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PHM LUN

PHNG PHP PHN TCH


PH NGUYN T
(In Ln th 2 c sa cha v b sung)

NH XUT BN I HC QUC GIA H NI

LI M U
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

1.1 S phn loi ph


Phn tch quang ph l tn gi chung cho mt h cc phng php phn tch
quang hc da trn c s ng dng nhng tnh cht quang hc ca nguyn t, Ion,
phn t v nhm phn t. V d, tnh cht pht x hay hp th quang ca nguyn t,
tinh cht hp th quang ca phn t, v.v... V vy ty theo quan nim, da theo nhng
iu kin kch thch ph, phng tin thu ghi v quan st ph, cng nh bn cht ca
qu trnh sinh ra ph m ngi ta c mt s cch phn chia thnh nhng php o khc
nhau, nh php o ph pht x nguyn t, hp th nguyn t, php o ph hng
ngoi,... Tuy th, nhng c hai cch phn chia sau y l ph hp hn:
1.1.1 S phn chia theo c trng ca ph
Theo cch ny ngi ta c nhng phng php phn tch quang hc sau:
Phng php phn tch ph nguyn t, gm c:
a) Ph php x nguyn t
b) Ph hp th nguyn t
c) Ph hunh quang nguyn t
y l ph do s chuyn mc nng lng ca cc in t ha tr ca nguyn t
trng thi kh (hi) t do, khi b kch thch m sinh ra.
Phng php phn tch ph phn t, gm c:
a) Ph hp th phn t trong vng UV-VIS
b) Ph hng ngoi (IR v NIR)
c) Ph tn x Raman
Ph ny c quyt nh bi cc in t ha tr ca nguyn t trong phn t,
l nhng in t ha tr nm trong lin kt hay mt cp cn t do, chuyn mc
nng lng khi b kch thch.
Ph Rn-ghen (tia X), l ph ca in t ni ca nguyn t, gm c:
+ Ph pht x tia X
+ Ph hunh quang tia X
+ Ph nhiu x tia X
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Ph cng hng t, gm:


a) Cng hng t in t (ERMS).
b) Cng hng t proton (ht nhn: NRMS))
Phng php phn tch khi ph: Ph ny c quyt nh bi khi lng ca
cc Ion phn t hay cc mnh Ion ca cht phn tch b ct ra (t s m/z).
y l cch phn chia c s dng rng ri v c coi nh l hp l nht v
tng ng vi ngay tng php o c th..
1.1.2 Phn chia theo di sng
Nh chng ta bit, bc x in t c mi bc sng, t sng di hng ngn
mt n sng ngn vi micromet hay nanomet. Do ph ca bc x in t y
phi cha ht tt c cc vng sng . Nhng trong thc t khng c mt dng c
quang hc no c th c kh nng thu nhn, phn li hay pht hin c ton b vng
ph nh th. V th ngi ta chia ph in t thnh nhiu min (vng ph) khc nhau.
l nguyn tc ca cch chia th hai ny (bng 1.1).
Bng 1.1
S phn chia ph theo di sng
STT

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

Trong bng 1.1, vng ph t 3 n 5 l vng ph quang hc. Cc ph ny xut


hin do s chuyn mc nng lng ca cc in t ha tr ca nguyn t v phn t,
khi b kch thch. Vic phn chia theo cch ny cng c nhng im cha r rng, nh
trong vng t ngoi v kh kin th c c ph ca nguyn t v phn t, m bn cht
ca hai loi ph v s kch thch ca hai loi li rt khc nhau.
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Trn y l hai cch phn chia chnh cn hay c dng. Tt nhin cn c mt


s cch phn chia khc. Nhng c nhiu nhc im v t c s dng, nn khng
cp n y.
S phn chia ny c tnh cht gii thiu chung ton b vng ph. Song, trong
gio trnh ny chng ti ch cp n ph pht x nguyn t, v phng php phn
tch ng dng tnh cht pht x ca nguyn t trng thi hi c gi l K thut
phn tch ph pht x nguyn t.
1.2 S xut hin ph pht x nguyn t
1.2.1 Tm tt v cu to nguyn t
Hng ngy chng ta thng quen vi nhng tn gi, st (Fe), ng (Cu) ch
(Pb), bc (Ao), vng (Au), nhm (Aj), km (Zn),... l nhng nguyn t ha hc.
n nay ngi ta bit trn 110 nguyn t ha hc khc nhau. Nhng v mt ha
hc v theo thuyt ca alton, nguyn t ha hc bao gm nhng nguyn t ca cng
mt loi v nguyn t l phn t nh nht cn gi c tnh cht ha hc ca nguyn
t. Nguyn t ca mi nguyn t ha hc c cu to khc nhau nn chng c tnh cht
khc nhau. Quyt nh tnh cht vt l v ha hc ca chng l cu to ca lp v
electron trong nguyn t, c bit l cc in t ha tr.
Nguyn t ca mi nguyn t ha hc u c xy dng t mt ht nhn
nguyn t v cc electron (in t). Trong nguyn t, ht nhn gia, cc in t
chuyn ng xung quanh ht nhn theo nhng qu o (orbital) tng i. Ht nhn
chim th tch rt nh trong khng gian ca nguyn t (khong 1/10.000 th tch
nguyn t), nhng li chim hu nh ton b khi lng ca nguyn t. Nu coi
ng knh nguyn t l 10-8cm, th ng knh ht nhn ch chim khong 10-12cm.
Nh vy, lp v ca nguyn t ngoi ht nhn l rt rng, n chnh l khng gian
chuyn ng ca in t. S chuyn ng ca in t trong khng gian ny rt phc
tp. N va tun theo quy lut ca chuyn ng sng, li va tun theo quy lut
chuyn ng ca cc ht vi m. Song trong mt iu kin nht nh v mt cch tng
i, ngi ta vn tha nhn cc in t chuyn ng trong khng gian ca nguyn t
theo cc qu o. Nhng theo quan im hin i ca c lng t th l cc m
my electron.
Trong lp v nguyn t, in t phn b thnh tng lp ng vi s lng t
chnh ca nguyn t (n). Trong tng lp li c nhiu qu o ng vi s lng t ph
1 ca nguyn t. l cc phn lp. Nhng theo nguyn l vng bn th in t bao
gi cng chim v lm y nhng qu o c mc nng lng thp trc. Sau mi
n nhng qu o c mc nng lng cao hn. Th t sp xp l: ls, 2s, 2p, 3s,
3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p, v.v... (hnh 1.1a).

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.

Qu trnh pht x v hp th ca mt nguyn t.


E0: Nng lng trng thi c bn; cm: Nng lng trng thi kch thch; + hv
v + E: Nng lng kch thch; - hv: Tia pht x.

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
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ngoi (in nng, nhit nng, ha nng,...) th in t s chuyn ln mc nng lng


cao hn. Khi nguyn t b kch thch. N tn ti trng thi kch thch. Nhng
trng thi ny khng bn vng. Nguyn t ch lu li trng thi ny nhiu nht l 10
8 giy. Sau n lun lun c xu hng tr v trng thi c bn ban u bn vng.
Ngha l gii phng nng lng m chng hp th c trong qu trnh trn di
dng ca cc bc x quang hc. Bc x ny chnh l ph pht x ca nguyn t, n c
tn s c tnh theo cng thc:
E = (En E0) = hv
hay: E =

(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
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ph ca phn t MeO, CO v nhm phn t CN. Cc m ph ny xut hin thng


c mt u m v mt u nht. u m pha sng di v nht pha sng ngn.
Trong vng t ngoi th ph ny xut hin rt yu v nhiu khi khng thy. Nhng
trong vng kh kin th xut hin rt m, v lm kh khn cho php phn tch quang
ph v nhiu vch phn tch ca cc nguyn t khc b cc m ph ny che lp.
3. Ph nn lin tc. y l ph ca vt rn b t nng pht ra, ph ca nh sng
trng v ph do s bc x ring ca in t. Ph ny to thnh mt nn m lin tc
trn ton di ph ca mu. Nhng nht sng ngn v m dn v pha sng di. Ph
ny nu qu m th cng s cn tr php phn tch.
Ba loi ph trn xut hin ng thi khi kch thch mu phn tch v trong phn
tch quang ph pht x nguyn t ngi ta phi tm cch loi bt ph m v ph nn.
l hai yu t nhiu.
1.3 Nguyn tc ca php o ph pht x (AES)
T vic nghin cu nguyn nhn xut hin ph pht x, chng ta c th khi qut
phng php phn tch da trn c s o ph pht x ca nguyn t phi bao gm cc
bc nh sau:
1. Trc ht mu phn tch cn c chuyn thnh hi (kh) ca nguyn t hay
Ion t do trong mi trng kch thch. l qu trnh ha hi v nguyn t ha mu.
Sau dng ngun nng lng ph hp kch thch m hi chng pht x.
y l qu trnh kch thch ph ca mu.
2. Thu, phn 1i v ghi ton b ph pht x ca vt mu nh my quang ph.
Trc y, ph c ghi ln knh nh hay phim nh. Chnh my quang ph s lm
nhim v ny. Nhng nhng trang b hin i ngy nay c th thu v ghi trc tip cc
tn hiu cng pht x ca mt vch ph di dng cc lc trn bng giy hay ch
ra cc sng cng vch ph trn my in (printer), ghi li vo a t ca my tnh.
3. nh gi ph ghi v mt nh tnh v nh lng theo nhng yu cu t
ra. y l cng vic cui cng ca php o.
Chnh v vy, ng vi cc nhim v v nguyn tc ny, thc hin mt php
phn tch da theo ph pht x ca nguyn t ngi ta phi cn mt h thng trang b
cng gm ba phn tng ng nh th.
A. Trang b c bn (ti thiu phi c):
Phn 1: Ngun nng lng ha hi, nguyn t ha mu v kch thch ph
ca mu phn tch, c ph ca nguyn t phn tch.
Phn 2: My quang ph thu, phn li v ghi li ph pht x ca mu phn tch
theo vng ph ta mong mun.
Phn 3: H thng trang b nh gi nh tnh, nh lng v ch th hay biu
th cc kt qu.
Mt cch tng qut, ta c th m t nguyn tc ny theo s hnh 1.3.

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B. Trang b hon chnh:


C thm cc b phn sau:
1. B t ng bm hay a mu vo o.
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2. H my tnh v phn mm ca n.

Hnh 1.3
S nguyn l ca qu trnh phn tch AES

12

13

1.4 i tng ca phng php phn tch ph pht x


Bn cnh mc ch nghin cu vt l quang ph nguyn t, php o ph pht x
nguyn t l mt phng php phn tch vt l da trn tnh cht pht x ca nguyn t
trng thi hi xc nh thnh phn ha hc ca cc nguyn t, cc cht trong mu
phn tch. V vy n c tn phn tch quang ph ha hc. Phng php ny c s
dng phn tch nh tnh v nh lng cc nguyn t ha hc, ch yu l cc kim
loi trong mi i tng mu khc nhau, nh a cht, ha hc, luyn kim, ha du,
nng nghip, thc phm, y dc, mi trng... thuc cc loi mu rn, mu dung dch,
mu bt, mu qung, mu kh. Tuy phn tch nhiu i tng, nhng thc cht l xc
nh cc kim loi l chnh, ngha l cc nguyn t c ph pht x nhy, khi c kch
thch bng mt ngun nng lng thch hp; sau l mt vi kim nh Si, P, C. V
vy, i tng chnh ca phng php phn tch da theo php o ph pht x ca
nguyn t l cc kim loi nng nh trong cc loi mu khc nhau. Vi i tng
kim th phng php ny c nhiu nhc im v hn ch v nhy, cng nh
nhng trang b thu, ghi ph ca chng, v ph ca hu ht cc kim li nm ngoi
vng t ngoi v kh kin, ngha l phi c thm nhng trang b phc tp mi c th
phn tch c cc kim.
1.5 Cc u im v nhc im
Phng php phn tch quang ph pht x nguyn t s d c pht trin rt
nhanh v c s dng trong nhiu lnh vc ca khoa hc, k thut cng nghip, nng
nghip v i sng v n c nhng u im rt c bn:
a) Phng php ny c nhy rt cao. Bng phng php ny nhiu nguyn t
c th c xc nh t n nhy t n.103 n n.104 %. Nhng vi nhng trang b
hin i v vi nhng ngun kch thch ph mi (ICP) ngi ta c th t n nhy
t n.10-5 n n.10-6 % i. Vi nhiu nguyn t m khng cn phi lm giu mu phn
tch (bng 1). V th n l phng php kim tra, nh gi tinh khit ca nhiu
ha cht v nguyn liu tinh khit cao, phn tch lng vt cc kim loi nng c hi
trong i tng thc phm, nc gii kht, mi trng. Trong khi vi nhng i
tng ny th phng php ha hc khng th no t c.
b) Phng php ny gip chng ta c th tin hnh phn tch ng thi nhiu
nguyn t trong mt mu, m khng cn tch ring chng ra khi nhau. Mt khc, li
khng tn nhiu thi gian, c bit l phn tch nh tnh v bn nh lng.
c) Vi nhng tin b ca k thut hin nay v vi nhng trang b hin nay t
c, th phng php phn tch theo ph pht x nguyn t l mt php o chnh xc
tng i cao. Trong nhiu trng hp, vi nng nh (c ppm) m sai s ca php
o l di 10%. Tt nhin vi nhng trang b v my mc c in th sai s c th ln
hn. Song thc t n b nhng trang b hin i y li.
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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.
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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

2.1 Yu cu v nhim v ca ngun kch thch


Trong phn tch quang ph pht x nguyn t, ngun sng c gi l ngun
kch thch ph v c mt vai tr ht sc quan trng. V nh ngun nng lng kch
thch ngi ta c th chuyn vt liu mu phn tch thnh trng thi hi ca cc
nguyn t v kch thch m hi pht sng (pht x), ngha l ngun nng lng nh
hng trc tip n kt qu ca php phn tch. V vy ngun nng lng mun dng
c vo mc ch phn tch quang ph pht x nguyn t cn phi thc hin c hai
nhim v sau y:
Trc ht ngun nng lng phi ha hi, nguyn t ha v chuyn c hon
ton cc nguyn liu mu phn tch vo vng phng in (plasma). C nh th thnh
phn ca m hi trong plasma mi ng nht vi thnh phn ca vt mu. ng thi
ngun nng lng phi c nng lng ln (nhit ) c th kch thch c tt
nht cc nguyn t ca nguyn t cn phn tch i n pht x ra ph ca n.
Song nh th vn cha hon ton . V mt phng php phn tch ch c gi tr
khi n c nhy v lp li cao. Chnh v th, ngoi hai nhim v trn mt ngun
sng mun dng c lm ngun kch thch ph pht x n cn cn phi tha mn mt
s yu cu nht nh sau y:
1) Trc ht ngun sng phi m bo cho php phn tch c nhy cao v
cng ca vch ph phi nhy vi s bin thin nng ca nguyn t phn tch;
nhng li khng nhy vi s dao ng ca iu kin lm vic.
2) Ngun nng lng phi n nh v bn vng theo thi gian, m bo cho
phng php phn tch c lp li v n nh cao. Ngha l cc thng s ca
ngun sng chn nht thit phi duy tr v lp li c.
3) Ngun nng lng phi khng a thm ph ph vo lm ln vi ph ca mu
nghin cu. Nu khng s lm kh khn thm cng vic nh gi nh tnh v nh
lng v c khi lm sai lc c kt qu phn tch.
4) Ngun kch thch phi c s cu to khng qu phc tp; nhng li c kh
nng thay i c nhiu thng s, c th chn c nhng iu kin ph hp theo
tng i tng phn tch hay tng nguyn t.
5) Yu cu cui cng l ngun nng lng kch thch phi lm tiu hao t mu
phn tch v trong mt s trng hp phi khng lm h hi mu phn tch, nh trong
17

kim tra thnh phm.


Trn y l nhng yu cu chung, nu ngun sng tha mn c y cc yu
cu l mt iu rt l tng. Song trong thc t khng c c iu kin l tng
nh th. V vy, mi ngi lm phn tch quang ph pht x cn phi hiu bit tng
tn v ty theo tng trng hp c th m xem yu cu no cn c ch nghim
ngt trc ht v yu cu no c th chnm chc c.
2.2 Cc loi ngun kch thch ph pht x
Do nhng yu cu nu trn, nn ch c mt vi loi ngun nng lng c
dng lm ngun kch thch cho phng php phn tch quang ph pht x. l:
Ngn la n kh; H quang in dng xoay chiu v mt chiu; Tia la in; Tia
lc; Plasma cao tn cm ng (ICP); tia X.
Trong cc loi ngun nng lng ny, ngn la n kh, h quang v tia la in
c dng t lu, nhng c nhy khng cao (ngun sng c in). Tia lc v
ICP l nhng ngun nng lng cho nhy cao. Nhng tia lc t c dng. V
c c tia lc ph hp cho mc ch phn tch phi c nhng trang b phc tp, tn
km. Ring ICP l ngun nng lng hin ang c ng dng ph bin v c nhiu
u vit. N l ngun sng mi c pht trin trong vng hn chc nm li y. Li
khng t nh ngun lc. V nhy ca cc ngun nng lng ny chng ta c th
xem trong hnh 1.4 v bng ph lc A.
2.2.1 Ngn la n kh
2.2.1.1 Cu to v c im ngn la n kh
Ngn la n kh l ngun nng lng u tin c dng trong phn tch quang
ph pht x nguyn t, ngay t khi phng php ny ra i. Bunsen v Kirschoff l
nhng ngi u tin dng ngun sng ny phn tch cc kim loi kim v kim
th. Nhng do s n gin, n nh, nhy tng i v r tin, nn ngy nay n vn
c s dng ph bin.
1. c im. Ngn la n kh c nhit khng cao (1700 32000C), c cu
to n gin, nhng n nh v d lp li c cc iu kin lm vic. Do c nhit
thp, nn ngn la n kh ch kch thch c cc kim loi kim v kim th. V ng
vi loi ngun sng ny ngi ta c mt phng php phn tch ring. l phng
php phn tch quang ph ngn la (Flame Spectrophotometry). Song v bn cht n
vn l ph pht x ca nguyn t trong ngn la. Cc cht kh t to ra ngn la
ca n kh thng l mt hn hp ca hai kh (1 kh oxy ha v 1 kh nhin liu)
c trn vi nhau theo mt t l nht nh. Bn cht v thnh phn ca hn hp kh
quyt nh nhit ca ngn la v hnh dng cu to ca ngn la. Di y l mt
vi hn hp kh c s dng to ra ngn la trong php o ph pht x:
18

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

2. Cu to. V hnh dng cu to v s phn b nhit ca ngn la, n kh gm


ba phn nh sau (hnh 2.3 v 2.4):
Phn mt (a). Phn trong cng st ming n l phn ti (a). Trong phn ny
cht t c trn v nung nng chun b t chy phn hai (b). Nhit trong
phn ny thp (di 700-12000C).
Phn hai (b) l li ca ngn la.
Trong phn ny xy ra cc phn ng t chy
cht kh. N khng mu hay c mu xanh
nht v nhit l cao nht. Chnh nh b l
ch c nhit cao nht ca ngn la. Nu
t bng hn hp kh axtylen v oxy hay
khng kh nn th nhit ca ngn la c
cung cp nh phn ng:
2C2H2 + 2O2 = 4CO + 2H2 + Q
Phn th ba (c) l v ca ngn la.
Trong phn ny thng xy ra cc phn ng
th cp, c mu vng v nhit thp. N to
thnh ui v v ca ngn la.

Do s phn b nhit ca ngn la nh vy, nn kh phn tch phi a mu


vo vng tnm c nhit cao nht. l vng b ca ngn la v trong vng ny cc
qu trnh s n nh, v hiu sut kch thch ph s cao nht.

19

2.2.1.2 n nguyn t ho mu (burner head)


L b phn t chy hn hp kh
to ra ngn la. Tuy c nhiu kiu n khc
nhau, nhng u c nguyn tc cu to
ging nhau (hnh 2.4 v 2.5). l h thng
nguyn t ha mu. Song bt k mt loi
n no mun dng c cho php phn
tch quang ph, ngoi nhng yu cu nu
(mc 1) n cn phi m bo trn u hn
hp kh trc khi t v ngn la phi chy
ngoi ming n.
Hnh 2.4.
n v h thng NTH mu ca hng
Philips
(1) n nguyn t ha mu; (2) Mng bo him; (3) ng thi phn mu tha;
(4) ng dn cht oxy ha; (S) ng dn mu vo bung aerosol ha; (6) ng
dn cht chy C2H2; (7) Vin bi to bi aersol.
H nguyn t ha mu bao gm:
+ Bung ht mu v to th si kh (1)
+ n nguyn t ha mu (2)

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

(Nebulizer system) a dung dch ny vo ngn la di dng th sng m (th


si kh - aersol) cng vi hn hp kh t. Khi vo ngn la, di tc dng ca nhit
, trc ht dung mi bay hi, li cc ht bt mu mn ca cc cht phn tch, ri
n c t nng v chuyn thnh hi ca nguyn t v phn t. Trong ngn la cc
phn t hi ny chuyn ng, va chm vo nhau, trao i nng lng cho nhau,... Kt
qu ca cc qu trnh lm cc phn t b phn li thnh nguyn t, b Ion ha v b
kch thch. Nh vy trong ngn la tn ti c nguyn t t do, phn t, Ion, nhm phn
t v cc in t. Trong tp hp ch yu ch cc nguyn t t do b kch thch v
pht x. V th ph pht x ngn la l ph ca nguyn t trung ha. Nguyn nhn gy
ra s kch thch ph y l s va chm ca cc nguyn t vi cc in t c ng
nng ln trong ngn la. V th nhit ngn la cng cao th cc in t c ng
nng cng ln. V th n l s kch thch nhit. Do c ch ca qu trnh kch thch
trong ngn la l:
1. Trc ht l dung mi bay hi, li cc ht mu dng bt. 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, v gm c.
2. Hai qu trnh chnh:
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).Th. Men Xm(k) mMe(k) + nX(k)
Me(k) + E Me(k)* Me O + n(Hv)
Nng lng K Chm tia pht x
C ch ny (c ch 1) cho nhy v n nh cao ca s pht x. Cc hp
cht mui halogen (tr F), axetat, mt s nitrat, sunphat... ca kim loi thng theo c
ch ny.
Nu Eh > Ent th mu s b nguyn t ha trc, sau ha hi thnh nguyn
t, ri b kch thch ph sinh ra ph pht x (AES).
MenXm(r) Mn(r) + Xm(r) mMe(k) + nX(k)
Me(k) + E Me(k)* Me O + n(Hv)
Nng lng K.Th. Chm tia pht x
C ch ny (c ch 2) cho nhy v n nh km so vi c ch 1 ca s
pht x.
Cc hp cht mui SIO2-3, PO3-4, F-, mt s nitrat, sunphat,.. ca kim loi thng
theo c ch ny.
Do c im ca 2 c ch chnh , nn trong phn tch ngi ta thng to iu
21

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 axetat ca kim loi kim lm nn, hay cht ph gia
cho mu phn tch.
3. Qu trnh ph
Trong ngn la thng c cc qu trnh ph km theo hai qu trnh chnh, cc
qu trnh ny ty iu kin ca ngn la m xut hin trong mc khc nhau, v n
u khng c li, nn cn c loi tr trong phn tch. Cc qu trnh l:
- To ra cc 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 ca ht rn v electron b nung nng.
Ni chung, cc qu trnh ny u khng c li. Ngi ta phi 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 l 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.
So vi cc loi ngun kch thch khc, ngn la l ngun kch thch n gin,
nhy trung bnh (0,1 - 10g) v tng i n nh. Nhng cng ca vch ph
cng b nh hng bi mt s yu t nht nh, nh:
+ Trc ht l dng lin kt ca cc nguyn t trong cht mu.
+ Th hai l nh hng ca cc gc axit. Ni chung, cc axit d bay hi th nh
hng ny l nh.
+ Th ba l cht nn hay thnh phn ca dung dch mu, v vy dung dch phn
tch v dung dch mu chun u phi c cng thnh phn vt l v ha hc, nht l
cht nn phi cng loi.
+ nh hng th t l cc phn ng ha hc xy ra trong ngn la. c bit l
nh hng ca cc phn ng to ra cc hp cht bn nhit. Cc hp cht ny thng
lm gim cng ca vch ph, ngha l lm gim nhy ca phng php phn
tch. l khi qut chung, tt nhin cc yu t trn khng phi bao gi cng xut
hin ng thi v tc dng nh nhau trong mi trng hp, m ty tng trng hp
yu t no l ni bt v cn c ch . Song mt iu cn nh l nhit ngn la l
yu t quan trng nht, n quyt nh cc qu trnh xy ra trong khi kch thch ph.
22

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

3. H quang l ngun kch thch c s mch tng i n gin, nhng li c


nhiu thng s c th iu chnh c chn c mt nhit tng i ph hp
cho php phn tch mi cht.
4. H quang l s phng in gia hai in cc c th thp (di 260V) v dng
cao (t 8 - 20A). Th v dng ca mch h quang c lin h vi nhau theo cng thc:
U = A+

U
B
v I m =
R1 + R2
Im

Trong A v B l cc hng s, R1 l in tr plasma h quang. Cng thc ny


gii thch ti sao h quang km bn vng. V th phi a vo mch h quang mt
23

bin tr ph R2 tht ln (R2 >> R1) hn ch s thay i cng dng in trong


mch v gi cho h quang n nh.
2.2.2.2 Cu to v hot ng ca h quang
Tuy c nhiu loi my pht h quang khc nhau, nhng v nguyn tc cu to, tt
c cc my pht h quang u gm hai phn chnh.
- Phn 1 l mch pht h quang (mch chnh), n c nhim v cung cp nng
lng ha hi, nguyn t ha mu v kch thch m hi i n pht x. Nu h
quang mt chiu th l mch ca dng in mt chiu (hnh 2.6). Nu l h quang
xoay chiu, th l dng in xoay chiu.
- Phn 2 l mch ch huy (mch iu khin), c nhim v ch huy phn mch
chnh hot ng theo nhng thng s c chn cho mt mc ch phn tch nht
nh. Theo s hnh 2.6, nu cng tc K c ng v tr AA, ta c h quang
dng xoay chiu. Cn khi v tr BB' ta c h quang dng mt chiu. S hot ng
ca h quang din ra nh s (s hnh 2.6):
Khi ng cng tc K', ngha l a in vo my, qua h thng bin tr Ri ta
chn c th lm vic ph hp a vo bin th Tr1 tng th. Khi th hai u
cun th cp ca bin th ny t n hng ngn vn (2000-7000V). Hai u cun ny
c ni vi cun cm Ll, t in C1 v khong n ph E. Lc t C1 c tch in
v khi t n th Vf chn th c mt tia in c nh qua khong E, nh th lp
tc trn mch dao ng L1c1 xut hin mt dao ng cao tn. Do mch dao ng L2C2
cng ghp vi mch dao ng LlC1, nn trn mch L2C2 cng xut hin mt dao ng
cao tn cm ng nh th. Nhng s vng ca L2 l ln hn nhiu L1, nn th trn hai
ct ca t C2 cng s ln hn C1. Th ny li xut hin tc khc khi c tia in nh
E v iu khin s phng in qua khong F ca hai in cc h quang. Nh th mt
chu k phng in th nht c thc hin v kt thc, ri li tip din n chu k
phng in th hai, th ba,... v c th din ra cho n khi no ta ngt cng tc K', tc
l ngng s phng in ca h quang.

24

Khi h quang lm vic, in cc F s c t nng v di tc dng ca


in trng cc in t bt ra khi b mt in cc nm, chng c gia tc v chuyn
ng v cc dng. Nhng in t ny c ng nng rt ln, v khi chuyn ng
trong plasma gia hai in cc, cc in t va chm vo cc phn t khc (nguyn t,
Ion, phn t...) trong plasma F, n truyn nng lng cho nhng phn t . Khi
trong plasma c phn t b Ion ha, b phn li v b kch thch. Kt qu li c thm
in t t do na cng vi mt s nguyn t, Ion, phn t b kch thch. Nh vy chnh
cc phn t mang in tch dng v nm duy tr dng in qua ct kh ca plasma.
Gia hai in cc F cc phn t b kch thch s sinh ra ph pht x ca n. Trong
h quang mt chiu in t lun lun p vo in cc dng, nn in cc dng
nng hn in cc nm. Cn ngc li, trong h quang dng xoay chiu, hai in
cc li c t nng nh nhau.
H quang dng mt chiu thng xut hin s st th hai u ca in cc.
Hiu ng ny xut hin rt r rng trong thi gian u ca s phng in v h
quang c dng thp (di 5A). Nhng sau c nng lng ca ngun kch thch
b vo th s st th s gim i. Nguyn nhn ca s st th ny l do s xut hin
lp in kp hai u ca in cc v lp in kp ny c t trng ngc vi t
trng chnh ca h quang. Vi h quang xoay chiu, do dng in lun lun i
chiu, nn s st th xut hin khng r rng v rt t c tc dng. chnh l l do
gii thch ti sao s kch thch ph pht x bng h quang dng in xoay chiu lun
lun n nh hn s kch ph trong h quang dng in mt chiu.
2.2.2.3 Nhit ca plasma h quang
1. Yu t th nht, yu t chnh quyt nh nhit ca h quang l cng
dng in trong mch h quang chnh. Trong mt khong nht nh ca nhit , khi
tng cng ca dng in th nhit ca h quang cng tng theo. Ngha l ta c:
T = k. I (2.2)
Trong k l h s t l, T l nhit ca h quang (OC). Nhng n mt gi tr
nht nh ca cng dng in I0, th nhit h quang tng rt chm theo s tng
nhit (hnh 2.7). Gi tr I0 c gi l dng in gii hn ca h quang. Nhng
cng dng in trong mch h quang thay i tng i mnh. V ct kh ca
plasma lun thay i c v di v b rng, do im phng in trn b mt in cc
lun lun di ng. l nhc im ca h quang. Do ngi ta phi dng in cc
i c hnh nn ct.
V vy, mun cho cng dng in I trong mch h quang n nh (t thay
i) ngi ta phi mc trong mch h quang h in tr R2 tht ln, s thay i ca
R1 do ct kh gy ra t b nh hng n I. V th trong cc my pht h quang ngi
ta thng lm mt h in tr ni R2 rt ln v cng dng in c tnh theo
cng thc:

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

2.2.2.4 S kch thch ph trong plasma h quang in

Trong plasma ca h quang, s kch thch ph pht x c th xy ra theo cc qu


trnh sau:
1. Nu l mu dung dch, th trc ht l dung mi bay hi, li cc ht bt
mu. Ri cc cht (c mu bt v b ca mu dung dch cn li), bt mu b nung
nng, nng chy. Sau l cc qu trnh nhit ha ca cht mu xy ra theo tnh cht
ca n. C th l cc ht mu s bay hi hay chuyn khi vo plasma gia 2 in cc.
Ti y s xy ra cc qu trnh chnh v ph khc nhau, ty thuc vo thnh phn v
bn cht ca cht mu.
2. Nu mu l dng bt c nhi vo trong l in cc mang th c cc qu
trnh trong in cc mang mu l:
+ S nung nng v nng chy,
+ S chuyn ng nhit khuch tn v i lu ca cc ht trong l in cc,
+ Cc phn ng ha hc phn hy ca cc cht mu km bn nhit,
+ S bay hi ca cc phn t cht mu vo plasma,
+ S vn chuyn ca cc ht mu cha ha hi vo plasm.
Bn cht v thnh phn ca mu trong l in cc v nhit ca in cc l yu
t quyt nh s din bin ca cc qu trnh trn.
Sau l cc qu trnh trong plasma. Gm c 2 qu trnh chnh sinh ra ph pht
x nguyn t (AES) v mt s qu trnh ph nh sau:
A- Hai qu trnh chnh:
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)
Me(k) + E Me(k)* MeO + n(hv)
Nng lng K.Th.

Chm tia pht x

C ch 2 ny cho nhy v n nh cao ca s pht x. Cc hp cht mui


halogen (tr F), axetat, mt s nitrat, sunphat,... ca kim loi thng theo c ch ny.
Nu Eh > Ent th phn t ca cht mu s b nguyn t ha trc, sau ha
hi thnh cc nguyn t t do, ri mi b kch thch ph sinh ra ph pht x (AES).
Men Xm(r) Men (r) + Xm(r) mMe(k) + nX(k)
Me(k) + E Me(k)* MeO + n(hv)
Nng lng K.Th.

Chm tia pht x

C ch 2 ny cho nhy v n nh km so vi c ch 1 ca s pht x. Cc


27

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

tnm plasma tia la in t 4000 6000OC. V th tia la in c gi l ngun kch


thch cng (giu nng lng). Nn ph pht x ca tia la in ch yu l ph ca cc
Ion bc 1 ca cc kim loi.
2. Tia la in l ngun kch thch tng i n nh v c lp li cao. Nhng
v nhy li km h quang in. Do thi gian ghi ph cn phi di hn h quang.
3. V bn cht ca s phng in, tia in l s phng in gia hai in cc c
th hiu rt cao (10.000 - 20.000kV) v dng in rt thp (<1A). N l s phng in
gin on t 50 - 300 chu k trong mt giy, ty thuc vo cc thng s ca my pht
tia la in c chn. Do in cc khng b t nng . Do c im ny m
tia la in l ngun kch thch ph hp i vi php phn tch cc mu thp, hp kim
v dung dch, nhng li khng ph hp cho vic phn tch cc mu qung, t v
bt v khng ha hi tt cc mu loi ny.
4. Trong tia la in qu trnh chuyn vt cht mu t in cc vo plasma l
gin on theo tng chu k phng in gia hai in cc.
2.2.3.2 Nhit ca plasma tia la in
Yu t quyt nh nhit plasma ca tia la in khng phi l cng dng
in nh trong h quang m l mt dng lc xy ra s phng tia in gia hai in
cc. Nhng mt dng in li thay i theo s phng in. N t c gi tr ln
nht ti lc bt u c tia in xy ra gia hai in cc v sau li gim v l nh
nht ti thi im ngh nh in. Qu trnh tip din mt cch tun hon theo nhng
thng s ca my pht tia la in c chn. Ni chung, trong mt gii hn nht
nh, nhit plasma ca tia la in ph thuc vo mt dng in (hnh 2.8),
ngha l n mt gi tr mt dng j0 no th nhit ca tia in khng tng theo
mt ca mt dng in na. Song mt dng in li ph thuc vo ba thng
s chnh ca my pht gia la in Vf, C, L (th, in dung, t cm). Cho nn nhit
ca tia la in cng ph thuc vo cc thng s . Ni chung n t l thun vi
Vf v C v t l nghch vi t cm L. Trong ba thng s th Vf l yu t quan
trong nht v Vf li ph thuc vo:
- Khong cch gia hai in cc.
- Trng thi b mt ca in cc chnh v ph.
- Cc thng s ca mch in nh V, C, L, I, S.

29

V vy, mun m bo cho


qu trnh phng in n nh, th
phi gi cc iu kin lm vic tht
n nh. Nhng cng khng nn
chn cc thng s mt dng
t gi tr gii hn j0 v mt
dng in ny s phng in km
bn vng v khng n nh, tc l
lm cho nhit ca tia in dao
ng nhiu. Mt cch gn ng,
trong plasma tia la in ta c tn
s phng in:
f =

I = Vi C / L

Cng dng in:


V mt dng:

1
1 / LC
2

j=

Vf C / L
I
hay a =
S
S

2.2.3.3 S kch thch ph trong plasma ca tia la in


Trong plasma ca tia la in s kch thch ph pht x xy ra cng tng t nh
trong h quang in. Nhng vi mu bt th s ha hi din ra rt km v khng n
nh. Nhng do nhit ca plasma cao nn s hnh thnh cc hp cht bn nhit, t
gp hn trong h quang. Mt khc, tia la in dng ch yu phn tch mu thp,
hp kim (mu rn) v mu dung dch. Nn cc qu trnh xy ra ch yu ch trn b mt
in cc mang. C th l:
1. Nu l mu dung dch, th trc ht dung mi bay hi, li cc ht bt mu.
Ri cc cht (c mu bt v b ca mu dung dch cn li), bt mu b nung
nng, nng chy. Sau l cc qu trnh nhit ha ca cht mu xy ra theo tnh cht
ca n. C th l cc ht mu s bay hi hay chuyn khi vo plasma gia 2 in cc.
Ti s xy ra cc qu trnh chnh v ph khc nhau, ty thuc vo thnh phn v
bn cht ca cht mu.
2. Nu mu l dng rn, mu l chnh in cc mang, th c cc qu trnh trong
in cc mang mu l:
+ S nung nng b mt v b bn ph,
+ S bay hi ca cc phn t cht mu vo plasma,
+ S vn chuyn ca cc ht mu cha ha hi vo plasma,
Bn cht ca mu, thnh phn ca mu, th phng in, v nhit b mt ca
30

in cc l cc yu t quyt nh din bin ca cc qu trnh trn.


Sau l cc qu trnh trong plasma. Gm c 2 qu trnh chnh sinh ra ph pht
x nguyn t (AES) v mt s qu trnh ph nh sau:
A- Hai qu trnh chnh
A1- Khi mu l dung dch nh ln in cc
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)
Me(k) + E Me(k)* MeO + n(hv)
Nng lng K.Th.

Chm tia pht x

C ch 1 ny cho nhy v n nh cao ca s pht x. Cc hp cht mui


halogen (tr F), axetat, mt s nitrat, sunphat,.. ca kim loi thng theo c ch ny.
Nu Eh > Ent th phn t ca cht mu s b nguyn t ha trc, sau ha hi thnh
cc nguyn t t do, ri mi b kch thch ph sinh ra ph pht x (AES).
Men Xm(r) Men (r) + Xm (r) mMe(k) + nX(k)
Me(k) + E Me(k)* MeO + n(hv)
Nng lng K.Th. Chm tia pht x
C ch 2 ny cho nhy v n nh km so vi c ch 1 ca s pht x. Cc
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 iu
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 axetat 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.
A2- Khi mu l thanh kim loi lm in mang
+ Lp cc nguyn t trn b mt in cc, di tc dng ca lc in trng
in mnh (v th phng in rt cao gia 2 in cc, 15- 20 kV), nn cc nguyn t b
bt ra khi mt in cc v bay vo plasma, hoc l dng hi, hay l dng ht rn. Sau
c cc qu trnh sau:
- Ha hi ca ht rn:

Men) + E1 Me(k)

- Nguyn t b kch thch:

Me(k) + E2 Me(k)*

- Nguyn t b Ion ha:

Me(k) + E3 Me(k)+

- Ion b kch thch:

Me(k)+ + E4 Me(k)+*
31

- Pht x ca nguyn t:

Me(k)* Me(k) + n(hv)

- Pht x ca Ion:

Me(k)+* Me(k) + n(hv)

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

Trong my ny c mt tia in chnh v mt tia in ch huy. Theo s hnh


2.9, khi ng mch in K, bin th Tr c np in v tng th ln hng ngn vn
(V). Lc h t in C c tch in v th hai ct ca t C l th ca khong n
gia hai qu cu E. Lc ny trn mch in LC khng c dng in, t C c tch
in cho n khi t c th Vf (th phng in gia hai qu cu E) th tia in s
nh qua hai qu cu E, t C phng in qua E lm cho trn mch dao ng LC xut
hin tc khc mt dao ng cao tn, dao ng ny khng qua c L2 (hay R1); do
bt buc phi nh qua khong n F (khong cch gia hai in cc chnh). Nh vy,
h c mt dao ng v mt tia in nh E, th cng c mt tia in phng qua F,
ngha l tia in E iu khin tia in F. Sau qu trnh c th tip din cho
n khi ta ngt cng tc K.
Mun cho qu trnh phng in
c n nh th hai qu cu E phi c
kch thc xc nh, khong cch
khng i v b mt phi nhn. C
nh th in th Vf mi c nhng gi
tr xc nh ng vi tng cp thng s
ca my pht tia in c chn,
m bo cho qu trnh phng in
F n nh V mt nng lng, v c
hai tia in xy ra ng thi, nn nng Hnh 2.9
lng phi chia i hai khong n E My pht tia in dng hia tia in
v F. V th mun c nng lng ln
(nhit cao) th th Vf phi rt ln.
My pht dng ngt in ng b (hnh 2.10).
My pht loi ny ch to
theo s ca Fressner. y s
phng in c ch huy nh mt
m t ng b c gn b ngt in
mc ngay trn mch ca my pht
tia in. My pht gm bin th Tr
tng th, mch dao ng LC,
khong phng in chnh F, hai
cun cm L1, L2 ngn khng cho
dao ng cao tn tr v bin th Tr
v m t ng b M ng v
m mch in ca qu trnh phng Hnh 2.10
in gia 2 in cc F.
My pht tia in dng ngt in ng b
33

Khi cho in vo my, bin th Tr tng in, t C c tch in dn, m t M


quay u c mang theo hai tip im A v A, cng quay, khi n v tr B v B1 mch
in trong my c ng, lc th t C cng t cc i, khin cho tia in phi
phng qua F, sau tia in li tt. Nhng v m t M quay u lin tip, nn tia in
cng nh u n lin tip qua F theo s quay ca mt M tun hon n v tr B v
B1 ln lt theo thi gian chu k c chn, cho n khi no ta ngt cng tc K.
Nh vy, chnh m t ng b M iu khin s phng in theo cc thng s
c chn.
2.2.4 Plasma cao tn cm ng ICP
2.2.4.1 c im v tnh cht
y l ngun nng lng mi c s dng trong php phn tch quang ph pht
x nguyn t khong 10 nm li y; song li c s dng rng ri v c hiu qu
cao v n c nhng c im sau y:
1. Ngun nng lng ny c nhit cao. Thng thng tnm ca plasma c th
t c nhit t 5000 10000OC nn ha hi v nguyn t ha c ht mi trng
thi ca vt liu mu vi hiu sut cao. Vi plasma ny, mi nguyn t kim loi u b
kch thch to ra ph pht x ca n. Cc hp cht bn nhit cng b ha hi v
phn li thnh nguyn t t do, nhng trong ngun nng lng ny ph pht x ca Ion
l ch yu.
2. ICP (Inductivity Coupled Plasma) l ngun nng lng kch thch ph pht x
m bo cho php phn tch c nhy rt cao. Ni chung c th t t n.10-4: n.106%
(0,l - 5) ngng i vi hu ht cc nguyn t. Tt nhin nhy ca php phn tch
y ph thuc nhiu vo cng sut ca my pht cao tn HF to ra plasma ICP (hnh
2.11).
3. ICP l ngun kch thch ph khng nhng c nhy cao, m cn c n nh
cao. N hn hn h quang v tia in. V th php phn tch dng ngun nng lng ny
cho sai s rt nh; ni chung l nh hn 10% trong vng nng t n.10-3- n.10-5%.

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.

Chnh do nhng c im v u vit ca ngun nng lng ICP nh th, nn n


nhanh chng c ng dng rng ri v thay th cho ngun nng lng c in: tia
in v h quang. Tt nhin, trang b to ra ngun nng lng ny t hn. Nhng
trong iu kin ngy nay v do tnh cht u vit ca n nn cc phng phn tch quang
ph pht x u c trang b loi ngun nng lng ny.
2.2.4.2 Cu to ca h thng 1CP
V nguyn tc, h thng thit b to ra ngun nng lng ICP gm hai phn
chnh: my pht cao tn HF v h thng to th si kh v n nguyn t ha kch
thch ph ca mu phn tch.
1. My pht cao tn HF
Cc my ny lm vic tn s rt cao nhng ph bin l hai tn s 27,12 MHZ
v 450 MHZ. Trong my trung tn s 27,12 MHZ c s dng nhiu hn. l
tn s sng mang rai. My pht cao tn HF c nhim v pht tn s cao cung cp
nng lng cho cun cm cao tn u ming n nguyn t ha mu, to ra plasma
nhit cao cho s ha hi mu, nguyn t ha v kch thch ph (hnh 12a).
35

2. Phn th hai ca h thng ICP l b phn nguyn t ha mu, bao gm b


phn to soi kh mu v n nguyn t ha mu (nebulizer system v khch burner).
B phn burner c ch to bng thch anh chu nhit. N gm ba ng lng vo
nhau, gn chc vo nhau phn y, v mi ng u c ng dn kh vo (hnh
2.12a). Trong , ng trong cng l mt ng mao dn dn mu vo plasma nh kh
mang; ng th hai l ng to ra kh plasma. Cn ng th ba l ng to kh lm lnh
cho n nguyn t ha. Pha ngoi ng th ba v ngay u c cun cm cao tn bng
ng. Cun cm ny c ni vi my pht cao tn HF v lun c lm lnh bng
dng nc chy qua khi lm vic. ng thi chnh cng sut lm vic ca cun cm
ny s quyt nh nhit ca plasma kch thch ph. Cn h thng nebulizer, v
nguyn tc, hon ton tng t nh trong ngn la n kh nu trn.
Kh dng trong plasma ca ICP l cc kh tr nh argon, hli, nit. Trong
argon l u vit nht. y ngi ta c th dng kh mang v kh plasma l argon,
cn dng nit lm lnh. Hoc c th dng ch mt kh Ar cng c. Trong tng
lng kh cho c ba dng l t 13 - 18 lt/pht v c phn chia nh nhau:
- Kh mang: 0,7 - 1,0 l/pht.
- Kh plasma: 6 - 8 l/pht.
- Kh lm lnh: 5 - 9 l/pht.
Nhng ngy nay, ngi ta ci tin v dng loi mini - ICP nn ch cn n 1/3
lng kh so vi loi thng thng 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

nht. Song mi my pht thng ch dng mt tn s cm ng nht nh 27,12 MHZ


hay 450 MHZ, nn cng sut ca my pht ng vai tr chnh. V th cng ca
vch ph ph thuc vo cng sut ca my pht HF (hnh 2.11).
Tt nhin, bn cnh cn c nhng yu t khc nh hng n nhit ca
plasma ICP. Trc ht l tnh cht ca kh plasma, kh mang v tc chy ca chng
vo plasma. Sau l thnh phn ca hn hp mu c dn vo plasma kch thch
ph. Ni chung dng lin kt, th Ion ha ca cc nguyn t cng c nh hng n
nhit ca plasma. Nhng cc yu t ny khng mnh nh trong h quang v tia
in. Yu t matrix effect cng c tc dng, nhng cng khng ln nh trong ngn la
n kh v trong h quang in. Cc yu t trn nh hng n nhit ca plasma,
tc l nh hng n cng ca vch ph. Nhng khi chn c cng sut ln ph
hp, th nh hng ny s rt nh, hay khng cn na.
2.2.4.4 S kch thch ph pht trong plasma ICP
Khi ta ng mch in ca my pht cao tn HF th cun cm A u n s
xut hin tc khc dng in cao tn cm ng c nng lng ln. Nng lng ny
c quyt nh bi cc thng s ca my pht HF c chn. ng thi tia la
K cng c bt, hn hp kh v mu c t chy, plasma nhit cao xut hin,
ngha l ngn la hnh thnh. Trong ngn la nhit cao ny, trc ht dung mi bay
hi ( phn trong, phn ti ca ngn la), li cht mu dng ht bt mn. Ri cc
bt mu ny b nung nng, nng chy, c ha hi, phn li, b nguyn t ha v Ion
ha to ra trong plasma c phn t, nguyn t, Ion, in t trng thi kh.
Trong ch yu l cc nguyn t, Ion v in t. Sau cc phn t kh ny c trong
plasma s b kch thch v sinh ra ph pht x. Bn cht s kch thch ph y l s
kch thch nhit, n ging nh s kch thch ph pht x trong ngn la n kh.
Nhng v plasma c nhit cao (nng lng ln) nn hiu sut nguyn t ha v kch
thch ph cao v ph ca ngun nng lng ny vi cc kim loi kim v kim th ch
yu l ph ca cc Ion bc 1. C ch ca qu trnh trong plasma ICP c th tm tt
theo s sau:

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

Me(k) + E Me(k)* MeO + n(hv)


Nng lng K.Th.

Chm tia pht x

C ch 1 ny cho nhy v n nh cao ca s pht x. Cc hp cht mui


halogen (tr F), axetat, mt s nitrat, sunphat,.. ca kim loi thng theo c ch ny.
- Nu Eh > Ent, th phn t ca cht mu s b nguyn t ha trc, sau ha
hi thnh cc nguyn t t do, ri mi b kch thch ph sinh ra ph pht x (AES).
Men Xm(r) Men(k) + Xm(k) mMe(k) + nX(k)
Me(k) + E Me(k)* MeO + n(hv)
Nng lng K.Th.

Chm tia pht x

C ch 2 ny cho nhy v n nh km so vi c ch 1 ca s pht x. Cc


hp cht mui SiO3-2, PO4-3, F, mt s nitrat, sunphat... ca kim loi thng theo c
ch ny.
- S Ion ha sinh Ion, sau cc Ion b kch thch v sinh ra ph ca n.
C th l:
Men Xm(r) Men Xm(k) mMe(k) + nX(k)
Me(k) + Ei Me(k)+ + e
Me(k) + E Me(k)+* MeO + n(hv)
Nng lng K.Th. Chm tia pht x
V trong ngun ICP c nhit cao, nn cc kim loi c th Ion ha thp s din
ra theo c ch ny, v d cc kim loi kim, kim th.
3. Qu trnh ph gm c:
+ To ra cc hp cht bn nhit, ch yu l cc monoxit (dng MeO). Nhng
trong plasma ca ngun ICP th cc qu trnh ny xy ra khng ng k. chnh l
u vit ca ICP.
+ S hp th bc x ca nguyn t (qu trnh t o).
+ S pht x nn (nhng cng nh).
+ S Ion ha bc hai ca nguyn t kim loi kim v cc nguyn t c th Ion
ha bc hai thp.

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

go v gm l trng lng thng k ca nguyn t A trng thi ban u, nng


lng Eo v trng thi kch thch nng lng cm;
Na l s nguyn t ca nguyn t Ao c trong plasma (trng thi hi);
41

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

Nhng i vi mt loi nguyn t v trong mt iu kin th nghim nht nh


ca plasma (ch yu nhit plasma) th cc yu t tri Amo, go, gm, cm, hv l nhng
hng s. Cho nn cng vch ph Ia ch cn ph thuc vo s nguyn t b kch
thch Na m thi. Nh vy ta c:
I a = K1 N a

Vi

ka = f .

(2.6)

g
l
. Amo . Aa . m .hv.e ( E ) / kT
tm
go

l cng vch ph ca nguyn t.


Song cng thc (2.6) mi ch cho ta bit mi quan h gia cng vch ph Ia
v nng ca nguyn t trng thi hi trong plasma, m cha ch cho ta c mi
quan h gia cng vch ph v nng ca nguyn t trong mu phn tch. Mun
th ta phi xt mi quan h gia nng C trong mu v s nguyn t Na trong
plasma. Ni chung, mi quan h ny l phc tp, n ph thuc vo nhiu yu t, nh:
- Kh nng ha hi, bn cht ca cht mu, cht nn;
- Thnh phn ca mu, cht ph gia thm vo;
- Trng thi lin kt, tn ti ca cht mu;
- Cc iu kin ha hi, nguyn t ha mu, kch thch ph;
- Mi trng kch thch ph, v.v...
Tuy nhin ngi ta thy t thc nghim, trong mt phm vi nht nh ca nng
42

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)

Do , mt cch tng qut, ta c th vit cng vch ph pht x:


I = a.Cb

(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

iu ny cho thy cng ca vch ph ph thuc vo nhit ca plasma.


Nhng, tt nhin, s ph thuc ny i vi vch nguyn t v vch Ion l khc
nhau v khng n iu, m theo hm s m (e-Em/kT). Chnh hai cng thc trn d
dng cho ta thy rng, nhit no ca plasma to ra c s nguyn t N(1 x)
trong cng thc tnh cng vch nguyn t v s phn t (N.x) trong cng thc
vch ph ln l ln nht, th lc s c c cng ca vch ph ln nht. l
nhit ti u ca s kch thch ph.

44

Vi mt vch ph ca mt nguyn t, thc t ch c mt nhit to ra c


cng I cc i. Nhit ny c gi l nhit ti hn ca vch ph v c
k hiu l To. Tt nhin i vi mi vch th nhit To ny khc nhau (hnh
2.15a,b,c). Ngay i vi vch ph ca mt nguyn t, nu n tn ti trong cc nn mu
khc nhau (matric khc nhau) th nhit To ny cng khc nhau (hnh 2.15c). iu
c ngha l, ngoi bn cht ca cht phn tch, nhit To cn ph thuc vo c
thnh phn v nn ca mu phn tch.
Tnh cht ny c ngha thc t rt ln khi xc nh lng nh cc nguyn t
trong mu phn tch. V trong nhng trng hp ny ta cn phi chn nhng iu kin
lm vic v iu kin kch thch ph sao cho thu c vch ph c cng ln nht,
tc l chn cc iu kin kch thch ph c c nhit ca plasma gn vi nhit
To ca vch ph cn o, hoc bng ng c To l l tng. Tt nhin bng c
l trng hp rt him, ta ch c th lm cho nhit ca plasma cng gn vi nhit
To th cng tt.
2.5 Hin tng t hp th (t o)
trng thi hi trong plasma, hin tng mt nguyn t c kh nng hp th tia
bc x do chnh mt nguyn t khc cng loi ca chng pht ra c gi l hin
tng t hp th (hay t o). Hin tng ny xy ra theo nh lut Kirschhoff. Ngha
l mt nguyn t ch hp th nhng tia bc x m chnh n c th pht ra c trong
qu trnh pht x. Hin tng ny thng xy ra mnh v ch yu i vi cc vch
cng hng, vch cui cng ca ph pht x ca mt nguyn t, v nng cng
ln, th hin tng ny xy ra cng mnh. Chnh do hin tng ny, m a n kt
qu lm cho cng vch ph pht x I khng ph thuc tuyn tnh vo C, khi nng
C tng gi tr Cx > Co, Gi tr Co c gi l nng gii hn, cn c quan h
gia I v C l tuyn tnh. Vi mi vch ph, Co l khc nhau. Vch cng nhy th Co
cng nh. ng thi, trong qu trnh pht x, cng sut pht x ca mt vch ph c
tnh theo cng thc:
W = f.Wo

(2.13)

vi f l h s hot ng pht x ca vch ph v n nhn gi tr: 0 < f < 1.


Khi khng c hin tng t o, ngha l nng Cx nh hn Co th f = 1, tc
l W = Wo. Cn mi trng hp khc, khi c hin tng t o th lun lun c W <
Wo. Trong :
V

Vo = Am .N a .hv.e Em kT )dv

(2.14)

y: Na l s nguyn t trong n v th tch V ca plasma.


Amo l xc sut chuyn mc;
Cm l nng lng kch thch trng thi mi
T l nhit ca plasma (oK);
45

hv l lng t sng c bc x ra;


k l hng s Bolzmans.
V ngha thc t, khi hin tng t hp th xut hin, ni chung u khng c
li cho php phn tch ph pht x nguyn t. iu c ngha l trong phn tch
khng nn xc nh mt nguyn t vng nng bt u xut hin hin tng t
o, tc l nm ngoi vng tuyn tnh, phi pha long mu kt qu s chnh xc hn.
2.6 Bc x nn trong ph pht x
Khi kch thch mu phn tch ta thu c ph pht x ca n. Ph ny gm c
ph vch ca nguyn t v Ion, ph m ca phn t v nhm phn t. Sau n ph
nn hay gi l bc x nn. Bc x nn thng l ph lin tc. N to thnh mt di
en m trn ton b vng ph ca mu phn tch. en ca di ph nn ny mi
vng ph l khc nhau. Thng thng vng sng di m hn vng sng ngn.
Nhn chung, n tng dn t vng sng ngn sang vng sng di, n th hin r rt
vng kh kin (360 - 500 mm). Cn vng t ngoi (UY) th ph nn thng rt nh.
Trong mt mc va th bc x nn l c li v n lm nn cho vch ph
xut hin ln trn m hn, ngha l lm tng cng ca vch ph. Do , trong
mt s trng hp nn qu yu ngi ta thng phi chiu sng ph knh nh bng
nh sng trng vi mt thi gian ph hp. Song trong nhiu trng hp ph nn
thng qu mnh, c bit l trong vng kh kin v khi dng h quang. Lc ny n
che lp mt vch ph ca nguyn t phn tch, nht l nng nh. Trong trng
hp ny ngi ta phi tm cch kh bt bc x nn. Vy nguyn nhn no gy ra
bc x nn ?
T nhng kt qu nghin cu ngi ta thy c cc yu t sau y to ra bc x
nn (ph nn):
- S pht sng ca ht vt rn c t nng trong plasma.
- Tc dng ca nh sng trng.
- S bc x ca in t trong plasma nhit cao.
Do in cc b t nng sng v pht x (vt rn pht sng nhit cao).
Trong ba yu t ny, yu t th ba th hin khng r nt bng hai yu t u.
loi tr bc x nn ngi ta c th p dng nhiu bin php khc nhau. V d vi
nguyn nhn th nht, ngi ta dng mn chn trc khe sng khng cho nh sng do
hai u in cc c t nng chiu vo khe my quang ph. Hoc cng c th
thm cht ph gia vo mu phn tch kh bt mt phn cng nn, lm cho nn
ca ph khng qu en. Nhng tt nht l kch thch ph trong mi trng kh tr Ar
(argon) hay hn hp ca kh tr Ar v oxy theo nhng t l ph hp. Bin php ny
loi tr c c ph nn v ph xm ca nhm CN v ph phn t H2O, mt khc li
cn tng c cng vch ph, ngha l tng c nhy ca phng php phn
tch. l u vit ca mi trng kh tr trong s kch thch ph pht x nguyn t.
46

Chng 3
MY QUANG PH V S PHN LI CHM SNG

3.1 Nguyn tc cu to ca my quang ph pht x


My quang ph l mt dng c dng thu, phn li v ghi li ph ca mt vng
ph quang hc nht nh. Vng ph ny l mt i ph ca vt mu nghin cu t
sng ngn n sng di. Ty theo b phn dng phn li nh sng trong my da
theo hin tng vt l no (khc x hay nhiu x) m ngi ta chia cc my quang ph
thnh hai loi.
1. My quang ph lng knh. l nhng my quang ph m h tn sc ca
chng c ch to t 1 hay 2 hoc 3 lng knh. S phn li nh sng y da theo
hin tng khc x ca nh sng qua hai mi trng c chit sut khc nhau (khng
kh v thy tinh hay khng kh v thch anh).
2. My quang ph cch t. L nhng my quang ph m h tn sc l mt cch
t phng hay lm phn x. Bn cht ca s tn sc nh sng y l s nhiu x ca
tia sng qua cc khe hp.
Tuy c 2 loi my quang ph khc nhau, nhng v nguyn tc cu to th u
nh nhau, u gm 3 phn chnh. l h chun trc, h phn li v h hi t chm
sng (hnh 3.1).
1. H chun trc v phn u ca my quang ph. N gm mt hay mt h
thng thu knh ghp vi nhau hay h gng hi t v mt khe hp (khe vo ca chm
sng v c th iu chnh c) t tiu c ca h thu knh ny. H chun trc c
nhim v nhn v to ra chm sng song song hng vo h tn sc phn li
thnh ph.
2. H tn sc. l mt h thng lng knh hay mt tm cch t. H ny c
nhim v phn li (tn sc) chm sng a sc thnh cc tia n sc, tc l phn li mt
ngun sng phc tp nhiu bc sng khc nhau thnh mt di ph ca chng theo
tng sng ring bit lch i nhng gc khc nhau. Nu h tn sc c ch to bng
lng knh th chng ta c my quang ph lng knh. V ngc li, nu h tn sc l
cch t ta c my quang ph cch t. Trong my lng knh, tia sng ngn s b lch
nhiu, sng di lch t, cn trong my cch t th ngc li.

47

48

49

3. H bung nh. l mt h thng thu knh hay mt h gng hi t v mt


mt phng tiu ca cc chm sng. H ny c nhim v hi t cc tia sng c cng
bc sng sau khi i qua h phn li li vi nhau to ra nh ca khe my trn mt
phng tiu. chnh l cc vch ph.
Thm vo l mt s b phn ph khc my quang ph c th hot ng
c chnh xc, d dng v c hiu qu cao hn. V d nh:
- H thng gng hay thu knh chiu sng khe my.
- H thng gi in cc.
- Cc loi chn sng v lc sng trc khe my.
- B phn t ng a mu.
- My tnh v phn mm iu khin v x l s liu.
3.2 Cc loi my quang ph pht x
3.2.1 Lng knh v my quang ph lng knh
3.2.1.1 Lng knh v my quang ph
Lng knh l mt b phn quan
trng ca my quang ph lng knh.
N quyt nh kh nng, tnh cht
phn li nh sng ca my quang ph.
Lng knh l mt mi trng trong
sut, ng nht v ng hng trong
mt vng ph nht nh. N c gii
hn bi 5 mt phng, nh trong hnh
3.2 ta c: ABC v A,B'C' l hai mt
tit din ca lng knh, n song song
vi nhau.
BB'CC' l mt y ca lng knh. Cc mt ABB'A, v AAICC' l hai mt bn
ca lng knh. Cnh AA, gi l cnh nh ca lng knh. Gc i din vi mt y gi
l gc nh ca lng knh. Mt lng knh thng c c trng bi hai i lng
chnh. l gc nh A (hay cnh y) v chit sut n ca vt liu lm lng knh. Nu
ta chiu mt chm sng Si vo mt mt bn ca lng knh th hin tng khc x s
xy ra nh trong hnh 3.3.
Trong :
Si l tia ti; KH l tia l.
i l gc ti v i' l gc l ca tia sng;
50

D l gc lch ca chm sng sau khi qua lng knh;


ABC l tit din chnh ca lng knh;
Di l gc lch ti thiu;
y ta c cng thc c trng cho 1 lng knh l:
Sin

( 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

tnh theo cng thc:


Dg =

Dd
dn
2 sin( A / 2)
x
.sin
2
2
d
1 n sin ( A / 2) d

(3.3)

Nu gc nh A ca lng knh bng 60 th cng thc trn s l:


Dg =

2
1 n

dn
d

(3.4)

Nu my quang ph c m lng knh nh nhau trong h tn sc, th tn sc ca


my s bng m ln ca my 1 lng knh. Cn nu cc lng knh c gc nh A khc
nhau, th tn sc chung s l tng ca tn sc tng lng knh theo cch b tr.
Ngha l tn sc gc chung bng tng tn sc gc ca tng lng knh c trong h
tn sc ca my quang ph.
Nh vy, theo cc biu thc trn, chng ta thy tn sc gc ca mt my
quang ph lng knh ph thuc vo cc yu t sau:
1. S lng knh c trong h tn sc.
2. Gc nh A ca lng knh.
3. Chit sut ca vt liu lm lng knh.
4. Bin thin theo bc sng (sng ngn lch nhiu, sng di lch t).
V th, mun tng tn sc gc ca mt my quang ph lng knh ngi ta phi
ch to h tn sc c nhiu lng knh ghp li vi nhau. Trong thc t ngi ta thng
ghp hai hoc ba lng knh. Bin php th hai l chn nhng vt liu c chit sut ln
ch to lng knh v ch to cc lng knh c gc nh A ln. Nhng bin php ch
to gc A ln cng ch thc hin c trong mt mc nht nh, thng thng n
90 l ln nht. V khi tng gc nh A ca lng knh th hin tng phn x ton phn
mt bn ca lng knh s nhanh chng xut hin, lm mt phn chm sng s khng
ra khi lng knh, v ta b mt chm tia .
2. tn sc di. tn sc gc ch cho bit s khc nhau v gc lch ca 2 tia
sng, ngha l tia sng b lch i ni gc ln bao nhiu sau khi phn li, m cha
ch ra c hai vch ph gn nhau s cch nhau l bao nhiu trn mt phng tiu (hay
knh nh). Do , trong thc t, nh gi kh nng tn sc ca mt my quang ph
ngi ta cn phi s dng thm c tn sc di. Nhng tn sc di ph thuc vo
tn sc gc v tiu c ca thu knh bung nh f2, v n c tnh theo cng thc:
Dl =

f
dl
dD
= 2 x
d sin E d

(3.5)

Trong di l khong cch gia hi vch ph trn mn nh (mt phng tiu); E l


gc nghing ca hp nh vi quang trc bung nh ca my v do hiu s di sng
ca 2 vch ph, tc l : d = (1 - 2) v = (2 + 1)/2.
52

Theo cng thc trn, mun tng tn sc di ca mt my quang ph lng knh


ngi ta phi:
- Tng tn sc gc ca n.
- Tng tiu c ca thu knh bung nh f2. Nhng bin php ny ch t c
trong mt gii hn nht nh. V khi f2 cng ln th cng sng ca vch ph cng
gim, ngha l c v tn sc th mt v cng (hai yu t ny t l nghch vi
nhau). Do , trong thc t, ngi ta phi tnh ton v chn gi tr f2 cho ph hp
sao cho c tn sc ln, m cng vch ph vn m bo cn trn 80%.
Tuy nhin, d nh gi v so snh tn sc di ca cc my quang ph vi
nhau, trong thc t ngi ta li thng dng gi tr nghch o ca tn sc di,
ngha l thay biu thc dl/d bng biu thc dl/d. Nh vy, i lng mi quy c
ny cho ta bit c trn n v di ca knh nh (mm) hay mt phng tiu c cha
bao nhiu n v di sng (amstrong hay nm), ngha l my quang ph no c gi
tr d/dl cng ln th c tn sc di cng nh. V d hai my quang ph Ql v Q2,
m Q1 c dl bng 4 A/mm v Q2 c d/dl bng 2 A/mm, th my Q2 c tn sc di
gp i tn sc di ca my Q1.
tn sc di ca mt my quang ph c lin quan trc tip n di ca vng
ph m my thu nhn c. Vi mt vng ph nht nh tn sc di cng ln th
vng ph ca my cng ri ra trn mt khong rng, ngha l mt phng tiu ln, nh
th trn mt knh nh c chiu di nht nh th ch thu c mt phn ca ton vng
ph ca my, nu my c tn sc ln. Nh trong v d trn ca hai my quang
ph Ql v Q2, i vi vng ph t 2000 - 4000 A th ton b vng ph thu c ca
my Q2 chim di gp i ca my Ql.
Do vi nhng my c tn
sc ln, ngi ta khng th thu c
ton b vng ph ca chng ln mt
knh nh, v phi cn mt knh nh
qu di. Cho nn ngi ta phi ghi
tng phn ca ton b vng ph ca
my ln mt knh nh c di nht
nh (24 hay 30 cm), ngha l i vi
nhng my quang ph c tn sc
ln ngi ta phi c b phn quay v
hng vng ph cn nghin cu vo
mn nh thu ghi.
Trong my quang ph lng knh, tn sc ca chng gim theo s tng ca
di sng, ngha l trong mt my, th vng sng di c tn sc nh hn vng sng
ngn (hnh 3.4).
53

3. Nng sut phn li.


Nng sut phn li (kh nng phn gii) ca mt my quang ph trong mt vng
no c biu th bng t s:
R=

hay

R=

(3.6)

Trong 1 v 2 l di sng ca hai vch ph gn nhau m cn c th tch ra


thnh hai vch r rt trn hnh nh (mt phng tiu); hay d l hiu s ca 1 v 2.
Nhng my quang ph c nng sut phn gii R cng ln th hai vch ph c
di sng 1 v 2 ny cng nm xa nhau trn knh nh (hnh 3.5).
Nhng gi tr d phi bng bao nhiu hai vch ph 1 v 2 cn c th tch ra r
rt thnh hai vch trn knh nh? Nghin cu vn ny v t nhng kt qu thc
nghim Rayley nu ra quy tc: Hai tia sng c bc sng gn nhau 1 v 2 ch tch
ra c thnh hai vch
ph r rng, nu cc tiu
nhiu x th nht ca vch
ny trng vi cc i
nhiu x th nht ca vch
kia. l khong cch ti
thiu ca 2 vch ph (hnh
3.6).Trn c s , nng
sut phn li ca mt my
quang ph lng knh c
tnh theo cng thc:
Nu my quang ph c h tn sc gm m lng knh nh nhau th
Rt= mRi

(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

Tch thnh hai vch

Khng tch thnh hai vch

V vy, nu chn cc thng s trn cho ph hp khi ch to lng knh v ch to


my quang ph ta s thu c kh nng phn gii tt nht ca mt my quang ph.
Nhng ng knh ca thu knh bung nh li c tnh theo cng thc:
d2 =

d
x
2 sin( A / 2)

[1 n

sin 2 ( A / 2)

(3.8)

trong b l chiu di cnh y ca lng knh.


Nh vy, nng sut phn gii ca my quang ph lng knh s l:
R = m.b.(dn/d)

(3.9)

Ngoi nhng yu t ni, nng sut phn li ca mt my quang ph cn b nh


hng bi mt s yu t khc nh:
- Tnh cht v mn (c ht) ca lp nh tng trn knh nh, nu ph c ghi
ln knh nh. Vi yu t ny, nhng kt qu thc nghim cho thy rng, lp nh tng
trn knh nh cng nhy th nh hng cng nhiu n kh nng phn li ca vch ph.
V nhng knh nh c nhy cao thng c lp nh tng cha cc ht AgBr bt nh
sng c kch thc ln. Nhng trong nhng h thng my mi ca th h th ba, yu
t ny hon ton c loi tr, v ph c ghi trc tip ln bng giy hoc o trc
tip m khng phi ghi ln knh nh na.
- Mt yu t na nh hng n nng sut phn li ca my quang ph l rng
ca khe my (khe vo ca chm sng). Ni chung, vic tng rng ca khe my s
a n kt qu lm gim nng sut phn li ca my v rng ca khe my cng ln
th rng ca vch ph cng cng ln.
3.2.2.3 Nng sut phn li v rng khe my
Nng sut phn li ca mt my quang ph nhn chung ph thuc vo rng ca
khe my. Khe my cng rng th nng sut phn li ca my cng gim. Nhng mi
quan h ny l khng n gin. V th chng ta c th xt trng hp c th sau y:
Nu gi a l rng ca khe my quang ph; f1 v f2 l tiu c ca thu knh chun
55

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)

Trong t s f2/fl c gi l phng i ca my quang ph. Ni chung trong


cc my quang ph ngi ta c gng ch to t s ny bng 1. Nh vy, vch ph l
nh khng phng i ca khe my, ngha l a, = a. V cho vch ph r nt th s
phn b cng phi tha mn iu kin:
a, < 2s

(3.11a)

s = .(f2/d)

(3.11b)

trong

s l na rng hnh hc ca cc i th nht ca vn nhiu x. Do trong


iu kin ti thiu ta phi c:
a, = 2(f2/d)

(3.12)

Hay t cng thc (3.10) v (3.12) chng ta c:


a = 2(f1/d)

(3.13)

Gi tr rng ca a theo cng thc (3.13) ny c gi l rng tiu chun


ca khe my quang ph v k hiu l ao, ngha l lc ny ta c:
ao = 2 (fl/d)
Nh vy rng tiu chun ao ph thuc vo:
- di sng ca tia sng.
- Tiu c f1 ca thu knh chun trc.
- T l nghch vi ng knh d ca thu knh.
L thuyt v thc nghim chng minh rng rng tiu chun ao ca khe my,
nng sut phn gii ca mt my quang ph thc s ch bng 90 phn trm theo l
thuyt. V th, mun c nng sut phn gii cao ta phi m khe my nh hn ao mt
cht (10%). Nhng khi m khe my nh hn gi tr ao ta mt v cng vch ph, v
trong mt gii hn nht nh, th rng khe my quang ph v cng vch ph l
t l nghch vi nhau. Bng 3.1 l vi v d v rng ca khe my quang ph pht x.
Cho nn tt nht vn l chn rng khe my ng bng ao hay ln hn mt t
c v cng trong phn tch nh lng.

56

Bng 3.1
Quan h rng khe my v nng sut phn gii - cng vch ph
Khe my

Cng vch ph (%)

Nng sut phn gii (%)

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

V khi khe my rng tiu chun th ch c cc i th nht ca vn nhiu


x lt vo c h thng chun trc cho nn trong cc php phn tch khng c
chn khe my nh hn rng tiu chun ao. Thng thng, theo kinh nghim thc t
ngi ta hay chn khe my c rng t 1ao n 1,5ao l ph hp (phn tch T chn:
0,9 - 1ao; Phn tch L chn t: 1,0 - 1,5ao).
3.2.2.4 rng ca vch ph
Nu khe my quang ph c rng l th rng ca vch ph bng rng
hnh hc ca khe my cng vi rng ca vn nhiu x chnh gia, ngha l ta c:
s = a'+2

f2
d . sin E

(3.14)

Nu khe my rt hp, th rng ca vch ph ch l rng ca vn nhiu x


chnh gia, ngha l ta c:
s=

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

Nu knh nh c t vung gc vi quang trc ca h thng thu knh bung


nh th rng vch ph s l:
s = a, + 2(f2/d)

(3.16a)
v

s = 2v.(f2/)

(3.16b)

cho c hai trng hp nu trn, v trong trng hp ny sin E = 1.


3.2.2.5 Cng vch ph v rng khe my
Trong phn tch quang ph nh tnh v nh lng, c bit l phn tch hm
lng vt ca cc nguyn t, mt yu cu quan trng l phi thu c vch ph c
cng ln nht, ngha l phi bit c s truyn nh sng t ngun pht x qua
khe my quang ph n vt thu cng vch ph (knh nh, etector) l nh th no.
Nu gi Io l cng ca chm sng pht x ca tia sng th quang thng
tng cng i vo h chun trc s l:
= I o =

(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)

y l h s mt mt nng lng ca chm sng qua h quang hc ca my


quang ph, nh thu knh, lng knh... Trong trng hp l tng th bng 1, cn
mi trng hp khc u ln hn 1. Quang thng ' ny s tc dng ln knh nh vi
ri l:
E=

' '
=
S a'.l '

trong S l din tch ca vch ph v ta c:


58

(3.19a)

S = a,.l'
a,= a.f2/(f1.sin) v l' = l.(f2/fl)

vi

Nn din tch ca vch ph s l:


S = a.l.(f2/fl)2.(l/sin )

(3.19b)

Do , nu nh sng l n sc v b qua hin tng nhiu x, khc x, tn x,


khi chm sng Io qua h quang hc ca my quang ph th ri ca chm sng s l:
E=

' d 2
=
.
sin
S
4 ( f2 )2

(3.20)

y l trng hp l tng, n gin v gi tr ri E trong trng hp ny


c k hiu l Eo. Nh vy, chm sng Io tc dng ln knh nh to ra vch ph c
cng l:
I = Eo .t

B
4

(d / f 2 ) 2 .t. sin

(3.21)

Ngha l nu vch ph hon ton n sc th cng IM ca vch ph t l vi


bnh phng khu t i ca thu knh bung nh v sin ca gc nghing ca hp
nh , cng nh thi gian t m ri Eo ca chm sng tc dng ln knh nh hay vo
khe o ca nhn quang in.
Trn y l trng hp n gin, nhng thc t th phc tp hn, v nh sng vo
my quang ph khng phi khng c cc hin tng nhiu x, tn x, cc sai st ca
h thng quang hc, l nhng yu t thc t khng th loi tr c hon ton. Chnh
v th m vch ph trn knh nh thng rng hn mt cht (10%) so vi trng hp
tnh ton trn y.
Nu gi mt cch tng qut, a1, a2, a3, l rng do cc hin tng nhiu
x, tn x, tnh khng tuyt i n sc ca vch ph gy ra, th rng thc t ca
vch ph phi l:

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

Nh vy nu a >> (a1 + a2 + a3).(f1/f2) th chng ta li c E - Eo, ngha l tr


li trng hp c bit trn. Tc l cng vch ph khng ph thuc vo rng
ca khe sng. Cn tt c cc trng hp khc th rng ca vch ph t hoc nhiu
u c b nh hng bi rng ca khe sng. V cng vch ph trong cc trng
hp lun lun phi tnh theo cng thc:
I = E.t = Eo t

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)

Trong d2 v f2 l ng knh v tiu c ca thu knh bung nh. Nh vy,


sng ca vch ph t l thun vi bnh phng ng knh ca thu knh bung nh d2
v t l nghch vi bnh phng ca tiu c bung nh f2, ngha l ph thuc vo
m ca thu knh bung nh (t l f2/d2). Nu tiu c f2 cng ln th sng L ca vch
ph cng gim, tc l mt v cng v ngc li.
3.2.2.7 S quang hc mt s my quang ph lng knh
V d v cc s h quang hc ca mt s my quang ph pht x c ch ra
trong hnh 3.7.
60

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).

Cc i lng c trng cho mt cch t l hai thng s chnh sau y:


- Chu k ca cch t: L khong cch gia hai vch trn cch t v c k hiu
l d (hnh 3.8a).
- Hng s ca cch t: L s vch trn mt n v di ca cch t v c k
hiu l k, tc l s vch c khc trn 1mm.
Nh vy, gia chu k v hng s ca cch t lin quan vi nhau theo biu thc:
d. k = 1

(3.27)

Nu gi L l chiu di ca cch t, th tng s vch trn mt cch t s l:


N = k. L

(3.28)

V cu to th cch t phn x gm c hai phn. l b v mt cch t. B


l tm thu tinh hay thch anh dy t 1,5 n 2 cm, c hai mt song song vi nhau
v thng c din tch t 4 x 4 hay 4 x 6 n 8 x 12cm. Mt cch t l lp kim loi
nhm (Al) tinh khit (99,999 %) v dy t 0,2 - 0,5 mm. Lp kim loi ny c a
ln b bng con ng in phn c bit trong mi trng tr. Mt lp kim loi
nhn bng v c khc ln nhiu vch song song v cch u nhau. S vch c
khc ln lp kim loi ny thng l t 650 - 3600 vch/mm. S vch trn 1 mm cng
nhiu th kh nng phn li nh sng ca cch t cng ln.
62

Nh th, nu chng ta chiu mt chm sng song song khng n sc vo mt


cch t theo mt gc ti no th ch c vch trn cch t nh mt chn sng, ch
khng c vch nh mt khe sng v di tc dng ca hin tng nhiu x trn b mt
cch t th chm sng a sc s c phn li thnh ph. Nu gi l gc l ca tia
sng, di sng l th ta lun lun c biu thc:
- sin + swin = m.k.

(3.29)

Biu thc ny c gi l cng thc c bn ca cch t. Cng thc ny gii


thch cho ta nguyn nhn s tn sc ca cch t, v t cng thc (3.29) ta c:
sin = m.k. + sin

(3.30)

y l gc ti ca chm sng, m v k l khng i i vi mt cch t. Nn


ng vi mi bc sng ta s c mt gi tr sin tc l c 1 gi tr . iu c
ngha l cch t phn li chm sng a sc thnh tng tia n sc lch i theo tng gc
13 khc nhau. Nhng y sng di b lch nhiu, cn sng ngn b lch t hn. ng
thi cch t cho ta ph c nhiu bc, ng vi cc gi tr m ca cng mt di sng
S m c gi l bc ca ph cch t.
Nu tia ti vung gc vi mt cch t, tc l gc ti - 0 th cng thc (3.30) s
c dng l:
sin = m.k.

(3.31)

Trong trng hp ny gc phn x ca cc tia sng khng ph thuc vo gc ti


m ch ph thuc vo hng s k ca cch t v di sng ca tia sng m thi.
Trong thc t ngi ta hay t cch t v tr ny trong my quang ph.
Nu gc ti = 13 th cng thc (3.30) s l:
sin = (mk/2).

(3.32)

y chnh l tia sng c gc ti tc dng ng vo gia knh nh ca mt


vng ph ca hp nh. V th cng thc ny c s dng tnh gc ti khi chn
vng ph cho mt php phn tch. cng l v tr cc tiu ca tia sng trung tnm ca
vng ph cn chn trong my.
Mt khc, cng chnh do hin tng nhiu x qua khe hp to ra ph ca cch t
cho nn khong cch t v tr cc i cc vn sng n tnm hnh nhiu x c tnh
theo cng thc:
xt = m.f0.(/k)

(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

- Cc i th 3 cch tnm mt on xt3 = (3.f2)/k

- Cc i th m cch tnm mt on xtm = (m.f2)/k.


iu ny gii thch cho ta ti sao tn sc di ca cch t bc th m gp m
ln bc th 1, ngha l c tn sc bc th m l:
DDM =

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)

Biu thc ny chnh l cng thc tnh tn sc gc ca my quang ph cch t.


Nh vy, tn sc gc ca mt my quang ph cch t s:
+ T l thun vi hng s k ca cch t v bc m ca ph cch t.
+ T l nghch vi cos ca gc phn x .
Ngha l mt cch t th vi cc bc ph cng cao tn sc gc ca my cng
ln. V d:
- Nu m bng 1 ta c d/d = 1.k/cos
- Nu m bng 2 ta c d/d = 2.k/cos
- Nu m bng 3 ta c d/d = 3.k/cos
v.v...
Mt cch tng qut, ngha l tn sc bc m th ln gp m ln tn sc gc
bc 1:
64

Dmg =

Dgl
m

Nhng cc bc ph ca cch t li xut hin ng thi, ph ca cc bc cng cao


th cng cng yu. Gn n 70% nng lng l tp trung bc 1 (vn nhiu x th
nht). Chnh v th khi ghi ph phi dng knh lc ph hp loi b nhng bc ph
khng cn thit. Cho nn tnh cht a bc ca ph cch t va l u im, nhng cng
va l nhc im ca my quang ph cch t, v ph ca cc bc cao ta c v
tn sc, nhng li mt v cng . Nn trong thc t, ngi ta ch dng ph bc 1,
hay i khi n bc 2 m thi.
2. tn sc di
i vi my quang ph cch t, ngi ta cng gi t s dl/d l tn sc di
ca n v c tnh theo cng thc:
dl
1
=
m.k . f 2
d cos

(3.36)

Nh vy, tn sc di ca my quang ph cch t t l thun vi tn sc gc


ca n v tiu c f2 ca h bung nh. Hay ni mt cch khc, tn sc di l:
- T l thun vi hng s ca cch t, tiu c ca bung nh, v s bc ca ph
cch t, v
- Thay i trong quan h t l nghch vi cos ca gc phn x ca tia sng. V d
t cng thc trn chng ta c:
+ Nu m = 1 th d/d = (1.k.f2)/cos;
+ Nu m = 2 th d/d = (2.k.f2)/cos;
+ Nu m = 3 th d/d = (3.k.f2)/cos;
Ngha l di tn sc bc th m th cng gp m ln tn sc di bc 1
(cng thc 3.34).
Nhng trong thc t, d so snh, ngi ta cng dng gi tr nghch o ca i
lng ni trn, nh quy c trong my quang ph lng knh. Nh vy chng ta s c:
1
cos
=
Ddm m.k . f 2

(3.37)

Cng thc (3.37) ny l tn sc di nghch o ca my quang ph cch t


bc th m v ti im chnh gia ca vng ph. Cn tn sc di ti mt im X no
cch tnm knh nh mt khong x s c tnh theo cng thc:
Ddm = Ddm 0,00016.

10 3

(3.38)
65

T biu thc ny ta thy tn sc di ca my quang ph cch t hu nh ph


thuc rt t vo di sng ca tia sng (bng 3.2). Cng thc trn nhn du (-) khi i
t tnm knh nh theo chiu di sng tng dn v nhn du (+) theo chiu ngc li.
Bng 3.2
So snh tn sc ca hai my
Vng ph ()

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 -

3. Nng sut phn gii


Nng sut phn gii R ca mt my quang ph cch t c nh ngha nh sau:
R=

Vi d = (2 - 1), = (2 - 1)/2 v c tnh theo cng thc sau:


R=

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

vch ph 1 v 2 khc nhau mt gi tr sau y s c phn li thnh tng vch


ring bit:
Nu m = 1, ta s c = 0,02 ,
- Nu m = 2, ta s c = 0,01 ,
- Nu m = 4, ta s c = 0,005 ,
Ngha l bc m=1, hai vch 1 v 2 mun tch thnh hai vch r rng th phi
khc nhau mt gi tr di sng ti thiu l 0,02 . Khi bc 2, hai vch ny ch
cn khc nhau mt gi tr = 0,01 l tch thnh hai vch ring bit. Nhng
trong thc t ngi ta t dng ph bc cao ca cch t. Ngi ta thng hay dng ph
bc I v bc II, v n 70% nng lng l tp trung bc I. Cho nn trong thc t hin
nay ngi ta dng nhng cch t c hng s k rt ln (k:2400-3600) ch to nhng
my quang ph c kh nng phn gii cao. Hnh 3.1a, b l s quang hc ca mt s
k my ph cch t.
3.3 Vng lm vic ca my quang ph
y cng l mt ai lng nh gi mt my quang ph.
Do tnh cht quang hc ca vt liu dng ch to h tn sc l trong sut v
ng nht trong mt min nht nh, nn mi my quang ph ch c th thu, phn li v
ghi nhn c mt vng sng nht nh ca ton b gii ph quang hc. Vng ph ny
c gi l vng lm vic ca mt my quang ph. Vng ph lm vic ca my quang
ph lng knh l do trong sut v tnh cht ca vt liu lm lng knh quyt nh v
ph thuc vo cch b tr (cu to) ca my quang ph y. V d: Cc my quang ph
lng knh thch anh thng c vng ph lm vic l min t ngoi gn (2000-4000 ).
Cc my quang ph lng knh thu tinh c vng lm vic l min kh kin (36007800 ), v thch anh ch trong sut trong vng t ngoi; cn thy tinh ti trong sut
trong vng kh kin (nhn thy). My quang ph cch t thng c vng lm vic
rng hn my quang ph lng knh. Vng lm vic ca mt my quang ph cch t l
cu to, tnh cht, di sng blanz b) v s bc ca cch t quyt nh. Ni chung,
my quang ph cch t thng c vng lm vic rng hn my quang ph lng knh.
V d: Vi my quang ph cch t PGS-2 lp cch t c k:650 v b = 2700 ,
c vng lm vic l: bc 1: 2000 - 7800 v bc 2: 2000 - 4000 ...
Nh vy, vi my cch t th vng lm vic bc ph th m hp hn bc 1 l m
ln, ngha l chng ta lun lun c:
m = 1/m
Vng lm vic ca mt my quang ph c lin quan cht ch n di ca c
di ph m n thu c. Cc my c tn sc cng ln th di ca di ph
cng ln. V th nhng my quang ph c tn sc ln, vi mt tm knh nh c
67

di nht nh (v d 24 hay 30 cm), chng ta ch c th ghi c mt phn ca vng


ph lm vic ca my . T thc t , trong cc my quang ph c tn sc ln
ngi ta phi c b phn quay cch t hng phn ph cn nghin cu vo knh
nh, ngha l vng ph lm vic ca my cn phi c ghi ln nhiu tm knh. V
d: Vi my Q 24 vng ph lm vic ca n ch cn ghi trn mt tm knh nh di 24
cm. Khi vng ph ny my PGS-2 ta phi cn hai tm knh 24 cm mi c th ghi
ht c vi ph bc I.
3.4 Trang b ca h thng my quang ph pht x
T nhng nghin cu c cp trn, chng ta c th minh ha tm tt
trang b ca mt h thng my quang ph pht x gm nhng phn sau y:
1. Trang b chnh, c bn ti thiu: Gm ba phn
- Ngun cung cp nng lng ha hi mu, nguyn t ha v kch thch m
hi pht x. l ngn la n kh, h quang in, tia la in, ICP.
- My quang ph c nhim v thu, phn li v ghi li vng ph cn nghin cu.
- Nh cc my quang ph lng knh Q-24, ISP-28, ISP-30, KSAI,... v cc my
cch t PGS-2, D-3, D-13.
- Cc trang b nh gi nh tnh (my chiu ph) v nh lng (my o en).
2. H trang b hon chnh, c thm:
+ B phn t ng dn mu vo bung o, pha long t ng.
+ H my tnh v phn chng trnh iu khin, x l kt qu o.
3. Trang b ph thm, Cn c:
+ H thng chiu sng khe my quang ph. N l mt h thng thu knh hi
t v hng chm sng pht x ca mu phn tch vo my quang ph vi hiu sut
cao v ph hp cho tng mc ch phn tch.
+ Cc lc sng v chn sng c nhim v chn v a vng ph cn thit vo
khe my quang ph cng v phm vi nht nh theo yu cu ca php phn tch.
Tt nhin cc th ph tr ny c th khng c cng c.
3.5 Trang b pht hin v thu nhn ph
Cho n nay, thu nhn ph pht x ca vt mu c hai loi trang b. l loi:
1. Knh nh hay phim nh (k thut c in) v 2. Cc loi nhn quang in kiu
ng (photomultiplier tube detector), hin nay l cc mng git (diode array).
3.5.1 Knh nh quang ph
Knh nh quang ph c nhiu loi, nhng v cu to, n gm hai phn: Phn
v phn lp nh tng bt nh sng. l tm thy tinh trong sut v ng nht, c
dy u n, thng t 1 n 2 mm, din tch 6 x 12 cm, 9 x 24 cm hay 9 x 30 cm.
68

Lp nh tng bt nh sn l lp glatin c dy t 0,1 n 0,05 mm, nhng phi


ng nht v u n trn mt tm thy tinh. Lp glatin ny c cha cc ht AgBr
mn. nhy ca knh nh ph thuc vo cc ht AgBr trong lp glatin ny. nhy
l mt thng s c trng cho mi loi knh nh v mi loi knh nh cng ch nhy
trong mt vng ph nht nh (hnh 3.9). c trng ny do qu trnh sn xut quyt
nh, theo loi nguyn vt liu v thnh phn ca chng, cng nh iu kin ch to
knh nh. V th mi loi c nhy khc nhau trong cc vng ph khc nhau.

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

Dung dch hin v dung dch hm knh nh


Dung dch hin hnh

Dung dch nh hnh

1. Mentol: 1g.

1. Natri thiosunphat: 250g.

2. Natri sunfit khan: 26g.

2. Natri cacbonat khan: 25g.

3. Hydroqu Ione: 5g.

3. CH3COOH 99%: 8,5 mm.

4. Natri cacbonat khan: 20g.

Pha trong mt lt.

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)

Trong ao v a l lch ca in k ng vi chm sng cng Io v I. Do


, thang o en S ch c gi tr t 0 - 2. Nhng vng en va phi (vng m
mi quan h gia S v C l tuyn tnh) ch nm trong khong t 0,3 - 1,7 (hnh 3.11).
Cn khi S nh hn 0,3 l vng non, khi S ln hn 1,7 l vng gi. Trong 2 vng ny
kt qu o l khng chnh xc. V th phi chn iu kin ghi ph ph hp en
70

ca vch cn o ri vo vng tuyn tnh (0,3 - l,7).


Nhng trong phn tch
lng vt th en ca vch
ph li c th nh hn 0,3 n v
S. V th ngi ta m rng
thang o en S v pha cng
nh. y c 2 cch bin i
en ca vch ph, v tng
ng n l hai thang o mi W v
P.
Theo thang W th en
vch ph c tnh theo cng
thc:
W = log .(

ao
1)
a

V theo thang P th en vch ph li c tnh theo cng thc:


P=

S+ W
2

Do thc t nn hin nay cc my o en u c c ba thang o en


S, W v P. Vi thang W en c th m rng c n 0,1. Cn vi thang P th c
th n gi tr -0,3 n v S. V th trong phn tch lng vt ngi ta hay dng thang
P. Tt nhin t cc gi tr ca P ngi ta cng d dng tm c cc gi tr ca S hay
W tng ng, nh mt bng chuyn i en c sn (xem ph lc).
3.5.3 ng nhn quang in (Photomultiplier tubes)
Trong cc my quang ph hin nay, ngi ta c th pht hin v o trc tip
cng ca cc vch ph bng cc nhn quang in, m khng cn ghi ph ln knh
nh. Do loi tr c sai s do knh nh gy ra.
Nhn quang in kiu ng hay detector tubes l mt loi dng c quang hc
thu nhn v pht hin tn hiu quang hc (tc l o cng chm sng) theo hiu
ng quang in ca n. Vi s pht trin ca khoa hc v k thut, ngy nay ngi ta
ch to c nhiu loi nhn quang in kiu ng (photomultiplier tubes) thu
nhn tn hiu quang hc v khuch i ln hng ngn, n hng triu ln, lm cho cc
my quang ph c th phn tch c nhiu nguyn t nng rt nh (t g n
ng). Hnh 3.12 l s nguyn tc cu to ca nhn quang in v vng ph lm vic
ca n. Nhn quang in l mt dng c vn nng thu nhn tn hiu quang hc. N
c nhy v chn lc cao. Vng ph lm vic ca nhiu loi nhn quang in
thng l t 190 n 900 nm, cho vng ph t ngoi v kh kin. Tt nhin, vng ph
71

lm vic ca mt loi nhn quang in ph thuc vo bn cht kim loi dng ch


to bn catot ca nhn quang in (hnh 3.12). Cc kim loi ch to catot ca nhn
quang in kiu ny thng l Na-Cs-K-Li-Sb. H s khuch i ca cc nhn quang
in thng l t 10+5 n 10+6, i khi c th n 10+7 ln.

72

73

74

Chng 4
CC YU T NH HNG TRONG AES

4.1 Khi qut chung


Cc yu t nh hng n kt qu phn tch trong php o ph pht x nguyn t
l rt a dng v phc tp, c khi xut hin v cng c khi khng xut hin, c nh
hng hay khng c l ty thuc vo thnh phn ca mu phn tch v cht nn
(matrix). Nhng nghin cu mt cch ton din, chng ta im qua tt c cc yu t
nh hng c th c trong php o ny. Cc yu t c th c chia thnh 6 nhm
nh sau:
Nhm 1. Cc thng s ca h my o ph. Cc thng s ny cn c kho st
v chn cho tng trng hp c th. Thc hin cng vic ny chnh l qu trnh ti u
ha cc thng s ca my o cho mt i tng phn tch.
Nhm 2. Cc iu kin ha hi, nguyn t ha mu v kch thch ph. Cc yu
t ny th hin rt khc nhau ty thuc vo k thut c chn thc hin qu trnh
ha hi, nguyn t ha, kch thch ph v n c nghin cu k trong chng 2.
Nhm 3. K thut v phng php c chn x l mu. Trong cng vic ny
nu lm khng cn thn s c th lm mt hay lm nhim bn thm nguyn t phn
tch vo mu. Do kt qu phn tch thu c s khng ng vi thc t ca mu. V
th, vi mi mt loi mu ta phi nghin cu v phi chn mt quy trnh x l ph hp
nht, c c ng thnh phn ca mu v khng lm nhim bn mu. Vn ny
s c nghin cu trong mt chng ring.
Nhm 4. Cc nh hng v ph.
Nhm 5. Cc yu t nh hng vt l.
Nhm 6. Cc yu t ha hc.
Trong chng ny chng ta s nghin cu k cc yu t thuc cc nhm 4, 5 v 6.
4.2 Mt s nh hng trong php o AES
4.2.1 Cc yu t v ph
4.2.1.1 S pht x ph nn
Yu t ny c trng hp xut hin r rng, nhng cng nhiu trng hp khng
xut hin. iu ny ph thuc vo vng ph v vch ph c chn o nm trong
vng ph no. Ni chung, trong vng kh kin th yu t ny th hin r rng, cn
trong vng t ngoi nh hng ny t xut hin, v ph nn trong vng t ngoi thng
yu. Hn na, s pht x nn cn ph thuc rt nhiu vo thnh phn ca mu phn
75

tch, c bit l matrix ca mu, ngha l nguyn t c s ca mu, v ngun nng


lng kch thch ph.
V d: Khi xc nh
Pb trong mu sinh hc
bng php o ngn la th
s hp th nn l khng
ng k. Nhng khi xc
nh Pb trong nc bin
(nn 2,9% NaCl) th nh
hng ny li l v cng
ln v bt buc phi b
chnh loi tr (hnh
4.1). Do , trong mi
trng hp c th phi
xem xt tm bin loi
tr. loi tr ph nn,
ngy nay ngi ta lp
thm vo my quang ph
nguyn t h thng b
chnh nn. Hoc a vo
mu cc cht lm gim s
pht x nn.
4.2.1.2 S chen ln ca cc vch ph gn nhau
Yu t ny thng thy khi cc nguyn t th ba trong mu phn tch c nng
ln v thng l nguyn t c s ca mu. Tuy nguyn t ny c cc vch ph
khng nhy, nhng do nng ln, nn cc vch ny vn xut hin vi rng ln,
nu n li nm cnh cc vch phn tch (bng 4.1), th cc vch ph ny s chen ln
cc vch phn tch, lm cho vic o cng vch ph phn tch rt kh khn v thiu
chnh xc, nht l i vi cc my c phn gii khng cao. V th trong mi mc
ch phn tch c th cn phi nghin cu v chn nhng vch phn tch ph hp
loi tr s chen ln ca cc vch ph ca nguyn t khc. Nu bng cch ny m
khng loi tr c nh hng th bt buc phi tch b bt nguyn t c vch ph
chen ln ra khi mu phn tch trong mt chng mc nht nh, cc vch chen ln
khng xut hin na. Tt nhin vic ny l hn hu.

76

Bng 4.1
S chen ln v s trng vch ca cc nguyn t
Nguyn t v vch
phn tch (nm)

Nguyn t c vch chen ln


Vch chen ln

Nng xut hin nguyn


t chen ln (ppm)

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)

S % b Ion ha nhit (oC):


2000

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

- Nhng nu o vch ph Ion th yu t ny li l cn thit v ta phi chn iu


kin qu trnh Ion ha t hiu sut cao v n nh nht, c c nng ln
ca nguyn t cn xc nh (phn tch) cao nht.
Thc t cho thy rng, qu trnh Ion ha thng ch c ngha i vi cc kim
loi kim v sau l cc kim loi kim th, cn i vi cc nguyn t khc s Ion
ha l khng ng k trong mi trng ca ngn la n kh v h quang in. loi
tr s Ion ha mt nguyn t phn tch chng ta c th dng cc bin php sau y:
+ Chn iu kin nguyn t ha c nhit thp, m trong iu kin nguyn
t phn tch hu nh khng b Ion ha.
+ Thm vo mu phn tch mt cht m cho s Ion ha. l cc mui halogen
ca cc kim loi kim c th Ion ha thp hn th Ion ha ca nguyn t phn tch vi
mt nng ln ph hp. Nh vy trong iu kin nguyn t phn tch s khng b
Ion ha na.
4.2.2.3 Hin tng t o (t hp th) ca vch phng
Hin tng ny thng xut hin trong vng ngoi ca plasma l r rt nht hay
khi nng cht phn tch ln. V vng ny c nhit thp, nn cc nguyn t ca
cht phn tch li hp th chnh tia pht x m cc nguyn t trong li ca ngn la
sinh ra, v th lm mt bt i mt phn cng pht x ca cht phn tch. iu ny
cng gp phn gii thch ti sao nng ln th mi quan h gia cng vch
ph pht x Iv nng Cx ca cht l khng cn tuyn tnh na.
Trn y l mt s yu t vt l c th xut hin trong php o AES v c th nh
hng n kt qu phn tch. Nhng mc xy ra l rt khc nhau trong mi trng
hp c th, c khi c, c khi khng. Mc ny xut hin ln hay nh ph thuc vo:
+ Nhit ca plasma,
+ Cc iu kin ca mi trng kch thch ph pht x,
+ Tnh cht ca nguyn t phn tch v hp cht ca n,
+ Cht nn ca mu v thnh phn ca mu phn tch.
Do cn phi xem xt tm bin php loi tr khi chng xut hin, theo tng
loi mu c th.
4.2.3 Cc yu t ha hc
Trong php o ph pht x nguyn t cc nh hng ha hc cng rt a dng v
phc tp. N xut hin cng rt khc nhau trong mi trng hp c th v cng nhiu
trng hp khng xut hin. Cc nh hng ha hc thng c th dn n kt qu
79

theo bn hng sau y:


- Lm gim cng ca vch ph ca nguyn t phn tch, do s to thnh cc
hp cht bn nhit, kh ha hi v kh nguyn t ha. V d nh nh hng ca cc
Ion silicat, sunfat, photphat, florua.
- Lm tng cng ca vch ph, do s to thnh cc hp cht d ha hi v d
nguyn t ha, hay do hn ch c nh hng ca s Ion ha ca nguyn t phn
tch. chnh l tc dng ca mt s hp cht, ch yu l mui halogen ca kim loi
kim v kim th hay lantan Clorua.
S tng cng vch ph khi nguyn t phn tch tn ti trong nn ca mu l
nhng hp cht d ha hi. Lc cc cht nn ny c tc dng nh l mt cht mang
cho s ha hi ca nguyn t phn tch v lm n c ha hi vi hiu sut cao hn.
S gim cng ca vch ph khi nguyn t phn tch tn ti trong nn mu l
nhng hp cht bn nhit, kh ha hi. Lc ny cc nguyn t nn km hm s ha hi
ca nguyn t phn tch. Cc cht nn ny thng l nhng hp cht bn nhit ca cc
nguyn t, nh Al, t him, silicat, v.v...
V th vic nghin cu cc nh hng ha hc c trnh by trong chng ny
c tnh cht khi qut chung tt c cc loi c th c chng ta lu khi ng dng
php o ph pht x nguyn t, vi mc ch bit v loi tr cc nh hng ha
hc, nu chng xut hin. Cc nh hng ha hc c th c sp xp theo cc loi
sau y:
4.2.3.1 Nng axit v loi axit trong dung dch mu
Ni chung nng axit trong dung dch mu lun lun c nh hng n cng
ca vch ph ca nguyn t phn tch v nh hng ny thng gn lin vi loi
Anion ca axit. Cc axit cng kh bay hi thng cng lm gim nhiu cng vch
ph. Ngc li, cc axit d bay hi gy nh hng nh (hnh 4.3). iu ny c th
thy r rng khi xc nh Ca o vch ph Ca-422,7 nm trong cc mi trng ca cc
axit HClO4, CH3COOH, HCl, HNO3, H2SO4, H3PO4, HF vi cng mt nng l 2%
(hnh 4.4).
Ni chung, cc axit lm gim cng vch ph theo th t: HClO4 < HCl <
HNO3 < H2SO4 < H3PO4 < HF, ngha l axit HClO4, HCl v HNO3 gy nh hng nh
nht. Chnh v th trong thc t phn tch ca php o ph pht x nguyn t (AES)
ngi ta thng dng mi trng l axit HCl hai HNO3 1 hay 2%, v nng ny
nh hng ca hai axit ny l khng ng k (nh hn 5%).

80

4.2.3.2 V nh hng ca cc Cation khc trong mu


Dung dch mu phn tch, ngoi nguyn t cn xc nh, cn cha cc nguyn t
khc. Cc nguyn t ny tn ti di dng cc Cation hay Anion tan trong dung dch
81

mu. Cc Ion ny c th lm tng, cng c th lm gim, hoc cng c th khng gy


nh hng g n cng vch ph ca nguyn t phn tch. Khi c nh hng th
mc nh hng ca mi Ion cng rt khc nhau trong tng trng hp c th.
Nhng mt cch tng qut th chng ta c th quy nh hng ca cc Cation theo 7
loi nh trong hnh 4.5 d xem xt.
- Loi 1, 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 (xem ng 1, hnh 4.5).
- Loi 2, th ti nng Cl 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 Cl (ng 2, hnh 4.5).
- 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 (ng 3 trong hnh 4.5).
- 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 C4. Do vy, nu nng ca cc Cation
trong mu nh hn gi tr C4 th khng phi quan tnm n tm bin php loi tr
(ng 4, hnh 4.5).
- 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
(ng 5, hnh 4.5).
- Loi 6. Khi nng ca cc Cation khc trong mu ln hn gi tr C5 th chng
khng lm gim 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 C6, 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 (ng 7, hnh 4.5).
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.
nh hng ca cc Cation c trong mu n cng vch ph ca nguyn t
phn tch trong php o ph nguyn t cng rt khc nhau. V d: Ion La(III) trong
php o F-AAS l yu t loi tr nh hng ca cc Ion l c trong mu khi xc
nh Ca, Mg, Mn, Al, Fe. Nhng chnh La(III) li l Ion nh hng v lm gim cng
82

vch ph ca chnh Ca, Mg, Al, Fe rt ln trong php o F-AES. iu c ngha


l mi Cation trong tng trng hp c th v trong mi php li c tc dng khc
nhau, m chnh n trong php o ny th nh hng, nhng trong php o khc li
khng gy nh hng.
Nh vy, nh hng ca cc Cation n cng vch ph ca nguyn t phn
tch c th c hiu ng dng, hiu ng nm v cng c th c hiu ng va nm va
tng i vi mt Ion, khi n cc nng khc nhau. minh ho v nh hng
ca cc Cation i vi vch ph ca nguyn t phn tch chng ta c th xem xt mt
s v d trong cc hnh t 4.6 - 4.8.

loi tr nh hng ca cc Cation n cng vch ph ca nguyn t phn


tch chng ta c th s dng mt s bin php sau y hoc ring bit, hoc t hp ca
chng vi nhau, ty tng trng hp c th, v d c th:
+ Thm cht ph gia kh nh hng;
+ Thay i nn ca mu loi tr nh hng;
+ Pha long mu bng cht ph gia lm gim thiu nh hng,
+ Thay i iu kin ha hi, nguyn t ha v kch thch ph;
83

+ Thay i mi trng kh quyn kch thch ph, dng kh tr argon, v.v...

84

4.2.3.3 nh hng ca cc Anion


Cng vi cc Cation, cc Anion cng nh hng n cng vch ph ca
nguyn t phn tch, v nh hng ny cng tng t nh nh hng ca cc loi axit.
Ni chung, cc Anion ca cc axit d bay hi thng lm gim t cng vch ph.
Ch ring c hai Anion ClO 4 v CH 3CPPOO , l gy hiu ng dng (lm tng), tc
l lm tng cng vch ph ca nguyn t phn tch trong mt s trng hp mt
85

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%.

4.2.3.4 Thnh phn nn ca mu


Yu t nh hng ny ngi ta quen gi l matrix effect. Nhng khng phi lc
no n cng xut hin, m ch thy trong mt s trng hp nht nh. Thng thng
l cc 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 lm gim hng trm ln cng ca vch ph
(bng 4.4). Nguyn nhn chnh ca nh hng ny l s tn ti ca cc hp cht bn
nhit trong mi trng pht x. Cc hp cht ny lm kh khn, cn tr qu trnh ha
hi v nguyn t ha ca cc nguyn t phn tch.
loi tr nh hng ca thnh phn nn ca mu phn tch ngi ta c th
dng cc bin php khc nhau, nh:
86

1. Tng nhit ca plasma kch thch ph;


2. Thm vo mu cc cht ph gia c nng ph hp;
3. Thay i nn ca mu sang nn khc;
4. Tch loi b nguyn t nn cn tr, khi ba bin php trn khng t kt qu.
Tt nhin bin php ny l hn hu.
Bng 4.4
nh hng ca thnh phn nn ca mu phn tch

Cht nn ca mu

Cng vch ph C=30 ppb


php o AES
Mg-202,60 nm

Ca-422,70 nm

1. Dung dch HCl 1%

0,220

0,250

2. Nh 1, thm 2% LaCl3

0,008

0,005

3. Nh 1, thm 0,5% LaCl3

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

5.1 Nguyn tc chung


Nh chng ta bit, khi cung cp nng lng ha hi, nguyn t ha mu
phn tch v kch thch m hi nguyn t i n pht x th chng ta s thu c
ph pht x ca mu phn tch. Ph gm ba thnh phn:
1. Ph vch ca nguyn t v Ion.
2. Ph m ca phn t v nhm phn t.
3. Ph nn lin tc.
Trong ba thnh phn , th ph vch l thnh phn chnh c trng cho nguyn
t v Ion trng thi hi t do, khi chng b kch thch, ngha l trng thi hi. Khi
b kch thch, cc nguyn t v Ion s pht ra mt chm bc x quang hc gm nhiu
tia c bc sng khc nhau nm trong di ph quang hc (190-1100nm). Nu thu,
phn li v ghi chm sng li ta s c mt di ph gm cc vch pht x ca
nguyn t v Ion ca cc nguyn t c trong mu. Trong tp hp cc vch ph , th
mi loi nguyn t hay Ion li c mt s vch c trng ring cho n. Cc vch ph
c gi l cc vch ph pht x c trng ca loi nguyn t y. V d khi b kch
thch: Nguyn t Al pht ra vch c trng trong vng UV: 308,215; 309,271nm.
Nguyn t Cu pht ra vch c trng trong vng UV: 324,754; 327,396nm. - M pht
ra vch c trng trong vng UV: 259,373; 260,570nm.
- Nguyn t m pht ra vch c trng trong vng UV:279,553; 280,270nm.
Chnh nh cc vch ph c trng ny ngi ta c th nhn bit c s c mt
hay vng mt ca mt nguyn t no trong mu phn tch qua vic quan st ph
pht x ca mu phn tch, v tm xem c cc vch ph c trng ca n hay khng,
ngha l da vo cc vch ph pht x c trng ca tng nguyn t nhn bit
chng. l nguyn tc ca phng php phn tch quang ph pht x inh tnh.
T c s vt l chng ta c th khi qut qu trnh phn tch quang ph pht
x nh tnh gm cc giai on sau y:
1. Cung cp nng lng ha hi, nguyn t ha mu phn tch to ra m hi
nguyn t t do v kch thch m hi pht ra ph pht x ca chng.
2. Thu chm sng pht x , phn li v ghi ph pht x ca mu phn tch.
3. Quan st ph thu c ca mu phn tch theo cc vch c trng ca cc
88

nguyn t pht hin chng.


Cc giai on ny c thc hin nh mt h thng my quang ph pht x. H
thng my ny cng gm ba phn chnh tng ng vi ba nhim v nu trn. l:
Phn 1. Ngun nng lng ha hi, nguyn t ha v kch thch m hi
nguyn t ca mu n pht x.
Phn 2. My quang ph thu, phn li v ghi ph pht x ca mu.
Phn 3. H thng trang b quan st nh tnh v nh lng.
Trong phn tch nh tnh, khi quan st khng thy vch ph pht x c trng
ca mt nguyn t trong ph ca mu phn tch, iu c th xy ra hai kh nng:
1hoc l hon ton thc t khng c nguyn t trong mu phn tch, 2. Hoc l
nguyn t c trong mu phn tch, nhng nng ca n nh hn nhy pht
hin ca phng php phn tch. V th khng xut hin vch ph pht x c trng
ca n. V d: Nu dng 2 loi ngun HQ v ICP kch thch ph pht x th:
+ Vi ngun HQ: 2 vch Cu nu trn xut hin nng C > 0,0004%
+ Vi ngun ICP: Cng 2 vch Cu ny, nhng xut hin nng C >
0,00004%. Do vic kt lun kt qu phn tch phi theo phng php phn tch v
cc iu kin trang b dng thu ghi ph ca mu phn tch v nhy ca
phng php s dng.
l hin tng thc t, song ngi ta thng hay quy c v coi nh l khng
c nguyn t trong mu phn tch, khi khng tm c cc vch c trng (2 vch
ph) ca nguyn t trong ph pht x ca mu phn tch, theo k thut dng
nh tnh.
5.2 Vch chng minh nh tnh v cch chn
Mun xc nhn s c mt hay khng c mt ca mt nguyn t no trong mu
phn tch, ngi ta phi tm mt s vch ph c trng ca nguyn t trong ph ca
mu phn tch xem c hay khng, t m kt lun c n hay khng c n trong
mu phn tch. Nhng vch ph c trng c chn c gi l vch chng minh
ca nguyn t y. Ni chung, pht hin mt nguyn t t kt qu chnh xc v
chc chn, ngi ta phi chn t nht hai vch chng minh khi quan st ph ca mu
phn tch. Cc vch ph ny phi tha mn mt s iu kin sau y:
1. Nhng vch ph ny phi r rng v khng trng ln vi cc vch ca nguyn
t khc, nht l nguyn t nng ln.
2. N phi l nhng vch ph nhy, c th pht hin c cc nguyn t trong
mu vi nng nh (phn tch lng vt).
3. Vic chn cc vch ph chng minh cho mt nguyn t phi xut pht t
ngun nng lng dng kch thch ph ca mu phn tch, v trong ngun kch
89

thch c nng lng thp th ph ca nguyn t l ch yu v vch nguyn t ca n


thng l nhng vch nhy. Ngc li, trong ngun kch thch giu nng lng (ICP)
th ph ca Ion l ch yu. Cho nn phi ty thuc vo ngun nng lng dng
kch thch ph m chn vch chng minh l vch nguyn t hay vch Ion cho ph hp.
4. Phi cn c vo my quang ph c th thu, phn li v ghi c trong vng
sng no m chn vch chng minh cho mt nguyn t nht nh. V d chng
minh Na, nu ph mu c ghi trn my Q-24 (vng ph 200-400 no th ta phi
chn hai vch Na 330,30 v Na 330,27 nm. Ngc li, nu ghi trn my lng knh thy
tinh (vng ph 360-780 nm.), th li phi chn hai vch Na 589,60 v 589,00 nm. Nu
dng my cch t PGS-2 (vng ph 200- 1100 nm) th chn 4 vch trn u c.
5.3 nhy ph v kh nng pht hin
Trong phn tch quang ph pht x nguyn t ngi ta thng s dng hai khi
nim v nhy. l nhy tuyt i v nhy tng i xem xt hay nh
gi kh nng phn tch ca mt phng php.
5.3.1 nhy tuyt i (cn gi l nhy khi lng)
nhy tuyt i l lng gam nh nht ca mt nguyn t cn phi a vo
kch thch ph trong plasma cn pht hin c t nht hai vch ph c trng ca
nguyn t y trong mt iu kin nht nh chn, ngha l cn chng minh c
nguyn t y. V d, ch c th pht hin c cc nguyn t:
+ Pb khi trong plasma h quang kch thch ph phi c 0,000007 g Pb.
+ Al khi trong plasma h quang kch thch ph phi c 0,0000055 g Al.
Cn cc gi tr nh hn th khng th pht hin c Pb v Al. Cc gi tr
(lng gam) 0,000007 g v 0,0000055 g c gi l nhy tuyt i ca Pb v Al
trong php phn tch . Nh vy, mi nguyn t khc nhau c nhy tuyt i khc
nhau v ph thuc vo mi nguyn t, cc iu kin kch thch v ghi ph ca mu
(bng 5.1).
5.3.2 nhy tng i (cn gi l nhy nng )
nhy tng i l nng nh nht ca mt nguyn t phi c trong mu
phn tch cn c th pht hin c t nht hai vch ph c trng ca n, trong
cc iu kin thc nghim nht nh chn. Cn nu nh hn nng th ta
khng th tm c mt vch c trng no ca n trong ph ca mu phn tch. V
d: pht hin c hai vch ph c trng ca cc nguyn t sau trong ngun h
quang, phi c:
90

+ Pb vi nng trong mu l => 0,0008 %


+ Al vi nng trong mu l => 0,0004 %
+ Cu vi nng trong mu l => 0,0005 %
Cc gi tr 0,0008; 0,0004; 0,0005 % c gi l nhy tng i ca Pb, Al
v Cu trong php phn tch ny. l nng nh nht cn pht hin c cc
nguyn t theo 2 vch ph pht x ca n trong mt iu kin nht nh chn .
Cng nh khi nim trn, mi nguyn t khc nhau cng c nhy tng i
khc nhau. Ni chung, cc nguyn t c t vch ph thng c nhy cao (bng 5.1).
Trong phn tch ngi ta hay dng khi nim nhy tng i v ch i khi cn
thit mi dng khi nim nhy tuyt i, v dng khi nim nhy nng chng
ta d so snh nhy ca cc nguyn t vi nhau hn. Nh vy, kh nng chng minh
ca mt nguyn t ph thuc vo nhy ph ca nguyn t . Nguyn t no cng
nhy ph th cng c th pht hin c n ngay nng rt nh (tt nhin l nng
ny phi cn ln hn nhy tng i).
Ngoi nhy ph ca mt nguyn t, kh nng chng minh ca nguyn t cn
ph thuc vo mt s yu t khc, nh:
+ Cc iu kin thc nghim ha hi, nguyn t ha mu, kch thch cc
nguyn t v iu kin trang b ghi o ph ca mu phn tch.
+ Cht lng ca h thng quang hc ca my quang ph;
+ Cu to, thnh phn vt l v ha hc ca mu phn tch;
+ Mi trng kch thch ph;
+ Trng thi tn ti ca nguyn t trong mu;
+ Cht ph gia thm vo mu phn tch.
Nhng trong mt iu kin th nghim nht nh ph hp c chn, vi h
thng trang b nh nhau v cng mt loi mu, th kh nng chng minh ca mt
nguyn t ch cn ph thuc vo nhy ph ca nguyn t phn tch v trang b thu
nhn ph m thi.
V th mun nh gi, so snh kh nng chng minh ca mt nguyn t bng ph
pht x nguyn t, chng ta phi nghin cu chng trong nhng iu kin nht nh
nh nhau v ph hp, nh ngun nng lng ha hi, nguyn t ha v kch thch
ph, cng nh cc iu kin ghi ph ca chng.
Bng 5.1
91

Vch c trng ca mt s nguyn t


Nguyn t
Ag

Al

Ba
Ba

Ca

Cu

Fe

92

Vch ph (nm)

Cng

Nng xut hin (%)

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

5.4 S trng vch v cch loi tr


Ph pht x ca mt nguyn t thng c rt nhiu vch, c khi n hng ngn
vch. Cc vch ny phn b t vng sng ngn n sng di ca di ph quang hc
(190-1100 nm). Nguyn t no c cu to lp v in t cng phc tp, nht l s in
t ha tr cng nhiu, th ph pht x ca chng cng c nhiu vch, v d nh Fe. V
th, ph pht x ca mu phn tch, nht l cc mu a kim loi, th ph pht x ca n
tt nhin cng c nhiu vch. Trong di ph tt nhin c th c hai nguyn t khc
nhau, nhng chng li c th pht ra tia bc x cng di sng, hoc khc nhau
khng n 0,01 nm. Trong trng hp ny vch ph ca hai nguyn t l trng
nhau hon ton hoc l chng ln nhau mt phn, ngha l c hin tng trng vch,
hin tng quy ri v chen ln ca cc vch ph ca cc nguyn t vi nhau.
5.4.1 Vch ph trng
Vch ph trng l cc vch ph ca cc nguyn t khc nhau, nhng c cng mt
gi tr di sng. V th trn knh nh ta ch thy c mt vch duy nht. V d vch
La 412,323nm trng vi vch ph Er 412,823nm (khng nhy). Nn khi nh tnh
khng c chn vch La 412,323nm chng minh nguyn t La, mc du l mt
vch nhy ca La.
5.4.2 Vch quy ri v chen ln
Vch quy ri v chen ln l vch ph ca cc nguyn t khc nhau, nhng
chng c i sng xp x bng nhau m my quang ph khng phn gii c
thnh cc vch ring r. V th trn knh nh hai vch ph ny nm k nhau v c mt
phn chng ln nhau. Do khi quan st ta cng ch thy c mt vch rng. Song c
trng hp hai vch c th tch ra c nng nh ca c hai nguyn t, nhng
khi mt trong hai nguyn t c nng ln, tt nhin l vch ca nguyn t c nng
ln s ln t vch ca nguyn t c nng nh. l s quy ri v chen ln ca
cc vch ph ca cc nguyn t. V th, chng minh nh tnh mt nguyn t chng
ta cng phi loi tr nhng vch ph c hin tng .
5.4.3 Ph m
Bn cnh s trng vch v s quy ri ca cc vch ph ca cc nguyn t khc
nhau, th ph m ca cc phn t v nhm phn t cng l mt yu t gy kh khn
cho php phn tch nh tnh, v trong nhiu trng hp th ph m ca cc phn t
che lp mt cc vch c trng ca cc nguyn t khc. iu ny th hin rt r trong
vng kh kin (380-780 nm), nu ta kch thch ph ca mu phn tch trong mi
trng khng kh, hay trong cc my quang ph c phn gii khng ln.
l nhng kh nng c th xy ra khi quan st bt k mt bng vch ph no
ca cc nguyn t ha hc. Song khng phi v th m khng chng minh nh tnh
c mt nguyn t theo ph pht x ca n. Bng thc t, ngy nay ngi ta c rt
nhiu cch khc nhau loi tr cc yu t nh hng . V d: Trong iu kin kch
93

thch ph thng thng th tt nhin khng th xut hin cc vch ph ca cc cht kh


nh oxy, halogen, nit,... Hoc khi phn tch cc mu thng thng tt nhin khng
th c kh nng trng vch vi cc nguyn t phng x, t him, nguyn t qu,...
Mt khc cn c vo cng ca cc vch ph hay nng xut hin ca cc vch
ph khc nhau ca cc nguyn t, chng ta cng c th d on c trong iu kin
c th th vch ph c xut hin hay khng, ngha l trong mi trng hp c
th cn phi lun lun ch n nhng kh nng trng vch, s quy ri v chen ln
ca cc vch ph vi nhau. Song cng t cc trng hp c th m tm cch khc
phc cho ph hp.
Sau y l mt s v d v mt vi phng php loi tr mt s yu t nh
hng nu.
1. Li dng tnh cht bay hi khc nhau ca cc nguyn t theo thi gian chn
thi gian ghi ph cho thch hp (theo ng cong bay hi). T c th loi tr c
s quy ri ca cc nguyn t khc i vi nguyn t phn tch.
2. Chn iu kin v ngun nng lng kch thch ph ph hp, to ra s
kch thch ph c u tin v chn lc i vi mt vi nguyn t chng ta cn kho
st, phn tch.
3. Chn mi trng kch thch ph cho ph hp. V d: Khng kch thch ph
trong khng kh m kch thch chng trong mi trng ca mt kh tr hay hn hp
ca kh tr vi oxy. Trong trng hp ny ngi ta c th loi tr c hon ton nh
hng ca ph m ca cc phn t v nhm phn t CN. Chnh v th hin nay trong
phn tch quang ph pht x, ngi ta thng kch thch ph ca mu phn tch trong
mi trng ca kh tr Al v hn hp ca argon vi oxy.
4. Thm vo mu nhng cht ph gia thch hp c th loi tr cc hp phn
sinh ra ph quy ri khng c li, nh to ra s bay hi chn lc, s bay hi phn
on ca cc nguyn t khc nhau.
5. Chn my quang ph c phn gii ln v vng ph ph hp thu, phn li
v ghi ph ca mu phn tch. Trong thc t phn tch, th bin php ny trong nhiu
trng hp c kh nng loi tr hon ton cc yu t nh hng nu.
Nu tt c cc bin php trn s dng m vn cha loi tr c nh hng,
th phi dng phng php tch chit no loi cc nguyn t cn tr ra khi mu
phn tch. Tt nhin y l bin php cui cng v thc t hu nh rt t khi phi s
dng n.
5.5 Cc phng php phn tch nh tnh
Mc ch ca phn tch quang ph pht x nh tnh l pht hin cc nguyn t,
ch yu l cc kim loi trong cc mu phn tch, n gm c hai loi yu cu, do
cng c 2 kiu nh tnh:
94

1. Phn tch nh tnh tng phn v


2. Phn tch nh tnh ton din.
Phn tch nh tnh (T) tng phn tc l kim tra xem trong mu phn tch c
cha nhng nguyn t m ngi ta cn quan tnm n hay khng, cn cc nguyn t
khc th khng cn bit n. V d ngi a mu yu cu tm xem trong mu ny c
Pb hay khng?
y l phn tch T tng phn, v ch cn tm nguyn t Pb trong mu. - Ngc
li, phn tch nh tnh ton din l phi xc nh xem trong mu phn tch cha bao
nhiu nguyn t c thy. V d ngi a mu yu cu tm xem trong mu ny c bao
nhiu kim loi c thy? y l phn tch T ton din.
Chnh t thc t m ngi ta cng c mt s cch quan st nh tnh khc
nhau, da theo ph pht x ca mu.
5.5.1 Phng php quan st trc tip trn mn nh
Nguyn tc ca phng php ny l trn mn nh ca my quang ph (mt phng
tiu) ngi ta t mt mng m, trn mng m ny c nh du v tr cc vch c
trng ca mt s nguyn t nht nh. ng thi b tr mt h thng thu knh lp
phng i quan st trc tip mn nh .
Nh vy, mun nh tnh mt mu no , ta thu ph ca mu phn tch, khi kch
thch chng bng mt ngun nng lng ph hp v quan st ph mt cch trc tip
trn mn nh ca my nh h thng knh lp phng i.
Khi da theo cc vch ph c trng nh du trn mng m m kt lun
c mt hay khng c mt nguyn t trong mu phn tch.
Phng php ny nhanh, n gin. Nhng ch gii hn trong nhng mu n
gin v nhng nguyn t cn phn tch c nh du cc vch ph c trng ca n
trn mng m ca my quang ph.
N ch yu phc v cho phn tch luyn kim, kim tra nhanh mt vi nguyn
t cn thit, nh Mn, Cr, Si, C, Al,...V cng v th m c mt loi my quang ph
chuyn dng cho mc ch ny. l cc loi my Styloscop. My quang ph ny
phc v cho ni dung phn tch nh tnh tng phn ca ngnh luyn kim l ch yu.
5.5.2 Phng php so snh ph
y l phng php n gin, chnh xc, nhng cng ch phc v cho mc ch
phn tch nh tnh tng phn.
Nguyn tc ca phng php ny l: Mun nh tnh mt nguyn t X no ,
95

chng ta phi ghi ph ca nguyn t X nguyn cht k vi ph ca mu phn tch. Ri


tm mt nhm vch c trng ca nguyn t X trong mu nguyn cht v so snh
nhm vch ph vi ph ca mu phn tch xem c nhng vch ph c trng
hay khng trong ph ca mu phn tch.
Trn c s m kt lun c mt hay khng c mt ca nguyn t X trong mu
phn tch. Phng php ny tuy n gin, nhng vi mi nguyn t cn tm ta li phi
ghi mt ph ca nguyn t nguyn cht.
V th chng nhng tn km knh nh, in cc v thi gian, m nhiu khi cn
khng c ca nguyn t X tinh khit lm ph so snh. Do n cng b hn ch
v khng c ng dng nhiu trong thc t.
5.5.3 Phng php ph chun (Dng bn atlas)
Ph chun hay cn gi l bn atlas ph l cc bng vch ph ca Fe theo mt
my quang ph nht nh. N c xem nh l mt thang di sng phc v cho
vic nh du v tr cc vch ph c trng ca cc nguyn t. N c cu to gm 2
phn.
Phn trn l mt dy cc vch ph ca Fe trong mt vng ph nht nh ca my
quang ph. Phn di, tc l k vi ph ca Fe, l v tr cc vch ph c trng ca
cc nguyn t khc v trn cng l thang s sng (hnh 5.1).
Nh vy, mun nh tnh mt mu no , ta cn phi ghi ph ca Fe v k l
ghi ph ca mu phn tch.
Sau nh my chiu ph v bn atlas ta c th nhn bit c trong mu phn
tch c cha nhng nguyn t no khi quan st ph ca mu phn tch theo cc vch
ph c trng ca tng nguyn t, bng cch em ph ca Fe trn knh nh lm trng
vi ph ca Fe trn bn atlas.
V th, nh tnh bao gi cng phi ghi ph theo tng cp, mt ph ca Fe v
k l ph ca mu phn tch, ngha l c bao nhiu mu phn tch th c by nhiu
cp ph tng ng.
Phng php ny ph hp cho c hai mc ch phn tch nh tnh tng phn v
nh tnh ton din. Nhng mi my quang ph cn phi c mt b atlas hon chnh
cho n i vi tt c mi nguyn t cn nghin cu.
V th ngy nay hu ht cc phng th nghim ch dng phng php ny cho c
hai mc ch phn tch nh tnh. Cc hng bn my quang ph cng cung cp
cc bng atlats cho cc my ca h.
Hnh 5.1 l v d v mt on ca bn atlas ca my quang ph.
96

97

98

Chng 6
PHN TCH PH PHT X NH LNG

6.1 Nhng vn chung


6.1.1 Phng trnh c bn v nguyn tc
Phng php phn tch quang ph pht x nguyn t nh lng da trn c s
gia nng ca nguyn t cn phi xc nh v cng ca vch ph pht x do n
pht ra, khi b kch thch trong nhng iu kin thch hp, c mi lin h tuyn tnh v
n tr theo hm s.
I = f (C)

(6.1)

trong mt gii hn nht nh ca nng C ca nguyn t phn tch, trong I


l cng ca vch ph pht x ca nguyn t , cn C l nng ca nguyn t
trong mu phn tch.
Bng l thuyt v thc nghim ngi ta tm c mi lin h v c m t
theo phng trnh Lmaskin - Schraib nh trnh by trong chng II trn l:
I = a.Cb

(6.2)

Theo phng trnh ny, nu c mt s mu u (mu chun) c nng C


bit chnh xc, v d C1, C2, Cn v xc nh c cng ca 1 vch ph pht x
I tng ng ca chng, th ta c th dng c ng chun I - C, ri t c th d
dng tm c nng Cx cha bit.
Nhng trc y (trc 1965), do khng xc nh trc tip c gi tr cng
pht x I ca mt vch ph, m ngi ta phi chiu chm sng pht x cng I
ln knh nh. Sau xc nh cng hay en ca chng trn knh nh ti ch
b chm sng I tc dng ln. en S ny c tnh theo cng thc:
S = .log.I

(6.3)

trong l h s nh tng ca knh nh. Nh vy, ta c phng trnh h qu


nh sau, vi k = .log a:
S = . b.log.C + k

(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

c gi tr cng I th chng ta tnh ton theo phng trnh (6.2). Nu cc my


quang ph phi xc nh gin tip cng I qua vic xc nh en S, th phi tnh
ton theo phng trnh (6.4), ngha l phng trnh th nht c dng y = ax, cn
phng trnh th hai th c dng y = ax + b, song chng u l phng trnh ca mt
ng thng. Nhng nu o theo phng trnh en S, chng ta phi loi en ca
ph nn. V th trong trng hp ny phng trnh thc nghim s phi l:
S = .b.logC + ko

(6.5)

Do , phng trnh (6.3) v phng trnh (6.5) c gi l phng trnh c bn


ca phng php phn tch quang ph pht x nguyn t nh lng. ng biu din
cc phng trnh ny c m t trong hnh 6.1.

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

6.1.2 Vch phn tch v cch chn


loi tr ph nn khi xc nh en S ca vch ph phn tch, ngi ta
thng thc hin theo mt trong hai cch sau:
Cch 1: o hiu s en gia vch ph phn tch v ph nn, tc l tnh gi tr
S trong phng trnh (6.4) theo cng thc S = (Sv - Sn). Trong Sv v Sn l en
ca vch v en ca nn bn vch o (hnh 6.1).
Cch 2: o hiu s en gia mt vch phn tch Spt v mt vch ph so snh
Sss (hnh 6.1), ngha l c S = (Spt - Sss). Trong :
+ Vch phn tch l nhng vch ph ca nguyn t cn phi xc nh c chn
xc nh nng ca n trong mu phn tch. N c chn ra t nhng vch c
trng ca nguyn t y. Khi cn xc nh nhng nng nh th phi chn nhng
vch c nhy cao.
+ Vch so snh l nhng vch ph ca mt nguyn t no c chn o
en phc v cho vic b chnh nn theo phng php 2 vch ph. Nguyn t cung cp
cho vch so snh ny c gi l nguyn t so snh. N phi c nng khng i
trong c mu u v mu phn tch. N c th l nguyn t c s ca mu phn tch
hay l mt nguyn t khc c thm vo vi nng ph hp v khng i tt c
mu v cng ca n phi nm trong vng 10 - 25 % en ca vng tuyn tnh.
Nh vy, vch ph phn tch v vch ph so snh to thnh mt cp vch phn
tch. Do , c c kt qu chnh xc trong cp vch phn tch th vch so snh v
vch phn tch cn phi tha mn mt s iu kin nht nh nh sau:
1. Chng phi l hai vch cng loi, hoc l hai vch nguyn t, hoc l 2 vch
ln cng bc Ion ha.
2. Th kch thch ca hai vch ny phi gn bng nhau. Nu bng nhau l iu l
tng. Tt nhin trng hp bng nhau l iu him c, do cn chn bi vch c
th kch thch ph cng gn bng nhau th cng tt. V nh th s loi b c nh
hng ca s dao ng ca nhit plasma.
3. Hai vch phi khng xa nhau qu 10 mm trn knh nh (mt phng tiu), v ch
trong iu kin h s nh tng knh nh mi thc s l hng s, ngha l hu nh
khng ph thuc vo di sng ca cc vch ph.
4. Hai vch phi nt, r rng v gi tr S ca chng phi thay i nhy vi s
bin thin nng ca nguyn t phn tch trong mu, nhng li khng nhy vi
nhng dao ng ca iu kin thc nghim.
5. Gi tr S phi khng qu ln, m cng phi khng qu nh. N phi nm
trong vng gi tr en tuyn tnh ng cong, c trng ca knh nh ghi ph.

101

6. Trong mt s trng hp c th khng nn chn vch phn tch l nhng vch


d xut hin hin tng t o (t hp th), v khi phm vi tuyn tnh ca ng
chun s b hp. Tt nhin yu t ny l khng bt buc cho mi trng hp. N ch l
mt iu ch thm trong nhng trng hp cn thit, khi xc nh vng nng
khng qu nh.
Nhng hin nay, vi cc my quang ph th h mi, o trc tip cng vch
pht x I v trong my c sn h thng b chnh nn ca vch phn tch, th ngi ta
ch cn o mt vch phn tch l .
6.1.3 Cch biu din nng trong phn tch quang ph
Trong phn tch quang ph nh lng ngi ta thng dng v biu din nng
theo cc khi nim sau:
- Nng phn trm (%).
- Nng phn triu (ppm) v cc n v c s ca n.
- Nng microgam (g/mL) v cc n v c s ca n.
6.1.3.1 Nng phn trm
Trong phn tch quang ph ngi ta thng hay biu din nng phn trm (%)
theo hai cch:
a. Nng phn trm tuyt i: Ch cho ta s phn trm ca nguyn t phn tch
so vi tng khi lng m ca mu phn tch, ngha l c tnh theo cng thc:
%C xt =

mx
100
m

(6.6)

trong mx l s g ca nguyn t phn tch c trong khi lng mu mg.


b. Nng phn trm tng i: Ch cho ta bit s phn trm ca nguyn t
phn tch so vi khi lng m ca nguyn t c s (nguyn t c thnh phn > 90%)
ca mu phn tch. N c tnh theo cng thc:
%C xd =

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)

3.1.3.2 Nng phn triu (ppm) v cc n v sau n


i lng nng ppm (phu pa mill Ion) l n v nng c tnh theo n
v l mt phn triu (1/1.000.000) theo n v khi lng hay mt phn triu theo n
v th tch ca mu phn tch (cho mu lng). Nn theo khi nim n v ny, mt
nguyn t phn tch c nng 10-6g trong 1 gam mu, th gi tr ny c gi l 1
ppm. Nh th, nu vit theo khi lng: 1g/T, hay 1 mg/kg, hay 1g/g, hay theo th
tch 1 l/mL; hay 1 mL/L; hay 1 L/m3, th u tng ng 1 ppm.
Cn cc n v nh hn sau ppm l:
- ppb v 1 ppb bng 0,001 ppm
- ppp v 1 ppp l bng 0,001 ppb = 0,000001 ppm
- ppf v 1 ppj l bng 0,001 ppp = 0,000001 ppb = 0,0000000001 ppp
Cc n v ny hn km nhau 1000 ln. Trong phn tch vi lng v siu vi
lng, h n v ny c dng ph bin nht.
6.1.3.3 Nng microgam
Loi nng ny c biu th theo hai cch, c th l:
A. Theo th tch mu (khi lng th tch)
A1. Microgam/L: S microgam ca cht phn tch c trong mt lt dung dch
mu, k hiu l g/l. V d, nu vit nng ca Pb l Cpb: 1,2 tg/l th c ngha l c
trong 1 lt dung dch mu s c 1,2 microgam ca Pb.
A2. Microgam/ml: S microgam cht phn tch c trong mt mnh dung dch
mu, k hiu l g/mL. Nu t trng ca dung dch d = 1, th n v ny tng ng
ppm. V d nu vit Cpb: 1,2 g/mL th c ngha l trong 1 mun dung dch mu s c
1,2 microgam ca Pb.
B. Theo khi lng mu (khi lng/khi lng)
B1. Microgam/gam: S microgam ca cht phn tch c trong mt gam mu v
k hiu l g/g. V d, nu vit Cpb: 2,5 g/g, th c ngha l c trong 1 gam mu s c
2,5 microgam ca Pb.
Cng hon ton tng t nh trn chng ta cng c cc n v biu din nng
theo khi lng mu l: g/g; mg/kg; g/T. Cc n v ny u l tng ng ppm.
B2. Microgam/ml: S microgam ca cht phn tch c trong mt ml dung dch
mu v k hiu l g/mL. V d, nu vit Cpb = 2,5 g/mL, th c ngha l c trong 1
ml dung dch mu s c 2,5 microgam ca Pb.
C. Cc n v c s ca g
l nanogam (ng), picrgam (pa). Do cng c cc khi nim tng ng l:
103

ng/L, ng/mL, pg/L, pg/mL v ng/g hay pg/g. Cc n v nng sau g l: ng v pg


chng u km nhau 1000 ln v mi tng quan ca chng c ch ra trong bng
6.1, 6.2, v 6.3.
6.1.4 Mu chun trong phn tch quang ph pht x
Trong phn tch quang ph nh lng, dng mt ng chun phn tch ca
mt nguyn t no phc v cho mc ch xc nh n trong mt i tng nht
nh, hay xc nh cc hng s vt l ca phng trnh c bn, ngi ta phi dng
mt dy mu chun (mu u). Thnh phn, tnh cht v nng ca dy mu u ny
s quyt nh chnh xc v ng n ca kt qu phn tch. V vy, m bo cho
php phn tch t kt qu tt th dy mu u ny phi tho mn mt s iu kin sau:

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

Chuyn sang nng th hai


Nng
H s phi nhn vo
g/L
0,01 p

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

Trong phn tch quang ph, gii hn di ca phng php nh lng mt


nguyn t c biu th bng nng Cmin' m ng vi cc nng Cx ca cht phn
tch m nh hn Cmin th vch phn tch ca nguyn t bin mt vo nn ca ph
(khng xut hin), v ta khng quan st c n na. Ngc li, ng vi cc nng
Cx no ln hn Cmin th vch phn tch cn xut hin r rng, php o cho kt qu
tin cy V th khi khng thy vch phn tch ca mt nguyn t trong ph ca mu
phn tch, th c th xy ra theo hai trng hp. C th nng ca nguyn t trong
mu l thc t bng 0, tc l khng c nguyn t . Hoc cng c th l c nguyn t
trong mu phn tch, nhng nng ca n trong mu l nh hn nng gii hn
di ca phng php phn tch (Cmin).
Theo Kaiser gii hn di (cn di) ca phng php phn tch quang ph mt
nguyn t theo 1 vch ph nht nh c tnh theo cng thc sau:
3(n) = 3(Iv - In)

(6.9)

trong : I(v) l cng pht x ca vch phn tch ng vi nng Cmin;


I(n) l cng ca nn; l s dao ng ca gi tr en ca nn.
Trong phng php phn tch quang ph, ngi ta phn bit cn di (gii hn
di) thnh hai khi nim:
- Gii hn pht hin: L nng nh nht ca mt nguyn t trong mu phn
tch cn pht hin c cc vch ph ca n (t nht hai vch nhy) theo cc iu
kin thc nghim chn.
- Gii hn xc nh (nh lng): L nng nh nht ca mt nguyn t
trong mu phn tch cn c th nh lng c nguyn t cho kt qu tin cy,
chc chn v chnh xc (95%). Nu gi gii hn pht hin l Ch v gii hn xc nh l
C th chng ta lun c:
Cd Ch

(6.10)

Khng nhng ch gii hn di, m gii hn trn (cn trn ca mi nguyn t


trong mt php o cng khc nhau. Trong mt nguyn t, nhng vch ph no cng
nhy th nng gii hn trn l nh. Nhng vch khng nhy th nng gii hn
trn l tng i ln (bng 6.4).
Cn trn ca mt phng php phn tch quang ph cng c xc nh bng
thc nghim. l gi tr nng Cmax m t nhng nng Cx ln hn, th mi quan
h gia cng pht x I v nng C ca nguyn t trong mu phn tch khng
tuyn tnh na. Ngha l ng chun biu th mi quan h bt u gc xung trc
honh k t gi tr nng Cmax.
Gii hn xc nh, khong xc nh ca mt phng php phn tch khng nhng
ph thuc vo chnh tng nguyn t, vo tng vch ph c chn o nh lng,
m cn ph thuc vo mt s yu t khc, nh:
107

+ iu kin ha hi, nguyn t ha v kch thch ph ca mu phn tch.


+ Trang thit b thu v ghi ph ca mu.
+ K thut v phng php nh gi nh tnh v nh lng.
Bng 6.4
V d v gii hn xc nh v khong xc nh

Nguyn t
Vch ph(nm)

Gii hn pht hin (%)


nhy

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

pht x ca nguyn t, Ion, phn t ca cc cht mu. Trong cc qu trnh ti in cc


v plasma th s bay hi, nguyn t ha ca mu v s kch thch m hi l qu
trnh chnh. Song i vi mi nguyn t v i vi mi loi mu phn tch th cc qu
trnh ny rt khc nhau. Ngha l c nguyn t d ha hi, c nguyn t kh ha hi,
c nguyn t bay hi nhanh, c nguyn t bay hi chm. V th cn phi nghin cu
mi quan h gia cng pht x ca mt vch ph ca mt nguyn t vi thi gian
bay hi ca n vo vng kch thch ph (plasma). ng cong biu din mi quan h
ny c gi l ng cong bay hi cua nguyn t . Ni cch khc, ng biu din
s bin thin cng pht x ca mt vch ph ca mt nguyn t theo thi gian bay
hi ca mu c gi l ng cong bay hi. V d: Khi nghin cu s bay hi v
pht x ca cc nguyn t trong nn oxit t him ta thu c cc ng biu din nh
trong hnh 6.2. l cc ng cong bay hi ca cc nguyn t Fe, Mn, Mg, Si, Ce...
T nhng ng cong bay hi ny chng ta thy c nguyn t bay hi nhanh, c
nguyn t bay hi chm. Cng chnh t cc ng cong bay hi ny chng ta d dng
chn c thi gian ghi ph ph hp cho qu trnh phn tch nh lng tng nguyn
t. Cng nh trong trng hp no v i vi nguyn t no th cn chn thi gian
khi phng v i vi nhng nguyn t no th phi ghi ph ngay t lc bt u kch
thch ph. Nh v d (hnh 6.2), i vi cc nguyn t Fe, Mn, Mg,... ta phi ghi ph
ngay t u cho ti giy th 150 l , ngc li, vi Ce ta c th b 100 giy u tin
v ghi ph bt u t giy th 100 cho n giy th 250 l thch hp. Chnh nh chn
c thi gian ghi ph ph hp nh th chng ta lm cho ph thu c ca mu
phn tch phc tp v d quan st nh tnh cng nh nh lng. l ngha
thc tin ca vic nghin cu ng cong bay hi ca mi nguyn t trong cc i
tng khc nhau, v trong thc t, khng nhng cc nguyn t khc nhau c ng
cong bay hi khc nhau, m ngay mt nguyn t, khi chng tn ti trong cc loi mu
khc nhau, th cng c ng cong bay hi khc nhau. iu c ngha l dng ca
cong bay hi ca cc nguyn
t ph thuc vo thnh phn
nn ca mu phn tch, trng
thi lin kt vt l, ha hc ca
mu, cu trc tinh th ca hp
cht mu, dng hp cht m
nguyn t tn ti trong
mu,... Nhn chung trong cc
hp cht ha hc, kh nng
bay hi ca chng theo th t
MeX > Me(NO3)2 > MeO >
Mex(PO4)y > MeSO4 > MexSy
> Mecx v.v...
Chnh v th i vi mi loi mu, nht thit phi nghin cu, xy dng ng
109

cong bay hi cho tng nguyn t v ch trn c s mi c th chn c thi gian


ghi ph ph hp.
6.1.7. Kh quyn kim tra
Mi trng kch thch ph c nh hng trc tip n thnh phn ph ca mu
Mi trng kch thch ph pht x phn tch. Nhiu trng hp chnh mi trng kch
thch ph lm cho ph ca mu phc tp thm v kh quan st; c khi khng th thc
hin c php nh tnh cng nh nh lng. V d: Khi kch thch ph trong mi
trng khng kh th ph ca mu lun c cc bng CN. l ph m ca nhm
phn t CN.
Ph ny che lp nhiu
vch phn tch ca nhiu
nguyn t v n th hin rt
r trong vng kh kin.
Nhng chnh trong vng ph
ny li c nhiu vch c
trng nhy ca nhiu
nguyn t. V th ngi ta
thng khng kch thch ph
trong mi trng khng kh,
m trong mi trng kh
quyn kim tra c. l
mi trng kh tr, hay kh
tr c thm oxy.
6.1.7.1 Khi nim v kh quyn kim tra
Vi tn gi l kh quyn tr hay kh quyn kim tra, ngi ta hiu l mt mi
trng kch thch ph pht x ca mu phn tch c th iu khin v kim tra c
Mi trng ny khng cha nit (N2) nh khng kh bnh thng. N c th ch l mt
kh tr thc s nh: He, Ne, hay l hn hp ca mt kh tr vi oxy theo mt t l nht
nh. V d nh hn hp ca (Ar + O2) hay (He + O2) Mi trng cng c th l
CO2 hay hn hp ca (CO2 + O2). Nhng trong tt c cc loi th u vit nht v
c s dng nhiu nht vn l hn hp ca argon v oxy, bi v nu ch dng kh tr
lm mi trng kch thch ph th mu kh bay hi v thi gian kch thch ph qu di.
Nhng nu thm vo kh tr mt lng oxy ph hp th li to iu kin thun li cho
mu bay hi v qu trnh kch thch ph d dng hn. Thnh phn kh ca mi trng
ny cn phi c khng ch v kim tra theo mt nhim v phn tch. Chnh v th
m xut hin khi nim S kch thch ph trong mi trng kh quyn kim tra. Mun
kch thch ph trong mi trng kh quyn tr, ngi ta phi thc hin trong mt
bung kn. Kh tr v oxy dn vo theo mt thnh phn nht nh, ph hp v phi gi
110

khng i sut trong qu trnh kch thch ph. Hn hp kh cn c trn u trc


khi dn vo bung kch thch ph. C nh th mi m bo cho qu trnh kch thch
ph n nh.
5.1.7.2 Vai tr v tc dng ca kh quyn kim tra
Trong phn tch quang ph pht x nguyn t, a mu vo vng phng in
v kch thch ph, ngi ta phi dng in cc than hay graphit tinh khit, v nguyn
liu ny tha mn c nhng yu cu ca nguyn liu lm in cc. Nhng khi dng
nguyn liu ny lm in cc kch thch ph trong mi trng khng kh, tt nhin
s c nhiu ph m trong ph ca mu phn tch. Trong ch yu l ph m ca
nhm phn t CN, MeO. Ph m ny che lp nhiu vch phn tch ca nhiu nguyn
t lm kh khn cho cng vic quan st nh tnh v nh lng; c khi khng th no
thc hin c. V th nht thit phi loi tr ph m CN. loi tr hay hn ch s
xut hin ca ph m ca cc phn t v nhm phn t CN, MeO,.. ngi ta
nghin cu v nu ra nhiu bin php khc nhau. Song chng ta c th khi qut theo
ba hng sau y:
Cch l: Khng dng in cc than hay graphit a mu vo phng in v
kch thch ph, v mu phn tch khng trn vi bt than quang ph, m dng in cc
kim loi. Nhng in cc kim loi thng kh ch to thnh dng ph hp cho qu
trnh kch thch ph. Mt khc kim loi thng nng chy nhit cao. Nn khng
th dng h quang kch thch ph. M h quang li l ngun kch thch tt cho phn
tch mu bt. ng thi khi phn tch cc mu qung, oxit, t ,... nu khng trn
thm bt than quang ph vo mu phn tch lm cht m th vic ha hi nguyn t
ha mu rt kh khn v khng n nh, nhit ca plasma li thp. Cho nn in
cc kim loi vn khng c th thay th cho in cc than c, m ch c th dng
c trong mt vi trng hp phn tch dung dch. V th bin php ny khng thch
hp cho tt c v t c s dng.
Cch 2: Theo cch ny, ngi ta vn dng in cc than, nhng thm vo mu
phn tch nhng cht ph gia thch hp hn ch s xut hin ca ph m v ph
bng (CN, MeO), v d thm mui halogen ca kim loi kim CsCL, CsF, LiF,...
Nhng bin php ny cng khng trit , v n ch hn ch bt, ch khng loi tr
hon ton ph m ca CN, MeO. Mt khc, mun loi tr c mt phn ph m,
chng ta phi thm mt lng ln cht ph gia. Nh th trong nhiu trng hp li
lm gim cng vch ph. iu ny khng ph hp vi yu cu ca php phn tch
lng vt, ngha l trong nhiu trng hp khng dng c bin php ny.
Cch 3: Cch th ba l kch thch ph trong mi trng kh quyn kim tra khng
c nit. Nh th s c kh nng loi tr c hon ton ph m ca nhm phn t
CN m vn dng c in cc than v bt than quang ph lm cht m. y l
phng php tt nht. N chng nhng loi tr c cc bng CN m cn c nhiu tc
dng tch cc khc. Ngy nay phng php ny c s dng rt ph bin v
111

khng c iu g phi nghi ng na v tc dng c li ca n. S d nh vy l v vic


kch thch ph trong mi trng kh quyn tr ny c nhng u vit nh sau:
- Ph ca mu phn tch l tuyt i sch, khng c ph m ca cc phn t v
nhm phn t CN, m thun khit l ph vch ca nguyn t v Ion. Do vic quan
st nh tnh v nh lng khng kh khn, c bit l trong vng ph kh kin. V
d: Khi xc nh Gd-4184,26 th hon ton b bng CN che lp. Nhng nu kch
thch ph trong mi trng kh quyn kim tra ca hn hp Al (80%) v oxy (20%) th
vch ph ca Gd l mt vch nhy, r nt v rt thch hp cho phn tch Gd trong
nn t him.
- u im th hai l khi kch thch ph trong mi trng kh quyn kim tra,
trong nhiu trng hp cng ca vch ph c tng ln r rng. y chnh l
mt bin php tng nhy ca phng php phn tch. Vic xc nh Sm, Eu l
mt v d v ngha ny (bng 6.5).

Bng 6.5
So snh kt qu trong hai mi trng kch thch ph
Nguyn t

Mi trng khng kh

Mi trng kh quyn kim tra

Cng

nhy

Cng

nhy

Eu 4435,60

67

0,0004%

120

0,0001%

Sm 4424,34

65

0,0008%

104

0,0003%

Khi kch thch ph trong mi trng kh tr ph ca mu thng c nn sng,


nhiu vch yu li bin mt, khng xut hin. Do ph thu c ca mu thng t
vch hn so vi trng hp kch thch trong khng kh.
Trong nhiu trng hp vic kch thch ph ca mu phn tch trong mi trng
kh tr li to ra s bay hi chn lc thun li i vi nguyn t phn tch. iu ny
rt c ngha khi phn tch nhng mu c thnh phn phc tp, cng nh thch hp.
Mt u im na l vic kch thch ph trong mi trng kh quyn kim tra
trong nhiu trng hp cn c kh nng loi tr c nh hng ca nguyn t c s
ca mu (matrix effect). ng thi theo nhng kt qu nghin cu ca V. F. Fassel th
vic kch thch ph trong mi trng kh quyn tr cn c tc dng hn ch c c
hin tng t o ca nhiu vch ph nhy. V th vng tuyn tnh rng hn. Tt
nhin bn cnh nhng u im th vic kch thch ph trong mi trng kh kim tra
cng c nhng kh khn nht nh, nh cn c kh tr, oxy tinh khit cao (>99,99%),
cn c nhng trang b ph tr. V th, ngy nay trong php do ph pht x hin i
ICP-AES, ph pht x ca mu lun c kch thch trong mi trng kh tr argon.
112

6.1.8 Cht m v cht ph gia trong phn tch ph pht x


Trong phn tch quang ph pht x, mu th nghim d dng rn, dung dch hay
bt cng u c lm bay hi trong mt ngun sng, nh ngn la n kh, h quang
in, tia in, ICP,... ngha l mu phn tch c chuyn thnh trng thi hi di tc
dng ca nng lng nhit. Trong cc nguyn t, Ion, v c phn t trng thi hi
cng c th c kch thch n pht sng v cng ca vch ph pht x do cc
nguyn t pht ra c dng xc nh nng ca n trong mu phn tch, v
cng vch pht x ca mt nguyn t ph thuc vo nng ca n trong mu
phn tch.
Nhng trong nhiu trng hp cng vch ph ca mt nguyn t trong mu
phn tch khng nhng ch ph thuc vo nng ca n, m cn b nh hng bi
nng ca cc hp phn khc c trong mu phn tch. Nht l khi trong h c cha
nhiu nguyn t v thnh phn phc tp m nguyn t cn xc nh li l nguyn t
vt. l yu t nh hng tng h gia cc hp phn trong mu phn tch. c bit
l khi thm vo mu phn tch mt s hp cht ph no th ngi ta c th lm thay
i cng vch ph ca cc nguyn t. Cc cht thm vo c gi l cht ph
gia. Nhng cht khi thm vo mu lm thay i thnh phn ca mu, v qua
lm nh hng n thnh phn ca ph v cng ca vch ph. Cc cht ph gia c
th lm gim hay cng c th lm tng cng vch ph ca mt nguyn t. S d
nh vy l v s thay i thnh phn ha hc ca mu thng nh hng n mi qu
trnh trong khi kch thch ph, nh:
- S thay i nhit plasma,
- Thay i nng in t (Pe) trong plasma,
- S khuch tn v chuyn vn ca cc phn t,
- Cc phn ng ha hc in cc v plasma,
- Qu trnh ha hi ca cht mu,
- S bay hi v nguyn t ha cht mu,
- Thi gian tn ti ca cc phn t trong plasma,
- S Ion ha, s phn li ca cc cht,
- S kch thch ph ca cc phn t trong plasma.
Trong tt c cc thay i th s thay i p lc in t (Pe) v nhit ca
plasma l yu t chnh, c tnh cht quyt nh. Cn cc thay i khc ch l hu qu
ca hai thay i ny.
Cht ph gia c dng trong phn tch quang ph c rt nhiu loi khc nhau,
nhng c chia thnh mt s loi (thnh nhm) theo c trng ring v tnh cht
nhit ng ha hc ca chng trong plasma kch thch ph, nh:
113

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

3. Cht tr lc cho s t chy, ha hi mu. Thng thng khi phn tch cc


mu bt, c bit l cc mu khng dn in, nh cc mu qung, t , khong st,
thng c hin tng kh t chy mu, kh ha hi v t bay hi thng khng n
nh. Khi cng vic phn tch gp kh khn v kt qu thu c khng lp li tt
Lc ny ngi ta thng thm vo mu nhng cht lm cho s chy, s ha hi v
nguyn t ha ca mu c d dng hn. Nhng cht nh th c gi l cht tr lc
cho s bay hi ca mu. Cht in hnh cho loi ny li l bt than quang ph hay bt
graphit quang ph. Sau l bt lu hunh, bt oxit nhm. Nhng bt lu hunh v
bt xit nhm khng th dng ring mt mnh, m phi lun lun dng cng vi bt
than. V th ngi ta gi bt than quang ph l mt cht ph gia vn nng.
4. Cht dn in. Khi phn tch cc mu khng dn in, vn n nh dng
in qua ct kh ca plasma h quang hay tia la in l mt yu t rt quan trng. V
nu khng, s phng in khng n nh v iu ny s a n nhng kt qu phn
tch khng tt. Nguyn nhn chnh l do trong nhng trng hp trong plasma
khng c nng ln v n nh ca cc phn t mang in tch dng v nm ( Ion
dng v in t). V th ngi ta thng thm vo mu phn tch nhng hp cht d
bay hi ca cc kim loi d b Ion ha (c th Ion ha thp). Nhng cht c gi
l nhng cht dn in. i din cho nhm cht ny l cc mui halogen ca cc kim
loi kim nh CsF, CsCl, LiF,... Nh c nhng cht ny dng in qua ct kh c n
nh, v qua cng lm cho s phng in, s kch thch ph trong plasma cng
c n nh. S d nh vy l v nhng cht ny cung cp cho plasma mt nng
ln ca Ion dng v in t, m yu t khc (s b sung khc) v in tch nm v
dng l khng ng k, ngha l duy tr dng in n nh qua ct kh ca plasma.
5. Cht pha long. L nhng cht khi thm vo mu phn tch c tc dng lm
long nng ca cc hp phn trong mu, nhng li khng nh hng n cng
vch ph ca nguyn t phn tch, ngc li c khi cn lm tng cng vch ph
phn tch. Thc t chng minh rng, trong hu ht cc trng hp phn tch cc mu
qung, khi pha long mu bng bt than quang ph, mui halogen kim loi kim, th
cng vch ph ca cc nguyn t cn xc nh ch c tng hoc khng i. Ngoi
bt than quang ph th mt s mui cacbonat, halogen ca kim loi kim v kim th,
mt s mui sunfat kim loi kim th, mt vi oxit, v d nh Li2COa, Na2CO3, LiF,
LiCl, BaCO3, CaCO3, CaSO4, SrSO4, SiO2, cng thng c dng cng vi bt
than quang ph theo nhng t l thch hp. Tc dng ca cht pha long l lm cho ph
ca mu n gin hn v d quan st. Trong mt s trng hp cht ny c tc dng
kh bt ph ca nguyn t c s, lm tng cng vch ph ca nguyn t phn tch
(bng 6).
6. Cht chy. L nhng cht d nng chy, c tc dng lm cho mu d nng
chy v d ha hi. V d nh LiBO2, cc mui hydropyrosunphat ca kim loi K v
Na hay Li. i vi mt s mu c thnh phn phc tp, nh cc mu qung a kim
115

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

Mu + cht pha long t l: (gng)

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

7. Cht kh nn. Trong mt s trng hp phn tch quang ph pht x, nh cc


mu qung, th ph thu c thng c nn ph lin tc rt en, nht l khi kch thch
ph bng h quang. C khi nn ny che lp mt c nhng vch phn tch c cng
nh. Trong nhng trng hp nh vy ngi ta phi thm vo mu nhng cht c tc
dng lm gim bt nn ca ph lin tc. Nhng cht c tc dng nh th c gi l
cht kh nn. Cht thuc loi ny thng l mt s mui sunphat ca kim loi kim
th v mt vi oxit: CaSO4, BaSO4, SrSO4, SiO2, Al2O3. Nhng cht ny c th dng
ring bit hay ng hn hp ca hai cht vi nhau, nhng chng cng phi c ng
cng vi bt than quang ph. V d: Khi xc nh V v Ni trong du m, ngi ta
thng dng SiO2 hay SrSO4 thm vo mu khi tro ha mu du. Nhng cht ny
va c tc dng l cht gp, cht bo v hay l n nh qu trnh tro ha trnh mt
mt, mt khc li chnh l cht kh bt nn khi ghi ph ca mu tro du .
Trn y l mt s tc dng quan trng ca cht ph gia, nhng s trnh by v
phn loi nh th ch l tng i, v trong thc t mt cht ph gia c th biu l
ng thi nhiu chc nng v tc dng cng mt lc. Trong c chc nng chnh, c
chc nng ph. V d nh bt than quang ph va l cht m, va l cht mang.
Nhng tc dng m ca n l chnh. V th ngi ta thng gi bt than quang ph l
cht m quang ph.
Cht ph gia c nhiu tc dng khc nhau, nn khi s dng n ngi ta thng
xut pht t nhng mc ch khc nhau. Nhng c th khi qut theo hai hng chnh:
- Hng I. S dng cht ph gia nhm mc ch gy ra s bay hi chn lc ca
mt s hp phn trong mu m bo cho php phn tch thc hin d dng v t
kt qu tt. V d: Vic thm cc cht ph gia l cc mui halogen ca cc kim loi
116

kim thng gy ra s bay hi chn lc ca nhng nguyn t vt trong mu c kh


nng to vi cc halogen nhng hp cht d bay hi. Trong nhng trng hp ny
thng ko theo s tng cng ca vch ph. l iu kin thun li trong php
phn tch nguyn t vi lng. cng l u im ca cht ph gia.
- Hng II. Ngi ta s dng cht ph gia nhm mc ch lm thay i cc qu
trnh chnh trong s phng in v kch thch ph ca mu. V d: S ha hi, s kch
thch ph ca mt hp phn trong plasma vi mc ch c th lm tng hay gim
mnh cng vch ph ca mt nguyn t. Nhng kt qu nghin cu n nay
chng minh rng, nhng yu t gy ra cc thay i trn phi l cc phn ng ha hc
trong in cc v trong s bay hi ca mu khi c mt ca cht ph gia.
Trong cc cht ph gia th cc halogen ca kim loi kim v mt s kim loi
kim th c ngha ln i vi mc ch ny, bi v s c mt mt lng ln v
ph hp ca cht ph gia nh th trong mu phn tch lm thay i tt c cc qu
trnh trong in cc v trong s kch thch ph ca mu.
Trong nhit v p lc in t trong plasma l cc yu t chnh, quyt nh
cc yu t khc. Nhng thay i cui cng dn n s thay i cng ca vch
ph.
Tc dng ny c th l dng v cng c th l nm, ty thuc vo tng trng
hp c th. Tt nhin trong thc t phn tch ngi ta lun lun chn tc dng no c
li cho cng vic phn tch, nh lm tng cng vch ph ca nguyn t phn tch
v lm gim cng vch ph ca nguyn t nn.
V mt ha hc, khi thm cht ph gia vo mu phn tch tt nhin c nhiu phn
ng ha hc khc nhau xy ra, c phn ng chnh, c phn ng ph. Nhng c th tm
chia thnh my loi phn ng sau:
- Phn ng oxy ha;
- Phn ng sunfua ha;
- Phn ng cacbua ha;
- Phn ng halogen ha;
- Phn ng phn li v phn hy ca cc phn t,...
Trong cc loi phn ng th phn ng halogen ha l quan trng nht v c
ngha thc t nht, v nh phn ng ny cc hp phn ca mu d ha hi, c bit l
cc hp phn lng vt, qua lm tng cng vch ph ca nguyn t phn tch
v lm gim cng vch ph ca nguyn t c s v nn.
Cht ph gia to ra phn ng ny l cc halogen ca kim loi kim v mt s kim
loi kim th.
Ngc li vi phn ng halogen ha, phn ng sunfua ha v carbua ha thng
117

to ra cc hp cht bn nhit, kh bay hi, kh nguyn t ha, ngha l gim qu trnh


bay hi v nguyn t ha ca cc hp phn v cui cng lm gim cng vch ph.
V th phn ng ny c s dng kh bt ph ca nguyn t c s.
Xut pht t nhng nghin cu nu, ngy nay trong phn tch quang ph pht
x ngi ta thng s dng cht ph gia khc nhau thm vo mu phn tch vi nhng
mc ch sau:
1. To iu kin lm cho qu trnh ho hi, nguyn t ha mu, kch thch ph n
nh, m bo cho php phn tch t chnh xc v lp li cao, ngha l thu
c kt qu tt.
2. Tng cng vch ph ca nguyn t nghin cu, ngha l tng nhy ca
phng php phn tch c th xc nh c nhng nng nh m khng phi
lm giu mu phn tch (bng 6.7 v hnh 6.4).
3. Loi tr bt nhng nh hng ca cc hp phn cn tr, nh ph nn lin tc,
nh hng ca nguyn t c s, nguyn t th ba.
4. Pha long mu phn tch loi b nh hng ca hin tng t o, hoc lm
n gin ph ca mu phn tch d quan st nh tnh v nh lng.
5. iu chnh s bay hi ca mt s hp phn trong mu theo nhng xu hng
c li cho qu trnh phn tch mt hay vi nguyn t.
Bng 6.7
nh hng ca cht ph gia n cng vch ph

Nguyn t

Cng vch ph trong iu kin


Khng ph gia

C cht ph gia thm vo:


CsCl (2%)

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

6.2 Phn tch quang ph pht x bn nh lng


Phng php phn tch quang ph bn nh lng l php phn tch nh gi gn
ng hm lng (nng ) ca mt nguyn t trong mu phn tch da theo s quan
st v so snh en S hay cng IM ca vch ph phn tch.
Php phn tch quang ph bn nh lng c nhiu phng php khc nhau.
Song trong cun sch ny ch nu hai phng php chnh cn ang c s dng
nhiu.
6.2.1 Phng php so snh
Nguyn tc ca phng php ny l mun phn tch bn nh lng mt nguyn
t X no , trc ht phi chun b mt dy mu u ca n c nng t nh n
ln.
V d: Dy mu u (mu chun) c nng ca nguyn t phn tch X l Cl,
C2, Ca, C4, C5, C8.
ng thi cng chun b mu phn tch Cx trong cng iu kin. Sau tin
hnh ghi ph ca tt c dy mu cng mu phn tch trong mt iu kin ph hp
c chn cho nguyn t X.
Nhng vic quan st v nh gi d dng chng ta nn b tr ph theo th t:
Cl, Cx, C2, Cx, C3, Cx, C4, Cx, C5,
Sau khi thu c knh nh ta chn mt vch phn tch ca nguyn t X v so
snh cng ca chng trn tt c cc nng xem nng Cx nm trong khong
119

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

S vch xut hin tng ng (Ao)


2614,20 ; 2802,00 ; 2933,06

C2 0,005

Ba vch trn r, c thm vch 2663,17 (m)

C3 0,01

Bn vch trn r, c thm vch 2873,30

C4 0,05

Nm vch trn r nt.

C5 0,1

Nm vch trn r nt v thm vch 2474,38

C6 0,5

Su vch trn r, thm 2393,61 (cn m)

C7 1,0

Ba vch u to, nhe, thm 2401,95; 2443,86

C8 1,5

Ba vch u nhe, cc vch sau m.

..

Cx

Xut hin: 2614,20; 2802,00; 2933,06;2633,17.

Phng php ny n gin, d thc hin v c ng dng rt rng ri, c bit


l trong ngnh a cht, v ta ch cn lp bng ph cc vch ph xut hin ln u tin,
sau c th s dng bng ny phn tch nguyn trong cc ln sau, m khng
phi ghi ph li ca mu u. Trong hai phng php bn nh lng trnh by, th
phng php hin vch c s dng rng ri, nht l trong nghnh a cht, v
phng php d thc hin v c nhiu u im.
6.3 Phn tch quang ph pht x dinh lng
6.3.1 Phng php ng chun
Phng php ng chun da theo phng trnh c bn ca php o ph pht
x nh ch ra trong chng II l:
I = a.Cb (a)
hay

S = . b.log C + k (b)

Trong iu kin b: 1, th y l phng trnh ca ng thng c dng: y= a.x v


y: a.x + b.
Phng trnh (a) l i vi nhng my o c trc tip cng pht x IM
121

ca vch ph, cn phng trnh (b) l trng hp o en S ca vch ph trn knh


nh.
Nh vy, mun xc nh nng Cx ca mt nguyn t X trong mt mu no ,
trc ht chng ta phi chun b mt dy mu u c cha nguyn t X vi nng
C1, C2, Ca, C4,V Cx trong cng mt iu kin nh cc mu phn tch. Song dng
1 ng chun, trong thc nghim, t nht cn ba mu u.
V th phng php ny gi l phng php ba mu u, tc l s mu u cn
thit dng mt ng chun. Nhng trong thc t, ngi ta hay dng 5 mu u,
cng v th phng php ny c gi mt tn chung l phng php ng chun.
Sau khi chun b xong cc mu u v mu phn tch, tin hnh ha hi, nguyn
t ha, kch thch ph, v ghi ph ca cc mu theo nhng iu kin ph hp
c chn (theo mt quy trnh phn tch).
Tip chn mt cp vch phn tch o en S hay chn vch phn tch
o cng I theo mt trong hai phng trnh c bn trn ty thuc vo h thng
trang b ca phng th nghim. Tnh cc gi tr trung bnh ca cng vch ph I
hay en S tng ng vi tng nng . Nh th ta c:
Bng 6.9. Dy chun ca phng php ng chun
Cht

Cht phn tch X

Dy chun
0

Co

C1

C2

C3

C4

C5

Cc cht khc (nn, mi trng)

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

6.3.2 Phng php th chun khng i


Nguyn tc ca phng php ny l mun xc nh mt nguyn t no , trc
ht ngi ta cng phi dng mt ng chun nh trong phng php ba mu u.
ng chun ny c gi l ng chun c nh (ng chun khng i).
Nhng c khc l ph ca cc mu u dng ng chun c ghi trn mt knh
nh ring, gi l knh nh c s; cn ph ca cc mu phn tch li c ghi trn mt
knh nh khc, knh nh th hai - knh nh phn tch. Nh vy, mun xc nh c
nng Cx cha bit, ta phi chuyn cc gi tr Sxl tng ng v cc gi tr Sxo
ca knh nh c s th mi chiu ln th chun xc nh Cx hay loa Cx c.
gii quyt vn ny ngi ta c hai cch khc nhau:
- Cch th nht: Xc nh h s chuyn k theo cng thc:
Sxo = k.Sxl

(6.13)

y k c gi l h s chuyn ca gi tr en ca vch ph gia hai knh


nh (knh nh c s v knh nh phn tch) trong cng mt iu kin th nghim.
Mun th trn knh nh phn tch ta ghi li ph ca mt mu u, v d nng
Ca. Nh th trn knh nh c s ta c Sxo-3, v trn knh nh phn tch ta cng c
Sxl-3 v h s chuyn k s c tnh theo cng thc:
S xo3
=k
S xl 3

(6.14)

Sau khi c h s k ta em n nhn vi cc gi tr en Sxl trn knh nh phn


tch ta s thu c cc gi tr en tng ng trn knh nh c s dng ng
chun. By gi ch chiu cc gi tr vo ng chun c nh l tm c loa Cx'
Ri t suy ra Cx.
- Cch th hai: T thc t phn tch
khi nghin cu cc ng chun ngi ta
thy rng, trong cng mt iu kin th
nghim, i vi mt nguyn t khi o trn
mt cp vch phn tch, th ng chun
dng c t dy ph ca cc mu u ghi
trn cc ln khc nhau ca mt loi knh
nh, u l nhng ng thng song song
vi nhau hoc trng nhau (hnh 6.7), ngha
l cc ng c cng h s gc.
Phng php th khng i rt ph
hp i vi php phn tch hng lot mu t
ngy ny qua ngy khc, v trong mi ngy
124

phn tch chng ta khng phi ghi ph li


ca ton b dy mu u, nn tit kim c
thi gian, in cc, mu chun v knh nh,
ngha l c tnh kinh t hn phng php
ng chun. Tuy th, nhng phng php
ng chun (Ba mu u) hay phng
php ng chun c nh u ging nhau
ch u phi chun b mt dy mu u c
iu kin ca mu u trong php phn
tch quang ph nh lng. iu ny nhiu
khi khng thc hin c. c bit i vi
nhng trng hp mu phn tch c thnh
phn phc tp m chng ta cha th bit
c chnh xc.
V th cng khng th chun b c mt dy mu u c thnh phn ha hc v
vt l ng nht vi mu phn tch. l thc t v trong nhng trng hp th nh
hng nguyn t c s v nguyn t th ba n kt qu phn tch l rt r. iu ny
th hin r khi xc nh cc nguyn t vi lng. Lc ny chng ta phi hoc l thay i
nn ca mu (modify matrix) nu cch ny c hiu qu, hay l dng phng php
thm tiu chun.
6.3.3 Phng php thm tiu chun
Nguyn tc ca phng php thm l mun xc nh mt nguyn t phn tch X
no trong mu phn tch, ngi ta dng ngay mu phn tch lm nn chun b
mt dy mu u bng cch ly mt lng chnh xc mu phn tch v thm vo
nhng lng ph hp v theo tng bc ca nguyn t X. Nu gi mu phn tch c
nng l Cx th dy mu chun s l (bng 6.10):
Bng 6.10
Dy chun ca phng php thm

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

Trong cc gi tr C1, C2, C3, C4 l nng dc thm vo ca nguyn t


phn tch X di dng mt hp cht c dng lin kt ph hp nh trong mu phn tch
v theo cp s cng.
Sau cng tin hnh ghi ph ca dy mu theo nhng iu kin ph hp,
chn mt cp vch o en S hay gi tr cng Ic tng ng. Nh vy ng vi
mi nng ta cng s c c nh trong bng trn.
n y chng ta dng phng php ngoi suy xc nh nng Cx cha bit
trong mu phn tch. Theo phng php ny, xc nh Cx chng ta phi dng ng
chun theo h to I - C. Nh vy, nu cng vch ph I c o trc tip th
cng vic s n gin, ta dng ngay c ng chun I - C t nhng gi tr I
o c. Nhng nu o theo cc gi tr S th chng ta tnh chuyn cc gi tr S
thnh gi tr I tng ng theo cng thc:
.log.I = S

(6.15)

Ri sau cng dng ng chun nh trn I - C. ng chun va dng


c l mt ng thng. N ct trc tung ti im c ta (Ix, Cx). By gi mun
xc nh Cx ta ch vic ko di ng chun pha nng nh, ng chun ny
s ct trc honh ti mt im Cx.. chnh l gi tr nng Cx cn tm (hnh 6.9).
Ta cng c th xc nh Cx theo cch khc, ngha l t gc to chng ta k
ng song song vi ng chun v t gi tr IX chng ta k ng song song vi
trc honh; hai ng ny ct nhau ti im B. T B k ng vung gc vi trc
honh, n ct trc honh ti Cx. chnh l gi tr nng Cx cn tm.

- Xc nh y: Nguyn tc da theo hai mu chun bit chnh xc nng v


126

d: C1,C2 (C2 > C1).


Nh vy ta c:

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)

Do em (a) chia cho (b) chng ta c:


Cx = (Ix/Io).C1

(6.17)

Nh vy khi o c gi tr Ix v I1 ta c t s ca chng, v ch vic nhn n vi


gi tr Cl l chng ta c gi tr nng Cx phi tm theo biu thc (6.17).
Nhng cn phi nh rng, nu o S trc ht phi tnh chuyn cc gi tr S sang
cc gi tr cng I tng ng ri mi ng dng c phng php ny, gi tr nng
chun Cl v c nng cht phn tch phi nm trong vng tuyn tnh ca php o
xc nh cht m chng ta bit r trc.
b) Khi khng c mu chun
Trong trng hp ny, chng ta cng khng cn pha mt dy chun dng
th chun, m dng ngay 1 mu phn tch lm nn chun b mt mu phn tch v 1
mu thm chun theo phng php thm v tnh ngay gi tr Cx nh mt lng chun
C1 ca cht phn tch c thm vo. Ngha l chng ta c:
Vi mu phn tch khng thm chun:

Ix = a.Cx

(a)

Vi mu u phn tch c thm chun:

Itch = a(Cx + C1)

(b)

Do em (a) chia cho (b) chng ta c:


Cng = [Ix/(Itch Ix)]C1

(6.18)
127

Nh vy khi o c gi tr Ix v Itch ta c tnh c nng Cx phi tm theo


biu thc (6.18).
Nhng cn phi nh rng, nu o S trc ht phi tnh chuyn cc gi tr S sang
cc gi tr cng I tng ng ri mi ng dng c phng php ny v gi tr
nng chun Cl v c nng cht phn tch phi nm trong vng tuyn tnh ca
php o xc nh cht chng ta bit.
Trn y l cc phng php nh lng ch yu hay c s dng. Tt nhin
mi phng php u c nhng u im v nhc im nht nh ca n, v ngi
dng tu iu kin m p dng cho thch hp.
6.4 Cc phng php xc nh gin tip bng AES
6.4.1 Nguyn tc
xc nh gin tip cc cht khng c ph pht x nguyn t theo php o ph
pht x nguyn t, ngi ta thng da theo mt trong hai nguyn tc sau y v ng
vi mi loi nguyn tc ngi ta c mt kiu xc nh ring nht nh theo bn cht
ca cht phn tch.
- Cch 1: Cho cht cn phn tch X (cn xc nh) tc dng vi mt thuc th l
mui ca mt kim loi c ph pht x nguyn t trong nhng iu kin thch hp v
phn ng ny c tnh cht nh lng hon ton. V d: xc nh Ion Cl, ngi ta
cho mu c Ion Cl tc dng vi dung dch AgNO3 trong mi trng axit HNO3 2%,
sinh ra kt ta AgCl theo phn ng:
C + Ag+ = AgCl
Sau lc hay li tnm ly kt ta AgCl, ho tan n trong dung dch NH4OH 5%
v xc nh hm ljng Ag trong dung dch ny, ri suy ra nng ln C , v theo
phn ng trn, 1 Ion Cl s tng tc vi 1 Ion Ag+.
- Cch 2: Da theo hiu ng ca cht cn xc nh trong mt vng nng nht
nh, n lm gim hay lm tng cng vch ph pht x ca mt kim loi mt cch
tuyn tnh. V d: xc nh Anion F1- ta o ph pht x ca nguyn t Mg nng
2 ppm, v trong vng nng Anion F1- t 2 - 20 ppm, th cng vch ph pht x
Mg - 285,20 nm s b gim mt cch tuyn tnh theo s tng nng F.
6.4.2 Cc phng php phn tch gin tip
6.4.2.1 Theo nguyn tc th nht
1. Theo phn ng to kt ta khng tan
Theo loi phn ng ny, ngi ta c th thc hin cc phn ng ha hc c tnh
cht nh lng bit, nh:
- To kt ta l mui khng tan
128

Cc phn ng kt ta nh lng trong ha hc th c rt nhiu, v d nh phn


ng to kt ta: AgCl, AgBr, AgI, PbSO4, BaSO4, v.v...Theo cch ny, ngi ta ly
mt lng nht nh cht mu (theo Vml hay a mg) cho tc dng vi mt thuc th
thch hp v d, trong iu kin nht nh phn ng kt ta xy ra hon ton.
Sau li tnm hay lc tch kt ta khi dung dch, ri thc hin xc nh kim loi theo
mt trong hai cch sau:
+ Ho tan kt ta v xc nh kim loi trong kt ta, ri suy ra hm lng cht
phn tch X.
+ Xc nh lng kim loi thuc th d sau khi kt ta ht cht phn tch cn li.
T suy ra lng kim loi phn ng vi cht phn tch X, v tnh hm lng
cht phn tch X.
Cch ny thng c s dng xc nh cc mui: Halgen (F, Cl, Br, I),
sunphat (SO42-), photphat (PO43-), oxalat (C2O42-), v.v... Sau y l cc phn ng .
C + Ag+ AgCl xc nh Anion Cl
Br + Ag+ AgBr xc nh Anion Br
I + Ag+ AgI xc nh Anion r
C2O42- + Ca2+ CaC2O4 xc nh Anion C2O42 PO4 + Ca2+ Ca3(PO4)2 xc nh Anion PO4
SO42- + Ba2+ BaSO4 xc nh Anion SO42 SO42- + Pb2+ PbSO4 xc nh Anion SO42 PO43- + Mg2+ + NH4+ MgNH4PO4 xc nh Anion PO4
V d: xc nh hm lng Anion Cl trong nc, ngi ta ly 100 ml mu
nc, thm 5 ml HNO3 65%, thm 2 ml dung dch AgNO3 5 mg/mL Ag (lng Ag
thm vo l 10 mg), lc u, sinh ra kt ta AgCl theo phn ng:
C + Ag+ AgCl
Lm mui kt ta, sau lc hay li tnm ly kt ta AgCl, ra sch kt ta bng
10ml HNO3 1%, thu nc lc v nc ra nh mc thnh 100 ml bng dung dch
HNO3 1%, v xc nh lng Ag d trong dung dch ny bng php o ph pht x
ca nguyn t Ag. Nh th ta tnh c lng Ag, v suy ra lng Ag phn ng vi
mun Cl, sau tnh hm lng mun Cr trong mu nc, v theo phn ng trn, 1
Ion Cl s tng tc vi 1 Ion Ag+.
- To kt ta l sunphua khng tan
Mt s cht, v d cc hp cht hu c, dc phm thuc h thioo (c cha Ion
S , trong nhng iu kin thch hp c th tc dng vi mt s Ion kim loi to ra hp
2-

129

cht sunphua khng tan, v cng c s dng xc nh cc cht hu c .


V d: xc nh vitamin B1 (trong 1 phn t B1c 1 Ion S2-), ngi ta ly a mg
mu c B1 cho tc dng vi b mg NaPbO2 trong mi trng KOH nng chy trong ng
nghim, phn ng sinh ra PbS rt nh lng l c 1 phn t B1, th bao gi cng to
ra 1 phn t PbS.
1 phn t vitamin Bl + NaPbO2 PbS
Sau ho tan hn hp phn ng trong 20ml dung dch NH4C11%, lc v ra kt
ta PbS, ho tan kt ta PbS trong 15 ml HNO3 1/1, nh mc thnh 25 mg v xc nh
Pb trong dung dch ny. Sau suy ra hm lng vitamin Bi trong mu a mg. theo
phn ng trn.
Phn ng ny trc y c dng xc nh vitamin B1, cng nh hm
lng penicillin trong thuc, hay trong cc sn phm thc phm, bng phng php
khi lng, nn ch xc nh c hm lng ln, v tin hnh rt lu cc thao tc kt
ta, sy kh, cn kt qu. Hin nay nh php o ph AES hay AAS, xc nh c c
hm lng nh, m li nhanh.
2. Theo phn ng kh mui kim loi
y chnh l phn ng trng gng, phn ng kh Ion Ag v Ag+ kim loi, dng
thuc th Tulen, l phn ng xc nh cc cht andehit. V th phn ng ny ch
yu c dng xc nh hm lng cc cht c chc andehit trong phn t. Trong
phn ng ny, c 1 nhm chc andehit - CHO trong phn t cht, th lun gii phng
ra 1 nguyn t Ag.
R (CHO)n + n(Ag+) nAgo
V th cch ny hin nay c s dng xc nh cc hp cht hu c c cha
andehit dng R-(CHO)n, ch yu l theo phn ng trng gng.
V d: xc nh hm lng andehit fomic, ta ly V ml mu cho tc dng vi
V ml thuc th Tulen, khi un nng nh, qu trnh kh Ion Ag+ xy ra theo phn ng:
HCHO + Ag+ A go
Nh vy, kim loi Ag c gii phng v bm vo thnh ng nghim. Sau
loi b dung dch, ho tan kt ta Ag kim loi bng 10 ml axit HNO3 1/1 nng, un
nh cho tan ht, nh mc thnh 25 ml, v xc nh Ag trong dung dch ny. Theo kt
qu nng Ag, ta suy ra hm lng andehit trong V ml mu theo phn ng trn.
3. Theo phn ng ho tan mt kim loi
Mt s cht, m ch yu y l cc axit hu c c kh nng ho tan cc kim
loi hot ng nh Cd, hay Zn rt nh lng, nn cng c s dng xc nh n,
theo phn ng to ra mui tan nh sau:
2R-(COOH) + Zn (R-COO)2Zn
130

Sau li tnm ly dung dch mui ny v xc nh nng Zn bng php o ph


pht x ca Zn, ri suy ra nng (hm lng) axit R-COOH tc dng vi Zn kim
loi sinh ra dung dch mui Zn(R-COO)2.
4. Theo phn ng to hp cht phc bn chit c
Cch ny dng xc nh mt s Anion, hay cht hu c, ngha l cc Anion
no c th tc dng c vi mt Ion kim loi to ra c mt hp cht phc bn
trong mt iu kin nht nh v chit ra c khi dung dch mu, th u c th s
dng xc nh cc Anion .
V d: Xc nh Anion CNS-1 qua phn ng ca Anion ny vi dung dch mui
FeCla trong mi trng pH=1, theo phn ng:
Fe3+ + CNS Fe(CNS)
Sau chit phc Fe(CNS) vo dung mi etyl e v xc nh Fe trong dch chit
ny (c th gii chit phc vo dung dch HCI 2M, v xc nh Fe trong dung dch gii
chit ny). Sau ta cng tnh c nng ln CNS trong mu phn tch.
5. Theo phn ng to hp cht d a
Cch ny thng c dng xc nh P, Si, qua thuc th molipdic trong mi
trng axit nc c 6M, sinh ra hp cht d a ca P vi Mo, m chng ta dng
trong phn tch ha hc xc nh P trong t trng bng phng php trung ha.
Cch lm cng hon ton tng t nh th, 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 pht x ca Mo, sau suy ra hm lng P trong mu
phn tch, theo phn ng sau.
PO4 + NH4+ + MoO42- + HNO3 (NH4)3[P(Mo3O10)4]
Hp cht d a ca P
6. Phn ng kh hp cht c nhm Nitro (-NO2)
Mt s hp cht Nitro trong mi trng pH thch hp c th b kh v amin (RNO2 R-NH2) bng kim loi hot ng, v d nh Cd, Zn, rt nh lng, v phn
ng ny c s dng xc nh mt s hp cht hu c c nhm nitro, v d nh
xc nh Chloramphenicol, qua chun lng Ion Cd(II) sinh ra trong phn ng hay
o ph pht x nguyn t (AES hay ICP-OES) ca dung dch Ion kim loi Cd(II). V
d trong mi trng axit long (HCl 0,05M), bt kim loi xp Cd kh nhm -NO2 v
NH2 hon ton nh lng theo phn ng sau.
3Cd + R-NO2 + 6HCl 3CdCl2 + H2O + R-NH2
Chloramphenicol
Nh vy sau khi phn ng kt thc, ly tnm ly dung dch Anion CdCl2 v xc
nh Cd bng php o AES v suy ra hm lng Chloramphenicol theo phn ng trn.
131

Vi cch ny c th xc nh c Chloramphenicol n nhy 0,005 ppm.


Hon ton tng t, nhiu hp cht hu c nitro u c th xc nh gin tip
theo php o ph hp th nguyn t.
7. Theo phn ng to hp cht hydrua bay hi
y l phn ng ca mt s Anion ca mt s nguyn t vi nguyn t hydro
mi sinh to ra hp cht kh hydrua dng MeHn (vi n = 3,4,5,v 6). V d: HgH2,
AsHa, ASH5, SbH3, SbH5, SeH4, SeH8, TeH4, TeH3, v.v... Phn ng ny rt nh
lng, trong nhng iu kin ph hp cho mi cht. V th n cng c s dng
xc nh cc nguyn t Hg, As, Se, Te.. trong cc i tng khc nhau, nh trong
qung, trong nc, trong thc phm,.. bng php o ph pht x v hp th nguyn t.
Song trc ht l mu phn tch cn c x l a cc nguyn t ny v dng
mui ca Ion tan trong dung dch nc mi trng axit, v d HgCl2, SbCl5, SnCl4,
Na3AsO4, Na2SeO0, Na2TeO4. Sau thc hin theo cc phn ng sau:
+ Vi Hg:

HgCl2 + Na2BH4 + HCl HgH2

+ 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 TeHs

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.
6.4.2.2 Theo nguyn tc hai
1. Theo tc dng lm gim cng vch ph
Theo cch ny, ngi ta cho cht phn tch X (cn xc nh) tc dng vi dung
dch mui ca mt kim loi c ph pht x nhy mt nng nht nh ph hp v
khng i to thnh hp cht bn, v hp cht ny s lm gim cng vch ph
pht x ca kim loi mt cch tuyn tnh trong mt vng nng nht nh ca cht
cn xc nh X, ngha l y chng ta c cng vch ph (lc ph) c gi tr
132

nm.V d 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. v nh lng F theo phng php ng
chun. Dy chun c pha theo bng sau.
Bng 6.11
Dy chun xc nh nng Anion F

Cc cht

Co

C1

C2

C3

C4

C5

Cx

Ng Mg(ppm)

Ng. F (ppm)

10

Cx

HCl (%)

I5

Ix

Cc cht khc nh nhau


o I (Mg285,20 nm)

Io

I1

I2

I3

I4

Sau dng ng chun v pht hin nng ln F trong mu phn tch Cx


(hnh 6.10).

2. Theo tc dng lm tng cng vch ph


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 tnh theo s tng nng ca cht phn tch X c trong mu vi mt vng nht
nh.
133

V d: Trong mu dung dch th ph pht x ca Zr, hay Ca khi c mt ca


glucose, amino axit, hay protein, v.v. trong vng nng t n.10-4 - n.10-5 mol/l s
c tng theo tuyn tnh. Tnh cht ny c s dng xc nh glucose trong
cc i tng mu sinh hc (hnh 6.11).
Bng 6.11
Dy chun xc nh nng Protein
Cc cht
Co

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

Nh nhau tt c, nh mi trng, cht m, v.v.


Io

I1

I2

I3

I4

I5

Ix

Phn II

Chng 7
NHNG VN CHUNG CA PHP O ASS

7.1 S xut hin ph hp th nguyn t


Nh chng ta bit, vt cht c cu to bi cc nguyn t v nguyn t l
phn t c bn nh nht cn gi c tnh cht ca nguyn t ha hc. Nguyn t li
bao gm ht nhn nguyn t nm gia v chim mt th tch rt nh (khong
1/10.000 th tch ca nguyn t) v cc in t (electron) chuyn ng xung quanh ht
nhn trong phn khng gian ln ca nguyn t. Trong iu kin bnh thng nguyn
t khng thu v cng khng pht ra nng lng di dng cc bc x. Lc ny nguyn
t tn ti trng thi c bn. l trng thi bn vng v ngho nng lng nht ca
nguyn t. Nhng khi nguyn t trng thi hi t do, nu ta chiu mt chm tia sng
c nhng bc sng (tn si xc nh vo m hi nguyn t , th cc nguyn t t
do s hp th cc bc x c bc sng nht nh ng ng vi nhng tia bc x m
n c th pht ra c trong qu trnh pht x ca n. Lc ny nguyn t nhn nng
lng ca cc tia bc x chiu vo n v n chuyn ln trng tha kch thch c nng
lng cao hn trng thi c bn. l tnh cht c trng ca nguyn t trng thi
hi. Qu trnh c gi l qu trnh hp th nng lng ca nguyn t t do
trng thi hi v to ra ph nguyn t ca nguyn t . Ph sinh ra trong qu trnh
ny c gi l ph hp th nguyn t.
Nu gi nng lng ca tia sng b nguyn t hp th l XE th chng ta c:
E = (Cm - Eo) = hv

(7.1)

E = h.c /

(7.2)

hay l.

trong Eo v Cm l nng lng ca nguyn t trng thi c bn v trng thi


kch thch m; h l hng s Plank; c l tc ca nh sng trong chn khng; l
di sng ca vch ph hp th.
Nh vy, ng vi mi gi tr nng lng E; m nguyn t hp th ta s c
mt vch ph hp th vi di sng i c trng cho qu trnh , ngha l ph hp
th ca nguyn t cng l ph vch.
135

Nhng nguyn t khng hp th tt c cc bc x m n c th pht ra c


trong qu trnh pht x. Qu trnh hp th ch xy ra i vi cc vch ph nhy, cc
vch ph c trng v cc vch cui cng ca cc nguyn t. Cho nn i vi cc
vch ph qu trnh hp th v pht x l hai qu trnh ngc nhau (hnh 7.1). Theo
phng trnh (7.1), nu gi tr nng lng E l dng ta c qu trnh pht x; ngc
li khi gi tr E l nm ta c qu trnh hp th. Chnh v th, ty theo tng iu kin c
th ca ngun nng lng dng nguyn t ha mu v kch thch nguyn t m qu
trnh no xy ra l chnh, ngha l nu kch thch nguyn t:
+ Bng nng lng Cm ta c ph pht x nguyn t,
+ Bng chm tia n sc ta c ph hp th nguyn t.
Trong php o ph hp th nguyn t m hi nguyn t ca mu trong ngn la
hay trong cuvet graphit l mi trng hp th bc x (hp th nng lng ca tia bc
x) Phn t hp th nng lng ca tia bc x hv l cc nguyn t t do trong m hi
. Do , mun c ph hp th nguyn t trc ht phi to ra c m hi nguyn
t t do, v sau chiu vo n mt chm tia sng c nhng bc sng nht nh ng
ng vi cc tia pht x nhy ca nguyn t cn nghin cu. Khi cc nguyn t t
do s hp th nng lng ca chm tia v to ra ph hp th nguyn t ca n.

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)

trong Kv l h s hp th nguyn t ca vch ph tn s v v Kv l c trng


ring cho tng vch ph hp th ca mi nguyn t v n c tnh theo cng thc:
K v = K o .e

A ( v vo ) 2
2 RT ( v ) 2

(7.4)

Ko l h s hp th ti tnm ca vch ph ng vi tn s vo.


A l nguyn t lng ca nguyn t hp th bc x.
137

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)

y A chnh l tt nguyn t ca chm tia sng cng Io sau khi qua mi


trng hp th. A ph thuc vo nng nguyn t N trong mi trng hp th v
ph thuc c vo b dy L ca lp hp th (b dy chm sng i qua). Nhng trong
my o ph hp th nguyn t, th chiu di ca n nguyn t ha hay cuvet graphit
l khng i, ngha l L khng i, nn gi tr A ch cn ph thuc vo s nguyn t N
c trong mi trng hp th. Nh vy cng ca vch ph hp th s l:
A = k.L

(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)

y l cng thc tng qut tnh gi tr N trong ngn la nguyn t ha mu theo


Winefordner v Vicker. Trong :
F l tc dn mu vo h thng nguyn t ha (ml/pht),
W l hiu sut aerosol ha mu,
s l hiu sut nguyn t ha,
nRo l s phn t kh nhit ban u (ambient), To(oK),
nT l s phn t kh nhit T(oK) ca ngn la nguyn t ha,
138

- Q l tc ca dng kh mang mu vo bung aerosol ha (lt/pht),


- C l nng ca nguyn t phn tch c trong dung dch mu.
Phng trnh (7.6) cho ta bit mi quan h gia A v N, phng trnh (7.7) cho
ta bit mi quan h gia N v C. Mi quan h ny rt phc tp, n ph thuc vo tt c
cc iu kin nguyn t ha mu, ph thuc vo thnh phn vt l, ha hc, trng thi
tn ti ca nguyn t trong mu. Nhng nhiu kt qu thc nghim ch ra rng, trong
mt gii hn nht nh ca nng C, th mi quan h gia N v C c th c biu
th theo cng thc:
N = Ka.Cb

(7.8)

trong Ka l hng s thc nhim, ph thuc vo tt c cc iu kin ha hi v


nguyn t ha mu; cn b c gi l hng s bn cht, ph thuc vo tng vch ph
ca tng nguyn t, b c gi tr bng 1 v nh hn 1, tc l 0 < b <=l. Gi tr b = 1 khi
nng C nh v ng vi mi vch ph ca mi nguyn t phn tch, ta lun lun tm
c mt gi tr C = Co b bt u nh hn 1, ngha l ng vi:
+ Vng nng Cx < Co, th lun lun c b = 1, ngha l mi quan h gia
cng vch ph v nng Cx ca cht phn tch l tuyn tnh c dng ca phng
trnh y = ax.
+ Vng nng Cx > Co th
b lun nh hn 1, tc l b tin v
0, tt nhin l khng bng 0. Nh
vy trong vng ny mi quan h
gia cng vch ph v nng
Cx ca cht phn tch l khng
tuyn tnh.
Nn Co c gi l gii hn
trn ca vng tuyn tnh.
n y kt hp phng
trnh (7.6) v (7.8) chng ta c:
A = a.Cb

(7.9)

trong a = K.Ka v c gi l hng s thc nghim, ph thuc vo tt c cc


iu kin thc nghim ha hi v nguyn t ha mu, nh trnh by trn.
Chnh do thc t ny m trong mt php o nh lng xc nh mt nguyn t phi
gi cho cc iu kin ha hi, nguyn t ha mu n nh v khng i. Phng trnh
(7.9) c gi l phng trnh c s ca php o inh lng cc nguyn t theo ph
hp th nguyn t ca n. ng biu din ca phng trnh ny c 2 on, mt on
thng (trong on ny b = 1), v quan h gia A v C l tuyn tnh) v mt on
cong, trong on ny b < 1 (hnh 7.2).
139

7.3 Cu trc ca vch ph hp th nguyn t


Cc vch ph hp th nguyn t cng c cu trc nht nh nh cc vch ph
pht x tng ng vi n. Nhng vch ph hp th thng khng n sc nh vch
ph pht x. iu c ngha l rng ca vch ph hp th thng ln hn rng
ca vch ph pht x tng ng (hnh 7.3).
rng vch ph hp th
c xc nh bi nhiu yu t v
n l tng nhiu rng ring phn
ca cc yu t khc nhau, mt cch
tng qut, rng ton phn ca
vch ph hp th bao gm cc
- rng t nhin, Hn.
- rng kp, Hd.
- rng Lorenz, HL.
- rng cu trc tinh vi, Hc.
Tc l:
Ht = (Hn + Hd + HL + Hc )
- rng t nhin, Hn. Trong bn yu t trn, rng t nhin Hn c quyt
nh bi hiu s ca bc chuyn gia hai mc nng lng ca nguyn t trng thi
c bn v trng thi kch thch. rng ny ph thuc vo thi gian lu ca nguyn t
trng thi kch thch, v c tnh theo cng thc:
Hn =

1
2t m

(7.10)

trong tm l thi gian lu ca nguyn t trng thi kch thch m. a s cc


trng hp, rng t nhin ca vch ph hp th thng khng vt qu 1.10-3cm-1
(bng 7.1).
Bng 7.1
rng t nhin ca mt mt s vch ph hp th
Vch ph hp th ng.t

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

- rng kp, Hd- khc vi rng t nhin, rng kp li c quyt nh


bi s chuyn ng nhit ca nguyn t t do trong mi trng hp th theo hng
cng chiu hay ngc chiu vi chuyn ng ca phtn trong mi trng . V th
rng ny ph thuc nhiu vo nhit ca mi trng hp th. Mt cch gn ng,
rng kp c tnh theo cng thc:
H d = 1,76.10 5.vo T / A

(7.11)

y, T l nhit ca mi trng hp th (oK), A l nguyn t lng ca


nguyn t hp th bc x v vo l tn s trung tnm ca vch ph hp th.
Nh vy, rng kp ph thuc vo ba yu t T, A v vo. Ni chung, rng
ny ca hu ht cc vch ph hp th nguyn t thng nm trong khong t n.10-3
n n.10-1 cm-1 (bng 7.2).
Bng 7.2
rng kp ca mt s vch ph hp th

Vch ph (nm) Nguyn t lng

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

- rng Lorenz, HL: L yu t th ba gp phn m rng rng ca vch ph


hp th. rng ny c quyt nh bi s tng tc ca cc phn t kh c trong
mi trng hp th vi s chuyn mc nng lng ca nguyn t hp th bc x
trong mi trng . rng Lorenz HL c tnh theo cng thc:
H L = 12,40.10 23.Po 2

2 1 1
( + )
RT A M

(7.12)

trong P.o laf p lc kh v M l phn t lng ca kh trong mi trng


hp th ()2 l tit din va chm hiu dng gia nguyn t hp th bc x v phn t
kh tc dng vi n trong mi trng hp th. V cu trc hnh hc th rng Lorenz
cng c dng ging nh rng t nhin.
- Trn y l ba yu t chnh quyt nh rng ca vch ph hp th. Ngoi ra
cn c cc yu t khc, nh s m rng rng do cu trc tinh vi ca lp v in t
ca nguyn t. V d, khi m hi nguyn t hp th nng lng c t trong mt
t trng hay trong mt in trng, th yu t ny mi th hin r. l hiu ng
141

Stark ca cu trc nguyn t. Hiu ng ny cng gp phn lm tng rng ca vch


ph hp th. Do , mt cch y , rng ca vch ph hp th nguyn t phi l:
Ht = (Hn + Hd + Hl + Hc)

(7.13)

y l cng thc tng qut y


cho rng ca vch ph hp th
nguyn t. Nhng trong thc t ca
php o ph hp th nguyn t, khi
khng c tc dng ca t trng
ngoi v vi cc my quang ph c
tn sc nh hn 2 /mm, th l
thuyt v thc nghim ch ra rng,
rng chung ca mt vch ph hp th
ch do ba thnh phn u (chim trn
95%) ca biu thc (7.13) quyt
nh;

ngha l chng ta c:
Ht = (Hn + Hd + Hl)

(7.14)

iu ny hon ton ng i vi hu ht cc vch ph cng hng trong iu


kin mi trng hp th c nhit t 1600 - 3500oC v p sut l 1 atm. y, phn
trung tnm ca vch ph l do rng t nhin Hn v rng kp Hd quyt nh, phn
rng Lorenz quyt nh (hnh 7.4).
Trong tng rng ,
rng Hn chim 45- 50 % cn li l
ca rng Hd (25%) v Hl
(20%). Cn rng Hc thng
khng ng k, n ch c ngha
khi nguyn t c t trong mt
t trng mnh.
- Ngoi nhng nghin cu trn,
so snh rng ca cc vch ph
hp th vi nhau ngi ta thng
dng i lng na rng ca
vch ph (Wl/2).
l 130 rng ca vch ph hp th v tr ng vi mt na (1/2) ca h s
hp th cc i Kmax (hnh 7.5). Gi tr ny ca vch ph hp th lun lun ln hn ca
vch ph pht x tng ng, tc l vch ph hp th c rng ln hn vch ph pht
x nguyn t tng ng vi n, v vch ph pht x, rng t nhin Hn quyt nh
n 90% tng rng chung ca vch ph.
142

7.4 Nguyn tc v trang b ca php o AAS


Phng php phn tch da trn c s o ph hp th nguyn t ca mt nguyn
t c gi l php o ph hp th nguyn t (php o AAS). Nh trong mc 7.1.
chng ta nghin cu, c s l thuyt ca php o ny l s hp th nng lng (bc
x n sc) ca nguyn t t do trong trng thi hi (kh) khi chiu chm tia bc x
qua m hi ca nguyn t y trong mi trng hp th. V th mun thc hin c
php o ph hp th nguyn t ca mt nguyn t cn thc hin cc qu trnh sau y:
1. Chn cc iu kin v mt loi trang b ph hp chuyn mu phn tch t
trng thi ban u (rn hay dung dch) thnh trng thi hi ca cc nguyn t t do.
l qu trnh ha hi v nguyn t ha mu. Nhng trang b thc hin qu trnh
ny c gi l h thng nguyn t ha mu (dng c nguyn t ha mu). Nh
chng ta c c m hi ca cc nguyn t t do ca cc nguyn t trong mu phn
tch. m hi chnh l mi trng hp th bc x v sinh ra ph hp th nguyn t.
2. Chiu chm tia sng bc x c trng ca nguyn t cn phn tch qua m
hi nguyn t va iu ch c trn. Cc nguyn t ca nguyn t cn xc nh
trong m hi s hp th nhng tia bc x nht nh v to ra ph hp th ca n.
y, phn cng ca chm tia sng b mt loi nguyn t hp th l ph thuc
vo nng ca n mi trng hp th. Ngun cung cp chm tia sng pht x ca
nguyn t cn nghin cu gi l ngun pht bc x n sc hay bc x cng hng.
3. Tip , nh mt h thng my quang ph ngi ta thu ton b chm sng,
phn li v chn mt vch ph hp th ca nguyn t cn nghin cu o cng
ca n. Cng chnh l tn hiu hp th ca vch ph hp th nguyn t. Trong
mt gii hn nht nh ca nng C, gi tr cng ny ph thuc tuyn tnh vo
nng C ca nguyn t trong mu phn tch theo phng trnh (7.9).
Ba qu trnh trn chnh l nguyn tc ca php o ph hp th nguyn t. V vy,
mun thc hin php o ph hp th nguyn t, h thng my o ph hp th nguyn
t phi bao gm cc phn c bn sau y:
- Phn 1. Ngun pht tia pht x cng hng ca nguyn t phn tch (vch ph
pht x c trng ca nguyn t cn phn tch), chiu vo mi trng hp th cha
cc nguyn t t do ca nguyn t. l cc n canh rng (HCL), cc n phng
in khng in cc (EDL), hay ngun pht bc x lin tc c bin iu (xem
mc 9.1. chng 9).
- Phn 2. H thng nguyn t ha mu phn tch. H thng ny c ch to
theo hai loi k thut nguyn t ha mu. l k thut nguyn t ha bng ngn la
n kh (lc ny ta c php o F-AAS) v k thut nguyn t ha khng ngn la (lc
ny ta c php o ETA-AAS).
Trong k thut nguyn t ha bng ngn la, h thng ny bao gm:
143

+ B phn dn mu vo bung aerosol ha v thc hin qu trnh aerosol ha


mu (to th sol kh).
+ n nguyn t ha mu (Burner head) t chy hn hp kh c cha
mu th huyn ph sol kh (hnh 7.6).
Ngc li, khi nguyn t ha mu bng k thut khng ngn la, ngi ta thng
dng mt l nung nh bng graphit (cuvet graphit) hay thuyn Tangtan (Ta) nguyn
t ha mu nh ngun nng lng in c th thp (nh hn 12 V) nhng n c dng
rt cao (50-800 A).

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

Vi cc my hin i cn c thm mt microcomputer hay microprocessor, v h


thng phn mm. Loi trang b ny c nhim v iu khin qu trnh o v x l cc
kt qu o c, v th, tnh nng ca mu phn tch, v.v... Mt cch tm tt,
chng ta c th minh ho mt h thng my o ph hp th nguyn t nh s trong
hnh 7.7.

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

n 1.10-5 %. c bit, nu s dng k thut nguyn t ha khng ngn la th c th t


n nhy n.10-7% (bng 7.3). Chnh v c nhy cao, nn phng php phn tch
ny c s dng rt rng ri trong nhiu lnh vc xc nh lng vt cc kim loi
c bit l trong phn tch cc nguyn t vi lng trong cc i tng mu y hc, sinh
hc, nng nghip, kim tra cc ha cht c tinh khit cao.
Bng 7.3
nhy ca cc nguvn t theo php o AAS

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

nhim v ha hi v nguyn t ha mu phn tch, to ra m hi ca cc nguyn t t


do c kh nng hp th bc x n sc to ra ph hp th nguyn t. V th ngn
la n kh mun dng vo mc ch ha hi v nguyn t ha mu phn tch cn
phi tho mn mt s yu cu nht nh sau y:
1. Ngn la n kh phi lm nng u c mu phn tch, ha hi v nguyn
t ha mu phn tch vi hiu sut cao, bo m cho php phn tch t chnh
xc v nhy cao.
2. Nng lng (nhit ) ca ngn la phi ln v c th iu chnh c ty
theo tng mc ch phn tch mi nguyn t. ng thi li phi n nh theo thi gian
v c th lp li c trong cc ln phn tch khc nhau m bo cho php phn
tch t kt qu ng n. Yu cu ny c lc khng c tha mn, v nhit cao
nht ca ngn la cng ch n 3300oC. Do vi nhng nguyn t to thnh hp cht
bn nhit th hiu sut nguyn t ha ca ngn la l km.
3. Yu cu th ba l ngn la phi thun khit, ngha l khng sinh ra cc vch
ph ph lm kh khn cho php o hay to ra ph nn qu ln quy ri php o. Qu
trnh Ion ha v pht x phi khng ng k v qu trnh ny lm mt cc nguyn t t
do to ra ph hp th nguyn t.
4. Mt yu cu na l ngn la phi c b dy ln c c lp hp th
dy lm tng nhy ca php o. ng thi b dy ca lp hp th li c th thay
i c khi cn thit, o nng ln. Trong cc my hin nay, b dy ny c
th thay i c t 2 ci n 10 cm.
5. Tiu tn t mu phn tch.
to ra ngn la, ngi ta c th t chy nhiu hn hp kh khc nhau, bao
gm mt kh oxy ha v mt kh chy, trong cc n kh thch hp. Nhng vi nhng
yu cu ni trn th ch c mt vi loi n kh l to ra c ngn la tng i
ph hp cho php o ph hp th nguyn t. l nhng mi trng nguyn t ha
mu tng i bn vng v kinh t (bng 8.1). c bit c ng dng nhiu nht
trong php o AAS l ngn la ca n kh c t bng hn hp kh: (axetylen v
khng kh nn) hay ngn la ca n kh (N2O v axetylen), hay (hydro v axetylen).
Bng 8.1a v 8.1b l mt s v d v nhit ca ngn la mt s n kh c
dng trong php o AAS (Ox: cht oxy ha; K.K: khng kh.).

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

t nng cng vi cc ht sol kh (th aerosol) ca mu phn tch. Phn ny c nhit


thp (700-1200oC). Dung mi ha tan mu s bay hi trong phn ny v mu c
sy nng.
- Phn b: L vng trung tm ca ngn la. Phn ny c nhit cao, nht l
nh b, v thng khng c mu hoc c mu xanh rt nht. Trong phn ny hn hp
kh c t chy tt nht v khng c phn ng th cp. V th trong php o ph
hp th nguyn t ngi ta phi a mu vo phn ny nguyn t ha v thc hin
php o, ngha l ngun n sc phi chiu qua phn ny ca ngn la.
- Phn c: L v v ui ca ngn la. Vng ny c nhit thp, ngn la c
mu vng v thng xy ra nhiu phn ng th cp khng c li cho php o ph hp
th nguyn t.
Chnh do cc c im v cu to nn trong mi php phn tch cn phi kho
st chn c cc iu kin ph hp, nh thnh phn v tc ca hn hp kh
chy to ra ngn la, chiu cao ca ngn la, v.v...
8.2.3 Trang b nguyn t ha mu
Mun thc hin php o ph hp th
nguyn t (F-AAS), trc ht phi chun b
mu phn tch trng thi dung dch. Sau
dn dung dch mu vo ngn la n kh
ha hi v nguyn t ha mu phn tch v
thc hin php o. Qu trnh nguyn t ha
trong ngn la gm hai bc k tip nhau.
Bc mt l chuyn dung dch mu phn tch
thnh th cc ht nh nh sng m trn u
vi kh mang v kh chy. l cc ht sol
kh (th aerosol). Qu trnh ny c gi l
qu trnh aerosol ha hay nebulize ha. K
thut thc hin qu trnh ny v hiu sut ca
n nh hng trc tip n kt qu ca php
o AAS.
Sau dn hn hp aerosol cng hn hp kh t vo n (burner head)
nguyn t ha. Kh mang l mt trong hai kh t chy to ra ngn la. Thng
thng ngi ta hay dng kh oxy ha (khng kh nn hay kh N2O). Hai giai on
trn c thc hin bng mt h thng trang b nguyn t ha mu (hnh 7.6). H
thng ny gi l Nebulizer System, gm hai phn chnh:

- n nguyn t ha mu (burner head). Cc n ny thng c hai dng khc


nhau, hoc hnh trn c nhiu l hay hnh mt khe hp c rng t 0,5 - 1,0 mm v
152

chiu di 5 cm hay 10 cm.


Loi khe di 10 cm cho hn hp kh t axetylen v khng kh nn; loi khe di
5 cm l cho hn hp kh t axetylen v kh N2O (hnh 8.3). Cn loi ming trn ch
thch hp cho php o ph pht x.
- Phn hai l bung aerosol
ha mu. l bung iu ch
cc ht sol kh ca mu vi kh
mang. thc hin cng vic ny
ngi ta p dng hai k thut theo
nguyn l khc nhau. l k thut
pneumatic-mao dn (phun kh) v
k thut ultrasonic (siu nm). Do
cng c hai loi h trang b khc
nhau (hnh 8.4 v 8.5) iu ch
sol kh ca mu.
a. Aerosol ha mu theo k thut pneumatic-mao dn.
Theo cch ny ngi ta dng h thng nebulize v kh mang to ra th si kh
ca mu phn tch nh hin tng mao dn (hnh 8.4).
Trc ht nh ng mao dn S v dng kh mang K m dung dch mu c dn
vo bung aerosol ha. Trong bung ny, dung dch mu c nh tung thnh th bi
(cc ht rt nh) nh qu bi E v cnh qut Q, ri c trn u vi hn hp kh t
v c dn ln n nguyn t ha (burner head).
Khi hn hp kh t chy burner head s to ra ngn la, di tc dng ca
nhit ca ngn la cc phn t mu th si kh s b ha hi v nguyn t ha to ra
cc nguyn t t do ca cc nguyn t c trong mu phn tch.
l nhng phn t hp th nng lng v to ph hp th nguyn t ca
nguyn t cn nghin cu.
Nhng cn ch rng, ngoi nh hng ca thnh phn kh t v tc dn
hn hp kh n cng vch ph, th tc dn dung dch mu vo bung aerosol
ha cng nh hng ng k n cng vch ph (bng 8.2).
Tc dn mu ph thuc vo nhiu yu t v c tnh gn ng theo cng
thc:

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

Ngha l tc dn mu V ph thuc vo cc tham s r, P, L v . Nhng trong


mt h thng my th r v L thng l c nh, P c gi khng i, cho nn V ch
154

cn ph thuc ch yu vo nht ca dung dch mu (hnh 8.5).


b. Aerosol ha mu bng siu nm.
Theo k thut ny, aerosol
ha mu phn tch ngi ta dng
h thng siu nm c tn s t 1-4,5
MHz. Lc siu nm c th c
truyn qua tng rn (hnh 8.6a)
hay qua th lng (hnh 8.6b) n
dung dch mu thc hin vic
aerosol ha mu, ngha l di tc
dng ca lc siu nm, mu dung
dch cng c phn tn (nh ti)
thnh nhng ht rt nh v trn u
vi hn hp kh dn ln n (burner head) nguyn t ha. y ng knh (d) ca
cc ht sol kh c tnh theo cng thc:
d = ( .s / 4.Di.F 2 )

(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

k thut pneumatic. Mt khc, s aerosol ha bng siu nm thng cho lp li tt


hn (bng 8.3).
Bng 8.3
nhy theo hai k thut aerosol ha mu

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

8.2.4 Nhng qu trnh xy ra trong ngn la


Ngn la l mi trng nguyn t ha mu ca php o ph hp th nguyn t
(F- AAS). Trong ngn la c nhiu qu trnh ng thi xy ra: c qu trnh chnh v
cng c qu trnh ph (th cp). Trong nhit ca ngn la l yu t quyt nh
mi din bin ca cc qu trnh .
Trc ht, khi mu th si kh c dn ln n nguyn t ha, di tc dng
nhit ca ngn la, ming n, l s bay hi ca dung mi ho tan mu v cc cht
hu c (nu c) trong th si kh. Nh vy mu cn li l cc ht bt mu rt nh mn
156

(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

Bn cnh cc qu trnh chnh, trong ngn la n kh thng cn c mt s qu


trnh ph. Cc qu trnh ph ny thng nh hng n cng vch ph trong
nhng mc khc nhau, nh lm gim cng ca vch ph, n xy ra nh th no
l ty thuc vo nhit ca ngn la v thnh phn ca mu, v d nh:
- S Ion ha ca nguyn t phn tch. Qu trnh ny xy ra d dng i vi cc
nguyn t c th Ion ha thp v mc b Ion ha ca mt loi nguyn t l ty
thuc vo nhit ca ngn la v th Ion ha ca nguyn t . Nu th Ion ha
cng nh, th n b Ion ha cng nhiu. V th qu trnh ny c ngha rt ln i vi
cc kim loi kim v sau l cc kim th (bng 8.4).
Bng 8.4
Mc b Ion ha ca cc nguyn t theo nhit ngn la v th Ion ha ca n
Nguy

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

Nh vy, qu trnh Ion ha l lm gim s nguyn t t do trong ngn la, c


ngha l lm gim cng ca vch ph hp th. V th cn phi hn ch nh hng
ny, bng cch chn cc iu kin ph hp gi cho nhit ca ngn la n nh v
khng qu ln xy ra s Ion ha nguyn t phn tch; hoc thm vo mu Anion
ca mt nguyn t kim loi c th Ion ha thp hn th Ion ha ca nguyn t phn
tch hn ch qu trnh Ion ha ca nguyn t phn tch.
S pht x: ng thi vi qu trnh Ion ha, cn c s kch thch ph pht x ca
cc nguyn t t do ca nguyn t phn tch di tc dng nhit ca ngn la. S
nguyn t b kch thch v mc b kch thch ph pht x cng ph thuc vo nng
lng kch thch ph pht x ca tng nguyn t. Nguyn t no c nng lng kch
thch ph pht x cng nh th s b kch thch cng nhiu (bng 8.5). Nhit ca
ngn la cng cao th cng b kch thch cng nhiu. loi tr yu t nh hng ny,
ngi ta cng thm vo mu Anion ca cc nguyn t kim loi c th kch thch ph
pht x thp hn nguyn t phn tch, qu trnh ny ch xy ra vi nguyn t thm
vo .
158

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

T s (Nhng) nhit (0C).

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

S to thnh hp cht bn nhit. Trong ngn la n kh, mt s kim loi c th


hnh thnh cc hp cht bn nhit kiu monoxit dng MeO, nh AlO, Bao, MgO, Beo,
ZrO,... Loi hp cht ny rt bn, khi hnh thnh th kh phn li thnh cc nguyn
t t do trong ngn la n kh. V th lm gim nhy ca php o.
Cc qu trnh ph tuy c mc khc nhau, nhng trong mt mi tng quan
nht nh trong ngn la, c bit l nhit ngn la, th tt c cc qu trnh u
c th xy ra cng vi cc qu trnh chnh ca php o F-AAS. Do iu quan trng
i vi chng ta l phi chn cc iu kin ph hp hn ch n mc nh nht cc
qu trnh ph v gi cho n khng i sut trong mt php o xc nh mt nguyn t.
l mt phn ca cng vic ti u ha cc iu kin cho php o ph hp th
nguyn t trong ngn la.

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

3. Ha hi, nguyn t ha.


MeA(r) MeA(l) MeA(k)
4. S phn li, kch thch, hp th, Ion ha, pht x.
1 Meo + A (phn li)
1 Meo + vh (hp th bc x)
MeA

1 Meo + E (kch thch)


1 Meo - e ( Ion ha)
1 Meo +......

5. S kh oxy ca oxit bi cacbon.


MeO + C Me + CO
6. Cc phn ng ha hc ph khc (hp cht bn nhit monoxit):
Me + O Meo
Me + C MeCx

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

a) Cc qu trnh trong ngn la ca CaCl2 khng c PO4

162

c) cc qu trnh trong ngn la ca CaCl2 khi c Al


Hnh 8.9
V d v cc qu trnh trong ngn la n kh (a, b, c).

8.2.5 Ti u ha cc iu kin nguyn t ha mu


Nh trn chng ta xc nh, nguyn t ha mu l cng vic quan trng nht
ca php o F-AAS. Qu trnh ny thc hin khng tt s nh hng trc tip n kt
qu ca php o. Do mun t c kt qu chnh xc v ng n, chng ta phi
kho st, pht hin v chn cc iu kin nguyn t ha mu ph hp nht cho tng
nguyn t cn phn tch trong mi loi mu c th. Cc iu kin c th l: Thnh
phn v tc ca hn hp kh t to ra ngn la. y l yu t quyt nh nhit
ca ngn la. V th qua vic thay i thnh phn v tc ca hn hp kh t to ra
ngn la chng ta c th chn c nhit ph hp ha hi v nguyn t ha
nguyn t cn nghin cu (hnh 8.1 v hnh 8.10) v (bng 8.1).
- Tc dn dung dch mu vo h thng nguyn t ha. Ni chung, trong nhiu
trng hp tc dn mu ph hp nm trong khong t 4-5 ml/pht vi php o ca
nhiu nguyn t (hnh 8.11).
- Chiu cao ca n nguyn t ha. Yu t ny cng nh hng trong mt mc
nht nh v ty thuc vo tng nguyn t (hnh 8.12), nn chn chiu cao ca
burner head sao cho c c cng vch ph ln nht v n nh nht

163

- B dy ca mi trng hp th L: Khi thay i b dy ca lp hp th (mi


trng hp th) chng ta c th tng hay gim nhy ca php o. Ngha l ty theo
nng ln hay nh ca nguyn t phn tch m chng ta thay i gc nghing ca
n nguyn t ha mu (burner head) c c b dy L ca lp hp th ph hp
nht. Khi L ln nht ta s c nhy cao nht, lm gim L th nhy gim theo,
ngha l khi o nng ln th ta phi quay n nguyn t ha mt gc cho ph hp
m khng cn pha long, nhng sau cn phi gi khng i sut trong qu trnh o.
- Tn s my siu m: Nu to soil kh mu phn tch trong h thng aerosol ha
bng siu nm th tn s v cng sut ca h thng siu nm cng cn c chn cho
ph hp. Yu t ny cng nh hng n hiu sut nguyn t ha mu (hnh 8.7). Tip
l tc dn mu vo bung siu nm cng cn c chn cho ph hp.
- nht ca dung dch mu: Tip theo cc yu t trn l nht ca dung dch
mu. Yu t ny nh hng rt nhiu n hiu sut nguyn t ha thng qua qu trnh
aerosol ha mu theo k thut pneumatic (hnh 8.5) v (bng 8.2). Do mu phn tch
164

v cc mu chun dng ng chun cn phi c chun b trong cng mt iu


kin, phi c cng thnh phn ha hc, vt l, c bit l thnh phn ca cht nn ca
mu, axit, loi axit dng lm mi trng chng c cng nht.
Trn y l cc yu t c nh hng n qu trnh nguyn t ha mu, ngha l
nh hng n kt qu ca php o F-AAS. Tt nhin mi yu t c nh hng trong
mc khc nhau, c trng hp xut hin, song cng c trng hp khng xut hin
r rt. Trong yu t u tin, nhit ngn la l quan trng nht, n quyt nh
hiu sut ca qu trnh nguyn t ha mu. Cc yu t khc cn li nh hng n yu
t th nht v qua m gy nh hng n kt qu ca php o.
Do , vic nghin cu pht hin v chn cc thng s cho ph hp nht i
vi mc ch phn tch nh lng mt nguyn t vi lng trong mi i tng mu l
mt cng vic ht sc cn thit v quan trng cho k thut phn tch F-AAS, chn
v xy dng mt quy trnh chun.
Mt khc, nu chn c cc iu kin nguyn t ha mu ph hp, th trong
nhiu trng hp li loi tr c mt s yu t nh hng nht nh, nh nh hng
ca ph nn, s Ion ha, s pht x hay cc qu trnh th cp trong ngn la khng c
li cho php o. Thc hin cc cng vic trn chnh l tiu chun ha xy dng mt
quy trnh phn tch mt nguyn t bng php o ph hp th nguyn t ca n.
8.3 K thut nguyn t ha khng ngn la
8.3.1 c im v nguyn tc
K thut nguyn t ha khng ngn la ra i sau k thut nguyn t ha trong
ngn la. Nhng k thut ny c pht trin rt nhanh v hin nay ang c ng
dng rt ph bin, v k thut ny cung cp cho php o AAS c nhy rt cao (mc
nanogam ppb); c khi gp hng trm n hng nghn ln php o trong ngn la (bng
1.3). y l u im chnh ca k thut nguyn t ha khng ngn la. Do , khi
phn tch lng vt cc kim loi trong nhiu trng hp khng cn thit phi lm giu
s b cc nguyn t cn xc nh. c bit l khi xc nh cc nguyn t vi lng
trong cc loi mu ca y hc, sinh hc, dc phm, thc phm, nc gii kht, mu,
srum.
Tuy c nhy cao nhng trong mt s trng hp, n nh ca php o
khng ngn la thng km php o trong ngn la, nh hng ca ph nn thng
rt ln. l c im v cng l nhc im ca php o ny. Song vi s pht trin
ca vt l v ca k thut o hin i, ngy nay ngi ta c th khc phc c nhc
im ny khng kh khn lm. V th cc h thng my o ph hp th theo k thut
khng ngn la ca nhng nm 1980 lun lun c km theo h thng b chnh nn v
n nh ca n cng khng km cc h thng ca php o trong ngn la v m
bo nhy cao c ppb i vi nhiu nguyn t.
c im na ca php o khng ngn la l i hi mt lng mu tng i
165

nh. Thng thng mi ln o ch cn lng mu t 20 n 50 L. Do khng cn


nhiu lng mu phn tch, vic chun b mu cng d dng v khng tn nhiu ha
cht cng nh cc dung mi tinh khit cao t tin.
- V nguyn tc, k thut nguyn t ha khng ngn la l qu trnh nguyn t
ha tc khc trong thi gian rt ngn nh nng lng ca dng in cng sut ln v
trong mi trng kh tr. Qu trnh nguyn t ha xy ra theo ba giai on k tip
nhau: sy kh, tro ha luyn mu, nguyn t ha o ph hp th v cui cng l
lm sch cuvet. Trong hai giai on u l chun b cho giai on nguyn t ha
t kt qu tt. Nhit trong cuvet graphit l yu t chnh quyt nh mi s din
bin ca qu trnh nguyn t ha mu.
8.3.2 Cc yu cu h thng nguyn t ha mu
1. H thng nguyn t ha phi ha hi v nguyn t ha mu phn tch vi hiu
sut cao v n nh, m bo cho php o c nhy cao v lp li tt.
2. Phi cung cp c nng lng (nhit cao) ln, c th nguyn t ha
c nhiu loi mu v phn tch c nhiu nguyn t.
3. Cuvet cha mu nguyn t ha phi c tinh khit cao. Khng lm nhim
bn mu, khng c ph ph gy kh khn cho php o nguyn t cn phn tch.
4. Hn ch, c t hay khng c cc qu trnh ph trong qu trnh nguyn t ha
mu thc hin php o.
5. Tiu tn t mu.
l nhng yu cu ti thiu cn thit i vi mt h thng trang b nguyn t
ha mu trong php o khng ngn la. Trn c s cc yu cu ny, mi hng ch to
my ph hp th nguyn t u c nhng h trang b ring cho cc my ca h. Song
v nguyn tc v cc bc ca qu trnh nguyn t ha th u nh nhau.
8.3.3 Nguyn tc v cc giai on ca qu trnh nguyn t ha mu
Nguyn tc v cch thc hin ca k thut nguyn t ha khng ngn la l hon
ton khc vi k thut nguyn t ha trong ngn la. y ngi ta thng dng nng
lng nhit ca mt ngun nng lng ph hp nung nng, ha hi v nguyn t
ha mu phn tch trong ng cuvet graphit hay trong thuyn tng tan (Ta) nh. Ngun
nng lng thng c dng hin nay l dng in c cng dng rt cao (t 50 600 A) v th thp (di 12 V) hay l nng lng ca dng in cao tn cm ng.
Di tc dng ca cc ngun nng lng ny, cuvet cha mu phn tch s c
nung nng tc khc v mu s c ha hi v nguyn t ha to ra cc nguyn
t t do trng thi hi c kh nng hp th bc x n sc, to ra ph hp th
nguyn t ca n. Dng c nguyn t ha mu theo k thut ny hin nay c rt
nhiu loi khc nhau c ch to ty thuc theo tng hng v tng phng th nghim.
Nhng c th khi qut theo cc nhm chnh di y:
166

+ Cc loi cuvet graphit;


+ Cc loi cc graphit;
+ Cc loi thuyn kim loi chu nhit, nh Ta.
Trong cc loi trn, c dng ph bin nht l cc cuvet graphit, v n tho mn
c nhng yu cu chnh ca php do khng ngn la. V cuvet graphit, mi hng
ch to my quang ph hp th nguyn t u c cuvet graphit ring cho cc my ca
h v h thng nguyn t ha khng ngn la tng ng.
H thng nguyn t ha mu theo k thut khng ngn la gm c:
+ Bung nguyn t ha v cuvet graphit cha mu phn tch thc hin qu
trnh nguyn t ha;
+ Ngun nng lng nung nng l graphit n nhit nguyn t ha mu
v b iu khin hay b chng trnh (programer) t chng trnh v ch huy qu
trnh nguyn t ha mu theo cc giai on nht nh. V d: Hng Perkin Elmer c h
thng khng ngn la HGA-70, HGA-400, HGA-5001 Hng Philips'pye Unicam c
SP9- 041.
Tuy mi hng c nhng dng c khc nhau, nhng qu trnh nguyn t ha trong
cc dng c u xy ra theo 4 giai on k tip nhau trong thi gian tng cng t
80 - 60 giy. Cc giai on l:
8.3.3.1 Sy kh mu
y l giai on u tin ca qu trnh nguyn t ha mu. N l rt cn thit
m bo cho dung mi ho tan mu bay hi nh nhng v hon ton, nhng khng lm
bn mu, mt mu. V nu khng thc hin sy tt, mu s b bn lm sai lch kt qu
phn tch. thc hin qu trnh sy tt, i vi mi mt loi mu cn phi tin hnh
nghin cu, pht hin v chn nhit v thi gian sy cho ph hp. Nhit v thi
gian sy kh ca mi loi mu ph thuc vo bn cht ca cc cht trong mu v
dung mi ho tan n. Thc nghim cho thy rng, khng nn sy mu nhit cao
v sy kh nhanh. Ni chung nhit sy kh ph hp i vi ba s cc mu v c
trong dung mi nc nm trong khong t 100 - 150oC trong thi gian t 25-40 giy
vi lng mu c bm vo cuvet nh hn 100 l. Tt nhin qu trnh sy kh chm
nhit thp bao gi cng cho kt qu n nh. Vic tng nhit khi sy, t nhit
phng n nhit sy mong mun cng cn c thc hin t t, vi tc tng
nhit t 8 n 50C trong mt giy l ph hp.
i vi cc mu c cha cc cht hu c hay ho tan trong dung mi hu c,
thng phi sy nhit thp hn v tc tng nhit phi chm hn dung mi
nc. Vi loi mu ny, nhit sy thng l di 1000C. Hnh 8.13 l mt v d v
qu trnh sy kh mu. Trong T8 l nhit sy ti a (ti hn) v trong 6 tc
tng mhit sy, th ch c qu trnh theo ng s 5 v 6 l cho kt qu tt. ng
167

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

Nn khc nhau ca mu (matrix effect), nht l cc cht nn bn nhit. Hnh 8.18


l mt v d v vn ny khi o ph hp th nguyn t ca Mg trong cc nn khc
nhau.
Ngha l Mg trong cc cht nn khc nhau c nhit tro ha gii hn l T1, T2,
T3 v T4 (tc l 600, 1000 v 1100oC).
ng thi qua chng ta thy ngha ca cht ph gia c thm vo mu
phn tch.
Bng 8.6
Mt s v d v nhit sy, tro ha luyn mu, nguyn t ha mu gii hn ca
mt s nguyn t (theo W. Fuller)
Nguyn t

Nhit ti hn ca qu trnh (oC)


Sy mu

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

i vi cc mu c cht hu c hay trong dung mi hu c th giai on ny


cng phi cn thn v nhit chn tro ha phi thp hn dung mi l nc,
trnh s bay hi trc ca nguyn t phn tch dng hp cht c kim. Do , vi
mi loi mu, trong mi loi dung mi, chng ta cn kho st pht hin c nhit
tro ha ph hp cho n.
8.3.3.3 Nguyn t ho
y l giai on cui cng ca qu trnh nguyn t ha mu, nhng li l giai
on quyt nh cng ca vch ph. Song n li b nh hng bi hai giai on
trn. Giai on ny c thc hin trong thi gian rt ngn, thng thng t 3 n 6
giy, rt t khi n 8-10 giy.
Nhng tc tng nhit li l rt ln t ngay tc khc n nhit
nguyn t ha v thc hin php o cng vch ph. Tc tng nhit thng
l t 1800 - 2500oC/giy, thng thng ngi ta s dng tc ti a. nguyn t
ha ca mt nguyn t rt khc nhau (hnh 8.17).
ng thi mi nguyn t cng c mt nhit nguyn t ha gii hn Ta ca n.
Nhit Ta ny ph thuc vo bn cht ca mi nguyn t v cng ph thuc trong
mc nht nh vo trng thi v thnh phn ca mu m n tn ti, nht l cht nn
ca mu (hnh 8.18).

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

Khi nghin cu qu trnh nguyn t ha ca nhiu nguyn t trong cc iu kin


khc nhau, ngi ta thy s din bin ca nhit nguyn t ha ca mt nguyn t
v cng vch ph ca n thng theo hai loi nh trong hnh 8.19. Cc nguyn t
theo loi (1) c nhit nguyn t ha gii hn l Ta1, ngc li, cc nguyn t theo
loi (2) c nhit nguyn t ha gii hn l Ta2.
Tiu biu cho loi (1) l cc nguyn t Zn, Fe, Pb, Cu v Mo, tiu biu cho loi
(2) l cc nguyn t, Si. Sn, Mg, Ca (hnh 8.17). Cc gi tr nhit Ta1 v Ta2 l
nhit nguyn t ha gii hn ca mi loi. Khi nguyn t ha mu o cng
vch ph ca mt nguyn t nhit cao hn nhit gii hn ny thng khng
c li thm v cng , m kt qu thc nghim cho thy cc kt qu o thng
khng n nh v thng lm hng nhanh cuvet graphit.

172

Ngoi vic chn


nhit , trong giai on
ny cn cn phi chn
thi gian nguyn t ha
cho ph hp lm sao m
bo cc lc cng vch
ph thu c phi gn v
ch c mt nh. Nh v
d trong hnh 8.20 ch c
trng hp (a) l tt.

Hnh 8.20
Quan h gia hnh dng lc vch ph v thi gian nguyn t ha

Ca-422,7nm. a: 3 giy, b: 4 giy, c: 6 giy v d: 8 giy


n y chng ta c th khi qut ton b qu trnh nguyn t ha mu theo k
thut khng ngn la nh trong hnh 8.21. Trong : (1) l giai on sy mu; (2) l
giai on tro ha luyn mu; (3) l giai on nguyn t ha o cng vch ph v
(4) l giai on lm sch cuvet graphit. on R l thi gian tng nhit ca hai giai
on u (thi gian Ramp).

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

Hnh 8.24 l cc lc vch ph


ca qu trnh nguyn t ha 10 ppb
Pb vi cc tc t nng cuvet: 1)
2300; 2) 1600; 3) 1000 v 4)
800oC/giy. y chng ta thy vi
tc t nng 1, vch ph c
chiu cao ln nht, sau n tc
2 v cui cng l tc 4.
Nhng vn chnh l ch, khi
nguyn t ha vi tc t nng
cuvet thp, ta thng phi nguyn
t ha thi gian di, do trng
hp dn n lc ca vch ph khng nhng c chiu cao thp, m cn c nhiu nh
v dng phc tp gy kh khn cho vic nh gi nh lng.
- Yu t th t l loi cuvet graphit dng nguyn t ha mu, ngha l cc loi
nguyn liu graphit khc nhau cng nh hng n cng vch ph v thi gian
nguyn t ha mu (hnh 8.25).
Ni chung, cc loi graphit hot ha ton phn thng cho kt qu tt nht,
nhy cao, n nh.
Hnh 8.25 l mt v d v vn ny. l vic nguyn t ha Cr v Al vi ba
loi cuvet khc nhau. Pic 1 l vi cuvet graphit c hot ha nhit ton phn; tc 2 l
cuvet graphit ch c hot ha b mt v tc 3 l cuvet graphit thng khng hot
ha.

176

8.3.5 Cc qu trnh trong cuvet graphit


Cc qu trnh xy ra trong cuvet graphit v c ch ca qu trnh nguyn t ha
mu l nhng vn ht sc phc tp, nhng li quyt nh cng ca vch ph.
Mun hiu bit c ch ca vn ny, chng ta phi xem xt tt c cc yu t ng
hc, nhit ng hc v cc phn ng ha hc c th xy ra trong cuvet, v cc qu trnh
l xy ra ng thi v c tc ng qua li ln nhau. Nhng khi nghin cu mt yu
t ny, thng thng ngi ta phi c lp hay gi cho cc yu t khc khng i. Song
thc cht khng phi nh th, cc qu trnh xy ra trong cuvet graphit khng c lp v
tch bit ln nhau, m chng gn cht vi nhau v c tc ng qua li nh hng ln
nhau nhng mc nht nh di tc dng quyt nh ca nhit trong cuvet
graphit. V th vic xem xt mt yu t trong khi cc yu t khc c gi khng i
ch l tng i trong mt iu kin nht nh dt ra, theo di s thay i ca
mt yu t.
Nhiu tc gi nghin cu cc qu trnh xy ra trong cuvet graphit, song cho
n nay cng ch c nhng kt qu bc u trong mt vi trng hp c th. Chnh v
th cha th nu mt c ch chung ca qu trnh nguyn t ha mu trong cuvet
graphit, do chng ti ch mun cp n mt vi vn chnh c th chp nhn
177

c theo quan im ng hc v nhit ng hc ha hc nhit cao, theo trt t


ca qu trnh nguyn t ha mu.
Qu trnh nguyn t ha mu xy ra theo ba giai on k tip nhau, nh hng
ln nhau. Trong hai giai on u l chun b cho giai on th ba nguyn t ha
mu o cng vch ph. l mt tng th lin tip din bin ca nhiu qu trnh.
Nhng d hiu chng ta c th tch ring v khi qut theo nhng vn sau y:
a. S bay hi ca dung mi. y l qu trnh vt l n gin, n xy ra trong giai
on u (sy mu) ca qu trnh nguyn t ha mu v nhit l yu t quyt nh
s din bin ca qu trnh ny. Nhng thnh phn ca mu, cc cht hu c c mt
trong mu cng nh hng n qu trnh ny. Sau khi dung mi bay hi s li cc
ht mu l bt mn ca cc mui kh trong cuvet.
b. S tro ha (t chy) cc cht hu c v mn. Qu trnh ny xy ra trong giai
on th hai ca qu trnh nguyn t ha. Khi cc cht hu c b tro ha, s to ra cc
cht kh (CO, CO2, H2O) bay i v li phn b v c ca mu. l cc mui hay
cc oxit ca cc cht mu. Tip b ny c nung nng, nng chy hay b phn hy
ty theo nhit tro ha chn v ty thuc vo bn cht ca hp cht mu tn ti
trong cuvet sau khi sy kh. Lc ny mu c luyn thnh th nng chy ng nht.
ng thi y cng c s phn hu ca mt s mui khng bn thnh oxit hay mui
hay oxit n gin. V d, nu trong mu c CaCO3 th c th c phn ng phn hy
nh sau:
CaCO3 (r) Cao(r) + Co2(k)
c. S ha hi ca cc hp phn mu dng phn t. Nu nhit ha hi (nng
lng ha hi) ca cc hp phn mu nh hn nhit phn li ca chng th cc hp
phn mu ny s ha hi dng phn t, sau chng b phn li thnh cc nguyn t
t do. l c ch ha hi ca cc phn t c p sut ha hi cao v nhit ha hi
thp hn nhit phn li (Eh < Ea). Tiu biu cho cc hp cht thuc loi ny l cc oxit
Sb2O3, Ga2O3, cc mui halogen ca cc kim loi nh SbCl5, SnCl4, SnBr4, AlCl3,
TiCl4, GaCl3, cc mui axetat, Clorat ca kim loi, v.v... C ch din bin ca cc hp
cht loi ny c th minh ho theo hai kiu s sau y
- C ch chnh 1:
(a) MxXy(r,l) -- MxXy(k) -- xM(k) + X
(b) MxOy (r,l) -- MxOy(k) -- xM(k) + O2
(c) M(k) + n(hv) ph AAS
Qu trnh (a) xy ra i vi cc mui halogen kim loi v qu trnh (b) l i vi
cc oxit kim loi d ha hi. Nh cc hp cht ZnCl2, CuCl2, FeCl3, CdCl2,Cn qu
trnh (c) l s hp th bc x ca nguyn t, to ra ph.
178

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

theo kiu ny l cc hp cht, cc mui cacbonat, sunphat v photphat ca kim th


Ca, Ba, Si. V d:
FeCl3(r,l) Fe(r,l) Fe(k)
Mn(NO3)2(r) Mno(r,l) Mn(k)
CaO(r) Ca(r) Ca(k)
V2O5(r) VO(r) V(k)
Nh vy, cc qu trnh ny xy ra trong cuvet nh th no ty thuc vo:
+ iu kin nguyn t ha mu (ch yu l nhit ).
+ Tnh cht nhit ha ca cc hp cht mu ,
+ nh hng thnh phn nn ca mu, v
+ Mi trng tin hnh nguyn t ha mu.
+ Cht nn ca mu, cht ph gia thm vo.
e. S to thnh hp cht cacbua kim loi.
Trong cuvet graphit s xut hin hp ht cacbua kim loi l iu tt nhin, nhng
mc rt khc nhau i vi mi kim loi. Ch yu l cc kim loi bn nhit nh
kim th, t him. Phn ng ny thng may xy ra gia cc monooxit kim loi vi
cacbon ca cuvet graphit hay ca kim loi th lng v rn vi cacbon:
(k) M + xC MCx
(l) MO + xC MCx + O2
trong x c th l 1,2,3,4.
Sau cc hp cht cacbua va hnh thnh s ha hi v b nguyn t ha theo
tnh cht, c trng nhit ha ca n. Tt nhin qu trnh ha hi v nguyn t ha ca
cc hp cht loi ny tng i kh khn v phi nhit kh cao, v n l cc hp
cht bn nhit. V th phi ngn nga khng cho cc qu trnh (k) v (l) xy ra. Mc
hnh thnh cc hp cht loi ny rt khc nhau i vi tng kim loi v ph thuc
vo nhiu yu t nh:
+ Tnh cht ca mi kim loi;
+ iu kin nguyn t ha mu, nhit nguyn t ha;
+ Thnh phn ha hc ca mu;
+ Loi cuvet graphit nguyn t ha mu.
Ni chung, cc cuvet graphit hot ha nhit ton phn (pyrolitic coated
graphit) thng hn ch xu hng to thnh hp cht cacbua kim loi. Ngc li, cc
loi cuvet graphit thng (standard graphit cuvet) kh nng hnh thnh cc hp cht
180

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

+ Thnh phn ca mu phn tch, c bit l nguyn t c s (nn);


+ Trng thi b mt v loi cuvet graphit;
+ Mi trng kh tr tin hnh nguyn t ha mu;
+ Cui cng l cht ph gia c thm vo mu.
Chnh do c nhng quan h ph thuc ny, m chng ta c th iu chnh v
khng ch cho mt qu trnh no u vit s xy ra, cn qu trnh no khng c li
s c hn ch hay loi tr.
8.3.6 Trang b nguyn t ha mu
H thng trang b nguyn t ha mu theo k thut khng ngn la bao gm
hai phn chnh:
1. B phn ng mu
nguyn t ha. chnh l
cc loi cuvet graphit, cc
graphit, hay thuyn tantan,
hay l cc loi filamen cha
mu. Trong cc loi ny,
cuvet graphit c dng ph
bin nht v tt nht l cuvet
graphit c hot ha
nhit luyn ton phn. V loi
ny th mi hng ch to my
o ph hp th nguyn t
cng c nhng loi c hnh
dng v kch thc ring cho
my ca h (hnh 8.26).
2. Phn th hai l ngun nng lng nung nng cuvet v gi cuvet.
Phn ny bao gm b chng trnh iu khin theo bn giai on (bn phase)
sy, tro ha, nguyn t ha v lm sch cuvet theo nguyn l ca php o v ngun
nng lng c cng sut cc i l c 3,5 - 7,5 KVA cung cp nng lng cho qu
trnh nguyn t ha mu.
N thng l ngun nng lng in c dng rt cao (thay i c t 50 n
600 A), nhng th rt thp (di 12 V).

182

Hnh 8.26b
H thng nguyn t ha mu trong ngn la (Philips Pye Unicam)

8.3.7 Ti u ha cc diu kin cho php o khng ngn la mu.


N c nghin cu k trn. Do y ch nu li mt s iu cn ch .
C th vi php o ETA-AAS bao gm nhng iu kin:
Cc iu kin nguyn t ha mu:
+ Thi gian, nhit nung nng cuvet ca cc giai on sy mu, tro ha luyn
mu v nguyn t ha o cng vch ph,
183

+ Kh mi trng cho qu trnh nguyn t ha mu (tc , loi khi)


+ Cng sut, tc t nng cuvet graphit nguyn t ha mu;
+ iu kin lm sch cuvet graphit;
+ Lng mu v cch a vo cuvet nguyn t ha cho php o.
- Cht nn ca mu phn tch v cc mu chun cn phi c pha ch v chun
cho ng nht.
Mi trng axit v loi axit pha ch mu v lm mi trng cho dung dch mu
chun v mu phn tch.
- Cc yu t nh hng sau y cng cn c xem xt.
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 trong mu;
+ V nh hng ca thnh phn nn ca mu.

184

Chng 9
TRANG B CA PHP O ASS

9.1 Ngun pht bc x n sc


Mun thc hin c php o ph hp th nguyn t ngi ta cn phi c mt
ngun pht tia bc x n sc (tia pht x cng hng) ca nguyn t cn phn tch
chiu qua mi trng hp th. Ngun pht tia bc x n sc trong php o ph hp
th nguyn t thng l cc n canh rng (HCL), cc n phng in khng in cc
(EDL) v cc n ph lin tc c bin iu ( c n sc ha). Nhng d l loi
no, ngun pht tia bc x n sc trong php o ph AAS cng phi tha mn c
nhng yu cu ti thiu sau y mi c th chp nhn c.
1. Ngun pht tia bc x n sc phi to ra c cc tia pht x nhy (cc vch
pht x nhy, c trng) ca nguyn t cn phn tch. Chm tia pht x phi c
cng n nh, phi lp li c trong nhiu ln o khc nhau trong cng iu kin,
phi iu chnh c vi cng mong mun cho mi php o.
2. Ngun pht tia bc x phi cung cp c mt chm tia pht x thun khit
ch bao gm mt s vch nhy c trng ca nguyn t phn tch. Ph nn ca n phi
khng ng k. C nh th mi hn ch c nhng nh hng v vt l v v ph cho
php o AAS.
3. Chm tia pht x n sc do ngun cung cp phi c cng cao, nhng
li phi bn vng theo thi gian v phi khng b cc yu t vt l khc nhiu lon, t
b nh hng bi cc dao ng ca iu kin lm vic.
4. Ngun pht tia bc x n sc phi bn lu, khng qu t tin v khng qu
phc tp cho ngi s dng.
Tt nhin trong 4 yu cu trn th 3 yu cu u tin l quan trng nht v bt
buc phi tha mn, cho php o t kt qu chnh xc, n nh v tin tng. Ring
yu cu th 4 th c th chnm chc c trong nhng trng hp c th nht nh.
Xut pht t nhng nhim v v yu cu phi tha mn, hin nay trong php o
ph hp th nguyn t, ngi ta thng dng ch yu ba loi ngun pht tia bc x
n sc. l:
+ n catot rng (HCL - Hollow Cathode Lamp),
185

+ n phng in khng in cc (EDL- Electrodeless Discharge Lamp),


+ n pht ph lin tc c bin iu (D2-lamp, W-lamp).
+ Cc loi ngun n sc khc.
Trong ba loi , n HCL c dng ph bin nht. n pht ph lin tc mi
c pht trin v s dng trong vi nm nay, nhng li c nhiu u vit trong cc
my nhiu knh v qu trnh phn tch t ng lin tip nhiu nguyn t, tuy nhin gi
thnh cn t v nhy cn km nn cha c dng ph bin.
9.1.1 n catot rng (HCL)
n pht tia bc x n sc c dng sm nht v ph bin nht trong php o
S l n catot rng (HCL). n ny ch pht ra nhng tia pht x nhy ca nguyn t
kim loi lm catot rng. Cc vch pht x nhy ca mt nguyn t thng l cc vch
cng hng. V th n catot rng cng c gi l ngun pht tia bc x cng hng.
N l ph pht x ca cc nguyn t trong mi trng kh km.
V cu to, n catot rng gm c ba phn chnh:
- Phn 1 l thn n v ca s,
- Phn 2 l cc in cc catot v anot, v
- Phn 3 l kh cha trong n. l kh tr He, Ar hay N2.
- Thn v v. Thn n gm c v n, ca s v b cc in cc anot v
catot. B bng nha PVC. Thn v v n bng thu tinh hay thch anh. V n c
hai dng (hnh 9.1).
Ca s S ca n c th l thu tinh hay thch anh trong sut trong vng UY hay
VIS l ty thuc vo loi n ca tng nguyn t pht ra chm tia pht x nm trong
vng ph no. Ngha l vch pht x cng hng o ph hp th vng no th
nguyn liu lm ca s S phi trong sut vng .
- in cc. in cc ca n l catot v anot. Anot c ch to bng kim loi
tr v bn nhit nh W hay Pt. Catot c ch to c dng hnh xylanh hay hnh ng
rng c ng knh t 3 - 5 mm, di 5 -6 mm v chnh bng kim loi cn phn tch vi
tinh khit cao (t nht 99,9 %).
Dy dn ca catot cng l kim loi W hay Pt. C hai in cc c gn cht trn
b ca thn n v cc catot phi nm ng trc xuyn tnm ca n (hnh 9.1).
Anot t bn cnh catot hay l mt vng bao quanh catot. Hai u ca hai in cc
c ni ra hai cc gn cht trn n, cm vo ngun in nui cho n lm vic.
Ngun nui l ngun 1 chiu c th 220-240 V.
- Kh trong n. Trong n phi ht ht khng kh v np thay vo l mt kh
tr vi p sut t 5 - 15 mHg. Kh tr l argon, heli hay nit nhng phi c sch
186

cao hn 99,99 %. Kh np vo n khng c pht ra ph lm nh hng n chm


tia pht x ca n v khi lm vic trong mt iu kin nht nh th t s gia cc
nguyn t b Ion ha v cc nguyn t trung ho phi l khng i. C nh th n
lm vic mi n nh.
- Ngun nui n. n c t nng pht ra chm tia pht x cng hng
nh ngun in mt chiu n nh. Th lm vic ca n HCL thng l t 250 220V ty thuc vo tng loi n ca tng hng ch to v ty thuc vo tng nguyn
t kim loi lm catot rng.
Cng lm vic ca cc n catot rng thng l t 3- 50 ma v cng ty
thuc vo mi loi n HCL ca mi nguyn t do mi hng ch to ra n.
Th v cng dng in lm vic ca n HCL c lin quan cht ch vi cng
tch kim loi ra khi b mt catot rng to ra hi kim loi sinh ra chm tia pht
x ca n HCL.
Dng in qua n
HCL ca mi nguyn t
rt khc nhau. Mi n
HCL u c dng in
gii hn cc i m n
c th chu ng c v
gi tr ny c ghi trn
v n. Tt nhin khi s
dng khng bao gi c
php dng n dng in cc i , m thch hp nht l trong vng t 65 - 85 % gi
tr cc i, v iu kin dng cc i n lm vic khng n nh v rt chng hng,
ng thi php o li c nhy v lp li km.
Theo l thuyt v thc nghim ca thc t phn tch theo k thut o ph hp th
nguyn t, tt nht ch nn dng cng dng trong vng t 60 - 85 % dng gii hn
cc i ghi trn n HCL.
Mun c nhy cao, nn s dng cng dng gn gii hn di. Mun c
n nh cao, nn dng cng dng gn gii hn trn. Nhng nn nh rng
cng dng lm vic ca n HCL v cng ca vch ph hp th c quan h
cht ch vi nhau.
Ni chung, nhiu trng hp cng ca vch ph hp th l t l nghch vi
cng dng in lm vic ca n HCL (hnh 9.2), tuy nhin cng c vi trng
hp khng tun theo quy lut .
187

Quan h gia cng vch ph v cng dng in lm vic ca n HCL


(A) l trng hp ph bin (Cd-228,8 nm), Cu, Ca, Fe; (B) l ca Pb 283,3 nm,
c bit;
(C) l ca Al 309,3 nm, c bit.
Khi n lm vic, catot c nung , gia catot v anot xy ra s phng in
lin tc. Do s phng in m mt s phn t kh b Ion ha. Cc Ion va c
sinh ra s tn cng vo catot lm b mt catot nng v mt s nguyn t kim loi
trn b mt catot b ha hi v n tr thnh nhng nguyn t kim loi t do. Khi
di tc dng ca nhit trong n HCL ang c t nng , cc nguyn t kim
loi ny b kch thch v pht ra ph pht x ca n. chnh l ph vch ca chnh
kim loi lm catot rng. Nhng v trong iu kin c bit ca mi trng kh tr c
p sut rt thp, nn ph pht x ch bao gm cc vch nhy ca kim loi m
thi. chnh l s pht x ca kim loi trong mi trng kh km. Chm tia pht x
ny l ngun tia n sc chiu qua mi trng hp th thc hin php o AAS.
Cc n catot rng c cu to nh m t trn l nhng n HCL n nguyn
t, ngha l mi n HCL ch phc v cho phn tch mt nguyn t. Ngy nay ngoi
cc n HCL n, ngi ta cng ch to c mt s n kp i, kp ba hay kp
su nguyn t. V d cc n kp i l (Ca+Mg), (Cu+Mn), (Cu+Cr), (Co+Ni),
(K+Na), (Cu+Pb); cc n kp ba nh (Cu+Pb+Zn) v n kp su l
(Cu+Mn+Cr+Fe+Co+Ni).
ch to cc n kp ny, catot ca n HCL phi l hp kim ca cc nguyn
t . Hp kim ny phi c thnh phn ph hp, sao cho cng pht x ca cc
nguyn t l gn tng ng nhau; ngha l s pht x ca kim loi ny phi khng
c ln t s pht x ca nguyn t kia. Do phi ch to trong iu kin dung ha
cho tt c cc nguyn t. V d: n HCL kp su ca Cu, Mn, Cr, Fe, Co, v Ni th
hp kim lm catot rng phi cha 25% Cu, cc nguyn t khc c thnh phn l 15%.
188

Xt v nhy, ni chung cc n kp thng c nhy km hn cc n n


tng ng, hay tt nht cng ch gn bng l cng. Mt khc, v ch to li kh khn
hn n n. V th cng ch c mt s t n kp v cng ch c dng trong mt s
trng hp khi vic thay i n c nh hng n qu trnh phn tch v trong cc
my nhiu knh th n HCL kp l u vit hn n n.
n HCL lm vic ti mi ch dng nht nh th s cho chm sng pht x
c cng nht nh.
Mi s dao ng v dng in lm vic ca n u lm nh hng n cng
ca chm tia sng pht x (hnh 9.2). Do trong mi php o c th phi chn
mt gi tr cng dng in ph hp v gi c nh trong sut qu trnh o nh
lng mt nguyn t.
9.1.2 n phng in khng din cc (EDL)
Ngun pht tia bc x n sc th hai c dng trong php o ph hp th
nguyn t l n phng in khng in cc.
Loi n ny cng nh n HCL u c nhim v cung cp chm tia pht x c
trng ca nguyn t phn tch, c bit l cc kim, th n EDL cho nhy cao hn,
n nh hn n HCL. Bng 9.1 v hnh 9.3 l nhng v d v iu .
Bng 9.1
So snh nhy v gii hn pht hin ca n HCI v EDL
Nguyn t

nhy (l/mL)

Gii hn pht hin (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

V cu to, n EDL thc cht cng l mt ng phng in trong mi trng kh


km c cha nguyn t cn phn tch vi mt nng nht nh ph hp to ra
c chm tia pht x ch bao gm mt s vch ph nhy c trng ca nguyn t
phn tch. n EDL cng gm cc b phn:

189

- Thn n: Mt ng thch anh chu nhit, di 18 - 15 cm, ng knh 6 - 5 cm.


Mt u ca n EDL cng c ca s S. Ca s cho chm sng i qua cng phi trong
sut vi chm sng .
Ngoi ng thch anh l cun cm bng ng. Cun cm c cng sut t 800 400 W ty loi n ca tng nguyn t, v c ni vi ngun nng lng cao tn HF
ph hp nui cho n EDL lm vic (hnh 9.4). Ngoi cng l v t chu nhit.
- Cht trong n l vi miligam kim loi hay mui kim loi d bay hi ca
nguyn t phn tch, lm sao khi ton b cht ha hi bo m cho p sut hi ca
kim loi trong n iu kin nhit t 800 - 550oC l khong t 1 - 1,5 mmHg.
Cht ny thay cho catot trong n HCL, n l ngun cung cp chm tia pht x
ca nguyn t phn tch, khi chng b kch thch, trong qu trnh n EDL hot ng.
- Kh trong n. Trong n EDL cng phi ht ht khng kh v np thay vo
l mt kh tr Al, He hay Nit c p sut thp, vi mmHg khi u cho s lm vic
ca n EDL.
- Ngun nui n lm vic. Ngun nng lng cao tn nui n EDL lm vic
c ch to theo hai tn s. Tn s sng ngn 450 MHz v tn s sng raio 27,12
MHz, c cng sut di 1 kW.
Do ngun nui l nng lng cm ng in t vi hai tn s khc nhau nn n
EDL cng c chia thnh hai loi: 1. n EDL sng ngn, ngun nui tn s 450
MHz, v 2. n EDL sng raio, ngun nui tn s sng raio 27,12 MHz.

190

191

Cng vch ph v vng tuyn tnh ca As-193,7 v Se-196,1 i vi hai loi


n HCL v EDL. Khi n lm vic, di tc dng ca nng lng cao tn cm ng
n c nung nng , kim loi hay mui kim loi trong n c ha hi v b
nguyn t ha. Cc nguyn t t do c sinh ra s b kch thch v pht ra ph
pht x ca n trong iu kin kh km di tc dng nhit khi n lm vic. chnh
l ph vch ca kim loi cha trong n EDL.
Ngoi u im v nhy v gii hn pht hin, n EDL ca cc kim hay bn
kim thng c bn cao hn n HCL. ng thi vng tuyn tnh ca php o mt
nguyn t khi dng n EDL thng rng hn so vi vic dng n HCL (hnh 9.4).
Ngy nay cc hng sn xut my o ph hp th nguyn t sn xut c n
30 loi n EDL cho 30 nguyn t. Nhng tt v c dng nhiu ch c 12 nguyn t
kim v bn kim l As, Bi, Cd, Hg, P, Pb, Se, Sn, Te, TI v Zn. Cc n EDL ca
cc nguyn t ny u c bn theo cc my ca hng. Nhng n EDL ca cc
nguyn t khc cn li t c s dng, v n khng u vit hn n HCL, m gi
thnh li t hn.
Ngoi n catot rng v n phng in khng in cc, ngi ta cng ch
to ra c nhiu loi n pht tia bc x n sc ca cc nguyn t, nh n catot
rng cng cao (trnh intensity cmiss Ion lamp - HIEL), n gradient nhit
(controlled temperature-gradient lamp - CTGL), n phng in c chi sng cao
(glow- discharge lamp - GDL). Cc loi kin ny c u im hn n HCL mt cht
v nhy, v vng tuyn tnh, v gii hn pht hin. Nhng cc n loi ny li kh
ch to v t tin, mt khc li km bn vng. V th n t c dng v khng c
bn ngoi th trng, ch yu ch c ng trong nghin cu l thuyt v ph.
9.1.3 n ph lin tc c bin iu
Trong khong vi nm li y, mt loi ngun pht x ph lin tc cng c
dng lm ngun pht bc x cng hng cho php o AAS. l n hydrogen nng
(D2-lamp), cc n xenon p sut cao (Xe-lamp), cc n hot ca kim loi W. l
cc loi n pht ph lin tc trong vng t ngoi v vng kh kin (UV-VIS). Cc tc
192

gi Fassel, Ivanop, Gibson, Mc G, Winerfordner l nhng ngi u tin nghin


cu v s dng cc loi n ny lm ngun pht bc x cng hng cho php o AAS.
n ny tuy pht ra ph lin tc, nhng nh h thng bin iu v h lc giao
thoa, nn chm sng pht x b bin iu v lng t ha thnh chm sng
khng lin tc c ph dng rng ca, mi rng ca cch nhau 0,2 nm, nn mi rng
ca c coi nh l 1 tia n sc. Hnh 9.5 l mt v d v h my o ph hp th
nguyn t dng ngun sng bc x lin tc. Trong ngun sng c t trc h
thng bin iu v b lc giao thoa. Chm sng ny khi i qua h thng bin iu v
b lc giao thoa s b bin iu theo nhng di sng nht nh dao ng vi bin
nh nhau. Sau cng c chiu vo mi trng hp th l ngn la hay cuvet
graphit. Cc nguyn t t do trong mi trng hp th s hp th mt phn nng lng
ca chm sng ng vi mt di bin iu ca vng ph. Phn cn li s i vo b
n sc v detector pht hin v o cng sau khi qua b khuych i bng sng
theo di ph ca n nn li tn s. Tip cng vch ph hp th cng c
o v ch th theo cc cch bit, nh hin s digital, ghi pic trn recorder, hay dng
printer in ln bng giy.

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

cao, v ch cn mt n c th thc hin c php o AAS i vi nhiu nguyn t


trong mt vng ph UY hay VIS. Do n rt u vit i vi cc my ph hp th
nhiu knh v xc nh ng thi hay lin tip nhiu nguyn t trong cng mt mu
phn tch, m khng phi thay n HCL cho vic o ph mi nguyn t. Vi n ny,
vng tuyn tnh rng, li khng c hin tng t hp th ring (t o). Song v
n sc v chn lc hay nhy, th ni chung trong nhiu trng hp cn km cc
n HCL hay n EDL nhng li u vit v d dng i vi qu trnh phn tch t
ng hng lot trong cc my o ph hp th nhiu knh. Chnh v th m trong
khong nm nm li y cc loi n ph lin tc c pht trin, ci tin v bt
u c s dng rt nhiu trong php o AAS v nhiu h thng my o ph hp th
vi ngun pht ph lin tc cng c bn trn th trng th gii.
9.1.4 Cc loi ngun n sc khc
Ngoi ba loi ngun pht bc x n sc ch yu c trnh by trn, trong
php o ph hp th nguyn t, ngi ta cng s dng mt vi loi ngun pht tia bc
x n sc khc na nh n catot rng c di cao, ng pht x c bit, tia laze.
Nhng nhng loi ny ch ch yu dng trong nghin cu l thuyt vt l.
9.2 Trang b nguyn t ha mu
nguyn t ha mu, trong php o ph hp th nguyn t ngi ta thng
dng hai k thut khc nhau. l k thut nguyn t ha bng ngn la ca n kh
v k thut nguyn t ha khng ngn la. ng vi hai k thut nguyn t ha c
hai loi dng c nguyn t ha mu.
K thut ngn la. H thng nguyn t ha mu bng ngn la gm hai phn
chnh:
+ Bung aerosol ha (Nebulizer system), to th si kh mu,
+ n nguyn t ha mu (burner head).
Kh to ra ngn la nguyn t ha mu thng hay c dng l hn hp ca
2 cht kh (1 cht oxy ha v 1 cht chy), v d nh hn hp khng kh nn vi
axetylen hay kh N2O vi kh axetylen. i khi cng dng hn hp ca kh hydro vi
axetylen hay khng kh v kh propan.
- H thng nguyn t ha khng ngn la. H thng ny gm ba phn chnh l:
+ Cuvet graphit hay thuyn Ta cha mu, nguyn t ha.
+ Ngun nng lng nung cuvet hay thuyn Ta.
+ B iu khin thc hin vic nguyn t ha mu theo cc giai on ca mt
chng trnh ph hp.
Nguyn l cu to, qu trnh hot ng ca cc loi trang b nguyn t ha
mu c m t chi tit trong chng 8 v k thut nguyn t ha mu.
194

9.3 H thng n sc v my quang ph hp th nguyn t


H thng n sc chnh l h thng thu, phn li, chn v pht hin vch ph
hp th cn phi o. Trong php o ph hp th nguyn t h thng n sc ny l
mt my quang ph c phn gii tng i cao c th l h my mt chm tia hay
h my 2 chm tia. Cu to ca n gm ba phn chnh:
- H chun trc, chun trc chm tia sng vo;
- H thng tn sc (phn li) phn li chm sng a sc thnh n sc;
- H bung ti (bung nh) hi t, hi t cc tia cng bc sng li.
c trng cho h quang ca my AAS l cc thng s.
+ tn sc gc;
+ tn sc di;
+ phn gii (tn sc);
+ Vng ph lm vic ca h.
Bn thng s ny cng l cc yu t xem xt cht lng ca mt my quang
ph AAS.
Trc h chun trc l khe vo ca chm sng a sc v sau h bung nh l khe
ra ca chm tia n sc cn o. Hnh 3.6 l s quang hc, nguyn tc ca h thng
my quang ph hp th nguyn t. Theo s ny, chm tia pht x cng hng ca
nguyn t cn nghin cu c pht ra t n catot rng sau khi qua mi trng hp
th, s c hng vo khe my v vo h chun trc, ri vo b phn tn sc, vo h
hi t chn 1 tia cn o. Nh vy chm sng a sc c chun trc, c phn li
v sau ch mt vch ph cn o c chn v hng vo khe o tc dng vo
nhn quang in (detector-photomultiveler) pht hin v xc nh cng ca
vch ph hp th .
Mun h thng my quang ph hp th nguyn t cho c kt qu tt th h
thng tn sc phi bo m c mt s yu cu bt buc sau y:
1. N phi c tn sc ln c th tch v c lp c tt cc vch ph
cn o, trnh s quy ri, s chen ln ca cc vch ph khc bn cnh. Trong cc
my hin nay, b phn ny thng l mt h cch t c hng s t 1200 n 2400
vch/mm.
2. Phi khng gy ra bt k mt hin tng sai lch no lm mt nng lng ca
chm sng trong my, nh s hp th, s tn x, s khuych tn ca cc b phn cu
to thnh my. c bit l cc h thng gng, cc thu knh, khe vo, khe ra ca
chm sng. Cc thu knh phi trong sut trong vng ph lm vic ca my.
3. Khe vo v khe ra ca my phi c m chnh xc v phi iu chnh c
cho ph hp vi tng vch ph v c lp li cao trong mi php o.
195

4. Detector pht hin cng vch ph phi c nhy cao. C nh th mi


c th pht hin c s thay i nh trong qu trnh hp th ca vch ph ca mi
nguyn t. l cc iu kin ti thiu ca h quang hc trong my ph hp th
nguyn t. Vi s pht trin ca khoa hc v k thut, ngy nay ngi ta c th tha
mn c tt c cc yu cu . Chnh v th hin nay c rt nhiu my o ph hp
th nguyn t c cht lng cao c bn trn th trng quc t. l cc my o
ph hp th nguyn t ca hng Perkin Elmer, Varian, Becman, Philips Pye Unicam,
Wet Zeiss, Shimadu, Instr, Lad, Alpha,...

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

9.5 K thut o cng vch ph hp th


Cng ca cc vch ph hp th sau khi c detector pht hin v khuych
i s c a sang h thng ch th kt qu. y n c th c khuych i tip
v x l c c cng thc ca vch ph hp th. n nay ch th (biu th)
cng ca vch ph hp th nguyn t, c nhiu cch khc nhau t n gin n
tinh vi phc tp. Sau y l mt vi k thut v ang c s dng trn cc my o
ph hp th c bn trn th trng quc t.
1. Thang o mt quang (thang o
nng lng hp th ca vch ph).
y l mt phng php n gin
nht v c dng t khi my quang
ph hp th nguyn t mi ra i.
Theo cch ny, cng ca vch
ph hp th c biu th theo thang
o mt quang D. Thang o ny
c cu to v phn chia theo quy
lut ca thang logarit ca t s gia
cng tia sng i vo v i ra khi
mi trng hp th.
Nh vy, im gc ca thang o s c mt quang D = 0, ngha l khng c s
hp th. im cui ca thang o l im c hp th l 100%, ngha l D = 2. Trn
tt c cc my hin nay u c thang o ny. Cc gi tr D c c trc tip trn
thang o theo lch ca kim in k ch nng lng hp th E ca vch ph.
2. Phng php hin s (digital) ch hp th ca vch ph. y l mt k thut
biu th cng vch ph cng ang c dng hin nay. Cc s o hin trn mn
digital ch trc tip nng lng hp th ca vch ph cn o. Cng tng t nh thang
o mt quang D, cc s o ny cng t l vi nng ca nguyn t trong mu
theo phng trnh c bn ca php o AAS. Ngy nay tt c cc my o ph hp th
nguyn t u c b phn ch th cng vch ph theo nguyn tc ny. N c tn l
b Readout. B Readout ca cc my thng c 4 hng s l t 0 n + 9999.
3. Ghi cng vch ph dng pic. Cng ca vch ph hp th c th
c a sang my ghi (Recorder) ghi li di dng cc lc. S o cng vch
ph lc ny c th c tnh theo chiu cao ca lc hay din tch ca lc. V trong mt
gii hn nht nh nng C ca nguyn t phn tch chng ta lun lun c quan h:
H = kC
hay l

S = kC

Trong H l chiu cao v S l din tch ca lc. Cn k l mt h s t l. Hnh


9.9 l mt v d v cc lc ca vch ph hp th vi cc nng khc nhau.
198

Nh vy, qua vic o gi tr H hay S chng ta cng dng c ng chun v


xc nh c nng Cx cha bit theo mt cch ph hp tng ng. Cc my o
ph hp th nguyn t hin nay u c u sang my t ghi th o 0 - 10 mV v
a ra b intergrator t 0 - 1 V.
4. Phng php in trc
tip gi tr o bng my in
(printer). y l mt k thut
hin i, nhanh v tin li.
y cc s o cng vch
ph hp th c in ngay trn
bng giy nh my in (printer)
theo tng ln o v sau c
gi tr trung bnh ca n ln o.
y l k thut mi c pht
trin. Do ch nhng my o
ph hp th nguyn t hin i
mi c u a tn hiu ra
ch th theo cch ny. Bng 9.2
l mt v d v cch o ny.
Bng 9.2
V d v bng kt qu o ph ca mu (trch trong Report 09/20 - hng Philips)
Sample ID

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

5. Microcomputer v mn video. y l mt k thut ch th s o hin i nht


hin nay, nhanh v tin li. Cc my o ph hp th nguyn t hin nay u c u
ghp vi b phn ny. Microcomputer l trung tnm ch huy ton b mi hot ng ca
h thng my AAS, iu khin mn video ch th cc thng s nghin cu v cc kt
qu o c t ra theo mt chng trnh nht nh. Microcomputer nhn s o t
199

detector, n x l theo cc yu cu t ra v sau ch theo mt cch nht nh ca


s o cng vch ph, nh printer, ghi chiu cao hay din tch lc, hoc hin s
trn mn vi deo. V th y l k thut vn nng nht.
Trn y l cc phng php ang c dng ch th cng ca vch ph.
Hin nay, cc h thng my o ph hp th nguyn t bn trn th trng quc t
u c cc cch o cng vch ph nh th. Song chng ta c th s dng ng
thi, hay chn mt k thut no l ty thuc vo mc trang b hin c ca tng
phng th nghim v tng ngi nghin cu c nhng yu cu cn thit nht nh cho
ph hp. Nhng mun c c kt qu ng n v chnh xc, ngoi vic c c
trang b hin i, cn phi c con ngi c kin thc v hiu bit chnh xc v php o
AAS; Nh th mi lm ch c trang b phc v cho cng vic nghin cu ca mnh.

200

Chng 10
CC YU T NH HNG TRONG AAS

10.1 Khi qut chung


Cc yu t nh hng n kt qu phn tch trong php do ph hp th nguyn t
rt a dng v phc tp, c khi xut hin v cng c khi khng xut hin, c nh
hng hay khng l ty thuc vo thnh phn ca mu phn tch v matrix ca n.
Nhng nghin cu mt cch ton din, chng ta im qua tt c cc yu t nh
hng c th c trong php o ny. Cc yu t c th c chia thnh 6 nhm sau:
Nhm l: Cc thng s ca h my o ph. Cc thng s ny cn c kho st v
chn cho tng trng hp c th. Thc hin cng vic ny chnh l qu trnh ti u
ha cc thng s ca my o cho mt i tng phn tch.
Nhm 2: Cc iu kin nguyn t ha mu. Cc yu t ny th hin rt khc
nhau ty thuc vo k thut c chn thc hin qu trnh nguyn t ha mu v n
c nghin cu k trong chng II.
Nhm 3: K thut v phng php c chn x l mu. Trong cng vic ny
nu lm khng cn thn s c th lm mt hay lm nhim bn thm nguyn t phn
tch vo mu. Do kt qu phn tch thu c khng ng vi thc t ca mu. V
th, vi mi mt loi mu ta phi nghin cu v phi chn mt quy trnh x l ph hp
nht, c c ng thnh phn ca mu v khng lm nhim bn mu. Vn ny
s c nghin cu trong mt chng ring.
Nhm 4. Cc nh hng v ph.
Nhm 5. Cc yu t nh hng vt l.
Nhm 6. Cc yu t ha hc.
Trong chng ny chng ta s nghin cu k cc yu t thuc cc nhm 4, 5 v 6.
10.2 Mt s nh hng trong php do AAS
10.2.1 Cc yu t v ph
10.2.1.1 S hp th nn
201

Yu t ny c trng hp xut hin r rng, nhng trong nhiu trng hp khng


xut hin. iu ny ph thuc vo vch ph c chn o nm trong vng ph no.
Ni chung, trong vng
kh kin th yu t ny th
hin r rng. Cn trong vng
t ngoi th nh hng ny t
xut hin, v ph nn trong
vng t ngoi yu. Hn na,
s hp th nn cn ph thuc
rt nhiu vo thnh phn nn
ca mu phn tch, c bit l
matrix ca mu, ngha l
nguyn t c s ca mu. V
d: Khi xc nh Pb trong
mu sinh hc bng php o
ngn la th s hp th nn l
khng ng k, nhng khi xc nh Pb trong nc bin (nn 2,9% NaCl) th nh
hng ny l v cng ln (hnh 10.1).
Do , trong mi trng hp c th phi xem xt tm bin php loi tr.
loi tr ph nn, ngy nay ngi ta lp thm vo my quang ph hp th nguyn t h
thng b chnh nn.
Trong h thng ny
ngi ta dng n hydro
nng (D2-lamp) b chnh
nn trong vng t ngoi v
dng n W (W-habit lamp)
cho vng kh kin. Do ,
trong mi php o xc
nh mt nguyn t chng ta
c th thc hin b chnh
nn hay khng l ty thuc
vo yu t c nh hng
hay khng. Hn na, ngy
nay ngi ta dng c hiu
ng Zeeman b chnh
nn. K thut ny khng
nhng b chnh c nn c
hiu qu cao hn (hnh
10.2b), nht trong cc mu
202

nng mui nn ln, m cn tng c nhy ca php o ln nhiu ln, v hiu


ng Zeeman c tc dng lm tng cng ca vch ph hp th nguyn t ca cc
nguyn t. K thut b chnh th ba l dng n HCL hot ng hai ch k tip:
ch dng thp (o tn hiu hp th tng) v ch dng cao (ch o cng hp
th nn). Hiu gia 2 ln o l tn hiu hp th thc ca vch ph. Cch b chnh
ny tuy c tin hn, v ch cn 1 n HCL, nhng n HCL li chng hng, do phi
dng ch dng cao lin tc trong qu trnh o ph.
10.2.1.2 S chen ln ca vch ph
Yu t ny thng thy khi cc nguyn t th ba trong mu phn tch c nng
ln v thng l nguyn t c s ca mu. Tuy nguyn t ny c cc vch ph
khng nhy, nhng do nng ln, nn cc vch ny vn xut hin vi rng ln,
nu n li nm cnh cc vch phn tch (bng 10.1a), th cc vch ph ny s chen ln
cc vch phn tch, lm cho vic o cng vch ph phn tch rt kh khn v thiu
chnh xc, nht l i vi cc my c phn gii khng cao. V th, trong mi mc
ch phn tch c th cn phi nghin cu v chn nhng vch phn tch ph hp
loi tr s chen ln ca cc vch ph ca nguyn t khc. Nu bng cch ny m
khng loi tr c nh hng th bt buc phi tch b bt nguyn t c vch ph
chen ln ra khi mu phn tch trong mt chng mc nht nh, cc vch chen ln
khng xut hin na.
Bng 10.1a
S chen ln v s trng vch ca cc nguyn t
Nguyn t

Nguyn t c vch chen ln (ppm)

v vch phn tch (nm)

Vch chen ln

Al-308,215

V-308,211

Nng xut hin s chen ln


(ppm)
800

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

hp th gi, do cng gy ra nhng sai s cho kt qu o cng vch ph thc.


Yu t ny th hin rt r khi chn khng ng chiu cao ca n nguyn t ha mu
v khi hn hp kh chy khng c t chy tt, hay do thnh phn ca hn hp kh
chy khng c chn ph hp (thng l qu d axetylen).
10.2.2 Cc yu t vt t
Thuc v loi yu t vt l ny thng c:
10.2.2.1 nht v sc cng b mt ca dung dch mu
Trong php o AAS, vi k
thut nguyn t ha mu
trong ngn la, 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 mu t
l nghch vi nht ca
dung dch mu (hnh 10.3).
Chnh s khc nhau v nng axit, loi axit, nng cht nn ca mu, thnh
phn ca cc cht c trong dung dch mu l nguyn nhn gy ra s 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 lp 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 FAAS. loi tr nh hng ny chng ta c th dng cc bin php sau y:
+ o v xc nh theo phng php thm tiu chun,
+ Pha long mu bng mt dung mi hay mt nn ph hp,
+ Thm vo mu mt cht m c nng ln, ng nht nht,
+ Dng bm y mu vi mt tc xc nh m chng ta mong mun.
10.2.2.2 Hiu ng 1u li
Yu t ny th hin r rng c bit trong php o ph hp th khng ngn la
v cng ln khi cht phn tch c nng ln, ng thi cng ph thuc vo bn cht
ca cc nguyn t, hp cht n tn ti trong mu, cng nh loi cuvet graphit c
dng nguyn t ha mu. Ni chung, cc nguyn t kh bay hi v d sinh ra hp
cht bn nhit lun lun gy ra nh hng ny. Cc cuvet c ch to t graphit
hot ha thng hn ch c hiu ng ny. Hn na, b mt bn trong ca cuvet
204

cng l mt yu t ng gp vo hiu ng ny, ngha l b mt cng mn th nh


hng cng nh, b mt cng xp th nh hng cng ln. Do tnh cht ny m khi
nguyn t ha mu o cng vch ph th mt lng nh ca nguyn t phn
tch khng b nguyn t ha, chng c lu li trn b mt cuvet v c th tch t li
qua mt s ln nguyn t ha mu. Nhng n mt ln no th n li b nguyn t
ha theo v do to ra s nguyn t t do ca nguyn t phn tch tng t ngt
khng theo nng ca n trong mu, ngha l lm tng cng ca vch ph v
dn n lm sai lc kt qu phn tch. V th cn phi loi tr nh hng ny. loi
tr nh hng ny chng ta c th theo cc cch sau:
+ Lm sch cuvet sau mi ln nguyn t ha mu, lm bay hi ht cc cht
cn li trong cuvet. Tt nhin phi thc hin nhit cao hn nhit nguyn t ha
nguyn t phn tch;
+ Dng cc loi cuvet c ch to t cc loi graphit c hot ha ton
phn, c b mt chc v mn;
+ Khi phn tch nn o cc mu c nng nh trc;
+ Thm vo mu nhng cht m c nng ph hp;
+ Trng b mt trong ca cuvet graphit bng mt lp cc hp cht bn nhit.
Tt nhin y ch l nhng nguyn tc chung. Cn trong thc t phi ty tng
trng hp c th m chn cc bin php ph hp nht.
10.2.2.3 S Ion ha ca cht phn tch
y l yu t vt l th ba nh hng n kt qu phn tch, v qu trnh Ion ha
thng lm gim s nguyn t t do ca nguyn t phn tch trong mi trng hp th
to ra ph, do lm gim cng vch ph hp th, nu nguyn t phn tch b Ion
ha cng nhiu. Nhng mc b Ion ha ca mi nguyn t l khc nhau, v cn ph
thuc vo nhit ca mi trng hp th. 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,
th khi nhit ca mi trng hp th cng cao, nguyn t cng b Ion ha nhiu
hn. Bng 10.1b l mt v d v iu ny.
Bng 10.1b
Mc Ion ha ca mt s nguyn t
Nguyn t

Ion ha (eV)

S % b Ion ha nhit (oC):


20,00

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

Thc t cho thy rng, qu trnh Ion ha thng ch c ngha i vi cc kim


loi kim v sau l cc kim loi kim th, cn i vi cc nguyn t khc s Ion
ha khng ng k trong mi trng hp th ca php o ph hp th nguyn t (FAAS hay ETA-AAS). loi tr s Ion ha ca mt nguyn t phn tch chng ta c
th dng cc bin pht sau y:
+ Chn iu kin nguyn t ha c nhit thp ph hp, m trong iu kin
nguyn t phn tch hu nh khng b Ion ha.
+ Thm vo mu phn tch mt cht m cho s Ion ha. l cc mui halogen
ca cc kim loi kim c th Ion ha thp hn th Ion ha ca nguyn t phn tch vi
mt nng ln ph hp. Nh vy trong iu kin nguyn t phn tch s khng b
Ion ha na. Hnh 10.4 l mt v d v tc dng ca cht m KCl v NaCl trong vic
loi tr s Ion ha ca hai
nguyn t phn tch Ba v
Rb. Trong trng hp ny
nng ca kim loi m
phi thm vo ti thiu l
250 g/mL th nh hng
ca s Ion ha l khng
cn na. Ni chung, khi
xc nh cc nguyn t
kim th th ngi ta
thng dng KCl, khi phn
tch cc kim loi kim
ngi ta thng thm CsCl
vo mu phn tch theo
trong ph hp (500 1000 ppm).
10.2.2.4 S pht x ca nguyn t phn tch
Yu t ny xut hin thng lm gim nng ca cc nguyn t trung ho c
kh nng hp th bc x trong mi trng hp th, do cng lm gim cng ca
vch ph hp th. Ni chung cc nguyn t c th kch thch ph pht x thp thng
b nh hng nhiu. ng thi mi trng hp th c nhit cng cao th nh hng
ny cng ln (bng 10.2). Nhng trong nhit ca php o AAS, th s kch thch
ph pht x thng ch xy ra mnh ch yu i vi cc kim loi kim v sau l cc
kim th, v cc nguyn t ny c th kch thch ph pht x tng i thp. Cn cc
kim loi khc th s kch thch ph pht x l khng ng k (bng 10.2).
206

loi tr nh hng ca s pht x ca nguyn t phn tch chng ta c th


dng cc bin php sau y:
- Chn nhit nguyn t ha mu thp ph hp m ti nhit s kch thch
ph pht x l khng ng k hoc khng xy ra i vi nguyn t phn tch.
- Thm vo mu cc cht m hn ch s pht x ca nguyn t phn tch.
chnh l cc mui halogen ca cc kim loi kim, c th kch thch ph pht x thp
hn th kch thch ph pht x ca nguyn t phn tch.
Bng 10.2
Mc b kch thch ph pht x ca cc nguyn t trong cc nhit khc nhau
No- S nguyn t trung ho ban u; Ni - S nguyn t b kch thch ph pht x
Nguyn t

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

Trn y l mt s yu t vt l c th c xut hin trong php o AAS v c th


nh hng n kt qu phn tch. Nhng mc xy ra l rt khc nhau trong mi
trng hp c th, c khi c, c khi khng. Mc ny xut hin ln hay nh l c
ph thuc vo nhit ca mi trng hp th, tnh cht ca nguyn t phn tch, v
thnh phn ca mu phn tch. Do cn phi xem xt tm bin php loi tr khi
chng xut hin.
10.2.3 Cc yu t ha hc
Trong php o ph hp th nguyn t cc nh hng ha hc cng rt a dng v
phc tp, n xut hin cng rt khc nhau trong mi trng hp c th v cng nhiu
trng hp khng xut hin. Cc nh hng ha hc thng c th dn n kt qu
theo bn hng sau y:
- Lm gim cng ca vch ph ca nguyn t phn tch, do s to thnh cc
hp cht bn nhit, kh ha hi v kh nguyn t ha, v d nh nh hng ca cc
Ion silicat, sunfat, photphat, florua.
- Lm tng cng ca vch ph, do s to thnh cc hp cht d ha hi v d
nguyn t ha, hay do hn ch c nh hng ca s Ion ha v s kch thch ph
pht x ca nguyn t phn tch. chnh l tc dng ca mt s hp cht, ch yu l
mui halogen ca kim loi kim v kim th hay lantanClorua.
- S tng cng vch ph khi nguyn t phn tch tn ti trong nn ca mu l
nhng hp cht d ha hi. Lc cc cht nn ny c tc dng nh l mt cht mang
cho s ha hi ca nguyn t phn tch v lm cho n c ha hi hiu sut cao hn.
- S gim cng ca vch ph khi nguyn t phn tch tn ti trong nn ca
mu l nhng hp cht bn nhit, kh ha hi. Lc ny cc nguyn t nn km hm s
207

ha hi ca nguyn t phn tch. Cc cht nn ny thng l nhng hp cht bn nhit


ca cc nguyn t, nh Al, t him, v.v...
V th vic nghin cu cc nh hng ha hc c trnh by trong chng ny
c tnh cht khi qut chung tt c cc loi c th c chng ta lu khi ng dng
php o ph hp th nguyn t, vi mc ch bit v loi tr cc nh hng ha
hc nu chng xut hin. Cc yu t nh hng v mt ha hc c th c sp xp
theo cc loi sau y, d xem xt v tm cch loi tr:
10.2.3.1 Nng axit v loi axit trong dung dch mu
Nng axit trong
dung dch mu lun lun
c nh hng n cng
ca vch ph ca
nguyn t phn tch thng
qua tc dn mu, kh
nng ha hi v nguyn t
ha ca cht mu. nh
hng ny thng gn lin
vi loi Anion ca axit.
Ni chung, cc axit cng
kh bay hi v bn nhit,

cng lm gim nhiu cng vch ph hp th ca nguyn t phn tch.


Cc axit d bay hi gy nh hng nh (hnh 10.5). iu ny c th thy r rng
khi xc nh Ca lc o vch ph Ca-422,7 nm trong cc mi trng ca cc axit
HClO4, CH3COOH, HCl, HNO3, H2SO4, H3PO4, HF vi cng mt nng l 2%
(hnh 10.6).
Ni chung, cc axit lm gim cng vch ph theo th t: HClO4 < HCl:

208

HNO3 < H2SO4 < HaPO4


< HF, ngha l axit HClO4 <
HCl v HNO3 gy nh hng
nh nht trong vng nng
nh. Chnh v th trong thc t
phn tch ca php o ph hp
th nguyn t (AAS) ngi ta
thng dng mi trng l
axit HCl hay HNO3 1 hay 2%.
V nng nh th nh
hng ca hai axit ny l
khng ng k (nh hn 5%).
10.2.3.2 V nh hng
ca cc Cation c trong mu:
Dung dch mu phn tch, ngoi nguyn t cn xc nh, thng cn cha cc
nguyn t khc. Cc nguyn t ny tn ti di dng cc Cation hay Anion tan trong
dung dch mu. Cc Ion ny c th lm tng, cng c th lm gim, hoc cng c th
khng gy nh hng g n cng vch ph ca nguyn t phn tch. Khi c nh
hng th mc nh hng ca mi Ion cng rt khc nhau trong tng trng hp c
th. Nhng mt cch tng qut th chng ta c th quy nh hng ca cc Cation theo
7 loi nh trong hnh 10.7 d xem xt.
Nh vy nh hng ca cc Cation n cng vch ph ca nguyn t phn
tch c th c hiu ng dng, hiu ng nm v cng c th c hiu ng va nm va
dng i vi mt Ion, khi n cc nng khc nhau.

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

nh hng cc Cation trong dung dch mu n cng vch ph ca nguyn


t phn tch trong php o ph hp th nguyn t vi k thut nguyn t ha trong
ngn la v khng ngn la cng rt khc nhau.
V d. Ion La(III) trong php o F-AAS l yu t loi tr nh hng ca cc
Ion l khi xc nh Ca, Mg, Mn, Al, Fe. Nhng chnh La(III) li l Ion lm gim
cng vch ph ca chnh Ca, Mg, Al, Fe rt ln trong php o ETA-AAS. iu
c ngha l mi Cation trong tng trng hp c th v trong mi php li c tc
dng khc nhau, m chnh n trong php o ny th nh hng, nhng trong php o
khc li khng gy nh hng.
minh ho v nh hng ca cc Cation l i vi vch ph ca nguyn t
phn tch chng ta c th xem xt mt s v d trong cc hnh t 10.8 - 10.11.
Hnh 10.8 l nhng v d v cc nh hng cc Cation thuc loi 1, 2 v 3. Cc
ng 1, 2 v 3 l thuc loi 1. ng 4 v 6 thuc loi 2. ng 5 l thuc loi 3.
Khi cc ng trong hnh 10.7 l biu din cc nh hng ca cc Cation thuc
loi 4. Trong hnh 10.10b, ng s 1, 2 v 3 m t cc nh hng thuc loi 6. Cui
cng ng s 5 m t cc nh hng thuc loi th 7 nh trnh by trn. Ngc
li vi cc nh hng trn, hnh 10.9 l m t nh hng tng hp ca cc Ion Mg(II),
TI(IV), Al(III), Fe(III), Si, P n cng vch ph ca nguyn t Ca 422,7 nm trong
php o F-AAS vi ngn la n kh nguyn t ha mu bao gm khng kh v
axetylen, khi khng c mt v c mt LaCl3 vi nng khc nhau.
y vi s c mt ca LaCla dung dch mu nng t 1 % tr ln th nh
hng ca cc Ion l nu l hon ton c loi tr. V th mui LaCla l mt cht
ph gia c dng loi nh hng ca cc Cation v Anion trong php o F-AAS
vi hiu lc tt nht.
loi tr nh hng ca cc Cation n cng vch ph ca nguyn t phn
tch chng ta c th s dng mt s bin php sau y hoc ring bit, hoc t hp ca
chng vi nhau:

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.

nh hng ca nng NaCl/Pb-217,0 nm nh hng ca cc Cation loi 5, 6, 7


ng 1: Ti/Ca 422,7 nm, F-AAS

(kh. kh + C2H2)

ng 2: Ti/Sr 460.7 nm, F-AAS

(-nt- )

ng 3: Ti/Ba 553,6 nm, F-AAS

(-nt- )
213

ng 4: Si/ca 422,6 nm. F-AAS

(-nt- )

ng 5: Si/Mg 285,2 nm. F-AAS

(-nt- )

ng 6: Si/Ca,Mg, F-AAS

(khi c mt 1% LaCl3)

ng 7: Ti/Mg 285,2 nm, F-AAS

(kh. kh + C2H2)

10.2.3.3 nh hng ca cc an Ion c trong mu


Cng vi cc Cation, cc Anion cng nh hng n cng vch ph ca
nguyn t phn tch nh hng ny v tnh cht tng t nh nh hng ca cc loi
axit. Ni chung, cc Anion ca cc axit d bay hi thng gim t cng vch ph.
Ch ring c hai Anion ClO 4 v CH3COO l gy hiu ng dng (lm tng),
tc l lm tng cng vch ph ca nguyn t phn tch trong mt s trng hp
mt vng nng nht nh. Cc Anion khc thng gy hiu ng nm (lm gim)
theo th t Cl < NO 3 < CO 3 < SO 4 < F < PO 34 < SIO 32 v.vTrong Anion
SIO 32 c nh hng ln nht, cn t nht l Ion Cl. ng thi khi nng ca cc
Anion tng th tc dng nh hng cng tng theo (hnh 10.5).
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
AAS m ch nn dng axit HCl hay HNO3 vi nng di 2% (hnh 10.12).

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

Cng vch ph C=30 ppb


php o ETA-AAS
Mg-202,60 nm Ca-422,70 nm

1 Dung dch HCl 1%

0,220

0,250

2. Nh 1, thm 2% LaCl3

0,020

0,025

3. Nh 1, thm 0,5% LaCl3

0,050

0,060

4. Nh 2, thm 1% NH4NO3+LiBO2

0,210

0,245

loi tr nh hng ca thnh phn nn ngi ta c th dng nhiu bin php


khc nhau:
1. Tng nhit nguyn t ha mu.
2. Thm vo mu cc cht ph gia c nng ph hp ngn cn s xut hin
cc hp cht bn nhit.
3. chuyn mu sang cht nn khc, y l 1 bin php c dng kh ph bin
trong php o AAS loi tr nh hng ca cht nn mu.
4. Tch b nguyn t nn, khi hai bin php trn khng t kt qu. Tt nhin
bin php ny l hn hu.
216

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

Dung dch HCl 0,1 M

Nh 1, thm 40% CH3OH

1,670

Nh 1, thm 40% C2H5OH

1,750

Nh 1, thm 40% Axeton

2,000

Nh 1, thm 20 % Izobutanol

2,400

Nh 1, thm 70 % Axeton

2,500

Nh 1, thm 50 % EAK

2,600

Nh 1,80 % Ethyl Amine Ketone (EAK)

2,800

Trong MIBK (Methyl Izobutyl Ketone)

3,000

Chng 11
PHN TCH NH LNG BNG PH AAS

11.1 Nhng vn chung


11.1.1 Phng trnh c bn ca php o
Trong php o ph hp th nguyn t, mi quan h gia cng ca mt vch
ph hp th ca mt nguyn t phn tch v nng ca n trong mi trng hp th
cng tun theo nh lut hp th quang Lamber-Bia. Ngha l, nu chiu chm tia sng
n sc cng Io i qua mt mi trng cha mt loi nguyn t t do nng N
v c b dy l L cm, th mi quan h gia Io v phn cng sng Itq qua mi
trng c tnh theo cng thc:
log

Io
K '.N .L
I

(11.1)

y i lng lgIo/I chnh l nng lng ca tia sng b mt i do s hp th


ca cc nguyn t t do trong mi trng . Nh vy, n chnh l cng ca vch
ph hp th v chng ta c:
A = k'.N.L

(11.2)

Cng thc ny cho chng ta bit mi quan h gia cng ca mt vch ph


hp th v nng ca nguyn t trng thi hi trong mi trng hp th. Nhng n
cha cho bit mi quan h gia cng ca vch ph v nng ca nguyn t
trong mu phn tch. Nh vy, nu gi nng ca nguyn t trong mu phn tch l
C th chng ta cn phi tm mi quan h gia C v N v t s suy ra c mi quan
h gia C v A. M t nng C trong dung dch chuyn thnh nng N trng thi
kh, c c bi qu trnh ha hi v nguyn t ha mu phn tch. Nghin cu vn
ny, nhiu kt qu thc nghim ch ra rng, mi quan h ca s chuyn ha gia C v
N l rt phc tp v n ph thuc vo nhiu yu t nh:
+ Bn cht ha hc ca mi nguyn t, trng thi lin kt,
+ Tnh cht ca hp cht m cc nguyn t tn ti trong mu,
+ Thnh phn vt l v ha hc ca mu phn tch, c bit l cht nn,
+ Cc iu kin thc hin qu trnh nguyn t ha mu.
Tuy c phc tp, nhng t nhng kt qu thc nghim v trong mt phm vi nht
219

nh ca nng C ca nguyn t cn nghin cu trong mu phn tch, mt cch


tng qut, th mi quan h gia C v N c xc nh theo cng thc:
N = k.Cb

(11.3)

trong k l mt hng s thc nghim, n ph thuc vo tt c cc iu kin


ha hi v nguyn t ha mu v khng i trong nhng iu kin nht nh c
chn cho mt php o, c bit l nhit ca mi trng hp th.
Cn b l mt hng s, c gi l hng s bn cht, n ph thuc vo nng C,
tnh cht hp th ph ca mi nguyn t v tng vch ph ca nguyn t . Hng s
b c gi tr bng v nh hn 1 (0 < b 1).
Khi nng C ca nguyn t phn tch nh th b lun lun bng 1. Khi C tng
th b nh dn xa gi tr 1, tin v 0, tt nhin khng bao gi bng 0. Nh th, vi mi
mt vch ph ca mt nguyn t phn tch, chng ta lun lun c mt gi tr nng
Co, m vi mi gi tr:
+ Cx < Co th b lun lun bng 1, lc ny A ph thuc tuyn tnh vo C.
+ Cx > Co th b nh hn 1. A ph thuc vo C theo cng thc (11.4) - khng
tuyn tnh.
Nh vy, t hai phng trnh (11.2) v (11.3) chng ta c:
A = K.L.Cb

(11.4)

trong K = k'.k v c gi l hng s thc nghim ca php o AAS. ng


thi t cng thc (11.4) ny chng ta thy, cng A ca mt vch ph hp th ph
thuc vo ba i lng (thng s K, L v C).
Nhng trong mt php o th K lun lun l hng s, L l chiu di ca ngn la
trong php o F-AAS hay chiu di ca cuvet graphit trong php o ETA-AAS, tc l
b dy ca mi trng hp th v nh th trong mt php o th n cng khng i.
Do A ch cn ph thuc vo nng C ca nguyn t cn xc nh trong mu
phn tch. Do vy, mt cch tng qut chng ta c:
A = a.Cb

(11.5 )

y chnh l phng trnh c s ca phng php phn tch nh lng da theo


vic o ph hp th ca mt nguyn t xc nh nng (hm lng) ca n v
mi quan h ny c minh ho trong hnh 11.1.

220

Nu b bng 1 th mi quan h gia A


v C l tuyn tnh theo phng trnh c
dng y = a.x. Khi ng biu din mi
quan h ny l mt ng thng i qua gc
to . Nhng thc nghim cho thy rng
trng hp ny l ch c trong mt vng
nng nh. y l trng hp l tng,
n ch c c i vi mt s vch ph
khng nhy ca mt vi nguyn t nh Fe,
Ni, Si (hnh 11.1b). Ph bin nht l trng
hp trong hnh 11.1a. l trng hp
chung cho hu ht cc vch ph hp th ca
cc nguyn t. N gm mt on tuyn tnh
(b=1) v mt on khng tuyn tnh (b<1).
Ni chung trong trng hp ny thng
lun lun c mt on thng ca ng biu
din mi quan h gia A v C vng nng
nh ca nguyn t phn tch. l on
OA. Vi cc vch ph cng nhy th on
OA ny cng ngn. Tc l vng nng
ng vi on tuyn tnh l hp. Vng nng
ng vi on tuyn tnh OA c gi l
vng tuyn tnh ca php o AAS.
i vi mi nguyn t v mi mt vch ph th vng ny l khc nhau r rng
(bng 11.4). Trng hp th ba cn li (hnh 11.1c) l mt dng phc tp. Trong
trng hp ny mi quan h gia A v C l khng tuyn tnh trong bt k vng nng
no. Song ch rt t vch ph, c bit l cc vch ph rt nhy v c kh nng t
o ln mi tun theo quan h ny. Trong phn tch, nu gp phi trng hp ny cn
phi ht sc ch khi lp ng chun, ngha l phi dng nhiu mu u c nng
gn nhau dng ng chun v ch c nh th chng ta mi xc nh c chnh
xc v tr ca ng chun. Vch ph hp th Na-589,00 nm i din trng hp ny.
11.1.2 Mu chun trong php o AAS
Trong phng php phn tch nh lng theo ph hp th nguyn t, mu u
(mu chun) dng ng chun cng bt buc phi tha mn mt s iu kin nht
nh. Cc iu kin l:
1. Cc mu u phi c trng thi vt l v ha hc nh mu phn tch, ngha l
mu phn tch tn ti trng thi, dung mi, mi trng v dng lin kt no th mu
u cng phi c tnh cht ging nh th. C nh th mi loi tr c nh hng ca
cht nn, ca thnh phn ca mu n kt qu phn tch.
221

2. Cc mu u v mu phn tch phi c pha ch hay ch luyn, x t trong


cng mt iu kin nh nhau.
3. Cc mu u phi bn vng theo thi gian, ngha l khng b thay i thnh
phn sau khi ch luyn v bo qun s dng lu di, khng b sa lng, khng b
phn hy to thnh cc cht khc lm thay i thnh phn ca mu u. C nh th
mi bo m c thnh phn ca n nh tnh ton pha ch v s dng lu di.
4. Nng ca cc nguyn t cn phn tch trong cc mu u phi rt chnh xc
theo yu cu ca phng php phn tch. ng thi khong nng ca mt dy mu
u phi phn b u trong vng tuyn tnh hay trong ton b ng chun ca php
o v bao trm nng ca cc mu phn tch.
Ngha l nng cc mu phn tch phi trong vng tuyn tnh ca ng chun.
Cn nu khng, chng ta phi pha long mu phn tch cho ph hp.
11.1.3 Biu din nng trong php o AAS
Trong php o ph hp th nguyn t, ngi ta thng biu din nng ca
nguyn t phn tch theo cc cch sau y:
a) Nng phn trm (%)
y l khi nim thng thng, n c biu th bng s gam ca cht phn
tch, c trong 100g mu em phn tch. Nng ny c tnh theo cng thc:
C (%) =

mx
.100
m

(11.6)

trong mx l s gam cht phn tch c trong mu ly phn tch, cn m l s


gam mu phn tch.
V d, nu vit dung dch NaOH 0,1%, ngha l trong 100 gam dung dch c 0,1
gam NaOH.
b) Nng microgam 1 ml hay microgam li
Loi nng ny c c s dng ph bin trong phn tch lng vt v
thng c biu th theo hai cch:
1. S microgam ca cht phn tch c trong mt lt dung dch mu (g/mL) hay
s microgam cht phn tch c trong mt mnh dung dch mu (g/mL).
V d, nu vit Cpb = 1,2 g/l th c ngha l c trong 1 lt dung dch mu s c
1,2 microgam ca Pb. Hay nu vit Cpb: 1,2 g/mL th c ngha l trong mt minilit
dung dch mu s c 1,2 microgam ca Pb.
2. S microgam ca cht phn tch c trong mt gam mu (g/g), hay s
microgam cht phn tch trong 1 kg mu (g/kg). V d, nu vit Cpb = 2,5 g/g th c
ngha l c trong 1 gam mu s c 2,5 microgam ca Pb.
222

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

trong : ag- attogram; fg- femtogram;


pa- picogram; ng- nanogram v g- microgram.
Cng hon ton tng t, ngi ta cn dng cc n v c s ca g.
l nanogam (ng), picrogam (pa). Do cng c cc khi nim nng ng/L,
ng/mL, ng/g, pg/L,pg/mL v pg/g. Cc n v g, ng v pa u km nhau 1000 ln v
mi tng quan ca chng c ch ra trong bng 11.1.
c) Nng ppm v c s ca n
Loi nng ppm (part per mill Ion: mt phn triu) thng hay c dng
trong phn tch lng vt cc cht, v cng c biu th theo hai cch, da theo mu
dng lng (theo n v ml hay lt), hay dng rn, hay bt (theo n v g, hay kg.):
223

Bng 11.2
Chuyn i gia cc nng

Nng u c

Chuyn sang nng th 2


Nng

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

11.1.4 Khi nim v nhy


nhy l mt i lng ch ra kh nng ca mt phng php phn tch theo
mt k thut o no c p dng cho phng php phn tch . Phng php
phn tch c nhy cao tc l nng gii hn di c th phn tch c l nh.
Cng nh cc phng php phn tch khc, nhy ca phng php phn tch theo
ph hp th nguyn t cng ph thuc vo nhiu yu t khc nhau, nh.:
1. Trc ht phi k n cc c trng, tnh cht ca h thng my o, nh h
quang hc, dng c thu nhn v pht hin tn hiu cn o, h thng khuch i v ch
th tn hiu o. chnh l cc c trng k thut ca h thng my quang ph.
2. Yu t th hai l cc iu kin v k thut thc hin nguyn t ha mu o
ph ( nghin cu k trong chng 2). V th phng php nguyn t ha trong ngn
la c nhy km phng php nguyn t ha khng ngn la. Bng 11.3 v bng
11.4 l nhng v d v vn ny.
3. Yu t th ba l kh nng v tnh cht hp th bc x ca mi vch ph, ca
mi nguyn t. Vch ph no, nguyn t no c kh nng hp th cng mnh th php
o theo vch c nhy cng cao. Ngha l i vi mt nguyn t cc vch ph
khc nhau cng s c nhy khc nhau (bng 11.3, bng 11.4 v bng 11.5). V th,
khi ni n nhy ca mt nguyn t phn tch l phi gn lin vi nhng iu kin
phn tch c th nht nh ca mt php o.
l ba yu t chnh, tt nhin cn nhiu yu t khc cng nh hng n
nhy ca mt phng php phn tch, nh axit ca mu, nguyn t c s ca mu.
V vy, nu lm tt, ngha l tiu chun ha c cc yu t nu, chng ta s thu
c nhy tt nht ca mt php o. Nh vy nhy l g? V vn ny, hin
nay ngi ta c hai khi nim.
1. nhy tuyt i. Trong php o AAS, nhy tuyt i l lng gam (khi
lng nh nht ca nguyn t cn phn tch phi c trong mi trng hp th cn
thu c cng ca vch ph hp th chn chim 1% ton bng hp th, hay
bng 3 ln tn hiu nn. Nh vy, mi nguyn t v mi vch ph s c nhy tuyt
i khc nhau (bng 11.4). Do , khi phn tch cc nguyn t c nng nh phi
chn cc vch c nhy cao o v ngc li.
2. nhy tng i. nhy tng i cn c gi l nhy nng .
nhy ny c nh ngha l nng nh nht ca nguyn t phn tch c trong mu
cn c th pht hin c tn hiu hp th ca n theo mt vch ph nht nh
chn v tn hiu ny phi bng 1% ca bng hp ton phn, hay bng 3 ln dao ng
ca gi tr nn. Loi nhy ny c dng ph bin trong php o AAS hn khi
nim v nhy tuyt i. K c cc phng php phn tch khc, th khi nim
nhy ny cng c dng ph bin hn, v hm lng cc cht trong mu phn tch
hay mu chun thng c biu th theo nng . Do , vic so snh nhy gia
225

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

Gii hn pht Khong xc nh


hin (g/mL)
(g/mL)
4

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

11.1.5 Gii hn pht hin trong AAS


Bn cnh khi nim v nhy ngi ta cn s dng khi nim v gii hn pht
hin i vi mt nguyn t khi dng mt vch ph chng minh n. Gii hn pht
hin cng c hai khi nim tng t nh nhy. l gii hn pht hin tuyt i v
tng i.
1. Gii hn pht hin tng i ca mt nguyn t theo mt vch ph nht nh
c th xem l nng nh nht ca nguyn t trong mu phn tch cn c th
pht hin c tn hiu hp th ca n theo vch ph trong mt iu kin nht
nh chn.
2. Ngc li gii hn pht hin tuyt i ca mt nguyn t l khi lng ti
thiu ca nguyn t cn c trong mi trng hp th cn c th pht hin c
tn hiu hp th ca n cng trong mt iu kin nht nh chn. Bng 11.5 l mt
vi v d v vn ny.
Nh vy, mi mt nguyn t v mi mt vch ph cng c gii hn pht hin
khc nhau. Trong mt nguyn t, vch ph no c kh nng hp th mnh s c gii
hn pht hin lng nh hay nng nh (bng 11.5).
Nhng ngoi cc yu t trn, gii hn pht hin mt nguyn t theo php o ph
hp th nguyn t cn ph thuc vo:
+ Tnh cht, cht lng v cc c trng k thut ca mi my quang ph ca
tng hng sn xut my o ph hp th nguyn t (bng 11.5a).
+ Cc iu kin thu nhn tn hiu cng vch ph. Yu t ny lin quan n
h nhn quang in v vng ph.
Bng 11.5
Gii hn Pht hin ca cc nguyn t theo AAS
Nguyn t

Theo php o F - AAS

Theo php ETA - AAS.


Tng i
(g/mL)

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

Gii hn pht hin (pa) tuyt i


HGA-74
0,1
2,0
10,0
0,1
5,0
10,0
2,0
3,0
0,1
0,2
3,0
10,0
2,0
200,0
100,0
0,05

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,

Ghi ch: - HGA-74: My ca hng Perkin Elmer, CRA-63: My ca hng


VARIAN,
- A-3470: My ca hng Shandon, USA.
- IL-355: My ca hng Instrumentat Ion Lao.
11.1.6 Khong xc nh trong php o AAS
Khi nim ny gn lin vi mt nguyn t v mt vch ph ca nguyn t
c s dng phn tch n trong mt iu kin nht nh chn. Trong php o
ph hp th nguyn t, vic nh lng mt nguyn t da vo phng trnh c bn
A. = K.Cb

(11.7)

Nh chng ta nghin cu trn (mc 11.1.1), trong mi quan h ny A ch


ph thuc tuyn tnh vo C khi b = 1, ngha l khi nng C rt nh. Khi chng ta
c th vit:
A = K.C

(II.8)

Ngha l ch trong mt khong nng C nht nh v nh, th mi quan h gia


231

A v C l tuyn tnh, ng ng vi phng trnh (11.8). Khong nng C ca


nguyn t phn tch ng ng vi phng trnh (11.8) ny c gi l khong xc
nh (hay l khong tuyn tnh) ca nguyn t theo phng php nu. Trong
khong nng ny th quan h gia A v C c dng ca phng trnh ton hc y =
ax.
Thc nghim cho thy rng khong xc nh i vi mi nguyn t l khc nhau,
mi vch ph khc nhau l rt khc nhau (bng 11.4).
Ngay trong mt nguyn t th cc vch ph khc nhau cng s c khong tuyn
tnh khc nhau (bng 11.6). Vch ph no c hp th cng nhy th c khong nng
tuyn tnh cng hp v ko v pha nng nh.
V th khi nim v khong xc nh ca mt nguyn t trong mt phng php
phn tch gn lin vi mt vch ph c chn o v cc iu kin th nghim
c chn. Bng 11.6 l mt s v d v khong xc nh ca mt s nguyn t theo
cc vch ph ca n trong php o AAS.
11.1.7 B chnh nn trong php o AAS
11.1.7.1 Ti sao phi b chnh nn
- Ph hp th ca nguyn t lun c ph nn km theo. Ngha l ti v tr vch
ph cng c cng nn cng thm vo. Trong phn tch nng nh (mc ppm
hay ppb) th phn ca ph nn cng kh ln, ph nn ny l:
+ Ph lin tc, che vch ph AAS chnh cn o,
+ Tng dn t sng ngn sang sng di,
+ Cng ph nn t 0 n 1,7 aufs, c khi n 2,0 aufs.
- V th phi loi tr, nht l khi o nng nh trong vng VIS.
11.1.7.2 Cc phng php b chnh nn
Hin nay c 4 phng php b chnh (loi tr) ph nn:
1. Phng php 2 vch ph.
2. Phng php dng ngun sng lin tc b chnh.
3. Phng php da theo hiu ng Zeeman.
4. Phng php dng ngun n sc hot ng theo 2 ch dng.
Hin nay cc my AAS bn trn th trng thng thit k dng 2 phng php
b chnh nn. l phng php 2 v 3. Ngi mua ty yu cu m chn loi no
cho thch hp. Sau y l nguyn tc ca mi phng php b chnh nn (BC).

232

1. Phng php 2 vch ph


- Nguyn tc:
Chn 2 vch ph o, l:
+ 1 vch ca nguyn t phn
tch (gi l vch PT- PT) ta c APT
+ v 1 vch ca nguyn t so
snh (vch so snh- SS) ta c Ass
+ Cng thc s c tnh
nh sau (hnh 11.2):
Ath = (APT - ASS)
- iu kin:
+ Cng ca ASS nm trong vng tuyn tnh, nhng phi nh.
+ Nng ca cht so snh phi nh v khng i trong mi mu.
+ Vch so snh phi gn vch PT, phi cch nhau t hn 10 nm.
+ Vch SS phi gn, v r rng.
- u v nhc im:
+ n gin, khng cn trang b BC.
+ B chnh trit .
+ Nhng li lm gim mt nhy.
2. Phng php dng ngun sng lin tc
- Nguyn tc:
+ V ph nn l lin tc,
+ Nn dng ph lin tc BC.
+ Ngun sng lin tc c dng:
n HQ Hydro (D2-lamp) cho vng t ngoi (UY:190-360nm), n W-Halid
cho vng kh kin (VIS: 380-1000 nm).
- Cch o ph:
+ Phi o cng ca vch ph phn tch 2 ln.
+ Trc tin o cng tng Atot (khi D2-lamp khng hot ng), o nn An,
khi D2-lamp hot ng (n HCL khng hot ng).
233

Nh vy cng thc s l: Am = (Atot - An)


- iu kin:
+ C trang b BC h n D2Lamp (UY) v n W-Halid (VIS),
+ C mch in t BC (BC'Modul).
- u v nhc im:
+ Trang b BC khng t,
+ D thc hin,
+ B chnh khng trit , ch
c khi nn nh hn 1,3 aufs.
3. Phng php da theo hiu ng Zeeman - Nguyn tc:
+ Khi c hiu ng Zeeman, vch ph ca
nguyn t PT b phn thnh 2,4,... nhnh i
xng qua tnm vch (v tr o), cn ti v tr tnm
vch ch l nn ca ph lin tc (hnh 11.4).
+ Nh vy nu o ph khi c v khng
c hiu ng Zeeman th ta kh b c ph
nn lin tc.
- iu kin:
+ C h thng in t iu khin BC
(BC- Modul),
+ C trang b ngun cp hiu ng
Zeeman.
- Cch o:
BC nn ta o ph ca vch phn tch
ti 2 thi im:
+ o cng tng Atot, khi khng c hiu ng Zeeman,
+ Sau o cng nn An, khi c hiu ng Zeeman.
Nh vy cng thc ca vch ph Ath l:
Ath = (Atot - An)
- u im v nhc im:
234

+ D thc hin, nhanh


+ B chnh trit , n ht c 2 aufs cng nn.
+ Thm b phn trang b BC hi t tin:
4. Phng php dng ngun n sc hot ng 2 ch dng
- Nguyn tc:
Da theo hin tng t o ca vch ph cng hng (vch nhy) ca nguyn t
cng n HCL rt ln. Lc ny vch ph b ch i, phn tnm vch ph ch cn
nn.
Nh vy nu ta o cng lc u cng n HCL bnh thng ta s
c Atot, sau cho n HCL ln cng cao (100-150 bnh thng) v o th ta
ch c cng ph nn. Nh vy cng thc ca vch ph Ath l:
Ath = (Atot - An)
Hiu ng ny do Smith Hieftje (H Lan) pht hin. Nn phng php ny gi l
phng php BC Smith Hieftie.
- iu kin:
+ C mch BC theo nguyn.l Smith Hieftje.
+ C n HCL hot ng c dng rt cao.
- Cch o ph:
+ Trc tin o cng hp th, khi HCL dng bnh thng,
+ o cng hp th, dng
cao ca n HCL,
+ Sau ly hiu s 2 ln o, ta
c cng thc.
- u v nhc im:
+ Phng php ny BC trit .
+ n HCL dng kh cao l rt
t (gp 3 ln n HCL thng).
+ n HCL hot ng c dng
rt cao, rt chng hng.

235

Bng 11.6
Vng tuyn tnh ca php o
Nguyn t vch (nm)

236

nhy (g/mL)

Vng tuyn tnh (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,

11.1.8 Ti u ha cc iu kin cho php o AAS


Mun xc nh mt nguyn t theo mt k thut o no , chng ta cn phi c
mt quy trnh phn tch c th theo k thut . Ngha l phi c mt phng php
phn tch n nh. C nh th chng ta mi thu c kt qu chnh xc. Mun th,
nhng ngi lm phn tch trc ht phi tin hnh nhng nghin cu, th nghim
ti u ha cc iu kin phn tch v xy dng mt quy trnh phn tch c th theo k
thut m mnh nh p dng cho mc ch ca mnh t ra. Cng vic ny bao gm
nhng vn sau y cn c gii quyt:
11.1.8.1 Chn cc thng s ca my o ph
Cc thng s ca h my o ph AAS thng bao gm cc yu t.
1. Vch ph o. Vch ph c chn xc nh nguyn t mnh mong mun.
Vch ph ny phi tha mn iu kin:
+ Khng b cc vch khc quy ri, chen ln gy nhiu hay trng lp.
+ Phi r rng v nt, c di sng chnh xc.
+ Cng vch ph hp th A phi ph thuc tuyn tnh vo nng C trong
mt vng nng nht nh.
+ Vch ph phi nm trn mt nn khng qu ti.
Tt nhin khi cn xc nh cc nng rt nh th phi chn vch ph c
nhy cao v ngc li, khi xc nh cc nng khng nh th cn chn cc vch km
nhy hn.
2. Cng dng lm vic ca n HCL. Cng dng in lm vic ca n
catot rng (HCL), ni chung nn chn cng dng nm trong vng t 60% n
85% so vi cng cc i ghi trn n HCL. Khi cn nhy cao th chn cn
di, cn khi cn n nh cao th chn cn trn.
3. Khe o ca my quang ph. Khe o (khe vo v khe ra ca chm tia) c nh
hng n nhy v vng tuyn tnh ca php o. Ni chung nhiu my quang ph
hp th thng c khe o thay i c theo cc gi tr t 0,2 n 10 nm theo 5 hay 4
bc. V d 0,2; 0,4; 0,8; 1; 2 v 10 nm. Nhng i vi nhiu vch ph th khe o ph
hp l nm trong vng t 0,2 n 1 nm. Do cn phi chn ch mt gi tr ph hp
nht cho php o nh lng mt nguyn t theo vch ph c chn, lm sao ch
cho va vch ph cn o vo khe o l tt nht.
4. Burner Head Hight. Chiu cao n nguyn t ha mu, nu chn khng ng
ra s khng nhng thu c nhy km v tn hiu o khng n nh, m ng thi
li b nhiu yu t nh hng.
5.Thi gian o. Thi gian o, s ln o cng vch ph. Yu t ny ph thuc
vo c trng k thut ca tng my quang ph v ty thuc vo k thut nguyn t
237

ha mu. Vi php o F-AAS th l thi gian thu c tn hiu hp th n nh, vi


php o ETA-AAS th li l thi gian nguyn t ha mu (xem chng 8).
6. Lng mu. l tc dn mu, lng mu bm vo.
7.Vng tuyn tnh ca vch ph c chn nh lng. Yu t ny cng cn
c xc nh chnh xc cho tng vch ph chn nh lng nguyn t phn tch.
C nh th mi c th chun b mt dy mu chun ph hp cho php o ca mnh. V
cc kt qu thu c nm trong vng tuyn tnh ca vch ph bao gi cng c
chnh xc cao.
8. Phng tin ch th kt qu o. N c th l my t ghi lc cng vch
ph, my hin s digital, my printer hay my tnh ch trc tip hm lng (nng )
ca nguyn t phn tch. Tt nhin chn phng tin no l ty thuc vo trang b m
mnh hin c v l ph hp nht i vi mnh trong iu kin thc t .
9. B chnh nn khi o. Yu t ny c thc hin hay khng l ph thuc vo vch
ph c chn o. Nu nn ca ph c nh hng th phi thc hin php o c b
chnh nn loi tr nh hng v ngc li, nu khng nh hng th khng cn
thit. Trong php o ETA-AAS th yu t ny rt quan trng, n nh hng rt ln n
kt qu phn tch. Do cn phi ht sc cn thn trong mi trng hp c th ca
mi loi mu phn tch. V nn ca mu l mt nguyn nhn gy ra nh hng n kt
qu phn tch.
10. H nhn quang in nhn tn hiu AAS. Yu t cui cng trong vn ny l
th lm vic ca nhn quang in. Yu t ny l thang nng lng hp th ca php o
AAS. Trn cc my thang ny c chia thnh 100 n v.
Trong vng t 70 n 100 l vng lm vic ph hp ca th nui nhn quang in
cho cc my o ph hp th nguyn t v vng ny c nh du mu xanh hay mu en.
Trong cc php o phi iu chnh nm GAIN kim ch thang nng lng nm trong vng
ny v phi gi mt gi tr chn trong sut qu trnh o nh lng mt nguyn t.

11.1.8.2 Cc iu kin nguyn t ha mu


Vn ny ty thuc vo k thut c chn nguyn t ha mu. N c
nghin cu k trong chng II. Do y nu li mt s iu cn ch . C th l:
1. Vi php o F-AAS. Cn phi chn cc thng s sau y:
- Nhit ngn la, tc l chn thnh phn kh chy to ra ngn la c nhit
ph hp.
+ Chiu cao ca n nguyn t ha mu (burner head).
+ Tc kh mang v tc dn mu vo bung aerosol ha.
+ B dy ca lp hp th, tc gc nghing n nguyn t ha mu (burner head).
2. Vi php ETA-AAS. Bao gm nhng iu kin:
238

- 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

c trao i chi tit trong mt xemina ring.


11.1.8.5 Phng php chun ha nh lng
Ngoi 4 yu t trn, nhng nu phng php chun ha c chn nh lng
khng ph hp th cng cha thu c kt qu chnh xc v ph hp vi thc t. Vn
ny ty thuc vo bn cht v thnh phn vt l ha hc ca mu phn tch.
V th phi ty theo tng trng hp c th m chn phng php ng chun
hay phng php thm tiu chun xc nh nng ca nguyn t phn tch trong
mt i tng mu nht nh.
Trn y l tm tt cc vn cn thit trong qu trnh ti u ha cc iu kin
th nghim chn ra cc iu kin ph hp xy dng mt phng php theo mt
k thut o nht nh.
Ngha l mun xut mt phng php phn tch th phi tr li c nhng
vn mt cch chnh xc v r rng.
chnh l cng vic nghin cu xy dng quy trnh ca cc nh phn tch. Cn
khi c mt quy trnh phn tch n nh ri th bt k k thut vin phn tch no
cng c th tin hnh phn tch c.
11.2 Cc phng php phn tch c th
xc nh nng (hm lng) ca mt nguyn t trong mu phn tch theo
php o ph hp th nguyn t ngi ta thng thc hin theo cc phng php sau
y, da theo phng trnh nh lng c bn ca php o ny qua vic o cng
ca vch ph hp th ca nguyn t phn tch v xc nh (hay pht hin) nng ca
cht phn tch trong mu o ph theo mt trong cc phng php chun ha sau:
1. Phng php ng chun;
2. Phng php thm tiu chun;
3. Phng php th khng i;
4. Phng php dng 1 mu chun.
11.2.1 Phng php th chun (ng chun)
Phng php ny cn c gi l phng php ba mu u. V nguyn tc ca
phng php ny l ngi ta da vo phng trnh c bn ca php o A - K.C v mt
dy mu u (t nht l ba mu u) dng mt ng chun v sau nh ng
chun ny v gi tr Ax xc nh nng Cx ca nguyn t cn phn tch trong mu
o ph, ri t tnh c nng ca n trong mu phn tch.

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

Tip nh ng chun ny v cc gi tr Ax chng ta d dng xc nh c


nng Cx. Cng vic c th l em cc gi tr Ax t ln trc tung A ca h ta , t
k ng song song vi trc honh C, ng ny s ct ng chun ti im M,
t im M ta h ng vung gc vi trc honh v n ct trc honh ti im Cx, Cx
y chnh l nng phi tm (hnh 11.6).
Phng php ny n gin, d thc hin v rt thch hp vi. mc ch phn tch
hng lot mu ca cng mt nguyn t, nh trong kim tra cht lng thnh phm,
kim tra nguyn liu sn xut. V mi khi dng mt ng chun chng ta c th xc
241

nh c nng ca mt nguyn t trong hng trm mu phn tch. l u im


ca phng php ny. Song trong nhiu trng hp chng ta khng th chun b c
mt dy mu u tha mn cc iu kin quy nh cho phng php ny ( trnh
by trong mc 11.1.2) nn khng xc nh c chnh xc v tr ca ng chun v
nh th tt nhin kt qu phn tch s mc sai s ln. Ngha l khi mu phn tch c
thnh phn phc tp v chng ta cha bit chnh xc th khng th chun b c mt
dy mu u ng n nn s b nh hng ca nn, ca thnh phn ca mu.
chnh l nhc im ca phng php ny. Trong nhng trng hp nh th, tt nht
l dng phng php thm tiu chun xc nh nng ca nguyn t phn tch
trong mu, hay bin i ca mu sang nn t to ph hp cho c mu u v cc mu
phn tch.
11.2.2 Phng php thm tiu chun
Trong thc t phn tch, c bit l xc nh lng vt cc kim loi, khi gp phi
cc i tng phn tch c thnh phn phc tp v khng th chun b c mt dy
mu u (mu chun) ph hp v thnh phn vi mu phn tch, th tt nht l dng
phng php thm tiu chun. Ch nh th mi loi tr c yu t nh hng v
thnh phn ca mu (matrix effect).
Nguyn tc ca phng php ny l ngi ta dng ngay mu phn tch lm nn
chun b mt dy mu u, bng cch ly mt lng mu phn tch nht nh v gia
thm vo nhng lng nht nh ca nguyn t cn xc nh theo tng bc nng
(theo cp s cng). V d lng thm vo l C1, C2, C3, C4, nh th chng ta s
c mt dy mu chun nh trong bng sau, trong Cx l nng (hm lng) ca
nguyn t cn xc nh trong mu phn tch.
Bng dy chun ca phng php thm tiu chun.
Co

C1

C2

C3

C4

C5

Lng mu phn tch

Cx

Cx

Cx

Cx

Cx

Cx

Lng thm vo

C1

C2

C3

C4

C5

Cht khc
A o c

Cc cht khc l nh nhau


Ao

Al

A2

A3

A4

A5

Tip cng chn cc iu kin th nghim ph hp v mt vch ph ca


nguyn t phn tch, tin hnh ghi cng hp th ca vch ph theo tt c dy
mu u. V d chng ta thu c cc gi tr tng ng l Ao, Al,A2, A3, v A4.. By
gi t cc gi tr cng ny v ng vi cc nng thm vo ca nguyn t phn
tch chng ta dng mt ng chun theo h ta A - C. chnh l ng chun
ca phng php thm (hnh 11.7). ng chun ny ct trc tung A ti im c ta
242

(Ao, O). Sau xc nh nng Cx cha bit chng ta lm nh sau:


Cch I. Ko di ng chun v pha tri, n ct trc honh ti im Cx. on
OCX chnh bng gi tr nng Cx cn tm (hnh 11.7).
Cch II. Cng c th xc nh Cx bng cch t gc ta k mt ng song
song vi ng chun v t im Ao k ng song song vi trc honh, hai ng
ny ct nhau ti im M, t im M h ng vung gc vi trc honh, ng ny
ct trc honh ti im Co, Chnh on OCX l bng gi tr Cx phi tm (hnh 11.7).
Phng php ny c u
im l qu trnh chun b mu
d dng, khng cn nhiu ha
cht tinh khit cao chun b
dy mu u nhn to. Mt
khc li loi tr c hon
ton nh hng v thnh phn
ca mu cng nh cu trc vt
l ca cc cht to thnh mu.
Nhng phi ch rng, nng
thm vo ca nguyn t
phn tch phi theo tng bc v
khong cch ca cc bc
phi xp x bng nng Cx
phi tm.
C nh th th phn ni suy tuyn tnh mi c ngha chnh xc.
Phng php ny c s dng rt nhiu trong phn tch lng vt v lng cc
nh cc nguyn t kim loi trong cc loi mu khc nhau, c bit l cc loi mu c
thnh phn vt l v ha hc phc tp, cc mu qung a kim.
ng thi y cng l mt phng php xc nh pht hin ca mt
phng php phn tch.
11.2.3 Phng php th chun c nh
Nguyn tc ca phng php ny l mun xc nh mt nguyn t no , trc
ht ngi ta cng phi dng mt ng chun nh trong phng php ba mu u,
phng php ng chun.
ng chun ny c gi l ng chun c nh (ng chun khng i) v
ng chun ny c dng lu di. Nh vy mun xc nh c nng Cx cha
bit, ta phi chuyn cc gi tr Axl tng ng v cc gi tr A xo ca ng chun c
nh xc nh Cng. gii quyt vn ny ngi ta c hai cch khc nhau:
- Cch th nht: Xc nh h s chuyn k theo cng thc:
243

Axo = k.Axl

(a)

y k c gi l h s chuyn ca gi tr cng A ca vch ph gia hai


ln o trong cng mt iu kin th nghim.
Mun th mi khi phn tch ta ghi li ph ca mt mu chun, v d thng dng
nng Ca. Nh th, ta c gi tr Axo-3 ca ng chun c nh, v hm nay ta li
c gi tr Axl-3, do h s chuyn k s c tnh theo cng thc:
k: Axo-3/Axl-3

(b)

Sau khi c h s k ta em n nhn vi cc gi tr cng Axl ca ngy lm phn


tch ta s thu c cc gi tr cng tng ng vi ng chun c nh. By gi
ch chiu cc gi tr vo ng chun c nh l tm c cc nng Cx.
- Cch th hai: T thc t phn tch khi nghin cu cc ng chun ngi ta
thy rng, trong cng mt iu kin th nghim, i vi mt nguyn t khi o trn mt
vch phn tch, nu ng chun dng c t dy ph ca cc mu chun ghi trn
cc ln khc nhau, th chng u l nhng ng thng song song vi nhau hoc trng
nhau (hnh 11.8a). Ngha l cc ng c cng h s gc. T thc t ny c th suy
ra cch dng ng chun phn tch mi ch nh mt mu chun m khng phi tnh
h s chuyn k nh trn. Mun th, khi ghi ph ca cc mu phn tch chng ta cng
ghi li ph ca mt mu chun dng dng ng chun c nh, v d nng
Ca. Sau cng chn mt vch phn tch dng dng ng chun c nh, o
cc gi tr Ax ca chng v gi tr Ax-3 ng vi nng Ca. T cc gi tr Ax-8 v nng
Ca t ln h to dng ng chun c nh chng ta c mt im A, ri qua
im A ny ta v mt ng song song vi ng chun c nh th ng ny chnh
l ng chun phn tch. Dng n v cc gi tr Ax ta s tm c cc nng Cx ca
mu phn tch (hnh 11.8b).
Trong thc t, nu my o tt, iu kin mi trng khng kh ( m, nhit )
khng i v cc iu kin thc nghim tht n nh, th cc ng chun (I) v (II)
hu nh trng nhau Trong hai cch nu, th cch th hai c ng dng nhiu hn
v n n gin v khng phi tnh ton phc tp nh cch th nht.
Phng php th khng i rt ph hp i vi php phn tch hng lot mu
t ngy ny qua ngy khc. V trong mi ngy phn tch chng ta khng phi ghi ph
li ca ton b dy mu u nn tit kim c thi gian, mu chun, ngha l c tnh
cht kinh t hn phng php ng chun.
Tuy th nhng phng php ng chun (ba mu u) hay phng php ng
chun c nh u ging nhau l u phi chun b mt dy mu chun c iu kin
ca mu u trong php phn tch quang ph nh lng. iu ny nhiu khi khng
thc hin c. c bit i vi nhng trng hp mu phn tch c thnh phn phc
tp m chng ta cha th bit c chnh xc. V th cng khng th chun b c
mt dy mu u c thnh phn ha hc v vt l ng nht vi mu phn tch. l
244

thc t v trong nhng trng hp th nh hng nguyn t c s v nguyn t th


ba n kt qu phn tch l rt r. iu ny th hin r khi xc nh cc nguyn t vi
lng. Lc ny chng ta phi hoc l thay i nn ca mu (Modify matrix) nu cch
ny c hiu qu, hay l dng phng php thm tiu chun.

11.2.4 Phng php mt mu chun


a) Khi c mu chun
Trong nhng trng hp n gin, chng ta cng 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:

Ax = a.Cx (a)

Vi mu u:

Ao = a.Cl (b)

Do em (a) chia cho (b) chng ta c:


C: (Ax/Ao).Cl (11.6) Nh vy khi o c gi tr Ax v Ao ta c t s ca chng,
v ch vic nhn n vi gi tr C1 l chng ta c gi tr nng Cx phi tm theo biu
thc (11.6).
b) Khi khng c mu chun
Trong trng hp ny, chng ta cng khng cn pha mt dy chun dng
th chun, m dng ngay 1 mu phn tch lm nn chun b mt mu phn tch v 1
mu thm chun theo phng php thm v tnh ngay gi tr Cx nh mt lng chun
C1 ca cht phn tch c thm vo. Ngha l chng ta c:
Vi mu phn tch khng thm chun:
Ax = a.Cx

(a)
245

Vi mu u phn tch c thm chun:


Atch= a.(Cx + Cl)

(b)

Do cm (a) chia cho (b) chng ta c:


C = [Ax/(Atch-Ax)]. C1

(11.7)

Nh vy khi o c gi tr Ax v Atch ta c tnh c nng Cx phi tm theo


biu thc (11.7).
Nhng mt iu phi ch l nng thm vo Cl v cc gi tr Cx phi nm
trong vng tuyn tnh ca phng php.
Trn y l cc phng php nh lng ch yu hay c s dng. Tt nhin
mi phng php u c nhng u im v nhc im nht nh ca n, v ngi
dng tu iu kin m p dng cho thch hp.
11.3 Cc kiu phng php phn tch theo AAS
Trong php o ph hp th nguyn t xc nh mt nguyn t hay mt hp
cht ngi ta c th tin hnh phn tch ngay chnh cht theo ph hp th nguyn t
ca n, nh phn tch cc kim loi, hay qua vic o ph hp th nguyn t ca mt
cht khc, khi cht phn tch khng c tnh cht hp th nguyn t, nhng cht ny li
c mt s tng tc rt nh lng v mt ha hc theo mt phn ng ha hc nht
nh vi mt kim loi c ph hp th nguyn t nhy. Do xut hin hai loi phng
php phn tch nh lng theo ph hp th nguyn t, l:
- Cc phng php phn tch trc tip, cho cht c ph AAS v
- Cc phng php phn tch gin tip, cho cht khng c ph AAS.
Sau y chng ta s nghin cu mt cch tm tt v hai loi phng php phn
tch ny.
11.3.1 Cc phng php xc nh trc tip
V nguyn tc th tt c cc nguyn t v cc cht c ph hp th nguyn t
chng ta u c th xc nh n mt cch trc tip theo ph hp th nguyn t ca n
t dung dch mu phn tch. Ngha l cc phng php xc nh trc tip ch ph hp
cho vic xc nh cc kim loi c vch ph hp th nguyn t. V cc kim loi u c
ph hp th nguyn t ca n trong nhng iu kin nht nh. Theo cch ny, ni
chung trong nhiu trng hp, mu phn tch trc ht c x l theo mt cch ph
hp c dung dch mu c cha cc Ion kim loi cn phn tch. Tip tin hnh
nh lng n theo mt trong cc cch chun ha bit (nh theo phng php
ng chun, phng php thm, hay phng php mt mu u,... c trnh by
trong mc 11.2 trn). y l cc phng php phn tch thng thng, v ang
c dng rt ph bin, xc nh lng vt cc kim loi trong cc i tng mu
hu c v v c khc nhau theo ph hp th nguyn t ca n. V th ngi ta gi i
246

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

11.3.12 Cc phng php phn tch gin tip


Cc phng php theo cc phn ng ho hc
Theo cch xc nh gin tip ny, ngi ta c cc phng php phn tch c th
sau y da theo mt s phn ng ha hc bit:
1. Phn ng to ra kt ta khng tan (mui hay sunphua)
Ni chung, cht no khi tc dng vi mt Ion kim loi trong dung dch to ra
c mt kt ta t tan, c tnh cht nh lng v c th tch ra c khi dung dch
mu th phn ng c th dng c cho php o ny. Theo nguyn tc ny ngi ta

xy dng 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

sunphua kh tan c tnh cht nh lng. V th thuc vitamin B1 cc hp cht hu c


kiu diol cng c xc nh theo cch ny.
Penicillin + NaPbO2 ----------- PbS
trong KOH nng chy, 280oC
Vitamin B1 + NaPbO2 ----------- Pbs
trong KOH nng chy, 280oC
2. Theo phn ng to hp cht phc
- Cht phn tch X phn ng vi thuc th l mt hp cht phc. Nguyn tc ca
cch ny l cho cht X cn xc nh tc dng vi mt phc cht thuc th kim loi
to ra mt hp cht phc bn c th chit tch ra c. Nhng phn ng ny phi c
tnh cht nh lng. Sau tch ly phc cht v xc nh hm lng kim loi trong
phc cht , ri t tnh ra hm lng ca cht cn phn tch X. V d axit phthalic
hay cc mui phthalat c th c xc nh qua phn ng ca n vi thuc th phc
Cu(I)-Neocuproine to ra phc cht mi l Cu(I)-(Neocuproine)2 Phthalat. Sau
chit ly phc cht ny vo mt dung mi hu c ph hp, nh MIBK v xc nh
hm lng Cu trong phc ny, t tnh ra hm lng phthalic trong mu phn tch.
Cng tng t nh vy, ngi ta xc nh nng NO 3 qua phn ng ca Ion
NO 3 vi thuc th Cu(I)-Neocuproine to ra phc cht Cu(I)-(Neocuproine)2-NO3chit c vo MIBK. Sau xc nh Cu trong phc ny bng php o AAS, v sau
suy ra hm lng Anion NO 3 trong mu.
- Cht phn tch X phn ng vi dung dch mui kim loi. Cch ny dng xc
nh cc Anion. Tt c cc Anion no c th tc dng c vi mt Ion kim loi to ra
c mt hp cht phc bn trong mt iu kin nht nh v chit ra c khi dung
dch mu th u c th s dng xc nh cc Anion .
V d xc nh Anion SCN qua phn ng ca Anion ny vi dung dch mui
FeCl3 trong mi trng pH=1, theo phn ng:
Fe3+ + SCN Fe(SCN)2+
Sau chit phc Fe(SCN) vo dung mi etyl ete v xc nh Fe trong dch chit
ny bng php o AAS (c th gii chit phc vo dung dch HCl 2M v xc nh Fe
trong dung dch gii chit ny). Sau ta cng tnh c nng ln SCN trong mu
phn tch.
3. Qua phn ng to thnh hp cht d a axit
Theo cch ny, nhng kim loi, Ion hay hp cht c kh nng to thnh nhng
hp cht axit d a u c th xc nh c mt cch gin tip qua hp cht d a. V
d nh photpho (P), Anion photphat (PO43-) hay ton silicat (SiO32-),... c th c xc
249

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

Bng cch ny La v Ce l cc nguyn t khng nhy ph hp th nguyn t


trong ngn la axetylen-khng kh (DL > 20 g/mL) li xc nh c n nhy l
0,5 - 1 l/mL. Bng cch bm mu phn tch cha La hay Ce vo dng cht mang nn
l dung dch phc Fe(III)-tartat hay Fe(III)-EDTA. Khi chiu cao ca lc hp th
ca vch ph Fe-248,3 nm l ph thuc tuyn tnh vo nng ca La v Ce trong
phm vi t 0,5 - 18 g/mL. y chnh l mt hng mi phn tch lng vt t
him bng php o F-AAS vi nhy cao.
6. Phn ng kh hp cht c nhm Nitro (-NO2)
Mt s hp cht Nitro trong mi trng pH thch hp c th b kh v amin (RNO2 R-NH2) bng kim loi hot ng, v d nh Cd, Zn,... rt nh lng, v phn
ng ny c s dng xc nh mt s hp cht hu c c nhm nitro, v d nh
xc nh Chloramphenicol, qua chun lng ln Cd(II) sinh ra trong phn ng hay
o ph hp th nguyn t ngn la (F-AAS ) ca dung dch Ion kim loi Cd(II). V d
trong mi trng axit long (HCl 0,05M), bt kim loi xp Cd kh nhm -NO2 v
NH2 hon ton nh lng theo phn ng sau.
3Cd + R-NO2 + 6HCl 3CdCl2 + H2O + R-NH2
Chloramphenicol
Nh vy sau khi phn ng kt thc, ly tnm ly dung dch mui CdCl2 v xc nh
Cd bng php o F-AAS v suy ra hm lng Chloramphenicol theo phn ng trn.
Vi cch ny c th xc nh c Chloramphenicol n nhy 0,1 ppm.
Hon ton tng t, nhiu hp cht hu c nitro u c th xc nh gin tip
theo php o ph hp th nguyn t [20].
Theo hiu ng tng hay gim cng vch ph AAS
Vic xc nh theo cch ny l da trn nguyn tc l cc cht cn xc nh trong
mt gii hn nng no n c kh nng lm tng hay gim tn hiu hp th
(cng ) ca mt vch ph ca mt nguyn t mt cch tuyn tnh. S tng tc ny
c th theo ba cch sau.
1. Tng tc an Ion-Cation
y Anion cn phn tch khi tc dng vi Ion kim loi s lm gim cng
ca vch ph hp th ca n, mt cch tuyn tnh, hay lm tng, khi Anion ny nm
trong mt khong nng nht nh. V d dung dch nn Mg 5 g/mL, Anion F lm
gim cng hp th ca vch ph Mg-285,2 nm trong ngn la n kh axetylenkhng kh rt tuyn tnh, khi nng ca Ion F- trong dung dch mu tng t 1-20.
g/mL. V d, theo tc dng lm gim cng vch ph, ngi ta cho cht phn tch
X (cn xc nh) tc dng vi dung dch mui ca mt kim loi c ph hp th nhy
mt nng nht nh ph hp v khng i to thnh hp cht bn v hp cht
251

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

Cc cht khc nh nhau


o AN (Mg-285,20 nh

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.

y l hiu ng ca s tng tc ca Cation-phn t. Trong nhiu trng hp,


mt s cht phn tch dng phn t, m bn thn n khng c ph hp th nguyn t,
252

nhng li c tc dng lm tng hay gim cng ca mt vch ph hp th ca kim


loi mt cch u n, khi nng ca n bin thin trong mt khong nht nh. Do
ngy nay ngi ta li dng tnh cht ny xc nh cc cht hu c bng
php o AAS. V d glucoz v cc hp cht amino hu c c tc dng lm tng
cng vch ph hp th nguyn t ca Ca, Zr,... tuyn tnh khi nng ca cc
cht bin thin trong vng nh hn 1.10-6M.
Dy chun xc nh nng protein
Cc cht

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

Cc cht khc nh nhau


o A (Ca-422,70 nm)

Ao

A1

A2

A3

A4

V d trong mu dung dch th vch ph hp th ca Ca-422,70nm, khi c mt


ca glucoz, trong vng nng t n.10-4 - n.10-5 mol/l s c tng theo tuyn tnh,
khi thc hin php o trong ngn la n kh l khng kh nn v axetylen (hnh
11.10a v 11.10b). Tnh cht ny c s dng xc nh mt s glucoz hay
amino axit trong cc i tng mu sinh hc. Sau y l dy chun xc nh
glucoz qua ph AAS ca Ca.

3. Tng tc Cation-Cation
Cch ny thng c dng xc nh mt nguyn t kim loi khng nhy ph
253

hp th nguyn t qua mt kim loi nhy ph hp th nguyn t hn. V d trong ngn


la axetylen-khng kh Ion Ti(IV) lm tng tn hiu AAS ca vch Fe-248,3 nm tuyn
tnh khi nng TI(IV) thay i t 2 - 50 g/mL. Cc Ion La(III), Ce(IV) lm tng tn
hiu AAS ca vch Fe-248,3 nm cng tuyn tnh khi nng La v Ce trong mu i t
0,5 n 20 g/mL. Tnh cht ny hin ang c nghin cu ng dng xc nh Ti
La, Ce v mt s nguyn t khc km nhy ph hp th trong ngn la n kh
axetylen-khng kh nn.
Theo phn ng to ra hp cht d bay hi
1. Theo phn ng sinh hp cht hydrua
Cch ny ch yu c dng xc nh cc nguyn t As, Bi, Ge, Pb, Sb, Sn,
Te, Hg. V n cho kt qu vi nhy cao hn php o trc tip bnh thng hng
chc n hng trm ln (bng sau). y ngi ta cho Zn kim loi tc dng vi cht
phn tch trong mi trng axit HCl, hay cht kh NaBH4 sinh ra cc hp cht
hydrua, v d AsH3, SbH3, PbH2 trong mt h thng phn ng ng kn, sau nh
mt dng kh mang tr (v d nh kh argon) m hp cht hydrit ny c dn vo
mi trng hp th nguyn t ha v o ph hp th ca nguyn t trong hp cht
hydrua .
Nguyn t

nhy ca F-AAS (g/L)


Trc tip

Qua Hydro

As

140

0,2

Sb

30

0,1

Bi

29

0,2

Se

30

0,2

Sn

110

0,5

y l phn ng ca mt s Anion ca mt s nguyn t vi nguyn t hydro


mi sinh to ra hp cht kh hydrua dng MeHn (vi n = 3, 4, 5 v 6). V d nh:
HgH2, ASH3, ASH5, SbH3, SbH5, SeH4, SeHs, TeH4, TeH6, v.v... Phn ng ny rt
nh lng, trong nhng iu kin ph hp cho mi cht. V th n cng c s dng
xc nh cc nguyn t Hg, As, Se, Te.. trong cc i tng khc nhau, nh trong
qung, trong nc, trong thc phm,... bng php o ph pht x v hp th nguyn t.
Song trc ht l mu phn tch cn c x l a cc nguyn t ny v dng
mui ca Ion tan trong dung dch nc mi trng axit, v d nh cc mui: HgCl2,
SbCl5, SnCl4, Na3ASO4, Na2SeO4, Na2TeO4, Sau thc hin theo cc phn ng sau.
+ Vi Hg:
HgCl2 + Na2BH4 + HCl HgH2
254

+ 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

c bit l trong vic phn tch cc cht hu c, cc sn phm dc v ha du


cc nc cng nghip pht trin, nh M, Php, CHLB c, Anh, Nht, H Lan,v.v...
Theo hng ny mt cun sch mang tn "Organic compound Analysis hy Atomic
Absorpt Ion Spectrometry" c cng b bi tc gi H. Hassan, 1988.

256

Chng 12
CC IU KIN O PH HP TH NGUYN T
V PHT X NGN LA CA MT S NGUYN T

Phn I. PHP O PH NGN LA

1. Nguyn t.

Al

- Nguyn t lng: 26,8915. Th Ion ho I: 5,98 eV.


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
Mc nhy ph

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax.
- Loi Burner: Khe di 5 cm.
- Chiu cao Burner: 7 - 6 mm.
- Kh ngn la: (N2O + C2H2) vi t l 5,5/4,5 L/ph (V/V).
- nhy LOD vch No1: 0,2 g/mL (ppm).
- Vng tuyn tnh: 1 - 12 g/m.
2. Nguyn t.

Ag

- Nguyn t lng: 107,8680. Th Ion ho I: 7,57 eV.


- Ch o ph: F-AAS (Hp th nguyn t).
257

- 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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax.
- Loi Burner: Khe di 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,2 L/ph (V/V).
- nhy LOD vch Nol: 0,05 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 6,0 g/mL.
3. Nguyn t.

Au

- Nguyn t lng: 196,9665. Th Ion ho I: 9,22 eV.


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph AAS:
No

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 50 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,2 L/ph (V/V).
- nhy LOD vch Nol: 0,05 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 5 g/mL.
258

4. Nguyn t.

Ba

- Nguyn t lng: 137,3400. Th Ion ho I: 8,29 eV.


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph AAS:
No

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 5 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la. (N2O + C2H2) vi t l 5,514,5 L/ph (V/V).
- nhy LOD vch Nol: 0,5 g/mL (ppm).
- Vng tuyn tnh: 2 - 18 g/mL.
5. Nguyn t.

Be

- Nguyn t lng: 9,0122. Th Ion ho I: 9,32 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 5 cm.
- Chiu cao Burner: 5 - 6 mm.
259

- Kh ngn la: (N2O + C2H2) vi t l 5,5/4,2 L/ph (V/V).


- nhy LOD vch Nol: 0,5 g/mL (ppm).
- Vng tuyn tnh: 1 - 15 glml.
6. Nguyn t.

Bi

- Nguyn t lng: 208,9806. Th Ion ho I: 7,29 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,3 L/ph (V/V).
- nhy LOD vch Nol: 0,1 g/mL (ppm).
- Vng tuyn tnh: 0,5 - 8 g/mL.
7. Nguyn t.

Ca

- Nguyn t lng: 40,0800. Th Ion ho I: 6,11 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:

260

No

Vch ph (nm)

Mc nhy ph km
vch s 1

Ca-422,70

Ca-239,90

150 ln km

Ghi ch

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,3 U/ph (V/V).
- nhy LOD vch Nol: 0,05 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 5,0 g/mL.
8. Nguyn t.

Cd

- Nguyn t lng: 112,4000. Th Ion ho I; 6,12 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:

Vch ph (nm)

Mc nhy ph km
vch s 1

Cd-228,80

Cd-326,90

500 ln km

Ghi ch

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 50 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,2 L/ph (V/V).
- nhy LOD vch Nol: 0,025 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 2,5 g/mL.
9. Nguyn t.

Co

- Nguyn t lng: 58,9332. Th Ion ho I: 7,86 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,25 L/ph (V/V).
- nhy LOD vch Nol: 0,1 g/mL (ppm).
- Vng tuyn tnh: 0,5 - 8,0 g/mL.
10. Nguyn t.

Cr

- Nguyn t lng: 51,9960. Th Ion ho I: 6,76 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,3 L/ph (V/V).
- nhy LOD vch Nol: 0,1 g/mL (ppm).
- Vng tuyn tnh: 0,5 - 8,0 g/mL.
262

11. Nguyn t.

Cu

- Nguyn t lng: 63,5460. Th Ion ho I: 7,72 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,2 L/ph (V/V).
- nhy LOD vch Nol: 0,025 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 4,0 g/mL.
12. Nguyn t.

Fe

- Nguyn t lng: 55,847. Th Ion ho I: 7,87 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
263

- Chiu cao Burner: 5 - 6 mm.


- Kh ngn la: (Khng kh + C2H2) vi t l 5,211,3 L/ph (V/V).
- nhy LOD vch Nol: 0,05 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 8,0 g/mL.
13. Nguyn t.

- Nguyn t lng: 39,1000. Th Ion ho I: 4,34 eV


- Ch o ph: F-AES (Pht x ngn la).
- Vch ph o F-AES:
No

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

- Khe o: 0,2 - 0,5 nm.


- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,25 L/ph (V/V).
- nhy LOD vch Nol: 0,05 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 8,0 g/mL.
14. Nguyn t.

Li

- Nguyn t lng: 6,9410. Th Ion ho I: 5,39 eV


- Ch o ph: F-AES (Pht x ngn la).
- Vch ph o F-AES:
No

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

- Khe o: 0,2 - 0,5 nm.


264

Ghi ch

- Loi Burner: 10 cm.


- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,2 L/ph (V/V).
- nhy LOD vch Nol: 0,05 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 8,0 g/mL.
15. Nguyn t.

Mg

- Nguyn t lng: 24,3050. Th Ion ho I: 7,64 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60-80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (K.kh + C2H2) vi t l 5,2/1,25 L/ph (V/V).
- nhy LOD vch Nol: 0,02 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 3,0 g/mL.
16. Nguyn t:

Mn

- Nguyn t lng: 54,9380. Th Ion ho I: 7,43 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,25 L/ph(VN).
- nhy LOD vch Nol: 0,025 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 5,0 g/mL.
17. Nguyn t.

Na

- Nguyn t lng: 22,9898. Th Ion ho I: 5,14 eV


- Ch o ph: F-AES (Pht x ngn la).
- Vch ph o F-AES:

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

- Khe o: 0,2 - 0.5 nm.


- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,2 L/ph (V/V).
- nhy LOD vch Nol: 0,02 g/mL (ppm).
- Vng tuyn tnh: 0,05 - 2,0 g/mL.
18. Nguyn t.

Ni

- Nguyn t lng: 58,7900. Th Ion ho I: 7,61 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
266

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,30 L/ph (V/V).
- nhy LOD vch Nol: 0,05 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 8,0 g/mL.
19. Nguyn t.

Pb

- Nguyn t lng: 207,2000. Th Ion ho I: 7,42 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,25 L/ph (V/V).
- nhy LOD vch Nol: 0,1 g/mL (ppm).
- Vng tuyn tnh: 0,5 - 8,0 g/mL.
267

20. Nguyn t.

Rb

- Nguyn t lng: 85,4680. Th Ion ho I: 4,18 eV


- Ch o ph: F-AES (Pht x ngn la).
- Vch ph o F-AES:
No

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

- Khe o: 0,2 - 0,5 nm.


- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,2 L/ph (V/V).
- nhy LOD vch Nol: 0,05 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 5,0 g/mL.
21. Nguyn t.

Sb

- Nguyn t lng: 121,7500. Th Ion ho I: 8,68 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,25 L/ph (V/V).
268

- nhy LOD vch Nol: 0,1 g/mL (ppm).


- Vng tuyn tnh: 0,5 - 8,0 g/mL.
22. Nguyn t.

Si

- Nguyn t lng: 28,0860. Th Ion ho I: 8,15 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 5 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (N2O + C2H2) vi t l 5,5/4,5 L/ph (V/V).
- nhy LOD vch Nol: 0,5 g/mL (ppm).
- Vng tuyn tnh: 2 - 20 g/mL.
23. Nguyn t.

Si

- Nguyn t lng: 87,6200. Th Ion ho I: 5,69 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

Vch ph (nm)

Mc nhy ph km
vch s 1

sr-460,70

Sr-407,80

25 ln km

Ghi ch

- Khe o: 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Burner: 10 cm.
269

- Chiu cao Burner: 5 - 6 mm.


- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,3 L/ph (VN).
- nhy LOD vch Nol: 0,025 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 5,0 g/mL.
24. Nguyn t.

Zn

- Nguyn t lng: 65,3700. Th Ion ho I: 9,39 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

Vch ph (nm)

Mc nhy ph km
vch s 1

Zn-213,90

Zn-307,60

2000 ln km

Ghi ch

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 50 - 80% Imax
- Loi Burner: 10 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Khng kh + C2H2) vi t l 5,2/1,2 L/ph (V/V).
- nhy vch Nol: 0,02 g/mL (ppm).
- Vng tuyn tnh: 0,1 - 2,5 g/mL.
25. Nguyn t.

Zr

- Nguyn t lng: 91,2200. Th Ion ho I: 7,80 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS: -

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 50-80% Imax
- Loi Burner: 5 cm.
- Chiu cao Burner: 5 - 6 mm.
- Kh ngn la: (Kh N2O + C2H2) vi t l 5,5/4,5 L/ph(V/V).
- nhy LOD vch Nol: 0,5 g/mL (ppm).
- Vng tuyn tnh: 2 - 10 g/mL.

271

Phn II. PHP O KHNG NGN LA

1. Nguyn t.

Al

- Nguyn t lng: 26,8915. Th Ion ho I: 5,98 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 600 - 800oC, Thi gian: 25 giy.
+ Giai on NTH: Nhit : 2650oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2800oC, Thi gian: 2 giy
- nhy LOD vch Nol: 0,5 ng/mL (ppb).
- Vng tuyn tnh: 2,5 - 25 ng/mL.
2. Nguyn t.

Ao

- Nguyn t lng: 107,8680. Th Ion ho I: 7,57 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
272

No

Vch ph (nm)

Mc nhy ph km
vch s 1

Ag-328,10

Ag-328,30

2,5 ln km

Ghi ch

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 50 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- B chnh nn: C BC
- 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 : 500 - 800oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2550oC, 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: 1 - 20 ng/mL.
3. Nguyn t.

Au

- Nguyn t lng: 196,9665. Th Ion ho I: 9,22 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph AAS:
No

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 50 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn
- Kh tr mi trng: Argon.
273

- 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

- Nguyn t lng: 137,3400. Th Ion ho I: 8,29 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph AAS:
No

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy; Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 600 - 900oC, 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: 0,5 ng/mL (ppb).
- Vng tuyn tnh.4 - 40 ng/mL.

274

5. Nguyn t.

Be

- Nguyn t lng: 9,0122. Th Ion ho I: 9,32 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 550 - 800oC, Thi gian: 20 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: 0,5 ngi (ppb).
- Vng tuyn tnh: 2 - 20 ngi.
6. Nguyn t.

Bi

- Nguyn t lng: 208,9806. Th Ion ho I: 7,29 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
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

35 ln km

Ghi ch

275

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- 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 : 400 - 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: 0,5 ngi (ppb).
- Vng tuyn tnh: 4 - 40 ngi.
7. Nguyn t.

Ca

- Nguyn t lng: 40,0800. Th Ion ho I: 6,11 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

Vch ph (nm)

Mc nhy ph km
vch s 1

Ca-422,70

Ca-239,90

150 ln km

Ghi ch

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 600 - 800oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2550oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2700oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,5 ng/mL (ppb).
- Vng tuyn tnh: 2 - 20 ng/mL.
276

8. Nguyn t.

Cd

- Nguyn t lng: 112,4000. Th Ion ho I: 6,12 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

Vch ph (nm)

Mc nhy ph km
vch s 1

Cd-228,80

Cd-326,90

500 ln km

Ghi ch

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 50 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn. 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 : 400 - 600oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2200oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2400oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,05 ng/mL (ppb).
- Vng tuyn tnh: 0,5 - 15 ng/mL.
9. Nguyn t.

Co

- Nguyn t lng: 58,9332. Th Ion ho I: 7,86 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,7 - 0,5 nm.


- Cng n HCL: 60 - 80% Imax
277

- Loi Cuvt Graphit: Hot ho ton phn.


- 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 : 500 - 700oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2550oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2700oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,5 ng/mL (ppb).
- Vng tuyn tnh: 2,5 - 25 ng/mL.
10. Nguyn t.

Cr

- Nguyn t lng: 51,9960. Th Ion ho I: 6,76 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit ; 120 - 250 oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 500 - 800 oC, Thi gian: 20 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: 0,5 ng/mL (ppb).
- Vng tuyn tnh: 2 - 30 ng/mL.
278

11. Nguyn t.

Cu

- Nguyn t lng: 63,5460. Th Ion ho I: 7,72 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 50 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- 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 : 450 - 600oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2400oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2500oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,2 ng/mL (ppb).
- Vng tuyn tnh: 1 - 20 ng/mL.
12. Nguyn t.

Fe

- Nguyn t lng: 55,847. Th Ion ho I: 7,87 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- 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 : 550 - 800oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2550oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2700oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,5 ng/mL (ppb).
- Vng tuyn tnh: 2 - 25 ng/mL.
13. Nguyn t.

Mg

- Nguyn t lng: 24,3050. Th Ion ho I: 7,64 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 50 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on gy: Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 600 - 900oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2600oC, Thi gian: 3 giy.
280

+ Giai on lm sch Cuvt: Nhit : 2700oC, Thi gian: 2 giy.


- nhy LOD vch Nol: 0,25 ng/mL (ppb).
- Vng tuyn tnh: 2 - 20 ng/mL.
14. Nguyn t.

Mn

- Nguyn t lng: 54,9380. Th Ion ho I: 7,43 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 50 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on gy: Nhit : 120 - 200oC, Thi gian: 30 giy
+ Giai on tro ho: Nhit : 500 - 700oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2450oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2600oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,2 ngi (ppb).
- Vng tuyn tnh: 1 - 20 ngi.
15. Nguyn t.

Mo

- Nguyn t lng: 95,94. Th Ion ho I: 7,80 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:

281

No

Vch ph (nm)

Mc nhy ph km
vch s 1

Mo-

Mo-

Ln km

Mo-

Ln km

Mo-

Ln km

Ghi ch

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on gy: Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 600 - 900oC, Thi gian: 30 giy.
+ Giai on NTH: Nhit ; 2700oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2800oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,5 ng/mL (ppb).
- Vng tuyn tnh: 5 - 60 ng/mL.
16. Nguyn t.

Ni

- Nguyn t lng: 58,7900. Th Ion ho I: 7,61 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
282

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

- Nguyn t lng: 207,2000. Th Ion ho I: 7,42 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
Mc nhy ph km
vch s 1

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- 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 : 450 - 550oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 1900oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2200oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,5 ng/mL (ppb).
283

- Vng tuyn tnh: 2 - 50 ng/mL.


18. Nguyn t.

Sb

- Nguyn t lng: 121,7500. Th Ion ho I: 8,68 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit : 120 - 180oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 400 - 600oC, Thi gian: 30 giy.
+ Giai on NTH: Nhit : 2400oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2600oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,5 ng/mL (ppb).
- Vng tuyn tnh: 2,5 - 40 ng/mL.
19. Nguyn t.

Si

- Nguyn t lng: 28,0860. Th Ion ho l: 8,15 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:

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

- Khe o: 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 600 - 1000oC, Thi gian: 30 giy.
+ Giai on NTH: Nhit : 2700oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2800oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 1 ng/mL (ppb).
- Vng tuyn tnh: 5 - 100 ng/mL.
20. Nguyn t.

Si

- Nguyn t lng: 87,6200. Th Ion ho I: 5,69 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

Vch ph (nm)

Mc nhy ph km
vch s 1

Sr-460,70

Sr-407,80

50 ln km

Ghi ch

- Khe o: 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
285

- iu kin nguyn t ho:


+ Giai on sy: Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 550 - 700oC, Thi gian: 30 giy.
+ Giai on NTH: Nhit : 2550oC, 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.
21. Nguyn t.

Ti

- Nguyn t lng: 47,90. Th Ion ho I: 6,82 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 600 - 900oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2650oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2800oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,5 ng/mL (ppb).
- Vng tuyn tnh: 5 - 80 ng/mL.
286

22. Nguyn t.

- Nguyn t lng: 50,9441. Th Ion ho I: 6,75 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

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

- Khe o: 0,5 - 0,7 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- Kh tr mi trng: Argon.
- B chnh nn: C BC
- iu kin nguyn t ho:
+ Giai on sy: Nhit : 120 - 250oC, Thi gian: 30 giy.
+ Giai on tro ho: Nhit : 550 - 700oC, Thi gian: 20 giy.
+ Giai on NTH: Nhit : 2700oC, Thi gian: 3 giy.
+ Giai on lm sch Cuvt: Nhit : 2800oC, Thi gian: 2 giy.
- nhy LOD vch Nol: 0,5 ng/mL (ppb).
- Vng tuyn tnh: 5 - 80 ng/mL.
23. Nguyn t.

Zn

- - Nguyn t lng: 65,3700. Th Ion ho I: 9,39 eV


- Ch o ph: F-AAS (Hp th nguyn t).
- Vch ph o AAS:
No

Vch ph (nm)

Mc nhy ph km
vch s 1

Zn-213,90

Zn-307,60

2000 ln km

Ghi ch

287

- Khe o: 0,5 nm.


- Cng n HCL: 60 - 80% Imax
- Loi Cuvt Graphit: Hot ho ton phn.
- 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 : 450 - 700oC, 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: 0,1 ng/mL (ppb).
- Vng tuyn tnh: 0,5 - 10 ng/mL.

288

TI LIU THAM KHO

1. RiChard D. Beaty & Jack D. Kerber, 1979 & 1983, Concepts on


Instrumentation and Techniques in Atomic Emission Spectrophotometry, Perkin Elmer
Company.
2. Hobart H. Willard, Lynne L. Merritt, John A. Dean & Frank A. Settle, 1993,
Instrumental Methods for Analysis, Wadsworth Pub. Company, 6th Edition.
3. E.L. Grove, 1978, Applied Atomic Spectroscopy, Plenum Press, New York.
4. M. Pinta, 1979, Atomic Absorption and Emission Spectrometry, Vol. I & II,
London, Hilger.
5. Peter J. Whitesside, 1979 & 1985, Atomic Spectrometry Data Book, Pye
Unicam, Ltd.
6. R.E. Stuegeon & C.L. Charrabarti, 1979 & 1985, Recent Advances in Atomic
Emission Spectrometry, Perkin Elmer.
7. Douglas A. Skoog & James J. Leary, 1995. Principles of Instrumental
Analysis, Saunder8 College Pub., 4th Edit Ion, New York, London.
8. Perkin Elmer Company, 1985-90, Some Application Notes In AAS, Perkin
Elmer Ltd.
9. S.S. M. Hassan, 1984, Organic Analysis Using Atomic Spectrometry,
Amsterdam, Hilger, London.
10. J.B. Dowson, 1989, Annual Reports on Analytical Atomic Spectroscopy,
Vol. 7 & 8, Amsterdam, London.
11. Daniel C. Harris, 1998, Quantitative Chemical Analysis, Fifth Edit Ion, W.H.
Freeman & Company, New York.
12. Douglas A. Skoog, Donald M. West & F. James Holler, 1995. Fundamentals
of Instrumental Analysis, 7th Edit Ion, New York, London, Amsterdam, Tokyo.
13. James D. Ingle, Jr. & Stanley R. Grouch, 1992, Spectro-chemical Analysis,
Prentice Hall, Upper Saddle River, New Jersey.
14. Geoge R. Harrison, 1979, Wavelength Tables, The M.I.T. Press, Cambridge,
London.
15. R.M. Barnes, 1987, Application Inductively Coupled Plasma Emission
Spectroscopy, Easten Analytical Symposium.
16. John H. Kennedy, 1990, Analytical Chemistry Principles, Saunders College
Pub., 2nd Edit Ion, New York, London.
289

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

4.2 Mt s nh hng trong php o AES ................................................................75


4.2.1 Cc yu t v ph..........................................................................................75
4.2.2 Cc yu t vt l.............................................................................................77
4.2.3 Cc yu t ha hc ........................................................................................79
Chng 5: PHN TCH QUANG PH PHT X NH TNH ...............................88
5.1 Nguyn tc chung ................................................................................................88
5.2 Vch chng minh nh tnh v cch chn............................................................89
5.3 nhy ph v kh nng pht hin.....................................................................90
5.3.1 nhy tuyt i (cn gi l nhy khi lng) ......................................90
5.3.2 nhy tng i (cn gi l nhy nng ) .........................................90
5.4 S trng vch v cch loi tr .............................................................................93
5.4.1 Vch ph trng..............................................................................................93
5.4.2 Vch quy ri v chen ln.............................................................................93
5.4.3 Ph m.........................................................................................................93
5.5 Cc phng php phn tch nh tnh ..................................................................94
5.5.1 Phng php quan st trc tip trn mn nh...............................................95
5.5.2 Phng php so snh ph..............................................................................95
5.5.3 Phng php ph chun (Dng bn atlas) ....................................................96
Chng 6: PHN TCH PH PHT X NH LNG ..........................................99
6.1 Nhng vn chung ............................................................................................99
6.1.1 Phng trnh c bn v nguyn tc...............................................................99
6.1.2 Vch phn tch v cch chn.......................................................................101
6.1.3 Cch biu din nng trong phn tch quang ph....................................102
6.1.4 Mu chun trong phn tch quang ph pht x ...........................................104
6.1.5 Gii hn chng minh v khong xc nh ..................................................106
6.1.6 S bay hi v ng cong bay hi .............................................................108
6.1.7. Kh quyn kim tra.....................................................................................110
6.1.8 Cht m v cht ph gia trong phn tch ph pht x ...............................113
6.2 Phn tch quang ph pht x bn nh lng.....................................................119
6.2.1 Phng php so snh...................................................................................119
6.2.2 Phng php hin vch ...............................................................................120
6.3 Phn tch quang ph pht x dinh lng ...........................................................121
6.3.1 Phng php ng chun..........................................................................121
6.3.2 Phng php th chun khng i .........................................................124
6.3.3 Phng php thm tiu chun.....................................................................125
6.3.4 Phng php theo 1 mu chun ..................................................................127
6.4 Cc phng php xc nh gin tip bng AES ................................................128
6.4.1 Nguyn tc ..................................................................................................128
6.4.2 Cc phng php phn tch gin tip..........................................................128
Phn II..........................................................................................................................135
292

Chng 7: NHNG VN CHUNG CA PHP O ASS..................................135


7.1 S xut hin ph hp th nguyn t ..................................................................135
7.2 Cng ca vch ph hp th nguyn t .......................................................137
7.3 Cu trc ca vch ph hp th nguyn t..........................................................140
7.4 Nguyn tc v trang b ca php o AAS..........................................................143
7.5 Nhng u v nhc im ca php do AAS .....................................................145
7.6 i tng v phm vi ng dng ca AAS ........................................................147
Chng 8: Cc k thut nguyn t ha mu ..................Error! Bookmark not defined.
8.1 Mc ch v nhim v .......................................................................................149
8.2 K thut nguyn t ha mu bng ngn la.......................................................149
8.2.1 Yu cu v nhim v ca ngn la .............................................................149
8.2.2 c im v cu to ca ngn la n kh .................................................151
8.2.3 Trang b nguyn t ha mu...................................................................152
8.2.4 Nhng qu trnh xy ra trong ngn la.......................................................156
8.2.5 Ti u ha cc iu kin nguyn t ha mu .............................................163
8.3 K thut nguyn t ha khng ngn la ............................................................165
8.3.1 c im v nguyn tc ..............................................................................165
8.3.2 Cc yu cu h thng nguyn t ha mu ..................................................166
8.3.3 Nguyn tc v cc giai on ca qu trnh nguyn t ha mu..................166
8.3.4 Cc yu t nh hng..................................................................................174
8.3.5 Cc qu trnh trong cuvet graphit................................................................177
8.3.6 Trang b nguyn t ha mu...................................................................182
8.3.7 Ti u ha cc diu kin cho php o khng ngn la mu. .....................183
Chng 9: TRANG B CA PHP O ASS.............................................................185
9.1 Ngun pht bc x n sc................................................................................185
9.1.1 n catot rng (HCL) .................................................................................186
9.1.2 n phng in khng din cc (EDL) ......................................................189
9.1.3 n ph lin tc c bin iu......................................................................192
9.1.4 Cc loi ngun n sc khc.......................................................................194
9.2 Trang b nguyn t ha mu .........................................................................194
9.3 H thng n sc v my quang ph hp th nguyn t...................................195
9.4 Trang b pht hin, Detector, Photomultivlier ...................................................197
9.5 K thut o cng vch ph hp th.............................................................198
Chng 10: Cc yu t nh hng trong AAS ...........................................................201
10.1 Khi qut chung ...............................................................................................201
10.2 Mt s nh hng trong php do AAS............................................................201
10.2.1 Cc yu t v ph......................................................................................201
10.2.3 Cc yu t ha hc ....................................................................................207
Chng 11: Phn tch nh lng bng ph AAS.......................................................219
11.1 Nhng vn chung ........................................................................................219
293

11.1.1 Phng trnh c bn ca php o..............................................................219


11.1.2 Mu chun trong php o AAS.................................................................221
11.1.3 Biu din nng trong php o AAS .....................................................222
11.1.4 Khi nim v nhy ...............................................................................225
11.1.5 Gii hn pht hin trong AAS ..................................................................229
11.1.6 Khong xc nh trong php o AAS .......................................................231
11.1.7 B chnh nn trong php o AAS .............................................................232
11.1.8 Ti u ha cc iu kin cho php o AAS .............................................237
11.2 Cc phng php phn tch c th...................................................................240
11.2.1 Phng php th chun (ng chun) ................................................240
11.2.2 Phng php thm tiu chun...................................................................242
11.2.3 Phng php th chun c nh............................................................243
11.2.4 Phng php mt mu chun....................................................................245
11.3 Cc kiu phng php phn tch theo AAS ....................................................246
11.3.1 Cc phng php xc nh trc tip .........................................................246
11.3.2 Cc phng php xc nh gin tip cc cht bng AAS .........................247
Chng 12: CC IU KIN O PH HP TH NGUYN T V PHT X
NGN LA CA MT S NGUYN T ..............................................................257
Phn I. PHP O PH NGN LA .........................................................................257
Phn II. PHP O KHNG NGN LA .................................................................272
TI LIU THAM KHO ...........................................................................................289

294

NH XUT BN I HC QUC GIA H NI


16 Hng Chui - Hai B Trng - H Ni
in thoi: (04) 9718312; (04) 7547936; Fax: (04) 9714899
Email: nxb@vnu.edu.vn
***
Chu trch nhim xut bn:
Gim c: PHNG QUC BO
Tng bin tp: PHM THNH HNG
Chu trch nhim ni dung:
Hi ng nghim thu gio trnh
Trng HKHTN - i hc Quc gia H Ni
Ngi nhn xt:
GS. TSKH TRNH XUN GIN
TS. NGUN HONG
Bin tp:
H TH IP - QUC THNG
Bin tp ti bn:
INH QUC THNG
V hnh:
INH QUC THNG
Trnh by ba:
NGUYN NGC ANH

PHNG PHP PHN TCH PH NGUYN T


M s 1K-25 H2006
In 1000 cun, kh 19 x 27cm ti Xng in Tng cc Cng nghip Quc phng
S xut bn: 105 - 2006/CXB/62 - 08/HQGHN, ngy 10/02/2006.
Quyt nh xut bn s: 173 KH/XB
In xong v np lu chiu qu 11 nm 2006.

295