You are on page 1of 74

M U

Cc phng php phn tch bng cng c c vai tr c bit quan trng trong s pht trin ca cc ngnh khoa hc k thut v cng ngh. Vi s pht trin nhanh chng ca k thut in t v tin hc, cc my mc thit b phn tch cng c hin i ha, cho php xc nh nhanh chng vi chnh xc cao cc mu cha hm lng rt nh ca cc cht phn tch. Nhm cc phng php phn tch quang hc da trn cc tnh cht quang hc ca cht cn phn tch, c mt s phng php sau: 1. Phng php trc quang da trn php o lng bc x in t ( bxt ) do dung dch phn tch hp th. y cn k n phng php hp c, da trn php o lng bxt b hp th bi cc ht huyn ph (dung dch keo); Phng php khuych c, da trn php o lng bxt b khuych tn bi cc ht huyn ph. 2. Phng php quang ph pht x nguyn t AES (Atomic Emision Spectrometry), da trn s kho st ph pht x nguyn t ca nguyn t cht phn tch. 3. Phng php quang ph hp th nguyn t AAS (Atomic Absorption Spectrometry), da trn s kho st ph hp th nguyn t ca nguyn t ca cht phn tch. 4. Phng php pht quang, da trn php o cng bc x do cht phn tch pht ra, di tc dng ca nng lng bxt chiu vo n. Ngoi ra, thuc vo cc phng php quang hc cn c phng php khc x, da trn php o chit sut ca cht phn tch; Phng php ph hng ngoi IR, Phng php ph Rntgen; Phng php ph Raman

CHNG 1. CC VN CHUNG
1.1. Bn cht ca bc x in t v cc phng php ph 1.1.1. Bn cht ca bc x in t Bc x in t ( bxt ) bao gm t sng v tuyn n cc bc x Rntgen v Gamma u c bn cht sng v ht. Bn cht sng ca bxt th hin hin tng nhiu x v giao thoa, bxt l nhng dao ng c hai thnh phn l in trng v t trng, cc sng ny truyn i trong khng gian vi vn tc ca nh sng theo hnh sin c cc cc i v cc tiu; khong cch gia 2 u mt ca mt sng c gi l bc sng, k hiu . Cng ca bxt t l vi bin ca dao ng. Nhng bxt khc nhau c di bc sng khc nhau hay bc sng l i lng c trng cho bxt. Ngoi ra bxt cn c c trng bng tn s , gia bc sng v tn s lin h vi nhau qua biu thc: c= hay = c / trong c l tc nh sng, c = 3.108 m/s Trong cc phng php ph, ngi ta cn dng i lng nghch o ca ( 1/ ) gi l s sng c trng cho sng, n v ca s sng lun l cm-1 = 1/ photon, cc dng bxt t khc nhau c nng lng khc nhau. S thng nht gia bn cht sng v bn cht ht ca bxt c th hin trong biu thc: = h = hc/ trong h l hng s Planc, h = 6,62.10-34J.s 1.1.2. n v o v s phn chia cc vng bxt Trong biu thc 1.4 l cc i lng c trng cho bxt. Bc sng c th nguyn l di. o , ngi ta dng cc n v o di l mt (m) cng cc c s ca mt, cc n v hay dng l m; nm v Ao ( 1A = 10-10m ).
2

(1.1) (1.2)

( 1.3)

Vi bn cht ht, bxt l nhng phn nh mang nng lng c gi l

(1.4)

i lng nghch o ca bc sng l s sng ch o bng mt loi n v l cm-1. Tn s c nh ngha l s dao ng m bxt thc hin trong mt giy, nn c th nguyn l s-1. n v o ca l hec ( hertz ) c k hiu l Hz v cc bi s ca n l kHz ( kilohec ); MHz ( megahec ). c th gy hiu ng quang ph, nng lng ca bxt phi ph hp vi hiu s mc nng lng E tng ng vi cc trng thi nng lng ca nguyn t hay phn t, ngha l bc sng ca bxt phi ph hp vi h thc: E = = h = hc/ hay = hc/E phn tch m ta c cc phng php quang ph khc nhau, c th l: - Min sng v tuyn, viba cho phng php ph cng hng t. - Min sng tia Rntgen v tia cho cc phng php ph Rntgen v ph tia . - Min sng nh sng quang hc cho cc phng php ph nhn thy ph t ngoi ( UV - VIS ); ph hng ngoi ( IR ). - Trong min sng nh sng quang hc cng c cc phng php ph pht x nguyn t; ph hp th nguyn t v ph hunh quang. Di y l cc vng sng chia theo chiu di bc sng. Bng 1.1. Phn loi cc vng bc x in t Bc x Tia Tia Rntgen T ngoi v kh kin Hng ngoi Vi sng Sng v tuyn , cm 10-11 - 10-8 10-8 - 10-6 10-6 - 10-4 10-4 - 10-2 10-1 - 10 > 10 E, eV ~ 107 ~ 105 ~ 10 ~ 10-1 ~ 10-3 < 10-6 ( 1.5) Ty theo bn cht ca bxt tng tc vi nguyn t hay phn t ca cht

1.2. S tng tc gia vt cht v bxt


3

Khi chiu mt chm bxt vo mt mi trng vt cht, s xy ra hin tng cc phn t hay nguyn t ca vt cht hp th nng lng hay pht x nng lng. Nng lng m phn t hay nguyn t pht ra hay hp th vo l: E = E2 - E1 = h s ca bxt b hp th hay pht x ra. Nu nng lng trng thi cui cao hn trng thi u ( E > 0 ) th xy ra s hp th bxt, ph sinh ra trong qu trnh ny l ph hp th; Cn nu nng lng trng thi u cao hn trng thi cui ( E < 0 ) th xy ra s pht x nng lng, ph sinh ra trong qu trnh ny l ph pht x. Cc phng php phn tch da vo ph nguyn t thc hin trn cc my quang ph hp th nguyn t AAS hay my quang ph pht x nguyn t AES. Cc phng php phn tch da vo ph phn t th phong ph hn, thc hin trn cc my o quang UV-VIS; my quang ph hng ngoi IR. 1.3. Trng thi nng lng ca phn t, ph phn t Mt phn t d l n gin nht cng c cc chuyn ng sau: - Chuyn ng ca cc in t quanh cc ht nhn: cc in t ha tr v cc in t khng tham gia to lin kt ha hc - gi chung l chuyn ng in t. - Chuyn ng thay i tun hon cc v tr ca cc ht nhn so vi nhau gi l chuyn ng dao ng ca phn t. - Chuyn ng thay i phng hng ca ton phn t trong khng gian - gi l chuyn ng quay ca phn t, chuyn ng ny ch c cc phn t cc cht trng thi kh v hi. Nh vy, nng lng ton phn Etf ca phn t c th biu din: Etf = Ee + Ev + Er lng in t. Ev l nng lng lin quan n chuyn ng dao ng ca ht nhn ( vibration ) - gi l nng lng dao ng.
4

( 1.6 )

Trong E1 v E2 l mc nng lng trng thi u v trng thi cui; l tn

( 1.7 )

trong : Ee l nng lng lin quan n chuyn ng ca in t - gi l nng

Er l nng lng lin quan n chuyn ng quay ca phn t ( rotation ) - gi l nng lng quay. L thuyt v thc nghim chng minh Ee >> Ev >> Er , nu nng lng o bng n v kcal/mol th Ee khong 60 150 kcal/mol; Ev khong 1 10 kcal/mol; Er khong 0,01 0,1 kcal/mol. Trong iu kin bnh thng, cc phn t tn ti trang thi c bn, c nng lng thp nht Eotf, khi phn t nhn nng lng, v d khi hp th bc x, c th chuyn ln mc nng lng cao hn. Khi phn t nhn nng lng ln, v d bxt c nng lng ln, phn t chuyn ln trng thi c nng lng cao hn E*tf gi l trng thi kch thch v: E*tf = E*e + E*v + E*r phn t. Etf = E*tf - Eotf = Ee + Ev + Er ( 1.9 ) Etf l bc chuyn nng lng ton phn ca phn t; Ee l bc chuyn nng lng in t; Ev l bc chuyn nng lng dao ng; Er l bc chuyn nng lng quay. Nh vy do hin tng hp th bxt ca phn t gy nn cc bc chuyn nng lng in t, nng lng dao ng, nng lng quay ca phn t, l ngun gc cc loi ph hp th phn t: ph quay, ph dao ng - quay, ph in t - dao ng - quay.... Ngoi ra, phn t c th hp th cc bxt gy nn cc bc chuyn nng lng, ngoi vic cn c iu kin nng lng ph hp theo h thc ( 1.5 ) cn c cc yu cu khc, gi l theo quy tc chn lc. C hai loi quy tc l quy tc cho php v quy tc cm: quy tc cho php quy nh cc iu kin cho php xy ra cc bc chuyn; Quy tc cm nu cc iu kin m vi cc iu kin bc chuyn nng lng khng xy ra c. Chnh v bn cht nh vy m ph phn t c cu trc rt phc tp, chng ta thng ni l c cu trc m. Vi cc my quang ph c tn sc khng ln, ph phn t hu nh l min bc x lin tc; Vi cc my quang ph c tn sc ln ph phn t gm v s vch st nhau. (1.8 ) S thay i trng thi ca phn t do c s thay i v nng lng ca

Mi phn t ca mt cht th c cu trc khc nhau nn c cc bc chuyn nng lng khc nhau, s c ph hp th phn t c trng v khc nhau, mt khc vi cc k thut ph hp, ngi ta to ph in t, ph dao ng, ph quay ca phn t ca cht nghin cu, chnh l c s ca cc phng php phn tch nh tnh. Cn phn tch nh lng, ngi ta da vo nh lut v s hp th bxt Lambert-Beer . 1.4. Ph hp th nguyn t v ph pht x nguyn t trn ta xt s to thnh ph ca phn t, to bi s lin kt ca t nht l hai nguyn t. Cn khi l nguyn t trng thi hi t do th s c trng bi ph hp th hoc ph pht x nguyn t, c ch to thnh c th gii thch nh sau: Trong iu kin bnh thng nguyn t trng thi c bn, khng thu v cng khng pht nng lng di dng cc bc x. y l trng thi bn vng v ngho nng lng. Nu nguyn t nhn nng lng di dng nhit th nguyn t s chuyn ln trng thi c nng lng cao hn, gi l trng thi kch thch, trng thi kch thch ny khng bn, ch khong 10-8 10-9 s, sau nguyn t c xu hng tr v trng thi c mc nng lung thp hn, khi ny nguyn t s gii phng nng lng di dng bxt bao gm nhiu tia n sc c bc sng khc nhau nm trong di ph quang hc ( 190 - 1100nm ). Nu thu, phn li v ghi chm tia ta s c di ph gm cc vch pht x ca nguyn t hoc ion. Trong tp hp cc vch ph th mi nguyn t hoc ion li c nhng vch c trng ring. Mt c im quan trng l cc nguyn t t do c kh nng hp th nhng tia bc x m n c th pht ra trong qu trnh pht x ca n. Nu nguyn t nhn nng lng di dng bxt ng ng vi nhng tia m n pht ra trong qu trnh pht x th nguyn t chuyn ln trng thi kch thch. Ph sinh ra trong qu trnh ny gi l ph hp th nguyn t. Nu gi nng lng ca bxt b nguyn t hp thu l = h th ta c: = h = E = Em - Eo hay E = h.c/ ( 1.10 ) (1.11 )

Trong Em v Eo l nng lng trng thi kch thch v trng thi c bn ca nguyn t; h l hng s Planck; c l tc nh sng; l bc sng ca vch ph hp th. Vy ph hp th nguyn t cng l ph vch. Nhng nguyn t khng hp th tt c cc bc x m n c th pht ra c trong qu trnh pht x. Qu trnh hp th ch xy ra vi cc vch ph nhy, cc vch ph c trng v cc vch ph cui cng ca nguyn t. Cho nn i vi cc vch ph qu trnh hp th v pht x l hai qu trnh ngc nhau. Trong phng trnh ( 1.10 ), nu gi tr E l dng ta c qu trnh pht x, nu gi tr E l m ta c qu trnh hp th. Nh vy ty theo tng iu kin c th nguyn t ha mu v kch thch nguyn t m qu trnh no xy ra l chnh, c th l: - Nu kch thch nguyn t bng nng lng nhit ta c ph pht x nguyn t. - Nu kch thch nguyn t bng chm tia n sc ta c ph pht x nguyn t. Phng php phn tch da trn ph pht x nguyn t gi l phng php quang ph pht x nguyn t AES (Atomic Emision Spectrometry ) vi my phn tch tng ng. Phng php phn tch da trn ph hp th nguyn t gi l Phng php quang ph hp th nguyn t AAS ( Atomic Absorption Spectrometry ) vi cc my phn tch AAS.

Chng 2. PHNG PHP QUANG PH HP TH PHN T UV-VIS


(Phng php trc quang phn t) Phng php quang ph hp th phn t hay cn gi l phng php o quang, phng php phn tch trc quang phn t l mt trong nhng phng php phn tch cng c thng dng vi rt nhiu th h my khc nhau, t cc my n gin ca th h trc cn c gi l cc my so mu n cc my hin i c t ng ha hin nay, gi l my quang ph hp th phn t UVVIS. Cc my o quang lm vic trong vng t ngoi (UV) v kh kin (VIS) t 190nm n khong 900nm. 2.1. C s l thuyt ca phng php 2.1.1. S hp th nh sng ca dung dch mu Dung dch c mu l do bn thn dung dch hp th mt phn quang ph ( mt vng ph ) ca nh sng trng, phn cn li l ra cho ta mu ca dung dch, chnh l mu ph ca phn nh sng trng b hp th (vng quang ph cn li). V d: dung dch Fe(SCN)3 ta nhn thy mu l do khi nh sng chiu vo dung dch, dung dch ny hp th mnh bc x n sc mu xanh v xanh l cy, vng quang ph cn li l ra cho ta mu . S hp th ca dung dch theo mu c trnh by trong bng 2.1 Bng 2.1. S hp th mu ca cc dung dch mu TIA SNG N SC B HP TH 400nm 450nm: vng tm 450nm 480nm: vng chm 480nm 490nm: vng chm lc 490nm 510nm: vng lc chm 510nm 560nm: vng lc 5600nm 575nm: vng lc nh vng MU CA DUNG DCH lc nh vng vng da cam ta tm

575nm 590nm: vng vng 590nm 640nm: vng da cam 640nm 720nm: vng 720nm 800nm: vng ta

chm chm lc lc chm lc

S hp th bc x n sc (bxs) ca dung dch cn ph thuc vo nng ca cht hp th. v d trn, dung dch Fe(SCN)3 c nng cng ln th s hp th cng mnh, biu hin mu ca dung dch cng m. 2.1.2. Cc nh lut c bn v s hp th nh sng nh lut Bug - Lambe (Bourguear - Lambert): Khi chiu mt chm bxs c cng I0 qua mt lp vt cht c b dy l, th cng bxs l ra I bao gi cng nh hn I0 . C th biu din bng biu thc: I0 = I + Ia + Ir Trong : Ia l phn cng b hp th Ir l phn cng b phn x li I l phn cng l ra Da vo v s thc nghim, hai nh bc hc a ra nh lut hp th nh sng, biu din bng biu thc: I = I0 . e-kl cht v vo bc sng ca bxs. nh lut Lambe - Bia ( Lambert - Beer): Khi p dng nh lut Bug - Lambe cho trng hp vt cht l dung dch c dy l ( dung dch ng trong cuvt c dy l ) cha cht hp th c nng C. Nh bc hc Bia a ra nh lut Lambe - Bia: - Ni dung: Vi cng b dy ca lp dung dch, h s hp th k t l vi nng ca cht hp th ca dung dch. - Biu thc: k = *.C hay I = I0 . e-*C.l
9

(2.1)

(2.2)

Trong k l h s hp th, gi tr ca k ph thuc vo bn cht ca vt

(2.3) (2.4)

Nu i logarit t nhin v logarit thp phn th biu thc ca nh lut Lambe - Bia c th biu din bng biu thc: I = I0 . 10-.l.C Trong : C- l nng dung dch, o bng mol/l l - l b dy ca cuvt ng dung dch, o bng cm - c gi l h s tt phn t hay h s hp th phn t. l i lng xc nh, ph thuc vo bn cht ca cht hp th, vo bc sng ca bxs v vo nhit . 2.1.3. Cc i lng hay s dng Biu thc ( 2.5 ) chnh l c s cho phng php phn tch nh lng. Tuy nhin, quan h gia cng nh sng v nng ca dung dch thng qua hm logart, thun tin cho s dng, chng ta thng s dng cc i lng sau: truyn quang T: l t l gia cng chm sng n sc sau khi i qua dung dch I vi cng chm sng n sc chiu vo I0. T = I/I0 = 10-.l.C Nu l = 1cm th T gi l h s truyn quang. Trn cc my phn tch, T thng c biu din bng %, Thang o T t 0 100 Mt quang D (Dentisity) hay hp th A (Absorption) hay tt E (Extinction): c nh ngha theo biu thc sau D = A = E = - lg T = lg(I0 /I) = .l.C Vi cc dung dch cha cht hp th xc nh, ng trong cc cuvt c kch thc nh nhau th v l l khng i, khi ny c th biu din: D = A = K.C (2.7) Hay ni cch khc, s ph thuc gia mt quang v nng dung dch l tuyn tnh, chnh l c s ca phng php phn tch nh lng trc quang phn t. Nh vy nguyn tc chung ca phng php o quang xc nh mt cht X no , ta chuyn n thnh mt cht c kh nng hp th nh (2.6) (2.5)

10

sng ( bxs ) ri o s hp th nh sng ca n v suy ra hm lng cht cn xc nh. Tuy nhin c th p dng biu thc ny i hi phi cp n cc yu t nh hng. 2.1.4. Tnh cht ca mt quang v ng dng trong ha phn tch Biu thc D = A = .l.C cng c th coi l ni dung ca nh lut Lambe - Bia. Nu ta o mt quang ca dung dch c nng 1mol/l ng trong cuvet c b dy 1cm th gi tr mt quang o c chnh l h s hp th phn t, = D, y chnh l ngha vt l ca h s hp th phn t ca mt cht nht nh; ph thuc vo bn cht ca cht hp th nh sng v vo bc sng ca bxs c hp th. o mt quang ca dung dch bng mt cuvt (l, C = const) cc bc sng khc nhau th ta c ng cong biu din ph hp th ca dung dch, D = f() hay = f().

Hnh 2.1. Dng ng cong hp th D = f()


11

o mt quang ca mt dy dung dch c nng khc nhau bng mt cuvt ti mt bc sng nht nh ( l, = const ) th ng biu din D = f(C) s l ng thng.
Mt quang

D6 D5 D4 D3 D2 D1

C1 C2 C3 C4

C5

C6

Nng

Hnh 2.2. Dng ng biu din D = f(C) Mt c tnh rt quan trng ca mt quang l tnh cng tnh, c th chng minh nh sau: Gi s c mt chm bxs c cng I0 i qua 2 dung dch c b dy l1 v l2 tng ng vi cc nng C1, h s tt 1 v C2, h s tt 2 D = lg(I0 /I2 ) = lg(I0 /I1 ) + lg(I1 /I2 ) = D1 + D2 = 1.l1.C1 + 2.l2.C2 Nh vy mt quang ch ph thuc vo s cc phn t hp th nh sng nm trn ng nh sng truyn qua. Trong dung dch c nhiu cht tan hp th bxs th mt quang o c chnh l tng cc mt quang ca cc cht c trong dung dch, D = Di. Khi mun o mt quang ca cht phn tch trong dung dch c nhiu cht th phi loi tr mt quang ca cc thnh phn cn li, chnh l mt quang ca dung dch trng hay dung dch so snh. Dung dch trng hay dung dch so snh l dung dch cha tt cc cc thnh phn trong dung dch phn tch tr cht phn tch. Trong thc t, nhiu khi hp th ca dung dch so snh rt nh, khng ng k th ngi ta c th thay bng nc ct.
12

2.2. Cc iu kin ti u cho mt php o quang Ta bit D = f(,l,C) v theo nh lut Lambe - Bia khi 2 i lng ,l khng i th s ph thuc D = f(C) l tuyn tnh, phi c dng y = ax l mt ng thng, y cng chnh l c s ca phng php phn tch nh lng. Nh vy nhng yu t nh hng n s hp th nh sng l bc sng ca nh sng ti v cc yu t gy nh hng ti nng C c th lm sai lch nh lut Lambe - Bia gy sai s cho php phn tch, v vy ta phi c bit ch n cc yu t ny. 2.2.1. S n sc ca ngun bxt Gi s chm sng ti c cng I0 khng phi l tia sng n sc m l mt chm tia c cng I01, I02, I03 v cht phn tch ch hp th tia th 2 cn khng hp th tia 1 v tia 3, khi ny D = lg( I0 /I) = lg( I01+ I02+ I03)/I01+I2+ I03) Nu tng nng C th I2 s gim cn I01 v I03 vn khng b hp th, khi tng C n mt mc no y th I2 = 0, lc : D = lg( I01+ I02+ I03)/(I01+ I03) = const Lc ny D = f(C) khng tuyn tnh na. Vic to c chm tia bxs c tnh n sc cao li ph thuc vo thit b, ty theo cc my phn tch m b phn to bc x n sc c th l knh lc mu; h lng knh hay cch t vi phn gii c th, khi ny s quy nh tnh chnh xc ca php o. 2.2.2. Bc sng ti u max Cc cht hp th bxs mt cch chn lc, min bxs b hp th mnh nht ng vi nng lng ca bc chuyn in t. Hay ni cch khc, dung dch cht mu m ta phn tch hp th bxs mt cch chn lc, ph hp th cng l mt c trng in hnh ca cht mu. Khi s dng phng php o quang phn tch nh lng mt cht, ngi ta phi dng tia n sc no m khi chiu vo dung dch gi tr mt quang o c l ln nht, gi l mt quang cc i Dmax, khi ny cho kt qu phn tch c nhy v chnh xc tt nht. Bc sng tng ng vi mt
13

quang cc i Dmax gi l bc sng ti u max. Vi mi dung dch nghin cu nht nh, chng ta phi xc nh bc sng max trc khi tin hnh phn tch nh lng. Thng thng cc gi tr max ca cc cht c nghin cu kho st v lit k trong cc bng tra hay cc quy trnh phn tch c sn, chng ta c th tham kho. Hoc chng ta c th xy dng ng cong hp th trn my o quang v t chn max thch hp. 2.2.3. nh hng ca nng Thc nghim chng minh rng quan h gia mt quang D v nng dung dch C ch tuyn tnh trong mt khong gi tr nng xc nh gi l khong tuyn tnh ca nh lut Lambe-Bia, ngi ta quan st c lch khi s ph thuc tuyn tnh gia nng v hp th (H.2.4) .

Hinh 2.3. Khong tuyn tnh ca nh lut Lambe-Bia

Khong tuyn tnh l khc nhau i vi cc my o khc nhau v vi cc i tng phn tch khc nhau. Do phi xc nh khong tuyn tnh cho tng php phn tch c th. 2.2.4. S n nh ca dung dch Trong cc phng php o quang, ngi ta thng a dung dch phn tch v dng dung dch c mu bng cch to phc vi thuc th trong mi trng xc nh. S n nh ca dung dch o l mt yu t rt quan trng php o

14

c chnh xc, s n nh ny thng l: mi trng pH; S c mt ca ion l; Thi gian n nh mu; Nhit ... Nu thuc th dng trong phng php ny thuc dng axit mnh th pH hu nh khng nh hng n s hp th bc x in t. Nu thuc th thuc dng axit yu th yu t pH s nh hng n s to phc v phi tm iu kin mi trng pH ti u cho qu trnh xc nh. Ngoi ra cng phi k n mt s phc mu c mu v bn thay i theo pH, v d phc ca ion Fe3+ vi axt salixilic (H2Sal) mi trng axt pH < 2 c mu tm; mi trng pH t 4 10 c mu v trong mi trng kim pH > 10 c mu vng. Thng thng trong cc mu phn tch ngoi cht phn tch khng th khng k n s c mt ca ion l, cc ion ny c kh nng tng tc vi cht cn phn tch hay to mu vi thuc th trong dung dch cho nn s nh hng n qu trnh xc nh, bt buc phi tm cch loi tr. Hai cch hay s dng nht loi tr l tch chng ra khi dung dch phn tch hoc tm cch che. Vic tch cc ion l ra khi dung dch phn tch ni chung rt kh thc hin do nng ca chng trong dung dch phn tch rt nh cho nn trong thc t phn tch ngi ta thng tm cch che nh hng ca chng bng bin php thch hp, ngha l chng vn trong dung dch phn tch nhng c a vo dng hp cht, thng l dng hp cht phc bn, nn khng nh hng n qu trnh phn tch. V d: ion Fe3+ nh hng n qu trnh phn tch phtpht trong nc, ngi ta thng che nh hng ca n bng cch a v phc bn vi F-; ion Ca2+, Mg2+ nh hng n qu trnh phn tch nitrat v amoni, c che nh hng bng cch a v phc bn vi TrilonB Thi gian n nh mu ca phc gia cht cn phn tch vi thuc th cng l mt yu t quan trng, ta nn kim tra xem thi gian no n nh mu v cng mu ca mt s dung dch th bn nhng i mt s dung dch mu khc th li ch bn trong mt thi gian nht nh. Ni chung vi nguyn tc chung ca phng php l da vo nh lut Lambe - Bia nhng trong tng quy trnh c th cho tng i tng phn tch bao gi cng phi xc nh cc iu kin ti u, l: bc sng cc i max ;
15

khong tuyn tnh v cc iu kin c th nh hng nh nhit ; thi gian; lng thuc th v nu cn phi loi tr nh hng ca cc ion l trong dung dch phn tch. 2.3. Cc my o quang Khng ph thuc vo vng ph, cc my o truyn quang v hp th ( mt quang ) ca dung dch bao gm 5 b phn c bn: - Ngun bc x c nng lng n nh. - B phn to bc x n sc cho php ta chn bc sng ca bc x n sc thch hp vi cht nghin cu. - Cc cuvet cha dung dch o. - tect chuyn tn hiu quang - nng lng bc x - thnh tn hiu o c, thng l tn hiu in. - B phn ch th kt qu o ca tn hiu. S khi tng qut ca mt thit b o quang nh sau:
Ngun bc x lin tc B phn to tia n sc Cuvet ng dung dch Detect Ch th kt qu

Tu theo cu to ca cc loi thit b m ngi ta chia ra lm 2 loi my o quang l my 1 chm tia v my 2 chm tia. phc tp ca cc b phn ring ca cc my o ph hp th ca dung dch cng ph thuc vo cc my khc nhau, vo vng bc sng k c vng s dng cc s liu. V d: o hp th trong vng kh kin ta c cc my so mu bng mt, my so mu quang in, trong vng hng ngoi ta c my quang ph hng ngoi IR, hin nay cc my quang ph hp th phn t thng cho php o trong vng t ngoi UV v c vng kh kin VIS t 190nm n 1100nm, gi chung l cc my quang ph hp th phn t UV - VIS. Sau y chng ta cp n mt s thit b. 2.3.1. Cc my so mu bng mt Trong cc my so mu bng mt th ngun bc x lin tc chnh l nh sng mt tri; etect chnh l mt v b no ca con ngi. Tuy nhin mt v
16

b no ch c kh nng so snh mu ch khng c kh nng cho thng bo v gi tr cng hp th hay mt quang do vy chng ta cn c cc dung dch cht chun so snh mu ca chng vi mu ca cc dung dch cn phn tch. Nh vy nguyn tc chung y l vic so mu ca mu vi mu ca mt dy dung dch chun tm ra cc mu bng nhau, tc l c nng cht cn xc nh nh nhau. Trong phng php ny ngi ta dng cc ng nghim so mu Nexxler, c chun ha sao cho b dy ca cc dung dch u ging nhau. Vi nguyn tc ny ngi ta cng tin hnh qu trnh chun so mu. Cc phng php so mu bng mt c nhiu hn ch nhng chng cng c ng dng rng ri i vi cc php phn tch hng lot nu nhu cu v chnh xc khng cn tht cao. 2.3.2. Cc my so mu quang in My so mu quang in c cu to n gin, tng i r tin thc hin php phn tch nh lng bng phng php o quang. u im ca chng so vi cc my quang ph phc tp chnh l s n gin trong cu to v cch s dng. Mt my so mu quang in thng c 2 chc nng o l truyn quang T hoc mt quang D v b phn ch th kt qu ch l thang o hoc mn hnh digital hin s. Ngun bc x: Ngun bc x hay s dng nht trong my so mu quang in nhn c bc x vng kh kin l si ch ca n vonfram m tnh cht ca n gn vi tnh cht ca vt en tuyt i, khi nung nng n sng trng s pht ra bc x lin tc, bc x ny c nng lng ph thuc vo nhit ly tha bc bn v cng sut bc x mt nhit nht nh li ph thuc vo di sng ly tha bc nm. Ni chung nhit lm vic ca si vonfram t c gn n 2870K, phn chnh ca nng lng do vy c pht x trong vng hng ngoi, ngi ta dng n vi si vonfram trong khong bc sng t 320nm n 2500nm. n cho bc x lin tc v n nh trong vng kh kin phi c s kim tra nghim ngt v hiu th, thng dng my bin th c hiu th c nh hoc mt c quy cung cp cho n mt ngun n nh.
17

B phn to bc x n sc: Knh lc sng c kh nng hp th mt phn xc nh ca ph v tch ra mt chm bc x, coi nh to c mt chm tia n sc, tuy nhin n sc l khng cao. Cc knh lc sng hay dng l cc thy tinh mu hay cc bn thy tinh m gia cc bn ny ngi ta t nhng cht nhum c pha trong gelatin, ty theo my o s c cc b knh lc sng ( knh mu ) vi s lng nht nh. Knh lc giao thoa nh sng c th to c di sng hp hn ( khong 10nm ), c lm t vt liu trong sut t CaF2 hay MgF2, c t gia hai bn thy tinh m b mt ca chng c ph bng cc mng kim loi na trong sut. B dy ca lp vt liu xc nh di sng ca bc x i ra, c kim tra cht ch. S giao thoa nh sng thc hin nh hai lp kim loi, to di truyn quang hp hn, c ngha l c kh nng ln hn to ra bc sng mong mun so vi knh lc hp th. Cc knh lc giao thoa nh sng c sn xut vi cc gii truyn quang trong khong t vng t ngoi cho n gn 6m trong vng hng ngoi. Cuvet ng dung dch o: Cc cuvet c dng trong cc my so mu quang in thng c ch to t thy tinh, mc d cc cuvet cht do trong sut cng c mt s ng dng. Cc cuvet phi c t hon ton vung gc vi chm sng lm gim s mt mt do phn x. tin cy ca php o cng ph thuc nhiu vo cch lm vic ng vi cuvet. Du vn tay, du m v cc cht bn lm thay i ng k kh nng truyn quang ca chng. Do vy nht thit phi lm sch cuvet trc v sau khi dng. Khng c sy cuvet trong t sy hay h trn ngn la. Cc cuvet thng phi c chun ha c h thng so vi nhau nh dung dch so snh. tect: tect c nhim v bin i nng lng bc x thnh tn hiu in, trong cc my so mu quang in hay dng t bo quang in hay nhn quang in. tect ca bc x cn phi tc ng ln bc x trong mt vng rng ca
18

bc sng; phi nhy vi bc x c cng nh v phn ng nhanh vi bc x cho tn hiu in c th d dng khuych i ln. Quan trng nht l lm sao cho tn hiu nhn c t l thun vi cng ca chm sng n, c th nh sau: S = I.k + d Trong : S l tn hiu ca tect trong cc n v cng dng, in tr hay hiu in th. Hng s k l s o nhy ca tect trong cc n v ca tn hiu in trn mt n v cng bc x. i lng d cn gi l dng ti ( dark current ), l mt tn hiu hng nh i vi tect khi khng c bc x. Gi tr ca d thng khng ln, v nguyn tc cc my vi tect c dng ti c trang b mt in k cho php nh mt tn hiu ngc li dn n gi tr d bng khng. Nh vy: I = S/k I0 = S0/k Trong S v S0 l cc tn hiu in ca tect khi bc x i qua dung dch phn tch v dung dch so snh ( dung dch trng ). Thay cc phng trnh ny vo phng trnh nh lut Lambe - Bia ta c: lg( I0/I ) = lg( S0/S ) = D Vi nguyn tc hot ng nh vy, c mt s loi t bo quang in c cp di y. T bo quang in lp chn: c cu to t in cc ng hay st trn c a vo vt liu bn dn, b mt ca cht bn dn c ph mt lp mng trong sut t vng bc hay ch, mng ny cng chnh l in cc th hai hay in cc thu nhn, tt c h c bo v bng mt v bc trong sut. C ch hot ng nh sau: Khi chiu mt chm sng th mt s electron trong lp cht bn dn c mt nng lng ln vt qua bn chn v thm nhp vo mng kim loi. Nu ni mng vi bn theo mt pha khc ca lp bn dn bng si ch bn ngoi v nu in tr khng qu ln th xut hin dng in, dng in ny thng l ln hoc c th c khuych i o bng mt in k hay mt microampe k. Nh vy lc ca dng in t l vi cng ca bc x chiu
19

vo t bo quang in, ni chung cc dng c t 10 n 100A. Cc t bo quang in lp chn ch yu c s dng o bc x trong vng kh kin, nhy cc i vi bc sng khong 550nm v gim cho n bc sng khong 250nm v 750nm. T bo quang in chn khng ( T bo quang in vi hiu ng quang in ngoi ): T bo quang in bao gm mt catt na hnh ng v mt ant dy c t gia mt bnh chn khng. B mt lm ca catt c ph mt lp vt liu nhy nh sng v pht ra electron di tc dng ca bc x. S trn hnh 2.4.

Hnh 2.4. S t bo quang in vi hiu ng quang in ngoi 1- Ch anot; 2- Catot nhy quang; 3- Acquy; 4- in tr; 5- B phn ch th Nu t mt hiu in th vo cc in cc th cc electron bn ra c hng n ant, kt qu s xut hin mt dng in quang, s c khuych i v cho tn hiu o. Dng in nhn c gy ra s gim hiu th dc theo in tr R sau c khuych i v o nh b phn ch th. B mt ca catt nhy quang ca t bo quang in c cu to t mt kim loi kim hay oxyt ca n, c khi l s t hp vi oxyt ca cc kim loi khc; Vt liu catt xc nh c tnh quang ph ca t bo quang in. Cc my so mu quang in do cc hng khc nhau sn xut s khc nhau v phc tp, cc c tnh lm vic v gi thnh. Khng mt my no c th
20

xem l ton nng m vic chn my c xc nh bng loi cng vic m my phi phc v. Di y l s my so mu quang in mt chm tia v hai chm tia.

Hnh 2.5. S my so mu quang in mt v hai chm tia a) My mt chm tia: 1- n vofram; 2- Mng di ng chun ha 100%T; 3Cuvet cha dung dch so snh; 4- Microampe k; 5- Knh lc sng; 6- Cuvet cha dung dch phn tch; 7- T bo quang in vi hiu ng quang in ngoi. b) My hai chm tia: 8- Gng; 9- T bo quang in; 10- in k chun ha 100%T. my hai chm tia dng sng c phn gii nh gng, mt phn i qua dung dch phn tch, phn th hai i qua dung dch so snh. B phn ch th

21

tn hiu l thang o ca truyn quang trong cc n v tuyn tnh t 0 n 100, hoc cng c th l thang o mt quang D. 2.3.3. Cc my quang ph UV- VIS Khc vi my so mu quang in, cc my quang ph UV-VIS hin nay c thit k o ph trong vng t ngoi v trng thy, thng s dng lng knh hay cch t cho php thay i mt cch lin tc di sng; tect l nhn quang in hay ng nhn quang in. Ngun bc x: Trong cc my quang ph UV-VIS hin nay thng trang b 2 loi ngun, trong vng kh kin th dng n vonfram W- Lamp, cn ngun bc x t ngoi c bit n nhiu nht l n hir hay n teri D- Lamp. Cc n hir hay n teri bc x mt ph lin tc do c s chuyn cc phn t kh vo trng thi kch thch. S tr v trng thi ban u c km theo s phn hy ca phn t b kch thch to ra photon ca bc x t ngoi v 2 nguyn t hir trong trng thi c bn. Nng lng c hp th tch ra hai dng v chnh l nng lng ng hc ca cc nguyn t hir v nng lng photon ca bc x t ngoi . Nng lng ng hc cung cp cho c 2 nguyn t hir khng b lng t ha, do vy m nhn c mt ph rng ca nng lng cc 2 nguyn t hir. Cc ngun to bc x n sc ( my to bc x n sc ): lm nhim v phn li bc x thnh bc x n sc c di sng khc nhau, c mt s loi nh sau : - My to bc x n sc bng lng knh

Hnh 2.6. S h thng to bc x n sc bng lng knh


22

1- Khe vo ; 2- Thu knh tp hp ; 3- Lng knh ; 4- Thu knh tiu im; 5- Mt phng tiu im ; 6- Khe ra. C ch hot ng nh sau: bc x i qua khe vo c tp hp vo thu knh thnh chm tia song song v sau chiu n b mt ca lng knh di mt gc xc nh. Trn c 2 mt ca lng knh xy ra s khc x, bc x phn gii sau c tp trung trn mt mt phng hi lm trn c phn b khe ra. Bng cch quay lng knh c th hng bc x vi di sng cn thit vo khe ny. c th t c phn gii nh sng cao, cn c cc bin php k thut nht nh; Tuy nhin vic s dng my to bc x n sc vi quang hc thy tinh ch gii hn trong vng kh kin do thy tinh hp th bc x t ngoi. - My to bc x n sc bng cch t ( mng li ):

Hnh 2.7. S phn gii to chm bc x n sc trn mng li phn x S phn gii cc bc x kh kin, t ngoi k c hng ngoi c th thc hin c bng cch cho chm bc x i qua cch t trong sut hay phn x bc
23

x t mt li phn x. Cc cch t l mt cc thy tinh hay mt vt liu trong sut khc trn c vch ra cc ng song song. Khi c s chiu sng cch t bng mt chm bc x i qua khe th mi vch s tr nn mt ngun bc x mi. Kt qu giao thoa ca nhiu chm sng th bc x s c phn gii thnh cc phn vi cc di sng khc nhau. Nu chm bc x c tp trung trn mt mt phng ta s nhn c mt ph m dng ca n lp li dng ca khe vo. Cch t thch hp dng trong cc vng kh kin v t ngoi c gn 600 vch trn 1cm. Cc mng li phn x nhn c bng cch ct cc l rnh trn b mt c nh bng ca kim loi. Tng t, bc x c phn x t mi phn li ln ca mng li v s giao thoa ca cc chm phn x s gy ra s phn gii bc x. Ngoi ra cn c cc my to bc x n sc i, bao gm t hai cu phn phn gii, c ngha l gm hai lng knh, hai mng li hay lng knh v mng li. S kt hp ny lm cho kh nng phn gii ca my tng ln rt nhiu. Cuvet: thng s dng cuvet thy tinh cho vng kh kin, nu o trong vng t ngoi th phi dng cuvet thch anh. Cc tct : Trong cc my UV-VIS th tct l cc t bo quang in vi hiu ng quang in ngoi hay cc nhn quang in. Trn hnh 2.8 l s cu trc ca mt nhn quang in. B mt ca catot v thnh phn khng khc b mt catot ca t bo quang in pht ra cc electron khi chiu sng. Nhn quang in cn cha cc in cc ph c k

24

Hnh 2.8. S nhn quang in hiu bng s t 1 n 9 gi l cc inot. Hiu th trn inot 1 dng hn 90V so vi trn catot, do vy m cc electron c tng tc theo hng ca n. Khi p ln inot, mi electron gy ra s pht x mt s electron b sung, n lt cc electron ny li hng n inot 2 m hiu th ca n dng hn 90V so vi hiu th ca inot 1. Mt ln na c mi mt electron p ln b mt li pht ra mt s electron. Khi qu trnh ny lp li 9 ln th c mi mt photon nhn c 106 109 electron. Tp hp cc electron ny cui cng hng ti anot, dng in c tng cng nhn c ny i qua in tr R, sau c th khuych i b sung v c o. Tng t nh cc my so mu quang in, cc my UV-VIS ging nhau s khi nhng s khc nhau v phc tp, cc c tnh lm vic v gi thnh. Trong cc my hai chm tia, bng cch no chm sng c chia i hoc gia my to bc x n sc hoc theo li ra khi my ny : mt chm i qua dung dch phn tch v mt chm khc i qua dung dch so snh. Trong mt
25

s my, ngi ta so snh cng ca c hai chm nh mt h i ca cc tct v cc b khuych i sao cho nhn c ngay mt quang hay truyn quang. Trong cc my khc, bc x ca ngun c tch ra mt cch c hc v cc xung nh sng ln lt i qua cc dung dch phn tch v dung dch so snh. Sau chm sng cui cng c cu to li v ri vo mt tct, qua b phn khuych i v cui cng cho nhn tn hiu o l mt quang hay truyn quang. 2.3.4. Cc my quang ph hng ngoi IR Cc my IR c cu trc tng t nh my UV-VIS, trong ngun bc x lin tc l n vonfram cho bc x c bc sng < 2m); n Nernst cho bc x c bc sng trong khong 0,4 20m, l dy l xo t oxit ziriconi v ytri c nung nng bng dng in n 1500oC hoc Globar, l dy l xo t cacbit silic cho bc x c bc sng trong khong 1 4m khi c nung nng bng dng in n 1500oC hoc cng c th l dy Nicrom ( Ni + Cr ). i vi vng hng ngoi trong thy tinh v thch anh khng trong sut th ngi ta ch to cc lng knh t vt liu nh natri clorua, liti florua, canxi florua hay kali bromua. Cc vt liu ny cng dng to cuvet hay to mu o ph hng ngoi. Tuy nhin nhng cht ny chu s phn hy c hc v tng tc ca hi nc, do vy khi lm vic vi chng phi c cc bin php k thut thch hp. Cc my IR ni chung u l h thng hai chm tia v thng s dng thm d v ghi mt vng rng ca ph. 2.4. Cc phng php phn tch nh tnh v nh lng Ph hp th phn t c dng rng ri trong cc php phn tch nh tnh v nh lng. nhn bit cc hp cht, nht l cc hp cht hu c th ph hng ngoi IR c ngha c bit v chng c cha mt lng ln cc pic hp, c trng cho cht, mi hp cht hu c li c mt cu trc ph tinh vi. Ngc li ph hp th trong vng kh kin v t ngoi thng gm cc di ph b dn rng, iu ny lm che mt cc cu trc tinh vi ca chng nn khng thch hp nhn bit nhng li c gi tr quan trng phn tch nh lng.
26

Ngoi ra nhng nghin cu quang ph trong vng ny thng cho thng bo nh tnh b ch v s c mt hay khng c mt ca mt s nhm chc trong cc hp cht hu c ( nh nhm cacbonyl; vng thm ; nhm nitro hay lin kt i lin hp). Mt ng dng quan trng khc ca ph hp th phn t l pht hin hn hp hp th mnh trong mi trng khng hp th, nu h s hp th trong cc i hp th ln th d dng thit lp s c mt nhng lng vt nhim bn. Hnh 2.9 v 2.10 cho thy ph hp th ca mt s cht.

27

Hnh 2.9. Mt s ph hp th t ngoi 1- Hi natri; 2- Hi benzen; 3- Benzen trong hexan ; 4- dyphenyl trong hexan.
28

Hnh 2.10. Ph hng ngoi ca anehyt CH3 CH2CH2CHO 1- Cc dao ng ha tr ca lin kt C- H ca nhm metyl; 2- Cc dao ng ha tr ca lin kt C- H ca nhm anehyt; 3- Cc dao ng ha tr ca lin kt C=O; 4- Cc dao ng bin dng ca lin kt C- H ca nhm anehyt. Di y chng ta ch yu cp n phng php phn tch nh lng cho cc my so mu quang in hay my UV-VIS, cn gi l cc phng php trc quang phn t hay o quang. Cn cc phng php ph hng ngoi IR s c chuyn ring. phn tch nh lng trc quang phn t, c hai phng php hay c s dng l phng php ng chun; phng php thm chun; ngoi ra cn c phng php vi sai. Tuy nhin trc khi thc hin cc phng php ny, ngi phn tch phi tm c cc iu kin ti u cho s lm vic ca my o, xc nh bc sng cc i max v khong tuyn tnh ca nng . 2.4.1. Phn tch nh lng bng phng php ng chun Khi phn tch hng lot nhiu mu, ngi ta thng s dng phng php ng tiu chun, phng php ny cho php phn tch v tnh ton kt qu nhanh, c th trit tiu c cc sai s h thng, thng c lp trnh sn trong cc phn mm iu khin ca my. Quy trnh thc hin nh sau : Chun b mt dy dung dch chun c nng chnh xc, tng dn nht nh C1, C2, C3, C4, C5, C6 ca cht chun phn tch, cht chun phn tch X c a v dng phc mu bng thuc th thch hp.
29

o mt quang D1, D2, D3, D4, D5, D6 ca cc dung dch chun ti bc sng max kho st Xy dng ng chun D = f(C). Chun b mu trong iu kin tng t, o mt quang Dx Da vo ng chun suy ra nng Cx
Mt quang

D6 D5 D4 D3 D2 D1

C1 C2 C3 C4

C5

C6

Nng

2.4.2. Phn tch nh lng bng phng php thm chun o mt quang ca dung dch phn tch Dx Thm mt lng cht chun a vo dung dch phn tch, o mt quang Dx+a t cc gi tr o c, xc nh nng ca mu Cx
Cx D C a .Dx = x Cx = C x + C a Dx+ a Dx+ a Dx

2.5. Phng php trc quang c C s ca phng php trc quang c l da vo hin tng hp th hay tn x nh sng bi cc ht huyn ph ( keo ) c trong dung dch phn tch. Phng php phn tch da trn s o cng dng sng khuych tn ( tn x ) Ir bi cc ht keo ( huyn ph ) trong dung dch gi l phng php khuych c. Phng php phn tch da trn s o gim cng dng sng sau khi i qua dung dch do cc ht keo hp th mt mt phn gi l phng php hp c. 2.5.1. Phng php khuych c
30

Hnh 2.11. ng i ca tia sng qua h keo I0- cng dng sng ban u, Ir- cng dng khuych tn, It - cng dng cn li ra khi dung dch. C s ca phng php l s ph thuc cng dng khuych tn Ir (do cc ht huyn ph sinh ra) vo nng dung dch phn tch tun theo phng trnh R-ly (Relay), c dng rt gn nh sau: Ir = I0K(N.V2/4) Trong : N - tng s cc ht huyn ph trong dung dch, tc l t l vi nng cht phn tch. - bc sng ca nh sng ti I0 V- th tch ht huyn ph K - h s t l, ph thuc vo bn cht ca dung dch v iu kin o S ph thuc ny ni chung rt phc tp, ty thuc vo iu kin tin hnh th nghim, tin hnh o, tuy nhin nu c khng ch nghim ngt th l c s ca phng php phn tch nh lng. 2.5.2. Phng php hp c C s ca phng php da trn s o cng dng sng It i ra khi dung dch phn tch. T l I0/It tun theo phng trnh:
31

lg(I0/It) = k.Cbd3/( d4 + 4 ) trong : C - Nng cc phn t ( ht keo ) hp th nh sng trong dung dch b - Chiu dy lp dung dch d - ng knh trung bnh ca cc ht keo k, - Nhng h s, ty thuc vo bn cht cc ht keo v phng php o - Bc sng ca nh sng ti I0 Nu d, k, , c nh th: lg(I0/It) = KbC cng l phng trnh c bn ca nh lut Lambe-Bia, vy trong phng php hp c cng dng php o mt quang phn tch nh lng. Dhp c = lg(I0/It) = KbC Tuy nhin trong cc phng php trc quang c, c th thu c kt qu chnh xc, c tin cy cao cn phi tun th rt nghim ngt cc iu kin thc nghim, c th nh: - Cc ht keo ( huyn ph) phi t tan - Cc ht keo ( huyn ph) iu ch c phi ng nht - Cc ht keo ( huyn ph) phi bn vi thi gian, khng b lng ng. t c cc iu kin ny li ph thuc vo nhiu yu t thc nghim nh: nng , th t, tc khi cho cht phn tch v thuc th tc dng vi nhau to ht huyn ph; Thi gian cn thit thu c c cc i hay n nh ca ht keo; s c mt ca cc cht l nh cht tr keo, cht in gii ngoi lai k c yu t nhit

32

Chng 3. PHNG PHP QUANG PH HP TH NGUYN T AAS ( ATOMIC ABSORPTION SPECTROMETRY ) 3.1. C s l thuyt ca phng php 3.1.1. S xut hin ph hp th nguyn t Nh chng ta bit, vt cht c cu to bi cc nguyn t v nguyn t l phn t c bn nh nht cn gi c tnh cht ca nguyn t ha hc. Trong iu kin bnh thng nguyn t khng thu v cng khng pht ra nng lng, lc ny nguyn t trng thi c bn, y l trng thi bn vng v ngho nng lng nht ca nguyn t. Nhng khi nguyn t trng thi hi t do, nu ta chiu mt chm tia sng c bc sng xc nh vo m hi nguyn t , th cc nguyn t t do s hp th cc bc x c bc sng nht nh ng ng vi nhng tia bc x m n c th pht ra c trong qu trnh pht x ca n. Lc ny nguyn t nhn nng lng ca cc tia bc x chiu vo n v chuyn ln trng thi kch thch c nng lng cao hn trng thi c bn. Qu trnh ny gi l qu trnh hp th nng lng ca nguyn t t do trng thi hi v to ra ph ca nguyn t ca nguyn t , ph sinh ra trong qu trnh ny c gi l ph hp th nguyn t. Nu gi nng lng ca tia sng b nguyn t hp th l E th: E = Em - E0 = h = hc/ Trong : E0 v Em l nng lng ca nguyn t t do trng thi c bn v trng thi kch thch m; h l hng s Planck; c l tc ca nh sng trong chn khng; v l tn s v bc sng ca vch ph hp th. Nh vy ng vi mi gi tr nng lng Ei m nguyn t hp th s c mt vch ph hp th vi di sng i c trng cho qu trnh , ngha l ph hp th nguyn t l ph vch. Nhng nguyn t khng hp th tt c cc bc x m n c th pht ra trong qu trnh pht x, qu trnh hp th ch xy ra i vi cc vch ph nhy, cc vch ph c trng ca cc nguyn t. y chnh l s khc nhau c bn khi mun to ph hp th hay ph pht x ca nguyn t: to ph pht x, phi kch thch nguyn t bng nng lng Em, to ph

33

hp th th phi kch thch nguyn t bng chm tia n sc ph hp. Hnh 3.1 cho thy qu trnh to ph hp th v ph pht x ca nguyn t.

Hnh 3.1. Qu trnh pht x v hp th ca nguyn t E0 : nng lng trng thi c bn; Em : nng lng trng thi kch thch; +h v E : nng lng kch thch; -h : tia pht x Tm li, mun c ph hp th nguyn t trc ht phi to ra m hi nguyn t t do, sau chiu vo n mt chm sng n sc c bc sng nht nh, ng ng vi cc tia pht x nhy ca nguyn t cn nghin cu. Khi ny, nguyn t t do s hp th nng lng ca chm tia n sc v to ra ph hp th nguyn t, da vo cng vch ph hp th nguyn t phn tch nh lng. y cng chnh l iu kin quyt nh cu trc ca mt my quang ph hp th nguyn t AAS, chng ta s cp n phn sau. 3.1.2. Cng ca vch ph hp th Khi nghin cu s ph thuc ca cng mt vch ph hp th ca mt nguyn t vo nng C ca nguyn t trong mu phn tch, l thuyt v thc nghim cho thy rng, trong mt vng nng C nh ca cht phn tch, mi quan h gia cng vch ph hp th v nng N ca nguyn t trong m hi nguyn t t do cng tun theo nh lut Lambe-Bia. Ngha l

34

nu chiu mt chm sng c cng ban u l I0 qua m hi nguyn t t do ca nguyn t c nng nguyn t l N v b dy l L cm, th c: I = I0 .e-(K . N. L) ring cho tng vch ph hp th ca mi nguyn t. Nh vy nu gi D (hay A) l cng vch ph hp th nguyn t, chnh l tt ca chm sng cng ban u l I0 qua mi trng hp th, cn gi l hp th hay mt quang, th c: D = lg( I0/I ) = 2,303 K. N. L (3.2) Trong cc my o AAS, b dy L ph thuc vo cu trc ca my, nn c th coi nh khng i, vy D ch ph thuc vo s nguyn t N trong mi trng hp th, khi ny biu thc (3.2) c th vit l: D = K.N (3.3) trong K l h s thc nghim, ph thuc vo cc yu t: h s hp th K ca vch ph hp th; b dy ca mi trng hp th v nhit ca mi trng hp th. Ngoi ra gia s nguyn t N ca nguyn t trong mi trng hp th v nng C ca nguyn t trong mu phn tch cng c quan h nht nh, mi quan h ny rt phc tp, ph thuc vo iu kin nguyn t ha mu; thnh phn vt l, ha hc, trng thi tn ti ca nguyn t trong mu. Nhng cc kt qu thc nghim cng ch ra rng, trong mt gii hn nht nh ca nng C th mi quan h gia N v C c th biu th theo cng thc: N = Ka . Cb (3.4) Trong Ka l h s thc nghim, ph thuc vo tt c cc iu kin thc nghim ca php o ph. H s b c gi l hng s bn cht, n ph thuc vo tng vch ph ca tng nguyn t, b c gi tr bng 1 v nh hn 1. Gi tr b = 1 khi nng C l nh v ng vi mi vch ph ca mi nguyn t phn tch, ta lun tm c mt gi tr C = Co b bt u nh hn 1. By gi c th biu din l: D = k.Cb
35

(3.1)

Trong K l h s hp th nguyn t ca vch ph tn s , K c trng

(3.5)

Vi C < Co th lun c b = 1 v khi C > Co th b nh hn 1, gi tr Co c coi l gii hn ca vng tuyn tnh. Hnh 3.2 di y cho bit quan h gia D v C; phng trnh (3.5) c gi l phng trnh c s ca php o nh lng cc nguyn t theo phng php quang ph hp th nguyn t AAS.

Hnh 3.2. Quan h gia D v C 3.2. Nguyn tc v trang thit b ca php o AAS 3.2.1. Nguyn tc chung ca phng php Phng php phn tch da trn c s o ph hp th nguyn t ca mt nguyn t c gi l php o ph hp th nguyn t ( php o AAS ), c s l thuyt ca php o nh xt trn, l s hp th nng lng (dng bc x n sc) ca nguyn t t do trong trng thi hi ( kh ) khi chiu chm tia n sc qua m hi nguyn t t do ca nguyn t y trong mi trng hp th. V vy mun thc hin php o AAS ca mt nguyn t cn phi thc hin cc qu trnh sau y: 1. Chn cc iu kin v mt loi trang 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. Qu trnh ny gi l qu trnh ha hi v nguyn t ha mu. Nhng trang b thc hin qu trnh ny c gi l h thng nguyn t
36

ha mu. Nh chng ta c c m hi ca cc nguyn t t do ca cc nguyn t trong mu phn tch, m hi ny chnh l mi trng hp th bc x v sinh ra ph hp th nguyn t. 2. Chiu chm tia bc x c trng ca nguyn t cn phn tch qua m hi nguyn t va iu ch c trn, cc nguyn t ca nguyn t cn phn tch trong m hi s hp th nhng tia bc x nht nh v to ra ph hp th ca n. y, phn cng ca chm tia bc x b mt loi nguyn t hp th l ph thuc vo nng ca n trong mi trng hp th. Ngun cung cp chm tia bc x c trng ca nguyn t cn phn tch c gi l ngun bc x n sc hay bc x cng hng. 3. Tip theo, nh mt h thng quang hc, thu ton b chm sng, phn li v chn mt vch ph hp th ca nguyn t cn phn tch o cng ca n. Trong mt gii hn nht nh ca nng C, gi tr cng ny l ph thuc tuyn tnh vo nng C ca nguyn t trong mu phn tch theo phng trnh (3.5) vi b = 1. 3.2.2. S h thng my o ph hp th nguyn t AAS Ba qu trnh trn chnh l nguyn tc ca php o AAS, t cng quyt nh cc b phn c bn ca my o ph hp th nguyn t AAS, bao gm cc phn sau: 1. B phn th nht l ngun pht tia bc x n sc (chnh l vch ph pht x c trng ca nguyn t cn phn tch) nn cn gi l ngun bc x cng hng, chiu vo mi trng hp th cha cc nguyn t t do ca cc nguyn t trong mu phn tch. C cc loi ngun: n catt rng; n phng in khng in cc hay cc ngun pht bc x lin tc c bin iu. 2. B phn th hai l h thng nguyn t ha mu phn tch, h thng ny c ch to theo hai loi k thut nguyn t ha mu, l: - K thut nguyn t ha mu bng ngn la n kh, lc ny ta c php o F - AAS. H thng ny li bao gm b phn dn mu vo bung aersol ha mu to th sol kh v n nguyn t ha mu, t chy hn hp kh c cha mu th huyn ph sol kh.
37

- K thut nguyn t ha mu khng ngn la, lc ny ta c php o ETA - AAS. H thng ny c l nung nh bng grapht (cuvet grapht) hay thuyn Tantan (Ta) nguyn t ha mu nh ngun nng lng in c th thp (nh hn 12V) nhng c dng rt cao (50 800A). 3. B phn th ba l mt h quang hc, chnh l b n sc, c nhim v thu, phn li v chn vch ph hp th cn o hng vo nhn quang in (tct) pht tn hiu hp th AAS ca vch ph. 4. B phn th t l h thng ch th tn hiu hp th ca vch ph ( tc l cng ca vch ph hp th hay nng ca nguyn t phn tch). H thng ny c th l cc trang b sau: - n gin nht l mt in k ch nng lng hp th ca vch ph - Mt my t ghi pic ca vch ph - B hin s digital - B my in hay k c tch phn k Ni chung cc my hin nay u kt ni vi mt my vi tnh, cho php iu khin ton b qu trnh o; tm cc iu kin ti u cho php o; x l cc kt qu o. H thng my AAS cng bao gm hai loi l h mt chm tia v h hai chm tia. Hnh 3.3 di y l s nguyn tc chung ca cc my AAS

38

Hnh 3.3. S nguyn tc cu to h thng my AAS a) H mt chm tia; b) H hai chm tia 1-Ngun pht tia bc x n sc; 2- H thng nguyn t ha mu; 3- h thng n sc v tct; 4- h thng khuych i v ch th kt qu o. 3.2.3. Mt s b phn ca my AAS 3.2.3.1. Ngun pht bc x n sc thc hin php o ph hp th nguyn t trc ht phi c ngun pht ra tia bc x n sc ca nguyn t cn phn tch chiu vo mi trng hp th. Ngun pht tia bc x n sc phi tha mn nhng yu cu sau y: - Phi to c tia pht x nhy ( cc vch pht x nhy, c trng ) ca nguyn t cn phn tch. Chm tia ny phi c cng n nh v c th iu chnh c. - Phi to c chm tia pht x thun khit ch bao gm mt s vch nhy, c trng ca nguyn t cn phn tch cn ph nn khng ng k. - Chm tia pht x n sc phi c cng cao, bn vng theo thi gian v khng b cc yu t vt l nhiu lon hn ch s nh hng v vt l v v ph trong php o. Cc my AAS hin nay dng ch yu ba loi ngun, l: n catt rng; n phng in khng in cc; n pht ph lin tc c bin iu. Di y l nhng gii thiu s b v cc loi n ny. n catt rng HCL ( Hollow Cathode Lamp )
39

y l ngun pht tia bc x n sc c dng sm nht v ph bin nht trong php o ph AAS. n ny ch pht ra tia pht x nhy ca nguyn t kim loi lm catt. Cu to ca n nh trong hnh 3.4, bao gm ba phn chnh l: Thn v v n; in cc; Kh trong n v ngun nui n.

Hnh 3.4.Cu to ca n catt rng HCL Thn n gm c v n, ca s v b cc in cc ant v catt. Thn v v n bng thy tinh hay thch anh. Ca s S cng bng thy tinh hay thch anh trong sut trong vng UV hay VIS l ty thuc vo loi n ca tng nguyn t pht ra chm tia pht x nm trong vng ph no. in cc ca n l catt v ant. Ant c ch to bng kim loi tr v bn nhit nh W hay Pt; Catt c ch to bng chnh kim loi cn phn tch vi tinh khit cao 99,9% c dng hnh ng rng. Ant l mt vng bao quanh catt, c hai in cc c gn cht trn b v catt phi nm ng trc xuyn tm ca n. Hai u ca hai in cc gn cht trn n, cm vo ngun in nui cho n lm vic. n c t nng nh mt ngun in mt chiu n nh, th lm vic ca n HCL thng khong 250 220V ty thuc vo tng loi n ca tng hng v tng nguyn t kim loi lm catt. Cng lm vic ca n HCL thng khong 3 50mA v cng ty thuc vo tng loi n. Th v cng dng in lm vic ca n c lin quan cht ch n cng tch kim loi ra khi b mt catt to ra hi kim loi sinh ra chm tia pht x ca n. Mi n HCL thng c mt gi tr cng cc i ghi trn v n, khi s dng khng bao gi c php dng n dng in cc i , thch hp nht l trong khong 65 85% gi tr cc i.

40

Kh trong n l kh tr vi p sut khong 5 15mHg, l kh Ar, He hay N2 c tinh khit n 99.99%, phi m bo khng pht ra ph lm nh hng n chm tia pht x ca n v khi n lm vic trong mt iu kin nht nh th t s gia cc nguyn t b ion ha v cc nguyn t trung ha phi khng i. C ch lm vic ca n nh sau: nh ngun in, catt c nung , gia catt v ant xy ra s phng in lin tc, nh mt s phn t kh b ion ha, cc ion mi sinh ny s tn cng b mt catt ang nng lm cho mt s nguyn t ca kim loi trn b mt catt b ha hi v tr thnh nhng nguyn t t do, di tc dng ca nhit trong n ang c t nng, cc nguyn t t do ny b kch thch v pht ra ph pht x ca n. chnh l ph vch ca kim loi lm catt, v trong iu kin mi trng kh tr c p sut rt thp, ph pht x ch bao gm cc vch nhy ca kim loi m thi. Chm tia pht x ny l ngun n sc chiu vo mi trng hp th thc hin php o AAS. Cc n HCL c cu to nh m t trn l cc n n, mi n ch phc v cho phn tch mt nguyn t. Hin nay cc hng ch to c cc n kp i (Ca + Mg; Cu + Mn; K + Na ) , kp ba (Cu + Pb + Zn) hay kp su nguyn t (Cu + Mn + Cr + Fe + Co + Ni), khi ny catt ca n phi l hp kim ca cc nguyn t v thnh phn phi ph hp sao cho cng pht x ca cc nguyn t l gn tng ng nh nhau, khng nh hng ln nhau. Cc n kp thng c nhy km hn cc n n tng ng v ch to cng kh hn n n nn n nay cng ch c mt s loi m thi. n phng in khng in cc EDL (Electrodeless Discharge Lamp) n EDL l ng phng in trong mi trng kh him c cha nguyn t cn phn tch vi nng nht nh ph hp to ra chm tia pht x ch bao gm mt s vch ph nhy, c trng ca nguyn t phn tch. Cu to ca n gm cc b phn sau: - Thn n l ng thch anh chu nhit, di 15 18cm, ng knh 5 6cm. Mt u ca n cng c ca s S cho chm tia pht x i qua. Ngoi ng
41

thch anh l cun cm bng ng c cng sut t 400 800W ty loi n ca tng nguyn t v c ni vi ngun nng lng cao tn ph hp nui cho n lm vic. - Cht trong n l vi miligam kim loi hay mui kim loi d bay hi ca nguyn t phn tch, lm sao khi ton b cht ha hi bo m cho p sut hi ca kim loi trong n nhit 550 800oC l khong 1 1.5mHg. Cht ny thay cho catt trong n HCL, n chnh l ngun cung cp chm tia pht x ca nguyn t phn tch, khi chng b kch thch, khi n lm vic. - Trong n EDL cng phi ht ht khng kh v np thay vo l mt kh tr Ar, He hay N2 c p sut vi mHg khi u cho s lm vic ca n. - Ngun nng lng cao tn nui n c ch to theo hai tn s: tn s sng ngn 450MHz v tn s sng radi 27.12MHz c cng sut di 1kW nn c hai loi n tng ng hai tn s trn. C ch lm vic ca n nh sau: khi n lm vic, di tc dng ca nng lng cao tn cm ng, n c nung nng , kim loi hay mui kim loi trong n c ha hi v b nguyn t ha, cc nguyn t t do c sinh ra s b kch thch v pht ra ph pht x ca n. chnh l vch pht x nhy, c trng ca kim loi cha trong n. So vi n HCL, n EDL cho nhy cao hn, n nh hn. n EDL ca cc kim hay bn kim thng c bn cao hn v vng tuyn tnh ca php o cho mt nguyn t cng rng hn so vi n HCL. Tuy nhin s n EDL c sn xut t hn, khong hn 30 n v gi thnh li cao hn. n ph lin tc c bin iu Trong cc my AAS, hin nay c xu hng s dng ngun pht bc x lin tc nhng nh h thng quang hc ( bin iu v lc giao thoa ) to chm bc x n sc. l cc n Dteri D2-Lamp; n wonfram W-Lamp, pht ph lin tc trong vng t ngoi v vng kh kin UV-VIS. C ch lm vic ca n nh sau: chm sng khi i qua h thng bin iu v b lc giao thao s b bin iu theo nhng di sng nht nh dao ng vi bin nh nhau, sau c chiu vo mi trng hp th l ngn
42

la hay cuvet graphit. Cc nguyn t t do trong mi trng hp th s hp th mt phn nng lng ca chm sng ng vi mt di bin iu ca vng ph, phn cn li s i vo b n sc v etect pht hin v o cng sau khi qua b khuych i bng sng theo di ph ca n nn li tn s. Ngun pht ph lin tc c u im l d ch to, r tin v c bn tng i cao. Ch cn mt n c th thc hin php o AAS i vi nhiu nguyn t trong vng ph UV-VIS nn rt u vit i vi cc my ph hp th nhiu knh v xc nh ng thi hay lin tip nhiu nguyn t trong cng mt mu phn tch m khng phi thay n. V n sc v nhy th ngun pht ph lin tc km hn cc n HCL hay EDL, tuy nhin hin nay loi ngun ny c pht trin, ci tin v s dng rt nhiu trong cc my AAS. 3.2.3.2. Thit b nguyn t ha mu Qu trnh nguyn t ha mu l mt giai on rt quan trng trong php o AAS bi v ch cc nguyn t t do mi cho ph hp th nguyn t, s nguyn t t do l yu t quyt nh cng vch ph hp th v nh hng trc tip n kt qu phn tch. Mc ch ca qu trnh ny l to ra c m hi cc nguyn t t do t mu phn tch vi hiu sut cao v n nh, php o t kt qu chnh xc v c lp li cao. Hai h thng k thut nguyn t ha mu sau y to ra hai dng my AAS khc nhau. 3.3.1.1. K thut nguyn t ha mu bng ngn la My AAS vi h thng ny cho php o AAS c k hiu l F- AAS ( vit tt ca Flame Atomic Absorption Spectrometry ). Theo k thut ny ngi ta dng nng lng nhit ca ngn la n kh ha hi v nguyn t ha mu phn tch. Trang thit b nguyn t ha mu bng ngn la: mun thc hin php o F - AAS, trc ht phi chun b mu phn tch trng thi dung dch, sau dn dung dch mu vo ngn la n kh ha hi v nguyn t ha mu v thc hin php o. Qu trnh nguyn t ha trong ngn la gm hai bc k tip nhau: bc mt l chuyn dung dch mu thnh th cc ht nh nh sng m ( dng sol kh ) trn u vi kh mang v kh chy, qu trnh ny c
43

gi l qu trnh aerosol ha hay nbulize ha; bc hai l dn hn hp aerosol cng hn hp kh t vo n ( burner head ) nguyn t ha. C h thng ny gi l Nebulizer System, bao gm hai phn chnh l n nguyn t ha mu ( burner head ) v bung aerosol ha mu. to ra ngn la, ngi ta t chy hn hp kh bao gm mt kh oxyha v mt kh chy, thng s dng hn hp kh acetylen v khng kh nn hay hn hp kh acetylen v kh N2O. Khi hn hp kh c t chy, burner head s to ra ngn la, di tc dng nhit ca ngn la cc phn t mu th sol kh s b ha hi v nguyn t ha to ra cc nguyn t t do ca nguyn t c trong mu phn tch. l mi trng hp th nng lng v to ra ph hp th nguyn t ca nguyn t cn phn tch. Hnh 3.4 v 3.5 di y l mt v d v cc loi n v h thng nguyn t ha mu bng ngn la

Hnh 3.4. Hai loi n nguyn t ha mu

44

Hnh 3.5. H thng nguyn t ha mu bng ngn la 1- n nguyn t ha mu; 2- Mng bo him; 3- ng thi phn dung dch mu tha; 4- ng dn kh oxyha; 5- ng dn mu vo bung aersol ha; 6- ng dn kh chy; 7- Vin bi to aersol. Ti u ha cc iu kin nguyn t ha mu bng ngn la Qu trnh nguyn t ha mu l giai on rt quan trng trong php o FAAS, qu trnh ny thc hin khng tt s nh hng trc tip n kt qu o. V vy, mun t c kt qu chnh xc v ng n, chng ta phi kho st chn cc iu kin nguyn t ha mu ti u, ph hp nht cho tng nguyn t
45

cn phn tch trong mi loi mu c th. Sau y chng ta xem xt mt s iu kin c th. 1- Thnh phn v tc ca hn hp kh t to ra ngn la: vic thay i thnh phn v tc ca hn hp kh t cho php chn nhit ph hp ha hi v nguyn t ha mu, to ra m hi cc nguyn t t do c kh nng hp th bc x n sc to ra ph hp th nguyn t. Ngn la n kh phi tha mn cc yu cu sau: - Ngn la n kh phi lm nng u c mu phn tch; ha hi v nguyn t ha mu vi hiu sut cao. - Nhit ( nng lng ) ca ngn la phi ln v c th iu chnh c ty theo tng mc ch phn tch mi nguyn t. ng thi phi n nh theo thi gian v c th lp li trong cc ln phn tch khc nhau m bo cho php phn tch t c kt qu ng n. Yu cu ny c lc khng c tha mn v nhit cao nht ca ngn la cng ch t c l 3300oC, do i vi nhng nguyn t to thnh hp cht bn nhit th hiu sut nguyn t ha ca ngn la l km. - Ngn la phi thun khit, khng sinh ra cc vch ph ph hay to ra ph nn qu ln lm kh khn cho php o. Qu trnh ion ha v pht x phi khng ng k v qu trnh ny lm mt cc nguyn t t do to ra ph. - Ngn la phi c b dy ln c lp hp th dy lm tng nhy ca php o. ng thi b dy ca lp hp th li c th thay i c khi cn thit, o cc nng khc nhau. Trong cc my hin nay, b dy ny c th thay i c t 2cm n 10cm. - Tiu tn t mu phn tch. Ngn la l mi trng nguyn t ha mu, trong ngn la c nhiu qu trnh ng thi xy ra, c qu trnh chnh v c cc qu trnh ph ( gi l qu trnh th cp ), trong nhit ca ngn la l yu t quyt nh. Nhit ca ngn la ph thuc vo bn cht; thnh phn ( t l ) hn hp kh v tc dn hn hp kh vo n t chy. Cu trc ca ngn la li gm ba phn c nhit khc nhau, c m t trong hnh 3.6. Trong , phn (a) l phn ti
46

ca ngn la, c nhit thp trong khong 700oC 1200oC, trong phn ny hn hp kh c trn u v t nng cng vi cc ht sol kh ca mu phn tch, dung mi ha tan mu s bay hi v mu c sy nng. Phn (b) l vng trung tm ca ngn la, c nhit cao, nht l nh b, thng khng c mu hoc mu xanh rt nht. Trong phn ny hn hp kh c t chy tt nht v khng c phn ng th cp. V th trong php o phi a mu vo phn ny nguyn t ha, ni cch khc l ngun n sc phi chiu vo phn ny. Phn (c) l v v ui ca ngn la, vng ny c nhit thp, ngn la c mu vng v thng xy ra nhiu phn ng th cp khng c li cho php o.

Hnh 3.6. Cu to ca ngn la n kh Qu trnh xy ra trong ngn la c th m t nh sau: mu th sol kh c dn ln n nguyn t ha, ming n xy ra s bay hi ca dung mi ha tan mu v cc cht hu c (nu c) trong th sol kh. Khi ny mu cn li l nhng ht rn rt nh mn c dn tip vo vng trung tm ngn la, y s xy ra cc qu trnh chnh l ha hi v nguyn t ha ca cc ht mu kh, tuy nhin qu trnh ny s din bin theo tnh cht nhit ha ca ht mu: mu s
47

ha hi dng phn t sau cc phn t kh ny mi b phn li ( nguyn t ha ) thnh cc nguyn t t do; hoc ngc li, cc ht mu phn li thnh cc nguyn t t do ri mi ha hi. l hai c ch ca qu trnh ha hi v nguyn t ha mu trong ngn la n kh. Thc nghim cho thy rng cc loi hp cht ca kim loi dng halogenua; kim loi axetat; kim loi clorat; kim loi nitrat thng theo c ch th nht, c ch ny cho php o c nhy cao v n nh hn c ch th hai. Cc loi hp cht ca kim loi sunphat; kim loi phtphat; kim loi silicat thng theo c ch th hai, c ch ny km n nh, cho php o c nhy thp. V vy ngi ta thng thm vo mu cc mui halogen hay axetat ca kim loi kim hng cc qu trnh theo c ch th nht u vit hn. Bn cnh cc qu trnh chnh, trong ngn la cn c mt s qu trnh ph, cc qu trnh ny thng nh hng n cng vch ph trong nhng mc khc nhau, v d nh: S ion ha ca cc nguyn t ca nguyn t cn phn tch; S pht x ca cc nguyn t t do; S hp th nng lng ca cc ion v phn t, k c cc ht mu rn cha b ha hi; Cui cng l s to thnh cc hp cht bn nhit dng oxyt dng MeO, cc loi hp cht ny rt bn, khi hnh thnh th s kh phn ly thnh cc nguyn t t do trong ngn la n kh, lm nh hng n kt qu o. 2. Tc dn dung dch mu vo h thng nguyn t ha: Tc ph hp ca mt s my hin nay l trong khong 4 - 5ml/pht. 3. Chiu cao ca n nguyn t ha: Yu t ny cng nh hng trong mt mc nht nh. Ty thuc vo tng nguyn t m chn chiu cao burner head sao cho c c cng vch ph ln nht v n nh nht. 4. B dy ca mi trng hp th L. Khi thay i b dy ca lp hp th (mi trng hp th) chng ta c th tng hay gim nhy ca php o. Ngha l ty theo nng ca nguyn t cn phn tch m chng ta thay i gc nghing ca n nguyn t ha mu c c b dy ca lp hp th L ph hp nht. Khi L ln nht ta s c nhy cao nht, nu gim L th nhy gim theo, ni cch khc nu khi o nng ln ta phi quay n nguyn t ha i
48

mt gc cho ph hp, m khng cn pha long, nhng sau phi gi khng i trong sut qu trnh o. 5. Tn s my siu m to sol kh mu phn tch cng cn chn cho ph hp k c tc dn mu vo bung siu m. Trn y l cc yu t nh hng n php o F-AAS trong yu t th nht l quan trng nht, quyt nh hiu sut ca qu trnh nguyn t ha mu, cc yu t cn li nh hng n yu t th nhtv qua m nh hng n kt qu ca php o. 3.3.1.2. K thut nguyn t ha mu khng ngn la K thut nguyn t ha khng ngn la ra i sau k thut nguyn t ha bng ngn la, nhng k thut pht ny trin rt nhanh v hin nay ang c ng dng rt ph bin. K thut ny cho php o AAS c nhy cao hn rt nhiu so vi k thut nguyn t ha bng ngn la, mc nanogram - ppb. y l u im chnh ca k thut ny, v vy khi phn tch lng vt cc kim loi trong nhiu trng hp khng cn thit phi lm giu cc nguyn t cn phn tch, c bit l khi xc nh cc nguyn t vi lng trong cc loi mu y hc, sinh hc, dc phm, thc phm Nguyn tc v cc giai on ca qu trnh nguyn t ha mu khng ngn la Nguyn tc v cch thc hin ca k thut nguyn t ha khng ngn la l hon ton khc vi k thut nguyn t ha trong ngn la. y thng dng nng lng nhit ca mt ngun nng lng ph hp nung nng, ha hi v nguyn t ha mu phn tch trong ng cuvt graphit hay trong thuyn tantan (Ta) nh. Ngun nng lng thng c dng hin nay l dng in c cng dng rt cao (50 - 600A) v th thp (di 12V) hay l nng lng ca dng cao tn cm ng (ICP). Di tc dng ca cc ngun nng lng ny, cuvt cha mu s c nung nng tc khc v mu ha hi v nguyn t ha to ra cc nguyn t t do trng thi hi c kh nng hp th bc x n sc to ra ph hp th nguyn t ca n.

49

Nh vy, h thng nguyn t ha mu theo k thut khng ngn la gm c: - Bung nguyn t ha v cuvt cha mu phn tch. - Ngun nng lng nung nng l graphit n nhit nguyn t ha mu v b iu khin hay b chng trnh t chng trnh v ch huy qu trnh nguyn t ha mu. Ty theo cc hng sn xut m h thng nguyn t ha mu ny c th c cu trc v cch s dng khc nhau, nhng qu trnh nguyn t ha mu trong cc dng c ny u xy ra theo 3 giai on k tip nhau trong khong thi gian 60 n 80 giy, l: Sy kh mu; Tro ha luyn mu v cui cng l nguyn t ha mu. Sy kh mu l giai on u tin ca qu trnh nguyn t ha mu. Yu cu ca giai on ny l phi m bo dung mi ha tan mu bay hi nh nhng v hon ton, khng lm bn mu, mt mu. Nhit v thi gian sy kh ca mi mu l ph thuc vo bn cht ca cc cht trong mu v dung mi ha tan n. Thc nghim cho thy rng khng nn sy kh qu nhanh nhit qu cao, ni chung nhit sy kh ph hp vi a s cc mu v c trong dung mi nc nm trong khong t 100 - 150oC trong thi gian t 25 - 40 giy vi lng mu bm vo cuvt nh hn 100l. Cc mu hu c trong dung mi hu c phi sy nhit thp hn v tc tng nhit cng phi chm hn. Tro ha mu l giai on tip theo t chy cc hp cht hu c v mn c trong mu sau khi sy kh ng thi cng nung luyn mu mt nhit thun li cho giai on nguyn t ha tip theo t hiu sut cao v n nh. Giai on ny nh hng rt nhiu n kt qu phn tch nu chn nhit tro ha khng ph hp. Thc nghim cho thy mi nguyn t u c mt nhit tro ha luyn mu gii hn ca php o ETA-AAS, l nhit m s tro ha luyn mu ti nhit hoc nh hn n th cng vch ph hp th l khng i, cn nu tro ha nhit ln hn th cng vch ph b gim v khng n nh, iu ny c th l gii l do mu b phn hy mt. Nhit gii hn ca mi nguyn t l khc nhau v ph thuc vo bn cht, dng hp cht m nguyn t tn ti, k c matrix ca mu. Ni chung cc nguyn t bn
50

nhit v tn ti dng hp cht bn nhit thng phi tro ha luyn mu nhit tng i cao, v d Si c nhit tro ha gii hn l 1100oC, Ni c nhit tro ha gii hn l 1000oC, Pb li c nhit tro ha gii hn ch c 600oC Trong cc ti liu km theo my phn tch AAS thng gii thiu ngi s dng tham kho v nhit sy mu, nhit tro ha luyn mu v nhit nguyn t ha mu, tuy nhin khi phn tch cc mu c th chng ta nn da vo cc gi tr kho st hoc kim tra li. Ngoi ra cng phi k n tc tng nhit trong qu trnh tro ha luyn mu, nu tc tng nhit qu ln s lm bn mu, thng thng ngi ta dnh 1/3 tng thi gian tro ha luyn mu cho qu trnh tng nhit t nhit sy n nhit tro ha, nh vy tc tng nhit khong 60oC 100oC trong 1 giy; 2/3 thi gian cn li l gi nhit khng i chn luyn mu. i vi nhng mu ca hp cht hu c hay trong dung mi hu c th giai on ny cng phi cn thn trnh s bay hi trc ca nguyn t phn tch dng hp cht c kim. Ni chung vi mi loi mu, trong mi loi dung mi u phi kho st pht hin nhit tro ha, tc tng nhit cho ph hp. Nguyn t ha l giai on cui cng ca qu trnh nguyn t ha mu nhng l giai on quyt nh cng vch ph v b nh hng bi hai giai on trn. Giai on ny c thc hin trong thi gian rt ngn, thng thng t 3 n 6 giy, t khi n 8 - 10 giy nhng tc tng nhit li l rt ln t ngay tc khc nhit nguyn t ha v thc hin php o cng vch ph. Tc tng nhit khong 1800oC 2500oC trong 1 giy, thng s dng tc ti a m my c th cho php. 3.2.3.3. H thng n sc y l h thng quang hc, cng gi l my quang ph c phn gii cao, c nhim v thu, phn li v chn vch ph hp th cn o. H ny c th l mt chm tia hay hai chm tia bao gm ba phn chnh: - H chun trc, chun trc chm tia vo. - H thng tn sc (phn li) phn li chm sng a sc thnh n sc. - H bung ti ( bung nh ) hi t cc tia cng bc sng li.
51

Trc h chun trc l khe vo ca chm sng a sc v sau h bung nh l khe ra ca chm tia n sc cn o. Nh th hin hnh 3.7, chm tia pht x cng hng ca nguyn t cn phn tch c pht ra t ngun sau khi i qua mi trng hp th, s c hng vo khe my v vo h chun trc, ri vo b phn tn sc, vo h hi t chn mt tia cn o hng vo khe o ca etct o cng vch ph hp th. H thng n sc ca mi my AAS phi m bo mt s yu cu sau y: 1. Phi c tn sc ln c th tch v c lp c tt cc vch ph cn o, trnh s quy ri, s chen ln ca cc vch ph khc bn cnh. Trong cc my hin nay thng l h cch t c hng s t 1200 2400 vch/nm. 2. Phi khng gy ra cc hin tng sai lch lm mt nng lng ca chm sng trong my nh s hp th, s tn x, s khuych tn ca cc b phn cu thnh my, c bit l cc h thng gng, cc thu knh trong my. 3. Khe vo, khe ra ca my phi c m chnh xc v phi iu chnh c cho ph hp vi tng vch ph v c lp li cao trong mi php o. Cc thu knh phi trong sut trong vng ph lm vic ca my. 4. tct pht hin cng vch ph phi c nhy cao, c th pht hin s thay i nh trong qu trnh hp th ca vch ph ca mi nguyn t. Ni chung trong cc my AAS l loi tct nhy nht, l ng nhn quang in ( photomultivlier tube). 3.2.3.4. tct ng nhn quang in - photomultivlier tube tct l dng c quang hc c kh nng bin tn hiu quang thnh tn hiu in, ni cch khc l dng c quang hc thu nhn v pht tn hiu quang hc theo hiu ng quang in ca n. chng hai chng ta xt mt s loi t bo quang in, sau y chng ta xt mt loi tct c tnh cht vn nng, c nhy v chn lc rt cao, l ng nhn quang in ( photomultivlier tube), vng ph hot ng l 190 900nm c khi n 1100nm, c th khuych i tn hiu o ln n hng triu ln ( 106 107 ), s cu to

52

trong hnh 3.7. Nguyn liu ch to bn catt l cc hp kim ca kim loi kim vi Sb, Ga hay As, v d hp kim Cs - Sb; Ga - As; Na - K - Cs - S

Hnh 3.7. Nguyn tc cu to ca ng nhn quang in 3.3. Cc yu t nh hng n php o AAS Cc yu t nh hng n kt qu phn tch trong php o ph hp th nguyn t l rt a dng v phc tp, c khi xut hin v cng c khi khng, ngi ta thng chia thnh 6 nhm nh sau: Nhm 1 l cc thng s ca h my o. Cc thng s ny cn c kho st v chn cho tng trng hp c th. Thc hin qu trnh ny chnh l ti u ha cc thng s ca my o cho mt i tng phn tch. Nhm 2 l cc iu kin nguyn t ha mu. Cc yu t ny th hin rt khc nhau ty thuc vo k thut c chn thc hin qu trnh ha hi v nguyn t ha mu, c cp phn trn. Nhm 3 l k thut c chn x l mu. Trong qu trnh ny, nu thc hin khng cn thn c th s lm mt hay nhim bn thm nguyn t phn tch vo mu, do kt qu phn tch thu c l khng ng vi mu thc t.

53

V vy vi mi loi mu ta phi nghin cu v chn mt quy trnh x l mu ph hp nht. Nhm 4 l cc nh hng v ph. Trong php o AAS, ngoi vch ph c chn o cn c ph nn, hoc s chen ln ca cc vch ph ca cc nguyn t khc khng phi l nguyn t cn phn tch, chng nh hng rt mnh n kt qu phn tch, v vy cn quan tm nghin cu loi b s nh hng ny. Nhm 5 l cc yu t vt l. Nhm 6 l cc yu t ha hc. Sau y chng ta xem xt mt vi yu t. 3.3.1. Cc yu t nh hng v ph nh hng u tin phi k n s hp th bc x ca nn, yu t ny c lc xut hin r rng, nhng cng c khi khng xut hin. iu ny ph thuc vo vch ph c chn o nm trong vng ph no. Thc nghim cho thy, trong vng kh kin th yu t ny th hin r rng, cn trong vng t ngoi li t xut hin. Hn na s hp th nn cn ph thuc rt nhiu vo thnh phn nn ca mu phn tch, c bit l matrix ca mu, ngha l nguyn t c s ca mu. V d, khi xc nh Pb trong mu sinh hc th s hp th nn l khng ng k nhng khi xc nh Pb trong nc bin ( khong vi % NaCl ) nh hng ny li v cng ln. Trong cc my AAS hin nay u c h thng b chnh nn. Mt hin tng cng thng xy ra l s chen ln cc vch ph. Yu t ny thng thy khi cc nguyn t th ba trong mu phn tch c nng ln v thng l nguyn t c s ca mu. Tuy nguyn t ny c cc vch ph khng nhy nhng do nng ln nn cc vch ny vn xut hin vi rng ln, nu n li nm cnh cc vch phn tch th chng s chen ln cc vch phn tch, lm cho vic o cng vch ph phn tch rt kh khn v thiu chnh xc, nht l i vi cc my c phn gii khng cao. V th trong mi trng hp phn tch c th cn phi nghin cu v chn nhng vch ph hp loi tr s chen ln ca cc vch ph ca cc nguyn t khc, nu khng loi tr
54

c cc nh hng ny th li phi tm cch loi b cc nguyn t ny t qu trnh x l mu. Ngoi ra cn phi k n s hp th ca cc ht rn rt nh tn ti trong mi trng hp th ca ngn la n kh, l cc ht li ti ca vt cht mu phn tch cha b ha hi v nguyn t ha, hay cc ht mui ccbon ca nhin liu cha c t chy hon ton. Cc ht ny thng c lp v ca ngn la, chng hp th hoc chn ng i ca chm sng n sc t ngun bc x chiu vo mi trng hp th. Yu t ny c gi l s hp th gi, th hin rt r khi chn khng ng chiu cao ca n nguyn t ha mu v khi hn hp chy khng c t chy tt, hay do thnh phn ca hn hp kh chy khng c chn ph hp. 3.3.2. Cc yu t vt l Thuc v cc yu t ny, thng c nhng nh hng sau: 1. nht v sc cng b mt ca dung dch mu: Yu t ny nh hng n tc dn mu vo bung aerosol ha v hiu sut aerosol ha mu v t nh hng n kt qu phn tch. Ni chung tc dn mu l t l nghch vi nht ca dung dch. Nguyn nhn s khc nhau v nht v sc cng b mt ca dung dch mu l s khc nhau v nng axt, loi axt, nng ca cht nn ca mu, thnh phn ca cc cht c trong dung dch mu. li tr nh hng ny, chng ta thng dng cc bin php sau y: - o v xc nh theo phng php thm tiu chun. - Pha long mu bng mt dung mi hay mt nn ph hp. - Thm vo mu mt cht m c nng ln. - Dng bm y mu vi mt tc xc nh cn thit. 2. Hiu ng lu li, thng th hin trong php o ph khng ngn la, c th gii thch c ch nh sau: khi nguyn t ha mu o cng vch ph th mt lng nh ca nguyn t phn tch khng b nguyn t ha, chng c lu li trn b mt cuvet v c th tch t qua mt s ln nguyn t ha mu, nhng n mt ln no th n li b nguyn t ha theo v do to ra s nguyn t t do tng t ngt khng theo nng ca n trong mu, ngha l
55

lm tng cng vch ph v dn n lm sai lc kt qu phn tch. Yu t ny xy ra v cng ln khi mu phn tch c nng ln, ng thi cng ph thuc vo bn cht ca nguyn t cn phn tch, dng hp cht n tn ti trong mu, nht l loi cuvet grapht c dng. Cc cuvt c ch to t grapht hot ha thng hn ch c hiu ng ny, ngha l khi b mt cng mn th nh hng cng nh, b mt cng xp th nh hng cng ln. loi tr cc nh hng ny, c th lm nh sau: - Lm sch cuvt sau mi ln nguyn t ha mu, lm bay hi ht cc cht cn li trong cuvet. Tt nhin phi thc hin nhit cao hn nhit nguyn t ha nguyn t phn tch. - Dng cc loi cuvt c ch to t grapht hot ha ton phn, c b mt chc v mn. - Khi phn tch nn o nhng mu c nng nh trc. - Trng b mt ca cuvt bng mt lp nhng hp cht bn nhit. 3. S ion ha: l yu t nh hng mnh n kt qu phn tch, v s ion ha lm gim s nguyn t t do ca nguyn t cn phn tch trong mi trng hp th to ra ph, lm gim cng vch ph. Mc ion ha ca mi nguyn t l khc nhau v ph thuc vo nhit ca mi trng hp th. Ni chung, vi mt iu kin nht nh, cc nguyn t c th ion ha cng thp th cng b ion ha nhiu; Vi mt nguyn t, nhit ca mi trng hp th cng cao th nguyn t b ion ha nhiu hn. Thc nghim cng cho thy, qu trnh ion ha xy ra mnh vi cc nguyn t kim loi kim, sau l kim loi kim th, cn i vi cc nguyn t khc th khng ng k. loi tr s ion ha, c th dng cc bin php nh: - Chn iu kin nguyn t ha c nhit thp, m trong iu kin nguyn t phn tch hu nh khng b ion ha. - Thm vo mu phn tch mt cht m cho s ion ha, thng l mui halogen ca kim loi kim vi nng ln ph hp, chng c th ion ha thp hn th ion ha ca nguyn t phn tch, trong iu kin ny nguyn t phn tch s khng b ion ha na.
56

4. S kch thch ph pht x ca nguyn t phn tch trong mi trng hp th, yu t ny lm gim s nguyn t trung ha trong mi trng hp th, do cng lm gim cng ca vch ph hp th. Hin tng ny thng xy ra vi cc nguyn t kim loi kim, sau l kim loi kim th, cn i vi cc nguyn t khc th khng ng k. loi tr nh hng ny c th dng cc bin php nh: - Chn nhit nguyn t ha mu thp ph hp m ti s kch thch ph pht x ca nguyn t phn tch l khng xy ra hoc khng ng k. - Thm vo mu phn tch mt cht m hn ch s pht x ca nguyn t phn tch. Chnh l cc mui halogen ca kim loi kim, c th kch thch ph pht x thp hn th kch thch ph pht x ca nguyn t phn tch. Trn y l mt s yu t vt l c th xut hin trong php o AAS v c th nh hng n kt qu phn tch. Nhng mc xy ra l rt khc nhau trong mi trng hp c th, c khi c, c khi khng, do cn phi xem xt tm bin php loi tr ph hp. 3.3.3. Cc yu t ha hc Trong php o AAS, nh hng ca cc yu t ha hc cng rt a dng v phc tp, xut hin cng rt khc nhau trong mi trng hp c th, mt s yu t thng nh hng nh sau: 1. Nng axt v loi axt trong dung dch mu: Nng axt trong dung dch mu lun c nh hng n cng ca vch ph ca nguyn t phn tch, s nh hng ny thng gn lin vi loi anion ca axt. Cc axt cng kh bay hi thng cng lm gim nhiu cng ca vch ph, cn cc axt d bay hi gy nh hng nh hn. Thc nghim xc nh cc axt lm gim cng ca vch ph theo th t tng dn nh sau: HClO4 < HCl < HNO3 < H2SO4 < H3PO4 < HF. Chnh v th trong thc tin phn tch, ngi ta thng dng mi trng l HCl hay HNO3 nng khong 1% 2% v nng ny nh hng ca hai axt l khng ng k. 2. nh hng ca cation l: Trong dung dch mu, ngoi nguyn t cn phn tch, thng cn cha cc nguyn t khc, s tn ti ca cc nguyn t ny di
57

dng cation hay anion c th lm tng, cng c th lm gim, cng c khi khng nh hng n cng ca vch ph. Khi c nh hng th mc nh hng cng rt khc nhau trong tng trng hp c th, nhiu nghin cu chuyn mn su v phng php AAS cp c th tng loi v nng cation gy nh hng. Cng phi lu rng, nh hng ca cation trong dung dch mu n cng ca vch ph ca nguyn t cn phn tch trong php o AAS vi k thut nguyn t ha mu bng ngn la v khng ngn la cng rt khc nhau. V d ion La(III) trong php o F - AAS l yu t loi tr nh hng ca cc ion l khi xc nh Ca, Mg, Mn, Al, Fe. Nhng chnh ion La(III) trong php o ETA - AAS li lm gim cng ca vch ph khi xc nh Ca, Mg, Mn, Al, Fe. iu ny c ngha l mi cation trong tng tng hp c th v trong mi php o li c nh hng khc nhau v chng ta cn quan tm, kho st. 3. nh hng ca anion: s nh hng ny tng t nh nh hng ca cc loi axt, cc anion ca cc axt d bay hi thng t lm gim cng ca vch ph, ring hai anion ClO4- v CH3COO- li gy s tng cng ca vch ph (hiu ng dng). Cc anion gy hiu ng m (gim cng ca vch ph) theo th t tng dn l: Cl- < NO3- < CO32- < SO42- < PO43- < SiO32- , ngoi ra khi nng anion tng th tc dng nh hng cng tng theo. V vy trong mi php o phi gi cho nng ca cc anion trong mu phn tch v mu chun l nh nhau v mt gi tr khng i, mt khc cng khng nn chn H2SO4 lm mi trng ca mu cho php o AAS m ch nn dng HCl hay HNO3 nng di 2%. 4. nh hng ca thnh phn nn, yu t ny cn c gi l matrix effect. nh hng ny xut hin cc mu c cha cc nguyn t nn di dng cc hp cht bn nhit, kh bay hi v kh nguyn t ha, chnh cc cht ny lm kh khn v cn tr qu trnh ha hi v nguyn t ha ca cc nguyn t cn phn tch. loi tr nh hng ny c th dng cc bin php nh: - Tng nhit nguyn t ha mu. - Thm vo mu cc cht ph gia c nng ph hp ngn cn s xut hin cc hp cht bn nhit.
58

- Tch, loi b cc nguyn t nn, khi hai bin php trn khng t c. Trong ba bin php ny, bin php th nht cng ch thc hin c trong chng mc nht nh, v khng th tng nhit nguyn t ha mu ln cao mi c do s hn ch ca trang thit b, bn cht ca kh t, hn na nu tng nhit ln cao qu th s xut hin nh hng ca s ion ha v s pht x. Bin php th hai l thng dng nht, cc cht ph gia hay dng l LaCl3; SrCl2; LiCl; KCl; AlCl3 cho php o F - AAS, trong LaCl3 c s dng rng ri nht. Trong php o ETA - AAS hay s dng LiBO2, NH4NO3 hoc hn hp ca hai cht ny vi nng ph hp. 5. nh hng ca dung mi hu c: Thc nghim cho thy s c mt ca dung mi hu c trn ln vi nc trong dung dch mu phn tch, hay mu phn tch ha tan trong dung mi hu c thng lm tng cng ca vch ph ln nhiu ln. y chnh l mt phng php tng nhy ca phng php phn tch, khi phn tch cc nguyn t c nng nh st gii hn di ca php o, chng ta c th thm vo dung dch mu phn tch mt dung mi hu c c nng ph hp th c th tng nhy ca phng php phn tch ln n vi ln so vi khi ch dng dung mi nc. Tuy nhin dung mi hu c thm vo phi tinh khit trnh nhim bn mu v phi trn u c vi nc, trong thc t nu dung mi hu c khng ha tan c trong nc th chng ta c th chit nguyn t phn tch t dung mi nc dng hp cht phc vo dung mi hu c ri o ph hp th ca nguyn t phn tch trong dung mi hu c . 3.4. Cc phng php phn tch nh lng 3.4.1. Phng trnh c bn ca php o AAS Nh ni trn, phng trnh 3.5 chnh l phng trnh c bn ca php o AAS D = k.Cb (3.5) Vi Cx < Co th lun c b = 1 v khi Cx > Co th b nh hn 1, gi tr Co c coi l gii hn ca vng tuyn tnh. th di y cho bit quan h gia D v C v

59

khong tuyn tnh ca mi php o, khong tuyn tnh ny l thay i trong tng trng hp phn tch c th v phi kho st xc nh.

3.4.2. Mu u dng ng chun Trong phng php phn tch nh lng AAS, cc dung dch chun (cn gi l mu u) dng ng chun cng bt buc phi tha mn mt s iu kin nht nh, l: 1. Cc mu u phi c trng thi vt l v ha hc nh mu phn tch. Ngha l mu phn tch trng thi, dung mi, mi trng v dng lin kt no th mu u cng phi c tnh cht ging nh th. C nh vy th mi loi tr c nh hng ca thnh phn ca mu n kt qu phn tch. 2. Cc mu u v mu phn tch phi c x l, chun b trong cng iu kin nh nhau. 3. Cc mu u phi bn vng theo thi gian, thnh phn ng nh tnh ton ban u c th s dng lu di. 4. Nng ca cc nguyn t cn phn tch trong cc mu u phi rt chnh xc theo yu cu ca phng php phn tch, ng thi khong nng ca mt dy mu u phi phn b u trong vng tuyn tnh ca php o. 3.4.3. Khi nim v nhy v gii hn pht hin ca php o AAS
60

3.4.3.1. Khi nim v nhy nhy l mt i lng ch ra kh nng ca phng php phn tch, phng php phn tch c nhy cao tc l nng gii hn di c th phn tch c l nh. nhy ca php o AAS ph thuc vo cc yu t nh: h thng my o; iu kin v k thut nguyn t ha mu, php o F-AAS c nhy km php o ETA-AAS; Kh nng v tnh cht hp th bc x ca mi vch ph, vch ph no, nguyn t no c kh nng hp th bc x cng mnh th php o cng nhy, i vi mt nguyn t th cc vch ph khc nhau cng c nhy khc nhau. Chnh v vy khi ni n nhy ca mt nguyn t l phi gn lin vi iu kin phn tch c th. Trong php o AAS nhy tuyt i v nhy tng i c nh ngha l: - nhy tuyt i l lng gam ( khi lng ) nh nht ca nguyn t cn phn tch phi c trong mi trng hp th cn thu c cng ca vch ph chn gp 3 ln tn hiu nn ( hoc chim 1% ton bng hp th ). Nh vy mi nguyn t v mi vch ph s c nhy tuyt i khc nhau, khi phn tch cc nguyn t c nng nh phi chn cc vch c nhy cao o. - nhy tng i l nng nh nht ca nguyn t cn phn tch c trong mu cn pht hin c tn hiu hp th ca n theo mt vch ph chn v tn hiu ny phi bng 3 ln tn hiu nn ( hoc chim 1% ton bng hp th ). Loi nhy ny c dng ph bin hn nhy tuyt i, k c trong cc phng php phn tch khc. 3.4.3.2. Khi nim v gii hn pht hin Bn cnh khi nim v nhy, ngi ta cn s dng gii hn pht hin i vi mt nguyn t khi dng mt vch ph xc nh n. Cng tng t nh nhy, gii hn pht hin cng phn bit hai khi nim, l: - Gii hn pht hin tuyt i ca mt nguyn t l khi lng ti thiu ca nguyn t cn c trong mi trng hp th cn pht hin c tn hiu hp th ca n trong mt iu kin nht nh chn.
61

- Gii hn pht hin tng i ca mt nguyn t theo mt vch ph nht nh c th xem l nng nh nht ca nguyn t c trong mu cn pht hin c tn hiu hp th ca n theo vch ph trong mt iu kin nht nh chn. Trong cc ti liu chuyn mn, hoc catalo i km theo cc my AAS, bao gi cng lit k cc gi tr nhy tuyt i, nhy tng i, gii hn pht hin tuyt i, gii hn pht hin tng i ca tng vch ph ca tng nguyn t. 3.4.4. Cc phng php nh lng bng php o AAS Cng tng t nh cc phng php phn tch my khc, phn tch nh lng c hai phng php chnh l phng php ng chun v phng php thm chun. 3.4.4.1. Phng php ng chun Chun b mt dy dung dch chun ( mu u ), t nht l 3 mu, thng thng l 5 n 6 mu, c nng chnh xc, tng dn nht nh, v d: C1, C2, C3, C4, C5, C6 ca cht chun phn tch. Sau chn cc thng s ca my, cc iu kin ph hp v o cng ca vch ph hp th ca nguyn t phn tch trong cc dung dch mu chun, v d: gi tr cng tng ng vi cc nng trn l D1, D2, D3, D4, D5, D6 . Xy dng ng chun D = f(C). Dung dch mu phn tch c nng Cx cha bit cng c chun b v o nh cc dung dch mu chun, c gi tr Dx Da vo ng chun suy ra nng Cx Phng php ny n gin, d thc hin v rt tch hp khi phn tch hng lot nhiu mu ca cng mt nguyn t, nh trong kim tra nguyn liu sn xut, cht lng thnh phm..., y l u im ca phng php ny. Song trong nhng iu kin khi m chng ta khng th chun b c dung dch mu chun c thnh phn ging nh dung dch mu phn tch, nguyn nhn l do dung dch mu phn tch c thnh phn phc tp cha xc nh c, khi ny s

62

rt d mc sai s ln. Trong nhng trng hp ny, chng ta nn dng phng php thm tiu chun. 3.4.4.2. Phng php thm tiu chun Trong thc tin phn tch, c bit l khi xc nh lng vt cc kim loi, thng gp phi cc i tng phn tch c thnh phn phc tp nn khng th chun b c dung dch mu chun thch hp. Trong trng hp ny th tt nht l dng phng php thm tiu chun loi tr c nh hng ca thnh phn mu (Matrix effect ). Nguyn tc ca phng php ny l ngi ta dng ngay mu phn tch lm nn chun b mt dy dung dch mu u, bng cch ly mt lng dung dch mu phn tch v gia thm vo nhng lng nht nh ca nguyn t cn phn tch theo tng bc nng . V d lng thm vo l C1, C2, C3, C4, nh th chng ta s c mt dy mu chun l: C0 = Cx C1 = Cx + C1 C2 = Cx + C2 C3 = Cx + C3 C4 = Cx + C4 Trong Cx l nng ca nguyn t cn phn tch. Tip cng chn cc iu kin th nghim ph hp v mt vch ph ca ca nguyn t cn phn tch, tin hnh ghi cng hp th ca vch ph trong dy mu chun, v d ta c cc gi tr: D0, D1, D2, D3 v D4. T cc gi tr ny, xy dng mt ng chun theo h ta D - C. ng chun ny ct trc tung D ti im c ta ( D0; 0 ), sau xc nh nng Cx cha bit, ta lm nh sau: - Cch 1: Ko di ng chun v pha tri, ct trc honh ti im C0 , on OC0 chnh bng gi tr nng Cx . - Cch 2: T gc ta k mt ng song song vi ng chun v t im D0 k ng song song vi trc honh, hai ng ny ct nhau ti im M,

63

t M h ng vung gc vi trc honh, ct trc honh ti im C0 , on OC0 chnh bng gi tr nng Cx phi tm. Phng php ny c u im l chun b mu d dng, khng cn nhiu ha cht tinh khit cao chun b dy mu chun nhn to. Mt khc li loi tr c hon ton nh hng v thnh phn ca mu cng nh cu trc vt l ca cc cht to thnh mu. Tuy nhin phi ch rng nng thm vo ca nguyn t cn phn tch phi theo tng bc v khong cch ca cc bc phi xp x nng Cx th phn ni suy tuyn tnh mi chnh xc. Phng php ny c s dng rt nhiu trong phn tch lng vt v lng cc nh cc nguyn t kim loi trong cc loi mu, c bit l cc loi mu c thnh phn phc tp, cc mu qung a kim. ng thi y cng l phng php xc nh pht hin ca phng php phn tch. 3.4.5. Cc phng php phn tch trc tip v gin tip bng php o AAS Trong php o ph hp th nguyn t AAS xc nh mt nguyn t hay mt hp cht, ngi ta c th tin hnh phn tch ngay chnh cht theo ph hp th nguyn t ca n, nh phn tch kim loi, hay thng qua vic o ph hp th nguyn t ca mt cht khc, khi cht phn tch khng c tnh cht hp th nguyn t, nhng cht ny li c mt s tng tc rt nh lng v mt ha hc theo mt phn ng ha hc nht nh vi mt kim loi c ph hp th nguyn t nhy. V vy xut hin hai loi phng php phn tch nh lng theo ph hp th nguyn t AAS, l: - Cc phng php phn tch trc tip, p dng phn tch cc cht c ph hp th nguyn t AAS - Cc phng php phn tch gin tip, p dng phn tch cc cht khng c ph hp th nguyn t AAS 3.4.5.1. Cc phng php phn tch trc tip Cc phng php phn tch trc tip ph hp nht cho vic xc nh cc kim loi c vch ph hp th nguyn t. V th i tng ca cc phng php ny l phn tch kim loi trong cc mu v c v hu c, cc mu v c nh qung, t , , hp kim, xi mng, nc, khng kh... cn cc mu hu c nh
64

thc phm, ng, sa, hp, nc gii kht, cc mu sinh hc nh mu, serum, nc tiu, thc vt... Nguyn tc chung ca phng php phn tch trc tip bao gm hai giai on: - Giai on 1: x l mu a nguyn t kim loi cn xc nh c trong mu v trng thi dung dch ca cc cation theo mt quy trnh ph hp chuyn c hon ton nguyn t kim loi cn xc nh vo dung dch o ph. Giai on ny l cc k quan trng v nu x l mu khng tt s lm mt nguyn t cn xc nh hay lm nhim bn thm vo. Ni cch khc nu x l mu khng ng s l ngun sai s ln cho kt qu phn tch mc d phng php phn tch chn l ph hp nht. - Giai on 2: tin hnh phn tch nguyn t kim loi theo mt cch ph hp nh cp trn. 3.4.5.2. Cc phng php phn tch gin tip Trong nhng nm gn y cc phng php phn tch gin tip c s dng nhiu phn tch cc cht khng c ph hp th nguyn t, v d nh phn tch cc anion, cc nhm phn t, cc hp cht hu c, cc loi dc phm... Nguyn tc ca phng php phn tch gin tip l nh mt phn ng ha hc trung gian c tnh cht nh lng ca cht cn phn tch vi mt thuc th thch hp trong mt iu kin nht nh. Sau y chng ta xem xt mt vi phng php gin tip nh phn ng ha hc trung gian. 1. Phn ng ca cht phn tch vi mt ion kim loi to ra mt kt ta: Ni chung cht no khi tc dng vi ion kim loi to ra mt kt ta t tan, c tnh cht nh lng v c th tch ra c khi dung dch mu th phn ng c th dng c cho php o ny. Theo nguyn tc ny ngi ta xy dng cc phng php phn tch cc ion nh: Cl-, NH4+, SO42-, PO43-, C2O42-... V d xc nh hm lng ion SO42- trong mu, ngi ta cho ion ny tc dng vi dung dch BaCl2 hay Pb(NO3)2 c nng xc nh trong iu kin ph hp to ra kt ta BaSO4 hay PbSO4 , lc tch kt ta khi dung dch. Sau xc nh Ba hay Pb theo hai cch, hoc l trong kt ta sau khi ha tan chng, hoc
65

xc nh lng Ba hay Pb cn d trong dung dch sau khi phn ng hon ton vi lng ion SO42- trong mu. V t lng Ba hay Pb tiu tn kt ta hon ton ion SO42- chng ta d dng tnh c hm lng ion SO42- trong mu phn tch. 2. Phn ng ca cht phn tch vi mt phc cht kim loi to ra mt hp cht phc bn c th chit tch ra c. Sau tch ly phc cht v xc nh hm lng kim loi trong phc cht v t tnh ra hm lng ca cht cn phn tch. V d xc nh hm lng axit phtalic ngi ta cho n tc dng vi thuc th Cu(I)-neocupron to ra phc cht mi l Cu(I)neocupron phtalic. Sau chit ly phc cht ny vo dung mi hu c ph hp ri xc nh hm lng Cu trong phc ny, t tnh ra hm lng axit phtalic trong mu phn tch. Tng t nh vy ngi ta cng xc nh hm lng ion NO3- bng thuc th Cu(I)- neocupron. 3. Phn ng ca cht phn tch to thnh hp cht d a axit. Theo cch ny, nhng kim loi, ion hay hp cht c kh nng to thnh nhng hp cht axit d a u c th xc nh mt cch gin tip qua hp cht d a. V d xc nh P hay ion phtphat PO43- c th xc nh bng cch cho cho n tc dng vi thuc th molypdat trong mi trng axit HNO3 to ra hp cht d a phtphomolypdat kt ta, tch ly sn phm ny v xc nh Mo trong hp cht d a theo vch ph hp th nguyn t Mo - 313nm, ri t tnh ra lng P hay ion phtphat PO43-. Mui asenat ca mt s hp cht alcaloit cng c xc nh theo cch gin tip ny. 4. Phn ng kh ion kim loi v kim loi: Mt s hp cht hu c khi tc dng vi mui kim loi trong nhng iu kin xc nh, s kh ion kim loi v trng thi kim loi t do v phn ng ny c tnh cht nh lng. V d nh phn ng ca chc andehyd vi mui AgNO3 trong mi trng NH3 ( thuc th Tulene ). Tnh cht ny c p dng phn tch cc hp cht hu c c nhm -CHO bng php o AAS nh sau: cho andehyd tc dng vi lng d AgNO3 ton b lng andehyd trong mu phn ng vi AgNO3 gii phng ra Ag kim loi, tch Ag kim loi, ha tan n trong axit HNO3 v xc nh Ag bng
66

php o AAS theo vch ph Ag-328.1nm, ri t tnh ra hm lng andehyd trong mu phn tch. V trong iu kin ny, c 1 nhm -CHO th gii phng ra 1 nguyn t Ag kim loi. Ngoi ra, phn tch gin tip cn c mt s phng php khc nh: da vo kh nng lm tng hay gim cng hp th ca mt vch ph ca mt nguyn t no v s tng hay gim ny l tuyn tnh trong mt gii hn nht nh ca nng ca cht phn tch, v d vi dung dch nn Mg 10g/ml th ion F- lm gim cng hp th ca vch ph Mg- 285.2nm cn vi dung dch nn Cr 1300g/ml th ion F- lm tng cng hp th ca vch ph Cr360.1nm.

67

Chng 4. PHNG PHP QUANG PH PHT X NGUYN T ( ATOMIC EMISION SPECTROMETRY - AES ) 4.1. Phn tch nh tnh bng php o AES 4.1.1. Nguyn tc chung Nh chng ta bit, khi cung cp nng lng ha hi, nguyn t ha mu v kch thch m hi nguyn t i n pht x th chng ta s thu c ph pht x nm trong di ph quang hc ( 190 - 1100nm ) ca mu phn tch, bao gm ba thnh phn: 1. Ph vch ca nguyn t v ion 2. Ph m ca phn t v nhm phn t 3. Ph nn lin tc Trong ba thnh phn ny th ph vch l thnh phn chnh c trng cho nguyn t v ion trng thi hi t do khi b kch thch, gi l cc vch ph pht x c trng ca loi nguyn t y. V d khi b kch thch: - Nguyn t Al pht ra vch c trng: 308.2nm; 309.3nm - Nguyn t Cu pht ra vch c trng: 324.8nm; 327.4nm - Nguyn t Mn pht ra vch c trng: 259.4nm; 269.6nm Nh vy da vo cc vch ph c trng c th nhn bit c s c mt hay vng mt ca chng trong mu phn tch, y chnh l c s ca php phn tch nh tnh v qu trnh phn tch quang ph pht x nh tnh gm cc giai on sau: 1. Cung cp nng lng ha hi, nguyn t ha mu to ra m hi nguyn t t do v kch thch m hi pht ra ph pht x ca chng. 2. Thu chm sng pht x , phn li v ghi ph pht x ca mu phn tch. 3. Quan st ph thu c ca mu phn tch theo cc vch c trng ca cc nguyn t pht hin chng. Cc giai on c thc hin c nh h thng my quang ph pht x, h thng ny gm ba phn chnh tng ng vi ba nhim v nu trn, l:
68

1. Ngun nng lng ha hi, nguyn t ha mu v kch thch m hi pht ra ph pht x 2. H thng quang hc thu, phn ly v ghi ph pht x ca mu. 3. H thng thit b ch th kt qu v x l s liu. Vi nguyn tc chung nh vy nhng trong tng my ca tng hng sn xut c th khc nhau v cch s dng, k thut o, c cp c th trong cc catolog km theo my. Sau y chng ta xem xt mt s vn quan trng ca phng php. 4.1.2. Vch ph c trng ca nguyn t Mun xc nhn s c mt ca mt nguyn t no trong mu phn tch, ngi ta phi tm mt s vch c trng ca nguyn t trong ph ca mu phn tch t m kt lun, nhng vch c trng ny c gi l vch chng minh ca nguyn t. Ni chung, pht hin mt nguyn t t kt qu chnh xc v chc chn, ngi ta phi chn t nht hai vch chng minh khi quan st ph ca mu phn tch. Cc vch ph c chn ny phi tha mn nhng iu kin sau y: 1. Nhng vch ph ny phi r rng v khng trng ln vi vch c trng ca nguyn t khc. 2. Cc vch ph ny phi l nhng vch ph nhy, c th pht hin c nguyn t trong mu vi nng nh ( khi phn tch lng vt ). 3. Khi chn cc vch chng minh ca nguyn t phi lu ngun nng lng dng kch thch ph ca mu phn tch. V khi ngun kch thch c nng lng thp th ph ca nguyn t ch yu l vch nguyn t, cn khi ngun kch thch c nng lng ln th ph ca nguyn t ch yu l ph ca ion. Cho nn phi ty thuc vo ngun nng lng kch thch chn cc vch chng minh cho ph hp. 4. Vic chn cc vch chng minh ca nguyn t cng cn ph thuc vo my c s dng, vi my khc nhau, cc vch ph c trng c th c gi tr khc nhau tuy khng ln, iu ny ph thuc vo c quy trnh o. Ni chung vi

69

mi my quang ph thng c mt Atlas ph km theo dnh cho ngi phn tch s dng. Ngoi ra cn nh rng ph pht x ca mt nguyn t thng c rt nhiu vch, c khi n hng ngn vch, cc vch ny phn b t vng sng ngn n vng sng di ca di ph quang hc ( 190 - 1100nm ), nguyn t no c cu to lp v in t cng phc tp, nht l s in t ha tr cng nhiu th ph pht x cng nhiu vch. V th khi phn tch cc mu a kim loi, ngi phn tch phi rt cn thn khi chn cc vch chng minh ca nguyn t, trnh cc hin tng vch ph trng, cc vch ph chen ln quy ri, k c ph m ca cc phn t v nhm phn t. Mt vi kinh nghim thc t loi tr cc yu t nh hng nh sau: - Da vo tnh cht bay hi khc nhau ca cc nguyn t theo thi gian chn thi gian ghi ph cho thch hp, nh vy c th loi tr c s quy ri ca cc nguyn t khc i vi nguyn t cn phn tch. - Chn iu kin v ngun nng lng kch thch ph hp to ra s kch thch ph c u tin v chn lc i vi nguyn t cn phn tch. - Chn mi trng kch thch ph ph hp. V d khng kch thch trong khng kh m kch thch chng trong mi trng kh tr hay hn hp ca kh tr v xy, khi ny c th loi tr c ph m ca cc phn t v nhm phn t. Kh tr hay c s dng l kh argon. - Thm vo mu nhng cht ph gia thch hp c th loi tr cc hp phn sinh ra ph quy ri, nh to ra s bay hi chn lc, bay hi phn on ca cc nguyn t khc nhau. - Chn my quang ph c tn sc ln v vng ph ph hp thu, phn ly v ghi ph ca mu phn tch. Nu vi cc cch ny m vn cha loi tr c nh hng th phi dng cc phng php tch chit no loi cc cc nguyn t nh hng ra khi mu phn tch. 4.1.3. Cc phng php phn tch nh tnh

70

Mc ch ca phn tch quang ph pht x nh tnh l pht hin cc nguyn t, ch yu l kim loi trong cc mu phn tch. Thc t thng c hai trng hp phn tch nh tnh xy ra l: xc nh nguyn t no trong cc mu phn tch ( cn gi l phn tch tng phn ) hoc phn tch ton din mu phn tch xem mu phn tch cha cc nguyn t kim loi no. Di y l mt s phng php phn tch nh tnh da vo ph pht x nguyn t. 4.1.3.1. Phng php quan st trc tip trn mn nh Nguyn tc ca phng php ny l trn mn nh ca my quang ph (mt phng tiu) ngi ta t mt mng m, trn mng m ny c nh du v tr cc vch c trng ca mt s nguyn t nht nh. ng thi b tr mt h thng knh lp phng i quan st trc tip mn nh . Nh vy mun nh tnh mt mu phn tch no , ta thu ph ca mu phn tch khi kch thch bng ngun nng lng ph hp v quan st ph trc tip trn mn nh ca my nh h thng knh lp phng i, khi ny da vo cc vch c trng nh du trn mng m m kt lun c hay khng c mt nguyn t trong mu phn tch. Phng php ny nhanh, n gin nhng ch gii hn cho nhng mu n gin v mt s nguyn t c nh du v tr cc vch c trng trn mng m ca my quang ph. Phng php ny ch yu phc v cho phn tch luyn kim, kim tra nhanh mt vi nguyn t cn thit nh Mn, Cr, Si, C, Al V cng v th m c mt s my quang ph chuyn dng cho mc ch ny. 4.1.3.2. Phng php so snh ph y l phng php n gin, chnh xc nhng cng ch phc v cho mc ch phn tch tng phn. Nguyn tc ca phng php ny l ghi ph ca nguyn t X nguyn cht ( cht chun ) k vi ph ca mu phn tch, ri tm mt nhm vch c trng ca nguyn t X trong mu nguyn cht v so snh nhm vch ph vi ph ca mu phn tch xem c nhm vch c trng hay khng. Trn c s ny m rt ra kt lun v s c mt ca nguyn t X trong mu phn tch.

71

Phng php ny tuy n gin nhng vi mi nguyn t cn phn tch li phi c cht chun tinh khit lm ph so snh nn b hn ch, t c ng dng trong thc t. 4.1.3.3. Phng php ph chun Ph chun hay cn gi l bn atlas ph, l cc bng vch ph ca Fe theo mt my quang ph nht nh. Atlas c xem nh l thang di sng phc v cho vic nh du v tr cc vch ph c trng ca cc nguyn t, cu to gm hai phn: phn trn l mt dy cc vch ph ca Fe trong mt vng ph nht nh ca my quang ph; phn di, tc l k vi ph ca Fe l v tr cc vch ph c trng ca cc nguyn t khc v trn cng l thang s sng. Khi nh tnh mt mu no ta cn ghi ph ca Fe v k l ph ca mu phn tch trn knh nh; Sau nh my chiu ph v bn atlas ta c th nhn bit bng cch em ph ca Fe trn knh nh lm trng vi ph ca Fe trn bn atlas. V vy phn tch nh tnh bao gi cng phi ghi ph theo tng cp, mt ph ca Fe v k l ph ca mu phn tch. Phng php ny ph hp cho c mc ch phn tch tng phn v phn tch ton din, c s dng rng ri. Mi my quang ph AES phi c m b atlas hon chnh cho tt c cc nguyn t, thng thng cc hng bn my s cung cp cc bng atlas cho cc my ca h. 4.2. Phn tch nh lng bng php o AES 4.2.1. Nguyn tc chung Phng php phn tch quang ph pht x nh lng l da trn c s mi quan h gia nng C ca nguyn t cn xc nh vi cng I ca vch ph pht x do n pht ra khi b kch thch trong nhng iu kin thch hp, y l mi quan h tuyn tnh v n tr theo biu thc ging nh trnh by chng 3: I = k.Cb l gii hn ca vng tuyn tnh. (4.1) Vi Cx < Co th lun c b = 1 v khi Cx > Co th b nh hn 1, gi tr Co c coi

72

Nh vy, da vo phng trnh ny c th phn tch nh lng theo phng php ng chun hay thm tiu chun. Tuy nhin trc y ( trc nm 1965 ), do khng xc nh trc tip c gi tr cng pht x I ca mt vch ph, m ngi ta phi chiu chm sng pht x c cng I ln knh nh, sau xc nh cng hay en ca chng trn knh nh ti ch b chm sng I tc dng ln. en S c tnh theo cng thc: S = a. log I vi cng ca vch ph pht x ca n. Tm li, qu trnh phn tch quang ph pht x nh lng gm cc giai on sau: 1. Cung cp nng lng ha hi, nguyn t ha mu to ra m hi nguyn t t do v kch thch m hi pht ra ph pht x ca chng. 2. Thu chm sng pht x , phn li v chn mt vch ph pht x nhy ca nguyn t hng vo etect o cng . 3. Da vo cng ca vch ph pht x ca nguyn t nh lng. Cc giai on c thc hin c nh h thng my quang ph pht x nguyn t, h thng ny gm ba phn chnh tng ng vi ba nhim v nu trn, l: 1. Ngun nng lng ha hi, nguyn t ha mu v kch thch m hi pht ra ph pht x 2. H thng quang hc thu, phn ly v chn ghi vch ph pht x ca nguyn t cn phn tch trong mu. 3. H thng thit b ch th kt qu v x l s liu. 4.2.2. Cc yu t nh hng n php o AES Cc yu t nh hng n kt qu phn tch nh lng ca php o ph AES l rt a dng v phc tp, c khi xut hin cng c khi khng xut hin, ty thuc vo thnh phn ca mu phn tch v matrix ( cht nn ) ca mu, ph (4.2) Cui cng chng ta vn c mi lin h gia nng ca nguyn t cn xc nh

73

thuc vo ngun nng lng dng kch thch ph. Ngi ta thng chia cc yu t nh hng ny thnh 6 nhm nh sau: - Nhm 1 l cc thng s ca h my o ph, cc thng s ny cn c kho st v chn ph hp cho tng trng hp c th. Qu trnh ny cn gi l qu trnh ti u ha cc thng s ca my quang ph, cc thng s cn la chn nh khe o, iu kin ghi ph - Nhm 2 l k thut v phng php x l mu o ph. - Nhm 3 l cc iu kin ha hi, nguyn t ha mu v kch thch ph. Cc yu t nh hng ny cng th hin nh trong php o AAS. - Nhm 4 l cc yu t v ph, yu t nh hng vt l, yu t nh hng ha hc. Cc yu t nh hng ny cng th hin nh trong php o AAS. 4.2.3. Cc phng php phn tch nh lng Cc phng php nh lng cng tng t nh trong php o AAS, tuy nhin i lng o khng phi l mt quang D m l cng I ca vch ph pht x hoc en S ca n trn knh nh.

74

You might also like