Coulometric Determination of Plutonium in PWR Spent Fuels PWR
6
0
0
전체 글
(2) . *
(3) . ). (2000. 8. 10. Coulometric Determination of Plutonium in PWR Spent Fuels Se Chul Sohn*, Moo Yul Suh, Jung Suk Kim, Byung Chul Song, Kwang Yong Jee, In Kyu Choi, and Won Ho Kim Korea Atomic Energy Research Institute, Daejon 305-600, Korea Received August 10, 2000). .
(4) ! "#$ %&'() &$ *+. , -./ 01 2(AG MP-1)3 . ! *)4 5 &$, 67"8"#$ %& '( . *+. 9 :; < => ?@AB 67, C D E &$F => G 2 "#$ %&6HI JK L *+. MNOF , ?@AB3 67 ! ; P. &$OF J &QR3 S*)4, 5 "#$ %&OF TU; G 2 VW./I 5 X Y, Z[Z2 \]+. ^_` . ! a& "#$ &$OF J &QR; C D Z[b c 0.230d3.02 mg e8: 99.36%.f+.
(5) K`I 0.250d0.450 mg5 %& ! g, "#$ &$OF J hi &jR(AJ^_kl, RSD); 0.38%.f+. ABSTRACT. Separation and coulometric titration method were applied for the determination of plutonium content in samples of PWR spent fuel. Plutonium was separated on an anion exchange(AG MP-1) column and determined by the controlled-potential coulometric titration. In this study, we discussed some experimental conditions related to the separation and determination of plutonium in PWR spent fuel samples. Average accuracy(recovery of plutonium) for the determination of 0.2303.02 mg plutonium standard was 99.36%. Average precision(relative standard deviation, RSD) for the determination of 0.2500.450 mg plutonium in PWR spent fuel samples was 0.38%.. . 4,5. , m? nm : oD%.p &$%) q r)4 , 'sta(, m$ u( v; "#@w % '( x . ! oF%) &$q r+. yz%) 5 {. µg |8} c; ' sta(.Z m$ u(. ~ 4 mg |8} c ; "#@w% '(. % &$'(.+. 5 &$ .; "#@w% '(; "8l % 1. 2. 4-9. &'( F "#$ %&'( x. r+. : 67"8"#$ %&'(, MN'(. | p &$ p ; m J s . )4, 5 { . %, cR c &QR< &jR3 ; & $OF3 _+; . r + '( K 0 % . .p r+. < , m &$ ; c:< . F ?@ v; 1"83 ; v; I. &$ y); c.Z, v; 5 $. T$} 5 c. 3. 6-9. 10. 581.
(6)
(7) . 582. ;, &Q p &j u # 8K % 7 '() ! &$ ; P. , MNOF3 g; '(. r+. v, ; P, q. r; uOF3 g# 8K: ¡¢£ 's ¤ ¥) u3 ¦§ # 8K:R ¨ %} " © F&. r+. , ª"(.Z n «¬()R q r2 , .I '(, F& . ® ! ¯°(hot cell): ± # ²³. rp C DR v ´+. µ£:, J E &¶'(); yz%) -./01 '(. . %p r+. ·¸, < . ¹ m? nm K 5 ; -./01 '(. oD%.+. º, c£ J 5 I, ¹ m? nm : -./01 2 »¼2 \Z ½ »¼;¾ z ! 4 ./, Pu(NO ) ¼ ! -./01 2 ¿ »¼ À + I oF%) q r+. . c 3 < 6 ./, -./01 2 Á »¼2 \# Âà -./ 01 2 ²Ä %7 ?@¶ v ; 1¶3 ! 4 ?@AB 6 7 KÅ +. 9 :;
(8) (Pressurized water reactor, PWR) 5 &$F => !, F?@ 3 . ?@AB 6 7'( % +- -./01 2 *)4, 67"8"#$ %&'( % ! &$ *+. v, ^_` J 67"8"#$ %&OF3 . ! 9 : % %&'( J &QR E &jR3 a & *)4 5 "#$ &$ TU; G 2 %&6HI JK L *+. 11. 12,13. 2−. 3 6. 14. 14. . 5 67"8"#$ %&; Potentiostat/Galvanostat(EG&G PARC 263A), Digital coulo-. E Titration cell system(EG&G ) "#$ %&U3 . * +. "#$ %& ´Æ"Ç, ÈVÉ "Ç. meter(Scribner 279A) PARC 377A). (EG&G PARC E0002).f)4, ¦6"ÇF #_"Ç ); ÊÊ ÈV "Ç(EG&G PARC K0030)F @ ËÌ"Ç(saturated calomel electrode, EG&G PARC K0077) *+. . PWR E ^_5 K, E 22"Km5 ¶6 H O , NH OHÍHCl, FeSO Í7H O, NH SO H, AlCl Í6H O, HF, HNO , E HCl x, Aldrich v; Merck5 G.R v; A.C.S.Î .f+. PWR 5 ; BIO-RAD5 AG MP-1 -./ 01 23 *+. ^_`, ?@ (ORNL, PuO , Pu=99.93% v; NBL CRM 122, Pu=87.790 Wt.%) 15 M HNO -0.01 M HF Ï?) K ¶6 ! *+. 5 "#$ %&; @ AlCl `, Fe `(5 mg Fe/mL) E 1.5 M NH SO H ` ÊÊ 8 mL, 1 mL E 8 mL Ð Ñ ! 1 M HCl 1 L Òu 22"Km *+. !#:, aluminum, fluoride ./F ¼ ! ¶ # 8K, Fe(II); Pu (VI)3 Pu(IV) 1# 8K, sulfamic acid; nitrite ./ ÓÔ# 8K ÊÊ *+. . p Õ": 3Ö 3 ×Up 10Ö ØÙ ÚÊ PWR : Ñ 3 ¯° : K *+. ; y&$ &Q¸ Û a& ! Ñ +- KU Üp HNO (1+1) ` 1Ý ! K *+.
(9) . PWR , 8 M HNO nm : y&$5 F?@ 3 ! ?@AB3 67 +-, AG MP-1(200d400 mesh) +Þ 2 ßà áâ »¼p c£ F I 8 M HNO `) Áã 0.02 M NH OHÍHCl-0.5 M HNO `) ! *+. . -./01 23 . ! PWR ` 10 mL3 U 8: 0.5d1.0 mL ä Âå2 æÕç +- 22"Km ` 25 mL3 . ! "#$ %& ° èé+. 15 ØÙ ¡êë #ì purging ! 22"Km ` í?3 ¶ p +250 mV(vs. SCE): 30 µA, +900 mV(vs. SCE): 30 µA E +560 mV(vs. SCE): 20 µA5 îÝ"Ý gm 2. 2. 4. 2. 2. 3. 3. 2. 2. 3. 242. 2. 3. 3. 2. 3. 9. 3. 3. 3. 2. 3. Journal of the Korean Chemical Society.
(10) PWR. ! "#$% &$. Âå2 ï:J ?@ v; 1ð+. ÊÊ5 zñF&: 20d30 µA5 îÝ"Ý Ròó  "#$5 ôR y& ô ~2 *# Âà . Â3 zñ5 õO ) & *+. 5 { , 3ö÷ |t: g, ` J "#$ a& ô: 22"Km ` J Øy |t:5 ø ù"#$ a&ô ú ô) t? *+. A# û ü 5 "#$ %&F&, MN F5 ý þ ¤q rRÿ l glove-box : ± *+. 9.
(11) . 9 MN: % 5 67"8"#$ %&, Pu(III)Pu(IV) couple5 % ?@1zñ · . *+. "#$ %&F &, +250 mV5 "8: %&# 22"Km ` F Pu(III) E Fe(II) ? @AB 1ç +- +900 mV: Pu(III)< Fe(II) 3 ÊÊ Pu(IV)< Fe(III) AB ?@ç+. +560 mV :; s %) Pu(IV) Pu(III) 14 . g¹ "#$ ô . ! ` 5 { t? *+. .< , B5 ?@1z ñ ·, 5 "#$ %& 0% % ; '() MNZ a&6H µ£ %" 8 ½Ð l. r+. PWR "#$ %&'() &$ # : 22" Km ` J øù"#$ ô a& *+. a&O F, 22"Km ` J øù"#$ a&ô, n a&×+ 81 mC(milli-Coulomb)5 y& ô Z[b)4, . ô, `5 cZ v; 2 \, øù`5 cZ û Ø y ô.À "#$ %& 5 { t? ;¾; XY 2 \; P) |+. k, 9 MN:; PWR 5 "#$ %& 'K3 P) A; G 2 VW./I J XY L *+. VW./ I5 'KoF a&, PWR v; : 0% $. , P)
(12) ²¹ Nd(III), Zr(IV), Mo(VI), Ce(III), Ba(II), Pd(II), Sn(IV) E Fe(III) ./I J ! M N *+. a& '(, .I VW./ : 2 6-9. 2000, Vol. 44, No. 6. 583. VW./ M¶ {¦+ A ¸ F$} { K ; 0.2d4.0 mg e8: R 22"Km ` +- "#$ a&F& : 3ö÷ |t(+560 mV):5 "#$ a& p 22"Km ` J øù"#$F l.3 0 ! .I. %& TU; XY L *+. MNO F, .I VW./. ` J "#$ a& ô, "ì%) 91 mC) 22"Km ` J øù"#$ ô} 81 mCF Øy *+. PWR , " |t3 &$ # ÂÃ + ./I 5 XY, P ) A2 , M¶ .I ./I. MNe8 : ` í+ !R 5 &$OF ; XY 2 \;+; P
(13) rf+. c£ 5 cR Øy MNOF3 g rf+. º, c£ . ÊÊ 10, 50 E 100 mg 22"Km ` J "#$ ô a& OF, 22"Km ` J øù"#$ ôF Øy 81 mC5 "#$ ô g rf)4, . OF c£ . ` +$ í !R 5 "#$ a&; XY 2 \- K_+. Z, 5 c; . T ¦p ø< . { ! "#$ a&ôR æ ; Y Z[b+. 5 R@ µ "#$ a&ô5 æ &R3 R ! .T 2 2"Km ` r; 5 g/mL5 5 XY L OF, Miller x . . 22" Km ` í ; 5 g/mL5 , 5 "#$ %& 'K3 2 \; P) |f+. PWR , 0.02 M NH OHÍ HCl-0.5 M HNO `) # Âà ` NH OHÍHCl. "#$ %& XY . r P) A+. . J XY a& # 8K ` 10 mL r; { K ; 7.210 M5 NH OHÍHCl. ` J øù"#$ a& OF, "#$ %&F &5 2ö÷ |t: 30 .A5 zñ. F !R 30 µA5 , îÝ"Ý3 g ; x ' K A. Z[ +. .P KO # 8K NH OHÍ HCl ` U 8: ½ ! NH OH Kç +- "#$ a& OF "#$ a&F& 'K3 ; A ¶q r f+. 7. 9. 2. 3. 2. −3. 2. 2. 2.
(14)
(15) . 584. Table 1. Determination of plutonium in plutonium standard solution by controlled-potential coulometric titrationa). a). Table 2. Determination of plutonium in plutonium standard solution by controlled-potential coulometric titrationa). Pu taken, mg. Pu found, mg. Recovery, %. Mean (RSD, %). Pu taken, mg. Pu found, mg. Recovery, %. Mean (RSD, %). 0.1179 0.1189. 0.1244 0.1246. 105.51 104.79. 105.15 11.(0.48). 0.2390 0.2382 0.2362. 0.2347 0.2335 0.2332. 1 98.20 198.03 198.73. 98.32 1(0.37). 0.2308 0.2307 0.2291 0.2314. 0.2294 0.2294 0.2272 0.2298. 99.41 99.43 99.15 99.30. 99.32 (0.13). 0.4716 0.4757. 0.4770 0.4745. 101.19 199.75. 100.47 .1.(1.01). 0.4795 0.4828 0.4839 0.4809. 0.4779 0.4806 0.4819 0.4791. 99.67 99.53 99.59 99.61. 99.60 1(0.06). 0.9688 0.9683 0.9701 0.9670. 0.9622 0.9611 0.9608 0.9592. 99.32 99.25 99.38 99.20. 99.29 (0.08). 3.0221 3.0235. 2.9987 2.9999. 99.23 99.22. 99.23 (0.01). Plutonium standard material : ORNL PuO2 powder solution. &$ # : ^_`(ORNL ^_`) . ! T$5 J "#$ %&OF5 &Q R E &jR3 a& *+. .Â, , 0.120d 0.470 mg e8: ^_` y&$ Û a& ! Ñ +- &$ *+. Table 1; ^_` J "#$ &$OF3 ½ *+. & $OF J C D Z[ &QR; 5 { 0.120 mg &R ´ Ñ c; C D. 105% &R Z[ )4, 5 {. ÿ 100% åà &QR3 g rf+. Z, % &OF J &jR(RSD); 5 {F; Û = P) Z[ +. 5 &$F => ! R S, &$OF3 g# 8K:; 5 { . Ñ ; P. , '(.Z, mg5 &$ # 8K:; È mg5 3 K Å ; M%} ²³. r+. µ£:, 9 : ; , &$e85 ! &$q. r; '( cs%) p² p *+. Table 1 5 OF;, PWR &$ # 8K Ñ p ; 0.250d0.450 mg &R5 9 MN: % %&'() &$ ; c R , &QR3 ; MNOF3 g r- 5T+. k, 9 MN:; 5 "#$ & $ % '( J &QR3
(16) ¡¦# 8K NBL CRM-112 ^_` . ! a& &$OF3 L *+. "#$ &$OF J &Q R; ^_` %& &$OF J C D t? ! a& *)4 Table 2 OF3 ½ *+. ^_` J %&F&, : PWR. a). Plutonium standard material: NBL CRM-122 solution. ± MN F&F Øy *)4, . 5 { , 0.230d3.02 mg e8 Rÿ ^_` Ñ ! ± *+. %&, ÊÊ5 MNR J ! 2d4CÐ 3 Ñ ! %& *+. MNOF g, ^_` . "#$ &$OF J &QR; C D t? * c 0.230d 3.02 mg e8: hi C D 99.360.16%.f+.
(17) . PWR &$ # 8K: yl%) -./0 1 2 = . ! *+. # : 5 ?@AB 67. 5 &$% C TU; } L *+. MN, # " F?@ 3 ! 5 ?@ AB3 67 c< F?@ 3 2 \¡ 5 ?@AB3 67 2 \, c J "#$ &$OF3 0 *+. Table 3; .I 2 c J MNOF3 ½ *+. c:5 l. , 5 ?@AB3 67 2 \, c ? @AB3 67 c¦+ . ½ 10% &R % C ; P) Z[ +. µ£:, &$%) # 8K:; ¨. %) 5 ?@AB3 67 +- F & !Å +; P Q}q rf+. k, Table Journal of the Korean Chemical Society.
(18) PWR. ! "#$% &$. Table 3. Effect of pretreatment time on the coulometric titration of plutoniuma) Time, day. Sample, g. 1 2 4 6 uncontrolled. 3.567 3.384 3.720 3.783 3.646 3.846. Table 4. Determination of plutonium in PWR spent fuel samples by controlled-potential coulometrtic titrationa). Results Pu, µg. [Pu], µg/g. 300.5 283.6 313.7 317.4 276.9 293.0. 84.2 83.8 84.3 83.9 75.9 76.2. 585. Sample No. 1 2 3 5 8 110. Resultsb) [Pu], µg/g. RSD, %. 48.9 85.5 99.4 84.3 106.2 75.5. 0.18 0.32 0.37 0.40 0.53 0.47. a). a). 3; F?@ 3 ! 5 ?@AB3 6 7 µ "#$ %&OF3 " ¦!p r+. 5 ?@AB; 1d6y e8: & ! 67 *)4, ?@AB3 67 J 5 &$OF; ?@AB 67F &$: g, 5 { .; #$ l. - ¦!p r+. .< , MNOF3 øù) F?@. 3 PWR ` y&$ +- 3y 'U ! 5 ?@AB3 67 F& ± * +. 8 M HNO nm : 5 ?@AB3 67 `, AG MP-1 +Þ -./01 2 »¼ç +- 8 M HNO ) c£ F í ; I Áã -. /01 2 »¼ 0.02 M NH OHÍ HCl-0.5 M HNO `) C *+.
(19) . PWR K` , -./01 23 . ! +- 67"8"#$ %&() &$ *+. " #$ %& q 5 {. % 0.250d 0.450 mg. Rÿ 8 M m? nm 5 PWR K` 3 K J R a &OF3 &p ! 4d8 gram &R3 &Q¸ Û a & ! Ñ *+. ` F?@ 3 y&$ ! 3y 5 ?@AB3 67 -./ 01 23 . ! +- &$ *+. Table 4; 67"8"#$ %&'( . ! g, PWR 5 $ Z [b+. Table 45 OF; M¶ 0.250d 0.450 mg5 "#$ %& ! OF3 . ` gram 5 {) 1? ! Z[ ô.4, PWR 5 $, µ£ 0.5d0.9% &R3 Z[b+. 9 MN: g , PWR 5 &$OF J &jR(AJ^_kl, RSD); 6' JK ÊÊ 0.18d0.53%5 OF3 Z[b)4, .< , 9 MN :5 &$OF; Chitnis x . 0.270d0.550 mg5 "#$ %& *  g, 0.28d0.40% 5 a& &jR< ¿ 0 +.. Plutonium standard material : NBL CRM-122 solution. 3. 3. 2. 14. 3. 2000, Vol. 44, No. 6. PWR spent fuel samples from Kori-1. b) Number of titration: n =2~6.. 15. PWR "#$ % &() &$ *+. , -./01 23 . ! *)4 &$, 67"8"#$ %&'( . *+. ^_` . "#$ &$OF5 &QR; C D Z[b  0.230d3.02 mg e8: hi C D 99.360.16% .f+. PWR K` 0.250d0.450 mg5 -./ 01() 67"8 "#$ %&'() &$ OF J &jR(AJ^_kl, RSD); hi 0.38%.f+.. 9 ; Fw#(5 'ÕÆ5 y1 ) ±f)4 . )*++.. . !. 1. Mitchell, W. G.; Spaletto, M. I.; Lewis, K.; Sariano, M. D.; Smith, M. M. Report NBL-323, 1990..
(20) 586.
(21) . 2. Aggarwal, S. K.; Saxena, M. K.; Jain, H. C. J. Radioanal. Nucl. Chem. 1992, 136, 111. 3. Sorantin, H.; Determination of Uranium and Plutonium in Nuclear Fuels; Verlag Chemie: Weinheim. 1975. 4. Kuvik, V.; Vrbora, L. Report IAEA-AL-031, 1990. 5. Ronesch, K.; Tammet, G.; Berger, J.; Doubek, N.; Bagliano, G.; Deron, S. Report IAEA-AL-059, 1992. 6. Holland, M. K.; Weiss, J. R.; Pietri, C. E. Report NBL299, 1981. 7. Shults, W. D. Talanta, 1963, 10, 833. 8. Jackson, D. D.; Holland, R. M.; Roensch, F. R.; Rein, T. E. Anal. Chim. Acta, 1980, 117, 205. 9. Miller, F. C.; Hildebrandt, B. W.; Shurrock, S. C.. Report AECL-MISC-218. 10. Harrar, J. E.; Electroanalytical Chemistry; Bard, A. J., Ed.: Marcel Dekker Inc.: New York. 1975; Vol. 8. 11. Scott, F. A.; Freeman, R. M. HW-58491. 1958. 12. Coleman, G. H. NAS-NS-3058. 1965. 13. Cleveland, J. M. The Chemistry of Plutonium; Am. Nucl. Soc.: 1979. 14. Suh, M. Y.; Sohn, S. C.; Lee, C. H.; Kim, J. S.; Song, B. C.; Yoon, S. K.; Park, Y. J.; Park, K. K.; Jee, K. Y.; Kim, W. H. J. Korean Chem Soc. 2000, 44, 480. 15. Chitinis, R. T.; Talnikar, S. G.; Thakur, V. A.; Paranjapa, A. H. J. Radioanal. Chem. 1979, 49, 71.. Journal of the Korean Chemical Society.
(22)
관련 문서
