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5 −10.63±0.11 (g) −12.48±0.23 (g)5 0.14±0.15 (h,i) −1.64±0.34 (h,j)(a) [91KIM/KLE, 94NEC/KIM].(b) [83MAY].(c) [86GRE/ROB].(d) Best fit calculated in the present review.(e) Minimum solubility (and not mean or fitted values) assuming that the scatter of the data was due to solid transformation (see text and the discussionof [86GRE/ROB]).(f) A β 3 fixed value was added by this review.(g) [95NEC/RUN], 5 M NaCl.(h) Graphically estimated by this review from Figure 3d of [95NEC/RUN] and using the same correction as in that paper for chloride complexation.(i) Value of log 10 (K s,1 × β 3 );(j) Value of log 10 (K s,2 /K s,1 );(k) Uncertainties, 1.96 standard deviations of a weighted mean of the corresponding equilibrium constant (not increased for systematic error (see text)in this table to allow statistical comparison), and 1.96 / √ n values (n is the number of measurements) are calculated in the present review.A. Discussion of selected references 753
754 A. Discussion of selected referencesThe value of the solubility product for hydrated NaNpO 2 CO 3 (s), as measured byKim et al. [91KIM/KLE] and Neck et al. [94NEC/RUN] and extrapolated to zeroionic strength in the present review, was slightly greater than found in other reliablesolubility studies [83MAY, 86GRE/ROB, 93LEM/BOY]. The solubility values in 1 MNaClO 4 aqueous solutions were the same as those of Maya [83MAY], although differentvalues were used for the protonation constants for carbonate ion. For 3 M NaClO 4aqueous solutions the results are clearly different from the results of Grenthe, Robouchand Vitorge [86GRE/ROB]. The difference is too large to have resulted from the pHelectrode calibration problems discussed above, but might have resulted from differentsolid phases being present in the two studies. This discrepancy is reflected mainly inthe value of β 1 at I = 3 M, which would affect the accuracy of β ◦ 1 andhaveadramaticeffect on extrapolation to zero ionic strength (i.e., onthevalueofε (NpO2 CO − 3 ,Na+ ) ).The stepwise constants, K 2 and K 3 , are in agreement with the values selected by thisreview,evenuptoI = 5 M. This was quite surprising as the SIT approximation is usuallynot valid at such high ionic strengths and there was the possibility of systematicdeviation at high ionic strength. In conclusion, except for the value of log 10 β 1 noneof the complexation constants at high ionic strength deviate by more than a factor of10 0.3 from other published works as reinterpreted in the present review. The origin ofthe deviation in log 10 β 1 is not understood.The spectra of Np(V) carbonate complexes were also reported and were used later[94NEC/RUN] to calculate the formation constants for two Np(V) carbonate complexes.The spectra were in accord with those reported previously [90RIG]. The reportedvalue of β 1 is in quite reasonable agreement (within 0.2 in log 10 β) with the valuemeasured by the solubility technique, and the same was true for the β 2 values reportedin [94NEC/RUN]. The formation constants are inconsistent only within the rather optimisticestimates of the uncertainties by the authors. It is also interesting to note thatthe stepwise constant, k 2 = β 2 /β 1 , measured by each technique, was the same.[91OKA/REE]This study reported the use of absorption spectroscopy and laser photoacoustic spectroscopy(LPAS) to investigate the hydrolysis of 242 Pu(VI). A value of the first hydrolysisconstant, log10 ∗β1,1 =−(5.2±0.2) was reported for (21±1) ◦ Candamediumof0.1MNaClO 4 . The value was based on a least-squares fit to LPAS data and was dependenton the assumption that PuO 2 OH + is the sole major hydrolysis species for the Pu(VI) ata concentration of 2.6 × 10 −4 M for pH values below 5.3. It appears the reported hydrogenion concentrations are really 10 −pH . The authors later [93OKA/REE] includedpolymeric hydrolysis species in their data analysis, and recinded their proposed valuefor log10 ∗β1,1. Therefore, this value for log10 ∗ β is not credited in the present review.[91POS/ROV]The adsorption of Np(IV) on stainless steel in nitric acid solutions (no supporting electrolyte)of concentration 0.1 − 6 M has been investigated at an unspecified temperature.The Np concentration used is not reported, but from the figures it must have
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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 728 and 729: A. Discussion of selected reference
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Page 824 and 825: 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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