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ジエチルエーテルを用いるモリブドリン酸と陽イオン染料とのイオン対のフローテーション挙動並びにリン酸及びヒ酸,亜ヒ酸イオンのフローテーション : 吸光光度定量

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(1)Title. ジエチルエーテルを用いるモリブドリン酸と陽イオン染料とのイオン対 のフローテーション挙動並びにリン酸及びヒ酸,亜ヒ酸イオンのフロー テーション : 吸光光度定量. Author(s). 那須, 淑子; 西木, 祭; 鹿島, まなみ; 桑原, 宏子. Citation. 北海道教育大学紀要. 第二部. A, 数学・物理学・化学・工学編, 40(1) : 37-49. Issue Date. 1989-10. URL. http://s-ir.sap.hokkyodai.ac.jp/dspace/handle/123456789/6164. Rights. Hokkaido University of Education.

(2)      . 0巻 第1号 北海道教育大学紀要 (第2部A) 第4. 平成元年1 0月. r I A) Vol ion l ion (Sec i i t ido Un ty ofEducat lof Hokka j ver s ouma −l .40 , No. 9 oc tober ,198. ionic th Cat F1otat ion Behaviorof.on Pai rsofハ4o1ybdophosphate wi Dyes Us ing. Di ethyI Ether and F1otation−SPectrophoto1netric Deter−. ion of Phosphate, Arsenate, and Arsenite minat. i KASHIMA and M[ i NISHIK1 Toshiko N ASU M[atsur , anam , HirokO KUWA日ARA l Chemi ILaboratory ege ca , ,Sapporocol i i iver Hokka ido Un tyofEducat on s , Sapporo o02. ジ エチルエーテル を用いるモリ ブドリ ン酸と陽イ オ ン染料との イ オ ン対のフロ ーテーショ ン挙動並 び にリ ン酸及 びヒ酸, 亜ヒ酸イ オ ンのフローテーシ ョ ン−吸光光度定量. 那. 須. 淑. 子・西. 木. 祭・鹿. 島. まなみ・桑. 原. 宏. 子. 北海道教育大学札幌分校化学教室. Abstract. te Green, icabi l i Thi ty ofcationic dyes,such as M[ alachi s an investigation 。ftheapp. si l ine l l iant Green i。l i Ethy let ]mine B,to IVio ethyl ene B1ue et ,andRhoda ,R0sani ,M【 ,Br ,Crysta1 r ing diethyl ether lotat i。n of ion pa. rs of the th molybdophosphate us the f rs wi ‐ lon pai. i 1 1 iantGreenandRh。da M[a 1achi lnineB areeomp.ete1y te Green et o1 et ,Br ,CrystaIVio1 ,Ethy1Vi ie te Greeni thyle therPhoses s f loated atthe Phase boundary between aque。us andd alachi ‐ M【 i tabl thelr Iost su eforthe determination of phosphate and a determination methodfor Phos‐ i i bed ion。fせl t f t ltat s descr ei。n pairi phate ‐ , arsenate ,and arsen e a erf。. 7) (3.

(3)  . 2. Tosh iko NASU i N1 ↓ ASHIMAand Hi sur sHI K 1 anamiK roko KU r G VAHARA , Mat ,M[. 1ntroduct ion. Molybdophosphate whi id of phosphate wi s a con jugated base of he teropoly ac chi th , f i i i i i h t 江ー r t d olybdate r m a s i i d i d T h W i ion has been some ca on c yes n ac c me ia sreact , o s on p ‐ . −3 ) ) vv usedto determine phosphateaf terextraction oftheion pairsinto organicso1vents− i th loatedatthephaseboundarybetween someorganicsolventstheion pai rsarenotextractedbutf. the aqueousandorgad i ion terthephaseseparat loatedionpa i cphase i rsared ssolved ‐ Af ,thef into the organic phase by the add i ion of methanol etc. t sphate can be determined , and pho accurately.. Theauthourss iedsens i ivemethodsforthede tud t inat ionofphosphateus ter ingcationic na dyes such as Ma lachi te Green (MG),EthyIViol l l i l iant Green et(EV),CwstaIVio et(CV),Br ,. (BG),Rosani l ine (RA), Methy l ene B1ue (MB) and Rhodamine B (RhB). .. ln previousstudies i oundthation pairsof molybdophosphate Wi qG and RhB thn , t wasf. loatedatthephaseboundary whentheaqueousphasei aref i thd sshaken wi ter ethylether. Af d i ingthe aqueous phase,theion pairs are d scard i lvedintothe d i sso ethylether phase bythe i ion of methano l t五ors have deve t add loped sens i ive determinat ion methods for t − The au f l ion‐ ion‐ indi spectrophotometry and extract ion spectro‐ phosphate rect atomic absorpt , otat 4 )f 5 } )wi i l th M[ i df te Green h l h t t photometry wi t al ach t t t o a on… specrop o omery an uorop o ometry6 th ,. Rhodamine B. Theion pairsofthe othercationic dyes are alsof loatedatthephaseboundaryandthey di i lether phase bytheadd i ion of methanol ssolveinto the d ethy t ‐ The present paper descr ibesthe use of EV, CV, BG RA and MB in the f lotat ion of , , lybdophosphate asion pairreagentsforthe determination ofphosphate andthe ut mo l i i ty of , these and. MG and RhBis also di scussed .. Arsenate f orms molybdoarsenate andion pairs of molybdoarsenate wi ththese cationic dye ing agents are alsof A loated rsenate can be de termined using thesame procedure asfor . h te does not react wi i th e ther molybdate or these cationic dyes‐ phosphate , owever Arseni )areem lo edforthe determinat Therefore ox dat iveandreductivereactionsofarsenic2 iono f p y , i d te phosphate . , arsenate , an arseni. ExperlmentaI Reagents. The structure ofthecat ion i c dyes usedinthe present s tudy are shown in Schema .‐ Stock solutions of Q6 mM aqueoussolution of MG (Merck Darms tadt , ,F.R−G. , microscopy ),EV (Math俵 l IManufactur ingChemi ade s on Col eman & Be ),CV 鱒r st s ,Norwood ,ohio ,U‐S‐A. (Merck,i i d BG W r p ) nd ( k C h catorand mi i ll d ies croscopy gr ial a e, t a o ure em ca n us r ・ ,Ltd ,spec i Ko L d ) MB W r k P t ( C h i ll d L i d l t grade), RA (Tokyo Kase a r t o u e em n をwo c a u s r e s s e c ‐, , . , , p ia. 8) (3.

(4)         .  . っ J. f i i tuf F1otat ion D荏olybdPhosPhat th Cat s s on c Dye e wi +. R N クン 2. 搬2. クン. ′ R. R″. 一. 日 N に } 2 5 2. C { H } N 2 5 2. R′. R. R″. 18ch iteG 閥a n r ee. −C H3. ーH. −H. E IV iolet t hy. − −℃ 2H5. ‐[2 H5. −H. C lvio te t r ysta. . ‐C日 3. −C 日3. 一日. B lli ri r een antG. −C2 H5. −H. −”. R lin ni e osa. − −日. 一日. 一C 日3. +. ℃ 日}掲 { [ 32 ば. 鳶. 1 醐3 ゴ. ■ Te lue H th neB e y. R ho dam i neB. ft Schema l‐ Structureso ± l edyesusedinthe presentstudy‐ il ) was prepared‐ The llndustries, Ltd− IB (Wrako Pme Chemica grade),and RI , spec a grade ions we working solut reo−12 m公な aqueoussolutions−. i Standard solutions of phosphate, arsenate, and arsenite were prepared by d ssolving ia l grade), i ihydrogenphosphate (Wrako Pure Chemi t ium d cal lndus r es potass . , Ltd , spec l L i l i d d i P d ) h ( 五 k C h i l t t t W ァ i ( a di d s e s s e c r e n u r r a e o um o e n a r s e n a e u a o e m c a g n y so mコ g . , , p , rsod ) in water te (Me arseni rck,gL 1aranteed reagent ‐. ium α lybdate iu刀口 molybdate solution was prepared by di A O.2 公互 sod 1 o ssoIVing sod )in water llndus ialgrade i t rom (Wrako Pー皿e Chemi r ca es ‐ Toremove phosphorusf ‐ ,Ltd ,spec lofl‐butanol ‐chlorofornn lportion was washed with two portionsofloo ‐ n n thi i ‐n ssolution,a250 ingfu l (1+4) byshakingin aseparat r 口 ie ‐ The l‐Butanoldissolvedin the aqueous phase was lportions ofc l 冠 ー th four20 re ・noved wi ‐ni orofor l n byshakingthesolution‐ l i ; roughoutthese experiments wereofana 1chen・icals used th AI calreagent grade‐ yt Apparat l 1s. l l A Hi l139spectrophotometer wi th5 tachiPerkin‐E1mer Mode ‐mm orl ‐ swas cm glassce usedf or measuring absorbance‐. A Sh beam spectrophotometer imadzu Mode IUV‐ 200doubl ‐ e. wasusedto determinethe absorption spectra‐. Procedure i Procedure l(Procedu lotat i ) rs on behavioroftheion pa reforthestudy off ′ l beaker‐ A sa]mp1e solution containing up to 2‐5”g of phosphorL 1 si ‐ 1 1 s p1 acedin a 50 1 (39).

(5)  . 4. Tosh iko NAsU i Nー at sur sH I K I ー 諏 I anamiKAsH Aand Hi N VAHA Iい roko KU ,M[ ,M[. Then 5 mlof2 M sul fur i id ( for MB,3 mlof6 M sul fur i id),5 mlofo‐2 M sodi c ac c ac um molybdate solution, and 5 ml ofo.12 mM dye working solution are added d h i , an t e m xed o ioni i lutedto 25 ml wi th water sol ut ters tandi sd ngfor15 min at40 Cin a waterbathto ‐ Af l low thereactionto occur,thesol f d i i t t a 1andl0‐0 m1of u on s rans erre into aseparatingfu 1me di t五eri lut ioni loattheionPai ethyle sadded sshakenfor2 mintof rsofthe molybdo− . Theso h h d h i i i h t d A f h tert e phase separaton,t e aqueous Phasei P osP a ean t ecatonc ye s di scarded . ‐ M【 i lvetheion Pairs,andthesolutionistransferred ethanoli saddedtotheorganic Phaseto d sso into a 25 lask and d i luted to th i n netric f l ‐ml voluJ th methano s volunne wi s . The absorbancei l meast D red at 故e wave en淳h ofthe absorPtion maximunn against waterin a l l l − cm glassce . Procedure 2 (Procedur lachi e for the deterrnination of phosphate and arsenate with Ma te. Green) A samP1 ion containing up to2‐5〆gofphosPhorus or arsenici esol ut sP1acedi n a50 −ml beaker fur l i id i lybdateso lut ion cac u im mo . 5 mlof2 M su ,3 mlofo.2 M sod ,and3 mlofo.12 M G l h i i k l i M t d d d h lut aac e reen wor ng souton are a e,andt e mixedso ioni i luted to 25 ml m sd oCina waterbathtoa A f th water d i f t i t 5 wi 5 l l h i t2 e rs n n he a o r m na t r e a c o nto occt lr g ow e . ,t ・ f l i i d t t i i land lo.o mlofdi sou on s rans erre nto a separaton fu・ thyl etheri u le e s added . The ioni loattheion Pairs‐ After phaseseparation,the aqueous Phase sol ut sshakenfor2 mi ntof i i t力anoli sd scarded e saddedtotheorganic phaseto dissolvetheion Pairs,andthesolution ‐ 鮎[ i lask and d l i i stransferred into a 25 −mlvolumetricf th me故anol uted to th svolume wi . The b b a sor ancei 20 ni l l s measured at6 ゴ ロ against wateri n a5 ‐mm glass ce ‐ Procedure 3 (Proc edu i 「 e for 口l e determination of total amount of Phosphate, arsenate, and i t r n a se e A f teradd ionof5 mlof2D i fur t dsul i idasinProcedu i L cac こ re2 unn ,0‐l mlof2.5 mDqPotass o 雨chromatesolutioni i d d d dt h tfor5 min at25 C,and else procedu二 sa e an e m xturei sl ef re2i s. fol lowed ‐ Procedure 4 (Procedu i ) reforthe determinat onofphosPhate Here . 5 m i l uosu fat lof2 r l 1ut ion i l lハ4 sod tead ofthe potassiunn u止n t eso s addedins ‐ d di h ; r i d d l t f l l 2i r c u r 3 d c omae n p o e e an es e proce ure s o owe ‐. Res l l l tsand Di sc l u ss lon F1otat ion Behadoroflon Pai d [o lybdoPhosPhate wi ioni th Cat rsofa c Dyes                                             Thef lotat ionbehaviorofion Pairsus ing 虚ethy letheri i i th ssuエnmar zedin Tabl el . VV nαG,EV,CV and BG,on lyl i leofthe dyes were extracted andtheion pairs weref t t loated ‐ VV i 4B and RhB,the dyes were extracted al th凸 loated thoughtheion Pairs weref . Theion Pairs of!no1ybdoPhosphatewi 1 1oated thR〕A wasa i sof rformation ,buttheionpa (40).

(6)  .  . 5. f t l f i t ion s th Cat lybdphospha te Wi i c Dy巴s Fiotat o on M【 ion behavi rsof Tabl oroftheion pai e l. F1otat t h dyes molybdophosphate wi ion Behavior* F1otat Dye. Dye. lon pa l r + + + +. M[ te Green alachi E化ー et yI Viol Crys taI Violet. M[alach i te Green. Eせl IVi t ol e y Cn′ taI Violet s Br i l l iant Green. l iant Green Br i l. N1 ene Blue e化げl. N【 e B1ue l 1 ethyle. +. l Rosani ine. Rhoda I P ine B. Rosani l ine. +. ○. Rhoda lmine B. +. ○. Wave l − ength of absorp imul ion max t n/n Em U ^ U nV ﹁ 3 = V^ U ^ ^ U ^ △ ! にり にり u J QJ ^ / ム▲ つル ^ h Ur へ り ヘ リハ ヘ リハ h Ur にU にU r. Dye. i ion maximaoftheionpa rsof Tabl e 2. AbsoIPt theach dye‐ molybdophosphate wi. IM ; ]=40口 4 M 江Na ]=0 [日2S04 2Mo0, ‐ ]=24”M‐ [Dye * +, F1oated;− ‐not 日oated racted;and o,extracted orext ‐. r l i l fl l df nt‐ ions i f i i esecon両t c ent 皿ldertr wasinsuf ,and RA wase×cude rom t e o ow ngexPenme s Aるsのめすわ7 2 励解Z粥α i sted theachdye arel lybdoPhosPhate Wi i ftheion Pa 1 l The absorPtion 江laxi rsofl o ・ 1 la o i id Wi i t ththoseofthe dyes‐ h b in Table2 ,andt e a sorpt on spec ra co nc es. 閉 じ ‘ m通勿g わ 名の明りひ8 のにess メ ツ8 i I M i i cphaseWith ngoftheorga回 ExcessD 4B wasextractedintotheorga国 cphase ,and was i water wa edtoremovethis‐ st r. fb ththereagent b b th Af th water tershaking wi , e a sor anceo o. th凸江B lybdophosphateionpa l rswi twasshownthatthe mo blankandtheionpairs decreased‐ 1 ing wi deco駕ー th water‐ posed byshak. 1oremovetheexcessRhB extractedintothediethyletherphase, washing oftheorganlc inute of shaking w← as l of water one l l ・ i th 25 n l phase With water was also examined. VV h ds case‐ l i f i i t t eloss ofion pairsin亡 suf c ent − There wasl. i 〕 ば i red for the other dyes as they were neither VVashing ofthe orga c phase was not req豆 iethylether‐ loatedintothe d extracted norf. ionoftheionpai ionandthenotat Thefonnat rsof mol ybdophosphateWithcatio国c dyes id i id id i fur i id ionofac thcac cac f fectedbythetypeandconcent cac rat area , − Sul ,hydrocmor ,n i t t h i i d dt n a r e d d f h n e n r a o s i f f o c h c tso t eac san id were exam ne , an t ee ec er i l 頭or cac and perc i lt th i f i r t id l fur icac i 5‐ VV thsu showni n Figs ‐ −1 ,theabsorbanceo the onparswaspropo ona o e ids ththe other ac fphosphateand waslargerthanthe absorbances wi a l ェ 1ount o ‐ i noftheion i l f i id t bl f th n t t h MG 駅7 i t ,EV,CV,and BG 0‐4 M su urcac wassu a e or e o a o i id w′assui df D fur tabl AB,0‐7D dsul e cac pairs . ,an or. 1) (4.

(7)          .    . 6. Tosh iko NASU at卸唖 NI SHI K 1 ana lniKASH IMAand Hi roko KUWAHAzA ,鯛【 ,M[. ◎. O.6. −A. b ( ) −. 0‐5. :. −. 0.4. ミ. −. 0‐3. ー. 0.2. ー. 0‐I ^ U. 1. H2S04 HN03. HCI. −. こ ご ▼ −. ▼. 1. HCI04 0. 0.4. 0.2. 0‐6. 。. −. 旧 0.8. 1.O. S04 ]/M [H2. Ac id. Fig.1. Ef fect of acids( )andthe concentration ofsulfuric ac i d( b a )onabsorbance with Malachi te Green ‐. ln( d i ) 8 M exceptfor H2S04;[H2S04 a ]=0 ]=0‐4 M. . , [Ac [Na l ]=24 mM 式 Ma i te Gr ach een]=144gM‐ 2Mo04 A1 5 and B 0 75〆g o fphosphorus hereagentb l . ‐ ank , measured againstt ;C ank ,thereagentbl. measured against water .. 0‐3 一. ( a ). −. b ( ) o. −. 0.2. A O. O. 」 ′ Y ー. 0‐I. 。 o. B O. −. C ^ = U. ・ ▼− H2S04. .. 1. HN03. HCI. 1 HCI04 0. Ac id. −. 1. 0‐2. 0‐4. − 0.6. 0.8. [H2S04 ]白田. 顕g.2 f tofacids( ec i f )andtheconcent l i i d( b a rat onofsu cac )onabsorbanceWi IVi . Ef ur thE故y l t o e ‐ ln( A ) i d 8 tf [ H 0 a ]=0 M S H c e x c S 0 ep or 2 4;[ 2 , 4 M. ]=0 ‐ , ‐ [Na IVi l t ]=24”M‐ o e 2Mood=40 mM 江E故y A1 o and B 0 5”g o fphosphorus l ‐ ‐ ank ank ;C , measured againstthereagentb ,thereagentbl t water measured agains .. 2) (4.

(8)    . 7f. f i i tuf th Cat ion M[ s s F1 on c Dy巴 e wi ol otat ybdphosphat. b ) ‐(. ) a o‐4 . (. A. 0.3. : 0‐2. ◎. ◎\. ‐メド. 0‐I C 0. B. ー. HCI. H2S04 HN03. HCI04 0. 0‐6. 0‐4. 0‐2. 0.8. [H S0, ]月班. Ac id. fur i id( b)onabsorbance wi値 C taIViol fectofacids( ionofsul Fig.3. Ef et cac )andtheconcentrat ーWs a . f M H S O H S 0 0 ln( A t 4 id 8 M excep or 2 . 江 ]= ‐ . ) ]=0 a , ‐ ,[ c. l IVi t ]=24〆M‐ [Na ]=40 mM ;[Ethy o e 2Moo,. A Lo and B 0 5”g ofphosphorus tthereagentblank; C,thereagentblank ‐ , measured agains t water measured agains ‐. 0‐3. ( a ). b ( ) 一. A. A. 0‐2 B B. 0. O. 0.1 C o. 0. 1 H2S04. 1 HN03. 1. 1. HCI. HCI04. 0. c. 0.4. 0‐2. 0‐6. 0‐8. [H2S04 ]/M. Ac id. i l l iantGreen ionofsul fmi id(b)onabsorbance「 Fig‐4 th Br f ids( )andtheconcentrat wi tofac cac ec a . ‐ Ef. ln( id 8 M exceptfor H2SO。;[H2SOJ=0 4 M. ) ]=0 a . . ,[Ac l i [Na ]=40 mM ;[Bnl antGreen]=24”M. 2Mo04 hereagentb l AI tthereagentb l o and B 0‐5〆g ofphosphorus ank ank ;C ‐ measured agains . ,t t water measured agains ‐. 3) (4.

(9)     .  . 8. Tosh iko NASU iN1 at sur sHI K 1 anamiKASH IMAand Hi roko KU r wAHA I斌 ,M[ ,M[. H2S04 HN03. HCI. HCI04. 0‐6. Ac i d. 0.8. [H2S0 ] /M. Fig.5. Ef f tofacids( id( b ec )andtheconcentration ofsulfuric ac )onabsorbance with Methylene a B1ue ‐. l id 8 M exceptfor H2SO.;[H2S0, ) 4 M. n( ]=0 a ]=0 . ,[Ac . l [Na thy ]=24”M. ene B1ue 2Moo =40 mM ;[Me A1 o and B O 5”g o fphosphorus tthereagentblank; C,thereagentblank ‐ . , measured agains t water I r I easured agains .. Cα産み焔云わ7 i zあま夢 2g留めお αれd sg“s Ca l ibrat iongraphsforphosphate were deve loped using Procedure 1 ar ,andthe mol inedf ivi iesobta t lopesofthe absorpt rom thes. ’ l Beer 0‐1o mg l− range of s aw i nthe o‐01 ‐. lar t mo ‐ phosphate phosphorus ‐ The highes b i Z i ined wi ty was obta th RhB, but a sorpt、 ie thylether ractedintothed excessRhBi sext i l iminatedby washing wi th andth s mustbee. ion g t raphsforeach dye r. D ‘ [ l ty o arabsorptivi Dye. 51 mol…lcm− I 10. M【 te Green alachi EthyI Violet C巧′ staI Violet Br i l l iant Green Rhoda 1mine B. へ J リム ワ十 ^ ム ー▲                    . Ca l ibrat ion graphs are l i ted in Tabl e 3 s . Except ハdB, the cal ibrat ion graphs obeyed. Tab l ivi ies for phosphate t e 3‐ M【olar absoIPt ibra‐ obtainedf rom theslopesofthecal. ibed above water as descr s . Phosphate i de imple procedure when MGi termined wi th a mores s used.. Determinat ion of Phosphateand Arsenate with M[alachi te Green. Severa l orgamc solvents were examined for extraction orf l ing ofthei i oat r of on Pa lachi th M[ te Green. The results are shown in Tabl molybdophosphate wi a e4 ‐ (44).

(10)    .  . f io両 i tuf Fi i teP O I位 Cat s { 銚 s c Dy otat on M【 ol ybdphospha. 9. ‐ext ion ofion pai lotat ion ol Table 4 l ion ofsolventforf ract rsof ect ‐ Se i te Green molybdophosphate wi伍 Malach Solvent. l−ButanoI Chlorofonn 日e×ane Cyc lohe×ane Be斑乙ene ide Carbon tet rachlor Butylacetate l−Pentano1. ‘ 【 t hy l ‐1‐butano l 3−D e. D4a lachi te Green*. 0 0 0 + + ○ + +○ ○ +. ‐2‐pentanone 4−N[ ethyl. + ○ ○ ○ + + + + + + + +. Diethylether. 1on pai rs*. l−He×anol. 4”M‐ l i ]=14 4 M ; [Na Moo, ]=24 無M;[Ma t [H S04]=0 e Green ach ‐ . l * + F1oated; − notf racted racted;and o ext oatedfoext .. f In and 4‐宜I 2−Pentanone hi The ion pai th .−Butanol − ethyl r was extracted wi , , C oro or. id not i te Green wasalsoextractedintothesol ethyletherd vent s (MIBK) . onlyd ,but Malachi lachi idf loattheion pairs atthe phase boundary between loator extract M【 f te Green td a ,buti the 山e thylether and aqueous phases‐ Therefore,diethylether was adopted asthesolventfor lotat ion ofth i thef sion pair.. l ike lachi loated as a membrane‐ th ハ4a lon pair of molybdophosphate Wi te Green wasf. he phase boundary between the aqueous and 薫ethylether phases‐ substance att. To di ssolve. D位 BK couldbeused and αー h l theionpairs, methanol ethanolgavethehighest ,or , ,et ano,acetone Therefore methanol wasu i vethe noatedion paIrs. sedto d ssol , d i l i At least 3 ml of methanol was requi d t rs containing l‐5〆g of re o sso ve on pai. fion pairs‐ absorbance o. ivi ty wasindependentoftheamomi tof methanol used‐ phosphorus ‐ The molarabsorpt. The absorbance ofion pairs wasconstant abovetheso{五uln molybdateconcentration of lach i 16 m 1 te Green was added − VVhen more than 9−6”Dd D復a ,a , and 24 mDA was chosen D 僅 was chosen f constant absorbance of the ion pairs was obtained− Therefore 24“ or the M[ te Green concentrationinthe procedure− alachi inlater ixingthereagentst i l latleast A constant absorbance wasobtainedfrom nn 1 1 ‐201 ‐. loated f i ient i imeof2 min wassuf Forthef lotat ionofion Pai ssolvethef rsa shakingt c − To d f ic i i l l ion pairs, a 30 s shaking ti lne wa vedin n・ ‐山 ethyl ether ssol ethano ssuf ent ‐ lon pairs d ion we tabl solut res efor atleast9o min .. (45).

(11)  . 1O. Tosh [ iko NASU i NI iKASHIMA and Hi SHI K 1 at sur anal n roko KUW VAHAF汎 ,M ,M[ Arsenic ( V) determinedbythe sa]me experimentalcondi ions asforphosphate t. .. C扇ぎ ろ焔云の7 i互劣り α 2gmめ姦 e 7 2 s 2 7 2d P陀c鵜zo7 ,s Theca l ibrat ion graph wasl inear uP to 2.5”g ofphosphorus or arsemc (V)‐ The apparent mo larabsoロコ iv i t inedf ty obta l ibrat ion graph was rom theslope oftheca 3.3×1051 mo l→ cm‐lat620nnn T互 l i i i 4 5t h i h h v a h ue s inedby Babko s mes g ert ant atobta − 3 ) 1 ) imeshigherthanthatreported by D江otomi et al ‐ zu et al , andl ‐4t . Thepreclslonasre lat ives ionforせl tandarddeviat eabsorbancewas2‐3and3‐5% for2−o ando‐2〆gofphospho lus(n=loand6)‐ Wi th2‐5〆gofarseni c(V),theval ue was2‐9% (n=. 6 ) ‐. 1 )eterminat ion of Phosphate Arsenate and Arseni te ,                                  The oxidat ion of arseni te to arsenate and reduct ion of arsenate to arseni te were examined f orthe determination of phosphate,arsenate, and arsenite‐ For せ ま ionofarseロite to arsenate,0‐1 mlof2−5 mD4 potassiu工n d eoxidat i chromate was ioncontain ing2 5〆g ofarsen i addedto asolut c (m) ando−2 5 ofphos horus The a h. p ‐ gr p . 〆g . i i ofabsorbanceaga l nsttheconcent l ltothecal i brat rat iongraphfor onofphosphoruswaspara e i f ference in the absorbances showed that 2 5〃g of arsenic phosphorus ‐ The d ‐. (V) were. i recovered. vv i ion of potass thout add t iu ; romate Jn di ch ins t , the graph of absorbance aga ion o fphosphorus coi concentrat ided Wi ibrat ion graphfor phoshorus‐ ththeca1 nc                                 Forthereduction ofarsenateto arsenite 1.5 mlof2 mD僅sod i iosul fate wasadded uエnロ1 , to a so l ion containing 2‐5”g of arsen i ( V ) ut d f c an o一2 5”g o phosphonユ s The 惇「 aph of. . ‐ ins t concent ion of phosphorus coinc absorbance aga ided wi rat l ibrat ion graph for th the ca h h v v i t h d d i i f d t t i h i l f f ou a ono so u Jm t osu ate p osp orus ‐ ,thegraph o absorbance againstconcen− ion o trat fphosphorus waspara l l ltotheca l brat i iongraphforphosphorus e i f ferencein ‐ Thed theabsorbancesshowedthat2‐5”g ofarsen i c (V) wasrecovered ‐. 6) (4.

(12)  . f F1 i [ ion i tuf th cat c Dy巴 s s otat on M ol ybdPhosPhate wl. 11. 霊ffect of 壷verse lons iousions Table 5. Ef fectofvar. ing The ef fect of co‐exi st diverseions on t he deter・nination of. e 5 s sshown in Tabl phosphate i ‐ other ions such as sodiu至n , potas− les lu刀Q, Z1nc lul l l l l lnonlu刀Q s , , 座ーagl , al. ium, man‐ l ロ 1),ca山ゴ t (1 copper ,coba ganese. ( 1 1) ,. luoride alw【 ninium, f ,. and carbonate had no effect on the ion deternninat. of phosphate , ar‐. i ‐ senate ,and arsente. lon. Added as. Fe(皿) * Cr(m) * ‐(W) C1 * V(V). FeC1 3 K2Cr04. S i(W). NH4V03 Na 2Si03. Ci t rate. Ci i id tr c ac. was. idto 3 idi f i L i thhydroc剛 or cac ac ed wi. 0−2 0‐2. −1. 0.2 0.2. −2. 0‐1 0‐2. 十34 十22. 十29. −3. +4. 一2. Tar t rate. Tar i tar i d ca c. EDTA**. Na2H2EDTA. 0‐05 O.2. ・ 十25 十34. 0‐05. 十17. ion o i l i ftheinterference froln s nat ‐ Con, 25o‐mI of the sample. Re l r advee r ro ,%. 0‐05 0‐2. l A 1arge a庄ーount of si icon i iveerror inl i t ‐ gavea pos ‐ Fortheel. S04 K2Cr ( ) 4 2. A /mg t no I t u ・. phosphomsl ); 〆g(*,2”g * *,ethylenedia 1minetet raacetate ‐. ハ4and eraporated. Next20‐mlof3 i l [ 亘nandf i id wasaddedtotheresidue,andthesolution was heatedforlot tered △4su1 fur c ac l wi l i l i lutedto250 nl th water i through a o‐4 5‐〆m poresizelr ter t e lnbranef l rate wasd ‐ ‐ Thef. Appl icat ions ied to the The proposed flotation‐spectrophotometric determination method was appl deter ion o f phosphate, arsenate, and arsenite in natural water sampl 1ninat es ‐ A sea w÷ater. in (Muromachi Kagaku 1W‐X8 cation‐exchange res 200 mesh 50 ‐ sampl e was treated wi故 100 KOEwo L h f i l les were d df i l dt h i b ) o 4 5 t tere roug a ‐ ‐“m poresze mem rane er ‐ othersamp , t‐ an i l f i l teredthrough a o.45 ter priortothe deterlnination‐ Theresults ‐”n lporesizennembranef are giveni n Tabl e6 ‐ Because o fthe d i f f i l in ings f water wi tandard salr th known analyses, ty ofobta ー cu ples o. f i ia ion and recovery tests were performed on the natura1 Water samp1es‐ The i 1 add i t art c l i ing water andsea ftherecovery testsfor phosphate, arsenate,and arsel ts o tein hotspr resul water or phosphatein g!ound water areshown in Tab1 es7 and8 ‐ The a]mounts added ,andf. were coI皿pletely recovered‐ The proposed f lotat ion‐ lotat ion‐ ic method was compared wi th f spectrophotometr. idylazo)‐ lato] coba l 2 2 ie thylaminopheno t (m) th bi 5‐d spectrophotometry wi s[ ‐(5 ‐ chloro‐ ‐pyr 8 ) ideastheion pairreagent. Thephosphate th ‐ erwi chlor phosphorusdeterminedingroUmd wat ‐l thetwo me故odswasi ngoodagreement ,at48‐7士1.land46‐0±1‐9〆g1 phosphorus(mean± iat ion standarddev ,n=3)‐. 7) (4.

(13)   .  . 12. Tos l uko NASU ASHIMAa d Hi I 1 at SH K sロロ NI anamiK」 I 1 roko KぴwAHAI法 ,M[ , M[. Tab l ionofPhosPhate arsenate and arseni tein natural watersa lotat ion− e 6・ Dete江田nat l 工 I esbyf P1 , , spectrophotor r l etry. Found/mg l−I. Absorbance Procedure Sample. Taken/m1. Sea waterb River waterc Snowα P. lo‐0 10‐0. 2. 0.014 0‐176 0‐058 0.247 0‐058. 3. P. AS(V). 0‐282. 0‐278. 0‐053 0‐083. 2‐56**. 0.060 0‐250 0‐059. 0‐057 0‐248 0.057. 0‐027 0.058 0‐014. 0. As( l n) ^ = V ー ^ = V^ = V^ = V. 5‐0* 5‐0 5.0. Hotspr ing α t wa er. 4. 0 0. PhosPhatePhosPhoms;As(V) arsenatearsemc;As( l n) arseni tearsemc es weretaken . SamP1. f ispa( ikar iBay( b i ) rom Jozam【 ) } e a ) ido sh ra Ri ve r( c e Hokka ,l ,Toyoh ,andtheSapporocampusof廿 Un ive i i d t )i r s on( nsapporo yofEducat . fold pr *,Th i iortot i l ion r i ssample wasd ‐ edeight ut e determinat ‐ )i * *, Therepor ted value7 55 mgl‐1 s2 . . Tab l lotat ion−spectrophotomet e 7. Recovery ofphosphate,arsenate,and arsenitebyf ry Added/”g. Recovery, %. Sample. P Hotspring. AS(V). As(m). l‐0. water. P. AS(V). As(m). 100 l‐0. 102 1‐0. Sea water. o‐5. 97 100. 1‐25. 100. Sampl etaken 5‐oml ‐. Tab l e 8‐ RecoveIγ of phosphate in ground water by notat ion‐ spect rophotometry. References. P added/”g 1) S zu akimoto and K. . Mot。mi , T. wr Toe i T l 3 2 ) 1 3 1984 t 5( a n a a . , , ,. 2) S ・ Motomizu, T・ Wrakimot。 and K. Toe i 1982 ) . ,B1msekiKagaku ,31 ,717( iand 3) A‐ K‐Babko, Yu‐ F‐shkaravski V. 1 l ik l . Ku . Ana . Khim− , Zh , 21 , 196 (1966 )‐ 4) T. Nasu and M‐ Kan t , Analys , 113 ,. pf ound/”g. Recovery ,%. 0・200 0.400. o.238 0・454 0.643. 108. o.600. 0‐846」. 10I. o. 101. Samp1etaken 5.oml . The gr do University. i ow・d waterf rom Hokka. 1 63 1988 ) 8( ‐ i 5) T‐ Nasuands. Kaneko,Anal 1989 )‐ .Sc り5 ,449( A n l 6) T. Nasuand N‐ Minami 1 1 4 9 ( ) t 5 5 1 9 8 9 . , ays, ,. 8) (4.

(14)  . f i ion tuf th Cat l s F1 i c Dyes o otat on M【 ybdphosphate Wi )‐ 7) S. Nakaya,BunsekiKagaku,12 ,241(1963 i 1988 ) l 8) M‐Tagaand M.Kan ‐ . ‐Sc ,4 ,181( ,Ana. (49). 13.

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