I HC THI NGUYN TRNG I HC NNG LM TS. NGUYN TUN ANH (Ch bin) TS. TH LAN, TS.

NGUYN TH HNG

Gio trnh
PHN TCH MI TRNG

NH XUT BN NNG NGHIP H Ni - 2008

LI M U

Mi trng l vn chung ca nhn loi ang c ton th gii c bit quan tm. Nhiu ni trn th gii v Vit Nam mi trng ang b suy thoi, ti nguyn thin nhin tr nn cn kit, h sinh thi mt cn bng, cht lng cuc sng suy gim. Nhu cu o to cc chuyn gia v nghin cu v bo v mi trng nc ta hin nay l rt cn thit. Mn hc Phn tch mi trng l mn hc nhm cung cp nhng kin thc c bn nht v c s ca mt s phng php phn tch mi trng ph bin trn th gii v mt s phng php ly mu, bo qun mu, phn tch mu v nh gi kt qu ca cc s liu phn tch cho sinh vin chuyn ngnh khoa hc mi trng. Gio trnh ny cn l ti liu tham kho cho nhng nh qun l mi trng, nhng k thut vin phn tch trong cc phng th nghim khoa hc t, sinh hc, ho hc v mi trng. Gio trnh phn tch mi trng c tp th tc gi ca trng i hc Nng Lm Thi Nguyn bin son gm 7 chng, c phn cng nh sau: - TS. Nguyn Tun Anh bin son chng 1, 3, 4, 5 - TS. Th Lan bin son chng 6, 7 - TS. Nguyn Th Hng bin son chng 2 Cc tc gi cm n s gip v ti liu v ng gp kin cho vic bin son cun gio trnh ny ca cc ng nghip cc vin nghin cu, trung tm phn tch v cc thy c gio khoa Ti nguyn v Mi trng, trng i hc Nng Lm Thi Nguyn. Trong qu trnh bin son, chng ti tham kho nhiu ti liu ging dy v kt qu nghin cu c lin quan n phn tch mi trng trong v ngoi nc. Tuy c nhiu c gng, song chc chn khng trnh khi nhng thiu st. Tp th tc gi mong nhn c s gp ca cc thy c gio, sinh vin v c gi trong v ngoi nc gio trnh ny ngy cng c hon thin hn.

Cc tc gi

Phn 1 NHNG VN CHUNG

Chng 1 M U

1.1. Mi trng Mi trng bao gm tt c cc yu t l hc, ho hc, cc cht hu c v v c ca kh quyn, thch quyn v i dng. Mi trng sng l tp hp cc iu kin xung quanh c nh hng n c th sng, c bit l con ngi. Mi trng quyt nh cht lng v s tn ti ca cuc sng. Mt s nh nghin cu s dng thut ng "vi mi trng" ch r mi trng chc nng (functional environment), ngha l mi trng ring bit ca cc c th c bit. Theo ngha en, thut ng ny lin quan n mi trng nh, ngha l mi trng trc tip nh hng ca c th. 1.2. Phn tch mi trng Phn tch mi trng c th c nh ngha l s nh gi mi trng t nhin v nhng suy thoi do con ngi cng nh do cc nguyn nhn khc gy ra. V vy, phn tch mi trng bao gm cc quan trc v cc yu t mi trng ni chung. y l vn rt quan trng v qua chng ta c th th c yu t no cn c quan trc v bin php no cn c p dng qun l, gip chng ta c th trnh khi cc thm ho sinh thi c th xy ra. Trong nhng nm gn y, nghin cu sinh thi khng ch l s tip cn v cht lng m cn c v s lng. c th hiu bit v nh gi v mt h sinh thi i hi phi quan trc y s bin ng theo khng gian v thi gian ca c cc yu t mi trng, c v s lng v cht lng c lin quan n cu trc v chc nng ca h. l cc nh chi l, ho v sinh hc ca h sinh thi. 1.3. S la chn phng php phn tch mi trng Vic la chn phng php v cc quy trnh trong phn tch mi trng i hi phi c nhiu kinh nghim. Cc phng php la chn phi tr li c nhng cu hi sau: S dng phng php phn tch no? Lng mu c cho nhiu phng th nghim khng? Yu t no hn ch s pht hin, chnh xc ca cc phng php phn tch c s dng?

Ngi s tin hnh phn tch? Nhng vn g cn ch trnh lm bn mu trong qu trnh bo qun mu. Cc ch tiu no cn phn tch phn nh thc t kh nng c hi ca mi trng? Hm lng hay dng tn ti ca cc nguyn t ho hc?

l.4. Gi tr ca cc s liu trong phn tch mi trng Cng vic kh khn i vi cc nh nghin cu l phi xc nh c nhng ch tiu phn tch no l cn thit. Vic xc nh thnh phn cc nguyn t l hay cn cn phi phn tch cc phn t hay cc nhm chc ca cc cht? V d: Khi phn tch hm lng tng s cc nguyn t nh: Hg, Pb, P,... c th s khng nh gi ht c tim nng gy hi cho sc khe con ngi. iu ny cng tng t nh vic nh gi mi quan h gia hm lng tng s ca cc cht trong t vi kh nng s dng ca cy trng. Ch c mt phn trong hm lng tng s l d tiu i vi thc vt. Do vy vn kh khn l s dng phng php ho hc no phn nh ng cc hot ng ca h r thc vt. Trn thc t kt qu ny thng rt hn ch. V d i vi cy rau dip (lettuce), hm lng ch trong cy c quan h vi lng ch chit rt t t bng HNO3 im. Trong khi vi cy yn mch (Oat), hm lng ch trong cy li tng quan vi ch chit rt bng HNO3 0,01M hoc CH3COONH4 1M. Vic phun dung dch CuSO4 ln l hoc t lm tng hm lng ng trong cy la m, nhng hm lng ng trong cy li khng c tng quan vi lng ng d tiu c xc nh trong dung dch chit rt CH3COONH4 1M, axit mnh hoc cht to phc (EDTA). Mc d c nhng hn ch nht nh, vic quan trc cc yu t ring bit vn cn c tin hnh nh xc nh cc vng b nhim ghi nhn cc thay i v mc cc cht nhim v cc dn liu ca cc yu t bn ngoi nh: gi, ma, a hnh... nghin cu xu hng bin i c th xc nh mt chui quan trc. V d: s liu bng 1.1 a ra mc nhim 4 loi ch th c phn tch. Bng 1.1. nh hng ca hng t ngun i vi s tch lu ca ion kim loi trong mu
im ly mu Pb (ppm) A D Zn (ppm) A D Mu C 10 49 86 150 102 146 350 270 a y 130 1528 675 1135 Ru 120 1200 1213 4870 t 270 230 450 416

Cd (ppm) A D

8 13 9 9

68 83 -

93 137 -

7,1 7,7

S liu bng 1.1 cho thy mc nhim thay i theo hng a l (hng A,B,C,D). Tuy nhin nu vic la chn c nh hng s cho thy mc nhim so vi cc vng khc. Nhng quan trc tng t cng c th c p dng vi mi trng nc. Nhng vic phn tch n thun cc mu nc lc s hn ch ngha ca cc s liu phn tch. Trn thc t cc cht l lng v cc cht lng ng cc h nc c th gii phng n cc cht c hi trong cc chui thc n hoc i sng ca cc sinh vt thu sinh. Cn l lng thng l nhng hn hp phc tp bao gm cc cht hu c, v c v phc hu c - v c. Gia chng li c s tng tc khc nhau nh cc keo xt trong nc mn c th hp ph trn 2,5% axit mn. S c mt ca cc axit humic s lm tng kh nng hp ph ca cc cht l lng. S thay i ca cc cht in ly s lm thay i qua trnh ny (trong nc ngt lng axit humic c hp ph l nh hn 0,4%. Do vy ti ni tip gip gia cc vng nc ngt v nc mn (vng ca sng) s c s bin i t ngt v s phn b ca cc kim loi nng gia pha rn v lng. V cc sinh vt bin c xu hng tch lu cc kim loi nng khi sng trong mt trng nhim nn chng c th c coi nh cc vt ch th. Cc s liu ny c th so snh vi kt qu iu tra trung bnh trong ng vt gip xc (tm, cua...). i vi thc vt hm lng ln kim loi ca mt sinh vt c bin ng ln (hng chc ln) so vi v tr tng i ca n i vi ngun nhim, nhng hm lng ny l tng i n nh trong vng ly mu v c s khc nhau ln so vi cc gi tr c xc nh. Ti mt ni xc nh s dao ng hm lng ca mt cht c th l 20%. V vy s khc nhau nhng ni khc nhau phi ln hn s liu thng k c ngha . 1.5. nh hng ca cn bng Cc s liu trong bng 1. 1 c xem xt trn c s cc cn bng nh di y: V ru l vt bm trn cy nn s tch lu cc ion kim loi c th trc ht l t bi v khi xung quanh. V vy, hm lng ca mt s cht c th bi gim do nc ma ra tri. Cc cy mc trn t c kh nng s dng cc cht rt khc nhau v ph thuc vo cc tnh cht ca t. Kh nng hp ph cc cht ca cy cng b gim st khi c s cnh tranh gia cc tht hp thu. Nu h thng khng qu phc tp, qu trnh hp thu cc cht c th c biu din bng phng trnh ton hc nh sau:
(x/m)a = k1.Ca.Sv/(1+k1Ca + k2Cb+ k3Cc+...)

Trong : (x/m)a: s lng m loi a ht thu trn 1g cht; Sv: Gi tr cc i (hoc bo ho); CaCbCc: hm lng ca cc loi cnh tranh a, b, c; k1 k2 k3: h s ht thu tng ng; Trong trng hp k2Cb hoc k3Cc>> k1Ca th (x/m)a s gim rt mnh. Cc qu trnh trong h thng cn bng c trnh by hnh 1.1. Vai tr quan trng trong h thng ny l s hot ng ca vi khun, nh trng hp nhim thu ngn (Hg). S chuyn ho gia hp phn thu ngn v c thnh ion metyl thu ngn (CH3Hg+) xy ra rt ph bin tng mt ca cc cht trm tch hoc cc phn hu c l lng. Tc chuyn ho ph thuc vo qu trnh thu ngn xm nhp vo cht hu c Dng lin kt hu c - kim loi s nhanh chng c c v thc vt s dng, chng c xu hng tch lu trong c th sinh vt. S tch lu Hg trong h thng h hoc vng ca sng nh sau: Cht trm tch cha 90 - 99% thu ngn (khong 10% l CH3Hg+), pha nc t 1 n 10% (hu ht dng lin kt v c vi cc cht l lng), sinh vt < 0,1%(ch yu l CH3Hg+). c bit cc loi gip xc trong sinh quyn bin (nh trai, s tm, cua...) c kh nng tch lu thu ngn rt cao.

Mt s vi khun c kh nng chng chu vi nng Hg cao v c th chuyn

ho cc hp cht hu c - thu ngn thng dng thu ngn t do khng ha tan. Hn na trong iu kin k kh, cc vi khun kh sunphat cng c kh nng sinh ra hirosunfua c nh Hg2+ di dng sunfua, vi khun khng chuyn ho hp cht ny thnh metyl thu ngn. Xem xt cc cn bng phc tp trong hu ht cc h thng t nhin, iu cn lu khng ch l vic la chn cc ch th m cn kh khn trong cng vic ly, vn chuyn v bo qun mu. V l thuyt, iu cn thit l lm ngng tr tt c cc qu trnh ho hc cng nh sinh hc bng cc phng php thch hp. Cc qa trnh bin i ny s c gim ti mc ti thiu nhit thp hoc s dng nhng phng th nghim di ng. Tuy nhin tn ti mt vn l h thng cn bng trong t nhin lun lun b xo trn. V d nh ly mt mu nc pha trn trm tch (hoc tch cc cht l lng) s lm cho mt hp phn hoc cc cht ho tan thit lp mt cn bng mi. Tuy nhin, v mt tng s vn khng thay i v s l cc dn liu cho s nhim. Vn tip theo cn ch nh gi mc nhim l phi la chn phng php phn tch c chnh xc thch hp v cn c tin hnh trong thi gian nht nh

Chng 2 CHNH XC V TIN CY CA PHP PHN TCH

2.1. Bo m v kim sot cht lng trong phn tch mi trng Bo m v kim sot cht lng i hi tt c cc phng th nghim phi tun th theo cc hng dm c a ra m bo kt qu phn tch c tin cy cao. Bo m cht lng thng qua hng lot cc nguyn tc v s gim st cht ch chnh xc ca kt qu phn tch c tin cy v tnh php l cao. Vn bo m cht lng bao gm c vic ly mu v lo qun mu ca cc phng th nghim v trch nhim cng nh k nng ca cc c nhn phn tch v ngi chu trch nhim. Vi ngha rng hn th c k hoch cng c bao gm trong vic kim sot cht lng. Kim sot cht lng phng th nghim bao gm: cc ti liu v phng php tiu chun cc php th, chun bi cc ng chun v kim tra thng xuyn cc thuc th, my mc, xc nh chnh xc v tin cy ca php phn tch, chun b s kim tra. Chun b ng chun: Cc ng chun c xy dng trn c s cc php o mu hoc sc k kh cc nng khc nhau v c chun bi hng ngy trc khi phn tch mu. Nu kt qu o c sai s 15% th cn phi xy dng li ng chun. 2.2. Sai s v chnh xc Sai s c th hin qua kt qu phn tch ca cc ln lp li. Nu mt mu c phn tch lp li nhiu ln trong cng mt iu kin th kt qu cng s khc nhau do sai s th nghim hoc do thao tc. Cc kt qu ny s phn b mt cch ngu nhin xung quanh mt gi tr trung bnh l gi tr trung bnh cng ca cc php o. Khi cc kt qu o phn b nh dng hnh qu chung c gi l ng cong phn b chun hoc ng Gauss (Gaussian Curve) nh hnh 2.1 (trong nhiu mu mi trng b nhim bn th kt qu s khng theo s phn b chun).
x Gi tr trung bnh (x) c tnh bng (x: cc gi tr o; n: s ln o) n

 lch chun (S) s xc nh chiu rng ca th phn b v c tnh nh sau:

Trong trng hp hm phn b chun th 68,27% din tch nm trong khong

x 1S; 95,45% nm trong khong x 2S v 99,70% nm trong khong x 3S. Gi tr 3S xung quanh gi trij trung bnh l gii hn trn v di trong thij kim tra. Tt

c cc gi tr nm ngoi x 3S c xem l khng bnh thng. iu ny chng t rng c vn no trong qu trnh phn tch cn phi c xem xt ngay. lch chun cng c th c tnh theo cng thc nh sau:

n: s php o Mc d s s hoc kt qu phn tch lp li c th c biu din di dng ca lch chun nhng ln gi tr phn tch c th lm thay i ng k lch chun ln cc gi tr tng ng. C th minh ho iu ny qua 2 v d sau y: V d 1: Hm lng tng s hirocacbon du m - TPH (total petroleum hirocacbon, TPH) trong mu b nhim bn vi 6 ln phn tch l 5,3 - 4,9 - 5,1 - 5,5 4,7 v 5,0 mg/l. Xc nh lch chun nh sau: X 5,3 4,9 5,1 5,5 4,7 5,0 30,5 x2 28,09 24,01 26,01 30,25 22,09 25,00 155,45

V d 2: Nu kt qu phn tch TPH trong mu c gi tr ln gp 10 ln ngha l 53 - 49 -51- 55 - 47 v 50 mg/l th lch chun s l:

Nu gi tr o c ln hn, v d nh 530 - 490 - 510 - 550 - 470 v 500mg/1 th S = 28,6mg/l. Nh vy lch chun khi bin i theo ln cc gi tr o c l khng c ngha tr khi ln ca gi tr phn tch c xc nh trc. Ni mt cch khc, sai s phn tch s lun c gi tr khi lin quan vi gi tr ca mu o. Mt cch biu th khc l lch chun tng i (relative standard devlation - RSD) hoc h s bin thin (Coemcient of vanance - CV). y l t s gia lch chun v gi tr trung binh i s:

Trong v d 1 v 2 trn, RSD s l:

Nh vy RSD hai v d ny l bng nhau trong khi S c s khc nhau r rt (0,29 v 2,8mg/l.) Mt cch khc biu th sai s l sai s chun ca gi tr trung bnh (M), y l t s gia S v cn bc hai ca s ln o (n).

Trong phn tch mi trng, thng thng vic lp li nhiu ln l kh thc hin c. V vy sai s ca php tnh c tnh ton thng qua khc nhau phn trm tng i (Relative percent difference - RPD). T s ny c xc nh thng qua s phn tch lp li h ln mu trong mt iu kin xc nh. l t l phn trm gia hiu s ca kt qu gia hai ln phn tch vi gi tr trung bnh cng ca chng.

Trong : a1 v a2 l gi tr ca hai ln phn tch mt mu V d 3: Hm lng Cl- trong hai ln phn tch mt mau l 9,7 v 11,1 mg/l. Sai s s c xc nh nh sau:

chnh xc ca gi tr phn tch l mc chnh xc ca n so vi hm lng thc t c trong mu. chnh xc c nh gi qua vic cho thm vo mu mt lng nht nh dung dch chun c nng bit. Da trn phn trm ca nng cho thm c pht hin iu chnh chnh xc cho kt qu phn tch. Nhn chung trong phn tch mu mi trng khng yu cu cc php tnh iu chnh sai s ca kt qu phn tch. Tuy nhin trong nhng php phn tch c bit no , vic iu chnh sai s c th c t ra. Khi phn tch mt s cht hu c trong nc thi, USEPA- (The Unted States Envunment Protectlon Agency) a ra bn vng cho lng phn trm c xc nh. Nu gi tr ca bt k mt php phn tch no nm ngoi cc vng ny thi cc chi s QC cho php phn tch s khng c p ng. Mt ma trn lng b sung pht hin c c th xc nh bng hu cch: Phng php xc nh phn trm thu hi t lng tiu chun thm vo, chng hn nh phng php ca U.S.EPA(I) v phng php tnh phn trm thu hi gia mu cn o v dung dch chun(2) Lng tm thy c tnh ton bi hai phng php s cho cc gi tr khc nhau. Cch xc nh 1 (U.S.EPA):

Trong xi: gi tr o c cho mu ho trn; xu: gi tr o c cho mu khng ho trn th tch sau khi ho trn; k: gi tr bit nng ca mu chun trong mu ho trn. Cch xc nh 2:

Nng l thuyt c th tnh nh sau:

Trong : Cu: nng o c ca mu;

Cs: nng ca dung dch tiu chun; Vu, Vs: th tch ca mu v dung dch tiu chun. Phn trm lng thu hi theo cc cch tnh trn y c th c minh ho trong cc v d sau y: V d 4: Mt mu nc th c xc nh c nng xianua l 3,8 mg/l. Sau khi cho thm 10 ml dung dch tiu chun c nng xianua l 50 mg/l mu vo 100 mu nc thi trn. Nng ca xianua trong hn hp thu c l 8,1 mg/l . Tnh phn trm lng thu hi t dung dch ny (sau khi pha long) theo cch tnh 1. + Da theo nng xc nh:

+ Da trn khi lng (phng php chuyn i) khi lng tng s ca ion CN trong 110 ml mu v dung dch tiu chun l:
-

8,1 mu x 0,110 l = 0891 mg Khi lng ion CN- tnh theo phn trm trong 100ml mu cn xc nh ban u: 3,8 mg/l x 0,100 l = 0,38 mg Khi lng ion CN- trong 10 ml dung dch tiu chun l: 50 mg/l mu x 0,010 l = 0,500 mg Tnh phn trm lng tm c nh trong cch xc nh 2. + Tnh ton da trn nng : Nng CN- o c sau khi c b sung thm bng dung dch chun l 8,1 mu. Nng thc t ca CN- sau khi pha trn s c gi tr bng nng CN- ban u trong mu + nng CN- trong lng dung dch tiu chun b sung thm. Hay:

+ Tnh ton da trn khi lng (phng php chuyn i):

Khi lng xianua o c trong tng s 110 ml dung dch (100 ml mu + 10 ml dung dch chun b sung thm) s l:

Khi lng thc t ca xianua trong 110 ml dung dch ny l:

V d 5: Mt mu o c 11,7 mgl/1. Nu b sung thm 5 ml dung dch chun c nng 100 mg/l vo 50 ml dung dch ny s c dung dch c nng o c l 18,8 mg/l. Tnh lng b sung tm thy c nh trong cch tnh 1 v 2 (tnh trn c s nng ). + Cch xc nh 1:

+ Cch xc nh 2:

Khi lng tm thy l nh hn 100% theo U.S.EPA (cch tnh 1) s cho gi tr thp hn khi tnh theo cch 2 (v d 5). Tuy nhin nu lng tm li c m ln hn 100% s cho gi tr ngc li (v d 4). i vi vic phn tch cc mu t v cht thi rn th khng cn ph iu chinh nh i vi mu nc v t v cht thi rn phi dng mt cht lng chit rt, nh v d 6 di y. V d 6: Mt mu t c cht rt xc nh hirocacbon du m (PHC) bng phng php o ph hng ngoi. Hm lng PHC trong mu xc nh c l 285 mg/kg. Thm 2 ml dung dch chun PHC c nng 1000 mg/l vo 40 g mu. Nng

 PHC mu ny o c l 326 mg/kg. Xc nh tin cy ca php phn tch theo phn trm lng tm c t lng b sung ca dung dch chun. Khi lng ca PHC trong mu thm dung dch chun l:

Khi lng ca PHC trong mu trc khi b sung dung dch tiu chun cha PHC l:

Nh vy, khi lng mu c b sung bng dung dch PHC chun l 40g ch khng phi 43g (thm 2 ml dung dch chun c t trng khong 1,5 gian) theo tnh ton trn. Thc t l 2 ml dung mi thm vo s trn ln vo cht chit rt. V vy khi lng ca mu sau khi chit rt (tc l khi lng ca phn cht rn cn li) hu nh khng thay i so vi trc khi chit rt chng. Phn trm pht hin c t lng b sung thm vo mu ni trn c th c xc nh theo cng thc US.EPA nh sau:

Khng c s iu chnh chnh xc v khi lng hoc th tch no c a vo trong cch tnh ton trn. V vy, xu c ly l 285 mg/kg. Phn trm lng tm c trong v d trn c tnh theo cch 2 s l:

2.3. th kim tra C hai loi th kim tra l kim tra chnh xc v th kim tra sai s. thi kim tra chnh xc c xy dng t cc lng pht hin c (%) trong cc phn tch thng thng. th kim tra sai s c th c xy dng trn c s s khc nhau phn trm tng i (RPD) ca nng phn tch trong mu v s liu phn tch lp li. Cc khc nhau phn trm tng i (RPDS) c tnh ton cho phn trm lng pht hin c trong ma trn cc nng tiu chun v phn tch lp li cc ma trn cht chun trong mi t. Khong 20 im (hoc mt s lng hp l cc im s liu) c a ra s phn nh tn sut hoc s ln phn tch Nu nhng mu khng pht hin c, cn phi pha thm dung dch chun c cha cc cht phn tch v RPD cn phi c xc nh cho mt ma trn cc lng pht hin c. Cc s liu ny c th c kim tra da vo cc thng tin c sn trn th kim tra. Bt k mt vn no xut hin trong php phn tch c th c nhn bit thng qua lch ln so vi gi tr trung bnh. Trong php phn tch bnh thng, mt mu phn tch s c pha vi mt nng chun bit v s xc nh c phn trm lng pht hin c. th kim tra c xy dng nh hnh 2.2. Gii hn cnh bo cn trn UWL (Upper Waming Limits) v cn di LWL(Lower waming limits) c xc nh mc 2S. Gii hn kim tra cn trn UCL(Upper Control Limits) v cn di LCL (Lower Control Limits) c xc nh mc 3S xung quanh gi tr trung bnh. Nu s liu no nm ngoi vng UCL v LCL, th sai s phn tch cn phi c xc nh v c lm chnh xc li. Lng thu hi tt nht l nm trong gii hn gia UWL v LWL. Nu c 7 s liu lin tip nm pha trn hoc pha di gi t trung bnh s chng t c sai s trong phn tch. Cn thit phi c 2/3 s im phn tch nm trong phm vi ca lch chun quanh gi tr trung bnh. th kim tra c trnh by trn xc nh c sai s v chnh xc ca php phn tch, nhng chnh xc khng c th hin r rt, v d khi th c xy dng khng chnh xc. Tuy nhin th kim tra l rt hu ch trong nh gi cht lng s liu.phn tch mi trng. th kim tra sai s cng c c xy dng trn c s cc gi tr RPD t kt qu phn tch lp li cc mu. Gi tr trung bnh v lch

chun s c xc nh Cc gii hn UWL, LWL,UCL v LCL cng c xc nh ti 2S v 3S. Phng php ny c coi nh hnh thc kim tra sai s b sung cng vi th kim tra lng thu hi trn. Cc thi kim tra l mt phn quan trng ca chng trnh kim tra cht lng (QC programs) trong phn tch mi trng.

Phn 2 MT S PHNG PHP DNG TRONG PHN TCH MI TRNG

Chng 3 PHNG PHP TRC QUANG

3.1. Phng php so mu quang in Phng php so mu quang in v phng php phn tch da trn s so snh cng mu ca dung dch nghin cu vi cng mu ca dung dch tiu chun c nng xc nh. Phng php ny c dng ch yu xc nh lng nh ca cc cht, tn t thi gian so vi cc phng php ha hc khc. 3.1.1. nh lut cbn ca phng php so mu Nu chiu mt dng sng (cng I0) vo mt cuvet ng dung dch th mt phn ca n (cng Ir) b phn x t mt cuvet, mt phn khc (cng Ia) b dung dch hp th, phn cn li (cng It) i qua cuvet. Ta c:

Khi s dng mt loi cuvet c th xem cng dng nh sng phn x v khng i v thng khng ln nn c th b qua. Khi phng trnh trn c dng

I0 v It c th o trc tip cn Ia tm c theo cng thc Ia= I0 - It. Da trn nghin cu thc nghim Bug (Bougueur) v Lmbe (Lambert) thit lp nh lut v pht biu nh sau: Nhng lp cht c chiu dy ng nht trong nhng iu kin khc nh nhau, lun hp th mt t l bng nhau ca chm nh sng chiu vo nhng lp cht . Biu thc ton hc ca nh lut l:

Trong : I0: l chiu dy lp hp th k: h s tt, h s ny ch ph thuc vo bn cht ca cht tan v bc sng nh sng chiu vo dung dch. Do nh lut hp th nh sng Bug - Lmb ch ng cho tia n sc.

Khi nghin cu s hp th nh sng ca dung dch, Bia (Beer) thit lp c mi tng quan gia h s tt k vi nng cht hp th theo phng trnh:

Kt hp nhng nghin cu ca Bug- Lm be- Bia th: Nu nng C c tnh theo mol/1; Chiu dy lp dung dch (l) o bng cm th c gi l h s tt phn t hay h s hp th phn t; l mt i lng khng i ph thuc vo bc sng nh sng, bn cht ca cht tan, nhit dung dch. 3.1.2. Cc i lng thng dng trong phng php so mu T s gia cng chm sng sau khi i qua dung dch (It) vi cng chm sng chiu vo dung dich(I0) gi l truyn qua, k hiu bng T.

i lng T ng vi chiu dy lp dung dch bng 1 cm gi l h s truyn qua. Logant ca i lng nghch o vi truyn qua gi l mt quang D hay tt E (extinction):

T nh ngha ny thy rng mt quang D t l thun vi nng cht tan trong dung dch 3.1.3. Vng quang ph hp th c im hp th nh sng ca cc hp cht mu l s hp th chn lc. H s hp th phn t ca hp cht mu v mt quang ca dung dch khc nhau i vi chm nh sng i qua c bc sng khc nhau. V vy ph hp th cng l mt c trng in hnh ca cc hp cht mu.

Khi s dng phng php so mu nh lng mt cht cn phi dng tia n sc no m khi chiu qua dung dch, dung dch c kh nng hp th ln nht. xc

nh bc sng nh sng hp th cc i ngi ta o gi tr mt quang hoc h s hp thu phn t ca dung dch mu vi nhng bc sng khc nhau, cch nhau 1020nm. gi t bc sng no m mt quang o c l ln nht th l bc sng nh sng thch hp nh lng hp cht mu ny. 3.1.4. Knh lc mu m bo nhy v chnh xc ca php xc nh, ngi ta khng cho dung dch hp th mt chm nh sng m ch cho nhng tia n sc b dung dch mu hp th cc i i qua. Mun tch c nhng tia sang ny ngi ta phi dng knh lc sng (knh lc mu). Knh lc sng l tn gi chung cc mi trng nh: thu tinh, mng tng hp... ch cho nhng tia sng thuc mt vng xc nh ca quang ph i qua. Knh lc sng trong phng php so mu phi m bo cho nh sang n sc truyn qua t cc i nhng bc sng trng vi bc sng hp th cc i v i qua knh lc mu phi b dung dch hp thu chn lc cao nht. Mun vy, trc khi o mt quang dung dch mt hp cht mu cha bit max (bc sng nh sng b hp th cc i) cn tin hnh phng php thc nghim: quay cc knh lc mu xem knh no cho nh sng mu b hp th mnh nht, hoc c th da vo mu sc ca dung dch xc nh tm knh lc mu thch hp theo bng sau: Sng 3. 1. Cc knh lc s dng cho cc dung dch mu Mu ca dung dch Tm Xanh Xanh lc Lc xanh Lc Lc vng Vng Mu ca knh lc sng Lc vng Vng nu nu Tm Xanh hl

3.1.5. Phng php xc nh nng cc cht Khi tin hnh mt lot php xc nh, phng php thun li nht l phng php ng chun. xy dng ng chun ta o mu cc dung dch chun ca cht vi cc nng hoc hm lng bit. Tin hnh o gi tr mt quang D (hay phn trm truyn qua) ca dy dung dch chun ny v xy dng ng chun bng phng php hi quy tuyn tnh. Tc honh biu din gi tr D, trc tung biu din gi tr nng hoc hm lng ca cht chun.

Nu nng dung dch mu nm trong khong tun theo nh lut Bug- Lm be- Bia th tt c gi tr mt quang nhn c nm trn mt ng thng Sau o gi tr mt quang ca dung dch mu nghin cu vi cng cuvet v knh lc mu s dng o cc dung dch chun. Da vo ng chun, ta xc nh c nng dung dch mu nghin cu. Hnh 3.2 s minh ho vic xy dng mt thang chun trong xc nh hm lng photpho (P2O5) bng php hi quy tuyn tnh, im chm l im thc nghim v ng thng l ng hi quy.

V l thuyt cc im khu xy dng ng chun phi nm trn mt ng thng, nhng trong thc t do c nhng sai s kh trnh khi, chng c chnh lch t nhiu. V mu ca dung dch bin i theo thi gian (thng b nht dn), do vy khng nn keo di thi gian o, do s lng mu phi hn ch. Nhng nu dung dch c mu bn th khng i hi kht khe nh vy. 3.2. Phng php quang k ngn la (Flamephotomet) Phng php quang k ngn la l mt dng phn tch quang ph pht x. Nguyn l c bn ca phng php nh sau: Di tc dng ca nhit ngn la cc nguyn t phn t hoc ion ca cc cht b kch thch s chuyn sang trng thi cc dao ng ca in t pht x. Cng pht x ny c o bng dng c quang hc ri t tnh ra nng cht cn xc nh. Phm vi s dng quang k ngn la rt ln. Rt nhiu nguyn t c th dng phng php ny xc nh gin tip hoc trc tip vi tc nhanh v c chnh xc cao. 3.2.1. C s l thuyt S hp th hoc pht x nng lng nh sng lm cho nguyn t (hoc phn t, ion) chuyn t trng thi bnh thng sang trng thi kch thch v ngc li. trng thi bnh thng nguyn t c nng lng nh nht, khi hp th nng lng chng chuyn sang trng thi kch thch. Thi gian nguyn t trng thi kch thch rt ngn (thng l 10-8 giy) ri li chuyn v trng thi cn bng km theo s pht x. S pht x ph thuc vo mc nng lng ca chng trng thi bnh thng v trng thi kch thch.

Nh vy, mi mt nguyn t hay ion bin i trng th bnh thng sang trng thi kch thch c c trng bng mt gi tr nng lng nht nh. V vy, s pht x nguyn t ca bt k mt nguyn t no cng c thnh phn quang ph c trng hay cu to vch quang ph c trng. ng dng trong php tnh nh lng ngi ta chn ly mt vch quang ph c trng tc l vch ph xut hin cui cng khi gim dn nng cht. S thay i cng ca vch ny s xc nh lng nguyn t cn phn tch. S kch thch quang ph pht x tng ln khi tng ngun nng lng ban u cung cp tc l nhit . Tuy nhin mt s nguyn t nh kim loi kim, kim th c th pht x nh sng nhit khng cao lm, v vy vic xc nh nhng nguyn t ny khng cn thit phi t nhit rt cao. Nhn chung, nhn c nhng vch quang ph cn c nhit thch hp cho tng nguyn t. Bng 3.2. Nhit ca m s ngn la thng dng (Theo Poluectov) Hn hp chy Propan- khng kh Hiro-khng kh Axetylen Hiro - xy Axetylen- xy Propan - N2O Nhit ngn la (0C) 1700-1 800 2000-2O45 2125-2397 2550-2660 3100-3137 2850-2900

Khi tng nng nguyn t c th xy ra hin tng hp th pht x, tc l nhng nguyn t khng b kch thch s hp th mt phn nng lng pht x. V th nn bt u t mt gii hn nng no (i vi mi nguyn t xc nh) th quan h gia cng pht x 1 v nng C s khng l tuyn tnh (hnh 3.3) tc l phng php quang k ngn la ch ng v dng c trong phm vi nng nht nh i vi tng nguyn t.

Ngoi ra cn ch ti nhng iu kin sau: + Qu trnh xy ra trong ngn la: iu kin nhit cao thng c s bay hi ln, phn t cc mui phn li tham gia phn ng vi cc thnh phn khc, kt qu l cng mt lc trong ngn la tn ti mt lng electron t do, ion, phn t, nguyn t. Cn bng gia dng ny ph thuc vo nhit ca ngn la, thnh phn hi ca dung dch, iu kin xy ho - kh. V vy thnh phn dung dch cha nguyn t cn xc nh c nh hng n kt qu phn tch. loi tr nh hng ny, cn chun b dung dch chun c thnh phn ging nh thnh phn dung dch phn tch. + Thnh phn dung dch khng nhng nh hng n cc qu trnh xy ra trong ngn la m cn nh hng ti qu trnh bm mu. Nhit , sc cng b mt s thay i lng dung dch c ht qua vi phn tham gia vo trong ngn la, nn sng ca ngn la cng s thay i. iu s gy nn sai s cho php phn tch. + S c mt ca cc ion l vi lng ln trong dung dch s lm chuyn dch cn bng trong cc phn ng phn li v ion ho dung dch. v d nh cng pht x ca canxi v ca kim loi kim khc gim xung khi c mt nhm v khi to thnh mt hp cht kh phn li (nCaO.Al2O3). Lng Canxi cng nhiu th gi tr n cng ln. + Cc cation kim loi kim c nh hng n s pht x ca nhau, thng lm tng cng pht x nh hng ca cc cation kim loi kim gim theo th t sau:

+ nh hng ca anion: Khi c mt mt vi anion trong dung dch s lm gim nng v cng pht x ca nguyn t kim loi. Anion nitrat NO3- c nh hng nht n s pht x ca kim loi kim. Mc nh hng tng dn theo th t sau:

+ Rt nhiu cht c mt trong dung dch thng t pht x vi nhng bc sng gn vi bc sng phn tch ca nguyn t xc nh. iu lm tng kt qu xc nh. V d: Khi xc nh nitrat cn ch vch quang ph ca canxi, khi xc nh kim

cn ch vch ca li v rubii. 3.2.2. Quang k ngn la - Cu to: Bt k mt quang k ngn la no cng gm nhng b phn chnh sau: + Ngun pht x: Gm my bm khng kh ni vi ng phun m chuyn dung dch sang trng thu soi kh a vo ngn la, b phn cp hi t a vo n + Thit b n sc: Thng l cc knh lc phn lp, mi nguyn t c knh lc mu ring, thng c cc knh lc ca natri, kali, canxi... + My thu pht x: o cng pht x. a s cc nc thng dng t bo quang in. + in k nhy (n 10-10A). l kiu in k gng quay S dng: Chun b mt thang dung dch chun bit nng , c thnh phn tng t vi thnh phn dung dch phn tch. M bnh nn khng kh v kh t axetylen (trc khi i vo vi phun v n t, kh t v khng kh cn c lm sch bng dung dch H2SO4 c). iu chnh p sut kh t v khng kh cho thch hp tc l lm sao cho ngn la chy tt (nu ngn la c mu vng v c khi l tha kh t, iu chnh sao cho ngn la u, khng c mu) v dung dch b ht vo n nh, va phi. Quay knh lc tng ng. M cng tc, a vo dung dch chun c nng m nht. Nu ch s ca in k ch ngoi thang th phi gim mng chn c c ch s trn in k. Tip tc o thang chun vi nng t thp n cao. S c phi lp li hai ln. Mi ln thay i dung dch u phi ra n bng nc ct v kim in k phi ch v 0. V th chun. Thay dung dch chun bng dung dch phn tch. c t s trn in k. Da vo th xc nh c nng cht cn phn tch. ng vi kh t, ng t bo quang in. Ra vi phun bng nc ct. Thng kh ton b h thng. 3.3. Phng php quang ph hp th nguyn t (AAS) Nh bit, vt cht c cu to t cc nguyn t v nguyn t l phn t nh nht cn gi c tnh cht ca nguyn t. Trong iu kin bnh thng, nguyn t khng thu hay pht ra nng lng di dng cc bc x, lc ny nguyn t tn ti trng thi c bn. l trng thi bn vng v c mc nng lng thp nht ca nguyn t. Khi nguyn t t do trng thi hi, nu chiu mt chm tia sng c nhng bc sng nht nh vo m hi, nguyn t th cc nguyn t t do s hp th

cc bc x c bc sng nht nh, ng vi nhng tia bc x m n c th pht ra c trong qu trnh pht x. Lc nguyn t nhn nng lng di dng cc tia bc x v n chuyn ln trng thi kch thch, c nng lng cao hn trng thi c bn. l tnh cht c trng ca nguyn t trng thi hi. Qu trnh gi l qu trnh hp th nng lng ca nguyn t Ph sinh ra trong qu trnh ny c gi l ph hp th nguyn t. Nghin cu s ph thuc ca cng mt vch ph hp th ca mt nguyn t v nng C trong mu phn tch, l thuyt v thc nghim cho thy rng. trong mt vng nng C nh, mi quan h gia cng vch ph hp th v nng ca nguyn t trong m hi cng tun theo nh lut Bug- Lmbe-bia.

K: H s hp th, ph thuc vo chiu di sng; C: Nng nguyn t cn xc nh c trong ngn la; L: Chiu dy ca lp hp th;

Da vo gi tr mt quang, ngi ta xc nh nng nguyn t ca nguyn t cn xc nh trong th tch mu. Biu thc trn chng t mt quang ca lp hp th t l thun vi nng ca nguyn t cha trong ti bc sng hp th ng vi nguyn t . Tnh t l ny c bo ton trong mt khong nng nht nh, tu thuc vo tnh cht ca nguyn t cn xc nh v tnh cht ca n. S ph thuc trn l c s thc tin ca phng php phn tch hp th nguyn t nh lng. 3.3.1. Nguyn l v thit b ca php o quang ph hp th nguyn t (AAS) C s l thuyt ca php o AAS l s hp th nng lng (bc x n sc) ca nguyn t t do trng thi hi (kh) khi chiu chm tia bc x qua m hi ca nguyn t y trong mi trng hp th. V vy, mun thc hin c php o ph hp th nguyn t cn phi c cc qu trnh sau: + Chn cc iu kin v mt lot thit b ph hp chuyn mu phn tch t trng thi ban u (rn hay dung dch) thnh trng thi hi ca cc nguyn t t do. l qu trnh nguyn t ho mu. Nhng thit b thc hin qu trnh ny gi l h thng nguyn t ho mu. + Chiu chm tia sng pht x ca nguyn t cn phn tch qua m hi nguyn t va c iu ch trn. Cc nguyn t ca nguyn t cn xc nh trong m hi s hp th nhng tia bc x nht nh v to ra ph hp th ca n. y, mt phn cng ca chm sng b mt loi nguyn t hp th v ph thuc vo nng ca nguyn t trong mi trng hp th. Ngun cung cp ngun tia sng pht x ca nguyn t cn xc nh gi l ngun bc x n sc. + Da trn nguyn tc ca php o ph hp th nguyn t nn dng c dng trong phng php ny gm nhng b phn chnh nh sau: Ngun sng, b hp th,

thit b quang, thit b thu v ghi.

+ Ngun sng: Ngun sng chnh dng trong phng php phn tch quang ph hp th nguyn t l n canh rng. n ny l bnh hay ng hnh tr bng thu tinh c cc in cc dng t nng. Bnh c np y mt kh tr no c p sut thp (agon, neon, heli, xenon...). c vng bc x t ngoi, ca ra ca n c ch to bng thch anh hoc thu tinh c bit. Catt rng ca n c ch to bng mt kim loi tinh khit (hoc bng vt liu khc) di dng ng hnh tr m mt pha trong ca n c ph bng mt cht c cha nguyn t cn xc nh. Tnh n nh ca n khi lm vic l yu t rt quan trng, n nh hng n chnh xc v nhy cm ca phng php phn tch. Tnh n nh c xc nh bng tnh n nh ca ngun duy tr khi lm vic, bng c tnh cu trc v nhng tnh cht c th ca n. Tnh n nh ca n khi lm vic c bit c ngha trong trng hp s dng thang rng. Ngoi nhng loi n catt rng trong thc t phn tch ngi ta cn dng cc n khng cc cao tn. l cc bnh bng thch anh hay bng thu tinh c ng knh t 10 mm n 20mm, trong c a vo mt kim loi tng ng (hay hp cht ca n v mt kh tr-c p sut vi mmHg) dng duy tr s phng in trong n. S phng in trong n c sinh ra khi t n vo trong mt trng in t ca my pht c tn s lm vic 100-2450MHz. Cng c th s dng nhng ngun ph hp th nh l n hiro, n xenon, n teri, nhng cc n ny cha c s dng rng ri trong phn tch quang ph hp th nguyn t. + B hp th: B hp th dng chuyn cht phn tch sang trng thi m trong cc cht cn xc nh s tn ti di dng nhng nguyn t ty do, c kh nng hp th nh sng ca ngun sng bn ngoi. C th dng cc loi n kh lm b hp th. Cc kh thng dng t n l propan, bu tan, axetylen, hiro.

Cht oxy ho kh t chy l xy, c s dng di dng tinh khit hoc di dng hn hp vi khng kh v mt vi loi kh khc. c tnh c bn ca ngn la l nhit v thnh phn kh ca n, thnh phn kh ph thuc vo dng kh t v cht xy ho. Nhit v thnh phn kh ca ngn la xc nh phn li ca cc hp cht a vo v c to thnh trong ngn la. Tu thuc vo t l gia cacbon v oxy, ngn la s c tnh kh hay tnh xy ho. Ngn la c tnh kh khi t l C > 0 c tnh xy ho khi C < 0 v l trung ho khi C= 0. c tnh ca dung mi trong mu c a vo ngn la c th nh hng n nhit thnh phn kh v lm cho ngn la c tnh kh hoc tnh xy ha. Trong ngn la, s nguyn t ho cc nguyn t hoc cc hp cht ca chng xy ra trong nhng iu kin khc nhau, tu thuc vo hp cht ca nguyn t dng bn vng vi nhit hoc khng bn vi nhit. B phn phun v n l hai phn rt quan trng ca b hp th. Chng c tc dng quyt nh n nhy cm v chnh xc ca php phn tch. Thit b phun c dng chuyn dung dch phn tch thnh trng thi sol kh a vo ngn la. n cng gi vai tr ng k trong vic xc nh tnh n nh v v vy n cng xc nh c nhy v chnh xc ca php phn tch. n thng c mt khe lin hoc c mt s dy cc l ring bit. Hin nay ngi ta nghin cu thnh cng cc phng php nguyn t ho cht phn tch trong b phn hp th, l phng php khng dng ngn la v phng php kt hp l - ngn la. Nh nhng phng php ny m nhy tng ln rt nhiu khi xc nh mt lot cc nguyn t. K thut nguyn t ho khng ngn la K thut nguyn t ho khng ngn la ra i sau k thut nguyn t ho trong ngn la. Nhng k thut ny pht trin rt nhanh v hin ang. c ng dng rt ph bin, v k thut ny cung cp cho php o AAS c nhy rt co, c khi gp hng trm n hng nghn ln php o trong ngn la. Php o khng ngn la i hi mt lng mu tng i nh. Thng thng mi ln o chi cn t 20 n 50 l, do khng cn nhiu mu phn tch, vic chun b mu cng d dng hn. V nguyn tc k thut nguyn t ho khng ngn la l qu trnh nguyn t ho tc khc trong thi gian rt ngn nh nng lng ca dng in cng sut ln v trong mi trng kh tr. Dng c nguyn t ho theo k thut ny gm cc nhm chnh nh sau: - Cc loi cuvet graphit; - Cc loi cc graphit;

- Cc loi thuyn lm bng kim loi chu nhit nh tan. Qu trnh nguyn t ho khng ngn la thng gm 3 giai on: + Sy kh mu: Thng nhit 100- 1500C trong thi gian 20 n 40 giy vi lng mu nh hn 100 l - nhit v thi gian sy ph thuc vo bn cht cc cht trong mu v dung mi ho tan. + Tro ho: t chy cc cht hu c v nung luyn mu nhit thun li cho gia on nguyn t ho - nhit tro ho ph thuc vo bn cht ca mi nguyn t v dng hp cht m nguyn t tn ti - nhit tro ho thng thp hn nhit tro ho gii hn ca nguyn t t 30-500C; thi gian tro ho thng t 20-60 giy vi lng mu a vo cuvet nh hn 100 l, trong mt phn ba thi gian dng nng nhit t nhit sy n nhit tro ho t; h phn ba thi gian dng luyn mu nhit tro ho chn. + Nguyn t ho: L giai on quyt nh cng ca vch ph, thi gian rt ngn, t 3 n 6 giy, i khi c th n 1 O giy Tc tng nhit rt ln (1 500- 20000C/1 giy) t ngay tc khc n nhit nguyn t ho Nhit nguyn t ho ca mi nguyn t ph thuc vo bn cht ca nguyn t, trng thi v thnh phn ca mu. + Thit b quang hc: Thit b ny bao gm, dng c quang hc (my n sc hay knh lc) dng tch cc vch phn tch ca ngun, cc thu kinh, cc mng chn v cc gng ph a cc chm sng t ngun qua b phn hp th. + Thit b thu v ghi: Thit b ny gm b ghi nh sng bao gm b nhn quang v cc thit b in nui b khuch i dng quang in. B ghi c th l thit b c biu kin, thit b t ghi hoc thit b hin s cng cc s in tng ng ca ngun nui hay l thit b in. 3.3.2. Nhng u im v nhc im ca php o AAS Cng nh cc phng php phn tch khc, phng php phn tch ph hp th nguyn t cng c nhng u im v nhc im nht nh u im: + Php o ph hp th nguyn t c nhy v chn lc cao. Gn 60 nguyn t ho hc c th c xc nh bng phng php ny vi nhy t 1.10-4 n 1.10-5%. c bit nu s dng k thut nguyn t ho khng ngn la th c th t n nhy n.10-7%. Chnh v c nhy cao nn phng php phn tch ny c s dng rng ri trong nhiu lnh vc xc nh lng vt cc kim loi. c bit l trong phn tch cc nguyn t vi lng. Cng do nhy cao nn trong nhiu trng hp khng ph lm giu trc nguyn t cn xc nh.

+ C th xc nh ng thi hay lin tip nhiu nguyn t trong mu. Cc kt qu phn tch rt n nh, sai s nh. Trong trng hp sai s khng qu 15% vi nng mc ppm. Nhc im: + Phi c h thng my tng i t tin + V c nhy cao nn s nhim bn c nh hng ln n kt qu phn tch hm lng vt. + Phng php ch cho ta bit thnh phn nguyn t ca cht trong mu phn tch m khng ch ra trng thi lin kt ca nguyn t trong mu. V th y ch l phng php phn tch thnh phn nguyn t. 3.3.3. i tng v phm vi ng dng ca phng php i tng chnh ca phng php l phn tch lng nh v lng vt cc nguyn t kim loi ca cc cht v c v hu c trong cc loi mu khc nhau nh: qung, t, , nc, cc sn phm nng nghip, phn bn... Ngoi cc kim loi mt s phi kim nh Si, P, As,Te... cng c th xc nh chnh xc bng phng php ny. Trong khong hai chc nm tr li y php o ph hp ph nguyn t pht trin rt nhanh. N c s dng nh l mt cng c phn tch c lc cho nhiu ngnh khoa hc v kinh t. Hin nay nhiu my o ph hp th nguyn t c sn xut vi nhiu tnh nng u vit. V vy php o ph hp th nguyn t l mt trong nhng php o u vit trong h thng cc phng php phn tch hin nay.

Chng 4 PHNG PHP IN HO

4.1. Cc chn lc ion Phng php phn tch in th l mt trong nhng phng php phn tch ra i sm nht. Nguyn tc ca phng php l o th cn bng ca cc nghin cu xc nh nng cn bng ca cht phn tch hoc theo di s bin thin nng ca n khi n tham gia vo phn ng ha hc. Khi nhng cc lm bng Pt vo dung dch cha cht xy ho - kh lin hp s c hin tng trao i electron gia cc v cht trong dung dch. S trao i ny s gy nn phn ng in ho. Nu nh tc ca qu trnh kh nhanh hn qu trnh xy ho th cht xy ho nhn electron nhiu hn, Pt s nhng electron cho cht xy ho, lc b mt Pt s mang in tch dng, n s ht cc ion mang in tch m vo to nn lp in kp. Gia hai mt ca lp in kp s xut hin mt th E v th E s c o trong phng php phn tch ny. Khi tc ca qu trnh xy ho bng tc ca qu trnh kh, lc lng cht xy ho v lng cht kh khng thay i na. Th E t ti trng thi cn bng. Th cn bng c lin quan n nng hay chnh xc hn l lin quan n hot ng ca cht xy ho v cht kh theo phng trnh Nerst:

Trn thc t khng xc nh c gi tr th cn bng ca mt cc ring bit m ch xc nh th ca n so vi mt cc dng lm cc chun. Trong phn tch in th cc ny c gi l cc so snh (thng l cc cc loi 2 nh cc calomen bo ho hoc cc lc clora). Cc cn o th cn bng gi l cc o hoc cc ch th Trong s cc loi cc ch th dng trong phn tch in ho c mt loi cc rt c bit c ch to t nhng loi mng c bit, th ca cc ph thuc mt cch chn lc vo hot cht cn xc nh. Cc cc ny c gi l cc chn lc ion. Nhng cng trnh nghin cu ca Nerst v ca Reisenfeld v tnh cht c bn ca b mt mng v th xut hin trn ranh gii gia mng v dung ch gip hai nh bc hc ny a ra khi nim v ranh gii pha ca hai cht lng khng trn ln vi nhau. in ho hc v mng c chnh thc nghin cu t nm 1890, trong cc cng trnh ca Ostwald- ngi ta pht hin ra mng bn thm l loi mng cho chuyn qua n nhng loi ln xc nh. Ngay t thi gian u ngi ta ngh ra hai loi mng: mng c (gm mng

mng, mng rn) v mng l xp. Trong s cc loi mng c, ngi ta ch to c cc lo mng thu tinh rt mng v t pht sinh ra cc mng thu tinh l loi cc c th ph thuc chn lc vi hot ca ion hiro trong cc dung dch. Nh khoa hc ngi Nga l Nikolxki xy dng thuyt trao i ln ca cc mng thu tinh. Eisenman v cc cng s xy dng hc thuyt v th khuch tn trong mng thu tinh. Tip theo nh khoa hc ngi Hugari l Pngor v cc cng s nghin cu thnh cng cc loi mng rn chn lc ion ch to cc cc. Cc mng u tin l cc mng d th cha kt ta bc halogenua. Sau ngi ta nghin cu v ch to cc mng chn lc ton n tinh th Frant v Ross ch to c cc chn lc vi ion florua trn c s dng n tinh th lan tan florua. Trong nhng nm gn y, cc nguyn l sinh hc c ng dng ch to cc cc enzim trong mng ca cc c ph mt lp cht mang polyme cha enzim. Cht cn xc nh s phn ng trong lp enzim v to nn sn phm gy ra tn hiu c th o c 4.1.1. L thuyt v cc th mng ca cc cc chn lc ion Cc khi nim c s Mt cc chn lc ln gm thn cc, bn trong cha dung dch cht in li c thnh phn v nng xc nh (dung dch 1), cui cc l mt mng chn lc ion (c th l mng rn ng th hoc d th, hoc n tinh th, mng thu tinh hoc mng lng) v bn trong thn cc c mt cc so snh nhng vo dung dch 1.

Th in ng ca nguyn t in ho trn l:

Cc cc so snh 1 v 2 thng l cc cc loi 2 c th xc nh v khng i, do khi dng cc Cll trong phn tch ch c th mng M l c ngha quyt inh Tng s th ca cc bn trong v th mng gi l th ca cc Cl1, ECl1

Trong trng hp n gin nht, khi mng ca cc Cll ngn cch 2 dung dch trong v dung dch nghin cu ch cha ion cn xc nh j v trong c 2 dung dch hon ton khng c ion khc nh hng ti th mng c quyt nh bi ion j, v th mng c xc nh theo h thc:

Trong : z l in tch ca ion j; aj (l) v aj (2) l hot tng ng ca j trong cc dung dch 1, 2. Trong trng hp trong dung dch phn tch c ion K l ion ngn cn s xc nh hot ca ion j, th th ca Cll c xc nh theo phng trnh Nikolxki. Trong phng trnh ny c s ph thuc ca th vo h s chn lc ca cc ln K i vi ion cn xc nh j. H s chn lc thng l hm s ca thnh phn dung dch nghin cu v gip ta nh hng c nh hng ca cc ion cn tr ti s xc nh ion cn phn tch. Bc nhy th gia cc v mi trng trong trng hp n gin tun theo phng trnh:

E0: th in cc trong mi trng vi hot ca cc ion a = 1, ngha l in cc chun; R: Hng s kh; T: Nhit tuyt i ca mi trng (0K); F: S Faraay; n: S thay i in tch ca ion cn xc nh do kt qu ca phn ng in ho; ax: Hot ca ion X trong mi trng nghin cu. 200C, phng trnh c dng:

Th ca cc ph thuc tuyn tnh vo px cho php chng ta s dng cc trong thc tin phn tch.

4.1.2. Mt vi loi in cc ch th thng thng in cc mng kali: in cc mng kali xc nh hot ca ion K+, c cu to t mt ng thu tinh hoc ng nha, phn cui ca ng l mng mng chn lc ion. Bn trong ng c y dung dch KCl 0,1 M, in cc so snh bc clorua c nhng trong dung dch ny. in cc mng kali nhy vi ion km trong phm vi nng xc nh vi in cc EM.K-01 ca Lin X (c) gii hn ny l t 10-1 n l.10-4. Khi c mt Na+ vi t l K+:Na+ l 1:20 v NH4+ vi t l K+:NH4+ l 1:200 th cc ion Na+ v NH4+ s cn tr php xc nh K+ bng in cc EM.K-01. Trc khi bt u lm vic, cn ra khoang bn trong ca in cc hai ln bng nc ct ti nhit phng v hai ln bng dung dch KCl 0,1M. Sau rt vo in cc 1,5-2,5 ml KCl 0,1 M ri nhng in cc so snh bn trong vo. in cc vo dung dch KCl 0,1 M t nht l 1 ngy 1 m v sau vn gi trong dung dch ny. Dng dung dch KCl chun kim tra in cc sau khi chun b xong.
Dung dch KCl, mol/1 0,2000 0,1000 0,0500 0,0100 0,0050 0,0010 0,0005 0,0001 0,718 0,770 0,816 0,902 0,927 0,965 aK+ 0,436 0,O770 0,O408 0,0090 0,0O46 0,0010 0,0005 0,000 1 pK+ 0,84 1,11 1,39 2,O4 2,34 3,02 3,30 4,00

kim tra in cc cn thit lp mt mng o, in cc K c nhng vo trong dung dch KCl chun, in cc so snh c nhng trong dung dch KCl bo ho. Gia hai dung dch ny c ni bng cu dn lm y bng nga trn vi li axetat (CH3COOLi). o tr s sau khi nhng in cc vo dung dch sau 5 pht. Nu in cc hot ng tt, tin hnh o th ca dung dch th nghim. Da vo thang chun gia th v pK+ tnh ra c hot ca K+ trong dung dch nghin cu.

* in cc mng nitrat: in cc mng nitrat EM - NO3-01 do Lin X (c) ch to c cu to tng t nh in cc kali, ch khc l mng c bo ho bng ion NO3- Khoang bn trong ca in cc cha dung dch KNO3 0,1 M v dung dch KCl 0,005M, sau nhng in cc so snh bn trong vo. in cc so snh bn ngoi thng dng l in cc calomen (thng dng l in cc bc clorua). Th ca in cc mng nitrat trong gi tr pa t 2 - 9 v hot NO3- t 0,0011M tun theo phng trnh: E = E0 - 0,058.PNO3Cc anion khc nh Cl- HCO3-, SO42- vi t l l NO3-: Cl- = 1: 1; NO3-: HCO3= 1: 5; NO3-: SO42-: 1:5 s cn tr vic xc nh SO42-. Trc khi dng in cc nitrat mi, cn phi ra khoang bn trong cc hai ln bng nc ct v hai ln bng dung dch KNO3 v KCl vi nng nh trn, sau rt vo 1,5 - 2,5 ml dung dch ny ri nhng in cc so snh bn trong vo. in cc sau khi chun b xong, c gi qua mt ngy m trong dung dch KNO3 0,1 M v sau ny vn gi trong dung dch Sau khi chun b in cc xong, tin hnh kim tra s ph thuc th ca cc vo gi tr PNO3-. Thit lp mch o gm in cc so snh v in cc nitrat u nhng trong dung dch NaNO3 chun. Sau 5 pht, ghi s trn my o. Nng NaNO3(mol/1) 0,1000 0,0500 0,0100 0,0050 0,0010 0,0005 0, 0001

aNO30,O765 0,O406 0,0090 0,0064 0,0010 0,0005 0,0001

p NO31,11 1,30 2,O4 2,34 3,02 3,30 4,00

0,765 0,812 0,900 0,926 0,964 0,975 1,000

Xy dng th theo kt qu o th trong 3 - 4 dung dch chun. Khi thay i gi tr pNO3- theo n v dc ca th l 58mV.

Cc in cc nhy vi kh in cc nhy vi kh u tin c xem nh l b thu xc nh th c s dng l in cc dng xc nh CO2 trong khng kh. Hin nay c cc in cc nhy vi kh xc nh NH3, SO2, H2... v cc cht kh khc. Nguyn tc lm vic ca cc in cc ny da trn s ch th ca ion c to thnh do phn t kh phn ng vi nc.

Th ca in cc nhy vi kh c xc nh bng phng trnh:

Do vy cng c kh nng xc nh hm lng kh trong mu thng qua vic xc nh th. Kh khn c bn i vi cc in cc nhy vi kh l vic xy dng nhng iu kin thit lp nhanh cn bng gia cht kh v cht lng, v vic chn in cc bn trong kh khuch tn v tham gia thit lp cn bng to nn nhng ion c xc nh bng in cc chn lc ton. Cu to ca cc in cc nhy vi kh:

c tnh ca vi in cc nhy vi kh
Nguyn Cht in ly Gii hn Gc pH ca cht Cht t nhy bn trong di php nghing in ly bn cn o trong tr + -5 10 H NaHCO3 + 60 <4 0,01 M H+ H+ H+ Et2NH2Cl 0,01M NaHSO3 0,1M NaNO2 0,02M m xitrat H+ 1M m ng dng

CO2 NH3 Et2NH SO2

10-6 10--5 10-6 10-4

5.10-7

- 60 - 60 + 60

> 11 > 60 HSO4m m xitrat NH3 Cl2 NO2 SO2 CO2 O2 Kh thi thc phm, vng, cht t Kh thi, khng kh nitrua trong thc phm Phn tch ung, s ln

NO2

H+

+ 60

H2S HF C

S2FC

10-8

- 30 - 60 -60

<5 -2 <2

10-3
10-3

S tinh luyn

Cc in cc nhy vi kh hin nay c s dng xc nh cc ion thut trong t, trong nc bin vi vic kh trc NO3 n amoniac; in cc loi ny cn dng xc nh SO2 trong cc mu sinh hc, nghin cu thnh phn cc thot ra trong cc qu trnh to thnh t, trong qu trnh h hp v dinh dng ca thc vt, ngoi ra cn s dng in cc loi ny xc nh cc cht c hot tnh sinh hc.

Cc in cc so snh in cc so snh hin nay thng c s dng cng vi cc in cc chn lc ton l in cc bc clorua. y l in cc thun tin, n gin, bn v khng i hi phi bo qun ngoi vic lm y bn trong cc bng dung dch lit. in cc bc clorua c v lm bng thu tinh, cui cc c si aming tip xc gia in cc vi mi trng bn ngoi. Bn trong ng c dung dch kali clorua, dy dn bc c b mt xp c ph bng kt ta bc clorua. Th ca in cc c xc nh theo nng dung dch KCl. Khi nng KCl khng thay i th gi tr th ca in cc cng khng thay i Khi phn tch mu ngoi thc a nn dng dung dch KCl bo ho. Th ca in cc bc clorua: Dung dch KCl Dung dch KCl bo ho KCl 1,0 M KCl 0,1M HCl 0,1N HCl 1,0 M Cu dn in Cu dn in dng trc lp mng in vi cc cc chn lc ion l mt ng thy tinh hnh ch U, ng knh bn trong 3-5 mm; di khong 5 - 6 cm; c np y aga trong dung dch mt mui bo ho (KCl, KNO3, CH3COOLi... khi dng cc chn lc ion kali, np vo trong cu do 1 in dung dch liti axetat, cn khi dng cc bc clorua ngi ta np dung dch kali nitrat. chun b cu dn in ly 3g aga nghin nh cho vo cc, thm vo 100 ml nc ct gi qua m. Sau t ln bp, un cn thn v thm t t 10 g mui, khuy u bng tha thy tinh n khi tan hon ton. un hn hp trn nhit 50-600C ri rt cn thn vo ng ch U; gi cho n khi hn hp ngui i. Cn ch rng trong qu trnh cho hn hp vo v gi hn hp ngui khng to bt kh trong ng. Gi cu dn in trong dung dch mui bo ho (mui np vo trong ng). Trc khi dng, dng nc ct ra qua cu dn in, dng giy lc lau kh. Mt u cu c trong dung dch nghin cu cn u kia nhng vo trong dung dch KCl bo ho c cm in cu so snh. S dng cc in cc chn lc ion trong iu kin ngoi thc a Cc in cc ch th lm bng thu tinh v cc in cc chn lc bng mng c E(V) 250C + 0,202(200C) + 0,238 + 0,290 + 0,289 + 0,218

th dng xc nh hot ca cc ion trong cc iu kin ngoi thc a, ngha l xc nh trc tip trong t nu m ca t khng nh hn 15% trong nc thin nhin, nc thi, nc cng nghip, nc ti. Khi lm vic ngoi thc a, ngun in cho my l phi. Trc khi ra thc a cn kim tra cc in cc ch th theo cc dung dch chun. Tt c c cc in cc ch th, tr in cc chn lc ion bc clorua, u phi nhng trong dung dch bi v nu mng b kh, thm ch ch trong thi gian ngn cng c tc hi n cc, lm ri lon chc nng ca cc. Cn xy dng th chun trc ti nhit tin hnh php o ngoi a thc. Phn tch nc trong iu kin thc a, tin hnh tng t nh phn tch dung dch trong phng th nghim. Khi o hot ca cc ion trong t, in cc ch th lm bng thy tinh v in cc so snh c cm vo t vi khong cch chnh xc 5 - 6cm. Khi dng in cc mng cn o l trc vi su bng su ca php o v ng knh l tng ng vi ng knh ca cc. Sau khi nhng cc in cc vo trong t cn n nh lm cht xung quanh cc. Sau 15 - 30 pht, tu thuc vo m ca t, tin hnh o hot ln cn xc nh

Bng 4.1. S dng m s in cc chn lc ion trong phn tch mi trng

Cht phn tch NH4+ Br CO ClKiu n cc Cm ng kh Cc rn Cm ng kh Cc rn Mng lng Cc lin hp Cc rn Cc rn Cc lin hp Cc rn Mng lng Cc rn Mng lng Cm ng kh Mng lng Mng lng Cc rn Cc rn iu chnh cng ln (ISA) pH iu chnh theo ISA NaNO3 5M m CO2 a NaNO3 5M Thuc th iua NaNO3 5M TISAB b (NH4)2SO4 2M NaNO3 5M (NH4)2SO4 2M m axit (NH4)2SO4 2M SAOB c NaNO3 5M

Clorin CNFFlorua borat lNO3 Oxit nit Oxy ho tan ClO4S2SCNGhi ch:

a: m xitrat (Natri xitrat/ axit xitric). b: Dung dch m iu chnh cng ln tng s gm: axit 1,2 xyclohecxilendinitriltetraaxetic v xitrat hoc tactrat. C: Dung dch m chng oxit ho S2- gm: Trilon-B 0,2M; dung dch NaOH 2M v axit ascobic.

C th s dng cc phng php ng chun bng phng php thm xc nh nng ca mt s cu t trong mi trng. V d: xc nh Cu trong mu nc thi bng phng php thm, trc tin em o th ca mu nc tho gi s gi tr th ghi c v 17,5mV (E1); sau tin hnh nh sau: ly 5ml dung dch chun Cl- nng 75 ppm cho vo bnh nh mc 1 100ml, nh mc n vch mc bng mu nc thi cn phn tch. Chuyn dung dch ra cc v tin hnh o bng cc chn lc ion. Th o c s l 35,3 mV (E2) s dng cng thc:

Trong : Cy: Nng cht chun : T l ca th tch dung dch chun trong ton b th tch em o.

S: dc ca in cc. E = E2 - E1 p dng cng thc cho v d trn Cy = 75 ppm; = 5ml/100ml = 0,05 E = 35,3 - 17,5 = 17,8 mV; S = 58,1 mV. Do nng ca Cl- trong mu phn tch l 3,34 ppm. 4.2. Phng php cc ph Phng php l phng php phn tch do nh bc hc Tip Khc (c) Iaroslap Hayropski pht minh nm 1922. Phng php ny c s dng rng ri nh lng cc cht v c v hu c trong cc i tng khc nhau. Nh s hon thin ca k thut cc ph nn ngy nay c hng lot cc phng php cc ph khc nhau: cc ph mt chiu dng khuch tn, cc ph xoay chiu, cc ph hn hng, cc ph xung vi phn... 4.2.1. Cc ph mt chiu dng khuch tn (cc ph c in) Nguyn l: C s ca phng php l nghin cu ng biu din s ph thuc ca cng dng in vo th ca bnh in phn c cu to c bit cha ton can kho st I = f(E) ng biu din s ph thuc c gi l ng Von-Ampe hay cn gi l ng cc ph hoc sng cc ph. c ng Von-Ampe ta dng my cc ph. S n gin ca my nh sau:

Catt hay dng l in cc git thu ngn l in cc ch th cn nut l y thu ngn hay in cc calomen bo ho lm in cc so snh. Th E t vo s to nn phn cc catt (k) v ant (A). Cn bng tng qut ca th bn ngoi t vo c th biu th nh sau:

 y iR l s gim th khi dng i qua dung dch. Cc thnh phn (pH v iR trong cc ph c khuynh hng tin ti cc tiu do b mt ln ca in cc so snh v trong dung dch so snh c cht in ly tr (nn), lm gim in tr R ca dung dch. Do th bn ngoi t vo chi gy nn s phn cc ca in cc git thu ngn. Nu dng in cc git thu ngn lm in cc ch th v in cc so snh l cc Calomen bo ho (th ca cc ny trong cc ph c quy c bng khng) th:

S ph thuc gia th ca in cc git thu ngn v cng dng in biu th bng th di dng ng cong cc ph (cc ph ). Dng tng qut ca cc ph u c biu din hnh 4.8. Khi t c th kh (hoc xy ho) ca ion no c trong dung dch, qu trnh tch phn c bt u, cng dng in tng ln r rt. S tng ln ca cng dng ch khi trong dung dch cn lp khuch tn st in cc c cha ion gy nn dng in phn khi nng ln bng khng th qu trnh tng cng dng s ngng li. Khi bt u hin tng phn cc nng . Khi khng c cc ion c kh hay c oxy ho lp st in cc, cng dng lc ny c gi l dng gii hn khuch tn, n c gi tr khng i do c s khuch tn cht t dung dch n lp st in cc. Cng dng khuch tn gii hn t l vi tc khuch tn cht n in cc, tc l t l vi nng ca cht c trong dung dch. id = K.C Trong K l h s t l Phng trnh trn chnh l phng trnh dng khuch tn gii hn. D.Incovic a ra phng trinh chi tit:

Trong : n: s electron tham gia phn ng; D: h s khuch tn; m: khi lng thy ngn thot ra t mao qun trong mt n v thi gian, : chu k git thu ngn; C: nng ca cht. Gi tr h s t l K ph thuc vo c tnh ca in cc s dng, c tnh ca ion c kh hoc xy ho, c tnh ca cht in li tr v nhit ca dung dch cc ph. Trong trng hp kh cation, gi tr dng khuch tn gii hn c lin quan n

nng ca nguyn t phn tch ch l mt phn ca dng tng s t.

Trong : ik: dng t in; ig: dng in phn yu do cc tp cht trong dung dch gy nn; ih: dng di chuyn; Dng di chuyn xut hin l do s di chuyn ca cc ion di tc dng ca lc in trng, loi tr cn thm vo trong dung dch phn tch cht in li tr. Dng in phn yu c loi tr bng cch tinh ch cn thn cht in li tr. Dng t in sinh ra do lp in kp ca dng khuch tn st in cc tch in, dng ny ni chung cng kh loi tr. Dng t in v dng in phn cc gp li thnh dng d. Dng d trong nhiu trng hp ln n mc khng th o c sng cc ph, c bit khi xc nh cc kim loi nng trong t, trong nc v trong thc vt i hi tin hnh nhy cao. lm gim dng d mt cch ng k, hin nay trong tt c cc my cc ph u c thit b b chnh. S dng thit b b chnh cho php nhn c dng sng cc ph tt hn rt nhiu v nh th s nng cao hn nhy v lp li ca kt qu. Khi s dng ct thu ngn s thu c nhng kt qu tt v khi s tng ca dng b chnh nh hn nhiu so vi s tng ca dng khuch tn. Nguyn nhn lm tng dng khuch tn l do in cc chuyn ng tip tuyn ca git thu ngn, chuyn ng ny gy nn vic khuy trn lp dung dch cnh git, trn ng cong cc ph c xut hin cc i. loi tr cc i ngi ta thm vo dung dch nhng cht hot ng b mt nh aga- aga, gelatin... khi chuyn ng tip tuyn ca thu ngn s gim i. Sng cc ph ca ion xc nh thng b sai lch do c xut hin sng ca xy, xy cha trong dung dch ca ion xc nh c trn in cc git thu ngn.

loi oxy trc khi phn tch cc ph ngi ta cho kh H2 hay N2 sc qua dung dch. Trong trng hp nhng dung dch c tnh cht axit, loi xy c th dng CO2. Cn trong mi trng kim thng natri sunfit, thm 0,1 g Na2SO3 trong 100ml

dung dch c th kh hon ton c xy trong thi gian khong 5 pht. Phn tch cc ph nh tnh v nh lng Khi xc nh nh tnh ion c kh (hoc xy ho) ngi ta da vo gi tr th bn sng E1/2 Gi tr th bn sng bng gi tr th ca in cc ch th khi cng dng bng 1/2 gi tr ca dng gii hn. Gi tr th bn sng khng ph thuc vo nng ca cht phn ng, khng ph thuc vo vn tc chy ca git thu ngn qua mao qun v cc yu t khc. y l mt hng s c trng cho ion trong mt nn nht nh. V th vic la chn cht in ly tr (cht nn) c ngha to ln trong phn tch cc ph. Hin nay, ngi ta dng cc cht in ly c thnh phn khc nhau (cc axit, cc mui trung tnh, cc dung dch kim, cc cht to phc khc nhau) lm cht nn. i vi a s cht nn, ngi ta thnh lp c cc nguyn t c kh nng c kh hoc c xy ho v cc gi tr th bn sng. Cc bn ny c ghi trong cc sch chuyn kho hoc cc s tay. Khi phn tch mt nguyn t hay mt vi nguyn t phi chn cht in ly tr (cht nn) loi tr nh hng ca cc ion km theo. Gi tr ca dng gii hn hay chiu cao ca sng cc ph trong nhng iu kin nht nh t l vi nng ln cn kho st. xc nh chiu cao ca sng, ngi ta thng dng phng php ca Hon. Theo phng php ny ngi ta k 3 ng thng trn sng, t cc giao im li k cc ng song song vi trc honh. Khong cch gia cc ng thng ny l chiu cao sng cc ph. T im gia ca chiu cao sng cc ph k ng thng song song vi trc honh. T giao im ca ng thng ny vi sng cc ph, k ng thng song song vi trc tung. ng thng ny ct trc honh ti im l gi tr th bn sng. Gi tr th bn sng l gi tr tnh i vi in cc calome bo ho.

 phn tch cc ph, ngi ta thng ly nhng lng th tch nh (3 -5ml) rt ngn c thi gian gii phng oxy khi dung dch. Trong phn tch nh lng, xc nh nng ngi ta s dng cc phng php: phng php dung dch chun, phng php thm v phng php ng chun. Thun li nht khi phn tch hng lot mu l phng php ng chun. th ng chun: trc tung ghi gi tr chiu cao ca sng (h, mm), trc honh ghi gi tr nng C. ng chun thng i qua gc to . i khi th khng i qua gc to m ct trc tung hoc trc honh mt im no y. Trong trng hp ct trc tung c ngha cha hon ton trit tiu dng d hay dung dch nn b nhim nguyn t cn xc nh; khi ct trc honh c ngha l dng khuch tn gii hn c tnh cha hon ton. 4.2.2.Cc ph hn hng (hay Von-Ampe ho tan) C s l thuyt ca phng php. tin hnh cc ph hn hng, ngi ta thc hin qua 2 giai on: + in phn lm giu cht cn phn tch nn b mt cc o di dng mt kt ta (kim loi, hp cht kh tan). Cc o thng l cc thu ngn treo c kch thc nh nh git thu ngn trong cc ph c in, cc quay bng vt liu tr (nh than thu tinh, than nho tinh kt, than ngm tm platin...), cc mng thu ngn trn b mt cc rn tr. Qu trnh in phn thng tin hnh trn cc my cc ph thng thng ti th khng i khi khuy dung dch vi vn tc u. Nu dng cc rn th dng cc cc quay quanh trc ca n, nu dng cc thu tinh ngn tnh th khuy dung dch bng my khuy t. + Ho tan kt ta, lm giu v ghi o gi tr cng dng ti th thay i khng gin on (s tan nut). ng cong biu din s ph thuc ca cng trong qu trnh ho tan nut c dng pic. Theo chiu su pic ngi ta tm c nng ca ion kim loi trong dung dch v theo th ca pic s bit c bn cht ca kim loi. Hnh 10a biu din sng cc ph ca ion Pb2+ nng 2.10-4 M trong dung dch KCNS 0,1 M. Hnh 10b l ng cc ph hn hng (von - ampe ho tan) ca dung dch cha ion Pb2+ nng 10-6, KCNS 0,1 M khi in phn lm giu trong 5 pht ti th (- 0,7 V). Dng cc thu tinh thu ngn treo c kch thc tng t git thu tinh ngn khi o cc ph, tc phn cc ho tan nut l 25mV/s c hai ng cong c ghi cng mt nhy ca in k. Qua ta thy phng php cc ph hn hng c tc nhy cao hn phng php cc ph in rt nhiu. Nhng yu t ch yu xc nh cng dng nut l: nng kim loi trong dung dch, bn knh git thu ngn, th tch dung dch, thi gian in phn, th in

phn, nhng iu kin thu ng lc hc trong thi gian in phn, tc thay i trong thi gian ghi v v yu t khc.

S ph thuc vo nhiu yu t ca ta chng t qu trnh xy ra trong cc ph hn hng l phc tp. C th chia chng ra thnh 2 nhm + Nhng qu trnh xy ra khi in phn; + Nhng qu trnh lin quan vi s ha tan ca kim loi t hn hng Cng dng in phn id do phn ng Men+ + ne + Hg Me (Hg) gy nn, ph thuc vo nng ln kim lo trong dung dch (Co) v ph thuc vo din tch S ca in cc ch th.

y Kd l hng s ca dng in phn, ph thuc vo nhng iu kin thy ng lc hc khi in phn v ph thuc vo ho tr ca ion kim loi v nhiu yu t khc. Tu thuc vo s phi hp ca 3 yu t bn knh git thy ngn (r), thi gian in phn (t), th tch dung dch (v) m nng kim loi trong dung dch sau khi in phn (Cl) c th bng hoc nh hn nhiu so vi nng ban u (C0). Mc tiu hao ca dung dch () sau khi in phn c xc nh bng phng trnh (A.G.Xtromberg, 1962).

Theo cc dn liu ca A.G.Xtromberg, mc tiu hao ca dung dch c nh hng n c tnh ca s ph thuc ca cng dng nut ho tan kim loi t hn

hng v nng ca ion kim loi trong dung dch:

KA l hng s anot, KA ph thuc vo h s khuch tn ca kim loi trong hn hng, tc thay i th khi ghi cc ph, bn knh git thu ngn... Nu b < 0, 1 th, b v phng trnh trn c dng

Phng trnh ny ng khi tin hnh phn tch vi th tch dung dch ln, thi gian in phn ngn v bn knh git thu tinh nh. Nng cc ion kim loi cn li trong dung dch trong trng hp ny thc t khng i. Gi tr ant t l ca ion kim loi trong dung dch, thi gian in phn v bn knh ca thu ngn. Nu b > 3 th 1, phng trnh trn s c dng:

Khi th tch dung dch nh, thi gian in phn ln, bn knh git thu ngn ln th cng dng nut t l thun vi nng kim loi trong dung dch, th tch dung dch, t l nghch vi bn knh git thu ngn v khng ph thuc vo thi gian in phn. Nng ion trong dung dch khi kt thc qu trnh in phn thng nh hn 5% so vi nng ban u. Phng trnh (a) c tun theo trong khong gi tr 0, 1 < b < 3 K thut tin hnh xc nh xc nh mt hay mt vi nguyn t, ngi ta t vo bnh in mt th c gi tr cao hn th bn sng ca nguyn t b kh m nht l 0,2 - 0,3 V. Ti th ny trong thi gian cho, tin hnh in phn dung dch th nghim v thng xuyn khuy u dung dch. Sau khi dung dch khng b xo trn, ngi ta bt u ho tan dt kim loi t hn thng khi th gim u.

(Nng ca Zn2+, Cd2+, Bi3+, Cu2+ l 10-8m; Pb2+ v Te+ l 10-7 M in phn 5 pht ti e = - 1,4V so vi cc calomen bo ha, cc lm vic l git thu ngn treo) Trong phng php Von - Ampe ho tan thng nhng vo bnh in phn cha dung dch phn tch 3 cc: Cc lm vic l cc trn xy ra phn ng kt ta cht cn phn tch di dng kim loi hoc hp cht kh tan. Cc so snh, thng l mt lon cc loi II nh cc calomen hoc cc bc clorua. Cc so snh c th khng i v phi gi th ny khng i trong sut qu trnh lm vic c bit khi tin hnh lin tip cc thc nghim trong thi gian in phn di. bo m c iu , cn ch to cc so snh c din tch b mt ln mt dng qua cc nh. Cc ph tr thng l mt cc platin C 3 cc lm vic chnh: Cc git thu ngn tnh di dng git treo hoc git ngi Cc rn hnh a. Cc mng thu ngn c iu ch ti ch trn b mt cc rn a Trong cc ph hn hng ngi ta hay dng nht l cc git thu ngn tnh. l mt git thu ngn c kch thc nh (ng knh 0,8 - 1,5 mm) v bt ng c treo trn mt mao qun bng thu tinh hoc t trn mt mt thu tinh hi lm, gia c mt on nh v gn platin dn in. m bo tnh chnh xc v lp li ca cc php xc nh, yu cu ch yu ca cc git thu ngn tnh l phi c kch thc khng i v c lp cao, v sau mi mt ln o phi to mt git khc c kch thc nh git dng trong vn o trc. Thng thng ngi lm phn tch khng th ch to c cc git treo anh c cht lng cao v v vy ch c cc hng mi sn xut c cc treo tt. Cc git thu ngn tnh ca hng PAR (M) v cc git thu ngn treo kiu Kemula ca hng Birkmann (M) l cc tt nht.

Nu c c mt git Hg tnh c cht lng tt th vic phn tch s rt thun li v: + Khong th cho php dng cc thu ngn rt rng, xc nh c mt s ln kim loi. Trong mi trng axit khong th dng c tt nht l -0,15 n -1,2V; trong mi trng trung tnh v kim khong th c m rng nhiu: t -0,15 n gn -2V. + Thun li cho vic chn iu kin phn tch nh chn thnh phn dung dch nn, chn th in phn, c bit khi phn tch cc kim loi trong mu c thnh phn phc tp v c th tham kho, nghin cu nhng ti liu khc v phn tch cc ph bit tnh cht cc ph ca cc cht kh cc khc nhau trong cc nn cc ph khc nhau. Xc nh nng cht phn tch: Nng ca kim loi trong dung dch phn tch thng xc nh bng phng php thm. Khi phn tch nhiu mu c cng mt thnh phn c th s dng phng php ng chun. Cng c nhng trng hp gim nh hng do s bin i kch thc ca ht, do s thay i nhit , thi gian in phn v cc yu t khc n kt qu phn tch, c tc gi s dng cht chun trong Khi s dng cht chun trong tnh nng ngi ta khng dng chiu cao lc ca qu trnh ho tan nut kim loi t hn hng m dng t l chiu su gia lc ca nguyn t cn xc nh v lc ca nguyn t a vo trong dung dch lm cht chun trong. 4.2.3. Cc ph sung Nhng phng php phn cc in cc hot ng bng nhng xung in p gin on c bin v b rng (thi gian tn ti) xc nh gi l nhng phng php cc ph xung. C hai phng php cc ph xung c bn hin ang c s dng ph bin: Phng php cc ph xng bin i u (Normal pulse polarography -NNP) Phng php cc ph xung vi phn (Dfferential pulse polarography - DPP) 4. 2. 3.1. Phng php cc ph sung bin i u (NPP) 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 , in p ny c gi l in p khi im, tng ng vi cht sng trong phng php cc ph c in, trong mi mt chu k git, in cc c phn cc b sung bng mt xung vung gc c khong tn ti rt ngn (40 n 100 ms) c a vo st nt trc khi git ri (hoc chu k kt thc). 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 quyt th tuyn tnh trong cc ph c in. Cng dng cc ph c ghi theo mt trong hai cch sau: Ghi cng dng cc ph ti mt thi im xc nh sau khi t xung (thng l 17ms trc khi ngt xung), phn ln cc my hin ang s dng thc hin theo cch

ny. Ghi cng dng cc ph hai ln, ln th nht trc khi t xung v ln th hai sau khi t xung (trong 2 khong thi gian ging nhau: 17 ms trc khi t v 17 ms trc khi ngt xung). Cch ny cho hiu qu tt hn nhng kh phc tp. Phng php NPP c th t nhy 2.10-7M cho c hai qu trnh thun nghch v bt thun nghch. 4.2.3.2. Phng php cc ph sung vi phn (DPP) Trong trng hp ny, in cc c phn cc bng mt in p mt chiu bin thin tuyn tnh vi mt tc chm, nhng cui mi mt chu k git (git ri cng bc nh mt b g) trn khung in p bin i mt chiu, ngi ta t thm mt xung vung gc vi bin trong khong 10 - 100mV v di xung t 40- 100 ms. Cng dng cc ph c ghi hai ln, ln mt ti thi im 1, thng l trong 17ms trc khi np xung l ln th hai ti thi im 2, thng l 17ms trc khi ngt xung. Hai gi tr ny c a vo b so snh v kt qu chuyn ra b ghi l hiu s ca hai gi tr o. ng cc ph c dng pic. u im ni bt ca phng php ny v c nhy cao vi cc hp cht v c v hu c cc qu trnh thun nghch v khng thun nghch v quan trng hn l ng I-E c dng nh cc i, sau mi mt nh dng in ti tr v trng thi nn, do phng php c phn gii rt cao, c th t n 50.000 (v d c th ghi 10-7M Cd2+ khi c mt 5.10-3 Cu2+ m khng cn tch). iu ny cho php phn tch trc tip nhiu cht trong cng mt dung dch. Mt hng phn tch c nhiu trin vng l s dng kt hp DPP vi Von -Ampe ho tan, v d c th xc nh 10-9 M Pb2+ v thi gian khng qu 3 pht. C th ni, hin nay DPP l phng php cc ph hon chnh nht v phng php ny c nhy cao, chn lc cao v c tnh vn nng i vi hu ht cc i tng phn tch.

Chng 5 CC PHNG PHP PHN TCH SC K

5.1. M u Nm 1906, nh bc hc Nga Michael Tvest cho dung dch cc sc t thc vt trong ete du ho ln ct nhi bt mn canxi cacbonat, ng thy cc sc t b hp ph ln trn u ct. Khi cho ete du ho ln ct, cc sc t di chuyn trong ct t trn xung di, mi sc t c mt tc ring, tch thnh nhng vng hay vng mu xp chng ln nhau, hnh thnh mt h m Tvest gi l sc . ng t tn cho phng php tch ny l sc k (Chromatography). Trong ting Hy Lp chroma l mu, graphein l vit. Tn gi ny ngy nay vn c s dng mc d phng php ny cn c dng tch cc cht khng mu. 5.2. Mt s khi nim 5.2.1. Qu trnh sc k Sc k l mt nhm cc phng php ho l dng tch cc thnh phn ca mt hn hp. S tch sc k c da trn s phn chia khc nhau ca cc cht khc nhau vo hai pha lun tip xc v khng ho ln vo nhau: mt pha tnh v mt pha ng (trong th nghim ca Tvest: pha tnh l canxi cacbonat, pha ng l ete du ho). Qu trnh sc k gm 3 giai on chnh a) a hn hp ln pha tnh (v d: a dung dch cc sc t ln u ct canxi cacbonat). Cc cht c gi trn pha tnh. b) Cho pha ng chy qua pha tnh (dung mi e du ho qua ct), pha ng s ko theo cc cht di chuyn trn pha tnh vi tc khc nhau, tc khi nhau v c v tr khc nhau trn pha tnh to thnh sc . Giai on ny gi l khai trin sc k. Nu tip tc cho pha ng chy qua th cc cht c th ln lt b ko ra ngoi pha tnh (v d: ra khi ct). l qu trnh ra gii v dung mi dng c v dung mi ra gii (eluent), dch hng c cui ct gi l dch ra gii (eluate). Nu cc cht c tch trn pha tnh (sc k khai thm ta c th ly tng phn pha tnh c mang cht (phn on bt trn ct) em chit ly cht. Nu cc cht c tch ra ngoi pha tnh (sc k ra gii) ta c th hng thu ly cc phn on dch ra gii c cc cht cn phn tch. c) Pht hin cc cht: Cc cht mu c th pht hin d dng, cc cht khng mu c th pht hin bng n t ngoi hay bng cc thuc th. Trong sc k ra gii c th pht hin cc cht khi chng i ra khi ct bng cch cho dung dch ra gii i qua mt b phn pht hin gi l etect t sau ct.

5.2.2. Phn loi cc phng php sc k - Theo bn cht vt l cc pha Pha ng c th l mt cht lng hay cht kh, pha tnh c th l mt cht rn (ht xp hay bt mn) hay mt cht lng (c gi trn mt cht mang rn). Do , da vo bn cht cc pha ta phn bit cc phng php (trong tn ca phng php, pha ng c nu trc pha tnh): Sc k lng - lng (liquid - liquid chromatography LLC) Sc k lng - rn (liquid - song chromatography LSC) Sc k kh - lng (gas - liquid chromatography GLC) Sc k kh - rn (gas - solid chromatography GSC) Hai phng php u gi chung l sc k lng (LC). Hai phng php cui gi chung l sc k kh (GC). - Theo hin tng sc k Sc k hp ph (absorption chromatography): pha tnh l mt cht rn c kh nng hp ph, l cc phng php sc k lng - rn v kh - rn. Sc k phn b (partition chromatography): pha tnh l cht lng khng ho ln c vi pha ng, cht lng ny c bao trn b mt ca mt cht rn gi l gi hay cht mang v phi l cht tr, khng tham gia vo sc k. Sc k phn b bao gm sc k lng - lng v sc k kh - lng. Sc k trao i ion (ion - exchange chromatography): pha tnh l cht nha trao i ion chp cht cao phn t c mang nhng ion c kh nng trao i vi cc ion cng du ca dung dch hn hp sc k). Sc k theo loi c (size - exclusion chromatography): cn gi l sc k trn gel. Cc phn t c ln s c lot cc phn t nh hn s c tch theo kch thc do cc phn t nh di chuyn chm hn. - Theo k thut v phng tin sc k a) Theo phng php gi pha tnh: Sc k trn ct (column chromatography: CC) pha tnh c cha trong mt ct bng kim loi hay thu tinh. Sc k lp mng (thin layer chromatography: TLC): pha tnh c trng u v gi trn mt phng ca bn thu tinh, nha hay nhm. Lp mng pha tnh thng l: silicagel, nhm oxit, xenluloz, cht nha trao i ln v c chiu dy khong 0,25 0,5mm. Sc k giy (paper chromatography - PC) pha tnh (lng) c thm trn mt loi

giy lc c bit gi l giy sc k b) Theo cch cho pha ng chy ta c: Sc k khai trin (development chromatography) cho pha ng kp cc cht chy v tch trn pha tnh (Sc nm trn pha tnh). Sc k ra gii (elution chromatoglaphy) cho pha ng chy v kp cc cht ln lt ra ngoi pha tnh (ra khi ct, ra khi giy). Ghi ch: Sc k lp mng v sc k lp giy c gi chung l sc k mt phng (planar chromatography). Sc k lng c th tin hnh trn ct, trn mt phng (lp mng, giy). Sc k c tin hnh trn ct Sc k c khai trin thng c thc hin trn mt phng (giy v lp mng). Sc k ra gii thng tin hnh trn ct - Phn loi sc k theo bn cht cc pha Ghi ch: GSC: sc k kh - rn LSC: sc k lng - rn BPC: sc k pha lin kt. LLC: sc k lng - lng AC: sc k i lc TLC: sc k lp mng 5.2.3. S tch sc k v sc - S tch sc k v sc Khi cho mt dung dch cha cht A v B chy qua mt ct cha cht hp thu Nng ca cht A v B trong dung dch s gim i do mt phn cc cht ny phn b chuyn vo cht hp thu. Nng ca cc cht tan A, B trn cht hp thu s tng dn v A, B b cht tch ra khi dung dch. ng thi cng xy ra mt qu trnh ngc li, cc cht A, B trn ct hp th li phn b tan tr li vo dung dch. Qu trnh ny ph thuc vo h s phn b ca A, B trong dung dch v cht hp thu cho n khi t cn bng. Tc hp thu = tc gii hp Tuy nhin v pha ng (dung dch) lun di chuyn nn cn bng trn li b ph v, v mt cn bng mi li c thit lp. C nh vy qua rt nhiu cn bng (c khi hng nghn cn bng pha) cc cht A, B c tch ra khi nhau do kh nng phn b GLC: sc k kh - lng IEC: sc k trao i ln IC: sc k ion SEC: sc k loi c. PC: sc k giy

ca A, B vo cht hp thu hay kh nng b gi trn ct ca A v B l khc nhau. V d: cho mt dung dch cha cha ion ng v ion coban ln trn mt ct c cht hp thu (1), nh th ng v coban b hp thu trn ct (2). Sau tip tc cho dung mi qua ct, ng v co ban s ko dn xung v dn dn chng tch ra thnh cc lp (3), dung mi tip tc c cho qua ct v 2 lp Cu2+ v Co2+ s c tch ra khi nhau (4,5), ti thi im t2 s thy c 2 di tch ring ra khi nhau trn ct: ta c sc ngay trn ct. Nu dng y ta c sc k khai trin

Nu tip tc thm dung mi, ti thi im t3, di Co2+ s tch ra khi ct, nh thit b etect ta s thu c tn hiu di dng mt nh hay mt lc, thi im t4 di Cu2+ ra khi ct li v cho ta thm mt tc tng ng. Ta thu c mt sc gm hai lc ring bit ng vi 2 cht trn. y l phng php sc k ra gii v sc thu c gi l sc ra gii. V tr ca lc trn trc thi gian l c s nh tnh cht tng ng v din tch di tc l c trng nh lng ca cht. Trong qu trnh ny ta thy mt s khc bit v kh nng phn b trong cht hp thu trn ct: Cu2+ c hp thu mnh hn nn s y Co2+ ra, s d c hin tng l v: tan ca ng trong dung mi nh hn so vi coban i lc ca cht hp thu i vi Cu2+ mnh hn so vi Co2+ V hai l do trn nn ng s b gii hp thu t hn. Nng ln Co2+ trong dung mi t nh n cc i ri gim n 0. Tc di chuyn ca di ph thuc vo tc di chuyn ca pha lng (pha ng) v mc hp thu ca cht hp thu i vi cht tan. Cht no b hp thu mnh nht s di chuyn chm nht v n b dung mi gii hp t nht. C nh vy trong iu kin thch hp ta s tch c hon ton cc cht ra khi nhau: Do tc dng lm chm (retardation), do s phn b hp thu khc nhau ca pha

tnh i vi tng hp phn trong hn hp, ngi ta c th tch ra tng hp phn trong hn hp. V vy, nguyn tc ca phng php sc k lm Da vo s phn b khc nhau ca cc hp phn trong hn hp gia hai pha ng (moving phase) v tnh (stationary phase) - Tc di chuyn ca mt cht Tc di chuyn ca mt cht c th c c trng bi h s phn b ca n gia hai pha hoc bi cc i lng v s lu gi ca cht trn pha tnh (thi gian lu, th tch lu) a. Thi gian lu v th tch lu: Thi gian lu l thi gian cn mt cht di chuyn qua ct sc k, khi ra khi ct nh thit b etect ghi nhn tn hiu v xut hin rc trn sc (tnh t lc bm mu n khi xut hin pic).

TM l thi gian lu ca mt cht khng b lu gi, ngha l tc di chuyn ca n bng tc di chuyn trung bnh ca dung mi, thi gian ny c gi l thi gian cht. tR cng ln, cht cng b lu gi mnh v tc di chuyn ca n cng nh. Thi gian lu hiu chnh tR c tnh theo cng thc:

Nu trn trc honh ca sc , dng n v o l th tch dung mi th ta c cc i lng tng t: th tch lu VR v th tch lu hiu chnh VR' th tch VM c gi l th tch cht ca ct hay cn gi l th tch rng Vo.

b. H s phn b

Trong : Cs v CM l nng cht tan trong pha tnh v pha ng khi cn bng c thit lp. Khi nng nh K ph thuc vo bn cht cc pha, cht tan v nhit K cng ln th cht phn b cng nhiu trong pha tnh v di chuyn cng chm.

c. H s dung lng K' (h s phn b khi lng)

Trong : Qs v QM l lng cht tan phn b trong pha anh v pha ng, K' ph thuc vo bn cht cc pha, bn cht cht tan, nhit v c im ca ct. tch mt hn hp cht, ngi ta thng chn ct, pha ng v cc iu kin phn tch khc sao cho K' nm trong khong t 1 n 8. - S dong pic v hnh dng pic a. Hnh dng pic: Hnh dng l tng ca tc l lc i xng, nhng thc t lc sc k ch gn i xng. Chiu rng ca tc c o 1/10 chiu cao ca pic. b. S dong pic: S dong pic l kt qu ca s di chuyn nhanh, chm khc nhau ca cc phn t ca cng mt cht khi i qua ct sc kh. Cc lc ra chm bao gi cng t hn. c. Hiu lc ca ct: Hiu lc ca ct thng c o bng hai thng s: s a l thuyt N v chiu cao a l thuyt H. Ta c th coi nh ct sc kh c chia thnh N lp hay N tng mng, mi mt lp s phn b cht tan vo hai pha t trng thi cn bng. Nhng tng mng gi nh ny c gi l a l thuyt. Nu ct sc kh c chiu di l L th: H =
L . Ct c N ln l ct c hiu lc cao. N

d. phn gii: phn gii Rs l t s khong cch gia hai pic v rng trung bnh ca pic. Rs = 0,75 hai pic tch khng tt, cn xen ph nhau nhiu; Rs = 1,0 hai pic tch kh tt, cn xen ph nhau 4%; Rs = l,5 hai pic tch hon ton (chi xen ph 0,3%). 5.3. Sc k lng hiu nng cao Sc k lng hiu nng cao (high perfonnance liquid chromatography-HPLC) cn c gi l sc k lng cao p hay sc k lng hin i. Trong phng php ny pha tnh c dng l nhng ht c kch thc rt nh, khong 10 micromet, c hiu sut tch rt cao, c ht nh i hi phi dng bm nn dung mi qua ct. 5 3.1. My sc k lng hiu nng cao S nguyn tc ca mt my sc k lng hiu nng cao nh sau:

- Cc thnh phn chnh ca my sc k lng hiu nng cao a) Bnh cha dung mi Thng lm bng thu tinh, i khi lm bng thp khng r, trong phng php ra gii thng thng ch cn mt bnh cha dung mi, trong phng php ra gii gradient thng dng 2, 3, 4 bnh cha cc dung mi khc nhau v h dung mi ra gii l hn hp ca cc loi dung mi trn trn ln vi nhau theo ti l c xc nh. Cn loi cc ht v cc kh ho tan trong dung mi. b. H thng bm Bm dng trong phng php phi to c p sut cao (3000 - 6000 psi hay khong 250 - 500 at), lu lng bm khong 0,1 n 10 ml/ph, phi tr vi cc dung mi. H thng bm ny phi c kh nng bm pha ng qua ct p sut cao m khng b ngt qung hoc to nhp sng c th lm sai lch cc lc thu c. C nhiu kiu bm dng trong cc my HPLC; nhng kiu phng xoay chiu hin nay c dng ph bin nht. c) H bm mu (h tim mu) Mu c bm vo ct nh h thng van mu. Ngi ta bm mu vo vng mu vi th tch thng l t 10 n 20 l. d. Ct sc k Kiu ct thng ph thuc vo phng php dng tch, nhng thng l nhng ct bng thp khng g, c c l chnh xc ng knh t 3 n 4 tm v di t 10 n 30cm (nhng ct dng cho SEC ng rng hn v di n 100cm). Loi ct ny c hiu lc rt cao, c s (ra l thuyt ln n 100.000 a cho 1m chiu di ct)

e) etect L b phn pht hin cc cht khi chng ra khi ct v ghi nhn cc tn hiu ghi trn sc . Hin ang s dng cc loi etect sau: etect t ngoi (UV): Dng n thu ngn cho vch 254nm. Nhiu cht hp th bc sng ny. etect t ngoi v kh kin (UV-VIS): Dng ph quang k la chn bc sng t 195 n 750 nm. Loi ny hin nay c dng nhiu nht. etect in ho v etect hunh quang c nhy v chn lc cao dng trong phn tch vt. Dng etect in ho c th pht hin c nhng lng picrogam (10-12g) 5.3.2. Cc phng php sc k hiu nng cao a) Sc k phn b hiu nng cao Gm hai loi: Sc kh lng - lng v sc k pha lin kt. - Sc k lng - lng (LLC): Pha tnh l cht lng c bao trn b mt ca cc ht cht mang, tc l c hp ph trn cht mang. - Sc k pha lin kt (BPC): Pha tnh c gn ho hc vi cht mang to ra lin kt siloxan ni nhm c - silic vi silicagen. b. Sc k hp ph hiu nng cao (sc k lng - rn LSC) Pha tnh l cht rn m trn b mt c cha cc nhm hiroxil phn cc, pha ng l mt dung mi khng phn cc. c) Sc k trao i ion hiu nng cao (IEC) Pha tnh rn cha cc nha trao i ln di dng bt mn, pha ng thng l dung dch nc. d. Sc k lng hiu nng cao trn gel (sc k loi c SEC) Phng php ny c ng dng ch yu cho cc cht c phn t lng ln. Cht nhi cho SEC l nhng ht xp ca silicagent hay cc polyme c kch thc nh ( 10 m). Pha tnh l dung mi nm trong cc l xp ca ht, pha ng l dung mi chy gia cc ht. Ch nhng phn t nh mi khuch tn vo lp xp, khi ra gii cc phn t s ln lt ra theo c t ln n nh. 5.4. Sc k kh (GC - Gas chromatography) Sc k kh l phng php c dng tch cc cht th kh bay hi, vi pha l cht kh, gi l kh mang (carrier gas). Nh nu trn, c th cha php sc k kh thnh sc k kh rn (GSC - gas solid chromatography) trong pha tnh rn l mt cht hp ph, y l sc k kh hp

ph v sc k kh lng (GLC - gas liquid chromatography) trong pha tnh lng c bao hay gn trn mt cht mang rn solid support) y l sc k kh phn b. S dng phng php sc k kh c kh nng tch c hon ton nhng cht hu c tng t, v d nh o-; m-; p-xilen khng th tch c bng phng php chng ct phn on nhng tch c kh n gin bng sc k kh, cng nh s dng tch nhng hn hp rt phc tp nh kh thi t cha trn 300 hp cht. Vi vic ra i ca nhiu loi etect, nhiu phng php mi xut hin nh: sc k kh - khi pho (GS - MS), sc k kh - hng ngoi (GC - IR)... lm tng kh nng phn tch ca sc k kh My sc k kh - S nguyn tc ca mt my sc k kh nh sau:

Kh mang Kh mang l mt kh tr nh nh, hen, ngon, hidro... trong hai l kh mang ph bin nht. Kh c cha trong bom kh c gn van gim p v iu chnh. Kh mang cn c tinh khit cao v phi khng tng tc vi mu, ch mang mu i qua ct: Tn hiu etect c ph thuc vo s khc nhau v tnh cht gia kh mang v cht cn phn tch. B bm mu Thng dng bm tim bm trc tip mu qua mt vch polime silicon chu nhit cao vo ct hoc vo phng un nng mu mu lng c th bay hi nhanh chng. Yu cu cn thit l mu phi c p sut hi c th c lm bay hi trong phng mu. Nhit phng mu c th cao hn nhit trong ct mt cht qu trnh bay hi c thc hin d dng. Ct sc k Ct c t trong l c th iu chnh nhit trong qu trnh thc hin. Ct thng dng nht trong phn tch l nhng ng bng thp khng r (ng,

thp) hoc bng thu tinh di t 1 n 10 m v c ng knh t 2 n 4 mm. Chng c un cun trn cho khp vi phng l. Ct c nhi bng nhng phn t rn hot ng nh mt pha tnh (GSC): l nhng ht nh xp gn trn mt trong ct hoc pha tnh c tm trn cc ht nh . Trong sc k kh lng (GLC), pha tnh c gi trn cht mang, l nhng ht cht rn nh, bn nhit, tr v mt ho hc, c l c 1 - 5 m, b mt ring ln t 1 - 10 m2/g. Pha tnh phi chu nhit, ho lng nhit phn tch, tr v ho hc. Thng hay s dng cc polyme xp hoc gel aluminosilicat kh nc. etecl Yu cu v etect rt nghim ngt: Mi hp phn c trong 0,1 l mu phi c pht hin mc 1% cho nn phi nhanh chng pht hin c 0,002 l (c khi lng c 10-6 g) mu. Cc etect hin nay o c nhng lng nh hn n my bc. Hin nay trong phng php GC ngi ta s dng nhng loi etect sau: etect dn nhit (TCD): Vic vn hnh ca etect da trn s cn bng nhit ca mt dy dn nung nng. Khi c cht cn phn tch i qua th dn in ca hn hp kh s thp i, dy s nng ln, xut hin mt tn hiu in. etect dn nhit thch hp vi nhiu cht cn phn tch. etect ion ho ngn la (FID): Khi t chy cc hp cht hu c trong ngn la, chng s to ra cc ion. Cc in cc gn ngn la s pht hin ra s c mt ca cc ion bng s xut hin mt dng in nh chy qua mch in. C th o c nhng dng ngay c khi chng ch xp xi bng 10-12A. y l etect c dng nhiu nht, pht hin c n 10-9g. etect hp th electron (etect bt electron - ECD): Nh c ngun phng x nh H hoc 63Ni, kh mang b ion ho to nn mt "dng nht nh" trong mch etect. Khi mt cht phn tch hp th electron c gii hp n s lm gim dng ny, c bit khi hp cht c cha nguyn t c m in cao. Dng s gim i, to ra tn hiu ghi . etect c bit nhy cm vi nhng hp cht cha halogen. etect hp th electron rt thun li cho vic phn tch mi trng. nhy cao, t ti 10-12g.
3

Thng tin GC Sc thng thng biu th trn hai trc x v y, trong tn hiu etect ghi trn trc y v thi gian ghi trn trc x. Khi mt hp phn ca mu c gii hp v pht hin nh etect th tn hiu s c ghi li. Thi gian ghi c lc tn hiu l hm ca KD v v th n cung cp thng tin nh tnh v mu ging nh th bn sng trong cc ph, v s nhn bit c mt hp phn trong mu. Thng tin nh lng t sc c rt ra t ch tn hiu etect l hm ca thi

gian. Din tch di lc t l vi lng cht phn tch. Lng ny c th biu th bng n v mol hoc n v khi lng, tuy nhin hng s t l s khc nhau: SA = din tch di pic - R A Trong R l din tch trn mt mt kh A c biu th bng mt hoc l din tch trn mt gam kh A biu th bng gam.

Chng 6 CC LOI NC V CC PHNG PHP PHN TCH NC

6.1. i cng v cc loi nc 6.1.1. Nc thin nhin Nc thin nhin bao gm cc loi nc c ngun thin nhin nh sng ngi, h, ao, sui, mch ngm, bin, i dng. C th ni nc thin nhin l mt h d th nhiu thnh phn, v nc thin nhin lun cha nhng lng no cc cht tan v khng tan c ngun gc v c cng nh hu c. Cc cht c a vo t kh quyn, t t v cc ngun cha hoc cc mch nc chy qua. Cc cht cn c to thnh do hot ng sng v s phn hu ca cc c th ng vt, thc vt sng trong nc hoc y cc ngun nc. Cc hot ng ca con ngi trong cc lnh vc khc nhau ca sn xut v i sng hng ngy cng nh hng ti thnh phn nc trong thin nhin. Vic bn phn v s ci to t bng phng php ha hc, cc ph thi ca cc nh my, cc khu cng nghip c bit l nc thi cng nghip v hot ng khc ca con ngi cng a vo nc thin nhin nhng cht v c v hu c. C nhiu cch phn loi nc thin nhin, nguyn tc ca s phn loi ph thuc vo mc ch phn loi v nghin cu nc. Da vo ngun gc ca nc, c th chia thnh cc loi; nc kh quyn (nc ma, tuyt), nc ngm, nc b mt (nc sng, ngi, h ao, bin...). Da vo nguyn tc v mc ch s dng nc c cc loi nh: nc n, nc sinh hot, nc k thut, nc cha bnh,... Da vo hm lng v c tnh ca cc cht c trong nc, chia thnh: nc ngt (cha hm lng cht tan < 0,1%), nc khong (hm lng cht tan t 0,1 2,5%) nc bin (hm lng cht tan t 2,5-5,0%), nc mui (hm lng cht tan >5%). Ngoi ra ngi ta cn phn chia thnh cc loi nh nc cng, nc mm, nc trong, nc c, nc c mu, nc c mi,... Nc thin nhin c c trng bng mt lot cc tnh cht nh c, mi vi, kim, cung, cn khng tan,... s tn ti ca cc loi vi sinh vt khc nhau, cc qun th ph du, cc loi rong ru cng c th lm cho nc b nhim bn. Da trn cc tnh cht ho l c th chia cc hp phn ha hc thnh 3 nhm ln nh sau: a. Cc cht ho tan trong nc di dng cc ion v phn t: Cc con v c trong nc vi hm lng ln nht l Na+, K+, Ca2+, Mg2+, Cl-, HCO32-, CO32-, SO42-. Cc ion c hm lng nh hn l Fe2+, Fe3+, Mn2+, Br-, I-, F-, BO2-, HPO-24, HSO3-, HS-, HSiO3-. Cc ion v c cn li c hm lng rt nh trong nc c gi l cc

ion ca cc nguyn t vi lng v siu vi lng. Cc kh c hm lng ln l O2, CO2, N2, H2S. Cc kh nh CH4, Ar, RN,... c hm lng nh. Cc cht tan hu c thng gp trong nc t nhin l fomanehit, phenol. b. Cc hp phn to nn nhng h keo trong nc bao gm cc h keo v c nh SiO2, Al(OH)3, Fe(OH)3. Cc h keo hu c nh cc cht mn. Cc h keo thng lm cho nc c mu. c. Cc cht to vi nc cc phn t nh ct, st v cc hp cht hu c khc nhau. Cc hp phn sinh hc ca nc thin nhin bao gm cc loi vi khun, vinh ng vt c kch thc ln, rong ru, to... trong nc thin nhin c cha mt lng thc n cho cc thu sinh vt. V vy, thnh phn nh lng v nh tnh ca chng ph thuc nhiu vo thnh phn ho hc ca nc. i vi cc vi sinh vt trong nc, bn cnh nhng vi sinh vt c li cn c nhng vi sinh vt c hn. V vy trong vic phn tch nc th xc nh ch tiu vi sinh vt cng c ngha ht sc quan trng 6.1.2. Nc thi Cng vi s pht trin ca vn minh nhn loi, nhu cu v nc ngy cng tng, lng nc cng nghip cng nh nc sinh hot thi ra ngy cng nhiu, gy nhim ng k n nc mt v mi trng. Do , nhiu vng nc mt b nhim cc loi hp cht ha hc v cc loi vi sinh vt c hi. Trong nhng nm gn y, nguy c lm nhim mi trng do cc cht hu c, c bit l cc sn phm cng nghip v khai thc ch bin du m gy ra ngy cng tng. Vic nhim cc loi thuc tr su, dit c, cc cht ty ra tng hp cng l mi e do ng k n s tn ti ca cc loi thu sinh v con ngi. Ngoi ra cn phi k ti cc cht thi phng x thi ra t cc phng th nghim. C th ni nc thi l mt h d th phc tp, bao gm rt nhiu cht tn ti di cc trng thi khc nhau. Nu nh nc thi cng nghip cha rt nhiu cc ho cht v c v hu c th nc thi sinh hot li cha rt nhiu cc cht di dng prtein, hiratcacbon, m, cc cht thi ra t ngi v ng vt, ngoi ra cn phi k n cc loi rc ri nh giy, g. cc cht hot ng b mt,... Cc hp cht v c thng gp y l cc ion nh: Na+, K+, Mg2+, Ca2+, Cl-, CO32-, SO42-. Ngoi ra nc thi sinh hot cn cha cc vi khun, virut, rong, ru. Vi nhng ngnh sn xut khc nhau th trong cc nc thi s c nhng loi ho cht khc nhau nh: - Khai khong: Cc kim loi, cc axit v c. - Gia cng g flo, km. - gm: Ba, Cd, Li, Mg, Se

- da: Ca, H2S, Na2S, CR, Zn, Ni... - Luyn cc: NH3, H2S, Cc kim,... - Cng nghip sn: Ba, ClO3-, Cd, Co, Pb, Zn, Mn... - Ho dc: B, Br, NH4+, K, cc axit, kim, cc cht hu c,... - Thu tinh: H3BO3, As... Trong s cc ho cht gy nhim bn ngun nc th Hg, Be, Cd, Pb, As, Se c c tnh rt cao. Nc thi sinh hot c thnh phn ha hc n gin hn, ch yu bao gm: K, Na, Fe, Pb, Zn, Ni, Mn, Hg, Ag, Co. Vic phn tch nc thi rt kh khn v phc tp. Khi phn tch cn phi tin hnh cc qu trnh tch, lm giu, la chn cc phng php c nhy, chn lc cao. Mt trong nhng c dnh gy kh khn cho vic phn tch nc thi l tnh cht khng bn vng ca ni i vi nc n, vic phn tch ha hc n gin v loi nc ny c x l v mt c, ho v sinh hc. 6.2. Phn tch nc 6.2.1. Phn tch nc thin nhin Vic phn tch nh gi cht lng nc thin nhin ph thuc vo mc ch s dng loi nc , nhng ni chung phn tch y mt mu nc ti nguyn cn xc nh kho st mt s loi ch tiu sau y: - Cc thng s v vt l v cm quan nh nhit , v, c, t trng - Cc thng s v thnh phn ha hc nh hm lng cc cation, anion v cc cht hu c. - i vi nc sinh hot, ngoi cc ch tiu trn cn phi xc nh v nh gi c v ch tiu vi sinh vt. 6.2.2. Phn tch nc thi Thnh phn nc thi khc nhiu so vi nc thin nhin, v th phn tch nc thi li theo mt s khc. Mu nc thi thng phn tch ngay trong ngy ly mu. Sau y l cc ch tiu cn phn tch i vi nc thi: - Nhit - Mu sc. - Mi v - c

- pH. - Lng kt ta - bn tng i ca nc. - Cc cht l lng. - Tng s mui tan - Cc cht mu, cht hu c c hi. - Kim loi nng 6.2.3. Nhng iu cn lu khi phn tch nc Phi ly v bo qun mu ng quy cch v tun theo mt cch nghim ngt cc quy tc ly mu. Thng thng mu phi ng trong bnh polietylen. Phi chn phng php phn tch thch hp. Phi s dng ng quy cch cc dng c v ho cht. 6.3. Ly v bo qun mu nc 6.3.1. Xc nh v tr ly mu Mu ly xc nh tnh cht thng thng ca nc c th lay ngu nhin t b mt vo thi gian bui sng. Tuy nhin, khi nghin cu mt cch ch tit hn, cn phi t k hoch v xc nh vi tr ly mu trc i vi vng nc rng nh: ao h, mu ly phi i din cho nc ton b vng cn phi ly nc ngun thi vo v ra khi h cng nh tc ng ca con ngi n ngun nc. Tu theo vng nc nng hay su m c th ly mu mt tng, hai tng (tng mt v tng y), ba tng hoc nhiu hn na cc sng, sui c th ly dc theo dng nc v theo chiu ngang nu rng nhng ni c ngun nc thi, cn ly cc im trc v sau im ho nhp ca ngun nc thi. 6.3.2. Ly mu nc V tr ly mu ph thuc vo mc ch ca nghin cu. Thi gian v tn sut ly mu ph thuc vo mc bin ng ca cc cht, c th theo cc thi gian trong ngy. Trong cc ngy nng, pa ca nc c th tng, c bit l nc c kh nng m thp do kh nng trao i CO2 ca thc Vt thu sinh v nng P c th s b gim i. Trong nhiu trng hp ly mu vo bui sng l thch hp v lc s bin ng cc cht din ra chm. Trong trng hp chung, c th ly mu 3 thng mt ln, nhng khi nghin cu chi tit c th ly mu theo chu k 7 hoc 14 ngy t ma xun n ma thu.

Trong trng hp nc ng nht, c th ch cn ly mt mu n l cng i din cho mi trng nc thi im ly mu. V d nh dng sui chy v khng khc bit nhiu th c th ly su trung bnh gia sui. Tng t nh vy khi ly mu trong h cha nc hoc trong b cha nc. Tuy nhin, tnh ng nht gia cc tng nc cng cn phi khng nh bng vic ly mt lot cc mu cc su khc nhau kim tra s b trc. Nu ly nc qua my bm, ng dn hoc vi nc th cn phi nc chy khong 5-6 lt trc khi ly mu. Trong trng hp cht lng nc b bin i theo thi gian th mu cng cn phi c ly theo cc thi gian thch hp. Nh trong trng hp c s thay i ca dng chy, ca cc ngun nc thi,... mu c th ly nhiu ngun khc nhau ph thuc vo ngun: nc. Cn phi trnh ly mu nhng khu vc c bit nh vng nc ng, c di mc nhiu hoc c nc ngm xm nhp vo. Lng nc cn ly ti thiu m bo cho cc php phn tch, thng t 1 n 2 lt. Dng c ng mu cn phi c lm sch bng cc bin php cn thit nh ra bng cc cht ty ra hoc dung dch axit. i vi phn tch vi sinh vt th dng c ng mu cn phi c v trng. C th lm gim cc tc ng ca cc qu trnh xy ra trong mu bng vic thm cc ho cht cn thit, iu chnh pH hoc gi mu nhit thp (40C). 6.3.3. Ly v bo qun mu Mc tiu chnh ca cng vic ny l nhm chuyn mu n cc ni phn tch v m bo s bin i ca mu l ti thiu, cht phn tch s khng c s thay i ng k v hm lng. Tuy nhin, trong nhiu trng hp, tnh cht ca nc c th b thay i, v d nh Na+ hay Ca2+ c s bin ng rt t trong khi Mo v cc vitamin th b bin i rt nhiu. V vy, dng c ly mu v dng c ng mu phi m bo sch v phi p dng cc bin php cn thit gim s bin i ca mu n mc ti thiu. - Ly mu nc Khi ly mu nc cn phi m bo khng lm xo trn cc tng nc. Ngi ta thng dng 4 loi dng c ly mu sau: Dng c ly mu hnh tr m. Loi Runner v Kemmerer: c dng hnh tr m, dung tch t 1 n 3 lt c np y mi u. Cc np ny c th c m ra hoc ng vo nh mt h thng dy ng Ruttner lm bng nha cn ng Kemmerer lm bng ng. Khi np ng c m ra, nc s qua, n su cn ly mu, ngi ta thng ko, h ng ln xung vi ln (dao ng trong khong 25cm) trc khi ng np li ly mu. Dng c ly mu Friedinger: dng c ny c dng gn ging vi loi Runner v Kemmerer, nhng np c m ra 900. Tt c cc phn bn trong u khng lm bng

kim loi. Dung tch dao ng t 3,5-5 lt, dng c ny c khung gn nhit k. - Dng c ly mu c thot kh, c hp Dng bnh Dussart: dng c ny rt n gin, c th t lm ly c. Dng mt bnh c c hp (dng c chai) c nt cao su vi hai ng nh. Mt ng c ko di xung tn y bnh, cn mt ng ch cn xuyn qua np cao su. u trn ca hai ng nh ny c ni vi nhau bng mt ng nh hnh U hoc ni bng ng cao su mm. Mt vt nng buc pha di bnh ko bnh chm xung nc ng ch U c buc cht vo c bnh v ni vi dy ko iu khin khi ly mu. Th bnh n su cn thit, ko ng ch U, nc s trn vo bnh, y khng kh thot ra. Dng c ly mu Valas: Tng t nh dng c Dussart nhng phn ng m c t tnh v cu to phc tp hn. Sau khi m ly mu, np s c y kn li. Dng c ny thng s dng ly mu phn tch vi sinh vt. - Dng c ly mu bng bm Dng mt ng bng cao su hoc nha ( nng) th xung su cn thit. Dng bm ht to dng nc lin tc v mu nc c ly. Nu cn phn tch cc cht kh th u ng cn t st y bnh ng mu v lng nc chy qua t nht khong gp 3 ln th tch bnh ng mu. ly mu nc mt tang nht nh, ng cao su cn t song song vi nhau khong gia ca hai a nha c ng knh khong 10cm. Dng c ly mu ny s dng cc loi bm tay trnh s tip xc ca kim loi vi nc. N c u im l t lm xo trn mu nc. Th tch ca ng di 10m, thit din lcm2 ch l 1 lt. Dng c ny thch hp ly cc mu hn hp vi cc su khc nhau. - Dng c ly mu nc c nhiu chc nng khc nhau. Dng c ly mu Vondorn: y l dng c c dng rt ph bin ly mu nc. Gm mt ng hnh tr bng cht do, 2 van cao su ni vi nhau bng ng cao su pha trn v pha di ng. Hai van cao su ny c th ng m nh mt chic kho pha ngoi ng tr. Khi th dng c xung nc, 2 van cao su u m, n su cn thit s c ng li nh h thng iu khin (messenger). Mu c chuyn sang bnh cha nh l nh thnh hnh tr. 6.3.4. Mt s ch dn khi ly mu nc. Khi ly mu i vi ngun nc chy nh sng, sui th nn ly mu ch chy mnh nht. Mu ly cc h thin nhin, h cha cc ao m th ly mu cc v tr khc nhau v nhng su v nhng su khc nhau. Khng nn ly mu trung bnh i vi loi mu ny.

Mu ly t cc mch, cc ging, cc h cha nc nhn to th nn ly nhng su cn thit. Mu nc ma ch cn hng vo lc tri ma v cn ghi r thi im ly mu. Mu t cc trm v cc vi nc sinh hot, thng thng c ly trc tip ti cc ng nc dn ra. Mu nc thi, nn ly mau trung bnh, trc khi ly mu cn nu cu k yu cu, mc ch s dng nc v cc iu kin sinh hot khc. 6.3.5. Bo qun mu nc trc khi phn tch Trong khong thi gian t lc ly mau nc n khi phn tch, hm lng ca cc phn c th b thay i vi mc khc nhau Nhit v pH ca nc l i lng bin i nhanh nht, v vy hai ch tiu ny cn xc nh ngay ti ni ly mu. Hm lng mt s kh cng cn phi c xc nh ngay nh O2, CO2, H2S, Cl2. i vi vic xc nh cc kim loi nng trong nc th cn tun th theo nhng quy trnh sau y bo qun mu thm cc ho cht tinh khit vo trong mt lt nc. Ag Ai As Ca Cd Co Cr : Thm 5 ml HNO3 c, : Thm 5 ml HCl c, : Thm 5 ml HCl : Thng khng phi x l, : Thm 5ml HNO3 c, : Thm 5ml HNO3 c, : Thm 5ml HNO3 c,

Cu: Thm 5ml HNO3 khi xc nh tng hm lng st. Thm 25 ml CH3COONa 1M dng xc nh cc dng khc nhau ca st, Hg Mg Mg NH3 Ni PO43Pb : Thm vo 1 ml HNO3 c, : Khng cn phi x l, : Thm 5 ml HNO3 c, : Thm 1 ml H2SO4 c v 2 - 3 ml CHCl3, bo qun nhit 3 - 40C, : Thm 5 ml HNO3 : Thm vo 1 - 2 ml CHCl3, : Thm 3 ml NHO3 c v 2 ml CH3COOH c,

Zn SO42CNSIO32ml H2SO4 (1:3), FCr

: Thm 1 ml H2SO4 c. : Thm 2 - 4 CHCL3. : Gi mu nhit 3 -40C, tng ph, cn xc nh ngay, : ng trong bnh polietylen, khi hm lng SiO2 cao cn thm 1 : phi ng trong bnh polietylen, : Thm 2 - 4 ml CHCl3.

Borat: ng trong bnh polietylen, hoc bnh thu tinh khng c bo (nn xc nh ngay khi ly mu), SCN-: Nn xc nh ngay, khng nn qu mt m, Phenol: Nu hm lng vt qu 100 mg/l th khng cng x l mu v khng c lu gi qu 5 m, nu hm lng < 100 mg/l c th thm vo 4 g NaOH/11, nu hm lng < 0,5 mg/l cn phi phn tch ngay sau khi ly mu, HCHO: Khng cn x l, cn phn tch ngay ng v tinh bt: khng nn xc nh chm hn 1 ngy m sau khi ly mu. 6.4. Xc nh thnh phn ho hc ca nc 6.4 1. Xc nh pH Ngy nay, vic xc nh pH tr nn n gin do s pht trin ca khoa hc cng ngh. Gi tr pH c xc nh bng php o trn my o pH (pH meter). im cn lu khi o pH l vic bo qun in cc do cc c im v kh hu ca vng nhit i. Trc khi tin hnh o cn phi kim tra my bng cch iu chnh my vi cc dung dch m c gi tr pH = 4,00; 7,00; 10,00. in cc phi lun c bo qun trong dung dch bo qun. 6.4.2. cng cng ca nc do cc kim loi kim th ho tr hai, ch yu l Ca v Mg gy nn. Ngi ta thng phn bit cng cacbonat v cng phi cacbonnat. Lng ln Ca v Mg tng ng vi cc mun ca cc axit v c mnh nh HCl, H2SO4, HNO3 gi l cng phi Cacbonat. cng ton phn l tng ca hai loi cng trn. cng thng c biu th bng s mt ng lng gam ca cc ion Ca, Mg trong 1 lt nc hoc i khi bng thang cng ca c, k hiu l OH (l n v cng ca c tng ng vi 10mg/l CaO/l). a. Xc nh cng ca nc bngphngphp chun Comptexon Phng php ny da trn phn ng to phc ca cc ion Ca2+, Mg2+ vi anion

etyleniamintettraaxetat (k hiu l Y4-) cc phc c bn khng cao, phc CaY2c hng s bn l 1010,7, bn hn phc MnY2- c hng s bn l 108,7 v nng ca cc ion Ca2+ v Mg2+ trong nc thng khng cao, nn phn ng chun xy ra hon ton, ngi ta thng tin hnh chun trong mi trng m NH4OH + NH4Cl c pH = 10,00. Dung dch chun l Complexon III. xc nh im tng ng ngi ta dng ch th ET_OO (Eriocrom T en). Trong mi trng chun , cht ch th s phn ng vi ion Ca2+ v Mg2+ to thnh phc c mu . Trnh t phn tch Ly 100 ml nc cn xc nh cng, thm vo 10 ml dung dch m (nu kim ca mu nc ln th phi dng dung dch HCI 0,1 M iu chnh cho pH dung dch bng 7-8 theo giy ch th ng hp trc khi thm dung dch m), thm mt lng nh cht ch th (khong bng mt ht xanh), dung dch c mu . Chun dung dch bng dung dch chun Complexon III cho ti khi dung chuyn t mu sang mu xanh. Nu trong dung dch c mt cc ion cn tr nh Fe3+, Cu2+ th cn chun li vi mu nc khc v cch tin hnh nh sau: Sau khi cho 10 ml dung dch m, ta thm vi git KCN 5% che ion cn tr ri mi thm cht ch th v tin hnh chun nh trn. Tnh kt qu cng ton phn ca nc c tnh nh sau:

Trong : a: th tch dung dch Complexon III tiu tn; V: th tch mu nc ly phn tch (ml); 0,025: nng dung dch Complexon III (mol/l); 2: s ng lng gam cng tng ng vi 1 mol Complexon III. Ho cht - Dung dch Complexon III 0,025M: ho tan 9,306g Complexon III trong 1 lt nc ct hai ln - KCN 50%: cn 5g KCN ho tan trong 100 ml nc ct hai ln. - Eriocrom T en cn 0,05g cht ch th trn vi 10g NaCl. - m NH4OH + NH4Cl (pH = 10), ho tan 25g NH4Cl trong 100 ml nc thm 200ml NH4OH 20%, sau thm nc ct n 1 1t. b. Xc nh Ca v Mg xc nh hm lng Ca v Mg trong nc sinh hot, nc ung, cc loi

nc b mt, nc thi, ngi ta thng dng phng php chun Complexon III (Trilon B). Phc EDTA - Ca bn hn EDTA - Mg. Khi pH ca dung dch nm trong khong 12- 13, EDTA - Ca bn vng trong khi EDTA - Mg b phn hu v to ra hiroxit Mg. Do c th chun Ca trong mi trng ca NaOH c pH = 12- 13 vi ch th Murexit. Xc nh Ca. Trnh t phn tch Cho mu nc vo bnh tam gic c V: 250ml, th tch mu nc c ly khng cha qu 15mg Ca. Dng nc ct pha long thnh 100 ml, nu thy cn thit. Nu mu nc c tnh axit th cn trung ho bng dung dch NaOH. Nu mu nc c kim cao hn 6 mlg/l th cn thm vo lng tng ng dung dch HCl 0,1N, un si dung dch v ngui. Sau thm vo 2ml NaOH 2M v mt t cht ch th murexit. Chun t t bng dung dch EDTA 0,025M cho n khi dung dch chuyn t mu hng sang tm. Tnh kt qa:

Trong a: th tch dung dch EDTA 0,025M; V: th tch mu nc chun (ml); 1000: 2 x 0,025 x 20 x 1000. Ho cht - EDTA 0,025M. Xem phn trn - NaOH 2M: ho tan 8g NaOH trong 100 ml nc ct hai ln. - HCl 0,1 N: pha 8,2ml HCl c trong 1 lt nc ct hai ln Xc nh Mg. Sau khi xc nh Ca nh trn, tin hnh xc nh tng s Ca + Mg ti cc gi tr pH = 10 vi ch th Enocrom T en. Trnh t phn tch Ly vo bnh tam gic c V = 250ml lng th tch nh trong xc nh Ca. X l mu nh lm i vi Ca. Thm vo 5ml Hiroxilamin 10%, vi git KCN 10% v mt lng nh ch th Eriocrom T en ri tin hnh chun bng EDTA 0,025M. Tnh kt qa

Trong : V1: th tch EDTA chun Ca + Mg (ml); V2: th tch Ca (ml); V: th tch mu nc (ml). Ho cht Hidroximalin 10%: ho tan 10g NH2OH.HCl trong 100 ml nc ct hai ln 6.4.3. Xc nh Cu Hm lng ng trong cc loi nc thin nhin v trong cc ngun nc sinh hot thng khng ln lm, dao ng trong khong t 0,001 - 1 mg/1. Trong nc, Cu thng tn ti dng ion Cu2+, hoc di dng phc xianua, tactrat... xc nh Cu ngi ta thng dng phng php trc quang vi ietylithiocacbonat (DDC). Phn ng gia Cu2+ vi Pb-DDC xy ra ti gi tr pH = 1 - 1,5. Trong trng hp ny cng vi Cu cn c Bi, Hg, Ag tham gia vo phn ng. Cc nguyn t cn li khng tham gia phn ng nn phng php ny c chn lc cao. Hg v Ag khng gy cn tr v phc ca chng khng c mu. Bitmut (Bi) ch gy cn tr kh nng ca n vt qu 30 g/l. Nu nng Bi vt qu gii hn th cn phi lc phc DDC- kim loi vi 25ml HCl 5M trong 5 pht, khi phc Bi-DDC b phn hu cn Cu-DDC khng b phn hu. Khi trong mu c cha phc Cu-xianua, th cn phi ph hu phc bng cch thm 0,5ml H2SO4 (1 : l); 5mL HNO3 c Vo 200-250ml mu, cho mu vo cc chu nhit ri t ln bp, lm bay hi dung dch cho n khi gn cn kh (qu trnh ph hu ny nn tin hnh trong t ht). ngui thm vo 1 ml HCl c v lm bay hi n kh. ngui, thm vo nc ct 2 ln, un nng dung dch n si ho tan ht lng mui rn, lc v chuyn ton b dung dch thu c vo bnh nh mc thch hp, inh mc bng nc ct hai ln v gi ly phn tch. Trnh t phn tch Ly mt th tch nc cn phn tch trong mu cha khong 0,2-0,6 g Cu/l, cho vo phu chit dung tch 200-500 ml. Pha long mu nc nu cn n th tch 100 ml ri thm vo 5 git HCl (1:1), t buret thm vo mt cch chnh xc 10 ml PbDDC trong toluen. Cn thn y nt phu chit ti v lc trong hai pht. Gi yn phu chit cho hai tng phn lp, tch b phn tng nc pha di, phn tng hu c cha Cu-DDC c mu vng c chuyn vo cuvet v tin hnh so mu ti bc

sng = 430nm. Lp ng chun Ly vo cc phu chit 0,00; 0,2; 0,5; 1,0; 2,0; 3,0; 4,0; 5,0; 6,0 ml dung dch chun Cu2+ c nng 1g Cu/ml, pha long bng nc ct n 100 ml v tin hnh nh vi mu. Tnh kt qu Da vo ng chun xy dng mi tng quan y = a.x + b Trong y: hm lng Cu2+ x: mt quang o c Ho cht - Pb-DDC trong toluen: Chun bi mt phu chit sch c V =1000 ml, thm vo 50 -100 ml nc ct hai ln, 0,1g Pb(NO3)2 loi tinh khit ho hc, tc k mui tan ht. Ho tan 0,1 g Na-DDC trong lng nc ti thiu ri thm vo phu chit kt ta ht Pb-DDC. Thm vo phu chit 250ml toluen, y nt phu chit v lc mnh, ton b kt ta Pb-DDC s tan ht vo trong toluen, tch b tng.nc, phn tng hu c c lc qua giy lc vo bnh mu nu, dung dch ny bn trong khong 3 thng HCl long: Pha dung dch HCl 0,01N. - Dung dch Cu2+ nng 1 g Cu/ml: Ho tan 3,906 mg CuSO4.5H2O trong 1 lt nc ct hai ln. 6.4.4. Xc nh Pb bng phng php trc quan ithizon Hm lng Pb trong nc thin nhin rt nh, nm trong khong 0,0010,02mg/1. Trong nc sinh hot cng c lng vt Pb do ng nc c lm bng Pb. Trong nc thi c bit l nc thi ca cc nh my sn xut Pb, Zn, hm lng Pb c th ln ti 6 -7 mu. Ch trong nc thi c th dng tan hoc dng mui kh tan nh sunfat, cacbonat, sunfua. ithizon-iphenylthiocacbonat l thuc th hu c c kh nng to phc cng ca vi Pb2+. Phc Pb-ithiozonat c mu tan trong toluen, phc ny c so mu ti bc sng =520 nm. Pb-ithiozonat c chit chn lc v nh lng t dung dch c pH= 8 - 9, c cha lng d CN- l cht dng che nhiu kim loi khc cng b chit vi Pb. Trong mi trng trn cng b chit vi Pb ch c Ta, Bi,Sn. y Tali khng cn tr, nhng Bi v Sn gy cn tr, do vy chng cn c tch trc t mi trng axit. Thm hirazin vo dung dgui thm dung ch mu nc, un nng kh Sn (IV) xung Sn (VI) v kh cc cht khc. Sau khi ngui thm dung dch kalinatritactrat vo, a dung dch n pH = 2,5 - 3 bng axit tactric, ri tin hnh trit nhiu ln, mi

ln bng 5/ ml ithizon trong toluen cho ti khi mu xanh ca ithizon khng i. Tch ly tng nc. Tin hnh chit nh vy khng nhng tch c thic m cn tch c c Hg, Ag, Cu. Nu trong mu c cha lng ng k cc cht hu c th cn phi v c ho chng bng hn hp axit mnh nh H2SO4 v HClO4. Cc cht xy ho cn kh trc bng hirazin. Trnh t phn tch Thm vo cc 100 ml mu nc c pha long hoc c nc trong cha t 0,01 - 0,1 mg Pb. S dng bp cch thu, lm bay hi dung dch n khi cn 30 ml, chnh pH ti 7 theo giy ch th tng hp. Thm vo 10 ml hiroxilamin 10% v un nng hn hp to = 90 - 950C trong khong 12 pht. ngui dung (tch, dng axit HCl long hoc axetec long chnh pH dung dch ti 3. Chuyn ton b dung dch trn vo phu chit, t buret thm cn thn 10 ml dung dch ithizon v tin hnh chit cho n khi mu xanh ca ithizon khng thay i. Tch ly tng nc, ri chnh pH ca dung dch ti 8-9 bng dung dch amoniac, thm vo 5 - 1 0 ml dung dch KCN 10%. Sau chuyn ton b dung dch vo phu chit, thm vo chnh xc 10 ml dung dch ithizon v tin hnh chit cho ti khi mu xanh ca ithizon khng thay i. Gp tt c cc phn ithizon chit c li, chuyn vo mt phu chit sch ri tin hnh ra bng dung dch amoniac long, khi phc ca Pb-ithizonat c mu . Lp ng chun Thm vo mt lot cc 0; 2,5; 5,0; 10,0; 20,0; 30,0; 40,0; 50,0 ml dung dch chun cha 0,002 mgPb/ml v thm nc ct vo mi cc n th tch 100 ml. Nh vy ta c cc dung dch c hm lng tng ng 0; 0,05; 0,1... mg Pb/lt. Ri tin mu tng t nh i vi mu. Tnh kt qu Da vo ng chun xy dng mi tng quan y = a.x + b y: hm lng Pb trong mu x: mt quang o c. T thay gi tr mt quang o c ca mu vo phng trnh trn ta s tnh c hm lng Pb c trong mu. Ho cht ithizon: Ho tan 50 mg ithizon trong 100 ml toluen trong phu chit th tch 1000ml. Thm vo 200ml nc ct v 5 - 10 ml dung dch NH3 c. y nt phu chit cn thn v lc trong hai pht. Lc ny ithizon chuyn sang tng nc, sau khi hai tng phn lp, tch b phn dung mi pha trn, li thm vo tng nc 20ml toluen, lc hn hp, tch b phn toluen. Cn thn thm vo phu chit 200ml toluen v dung dch HCl long cho n khi tng nc c phn ng axit r th bng giy ch th pH. y nt phu li v lc hn hp chuyn hon ton ithizon sang

tng hu c. Chuyn tng hu c sang mt phu chit khc, ra n vi ln, mi ln bng 50 ml nc ct h ln cho n khi tng nc ht phn ng axit. Tch b phn tng nc, tng hu c cha ithizon c chuyn vo bnh mu nu sch v kh, bo qun dung dch nhit thp v trnh nh sng. Dung dch bn trong vi thng. - Dung dch lm vic: Ly mt th tch dung dch ithizon gc pha cng vi mt th tch toluen, ng trong bnh thu tinh mu nu sm. Dung dch bn trong mt tun. - Dung dch ra amoniac long Pha 175 ml NH3 c bng nc ct hai ln ti th tch 1 lt. - Kali natri tactrat 10%: Ho tan 10 gam KNaC4H4O6.2H2O trong 100 ml nc ct hai ln. - KCN 10%: Ho tan 10 gam KCN trong 100 ml nc ct hai ln c kim ha. - Dung dch 0,002 mg Pb/ml: Ho tan 3,197 mg Pb(NO3)2 trong nc ct hai ln thnh 1 lt 6. 4.5. Xc nh Zn bng phng php trc quan ithizon Km trong nc t nhin ch yu t cc ngun nc thi, c bit nc thi ca cc nh my luyn kim, cng nghip ho cht, cc nh my si tng hp. Cc dng tn ti ca Zn trong nc v cc ion n, ton phc vi xianua, cacbonat, sunfua... Ni chung khi ly mu nc phn tch cn thm 1 ml axit H2SO4 c vo 1 lt nc, tr trng hp mu c cha xianua. xc nh Zn trong nc ngi ta dng phng php trc quan ithizon l phng php cho php xc nh n vi phn trm miligam km trong 1 lt nc. Ion Zn to phc vi ithizon to thnh Km-ithizonat c mu hng. Phn ng gia km v ithizon xy ra ti pH = 5 v dung dch c cha lng d S2O32-, CNdng che Cd, Ni, Pb... Do nu trong mu nc khng c cc ion ny hoc c nhng vi hm lng nh hn kem th khng cn dng xianua. Thic (II) cn c xy ho trc thnh Thic (IV) bng H2O2 v un si k phn hu H2O2 cn d. Cc cht xy ho c ithizon cn c loi tr trc khi xc nh. Fe (III) cn c loi tr trc bng cch kt ta n di dng hiroxit v lc b. Trnh t phn tch Ly 100 - 200 ml nc cn phn tch cho vo phu chit, mu nc cn c pha long trc hoc lm bay hi cha khong 0,005 - 0,03 mg Zn. Dng axit axetic hoc NaOH long chnh pH ca dung dch ti 7 ri thm vo chnh xc 20ml dung dch m, c pH:5 v 20ml dung dch che. T buret thm vo chnh xc lon dung dch ithizin, y nt phu, lc cn thn trong khong 2 pht. Qu trnh chit kt thc khi mu ca ithizon gi nguyn mu xanh. Gp tt c cc phn ithizon c chit l

chuyn vo mt phu chit sch kh khc ri tin hnh ra ithizon d bng dung dch amoniac long nh i vi ch. Khi phc Zn - ithizonat c mu hng xut hin. Phc mu ny c em so mu ti bc sng = 530 nm. Lp ng chun Chun b 7 phu chit sch, thm vo ln lt tng phu 0; 10;20;30;40;50;60 m dung dch c nng 0,0005 mg Zn/ml. Thm nc ct 2 ln vo c th tch l 100ml ri tin hnh nh i vi mu phn tch. Tnh kt qu Da trn vic lp thang chun s xc nh c mi tng quan hm s y = a.x + b. Trong : y: hm lng Zn trong mu. x: mt quang Ho cht Dung dch che: Ho tan 120 g Na2S2O3.5H2O; 0,15g (NH4)2C2O4.2H2O; l,5g KCN (nu cn), 24 g CH3COONa.3H2O, 10 ml NH3 2N, 70 ml HCl l trong nc ct hai ln ri chuyn vo bnh nh mc 1 lt v nh mc n vch mc. Dung dch m pH = 5. Ly 73,4 ml CH3COOH 1N v 50 ml NaOH lN thm nc ct n 500 ml v lc u. - ithizon: S dng nh trong xc nh Pb. - Dung dch chun Zn: Xem phn xc nh Hg trong t. 6.4.6. Xc nh Hg bng phng php trc quan ithizon Thu ngn i khi c trong nc chy ra t cc m v trong nc thi sn xut cc cht mu, dc phm v cht n. Vic xc nh Hg l rt quan trng v cn thit, v cc hp cht ca n thng rt c. xc nh Hg thng dng phng php chit trc quang ithizon. Phng php ny rt c trng v chn lc i vi Hg, v n c chit hon ton t mi trng c axit rt cao, trong mi trng ny tuyt i a s cc kim loi khc khng b chit. Phng php cho php xc nh t vi phn trm miligam ti hng chc miligam trong 1 lt nc. Nu mu nc lu mi tin hnh phn tch th cn thm vo 1 ml HNO3 c cho 1 lt mu. Trong mi trng axit ch c Au, Cu cng b chit vi Hg. che hai nguyn t ny phi dng Complexon III v Thioxianat (SCN-). Trong mi trng m axetat c cha Complexon III v Thioxianat (SCN-) ch c Au (m) v c th c Pt (II) c nh hng n vic xc nh, nhng hai nguyn t

thng t khi c mt trong nc. Cht hu c c mu thng tch nc bng toluen. Nu mu c cha nhiu cht hu c th cn v v ho trc khi xc nh. Trnh t phn tch Cho vo phu chit mt th tch nc thch hp trong c cha 0,005 - 0,1 mg Hg, pha long n 100 ml bng nc ct hai ln. Thm vo 20ml dung dch m, 10 ml Complexon (m), 10 ml KSCN. T buret thm chnh xc 10 ml ithizon, y nt phu chit, lc cn thn trong khong 2 pht. Qu trnh chit kt thc khi mu xanh ca ithizon khng thay i. Gp tt c cc phn ithizon chit c li, chuyn vo mt phu chit sch kh. Dng dung dch amoniac long 5% ra ithizon d. Tch b phn tng nc, khi phc Hg - ithizonat c mu da cam xut hin Phc mu ny c so mu ti bc sng = 490 nm. Lp ng chun Php tp ng chun tng t nh khi xc nh cc nguyn t khc. ng chun y c lp vi cc dung dch ng vi 0; 0,05; 0,1 mg Hg/l. Tin hnh tng t nh i vi mu phn tch. Tnh kt qu Tng t nh i vi cc nguyn t khc ta xy dng hm tng quan; y = a.x + b Trong : y: hm lng Hg trong mu; x: mt quang Ho cht Dung dch m axetat (pH = 4): Ho tan 57 ml CH3COOH c v 82g CH3COONa.3H2O trong nc ct thnh 1 lt. Complexon III 0,05N. Ha tan 9,306 g EDTA trong nc ct thnh 1 lt. KSCN: Pha dung dch 0,1 M Dung dch chun Mg: Xem phn xc nh Hg trong t. 6.4.7. Xc nh Fe Hm lng ca Fe c trong nc thin nhin ph thuc rt nhiu vo ngun nc v nhng vng m ngun nc chy qua. Ngoi ra cn tu thuc vo pH v s c mt ca mt s cht nh CO32-, O2, S2 v cc cht hu c tan trong nc, chng s oxy ho hay kh Fe v c th lm cho Fe nm dng tan hay kt ta. xc nh Fe trong nc, thng dng phng php so mu vi cc thuc th nh axit sunfoxalixilic hoc o-phenalthrolin. Mun xc nh st nm cc dng khc nhau, mt iu quan trng cn phi ch

 l cch y mu. xc nh tng lng st c trong mu cn phi x l mi mu nc vi 25 ml HNO3 c. Nu mun xc nh Fe trong mu cc dng khc nhau th mi lt nc cn phi x l bng 25 ml dung dch m CH3OONa 1 M. a) Xc nh Fe bng thuc th o- phenalthrolin. Thuc th o- phenalthrolin phn ng vi ion Fe2+ to thnh phc cht c mu tm . Khong pH cho qu trnh to phc kh rng, t 3 - 9. Mn c nh hng rt ln n qu trnh xc nh nn khi mu phn tch c mt Mn th khng nh lng c Fe bng phng php ny. Lng Cu ln hn 10 mg/1 cng gy nh hng khi xc nh nhng c th loi tr nh hng bng cch tin hnh phn ng trong khong pH t 3 n 4. Nu trong mu c cha lng ln cc cht hu c th trc cn phi v c ho. Trnh t phn tch. Ly lng mu nc cn phn tch (sao cho lng Fe trong khng qu 0,2 mi cho vo bnh nh mc 50 ml. Thm 1 ml HCl long, c n th tch cn khong 40 ml. Lm ngui, thm 1 ml Hiroxilamin kh Fe3+ thnh Fe2+, ri thm lu ophenalthrolin. Nh tng git NH3 n khi giy ch th Cngg chuyn sang mu xanh. nh mc bng nc ct lc u. Sau tin hnh so mu ti bc sng = 540 nm. Lp ng chun Ly ln lt vo mi bnh 0; 0,5; 1,0; 2,0; 5,0; 10,0; 20,0; 30,0; 40,0; 50,0 ml dung dch 0,005mg Fe/ml, ri tin hnh tng t nh i vi mu. Tnh kt qu Da vo ng chun xc lp hm tng quan y = a.x + b y: hm lng Fe trong mu; x: mt quang. Ho cht - O- phenalthrolin: Ho tan 0,28 g o- phenalthrolin trong nc ct thnh 100 ml. - Hiroxilamin 10%: Ha tan 10 g Hiroxilamin trong nc ct thnh 100 ml. - HCl: Dung dch long(1: 9). - Dung dch NH3 c - CH3COONa lM: Ho tan 68g CH3COONa.3H2O trong 500 ml nc, thm 25 ml CH3COOH 6M sau thm nc ct n 1 lt. b. Xc nh Fe bng thuc th axit sunfoxalixilic

Ion Fe3+ phn ng vi thuc th axit sunfoxalixilic trong mi trng kim to thnh phc c mu vng. Lng ln Al, Cu c trong mu s cn tr php xc nh. Trnh t phn tch. Cn ly lng mu nc thch hp trong c cha t 0,01 - 1,00 mg Fe, cho vo cc c dung dch 100 ml. Thm 0,5ml HNO3 c, lm bay hi n cn khong 10 ml. Sau pha long bng nc ct, lc, thu ton b nc lc v nc ra vo bnh nh mc 100 ml, thm nc ct n khong 90 ml. Thm 2ml dung dch NH4Cl, 2ml dung dch axit sunfoxalixilic v 2ml dung dch NH3. Thm nc ti vch mc, lc u, sau 5 pht o mt quang ca dung dch ti bc sng = 430nm. Lp ng chun Ln lt ly vo mi cc 0; l;2; 3;4; 5; 6; 7; 8; 9; 10 ml dung dch c nng 0,1 mg Fe/ml. Ri tin hnh tng t nh vi mu phn tch. Tnh kt qa Da vo ng chun lp hm tng quan y = a.x + b y: hm lng Fe c trong mu x: mt quang o c Ho cht - Axit sunfoxalixilic 20% - NH3 c - NH4Cl 2N: Ho tan 1O7 g NH4Cl trong 1 lt nc ct hai ln - HNO3 c. - Dung dch chun sc: Ho tan 0,864 g NH4Fe(SO4)2.12H2O tinh khit phn tch trong nc, thm 2 ml HCl c, nh mc n 1 lt, dung dch ny cha 0,1 mg Fe/ ml. Ly 50ml dung dch chun ny pha thnh 1 lt c dung dch cha 0,005 mg Fe/ ml. 6.4.8. Xc nh Mn Trong nc Mn thng nm hai dng tan v khng tan. dng tan Mn tn ti di dng ion Mn2+, cn dng khng tan l kt ta hiroxit. Hm lng Mn c trong nc tu thuc vo ngun nc, hm lng Mn cao trong nc thi ca nh my luyn kim v nh my ho cht. xc nh tng lng Mn c trong nc ngi ta thng dng phng php trc quan (so mu). Khi Mn s b xy ho thnh Mn7+ bi cht xy ho mnh nh amonipesunfat (NH4)2S2O8. Ch khi ly mu phi thm vo mi lt nc 5ml NH3 c.

Trnh t phn tch Cho 50 n 100 ml mu nc vo cc 150ml sao cho lng Mn trong l 0,005 - 1 mg, thm 2ml HNO3 nh tng git dung dch AgNO3 cho n khi kt ta ht ion Cl- thm tip 1 - 2 ml dung dch AgNO3 lng ri lc. Nu hm lng clorua v cc cht hu c ln th phi tin hnh v v ho mu, khng th loi tr Cr bi AgNO3 khi hm lng ca chng qu ln v s gy hin tng hp ph Mn. Thm 0,5g pesunfat vo nc lc. in dung dch ti gn si khong 10 pht. ngui ri chuyn vo bnh nh mc c ung tch 100 ml, thm nc ti vch mc. Tin hnh so mu ti bc sng = 525nm. Lp ng chun Cho vo 10 cc 150 ml chu nhit ln lt theo th t 0; 0,5; l; 2,5; 5; 10; 20; 30; 40; 50 ml dung dch chun Mn c nng 0,01 mg/ ml ri tin hnh nh i vi mu phn tch Tnh kt qu Da vo thang chun thit lp mi tng quan hm s y = a.x + b. Trong : y: hm lng Mn x: mt quang o c Ho cht - HNO3 c. - AgNO3 c: Ho tan 17g AgNO3 trong 500ml nc ct hai lan. - (NH4)2S2O8 mui rn. Dung dch chun: Ho tan 0,2748g MnSO4 trong 1 lt nc ct hai ln c axit ho bng H2SO4, dung dch ny c nng 0,1 mg. Pha long dung dch ny 10 ln ta c dung dch c nng 0,01 mg/ml. 6.4 9. Xc nh Cr Trong mi trng axit, cromat v bicromat phn ng vi iphenycacbazit to thnh hp cht tan mu tm rt thun li cho vic o mu. Phn ng ny dng nh lng Cr c hm lng t 0,005 - 1,00 mg/l. Cc ion Hg2+ v Hg22+ (khi hm lng >200 mg/l), Mo6+ cng c kh nng to phc mu vi thuc th, tuy nhin nhng ion ny thng c rt t trong nc. St vi hm lng ln hn 1 mol cng phn ng vi thuc th to thnh hp cht c mu vng nu, nhng c th loi tr Fe bng cch thm vo lng nh H3PO4. Nu trong mu c cha hm lng Mn th phi xy ho bng pesunfat trong mi trng kim hoc trung tnh, n s to thnh kt ta MnO2 v c lc b bng bng thu tinh. Nu mu nc c tnh kim hay trung tnh th rt kh xc nh ring Cr3+ v Cr6+.

Bi v khi axit ho, nu trong dung dch c cht kh nh Fe2+, sunfit v cc cht hu c th Cr6+ s bi kh xung Cr3+. Trong trng hp ny ch nn xc nh tng hm lng Cr. Mun xc nh ring ta phi tch ring Cr3+ bng cch kt ta n bng MgO (pH = 10,5 - 11). Khi Cr(OH)3 kt ta trn b mt MgO, cn Cr6+ vn tan trong dung dch. Lng ln cht hu c, cc cht kh v ion Cr khng cn tr php xc nh a) Xc nh Cr6+ Trnh t phn tch Ly lng mu phn tch vo bnh nh mc sao cho trong c khong 0,0050,1 mg crom. Mu nc c cho vo bnh nn c 25ml, thm vi git phenotphtalein, nu dung dch c mu hng th thm tng git H2SO4 1N ti khi mt mu, ghi th tch dung dch H2SO4 1N dng: nu dung dch khng c mu th thm tng git NaOH lN. Thm bng y git H2SO4 lN hoc NaOH l vo mu trung ho. Sau thm 1 ml H2SO4, 0,2ml axitphotphoric v 2 ml dung dch iphenylcacbant, thm nc tt vch mc, sc u. Sau 5 - 10 pht th em so mu ti bc sng = 540nm. Lp ng chun Chun b 10 bnh nh mc c dung tch 100 ml. Ln lt ly vo mi bnh 0; 1;2;5; 10; 15; 30; 40; 50ml dung dch c nng 0,002mg Cr/ml ri tin hnh tng t nh i vi mu phn tch Tnh kt qu Da vo ng chun thit lp mi tng quan hm s y = a.x + b. Trong : y: hm lng Cr x: mt quang o c. b. Xc nh tng hm lng Cr Ly lng mu nc cn phn tch cho vo cc c th lch 250ml sao cho lng Cr trong khong 0,005 - lmg. Trung ho bng H2SO4 hoc NaOH 1N. Sau thm 0,3ml H2SO4 1N, 5 - 10 ml dung dch amonipesunfat, un si dung dch 20 - 25 pht ( phn hu ht pesunfat d). Lm bay hi bt .dung dch cn khong 50ml. Chuyn tt c vo bnh nh mc v tin hnh nh xc nh Cr6+. Ho cht dng xc nh cc dng Cr - NaOH 1N: Ho tan 40 g NaOH trong 1 nc ct hai ln. - H2SO4 1N: Cho 28 ml H2SO4 c vo 500 ml nc ct hai ln ri nh mc ti 1 lt. - H3PO4 c 85%. iphenylcacbazit 0,5% trong axeton: Ho tan 0,25g iphenylcacbazit trong 50ml axeton.

- Amonipesunfat 0,1 %: Ho tan 0,1 g amonipesunfat trong 100 ml nc ct hai ln. - Dung dch chun: Ho tan 2,8285g K2Cr2O7 trong 1 lt nc ct hai ln c dung dch c nng 1 mg/ml. S dng dung dch ny pha thnh dung dch c nng 0,002 mg/ml. 6.4.10. Xc nh Ni bng thuc th imetylglioxim Trong nc sinh hot v nc t nhin thng khng c Ni hoc l lng vt. Ni ch c trong nc mt s h hoc sng m ngun nc chy qua nhng vng ni v vng m c Ni. Ni c trong nc thi ca mt s nh my luyn kim v ho cht c s dng Ni. Trong nc Ni tn ti di dng Ni2+, dng phc xianua v dng t tan nh sunfua, cacbonat, hiroxit... xc nh Ni ngi ta thng dng phng php so mu khi hm lng Ni nm trong khong 1 - 20 mg/l, nu hm lng Ni ln hn 5 mg/l th c th dng phng php khi lng, cn khi hm lng khong 0,02 mg/l dng phng php cc ph. Mu nc ly xong cha phn tch ngay th phi thm 2 - 5ml HNO3 c vo 1 lt mu nc. Nu cn nh lng ring Ni dng tan v khng tan th khi ly mu ta phi lc ngay ri mi ng chai bo qun v xc nh Ni dng tan v tng lng Ni, t suy ra hm lng Ni dng khng tan. Trong mi trng amoniac yu, khi c mt cht xy ho mnh, ion Ni2+ phn ng vi imetylglioxim to thnh phc cht c mu . St Crom v ng cn tr php xc nh nn cn loi b trc. loi b Fe thm 2 ml H2O2 3% vo 100 ml mu phn tch, un si v kt ta hiroxit bng dung dch amoniac, lc b kt ta. Loi b Cu bng cch axit ho mu HCl n ph = 2, sau sc kh H2S, lc b kt ta, nc lc trc khi phn tch phi un si k ui ht H2S d. Trnh t phn tch Cho vo bnh nh mc 100 ml mt th tch mu sao cho lng Ni trong mu l 0,01 - 0,25mg thm vo 10ml dung dch nc tham bo ho, lc hn hp. Sau thm 12ml dung dch amoniac, 4 ml dung dch imetylglioxim, thm nc ct ti vch mc. Sau tin hnh o mt quang ti bc sng =540nm. Lp ng chun Chun b 8 bnh nh mc c dung tch 100 ml, ln lt ly vo mi bnh 0; 2,5; 5;10; 20; 30; 40; 50ml dung dch c nng 0,005 mg/ml. Sau pha long thnh 50 ml bng nc ct ri tin hnh nh i vi mu phn tch Tnh kt qu

Da vo ng chun thit lp mi tng quan hm s y = ax+b. Trong : y hm lng Ni trong mu; x: l mt quang o c. Ho cht - Dung dch nc brom bo ho. - Amoniac c. - imetylglioxim 1,2%: Ho tan 1,2g mui nam imetylglioxim trong nc ct v pha long thnh 100 ml. - Dung dch chun: Ho tan l dy Ni v 15ml HNO3 35 %, thm 5ml H2SO4 (1:3), un en bc khi trng. Ho tan phn cht rn vo thm nc ct n 1 lt. Dung dch ny c nng 1mg Ni/ml. T dung dch ny pha thnh dung dch c nng 0,005mg/ml. 6.4.11. Xc nh Asen(As) bng phng php trc quang Trong nc As thng nm dng asenat. As hu nh khng c trong nc ngm, n chi c trong cc ngun nc thi ca cc nh my luyn kim, cng ngh ho hc, cc nh my da v sn xut cht mu. xc nh Asen ngi ta thng dng phng php so mu vi thuc th Aoietylithiocacbamat. Bng phng php ny c th xc nh c n 0,05mg Asen trong 1 lt nc. Di tc dng ca dng hidro mi sinh, asenat b kh thnh asin (AsH3) v sau phn ng vi Ag-ietylithiocacbamat to hp cht c mu khi c mt ca pirii. Trong iu kin ny, H2S cng phn ng vi thuc th to thnh hp cht c mu tng t. Ta phi loi b nh hng ca H2S bng cch cho hp th trn ng c ng giy lc c tm ch axetat hoc bng cch v c ho n nh mt cht hu c SbH3 cng c kh nng phn ng tng t nh AsH3 nhng n ch to thnh hp cht mu hng nht khi c hm lng cao hn 0,1 mg/l, cho nn thc t c th b qua. Lng cht hu c trong nc cng gy cn tr php xc nh nn cn loi b chng bng cch v c ho mu. Ly lng mu sao cho c 0,002 - 0,4mg As, thm vo 2 - 3ml H2SO4 c 5ml HNO3 c V 0,5ml H2O2 3%, lm bay hi dung dch n khi bc khi trng. ngui, thm 5ml nc ct, chuyn ton b vo bnh ct, trng nhiu ln bng nc ct v thm nc ct ti th tch khong 50ml. Nu lng cht hu c c trong nc t th ta c th lm giu asen bng cch cng kt n vi hiroxit. Ly 100 - 1000m1 mu sao cho lng asen trong khng nh hn 0,002mg, cho vo phu chit, thm vo 0,5 - 1ml dung dch FeCl3(ho tan 115g FeCl3 trong 1 lt nc ct hai ln. Trung ho bng NH4OH(1:1) n khi xut hin

kt ta. Lc nh phu chit khong 15 pht, yn cho kt ta lng xung, tch ly phn kt ta cho vo bnh ct ca my ct. Lp li kt ta mt ln na trong phu chit tch ht kt ta. Nu cn kt ta th tch v gp n cng vi kt ta trc. Ho tan kt ta bng mt lng va HCl(1:4). Nu kt ta khng tan ht th lc b. Thm nc ct ti khong 50ml. Trnh t phn tch Trc khi tin hnh phn tch cn kim tra xem hm lng asen c trong thuc th. Ly khong 50ml mu nc cn phn tch cho vo bnh tam gic sao cho lng asen trong bnh khong 0,002 - 0,04mg. Thm vo 15ml dung dch HCl long. Sau thm tip 6ml dung dch KI v 0,5ml dung dch SnCl2. Lc u hn hp v yn 15 pht. Nhi giy lc tm ch axetat vo ng thu tinh. Ly 15ml dung dch hp th Ag-ietylithiocacbamat vo bnh hp th ri ni tt c cc b phn ca bnh hp th vi nhau. Cho vo bnh tam gic 5g km ht hay 2 - 3g km bt, y ngay bnh li. Zn s kh H+ gii phng ra hiro. Hiro mi sinh s kh asen to thnh asin bay ra v b dung dch trong bnh hp th. Phn ng xy ra trong 60 pht. Nu thy phn ng xy ra chm th cho thm 0,5ml SnCl2, 5 - 1 5ml HCl c qua phu. Sau khi phn ng xong, chuyn dung dch bnh hp th vo cuvet v em o mt quang ti bc sng 560nm. Lp ng chun Pha mt dy dung dch chun c cha 0; 2; 5;10; 20; 30; 40; 50ml dung dch chun c nng 0,001mg/ml. Tin hnh nh i vi mu phn tch. Tnh kt qu Da vo ng thit lp mi tng quan hm s y = ax + b. Trong : y: hm lng As trong t; x: mt quang o c. Ho cht - Bc ietylthocacbamat, dung dch trong pirin: + Dung dch 1: Ho tan 2,25g nam ietylthocacbamat trong 100 ml nc ct; + Dung dch 2: Ho tan 1,7g AgNO3 tinh khit phn tch trong 100 ml nc ct. Nh dn dung dch 1 vo dung dch 2 n khi kt ta ht. Lc, ra sch bng nc ct, sy kh trong bnh ht m p xut thp, kt ta thu c c mu vng nht. Ho tan 1 g kt ta thu c trong 200ml piriin. - KI 15% - SnCl2: dung dch 40% trong HCl c. - Km ht tinh khit phn tch khng cha asen.

- Giy tm dung dch ch axetat 10% sy kh - Natri asenit, dung dch chun: + Dung dch chun gc: Ho tan 0.1320g As2O3 tinh khit phn tch vo 10 ml dung dch NaOH 1 N tinh khit phn tch, lc mnh, sau khi tan ht thm vo 10ml dung dch H2SO4 1 N tinh khit phn tch, ri thm nc thnh 1 lt, c dung dch 0,100 mg As/ml; + Dung dch chun s dng: Ly 10 ml dung dch chun gc pha long bng nc ct n 1 lt c dung dch 0,001 mgAs/ml. Ch pha trc khi dng.

6.4.12. Xc nh bc (Ag) Bc thng c trong nc chy ra t mt s m, v thng c trong nc thi ca cng nghip nh. Trong nc bc tn ti di dng phc tan hoc hp cht khng tan, ch yu v bc halogenua. xc nh bc trong nc c th dng phng php trc quang ithizon hoc rodanin. bo qun mu nc khi phn tch bc cn thm 5ml HNO3 c vo 1 lt nc Ion Ag+ phn ng vi rodanin to thnh kt ta , khi lng bc nh th to

thnh dung dch keo. lm n nh dung dch keo , thng dng dung dch gelatin. Phn ng ny kh c trng v chn lc i vi bc. Trc khi xc nh cn ph hu cc vn c bng cch v c ho mu nc. Trnh t phn tch Ly 50ml dung dch mu trong sut (a c v c ho), cho vo cc dung tch 100 ml, thm vo 2ml dung dch kalinatritactrat, 2ml NH3 1ml galatin. Sau khi trn u hn hp, thm vo 0,5ml rodanin v sau 5 pht th tin hnh o mt quang. Lp ng chun ng chun c lp vi dy dung dch c cha 0; 0,5; 1; 8; 10 ml dung dch c cha 0,01 Ag/ml. Sau pha long bng nc ct hai ln ti th tch 50ml. Tin hnh nh i vi mu phn tch. Tnh kt qu Da vo ng chun thit lp mi tng quan hm s y = a.x + b. Trong : y: hm lng Ag c trong mu; x: mt quang o c. T s xc nh c hm lng Ag c trong mu Ho cht - Kh natri tactrat 20%. - Amoniac 10%. - Gelatin 1 %. - Rodanin 0,03% trong axeton, ng trong chai mu nu, ch mt, dung dch bn trong 2 tun - Dung dch chun + Dung dch chun gc: Ho tan 1,4450g Ag2SO4 tinh khit phn tch ( sy kh 1050C) trong nc ri nh mc n 1 lt trong cha 1 ml HSO4 c. Dung dch ny cha 1,00mgAg/ml. - Dung dch chun s dng cha 0,01 mg Ag/ml: Ly 10 ml dung dch chun gc v nh mc bng nc n 1 lt. 6.4.13. Xc nh Beri (Be) Beri l kim loi mu xm sng, khng gp trong thin nhin dng tinh khit, t khi l,85; nhit nng chy 12840C, nhit si 24710C, Ben clorua v Beri sunfat n nh trong nc, nng ca chng gim n 30-35% so vi nng ban u ch trong khong 5 giy. Hm lng trong nc thin nhin ca Be dao ng trong khong 0,00001 -

0,0012mg/l. Hm lng Be cao trong nc thin nhin thng gp cc ni c va Beri v trong nc c lng ln cc ion F- v SO42-. Beri thng c trong nc thi ca cc nh my luyn kim, ch to my, x l du m v cc x nghip in t. i vi ngi v ng vt mu nng, khi hm lng Be trong nc cao s gy nhim c cp tnh v tc ng tch lu. Cc mui NO3-, Cr v SO42- ca Be rt c. khi hm lng Be2+ (mg/kg trng lng c th) dng mui sunfat l 80 th 50% chut b cht; dng clorua l 92. C hai dng hp cht ny u c kh nng tch lu. Vi lng 0,0001 mg/kg th trng hay 0,0002 mu nc th khng gy nguy him. i vi ng vt sng trong nc, khi hm lng mui ben clorua l 15mg/l nc cng th lm cht c tu 0,05mg/1 lm cht rn nc. Khi hm lng mui bensunfat l 13mg/l nc mm th lm cht c r. Khi nng Be l 10 mg/l th lm gim trong ca nc; 0,5-1,0 mg/l s km hm cc qu trnh t lm sch sinh hc trong h cha v qu trnh sinh sn ca h vi thc vt; nng 0,005 mg/l th khng c nh hng n qu trnh t lm sch ca h cha. Nng Be t 15-20ml/l s km hm s ny mn ca ht rau dip v ci canh. Nng gii hn cho php (mg/l). + Nc ung: Tu theo tiu chun tng nc, Lin X (c) l 0,0002; + Nc s dng nng nghip v nc sinh hot: Lin X (c) l 0,0002; + Nc ti cho tt c cc loi t (ti lu di): 0,5. Phng php xc nh C th xc nh Be theo phng php quang ph hp th nguyn t, phng php ph pht x plasma ICP (Inductively Coupled Plasma) v phng php trc quang. Tuy nhin, phng php trc quang cho chnh xc km hn so vi hai phng php trn. Phng php aluminon Nguyn l: Dung dch thuc th aluminon phn ng vi Be to thnh hp cht mu sm, hp th cc i ti bc sng 515 nm. Thm mt lng nh cht to phc EDTA s ngn cn nh hng ca Al, Co, Cu, Fe, Mg, Ni, Ti, Zn v Zirconi hm lng va phi n qu trnh xc nh Be. Trong iu kin nh vy, khi hm lng Cu khng vt qu 10 mg trong lng mu phn tch th khng nh hng n php xc nh. Nu lng cao hn th cn tng lng EDTA thm vo. Phc ca Cu hp th khng ng k bc sng 515 nm. C th loi tr nh hng ny bng cch thm mt lng Cu tng ng vo thang chun. Bo qun mu

Axit ho ton b mu phn tch trong khi bo qun gi cc kim loi trong dung dch v ngn nga chng bm ln thnh bnh. Nu nc sch khng c cc cht l lng th mi lt mu thm vo l,5ml HNO3 c a pH ca mu n 2. Nc mt ao h v nc thi c th cha cc trm tch th cn phi thm nhiu axit hn Dng c: My so mu quang in, knh lc mu xanh lc, bc sng 515 nm, cuvet dy 5cm. Thuc th - Dung dch beri gc: Ho tan 0,9837g berisunfat ngm 4 phn t nc, tinh khit 99,9% trong 100ml nc ct, nu cn th tc, sau thm nc ct ti 500ml 1ml dung dch ny cha 100 Be. - Dung dch chun s dng: Ht 5ml dung dch gc cho vo bnh nh mc 100 ml ri nh mc bng nc ct ti vch mc, lu dung dch ny cha 5 gBe. - Dung dch EDTA: Ha tan 2,5g EDTA trong 30ml nc ct, thm vo 1 git metyl 0,05% pha trong ru. Trung ho dung dch bng NH4OH c lnh v thm nc ct n 100 ml. - Dung dch m aluminon: Cn 500g CH3COONH4 cho vo cc dung tch 2 lt trong c sn 1 lt nc ct. Thm vo 80ml axit axetic c v khuy cho n khi c dung dch ng nht, nu cn th lc. Ho tan lg aluminon (aurintricacboxilic axit trianmonium) trong 50ml nc ct ri vo cc cha dung dch m trn. Ho tan 3g axit benzoic (C7H6O2) trong 20ml ru metylic ri thm vo cc ng dung dch m trn, nh mc bng nc ct ti vch mc 21t. - Gelatin: Cn 10g gelatin cho vo trong cc c th tch 400ml c sn 250ml nc ct, t cc trn bp cch thu vo khuy cho n khi gelatin tan hon ton. Rt gelatin nng vo trong bnh nh mc 1 lt c sn 500ml nc ct. ngui n nhit phng, thm nc ct ti vch mc v lc u. dung dch gelatin v dung dch m trn vo l thu tinh ti mu c th tch 41t. Lc u, gi ni lnh v ti, dung dch bn trong khong t nht 1 thng. Trnh t phn tch X l mu: Nu trong mu c cht hu c m cn xc nh hm lng Be tng s th phi x l mu bng dung dch HNO3 v H2SO4. Cn ch xc nh Be ho tan th lc qua mng lc 0,45m. To phc vi thuc th aluminon: Dng pipet ht 0; 0,1; 0,5; 1; 2; 3; 4 ml dung dch Be chun s dng cho vo cc bnh nh mc 100 ml. Ly 50ml dung dch mu hoc lng mu cha t hn 200 g Be cho vo bnh nh mc 100 ml. Thm vo mi bnh 2ml EDTA ri thm nc ct ti th tch khong 75ml, lc u. Thm 15 ml dung dch m aluminon, ri thm nc ct ti 100 mlv lc u hn hp. Gi yn 20 pht

sau khi thm aluminon, ch khng ni nh sng, lc nu thy cn thit. o mt quang trong cuvet c chiu dy 5cm ti bc sng = 515 nm (knh lc mu xanh lc). Dung dch so snh l mu trng. Tnh kt qu Da vo ng chun xy dng mi tng quan hm s y = ax + b. Trong : y: hm lng Be; x: mt quang T thay gi tr mt quang o c ca mu vo s xc nh c hm lng Be chnh xc v lch Kt qu ca 32 phng th nghim khi phn tch mu tng hp cha 250 g Ben; 40 g As/l; 240g Se/l; 6gV/l cho thy Be c phn tch vi lch chun tng i l 7,13% v sai s tng i l 13%. 6.5. Xc nh mt s tnh cht khc ca nc 6.5.1. Xc nh hm lng xy ho tan trong nc (DO) Lng xy ho tan trong nc rt nh, thng khong 8- 1 Omg/1. bo ho ca xy ho tan trong nc ngt sch 00C l 14-15mg/l. Thng thng lng xy ho tan trong nc cho chim 70-85% lng bo ho. Lng xy ho tan trong nc thin nhin v nc thai ph thuc vo cc hot tnh sinh ho, ha hc v l hc trong nc. Phn tch DO l mt trong nhng mc tiu quan trng nh gi mc nhim nc, kim tra nhng hot tnh v qu trnh x l cht thi. xc DO c th s dng cc phng php nh: phng php ci tin azid, phng php in cc mng nhy vi xy v my o. Phng php ci tin azid c s dng cho mu nc cng c, cc mu nc sng,... Nguyn l ca phng php ny nh sau: Trong mi trng kim Mn2+ b xy ho tan trong nc xy ho n Mn4+ di dng MnO2.

Khi c mt H+, Mn4+ b I- kh n Mn2+:

Dng Na2S2O3 chun lng I2 gii phng ra vi ch th h tinh bt, t xc nh c hm lng xy ho tan Trnh t phn tch

Ly 300ml mu nc cho vo chai c th tch ln hn 300ml. Thm vo 2ml dung dch MnSO4 v 2ml dung dch I-. y nt v dc ngc chai 15 ln trn u dung dch. Thm cn thn 2ml H2SO4 c vo thnh chai ri y nt v dc ngc chai vi ln. Ly 2O4ml dung dch tng ng vi 200ml mu nc cho vo bnh tam gic, thm vo 3-4 git tinh bt ri ( hun bng dung dch Na2S2S3 0,025N n khi dung dch mt mu xanh v tr ln trng ng. Tnh kt qu Lng xy ho tan c tnh theo mu. C lu dung dch Na2S2O3 0,025N tng ng vi 0,2 mg DO Ho cht - Dung dch MnSO4: Ho tan 480g MnSO4.4H2O trong nc ct, lc ri nh mc ti 1 lt - Dung dch I- trong kim: Ho tan 500g NaOH (hay 700g KOH) v 135g NaI (hay 150g KI) trong nc ct v nh mc ti 1 lt. Thm vo dung dch ny NaN3 ho tan trong 40ml nc ct. - H2SO4 c - H tinh bt 1%. - Dung dch Na2S2O 0,025N: Ho tan 6,205g Na2S2O3.5H2o trong nc ct mi si ri lm lnh bng nc ct, thm nc ct ti 1 lt. Ngoi phng php trn ngi ta cn dng phng php xc nh hm lng xy ho tan trong nc bng cch o trn in cc Di y l bng th hin hm lng xy ho tan (mg/l) trong nc p sut 760nmHg v m tng i l 100% (theo EAWAF, 1973).
0

0,0 14,60 14,21 13,83 13,46 13,11 12,78 12,45 12,14 11,84 11,56 11,28 11,02 10,76 10,52 10,29 10,07 9,85 9,65

0,1 14,56 14,17 13,79 13,46 13,08 12,74 12,42 12,11 11,81 11,35 11,25 10,99 10,74 10,50 10,27 10,O4 9,83 9,63

0,2 14,52 14,13 13,75 13,39 13,O4 12,71 12,39 12,08 11,78 11,50 11,23 10,97 10,72 10,47 10,24 10,02 9,81 9,61

0,3 14,48 14,09 13,72 13,36 13,01 12,68 12,36 12,05 11,76 11,47 11,20 10,94 10,69 10,45 10,22 10,00 9,79 9,59

0,4 14,44 14,05 13,68 13,32 12,98 12,64 12,33 12,02 11,73 11,44 11,17 10,91 10,67 10,43 10,20 9,98 9,77 9,57

0,5 14,40 14,02 13,64 13,29 12,94 12,61 12,29 11,99 11,70 11,42 11,15 10,89 10,64 10,40 10,18 9,96 9,75 9,55

0,6 14,36 13,98 13,61 13,25 12,91 12,58 12,26 11,96 11,67 11,39 11,12 10,86 10,62 10,38 10,15 9,94 9,73 9,53

0,7 14,33 13,94 13,57 13,22 12,88 12,55 12,23 11,93 11,64 11,36 11,10 10,84 10,59 10,36 10,13 9,92 9,71 9,51

0,8 14,29 13,90 13,54 13,18 12,84 12,52 12,20 11,90 11,61 11,34 11,O7 10,81 10,57 10,34 10,11 9,98 9,69 9,49

0,9 14,25 13,87 13,50 13,15 12,81 12,48 12,17 11,87 11,58 11,31 11,O4 10,79 10,55 10,31 10,09 9,87 9,67 9,47

9,45 9,26 9,08 8,91 8,74 8,58 8,42 8,27 8,13 7,99 7,85 7,72 7,59

9,43 9,24 9,06 8,89 8,72 8,56 8,41 8,26 8,11 7,97 7,84 7,70 7,57

9,41 9,23 9,05 8,87 8,71 8,55 8,39 8,24 8,10 7,96 7,82 7,69 7,56

9,39 9,21 9,03 8,86 8,69 8,53 8,38 8,23 8,08 7,94 7,81 7,68 7,55

9,37 9,19 9,01 8,84 8,67 8,51 8,36 8,21 8,7 7,93 7,80 7,66 7,54

9,36 9,17 8,99 8,82 8,66 8,50 8,35 8,20 8,06 7,92 7,78 7,65 7,52

9,34 9,15 8,98 8,81 8,64 8,48 8,33 8,18 8,O4 7,90 7,77 7,64 7,51

9,32 9,13 8,96 8,79 8,63 8,47 8,32 8,17 8,03 7,89 7,76 7,63 7,50

9,30 9,12 8,94 8,77 8,61 8,45 8,30 8,16 8,01 7,88 7,74 7,61 7,49

9,28 9,10 8,92 8,76 8,59 8,44 8,29 8,14 8,00 7,86 7,73 7,60 7,47

Nu gi l hm lng O2 ho tan trong nc mt p sut xc nh th ta c:

Trong : Pm: p sut ti thi im xc nh; S: Hm lng O2 ho tan trong nc ti p sut 760mm Hg theo bng trn. 6.5.2. Xc nh nhu cu xy ho (COD) Ch s ny dng nh gi hm lng cht hu c ca nc thi v s nhim nc t nhin. COD l lng xy cn thit cho qu trnh xy ho ho hc cc cht hu c trong nc thnh CO2 v nc. xc nh con ngi ta thng s dng mt cht xy ho mnh trong mi trng axit, cht thng c s dng l K2Cr2O7. Khi xy ra phn ng:

Lng d Cr2O72- c chun bng dung dch mui Fe2+ vi ch th axit Phenylanthranilic, mu ch th chuyn t tm sang xanh tri cy. Trnh t phn tch Ly 20ml mu nc cho vo bnh hi lu, ri thm vo HgSO4 (10 mg Cl- th cn 0,1 g HgSO4. Thm vo 10ml dung dch K2Cr2O7 0,025N v mt vi ht thu tinh. Lp ng thu sinh hn thu tinh nhm. Thm vo t t 30ml H2SO4 c c cha Ag2SO4 qua phn cui ng sinh hn v lc u hn hp trong khi thm axit. un hi lu trong h gi. ngui v ra sinh hn hi hu bng nc ct. Pha long hn hp bng nc ct ti th tch khong 150ml, ngui. Chun lng bicronat d bng mui Fe2+, vi ch th axit Phenylanthranilic. Cng tin hnh mt th nghim mu trng nh i vi mu phn tch.

Tnh kt qu

Trong : a: th tch Fe2+ Chun mu trng (ml) b: th tch Fe2+ chun mu (ml) N: nng ng lng ca Fe2+ Ha cht - K2Cr2O7 0,025N: Ho tan 12,259 g K2Cr2O7 ( sy kh 2 gi 1050C) trong nc ct v thm nc ti vch mc - H2SO4 c c thm 22g Ag2SO4 cho mt chai 9 lt. - Dung dch Fe2+ 0,1 N: Ha tan 39g Fe(NH4)2SO4.6H2O tinh khit trong nc ct, thm 20ml H2SO4 c ngui ri nh mc ti 1 lt - Ag2SO4 tinh khit ho hc. - H2SO4 tinh khit ho hc Ch th l%: Ho tan 0,2g axit Phenylanthranilic trong 100 ml Na2SO3 0,2%. 6.5.3. Xc nh nhu cu xy sinh ho (BOD) Nhu cu xy sinh ho l lng xy s dng trong qu trnh xy ho cc cht hu c bi cc vi sinh vt. Trong nc, khi xy ra qu trnh xy ho sinh hc th cc vi sinh vt s dng xy ho tan. V vy vic xc nh tng lng xy ho tan cn thit cho qu trnh phn hu sinh hc l rt quan trng nh gi nh hng ca dng chy i vi ngun nc. Trong thc t, ngi ta khng the xc nh c lng xy can thit phn hu hon ton cht hu c, m chi cn xc nh lng xy cn thit cho 5 ngy u vi nhit 200C trong phng ti trnh qu trnh quang hp, ch tiu ny k hiu l BOD5. Phng php xc nh Chun b dung dch pha long: Nc pha long c chun b chai to, rng ming bng cch thi khng kh sch 200C vo nc ct v lc nhiu ln. Cho n khi bo ho xy sau thm 1 ml dung dch m photphat, 1 ml dung dch MgSO4, 1 ml CaCl2 v 1 ml FeCl3, ri nh mc ti 1 lt bng nc ct. Trung ho mu nc phn lch n pH = 7 bng H2SO4 1N hay bng NaOH 1N. Pha long mu nc trc khi xc nh nc bng hiu kh chun b trc theo cc bc sau: + 0,1 - 1% i vi nhng mu nc c dng chy mnh + 15% i vi nhng mu nc cng cha hoc lng

+ 5 - 25% i vi nc b xy ho + 25 - 100% i vi nc sng b nhim Khi pha long cn phi ht sc trnh khng xy ho cun theo. Sau khi pha long xong cho mu vo chai xc nh BOD (thng l chai c th tch 300ml), ng kn nt chai, mt chai dng 5 ngy ni ti ti nhit 200C, mt chai dng xc nh. Do ban u trong mu pha long. Tnh kt qu Lng BOD c tnh theo mg O2/l

Trong D1: lng xy ho tan (mu) ca dung dch mu pha long sau 15 pht; D2: lng xy ho tan (mu) trong mu sau 5 ngy ; P: h s pha long c tnh nh sau

Ho cht - Dung dch m photphat: Ho tan 8,5g K2HPO4, 21,75K2HPO4, 33,4g NaHPO4.7H2O v l,7g NH4Cl trong khong 500ml nc ct ri nh mc ti 1 lt. - Dung dch MgSO4: Ho tan 22,5g MgSO4.7H2O trong nc ri nh mc ti 1 lt - CaCl2: Ho tan 27,5g trong 1 lt nc ct. - FeCl3: Ho tan 0,25g FeCl3.6H2O trong 1 lt nc ct. - H2SO4 1N v NaOH 1N. 6.5.4. Xc nh mu sc Ni chung nc thin nhin sch khng c mu. Trong thc t nc thng c mu do s c mt ca mt s cht mu hu c v cc cht ca Fe3+. Nc thi c th c sc thi khc nhau. Trong nhiu trng hp mu ca nc cn do cc vi sinh vt, cc ht bn, cc thc vt sng trong nc, cc sunfua, cc cht l lng gy nn Trc khi xc nh mu cn lc mu nc. i vi nc c cha nhiu cht l lng, cn lng ri xc nh mu ca phn nc trong. Vic xc nh chnh xc v hon ton khch quan mu ca nc l vic tng i kh, nhiu khi phi m t v sc thi v cng mu bng li ch khng phi bng con s nh lng.

C th xc nh mu sc ca nc bng mt da trn s so snh vi mt lot mu chun hoc bng cch ghi ph hp th ca mu nc trong min kh kin. Cch th nht r rng khng c chnh xc, chi cho ta bit sc thi v cng gn ng ca mu ( m nht). Cch th hai chnh xc, khch quan, nhng i hi phi c thit b t tin v khng thc hin c trong iu kin phn tch ti ch. Di y l phng php xc nh mu sc ca nc theo cch so snh vi dy dung dch chun c mu sc tng t v vic so snh c thc hin bng cch o trn my so mu quang in. Trong thc t nc thng c mu sc gn vi mu ca dung dch hn hp K2Cr2O7 v CoSO4, nn ngi ta thng dng dy dung dch ca hn hp lm dy chun so snh xc nh mu ca nc. Trnh t tin hnh ng chun: Chun b 10 ng o Nessler, dng pipet ly ln lt vo mi ng 1, 2, 3, 4, 5, 6, 8, 10, 12, 14 ml dung dch I v thm dung dch II n th tch 100ml. mu ca dy dung dch chun c biu din trn thanh mu theo bng sau:
Th tch dung dch I (ml) mu 0 0 1 99 5 2 98 10 3 97 15 4 96 20 5 95 25 6 94 30 8 92 40 10 90 50 12 84 80 Th tch dung dch II (ml) 100

o mt quang ca dung dch chun trn my so mu, s dng cuvet c chiu dy 1-10mm. xc nh mu ca mu nc, cho nc vo cuvet v tin hnh o mu nh lm i vi mu. Ho cht v dng c - My so mu quang in - ng o Nessler, th tch 100 ml. - Dung dch I: Ho tan 0,0876g K2Cr2O7 2g COSO4.7H2o v lu dung dch H2SO4 c trong nc ct thnh 1 lt. - Dung dch II: Dung dch H2SO4 long (1:1000). 6.5.5. Xc minh dn in ring Nc tinh khit hu nh khng dn in, v nc phn ly rt t. Nhng cc cht tan trong nc phn ly thnh cc cation v anion nn cc loi nc thin nhin cng nh nc thi li c tnh dn in dn in ring theo nh ngha l gi tr nghch o ca in tr ring (l in tr ca dung dch nm gia hai cc c b mt lcm2 v cch nhau l cm) ca dung dch. Ti mt nhit xc nh, dn in ring ph thuc vo nng cation v anion, tc l vo thnh phn ca dung dch. xc nh dn in ring ca dung dch ngi ta dng my o dn (c th o in tr trong khong 50 - 100.000 ) dng cc cc platin v bnh ng dung dch nghin cu km theo my.

Mu nc xc nh dn in th khng c x l v nn xc nh ngay sau khi ly mu. o dn in ca dung dch, ngi ta cho dung dch vo bnh o, nhng vo hai cc platin, ni hai cc vi my o. dn in ring c tnh theo cng thc:

Trong : : dn in ring; R: in tr o c; K: hng s t l thng c gi l hng s bnh o hoc hng s h cc. K ph thuc vo cu to, kch thc ca h cc v hnh dng ca bnh o. Trc khi xc nh dn in ring ca dung dch nghin cu phi xc nh K, hoc thng ni l chun ho h cc. chun ho h cc ngi ta o in tr ca dung dch KCl c nng xc nh. K c tnh theo cng thc:

Trong : R: gi tr trong bnh ca in tr dung dch o c 1278: dn in ring ca dung dch KCl 0,01 M 200C, -l.cm-1. Trnh t tin hnh Chun ho h cc: Trng bnh o 3 ln, mi ln bng vi ml dung dch KCl 0,01M, trng h cc cng bng dung dch . Ngm dung dch v h cc trong my iu nhit c nhit 200C (kim tra bng nhit k c chnh xc 0,10C). o in tr ca dung dch trn my o dn v xc nh K da vo cng thc trn. Cho dung dch chun vo 5 - 10 bnh v tin hnh o nh vy, ly kt qu trung bnh tnh K. nc vo hai bnh c trng trc 3 ln mi ln bng vi ml nc cn xc nh dn, ngm cc bnh vo b nc ca my iu nhit iu chnh sn 200C cho n kh nc trong bnh c c nhit . Nhng h cc vo bnh th nht nhiu ln ra h cc. Nhng h cc vo bnh th hai v o in tr. Ghi kt qu R o c. Nu phi o nhiu mu c dn khc nhau th mi mu dng 3 bnh, hai bnh ra h cc, bnh th 3 o dn. C th o nhit khc nhau, nhng phi xc nh chnh xc nhit o ca nc ri dng bng hiu chnh a v dn 200C. dn 200C c tnh theo cng thc:

Trong : K: Hng s h cc f: H s hiu chnh nhit

R: in tr o c Ho cht v dng c - Dung dch KCl 0,01M: Ho tan 0,7456g KCl tinh khit ho hc ( c sy kh 1000C v ngui trong bnh ht m) trong nc ct hai ln thnh 1 lt dung dch 200C. - My o dn (dng dng xoay chiu), c th o c in tr 50 - 100.000 - My iu nhit

Chng 7 PHN TCH T

7. 1. Gii thiu chung t l mi trng h tr cho s sinh trng v pht trin ca thc vt v h sinh tho. Vi mc ch nh vy, tnh bn vng ca t ch yu ph thuc vo khng gian i vi s pht trin ca b r thc vt v kh nng trao i ca n vi nc, khng kh, nhit v cc cht dinh dng. Nhng yu t ny th hin ph nhiu ca t. Khng gian pht trin ca r thng c xc nh bng s vn su (solum) ca r. Tuy nhin, i vi cc loi t, c tnh xp v lin kt khng cht s thc y kh nng m su ca r. Mt r ph thuc ln vi mt s tnh cht t nh s thay i v dung trng, thnh phn rng, mc nc ngm v s phn b ca cc thnh phn nh mui, pH, th kh. Bng 7.1. bn ca r i vi kh nng m xuyn
su t hn 10 cm 10 - 25 cm 25 - 50 cm 50 - 100 cm Ln hn 100 cm S m xuyn ca r Rt hp Hp Trung bnh Su Rt su

Cc nghin cu v t c th theo mt s hng sau: Xc nh kh nng trao i dinh dng Xc nh cc vt cht c kh nng gy nh hng nguy hi ti nc ngm. Xc nh cc tnh cht n mn i vi ng ng Xc nh s mn ho Kim tra hiu qu lc Xc nh cht lng t Xc nh mc nhim bn mi trng t Hm lng cc cht dinh dng c th trao i t t l yu t quan trng quyt nh kh nng cung cp dinh dng cho cy trng v do vy vic xc nh chng phi s dng phng php thng nht. T c th tnh ton nhu cu cung cp thm cht dinh dng cho cy (bn phn). Kh nng trao i cc cht inh dng c tng kt trong bng 7.2.

Bng 7.2. Dng cht dinh dng lin kt trong t

Dng lin kt B ho tan nhng khng lin kt trong t Mt phn lin kt vi cc cht trao i Khng linh ng, d b linh ng Khng linh ng, kh b linh ng Kh nng trao i Rt d D dng Kh Rt kh Xc nh bng Cc cht dinh dng ho tan trong nc Cc cht dinh dng trao i (bao gm phn ho tan trong nc) Cc cht dinh dng trao i (bao gm phn ho tan trong nc) Phn b d li ca cc cht dinh dng

Tuy nhin, t l trao i ca cc cht dinh dng c bn ph thuc vo thnh phn st hu c, m t, pH, v th kh. Hm lng cc cht b linh ng trong mi trng thc cht ph thuc vo cc iu kin kh hu v tng t. nh gi s nhim bn cc cht v c (kim loi nng) trong t l rt kh khn do nng vn c ca kim loi nng c th ph thuc rt ln vo trng thi khong vt hc (thnh phn m). S dng cc cht dinh dng (bn phn) cng l nguyn nhn dn n nhim bn t. nh gi s nhim bn c th c xem xt t quan im v li nhun hoc hiu qu ca t khi xem n nh l mt lp lc nc t nhin. i vi vn ny cn quan tm cc im sau: - Vai tr quan trng ca t nh l vt mang i vi cy trng - Kh nng lc ca t i vi vic bo v nc ngm. Vic chn la cc th nghim i vi vic nghin cu kh nng linh ng ca kim loi nng ang tn ti mt s vn . gii quyt vn ny, cc kt qu o c tnh d tan ca kim loi nng i vi thc vt bng phng php chit cho php s dng so snh vi lng kim loi nng c ht bi r thc vt. S dng axt mnh hoc cc cht to phc mnh chit kim loi nng trong t khng cho kt qu n nh. S dng NH4OH cho kt qu tng i n nh i vi vic xc nh cc dng linh ng ca cc nguyn t vt. Ngy ny, c rt nhiu phng php chit c s dng trong cc nghin cu lin quan n kim loi nng c cng b bi nhiu tc gi. Phng php chit thng dng nht thng c thc hin theo quy trnh chit lin tc c cng b bi Tissier 1979). Kh nng chit hu ht cc kim loi nng t t ln hn hu ht cc nguyn t thng thng (photpho: 1%, Al 2% n 3%, Na: 0,1 n 0,5%). Tuy nhin, kim loi nng cng c bit n lin kt mnh vi cc vt cht humus hn cc nguyn t c cp trn. Gii hn chng chu ca kim loi nng trong t l rt quan trng. Bng 7.3 cung cp ngng c tng ng vi nng ca chng trong cy trng. Gii hn ny thay

i tu thuc vo loi thc vt. Bng 7.3. Khong gy c ca m s kim loi nng trong t Nguyn t Cu Zn Cd Ni Pb Cr Hg Ngng (mg/kg) 200-400 500-5000 10-175 200-2000 500-1500 500-1500 10-1000

Nhim bn t do cc cht hu c nh ho cht bo v thc vt cng phi c xem xt n. Trong qu trnh s dng ho cht bo v thc vt, mt phn c a vo hoc ri xung trc tip xung t. Lng hp ph vo t thay i theo tuyn v c mi quan h khng ln. S tn ti ca HCBVTV trong t c m phng trong hnh 7.2. Khi i vo t, cc vt cht ny thay i c tnh sinh hc l thuc vo mt s tnh cht t, chng b chuyn ho thm tr b khong ho hon ton. Cc lp t b mt c cha cc cht hu c s hp ph HCBVTV. S thm su ca chng ph thuc vo thnh phn khong st, thnh phn Nit, oxt Fe, Al v cc l hng trong t.

Nghin cu v cc tnh cht n mn ca t cng nh vic xc nh s mn ho c bit quan trong ti cc khu vc kh hn. Bng 7.4. Cc ch tiu cn quan trc i vi cc nghin cu c th
Thnh phn nh gi cc dinh dng vt cht gy c Thnh phn cp ht Thnh phn nc pH Th kh dn n Tnh chua/ kim Hu c ccbon Na K Ca Mg Mn Cu Zn Cr, Ni, Cd, Hg Br Mo N tng s, N hu c NH4 NO3 Pht pho tng s ClSO4 Cacbont, Hydro cacbonat S HCBVTV mn. X X X X X X X X X X X X X X X X X X X nh gi tnh cht n mn ng ng X X X X X X X S mn ho

X X X

X X X X X X X X

X X

X X X X X X X X X X X X

7.1.1. T chc thc hin v phng php ly mu t a- Nguyn tc

Nhim bn t c th n t nhiu ngun, cht nhim bn c th tip xc trc tip, do cht thi bc hi, pht tn do gi, nc mt v nc ngm. Khi nghin cu mt khu vc bit trc c cc ngun gy nhim, vi tr ly mu c th c la trn trn c s cc thng tin xc nh v cc im nng, tuy nhin, phng php ly mu ny cn ch v tnh chnh xc ca cc thng tin, nu khng s dn ti cc kt lun sai lch. Lp t b mt c th b nhim bn theo cc cch sau: Qun l rc thi khng ng cch Tai nn, nh trn Trm tch khng kh Hot ng cng nghip Hot ng nng nghip v.v.. Mc ch nghin cu cng cn phi c lm r trc khi tin hnh ly mu (mu nng ho, mu th nhng, mu nh gi nhim bn. i vi tng mc ch nghin cu, thng tin ca a bn nghin cu cng cn c lm r nh: loi t su tng t, chui a hnh, chui kh hu, chui sinh hc, chui thch quyn, din tch...) phn bit c tnh ng nht hay khng ng nht ca khu vc nghin cu. Phng php ly mu theo ng k c th s dng i vi cc khu vc b nhim bn trn din rng. chn la khu vc ly mu t mt, k vung trn ton b khu vc d inh ly mu. vung c v da trn c s v cc thng tin chung ca khu vc hoc s dng phng php thng k (s c ly phi m bo ti thiu l 25% trn tng s , s mu c ly trn mi phi m bo ti thiu l 10 mu). Cch lm ny c th dn ti vic mt s im "nng" b b qua, nhng k vung c th lin kt c ton b cc im ly mu. Hin nay, khi tin hnh ly mu cc thit b nh v ton cu thng c s dng km theo. Cng c ny gip cho vic xy dng cc bn phn b cht nhim tch hp cc thng tin cho ci nhn tng th v s bin i cht lng t theo thi gian do nh hng ca cc hot ng sn xut.

Tu thuc vo mc ch nghin cu trng lng mu t c ly c th t 300500 gram. b- Dng c ly mu, ti ng mu Dng c ly mu c th dng bng cuc, xng, hoc cc dng c chuyn dng nh hnh di y. Ti dng mu c th dng ti plastic. Cc mu t c ly yu cu phi ghi r tn mu, a im, thi gian ly

c. Bo qun Cng ging nh i vi mu nc, tu thuc vo i tng nghin cu s yu cu cc phng php bo qun mu khc nhau. i vi cc mu phn tch cc ch tiu nh NO2-, NO3-, NH4+, cc ch tiu vi sinh vt... phi c bo qun trong iu kin lnh trnh s phn hu v hot ng ca cc vi sinh vt trong mu. Mu phn tch cc ch tiu ny i hi phi phn tch ngay trong trng thi mu ti, khng qua cc

bc x l s b s c cp phn di y. i vi cc ch tiu phn tch l ho hc khc i hi phi qua bc x l s b trc khi phn tch.

7.1.2. X l s b phn tch l - ho 7.1.2.1. Nguyn tc Mu t kh trong khng kh, hoc trong t sy nhit khng qu 400C hoc lm lnh kh. Nu cn, lm v t trong khi vn cn m, cn b v nghin li sau khi kh. t c ry v kch thc phn ht nh hn 2 mm c chia thnh tc phn bng my hoc bng tay c th ly mu i din phn tch. Nu yu cu mu nh (<2 g) phn tch th c ht c phn nh hn 2 mm phi gim i hn na. Cc trnh t cn thit c th hin trong s di y.

Ch : 1. Lm kh nhit 400C trong t sy thch hp hn phi trong khng kh nhit phng, v tc lm kh nhanh s hn ch nhng thay i do hot ng ca vi sinh vt. 2. Cn lu rng mi mt kiu x l s b nh hng n mt s tnh cht t. 3. Bo qun cc mu t gm cc mu nhn c, phi kh trong khng kh, lm lnh hoc bo qun trong mi trng khng c nh sng, trong mt thi gian di c th nh hng n mt s thng s t c bit l cc ho tan ca c phn v c v phn hu c. 4. i vi cc mu t ly t ngun nhim, nn p dng cc php o c bit, cn trnh tip xc vi da v nn c cc bin php c bit khi lm kh cc mu t loi ny (thng gi, lu thng khng kh). 5. Khi lng mu yu cu phi c sn t nht 500 g t va mi ly 7.1.2.2. Thit b, dng c T sy, t lnh kh, my lm v, ry phng, my trn, sng rung, ry li, cn phn tch ( chnh xc ti thiu ti 1g). Cch tin hnh a- M t mu Xem xt mu nhn c v ghi li dng mu theo thut ng thch hp gm c cc chi tit v vt ngoi lai, nhng thc vt cn li v cc c im ng lu hoc c lin quan khc. b- Lm kh Lm kh ton b trong khng kh hoc trong t sy thng gi loi b khng kh m hoc trong t lm kh lnh. Lm kh mu cho ti khi khi lng mu t gim khng qu 5% (m/m) trong 24 h. tng tc trong qu trnh lm kh, p nh cc cc t c kch thc ln hn (ln hn 15 mm) trong khi lm kh. Khi mu c phi kh trong khng kh, nghin nh bng tay bn cch s dng ba g h mt ci gi v chy. Khi mu c sy kh trong t sy, tm thi sy mu ra khi t v x l nh cc trn. Cc ny cng lm cho vic tc cc ht c kch thc ln hn 2 mm d dng hn. Lm kh khng kh Dn mng tt c cc vt liu thnh mt lp khng dy qu 15 mm trn mt ci khay khng ht m t t v khng nhim bn. Ch yu l trnh nh nng mt tri trc tip nh sng mt tri trc tip c th to

ra s chnh lch nhit ln trong mu, c bit gia lp t pha trn kh mt phn hoc ton b vi nhng lp t pha di vn cn m. Lm kh trong t sy Dn mng tt c cc vt liu thnh mt lp khng dy qu 15 mm trn mt ci khay khng ht m t t, khng nhim bn. t khay trong t sy v lm kh nhit khng cao qu 400C. c- Nghin v loi b cc vt liu th Loi b Trc khi nghin phi loi b . cc mnh thu tinh v rc v.v.. c kch thc ln hn 2 mm bng cc ry v nht bng tay. Xc nh v ghi li tng khi lng mu kh v khi lng vt liu no b loi b bc ny Loi b cc vt liu t nhin nh hn 2 mm Ry vt liu nh hn 2 mm, ghi li khi lng ca vt liu ln v nh hn 2 mm, nghin loi ln hn 2 mm, dng my hoc bng tay trn u mu. d- Nghin ton b mu Gim c ht ln hn 2 mm Nghin t kh thnh cc ht khng ln hn 2 mm bng cc dng c thch hp. Cc dng c cn thit phi c iu chinh hoc s dng sao cho hn ch n mc ti thiu vic nghin nh cc ht ban u (kt vn v khi lin kt). e- Ry C th s dng ry my hoc bng tay. f- Ly mu chun b mu th nghim, cha phn mu c lm kh, nghin nh v ry (kch thc hin ti < 2 mu thnh cc phn i din t 200 g n 300 g hoc theo mt trnh t thch hp khc. chun b mt mu th, chia mu th nghim thnh cc phn i din cho n khi t c c mu yu cu. Trnh vic to bi cng nhiu cng tt Ly mu bng tay (chia t) Trn k mu trn bng my hoc bng tay v dn mu thnh mt lp mng trn mt ci khay khng nh hng ti thnh phn ca mu. Chia t thnh bn phn bng nhau. Gp hai trong bn phn theo ng cho, loi b hai phn kia. Lp li trnh t ny cho n khi t c khi lng t mong mun. S dng dng c chia mu S dng loi hp c nhiu rnh, chia mu thnh hai phn bng nhau. Ly mu bng my

 mu t vo trong phu ca thit b ly mu, vn cht cc chai ng mu vo vi tr. Khi ng thit b ly mu. Sau khi ly mu, nhng phn trong chai vo hp ng mu khc. Lp li trnh t trn nu cn g- Nghin Nu phi ly mu th nh hn 2 g phn tch, iu thit yu nht l phi nghin nh hn na phn ht nh hn 2 mm. Nghin mu t i din ca t c phi kh, gi nh v ry cho n khi ton b mu lt qua ry 250 cm hoc mt c quy nh khc trong phng php th.

7.2. Phn tch mt s tnh cht l ho hc c bn ca t 7.2.1. Thnh phn c gii t t l mt h thng d th gm nhng phn t khong, khong - hu c v hu c c kch thc khc nhau, t phn t n nhng nguyn t c hc c kch thc ln nh st, limn, ct v gim cui. Trong nghin cu t, nhiu khi cn phi xc nh kch thc ca nhng hp phn ny v mt s lng v cht lng. Thnh phn c gii c ngha quan trng, n c trng cho ngun gc pht sinh ca t, cc tnh cht t v ph ca t. Vic phn loi t v c bn cng da vo thnh phn c gii ca t. V d, t ct, ct pha, t tht, t st... i vi dinh dng ca cy trng th thnh phn c gii t li cng c vai tr to ln, t c thnh phn c gii nng gi c nhiu cht dinh dng hn. Nhiu tnh cht vt l ca t nh xp, tr m, tnh thm, kh nng gi kh, gi nhit... u ph thuc vo thnh phn c gii. a. Phn loi nhng nguyn t c hc trong t Nguyn t c hc ca t tn ti 3 dng: Khong, hu c v hu c khong (cn gi l humat). Trong th nhng hc c nhiu bng phn loi nguyn t c hc theo ln ca chng v bng phn loi ca Katrinski c tha nhn rng ri nht. Trong bng phn loi ny tc gi chia thnh: vn, si, cui, ct, limon v st. Bng 7. 5. Phn loi nhng nguyn t c hc ca t (theo Katrinski) ng knh (mm) >3 3-1 1 - 0,5 0,5 - 0,25 0,25 - 0,05 0,05 - 0,01 0,01 - 0,005 0,005 - 0,001 < 0,001 > 0,01 < 0,01 Tn gi Phn vn ca t Si cui Ct th Ct trung bnh Ct mn Limn th Limn trung bnh Limn mn St Ct vt l St vt l.

Tt c nhng phn t c kch thc ln hn 1 mm gi l "phn xng" ca t, nhng phn t nh hn nam gi l "Phn mn" ca t. N.M. Xibicxep (1899) phn chia nhng phn t ca t thnh "ct vt l" - tc l nhng cp ht ln hn 0,01 mm

v "st vt l" - nhng cp ht nh hn 0,01mm. Nhng khi nim ny hin nay c s dng rng ri trong phn loi t theo thnh phn c gii. b. Chun b t phn tch thnh phn c gii i vi nhng t cha cacbonat i vi nhm t ny vic chun b phn tch thnh phn c gii rt phc tp, ngi ta thng s dng cc dung dch mui khc nhau nh: natrioxalat (Na2C2O4); pirophotphat (Na4P2O7) v hecxametaphotphat (Na6P6O18). Tu thuc vo hm lng cacbonat v dung tch hp ph ca t m s dng Na2C2O4 0,5N vi lng khc nhau. Vic s dng cc dung dch mui nam x l mu t l y nhng cacbonat ca t di dng cc mui khng tan, do trong t s c hnh thnh nhng nguyn t c hc mi. Nhng Hp cht mi ny l.(Ca, Mg); C2O4; (Ca2, Mg2) P2O7; (Ca3, Mg3) P6O18; Na2Ca2 (PO3)6. Trong thc t vic x l t bng nhng mui kim trn y thng c kt hp vi nhng phng php c hc, ngha l nghin, cn t. P.F. Menhicp (1952) ngh phng php pirophotphat nh sau: Cho t t dung dch pirophotphat 5% vo mu t phn tch n trng thi sn st. i vi t mn v t cacbonat c thnh phn c gii nng th s dng t 20 - 25ml cho 10 g t, cn i vi t ct pha v t ct th s dng 15ml cho 15g t. i vi t khng mn v khng cha cacbonat c thnh phn c gii nng th s dng 5ml; t tht, ct pha v ct th s dng 3ml cho lp t. Mu t c nho trn trong 20 pht, sau dng chy s c bt u cao su nghin, tn trong 5 pht v vo cc va nghin tn va gn cho n khi xut hin nc trong khi t gng. Cho t qua ry kch thc 0,1 hoc 0,25mm vo ng ong c dung tch 1 lt. Thm nc vo ng ong cho n 1 lt v phn tch thnh phn c gii theo phng php pipet ca Katrmski. Phng php hecxa - metaphotphat x l mu t: ly khong 300g t, nu l t mn th trc ht phi loi ch bng cch ra t qua giy lc trn phu, dng nc ct ra nhiu ln cho n khi ht ln Cr (dng AgNO3 5% trong mi trng c axit ho bng HNO3 10% th phn ng clo). t sau khi ra sch em phi trong phng n trng thi kh khng kh, ry qua ry 1 mm v ly 20g phn tch. Dung dch dng x l mu t c chun b nh sau: ly 3,7 g Na6P6O18 + 7,94g Na2CO3 ho tan trong 1 lt nc. Natri cacbonat thc y s thy phn ca hecxa- metaphotphat thnh octophotphat. Ly 20ml dung dch ny thm vo mu t c ra (nu m t mn) v 10 ml i vi t khng mn, dng a thu tinh u c gn cao su khuy cn thn v sau khong 15 - 20 pht dng nc ct chuyn dn t sang bnh tam gic dung tch 250ml. un dung dch huyn ph ny trong 1 gi, sau chuyn t vo ng ong c dung tch 1 lt qua ry c 0,1 mm, cn c nh v ra khng cho cc phn t st bm vo. Dung dch t trong ng ong trng thi huyn ph v xy ra hin tng t keo.

Nu qu trnh t keo xy ra chm th c th thm mt t dung dch x l vo dung dch huyn ph. Trng hp qu trnh t keo xy ra nhanh th cn thn gn phn nc trong v thm nc ct cng vi mt phn dung dch x l. c. Nguyn tc v k thut phn tch thnh phn c gii t Cc phng php phn tch thnh phn c gii t bao gm phng php ngoi ng rung, phng php ry, phng php trong mi trng nc (phng php gng gn, phng php t trng k, phng php pipet). Phng php ngoi ng rung (xc nh nhanh, khng c dng c Phng php t: Tm t mu t ri dng hai lng bn tay v thnh si di 5 - 6cm. K thut tm t t cn ch va , khng kh qu, khng nhau qu, ngha l m tng ng vi "gii hn chy di". Sau khi v thnh si, tip tc un thnh vng trn. S th hin hnh dng ca vng trn tng ng vi thnh phn c gii t c minh ho bng 7.6. Bng 7.6. Xc nh thnh phn c gii theo phng php ngoi ng rung

Phng php ny nu c thc hin cn thn cng cho nhng kt qu tt gn ng vi kt qu phn tch trong phng. - Phng php phn tch thnh phn c gii trong mi trng nc ng yn tnh (phng php pipet ca Katrinski - Gluskop). Phng php ny do Gluskop xut nm 1912. n 1922 Robinson ngh dng ng ht vi th tch 25ml ly dung dch huyn ph cho nn cn gi l ng ht Robinson hay pipet.

Nm 1930, ti Hi ngh Quc t Th nhng, phng php ny c cng nhn l phng php tiu chun xc nh thnh phn c gii t v c s dng rng ri nhiu nc trn th gii. Trnh t phn tch mu t phn tch sau khi phi trong phng n trng thi "kh khng kh", dng ci chy s gi t v ry qua ry c 1 mm. Trn u, ly 3 mu t phn tch theo yu cu:
t tht v tht nng (g) - xc tnh ht m khng kh (1) - xc tnh lng tiu hao khi x l bng HCl (2) - chun b dung dch huyn ph (3) 4-5 10 - 15 10 - 15 t ct v ct pha (g) 10 20 - 30 20 - 30

Lng t phn tch nhiu hay t tu thuc vo c tnh ca t, t c thnh phn c gii cng nh th lng t ly phn tch cng nhiu v ngc li. Mu t s 2 v 3 cho vo bt s v kim tra mc cha cacbonat ca t bng cch cho nh git HCl 10% vo mu. Nu t c cacbonat th xut hin bt kh CO2 bay ra v lc ny cn tip tc x l bng ng dch HCl 0,2N cho n khi khng thy xut hin bt kh CO2,vic ph hu cacbonat khi phn tch thnh phn c gii l cn thit v Ca v Mg trong t c vai tr cht kt dnh, chng lin kt cc nguyn t c hc li vi nhau to thnh nhng on lp c kch thc ln hn. Tip tc HCl 0,2N vo mu t, dng a thu tinh khuy lng mt thi gian ri gn phn nc trong bt s theo a thu tinh qua phu lc. Hai mu t c x l song song cho n khi nh HCl 0,2N khng thy xut hin bt kh th dng li. Sau khi ph hu cacbonat, dng dung dch HCl 0,05N chuyn dn mu t bt s ln giy lc t trong phu. Mu t dng xc nh lng tiu hao khi x l HCl cn chuyn ln giy lc t trong phu nhng cn trc khi lng ca giy lc. t trn phu tip tc c ra bng HCl 0,05N cho n khi ht phn ng vi Ca2+, th phn ng, dng ng nghim hng mt t dch lc, thm hai git ch th phenol phtalein v dng NH4OH 10% trung ho theo tng git cho n khi xut hin mu hng, phn ng lc ny hi kim. Thm vi git CH3COOH 10% axit ho dung dch, thm vi git (NH4)2C2O4 4% v un n si. Nu c Ca2+ th s xut hin tinh th CaC2O4 rt r. Nu ht Ca2+ (khng c kt ta) chuyn ht t nn phu bng dung dch HCl 0,05N. Tip tc ra mu t trn bng nc ct cho n khi ht phn ng vi clo. th phn ng, dng ng nghim hng mt t dung dch lc, dng vi git HNO3 10% axit ho dung dch, sau thm vi git AgNO3 5%, nu cn do s xut hin kt ta mu trng AgCl.

i vi nhng mu t khng c cacbonat th dng ngay axit HCl 0,05N x l, sau cng chuyn qua phu lc, ra cho n khi ht canxi v clo nh trnh t trn. Mu t dng tnh lng tiu hao khi x l HCl, sau khi ra t v giy lc c cho vo trong cc s hoc nhm cn trc khi lng, sy kh 1050C n khi lng khng i ri cn. Cn c vo hiu s khi lng, xc nh lng tiu hao khi x l HCl. Mu t dng phn tch thnh phn c gii, sau khi ra sch Ca2+ v do dng a thu tinh chc thng giy lc, dng nc ct c ra trc tip vo bnh c dung tch khong 750cm3. Thm nc ct vo bnh n th tch khong 250cm3 v thm NaOH l theo dung tch hp ph ca t. C 1 ml NaOH l tng ng vi 10 mgl ca dung tch hp ph. Vic thm NaOH l vi mc ch ph v hon ton cc vi on lp v chuyn sang cc nguyn t c hc. V cc mu t dng phn tch thnh phn c gii nhiu khi cha xc nh dung tch hp ph trc, cho nn thun tin ngi ta quy nh lng NaOH 1N (ml) thm vo cc loi t bng sau. Bng 7. 7. Lng NaOH l dng cho cc loi t khc nhau
Loi t 1. t feralit: Tng 0 - 50cm Cc tng di 2. t feralit trn sn phm vi: tng 0 - 50cm Cc tng di 3. t macgalit: Tng 0 - 50cm Cc tng di 4. t ph sa: t ph sa c tng ra tri, bc mu Cc loi ph sa khc Lng NaOH 1N(ml) 1-2 1 - 1,5 1,5 - 3 2-3 2-5 2 -3 0,5 - 1,5 0,5 - 1,5 1-3

Sau em un si th huyn ph 1 gi, thi gian tnh t lc bt u si. Lm ngui dung dch v chuyn ton b dung dch vo ng ong c dung tch 1 lt qua ry c 0,25mm. Dng nc ct ra phn cha trn ry v sau thm nc ct n 1 lt. Nh vy, phn cn li trn ry gm nhng cp ht c kch thc t 0,25 - l,0mm, phn cha trong ng ong l nhng cp ht c kch thc < 0,25mm. Phn cha trn ry cho vo chn s bit khi lng, sy 1050C trn khi lng khng i. Nu cn tch cp ht ct kh 1 - 0,5 mm th dng thm ry 0,5mm v s thu c 2 cp ht ct th: 1 - 0,5mm v ct trung bnh 0,5 - 0,25mm. Tin hnh phn tch cc cp ht phn trong ng ong da vo vn tc lng ca phng trnh Stockes. Tng quan gia kch thc cp ht v su ng ht (pipet) trong dung dch nh sau:

+ i vi cp ht < 0,050 mm th su ng ht l 25cm + i vi cp ht < 0,01 mm th su ng ht l 10 cm + i vi cp ht < 0,005mm th su ng ht l 10 cm + i vi cp ht < 0,001 mm th su ng ht v 7cm. Thi hn ly mu t nhng su khc nhau c tnh t khi ngng khuy c dung dch, thi hn ny thay i ph thuc vo nhit v t trng th rn ca t. Trong khi phn tch cn gi iu kin nhit c nh. V d, nhng ng ong cha mu c t trong mt b nc lm bng min trong sut, nc trong b c iu ho nhit nh hai vi nc nng v lnh, hoc ng ong c y np gi nhit, hn ch khng cho nhit dao ng gy nh hng n vn tc chm lng. theo di nhit , t nhit k vo ng ong cha nc v gi nhit nh iu kin ca nhng ng dung dch t. Bi v khong thi gian gia nhng ln lc ht i vi nhng cp ht < 0,05; < 0,01 v < 0,005 mm khng lu lm nn nhit c th ch o mt ln. Khi cn ly cp ht < 0,001 mm nn o nhit ba ln: sau khi mc dng dch, trc khi ht v 1 ln vo gia hai thi im trn. Ly nhit trung bnh sau 3 ln o, i chiu vi tc lng tng ng chn phn tch. V t trng th rn, nn ly gi tr chnh xc ca tng loi t nghin cu. Tuy nhin, trong phn tch c th dng nhng t s tng i gn ng cho mt s trng hp Bng 7.8. T trng th rn ca m s nhm t chnh Vit Nam
su (cm) 0 - 20 20-50 50 - 100 100 - 150 150 - 200 Nhm t feralit (t vng) 2,55 - 2,65 2,60 - 2,65 2,65 2,70 2,70 Nhm t ph sa trng la 2,65 (chung cho c cc tng di)

bng ch dn thi hn ly mu dung dch huyn ph trong ng ong cc su khc nhau tng ng vi vn tc lng ca cc cp ht theo phng trnh Stockes trong iu kin nhit v t trng th rn ca t khc nhau. Vn tc chm lng ca cc cp ht (V) tnh theo phng trnh Stockes:

Trong : r: bnh knh ca cp ht (mm); d1: t trng th rn ca t;

d: t trng cht lng khi dng phn tch; g: gia tc trng trng khi vt ri t do (981 cm/s);
: nht ca cht lng (poaz)

Dng c phn tch thnh phn c gii t bng pipet theo Katrinski c trnh by hnh 7.7. K thut ly mu dung dch huyn ph bng dng c ny nh sau khuy dung dch huyn ph trong ng ong bng que khuy. Que khuy gm mt ng cao su hnh trn gn vi a thu tinh hoc que kim loi khng g. Tm cao su hnh trn c c thnh nhiu v, ng knh mi l khong 3mm, que khuy cho chuyn ng t trn xung di v ngc li 10 ln trong 20 giy. Theo thi hn tnh sn (xem ph lc 8) nhng ng ht xung su quy nh ht ly thnh phn cp ht cn tm, dung dch c ht vo pipet mt cch t t. Ly 25ml dung dch huyn ph khi xc nh thnh phn cp ht nh hn 0,05mm trong thi hn 30 giy, i vi cp ht < 0,01 mm trong thi hn 25 giy v cp ht nh hn 0,05 mm trong thi hn 20 giy. Mu ly xong cho bc hi trn bp cch ct hoc trn ni cch thu, sau sy nhit 1050C trn nhit khng i. Khi lng cc c cn sn sau khi cn song tnh kt qu. Hm lng cc cp ht c tnh ra phn trm theo cng thc:

Trong : x: thnh phn cn tm tnh ra %, thnh phn nh hn kch thc cp ht no , v d < 0,05mm; < 0,01 mm... a: khi lng ca thnh phn nh hn kch thc cp ht cn tm (g); b: th tch dung dch huyn ph (ml); m: khi lng t kh tuyt i ly khi phn tch (g).. Trong thc t phn tch khng nn tnh theo t "kh tuyt i" m tnh theo t

"kh khng kh", lm nh vy s c nhiu thun li trong vic tnh kt qu. Mun vy, nhn cng thc trn vi h s kh kit (k). H s k c xc nh theo cng thc:

Theo cng thc ny Why l ht m khng kh ( m hydroscopic). Khi lng thnh phn c kch thc xc nh (0,05 - 0,01; 0,01 - 0,005mm; 0,005 - 0,001 mm v < 0,001 mm c tnh bng cch tr khi lng hoc hm lng phn trm ca thnh phn tip theo. V d c th v cch tnh 1) Khi lng t kh khng kh ly kh phn tch l 10g; 2) Khi lng thnh phn c kch thc 1 - 0,25mm l 0,81g; 3) Lng tiu hao khi x l bng HCl l 0,232g; 4) Khi lng thnh phn trong 25cm3 dung dch: Kch thc cp ht (mm) < 0,05 < 0,01 < 0,005 < 0,001 Khi lng thnh phn cp ht (g) 0,116 0,075 0,015 0,009

5) Thnh phn cp ht tnh ra % so vi khi lng t kh Khi lng cp ht(mm) Thnh phn (%)

Khi thm vo dng dch huyn ph 2ml NaOH 1N, tng ng 0,08g, nu tnh vi lng t dng phn tch ln th chim t l 0,8%. Nh vy thc t hm lng cp ht

nh hn 0,001mm ch bng 3,64 - 0,8 = 2,84%. 6) Khi lng thnh phn (%) so vi lng t Kch thc cp ht (mm) 1 - 0,25 0,05 - 0,01 0,01 - 0,005 0,005 - 0,001 < 0,001 Thnh phn (%) = 8,18 = 46,8 - 30,3 = 16,5 = 30,3 - 6,06 = 24,24 = 6,06 - 3,64 = 2,42 = 3,64 - 0,8 = 2,84

7) Lng tiu hao khi x l bng HCl:

8) Thnh phn cp ht c kch thc 0,25 - 0,05mm so vi khi lng t kh l: 100 - (8,18 +16,5 + 24,24 + 2,42 + 2,84 + 2,34) = 43,48% i vi nhng t c thnh phn c gii nh, dng ry khi phn tch c th phn chia thm nhng thnh phn chi tit hn. V d, c th ry c 0,1mm. Nh vy, cng vi c ry c kch thc 0,5 v 0,25mm c th chia c 1 - 0,5; 0,5 - 0,25 v 0,25 0,1mm. Hm lng ca chng trong t c tnh bng %. Tng lng ca chng cng vi nhng thnh phn thu c khi ht bng ng ht cng gp li, ly 100% tr cho ton b cc thnh phn trn s thu c thnh phn cp ht 0,1 - 0,05 mm, nh vy c th thu c mt c trng chi tit hn i vi cc thnh phn ct ca t nh. i vi nhng t cha cacbonat, lng "tiu hao" khi x l bng HCl nn phn chia thnh ct ting gi l "thnh phn tng hp" cng gp vo trong 100% ca thnh phn c gii t. d) Cc phng php th hin kt qu phn tch thnh phn c gii t Kt qu phn tch thnh phn c gii t thng ghi thnh bng. Trong bng s liu ny, bn cnh nhng thnh phn cp ht cn ghi thm ct " m khng kh" v "lng tiu hao" khi x l bng HCl. Tr s v "lng tiu hao" c trng cho s c mt t nhng cacbonat v nhng mui ho tan trong t. hnh dung nhng kt qu phn tch thu c, ngi ta thng th hin di dng th. V d, phng php phu din, phng php hnh trn (hnh 7.8; 7.9)

Vic th hin trn th theo phng php phu din hin nay c s dng rng ri trong th nhng bi v n c th biu th c nhng dn liu phn tch theo su cc tng pht sinh khc nhau. Trc tung ghi su, trc honh ghi hm lng % thnh cp ht. Khi v nh tnh tr s sau cng tip theo tr s trc trc honh.

e) ng dng thc tin ca thnh phn c gii C nhiu bng phn loi thnh phn c gii t, nhng bng phn loi ca Katrinski hin nay c dng rng ri trong th nhng hc. Theo bng phn loi ny th vic xc nh tn gi v phn chia nhm t u da vo kt qu phn tch thnh phn c gii. t gi theo thnh phn c gii cn c vo hm lng ct vt l v st vt l v theo u th tri ca cc thnh phn; si, sn 1 - 3mm, ct 1 - 0,05mm, limon th 0,01 - 0,05mm, limon 0,01 - 0,001mm v st < 0,001mm.

Bng 7.9. Phn loi d theo thnh phn c gii ca katrinski

Hm lng st vt l (cp ht < 0,01 mm) t Kiu ptzn 0-5 5 -10 10 - 20 20 - 30 30 - 40 40 - 50 50 - 65 65 - 80 > 80 Kiu t ng c; t ; t t mn vng 0- 5 5 - 10 10 - 20 20 - 30 30 - 45 45 - 60 60 - 75 75 - 85 > 85 0-5 5 -10 10 - 15 15 - 20 20 - 30 30 - 40 40 - 50 50 - 65 > 65 Kiu ptzn 100 - 95 95 - 90 90 - 80 80 - 70 70 - 60 60 - 50 50 - 35 35 - 20 < 20 Kiu t ng c; t ; t vng 100 - 95 95 - 90 90 - 80 80 - 70 70 - 55 55 - 40 40 - 25 25 - 1 5 < 15 t mn Hm lng ct vt l (cp ht < 0,01mm)

t c coi theo thnh phn c gii

100 - 95 Ct xp 95 - 90 Ct dnh 90 - 85 85 Ct pha - 80 Tht nh 80 - 70 Tht tr. bnh 70 - 60 60 Tht nng - 50 St nh 50 - 35 St tr bnh < 35 St nng

g. Xc nh thnh phn c gii theo FAO - UNESCO Nguyn l Tch phn khong ca t thnh nhng cp ht c kch thc khc nhau v xc nh t l ca chng. Qu trnh phn tch p dng cho ton b vt liu t, ngha l gm vt liu th v . Nhng phng php ny ch p dng i vi nhng t mn (< 2mm). Phn quan trng trong phn tch l x l s b mu lm phn tn ton b cc cp ht nguyn sinh. Do , cc vt liu c tnh dnh kt (thng c ngun gc th sinh), v d: cht hu c, CaCO3 cn phi loi trong mt s trng hp, setquioxit cng cn phi loi tr Tuy nhin cn nhn mnh, i vi mc ch sn xut nng nghip th vic loi tr ny v c bn khng cn thit. V vy, tu theo mc ch nghin cu, vic x l l khng bt buc. Vi mc nh nh gi cc c trng ho hc t cn tin hnh tch cht hu c bi H2O2 v CaCO3 bi mt dung dch m c tnh axit yu pH = 5. Dng c - Bp cch thu - Bp in - My lc - My ry - ng h bm - Cc xc nh m - H thng ry c y (ng knh khong 20cm) - Phu nang bng ng (ng knh khong 23cm) - Ry nh c 50 m (ng knh khong 8cm) - ng ong thu tinh dung tch 1 lt - T sy

Ho cht - H2O2 30% - Dung dch m axetat nng 1 M: ho tan 680g CH3COONa.3H2O trong khong 4 lt nc, chnh ti pH = 5,0 bng 250ml CH3COOH, thm nc ct n 5 lt. Thuc th lm phn tn: Dung dch Pirophotphat 5%: ho ta 50g Na4P2O7.10H2O trong chai c dung tch 1 lt, sau thm nc ct n vch mc. Dung dch NaCl bo ho ho tan 350g NaCl trong 1 lt nc nng, lm ngui. Trnh t phn tch i vi t c cha cacbonat (pH H2O > 6,8) th tin hnh loi cacbonat bng x l bi dung dch m axit yu. Nu t khng cha cacbonat (pHH2O 6,8) th tin hnh xy ho cht hu c 1) Loi cacbonat: Cn khong 20g t mn cho vo cc dung tch 1 lt (nu hm lng cacbonnat nhiu hn 10 th c th cn nhiu hn 20g t). Thm khong 100 ml dung dch m v un nng trn bp cch thu (1000C). y cc bng ming knh. Sau khi ngng si bt thm khong 25ml dung dch m n khi s si bt khng ti din sau khi thm xp dung dch m mi. Trong trng hp hm lng cacbonat rt nhiu c th thm 5ml axit axetic bng thay cho dung dch m. Trong trng hp ny c th dng giy qu tm th pH. Li tm v gn qua m ri dng xi phng ht dung dch bn trn. Trng hp b t keo (Peptit ho), thm mt vi minilit dung dch NaCl bo ho. Ch : Phng php ra ny nhm loi Canxi axetat t dung dch l lng v n c th truyn sang dng canxi oxenat khng tan. 2) xy ho cht hu c: Cn khong 20g t mn, cho vo cc dung dch 1 lt thm 15ml nc vo 15ml H2O2 30% (trong trng hp x l s b th khng cn thm H2O2 hoc thm t), y cc bng ming knh. Trng hp si bt mnh, t cc vo trong b nc lnh Cng c th ngn s si bt bng cch thm vi git cn. qua m, hm sau t ln bp cch thu (khong 800C) v thm u n 5 - 10 ml H2O2 30% cho n khi phn hu cht hu c xy ra hon ton (thng thng dung dch bn trn tr nn trong). Thm H2O tin th tch khong 30ml. t ln bp nng v un si cn thn trong 1 gi loi b ton b H2O2 cn d. Ly cc ra v ngui. Ly tm hoc gn cc vt liu lng trong bnh v dng xi phng ht. Thm khong 300ml H2O v lm phn tn li kt ta. Nhc li 8 - 9 ln cho n khi xut hin petit ho. Mun vy phi ra nhiu ln (hn 4 ln), sau thm mt vi ml dung dch NaCl bo ho xc tin peptit ho. Ch : i vi nhng t c cha thch cao cn ra nhiu ho tan chng

3) Tch hp cht st: Thao tc ny thng thc hin sau nhng x l s b, trc khi lm phn tn t. Thuc th Dung dch m Natri xitrat 0,3M v Natri icacbonat 0,1M: ho tan 88g Na xitrat. 2H2O v 8,4g NaHCO3 trong nc v thm nc ti vch 1 lt. Natriithionit Trnh t phn tch Thm khong 200ml dung dch m vo 20g t mn cha trong cc dung dch 1 lt. un nng trn bp cch thu ti khong 750C (khng c vt qu 800C v S nguyn t s kt ta). Dng tha thm khong lg Naithionlt v khuy lin tc khong 1 pht, sau khuy ngt qung trong 5 pht. Nhc li 3 - 4 ln. Ly tm v gn lc cho lng ri dng xiphng ht. i vi nhng mu cha nhiu hn 5% Fe2O3 c dng cht d rt, cn nhc li trnh t 1 - 2 ln mu nu hoc mu ca mu chng t cha loi Fe hon ton. Ra thm ln na vi khong 250m hoc 500ml NaCl 1M. Tip tc lm nh khu cui cng ca phn xy ho cht hu c. 4) Lm phn tn t: Chuyn ht dung dch l lng vo chai nha dung tch 1 lt (nu khng x l s b, cn khong 20g vo chai). Thm 25ml thuc th phn tn dng nc a th tch n khong 400ml ri nt chai, lc qua m (6 gi) 5) Tch ring cc cp ht: Ry dung dch l lng qua c 50 m qua phu t trn ng ong. Dng nc a th tch trong ng n 1 lt. Ra cp ht ct trn ry v chuyn vo cc, cho bay hi trn bp cch thu, sy 1050C khong 1 gi. 6) Xc nh cp ht ct: Chuyn ct va sy kh vo ry trn cng ca mt chng ry theo th t 1000m, 500m, 250m, 100m, 50m vo y Ry khong 10 pht trn my ry, c thit t bin : rng 7,0 v khong cch 4 ( v tr lp t ny cc ry s rung vi tn s 3000 dao ng/pht v bin khong 2mm). Ra sch cc cp ht tng ry cc cc cn trc, sy, cn. Khi lng A qua E l cp ht ct. Nu c vt liu t li ry y (< 50m) th chuyn n sang dng l lng trong ng ong lng ng nh cch lm phn tch ring cc cp ht. 7) Xc nh limon (slit) v st (clay): Cp ht < 50m: Vt liu < 50 m c th ng li trong qu trnh ry (xem xc nh cp ht ct), do vy cn y ng ong bng nt cao su v lc u. t ng ong trn bn, m nt v dng pipet ht 20 ml gia tm ng ong. Chuyn dung dch vo cc cn trc cho bay hi trn bp cch thu v sy qua m 1050C. Ly cc ra v lm ngui trong bnh ht m ri cn (khi lng kh F cho cp ht < 50m).

Cp ht < 20m: y np ng ong v lc u. t ng ong ln bn di ng ht pipet. Sau ng 5 pht, dng pipet ht 20ml su nh bng 7.10. Chuyn dung dch l lng va ly vo cc cn trc, cho bay hi trn bp cch thu, sy kh 1050C, cn. Khi lng mu G l cp ht < 20 cm. Cp ht < 2m: Sau 5gi 30 pht dng pipet ht 20ml su ca bng 7.10. Chuyn dung dch mi ly vo cc cn trc, cho bay hi trn bp cch thu, sy kh 1050C v cn. Khi lng H+ l cp ht < 2m. Ch : Sau mi ln ly mu bng pipet, o nhit ca dung dch l lng. Bng 7.10. su (cm) ly mu cp ht ph thuc vo nhit (0C)
Nhit (0C) 19 20 21 22 23 24 25 26 27 5 pht (< 0,02mm) 10,5 10,8 11,0 11,3 11,6 11,9 12,1 12,4 12,7 5h30' (0,002 ml 6,9 7,1 7,2 7,4 7,6 7,8 8,0 8,2 8,4 Nhit (0C) 28 29 30 31 32 33 34 35 36 5 pht (< 0,02mm) 13 13,3 13,6 13,9 14,2 14,4 14,8 15,1 15,4 5h30' (0,002 ml) 8,6 8,8 9,0 9,1 9,3 9,5 9,7 9,9 10,1

Kt qu theo khi lng sau khi sy kh. l tng ca tt c cc cp ht ring bit. Cnh tnh: St (clay) (< 2m) = (H x 50) - 0,75g* Limon (silt) (2 -20 m) = (G x 50) - 0,75 - K Limon (20 -50 m) = (F x 50) - 0,75 - K - L Ct (> 50 m) -A +B + C + D +E Khi lng mu = K + L + M + N Khi lng cc cp ht theo % tnh nh sau: (khi lng K) (khi lng L) (khi lng M) (khi lng N) (tnh theo gam)

Ch : Vi cch tnh nh trn th cc cp ht st, limon v ct tnh ra % l ca t ct mn (tr cacbonat v cht hu c b loi trc). Cp ht th > 2mm nu c, tnh ra % ca tng s t. Nu tt c cc cp ht cn tnh ra tng s t th:

Trng hp tch Fe th % "st t do" s tnh c vo phn ngoc n ca cng thc. 8) Xc nh st mn (< 0,2 m): Nguyn l

V tc lng chm ca ht st nn khng thun tin cho lng trong ng ong. Do phi dng my ly tm tng tc lng. Trnh t phn tch Sau khi dng pipet ly mu cp ht < 2 m, y nt ng ong v lc u. yn tnh khong 1 gi v ly khong 200ml dung dch l lng v tm my ly tm trong khi quay l khong 16cm. Cho my quay vi vn tc 1800 vng/pht theo thi gian ch dn bng 7.11 (tr thi gian bt u v kt thc). Ch : Nu quay 2500 vng/pht th thi gian s t hn. Trong trng hp ny s dng chai nha. Tt my ly tm, ly cc chai ra khi my v t di pipet. Dng pipet ht 20ml su 4,5 cm. o nhit ca dch l lng. Chuyn th tch ly vo cc cn trc, cho bay hi trn bp cch thu, sy nhit 1050C qua m. Lm ngui cc trong bnh ht m v cn khi lng cp ht P (g). Tnh kt qu:

Bng 7.11. Tc ly tm, thi gian quay v nhit xc nh cp ht st mn < 0,2 m

Nhit 0C 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 1800 vng/ pht 32,0 31,0 30,0 29,5 29,0 25,0 27,5 27,0 26,5 26,0 25,0 24,5 24,0 23,5 23,0 22,5 22,0 22,0 21,5 21,0 20,5 2500 vng/ pht 16,5 16,1 15,7 15,3 15,0 14,6 14,2 14,0 13,5 13,3 13,0 12,8 12,5 12,3 12,0 11,8 11,5 11,3 11,1 10,9 10,6

9) St phn tn trong nc Nguyn l St phn tn trong nc l hm lng st xc nh c khi khng x l s b mu v khng thm tc nhn phn tn trc khi lc vi nc. Trnh t phn tch Cn khong lp t mn cho vo chai dung dch 1 lt. Thm khong 400ml nc v lc qua m. Chuyn sang ng ong lc, dung tch 1 lt v thm nc n vch mc. Sau 5h30' dng pipet ht 20ml su theo bng 7.10. Chuyn dung dch l lng va ly vo cc cn nc, cho bay hi trn bp cch thu, sy l050C qua tim. Lm ngui cc trong bnh ht m ri cn (khi lng cp ht Q(g). Cch tnh

Trong : s: khi lng mu kh khng kh tnh theo gam; mef: h s m. 10) Mt s phng php khc trong phn tch thnh phn c gii t Nhn chung nhiu nh khoa hc trn th gii tha nhn phng php pipet l phng php chnh xc nht, thun tin nht. Tuy nhin, mt s nc li s dng nhng phng php ring. V d, M kch thc cp ht st c quy inh l < 0,002mm; dng H2O ph hu Cacbonat. Cp ht limon c quy nh c kch thc t 0,05 - 0,002mm, trong khi cng cp ht li mon ny c Hi th nhng Quc t quy nh l 0,02 0,002mm. Cc nc ny s dng my lc nh l bin php c hc phn tn cc cp ht v khi phn loi ngi ta s dng tam gic u vi thang phn loi nh sau: 1. Ct (sand) 2.Ct pha tht (Loamy - sand) 3.Thit pha ct (Sandy - loam) 4. Tht (loam) 5. Tht pha limon (Silty - Loam) 6. Limon (Silt) 7. Tht pha st v pha ct (Sandy clay - loam) 8.Tht pha st v pha limon (Silty ay - loam) 9. Tht pha st (Clay - loam)

10. St pha limon (Silty - clay) 11. St pha ct (Sandy - clay) 12. St (clay)

Cn ch rng khi phn loi cc cp ht c tc gi dng tam gic u hnh 7.10, c tc gi li dng tam gic vung vi trc tung biu th % ca hm lng cp ht st; trc honh (cnh y) biu th % ca hm lng cp ht ci cn cnh huyn trng. Thnh phn c gii theo nhng phng php ca M c trnh by bng hnh tam gic u (hnh 7.8) bao gm 12 loi; 3 nhm cp ht. st; li mon v ct c biu thi 3 cnh. nh tam gic vung tng ng 100%. T y tam gic n nh chia thnh 10 hng, mi hng tng ng 10%. Hm lng ca 3 nhm cp ht: ct, limon, st c biu th 3 ng thng song song vi y tam gic theo im giao nhau ca ba ng thng trong tam gic s bit c loi t cn tm. 7.2.2. Xc nh dung trng ca t Dung trng (khi lng ca mt n v th tch) ca t l t s gia khi lng t kh tuyt i trng thi ty nhn(k c nhng l hng ca mt th tch xc nh vi khi lng ca nc c cng th tch 40C. Dung trng c trng cho cht ca t trong th nhng hc, dung trng s ng : - Tnh tr lng nhiu nguyn t v chuyn chng t % sang th tch. - nh gi mt cch khch quan qu trnh ra tri theo chiu su v vic chuyn ri cc nguyn t t tng ny sang tng t khc.

- Tnh hng hay xp ca t. C nhiu phng php xc nh dung trng nhng thun tin v ph bin nht hin nay v phng php dng ng ng. Trnh t phn tch: t nhng ng ng hnh tr c th tch 100 m3 nn khu vc ca thnh phu din t c lm bng phng, t nht pa xc nh 3 ln tp li v nh vy phi s dng 3 ng song song cng mt lc. t cc khun nh hng nn trn nhng ng ny sau dng chong (nm) t ln trn cng dng ba g ng cc ng vo t (hnh 7.11) Nh h thng chong v ng khun nh hng nn cc ng ng c ng thng v ln su vo t. Khi ng ng ln su vo t ht c th nhc chong ra, dng dao hoc xng o, gt, nhc ng ng ra dng tm g mng ri lt ngc ng ng dng dao sc gt bng phng t mt y di ca ng. y np, sau gt pha u trn cng bng phng nh vy. Lau chi sch t dnh bm xung quanh ng. Dng dao xn cy t trong ng vo hp nhm ln, trng hp khng c hp nhm th dng ti polyetilen hoc giy bng m gp sn thnh phong b. em cn hp nhm cng vi t ti chnh xc 0,01 g. Sau c th s dng mu t ny xc nh t trng th rn, ht m cc i... Bit c khi lng hp nhm (hoc khi lng ti plyetilen, ti giy) khi lng t v hp c th tnh c khi lng t kh tuyt i. Bit khi lng t kh tuyt i v th tch ca ng ng ta s tnh c dung trng theo biu mu sau:

Bng 7. 12. Biu mu ghi v tnh kt qa dung trng ca t

t Tng S ht Khi lng t Th tch Dung Khi Khi Khi ng cy trng hp lng lng b lng t m khng kh tuyt i ng trng su nhm b (hp + t kh ti P P .100 Dv = P= 1 3 a (cm) hoc nhm t (b) (P1 = b - (Why%) V 100 + Why (V) cm a) im ti hoc ti) (a)

Theo thang nh gi ca Katrinski Dung trng nh hn 1 g/cm3 T 1,0 n 1,1 1,2 1,3 n 1,4 1,4 - 1,6 1,6 - 1,8 : t giu cht hu c : in hnh cho t trng trt : t hi cht : t qu cht : in hnh cho tng cy. : tng tch t qu cht

7.2.3. Xc nh cht hu c trong t S tch lu cht hu c dng mn trong t l do hot ng vi sinh vt, thc vt cng nh bn phn hu c. Hm lng, thnh phn mn quyt nh hnh thi v cc tnh cht l, ho hc, ph ca t. Trong tng mn cha gn 90% nh dng d tr v phn ln cc nguyn t dinh dng nh P, S, nguyn t vi lng, l kho d tr cht dinh dng cho cy trng. Hin c nhiu phng php xc nh cht hu c ca t phng php t kh, phng php t t (chiurin, Walkley - Black), phng php t mn trong t sy 1500C thi gian 20 pht (Nikitin) v phng php xy ho mn 24 gi nhit 200C(P. Antanova). Di y l mt s phng php ph bin Vit Nam. a) Xc nh cht hu c theo phng php Chiurin Nguyn l Cht hu c ca t, di tc dng ca nhit , b dung dch K2Cr2O7 + H2SO4 (1:1) xy ho:

Lng K2Cr2O7 cn d c trung dung dch mui c tnh kh l FeSO4 hay mui Morh (FeSO4. (NH4+)2SO4.6H2O) chun:

Cht ch th cho qu trnh chun ny thng dng l axit phenylanthranilic (C13H11O2N), mu chuyn t m sang xanh l cy, hoc diphenylamin (C12H11N) mu s chuyn t lam tm sang xanh l cy. Trong qu trnh chun , Fe3+ to thnh c th nh hng ti qu trnh chuyn mu ch th, v vy trc khi chun c th cho thm mt lng nh H3PO4 hoc mui cha ion F- to phc khng mu vi Fe3+. Trnh t phn tch t phn tch mn v m phi c chun b cn thn ly 5 - 10g t ry qua ry 1 mm, nht ht xc thc vt ri gi nh, ry qua ry 0,25mm, trn u. Dng cn phn tch cn 0,2g (t ngho mn - di 1 % th cn 0,4g, cn t giu mn th cn 0,1 g) cho vo bnh tam gic 100 ml. Dng buret cho t t chnh xc lon K2Cr2O7 0,4N vo bnh lc nh bnh, trnh t bm nn thnh bnh. y bnh bng mt chic phu nh. un trn bp cch ct cho dung dch si nhit 1800C trong 5 pht. Ly ra ngui dng nc thm 10 - 20 ml vo xung quanh thnh bnh ra icromat bm vo. Cho vo 4 git ch th axit phenylanthranilic 0,2% v chun bng dung dch mui Morh 0,2N n khi dung dch chuyn t mu tm mn sang mu xanh l cy. ng thi lm mt th nghim trng: cn 0,2g t nung ht cht hu c cho vo bnh tam gic, cho vo ng lon K2Cr2O7 0,4N v tin hnh cc bc nh phn tch mu. Tnh kt qu:

Trong : V0: s m mui Morh dng chun th nghim trng; V: s ml mui Morh dng chun mu th nghim; N: nng ng lng ca dung dch mui Morh; a: lng mu t ly phn tch (g); K: h s chuyn i t mu kh khng kh sang mu kh tuyt i Ho cht - K2Cr2O7 0,4N trong H2SO4 (l:1): cn 40g K2Cr2O7 tinh khit, nghin bng chy trong ci s, ho tan trong 500ml nc. Nu cn, un nng nh tan hon ton. ngui, lc ri nh mc n 1 lt. dung dch vo bnh nh mc 2 lt ri rt t t H2SO4 c (d = l,84) vo, va rt va lc nh, nu qu nng th phi ngui ri mi rt tip cho n th tch 2 lt. Nng ca dung dch ny c kim tra bng dung

dch FeSO4 (hoc mui Morh) 0,2N. C trng hp sau khi pha xong, mt vi hm thy c tinh th mu hnh kim xut hin, trong trng hp ny ch cn thm t nc, lc u tinh th s mt. - Dung dch mui Morh 0,2N: cn 80g (NH4)2SO4, FeSO4.6H2O ho tan trong nc, thm 20ml H2SO4 c nh mc n 1 lt. Nng ca dung dch ny c xc nh bng cch chun vi dung dch KMnO4 chun: ly lng mui Morh cho vo bnh tam gic 250ml, thm lu H2SO4 c, 50ml nc ct chun bng dung dch KMnO4 ln n khi xut hin mu hng bn trong 1 pht. - Ch th axit phenylanthranilic 0,2g ho tan trong 100 ml Na2CO3 0,2%. S chuyn mu en dn v sau ny khng nh hng g n vic s dng ch th. Ch thch Trong phng php ny phi ch khng ch nhit khi un xy ho mu. Nhit cao qu 1800C s dn ti vic phn hu Cromic. NikitinB.A. (1972) a ra phng php xy ho cht hu c bng cch un trong t sy ti nhit 1500C trong 20 pht. t cha nhiu clorua cng nh hng n kt qu phn tch v c mt phn Cr2O7 - tiu tn cho xy ho Cr:

V vy khi phn tch t mn cn ra sch ht Cr trc khi phn tch cht hu c. b. Xc nh cht hu c theo phng php Walkley - Black Nguyn l Phng php da trn nguyn tc xy ho cht hu c ca t bng dung dch K2Cr2O7 sau chun li lng K2Cr2O7 d, t tnh c hm lng cht hu c d im khc nhau phng php ny so vi phng php Chiurin ch: nhit dng cho qu trnh xy ho c to ra do qu trnh ho tan H2SO4 c trong trung dch kalidicromat. Trnh t phn tch Cn 1 g t kh khng kh cho vo bnh tam gic 500ml thm 10ml dung dch K2Cr2O7 lN. Thm 20ml H2SO4 c vo (thm nhanh theo kh nng c th thm). Lc nh v gi 30 pht. Thm 200ml nc ct v lng H3PO4 85%. Thm lu ch th iphenylamin. Chun bng dung dch FeSO4 0,5N n khi dung dch c mu xanh l cy. Ho cht - Ho tan 49,039 K2Cr2O7 trong nc ct v thm th tch n 1 lt. - FeSO4 0,5N: ho tan 139g FeSO4.7H2O trong 800ml nc, thm 20ml H2SO4 c ri nh mc n th tch 1 lt.

- iphenylamin: ho tan 0,5g ch th trong 20ml nc ri thm tip 100 ml H2SO4 c. Tnh kt qu

Trong : N: nng ng lng ca mui FeSO4; V0, V1: th tch mui FeSO4 dng chun th nghim trng v thun mu; a: lng mu ly phn tch (g); K: h s chuyn i t mu khng kh sang mu kh tuyt i;

3: ng lng gam ca C; 1,3: h s "b" cho qu trnh xy ho cha hon ton cht hu c trong phng php ny. % cht hu c = 2 x C (%) Trc y dng h s 1,72 nhng hin nay thy h s 2 l thch hp hn (ISRIC, 1986). Ch thch Trc khi chun lng K2Cr2O7 cn d ( c 2 phng php) cn phi ngui dung dch xy ho nu khng mt phn Fe2+ dng lng K2Cr2O7 cn d c th b xy khng kh xy ha. Vi 10 ml K2Cr2O7 1N ch c th xy ho ti a 25mg C, v vy khi p dng phng php Walkley - Black cn ht sc ch lng mu ly i phn tch. i vi nhng t hm lng mn < 2,6% c th ly 1 g mu em i phn tch, nu hm lng mn cao hn nn ly 0,2g t cn khi hm lng mn >13,5% th lng mu ly l 0,1g (L c - Tp ch Khoa hc t 10 - 1998) Nu dng ch th fenoin (0,695g FeSO4.7H2O v 1,485g- phenaltrolinmonohidrat (Cl2H8N2.H2O) trong 100 ml nc th dng 4 git ch th - khi kt thc chun , mu ca dung dch chuyn t xanh sang . C th dng phng php so mu xc nh cht hu c bng cch o mu Cr ti bc sng 625nm. Dng saccaroz(C12H22O11) lm trung dch chun kh Cr5+ trong K2Cr2O11; lm dung dch chun kh Cr6+ trong K2Cr2O7 thnh Cr3+.
3+

7.2.4. chua v cch xc nh chua ca t chua l yu t ph quan trng ca t, n nh hng n cc qu trnh l ho v sinh hc trong t v c tc ng n cy trng. a s cy trng thch ng t trung tnh (pH t 6 n 7); mt s c th chu t chua nh ch (pH t 4,5 n 5,5), khoai ty pH t 4,8 n 5,4. t chua l do c mt cc ion H+ v Al3+ trong dung dch t cng nh trong cc phc h hp th ca t c kh nng trao i gy nn. Kh nng to thnh H+ v Al3+ cng ln th t cng chua v ngc li chua ca t ph thuc vo cc phng php xc nh, trong cht chit rt c ngha ln trong trao i cc ion H+ v Al3+. Trn cng mt loi t, s dng cht chit rt NaOH 0,01N (pH = 12) s c chua ln (19mgl/100g t); trong khi vi NaCH3COO 1N (ph = 8,2) th chua thp hn (6,0 mgl/100g t); v thp nht l khi tc ng vi t bng NaCl 1N (pH = 6,0), chua xc nh c l 0,2 mgl/100g t. Nguyn nhn l do ion OH- c kh nng lin kt mnh vi H+ hng s phn ly ca H2O l 10 - 14) trong khi lin kt ca CH3COO- vi H+ l nh hn (hng s phn ly ca CH3COOH l 1,8 x 10-5), Cn Cr hau nh khng lin kt vi H+. chua ca t thng thng c chia lm 2 loi: - chua hin ti ( chua hot tnh): l chua gy nn do cc ion H+ t do trong dung dch t v c xc nh khi tc ng t vi nc ct v c biu th bng pHH2O. - chua tim tng: c xc nh khi chit rt t bng dung dch mui. Da vo cht trit rt, chua tim tng l c chia thnh chua trao i v chua thu phn chua trao i s dng cht chit rt t l cc dung dch mui trng tnh nh KCl. NaCl, BaCl2 cc Cation ca cc mui ny y H+ v mt phn Al3+ ra khi phc h hp ph, Al3+ b thu phn to thnh chua ca t. chua trao i l mt ch s xc nh nhu cu bn vi cho t. chua thu phn: chua ca t c xc nh khi s dng cht chit rt l mt mui thu phn (gm gc axit yu v baz mnh nh CH3COONa). Thng thng chua thu phn c tr s ln hn chua trao i. V lc ny gn nh ton b H+ v Al3+ trao i c trao i ra ngoi dung dch t. chua thu phn cng thng c s dng tnh lng vi bn ci to t chua. Theo nghin cu ca vin khoa hc K thut Nng Nghip th t la Vit Nam ch nn trung ho 1/2 chua thu phn l tt nht. a) Xc nh pH bng phng php cc chn lc hiro

Hin nay phng php o pa trc tip trn my (pH meter) c dng ph bin php o nhanh, chnh xc v phm vi pH xc nh c rng (pH = 1 9). Nguyn l Ion H+ c chit rt ra bng cht chit rt thch hp (nc ct hoc mui trung tnh) dng 1 in cc ch th (in cc chn lc hiro) v mt in cc so snh xc nh hiu th ca dung dch. T tnh c pH ca dung dch. Trong cc loi my pH, in cc ch th thng dng l in cc thu tinh, in cc so snh l in cc calomen. Trnh t phn tch Lc 10 g t ( qua ry 1 mm) 15 pht trn my lc (hoc sc tay 30 pht) vi 25ml KCl 1N (vi pHKCl) hoc nc ct (pHH2O). Sau yn 2 gi (khng qu 3 gi), lc 2 - 3 ln ri o pH ngay trong dung dch huyn ph. Hiu chnh my o ph: My trc khi o phi hiu chnh bng cch o dung dch m pH tiu chun. Chnh cho kim ch ng tr s pH ca dung dch m. o mu: Gi cho in cc cch mt mu t l 1 cm v ngp nc khong 2cm. Khi my n nh, c gi tr pH trn my. Ghi ch: in cc thy tinh c ngm trong nc ct khi khng dng. T l t v dch chit c khc nhau ph thuc phng php. V vy, trong kt qu phn tch cn ghi r t l t: dch chit rt v cht chit rt. V d: "pH trong KCl 1N 1: 5W/V". Ngha l pH khi chit rt bng KCl 1N vi t l t dung dch chit rt l 1:5 (khi lng/ th tch). Nu khng ghi ch g th thng c hiu l pHH2O theo t l t nc l 2:5. Pha dung dch m tiu chun - Dung dch KHC8H4O4 0,05M: 10,21g KHC8H4O4 pha thnh 1000 ml - Hn hp KH2PO4 + NaHPO4 0,025m: 3,10g KH2PO4 pha thnh 1000m1; 3,55g NaHPO4 pha thnh 1000ml. Trn ln 2 dung dch ny thnh 2 lt hn hp. Thi hn s dng khng qu 2 thng. - Dung dch Na2B4O7 0,01N : 3,81 g Na2B4O8.10H2O pha thnh 100 ml - Dung dch KHC4H4O6 bo ho: 6g KHC4H4O6 trong 1 lt nc ct. - Cc dung dch trn pha song ng trong bnh polyetilen, thi hn khng qu 3 thng. - Tr s pH ca cc dung dch m trn nh sau:

Nhit KHC8H4O6 bo ho 0 C 15 20 25 30

KHC8H4O4 0,05M 4,00 4,00 4,00 4,01

KH2PO4 -NaHPO4 0,025M 6,90 6,88 6,86 6,85

Na2B4O7 0,01M 9,27 9,22 9,18 9.14

3,56 3,55

Da vo chua (pHKCl) chua ca t c chia ra nh sau: b. Xc nh chua trao i theo phng php Daicuhara Nguyn l S dng cht chit rt KCl, ion K+ s y H+ v Al3+ trao i ra khi phc h hp th (keo t):

Dng NaOH chun chun H+ to thnh vi ch th mu phenolphtalein. Nc chit ny c th kt hp o pHKCl. Xc nh nhm di ng (Al - trao i) v Ca, Mg trao i. Trnh t phn tch Cn 40g t ( qua ry 1 mm) lc 1 gi vi 100ml dung dch KCl 1N (hoc sc vi pht ri yn mt ngy), sau tin hnh lc. Ly 50ml dch lc + 3 git phenolphtalein ri chun bng NaOH 0,02N tiu chun n xut hin mu hng khng bin mt trong vng 1 pht Tnh kt qu

Trong : Ht: chua trao i; V: s ml NaOH chun mu; N: nng ng lng ca NaOH (0,02N) W: lng t em phn tch (40g) K: h s pha long 9100/50 = 2. Rt gn ta c: Ht(mgl/100g t) = V. 0,1 Ho cht NaOH 0,02N: ly 200ml NaOH 0,1N pha thnh 1000m1 trong bnh nh mc

Dng axit chun (H2SO4 0,02N) kim tra li nng . - Phenolphtalein: 0,1g phenolphatlein ho tan trong 60ml ru etylic ri pha thnh 100 ml bng nc ct KCl 1N: 75g KCl pha thnh 1 lt. Ghi ch: chua trao i xc nh bng chun ch p dng t chua. Khi t c PHKCl > 7,5 s khng xc nh c v phenolphtalein to thnh mu hng ngay trong dung dch mu. c) Xc nh H+ v At3+ trao i theo phng php Xlcp (1939) Nguyn l Khi tc ng vi t bng dung dch mui trung tnh (KCl chng hn) th ng thi c H+ v Al3+ trao i u c gy ra khi tng hp th trao i ca keo t

Khi Alcl3 li b thu phn to thnh H+

T 1 ion Al3+ thu phn s to thnh 3 ion H+. Nh vy thc cht kh chun xc nh chua trao i bao gm c H+ trao i, H+ t do trong dung dch t, H+ c to thnh do Al3+ trao i c xc nh theo cng thc: Al3+ trao i = chua trao i - H+ trao i. Xlcp s dng NaF lin kt vi AI do s xc nh c ring H+ trao i

Lc ny trong dung dch ch cn H+t do, dng phng php chun xc nh chng. Thng thng Al3+ di ng tn ti iu kin pHKCl < 5,5. Do vy Al3+ ch c ngha cc t chua, v c xc nh cng vi khi xc nh chua trao i. Trnh t phn tch Cn lng t lc vi 250ml KCl l trong 1 gi ri lc Xc nh chua trao i: Ly 50ml dch lc vo bnh tam gic 250ml, un si 5 pht, cho vo 2 git phenolphlein, ngui ri chun vi NaOH 0,02N tiu chun n mu hng bn vng (trong 1 pht). Xc nh H+ trao i (gm H+ trao i v H+ c sn trong dung dch t). Ly 50ml dch trn vo bnh tam gic 250ml, un si 5 pht, cho vo 5ml NaF 3,5% ngui, cho vo 2 git ch th phenolphtalein, dng NaOH 0,02N (dung dch tiu chun) chun n mu hng.

Tnh kt qu

hay Al3+ trao i = chua trao i - H+ trao i Trong : V1: s ml NaOH chun mu khng c NaF; V2: S mol NaOH chun mu c NaF; N: nng ng lng ca NaOH (0,02N); W: Lng t cn (100g); K: h s pha long (250/50: 5); Al3+ thng c biu th bng mt mg/100g t. Ly kt qu mgl/100 g t x 9 hoc:

Ho cht - NaOH 0,02N chun. - KCl 1N: 75g KCl pha thnh 1 lt Phenolphtalein 0,1% : 0,1g phenolphtalein pha trong ru etylic 100 ml. - NaF 3,5%: 3,5g NaF pha trong nc ct 100 ml. NaF pha xong phi chnh pH n trung tnh. Ghi ch Khi cho u lng NaF nh nhau vo mu, c th lm i chng kh H+ t do trong dung dch NaF. Thc t lng NaF cho vo c th khng c nh, ph thuc vo lng Al3+. Lng 5ml NaF ch tc dng vi 1,80 mgl Al3+ l tt nht. Khi Al3+ ln hn 6,3mgl/100 g t th s khng . C th tnh lng NaF 3,5% cn thit:

d. Xc nh chua thu thy phn theo phng php Kappen

Nguyn l Dng mt mui kim mnh axit yu (thng l CH3COONa) trao i H+ v Al3+ t keo t:

Ngoi tc dng trao i ca Na+, ion CH3COO- c kh nng lin kt vi H+ v Al3+ lm tng cng qu trinh trao i. Do vy kt qu trao i s trit hn dng mui trung tnh ( chua trao i). Qu trnh thu phn ca (CH3COO)3Al lm tng H+ trong dung dch: (CH3COO)3Al + HOH CH3COOH + Al(OH)3 Chun b trc tip lng H+ to thnh bng dung dch CH3COONa 1N (pH = 8,2) trong 1 gi ri lc. Ly 50 ml dch lc + 2 git phenolphtalein ri chun bng NaOH 0,02 N ti mu hng (bn trong 1 pht). Tnh kt qu

Trong : V: th tch (ml) NaOH chun ; N: nng ng lng NaOH (0,02N); K: h s pha long (100/50 = 2); W: khi lng t (40g); l,75: dng CH3COONa trao i 1 ln khng trit . Mun trao i hon ton H+, Al3+ cn lp li nhiu ln, nh vy mt thi gian v phc tp. Qua thc nghim cho thy nhn vi h s 1,75 l thch hp (h s thc nghim); Htf: chua thu phn (mgl/100g t); Rt ngn: Htf (mgl/100g t) = V. 0,175 Ho cht - CH3COONa 1N (pH = 8,2): 136,1 g CH3COONa.3H2O ho bng nc ct n 1 lt. iu chnh cho pH = 8,2 (va lm i mu ch th phenolphtalein). - Ho cht khc: xem xc nh chua trao i trn. Ghi ch: chua thu phn thng c s dng tnh no baz ca t v tnh lng vi bn (theo nghin cu ca Vin Khoa hc K thut nng nghip, vi t la nc ta ch cn trung ho 1/2 chua thu phn). Nu ly su cn trung ho 1/2 chua thu phn s l:

CAO (tn/ha) = 0,42.Htf Trong : Htf tnh theo mgl/100 g t 7.2.5. Xc nh dung tch trao i cation ca t Dung tch trao i cation ca t hay kh nng trao i cation (CEC - cation exchange capacity) l lng ion ln nht c t hp th l ho hc c thc hin nh keo t. Cn phn bit qu trnh trao i cation (do keo m m nhn) vi trao i cation (do keo dng m nhn). Di y ch cp n vic xc nh dung tch trao i cation. Xc nh dung tch trao i cation theo phng php amoni axetat (phng php Schachtschabel). Nguyn l dng CH3COONH4 l lm bo ho dung tch hp th trao i cation ca t. Phn ng trao i nh sau:

Sau cation NH4 hp ph c trao i ra bng cation K+ (KCl 0,1 N):

Lng NH4 trau i ny c xc nh bng chun bng NaOH 0,1 N vi s c mt ca fomalin (HCHO).

Vi 4 NH4 s gii phng 4H+. Do vy da vo lng NaOH tiu tn m tnh c lng NH4 hay lng cation trao i. Trnh t phn tch Cn 10g t (qua ry 1 mua cho vo phu Mehlich chun bi sn. Dng 100 ml CH3COONH4 1N (pH = 7) chia 10 ln (10 ml x 10 ln) bo ho t bng NH4. Ra t 3 ln bng ru etylic (15 ml x 31n). Dch trao i xc nh thnh phn cation trao i (Ca2+, Mg2+, Al3+,K+,.. ) nu cn thit. Chuyn ton b phu v t sang bnh nh mc 250ml, ri dng 250ml KCl 0,1N trao i (25ml x 10 ln) ln th tch n 250 ml. Ly 25ml dch trao i ny + 10ml fumalin 20% + 5 git phenolphtalein, ri chun bng NaOH 0,05N tiu chun n mu hng nht (bn trong 1 pht). Tnh kt qu

Trong : CEC: dung tch trao i cation (mgl/ 100 g t); V: th tch NaOH chun (ml); N: nng NaOH chun (0,05N); W: lng t cn (loa); K: h s pha long (250/25 = 10); Rt gn: CEC (mgl/100 t) = V.5 Ho cht CH3COONH4 1N: 77g CH3COONH4 pha thnh1 lt bng nc ct (dng NH4OH hoc CH3COOH iu chnh cho pH = 7. - KCl 0,1N; 7,5g KCl pha thnh 1 lt. - Fomalin 20%: pha t fomalin thng dng (khong 38%). Sau trung ha bng NaOH 0,05N vi ch th phenolphtalein. - Phenolphtalein 0,1% (pha trong cn, ru). - NaOH 0,05N tiu chun. Ghi ch Phng php dng CH3COONH4 c dng ph bin nhng ph hp nht vi t trung tnh v khng cacbonat. N cng c s dng cc t chua nh. NH4 c th b gi cht bi cc khong st 1:1 (kaolinit) v mn nn kh thu li c. Do vy t nhiu st, kt qu c th thp hn thc t. Lng t cn c the thay i ph thuc t. Thng thng t thnh phn c gii nng c th cn 5g t + 5g ct sch ( c x l bng H2SO4 c) tng cng tc trao i. C th lm chun trng vi focmaLin (i chng) loi tr H+ cha c trung ho. Kt qu xc nh mu phi tr i lng chun ny (nu c). 7.3. Xc nh mt s kim loi nng trong t Trong dinh dng ca thc vt v vi sinh vt, ngoi cc nguyn t no, photpho v kali, cc kim loi nng nh bo, mangan, ng, km, coban, molipden,.. cng c ngha ln. Mt lng nh ca cc nguyn t ny cn thit cho nhiu qu trnh sinh hc xy ra trong cc c th thc vt v ng vt. Ngun cung cp ch yu cc kim loi nng trong t l cc to thnh t. Trong qu trnh to thnh t v hot ng sng ca thc vt v ng vt xy ra qa trnh phn b li cc kim loi nng theo phu din t.

Hm lng cc kim loi nng trong cc loi t khng vt qu 10-4 %, tr mangan, hm lng ca n trong mt s trng hp, v d nh trong cc thnh to mi ca ma ngan - st i khi c tnh n phn trm. Khi nghin cu hm lng cc kim loi nng trong. t ngi ta thng xc nh hm lng tng s v hm lng c th s dng c i vi dinh dng ca thc vt nh thng c gi l dng di ng ca cc kim loi nng. Chn phng php xc nh, chun b t v cc thuc kh Khi tin hnh nghin cu hm lng cc dng khc nhau ca cc kim loi nng cn la chn cc phng php xc nh chng, phng php phi m bo c chnh xc, nhy v chn lc. Ch c th xc nh mt lng nh cc cht bng cc phng php c nhy cao. Tuy nhin cc phng php c nhy cao thng c chnh xc thp, v d nh phng php khi lng c sai s tng i tnh theo phn trm < 0,01%, phng php trc quang l 2 - 3%, phng php cc ph dng khuch tn l 5 - 10 %. Mu t c nghin trong ci m no v ry qua ry lm bng si capron v khung ry lm t cc vt liu hu c. Nc dng trong phn tch l nc ct c ct li hay cho i qua nha trao i ln, thng s dng nc ct hai ln. Cc axit v amoniac cng c tinh ch bng cch ct hay s dng thuc th loi c bit tinh khit. Cc thuc th khc c tinh ch theo m t trong phng php xc nh ca tng nguyn t. Cc thuc th thng b bn nguyn t km v th khi xc nh nguyn t ny cn phi tin hnh th nghim kim tra s c mt ca n trong cc thuc th s dng. Thnh phn ca thu tinh ch to dng c th nghim cng cn phi c lu tm, c bit khi xc nh b. Nhng ho cht dng pha dung dch chun nn kt tinh li. Thng hay pha hai loi dung dch chun: dung dch chun gc v dung dch s dng. Dung dch chun gc thng c pha vi hm lng 0,1 mg nguyn t trong 1 ml; cn nhng lng m vi hm lng nguyn t nh vy cho php chng ta c th trnh c sai s. Dung dch chun s dng c chun b bng cch pha long dung dch chun gc Khi pha long 10 ln ta c dung dch cha 0,01 mg hay 10g/ml. Khi pha long 100 ln nhn c dung dch c hm lng 0,001 mg hay 1g/ml. V nhng dung dch qu long khng bn nn ngi ta ch chun b cc dung dch ny trong ngy tin hnh phn tch v ch gi trong ngy . Tnh kt qu xc nh cc kim loi nng Kt qu xc nh cc kim loi nng trong t c biu th bng m trong 1 kg t (mg/kg) hoc biu th bng ppm (parts pa million) ngha l mt phn triu, tng

ng vi 10-4% 7.3.1. Phng php phn hu mu truyn thng a. Chun b mu Lm kh cc mu t: Nhng mu t ti cn phi a v trng thi kh khng kh. Lm kh mu nn tin hnh ch sch, thong, trng hp c bit c th dng t sy khng ch nhit t 30 - 400C. Dn mu t (trng lng 800 - 1000 g) thnh lp mng trn giy thuc hoc giy bng m, nht ht r cy, , si,... c ln trong mu. p nh mu t mu c kch thc 5 - 10mm. C th dng my hay ci sc khng c cc kim loi nng p nh mu trc khi ly mu trung bnh. Vic chn, nghin v ry mu t c tin hnh trong phng ring c thit b thng gi v ht bi tt Ly mu trung bnh: T mu ban u ly ra khong 200 g, dng thit b trn u mu. Nu khng c thit b ny c th dng php chia t ly mu (hnh 7.12). Mu t c trn ri ri u trn giy sch thnh mt lp mng c dng hnh vung. Chia hnh vung theo hai ng cho thnh 4 phn bng nhau. Ly hai phn i din (phn 1 v 3 hoc 2 v 4) gp li vi nhau, hai phn cn li c th b i hoc dng vo vic khc. Sau khi chn xong, mu c nghin nh trong ci m no, ry qua ry c ng knh 1 mm. Nn dng loi ry lm bng si capron v khung lm bng vt liu hu c Mu t sau khi ry c dng xc nh cc kim loi nng. b. Phn hu t khi xc nh hm tng tng s cc kim loi nng. Trong t, cc kim loi nng ch yu tham gia trong thnh phn cc khong nguyn sinh th sinh v trong cc hp cht v c, hu c khc nhau. xc nh hm lng tng s cc kim loi nng trong t cn phi thiu hu cc cht hu c v phn hu phn khong ca t nhn c nhng mui d ho tan. Mun phn hu t ngi ta thng s dng 2 phng php phng php nung chy t vi hn hp cacbonat ca cc kim loi kim v phng php phn hu bng cc axit v c c. Qu trnh nung chy vi hn hp cacbonat ca cc kim loi kim c tin hnh trong cc chn phm c np nhit 10000C. Sau khi nung chy, ngi ta nhn c mui kim ca axit silicic v cc hp cht d ho tan khc. Chuyn hn hp chy sang dng dung dch, dng axit clohidric tch axit silicic, ri tin hnh xc nh cc kim loi nng trong dung dch. Khi x l hn hp bng axit clohidric (HCl, d = 1,19) s to nn mt lng tng i ln kt ta ht nh SiO2, kt ta ny c th gi mt

lng ng k cc kim loi nng v nh vy kt qu phn tch s gim xung. Axit clohidric dng x l hn hp c th cha cc kim loi nng di dng tp cht v cng c th ho tan mt lng phm chn ng mu, nguyn t ny s cn tr vic xc nh cc kim loi nng (v d: molipden, vanadi... ). Phng php phn hu mu bng hn hp axit HF v H2SO4 l phng php c S dng nhiu nht khi xc nh hm lng tng s cc kim loi nng. Phng php ny m bo phn hu hon ton mu t v tch axit silicic di dng SiF4. Tuy nhin trong trng hp ny c mt vi phn khong (hay mt phn trong ) nh topaz, analuzit zirkon, sillimanit s khng b ph hu, v vy t cha nhiu cc loi khong ny khng nn ph hu mu bng HF. Vic la chn cc phng php phn hu mu t tu thuc vo cc kim loi nng cn xc nh trong mu. V HF (loi tinh khit phn tch) c cha hn hp cc kin loi nng, cho nn khi xc nh cc kim loi nng nh km, co ban cn phi ct HF trong cc dng c ct c bit ch to t pladi hay platin. Axit clohidric loi c bit tinh khit khng cn phi tinh ch. Khi s dng HF phi ht sc cn thn, cn eo gng tay cao su v ch lm nhng ni c thit b thng gi tt. Khi xc nh km, ng, co ban trong t phi dng axit flohidnc ct li 3 ln phn hu mu t v sau ho tan kt ta, axit clohidric phi dng loi ct hai ln. i vi cc nhm kim loi nng khc (molipden, valadi, ma ngan,...) khng nht thit phi nh vy. Khi xc nh cc nguyn t ny ch cn axit flohidric loi tinh khit ho hc (khng cn ct li) v axit clohidric ct li mt ln. Nhng theo qu trnh phn tch nhm cc nguyn t ny i hi phi chng phn cn li 2 - 3 ln vi nc sau khi phn hu mu ( tch flo trit hn), nung phn cn li 1 - 2 pht trn n kh hay trong l nung v tip theo cn x l nc lc c cn bng axit pecloric (HClO4) tch crom. Khi phn hu mu bng HF v H2SO4 cn ch n lng mu ly phn hu; khng nn ly lng mu ln hn 3g v khi lng mu l 5 - 6g th kh c th phn hu hon ton phn khong ca t v kh tch SiO2. Di y l mt vi cch phn hu mu bng hn hp HF v H2SO4 i vi hai nhm kim loi nng nu phn trn. Xc nh ng, km, coban trong t, tin hnh phn hu theo phng php sau: Cn mu t xc nh hm lng tng s cc kim loi nng trn cn phn tch. i vi t st v t st pha ly 1,5g mu, cn i vi t ct v ct pha ly 2 -3g mu. Sau khi cn xong, cho mu vo chn phm v nung nng trong l nung nhit 500 - 550oC trong 3 gi phn hu cht hu c. Trnh nung nhit cao hn v c kh nng lm mt cc kim loi nng. Sau khi nung mu xong ngui, cho vo chn 1 -2 ml nc ct 2 ln, 1 ml H2SO4 (d = l,84) v 20 ml axit flohidric, t chn ln

bp in kn v un n khi xut hin kh SO2 mu trng. Khng nn un qu mnh (khng vt qu 200 - 250oC) trnh lm bn cc cht ra ngoi. Sau khi xut hin kh SO2, ly chn ra khi bp in, ngui v thm vo khong 10- 15 ml HF ri li tip tc un trn bp in cho n khi kh hon ton. Chuyn chn sang bp in c kh nng un nng hn tip tc un n khi ht kh SO3 bay ra. Nhc chn ra khi bp in, ngui ri cho vo chn 10 ml HCl 22% (loi c bit tinh khit) v 10 ml nc ct hai ln ho tan phn kh cn li. Tip tc t ln bp v un nng nh 30 - 40 pht. Khi phn cn li tan ht, em lc dung dch qua giy lc bng trng (ng knh 9cm) c ra trc bng HCl 10 % loi ht vt cc kim loi nng. Sau khi lc xong ra giy lc bng nc ct hai ln nng c axit ho bng HCl n khi ht vt st. Gp hai phn nc lc v nc ra li vi nhau (khong 100 ml) ri chng ct dung dch n th tch khong 50ml. Dung dch ny dng xc nh cc kim loi nng (km, coban, ng) theo cc phng php khc nhau. Xc nh molipden, valadi, ma gan t mt mu t, dng phng php ph mu sau: Cn 2,5 - 3g t c nghim nh n dng bt cho vo chn phm, t chn vo l nung ri t nng n nhit 500 - 550oC v gi nhit ny t nht 3 gi phn hu cht hu c. ngui, cho vo chn 2ml nc ct hai ln, 2ml H2SO4 c 20ml HF 30 - 40 %. t chn ln bp in v y np kn, un n khi xut hin kh SO3 th thm vo 0,5ml H2SO4 v 10 ml HF, li chng mu n kh. tch flo v phn axit cn li trong chn, ta chng phn kh trong chn 2 ln, mi ln 5ml nc, t nh phn kh cn li trn n kh hay trong l nung tch hon ton axit. Lm lnh chn, x l phn cn li trong chn bng 20ml HCl 22%, y chn li ri un trn bp in n khi tan hon ton phn cn li. Thm vo lng nc ct hai ln lc dung dch qua giy lc v hng vo bnh 250ml, ra dung dch bng nc nng c axit ho bng HCl (98:2) n khi ht phn ng ca st trong nc lc vi KSCN. Chng dung dch lc n kh, cho vo bnh 5ml HCl 22%, 2ml HClO4 v li chng dung dch n kh tch crom. Thm vo phn kh 5ml nc ct 2 ln, li chng n kh tch ht vt HClO4. Thm vo phn kh trong bnh 2ml HCl chuyn mui sang dng clorua, chung kh dung dch. Thm 20ml HCl 22% v 15ml v un nng nh ho tan phn kh. Chuyn dung dch vo bnh nh mc 50ml. Thm nc ct n vch mc. Phn dung dch ny c dng xc nh molipden, valadi, mangan. 7.3.2. Phng php phn hu mu bng k thut vi sng (micyo wave) a. Gii thiu v k thut vi sng (micro wave) Vi sng (micro wave) l sng cc ngn hay cn gi l sng vi ba c bc sng t 1 mm n 1m. Nng lng ca vi sng l nng lng in t. Trong phn tch ngi ta thng s dng vi sng vi tan s 2,45 Mhz.

Cc phng php t truyn thng thng da trn cc hin tng dn nhit, i lu v bc x. Nhit c truyn t bn ngoi vo thng qua s tip xc trc tip hoc gin tip. Lng nhit ny s lan ra ton b vt c t nng nh s chnh lch nhit ti hai im khc nhau, s chch lch ny t l nghch vi dn nhit ca vt c t nng. Phng php ny c nhc im l chm v khng n nh.

S t nng vi sng ngc li vi phng php t nng truyn thng. Nhit c sinh ra ngay ti trung tm ca vt c t nng v lan theo hng t trong ra ngoi. Phng php ny c u im: - Khng c qun tnh nhit (c khi bt u v kt thc); - y l nng lng sch, d to v d kim sot; - t nng nhanh; - C tc dng c bit vi cc phn t c lin kt phn cc. Nng lng vi sng c pht ra t mt ngun pht sng in t (maglletron). Bn cht ca vi sng l sng in t gm hai yu t: yu t t trng v yu t in trng. Qu trnh chuyn ho nng lng in t thnh nng lng nhit bao gm hai c ch c ch chuyn dn ion v c ch quay cc phn t. Nhit sinh ra cho s chuyn dn ln nh l kt qu ca s tng tr khng ca mi trng chng li s dch chuyn ca cc ln trong trng in t. Cn c ch quay cc phn t l qu trnh quay phn t phn cc theo s i hng ca in trng. S t nng bng k thut vi sng da trn s hp thu trc tip nng lng vi sng ca mu, do vy cc hin tng nh dn nhit, i lu v bc x nhit ch ng vai tr th yu trong qu trnh cn bng nhit. u im ca phng php phn hu mu bng vi sng trong phn tch kim loi nng: Tin hnh cc phn ng phn hu mu rt nhanh, tit kim thi gian. c bit c hiu qu i vi cc mu kh phn hu bng cc phng php thng thng;

- Lng mu s dng t, thng t 0,5 - 5 g; - Hiu sut ca phn ng phn hu rt cao do vy kt qu phn tch thu dc chnh xc hn so vi phng php khc; - Tiu hao ho cht t, do vy chi ph cho qu trnh x l thp; - Thit b d s dng, an ton v bo v mi trng. b. Phn hu mu bng vi sng Cc hn hp axit dng cho phn hu mu Cc axit thng s dng trong qu trnh phn hu mu l H2SO4, HNO3, HCl, HF, HClO4, H2O2. Vic s dng hn hp cc axit ny trong qu trnh phn hu mu ph thuc vo nguyn t cn xc nh v d nh xc nh cc nguyn t Ba, Si, Pb, Ca, Ao, Hg khng nn s dng axit sunfumic cng ph mu v mui sunfat ca cc kim loi ny t tan. Cc axit ny c nhit si khc nhau (H2SO4 98%: 3400C; HCl 20,4%: 1100C; HNO3 65%: 1200C; HF 40%: l080C; HClO4 72%: 2030C) do tu theo hn hp axit ph hu mu ta phi s dng cc bnh ph mu ph hp. i vi cc axit c nhit si thp ngi ta thng s dng loi bnh nha teflon ph mu. Cn axit c nhit si cao (axit sunfuric) ngi ta thng s dng cc loi bnh lm t thu tinh borosilicat hoc thch anh (ch khng s dng bnh loi ny khi c mt axit flohiric).

Bng 7.13. Mt s v d so snh gia phng php ph mu vi sng v phng php truyn thng
i tng phn tch Mu thc phm Mu bn thi Mu a cht Mu du Mu cao phn t Lng mu 0,1-2g 0,1 - 2 g 0,1 - 1 g 0,5 - 5 g 5g V c ho bng phng V c ho bng phng php vi sng php c in 15 - 30 pht 10 - 40 pht 10- 50 pht 50 - 75 pht 50 - 75 pht 2 - 4 gi 2 - 4 gi 4 - 16 gi 2 - 8 gi 2 - 4 gi

c. Mt s hng dn v an ton khi s dng thit b phn hu mu bng vi sng Khi c mt cc cht xy ho mnh (H2O2,HClO4, HNO3...) khng c s dng cc cht bi trn c gc du v m. Khng trn trc tip cc cht xy ho mnh nh H2O2, HClO4... vi cc mu dng nn hu c v v c m phi x l trc bng axit (sunfuric, sunfonitric, nitric...). Khi s dng cc cht xy ho mnh phi lu khng mu qu kh trong thi gian tin hnh x l. Khng c s dng cc axit bc khi (m c). i vi cc cht ht m mnh (nh tinh bt) khng c trn trc tip vi cc cht xy ho, hoc thm ch vi axit trc khi lm t chng bng nc. c bit ch khi s dng axit nc vi cc cht hu c c cha xenlulo, v chng c kh nng to ra cc hp cht nitro-xenlulo d gy n. 7.3.3. Chun b mu thc vt xc nh hm 1ng cc kim loi nng Mu thc vt xc nh hm lng cc kim loi nng cn phi c phi, sy kh hoc gi trong t m nhit 30 - 400C. i vi nhng cy c c, thc vt thn m (cy ng,... ) c ct s b thnh nhng phn nh hn cho mu chng kh v tin cho vic nghin nh mu. Sau khi sy kh mu c nghin nh bng cc loi my xay, my nghin hoc s dng thuyn tn tn nh. Cc dng c ny phi m bo khng lm nhim bn cc kim loi nng vo mu. Mu thc vt sau khi nghin nh c th dng mt trong hai phng php tro ho kh v tro ho t phn hu mu. Phng php tro ho kh i vi phng php tro ho kh, mc nghin v "lm cht" trong chn gi vai tr quan trng. Mu nghin qu nh, nm hon ton di y chn s ngn cn s xm nhp ca xy lm chm qu trnh tro ho mu. V th mu trong chn phi xp

tng kh nng sm nhp ca xy lm cho qu trnh phn hu mu din ra nhanh hn. Lng mu ly tro ho tu thuc vo hm lng ca kim loi nng cn xc nh trong mu. xc nh ring tng nguyn t ngi ta thng ly lng mu nh sau: ng : Mangan: Molipden: 0,2 - 0,5 g 1-2g 1-4g Km: Co ban: Bo: 0,05 - 0,2 g 5 - 10 g 0,25 - 1 g

Thc t ngi ta thng xc nh ng, km, mangan, molipden trong cng mt mu, khi lng mu ly thng l 5 g. xc nh b v coban ngi ta ly cc lon mu ring: Coban: 5 - 10 g; Bo: 0,25 - 1 g. Tro ho: Ngi ta thng tin hnh tro ho kh trong l nung nhit 450 500 C, thi gian tro ho l 5 - 8 gi. Trong qu trnh tro ho cht hu c, nhng hp cht ca kim loi nng c nhit nng chy khc nhau c to thnh. trnh mt kim loi nng, nhit trong l nung cn khng ch di 5000C (Troitxky, 1957). tro ho, tt nht nn dng chn bng thch anh, nu khng c loi ny c th dng chn s hoc chn thy tinh chu nhit. Khi dng chn s nu nung nhit qua 5000C c th dn n vic nung chy sn phm tro ho vi men ca thnh chn. Thnh phn mu tro ho c nh hng ln n qu trnh tro ho. i vi mu thc vt khng nhng thnh phn mu c nh hng n qu trnh tro ho m ngay c ni thc vt sinh trng v pht trin cng c nh hng n qu trnh tro ho mu. Ngi ta tin hnh th nghim v thy rng nhng cy thuc h ho tho trng pha nam tro ho nhanh hn nhng cy trng pha bc (Gribovxcaia - 1968). iu cho thy mt s khng ng u v kim v SiO2 trong t bo thc vt nhng vng khc nhau.
0

Mt lng ln SiO2 s ngn cn qu trnh tro ho hon ton mu thc vt. Phn cn li khng ho tan ca axit silicic, to thnh do kt qu ca qu trnh tro ho mu thc vt c th cha mt lng ng k cc kim loi nng tro ho ta cn mu (mu trng thi kh khng kh), cho vo chn v t vo l nung. Mu thc vt trong chn cng xp cng tt, iu s lm tng tc ca qu trnh tro ho. Trong qu trnh nung mu, nn khng ch nhit tng t t Nhit tng qu nhanh c th lm mu bn ra ngoi trong qu trnh t nng mu. Sau , trong qu trnh tro ho nn cn thn m ca l nung tng thm s tham gia ca xy vo mu tro ho nhm nng cao tc tro ho v phn tro nhn c s khng c hn hp cacbon. Thi gian tro ho ph thuc vo thnh phn mu tro ho, mc nhim mu v lng mu em tro ho. tng tc xy ho phn mu hu c cn li, ta thm vo trong chn 1 - 2 ml HNO3 bc, chung kh trn bp in v nung nng trong l nung nhit 450 5000C trong 1 gi. Lp li qu trnh x l mu bng axit ri chng v nung trong l

n khi xy ho hon ton cht hu c, sau ho tan phn kh bng axit HCl 10%, lc dung dch qua giy lc tng trng vo bnh nh mc 100 ml. Nu trong chn v trn giy lc c mt lng ln phn khng ho tan (bao gm SiO2 v hn hp cc cht kh tan khc) th tt nht nn ph hu phn khng tan ny trnh mt cc kim loi nng can xc nh. chuyn hp cht kh tan ny sang trng thi ho tan, ta chuyn ton b phn ny ln trn giy lc ri sy kh giy lc. Cho giy lc ny vo chn phm ri thiu hu trong l nung nhit 450 - 5000C. Qa trnh thiu hu tin hnh n khi nhn c phn tro khng c hp cht cacbon. Thm vi git nc lm t phn mu tro ho ri thm vo O,2m! H2so4' 5ml HF ph hu v tch SiO2 chung mu n kh trn bp in. Nu lng tro cn li ln th cn phi x l bng HF mt ln na. Trong trng hp ny, khi x l mu bng HF ban u ta khng cn chung mu n kh m ch chng n khi xut hin kh SO2. Ho tan mu bng HCl 10% ri lc qua giy lc ( c ra sch trc bng HCl long) sau gp cc phn dung dch li vi nhau. Phn dch lc cui cng c dng xc nh cc kim loi nng trong thc vt theo cc phng php khc nhau. Phng php tro ho t Khi tro ha t, cc cht hu c c xy ho di tc dng ca nhng cht xy ho mnh nh: H2SO4, HNO3, HClO4. Phng php ny n gin v mt thc hin v u vit hn phng php kh v mt tc , c bit trong trng hp mu thc vt c cha mt lng ln phn tro khng tan. Nu tun theo nghim ngt nhng iu kin tro ho ta c th loi tr kh nng mt kim loi nng. Tro ho bng hn hp H2SO4 v HNO3 (Troitxky, 1957): ly 5g mu cho vo bnh Kendan dung tch 300ml, cho vo 5ml H2SO4 c (d= 1,84) v 5ml hoc nhiu hn HNO3 (d = 1,4). un nh bnh trnh si bt mnh (ngoi ra khi un nng nh ta c th duy tr su tc dng ca HNO3 v n d b phn hu v bay hi). Sau khi ui ht hi HNO3, lm lnh bnh, nu nh cha xy ho hon ton cht hu c trong mu, ta li thm HNO3 vo v un nng mu nhit cao hn trong khong 10 pht ri lm lnh. Khi xy ho hon ton cht hu c trong mu, dung dch tr nn trong sut. Tro ho mu bng hn hp cc axit H2SO4 v HNO3 v HClO4: ly 5g mu thc vt trng thi kh khng kh cho vo bnh Ken dan dung tch 300 ml. Thm vo 5ml H2SO4 c (d = 1,84) v 7ml HNO3 (d = 1,4) v c mi gam mu th thm vo 4 ml HClO4 (d = 1,54). qu trnh tro mu ho c tin hnh mt cch an ton, th tch H2SO4 khng c nh hn 2 ml, c bit trong giai on HNO3 bc hi, v th tch H2SO4 nh hn 2ml, c th bnh do s phn hu amoni pecnorat, c to thnh trong qu trnh xy ho cht hu c. Sau khi cho ht cc axit vo bnh, un nng dn dn trn bp in hoc n kh n 1000C, khi xut hin NO2 mu nu, ly bnh ra

 ngui. iu ny cn thit v n lm chm qu trnh phn hu HNO3, sau bnh c t nng n khi xut hin kh SO2 mu trng. Phn ng cn c tin hnh t t. Sau khi xut hin SO2 un nng bnh t 5 - 10 pht, ri tng nhit ln v tip tc un nng 1 - 2 pht. giai on ny cht hu c ca mu c phn hu hon ton, dung dch tr nn khng mu. Nu mu b tro ho cn c cacbon th thm vo 1 - 2ml HNO3 ri un nng bnh n khi xut hin kh SO3. Vic x l ny tin hnh cho n khi no dung dch tr nn khng mu. Sau khi ngui, un pha long dung dch trong bnh n 50ml, lc vo bnh nh mc dung tch 100 ml. Dung dch ny c dng xc nh cc kim loi nng. Phng php nh lng tng t nh khi xc nh chng dng di ng. 7.3.4. Mt s v d v gii hn pht hin ca cc phng php phn tch cng c trong phn tch cc kim loi nng Trong phn tch lng vt cc nguyn t kim loi nng, vic la chn phng php ng vai tr ht sc quan trng. Mi phng php c kh nng pht hin v c nhy khc nhau i vi cc nguyn t kim loi nng. Gii hn pht hin y c tnh bng n v ~g/ml (Bng 7~14) 7.3.5. Xc nh ch trong t Hm lng ch trung bnh trong cc t ca Lin X (c) l 1,2. 10-3% (12mg/kg), trong thc vt l 5.10-5 %, trong t xtrylia: 10 - 130 ppm; Trung Quc l 25ppm, trong cc t M l 17 - 26 ppm. Hm lng ch cao hn trong t thng lin quan n t b nhim do hot ng sn xut ca con ngi. Bng 7.14. Gii hn pht hin ca m s phng php phn tch kim loi nng
Phng php phn tch - UVNIS - AAS (ngn la) - Pht x h quang - Ph pht x Plasma - Hunh quang tia X - Ph khi lng As Cd Cu Pb Zn 0,02 0,02 0,00006 3 0,005 1 0,01 0,5 0,003 Hg 0,08 15 0,2 20 0,02 1 0,06 1 Se 0,2 0,3 0,006 1 0,002 1 0,1 0,5 0,00002 Phng php quang Ph 0,05 0,04 0,03 0,08 0,02 0,05 0,2 0,6 0,004 0,001 0,003 0,002 20 2 0,05 2 0,05 0,005 0,005 0,02 1 0,7 1 2 0,006 0,3 0,1 0,03

Phng php in ha - Cc ph 0,1 0,2 0,2 0,4 - Cc ph xung vi phn 1,004 0,002 0,002 0,003 - in cc chn lc ion 0,03 0,1 0,03

Ch c cc mui Pb(NO3)2 v Pb(CH3COO)2 tan trong nc. Trong dung dch axit clohiric, ch (II) nm dng phc vi clorua (PbCl3)-. Trong cc dung dch axit yu, ch b thu phn v pH cao hn 7, ch dng kt ta hidroxit mu vng nu; trong mi trng kim d b ho tan to thnh ion Pb(OH)42-. V vy trong qu trinh phn tch cn lu kh nng thu phn ca ch (II). Ch cng b giy lc v cc dng c thu tinh hp th mnh, trong cc dung dch axit khi c mt H2o2 S hp th Pb gim i ng k. Phng php xc nh Phn hu t - Phn hu t bng axit: Khi xc nh Pb trong t ngi ta x l mu bng axit HF cng axit HNO3 hay HClO4. Qu trnh phn hu tin hnh trong l nung ( phn hu cht hu c), ti nhit khng vt qu 500oC trnh mt kim loi nng do bay hi. phn hu mu t v mu qung ngi ta cng s dng hn hp HNO3 v cc cht xy ho nh H2O2, HClo4, KClO3. Khi x l bng hn hp ny cc cht hu c bi khong ho, cc hp cht kh tan ca ch chuyn hon ton sang dng dung dch. Qu trnh phn hu tin hnh trong bnh Kendan v sinh hn khng kh di dng ng thu tinh. Phn hu bng phng php nung chy: phn hu mu t khi xc nh ch, c th s dng hn hp Na2CO3 + MgO (1:2) hoc hn hp Na2CO3 + ZnO (l:4). Qu trnh thu phn tin hnh ti nhit khng cao qu 700 - 800oC trong thi gian 1,5 2 gi. Lm lnh ri ho tan trong nc nng. Ch chuyn vo trong nc di dng Pb(OH)42- Xc nh ch: xc nh mt lng nh ch, thng s dng phng php chit trc quang vi thuc th ithizon. Trong mi trng trung tnh hoc kim yu, ithizon to vi ion Pb (n) thnh hp cht ch ithizonat. Trong cc dung mi hu c ch ithizonat c mu . tan ca ch (II) ithizonat trong CHCl3 cao gp 17 ln so vi trong CCl4. H s hp th phn t bng 6,86.1O4 hp th cc i bc sng 520nm; gii hn pht hin ca phng php l 0,05 g Pb/ml. nh lut Bia c tun theo n khong nng 70 g Pb trong 50ml CCl4. iu kin thch hp chit phc l ti pH = 8 - 10. Ti mi trng kim (pH>10,5) v trong mi trng axit (pH < 3,5) nu tin hnh chit trong CHCl3 (hay ti pH<4,5 nu chit bng CCl4) ch ithizonat s b ph hu v ch s chuyn sang tng nc Trnh t phn tch Cn 2,5g t nghin n trng thi bt mn cho vo bnh Kendan, thm vo y 1 5ml HNO3 c v vi git H2O2 y bnh bng phu thu tinh cung di dng lm sinh

hn. un nng nh n khi xut hin cc oxit ca no. ngui bnh ri thm tip nhng phn HNO3 v H2O2 mi tin hnh un cho n khi mu t tr nn trng. X l mu bng HCl v lc vo cc thu tinh chu nhit. Chng dung dch lc n kh, thm vo cc HCl 1: 1, un si n 80 - 90oC, lc v ra phn khng ho tan ca t. Cho dung dch lc vo bnh nh mc v nh mc bng nc ct n vch mc. Ly mt th tch dung dch trn cho vo phu chit, thm 5 - 10ml amoni xitrat 10 % v 1 - 2 git ch thi thimol xanh. Dng amoniac trung ho dung dch n pH9-10 (ch th c mu xanh). Sau thm 5ml dung dch ithizon 0,001 % trong CCl4 ri lc u phu. Sau khi phn lp, rt phn hu c vo phu chit khc. Tin hnh chit li ch trong mu n khi mu ca ithizon khng thay i. Gp ton b phn chit. Thm vo phu chit c hn hp cc ithizonat ca cc kim loi 10ml HCl 0,02 N v lc mnh chuyn ch sang tng nc; chuyn phn tng nc vo phu chit khc. Ra phn hu c bng nc v nc ra ny cng gp vo phu chit cha dung dch ch. Thm vo dung dch cha ch 5ml amoni xun 10% v trung ho bng amoniac n pH = 9. Thm 1ml KCN 5%, 5ml dung dch ithizon 0,001 % trong CCl4 v lc mnh. Sau khi phn lp, rt phn hu c vo bnh nh mc dung tch 25 - 50 ml (hoc ng nghim chia ) v lp li qu trnh chit ch n khi mu ca ithizon khng thay i nh mc th tch n vch mc bng CCl4. Lc u v o mu bc sng 520nm. Dung dch so snh l CCl4. Ho cht - Dung dch chun gc: 0,1 Pb/ml. Ho tan 0,1598 g Pb(NO3)2 kt tinh li v sy kh 1100C trong nc, thm 1 ml HNO3 v thm nc ct n vch mc. - Dung dch chun s dng: g Pb/ml. - Dung dch ithizon 0,001 % trong CCl4. - Dung dch gc: Ho tan 0,4g ithizon trong 200ml CCl4, chuyn dung dch vo phu chit 1,5 - 2 lt, thm vo 500ml NH4OH long (1:200), lc 3 - 5 pht. Loi b phn tng hu c. Ra phn nc mt vi ln bng CCl4 mi ln 5 - 10ml cho n khi CCl4 c mu xanh, sau thm vo phu chit 12,5ml H2SO4 l:5, lc u. Thm 400ml CCl4 v tc phu, rt dung dch ny vi ln bng nc ct 2 ln tch ht lng axit d (thng t 2 - 3 ln). Lc dung dch ithizon qua giy lc kh (giy lc c ra bng HCl v nc ct hai ln) vo trong l thu tinh mu nu. Dung dch phi c bo qun lnh. - T dung dch ny pha long bng CCl4 ta c dung dch ithizon s dng c nng 0,01%. 7.3.6. Xc nh thu ngn trong t Thu ngn t kh quyn khi xm nhp vo t s b cc cht hu c v cc hiroxit ca cc kim loi ht thu; ma ngan hiroxit c kh nng ht thu thu ngn

mnh nht. Theo Vinagradova A.PA hm lng thu ngn trong t l: 1 - 14.10-6%, theo Glauseva V.PA v cc cng s, hm lng thu ngn trong t dao ng trong gii hn 1.10-7 - 1.10-6 %. Hm lng trung bnh ca thu ngn trong thu quyn l 0,03 g/1, trong thc vt n.10-5 - n.10-7 %. Trong t khong pH = 6, thu ngn b c nh cht nht. Thng hay phn tch hp cht thu ngn (II). Cc hp cht ny tan tt trong nc nhng cng b thu phn mnh. Khi pH > 5 s xut hin di dng HgO kt ta mu vng, khi pH > 11,5 bt u b ho tan. Hp cht ca thu ngn vi halogen [Hg(hal)]+... [Hg(hal)4]2- l nhng hp cht d bay hi. Hg2- cn tham gia to phc vi cc mun CN-, SCN-, S2O32- , NO2 hoc vi NH3. Hg c th b hp th bi dng c thu tinh, polietylen, teflon cng hp th mt lng nh thu ngn. Thu tinh thic, thch anh hp th thu ngn t nht. lm gim kh nng hp th cn phi x l trc thu tinh bng HNO3 c v ra nc hoc bng ung dch cromic. Phng php xc nh Phn hu t: C th dng phng php thiu kt hoc x l mu bng axit. Trong phng php thiu kt khng dng cc mui cacbonat ca kim loi kim v khi c th mt hon ton thu ngn. xc nh thu ngn ngi ta dng phng php thiu kt trong cc iu kin kh, khi thu ngn s c kh n kim loi ri ct trong dng c c bit, thng s dng canxi oxit v bt st, ch oxit v canxi nitrat lm cht thiu kt. Hg thu c s c ho tan trong HNO3. Trong phng php x l mu bng axit ngi ta thng dng H2SO4 khi c mt cht xy ha nh HNO3, cc mui thut hoc KMnO4. Qu trnh ph mu khi un nng cho n khi mu tr nn trng, sau loi cht xy ho cn d bng cch thm vo cc cht kh nh ur, fomalin. phn hu mu thc vt hoc cc i tng sinh hc khc ngi ta dng hn hp H2SO4 v HClO4 khi c mt nit molipdat. y nhanh qu trnh phn hu ngi ta tm t mu trc bng dung dch HNO3 c. Trong mi trng axit khi d thuc th, ithizon phn ng vi Hg(II) to thnh phc Hg(HDZ)2 tan trong cc dung mi hu c. Dung dch thu ngn (li) ithizonat trong CHCl3 v CCl4 c mu vng da cam; hp th cc i bc sng 485nm. H s hp th phn t bng 7,1.1O4; nh lut Bia tun theo trong khong nng n 50g H trong 50ml dung dch chit. iu kin thch hp to phc v chit phc l trong dung dch H2SO4 0,5 N 1 N hay HNO3 0,5 - 1N. Trnh t phn tch Thiu hu 1 g t nghin n trng thi bi bng hn hp PbO2 + Ca(NO3)2: lg t c mi mn trong ci vi 2g PbO2 v 0,15g Ca(NO3)2 lm kh trc trong

bnh ht m. Cho hn hp vo phn hnh cu ca ng 1 ca dng c v un nng, lc u un nh phn trn ngn la n kh v sau nung . Khi thiu kt dung c c t hi nghing. Sau 5 - 6 pht nung nng, di chuyn ngn la n kh n 3, t nng phn ny sau li chuyn xung di. Lm lnh, ho tan thu ngn thng hoa gom ng 2 trong 1 ml HNO3 1: 1 nng ri chuyn dung dch vo phu chit. Ra ng mt vi ln bng nc ct ri gp c vo phu chit trn. Pha long dung dch bng nc ct n nng HNO3 1N. Sau rt vo phu chit dung dch KMnO4 0,1N n khi dung dch c mu hng ri lc u. Sau 1 - 2 pht kh lng MnO4cn d bng 1 - 2 git H2O2 30%. Sau thm vo phu chit 1 ml dung dch complexon III 1 %, 4ml dung dch Na2SO3 20%, lc u. Thm vo phu chit 4 ml dung dch ithizon 0,001 % trong CHCl3 v tc phu chit 1 pht. Tin hnh chit ithizonat n khi ithizon khng i mu. Sau khi tch lp, rt phn chit vo cuvet v o mt quang bc sng 485nm. Dung dch chun gc Ho tan 0,3336g Hg(NO3)2 0,5H2O tinh khit ho hc trong nc ct, thm lu HNO3 c ri thm nc ct n 1 lt, c dung dch chun c nng 0,1g Hg/ml. ng chun c xy dng t dung dch chun c hm lng 2g Hg/ml trong HNO31N. 7.3.7. Xc nh dng di ng ca mt s nguyn t Nhng hp cht ca cc kim loi nng d dng chuyn vo trong cc dung dch chit rt khc nhau c gi l dng di ng ca cc kim loi nng. Nhng hp cht ho tan trong nc, nhng dng trao i v nhng hp cht ho tan trong cc axit c nng thp cng nh trong cc dung dch m u c xp vo cc hp cht di ng. Cc dung dch dng chit rt cc hp cht di ng hin c rt nhiu, thng l cc dung dch axit v cc dung dch m. Cc dung dch ny khc nhau v lc tc dng ca chng i vi t v mt s trng hp dung dch chit rt c s dng nh l mt thuc th nhm ri xc nh mt s kim loi nng trong , ngi ta s dng nhng thuc th khc nhau. S la chn mt dung dch chit rt thch hp chit rt kim loi nng di ng trong t c nh gi bng cch so snh nhng s liu phn tch nhn c vi cc

kt qu ca cc th nghim ngoi ng c s dng cc phn vi lng cc cy trng v trong nhng iu kin th nhng khng ging nhau; t gii thch v mc m bo ca t v cc kim loi nng i vi dinh dng ca thc vt c nhiu nghin cu cng phu chn la, so snh cc dung dch chit rt nhm v cc dung dch chit rt ring bit cc kim loi nng. Cc dung dch chit rt nhm thng c cp n l: - Dung dch axetat-lactat theo phng php Egner-Rim-Doming (phng php AL). - Dung dch HCl l (phng php Rinhkis). - Dung dch EDTA 0,01 M + dung dch m amoni axetat pH = 4,7 (amoni axetat 0,5N v axit axetic 0,5N). - Dung dch m oxalat (phng php Grigg) - Dung dch m amoni axetat pH = 4,8 theo phng php ca KrupskiAlecxandrova (dng cho t cacbonat v trung tnh). Dung dch Baron pH = 4 (gm amoni axetat, amoni sunfat v axit axetic). Vi tng nguyn t, s dng cc dung dch chit rt ring sau y: B: Cu: Zn: Mo: nc ct nng (theo Berger v Trung). HNO3 0,43N (theo Vesterhoff); HCl l (theo Rinhkis). KCl l (theo Rinhkis); EDTA + (NH4)2CO3 (theo Trierveiler v Lindsay); HCl 0,1N (theo Zommer). dung dch m oxalat pH = 3,3 (theo Grigg).

T cc kt qu phn tch t, phn tch cy trng trong cc th nghim trong chu v ngoi ng, nhiu nh nghin cu rt ra nhn xt: Dung dch chit rt c axit cng mnh th lng cc kim loi nng c chit rt ra cng ln. Lng cc kim loi nng c chit rt ra bng HCl 1N l ln nht. Ba Lan, Cng ho Sc s dng HCl l lm dung dch chit rt nhm xc nh km, ng, mangan; Lin X (c) dng dung dch m amoni axetat (pH = 4,8) lm dung dch chit rt nhm xc nh mangan, km, ng v coban trong t trung tnh v t cacbonat (hm lng cacbon khng qu 10%). Lin X (c) s dng ph bin h thng dung dch chit rt do I.V.Peive v G.I.Rinhkis a ra xc nh dng di ng ca cc kim loi nng i vi t khng phi cacbonat. Trong h thng ny, chit rt mi kim loi nng ngi ta s dng nhng thuc th ring. Phng php ny c phng th nghim ho hc t - Hc vin Th nhng mang tn V.V. Docutraev ci tin. T l gia t v dung dch chit rt l

1:10, lc trong 1 gi. 7.3.7.1. Xc nh bo di ng chit rt b di ng t t ngi ta thng x l t bng nc si. Phng php ny c Berger v Trung a ra nm 1939. Hin nay phng php ny c ci tin v t l gia t, nc v thi gian un si. Chit b di ng t t Cn 20 - 50g t kh khng kh ry qua ry 1 mm cho vo bnh lm t thch anh hay t thu tinh khng b. Thm nc ct vi lng gp hai lng t cn theo t l 1:2 (i vi t than bn 1:10). un nng bnh n si v gi si trong 10 pht. Bnh un phi c sinh hn, nu khng c th thay bng mt ng thu tinh di 25 - 30cm lm t thu tinh khng b, cm vo nt tre. Lc dung dch nng qua giy lc khng tn. Ly 20 - 40 ml (tu thuc vo hm lng bo) dung dch lc trong cho vo bt thch anh hay bt platin, thm vo lu dung dch NaOH hay KOH 1N ri chng dung dch trn bp cch thu n kh. Nung phn kh ny trong l nung ti nhit 450 - 500oC n khi ph hu hon ton cht hu c v thut (1 - 2 gi). Sau c th dngphngphp cannin hay phng phpq inazann xc nh bo. a. Xc nh bo di ng bng phng php carmin Ho tan phn kh sau khi nung trong 5 - 10 ml dung dch H2SO4 0,5 N, nghin cn thn bng mt que thu tinh kh lm t thu tinh khng bo. Lc dung dch qua giy lc khng tan, trung dung dch lc. Dng pipet ht 1 ml cho vo ng nghim nt nhm, thm chnh xc 9 ml dung dch carmin 0,005% trong H2SO4 (d = 1,84), nt ng nghim, sc u v gi nguyn 1 2 - 18 gi sau o mt quang trong cuvet dy 3mm, y cuvet bng np thu tinh. Kt qu phn tch c tnh theo ng chun. Cn ch v dung dch phn tch v dung dch chun c ly cng bng mt phit. Ho cht - H2SO4 c loi tinh khit c bit hay tinh khit ho hc. Nng c xc nh bng t trng k. - Kim tra xem c NO3- trong axit ny bng cch rt 9ml nc ct vo trong ng nghim sch, kh, sau rt vo ln H2SO4 c, lc u. Sau khi ngui, thm t t, dc theo thnh ng 5ml dung dch diphenylamin trong H2SO4 c vo trong ng nghim. Nu c nitrat, trn ranh gii gia hai cht lng xut hin mt vng hoc mt vng mu xanh nc bin. - Axit b bn HNO3 v nhng axit c mu nht cng khng nn dng xc nh bo. xc nh bo tt nht l s dng loi c bit tinh khit, c th s dng loi tinh khit ho hc kh trc khng c NO3- v bo.

- Dung dch cannin 0,005% trong H2SO4 c, cn phi th trc cht lng carmin; cho dung dch axit hoc vo ng nghim ri thm vo mt lng va phi dung dch can nin trong axit sunfuric c. Thm dung dch can nin cn phi lng ti thiu. Nu dung dch axit hoc c mu xanh nc bin th can nin c th s dng c. Sau khi kim tra, cn trn cn phn tch 50mg cannin cho vo bnh nh mc 1 lt, thm 500 - 600ml H2SO4 c (d=1,84) khuy u dung dch cho n khi ho tan hon ton (tt nht l qua m), sau thm H2SO4 c n vch mc. y bnh v lt ngc bnh mt vi ln dung dch tr nn ng nht. Dung dch can nin ng trong l nt nhm ch tt. Dung dch c mu , nu dung dch c mu khc, khng thun li nh lng bo. - Axit hoc H3BO3 Xy dng ng chun cn phi dng H3BO3 kt tinh li hai ln. tan ca axit hoc ti 00C l 2g trong 100 mg nc ct, ti 200C l 5 g v ti 1000C l 40g. Cn 10 - 12g axit hoc, ho tan khi un nng v khuy lin tc trong 100ml nc ct. un dung dch n si, lc dung dch nng qua giy lc bng trng, hng dung dch lc vo trong bnh rng lm t thu tinh khng b. Lm lnh bnh bng vi nc hoc nc . Dng phu Busner lc H3BO3 qua giy lc bng trng, ra axit ny bng 3 - 4 ln bng nhng lng nh nc ct lnh. Ly H3BO3, lm kh ngoi khng kh, trn t giy lc, y bng mt t giy lc khc, cng loi. Chuyn kt ta vo trong cc cn rng y, khng y np cc cn ri t cc vo trong bnh ht m c cha H2SO4 c trn khi lng khng i. Axit hoc kt tinh li c gi trong cc cn y np v trong bnh ht m. - Dung dch chun gc: Cn 0,2858g axit hoc kt tinh li trn cn phn tch sau chuyn lng cn vo bnh nh mc 500ml nt nhm. Ho tan bng H2SO4 0,5N. Sau nh mc n vch mc cng bng chnh dung dch axit ny. y nt v lt ngc bnh vi ln trn u dung dch. Ta c dung dch chun gc c hm lng b l 0,1 mg/ml. - H2SO4 0,5N: ly 14ml H2SO4 bc ho tan, thm nc n 1 lt. - Dung dch chun s dng: Dng H2SO4 0,5N pha long dung dch chun gc ln 10 ln ta c dung dch chun s dng c hm lng bo l 0,01mg/ml. Thang chun: Dng 2 micro buret c th tch 1 hoc 2ml, ng dung dch chun s ng, mt ng H2SO4 0,5N. Ly Cc th tch dung dch chun s dng: 0,00; 0,05; 0,10; 0,20; 0,40; 0,60; 0,80; 1.00ml cho vo ng nghim sch, kh lm t thu tinh khng b hoc lm t thch anh; sau thm cc th tch H2SO4 0,5N th tch dung dch trong mi ng nghim ng bng la. Lc u ri thm vo mi ng nghim chnh xc 9ml dung dch cannin 0,0055. Lc u v gi yn trong 24 gi mu n nh hon ton, ta c thang mu chun. b. Xc nh b theo phng php quinalizarin

Nguyn l Phng php da trn s thay i mu tm ca quinalizanin (1,2,5,8-tetraoxianthraquinon) trong mi trng H2SO4 c sang mu xanh nc bin khi c mt bo. Khi c mt bo, quinaizarin s to thnh mt hp cht ni phc. nhy ca quinalizann cao hn so vi can nin v h s hp th phn t cao hn ( = 7000 ti bc sng 615nm). V mu ca hp cht phc boquinalizarin ch tun theo inh lut Bia khi hm lng b khng vt qu 1 g nn trong ng chun cng ch xy dng vi hm lng bo t 0 - 1 g. Trnh t phn tch Ly dung dch phn tch cho vo ng nghim hay ng tr lm t thu tinh khng bo hoc lm t thch anh c th tch l 20 - 25ml. Tu thuc vo nng axit s dng, dng buret thm 19,0-22,0m dung dch quinalizarin trong axit sunfunc. y nt ng nghim, lc u dung dch v gi yn 1218 gi cho mu n nh hon ton sau o mu trn my trong cuvet 3cm, dng ming thu tinh y cuvet. Ho cht - H2SO4 93,56 - 95,60 % loi c bit tinh khit hoc tinh khit ho hc. - Dung dch quinalizarin trong axit sunfuric ho tan 10 - 20mg quinalizarin trong 1 lt H2SO4 c. Do s ml dung dch ny thm vo mu ph thuc vo hm lng phn trm H2SO4 nn cn phi xc nh hm lng ca n. a cn phn tch bn tri t cc cn hoc bnh tam gic c nt nhm dung tch 100ml; a cn bn phi t qu cn 2g. Dng pipet c qu bp bng cao su thm cn thn H2SO4 c vo cc hoc bnh tam gic cho n khi cn thng bng. y cc cn hoc bnh tam gic v xc nh chnh xc hm lng H2SO4 ly. Khi cho axit vo cn ch khng cho axit ri ra a cn hay ra ngoi cc hay bnh tam gic. Chuyn ton b lng axit cn vo bnh nh mc 500ml trong c sn 100 - 200ml nc ct. Ra cn thn cc cn hay bnh tam gic mt vi ln bng nc chuyn ht axit sang bnh nh mc. Thm nc n vch mc v khuy u. Dng pipet ly 3ml mu, mi mu 25ml cho vo bnh tam gic 250ml, thm vo 2 git ch th metyl da cam 0,1 % v dng dung dch NaOH 0,1N chun. Hm lng H2SO4 theo phn trm c tnh theo cng thc:

Trong : V: th tch NaOH 0,1 N dng chun (ml);

0,004904: lng H2SO4 tnh ra gam, tng ng vi ng 1ml dung dch NaOH 0,1N; 2: lng H2SO4 tnh theo gram. Tu thuc vo hm lng phn trm H2SO4 tm c, gi vi 1 ml dung dch th nghim hoc dung dch chun ly cc lng quinalizarin khc nhau: Hm lng H2SO4 (tnh theo %) 93 - 94 94,5 95 v cao hn Dung dch quinalizarin (ml) 22,0 20,0 19,0

Khi s dng axit c nng cao hn 94,5 %, thun li hn c l nn pha long c dung dch c nng 93 - 94%. Thng pha 1 - 2 l hoc nhiu hn dung dch quinalizann trong axit sunfuric. Dung dch c gi trong l thu tinh nt nhm, t ch tt. Thang chun Dng nc ct pha long dung dch chun gc c cha 0,1 mg Bo/ml ra 100 ml ln ta c dung dch chun s dng. Dng micro buret cho vo cc ng nghim nt nhm sch, kh lm bng thch anh hoc thu tinh khng bo. Cc th tch dung dch chun s dng nh sau (ml): 0,00;0,20; 0,40; 0,60; 0,80; 1,00, dng nc ct hai ln a th tch ln ng 1 ml. Thm vo mi ng 9ml dung dch quinalizann trong H2SO4, y ng nghim, lc u ri gi yn trong khong thi gian t 12 - 1 8 gi, sau o mt quang v xy dng ng chun. 7.3.7.2. Xc nh ng di ng a. Xc nh ng di ng theo Rinhkis. Nguyn l Phng php da trn qu trnh chit rt ng di ng t t bng dung dch HCl 1 N. T l gia t v dung dch l 1:10. Lc trn my lc 1 gi sau inh lng Cu di dng phc mu ca Cu vi dietyldithiocacbaminat trong CCl4. Trnh t phn tch Cn trn cn phn tch 5g t kh khng kh ry qua ry 1 mm, cho mu vo bnh tam gic nt nhm dung tch 100 ml. Thm chnh xc 50ml HCl 1N, lc trn my lc 1 gi sau lc qua giy lc bng trng. Dng pipet ht 10 - 25ml dung dch lc (tu thuc hm lng ng) cho vo phu chit 50 - 100 ml, thm 5ml dung dch amonixitrat 5%, 1 git phenolphtalein ri thm tng git amoniac n khi dung dch c mu hng nht. Cho vo chnh xc 15ml

dung dch ch dietyldithiocacbaminat trong CCl4, lc trn my 10 pht. dung dch trong phu phn lp ri rt CCl4 cha phc ca ng vi thuc th c mu vng qua giy lc kh vo cuvet 2cm. o mu vi knh lc mu 453 mm, dung dch so snh l CCl4. Kt qu phn tch theo cng thc: X=
a b

Trong X: Hm lng ng trong t mg/kg a: Lng ng trong th tch ly phn tch, tm thy theo ng chun (g); b: Khi lng t, tng ng vi th tch ly phn tch (g) Ho cht - Dung dch ch dietyldithiocacbaminat trong CCl4, lc 664mg natri dietyldithiocacbaminat vi 1 lt CCl4trong phu chit; thm vo phu dung dch ch nitrat (489 mg Pb(NO3)2 ho tan trong 100 ml nc ct hai ln. Lc phu 5 pht. cho phn lp ri lc lp CCl4c ch dietyldithiocacbaminat tan trong qua giy lc kh vo trong bnh thu tinh mu nu. Dung dch c gi trong t lnh - Dung dch chun CuSO4: Ho tan 3,993g CuSO4.5H2O kt tinh li trong nc ct hai ln, nh mc n 1 lt, c dung dch cha leng Cu/ml. Pha long dung dch ny 100 ln (10 ml pha long n 1 lt) thu c dung dch cha 0,1 mg Cu/ml; li pha long dung dch 10 ln ta c dung dch cha 1 g Cu/ml, s dng dung dch ny pha thang chun. Bng 7.15. Thang nh gi (mg Cu/kg) Rt ngho ng Ngho ng Trung bnh Cao b. Xc nh ng di ng theo Vesterhoff 0,3 0,3 - 1,5 1,5 - 3,3 > 3,3

Hin nay nhiu nc tha nhn phng php xc nh ng di ng trong dung dch HNO3 long ( chit rt ng) ca Vesterhoff l phng php chun. Trnh t phn tch Ly lp t cho vo bnh tam gic 250ml, thm vo 100 ml HNO3 (30ml HNO3, d = 1,39 nh mc n th tch 1 lt bng nc ct hai ln), lc 2 gi ri lc. Ly 25ml dung dch lc cho vo bnh tam gic. Thm vo 2ml dung dch KMnO4 0,5% v un dung ch n si. Cho vo dung dch nng 0,5ml axit oxalic 5% lm mt mu dung dch. dung dch ngui ri chuyn dung dch vo phu chit 100 ml (ra bnh tam gic bng nc ct) v a th tch n 50ml. Cho vo phu chit lu dung dch Na3PO4 bo ho, 4ml dung dch natri xitrat 50 % v 4ml dung dch NH4OH c (d = 0,92) sau mi ln thm thuc th vo u phi lc phu chit cn thn.

Cho vo chnh xc 15 ml dung dch ch ietyldithiocacbaminat trong CCl4 lc phu chit 2 pht. cho phn lp, lc ch ietyldithiocacbaminat trong CCl4 qua phu lc kh vo cuvet chiu di 2cm. o mt quang vi knh lc mu xanh l cy (536nm); CCl4 l dung mi so snh). ng chun c xy dng t dung dch c hm lng ng l 10 g Cu/ml. xy dng ng chun ngi ta cho vo cc phu chit 0; 0,2; 0,5; 1,0; 2,0; 3,0; 4,0 ml dung dch ong, thm nc ct 2 ln n th tch 50 ml ri tip tc x l nh i vi dung dch phn tch Bng 7.16. Thang nh gi (mg Cu/kg) nh gi Tt Trung bnh Km 7.3.7.3. Xc nh mangan di ng a. Phng php Dobritxcaia Nguyn l Phng php da trn qu trnh chit rt ma ngan di ng bng dung dch H2SO4 0,1N. T l gia t v dung dch l 1: 10. Thi gian tng tc l 1 gi, xy ho mangan n trng thi ho tr 7 bng pensunfat khi c mt bc nitrat v axit phosphoric. Trnh t phn tch: Cn trn cn phn tch 5 g t kh khng kh ry qua ry 1 mm. Cho lng cn vo trong bnh tam gic nt ni m dung tch 100 ml; thm vo 50 ml H2SO4 0,1 N; lc trn my lc 1 gi, lc dung dch lua giy lc mn bng trng. Ly 10 - 15ml dung ch lc cho vo cc chu nhit dung tch 50ml. Thm vo y 5ml HNO3 c v 2ml H2O2 30%; Chng trn bp in n kh. Lp li qa trnh xy ho bng HNO3 v H2O2 2 - 3 ln sau thm 3ml HNO3 v chng n kh. Thm vo phn kh 25ml H2SO4 10%. un trn bp in n khi phn kh tan hon ton, thm vo cc 15ml nc, 2ml H3PO4 (d = 1,7) v 2mg AgNO3 1% un 5 - 10 pht; nu thy c th cn tip tc un n si ri lc dung dch qua giy lc bng xanh. Thm vo dung dch nng trong cc khong 2 g amoni pensunfat (thm vi ln) khuy dung dch cn thn bng que thu tinh, t cc ln trn bp in, un 10 - 15 pht xy ho nhanh v hon ton ma ngan n axit manganic, khi xy ra qu trnh phn hu mnh lit amoni pensunfat v c kh ozon thot ra. Sau khi ht kh thot ra, ly cc ra khi bp, ngui, chuyn dung dch vo bnh nh mc 50ml. Thm nc ct hai ln n vch mc v o mt quang ngay ry lem hay 2cm ti bc sng 536nm, dung dch H2SO4 5 % dng lm dung dch so snh. t ct > 3,5 2,1 - 3,5 < 2,0 t st v st pha > 2,5 1,6 - 2,5 < 1,5

ng chun c xy dng t dung dch KMnO4 0,1N (t ng chun). Ly 10 ml dung dch cho vo bnh nh mc 100 ml, thm nc ct 2 ln n vch mc, khuy u. T dung dch mi pha ny ly 10ml cho vo bnh nh mc 100 ml ri thm nc ct hai ln n vch mc. Dung dch ny c nng 0,001 N. Trong 1 ml dung dch cha 1 g mangan. Dng pipet ly 2; 5; 10; 20; 25ml dung dch KMnO4 0,001N cho vo bnh nh mc 50ml. Thm nc ct n vch mc v o mt quang ngay vi knh lc mu xanh l cy (536nm), dng cuvet c chiu di nh khi o vi dung dch phn tch. Kt qu phn tch tnh theo cng thc:

Trong : X: hm lng Mn trong t (mg/kg) a: Lng dung dch KMnO4 0,001 N nhn c theo ng chun i vi th tch dung dch th nghim ly phn tch (ml); b: Khi lng t, tng ng vi th tch dung dch th nghim ly phn tch (g); 11: Hm lng Mn tnh theo g trong 1 ml dung dch KMnO4 0,001 N. b. Xc nh Mn di ng theo Schachtschabel nh gi hm lng Mn di ng trong t, Schachtschabel (1957) ngh tin hnh xc nh ma ngan tan trong sunfit v mangan d c kh. Xc nh mangan tan trong dung dch sunflt: Cn 5g t ry qua ry hm cho vo bnh tam gic 250ml, thm vo 0,2g tham hot tnh v 50ml dung dch chit rt, lc trn my sc 1 gi. Sau lc dung dch qua giy lc bng trng, kh. phn tch c th s dng nhng phn dung dch lc u tin. Ly 15 - 20ml dung dch lc cho vo bnh nh mc 50ml, che nh hng kh ca ch v to phc vi ion st, thm vo bnh 2,5ml hn hp gm thu ngn sunfat, axit nc, bc thut v axit photphoric. Sau , xy ho ma ngan ln ho tr 7 ngi ta thm vo 2g amoni pensunfat. t bnh vi dung dch vo trong my n nhit 20 - 30 pht nhit 90 950C n khi ngng thot bt kh. Nu dung dch c mu nu th cn phi ly nhng phn dch lc mi (5 - lon) ri lp li qu trnh x l nh trn. Dung dch lc sau khi ngui c thm nc n vch mc ri o mu nh m t trn. Ho cht Dung dch chit rt: Cn 123,3g MgSO4.7H2O v 2g Na2SO4 ho tan trong nc ri nh mc n th tch 1 lt bng nc. Dung dch thu ngn sunfat: ho tan 75g Hg2SO4 trong 400ml HNO3 (d=1,4) v 300ml H3PO4 (d=1,7), thm vo 0,2g AgNO3 v dng nc ct a th tch n 1 lt.

Xc nh mangan d kh (pH = 8,0): Qu trnh chit rt ma ngan tin hnh bng dung dch magie sunfat c thm 2g hiroquinon trong 1 lt dung dch. Tt c qu trnh chit rt v xc nh mangan sau ny tin hnh nh khi xc nh mangan tan trong dung dch sunfit. Thang nh gi Mn d kh pH = 8,0 Ngho Trung bnh Giu < 20 mg/kg (ppm) 20 - 30 mg/kg > 30 mg/kg

7.3.7.4. Xc nh km di ng Km di ng c chit rt t t bng dung dch kim clorua 1N. Phng php ch s dng cho t axit. T l gia t: dung dch l 1: 10, lc 1 gi trn my. Cui cng xc nh km bng phng php do mu di dng phc vi ithizon theo mu n. Trnh t phn tch Cn trn cn phn tch 2,5g t kh khng kh ry qua ry 1 mm, cho mu vo chn thch anh dung tch 50ml. Thm vo 25ml dung dch KCl 1N, lc trn my lc 1 gi ri lc qua phu lc thch anh, dng giy lc bng trng tnh ch khi cc vt kim loi nng. Ly 5ml dung dch lc cho vo phu chit 50ml, thm vo 2 git ch th metyl da cam, tin hnh trung ha bng dung dch nam axetat 5% n khi ch th chuyn sang mu vng, li thm vo 0,2ml dung dch natri axetat 5% v 2ml dung dch thiosunfat 50%. Chit km hai ln bng dung dch ithizon 0,02% trong CCl4, ln u dng 2ml, ln sau lu. Sau mi ln thm ithizon, phu chit c lc trn my 3 pht, gi yn cho tch tng ri chuyn tng hu c vo phu chit sch khc. Chit li tng nc bng dung dch ithizon mi; dung dch ithizon cng c rt vo phu chit sch trn. Thm vo phu chit cha km ithizonat 25ml dung dch amoniac 0,01 N, lc 1 - 2 pht. Lp km ithizonat c mu c chuyn vo bnh nh mc kh 25ml, ri thm CCl4 n vch mc. o mt quang trong cuvet chiu dy 1 cm ti bc sng 536nm, dung dch so snh l CCl4. xy dng thang chun cho vo cc phu chit 0; 0,5; 1; 2; 3; 4; 5ml dung dch km c nng 1 g Zn/ml thm nc ct n 5ml ri cho vo 2 git metyl da cam v tin hnh phn tch nh i vi dung dch th nghim. Kt qu phn tch theo cng thc:

Trong :

X: hm lng km di ng trong t (mg/kg); a: lng km trong th tch ly phn tch, tm thy theo ng chun (g); b: khi lng t tng ng vi th tch mu ly phn tch (g). Ho cht - Tt c cc ho cht dng xy dng km u phi tinh ch cn thn bng ithizon. Dung dch chun km: Cn 0,2g km kim loi tinh khit trn cn phn tch cho vo bnh nh mc 1 lt v ho tan trong lng nh nc ct hai ln c ln H2SO4 c (d = 1,84). Sau khi tt c kem ho tan, dng nc ct hai ln a th tch n vch mc. Trong lu dung dch ny cha 200 g km. Pha long dung dch ny 200 ln c dung dch cha 1 g Zn/ml. Bng 7.17. Thang nh gi (mg Zn/kg) Rt ngho Ngho Trung bnh Giu Rt giu < 0,2 0,2 - 1,0 2-3 4-5 >5

Ghi ch: i vi t ngp nc c th dng HCl 0,05N lm dung dch chit rt: 10g t v 20ml dung dch HCl 0,05 N. Lc 5 pht ri lc.

7.3.7.5. Xc nh coban di ng Phng php da trn qu trnh chit coban di ng trong t bng HNO3 1N. T l gia t: dung dch l 1:10, lc trn my lc 1 gi. Xc nh coban bng phng php o mu di dng phc mu vi mui nitrozo -R. Trnh t phn tch Cn lp t kh khng kh ry qua ry hm trn cn phn tch, cho mu vo bnh tam gic nt nhm dung tch 250ml. Thm vo chnh xc 100ml HNO3 1N lc trn my lc 1 gi, lc qua giy lc bng trng. Ly 25ml dung dch lc cho vo cc thu tinh chu nhit, thm vo ln HNO3 gc, 1 ml H2O2. Chng trn bp in n kh. Qu trnh x l ny c lp li mt ln na v chng dung dch n khi bt u kt tinh mun. Rt vo cc 6ml nc ct hai ln axit ho bng HCl (1:10), un dung dch n si. Thm vo 1 ml natrixitrat 40% v un si khong 1 pht, pH ca dung dch cn phi ln hn 5,5 (kim tra theo giy ch th vn nng). Nu cha t gi tr mong mun, c th dng natri xitrat iu chnh thm vo dung dch phn tch lu dung dch mui nitrozo-R 0,05% ri un si. Nu dung dch phn tch c mu vng th thm tip 1 ml dung dch nitrozo-R na, 5ml nc ct hai ln ri un dung dch n si. dung dch ngui, thm vo 3ml hn

hp H3PO4 v HNO3 (5 phn H3PO4 85% v 1 phn HNO3 c), khuy dung dch nhanh v cn thn. Chuyn dung dch vo bnh chia ri pha long n 10ml. Dung dch o phc mu ca phc co ban vi mui nitrozo-R trong cuvet 2cm, tinh lc mu xanh l cy (536nm), dung dch so snh l nc ct hai ln. Thang chun c chun b nh sau: Cn 0,477g CoSO4.7H2O cho vo cc v ho tan bng nc ct hai ln. Chuyn dung dch vo bnh nh mc 1 lt, axit ho bng 1 ml H2SO4 (d = 1,84) ri thm nc ct hai ln n vch mc. Dung dch nhn c cha 100 g Co/ml. Ly 50ml dung dch ny pha long bng nc ct hai ln n th tch 500 ml c dung dch cha long Co/ml, c dung dch chun s dng. Ly cc th tch 0,5; l; 2; 3; 4; 5; 6; 7; 8; 9ml dung dch chun s dng cho vo bnh inh mc 100 ml. Thm nc ct hai ln n th tch 50 ml, thm 5ml dung dch natrlxitrat 20% v 5ml dung dch natriaxetat 40%, thm lon dung dch mui nitrozo-R 0,05% ri un n si. ngui, thm vo 5ml hn hp HNO3 v H3PO4, nh mc n vch mc bng nc ct hai ln. Tin hnh o mt quang nh i vi dung dch phn tch. Kt qu phn tch c tnh theo cng thc

Trong : X: hm lng co ban trong t (mg/kg); N: lng t tng ng vi th tch dung dch ly phn tch (g); a: Lng coban tm thy theo th chun g/ml; b: th tch dung dch so mu (ml). Ho cht Axit nc tinh khit ho hc: Ht 68,9 ml HNO3 c (d = l,40) thm nc ct hai ln n th tch 1 lt c dung dch HNO3 1N. - Natrixitrat 3 ln th (dung dch 20%). - Natriaxetat 40%. - Mui nitrozo-R (dung dch nc 0,05%). - Hn hp axit nc v octhophotphoric: Hn 2 axit trn theo t l 100 ml H3PO4 v 20ml HNO3. - H2O2 7.3.7.5. Xc nh molipden di ng Phng php so mu ca Grigg (theo Dobritxcala - 1969) Cn mu t ry qua ry mm vi lng 15g i t st, 25g i vi t ct v

ct pha; cho mu vo bnh nt nhm, rt vo 150ml hay 250ml (tng ng vi lng mu l 15g hay 25g) dung dch m oxalat ca Grigg c pH = 3,3, lc dung dch 1 gi. Lc dung dch qua giy lc bng trng, ly 125ml hay 200ml dung dch cho vo cc chu nhit ri cho dung dch bay hi ti khi th lch dung dch cn 1/4. ph hu cc oxalat v cc cht hu c trong dch lc ngi ta thm vo cc 3ml H2O2 30% v 3 ml HNO3 c, tip tc chng n kh. Thm vo 5ml nc ct hai ln ri chng n kh tch ht vt axit pecloric. Thm vo tip 5ml HCl 22% chuyn mui sang dng clorua ri li chung dung dch n kh. Ho tan phn kh bng cch un nng trong 1 1ml HCl 22%, chuyn dung dch vo bnh nh mc 50ml, thm vo 15ml dung dch NaF 4% ( to phc vi nhm, st v than), 5ml dung dch nam thut 20% ( ngn nga vic kh molipden n ho tr thp hn +5), thm nc ct n vch mc, khuy u dung dch. Chuyn ton b dung dch vo phu chit 100 ml, ra thnh bnh bng 2 - 3ml nc, ri rt c vo phu chit trn. Thm vo phu chit 4ml kalithloxianat 20% ( to thnh phc molipden thioxianat), sc u, cho vo phu 3 - 4ml dung dch SnCl2 1 0%, lc phu v sau khi mu nu ca phc st thioxianat hon ton mt (Fe3+ chuyn thnh Fe2+) th cho vo phu chit 20ml dung dch ru n-butylic ( c ra c bng nc v dung dch thic clorua bo ho) v chit phc molipden thioxianat cn lc mnh phu chit 1 pht. cho phn lp ri tch lp nc pha di phu chit ra nhng gi li khong lu lp nc. Phn chit trong phu c th li c mu hng do mt phn Fe2+ c xy ca khng kh xy ho chuyn thnh Fe3+, v th cn phi ra tip phn chit bng dung dch mui thic bng cch cho vo phu chit c phn chit 20ml dung dch mui thic mi pha (2ml SnCl2 10% + 18ml nc), lc u phu chit. Sau kh phn chit hon ton mt mu hng th tch b lp nc, cn phn chit trong tng hu c cho vo cuvet 3cm. Thm vo cuvet lu ru etylic loi nhng git nc cn ln v 1 - 2 git dung dch mui thic, quy dung dch trong cuvet cn thn bng que thu tinh nh. Phn chit lc ny s tr nn trong sut, khng c mu hng, em o mt quang ca phn chit vi knh lc mu xanh nc bin (435 nm) (ch tin hnh o mt quang t nht l sau 20 - 30 pht k t khi thm ru n-butylic). Dung dch so snh l ru n-butylic, khng x l bng thic v nc. Xy dng ng chun Cho vo cc bnh nh mc 50ml cc th tch: 0,5; 1.0; 2.0; 3.0; 4.0 v 5.0ml dung dch molipden chun c hm lng g/ml; thm vo mi bnh lm HCl 6N, 3ml FeCl3 c hm lng 5 mgFe3+ 1 ml, khuy cn thn cc bnh ny ri thm nc ct n vch mc. Sau tin hnh nh i vi dung dch phn tch. Ho cht - Dung dch m oxalat: ho tan 25 g amoni oxalat v 12,6 g axit oxalic trong nc ct hai ln khi un nng ri thm nc ct n 1 lt. - Axit clohidric 22% (6N, d = l,l): Ct hn hp gm 550ml HCl c v 450ml

nc ct hai ln trong dng c ct lm bng thu tinh, thu c 550ml HCl 22% Thic (II) clorua 10%: Nung chy thit kim loi trong chn s v nghin nhanh bng chy s n khi nhn c bt thic mn. Cn 5,3 g bt ny v ho tan khi un nng trong 20ml HCl 6N. Dung dch nn chun b trc khi dng. C th chun b dung dch ny t mui SnCl2 tinh khit ho hc bng cch ho tan ln mui ny khi un nng trong 20ml HCl 6N, sau thm mt t thic kim loi. - Ru n-butylic: Ra n-butylic bng nc ct hai ln loi ht cht xy ho c trong , cho 250ml ru vo trong phu chit ln, thm 250ml nc ct hai ln, lc 1 pht, sau khi tch tng, rt lp nc pha di, cn lp ru tin hnh bo ho bng thic (II) clorua (c 100 ml ru butylic thm vo 10 SnCl2 10%, lc 3 - 5 pht; thm vo 5ml ln etylic, khuy u). - Dung dch chun molipden: Ho tan mui amoni molipdat tinh khit trong NH4OH trc ch; un nng lin tc ( mi thi im dung dch u phi c phn ng kim), sau lm lnh v kt ta amoni molipdat bng ru etylic, cho kt ta vo nhng t giy lc lm kh mui. Ly 5 - 6g mui kt tinh cho vo chn s ri nung trong l nung nhit 450 - 480oC trong thi gian 40 - 60 pht. Cn 1,5g MoO3 thu c ri ho tan trong 10ml NaOH 1N, thm vo dung dch 10ml HCl 22%, dng nc ct hai ln nh mc n 1 lt Ta c dung dch cha leng Mo/ml. Pha long dung dch ny 1000 ln c dung dch chun s dng. Ch thch + C th tch cht hu c ra khi dung dch phn tch bng cch chung th tch mu n kh trn bp cch thu, sau t chn s vi phn kh vo trong l nung 4500C trong 4 gi. + C th dng ete (tinh khit ho hc) thay cho ru n-butylic chit phc ca molipden vi thioxianat. 7.3.7.7. Xc nh dng di ng ca ng, km, coban, mangan khi chit rt cc nguyn t ny trong t bng dung dch m amoni axetat Phng php da trn s chit rt Cu, Co, Zn v M bng dung dch amoni axetat (pH = 4,8). T l gia t: dung dch chit rt l 1:5. Thi gian lc trn my lc l 30 pht (Crupxky, 1994). Phng php ny dng cho t cacbonat v khng cacbonat. a. Chun b dung dch m Dung dch c chun b t axit axetic v amoniac. Pha long 108ml axit axetic c (98%) bng nc ct hai ln n th tch 600 - 700ml, thm vo 75ml NH4OH 25%, khuy u; Sau khi ngui a th tch dung dch n 1 lt. Kim tra pH dung dch bng pH mt. Axit axetic v amoniac dng chun b dung dch m cn phi

tinh ch khi vt cc kim loi nng. Axit axetic c ct trong bnh thu tinh c sinh hn nhm. Khi ct cn thm mt lng va phi nam axetat khan vo bnh ct. Nng axit c kim tra theo t trng. tinh ch amoniac khi vt cc kim loi, ngi ta rt NH4OH 25% vo y bnh ht m ln, phn trn bnh ht m t cc cc thu tinh ln c rt vo nc ct hai ln n 1/2 th tch cc. y np bnh ht m v gi yn t nht l 48 gi. nhn c amoniac c nng cao hn cn x l nc bo ho amoniac mt ln na bng cch thay dung dch amoniac trong bnh ht m bng dung dch amoniac 25% mi. Nu x l nc bo ho amoniac hai ln c th nhn c amoniac c nng 20%. Kim tra t trng dung dch amoniac nhn c, tnh lng amoniac, axit axetic cn thit pha dung dch m theo t l nu trn. b. Chit rt cc kim loi nng Cn trn cn phn tch 50g t ry qua ry mm, cho lng cn trn vo bnh tam gic nt nhm th tch 500ml, cho vo chnh xc 250ml dung dch m amoni axetat, lc trn my lc 1 gi. Lc qua giy lc bng trng. Ly 150ml dung dch lc cho vo bt s, cho vo bt 10ml HNO3 (d = 1,4), 10ml H2O2 30%, ri chng dung dch trong bt trn bp cch thu n trng thi st. Thm vo 2ml HNO3, 2ml H2O2 ri chng n kh. Ho tan phn kh trong 50ml nc ct hai ln (c 3 - 4ml HCl ct li hai ln) khi un nng. Lc dung dch thu c vo bnh nh mc 100 ml, ra giy lc bng nc ct hai ln c axit ho bng HCl. Dng nc ct hai ln a th tch dung dch n vch mc v ly dung dch ny xc nh cc kim loi nng. Nu xc nh Zn, cn chun b phn dch chit rt ring trong dng c thch anh. Sau nh lng theo cc phng php nu. 7.3.7.8. Xc nh hm lng Cu Pb, Zn di ng trong dung dch chit rt amoni axetat theo phng php Von-Ampe ho tan Ly 10g t kh khng kh cho vo bnh tam gic 250ml, thm vo 100 ml dung dch m anloni axetat c pH = 4,8. Lc trn my lc 1 gi. Lc dung dch qua giy lc bng trng Ly 80ml dung dch lc cho vo cc hay bt thch anh, thm vo 1ml HNO3 c v chng trn bp in n trng thi st. Thm vo 2ml HNO3 c na ri li chng dung dch trong cc. Qu trnh x l mu bng HNO3 tin hnh n khi phn cn li cha t nc c mu trng hay mu vng sng. Sau chng lng cha trong cc n kh, "xi nh" phn kh bng HCl c ri chng dung dch trong cc n trng thi mui m ho tan mui khi un nng trong 20ml nc ct hai ln c axit ho bng HCl (1:100). Lc dung dch qua giy lc c ra c bng HCl long, hng dung dch lc vo trong bnh nh mc 50ml. Ra phn cn li trn giy lc bng nc ct nng c axit ho ri a th tch dung dch n vch mc. xc nh ng, km, c ngi ta ly 8ml dung dch cho vo cc dung tch 50 100ml, thm vo 0,5ml dung dch Cd (4g/ml) dng lm dung dch chun trong, mt

lng nh axit ascorbic. Khuy u dung dch ho tan hon ton axit ascothic. Thm vo trong cc l,5ml dung dch m amoni axetat (NH4OH 1N; NH4Cl 2,7M, CH3COOH 2M). Chuyn dung dch vo bnh in phn to git thu ngn; cho hng (hay nui qua dung dch ri tin hnh in phn ti th - 1,2 V trong 3 pht. Sau ngng cho hidro qua; gi yn dung dch 30 giy, bt u ghi ng biu din qu trnh ho tan qut cc kim loi ng, ch, km. Sau khi ghi c mi mt lc u cn dng khng cho th bin thin trong mt khong thi gian ngn. Nng ca nguyn t c xc nh theo phng php ng chun. 7.4. S dng phng php quang ph hp th nguyn t xc nh cc kim loi nng T khi quang ph hp th nguyn t hidro ra i, nhiu nh nghin cu vn dng xc nh lng vt cc nguyn t trong cc i tng khc nhau. L.A. Lemer v D.N. Ivanov (1970) xc nh hm lng ng, km, mangan, coban trong cc dung dch chit rt t HCl 1N; HNO3 1N; HCl 0,1 N; HNO3 0,1 N; H2SO4 0,1 N; CH3COOH 0,5N; CH3COONH4 1N; dung dch m amoni axetat (pH = 4,8). Nhng s liu nhn c ch ra rng: c th xc nh trc tip Mn trong tt c cc dung dch chit rt trn; km trong tt c cc dung dch chit rt trn tr amoni axetat; ng v co ban ch trong hai dung dch chit rt HCl 1N v HNO3 1N. Khi dng cc dung dch axit mnh khc nhau v tnh cht nhng c cng nng ng lng, chit rt cc kim loi nng th kt qu xc nh hm lng ca chng rt gn nhau. Khi s dng dung dch KCl 1N, ch chy ca ngn la b vi phm nhiu. T l gia t v dung dch chit rt l 1: 10, thi gian lc l 1 gi. Dy cc mu u ca cc nguyn t cn xc nh c chun b bng cch ho tan cc mui tinh khit ca cc nguyn t cn xc nh trong cc dung dch chit rt tng ng. i khi c th tin hnh phn tch theo cc mu u trong nc. nhy khi xc nh cc nguyn t nh sau: Bng 7.18. nhy ca phng php quang ph hp ph nguyn t khi xc nh cc kim loi nng
Nguyn t Vch phn Dng ca Chiu rng 0 n (A) ca khe tch ( A ) (m) 3247,54 2407,25 2138,56 2794,82 8 20 10 14 50 25 300 100 Chiu cao ca chm sng khi i qua trn phn trn ca n kh (mm) 2 2 2 2 nhay g/ml/1% 0,05 0,1 0,02 0,07

Cu Co Zn Mn

Khi cc iu kin lm vic ca cc thit b n nh th qua vi phun, a cc dung dch mu u v dung dch phn tch vo trong ngn la ri xc nh cc gi tr mt quang D tng ng. Theo cc gi tr mt quang thu c v nng cc mu t tng ng, v th chun trn hai trc; da vo gi tr mt quang o c ca mu phn tch v ng chun ngi ta xc nh c nng ca nguyn t cn phn tch. Khi xc nh cc nguyn t c nng cao th mt quang tng ng DL ca cc nguyn t s c gi tr cao hn ng k so vi gi tr mt ng quang ca s hp th khng chn lc Di(DL Di), khi cn phi hiu chinh kt qu gi tr s hp th khng chn lc. S hiu chnh kt qu theo s hp th khng chn lc c thc hin nh sau: Sau khi o cc gi tr mt quang (DL +i) theo cc mch hp th ca cc nguyn t tng ng, tin hnh xc nh gi tr mt quang DL, khi s dng gii ph lin tc ca n hiro, hay l nhng vch khng hp th ca st (nhng vch gn vi cc vch phn tch) c pht ra t n phng in kp nhiu nguyn t Mt quang DL ca nguyn t cn xc nh s bng DL = DL +i - Di. S dng gi tr DL v th chun v xc nh c nng cha bit. S hiu chnh theo s hp th khng chn lc gn lin vi vic thc hin hai qu trnh o lin tc khi nghim ngt tun theo tt c cc iu kin phn tch.

Chng 8 PHN TCH KH

8.1. Gii thiu chung 8.1.1. Cc cht c hi gy nhim mi trng khng kh Ngun gc cc cht c hi, gy nhim mi trng khng kh l do sn xut cng nghip, nng nghip v do qu trnh t nhin liu. Cc cht c hi i vo c th ngi qua ng h hp, tiu ho v qua da. Cht c hi trong khng kh i vo c th ngi qua ng h hp l nguy him nht v thng gp nht. N xm nhp qua ph qun v cc t bo i vo mu. Cht c hi thm qua da (ch yu l cc cht c th ho tan trong m v trong nc) vo mu nh benzen, ru etylic. Da vo tc dng ch yu ca cht c hi c th chia ra cc nhm sau Nhm 1: Cht gy bng, kch thch da, nim mc v d nh a xt c, kim c v long (vi ti, amoniac). Nhm 2: Cht kch thch ng h hp trn nh: Clo, NH3, SO3, SO2, NO, HCl, hi flo. Nhm 3: Cht gy ngt Gy ngt n thun nh CO2, etan, me tan... Gy ngt ho hc: Co ha hp vi cc cht khc lm mt kh nng vn chuyn oxy ca hng cu lm ri lon h hp. Nhm 4: Cht c tc dng thn kinh trung ng, gy m, gy t nh cc loi ru, cc hp cht hydro cacbua, H2S, Cs2, Xng... Nhm 5. Cht gy c Cht gy c tn thng c th: cc loi hydro cacba, halogen, clorua metin, bromua metin... Cht gy c tn thng cho h thng to mu nh benzen, phenol, ch, asen. Cc kim loi v kim c nh: ch, thu ngn, ma ngan, photpho, fluo, cadimi, hp cht asen... c tnh ca cc cht nhim trong khng kh c th tham kho trong rt nhiu ti liu lin quan. 8.1.2. Phng php ly mu kh Tng thp nht ca kh quyn n cao 11 khi c gi l tng i lu. Cc kh

trn vn trong tng i lu c thnh phn tng i n inh v c ngha ln i vi i sng sinh vt y, s vn chuyn khng kh xy ra mnh v hnh thnh cc m my c xem nh l yu t thi tit c nh hng ti cc h sinh thi ca sinh quyn. Bng vic s dng cc dng c c bit, ngi ta c th xc nh c cc tnh cht khc nhau ca khng kh. Nhng phng php sau y c s dng ly mu khng kh. C hai nhm phng php chnh a. Phng php tip cn ly mu t S dng chai hoc ng ly mu c lm y bng cht lng c kh nng ho tan t cc cht kh. Trong nhiu trng hp hay s dng nc c a xt ho. Khi nc tho i. Khng kh s thm nhp vo thay th. Trong phng th nghim, mu khng kh c th chuyn sang dng c phn tch bng cch cho cht lng tng t vo bnh ly mu.

Nhc im ca phng php ny l mt s cht kh c th ho tan vo cht lng Ngc li, cht lng cng c th bay hi vo trong mu kh. Hn na, khi ly mu kh cng nh khi chuyn cht kh vo dng c phn tch cn phi s dng lng kh tm cc cht lng. b. Phng php ly mu kh Trong phng php ny, kh c ly vo trong bnh ly mu nh h thng bm hoc my ht cho n khi th tch trong bnh c trao i vi khng kh t nht l 6 ln. Trong phng th nghim, khng kh trong bnh ly mu c chuyn trc tip ti dng c phn tch bng cht lng (thch hp nht l dng thy ngn).

Thng thng, kim tra nhng hp phn c bit nh hi cn, hi cht c trong khng kh ti vng cng nghip, mu kh c th c a trc tip vo trong cc dng c o ti v tr cn xc nh. Bn cht ca php o l khc nhau t n gin nh ng hp ph vi cc cht c bit cho vng mu sc tng ng vi hm lng ca chng, n dng c t tin o Co v SO2. Khng kh cn phn tch c bm qua bnh phn ng ni c sn cc ho cht cn thit. Sn phn c hnh thnh c th c xc nh bng phng php so mu hoc mt s k thut khc. ly mt lng nh mu kh, c th s dng bm ht bng nha c np y rt thun tin ly mu v chuyn mu kh vo dng c o. Mt s dng c khc ly mu kh l mt bnh c th bm kh vo p sut ln hn kh quyn. Do c nn p sut ln nn chng d dng chuyn sang dng c o. Tuy nhin, do b nn p sut cao nn cc kh c th khuch tn qua v bnh vi cc tc khc nhau. V vy, khng nn mu qu lau s nh hng n thnh phn ca chng. i vi mt cht kh no c kh nng ho tan tt trong nc, c th dng nc hp th lm tng hm lng ca chng cho qu trnh phn tch. Thng s dng nc c thm nhng cht thch hp tng kh nng hp th ca chng. Kh c phn tch c lc qua mng lc xc nh cc phn t rn bng knh hin vi hay phng php ho hc. quan trc khi x t nh my hoc xe c trong khng kh vic phn tch cn tin hnh c dng t kit v ti ng s ca xe.

8.2. Phn tch kh 8.2.1. Xc nh m s tnh cht vt l ca khng kh a. Cng gi: Gi c xem l yu t sinh thi quan trng v n c kh nng lm thay i khng kh v cc yu t mi trng nh nhit , nh sng, cn bng nc... Gi cng l yu t nh hng n i sng ca thc vt cng nh ng vt Bawfort a ra 12 cp nh gi da vo tc gi nh sau Bng 8.1. Phn loi cp gi
Cp gi 0 1 2 3 4 5 6 7 8 9 10 11 12 Loi gi Lng gi (Calm) Khi chuyn ng nh (Light air) Gi rt nh (Light breeze) Gi nh (Gentle breeze) Gi mt (Fresh breeze) Gi trung bnh (Moderate breeze) Gi mnh (Strong breeze) Gn lc (Near gale) Lc (Gale) Lc mnh (Strong gale) Bo (Storm) Bo mnh (Violent storm) Bo rt mnh (Huricance) Tc gi (km/gi) <1 1-5 (3) 6-11 (9) 12-19 (16) 20-28 (24) 29-38 (34) 39-49 (44) 50-61 (55) 62-74 (68) 75-88 (82) 89-102 (96) 103-117 (110) > 117

C nhiu dng c o tc gi (c gi chung l my o gi Anemometer). Loi quay vng: Gm ba na hnh cu hng gi v lm quay ng h o gn trc xung quanh. Loi ny c s dng ph bin cc trm kh tng. Tc gi c tnh bng m/s hoc km/h. Loi o gi dng a p lc: a p lc c ng knh khong 30cm. Khi gi tc ng vo a ny s chuyn thnh s chuyn ng ca t l chia bng chia . b. Hng gi: Hng gi c xc nh da vo a bn t tnh. Cc hng c chia lm 16 t l theo hng a l. c. p sut kh quyn: Khi ln cao p sut s gim, trung bnh s gim i 1/30 khi ln cao 275 m. Tuy nhin, t l v thnh phn ca khu quyn th hu nh khng thay i so vi tng gn mt t. p sut khng chi thay i theo cao m cn thay i theo nhit . Ti cao 0 m (so vi mt bin trung bnh) th p sut khng kh v 10 13,25 milibar (760 mmHg). Do s bin ng ca p sut khi quyn gia cc vng khc nhau nn hnh thnh s chuyn ng khng kh trn mt t, p sut kh quyn c lin quan ti nhiu yu t vt l nh thi tit v kh hu. p sut kh quyn cng l mt ch tiu mi trng.

 o p sut, ngi ta s dng my o (Barometer) da trn nguyn tc nng cao hay h thp ca ct thu ngn bn trong ng thu tinh. Kt qu c biu din bng mmHg hoc milibars. d. Nhit : Nhit l yu t sinh thi c cp ti rt nhiu v tc ng quan trng ca n ti cc qu trnh tng hp vt cht, sinh trng v pht trin ca sinh vt. Cc sinh vt c kh nng thch ng vi bin dao ng rng ca nhit c gi l Eurythemlal v dao ng hp c gi l Stenothermal. Nhit bin ng mnh trong mi trng khng kh v nc c nh hng ti mi trng, nht l m v gi. Tuy nhin dao ng nhit theo ngy m, ma c ngha quan trng hn trong sinh thi hc so vi cc ch tiu n l. e. m tng i: m hin th hm lng hi nc c trong khng kh thng thng dao ng trong khong 0,02 - 4% khi lng. m ph thuc rt nhiu vo cao v nhit . m s gim dn khi ln cao gn nh bng khng ti cao 8 - 10 km. m tuyt i l lng hi nc c mt trong khng kh (biu th bng t l v p sut no ). Bin m c nh hng n qu trnh bay hi nc. N c nh hng n nhit , nh sng v c vai tr quan trng nhm iu chnh s phn b v hot ng ca sinh vt. o m tng i ngi ta dng my o m loi quay s (Dial type hydrometer), loi gi th (Hydrographs), hay b cm ng in t (Electrlcal sensing device). Tuy nhin loi o m (Psychrometer) c s dng nhiu nht.

g. Xc nh hm lng bi 1. Phng php trng lng xc nh bi lng Nguyn l: Phng php da trn s cn dng c hng mu c phn ng cht bt dnh trc v sau khi ly mu xc nh lng bi lng trong thi gian khng ma. Kt qu c biu th bng g/m2 ngy hoc mg/m2 ngy. Dng c: Khay hng mu: bng nhm hoc thu tinh - khay cng c chiu dy 1 mm, chiu cao 11 mm, ng knh trong 85 mm, din tch 57 cm2 c bi mt lp vazlin vi khi lng trong khong 50 mm - 60 mm; sy trong t sy t 5 - 10 pht nhit 400C to mt bng u trn khay. Xc nh trng lng khay trc khi hng mu (m1). Khay c y np, cho vo ti PE, xp trong hp bo qun Ly mu: Khay ly mu bi lng kh c t trn cc gi cao ng nht cch mt t 1,5 hoc 3,5 m. im ly mu phi b tr ni thong gi t mi pha, khong cch gia cc im ly mu vi cc vt cn (nh cao tng, cy cao,...) phi m bo sao cho gc to thnh gia nh ca vt cn vi im o v mt nm ngang khng ln hn 300. S lng mu, s phn b cc im ly mu trong khu vc quan tm c xc nh theo yu cu c th nhng khng t hn 4 mu cho mi im o. Thi gian hng mi mu bi lng kh khu cng nghip, dn c tp trung khng t hn 24 gi nhng khng qu 7 ngy.

X l mu: Dng khn sch lau cn thn bn ngoi khay, sau t vo t sy, sy nhit 400C trong 2 gi. Sau khi sy, cn khay hng trn cn phn tch vi chnh xc 0,1 mg (m2). Tnh ton kt qu:

Trong : m1, m2: kt qu cn khay trc v sau khi hng mu (g, mg) S: din tch hng mu (m2) T: thi gian hng mu, ngy (24 gi) 2. Phng php xc nh lng bi lng tng s Nguyn l: Phng php da trn vic cn trng lng bi thu c trong bnh hng mu bao gm dng ho tan trong nc. S dng xc nh lng bi lng tng cng thng, kt qu c biu th bng g/m2 hoc m/km2. Dng c: Dng c ly mu: Bnh hng mu hnh tr, y phng, ng knh khng nh hn 12 cm, chiu dy khong nh hn 2 ln ng knh ming. Chiu dy ca thnh bnh khng qu 3 lm. C th s dng bnh thu tinh hoc kim loi khng g. Ho cht:

Ho cht chng to, nm... clorofom hoc H2O2 tinh kit. - Nc ct hai ln. Ly mu: V tr t thm hng mu nh phng php trn Thi gian ly mu l 10 ngy hoc 30 ngy. Trc khi ly mu c ra sch, trng nc ct, y np. Trc khi t ly mu cho vo bnh hng 250 ml nc ct, 2 - 4 ml ho cht chng to nm Trong thi gian ly mu, cn b sung lng nc ct gi mu, trnh bnh hng b kh. Trong qu trnh hng mu, nu lng ma hng c trung bnh t cao 2/3 cao bnh hng, thay bnh hng khc hng mu tip, cc mu ny ti mi im trong cng mt khong thi gian ly mu (10 hoc 30 ngy) c th x l ring bit ri cng gp kt qu. Cch tin hnh: Xc nh cc cht khng ho tan trong nc (ml): - Loi b cc vt ngoi lai khng mang tnh cht bi: c th dng tranh gp cc vt ngoi lai c kch thc ln hn 1 mm, trc khi b cc vt ny cn trng qua vi nc ct, nc ct thu c nhp chung vo mt mu. Hoc c th lc qua ry 1 mm, dng nc ct ra bnh hng cho qua ry v nhp nc ny v mu chung. - Lc ton b mu qua phu lc thu tinh xp, sch, kh bit trc khi lng. - Dng nc ct ra cn trn phu, nc ny nhp vo mu chung. - Sy kh phu lc thu tinh xp vi cn 1050C trong 2 gi lm ngui trong bnh ht m, cn vi chnh xc 0,1 mg. Hiu ca hai ln cn phu thu tinh xp trc v sau khi lc v lng cht khng tan trong nc, ml. Xc nh lng cht tan trong nc m2: - Xc nh ton b th tch ca mu sau khi lc bng ng ong: V ml - Ly i din 250 ml dung dch mu lc cho vo cc s, cho bc hi ht trn bp cch thu, sau sy kh 1050C trong 2 gi, cho ngui trong bnh ht m ri cn trn cn phn tch vi chnh xc 0,1 mg. - Sy n khi lng khng i. - Tng lng cht ho tan trong nc:

- Lng bi lng tng s thng tnh bng g/m2 hay mg/m2:

Trong : S: l din tch ming bnh hng m2 Trong trng hp ly mu 10 ngy, lng bi lng thng l tng ca 3 kt qu bi lng trong 10 ngy trong thng 8.2.2. Xc nh mt s tnh cht ho hc ca khng kh a. Xc nh NO v NO2 Nit oxt v nit ioxt c xc nh bng phng php gin tip nh sau. Dng dung dch pemanganat x l hn hp cha cc khi ot nit. Khi nit oxt v nit ioxt c oxy ho thnh nitrat. Phn ng ho hc din ra nh sau:

Lng nitrat to ra tng ng vi hm lng ton phn ca NO v NO2. Lng pemanganat c dng oxy ho cc NO v NO2 thnh NO3 c xc nh bng cch thm vo mt lng d Fe(II) sunpht, sau chun lng d bng dung dch Kali pemanganat, cn hm lng thut th chun tip theo bng dung dch Fe(II) sunphat trong mi trng a xt H2SO4 m c. Xc nh im tng ng theo phn ng to thnh sn phn kt hp Fe2(SO4)3.2NO l cho dung dch c mu hng. Tin hnh xc nh Vic xc nh lng tin hnh trong pipet c chun ho v c cu trc c bit. Rt chn khng trong pipet trc, rui a qua phu vo 25ml dung dch kali pemanganat 0,5N v trng phu bng mt lng nc o trc. Sau cho hn hp kh kho st v pipet qua mt kho 3 nhnh, cn bng nhit v p sut, lc mnh pipet cho vo 25 ml dung dch Fe(n) sunphat 0,5N v mt t nc ( trng phu) v lc pipt trong vi pht. Ht cht lng b mt mu ra khi pipet qua kho 3 nhnh vo bnh hnh nn v trng k pipet bng nc ct. Chun lng Fe(II) sunphat d bng dung dch kali pemanganat 0,5N. Nh vy xc nh c lng dung dch kali pemanganat tiu tn oxy ho NO v NO2. Mun xc nh hm lng ton phn ca Nit chuyn thnh nitrat ngi ta chuyn ton b dung dch cn chun vo bnh nh mc dung tch 500 ml, trng

bng mt lng nh nc ct. Ri va cn thn thm lng nh axt sunphuric m c, va lin tc lm lnh bnh bng hn hp nc v nc , dng a xt sunphunc a th tch dung dch ln n vch mc. Dng pipet ht 2 mu, mi mu 100 ml dung dch thu c vo mt hnh nn c dung tnh 500 ml. Thm vi tinh th kim bicromat ( gii phng xy ho tan) v va lin tc xoay bnh va chun bng dung dch Fe(II) sunphat 0,5N. u tin dung dch khng mu, ri c mu lc hi vng nht v ti im tng ng c mu hng. Lng d ca Fe(II) sunphat to cho dung dch mu ta m. Tnh kt qu Theo nhng phng trnh phn ng trnh by trn, lng chng ca kh NO v NO2 tng ng vi lng thut to thnh. Da theo nhng phn ng trn xc nh th tch ca NO v NO2 ta c phng trnh sau:

Trong : N: lng chung ca cc kh NO v NO2 (ml) P: lng dung dch kim pemanganat 0,5N dng oxy ho (ml). Trong chun lng thut bng php chun tip theo vi Fe(II) sunphat, 1 ml dung dch Fe(n) sunphat 0,5N tng ng 5,6 ml kh trn. b. Xc nh hm lng lu hunh dioxit (SO2) Xc nh lu hunh theo phng php trc quang thorin Phng php ny c dng xc nh nng SO2 trong khng kh xung quanh cc khong nng 3,5 - 150 g/m3. Vi th tch ly mu 2m3 v th tch dung dch l 50 ml. Vi nhng nng cao hn, phi pha long trc khi xc nh. Nguyn l Cho mu khng kh i qua dung dch H2O2 ( c axt ho) trong mt thi gian quy nh. Lng SO2 c trong mu s c hp th v oxy ho thnh SO42- . Kt ta SO42- di dng BaSO4 bng mt lng Ba(ClO4)2 d. Bari d c xc nh bng cch to phc mu vi thorin v o bc sng 520 nm bng my so mu. Ho cht - H2O2 27 - 30% - Dung dch hp th: Pha long 10 ml dung dch H2O2 27% vi nc thnh 1 lt. - iu chnh pH dung dch v khong 4- 4,5 bng dung dch HClO4, dng in cc pH kim tra. - Dung dch Bari peclorat: Ho tan 0,252 g Ba(ClO4)2 trong mt lng nh HClO4 0,1 M trong bnh nh mc 250 ml ri nh mc n vch bng axt HClO4

0,01 M. - Bari peclorat/dioxan: Cho 10 ml dung dch ban peclorat v 40 ml nc vo bnh nh mc 1000 ml, thm dioxan n vch mc v trn u. - Dung dch H2SO4 0,5: T ng nghim tiu chun pha thnh 1 lt dung dch. - Thorin 0,25%: Ho tan 0,25 g thorin trong 40 ml dung dch sunphat tiu chun v thm nc ct n th tch dung dch 100 ml. Qu trnh xc nh T bnh hp th ly ra 5 ml dung dch, trn u vi 10 ml ung dch ban peclorat/dioxan v 0,25 ml thorin. Khi cng mu ca dung dch t l vi lng ban d v t l nghch vi lng ln SO42- c trong mu. Da theo ng chun tnh hm lng SO2 c trong mu. Trong khi tin hnh, thorin c th to phc vi nhiu ton kim loi lm cn tr php xc nh do vic lc bi giai on thu mu c th loi b c nh hng ny. S c mt ca PO43- s to thnh kt ta vi Ba3(PO4)2 lm cn tr php xc nh. Khi hm lng SO2 ln, c bit nhng ngun thi tnh, c th dng phng php H2O2/Ba(ClO4)2/thorin thay bng phng php trc quang thorin. Trong phng php ny ngi ta chun mu bng dung dch Ba(ClO4)2 vi ch th thorin. Ti im cui ca qu trnh chun , dung dch xut hin mu hng. c. Xc nh CO bng phng php sc k Nguyn l Cho mt th tch mu khng kh i qua ct sc k tch CO ra khi cc thnh phn kh khc. Kh CO va tch ra thnh me tan bng dng kh hydro vi xc tc niken nng (c th dng cc cht xc tc v cht h tr khc).

Tn hiu sc k nhn c t l vi lng Co c trong mu. Ho cht v thit b - Cc kh: Hydro c s dng l khi mang trong tch sc k kh, lm cht kh Co thnh metan v cng cn cho hot ng ca detector ngn la ion ho. Nit, heli: i vi mt s u t, kh nh hoc hai hoc hn hp c hai kh ny c thm vo kh t tng nhy v n nh. Cc kh metan v Co chun Ct sc k: Dng ct sc k tch Co ra khi cc thnh phn khc c trong mu.

iu quan trng l nguyn liu nhi ct khng thng xuyn gi nc v ct s c ra ngc gia cc ln phun mu Quy trnh tin hnh Trong khi tin hnh cn ch nhng im sau: - Khong nhng nng d kim - Tn hiu sc k v nng ti thiu c th pht hin so vi tn hiu nhim; - S mu gin on c o trong mt n v thi gian; - tri ca "im khng" v thi gian tri; - lp li ca php o; - Hiu sut chuyn ho; - Khong nhit cc mu s c ly. 1. Chun b xc tc: Bo ho niken nitrat hecxahirat (Ni(NO3)2.6H2O) trong 25 ml nc ct, lc b phn khng tan. Ngm 10 g diatomit c kch c t 0,125 - 0,15 mm trong dung dch ny, lc chn khng v lm kh qua m nhit 1100C. Nung trong khng kh 5 gi nhit 5000C. 2. Chun b ng chuyn ho: Nhi diatomit x l vi niken nitrat vo mt ng thp khng g. 3. L chuyn ho cht: Lp rp h thng ly mu, ng chuyn ho vo my sc k kh. iu chnh h thng sao cho n c th hot ng theo cch thc ng vng. Trong giai on ny nt iu kin t ng v b ghi u khng hot ng. Bt my sc k v iu chnh cc ch dn ca nh sn xut. iu chnh nhit l chuyn ho n 3500C v vn hnh h thng trong 10 gi kh cc niken oxt thnh niken kim loi. 4. Xc nh: Dng bm ly mu ht lin tc kh qua vng mu v ng vng ca n. Lu lng ca dng kh mu (khong 100 cm3/giy) lm sch v lm y vng mu. Vo nhng thi im thch hp trong chng trnh ly mu, kh cha trong vng mu s c phun t ng vo h thng sc k o hm lng CO. Kt qu Nng Co c xc nh bng cch so snh cc din tch peak thu c t cc hn hp kh chun v mu. Nng Co c tnh chuyn t mg/m3 thnh ppm nh sau: - nhit 250C v p sut 101,3 kPa: 1 ppm 1,14 mg/m3 - cc nhit khc vi p sut 101,3 kPa:

Trong t nhit tnh bng 0C. d. Phng php indophenol xc nh hm lng amoniac Nguyn l Phng php da trn c s tc dng ca amoniac vi hipoclorit v phenol c s tham gia ca cht n nh phn ng l natri nitro pruxit, to ra hp cht mu xanh, hp ph cc i ti bc sng 625 nm. Phng php ny c s dng xc nh hm lng amoniac trong khng kh tng ln vo trung bnh ngy m trong khong t 0,1 n 1,0 mg/m3 Cc amin thm v fomadehit gy cn tr php xc nh. Dng c - My ht kh c lu lng k c vch chia n 0,005 lt/pht; nhit k, p k, m - Bnh hp th Ricte c vch o 6 ml hoc dng c hp th khc. - My so mu c knh lc mu 625 mm, hoc my quang ph, cuvet c b dy khm. - ng nghim c nt mi dung tch 100 ml. - Phu Bucne. Ho cht v thuc th - S dng loi tinh khit ho hc hay loi tinh khit phn tch. - NaOH - KI - dung dch 10% - NH4Cl - Natri nitro pruxit Na2[Fe(CN)5]NO - NaCO3 - H2SO4 (d= 1,18) trung dch 10% theo th tch - NaCl - Axt salixilic [HO(C6H4)COOH] - Natri thiosunphat: Na2S2O3.5H2O dung dch 0,05 mol/1 - A xt oxalic H2C2O4 - Phenol C6H5OH - Corua vi CaOCl2

- Nc ct hai ln kh amoniac Chun b ho cht - Dng c hp th: pha long 0,5 ml H2SO4 (d= 1,84) trong 1 lt nc ct. Bo qun dung dch trong bnh hnh ng tr y kn bng nt c ng thu tinh cha y tinh th axt oxalic. Thuc th phenol: Ho tan 5 g phenol mi chng ct, 25 mg natri nitro pruxit trong 100 ml nc. Bo ho thuc th khng qu 6 thng 40C. H tinh bt, dung dch 0,5%: trn u 0,25 g tinh bt vi 10 ml nc, cho thm 40 ml nc nng 60-700C dung n si, dung dch sau 1 pht lm lnh - Thuc th hipoclorit: Ho tan 10 g NaOH v 11,7 g NaCl trong 100 ml nc qua bo ho vi Clo (nng t 0,6 - 0,8 g Clo). Thuc th c bo qun khng qu 6 thng. Thuc th phi cha lng ch t 0,6 n 0,8 g ch trong 100 ml. Tin hnh xc nh hm lng ch hot tnh: Ly 20 ml dung dch thuc th cho vo bnh cu c nt mi, thm 10 ml H2SO4 10%, 10 ml KI 10%. y kn bnh cu v trong bng ti khong 10 pht, sau chun I2 gii phng bng Na2S2O3 0,05 mol/l n vng nht. Thm vo vi git h tinh bt, chun tip bng Na2S2O3 n khi dung dch mt mu; 1 ml dung dch natri thiosunphat 0,05 mol/l tng ng vi 0,00354 g clo. C th dng clorua vi chun b thuc th Dung dch chun amoniac gc: 100 g amoniac trong 1 lt; ha tan 0,3141 g NH4Cl trong 1 lt nc. Bo qun dung dch khng qu hai thng. Dung dch chun amoniac s dng c hm lng 1 amoniac trong 1 ml. Dung dch ny c chun b bng cch pha long dung dch chun gc. Ch pha long dung nh chun trc khi dng. Ly mu xc nh hm lng tng ln amoniac, cho khng kh cn nghin cu i qua hai ng hp th mc ni tip nhau, mi ng cha 5 ml dung dch hp th vi lu lng 0,51/pht, lin tc trong thi gian t 10 n 30 pht xc nh hm lng amoniac trng bnh ngy m c th ly mu theo hai cch: - Ly mu nh xc nh hm lng tng ln amoniac vi s lan khng t hn 6, cch nhau u trong mt ngy m - Cho khng kh (trong mu) cn nghin cu i qua dung dch hp th c cha 50 ml dung dch hp th vi lu lng 0,2 lt/pht lin tc trong 24 gi. Phi theo di qu trnh ly mu, nu dung dch b cn cn b sung thm nc ct

Tin hnh phn tch - Dng nc ct hai ln thm vo dung dch trong bnh hp th n 10 mg. - Ht 2 ml dung dch mu th cho vo ng nghim nt mi, thm 3 ml dung dch hp th, 1 mg thuc th phenol. Sau va lc. - Sau 2 gi tin hnh o mt quang ca dung dch, s dng cuvet 1 cm, bc sng 625 nm, dung dch so snh l nc ct. Thi gian cho thuc th cui cng n lc o mt quang ca dung dch i vi tt c cc mu phi nh sau. - Chun b mu trng t dung dch hp th; o mt quang ca 5 ml dung dch thuc th iu ch thnh "mu trng"; gi tr mt quang ca mu trng khng vt qu 0,02. Nu qu kim tra sch ca nc, dng c, cuvet v cht lng dung dch. Lng NH3 trong mu th c xc nh bng phng php ng chun theo hiu s gia mt quang ca mu em i phn tch v mt quang ca mu trng. Ly 5 ml dung dch t mi bnh trn ng nghim nt mi ri tin hnh lm nh dung dch th nghim Tnh kt qu Hm lng amoniac (C) trong khng kh c tnh bng mg/m3 theo cng thc:

Trong : a: lng NH3 trong dung dch mu ly phn tch(mg); B: tng lng dung dch mu th (ml); Ba: th tch dung dch mu th ly phn tch (ml); Vo: th tch mu khng kh a v iu kin tiu chun (m3) Khi xc nh nng trung bnh ngy m th th tch khng kh khng cn a v iu kin tiu chun.

Chng 9 CC THNG S NHIM CN KIM SOT

9.1. Khi nim chung nhim mi trng (ONMT) nhim mi trng l s lm thay i trc tip hoc gin tip cc tnh cht vt l, ho hc, sinh hc ca bt k thnh phn mi trng no lm cho tiu chun cht lng ca thnh phn mi trng b vi phm dn n lm nguy hi hoc c kh nng nguy hi cho mi trng v sc kho con ngi (Cc Mi trng, 12/2000). Kim sot nhim mi trng (KSONMT) Kim sot nhim mi trng (KSONMT) l s tng hp cc hot ng, hnh ng, bin php v cng c nhm phng nga, khng ch khng cho s nhim xy ra, hoc khi c s nhim xy ra th c th ch ng x l, lm gim thiu hay loi tr c n (Cc Mi trng, 2000). 9.2. Cc nguyn tc chung trong kim sot nhim mi trng: Kim sot nhim mi trng bt k mt lnh vc, i tng no cng u phi tun th nhng nguyn tc chnh sau: - m bo s pht trin kinh t - x hi mt cch bn vng. - m bo tnh lng ghp: i vi cc nh qun l, mt trong nhng trng tm quan trng i vi cng tc lng ghp l cch tip cn lin ngnh i vi cng tc kim sot nhim. Ngoi ra, nhu cu lng ghp xuyn sut cc trch nhim qun l mi trng nhm m bo tp trung c ngun lc v con ngi, cng ngh v ti chnh cho cc vn c u tin. Lng ghp cc khu vc, cc ngnh, cc i tng kim sot nhim vi nhau s to c hi thun li trong cng tc kim sot nhim, nht l trong khu tng hp, x l mang tnh khu vc tm ra cc quy lut chung nht. Ngn nga nhim mi trng l nguyn tc chu o trong cng tc kim sot nhim. Khc phc v phc hi l quan trng; Cc tiu chun mi trng, cht thi v tiu chun s dng cng ngh l ch da v cn c chnh. - Mt s lu c th: Phi s dng cc thng s v ch th mi trng kim sot nhim. Phi thc hin nh gi hin trng v tc ng mi trng: phm vi, cc bc tin hnh. Cc tiu chun v mi trng tiu chun x hay pht thi (emission oi emuent standards); tiu chun cht lng mi trng bao quanh hay tiu chun cht lng ca ngun tip nhn cht thi (ambient standards).

Cc nguyn tc gim thiu ngay t ngun pht sinh, s dng li cht thi: vic gim thiu lng cht thi l mt hng rt quan trng, c ngha rt ln i vi cc cht thi, c bit nhng cht thi bn vng kh phn hu v nhng cht nguy hi. V vy vic gim thiu v s dng li cc cht thi l nhng vic lm rt cn thit nhng ng thi l nhng vic lm rt phc tp. Quan trc cht lng mi trng (Monitoring Environmental Quality). xc nh hiu qu ca cc hot ng ci thin cht lng mi trng cn thit phi lng ho cht lng mi trng theo cc thng s mi trng: cc s liu v ngun thi v lng thi cc cht nhim; cc thng s cn quan trc, tp trung ch yu vo quan trc cc ngun thi gy nhim mi trng. 9.3. Cc thng s cht lng hay nhim mi trng cn kim sot 9.3.1. Cc cht nhim mi trng Cc cht gy nhim l nhng cht khng c trong t nhin hoc vn c trong t nhin nhng ti mt thi im no c hm lng ln hn v gy tc ng c hi cho mi trng t nhin, cho con ngi cng nh sinh vt sng. Cht gy nhim c th do hot ng ca con ngi (cht thi cng nghip v sinh hot) hoc do cc hin tng t nhin gy ra. Trong mi trng, cu trc ho hc cng nh nng ca n s quyt nh mc nhim ca mi trng nc, t v khng kh. Vic xc nh cc cht nhim rt quan trng. l c s cho vic xc nh ngun gc v mc nhim mi trng. Theo phng thc xut hin, cht nhim c phn loi thnh cht nhim s cp (xm nhp trc tip t ngun pht sinh) v nhim th cp (l nhng cht nhim c hnh thnh t nhim s cp trong iu kin t nhin). Tuy nhin tin li cho qu trnh kim sot nhim, vic phn loi cc cht nhim c xc nh da vo c tnh ca chng theo cc nhm nh sau: 9.3.1.1. i vi mi trng nc v t a. Cc cht hu c y l nhng cht tiu th xy trong mi trng nc. Do c tnh khng bn, chng c xu hng b xy ho thnh cc dng n gin hn Qu trnh ny nh hng trc tip n ho tan xy trong nc (DO). Ngoi ra cc ch tiu khc mu BOD (nhu cu xy sinh ho) v COD (nhu cu xy ho hc) c s dng nh gi mc nhim hu c trong nc. Ngun gc cc cht nhim dng hu c c th t cc dng sau: - Nc thi sinh hot: Hu ht cc cht hu c dng ny u c kh nng phn hu sinh hc. L nguyn nhn chnh gy ra hin tng thiu ht xy trong nc. - Nc cun tri b mt: Thnh phn hp cht hu c rt a dng, tu thuc vo c tnh b mt.

- Sinh ra do qu trnh pht trin - cht ca ng thc vt ph du, ng thc vt y. y l ngun pht sinh ng k trong cc lu vc giu cht dinh dng. - T hot ng ng sn xut hoc sn phm ca cng nghip: Thng thng cc cht hu c dng ny bn, kh nng phn hu sinh hc thp, gy nhim nng n cho cc ngun nc. l cc cht nhin liu, cht do, cht mu, thuc tr su, ph gia dc phm thc phm m ngun gc t cc nh my thc phm, giy, thuc da, hp, ho cht, hoc do ti tiu * Mt s cht hu c tng hp in hnh tn ti trong ty nhin gy nhim mi trng nc l: Ho cht bo v thc vt: Bao gm thuc tr su, thuc dit c, thuc dit nm mc, dit loi gm nhm, thuc tr cn trng. Theo quan im ho hc cc cht bo v thc vt c phn thnh cc dng sau: - Hp cht hu c halogen - Hp cht hu c phi pho - Cc cacbamat - Cc clorophennoxyaxit Cc cht bo v thc vt thm nhp vo c th con ngi thng qua qu trnh pht tn trong nc hoc do tn lu sinh vt, sau khi sinh vt cht b cun tri theo nc. Chng c tch t trong chui thc n m mt xch cui cng l con ngi. Cht bo v thc vt c trong nc s tc ng trc tip n qu trnh pht trin ca sinh vt, thay i cu trc sinh hc, gy ra cc cc bnh l nh ung th, qui thai... * X phng, cc cht ty ra v ph gia L nhng ngun tim tng cc cht nhim dng hu c do c kh nng to nh tng to cc cht hu c l lng trong nc. Trong qu trnh ny cc anion to ra cc mixel x phng dng keo * Cc cht hu c tng hp khc. Tt c cc cht hu c c trong nc u l nhng cht tiu th xy do c tnh khng bn v c xu hng xy ho thnh cht n gii. Trong nc khi ch s DO thp, BOD v COD cao chng t nc b nhim nng bi cc cht hu c tiu th xy. Mt s dng c trng ca cht hu c in hnh trong t, nc cn quan tm nh bng 9.l:

Bng 9.1. Mt s cht nhim hu c in hnh trong t, nc

TT 1 2 Loi hp cht hu c Hp cht hyrocachon Hp cht halogen hyrocacbon V d Cydohexen, Benzine, Benzen, toluen, Styren. Naphtalen, Benzopyren Chloroform, Vinyclorua, tetrachloethen, Hexachorychohexen. Hexachlobenxen, polydorua, Byphenyl 2,3,7,8 tetracl(Hlibenzodioxin Tributyphotphat Acrylamid,Acrylnitnt, O-nitrotoluen Methyclorua thu ngn Methyl-mercaptan Alkybenzensunfonat Methyl-hexanol, dipphenylether Formaldehyd. axeton, axitbenzoicPhenol, Cresol M, xt amin, lng trng trng

3 4 5 6 7 8 9 10 11 12

Plyclobenzodioxin Hp cht phtpho hu c Hp cht nh hu c Hp cht hu c kim loi Hp cht hu c lu hunh Cht hot ng b mt Alkohole & Ather Alehyt, keton Phenol Hp cht thin nhin

- Cc hp cht hu c hyrocacbon mch thng hay mch vng thng thng v sn phm ca du m, thm nhp v lm nhim ngun nc thng qua cc qu trnh khai thc, vn chuyn, gia cng, s dng. nh hng ca cc hp cht thm ny gy ra mi rt kh chu. i vi ngi v thc vt, chng gy nn cc bnh mn tnh v cp tnh nh ung th, nh hng n h thn kinh trung ng, mt, bnh ngoi da. Cc hp cht hyrcacbon a vng c cc ht keo hp th hoc bm dnh trn cc cht hot tnh b mt, do vy chng c kh nng tch t ln v cng c kh nng gy ung th. - Cc hp cht hu c halogen l nhng cht v cng c hi. Cc hp cht ny bao gm Cacbuahydro clorua, polyclorua byphenyl, thuc tr su cha do, cc phnol clo, PCDD, PCDF. - Cc hp cht plyclobiphenyl (PCB). - y l nhng cht nhim c tm thy trong cc ngun trn ton th gii, thm ch trong c cc m t bo chim v c. Cc PCB c bn ho hc, nhit v sinh hc rt cao. Ngun gc ca PCB ch yu t dung dch lnh cch in, lm thm thu bng v si aming, lm ho cht do v lm cc cht ph gia cho mt s loi sn. * nhim du m nhim nc do du m v sn phm ca chng (Xng, mazut, du bi trn,..) th hin nh sau: - Lm gim tnh cht l ho ca nc (nh thay i mu, mi v): Nc s c mi c trng khi nng ca n t ti 0,5 mg/l, cc ch tiu ho hc s thay i mnh khi nng ln hn 100 mg/l.

- Tc ng n qun th sinh vt: Nc b nhim gy thit hi v cng i vi sinh vt c nhy cm cao, qun th sinh vt gim xung rt nhanh do s phn hu ca du trong c th sng v d lp vng du ngn cn qu trinh trao i xy gia pha nc v kh. Hm lng du trong nc t 20-30mg/l s gy ri lon cc hot ng phn x ca c hm lng ln hn c th gy cht c. Khi hm lng cc hp cht thm ca u t ti 0,3 mg/l th qun th sinh vt trong nc c th b cht. b. Cc cht nhim di dng v c C rt nhiu cht v c gy nhim nc, t. Tuy nhin c mt s nhm in hnh cn lu nh sau * Cc loi phn bn v c l hp cht v c m thnh phn ch yu l cacbon, hyro v xy ngoi ra chng cn cha cc nguyn t nh N, P, K cng cc nguyn t vi lng khc. Cc loi ho cht ny s i vo nc do mt phn phn bn b cun tri khi s dng, bc hi hoc chuyn ho thnh cc dng khc v lu tn trong mi trng. Vic d tha cc cht dinh dng (Pht pht, mui amoni, ur, nitrat, mui kali...) gy nn s pht trin nhanh ca mt s loi thc vt bc thp nh to, rong ru v cc thc vt thn mm, gy nn hin tng thc vt cht hng lot. Chng b phn hu v to thnh lng ln hp cht hu c. Mt khc do pht trin t, mt lng ln xy trong nc s b tiu th gy nn tnh trng thiu ht xy mt cch trm trng (BOD cao), xut hin cc qu trnh kh, cc cht c tnh kh nh H2S, NH3 tng ln. Cc ion kim loi v HPO4- c chuyn ho t cc cht lng cn, ho tan vo nc gy c cho ngun nc mt. Cc khong axt Ngun gc chnh l t cc m than khng cn khai thc FeS2 (C nhiu trong m) l cht bn trong mi trng thiu xy. Khi tip xc vi mi trng khng kh, c s tham gia ca vi sinh vt s to thnh H2SO4 v Fe(OH)3 mu . S xut hin cc cht ny l nguyn nhn gy nn tnh trng mt cn bng sinh thi trong ngun nc (ng thc vt cht). Cn Ngun pht sinh do xi mn (ch yu) nc thi sn xut, sinh hot. Cc cht cn y thng trong tnh trng ym kh, tham gia qu trnh kh, gy nn tnh trng thiu ht xy trong nc. Cc cht cn l lng v ht huyn ph l mi trng hp th rt tt, chng nh l cc kho cha cc kim loi nng nh Cr, Cu, Mo, Ni, Co, Mn... gy c cho ngun nc. * Cc nguyn t vt y l cc nguyn t c rt t trong nc, tuy nhin kh nng gy c rt cao cho

h sinh thi v con ngi. Mt s nguyn t vt cn lu trong qu trnh kim sot cht lng nc bao gm: Bng 9.2. Cc nguyn t vt trong nc
Nguyn t Arsen Cadmium K hiu As Cd Ngun gc Cc loi khong, thuc tr su, cht thi ho hc Tc hi c, c kh nng gy ung th

Cht thi cng nghip, qung. m Thay th km trong qu trnh sinh ho. kim loi gy huyt p cao, au thn, ph hu m t bo mu, nhim c cc sinh vt di nc M kim loi, sn phm gc Crom Vim nga da, ni mn Than, cht tc nc, nc thi cng nghip Nhim c mt s thc vt

Crom Boren ng Flo Mangan Ch Thu ngn Selen

Cr Bo Cu F Mg Pb Hg Se

M kim loi, tuyn khong, khai Nhim c thc vt v to m Ngun a cht t nhin, cht thi Gy hng rng, mm xng cng nghip Cht thi cng nghip m Cng nghip, m, than du kh c vi thc vt hm lng cao c, nh hng ti thn v thn kinh

Cht thi cng nghip than, thuc Rt c tr su Ngun nc t nhin, qung c vi hm lng cao sunfua, than

Ngoi cc nguyn t vt, cc cht phng x cn c quan tm trong vic kim sot nhim phng x trong mi trng nc trong tng lai. 9.3.1.2. i vi mi trng khng kh Cc cht nhim trong khng kh cng bao gm cc cht hu c, v c v vi sinh vt. Bng 9.3 l mt s cht nhim khng kh t cng nghip v th. Bng 9.3. M s cht nhim chnh ca cng nghip v tc ng bnh l ca chng i vi sc khe con ngi
TT Cht kh nhim Ngun pht sinh Tc dng bnh l i vi ngi 1 Andehyt T phn ly cc cht du, m v Gy bun phin, cu gt, lm nh glyxerin bng phng php nhit. hng n b my h hp 2 3 Amoniac NH3 Asin (AsH3) Qu trnh ho hc sn xut phn Gy vim ty ng h hp m, sn hay thuc n. Qu trnh hn ni st thp hoc qu Lm gim hng cu trong mu, tc trnh sn xut que hn c cha axit hi thn, gy mc bnh vng da asen (arsenic)

4 5 6 7

Cacbon oxit Co Clo Hydroxyanit Hydroflorua HF

ng x kh xe my, t, ng khi Gim bt kh nng lu chuyn xy t than, du. trong mu. Ty vi, si v cc qu trnh ha hc Gy nguy hi i vi ton b ng tng t h hp v mu. Khi phun ra t cc l ch bin ha Gy tc hi i vi t bo thn kinh, cht, m kim loi. au u v lm kh hng, m mt Tinh luyn du khi, khc knh bng Gy mt mi ton thn, vim da. axit, sn xut aluminium v phn gy bnh v thn v xng bn, sn xut snh s, gm, thy tinh

TT Cht kh nhim Ngun pht sinh Tc dng bnh l i vi ngi 8 Hydrosulfit H2S Cng nghip ha cht v tinh luyn Mi ging nh mi trng thi, gy nhin liu c nha ng, cng bun nn, gy kch thch mt v nghip cao su, phn bn hng. 9 Nao oxit NOx ng x khi ca t, xe my, cng Gy nh hng n b my h hp, ngh lm mm ha than. mui xm nhp vo phi Gy ho, bun phn, nguy him i vi ngi bnh h hp. Gy tc ngc, au u, nn ma, t vong do bnh h hp.

10 11 12

Photgen (cacbon Cng nghip ha hc v nhum oxyclorua) Sulfuro SO2 Qu trnh t than v du

Tro, mui, khi, T l t mi ngnh cng nghip Gy bnh kh thng, au mt v c bi mn v ng x kh ca xe c th gy bnh ung th, cc bnh ng h hp. Bi, hi ch v Sn xut sn, mu, m kim loi, Bnh ng h hp, cc bnh v cc kim loi nng luyn kim, i cht mi rn y t v thn, cc bnh ung th cng nghip. khc Cc kh axit (HCl, H2SO4, HNO3...) VOC, HC mch thng, mch vng, Halogen Cng nghip ha cht, m kim loi, Bnh ng h hp, chng mt. ty ra, t cht thi nguy hi. bun nn, co git, vim phi, vim da, nguy him i vi h thn kinh... Cng nghip ha du, cc loi dung Vim ty mt, d ng da, bnh ng mi ha m phm, sn xut sn, h hp, h tun hon mu, h thn vecni, xng du xe kinh.

13

14

15

9.3.2. Cc ch tiu hay thng s cn kim sot i vi khu vc th v khu cng nghip i vi mi trng nc xc nh mc nhim mi trng nc, cn thit phi xc nh cc ch tiu hay cn gi l cc thng s cht lng nc nh trn. Thng thng cc thng s ny c quan h mt thit vi nhau, v vy khi nghin cu nh gi cht lng nc,

cn thit phi xem xt mt cch cn thn, chun xc. Cc thng s ny c chia thnh cc nhm: vt l, ho hc v sinh hc. Nhm ch tiu vt l: nh gi mc nhim hay cht lng nc theo cc ch tiu ny ngi ta xc nh nhit , mu mi, trong, c hay hm lng cn rn l lng, tng hm lng cc cht rn, dn in,... - Mi: Nguyn nhn to ra mi, l cc qu trnh phn hu cht hu c (to mi thi), hoc mi tanh ca st. Nh vy, thng qua mi c th nh gi mc phn hu cht hu c (hiu kh, k kh), qu trnh pht trin ca ng thc vt ph du,... - Mu: Cn c ch th mu c th nh gi s b cht lng nc. V d: cn c mu xanh xc nh mc dinh dng trong sng h, nh hng ca nc thi cng nghip c mu c trng, nh hng cc b bi nc thi sinh hot c mu nu xm, ngun nc trong mi trng k khu H2S tc ng vi Fe+2 to thnh FeS c mu en,... - Cc cht rn hay cn l lng thng l cc cht b cun tri theo dng nc, do xc ng thc vt cht hay do hot ng ca ngi, sc vt to ra. Hm lng cn ln s lm gim kh nng t lm sch ca ngun nc, cn tr qu trnh sinh thi din ra trong nc hoc cn tr qu trnh dit khun trong nc. Trong qu trnh kim sot cht lng nc, tu tng trng hp c th cng nh c tnh cht pht thi m ta a ra cc cht nhim cn kim sot cng nh cc ch tiu nh gi cht lng ngun nc. Nhm ch tiu ho hc y l nhm ch th rt quan trng. Trng thi tn ti ca chng phn nh r nt cht lng ngun nc cng nh nguyn nhn chnh gy nn. - pH: Biu th nng H+ trong nc, nu pH b hn 7, nc c tnh axit; ln hn 7 c tnh kim; bng 7 c tnh trung tnh. Cht nc trng thi bnh thng pH = 6-8,5 (ngun A) v 5.5-9 (ngun loi B). - Nhm nhim hu c: c trng cho nhm ny l BOD (nhu cu xy ho sinh ho) v DO (xy ho tan). Cc thng s ny phn nh y trng thi nhim cht hu c trong ngun nc cng nh trng thi ca h sinh thi ca n (quan h cht ch vi qu trnh sinh vt trong nc v bn y). ng thi vi BOD cn phn xc nh nhu cu xy ho hc (COD). - Ngoi cc hp cht hu c tc ng n nng xy trong nc cn c cc hp cht v c nh ammonla, nitrite, Sulphit, Hydrogen sulphit, Fe2+ - Mc dinh dng:

c trng cho nhm dinh dng l nh v pho pho. S c mt ca cc hp cht ny chng t nc ngun bi nhim bn bi nc thi sinh hot. Hp cht no l thnh phn quan trng cho qu trnh sng ca thc vt, ng vt trong nc. Lin quan n hp cht ny l qu trnh ph dng, gy ra hin tng ti nhim bn ln th hai. Cn c vo nng ca chng ngi ta phn ra cc trng thi ngun nc nh sau: Bng 9.4. Phn loi ngun nc theo mc dinh dng
Trng thi h, sng Rt ngho dinh dng Ngho dinh dng Dinh dng trung bnh Ph dng Dinh dng qu cao Thc vt l lng (mg/cm) 20 -50 50-100 100-300 >300 Tng cacbon hu c (mg) 3-30 1 -3 1-5 5 - 30 Tng P (g/1) 1-5 5-10 10-30 30 - 500 500-5000 Tng N (g/l) 1 -250 250 - 500 500-1100 1100-1500 > 1500

Ngun: jorgensen, 1980.

Phn 3 THC HNH

Chng 10 X L S LIU THNG K TRONG MI TRNG

Mc tiu: - Gip hc sinh hiu c kin thc thng k c bn ng dng trong mi trng. Gip hc sinh tnh ton v x l c cc php tnh thng k c bn, tng quan nhiu chiu, tnh sai khc, hi quy tuyn tnh, v xc nh cc yu t hn ch trong b tr th nghim. Yu cu: My tnh c cu hnh tt v ci t phn mm x l s liu thng k Ci t phn mm SAS 1. Tnh thng k c bn kt qu phn tch s liu ca cc nguyn t ho hc trong t. Yu cu - Gi tr trung bnh - Gi tr b nht - Gi tr ln nht - Tng - lch chun - H s bin ng Cch tnh ton Data direct; input S liu X1, X2, X3, X4,... Xn; cards; 21.08 28.9 22.18 27.31 24.1 24.4 25.0 24.2 1242.0 1129.0 1507.0 12630.0 2074.1 1232.0 1659.0 1861.1

proc corr data-direct; var X1, X2, X3, X4,...Xn; run; 2. Phn tch tng quan mt chiu v nhiu chiu gia cc yu t th nghim Yu cu - Tnh tng quan mt nhn t - Tnh tng quan nhiu nhn t - Lp bng tng quan nhiu nhn t Cch tnh ton: Data direct; input S liu X1, X2, X3 X4... Xn; cards; 21.08 28.9 22.1 27.31 ; proc corr data-direct; var Xl, X2, X3 X4... Xn; run; 3. Xc nh cc yu t nh hng Yu cu Phn tch sai s th nghim Cch tnh ton Data direct; input S liu X1, X2, X3, X4...Xn; cards; 21.08 28.92 22.18 24.11 242.0 2074.1 4.41 25.0 129.0 1232.0 1507.01659.0 24.1 1242.0 2074.1 1232.0 1659.0 1861.1

24.41 129.0 825.0 1507.0 24.21 263.0

27.31

24.2

1263.0 1861.1;

proc reg data=direct; model Y1 = X1, X2, X3, X4,... Xn/method=forward sle=0.05; run; 4. Phn tch sai khc gia cc cng thc th nghim Yu cu Xc nh cc yu t hn ch Phn tch mc nh hng ca cc yu t th nghim Cch tnh ton: data lsd; input treat $ germ @@; cards;

; proc anova; class treat; model germ treat; means treat~sd; means treat/1sd alpha-o~05; run;

Chng 11 THC HNH PHN TCH TRONG PHNG TH NGHIM

l. Xc nh pH ca nc Ngy nay, vic xc nh pa tr nn n gin do s pht trin ca khoa hc cng ngh. Gi tr pa c xc nh bng php o trn my o pa (pa meter). im cn lu khi o pH l vic bo qun in cc do cc c im v kh hu ca vng nhit i. Trc khi tin hnh o cn phi kim tra my bng cch iu chnh my vi cc dung dch m c gi tr pH = 4,00; 7,00; 10,00. in cc phi lun c bo qun trong dung dch bo qun. Tin hnh bng cch lc u mu dung dch sau cho u cm ng in cc ngp 1/3 trong dung dch o, quan st ng h bo gi tr pH trng thi cn bng ghi gi tr. 2. Xc nh cng ca nc Ly 100 ml nc cn xc nh cng, thm vo 10 ml dung dch m (nu kim ca mu nc ln th phi dng dung dch HCl 0,1N iu chnh cho pH dung dch bng 7- 8 theo giy ch th tng hp trc khi thm dung dch m), thm mt lng nh cht ch th (khong bng mt ht xanh), dung dch c mu . Chun dung dch bng dung dch chun Complexon III cho ti khi dung chuyn t mu sang mu xanh. Nu trong dung dch c mt cc ion cn tr nh Fe3+, Cu2+ th cn chun li vi mu nc khc v cch tin hnh nh sau: Sau khi cho 10ml dung dch m, ta thm vi git KCN 5% che ion cn tr ri mi thm cht ch th v tin hnh chun nh trn Tnh kt qu: cng ton phn ca nc c tnh nh sau:

Trong : a: th tch dung dch Complexon III tiu tn (ml); V: th tch mu nc ly phn tch (ml); 0,025: nng dung dch Complexon III (mol/1); 2: s ng lng gam cng tng ng vi 1 mol Complexon III. Ho cht - Dung dch Complexon III 0,025M: ho tan 9,306g Complexon III trong 1 lt nc ct hai ln - KCN 50%: cn 5g KCN ho tan trong 100 ml nc ct hai ln. - Enocrom T en: cn 0,05g cht ch th trn vi 10g NaCl.

- m NH4OH + NH4Cl (pH= 10), ho tan 25 g NH4Cl trong 100 ml nc thm 200ml NH4OH 20%, sau thm nc ct n 1 lt. 3. Xc nh Ca v Mg trong nc sinh hot Trnh t phn tch Cho mu nc vo bnh tam gic c V = 250ml, th tch mu nc c ly khng cha qu 15mg Ca. Dng nc ct pha long thnh 100 ml, nu thy cn thit. Nu mu nc c tnh axit th cn trung ho bng dung dch NaOH. Nu mu nc c kim cao hn 6 mlg/1 th cn thm vo lng tng ng dung dch HCl 0,1N, un si dung dch v ngui. Sau thm vo 2ml NaOH 2M v mt t cht ch th murexit. Chun t t bng ung dch EDTA 0,025M cho n khi dung dch chuyn t mu hng sang tm. Tnh kt qu:

Trong : a: th tch dung dch EDTA 0,025M (ml); V: th tch mu nc chun (ml); 1000: 2 x 0,025 x 20 x 1000. Ha cht - EDTA 0,025M: Xem phn trn. - NaOH 2M: ho tan 8g NaOH trong 100 ml nc ct hai ln. HCl 0,1N: pha 8,2ml HCl c trong 1 lt nc ct hai ln (Cch xc nh Mg tnh tng t nh Ca) Trnh t phn tch Ly vo bnh tam gic c V: 250ml, lng th tch nh trong xc nh Ca. X l mu nh lm i vi Ca. Thm vo 5ml Hiroxilamin 10%, vi git KCN 10% v mt lng nh ch th Eriocrom T en ri tin hnh chun bng EDTA 0,025M. Tnh kt qu

Trong : V1: th tch EDTA chun Ca + Mg (ml); V2: th tch Ca (ml); V: th tch mu nc (ml). Ho cht - Hidroximalin 10% ho tan 10g NH2OH.HCl trong 100 ml nc ct hai ln

4. Xc nh nhu cu xy ha hc (COD) Trnh t phn tch Ly 20ml mu nc cho vo bnh hi lu, ri thm vo HgSO4 (trung Cr th cn 0,1 g HgSO4). Thm vo 10ml dung dch K2Cr2O7 0,025N v mt vi ht thu tinh. Lp ng thu sinh hn thu tinh nhm. Thm vo t t 30ml H2SO4 c c cha Ag2SO4 qua phn cui ng sinh hn v lc u hn hp trong khi thm axit. un hi lu trong h gi. ngui v ra sinh hn hi lu bng nc ct. Pha long hn hp bng nc ct ti th tch khong 150ml, ngui. Chun lng bicronat d bng mui Fe2+, vi ch th axit Phenylanthranilic. Cng tin hnh mt th nghim mu trng nh i vi mu phn tch. Tnh kt qu

Trong : a: th tch Fe2+ chun mu ng (ml) b: th tch Fe2+ chun mu (ml) N: nng ng lng ca Fe2+ Ha cht: - K2Cr2O7 0,025N: Ho tan 12,259 g K2Cr2O7 ( sy kh 2 gi 1050C) trong nc ct v thm nc ti vch mc. - H2SO4 c c thm 22g Ag2SO4 cho mt chai 9 lt. - Dung dch Fe2+ 0,1 N: Ha tan 39g Fe(NH4)2SO4.6H2O tinh khit trong nc ct, thm 20ml H2SO4 c ngui ri nh mc ti 1 lt - Ag2SO4 tinh khit ho hc. - H2SO4 tinh khit ho hc. Ch th 1%: Ho tan 0,2g axit Phenylanthranilic trong 100 ml Na2SO3 0,2%. 5. Xc nh pH trong t Trnh t phn tch Lc lp t ( qua ry 1 mm) 15 pht trn my lc (hoc lc tay 30 pht) vi 25ml KCl l (vi pHKCl) hoc nc ct (pHH2O) sau yn 2 gi (khng qu 3 gi), lc 2 - 3 ln ri o pH ngay trong dung dch huyn ph.

Hiu chnh my o ph: My trc khi o phi hiu chnh bng cch o dung dch m pH tiu chun. Chnh cho kim ch ng tri s pH ca dung dch m. o mu: Gi cho in cc cch mt mu t l lem v ngp nc khong 2cm. Khi my n nh, c gi tr pH trn my Ghi ch: in cc thy tinh c ngm trong nc ct khi khng dng. T l t v dch chit c khc nhau ph thuc phng php. V vy, trong kt qu phn tch cn ghi r t l t dch chit rt v cht chit rt. V d: "pH trong KCl 1N 1:5W/V". Ngha l pH khi chit rt bng KCl 1N vi t l t dung dch chit rt l 1:5 (khi lng/ th tch). Nu khng ghi ch g th thng c hiu l pHH2O theo t l t nc l 2:5. Pha dung dch m tiu chun - Dung dch KHC8H4O4 0,05M: 10,21g KHC8H4O4 pha thnh 1000 ml. - Hn hp KH2PO4 + NaHPO4 0,025m: 3,10g KH2PO4 pha thnh 1000 ml; 3,55g NaHPO4 pha thnh 1000 m1. - Trn ln 2 dung dch ny thnh 2 lt hn hp. Thi hn s dng khng qu 2 thng. - Dung dch Na2B4O7 0,01N: 3,81g Na2B4O8.10H2O pha thnh 100ml - Dung dch KHC4H4O6 bo ho: 6g KHC4H4O6 trong 1 lt nc ct. - Cc dung dch trn pha song ng trong bnh polietilen, thi hn khng qu 3 thng. - Tr s pH ca cc dung dch m trn nh sau: 6. Xc nh cht hu c trong t (Walkley-Black) Trnh t phn tch Cn l t kh khng kh cho vo bnh tam gic 500ml thm 10 ml dung dch K2Cr2O7 1N. Thm 20ml H2SO4 c vo (thm nhanh theo kh nng c th thm). Lc nh v gi 30 pht. Thm 200ml nc ct v 10ml H3PO4 85%. Thm 1 ml ch th iphenylamin. Chun bng dung dch FeSO4 0,5N n khi dung dch c mu xanh l cy. Ho cht Ho tan 49,039 K2Cr2O7 trong nc ct v thm th tch n 1 lt - FeSO4 0,5N: ho tan 139g FeSO4.7H2O trong 800ml nc, thm 20ml H2SO4 c ri nh mc n th tch 1 lt. - iphenylamin: ho tan 0,5g ch th trong 20ml nc ri thm tip 100 ml H2SO4 c.

Tnh kt qu

Trong : N: nng ng lng ca mui FeSO4 V0, V1: th tch mui FeSO4 dng chun th nghim trng v chun mu; a: lng mu ly phn tch (g); K: h s chuyn i t mu khng kh sang mu kh tuyt i; 0,39 = 3x 10-3 x 100% x 1,3; 3: ng lng gam ca C; 13: h s "b" cho qu trnh oxy ho cha hon ton cht hu c trong phng php ny. % cht hu c = 2xC (%) Trc y dng h s 1,72 nhng hin nay thy h s 2 l thch hp hn (ISRIC, 1986). Ch thch Trc khi chun lng K2Cr2O7 cn d ( c 2 phng php) cn phi ngui dung dch xy ho, nu khng mt phn Fe2+ dng lng K2Cr2O7 cn d c th b xy khng kh xy ho. Vi 10ml K2Cr2O7 l ch c th xy ho ti a 25mg C, v vy khi p dng phng php Walkley - Black cn ht sc ch lng mu ly i phn tch. i vi nhng t hm lng mn < 2,6% c th ly 1 g mu em i phn tch, nu hm lng mn cao hn nn ly 0,2g t cn khi hm lng mn >13,5% th lng mu ly l 0,1 g (L c - Tp ch Khoa hc t, 10 - 1998). Nu dng ch th ferroin (0,695g FeSO4.7H2O v 1,485go phenaltrolininonohidrat (Cl2H8N2.H2O) trong 100 ml nc th dng 4 git ch th - khi kt thc chun , mu ca dung dch chuyn t xanh sang . C th dng phng php so mu xc nh cht hu c bng cch o mu Cr ti bc sng 625nm. Dng saccaroz(C12H22O11) lm trung dch chun kh Cr6+ trong K2Cr2O11; lm dung dch chun kh Cr6+ trong K2Cr2O7 thnh Cr3+.
3+

7. Xc nh m d tiu (NH4+) trong t Trnh t phn tch Cn 5 gam t v vo bnh tam gic, sau cho 50ml dung dch 2M.KCL, y nt li v lc c hc trong vng 1 gi ng h. lng t v lc v tch t v dung dch cho phn tch. Nu mu phn tch m cha phn tch ngay th phi gi trong t lnh gi. Khi phn tch, lc u ng nghim ng mu v ly 10 ml dung dch mu, b vo ng nghim chuyn dng phn tch, sau phn tch bng my Spectrophotometter. Ho cht Dung dch KCl 2 M: Ho 149 gam KCl trong 800 ml nc ct v vo bnh tam gic 1l, v sau thm nc ct vo bnh cho n khi chm vch nh du.

PH LC 1. Ch th mu
Ch thi mu Metyl tm thc chuyn 1) Metyl tim (bc chuyn 2) Crezon ta (bc chuyn 1) Timn xanh (bc chuyn 1) Crezon thc chuyn 1) -inttrophenon -initrophenon Metyl vng Bromphenon xanh Cng g Metyl da cam Bromcrezon xanh - dintrophenon Metyl Lacmolt (qu) - nitrophenon Clorophenon Azolitmin Bromezon ta Bromphenon Nng % 0,1 0,1 0,005 0,1 0,1 0,1 bo ho 0,1 0,01 0,1 0,1 0,1 0,1 0,1 v 0,2 0,2 v 0,5 0,1 0,1 Dung mi nc nc Cn 20% b.5,3ml NaOH 0,05N + nc ti 100ml a.cnn 20% b.4,3 ml NaOH 0,5N + nc ti 100ml a.cn 20% b.5,3ml NaOH 0,05N + nc ti 100ml nc nc Cn 90% a.cn 20% b.2,9ml NaOH 0,05N + nc ti 100 ml nc nc a. cn 20% b.2,9ml NaOH 0,05N + nc ti 100ml nc Cn 60% Cn nc Khong pH i mu 0,1 0,5 1,0 - 1,5 0,5 2,5 1,2 2,8 1,9 3,1 2,4 4,0 2,8 4,4 2,9 - 4 3,0 4,0 3,0 5,2 3,1 4,4 3,8 5,4 4,0 5,4 4,4 6,2 4,4 6,4 5,0 7,0 5,0 - 6,6 5,0 8,0 5,2 6,8 5,4 - 7,0 Bin i mu ch th Vng- xanh lc Xanh lc - xanh bin vng -vng Da cam- vng Khng mu - vng Khng mu - vng vng Vng- xanh bin Tm xanh - - da cam Vng- xanh bin Khng mu - vng vng -xanh bin Khng mu - vng Vng - -xanh bin Vng - tm Vng -

Bromtimon xanh

a.cn 20% b. 4,7 ml NaOH 0,05N + nc ti 100ml 0,1 v 1,0 Nc a.cn 20% 0,1 b. 3,7 ml NaOH 0,05N + nc ti 100ml a.cn 20% 0,05 b.3,9 ml NaOH 0.05N + nc ti 100ml a. cn 20% 0,05 b. 3,2 ml NaOH 0,05N+ nc ti 100ml 0,1 0,3 0,5 a.cn 20% b. 5,7 ml NaOH 0,05N + nc ti 100ml nc Cn 50%

6,0 -7,6

Vng- xanh bin

Phenon m -nitrophenon Axit rozolic

6,8 8,0 6,8 8,4 6,9 - 8.,

vng Khng mu - vng Vng-

Crezon (bc chuyn 2) -naphtophtalein Crezon ta

0,1 1,0 v 0,1 0,5

a.cn 20% b. 5,3 ml NaOH 0,05N + nc ti 100ml Cn 50% a.cn 20% b. 5,2 ml NaOH 0,05N + nc ti 100ml a.cn 20% b. 4,3 ml NaOH 0,05N + Nc ti 100ml Cn 90% Cn 60% Cn 90% nc nc Cn 60% Cn 50% 0,15 g metyl trong 100ml cn v 0,05 g metilen xanh trong 5ml nc ct v trn u

7,2 8,8 7,3 8,7 7,6 9,2

Vng h phch - hi ta Hng vng - lc xanh Xanh vng - ta

Timn xanh (bc chuyn 2) -Crezonphtalein Phenonphtalein Thimonphtalein Xanh Nil B Alizarinddor (bc chuyn 2) Nitroamin Indigocacmin Tassiro (ch th hn hp)

0,1 0,2 0,1 v 1,0 0,1 0,1 0,1 0,1 0,25

8,0 9,6 8,2 9,8 8,2 - 10,0 9,3 10,5 10,0 - 11,0 10,0 12,0 10,8 - 13,0 11,6 - 14,0 54

Vng - xanh bin Khng mu Khng mu hng Khng mu- xanh bin Xanh bin - Tm - vng nht Khng mu - nu Xanh bin - vng Tm - xanh lc

2. Dung dch m Hn hp m CH3COOH +CH3COO Na pH 3,8 3,9 4,0 4,1 4,2 4,3 4,4 4,5 4,6 CH3COOH 1N 421,5 345,1 284,4 236,2 197,9 167,4 143,3 124,1 108,9 pH 4,67 4,7 4,8 4,9 5,0 5,1 5,2 5,3 5,4 CH3COOH 1N 100,0 96,8 87,2 79,5 73,4 68,6 64,8 61,7 59,3 pH 5,5 5,6 5,7 5,8 5,9 6,0 6,1 6,2 6,3 CH3COOH 1N 57,4 55,9 54,7 52,7 53,0 52,3 51,9 51,5 51,2

hn hp m vi gi tr pH cn thit, ly nhng th tch dung dch CH3COOH l bng trn, thm 50ml NaOH 1N, thm nc n 500ml ri lc u.

Hn hp m CH3COOH + CH3COONH4
pH 3,0 3,4 3,8 4,2 4,6 5,0 5,4 5,8 6,2 6,6 7,0 7,4 7,8 8,2 8,6 9,0 9,4 9,8 10,2 10,6 11,0 CH3COOH 0,2N 99,24 93,40 88,20 80,20 66,00 58,60 54,60 50,90 50,40 50,30 50,00 48,40 47,80 46,40 44,70 41,00 34,00 28,80 16,00 9,80 2,48 NH4OH 0,76 6,60 11,80 19,80 34,00 41,40 45,40 49,10 49,60 49,70 50,00 51,60 52,20 63,60 55,30 59,00 66,00 76,20 84,00 90,20 97,52

Hn hp nhng th tch CH3COOH 0,2N v NH4OH 0,2N ly theo bng trn ri thm nc n 200ml v lc u. 3. Pha dung dch % axt v amoniac (ml dung dch c pha thnh 1 lt)
Ho cht pha HCl H2SO4 HNO3 CH3COOH T trng ca Nng ho cht phn % 150C 1,19 37,23 1,84 1,40 1,05 95,6 65,6 99,5 Cc nng phn trm mui pha 634,8 167,7 313,6 217,8 496,8 129,9 243,6 196,7 236,4 60,6 115,0 97,1 115,2 29,3 56,0 48,2 45,5 11,5 22,0 19,2 22,6 5,60 10,80 9,00

4. Nng v t trng axt H2SO4 v HCl

% 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 dH2SO4 1,1391 1,1471 1,1548 1,1626 1,1701 1,1783 1, 1 862 1,1942 1,2023 1,2104 1,2185 1,2267 1,2319 1,2432 1,2515 1,2509 1,2684 1,2769 1,2865 1,2941 1,3028 dHCl 1,098 1,103 1,1083 1,1135 1,1187 1,1239 1,1290 1,1342 1,1392 1,1443 1,1493 1,1514 1,1593 1,164 3 1,1691 1,1741 1, 1 789 1,1837 1, 1 885 1,1933 % 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 89 60 dH2SO4 1,3116 1,3205 1,3294 1,3384 1,3476 1,3569 1,3663 1,3758 1,3851 1,3951 1,4O49 1,4148 1,4218 1,4453 1,4453 1,4557 1,4662 1,4768 1,4875 1,4983 % 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 dH2SO4 1,5091 1,5200 1,5310 1,5421 1,5533 1,5646 1,5760 1,5874 1,5989 1,6105 1,6221 1,6338 1,6456 1,6571 1,6692 1,6810 1,6927 1,7013 1,7158 1,7272 % 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 dH2SO4 1,7383 1,7494 1,7594 1, 7693 1,7786 1,7872 1,7951 1,8022 1,8087 1,8144 1,8195 1,8210 1,8279 1,8312 1,8337 1,8355 1,8364 1,8364 1,8312 1,8305

5. Pha cc dung dich c nng ng lng khc nhau

Ho cht H2SO4 (d =1,84) HCl (d = 1,19) H2C2O4.2H2O KMnO4 NaOH KOH AgNO3 Na2S2O3.5H2O Mui Mohr K2Cr2O7 ng lng 49,04 36,46 63,04 31,61 40,00 56,11 169,89 218,21 392,16 49,04 1N 0,5N 0,2N 0,1N 28,0 14,0 5,6 2,8 82,0 41,0 16,4 8,2 6,3 3,16 40,0 20,0 8,0 4,0 56,1 28,0 11,2 5,6 17,0 24,8 78,4 39,2 9,81 4,90 0,05N 0,02N 0,01N 1,4 0,56 0,28 4,1 1,64 0,82 3,15 1,26 0,63 1,58 0,63 0,32 2.0 0,80 0,40 2,8 1,12 0,56 8,5 3,4 1,7 12,4 5,0 2,5 19,6 7,84 3,92 2,45 0,98 0,49 n v MI MI g g g g g g g g

Mui Mohr: Sunphat amon st (II) (FeSO4.(NH4)2SO4.2H2O Trilon B: Axit etylen diamin tetra axetic dinatri = Na2H2(CH2COO)4N2(CH2)2.2H2O = Chelaton 3 = 272,242 6. nh gi mt s ch tiu trong t Mn trong t Rt ngho: Ngho: <1% 1 -2%

TB: Giu:

2 - 4% 4 - 8%

Nit tng s (phng php Kjeldahl) Ngho: TB: Kh giu: Giu: Photpho tng s Ngho: TB: Giu: Kali tng s Ngho: TB: Giu: pHKCl Khng chua: Chua t: Chua: Chua nhiu: Rt chua: > 5,5 5,0 5,5 4,5 5,0 4,0 - 4,5 < 4,0 < 0,8% 0,8 - 2 % > 2% < 0,06% 0,06 0,1% >0,1 % < 0,08% 0,8 1,5% 0,15 0,2% > 0,2%

7. Thanh nh gi mt s kim loi nng trong t ng (Cu tng s) a) Tiu chun MAC ca Cu mt s nc trn th gii n v: ppm
Quc gia Hm lng o 100 Canada 100 Ba Lan 100 Nht 125 Anh 50 c 50

b) nh gi mc nhim t mt bi ng ca Ba Lan n v: ppm

Nhm t 0 I A < 15 1 5 - 30 B < 25 25 - 50 C < 40 40 - 70 (Ngun: Kabata & Pendias, 1992) II 30 - 50 50 - 80 70 - 100 II 50 - 80 80 - 100 100 - 150 IV 80 - 300 100 - 500 150 - 750 V > 300 > 500 > 750

Nhm t A: t c thnh phn c gii nh v trung bnh, pH < 5.5 Nhm t B: t c thnh phn c gii nng v trung bnh, pH < 5.5 Nhm t C: t c thnh phn c gii nng, giu cht hu c, pH: 5.5 6.5 Hng dn s dng cc loi t trn: * t nhim loi I: t bi nhim ng nh, c th canh tc vi tt c cc cy trng, khng nn trng rau cho tr nh * t nhim loi II: t b nhim trung bnh, c th trng cc loi ng cc, trnh ra dip v rau Bina. * t nhim loi III: t b nhim tng i nng, loi t ny ch nn s dng cho vic trng cy cng nghip * t nhim loi IV: t b nhim nng, tuyt i khng nn trng cc cy lm thc n, nn trng cy cng nghip c bit l cc loi cy ly cn, ly du dng lm cht t. t nhim V: t b nhim rt nng, phi c lm sch trc khi s dng. Km Tiu chun MA C ca Zn m s nc trn th gii n v: ppm
Quc gia Hm lng o 300 Canada 400 Ba Lan 300 Nht 250 Anh 150 c 300

Ch Tiu chun MA C ca Pb m s nc trn th gii n v: ppm

Quc gia Hm lng o 100 Canada 200 Ba Lan 100 Nht 400 Anh 50 c 500

Caimi Tiu chun MAC ca C mt s nc trn th gii n v: ppm

Quc gia Hm lng o 5 Canada 8 Ba Lan 3 Nht Anh 1 c 2

8. Gii hn ti a cho php hm 1ng tng s ca As, Cd, Cu, Pb, Zn trong t (TCVN 7209: 2002)
Thng s nhim 1.Asen (As) 2.Cadmi (Cd) 3.ng (Cu) 4.Ch (Pb) t s dng cho mc ch nng nghip 12 2 50 70 t s dng cho mc ch lm nghip 2 2 70 100 t s dng cho mc ch dn sinh, vui chi gii tr 12 5 70 120 t s dng t s dng cho mc ch cho mc ch mc ch thng mi, dch cng nghip v 12 12 5 10 100 100 200 300

9. Tiu chun nc mt 5942 - 1995

TT 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 Thng s pH BOD5 COD DO SS As Ba Cd Pb Cr6+ Cr3+ Cu Zn Mn Ni Fe Hg Sn NH4+ (tnh theo N) NO3- (tnh theo N) NO2- (tnh theo N) FCNPhenol (tng s) Du m Cht ty ra Coliforn n v mg/l mg/l mg/1 mg/l mg/l mg/l mg/1 mg/1 mg/l mg/l mg/l mg/1 mg/l mg/1 mg/1 mg/l mg/l mg/1 mg/1 mg/l mg/1 mg/l mg/1 mg/1 mg/1 mg/l MPN/100ml Gi tr gii hn A 6 - 8,5 <4 <10 >6 20 0,05 0,05 0,01 0,05 0,05 0,1 0,1 1 0,1 0,1 1 0,001 1 0,05 1,0 0,01 1 0,01 0,001 khng 0,5 5000 B 5,5 - 9 < 25 < 35 2 80 0,1 4 0,02 0,1 0,05 1 1 2 0,8 1 2 0,002 2 1 15 0,05 1,5 0,05 0,02 0,3 0,5 10000

28 29 30 31 Ch :

Tng HCBVTV (tr DDT) DDT Tng hot phng x Tng hot phng x

Bp/1 Bp/l

0,15 0,01 0,1 1

0,5 0,01 0,1 1

A: p dng i vi cc ngun nc dng lm nc ct sinh hot (phi qua x l). B: p dng i vi nc mt dng cho cc mc ch khc.

10. Tiu chun nc ngm 5944 - 1995

TT 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 Thng s pH Mu cng (tnh theo cacoa) TSS As Cd Pb Cr
6+

n v mg/l Pt/Co mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1

Gi tr gii hn 6,5 8,5 5-50 300 - 500 750 - 1 500 0,05 0,01 0,05 0,05 1 5 0,1 0,5 15 0,001 0,01 0,01 1 0,01 45 200 - 400 0,001 3 khng

Cu Zn Mn Fe Hg Se Cl F
-

CNNO3
-

mg/1 mg/1 mg/1 MPN/100ml MPN/100ml

SO4Phenol Coliform Fecal coli

11. Tiu chun nc thi cng nghip 5945 - 1995

TT 1 2 3 4 pH BOD5 COD SS mg/1 mg/1 mg/1 Thng s n v Gi tr gii hn A 6-9 20 50 50 B 5,5 - 9 50 100 100 C 5-9 100 400 200

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 Ch :

As Cd Pb Cr Cr3+ Cu Zn Mn Ni Fe Sn Hg Clo Flo CN

6+

mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 MNP/100ml

0,05 0,01 0,1 0,05 0,2 0,2 1 0,2 0,2 1 0,2 0,005 1 1 0,05 0,2 30 0,1 4 0,2 5 0,02 0,001 5000

0,1 0,02 0,5 0,1 1 1 2 1 1 5 1 0,005 2 2 0,1 0,5 60 1 6 0,5 1 10 0,1 0,05 1000

0,5 0,5 1 0,5 2 5 5 5 2 10 5 0,01 2 5 0,2 1 60 10 8 1 2 30 0,1 1

Sunfua Tng Nit NH4 (tnh theo N) Pht pho tng s Pht pho hu c Du m khong Du ng thc vt Tetracloetylen Phenol Coliform
-

A: c th vo vc nc dng lm nc cp sinh hot; B: ch cho ch vo cc vc nc dng cho cc mc ch nh giao thng thu, ti tiu, nui trng thu sn, trng trt... C: khng c php thi ra mi trng.

12.Tiu chun nc bin ven b 5943 1995

TT 1 2 3 4 5 6 7 8 9 Thng s Nhit pH DO BOD5 SS As Cd Pb Cr6+ n v C mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 Gi tr gii hn Bi tm 30 6,5 8,5 4 < 20 25 0,05 0,005 0,1 0,05 Nui thy sn 6,5 8,5 5 < 10 50 0,01 0,005 0,05 0,05 Cc ni khc 6,5 8,5 4 < 20 200 0,05 0,01 0,1 0,05

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

Cr3+ Cu Zn Mn Fe Hg NH4 (tnh theo N) Cl F

-

mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1 mg/1

0,1 0,02 0,1 0,1 0,1 0,005 0,1 1,5 0,01 0,01 0,001 khng 2 0,05 1000

0,1 0,01 0,01 0,1 0,1 0,005 0,5 0,01 1,5 0,005 0,01 0,001 khng 1 0,01 1000

0,2 0,02 0,1 0,1 0,3 0,01 0,5 1,5 0,01 0,02 0,002 0,3 5 0,05 1000

SO4 CN

Phenol tng s Vng du m Nh du m Tng HCBVTV Coliform

TI LIU THAM KHO CHNH

1. A.P.Kreskov, ngi dch: T Trng Nghi, Trn T Hiu (1989): C s ho hc phn tch: C s l thuyt phn tch nh tnh, Nxb i hc v Gio dc chuyn nghip. 2. A.P.Kreskov, ngi dch: T Trng Nghi, Trn T Hiu (1989): C s l thuyt phn tch nh lng, Nxb i hc v Gio dc chuyn nghip 3. Cc tiu chun nh nc Vit Nam v mi trng(1995), H Ni. 4. L c v cc tc gi (2004): Mt s phng php phn tch mi trng, Nh Xut Bn i hc Quc gia H Ni 5. F.W.Fifield and P.J. Haines (2000): Environmental Anlytical Chemistry, Blackle Academic & Professional 6. L Vn Khoa, Nguyn Xun C, Bi Th Ngc Dung, L c, Trn Khc Hip, Ci Vn Tranh (2000): Phng php phn tch, nc, phn bn v cy trng, NXB Gio dc, H Ni. 7. T Vn Mc(1995): Phn tch ho l, NXB KHKT, H Ni. 8. T Vng Nghi, Hunh Vn Trung, Trn T Hiu(1986): Phn tch nc, NXB KHKT, H Ni. 9. AmoldE. Greenberg et al.(1992): Sandard Methods for the Examination of Water and Waste Water, 18h - Enition, Amencan Public Health Association 10. G.R. Chhatwal et al.(1989): Environmental Analysis, Anmol Publications, NewDelhi. 11. Pradyot Patnaik (1997): Handbook of EnvironmentaIAnaIysis, Lewis Publishers. 12. Stewart E.Allen (1989): Chemical analysls of Ecologlcal materials, Blackwell Scientific Publications. 13. Lm Minh Trit, Dip Ngc Sng (2000): Cc phng php phn tch kim loi trong nc v nc thi, Nh xut bn khoa hc v k thut. 14. W.Schneider (1988): Water Analysls, Springer - Verlag Berlin Heidelberg

MC LC Trang
LI M U ............................................................................................................................ 2 Phn 1: NHNG VN CHUNG ......................................................................................... 3 Chng 1: M U .................................................................................................................. 3 1.1. Mi trng................................................................................................................... 3 1.2. Phn tch mi trng ................................................................................................... 3 1.3. S la chn phng php phn tch mi trng .................................................... 3 l.4. Gi tr ca cc s liu trong phn tch mi trng ....................................................... 4 1.5. nh hng ca cn bng ............................................................................................. 5 Chng 2: CHNH XC V TIN CY CA PHP PHN TCH ............................ 8 2.1. Bo m v kim sot cht lng trong phn tch mi trng ................................... 8 2.2. Sai s v chnh xc ................................................................................................. 8 2.3. th kim tra........................................................................................................... 15 Phn 2: MT S PHNG PHP DNG TRONG PHN TCH MI TRNG............. 17 Chng 3: PHNG PHP TRC QUANG......................................................................... 17 3.1. Phng php so mu quang in............................................................................... 17 3.2. Phng php quang k ngn la (Flamephotomet)................................................... 20 3.3. Phng php quang ph hp th nguyn t (AAS) .................................................. 23 Chng 4: PHNG PHP IN HO................................................................................ 29 4.1. Cc chn lc ion........................................................................................................ 29 4.2. Phng php cc ph ................................................................................................ 39 Chng 5: CC PHNG PHP PHN TCH SC K ..................................................... 49 5.1. M u....................................................................................................................... 49 5.2. Mt s khi nim ....................................................................................................... 49 5.3. Sc k lng hiu nng cao ......................................................................................... 54 5.4. Sc k kh (GC - Gas chromatography) .................................................................... 56 Chng 6: CC LOI NC V CC PHNG PHP PHN TCH NC ................. 60 6.1. i cng v cc loi nc ....................................................................................... 60 6.2. Phn tch nc ........................................................................................................... 62 6.3. Ly v bo qun mu nc........................................................................................ 63 6.4. Xc nh thnh phn ho hc ca nc..................................................................... 67 6.5. Xc nh mt s tnh cht khc ca nc.................................................................. 87 Chng 7: PHN TCH T.................................................................................................. 95 7. 1. Gii thiu chung ....................................................................................................... 95 7.2. Phn tch mt s tnh cht l ho hc c bn ca t.............................................. 105 7.3. Xc nh mt s kim loi nng trong t................................................................. 135 7.4. S dng phng php quang ph hp th nguyn t xc nh cc kim loi nng ........................................................................................................................................ 164 Chng 8: PHN TCH KH................................................................................................. 166 8.1. Gii thiu chung ...................................................................................................... 166 8.2. Phn tch kh ............................................................................................................ 169 Chng 9: CC THNG S NHIM CN KIM SOT............................................... 181 9.1. Khi nim chung...................................................................................................... 181 9.2. Cc nguyn tc chung trong kim sot nhim mi trng:.................................. 181 9.3. Cc thng s cht lng hay nhim mi trng cn kim sot............................ 182 Phn 3: THC HNH ........................................................................................................... 190 Chng 10: X L S LIU THNG K TRONG MI TRNG................................. 190 Chng 11: THC HNH PHN TCH TRONG PHNG TH NGHIM ........................ 193

l. Xc nh pH ca nc ................................................................................................. 193 2. Xc nh cng ca nc ........................................................................................ 193 3. Xc nh Ca v Mg trong nc sinh hot................................................................... 194 4. Xc nh nhu cu xy ha hc (COD) ....................................................................... 195 5. Xc nh pH trong t ................................................................................................ 195 6. Xc nh cht hu c trong t (Walkley-Black).......................................................196 7. Xc nh m d tiu (NH4+) trong t ...................................................................... 198 PH LC ............................................................................................................................... 199 TI LIU THAM KHO CHNH ........................................................................................ 209