Xác định thành phần phức chất khi chiết Gadolini bằng Triphenylphotphin oxit - toluen từ môi trường Axit Clohyđric

^ ^ .nmmfsm»-m.<br /> XAC DjNH THANH PHAN PHUfC CHAT KHI CHIET GADOLINI<br /> BANG TRIPHENYLPHOTPHIN OXIT - TOLUEN TUT MOI TRlTtfNG<br /> AXIT CLOHYDRIC<br /> NGUYIN DINH LUYgN\ TRAN HOANG KHANH'<br /> 'D^i hpc Su pham, Dai hpc Hui<br /> 'Trudng THPT Blnh Sdn, Quing Ngai<br /> <br /> <br /> SUMMARY<br /> The gadolinium complexation of triphenylphosphine oxide (TPPO) was demonstrated by its UV-VIS<br /> and infrared spectra. The complex's composition upon the extraction ofGd^* by TPPO from chloride<br /> medium was determined.<br /> <br /> <br /> L M d DAU<br /> <br /> Photphin oxit thudng dupc chpn lam phdi tQ tao [1], axit tricloaxetic [4], cung nhu xac djnh thanh phln<br /> phQc vdi cac ion nguygn td dlt hidm (NTDH) va dupe phQc eua chung [2], [3] da dupc nghign cQu. Treng<br /> sQ dgng lam dung mOi chidt trong qua trinh phan chia, bai bao nay chung tOi thflng bao kdt qui vd khi nang<br /> lam giau Chung [7]. Vigc chidt mflt sd NTDH blng tao phQc, thanh phln phQc chit dupe chidt cua Gd^*<br /> triphenylphotphin oxit (TPPO) tQ mOi trQdng axit nitric blng TPPO tQ mOi trQdng axit clohydric.<br /> <br /> <br /> n. THl^C NGHlIlM<br /> <br /> - Dung djch GdClj dupe didu chd blng each hda tan 3ml nhu trong [2, 3, 4]. Thdi gian chidt va phan pha<br /> oxit gadolini tUdng Qng ed dO sgch 99,9% trong HCI. ij io phut. Ndng dfl Gd^* trong pha nude va pha hQu<br /> fD%"t„',t*6iT,lt(.SS."^?Pra°rsS " (sau . . ,lil o h * , .>.o xic di„h bin, ph^g ph.p<br /> (III),... ddu cd dO sach PA. ^^"''" ''d VI lupng bang dung d|eh chuln DTPA vdi<br /> -"phUdng phap chidt NTDH blng tac nhan chidt ''^'^'^ *^^ ^^5^"^° ('")• ^^^ ^""9 "9°^j "^^^ 9^^ *r«"<br /> TPPO dupe tidn hanh trgn phiu chidt cd dung tfch "^^V 'R - Equnox 55 - Bruker (DQc), phd tQ ngoai dope<br /> 20mL. Ty Ig thd tfch pha nude va pha hOu cd la 3ml: ghi trgn may T80 - UV - VIS Spectrometer (Anh).<br /> <br /> <br /> HI. KET QUA VA T H A O L U ^ N<br /> <br /> <br /> 1. H I ^ U tfng t^o phtfc cua Gd^ vdi tdc nhSn Trgn phd tQ ngoai ta thly cd sg chuydn djch tQ<br /> chig't TPPO 273nm (phd UV cua GdCy va 284nm (phd UV cua<br /> ^^, X * ^.- ' ^.3, ^-rnno. u. u-.- TPPO) vd 286 va 309nm (ohd UV cua GdCl3-TPP0). TQ<br /> Khi nang tao phQc eua Gd^* vdi TPPO trpng hg ehigt sg chuydn djch trgn ed thg khIng djnh cd sg tao phQc<br /> GdCl3-TPPO-toluen b didu kign t?o phQc thfch hpp nhQ cua Gd^* vdi TPPO.<br /> [5] dupc thd hign trgn phd tQ ngoai (UV) 6 hlnh 1 va jrgn phd hdng ngoai eua GdClj, b vung tin sd<br /> hdng ngoai (IR) b hlnh 2 3432,82 va 1635,55cm-i la vung dao dflng cua nhdm<br /> <br /> <br /> H6a hpc & Lfng dung<br /> Si 22 (jo6)/20og ( S ^<br /> -OH ciJa HjO tg do va d dang hydrat, dai hip thg ' (phd IR cua TPPO-toluen) ddn 1118,13 (phd IR cua<br /> 663,45cm-^ la vijng dao dflng eua lign kg't Gd-CI. GdCl3-TPPO-toluen), cae sQ chuyen djch nay cd thd do<br /> cac cap electron tg do eua oxi trong nhdm -P=0 tUdng<br /> Trgn phd hdng ngoai cua TPPO-toluen, b vung tan sd<br /> tac vdi Gd^*. Do sg tao phQc nay lam giam m$t dg<br /> cao 3449,04cm-^ la viing dao dpng nhdm -OH cua HjO,<br /> electron b nguygn tQ photpho, lam yg'u lign kdt giQa 0<br /> dai hip thg 2919,55em-^ la viing dao dflng hda trj cua<br /> va P trong nhdm -P=0 d i n ddn sg chuyen djch cac<br /> nhdm -CH3 cQa toluen, dai hip thg d 1646,07 va<br /> tan sd dao dflng b trgn.<br /> 1512,79cm-^ la vung dao dpng dac trung cua cac nhdm<br /> CeHs- cua TPPO va toluen, dai hap thg eua nhdm -P=0 TQ phd tQ ngoai va hdng ngoai chQng to ring cd sg<br /> d 1025,30cm-\ tao phQc eua Gd^* vdi tac nhan chig't TPPO trong mfli<br /> trQdng axit clohydric.<br /> <br /> 2. Thanh phan phtfc chS't cua Gd*" vtfi TPPO<br /> ttf moi trtfcfng axit clohydric<br /> Trong hg GdCl3-TPPO-toluen, ion Gd^* dupe chidt vao<br /> pha hQu Cd theo phan Qng:<br /> Gd^;, + 3CI(n) + xTPPO(hc) « LnCl3.xTPP0(hc) (1)<br /> <br /> Khi hg d?t trgng thai can blng, ta cd:<br /> <br /> [GdCl3.xTPP0](t,c) D<br /> \b (2)<br /> 250 300<br /> [Sd'l(n)-[TPPOt.[Cr]J, [Tppo];,).[ci-<br /> wavelength<br /> Suy ra: IgD = IgK,, + 3lg[Cn(n) + xlg[TPPO](,„<br /> Hinh 1: Pho ttf ngoai cua GdClj, TPPO d nhigt dfl khflng ddi, K^^ la hing sfl', khi ndng dg<br /> va phtfc GdClj-TPPO Gd^* r l t nho, ndng dfl phQc tao thanh ed the bd qua<br /> 1) GdClj 2) TPPO 3) GdClj-TPPO ngn [TPPO] = CTPPO, [Cl"] = CHCI, khi dd phQdng trinh<br /> (2) trd thanh:<br /> IgD = A + xlgCTPPo,^^, (trong dd A la hIng so)<br /> •E^<br /> Cac thf nghigm xac djnh thanh phln phQc chit dupc<br /> -"V chig't eua Gd'* dupe tidn hanh trong dieu kign: C^^i* =<br /> GdClj<br /> 0,0005M; CHCI = 0,5M; thdi gian lie chig't 10 phut; ndng<br /> •8SS- dfl TPPO-toluen thay ddi, the tfch pha hQu cd : the tfch<br /> pha nude = 3ml : 3ml, ndng dp eua Gd'* trong pha<br /> TPPO nudc va pha hQu ed (sau khi giai chiet) dupe xac djnh<br /> blng phUdng phap chuln dp vi lupng. Tri sd x chfnh la<br /> hg sd gdc cua dd thj IgD = f(lgCTppo) vdi CTPPO la ndng<br /> Gd-TPPO dfl ban dau dupc pha che tQ lupng can chfnh xac. Ket<br /> qui dQpc trinh bay b hlnh 3.<br /> 3500 3000 2500 2000 1500 1000 500<br /> IgD<br /> Wavenumber cm' Gd<br /> -0.6<br /> Hinh 2: Pho hong ngoai cua GdClj,<br /> TPPO - Toluen va GdClj - TPPO - Toluen -0.8 Linear Regression for Dalai B;<br /> <br /> <br /> <br /> Tren phd hdng ngoai cua GdCl3-TPP0-toluen, 6 vung<br /> -1.0 -Parameter Value En-or<br /> 0 89866 0.11<br /> tan sd cao 3464,76cm-' la vung dao dpng cua nhdm - -1.2 B ^L??352__ 0^104_3_9<br /> OH ciJa H2O, dai hip thg 2921,53cm-' la viing dao dpng Ff_ SD N P<br /> -1.4<br /> hda tri ciJa nhdm -CH3 cua toluen, dai hap thg ciJa 0 99512 0.03951 T T o s b Y s T i<br /> nhdm CgHj- cd sg chuydn djch tQ 1646,07 va -1.6<br /> 1512,79cm-' (pho IR cua TPPO-toluen) den 1606,47 va 1.3 -1,2 -1.1 -1.0 -0.9 -0.8 IgC,,,,<br /> 1435,99em-' (phd IR cua GdCla-TPPO-toluen), dli hap<br /> thg cua nhdm -P=0 cd sg chgydn djch tQ 1025,30cm- Hinh 3: Stf phu thupc IgD vao IgC^<br /> <br /> <br /> Hoa hpc & Ung dung<br /> O)) Si 22 (to6)/2oog<br />  Hlnh 3 cho thly, sQ phg thuflc cua IgD vao IgCrppo Thanh phln phQc cua Y^* dupc chidt trong hg TPPO-<br /> la tuydn tfnh va hg sd gdc cua dudng thing IgD = toluen tQ mfli axit nitric dupc xac djnh la Y(N03)3.3TPP0<br /> t(lgCTPpo). tga = X = 1,8. Do dd phQc cua Gd^* dupe<br /> chidt vao pha hOu cd la GdCl3.2TPP0. Vay qua trinh [2], tQ mfli trudng axit tricloaxetic la Y(CCl3C0O)3.2TPP0<br /> chidt Gd'* blng TPPO trong mfli trudng HCI xly ra theo [3]. Nhu vgy, thanh phln phQc cua NTDH dupc chidt<br /> phUdng trinh phln Qng:<br /> trcng hg TPPO-toluen tQ mfli trudng axit clohydric tuong<br /> Gd3;, + 3CI(n) + 2TPP0(hc) « LnCl3.2TPP0(hc) tg nhu tu mfli trodng axit tricloaxetic.<br /> <br /> rV. KET LUAN<br /> - Da khio sat higu Qng tao phQc cua Gd'* vdi tac - Da xac djnh dupe thanh phln cua phQc khi chidt<br /> nhan chidt TPPO-toluen trong mOi trudng axit clohydric Gd'* blng TPPO-toluen tQ mfli trQdng axit clohydric la<br /> blng phd tQ ngoai va hdng ngoai, kdt qui cho thly cd<br /> higu Qng tao phQc giQa chung. 6dCl3.2TPP0.<br /> <br /> TAI LI?U THAM KHAO<br /> 1. LUU Minh Dgi, Dao Ngpc Nhigm (2006), Chiit trudng axit tricloaxetic, Tap chf Hda hpc va Lfng- dgng.<br /> neodym vi ytri bing triphenylphosphin oxit (TPPO) td 5. Nguyin Dinh Luygn, TrIn Hoang Khanh, Nguyin<br /> mdi trudng axit nitric, Tgp chf Hda hpc, T.44 (5), Thj Hdno Md, Nguyin Thj Trang (2009). ChiSt La, Nd<br /> tr.571-573. Gd, Er bang triphenylphotphin exit til mdi trUdng cirua<br /> 2. Luu lyiinh Dai, Dao Ngpc Nhigm (2007), Xic djnh vi thioxianat. Tap chf Khoa hpc & Giao dgc, Trudng<br /> thinh phin cua phdc chat triphenylphosphin oxit-ytri DHSP, Dai hpc Hud (Da nhan dang).<br /> til mdi trudng axit nitric. Tap chf Hda hpc, T.45 (2), tr. 6. Nguyin Dinh Trigu (2001), Cic phUdng phip phin<br /> 195-198. tich vit ly vi hda ly, NXB Khoa hpc v l Ky thudt. Ha Nfli.<br /> 3. Nguyin Dinh Luygn, Nguyin HQu Hidn, Pham Quy, 7. Barbara Stuart (2004), Infrared Spectroscopy:<br /> Vo Tidn iJung (2009), Chiit fim giiu ytri vi xic djnh Fundamentals and Applications, Wiley, Chichester, UK.<br /> thinh phin phdc cua nd vdi triphenylphosphin oxit til<br /> mdi trudng axit tricloaxetic. Tap chf Khoa hpc & Giao 8. T.S. Lobana, F.R. Hartley (1992), The Chem-<br /> dgc, Trudng DHSP, Dai hpc Hug, sd 01(09), tr.19-23. istry of Organophosphorus Compounds, Wiley, New<br /> York, USA. *<br /> 4. Nguvin Dinh Luygn, Pham Quy (2009), ChiS'tcic<br /> nguySn todit hiim bing triphenylphosphin oxit til mdi NgUttiphin biin: TS NGUviN V A N H A I<br /> <br /> <br /> <br /> NGHIEN cufu Sir TAO PHUfC DA PHOI TUf...<br /> (Ti^p theo trang 39)<br /> <br /> TV. KET LUAN<br /> SQ dgng phuong phap chidt - trie quang dd nghign - Da xac djnh dope cac tham sd djnh lopng cua phQc.<br /> cQu sg tao phQc PAN-La(lll)-SCN' trong dung mfli hOu<br /> cd izoamylie. Chung tfli dua ra kdt luIn: - Da xac djnh dupc phUdng trinh dudng chuln va<br /> - Da nghign cQu mflt each cd hg thdng sg tao phQc, khoing ndng dfl phQc tuan theo djnh luat Beer.<br /> cac didu kign tao phQc va chidt phQc tdi QU.<br /> - Da xac djnh dupc ham lupng lantan trong mlu<br /> - Da xac djnh dQpe thanh phln, cd chd ciia phln<br /> Qng tao phQc daligan. nhan tao va mlu that cho kdt qui phii hpp vdi thgc td.<br /> <br /> TAI LitU THAM KHAO<br /> 1. Hd Vidt Quy (1999): Cic phUdng phip phin tich 3. Bhoon Y. K, Pandeya K. B. (1974) "Metal com-<br /> quang hpc trong hoi hpc. NXB. OHQG Ha Nfli. plexes of 1- (2- Pyridylazo)- 2- Phananthrol (PAP) as<br /> 2. TrIn COng Vigt (1993), luan an tidn sy, "NghiSn Visual Indicators in acid- Base Titrations" J. Indian<br /> cdu stf hlnh thinh vi chief phdc da phCfi tit cua mdt Chem. Soe, Vol. LI, pp. 960-962. «<br /> s6 nguySn t6 dit hiim vdi PAR - axit axetic vi din<br /> xu5?cua/?d". tr.16-19. NgUtiphin bifn: PGS, TS DINH XUAN DJNH<br /> <br /> <br /> <br /> H6a hpc & tfng dyng<br /> S r 2 2 (io6)/20og<br /> m<br />