CHNG 1.

TNG QUAN
1.3. TNH CHT HA HC CA ASEN 1.3.1. Tnh cht ca asen n cht 1.3.2. Tnh cht cc hp cht ca asen a. Cc hp cht asen v c [10, 26] Tnh cht ca As(III) Hp cht c tnh thng phm quan trng nht l As(III) oxit c cng thc phn t As2O3 hoc As4O6 t tan trong nc( ~ 2% nhit 25 oC v ~8,2 % 98oC), khi tan trong nc to thnh dung dch c tnh axit yu. Asin AsH3 c mi ti v rt c. Asin c iu ch bng cch cho km trong axit clohyric tc dng vi mt hp cht tan c ca asen. Mui AsCl3 khng bn trong nc d b thy phn to thnh As(OH)3. Axit ca As(III) tc dng c vi AgNO3, dung dch CuSO4 v phn ng vi I2 trong mi trng axit [10]. Tnh cht ca As(V) 1.2.3. Phn ng pht hin asen 1. Phn ng to thnh AsH3 Khi lng asen rt nh (< 0.1 mg), tt nht l pht hin n di dng hidroasenua AsH3, hp cht ny nhn c bng cch kh hp cht asen bng km trong mi trng axit sunfuric [19] (cn s c mt ca Fe2+) : * 2Fe2+ + HAsO42- + 3H+ 2Fe3+ + AsO2- + 2H2O Fe2+ - 1e Fe3+ HAsO42- + 2e + 3H+ AsO2- + 2H2O * 3Zn + 2AsO2- + 7H+ 3Zn2+ + AsH3 + 2H2O Zn - 2e Zn3+ AsO22- + 6e + 7H+ AsH3 + 2H2O AsH3 to thnh, b phn hu khi un nng to thnh mt gng asen, vi AgNO3 n kt ta mu en (Ag); vi HgCl 2 to thnh hp cht mu vng nu AsH2(HgCl), AsH(HgCl2), As(HgCl)3, As2Hg3. [2] Thc t phn ng c thc hin nh sau: - Cho vo ng nghim 1-2ml axit H2SO4 tinh khit - Thm vo vi git dung dch th nghim - Thm vo 1 vi ming Zn khng cha tp cht asen Khi AsH3 c tch ra, c th pht hin bng 1 s phng php: a. Phn ng kh Ag+ y ng nghim c cha AsH3 tch ra bng bng gc c thm t bng dung dch Pb(CH3COO)2. Che ming ng bng t giy lc tm t bng dung dch AgNO3 50%. Nu c asen, trn giy lc s xut hin vt nu hay en. [19] kim tra tinh khit ca thuc th (axit v kim), cn lm th nghim rng_ l nhng phn ng tng t nhng khng thm dung dch th nghim. iu kin tin hnh phn ng: - Tt c cc phng php da trn s to thnh AsH 3 phi khng c mt cc cht m trong iu kin th nghim chng to thnh H2S, SO2, PH3. 1

- kh asen, dng cc hp kim ca km vi ng, nh hp kim Cu-Al-Zn cng thun tin. - Phi dng nhng nguyn liu ban u l loi tinh khit ho hc, thm ch c vt asen cng khng c c trong . - S un nng cng nh thm trc st (II) sunfat FeSO 4 s lm tng kh nng phn ng kh hp cht As(V). * AsH3 rt c, cn ch thng gi khi lm th nghim 2. Kh cc hp cht Asen thnh As 3. Phn ng ca ion Asenit [26] a s cc Asenit khng tan trong nc, ch c cc Asenit ca kim loi kim, amoni v magi l c th tan, l c im khc vi Asenat. - Phn ng xi ha Asenit thnh Asenat bng H2O2 trong mi trng kim: AsO33+ H2O2 AsO43- + H2O Phn ng xi ha Asenit thnh Asenat c th tin hnh bi nhiu cht xi ha khc nhau, nhng tt nht l s dng H 2O2, v lng d H2O2 d b phn hy khi un nng. - Trong mi trng kim yu Asenit b xi ha bi I2 thnh Asenat: AsO33+ I2 +2OH- AsO43- + 2I- + H2O 4. Phn ng ca ion Asenat [26] - Phn ng vi hn hp magi (MgCl2 + NH4OH +NH4Cl) to tinh th trng: HAsO42- + Mg2+ + NH4OH MgNH4AsO4+ H2O - Phn ng vi Molipdatamoni to thnh kt ta mu vng: (NH4)3AsO4 + 12MoO4- +24H+ (NH4)3H4[As(Mo2O7)] +10H2O Asenit khng c phn ng vi Molipdatamoni. - Phn ng kh n Asin: Tt c cc hp cht As(III) v As(V) u b kh trong mi trng axit bng Zn kim loi: 4Zn + AsO43- + 11H+ AsH3 + 4Zn2+ + 4H2O C th tin hnh phn kh ng thi As(III) v As(V) bng Al kim loi trong mi trng kim. Asin c tnh kh mnh (phn ng Gtaita): AsH3 + 6AgNO3 + 3H2O H3AsO3 + Ag+ 6HNO3 1.3.3. Phn ng pht hin Asenit v Asenat [28] a s cc Asenit khng tan trong nc, ch c cc Asenit ca kim loi kim, amoni v magi l c th tan, l c im khc vi Asenat. Phn ng pht hin Asenit: 3Ag+ + AsO33 Ag3AsO3 vng (1.8) Phn ng pht hin Asenat: - Phn ng to kt ta mu socola: 3Ag+ + AsO43 Ag3AsO4 mu socola (1.9) - Phn ng vi hn hp magi (MgCl2 + NH4OH + NH4Cl) to kt ta tinh th trng: HAsO42- + Mg2+ + NH4OH MgNH4AsO4+ H2O (1.10) - Phn ng vi amonimolipdat to thnh kt ta mu vng: (NH4)3AsO4 + 12MoO4- +24H+ (NH4)3H4[As(Mo2O7)] +10H2O (1.11) 2

- Asenit khng c phn ng vi amonimolipdat. 1.4. CC PHNG PHP PHN TCH ASEN [14] 1.4.6. Phng php trc quang trn c s hp cht mu xanh Molipden Nh trn trnh by, xc nh hm lng As c nhiu phng php khc nhau, trong bn lun vn ny chng ti s dng phng php trc quang ng chun trn c s hp cht mu xanh molipden. y l phng php c nhy cao, kt qu phn tch n nh. C s khoa hc ca phng php da trn cc phn ng sau: Phn ng kh n Asin [28] Cc hp cht Asenit v Asenat u b kh trong mi trng axit bng Zn kim loi: 4Zn + AsO43- + 11H+ AsH3 + 4Zn2+ + 4H2O (1.13) + 2+ 3Zn + 2AsO2 + 7H 3Zn + AsH3 + 2H2O Zn - 2e Zn2+ AsO22- + 6e + 7H+ AsH3 + 2H2O C th tin hnh phn kh ng thi As(III) v As(V) bng Al kim loi trong mi trng kim. Phn ng oxi ha Asin thnh Asenit [28] Asin c tnh kh mnh (phn ng Gtaita): AsH3 + 6AgNO3 + 3H2O H3AsO3 + Ag+ 6HNO3 (1.14) Phn ng oxi ha Asenit thnh Asenat [28] - Dng H2O2 trong mi trng kim: AsO33+ H2O2 AsO43- + H2O (1.15) Phn ng oxi ha Asenit thnh Asenat c th tin hnh bi nhiu cht oxi ha khc nhau, nhng tt nht l s dng H 2O2, v lng d H2O2 d b phn hy khi un nng. Hydro peroxit (H2O2) l cht oxi ha c hiu qu, c bit nu trong nc th c cha st ha tan nng cao v nhim As. Cc ion st c hnh thnh s kt ta trc tip cc As b oxi ha. Ngoi ra, As(III) c th b oxi ha trc tip bi nhiu ha cht khc bao gm: clo, hypoclorit, ozon, kali pemanganat,... v tc nhn Fenton (H2O2/Fe2+) [23] - Clo v hypoclorit l cht oxi ha mnh v c hiu qu nhng n li c th dn n phn ng vi cc cht hu c to cht c. Lng clo thm vo ph thuc vo thnh phn ca nc. Cho vo nc khong 0,8 2mg/l clo to ra 0,2 g/ml clo d dng cho mc ch kh trng sau khi x l. - Ozon l cht oxi ha mnh, khi cho ozon vo nc vi hm lng 2mg/l tip xc vi nc khong 1 pht trc khi lc s c hiu qu rt cao trong vic oxi ha st v mangan v loi b asen v cc kim loi khc ti di gii hn cho php. Ozon cng l cht st khun mnh nhng khng ging nh clo, d lng ca n khng tn ti lu trong nc x l. - Kali pemanganat (KMnO4) c hiu qu oxi ha As(III) cao cng vi Fe(II) v Mn(II) nhng li c hiu qu kh trng thp mc d n c tc dng km hm s pht trin ca vi khun. KMnO4 c nhiu cc nc ang pht trin n c s dng nh l cht khng sinh cc b. Mangan d trong nc x l khng c vt qu khuyn co ca WHO 0,05 mg/l (WHO 1993). - Trong mi trng kim yu Asenit b oxi ha bi I2 thnh Asenat: 3

AsO33+ I2 +2OH- AsO43- + 2I- + H2O (1.16) Phn ng to thnh hp cht mu xanh molipden: - Phn ng vi Molipdatamoni to thnh kt ta mu vng: (NH4)3AsO4 + 12MoO4- +24H+ (NH4)3H4[As(Mo2O7)] +10H2O (1.17) Asenit khng c phn ng vi Molipdatamoni. - S phn ng kh bng axit ascobic thnh hp cht mu xanh molipden: (NH4)3H4[As(Mo2O7)6] + C6H8O6 Xanh molipden + C6H6O6 (1.18)
(vng) (Axit ascobic) (Axit dehidro ascobic)

Axit heteropolyasenomolipdic v mui ca chng l nhng cht oxi ho rt mnh, oxi ho dc nhiu cht kh, trong khi axit H2MoO4 khng oxi ho c. Hp cht mu xanh molipden c thnh phn ch yu l (Mo 8O23.H2O; Mo4O11.H2O; Mo2O5.H2O...), tn ti di dng cc tiu phn keo trong dung dch, d b hp ph bi cc cht hp ph, nn trc khi o quang khng c lc dung dch mu. Phn ng (1.18) rt t lng, cng mu xanh t l vi nng asen, o cng mu cho php xc nh nng As. - Yu t cn tr: Cc ion PO43-, SiO32- cng c phn ng tng t, to cc kt ta (NH4)3H4[P(Mo2O7)6], (NH4)3H4[Si(Mo2O7)6][3]. Kt ta Axit heteropolyasenomolipdic d tan trong mi trng kim, hoc dung dch NH3 [3]: (NH4)3H4[P(Mo2O7)6] +27OH- 3NH3+12MoO42- + PO43-+17H2O (1.19) V vy, phn ng cn phi thc hin trong mi trng axit mnh (pH < 1) Phng php ny c ng dng phn tch nhng mu c hm lng As nh, trong khong nng 0,01 6,00mgAs/l. Khi dng phng php t ng, cng vi cht kh axit ascobic c th nng cao gii hn xc nh ti 0,001 10,00mgAs/l [14].
Tham kho Hp ph ln vt liu c thnh phn mangan dioxit C ch ca vic loi b asen bi MnO 2 bc u c nghin cu trn cc tinh th MnO2 tng hp trong phng th nghim. Phn ng oxi ho As(III) bi MnO2 xy ra theo 2 bc sau: 2MnO2 + H3AsO3 + H2O 2MnOOH + H2AsO42- + H+ (1.20) + 2+ 22MnOOH + H3AsO3 + 3H 2Mn + H2AsO4 + 2H2O (1.21) Mc d c ch phn ng ca As(III) vi MnO2 c bit kh chi tit nhng c rt t thng tin v s hnh thnh cc hp cht ca As(V) sau qu trnh oxi ho As(III).

CHNG 2. THC NGHIM

2.1. DNG C, MY MC, HA CHT 2.1.3. Ha cht Cc ha cht dng cho phn tch As u s dng cc loi PA ca hng Merck- c, nc ct 2 ln. 1. Dung dich H2SO4 10M. 2. Dung dch kaliantimonyl tactrat: ho tan 1,3715g K(SbO)C 4H4O6..1/2H2O trong 400ml nc ct, thm nc ct n vch ca bnh nh mc 500ml. Bo qun dung dch trong l thu tinh c nt. 3. Dung dch amonimolipdat: ho tan 20g (NH 4)6 Mo7O24. 4H2O trong 500ml nc ct. Gi dung dch trong chai thu tinh. 4. Dung dch axit ascobic 0,1M: Ho tan 1,76g C 6H8O6 bng nc ct, nh mc n 100ml. Dung dch n nh 1 tun 40C. 5. Tc nhn kt hp (TNKH): Trn cc dung dch theo t l sau: 50ml H 2SO4 5N + 5ml dung dch kaliantimonyl tactrat +15ml dung dch amonimolipdat + 30ml dung dch axit ascobic 0,1M. Trn tng tc nhn theo th t trn, lc k mi ln thm tng tc nhn. Nu xut hin vn c khi trn, cn lc k, yn trong vi pht cho n khi c mt i trc khi tin hnh. Thu c hn hp dung dch gi l TNKH, dung dch n nh trong thi gian 4h. 6. Dung dch As(V) chun (5mgAs/l): 7. Dung dch As(V) gc (1000mgAs/l): Dung dch As(V) gc H3AsO4 trong HNO3 1g As/l hiu MERCK- c. 8. Dung dch AgNO3 10% 9. Dung dch H2O2 30% 10. Km ca Anh sn xut 2.1.4. Chun b ha cht v thuc th Cc ha cht dng cho phn tch As u s dng cc loi PA ca hng Merckc, nc ct 2 ln. 1. Dung dich H2SO4 10M (R1) - Ht 68ml dung dch axit sunfuric c (d = 1,84g/ml) cho vo bnh nh mc 500ml c sn khong 200ml nc ct hai ln, nh mc n vch. 2. Dung dch kaliantimonyl tactrat (R2) - Cn chnh xc 1,3715 K(SbO)C4H4O6.1/2H2O tinh th ha tan vo cc, nh mc vo bnh 500ml bng nc ct hai ln. - Bo qun dung dch trong l thy tinh c nt. 3. Dung dch amonimolipdat (R3) - Cn chnh xc 20g tinh th Amonimolipat (NH 4)6 Mo7O24. 4H2O ha tan vo cc, sau nh mc vo bnh 500ml bng nc ct hai ln. Gi dung dch trong chai thy tinh ti mu. 4. Dung dch axit ascobic 0,1M (R4) Cn 1,76g C6H8O6 tinh th, pha vo cc ri nh mc vo bnh 100ml bng nc ct hai ln . Dung dch n nh trong 1 tun 40C 5. Tc nhn kt hp (TNKH) R dng cho th nghim c pha nh sau: R = 50ml R1 + 5ml R2 + 15ml R3 + 30ml R4 = 115ml 5

- Trn tng tc nhn theo th t trn, lc k mi ln thm tng tc nhn. Nu xut hin vn c khi trn, cn lc k, yn trong vi pht cho n khi c mt i trc khi tin hnh. Thu c hn hp dung dch gi l TNKH. - TNKH bn trong 4 gi. Do phi pha trong mi ln tin hnh th nghim 6. Dung dch Asen A (1mg/l): Ht 10ml dung dch Asen gc 1g/l cho vo bnh nh mc 1000ml v nh mc bng nc ct hai ln ti vch. Thu c dung dch Asen A c nng 1mg/l. 7. Dung dch Asen B (5mg/l): Ht 5ml dung dch Asen gc nng 1g/l, cho vo bnh nh mc 1000ml v nh mc bng nc ct hai ln ti vch. Thu c dung dch Asen B c nng 5 mg/l. 8. Dung dch AgNO3 10%. 9. Dung dch H2O2 2M Ht 20ml dung dch H2O2 30%, chuyn vo bnh nh mc 100ml v nh mc ti vch bng nc ct hai ln. 10. Km ca Anh sn xut (dng bt ). 11. Dung dch Axit sunfuric H2SO4 2M Ht 10,88ml dung dch Axit sunfuric c (d = 1,84g/ml) cho vo bnh nh mc 100ml c sn khong 50ml nc ct hai ln, nh mc bng nc ct 2 ln ti vch. 2.2. KHO ST CC IU KIN TI U CHO PHN NG TO HP CHT MU XANH MOLIPDEN 2.2.1. Kho st s hnh thnh cc ph hp th electron Cch tin hnh: - DD1: Ht 5ml dung dch asenat chun (5mgAs/l) cho vo bnh nh mc dung tch 100ml (bnh 1). - DD2: Ht 5ml TNKH cho vo bnh nh mc 100ml (bnh 2). - DD3: Ht 5ml dung dch asenat chun (5mgAs/l) v 5ml dung dch TNKH cho vo bnh nh mc 100ml (bnh 3). Cc bnh u c nh mc n vch bng nc ct, lc u. i mu pht trin n nh, qut ph trn my UV-Vis ca 3 dung dch ny trong khong bc sng t 200 1000nm, s dng nc ct lm nn. T DD3 s c mt gi tr bc sng hp th cc i (nm s b). 2.2.2. Kho st cc iu kin ti u 2.2.2.1. nh hng ca pH n phn ng to hp cht mu xanh molipden Chun b 10 bnh nh mc 100ml, ly vo mi bnh 5,00ml dung dch chun H3AsO4 (5mg As/l). iu chnh pH ca cc dung dch trong bnh thay i trong khong 0,00 1,80 bng dung dch H2SO4 10M. Thm ln lt vo mi bnh 5ml TNKH, lc k, nh mc n vch bng nc ct. i mu pht trin n nh, o mt quang ca lot dung dch mu trn my UV-Vis bc sng s b 850nm . T kt qu thu c, tm c gi tr mt quang A n nh ng vi khong pH ti u. 2.2.2.2. nh hng ca t l th tch TNKH/ nng Chun b 8 bnh nh mc 100ml, ht vo mi bnh 5ml dung dch chun H3AsO4 (5mgAs/l). Thm ln lt vo mi bnh cc th tch TNKH khc nhau, lc 6

k, thm nc ct n vch. i mu pht trin n nh, o quang lot dung dch mu trn my UV-VIS bc sng s b 850nm. T kt qu thu c, ta tm c t l th tch TNKH ti u, ng vi dung dch c cng mu ln v n nh nht. 2.2.2.3. nh hng ca thi gian n bn ca hp cht mu xanh molipden Chun b mt dung dch mu: ht 5,00ml dung dch As(V) chun H 3AsO4 (5mgAs/l), cho vo bnh nh mc dung tch 100ml. Thm tip 5ml dung dch TNKH, lc k, nh mc n vch. i mu pht trin n nh, o quang dung dch mu trn my UV-Vis bc sng s b 850nm trong khong thi gian t 0 60 pht k t khi to mu. T kt qu thu c, ta tm c khong thi gian ti u, ti mu bn v n nh nht. 2.2.3. Xy dng ph hp th electron ca hp cht mu xanh molipden - Chun b mt dung dch mu tng t nh trn, cc iu kin ti u chn, qut ph ca dung dch mu trn my UV-Vis trong khong bc sng t 400 1000nm, s chn c max ng vi tr s Amax. - Tng t nh trn, chun b mt lot dung dch mu cc nng khc nhau, qut ph ca lot dung dch mu trn my trong khong bc sng t 400 1000nm, so snh cc gi tr max ca cc ph cc nng khc nhau. Nu chng c cc i hp th cng mt bc sng, chng t hp cht mu bn, n nh v c thnh phn cc cu t trong phn ng ng bng quan h t lng. l bc sng thc nghim ti u, c s dng cho cc php o tip theo [8]. 2.2.4. Xy dng ng chun xc nh hm lng As Chun b mt dy gm 7 bnh nh mc dung tch 100ml, ln lt thm vo cc bnh cc th tch dung dch chun asenat khc nhau c dy cc dung dch c nng t 0,00 1,00mgAs/l. Thm vo mi bnh 5ml dung dch TNKH, lc k, nh mc n vch. i mu pht trin n nh trong khong thi gian ti u, o quang ca lot dung dch mu trn my gi tr max chn v ng chun s t thit lp. Dung dch nn c chun b tng t, nhng khng cha As. 2.2.5. nh gi tin cy ca ng chun xc nh As Chun b mt s dung dch As bit chnh xc nng (nm trong khong tuyn tnh ca ng chun), tin hnh to phn ng mu nh khi xy dng ng chun v xc nh li nng theo ng chun. Lp li nhiu ln v x l cc kt qu o bng thng k ton hc [13]. Kt qu thu c nu nm trong phm vi sai s cho php th ng chun c tin cy v c s dng cho cc mu phn tch tip theo. 2.4. PHN TCH HM LNG As TRONG CC MU NC NGM 2.4.1. Chun b mu nc ging ti huyn Bnh Lc, H Nam Phng php ly mu v bo qun mu Cc mu nc ging khoan c ly nh sau: Nc c ly trc tip t ging khoan cho vo bnh nha polietylen dung tch 500ml v 1000ml c ra sch bng axit HNO3 v HCl, trng bng chnh nc ging khoan c. Thm ngay vo mi bnh 5ml dung dch HCl 2M, sau mu c bo qun lnh 50C. 2.4.2. X l v phn tch xc nh CAs trong cc mu nc ging X l mu 7

- Giai on asin ha mu: Ly V = 250 500ml mu nc ging khoan cho vo bnh Kjeldahl dung tch 500ml. Thm 15g Zn bt v 20ml dung dch H2SO4 2,5M vo bnh. Nhanh chng ni ng n khi asin sc vo bnh hp th. un nh bnh trong thi gian ~2h. - Giai on hp th asin v xi ha: Hp th asin vo bnh dung tch 100ml c cha ~20 50ml nc ct c sn 10ml dung dch AgNO3 10%. Cn lu h thng ng dn kh asin phi tuyt i kin v c nhi bng tm Pb(CH3COO)2 gi li H2S (nu c). Thm ~2ml dng dch NaOH c ( kim ha) v 10ml H 2O2 30% vo bnh hp th chuyn ton b As(III) thnh As(V). Chuyn ton b dung dch trong bnh hp th, c trng ra cn thn vo bnh nh mc dung tch 100ml. nh mc n vch (gi l DDo). To phn ng mu v phn tch mu Ht chnh xc vo = 10ml DDo chuyn vo bnh nh mc dung tch 100ml, tin hnh phn ng to hp cht mu xanh molipden v o quang hp cht mu ti bc sng 850nm.