XC NH HM LNG KIM LOI NNG TRONG THC PHM TNG QUAN Kim loi nng l nhng kim lai

c khi lng ring ln hn 5g/cm3. Mt s kim loi nng c th cn thit cho sinh vt, chng c xem l nguyn t vi lng. Mt s khng cn thit cho s sng, khi i vo c th sinh vt c th khng gy c hi g. Kim loi nng gy c hi vi mi trng v c th sinh vt khi hm lng ca chng vt qu tiu chun cho php. Cc kim loi nng c hp th vo c th chng ta vi mt hm lng va phi, chng ng vai tr ht sc quan trng i vi c th: xc tc tng hp ra noradrenalin, cht dn chuyn hot ng thn kinh thc tnh v ch . Tham gia vo vic tng hp ra sc t melanin, tham gia hot ng chuyn ho cc m lin kt v chui phn ng ho hc lin kt ca t bo. Tham gia vo qu trnh tng hp gen, tng hp protein, trong chuyn ho acid bo cha no to ra mng t bo 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, Cugy ra nhng bnh m v nguy hi i vi con ngi v ng vt. Cc kim loi nng ny c hp th vo c th vt qu gii hn cho php, chng s gy c i vi c th nh: ng c cp tnh, khi cc kim loi c nh asen, ch, thu ngn b hp th vo c th vi lng nh c th gy cht ngi, gy ra cc bnh mn tnh, c th gy t bin gen, ung th, thiu mu, cc bnh tim mch, bnh ngoi da, bnh gan, cc vn lin quan n tiu ho, ri lon thn kinh Cc kim loi ny c hp th vo c th qua lng thc - thc phm, nc ung cng c th qua bt a, chi. Lng thc thc phm b nhim kim loi nng th cc kim loi ny s thc y qu trnh h hng thc phm, lm gim gi tr dinh dng cng nh gi tr cm quan ca thc phm.

Thc phm c th b nhim cc kim loi nng t nhiu ngun khc nhau: Nguyn liu dng ch bin thc phm, trong qu trnh ch bin, bo qun thc phm, qu trnh chuyn ch thc phm.. Trong thi i ngy nay vic s dng ho cht a vo sn xut kh ph bin nn nguy c nhim cc kim loi nng vo thc phm ngy cng tng do tnh trng ng c do cc kim loi nng ang gia tng. V vy vic tm ra cc phng php xc nh hm lng kim loi nng c trong thc phm l vn cn quan tm hng u bo v sc kho v mi trng.

Phn I: C S L THUYT CA CC PHNG PHP XC NH MT S KIM LOI Cu, Zn, Pb, Cd I. Phng php trc quang Phng php phn tch o quang l phng php phn tch cng c da trn vic o nhng tn hiu bc x in t v tng tc ca bc x in t vi cht nghin cu. Nguyn tc ca phng php l da trn kh nng to phc mu ca cht phn tch vi mt thuc th no . o hp th quang ca phc mu ta s bit c nng cht phn tch. Phng php c u im l tin hnh nhanh, thun li. C nhy cao, chnh xc c ti 10-6mol/l. Tu thuc vo hm lng cht cn xc nh m c chnh xc t 0,2 ti 20%. 1.1. nh lut Lambe-Beer Khi chiu mt chm bc x n sc (cng bc x ban u l I0) i qua mt lp dung dch c b dy l v c nng l C, th sau khi i qua dung dch cng bc x b gim i (cng ca bc i ra khi dung dch l I) do qu trnh hp th, phn x, tn x... hp th quang ca dung dch t l thun vi C v l. A = lg
I I0 = .l.C I

% truyn qua: T = I . 100 (%) A = lgT 0 Trong : A : hp th : h s hp th mol (lit.mol-1.cm-1). c trng cho kh nng hp th nh sng ca dung dch. Ph thuc vo bn cht dung dch v bc sng . l: b dy dung dch (cm) C: nng dung dch (mol/l) 1.2. Phng php trc quang (phng php ditizon)
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1.2.1. Bn cht ca phng php ditizon. Ditizon ( Diphenyl thiocacbazon) c cng thc: NH NH C6H5 S=C N = N C6H5 Tan trong cacbon tetra clorua v clorform to thnh dung dch c mu xanh l cy. dng phn t tc l trong mi trng acid hoc trung tnh. Ditizon rt kh tan trong nc. Dung dch cng c phn ng kim th tan ca ditizon cng tng do to thnh ion Dz -. HDz Dz- + H+ Ditizon to vi ion nhiu kim loi nhng ditizon c mu, t tan trong nc nhng tan trong cacbon tetra clorua hay cloroform. Cc ditizon c th tn ti di hai dng, tu thuc vo acid ca mi trng. - Trong mi trng acid hay trung tnh th chng tn ti di dng xeton. - Trong mi trng kim chng tn ti di dng enol. NH N C6H5 S=C MI N = N - C6H5 Cn bng chnh xy ra khi chit l Mn+ + nHDz Ngoi ra cn phai k ti cn bng: H+
1.2.2. ng dng.

N N - C6H MI S C MI N = N - C6H5

Dng enol thng t tan trong cacbon tetra clorua v cloroform. MDz + nH+ = HDz pKA = 8,7

Dz-

Hin nay phng php ditizon c dng rng ri xc nh cc c t kim loi trong lng thc thc phm. Phng php ny xc nh c lng nh kim loi t 0,1 ti 200 microgam ().
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1. 3. Chun b mu Km, ng, ch c trong lng thc phm vi lng nh nn mun xc nh chng cn phi v c ho lng thc thc phm. C hai phng php v c ho: 1.3.1. Phng php kh. a. Dng c, ho cht Capxun dung tch 250 ml Pipet 100 ml Bnh nh mc dung tch 250 ml Cn k thut Phu b. Tin hnh - Dng pipet ly chnh xc 100 ml thc phm ( nu l sn phm lng) hoc ly cn 100 g thc phm ( nu l sn phm kh) cho vo capxun. - Thm vo capxun 0,5g MgO2 v 0,5g Ca(CH3COO)2 tng tc v c ho v chng vic to thnh cc hp cht bay hi cha kim loi nng khi t ( v c ho). Cc cht ny nht thit khng c cha thic, ng v ch. - t capxun trn bp cch ct, t cho thc phm chy hon ton thnh than. - t capxun vo l nung, nung nhit 600- 7000C, n khi sn phm bin hon ton thnh tro xm, khong 3 gi. - Ly capxun ra khi l nung, ngui, cho vo capxun 20 ml acid nitric c ( tuyt i khng cha ng v ch) v 50 ml nc ct hai ln, nc trng cng chuyn vo bnh nh mc. - Thm nc ct n vch mc, lc k. 1.3.2. Phng php t a. Dng c, ho cht Capxun dung tch 250 ml Bp cch ct
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Bp cch ct Giy lc Magie dioxyt (MgO2) Canxi acetat Ca(CH3COO)2 Acid nitric c (d=1.4)

Bp in, l nung iu chnh c nhit ( 600- 7000 C)

Pipet 100 ml Bnh nh mc dung tch 250 ml Cn k thut

Giy lc Phu

Bp in, l nung iu chnh c nhit ( 600- 7000 C) - Ho cht: Acid nitric c ( d = 1,4) Acid sunfuric c (d = 1,84) Amon axetat NH4(CH3COO)2 b. Tin hnh - Ly lng mu nh trn cho vo capxun. Thm vo capxun 3 ml acid nitric c v 50 ml acid sunfuric c. - t capxun ln bp in, un si dung dch trong capxun. Tip tc un v c mi pht li nh thm 5- 20 git acid nitric c. Kh NO 2 mu nu s thot ra (lm trong t ht hi). - Nu thy dung dch trong capxun thm mu li th tng tc nh acid nitric c. Khi dung dch tr nn nht mu th gim tc nh acid nitric c, n khi dung dch khng mu th thi. Tip tc un cho khi trng bc i ht, ri li tip tc un si 10 pht na. - Nu sau dung dch vn khng mu th vic v c ho hon ton xong. Nu dung dch en tr li th nh acid nitric. - Ly capxun ra khi bp in. Cho vo capxun 0,20g amonaxetat, khuy cho tan ht. - Chuyn ton b dung dch t capxun vo bnh nh mc dung tch 250 ml. Thm nc ct hai ln n vch mc, lc k. Nu dung dch capxun b c th phi lc trc khi chuyn vo bnh nh mc.

Ghi ch: Phng php t kh ni trn xc nh ng v ch cng

c tha nhn xc nh thic. MgO 2 tch ra oxy hot ng gip oxy ho nhanh cc cht hu c. Ca(CH3COO)2 ng vai tr ph v MgO2 lm tng oxy hot ng phng vo cht hu c, do lm tng tc t. Cng c th
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dng Mg(CH3COO)2 v NaCl: Mg(CH3COO)2 v Ca(CH3COO)2; NH4Cl v NaCl, (NH4)2CO3 Song hn hp MgO2 v Ca(CH3COO)2 t l 1/1 lm cho tc t cht hu c nhanh nht. II. Phng php nh lng bng quang ph hp th nguyn t. 1. Nguyn tc chung ca phng php AAS Cc mu thc phm sau khi c v c ho hon ton, c phun vo h thng quang ph hp th nguyn t, ri ngi ta o hp th bc x t ngun pht bi hi nguyn t trong mu (c chuyn thnh hi nguyn t t do). Nguyn l ca phng php ny nh sau: Ngun sng n sc c pht t n Cathod rng ( HCl) hoc n phng in phi cc (EDL) hay n ph lin tc c bin in qua vng nguyn t ho n b cm bin ( detector) o cng bc x hay hp th. Mi kim loi c bc sng hp th c trng ring. n cathod rng (HCL) hay n phi cc (EDL) c cu to do chnh nguyn t c lm ngun pht bc x c trng. iu ny lm cho phng php n nh v t b nhiu. Cng bc x b hp th t l thun vi nng nguyn t c trong mu ( trong mt gii hn nng ). y chnh l c s phn tch nh lng. + Vi phng php F-AAS s dng ngn la l hn hp kh (khng kh-axetilen) 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

gian 20 giy; nguyn t ho nhit 1900oC, trong thi gian 3 giy. Vng tuyn tnh l: 2 50 ng/ml. 2. ng dng. Phng php ny c dng xc nh hm lng kim loi c trong mu thu sn, mu nc v nc thi. III. Phng php cc ph. Phng php Von Ampe l nhm cc phng php phn tch in ha da vo vic o dng ti in cc ch th theo th p vo, qua xc nh nng cht cn phn tch. Mt trong hai in cc c din tch b mt kh nh (b hn din tch b mt in cc kia kh nhiu ) nn rt d b phn cc v qu trnh kh hay oxi ha ca ion kim loi kho st xy ra trn chnh in cc ny. o cng dng in chy qua bnh in phn ng vi cc gi tr in th khc nhau t vo hai in cc, v I = f(E) ta s nhn c mt ng cong gi l ng cong phn cc. Qua xc nh nng cht cn phn tch. Phng php Von Ampe c hai nhm chnh l phng php cc ph v phng php Von Ampe ha tan. y l nhng phng php s dng rng ri nht trong phn tch in ha. 3.1. Khi nim v phng php cc ph. Phng php cc ph cng l phng php in phn, nhng y vic xc nh nng thng qua vic nghin cu quan h gia in p t vo hai in cc (E) vi dng in (I) hnh thnh trong qu trnh phn cc. Phng php cc ph c th nh tnh v nh lng nhiu cht bng cch in phn dung dch phn tch trn in cc git thu ngn, ri sau v ng biu din Dng-Th ghi s bin i cng dng theo s bin i cng th in cc ca s thu phn. V nguyn tc ca phng php cc ph Phng php cc ph bao gm cc giai on: - t cc th khc nhau vo in cc kh cc ion khc nhau v mi ion c mt th kh tng ng xc nh, do qua th kh ca ion c th nh tnh c ion .

- Nu tng dn th ca in cc nhng vo dung dch cht cn xc nh th cng dng s tng ln ng thi cho ti khi t c th kh ca ion trong dung dch. Trong iu kin nht nh, cng dng tng t l thun vi nng ion kh. Do s ph thuc gia cng dng v nng m nh lng c ion . S nguyn tc ca phng php cc ph

Tin hnh phn tch: Dung dch phn tch c np vo bnh nh phn c in cc thu ngn. Anot l lp thu ngn y bnh. Catt l git thu ngn ri lin tc t git m qun. t vo in cc th tng dn s to c dng c in cc tng dn, cng ny c iu chnh bng mt in k. Sau s thu c mt ng ph thuc Dng - Th (ng cong vn ampe) Dng khuych tn l dng c to do s kh ion trn in cc git thu ngn.
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Dng khuych tn c tnh theo cng thc Incovit: id = 605.Z.D1/2 .m2/3 . t1/6 Trong : id : cng dng khuych tn Z : ho tr ion b kh D : h s khuych tn hoc s phn t gam ion kh khuych tn qua b mt 1 cm2 trong 1 n v thi gian cho gadian nng bng n v. C : nng ion kh miliion g/ lit. M : khi lng thu phn ri khi mao qun trong n v thi gian, tnh ra mg/giy. T : thi gian git thu phn ri khi mao qun, s. Trong thc t kh xc nh c h s khuych tn D, nn ngi ta o song song dung dch cht tiu chun v cht phn tch, ri thit lp ng cong vn ampe ca c hai dung dch v tnh nng (X) cht cn phn tch theo cng thc: x= h tc
a.hx

Trong : a: khi lng cht trong dung dc tiu chun. hx v htc : chiu cao sng ca dung dc phn tch v dung dch tiu chun. Phng php cc ph khng ch xc nh cc cation, n cn c th xc nh c cc anion v phn t c kh nng kh trn in cc git thu ngn. u im ca phng php: nhy cao c th xc nh cc cht c nng 10-5 - 10-6 gam/lit. C th ng thi xc nh nhiu cht khng cn tch bit chng. Nhanh: ch tn vi pht xc nh nng cht trong dung dch. Chun b dung dch xc nh: Cn 10 50 g sn phm vo bt s ri em sy kh hoc c trn ni cch thu n cn kh. Sau thm vo bt 10 12 git acid sunfuric c (d = 1,84) ri a vo l nung t 5000C n thnh tro. Ly bt ra ngui thm vo 2 3ml acid clohydric c (d = 1,19) v c n kh trn ni cch thu.

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Cn trong bt c ho tan bng acid hydric long (1/1) un nh trn ni cch thu. Chuyn tt c vo bnh nh mc dung tch 50 ml (dung dch ch chim na th tch ca bnh). Trung ho acid bng amoniac. Thm nc ct n vch mc lc k ri lc. Gi ly kt ta hydroxyt ch v thic trn giy lc. Nc lc I dng xc nh ng. Kt ta trn giy lc c ho tan bng acid HCl (1/1) nng, thm vo 2 3 g acid tactric, 1 lng natri sunfit v un trn ni cch thu cho bc ht SO2 i. Sau khi lm lnh dung dch c chuyn vo bnh nh mc dung tch 50 ml, trung ho acid d bng amoniac c n d, thm nc ct n vch mc lc k ri lc. Nc lc II dng xc nh ch. Kt ta hydroxyt thic c ho tan trong HCl(1/1) trong bnh nh mc 50 ml, thm 0,1g canxi hypophotphit CaH2PO2 v thm acid Clohydric (1/1) n vch. Lc dung dch ny, nc lc III dng xc nh thic. 3.2. ng dng. Trong phn tch thc phm phng php cc ph dng xc nh cc ion kim loi nng, mui n, ng fructoza, saccaroza, cc vitamin C, B1, xc nh c tnh nm men v vi c t cht hu c. 3.3. Phng php Von Ampe ha tan xung vi phn DDP Qu trnh xc nh bng phng php Von ampe ho tan xung vi phn gm hai giai on: - Giai on 1: in phn lm giu kim loi trn b mt vi in cc mng thy ngn (catot): M2+ + 2e = M (Pb, Cu, Zn, Cd) - Giai on 2: Ha tan kim loi kt t trn b mt in cc v ghi dng ha tan bng phng php Von ampe kt hp xung vi phn (DPP) di dng pic. L phng php ti u nht xc nh kim loi nng. Trong nhng iu kin thch hp cng dng ha tan t l thun vi lng kim loi kt ta trn b mt in cc tc l nng cht cn xc nh trong dung dch. E Phng php ny c nhy, chn lc v lp li cao, thc hin nhanh v kh n gin . Trong phng php cc ph xung vi phn,Fei cc git thu ngn in c phn cc bng mt in p mt chiu bin thin tuyn tnh vi tc
Estep 11

tstep

Chu k git

 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.

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 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
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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.

Phn III: Cc phng php xc nh I. Cc phng php xc nh Ch (Pb)

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 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. 1. Phng php cc ph Trong phng php ny, ngi ta phn cc in cc git thy ngn bng mt in p mt chiu bin thin tuyn tnh vi thi gian nghin cu cc qu trnh kh cc ca cht phn tch trn in cc . V vy, thit b cc ph gm hai phn chnh l my cc ph v h in cc bao gm in cc git thu ngn v in cc so snh. ng cc ph biu din s ph thuc ca chiu cao cng dung vi nng cht phn tch. 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) 3 b kh thun nghch v cho sng cc ph vi th bn sng -0,76 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.
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+ 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. Nu mu cha lng ln cht hu c cn ph hu chng nh trong phng php dithizon trn. loi oxi khng dng Na2SO3 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 . 2. Phng php nh lng bng quang ph hp th nguyn t. * Thit b, dng c: - My quang ph hp th nguyn t c trang b n catt ch rng bc sng ci t l 283,3 nm, s dng ngn la axetilen khng kh vi chiu rng ca u t l 4 inch. - Chn s dung tch 50ml, su 5cm hoc cc thu tinh c m bng thch anh dung tch 100ml. - T sy nhit 1500C - L nung kim sot c nhit t 2500C 6000C vi sai lch khng qu 100C.

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- Dng c thu tinh c ra sch bng acid nitric nng 8N v trng li bng nc ct trc khi s dng. - Cn phn tch c chnh xc loi n 0,01g v loi n 0,001g. * Ho cht v cht chun: -Dung dch acid clohidric (HCl) nng 1N : pha long 82ml dung dch acid clohidric m c bng nc ct 1000ml. - Dung dch acid nitric 1N - Acid Percloric HClO4 m c 70,5% - Oxyt Lantan La2O3 - Etylen dinitritetraaxetac EDTA - Dung dch m + Cho 163g EDTA vo trong bnh nh mc 2000ml, sau thm 200ml nc ct v mt lng va NH4OH ho tan ht EDTA. Thm 8 git ch th methyl da cam vo dung dch EDTA. + Cho 500ml nc ct vo mt cc thu tinh ri t t cho thm 60ml dung dch acid percloric m c, khuy u ri ngui. Sau , cho 50g acid lantan vo cc ri khuy u ho tan ht lng acid lantan ny. + Rt t t dung dch oxyt lantan vo dung dch EDTA pha trn, va rt va khuy mnh. Nu cn thit, thm NH4OH vo dung dch trn gi cho dung dch c tnh kim vi methyl da cam (dung dch c mu vng). - Dung dch ch chun: + Dung dch chun gc 1mg /l: ho tan 1,5985g nitrat ch chun trong khong 500ml dung dch acid nitric 1N. Sau nh mc thnh 1000ml bng dung dch HNO3 1N trong bnh nh mc. + Dung dch chun trung gian 10mg/ml: ly chnh xc 10ml dung dch chun gc cho vo bnh nh mc 1000ml, thm 82ml dung dch HCl 1N vo bnh. Sau nh mc ln bng nc ct. + Dung dch chun lm vic Pha long dung dch chun trung gian thnh cc dung dch chun lm vic c hm lng ch ln lt l 0,1; 0,2; 0,6; 1; 3; 5 v 10mg Pb/ml bng dung dch HCl 1N trong cc bnh nh mc dung tch 50ml. Phng php tin hnh - Chun b mu trng
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Lm bay hi 4ml dung dch HNO3 m c trong chn s n kh trn bp cch thu. Ho tan cn bng 20ml dung dch HCl 1N v chuyn dung dch vo bnh nh mc 25ml. ngui bnh v nh mc ti vch bng HCl 1N. Yu cu hm lng ch trong mu trng khng c ln hn 10mg. - chun b mu th + Cn khong 25g mu cho vo chn s ri sy kh trong t sy trong thi gian 2h nhit t 1350C 1500C. chuyn chn s vo l nung v tng dn nhit n 5000C. gi nhit l 5000C trong 16h tro ho mu. + Ly chn s ra ngui n nhit trong phng. Cho 2ml HNO 3 m c vo chn ri bay hi dung dch trong chn cho n kh trn bp cch thu. t ch s tr li vo l nung nhit thng, sau tng dn nhit n 5000C v gi nhit ny trong vng 1gi. + Ly chn ra ngui v lp li thao tc nh trn cho n khi tro c mu trng hon ton. + Cho 10ml dung dch acid clohydric nng 1N vo chn c tro ri ho tan tro bng cch nung nng. chuyn gn dung dch vo bnh nh mc 25ml. + un nng phn tro cn li trong chn 2 ln, mi ln vi 5ml dung dch clohydric nng 1Mri rt dung dch vo bnh nh mc 25ml ni trn. ngui v nh mc ti vch bng acid clohydric nng 1N ri lc u. Tin hnh phn tch: + Ti u ho cc iu kin lm vic ca my quang ph hp th nguyn t ti bc sng cng hng 283,3nm v t tc dng ca hn hp acetylen khng kh theo hng dn ca nh sn xut v iu kin lm vic chun vi ch. + Xy dng ng chun vi cc hm lng ca ch ln lt l 0,0; 0,2; 0,4; 1,0; 3,0; 5,0; v 10,0mg/ml da trn hp th ca chng. Trong trng hp tn hiu nhn c yu, phi iu chnh khuych i c hp th A ca dung dch chun (0,2mg/ml) khng nh hn 1%. + Khi ng chun c tuyn tnh tt, tin hnh o hp th ca dung dch mu th v mu trng c chun b nh sau: i vi dung dch mu th trong, khng c cn lng: Tin hnh xc nh hp th 3 ln theo cc bc sau: bm ln lt dung dch chun sau l dung dch mu th. nu s lng dung dch nhiu th th bm ln lt mt
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dung dch chun v 3 dung dch mu th cho n khi bm ht lng dung dch chun v mu th, mu trng. i vi dung dch mu th c: thm 1ml dung dch m vo cc dung dch mu th, mu trng chun b trn v cc dung dch chun. Sau tin hnh xc nh hp th ca cc dung dch nh i vi dung dch mu th trong. + Tnh hm lng ch trong mu thng qua ng chun sau khi tr i mu trng. Yu cu tin cy ca php phn tch. + hp th li ca bm 2 ln. lch chun (CVs) tnh theo hp th ca hai ln bm lin tip ca cng mt dung dch chun phi nh hn 0,5%. thu hi c xc nh bng cch s dng 5 mu cho vo mt lng dung dch ch chun bit chnh xc nng . thu hi tnh c phi nm trong khong t 85% - 115%, thu hi trung bnh ln hn 90%. Tnh kt qu: Hm lng ch trong mu thu sn c tnh theo cng thc sau: + i vi dung dch mu th trong, khng c cn lng. CPb =
m Pb . 25 M Vd 25

+ i vi mu th c phi b xung thm dung dch m. CPb = mPb . V 1 . M d

Trong : CPb: hm lng ch c trong mu th (mg/g) mPb: hm lng ch c trong dung dch mu tnh c theo ng chun mg/mol. 25: th tch dung dch acid clohydric nng 1M dng ho tan mu (ml) Vd: th tch dung dch mu th b sung 1ml dung dch m phn tch (ml) M: khi lng mu th (g)

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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 Diphenylthiocacbazon l thuc th hu c c kh nng to phc cng cua vi hng lot ion kim loi, trong c ch. Phc ch ithizonat kh tan trong nc nhng d tan v tan nhiu trong cc dung mi hu c nh CHCl3 hoc CCl4. V vy, ngi ta thng dng phng php chit trc quang xc nh ch. Trong CCl 4 th dithizonat c mu , cc i hp ph = 520nm. Ch dithizonat c chit chn lc v nh lng t dung dch nc c pH = 8 9 cha lng d xianua l cht dng che nhiu kim loi khc c th cng b chit vi ch. Trong mi trng k trn, cng b chit vi ch c c tali, bbitmut v thic (II). Tali khng cn tr vic xc nh ch nhng thic v bitmut ngn cn nn cn c tch trc bng cch chit chng t mi trng axit. Trong mi trng axit ch khng b chit, cn li trong pha nc. Thic v bitmut c tch trc nh sau: thm hhidrazin vo dung dch mu nc, un nng kh Sn4+ xung Sn2+ v kh cc cht khc. Sauk hi ngui, thm dung dch natritactrat vo, a pH ca dung dch n 2,3 3 ( bng dung dch axit tactric). Tin hnh chit nhiu ln, mi ln bng 5ml dung dch dithizon 0,1 % trong CHCl3. Tin hnh chit cho n khi pha hu c vn gi nguyn mu xanh ca dithizon cho n khi pha hu c vn gi nguyn mu xanh ca dithizon. Cui cng, lc pha nc vi ln vi CHCl3 ( mi ln dng 5ml ) n khi pha khng cn mu xanh. Tin hnh chit nh vy khng nhng tch c thic m cn tch c c thy ngn, bc v ng.

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Nu nh trong mu nc cha lng ng k cc cht hu c cn phi v c ha chng bng cch chho vo vi ml HNO3 c v HClO4 c ri c mu n kh, sau tm t b kh bng axit nitric v ha tan bng nc ct. cc cht oxi ha cn c kh trc bng hidrazin. 4. Phng php Von Ampe ha tan xung vi phn Hin nay ngi ta s dng phng php Von Ampe ha tan kt hp xung vi phn (DPP) c th xc nh c 10-9M Pb2+ vi thi gian khng qu 3 pht. C th ni hin nay DDP l phng php cc ph hon chnh nht xc nh hm lng kim loi nng v phng php ny c nhy, chn lc cao v c tnh vn nng i vi hu ht cc i tng phn tch. II. Cc phng php xc nh Cadimium ( 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 sng = 515 nm. Bng phng php ny c th xc nh hm lng t phn trm mg n miligam Cd. Trong mi trng kim c mt s kim loi cng b chit cng cadimi nh bc, niken, coban, ng, loi tr cc nguyn t ny ngi ta chit chng trong mi trng axit trc khi xc nh cadimi. 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

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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 CHCl 3, 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 CCl 4. Nu trong mu c cha Ni th tch bng dimetylglioxim nh sau: 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 NH 3 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 CHCl 3. Cui cng ra tng nc bng 5 ml CCl4.

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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 CCl4 mi ln chit. 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 HNO3, 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 da vo ng chun tnh kt qu (mu chun c chun b trong MIBK). Phng php AAS c ng dng xc nh cadimi trong nhiu i tng khc nhau. bc song 228,8nm th t nhy 0,01g/ml, gii hn pht hin 0,004g/ml i vi k thut ngn la. i vi k thut khng ngn la th t nhy 0,008g/ml , gii hn pht hin 0,002g/ml.

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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. 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
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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. 4. Cc phng php in ha Cadimi c th xc nh bng phng php cc ph. Nguyn tc ca phng php ny da trn s kh ion Cd2+ trong mi trng axit, trung tnh hoc kim. Trong mt khong nng nht nh ca Cd2+ th cng dng khuch tn (hay chiu cao song cc ph) t l vi nng Cd2+ theo phng trnh Incovich: I= k.C Phng php in ha dc s dng ph bin hin nay l phng php von ampe ha tan anot, l mt phng php xc nh cadimi c nhy cao. y l phng php va xc nh va lm giu cht phn tch. Trc tin cadimi c in phn lm giu ln in cc lm vic th khng i. Sau ha tan Cd bng cch phn cc ngc anot ri ghi li ng cong von ampe ha tan ca cadimi. Khi xc nh cadimi theo phng php cc ph nu trong mu nc hm lng Cu ln th cn che bng xianua. 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.

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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) 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 1,23.10 5l.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).

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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 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 1,78.10 5 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 1,27.105l.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 Zn 2+ 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 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%.

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 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 NH 3 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 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

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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 Na2SO3 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 0,010,5mg 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

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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.4.2.2 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 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 H2SO4 c, 3 5 ml HNO3 c v lm bay hi dung dch trong t ht cho n khi

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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 NH 3 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 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 Na2SO3 + 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.

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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.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 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)

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Bc 2 : Ho tan kt ta trn anot : qu trnh anot, qut th t m sang dng dn. M(Hg) - ne Mn+ + Hg Phng trnh pc : ip = K . n3/2 . D1/2M(Hg) . CoM . V1/2 . r2 . tacc Trong : ip : Dng pc D1/2M(Hg) : H s khuch tn ca kim loi M trong hn hng K : Hng s n : S electron trao i r : Bn knh git tacc : Thi gian lm giu V : Vn tc qut Lng kim loi c lm giu catot trong hn hng :

iacc . tacc
C
o M

= 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

Hg2A2

2e

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.
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