CHNG I :

I CNG V PHNG PHP PHN TCH HA L

1.1. ai cng
Bn cnh cc phng php phn tch ha hc, phng php phn tch ha l
da trn tnh cht vt l v ha hc ca vt cht, kho st hin tng xy ra khi
vt cht chu tc ng ca nhng yu t: bc x, in, nhit. Kt qu tng tc
c ghi nhn, t c th nh tnh hay nh lng mu vt cht. to s tc
ng v ghi nhn kt qu tng tc, cn dng c v thit b thch hp, do
phng php cn c c gi l phng php phn tch cng c.
Hin nay, cc thit b dng trong phn tch cng c pht trin v hin i
ha, do cng m rng phng php v tn ng dng nhng thit b ny.
So vi cc phng php phn tch ha hc, nhng phng php phn tch
ha l c u im:
-

nhy cao, c th nh lng n nng vi ppm hay c th vi ppb.

C chnh xc cao, lp li cao.

C tnh chn lc, c th xc nh ng thi nhiu cu t m khng qua giai

on tch chng

Nhanh, vi h thng t ng c th xc nh hng lot mu

Nhc im:
-

Cn thit b v chuyn vin vn hnh, bo tr .

Thit b t tin

1.2. Phan loai

Ty thuc bn cht ca hin tng gy tc ng v ty thuc thit b s dng
c th chia lm 4 nhm phng php chnh.
1.2.1.

Nhom cac phng phap quang

Nguyn tc da trn s tng tc gia mu v bc x. Ty bn cht ca mu

v bc x, thu c kt qu di dng tn hiu hay i lng o, t nh tnh
v nh lng mu.

Nhng phng php thng dng gm :

-

Phng php quang ph hp thu: t ngoi, thy c, hng ngoi, cng

hng t ht nhn.

Phng php quang ph pht x

Phng php quang ph ngn la: hp thu v pht x

1.2.2.

Nhom cac phng phap ien hoa

Da trn hin tng lin quan n tnh cht in ca mu kho st, hay da
trn tnh bin thin ca mt s i lng vt l ca dng in khi c s hin din
ca mu trong h thng mch.
Gm:
-

Phng php in khi lng

Phng php chun in th

Phng php cc ph v chun ampe

Phng php o in dn

1.2.3.

Nhom cac phng phap sac ky

Da trn tnh cht phn b hay hp ph khc nhau ca nhng cu t trong

mu gia hai dung mi hay hai pha ng khng trn ln vo nhau, c th tch ri
nhng cu t trong mu nh tnh v nh lng chng .
-

Cc phng php sc k n gin

Sc k kh : lng kh v rn kh

Sc k lng: lng lng v rn lng

1.2.4.

Nhom cac phng phap khac

Gm nhng phng php khc khng thuc 3 nhm trn:

-

Phng php phn tch nhit

Phng php phn tch nhit in

Phng phn o dn in

Phng php chun nhit lng

CHNG II: I CNG CC PHNG PHP PHN TCH QUANG PH

2.1 Khi nim v phng php quang ph
Phng php quang ph hc l phng php nghin cu s tng tc in t cc loi bc
x khc nhau ca vi vt cht. Cc bc x tng tc vi vt cht nh th no l ty thuc

vo nng lng ca n. V d cc tia cc tm, tia kh kin c nng lng cao nh hng
ti cc mc nng lng ca cc electron bn ngoi. Bc x hng ngoi c hp th bi
vt cht dn n s quay hay dao ng ca cc phn t. Ngoi ra khi vt cht hp th
nng lng t cc ngun khc nh nng lng nhit, nng lng in chng s chuyn
ln trng thi cao hn. trng thi ny chng khng bn v pht ra nhng bc x c
trng tr v trng thi c bn. V vy trong phng php quang ph nu phn loi
theo hin tng ta c phng php ph hp th v phng php ph pht x. Nu phn
loi theo bn cht sng in t ta c ph IR, ph UV-Vis, ph tia X v.v.... Trong phng
php quang ph cc cht c nhn bit thng qua tn s hay bc sng t trng t qu
trnh hp thu hay pht x v c nh lng thng qua lng bc x in t c hp
th hay pht x, Vn ny s c lm sng t trong cc chng tip theo
2.2 Sng in t
2.2.1 Tnh cht sng in t

a. Mt s quan nim v bc x in t
Thuyt v sng in t do Maxwell a ra. Theo ng th mi bin
thin ca in trng u lm pht sinh ra mt t trng v ngc li, mi
bin thin ca t trng u lm xut hin mt in trng trong khng
gian xung quanh.
V vy khi mt in tch dao ng vi tn s s lm xut hin mt in
trng v mt t trng bin thin cng tn s . Trng tng hp ca in
trng v t trng gi l trng in t. Trng in t truyn trong khng
gian gi l sng in t
Chnh Maxwell, ngi u tin tin on sng in t vi tn s
thch hp phi ng nht vi nh sng nhn thy. iu c ngha l nh
sng c bn cht l sng in t. L thuyt ny gi thuyt sng in t .
Trong sng in t, in trng

v t trng

lun lun c

phng vung gc vi nhau v gc vi phng truyn ca sng in t

( ti mi im cng in trng v cng t trng tng ri gim
v i chiu

 Qung ng m sng in t truyn i trong mt chu k T ( thi

gian thc hin mt dao ng ) c gi l bc sng hay di sng .
Nu gi c l vn tc truyn sng ta c h thc: = c.T= c/ ( l s chu k
trong mt giy)
Sng radio, vi sng, bc x hng ngoi ( IR), nh sng thy c
( kh kin vis) , bc x t ngoi( UV) tia rngen (X), tia u l sng
in t. Bn cht ca chng ging nhau ch khc nhau di sng .
Trong ph sng in t c mt vng hp t 390nm < < 770nm c
th thu nhn c bng mt gi l bc x kh kin.
Min kh kin chia lm 7 vng hp vi mu sc khc nhau. Nu i
t vng bc sng di ti vng bc sng ngn ta c cc min : , cam,
vng, lc, cam, vng, tm
Ni tip vi min tm v pha bc sng ngn l vng t ngoi
(UV). Tia v tia rngen (X) l nhng bc x in t c bc sng ngn.
Ni tip vi vi min vng bc sng di l min bc x hng
ngoi (IR) , tip theo l min vi sng v sng radio ( i truyn thanh)

 Thuyt lng t ca Planck (1900)

Mt vt rn khi c t nng s pht ra bc x, ph thu c gi l ph
bc x nhit. Bc x nhit pht ra l do chuyn ng dao ng ca cc ht tch
in c th l ion, electron cc vt th c t nng. gii thch ph bc x
nhit nm 1900 Planck a ra thuyt lng t gi l thuyt lng t Planck
Theo thuyt lng t th Mt dao ng t dao ng vi tn s ch c th
pht ra hay hp thu nng lng tng n v gin on, tng lng nh mt,
nguyn vn, gi l nng lng lng t , lng t nng lng ny t l vi tn s
ca dao ng t
= h
h l hng s Planck , h = 6,625.10-34j.s
Thuyt Planck nh vy pht hin ra tnh gin on ca nng lng. Gi l
tnh lng t.
Mt khc, v nng lng ca dao ng t pht ra hay hp thu di dng nng
lng bc x nn thuyt lng t Planck cng c ngha l: nh sng hay bc x
ni chung gm nhng lng t nng lng = h pht i t ngun sng.
6

V vy thuyt lng t Planck cn gi l thuyt lng t nh sng

Tnh nh nguyn sng ht ca nh sng
Theo thuyt lng t nh sng th nh sng gm nhng lng t c nng
lng = h pht ra t ngun sng. Mc khc theo h thc tng i Eintein
(1903) E = mc2 th vt th bt k nu c nng lng l E th s c khi lng m =
E/ c2. Nh vy ng vi nng lng lng t = h th nh sng c khi lng:
m

h
h

2
c
.c

T ta c tnh ht ca nh sng.
Thuyt lng t nh sng c Planck a ra nm 1900 v tnh ht nh sng
c suy ra mt cch t nhin t h thc tng i ca Eintein. Thuyt lng t
hay thuyt ht nh sng ch l mt v do s pht minh ng gp ca hai nh bc
hc li lc l Planck v Eintein
Theo h thc tng i Eintein :

m0
V2
V 2 hay m0 m 1 2
1
c
c2

i vi chnh nh sng th v = c suy ra : m 0 = 0 vy khi lng ngh m0 ca

nh sng bng khng.
Theo thuyt lng t nh sng th mu sc ph thuc vo nng lng ca
photon( lng t nh sng ) = h = h , ngha l ph thuc vo tn s nh sng
cn cng nh sng ph thuc vo nng ht nh sng trong chm sng.
Tnh nh nguyn ca nh sng
Trc khi c thuyt ht nh sng c thuyt sng nh sng do Maxwell
a ra 1865. N gii thch c cc hin tng nh giao thoa nh sng, nhiu x
nh sng nhng khng gii thch c cc hiu ng quang in Ngc li
thuyt ht gii thch c cc hiu ng quang in nhng khng gii thch c
cc hin tng nh giao thoa nh sng.
Lch s khoa hc ghi nhn trong thi k ny c cuc tranh ci gia hai
trng phi sng v ht. Nhng ngi theo trng phi sng th c gii thch

nhng hin tng nh hiu ng quang in, cn nhng ngi theo trng phi ht
th c gng gii thch cc hin tng nh giao thoa nh sng.
Nm 1924 Louis de Broglie mt nh bc hc ngi Php thng nht hai
thuyt. Theo ng chnh thuyt ht v nh sng tha nhn tnh sng, v theo
thuyt ny, ht nh sng c nng lng c tnh theo cng thc h , trong
c cha tn s , mt i lng c trng cho bn cht sng, v vy theo ng
khng th n thun coi nh sng l ht m cn tha nhn tnh sng ca nh sng.
iu c ngha l nh sng va c tnh sng va c tnh ht. Ngi ta ni nh
sng c tnh nh nguyn sng- ht
2.2.2 Cc i lng biu din sng in t v biu thc lin quan gia cc i lng

- di sng : Khong cch gia hai cc i hay hai cc tiu k tip nhau.
n v l cm, nm, m, A0
- Chu k T : thi gian sng truyn t cc i ny sang cc i k tip. n
v l giy
- Tn s : s dao ng trong mt giy. n v = 1/T
- Tc truyn sng trong chn khng
C = . = 3.1010 cm/s
- S sng = 1/ ( cm-1 ) m t s sng thc hin c trong mt giy
2.3 Nng lng ca vt cht v tng tc sng in t ti vt cht
2.3.1 Nng lng ca vt cht

Theo l thuyt ca Albert Einstein mi vt c khi lng u c nng lng, do

cng c th ni mi dng thc th ca vt cht trong t nhin u c nng
lng. Nng lng ca vt cht ph thuc vo khi lng ca n. Nu mt vt c
khi lng l m th n c nng lng tng ng l E=mc. Trong phn ng ht
nhn, nu khi lng thay i mt lng l m th nng lng cng thay i mt
lng tng ng l E. Phn nng lng thay i E c th l ta ra hay thu vo.
Nu l ta ra th tn ti di dng nng lng nhit v bc x ra cc ht c bn.
S phn b nng lng trong phn t ca mt cht bao gm ba trng thi: Trng
thi in t- trng thi Dao ng v trng thi Quay. Nh vy nng lng bn
trong phn t l tng cc dng nng lng :
E = Eel + Ed + Eq
8

Eel : l nng lng in t ph thuc vo s phn b in t. Bin thin ca n ph

thuc vo s chuyn in t t orbital phn t ny sang orbital phn t khc.
Ed : l nng lng dao ng , c trng cho s dao ng ca cc ht nhn nguyn
t xung quanh v tr cn bng ca chng trong phn t
Eq : l nng lng quay, lin quan ti s quay ca phn t xung quanh nhng trc
no trong phn t
2.3.2. Tng tc sng in t vi vt cht

Khi chiu bc x in t vo dung dch cha cc phn t th bc x in t c th

b khuych tn hoc b hp thu. Ph phn t chnh l ghi li s hp thu bc x bi
phn t.
Khi phn t hp thu bc x, chuyn t trng thi c bn ln trng kch thch, ngha
l bn thn n thay i mc nng lng E = Ekt Ecb = Eel +E d+ Eq
V : Eel > E d> Eq

Cc trng thi nng lng ca phn t gm hai nguyn t

Cc mc nng lng quay J rt gn nhau, cc mc nng lng dao ng v xa
nhau hn, cn cc mc nng lng in t th cn xa nhau hn na. Mi mt
trng thi in t bao gm cc trng thi dao ng khc nhau, v mi trng thi
dao ng n lt n bao gm cc trng quay khc nhau. V th nhng chuyn
mc nng lng in t thng km theo s bin thin nng lng dao ng v c
nng lng quay .

Nhng phn t c nhiu nguyn t s c nhiu chuyn mc nng lng khc nhau
m mi loi chuyn mc cng c th c biu din bng s nh trn.
nhit khng tuyt i, lp v in t ca phn t khng b kch thch , s
quay ca phn t s khng xy ra , nhng phn t vn c mt nng lng dao
ng no gi l nng lng dao ng im 0. Khi tng dn d tr nng
lng nhit ca phn t n gi tr 0,03- 0,3 Kcal/mol, trng thi quay ca phn t
bt u b kch thch nhng trng thi dao ng v trng thi in t vn khng
i.
Khi nng lng chuyn ng nhit tng ln 0,3- 12Kcal/mol, trng thi in t ca
phn t cng cha b kch thch nhng trng thi dao ng bt u b kch thch .
Nhng photon tng ng vi bin thin nng lng dao ng c bc sng vo
c: = 2500nm- 0,1mm ng vi bc x vng hng ngoi.
Mun kch thch cc in t th cn phi dng nng lng cao hn, vo khong
vi chc n vi trm Kcal/mol . Nng lng ng vi vng kh kin v t
ngoi.
Cc bc x c nng lng thp nh sng cc ngn hoc hng ngoi xa ta s thu
c ph quay thun ty. Ph thun ty bao gm nhng vch ph cch u nhau
v gn nhau, mi vch c tn s:
q

Eq
h

Khi phn t b kch thch vng hng ngoi gn, trng thi dao ng b kch thch
nhng lng t nng lng ng vi tn s :
d

Ed
h

Cui cng khi phn t hp thu bc x c nng lng ln nh bc x kh kin hay

t ngoi th nng lng in t ca chng thay i. Nu trng thi in t b thay
i th vch hp thu tng ng s c tn s :
el

Eel
h

10

Nh vy khi trng thi in t ca phn t thay i, nhng trng thi dao ng v

quay cng thay i ng thi, ta thu c ph electron- dao ng- quay m
thng ch gi l ph electron ca phn t v so vi s thay i ca trng thi dao
ng v trng thi quay th trng thi in t qu ln.
Thc ra mi vch ring ca ph clectron c tn s cho bi biu thc:
= el + d + q
i lng el c xc nh bi bin thin nng lng in t ca phn t.
Thng el > d vi chc ln v ln hn q vi nghn ln
Nn: el . V vy khi s hp thu bc x c nh hng ti trng thi in t th
ph thu c xem nh ph in t
Vt hp thu dng nguyn t hay phn t ta c ph hp thu nguyn t hay
phn t tng ng
- Tn s bc x b hp thu c ngha c trng c cu trc vt cht . Nghin
cu tn s (bc sng) hp thu trn ph nhn din hay nh tnh mu. Da vo
ph hp thu c th nh lng mu.
2.3.3 Cc loi ph hp th
Ph hp th phn t UV- Vis
Cc cht hp th l cc phn t, c kh nng hp th cc bc x in t trong
vng UV-Vis. Do nng lng ca bc x trong vng nay tng i ln, nn chng
kch cc in cc lin kt hay cc in t t do, dn ti ph hp thu. Trong ph
hp th UV-Vis cc nhm chc khc nhau s hp th cc bc sng cc nhau.
V vy dng ph UV-Vis c th d on s c mt ca cc nhm. Ph thu c
cho qu trnh ny l nhng mi hp th ni tip nhau, nn c gi l ph m.
V mt nh lng c th dng ph UV-Vis nh cc cht thng qua nh lut
Lambert- Beer

11

Hnh trn l ph hp thu ca phn t Benzen 2 trng thi lng (a) v hi (b)
Ph hp thu nguyn t
Cc cht hp th cc nguyn t kim loi trng thi hi. trng thi ny chng
c kh nng hp th nhng bc x in t t trng trong vng t ngoi, gy ra
ph hp th nguyn t. Ph thu c cho qu trnh ny l nhng vch ph t
trng, nn c gi l ph vch. Nhng nguyn t kim loi khc nhau trng thi
hi nguyn t c kh nng hp th nhng bc x in t c bc sng khc nhau.
Chnh v vy, ngi ta c th da trn bc sng b hp th d on s c mt
ca kim loi . V mt nh lng cng da trn ng dng nh lut LambertBeer.

12

Hnh trn l vch ph hp thu ca nguyn t As, bao gm hai vch 197,2nm c
nhy cao v 193,7nm c d nhy thp hn
Ph Hng ngoi
L ph hp thu trong cc phn t hp th bc sng nh sng tng ng vi
trong vng IR. Phng php phn tch theo ph hng ngoi l mt trong nhng k
thut phn tch rt hiu qu. Mt trong nhng u im quan trng nht ca
phng php ph hng ngoi vt hn nhng phng php phn tch cu trc
khc (nhiu x tia X, cng hng t in t vv) l phng php ny cung cp
thng tin v cu trc phn t nhanh, khng i hicc phng php tnh ton
phc tp. K thut ny da trn hiu ng n gin l: cc hp chp ho hc c
kh nng hp th chn lc bc x hng ngoi. Sau khi hp th cc bc x hng
ngoi, cc phn t ca cc hp cht ho hc dao ng vi nhiu vn tc dao ng
v xut hin di ph hp th gi l ph hp th bc x hng ngoi. Cc m ph
khc nhau c mt trong ph hng ngoi tng ng vi cc nhm chc c trng
v cc lin kt c trong phn t hp cht ho hc. Bi vy ph hng ngoi ca
mt hp cht ho hc coi nh "du vn tay", c th cn c vo nhn dng
chng.Trong ph hng ngoi ngi ta chia lm 3 vng da trn bc sng ca
chng:

1- Cn hng ngoi ( near infrared)

= 0,8 2,5m

2- Trung hng ngoi ( medium infrared)

= 2,5 50m

3- Vin hng ngoi ( far infrared)

= 50 - 100m

* Trong vng hng ngoi gn (NIR):

T 12500 cm-1 tri di n khong 4000 cm-1 c rt nhiu m ph c lin quan
n nguyn t H. Trong s , dao ng co gin (bi) ca O - H gn 7140 cm-1 v N-H
gn 6667 cm-1, m ph t hp do cc dao ng co gin v dao ng bin dng ca C-H
ca nhm ankyl 1548 cm-1 v 3856 cm-1.
hp th ca m ph NIR thp hn t 10 n 1000 ln so vi cc m ph vng
hng ngoi gia.

13

Vng NIR c th ghi c vi h quang hc thch anh, kt ni vi cc detect nhy

vi NIR v ngun bc x mnh hn.
* Vng hng ngoi gia:
tm c rt nhiu tng quan b ch trong vng hng ngoi gia.Vng ny
c chia thnh min "tn s nhm" 4000 1300 cm-1 v vng"du vn tay" 1300 - 650
cm-1.
Trong khong 4000 2500 cm-1 s hp th c trng cho dao ng co gin ca H vi
cc nguyn t khi lng < 19.
Phn ch yu trong ph gia 1300 v 650 cm-1, l cc tn s co gin ca lin kt
n v tn s cc dao ng un (cc tn s b khung) ca h nhiu nguyn t. l vng
"nhn dng" "(vng "du vn tay"). Vng ph ny ht sc a dng , kh cho vic nhn
bit ring r cc m ph mt cch chc chn, nhng kt hp cc m ph hp th, gip
cho vic nhn bit cc cht.
* Vng hng ngoi xa:
Vng 667 - 10cm-1 bao gm cc dao ng bin dng ca C, N, O, F vi cc nguyn
t khi lng > 19 v cc dao ng bin dng trong h thng mch vng hoc cha no.
Vng dao ng tn s thp trong ph hng ngoi rt nhy i vi s thay i cu trc
phn t, bi vy m ph vng hng ngoi xa thng cho php d on cc dng ng
phn. Ngoi ra, vng ny c bit tt cho vic nghin cu cc c kim v cc hp cht v
c c cc nguyn t nng v lin kt yu.
Trn y ta thy c s lin quan gia cu trc phn t v s xut hin cc m
ph dao ng (ph hp th hng ngoi).
Tn s dao ng ca nhm nguyn t no trong phn t t ph thuc cc phn
cn li ca phn t c gi l tn s c trng cho nhm .
Khi ni tn s c trng ca nhm khng thay i th khng c ngha l max hp
th l khng i m ch c ngha l max nm trong mt min ph kh hp. V d lin
kt C-H c tn s c trng trong khong 2800 2900 cm-1
2.4. S pht x v cc loi ph pht x
2.4.1. . S pht x ca vt cht

Vt cht dng nguyn t hay phn t , nhn nng lng bc x thch hp,
chuyn mc nng lng thp (bn) ln mc nng lng cao hn (km bn ), c
khuynh hng tr li mc nng lng thp hn v c th pht ra bc x, l
hin tng pht x.
d tm hiu qu trnh pht x chng ta xt gin nng lng v ph pht
x ca nguyn t Hydro
Cc trng thi nng lng ca e trong nguyn t H
Nng lng ca e tnh c khi gii phng trnh Schroedinger:
14

En

13,6
(ev)
n2

Ta thy nng lng ca cc e ph thuc vo s lng t chnh n (lp)

- Vi n = 1 ( lp K )ta c E1= -13,6ev ng vi trng thi c bn
- Vi n = 2 ( lp L )ta c E2= -3,4ev
- Vi n = 3 ( lp M )ta c E3= -1,51ev

Gin nng lng v s xut hin cc dy ph pht x hydro

15

Dy Lyman : tp hp cc dy ph ng vi nhng bc chuyn e t nhng

mc nng lng cao ( lp ngoi nc 2) v mc c bn (nt=1) to nn dy vch gi
l dy Lyman do ng tm ra vo nm 1916.
Nh vy i vi dy Lyman th nc = 2,3,4. v nt =1
V hiu cc mc nng lng ln nn nhng bc x trong vng ny c bc
sng ngn ( = h ) thuc min t ngoi
Dy Balmer: Nhng vch ph thu c do su chuyn ng e t cc lp bn
ngoi ( nc 3) v lp nt =2 to dy Balmer. Bc sng ca cc bc x pht ra
trong dy Balmer thuc vng kh kin c th quan st bng mt, y l dy ph
quan trng c Balmer tm ra vo nm 1885.
Di y l nhng vch ph thuc dy Balmer thng gp
H mu : nc = 3, nt = 2 v = 656nm
H mu lam : nc = 4, nt = 2 v = 486nm
H mu tm : nc = 5, nt = 2 v = 434nm
Dy Paschen: Nhng vch ph thu c do s chuyn e t cc lp c n c 4
v lp nt=3 to thnh dy Paschen. Nhng bc x trong vng ny thuc vng hng
ngoi c bc sng c 1000nm 770nm

16

S pht x ca hai nguyn t Na v hydro

2.4.2. Cc loi ph pht x
Ph pht x nguyn t
Ph thu c t s pht x ca cc nguyn t trng thi hi ang trng
thi kch thch. L mt phng php phn tch vt l da trn tnh ch t pht
x ca nguyn t trng thi hi xc nh thnh ph n ha hc ca cc
nguyn t, cc cht trong mu phn tch. 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. Trong phng php ny cn thit
phi c ngun nng lng p ng cho qu trnh ha hi, nguyn t ha v
kch thch cc nguyn t ca cc nguyn t ln trng thi kch thch, trng
thi kch chng khng bn v pht ra nhng bc x c trng. Cc nguyn
t kim loi khc nhau s pht ra nhng bc x khc nhau, c bc sng xc
nh. Phn tch nh tnh s da trn bc sng t trng, phn tch nh
lng da trn cng vch pht x.
Ph pht x ion
Nguyn tc: Trong quang ph pht x (OES), mu c t nhit
cao gy ra khng ch phn ly thnh cc nguyn t m cn ion ha cc
nguyn t. Khi cc nguyn t hoc ion trng thi kch thch c th phn

17

hy v mc nng lng thp hn thng qua qu trnh chuyn di nng

lng v pht x. Trong OES, cng nh sng pht ra cc bc sng
c th c o v c s dng xc nh nng ca cc kim loi. Gn
y vic p dng k thut plasma vo phn tch OES mang li tim nng
ln.
My quang ph ICP-OES
Kh Argon c dn qua mt ngn la gm ba ng ng tm lm bng
thch anh, mt cun dy ng, gi l cc cun dy ti, bao quanh cui cng ca
ngn la v c kt ni vi my pht tn s (RF).
Nng lng RF (thng l 700-1500 watt) c duy tr trong cun dy vi
t l tng ng vi tn s ca my pht in. Trong hu ht cc thit b ca ICP
tn s ny l 27 hoc 40 megahertz (MHz). Dng in trong cun dy gy ra in
trng v t trng c thit lp trong khu vc trn cng ca ngn la. Vi kh
argon c i qua b phn t, tia la in c nh vo dng kh gy ra hin
tng mt s electron b vng ra t nguyn t argon. Nhng electron ny sau b
cun vo t trng v gia tc. Cc electron nng lng cao ln lt va chm vi
cc nguyn t argon gy ra s ion ha. S Ion ha ny tip tc trong mt phn ng
dy chuyn, ph v kh thnh mt plasma bao gm argon nguyn t, in t, v
argon ion.

18

Hnh 2.9. Bng gii hn pht hin ICP-OES

Hnh 2.10. Mt ct ngang ca mt ngn uc ICP v cc cun dy ti

m t mt chui nh la.
A Kh Argon l xoay qua ngn uc.
B Nng lng RF c p dng cho cc cun dy ti.

19

C Mt tia la to ra mt s electron t do trong argon.

D Cc in t c gia tc bi in trng gy ion ha vto thnh mt plasma.
E Mu c phun vo ngn.
Hu ht cc mu dng lng c a vo mt bnh phun sng m v
a vo trung tm ca plasma. u tin nhit trong ngn uc s loi b cc
dung mi. Cc bc tip theo lin quan n vic phn hy v sau in ly thnh
cc nguyn t. Cc qu trnh ny xy ra ch yu khu vc sy s b (PHZ),
plasma c chc nng kch thch v ion ha. Cc kch thch v ion ha cc quy trnh
xy ra ch yu trong vng bc x ban u (IRZ) v phn tch thng thng khu
vc (Naz).
Mu c vn chuyn vo thit b thnh mt dng cht lng v c
chuyn thnh dng sng thng qua mt b phn c gi l bnh phun. Mu
c phun dng sng sau c vn chuyn n bung t, ti y c
ui ht dung mi, bay hi, v ion ha. Cc nguyn t c kch thch v pht ra
bc x ion c trng ca n v c thu thp bi mt thit b c bit. Bc x
c pht hin v bin thnh tn hiu in t

20

Hnh 2.13. Cc thit b chnh v b tr ca mt thit b ICP-OES in hnh.

2.5. Cc chi tit trong my quang ph
2.5.1 Thit k c bn trong thit b quang ph
Thit k c bn trong my quang ph bao gm 5 b phn chnh:

21

Da vo nguyn tc ca phng php trong my o quang c cc b phn

chnh nh sau :

Trong :
1. Ngun bc x tn hiu
2. B phn to n sc
3. Mu
4. B phn nhn kt qu v chuyn thnh tn hiu
5. My o hay my ghi

22

2.5.2. Ngun bc x
Da vo bn cht ca qu trnh to ra bc x m ngi ta chia lm hai loi
ngun bc x: Ngui bc x lin tc v ngun bc x khng lin tc
+ Ngun bc x lin tc.
Ngun bc x lin tc l ngun pht ra di cc bc x lin tc c di sng
khc nhau, sau cc bc x ny i qua b phn to bc x n sc c bc x
n sc trc khi i n mu
Ty vo di sng ca bc x cn pht ra , ngi ta dng cc loi ngun
sau :
- Ngun t ngoi : gm c n hydro ( cha kh H 2) v n deterium ( cha
kh D2)
Cu to n :

Hot ng ca n : Th cao 2000 6000v p c vo hai in cc nhm ,

kch thch phn t bn trong, chuyn chng t trng thi nn( trng thi c bn)
ln trng thi kch thch , khi cc phn t kh b kch thch khng bn pht ra nng
lng di dng nhng bc x c bc sng xc nh tr v trng thi c bn, qu
trnh xy ra lin tc nh vy v ta c nhng bc x cn thit. Vi loi n ny bc
xa pht ra c = 180 375nm
- Ngun n thy c : pht ra nhng bc x thy c
Cu to n :

23

Hot ng : Ngi ta p t th khong 6 V vi cng dng ln , t

nng dy tungsten. Dy ny chy v a kh tr trong n ln trng thi kch
thch t pht ra bc x c =320 2500nm. Nhit n khong 30000K.
- Ngun n hng ngoi :
Gm 3 loi n :
*Nernst: cu to bi oxyt t him l nhng nguyn t Lantanic v Actinic ,
dng hnh tr , chiu di 20mm. ng knh 1- 2mm
*Globar: Thanh silicol carbide mt hl kim ca Si- C , di 50cm, ng knh
0,5cm
*Dy xon nichrom ( mt hp kim c lm t Ni-Cr)
Thng dng nht l dy xon Nichrome
Hot ng ca n : Ap t th thch hp to dng in chy qua lm dy
nichrome nng pht ra nhng bc x hng ngoi . Nhit n khong 20000K.
+ Ngun bc x khng lin tc
Ngun bc x khng lin tc l ngun bc x pht ra c di sng nht
nh
n catot lm : hollow cathode tube
Cu to n:

24

Cathode: lm bng kim loi tinh kit cng nguyn t vi cu t kho st

ngha l nu nh ta kho st nh lng Cu th ta dng n c cc catot l Cu
.
Anode: Dy tungsteng
Hot ng n : Ap th thch hp gia hai in cc , ion ho kh bn trong ,
do s di chuyn cc ion n in cc lm to ra dng in gia hai in cc. Nu
th p t ln , cc cation khi ng nng s p mnh vo bng cc catot l
bc cc nguyn t kim loi catot ra khi in cc ny , to m my nguyn t ,
dng nguyn t n hp th nng lng chuyn ln trng thi kch thch khng
bn v pht ra nhng bc x c bc sng xc nh tr v trng thi c bn ban
u.
V d ; cu to n c catot lm bng Pb khi bc x pht ra do nguyn t Pb
b kch thch c = 283nm.
2.5.3.B phn to bc sng n sc.
+ Knh lc : thng s dng loi lnh lc hp thu.
Cu to : knh lc c th l
Knh lm bng thy tinh mu
Knh lm bng phm mu dng huyn ph trn vi gelatin p gia hai
bn thy tinh.
t im:
n gin r tin
Ch o hp thu nhng bc x c nh

25

 Nng sut truyn yu

Khng to ra bc x n sc , ch truyn qua dy bc x (30-50) nm
V d : Knh lc 470nm theo l thuyt th ch c bc x c = 470nm nhng
thc t th nhng bc x c = 470 30 nm cng i qua .
+ My bit sc : monochromator
Cu to : H thng gm cc khe, knh lc v b phn tn sc
Hot ng :

nh sng t khe vo, qua knh phn k n b phn tn sc , Bc s khuych

tn qua thu knh hi t n mt b mt c khe ra . Bc x c di sng mong
mun s i ra khe do s quay ca b phn tn sc .
B phn tn sc ( Dispersing element)
Gm 2 loi : Lng knh ( prism) v cch t ( grating)

26

S tn x di tc dng ca lng knh

Lng knh : C cu to ph hp cho php truyn bc x vo vng ph m ta
kho st .
V d:
+ c vng bc x t ngoi dng lng knh thch anh (quartz)
+ Vng bc xthy c dng lng knh thy tinh hay thch anh.
+ Vng hng ngoi dng lng knh trong c cha mui halogenua ca
kim loi kim nh KBr hay NaCl
Cch t : C hai loi l cch t truyn sut v cch t phn x
Cch t truyn sut : Transmission grating.
Cu to : Bn thy tinh trn c khc cc vch song song u nhau, c th
vi trm vch trn 1cm.

27

Hot ng : Khi bc x chiu n cch t truyn sut , mi vch ng vai tr

nh mt ngun sng mi , c hin tng giao thoa gia cc bc x , kt qu l c
theo cc di sng .
Cch t phn x:

Cu to : bn kim loi bng nhm c khc cch vch .

Hot ng : Do khong ng i ca bc x n b mt cch t l khc
nhau , to tia phn x gy ra hin tng giao thoa , kt qu l c s phn tch cc
bc x theo cc di sng.
t im :
- Khc phc c cc nhc im ca knh lc .
Cch t c n sc cao : 0,1nm
o cc di sng khc nhau
Nng sut truyn sut khng i
To c bc sng tht n sc
C cu to phc tp v rt t tin
2.5.4.B phn cha mu: ( Sample container)

28

+ Cu to : B phn cha mu lm bng vt liu ng nht , cho php truyn

qua bc x trong vng kho st
+ Hnh dng : Hnh khi ch nht hay ng nghim
+ Kch thc : Khong cch bn trong gia hai thnh hay ng knh thay
i t 0,05mm 5 cm
+ Lu : Trnh cc vt bn , du bm ln thnh b phn cha mu
2.5.5. B phn nhn kt qu v chuyn thnh tn hiu: ( Detector)
Nguyn tc : Nhn nng lng ca bc x ra khi mu v chuyn thnh dng
nng lng khc c ghi nhn bng tn hiu.
Phn loi : chia lm hai loi
+ Hiu ng quang in : Nhn quang nng ca bc x ra khi mu v chuyn
thnh tn hiu in . S dng t bo quang in dng cho bc x vng t ngoi v
vng thy c .
+ Hiu ng nhit in : Nhn nhit nng ca bc x ra khi mu v chuyn
thnh tn hiu in . Thng s dng cp nhit in , t bo Golay , balometer.
Da trn s thay i nhit lm thay i in tr ca chng , do lm thay i
in th v ghi nhn s thay i di dng tn hiu in . Dng cho bc x hng
ngoi v bc x ny c nng lng nh nn ch ghi nhn d thay i nhit trc
v sau khi qua mu.
2.2.5. My o v my ghi :
29

Tn hiu nhn c t detector c ghi di dng ng biu din trn my

ghi hay chuyn thnh i lng o trn my o. Ngy nay ta thy c c mng hnh
vi tnh km theo my ghi

CHNG III
PHNG PHP PH HP THU T NGOI V KH KIN
30

S tng tc bc x ca trng in t n vt cht trong vng bt u bc

x t ngoi n hng ngoi, c bc sng : 180nm- 1100nm, c
nghin cu k. Vng ph in t ny c gi l t ngoi v kh kin, v n
cha nhng bc x pht ra m mt con ngi c th thy c, n gii thch
c cu trc ca phn t v s hin din ca trng thi khng bo ha
trong phn t. N tht s quan trng trong phn tch nh lng.Tnh ton
hp thu bc x t ngoi v kh kin bng cch p dng nh lut
LamBert- Beer l nn tng ca phng php ( nh phng php o quang).
Phng php rt hu hiu trong phng th nghim trong qu trnh nh
lng hm lng mu. Phng php ny khng ch p dng cho nhng hp
cht c kh nng hp thu bc x trong vng ny m cn cho tt c cc hp
cht c kh nng hp thu.
Trong phm vi lin quan ti phn tch k c nhng dng c t nhng thit b
n gin nh my so mu n nhng my o quang ph t ng n phn
tch nhiu thnh phn cu t trong hp cht. Phng php sc k lng v
in di mao qun pht trin hn nh vic p dng nhn bit bng cc loi
detector UV-VIS. Nhng detector ny to nn nhng sc k .
3.1.

Nhng khi nim c bn

Dy ph thu c t qu trnh tng tc c th phn chia thnh 3 vng: Cn

t ngoi- kh kin v vng hng ngoi gn ( ln lt t : 185- 400, 400700, 700- 1100nm). Hu ht cc my o u o trong vng bc sng t
185- 900nm. S hp thu bc x trong vng bt u c = 185nm l gii hn
lm vic trong vng bc sng thp. Khong bc x thp hn 10-20nm l
vng bc x t ngoi chn khng gi l vng t ngoi xa.
Nhng dng c ny cho php ph nhn c biu din hp thu theo
bc sng. Bc sng c tnh theo n v nm v c xem l n v biu
din trong ph .
31

Hnh trn l ph khc nhau trong vng ph kh kin v t ngoi

Hnh a: Ph thu c trong trng hp hp cht trng thi dung dch
( Hu ht l trng hp ny )
Hnh b: Ph c cu trc p d nhn bit
Hnh c: Ph thu c khi s dng thit b c phn gii cao.
V tri hp thu cc i ca mt hp cht c thay i vi nm, ph thuc vo
bn cht ca dung mi hay gi tr pH ca dung dch. Bc sng hp thu cc

32

i c xc nh bng cch thng qua ph phn gii cao ca hp cht

ng vi mt di hp thu trong mt vng bc sng no .
i lc, di hp thu ch thu c khi nghin cu trng thi m c nh
th tinh kit ca cht hay dung dch. Tuy nhin cng c mt vi mu nghin
cu th hi cng cho cu trc ph p, v ch c mt vi phn t cht
cho ph thng.
3.2. S hp thu ca phn t
S tc ng photon ca bc x t ngoi v kh kin ln mt phn t c lp
ch yu lm thay i trng thi in t, tc l Eel thay i nhiu nht, c
ngha l s thay i ca mc nng dao ng v mc nng lng quay khng
ng k so vi mc nng lng in t.

Eele >>Ed >>Eq nn: Etng Eele

Ta c th thy iu ny qua hnh sau:

33

 th m t trng thi nng lng cc trng thi quay, dao ng v in t

ca phn t.Trn th ta thy nng lng quay, nng lng dao ng nh
hn rt nhiu so vi nng lng in t T l phn b gia cc mc nng
lng l : 1000: 50: 1.
Sau khi hp thu nng lng c th c gii phng bng cch pht x bc x
hay chuyn nng lng sang dng khc. Hu ht cc bc x chuyn bao gm
l ln quang v hunh quang

th cho thy s chuyn t trng thi kch thch v trng thi c bn ca

phn t, s gii phng nng lng c th xy ra bng cch di dng nhit
hay di dng bc x hoc c hai. S chuyn i xy ra ngay tc th ( di
phn triu giy), i vi nguyn t th tn s hp thu bc x bng tn s pht
x khi chng chuyn t trng thi kch thch v c bn
3.3. S thay i cc orbital phn t trong qu trnh hp thu
Trong th cc hp cht hu c, khi quan tm nhng lin kt to ra, gia cc
nguyn t nh C, H, O, N c s chuyn hin din cc in t lin kt , ,
v in t khng lin kt n ln cc orbitn phn lin kt *, * . S chuyn v
ca cc in t cc orbital lin kt ln phn lin kt khi hp thu nng
lng, hnh thnh ph gi l ph chuyn v.
Qu trnh chuyn v c xc nh bi bc sng ca n v h s hp thu
mol ( mol-1.cm-1) ti bc sng ny.
3.3.1. Chuyn v *
34

Kh nng chuyn v trong lin kt trong cc hp cht hu c tng ng

vi mc nng lng cch bit gia hai orbital lin kt v phn lin kt *..
S chuyn v ny i hi mt nng lng kh ln, v vy qu trnh chuyn v
nm trong vng t ngoi xa ( UV). y l l do v s tch cc hydrocacbon
nh hexan v cyclohexan, trong phn t ch cha lin kt c xc nh
r trong vng t ngoi hexan c max= 135nm ( = 10000).
Hexan v heptan c dng cho nh nhng dung mi trong vng t
ngoi gn v chng hp thu mnh bc sng trn 200nm. Tt nhin
hai dung mi ny khng ha tan hp cht hu c phn cc.
3.3.2. Chuyn v n *
S di chuyn ca cc in t khng lin kt n ln cc orbital * trong cc
nguyn t nh O, N, S trong cc hp cht hu c vng ph t ngoi gn
c cng khng ln. S dch chuyn ny dao ng 180nm cho alcol,
dn xut halogen ca n l 190nm. i vi cc amin l 220nm
V d : Ete c max= 190nm ( =2000), metanol c max= 183nm ( =50)
Etylamin c max= 210 nm ( =800)

3.3.3 Chuyn v n *
y l qu trnh dch chuyn c nng lng thp, mt in t t orbital
khng lin kt n ln orbital phn lin kt *. y l qu trnh thng xy ra
trong phn t c mt nguyn t cha bo ha in t. Hu ht cc qu trnh
chuyn ny xy ra nhng phn t cha nhm chc cacbonyl (C=O) v
bc sng hp thu t 270nm- 295nm. H s hp thu mol trong trng hp

35

ny l thp. Bn cht ca cc dung mi c nh hng n bc sng hp thu

v n tc ng n lin kt trong phn t.
3.3.4. Chuyn v *
Cc hp cht ng phn vi etylen cha lin kt i trong phn t c kh
nng hp thu mnh trong khong bc sng 170nm, v tr hp thu ph thuc
vo s hin din ca nhm th v d etylen c max= 165nm ( =16000)
Nhng hp cht khng mu thng c ph hp thu trong vng cn t ngoi.
Khi chng hp thu bc x th chng s chuyn ti trng thi thng qua c
ch cho- nhn in t. Lc ny in t t orbital cho in t s chuyn ln
orbital nhn in t to thnh nhng ion hay c s phn cc trong phn t
Chuyn v dd*
Mt s mui v c , trong cu trc phn t c cha orbital d trng ( nh
Cu,Ni, Mn) c kh nng chuyn v dd* ( Chuyn v c mc nng
lng thp) trong vng kh kin, lm cho mui ca chng thng c
mu. iu ny gii thch ti sao phc ca chng vi cc phi t nh
CN-,NH3, H2O c mu nh Cu(NH3)42- c mu xanh.
3.4.S lin hp trong cho nhn in t
Mt hp cht l c s dch chuyn r rng khi m trng thi ring bit
chng c th hp thu nhng phn nng lng c th thc hin s chonhn in t. Hin tng ny lin quan ti vic in t nhy t orbital lin
kt cho ( to cation) ln orbital phn lin kt nhn ( to anion), tng ng
vi s mt nng lng. V tr hp thu ca ph ty thuc vo kh nng ion
ha ca cation v mc i in t ca nhm ht in t. Ga tr ( hp
th mol trong trng hp ny thng ln)

36

Gin m t qu trnh dch chuyn in t. Trng thi kch thch c xem

l s hnh thnh cc ion hay c s phn cc trong phn t
3.5. Cc nhm chc
Nhm chc l nhng nhm nh c to thnh t nhng nguyn t, n lin
quan ti qu trnh hp thu. Ti v tr cc nhm chc trong phn t cc dch
chuyn in t xy ra, nn bc sng hp thu ca phn t hu c lin quan
ti cc nhm chc trong phn t. Bng nhng my o bc sng hp thu
cc i ngi ta tm c cc bc sng hp thu cc i cho tng nhm
chc. Bc sng hp thu ca phn t chu nh hng ca tc ng ca cc
nhm chc.
Sau y l bc sng hp thu cc i ca mt s nhm chc ca N

3.6. nh hng ca dung mi- Qu trnh solvate ha cc nhm chc

Bc sng hp thu v cng hp thu ca cc hp cht chu nh hng
ca dung mi. S tc ng ca nhng dung mi khc nhau ln cc phn t
37

lm thay i mc nng lng gia cc rng thi kch thch v c bn.Nghin

cu vng hp thu v bc sng hp thu, chng ta c th bit c loi dch
chuyn trong phn t khi chng hp thu.
3.6.1. Chuyn dch xanh
Trong mt vi dch chuyn, nhng dung mi phn cc th buc sng hp
thu ngn hn so vi bnh thng. V d nh trong chuyn dch n * ca
nhm cacbonyl trong mch phn t . Trong phn t hu c c s phn cc
ca v tr C+-O- , nu dung mi l phn cc th v tr s c s tng
tc ca in t n vi cc dung mi lm bn trng thi in t n( nng lng
gim) . S gim nng lng trng thi n lm tng mc chnh lch nng
lng gia n * , E tng dn ti bc sng hp thu gim nn ta gi l
dch chuyn xanh.
Ch l nng lng trng thi * nhng trng thi n gim nhiu hn nn
kt qu l mc chnh lch nhit gia hai trng thi tng

Ph hp thu ca benzophenol trong cyclohexan v etanol. Ta thy mc s

chuyn dch xanh hay chuyn dch l ph thuc bn cht cu trc ca
nhm vo bn cht ca dung mi.
3.6.2. Chuyn dch

38

Hin tng chuyn dch xy ra thng nhng hp cht hu c h etylen

c lin kt ni i km bn.Trong dung dch th c s tng tc ca nhm
phn cc ca dung mi vi in t , s tng tc ny trong dung mi
phn cc mnh hn so vi dung mi khng phn cc. V vy mc chnh
lch nng lng chuyn trong dung mi phn cc thp hn ( mc nng
lng trng thi kch thch thp hn so vi trong dung mi phn cc ) ,
hp thu bc sng di hn.
3.7. nh hng ca s lin hp n hp thu
Ph hp thu ca nhng phn t l ng phn ca nhau, khc nhau bi mt
nhm CH2 ca cc phn t hu c m trong cu trc phn t ca n c s
lin hp, th bc sng hp thu ca cc phn t ny tng ln so vi di
mch C. Nguyn nhn ca hin tng ny l do khi mch C cng di th hiu
ng kin hp cng tng, dn ti mc chch lch gia hai trng thi kkch
thch v c bn gim. Bc sng hp thu c xu hng v pha c bc sng
di hn ( dch chuyn )

39

 th m t nh hng ca hiu ng lin hp. Hiu ng ny l ngun gc

to ra mu ca nhiu hp cht khc nhau trong thin nhin.
S hp thu ca cc hp cht thm, ph hp thu thu c phc tp
hn nhiu so vi cc hp cht h etylen. S chuyn dch in t t
* to nn s hin din cu trc ph.

Bng trn cho thy v tr hp thu cc i ca cc cht trong h

polyetylen tng ln theo gi tr n( hiu g lin hp cng ln th bc
sng hp thu cc i cng nh)
3.8.

nh hng ca pH

pH ca dung dch m cht tan tn ti c nh hng ti ph. Phn ln

cc hp cht, s tn ti hay bin i ca n c lin quan ti pH ca dung
dch nh mt s ch th m chng ta thng gp.

40

Trn y l nh hng ca pH n dung dch phenolphtalein. Hp cht ny

khng mu pH nh hn 8 v c mu hng sng pH ln hn 9.5
3.9.

Quy tc Woodward- Fieser

T vic phn tch cu trc ca ph in t thng qua cu trc phn t, vo

1940 trc khi k thut xc nh nng lng lin kt ra i th Wood- Fieser
v Scott xc nh c mi quan h r rng gia v tr hp thu cc i v
cu trc phn t. Qu trnh kho st bao gm nhng hp cht c nhm
dien, cabonyl , steroid. Kt qu th s kho st gia tnh ton kinh nghim v
kt qu thc t c s sai bit rt t . Sau y l mt s v d:

41

Mt s quy tc:
*H thng dien: c tnh tyrn cn bng 1-3 butadien
Nhm mang mu
* 1-3 butadien
* H thng ng vng
* 1 ni i ko di lin hp
* 1 ni i ca dien gn trc
tip vo vng (C = )
* 1 nhm alkyl
* 1 nhm th RS
RO- , HOXR2NTh d :
+ 1-3 butadinen

(nm)
217
+36
+30
+5
+5
+30
+6
+5
+60

217

+ h thng ng vng

36

+ 1 ni i ko di lin hp

+ 1 ni i gn vo vng

+ 4 nhm th alkyl

20

Tng cng = 308nm

Thc nghim = 309 nm
Ceton v aldehyde

42

C=C-C=C-C=O

Nhm mang mu
Ceton vng 6
Ceton vng 5
Aldehyde
Ni i ko di lin hp
Dien ng vng
Ni i vng ngoi
Th alkyl ,,,
Th OH ,
Th OAC,,,
Th =O-Me ,,,
Th Cl ,
-Br ,
-n-R2

(nm)
215
202
207
+30
+39
+5
+10,12,18,18
+35
+6
+35,30,17,30
+15,12
+25,30
+25

Th d :
Ceton vng 6

215nm

Din ng vng

+ 39

Ni i ko di lin hp

+ 30

Alkyl ,,, 10,12,18,18

+ 58

3 ni i trctip vi vng

+ 15

Tng cng = 357nm

Thc nghim = 359 nm

43

Hp cht c dng:
Nhm X l : Alkyl

= 246nm

OH,OR = 230nm
H

= 250nm

Quy tc Scott
Nhm th

V tr nhm

V tr nhm

V tr nhm

Alkyl
-OH,OR
-Br
-NH2
-NR2

th orto
3
7
2
15
20

th meta
3
7
2
15
20

th para
10
25
15
58
85

V d: X l OH c

Z l Br (para)

230nm
+15nm

Theo l thuyt = 245nm

Theo thc nghim = 244nm
10. Thit b o quang ph t ngoi v kh kin
Thit b quang ph UV-Vis cha ba b phn chnh : Ngun to bc x- B
phn phn tn bc x ( bao gm c b phn to bc x n sc)- Detector.
Nhng thit b ny c th dng c lp khng ph thuc vo nhau, to
nn mt thit b dng cho mc ch phn tch mu. Mu c th c t
trong ng dn bc x trc hay sau b phn phn tn nh sng v ph
nhn c c x l bng mt s thut ton khc nhau trn computer.
3.10. Ngun to bc x
Da vo bn cht ca qu trnh to ra bc x m ngi ta chia lm hai
loi ngun bc x: Ngui bc x lin tc v ngun bc x khng lin tc
+ Ngun bc x lin tc.

44

Ngun bc x lin tc l ngun pht ra di cc bc x lin tc c

di sng khc nhau, sau cc bc x ny i qua b phn to bc x n
sc c bc x n sc trc khi i n mu
Ty vo di sng ca bc x cn pht ra , ngi ta dng cc loi
ngun sau :
- Ngun t ngoi : gm c n hydro ( cha kh H 2) v n deterium
( cha kh D2)
Cu to n :

Hot ng ca n : Th cao 2000 6000v p c vo hai in cc

nhm , kch thch phn t bn trong, chuyn chng t trng thi nn( trng
thi c bn) ln trng thi kch thch , khi cc phn t kh b kch thch
khng bn pht ra nng lng di dng nhng bc x c bc sng xc
nh tr v trng thi c bn, qu trnh xy ra lin tc nh vy v ta c
nhng bc x cn thit. Vi loi n ny bc xa pht ra c = 180 375nm
- Ngun n thy c : pht ra nhng bc x thy c
Cu to n :

45

Hot ng : Ngi ta p t th khong 6 V vi cng dng ln ,

t nng dy tungsten. Dy ny chy v a kh tr trong n ln trng
thi kch thch t pht ra bc x c =320 2500nm. Nhit n khong
30000K.

46

Ph pht x ca n Deuterium v cu to ca n Deuterium.

3.10.1. Cc loi ngun o trong my quang ph

47

1. Ngun n- my o ti mt bc sng c nh
My o ti mt bc sng xc nh no nh trong my o quang. Di o
rng nh b phn lc mu. Mu blank l mu ch c cha thuc th v
dung mi m khng cha cu t cn phn tch, c o u tin tr i
hiu ng hp th nn, sau mu chun v mu o c o theo th t t
thp ln cao. B phn phn tch thu bc x n sc dng trong my ny
c l cch t.
Cu to ca ngun o loi ny n gin, cc b phn in lin quan ti s
pht x v n nh ngn cng khng i hi phc tp. V vy gi tr ca
loi my ny tng i r.
2.

Ngun n- My o nhiu bc sng nhau trong cng mt lc

y l thit b hin i, n cho php o cng mt lc cc bc sng khc

nhau. Di ph thu c c trn 2000 vch ph bc x. Ph thu nhn c
ch trong 1/1000 giy t vic nhn bit tc th ca detector. phn gii ph
thuc vo kch thc ca diodes thng t 1-2 nm

3.

My quang ph hai chm tia.

48

Thit b o tt nht trong lnh vc ny vn l loi my quang ph hai

chm tia. Trong mt ngun xuyn qua cuvet cha mu v mt ngun
sng khc th i qua mu i chng ( mu chun hay mu blank ). Ngun
sng khi i ti gng quay th chng s to ra hai ngun sng c bc sng
nh nhau i qua hai cuvet. Trong thit b o hai ngun ny th ngi ta b tr
hai detector thu nhn cng nh sng. Dng in lin quan ti hot
ng ca ng quang nhn in( photomultiplier tube) nh hng ti nhy
ca php o nh phn trm nh sng thu nhn bi detector.
u im ca loi my ny l :
- Chng ta c th o mu v chun cng mt lc v c th kim sot
c qu trnh o xem c g sai bit khng.
- Loi tr c phn nh sng b sai lch khng i qua mu
- Thit b ny c kh nng qut rt nhanh khong 30nm/ giy, nn
chng c dng trang b trong cc my o hp thu.

49

3.11. B phn phn tn v to bc x n sc

Bc x pht ra t ngun c phn tch bi cch t b mt phng hay cong.
B mt cch t c khong 1200 vch trn 1mm. Khi bc x n b mt ca

50

cch t th c hin tng giao thoa, to ra nhng bc x n sc c bc

sng xc nh. Sau bc x c chn ny uc tch bng cch i qua
mt khe hp. Bc sng c to ra bng cch ngi ta thay i gc tip
xc ca bc x khi n b mt cch t. ng dn c chiu di tiu c
khong 0,2-0,5m cho phn gii tt nht.

Cu to ca mt s cch t :
a.

Ebert thit k vi mt knh cu lm M 3 khc phc phn bc x b

phn tn.

b.
c.

Czeny-Turner thit k vi hai knh cu lm hp nht M3 v M4

Thit k vi cch t lm Gc c th tch cch bit bc x mt bc
sng xc nh 0,01nm. Chiu rng ca chm bc x n sc l ph
thuc vo hp ca khe F

3.12. Detector
51

Detector l mt loi dng c quang hc dng thu nhn, pht 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. Nhng
dngc ny c in c nhy km, nht l knh nh. Knh nh c nhc
im kh bo qun , b nh hng bi thi tit, m. Mt khc n l
dng c trung gian nhn c trung gian nhn chm sng v sau s l
tip mi c c vch ph.
Ngy ny dng c c dng nhiu nht l loi detector quang hc kiu ng
c th khuych i c vi triu ln, ngi ta gi l nhn quang in
( photomultiplier) v mt loi detector c cu to l nhng diodes bn dn.
Nhng diode bn dn ny s hp thu nng lng dng in sinh ra do dng
bc x sau khi b hp thu mu.
Nhn quang in kiu ng ( photomultipliers tubes) l mt loi dng c thu
nhn tn hiu quang hc c tnh cht vn nng , n nhy v chn lc
cao. Vng ph hot ng ca cc detector dng ny thng t 190nm900nm. Tt nhin thng s ny ph thuc vo bn cht ca nguyn liu lm
bn catot. H s khuych i ca detector loi ny khong 106 ln , i khi
c loi ti 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 nh : Cs-Sb, Ga-As, Na Cs, K -Sb
Nhng my quang ph thng thng, nhn quang in dng ng l c
thit k nh ng hai cc, c nhy, rng khong o v tn hiu o rt
chnh xc. Dng quang nng sinh ra khong 1ev, cho php xc nh bc
sng ln hn 1100nm.

52

Trong h thng diode, cc diode c hnh dng ch nht bn trong kt ni vi

bng kim loi. Dng in t c to ra t bc x sau khi i qua mu c
tch trn bng kim loi, to ra nhng bc x t ta c ph thu c. n v
o trong thit b nhn quang in l Watt.
3.3. C s ca phng php o quang
3.3.1.Tnh cht hp th nh sng ca h keo
Tnh hp th nh sng c nghin cu bi nh bc hc Lambert khi
ng chiu mt lung nh sng n sc qua dung dich keo. ng nhn thy
Lp dung dch keo b nng ln v cng tia l khi i ra khi lp dung
dch keo nh hn so vi cng tia ti lp dung dch. iu ny chng t
lp dung dch keo hp thu mt phn nh sng. Sau mt thi gian nghin
cu ng rt ra c cng thc thc nghim sau:

Il=I0.e-kd

53

Trong :

IL : l cng tia l
I0 : l cng tia ti
k: h s hp th
d: dy cu lp dung dch keo

T y ta thy khi d tng theo cp s cng th Il gim theo cp s nhn

Sau ny Beer nhn thy h s hp th k t l vi nng ht nn c th
biu din cng thc lin h gia k v nng ht C l :
k = .C
: l h s hp th mol
T y ta thy Il = I0. e- cd

ln

I
I

.C.d

lg I 0 A
t

c gi l hp th

Ta c : A = .C.d c dng y = ax phng trnh m t s bin thin hp th

nh sng theo nng ht
Trong k thut ngi ta o hp th nh sng ca cc dung dch bng
nhng Cuvet c chiu dy c nh thng l 1cm.
i vi mt dung dch trong mt iu kin o nht nh th l hng s nn
A t l vi C
3.3.2.C s phng php o quang
C s ca phng php o quang c da trn ng dng tnh cht hp th
nh sng n sc ca cc h keo.

54

C th m t phng php ny nh sau: xc nh mt cht no c

trong mu phn tch , ngi ta tin hnh cho cht cn xc nh to phc bn vi
mt thuc th mt mi trng xc nh c pH xc nh .
Song song vi qu trnh trn ngi ta tin hnh trn mt lot bnh nh mc .
mi bnh c cha dung dch cht cn xc nh c nng xc nh, v cng tin
hnh to phc trong cng iu kin vi mu cn xc nh trn.Lc ny ta c dy
mu chun c mu tng dn theo nng m chng ta pha. Ngi ta gi y l
dy chun.
o mt quang ca dy chun nh vy ng vi nng :
C1

ta c

A1

C2

ta c

A2

C3

ta c

A3

C4

ta c

A4

.
Cn

ta c

An

i vi mu cn xc nh :
CX

ta c

AX

Dng ng thng A theo C t xc nh gi tr Ax trn th t tm

c gi tr Cx .
Trong thc t nh gi chnh xc ca qu trnh lm , thng ngi ta
dng phng php bnh phng cc tiu x l s liu thu c. T phng
php bnh phng cc tiu ngi ta tm c phng trnh y = ax trong y
tng trng cho A v x tng trng cho C. Thay gi tr Ax vo phng trnh ta c
gi tr Cx . V nh gi chnh xc ca qu trnh c th kim nh thng qua gi
tr R2 . Gi tr ny phi t ti thiu l : R 2 > 0,99 th ng chun mi t yu
cu.
th c dng nh sau :

55

3.3.3.Nhng yu t nh hng n hp th nh sng.

T c s ca phng php ta thy vic o hp th nh sng ca dung
dch cng chnh xc , gi tr thu gia cc dung dch chun l hp l th kt qu
phn tch ca chng ta cng d chp nhn.Nn trong k thut phn tch ngi
ta c gng loi b nhng sai st trong qu trnh tin hnh c nh vy th kt
qu mi chnh xc . Sau y l mt s yu t nh hng n qu trnh o.
a. Vn hnh my
+ Cn to bc x tht n sc c s hp th c thnh chn lc v K l
hng s .
+ Chn bc x ng vi hp th cc i theo gin A = f ()
+ Gi nhit c nh 30C
+ Chn loi cuvet thch hp tt nht l thch anh
+ C th chn cuvet dy hn c D ln hn
+ Phi lm mu trng loi nh hng ca dung mi v cu t ph.
Chnh my c A = 0 v T = 100%
b. K thut o
56

+ C th tng chnh xc ca php o bng cch tng thc o khi mu

c nng qu cao hay qu thp ( phng php o vi sai )
+ Nu mu c nng qu cao th , dng dung dch chun c nng
thp hn iu chnh my c T = 100%
+ Nu mu c nng qu thp , dng dung dch chun c nng cao
hn iu chnh my c T = 0%
+ Hy dng hai dung dch chun c nng cn nng dung dch mu,
iu chnh my T = 100% v T = 0%
c. Bn cht dung dch
+ Chn nng dy chun sao cho c t l tuyn tnh D = f(C )
+ C th khi pha long dung dch s nh hng ti s tn ti ca phc
lm cho mu ca dung dch gim dn ti mt quang o c l gim
V d : [Cu(NH3)4]2+ + 2H2O [Cu(NH3)3H2O]2+ + NH4OH
+2 H2O
[Cu(NH 3)2H2O]2+ + NH4OH
+ Yu t pH rt quan trng khi gi tr pH ca dung dch thay i th n s nh
hng ti s tn ti ca phc,tc l nh hng ti gi tr o A
V d : 2 CrO42- +2 H+ Cr2O72- + H2O
d. Anh hng ca thi gian:
Mi phc hnh thnh u c bn ca n v sau mt thi gian di tc
dng ca mi trng n b phn hu v vy cn phi o trong khong thi gian bn
ca phc. Lc th cng mu l ln nht , hp th l cc i.

57

UV-3101
UV-1650PC

UV-3600

58

3.3.4. Mt s v d p dng phng php o quang

a. Xc nh hm lng Fe c trong nc
+ Nguyn tc:
St trong dung dch c kh thnh dng Fe 2+ (tan trong nc) bng cch
un si trong mi trng acid v hydroxylamine, sau Fe 2+ to phc c mu vi
1,10 phenanthroline pH = 2,8 3,5. Mi nguyn t Fe2+ s kt hp vi ba phn
t ca phenanthroline to thnh phc cht mu cam. Cng mu tun theo
nh lut Lambert-Beer v ph thuc vo pH. Phn ng s t tc cc i khi
pH ca mi trng trong khong t 2,9 3,5 v s dng mt lng tha
phenanthroline. Cc phng trnh phn ng c biu din nh sau :
3H+

Fe(OH)3

4 Fe

+ 2NH2OH

3+

Fe

3+

+
4 Fe

H2O

59

3H2O
2+

N2O

4H+

2+

N-

+ Fe2+

N-N
Fe
N
N-

(mau
o cam)
1.3. Tr ngi:
Nhng cht oxy ha mnh nh cyanide, nitrite v phosphate (polyphosphate
mnh hn orthophosphate), chromium, zine vi hm lng ln hn st 10 ln,
cobalt, copper ln hn 5mg/l v nicken ln hn 2 mg/l u gy nh hng n kt
qu phn tch. Bismuth, cadmium, mercury, molybdate v silver kt ta vi
phenanthroline. Trong qu trnh thc hin th nghim, bc un si vi acid nhm
chuyn polyphosphate thnh orthophosphate, loi b nh hng ca nitrite v
cyanide. Thm mt lng tha phenanthroline loi b nhng sai s gy ra bi
cc cht oxyha mnh v to phc vi mt s ion kim loi c trong dung dch.
Nu hm lng cc ion kim loi qu cao, cn phi s dng phng php trch ly.
Nu mu c mu hay cht hu c, x l mu bng cch un si mu nhiu
gi vi acid HCl 1:1 trong cc c quai bng silica, s hay platinum. Khi mu cn,
t nh, phn tro cn li c ha tan bng acid. Nu hm lng cht hu c qu
cao, bc phn hy s c thc hin trc giai on trch ly.
Phng php phenanthroline c th xc nh hm lng st nh nht l 10g.
Dung dch chun m:
20ml H2SO4 m c vo 50ml nc ct v thm vo 1,404
Fe(NH4)2(SO4)2.6H2O. Sau khi dung dch ng nht (1,00ml = 200g Fe =
200ppm).
Dung dch chun : chun b mi khi s dng.
Ly 50ml dung dch lu tr st cho vo bnh nh mc 1000ml, thm nc
ct ti vch nh mc (1,00ml = 10,00g Fe= 10ppm).

60

Thc hnh:
Xc nh St tng cng : (Fe tc)
Mu phi c lc u trc khi phn tch, ly 50ml mu cho vo erlen.
Nu th tch mu c hm lng st cao hn 200g, s dng mt lng mu t hn
v pha thnh 50ml. Thm 2ml HCl m c v 1ml NH 2OH.HCl. Thm vi vin bi
thy tinh vo erlen, un si n khi th tch cn khong 15 20ml (nu mu b
cn, cho vo 2ml HCl m c v 5ml nc ct).
Lm ngui mu nhit phng, chuyn dung dch vo bnh nh mc
100ml, thm 10ml dung dch m NH 3C2H3O2 v 4ml dung dch phenanthroline.
Cho nc ct ti vch nh mc v lc u, sau khong 10 15 pht cho
cng mu t cc i v n nh. o hp thu trn my spectrophotometer
bc sng 510nm.
Thit lp ng chun v xc nh mu
S dng dung dch chun c nng 10ppm .
Pha lot dung dch chun st nh sau :

STT
V chun (ml) Fe 10ppm
V mu nc (ml)
V HCl m c (ml)
V NH2OH.HCl (ml)
V NaOH 30% (ml)
V m Amoniaxetat(ml)
V 1-10 phenanthroline (ml)
H2O ct (ml)
Hm lng ppm Fe

0
0

1
1

2
2

3
3

4
4

M1
0
3
0,5 0,5 0,5 0,5 0,5 0,5
1
1
1
1
1
1
0,5 0,5 0,5 0,5 0,5 0.5
3
3
3
3
3
3
1
1
1
1
1
1
4
3
2
1
0
1
0
1
2
3
4
Cx1

M2
0
3
0,5
1
0.5
3
1
1
Cx2

Ch thch :
* un si cho ti th tch dung dch cn khong 1015 ml.
* nh mc thnh 100ml bng nc ct. Lc u v o hp th.
61

Ly mt mu nc ct v thc hin tt c cc bc nh trn lm mu

trng chun.
Nu mu b c v c mu, thay v s dng nc ct lm mu chun trng,
s dng chnh mu lm mu chun trng v x l mu qua tt c cc bc nh
trong qu trnh thc hin nhng khng cho phenanthroline.
TNH TON
Sau khi c hp th ca mt lot chun. V gin A = f(C), s dng
phng php bnh phng cc tiu lp phng trnh y= ax + b. T tr s hp
th ca dung dch mu Am suy ra Cm t phng trnh trn. Kt qu biu din bng
n v mg/l.
a. Xc nh NO3- trong nc
Nguyn tc :
Phn ng gia nitrate v brucine cho sn phm c mu vng c p dng
xc nh hm lng nitrate bng phng php so mu. Cng mu c o
bc sng = 410nm. Tc phn ng gia nitrate v brucine chu nh hng r
rt vo lng nhit ta ra trong qu trnh phn ng. V th, cc cht phn ng c
thm vo ln lt v mt khong thi gian chnh xc ti nhit bit. Nng
acid v thi gian phn ng c la chn to mu tt nht v n nh.
Phng php ny thch hp vi c nc ngt v nc bin, vi hm lng N-NO 3
xp x 0,1-2 mg/l.
Cc nh hng :
S hin din ca tc nhn oxy ha c th c loi tr bng cch thm cht
phn ng orthotolidine. Tr ngi bi clor d c th b loi bng mt lng sodium
arsenite khi chlor d khng qu 5 mg/l. Mt lng d sodium arsenite nh khng
nh hng n vic xc nh nitrate. Ion Fe 2+, Fe3+ v Mn4+ s gy nh hng nh,
nhng nu hm lng cc ion ny nh hn 1mg/l th nh hng khng ng k.
Tr ngi do nitrite gy ra khi N-NO 2 < 0,5 mg/l c ngn nga bng acid

62

sulfanilic. Hm lng cht hu c cao trong nc thi cng s gy tr ngi cho

vic xc nh nitrate.
Dung dch NO3- lu tr 100ppm : Ha tan 0,7218g Anhydrous Potassium
Nitrate KNO3 + nc ct = 1 lt.
Dung dch NO3- chun 50 ppm . Pha long 50ml dung dch lu tr thnh
100ml
Qu trnh xc nh
Nu mu c chlorine, kh lng clor d ny bng cch thm 1 git sodium
arsenite cho mi 0,1mg Cl2 trn 50ml mu.
Chun b dung dch tham chiu nh sau:
STT
0
Chun NO3 50ppm
0
Mu nc xc nh
H2SO m c
3
Brucine
1
H2O
6
Cppm
0
Th t thc hin nh sau :

1
1

2
2

3
1
5
5

3
1
4
10

3
3
3
1
3
15

4
4
3
1
2
20

M1

M2

2
3
1
4
Cx1

2
3
1
4
Cx2

Do phn ng xy ra ph thuc vo rt nhiu nhit to ra t qa trnh hydrat ha

ca H2SO4 m c, nn khi cho H2SO4 vo th lp tc cho thuc th Bruccine
vo lc u. yn trong bng ti 20 pht, em ra nh mc thnh 10ml nh
trong bng , sau em i o hp th
o hp thu A = 410nm.
4. Cch tnh
T lot chun o hp thu.
V gin A = f(C), s dng phng php bnh phng cc tiu lp
phng trnh
y = ax .
T tr s hp thu Am ca mu tnh nng Cx.

63

10 1000
ppmNO 3 Cx.
1000 2

CHNG 4:PHNG PHP PH AAS V NG DNG TRONG PHN TCH

THC PHM
4.1 C s ca phng php ph hp thnguyn t AAS
4.1.1 S xut hin ca ph hp th nguyn t
Nguyn t bao gm ht nhn v cc in t chuyn ng xung quanh
ht nhn theo nhng obital c nng lng xc nh. Cc in t trong
nguyn t c phn b vo cc orbital theo quy lut t thp ti cao,
v iu kin thng nguyn t trng thi bn vng, c nng lng
thp nht. Nu cung cp nng lng cho nguyn t (in nng , nhit
nng, ha nng) th trng thi khng tn ti na th in t s
chuyn ln mc nng lng cao hn khi nguyn t b 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 c xu hng tr v
trng thi c bn gii phng nng lng, nguyn t gii phng ra nng
lng di dng cc bc x. Nu nguyn t b kch thch bi ngun bc
x in t th chng ta c ph hp thu nguyn t.
Nu nng lng gii phng di dng bc x in t th ta ph ph
pht x v nu tn pht pht x bng tn s hp thu th ta c s pht
x ton phn. trng thi hi, nu nguyn t b kch thch bi mt

64

chm tia sng c nhng bc sng (tn s) mang nhng nng lng
xc nh ng ng vi nng lng cn thit chuyn cc in t t
trng thi c bn ln cc trng thi kch thch tip theo.
Cc nguyn t t do s hp th cc bc x c nng lng xc nh .
Ph sinh ra trong qa trnh ny gi l ph hp thu nguyn t. Nu gi
nng lng ca tia sng b nguyn t hp th l E
Ta c:
E = ( Em E0 ) = h hoc E = h.c /
Eo : nng lng trng thi c bn
Em: nng lng trng thi kch thch
h : hng s Planck, C : tc nh sng
: di sng ca vch ph hp th
nhy ca cac phng phap:

ICP-MS

ppt

GF AAS+ ha hi

ppb

ppm

65

AAS-F

Pht x ngn la

0,1%

100%

ng vi mi mc nng lng in t c nhiu mc nng lng dao ng. ng vi mi

mc nng lng dao ng c nhiu mc nng lng quay. S hp th nng lng ca
phn t c tnh c trng. Mun chuyn t mc nng lng E0 ln mc nng lng E1
cn mt bc x c nng lng:
E = hv = E1- E0

Ch nhng bc x c nng lng ng vi khong cch ca cc mc nng lng trong

phn t mi c hp th. Qu trnh nguyn t ha c th thc hin vi phng php
ngn la: bng cch phun dung dch phn tch trng thi aerosol vo ngn n kh;
hoc khng ngn la: nh tc dng nhit ca l garphit. Cht nghin cu b nhit phn v
to thnh cc nguyn t t do. Trong iu kin nhit 1500 3000oC a s cc nguyn
t c to thnh trng thi t do. By gi nu ta hng vo lun hi nguyn t mt
chum bc x in t c tn s bng tn s cng hng, cc nguyn t t do s hp th
cc bc x ny lm gim cng chm bc x in t
4.2 Nguyn tc ca phng php
4.2.1 Nguyn tc ca phng php
nh ngha: Phng php phn tch da trn c s o ph hp thu nguyn t ca mt
nguyn t c gi l php o ph hp thu nguyn t
Mun thc hin c php o ph hp thu nguyn t ca mt nguyn t cn phi thc
hin qu trnh sau:
1/ Mu t dng lng di tc dng ca u t c nhit ln ti 30000C chuyn thnh
trng thi hi ca cc nguyn t t do( m my nguyn t)- y l qa trnh ha hi v
nguyn t ha mu.
2/ Mt chm tia sng bc x c trng ca nguyn t cn phn tch c chiu qua m
hi nguyn t. Cc nguyn t ca nguyn t cn xc nh s hp th nhng bc x nht
nh v to ra ph hp th ca n.
3/ Nh vo h thng quang ph ngi ta thu ton b chm sng sau khi i qua m my
nguyn t v chn mt vch ph hp th ca nguyn t cn xc nh o cng ca

66

n. Cng ca vch ph hp th t l thun vi nng ca nguyn t cn xc nh.

Cc nguyn t cng nh phn t hp th bc x in t theo nh lut Lambert- Beer
nh lut Lambert- Beer:
Khi chiu mt chm bc x n sc i qua mt dung dch, hp th bc x n sc ca
dung dch t l vi nng v chiu dy ca lp dung dch .

To c cng thc:

A = K LC = lgI0,
I
Vi:
A: hp thu
K : H s hp x ty thuc vo lc dao ng ca php chuyn di in t gy ra s hp
x.
L: Chiu di ngn la trong phng php F-AAS hoc chiu di on ng i qua l
GF-AAS.
C: Nng hi nguyn t cn xc nh trong Plasma.
I0,: Cng pht x pht ra t n cathode rng ti bc sng .
I: Cng hp x sau khi ra khi mi trng hp x. Thc t cng bc x sau khi
i qua ngn la cha mu.
iu kin thu c ph hp th nguyn t
+ Cc nguyn t trng thi ri rc khng lin kt ha hc vi nhau
+ C mt ngun sng ngoi thch hp (thng chn n cathode rng ca chnh nguyn
t cn thu ph hp x) di vo m hi nguyn t.
+ C mt thit b phn tch ph v ghi o thch hp.
4.3 Thit b php o ph AAS.
Thit b php o ph AAS ch yu bao gm nhng chi tit quang trng sau:
(1) Ngun pht tia bc x : thng l n cathod rng (hollow cathode lamp) : dng
pht ra cc bc x n sc, c trng cho tng nguyn t.
(2) H thng nguyn t ha : dng chuyn mu (thng l ion, th lng) t dng phn
tch dng lng sang th hi nguyn t:
C hai loi k thut nguyn t ha mu :
- Nguyn t ha bng ngn la ( Kh + Axetylen)

67

- K thut nguyn t ha khng ngn la

K thut nguyn t ha khng ngn la thng s dng :
-L grapht
- B to hydrua (hydride vapor generator HVG).
- B ha hi lnh phn tch thy ngn (MVU)
(3) H thng my quang ph : b n sc
(4) B n sc : thu phn ly v chn tia sng (vch ph) cn o nhm loi bt cc tia gy
nhiu, n sc thm mt ln na nh sng trc khi vo u d.
(5) u d (photomultiplier tube) : chuyn tn hiu quang thnh tn hiu in
(6) B phn tip thu v x l tn hiu.

4.3.1 B phn pht tia bc x

Nh ni trn, trong phng php hp thu nguyn t(AAS) ngun pht ra bc x phi
pht ra nhng bc x ph hp vi bc nhy ca nguyn t cn phn tch. t c
iu ngi ta dng ngun kch thch thch phi lun hin din m hi nguyn t ca
nguyn t cn phn tch khi lm vic.
n phi pht ra ngun bc x mnh v n nh, cc vch ny phi rt hp. V vy
thng ch to mi nguyn t ha hc mt n ring nh th lm tng tnh chn lc trong
phng php AAS.
C 2 loi n c s dng l n cathode rng (hollow cathode lamp: HCL) v n
phng in khng cc Electrodeless discharge lamp: EDL).
n cathode rng(HCL HOLLOW CATHODE LAMP)
Cu to gm 4 phn

68

Phn 1: Thn n
Thn n, v n, ca s lm bng thy tinh hoc thch anh. Nguyn liu lm ca s n
phi trong sut trong vng UV hoc VIS ty thuc vo loi n ca tng nguyn t. B
cc in cc catot v anot lm bng nha PVC.
Phn 2: in cc
Catot : C dng hnh xylanh hoc hnh ng rng, c ch to bng chnh kim loi cn
phn tch c tinh khit cao (>99.9%). Dy dn ca catot l W hoc Pt . Bao quanh
catot c lp mica khng dn in m bo s phng in tp trung vo catot v tng
cng vch cng hng.
i vi kim loi c im chy thp c ph mt lp mng trn ct ng. i vi kim
loi cng hoc gin th p bt hoc ch thnh hp kim lm catot.
Anot: c ch to bng kim loi tr v bn nhit nh W hoc Pt. c t bn cnh
catot hoc l 1 vng bao quanh catot.
Phn 3: Kh trong n
Kh np vo n khng c pht ra ph lm nh hng n chm tia pht x ca
n.Trong iu kin nht nh, t s gia cc nguyn t b ion ha v cc nguyn t
trung ha phi khng i n lm vic n nh. i vi kim loi c nng lng ion
ha cao cn s dng kh Ne v Ne c nng lng ion ha cao hn Ar. Trong n phi ht
ht khng kh v np vo kh tr: Heli, Ar, Ne ( tinh khit >99.9%) vi p sut 515
mmHg. Thay Ne bng Ar trong trng hp vch cng hng ca nguyn t cn xc nh
k cn vch ca Ne. Kh Heli t c s dng do s tc ng vo catot km v s hao ht
kh Heli trong n xy ra nhanh do Heli hp ph ln trn b mt n lm gim p sut kh
trong n v gim tui th ca n.
Phn 4: Ngun nui n
Th lm vic thng t 220 250 (V).
Ngun in mt chiu n nh.
Cng dng lm vic t 3 50 (mA).

69

Khi s dng khng nn dng n dng in cc i v n mau hng, nhy v lp

li ca php o km. Cng dng s dng tt nht l 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 s dng cng dng gn gii hn trn.
Nguyn tc hot ng ca n HCL bao gm 3 bc:
B1: Khi n lm vic, gia hai cc xy ra s phng in kh, lm ion ha kh tr thnh
ion. Kh tr s dng c th l Ar hoc Ne .
B2: Ion kh tr c tng tc bi in trng p vo catot lm sinh ra nguyn t kim
loi trng thi hi t do. .

B3 :Nguyn t kim loi t do b va p tip tc v chuyn thnh trng thi kch thch ri
pht ra bc x c trng. Chm tia pht x ny l ngun tia n sc chiu qua mi trng
hp thu thc hin php o AAS.
n phng in khng in cc (EDL Electrodeless Discharge Lamp)
Cu to bao gm 4 phn
Phn 1: Thn n
L ng thch anh chu nhit, mt u n EDL cng c ca s S, trong sut vi chm
sng cn phn tch. Cun cm bng ng cng sut 400-800 W c ni vi ngun nng
lng cao tn HF nui n lm vic. Ngoi cng l v n chu nhit.
Phn 2: Cht trong n
Kim loi hoc mui (iodua) ca kim loi ca nguyn t d bay hi thay cho catot trong
n HCL. y chnh l ngun cung cp tia pht x ca nguyn t phn tch khi chng b
kch thch. p sut hi kim loi trong n khong 1 1.5 mmHg v nhit t 500
800oC.
Phn 3: Kh trong n
n phi c ht ht khng kh v np vo n kh tr Ne, Ar, Heli p sut thp
(khong vi mmHg).
Phn 4: Ngun nui n:
Dng ngun nng lng cao tn cm ng in t nui n EDL lm vic, c ch to
theo 2 tn s:
Tn s sng ngn 450MHz n EDL sng ngn.
Tn s sng radio 27.12MHz n EDL sng radio.

70

Tm li: V cu to, n EDL thc cht l ng phng in trong mi trng kh tr c

cha nguyn t cn phn tch vi nng nht nh ph hp to ra chm tia pht x
ch bao gm mt s vch ph nhy c trng ca nguyn t phn tch.
Nguyn tc hot ng ca n EDL nh sau: di tc dng nng lng t ngun cao tn
lm ha hi cc mui kim loi ang t do, sau nguyn t kim loi ang t do chuyn
ln trng thi kch thch v pht ra bc x c trng khi n lm vic.
n EDL cung cp bc x c cng mnh hn nhiu so vi HCL
Php o n EDL c nhy v chnh xc cao hn HCL (xt cng 1 nguyn t).
4.3.2 B phn nguyn t ha
y l qu trnh chuyn cc cht cn phn tch thnh cc nguyn t t do dng hi, cho
php nguyn t hp thu nh sng nhng bc sng rt c trng

C hai kiu nguyn t ha:

(1) S dng ngn la (Flame)
(2) Khng s dng ngn la (Flameless)
- S dng l graphite (Graphit Furnace Atomisation-GFA)
- S dng b to hydrua (hydride vapor generator HVG)
- B ha hi lnh phn tch thy ngn (MVU)
4.3.2.1 K thut nguyn t ha bng ngn la
Ngn la c to thnh bng cch t chy hn hp ca cht oxi ha (thng l khng
kh hoc N2O) v nhin liu (thng l acetylene).

Nhit ca ngn la gip cho qu trnh nguyn t ha xy ra. Tin trnh xy ra i qua
nhiu giai on c th tm tc hnh sau:

71

Cc bc hnh thnh hi ngyn t:

+ Bay hi dung mi, ch cn li cc cht rn
+ Cc cht rn s bay hi di tc dng ca nhit
+ Di nhit cao cc phn t s b phn ly thnh cc nguyn t t do
+ Mt phn nguyn t s b ion ha thnh cc ion
S lng ion hay phn t s ph thuc vo bn cht ca tng nguyn t cng nh nhit
ngn la
Qu trnh by hi dung mi
+ Mu sau khi vo b phun mu s c phn tn thnh cc ht rt nh di dng sng
m, khi i qua mt mt vin bi lm bng ceramic
+ Mu di dng sng c i vo ngn la.
+ Cc dung mi bay hi ti y
+ Qu trnh bay hi dung mi s to thnh sol kh bao gm cc ht cht rn dng nng
chy
thch hp
Qu trnh bay hi cht rn
+ Sau khi bay hi dung mi, cht rn do c nhit bay hi cao hn s vn cn tn ti
trong ngn la di dng b nng chy.
+ Di tc dng tip tc ca ngn la nhit cao, n s b bay hi v phn ly thnh
cc nguyn t t do.
+ Ty thuc vo bn cht ca cht m c th l qu trnh to phn ly xy ra trc hay sau
qu trnh bay hi

72

Cc yu t nh hng ti qu trnh bay hi v phn ly:

+ Nng lng ca ngn la phi ln lm bay hi hon ton v b gy lin kt

+ Nhit cng cao cng c khuynh hng tng kh nng bay hi ng thi gim s to
thnh ca cc oxit vn chu nhit cao. Qu trnh bay hi khng hon ton s dn n hin
tng khng tuyn tnh ca ng chun
+ Kch c ht sol kh: Qu trnh bay hi cng mnh khi c ht i vo bung nguyn t
ha cng nh.
Cu trc ngn la:
V hnh dng cu to v s phn b nhit ca ngn la, n kh gm ba phn nh
sau:
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 (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 l a. 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

73

phn tch phi a mu vo vng 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.

Tc chy ca ca ngn la ph thuc vo:

+ Loi kh oxi ha v kh t.
+ T l thnh phn ca loi kh oxi ha v kh t v tc phun ca chng. Cc thnh
phn ny rt quan trng trong vic xc nh n nh cng nh hnh dng ca ngn la
Nhit ngn la theo loi kh

74

4.3.2.2 K thut nguyn t ha bng l Graphit

c im v nguyn tc chung k thut nguyn t ha khng ngn la
c im: 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. 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

75

khng km cc h thng ca php o trong ngn la v m bo nhy cao c ppb i

vi nhiu nguyn t.
Mt c im na ca php o khng ngn la l i hi mt lng mu tng i nh.
Thng thng mi ln o ch cn lng mu t 20 n 50L. 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 bn giai on k tip nhau: sy kh,
tro ha mu, nguyn t ha v lm sch l Graphite. Trong hai giai on u l chun
b cho giai on nguyn t ha t kt qu tt. Nhit trong l graphit l yu t
quyt nh mi s din bin ca qu trnh nguyn t ha mu.
Qu trnh lm kh mu
Tng t qu trnh loi dung mi trong phng php F- AAS, dung mi s c bay hi.
Thng thng nhit qu trnh ny khong 110oC (trnh si qu mnh lm bn mu).
Vic la chn nhit thng ph thuc vo nhit bay hi ca dung mi cng nh
trnh xy ra hin tng bn mu lm phn tn hoc mt mu. thc hin qu trnh sy
tt, i vi mi mt loi mu cn phi tin hnh nghin cu 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.
Qu trnh tro ha
Trong qu trnh ny cc hp cht hu c trong mu b tro ha hoc chuyn thnh nc,
CO2 v cc hp cht v c. Tip hp cht 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 l Graphite 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. iu kin l tng l nhit cao loi b cc hp cht bay hi
m khng lm mt cht phn tch. Giai on ny c nh hng rt nhiu n kt qu phn
tch, v 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. Mi
nguyn t c mt nhit tro ha gii hn gi l Tr trong php o ETA-AAS. 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. 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.
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 Si c nhit tro
ha gii hn l 1100oC, Ni l 1000oC, cn Pb l 600oC

76

Nn khc nhau ca mu (matrix effect), nht l cc cht nn bn nhit. Mt v d v vn

ny khi o ph hp th nguyn t ca Mg trong cc nn khc nhau nh hnh di y

77

Nhit ti hn ca mt s nguyn t ph bin

Qu trnh nguyn t ha
y l giai on cui cng ca qu trnh nguyn t ha mu, v l giai on quyt nh
cng ca vch ph. Hiu qu qu trnh ny chu 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. V
vy tc tng nhit li l rt ln gn nh ngay tc khc n nhit nguyn t
ha. Tc tng nhit thng l t 1800 - 2500 oC/giy, bng tc tng nhit ti a
ca my. Mc nguyn t ha ca mt nguyn t rt khc nhau. ng thi mi nguyn
t cng c mt nhit nguyn t ha gii hn gi l Ta. Nhit Ta ny ph thuc vo
bn cht ca mi nguyn t, trng thi v thnh phn ca mu m n tn ti, nht l cht
nn ca mu.

78

Cc kiu hnh thnh nguyn t ha trong l Graphit

S ha hi ca cc hp phn mu dng phn t.
Nu nhit 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. (Eh < Ea). Tiu biu cho cc hp cht thuc loi ny l cc oxit Sb 2O3, Ga2O3, cc
mui halogen ca cc kim loai nh SbCl5, SnCl4, SnBr4, AlCl3, TiCl 4, GaCl3, cc mui
axetat, Clorat ca kim loi, v.v... C ch din bin ca cc hp cht loi nyc 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.
Sau y l vi v d v c ch ny:
CdCl2(r,l) CdCl2(k) Cd(k)
CuCl2(r,l) CuCl2(k) Cu(k)
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 nhit phn li nh hn nhit ha
hi phn t ca chnh n Eh > Ea. 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) xM(r,l) + yX(k) xM(k)

79

xM(k)
(g) MxXy(r,l) xMO(r,l) + yX(k)xM(k)
xM(k)
(h) MxOy(r,l) xM(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, sufat,
photphat, 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 c nhy thp
hn cc qu trnh ca cc mui halogen trn. Tiu biu cho s din bin theo kiu ny
l 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
+ Mi trng tin hnh nguyn t ha mu.
+ Cht nn ca mu, cht ph gia thm vo.
Giai on lm sch Cuvet
Mc ch nhm lm bay hi cc cht bn nh cc kim loi hoc mui cn nm li trong
ng graphite. C th thc hin 3000oC nhng nhiu trng hp cng thc hin nhit
thch hp thp hn. Thng thng nhit lm sch s cao hn nhit nguyn t
ha khong 2000C .

80

M t cc bc gia nhit trong GFA

Cc loi Graphite
Thng thng c 3 loi l Graphite
+ ng graphite High density
+ ng graphite Pyrolytic
+ ng graphite c Platform
Kiu ng graphit t trng cao:
Loi ny c s dng o hu ht cc nguyn t vi kt qu chnh xc v l p
li cao. Tuy nhin vi cc nguyn t d dng phn ng vi cacbon to thnh cacbua kim
loi, nhng hp cht ny khng bay hi hon ton trong qu trnh nguyn t ha lm
gim .

Kiu ng graphit pyrolytic:

im khc bi t vi kiu ng graphit t trng cao l b m t ca ng graphit c
trng m t lp Titan c th ngn ch n phn ng gia cc nguyn t kim loi vi cacbon.
Khi s dng h thng ny nhy c th tng t 2 n 3 ln so vi kiu ng graphit t
trng cao cho cc nguyn t Al,Si, cc nguyn t thu c nhm 4b,5b,6b,7b,

81

(Ti,V,Cr,Mo,Fe,Co,Ni,Cu...) v cc nguyn t thu c h lantan.Tuy nhin l p li km

hn so vi kiu ng grapht t trng cao.

Kiu ng graphit c sn :
Sn l 1 thanh cacbon c b dy 1mm v di n tch vi mm2 c t vo trong ng
graphit.Vi kiu ny mu s c lm nng gin tip v ng u,lm gim nh hng
ca cht nn v tn hi u nn.

Rt hiu qu phn tch cc nguyn t Cd, Pd v cc nguyn t c nhi t si thp.

4.3.2.3 K thut hydride (Hydride Vapor Generator)
Nguyn tc: K thut to hydride c mt im ging k thut ha hi ngui (Cool
vapor) l mu c cho phn ng vi mt cht kh, sau kh sinh ra c dn n b
phn hp thu o. Tuy nhin, khc vi k thut ha hi ngui, kh sinh ra khng phi l
hi nguyn t t do m l hi phn t ca cc hp cht hydride. Cc phn t ny khng
gy ra hp thu nguyn t nn cn phi cung cp nhit phn hy chng thnh cc
nguyn t t do. K thut hydride c th c s dng phn tch cc nguyn t As,
Pb, Sn, Bi, Sb, Te, Ge, Se.
Trc y s to thnh cc hp cht hidrua AsH3, SbH3 v H2Se trong dung dch
thng c thc hin nhiu nht bng phn ng:
Zn + 2 HCl
ZnCl2 + 2 [H]
Em+ + (m+n) [H]
EHn + mH+
Trong : E l kim loi cn phn tch, m c th bng hoc khc n.

82

Nhng do phn ng trn c nhiu hn ch nh:

* Xy ra chm.
* Kh t ng ho.
* Kt qu phn tch ph thuc nhiu vo tinh khit ca km.
* Hiu qu phn ng b gii hn v phn ng xy ra khng hon ton v cc hp
cht hidrua d bay hi b hp ph hoc b by trong lp mt km.
V th, thay cho qui trnh trn ngi ta s dng mt cht kh c hiu qu hn l NaBH4.
NaBH4 + 3 H2O + HCl
H3BO3 +NaCl + 8 [H]
E+ + n[H]
EHn
V d:
Phn ng kh chuyn As (V) v As (III) trong qu trnh x l mu:
H3AsO4 + 3I- + 2H3O+
H3AsO3 + I3- + 3H2O
Phn ng vi cht kh NaBH4
H3AsO3 + BH4- + H+
AsH3 + H2O + H3BO3
Phng php ny c s dng nhiu hn hn so vi phng php Zn/HCl do c th p
dng vi nhiu nguyn t hn, do tc , hiu qu ca phn ng v gim c tp cht.
Phn ng xy ra hon ton trong khong thi gian t 10- 30s. Tc cht c thm vo
dung dch mu c acid ho trong khong t 0.1- 10%. Cc nhn t trn y gip
cho s t ng ho d dng hn v l yu t quan trng to nn s thnh cng cho k
thut to thnh cc hp cht hidrua. Acid dng cho qui trnh nu trn l HCl, HNO 3 v
H2SO4 cng c s dng. Nng ti u ca acid l mt thng s cho s ti u ho, n
ph thuc vo nguyn t phn tch v cht nn.
Hn ch ca phn ng:
* Tc cht khng phi hon ton khng ln tp cht, lm nh hng n nhy
gii hn pht hin.
* Lng ln kh H2 c phng thch cng gy cn tr.
u im:
k thut hydride c nhy cao v loi b c nh hng ca nn (matrix interference).
Nhc im:
- Hiu sut to hydride v nguyn t ha ph thuc mnh vo nhiu yu t bao gm trng
thi oxi ha ca nguyn t cn phn tch, thi gian phn ng, p sut kh, nng axit v
nhit ca b phn hp th.
- S to thnh hydride cng b nh hng bi cc cht trong thnh phn mu, do , k
thut ny vn b nh hng v mt ha hc (chemical interference).
Cn nhiu
Trong giai on to hp cht hidrua, s cn nhiu c to nn do s c mt ca
cc ion kim loi ngoi cht phn tch.
Cc nghin cu cho thy phng php phn tch bng k thut to hp cht
hidrua cng chu s cn nhiu c giai on to hp cht hidrua v giai on nguyn t
ho. S cn nhiu lm thay i tn hiu phn tch (thng l lm gim tn hiu).

83

Chng hn nh khi phn tch As v Se nu trong mu cn c cc ion kim loi

chuyn tip khc nh Cu(II), Co(II), Ni(II)... th hiu sut to thnh cc hp cht hidrua
vi cht phn tch s gim, ng thi cc tn hiu phn tch ca As v Se cng b che i.
l do hidrua ca cht phn tch phn ng vi cc sn phm to thnh t phn ng ca
cc kim loi vi NaBH4.
Tuy nhin cng c th gim nhiu bng cch thm NaBH4 vo t t vi nng
thp. Trong h thng tim theo dng lin tc th s cn nhiu cng c gim thiu, do
trong h thng ny hu nh khng c mt thi gian no m cht kh v sn phm phn
ng hin din vi nng qu cao.
Khi phn tch cc nguyn t trong cc mu sinh hc, acid Nitric thng c
dng ph mu v acid ho mu trc khi thm cht kh NaBH 4 v iu ny gy
nn vn l c s hin din ca cc oxit nit trong by nhit thp dng thu
thp cc phn t cht hidrua lm gim hiu sut to hp cht hidrua.
khc phc hin tng ny ngi ta thm mt lng acid sunfamic khi ph
mu. Trong giai on nguyn t ho, tn hiu phn tch thng b trit tiu do b mt ng
nguyn t ho thch anh khng b thu tinh ho, v hoc b nhim bn do s tch t cc
git cht lng nh b bm trn b mt ng.
Qu trnh nguyn t ho cng c th b dp tt nu c s hin din ca cc vt
dung mi hu c.
Ngoi ra, hiu sut nguyn t ho cn gim st do s hnh thnh cc phn t bn
nhit.
gim nhiu do nhng nguyn nhn trn, c th lm sch b mt ng nguyn t
ho thch anh bng HF, tng nhit nguyn t ho bng cch s dng cc h thng
nguyn t ho c nhit cao v tng nng cc gc hidro t do trong ng thch anh
Kt lun :
Phng php ny c nhy cao, gii hn pht hin thp, c th xc nh c cc
nguyn t c hm lng rt nh (mg/l hoc g/l), c chn lc rt cao do mi kim loi
hp th mt bc sng c trng do ngun bc x ngoi c to bng chnh nguyn t
cn xc nh.
Khng cn tch cc cht, kim loi khc trong mu. V vy phng php AAS
c s dng rt ph bin xc nh hm lng cc kim loi nng nh: As, Bi, Ge, Sb,
Se, Te, Sn, Pb
Tuy nhin phng php ny c nhc im l khng th xc nh cng lc nhiu
nguyn t, v th phng php ny tng i chm khi cn xc nh ng thi nhiu kim
loi trong cng mt mu phn tch.
4.3.2.4 K thut ha hi lnh (Mercury Vapor Unit)
Gii thiu
- CV-AAS l phng php quang ph hp x nguyn t khng ngn la, s nguyn t
ho thu ngn (Hg) c thc hin ngay ti nhit thng v Hg l nguyn t tn ti
th lng v c th bay hi ti nhit phng. Nh c tnh ring bit ny nn Hg l

84

nguyn t duy nht thch hp cho vic xc nh m khng cn nguyn t ho sau khi
c kh ti trng thi c bn. V vy hu nh ton b hi thu ngn u tham gia vo
qu trnh hp th.
- H thng CV - AAS c b ho hi lnh Hg gm cc bnh phn ng v h thng li cun
hi thu ngn.
Nguyn tc
Trong k thut ha hi ngui, ion Hg2+ trong dung dch mu c kh thnh nguyn t t
do bng cch cho phn ng vi mt cht kh mnh nh thic clorua (SnCl 2) hoc natri
tetrahydroborate (NaBH4) trong mt h thng kn. Sau , hi thy ngn t do c dn
t bnh phn ng n b phn hp th bng cch sc mt dng kh mang thch hp, tr
vi Hg (khng kh, nit hoc argon) vo dung dch mu. i khi b phn hp th c
gia nhit cht t (khong 100oC) trnh ngng t hi nc.

Nu cht kh l SnCl2 th Hg2+ b kh theo phng trnh:

Sn2+ + Hg2+
Hg0 + Sn4+

Nu cht kh l NaBH4 th Hg2+ b kh theo phng trnh:

Hg2+ + 2BH4Hg0 + H2 + B2H6
u im
- nhy ca phng php CV- AAS l ln hn khi so vi kt qu thu c t
phng php F-AAS. C th hiu sut ly mu l 100% (so vi 10% ca k thut ngn
la). Ton b Hg trong dng dch mu t trong bnh phn ng u c nguyn t
ho v c vn chuyn n cell mu v o.
- nhy c th tng ln nh s dng cc mu c th tch ln hn v ton b hi Hg
cha trong mu c gii phng o. Khi tng th tch mu th c ngha l c nhiu
nguyn t Hg c hiu lc c chuyn di ti cell mu v o.
- Gii hn pht hin ca CV-AAS khong 0.02ug/L.
4.4. Phn tch nh lng bng AAS
Mu chun trong php o AAS
Trong phng php phn tch nh lng theo ph hp th nguyn t , mu chun
dng ng chun cng bt buc phi tha mn mt s iu kin nht nh. Cc iu
kin l:
1. Cc mu chun 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 chun
cng phi c tnh cht ging nh th. C nh th mi loi tr c nh hng ca nn,
v thnh phn ca mu n kt qu phn tch.
2. Cc mu chun v mu phn tch phi c pha ch, x l trong cng mt iu kin
nh nhau.
3. Cc mu chun 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 chun. C nh th mi bo
m c thnh phn ca n nh tnh ton pha ch v s dng lu di.

85

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 chu n ca php o v
bao trm nng ca cc mu phn tch. Ngha l nng cc m u phn tch phi trong
vng tuyn tnh ca ng chu n. Cn nu khng, chng ta phi pha long mu phn
tch cho ph hp.
Cc phng php phn tch nh lng 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:
1. Phng php ng chun;
2. Phng php thm tiu chun;
3. Phng php th khng i;
4. Phng php dng mt mu chun.
Phng php ng chun
Nguyn tc ca phng php ny l ngi ta da vo phng trnh c bn ca php o
A theo nng mt dy chun (t nht l ba chun) 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.

th chun ca ca phng php ng chun

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 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
chun tha mn cc iu kin quy nh cho phng php 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

86

khng th chun b c mt dy mu chun ng n nn s b nh hng ca nn, ca

thnh phn ca mu. chnh l nhc im ca phng php ny. Trong nh ng 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.
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 chun
ph hp v thnh phn vi mu phn tch, th tt nht l dng phng php thm chun.
Nh vy 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 chun, 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
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 chu n.

th thu ng t phng php thm chun

xc nh Cx ta c th thc hin theo hai cch:

87

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.
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.
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 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, ngi ta ch
vic thay gi tr Ax o c vo phng trnh tnh Cx

Hin nay phng php ny c s dng rng ri trong phng th nghim, cc thit b o
c ci t sn phng trnh ng chun t tnh kt qu ca mu o. Tuy nhin
cn phi kim tra nh k, v theo thi gian th iu kin hot ng ca my s khng cn
ng nht gy ra s sau lch cho php o.
Phng php mt mu chun
+ 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 C l 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.

88

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

tr C1l chng ta c gi tr nng Cx phi tm theo biu thc trn.
+ 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 v1mu
thm chun theo phng php thm chun v tnh ngay gi tr C x 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)
Vi mu u phn tch c thm chun: Ach= a.(Cx+ Cl)
(b)
Do ly (a) chia cho (b) chng ta c: Cx = [Ax /(Ach-Ax)]. C1
Nh vy khi o c gi tr Ax v Atch ta tnh c nng Cx phi tm theo biu thc
trn.
Nhng mt iu phi ch l nng thm vo C l v cc gi tr Cx phi nm trong
vng tuyn tnh ca phng php.
4.5. ng dng quang ph AAS trong phn tch thc phm
4.5.1 Xc nh mt s nguyn t vi lng (Fe, Cu, Zn) trong rau qu bng AAS (F
AAS).
4.5.2 Xc nh ch, cadmium, km, ng v st trong thc phm bng ph AAS ( AOAC
999-116)
4.5.3 Xc nh Cd trong thc phm bng k thut nguyn t ho ngn la (FAAS)
AOAC 973-34
4.5.4 Xc nh thu ngn trong thc phm bng FAAS ( 971-21)
4.5.5 Xc nh Cadmium, chromium, copper, iron, lead, magnesium, manganese, silver,
zinc trong thc phm bng AAS (AOAC 974-27)
4.5.6 Xc nh Nickel trong Tea Atomic Absorption Spectrophotometric Method (AOAC
975-34)
4.5.7 Phn tch Pb trong Milk bng ph AAS )

89

CHNG IV
PHNG PHP CHUN IN TH
4.1.C s ca phng php chun in th

90

4.1.1.nh ngha: phng php chun in th mt phng php phn tch

da trn vic o s bin thin th trong sut qu trnh chun dung dch
nghin cu.
4.1.2.t im ca phng php
- Trong sut qu trnh chun th dung dch thay i, s thay i xy ra
t ngt ti thi im st trc v st sau im tng tng.
- Cn chn in cc thch hp vi loi phn ng chun .
u im so vi phng php ha hc l:
+ nhy cao c th ln ti 10-5mol
+ Chun c nhng dung dch c mu
+ Chun nhng trng hp khng c cht ch th
4.1.3. Pin
Pin in ha

91

Gm mt bnh in phn c phn lm hai phn. Mt bn cha dung dch CuSO 4

trong c nhng in cc Cu, mt bn th cha dung dch ZnSO 4 v c nhng
in cc Zn. Khi ni 2 in cc i qua mt in k G, ngi ta thy mt s hin
tng nh sau :
- Kim in k G ch chiu dng in i t Cu sang Zn
- Khi lng Zn gim, khi lng Cu tng
- [ZnSO4] tng , [CuSO4] gim
Nguyn nhn ny c gii thch nh sau :
Dng in i t cc Cu sang Zn => dng in t s i t cc Zn sang Cu. Cc Zn
cho in t , cc Cu nhn in t.
Suy ra:

Zn 2e

Zn2+ qu trnh lm cho [ZnSO4]tng -> m Zn gim

Cu2+ + 2e

Cu. ng sinh ra kt tinh ln cc Cu lm khi lng Cu

tng , [CuSO4] gim

Tng hp cc phn ng 2 in cc ta c :
Cu2+ + Zn

Cu + Zn2+

Phn ng ny chuyn ha nng thnh in nng, v h hot ng nh vy

gi l h pin
Zn/ ZnSO4 // CuSO4 /Cu
Hay:

Zn/ Zn2+ // Cu SO4 /Cu

4.1.4.Th in cc
Kho st 1 thanh kim loi nhng trong mt dung dch in ly, nh vy s c s
tip xc b mt thanh kim loi vi dung dch. S tip xc ny sinh ra mt s
chuyn di cation t thanh kim loi i vo dung dch hay t dung dch kt tinh ln
b mt kim loi.

92

DD
* TH1 : Khi KL
th mt lng cation kim loi c xu hng bc khi b

mt i vo dung dch.
Khi cation kim loi bc khi b mt i vo dung dch in t li trn b mt
kim loi lm b mt tch in (-), b mt tch in (-) c xu hng ht cc cation
ln b mt ca n to nn lp in kp v hnh thnh th in cc.

DD
* TH2:Ngc li KL
th cation trong dung dch s kt tinh ln b mt

kim loi, s kt tinh ca cc cation kim loi lm b mt kim loi tch in (+) v
c xu hng ht cc anion ti b mt ca n v sinh ra th in cc.
xc nh gi tr ca th in cc ngi ta khng th xc nh gi tr
tuyt i ca n m ch xc nh gi tr tng i qua th c gia 2 in cc
ch khng th xc nh th ca mi in cc. V vy trong k thut xc nh
gi tr ln, nh v th ngi ta phi chn mt th in cc chun v t cho n
mt gi tr , cc in cc khc s c gi tr sau khi so snh vi n, in cc
ngi ta chn l in cc Hydro v xem E02H+/H2 = 0
Cch xc nh th tiu chun : Th tiu chun l th c xc nh trong
iu kin tiu chun 250C- 1atm
93

V d 1: Xc nh

E Cu

/ Cu

=?

E = E0Cu2+/Cu E02H+/H2

Chiu dng in chy t cc Cu n cc Hydro

Lp pin nh sau : (Pt)H2/ H+//Cu2+ /Cu
Theo thc nghim o c E= 0,34V. V E02H+/H2 = 0
Suy ra :E0Cu2+/Cu = 0,34V
V d 1: Xc nh E0Zn2+/Zn
Thc nghim o c: E= 0,77V
Chiu dng in chy t cc Hydro n cc Zn
Lp pin nh sau: Zn/Zn2+//H+/(Pt)H2
M : E = 0,77V = E02H+/H2 - E0Zn2+/Zn = 0,77v
Suy ra : E0Zn2+/Zn = - 0,77v

94

95

Gi tr th ca cc cp oxy ha kh

96

Th tiu chun
Gi tr th o c gia kim loi v dung dch mui ca n c xc nh
bng phng trnh Nerst

RT
E E0
ln C
nF
Trong E0 l th tiu chun ca kim loi
iu kin chun 250C, 1at th phng trnh c vit li nh sau :
0,059 OX
E E0
lg
Kh
n

V d: i vi cp Fe3+/ Fe2+
0,059 Fe3
E E0
lg
1
Fe2

i vi cp Cu2+/ Cu
0,059 Cu 2
E E0
lg
2
Cu

V kim loi Cu lm in cc nn c th xem hot ca n khng i v vy

c th vit li nh sau :
0,059
E E0
lg Cu 2
2

Th thc
Thc t th th o c ca mt cp oxy ha kh khng ch ph thuc vo bn
cht kim loi lm in cc v nng ion ca n m cn ph thuc vo cc
yu t khc nh mi trng m chng tn ti
V d nh phn ng c s tham gia ca cc ion H+ vo qu trnh oxy ha kh :
MnO4- + 5e + 8H+ = Mn2+ + 4H2O
Ta thy lc ny th c tnh nh sau:
0,059 MnO 4 H 8
0
EE
lg
5
Mn

Hay xt phn ng : Cr2O72- + 6e + 14H+ = 2Cr3+ + 7H2O

97

Th lc ny c tnh nh sau :
0,059 CrO 72 H 14
E E0
lg
6
Cr 3 2

Th cn bng
Trong phng php chun in th, qu trnh kho st phn ng xy ra khi
chun chnh l kho st s bin thin th sinh ra gia cc cp oxy ha kh tham
gia phn ng. Trong qu trnh cht ng vai tr oxy ha s tham gia vo qu
trnh kh v nhn in t lm cho gi tr th ca n gim xung cn cht ng vai
tr cht kh s tham gia vo qu trnh oxy ha, cho in t lm cho th ca n tng
ln. Khi th ca hai cp oxy ha kh bng nhau th qu trnh chm dt. Th o
c ti thi im gi l th cn bng .
Nh vy th cn bng l th m ti cht oxy ha phn ng va vi cht
kh trong qu trnh chun .
V d: xt qu trnh phn ng xy ra trong h gm mt thanh Pt nhng trong
dung dch Fe2+ v Fe3+ c nng bng nhau. Cng trong iu kin y trong dung
dch Cu2+ v Cu+ . Ngi ta ni hai in cc qua mt b phn o th quan st s
bin thin ca th t trong qu trnh.
Phn ng chun xy ra nh sau :
Fe3+ + Cu+ = Cu2+ + Fe2+
Lc ny th ca cc Fe c tnh nh sau :
E 0,77

0,059 Fe3
lg
1
Fe2

Th ca cc Cu : E 0,17

0,059 Cu 2
lg
1
Cu

Qu trnh phn ng lm sinh ra Fe 2+ nng Fe2+ tng dn n th cc Fe

gim.
Ngc li nng Cu2+ tng nn th cc Cu tng
Khi EFe = ECu ta c ECB = EFe = ECu

98

Hay : 2ECB = 0,77 + 0,17 +

0,059 Cu 2 Fe3
lg
(1)
1
Cu Fe2

Theo phn ng va trnh by trn s mol Fe 3+ b kh bng s mol Cu+ b oxy

ha. Nu nng ban u ca hai ion l bng nhau th ti thi im bt k ca
phn ng ta lun lun c :
[Fe3+] = [Cu+]
[Fe2+] = [Cu2+]
Suy ra:

Cu

Fe3
Cu 2 Fe3 1

suy
ra
Cu 2 Fe2
Cu Fe2

Thay vo (1) ta c :
ECB =

0,77 0,17
0,47V
2

Tng qut phng trnh oxy ha kh xy ra nh sau :

a[Ox1] + b[Kh2] = a[Kh1]+b[Ox2]
Trong : [Ox] l dng oxy ha v [Kh] l dng kh
Nu c t s cn bng a[Ox1] = b[Kh2] v a[Kh1= b[Ox2] th th cn bng
xc nh nh sau: Ecb

aE1 bE 2
ab

Vi:
- E1 l th tiu chun ca cht oxy ha
- E2 l th tiu chun ca cht kh
4.1.5. Cc loi in cc
Cc loi in cc : C 3 loi
Loi 1 : L mt thanh kim loi M c nhng vo mt dung dch c cha
cation ca n.
V d: Ag| Ag+, Cu|Cu2+
Mn+ + ne M

99

E E0Mn /M

0,059 [ Mn ]
lg
n
[M ]

V kim loi lm in cc nn hot ca n khng i

E E0Mn /M

0,059
lg[ Mn ]
n

V d : in cc Ag| Ag+ ta c : E E0 Ag /

/ Ag

0,059
lg[ Ag ]
1

in cc Clo (Pt)Cl2|ClCl2 + 2e 2ClE E0 Cl 2 / Cl

0,059 [Cl 2]
lg
2
[Cl ]2

V y l kh bo ha nn : E E0 Cl2 / Cl

0,059
1
lg
1
[Cl ]

in cc Hydro: (Pt) H2| 2H+

2H+ + 2e H2
E E0 H / H 2

0,059 [ H ]2
lg
2
[ H2 ]

V y l kh hydro bo ha nn hot khng i v vy c th vit:

E E0 H / H 2

0,059
lg[ H ]
1

Loi 2 : c cu to gm kim loi M, ph ln b mt ca n mt lp mui t

tan, sau nhng vo dung dch c cha anion mui ny. M.MA/ AnMA + ne M + An-

100

E E0 MA/

An

0,059
[ MA]
lg
n
[ M ][ An ]

V hot ca MA v M khng i nn biu thc tnh th trong trng hp

E E0 MA/

ny l :

An

0,059
1
lg
n
[ An ]

V d: in cc Calomen : Hg. Hg2Cl2/ ClHg2Cl2 + 2e -> 2Hg + 2ClE E0 Hg2 Cl 2/ Cl

0,059
1
lg
2
[Cl ]2

Loi 3 : Cn gi in cc oxy ha kh c cu to gm thanh kim loi tr (Pt)

nhng trong dung dch c cha thnh phn kh v oxy ha ca cp oxy ha kh.
2

Fe Cr O
(Pt)
(Pt)
Fe Cr
3

2
3

Cr2O72- + 6e + 14H+ -> 2Cr3+ + 7H2O

Fe2+ - 1e -> Fe3+
Cr2O72- + 6Fe2+ + 14H+ -> 2Cr3+ + 6Fe3+ + 7H2O

2 Fe3+ + Sn2+ -> Sn4+ + 2Fe2+

101

Ag+ + Sn2+ -> Ag + Sn4+

Cc in cc thng dng
Cc in cc thng lm ch th cho qu trnh
-

in cc bc: Ag/ Ag+

Phng trnh trao i in t : Ag e = Ag+

E E0 Ag /

/ Ag

0,059
lg[ Ag ]
1

in cc ng: Cu/Cu2+

Phng trnh trao i in t : Cu -2 e = Cu2+

0,059
E E0
lg Cu 2
2

in cc Clo:

(Pt) Cl2/ 2ClCl2 + 2e -> 2ClE E0 Cl 2 / Cl

-

0,059
1
lg
1
[Cl ]

in cc Hydro
(Pt) H2/ 2H+
2H+ + 2e H2
E E0 H / H 2

0,059
lg[ H ]
1

in cc mng: (in cc chn lc ion, ion selective electron)

102

Trong nhng nm gn y ngi ta ch to ra nhng in cc mng

chn lc. y l nhng pin, phn cch vi dung dch kho st bng mt
mng. Mng tc dng thun nghch vi mt ion hay mt nhm ion no
trong dung dch mt cch chn lc, bn trong in cc cha dung dch nng
xc nh cng loi vi ion cn kho st. Khi nhng in cc vo dung
dch cn kho st, xc nh hiu th gia hai bn b mng, t xc nh
nng ca dung dch cn kho st. S trao i e thng qua s di chuyn
cc ion chn lc qua mng
in cc mng gm 2 loi : Mng rn v mng lng
in cc mng rn: bao gm mng thy tinh, mng n tinh th,
mng rn ng th
* in cc thy tinh
Gm cc kim loi silicat c in tr ln thng dnh cho vic xc
nh ion H+ v Na+. Mng l mt lp thy tinh mng, bn trong cha dung
dch H+ dng o nng H+ hay OH- ca dung dch kho st. Khi nhng
in cc vo dung dch o, c phn ng trao i thun nghch gia H + trong
dung dch v Na+ trong thy tinh ca lp mng.
Na+tt + H+dd Na+dd + H+tt
Ty thuc vo t l thnh phn cc oxit to ra mng m mng s chn
lc nhng ion no
V d: 27% Na2O-5%Al2O3- 68%SiO2 ta c ic cc mng chn lc
H+. Nhng 11% Na2O-18%Al2O3- 71%SiO2 ta c ic cc mng chn lc
Na+.
*in cc mng tinh th
Nhng in cc mng ny c chm lc rt cao v thng khng b
nh hng bi cc ion khc.
V d: in cc mng F- vi tinh th LaF3 ch cho ion F- i qua v c th xc
nh hm lng F nng 10-6M ch chu nh hng bi OH-.
*in cc mng rn ng th
103

Cc mng loi ny c in tr thp v dn in cao. Mng c

hnh thnh t vic nn p sut cao, dy thch hp nn bn c hc.
Cc vt liu to mng thng l: Ag2S, AgBr, AgCl hay l s kt hp : Ag 2SAgCl, Ag2S- AgBr, Ag2S- MS vi M c th l Cu, Cd, Ni
*in cc mng lng
y l cc in cc m cc vt liu ch to mng l nhng cht trao
i ion (cation hay anion) dng hu c khng tan trong nc hay cht rn
ha tan dung mi hu c. Cc cht ny thng c phn tn trong pha rn
xp c din tch b mt ln, tr k nc. Thng cc mui hu c ca cc
kim loi.
Cc in cc c gii hn pht hin ph thuc vo tan ca cc ion
trong nc v b nh hng b cc ion c cu to tng t. Mng l mt
lp thy tinh xp, bn trong cha dung dch nng xc nh ca ion kho
st. Cc phn ng trao i hai bn mng thy tinh xp. Tu theo dung dch
cha bn trong in cc, c nhng loi in cc mng K+, Ca2+.
-

in cc so snh

Thng l nhng in cc loi 2

+ in cc calomen
S in cc : (Pt) Hg.HgCl2/ ClPhn ng in cc : HgCl2 + 2e Hg + 2Cl0,059
1
E E 0 HgCl 2 / 2 Hg
lg
2
Cl 2

Th ca in cc calomel tu thuc vo nng KCl

ic cc Calomel bo ha: ( SCE Satured Calomel electrode) vi
dung dch KCl bo ha. in cc ny c E = 0,247v 250C.
in cc Calomel nguyn chun ( N.C.E normal calomel electrode)
vi nng dung dch KCl bng 1M . in cc ny c E = 0,284V 250C.
Ngi ra cn c hai loi in cc c th l 0,25v vi nng [ Cl -] =
3,5M v E = 0,337V vi [Cl-] = 0,1M.
104

in cc Sulfat thy ngn

S in cc: (Pt) Hg/HgSO4/ SO42Phn ng in cc : HgSO4 + 2e Hg + SO420,059
1
E E 0 HgSO 4 / Hg
lg
SO 42
2

Th ca in cc E = 0,682v khi [ SO42-] = 1M

in cc Clorua Bc:
S in cc : Ag.AgCl|ClPhn ng in cc : AgCl + e Ag + Cl0,059
1
E E 0 AgCl / Ag
lg
1
Cl

Th ca in cc E = 0,237V khi [ Cl-] = 1M.

E = 0,290V khi [ Cl-] = 0,1M.
4.1.6. Phng php o th gia hai cc
Ngi ta khng th o sut in ng ca pin bng cch ngi ta ni 2 in
cc ca n qua mt vn k v khi ni nh vy s to ra dng in ngha l c mt
gim in th U ca pin, sut in ng o c khng chnh xc. trnh
tnh trng ny ngi ta dng phng php b chnh ngha l ngi ta mc t bn
ngoi vo mt ngun b sung trong qu trnh o, ngun l mt acqui c sut in
ng khong 2V , v mc mch nh sau:

105

Ex: th pin cn o
Ew : sut in ng ca pin chun
( c gi tr xc nh chnh xc )
Ea : ngun b chnh
G: in k
Cch o:
- Cho kha K vo v tr 1 sau ngi ta di chuyn con chy n im C
sao cho kim in k G ch 0 ta c:

(1)
- Sau a k vo v tr 2 , di chuyn con chy n C`sao

cho kim in k G ch 0

(2)

T (1) v (2) =>

106

V dy dn AB l ng cht

My chun in th hiu Metrohm

107

Set Endpoint Titration

Signal
[pH/mV]
End
point

volum
e

4.1.7. K thut xc nh im tng ng

K thut chun

ng cong chun thng c dng hnh ch S, s dng quy trnh lp

li hi quy khng tuyn tnh xc nh t nht 5 im xung quanh im
un.

K thut gia tng th tch hng nh

108

Th tch thm vo gi nguyn khng i. Ghi nhn s bin i ca in

th theo th tch, qua s xc nh c im tng ng. Thng ng
dng cho chun oxy-ha kh v chun phc cht.
K thut ng lc hc
Gi cho s bin i theo thi gian ca in th l khng i, thay i th
tch thm vo gia cc i v cc tiu.Thng ng dng cho chun
acid / base v chun kt ta.

K thut cn bng c kim tra

Cc thng s cn bng ca chun c thit lp theo s bin i ca in th

trong mt khong thi gian no , iu ny c ngha l khi s bin i ca th
va t ti gi tr gn vi gi tr cn bng th my chun s ghi nhn s liu v
tip tc nh lng mi, khong thi gian gii hn gia cc ln gia tng cht chun
c quy c l t(min) v t(max). Thng ng dng cho mi chun .
4.2.

Cc phng php chun in th .

Khi chun in th cn phi nhng vo dung dch nghin cu hai cc. Mt

cc th ca n cho bit nng ca cht b chun, cc gi l cc ch th . cc
kia tr i vi ion b chun, ch dng xc nh th ca cc ch th, cc ny gi
l cc so snh .
Da vo bn cht ca phn ng xy ra trong qu trnh chun m ngi ta
chia thnh cc phng php chun in th sau :
4.2.1.Phng php kt ta:
C th minh ha phng php kt ta trong chun in th qua v d xc nh
bc. C th dng cc bc lm cc ch th i vi ion bc. Cc so snh l cc
calomen.
Eo = Ech th - Echun
(Pt)Hg.HgCl2/ Cl- || Ag+ |Ag
Gi s ly 100ml dung dch AgNO 3 0,1N chun . Th ca cc bc
trong dung dch u c xc nh bng cng thc:
109

Ech th = 0,81 + 0,059lg0,1 = 0,742 v

Khi thm dung dch Cl- 1N vo, nng ion bc gim i v ion bc chuyn
vo kt ta.
Gi s thn 5ml dung dch Cl- 1N tng ng vi na hm lng ion bc
tham gia phn ng, nng ion bc gim xung mt na cn 0,05N. (b qua s
tng th tch ) v th ca cc bc s l :
Ech th = 0,81 + 0,059lg0,05 = 0,725 v
Khi thm n 9ml Cl- 1N tng ng vi qu trnh chun t 90%
Ta c : Ech th = 0,81 + 0,059lg0,01 = 0,684v
Khi thm 9,9ml Cl- 1N vo, tng ng t 99% qu trnh chun
Ta c : Ech th = 0,81 + 0,059lg0,001 = 0,626 v
Khi thm 9,99ml Cl- 1N vo, tng ng t 99,9% qu trnh chun
Ta c : Ech th = 0,81 + 0,059lg0,0001 = 0,574v
Ti im tng ng lc ny nng bc c tnh nh sau:
[Ag+] = TAgCl / [Cl-]= 1,7.10-10/ [Cl-]
Theo tin trnh phn ng ta thy: [Ag+] = [Cl-]
Suy ra : [Ag+] = 1,7.10 10 1,3.10 5
Th ti im tng ng : Ech th = 0,81 + 0,059lg 1,7.10 10 = 0,516v
Sau im tng ng nng ion bc ph thuc vo lng d ion Cl - v
cng c tnh bng tch s tan ca AgCl . Nu thm 0,01ml dung dch Cl - vo
dung dch tng ng vi nng Cl- t c l 10-4M.
Lc ny [Ag+] = 1,7.10-10/ 10-4 = 1,7.10-6
Tng ng vi E = 0,81 + 0,0ng1,7.10-6 = 0,465 v
Khi cho d 0,1ml dung dch Cl- vo dung dch, tng ng vi nng Clt c l 10-3M.
Lc ny [Ag+]= 1,7.10-10/ 10-3 = 1,7.10-7
Tng ng vi E = 0,81 + 0,059lg1,7.10-7 = 0,408 v
Nhn xt :

110

+ Ti nhng thi im ban u ca qu trnh chun , cng ging nh

nhng thi im sau qu trnh chun , gi tr th ca h thay i khng ng k
mc d lng thuc th cho l kh ln.
+Ti nhng thi im st trc v st sau im tng ng, khi thiu
0,01% v d 0,01% th gi tr th ca cc ch th c s thay i r rt t 0,574v
n 0,465v. Ngi ta gi l bc nhy in th ng vi 0,109v.
Nu ta o hiu th gia hai cc ch th v so snh th bc nhy gim th E
= (0,574 - Eso sanh ) - (0,465 - Eso sanh ) = 0,109 v
y l im gip cho ngi kim nghim vin phn tch nhn bit v kt
thc s chun ti y. T nng ,th tch tiu tn ca thuc th v th tch ca
dung dch em i xc nh, ngi ta tnh c nng ca cht cn nh phn.
th s chun dung dch Ag+ bng dung dch Cl- c m t nh sau :

th c tnh i xng qua im tng ng

Nhn xt:
+ Bc nhy th ca ng nh phn ph thuc vo tch s tan ca kt ta
to thnh. Nu kt ta cng c tch s tan cng ln th bc nhy ng nh phn
cng di. V d khi chun Ag + bng I- th bc nhy ng nh phn di hn do
TAgI = 10-16

111

+ Bc nhy ng nh phn ph thuc vo nng cc dung dch chun

. Nng dung dch chun cng ln th bc nhy ng nh phn cng di
4.2.2.Phng php to thnh cc phc cht t phn ly
Phn ng to thnh trong phng php ny to ra phc cht c bn tng
i ln.
Ta xt v d chun cation kim loi bng EDTA
Phn ng chun M + Y = MY (1)

MY

Hng s bn: MY
M Y
in cc ch th: in cc Hg
in cc so snh: in cc calomen
Pin to c (Pt)Hg.HgCl2/ Cl- // Hg2+/Hg(Pt)
0,058
Echithi E 0 Hg 2 / Hg
lg Hg 2
2

Eo = Ech th - Echun
Tnh [Hg2+]
Nu ngay t u ta thm mt lng chnh xc HgY 2- vo dung dch. Ta c
cn bng: HgY2- = Hg2+ + Y4

HgY

HgY 2
21,8
Hg 2 Y 4 = 10 (2)

Khi thm dung dch chun Y vo ta c Y s tham gia vo c hai cn bng (1) v
(2)

HgY 2 HgY 2 . M MY
HgY Y 4
HgY
MY
HgY 2 . M
=
HgY MY MY

Ta c : [Hg2+] =

Thay vo biu thc tnh Echi thi ta c :

M
0,058 HgY 2
MY .
Echithi E 0 Hg 2 / Hg
lg
HgY
MY
2
Nu nng HgY2_ ln th c th xem [HgY2-] khng i
112

Ta c Echithi A

M
0,058
lg
MY c dng phng trnh Nerst
2

Ta thy E chi thi ph thuc vo [M] v [MY]

Dng th thu c khi chun :

Ta xt mt v d khc : Ag+ + 2CN- = Ag(CN)2Hng s khng bn ca phc: Kkb

[ Ag ][CN ]2.
10 21
2
[ Ag (CN ) ]

Ta dng cng thc ny tnh nng ca bc v th ca cc bc trong qu

trnh chun . Gi s thm 0,5ml dung dch AgNO 3 1N vo 100ml dung dch
KCN 0,1N. y vic to phc, nng ion CN - gim ti khi [CN-] = 0,09N cn
nng ion phc mi to thnh s bng [Ag(CN)-2] = 0,005N . T y ta c :
[Ag+]= 10-21 .

0,005
6,2.10 22
2
(0.09)

Echi thi = 0,8 + 0,058lg 6,2.10 22 0,433v

Khi thm 2,5ml Ag+
Ta c : [Ag+]= 10-21 .

0,025
.10 20
2
(0.05)

Echi thi = 0,8 + 0,058lg .10 20 0,360v

Khi thm 4,5ml Ag+
113

Ta c : [Ag+]= 10-21 .

0,045
4,46.10 19
2
(0.01)

Echi thi = 0,8 + 0,058lg 4,46.10 19 0,265v

Khi thm 4,95ml Ag+
Ta c : [Ag+]= 10-21 .

17
0,0495
.4,9610
(0.001)2

Echi thi = 0,8 + 0,058lg 4,96.10 17 0,145v

Ti im tng ng nng ion bc c tnh nh sau :
T phng trnh to phc trn ta thy ti im tng ng nng Ag + v
CN- c mi quan h l : 2[Ag+]= [CN-]
Thay vo Kkb ta c Kkb
[ Ag ] 3

[ Ag ](2[ Ag ])2.
10 21
(0,05)

10 21.0,05
2,32.10 8iong / l
4

Th tng ng :
Echi thi = 0,08 + 0,058lg2,32.10-8 = 0,415V
Nu tip tc thm Ag+ th lc ny c phn ng to kt ta :
Ag(CN)-2 + Ag+ = 2AgCN
Lc ny th ca dung dch khng i cho n khi kt ca to thnh ht c
ngha l kt ta AgCN l hon ton. Nu tip tc thm Ag + th th tip tc tng do
nng ion Ag+ t do trong dung dch tng
Echi thi = 0,8 + 0,058lg [ Ag ]
C th m t th chun nh sau :

114

im
tng

4.2.3.Phng php oxy ha kh

Xt qu trnh chun 50ml Fe3+ 0,1N bng dung dch Sn2+ 0,1N ta c
phng trnh chun nh sau :
2Fe3+ + Sn2+

Fe2+ + Sn4+

ddSn4+

DD Fe3+
Th tiu chun ca cc in cc nh sau :
E0Fe3+/Fe2+ = 0,77v , E0Sn4+/Sn2+ = 0,15v
Nu nhng mt in cc Pt vo dung dch v tin hnh kho st s bin thin
th trong dung dch. Ta thy th bin thin ca dung dch c th tnh :
+ Khi qu trnh chun c mt na c ngha l thm c 25ml Sn 2+ lc
ny nng Fe3+ cn li l 0,05N v nng Fe2+ cng to c l 0,05N
E = 0,77 + 0,058lg

[0,05]
[ Fe3]
= 0,77 + 0,058lg
2

[0,05]
[ Fe ]

E = 0,77V

115

+Khi chun c 90% tc l tng ng vi 45ml Sn 2+. Lc ny nng

Fe3+ cn li l 10% tng ng vi 0,01N. Nng Fe2+ to thnh l 0,09N
E = 0,77 + 0,058lg

[0,01]
= 0,715v
[0,09]

+Khi chun c 99% tc l tng ng vi 49,5ml Sn 2+. Lc ny nng

Fe3+ cn li l 1% tng ng vi 0,001N. Nng Fe2+ to thnh l 0,099N
E = 0,77 + 0,058lg

[0,001]
= 0,654v
[0,099]

Ti im tng ng th c tnh nh sau :

Etd

E 0 Fe 2 E 0sn 0,77 2.0,15

0,35v
2 1
3

Sau im tng ng nu tip tc thm Sn 2+ th th dung dch lc ny ph

thuc vo nng Sn4+ v nng Sn2+ cn nng Fe3+ v Fe2+ khng thay i.
Nng Sn4+ lc ny l 0,05N
Khi thm d 0,1ml Sn2+ 0,1N th nng [Sn2+] = 10-4 ( 0,1.
E = 0,15 +

0.1
0,0001 )
100

[0,05]
0,059 [ Sn4]
0,059
lg 2 = 0,15+
lg
=0,24v
[0,0001]
2
[ Sn ]
2

Tng t khi d 1ml Sn2+ 0,1N th nng [Sn2+] = 10-3

E = ,15+

0,059 [0,05]
lg
= 0,21v
[0,001]
2

Nu tnh bc nhy th bt u t thi im thiu 1% v d 1% so vi qu

trnh chun ta c : bc nhy th = 0,654 0,21= 0,444v
4.2.4. Phnng php trung ha
Phn ng xy ra trong qu trnh chun ny l phn ng gia axit v baz.
y trong qu trnh chun [H+] s bin thin v thc cht ca qu trnh chun
l :

H + + OH- = H2O
Nn in cc dng o th qu trnh phi lin quan ti nng [H +] v d nh

in cc Hydro, in cc thu tinh, in cc quihyron.

116

ng cong chun trong chun trung ha c tnh i xng qua im

tng ng v bc nhy th ph thuc vo :
+ Hng s phn ly ca axit, hng s phn ly ca axit cng ln th bc nhy
cng di.
+ Nng axit, baz tham gia vo qu trnh chun cng ln th bc nhy
cng di.
4.2.5.Chun hn hp ion
y l phng php rt hu dng , c th ng thi xc nh cc ion khc
nhau trong cng mt dung dch do kh nng to phc bn ca chng vi thuc th
l khc nhau , do tch s tan ca chng vi kt ta l khc nhau hay do th oxy ha
kh ca chng khc nhau. Nn khi phn ng vi thuc th phn ng xy ra c tnh
cht tun t cho tng ion. V vy m ta c th nh lng tng ion mt trong hn
hp nhiu ion.
V d trong dung dch c ng thi 2 ion Cl- v I- th ta c th xc nh ng
thi c hai ion m khng cn tch chng ra, bng cch cho tc dng vi
thuc th Ag+ . V TAgI = 10-16 < TAgCl = 10-10 nn phn ng xy ra tun t nh
sau:
Ag+ + I- = AgI
Sau o:

Ag+ + Cl- = AgCl

Khi AgCl bt u kt ta cng vi AgI th [Ag+] trong dung dch l :

[Ag+]= 10-16/[I-] = 10-10/[Cl-] suy ra : [I-]/[Cl-]= 10-6. Chng t khi bt u qu
trnh chun Cl- th I- chun hon ton.
I.

Cc yu cu i vi cc phn ng trong chun in th

1.Cc phn ng ion phi xy ra nhanh. Khi tc phn ng chm cn

phi c bin php thc y phn ng nh : dng xc tc, tng nhit .
2.Cc phn ng cn xy ra mt cch hp thc. Trong trng hp cc cht c
thnh phn phc tp v khng xc nh th khng dng phn ng hay phi thay
i iu kin c thnh phn xc nh.

117

3.Phn ng cn phi xy ra theo mt chiu xc nh. Trong qu trnh oxy ha

kh thng c cc phn ng ph xy ra nn ta thng tin hnh chun trong
nhng iu kin khng c cc phn ng ph .
4.Phn ng cn phi xy ra nhanh , xy ra hon ton . cho phn ng xy
ra hon ton th phi chn kt ta c T l nh nht, hng s bn ca phc l cao
nht hay hiu th oxy ha kh chun ca cc cht l ln nht.
5.i vi phn ng chun cn phi chn c in cc ch th c trng.
y l iu kin phn no hn ch phm vi ng dng ca phng php v khng
phi phn ng no cng tm c cc ch th .
4.3. Cc phng php o th ca dung dch
4.3.1.Phng php chun ti im khng
Phng php chun ti im 0 l phng php ph bin nht trong cc
phng php chun khng b chnh. Bn cht ca phng php l khi thm t
t dung dch chun vo v khuy u c th nhn thy rng cng gn im tng
ng lch ca kim in k cng gim dn v cui cng khi d mt got dung
dch chun kim in k lch theo hng ngc li.

1. in tr, 2. Cng tc, 3. Ac quy, 4. in k, 5. in cc calomen, 6. Bnh

chun , 7. in cc Pt
118

u im ca phng php ny l cc thit b n gin v vic tin hnh

nhanh. Thiu st ca phng php l th ca cc ch th v qu trnh bin thin th
ph thuc vo cc cht in ly l c trong dung dch.
4.3.2.Phng php chun vi hai cc kim loi
Phng php chun vi hai cc kim loi da trn tnh tr ca cc lm
bng cc kim loi tr nh Pt. Pd, W i vi s thay i thnh phn im
tng ng. Nhng cc ny c th xem nh nhng in cc so snh .

1. Bnh chun , 2. in k, 3. Ac quy, 4. Cng tc, 5. in tr, 6. in

cc Wonfram, . 7. Cnh khuy, 8. in cc Platin
Khi chun theo s trn vic thm mt git thuc th cui cng
im tng nggay ra s sai lch bt thng ca kim in k. Phng
php chun vi hai in cu75ckim loi tin dng cho tt c cc loi
chun in th. Phng php ny cho php tin hnh phn tch nhanh,

119

thit b chun n gin. Nhc im ca phng php l khng c

du hiu chng t sp ti im tng ng.

120

CHNG V:
C S CHUNG V PHNG PHP SC K
Phng php sc k xut hin t nm 1903 do mt chuyn gia thc vt
Lin x Tswett khi nghin cu v sc t thc vt. ng l ngi u tin tch c
cc sc t trong l cy. Mu c trch bng ete, cho dung dch qua ct cha cht
hp th CaCO3, xut hin trn ct nhiu vng c mu khc nhau. Do , phng
php c tn l sc k xut pht t HyLp: mu sc v hi.

S tch bng phng php sc k c da trn s phn b khc nhau ca

cc cht khc nhau vo hai pha lun tip xc nhng khng ha tan vo nhau:
mt pha tnh v mt pha ng
Qu trnh tch sc k thng bao gm 3 giai on chnh:
- a hn hp ln pha tnh: ty theo nhng k thut sc k khc nhau m
qu trnh gi mu ln pha tnh khc nhau. Trong sc k bng mng ngi ta a
mu bng cch chm ln mt im trn vch xut pht. Trong sc k ct ngi ta
dng nhng Syringe tim mu trong sc kh hay lng hoc n gin chuyn
mu vo ct qua phu.

121

- Cho pha ng chy qua pha tnh: Sau khi chuyn mu ln pha tnh, qu
trnh tip theo l phn tch cc cht ra khi nhau trong mu ban u. Tin trnh
c thc hin bng tc ng ca pha ng, pha ng di chuyn qua b mt pha
tnh em theo cc cu t trong mu. Cc cu t khc nhau s tng tc vi pha
tnh nhng cng lc tng tc khc nhau. Chnh v vy khi i qua ht b mt pha
tnh chng mt nhng khong thi gian khc nhau, ngha l chng tch ra khi
nhau.
- Pht hin cc cht: Cc cu t c th pht hin d dng bng nhng tng tc
ha hc hay vy l. Ngi ta c th dng nhng thuc th ha hc to nhng
phn ng t trng nhn bit cc cu t. C th qu trnh nhn bit c tin
hnh thng qua nhng tng tc vt l nh : o h hp th trong vng UV-Vis, o
ph pht x nguyn t, o ph pht x hunh quang hay o o ph khi lng
v.v... nhng thit b ngi ta gi l nhng Detector.
T khi ra i (nm1906) cho n nay, sc k khng ngng pht trin tr
thnh mt k thut phn tch c ng dng rng ri. Sc k c nhiu loi ty thuc
vo cch phn loi:
+ Theo bn cht sc k cc pha
- Sc k lng lng (Liquid- Liquid Chromatography: LLC) : SC K
LNG (LC)
- Sc k lng rn (Liquid- Solid Chromatography: LSL) :

- nt-

- Sc k kh lng (Gas- Liquid Chromatography: GLC) :

SC K KH

(GC)
- Sc k kh rn (Gas- Solid Chromatography: GSC) :

- nt-

+ Theo bn cht hin tng sc k

- Sc k hp ph : Pha tnh l cht rn c kh nng hp ph (LSC; GSC)
- Sc k phn b : Pha tnh l cht lng c ph ln mt gi mang rn v
tr(LLS;GLC)
- Sc k trao i Ion : Pha tnh l cht nha trao i Ion

122

- Sc k phn loi theo kch c : Pha tnh l mt loi Gel sng lc phn t
theo kch c
+ Theo k thut v phng tin sc k
- Theo phng tin gi pha tnh: Sc k ct; Sc k lp mng; Sc k giy
- Theo cch cho pha ng chy: Sc k khai trin; Sc k ra gii
Qu trnh sc k l qu trnh trong cc thnh phn trong hn hp cht
cn xc nh tch ra khi nhau. Phng php sc k thc s tr thnh mt phng
php phn tch trong vic nh tnh v nh lng cc hp cht trong mu trng
thi lng hoc kh. Nguyn tc ca phng php da trn qu trnh cn bng nng
ca cc cu t trong mu khi chng tng tc gia hai pha. Mt pha c gi
l pha tnh v n khng chuyn ng trong ct. Mt pha khc c gi l pha ng
v n chuyn ng xuyn qua h thng. S phn b khc nhau ca cc cu t khi
i qua ct dn ti s tch cc cu t trong ct .
5.1. C s chung ca phng php sc k
Qu trnh sc k l mt qu trnh ha l trong c s phn tch ging nh
qu trnh chng ct, kt tinh hay trch ly. Phng php c xem l mt phng
php tch cc cu t trong mu hin i nht t trc ti nay m Tswett ngi
c xem nh l cha ca phng php sc k. Chun b cho qu trnh sc k
gm rt nhiu khu, mc ch nhm tch v lm tinh kit cc thnh phn trong
mu nh mu chun dng cho k thut phn tch. Cho n by gi sc k c th
tch cc thnh phn rt nh phc v trong lnh vc sinh hc.
Qu trnh sc k c th c m t nh sau:
+ Mt dng c hnh ng c lm y bn trong bi nhng ht rt mn, rn
c gi l pha tnh (stationary phase) thng gi l ct sc k
+ Trn cng ca ct ny c cho vo mt th tch nh ca cc cu trong
mu cn tch ra khi nhau
+ Mu c di chuyn lin tc i vo ct bng dng pha ng v xuyn qua
ct. S tng tc ca cc cu t xy ra trong ct, cng lc tng tc ph thuc

123

vo bn cht ca cc cu t v c cng vi dng pha ng. Qu trnh ny gi l s

ra gii

Phng php sc k t ti nh cao l vo nm 1940 khi m con ngi c

th lm ra nhng ct. Nhng ct ny c th xc nh thi gian lu tr ca cc cu
t khi i qua ct ny m khng cn thu gi chng. Cui cng l nhng thit b c
c gi l detector c th nhn bit v nh lng nhng cu t khi i ra khi ct
vi nhng thnh phn rt nh (vi nanogam). Tn hiu ca detector cho mt cu t
no khi ra khi ct, c ghi nhn bng mt mi, xc nh mt v tr trong
sc k .
Khi ct dng l ph hp vi qu trnh chy sc k, sc k thu c l rt
p v nhng thng s cho qu trnh tch ng tin cy. V vy c mt kt qu
tt ngi ta phi chun b cho qu trnh vi thi gian di c th vi gi m khng
th mt vi giy .

124

5.1.1. Phn loi cc k thut sc k

K thut sc k kh c th phn thnh ba loi: th nht da trn trng thi
vt l ca cc pha, th hai l da trn qu trnh s dng, th ba da trn hin
tng ha l m c s ca n l h s phn b Nerst, c xc nh :

T s nng cht tan trong pha tnh so vi nng cht tan trong pha
ng
H s K ph thuc vo trng thi vt l ca cc pha v d gi tr K s rt ln
khi pha ng l kh v pha tnh l lng
5.1.2. Sc k lng - rn ( LSC)
y l loi sc k c t u tin. Pha ng l lng v pha tnh l rn. Loi
sc k ny c p dng rng ri v s phn chia cc cu t ra khi nhau l da
trn tnh lu gi.

125

Hnh trn l nhng loi pha tnh c trng thi l rn, lng v bn cht ca
chng c th khc. S khc nhau v bn cht v trng thi ca hai pha dn n cc
loi sc k khc nhau.
Sc k hp ph :K thut sc k ny c xem l tt nht trong cc k
thut p dng vo cui th k th 20 trong cc phng php tch. Pha tnh c
thit k rt nhiu tin b ng k so vi thi ca nh bc hc Tswett, ngi s
dng pha tnh l CaCO3 v ng .Qu trnh tch cc hp cht hu c trn nhng
tm mng SiO2 v Al2O3 khi cho dng dung mi ng vai tr l pha ng i qua
c xem nh l c trng cho sc k loi ny. Cht tan lin kt vi pha tnh bng
nhng lin kt hp ph vt l hay ha hc. Thng s ha l gm c h s hp ph.
Sc k ion : Pha ng trong k thut sc k ny l mt dung dch m v
pha tnh cha nhng ht hnh cu ca th polyme c ng knh rt nh ( m). B
mt ca nhng ht c ci tin v mt ha hc trn c gn nhng ion hay
nhng nhm mang in. Nhng ht ny cho php trao i nhng ion trong pha
ng vi ion tng t hin din trong mu. Qu trnh tch ny da trn h s phn
b ion.
Sc k ray phn t : Pha tnh trong sc k ray phn t c lm bng mt
vt liu cha nhng l. Kch thc ca nhng l l quyt nh n vic tch cc
cht tan trong mu da trn kch thc phn t ca chng. iu ny c th c
hiu nh mt ci ry cho php chn la c i qua c hay khng. K thut ny

126

c xem nh l lc gel hay thm gel ty thuc vo trng thi ca pha ng , n l

nc hay l dung mi hu c. H s phn b trong k thut tch ny c gi l
h s khuych tn.
5.1.3. Sc k lng lng ( LLC)
Trong k thut sc k ny pha tnh l pha lng khng di chuyn nm trn
ct. Theo pha tnh c thit k bng cch c bm ln mt cht mang tr v
mt ha hc.Trong k thut sc k ny rt d xy ra hin tng gi l chy mu
ct do khi pha ng i qua ct c th cun theo c pha tnh lng ra khi ct. Tuy
vy k thut sc k vn cn c s dng khi pha tnh l kh .
Pha tnh lng trong trng hp ny lin kt vi lp m bng nhng lin
kt cng ha tr. Qu trnh tch da trn s phn b trn b mt hai pha. H s cho
qu trnh ny gi l h s phn b ( Trong lnh vc c kh ngi ta gi qu trnh
ny l qu trnh trch ly lng lng)
5.1.4. Sc k kh lng ( GLC)
K thut ny, thng c gi l sc k kh, pha ng l kh v pha tnh l
lng. Pha tnh c to bng cch cho thm t hay to c nhng lin kt vi
cht mang nh trong trng hp ct mao qun ( capillary column) cht mang tr
s c bm ln b mt trong ca ct. i vi k thut ny h s phn b l h s
qu trnh
Nm 1941 hai nh nghin cu Martin v Synge xut thay pha lng
bng pha kh trong qu trnh tch. y chnh l thi im m k thut sc k tht
s pht trin mnh m.
5.1.5. Sc k kh - rn ( GSC)
Trong k thut sc k ny , pha tnh l nhng cht rn xp ( nh than hot
tnh , silicagel) v pha ng l kh . y l loi sc k kh in hnh rt thng gp
trong phn tch hn hp kh v nhng thnh phn c im si thp.
5.1.6. Sc k dng lng siu hng ( SFC)

127

Trong k thut ny, pha ng l dng lng trng thi siu chy nh CO 2
500C, 150 bars. Pha tnh c th l lng hay rn. y l k thut sc k c xem
nh l hin i nht nhng cn thit phi c nhng thit b ti tn p ng.
5.2.

Sc k
Qu trnh phn tch sc k da trn sc k . Sc k l th m t hai

thng s thi gian v nng cht tan khi ra khi ct ti thi im tc th.Trong
thi gian biu th trc honh cn tn hiu detector biu th trc tung.Qu
trnh tch xy ra trn ct dn n mt dy pick xut hin mc ln t ng nn.
chnh l du hiu thu c t mu hin din. Nu cng tn hiu detector
thu c l t l tuyn tnh vi nng cht c trong mu th din tch peak thu
c trn sc k l tng ng vi nng cu t trong mu.
Cc thnh phn l c m t bi thi gian lu ca n t R, c xc nh
khong thi gian t khi tim mu vo h thng sc k n lc xut hin tn hiu
cc i trn sc k . Trong mi trng hp th thi gian lu c lp vi lng
tim vo. Thi gian m pha ng i ct (khng c s tng tc vi ct) gi l t M,
gi l thi gian cht.
Qu trnh tch c xem nh l hon tt khi s peak xut hin trn ng
nn l ng vi s thnh phn cc cu t trong mu . Trong phn tch nh lng,
chng ta ch quan tm tch cc thnh phn cn thit o thnh phn ca chng.

128

Hnh a: m t thi gian lu ca pick, hnh b: trng thi ca peak, hnh c: m t mt

peak chun theo Gausisan
Xc nh mt thnh phn no m ch da vo thi gian lu l khng
chc chn. Tt nht l phi thc hin song song trn hai phng php l sc k
cng vi phng php khi ph hay ph hng ngoi xc nh. Nhng cp
phng php ny thng c gi l phng php ni kt, n cho php chng ta
c c nhng thng tin t nhng ngun khc nhau, c lp vi nhau , c nh vy
th kt lun ca chng ta mi chnh xc.
Phng php sc k c th xc nh nhng thnh phn tn ti trong cc hp
cht m nng ca chng rt nh vi nanogam hay nh hn.
5.3.

Tiu chun ca sc k v peak Gausisan

Nhng im c trng ca sc k l tng l nhng h s lin quan ti

sai s ngu nhin trong phng trnh Gaussian:

129

Trong l thi gian lu ca pick cc cu t

l lch chun ca pick
2 l h s bnh phng lch
Y tiu biu cho tn hiu nhn c t detector ti im cui ca ct
X l khong cch t chiu cao ca pick n hai cch bn ca pick
Trong k thut sc k thng ngi ta xc nh y theo cng thc:

Gi tr ny t cc i l 0,399 khi x = 0 . Gi tr ny cng c hai im

un ti x = 1 lcx t gi tr y = 0,242 t 60,6 % so vi gi tr cc i .
rng ca pick ti im un l 2 ( =1). Trong sc k hin i ,
rng ca pick ti v tr chiu cao pick t 1/2

biu th cho

. Chiu rng ca pick

ti ng nn c o bng 13,5% chiu cao pick. Ti im ny th theo phng

trnh Gaussian W c xc nh
5.4.

Peak thc
Sc k thc thu c ca cc peak thng c nhng sai lch so vi so

vi peak ca Gaussian a ra. C rt nhiu l do dn ti iu ny. Bn cnh s

chp nhn tng i nh s bin i khng u trong phn b v nng , c
nhng sai lch nng khi tim vo nhng thi im khc nhau ti u ct.
Thm vo l tc ca dng pha ng bng khng ti st vch ct v t
maxium ti v tr gia ct. Cc peak nhn c trong sc k thng c hnh
dng khng cn i, h s nghin F tnh cho s sai lch ny l 10% so vi chiu
cao ca peak.

130

Trng hp a: peak to ra c nghin Ft =1, peak cn i

Trng hp b: peak to ra c nghin Ft < 1, peak nghin pha trc
Trng hp c: peak to ra c nghin Ft >1, peak nghin pha sau
5.5.

Thuyt a ng lng
C nhiu thuyt gii thch v qu trnh di chuyn v phn tch cc cht tan

khi i qua ct. Trong thuyt hin i nht l thuyt a l thuyt v quan im
ca thuyt ny c nhiu ngi ng tnh nht, cho n by gi thuyt a l
thuyt cng c coi l hp l nht.
Theo quan im ca thuyt ny th cc phn t cht tan di chuyn tnh tin
dc theo ct theo mt chui ring bit, v th qu trnh sc k l mt qu trnh
131

ng v xy ra lin tc. Chui cht tan ny c m t nh s di chuyn ca dng

xuyn qua ct trong c s phn hng cc cht tan. Nhng cht tan c i lc
tng tc vi ct mnh v tr sau cn cc cht tan c i lc tng tc vi ct t
th v tr trc. S phn b ny xy ra trn mt v tr no b mt ct to ra
mt cn bng ca cc cht tan phn b gia hai pha tnh v ng, lc ta gi
l mt a l thuyt. Cn bng ny nhanh chng b pha v do dng pha ng di
chuyn v s tng tc mi li xy ra gia cc cu t cht tan vi b mt hai pha
tnh ng dn ti mt cn bng mi c thit lp, ta c a l thuyt mi. Qu
trnh sc k xy ra lin tc nh vy vi v s cn bng c thit lp trn v s
a l thuyt cui cng cc cu t cht tan tch ra khi nhau trc khi ra khi b
mt ct.
Trong sc k lng - rn th s tng tc l qu trnh hp ph (adsorption)
cc cu t cht tan b hp ph ln b mt ct, pha ng gii hp ph bc cc cu t
ra khi b mt ct. Cc cu t c tng tc mnh ngha l b hp ph mnh, s kh
b gii hp ph nn theo qu trnh chng s v tr sau trong s phn tch. Cc cu
t c tng tc yu s c v tr trc trong s phn tch .
Tng thi gian di chuyn tR ca cc cu t c th chia lm hai phn : th
nht l tM biu th cho thi gian di chuyn pha ng qua ct phn tch ( cn gi l
thi gian cht), n ph thuc vo tc ca pha ng , th hai l t S biu th thi
gian cc cu t cht tan tri qua b mt pha ng (gi l thi gian thc).
Chiu cao ca mt a l thuyt c xem nh l khong cch m cc phn
t cht tan ri b cn bng ny cho n khi t c mt cn bng mi.
Nhng cn bng lin tip ny l c s ca vic tnh s a l thuyt trong
ct sc k. Nu gi chiu di ca ct l L, s a l thuyt l N. Ta c chiu cao
ca mi a l thuyt l:

132

Gi s ti thi im th I , a th J cha tng khi lng cht cn phn

tch l mT. Tng khi lng ny l t hp ca m M l lng cht chuyn t a ( J1 ) ca pha ng trong cn bng t ti thi im (I -1), v m S l lng cht thc
s c sn trong pha tnh a J ti thi im ( I -1)

Nhc im ca thuyt a l thuyt ny l thuyt cha n cp n s

khuych tn ca cc hp cht trong qu trnh phn tch xy ta trong ct.

Sc k nhn c t s phn tch hao cu t A v B trn ct gm 30 a

l thuyt

cho thy v tr ca cc

cu t khi i ra khi ct
5.6.

Hiu qu ct

133

Hiu qu tch l thc o rng ca cc nt cht phn tch khi n

chuyn dch dc theo chiu di ct. Hiu qu ct c nh ngha l bnh t s
gia thi gian lu tuyt i v lch chun ca pick sc k . Gi s pick cn i
th hiu qu ca ct l s a l thuyt n, c th tnh bng phng trnh
t 2
n ( r)

lch chun ca pic c th c xc nh t rng ca pic nh hnh v:

Nh vy hiu qu tch ca ct c th c biu din thng qua rng pick
o na chiu cao pick (Wh =2 ) hoc rng pick o chn ng nn (W b= 4
) theo phng trnh :
t
2
n 16( r )
Wb

V rng pick thng c o na chiu cao ca pick nn phng trnh

thng c dng xc nh hiu qu ct l phng trnh
t 2
n ( r)

Hiu qu tch ca ct cng c th c tnh cho mt n v chiu di ca

ct, tc l s a l thuyt trn mt chiu di .
Hiu qu tch ca ct cng c th din t qua chiu cao ca a l thuyt h
hay HETP. y l s o chiu di ca ct, n v l milimet, b chim bi 1 a l
thuyt v n t l nghch vi s a l thuyt ca ct N
h

134

L
N

N ' 5,545(

t/r 2
)
Wh

S a l thuyt hiu dng v s a l thuyt lin h nhau qua t s phn b k

N' N (

k 2
)
1 k

Nhng ct c kh nng phn b ln th N N v chiu cao ca a l

thuyt hiu dng H t l nghch vi N
H

5.7.

L
N'

Nhng thng s lin quan:

Trong qu trnh sc k thng c ba thng s cn cp th tch
1.Th tch ca pha ng trong ct( th tch cht)
Th tch ca pha ng trong ct VM tng ng vi th tch ca khe h m

pha ng i qua. i lng ny c tnh t gi tr tc F ca pha ng v thi

gian lu tM ca pha ng:

2. Th tch ca pha tnh

y l th tch c thit k v n khng c mt trn sc k , c k
hiu l VS . i lng ny c th xc nh bng cch ly tng th tch bn trong
ca ct tr i th tch ca pha ng trong ct.
3. Th tch phn gii VR
Th tch phn gii VR ca mi mt cu t trong mu phn tch biu th cho
th tch pha ng cn thit di chuyn chng xuyn qua ct. Trn sc k th
tch phn gii ph thuc vo thi gian lu tR ca cc cu t trong. Nu tc dng
l hng s th :

135

Dng c tim v detector cng tn ti mt th tch cht , v lng ny nh

hng n tng th tch phn gii. Trong sc k kh do dng kh c th b nn ,
nn gi tr dng o c cui ct cn phi c lm chnh xc bi h s nn. H
s ny mun tnh phi so vi p sut u ct.
4. H s phn b K
Khi mt hp cht c tim trn ct , th tng khi lng m T ca n c
phn vo hai i lng : m M l khi lng ca hp cht phn tn trong pha ng
v mS l khi lng ca hp cht phn tn trong pha tnh. T s khi lng ca
hp cht phn b gia hai pha tnh v ng l hng s k

H s k khng ph thuc vo t l dng v chiu di ca ct, c gi tr khc

nhau trong nhng iu kin khc nhau. H s k l mt h s quan trong trong qu
trnh chy sc k v ph thuc vo cu trc ca ct.Gi tr k khng c qu ln
v nh vy th thi gian phn tch s lu.
Xc nh h s phn b k
Khi pha ng di chuyn c nh hng dc theo ct v pha cui ct n
em theo khi lng cht cn phn tch . Trong qu trnh cht cn phn tch s
phn b gia hai pha tnh v ng .H s phn b k c tnh thng qua th tch
phn b VR v th tch cht VM:

Hay:
M :

VR VM

tR
tM

Suy ra :
Vy :

t tM
t'
k R
R
tM
tM

Th tch phn b VR ca mi mt cu t trong mu phn tch l lin quan

ti h s phn b cu t gia hai pha K. Phng trnh c th vit li nh sau :
136

Hay:
5. chn lc
chn lc c lin quan ti tc ng ha l qua li gia cc cht phn tch
v h thng sc k. Trong sc k kh, chn lc c xc nh bi tnh cht t
nhin vn c ca pha tnh. Cc dng pha tnh c s dng trong sc k kh c
tng kt trong cc ti liu. chn lc ca pha tnh thng c biu hin qua gi
tr lu gi tng i ca cp ti hn trong mu.

t /R 2
/
tR
1

y l h s chn lc
t /R 2

t /R1

Hay :
k2 v k1 l h s phn b ca cu t f v i trong ct

Gi tr ln hn 1 th cp ti hn mi c th tch ra khi nhau.

Cc tc ng qua li gia cht phn tch v pha tnh c th bao gm t hp
cc tc ng qua li ca cc nhm phn cc c bit v khng phn cc, chng

137

hn tc ng qua li ca cc lng cc v lin kt hydro. Cc thut ng phn cc

v khng phn cc thng c s dng din t chn lc ca pha tnh .
Tuy nhin s dng ng ngha phn cc vi chn lc l khng ng .
phn cc n thun ch l mt kha cch ca chn lc gy ra tc ng qua li
gia pha tnh vi cc na phn cc ca cht phn tch . chn lc c s dng
din t kt qu ca cc nh hng phc tp qua li ln nhau do cc tc ng
gia cht phn tch v pha tnh .
6. H s phn gii R
Bc ti hn ca phng php sc k kh l h s phn gii cn thit t
c hiu qu tch mong mun. H s phn gii sc k R c tnh theo cng
thc:

(t t )
R 2. RJ Ri
(Wbi Wbj )

Trong tRj v tRi l thi gian lu ca cu t j v i

Wb l rng ca pick trn ng nn.
Kh nng tch ca ct h sc k i vi mt cp ti hn khng ch ph
thuc vo thi gian tuyt i ca chng , m cn ph thuc vo sc nt ca cc
pick sc k tng ng ( l hiu qu tch ca ct)
H s phn gii gm t hp cc thng s sc k nh hng nhau, bao gm:
hiu qu, chn lc v kh nng phn b k theo phng trnh:
R

n 1
k
.(
).(
)
4
k 1

Trong : n l hiu qu tch ca ct

l chn lc
k l t s phn b ca cht phn tch
th m t s ph thuc h s R vo chiu di ca ct ( ph thuc vo n ct
cng di th s a l thuyt cng ln )

138

Trong trng hp ct sc k hiu qu thp , th chn lc l u t ng

gp c ngha vo h s phn gii, do vy trong ct sc k ct nhi cn s dng
nhiu pha tnh khc nhau, trong khi vi ct sc k mao qun hiu qu cao ct
ng h ch cn dng 1 s pha tnh thch hp cng c th t c phn gii cao
i vi mt hn hp phc tp.
7. Phng trnh Vandeemter trong sc k kh
Khi chng ta cp nhng nh hng ca cc thng s n qu trnh tch,
chng ta cha cp n tc pha ng trong ct.Thc ra tc ca pha ng
c nh hng n qu trnh phn tch cc cu t trong mu trong qu trnh sc k.
V d khi dng pha ng c tc ln th kh nng ra gii ca cc cu t d hn
v n nh hng trc tip n kt qu phn tch .Phng trnh Van Deemter a
ra nhm cp ti vn ny, u tin th phng trnh ny s dng trong sc k
kh, sau c m rng cho sc k lng.Phng trnh Van Deemter m t mi
quan h gia chiu cao H v tc thng ca dng pha ng trong ct

. Phng

trnh nh sau :

C ba thng s A, B,C l lin qua ti kh nng tch ca ct v iu kin th

nghim Nu H c tnh l cm, B l cm2/s v C l s ( y tc c o l
cm/s). th m t phng trnh trn l mt hyperbol v t cc tiu Hmin khi :

139

Trong :
A l h s khuych tn xoy din t cc ng i khc nhau ca dng kh
mang do khuych tn xoy trong ct gy ra .
B l h s khuych tn dc .
C l h s tr khng chuyn khi .
i vi cc ct ng h c cha cht nhi, th h s A khng c mt trong
trong phng trnh, nh vy phn cn li ca phng trnh VanDemter ph hp
vi phng trnh Golay:

_
B
h Cu
u
Trong thc t ngi ta xc nh cc gi tr A,B,C bng cch thay i t l
dng pha ng khc nhau trn mt mu nht nh. T ngi ta thu c nhng
dng ng hyperbol tng ng , ri dng phng php hi quy tnh A,B,C
Phng trnh :

c m rng nhng dng khc nhau trong sc k lng cho thy rng c
mt t l dng tt nht cho mi qu trnh tch. Gi tr ny ng vi im un trong
th ca phng trnh ( gi tr cc tiu ca th ) cn khi tc dng ln hn
hay nh hn gi tr ny u lm gim hiu qu tch .
140

8. Ti u ha trong qu trnh sc k
V phng php sc k vn c l phng php phn tch nh lng , n
da trn vic o chnh xc din tch peak. V th cc cht mun c xc nh
phi c tch tt. c c kt qu ny cn phi s dng cc thit b phn
mm iu kin sao cho cc thng s vt l ca qu trnh t kt qu tt nht. ng
thi chng ta phi hiu tt v bn cht ca qu trnh.
Trong sc k kh, qu trnh tch c th rt phc tp, v n rt kh a ra
gi tr cho mt thng s no .Liu nhit lm tng hay lm gim hiu qu ca
qu trnh, tt c cc cng vic nh : chn loi ct, chiu di ca ct, ng knh
ca n , chn pha tnh, t s pha .v.v.. tt c nhng ci ny u nh hng trc tip
n qu trnh tch. Cha k l cc thng s ny c nh hng ln nhau.
Trong qu trnh sc k, dung dch ra gii v thi gian ra gii l hai thng
s quan trng v gi tr ca chng ph thuc vo nhau. Mc ch l hng ti tch
cc thnh phn trong mu phn tch ra khi nhau trong thi gian ngn nht,
khng mt thi gian a thit b v trng thi ban u nhm thc hin qu trnh
phn tch tip theo. Nu dung mi ra gii l tt, th n s nh hng tt n thi
gian lu ca cc cu t. Lc chng ta c th s dng nhng ct ngn hn m
vn thc hin tt qu trnh tch .
Hnh di y cho chng ta thy c s nh hng ca thnh phn pha
ng trong sc k lng n kh nng tch cc thnh phn hydrocacbon trong mu
ban u. Sc k cng cho chng ta thy khi thay i thnh phn pha ng th
chu k thi chy mu cng thay i.

141

Qu trnh tch sc k : pha ng c thay i theo nhng t l khc nhau

gia hai thnh phn : ncv acetonitril a.50/50 b. 55/45 c. 60/40 d. 65/35
Trong sc k lun c s tn ti ph thuc gia ba thng s c c trng
bi hnh tam gic l: dung dch ra gii, tc pha ng v dung lng ct. Ba
thng s ny l mu thun ln nhau. Thng thng trong qu trnh sc k ngi ta
lu ti tnh cht chn lc ca dung dch ra gii. V vy m trong s ph thuc
ln nhau theo hnh tam gic th hai yu t dung lng ct v tc ca pha ng t
xt n coi nh l hng s kho st tnh ra gii ca pha ng.

142

S ph thuc tam giac ca ba thng s trong sc k.Vng ti v tr cao hn

trong biu , m t tng ng vi qu trnh phn tch sc k . Nn tng ca
chng da trn 5 thng s K,k,N,R v .

143

CHNG VI:
PHNG PHP SC K KH
Sc k kh (GC) l mt k thut c s dng rng ri. N c p dng
sau nm 1940 khi tin hnh phn tch nhng thnh phn nh trong du m.GC
c p dng rng ri do s pht trin ca cc kha cnh nh nhy, p dng
nhiu lnh vc khc nhau, s a dng ca pha tnh, v tc pht trin ca nhiu
k thut mi ra i.V qu trnh tch c xy ra trong pha kh nn mu dng
rn hay lng phi c ha hi. y chnh l im chnh ca k thut ny, nhng
hp cht c phn tch bng k thut GC phi chu nhit v d ha hi. Thng
thng pha tnh s dng trong sc k kh l lng, mt t l rn. K thut ny c
p dng trong nhiu lnh vc nh : du m, dc phm, mi trng, phn tch
kh .v.v
6.1. Cc b phn chnh trong my sc k kh
Sc k kh l c cu to bi nhiu b phn. Nhng b phn ny bao gm:
bung tim ,ct v detector. Pha ng di chuyn xuyn qua thit b phn tch l
dng kh v n c cha trong bnh kh. Dng kh c iu khin bi h thng
o p sut kh v c n nh cao.
Qu trnh phn tch bt u khi mt lng nh mu dng lng hay kh
c tim vo. C hai dng khi tim vo c ha hi v c trn u vi pha
ng. Sau mu c pha ng cun vo trong ct, ct l cun ng c ng
knh rt nh c chiu di t 1 ti hn 100m. Ct cha pha tnh c kh nng chu
c nhit b phn ha hi. cui ct, pha ng i xuyn qua detector trc
khi i ra khng kh. Vi loi sc k c ghi r khong p ng ca chng, theo
chng ch s dng trong khong no.

144

1. Bm kh .
2. ng h o p sut dng kh.
3. B lc kh .
4. Bung bm mu .
5. Bung iu nhit cha ct tch .
6. B phn Detector.
7. B phn khuch i .
8. B ghi .
9. Tch phn k c my tnh .
10. B phn ghi kt qu.

145

146

Trn y l mt loi biu sc k kh v hnh nh ca th h my sc k

Model 6890-GC c chng trnh iu kin dng kh. Thit b ny cho php qu
trnh tim mu t ng
6.2. B phn cha kh v iu chnh dng
Pha ng l kh ( c th l He, N2 hay Hydro). B phn cha kh khng
c cha nhng tp cht nh nc hay oxy bi v nhng thnh phn ny s
tng tc vi pha tnh hay tng tc vi mu dn ti pha tnh b h hay mu b
bin i. V vy c mt phn loi m v kh oxy trong pha ng trc khi pha
ng i vo h thng sc k.

Trong sc k kh, b phn cha kh khng lin quan ti s bin i ca h

s phn b K gia hai pha ng v tnh.Tuy vy m c ca n v tc dng
kh c nh hng ti s phn tch trong pha ng( iu ny c m t trong
phng trnh Van Deemter). V vy c nh hng ti hiu qu v nhy ca
Detector. p sut u ct c th t vi chc n vi trm n v atm, gi tr ny

147

c thit lp bi mt thit b o bng dng in m bo chnh xc tc dng

kh, ngha l tc dng kh l khng i trong ct. Khi chng trnh nhit l
c s dng th m c ca pha ng tng ln lm gy nn s bin i dng
kh. V vy m bo cho dng kh khng i trong sut qu trnh l mc tiu
trong k thut.

Biu m t vn tc khng i ti u v m c ca cc loi kh. Gi

tr ca cc vn tc ti u ca cc dng kh ph thuc vo ng knh ct. S dng
dng kh l hydro cho php tch nhanh hn s dng dng kh He . iu ny gii
thch ti sao chng trnh nhit c s dng. Hot ng ca cc detector l
ph thuc vo loi kh s dng .
Nu sc k ch cha mt peak ca mt cht no m cht ny khng
phi ca pha ng, th rt d tnh vn tc thng trung bnh

ca pha ng

trong ct. Chng ta cng d dng tnh c vn tc ca dng kh khi i ra khi

thit b p sut khng kh P0 bng cch t mt thit b o dng cui ct. T l
gia hai vn tc chnh l h s gim J, n lin quan ti s khc nhau gia trong v
ngoi ct( P/P0) vi P l p sut u ct.

6.3. Dng c tim vo v bung tim

148

6.3.1.Dng c tim
Vt tim vo thng dng dung dch khong 0,5 l c a vo h
thng sc k bng mt syringe nh. C nhiu loi syringe khc nhau do tnh a
dng ca dng c tim v ct.Vi nhng mu tim l kh, dng c tht vng (uc
xem nh bm nh lng) c th ci vo ging nh cch tim trn sc k lng.

K thut tim mu t ng ci thin ng k nhng sai st trong k thut

tim mu bng tay do lng mu tim c sai lch ng k trong mi ln tim. Cc
nh sn xut ci thin vn ny da trn t ng ha syringe hay bung tim
v dung lng mu. Nhng dng c ly mu t ng ny c th ly vi nhiu mu
khc nhau v rt chnh xc. B phn cha mu c hnh dng trn v cc mu c
xp trn theo mt th t nht nh m ngi thc hin ln chng trnh. Sau
chng c ly chnh xc bng b phn ly mu t ng theo chng trnh ci ri
tim vo h thng sc k.

y l loi syringe 10 l , s dng trong sc k kh. Loi ny c lp bo v

picton khi v. C vi loi syringe th tch c th t 0,1- 1l. u kim gn vo
picton phi tht ph hp mu i d dng v trnh th tch cht trong (lng
cht khng ra khi syringe c )
6.3.2. Bung tim
Bn cch vai tr ca n nh a mu vo ct th bung tim phi ha hi
v trn u mu vi kh mang trc khi mu i vo u ct. K thut tim mu l
149

nh hng rt ln n cht lng qu trnh tch. Phn loi k thut tim v t

trng ca bung tim ph thuc vo loi ct s dng trong qu trnh phn tch.
Bung tim gm: B phn tip nhn mi tim, thn bung, vng xoay
chuyn mu, b phn nhn mu, b phn tht ly phn dung tch mu xc nh
- K thut tim mu ha hi trc tip
K thut ny thng c ng dng cho ct nhi v nhng ht nhi c kch
thc khong 530m. Dng kh pha ng c t l 10ml/ pht, cun trc tip mu
a vo. Tt c nhng mu c tim theo k thut ny thng qu trnh ha hi
c thc hin trong ng kim loi, bn trong c lng ng thy tinh. ng thy tinh
lng vo thit b cun bi dng pha ng i qua v c gia nhit n nhit
ha hi ca cc cu t cn phn tch.

Mt im u ca bung tim c mt vch ngn, c lm bng silicon,

n cho php syring xuyn qua n vo bn trong. Mt im cui khc ca bung
tim c ni tip vi u ct. Ton b mu c tim vo ct trong vi giy.
K thut tim slipt/ sliptless: K thut ny thng dng khi s dng ct
mao qun vi t l dng nh, thm ch vi th tch tim rt nh cng c th tch
trn ct. Bung tim hot ng theo hai dng chia gi l slipt v sliptless tc l k
thut tm chia dng v k thut tim khng chia dng.

150

Trong k thut tim chia dng ( slipt), kh mang n trong th hi vi t l

dng tng i ln. Mt l van tch dng kh mang lm hai phn trong dng
nh i vo ct. C mt thit b phn tch iu chnh l van. Gi tr t l ca k
thut tim chia dng khong t 1:20 n 1: 500 th tch mu.

Hnh a : bung tim slipt/sliptless (ch tim slipt c iu chnh bi

van s 2). Van s1 gi l vch ngn lm sch
Hnh b: Tim trn ct lnh
Khi lm vic vi ct mao qun, k thut tim khng chia dng (sliptless)
c dng khi hm lng mu l nh. Vi k thut ny qu trnh tim thc hin
rt chm khong 2 giy, lc van s 2 v tr ng khong 0,5- 1 pht. Qu
trnh ha hi cc hp cht v dung mi ngay ti 10 cm u ct.. tin hnh k
thut ny n yu cu vi iu kin, i hi mt chng trnh nhit m bt u l
chy nhit thp. K thut ny dng khi cn xc nh hm lng thp. Van s

151

2 sau c m loi b nhng cht cn li, nhng cht ny c th nh hng

n qu trnh.
Trong phn tch nh lng, vic s dng k thut slipt v sliptless c th
dn ti sai s nng , bi v qu trnh phn tch cc cht trong ct lin quan ti
s ha hi ca chng nn thnh phn ca qu trnh phn tch khi i vo ct rt
khc so vi thnh phn mu ban u. Vn ny c th c gii quyt bng cch
s dng ngoi chun hoc c th gii quyt bng cch dng ng thy tinh ph hp
t bn trong bung tim
K thut tim trn ct lnh
Vi k thut ny mu c tim trc tip trn ct v ha hi sau khi tim.
K thut ny i hi mt microsyring c bit. Mi kim lm bng thp hay silicon
c ng knh khong 0,15mm i vo bn trong ct. Ct c gi 40 0C
trc khi thc hin quy trnh tin hnh phn tch. Vi k thut ny rt hu hiu i
mu c nhit phn hy thp hay c nhng cht bn nhit ( p dng trong mu
sinh hc). tin hnh k thut ny cn thit phi c chng trnh t ng ha.
K thut rt hu hiu khi mu c cha nhng thnh rt khc bit v nhit ha
hi.

152

K thut ha hi theo chng trnh nhit .

K thut ny tn gi l PTV ( Programmed temperature vaporizer), thit k tng
t nh bung tim slipt v sliptless. Nhit ca bung tim c th ci t hot
ng s bit thin nhit theo thi gian, S bin thin ny c th thay i nhit
t 20 n 3000C trong vi chc giy. V vy nhng u im ca k thut tim slipt
v sliptless u c th thc hin trn ct lnh trong bung tim ny.
K thut ny cho php tim lng mu ln hn bng syring tiu chun, trnh c
s sai s v lng mu tim. Hn na nhng cht c im si thp cng tin hnh
c. Vi bung tim PTV c ba k thut c th tin hnh l : K thut tim chia
dng trn ct lnh, k thut tim khng chia dng trn ct lnh v k thut tim
loi b dung mi.
K thut tim chia dng trn ct lnh
Sau khi mu c a vo bung ha hi lp tc van chia dng m v bung
c gia nhit. Dung mi v cc thnh phn khc nhau c trong mu theo th t i
vo ct theo nhit si ca n. Vi k thut tin hnh ny ct khng bao gi b
qu ti.

153

K thut tim trn ct lnh khng chia dng

K thut ny p dng khi phn tch hm lng vt. Van chia dng c ng trong
sut qu trnh tim. Bung tim c gia nhit theo s sp t ca chng trnh,
chuyn mu vo ct. thng ct l lnh.
K thut tim loi b dung mi
Mu l c a vo bung tim lnh, sau khi van chia dng m. Dng kh i ra
van s 2 rt ln c th t 1000ml/pht loi b ton b dung mi. Sau bung
tim c gia nhit cho php ton bt cc cht u ha hi, lc ny van 2 ng.
K thut ny cho php tim n 50l hay c th ln n 500l cho mi ln tim,
ng thi khng cn phi lm giu mu trc khi tim.
6.4. B phn gia nhit
Sc k kh c bung gia nhit vi th tch p ng vi th tch ca ct v
n c kh nng nng nhit n nhit ca chng trnh ci t ( khong t
400C n 4500C, vi n nh l 0,10C). Kh quyn bn trong bung nhit
thng khng i nh c h thng n nh. Bung gia nhit c th iu chnh
nhit thp bng cch s dng h thng lm lnh bng kh N2 hay CO2.
154

6.5. Ct
C 3 loi ct s dng trong h thng sc k kh l loi ct nhi (packer
columns), ct mao qun (capillary columns) v ct 530 (wide columns hay 530
columns). i vi loi ct nhi pha tnh c ph ln mt cht mang xp. Hai pha
tnh ca hai ct cn li th ph ln hay lin kt vi mt trong ca ct. Hnh di
y m t ba loi ct

Hnh a: Mt ct ca ct c v l thp khng r c ng knh trong l 1/8 in tng

ng 3,16mm
Hnh b: loi ct 530 c ng knh trong l 0,53mm
Hnh c: Ct mao quan c ng knh trong l 0,25mm
Hnh bn: l mt ct ca ct mao qun
6.5.1. Ct nhi
Nhng loi ct ny thng
ngy nay t khi s dng , n c
lm t thp khng r hoc thy
tinh. ng knh trong ca chng
khong n 1/8 in tng ng
t 3,18 n 6,36 mm v c chiu
di t 1 ti 3 mt. B mt ca ct
phi c x l sao cho thch ng
vi mu.Nhng loi ct ny dng
vi tc dng kh thp t 10 ti

155

40ml/pht. D vy loi ct ny chim khong 10% trong cc trng hp chy

GC .
Ct nhi bn trong cha mt lp cht mang xp tr v bn, pha tnh s
ph ln hay c gi bng nhng lin kt ha hc hay vt l (t l pha tnh to ra
khong t 3% ti 25% din tch b mt cht mang. Cht mang rn ph ln b mt
c chiu dy khong 0,2mm, thng cha hp cht diatomit, cc loi silicat.
Nhng cht ny c din tch b mt rt ln t 2 ti 8 m 2/gam, c bin tnh
bi nhng nh sn xut di tn gi l Chromosorb , dng nh mt quy c. Mt
th hp cht khc cng c trnh by l spherosil c lm t nhng ht rt nh
silicat. Tt c cc cht mang u l nhng th khc nhau ca silicat v trong thnh
phn phn t cha nhng nhm silanol.
6.5.2. Ct mao qun
Ct mao qun thng c
lm t nhng th silicat c tinh
kit cao c lm t phn ng t
chy SiH4 hay SiCl4 vi oxy p
sut cao. ng knh bn trong ct t
0,1 n 0,35mm v di t 15 ti
100m.
Tc dng khong vi ml/
min. Ct mao qun thng c ph
bn ngoi mt lp polyimide hay hay mt phim mng aluminium. Tnh c hc v
ha hc ca polyimide l bo v ct( Tmax= 3700C) nhng ct mao quan c cun
trn, rt nh . Mt trong ca lp silicat c x l k thut ph hp lin kt
vi pha tnh.
i vi ct WCOT ( Wall coated open tubular ), pha tnh ca ct ny ph
bn mt trong ca ct. Lp phim mng ca pha tnh c chiu dy khong 0,05 ti
5m. N c th c bm ln trn b mt hay to lin kt ng ha tr vi b mt

156

ca lp silica (cht mang) . Sau lp silica ny ph ln b mt trong polyme ca

ct. B mt silica c x l trc khi pha tnh ph ln , trnh cc hin
tng nh thm t, khng hp th hay thi gian n nh qu lu. Qu trnh x l
ny c th bng HCl 3500C hay ty sch b mt trong ca ng nhm. Sau khi x
l b mt trong ca ct th pha tnh c phun ln hay c hnh thnh bng qu
trnh trng hp bn trong ct. Nhng lin kt cng ha tr Si-O-Si-C cho php cc
hp cht ha hc gi trn bn mt silica . Vi loi ct ny h s a l thuyt c
th t n 150000 a
6.5.3. Ct 530 m (Wide bore columns)
Loi ct ny c lm t nhng ng silica c ng knh trong l 530m,
chiu di t 5 ti 50m, loi ct ny gn ging vi ct capillary. N xut hin vo
nm 1983 cng vi s c mt ca cc ng silica mm, do. Ct c quy c gi
l Megabore , Macrobore hay Ultrabore . T l dng pha ng x dng cho
nhng loi ct ny c th n 15ml/pht, thp hn so vi ct nhi.V vy c th
thay th ct nhi bng ct 530 do c th dng tng t bung tim v detector.
Tuy vy tnh phn gii ca nhng ct ny thp hn so vi ct capillary (tnh phn
gii t l vi ng knh trong ca ct). u im ca ct 530 so vi ct nhi l
khng c hin tng chy mu ct.( pha tnh mt dn theo thi gian)

Tnh cht trung gian ca loi ct ny l lin quan ti h s t s pha = VM/VS

. Nu gi dc l ng knh ct. df l chiu dy lp phim

Ta c :

157

Nu cc hp cht c tch l d bay hi, th ct no c t s pha nh c

chn.
V d ct 320m c chiu dy lp phim l 1m s cho t s pha = 80.
Trong khi ct 250 m, chiu dy lp phim l 0,2 m cho t s pha = 310 , ct c
= 80 chn.
V K= k. ta thy khi gim th k tng tc l h s phn b gia hai pha
tng c li cho qu trnh tch.
6.6.Pha tnh lng ( liquid type)
Lc ny pha tnh trng thi lng. Trc y th pha tnh loi ny c s
dng rt nhiu, nht l i vi ct nhi m v l nhm. Ct pha tnh l lng c
gia cng bng cch ngi ta cho nhng dung mi dng tch trn vi cht mang
to ra nhng th paste (trng thi nho nh kem nh rng ). Th paste ny c
phun vo bn trong ct , sau sy kh. Cht mang c tc dng phn b u pha
tnh trn ct v gi pha tnh kt dnh vi b mt ct.
Hai h hp cht chnh c s dng to ct l polysiloxanes v
polyethylene( silicones) glycols. Ngoi ra c nhng cht t bit khc nh
cyclodextrin tch cc hp cht i quang.
Cc loi ct h dng trong sc k kh lng
+ Vt liu ch to ct
- Vt liu chnh cht mang l Fused silica ( thch anh c tinh kit cao )
(Thch anh thng cha oxyt kim loi cao nhng Fused silica th c hm
lng oxyt kim loi < 1ppm)
-

C mm do cao

Khng d b gy v c lp bo v bn ngoi l polyme

Hm lng kim loi thp <1g/ gam

tr cao

158

Chu c nhit cao khong 3500C

Nhit

Nhit thp cho thi gian lu tng . Theo quy lut chung nu gim

nhit 10- 150C th lu gi tng 2 ln. Nhit ct cao hn nhit mi

trng thng s dng sc k kh. Nhit gii hn trn thng khng ch bi
ni ch to .
-

dy ca lp phim:

H s dung lng v dy ca lp phim t l thun vi nhau (hay ni ng

hn l t l pha v h s dung lng t l vi nhau). Ct c lp phim dy d b
chy mu ct hn, nhng lu gi cao hn .
phn cc
+ Thang phn cc da vo hng s MC Reynold
Ch s MC Reynolds l ga tr khc nhau gia ch s lu nhn c trn
Squalan ( pha tnh rt khng phn cc ) v pha tnh bt k
I= I i,x I i/sq
Cc cu t c trng m McREYnolds ngh s dng kim tra pha
tnh
Cc cu t

c trng lng c

trng c

trng

cc
nhn proton
cho proton
Benzen ( a)
Cm ng
Khng
Khng
1- butanol (b)
Bn/ yu
C
C
2- pentanol ( c)
Bn / trung bnh C
C
1- nitropropan (d) Bn /mnh
Yu
Yu
Pyridin (e)
Bn / yu
Mnh
Mnh
Tnh ch s Raynolds c tnh t tng cc hng s c trng cho mu( c
trng bng k hiu a,b,c,d v e) v cc hng s c trng cho pha ( x/, y/, z/, u/ v
s/ ). Mi cu t v mi pha tnh c th c trng bng t nht 5 thng s, t thng
s ny cho php tnh ton c ch s Raynolds theo phng trnh sau

159

I = ax/+ b y/+ cz/+ du/ + e s/

Ch s lu ca benzen trn cc pha tnh khc nhau:
Trn Squalan I = 649
Trn DEGS I = 1145
I = 1145 649 = 496
I cho bit tan ca benzen trong DEGS hoc cc pha tnh phn cc khc
Bng hng s Raynolds
Pha tnh
Squalan

Benzen (x/)
0

Butanol (y/)
0

SE- 30( OV- 1)

16

55

Apiozon L

32

39

OV- 17

119

158

DEGS
496
Theo thang phn cc ca hng Chrompack

746

phn cc
0

Pha tnh
Squalan

CP-sil 5 CB

CP-sil 8 CB

13

CP-sil 13 CB

19

CP-sil 19 CB

43

CP-sil 43 CB

52

CP-wax 52 CB

57

CP-Wax 57 CB

58

CP-Wax 58CB

88

CP- sil 88

100
OV- 275
Ch : Trong thc t , trong tt c cc qu trnh tch sc k c th thc hin
c ch cn 10 pha tnh khc nhau.

160

Hin ny nhiu hng sn xut a ra bn cc ct ng dng ring cho tng

i tng : TAP, FAME, FEAP, PAH, Dioxin, VOC, Pesticides ( thuc tr su)
organochlorine ( Clo hu c ) , GC-MS column ( ct cho sc k khi ph )
Cc pha tnh khc nhau
Cc pha tnh hin dng trong sc k phn ln da trn khung polysilicon:

Tnh vn c ca nhm R xc nh phn cc ca ct. Ni ng hn l xc

nh mi tng tc chn lc gia pha tnh v cht phn cc .
Cc pha tnh khng phn cc :
Pha tnh khng da trn siloxan
+ Squalan: C30H62 ( 2,6,9,15, 19,23- hexanmetyltetracosan)
+ Apiozon: [-CH2-]n ( n 50)
Nhit cn trn thp , rt nhy cm vi oxy, phn cc tng khi b oxy
ha tng phn
Pha tnh da trn siloxan :
100% dimetysiloxan

161

Tn thng dng : CP- Sil-5, OV-1,OV-101, metyl-100, BP- 1, DB-1.SP2100. Ultra-1, SE- 30, HP-1
Phenylmetylsiloxan

Phn trm nhm phenyl khc nhau ty thuc vo pha tnh v nm gia 5%
n 50%.
Pha tnh rt ph bin : cha 55 phenyl v 95% metyl
Tn thng dng CP-sil- 8, BP-5, HP-5, OV- 73, SE-54, Ultra-2
Diphenyldimetylpolysiloxan:

n nhit c ci thin ti 4300C . Thng dng cho php phn tch

nhit cao.
Thng dng l CP- Sil- 13: 86% dimetyl 14% diphenylpolysiloxan.

162

Cc pha tnh phn cc va phi

-

Cc pha tnh khng da trn siloxan

Polyphenylete: -[C6H5- O-]- n (n = 5 -8)

Nhit cn trn thp, rt nhy cm vi Oxy, phn cc tng khi b oxy
ha tng phn
Cc pha tnh phn cc nh cc lng cc bn
-

Cc pha tnh khng da trn siloxan

Cc pha tnh da trn siloxan

Phenyl- metyl-cyanopropyl- siloxan

Cu trc chung :

86% metyl- 7% phenyl - 7%cyanopropyl: CP-Sil19, DB = 1701, BP- 10,

OV- 170

163

50% metyl- 25% phenyl- 25% cyanopropyl:

CP-Sil- 43 , BP-225, DB- 225, HP- 225, OV225, SP- 2300
100% cyanopropyl: CP- Sil88, DB-23, SP-2330, SP- 2340, Silar- 10C
Cc nhm pha tnh phn cc c nhm cho nhn proton
-Cc pha tnh khng da trn siloxan :
Polyetylenglycol 20M
-[O-CH2-CH2-]n-OH
Tn thng dng : CP-WAX52CB, BP-20M,CW-20M,DB-WAX,HP-20M,
Supelcowax-10
-

Pha tnh da trn vic phn hot ha Carbowax

Pha tnh da trn siloxan

Cc pha tnh tch cht i quang

Cc pha tnh tch cc chiral tch khng n nh , trch dng nhit
cao v thp. Trnh dng chng trnh nhit vi tc t v lm ngui qu
nhanh . Khng thay i tc kh mang ngt
Cc pha tnh c nhm silonol lng tnh ( axit v baz)
Kh khn bt gp trong phn tch : amin, axit, ancol, ancaloit. Cc cu t ny
thng cho pic dong phn ui ( hoc khng xut hin tt c cc pic ) trn pha
tnh khng phn cc .
Cc pha tnh n nh c hc / bn vi dung mi :
+ Khi s dng k thut bm mu trc tip ( on- column) v khng chia
( splitless) , th cc pha tnh lin kt ha hc thng c dng
+ Nc c th lm hng lp phim pha tnh ( Cc pha tnh khng phn cc)
ch c nhng pha phn cc mi mi bn vi nc
+ S to thnh cc git pha tnh nh dn n lm gim hiu qu tm ca ct .
Lp phn hot ha b phn hy dn n pic ca cc cht kh tnh ko di phn
ui
tr
C ch lu gi xy ra do c s phn b kh lng, khng c s hp ph .
164

Nu c hp ph th qu trnh hp ph ng nhit b bin i v pic dong

ui
T trng ca ct
+ Qu ti dn n dong pha trc ca pic
+ Ti trng ph hp nhn c nu pha tnh v cht phn tch c cu trc
ha hc gn ging nhau
phn cc ca cc cht
Cht khng phn cc :
+ Hydrocacbon
+ Cc hp cht thm- PAH
+ PCB
Cc hp cht dit su Clo hu c.
Cc cht phn cc trung bnh :
+ Ete, este, aldehyde, ceton
+ Dioxin
+ Phtalat
Cht phn cc
+ Ancol, Diol
+ axit.
Kch thc ct
+ Kch thc ct khng nh tc phn tch , ti trng v gii hn phn tch
.
+ nh hng ca ng knh ct n tc phn tch
Dc( m)

Hmin ( m)

Nmax/m

L(m) tnh cho tr

105

530
320
250
150

446
269
210
121

2242
3713
4753
7921
165

thuyt
55,8
33,7
26,3
15,8

l
100
37
22
8

+ ng knh ct di 150 ( m) i hi phi c ci tin my ( rng di

bng li vo , p sut )
+ Dung lng mu gim t l thun vi dc 3
+ K thut bm on column i hi ng knh ct dc > 320( m) .
2.6.1. Polysiloxanes
Polysiloxanes c bit nh nhng du silicon hay gum
6.7. Pha tnh rn
ng dng
+ Cc cht c nhit si thp hn 25 0C khng th tch trn ct thng
thng
+ Cc cht ny i hi dng cc ct nhi hoc cc ct PLOT( porous Layer
Open Tubular Column) c lu gi cao .
+ Cc cht bay hi cao c th tch nhit phng hoc cao hn .
Kch thc :
+ ng knh trong : 320- 530 ( m)
+ dy lp phim : 5-50 ( m)
+ Kch thc ht : 0,1 1 ( m)
+ Ct c cha khong 1011 ht
Pha tnh
-

Molsieve 5A0 ( ry phn t )

ng dng : Dng phn tch cc kh He, H 2, Ar2, O2,N2, CO, CH4...Tch

tt cc kh ny nhit phng
-Al2O3/KCl
ng dng : Dng phn tch ch ti 2000C ,b mt khng phn cc. Hp
th thun nghch vi nc .
-Al2O3/ Na2SO4

166

ng dng : Dng tch kh t C1 ti C10 . n nh phn tch ch t ti

2000C ,b mt phn cc. Chn lc cao i vi lin kt i. Hp th thun nghch
vi nc
Cc vt liu Poraplot ( Polystyren divinylbenzen)
Cc nhn xt chung :
C lu gi cao, tr cao . ng dng trong phn tch cc cht bay hi
phn cc v khng phn cc. Phn tch cc cht ( SO 2, H2S, N2O, CO2 ) cho pick
cn i. Tch cc cht bay hi nhit phng hay cao hn. Thi gian lu khng
b nh hng bi vt nc trong mu
Cc vt liu dng t dng Q, S, U c phn cc t Q, S ti U
* Poraplot Q:
ng dng : phn tch cc alcol,nc ,cc cht bay hi khng phn cc
trong nc, cc hydrocacbon, cc kh, cc dung mi.
* Poraplot S: ng dng phn tch cc hydrocacbon, cc ceton, cc este, cc hp
cht halogen
* Poraplot U: ng dng phn tch tt c cc hp cht d bay hi phn cc , cc
hp cht nitril/nitro, cc alcol( cho ti C 4OH, cc aldehyde, etan/etylen, cc kh
sulfua, CO2, lng vt nc trong kh .
Carboplot: ng dng phn tch cc kh nh H 2, He,Ar, O2,CO,CO2, Kr, CH4,
C2H6, C2H4 chu c nc c th p dng c k thut bm Splitless.
Tenax- GC : l polyme phn cc
ng dng : phn tch cc cht phn cc , cc Diol, c phenol, cc
metylesteca cc dicacbocylicaxit, cc amin, cc etanollamin, cc aldehyde, cc
ceton. Tt c cc cht ny c nhit si nh hn 3000C

167

Cc ht polyme phn cc :
Chromosorb 101

STY- DVB

Chromosorb 102

STY- DVB

Chromosorb 103

polystyren

Chromosorb 104

ACN- DVB

Chromosorb 105

Acrylic este

Chromosorb 106

polystyren

Chromosorb 107

Acrylic este

Chromosorb 108

Acrylic este

Porapak:
N

Vinylpyrolidon

STY- DVB

EVB - DVB

Vinylpyrolidon

Vinylpyrolidon

EGDMA

PS

Silanized P

QS

Silanized Q

Vi

STY:

styren,

DVB:

divinylbenzen,

ACN:

etylvinylbenzen, EGDMA: etylen glycol dimetacrylat

6.8. Mt s detecter thng dung

168

acrylnitril,

EVB:

Thng la nhng loai nh sau :

1. Detector dn nhit : Thermal conductivity detector ( TC D)

Da trn nguyc tc cu Wheatstone, i khi cn c gi l Katharometer.

Cc in tr ca cu bng kim loi tr, c dn nhit tt, nh : vng, bch kim,
tungsteng. Cu t mu ra khi ct , i vo mt nhnh ca detector. Khi c s hin
din ca mu lm thay i nhit , da trn s thay i in tr ca cu , gy s
mt cn bng trong mch , to mt tn hiu di dng mi sc k . Khi mu ra
khi ct tn hiu bin mt.
c im:
- n gin, dng c cc mu hu c v v c, khng phn hy mu
-

Thi gian cho tn hiu ln v km nhy

2. Detector ion ha ngn la: Flame Ionization Detector (FID)

169

Cch in

Detector FID l mt trong nhng detector c nhy cao. Nguyn tc lm

vic ca n da trn s bin i dn in ca ngn la ca hydro t trong mt
in trng khi c cht hu c cn tch chuyn qua. Nh nhit cao ca ngn
la hydro, cc cht hu c t ct tch i vo detector b b gy mch, b ion ha
nh c oxy ca khng kh to thnh cc ion tri du tng ng. C ch to
thnh ion trong trng hp benzen nh sau:
C 6 H6

6CH

6CH + 3O2

6CHO+ + 6e

Cc ion to thnh c chuyn v cc bn in cc tri du nm hai pha

ca ngn la (th hiu gia hai bn in cc ny khang 250-300V).
Dng ion c gim p trn mt in tr c ch s rt cao (10 8-1012) v
gim hiu in th ny c khuch i v ghi li trn my t ghi. S lng ca
ion to thnh (chnh l nhy ca detector) ph thuc vo cc yu t sau:
- Cu trc hnh hc ca detector
- T l thnh phn ca hydro/khng kh
- Nhit ca ngn la.

170

- Cu trc ca cc phn t mu cn xc nh
S nguyn l hot ng ca detector ion ha ngn la (FID)

Cc hp cht hu c c t chy bng ngn la hydrov khng kh to

thnh cc ion. Kh mang t ct s c c trn trc vi hydro v t chy
bng ngn la bung t. Mt in cc hnh tr c t cch vi mm pha trn
ngn la thu thp cc ion sinh ra. Dng ion ny s c o bng cch t mt
in th gia u phun ca ngn la v in cc hnh tr hn ch n mc ti
a s ti kt hp ca cc ion, phi t in th chn lc vo vng bo ha (vng
m khi tng in th s khng lm tng dng ion) cc tnh hiu to thnh s c
khuch i bng b khch i in t ri qua b s l v ghi tnh hiu.
c im:
Khng b nh hng bi vn tc kh mang.
Thi gian ghi tn hiu nh hn 0,1giy v c nhy gp 1000 detector TCD
Gii hn pht hin di 10-12 g/s
Tuy nhin cng c nhng im bt li l phi dng thm h thng kh t,
ngoi kh mang khng c dng khi c cc kh nh: SO 2, CO2, H2O, NOx. Ngoi

171

ra cu t mu b phn hy trong ngn la nn khng th dng trong trng hp

mun cho cu t qua tip mt thit b phn tch khc (th d my hng ngoi)
Ch p ng vi cc hp cht hu c, khng c p ng i vi cc kh bn
v nc.
n nh cao t b nh hng ti s thay i nhit v tc dng.
Khong ng hc t 106-107.
Nhit lm vic ti 4000C.
Phn hy cht i hi 3 kh: kh mang, hydro, oxi
y cng l mt trong nhng Detector thong dng
3. Detector cng kt in t (electron capture detector):

ECD s dng hot phng x phng ra ion ha cc kh mang v pht

sinh ra dng in gia cp in cc. khi nhng phn t hu c c cha nhm
electron mang in tch nh: halogen, photpho v nhm nitro i qua detector,
detector gi li mt vi electron v lm bin i s o ca dng in gia cc in
cc.
Detector gm c in trng, bn trong c ngun pht tia (do Ni 63, c
ph bn ngoi tm bch kim hay titan), kh mang c dng l Ar. in t s cp
ca tia s ion ha phn t kh mang lm bn ra in t th cp, to dng in
trong in trng, phn ng dy chuyn xy ra. Khi c s hin din ca mu,
172

thng l cht c m in cao, s nhn in t th cp, lm gim cng

dng in, tng ng vi s xut hin mi sc k
Detector hot ng da trn t tnh ca cc cht c kh nng cng kt cc
in t t do trong pha kh (tr trng ngoi l ca cc kh tr) kh nng cng kt
in t ln hay nh l ph thuc vo cc hp cht cn c pht hin. Kh nng
tng i nh i vi cc hp cht hdrocacbon no. Ngc li, khi cc hp cht
c cha cc nhm chc hoc a lin kt (i hoc ba) th kh nng cc in t s
tng hn ln. c bit l nu trong phn t ca hp cht ny c cha cc nguyn
t halogen (Cl, Br.) Bi vy, nhy pht hin ca detector ECD rt c th
cho cc nhm chc v c th dao ng trong phm vi kh rng (1-106)
B phn chnh ca detector ECD l mt bung ion. Ti y din ra qu
trnh ion ha, bt gia in t v ti kt hp.

M: l phn t kh mang, EC: l phn t ca cht c kh nng bt gi in

t.
Cng chnh v kh nng bt gi in t (electron-capture) m
detector cn c gi l detector bt gi in t.
* Qu trnh ion ha: mt ngun tia phng x c lp sn trong detector,
pht ra mt chm tia - vi tc 108-109 ht/s. Cc ht - ny s ion ha phn t
173

kh mang (M) to ra cc ion dng ca phn t kh mang v in t t do s cp

(e-). So vi cc in t ca chm tia - cc in t t do ny chm hn hn. Chng
c gia tc nh mt in trng v c chuyn dch v pha ant. Ti y
chng b ly mt in tch v qua cho dng in nn ca detector.
* Qu trinh cng kt in t cc nguyn t hoc l phn t ca cc cht
(EC), sau khi ri b ct tch, c a thng vo bung ion cng vi kh mang.
Ty theo i lc in t ca cc phn t ny, cc in t t do s cp ni trn s b
cc phn t bt gi v do vy to ra cc ion m.
* Qu trnh ti kt hp: cc ion m c to ra nh vy s kt hp vi cc
ion dng ca phn t kh mang to thnh cc phn t trung ha.
Nh vy do kh nng ct kt in t ca cht cn phn tch, in t b ly
mt khi h v dng in nn b gim i so vi lc ch c kh mang tinh khit i
qua detector. Mc suy gim ca dng in nn trong thi im c cht i qua
c th hin bng pic sc k ca cht .

Lp cch in

V detector

Kp
ln

ng hnh tr

nhy ca detector ECD ph thuc vo :

174

Tay n
u nhn xung t bung detector

ln ca dng in nn

Mc nng lng i in t ca cht cn pht hin

Bn cht ca kh mang

in th c t vo detector

R rng nhng cht c i lc in t cao s cho cc tnh hiu mnh, to

ra cc in th cn thit cho qu trnh vn chuyn ion, c th t vo detector th
mt chiu khng i hoc l th mt chiu di dng xung. Trong trng hp s
dng th mt chiu khng i, vng lm vic ti u ca in th t vo detector
ph thuc vo bn cht ca cht nghin cu v nhit ca detector cc gi tr ny
thng dao ng gi 1-30V. Ngc li, nu s dng in th dng xung khong
lm vic ti u ca detector s khng ph thuc vo bn cht ca cht nghin cu,
m ch ph thuc khong cch gi cc xung trong mt iu kin nht nh. Thng
thng s dng th hiu mt chiu gin an khang 50V, vi di xung t
0,75-3s v khong cch gi hai xung 5-200s.
c im:
nhy cao, nht l khi mu thuc cc nhm chc: halogenua, peroxid,
quinon, nitroc bit dng phn tch thuc st trng.
Nhng nhy cao, phi dng kh Ar (gi tr cao), v N2 c lin kt
kh bn nn kh to in t th cp.
4. Detector pht x nguyn t (atomic-emission detector):

175

y l loi hin i. Cu t ra khi ct c a qua trng plasma (to

bi heli) c nng lng ca bc x vng vi sng. Cu t mu nhn nng lng, b
nguyn t ha v nguyn t b kch thch, do chng c kh nng pht x.
Cng pht x c ghi nhn v chuyn thnh mi sc k.
c im:
+ nhy rt cao, thi gian pht x tnh hiu nh.
+ c bit my c th ghi nhn ng thi nhiu cc t.
+ Tuy nhin chi ph phn tch rt cao v phi dng kh heli.
Th mnh ca detector AED l n c kh nng xc nh nhng pht x
nguyn t ca nhiu phn t trong mt php phn tch ra gii t ct mao qun
GC. Khi dung dch ra gii ra khi ct mao qun, chng c a vo trong mt
trng plasma (hoc s phng in) ni m cu t mu nhn nng lng v b
kch thch bi nng lng t plasma, do chng c kh nng pht x. My tnh
c ghi li cng pht x v chuyn thnh mi sc k.
5. Detector quang ha ion (photoionization detector):

176

Cung cp
in

V bc cch ly
chn tia UV

Ca trong sut cho UV

i qua
Kh hoc my d kt ni c
th tch nh

Bung gia
nhit s ion
ha

Phn ng s dng hn mt loi detector cho sc ph kh, n t c

nhy cao nh hiu qu ca cc hp cht c bit vi k thut phn tch sc ph
ring bit. S xc nhc chn lc ca hydrocacbon thm hoc nhm organoheteroatom l cng vic ca u d quang ph PID. Thit b s dng nng lng
nh sng cc tm nh phng tin ca k thut phn tch r ct GC. Cc ion to ra
t qu trnh ny bi tin trnh hot ng ca electron. Dng in pht ra c tp
trung cho k thut phn tch.
7. Chemiluminescence Spectroscopy:
Tn hiu

Ct mao qun t
sc k kh

my bm chn khng

177

S pht quang bng phn ng ha hc, ging nh nguyn t pht ra quang

ph, dng nh lng s pht quang t nhng nguyn t b kch thch trong
php phn tch c c, tuy nhin khng ging AES.
S pht quang bng phn ng ha hc thng pht ra nhng phn t mnh
thay th khi chng b kch thch, dy nh sng c xc nh bi k thut bt
ngun t vic to ra phn t, t n gin n phc tp.
Hn na s trc quang bng phn ng ha hc c th xy ra bn trong pha
lng hay pha kh. Trong khi AES gn nh chnh xc so vi pha kh. Tuy nhin
s pht quang bng phn ng ha hc trong pha lng ng vai tr quan trng
trong k thut phn tch phng th nghim. Phng php ny thng s dng vi
sc k lng. Chng ta s tp trung vo nhng phn ng ca s pht quang bng
phn ng ha hc pha kh vi nhng cht cu thnh nn n c phn n gin
hn.
Nhng my d tm ny cng c s dng nh nhng my d tm cho k
thut phn tch thnh phn cc cht.
Th mnh ca phng php trc quang bng phn ng ha hc trong u
d ca bc x in t c tiu chun thp.
Vn u tin ca loi hnh phn ng ny l to ra nng lng cn thit,
kch thch cc electron ln mc nng lng cao hn, nh nhng chn ng v tnh
trng xoay vng (t chng b ph hy trng thi ny bng s pht x ch khng
n gin nh nh sng pht t ngn n hay tia laze.
Detector Nit-photpho NPD:
Detector NPD cn gi l detector ion ha ngn la s dng mui kim hay
detector nhit ion (AFID-Alkali flame ionization detector ), detector ion ha nhit
ngn la (FTD- flame thermionic detector) detector ny cho nhy cao khi phn
tch cc hp cht c cha nit-photpho, ph thuc vo iu kin phn tch n t ra
rt hu hiu trong vic phn tch cc dc phm, d lng ca cc hp cht
cacbamat v photphat s dng trong nng nghip v phn tch lng vt cc hp

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cht cha nit v photpho nh nitrosamin, trimetylamin, acrylomitricl trong cc

cht tng hp nhn to.
Mt d c ch phn ng chnh xc ca detector ny vn cha c hiu
mt cch y nhng c th a ra mt c ch phn ng chp nhn c nh
sau:
Cc hp cht cha nit i ra t ct sc k tr thnh gc CN*. Sau khi phn
hy nhit trn b mt kim loi kim nung gc CN* kt hp vi cc electron
that ra t b mt kim lai kim nung (Rb) v tr thnh ion CN -. Cc ion ny
kt hp vi cc nguyn t hyro. Trong khi ngun kim lai kim (Rb) tr thnh
cation sau khi gii that cc electron, to ra mt dng tp hp v chuyn thnhtn
hiu.
Trong Detector ( NPD-17) ngun ion l mt kim lai kim c ph ln
mt dy palatin dng xon c. ngun ny c ni vi dng Ac nung nng si
palatin.
Mu cht ra t ct c tch ra khi ming ng sau khi trn vi mt lng
nh hydro, tip xc vi ngun kim lai kim nung trn. Nhiu phn ng din
ra ti b mt v mi trng xung quanh. Phn mu c that ra ngai qua trung
tm ca b phn thu mu.
4.3.

B phn ghi nhn kt qu

Sc k ghi nhn kt qu qua my ghi hay xut hin trn mn hnh . Hin
nay tt c cc my u ghp vi my vi tnh , s l s liu v tnh ton , lu tr
kt qu

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Flame Ionization Detector (FID)

180

detector MS
NG DNG
1. nh tnh
Cu t c nh tnh theo gi tr t R. So snh tR ca mu v tR ca cu t
chun trong cng iu kin o trn my. c kt qu chnh xc c th dng c
hai loi ct phn cc v khng phn cc, ngoi ra c th thm cu t chun vo
mu.
2. nh lng
nh lng cu t trong mu bng cch so snh vi dung dch chun, c th
so snh theo :

Chiu cao h ca mi, nu mi hp v c dng i xng

Din tch mi

C th nh lng theo cch thm cht chun hay cch lp ng chun h,S
= f. Din tch mi c tnh theo cc cng thc sau:
S = 0,5 h.W

S=1,064h.w1/2=1,032(0,5hw)

Nhng hin nay, vi my vi tnh km theo, kt qu c tnh theo nhng

chng trnh c sn
Mot so ng dung sac ky kh trong thc pham

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Phng phap phan tch thuoc tr sau c Clo

Thuoc r sau c Clo c phan tch bang detector ECD v
o nhay cao cua no oi vi cac cau t halogen.
Detector ECD co the xac nh mot cach de dang oi
vi cac thuoc tr sau nong o ppb
Hnh 2: la hnh thu c khi chay sac ky kh ieu kien
sau :
+ au do ECD
+ Cot OV 17
+ Nhiet o cot : 2150C
+ Pha ong la kh N2
+ Toc o dong kh la 30ml/min
Nam mui thu c th t la : Lindan Heptaclo
Aldrin Dieidrin p-p/ DDT

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Hnh 3: la hnh thu c khi chay sac ky kh ieu

kien sau :
+ au do ECD
+ Cot thuy tinh vi chat khong phan cc la Dow 11
+ Nhiet o cot : 1850C
+ Pha ong la kh N2
+ Toc o dong kh la 50ml/min
Tam mui thu c th t la : Lindan Heptaclo Aldrin
Heptaclo epoxide - Dieidrin p-p/ DDT- p ,p DDT- Tedion
Xac nh cac axit phenoxyalkanoic

Hnh 15 thu c khi chy mu thuc tr su vi iu kin chy nh sau:

+ u d ECD
+ Ct thy tinh vi cht khng phn cc l Dow 11
+ Nhit ct : 1850C
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+ Pha ng l kh N2
+ Tc dng kh l 25ml/min
Tm mi thu c th t l : 2,4- D ( izopropylEste 2,4,5,T ( MeEste)
Parathion Suphenone - Ethion EPt-

Phn tch nc hoa qu , nc mn

iu kin chy :
+ Ct : Shim park SCR 101C
+ Pha ng : nc
+ Nhit ct : 800C
+ T l dng : 10ml/min
+ Detector: Refractive index

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Hnh 30 va 31 la sac ky o thu c khi xac nh

triglyxerit trong b va dau co
ieu kien xac nh nh sau:
+ Cot : CBM65- M25- 010 25. 0,25 fused Silica
+ Nhiet o cot : 2900C
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+Pha ong : kh He
+Detector: FID

186