concluded this inconsistency was dueto trying to simultaneously determine the unknown molar absorptivity coefficients ofNpO 2 (CO 3 ) 3−2from the fit of the data.b) Np(V) solubility in sodium carbonate mediaThis thesis also reported and discussed a study of Np(V) solubility in carbonicacid/bicarbonate/carbonate aqueous solutions. The experimental data were thosereported in several earlier publications [84VIT, 86GRE/ROB], and reports ofEuropean joint research contracts [85CÔM, 85KIM]. Sensitivity analysis was done(page 153 [90RIG]). The thermodynamic values deduced by the author and in thosefrom recalculation in the present review are consistent within the stated uncertainties(Table A.20). Riglet noted that the main uncertainty was due to poor crystallisationof the solid phase when NpO + 2was the major soluble neptunium species. This seemsto have been substantiated in later studies (e.g., [93LEM/BOY]). As mentionedelsewhere in this appendix (see the discussion of [84VIT]), this relatively pooraccuracy probably cannot be attributed to ion exchange equilibria in the solid phase asproposed by Volkov et al.[79VOL/VIS2]2(x − 1)Na + + NaNpO 2 CO 3 (s) Å Na (2x−1) NpO 2 (CO 3 ) x (s) + (1 − x)CO 2−3The solids, typically hydrated Na 0.6 NpO 2 (CO 3 ) 0.8 (s), did not usually result fromlengthy equilibration with aqueous solutions. Vitorge carried out measurements[84VIT], for the chemical conditions under which NpO + 2was the major solublecomplex by assuming the equilibriumNa (2x−1) NpO 2 (CO 3 ) x (s) Å (2x − 1)Na + + NpO + 2 + xCO2− 3controlled the solubility and deduced values of the corresponding solubilityproduct, K s,x , and x values (Table A.21) from linear regression (the plot oflog 10 [Np(V)] vs. log 10 [CO 2−3] was a straight line with slope of approximately −1).He found the “best” stoichiometry to be Na 0.72 NpO 2 (CO 3 ) 0.86 (s), but after severalweeks a hydrated NaNpO 2 CO 3 (s) was formed. Reanalysis of the data for eachsuccessive dissolution and precipitation of Np(V) indicates the linear regressionresults were more accurate for dissolution than for precipitation; over time the x valuebecame closer to 1 and the K s,1 decreased (Table A.21). This is evidence that hydratedNa (2x−1) NpO 2 (CO 3 ) x (s) with x < 1 was formed initially, but that this solid phase wasmetastable, and was slowly transformed to a thermodynamic stable phase, hydrated
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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 716 and 717: A. Discussion of selected reference
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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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