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Php o ph pht x v hp th nguyn t l nhng k thut phn tch ha l,
v ang c pht trin v ng dng rng ri trong nhiu ngnh khoa hc k thut,
trong sn xut cng nghip, nng nghip, y dc, a cht, ha hc. c bit cc
nc pht trin, phng php phn tch ph pht x nguyn t tr thnh mt trong
cc phng php dng phn tch lng vt cc kim loi trong nhiu i tng khc
nhau nh t, nc, khng kh, thc phm, v.v... Hin nay trong cng tc nghin cu
bo v mi trng, phng php phn tch ny l mt cng c c lc xc nh cc
kim loi nng c hi.
nc ta, k thut phn tch theo ph pht x v hp th nguyn t cng c
pht trin v ng dng trong khong hn hai chc nm nay. Mt s phng th nghim
c trang b my o ph pht x v hp th nguyn t, hoc do Nh nc ta u
t, hoc do s vin tr ca cc t chc nc ngoi theo cc chng trnh khc nhau.
Mt s cn b khoa hc ca ta c c ra nc ngoi hc tp, nghin cu v o
to. Song i a s khng c iu kin , nhng li cn s dng k thut phn tch
ny cho cng vic phn tch ca h. Hu ht cc ti liu hay sch khoa hc v k thut
ny li bng ting Anh. Mt khc, chng ta li cha c mt cun sch hoc cc ti liu
c s l thuyt bng ting Vit v k thut phn tch ny.
Do thc th , ng gp cho cng tc o to sinh vin trn lnh vc k thut
phn tch ny ca Khoa Ha hc, Trng i hc Khoa hc T nhin - i hc Quc
gia H Ni, cng nh to iu kin cho mt s cn b khoa hc, cng nhn vin phn
tch ca cc phng th nghim khc c ti liu tham kho, chng ti mnh dn bin
son cun sch ny. N c coi nh l gio trnh c s l thuyt v Phng php
phn tch ph nguyn t. y cng l ni dung nhm phc v o to cao hc v k
thut phn tch ny.
y l gio trnh ting Vit u tin v k thut phn tch hin i ny nn khng
th trnh khi nhng hn ch v thiu st nht nh. V th rt mong s ng gp thm
kin ca cc bn b ng nghip v cc c gi quan tnm, tc gi c iu kin b
sung cho hon chnh hn.
Nhn dp ny chng ti xin chn thnh cm n GS. TS. J.F.M. Maessen, GS. TS.
J. Kragton, GS. TS. Ban, TS. J.C. Kraak, cc k s H. Balker v J.W. Elgersma (khoa
Ha, trng i hc tng hp Amsterdam, H Lan), GS. TSKH. Trnh Xun Gin
(Vin Ha), TS. Nguyn Hong (HQGHN), PGS. TS. Phm Gia Hu (H Dc) v
cc ng nghip B mn Ha Phn tch khoa Ha hc c nhiu kin ng gp
cho ni dung ca gio trnh ny.
Phm Lun
PHN I
Chng 1
I CNG V PHNG PHP AES
Tn vng ph
di sng
Tia gama ()
< 0,1 nm
Tia X
0,1+ 5 nm
T ngoi
80 + 400 nm
Kh kin
400 + 800 nm
Hng ngoi
1+ 400 m
Sng ngn
400 + 1000 m
Sng Raa
0,1+ 1 cm
Sng cc ngn
0,1 - 50 cm
Tivi - FM
1 +10 m
10
Sng raio
10 + 1500 m
Hnh 1.1a
S phn b nng lng trong nguyn t
(1)-cu to nguyn t: (2)-phn b nng lng trong lp v nguyn t.
Hnh 1.1 b
S phn b nng lng trong nguyn t v sinh ph
1.2.2 S xut hin ph pht x
Trong iu kin bnh thng, cc in t chuyn ng trn cc qu o ng vi
mc nng lng thp nht. Khi nguyn t trng thi bn vng, trng thi c bn.
trng thi ny nguyn t khng thu v cng khng pht nng lng. Nhng nu
cungcp nng lng cho nguyn t th trng thi khng tn ti na. Theo quan
im ca thuyt lng t, khi trng thi kh, in t chuyn ng trong khng gian
ca nguyn t, c bit l cc in t ha tr, nu chng nhn c nng lng bn
7
(1.1)
hc
trong :
En v E0 l nng lng ca nguyn t trng thi c bn v trng thi kch thch n;
h l hng s Plank (6,626.10-7 erk.s) hay h = 4,1.10-15 eV.s;
c l tc nh sng (3.108 m/gy) - 2,99793.108 m/gy;
v l tn s ca bc x ;
l bc sng ca bc x .
Trong biu thc trn, nu gi tr E l nm ta c qu trnh hp th v khi gi tr
E dng ta c qu trnh pht x ca nguyn t.
Nhng trong nguyn t, s chuyn mc ca in t t mc nng lng En khng
phi ch v mc E0, m c rt nhiu s chuyn mc t En v cc mc khc E01, E02,
E03 cng vi mc E0. Ngha l c rt nhiu s chuyn mc ca in t c lng
t ha, v ng vi mi bc chuyn mc ta c 1 tia bc x, tc l mt vch ph.
Chnh v th m mt nguyn t khi b kch thch thng c th pht ra rt nhiu vch
ph pht x. Nguyn t no c nhiu in t v c cu to phc tp ca cc lp in t
ha tr th cng c nhiu vch ph pht x. Mt cch tng trng ta c th m t qu
trnh kch thch v pht x ca nguyn t theo m hnh trong hnh 1.2.
Nu dng my quang ph thu chm ra pht x , phn li v ghi li cc chm
tia pht x do nguyn t pht ra ta s c mt di ph t sng ngn n sng di.
l ph pht x ca nguyn t ca cc nguyn t v n l ph vch. Nh vy, ph pht
x nguyn t l sn phm sinh ra do s tng tc vt cht, m y l cc nguyn t
t do trng thi kh vi mt ngun nng lng nhit, in... nht nh ph hp.
Nhng trong ngun sng, khng phi ch c nguyn t t do b kch thch, m c c
Ion, phn t, nhm phn t. Cc phn t ny cng b kch thch v pht ra ph pht x
ca n. Tt nhin l trong mc khc nhau ty thuc vo kh nng kch thch ca
ngun nng lng. V vy, ph pht x ca vt mu lun bao gm ba thnh phn:
1. Nhm ph vch. l ph ca nguyn t v con. Nhm ph vch ny ca
cc nguyn t ha hc hu nh thng nm trong vng ph t 190-1000nm (vng UVVIS). Ch c mt vi nguyn t kim hay kim loi kim mi c mt s vch ph nm
ngoi vng ny.
2. Nhm ph m. l ph pht x ca cc phn t v nhm phn t. V d
8
10
2. H my tnh v phn mm ca n.
Hnh 1.3
S nguyn l ca qu trnh phn tch AES
12
13
d) Phng php phn tch theo ph pht x l mt phng php phn tch tiu tn
t mu, ch cn t 1 n vi chc miligam mu l . c bit l k thut ph pht x.
e) Phng php phn tch ny c th kim tra c ng nht v thnh phn
ca vt mu nhng v tr (ch) khc nhau. V th cng c ng dng kim tra
ng nht ca b mt vt liu.
f) Trong nhiu trng hp, ph ca mu nghin cu thng c ghi li trn
phim nh, knh nh hay trn bng giy. N l nhng ti liu lu tr v khi cn thit c
th nh gi hay xem xt li m khng cn phi c mu phn tch.
Bn cnh nhng u im nu, phng php ny cng c mt s nhc im
v hn ch nht nh. Trc ht phi ni n l: Phng php ny ch cho chng ta
bit c thnh phn nguyn t ca mu phn tch, m khng ch ra c trng thi
lin kt ca n trong mu. chnh xc ca php phn tch ph thuc vo nng
chnh xc ca thnh phn ca dy mu u v cc kt qu nh lng u phi da
theo cc ng chun ca cc dy mu u c ch to sn trc.
Mc du c mt s nhc im v hn ch, nhng phng php phn tch quang
ph pht x nguyn t ngy cng c pht trin v ng dng rng ri trong nhiu lnh
vc khc nhau xc nh lng vt cc nguyn t trong cc i tng mu khc
nhau. l mt phng php phn tch nhanh, c chnh xc bo m v nhy
kh cao, c bit thch hp cho phn tch t him, cc loi nc, khng kh, v.v.
1.6 Kh nng v phm vi ng dng
Phng php phn tch quang ph pht x nguyn t ngy nay gi vai tr quan
trng trong ha hc phn tch. Cng vi s pht trin mnh m ca cc ngnh khoa
hc k thut, c bit l vt l v ha hc, s pht trin ca k thut o v ghi tn hiu,
lm tng kh nng ng dng to ln ca n. Bng phng php ny ngi ta c th
xc nh nh tnh, bn nh lng v nh lng c hn nm chc kim loi v gn
mt chc nguyn t kim trong cc i tng mu khc nhau (v c v hu c).
Phng php phn tch ny tr thnh cng c phn tch nguyn t c lc ch nhiu
lnh vc, nht l sau khi c ngun kch thch ICP.
a) Phn tch quang ph pht x trong ngnh ha v cng nghip ha hc. N l
cng c cc nh ha hc xc nh thnh phn nh tnh v nh lng ca nhiu
cht, kim tra tinh khit ca cc ha phm, nguyn liu v nh gi cht lng ca
chng. N cng l mt phng php xc nh cc ng v phng x v nghin cu
cu trc nguyn t.
b) Phn tch quang ph pht x nguyn t trong a cht. Ngay t khi mi ra
i, phng php ny c cc nh a cht s dng phn tch cc mu qung phc
v cho cng vic thm d a cht v tm ti nguyn khong sn. V th ngnh a cht
ca tt c cc nc u c phng phn tch quang ph pht x rt hin i v hon
chnh.
15
c) Phn tch quang ph pht x trong luyn kim. Luyn kim cng l mt ngnh
s dng phng php phn tch quang ph pht x u tin vo mc ch ca mnh
trc c ngnh ha. Chnh tnh cht nhanh chng v nhy ca phng php ny l
mt iu rt cn thit i vi ngnh luyn kim. N c th l cng c gip cc nh
luyn kim xc nh ngay c thnh phn ca cc cht ang nng chy trong l luyn
kim; qua m h c th iu chnh nguyn liu a vo ch to c nhng hp
kim c thnh phn mong mun, kim tra thnh phn, kim tra nguyn liu.
d) Phn tch quang ph pht x trong tiu ch un hc. Trc y con ngi
tng rng kh c th hiu bit c thnh phn ha hc ca cc hnh tinh xung
quanh tri t chng ta. Nhng phng php phn tch quang ph pht x ra i m
rng tm vi cho con ngi. Bng phng php ph pht x v kt hp vi mt s
knh thin vn, cc nh thin vn c th quan st c thnh phn ca cc nguyn t
ha hc ca cc hnh tinh khc nh mt trng, cc v sao. Chnh nhng kt qu phn
tch thnh phn ca cc mu t do v tinh ly t mt trng v ni ln ngha ca
php o ph pht x trong lnh vc nghin cu thin vn. V nhng kt qu phn tch
thc t cc mu l rt ph hp vi nhng s liu thu c trc y qua phn tch tia
sng t mt trng bng h thng my quang ph v knh thin vn.
e) Phn tch quang ph pht x trong nng nghip, y v sinh hc. y l nhng
ngnh khoa hc s dng phng php ny cm li nhiu kt qu rc r, c bit l
trong vic nghin cu th nhng, nghin cu cc nguyn t vi lng trong t trng,
trong cy trng, trong phn bn ca nng nghip, hay nghin cu thnh phn thc n
phc v chn nui, phn tch nguyn t vi lng trong mu, serum, nc tiu, phc v
cha bnh.
f) Phn tch quang ph trong cc lnh vc khc. Ngoi nhng lnh vc nu,
phng php phn tch quang ph pht x nguyn t cn c mt s ngnh khc s
dng nh l mt cng c phn tch. V d nh trong ngnh dc kim tra mt s
kim loi c hi trong cc dc phm (Pb, Cu, Zn, Hg,...). Ngnh nghin cu c s,
cng an, to n, ngoi thng, cng l nhng ni s dng phng php phn tch
quang ph trong cc lnh vc nghin cu v nng php o ph nguyn t ln ngang
tm ca thi i.
Hnh 1.5
S phn chia cc loi ph theo di sng
16
Chng 2
S KCH THCH PH PHT X NGUYN T
Bng 2.1
Nhit ca mt s loi n kh
STT
Loi hn hp kh t
Nhit (oC)
Axetylen v oxy
2400-3100
Butan v oxy
2000-2550
Kh t v oxy
2200-2500
Hydro v oxy
2100-2300
Axetylen v khng kh
2000-2450
19
Hnh 2.5
H thng nbiulai theo k thut pneumatic
K: Kh mang (oxy ha); S: ng dn mu; F: Kh chy; Q: Cnh qut quay u;
G: Mng bo him; A: ng dn th aetosol ln n nguyn t ha.
2.2.1.3 Qu trnh kch thch ph trong ngn la
Trong phn tch quang ph pht x, nu dng ngn la lm ngun kch thch th
mu phn tch phi chun b dng dung dch. Sau nh mt h thng phun
20
2.2.2 H quang in
2.2.2.1 c im v tnh cht
1. H quang l ngun kch thch c nng lng trung bnh v cng l ngun kch
thch vn nng. N c kh nng kch thch c c mu dn in v khng dn in.
Ty thuc vo cc thng s (A, C, R) ca my pht h quang v loi in cc ta chn
m h quang c nhit t 3500 60000C. Vi nhit ny nhiu nguyn t t cc
nguyn liu mu khc nhau c th c ha hi, nguyn t ha v kch thch ph pht
x. Nhit ca h quang ph thuc rt nhiu vo bn cht ca nguyn liu lm in
cc. V th trong mt iu kin nh nhau, h quang in cc than (graphite) c nhit
cao nht (bng 2.2). Cng dng in trong mch h quang l yu t quyt nh
nhit ca h quang.
2. H quang l ngun kch thch cho nhy tng i cao, v trong h quang
mu phn tch c ha hi tng i d dng hn trong cc loi ngun nng lng
khc, c bit l h quang dng mt chiu. Nhng cng do tnh cht ny m php phn
tch dng h quang c n nh v lp li km ngn la v tia in. y h
quang dng xoay chiu cho kt qu n nh hn h quang dng mt chiu, v th h
quang dng xoay chiu c s dng nhiu hn.
Bng 2.2
Th Ion ha v nhit h quang ca mt s kim loi
Nguyn t lm
in cc
Th Ion ha ca
nguyn t (eV)
Dng in h
quang (A)
Nhit ca h
quang (oC)
11,30
10
6000
Zn
9,40
10
5200
Fe
7,80
10
4800
Cr
6,90
10
4400
Al
5,67
10
4000
U
B
v I m =
R1 + R2
Im
24
25
I=
UR1
+ R2
(2.3)
trong :
R1: in tr ct kh ca plasma gia hai in cc.
R2: in tr ni ca my pht h quang.
U: Th ca ngun in ca my pht t ln hai u in cc F.
2. Yu t th hai quyt nh nhit ca h quang l bn cht ca nguyn liu
lm in cc. Ni chung, nguyn liu no kh bay hi v cu to t nhng nguyn t
ha hc c th Ion ha cng cao, th h quang dng in cc nguyn t s cho nhit
cng cao. V th h quang in cc than (graphite) s c nhit cao nht so vi
cc h quang in nguyn liu khc trong cng mt iu kin dng in th nghim
(bng 2.2).
3. Yu t th ba l th Ion ha ca cc cht c trong mu phn tch, ch yu l
cht nn v nhng cht c nng ln. Ni chung, nguyn t no (nht l cht nn ca
mu) c th Ion ha cng nh th cng lm gim nhiu nhit ca h quang, ngha l
cc kim loi kim c tc dng mnh nht, sau n cc kim loi kim th. Chnh v
th th ngi ta thng thm cc mui halogen ca kim loi kim vo mu gp
phn iu chnh nhit ca plasma ca h quang cho s kch thch ph ca cc
nguyn t phn tch. Bn cnh th Ion ha, th nng ca cc nguyn t cng c nh
hng n nhit ca h quang, c bit l cc nguyn t c th Ion ha thp s lm
gim nhit ca h quang cng nhiu, khi nng ca n trong plasma cng ln.
4. Trong plasma ca h
quang thng lun lun xy ra
cc phn ng ha hc v vt l.
l qu trnh phn li, Ion ha,
t hp phn t v s kch thch
ph. Nhng qu trnh ny
thng l cc qu trnh nhit
ng hc v m hi trong
plasma cng c mt nhit
nht nh ng vi nhng thng
s xc nh ca my pht h
quang c chn. Nhit
m bo cho plasma c mt
p lc in t xc nh duy
tr s kch thch ph.
26
hp cht mui SiO3, PO4, F, mt s nitrat, sunphat... kim loi thng theo c ch ny.
Do c im ca 2 c ch chnh , nn trong phn tch ngi ta thng to diu
kin s kch thch ph xy ra theo c ch 1 c li. iu gii thch ti sao ngi
ta hay dng cc mui halogen, v xetat ca kim loi kim lm nn, hay cht ph gia
cho mu phn tch v mu chun, bin i nn mu gc sang nn nhn to tt hn
v li cn loi tr c cc yu t nh hng, ng thi c khi cn tng c c
nhy ln hng chc ln.
B- Cc qu trnh ph:
Trong plasma ca h quang thng c:
- S hnh thnh hp cht bn nhit, ch yu l cc monoxit (dng MeO).
- S Ion ha to ra cc Ion, ch yu l s Ion ha bc 1.
- S hp th bc x ca nguyn t (qu trnh t o).
- S pht x ph nn lin tc.
Bn cht ca cht mu, thnh phn ca mu, cht ph gia trong l in cc v
nhit ca in cc l yu t quyt nh din bin ca cc qu trnh trn.
Ni chung cc qu trnh ny u khng c li, ngi ta tm bin php loi tr.
V d:
+ hn ch s hnh thnh hp cht bn nhit kiu MeO, ngi ta thm vo mu
mui Clorua ca kim loi kim (nh KCI, CsCl,) lm nn, kch thch ph theo c ch
1, hoc kch thch ph trong mi trng kh tr argon.
+ Hay loi tr s Ion ha ca nguyn t phn tch, ngi ta thm vo mu
cht ph gia mui halogen kim loi kim c th Ion ha thp hn th Ion ha ca
nguyn t phn tch. Nh th nguyn t phn tch s khng b Ion ha na.
2.2.2.5 Cc loi my pht h quang
My pht h quang c rt nhiu, c nhiu hng cung cp, song xt v c ch
mch in ca mch h quang chnh, th c th chia thnh hai loi:
+ My pht h quang dng mt chiu.
+ My pht h quang dng xoay chiu.
Tuy l hai loi, nhng u c nguyn tc cu to nh nhau (hnh 2.6). Trong mi
loi h quang li c nhiu ch khc nhau. Thng thng c mt ch lin tc v
nhiu ch gin on. Chnh v th m chng ta c th chn c nhng gi tr nng
lng khc nhau cho tng mc ch phn tch c th.
2.2.3 Tia la in
2.2.3.1 c im v tnh cht
1. Tia la in l ngun kch thch ph c nng lng tng i cao. Ty theo
cc thng s ca my pht tia la in (C, L, R, T) chn, ta c th t c nhit
28
29
I = Vi C / L
1
1 / LC
2
j=
Vf C / L
I
hay a =
S
S
Men) + E1 Me(k)
Me(k) + E2 Me(k)*
Me(k) + E3 Me(k)+
Me(k)+ + E4 Me(k)+*
31
- Pht x ca nguyn t:
- Pht x ca Ion:
Trong : n(hv) l chm tia pht x ca nguyn t hay Ion b kch thch.
Cn El, E2,.. l nng lng nhit do plasma tia in cung cp.
B- Cc qu trnh ph
Trong plasma gm c:
S hnh thnh hp cht bn nhit, ch yu l cc monoixtit (dng MeO).
- S Ion ha to ra cc Ion, ch yu l s Ion ha bc 1.
- S hp th bc x ca nguyn t (qu trnh t o).
- S pht x ph nn lin tc.
Bn cht ca cht mu, thnh phn ca mu, cht ph gia trong l in cc v
nhit ca in cc l yu t quyt nh s din bin ca cc qu trnh trn.
Song qu trnh ph trong plasma tia in khng mnh nh trong ngn la v
trong h quang, ch c s Ion ha l ng k. V th cc kim loi kim phi o theo
cc vch Ion bc 1.
Ni chung, cc qu trnh ny u khng c li. Ngi ta phi tm bin php loi
tr. V d vi mu dung dch:
+ hn ch s hnh thnh hp cht bn nhit kiu MeO, ngi ta thm vo mu
mui Clorua ca kim loi kim (nh KCI, CsCL,) lm nn, kch thch ph theo c ch
1, hoc kch thch ph trong mi trng kh tr argon.
Vy, loi tr s Ion ha ca nguyn t phn tch, ngi ta thm vo mu cht
ph gia mui halogen kim loi kim c th Ion ha thp hn th Ion ha ca nguyn t
phn tch. Nh th, nguyn t phn tch s khng b Ion ha na.
2.2.3.4 Cc loi my pht tia in
V nguyn tc cu to, my pht tia la in cng c hai loi: my pht tia la
in c ch huy v my pht tia la in khng ch huy. Song trong mc ch phn tch
quang ph pht x, ngi ta ch dng my pht tia in c ch huy. Trong loi my
pht ny, vic ch huy (iu khin) cng theo hai nguyn tc v ng vi hai cch iu
khin ny ngi ta ch to hai loi my pht tia in khc nhau:
+ My pht tia in dng hai tia in, tia in chnh, tia in ph (hnh 2.9),
tng t nh my h quang.
+ My pht tia in dng ngt in ng b (hnh 2.10), ngha l iu khin bng
m t ng b.
My pht tia in dng hai tia din (hnh 2.9)
32
34
4. Tuy c nhit cao nhng s kch thch ph pht x trong ngun nng lng
ny li rt m du. N tng t nh s kch thch ph trong ngn la n kh. Chnh v
th m phng php phn tch t n nh cao v sai s nh.
5. Vi ngun nng lng ny, ngi ta c th nh lng c ng thi nhiu
nguyn t mt lc, nn tc phn tch rt cao (t 40 - 120 mu/gi). Mt khc, khi
dng ngun nng lng ICP, vng tuyn tnh ca phng php nh lng l rt rng
(t 1 - 10.000 ln).
6. c im cui cng l rt t xut hin nh hng ca cht nn (matrix effect).
l im hn hn cc ngun nng lng c in nu.
Hnh 2.12a
H thng ngun ca ICP-AES
2.2.4.3 Nhit ca plasma ICP
ICP l ngun nng lng kch thch ph c nhit cao, nhng li n nh hn
so vi cc loi ngun kch thch khc, nh h quang, tia la in. Nhit ca plasma
ca ngun ny c quyt nh bi dng in cm ng trong cun cm A u ca
n nguyn t ha, tc l nng lng cao tn ca my pht HF. V vy, ng vi nhng
thng s nht nh ca my pht HF th plasma ny c mt nhit xc nh. Trong
cc thng s ca my pht HF, cng sut v tn s cm ng l hai thng s quan trng
36
37
Hnh 2.12b
Hai loi my o ph pht x ICP (ICP-AES)
HF: My pht cao tn; Pm: H thng nguyn t ha mu; L: Thu knh; T: Khe
sng; G: Cch t; PM: H nhn quang in; >>: H in t; Mr: My tnh; Sig: B ch
th kt qu o; AB: Cung mt phng tiu; M1, M2: cc gng chun trc v hi t.
1. Trc ht l dung mi bay hi, li cc ht bt mu. Tip theo l bt mu b
nung nng, nng chy. Sau l cc qu trnh nhit ha ca cht mu xy ra theo tnh
cht ca n.
2. Ba qu trnh chnh: Cc qu trnh chnh y cng tng t nh trong ngn
la n kh. Nhng c khc ngn la n kh l hiu qu ha hi, nguyn t ha v
kch thch ph cao hn nhiu.
- Nu Eh < Ent, th mu s ha hi, nguyn t ha to ra cc nguyn t t do,
chng b kch thch v pht x c ph pht x (AES).
Men Xm(r) Men Xm(k) mMe(k) + nX(k)
38
39
Hnh 2.13
S qu trnh nguyn t ha mu
2.3 Nguyn tc v cch chn ngun kch thch ph
Cc iu kin kch thch ph l nhng yu t c nh hng trc tip n cng
ca vch ph v nhy ca phng php phn tch. V th chn ng cc iu
kin kch thch ph l mt m bo cho phng php phn tch t kt qu chnh xc,
tin cy v nhy cao. Mt khc, qua vic chn c iu kin kch thch ph ph
hp ta c th loi tr c mt suyn t nh hng, nh matrix effect, nng cao
nhy. Do chn c nhng iu kin, ngun kch thch ph ph hp cho mt i
tng phn tch no chng ta phi da theo mt s nguyn tc c bn sau y:
1. Phi xut pht t i tng phn tch thuc dng mu no (mu bt, mu rn,
mu dung dch hay hp kim), cng nh nhng tnh cht c l ca tng loi mu
thuc loi mu d bay hi hay kh bay hi, dn in hay khng dn in. V d khi
phn tch mu bt (qung, t ,...) th h quang c dng trn 10A l thun li. Song
khi phn tch mu hp kim th tia in li u vit. Mu dung dch dng ICP.
2. Phi da theo tnh cht v c trng s kch thch ph ca mi nguyn t cn
xc nh m chn ngun nng lng kch thch v cc thng s ca ngun kch thch.
V d phn tch kim loi kim th nn dng ngn la n kh hay h quang gin on.
V th kch thch ph pht x ca cc kim loi kim l khng ln (3 - 5eV).
40
Ngc li, vi cc nguyn t V, Zn, W,... hp cht bn nhit, li phi chn ngun kch
thch c nng lng cao, h quang in dng ln hay ngun ICP.
3. Khi chn ngun kch thch phi m bo cho php phn tch c nhy cao,
n nh, c th d dng phn tch c cc nguyn t c nng nh.
4. Chn ngun kch thch phi m bo cho php phn tch tiu tn t mu v khi
cn phi khng ph hy mu. Yu t ny trong mt s trng hp khng yu cu, bt
buc nh ba yu t trn.
2.4 Cng vch ph pht x nguyn t
2.4.1 Cng vch ph :
Trong ngun pht sng hay trong plasma, nguyn t (Ao) ca mt nguyn t
c kch thch t trng thi nng lng thp Eo, ln trng thi nng lng cao. Cm
c biu din theo phng trnh:
Ao + XE = A* (a)
Vi mu phn tch c nng xc nh ca Ao th qu trnh ny lc u tng
nhanh, sau chm dn v ti mt thi im nht nh th khng tng na. Ngha l s
nguyn t Ao b kch thch l khng i, ng vi mt nhit xc nh ca plasma.
ng thi vi qu trnh trn l qu trnh ngc li, tc l nguyn t b kch thch A*
gii phng nng lng m n nhn c di dng cc tia pht x n(hvi) tr v
trng thi nng lng thp bn vng ban u. Chnh qu trnh ny l qu trnh pht x
ca nguyn t v sinh ra ph pht x ca nguyn t, c th c biu din theo
phng trnh:
A* = hv + Ao (b)
Qu trnh ny lc u chm, sau tng dn theo s nguyn t A* b kch
thch v n mt thi im nht nh th cng khng tng na ng vi mt nhit
nht nh ca plasma. Ngha l sau mt thi gian nht nh ca s kch thch ph, th
hai qu trnh trn (a) v (b) s t n trng thi cn bng. l hai cn bng ng
hc thun nghch. Cn bng ny ch ph thuc ch yu vo nhit ca plasma, ngha
l s nguyn t A* b kch thch v pht x l khng i, ng vi mt nhit xc nh
ca plasma.
Nu gi Nm l s nguyn t ca nguyn t Ao b kch thch n trng thi nng
lng cao cm, th theo quy lut Bolzmans ta c:
Nm = Na
gm
e( E m ) / Kt
g0
Em l nng lng kch thch nguyn t o t trng thi Eo ln trng thi cm;
T l nhit ca plasma (oK);
k l hng s Bolzmans.
Nu gi Ia l cng ca vch ph do qu trnh kch thch ph ni trn
sinh ra, th trong mt gii hn nht nh ca nhit plasma v nng ca nguyn t
Ao trong plasma, ngi ta thy Ia ph thuc vo:
- S nguyn t Ao b kch thch ln trng thi A*, (Nm).
- Thi gian tn ti ca nguyn t A* trng thi kch thch, (tm).
- Nng lng kch thch nguyn t A t trng thi c bn n trng thi kch
thch, (Em).
- Xc sut chuyn mc ca nguyn t A t trng thi kch thch nng lng Cm
v trng thi ban u nng lng Eo, (Amo).
V mi quan h ny c th biu din theo cng thc sau:
Ia = f .
g
l
. Amo . Aa . m .hv.e ( E ) / kT
tm
go
Vi
ka = f .
(2.6)
g
l
. Amo . Aa . m .hv.e ( E ) / kT
tm
go
C th ta lun lun c:
Na = k2.Cb (2.7)
Nh vy, cng vch ph s l:
Ia = a.Cb (2.8)
Trong : a: k1.k2 v a c gi l hng s thc nghim. N ph thuc vo tt c
cc iu kin thc nghim ha hi, nguyn t ha v kch thch ph mt nguyn t. V
th trong mt php phn tch phi gi cho cc iu kin thc nghim n nh, m
bo a thc s l hng s ca php o. Cn b l hng s bn cht, n ph thuc vo bn
cht ca tng loi nguyn t, b ch nhn nhng gi tr bng 1 v nh hn 1, nhng ln
hn 0. Gi tr ca b nh hn 1 khi nng C ln, cn khi C nh th b lun lun bng
1. Khi b nh hn 1 l lc qu trnh t hp th xy ra. Qu trnh t hp th xy ra cng
nhiu (mnh) th b cng nh xa 1, tc l chnh hng s b l c trng cho qu trnh t
o ca mi loi nguyn t. Do , ng vi mi nguyn t v vi mi mt vch ph
pht x v trong nhng iu kin nht nh, ta lun c mt gi tr nng Co, m:
+ Khi vi mi Cx < Co th b lun lun bng 1.
+ Khi vi mi Cx > Co th b nh dn xa 1 (hnh 2.14).
Trn y cp n cng ca vch ph nguyn t trung ha nhng trong
plasma cn c c cc Ion. Chng cng b kch thch v sinh ra ph pht x. Qu trnh
kch thch v pht x cng ging nh cc nguyn t v cng tnh ton hon ton
tng t nn chng ta c cng vch ph Ion l:
li = Al. Cb (2.9)
(2.10)
43
Cng thc (2.10) l phng trnh c bn ca phng php phn tch nh lng
theo ph pht x nguyn t. Phng trnh ny do Lmakins (Nga) v Saiber (c) tm
ra, nn gi l phng trnh Lmakins-saiber.
2.4.2 Cng vch ph v nhit plasma
Nh trn chng ta bit, cng vch ph pht x ca nguyn t c tnh theo biu
thc sau: Ia = Pa.N(l-x)e-E(m)/kT
V vch Ion:
Ii = Pi.N.x.e-Em/kT
Trong , vi:
Pa =
l
t am
. Aam .
(2.12)
gm
hv
go
44
(2.13)
Vo = Am .N a .hv.e Em kT )dv
(2.14)
Chng 3
MY QUANG PH V S PHN LI CHM SNG
47
48
49
( A + D)
= n. sin( A / 2)
2
dD dn
2 sin( A / 2)
=
. sin
d d
1 n 2 sin 2 ( A / 2)
(3.1)
(3.2)
Chnh hai i lng ni trn c nh hng trc tip n s phn li chm sng,
ngha l quyt nh gc lch D ca chm sng. Chnh v th khi ch to lng knh
ngi ta phi chn nhng vt liu c chit sut ln v ch to gc nh ca lng knh
c ln cho ph hp.
Vt liu lm lng
knh cng phi trong sut,
ng nht v ng hng
trong mt vng ph nht
nh. N phi bn vi
nhit v nh sng.
Chit sut phi hu nh
khng ph thuc vo nhit
v m.
Trong vng kh kin, ch to lng knh ngi ta thng dng mt vi loi
thy tinh, nh thy tinh flin nng, flin nh, thy tinh krau. Trong vng t ngoi ngi
ta thng dng thch anh. Nu c vng ph (UY + VIS) phi dng thy tinh c bit.
3.2.1.2 Cc c trung ca my quang ph lng knh
nh gi cht lng, hiu qu v kh nng s dng ca mt my quang ph,
ngi ta thng dng ba thng s c trng c bn l tn sc gc, tn sc di v
phn gii.
1. tn sc gc.
Trong mi my quang ph, s bin thin ca gc lch D theo di sng ca tia
sng l mt c trng quan trng. N ni ln kh nng tn sc gc ca mt my quang
ph v c gi l tn sc gc ca my quang ph .
Trong cc my quang ph lng knh, lng knh thng c t v tr cc tiu
i vi tia sng trung tnm ca mt vng ph ca my. V th tn sc gc s c
51
Dd
dn
2 sin( A / 2)
x
.sin
2
2
d
1 n sin ( A / 2) d
(3.3)
2
1 n
dn
d
(3.4)
f
dl
dD
= 2 x
d sin E d
(3.5)
hay
R=
(3.6)
(3.7).
Cng thc ny cho ta thy nng sut phn li ca mt my quang ph lng knh
ph thuc vo nhiu yu t, nh:
+ S lng knh trong h tn sc (m);
+ Chit sut ca vt liu lm lng knh (n);
+ Sin ca 1/2 gc nh ca lng knh (A/2)
+ ng knh ca thu knh bung nh (d2);
+ S bin thin ca chit sut theo bc sng (dn/d)
54
Hnh 3.6a
Hnh 3.6b
d
x
2 sin( A / 2)
[1 n
sin 2 ( A / 2)
(3.8)
(3.9)
trc v thu knh bung nh; d l ng knh ca cc thu knh th rng hnh
hc ca vch ph s c tnh theo cng thc sau:
a, = a.(f2/f1)
(3.10)
(3.11a)
s = .(f2/d)
(3.11b)
trong
(3.12)
(3.13)
56
Bng 3.1
Quan h rng khe my v nng sut phn gii - cng vch ph
Khe my
0,50 ao
50
98
0,90 ao
75
96
0,95 ao
82
94
1,00 ao
90
90
1,20 ao
95
80
1,50 ao
98
75
2,00 ao
99
60
2,20 ao
100
50
f2
d . sin E
(3.14)
f2
d . sin E
(3.15)
Hai biu thc trn cho thy, rng ca mt vch ph c lin quan trc tip
rng ca khe my v nng sut phn gii ca my quang ph. Khi vch ph cng rng
th nng sut phn gii cng gim. ng thi rng vch ph cn ph thuc vo:
+ Tiu c ca thu knh bung nh.
+ T l nghch vi ng knh ca thu knh v sin gc nghing ca hp nh.
+ T l thun vi di sng ca vch ph, ngha l cc bc sng di th vch
ph cng rng hn, mc du c cng rng khe sng bng a.
57
(3.16a)
v
s = 2v.(f2/)
(3.16b)
(3.17)
.(d / f1 ) 2 B.a.l
Hay l
.I o = = kB.a.l I o =
kB.a.l
trong :
a v l l rng v chiu di ca khe my quang ph;
B l huy ca chm sng c gc y l .
Khi chm sng Io i qua h quang hc ca my quang ph th quang thng thc
t tc dng ln knh nh (hay vt thu) s l:
= a. = a
(d / f1 ) 2 B.a.l
' = .kB.a.l I o =
kB.a.l
(3.18a)
(3.18b)
' '
=
S a'.l '
(3.19a)
S = a,.l'
a,= a.f2/(f1.sin) v l' = l.(f2/fl)
vi
(3.19b)
' d 2
=
.
sin
S
4 ( f2 )2
(3.20)
B
4
(d / f 2 ) 2 .t. sin
(3.21)
a' =
f
1
.(a. 1 + a1 , a2 , a3 ,...)
sin
f2
(3.22)
v ri thc t lc ny s l:
E=
' B
a
(d / f 2 ) 2 sin
=
2
4
[a + (a1 , a2 , a3 ..., )( f1 / f 2 )]
(3.23)
hay l:
E = E0 .
a
[a + (a1 + a2 + a3 ).( f1 / f 2 )]
(3.24)
59
a
[a + (a1 + a2 + a3 ).( f1 / f 2 )]
(3.25)
Cho nn khi khe my thay i th rng ca vch ph cng thay i theo. Nhng
mi quan h ny khng n iu v cng khng tuyn tnh. V vy, trong mt php
phn tch bt buc phi gi cho khe sng c rng khng i trong mt php o.
Mt khc, cng thc (3.23) v (3.25) cn cho thy, ngoi rng ca khe sng,
cng ca vch ph cn ph thuc vo c khu ca my quang ph, tc l t s
d/f2. Cng vch ph s ln, nu my quang ph c khu ln. Ngha l tiu c
thu knh bung nh phi nh. Nhng nu tiu c thu knh bung nh f2 nh, th li
mt v tn sc di. Chnh v th trong ch to my quang ph ngi ta phi tnh
tm c gi tr khu sao cho ph hp nht, nhm bo m c tn sc m
cng ca vch ph cn ln c th o c v pht hin c d dng.
Nu ly gi tr nghch o ca khu th ta c t s f2/d. T s ny gi l m
ca thu knh bung nh. Trong thc t khi ch to cc my quang ph ngi ta
thng hay chn t s ny c gi tr t 10 n 20. Tri li, khi m ln hn 20, vch
ph c cng ln, nhng tn sc ca my li qu km.
3.2.2.6 sng ca vch ph pht x
Nu ta pht hin v o trc tip cng ca vch ph bng mt nhn quang
in, th sng ca vch ph l yu t quan trng. sng ca vch ph ph thuc
vo cng ca chm sng i vo my quang ph v cng ca chm sng sau
khi qua my quang ph vo nhn quang in. V th cu to, tnh cht ca h quang
hc ca my u c nh hng n sng ca vch ph. Mt cch gn ng v theo
thc nghim, sng ca vch ph c th c tnh theo cng thc:
L = (d2/f2)2
(3.26)
Hnh 3.7
S quang hc ca mt s my o ph pht x
P: Lng knh; G: Cch t; M, M1, M2: Cc h gng; L: Thu knh; E: Hp nh
ghi ph; T: Khe sng; S: Ngun pht x.
3.2.2 Cch t v my quang ph cch t
3.2.2.1 Gii thiu v cch t
Cch t l h gm nhiu khe hp (vch) song song vi nhau v cch u nhau.
Mi khe nh l mt chn sng, cn ch khng c vch nh l mt khe sng.
Cch t c tc dng phn li nh sng nh lng knh. Nhng bn cht s phn li nh
sng cch t khc lng knh. S phn li nh sng ca cch t l do hin tng nhiu
61
x ca chm sng qua khe hp. Khi s phn li nh sng ca lng knh l theo hin
tng khc x ca nh sng qua hai mi trng c chit sut khc nhau.Cch t c
hai loi:
1. Cch t phn x v 2. Cch t truyn x.
ch to my quang ph ngi ta thng dng cch t phn x, v dng cch
t truyn x s b mt nhiu nng lng khi chm sng i qua cch t.
Trong mi loi trn li c cch t phng v cch t lm. T thc t chng ta
s ch cp n cu to v bn cht ca cch t phn x l chnh (hnh 3.8a v 3.8b).
(3.27)
(3.28)
(3.29)
(3.30)
(3.31)
(3.32)
(3.33)
ngha l:
- Cc i th 1 cch tnm mt on xt1 = (1.f2,)/k
- Cc i th 2 cch tnm mt on xt2 = (2.f2. )/k
63
DDl
m
(3.34)
Vi m l s nguyn v m > 1.
3.2.2.2 My quang ph cch t
My quang ph cch t, v nguyn tc, cng c cu to nh my quang ph lng
knh. Nhng y h tn sc l mt cch t, v cng dng ba i lng c trng nh
trong my quang ph lng knh nh gi cht lng ca mt my quang ph cch
t. C th l:
1. tn sc gc
T cng thc c bn ca cch t (3.29), nu xt s bin thin ca gc lch theo
di sng th ta c:
cos.d = (m.k).d
hay l:
Dg =
D
mk
=
D cos
(3.35)
Dmg =
Dgl
m
(3.36)
(3.37)
10 3
(3.38)
65
tn sc di nghch o trong my
Cch t PGS-2, bc 1
Lng knh q 24
2000
7,390 /mm
4,00 /mm
2500
7,380 -
7,80 -
3000
7,370 -
13,00 -
3500
7,356 -
18,00 -
4000
7,340 -
31,00 -
d
.
d d
hay l
R = m.k.L
Nh vy, r rng nng sut phn gii mt my quang ph cch t t l thun vi:
- Hng s k ca cch t, ngha l k ln th tn sc ln
- Chiu di ca cch t L, v
- S bc ph ca cch t, m. Bc ph cao th phn gii cao.
Do , mun tng kh nng phn gii ca mt my quang ph cch t phi s
dng nhng cch t c hng s k ln v chiu di L ln. Nhng vic tng chiu di L
ch c gii hn (di nht l 15 cm). Nn ch yu l tng hng s k ca cch t, ngha l
phi ch to nhng cch t c nhiu vch trn 1 mm di. ng thi phi s dng
ph nhng bc cao, nh bc m=2. Song cc bc cao ca ph th cng vch
ph li nh. V d: ng vi cch t c k bng 1800, th trong vng sng 3000 hai
66
Hnh 3.9
nhy ph ca cc loi knh nh
(1): Vng 1800-4000 , (2): Vng 3600-7800 v (3): Vng 7000-10000 .
Thng thng knh nh c nhy cao thng c nh hng n phn gii
ca vch ph, v cc knh nh nhy chng c ht AgBr kch thch ln. Do , tng
nhy ca knh nh ngi ta thng thm vo mt cht kch hot quang hc, vn
dng lp nh tng c ht AgBr kch thc nh m knh nh t c nhy cao.
Khi ta chiu chm sng cng I ln tm knh nh th ch b nh sng tc dng
vo s ha en. Nu gi en ti im b nh sng tc dng vo l S, th ta c:.
S = log I
y l h s nh tng (tng phn) ca knh nh, v chnh cu to v bn
cht ca lp glatin quyt nh h s nh tng . H s ny cng ph thuc vo
di sng ca vch ph, nhng rt khc nhau trong mi vng ph (hnh 3.10a). Khi b
nh sng tc dng th c mt lng t sng hv s gii phng ra mt ht Ag kim loi
theo phn ng sau:
AgBr + hv = Ago + Br
Cc ht Ag nguyn t t do ny nm n tng trong lp glatin ta cha nhn thy.
V th, mun c nh thc v gi li c chng ta phi x l knh nh c
nh sng tc dng qua dung dch hin hnh v dung dch nh hnh. Sau y l thnh
phn ca cc dung dch .
69
1. Mentol: 1g.
5 KB kh
15
Ngoi nhy, thi gian chiu sng cng l yu t quan trng nh hng n
en ca vch ph. Ni chung, chiu sng cng lu th en cng ln. Song, tt nhin
cng ch trong mt thi gian nht nh ph hp. Cn nhiu hn na th ch lm gim
phn gii ca vch ph, v thi gian qu di s lm m rng chiu ngang ca vch
ph m khng lm tng en S vch ph.
Thi gian hin cng nh hng n cng vch ph. Mi quan h ny c thy
trong hnh 3.10b.
Ni chung, vi nhiu loi knh nh, thi gian hin ph hp l t 2 n 4 pht v
thi gian hm (nh hnh) l t 4 n 8 pht. Nhit thch hp l t 18 n 200C.
3.5.2 o en S ca vch ph trn knh nh
Nu chiu chm sng cng Io vo knh nh th ch c vch ph v khng c
vch ph, chm sng i qua s c cng l I v Io. Do en ca vch ph s l:
S = log(Io/I)
hay
S = log(ao/a)
ao
1)
a
S+ W
2
72
73
74
Chng 4
CC YU T NH HNG TRONG AES
76
Bng 4.1
S chen ln v s trng vch ca cc nguyn t
Nguyn t v vch
phn tch (nm)
Al-308,215
V- 308,211
>800
Cu-324,754
Eu-324,753
>254
Fe-271,903
Pt-271,904
>054
Pr-411,848
Fe-411,854
>050
Mn-403,307
Ga-403,298
>025
Zn-213,856
Fe-213,850
>200
4.2.1:3 S bc x ca cc ht rn
Trong mi trng pht x, c bit l trong ngn la n kh, h quang, nhiu
khi cn c cha c cc ht rn rt nh li ti ca vt cht mu cha b ha hi v nguyn
t ha, hay cc ht mui cacbon ca nhin liu cha c t chy hon ton. Cc ht
loi ny thng c lp v ca ngn la v n cng b kch thch pht x ra ph nn,
do cng gy kh khn cho vic quan st hay o cng vch ph phn tch. Yu
t ny th hin rt r khi chn khng ng chiu cao ca n nguyn t ha mu v
cc iu kin ca ngun kch thch ph khng ph hp.
4.2.2 Cc yu t vt l
Thuc v loi yu t vt l ny thng c:
4.2.2.1 nht v sc cng b mt ca dung dch mu
Trong php o ICP-AES, hay vi k thut nguyn t ha mu trong ngn la, nu
mu l dung dch, yu t ny nh hng nhiu n tc dn mu vo bung aerosol
ha v hiu sut aerosol ha ca mu v t m nh hng n kt qu phn tch.
Ni chung, tc dn ng chun phi c cng nng axit, loi axit v thnh phn
ha hc, vt l ca tt c cc nguyn t khc, nht l cht nn ca mu. Yu t ny
thng th hin nhiu trong php o AES dng ngun ngn la v h quang in.
loi tr nh hng ny chng ta c th dng cc bin php sau y:
Chnh s khc nhau v nng axit, loi axit, nng cht nn ca mu, thnh
phn ca cc cht c trong dung dch mu, nguyn nhn gy ra khc nhau v nht
ca dung dch mu. V th trong mi qu trnh phn tch mt nguyn t, nht thit phi
m bo sao cho mu phn tch v cc mu u lpmu t l nghch vi nht ca
dung dch mu (hnh 4.2)..
77
- 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 cht
m c nng ln,
- Dng bm y
mu vi mt tc xc
nh m chng ta mong
mun.
4.2.2.2 S Ion ha ca cht phn tch
- Nu o vch ph trung ha ca nguyn t, y l yu t vt l th ba nh hng
n kt qu phn tch, v qu trnh Ion ha lm gim s nguyn t t do ca nguyn t
phn tch, do lm gim cng vch ph pht x ca nguyn t trung ha, khi
nguyn t phn tch b Ion ha cng nhiu. Nhng mc b Ion ha ca mi nguyn
t l khc nhau, v ph thuc vo nhit ca mi trng pht x. Trong mt iu
kin nht nh, ni chung cc nguyn t c th Ion ha cng thp th cng b Ion ha
nhiu. Vi mt nguyn t, khi nhit ca mi trng pht x cng cao th nguyn t
cng b Ion ha nhiu hn. Bng 4.2 l mt v d v iu ny.
Bng 4.2
Mc Ion ha ca mt s nguyn t
N.t
78
Th Ion ha(eV)
3000
4000
Na
5,21
00,30
05,00
26,00
4,32
02,10
22,00
82,00
Rb
4,16
09,00
34,00
90,00
Cs
3,87
28,00
70,00
96,00
Mg
7,54
00,12
00,50
05,60
Ca
6,11
00,20
01,50
15,00
Sr
5,69
00,50
02,35
18,70
Ba
5,31
01,00
06,00
23,00
80
84
vng nng nht nh. Cc Anion khc thng gy hiu ng nm (lm gim) theo th
t Cl , ON 3 , CO3 , SO4 , PO4 , SiO3 . Trong Anion SiO3c nh hng ln nht, cn t
nht l hai Ion Cl v NO 3 . ng thi khi nng ca cc Anion tng th tc dng
nh hng cng tng theo (hnh 4.9). Do thc t nn 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 nht nh khng i. Mt khc, cng khng nn chn axit H2SO4 lm mi
trng ca mu cho php o AES m ch nn dng axit HCl hay HNO3 vi nng
di 2%.
Cht nn ca mu
Ca-422,70 nm
0,220
0,250
2. Nh 1, thm 2% LaCl3
0,008
0,005
0,050
0,060
3. Nh 2, thm 1% NH4NO3+LiBO2
0,210
0,245
Trong cc bin php trn, bin php th nht cng ch thc hin c trong
nhng chng mc nht nh, v chng ta khng th tng nhit nguyn t ha ln
cao mi c, do s hn ch ca trang thit b, bn cht ca khi t, hn na khi nhit
nguyn t ha qu cao th li xut hin nh hng ca s Ion ha. Cho nn bin
php hai v ba l thng dng nht. Cc cht ph gia thng hay c dng trong php
o F-AES, ICP-AES l LaCl3, SrCl2, LiCl, KCl, AlCl3 v cht ph gia c dng
nhiu nht l LiBO2, NH4NO3 hay hn hp ca hai cht ny vi mt nng ph hp.
87
Chng 5
PHN TCH QUANG PH PHT X NH TNH
Al
Ba
Ba
Ca
Cu
Fe
92
Vch ph (nm)
Cng
I 328,068
5500R
0,0001
I 338,289
2800R
0,0006
I 520,907
100R
0,02
I 546,549
100R
0,025
I 257,510
48R
0,08
I 308,216
320R
0,001
I 309,271
650R
0,0005
I 396,153
900R
0,0003
I 249,678
420R
0,005
I 249,773
480R
0,003
II 233,527
55R
0,02
II 234,758
16R
0,05
II 455,404
6500R
0,0005
II 493,409
2000R
0,001
II 553,555
650R
0,006
II 315,887
20
0,05
II 317,933
50
0,02
II 393,367
4420R
0,0005
II 396,847
2200R
0,001
II 422,673
1100R
0,003
I 2824,34
50
0,05
I 3247,54
5000R
0,0004
I 3273,96
2500R
0,001
I 5105,54
40
0,06
I 248,328
I 259,941
I 302,065
I 358,120
I 371,994
I 373,448
280rh
200
280R
600R
700R
700r
0,001
0,003
0,001
0,0005
0,00045
0,0005
97
98
Chng 6
PHN TCH PH PHT X NH LNG
(6.1)
(6.2)
(6.3)
(6.3)
T thc t , hin nay chng ta c hai phng trnh c bn ca php phn tch
nh lng theo ph pht x ca nguyn t. Nu cc my cho php xc nh trc tip
99
(6.5)
Hnh 6.1
Mi quan h gia cng vch ph v nng cht.
(A): Mi quan h I-Cx; (B): Mi quan h S-logCx
100
101
mx
100
m
(6.6)
mx
100
mg
(6.7)
Trong hai cch biu din ny th cch biu din th nht c ng dng nhiu
hn, cn cch th hai ch dng khi so snh nng ca nguyn t phn tch vi
nguyn t c s ca mu. Trong thc t, ngi ta quy c rng, khi ni nng phn
trm th ngi ta hiu l nng phn trm tuyt i. Ngc li mun dng cch
th hai ngi ta phi ni v ghi y l nng phn trm tng i.
Tt nhin gia hai cch biu din ny u c quan h vi nhau v t cch biu
din th nht, ngi ta c th suy ra cch biu din th hai theo cng thc sau:
%C xt =
102
C xd mg
m
(6.8)
Bng 6.1
Mi quan h gia cc loi n v nng
n v gc
Tng ng vi (*)
Tng ng vi (*)
1000 ppm
1 mg/mL
10-3 g/mL
1 ppm
1 g/mL
10-6 g/mL
1 ppb
1 ng/mL
10-9 g/mL
1 ppp
1 pg/mL
10-12 g/mL
1 ppf
1 fg/mL
10-15 g/mL
1 ppa
1 ag/mL
10-18 g/mL
Bng 6.2
Mi quan h gia cc loi n v nng
n v gc
1 mg
10-3
1 g
10-6
10-3
1 ng
10-9
10-6
10-3
1 pg
10-12
10-9
10-6
10-3
1 pf
10-15
10-12
10-9
10-6
10-3
10-15
10-12
10-9
10-6
1 ag
trong :
104
Tng ng vi cc n v
10-18
10-3
ag - attogam;
pa - picogam.
fg - femtogam;
ng - nanogam.
g - microgam.
ppm: mt phn triu (part per mil Ion)
Bng 6.3
Chuyn i gia cc loi nng
Nng u c
1 ppm
1 ppm
g/L
1 ppm
Mol/L (M)
1 ppm
% trng lng
1 g/L
ppm
1 g/L
% trng lng
1ppd
ng/mL
p
0,0001 p.A
0,0001
1/p
1/10000.p
p
trong :
- p: T trng ca dung dch
- A: Nguyn t gam hay phn t gam ca cht phn tch.
- Mu u phi c thnh phn ha hc v vt l ging nh mu phn tch, ngha
l trong mu phn tch c cha nhng nguyn t no v tn ti trng thi hp cht
no th cc mu u (mu chun) cng phi c thnh phn nh th, nht l cht nn
ca mu. C nh th mi loi b c nh hng ca sai khc v thnh phn n kt
qu phn tch.
Mu u v mu phn tch phi c x l v ch luyn trong cng mt iu kin
nh nhau v cng mt trng thi.
- Nng ca nguyn t phn tch trong cc mu u phi tht chnh xc.
Khong nng ca c dy mu u phi phn b ri u trn ton b phn vng
tuyn tnh ca ng chun.
105
- Thnh phn ca cc mu u phi bn vng theo thi gian, ngha l sau khi
chun b xong chng khng thay i v mi mt, t nng n trng thi lin kt v
cu trc.
Khi mu u v mu phn tch tha mn nhng iu kin trn, ngha l mu u
v mu phn tch ph hp vi nhau v mi mt th cc c trng v ph ca mu l
tng t nhau. V d:
+ Nn ca ph l nh nhau,
+ ng cong bay hi ca cc nguyn t trong mu u v mu chun c dng
ging nhau,
+ Thnh phn ph vch ca nguyn t l nh nhau, c bit l nguyn t c s
phi hon ton ng nht trong cc mu,
+ Thi gian kch thch ph ca cc mu l nh nhau.
Chnh nh nhng c trng c s ny ca ph mu m ngi ta c th pht hin
c xem mu phn tch v cc mu u c ch luyn c ng nht hay khng.
Mu chun v mu phn tch c th dng bt, rn hay dung dch l ty thuc vo
nguyn t phn tch, cc trang b v iu kin kch thch ph no cho kt qu tt nht.
6.1.5 Gii hn chng minh v khong xc nh
Cng nh cc phng php phn tch khc, phng php phn tch quang ph
pht x nh lng cng c mt gii hn nht nh i vi mi nguyn t trong mt
i tng nht nh. l mt khong nng ca nguyn t cn kho st (xc nh)
m php o nh lng cn cho kt qu tin cy, ngha l c mt cn trn v cn di
ca mt php xc nh i vi mt nguyn t. Vng nng nm gia gii hn trn v
gii hn di c gi l khong xc nh ca phng php phn tch. Tt nhin
khong xc nh ca mt phng php i vi mi nguyn t l khc nhau v ngay
mt nguyn t, nu o nh lng theo cc vch ph khc nhau th khong xc nh
ca n cng khc nhau. Vch ph no cng nhy th khong xc nh cng hp v n
nm trong vng nng cng nh (bng 6.4). Gii hn chng minh v khong xc
nh ca mt nguyn t c th c xc nh theo hai cch:
- Phng php thc nghim.
- Phng php ton thng k.
Trong thc t ca phn tch, vic xc nh v m rng cn di ca mt phng
php phn tch lun lun c ngha ln, v n rt cn thit trong cng vic phn tch
cc nguyn t vi lng v siu vi lng, ngha l nng gii hn di pht hin c
ca phng php phn tch cng nh, th trong nhiu trng hp c th b qua c
giai on lm giu s b mu cn phn tch, m ta vn xc nh c.
106
(6.9)
(6.10)
Nguyn t
Vch ph(nm)
Khong xc nh (%)
(Gii hn trn v di)
Al 236,706
0,03
0,05 0,4
237,208
0,1
0,15 2,0
309,271
0,001
0,003 0,15
396, 1 5
0,0003
0,0005- 0,05
Bi 240,088
0,1
0,15 0,9
262,791
0,03
0,04 0,5
289,798
0,003
0,005 0,2
Fe 238,204
0,001
0,002 0,25
259,940
0,0002
0,0003- 0,1
259,957
0,0003
0,0004- 0,15
Si 230,302
0,3
0,4 2,0
250,690
0,001
0,003 0,3
251,612
0,0003
0,0005- 0,15
Mg 278,142
0,03
0,05 0,25
280,270
0,001
0,002 0,10
285,213
0,0003
0,0005- 0,05
V th, mun nng cao nhy ca mt php phn tch, ngi ta c th chn
nhng iu kin thc nghim no, ph hp nht i vi tng nguyn t cn xc nh.
6.1.6 S bay hi v ng cong bay hi
Trong phn tch quang ph, mu phn tch c a vo ngun sng kch
thch ph v khi n cng tr thnh ngun pht sng, tc l ngun pht ra cc tia ph
108
Bng 6.5
So snh kt qu trong hai mi trng kch thch ph
Nguyn t
Mi trng khng kh
Cng
nhy
Cng
nhy
Eu 4435,60
67
0,0004%
120
0,0001%
Sm 4424,34
65
0,0008%
104
0,0003%
Nhm 1: Cc mui halogen ca kim loi kim v kim th: Lia, LiF, NaCl, NaF,
CsF, CsCL, AgCl, CaF2, CaCL2, MgCl2, v mt vi kim loi nng Ti, Sb, Sn, Ga,...
Nhm 2: Mt s oxit kim loi, nh oxit ca Ga, Sb, Sn, Ti, Mg, Al, Fe,...
Nhm 3: Mt s mui cacbonat, borat ca kim loi kim v kim th, nh
Na2CO3, Li2CO3, LiBO2, BaCO3,
Nhm 4: Mt s halogen ca hp cht hu c, nh CF4,
Nhm 5: Cc n cht v hp cht ca lu hunh: S. CaSO4, SrSO4,
Nhm 6: Cc hp cht ca Si: SiO2, Na2Sio3,
Cc cht ph gia ny c th lm tng hoc lm gim cng ca vch ph ca
mt nguyn t. Song mt cht ph gia c th c mt hay nhiu chc nng khc nhau
khi chng c thm vo mu phn tch. N c th l cht m, cht mang mu, cht
chy, cht pha long, cht tr lc cho s ha hi v bay hi ca mu,... ngha l ty
tng trng hp c th m nhng vai tr no l ch yu.
1. Cht m. L nhng cht khi thm vo mu c tc dng n nh mt iu
kin nay mt qu trnh no trong s kch thch ph. V d m cho nhit plasma,
m cho p lc in t trong plasma. in hnh cho loi cht m l bt than quang
ph. Bt than quang ph khng nhng c tc dng m nhit cho plasma, m cn
lm cho s bay hi ca mu c d dng v n nh. Mt khc n cn gi cho plasma
c nhit cao thch hp i vi s kch thch ph ca nhiu nguyn t. V th n rt
cn v quan trng i vi php phn tch cc mu bt v mu khng dn in. V d:
Khi phn tch cc mu qung, t , oxit,... ngi ta thng nghin chng thnh bt
v sau trn vi bt than quang ph theo mt t l thch hp. Ngoi bt than, mt s
mui halogen ca cc kim loi kim cng l cc cht m quang ph, nh CsCl, CsF,
LiF, LiCl,... Nhng cht ny c tc dng m cho p lc in t (P) trong plasma t
thay i trong qu trnh kch thch ph. Tt nhin ngoi tc dng m, cc halogen ca
cc kim loi kim v kim th cn c tc dng duy tr v n nh dng in qua ct
kh ca plasma.
2. Cht mang. Trong nhiu trng hp khi thm cht ph gia vo mu th s ha
hi v nguyn t ha ca cc hp phn trong mu li d dng hn, nhanh hn, hoc n
nh hn. Nhng cht ph gia c tc dng nh th c gi l nhng cht mang. N
thng l nhng cht d ha kh, d bay hi. V th khi vo trong mu, n bay hi c
th ko theo c cc hp phn mu bay hi, hoc tc dng vi cc hp phn ca mu
to thnh nhng hp cht mi d ha hi. Chnh v th m mu bay hi tt hn. Tiu
biu cho cc loi cht ny l cc mui halogen v cacbonat ca cc kim loi kim v
mt vi kim loi kim th nh CsF, CsCl, LiF, LiCl, NaF, NaCl, Li2Coa, Na2CO3,
CaCO3, SrCO3, BaCO3. ng thi c bt than quang ph cng c tc dng ny rt r
rt khi phn tch cc mu khng dn in. Ngoi ra, mt s oxit d bay hi ca mt s
nguyn t nh Ga, Sb, cng l nhng cht mang. Cc cht mang ny trong nhiu
trng hp cn c tc dng lm tng cng vch ph.
114
loi v cha nhng nguyn t dng hp cht bn nhit, kh bay hi ngi ta phi
thm vo mu phn tch cc cht chy theo nhng t l ph hp vi mc ch h thp
nhit nng chy ca mu v lm mu d bay hi. Ngoi tc dng y, nhng cht
chy c nhiu trng hp cn lm tng cng vch ph ca nguyn t cn nghin
cu. V d nh LiBO2 trong bng 6.6.
Bng 6.6
Vai tr ca cht pha long mu
STT
Cng vch ph
Mu
Bt than
LiBO2
Fe-248,30 nm
0,140
2
3
1
1
1
2
1
1
0,230
0 280
0,260
Nguyn t
LiF (2%)
4424,34 Sm
115
138
134
4435,60 Eu
120
148
145
4262,10 Gd
90
105
110
Trn y l khi qut chung v tc dng ca cc loi cht ph gia khc nhau.
Song thc t phn tch rt l phong ph v phc tp, nht l khi phn tch cc mu
qung c thnh phn phc tp, nhiu vn cn phi c nghin cu v bn bc
thm theo nhng kt qu nghin cu tip tc hin nay v sau ny na, c bit l qu
trnh kch thch ph pht x trong ngun nng lng mi ICP ca php o ICP-AES.
118
no ca cc mu u.
Nu en S, hay cng ca vch ph phn tch, ta quan st nm gia en
ca vch nng C2 v C3 th ta ni nng Cx ln hn C2 nhng li nh hn
C3, ngha l ta c th vit:
C2 < Cx < C3
l ni dung ca phng php so snh.
Phng php ny n gin, d thc hin. Nhng mi khi phn tch mt mu li
phi ghi ph ca mt dy mu u, nh th cng tn nhiu mu chun, in cc v
mt th gi. Phng php ny thng c ng dng phn tch cc mu dung dch. V
d, xc nh kim loi trong nc khong, nc t nhin (hnh 6.5).
6.2.2 Phng php hin vch
Nguyn tc ca phng php ny da trn c s s vch ph ca mt nguyn t
xut hin cng nhiu khi nng ca nguyn t trong mu cng ln, ngha l ng
vi mi mt nng nht nh th c mt s vch ph xut hin trong iu kin th
nghim c chn ph hp i vi mt nguyn t trong mt i tng mu nht
nh.
V d: nng 0,001% ca Pb mu, v nu kch thch ph trong iu kin h
quang dng 10A th ch c ba vch ca Pb: 2614,20; 2802,00; 2833,06 Ao xut hin.
V vy mun phn tch mt
nguyn t no , trc ht ngi ta
cng phi chun b mt dy mu u
cha nguyn t X vi nng , v
d: C1 C2, Ca, C4, C5, C6, C7,V
Cc mu phn tch Cx1, Cx2, trong
cng iu kin. Sau ghi ph ca
cc mu trong iu kin chn.
Quan st ph thu c ca tt c cc
nng xem mi nng c bao
nhiu vch ph ca nguyn t phn
tch xut hin v lp mt bng hin
vch ca chng ng vi tng nng .
Bng ny c dng phn tch
nguyn t sau ny. Bng 6.8 l mt
v d v xc nh Pb trong qung theo
phng php ny.
120
Bng 6.8
V d v xc nh Pb theo phng php hin vch
Nng Ph (%)
C1 0,001
C2 0,005
C3 0,01
C4 0,05
C5 0,1
C6 0,5
C7 1,0
C8 1,5
..
Cx
S = . b.log C + k (b)
Dy chun
0
Co
C1
C2
C3
C4
C5
Nh nhau trong tt c cc mu
o I
Io
I1
I2
I3
I4
I5
o S
So
S1
S2
S3
S4
S5
122
Ri t cc cp gi tr (s/log C)
hay (I/C) ta dng ng chun theo
h ta S - log C (nu ph ghi trn
knh nh cc my quang ph th h
1 v 2) hay I - C. ng ny chnh l
cc ng chun (hay ng cong ly
mu) xc nh nng Cx cha
bit ca nguyn t phn tch X. Mun
th ta ch cn cm cc gi tr Sx hay
Ix c t ln trc tung v t k
ng song song vi trc honh, n
ct ng chun ti im A, t im
A ny h ng vung gc vi trc
honh, th ta c c Cx (nu o I)
hay l logCx (nu o S) ri suy ra Cx
cn tm (hnh 6.6).
T ng chun trn, ngoi vic
xc nh Cx chng ta cng c th xc
nh c h s a trong phng trnh
(a) v h s k cng nh y; h s b
trong phng trnh (b). C th l:
Theo hnh 6.6a ta c:
a = tg (6.11)
V theo hnh 6.6b ta c:
.b = tg
v k l on OD (6.12)
Phng php ny rt thun li khi phn tch hng lot mu ca cng mt i
tng, v ch cn mt ng chun l c th xc nh c rt nhiu mu c nng
Cx cha bit.
Nhng mu phn tch v mu u phi ghi ph trong cng mt iu kin v trn
cng mt knh nh. V th nu phn tch nhiu i tng m mi i tng ch mt
hoc hai mu th tn mu u, knh nh, thi gian,... chnh l im cha u vit ca
phng php ny. V th xut hin phng php th khng i. Song trong nhng
iu kin nht nh th n cng vn l mt phng php c ng dng ph bin v c
nhiu u vit.
123
(6.13)
(6.14)
Cht
Co
C1
C2
C3
C4
C5
Cht PT X
Cx
Cx
Cx
Cx
Cx
Cx
X thm vo
C1
C1
C1
C1
C1
Cht khc
Nh nhau tt c
o c I
Io
I1
I2
I3
I4
I5
Hay o S
So
S1
S2
S3
S4
S5
125
(6.15)
S2 = .b log C2 + k
(a)
S1 = .b.log C1 + k
(b)
Ly (a) tr (b) ta c:
(S2 S1) = .b(log C2 - log C1)
Do ta suy ra: =
(S 2 S1 )
log(C 2 / C1 )
v b = 1
6.3.4 Phng php theo 1 mu chun
a) Khi c mu chun
Trong nhng trng hp n gin, chng ta khng cn pha mt dy chun
dng th chun, m c th tnh ngay gi tr Cx nh mt mu chun Cl ca cht phn
tch, ngha l chng ta c:
Vi mu phn tch:
Ix = a.Cx
(a)
Vi mu u:
I1 = a.C1
(b)
(6.17)
Ix = a.Cx
(a)
(b)
(6.18)
127
129
+ Vi As:
+ Vi
+ Vi
Cc cht
Co
C1
C2
C3
C4
C5
Cx
Ng Mg(ppm)
Ng. F (ppm)
10
Cx
HCl (%)
I5
Ix
Io
I1
I2
I3
I4
C1
C2
C3
C4
C5
Cx
Nng Ca(ppm)
Protein (mm)
0,02
0,04
0,06
0,08
0,10
Cx
HCl (%)
Cc yu t khc
o I
(Ca-422,70 nm)
134
Dy chun
I1
I2
I3
I4
I5
Ix
Phn II
Chng 7
NHNG VN CHUNG CA PHP O ASS
(7.1)
E = h.c /
(7.2)
hay l.
Qu trnh pht x v hp th ca mt
nguyn t Eo: Mc nng lng trng
thi c bn; cm: Mc nng lng trng
thi kch thch; E: Nng lng nhn vo
(kch thch);
+ hv: Photon kch thch;
+ hv: Photon pht x.
136
Hnh 7.1
S phn b nng lng trong nguyn t
7.2 Cng ca vch ph hp th nguyn t
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 cng tun theo
nh lut Lambe Bear, ngha l nu chiu mt chm sng cng ban u l Io qua
m hi nguyn t t do ca nguyn t phn tch nng l N v b dy l L cm, th
chng ta c:
I = I o .e K v N . L
(7.3)
A ( v vo ) 2
2 RT ( v ) 2
(7.4)
R l hng s kh.
T l nhit ca mi trng hp th (oK).
Nu gi A l cng ca vch ph hp th nguyn t, t cng thc (7.3)
chng ta c:
A =
hay l:
log I o
= 2,303.K v .N .L
I
A = 2,303.Kv.N.L
(7.5)
(7.6)
vi k = 2,303.Kv.L
trong K l h s thc nghim, n ph thuc vo cc yu t.
H s hp th nguyn t Kv ca vch ph hp th,
- Nhit ca mi trng hp th, v
- B dy ca mi trng hp th L.
Song cng thc (7.6) cha cho ta bit mi quan h gia cng vch ph v
nng C ca nguyn t phn tch trong mu. Tc l qua h gia N v C. y chnh
l qu trnh ha hi v nguyn t ha mu phn tch. Nghin cu qu trnh ny, l
thuyt v thc nghim ch ra rng, mi quan h gia nng N v nng C trong
mu phn tch c tnh theo biu thc sau:
N = 3.1012 x
F .W .s.n.R0 b
C
Q.T .nT
(7.7)
(7.8)
(7.9)
1
2t m
(7.10)
140
rng H Ni (cm-1.10-4)
Hg-253,70 nm
0,50
Na-589,90 nm
3,50
Cd-228,80 nm
2,70
(7.11)
rng Hd
cc nhit khc nhau (oK).10-2 cm-1
2500oC
3000oC
3500oC
Li-670,80
5,70
9,10
22,00
B -249,80
11
1,20
22,00
48,00
Cs 825,10
133
1,00
1,60
4,00
2 1 1
( + )
RT A M
(7.12)
(7.13)
ngha l chng ta c:
Ht = (Hn + Hd + Hl)
(7.14)
Hnh 7.6
H thng nguyn t ha mu trong ngn la
(1) n nguyn t ha mu, (2) Mng bo him, (3) ng thi phn mu tha,
(4) ng dn cht oxi ha, (5) ng dn mu vo bung aerosol ha, (6) ng
dn cht chy C2H2, (7) Vin bi to bi aerosol.
- Phn 3. H thng my quang ph hp th, n l b n sc, c nhim v thu,
phn li v chn tia sng (vch ph) cn o hng vo nhn quang in pht hin tn
hiu hp th AAS ca vch ph.
- Phn 4. H thng ch th tn hiu hp th ca vch ph (tc l cng ca
vch ph hp th hay nng nguyn t phn tch). H thng c th l cc trang b:
+ n gin nht l mt in k ch nng lng hp th (E) ca vch ph,
+ Mt my t ghi lc ca vch ph,
+ Hoc b hin s digital,
+ Hay b my tnh v my in (printer).
+ Hoc my phn tch (lntergrator).
144
Hnh 7.7
S nguyn tc cu to h thng my AAS.
a) H 1 chm tia; b) H 2 chm tia
1- Ngun pht tia bc x n sc; 2- H thng nguyn t ha mu; 3- H thng
n sc v detetctor; 4- B khuch i v ch th kt qu o; 5- Microcomputer.
7.5 Nhng u v nhc im ca php do 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. Cc u im v nhc
im l:
- Php o ph hp th nguyn t c nhy v chn lc tng i cao. Gn 60
nguyn t ha hc c th c xc nh bng phng php ny vi nhy t 1.10-4
145
No
Nguyn t
(nm)
F-AAS
ETA-AAS
nhy (ng/mL)
Flame
01
02
Ag-328,10
Al-309,30
AA
NA
nhy (g/mL)
0,05
0,10
03
04
05
06
07
08
09
Au-242,80
Ba-553,50
Be-234,90
Bi-223,10
Ca-422,70
Cd-228,80
Co-240,70
AA
NA
NA
AA
AA
AA
AA
0,05
0,10
0,10
0,10
0,05
0,03
0,10
0,05
0,50
0,30
1,00
0,05
0,04
1,00
10
11
12
13
14
15
16
17
Cr-357,50
Cu-324,70
Fe-248,30
K-766,50
Mg-285,20
Mn-279,50
Na-589,60
Ni-232,00
AA
AA
AA
AA
AA
AA
AA
AA
0,10
0,04
0,08
0,05
0,03
0,05
0,03
0,10
0,80
0,05
0,10
0 10
0,10
0,06
0,05
0,10
18
19
20
21
Pb-283,30
Sr-466,70
Si-251,60
Zn-213,90
AA
AA
NA
AA
0,10
0,08
0,30
0,03
0,20
0,20
1,00
0,10
0,10
0,50
Ghi ch: AA: Ngn la (Khng kh + Axetylen), NA: Ngn la (Khi N2O +
Axetylen)
ng thi cng do c nhy cao nn trong nhiu trng hp khng phi lm
giu nguyn t cn xc nh trc khi phn tch. Do tn t nguyn liu mu, tn t
thi gian, khng cn phi dng nhiu ha cht tinh khit cao khi lm giu mu. Mt
khc cng trnh c s nhim bn mu khi x l qua cc giai on phc tp. cng
146
l mt u im ln ca php o ph hp th nguyn t.
u im th ba ca phng php ny l cc ng tc thc hin nh nhng. Cc
kt qu phn tch li c th ghi li trn bng giy hay gin lu gi li sau ny.
Cng vi cc trang thit b hin nay ngi ta c th xc nh ng thi hay lin tip
nhiu nguyn t trong mt mu. Cc kt qu phn tch li rt n nh, sai s nh.
Trong nhiu trng hp sai s khng qu 15% vi vng nng c 1 - 2 ppm. Hn
na, bng s ghp ni vi my tnh c nhn (PC) v cc phn mm c hp qu trnh
o v x l kt qu s nhanh v d dng, lu li ng chun cho cc ln sau.
Bn cnh nhng u im, php o ph hp th nguyn t cng c mt s hn ch
v nhc im nht nh. iu hn ch trc ht l mun thc hin php o ny cn
phi c mt h thng my AAS tng i t tin. Do nhiu c s nh khng
iu kin xy dng phng th nghim v mua sm my mc.
- Mt khc, cng chnh do php o c nhy cao, cho nn s nhim bn rt c
ngha i vi kt qu phn tch hm lng vt. V th mi trng khng kh phng
th nghim phi khng c bi. Cc dng c, ha cht dng trong php o phi c
tinh khit cao. cng l mt kh khn khi ng dng phng php phn tch ny.
Mt khc, cng v php o c nhy cao nn cc trang thit b my mc kh tinh vi
v phc tp. Do cn phi c k s c trnh cao bo dng v chm sc, cn
cn b lm phn tch cng c thnh tho vn hnh my. Nhng yu t ny c th
khc phc c qua cng tc chun b v o to cn b.
Nhc im chnh ca phng php phn tch ny l 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 n ch l phng php phn tch thnh phn ha hc ca
nguyn t m thi.
7.6 i tng v phm vi ng dng ca AAS
i tng chnh ca phng php phn tch theo ph hp th nguyn t l phn
tch lng nh (lng vt) cc kim loi trong cc loi mu khc nhau ca cc cht v
c v hu c. Vi cc trang b v k thut hin nay, bng phng php phn tch ny
ngi ta c th nh lng c hu ht cc kim loi (khong 65 nguyn t) v mt s
kim n gii hn nng c ppm (micrgam) bng k thut F-AAS, v n nng
ppb (nanogam) bng k thut ETA-AAS vi sai s khng ln hn 15%.
Trong khong 10 nm tr li y, phng php phn tch ph hp th nguyn t
c s dng xc nh cc kim loi trong cc mu qung, t, , nc khong,
cc mu ca y hc, sinh hc, cc sn phm nng nghip, rau qu, thc phm, nc
ung, cc nguyn t vi lng trong phn bn, trong thc n gia sc, v.v... nhiu
nc trn th gii, nht l cc nc pht trin, phng php phn tch ph hp th
nguyn t tr thnh mt phng php tiu chun nh lng nhiu kim loi.
Bn cnh cc kim loi, mt vi kim nh Si, P, S, Se, Te cng c xc nh
147
bng phng php phn tch ny. Cc kim khc nh C, Cl, O, N, khng xc nh trc
tip c bng phng php ny, v cc vch phn tch ca cc kim ny thng nm
ngoi vng ph ca cc my hp th nguyn t thng ng (190 - 900nm). V d C165,701 N-134,70; O-130,20; Cl-134,78; S-180,70 nm. Do mun phn tch cc
kim ny cn phi c cc b n sc c bit. Cho nn n nay, theo phng php phn
tch trc tip, i tng chnh ca phng php phn tch theo ph hp th nguyn t
vn l phn tch lng nh v lng vt cc kim loi. Cn cc Anion, cc kim, cc
cht hu c khng c ph hp th nguyn t phi xc nh theo cch gin tip thng
qua mt kim loi c ph hp th nguyn t nhy nh mt phn ng ha hc trung gian
c tnh cht nh lng, nh phn ng to kt ta khng tan, to phc, y kim loi,
hay ho tan kim loi, v.v... gia kim loi o ph v cht cn phn tch. y l mt i
tng mi, phong ph ang c nghin cu v pht trin.
Vi i tng , khong chc nm tr li y php o ph hp th nguyn t
v ang c pht trin rt nhanh, khng nhng phn tch cc kim loi m phng
hng ang pht trin nht hin nay l nghin cu xc nh cc cht hu c, nh cc
hp cht hu c halogen, lu hunh, photpho. N cng v ang c s dng nh
l mt cng c phn tch c lc cho nhiu ngnh khoa hc v kinh t. Nhiu phng
th nghim v php o ph hp th nguyn t c xy dng. Cc hng trn th
gii ch to nhiu my mi c nhiu tnh nng u vit. Cc vin nghin cu khoa
hc quc gia, cc vin nghin cu nng nghip, vin a cht, cc ngnh a cht, cng
nghip luyn kim, cng nghip ha hc, cng nghip ha du, cng nghip thc phm,
ngnh y, bnh vin, cc trng i hc u c cc phng th nghim v php o ph
hp th nguyn t. C th ni n nay, hu ht cc lnh vc ca khoa hc k thut v
kinh t u s dng phng php phn tch ph hp th nguyn t. Ring nc
ta, tuy mi tip thu k thut ny trong vng 5 nm, nhng n nay trong ton quc
chng ta cng c gn ba chc phng th nghim v h thng my o ph hp th
nguyn t.
148
Chng 8
CC K THUT NGUYN T HA MU
8.1 Mc ch v nhim v
Nguyn t ha mu phn tch l mt cng vic ht sc quan trng ca php o
ph hp th nguyn t, bi v ch c cc nguyn t t do trng thi hi mi cho ph
hp th nguyn t, ngha l s nguyn t t do trong trng thi hi l yu t quyt
nh cng vch ph hp th v qu trnh nguyn t ha mu thc hin tt hay
khng tt u c nh hng trc tip n kt qu phn tch mt nguyn t. Chnh v
th ngi ta thng v qu trnh nguyn t ha mu l hot ng tri tim ca php o
ph hp th nguyn t.
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. p ng mc ch , nguyn t ha mu phn tch, ngy nay ngi ta
thng dng hai k thut. Th nht l k thut nguyn t ha mu trong ngn la n
kh. K thut ny ra i u tin cng vi s ra i ca php o ph hp th nguyn t.
Nhng k thut ny c nhy khng cao, thng l trong vng 0,05 - 1 ppm (bng
7.3). Sau l k thut nguyn t ha khng ngn la. K thut ny ra i sau, nhng
li c nhy rt cao t n 0,1ng (bng 7.3) v hin nay li c ng dng nhiu
hn k thut nguyn t ha mu bng ngn la. Chnh v c hai k thut nguyn t ha
mu khc nhau nn chng ta cng c hai php o tng ng. l php o ph hp
th nguyn t trong ngn la (F-AAS: Flame Atomic Absorpt Ion Spectrophotometry)
v php o ph hp th nguyn t khng ngn la (Electro-Thermal Atomizat Ion
Atomic Absorpt Ion Spectrophotometry: ETA- AAS).
8.2 K thut nguyn t ha mu bng ngn la
Theo k thut ny ngi ta dng nng lng nhit ca ngn la n kh ha
hi v nguyn t ha mu phn tch. V th mi qu trnh xy ra trong khi nguyn t
ha mu ph thuc vo cc c trng v tnh cht ca ngn la n kh, nhng ch
yu l nhit ca ngn la. l yu t quyt nh hiu sut nguyn t ha mu
phn tch, v mi yu t nh hng n nhit ca ngn la n kh u nh hng
n kt qu.
8.2.1 Yu cu v nhim v ca ngn la
Trong php o ph hp th nguyn t, ngn la l mi trng hp th. N c
149
Bng 8.1b
Quan h gia nhit v loi kh t
150
Loi kh
T l kh (l/ph)
Nhit (oC)
K.K
Propan
6/1,4
2200
K.K
Axetylen
4,2/1,2
2450
K.K
Hydro
4/3
2050
Oxy
Axetylen
1/1
3000
N2O
Axetylen
2/1,8
2900
Bng 8.1b
Thnh phn kh v nhit ngn la
K.K
Axetylen
4,2/0,7
1800
K.K
Axetylen
4,2/0,9
2000
K.K
Axetylen
4,2/1,1
2300
K.K
Axetylen
4,2/1,2
2450
K.K
Axetylen
4,2/1,5
2400
K.K
Axetylen
4,2/1,6
2300
8.2.2 c im v cu to ca ngn la n kh
Nhit l mt thng s
c trng ca ngn la n
kh. Nhit ngn la ca
mt loi n kh ph thuc rt
nhiu vo bn cht v thnh
phn ca cht kh c t
chy to ra ngn la,
ngha l ng vi mi mt hn
hp kh chy, ngn la s c
mt nhit xc nh v khi
thnh phn kh chy thay i
th nhit ngn la cng b thay i (bng 8.1a v 8.1b). Ngoi yu t trn, tc
dn ca hn hp kh vo n t chy cng nh hng n nhit ca ngn la v
qua m nh hng n cng ca vch ph (hnh 8.1).
Xt v cu to, ngn la n kh gm ba phn chnh (hnh 8.2):
- Phn a: L phn ti ca ngn la. Trong phn ny hn hp kh c trn u v
151
153
Hnh 8.4
H thng to soi kh (nebulize) theo k thut pneumatic
K: Kh mang (oxy ha); S- ng dn mu; F- Kh chy; Q: Cnh qut quay
u; G- Mng bo him; A: ng dn th aeresol ln n nguyn t ha.
V (ml / ph.) =
.r.P
8.L.
(8.1)
trong :
r- bn knh ca ng mao dn dn mu;
P- chnh lch p sut gia hai u ng mao dn;
L- chiu di ng mao dn;
- nht ca dung dch mu (g.cm.s).
Bng 8.2
nh hng ca tc dn mu n cng vch ph Cu - 324,70mm
Tc kh (lt/pht)
Cng vch ph
1,00
0,150 '
2,00
0,180
3,00
0,206
4,00
0,225
5,00
0,235
6,00
0,230
(8.2)
trong :
s: sc cng b mt ca dung dch mu;
Di: t trng ca dung dch mu;
F: tn s ca my pht siu nm.
Nh vy, mun c cc
ht aerosol nh th phi s
dng tn s siu nm cao.
Tn s v cng sut ca my
pht siu nm u nh hng
n kch thc ca ht
aerosol (hnh) Trong hai k
thut aerosol ha, th k
thut pneumatic l n gin,
trang b r tin, khng phc
tp nh k thut siu nm.
Nhng k thut siu nm c
u im cho nhy cao
hn. V kch thc cc ht
sol kh kh nh, hiu sut
to sol kh cao v qu trnh aerosol t ph thuc vo kh mang v qu trnh dn mu.
c bit l vic aerosol ha cc dung dch mu c nng mui cao th n u vit hn
155
Nguyn t
Cu
Fe
Mg
Pb
Ni
Cr
Co
Mn
Zn
Pneumatic
0,05
0,0
0,05
0,10
0,10
0,10
0,10
0,05
0,03
Ultrasonic
0,03
0,03
0,03
0,08
0,06
0,08
0,07
0,03
0,02
(cc mui ca cc cht) trong ngn la, v n c dn tip vo vng trung tnm ngn
la. Tip s nung nng, nng chy, cc qu trnh ha hi v nguyn t ha ca cc
ht mu bt kh . y cc cht s c cc qu trnh chnh sinh ra ph v qu trnh
ph khng sinh ra ph din bin theo tnh cht nhit ha ca cht mu.
A. Cc qu trnh chnh: Xy ra thng theo hai c ch chnh:
- Nu nng lng (nhit ) ha hi (Eh) ca cc hp phn c trong mu nh hn
nng lng nguyn t ha (Ea) ca n, tc l Eh<Ea, th trc ht cc hp phn ny s
ha hi dng phn t. Sau cc phn t kh ny mi b phn li (nguyn t ha)
thnh cc nguyn t t do (c ch I). Hoc cng c th chng khng b phn li thnh
cc nguyn t t do, nu l cc hp cht bn nhit.
C ch I: (Eh< Ea):
MnAm (l) MnAm (k) n.M(k) + m.A(k)
M(k) + n(hv) Ph AAS
Ni chung, cc mui halogen (tr F), mui axetat, mt s mui nitrat, mt s
mui sunphat ca kim loi thng xy ra theo c ch ny. V d: Cc hp cht: CuCl2,
ZnCl2, FeCl3, Cu(Ac)2, Zn(Ac)2. v.v... theo c ch 1 ny. C ch ny cho php o
AAS c nhy cao v n nh.
- Ngc li, nu nng lng phn li Ea ca cc hp phn ca mu nh hn nng
lng ha hi Eh ca chnh n, th trc ht cc hp phn s b phn li thnh cc
nguyn t t do, ri sau mi ha hi (c ch II).
C ch II (Eh > Ea):
MnAm (l) n.M(r,l) + mA(l.r) n.M(k)
M(k) + n(hv) Ph AAS
Cc loi hp cht mui ca kim loi vi -sunphat, -photphat, -silicat, flo, thng
theo c ch II. C ch ny khng n nh, nn php o AAS km n nh, v nhy
km hn c ch 1. V th ngi ta thng thm vo mu cc mui halogen, hay axetat
ca kim loi kim lm nn mu hng cc qu trnh chnh xy ra theo c ch 1 u
vit v c li hn.
l hai c ch ca qu trnh nguyn t ha mu phn tch (qu trnh chnh)
trong ngn la n kh. N l nhng qu trnh chnh to ra cc nguyn t t do
quyt nh cng ca vch ph hp th nguyn t ca nguyn t phn tch. Yu t
quyt nh cc qu trnh ny l:
+ Nhit ca ngn la;
+ Bn cht ca cht mu v thnh phn ca mu;
+ Tc dng nh hng ca cht ph gia thm vo mu.
B. Cc qu trnh ph:
157
Th Ion ha (eV)
Na
K
Rb
Cs
Ca
Ba
Al
Mg
Be
5,21
4,32
4,06
3,87
6,10
5,50
6,60
7,60
9,30
S % b Ion ha nhit 0C
2000
2500
3000
1,00
10,0
14,0
30,0
2,00
3,00
0,60
0,30
15,0
30,5
44,0
70,0
10,0
17,0
1,00
0,60
0,30
26,0
80,5
89,0
95,0
16,0
33,0
09,0
05,0
01,0
Bng 8.5 cng cho chng ta thy rng, trong ngn la c nhit di 30000C th
kh nng b kch thch ph pht x l khng ln v nu c cng ch gi vai tr quan
trng i vi cc kim loi kim m thi.
S hp th ca phn t: Trong ngn la, ngoi cc nguyn t t do cng cn c
c cc Ion v cc phn t trng thi hi. Cc phn t ny ty theo tnh cht ca n v
cng ty thuc vo nhit ca ngn la, vng ph ta quan st, m cn c s hp th
nng lng, s Ion ha hay s kch thch ph ca chnh cc phn t . Nhng qu
trnh ny, tuy l qu trnh ph nhng cng c trng hp c nh hng n cng
vch ph ca nguyn t phn tch. Thm vo l s hp th ca cc ht mu rn
cha b ha hi. Yu t ny gi l s hp th gi.
Bng 8.5
Mc b kch thch ph pht x ca cc nguyn t - ng vi nhit khc nhau
Nguyn t
Th kch thch
Vch ph(nm)
(ev)
2000
3000
4000
Cs-852,10
1,48
4,40.10-4
7,20.10-3
3,00.10-2
Na-589,00
2,11
1,00.10-5
5,90.10-4
4,40.10-3
Ca-422,70
2,95
1 20.10-6
3,70.10-5
6,00.10-4
Zn-213,90
5,89
7,50.10-13
5,60.10-10
1,50.10-8
Bng 8.6
Tm tt cc qu trnh khi nguyn t ha mu
1. Dn mu vo bung aerosol ha.
2. Qu trnh aerosol ha mu to ra th sol kh.
159
160
Hnh 8.8
S cc qu trnh trong ngn la
M1: Kim loi phn tch; M2: Cc kim loi khc trong mu; A: Anion khng oxy;
AxOz: Anion c oxy; Mo: Kim loi t do trng thi hi; x, y v z nhn gi tr 1,2,3,4,...
161
162
163
thi trong quan h t l gia thi gian Ramp (thi gian tng nhit ) v thi gian sy
thng nm trong t l t 3/4 - 2/4 l ph hp cho nhiu nguyn t. Mt khc, mi
nguyn t cng c mt nhit sy ti a cho n (bng 8.6), ngha l nu sy mu
nhit cao hn nhit th kt qu phn tch km n nh v s mc sai s rt ln.
8.3.3.2 Tro ho luyn mu
y l giai on th hai ca qu
trnh nguyn t ha mu. Mc ch
l tro ha (t chy) cc hp cht
hu c v mn c trong mu sau
khi sy kh, ng thi nung
luyn mt nhit thun li cho
giai on nguyn t ha tip theo
t hiu sut cao v n nh. Giai
on ny c nh hng rt nhiu
n kt qu phn tch, nu chn
nhit tro ha khng u ho th
mt s hp cht c th b phn hu mt trong giai on ny, nu nhit tro ha l
qu cao. L thuyt v cc kt qu thc nghim xc nhn rng, tro ha mu t t v
nhit thp hn nhit gii hn th php o lun lun cho kt qu n nh, v mi
nguyn t u c mt nhit tro ha luyn mu gii hn (Tr.) trong php o ETAAAS.
Nhit tro ha gii hn l nhit m s tro ha mu nhit v nh
hn n, th cng vch ph hp th l khng i (hnh 8.14). Cn nu tro ha mu
nhit ln hn nhit th cng vch ph b gim v khng n nh. Nhit
tro ha gii hn ca mi nguyn t rt khc nhau, n ph thuc vo bn cht ca
mi nguyn t v ph thuc vo dng hp cht m nguyn t tn ti, cng nh
matrix (cht nn) ca mu (hnh 8.14).
Ni chung, v mt ha
hc, cc nguyn t bn nhit v
tn ti trong cc dng hp cht
bn nhit thng phi tro ha
luyn mu nhit tng i
cao. Nh v d trong hnh 8.14,
Si c nhit tro ha gii hn
l 1100oC, Ni l 1000oC, cn Pb
l 600oC. Ngay i vi mt
nguyn t nhit tro ha gii
hn Tr cng c th khc nhau,
khi chng tn ti trong cc cht
168
Tro ha
Nguyn t ha
Al
130
1100
2850
Ba
150
1100
2900
Be
130
1100
2750
Ca
130
1100
2800
Cu
120
0650
2650
Fe
120
1000
2700
Pb
100
0600
2500
Mg
150
1100
2850
Mn
130
1000
2700
Si
150
1200
2850
Na
139
0800
2200
Sr
130
1100
2800
Zn
110
0600
2500
Co
110
1100
2750
Cr
110
1100
2750
169
Khi nghin cu k qu
trnh tro ha luyn mu ca
nhiu nguyn t, ngi ta thy
rng, mi quan h gia nhit
tro ha luyn mu v cng
ca vch ph hp th
nguyn t ca cc nguyn t
thng tun theo mt trong ba
loi nh trong hnh 8.14. Loi
(1) l tiu biu cho cc nguyn
t Pb, Zn, Co, Mg. Loi (2) l
Ni, Cu. Loi (3) l Si, Ca, Al.
Mt khc cc kt qu
thc nghim cng ch ra rng,
khng nn tro ha luyn mu nhit qu gii hn, v nh th vic luyn mu chun
b cho giai on nguyn t ha s khng tt.
Ch nn tro ha nhit cao nht l bng hay thp hn nhit tro ha gii
hn mt t (khong 30 - 50oC).
Ngoi yu t nhit th tc tng nhit trong qu trnh tro ha cng c nh
hng n n nh ca cng vch ph. Ni chung, tc tng nhit qu ln
thng lm bn mu. Vic tng chm bao gi cng cho kt qu tt hn, ngha l phi
thc hin tro ha luyn mu trong mt thi gian khng qu ngn. Thng thng l t
30 - 60 giy, vi lng mu a vo cuvet nh hn 100 L. Trong tng thi gian tro
ha, thng dnh 1/3 cho vic tng nhit t nhit sy n nhit tro ha, ngha
l tc tng nhit nm trong vng t 60-100 trong 1 giy l thch hp. Sau
thi gian cn li 2/3 l gi nhit khng i chn luyn mu.
170
Hnh 8.17
Quan h gia nhit nguyn t ha v cng vch ph ca cc nguyn t
171
Hnh 8.18
nh hng thnh phn nn ca mu n nhit nguyn t ha mt nguyn t
172
Hnh 8.20
Quan h gia hnh dng lc vch ph v thi gian nguyn t ha
173
8.3.4 Cc yu t nh hng
Cng vi cc
iu kin sy, tro
ha v nguyn t
ha mu nh
trnh by trn, qu
trnh nguyn t ha
mu theo k thut
khng ngn la cn
b nh hng bi
mt s yu t khc
na. Cc yu t ny
nh hng khc
nhau i vi mi
nguyn t v cng
c khi li khng gy
nh hng.
- Trc ht l mi trng kh tr thc hin qu trnh nguyn t ha.
Kh tr thng c dng lm mi trng cho qu trnh nguyn t ha l argon
(Ar), nit (N2) v hai (He), ngha l qu trnh nguyn t ha thc hin trong mi
trng khng c oxy. Do khng xut hin hp cht bn nhit loi MeO hay MeOX.
Nhng bn cht, thnh phn v tc dn kh tr vo trong cuvet graphit u
nh hng n cng ca vch ph v nhit trong cuvet graphit (hnh 8.22).
Trong ba loi kh tr ni
trn, th Ar l kh tt nht, sau
n N2. ng thi khi
tng tc dn kh vo cuvet
graphit th cng vch ph
lun lun gim v mc
gim cng khc nhau i vi
mi nguyn t (hnh 8.22a).
Do trong phn tch, khi o
cng vch ph bt buc
phi gi cho tc dn
khng i, hoc c th tt kh
mi trng trong giai on nguyn t ha o cng vch ph.
174
- Yu t th hai
l cng sut t nng
cuvet. Nhn chung, khi
tng cng sut t
nng cuvet th cng
vch ph tng theo
(hnh 8.23). Nhng s
ph thuc ny cng
ch trong mt gii hn
nht nh, khi cng
sut t nng cuvet
nh hn 6 KW.
Cn khi t nng cuvet cng sut ln hn 7 KW th hu nh cng vch
ph khng tng na (hnh 8.23).
- Yu t th ba l tc t nng cuvet. Tc t nng cuvet v thi gian
nguyn t ha t l nghch vi nhau. Nu o din tch ca lc th yu t ny hu nh
khng nh hng, nhng nu o chiu cao ca lc th li rt khc nhau (hnh 8.24).
Ni chung chiu cao ca lc t l vi tc t nng cuvet.
175
176
Sau y l vi v d v c ch ny:
CdCl2(r,l) CdCl2(k) Cd(k)
CuCl2(r,l) CuCl2(k) Cu(k)
SbCl5(r,l) SbCl5(k) Sb(k)
Nhng ring mui AlCl3 ngoi qu trnh chnh theo c ch (a) th cn qu trnh
ph sinh ra hp cht monooxit bn nhit dng AlO nh sau:
(d) AlCl3 (r,l) Al3(k) + Cl2
(e) Alo(k) A(k) + O2
Qu trnh ph ny ph thuc vo s c mt ca oxy v nhit ca cuvet.
nhit nh hn 2500oC th qu trnh (e) hu nh khng xy ra c. V th n lm
mt nguyn t t do Al, qua lm gim cng vch ph. Do phi tm cch
ngn cn khng cho hnh thnh AlO, tc l phi hn ch qu trnh (d) xy ra khi
nguyn t ha mu. kh b qu trnh (d), ngi ta phi nguyn t ha mu trong
mi trng kh tr hay thm vo mu nhng cht ph gia thch hp.
d. S phn li ca cc phn t cht mu trc khi ha hi. Khuynh hng ny
thng xy ra i vi cc phn t c p sut ha hi thp v nhit phn li nh hn
nhit ha hi phn t ca chnh n Eh > Ed. Cc phn t thuc loi ny, di tc dng
ca nhit trong cuvet graphit, trc ht chng b phn li thnh cc monooxit hoc
thnh cc nguyn t t do trng thi rn, hay lng, ri sau mi c chuyn thnh
th hi theo cc tnh cht ring ca sn phm va c hnh thnh. Din bin ca qu
trnh thuc loi ny c th minh ho theo cc s di y:
C ch chnh 2:
(f) MxXy (r,l) Mx(r,l) + yX(k)
xM(k)
(g) MxXy (r,l) xMO(r,l) + yX(k)
xM(k)
(h) MxOy(r,l) mX(r,l) xM(K)
(i) MxOy(r,l) xMO(r,l) xM(r,l) xM(k)
Sau l qu trnh hp th bc x ca cc nguyn t M(k).
M(k) + n(vh) Ph AAS
Cc qu trnh (f) v (g) ny l i vi cc mui ca kim loi vi nitrat, cacbonat,
sun pht, phtpht, ngha l cc mui c oxy. Cc qu trnh (h) v (i) l i vi cc
hp cht oxit. Cc qu trnh theo cc c ch ny thng km n nh v cho kt qu
nhy thp hn cc qu trnh ca cc mui halogen trn. Tiu biu cho s din bin
179
cacbua kim loi l rt ln. Hin tng ny th hin rt r rng khi phn tch cc kim
loi kim th, nhm v cc t him. c bit khi cc nguyn t ny l nn ca mu,
th s xut hin cc hp cht cacbua kim loi c th lm gim nhy ca phng
php phn tch hng trm ln, thm ch c khi n ngn ln.
V th trong nhiu trng hp ngi ta phi chn nhng iu kin nguyn t ha
mu ph hp loi tr s xut hin cc hp cht cacbua, hoc thm vo mu cc cht
chy nh NH4NO3, LiBO2 Vi nng thch hp hn ch vic tip xc ca cht
mu vi cacbon, hoc tin hnh cacbua ha b mt cuvet graphit trc bng mt hp
cht cacbua bn, sau mi a mu vo nguyn t ha hoc t mu trong thuyn Ta
trong cuvet.
f. S kh xit kim loi bi cacbon. Trong cuvet graphit, di tc dng ca nhit,
mt s hp cht mu cng c th b kh bi cacbon ca cuvet. Phn ng ny rt phc
tp v n cng ph thuc vo cc yu t nh trong qu trnh hnh thnh cc hp cht
cacbua kim loi. ng thi tc ca phn ng kh ny cn ph thuc vo p sut
ring phn ca nguyn t cacbon trong cuvet v kh tr lm mi trng nguyn t ha
mu. Phn ng ny thng din bin theo hai loi:
(m) MxOy(r,l) + C(r) Mx(r,l) + CO
(n) MxOy(k) + C(k) xM(k) + CO
Trong hai loi phn ng ny, loi qu trnh (m) thng d xy ra v chim u th
hn v trong nhng trng hp ca cc oxit bn nhit, th qu trnh ny li lm cho
vic nguyn t ha mu c th tt hn. Sau y l mt vi v d v cc phn ng kh
cc oxit:
NiO(4) + C Ni(r,l)
Ni(k)
PbO(r) + C Pb(r,l) +OC
Pb(k)
Cc hp cht oxit CaO, Cr2O3, MoO3, ZnO, CdO, CuO,.. thng xy ra theo kiu
c ch ny.
Trn y l minh ho cc qu trnh c th xy ra trong cuvet graphit. Tt nhin l
c tnh cht khi qut, nn khng phi lc no, trong mi loi mu u c cc qu
trnh , m trong thc t din ra cuvet graphit c s chn lc, c s tng tc ln
nhau v ng thi cng c s loi tr nhau. Trong , qu trnh chim u th hn l
ph thuc vo nhiu yu t, nh:
+ Nhit t nng cuvet (y l yu t quyt nh);
+ Bn cht ca nguyn t v hp cht m n tn ti trong cuvetl
181
182
Hnh 8.26b
H thng nguyn t ha mu trong ngn la (Philips Pye Unicam)
184
Chng 9
TRANG B CA PHP O ASS
nhy (l/mL)
HCL
EDL
HCL
EDL
As-193,70
1,10
0,80
0,80
0,400
Cd-228,80
0,03
0,02
0,01
0,008
Pb-283,20
0,10
0,07
0,05
0,030
Hg-253,60
6,00
4,50
0,50
0,200
Sn-286,30
2,50
1,60
0,20
0,100
Zn-213,90
0,03
0,02
0,02
0,018
189
190
191
Hnh 9.5
H thng my AAS dng ngun ph lin tc
1- Ngun ph lin tc; 2- H thng bin iu v lc giao thoa; 3- B phn
nguyn t ha mu; 4- B n sc v detector; 5- B nn v khuych i tn hiu o
AAS.
Ngun pht ph lin tc c u im l d ch to, r tin v c bn tng i
193
Hnh 9.6
S quang hc ca h thng my AAS
(1)- Loi 1 chm tia; (2)- Loi 2 chm tia; V d v 1 h my AAS ca hng
196
Perrkin Elmer
9.4 Trang b pht hin, Detector, Photomultivlier
Detector l mt loi dng c quang hc dng thu nhn v pht hin tn hiu
quang hc theo hiu ng quang in ca n. Trc y thu nhn cng ca
chm sng ngi ta thng dng knh nh hay phim nh sau l t bo quang in.
l cc dng c c in c nhy km, nht l knh nh, v knh nh c nhiu
nhc im, nh kh bo qun, d b nh hng bi m, nhit , thi tit. Mt
khc, n li l mt dng c trung gian thu nhn chm sng v sau phi x l tip
mi c c cng vch ph. Tc l o en ca knh nh b chm sng tc
dng vo. Vi s pht trin ca khoa hc v k thut, ngy nay ngi ta ch to ra
c nhiu loi detector quang hc kiu ng c th khuych i tn hiu o ln c
n c triu ln. l cc ng nhn quang in (photomultivler tube). Hnh 9.7 l s
ca mt nhn quang in kiu ng .
Nhn quang in kiu ng l mt loi dng c thu nhn tn hiu quang hc c
tnh cht vn nng, n c nhy v chn lc cao. Nhiu hng ch to c cc
detector loi ny. Vng ph hot ng ca cc detector kiu ng loi ny thng l t
190 - 900 nm, c khi n 1100 nm. Tt nhin l thng s ny ph thuc vo bn cht
ca nguyn liu ch to bn catot ca n.
Hnh 9.7
Nguyn tc cu to ca nhn quang in kiu ng
H s khuch i ca loi detector ny thng n 106, i khi c loi n 107.
Nguyn liu ch to bn catot ca cc detector kiu ng l cc hp kim ca cc
kim loi kim vi Sb, Ga hay As, v d hp kim Cs-Sb; Ga-As; Na-K-Cs-S (hnh 9.8).
197
S = kC
Cu Abs
Cu Conc.
Fe Abs
Fe Conc.
Al Abs
Al Conc.
Saple 1
0.4583
2.9201
0.1523
2.1677
02085
29.6433
Saple 2
0.6738
4.3051
0.2003
2.8481
0 1128
16.0784
Saple 3
0.2856
1.8102
0.3589
5.0961
0 3789
53.7964
Saple 4
0.4126
2.6220
0.4126
5.8566
0 4055
57.5667
Saple 5
0.4933
3.1453
0.1855
2.6383
0 2369
33.6688
Saple 6
0.6337
4.0475
0.3333
4.7333
0 1278
18.2046
Saple 7
0.8568
5.4806
0.3725
5.2889
0 3014
42.8112
200
Chng 10
CC YU T NH HNG TRONG AAS
Vch chen ln
Al-308,215
V-308,211
Cu-324,754
Eu-324,753
254
Fe-271,903
Pt-271,904
0,54
Mn-403,307
Ga-403,298
0,25
Zn-213,856
Fe-213,850
200
10.2.1.3 S hp th ca cc ht rn
Trong mi trng hp th, c bit l trong ngn la n kh, nhiu khi cn c
cha c cc ht rn nh li ti ca vt cht mu cha b ha hi v nguyn t ha, hay
cc ht mui cacbon ca nhin liu cha c t chy hon ton. Cc ht loi ny
thng c th c lp v ca ngn la. Cc ht ny hoc hp th hoc chn ng i
ca chm sng t n HCL chiu vo mi trng hp th. Yu t ny c gi l s
203
Ion ha (eV)
30,00
40,00
Na
K
Rb
5,21
4,32
4,16
00,30
02,10
09,00
05,00
22,00
34,00
26,00
82,00
90,00
Cs
3,87
28,00
70,00
96,00
205
Ca
6,11
00,20
01,50
17,00
Ba
5,31
01,00
06,00
23,00
Th kch thch
T s Ni/No nhit
(eV)
2000oC
3000oC
4000oC
Cs-852,10
1,76
4,00.10--4
7,10.10-3
3,00.10-2
Na-589,00
2,12
1,00.10-5
6,00.10-4
4,00.10-3
Ca-422,70
2,95
1,10.10-7
4,10.10-5
6,00.10-4
Zn-213,90
5,86
7,00.10-13
6,00.10-8
1,10.10-6
208
209
Hnh 10.7
Khi qut v nh hng ca Cation bao gm 7 loi
Loi 1: Khi C > C2 khng nh hng; Loi 2: nh hng cc i C1 ; Loi 3:
Gim lin tc theo ng cong li; Loi 4: Khi C < C2 khng nh hng; Loi 5:
Gim theo ng cong lm; Loi 6: Khi C > C2 khng nh hng na; Loi 7: Gim
lin tc tuyn tnh, khi C tng.
- Loi l: Khi nng ca Ion gy nh hng ln hn C2 th n khng lm tng
cng vch ph ca nguyn t phn tch na, nh hng ny c s dng tng
nhy ca phng php phn tch mt nguyn t, khi thm vo mu nguyn t nh
hng c nng ln hn C2.
- Loi 2: Ti nng C1 ca nguyn t gy nh hng, cng vch ph ca
nguyn t phn tch t gi tr cc i. V th nh hng ny cng c dng tng
nhy ca phng php phn tch. Nhng phi gi (khng ch) nng ca nguyn
t gy nh hng gi tr khng i C1.
- Loi 3: Trong trng hp ny cng vch ph gim lin tc theo ng
cong li, khi nng nguyn t nh hng tng dn u (xem v d ng 5 trong
hnh 10.8).
- Loi 4: Cc Cation ch gy nh hng n cng vch ph ca nguyn t
phn tch khi nng ca n ln hn gi tr C2. Do vy, nu nng ca cc Cation
trong mu nh hn gi tr C2 th khng phi quan tnm n tm bin php loi tr.
- Loi 5: Trong trng hp ny cng vch ph ca nguyn t phn tch li b
gim lin tc theo ng cong lm, khi nng Cation gy nh hng trong dung
dch mu tng dn v y nht thit phi tm bin php loi tr nh hng ny (xem
v d trong hnh 10.10a).
- Loi 6: Khi nng ca cc Cation khc trong mu ln hn gi tr C2 th chng
khng lm thay i cng vch ph ca nguyn t phn tch.
Do , nu khng tm c bin php loi tr ph hp th chng ta thm vo
mu Cation gy nh hng vi nng ln hn gi tr C2, a nh hng gim
thnh mt gi tr hng s cho tt c cc mu phn tch v mu chun. Nh th cng
loi b c nh hng ny. Nhng tt nhin l ta lm gim nhy ca phng
php phn tch i mt t.
- Loi 7: y cc Cation l lm gim lin tc cng vch ph ca nguyn t
phn tch theo chiu tng dn nng ca n mt cch tuyn tnh (xem v d trong
hnh 10.10b, ng s 7).
Do cng cn phi tm bin php ph hp loi tr nh hng ny, hoc gi
cho cc Cation l c nng nht nh v khng i trong tt c cc mu chun v cc
mu phn tch.
210
211
Hnh 10.8
nh hng ca cc Cation thuc loi 1, 2 v 3
ng 1: Na/Rb 780 nm, n kh (khng kh + C2H2);
ng 2: K/Ba 553,6 nm, n kh (N2O + C2H2);
ng 3: K/Sr 460,7 nm, n kh (N2O + C2H2);
ng 4: La/P 213,6 nm, n kh (ETA-AAS);
ng 5: Fe/Ca 422,7 nm, n kh (O2 + C2H2);
ng 6: Sr/Ca 422,7 nm, n kh (N2O + C2H2).
212
Hnh 10.9
nh hng ca cc Cation : (thuc loi 4)
Al, Fe, Ca n Pb 283,3 nm, ETA-AAS; Cu. Ni, Fe n As 193,7 nm, F-AAS
(kh.kh + C2H2).
+ Chn iu kin x l mu ph hp loi cc nguyn t nh hng ra khi
dung dch mu phn tch o ph.
+ Chn cc thng s ca my o thch hp.
+ Thay i hay chn vch ph khc, c th km nhy mt cht.
+ Thm vo mu phn tch nhng cht ph gia ph hp chuyn mu sang cht
nn khc ph hp nhm loi tr cc nh hng ca cc Cation, nh LaCl3, SrCl2,
AlCl3 trong php o F-AAS v LiBO2, NH4NO3 hay hn hp (LiBO2 v NH4NO3)
trong php o ETA-AAS hay nhng cht ph gia khc.
Tt nhin trong mi trng hp c th cn phi nghin cu chn c loi
cht v nng ph hp ca n.
+ Chn cc iu kin nguyn t ha mu thch hp v chn lc.
+ Vi tt c cc bin php trn m khng c, th bin php cui cng l bt
buc chng ta phi tch loi b cc Cation c nh hng. Tt nhin bin php ny
rt t khi phi p dng.
(kh. kh + C2H2)
(-nt- )
(-nt- )
213
(-nt- )
(-nt- )
ng 6: Si/Ca,Mg, F-AAS
(khi c mt 1% LaCl3)
(kh. kh + C2H2)
214
Hnh 10.11
nh hng t hp ca mt s nguyn t n Ca 422.7nm trong php o F-AAS
khi c v khng c mt LaCl3
10.2.3.4 Thnh phn nn ca mu
Yu t nh hng ny ngi ta quen gi l matrix effect. Nhng khng phi lc
no cng xut hin, m thng ch thy trong mt s trng hp nht nh. Thng
thng l nhng mu c cha cc nguyn t nn di dng cc hp cht bn
nhit, kh bay hi v kh nguyn t ha.
V d: Khi xc nh cc tp cht lng vt trong cc mu oxit t him, oxit kim
loi kim th, oxit nhm, oxit zircon, cc mu mui NaCl, th cc nn ny s kh
cng ca vch ph ca nguyn t phn tch, qua lm gim nhy ca phng
php phn tch.
Trong nhiu trng hp, yu t ny lm gim hng chc ln, thm ch c trng
hp hng trm ln cng ca vch ph (bng 10.4). Nguyn nhn chnh ca nh
hng ny l s tn ti ca cc hp cht bn nhit trong mi trng hp th.
Cc hp cht ny lm kh khn, cn tr qu trnh ha hi v nguyn t ha ca
cc nguyn t phn tch.
215
Bng 10.4
nh hng ca thnh phn nn ca mu phn tch
Cht nn ca mu
0,220
0,250
2. Nh 1, thm 2% LaCl3
0,020
0,025
0,050
0,060
4. Nh 2, thm 1% NH4NO3+LiBO2
0,210
0,245
Trong bn bin php trn, bin php th nht cng ch thc hin c trong
nhng chng mc nht nh, v chng ta khng th tng nhit nguyn t ha ln
cao mi c, do s hn ch ca trang thit b, bn cht ca kh t, hn na khi nhit
nguyn t ha qu cao th li xut hin nh hng ca s tn ha v s pht x.
Cho nn bin php hai l thng dng nht. Cc cht ph gia thng hay c
dng trong php o F-AAS l LaCl3, SrCl2, Li3, KCl, AlCl3, y LaCl3 c s
dng rng ri nht, cc cht cn li ch cho mt s trng hp ring bit. Ngc li,
trong php o ETA-AAS cht ph gia c dng nhiu nht l LiBO2, NH4NO3 hay
hn hp ca hai cht ny trong mt nng ph hp. iu ny chng ta c th thy
trong v d ca bng 10.4.
10.2.3.5 nh hng ca dung mi hu c
Trong php o ph hp th nguyn t, c bit l i vi k thut nguyn t ha
mu trong ngn la, 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 hp th nguyn t ca nhiu nguyn t ln nhiu ln (bng 10
5). y l mt phng php tng nhy. V th, khi phn tch cc nguyn t c
nng rt nh st gii hn di ca php o, chng ta c th thm vo mu phn
tch mt dung mi hu c c nng ph hp th c th tng nhy ca phng
php phn tch ln n hai hay i khi n ba ln so vi khi ch dng dung mi nc.
Song dung mi hu c thm vo phi trn u c vi nc v phi c tinh
khit cao.
Nu dung mi khng tinh khit cao th chng ta li lm nhim bn mu phn
tch. Hoc nu dung mi hu c khng tan trong nc th chng ta c th chit nguyn
t phn tch t dung mi nc dng hp cht phc, v d cc phc Me-APDC vo
trong dung mi hu c, sau o ph hp th ca nguyn t phn tch trong dung mi
hu c
V d dung mi MIBK (Methyl Izobutyl Ketone) l dung mi hu c in hnh
chit cc phc Me-APDC cho php o F-AAS (Me: l cc Ion kim loi nng,
APDC l Amonium Pyrolydine Dithio-carbamate. Cc phc Me-APDC c chit tt
vo MIBK, CHCl3, CCl4 trong mi trng pH t 2 - 6).
Vic s dng dung mi hu c y c hai cch:
- Nu dung mi hu c tan trong nc th ngi ta thm vo dung dch mu phn
tch mt nng dung mi hu c thch hp tng nhy ca phng php phn
tch.
- Nu dung mi hu c khng tan trong nc th ngi ta chit cht phn tch
dng hp cht phc ca n vi mt thuc th thch hp vo dung mi hu c . Nh
th va tng nhy, va loi tr c cc Ion cn tr.
217
Bng 10.5
nh hng ca dung mi hu c n cng vch ph
STT
218
Dung mi hu c thm vo
Cng Cu-324,70
nm
1,000
1,670
1,750
2,000
Nh 1, thm 20 % Izobutanol
2,400
Nh 1, thm 70 % Axeton
2,500
Nh 1, thm 50 % EAK
2,600
2,800
3,000
Chng 11
PHN TCH NH LNG BNG PH AAS
Io
K '.N .L
I
(11.1)
(11.2)
(11.3)
(11.4)
(11.5 )
220
mx
.100
m
(11.6)
Bng 11.1
Mi quan h gia cc loi n v nng (d=1)
n v gc
Tng ng vi (1)
Tng ng vi (1)
1000 ppm
1 mg/mL
10-3g/mL
1 ppm
1 g/mL
10-6g/mL
1 ppb
1 n/mL
10-9g/mL
1 ppp
1 pg/mL
10-12g/mL
1 ppf
1 fg/mL
10-15g/mL
1 ppa
1 ag/mL
10-18g/mL
n v gc
Tng ng vi cc n v sau
g
Ng
ng
pa
1 mg
10-3
1 g
10-6
10-6
1 ng
10-9
10-9
10-9
1 pa
10-12
10-12
10-12
10-12
1 fg
10-15
10-15
10-15
10-15
10-15
1 ag
10-18
10-18
10-18
10-18
10-18
fg
10-18
Bng 11.2
Chuyn i gia cc nng
Nng u c
H s phi nhn vo
mpp
g/L
0,001p
ppm
g/L
ppm
mol/ (m)
0,000.1p.A
ppm
% (trng lng)
0,0001
g/mL
ppm
1/p
g/mL
% (trng lng)
1/10000.p
ppb
ng/mL
trong :
p: t trng ca dung dch
A: nguyn t gam hay phn t gam ca cht phn tch.
- Vi mu rn: Nu trong 1 gam mu c cha 10-6g cht phn tch th gi tr ny
(10-6g) c gi l 1ppm. Cc c s ca n v ppm l ppb, ppp, ppf v ppa. Cc n
v ny km nhau 1000 ln (bng 11.1). V d: Hm lng Cu trong thp l 5 ppm,
ngha l c 1 kg thp th c 5 mg Cu, hay 1 Tn thp c 5 gam Cu.
- Vi mu lng: Nu trong 1 mL mu c cha 10-5g cht phn tch v khi t trng
ca dung dch mu bng 1 th i lng 10-5g/mL mu cng c nh ngha l 1 ppm.
V d: Hm lng Fe trong nc l 2 ppm, ngha l c 1 lt nc th c 2 mg Fe.
Hai khi nim ny c dng tng t nh nhau. Khi mu phn tch l cht rn
th ngi ta thng dng n v l g(g/g), kg(mg/kg), hay tn(g/t); cn khi mu l
cht lng th dng n v mu l m(g/mL), Lt(mg/L).
d) Nng mol/lit (M)
Khi nim nng ny biu th s phn t gam cht phn tch c trong mt lt
dung dch mu. N l khi nim thng thng trong ha phn tch (xem gio trnh Ha
phn tch nh lng c s).
V d vit NaOH 0,1 M, th c ngha l c trong 1 lt dung dch NaOH th c 0,1
phn t gam NaOH.
224
cc nguyn t, gia cc vch ph vi nhau s d dng v thun tin hn. Bng 11.3 l
mt vi v d v nhy ca mt s nguyn t kim loi theo mt vi vch ph hp th
nguyn t ca n trong nhng iu kin nguyn t ha nht nh ca ngn la n kh.
y cc nguyn t khc nhau, cc vch ph khc nhau cng c nhy khc nhau.
Nguyn t no, vch ph no c kh nng hp th bc x mnh th php o theo vch
s c nhy tng i cao.
Trong hai khi nim trn, trong php o ph AAS, nh ngha v nhy tng
i ( nhy nng ) lun c dng ph bin so snh hay nh gi cc phng
php phn tch c th cho tng i tng.
Bng 11.3
nhy ca mt s nguyn t
Vch ph (nm)
226
Tng i (g/l)
Tuyt i (pa)
Ag 328,10
0,002
03,5
238,30
0,010
07,5
Al 309,30
0,04
45,0
396,20
0,07
60,0
308,20
0,10
80,0
394,40
1,20
120,0
Cr 357,90
0,05
15,0
359,40
0,10
23,0
425,40
0,20
45,0
Cu 324,80
0,008
27,0
327,40
0,015
54,0
216,50
0,050
162,0
Fe 248,30
0,005
20,0
248,80
0,007
35,0
302,10
0,025
72,0
252,30
0,030
100,0
Bng 11.4
nhy, gii hn pht hin v khong xc nh ca cc nguyn t theo AAS
(theo VH2/2P)
Nguyn t
Vch o (nm)
1
n kh
nguyn t ha
Cc c trng ca AAS
nhy
(g/mL)
3
Al 309,3
N2O - C2H2
1,0
0,2
2 - 200
Sb 217,6
KK - C2H2
0,4
0,1
1 - 60
As 193,7
Ar - H2
0,5
0,2
1 - 50
As 193,7
KK - C2H2
1,2
2,0
10 - 100
Ba 553,6
N2O. C2H2
0,3
0,2
0,6 - 60
Be 234,9
N2O - C2H2
0,02
0,01
0,04 - 4
Bi 223,1
KK - C2H2
0,3
0,2
1 - 50
B 249,7
N2O - C2H2
12,0
10,0
25 - 1500
Cd 228,8
KK - C2H2
0,01
0,003
0,02- 2
Cs 852,1
KK - C2H2
0,1
0,03
0,2 - 10
Ca 422,7
KK - C2H2
0,05
0,006
0,1 - 8
Ca 422,7
N2O - C2H2
0,03
0,008
0,05 - 4
Cr 357,9
KK - C2H2
0,08
0,02
0,2 - 15
Cr 357,9
N2O - C2H2
0,15
0,15
0,4 - 25
Co 240,7
KK - C2H2
0,1
0,02
0,2 - 20
Cu 324,8
KK - C2H2
0,04
0,01
0,1 - 10
Ga 287,4
KK - C2H2
1,0
0,1
2 - 150
Ge 265,2
N2O - C2H2
1,5
0,4
3 - 200
Au 242,8
KK - C2H2
0,2
0,5
0,5 - 20
Hf 307,3
N2O - C2H2
15,0
10,0
30 - 2000
In 303,9
KK - C2H2
0,4
0,2
1 - 100
Ir 208,9
KK - C2H2
1,0
0,6
2,5 - 200
Ir 208,9
N2O - C2H2
8,0
3,0
20 - 1500
Fe 248,3
KK - C2H2
0,1
0,02
0,2 - 20
Pb 2 1 7,0
KK - C2H2
0,15
0,05
0,3 - 25
Pb 283,3
KK - C2H2
0,3
0,07
0,75 - 50
Li 670,8
KK - C2H2
0,02
0,005
0,05 - 4
227
Mg 285,2
KK - C2H2
0,005
0,001
0,1 - 4
Mn 279,5
KK - C2H2
0,03
0,01
0,05 - 5
Hg 253,7
KK - C2H2
4,0
0,5
10 - 150
Mo 813,3
KK - C2H2
1,9
0,15
4 - 200
Mo 313,3
N2O - C2H2
0,5
0,2
1 - 100
Ni 232,0
KK - C2H2
0,07
0,02
0,2 - 15
Ni 341,5
KK - C2H2
0,4
0,1
1 - 80
Nb 334,9
N2O - C2H2
25,0
50,0
100 - 4000
Os 290,9
N2O - C2H2
1,5
0,5
2 - 250
Pd 247,6
KK - C2H2
0,25
0,1
1 - 40
Pd 247,6
2O
- C2H2
2,2
1,0
5 - 200
K 766,6
KK - C2H2
0,02
0,01
0,04 - 4
Pt 265,9
KK - C2H2
1,5
0,3
5 - 300
Pt 265,9
N2O - C2H2
10,0
8,0
25 - 2000
Rh 343,5
KK - C2H2
0,5
0,1
1,100
Rb 780,0
KK - C2H2
0,05
0,03
0,1 - 10
Ru 349,9
KK - C2H2
1,0
0,3
2 - 150
Se 196,0
Ar - H2
0,2
0,2
1,20
Se 196,0
KK - C2H2
0,5
2,0
2 - 50
Si 251,6
N2O - C2H2
2,0
0,7
4 - 400
Ag 328,1
KK - C2H2
0,05
0,006
0,1 - 10
Na 589,0
KK - C2H2
0,01
0 004
0,02 - 2
Sr 460,7
N2O - C2H2
0,1
0,02
0,2 - 20
Ta 271,5
N2O - C2H2
12,0
4,0
30 - 2000
Te 214,3
KK - C2H2
0,5
0,2
1 - 80
Ti 276,8
KK - C2H2
0,4
0,06
1 - 80
Sn 224,6
KK - C2H2
0,4
0,1
1 - 60
Sn 224,6
N2O - C2H2
2,4
0,6
5 - 300
Ti 364,3
N2O - C2H2
2,0
0,4
20 -1500
W 255,1
N2O - C2H2
10,0
4,0
300-20000
U 358,5
N2O - C2H2
150,0
80,0
2 - 150
V 318,4
N2O - C2H2
1,0
2,0
0,02 - 2
Zn 213,9
KK - C2H2
0,01
0,003
50 - 2000
Zi 360,1
N2O - C2H2
15,0
5,0
4 - 400
228
Vch o
(nm)
Tng i
(g/mL)
Tuyt i
(pa)
Ag 328,10
0,002
5.000
0,000001
Al 309,30
0,02
20.000
0,00002
As 193,70
0,15
25.000
0,0001
20
Au 242,80.
0,01
100,000
0,0001
10
Ba 553,50
0,01
20.000
0,0005
50
Tuyt i
(pa )
229
230
Be 234,90
0,002
1.000
0,00003
Bi 223,10
0,003
500.000
0,0002
20
Ca 422,70
0,003
1.000
0,00001
Cd 228,80
0,001
1.000
0,000001
0,00005
1
10
2.000
0,0001
0,00002
0,00003
0,01
10.000
0,000001
Na 589,00
0,001
5.000
0,0001
0,1
C 357,90
0,001
100
0,00001
Cu 324,70
0,002
2.000
0,000002
0,2
Fe 248,30
0,02
200.000
0,00003
K 766,50
0,0002
2.000
0,000005
0,3
Pb 217,00
0,01
20.000
0,00002
Pt 265,90
0,1
100,000
0,002
200
Sb 217,60
0,04
250.000
0,0001
10
Se 196,00
0,2
50.000
0,0005
50
Sn 235,50
0,02
100.000
0,0001
10
Sr 460,70
0,002
10.000
0,00005
Ti 364,30
0,05
100.000
0,002
2000
V 318,50
0,05
20.000
0,001
100
Mg 285,20
0,003
3.000
Mn 279,50
0,001
Mo 313,30
Bng 11.5a
Gii hn pht hin ca php o ETA - AAS theo cc my khc nhau
Nguyn t
Vch o(nm)
Ag 328,1
Al 309,3
Au 242,8
Cd 288,8
Co 240,7
Cr 357,9
Cu 324,7
Fe 248,3
Mg 285,2
Mn 275,9
Mo 313,3
Ni 232,0
Pb 217,0
Pt 265,9
Sn 235,5
V 318,5
Zn 213,9
CRA-63
0,2
30,0
0,1
4,0
2,0
4,0
4,0
0,06
0,5
13,0
10,0
3,0
100,0
9,0
100,0
0,08
A-3470
10,0
0,6
8,0
5,0
10,0
0,2
3,0
20,0
10,0
3,0
200,0
400,0
0,08
IL-355
4,
90,
10,
2,
40,
20,
7,
100,
0,1
5,
200,
10,
100,
400,
1,
(11.7)
(II.8)
232
235
Bng 11.6
Vng tuyn tnh ca php o
Nguyn t vch (nm)
236
nhy (g/mL)
Al 309,3
0,2
0,5 - 15,
396,2
0,5
1 - 20,
237,3
1,2
2 - 30,
257,4
2,5
4, - 50,
Ba 553,6
0,08
0,1 - 10,
455,4
0,1
0,5 - 15,
350,1
48,0
50 - 500,
Cr 357,9
0,03
0,1 - 10,
359,4
0,06
0,2 - 15,
425,4
0,3
1 - 25,
429,0
0,6
1,2 - 30,
Fe 248,3
0,05
0,1 - 10,
252,3
0,15
0 3 - 15,
271,9
0,25
0,5 - 25,
372,0
0,5
0,8 - 30,
Mg 279,5
0,02
0,1 - 6,
279,8
0,04
0,2 - 8,
280,1
0,1
0 4 - 15,
403,1
0,3
0,5 - 20,
Ni 230,0
0,04
0,1 - 10,
331,1
0,1
0,2 - 16,
234,6
0,25
0,5 - 25,
341,5
0,3
0,6 - 30,
Cu 324,7
0,01
0,1 - 5,
327,4
0,02
0,3 - 8,
217,9
0,5
0,8 - 20,
216,5
0,7
1 - 25,
Si 251,6
0,06
0,2 - 12,
250,7
1,2
2 - 25,
288,2
8,0
10 - 80,
- Thi gian, nhit ca cc giai on sy mu, tro ha, luyn mu v thi gian
nguyn t ha o cng vch ph.
+ Kh mi trng cho qu trnh nguyn t ha mu.
+ Cng sut t nng cuvet graphit nguyn t ha mu.
+ Lm sch cuvet graphit.
+ Lng mu a vo cuvet nguyn t ha o ph.
11.1.8.3 Cc yu t nh hng
Trong mt php o c th cc yu t nh hng cn phi xem xt l:
Cc nh hng v ph.
- Cc nh hng v vt l.
- Cc nh hng ha hc ca cc Cation v Anion c tng mu.
- nh hng ca thnh phn nn ca mu.
Cc yu t ny c cp k trong chng 10. Tt nhin cc yu t ny cng
ch c trong mt s trng hp nht nh v nhiu trng hp l khng c. Nhng
cng cn phi bit chnh xc khi n xut hin th tm bin php loi tr ph hp.
11.1.8.4 Chn quy trnh x l mu ph hp
X l mu l cng vic u tin ca ngi lm phn tch. Nu x l mu khng
tt th tt nhin s c kt qu phn tch sai, hoc nh (lm mt), hoc ln (lm
nhim bn thm).
Trong phn tch lng vt (vi lng), giai on x l mu l cc k quan trng
i vi c qu trnh phn tch. V trong giai on ny chng ta c th lm mt hay lm
nhim bn thm nguyn t cn xc nh c khi n hng chc, thm ch c khi n
hng trm ln nu chn quy trnh x l mu sai v cc ng tc trong qu trnh x l
mu thc hin khng cn thn.
Cc ngun gy sai trong qu trnh x l mu c th l:
+ Mi trng lm vic khng sch yu cu.
+ Dung mi, ha cht (axit) dng x l mu khng tinh khit.
+ Dng c ng, cha mu khi x l khng tt, khng sch.
+ Nc ct khng tinh khit.
Phng php chn x l mu khng tch chit c tt nht nguyn t cn
phn tch vo dung dch phn tch.
- Cc cht chun khng t yu cu cao.
l cc vn cn c ch trong mi trng hp c th. Cc vn ny s
239
240
Do trc ht ngi
ta phi chun b mt dy
mu u, dy mu chun
(thng thng l 5 mu u)
v cc mu phn tch trong
cng mt iu kin. V d
cc mu u c nng ca
nguyn t X cn xc nh l
C1, C2, C3, C4, C5 v mu
phn tch l Cx1, Cx2, Sau
chn cc iu kin ph
hp v o cng ca mt
vch ph hp th ca nguyn
t phn tch trong tt c cc Hnh 11.6
mu u v mu phn tch th chun ca phng php ng chun
c chun b trn.
V d ta thu c cc
gi tr cng tng ng
vi cc nng l A1,
A2, A3, A4, A5 v Ax1, Ax2
v.v... By gi trn h ta
A - C theo cc im c ta
(C1A1), (C2A2), (C3A3),
(C4A4), (C5A5) ta s dng
c mt ng biu th
mi quan h A - C.
chnh l ng chun ca
phng php ny (hnh
11.6).
Hnh 11.6
th chun ca phng php ng chun
C1
C2
C3
C4
C5
Cx
Cx
Cx
Cx
Cx
Cx
Lng thm vo
C1
C2
C3
C4
C5
Cht khc
A o c
Al
A2
A3
A4
A5
Axo = k.Axl
(a)
(b)
Ax = a.Cx (a)
Vi mu u:
Ao = a.Cl (b)
(a)
245
(b)
(11.7)
tng ca cc phng php phn tch ny l phn tch kim loi trong cc loi mu v
c v hu c. V d cc mu v c l qung, t, , khong liu, mui, oxit, kim loi,
hp kim, xi mng, nc, khng kh v cc mu hu c l mu thc phm, ng, sa,
hp, rau qu, ung, gii kht, mu, se rum, nc tiu, cc mu cy v sinh hc.
Khi phn tch cc loi mu ny th nguyn tc chung l gm hai giai on.
- Giai on I: X l mu a nguyn t kim loi cn xc nh c trong mu v
trng thi dung dch ca cc Cation theo mt k thut ph hp, chuyn c hon
ton nguyn t cn xc nh vo dung dch o ph.
- Giai on II: Phn tch nguyn t cn thit theo ph hp th nguyn t ca n
theo nhng iu kin ph hp (mt quy trnh) c nghin cu v chn ra.
Tt nhin, y giai on I l cc k quan trng. V nu x l mu khng tt th
c th lm mt nguyn t cn phn tch hay lm nhim bn thm vo. Ngha l vic x
l mu khng ng s l mt ngun sai s rt ln cho kt qu phn tch, mc du
phng php phn tch c chn l ph hp nht. Vn ny c bit c ngha
ln trong phn tch lng vt cc nguyn t.
Cc phng php phn tch trc tip ny l thch hp xc nh cc kim loi,
m bn thn chng c ph hp th nguyn t. Nhng trong khong nm nm li y,
nhiu phng php phn tch gin tip xut hin phn tch cc cht khng c ph
hp th nguyn t, v d nh xc nh cc Anion, cc nhm phn t, cc hp cht hu
c, cc dc phm.
11.3.2 Cc phng php xc nh gin tip cc cht bng AAS
11.3.2.1 Nguyn tc chung
y l mt phm vi ng dng mi ca php o ph hp th nguyn t phn
tch cc cht khng c ph hp th nguyn t hay ph hp th nguyn t ca n km
nhy. Cc phng php ny hin nay ang c pht trin v ng dng phn tch
cc Anion v cc cht hu c.
Ni chung cc phng php xc nh gin tip cc cht khng c ph hp th
nguyn t bng php o ph hp th nguyn t c da theo hai nguyn tc chnh
sau y.
- Nguyn tc th nht ca cc phng php ny l nh mt phn ng ha hc
trung gian c tnh cht nh lng ca cht ta cn nghin cu X (cht X cn xc nh)
vi mt thuc th thch hp c ph AAS trong mt iu kin nht nh.
- Nguyn tc th hai l da theo hiu ng l khi cht phn tch X c mt trong
mu vi mt vng nng nht nh, th n lm gim hay lm tng cng , vch
ph hp th nguyn t ca mt kim loi mt cch tuyn tnh. Sau y l mt vi
phng php c th.
247
xy dng phng php phn tch cc Ion SO42-, Cl , C2O42-, po43-, NH4+. V d
xc nh SO42- 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 l xc nh lng Ba hay Pb cn d c trong dung dch
sau khi phn ng vi Ion sunphat. Nh vy t lng Ba hay Pb tiu tn kt
ta Ion SO42- chng ta d dng tnh c hm lng ca Ion sunphat c trong mu
phn tch. V d cc phn ng c s dng trong cch ny:
Cl + Ag+ AgCl xc nh Anion Cl
Br + Ag+ AgBr xc nh Anion Br
I + Ag+ AgI xc nh Anion I
C2O42- + Ca2+ CaC2O4 xc nh Anion C2O42PO43- + Ca2+, Ca3(PO4)2 xc nh Anion PO43SO42- + Ba2+ BaSO4 xc nh Anion SO42SO42- + Pb2+ PbSO4 xc nh Anion SO42PO43- + Mg2+ + NH4+ MgNH4PO4 xc nh Anion PO43- Cng bng cch ny ngi ta tin hnh xc nh penicillin, vitamin B1, v.v...
theo php o AAS bng cch cho mu vitamin Bl tc dng vi mt lng xc nh
NaPbO2 trong KOH nng chy 280oC. V trong iu kin ny, c mt phn t
vitamin B1 bao gi cng to ra mt phn t PbS. Sau tch ly kt ta PbS, ra sch
v ha tan n trong axit nitric 6M v xc nh Pb. Ri t hm lng Pb ta tnh c
hm lng ca vitamin B1 trong mu phn tch.
Mt khc, y chng ta cng c th xc nh lng Pb trong phn NaPbO2 d
khng tc dng vi vitamin B1, ri sau cng tnh c hm lng B1.
Hin nay, theo cch ny, c nhiu hp cht hu c c cha S (lu hunh)
c xc nh bng php o ph hp th nguyn t, nu Ion S2- trong phn t hu c
tc dng c vi mt Ion kim loi trong mt iu kin nht nh to ra c mt
248
nh bng cch cho n tc dng vi thuc th molipat trong mi trng axit HNO3a
6M, to ra hp cht d a photpho-molipat kt ta, tch ly sn phm ny, ho tan
n trong dung dch kim 0,5M v xc nh Mo trong dung dch hp cht d a theo
vch ph hp th nguyn t Mo-313,0 nm. T tnh ra lng P c trong mu. Mui
asenat v mt s hp cht alcaloit cng c xc nh theo cch gin tip ny.
Cch ny c dng xc nh P, Si qua thuc th molipic trong mi trng
axit nc c 6M sinh ra hp cht d a ca P vi Mo theo phn ng:
PO43- + NH4+ + MoO42- + HNO3 (NH4)3[P(Mo3O10)4]
m chng ta c dng trong phn tch ha hc xc nh P trong t trng
bng phng php trung ha. Nhng y sau khi c c hp cht kt ta d a ca
P, ngi ta ho tan n trong kim 0,5 M v xc nh hm lng ca nguyn t
molipden, bng ph hp th nguyn t ca Mo, sau suy ra hm lng P trong mu
phn tch.
4. Qua phn ng kh Ion kim loi v kim loi
Mt s cht hu c khi tc dng vi mt s mui kim loi trong nhng iu kin
xc nh, n kh cc kim loi v trng thi kim loi t do c tnh cht nh lng. V
d nh phn ng ca chc andehit vi mui AgNO3 trong mi trng NH3 (thuc th
Tulene). Tnh cht ny c ng dng phn tch cc cht hu c c nhm -CHO
bng php o AAS. Cc andehit c xc nh bng cch cho andehit tc dng vi
mt lng d AgNO3 ton b andehit 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
php o AAS theo vch ph Ag-328,1 nm, t tnh ra hm lng andehit c trong
mu phn tch. V trong iu kin ny c 1 nhm -CHO th lun lun gii phng ra 1
nguyn t Ag kim loi theo phn ng sau:
R-(CHO)n + n(Ag+) nAgo
V d vi andehit focmic (HCHO), th ta c:
HCHO + Ag+ Ago
5. Phn ng th hay ph hu hp cht phc
Nguyn tc ca cch ny l cho cht phn tch X tc dng vi mt hp cht phc
trong mt iu kin xc nh, to ra sn phm mi bn hn phc ban u. Bng
cch ny ngi ta c th xc nh c cc Anion hay mt s kim loi khng nhy
ph hp th qua mt kim loi nhy ph hp th.
V d nh xc nh Anion F khi cho n tc dng vi phc Fe(III)-SCN c nng
xc nh. Sau chit tch phn phc Fe(III)-SCN d v xc nh Fe trong phn
phc d ny theo vch ph hp th Fe-248,3 nm trong ngn la n kh axetylen
khng kh.
250
ny s lm gim cng vch ph ca kim loi mt cch tuyn tnh trong mt vng
nng nht nh ca X. Ngha l y chng ta c cng vch ph (pic ph) c
gi tr nm.
V d mun xc nh Anion F ngi ta dng Mg c nng 2 ppm (2 g/mL)
v o vch ph pht x ca Mg-285,20 nm. nh lng F theo phng php
ng chun dy chun c pha theo bng sau.
Dy chun xc nh nng Anion F
Cc cht
Dy chun
Co
C1
C2
C3
C4
C5
Cx
Nng Mg (ppm)
Nng F (ppm)
10
Cx
HCI (%)
A5
Ax
Ao
A1
A2
A3
A4
Sau dng ng chun v pht hin nng ln F trong mu phn tch Cng,
(hnh 11.9a v 11.9b).
2. Theo s tng cng vch ph (tng tc Cation-phn t)
Cng hon ton tng t nh nguyn tc ca cch trn, nhng c khc l khi c
mt ca cht phn tch X th cng vch ph ca nguyn t kim loi li c tng
tuyn theo s tng nng ca cht phn tch X c trong mu vi mt vng nht nh.
Dy chun
Co
C1
C2
C3
C4
C5
Cx
Ng Ca(ppm)
Protein (mM)
0,02
0,04
0,06
0,08
0,10
Cx
HCl (%)
A5
Ax
Ao
A1
A2
A3
A4
3. Tng tc Cation-Cation
Cch ny thng c dng xc nh mt nguyn t kim loi khng nhy ph
253
Qua Hydro
As
140
0,2
Sb
30
0,1
Bi
29
0,2
Se
30
0,2
Sn
110
0,5
+ Vi As:
ASO43- + Na2BH4 + HCl AsH3
ASO43- + Na2BH4 + HCl AsH5
+ Vi Se:
SeO43- + Na2BH4 + HCl SeH4
SeO43- + Na2BH4 + HCl SeH6
+ Vi Te:
TeO43 + Na2BH4 + HCl TeH4
TeO43 + Na2BH4 + HCl TeH8
Cc kh hydrua sinh ra trong cc phn ng trn c kh argon dn vo h thng
nguyn t ha mu ca my v o ph ca cc nguyn t theo cc iu kin thch hp
cho mi nguyn t.
Theo k thut ny, hin nay ngi ta c ring mt h phng php ha hi v
nguyn t ha lnh qua vic to hp cht kh hydrua d b phn hu phc v vic tch
v xc nh cc nguyn t ni trn. Phng php ny c nhy rt cao, c 1 - 5 ng.
Cc hng sn sut my o AES v AAS u c bn b trang b cho k thut ny
vi cc kiu khc nhau, t n gin n hon chnh v t ng.
2. Phn ng sinh ra hp cht alkyl v cacbonyl
Theo cch ny ngi ta da vo phn ng ca Ion kim loi vi nhm Co hay gc
alkyl sinh ra mt hp cht cacbonyl hay mt nhm alkyl ca kim loi trong mt
iu kin xc nh v c tnh cht nh lng, m cc kim loi li khng c kh
nng sinh ra cc hp cht hydrua kim loi.
V d Ni trong cc hp cht hu c c th c xc nh qua vic iu ch hp
cht Ni-cacbonyl, ri sau nh mt kh mang tr dn hp cht ny vo mi trng hp
th ca php o F-AAS xc nh Ni vi nhy c 1 ng.
Cng tng t, Pb cng c xc nh qua phn ng ca Pb(II) vi LiCH3
sinh ra Pb(CH3)4 v sau dn hp cht ch alkyl ny vo mi trng hp th o
ph ca Pb vi nhy cao hn nhiu ln so vi php o bnh thng nguyn t ha
Pb trong ngn la n kh.
Ni tm li cc phng php phn tnh gin tip hin nay l mt hng mi ng
dng php o ph hp th nguyn t, m rng phn tch cc kim, Anion v cc
hp cht hu c, hay phn tch cc kim loi m ph hp th nguyn t ca n qu km
nhy. y l mt hng mi, ang c pht trin v s dng trong vi nm li y,
nhng c nhiu trin vng.
255
256
Chng 12
CC IU KIN O PH HP TH NGUYN T
V PHT X NGN LA CA MT S NGUYN T
1. Nguyn t.
Al
No
Vch ph (nm)
Al-309,30
Al-396,20
1,5 ln km
Al-308,20
1,8 ln km
Al-394,40
3,5 ln km
km vch s 1
Ghi ch
Ag
- Vch ph o AAS:
No
Vch ph (nm)
Mc nhy ph km
vch s 1
Ag-328,10
Ag-328,30
2,5 ln km
Ghi ch
Au
Vch ph (nm)
Mc nhy ph km
vch s 1
Au-242,80
Au-267,60
2,5 ln km
Au-312,30
900 ln km
Ghi ch
4. Nguyn t.
Ba
Vch ph (nm)
Mc nhy ph km
vch s 1
Ba-553,60
Ba-455,40
6 ln km
Ba-350,10
20 ln km
Ghi ch
Be
Vch ph (nm)
Mc nhy ph km
vch s 1
1
2
3
Be-234,90
Be-313,04
Be-332,14
1
10 ln km
80 ln km
Ghi ch
Bi
No
Vch ph (nm)
Mc nhy ph km
vch s 1
Bi-223,10
Bi-222,80
4 ln km
Bi-306,80
4,5 ln km
Bi-227,70
20 ln km
Ghi ch
Ca
260
No
Vch ph (nm)
Mc nhy ph km
vch s 1
Ca-422,70
Ca-239,90
150 ln km
Ghi ch
Cd
Vch ph (nm)
Mc nhy ph km
vch s 1
Cd-228,80
Cd-326,90
500 ln km
Ghi ch
Co
261
No
Vch ph (nm)
1
2
3
4
Co-240,70
Co-242,50
Co-241,20
Co-252,10
Mc nhy ph km vch
s 1
1
1,5 ln km
2,5 ln km
8,5 ln km
Ghi ch
Cr
Vch ph (nm)
Mc nhy ph km
vch s 1
Cr-357,90
cr-359,40
2 ln km
Cr-360,30
3,6 ln km
Cr-429,00
10 ln km
Ghi ch
11. Nguyn t.
Cu
Vch ph (nm)
Mc nhy ph km
vch s 1
Cu-324,76
Cu-327,40
2 ln km
Cu-217,90
4,5 ln km
Cu-222,60
22 ln km
Ghi ch
Fe
Vch ph (nm)
Mc nhy ph km
vch s 1
Fe-248,30
Fe-248,80
2,5 ln km
Fe-271,90
3,5 ln km
Fe-372,00
12 ln km
Ghi ch
Vch ph (nm)
Mc nhy ph km
vch s 1
K-766,50
K-769,90
3 ln km
K-404,40
200 ln km
K-407,70
210 ln km
Ghi ch
Li
Vch ph (nm)
Mc nhy ph km
vch s 1
Li-670,80
Li-323,30
330 ln km
Li-610,40
1400 ln km
Ghi ch
Mg
Vch ph (nm)
Mc nhy ph km
vch s 1
Mg-285,20
Mg-202,60
40 ln km
Mg-279,60
100 ln km
Ghi ch
Mn
Vch ph (nm)
Mc nhy ph km
vch s 1
Mn- 279,50
Mn- 279,80
1,5 ln km
Mn- 280,10
3 ln km
Mn- 403,00
10 ln km
Ghi ch
265
Na
No
Vch ph (nm)
Mc nhy ph km
vch s 1
Na-589,00
Na-589,60
2,5 ln km
Na-330,30
300 ln km
Ghi ch
Ni
No
Vch ph (nm)
Mc nhy ph km
vch s 1
Ni-232,00
Ni-341,50
2,5 ln km
Ni-305,10
4,5 ln km
Ni-234,60
8 ln km
Ghi ch
Pb
Vch ph (nm)
Mc nhy ph km
vch s 1
Pb-217,00
Pb-283,30
2 ln km
Pb-261,40
40 ln km
Pb-368,40
100 ln km
Ghi ch
20. Nguyn t.
Rb
Vch ph (nm)
Mc nhy ph km
vch s 1
Rb-780,00
Rb-794,80
2,5 ln km
Rb-420,20
100 ln km
Rb-421,60
260 ln km
Ghi ch
Sb
Vch ph (nm)
Mc nhy ph km
vch s 1
Sb-206,80
Sb-217,60
2 ln km
Sb-231,20
8 ln km
Ghi ch
Si
Vch ph (nm)
Mc nhy ph km
vch s 1
Si-251,60
Si 250,70
3 ln km
Si-251,40
4 ln km
Si-252,90
12 ln km
Ghi ch
Si
Vch ph (nm)
Mc nhy ph km
vch s 1
sr-460,70
Sr-407,80
25 ln km
Ghi ch
Zn
Vch ph (nm)
Mc nhy ph km
vch s 1
Zn-213,90
Zn-307,60
2000 ln km
Ghi ch
Zr
270
No
Vch ph (nm)
Mc nhy ph km
vch s 1
Zr-360,10
Zr-303,10
2 ln km
Zr-352,00
2 ln km
Zr-298,50
4 ln km
Ghi ch
271
1. Nguyn t.
Al
Vch ph (nm)
Mc nhy ph km
vch s 1
Al-309,30
Al-396,20
1,5 ln km
Al-308,20
1,8 ln km
Al-394,40
3,5 ln km
Ghi ch
Ao
No
Vch ph (nm)
Mc nhy ph km
vch s 1
Ag-328,10
Ag-328,30
2,5 ln km
Ghi ch
Au
Vch ph (nm)
Mc nhy ph km
vch s 1
Au-242,80
Au-267,60
2,5 ln km
Au-312,30
600 ln km
Ghi ch
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit : 120 - 200oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 450 - 600oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2300oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2500oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,25 ng/mL (ppb).
- Vng tuyn tnh: 2,5 - 25 ng/mL.
4. Nguyn t.
Ba
Vch ph (nm)
Mc nhy ph km
vch s 1
Ba-553,60
Ba-455,40
5 ln km
Ba-350,10
22 ln km
Ghi ch
274
5. Nguyn t.
Be
Vch ph (nm)
Mc nhy ph km
vch s 1
Be-234,90
Be-313,04
8 ln km
Be-332,14
100 ln km
Ghi ch
Bi
Vch ph (nm)
Mc nhy ph km
vch s 1
Bi-223,10
Bi-222,80
4 ln km
Bi-306,80
4,5 ln km
Bi-227,70
35 ln km
Ghi ch
275
Ca
Vch ph (nm)
Mc nhy ph km
vch s 1
Ca-422,70
Ca-239,90
150 ln km
Ghi ch
8. Nguyn t.
Cd
Vch ph (nm)
Mc nhy ph km
vch s 1
Cd-228,80
Cd-326,90
500 ln km
Ghi ch
Co
Vch ph (nm)
Mc nhy ph km
vch s 1
Co 240,70
Co-242,50
1 5 ln km
Co 252,10
6,5 1nkm
Ghi ch
Cr
Vch ph (nm)
Mc nhy ph km
vch s 1
Cr-357,90
Cr-359,40
21n km
Cr-360,30
3,6 ln km
Cr-429,00
6 ln km
Ghi ch
11. Nguyn t.
Cu
Vch ph (nm)
Mc nhy ph km
vch s 1
Cu-324,76
Cu-327,40
2 ln km
Cu-217,90
4,5 ln km
Cu 222,60
21 ln km
Ghi ch
Fe
Vch ph (nm)
Mc nhy ph km
vch s 1
Fe-248,30
Fe-248,80
2,3 ln km
Fe-271,90
3 ln km
Fe-372,00
10 ln km
Ghi ch
279
Mg
Vch ph (nm)
Mc nhy ph km
vch s 1
Mg-285,20
Mg-202,60
40 ln km
Mg-279,60
100 ln km
Ghi ch
Mn
Vch ph (nm)
Mc nhy ph km
vch s 1
Mn- 279,50
Mn- 279,80
1,5 ln km
Mn- 280,10
3 ln km
Mn- 403,00
10 tn km
Ghi ch
Mo
281
No
Vch ph (nm)
Mc nhy ph km
vch s 1
Mo-
Mo-
Ln km
Mo-
Ln km
Mo-
Ln km
Ghi ch
Ni
Vch ph (nm)
Mc nhy ph km
vch s 1
Ni-232,00
Ni-341,50
2,5 ln km
Ni-305,10
4,5 ln km
Ni-234,60
8 ln km
Ghi ch
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit : 120 - 200oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 600 - 800oC, Thi gian: 30 giy.
+ Giai on NTH: Nhit : 2600oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2700oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,25 ng/mL (ppb).
- Vng tuyn tnh: 2,5 - 25 ng/mL.
17. Nguyn t.
Pb
No
Vch ph (nm)
Pb-217,00
Pb-283,30
2 ln km
Pb-261,40
40 ln km
Pb-368,40
100 ln km
Ghi ch
Sb
Vch ph (nm)
Mc nhy ph km
vch s 1
Sb-206,80
Sb-217,60
2 ln km
Sb-231,20
3 ln km
Ghi ch
Si
284
No
Vch ph (nm)
Mc nhy ph km
vch s 1
Si 251,60
Si 250,70
2,6 ln km
Si-251,40
4 ln km
Si 252,90
10 ln km
Ghi ch
Si
Vch ph (nm)
Mc nhy ph km
vch s 1
Sr-460,70
Sr-407,80
50 ln km
Ghi ch
Ti
Vch ph (nm)
Mc nhy ph km
vch s 1
Ti-364,30
Ti-365,40
1,6 ln km
Ti-320,00
2 ln km
Ti-399,00
5 ln km
Ghi ch
22. Nguyn t.
Vch ph (nm)
Mc nhy ph km
vch s 1
V-318,50
V-306,60
3 ln km
V-437,90
5 ln km
V-385,60
7 ln km
Ghi ch
Zn
Vch ph (nm)
Mc nhy ph km
vch s 1
Zn-213,90
Zn-307,60
2000 ln km
Ghi ch
287
288
17. Nguyn Phng Tho, 2005, Lun n thc s, Trng H KHTN - HQG
H Ni.
18. Jose A.C. Broekaet, 2002, Atomic Analytical Spectrophotometry, Wiley CH.
Ltd., New York - London - Amsterdam - Tokyo.
19. Shimadzu Company, 2002, AAS Cook Book, Shimadzu Company.
20. Phm Th Qunh Lng, 2002, Lun n thc s, Trng H KHTN - HQG
H Ni.
290
MC LC
PHN I ............................................................................................................................3
Chng 1: I CNG V PHNG PHP AES ....................................................3
1.1 S phn loi ph ........................................................................................................3
1.1.1 S phn chia theo c trng ca ph ..............................................................3
1.1.2 Phn chia theo di sng..............................................................................4
1.2 S xut hin ph pht x nguyn t ......................................................................5
1.2.1 Tm tt v cu to nguyn t..........................................................................5
1.2.2 S xut hin ph pht x.................................................................................7
1.3 Nguyn tc ca php o ph pht x (AES)..........................................................9
1.4 i tng ca phng php phn tch ph pht x.............................................14
1.5 Cc u im v nhc im ................................................................................14
1.6 Kh nng v phm vi ng dng ...........................................................................15
Chng 2: S KCH THCH PH PHT X NGUYN T....................................17
2.1 Yu cu v nhim v ca ngun kch thch.........................................................17
2.2 Cc loi ngun kch thch ph pht x.................................................................18
2.2.1 Ngn la n kh...........................................................................................18
2.2.2 H quang in ...............................................................................................23
2.2.3 Tia la in ...................................................................................................28
2.2.4 Plasma cao tn cm ng ICP.........................................................................34
2.3 Nguyn tc v cch chn ngun kch thch ph ..................................................40
2.4 Cng vch ph pht x nguyn t ................................................................41
2.4.1 Cng vch ph : .....................................................................................41
2.4.2 Cng vch ph v nhit plasma ........................................................44
2.5 Hin tng t hp th (t o) ............................................................................45
2.6 Bc x nn trong ph pht x ..............................................................................46
Chng 3: MY QUANG PH V S PHN LI CHM SNG ............................47
3.1 Nguyn tc cu to ca my quang ph pht x..................................................47
3.2 Cc loi my quang ph pht x..........................................................................50
3.2.1 Lng knh v my quang ph lng knh........................................................50
3.2.2 Cch t v my quang ph cch t ...............................................................61
3.3 Vng lm vic ca my quang ph......................................................................67
3.4 Trang b ca h thng my quang ph pht x....................................................68
3.5 Trang b pht hin v thu nhn ph .....................................................................68
3.5.1 Knh nh quang ph ......................................................................................68
3.5.2 o en S ca vch ph trn knh nh .....................................................70
3.5.3 ng nhn quang in (Photomultiplier tubes) ..............................................71
Chng 4: Cc yu t nh hng trong AES................................................................75
4.1 Khi qut chung ...................................................................................................75
291
294
295