1.

Ph nguyn t
 Ph pht x nguyn t (AES) Ph hp th nguyn t (AAS) ICP-MS
Ngun kch 1 ngun nng lng 1 tia n sc
thch
Nguyn tc Dung nng lng kch thch cc nguyn t trng
thi c bn ln trng thi kch thch
Sau 10^-8 s, cc ht chuyn v trng thi c bn,
nng lng pht ra di dng bc x
Cc bc Dung nng lng chuyn cht cn phn tch thnh
hi nguyn t ( nguyn t ha
Dung nng lng kch thch nguyn t hnh
thnh bc x nguyn t
Dung lng knh phn ly ra tia n sc
+ Da vo v tr quang ph pht x s xc inh
nh tnh c nguyn t
+ da vo cng vch ph xc nh hm lng
nguyn t trong cht phn tch
p dng c dung nh lng v nh tnh cht phn
tch ha tan hay hm trong dung dch h20 hay
cht lng hu c. Ngoi ra c th phn tch mu
rn

Xc nh cc nguyn t:
Trn l thuyt c th xc nh c tt c cc kim
loi c nng nh trong cc mu khc nhau tuy
vy cc kim loi kim b hn ch do
+ cc iu kin tin hnh nguyn t khc khng
ph hp v KL kim
+ ng vch ph ca ph kim loi gn vng ph
R. kh khan xc nh (detector thit k xc
nh bc song thuc visible
Vi i tng kim th phng php ny c nhiu
nhc im v hn ch v nhy, cng nh
nhng trang b thu, ghi ph ca chng, v ph ca
hu ht cc kim li nm ngoi
vng t ngoi v kh kin, ngha l phi c thm
 nhng trang b phc tp mi c th
phn tch c cc kim
Spectrometer 1 s tnh cht quan trng ca thit b
+ phn gii cao
+ tn hiu thu c nhanh
+ khong tuyn tnh rng (wide)
+ chm

Phn loi ::
+
u im + c nhy cao
Ex: nhng ngun kch thch ph mi (ICP) ngi ta
c th t n nhy t n.10-5 n n.10-6 % i
Xc nh nguyn t khng cn lm giu
+ phn tch c nhiu nguyn t trong cng 1 mu
m khng cn tch ring
+ vi nng nh, sai s thp
+tiu tn t mu
+ phn tch c ng nht v thnh phn vt
mu nhng v tr khc nhau

Nhc im + ch cho thnh phn trong mu phn tch, khng

cho bit trng thi lin kt trong phn t
+ chnh xc ca php phn tch ph thuc vo
nng chnh xc ca thnh phn ca dy mu u

Plasma cao + ngun nng lng c nhit cao nhng rt m

tn cm ng du
+ ngun nng lng kch thch c nhy cao,
n nh cao, sai s nh
+ t b nh hng bi nn mu
 Cu to:

1 s yu t 1.S pht x ph nn
nh hng - Trong vng ph visible th xut hin r rang
- Trong vng IR th khng xut hin
2.s chen ln cc ph gn nhau

PH PHT X.

10.1
 1. Atomic absorption spectrometry
1, qu trnh nguyn t
2 phng php chnh: flame atomization & electrothermal atomization
a. Flame atomization
Dung dch c nebulized bi 1 dng kh oxi ha, trn vi kh nhin liu to thnh ngn la, ni xy ra nguyn t ha
Cc bc ca qu trnh nguyn t ha
- Desolvation: dung mi c bay hi
- Volatilized:
- Dissociation: phn ct cc phn t thnh nguyn t, 1 vi nguyn t ion ha cation v electron
1 phn phn t, nguyn t v ion c kch thch bi nhit ca ngn la hnh thnh ph pht x nguyn t, phn t ion

Cu trc ca ngn la:

- Primary combustion zone: vng chy ca hydrocacbon c nhn ra mu xanh ca s pht quang xut hin t band emission
ca C2, CH v gc khc, cn bng nhit khng t c vng ny v n khng c p dng trong ph flame FAAS.
- Internal area, s dng 1 phn trong ph FAAS
- Secondary combustion zone: sn phm ca , s dng trong FAAS.
Cc yu t cung cp thng tin cho cc qu trnh khc nhau trong FAAS:
+ Nhit
+ Flame absorption profiles:
Hnh 9.4 ch ph ca 3 nguyn t
Mg c A max ti chiu cao gia ca ngn la bi 2 hiu ng i ngc nhau. 1 l s gia tang nguyn t Mg do tip xc vi nhit.
Khi n gn vng secondary combustion, Mg bt u b oxi ha lm gim hp th
Ag kh b oxi ha do hp th s tang dn khi tawg chiu cao
Cr to oxit bn nn A s gim ngay khi tip xc vs u ca gn la
Nhng phn khc nhau ca ngn la th xc nh 1 nguyn t rieeg bit

Flame atomizer: c s dugj trong AAS, AFS, AES

GF-AAS:
Hydride generation
I. UV-Vis molecular absorption spectrometry
1.Cc nguyn nhn v du hiu cho thy s hp ph nh sang khng tun theo nh lut Beer
- du hiu: th C-A khng tuyn tnh v cng iu kin bc song hp th li khc nhau
- nguyn nhn:
+ Beer law ch ng trong trng hp nng nh, khi C ln th s xut hin tng tc gia cht tan- dung mi, cht tan-
cht tan, lin kt hidro lm nh hng n mi trng v epxilon.
+ do s c mt ca stray radiation (xut hin do s tn x hoc phn x b mt ca gng, ca s) => hp th s nh
hn l thuyt nng cao.
+ Do nh sang khng n sc
+ Do s thay i nng trong dung dch
S pha long dung dch, to phc
+ nh hng pH n s hnh thnh phc mu:
X+HR=XR+H+
HR l acid mnh, R l anion acid mnh: p tin hnh trong mi trng acid trnh s thy phn ca kim loi nhng nu
pH thp qu s tang lc ion=> tang phn ly. Nu pH qu cao ion kim loi b thy phn, phc XR cng c th bj thy
phn.
2. Instrumental noise ( nh hng n accuracy v precision)
Cc ngun gy instrumental noise: do ln ca dng quang in
II. Intrumentation
1, light sources
a. n d2 hoc h2
1 continuum spectra c to ra t s kch thch in ca D2 v H2
P: D2+Ee=D2*=D+D+hv
Thng dung n deuteri hn l n hydrogen
C 2 n u to ra 1 dy bc sogs t 160-800nm, ph UV 190-400nm.
Cuvette thch anh c dung trong n detueari v hydrogen do knh hp th bc song di 350 nm
b. n tungsten filament (ngun to ra bc song gn ph IR v trong khong nhn thy
n ph hp trong khong bc song 350-2500nm
c. n xenon arc
To ra bc x mnh bng cch cho dng in i qua mi trng xenon
Ngun to ra bc song 200-1000nm
3. Sample container (cell hoc cuvette)
Cuvet thch anh dung trong vng UV (<350nm)
 Silicagel glass dung trong 350-2000nm
Plastic dung trong vng visible
III. Application of UV-vis molecular absorption spectrometry
14.1. ln ca epxilon,
14.2 absorbing species
S hp th nguyn t hoc phn t theo 2 qu trnh:
+ kch thch in t M+hv=M*
+M* ch tn ti trong 10^-9s sau n s tr v trng thi ban u M*=M+heat
S hp th xy ra t s kch thch cc linkt electron
Bc song hp th s tng ng vi loi lin kt trong phn t
Chc nng: xc nh nhm chc trong phn t
Xc nh nh lng hp cht cha nhm hp th
1. S hp th ca hp cht hu c
Tt c cc cht hu c u c kh nng hp th do u cha cc electron ha tr kch thch ln mc nng lng cao hn.
Xch ma => xch ma* .Nng lng kch thch ng vi electron hnh thnh lin kt n xay ra hp th l nng lng vng UV chn
khng (lamda< 185nm). Epxilon thng thp 100-3000 L.mol-1.cm-1 (nng lng cao)
Do rt kh c c mi trng chn khng, nn bc song hp th thng ln hn 185nm
n-> *: hp cht no khng cho in t hp th 150-250 nm
n->*, ->*
Nng lng kch thch cn cho electron hnh thnh lin kt i hay 3 l nng lng vng UV-Vis (200-700nm)
Requires unsaturated groups
n->* low (10 to 100): Shorter wavelengths
->* higher (1000 to 10000)
2. hp th ca hp cht v c

cc nguyn t kim loi chuyn tip hp th cc bc song trong vng nhn thy
filled orbitan d => unfilled orbitan d vi nng lng ph thuc vo phi t lin kt vi kim loi. s khc nhau v nng lng ca cc AOd
ph thuc vo v tr ca n trong bng tun hon, trng thi oxi ha, bn cht phi t
3. xc nh nh tnh bng UV-Vis
s dng xc nh chromophoric group ( cc nhm khng no)
UV-Vis khng c cu trc r rng cho php xc nh tt cht phn tch
cn kt hp vi cc phng php vt l v ha hc khc
 a. dung mi
nh lng thng s dng dung dch long ca cht phn tch. Tuy vy, i vi cc hp cht d bay hi, ta s dng gas-phase spectra
hn l liquid-phase spectra. Gas phase spectra
CHN DUNG MI: khng c mu v khng nh hng n h hp th. V d: h20, ancol, este, xeton ( dung mi phn cc),
hydrocacbon (dung mi khng phn cc)
Bn cnh bn cht ca dung mi cng nh hng n lam a max
b. xc nh nhm chc
s dng hiu qu xc nh 1 nhm chc nht nh (chromophores)

c. xc nh nh lng bng php o hp th

c tnh quan trng: p dng cho nhiu cht hu c v n=v c
LOD thp 10^-4-10^-5
chn lc tng i
Good accuracy
S liu d dng thu c
Applications to absorbing species: hp cht hu c 1 hoc nhiu nhm chc hp th
Ion kim loi chuyn tip c mu trong dung dch, nitrite, nitrate, cr2o72-, oxit nito, nguyn t halogen, ozon
Applications to nonabsorbing species: s dng p to sn phm c epxilon ln hn cht phn tch, dng nhiu xc nh ion kim loi chuyn
tip
V d: SCN-: st, coban, Mo
H202: Ti, V, Cr
I-: Bi, Palladium, Te
Diethylthicarbazone: Cu
Diphenylthiocarbazone: Pb
1-10-phenanthrolene: Fe
Dethyl glyoxime: ni

Quy trnh:
-xc nh bc sng: bc sng = bc sng ti cht hp th cc i
 - cc yu t nh hng n hp th: bn cht dung mi, nhit , nng cao cht phn tch, s c mt ca yu t gy cn tr
B. Molecuar luminscence spectrometry

S pht hunh quang S pht ln quang

Excited state

Singlet and triplet excited state

Singlet: trng thi electron phn t cha tt c cc electron c spin ghp i vi nhau, khng c s tch mc nng lng khi t vo t
trng.
Doublet: trng thi c bn l cc gc t do
Triplet: khi c 1 nng lng kch thch, spin ca 2 e ghp i khng cn to thnh cp m n tr thnh song song. Ch rn the
excited triplet c nng lng thp hn excited singlet tng ng

C 1 s chuyn i t singlet sang triplet hoc ngc li (t xy ra hn singlet sang singlet ( s pht ln quang) thi gian cho s
chuyn i t 10^-4 n 10s
1. Hiu sut nng lng v hiu sut lng t pht quang
c trng so vi ph hp th:
- 1 phn nng lng kch thch b tiu tn di dng nhit => nng lng pht quang (Epq) < nng lng kch thch (Ekt)
Lamda pht quang> Lam a hp th => ph hunh quang bao h cng chuyn dch v pha bc song di hn so vi ph hp th
( Quy lut Stock)
- Khong cch gia cc i ph hp th v ph hunh quang gi l chuyn dch stock. chuyn dch cng ln => cng loi tr c
nh hng ca nh sang kch thch mc d nh sang hunh quang khi o hay quan st u c vung gc vi nh sang kch thch nhng
nh sang kch thch vn nh hng do s tn x trn b mt cht lng hay thnh cuvet
- Mi quan h gia cn nh sang kch thch v cng nh snags hunh quang
B=Q. lamda hp th / lam da pht quang
B l hiu sut nawg lgj, Q l hiu sut lng t
Dung vng ph t ngoi kch thch

Cng ca dng pht hunh quang I(pq)= K. C vi K=k.Q.k.IO2.303. Epxilon.b.C ( ch ng trong khong nng b)

2. S tt hunh quang
a. S tt do nng
Khi tang nng , cng pht quag s gim dn v tt bc x do
+ c th hinh thnh cc tp hp ph t, khng hp th nh sags kch thch
 b. nh hng Ph Ca dung mi
c. nh hng ca nhit
d. nh hng ca cu t l
3. Molecular fluorescence
The most intense and useful fluorescence is found in compound containg aromatics functional group with low energy pi=> pi*
transitions. It may apply for compunds containg hp cht khng vng (aliphatic) v hp cht vng no (alicylic carbonyl) nhuwg s
lng t hn hp cht vng thm
Cc hp cht d vng n gin khng biu hi s pht quag, tuy vy s ghp vng benzene li th hin v d

Cc nhm chc cacboxylic acid v carbonyl trn nhm thm cugx u th hin tnh pht quang
NH HNG CA STRUCTURAL RIGIDITY ( S PHT QUANG THNG THUN LI TRONG PHN T C CHA RIGID
STRUCTURE)

V d:

S pht quang cng tang ln trong phc chelat

C. ph IR v Raman