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

More documents

Recommendations

Info

A. Discussion of selected references 775This value is used in the present review and, as in the original paper, the differencein the enthalpy effect corresponding to the transfer of the NpO + 2ion from 1.0 M HClto infinite dilution is assumed to be negligible.[94NEC/KIM]This review used the Np(V) solubility measurements tabulated in this report, withother data published by the same group of authors (as discussed in this appendix[91KIM/KLE, 94NEC/RUN]). Experimental data of Np(V) liquid-liquid extraction byNaDNNS from 0.2 to 5 M Na(ClO 4 ,Cl) aqueous solutions were also tabulated in thisreport. These were used by Neck, Kim and Kanellakopulos to estimate Np(V) activitycoefficients, however there are difficulties with the interpretation of the authors as explainedin the discussion of [94NEC/RUN] (work based on the same experimental datafrom the same group). In the present review we have interpreted interactions betweenNpO + 2 and Cl− solely in terms of the selected interaction coefficients rather than invokea model involving the formation of weak chloro-complexes (also see [96RUN/NEU]).The interpretation of the liquid-liquid extraction study neglected activity coefficientcorrections for the organic phase. These corrections might be important compared toactivity coefficient corrections. The corresponding uncertainty could not be deducedfrom statistical analysis since some of the possible errors were systematic (not random).The necessary activity coefficient corrections (especially for chloride media,cf. Section 12.1.2.1.3.c) increased the uncertainty in the interpretation of the data.Therefore these extraction measurements were not used in the present review to estimatethe stability constants of Np(V) carbonate complexes (see also the discussions of[91KIM/KLE, 94NEC/RUN] in this appendix).[94NEC/RUN]This paper incorporates and discusses the solubility and spectroscopic results describedin an earlier report [91KIM/KLE]. New activity coefficient values are also proposed.In this paper the SIT, as used in the present review, was used by Neck et al., while ina later paper [95FAN/NEC] the authors used a simplified Pitzer equation. The junctionpotential was measured (and not set to zero by using the same ionic medium forthe reference electrode and working solutions). The interpretation of the liquid-liquidextraction study [94NEC/KIM, 95NEC/FAN] neglected activity coefficient correctionsfor the organic phase. These corrections might be important compared to activity coefficientcorrections. The corresponding uncertainty could not be deduced from statisticalanalysis since some of the possible errors were systematic (not random). In addition,possible chemical systematic error (discussed above) could be even more important.For these reasons, the activity coefficients proposed in this work [94NEC/RUN] arenot accepted in the present review. However, as mentioned elsewhere in this appendix(see discussions of [91KIM/KLE, 94NEC/KIM]), some of the systematic errors, ifthey exist, will cancel, especially for the values of equilibrium constants extrapolatedto zero ionic strength. The ε value of the solubility products can be calculated fromε values used by this review (see Appendix B) that were determined from isopiestic
776 A. Discussion of selected references(for ε (Na + ,ClO − )), equilibrium constant (for ε 4 (Na + ,CO 2− )) and redox (for ε (NpO + 3 2 ,ClO−))4measurements. For this last value an analogy between NpO 2+2and UO 2+2was also assumedsince the experimental determinations of the values of the MO 2+2 /MO+ 2 redoxcouples were found to be the same for M = U, Np, Pu [87RIG/VIT, 89RIG/ROB,90RIG, 94CAP/VIT]. The ε value of the two solubility product reactions as determinedby Kim et al. and Neck et al. [91KIM/KLE, 95NEC/RUN] are not consistent withthe value calculated in the present review (Table A.29). The two ε (NpO+2 ,ClO− 4 ) valuescalculated from those ε values are also not consistent with later determinations bythe same group [95NEC/FAN]. A simplified Pitzer equation was used from which thisreview determined ε (NpO+2 ,ClO− 4 ) = 0.20 ± 0.03 kg·mol−1 , a value which is in accordwith the value 0.25 ± 0.05 accepted in the present review (Table A.29).Table A.29: Values of ε (NpO+2 ,ClO− 4 )recalculated in this review from the measurementsof [91KIM/KLE, 94NEC/KIM, 95NEC/FAN, 95NEC/RUN] (a) and auxiliary valuesfrom Appendix B. Similar values using auxiliary values calculated in this review fromexperimental data published in these references are reported in Table 12.5.ε (h) ε (e) ε (f) log 10 Ks,1◦this review (b) (0.25±0.05)[91KIM/KLE] (0.36±0.04)[95NEC/RUN] (0.34±0.04) (0.37±0.09) (0.42±0.09)0.1to3M (c) (0.38±0.07) −(10.95 ± 0.11)0.1to5M (c) (0.38±0.04) −(10.95 ± 0.07)[95NEC/FAN] (d) (0.20±0.05)[94NEC/KIM] (g) (0.18±0.03)(a) Unless noted otherwise, ε is ε(NpO +,ClO − 2 4 ) from ε s,i = iε (Na + ,CO2−) + ε (NpO + 3 2 ,ClO− 4 ) + (2i −1)ε (Na + ,ClO−4) + x ir as determined by SIT linear regression from the values determined at different ionicstrength for K s,i ,theNa (2i−1) NpO 2 (CO 3 ) i·x i H 2 O(s) solubility product, where r is a H2 O/m NaClO4 meanvalue, x 1 = 3.5 and x 2 is unknown; i=1 in column 2; i=2 in columns 3 and 4.(b) ε values calculated with the auxiliary values used by this review.(c) Calculated in the present review from the data reported in [91KIM/KLE].(d) Calculated in the present review from the Pitzer set of parameters proposed in [95NEC/FAN]. The uncertaintyhas been estimated in this review as the difference (ε(3 M) - ε(0.5 M)) where the ε values were calculatedfrom the mean activity coefficients.(e) Calculated from K s,2 using the arbitrary x 2 value x 2 = 0 in the solid phase.(f) Calculated from K s,2 using the arbitrary x 2 value x 2 = 3.5.(g) From liquid-liquid extraction data also published in [95NEC/FAN](h) Calculated using K s,1 (unless otherwise noted)Thus, the ionic strength corrections from this and related work [95NEC/RUN,96RUN/NEU] are not self consistent, and the ε values from the solubility productsare not consistent with currently accepted ε values. These two inconsistencies could
Page 1 and 2:
4VOLUMECHEMICALTHERMODYNAMICSCHEMIC
Page 3 and 4:
CHEMICAL THERMODYNAMICSVol. 1. Chem
Page 5 and 6:
Published under the imprint NORTH-H
Page 7 and 8:
viPREFACEviewed several of the othe
Page 9 and 10:
viiiACKNOWLEDGEMENTSand Whiteshell
Page 11 and 12:
xFOREWORDsending comments on the TD
Page 13 and 14:
xiiCONTENTSIII Discussion of neptun
Page 15:
xivCONTENTS11.1.4.2 Solid neptunium
Page 18 and 19:
CONTENTSxvii20.5.1 PuSb(cr) . . . .
Page 20 and 21:
List of Tables2.1 Symbols and termi
Page 22 and 23:
LIST OF TABLESxxi20.2 Experimental
Page 24 and 25:
List of Figures2.1 Standard order o
Page 26:
Part IIntroductory material1
Page 29 and 30:
4 1. IntroductionInorganic Complexe
Page 31 and 32:
6 1. Introductionlected, but form a
Page 34 and 35:
Chapter 2Standards, Conventions, an
Page 36 and 37:
2.1 Symbols, terminology and nomenc
Page 38 and 39:
Page 40 and 41:
Page 42 and 43:
Page 44 and 45:
Page 46 and 47:
Page 48 and 49:
2.2 Units and conversion factors 23
Page 50 and 51:
2.2 Units and conversion factors 25
Page 52 and 53:
2.3 Standard and reference conditio
Page 54 and 55:
2.3 Standard and reference conditio
Page 56 and 57:
2.5 Uncertainty estimates 31Table 2
Page 58 and 59:
2.7 Presentation of the selected da
Page 60:
2.7 Presentation of the selected da
Page 64 and 65:
Chapter 3Selected neptunium dataThi
Page 66 and 67:
41Table 3.1: Selected thermodynamic
Page 68 and 69:
43Table 3.1: (continued)Compound f
Page 70 and 71:
Page 72 and 73:
Page 74 and 75:
49Table 3.2: (continued)SpeciesReac
Page 76 and 77:
Page 78 and 79:
Chapter 4Selected plutonium dataThi
Page 80 and 81:
Page 82 and 83:
Page 84 and 85:
Page 86 and 87:
61SpeciesPu(OH) 3 (cr)ReactionTable
Page 88 and 89:
Page 90 and 91:
Chapter 5Selected auxiliary dataThi
Page 92 and 93:
Page 94 and 95:
Page 96 and 97:
Page 98 and 99:
Page 100 and 101:
Page 102 and 103:
(footnotes continued)(p) Data from
Page 104 and 105:
79Table 5.2: (continued)Species Rea
Page 106:
81Table 5.2: (continued)Species Rea
Page 110 and 111:
Chapter 6Elemental neptunium6.1 Nep
Page 112 and 113:
6.1 Neptunium crystal and liquid 87
Page 114:
6.2 Neptunium ideal monatomic gas 8
Page 117 and 118:
92 7. Neptunium aqua ionsE ◦′ (
Page 119 and 120:
94 7. Neptunium aqua ionsto the sta
Page 121 and 122:
96 7. Neptunium aqua ions(∂ E ◦
Page 123 and 124:
98 7. Neptunium aqua ionsnon-system
Page 125 and 126:
100 7. Neptunium aqua ionsto the re
Page 127 and 128:
102 7. Neptunium aqua ionsTable 7.4
Page 130 and 131:
Chapter 8Neptunium oxygen andhydrog
Page 132 and 133:
8.1 Aqueous neptunium hydroxide com
Page 134 and 135:
Page 136 and 137:
Page 138 and 139:
Page 140 and 141:
Page 142 and 143:
8.2 Crystalline and amorphous neptu
Page 144 and 145:
Page 146 and 147:
Page 148 and 149:
Page 150 and 151:
Page 152 and 153:
Page 154:
Page 157 and 158:
132 9. Neptunium group 17 (halogen)
Page 159 and 160:
Page 161 and 162:
Page 163 and 164:
Page 165 and 166:
Page 167 and 168:
Page 169 and 170:
Page 171 and 172:
Page 173 and 174:
Page 175 and 176:
Page 177 and 178:
Page 179 and 180:
Page 181 and 182:
Page 183 and 184:
Page 185 and 186:
Page 187 and 188:
Page 189 and 190:
Page 191 and 192:
Page 193 and 194:
Page 195 and 196:
Page 197 and 198:
Page 199 and 200:
Page 201 and 202:
Page 203 and 204:
178 10. Neptunium group 16 compound
Page 205 and 206:
Page 207 and 208:
Page 209 and 210:
Page 212 and 213:
Chapter 11Neptunium group 15compoun
Page 214 and 215:
11.1 Neptunium nitrogen compounds a
Page 216 and 217:
Page 218 and 219:
Page 220 and 221:
Page 222 and 223:
11.2 Neptunium phosphorus compounds
Page 224 and 225:
11.2 Neptunium phosphorus compounds
Page 226 and 227:
Chapter 12Neptunium group 14compoun
Page 228 and 229:
12.1 Neptunium carbon compounds and
Page 230 and 231:
cal 0.3-1.6 M Na 2 SO 4 25 r H m =
Page 232 and 233:
vlt 0 25 (0.340±0.002) (k) [95OFF/
Page 234 and 235:
sol K + ,CO 2−3 , 20 −(2.31±0.
Page 236 and 237:
Page 238 and 239:
Page 240 and 241:
Page 242 and 243:
Page 244 and 245:
Page 246 and 247:
Page 248 and 249:
Page 250 and 251:
Page 252 and 253:
sp 0.1 M NaCl 23 (4.68±0.03) [96RU
Page 254 and 255:
dis 0.2 M NaClO 25 2.93 (3.42±1.0)
Page 256 and 257:
sol 1 M NaCl 23 (2.06±0.13) [96RUN
Page 258 and 259:
sol 0.15 M Na 2 CO 3 −(2.58±0.64
Page 260 and 261:
sol 1 M NaClO 30 −(4.0±0.2) [93L
Page 262 and 263:
sol 3 M NaClO 25 −(2.14±0.18)
Page 264 and 265:
(f) Values selected in this review
Page 266 and 267:
Page 268 and 269:
Page 270 and 271:
Page 272 and 273:
Page 274 and 275:
Page 276 and 277:
Page 278 and 279:
Page 280 and 281:
Page 282 and 283:
(V vs. SHE) (V vs. SHE) (V · K −
Page 284 and 285:
(h) 1MK 2 CO 3 is written in Table
Page 286 and 287:
Page 288 and 289:
Page 290 and 291:
Page 292 and 293:
2 3 r H m (5.0±2.0)log 10 β 2 MO
Page 294 and 295:
Page 296 and 297:
Page 298 and 299:
Page 300 and 301:
Page 302 and 303:
Page 304 and 305:
Page 306 and 307:
Page 308 and 309:
Page 310 and 311:
Page 312:
Page 315 and 316:
290 13. Neptunium group 2 (alkaline
Page 317 and 318:
292 14. Neptunium group 1 (alkali)
Page 320:
Part IVDiscussion of plutonium data
Page 323 and 324:
298 15. Elemental plutoniumTable 15
Page 325 and 326:
300 15. Elemental plutoniumfrom 298
Page 327 and 328:
302 16. Plutonium aqua ionsthe prop
Page 329 and 330:
304 16. Plutonium aqua ions298.15 K
Page 331 and 332:
306 16. Plutonium aqua ionsE ◦ =
Page 333 and 334:
308 16. Plutonium aqua ionsSm ◦ (
Page 335 and 336:
310 16. Plutonium aqua ionsstandard
Page 337 and 338:
312 16. Plutonium aqua ions r H ◦
Page 339 and 340:
314 16. Plutonium aqua ionsE ◦′
Page 341 and 342:
316 16. Plutonium aqua ionsFigure 1
Page 343 and 344:
318 17. Plutonium oxygen and hydrog
Page 345 and 346:
Page 347 and 348:
Page 349 and 350:
Page 351 and 352:
1:1 pot RT 1 M NaClO 4 −5.71 [49K
Page 353 and 354:
Page 355 and 356:
Page 357 and 358:
Page 359 and 360:
Page 361 and 362:
Page 363 and 364:
Page 365 and 366:
Page 367 and 368:
Page 370 and 371:
Chapter 18Plutonium group 17 (halog
Page 372 and 373:
18.1 Plutonium halide compounds 347
Page 374 and 375:
Page 376 and 377:
Page 378 and 379:
Page 380 and 381:
Page 382 and 383:
Page 384 and 385:
Page 386 and 387:
Page 388 and 389:
Page 390 and 391:
Page 392 and 393:
Page 394 and 395:
Page 396 and 397:
18.2 Aqueous plutonium group 17 (ha
Page 398 and 399:
Page 400 and 401:
Page 402 and 403:
PuO 2+2+ 3F − Å PuO 2 F − (b)3
Page 404 and 405:
Page 406 and 407:
Page 408 and 409:
Page 410 and 411:
Page 412:
Page 415 and 416:
390 19. Plutonium group 16 compound
Page 417 and 418:
Page 419 and 420:
Page 421 and 422:
Page 423 and 424:
Page 426 and 427:
Chapter 20Plutonium group 15 compou
Page 428 and 429:
20.1 Plutonium nitrogen compounds a
Page 430 and 431:
Page 432 and 433:
Pu + NO 3Å PuNO 3sp 2 M HClO 4 20
Page 434 and 435:
3 3 3dis, TTA 6 M (? HCl or HClO 4
Page 436 and 437:
Page 438 and 439:
Page 440 and 441:
20.2 Plutonium phosphorus compounds
Page 442 and 443:
20.2 Plutonium phosphorus compounds
Page 444 and 445:
20.3 Solid plutonium phosphorus com
Page 446 and 447:
20.4 Plutonium arsenic compounds 42
Page 448 and 449:
20.6 The plutonium-bismuth system 4
Page 450:
20.6 The plutonium-bismuth system 4
Page 453 and 454:
Page 455 and 456:
Page 457 and 458:
Page 459 and 460:
Page 461 and 462:
Page 463 and 464:
Page 465 and 466:
Page 467 and 468:
Page 469 and 470:
Page 471 and 472:
446 22. Plutonium group 2 (alkaline
Page 474:
Chapter 23Plutonium group 1 (alkali
Page 477 and 478:
452 BIBLIOGRAPHY[47GIN/COR][48KRA/N
Page 479 and 480:
454 BIBLIOGRAPHY[49MAG/LAC][49ROB][
Page 481 and 482:
456 BIBLIOGRAPHY[51WES/EYR][51WES/W
Page 483 and 484:
458 BIBLIOGRAPHY[55COH/SUL]Cohen, D
Page 485 and 486:
460 BIBLIOGRAPHYmetals in connectio
Page 487 and 488:
462 BIBLIOGRAPHY[59SHE/TIM][59STU][
Page 489 and 490:
464 BIBLIOGRAPHY[61SCH][61STO/FRY][
Page 491 and 492:
466 BIBLIOGRAPHY[63ROB/WAL] Roberts
Page 493 and 494:
468 BIBLIOGRAPHY[64SIL/MAR][65CHO/K
Page 495 and 496:
470 BIBLIOGRAPHY[66DAN/ORL][66FRO/K
Page 497 and 498:
472 BIBLIOGRAPHY[67ERM/STA][67FRL/C
Page 499 and 500:
474 BIBLIOGRAPHY[68KRU/SAV][68KRY/K
Page 501 and 502:
476 BIBLIOGRAPHY[69KEN/LEA][69KRY/K
Page 503 and 504:
478 BIBLIOGRAPHY[70HIN/COB][70KRO/G
Page 505 and 506:
480 BIBLIOGRAPHY[71MOS][71MOS2][71M
Page 507 and 508:
482 BIBLIOGRAPHY[72MET/GUI][72NIK/S
Page 509 and 510:
484 BIBLIOGRAPHY[73PAT/RAM2][73PIT]
Page 511 and 512:
486 BIBLIOGRAPHY[74SAV][74SIM/VOL][
Page 513 and 514:
488 BIBLIOGRAPHY[75OSB/FLO][75PAT/R
Page 515 and 516:
490 BIBLIOGRAPHY298.15 K”, J. Che
Page 517 and 518:
492 BIBLIOGRAPHY[76VOL/VIS][77BAG/R
Page 519 and 520:
494 BIBLIOGRAPHY[78HAL/LEE][78HUR][
Page 521 and 522:
496 BIBLIOGRAPHYof plutonium(IV)”
Page 523 and 524:
498 BIBLIOGRAPHYNa 0.6 NpO 2 (CO 3
Page 525 and 526:
500 BIBLIOGRAPHY[81CHI/AKH][81CIA/F
Page 527 and 528:
502 BIBLIOGRAPHY[81WOO][82ALC/ROB][
Page 529 and 530:
504 BIBLIOGRAPHY[83ALL][83BES/LIN][
Page 531 and 532:
506 BIBLIOGRAPHY[83SCH/GOR]Schmidt,
Page 533 and 534:
508 BIBLIOGRAPHY[84LEM][84LIE/KIM][
Page 535 and 536:
510 BIBLIOGRAPHY[85CÔM][85EIS/KIM]
Page 537 and 538:
512 BIBLIOGRAPHY[85NEW/SUL][85RAI/R
Page 539 and 540:
514 BIBLIOGRAPHY[86FAH][86FRE/KEL]F
Page 541 and 542:
516 BIBLIOGRAPHY[87BEN][87BEN/HOF][
Page 543 and 544:
518 BIBLIOGRAPHY[88HIR/LIE][88ITU][
Page 545 and 546:
520 BIBLIOGRAPHYGeochim. Cosmochim.
Page 547 and 548:
522 BIBLIOGRAPHY[90BEN][90CAP/VIT][
Page 549 and 550:
524 BIBLIOGRAPHY254, 258, 258, 264,
Page 551 and 552:
526 BIBLIOGRAPHY[91MEI][91NIT][91OK
Page 553 and 554:
528 BIBLIOGRAPHYment”, Waste Mana
Page 555 and 556:
530 BIBLIOGRAPHY[93ERI/NDA][93GIF/V
Page 557 and 558:
532 BIBLIOGRAPHY[93TAY/LEM][93WEG/O
Page 559 and 560:
534 BIBLIOGRAPHYpages 222, 223, 226
Page 561 and 562:
536 BIBLIOGRAPHYK, gas-phase infrar
Page 563 and 564:
538 BIBLIOGRAPHY[96ALL/VEI][96CAP/V
Page 565 and 566:
540 BIBLIOGRAPHY[97CAP/VIT][97FEL/R
Page 567 and 568:
542 BIBLIOGRAPHY[99RAI/HES2][99RAR/
Page 569 and 570:
544 LIST OF CITED AUTHORSTable 23.1
Page 571 and 572:
Page 573 and 574:
Page 575 and 576:
Page 577 and 578:
Page 579 and 580:
Page 581 and 582:
Page 583 and 584:
Page 585 and 586:
Page 587 and 588:
Page 589 and 590:
Page 591 and 592:
Page 593 and 594:
Page 596 and 597:
Appendix ADiscussion of selected re
Page 598 and 599:
A. Discussion of selected reference
Page 600 and 601:
Page 602 and 603:
Page 604 and 605:
Page 606 and 607:
Page 608 and 609:
Page 610 and 611:
Page 612 and 613:
Page 614 and 615:
Page 616 and 617:
Page 618 and 619:
Page 620 and 621:
Page 622 and 623:
Page 624 and 625:
Page 626 and 627:
Page 628 and 629:
Page 630 and 631:
Page 632 and 633:
Page 634 and 635:
Page 636 and 637:
Page 638 and 639:
Page 640 and 641:
Page 642 and 643:
Page 644 and 645:
Page 646 and 647:
Page 648 and 649:
Page 650 and 651:
Page 652 and 653:
Page 654 and 655:
Page 656 and 657:
Page 658 and 659:
Page 660 and 661:
Page 662 and 663:
Page 664 and 665:
Page 666 and 667:
Page 668 and 669:
Page 670 and 671:
Page 672 and 673:
Page 674 and 675:
Page 676 and 677:
Page 678 and 679:
Page 680 and 681:
Page 682 and 683:
Page 684 and 685:
Page 686 and 687:
Page 688 and 689:
Page 690 and 691:
Page 692 and 693:
Page 694 and 695:
Page 696 and 697:
Page 698 and 699:
Page 700 and 701:
Page 702 and 703:
Page 704 and 705:
Page 706 and 707:
Page 708 and 709:
Page 710 and 711:
Page 712 and 713:
Page 714 and 715:
Page 716 and 717:
Page 718 and 719:
Page 720 and 721:
Page 722 and 723:
Page 724 and 725:
Page 726 and 727:
Page 728 and 729:
Page 730 and 731:
Page 732 and 733:
Page 734 and 735:
Page 736 and 737:
Page 738 and 739:
Page 740 and 741:
Page 742 and 743:
Page 744 and 745:
Page 746 and 747:
Page 748 and 749:
Page 750 and 751: A. Discussion of selected reference
Page 778 and 779: 5 −10.63±0.11 (g) −12.48±0.23
Page 788 and 789: dataarein1MNa + media, except as no
Page 824 and 825: Appendix BIonic strength correction
Page 826 and 827: B.1 The specific ion interaction eq
Page 836 and 837: B.2 Ion interaction coefficients ve
Page 838 and 839: B.3 Tables of ion interaction coeff
Page 848 and 849: Appendix CAssigned uncertainties
Page 850 and 851:
C.2 Two or more independent source
Page 852 and 853:
C.2 Two or more independent source
Page 854 and 855:
C.3 Several data at different ionic
Page 856 and 857:
C.3 Several data at different ionic
Page 858 and 859:
C.4 Procedures for data handling 83
Page 860 and 861:
C.4 Procedures for data handling 83
Page 862 and 863:
Index837
Page 864 and 865:
INDEX - GENERAL 839standard state p
Page 866 and 867:
INDEX - NEPTUNIUM 841elemental nept
Page 868 and 869:
INDEX - PLUTONIUM 843Index - pluton
Page 870:
INDEX - PLUTONIUM 845monobismuthide
show all

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

Create successful ePaper yourself

Delete template?

Save as template?