Nghin cu s to phc ca mangan vi 1-(2- PYRIDYLAZO) -2-NAPHTOL(PAN) trong mi trng nc - etanol v ng dng CH to KIT xc nh hm lng Mn(II) trong mi trng nc

Nguyn Th Nhung, Nguyn Th Kim Thng 1. M u Nhu cu v nc sch ngy cng gia tng v s lng v cht lng. nhim NH4+, NO2-, Fe v Mn trong nc sinh hot v nc ngm ang l vn c ton x hi quan tm. C rt nhiu phng php xc nh Mn trong cc i tng khc nhau, nh phng php hp th phn t, phng php ICP-MS, phng php so mu da trn c s oxy ho Mn2+ bng persulphat [1,2,3]. Cc phng php ny c nhy v chnh xc cao nhng cn phi u t ban u rt ln vi quy trnh phn tch kh phc tp v phi bo qun mu v vn chuyn v phng th nghim. y l vic lm kh tn km nht l khi khu vc kho st xa cc phng th nghim. gip cc nh quan trc mi trng, cc nh cng ngh ch ng c cng vic ca mnh, nht l cc vng nui trng thy sn ca nng dn, chng ti nghin cu ch to b KIT xc nh nhanh Mn2+ trong mi trng bng phng php o mu trc tip vi ch th PAN. 2. Phn thc nghim Tt c cc ho cht s dng u thuc loi tinh khit v tinh khit phn tch (P.A.) c bn trn th trng. Dung dch Mn(II) c nng 100mg/l c iu ch bng cch ly 9,09ml KMnO4 c nng 0,1N, thm nc ct 2 ln n khong 80ml, sau dng H2SO4(1:4) chnh pH ca dung dch n 2 , un nh trn bp in, dng H2O2 15% kh n ht mu dung dch sau un ui ht H2O2 d, ngui, cho vo bnh nh mc 100ml, nh mc bng nc ct 2 ln n vch. Dung dch Mn2+ long hn c pha hng ngy, trc khi s dng. Dung dch PAN vi nng 5.10-3 M c chun b nh sau: cn chnh xc 0,1245 g ha tan trong 100ml etanol 98%. Dung dch m pH=9 c pha ch theo ti liu [4]. Mt quang ca cc dung dch c o trn my DR. 2000, M. pH ca dung dch c o trn my Microprocessor pH ion-meter pMx 3000(WTW). 3. Kt qu v tho lun
3.1. Kho st s hp th nh sng ca thuc th PAN v phc Mn - PAN

Dung dch PAN trong nc c mu , khng bn, d b kt ta, nhng li d tan v bn trong etanol, metanol, CHCl3... cho mu vng [5]. Chng ti kho st tnh tan v bn ca PAN trong mi trng nc- etanol cc t l khc nhau. Kt qu thc nghim cho thy, khi t l etanol trong dung dch t10% th thuc th PAN bn trong 15 pht, t l etanol cng cao, bn ca dung dch PAN cng tng. Tng t, khi t l etanol tng th ca phc Mangan(II)-PAN cng bn. Tuy nhin, khi t l etanol cao gi thnh phn tch s t. Do vy, chng ti chn t l etanol l 10 % v tin hnh kho st s hp th nh sng ca dung dch thuc th PAN v phc Mn(II) - PAN : a. Ly 1ml thuc th PAN c nng 5. 10-3 M (pha trong cn tuyt i) cho vo bnh nh mc 10ml, thm 1ml m NH4CL/NH4OH c pH=9, nh mc bng nc ct 2 ln v yn 10 pht sau o ph hp th nh sng t bc sng 400-650nm, dung dch so snh l nc ct 2 ln.

b. Vi phc Mn(II)-PAN, tin hnh tng t phn trn, nhng sau khi cho thuc th thm vo 1ml Mn(II) c nng 1.10 -4 M, lc u, nh mc, yn 10 pht ri o ph hp th nh sng bc sng 400-650nm. Kt qu kho st c biu din trn hnh 1. Nh thy trn hnh 1, thuc th PAN c cc i hp th bc sng 470nm, cn phc Mn(II)-PAN c 2 cc i hp th, mt bc sng 470480nm, gn trng vi cc i hp th ca PAN, cn cc i kia 570-580nm. Ti bc sng 580nm, hp th ca PAN gn bng khng, nn gi tr o c chnh l mt quang ca phc Mn(II)-PAN to thnh. V vy, chng ti chn bc sng 580nm kho st hp th quang ca phc Mn(II)-PAN trong cc th nghim tip theo.
1.2 1

Mt quang

0.8 0.6 0.4 0.2 0

350 400 450 500 550 600 650 700

PAN Mn-PAN

Bc sng
Hnh 1. Ph ca thuc th PAN (5.10-4M); phc Mn(II)-PAN (Mn(II) = 10-5M); pH = 9

3.2. Kho st nh hng ca pH n s to phc

M t quang

tm iu kin ti u cho phn ng to phc gia Mn(II) vi PAN, chng ti kho st nh hng ca pH: chun b dy dung dch c pH thay i t 3-10, nng thuc th PAN l 5.10-4M, nng Mn(II) l 10-5M, mt quang c o bc sng 580nm. Kt qu c biu din trn hnh 2. Theo kt qu trn hnh 2, phc Mn(II)PAN to thnh tt nht trong khong pH= 8,5 - 9,5, gi tr pH ny cng hp th quang ca dung dch cao v n nh, v vy chng ti chn pH = 9,0 cho cc nghin cu tip theo.
3.3. Kho st nh hng ca thi gian dn s to phc

0.6 0.5 0.4 0.3 0.2 0.1 0 2 3 4 5 6 7 8 9 10 11 12

Hnh 2: S ph thuc mt quang ca phc Mn - PAN vo pH
pH

Cho vo bnh dnh mc 10ml, 1ml dung dch m pH=9, 1ml thuc th PAN c nng 5.10-3 M v 1ml Mn(II) c nng 1.10-4 M, nh mc bng nc ct 2 ln, thi gian o sau 1 pht k t khi cho Mn(II) vo v o bc sng 580nm. Kt qu kho st c trnh by trn hnh 3. Kt qu trn hnh 3 cho thy, phc Mn(II)PAN to thnh hon ton v bn mu trong khong t 5- 17 pht, nn chng ti chn thi gian o phc mu l 10 pht.

0.6 Mt quang 0.55 0.5 0.45 0.4 0.35 0.3 0 5 10 15 20 25 Thi gian( pht)

Hnh 3. Kho st bn ca phc theo thi gian

3.4. Xc nh thnh phn v h s hp th phn t gam ca phc

Thnh phn phc c xc nh theo phng php bin i lin tc mt trong hai tc nhn. Trong th nghim ny, chun b dy dung dch thuc th PAN c nng thay i t 0.6 0-0,6.10-5M, nng Mn(II) = 10-5 M c nh, 0.5 pH=9, thi gian tin hnh o quang l 10 pht 0.4 sau khi chun b xong dung dch. Kt qu biu 0.3 din s ph thuc gia gi tr mt quang ca 0.2 phc Mn(II) - PAN v nng thuc th PAN 0.1 c trnh by trn hnh 4.

M t quang

Trn hnh 4 cho thy phc to thnh c thnh phn 1: 2. (Mn(II) : PAN=1:2). Da vo thc nghim, tnh c h s hp th phn t l 0,05
3.5. Nghin cu nh hng ca ion cn v cch loi tr

0 0 0.1 0.2 0.3 0.4 0.5 0.6 Dung dch thuc th PAN( ml)
Hnh 4. S ph thuc D-CPAN

Theo ti liu th thuc th PAN ngoi Mn(II) cn to phc vi mt s ion kim loi nh Cu(II), Pb(II), Cd(II), Zn(II), Fe(II), Fe(III), Co(II), Hg(II), Ni(II)[5,6]. Hng s bn ca mt s phc ion kim loi vi PAN: logK[Mn(PAN)2]=16,4; logK[Cu(PAN)2]=23,9; logK[Ni(PAN)2]=25,3; logK[Zn(PAN)] = 10,9[5]. ng thi cc kim loi ny cng to phc vi ion CN-, nhng ring Mn(II) khng phn ng vi CN-. Hng s bn ca cc ion kim loi vi ion CN-: log[Cu(CN)4]2- = 25; log[Ni(CN)4]2-= 30,1; log[Zn(CN)4]2- =12,6; log[Cd(CN)4]2- =18,85[ 6]. Theo cc s liu trn th phc ca mt s ion kim loi vi CN- bn hn phc ca cc ion kim loi ny vi PAN. Chng ti tin hnh kho st nh hng ca cc ion kim loi Cd(II), Cu(II), Pb(II), Zn(II), Ni(II) n s to phc ca PAN vi Mn(II) v phng php loi tr: chun b 10 bnh nh mc 10ml c [PAN] =5.10-4 M, [Mn(II)]= 10-5M, pH = 9, t bnh th 1 n bnh th 5 ln lt cho cc ion kim loi Cd(II), Cu(II), Pb(II), Zn(II), Ni(II) vi nng 10-5M, nh mc bng nc ct 2 ln, o sau 10 pht bc sng 580nm. T bnh th 6 n bnh th 10 tin hnh tng t nh phn trn nhng sau khi cho cc ion kim loi thm vo 1m [CN-] =10-2M. Kt qu thc nghim cho thy khi trong dung dch c cc ion Cu(II), Pb(II), Cd(II), Zn(II), th mt quang ca phc Mn(II) - PAN bt u thay i khi nng ion [Mn] : [Cd] = 15 ln, [Mn] : [Cu] = 2,5 ln , [Mn] : [Pb] = 16, [Mn] : [Zn] = 1,0, khi thm[CN-] =10-3M vo dung dch th loi tr c nh hng ca cc ion kim loi . Kt qu thc nghim c trnh by trong bng 2.
Bng 2. S ph thuc mt quang ca phc Mn(II)-PAN vo cc ion nh hng khi khng c v khi c cht che CN-

STT 1 2 3 4 5

Cc ion nh hng ( 10-5M) Pb Cu Cd Zn Ni

Mt quang(D) C CN-10-3M Khng c CN1,02 0,52 0,94 0,49 1,11 0,51 0,88 0,49 0,80 0,52

3.6. Xy dng ng chun xc nh Mn(II)

hp th quang(D)

Cho vo bnh nh mc 10 ml, 1ml dung dch m pH=9, 1ml thuc th PAN c nng 5.10-3M v, nng Mn(II) thay i trong khong 0,1 -1,0mg/l, nh mc bng nc ct 2 ln, yn 10 pht ri o mt quang bc sng 580nm. Kt qu thc nghim c trnh by trn hnh 5. T hnh 5 c th thy hp th quang tun theo nh lut Beer trong khong nng Mn2+ t 0,1 - 1,0mg/l. Kt qu ny khng nh c th xc nh hm lng Mn2+ trong thc t vi gii hn pht hin (LOD) l 0,02mg/l.

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.2 0.4 0.6 0.8 1 Nng Mn(mg/l)

Hnh 5. S ph thuc D-CMn

3.7. Xc nh Mn2+ trong mt s mu thc t.

p dng cc iu kin ti u tm c trn, chng ti xc nh hm lng Mn(II) trong mt s mu nc ngm H Ni. Quy trnh phn tch: Ly 7,5 ml mu nc, cho thm 0,5 ml NaCN 10-3M, 1,0 ml dung dch PAN 5.10-3M pha trong cn tuyt i, 1ml dung dch m pH = 9. Sau 10 pht do mt quang bc sng 580nm.(Nu nng Mn2+ ln hn 1,0mg/l th cn pha long). Kt qu phn tch 10 mu nc ngm khu vc H Ni c trnh by trong bng 3.
Bng 3: K t qu phn tch Mn(II) trong nc ngm khu vc H Ni

STT 1 2 3 4 5 6 7 8 9 10

K hiu mu T1 T2 T3 T4 T5 T6 T7 T8 T9 T10

Hm lng Mn(II) (mg/l) (theo pp trc quang) 0,10 0,25 0,10 0,20 <0,02 0,25 0,50 0,05 0,10 3,15

Hm lng Mn(II) (mg/l) (theo pp AAS) 0,09 0,27 0,12 0,19 <0,01 0,26 0,51 0,04 0,11 3,20

Nhng kt qu thu c ch ra rng phng php so mu vi ch th PAN c tin cy cao, hon ton thch hp phn tch ion Mn(II) trong cc mu thc t c.
3.8. Ch to KIT kim tra hm lng Mn(II)

Da trn cc kt qu nghin cu trnh by trn, chng ti ch to KIT kim tra hm lng Mn(II) ti hin trng. s thay i mu gia cc nng Mn(II) trong dung dch c th phn bit bng mt thng, chng ti chn dy dung dch lm bng mu chun l: 0,0 ; 0,2; 0,4; 0,6; 0,8 mg/l.

Cch xc nh ion Mn(II) bng KIT ch to c: ly 1 lng mu cn phn tch l 5ml, thm 3 git dung dch che CN- (ddA), thm 5 git dung dch m pH= 9 (ddB ) v 5 git PAN (ddC). Sau 10 pht so snh mu trong ng nghim vi mu trn bng chun. 4. Kt lun 1) nghin cu s to phc ca Mn(II) vi thuc th PAN trong mi trng nc- etanol bng phng php trc quang. Kt qu cho thy phng php c tin cy cao, c th p dng xc nh Mn(II) trong cc mi trng nc.
Hnh 6: KIT kim tra nhanh hm lng Mn(II) sn xut c

2) p dng kt qu nghin cu s to phc MN(II)-PAN ch to b KIT kim tra nhanh nng Mn(II) trong mi trng nc.

Ti liu tham kho

1. P. K. Tarafder, R.K. Mondal, L.Kumkal, P. Murugan and D. P. S. Rathore. Liquid-Liquid Extraction and Spectrophotometric determination of Mn(II) in Geochemical samples. Chem. Anal. (Warsaw), 49 (2004), pp. 251-258. M.Noroozifar and M. Khorasani-Motlagh. Floww-Injection system for the Spectrophotomet-ric Determination of Mn(II), using Sodium Bismuthate as an Oxidant and Sym-diphenylcar-bazide as a complexing Agent, Chem. Anal. (Warsaw), 49 (2004), pp. 405-413. Michel Hoenig and Paul Van Hoeyweghen. Direct Determination of Manganese in Sea Water by Electrothermal Atomic Absorption Spectrometry with Deuterium Background Correction using a Platform and Platinum Matrix Modifier, Instute for Chemical Reaseach, N. AA-67(1965), pp 1-5. Phm Lun, Nguyn Xun Dng, Sch pha ch dung dch, NXB Khoa hc v K thut, H Ni, 1987, 67 tr. E. Gorodkiewicz and Z. Figaszewski. Study on the Stability and Formation Rate of the Complex Compounds of Ni(II), Cu(II), Hg(II) with PAN by Potentiometric and Spectrophotometric Methods. Chemical analyis, vol. 45(2000), N06, pp.867-879. . . . . . , , 1971,173c.

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