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H + + Th(OH) 3+ -2.500 Th(OH) 2 2+ Th 4+ + 2H 2 O(l) ! 2H + + Th(OH) 2 2+ -6.200 Th(OH) 4 (aq) Th 4+ + 4H 2 O(l) ! 4H + + Th(OH) 4 (aq) -17.400 Th 2 (OH) 2 6+ 2Th 4+ + 2H 2 O(l) ! 2H + + Th 2 (OH) 2 6+ -5.900 Th 2 (OH) 3 5+ 2Th 4+ + 3H 2 O(l) ! 3H + + Th 2 (OH) 3 5+ -6.800 Th 4 (OH) 8 8+ 4Th 4+ + 8H 2 O(l) ! 8H + + Th 4 (OH) 8 8+ -20.400 Th 4 (OH) 12 4+ 4Th 4+ + 12H 2 O(l) ! 12H + + Th 4 (OH) 12 4+ -26.600 Th 6 (OH) 14 10+ 6Th 4+ + 14H 2 O(l) ! 14H + + Th 6 (OH) 14 10+ -36.800 Th 6 (OH) 15 9+ 6Th 4+ + 15H 2 O(l) ! 15H + + Th 6 (OH) 15 9+ -36.800 ! g'+(!70(/24+,2(>!(%&*,%.!/#/&+3/@!0(+!08!&'+!30/&!23;0,&%(&!%,+%/!2(!P%&+,! 7'+32/&,#!2/!&'+!7%,"0(%&+!/#/&+3G!Q'+!7%,"0(%&+!/#/&+3!3%2(.#!70(/2/&/!08!>%/+0*/! DF B @!DF BM>N @! ! %<*+0*/!DF B @!DF BM%,%3!7%.7*.%&+4!*/2(>!R2/*%.!-O$QJjG!D &Q' hZGZX!S! AC [X !-@!OhCGA!-!$%$F Z G!! ! 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AA! /;+72+/!"+>2(!&0!"+703+!&'+!30,+!4032(%(&!/;+72+/!80,!&'+!,+3%2(4+,!08!&'+!;)! ,%(>+!P2&'!&'+!+S7+;&20(!08!Q'F) c M%!%&!QhBXiD!%(4!OhCG!-!%(4! %//072%&+4!.0>!f!:%.*+/G!b0>!f!70(/&%(&/!P+,+!7%.7*.%&+4!8,03!&'+,304#(%327!4%&%! >2:+(!"#!ML%(4@!6*>+,!+&!%.G!BCCeNG! Species Th(IV) Carbonate Complexation Reactions Log K Th(CO 3 ) 5 6- Th 4+ + 5CO 3 2- ! Th(CO 3 ) 5 6- 31.000 ThOH(CO 3 ) 4 5- Th 4+ + H 2 O(l) + 4CO 3 2- ! H + + ThOH(CO 3 ) 4 5- 21.600 Th(OH) 2 (CO 3 ) 2 2- Th 4+ + 2H 2 O(l) + 2CO 3 2- ! 2H + + Th(OH) 2 (CO 3 ) 2 2- 8.800 Th(OH) 4 (CO 3 ) 2- Th 4+ + 4H 2 O(l) + CO 3 2- ! 4H + + Th(OH) 4 (CO 3 ) 2- -15.600 ! ! ! ;&<,#3(787:(Q'MORN!/;+72%&20(!42%>,%3!7%.7*.%&+4!*/2(>!R2/*%.!-O$QJjG!D &Q' hZGZX!S! AC [X !-@!OhCGCW!$%$F Z kCGCA!-!$%)DF Z! ! AB! BGX!?0.*"2.2&#!08!Q'0,2*3!FS24+/! ?0.*"2.2&#!2/!08!>,+%&!23;0,&%(7+!&0!&'+!8%&+!%(4!&,%(/;0,&!08!70(&%32(%(&/G! -%(#!8%7&0,/!%8+7&!&'+!/0.*"2.2&#!08!%!/*"/&%(7+!2(7.*42(>!&+3;+,%&*,+@!;,+/*,+@! &'+!(%&*,+!08!&'+!/*"/&%(7+!"+2(>!42/0.:+4!M+G>G@!;0.%,2&#@!/2T+!08!/0.24@!+&7GN@!%(4! +S;+,23+(&%.!;,07+4*,+/!M+G>G@!/&2,2(>@!;,+&,+%&3+(&@!+&7GNG!b2E+!%.!7'+327%.! /#/&+3/!&'%&!%,+!%&!70(/&%(&!&+3;+,%&*,+!%(4!;,+/*,+@!,+%7&20(/!&%E+!;.%7+!2(!0,4+,! &0!32(232T+!&'+!&0&%.!52"`/!8,+!+(+,>#G!g'+(!&'+!52"`/!8,+!+(+,>#!2/!%&!%! 32(23*3!&'+!7'+327%.!,+%7&20(!2/!70(/24+,+4!&0!"+!%&!+<*2.2",2*3G!g'+(!4+/7,2"2(>! &'+!42/0.*&20(!08!%!/0.24!2(!%!.2<*24@!&'+!+<*2.2",2*3!70(/&%(&!2/!7%.+4!&'+!/0.*"2.2&#! ;,04*7&@!f /; G! ! ;&<,#3(78=:Q'MORN!/;+72%&20(!42%>,%3!7%.7*.%&+4!*/2(>!R2/*%.!-O$QJjG!D &Q' hZGZX!S! AC [X !-@!OhCGA!-!$%)DF Z! ! ! AZ! 60,!&'+!>+(+,%.!+<*%&20(@!! ! ! A x B y (s)"xA y+ yB x# ! MAN ! Q'+!/0.*"2.2&#!;,04*7&!2/! ! ! K sp = {A y+ } x {B x" } y { xy (s)} =[A y+ ] x [B x" ] y {# A y+ } x {# B x" } y ! MBN ! ! P'+,+!2(427%&+/!%7&2:2&#!%(4!q2r!2(427%&+/!70(7+(&,%&20(@!%(4!! 2 !2/!&'+!%7&2:&#! 70+8272+(&!08!/;+72+/!2G!F:+,!&'+!#+%,/!&'+,+!'%:+!"+(!3%(#!/&*42+/!70(7+,(2(>!&'+! /0.*"2.2&#!08!Q'MORN!0S24+/!%(4!'#4,0S24+/G!-0/&!08!&'+/+!/0.*"2.2&#!/&*42+/!P+,+! 70(4*7&+4!*/2(>!&'+!*(4+,/%&*,%&20(!%;,0%7'@!P'+,+!&'+!&'0,2*3!/0.24!P%/!;.%7+4! 2(&0!%!/0.*&20(!%(4!%.0P+4!&0!+<*2.2",%&+!ML#%(!%(4!L%2!AWedl!F/&'0./@!H,*(0!+&!%.G! AWWcl!6+.3#@!L%2!+&!%.G!AWdl!1.&3%2+,@!$+7E!+&!%.G!BCcl!f23@!H%2E!+&!%.G!BCACNG!1/! &'0,2*3!"+>2(/!&0!;,+72;2&%&+!2(!/0.*&20(@!&'+!/0.24!2/!70(/24+,+4!+2&'+,!%(! %30,;'0*/!'#4,0S24+@!Q'MF)N c M%3N@!0,!%!327,07,#/&%.2(+!'#4,0*/!0S24+! Q'F B "S) B FM%3N!M$+7E!%(4!f23!BCCNG!ML%2@!-00,+!+&!%.G!BCCCN!,+;0,&/!&'%&!%8&+,! /03+!&23+!Q'F B M%3N!&,%(/80,3/!2(&0!&'+!.+/!/0.*".+!7,#/&%.2(+!&'0,2*3!0S24+@! Q'F B M7,NG!Q'+!%30*(&!08!&23+!80,!Q'F B M%3N!&0!&,%(/80,3!2(&0!&'+!7,#/&%.2(+!/0.24! 4+7,+%/+/!%/!&'+!&+3;+,%&*,+!08!&'+!/0.*&20(!2(7,+%/+/!MBdC!4%#/!%&!BXiD!%(4!%"0*&! AB!4%#/!%&!ACCiDN!M$+7E!%(4!f23!BCANG!M$+7E!%(4!f23!BCAN!/&%&+!&'%&!P%&+,[8,++! Q'F B M7,N!,+<*2,+/!'+%&2(>!&'+!/0.24/!&0!&+3;+,%&*,+/!>,+%&+,!&'%(!dCiDG!18&+,! ,+:2+P2(>!&'2/!2(80,3%&20(@!%/!Q'F B M%3N!%>+4!&'+!/0.*"2.2&#!4+7,+%/+4!%(4!&P0! /0.*"2.2&#!70(/&%(&/!P+,+!/+.+7&+4!80,!&'+!%30,;'0*/!/0.24U!Q'F B M%3@!8,+/'N!%(4! Q'F B M%3@!%>+4NG!L%(4@!6*>+,!+&!%.G!MBCeN!%7E(0P.+4>+4!&'%&!&'+,+!2/(`&!%!4+82(2&+! &23+!P'+(!Q'F B M%3@!8,+/'N!"+703+/!Q'F B M%3@!%>+4NG!?&2.@!Q'+!/*>+/&+4! Ac! +<*2.2",%&20(!&23+/!*/+4!&0!428+,+(&2%&+!"+&P+(!Q'F B M%3@!8,+/'N!%(4!Q'F B M%3@! %>+4N!%,+!uBX!4%#/!%(4!VdC!4%#/@!,+/;+7&2:+.#!ML%(4@!6*>+,!+&!%.G!BCCeNG!Q'+! /0.*"2.2&#!;,04*7&/!80,!&'+/+!&P0!/0.24/!%(4!7,#/&%.2(+!Q'F B !%,+!/'0P(!2(!Q%".+!BGZG! b0>!/0.*"2.2&#!;.0&/!80,!&'+!&',+!/0.24/!%&!428+,+(&!7%,"0(%&+!70(7+(&,%&20(/!%,+! /'0P(!2(!62>*,+!BGc!%(4!62>*,+!BGXG! *1/63(78=:(Q'0,2*3!/0.*"2.2&#!,+%7&20(/!07*,,2(>!%&!QhBXiD!%(4!OhCGC!-!%(4! %//072%&+4!.0>!f /; !:%.*+/G!b0>!f /; !70(/&%(&/!P+,+!7%.7*.%&+4!8,03!&'+,304#(%327! 4%&%!>2:+(!"#!ML%(4@!6*>+,!+&!%.G!BCCeNG! ! Th(IV) Solubility Reactions Log K sp Th 4+ + 2H 2 O(l) ! 4H + + ThO 2 (am, fresh) -9.300 Th 4+ + 2H 2 O(l) ! 4H + + ThO 2 (am, aged) -8.500 Th 4+ + 2H 2 O(l) ! 4H + + ThO 2 (s) -1.766 ! 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K., V. A. Loganathan, S. R. Kanel, G. R. Jeppu and M. O. Barnet (2009). "Normalization, comparison, and scaling of adsorption data: Arsenate and goethite." Journal of Colloid and Interface Science 333(1): 6-13. 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A., R. A. Fjeld, D. I. Kaplan, J. T. Coates and S. M. Serkiz (2005). "PU(V)0(2)(+) adsorption and reduction by synthetic hematite and goethite." Environmental Science & Technology 39(7): 2107-2114. 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v +s " ' =6789mgL 10!4.73g .8 " $ % & ' =.16mgL# # U()'#"d## $-.K)*(#(-#s6-0_e#?sTB# f M .1 234gol ! 1 0g " $ % & ' ! 6 ?ol " $ % & ' 30.8?M# # U()'#Sd# b)()*63.)#'$# pC=!lo f l(.8M)=1.49# # >%?@AB#n'(&:)F#`# !"#$%&'( m3K).d#>-(&0#2&6'0)#K-016)F#A ( #h#SL,;"F#A-016)#-7#>%?@AB#2(-/:#2-01(3-.#3.#2&6'0)F# A >% #h#L,";QF#$-./).(*&(3-.#-7#>%?@AB#2(-/:#2-01(3-.F#$ 2(-/: #h#;L"!#6E_eF# b32-0K)4#>%?@AB#/-./).(*&(3-.#-7#2&6'0)F#$ 7 #h#Q,;\#6E_eF#T&2#-7#2-30#3.# 2&6'0)F#6#h#L,;!"#E# # U()'#;d## @.3(3&0#&`1)-12#>%?@AB#/-./).(*&(3-.F#$ L # C 0 = stock !V Th 105mgL!.1 32 =.40mg# # \;# U()'#"d# >%?@AB#/-./).(*&(3-.#&42-*D)4#(-#E)-6)43&F#`# ! q= C 0 "C f ( ) 1000 # V t m = 7.400mgL"7.166mgL ( ) 1000mLL # 30.112mL 0.0152g q=0.4636 mg g # 1000?gmg 232.04gmol $ % & ' ( ) q=1.998?molg # # X#>%?@AB#b322-0K)4#3.#2-01(3-.# !"#$%&'( m3K).d#>-(&0#2&6'0)#K-016)F#A (# h#SL,;;"F#b322-0K)4#>%?@AB#$-./).(*&(3-.F#$ 7# h#Q,;\\# 6E_eF#@.3(3&0#2&6'0)#>%?@AB#/-./).(*&(3-.F#$ L #h#Q,+L#6E_e# # U()'#;d# >-(&0#6&2#-7#(%-*316#3.#2&6'0)F#6 (# m t = C!V t 1L 4mg!.1 =.23mg# # U()'#"d# T&2#-7#(%-*316#432-0K)4#3.#2-01(3-.F#6 4 # # # d f ! t 0 .6L! .1# # U()'#Sd# X#>%?@AB#b322-0K)4#3.#2-01(3-.# # # = m d t !1 .2g 3 !0=96.8%# # I&*(3/0)#23f)#*)6-K)4#t#U(-:)u2#e&G# !"#$%&'( m3K).d#5&4312#-7#*-(&(3-.#-7#(%)#(-'#-7#(%)#2)436).(F#5#h#;",+#/6F#5&4312#-7#*-(&(3-.# -7#(%)#21*7&/)#-7#(%)#212').23-.#3.#(%)#(1D)F#U#h#\,;#/6F#$).(*371E&(3-.#2')4F#a 6 #h# MLL#*'6F#$).(*371E&(3-.#(36)F#( 63. #h#SL#63.1()2F#A32/-23(C#-7#03`134#v#"!w$#?'-32)BF# x#h#L,LLMW#E_/6H2F#b).23(C#-7#(%)#2-034#?>%N " BF#y >% #h#;L#E_/6 S F#b).23(C#-7#(%)#03`134# ?R " NBF#y G #h#;#E_/6 S F#b).23(C#-7#(%)#2-034#?2-30BF#y 2 #h#",\!#E_/6 S # # U()'#;d# U3f)#-7#>%?@AB#2-034#*)6-K)4# # # D ?m = 6.!1 8 log R S " $ % & ' N 2 (t inThw ) = 6.10 8 (.9gcm)s(lo 12.4c 6 " # $ % & ' (in )2 3i0 3 g 3 ) 0.3 # # \"# U()'#"d# U3f)#-7#2-30#'&*(3/0)#*)6-K)4# # # ! D ?m = 63.0"10 8 #log R S $ % & ' ( ) N m 2 *t min *+ Th ,+ w ( ) D ?m = 63.0"10 8 *0.0089gcm,s*log 12.4cm 6.1 $ % & ' ( ) (8000min ,1 ) 2 *30min*2.65gcm 3 ,1gcm 3 ( ) D ?m =0.074?m #