MC LC Li cm n M u Phn I: Tng quan I. Nguyn t Ch (Pb) v cc phng php xc nh I.1. Gii thiu v nguyn t Ch (Pb) I.1.2.

Cc phng php xc nh Ch (Pb) I.1.2.1 Phng php cc ph I.1.2.2 Phng php trc quang I.1.2.3 Phng php AAS I.1.2.4 Phng php chun Complexon I.1.2.4.1 Xc nh trc tip bng ch th Ecrioccrom en T I.1.2.4.2 Xc nh trc tip bng ch th Xylen da cam I.2 Nguyn t Cadimi (Cd) v cc phng php xc nh I.2.1 Gii thiu v nguyn t Cadimi (Cd) I.2.2 Cc phng php xc nh Cadimi (Cd) I.2.2.1 Phng php trc quang I.2.2.2 Phng php chun Complexon I.2.2.3 Phng php AAS I.2.2.4 Phng php cc ph I.3 Nguyn t Km (Zn) v cc phng php xc nh I.3.1 Gii thiu v nguyn t Km (Zn) I.3.2 Cc phng php xc nh Km (Zn) I.3.2.1 Phng php trc quang I.3.2.2 Phng php cc ph I.3.2.3 Phng php AAS I.4 Nguyn t ng (Cu) v cc phng php xc nh

I.4.1 Gii thiu v nguyn t ng (Cu)

I.4.2 Cc phng php xc nh ng (Cu) I.4.2.1 Phng php trc quang s dng thuc th DDC I.4.2.2 Phng php cc ph I.4.2.3 Phng php Neocuprionie I.4.2.4 Phng php AAS I.5 Phng php cc ph I.5.1 C s ca phng php I.5.2 C s ca phng php cc ph I.5.2.1 Phng php cc ph sng vung I.5.2.2 Phng php cc ph xung thng (NPP) I.5.2.3 Phng php cc ph xung vi phn (DPP) I.5.3 Phng php Vn-Ampe ha tan I.5.4 Phng php Vn-Ampe ha tan hp th (AdSV) I.5.5 Cc phng php phn tch nh lng trong phn tch in ha I.5.5.1 Phng php mu chun I.5.5.2 Phng php ng chun I.5.5.3 Phng php thm chun I.5.5.4 Phng php thm I.5.6. Cc loi in cc c s dng trong phn tch cc ph I.5.6.1 Cc rn hnh a (RDE) I.5.6.2 in cc mng thy tinh (TMFE) I.5.6.3 in cc git thy ngn treo (HMDE) Phn II: THC NGHIM V KT QU II.1 Thit b, dng c v ha cht II.1.1 Thit b, dng c II.1.2 Ha cht II.2 Ly v bo qun mu

II.3 V c ha mu

II.4 Xc nh Zn, Pb, Cu, Cd II.4.1 Thc nghim tm cc iu kin ti u cho php xc nh Zn, Pb, Cu, Cd II.4.1.1 Pha ch dung dch cho php xc nh Zn, Pb, Cu, Cd II.4.1.2 Kho st cc iu kin ti u cho php xc nh Zn, Pb, Cu, Cd II.4.1.2.1 Kho st s xut hin pic II.4.1.2.2 Kho st bin xung II.4.1.2.3 Kho st thi gian t xung II.4.1.2.4 Kho st tc qut th II.4.1.2.5 Kho st thi gian sc kh II.4.1.2.6 Kho st thi gian cn bng II.4.1.2.7 Kho st nh hng nng ca mi cht ln nhau II.4.1.2.7.1 nh hng nng ca Ni2+ ti Zn2+, Cd2+, Pb2+, Cu2+ trong nn m axetat II.4.1.2.7.2 nh hng nng ca Fe3+ ti Zn2+, Cd2+, Pb2+, Cu2+ trong nn m axetat II.4.1.2.7.3 nh hng nng ca Pb2+ ti Cd2+ trong nn m axetat II.4.1.2.7.4 nh hng nng ca Zn2+ ti Cd2+ trong nn m axetat II.4.1.2.7.5 nh hng nng ca Cu2+ ti Pb2+ trong nn m axetat II.4.1.3 Kt qu kho st cc iu kin ti u cho php xc nh ng thi Zn2+, Cd2+, Pb2+, Cu2+ II.4.2 Xc nh Zn2+, Cd2+, Pb2+, Cu2+ trong mu t to II.4.3 Tin hnh nh lng Km (Zn), Cadimi (Cd), Ch (Pb), ng (Cu) trong mu nc sng II.4.4 Tin hnh nh lng Km (Zn), Cadimi (Cd), Ch (Pb), ng (Cu) trong mu rau Phn III: KT LUN TI LIU THAM KHO

LI CM N hon thnh c kho lun ny em xin by t lng bit n su sc n ging vin Thc s inh Th Trng Giang giao ti, ht lng hng dn, ch bo, truyn t kin thc kinh nghim qu bu cho em trong sut qu trnh hon thnh kha lun ny. Em xin chn thnh cm n cc thy, c gio trong t b mn ha Phn tch, cc thy gio, c gio hng dn phng th nghim thuc khoa Ha hc trng HV to mi iu kin gip em trong qu trnh hon thnh kha lun tt nghip. Cui cng em xin gi li cm n su sc n b m, anh ch em v bn b quan tm, ng vin em hon thnh kha lun tt nghip ca mnh. Vinh, thng 5 nm 2010 Sinh vin Phm Th Lu

M U X hi cng pht trin, vn nhim mi trng cng t ln hng u, nhim mi trng t nhiu ngun khc nhau y l mi nguy c e da s sng ca mun loi. Qu trnh th ha nhanh, cng nghip ha, hin i ha cc nc pht trin l nguy c gy nhim kim loi nng cho nc, t v khng kh. S nhim c bi cc kim loi nng nh Zn, Cd, Pb, Cu gy ra nhng bnh m v nguy hi i vi con ngi v ng vt. Trong s cc kim loi nng th ng v Km l nhng nguyn t cn thit cho c th nng thp, nng cao chng gy ra cc vn v tim mch, tiu ha v thn c th dn n t vong. Ch v Cadimi l cc kim loi c c tnh cao vi ng vt v con ngi c th gy ra bnh ung th, bnh v xng. Khi hm lng Ch trong mu cao s lm gim hp th vi cht, gy thiu mu, km n v suy dinh dng, t lm gim tr tu ca tr em. V vy, vic xc nh v kim sot c hm lng cc kim loi nng l vic lm cn thit v cp bch. C nhiu cch xc nh hm lng kim loi trong phng php Vn-Ampe ha tan xung vi phn (DPP) trn in cc git thy ngn treo l phng php c chnh xc, chn lc, nhy v tin cy cao, c th xc nh c hm lng cc kim loi c nng thp.Do vy, em chn ti Xc nh ng thi hm lng Km, Cadimi, Ch, ng trong nc sng v rau bng phng php VnAmpe ha tan anot xung vi phn. Vi ti ny chng ti ra nhim v: - Tm cc iu kin ti u nh lng ng thi Zn, Cd, Pb, Cu. - Nghin cu nh hng hai nguyn t Ni(II), Fe(III) ti php xc nh ng thi Zn, Cd, Pb, Cu.

- Nghin cu nh hng ln nhau ca cc nguyn t Zn, Cd, Pb, Cu. - Th cc iu kin ti u chn vo vic phn tch mu t to ca Zn,Cd, Pb, Cu. - Phn tch mu nc sng, mu rau cha Zn, Cd, Pb, Cu. Chng ti hi vng rng kha lun ny s gp phn b sung thm cc phng php xc nh lng vt kim loi trong mt s i tng khc nhau

PHN I: TNG QUAN I. Nguyn t ch (Pb) v cc phng php xc nh I.1. Gii thiu v nguyn t Ch (Pb) Ch (Pb) thuc phn nhm chnh nhm IV, chu k 6 trong bng h thng tun hon. Ch c s th t: Z= 82 Khi lng nguyn t: 207,2 Cu to electron Nhit nng chy Nhit si Khi lng ring m in : [Xe]4f145d106s26p2 : 327,46oC : 1737oC : 11,34 g/cm3 : 2,33

Tr lng trong thin nhin ca ch l 1.10-4 % tng s nguyn t ca v tri t, tc l nguyn t t ph bin. Ch l kim loi mu xm thm, rt mm. iu kin thng ch b oxy ho to thnh lp oxt mu xm xanh bao bc trn mt bo v ch khng tip tc b oxy ho na. Pb tan c trong

cc axt. Ch ch tng tc trn b mt vi dung dch axit clohidric long v axit sunfuric di 80% v b bao bi lp mui kh tan (PbCl2 v PbSO4) nhng vi dung dch m c hn ca cc axit ch c th tan v mui kh tan ca lp bo v chuyn thnh hp cht tan: PbCl2 + 2HCl = H2PbCl2 = Pb(HSO4)2 PbSO4 + H2SO4

Pb d dng tc dng vi axit HNO3 bt k nng no, c th tan trong axit axetic v cc axit hu c khc. Ch c dng lm tm in cc trong cquy, dy cp in, u n v cc ng dn trong cng nghip ho hc. Ch hp th tt tia phng x v tia Rnghen nn c dng lm nhng tm bo v khi lm vic vi nhng tia . Tng ca phng th nghim phng x c lt bng gch ch, mi vin gch thng nng hn 10 kg. Ch v cc hp cht ca ch u rt c, nn khi tip xc cn phi cn thn. I.2.Cc phng php xc nh Ch (Pb) xc nh Pb trong nc b mt, nc sinh hot thng dng phng php chit trc quang vi thuc th Dithizon l phng php cho php xc nh t 0,11,0mg Pb/l. Pb l kim loi d xc nh bng phng php cc ph, phng php ny cho php xc nh Pb trong nc t 0,05mg n vi mg trong 1 lit nc. xc nh Pb trong nhng loi nc sch c hm lng nh hn 0,02 mg/l nn dng phng php phn tch in ho ho tan. I.2.1 Phng php cc ph Ion Pb (II) l mt trong nhng ion c hot tnh cc ph b kh trn catot thu ngn thnh kim loi. Trong nn NaOH 1 M phc Pb(OH)2 b kh thun nghch v cho sng cc ph vi th bn sng -0,7 V so vi cc calomen bo ho.

Nu trong dung dch c cha Fe (III) vi hm lng khng ln lm, st s b kt ta hidroxit trong nn NaOH v khng gy tr ngi n s xc nh Pb. Nu hm lng st ln kt ta Fe(OH) 3 s hp ph Pb, trong trng hp ny nn xc nh Pb bng phng php thm chun. Nu trong nc c lng tng i ln Cu (II) trong mi trng kim d n cng b tan mt phn di dng CuO22- v sng ca ng cng nh hng n s xc nh Pb. Trong trng hp ny sau khi thm NaOH vo dung dch phn tch lng kt ta ri dng pipet ly ra 10 ml dung dch trn thm vo 0,5ml KCN 1M che ng. Lng xianua khng c d nhiu v s d nhiu s lm gim bc sng ca Pb. Tu thuc vo hm lng Pb m ta tin hnh nh sau: Ly 25ml mu nc cho vo bnh nh mc dung tch 50ml nu cn pha long mu nc trong 25ml cha khong 0,13 mg Pb. Nu hm lng Pb trong mu ch nm trong khong 0,55 mg Pb/l th cn ly 250ml mu thm vo 1ml HNO3 c. Lm bay hi trong bp cch thu n cn kh, ho tan b kh trong nc ct v chuyn ton b dung dch thu c vo bnh nh mc 50 ml. Tip theo thm vo 5 ml NaOH, 1ml gielatin nh mc bng nc ct v lc u dung dch. Nu c kt ta hydroxit th cn lng v tin hnh ly phn dung dch trong v tin hnh ghi cc ph nhy thch hp t -0,4-1,0 V so vi anot y thu ngn. o chiu cao sng v da vo ng chun xc nh hm lng Pb. Nu hm lng mu c cha 0,051mg Pb/l th ly 250ml mu nc cho vo cc chu nhit thm vo 1ml HNO3 c v lm bay hi dung dch n kh. Thm vo b kh ngui 0,5ml HNO 3 c v c li ln na. Cho vo b kh ngui 5ml dung dch NaOH 10M +1ml gielatin + 44ml nc ct trn u (dung dch nn). Sau khi b kh ho tan ht tin hnh o ghi cc ph t -0,4-1,0 V so vi y anot thu ngn. Da vo ng chun xc nh hm lng Pb.

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Nu mu cha lng ln cht hu c cn ph hu chng nh trong phng php dithizon trn. loi oxi khng dng Na 2SO3 v ion Pb (II) s kt ta di dng PbSO4, c bit vi trng hp nng Pb ln. Cn dng khng kh tr nh N2 hoc H2 tinh khit cho chy qua dung dch trc khi ghi cc ph loi oxi. Dng gielatin loi tr cc i cc ph ca Pb. Phng php Vn-Ampe ho tan hp th (AdSV) vi thuc th 8hydroquinolin (pH= 7,88,5) Pb cho pic ti -0,54 V vi gii hn pht hin l 3.10-10M. Bng phng php Von-Ampe ho tan anot (ASV) trong nn m axetat (pH= 4,6) Pb cho pic ti -0,4 V vi gii hn pht hin ti 1.10-10M .

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I.2.2 Phng php trc quang Phng php phn tch trc quang l nhm cc phng php phn tch quang hc. Phng php ny chuyn cc cht phn tch thnh nng lng nh sng suy ra lng cht cn phn tch. Pb (II) l cation kim loi c kh nng to phc vi nhiu thuc th hu c khc nhau. V vy c th p dng phng php trc quang xc nh Pb. Vic xc nh Pb bng phng php trc quang vi dithizon l phng php ph bin nht bi tnh u vit ca n. Dithizon (diphenyl thiocacbazon) l thuc th hu c c kh nng to phc cng cua vi nhiu kim loi trong c ch. Ch dithizonat kh tan trong nc nhng d tan trong cc dung mi hu c nh CHCl 3, CCl4. Trong CCl4 ch dithizonat c mu cc i hp th bc sng = 520nm. Ch dithizonat c chit chn lc v nh lng t dung dch nc c pH = 89, cha lng d xianua, l cht dng che nhiu kim loi khc c th b chit cng Pb. Nu trong mu nc cha lng ng k cc cht hu c th cn phi v c ho chng bng cch cho vo vi ml HNO3 c v HClO4 c c mu n kh. Sau tm t b kh bng axit HNO3 v ho tan bng nc ct. Cc cht oxi ho cn c kh trc bng hidrazin. I.2.3 Phng php AAS Vi phng php F-AAS s dng ngn la l hn hp kh (khng khaxetilen) vi t l 5,2/1,25 L/ph (V/V) o ch bc sng = 217nm. C th dng thuc th APDC (amoni pyrolydin dithiocacbamat) trong MIBK (metyl isobutyl ketone) (mu c axit ho bng axit HCl n pH = 45). Vi phng php AAS khng dng ngn la th nguyn tc ca phng php l: mu c a vo l, ti y n c sy kh, tip n l tro ho v cui cng mui ca ch c phn ly di dng ch nguyn t, trong mi trng kh tr Argon. iu kin nguyn t ho l: sy nhit 120oC 200oC, trong thi gian l 30 giy; tro ho nhit 450 oC, trong thi

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gian 20 giy; nguyn t ho nhit 1900oC, trong thi gian 3 giy. Vng tuyn tnh l: 2 50 ng/ml. I.2.4 Phng php chun Complexon I.2.4.1 Xc nh trc tip bng ch th Ecriocrom en T Dung dch ch c hm lng trong mu phn tch khong 20mg ch trong 100ml th ngi ta dng 5ml dung dch tatrat (1:4) hoc tritanolamin ( TEA) to phc che cc ion kim loi gy cn tr cho php xc nh ch. Sau trung ho mt lng tng ng dung dch NaOH, trong mt s trng hp c th cht che nh KCN, sau thm 2ml dung dch m c pH = 10 v cht ch th, chun cho n dung dch chuyn t mu nu sang xanh. I.2.4.2 Xc nh trc tip bng ch th Xylen da cam Trong dung dch phn tch thng khng qu 50mg Pb trong 100ml. nu cn thit trung ho dung dch bng NaOH n pH = 23 sau thm lng thch hp dung dch m axetat (tt hn l dng dung dch Urotropinhexametlyentetramin) lc pH dung dch cn phi bng khong 5, thm cht ch th v chun cho n khi dung dch chuyn t mu tm chuyn sang vng. II Nguyn t Cadimi (Cd) v cc phng php xc nh II.1 Gii thiu v nguyn t Cadimi (Cd) Cadimium (Cd) l nguyn t ho hc thuc nhm IIB, chu k 5 trong bng h thng tun hon cc nguyn t ho hc, s th t 48, nguyn t khi 112,41. Cd c cu hnh lp v 18+2e l cu hnh tng i bn. Do nng lng ion ho th 3 rt cao lm cho nng lng sonvat ho hay nng lng to thnh mng li tinh th khng lm bn c cho trng thi oxy ho +3. trng thi oxy ho cao nht ca Cd ch l +2.

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c im ca nguyn t Cd S th t nguyn t 48 Cu hnh electron [Kr]4d10 5s2 Nng lng ion ho I1 8,99 I2 I3 16,90 37,47 Bn knh nguyn t, Ao 1,56 Th in cc chun, V -0,402

Cd l kim loi nng, mm, mu trng xanh, d nng chy, khi lng ring 8,65 g/cm3, tnc = 32 oC, ts = 767 oC, nhit thng hoa 112kJ/mol, dn in 13. trong khng kh m chng dn dn b bao ph bi lp oxit nn mt tnh nh kim v khng b g.Khi un nng tc dng c vi oxy v nc to thnh oxit. D tan trong axit HNO3. L mt nguyn t him,chim khong 7,6.10-6- % tng s nguyn t tng ng trong v tri t. Trong thin nhin Cd thng tn ti trong hp kim cng vi Zn, Cu. Cd l mt kim loi c hin i. N ch mi c pht hin nh mt nguyn t vo nm 1817 v c s dng trong cng nghip t khong 50 nm trc. hin nay Cd l mt kim loi rt quan trng trong nhiu ng dng khc nhau, c bit Cd c s dng ch yu trong m in, v n c c tnh khng n mn. Ngoi ra Cd cn c s dng lm cht mu cho cng ngh sn v cng ngh cht do v l catot cho cc ngun pin niken-cadimi; sn phm ph ca cng ngh luyn ch v km. II.2 Cc phng php xc nh Cadimi (Cd) Tu theo hm lng Cadimi trong mu v yu cu ca php phn tch m chng ta c cc phng php xc nh Cd ph hp khc nhau. Sau y l mt s phng php xc nh Cadimi. II.2.1 Phng php trc quang xc nh Cd bng phng php trc quang dng dithizon, ngi ta chit bng CCl4 t mi trng kim mnh cha tactrat. Dung dch dithizonat ca dung dch Cd trong dung mi hu c c mu hp ph cc i bc

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sng = 515 nm. Bng phng php ny c th xc nh hm lng t phn trm mg n miligam Cd. Hm lng Cadimi khong 0,01 0,5mg Cd/l c th dng phng php xc nh nh sau: Nu nh mu phn tch c cha lng ln cht hu c th cn v c ho chng bng cch thm vo th tch nc ly phn tch 12ml H2SO4 c, 35 ml HNO3 c v lm bay hi dung dch trong t ht. Nu dung dch cn c mu th li thm 5ml HNO3 c v li lm bay hi ln na, ng tc ny lp i lp li cho n khi thu c dung dch khng mu. Sau lm bay hi dung dch n kh thm tip vo b 1ml HCl c v lm bay hi ln na. Phn b sau khi ngui c ho tan bng nc ct 2 ln, un nng ho tan ht mui tan, lc qua phu lc kh bng giy lc v gi ly dung dch xc nh Cd. Trong mi trng kim mnh cc kim loi khc nh Ag, Cu, Ni,Co cng b chit cng vi Cd. Cc nguyn t ngn cn cn c chit trc khi xc nh Cd bng dithizon t mi trng axit. Nu trong mu c CN- th cn ph hu xianua bng cch thm 0,5 ml H2SO4 c vo 100ml mu nc un si 10 pht trong t ht. Sau thm 0,2 ml HCl c khuy u v yn ( kt ta AgCl lng xung) trong 2 gi. Lc dung dch ra phu bng vi ml nc ct, trong nc lc cn c th cha mt lng nh bc Cu, Hg v mt lng nh Ag cn trong nc lc c c chit loi b bng dithizon t mi trng c pH= 2. Thm vo nc lc 5ml dung dch mui xaynhet 20% iu chnh pH n 2 bng cch khuy v thm t t dung dch NH3 hoc HCl. Cho mu vo phu chit v chit mi ln bng 5ml dithizon 0,1% trong CHCl3, chit cho n khi lng dithizon sau khi chit vn gi nguyn mu xanh ban u ca n. Sau ra mu bng 10 ml CHCl 3 cho n khi dung mi ra khng mu.Cui cng ra thm 2 ln mi ln 5 ml CCl4. Nu trong mu c cha Ni th tch bng dimetylglioxim nh sau:

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Ly 50 ml dung dch mu u hoc dung dch mu sau khi v c ho, cho vo 10 ml dung dch kalinatritactrat 20% (nu ly mu sau khi tch Ag, Cu, Hg th ch cn thm 5 ml dung dch tactrat l ). Thm NH3 vo cho n khi pH= 8,59, thm vo tip 5 ml dung dch dimetylglioxim 1% trong ru etylic 96%. Cho ton b hn hp vo phu chit lc u trong 30 giy.Chit phc niken dimetylglixionat vi ln, mi ln bng 10 ml CHCl3. Cui cng ra tng nc bng 5 ml CCl4. Nu hm lng Zn gp 50 ln Cd th vic chit Cd khng hon ton v phm sai s m. Cc cht oxi ho cn c phn hu bng cch thm H2O2 vo v un si k. Cc cht hu c cn c chit tch bng 5 ml CCl 4 mi ln chit. I.2.2.2 Phng php chun Complexon Cd trong mi quan h vi EDTA v vi tt c cc cht ch th c dng nghin cu cho ti nay k c s c mt ca km th php xc nh complexon nguyn t ny khng gp kh khn g c lng ln v vi lng Cd trong mu phn tch. Trong s ln cc cht ch th c ngh xc nh Cd c th chn nhng cht sau: Pyrocactesin tm, Naphtolic, metyltimol xanh, galleon v glyxintymol xanh. Nhng cht ch th ny c s dng trong dung dch c pH= 10. Trong mi trng axit yu c pH=56 c th s dng PAN hoc CuY hoc CuYPAN, azoxin. Php chun Cd km la chn nhng c th nng la chn n mc nht nh nu s dng nhng phng php c th, php tch s b cng c s dng, v d chit phc tioxyanat. Nhng phng php s dng cc cht che hoc cc mu tng phn c ng dng xc nh hn hp nhiu cu t. Trong trng hp ny ngi ta s dng kh nng che Cd bng KCN v gii che n bng foocmanhit. Phng php cho php xc nh Cd khi

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c mt Pb, cc kim loi kim th v cc kim loi khc, trc ht l s c mt ng k ca st. trnh phn ng vi EDTA c th che Cd bng kaliItdat ( nng cao) l nhng cht che khng cn tr cho vic xc nh km. C th xc nh hm lng c mt cadimi v km theo mt ng chun o mu, nu php chun c tin hnh khi c mt ca murxit hoc xincon. Ngi ta thm cht mu d so vi km. Phc km vi cht mu l ch th cho cadimi theo lch ca ng chun, theo hai im gy trn ng chun c th tnh nh lng complexon tiu tn tng ng cho php chun Cd v Zn. I.2.2.3 Phng php AAS Vi phng php AAS s dng l nhit in, nguyn tc ca phng php l: Mu c a vo l, ti y n c sy kh, tip n l tro ho v cui cng mui ca cadimi c phn ly di dng cadimi nguyn t. S dng thuc th l APDC (amoni pyrolidin thiocacbonat) pH=9, mu c axit ho bng axit HNO3 (axit ho bng 100ml mu bng 1ml axit HNO3). Sau tim vo l 10g mu, loi dung mi 100oC trong 25 giy, tro ho 450oC trong 80 giy v nguyn t ho 1950oC trong 4 giy. o hp th ti bc sng = 228,8 nm. Da vo ng chun tnh kt qu. Trong trng hp ny hm lng Cadimi qu nh c th nng cao nng bng cch chit MIBK (metyl isobutyl ketone) vi thuc th APDC. Vi phng php F-AAS s dng ngn la l hn hp khng khaxetylen vi t l 5,2/1,2 L/ph (V/V), cng dngthuc th APDC chit mu, mu cng c axit ho bng axit HNO 3, thm vo dung dch axetat 40% pH= 34, thm 5ml thuc th APDC, yn trong 2 pht . Thm 10ml MIBK vo bnh lc mnh trong 30 giy, thm nc ct vo cho n khi dung mi hu c ln n vch ca bnh nh mc. Sau a mu vo ngn la ca my v phn tch mu. o hp th bc sng = 228,8 nm. V

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da vo ng chun tnh kt qu (mu chun c chun b trong MIBK). I.2.2.4 Phng php cc ph Nu trong mu phn tch m hm lng Cd cao khong trn 1 mg/l th c th dng phng php cc ph xc nh. V Cd trong nn hn hp m ammoniac v nhiu nn khc cho cc sng cc ph thun nghch v nh lng. xc nh Cd bng phng php cc ph, ngi ta thng dng nn m ammoniac-amoniclorua (NH3 1M + NH4Cl 1M ). Nu trong mu phn tch hm lng Cu khng ln hn hm lng Cd c th xc nh ng thi c 2 nguyn t v nn dng phng php thm chun. Trong trng hp hm lng Cu qu ln so vi hm lng Cd th cn che Cu bng xianua. Cc kim loi khc nh Fe (III), Bi, Sn, Sb, s kt ta di dng hydroxit trong dung dch m. xc nh Cd ta ly phn dung dch trong trn. Nu hm lng kt ta qu ln cn xc nh theo phng php thm. Zn, Co, Ni, Mn l nhng kim loi trong nn ny cho sng cc ph nhng th m hn sng ca Cd nn khng nh hng n vic xc nh n. Nu trong nc c lng ln Pb th cn tch trc bng cch kt ta n bng axit Sunfuric long v lc b kt ta Ch sunfat. Tu theo hm lng ca Cd trong mu m chng ta thc hin pha long hay c cn bt sao cho trong 25 ml mu cha t 0,051,25 mg Cd. Thm mt git Metyl da cam v trung ho bng HCl hoc NH3 n khi cht ch th va i mu. Tip theo thm 10 ml dung dch nn, 1 ml gielatin, 1 ml m Natri sunfit v nh mc bng nc ct, lc u dung dch, cho dung dch vo bnh in phn v ghi cc ph t -0,4 V -0,8 V so vi anot y thu ngn. C th nh lng bng phng php thm chun hoc phng php ng chun.

18

Nu mu cha 0,02 0,5 mg Cd/l th cn lm giu bng cch c nh sau: Ly 250 ml mu, cho vo bt s hoc cc chu nhit, thm vo 1ml HCl c, lm bay hi n cn kh. Thm vo phn b kh 5 ml dung dch c iu ch nh sau: Trn 10 ml dung dch nn + 1 ml gielatin + 1 ml Natrisunfit + 38 ml nc ct 2 ln. Cho ton b vo bnh in phn v ghi cc ph t - 0,4 V -0,8 V. Nn xc nh bng phng php thm chun. Ngy nay vi k thut tin tin nhiu phng php cc ph hin i c th xc nh Cd c nng 10-9 M trong cc nn khc nhau. c bit c th xc nh c ng thi ti 5 nguyn t cho chnh xc cao ( v d: Zn, Cd, Pb, Cu, Bi). Bng phng php Vn-Ampe ho tan hp ph (AdSV) s dng thuc th 5-hydroxy quinolin (8-HQ) trong nn m HEPES (pH= 7,8) Cd cho pic ti -0,69 V vi gii hn pht hin ti 1.10-10 M bng phng php Vn-Ampe ho tan anot (ASV), Cd trong nn m axetat pH= 4,6 V cho pic ti -0,59 V vi gii hn pht hin ti 1.10-10M. I.3 Nguyn t Km (Zn) v cc phng php xc nh I.3.1 Gii thiu v nguyn t Km (Zn) Km l tn gi ca mt nguyn t ha hc trong trong bng h thng tun hon c k hiu Zn v s hiu nguyn t bng 30. c im ca nguyn t Zn Khi lng nguyn t 65,37 Cu hnh electron [Ar]3d104s2 Bn knh nguyn t (Ao) 1,39 Th in Nng lng ion ho ( eV) cc tiu chun (V) Zn2+/Zn

I1 I2 I3 O,763 9,39 17,96 39,70 Km l mt kim loi mu trng xanh nht, nhit thng nhng khi

nu n 100 150oC n tr nn mm, do, d dt mng, d ko di.Trong khng kh n b ph bi mt lp oxit nn mt tnh nh kim. Km c khi

19

lng ring l 7,13 (g/cm3), nhit nng chy 419oC, nhit si 907oC. Km l mt kim loi hot ng trung bnh c th kt hp vi xy v cc kim khc, c phn ng vi axt long gii phng hidr.Trng thi xi ha ph bin ca km l +2. Km l nguyn t ph bin th 23 trong v Tri t.Cc loi khong cht nng nht c xu hng cha khong 10% st v 40-50% km. Cc loi khong cht tch km ch yu l sphalerit, blen, smthonit, calamine, franklinite. Km trong t nhin l hn hp ca 4 ng v n nh Zn 64, Zn66, Zn67, and Zn68 vi ng v 64 l ph bin nht (48,6% trong t nhin). 22 ng v phng x c vit n vi ph bin hay n nh nht l Zn 65 vi chu k bn r 244,26 ngy, v Zn72 vi chu k bn r 46,5 gi. Cc ng v phng x khc c chu k bn r nh hn 14 gi v phn ln c chu k bn r nh hn 1 giy. Nguyn t ny cng c 4 trng thi ng phn nguyn t. Km l kim loi c s dng ph bin hng th t sau st, nhm, ng tnh theo lng sn xut hng nm. +Km c s dng m kim loi, chng hn nh thp chng n r. +Km c s dng trong cc hp kim nh ng thanh, niken trng, cc loi que hn, bc c v.v. ng thanh c ng dng rng ri nh cng v sc khng r cao. +Km c s dng trong dp khun, c bit l trong cng nghip t. Km dng cun c s dng lm v pin. +xit km c s dng nh cht liu c mu trng trong mu nc v sn cng nh cht hot ha trongcng nghip t. S dng trong thuc m, n c kh nng chng chy nng cho cc khu vc da trn. S dng nh lp bt mng trong cc khu vc m t ca c th (b phn sinh dc) ca tr em chng hm.

20

+Clorua km c s dng lm cht kh mi v bo qun g. Sunfua km c s dng lm cht ln quang, c s dng ph ln kim ng h hay cc vt khc cn pht sng trong bng ti. +Methyl km (Zn(CH3)2) c s dng trong mt s phn ng tng hp cht hu c. +Stearat km c s dng lm cht n trong sn xut cht do (plastic) t du m. +Cc loi nc thm sn xut t calamin, l hn hp ca(hydroxycacbonat km v silicat, c s dng chng bng da. +Trong thc n hng ngy, km c trong thnh phn ca cc loi khong cht v vitamin. Ngi ta cho rng km c thuc tnh chng xi ha, do vy n c s dng nh l nguyn t vi lng chng s cht yu ca da v c trong c th (lo ha). Trong cc bit dc cha mt lng ln km, ngi ta cho rng n c tc dng lm nhanh lnh vt thng. + Gluconat glycin km trong cc vin nang hnh thoi c tc dng chng cm. I.3.2 Cc phng php xc nh Km (Zn) I.3.2.1 Phng php trc quang Phng php trc quang l phng php n gin nhanh v nhy, c dng ph bin xc nh cc kim loi. Km to c nhiu phc vng cng vi cc thuc th hu c c kh nng t phc mu vi ion Zn2+ c s dng trong phng php trc quang nh sau: Km to phc vi 2-(5-nitro-2-piridylazo)-5-(N-propyl-N-sunfupropilamino) phenol (nitro-PADS) pH = 8 9, c bc sng hp th cc i max = 565nm. Phng php ny c th s dng xc nh Km khi c mt ng thi ion Fe2+ v Cu2+. Do cc ion Zn2+, Fe2+ v Cu2+ c kh nng to phc vi Nitro-PADS cc pH cng nh cc bc sng khc nhau. Fe(II) to phc pH = 3,4 9, max= 582nm, Cu (II)

21

to phc 1:1 pH = 2,5 4,5 v mt phc 1:2 ng thi 3 kim loi trong khong nng 0,02 0,5mg/ml mt cch ring r, c th p dng phng php xc nh cc kim loi ni trn trong huyt thanh. Ngoi ra c th s dng thuc th hu c 1-(2thiazolylazo)-2-naphtol (TAN) to phc mu vi Zn2+, Fe2+ v Ni2+ pH = 6,4. Zn2+ to phc vi 2-(5-bromo-2-pyridylazo)-5-ietylaminophenol (5-BrPADAP) Phc Zn2+-(5 Br-PADAP) c ho tan bi ru etylic, phc c bc sng hp th cc i max = 555nm, h s hp th phn t gam l 1,09.105l.mol-1.cm-1. Khong tun theo nh lut Bia 0,1 0,5mg Zn2+/5ml.Phng php ny c th p dng xc nh trong nc v trong thc n. Mt khc c th s dng phng php trc quang xc nh Zn 2+, phc to thnh Zn2+-(5-Br-PADAP) pH= 9,5 (duy tr bi m borax) c ho tan trong ru etylic ri c chit bi naphtalen. Bc sng hp th cc i max= 555 nm, h s hp th phn t gam l 1,23.105l.mol.cm-1 .Khong tun theo nh lut Bia 0 5,0 mg Zn2+/ml. C th s dng Natrixitrat, thioue,calgon v iaxetylioxim lm cht che. Zn2+ to phc vi 5-(2-cacbometoxyphenyl) azo-8-quinolino. Trong mi trng mixen ion ca Natri dodexylsunfat pH = 4,0 4,8, phc s c mu da cam, bn trong khong 4 gi. Bc sng hp th cc i = 488 nm, h s hp th phn t gam l 4,14.104l.mol.cm-1. Khong tun theo nh lut Bia : 0 0,42 mg Zn2+/ml v nhy Sandnll l 1,75 ng/cm2. Zn2+ to phc vi axit 7-(4-nitrophenylazo)-8-hydroxyquinolin-5sunfonic (P-N-AZOXS). Km to phc nhanh vi (P-N-AZOXS) pH = 9,2 (duy tr bi m Borax), phc bn trong khong 24 gi h s hp th phn t gam l 3,75.104 l.mol-1. Khong tun theo nh lut Bia : 0,05 1,0mg Zn2+/ml. Phng php

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c p dng nh lng Zn trong dc phm, trong hp kim ng. lch chun R.S.D < 2% v ng tt. Trong phng php trc quang hiu chnh, c th s dng axit Crom xanh K(ACBK).Zn2+ to phc vng cng vi ACBK dng Zn(ACBK) 2 max = 530 nm, h s hp th phn t gam l 4,37.104l.mol-1.cm-1. Dng thuc th Phenylflorua (PF) khi c mt triton X-100 v xetylpiridin clorua (CP). Bc sng hp th cc i max = 573 nm, h s hp th phn t gam l 1,09.105 l.mol-1.cm-1. Khong tun theo nh lut Bia: 0,04 0,4 mg/ml. C th s dng phng php ny xc nh Zn2+ trong insulin. Km to phc c vi 2,3,7-trihydroxyl-9-ibromo hydroxyl phenyl florua (DBH-PF) khi c mt CPB v trixon X-100. Phc ny c mu ta pH = 11,4, s dng dung dch m Na2HPO4-/ NaOH. Bc sng hp th cc i 610 nm, h s hp th phn t gam l 1,78.105 l.mol-1.cm-1. Khong tun theo nh lut Bia: 0 326 mg Zn2+/l. tng nhy v chn lc ca phng php c th thm Natri metaphotphat. Phng php ny c ng dng xc nh Zn2+ trong qung pirit. chnh xc t 0,02 0,4%. S dng thuc th N- hydroxyl- N, N-iphenylbenzamidin (HDPBA) v iphenylcacbazon (DPCZO) xc nh Zn2+ trong khng kh. Chit phc Zn2+ vi HDPBA trong CHCl 3 pH = 8,2 10,3 vi s c mt ca DPCZO v NH4SO4. C s chuyn mu t hng sang vng, bc sng hp th cc i max = 525 nm, h s hp th phn t gam l 1,27.10 5l.mol-1.cm-1. Khong tun theo nh lut Bia: 00,8 mg/ml trong pha hu c. nh lng Zn ngi ta cn s dng phng php chun trc quang. y l phng php tng i ph bin trong vic nh lng km. S dng chun trc quang xc nh Zn2+ thng dng EDTA vi ch th XO. Phc gia Zn2+-XO c duy tr pH = 5,4 5,9 bi dung dch m axetat, khong tuyn tnh l 50 160 g/l, lch chun tng i

23

0,31%.Phng php c p dng xc nh Zn (II) trong dung dch km tinh ch vi thu hi 99,0 101,4%, sai s 0,76%. xc nh Zn (II) trong ng thau, ngi ta ho tan mu trong axit HNO3, sau oxi ho bi KClO3, chun bng EDTA vi ch th XO v xanhbromocrezol pH = 5,5. S dng KF, thioure, BaCl 2 lm cht che, th t cho cc cht che: KF ri sau l thioure v dung dch oxi ho c un si t nht trong 2 pht kt ta hon ton MnO2. Sai s tng i l 0,12 1,0%. Ngoi ra c th s dng 2,2-bipyridin nh mt thuc th che chn lc gin tip xc nh Zn. Zn (II) trong dung dch mu ban u c to phc vi lng d EDTA, lng EDTA d c chun bi Pb(NO3)2 pH = 5,0 6,0 dng XO lm ch th. Lng d 2,2- bipyridin oc thm vo, lc k hn hp, EDTA trong phc b y ra c chun vi dung dch Pb(NO3)2. I.3.2.2 Phng php cc ph xc nh km bng phng php cc ph, ngi ta dng nn NH3 1M + NH4Cl 1M . Trong nn ny th na sng ca km ng vi s trao i 2 electron l -1,35 V so vi cc Calomen bo ho. Phng php cc ph cho kh nng xc nh c km vi hm lng nh nht l 0,01 mg/l. Sai s ln nht khong 5 %. Nu trong mu nc cn cha ng thi ng, Cadimi v Niken vi hm lng xp x hm lng Km th dng nn ny ta c th xc nh c cc nguyn t , v sng ca chng trong trng hp ny hon ton tch khi nhau. Nu ghi cc ph t -0,2 V th cc sng thu c trn cc ph ln lt l Cu, Cd, Ni, Zn. Oxi ho tan trong dung dch c kh bng Natrisunfit. Nu cc nguyn t ng, Cadimi, Niken v Coban c trong nc vi hm lng ln hn hm lng ca Km nhiu th chng s cn tr vic xc nh Km v sng cc ph ca chng th dng hn sng Km. Nu trong my cc ph c b phn

24

chnh dng khuch tn ta s dng n b chnh dng cc ph ca cc kim loi cn tr . Khi hm lng ca chng khng qu cao th c th b chnh c v thu c sng ca Km khi ghi cc ph t -0,8 V. Nu vic b chnh khng thc hin c, th cn tch Km ra khi mu bng phng php chit, gii chit Km li tng nc v xc nh n bng phng php cc ph. Trong trng hp khng cn phi tch Km th nn xc nh n bng phng php thm. Sau khi ghi cc ph dung dch cn phn tch, thm lng nh dung dch chun c nng thch hp vo dung dch phn tch v ghi cc ph ln na. lng Km c thm vo nh th no sng th hai c chiu cao gp ri hoc gp i ca chiu cao sng th nht. Cch tin hnh nh sau: Trong bnh nh mc dung tch 50 ml, thm vo 25ml mu nc hm lng ca km trong l 1 25 mg. Nu trong mu c hm lng Km nh hn 0,15mg/l, th ly 250ml nc thm vo 1 ml HCl c v lm bay hi n cn kh hai ln nh nhau v ho tan b kh trong 25ml nc ct. Sau thm tip vo 5ml dung dch nn, 1ml gielatin, 1ml Na 2SO3 v nh mc bng nc ct, lc u dung dch trong bnh, chuyn 25ml dung dch vo bnh in phn v ghi cc ph t -0,8 V n -1,5 V, nhy ca my sao cho sng thu c c chiu cao t nht 20 mm. Thm vo bnh in phn 0,2ml dung dch chun (loi no tu thuc vo nng Km trong dung dch mu) v ghi cc ph dung dch ny nhy c. Chn nng dung dch chun thm vo sao cho sng th hai c chiu cao gp ri hoc gp hai ln sng th nht. Nu trong nc c ng, Cadimi, Niken vi hm lng hm lng cho php xc nh cng vi Km, th cng tin hnh nh trn v ghi cc ph t -0,2V n -1,5V. vic xc nh cng c tin hnh theo phng php thm chun. Nu hm lng ca cc nguyn t ngn cn qu ln th cn tch Km trc nh sau: ly mt th tch nc sao cho hm lng km trong t 0,01-

25

0,5mg trong 50ml. Ly 50ml thm vo 2 git metyl v trung ho cn thn bng HCl long hoc bng NH3 long cho n khi cht ch th va i mu. Thm tip vo 20ml dung dch che. Chit km mt vi ln, mi ln bng 20ml dithizon, chit n khi ln chit cui mu xanh ca dithizon khng thay i. Gp tt c cc phn chit khc, thm vo 25ml HCl 1:5 v lc phu gii chit km tr li tng nc. Gi tng nc v lp li s gii chit hai ln na, mi ln 25ml HCl. Gp ton b dung dch nc thu c, lm bay hi trn bp cch thu n cn kh v ho tan b kh trong nc ct. Tin hnh xc nh km nh trn. I.3.2.3 Phng php AAS Phng php AAS da trn nguyn tc tt c cc nguyn t khi trng thi nguyn t u c hp th bi mt bc sng nht nh, cng hp th th hin nng ca cc nguyn t c trong mu. Nu ta chiu mt chm tia sng c bc sng xc nh vo m hi nguyn t th cc nguyn t t do s hp th cc bc x c bc song ng ng vi nhng tia bc x m n c th pht ra c trong qu trnh pht x. Ph sinh ra trong qu trnh ny gi l ph hp th nguyn t. Phng php quang ph hp th nguyn t ha hi c p dng vi mt s nguyn t c kh nng nguyn t ha nh: Hg, As, Se, Zn Phung php AAS l phng php hin i c chnh xc cao, c th xc nh lng vt cc kim loi trong cc hp cht v c v hu c vi cc i tng nghin cu khc nhau. Vi php o AAS c nhy v chn lc cao. Gn 60 nguyn t ha hc c th xc nh bng phng php ny vi nhy 10-4 10-5%. I.4 Nguyn t ng (Cu) v cc phng php xc nh I.4.1 Gii thiu v nguyn t ng (Cu) ng l nguyn t ha hc trong bng h thng tun hon c k hiu Cu v s nguyn t bng 29, thuc nhm IB.

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Cc hng s vt l ca ng S th t Khi lng nguyn t Cu hnh electron Bn knh nguyn t (Ao) m in Khi lng ring (g/cm3) Nng lng ion ho (eV) 29 63,56 [Ar] 3d104s1 1,28 1,9 8,94 I1 II2 7,72 20,29

III3 36,20

ng l mt kim loi c mu vng nh , c dn in v dn nhit cao (trong s cc kim loi nguyn cht nhit phng ch c bc c dn in cao hn),l kim loi mm, d dt mng, d ko si. ng c l l kim loi c con ngi s dng sm nht do cc ng c nin i khong nm 8700 trc cng nguyn (TCN) c tm thy. Ngoi vic tm thy ng trong cc loi qung khc nhau, ngi ta cn tm thy ng dng kim loi (ng t nhin) mt ni. ng c ghi chp trong cc t liu ca mt s nn vn minh c i, v n c lch s s dng t nht l 10.000 nm. Trong thi ca nn vn minh Hy Lp, kim loi ny c bit vi tn gi chalkos. Trong thi k La M, n c bit vi tn aes Cyprium (aes l thut ng Latinh chung ch cc hp kim ca ng nh ng v cc kim loi khc, v bi v n c khai thc nhiu Sp). T nhng yu t lch s ny, tn gi ca n c n gin ha thnh Cuprum l tn gi Latinh ca ng. Trong Thn thoi Hy lp- La m cng nh trong thut gi kim, ng c lin quan n n thn Aphrodite (V N) v v p rc r ca n, vic s dng thi c i ca n trong sn xut gng, v s lin h ca n vi Sp, l qu hng ca n thn. Trong thut gi kim, k hiu ca ng cng l k hiu cho sao kim Trong t nhin ng c th tm thy nh l ng t nhin hoc trong dng khong cht. Cc khong cht chng hn nh cacbonat azurite

27

(2CuCO3Cu(OH)2) v malachite (CuCO3Cu(OH)2) l cc ngun sn xut ng, cng nh l ct sunfua nh chalcopyrite (CuFeS2), bornit (Cu5FeS4), covellit (CuS), chalcocit (Cu2S) v cc xt nh cuprit (Cu2O). Phn ln ng trch xut c trong cc m l thin trong cc khong sn c t hn 1% ng. C hai ng v n nh l Cu63 v Cu65, cng vi mt s ng v phng x. Phn ch yu ca cc ng v phng x c chu k bn r mc pht hay nh hn, ng v phng x bn nht, Cu64, c chu k bn r 12,7 gi, c hai cch phn r, to ra hai sn phm khc nhau. ng l vt liu d dt mng, d un, c kh nng dn in v dn nhit tt, v vy n c s dng mt cch rng ri trong sn xut cc sn phm:

Dy in. Que hn ng. Tay nm v cc vt khc trong xy dng nh ca. c tng: B dn sng cho cc bc x vi ba. Vic s dng ng trong cc mch IC tr nn ph bin hn thay th cho nhm v dn in cao ca n. L mt thnh phn trong tin kim loi. Trong nh bp, chng hn nh cho rn. Phn ln cc dng bng niken trng dng bn n (dao, na, tha) c cha mt lng ng nht nh. L thnh phn ca gm kim loi v thy tinh mu. . Cc hp cht ca ng u c.

I.4.2 Cc phng php xc nh ng (Cu) I.4.2.1 Phng php trc quang s dng thuc th DDC

28

Ion Cu (II) to c phc vng cng vi DDC (ietyl dithiocacbamat), phc c mu nu, kh tan trong nc nhng tan nhiu trong mt s dung mi hu c nh clorofom. Trong dung mi ny phc c mu nu nh vng. Do nh lng ng bng thuc th ny ngi ta thng tin hnh chit trc quang. tng tnh chn lc ca phng php thng chit phc bng clorofom t mi trng cha ammoniac, amoni xitrat v complexon III l nhng cht dng che cc ion cn tr vic xc nh ng. Nu ng tn ti trong nc di dng phc bn xianua th trc khi phn tch cn phi ph hu phc bng cch lm bay hi mu nc sau khi thm vo 0,5 ml H2SO4 c v 5ml HNO3 c. Sau khi lm bay hi mu n kh, thm vo b 1 ml HCl c v lm bay hi ln na.Tip theo thm nc ct hai ln vo, lc v gi ly phn nc lc phn tch. Trong mi trng c cha ammoniac, xitrat, v complexon III a s cc kim loi khc khng gy cn tr cho php xc nh Cu bng phng php ny, ch c Bimut (Bi), bc (Ag), Hg vn phn ng vi DDC v c th b chit cng vi phc ca Cu. Tuy vy ch c phc ca Bi c mu vng l c nh hng cn phc ca Hg v Ag khng mu hp th nh sng trong min t ngoi, nn thc t khng nh hng n vic xc nh ng. xc nh Cu di dng phc CuDDC c th dng NaDDC lm thuc th hoc c th dng phc PbDDC v c th tin hnh chit trao i xc nh Cu. Phc ng bn hn phc ch nn y ch ra khi phc ca n v Cu c chit hon ton t tng nc sang tng hu c.

I.4.2.2 Phng php cc ph Cu (II) c hot tnh cc ph, trong nhiu nn khc nhau cho sng cc ph nh lng. Trong a s cc nn cc ph, sng ca ng nm trong khong th kh dng so vi kim loi khc, t 0 0,6 V. V vy xc nh Cu bng

29

phng php ny rt thun li v kh chn lc. Nn hn hp m ammoniac l mt trong nhng nn tt xc nh Cu. Trong nn ny cc ion kim loi b kh th m hn nh Cd(II), Co(II), Ni(II), Zn(II), Mn(II)khng gy nh hng n vic xc nh Cu. Oxi ho tan trong nc c kh bng cch thm vo lng d Natri sunfit Na2SO3. Cromat, Co(III), Tl(III) cng cho sng cc ph trong khong th c sng ng nn gy cn tr nu hm lng ca chng ng k. Nu trong nc c hm lng ln Fe(III), Al(III), Bi, Mn l nhng kim loi kt ta hidroxit trong mi trng ammoniac, th kt ta c th hp ph mt phn ng, trong trng hp ny trnh sai s nn tin hnh nh lng ng bng phng php thm chun, khng nn dng phng php ng chun. Nu trong nc c cha lng ng k l cht hu c th cn phi v c ho mu nh sau: thm vo th tch nc ly phn tch 1 2 ml axit H 2SO4 c, 3 5 ml HNO3 c v lm bay hi dung dch trong t ht cho n khi xut hin khi trng SO3. Nu dung dch thu c cn c mu th thm 5ml HNO3 c v lm bay hi ln na, ng tc ny c lp li cho n khi thu c dung dch khng mu. Sau lm bay hi dung dch n cn kh. Phn b sau khi ngui c ho tan trong nc ct hai ln, un nng ho tan ht cc mui tan, lc qua phu kh bng thu tinh xp v gi ly xc nh ng. loi tr cc i cc ph dng dung dch gielatin. Nu mu cha t 2 50 mg Cu/l, th ly 25 ml dung dch mu cho vo bnh nh mc dung tch 50 ml. nu mu nc ch cha khong 0,2 3 ml Cu/l th ly 250 ml cho vo cc chu nhit sch, thm vo 1 ml HCl c v lm bay hi trn ni cch thu. Sau khi ngui tm t bng 1 ml HCl c, ho tan mui bng nc ct v chuyn ton b dung dch vo bnh nh mc 50 ml. Trung ho mu bng NH3 n khi i mu metyl da cam, thm vo 10 ml dung dch nn, 1 ml gielatin, 1ml Na2SO3 nh mc bng nc ct hai ln v lc u. trng bnh in phn bng vi ml dung dch , mt phn dung

30

dch trong bnh nh mc vo bnh in phn. Ghi cc ph t -0,2Vn -0,8 V nhy thch hp. Sau da vo ng chun xc nh hm lng ng. Nu mu c hm lng Cu trong khong 0,02 5ml Cu/ lit nc th ly 250 ml mu nc thm vo 1 ml axit HCl c, lm bay hi n kh, sau ngui thm vo 5ml HCl c na v li lm bay hi ln na n kh. Sau khi ngui thm vo 5 ml dung dch c ch nh sau: 10 ml dung dch nn c trn u vi 1 ml gielatin + 1 ml Na 2SO3 + 38 ml nc ct, dng a thu tinh nh khuy u cho mui trong cc tan ht. Chuyn ton b dung dch vo bnh in phn kh cha thu ngn kh v sch dng lm anot y. Ghi cc ph t -0,2 V n 0,8 V. Ri da vo ng chun tnh hm lng ca ng. Hin nay c nhiu phng php cc ph hin i c th xc nh Cu c nng 10-9 M v c th xc nh trong nhiu nn khc nhau. Bng phng php Vn-Ampe ho tan hp ph, s dng thuc th catechol (pH = 7,8) Cu cho pc ti -0,2 V vi gii hn pht hin ti 1.10-11 M. Vi thuc th 6-hydroxi quinolin (pH = 6 9) Cu cho pc ti -0,45 V vi gii hn pht hin l 2,4.10-10 M. Bng phng php Vn-Ampe ho tan trong nn m axetat (pH = 4,6) Cu cho pc ti -0,0038V vi gii hn pht hin l 1.10-10 M. I.4.2.3 Phng php Neocuproine Ion Cu (II) trong dung dch trung tnh hoc axit yu phn ng vi hp cht 2,9-dimetyl 1,1,10-phenanthroline (Neocuproine) to thnh phc cht trong 2 mol Neocuproine lin kt vi 1 mol Cu+. C th dng cc loi dung mi hu c khc nhau chit phc ny bao gm c hn hp clorofom + methanol cho dung dch mu vng, cho quang ph hp th phn t ti bc sng = 457nm. Phn ng ny rt c trng cho Cu. Mu vng ca phn ng tun theo nh lut Bia cho ti nng ca Cu l 0,2 mg/ 25ml dung mi.

31

Mu n nh trong dung dch nc c pH = 2 9, mu n nh trong CHCl 3CH3OH trong nhiu ngy. Mu c cho phn ng vi Hydroxylamin-Hydrocloric kh ion Cu2+ thnh ion Cu+. Dng xitrat natri to phc vi ion nhm trnh kt ta khi tng pH. iu chnh pH =4 6 bng NH4OH, thm dung dch Neocuproine trong methanol to phc vi ng v sau c chit bng clorofom. Sau khi pha long CHCl3 bng CH3OH ti mt th tch chnh xc. Mt quang ca dung dch c o ti bc sng = 457 nm. Mt lng ln Cr v Sn c th nh hng n php o. trnh nh hng ca Cr th thm axit sunfur kh Cr(IV) thnh Cr(III). Thm 20 ml Hydroxylamin-Hydrocloric khi c nhiu thic hoc mt lng ln cc cht oxy ho c trong dung dch. Xianua, sunfit v cc cht hu c c th loi tr trong qu trnh phn hu mu. I.4.2.4 Phng php AAS Vi phng php F-AAS th s dng ngn la l hn hp khng khaxetilen vi t l 5,2/1,2 L/ph (V/V), o Cu bc sng = 324,76 nm. Vi phng php AAS khng dng ngn la, th mu c sy 120 oC 200OC trong thi gian l 30 giy, tro ho nhit 450 oC 600oC trong thi gian l 20 giy, nguyn t ho nhit 2400 oC trong thi gian l 3 giy. Xc nh ng trong cc hp cht trn nn ca Fe ngi ta dng vic chit dng xalixialdocximat ng pH = 3, y ngi ta che Fe bng xitrat. S phun bi dch chit trong ngn la axetylen- oxi, xc nh bc sng = 324,7 nm v cho php xc nh n 0,5 g/ml Cu, cng pht x ca ng trong dung dch chit so vi s pht x trong dung dch nc tng ln 10 ln. lm dung mi ngi ta dng clorofom, hay amiaxetat. Xalixialdocximat ng ho tan tt trong clorofom nhng amiaxetat mc cao hn clorofom cho kh nng tng pht x quang ph. ng cng c chit di dng 8-

32

oxiquinolat ng vi dung mi l MIBK pH ca dung dch chit l 3 5, = 324,8 nm c nhy tng 6 8 ln so vi trc quang trong dung dch nc, dng ngn la Hidro-Oxi. I.5 Phng php cc ph I.5.1 C s ca phng php Phng php cc ph l nhm cc phng php phn tch da vo vic nghin cu ng cong Vn-Ampe hay cn gi l ng cong phn cc, l ng cong biu din s ph thuc cng dng in vo in th khi tin hnh in phn dung dch phn tch vi in cc git thu ngn.ng biu din cng dng ti thi im s kh ion cn phn tch b gy t ngt pha trn, to nn ng gi l sng cc ph.Da vo v tr sng c th xc nh thnh phn nh tnh ca cht in ly, da vo chiu cao ca sng c th xc nh hm lng ca ion b kh.Phng php ny thch hp cho vic phn tch nhiu ion kim loi nh Cd, Co, Cu, Mn, Ni, Sn, Zn, Fe, Bi, U,V v nhiu kim loi khc trong cc i tng : t, , qung,kim loai, hp kim y l phng php c chnh xc, chn lc, nhy v tin cy cao.Khi cc hp cht c in th na sng khc nhau ln ( thng th khi E1/2 100 mV) ta c th xc nh ng thi nhiu hp cht trong cng mt dung dch m khng cn tch chng ra khi nhau. Phng php ny c Heyrovsky pht minh vo nm 1920 v cho n nay cng vi s pht trin ca khoa hc k thut, phng php ny ngy cng c ci tin. C s ca phng php ny l da trn phn ng in ho ca cc cht in ho trong dung dch in li trn in cc git thu ngn treo theo phn ng : Ox + ne Kh Trong : Ox : Dng oxi ho Kh : Dng kh

33

n : S e trao i. Phng trnh nh lng l phng trnh Incovic : Id = 605 . n . D1/2 . m2/3 . t1/6 . C Id : Cng dng cc i gii hn ( A ) n : S electron tham gia vo phn ng in cc D : H s khuch tn ( Cm2/s ) m : Tc chy git Hg (mg/s) t : Chu k git ca in cc git (s ) C : Nng cht phn tch. ( mM ) Tuy nhin do nh hng ca dng t in nn nhy ca phn ng ch t c 10-4 10-5 M. Nhng cng vi s pht trin ca khoa hc v k thut c nhiu ci tin c p dng vi mc ch tng nhy ca phn ng. y chng ti gii thiu hai hng chnh : + Hng th nht : Tn dng cc thnh tu ca khoa hc k thut in t loi tr dng t in nng cao t s n hiu o/tn hiu nhiu ( nh : Phng php cc ph sng vung, cc ph xoay chiu chn pha, cc ph bin i u, cc ph xung vi phn,) + Hng th 2 : lm giu cht phn tch ln b mt in cc bng phn ng kh hay oxi ho kt ta cht , sau ho tan sn phm kt ta v ghi tn hiu ho tan ( phng php Vn ampe ho tan ). I.5.2 C s ca phng php cc ph : Phng php cc ph ng dng dng khuch tn, mt s trng hp s dng thm i lu, cn qu trnh in chuyn th phi bng mi cch trit tiu n. Trong mi trng hp hu ht ngi ta phi trit tiu c dng in di v i lu sao cho cht i ti in cc ch theo hin tng khuch tn v dng sinh ra l dng khuch tn. lm c iu ny ngi ta phi cho vo dung dch in phn mt dung dch nn c nng gp c 10 100 ln hoc 1000 ln so vi cht phn tch.

34

- Qu trnh xy ra trn in cc git catot thu ngn : in cc so snh c s dng c din tch ln, in cc ch th thu ngn c din tch b. Qa trnh xy ra in cc ch th ch yu trn thu ngn. Nu trong dung dch khng c qu trnh no ph th th v dng c mi quan h : I = E/R Phn ng trn in cc xy ra : Mn+ + ne + Hg M(Hg) Th in cc catot c xc nh :

RT EK = E + nF
o

CMn+ . aHg . fMn+ ln CM(Hg) . fM(Hg)

Trong dng khuch tn ph thuc vo : Nng kim loi trong dung dch, nng ion kim loi nhn electron ti catot. I = KM ( CoM - CM ) CoM : Nng ion kim loi su trong lng dung dch. CM : Nng ion kim loi st b mt in cc v nhn electron ti in cc. n lc CM = 0 ( ion gn in cc ht vcatot < v p. dng gii hn : Id = KM . CoMn+ Dng in ny c gi l dng khuch tn : I = Id V : CMn+ = ( Id I )/ KM ( KM l h s t l ) Tng t, nng kim loi trong hn hng cng t l vi cng dng : - KM.CMn+
in cc

) th sinh ra

35

CM(Hg) = Lc th in cc :

I . K = I . 1/K

RT E =E + nF
Trong :
o

( Id - I ) . aHg . fMn+ .Ka ln KM .I . fM(Hg)

fMn+, Ka, KM, fM(Hg), aHg l hng s.

Lc E ph thuc I, Id. S ph thuc E I l phng trnh sng cc ph. - Cc phng php cc ph xung : Nhm ny gm 3 phng php sau : + Phng php cc ph sng vung ( SWP ) + Phng php cc ph xung thng ( NPP ) + Phng php cc ph xung vi phn ( DPP ) Nguyn l chung ca nhm phng php ny l : in cc lm vic c phn cc bng dng mt chiu c in p khng i hoc bin i u c cng thm vo nhng thi im xc nh nhng xung in p gin on c bin v rng xc nh vung gc, bng cch ny sut thi gian t xung dng faraday IF tng theo t-1/2, dng t in s tng theo e-kt. Kt qu l trong php o v pha kt thc thi gian t xung hu nh ch o c dng faraday, ti thi gian ny dng t in ( ic ) hu nh trit tiu hon ton :
Ea . e-t/R.CD R

ic =

Trong :

36

- Ea : Bin xung - R : in tr - ic : Dng t in - t : Thi gian sau khi p xung - CD : Th tch lp kp ca in cc lm vic. Phng php cc ph xung thng c p dng vi cc loi in cc git thu ngn v in cc rn. I.5.2.1 Phng php cc ph sng vung : E

t Hnh 1.1 : Cc thnh phn in p trong SWP : in p mt chiu : in p xoay chiu ip = i1 i2

37 E

Hnh 1.2 : Dng tn hiu o ca phng php SWP Phng php cc ph sng vung c a ra bi Barker v Jenkin (1582 ). Phng php ny in cc git thu ngn c phn cc bng mt in p mt chiu bin thin theo thi gian, c cng thm vo mt in p xoay chiu dng vung gc c tn s 125 200Hz v c bin c th thay i t 1- 5mV. Mc d in cc c phn cc thng xuyn bng in p xoay chiu cng vo in p mt chiu nhng nh mt thit b ng b ngi ta ch ghi cng dng vo khong thi gian hp vo cui mi git, c th l 2 giy sau khi to thnh git trong mt khong 100 200 giy ng vi cui na chu k trong iu kin . Trong thc t ngi ta thng o cng dng in hai thi im, sau khi np xung khong 17ms v sau khi ngt xung 17ms. Hiu ca hai gi tr dng in ny l tn hiu u ra. S ph thuc ca hiu dng in ny theo th in cc c dng nh pc nh trn. ti nh pc l Epc tng ng nh E1/2 trong cc ph c in. Bng phng php cc ph sng vung c th t nhy ti 10 -7M v chn lc l 10000.

38

Nhc im ca phng php ny l nhy gim khi tng tnh thun nghch ca qu trnh in cc. Gi tr nh ipc c tnh theo phng trnh : ip = K . n2 . D1/2 . EA . CA Trong : K n D CA = Hng s : S electron trao i trong phn ng : H s khuch tn : Nng cht phn tch trong dung dch

EA : Bin xung

Hin nay phng php cc ph sng vung c m rng thnh phng php Von ampe sng vung. Ton b qu trnh o ca phng php ny trn git thu ngn vi bc qut th nhanh vi xung sng vung 5 10 giy, bin xung 50mV c thm vo, thi gian t xung vi tn s 250 Hz c tc qut 1000mV/s v th iu kin o ny ch xy ra trn git thu ngn l tt

39

I.5.2.2 Phng php cc ph xung thng ( NPP ) : E

EA

t Hnh 1.3 : Dng in p phn cc trong NPP I

t1

2t1

ID

E1/2 Hnh 1.4 : Dng th ca phng php NPP

40

IF = n . F . C . S .

D / ( .t )

. 1+ p

(*)

D : Din tch b mt in cc ti thi im o C : Nng cht in hot D : H s khuch tn t : Khong thi gian tnh t khi np xung n khi o dng p = ln [(
n.F RT

) . ( E - E21/2 ) ]
: Th xung

E1/2 : Th bn sng Trong phng php ny in cc git thu ngn c phn cc bng mt in p mt chiu chn trc v c gi khng i trong sut qu trnh o gi l in p khi im tng ng vi chn sng cc ph trong cc ph c in. Trong mi chu k git in cc c phn cc b sung bng mt xung vung gc c khong thi gian tn ti rt ngn 40 100ms tu theo tiu chun tng nc v tng my. Sau thi gian xung b ngt v th in cc tr v in p khi im. Bin xung tng dn theo thi gian vi mt tc u ging nh tc qut th tuyn tnh trong cc ph c in. Cng dng c ghi theo 1 trong 2 cch : - Ghi cng dng ti mt thi im sau khi t xung thng l 17ms trc khi ngt xung. - Cng dng cc ph c ghi 2 ln : ln 1 trc khi ngt xung v ln 2 sau khi ngt xung. Thng l 17ms trc v sau khi t v ngt xung. Cch ny cho hiu qu tt hn v thu c ng E I l dng pc nh trong cc ph sng vung. Dng Faraday c th hin bng phng trnh ( * ). Phng php ny c th t nhy 10-7M cho c hai qu trnh thun nghch v khng thun nghch. V nhiu d kin thun li cho php phn tch

41

cht hu c. Trong mt s trng hp ngay c phng php c in khng cho sng cc ph r rng th n vn cho sng cc ph r rng I.5.2.3 Phng php cc ph xung vi phn (DPP)
E

Fei

Estep
tstep
Chu k git

t
Hnh 1.5 : Dng in p phn cc trong phng php DPP Fei tstep : Bin xung : Thi gian np xung in
i ip = i1 i2

Estep : Bc th mt xung in

Hnh 1.6 : Dng tn hiu u ra ca phng php DPP

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Trong phng php cc ph xung vi phn in cc git thu ngn c phn cc bng mt in p mt chiu bin thin tuyn tnh vi tc chm ( 1 2 mV/s ) nhng vo cui mi chu k git ( git ri cng bc nh b g ), trn khung in p bin i mt chiu ngi ta t thm mt xung vung gc vi bin thay i trong khong 10 100 mV v di xung c 400 100 ms. Cng dng l hiu ca gi tr dng ghi 17ms trc khi np xung v 17ms sau khi ngt xung. u im ca phng php ny l c nhy cao ( 10-7 M ) i vi cc hp cht v c cng nh hu c, phn ng thun nghch cng nh khng thun nghch. Hn na dng ng cc ph l dng pc c cc i nn sau mi ln ghi ng nn li tr v v tr ban u nn chn lc ca phng php ny tng ln nhiu ln : c th xc nh ng thi nhiu nguyn t m khng cn tch hay lm giu. Tuy nhin cn lu rng do gii hn pht hin cc tiu trong cc ph xung vi phn l thp hn nhiu so vi phng php c in nn nh hng ca in tr h o cn c xem xt k. Thng nng nn in li phi ln hn cht phn tch 20 50 ln loi tr nh hng ca s in chuyn v loi tr nh hng ca dn in thp do nng nn nh phi s dng h o 3 in cc. I.5.3 Phng php Von ampe ho tan : Nguyn tc : Thit b dng mt my cc ph t ghi c 3 in cc : cc lm vic l cc git thu ngn tnh, ch yu l in cc HMDE. in cc so snh thng l calomen hoc cc AgCl c th khng i. in cc ph tr l in cc platin. Np bnh c mt l nh dn kh tr l kh nit hoc argon vo dung dch ui kh oxi ho tan. Khi in phn lm giu chn th in phn thch

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hp v gi khng i trong sut qu trnh in phn. Th ny phi kho st s b. i vi qu trnh kh trn catot th in phn thng m hn 300 500mV so vi th nh v i vi qu trnh anot th in phn thng dng hn th nh mt lng tng t. Khng phi th nh cng m hay cng dng th cng tt v lc s km tnh chn lc v gim hiu sut in phn. Trong qu trnh in phn s khuy dung dch t 2000 4000 vng/pht khuch tn dung dch di dng chy tng ch khng phi l chuyn ng xoy. Sau qu trnh in phn th ngng khuy v c mt thi gian ngh t 3 60s cho ton b h thng dung dch c yn tnh v kim loi c phn b u trn hn hng. Bc ho tan kt ta c lm giu trn in cc : in cc s b phn cc ngc vi qu trnh in phn v ghi o dng Vn Ampe. Nu qu trnh in phn l qu trnh catot th qu trnh ho tan s l qu trnh anot v ng vn ampe ho tan oc gi l ng vn ampe ho tan anot. Khi qut th trong qu trnh vn ampe anot th th s qut t m sang dng. + C ch ca phng php Vn Ampe ho tan Anot ( ASV ) : Bc 1 : Lm giu cht phn tch trn catot : Mn+ + ne + Hg M(Hg)

Bc 2 : Ho tan kt ta trn anot : qu trnh anot, qut th t m sang dng dn. M(Hg) - ne Phng trnh pc : Mn+ + Hg

ip

= K . n3/2 . D1/2M(Hg) . CoM . V1/2 . r2 . tacc

44

Trong :

ip
K n r tacc V

: Dng pc

D1/2M(Hg) : H s khuch tn ca kim loi M trong hn hng : Hng s : S electron trao i : Bn knh git : Thi gian lm giu : Vn tc qut

Lng kim loi c lm giu catot trong hn hng :

iacc . tacc
CoM = VHg . n . F

( F : l hng s Faraday ) Trong : VHg = AF . v AF : Din tch b mt mng v : dy ca mng + C ch ca phng php vn ampe ho tan catot ( CSV ): Bc 1 : 2Hg Hg22+ + 2e

Hg22+ + 2ABc 2 : Hg2A2 + 2e

Hg2A2

2Hg

2A-

Trong phng php CSV qu trnh lm giu l qu trnh anot, qu trnh ho tan l qu trnh catot, th qut trong qu trnh ho tan t dng sang m.

45

I.5.4 Phng php Vn ampe ho tan hp ph ( AdSV ) : ( Absorbtion Stripping Voltammetry ) Trong phng php Vn ampe ho tan anot v catot phng php lm giu bng in phn c s dng tuy nhin c nhiu qu trnh lm giu m in phn khng th thc hin c nh i vi niken v coban khng tan trong thu ngn. Khi ngi ta chuyn cht cn phn tch vo dng mt phc cht c th hp ph tt trn in cc. Ngy nay y l hng lm giu ch yu, c bit i vi hp cht hu c. C 3 trng hp hp ph xy ra : + Trng hp 1 : Thm vo dung dch mt thuc th c kh nng hp ph tt ln b mt in cc ti mt th xc nh. Sau khi b hp ph n s to phc vi cht cn xc nh tp trung n ln b mt in cc. B1 : Rdd Rh . ph + Mn+ Rh.ph (MRnn+ )h . ph

Trong trng hp ny qu trnh hp ph xy ra trc phn ng ho hc. Khi xc nh tin hnh qu trnh ho tan in ho cht c lm giu bng hp ph. B2 : ( MRnn+ )h . ph Trng hp 2 : Cht cn xc nh tham gia phn ng ho hc to phc vi thuc th thch hp c trong dung dch ri phc b hp ph ln b mt in cc (thng xy ra vi niken v coban ). + ne M + nRh . ph

46

C ch ca qu trnh : B1 : Mddn+ + MRndd B2 : (MRn)h . ph + ne Mdd + Rdd nRdd (MRn)h . ph MRndd

+ Trng hp 3 : S to phc sau khi c s thay i s oxi ho ca cht phn tch : B1 : Mm+ ne M( m n ) + MR( m n ) h . ph

M( m n ) + + ( m n )Rdd ( h . ph )

B2 : Qu trnh xy ra trng hp ny tng t nh trng hp 1. ng Vn ampe ho tan hp ph c dng mt nh pc. Epc v Ipc ph thuc vo nhiu yu t : nn in li, cht to phc, bn cht in cc lm vic, k thut ghi o ng vn ampe ho tan, Dng ca pc trong phng php vn ampe ho tan hp ph :
D

ip

= K . A . = K . CA [ R . Tacc + 2 ( D / ). tacc ]

Trong : A : Din tch b mt cc : Lng cht hp ph D : H s hp ph K = Hng s

47

R : Bn knh git

ip max

= K . A . max

CA . tacc2

Mt kiu hp ph mi xut hin gn y l in phn lm giu th E1, sau thi gian in phn t ngt chuyn v th E2 ho tan cht , ngay lp tc qut th ngc tr li. Ion kim loi va b ho tan cha khuch tn khi b mt hp ph b hp ph ln b mt di dng phc v b kh v kim loi. Nu s dng phng php ny c th nng nhy ln 10 100 ln so vi phng php vn ampe ho tan anot thng thng. Ngoi lm giu bng hp ph ngi ta cn kt hp vi xc tc. Vng lp c lp i lp li ( c th nng nhy ln ti 10-12 M ). I.5.5 Cc phng php phn tch nh lng trong phn tch in ho : I.5.5.1 Phng php mu chun : Ngi ta s dng hai dung dch ca cng mt cht : Dung dch 1 : c nng Cx ca cht phn tch cn xc nh Dung dch 2 : l dung dch chun bit chnh xc nng Cc. Tin hnh ghi cc ph ca dung dch 1 v 2 trong cng mt iu kin c : hx v hc tng ng. Do s tuyn tnh gia h v C nn ta c :
Cx hx = Cc hc Cx = Cc hx hc

I.5.5.2 Phng php ng chun : lp phng trnh ng chun ta chun b mt dy dung dch c nng bit ca cht cn xc nh : C1 , C2 , , Cn ( thng n = 1 3 ) (theo cp s cng ).

48

Ghi cc ph ca dy trn ta c : h1 , h2 , , hn ( chiu cao cc pc tng ng ). T cc gi tr v th v lp phng trnh ng chun s ph thuc ca nng v chiu cao pc. Phng trnh ng chun c dng : y = ax + b Vi dung dch nghin cu c nng Cx cha bit ta ghi c cc ph l hx . Thay hx = y vo phng trnh ng chun ta tnh c Cx I.5.5.3 Phng php thm chun : Nguyn tc ca phng php ny l dng ngay mu phn tch lm nn chun b mu u bng cch ly mt lng mu phn tch nht nh ( c nng Cx ) ri thm vo nhng lng chnh xc nguyn t cn xc nh theo tng bc nng , chng hn C1 , C2 , C3 , ( theo cp s cng ), ta thu c dy mu u : Cx + C1 , Cx + C2 , Cx + C3 , Chn cc iu kin phn tch thch hp ta tin hnh ghi o cc ph ca cc mu trong dy mu u chun b trn ta thu c chiu cao cc pc tng ng : h1 , h2 , h3 , T ta xy dng c th ca h theo C. h h2 h1 A

C1

C2

Hnh 1.5 : ng chun

49

Da vo th ny ngi ta xc nh c nng cht phn tch trong dung dch, bng cch : ko di ng chun t A ct trc honh ti im M . Khong OM l nng Cx cn tm. Phng php thm chun c u im l : qu trnh chun b mu d dng, khng phi s dng nhng ho cht c tinh khit cao, loi tr c hon ton nh hng v thnh phn cng nh cu trc vt l ca cc cht to thnh mu. I.5.5.4 Phng php thm : Trong phng php ny ngi ta tin hnh nh sau : S dng dung dch phn tch cha bit nng Cx , tin hnh ghi cc ph c pc tng ng hx . Thm vo dung dch trn mt lng bit chnh xc nng cht cn phn tch Cch , tin hnh ghi cc ph c pc l htng . Ta c : htng = hch + hx hx / hch = Cx / Cch ph : I.5.6.1 Cc rn hnh a ( RDE )( Rotating disc electrode ) l mt mt phng hnh trn ng knh 3 5 mm lm bng cc vt liu tr nh platin, vng v cc loi cacbon c tinh khit cao, tr v c b mt d nh bng din tch b mt khng i. Platin qu him nhng kh gia cng b mt cho din tch b mt c din tch khng i, v qu th hiro trn platin nh nn khong th s dng hp c bit l vi qu trnh catot. hch = htng - hx Cx = Cch . hx / hch Do s tuyn tnh ca C v h ta c : I.5.6 Cc loi in cc c s dng trong phng php phn tch cc

50

Vt liu tt nht sn xut in cc rn hnh a l cacbon thu tinh c bn ho hc cao, khng thay i k c khi ngm nhiu gi trong nc cng thu, d nh bng b mt. Thc nghim chng minh rng ly cc loi giy nhm mn nh bng b mt in cc a quay bng than thu tinh th b mt thc ca n bng b mt hnh hc ca n: S = . R2 Ngoi cacbon thu tinh c th dng cacbon ngm tm hoc cacbon nho ch to in cc a. Khong th hot ng ca in cc ny rt rng : - Trong mi trng axt : + 1 -1 V - Trong mi trng kim hoc trung tnh : + 1 -1,8 V. I.5.6.2 in cc mng thu tinh ( TMFE ): ( Thin Mecury film electrode ) Loi cc ny rt thun li cho vic xc nh lng vt cc kim loi d to hn hng vi thu ngn. Ch cn thm vo dung dch phn tch mt lng Hg2+ vi nng 10-5 10-4 M, khi in phn lm giu kim loi phn tch th ion Hg2+ cng b kh ng thi hoc kh trc to thnh mt mng mng v u thu ngn trn b mt cc rn. Kim loi cn xc nh c ho tan u trong mng , dng in cc TMFE hn ch c s hnh thnh hp cht gian kim loi hoc dung dch rn khi xc nh lng vt ca mt s ion kim loi c mt trong dung dch. Thng thng ngi ta dng in cc mng thu ngn trn nn than thu tinh . C 3 loi than thng dng : + Grafit ngm tm : loi ny t s dng v c l xp hp th kh + Grafit cacbon ( than thu tinh ) : c dng nhiu nht

51

+ Grafit nho : i khi cng c dng tuy nhin hnh dng ca n c th b bin i trong mt s trung hp. - Mng mng thu ngn c to ra bng hai cch : + To mng mng trc + To mng ng thi Mi cch c mt u vit ring c p dng cho tng i tng khc nhau tu v tr ca ion kim loi to mng. Nng thu ngn thng c dng gp 100 1000 ln so vi nng ca ion phn tch. I.5.6.3 in cc git thu ngn treo (HMDE) in cc git thu ngn bao gm 3 loi : in cc git thu ngn treo (HMDE ), in cc git thu ngn ri cng bc ( SMDE ), v in cc git ri DME in cc git thu ngn l mt git thu ngn c kch thc nh v bt ng ng knh khong 1mm c treo trn mt mao qun bng thu tinh hi lm gia c mt mu nh ngn platin dn in. m bo tnh chnh xc v lp li ca php xc nh yu cu ca git thu ngn tnh l c kch thc khng i v lp li cao. V sau mi ln o phi to mt git khc ging nh git ban u. u im ca in cc git thu ngn : + Khong th cho php ca thu ngn rt rng, nn xc nh c mt s ln kim loi. Trong mi trng axt khong th axt tt l -0,15 -1,2V v trong mi trng baz khong th tt l -0,15 2V. + Dng in cc thu ngn thun li cho vic chn nn phn tch, chn th in phn, c lp li cao. C th xc nh c nng thp tu phng php. Nu trong qu trnh ghi cc ph ca cht phn tch git thu ngn b ri cng bc theo mt chu k nht nh th c gi l in cc git thu ngn ri cng bc ( SMDE ).

52

u im ca in cc SMDE cng nh DME l in cc git ri nn in cc lun c lm mi, nhng SMDE li c u im nh HMDE kch c nh v tnh lng trong qu trnh xc nh. C hai loi in cc HMDE v TMFE c u im ging nhau v gii hn pht hin v nhy. Vi in cc mng thu ngn ( TMFE ) nng kim loi trong hn hng in cc cao hn, tc khuch tn kim loi ra khi in cc TMFE nhanh hn v c c im qu trnh in ho lp mng. Mt khc nu dng TMFE quay, iu kin i lu l s chuyn khi tt hn do TMFE c nhy v phn gii trong mt s trng hp cao hn. Tuy th i vi phng php s dng TMFE cc hp cht gian kim loi d hnh thnh khi phn tch theo phng php Vn ampe ho tan, gy ra s bin dng tn hiu dn n sai s.

53

PHN II : THC NGHIM V KT QU

II.1. Thit b, dng c v ho cht : II.1.1 Thit b, dng c : II.1.1.1 Thit b : Tt c cc php o u c thc hin trn my cc ph xung vi phn 797 VA Computrace ( Metrohm Thy S ) vi h 3 in cc : in cc lm vic l in cc git thu ngn ( HMDE, SMDE ) v in cc so snh l in cc Ag/AgCl, in cc ph tr platin. II.1.1.2 Dng c : - Pipet cc loi - Cc thu tinh : 250, 500 ( ml ) - Bnh nh mc - My o pH Milwaukee ( sn xut Italia ) - Cn phn tch c chnh xc 0,01mg II.1.2 Ho cht : Tt c cc loi ho cht s dng trong nghin cu u c cht lng Suprapure ca MERCK, cc dung dch chun kim loi c pha t dung dch gc nng 1000mg/l ca MERCK, nc ct s dng l nc ct hai ln. Ho cht : - Dung dch chun gc Zn2+ 1000ppm - Dung dch chun gc Pb2+ 1000ppm - Dung dch chun gc Cd2+ 1000ppm - Dung dch chun gc Cu2+ 1000ppm - Dung dch m axetat pH =4,6 - Tinh th NaOH - Axit HNO3 c

54

II.2 Ly v bo qun mu : Cc b phn ca dng c, thit b u lm bng Teflon khng kim loi trnh gy nhim bn kim loi cho mu, bnh ng mu lm bng nha PE Trc khi dng bnh ng mu c trng ra 3 ln bng chnh mu. Mu c bo qun bng cch: 1,5 lit mu + 5ml axit HNO3 c tinh khit trnh cc kim loi Zn, Cd, Pb, Cu b hp th ln thnh bnh cha mu. mu trong t lnh 4oC ch phn tch. II.3 Quy trnh v c ho mu Vi tng loi nc ca mi sng, ly 500ml mu cn phn tch c axit ho trn thm vo 5ml axit HNO3 c, un trn bp in cho n khi dung dch gn cn, nu c mu th li thm 5ml HNO 3 c v lm bay hi ln na, ng tc ny lp i lp li cho n khi dung dch khng mu. Ri lm bay hi dung dch n cn kh. Phn b sau khi ngui ho tan trong nc ct, un nng ho tan ht mui tan. Lc qua phu lc kh, gi ly ng th tch bng 500ml xc nh Zn, Pb, Cu, Cd. Vi tng loi rau th ta x l mu nh sau: 1. Ra rau, ra li theo nc ct kh t nhin. 2. Xay mt lng rau ti bng my xay sinh t. 3. Cn 1g cho vo bnh Kendan c th thay th bng cc chu nhit. 4. Thm 12ml hn hp (HNO3:HClO4) t l (5:1). Dng a thu tinh trn u yn qua m hoc vi gi Ci nhit ca bp 200 oC trong 40 pht. Khi un y phu trn ming bnh. Ch khng cn mu mu ngui, nu thy dung dch trong gn nh mt mu th dng thm t t 10ml HCl 3N un si 25 pht 150oC ngui thy dung dch trong trng l c nh mc sang bnh 50ml o cc ph

55

Song song tin hnh mt mu trng khng c rau mi ch ha nh mu tht II.4 Xc nh ng thi Zn, Cd, Cu, Pb. II.4.1 Thc nghim tm cc iu kin ti u cho php xc nh Zn, Cd, Cu, Pb. II.4.1.1 Pha ch dung dch cho php xc nh Zn, Cd, Cu, Pb. - Dung dch chun Zn2+ 10ppm - Dung dch chun Cd2+ 1ppm - Dung dch chun Cu2+ 2ppm - Dung dch chun Pb2+ 3ppm - Dung dch chun cha ng thi Zn2+ 10ppm, Cd2+ 0,1ppm, Cu2+ 2ppm, Pb2+ 3ppm - Dung dch m axetat(pH=4,6) - Dung dch HNO3 1M Cch tin hnh: - Dung dch chun Zn2+ 10ppm: Ly 1ml dung dch Zn2+ 1000ppm nh mc n 100ml bng nc ct 2 ln ta c dung dch Zn2+ 10ppm - Dung dch chun Cd2+ 1ppm: Ly 0,1ml dung dch Cd2+1000ppm nh mc n 100ml bng nc ct 2 ln ta c dung dch Cd2+ 1ppm - Dung dch chun Cu2+ 2ppm: Ly 0,2ml dung dch Cu2+1000ppm nh mc n 100ml bng nc ct 2 ln ta c dung dch Cu2+ 2ppm - Dung dch chun Pb2+ 3ppm: Ly 0,3ml dung dch Pb2+ 1000ppm nh mc n 100ml bng nc ct 2 ln ta c dung dch Pb2+ 3ppm - Dung dch chun cha ng thi Zn2+ 10ppm, Cd2+ 0,1ppm, Cu2+ 2ppm, Pb2+ 3ppm: Ly 1ml dung dch Zn2+ 1000ppm; 0,01ml dung dch Cd2+ 1000ppm; 0,2ml dung dch Cu2+1000ppm; 0,3ml dung dch Pb2+ 1000ppm ri nh mc n 100ml bng nc ct 2 ln ta c dung dch cha ng thi Zn2+ 10ppm, Cd2+ 0,1ppm, Cu2+ 2ppm, Pb2+ 3ppm

56

- Dung dch m axetat pH=4,6: Ly 47,46ml andehit axetic 99,2% pha thnh 500ml trong bnh nh mc bng nc ct 2 ln ta c 500ml dung dch CH3COOH 2M. Ly 68,04g CH3COONa.3H2O pha trong 250ml bng nc ct 2 ln ta c 250ml dung dch CH3COONa 2M. Ly 23,5ml dung dch CH3COONa 2M v 26,5 ml dung dch CH3COOH 2M pha long bng nc ct 2 ln thnh 500ml dung dch m axetat pH=4,6 - Dung dch HNO3 1M: T dung dch gc HNO3 c C% = 65%; D = 1,39kg/l. Ly 69,73 ml HNO3 c pha long bng nc ct 2 ln nh mc ti 1 lit ta c dung dch HNO3 1M II.4.1.2 Kho st cc iu kin ti u cho php xc nh Zn,Cd,Pb,Cu. II.4.1.2.1. Kho st s xut hin ca pic: kho st s xut hin ca pic Zn(II),Cd(II),Cu(II),Pb(II) chng ti tin hnh lm nh sau: Ly 20ml nc ct 2 ln + 0,05ml dung dch chun cha ng thi Zn 2+ 10ppm ,Cd2+0,5ppm, Pb2+1ppm, Cu2+1ppm + 0,5ml dung dch m axetat pH=4,6 cho vo bnh in phn, tin hnh in phn Up=-1,2V, qut th t -1,2V +0,2V v tin hnh ghi o ng xung vi phn chng ti thu c kt qu nh sau: Upic(Zn) l -1,20,05V Upic(Cd) l -0,5880,05V. Upic(Pb) l -0,380,05V. Upic(Cu) l 0,03080,05V. II.4.1.2.2 Kho st bin xung. kho st bin xung, chng ti s dng in phn th in phn Udp=-1,2V qut th t -1,2V +0,2V, thi gian sc kh N2 l 300s, thi gian in phn l 30s

57

Ly 20ml nc ct 2 ln + 0,05ml dung dch chun cha ng thi Zn2+ 10ppm, Cd2+0,5ppm, Pb2+1ppm, Cu2+1ppm + 0,5ml dung dch m axetat pH=4,6 cho vo bnh in phn Tin hnh ghi o ng vi phn ca dung dch cc bin xung khc nhau, kt qu thu c bng 2.1 Bng 2.1: S thay i chiu cao pic Zn, Cd, Pb, Cu theo bin xung. Chiu cao pic h (A) Bin xung (V) 0,02 0,03 0,04 0,05 0,06 0,07 0,08 4,80.10-8 6,87.10-8 8,78.10-8 1,01.10-7 1,09.10-7 1,18.10-7 1,20.10-7 2,07.10-8 2,90.10-8 3,70.10-8 4,28.10-8 4,66.10-8 4,98.10-8 5,10.10-8 1,27.10-8 1,81.10-8 2,30.10-8 2,64.10-8 2,90.10-8 3,09.10-8 3,16.10-8 6,14.10-8 8,74.10-8 1,15.10-7 1,32.10-7 1,43.10-7 1,54.10-7 1,58.10-7 Zn Cd Pb Cu

Qua bng 2.1 chng ti rt ra c kt lun: Khi bin xung cao th chiu cao pic tng, khi bin xung gim th chiu cao pic gim. Tuy nhin nu bin xung cao qu th ng nn cao, ng khng p cho nn ta chn bin xung 0,05V II.4.1.2.3 Kho st thi gian t xung kho st thi gian t xung chng ti t cc iu kin o nh th nghim II.4.1.2.2, nhng thay i thi gian t xung v kt qu thu c bng 2.2 Bng 2.2 S thay i chiu cao pic theo thi gian t xung

58

Chiu cao pic (A) Thi gian t xung(s)

Zn

Cd

Pb

Cu

0,01 1,48.10-7 6,43.10-8 3,69.10-8 1,75.10-7 0,02 1,01.10-7 4,28.10-8 2,64.10-8 1,32.10-7 0,03 1,64.10-7 6,54.10-8 3,66.10-8 1,37.10-7 Qua bng 2.2 chng ti thy khi thi gian t xung = 0,01s hay 0,03s th chiu cao pic tng nhng nn cao.Qua kt qu thc nghim thu c gi tr chiu cao pic n nh v nn thp thi gian t xung l 0,02s II.4.1.2.4 Kho st tc qut th. Cc iu kin o nh 2 th nghim trn thay i tc qut, kt qu thu c bng 2.3 Bng 2.3 S thay i chiu cao pic Zn, Cd, Pb, Cu theo tc qut th Chiu cao pic h (A) Tc qut th (V/s) 0,085 9,22.10-8 3,94.10-8 0,1 9,72.10-8 4,18.10-8 0,12 1,01.10-7 4,34.10-8 0,15 1,01.10-7 4,28.10-8 Qua kt qu thc nghim thu c bng 2,53.10-8 2,67.10-8 2,73.10-8 2,64.10-8 2.3 chng ti 1,18.10-7 1,26.10-8 1,31.10-7 1,32.10-7 nhn thy khi Zn Cd Pb Cu

gim tc qut th t 0,15V/s xung 0,085V/s th chiu cao pic li gim, nn cao. Chng ti chn tc qut th l 0,15V/s v lc chiu cao pic ln v n nh, th p, nn thp. II.4.1.2.5 Kho st thi gian sc kh kho st s nh hng ca thi gian sc kh (loi oxi ho tan) n chiu cao pic v nn pic chng ti tin hnh nh sau. S dng cc iu kin

59

o: th in phn, thi gian in phn, bin xung, thi gian t xung, tc , qut th nh trn v sc vi p sut PN2=1atm, thay i thi gian sc kh chng ti thu c kt qu th hin bng 2.4 Bng 2.4 S thay i chiu cao pic Zn, Cd, Pb, Cu theo thi gian sc kh. Chiu cao pic h (A) Thi gian Zn Cd Pb Cu

sc kh (s) 5 9,22.10-8 30 1,09.10-7 200 1,14.10-7 300 1,19.10-7 600 1,16.10-7 Qua bng 2.4 chng ti nhn gian sc kh l 300s

3,64.10-8 3,89.10-8 3,79.10-8 3,89.10-8 3,72.10-8 thy khi thi

2,00.10-8 1,52.10-7 2,34.10-8 1,23.10-7 2,43.10-8 1,18.10-7 2,48.10-8 1,23.10-7 2,47.10-8 1,15.10-7 gian sc kh l 300s th chiu

cao pic t gi tr ln nht, th p, nn thp. V vy chng ti chn thi II.4.1.2.6 Kho st thi gian cn bng Sau khi in phn thng ngng khuy dung dch, nu dng cc git thu ngn tnh hoc cc mng thu ngn iu ch ti ch trn b mt cc a th cn c thi gian ngh tc l yn h thng trong mt khong thi gian ngn (5s 60s) lng kim loi phn b u trn b mt cc. kho st thi gian cn bng ti php o chng ti tin hnh vi cc iu kin o nh cc th nghim trn v thay i thi gian ngh trong mi ln in phn v chng ti thu c bng sau: Bng 2.5 S thay i chiu cao pic Zn, Cd, Pb, Cu theo thi gian cn bng

60

Chiu cao pic h (A) Thi gian cn bng (s) 1 2 3 5 10 30 1,38.10-7 1,24.10-7 1,32.10-7 1,36.10-7 1,31.10-7 1,40.10-7 4,35.10-8 3,93.10-8 4,17.10-8 4,27.10-8 4,08.10-8 4,36.10-8 2,91.10-8 2,68.10-8 2,82.10-8 2,90.10-8 2,78.10-8 2,97.10-8 1,35.10-7 1,19.10-7 1,28.10-7 1,29.10-7 1,23.10-7 1,29.10-7 Zn Cd Pb Cu

Qua kt qu thc nghim thu c bng 2.5 chng ti thy thi gian cn bng l 1s hay 30s th chiu cao pic ln nhng th xu, nn cao. Khi thi gian cn bng tng t 2s n 5s th chiu cao pic tng nhng thi gian cn bng l 10s th chiu cao pic li gim. V vy chng ti chn thi gian cn bng l 5s II.4.1.2.7 Kho st nh hng ca nng mi cht ln nhau. II.4.1.2.7.1 nh hng nng ca Ni2+ ti Zn2+, Cd2+, Pb2+, Cu2+ trong nn m axetat kho st nh hng nng ca Ni2+ti Zn2+, Cd2+, Pb2+, Cu2+ trong nn m axetat chng ti tin hnh th nghim nh sau: Ly 10ml nc ct 2 ln cho vo bnh in phn, thm vo 0,05ml dung dch Zn2+ 10ppm+Cd2+ 0,1ppm+Pb2+ 3ppm+ Cd2+ 2ppm + 0,5ml dung dch m axetat pH=4,6. Tin hnh ghi o ng Vn-Ampe ha tan anot ca Zn2+, Cd2+, Pb2+,Cu2+ cc iu kin o : bin xung, thi gian cn bng, thi gian sc kh ti u kho st trn, th in phn Udp= -1,2V, qut th t -1,2V:+0,2V. Sau thm ln lt tng th tch khc nhau ca dung dch Ni2+1ppm. Tin hnh ghi o ng xung vi phn cc iu kin o nh trn, chng ti thu c bng sau:

61

Bng 2.5 : nh hng nng ca Ni2+ ti Zn2+, Cd2+, Pb2+, Cu2+ trong nn m axetat V Ni2+ 1ppm (ml) 0,000 0,025 0,125 0,325 Chiu cao pic Zn2+ (A) -1,8.10-7 -1,78.10-7 1,81.10-7 1,67.10-7 Chiu cao pic Cd2+ (A) 8,59.10-10 8,55.10-10 8,56.10-10 8,56.10-10 Chiu cao pic Pb2+(A) 1,30.10-8 1,29.10-8 1,29.10-8 1,20.10-8 Chiu cao pic Cu2+ (A) 2,44.10-8 2,38.10-8 2,44.10-8 2,37.10-8 T l nng Ni:Zn:Cd:Pb:Cu (CM) 0:100:1:30:20 5:100:1:30:20 25:100:1:30:20 65:100:1:30:20

Hnh 2.1 nh hng nng Ni ti Zn, Cd, Pb, Cu trong nn axetat

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Qua bng 2.5 v hnh 2.1 chng ti nhn thy chiu cao pic Zn2+, Cd2+, Pb2+, Cu2+thay i khng ng k khi thm th tch Ni2+ t 0,025ml n 0,125ml. Khi thm th tch Ni2+ t 0,325ml tr ln chiu cao pic Zn2+ ,Pb2+, Cu2+ thay i t bin.Nn ta ni 0,325ml Ni2+ 1ppm tr ln thm vo mu phn tch th gy nh hng ti php o Zn2+, Cd2+, Pb2+, Cu2+. Vy kt qu t l nng gii hn Ni bt u nh hng ti php xc nh ng thi Zn, Cd, Pb, Cu trong vng nng kho st l 65:100:1:30:20 II.4.1.2.7.2 nh hng nng ca Fe3+ ti Zn2+, Cd2+, Pb2+, Cu2+ trong nn m axetat kho st nh hng nng ca Fe3+ ti Zn2+, Cd2+, Pb2+, Cu2+ trong nn m axetat chng ti tin hnh th nghim nh sau: Ly 10 ml nc ct 2 ln cho vo bnh in phn, thm vo 0,05ml dung dch Zn2+ 10ppm+Cd2+ 0,1ppm+Pb 2+3ppm+ Cu2+ 2ppm + 0,5ml dung dch m axetat pH=4,6. Tin hnh ghi o ng Vn-Ampe ha tan anot ca Zn2+, Cd2+, Pb2+,Cu2+ cc iu kin nh trn . Sau thm cc th tch khc nhau ca dung dch Fe3+1ppm. Mt ln na ghi o ng Vn-Ampe ha tan anot cc iu kin o nh trn, kt qu thu c bng 2.6 Bng 2.6 nh hng nng ca Fe 3+ ti Zn2+, Cd2+, Pb2+, Cu2+ trong nn m axetat V Fe3+ 1 ppm (ml) 0 0,025 0,075 1,075 1,575 Chiu cao pic Zn2+ (A) 3,30.10-7 3,24.10-7 3,21.10-7 2,88.10-7 3,10.10-7 Chiu cao pic Cd2+ (A) 1,41.10-9 1,40.10-9 1,36.10-9 1,16.10-9 1,20.10-9 Chiu cao pic Pb2+ (A) 2,28.10-8 2,24.10-8 2,25.10-8 1,98.10-8 2,00.10-8 Chiu cao pic Cu2+ (A) 5,18.10-8 5,09.10-8 5,09.10-8 4,60.10-8 4,80.10-8 T l nng Fe:Zn:Cd:Pb:Cu (CM) 0:100:1:30:20 5:100:1:30:20 15:100:1:30:20 215:100:1:30:20 315:100:1:30:20

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Hnh 2.2 nh hng nng Fe (III) ti php o ng thi Zn, Cd, Pb, Cu trong nn axetat Qua bng 2.6 v hnh 2.2 chng ti rt ra c kt lun : Khi thm th tch ca dung dch Fe3+ 1ppm t 0,025ml n 0,075ml th chiu cao pic ca Zn2+, Cd2+, Pb2+, Cu2+ thay i khng ng k. Khi thm t 1,075ml tr ln th chiu cao pic Zn2+, Cd2+, Pb2+, Cu2+ thay i t bin . Vy kt qu t l nng gii hn Fe bt u nh hng ti php xc nh ng thi Zn, Cd, Pb, Cu trong vng nng kho st l 215:100:1:30:20 II.4.1.2.7.3 nh hng nng ca Pb2+ ti Cd2+trong nn m axetat

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 kho st nh hng nng ca Pb2+ ti Cd2+trong nn m axetat chng ti tin hnh th nghim nh sau: Ly 10ml nc ct 2 ln cho vo bnh in phn, thm vo 0,05ml dung dch Cd2+1ppm + 0,5ml dung dch m axetat pH=4,6. Tin hnh ghi o ng Vn-Ampe ha tan anot ca Cd2+ trong cc iu kin ti u trn. Sau thm ln lt cc th tch khc nhau ca dung dch Pb 2+ 3ppm. Mt ln na ghi o ng Vn-Ampe ha tan anot cc iu kin nh trn, kt qu thu c bng 2.7 Bng 2.7 nh hng nng ca Pb2+ ti Cd2+trong nn m axetat VCd2+1 ppm (ml) VPb2+3ppm (ml) 0,00 0,025 0,05 0,10 0,15 0,20 0,30 0,50 0,70 Chiu cao pic Cd2+ (A) 6,01.10-9 6,01.10-9 6,07.10-9 6,08.10-9 6,00.10-9 6,03.10-9 6,07.10-9 5,64.10-9 5,47.10-9 T l nng Pb2+:Cd2+ (CM) 0:5 15:10 10:1 6:1 9:1 12:1 18:1 30:1 42:1

0,05

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Hnh 2.3 nh hng nng Pb ti Cd trong nn m axetat Qua bng 2.7 v hnh 2.3 chng ti rt ra c kt lun: Khi thm th tch ca dung dch Pb2+ 3ppm t 0,025ml n 0,3ml th chiu cao ca pic Cd2+ thay i khng ng k. Khi thm t 0,5ml tr ln th chiu cao ca pic Cd2+ thay i t bin. Vy t l nng Pb2+ : Cd2+ m Pb2+ bt u gy nh hng ti php o Cd2+ l CPb2+ : CCd2+ = 30 : 1 II.4.1.2.7.4 nh hng nng ca Zn2+ ti Cd2+ trong nn m axetat kho st nh hng nng ca Zn2+ ti Cd2+ trong nn m axetat chng ti tin hnh th nghim nh sau:

66

Ly 10ml nc ct 2 ln cho vo bnh in phn, thm vo 0,05ml dung dch Cd2+1ppm + 0,5ml dung dch m axetat pH=4,6. Tin hnh ghi o ng Vn-Ampe ha tan anot ca Cd2+ trong cc iu kin ti u trn. Sau thm ln lt cc th tch khc nhau ca dung dch Zn2+ 10ppm. Mt ln na ghi o ng Vn-Ampe ha tan anot cc iu kin nh trn, kt qu thu c bng 2.8 Bng 2.8 nh hng nng ca Zn2+ ti Cd2+trong nn m axetat VCd2+ 1ppm (ml) 0,05 VZn2+ 10ppm (ml) 0,00 0,05 0,10 0,20 0,50 Chiu cao pic Cd2+1ppm (h) 6,95.10-9 6,88.10-9 6,81.10-9 6,90.10-9 6,35.10-9 T l nng Zn2+:Cd2+ (CM) 0:5 10:1 20:1 40:1 100:1

Hnh 2.4 nh hng nng Zn ti Cd trong nn m axetat Qua bng 2.8 v hnh 2.4 chng ti rt ra c kt lun:

67

Khi thm th tch ca dung dch Zn2+ 3ppm t 0,05ml n 0,2ml th chiu cao pic Cd2+ thay i khng ng k. Khi thm t 0,5ml tr ln th chiu cao pic Cd2+ thay i t bin.Vy t l nng Zn2+:Cd2+ m Zn2+ bt u gy nh hng ti php o l CZn2+: CCd2+ = 100 : 1 II.4.1.2.7.5 nh hng nng ca Cu2+ ti Pb2+ trong nn m axetat kho st nh hng nng ca Cu2+ ti Pb2+ trong nn m axetat chng ti tin hnh th nghim nh sau: Ly 10ml nc ct 2 ln cho vo bnh in phn, thm vo 0,05ml dung dch Pb2+3ppm + 0,5ml dung dch m axetat pH=4,6. Tin hnh ghi o ng Vn-Ampe ha tan anot ca Pb2+ trong cc iu kin ti u trn. Sau thm ln lt cc th tch khc nhau ca dung dch Cu 2+ 2ppm. Mt ln na ghi o ng Vn-Ampe ha tan anot cc iu kin nh trn, kt qu thu c bng 2.9 Bng 2.9 nh hng nng ca Cu2+ ti Pb2+trong nn m axetat VPb2+3 ppm (ml) VCu2+2 ppm (ml) 0 0,05 0,10 0,15 0,25 0,35 0,55 0,85 1,45 1,70 1,90 2,40 Chiu cao pic Pb2+ (A) 1,87.10-8 1,88.10-8 1,88.10-8 1,88.10-8 1,85.10-8 1,84.10-8 1,82.10-8 1,88.10-8 1,87.10-8 1,75.10-8 1,70.10-8 1,70.10-8 T l nng Cu2+:Pb2+(CM) 0:15 2:3 4:3 2:1 10:3 14:3 22:23 34:3 58:3 68:3 76:3 32:3

0,05

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Hnh 2.5 nh hng nng Cu ti Pb trong nn m axetat Qua bng 2.9 v hnh 2.9 chng ti rt ra c kt lun: Khi thm th tch Cu2+ t 0,05ml n 1,45ml th chiu cao pic Pb2+ thay i khng ng k. Khi thm th tch Cu2+ t 1,70ml tr ln th chiu cao pic Pb2+ thay i t ngt. Vy t l nng Cu2+: Pb2+ m Zn2+ bt u gy nh hng ti php o Pb2+ l CCu2+: CPb2+ = 68 : 3 II.4.1.3 Kt qu kho st cc iu kin ti u cho php xc nh ng thi Zn2+, Cd2+, Pb2+, Cu2+ Qua qu trnh kho st cc iu kin ti u, tin hnh ghi ph xung vi phn ca Zn2+, Cd2+, Pb2+, Cu2+, nn dung dch m axetat pH=4,6 chng ti

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rt ra mt s kt lun s dng cc tham s sau cho qu trnh nh lng Zn(II), Cd(II), Pb(II), Cu(II) l: - Tc khuy: 2000 vng/pht. - C git: 4 - Bin xung (V): 0,05 - Tc qut th (V/s): 0,06 - Thi gian sc kh (s): 300 - Thi gian in phn (s):30 - Thi gian cn bng (s): 5 - Th in phn (V):-1,2 - Th bt u qut (V):-1,2 - Kt thc qut (V):+0,2 II.4.2 Xc nh Zn2+, Cd2+, Pb2+, Cu2+ trong mu t to c c s chc chn p dng phng php xc nh Km (Zn), Cadimi (Cd), Ch (Pb), ng (Cu) bng phng php Von-Ampe ha tan anot xung vi phn vi cc iu kin ti u chn. Chng ti tin hnh nh lng Zn2+, Cd2+, Pb2+, Cu2+ trong hai mu t to vi hai ngng nng khc nhau: Ly 10ml nc ct 2 ln cho vo bnh in phn, thm vo 0,05ml dung dch Zn2+ 10ppm + Cd2+ 0,1ppm + Pb 2+3ppm + Cu2+ 2ppm + 0,5ml dung dch m axetat pH=4,6 + thm cc th tch Ni(II), Fe(III) trong gii hn khng cn. Tin hnh nh lng 4 nguyn t cc iu kin ti u trn v th tch mi ln thm dung dch cha ng thi Zn2+ 10ppm, Cd2+ 0,1ppm,Pb
2+

3ppm, Cu2+ 2ppm l 0,05ml. Kt qu o th hin hnh 2.6

Bng 2.10 Kt qu nh lng Zn, Cd, Pb, Cu trong mu t to th nht

Nguyn t

Nng trong bnh in phn

Nng xc nh c

Sai s (%)

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Zn Cd Pb Cu

(g/l) 50 15 5 20

(g/l) 50,022 15,036 4,987 20,056

0,044 0,24 0,26 0,28

Hnh 2.6 Ph xung vi phn ca Zn, Cd, Pb, Cu trong mu t to th nht Ly 10 ml nc ct 2 ln cho vo bnh in phn, thm vo 0,05ml dung dch Zn2+ 10ppm+Cd2+ 3ppm+Pb 2+1ppm+ Cu2+ 4ppm + 0,5ml dung dch m axetat pH=4,6 + thm cc th tch Ni(II),Fe(III) trong gii hn khng

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cn. Tin hnh nh lng 4 nguyn t cc iu kin ti u trn v th tch mi ln thm dung dch cha ng thi Zn2+ 10ppm, Cd2+ 0,1 ppm,Pb ppm, Cu2+ 2 ppm l 0,05ml. Kt qu o th hin hnh 2.7 Bng 2.11 Kt qu nh lng Zn, Cd, Pb, Cu trong mu t to th hai Nng trong Nguyn t Zn Cd Pb Cu bnh in phn (g/l) 50 0,5 15 10 Nng xc nh c (g/l) 50,012 0,049 15,720 10,102 Sai s (%) 0,024 2 4,8 1,02
2+

Hnh 2.7 Ph xung vi phn ca Zn, Cd, Pb, Cu trong mu t to th hai Vy php o nh lng ng thi Zn2+, Cd2+, Pb2+, Cu2+ bng phng php Von-Ampe ha tan anot xung vi phn l ng tin cy.

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II.4.3. nh lng Km (II), Cadimi(II), Ch (II), ng (II) trong mu nc sng Qu trnh nh lng Km (II), Cadimi(II), Ch (II), ng (II) trong mu nc sng bng phng php Vn-Ampe ha tan anot xung vi phn c tin hnh nh sau: Ly 0,5ml mu nc sng + 0,05ml dung dch axetat pH=4,6 +10 ml nc ct 2 ln vo bnh in phn. Tin hnh ghi o ng xung vi phn v th tch mi ln thm dung dch chun cha ng thi Zn2+ 10ppm, Cd2+ 0,1ppm,Pb 2.11
2+

3ppm, Cu2+ 2ppm l 0,08 ml. Kt qu thu c i vi 4 mu

nc sng SBN4, SBM9, SDM2, SDN1 c th hin hnh 2.8, 2.9, 2.10,

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Hnh 2.8 Ph xung vi phn ca Zn, Cd, Pb, Cu trong mu SBN4 Hnh 2.9 Ph xung vi phn ca Zn,Cd, Pb, Cu trong mu SBM9

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Hnh 2.11 Ph xung vi phn ca Zn, Cd, Pb, Cu trong mu SDN1 II.4.3.3 nh lng Km (II), Cadimi(II), Ch (II), ng (II) trong mu rau Qu trnh nh lng Km (II), Cadimi(II), Ch (II), ng (II) trong mu rau bng phng php Vn-Ampe ha tan anot c tin hnh nh sau: Ly 0,5ml nc rau + 0,05ml dung dch m axetat pH = 4,6 + 10ml dung dch nc ct hai ln cho vo bnh in phn. Tin hnh ghi o ng xung vi phn v th tch mi ln thm dung dch chun cha ng thi Zn 2+ 10ppm, Cd2+ 3ppm,Pb 2+1ppm, Cu2+ 4 ppm l 0,08 ml. Kt qu thu c vi 4 mu rau RV1-KLN, RV2-KLN, RV3-KLN, RV4-KLN th hin hnh 2.12, 2.13, 2.14, 2.15

75

Hnh 2.12 Ph xung vi phn ca Zn,Cd,Pb,Cu trong mu RV1-KLN

76

Hnh 2.14 Ph xung vi phn ca Zn, Cd, Pb, Cu trong mu RV2-KLN

Hnh 2.15 Ph xung vi phn ca Zn,Cd, Pb, Cu trong mu RV3-KLN

77

Hnh 2.15 Ph xung vi phn ca Zn,Cd, Pb, Cu trong mu RV4-KLN

78

PHN III: KT LUN 1. tng quan c cc phng php x l tch loi Zn, Cd, Pb, Cu t mi trng nc bng cc phng php: chit trc quang, phng php AAS, phng php Vn-Ampe ha tan anot xung vi phn. 2. kho st c cc iu kin ti u xc nh ng thi Zn, Cd, Pb, Cu bng phng php Von-Ampe ha tan anot xung vi phn. 3. tin hnh xc nh ng thi Zn, Cd, Pb, Cu trong mu t to. 4. nghin cu nh hng ca hai nguyn t Ni, Fe ti php xc nh ng thi Zn,Cd, Pb, Cu. 5. nghin cu nh hng ln nhau ca cc nguyn t Zn,Cd, Pb, Cu. 6. tin hnh nh lng ng thi Zn, Cd, Pb, Cu trong mu nc sng v rau - Kt qu nh lng trong mu nc sng Zn (mg/l) Cd (g/l) Pb (mg/l) Cu (mg/l) SBN4 0,090 0,000 0,009 0,003 SBM9 0,151 0,092 0,012 0,005 SDM2 0,125 0,088 0,021 0,006 SDN1 0,097 0,106 0,010 0,005

- Kt qu nh lng trong mu rau Zn (mg/l) Cd (g/l) Pb (g/l) Cu (mg/l) RV1-KLN 1,585 7,624 157,684 0,066 RV2-KLN 1,958 6,195 85,685 0,075 RV3-KLN 1,386 0,000 157,445 0,080 RV4-KLN 1,209 1,274 108,007 0,058

TI LIU THAM KHO

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[1]. [2]. [3]. [4]. [5]. [6]. [7]. [8]. [9]. [10]. [11]. [12].

Hong Minh Chu (1975), C s ha phn tch, NXBGD Phm Lun, Phng php phn tch ph nguyn t, NXB HQGHN. Hong Th Bnh Minh (2008), Lun vn tt nghip, khoa Ha, HV T Vng Nghi, Trn T Hiu (hiu nh Nguyn Tinh Dinh) (1986), Phn tch nc, NXBKH v KT, H Ni Nguyn Khc Ngha (1997), Gio trnh p dng ton hc thng k x l s liu thc nghim, HSPV Nguyn Khc Ngha (2000), Cc phng php phn tch ha l, HV Lng Th Nguyt (2008), Lun vn tt nghip, khoa Ha, HV Hong Nhm (2004), Ha hc cc nguyn t, tp 2, NXB HQGHN Nguyn Th Thu Thy (2009), Lun vn tt nghip, khoa Ha, HV H Vit Qu (1998), Cc phng php phn tch hin i - ng dng trong ha hc, NXB GD HQG, HN. H Vit Qu (1994), X l s liu thc nghim bng phng php ton hc thng k, HSP QN. H Vit Qu, C s ha hc phn tch hin i Cc phng php phn tch l ha, tp II NXB HSP

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