Luan Van Dieu Hoa

MC LC
MC LC.....................................................................................................................1
Bng k hiu cc t vit tt...........................................................................................3
Danh mc bng..............................................................................................................4
Danh mc hnh..............................................................................................................6
M U.......................................................................................................................7
CHNG 1. TNG QUAN........................................................................................8
1.1. Vai tr v c tnh phn tch ca ng, km, coban .........................................8
1.1.1. Vai tr ca ng, km, coban i vi s pht trin ca sinh vt.................8
1.1.2. c tnh phn tch ca ng, km, coban .................................................11
1.2. Mt s phng php quang xc nh Cu(II), Zn(II), Co(II)............................18
1.2.1. Phng php ph hp th nguyn t AAS ...............................................19
1.2.2. Phng php phn tch trc quang ...........................................................20
1.3. Thuc th 1-(2-pyridylazo )-2- naphtol (PAN) ..............................................27
1.3.1. Cu to, tnh cht vt l ca PAN .............................................................27
1.3.2. Kh nng to phc ca PAN.....................................................................28
CHNG 2. THC NGHIM.................................................................................34
2.1. Ni dung nghin cu.......................................................................................34
2.2. Thit b v ha cht ........................................................................................35
2.2.1 Thit b v phn mm.................................................................................35
2.2.2. Ha cht...................................................................................................35
2.3. Cch tin hnh thc nghim............................................................................37
2.3.1. Qui trnh nghin cu n bin .................................................................37
2.3.2. Qui trnh nghin cu a bin....................................................................37
2.3.3. Qui trnh phn tch mu.............................................................................37
2.4. Thut ton phn tch hi qui tuyn tnh a bin .............................................38
2.4.1. Phng php bnh phng ti thiu thng thng (CLS)........................38
2.4.2. Phng php bnh phng ti thiu nghch o (ILS)..............................38
2.4.3. Phng php bnh phng ti thiu tng phn (PLS)..............................39
2.4.4. Phng php hi qui cu t chnh (PCR)................................................39

CHNG 3. KT QU V THO LUN.............................................................41
3.1. Kho st iu kin ti u xc nh Cu(II), Zn(II), Co(II)...............................41
3.1.1. Nt c trng ph ca cc phc Cu(II)-PAN, Zn(II) -PAN, Co(II) PAN
.............................................................................................................................41
3.1.2. Kho st nh hng ca pH n s to phc............................................43
3.1.3. Kho st nh hng ca nng Triton X-100 n s to phc..............45
3.1.4. Kho st nh hng ca thuc th PAN .................................................46
3.1.5. Kho st nh hng ca thi gian ............................................................47
3.1.6. Kho st nh hng ca nng Cu(II), Zn(II), Co(II)...........................48
3.1.7. Kho st nh hng ca cc ion l............................................................57
3.2. Xc nh Cu(II), Zn(II), Co(II) trong hn hp................................................61
3.2.1. Xc nh Cu(II), Zn(II), Co(II) trong hn hp bng phng php tch....62
3.2.2. S dng thut ton hi qui tuyn ttnh a bin xc nh ng thi Cu(II),
Zn(II), Co(II) ....................................................................................................64
3.3. ng dng vo phn tch mu phn vi lng...................................................75
3.3.1. Qui trnh ph mu......................................................................................75
3.3.2. Phn tch mu phn vi lng.....................................................................75
KT LUN.................................................................................................................80
TI LIU THAM KHO...........................................................................................82
Bng k hiu cc t vit tt

STT
1
2
3
4
5
6
7
8
9
10
11
K hiu vit tt
AAS
Tn y
Atomic absorbtion spectrotometry
CLS
(Quang ph hp th nguyn t)
Classical least squares
ILS
(Phng php bnh phng ti thiu thng thng)

Inverse least squares
PC
PCR
(Phng php bnh phng ti thiu nghch o)

Principal component (Cu t chnh)
Principal component regression
PLS
(Phng php hi qui cu t chnh)

Partial least squares
PP
ppm
(Phng php bnh phng ti thiu tng phn)

Phng php
Part per million
UV-Vis
(Phn triu)
Ultraviolet visible spectrophotometry
SD
(Quang ph t ngoi kh kin)

Standard deviation
UV-Vis
( lch chun )
Ultraviolet visible spectrophotometry
(Quang ph t ngoi kh kin)
Danh mc bng
Bng 1. S hnh thnh phc Cu(II) trong mt s thuc th hu c............................20
Bng 2. Cc tnh cht ca mt s phc kim loi PAN............................................29
Bng 3. c trng ph hp th Cu(II) - PAN, Zn(II) PAN, Co(II) PAN...............43
Bng 4. Kt qu kho st nh hng ca pH n s hnh thnh cc phc.................43
Bng 5. nh hng ca nng m citrat n s hnh thnh cc phc...................44
Bng 6: S ph thuc ca hp th quang vo nng ca m axetat.................45
Bng 7. Kho st nh hng ca nng Triton X100 n s hnh thnh phc.....45
Bng 8: Kt qu kho st nh hng ca thuc th PAN..........................................46
Bng 9: Kt qu s ph thuc ca A vo nng Cu(II)...........................................48
Bng 11: Kt qu o hp th quang ca 12 mu trng...........................................50
Bng 12: hp th quang ca phc Cu(II)-PAN 3 nng khc nhau................51
Bng 13:Kt qu nh gi phng php xc nh Cu(II)...........................................51
Bng 14: Kt qu s ph thuc ca A vo nng Zn(II)..........................................51
Bng 15: Kt qu xy dng ng chun xc nh Zn(II)..........................................52
Bng 16: Kt qu o hp th quang ca 12 mu trng..........................................53
Bng 17: hp th quang ca phc Zn-PAN 3 nng khc nhau.....................54
Bng 18: Kt qu nh gi phng php xc nh Zn(II)...........................................54
Bng 19: Kt qu s ph thuc ca A vo nng Co(II).........................................54
Bng 20: Kt qu xy dng ng chun xc nh Co(II)........................................55
Bng 21: Kt qu o hp th quang ca 12 mu trng..........................................57
Bng 22: hp th quang ca phc Co-PAN 3 nng khc nhau.....................57
Bng 23:Kt qu nh gi phng php xc nh Co(II)...........................................57
Bng 24 : nh hng ca Mn(II) n hp th quang trong m axetat................58
Bng 25 : nh hng ca Mn(II) n hp th quang trong hn hp m...........58
Bng 26 : nh hng ca Fe(II) n hp th quang trong m axetat.................59
Bng 27 : nh hng ca Fe(II) n hp th quang trong hn hp m ............59
Bng 28 : nh hng ca Fe(III) n hp th quang trong m axetat................60
Bng 29 : nh hng ca Fe(III) n hp th quang trong hn hp m ...........60
Bng 30. Hiu sut thu hi theo phng php tch da vo ng chun.................63
Bng 31:Nng thm chun....................................................................................63

Bng 32: Hiu sut thu hi theo phng php tch da vo ng thm chun........64
Bng 33: hp th quang ca tng ion v ca hn hp trn ton ph ...................64
Bng 34: Sai s gia nng mu chun v nng xc nh c t phng php
CLS..............................................................................................................................68
ILS ..............................................................................................................................70
PLS..............................................................................................................................72
PCR.............................................................................................................................74
Bng 38: Hm lng Cu(II), Zn(II), Co(II) trn nhn mt s mu phn vi lng......75
Bng 39: Hm lng Cu(II), Zn(II), Co(II) trong mu o bng phng php AAS...76
Bng 40: Xc nh ng thi hm lng Cu(II), Zn(II), Co(II).................................76
Bng 41: Hm lng Cu(II), Zn(II), Co(II) trong mu o bng phng php tch...77
Bng 42 : Hm lng trung bnh ca cc ion ............................................................77
Bng 43: Kt qu phn tch hm lng Cu(II) (ppm).................................................78
Bng 44: Kt qu phn tch hm lng Zn(II) (ppm).................................................78
Bng 45: Kt qu phn tch hm lng Co(II) (ppm).................................................79
Danh mc hnh
Hnh 1. c trng ca ph hp th cc phc mu trong mi trng Tween 80.........41
Hnh 2. c trng ca ph hp th cc phc trong mi trng Triton X-100............42
Hnh 3. nh hng ca pH n hp th quang ca cc phc mu ......................44
Hnh 4. nh hng ca nng Triton X- 100 n hp th quang ca cc phc 46
Hnh 5: nh hng ca nng thuc th n hp th quang ca cc phc ....47
Hnh 6,7,8: Kho st bn ca cc phc mu theo thi gian.................................48
Hnh 9: Kho st khong tuyn tnh xc nh Cu(II)..................................................49
Hnh 10: ng chun xc nh Cu(II)......................................................................50
Hnh 11: Kho st khong tuyn tnh xc nh Zn(II).................................................52
Hnh 12: ng chun xc nh Zn(II).......................................................................53
Hnh 13: Kho st khong tuyn tnh xc nh Co(II)................................................55
Hnh 14: ng chun xc nh Co(II)......................................................................56
Hnh 15: Ph hp th ca cc phc Cu-PAN, Zn -PAN, Co-PAN v ph hn hp ca
3 phc theo l thuyt v theo thc t..........................................................................62
M U
Cc nguyn t ng, km, coban c vai tr quan trng trong i sng con
ngi, cc ngnh cng nghip, v s sinh tn ca ng thc vt ni chung. Chng l
cc nguyn t vi lng c tc dng thc y s pht trin ca sinh vt. i vi thc
vt, vic nng cao nng sut, pht trin cht lng ging cy trng l iu thit yu
v thng c thc hin bng vic b sung phn vi lng trong cc giai on pht
trin ca chng. S thiu ht cng nh vt qu ngng cho php ca hm lng cc
nguyn t ny u gy ra nhng tc hi khng nh. V vy, vic xc nh cc nguyn
t trn l rt cn thit.
phn tch, xc nh hm lng cc nguyn t nht l khi chng cng c mt
trong mu phn tch v hm lng thp l vn kh khn. C nhiu phng php
xc nh cc nguyn t vi lng nh in ho, phng php quang ph pht x AES,
ICP- AES, phng php hunh quang, phng php ph hp th nguyn t AAS...c
chn lc, nhy cao, cho kt qu phn tch tt nhng i hi trang thit b gi
thnh ln v k thut phn tch cao.
Phng php quang phn t vi trang b ph bin, chn lc thch hp, k
thut tin hnh n gin, kt hp vi phng php tch sc k, chit t n nhy
cao. Vic phn tch cc nguyn t chuyn tip ni chung v ba nguyn t ng, km,
coban ni ring u c nhng thuc th c trng nhng tn thi gian, s dng dung
mi c. khc phc iu , vic s dng mi trng mixen trong php o trc
quang l mt bc tin khng nh, lm gim thiu cng on chit, tch. c bit,
phng php o trc quang s dng mi trng mixen, thuc th thng dng kt hp
vi thut ton hi qui a bin em li hiu qu tt trong vic xc nh ng thi cc
nguyn t.
Trong cng trnh nghin cu ny, chng ti la chn phng php o
quang vi thuc th 1- (2-pyridilazo )- 2- naphtol (PAN) trong mi trng mixen
nhm xc nh ring r tng nguyn t v kt hp vi thut ton hi qui a bin
tuyn tnh xc nh ng thi Cu(II), Zn(II), Co(II). Nhng kt qu c ng
dng phn tch Cu(II), Zn(II), Co(II) trong cc mu phn vi lng, c bit l phn
bn l v so snh vi php o AAS.
CHNG 1. TNG QUAN

1.1. Vai tr v c tnh phn tch ca ng, km, coban
1.1.1. Vai tr ca ng, km, coban i vi s pht trin ca sinh vt
Cc nguyn t vi lng, tuy c khng nhiu trong c th nhng li ng mt
vai tr ht sc quan trng i vi s sng, chng hn nh h tr cc phn ng ha
hc trong c th; gip c th s dng cht m, m v ng; lm vng chc xng
v iu khin thn kinh, c; iu ha hot ng ca c th, tng tc vi cc cht
khc nh cc vitamin. Hu ht trong s chng c a vo c th u n cng vi
thc n. Hng ngy, ngi trng thnh a vo c th t vi trm g (Se, As...) n
vi mg (Fe, I....). Khi thiu ht nguyn t vi lng c th dn n cc biu hin bnh
l, hay cc s bt n cho c th chng ta. Vic b sung nh k c kim sot cc
nguyn t vi lng l rt c ch cho sc khe v gip ngn nga mt s bnh tt
i vi thc vt, c khong 74 nguyn t trong c 14 nguyn t a lng
(chim 99,95%) v 60 nguyn t vi lng v siu vi lng (0,05%) nhng vn c vai
tr quan trng. Vi lng l c s ca s sng v hu ht cc qu trnh tng hp v
chuyn ha l nh enzym m thnh phn ca enzym ch yu l cc nguyn t vi
lng. Hin nay, c khong 1000 enzym v 1/3 c hot ha bng kim loi. Cc
nguyn t tn ti nhiu dng khc nhau, ch yu gm B, Mn, Zn, Cu, Fe, Mo,
Co.... c tm thy di dng cc phc hu c khong. Cc phc hu c
khong ny c nhng tnh cht c bn v mt ha hc nh: tnh cht ca cc phc
cht khc bit vi tnh cht ca cc thnh phn cu to nn n, phc cht c th tham
gia vo cc phn ng m thnh phn khng c. Cy cn mt lng t phn vi lng
nhng l nhng vi cht thit yu, nu thiu s nh hng n nng sut.
Vi mi sinh vt, khng th ph nhn vai tr ca cc nguyn t vi lng ni
chung v cc nguyn t ng, km, coban ni ring.
ng tc ng n nhiu chc nng c bn v l mt phn cu thnh nn cc
enzym quan trng trong c th. N tham gia vo cc hot ng nh sn xut hng
cu, sinh tng hp elastin v myelin, tng hp nhiu hoormon (catecholamin, tuyn
gip, corticoid...), tng hp nhiu sc t, chuyn ha st v lipit... Do vy, ng l
mt cht dinh dng cn thit cho c th con ngi vi mt hm lng rt nh (80

99,4 mg trong c th ngi trng thnh). Tiu chun RDA ca M v ng i vi
ngi ln khe mnh l 0.9mg/ngy. ng vi hm lng khng thch hp s gy ra
nh hng tiu cc i vi con ngi. S thiu ht ng thng dn n thiu mu
i vi tr nh, mt sc t lng tc... Khi hm lng ng vt c th gy ra ri
lon d dy, nhng bnh v gan, thn v phi. Mc cao nht c th chu c v
ng theo DRI trong ch n ung i vi ngi ln theo mi ngun u l 10
mg/ngy.
i vi thc vt th ng (hm lng 5 20 ppm) - nguyn t rt c bit v
mt sinh vt hc nh hng trc tip n qu trnh sinh trng v pht trin sn
lng ca cy. ng l cht xc tc ca nhng qu trnh oxi ho ni bo; thnh phn
ca men cytochrome oxydase v thnh phn ca nhiu enzim ascorbic, axit axidase,
phenolase, lactase; xc tin qu trnh hnh thnh vitamin A; cn thit cho s hnh
thnh dip lc v lm xc tc cho mt s phn ng khc trong cy, nhng thng
khng tham gia vo thnh phn ca chng. Cy mun pht trin bnh thng, u cn
phi c mt t ng, cy hp th ng di dng Cu(II), nhiu loi cy rau biu hin
thiu ng vi l thiu sc trng, r xung v c mu xanh, chuyn sang qung
mu da tri ti trc khi tr nn bc l, bin cong v cy khng ra hoa c. Lng
ng thiu ht c th c b sung d dng trong mt thi gian di bng cch bn
ng sunfat hay ng oxit.v nu dng nhng hp cht ca ng bn cho t (c
bit l t bn ly) th thu hoch thng tng ln rt cao. Chelat hay ng sunfat
trung tnh (25% ng) rt ph hp cho vic bn l.
Km l nguyn t khng th thiu trong i sng ca ng thc vt. N ng
th hai sau st trong cc nguyn t cn thit vi tng lng km l 2 3 g vi ngi
trng thnh. Km l nguyn t vi lng c trong nhiu enzym quan trng, nht l
enzym tham gia tng hp ARN, protein, kch thch t sinh trng (auxin); cn thit
cho th lc, gip c th chng li bnh tt. Nhu cu v km hng ngy khong 10 -15
mg i vi ngi trng thnh. Vic thu np qu nhiu km ca c th c th sinh ra
s thiu ht ca cc khong cht khc trong dinh dng. S thiu ht km li
nhng hiu ng r nt trong vic tng trng ca ng vt, gy ra cc d tt mt,
xng, tim, no, gy ra s hot ng khng bnh thng ca cc c quan th gic, v

gic, khu gic v tr nh.
Trong thc vt, km (hm lng 25 150 ppm) c hp th di dng Zn(II)
c coi nh l mt trong cc nguyn t vi lng u tin cn thit cho cy trng,
lin quan n tng hp v hot ha enzym, l thnh phn ca cc auxin (c tc dng
iu ha sinh trng), cn thit cho vic sn xut ra cht Dip lc v cc
Hydratcarbon, lm tng tc trao i cht ca cy. Tuy ch c s dng vi liu
lng rt nh nhng c nng sut cao khng th khng c km. Km cng khng
c vn chuyn s dng li trong cy nn biu hin thiu thng xy ra nhng l
non v b phn khc ca cy, chc nng t bo ca cy b suy yu. Km thng c
bn cho cy bng cch phun ln l dung dch ZnSO4 (23% Zn) hay dng Zn - EDTA
bn trc tip cho t. Vic b sung km cn gip tng cng kh nng s dng ln
v m
Coban c nhiu vai tr quan trng trong c th nh kch thch to mu, kch
thch tng hp protein c, tham gia chuyn ho gluxit, chuyn ho cc cht v c.
Coban c tc dng hot ho mt s enzim v c ch mt s enzim khc. Coban tham
gia vo qu trnh to vitamin cobalamin - B12 (C36H88O24N14PCo). Coban kt hp vi
Mangan c tc dng rt tt i vi cc triu chng au na u. C th thiu Coban
c nhng biu hin u tin l cm gic mt mi, thiu tp trung v thiu mu. Coban
khng c nh hu ht cc hu ht cc kim loi nng v theo nhng nghin cu mi
y ti M th khng c s lin h gia coban trong nc v bnh ung th ngi.
Tuy nhin, vi hm lng ln coban s gy tc ng xu n c th ngi v ng
vt. Triu trng nhim c coban ngi l nn ma, tiu chy . Thc t lng
coban m con ngi hp th hng ngy t nc nh hn t thc phm.
Cng nh ng vt, trong thc vt, coban l thnh phn trung tm ca vitamin
cobalamin (vitamin B12). Hot tnh xc tc ca carbonxylase c gia tng khi c mt
Mg hoc Mn, Co. Coban cn cho vic ra hoa, qu, chng su bnh, nng nng, nh
hng tt n bn vng ca chlorophyll, tc dng tt n tng hp carotenoid, tia
gamma pht ra t 60Co hin ang c s dng dit vi khun v tng sc khng
trn rau qu. S c mt ca coban rt cn thit trong qu trnh ln men, trao i cht
10
v c ngha i vi c nh nit phn t bng con ng sinh hc. Co cha trong

thnh phn ca nhiu alumosilicat. Hm lng ca Co trong t nh hn Mn, Zn, Cu.
t hnh thnh trn baz giu Co hn trn axit. Co tn ti trong t ch yu
dng mui ca Co2+ v dng Co2+ hp ph trao i. iu kin phn ng ca t l
trung tnh v kim th tnh linh ng v d tiu ca Co gim.
Cc ion chuyn tip Zn2+, Cu2+, Co3+,Mn2+lm thay i tnh thm mng t
bo, pH t bo cht ca vi khun, nm lm chng t cht. Do vy khi cung cp cht
cho cy chng ta cn rt ch n tt c cc cht, mt d c cc cht ch dng vi
lng hay vt nhng nh hng thc s ca chng ln qu trnh sinh trng cng
ging nh cc vitanmin ln c th ng vt. Mui ca cc nguyn t vi lng thng
khng tan trong nc hoc t tan, phn t chng cng knh do cy kh hp thu d
trong t nhin, vic a chng vo cy qua thm thu cng kh hn. Tuy nhin, do
cc nguyn t vi lng a s l kim loi nng hay kim loi chuyn tip nn d to
phc v chng theo phc cht thm vo cy, gip cy d hp thu vi lng hn v cn
ci thin s hp thu cc nguyn t a lng (Mg, Ca, S, Fe...) [7],[15], [16], [17],
[24],[24], [46].
1.1.2. c tnh phn tch ca ng, km, coban

1.1.2.1. c tnh phn tch ca ng
ng l mt kim loi nng thuc nhm IB, chu k 4, th 29 trong bng tun
hon cc nguyn t ha hc v c cu hnh electrodn l 1s2 2s2 2p6 3s2 3p6 3d10 4s1.
ng c ba mc oxi ha: Cu, Cu(I), Cu(II).
ng kim loi
Cu kim loi th hin tnh kh, bn vi oxi, ch yu tc dng vi lu hunh, ch
tan c trong mi trng axit c tnh oxi ha, trong dung dch NH3 c mt oxi.
i vi cc halogen, ng phn ng rt d dng to thnh cc halogenua.
ng c th tan trong dung dch amoniac khi c mt ca O2 khng kh.
2Cu + 8NH3 +O2 +H2O 2[Cu(NH3)4](OH)2
Ngoi ra, ng d to nn hp kim vi cc kim loi khc, d to hn hng vi
thu ngn v to nn nhiu phc cht.
Hp cht ca Cu(I)
11
Hp cht ca Cu(I) c c tnh oxi ha v tnh kh.

Tuy c cu hnh d10 nhng trong nc mui Cu(I) t phn hu:
2Cu+
Cu + Cu2+
E0 = + 0,38 V
Cc hp cht Cu(I) d b oxy ha (ngay c bi oxy khng kh) chuyn thnh

dn xut bn ca Cu(II):
2Cu2Cl2 + O2 + 4HCl 4CuCl2 + 2H2O
Vy, hp cht Cu(I) khng bn, ch tn ti trong dung dch nc di iu kin
nht nh, v d CuCl tan t trong nc lnh nhng phn hu trong nc nng. Tuy
nhin, trong nc, Cu(I) c lm bn khi to thnh kt ta t tan nh CuI, CuCN
hoc ion phc tng i bn nh [Cu(NH3)2]+, [CuX2]- (trong X = Cl-, Br-, I-,
CN-). Mt nguyn nhn quan trng ca s lm bn l kh nng nhn ca nhng
anion I- v CN-. Khi c mt nhng anion ny trong dung dch, nhng cn bng trn
s chuyn dch sang pha to thnh Cu(I).
Cc halogen Cu2X2 khng tan trong nc v axit nhng li tan kh nhiu (c
bit khi un nng) trong dung dch m c ca cc axit hirohalogenua v dung dch
NH3 nh to thnh phc cht:
Cu2Cl2 + 2HCl 2H[CuCl2]
Cu2Cl2 + 4NH3 2[Cu(NH3)2]Cl
Hp cht ca Cu(II)
Trng thi oxy ha +2 l rt c trng i vi ng. Cc hp cht Cu(II) ni
chung u bn hn cc dn xut cng kiu ca Cu(I).
D to thnh Cu(OH)2, khi OH- va , to c kt ta Cu(OH)2. Khi d OH-,
to thnh CuO 2- (Cuprit). Khi nung nng, Cu(OH)2 chuyn thnh CuO:
0
50 80 C
Cu(OH)2
CuO + H2O
Cu(OH)2 cn th hin tnh cht axit yu.

Cu(II) oxit (CuO) l cht bt mu en nng chy 1026 oC v trn nhit
mt bt oxy bin thnh Cu2O. CuO khng tan trong nc nhng tan d dng trong
dung dch axit to thnh mui Cu(II):
CuO + 2HCl CuCl2 + 2H2O
12
Khi un nng vi dung dch SnCl2, FeCl2, CuO b kh thnh mui Cu(I):
2CuO + SnCl2 2CuCl + SnO2
3CuO + 2FeCl2 2CuCl + CuCl2 + Fe2O3
Cu(II) hiroxit Cu(OH)2 l kt ta bng mu lam, d mt nc bin thnh oxit
khi un nng. Cu(OH)2 khng tan trong nc nhng tan d dng trong dung dch axit,
v ch tan trong dung dch kim 40% khi un nng:
Cu(OH)2 + 2NaOH Na2[Cu(OH)4]
Cu(OH)2 + 4NH3 [Cu(NH3)4](OH)2
a s mui Cu(II) d tan trong nc, b thy phn v khi kt tinh t dung dch
thng dng hirat. Mui tan tt nht l mui Cu(II) vi cc anion NO3-, SO4 2-, Cl-.
Cu(II) c i lc i mnh vi sunphua.
Khi gp cc cht kh, mui Cu(II) c th chuyn thnh mui Cu(I) hoc thnh
Cu kim loi. Do tnh cht oxi ho m Cu c th c tch bng phng php in
ho qua qu trnh in phn lm giu.
Do cu hnh electron nh trn nn Cu(II) c nhiu kh nng to phc vi cc
phi t v c v hu c vi s phi tr bng 4. Cu(II) khng to phc clorua.
CuO tan d dng trong dung dch NH3 to thnh phc cht amoniacat:
CuO + 4NH3 + 2H2O [Cu(NH3)4](OH)2
Cu(OH)2 tan d dng trong dung dch NH3 c:
Cu(OH)2 + 4NH3 [Cu(NH3)4](OH)2
Mui Cu(II) c kh nng phn ng vi feroxianat Fe(CN)2 to thnh kt ta
nu Cu2Fe(CN)6. Trong dung dch amoniac, Cu(II) phn ng mnh lit vi cc phn
t NH3 to thnh ion phc Cu(NH3)42+ c mu xanh lam. N cng to phc vi mt
s tc nhn hu c nh 1-(2-pyridylazo)-2-naphtol, 8-hiroxylquinolin, -benzoin
oxim (C6H5CH(OH)C(NOH)C6H5),
natriietyldithiocacbamat, ithizon, Nhng
phc ny cho php xc nh ng bng phng php khi lng, th tch hay trc
quang. [9], [14].
1.1.2.2. c tnh phn tch ca km [3]
13
Km l mt kim loi nng thuc nhm IIB, chu k 4, th 30 trong bng tun
hon cc nguyn t ha hc v c cu hnh electron l 1s2 2s2 2p6 3s2 3p6 3d10 4s2.
Km c hai mc oxi ha: Zn, Zn(II).
Km kim loi
Km l kim loi c tnh kh mnh, do cu hnh nn c 2 mc oxi ha v c tnh
lng tnh c hai dng.
Trong khng kh, km b mt lp mng mng oxit hoc cacbonat baz bao ph
ngn cn n khng b oxi ho tip tc. nhit thng, Zn bn vi khng kh m
v nc do c mt lp mng bo v. l lp hyroxit to thnh mng trn b mt
km.
2Zn + 2H2O + O2 2Zn(OH)2
Do c th in cc kh m, Zn tc dng d dng vi cc loi axit:
Zn + 2H3O+ + 2H2O [Zn(H2O)4]2+ + H2
Km c tnh kh mnh nn c th kh HNO3 rt long n ion amoni:
4Zn + 10HNO3 4Zn(NO3)2 + NH4NO3 + 3H2O
Km c th tan d dng trong dung dch kim gii phng H2 nh nhm:
Zn + 2H2O + 2OH- [Zn(OH)4]2- + H2
Km c th phn ng d dng vi cc kim: Cl2, S, C
Km tan khng ch trong dung dch kim mnh m c trong dung dch NH3
Zn + 4NH3 + 2H2O [Zn(NH3)4](OH)2 + H2
Hp cht ca Zn(II)
Km oxit (ZnO) l cht bt xp, mu trng, ho vng khi un nng. Khi lm
lnh li c mu trng. ZnO l cht kh nng chy (t 0nc = 19500C), c th thng hoa,
khng phn hu khi nung nng. Hi ca ZnO rt c, ZnO khng tan trong nc, tan
trong dung dch axit, dung dch kim:
ZnO + 2KOH (nng chy) K2ZnO2 + H2O
Km hyroxit Zn(OH)2: l kt ta nhy, rt t tan trong nc v c mu trng.
L cht lng tnh in hnh, tan trong dung dch axit to thnh mui Zn(II) v tan
trong dung dch kim to thnh phc cht hyroxozincat.
14
Tnh lng tnh ca hyroxit cng vi th in cc kh m ca kim loi gii

thch tnh d tan ca Zn trong dung dch kim gii phng kh hyro.
Zn(II) to phc vi nhiu thuc th hu c.
Zn(II) to phc clorua [ZnCl4]2- trong mi trng HCl 2M.
Km hyroxit tan trong dung dch NH3 to thnh amoniacat:
Zn(OH)2 + 4NH3 + 2H2O [Zn(NH3)4](OH)2
Km sunfat (ZnSO4) tch ra t dung dch nc di dng tinh th hyrat c
thnh phn ZnSO4.7H2O v dng nh vy gi l cuporot km. N c dng trong
cng ngh in hoa v nhum, m km bng in phn.
Km clorua (ZnCl2) kh iu ch trng thi khc nhau. N thng cha 5%
nc v clorua baz. Dung dch ZnCl2 c th ty oxit khi b mt kim loi khi hn.
Amoni tetraclorozincat (NH4) [ZnCl4] cng c s dng cho mc ch ny khi hn.
Km sunfua (ZnS) l mt trong t sunfua c mu trng, ZnS c iu ch khi
cho sunfua kim loi kim hoc kh H2S tc dng vi mui km:
Zn 2+ + S 2- ZnS .
ZnS hnh thnh pH = 2 v khng tan trong S2- d. [9], [14].
1.1.2.3. c tnh phn tch ca coban [3]
Coban l mt kim loi nng thuc nhm VIIIB, chu k 4, th 27 trong bng
tun hon cc nguyn t ha hc v c cu hnh electron l 1s2 2s2 2p6 3s2 3p6 3d7 4s2.
Coban c cc mc oxi ha: Co, Co(II), Co(III)...
Coban n cht
nhit thng, coban tng i bn khng b tn cng bi oxi v nc do
c mng oxit bo v. nhit cao, n tc dng vi hu ht cc kim. Coban rt
c trng vi mc oxi ho +2 trong cc hp cht.
Trong mi trng kim, mui coban to kt ta mu xanh lam
CoCl2 + OH - CoOHCl- + ClKt ta ny sau chuyn thnh Co(OH)2 mu hng.
Coban tan rt nhanh trong axit HCl, HNO3, H2SO4 hoc axit pecloric nhng ch
tan rt chm trong axit HF gii phng ra kh H2.
15
Coban kim loi c tnh kh, kt hp vi halogen (X) hoc dung dch HX to ra
cc ihalogenua:
Co + Br2 CoBr2
Coban to phc cht vi NH3 trong dung dch NH3. Phc cht to thnh c mu
vng nht [Co(NH3)6]2+
Co2+ + 6NH3 [Co(NH3)6]2+
Sau phc cht b oxi ho trong khng kh to thnh phc cht mu nu .
[Co(NH3)6]2+ + O2 + 2H2O 4[Co(NH3)6]3+ +4OHCo(II) cng to phc cht vi CN-, nhng phc cht c bn km hn. Ngoi
ra, coban cn to phc cht vi nhiu thuc th hu c nh dimetylglyoxim,
diphenylglyoxi, 1-nitrozo-2-naphol....Cc phc cht ny c s dng phn tch
coban cho nhy cao.
Hp cht ca Co(II)
Coban oxit- CoO v coban hidroxit- Co(OH)2 u c tnh lng tnh yu, khng
tan trong nc, d tan trong axit to mui tng ng, tan trong dung dch kim mnh,
c nng to nn dung dch mu xanh lam cha ion [Co(OH)4]2-.
Cc mui coban nh: clorua, nitrat, sunfat u d tan trong nc. Mui hidrat
coban l nhng tinh th mu hng, mui khan c mu xanh. Dung dch mui coban
trong nc c mu hng v phc [Co(H2O)6]2+, nhng khi c cn hay thm cht hidrat
ho (HCl c, ru...) th chuyn sang mu xanh.
Mui n gin ca coban u khng bn, n ch tn ti dng mui phc:
K3[Co(NO2)6], K3[Co(CN)6]
Cc mui coban trong dung dch u b thu phn nn dung dch nc cc mui
u c phn ng axit yu.
Mui coban(II) dng khan c mu khc vi mui dng tinh th hidrat, v d
CoBr2 mu lc, CoBr2.6H2O c mu . Mui ca axit mnh nh clorua, nitrat, sunfat
tan d trong nc cn mui ca axit yu nh sunfua, cacbonat, oxatat kh tan. Khi
tan trong nc, cc mui u cho ion bt din [Co(H2O)6]2+ mu lc.
16
Co(OH)2 l kt ta khng nhy, khng tan trong nc, c kin trc lp. Co(OH)2
mu hng, trong khng kh chuyn chm thnh Co(OH)3 mu nu.
4Co(OH)2 + O2 + 2H2O 4Co(OH)3
Co(OH)2 tan c trong dung dch kim mnh, c nng.
Co(II) to phc clorua [CoCl4]2- trong mi trng HCl 4 9M.
Co(OH)2 tan trong dung dch NH3 to thnh phc cht :
Co(OH)2 + 6NH3
[Co(NH3)6] (OH)2
Cc ion Co2+ to nn nhiu phc cht bt din vi s phi tr 6.

Nhng ion phc bt din nh [Co(H2O)6]2+, [Co(NH3)6]2+, [CoF6]4-, [Co(CN)6]4Nhng ion phc t din nh [CoCl4]2-, [CoBr4]2-, [CoI4]2-, [Co(H2O)4]2-,
[Co(SCN)4]2-...
a s phc t din ca Co(II) u c dng mui kp, chng phn hu khi pha
long nc nn mu ca dung dch bin i:
[Co(SCN)4]2- + 6H2O [Co(H2O)6]2+ + 4SCNDo vy, nhn bit Co(II) trong dung dch bng cch cho Co(II) kt hp
vi SCN- to nn [Co(SCN)4]2- mu xanh lam v khi pha long nc, dung dch mu
xanh lam tr li mu hng.
Ngoi ra, Co2+ cn c kh nng to phc mu vi nhiu thuc th hu c nh:
PAN, PAR, 2 pyridyl hydrazone, 2 benzoylpyricdine.
Cc hp cht t tan ca coban c gi tr trong phn tch l Co(OH)2, CoS,
Co3(PO4)2a s cc mui ny u tan trong amoniac to thnh amoniacat.
CoS ch hnh thnh trong mi trng kim d bn.
Hp cht ca Co(III)
Khi un nng trong dung dch kim mnh v c, Co(OH)3 mi iu ch c th
tan to thnh hiroxocobantat.
Co(OH)3 + 3KOH K3[Co(OH)6]
Co(III) c tnh oxi ho.
Khi un nng, Co2O3 c th b H2, Co, Al, Co...kh n Co3O4, CoO, hay Co.
125 C
3Co2O3 + H2
2Co3O4 + H2O
0
17
Co2O3 l cht oxi ho mnh, khng tan trong nc, tc dng vi axit clohiric
gii phng kh clo v tc dng vi axit sufuric gii phng kh oxi.
Co2O3 + 6HCl 2CoCl2 + Cl2 + 3H2O
Co(OH)3 l kt ta mu nu, bn trong khng kh, khng tan trong nc. Khi
un nng nh, bin thnh Co3O4 v CoO.
150 C
250 C
940 C
Co(OH)3
CoOOH
Co3O4
CoO
0
Co(III) to c rt nhiu phc cht v hu ht chng c cu hnh bt din.

Phc cht Co(III) bn hn phc cht Co(II). Phng php chung iu ch phc
cht ca ion Co(III) l oxi ho mui Co(II) trong dung dch bng O2 hoc H2O2 khi c
mt cht xc tc c hot tnh b mt v phi t.
2[Co(NH3)6]Cl2 + 2NH4Cl + H2O2 2[Co(NH3)6]Cl3 + 2NH3 + 2H2O
Trong kt ta thu c, ngoi mui mu vng ca [Co(NH 3)6]Cl3 cn c mt t
kt ta mu hng ca [Co(NH3)5H2O]Cl3 v mu ca [Co(NH3)5Cl]Cl2. Vic to
nn nhng phc cht vi vi phi t khc nhau trong cu ni l mt c im ca ion
Co(III).[9], [14].
1.2. Mt s phng php quang xc nh Cu(II), Zn(II), Co(II)

xc nh Cu(II), Zn(II), Co(II), c khng t nhng phng php phn tch:
Cc phng php ho hc nh phng php phn tch th tch, phng php
oxi ho - kh, phng php chun complexon
Cc phng php phn tch cng c nh cc phng php phn tch in ha
( phng php cc ph, phng php Von ampe ho tan, phng php Von ampe
ho tan hp ph) v cc phng php quang (phng php quang ph pht x nguyn
t AES, phng php ph hp th nguyn t AAS, phng php ICP AES, phng
php trc quang).
Cc phng php xc nh cc nguyn t vi lng nh in ho, phng php
quang ph ph pht x AES, ICP AES, phng php hunh quang...c chn lc,
nhy cao, cho kt qu phn tch tt nhng i hi trang thit b gi thnh ln v
k thut phn tch cao. Bn cnh , phng php ph hp th nguyn t AAS v
18
trc quang d tin hnh hn vi nhng trang thit b thng thng v cho kt qu c
chnh xc kh cao, l cc phng php ph bin xc nh lng vt. [14].
1.2.1. Phng php ph hp th nguyn t AAS

Nguyn tc chung ca phng php ny l da vo kh nng hp th bc x
c trng ca cc nguyn t trng thi hi t do. y l phng php c nhy
v chn lc rt cao, c dng rt rng ri xc nh lng vt cc kim loi.
ng, km, coban c xc nh bng phng php hp th nguyn t trong
ngn la khng kh C2H2 bc sng hp th ln lt l 324,7nm; 219,3 nm v
240,7 nm.
Mt s nghin cu c th xc nh Cu(II), Zn(II), Co(II) nh sau:
Ngi ta s dng phng php hp th nguyn t xc nh ng trong nc
sau khi lm giu ng bng cch chit hoc dng nha trao i ion. C th chit
ng bng 5 cloxalixyl aldoxim. Xc nh ng trong ngn la khng kh axetilen.
Phng php AAS kt hp vi phng php chit c th xc nh vi lng Cu
v Zn trong du v m n. Vt kim loi trong du m vi nng thp cng c th
lm hng hng v v mu sc. Cng trnh nghin cu thu hi c tin hnh vi du
u nnh c hm lng kim loi thp. Mu x l vi dch chit (HCl 18% v EDTA
0,01%) axit HNO3 m c. Qua cc bc x l c th thu hi ti 96% Cu.
o km vch 219,3 nm; nhy 0,01 g/ml. nng cao nhy, cn lm
giu km trc khi o ph hp th nguyn t bng cch chit hoc dung nha trao
i ion. Km c chit bng dung dch 1, 2 naphtoquinon thiosemicabazon trong
metylisobutylxeton. T pha hu c ngoi, ngi ta xc nh km trong ngn la C2H2
khng kh. Gii hn pht hin trong pha hu c l 8.10 -7M. chit cng c th
dng pycolyandehit salixyloyl hydrazon trong metylisobutylxeton v phun phn
chit vo ngn la C2H2 khng kh.
Bng phng php F-AAS, cc tc gi Sibel Saracoglu, Umit Divrikli, Mustafa
Soylak v Latif Elci xy dng mt quy trnh hon chnh xc nh cc kim loi
Cu, Fe, Pb, Cd, Co, Ni trong cc mu sa v soda vi hiu sut hn 95%. Ngoi ra
19
cc tc gi Serife Tokalioglu, Senol Kartal v Latif Elci xc nh lng vt ion kim

loi trong nc sau khi lm giu vi lch chun trong vng 0,8-2,9% v gii hn
pht hin 0,006-0,277ppm.
Cc tc gi cng ng dng phng php ny xc nh ng thi coban,
st v niken trong dung dch cht in ly ca mangan. Bc sng hp th ca coban,
st v niken tng ng l 240,7; 248,3; v 232,0 nm. nh hng ca nn Mn2+ v
lng thch hp MnSO4 v (NH4)2SO4. Sai s tng i ca coban l 3,1%, hiu sut
thu hi t 97,6%. [3],[6].
1.2.2. Phng php phn tch trc quang

1.2.2.1. Phng php phn tch trc quang vi cc loi thuc th hu c
Nguyn tc chung ca phng php ny l da vo kh nng to phc mu ca
cc nguyn t cn xc nh vi thuc th thch hp v o hp th quang ca phc
. y l phng php c s dng ph bin nht trong cc phng php phn
tch ho l. Bng phng php ny c th nh lng nhanh chng, n gin vi
nhy v chnh xc kh cao, ng tin cy. [4].
Phng php trc quang dng thuc th dithizon: Dithizon phn ng vi Cu(II)
trong dung dch axit v c to thnh phc mu tm. Trong axit HCl 1N hoc
H2SO4, dithizon phn ng vi Cu2+, Au2+, Hg2+, Pd2+, Ag+. Bc c th b loi tr bi
kt ta vi HCl. Bi3+ phn ng vi dithizon pH = 2, cn Te(III) phn ng khong
pH = 3 - 4, ion gy cn s khng gy cn tr trong axit c tr khi chng c lng
ln. Phng php ny rt nhy, c th xc nh khong 5g Cu vi dung mi chit l
CCl4. o hp th nh sng cu dung dch bc sng = 535nm. [30]
Narinder Kumar Agnihotri, Vinay Kumar Singh, Har Bhajan Singh nghin
cu v tng hp t liu v s hnh thnh phc ca Cu(II) trong cc loi thuc th hu
c khc nhau v kt qu c tng kt nh sau:
Bng 1. S hnh thnh phc Cu(II) trong mt s thuc th hu c
ST
T
Thuc th
Mi trng/dung
mi
20
max
(nm)
(l/mol.cm)
Khong
tuyn tnh
g/ml
1
2
3
4
5
6
7
8
9
10
11
Dithizone
Natri ietyl ithio
cacbamat
Cuproine
Cuprizone
Bathocuperione
Neocuproine
CCl4
Axit axetic
550
430
4,52
1,89
0,4 2,0
--
H2O - DMF
546
600
479
454
0,64
1,6
1,42
0,79
<10
< 0,4
0,1 40
0,1 - 10
n hexanol
Isoamyl alcol/
n hexanol
Zephiramine/CHCl3
CCl4
Zincon
ithiocacbamat
4-(2-pyridylazo)resorcinol (PAR)
1-(2-pyridylazo )- Etanol nc
2- naphtol (PAN)
625
436
535
1,49
1,18
0,2 1,6
595
0,5 3,0
1-(2-pyridylazo )- Triton X-100

2- naphtol (PAN)
555
5,21
0,08 4,00
0,5 3,0
Cc phc cht ca Cu(II) thng thng c chit nh cc dung mi hu c

(CCl4, CHCl3, isopentanol...). Nhng dung mi ny khng nhng c m cn gy
nhim mi trng. Dithizone l mt trong s nhng tc nhn nhy nht khng ch c
chn lc km m cn km bn. Cuprizone c coi l tc nhn c nhy quang
hc cao hn i vi Cu(II) nhng c chn lc km hn tc nhn cuproine....i
hi phng php trao i ion. S la chn dung mi ph hp l rt quan trng i
vi vic chit tch phc kim loi vi PAN. Cloroform c s dng rng ri. Vic
chit thng khng hon ton vi CCl4 cng nh ete v benzen. Trong nghin cu
ny, phn ng to phc gia PAN v Cu(II) vi s c mt ca cht hot ng b mt
trung tnh l Triton X-100 c kho st. Cc iu kin ti u c pht trin
xc nh lng vt Cu(II). nhy v khong tuyn tnh ca phng php ci
tin ny c so snh vi cc phng php o quang thng thng. ng thi i
chiu, nh gi tnh ph hp vi phng php ph hp th nguyn t AAS. [40]
Mt s nghin cu khc cng xc nh Cu(II) bng cc loi thuc th hu c
nh dithizon natridiethyl dithiocacbamat, Alizarin S, dithizon, axit rubeanic,
natridiethyldithiocacbomat, 2,2-biquinoline, cupferon...
21
Vi thuc th Natridiethyl dithiocacbamat (NaDDC), phn ng to phc trong

mi trung axit long pH= 4 11, phc Cu (II) vi NaDDC, kh tan trong nc, tan
nhiu trong mt s dung mi hu c nh tetrecloruacacbon, ru amylic, clorofom.
xc nh Cu bng thuc th ny, ngi ta tin hnh chit trc quang. hp th
nh sng phc CuDDC ti bc sng 430nm. Trong php o ny, Cu c th b nh
hng bi Fe3+, Ni2+, Mn2+, Co2+,. Do cng to phc mu vi thuc th NaDDC.
C th loi tr nh hng ca cc ion ny bng cch thm vo mt lng cht che
nh amonixitrat, axit xitric, EDTA, kali natri tactratDng dimethylglyoxim khc
phc nh hng ca Ni2+ v Co2+. Loi tr nh hng gay nn bi lng ln Fe3+ v
Mn2+ bng cch x l phn chit tetraclorua cacbon vi amoni long, cupfferon, 2,2 biquinolin phn ng vi Cu(I) to thnh mt phc d chit bng ru amylic. o
hp th quang bc sng = 545nm. Thuc th ny phn tch Cu trong khong
vt hoc qung c cha 0,001 n 10% thu c kt qu tt v khng b nh
hng.[29]
Ngoi ra, ngi ta cng c th xc nh Cu2+ bng thuc th 2,9 dimity - 4,7
diphenyl - 1,10 - phenantronlin disufonat, hin nay c coi l mt trong cc phng
php tiu chun xc nh ng trong nc. Phc ca ng vi thuc th ny c
mu da cam, tan trong nc. Phn ng to phc vng cng pH = 3,5 n 11, tt
nht l pH = 4 - 5. a pH v 4,3 c th dng HCl v m citrat. hp th
quang ca phc ti = 484nm. Xyanua, thiocyanat, pesunfat v EDTA l nhng ion
c th gy nh hng n phng php xc nh. Phng php ny cho php pht
hin nng ng ti 20 g/l. [26]
Xc nh km bng phng php trc quang vi thuc th PAR pH = 8 trong
mi trng mixen trung tnh l cht hot ng b mt Triton X-100. Phc vng cng
ny cho cc i hp th 493 nm, h s hp th mol phn t ca phc = 77728
l/mol.cm v nhy Sandell tng ng S = 0,84 ng/cm 2. Khong tuyn tnh ca
Zn(II) l 0,18 2,0 g/l. Phng php ny c ng dng thnh cng xc
nh Zn(II) trong mu thuc nh mt v mu insulin vi kt qu tt. [41]
Shigeya Sato, Toshie Sato v Sumio Uchikaoa tng hp 2-(3,5 diclo-2
pyridylazo)-5-dimetylaminophenol (3,5-diCl-DMPAP) xc nh coban. Thuc th
22
3,5-diCl-DMPAP phn ng vi coban trong mi trng pH= 2,2 6,0, nhit

phng to thnh phc ML2 tan trong nc, hp th quang t cc i bc sng
max = 590 nm, h s hp th phn t gam ca phc = 8,4.104 (l/mol.cm). nh
hng ca cc ion kim loi chuyn tip khc c loi tr bng phng php chit
vi dung mi 8- hidroxylquinolin. Phng php ny c ng dng thnh cng xc
nh coban trong cc mu thp. [9]
Phng php trc quang tuy k thut v phng tin my mc khng qu phc
tp, lp li ca php o cao nhng chnh xc v nhy khng cao nn ch
c s dng khi hm lng ng trong nc kh ln hoc c lm giu trc khi
phn tch.
1.2.2.2. Phng php phn tch trc quang vi thuc th PAN
Diniz Maria Celeste Teixeira, Filho Orlando Fatibello v Rohwedder Jarbas [14]
lm giu v xc nh Cu bng thuc th PAN nh sau: dung mi c s dng
y l MIBK, Cu(II) to phc vi PAN v c chit bng MIBK. Nu t l th tch
pha nc:pha hu c = 2:1 th khong tuyn tnh ca Cu l 100 1600ppb vi
SD=2% (200ppb, n=5) v gii hn pht hin l 20ppb.(R=0,9995). Nu t l th tch l
10:1 th khong tuyn tnh ca Cu l 25 500ppb (R=0,9994), gii hn pht hin l
5,0ppb v SD=6% (50ppb, n=5)
Narinder Kumar Agnihotri, Vinay Kumar Singh, Har Bhajan Singh tin hnh
nghin cu xc nh lng vt Cu2+ bng phng php trc quang s dng thuc th
PAN trong s c mt ca cht hot ng b mt trung tnh l Triton X-100, h s hp
th mol phn t v nhy ( S) ca phc Cu2+- PAN bc sng 555nm tng ng
l 5,21.104l.mol-1cm-1 v 1,22 ng.cm-2. Gii hn pht hin ca Cu2+ l 4,0 ng .ml-1 v
khong tuyn tnh tun theo nh lut beer l 0,08 4,00 g.ml-1 Cu2+ hm lng
ng trong mt s mu sinh hc v cc mu hp kim tiu chun c tin hnh
xc nh kt qu t c l rt ph hp so vi phng php AAS. [40]
Thanasarakhan Wish, Liawruangrath Saisunee, Wangkam Sunanta v
Liawruangrath Boonsom xc nh Zn bng phng php o quang s dng thuc
th PAN to phc vi s c mt ca Triton X-100. Phc Zn-PAN c mu hng ti
23
pH=9,5 vi bc sng cc i max = 553 nm. Khong tuyn tnh l 0,1 1,0 ppb.
Gii hn pht hin LOD = 0,02 ppb, gii hn nh lng LOQ = 0,06 ppb.
G.A.Shar and G.A.Soomro xc nh Co(II), Ni(II), Cu(II) bng 1-(2
pyridylazo)-2 naphthol trong mi trng mixen vi cht hot ng b mt Tween 80
(5%). Khong tuyn tnh: Co(II) 0,5 4 (ppb), Ni(II) 0,5 4 (ppb), Cu(II) 0,5 3
(ppb). Gii hn pht hin: Co(II) 6,7 (ppb), Ni(II) 3,2 (ppb), Cu(II) 3,9 (ppb). Cc i
hp th: Co(II) 580 (nm), Ni(II) 570 (nm), Cu(II) 555 (nm). pH xc nh Co(II),
Ni(II), Cu(II) ln lt l 5; 5,5 v 6,5. So snh vi phng php AAS: thy khng
khc bit gia 2 phng php ( tin cy 95%). Phng php c ng dng xc
nh Co, Ni, Cu trong nc thi cng nghip, dc phm. [27], [33], [35], [36].
1.2.2.3. Phng php phn tch trc quang trong mi trng mixen
Mixen l cht hot ng b mt, tp hp cc phn t (c 100 1000 phn t)
c sp xp trt t, c nhy cao vi nhiu php phn tch nh phng php o
quang UV-Vis, sc k lng bn mng, quang ph hp th nguyn t. Mixen c tc
dng lm tng qu trnh ha tan ca cc cht v thng lm tng hp th phn t
mol. [42], [45].
Cc cht hot ng b mt c th c phn thnh bn loi da vo bn cht
ca nhm chc a nc v ion phn ly trong mi trng nc.
Cht hot ng b mt anion, mang in tch m.
Cht hot ng b mt cation, mang in tch dng.
Cht hot ng b mt khng ion.
Cht hot ng b mt lng ion, c in tch m hoc dng, tu theo pH
ca mi trng. [10].
Cc cht hot ng b mt Tween 80 v Triton X-100
Tween v Triton X-100 l cc cht hot ng b mt khng ion v c cng thc
cu to nh sau: [47], [48], [49]
Tween 80
24
Triton X-100
Mt s nghin cu o quang trong mi trng Tween 80

G.A.Shar and G.A.Soomro xc nh Co(II), Ni(II), Cu(II) bng 1-(2
pyridylazo)-2 naphthol trong mi trng cht hot ng b mt Tween 80 . Khong
tuyn tnh: Co(II) 0,5 4 (ppb), Ni(II) 0,5 4 (ppb), Cu(II) 0,5 3 (ppb). Gii hn
pht hin: Co(II) 6,7 (ppb), Ni(II) 3,2 (ppb), Cu(II) 3,9 (ppb). Cc i hp th: Co(II)
580 (nm), Ni(II) 570 (nm), Cu(II) 555 (nm). pH xc nh Co(II), Ni(II), Cu(II) ln
lt l 5; 5,5 v 6,5. Nghin cu kho st c t l to phc ca kim loi vi
phi t M:L = 1:4 v nng Tween ti u l 5%. So snh vi phng php AAS:
thy khng khc bit gia 2 phng php ( tin cy 95%). Phng php c ng
dng xc nh Co, Ni, Cu trong nc thi cng nghip, dc phm. [27]
M.Arab Chamjangali xc nh ng thi coban, niken v paladi trong mi
trng cht hot ng b mt Tween 80. C s ca phng php da trn s to
phc ca Co(II), Ni(II) v Pd(II) vi thuc th PAN trong mi trng tween 80.
Nghin cu kho st cc cc i hp th ca Co(II): 575 v 615 nm, ca Ni(II):
569 v 530 nm, ca Pd(II): 615 v 660 nm ti pH = 5, nng Tween ti u l 0,3%.
Tt c cc yu t nh hng n nhy ca phng php u c ti u ho v
xc nh c vng tuyn tnh ca Co(II), Ni(II) v Pd(II). Ma trn c chun thc
nghim c xy dng bng cch o hp th quang ca 21 mu vi hm lng
Co(II),Ni(II) v Pd(II) tng ng thuc khong 0,1 1,0; 0,05 0,5 v 0,05 4,0
mg/l, trong vng bc sng 520 700 mm. S dng m hnh bnh phng ti thiu
25
tng phn (PLS), bnh phng ti thiu nghch o (ILS), bnh phng ti thiu
thng thng (CLS) v hi quy cu t chnh (PCR) xy dng ng chun a
bin t xc nh hm lng cc kim loi c trong mu thc t (nc hoc hp
kim). [38]
G.Bagherian xc nh ng thi Co(II) v Pd(II) vi thuc th c s dng
l PAR trong s c mt ca cc loi cht hot ng b mt SDS, Tween 80 v Triton
X-100. Kt qu kho st trong ba loi cht hot ng b mt khc nhau c ch ra
trong bng sau:
Cht hot ng b
mt
max
(l.cm-1 mol-1)
bn phc
558
1,31.104
< 5 gi
4
572
1,26.10
> 2 ngy
Tween 80
569
1,22.104
> 2 ngy
4
Triton X-100
571
1,29.10
> 2 ngy
Tt c cc yu t nh hng n nhy ca phng php u c ti u ho
SDS
v xc nh c vng tuyn tnh ca Co(II) v Pd(II) ln lt l 0,2 2 g/ml v 0,4

4 g/ml. Kt qu nghin cu c ng dng phn tch cc mu thc t l hp
kim. [28]
Mt s nghin cu o quang trong mi trng Triton X- 100
Abbas Afkhami xc nh Co(II) v Ni(II) da trn c s s to phc ca
chng vi thuc th PAN trong mi trng Triton X-100. Qua kho st nhn thy pH
ti u cho php o l 5,8 (m citrat), nng ca Triton X-100 v PAN ln lt l
1,4% v 10-3 M. [19]
Trong mt nghin cu khc, ng xc nh Zn(II), Co(II) v Ni(II) trong
Triton X-100 nng 0,8 1,2%, nn pH = 9,2 (m amoni). Cc bc sng hp th
cc i tng ng vi Zn(II), Co(II) v Ni(II) l 564 nm, 584 nm v 552 nm. [18],
[20]
Narinder Kumar Agnihotri dng phng php trc quang phn tch lng vt
Cu(II) vi thuc th PAN, cht hot ng b mt Triton X-100, cc i hp th:
max = 555 nm, gii hn pht hin LOD = 4 ppb, khong tuyn tnh: 0,08 4 ppm.
i chiu vi phng php AAS cho kt qu tt. [40]
26
Olga Ch.Manouri v cng s nghin cu phn tch hm lng Zn(II) trong

dc phm bng mt s phng php. Phng php th nht l phng php o
quang da trn c s s to phc ca Zn(II) vi thuc th 4-(2-pyridylazo)resorcinol (PAR) ti pH = 8,07 v trong mi trng cht hot ng b mt trung tnh
Triton X-100, bc sng hp th cc i max = 493 nm, khong tuyn tnh 0,18
2,0 g/ml. Phng php th hai da trn c s s to phc ca Zn(II) vi 8hydroxyquinon, qua kho st iu kin ti u thu c khong tuyn tnh 0,26-1,05
g/ml. Phng php th ba l phng php o ph hp th nguyn t AAS vi thng
s k thut = 213,9 nm, n catot rng HCL, nhit ngn la 27000 K, khong tuyn
tnh 0,2 2 g/ml. So snh ng v chnh xc ca ba phng php trn.[41]
1.3. Thuc th 1-(2-pyridylazo )-2- naphtol (PAN)

1.3.1. Cu to, tnh cht vt l ca PAN
Cng thc cu to ca PAN:
Khi lng phn t ca PAN:
M = 249,27
Cng thc phn t ca PAN: C15H11ON3
N
N
HO
Trong cng thc cu to, PAN gm hai vng c lin kt vi nhau qua cu
-N = N-, mt vng l pyridyl, vng bn kia l vng naphtol ngng t. PAN l
thuc th hu c c dng bt mu vng , khng tan trong nc, tan tt trong cc
dung mi hu c nh ru, CH3Cl, CCl4, axeton Dung dch thng c mu vng,
hp th cc i cc bc sng 425nm, 470nm v 495nm.
Tu thuc vo pH ca mi trng m thuc th PAN c th tn ti cc dng khc
nhau, n c ba dng tn ti H2In+ (vng chanh, pH < 2,5), HIn (vng, pH > 2,5) v In (, pH > 12) v c cc hng s phn ly tng ng: pK1 = 2,9 v pK2 = 12,1.
Chng ta c th m t cc dng tn ti ca PAN qua cc cn bng sau:
27
PK1 = 2,9
NH+
N
HO
HO
PK2 = 12,1
N
-
1.3.2. Kh nng to phc ca PAN

PAN l mt thuc th n baz tam phi v, cc phc to c vi n c kh
nng chit v lm giu trong dung mi hu c nh CCl 4, CHCl3, ru isoamylic,
ru isobutylic, ru n-amylic, ru n-butylic
Thuc th PAN khng chn lc, phn ng vi hu ht cc ion kim loi, c
dng ph bin phn tch cc kim loi. Thuc th PAN to phc vi nhiu ion kim
loi nh: Fe, Co, Cu, Mn, Ni, Zn to hp cht ni phc c mu vng m trong
CCl4, CHCl3, benzen, ietylete.
Cc phc vng cng kim loi vi PAN c cc nguyn t kim loi (hay oxo hoc
hydroxo cation kim loi) lin kt vi nguyn t O ca nhm OH (H b thay th) v
nguyn t N ca pyridin, nguyn t N azo, cu trc ca phc c minh ho nh sau:
28
0 hoac 1
N
N
O
N
1 hoac2
N
N
M
O
M (II hoac III) ( M co the la M(OH)
+
2
M (II hoac III)
Thnh phn ca cc dng c chit vo trong cc dung mi khng trn ln

c vo nhau. Phc vng cng thng thng khng s dng c vi tt c cc
dng chit.
Axetat c th thay th clorua hay peclorat nng cao pH = 10; Cu(II) c
th c chit di dng CuL2, pH = 8, to thnh phc CuL+ mu tm khng chit
c tr khi c mt cc ion Cl-; Br-; SCN- hay axetat. Bng 2 a ra mt s c im,
tnh cht ca cc loi chelat kim loi PAN.
Cc phc vng cng khng mang in tch thng tan rt chm trong nc
nhng c th chit bi cc dung mi hu c khng tr ln c vo nhau; cloroforrm
(CHCl3). PAN (di dng HL) c mu vng trong cloroform,( max = 470nm), P
CHCl3/H2O
= 105,2. Phc vng cng ca cc kim loi di y c mu trong cloroform
(max thng nm trong khong 540 570 nm): Cd; Zn; Hg (II); Bi; Cu; La; In; Ga;
Fe(III) - nu; Sn (II); Pb; U(VI); Ni; Th; Ir. Cc phc ca PAN vi cc ion kim
loi Pd (II); Rh(III); v Co(II) c mu xanh, cn li ion phc ca PAN vi V(V);
Ti(III) c mu tm. Cc kim loi kim; Be; As; Ge; Se; v Te khng cho phn ng
mu vi PAN.
Bng 2. Cc tnh cht ca mt s phc kim loi PAN
29
Kim loi
Thnh phn phc

(M: PAN)
max (nm)
.10-3
Bi
1:1
580
21
Cd
1:2
550
50
Co(II)
1:2
525
30
Co(III)
1:2
580
23,1
Cu(II)
1:2 (CHCl3)
550
45
1:1 (H20)
550
575
22
16
1:1, 1:2
550
21,7
Fe(III)
Ga
Hg(II)
560
Mn(II)
1:2
550
40
Ni
1:2
575
51
Pd
1:1
620(675)
16
Zn
1:1
626(678)
515; 514
14,1 (678nm)
22,6; 20,8
[MLn] hu c . [H+]n
H s chit :
Kext =
[Mn+]. [HL]nhu c
Hu ht cc kim loi u cn dung dch axit yu hoc baz yu chit v cn

phi iu chnh pH mt cch cn thn, t m. S thay i pH c nh hng n qu
trnh lm tng chn lc ca phn ng to phc, i khi s dng EDTA lm tc
nhn che. V d, nu 1 dung dch phc PAN kim loi c lc vi dung dch EDTA
pH = 5 th tt c cc phc b phn hu ngoi tr phc ca kim loi Fe, Co, Ni, V,
Pd. V c th to phc vi H2O2, cn li Fe, Co, Ni c th xc nh mt cch ng thi
bng cch o hp th quang cc bc sng 565nm; 628nm v 764nm. Zn c th
30
xc nh c trong s c mt ca Cd; Cu; Hg; Pb v Ag bng cch che cc ion kim

loi ny bi ion I-; Ni vCo c th c che bi ion xianua (CN-).
S chit cc kim loi vi dung dch PAN trong cloroform v cc dung mi
tng t c th rt chm. Ni2+ c th c chit hon ton sau khi lc 40 gi. Qu
trnh chit s nhanh hn nu thm thuc th trong mt lng nh ancol.
Nhm c xc nh bng phng php hunh quang di dng phc ca
nhm vi PAN trong dung dch etylic. Xc nh Co trong dung dch vi thuc th
PAN trong s c mt ca cht hot ng b mt trong ho (TritonX 100).
p- PAN c th tng hp c, cc c im ca phc kim loi vi PAN
c nghin cu. Cc phn ng ca PAN vi hu ht cc kim loi nng nhy hn
cc phn ng ca cc ng phn - ortho. Trong mi trng axit mnh, thnh phn
phc vng cng ca Cu(II); Zn; Ni vi PAN theo t l 1 : 2. Thuc th PAN phn ng
dng C:
H2C
H3C
_
..
N
..
ON
a)
..
N
b)
N
_
..
N
N
..
c)
Cc tc gi dng phng php so mu xc nh Zn, Cu v Mn trong qu

trnh kim tra s thm tch ca cc cht lu. PAN c s dng lm cht o quang
trong dung dch mixen ca thuc th hnh thnh khi ho tan PAN trong dung dch
nc c cha Trion (5% v th tch). Ph thu c khi dng cc ion Zn, Cu, Mn
trong dung dch m borat c pH = 9,2. Nng cc cht thm tch trong mu thm
31
tch c xc nh trong khong 6-500ppm. Phng php ny c dng nh

tnh cc cht gy nhim.
Tc gi Ninh, Miugyuan dng phng php o mu xc nh Cu v Ni trong
hp kim nhm bng PAN khi c mt triton X-100, Dung dch m ca phc ny pH
= 3 khi c mt ca Al(NO3)3 v NaF nhng nh hng ca nhm b loi b, trong s
c mt ca triton X-100, phc Cu-PAN hp th cc i bc sng max = 550nm, =
1,8,10-4 L/mol,cm, Cn Ni-PAN hp th cc i bc sng max = 565nm, = 3,5,104
L/mol,cm, Khong tun theo nh lut Beer l 0 100gCu/50ml v 0 55g
Ni/50ml, Phc Cu-PAN b phn hy khi thm Na2S2O3,

Mt s tc gi cng b qu trnh chit phc PAN vi mt s ion kim loi
trong pha rn v qu trnh chit lng mt s nguyn t t him ho tr 3, Qu trnh
chit lng rn i vi RE (RE: La, Ce, Pr, Nd, Sn, Yb, Gd ) bng cch s dng PAN,
HL,PAN l cht chit trong parafin c nghin cu nhit 80 0,070C,
Nhng nh hng ph thuc thi gian, pH ca cht chit conen trong parafin
cng nh cht rn pha long ng vai tr nh dung dch m c s dng
Phn ng chit: RE3+ + 2 HL(o) + Cl- REL2Cl(o) + 2 H+
Trong nhng nm gn y PAN cng c s dng xc nh cc nguyn t
Cd, Mn, Cu trong xng, chit o mu xc nh Pd(II), Co trong nc tch ring
Zn, Cd, Tc gi xc nh cc ion trong v mu ca thuc vin, phng php o mu
trong quang ph k ph hp vi vic xc nh ion km thng qua vic to phc vi
PAN pH = 2,5; dung dch phc c mu , khong tun theo nh lut Beer t 2,0
40g/50ml max = 730nm,
Mt s tc gi khc xc nh Co bng phng php von ampe s dng in cc

cc bon b bin i b mt bng PAN, Gii hn pht hin 1,3,10-7 M nhng nh
hng ca cc ion cng tn ti v kh nng ng dng vo thc t phn tch cng
c kim tra
Thm vo tc gi cn xc nh Co bng phng php trc quang vi PAN
trong nc v nc thi to phc pH = 3 8 vi = 620nm, Vi Ni to phc pH
= 8 vi = 560nm,
32
Ngoi ra, cc nh khoa hc trn th gii s dng PAN cho cc mc ch

phn tch khc. [1], [21],[22], [25], [32], [33], [34], [35], [36], [39] .
33
CHNG 2. THC NGHIM

2.1. Ni dung nghin cu
T nhng nhim v nghin cu ra, chng ti ng dng phng php o
quang tin hnh phn tch Cu(II), Zn(II), Co(II) trong phn vi lng. Vic la
chn thuc th cng kh quan trng, trong ti ny, thuc th c s dng l PAN
- l thuc th hu c ph bin, tc dng c vi nhiu nguyn t, rt thun li cho
vic xc nh c ba nguyn t ch vi mt thuc th ny. Vi thuc th v trnh
vic chit vi dung mi hu c c hi, chng ti la chn gii php l dng mi
trng mixen trung tnh, c tc dng lm tng tan ca phc kim loi vi PAN.
Kho st c trng ca h M(II) PAN - Cht hot ng b mt
Xt ph c trng, nh hng ca pH, mixen, nng thuc th.
Xc nh khong tuyn tnh, xc nh gii hn pht hin, gii hn nh

lng.
ng dng, xt nh hng ca nguyn t ny n nguyn t kia v
cch loi tr nh hng, tch cc ion khi chng cng c mt.

Xc nh tng nguyn t
Xc nh tng nguyn t trong iu kin ti u trn bng phng php
tch sc k trao i ion.

Xc nh ng thi cc nguyn t
Xc nh hp th quang ng vi tng bc sng, kim tra tnh cng

tnh.
Xy dng ma trn s ph thuc ca hp th quang vo nng .
La chn php xc nh trong s cc thut ton CLS, ILS, PLS, PCR.
Xy dng ma trn cc mu kim tra, nh gi mc chnh xc ca
phng php, kh nng ng dng vo mu thc t.

Tin hnh phn tch mu
nh gi thu hi, i chiu kt qu vi phng php quang ph hp
th nguyn t (AAS)
34
2.2. Thit b v ha cht

2.2.1 Thit b v phn mm
My o hp th quang UV VIS Spectrophotometric - 1650 PC
(SHIMADZU, Nht Bn ), khong o 190 900nm , s dng cuvet thy tinh c
chiu di 1,0 cm.
My o pH in cc thy tinh kp (HANNA Italia).
My tnh c phn mm UVProbe 2.10 c th ghi v c hp th quang
tng bc sng.
X l thng k trn phn mm Origin 6.0
Lp trnh tnh ton hi qui a bin trn phn mm Matlab 7.0 (Chng trnh
CLS, ILS, PLSv PCR).
2.2.2. Ha cht
Tt c cc ho cht s dng u thuc loi tinh khit phn tch. Cc dung dch
c pha ch bng nc ct 2 ln.
Dung dch Cu(II) 1000 ppm: Cn 0,3906 g CuSO4.5H2O, ha tan trong nc ct
2 ln, chuyn vo bnh nh mc c 100ml, lc cho tan ht, nh mc bng nc ct
n vch. Kim tra li bng phng php chun complexon, dung dch m axetat
/ axit axetic pH=5 theo cht ch th PAN, 800C. im tng ng dung dch
chuyn t mu tm m sang mu vng lc. Nhng nng Cu(II) thp hn c
chun b hng ngy t dung dch Cu(II) 1000 ppm.
Dung dch Zn(II) 1000 ppm: Cn 0,4424 g ZnSO4.7H2O, ha tan trong nc ct
n vch. Kim tra li nng bng phng php chun complexon vi cht ch
th ET-OO dung dch m amoni/amoniac pH=9,5. Ti im tng ng, dung dch
chuyn t mu nho sang mu xanh lam. Nhng dung dch Zn(II) c nng thp
hn c pha t dung dch Zn(II) 1000 ppm.
Dung dch Co(II) 1000 ppm: Cn 0,4034 g CoCl2.6H2O, ha tan trong nc ct
n vch. Xc nh li nng ca dung dch Co(II) bng phng php chun
35
complexon vi cht ch th murexit, pH = 8. Ti im tng ng, dung dch

chuyn sang mu tm bn. Nhng dung dch Co(II) c nng thp hn c pha t
dung dch Co(II) 1000 ppm.
Dung dch thuc th PAN 2.10-3M: Cn 0,0500 gam PAN, chuyn vo bnh
nh mc c 100ml c sn 2ml H2SO4 2M v 10ml nc ct, cho thm 4 g Triton
X 100 hoc Tween, un m lc nh, nh mc bng nc ct n vch.
Pha Tween 80 (3%) (m/v): Ho tan 3 g Tween 80 bng nc ct 2 ln, nh
mc 100ml.
Pha Triton X-100 (10%) (m/v): Ho tan 10 g Triton X-100 bng nc ct 2 ln,
nh mc 100ml.
Dung dch m axetat 0,2 M (CH3COOH 0,1 M v CH3COONa 0,1 M). Cc
dung dch m axetat c pH khc c chun b t dung dch m trn khi thm
nhng lng HCl hoc NaOH thch hp vo v kim tra bng my o pH.
Dung dch m borac 0,1 M (M = 381,37): Cn 19,0863 gam Na2B4O7.10H2O
ha tan bng nc ct 2 ln v nh mc bng nc ct n vch 500ml. Cc dung
dch m borac c pH khc c chun b t dung dch m trn khi thm nhng
lng HCl thch hp vo v kim tra bng my o pH.
Dung dch m citrat 10-3M (M = 210,14 ): Cn 5,2532 gam axit citric ha tan
bng nc ct 2 ln v nh mc bng nc ct n vch 250ml. Cc dung dch m
citrat c pH khc c chun b t dung dch m trn khi thm nhng lng NaOH
thch hp vo v kim tra bng my o pH.
Cc dung dch ion kim loi khc Mn2+, Fe2+, Fe3+c pha bng cc mui tan
ca n.
Nha trao i anionit Dowex 1 (c ht khong 100-200 Mesh, ng knh 0,050,08 mm), nha ny c ngm trong nc mt m. Chuyn ln ct ng knh 10
mm, c mt lp chiu cao 27 mm, ra ct bng pha ng HCl 9M.
36
2.3. Cch tin hnh thc nghim

2.3.1. Qui trnh nghin cu n bin
Ly vo cc bnh nh mc c 25 ml c mt lng nht nh mt trong ba
ion kim loi Cu(II), Zn(II), Co(II) + dung dch m axetat 4.10-2M c pH = 6,5 +
cht hot ng b mt (Triton X-100 2%) + hn hp PAN 1,6.10-4 M, nh mc n
vch.
xt c trng ca ph, o hp th quang trong khong 500 700 nm, vi
dung dch so snh l mu trng.
i vi cc nghin cu khc, o hp th quang ca Cu(II), Zn(II), Co(II) ln
lt cc bc sng 558 nm, 556 nm, 580 nm, vi dung dch so snh l mu trng.
2.3.2. Qui trnh nghin cu a bin

Xc nh c trng ph khi c mt ba ion kim loi Cu(II), Zn(II), Co(II).
Ly vo cc bnh nh mc c 25 ml (cc bnh xy dng ma trn chun)
c mt lng nht nh mt trong ba ion kim loi Cu(II) (0,021 -1,41 ppm), Zn(II)
(0,03 1,56 ppm ) , Co(II) (0,06 2,12 ppm) + dung dch m axetat 4.10-2M c pH
= 6,5 + Triton X-100 2% + hn hp PAN 1,6.10-4 M, nh mc n vch. o hp
th quang trong khong 500 700 nm, vi dung dch so snh l mu trng.
Ly vo cc bnh nh mc c 25 ml (cc bnh xy dng ma trn kim tra)
c mt lng nht nh mt trong ba ion kim loi Cu(II) (0,021 -1,41 ppm), Zn(II)
(0,03 1,56 ppm ) , Co(II) (0,06 2,12 ppm) (mt s bnh kim tra khng c c 3
ion) + dung dch m axetat 4.10-2M c pH = 6,5 + Triton X-100 2% + hn hp PAN
1,6.10-4 M, nh mc n vch. o hp th quang trong khong 500 700 nm, vi
dung dch so snh l mu trng.
i vi mu phn tch, chun b cc bnh ging nh xy dng ma trn kim tra
v thc hin php o quang nh trn.
Cc d kin o quang s c x l bng thut ton hi qui a bin tuyn tnh
trn phn mm Matlab 7.0. T nh gi chnh xc, tnh sai s, xc nh nng
mu phn tch.
2.3.3. Qui trnh phn tch mu
37
Cn 1 gam mu phn vi lng, chuyn vo cc chu nhit, cho mt t nc,

10ml HNO3 , y bng np knh ng h, un nng nh (100 2000 C), cho t t
H2O2 vo dung dch n khi thy dung dch trong sut. C cn dung dch, ngui,
cho thm nc ct vo cc v tip tc c cn. Chuyn dung dch vo bnh nh mc
c 50ml, nh mc bng nc ct n vch. Ly cc th tch cn thit t dung dch
ny thc hin cc php o xc nh n v a bin.
Qui trnh tch:
Dowex 1 ngm trong HCl long, chuyn ln ct, di 5ml HCl 9M cn bng.
Ly mt lng dung dch mu phn tch trong HCl 9M, cho qua ct trao i
ion.
Khi dn mu qua ct v dng HCl 9M ra ct, dng bnh nh mc c 25 ml
thu phn nc lc v nc ra, xc nh Cu(II).
Tip tc dng HCl 4M ra ct, hng phn nc ra gii ny xc nh
Co(II).
Gii hp Zn(II) bng HCl 0,5 M, thu dung dch nc ra gii xc nh
Zn(II).
Xc nh ring r tng ion kim loi theo qui trnh n bin.
Xc nh ng thi theo qui trnh a bin.
2.4. Thut ton phn tch hi qui tuyn tnh a bin

[5], [11]
2.4.1. Phng php bnh phng ti thiu thng thng (CLS)

Nhp ma trn nng C (27x3) ca 27 dung dch chun cha ba cht phn tch
l Cu(II), Zn(II) v Co(II).
Nhp ma trn hp th quang A (27x100) cu 27 mu ti 100 thi im o.
Tnh ma trn h s hi qui theo cng thc: K = inv(C*C)*C*A
Nhp ma trn gi tr Ax(kx100) ca k mu cn nh phn 100 thi im.
Tnh nng Cu(II), Zn(II) v Co(II) theo cng thc: Cx = Ax*K*inv(K*K)
2.4.2. Phng php bnh phng ti thiu nghch o (ILS)

Nhp ma trn nng C (27x3) ca 27 dung dch chun cha ba cht phn tch
l Cu(II), Zn(II) v Co(II).
38
Nhp ma trn hp th quang A (27x20) ca 27 mu ti 20 thi im o.

Tnh ma trn h s hi qui: P = inv(A*A)*A*C
Nhp ma trn gi tr: Ax(kx20) ca k mu ti 20 thi im.
Tnh nng Cu(II), Zn(II) v Co(II) theo cng thc: Cx = Ax*P
2.4.3. Phng php bnh phng ti thiu tng phn (PLS)

Nhp ma trn nng C (27x3) v ma trn hp th quang A (27x100) ca 27
dung dch chun cha ba cht phn tch l Cu(II), Zn(II) v Co(II) ti 100 thi im
o.
Tnh vect trng s: w = (A*C)* inv(C*C)
Tnh tr s v trng s:
t = A*w
p = (A*t)*inv(t*t)
q = (C*t)*inv(t*t)
b = w*inv(P*w)*q
a = mean(C) -mean( A)*b
a0 = [ones(27,1)*a(1) ones(27,1)*a(2)ones(27,1)*a(3)]
27: S dung dch chun.
a(1), a(2), a(3): Cu t th 1, th 2 v th 3.
Nhp ma trn hp th quang Ax(kx100) ca k mu cn nh phn
Nng Cu(II), Zn(II) v Co(II) c trong mu c tnh theo cng thc:
C0 = a0 + Ax*b
2.4.4. Phng php hi qui cu t chnh (PCR)

Nhp ma trn nng C (27x2) v ma trn hp th quang A (27x20) ca 27
dung dch chun cha hai cht phn tch ti 20 thi im.
Bnh phng tp s liu cha bin ph thuc: D = A*A
Xc nh cc PC (s dng hm SVD): [V S] = svd(D)
Tnh ma trn phn trm phng sai ca cc PC:
d = diag(S)/sum(diag(S))*100
Chn s PC lm c s cho khng gian mi ca tp s liu n: f = V(:,1:n)
39
Chuyn i tp s liu ban u v tnh ma trn h s hi qui:

Aj =A*f
F = inv(Aj*Aj)*Aj*C
Fj = f*F
Nhp ma trn hp th quang Ax(kx20) ca k mu cn nh phn v tnh
nng Cu(II), Zn(II) v Co(II) theo cng thc: Cx = Ax*Fj
Ngoi ra, cu lnh tnh sai s: ss = (Ctnh - C)*100./C
40
CHNG 3. KT QU V THO LUN

3.1. Kho st iu kin ti u xc nh Cu(II), Zn(II), Co(II)
3.1.1. Nt c trng ph ca cc phc Cu(II)-PAN, Zn(II) -PAN, Co(II)
PAN
Thuc th PAN phn ng vi cc cation kim loi nh Cu(II), Zn(II), Co(II) ,
Ni(II)...to thnh cc phc mu khng tan trong nc, thng phi chit trong dung
mi hu c. Kt qu thc nghim cho thy, trong mi trng mixen cht hot ng
b mt trung tnh, cc phc ny tan c trong nc v c hp th cao trong vng
nh sng kh kin. V vy, chng ti tin hnh kho st ph hp th quang cc phc
mu Cu(II) - PAN, Zn(II) - PAN v Co(II) - PAN trong mi trng mixen (Tween 80 hoc Triton X-100).
Hnh 1. c trng ca ph hp th cc phc mu trong mi trng Tween 80
41
Ly vo cc bnh nh mc c 25 ml c mt trong ba ion Cu(II) 0,6 ppm,

Zn(II) 1 ppm, Co(II) 1ppm + dung dch m axetat 4.10-2M (pH = 6,5)+ cht hot
ng b mt (Tween 80 0,24% hoc Triton X-100 2%)+ hn hp PAN 1,6.10-4M,
nh mc n vch, sau 10 pht ghi ph trong khong 500 700 nm vi dung dch
so snh l mu trng tng ng. Kt qu c ch ra hnh 1,2.
Hnh 2. c trng ca ph hp th cc phc trong mi trng Triton X-100
T cc hnh trn v i chiu vi phng php dng dung mi chit [23], [41],
ta c bng kt qu trong bng 3.
Bng kt qu trn cho thy s cc i hp th ca cc phc mu Cu(II) - PAN,
Zn(II) - PAN v Co(II) - PAN trong c ba mi trng u ln lt l 1, 2, 2. Trong
mixen (Tween 80 hoc Triton X-100), cc cc i hp th u chuyn dch v pha
sng ngn, gi tr bc sng hp th cc i ca phc mu Cu PAN: 558 nm, Zn
PAN: 522 nm v 556 nm, Co PAN: 580 nm v 620 nm. T nghin cu ny, chng
ti chn l max = 558nm, 556 nm v 580 nm tng ng tng phc ca Cu(II), Zn(II)
v Co(II) trong mi trng Triton X-100 cho cc kho st tip theo.
42
Bng 3. c trng ph hp th Cu(II) - PAN, Zn(II) PAN, Co(II) PAN

Tween 80
555
Cu
Zn
max (nm)
Triton X-100
558
522
556
580
620
Co
Dung mi chit
564/CHCl3
595/ Et-OH, H2O
530/Axeton, H2O
555/iso C5H11OH
590/CHCl3
640/CHCl3
522
556
580
620
3.1.2. Kho st nh hng ca pH n s to phc

3.1.2.1. Kho st nh hng ca pH
Gi tr pH ca mi trng ng vai tr quan trng n kh nng hnh thnh
phc v bn ca phc. nh hng ca pH n hp th quang ca cc phc
c nghin cu trong khong 3,0 7,0. cc pH thp (pH < 3) v pH > 7 khng
c nghin cu v pH < 3 cu trc pyridyl ca PAN b proton ho v pH > 7, cc
ion OH- cnh tranh trong qu trnh tng tc ca PAN vi cc ion kim loi nh hng
ti qu trnh hnh thnh cc phc mu. Kt qu kho st trong khong pH t 3 n 9
(pH 3-7: dng m axetat, pH 7-9: dng m borac, iu chnh bng HCl hoc NaOH
theo my o pH) thu c bng 4 v biu din trn hnh 3.
Bng 4. Kt qu kho st nh hng ca pH n s hnh thnh cc phc
pH
A Cu PAN
A Zn PAN
A Co - PAN
4
0,264
0,521
0,359
5
0,312
0,581
0,354
6
0,361
0,646
0,353
43
7
0,365
0,682
0,351
8
0,377
0,706
0,323
9
0,386
0,724
0,315
Cu-PAN
Zn-PAN
Co-PAN
0.7
Do hap thu quang (A)
0.6
0.5
0.4
0.3
0.2
0.1
0.0
4
pH
Hnh 3. nh hng ca pH n hp th quang ca cc phc mu
T hnh trn, ta thy khi pH trong khong 5- 7: phc ca Cu(II) v Co(II) kh

bn, khng thay i nhiu, Zn(II) tng ln r rt. m borac khng nh hng n
phc, chn pH = 6,5 cho cc nghin cu tip theo. Khi , dng m axetat (4.10-3
M) hoc hn hp axetat(4.10-3 M) + citrat(1.10-3 M).
Khi thm m citrat vo dung dch m axetat pH =6, hp th quang ca
cc phc thay i nh bng sau:
Bng 5. nh hng ca nng m citrat n s hnh thnh cc phc
Nng citrat (M)
A Cu PAN
A Zn PAN
10-4
0,380
0,646
5.10-4
0,379
0,645
10-3
0,379
0,646
2.10-3
0,376
0,644
10-2
0,365
0,621
5.10-2
0,345
0, 597
A Co - PAN
0,353
0,354
0,353 0,352
0,348
0,343
-4
-3
Da vo kt qu ta thy nng m citrat t 1.10 M n 2.10 M th hp
th quang ca cc phc Cu(II)-PAN, Zn(II)-PAN, Co(II)-PAN n nh, t 2.10-2M
n 5.10-2M th hp th quang gim. V vy, la chn nng citrat 1.10-3M cho
cc kho st.
44
3.1.2.2. Kho st nh hng ca dung lng m

Tin hnh o quang khi thay i nng m axetat, thu c kt qu bng 6.
Bng 6: S ph thuc ca hp th quang vo nng ca m axetat
Nng
m axetat
8.10-3
1,6.10-2
2,4.10-2
3,2.10-2
4.10-2
4,8.10-2
A Cu PAN
0,512
0,513
0,517
0,518
0,519
0,512
A Zn PAN
0,646
0,645
0,646
0,644
0,641
0, 637
A Co - PAN
0,353
0,354
0,353
0,352
0,351
0,348
T kt qu thu c ta thy nng m axetat thay i t 8.10 -3M n 4.10-2M th

hp th quang tng i n nh, t 4.10-2M n 4,8.10-2M th hp th quang
gim. Do , chng ti chn nng m axetat l 4.10-2M tin hnh tip.
Nh vy, chng ti s dng hn hp m (axetat 4.10 -2M v citrat 1.10-3M) c
pH = 6,5 cho cc kho st tip theo.
3.1.3. Kho st nh hng ca nng Triton X-100 n s to phc

Bn cht ca cc mixen khc nhau dn n s hnh thnh phc khc nhau. Vi
loi mixen l Triton X-100, chng ti tip tc kho st nh hng ca nng mixen
ti qu trnh to phc. Kt qu kho st c ch ra trong bng 7 v hnh 4:
Bng 7. Kho st nh hng ca nng Triton X100 n s hnh thnh phc
Nng Triton X-100
(%)
A Cu PAN
A Zn PAN
A Co - PAN
0,5
0,548
0,493
0,365
0,556
0,503
0,367
0,56
0,51
0,368
0,555
0,496
0,363
0,541
0,482
0,357
45
Cu-PAN
Zn-PAN
Co-PAN
0.56
0.54
0.52
0.50
0.48
0.46
0.44
0.42
0.40
0.38
0.36
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
Nong do Triton X-100
Hnh 4. nh hng ca nng Triton X- 100 n hp th quang ca cc phc
T kt qu thu c ta thy nng Triton X 100 thay i t 0,5% n 1% th

hp th quang ca cc phc tng, t 1% n 3% th hp th quang hu nh
khng i v t 3% n 4% th hp th quang gim. Chng ti la chn Triton X100 (2%) cho cc kho st tip theo.
3.1.4. Kho st nh hng ca thuc th PAN

Nng ca PAN c thay i trong khong 0,16.10-4 2,4.10-4 M v tin
hnh o hp th quang ca cc phc mu cc bc sng cc i k trn. Kt
qu thu c th hin bng 8 v trn hnh 5.
Bng 8: Kt qu kho st nh hng ca thuc th PAN
Nng PAN (10-4M)
A Cu PAN
A Zn PAN
A Co - PAN
0,16
0,295
0,226
0,198
0,4
0,435
0,506
0,358
46
0,8
0,539
0,789
0,367
1,6
0,573
0,838
0,368
2
0,577
0,832
0,376
2,4
0,574
0,824
0,375
Cu-PAN
Zn-PAN
Co-PAN
0.90
0.85
0.80
0.75
0.70
0.65
0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0.0
0.5
1.0
1.5
2.0
2.5
Nong do PAN .10 M
Hnh 5: nh hng ca nng thuc th n hp th quang ca cc phc
T kt qu thu c trn, chng ti nhn thy t l to phc Cu(II)- PAN,

Zn(II)-PAN v Co(II) PAN ln lt l 1:2, 1:1, 1:1; khi nng thuc th PAN
tng dn t 0,16.10-4 M n 0,4.10-4 M th hp th quang ca cc phc mu tng
dn v khi nng PAN tng t 0,4.10-4 M n 2.10-4 M th hp th quang ca cc
phc t gi tr ln nht v n nh. V vy, chng ti chn nng PAN l 1,6.10-4
M cho cc kho st tip theo.
3.1.5. Kho st nh hng ca thi gian

pH = 6,5 v nhit phng, tc hnh thnh phc Cu PAN v Zn PAN
kh nhanh, ngc li Co PAN to phc tng i chm. Kt qu kho st thi gian
hnh thnh cc phc mu thu c cc hnh 6, 7, 8:
47
Hnh 6,7,8: Kho st bn ca cc phc mu theo thi gian
T cc hnh trn, chng ti nhn thy trong khong thi gian kho st 60 pht,
hp th quang ca cc phc mu rt n nh (phc bn). V vy, chn thi gian o
hp th quang ca cc phc trong khong 10 pht - 30 pht.
3.1.6. Kho st nh hng ca nng Cu(II), Zn(II), Co(II)

3.1.6.1. nh hng ca nng Cu(II)
Kho st khong tuyn tnh xy dng ng chun xc nh Cu(II)
Ly vo cc bnh nh mc c 25 ml c nhng lng bin i Cu(II) (0,021
-1,41 ppm) + dung dch m (axetat 4.10-2M v citrat 1.10-3M) c pH = 6,5 + Triton
X-100 2% + hn hp PAN 1,6.10-4 M, nh mc n vch. o hp th quang
bc sng max = 558 nm, dung dch so snh l mu trng. Kt qu thu c:
Bng 9: Kt qu s ph thuc ca A vo nng Cu(II)
STT
Cu
(ppm)
A
STT
Cu
(ppm)
A
0,06
0,13
0,26
0,38
0,51
0,64
0,021
7
0,069
8
0,184
9
0,266
10
0,370
11
0,455
12
0,77
0,90
1,03
1,15
1,28
1,41
0,563
0,635
0,758
0,832
0,916
1,030
48
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Nong do Cu(II)
Hnh 9: Kho st khong tuyn tnh xc nh Cu(II)
T hnh 9, ta thy khi nng Cu(II) tng th hp th quang cng tng tuyn
tnh. Tuy nhin, khi nng Cu(II) l 1,41 ppm th hp th quang kh ln nn sai
s ng k. Do , chn cc nng Cu(II) khng qu 1,41 ppm xy dng ng
chun xc nh hm lng Cu(II).
Bng 10: Kt qu xy dng ng chun xc nh
STT
CCu2+(ppm)
0,13
0,38
0,64
0,90
1,15
0,085
0,288
0,48
0,657
0,844
49
0.9
Parameter
Value Error
-----------------------------------------------------------A
-8.80195E-4
0.00905
B
0.737 0.0123
------------------------------------------------------------
0.8
0.7
0.6
R
SD
N
P
-----------------------------------------------------------0.99958
0.00996
5
<0.0001
------------------------------------------------------------
0.5
0.4
0.3
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Nong do Cu(II)
Hnh 10: ng chun xc nh Cu(II)
Phng trnh hi quy c dng nh sau: y = 0,00088 + 0,737x. Trong x l

nng ca Cu2+ (ppm) v y l hp th quang A. Mt khc, ta c lch chun
Sa= 0,00905 v Sb = 0,0123, t(0,95; 3) = 2,353 nn phng trnh hi quy y :
Y = ( 0,00088 0,02129 ) + (0,737 0,029)X
Phng trnh hi quy: y = 0,00088 + 0,737x c S 22 = 1,741.10-4
Nu coi a = 0 ta c phng trnh hi quy: y = bx vi b ' = 0,743 c S 12 = 1,62.10-4
S sai khc phng sai ca 2 phng trnh ny c so snh theo chun F:
Ftnh =S 22 / S 12 = 1,075
Ti P = 0,95, f1= n-2 = 3, f2 = n-3= 2 ta c: Fbng = 2,1916. [8]
Ftnh < Fbng nn s khc nhau gia a v gi tr 0 khng c ngha thng k. Nh
vy c th coi nh a = 0, phng php nghin cu khng mc sai s h thng.
Gii hn pht hin v gii hn nh lng
Tin hnh o 12 mu trng cc iu kin ti u chn ti bc sng 558 nm.
Bng 11: Kt qu o hp th quang ca 12 mu trng
STT
1
2
A Cu(II) PAN
0,086
0,085
STT
7
8
A Cu(II) PAN
0,088
0,087
lch chun: SD== 0,0011461
3
0,087
9
0,085
50
4
0,086
10
0,84
5
0,085
11
0,87
6
0,085
12
0,86
Gii hn pht hin (LOD): LOD = 3SD/b = 0,0047 (ppm)

Gii hn nh lng (LOQ): LOQ = 10SD/b = 0,0156 (ppm)
lp li trong php xc nh Cu(II)
nh gi lp li, ng v chnh xc ca ng chun ti 3 mc nng
Cu(II): 0,13ppm, 0,38 ppm v 0,9 ppm, mi im lm lp li 8 ln, ta c bng kt
qu:
Bng 12: hp th quang ca phc Cu(II)-PAN 3 nng khc nhau
Cu(II
) ppm
0,13
0,38
0,9
A1
A2
A3
A4
A5
A6
A7
0,08
0,085
0,086
0,086
0,086
0,087
0,087
7
0,27
0,277
0,278
0,277
0,279
0,279
0,278
7
0,63
0,639
0,640
0,640
0,639
0,638
0,638
9
Bng 13:Kt qu nh gi phng php xc nh Cu(II)
A8
0,086
0,278
0,639
Nng Cu(II) (ppm)

0,13
0,38
0,90
Nng trung bnh
0,117
0,376
0,88
lch chun SD
0,0012
0,00084
0,00076
H s bin thin (CV)
1,03 %
0,22%
0,09%
T kt qu trn nhn thy phng php trc quang xc nh Cu(II) bng thuc
th PAN c lp li tt (CV<3%) v chnh xc cao trn ton khong tuyn tnh.
3.1.6.2. nh hng ca nng Zn(II)
Kho st khong tuyn tnh v xy dng ng chun xc nh Zn(II)
Ly vo cc bnh nh mc c 25 ml c nhng lng bin i Zn(II) (0,03
1,95 ppm ) + dung dch m (axetat 4.10-2M v citrat 1.10-3M) c pH = 6,5 + Triton
bc sng max = 556 nm vi dung dch so snh l mu trng. Kt qu thu c:
Bng 14: Kt qu s ph thuc ca A vo nng Zn(II)

STT
Zn
ppm
A
0,03
0,06
0,13
0,26
0,39
0,52
0,65
0,78
0,91
0,027
0,037
0,073
0,156
0,22
0,29
0,34
0,398
0,482
51
STT
Zn
ppm
A
10
11
12
13
14
15
16
17
1,04
1,17
1,3
1,43
1,56
1,69
1,82
1,95
0,535
0,619
0,69
0,752
0,803
0,85
0,92
0,932
1.0
0.8
0.6
0.4
0.2
0.0
0.0
0.5
1.0
1.5
2.0
Nong do Zn(II)
Hnh 11: Kho st khong tuyn tnh xc nh Zn(II)
T hnh 11, nhn thy khi nng Zn(II) tng th hp th quang cng tng
tuyn tnh. Tuy nhin, khi nng Zn(II) l 1,56 ppm th hp th quang c xu
hng khng cn tuyn tnh na. Do , chn cc nng Zn(II) khng qu 1,56
ppm xy dng ng chun.
Bng 15: Kt qu xy dng ng chun xc nh Zn(II)
STT
CZn2+(ppm)
1,3
5,19
9,09
12,99
16,88
0,081
0,281
0,457
0,641
0,838
52
0.9
0.8
0.7
Y=A+B*X
0.6
Parameter
Value Error
-----------------------------------------------------------0.02237
0.0062
0.4 A
B
0.481 5.83072E-4
0.3 -----------------------------------------------------------0.5
R
SD
N
P
-----------------------------------------------------------0.1 0.99978
0.00718
5
<0.0001
-----------------------------------------------------------0.2
0.0
0
10
12
14
16
18
Nong do Zn(II)
Hnh 12: ng chun xc nh Zn(II)

nng ca Zn2+ v y l hp th quang A. Mt khc, ta c Sa= 0,0062 v Sb =
0,0006 , t(0,95; 3) = 2,353 nn phng trnh hi quy y :
Y = (0,02237 0,0062 ) + (0,0481 0,0006)x
Nu coi a = 0 ta c phng trnh hi quy: y = bx vi b ' = 0,478 c S 12 = 1,028.10-4
Ftnh =S 12 / S 22 = 1,123
Ti P = 0,95, f1= n-2 = 3, f2 = n-3= 2 ta c: Fbng = 2,1916.
Tin hnh o 12 mu trng cc iu kin ti u chn ti bc sng 556 nm.
STT
1
2
3
A Zn PAN
0,096
0,098
0,097
STT
7
8
9
A Zn PAN
0,097
0,098
0,099
lch chun: SD== 0,0011476
53
4
0,099
10
0,097
5
0,095
11
0,096
6
0,099
12
0,097
Gii hn pht hin (LOD):
LOD = 3SD/b = 0,007 (ppm)
Gii hn nh lng (LOQ):
LOQ = 10SD/b = 0,0239 (ppm)
lp li trong php xc nh Zn(II)

Zn(II): 0,13ppm, 0,39 ppm v 0,91 ppm, mi im lm lp li 8 ln, ta c bng kt
qu sau:
Bng 17: hp th quang ca phc Zn-PAN 3 nng khc nhau
Zn(II)
A1
ppm
A2
A3
A4
A5
A6
A7
A8
0,13
0,39
0,91
0,078
0,234
0,523
0,078
0,235
0,523
0,079
0,235
0,524
0,079
0,233
0,521
0,079
0,235
0,522
0,080
0,236
0,523
0,081
0,236
0,522
0,081
0,234
0,522
Bng 18: Kt qu nh gi phng php xc nh Zn(II)

Nng Zn(II) (ppm)
0,13
0,39
0,91
Nng trung bnh
0,14
0,40
1,00
lch chun SD
0,00119
0,00104
0,00093
H s bin thin (CV)
0,85 %
0,26%
0,09%
T kt qu trn nhn thy phng php trc quang xc nh Zn(II) bng thuc
3.1.6.3. nh hng ca nng Co(II)
Kho st khong tuyn tnh v xy dng ng chun xc nh Co(II)
Ly vo cc bnh nh mc c 25 ml c nhng lng bin i Co(II) (0,06
2,59 ppm) + dung dch m (axetat 4.10-2M v citrat 1.10-3M) c pH = 6,5 + Triton
bc sng max = 580 nm vi dung dch so snh l mu trng. Kt qu thu c nh
sau:
Bng 19: Kt qu s ph thuc ca A vo nng Co(II)
STT
Co (ppm)
A
STT
Co (ppm)
1
0,06
0,018
10
1,41
2
0,12
0,040
11
1,53
3
0,24
0,074
12
1,65
4
0,35
0,113
13
1,76
54
5
0,47
0,154
14
1,88
6
0,59
0,190
15
2,12
7
0,71
0,232
16
2,35
8
9
0,94 1,18
0,303 0,376
17
2,59
0,457
0,499 0,529 0,571 0,608 0,66
0,733 0,813
0.8
0.6
0.4
0.2
0.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Nong do Co(II)
Hnh 13: Kho st khong tuyn tnh xc nh Co(II)
T hnh 13, ta thy khi nng Co(II) tng th hp th quang cng tng
tuyn tnh. Tuy nhin, khi nng Co(II) l 2,12 ppm th hp th quang khng
cn tuyn tnh na. Do , chn cc nng Co(II) khng qu 2,12 ppm xy dng
ng chun.
Bng 20: Kt qu xy dng ng chun xc nh Co(II)
STT
CCo2+(ppm)
0,12
0,47
0,94
1,41
1,76
0,04
0,156
0,303
0,458
0,572
55
0.6
0.5
0.4
0.3
0.2
Y=A+B*X
Parameter
Value Error
-----------------------------------------------------------A
0.0016 0.0018
B
0.62362
0.00162
-----------------------------------------------------------R
SD
N
P
-----------------------------------------------------------0.99996
0.00216
5
<0.0001
------------------------------------------------------------
0.1
0.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
Nong do Co(II)
Hnh 14: ng chun xc nh Co(II)

nng ca Co2+ v y l hp th quang A. Mt khc, ta c Sa= 0,0018 v Sb =
0,00162, t(0,95; 3) = 2,353 nn phng trnh hi quy y :
Y = 0,0016 + (0,62362 0,0005)x
kim tra sai s h thng ca phng php, so snh hng s a ca phng
trnh hi qui vi gi tr 0:
Nu coi a = 0 ta c phng trnh hi quy: y = bx vi b ' = 0,6228 c S 12 =
1,028.10-4
S sai khc phng sai ca 2 phng trnh ny c so snh theo chun F:
Ftnh =S 22 / S 12 = 1,201
Ti P = 0,95, f1= n-2 = 3, f2 = n-3= 2 ta c: Fbng = 2,1916.
Tin hnh o 12 mu trng cc iu kin ti u chn ti bc sng 580
nm.
56

STT
1
2
A Co PAN
0,026
0,028
STT
7
8
A Co PAN
0,029
0,026
lch chun: SD== 0,00196
3
0,028
9
0,027
4
0,027
10
0,029
5
0,029
11
0,028
6
0,028
12
0,027
Gii hn pht hin (LOD): LOD = 3SD/b = 0,0094 (ppm)

Gii hn nh lng (LOQ): LOQ = 10SD/b = 0,0314 (ppm)
lp li trong php xc nh Co(II)
Co(II): 0,12 ppm, 0,47 ppm v 1,41 ppm, mi im lm lp li 8 ln, ta c bng
kt qu sau:
Bng 22: hp th quang ca phc Co-PAN 3 nng khc nhau
Co(II)
ppm
0,12
0,47
1,41
A1
A2
A3
A4
A5
A6
A7
A8
0,036
0,144
0,453
0,034
0,144
0,452
0,034
0,143
0,454
0,035
0,143
0,454
0,033
0,144
0,453
0,033
0,144
0,452
0,035
0,145
0,454
0,034
0,145
0,453
Bng 23:Kt qu nh gi phng php xc nh Co(II)

Nng Co(II) (ppm)
0,12
0,47
1,41
Nng trung bnh
0,106
0,464
1,409
lch chun SD
0,00104
0,00076
0,00083
H s bin thin (CV)
0,98 %
0,16%
0,06%
T kt qu trn nhn thy phng php trc quang xc nh Zn(II) bng thuc
3.1.7. Kho st nh hng ca cc ion l

i tng nghin cu trong ti l phn vi lng c thnh phn ch yu l N,
P2O5, K2O, S, Cu, Zn, B, Mo, Ca, Mn, Fe......Kt qu kho st thu c B, Mo khng
nh hng n cc phc Cu(II) PAN, Zn(II) PAN v Co(II) PAN. Mn(II), Fe(II)
v Fe(III) l ba ion gy nh hng ln n php o.
3.1.7.1. nh hng ca Mn(II)
Ly vo cc bnh nh mc c 25 ml c nhng lng Cu(II) 1 ppm hoc
Zn(II) 1 ppm hoc Co(II) 1 ppm, + dung dch Mn(II) (0 ppm 32 ppm) dung dch
57
m (axetat 4.10-2M) c pH = 6,5 + Triton X-100 2% + hn hp PAN 1,6.10-4 M,

nh mc n vch. o hp th quang cc bc sng tng ng.
Kt qu thu c :
Bng 24 : nh hng ca Mn(II) n hp th quang trong m axetat
M(II) ppm
Mn(II) ppm
A
Sai s(%)
A
Zn- PAN
Sai s(%)
A
Co- PAN
Sai s(%)
T cc bng s liu
Cu- PAN
1,0
0
0,735
1,0
1,0
1,0
1,0
4,0
8,0
16,0
24,0
0,718
0,688
0,656
0,622
2,45
6,52
10,87
14,13
0,575
0,525
0,503
0,482
0,468
8,70
12,52
16,17
18,61
0,388
0,391
0,398
0,405
0,416
0,77
2,58
4,38
7,22
ta thy, khi thm Mn(II) vi nng tng dn th
1,0
32,0
0,578
21,47
0,456
20,70
0,425
9,54
hp
th quang ca Cu-PAN, Zn-PAN gim dn v Co-PAN tng nh , v khi nng

Mn(II) gp 24 ln nng ion phn tch Cu(II), 16 ln nng ion phn tch Zn(II)
th sai s ln hn 15%, vt qu gii hn sai s cho php ca phng php trc
quang. V vy, chng ti chn ngng nh hng ca Mn(II) l gp 16 ln lng
Zn(II).
Ly vo cc bnh nh mc c 25 ml c nhng lng Cu(II) 1 ppm hoc
Zn(II) 1 ppm hoc Co(II) 1 ppm, + dung dch Mn(II) (0 ppm 32 ppm) + dung dch
m (axetat 4.10-2M v citrat 1.10-3M) c pH = 6,5 + Triton X-100 2% + hn hp
PAN 1,6.10-4 M, nh mc n vch. o hp th quang cc bc sng tng
ng.
Kt qu thu c nh sau:
Bng 25 : nh hng ca Mn(II) n hp th quang trong hn hp m
M(II) ppm
Mn(II) ppm
Cu- PAN
Zn- PAN
Co- PAN
A
Sai s(%)
A
Sai s(%)
A
Sai s(%)
1,0
0
0,732
0,569
0,384
58
1,0
16,0
0,683
-6,67
0,5111
-10,17
0,400
4,26
1,0
24,0
0,658
-10,13
0,4859
-14,61
0,411
7,03
1,0
32,0
0,641
-12,47
0,4683
-17,7
0,419
9,14
T bng trn, nhn thy khi dng hn hp m axetat 4.10-2M v citrat 1.10-3M s
loi tr c nh hng ca Mn(II).
3.1.7.2. nh hng ca Fe(II)
Kho st nh hng ca Fe(II) tng t nh nh hng ca Mn(II). Kt qu
nh sau :
Bng 26 : nh hng ca Fe(II) n hp th quang trong m axetat
M(II)
ppm
Fe(II)
ppm
ACu-PAN
Sai s(%)
AZn-PAN
Sai s(%)
ACo-PAN
Sai s(%)
0,5
0,5
0,5
0,5
0,5
0,5
0,5
0,5
0,5
0,25
0,5
1,0
2,5
10
25
50
0,555
0,719
0,911
15,53 28,81
50,87
95,47
0,881
139,3
0,289 0,295 0,301 0,337 0,387
0,466
0,519
16,61 33,91 61,25
79,58
0,368 0,380 0,388 0,425 0,474

3,24
2,08
5,32
4,15
0,195 0,208 0,219 0,257 0,345

6,67
12,31 31,79 76,92
0,438
124,6
0,562
188,2
3
0,606
109,6
9
0,618
216,9
147,61
0,685
137,02
0,723
270,77
2
1
2
T kt qu thu c, chng ti nhn thy ion Fe(II) gy nh hng ln n
php o xc nh M(II) . Khi nng Fe(II) vt qu 2 ln nng M(II) th sai s

ln hn 15%, vt qu gii hn sai s cho php ca phng php trc quang. V vy,
chng ti chn ngng nh hng ca Fe(II) l gp 2 ln lng M(II).
Khi tin hnh kho st trn nn hn hp m axetat 4.10-2M v citrat 1.10-3M ,
thu c kt qu nh sau:
Bng 27 : nh hng ca Fe(II) n hp th quang trong hn hp m
M(II) ppm
Fe(II) ppm
ACu-PAN
Sai s(%)
AZn-PAN
Sai s(%)
ACo-PAN
Sai s(%)
0,5
0
0,368
0,5
1,0
0,369
0,27
0,5
2,5
0,371
0,82
0,5
5
0,393
6,79
0,5
10
0,398
8,15
0,5
25
0,409
11,14
0,5
50
0,470
27,72
0,289
0.371
0.421
0.464
0.581
0.655
0.760
0,195
8,16
0,296
10,09
13,21
0,335
14,03
17,50
0,429
23,35
29,18
0,497
30,21
36,64
0,583
38,84
47,11
0,713
51,82
59
T bng trn, nhn thy khi dng hn hp m axetat 4.10-2M v citrat 1.10-3M s
loi tr c nh hng ca Fe(II).
3.1.7.2. nh hng ca Fe(III)
Kho st nh hng ca Fe(III) tng t nh nh hng ca Fe(II). Kt qu
nh sau :
Bng 28 : nh hng ca Fe(III) n hp th quang trong m axetat
M(II) ppm
Fe(III) ppm
ACu-PAN
0,5
0
0,368
Sai s(%)
AZn-PAN
Sai s(%)
ACo-PAN
0,289
0,195
Sai s(%)
0,5
0,25
0,392
0,5
0,5
0,405
0,5
1,0
0,484
0,5
2,5
0,574
0,5
5
0,688
6,47
10,16 31,65
55,93
87,08
0,301
2,16
0,208
0,340
4,25
0,218
0,398
17,65
0,260
0,477
37,82
0,340
0,505
65,13
0,428
6,43
11,59
33,12
74,35
119,42
0,5
10
0,883
139,8
2
0,613
74,63
0,539
176,3
0,5
25
0,955
159,63
0,645
112,21
0,593
203,97
1
T kt qu thu c, chng ti nhn thy ion Fe(III) gy nh hng ln n
php o xc nh M(II). Khi nng Fe(III) vt qu 2 ln nng M(II) th sai s

ln hn 15%, vt qu gii hn sai s cho php ca phng php trc quang. V vy,
chng ti chn ngng nh hng ca Fe(III) l gp 2 ln lng M(II).
Khi tin hnh kho st trn nn hn hp m axetat 4.10-2M v citrat 1.10-3M ,
thu c kt qu nh sau:
Bng 29 : nh hng ca Fe(III) n hp th quang trong hn hp m
Cu(II) ppm
0,5
Fe(III) ppm
0
ACu-PAN
0,367
Sai s(%)
AZn-PAN
0,289
Sai s(%)
ACo-PAN
0,195
Sai s(%)
T bng trn, nhn thy khi
0,5
0,5
1,0
2,5
0,368
0,370
0,37
0,93
0,363
0,403
7,36
11,41
0,286
0,315
9,08
12,02
dng hn hp m
loi tr c nh hng ca Fe(III).
60
0,5
0,5
5
10
0,395
0,399
7,68
8,65
0,454
0,560
16,51
27,13
0,408
0,487
21,34
29,15
axetat 4.10-2M v
0,5
0,5
25
50
0,422
0,477
15,04
29,92
0,633
0,740
34,42
34,42
0,553
0,701
35,84
50,64
citrat 1.10-3M s
3.2. Xc nh Cu(II), Zn(II), Co(II) trong hn hp

T hnh1, nu c ba ion c trong cng mt hn hp th ph ca cc phc c s
xen ph. Tin hnh kim tra s sai khc gia ph hn hp theo l thuyt v thc t
nh sau:
Ly vo 5 bnh nh mc c 25 ml c nhng lng Cu(II) 0,5 ppm (bnh 1) ,
Zn(II) 0,5 ppm (bnh 2), Co(II) 1 ppm (bnh 3), hn hp Cu(II) 0,5 ppm + Zn(II) 0,5
ppm + Co(II) 1 ppm (bnh 4) + dung dch m (axetat 4.10-2M v citrat 1.10-3M) c
pH = 6,5 + Triton X-100 2% + hn hp PAN 1,6.10-4 M, nh mc n vch. o
hp th quang khong bc sng 500 nm 700 nm vi dung dch so snh l mu
trng.
c trng ca ph hp th cc phc mu Cu- PAN; Zn PAN; Co PAN v
cc ph hn hp theo l thuyt v thc t nh hnh 15.
Ph hp th cho thy c s xen ph gia cc ph ca cc phc mu ca cc ion
kim loi nn mun xc nh ring r tng ion kim loi trong s c mt ca cc ion
khc, nht thit phi dng phng php chit hoc tch. Cc ph c tnh cng tnh th
thay v phi tch, c th dng phng php xc nh ng thi s dng thut ton hi
qui a bin.
61
Hnh 15: Ph hp th ca cc phc Cu-PAN, Zn -PAN, Co-PAN v ph hn hp ca 3

phc theo l thuyt v theo thc t
3.2.1. Xc nh Cu(II), Zn(II), Co(II) trong hn hp bng phng php tch

Cc cation Cu(II), Zn(II), Co(II), Fe(III), Mn(II) c kh nng to phc clorua
khc nhau. Cu(II) khng to phc clorua, Zn(II) to phc clorua [ZnCl4]2- trong mi
trng HCl 2M, Co(II) to phc clorua [CoCl4]2- trong mi trng HCl 4-9M. Da
vo s khc bit ny, chng ti la chn phng php tch sc k trao i ion vi
nha trao i l nha anionit (Dowex 1) tin hnh tch v xc nh ring r tng
cation Cu(II), Zn(II), Co(II). Pha ng dng tch Co(II), Zn(II) ln lt l HCl 4M
v 0,5M.
Trn c s qui trnh tch nh mc 2.3.3, chng ti tin hnh tch v xc nh
cc nguyn t trn cc mu gi.
3.2.1.1. Xc nh theo phng php ng chun
Tin hnh th nghim: Cho 5ml HCl 9M chy qua ct sc k. Ly vo bnh nh
mc c 10ml: 5ml hn hp gm cc ion Cu(II) 10ppm, Zn(II) 10ppm, Co(II) 10ppm,
Fe(II) 10ppm, Fe(III) 10 ppm, Mn(II) 10 ppm, dng HCl c iu chnh sao cho nn
axit trong bnh l HCl 9M.
62
Chuyn t t lng 10 ml trong bnh nh mc trn ln ct, hng dung dch

u ct bng bnh nh mc c 25ml (bnh 1), sau khi dung dch trn ct gn ht, tip
tc thm 5ml HCl 9M, dng nc ct hai ln nh mc bnh 1 n vch, lc u. Ly
5 ml dung dch t bnh 1, cho vo bnh nh mc c 25 ml (bnh 2).
ra gii Co(II), chuyn 5ml HCl 4M ln ct, hng dung dch chy ra vo
bnh nh mc c 10ml (bnh 3). Dng nc ct hai ln nh mc bnh 3 n vch,
lc u. Ly 5 ml dung dch t bnh 3, cho vo bnh nh mc c 25 ml (bnh 4).
ra gii Zn(II), chuyn 5ml HCl 0,5M ln ct, hng dung dch chy ra vo
bnh nh mc c 10ml (bnh 5). Dng nc ct hai ln nh mc bnh 5 n vch,
lc u. Ly 5 ml dung dch t bnh 5, cho vo bnh nh mc c 25 ml (bnh 6).
a dung dch trong cc bnh 2, 4, 6 v pH=5 ri thm cc cht cn thit
thc hin php o quang theo iu kin ti u (dung dch m axetat 4.10-2M
pH=6,5, hn hp PAN 1,6,10-4M, Triton X-100 2%, dung dch citrat 1.10-3M) ti cc
bc sng tng ng, dung dch so snh l mu trng.
T cc d kin o quang tnh nng ion da vo cc phng trnh ng
chun v tnh h s pha long ta c kt qu:
Bng 30. Hiu sut thu hi theo phng php tch da vo ng chun
Nng ly vo
Nng thu c
(nh trc)
Cu
Zn
Co
Cu
Zn
Co
10
10
10
9,725
10,234
10,062
3.2.1.2. Xc nh theo phng php thm chun
Hiu sut thu hi (%)

Cu
96,5
Zn
104,7
Co
103,8
Ly vo 3 bnh nh mc c 10 ml (trong nn HCl 9M) c nhng hm lng

khc nhau ca ba nguyn t v thm vo cc dung dch chun Cu(II) 50 ppm,
Zn(II) 50 ppm, Co(II) 50 ppm. Nng thm chun nh sau:
Bng 31:Nng thm chun
Mu
1
2
3
Cu
5,0
7,5
6
Nng thm chun (ppm)

Zn
3,0
5,0
3,5
63
Co
2,0
3,0
1,5
i vi mi mu, qui trnh tch c th nh mc 3.2.1.1. T cc d kin o

quang tnh nng ion da vo cc phng trnh ng thm chun v tnh h s
pha long ta c kt qu:
Bng 32: Hiu sut thu hi theo phng php tch da vo ng thm chun
Nng thm chun
Nng thu c (ppm)
Hiu sut thu hi (%)
(ppm)
Cu
Zn
Co
Cu
Zn
Co
Cu
Zn
Co
5,0
3,0
2,0
4.86
3.07
2.01
97,25
102,3
100,6
7,5
5,0
3,0
7.44
5.18
2.99
99,2
103,5
99,68
6
3,5
1,5
5.83
3.56
1.56
97,1
101,8
104,0
T cc gi tr hiu sut thu hi trn, nhn thy kt qu tch sc k trao i ion
kh tt, c bit l theo phng php ng thm chun. Tuy nhin, phng php
ny i hi nhiu thi gian v tri qua nhiu cng on ra gii.
3.2.2. S dng thut ton hi qui tuyn ttnh a bin xc nh ng thi

Cu(II), Zn(II), Co(II)
Trong ph hnh 15, nhn thy ph hn hp thc t v ph hn hp l thuyt
kh st nhau v kt qu hp th quang ca cc ph ti mi hai bc sng trong
khong 500 700 nm nh sau:
Bng 33: hp th quang ca tng ion v ca hn hp trn ton ph
Ahn hp
(nm)
500
502
504
506
508
510
512
514
516
518
520
522
524
ACu(II)
0,006
0,019
0,037
0,057
0,077
0,099
0,121
0,14
0,163
0,182
0,2
0,216
0,23
AZn(II)
0,018
0,032
0,052
0,074
0,099
0,125
0,152
0,175
0,199
0,214
0,224
0,227
0,226
ACo(II)
(l
-0,245
-0,207
-0,16
-0,109
-0,057
-0,004
0,052
0,106
0,158
0,204
0,248
0,286
0,321
thuyt)
-0,221
-0,156
-0,072
0,022
0,119
0,22
0,325
0,421
0,519
0,6
0,673
0,729
0,776
64
Ahn hp
Sai s
(thc t)
(%)
-0,222
-0,16
-0,078
0,012
0,106
0,203
0,303
0,396
0,491
0,569
0,639
0,693
0,738
-0,45
-2,56
-8,33
5,45
10,92
7,73
6,77
5,94
5,39
5,17
5,05
4,94
4,90
526
528
530
532
534
536
538
540
542
544
546
548
550
552
554
556
558
560
562
564
566
568
570
572
574
576
578
580
582
584
586
588
590
592
594
596
598
600
602
604
606
608
610
0,241
0,25
0,257
0,262
0,266
0,269
0,271
0,273
0,275
0,277
0,279
0,282
0,284
0,287
0,289
0,291
0,292
0,292
0,289
0,285
0,277
0,267
0,255
0,24
0,224
0,206
0,188
0,171
0,154
0,139
0,125
0,112
0,1
0,089
0,08
0,072
0,064
0,058
0,053
0,047
0,043
0,04
0,036
0,221
0,216
0,211
0,208
0,207
0,21
0,215
0,222
0,231
0,241
0,252
0,264
0,277
0,289
0,298
0,302
0,297
0,284
0,262
0,234
0,203
0,172
0,143
0,116
0,094
0,076
0,062
0,051
0,042
0,034
0,029
0,024
0,02
0,017
0,015
0,013
0,012
0,01
0,01
0,009
0,008
0,008
0,007
0,351
0,377
0,4
0,419
0,435
0,448
0,458
0,468
0,477
0,484
0,492
0,499
0,507
0,516
0,524
0,533
0,542
0,551
0,558
0,564
0,568
0,569
0,568
0,563
0,555
0,544
0,529
0,511
0,492
0,472
0,45
0,43
0,41
0,391
0,375
0,36
0,347
0,337
0,329
0,323
0,318
0,314
0,312
65
0,814
0,843
0,867
0,888
0,908
0,926
0,944
0,963
0,982
1,002
1,023
1,045
1,069
1,092
1,112
1,126
1,132
1,126
1,11
1,083
1,049
1,008
0,965
0,92
0,873
0,826
0,78
0,733
0,688
0,645
0,604
0,566
0,53
0,498
0,469
0,445
0,423
0,406
0,391
0,379
0,369
0,362
0,355
0,774
0,802
0,826
0,846
0,865
0,884
0,901
0,921
0,94
0,96
0,981
1,002
1,026
1,049
1,068
1,082
1,088
1,082
1,066
1,041
1,007
0,967
0,925
0,881
0,835
0,79
0,745
0,699
0,656
0,615
0,575
0,538
0,504
0,473
0,446
0,422
0,402
0,385
0,371
0,36
0,35
0,343
0,337
4,91
4,86
4,73
4,73
4,74
4,54
4,56
4,36
4,28
4,19
4,11
4,11
4,02
3,94
3,96
3,91
3,89
3,91
3,96
3,88
4,00
4,07
4,15
4,24
4,35
4,36
4,49
4,64
4,65
4,65
4,80
4,95
4,91
5,02
4,90
5,17
4,96
5,17
5,12
5,01
5,15
5,25
5,07
612
614
616
618
620
622
624
626
628
630
632
634
636
638
640
642
644
646
648
650
652
654
656
658
660
662
664
666
668
670
672
674
676
678
680
682
684
686
688
690
692
694
696
0,033
0,03
0,028
0,025
0,023
0,022
0,02
0,018
0,017
0,015
0,014
0,014
0,012
0,012
0,011
0,01
0,01
0,009
0,009
0,008
0,008
0,007
0,007
0,007
0,006
0,006
0,006
0,005
0,005
0,005
0,005
0,005
0,004
0,004
0,004
0,004
0,003
0,003
0,003
0,003
0,003
0,003
0,003
0,007
0,007
0,006
0,006
0,006
0,006
0,006
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,005
0,31
0,309
0,308
0,308
0,307
0,305
0,302
0,297
0,291
0,282
0,271
0,258
0,243
0,227
0,21
0,194
0,178
0,163
0,149
0,136
0,124
0,113
0,103
0,094
0,085
0,078
0,072
0,067
0,063
0,058
0,055
0,052
0,049
0,047
0,045
0,043
0,041
0,04
0,039
0,037
0,036
0,035
0,034
66
0,35
0,346
0,343
0,339
0,336
0,333
0,328
0,321
0,313
0,303
0,291
0,277
0,261
0,245
0,226
0,209
0,193
0,177
0,163
0,149
0,136
0,125
0,115
0,105
0,097
0,089
0,083
0,078
0,073
0,068
0,065
0,062
0,059
0,056
0,054
0,052
0,05
0,048
0,047
0,046
0,044
0,043
0,042
0,332
0,328
0,324
0,321
0,318
0,315
0,31
0,304
0,297
0,288
0,276
0,264
0,249
0,234
0,216
0,201
0,185
0,17
0,157
0,144
0,132
0,121
0,111
0,102
0,094
0,087
0,08
0,075
0,07
0,066
0,062
0,059
0,056
0,053
0,051
0,049
0,047
0,046
0,044
0,043
0,042
0,04
0,039
5,14
5,20
5,54
5,31
5,36
5,41
5,49
5,30
5,11
4,95
5,15
4,69
4,60
4,49
4,42
3,83
4,15
3,95
3,68
3,36
2,94
3,20
3,48
2,86
3,09
2,25
3,61
3,85
4,11
2,94
4,62
4,84
5,08
5,36
5,56
5,77
6,00
4,17
6,38
6,52
4,55
6,98
7,14
698
0,003
0,005
0,034
0,041
0,038
7,32
700
0,003
0,005
0,033
0,04
0,037
7,50
Ph hp th ca hn hp phc theo l thuyt v theo thc t trng nhau trong
gii hn sai s cho php (< 15%), cc phc Cu PAN, Zn PAN, Co- PAN c tnh
cng tnh tt. V vy, chng ti tin hnh s dng phng php hi quy a bin
tuyn tnh xc nh ng thi 3 ion trn.
Phng php hi quy a bin tuyn tnh (CLS, ILS, PLS, PCR)
Kim tra tnh cng tnh ca dung dch hn hp Cu(II), Zn(II) v Co(II)
bc sng cc i ca mi phc v trn ton ph.
Pha 27 dung dch chun cha ng thi Cu(II), Zn(II) v Co(II) trong khong
tuyn tnh kho st.
Ghi ph hp th ca cc dung dch phc trong khong bc sng thch hp
= 500- 700 nm.
Nhp s liu ma trn nng xy dng v ma trn hp th quang thu
c vo phn mm Matlab theo chng trnh my tnh.
Chy chng trnh Matlab tnh kt qu hm lng ca Cu(II), Zn(II) v
Co(II) trong mu t to (mu kim tra) v mu thc t.
3.2.2.1. Thut ton CLS
Nhp ma trn s liu nng cc cht trong cng hn hp khi xy dng
ng chun X (mxk).
Nhp tn hiu phn tch di dng vect ct hoc ma trn.
Vit cu lnh tnh h s K ca phng trnh hi qui vi:
K= inv(X*X)*X*y
Nhp tn hiu phn tch y0 ca mu cn nh phn.
Tnh X0=y0*K *inv(K*K)
D liu u vo
Ma trn nng Cchuan (27X3) (bin c lp) gm 27 dung dch chun ca
3 cu t Cu(II) , Zn(II) , Co(II).
67
Ma trn bin ph thuc hp th quang Achuan (27X100) ca 27 dung dch

chun o ti 100 bc sng trong vng ph 500-700 nm (chn khong bc
sng 540 639 nm).
Ma trn gi tr hp th quang Aktra (20X100) ca 20 mu kim tra o ti
100 bc sng trong vng ph 500-700 nm (bin ph thuc), (chn bc sng
540 639 nm).
Ma trn nng kim tra Cktra (20X3) gm 20 dung dch kim tra ca 3 cu
t Cu(II) , Zn(II) , Co(II) cn phn tch ng thi.
Ma trn gi tr hp th quang Amau (8X100) ca mu thc t o ti 100
bc sng trong vng ph 500-700 nm (bin ph thuc).
Cc thut ton
%Phuong phap CLS:
%Nhap ma tran nong do Cchuan(27x3)
%Nhap ma tran do hap thu quang Achuan(27x100)
%Tinh ma tran he so hoi quy K:
K=inv(Cchuan'*Cchuan)*Cchuan'*Achuan;
%Nhap ma tran do hap thu quang cua mau kiem tra: Aktra(20x100)
%Tinh nong do mau kiem tra:
Cktracls=Aktra*K'*inv(K*K');
%Tinh sai so giua nong do chuan voi nong do xac dinh duoc tu PP CLS:
Scls=(Cktra-Cktracls)*100./Cktra;
%Nhap ma tran do hap thu quang cua mau: Amau(8X100)
%Tinh nong do cac chat trong mau:
Cmaucls=Amau*K'*inv(K*K');
Kt qu
Bng 34: Sai s gia nng mu chun v nng xc nh c t phng
php CLS
Cktra (ppm)
Cu(II) Zn(II) Co(II)
0
0,6
0,6
Cktracls (ppm)
Cu(II) Zn(II) Co(II)
0,00
0,62
0,59
68
Cu(II)
-
Scls
Zn(II)
-2,88
Co(II)
1,05
0
0
0
0
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,8
0,8
0,8
0,8
0,8
0,8
0,6
0,8
0,00
0,53
0,79
12,05
0,87
0,8
0
-0,01
0,84
0,00
-5,32
0,8
0,6
-0,01
0,73
0,60
8,95
0,31
0,8
0,8
-0,01
0,79
0,80
1,48
0,36
0
0
0,61
0,01
0,00
-1,81
0
0,6
0,60
0,03
0,61
0,39
-0,89
0
0,8
0,59
0,02
0,82
1,57
-2,27
0,6
0
0,60
0,64
0,00
0,07
-6,93
0,6
0,6
0,58
0,50
0,61
4,04
17,32
-0,98
0,6
0,8
0,58
0,48
0,81
4,16
19,36
-1,02
0,8
0
0,59
0,77
0,00
2,33
4,32
0,8
0,6
0,58
0,70
0,59
3,69
12,84
0,93
0,8
0,8
0,57
0,57
0,81
5,52
28,96
-0,85
0
0
0,80
0,03
0,02
-0,11
0
0,6
0,78
0,02
0,60
2,07
-0,01
0
0,8
0,78
0,04
0,81
2,69
-1,42
0,6
0
0,78
0,57
0,00
2,93
4,69
0,6
0,6
0,77
0,52
0,60
3,54
12,84
-0,33
0,6
0,8
0,76
0,49
0,80
5,62
18,23
0,14
T bng kt qu trn, ta thy hu ht sai s thu c u thuc gii hn sai s
cho php, ngay c khi trong dung dch kim tra c mt hoc hai cu t vn cho kt
qu tt. Mt s mu kim tra, kt qu chy my xc nh c hm lng cu t (d
hm lng u vo = 0), nhng kt qu nhn c di LOD nn c th xem nh
y l do nhiu trong php o. Nh vy, thut ton CLS c kh nng p dng tt vo
vic phn tch mu thc t (qui trnh phn tch v xc nh nu mc 3.3.2.)
3.2.2.2. Thut ton ILS
D liu u vo
Ma trn (bin c lp) nng Cchuan (27X3) ca 27 dung dch chun cha
ba cu t Cu(II) , Zn(II) , Co(II).
Ma trn hp th quang Achuan (27X20) ca 27 dung dch chun o ti 20
bc sng c trng trong vng ph 500 700 nm (chn bc sng m ti
t tnh cng tnh tt 550 - 569).
Ma trn gi tr bin ph thuc hp th quang Aktra (20X20) ca 20 mu
kim tra o 20 bc sng.
Ma trn nng cc dung dch kim tra Cktra (20X3)
69
Ma trn gi tr bin ph thuc hp th quang Amau (8X20) ca mu cn

phn tch o 20 bc sng.
Cc thut ton
%Phuong phap ILS:
%Nhap ma tran do hap thu quang cua 27 dung dich chuan tai 20 buoc song:
Achuan(27x20)
%Tinh ma tran he so hoi quy:
P=inv(Achuan'*Achuan)*Achuan'*Cchuan;
%Nhap ma tran do hap thu quang cua mau kiem tra: Aktra(20x20)
%Tinh nong do chat trong mau kiem tra:
Cktrails=Aktra*P;
%Tinh sai so giua nong do chuan voi nong do xac dinh duoc tu ILS:
Sils=(Cktra-Cktrails)*100./Cktra;
%Nhap ma tran do hap thu quang cua mau Amau(8x20)
%Tinh nong do cua mau:
Cmauils=Amau*P;
Kt qu
php ILS
Cu
0
0
0
0
0
0,6
0,6
0,6
0,6
0,6
0,6
Cktra
Zn
0,6
0,6
0,8
0,8
0,8
0
0
0
0,6
0,6
0,6
Co
0,6
0,8
0
0,6
0,8
0
0,6
0,8
0
0,6
0,8
Cu
-0,03
0,02
-0,04
-0,03
0,05
0,65
0,62
0,63
0,60
0,63
0,59
Cktrails
Zn
0,69
0,30
1,05
0,75
0,59
-0,04
-0,24
0,07
0,88
0,44
0,52
70
Co
0,61
0,77
0,03
0,58
0,74
-0,03
0,57
0,81
0,01
0,57
0,80
Cu
-8,52
-3,16
-4,17
0,63
-4,58
1,00
Sils
Zn
-14,37
50,07
-31,66
5,82
26,69
-47,38
27,29
12,98
Co
-1,36
3,81
3,51
7,37
4,24
-1,04
5,05
0,26
0,6
0,6
0,6
0,8
0,8
0,8
0,8
0,8
0,8
0,8
0
0,60
0,93
0,01
0,27
-15,71
0,8
0,6
0,59
0,76
0,56
1,00
5,46
6,05
0,8
0,8
0,57
0,66
0,82
4,87
17,31
-2,47
0
0
0,80
0,14
0,03
-0,52
0
0,6
0,80
-0,06
0,58
0,52
4,13
0
0,8
0,84
-0,03
0,76
-5,02
4,51
0,6
0
0,87
0,62
-0,10
-9,31
-3,49
0,6
0,6
0,74
0,81
0,69
7,35
-35,42 -14,21
0,6
0,8
0,72
0,66
0,86
9,78
-9,32
-7,49
qu tt. Nh vy, thut ton ILS c kh nng p dng tt vo vic phn tch mu thc
t (qui trnh phn tch v xc nh nu mc 3.3.2.)
3.2.2.3. Thut ton PLS
D liu u vo
Ma trn nng chun Cchuan (27X3) ca 27 dung dch chun cha ba cu
t Cu(II) , Zn(II) , Co(II).
Ma trn hp th quang ca cc dung dch chun Achuan(27X100)
Ma trn hp th quang ca mu kim tra Aktra(20X100)
Ma trn hp th quang ca mu thc Amau(8X100)
Cc thut ton
%Phuong phap PLS:
%Nhap ma tran do hap thu quang Achuan(27x100)
%Tinh vecto trong so:
w=(Achuan'*Cchuan)*inv(Cchuan'*Cchuan);
%Tinh tri so va trong so:
t=Achuan*w;
P=(Achuan'*t)*inv(t'*t);
q=(Cchuan'*t)*inv(t'*t);
b=w*inv(P'*w)*q;
71
a=mean(Cchuan)-mean(Achuan)*b;
a1=[ones(20,1)*a(1) ones(20,1)*a(2) ones(20,1)*a(3)];
%Nhap ma tran do hap thu quang cua mau kiem tra:Aktra
%Tinh nong do mau kiem tra theo PLS:
Cktrapls=a1+Aktra*b;
a2=[ones(3,1)*a(1) ones(3,1)*a(2) ones(3,1)*a(3)];
%Nhap ma tran do hap thu quang cua mau thuc: Amau(8100)
Cmaupls=a2+Amau*b;
%Tinh sai so giua nong do chuan voi nong do xac dinh duoc tu PP PLS:
Spls=(Cktra-Cktrapls)*100./Cktra;
Kt qu
php PLS
Cu
0
0
0
0
0
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,6
0,8
0,8
0,8
0,8
0,8
0,8
Cktra(ppm)
Zn
0,6
0,6
0,8
0,8
0,8
0
0
0
0,6
0,6
0,6
0,8
0,8
0,8
0
0
0
0,6
0,6
0,6
Co
0,6
0,8
0
0,6
0,8
0
0,6
0,8
0
0,6
0,8
0
0,6
0,8
0
0,6
0,8
0
0,6
0,8
Cktrapls(ppm)
Cu
Zn
Co
-0,24
0,85
0,65
-0,21
0,73
0,84
-0,37
1,21
0,09
-0,19
0,91
0,64
-0,10
0,87
0,82
0,22
0,41
0,09
0,43
0,19
0,64
0,49
0,10
0,84
0,47
0,76
0,03
0,60
0,45
0,60
0,66
0,37
0,79
0,51
0,83
0,02
0,68
0,57
0,57
0,69
0,42
0,78
0,52
0,30
0,08
0,71
0,08
0,62
0,78
0,01
0,81
0,72
0,62
0,02
0,90
0,36
0,57
0,94
0,27
0,75
72
Cu
62,69
28,66
18,15
21,03
0,73
-10,48
15,67
-13,44
-14,34
34,59
11,47
2,08
10,61
-13,06
-17,10
Spls
Zn
-41,83
-20,91
-51,20
-13,89
-8,38
-26,10
24,27
38,49
-3,91
29,21
47,52
-2,94
40,05
54,22
Co
-7,86
-4,83
-6,75
-2,10
-7,21
-4,94
0,12
1,79
5,27
2,89
-2,63
-1,03
5,18
5,71

qu tt. Nh vy, thut ton PLS c kh nng p dng tt vo vic phn tch mu
thc t (qui trnh phn tch v xc nh nu mc 3.3.2.)
3.2.2.4. Thut ton PCR
D liu u vo
Ma trn nng chun Cchuan (27X3)
Ma trn hp th quang ca cc dung dch chun Achuan(27X100)
Ma trn hp th quang ca mu kim tra Aktra(20X100)
Ma trn hp th quang ca mu thc Amau(8X00)
Cc thut ton
%Phuong phap PCR:
%Binh phuong tap so lieu chua bien phu thuoc Achuan
D = Achuan'*Achuan;
% Su dung mot trong 3 ham tinh PC de xac dinh cac PC theo cau lenh sau, su
% dung ham SVD
[V S] = svd(D);
% Tinh ma tran phan tram phuong sai cua cac PC
d = diag(S)/sum(diag(S))*100;
% Tu gia tri phan tram phuong sai cua cac PC, can cu vao yeu cau cu the cua
% bai toan de quyet dinh so PC lam co so cho khong gian moi cua tap so lieu
% (n):
f = V(:,1:20);
% Chuyen doi tap so lieu ban dau va tinh ma tran he so hoi qui:
Yj = Achuan*f;
F = inv(Yj'*Yj)*Yj'*Cchuan;
Fj=f*F
% Nhap ma tran do hap thu quang cua mau kiem tra:Aktra
73
%Tinh nong do mau kiem tra theo PCR:

Xktra=Yktra*Fj;
%Tinh sai so giua nong do chuan voi nong do xac dinh duoc tu PLS:
Spcr=Cktra-Xktra)*100./Cktra ;
% TINH NONG DO CUA CHAT TRONG MAU BAT KI.
%Nhap ma tran do hap thu quang cua mau thuc: Amau
% Tinh nong do mau theo cong thuc:
Cmaupcr=Amau*Fj
Kt qu
php PCR
Cktra(ppm)
Cktrapcr (ppm)
Spcr
Cu
Zn
Co
Cu
Zn
Co
Cu
Zn
Co
0
0,6
0,6
-0,01
0,61
0,60
-0,87
0,55
0
0,6
0,8
-0,01
0,56
0,80
7,16
0,41
0
0,8
0
-0,01
0,89
0,00
-10,69
0
0,8
0,6
-0,01
0,69
0,60
13,33
-0,20
0
0,8
0,8
-0,01
0,82
0,79
-2,93
0,82
0,6
0
0
0,61
0,01
0,00
-1,50
0,6
0
0,6
0,59
0,00
0,60
2,28
0,59
0,6
0
0,8
0,59
0,02
0,82
2,14
-2,68
0,6
0,6
0
0,61
0,65
0,00
-1,78
-8,14
0,6
0,6
0,6
0,57
0,49
0,60
4,49
17,87
0,58
0,6
0,6
0,8
0,58
0,51
0,81
3,05
14,69
-1,48
0,6
0,8
0
0,60
0,80
0,00
-0,45
0,55
0,6
0,8
0,6
0,58
0,74
0,59
3,73
7,04
1,00
0,6
0,8
0,8
0,58
0,62
0,82
3,93
21,94
-2,34
0,8
0
0
0,81
0,04
0,02
-1,15
0,8
0
0,6
0,78
0,03
0,60
2,67
-0,01
0,8
0
0,8
0,78
0,07
0,82
1,98
-2,41
0,8
0,6
0
0,79
0,54
0,00
0,76
9,88
0,8
0,6
0,6
0,78
0,54
0,61
2,55
9,22
-2,01
0,8
0,6
0,8
0,76
0,43
0,81
5,43
28,54
-1,21
74
qu tt. Nh vy, thut ton PCR c kh nng p dng tt vo vic phn tch mu
thc t (qui trnh phn tch v xc nh nu mc 3.3.2.)
T kt qu tnh c cho thy c bn phng php: phng php hi quy cu
t chnh (PCR), phng php hi quy a bin CLS, ILS, PLS u cho kt qu kh
tt.
Da vo sai s tng i ca cc phng php PLS, CLS, ILS v PCR , chng
ti nhn thy sai s ca phng php PCR l nh nht v thuc khong sai s cho
php. Sai s ca phng php CLS trong mt s mu kh ln l do phng php
CLS xc nh ng thi cc cu t da trn d liu ton ph, v vy khng loi b
c nh hng ng k ca ph cc phc mu ca cc ion trong cng hn hp. V
vy chng ti chn phng php PCR kt hp vi phng php trc quang xc
nh ng thi 3 nguyn t Cu, Zn, Co trong mu thc t, vi phng php so snh l
phng php hp th nguyn t AAS.
3.3. ng dng vo phn tch mu phn vi lng

3.3.1. Qui trnh ph mu
Cn 1 gam mu phn vi lng, chuyn vo cc chu nhit, thm vo vi ml
nc, 10ml HNO3 , y bng np knh ng h, un cch ct, cho t t dung dch
H2O2 vo dung dch n khi thy dung dch trong sut. C cn dung dch, ngui,
cho thm nc ct vo cc v tip tc c cn. Chuyn dung dch vo bnh nh mc
c 50ml, nh mc bng nc ct n vch. Ly cc th tch cn thit t dung dch
ny thc hin cc php o quang. Lm th nghim tng t i vi mu trng
so snh.
3.3.2. Phn tch mu phn vi lng
Bng 38: Hm lng Cu(II), Zn(II), Co(II) trn nhn mt s mu phn vi lng
Mu
STT
1
2
3
Tn
Milo L1 *
Milo L2 *
Milo R2 *
Hm lng ghi trn nhn (ppm)

Cu
Zn
Co
Mn
500
300
500
300
300
500
500
300
400
75
Fe
-
4
5
6
7
8
Milo L3 *
Milo Ga3 *
Vitamin *
K-H Humat **
Vegamin **
200
500
600
900
100
300
350
400
900
500
+
120
400
300
1000
600
50
100
* Sn phm ca Cng ty sn xut v thng mi MINH LONG

** Sn phm ca Cng ty sn xut v thng mi MINH C
Sau khi thu c 8 mu, tin hnh pha long em phn tch Cu(II), Zn(II) v
Co(II) bng ba phng php: Phng php ph hp th nguyn t ngn la (F-AAS),
phng php trc quang vi thuc th PAN s dng phng php hi quy a bin v
phng php tch sc k. Trc khi tin hnh phn tch, chng ti tin hnh pha long
cc mu nh sau:
i vi mu dng xc nh bng phng php AAS: Chun b cc bnh nh
mc c 50 ml, ly 10 ml mu, nh mc n vch bng dung dch HNO3 1%.
Tin hnh o AAS v thu c kt qu nh sau:
Bng 39: Hm lng Cu(II), Zn(II), Co(II) trong mu o bng phng php AAS
Hm lng (ppm)
Cu
Zn
Co
1
2,013
1,293
2
1,320
1,280
3
2,007
1,260
4
0,793
1,220
0,007
5
1,996
1,460
0,005
6
2,434
1,647
0,007
7
3,613
3,600
1,181
8
0,420
1,987
0,473
i vi mu dng xc nh ng thi s dng thut ton hi qui a bin:
Mu o
Ly vo cc bnh nh mc c 25 ml c 2 ml mu + dung dch m (axetat 4.102
M v citrat 1.10-3 M) + hn hp PAN 1,6.10-4M + Triton X-100 2%. Lm lp li ba
ln i vi mi mu. Tin hnh o quang trong khong bc sng 500-700 nm, nhp
gi tr ma trn hp th quang vo chng trnh thut ton chy trn phn mm
matlab v thu c kt qu hm lng trung bnh tng mu o nh sau:
Bng 40: Xc nh ng thi hm lng Cu(II), Zn(II), Co(II)
76
Hm lng (ppm)
Cu
Zn
Co
0,802
0,493
0,517
0,514
0,829
0,502
0,345
0,491
0,802
0,587
0,973
0,668
1,450
1,447
0,466
0,166
0,795
0,186
mu dng xc nh ring r bng phng php tch sc k trao i
Mu o
1
2
3
4
5
6
7
8
i vi
ion: Ly 5ml mu vo cc bnh nh mc c 10ml, dng HCl c iu chnh sao cho

nn axit trong bnh l HCl 9M. Tin hnh theo qui trnh tch nh nu trn. Sau ,
o ph ca Cu(II), Zn(II) v Co(II) ln lt ti cc bc sng tng ng.Da vo
phng trnh ng chun n bin xc nh nng theo tn hiu o quang thu
c.
Bng 41: Hm lng Cu(II), Zn(II), Co(II) trong mu o bng phng php tch
Hm lng (ppm)
Cu
Zn
Co
1
0,405
0,613
2
0,240
0,648
3
0,405
0,650
4
0,160
0,613
5
0,405
0,745
6
0,485
0,863
7
0,730
1,875
0,588
8
0,080
1,005
0,238
T cc kt qu thu c, khi tnh n h s pha long, ta c kt qu sau:
Mu o
Bng 42 : Hm lng trung bnh ca cc ion

Mu
1
2
3
4
5
Phng php tch (1)

Cu
506,25
300,00
506,25
200,00
506,25
Zn
306,25
323,75
325,00
306,25
372,50
Co
-
Hm lng cc kim loi (ppm)

Phng php xc nh
ng thi (2)
Cu
Zn
Co
501,25 308,05
323,15 320,95
518,15 313,65
215,65 307,10
501,25 367,15
-
77
Phng php AAS (3)
Cu
503,25
330,00
501,75
198,25
499,00
Zn
323,35
320,00
315,00
305,00
365,00
Co
1,65
1,15
6
7
8
606,25
912,50
100,00
431,25
937,50
502,50
293,75
118,75
608,15
906,25
103,75
417,25
904,40
496,60
291,30
116,55
608,50
903,25
105,00
411,65
900,00
496,65
1,80
295,35
118,15
nh gi ba phng php
Bng 43: Kt qu phn tch hm lng Cu(II) (ppm)
Mu
1
2
3
4
5
6
7
8
PP (1)
506,25 0,883
300,00 1,217
506,25 0,867
200,00 1,150
506,25 1,783
606,25 1,367
912,50 1,350
100,00 1,333
C SD
PP (2)
501,25 0,910
323,15 1,170
518,15 0,840
215,65 1,170
501,25 1,750
608,15 1,320
906,25 1,410
103,75 1,260
PP (3)
503,25 0,790
330,00 1,380
501,75 0,960
198,25 1,080
499,00 1,900
608,50 1,530
903,25 1,140
105,00 1,590
Bng 44: Kt qu phn tch hm lng Zn(II) (ppm)

Mu
1
2
3
4
5
6
7
8
PP (1)
306,25 2,467
323,75 1,867
325,00 1,033
306,25 1,633
372,50 2,017
431,25 1,533
937,50 1,500
502,50 2,300
C SD
PP (2)
308,05 2,300
320,95 1,840
313,65 0,980
307,10 1,580
367,15 1,990
417,25 1,480
904,40 1,540
496,60 2,200
78
PP (3)
323,35 3,050
320,00 1,960
315,00 1,220
305,00 1,820
365,00 2,110
411,65 1,720
900,00 1,360
496,65 2,650
Bng 45: Kt qu phn tch hm lng Co(II) (ppm)

C SD
PP (1)
PP (2)
PP (3)
7
293,75 1,533
291,30 1,460
295,35 1,790
8
118,75 2,067
116,55 2,000
118,15 2,300
Da vo bng trn, dng chun t so snh 2 gi tr trung bnh ca 2 cp
Mu
phng php: phng php (1) v (2), phng php (2) v (3) trong cc mu, nhn
thy ttnh< tbng[8], t c th rt ra kt lun thng k: cc gi tr trung bnh ca cc
phng php khc nhau khng c ngha thng k (ging nhau) hay phng php
(2) cho kt qu ging phng php (1) v (3).
Phng php xc nh ng thi khng ch c nhy tt m cn tit kim thi
gian (so vi phng php tch), hiu qu kinh t (so vi phng php AAS) v tin
hnh n gin. Phng php ny c kh nng ng dng tt trong vic xc nh ng
thi Cu(II), Zn(II), Co(II) trong cc mu phn vi lng ni ring v cc mu thc t
khc ni chung.
79
KT LUN
Vi mc tiu ban u t ra cho lun vn l nghin cu o quang xc nh cc
nguyn t chuyn tip, sau mt thi gian nghin cu chng ti thu c mt s kt
qu sau:
1. Kho st ph c trng ca cc phc mu Cu- PAN, Zn- PAN v Co- PAN
trong mi trng mixen (Tween 80 hoc Triton X-100) trong khong 500 700 nm
nhn thy s lng cc cc i hp th ca cc phc ln lt l 1, 2, 2 ging nh
trong dung mi khc nhng gi tr chuyn dch v pha sng ngn: 558 nm (CuPAN), 522 v 556 nm (Zn- PAN), 580 v 620 nm (Co- PAN). T , chng ti la
chn php o quang trong mi trng Triton X-100 v o ti cc bc sng 558 nm
(Cu- PAN), 556 nm (Zn- PAN), 580 v 620 nm (Co- PAN).
2. Tm c cc iu kin thch hp nht cho php o quang:
hp th quang cho tn hiu n nh khong pH 5 7, hn hp m (axetat
2.10-4 M v citrat 1.10-3 M).
Nng ti u ca PAN l 1,6.10-4 M, nng Triton X-100 l 2% .
ng chun Cu(II) tuyn tnh hong 0,021 1,41 ppm, LOD = 0,0047 ppm,
LOQ = 0,0156 ppm,
ng chun Zn(II) tuyn tnh trong khong 0,03 1,56 ppm, LOD = 0,007
ppm, LOQ = 0,0239 ppm.
ng chun Co(II) tuyn tnh trong khong 0,06 2,12 ppm, LOD = 0,0094
ppm, LOQ = 0,0314 ppm.
Kh nng lp li ca 3 khong nng c h s bin ng di 3%. Cc ion
nh hng l Fe2+, Fe3+, Mn2+ v b loi tr bng citrat 1.10-3M.
3. Da trn ph hp th ca cc phc mu ca Cu(II), Zn(II) v Co(II) vi
thuc th PAN trong khong tuyn tnh, trn ton ph ca hp th quang, nhn
thy c s cng tnh gia cc ph. Do vy, chng ti tin hnh hai phng php:
80
Phng php th nht: xc nh ring tng nguyn t bng phng php tch
sc k trao i ion vi ct tch Dowex 1, pha ng tch Cu(II), Co(II), Zn(II) ln
lt l 9M, 4M v 0,5M.
Phng php th hai: xc nh ng thi Cu(II), Zn(II) v Co(II) trong cng
hn hp vi s kt hp thut ton hi qui a bin tuyn tnh thc hin trn phn mm
Matlab 7.0. Lp ma trn tnh cc h s hi qui t 27 dung dch chun, da trn kt
qu phn tch 20 mu gi tm c m hnh PLS, CLS, ILS v PCR thch hp vi sai
s tng i khi phn tch mu t to phn ln nh hn 15% tho mn sai s cho
php. Mt s mu kim tra khng c c ba ion, kt qu phn tch vn xc nh
c hm lng ca ion vng mt, nhng hm lng ca chng nh hn gii hn
nh lng nn c th coi l sai s do nhiu.
4. Phng php nghin cu xc nh ng thi vi cc thut ton CLS, ILS,
PLS, PCR c ng dng xc nh Cu, Zn v Co trong cc mu phn vi lng
vi kt qu ph hp vi phng php tch v php o AAS.
Qua ti ny, hy vng chng ti gp phn vo vic m rng phm vi ng
dng phng php o quang trong mi trng mixen kt hp vi cc thut ton hi
qui a bin tuyn tnh xc nh ng thi khng ch Cu, Zn, Co m cn nhiu
nguyn t vi lng trong phn bn ni ring, cng nh cc i tng khc ni chung.
81
TI LIU THAM KHO

Ting Vit
1.
Chu nh Bnh, Phm Lun, 2006, Nghin cu phn ng to phc cht gia
Co(II) v Ni(II) vi thuc th PAN trong mi trng Mixen, nh gi kh nng
p dng vo phn tch ng thi Co(II) v Ni(II), Tp ch phn tch Ho, L v
Sinh hc, Tp 11, S 4/2006.
2.
Trn Thc Bnh, Trn T Hiu, Phm Lun (1996), Xc nh trc quang Cu,
Ni, Mn, Zn...trong cng hn hp bng Pyridin-azo-naphtol(PAN), Tp
ch Phn tch Ho, L v Sinh Hc, tp 1, s (3+4).)
3.
Trn T Hiu, T Vng Nghi, Nguyn Xun Trung, Nguyn Vn Ri (2003),

Cc phng php phn tch cng c, NXB i hc Quc gia H Ni.
4.
Trn T Hiu (2003), Phn tch trc quang ph hp th UV VIS, NXB i

hc Quc gia H Ni
5.
T Duy Lim (2001), C s Matlab v ng dng,NXB Khoa hc k thut.
6.
Phm Lun (2005), C s ca phng php hp th nguyn t, NXB i hc

Quc Gia H Ni.
7.
L Vn Khoa, Nguyn Xun C, L c, Trn Khc Hip, Trn Cm Vn

(2003), t v mi trng, NXB Gio dc.
8. L c Ngc (2007), Bi ging x l s liu v k hoch ha thc nghim,

i hc Khoa Hc T Nhin i hc Quc Gia H Ni.
9.
Hong Nhm (2000) Ho hc v c , NXB Gio dc, tp 3.
10. Nguyn Hu Ph (2003), Ho l & ho keo, NXB KH v KT.

11. T Th Tho (2006), Bi ging chuyn Thng k trong Ha phn tch, NXB
i hc Quc gia H Ni.
12. T Th Tho (2005), Gio trnh chemometrics, i hc Khoa Hc T Nhin

i hc Quc Gia H Ni.
13. ng ng Vn (2007), Gio trnh ho tin c s, NXB i hc Quc gia H
Ni.
14. N.I. Bloc (1986), Ha hc phn tch nh tnh, NXB Gio dc.
82
15. http://forum.caycanhvietnam.com/diendan/showthread.php?t=4454
16. http://baigiang.violet.vn/present/show?entry_id=258546
17. http://www.webtretho.com/forum/f119/vai-tro-cua-cac-nguyenvi-luong-co-432315/
Ting Anh
18. Abbas Afkhami (2004), H-point standard addition method for simultaneous
spectrophotometric determination of Co(II) and Ni(II) by 1-(2 pyridylazo)-2
naphthol in micellar media, Spectrochimica Acta Part A, 60, pp. 181-186.
19. Abbas Afkhami (2004), Mean centering of ratio kinetic profiles as a nouvel
spectrophotometric method for the simultaneous kinetic analysis of binary
mixtures, Analytical Chimica Acta, 526, pp. 211 - 218.
20. Abbas Afkhami (2004), Successive ratio - derivative spectra as a new
spectrophotometric
method
for
the
analysis
of
ternary
mixtures,
Spectrochimica Acta Part A, 61, pp. 869 - 877.

21. Ana Cristi B.Dias, Josiane M.T. Carneiro (2004), Spectrophotometric flowinjection determination of zinc in plant digests based on a spot test, Atlanta,
63, pp. 245 - 250.
22. Alfonso Fernndez - Gonzlez (2005), Insights into the reaction of -lactam
antibiotics with copper(II) ions in aqueous and micellar media: Kinetic and
spectrophotometric studies, Analytical Biochemistry, 341, pp. 113 - 121.
23. Barry Chiswell and Guy Rauchle (1990), Spectrophotometric method for the
determination of manganese, Atlanta, 37, pp. 237 - 259.
24. Barbara A.Bowman, Robert M.Russell (2001), Present knowledge in
nutrition, ILSI Press Washington, DC, eight edition.
25. Coleman JE (1998), Zinc enzymes, Curr Opin Chem Biol.
26. E.B. Sandell, Photometric determination of trace of element, Wiley
Interscience
27. G.A.Shar and G.A.Soomro (2004), Spectrophotometric determination of
cobalt(II), nickel(II) and copper(II) with 1-(2 pyridylazo)-2 naphthol in micellar
medium, The Nucleus, 41 (1-4) 2004: 77 82.
83
28. G. Bagherian, M. Arab Chammjangali (2007), Simultaneous determination of

cobalt and palladium in micellar media using H- point standard addition method
and partial least square regression, Spectrochimica Acta Part A, 67, pp. 378 384.
29. G.Bryan Balas, Robert S, Glass Leslie(1995), Analyst, Vol,120 : 523-527.
30. H. M. N. H. Irving and A. M. Kiwan (October 1971), Studies with dithizone:
Part XXV, Secondary copper(II) dithizonate, Analytica Chimica Acta, Volume
56, Issue 3, Pages 435-446.
31. I.A. Starovoitova, V.G.Khozin, L.A. Abdrakhmanova (2008), Application of
nonlinear PCR for optimization of hybrid binder used in construction
materials, Chemometrics and Intelligent Laboratory Systems.
32. Kuang Lu Cheng and Roger H. Bray, Analytical Chemistry - 1-(2-Pyridylazo)2-naphthol as Possible Analytical Reagent , University of Nlinois Urbana, III.
33. K.
Zarei,
M.
Atabati,
Z.
Malekshabani
(2006),
Simultaneous
spectrophotometric determination of iron, nickel and cobalt in micellar media

by using direct orthogonal signal correction partial least squares method,
Analytica Chimica Acta, 556, pp. 247 - 254.
34. Leila Hejazi, Diako E. Mohammadi, Yadollah Yamini, Richard G. Brereton,
Solid-phase extraction and simultaneous spectrophotometric determination of
trace amounts of Co, Ni and Cu using partial least squares regression
Talanta, Volume 62, Issue 1, 9 January 2004, Pages 183-189.
35. Lilibeth dlC. Coo, Terence J. Cardwell, Robert W. Cattrall and Spas D. Kolev,
Spectrophotometric study of the solubility and the protolytic properties of 1-(2pyridylazo)-2-naphthol in different ethanolwater solutions , Analytica
Chimica Acta, Volume 333, Issues 1-2, 30 October 1996, Pages 119-124.
36. L. Sommer, G. Ackermann, D. Thorburn Burns, 1990, Inorganic chemical
analysis classical methods, molecular spectroscopy (Absorption and extraction)
and solvent extraction, Pure & Appl, Vol 62, No. 12, pp 2323-2338.
37. MacDonald RS (2000), The role of zinc in growth and cell proliferation, J
Nutr.
84
38. M. Arab Chammjangali, G. Bagherian (2005), Simultaneous determination of

cobalt, nickel and palladium in micellar media using partial least square
regression and direct orthogonal signal correction, Spectrochimica Acta Part
A, 62, pp. 189 - 196.
39. M.Arvand,
S.Abolghasemi,
M.A.
Zanjanchi
(2007),
Simultaneous
determination of Zinc and Copper(II) with 1-(2-pyridylazo)-2-naphthol in

Micellar Media by Spectrophotometric H point Standard Addition Method,
Journal of Analytical Chemistry, 62, pp. 342 - 347.
40. Narinder
Kumar
Agnihotri
(1997),
Derivative
spectrophotometric
determination of copper (II) in non-ionic micellar medium, Atlanta, 45, pp.

331-341.
41. Ogla Ch. Manouri, Nikolaos D. Papadimas, Sophia E. Salta (1998), Three
approaches to the analysis of zinc(II) in pharmaceutical formulations by means
of different spectrometric methods, Il Farmaco, 53, pp. 563 569.
42. Qin Wei, Liangguo Yan, Guohua Chang, Qingyu Ou (2003), Kinetic
spectrophotometric determination of trace manganese (II) with dahlia violet in
nonionic microemulsion medium, Atlanta, 59, pp. 253 - 259.
43. R. Codony, M.D. Prat, J.L. Beltran (2000), Study on partition equilibria of
metal complexes in non ionic micellar solutions from spectrophotometric
data, Atlanta, 52, pp. 225 - 232.
44. Saonli Basu, Saktipada De, Benoy B. Bhowmik (2007), Photophysical studies
of Merocyanine 540 dye in aqueous micellar dispersions of different surfactants
and in different solvents, Spectrochimica Acta Part A, 66, pp. 1255 - 1260.
45. Senay
Tacioglu
(2007),
Micellar
effect
on
the
sensitivity
of
Spectrophotometric Mo(VI) determination based on the formation of gallic acid

complex providing evidence for the polyoxoanion structure of molybdate ions,
Analytica Chimica Acta, 590, pp. 217 - 223.
46. Turnland JR (1998), Human whole body copper metabolism, Am J Clin
Nutr.
47. http://en.wikipedia.org/wiki/Polysorbate_80
85
48. http://en.wikipedia.org/wiki/Triton_X-100
49. http://msds.chem.ox.ac.uk/PY/1-(2-pyridylazo)-2-naphthol.html
86

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MC LC

2.4.4. Phng php hi qui cu t chnh (PCR)................................................39

Bng k hiu cc t vit tt

(Phng php bnh phng ti thiu thng thng)

(Phng php bnh phng ti thiu nghch o)

(Phng php hi qui cu t chnh)

(Phng php bnh phng ti thiu tng phn)

(Quang ph t ngoi kh kin)

Bng 31:Nng thm chun....................................................................................63

CHNG 1. TNG QUAN

mt cht dinh dng cn thit cho c th con ngi vi mt hm lng rt nh (80

xng, tim, no, gy ra s hot ng khng bnh thng ca cc c quan th gic, v

v c ngha i vi c nh nit phn t bng con ng sinh hc. Co cha trong

1.1.2. c tnh phn tch ca ng, km, coban

Hp cht ca Cu(I) c c tnh oxi ha v tnh kh.

Cc hp cht Cu(I) d b oxy ha (ngay c bi oxy khng kh) chuyn thnh

Cu(OH)2 cn th hin tnh cht axit yu.

natriietyldithiocacbamat, ithizon, Nhng

Tnh lng tnh ca hyroxit cng vi th in cc kh m ca kim loi gii

Cc ion Co2+ to nn nhiu phc cht bt din vi s phi tr 6.

Co(III) to c rt nhiu phc cht v hu ht chng c cu hnh bt din.

1.2. Mt s phng php quang xc nh Cu(II), Zn(II), Co(II)

1.2.1. Phng php ph hp th nguyn t AAS

cc tc gi Serife Tokalioglu, Senol Kartal v Latif Elci xc nh lng vt ion kim

1.2.2. Phng php phn tch trc quang

1-(2-pyridylazo )- Triton X-100

Cc phc cht ca Cu(II) thng thng c chit nh cc dung mi hu c

Vi thuc th Natridiethyl dithiocacbamat (NaDDC), phn ng to phc trong

3,5-diCl-DMPAP phn ng vi coban trong mi trng pH= 2,2 6,0, nhit

Mt s nghin cu o quang trong mi trng Tween 80

v xc nh c vng tuyn tnh ca Co(II) v Pd(II) ln lt l 0,2 2 g/ml v 0,4

Olga Ch.Manouri v cng s nghin cu phn tch hm lng Zn(II) trong

1.3. Thuc th 1-(2-pyridylazo )-2- naphtol (PAN)

1.3.2. Kh nng to phc ca PAN

M (II hoac III)

Thnh phn ca cc dng c chit vo trong cc dung mi khng trn ln

= 105,2. Phc vng cng ca cc kim loi di y c mu trong cloroform

Thnh phn phc

Hu ht cc kim loi u cn dung dch axit yu hoc baz yu chit v cn

xc nh c trong s c mt ca Cd; Cu; Hg; Pb v Ag bng cch che cc ion kim

Cc tc gi dng phng php so mu xc nh Zn, Cu v Mn trong qu

tch c xc nh trong khong 6-500ppm. Phng php ny c dng nh

L/mol,cm, Khong tun theo nh lut Beer l 0 100gCu/50ml v 0 55g

Ni/50ml, Phc Cu-PAN b phn hy khi thm Na2S2O3,

Mt s tc gi khc xc nh Co bng phng php von ampe s dng in cc

Ngoi ra, cc nh khoa hc trn th gii s dng PAN cho cc mc ch

CHNG 2. THC NGHIM

Xt ph c trng, nh hng ca pH, mixen, nng thuc th.

Xc nh khong tuyn tnh, xc nh gii hn pht hin, gii hn nh

ng dng, xt nh hng ca nguyn t ny n nguyn t kia v

cch loi tr nh hng, tch cc ion khi chng cng c mt.

Xc nh tng nguyn t trong iu kin ti u trn bng phng php

tch sc k trao i ion.

Xc nh hp th quang ng vi tng bc sng, kim tra tnh cng

Xy dng ma trn s ph thuc ca hp th quang vo nng .

La chn php xc nh trong s cc thut ton CLS, ILS, PLS, PCR.

Xy dng ma trn cc mu kim tra, nh gi mc chnh xc ca

phng php, kh nng ng dng vo mu thc t.

nh gi thu hi, i chiu kt qu vi phng php quang ph hp

2.2. Thit b v ha cht

complexon vi cht ch th murexit, pH = 8. Ti im tng ng, dung dch

2.3. Cch tin hnh thc nghim

2.3.2. Qui trnh nghin cu a bin

2.3.3. Qui trnh phn tch mu