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I HC THI NGUYN

TRNG I HC S PHM

NGUYN TH HN

XC NH HM LNG CADIMI V CH TRONG MT S LOI RAU


XANH TI HUYN I T- TNH THI NGUYN BNG PHNG
PHP PH HP TH NGUYN T NGN LA (F-AAS)

LUN VN THC S HO HC

Thi Nguyn, nm 2010


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I HC THI NGUYN
TRNG I HC S PHM

NGUYN TH HN

XC NH HM LNG CADIMI V CH TRONG MT S LOI


RAU XANH TI HUYN I T- TNH THI NGUYN BNG
PHNG PHP PH HP TH NGUYN T NGN LA (F-AAS)

Chuyn ngnh: Ho phn tch


M s: 60.44.29

LUN VN THC S HO HC

NGI HNG DN KHOA HC: PGS.TS NGUYN NG C

Thi Nguyn, nm 2010


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LI CM N
Li u tin ca lun vn ny ti xin chn thnh cm n PGS.TS Nguyn
ng c. Thy tn tnh hng dn v gip ti trong qu trnh thc hin
lun vn.
Ti xin chn thnh cm n cc thy c trong Khoa Ha hc, Trng i hc
S phm, i hc Thi Nguyn; cc thy c, anh ch v cc bn trong b mn Ha
hc, Trng i Hc Khoa Hc, i hc Thi Nguyn gip to iu kin cho
ti trong sut qu trnh lm lun vn.
D c nhiu c gng, song do nng lc cn hn ch nn trong lun vn ca
ti chc chn khng th trnh khi thiu st. Ti rt mong nhn c kin ng
gp ca cc thy c v cc bn lun vn ny c hon chnh hn.
Thi Nguyn, thng 8 nm 2010
Hc vin

Nguyn Th Hn

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DANH MC CC CH VIT TT
Vit tt

Ting Anh

Ting Vit

Abs

Absorbance

hp th

AAS

Atomic Absorption

Php o quang ph hp th

Spectrometry

nguyn t

Flame - Atomic Absorption

Php o quang ph hp th

Spectrometry

nguyn t ngn la

HCL

Hollow Cathoe Lamps

n catt rng

ppm

Part per million

Mt phn triu

F- AAS

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MC LC
Trang
M U ..................................................................................................................1
CHNG 1: TNG QUAN ...................................................................................3
1.1. Gii thiu chung v rau xanh ..........................................................................3
1.1.1. Vai tr ca rau ..........................................................................................3
1.1.2. Th no l rau sch ...................................................................................3
1.1.3. Cng dng ca mt s loi rau ..................................................................4
1.1.4. Mt s tiu ch rau an ton ........................................................................6
1.1.4.1. nh ngha .........................................................................................6
1.1.4.2. Cc yu t gy nhim cho rau ..........................................................7
1.1.4.3. V cht lng ca rau an ton ............................................................9
1.2. Tnh cht ca Cd v Pb [14,22,23] ..................................................................9
1.2.1. Tnh cht vt l .........................................................................................9
1.2.2. Tnh cht ha hc. .................................................................................. 11
1.2.3. Cc hp cht ca Cd v Pb .....................................................................12
1.2.3.1. Cc xt............................................................................................ 12
1.2.3.2. Cc hyroxit..................................................................................... 13
1.2.3.3. Cc mui .......................................................................................... 13
1.3. Vai tr, chc nng v s nhim c Cd, Pb [5,17] ......................................... 14
1.3.1. Vai tr, chc nng v s nhim c Cd................................................... 14
1.3.2. Vai tr, chc nng v s nhim c Pb [10] ............................................ 16
1.4. Cc phng php xc nh Cd, Pb.................................................................17
1.4.1. Phng php phn tch ho hc [13] ....................................................... 17
1.4.1.1. Phng php phn tch khi lng ................................................... 17
1.4.1.2. Phng php phn tch th tch ........................................................ 18
1.4.2. Phng php phn tch cng c .............................................................. 19
1.4.2.1. Phng php in ho [7,13]............................................................ 19
1.4.2.2. Phng php quang ph ...................................................................21

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1.5. Phng php x l mu phn tch xc nh Cd v Pb [12,25] ........................ 24


1.5.1. Phng php x l t (bng axit c oxi ha mnh) ............................. 25
1.5.2. Phng php x l kh ........................................................................... 25
CHNG 2. I TNG V PHNG PHP NGHIN CU .................... 27
2.1. i tng v mc tiu nghin cu.................................................................27
2.1.1. i tng v mc tiu ............................................................................ 27
2.1.2. Cc ni dung nghin cu ........................................................................27
2.2. Gii thiu phng php ph hp th nguyn t [9] .......................................27
2.2.1. Nguyn tc ca phng php ..................................................................27
2.2.2. H trang b ca php o .......................................................................... 28
2.3. Gii thiu v phng php x l t mu bng axit ......................................29
2.3.1. Nguyn tc ca phng php ..................................................................30
2.3.2. C ch phn hy ..................................................................................... 30
2.4. Dng c - ha cht ........................................................................................ 31
2.4.1. Dng c my mc ................................................................................... 31
2.4.2. Ho cht .................................................................................................31
CHNG 3. THC NGHIM V BN LUN KT QU .............................. 32
3.1. Kho st cc iu kin thc nghim o ph ca cadimi v ch .................. 32
3.1.1. Kho st chn vch o ph .....................................................................32
3.1.2. Kho st cng dng n catot rng (HCL) .......................................33
3.1.3. Kho st rng khe o ......................................................................... 34
3.1.4. Kho st chiu cao ca n nguyn t ho mu ......................................35
3.1.5. Kho st thnh phn hn hp kh chy .................................................... 36
3.1.6. Tc dn mu ...................................................................................... 37
3.2. Kho st cc yu t nh hng n php o .................................................. 37
3.2.1. Kho st nh hng ca cc loi axit v nng axit ............................. 38
3.2.2. Kho st thnh phn nn ca mu ........................................................... 40
3.2.3. Kho st nh hng ca cc ion.............................................................. 42
3.2.3.1. Kho st nh hng ca cc cation ................................................... 42

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3.2.3.2. Kho st nh hng ca cc anion.................................................... 44


3.2.3.3. nh hng ca tng cc cation v anion .......................................... 45
3.3. Phng php ng chun i vi php o F- AAS......................................47
3.3.1. Kho st xc nh khong tuyn tnh ca Cd v Pb .................................47
3.3.2. Xy dng ng chun, xc nh gii hn pht hin (LOD) v gii
hn nh lng (LOQ) ca Cd v Pb ................................................................ 49
3.3.2.1. ng chun ca Cadimi .................................................................49
3.3.2.2. ng chun ca ch ........................................................................51
3.4. nh gi sai s v lp li ca php o ...................................................... 53
3.5. Tng kt cc iu kin o ph F-AAS ca cadimi v ch .............................. 56
3.6. Phn tch mu thc ........................................................................................ 56
3.6.1. Ly mu..................................................................................................56
3.6.2. Kho st qu trnh x l mu ...................................................................58
3.7. Thc nghim o ph v tnh ton kt qu ...................................................... 60
3.7.1. Phng php x l kt qu phn tch theo phng php ng chun .....60
3.7.2. Kt qu xc nh hm lng cadimi, ch trong cc mu rau .................... 60
3.8. Kim tra qu trnh x l mu......................................................................... 62
3.8.1. Mu lp ..................................................................................................62
3.8.2. Mu thm chun ..................................................................................... 66
KT LUN ............................................................................................................ 69
TI LIU THAM KHO ..................................................................................... 71
PH LC .................................................................... Error! Bookmark not defined.

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DANH MC BNG
Trang
Bng 1.1: Hng s vt l ca Cd ............................................................................ 10
Bng 1.2: Hng s vt l ca Pb ............................................................................ 10
Bng 3.1: Kt qu kho st vch ph ca cadimi ................................................... 32
Bng 3.2: Kt qu kho st vch ph ca ch ......................................................... 33
Bng 3.3: Kho st cng dng n vi nguyn t Cd ...................................... 33
Bng 3.4: Kt qu kho st cng dng n vi nguyn t Pb .......................... 34
Bng 3.5 : Kt qu kho st khe o vi nguyn t Cd ........................................... 34
Bng 3.6 : Kt qu kho st khe o vi nguyn t Pb ........................................... 35
Bng 3.7: Kt qu kho st chiu cao n nguyn t ho mu ca Cd ................... 36
Bng 3.8: Kt qu kho st chiu cao n nguyn t ho mu ca Pb .................... 36
Bng 3.9: Kt qu kho st thnh phn kh chy C2H2 i vi Cd.......................... 37
Bng 3.10: Kt qu kho st thnh phn kh chy C2H2 i vi Pb ........................ 37
Bng 3.11: nh hng ca cc loi axit v nng axit ti php o Cd................ 39
Bng 3.12: nh hng ca cc loi axit v nng axit ti php o Pb ................ 39
Bng 3.13: Kho st nh hng ca thnh phn nn .............................................. 41
Bng 3.14: Kt qu kho st nng LaCl3 ........................................................... 41
Bng 3.15: nh hng ca nhm cation kim loi kim ......................................... 42
Bng 3.16: nh hng ca nhm cation kim loi kim th.................................... 43
Bng 3.17: nh hng ca nhm cation kim loi nng ho tr II ........................... 43
Bng 3.18: nh hng ca nhm cation kim loi ho tr III .................................. 43
Bng 3.19 : nh hng tng ca cation ................................................................. 44
Bng 3.20: Kho st nh hng ca anion SO42- ,H2PO4-, F-, I- .............................. 45
Bng 3.21: Kho st nh hng ca tng cc anion ............................................... 45
Bng 3.22 : nh hng ca tng cc cation v anion ............................................. 46
Bng 3.23: Kt qu kho st khong nng tuyn tnh ca Cd ............................ 47
Bng 3.24: Kt qu kho st khong nng tuyn tnh ca Pb ............................ 48
Bng 3.25: Kt qu sai s v lp ca php o cadimi ........................................ 54

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Bng 3.26: Kt qu sai s v lp ca php o ch .............................................. 55


Bng 3.27: Tng kt cc iu kin o ph F- AAS ca Cd, Pb .............................. 56
Bng 3.28: a im v thi gian ly mu ............................................................. 57
Bng 3.29: T l khi lng ca mt s loi rau trc v sau khi sy kh .............. 58
Bng 3.30: Kt qu kho st lng HNO3 ng vi 1 gam mu rau kh .................. 59
Bng 3.31: Kt qu o ph F- AAS i vi nguyn t Cd ..................................... 61
Bng 3.32 : Kt qu o ph F- AAS i vi nguyn t Pb ..................................... 61
Bng 3.33 : Kt qu x l s liu hm lng Cd .................................................... 63
Bng 3.34 : Hm lng chnh xc Cd trong rau ..................................................... 63
Bng 3.35: Kt qu x l s liu hm lng Pb ..................................................... 64
Bng 3.36: Hm lng chnh xc Pb trong rau ...................................................... 65
Bng 3.37 : Mu thm chun ................................................................................. 66
Bng 3.38: Kt qu phn tch cadimi ..................................................................... 67
Bng 3.39: Kt qu phn tch ch ........................................................................... 67

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DANH MC HNH
Trang
Hnh 2.1 : S cu to my ph hp th nguyn t .............................................. 29
Hnh 3.1: th kho st khong nng tuyn tnh ca Cd.................................. 48
Hnh 3.2: th kho st khong nng tuyn tnh ca Pb .................................. 49
Hnh 3.3: th ng chun ca cadimi ............................................................... 50
Hnh 3.4: th ng chun ca ch .................................................................... 52
Hnh 3.5: th hm lng Cd qua kt qu phn tch rau mt s x
ca huyn i T tnh Thi Nguyn ....................................................... 64
Hnh 3.6: th hm lng Pb qua kt qu phn tch rau mt s x ca
huyn i T tnh Thi Nguyn ............................................................. 65

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M U
Ngy nay vic bo v mi trng v an ton thc phm l vn quan trng
i vi mi quc gia. Trong i sng, rau xanh lun l ngun thc phm cn thit
v quan trng. Hin nay do nhiu nguyn nhn khc nhau m ch yu l vic s
dng phn bn ho hc, thuc bo v thc vt, thuc tr su, dit c, cht thi ca
cc nh my, khu cng nghip dn n s nhim ngun t, ngun nc v bu
kh quyn. Do rau xanh c th b nhim mt s kim loi nng nh Sn, Pb, Hg,
Mn, Zn... v cc vi sinh vt gy bnh. Nu con ngi s dng phi s b ng c c
th gy ra nhng cn bnh him ngho nh ung th s dn n t vong.
Vn ang c t ra Thi Nguyn ni ring v c nc ni chung l
lm th no c c rau xanh an ton (rau sch)?
Nh vy vic iu tra, nh gi cht lng rau sch tr nn v cng cp thit.
Mt trong cc ch tiu dng nh gi an ton thc phm ni chung v rau sch
ni ring l hm lng cc kim loi nng. Do , vic phn tch tm ra hm lng
cc kim loi nng trong rau xanh trn a bn huyn i T - tnh Thi Nguyn s
gp phn kim sot c cht lng rau sch theo tiu chun rau sch ang c p
dng Vit Nam. C nhiu phng php xc nh hm lng cc kim loi, ty
thuc vo hm lng cht phn tch m c th s dng cc phng php khc nhau:
phng php phn tch th tch, phng php phn tch trng lng, phng php
in ha, phng php phn tch cng c (phng php quang ph, phng php ph
pht x nguyn t AES, phng php ph hp th nguyn t AAS) trong phng
php ph hp th nguyn t ngn la F- AAS l phng php c nhy, chn
lc cao, ph hp vi vic xc nh lng vt cc kim loi nng trong thc phm.
Xut pht t nhng l do trn chng ti chn ti: "Xc nh hm lng Cadimi
v Ch trong mt s loi rau xanh ti huyn i T- tnh Thi Nguyn bng
phng php ph hp th nguyn t ngn la (F-AAS)".
Mc ch: Xc nh c hm lng Cadimi v Ch gy nhim trong rau
xanh v nh gi hin trng nhim bi hai kim loi ny trong rau xanh mt s
x ca huyn i T tnh Thi nguyn.

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thc hin ti ny, chng ti tp trung gii quyt cc nhim v sau:


1. Nghin cu ti u ha cc iu kin xc nh Cd, Pb trong rau xanh bng
php o ph hp th nguyn t ngn la (F- AAS)
2. Nghin cu ti u ha qu trnh x l mu i vi cc mu rau xanh.
3. Xc nh hm lng ca Cd, Pb trong mt s mu rau xanh ti huyn i
T tnh Thi Nguyn bng phng php ng chun v thm chun.

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CHNG 1: TNG QUAN


1.1. Gii thiu chung v rau xanh
1.1.1. Vai tr ca rau
Cc loi rau ti ca nc ta rt phong ph. Nhn chung ta c th chia rau
ti thnh nhiu nhm: nhm rau xanh nh rau ci, rau mung, rau x lch, rau
cn... nhm r c nh c rt, c ci, c su ho, c u...nhm cho qu nh c chua,
da chut... nhm hnh gm cc loi hnh, ti. Trong n ung hng ngy rau ti
c vai tr c bit quan trng. Rau ti nm trong nhm th 4, cung cp vitamin v
mui khong. Nu tnh lng m c trong 100 gam c th thy mt s loi rau rt
giu cht m nh b ngt, rau mung. Mc d cht m c nhiu trong tht, c t
14 15 gam nhng tht c t tin, khng phi ai cng c kh nng mua thng
xuyn trong khi rau rt r m lng m cung cp cng kh. 1kg rau mung cung
cp 300 gam lng m tng ng 200 gam tht. Nh vy rau l loi thc n r
tin nhng li c vai tr dinh dng rt cao. Rau cn quan trng ch n cung cp
cht x. Cht x khng d tiu ho hp th c, khng cung cp nng lng, n
to ra cht thi ln trong rut, lm tng nhu ng rut, chng to bn. y l iu
rt quan trng trong vic trnh hp th c hi cho c th. Nu phn lu trong rut
do thiu cht x cng tng t l ung th tiu ho, i trng, gy x va ng mch.
Ngoi ra, cht x cn thc y s hp th ca c th i vi 3 nhm thc n m,
bo, ng. Rau cn l ngun cht st quan trng. St trong rau c c th hp th
tt hn st cc hp cht v c. Cc loi rau, u, x lch l ngun mangan tt.
Tm li, rau ti c vai tr quan trng trong dinh dng, trong ba n hng ngy
ca chng ta khng th thiu c. iu quan trng l phi m bo rau sch,
khng c vi khun gy bnh v cc ho cht c nguy him.
1.1.2. Th no l rau sch
Rau sch l rau khng b nhim bi cc tc nhn sinh hc, ho hc, vt l vt
qua gii hn cho php v khng gy nguy hi ti sc kho cho ngi tiu dng.

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nhim sinh hc: nhim vi khun, vi rt, k sinh trng.


+ Vi khun: phn ti l cha ca nhiu loi vi khun gy bnh t, l,
thng hn, trng giun sn...do vy chng c th ly nhim sang rau, khi n rau
sng hoc nu rau khng chn th chng s theo vo c th v gy bnh.
+ Vi rt : gy vim gan thng gp trong cc mi trng khng m bo v
sinh nh nc bn, thc n nhim bn (do cn trng, phn ngi...). ng lu l
cc loi rau thu sinh trng di nc gn ngun nhim phn nh cu tiu, trn
ao, h, sng...
+ K sinh trng: rau trng khu vc t c nhiu ngun nhim nh bn
phn ti ca gia sc, gia cm, phn ngi kh nng nhim rt cao v gy nguy
him cho ngi s dng.
nhim ho hc: nhim kim loi nng, ho cht bo v thc vt, ph
gia bo qun
+ nhim kim loi nng: xy ra khi trng rau qu, c gn ni nhim kh
thi ca cc nh my hay khi xng, gn quc l hoc dng nc thi ca cc nh
my thi ra ti rau.
+ nhim tn d thuc bo v thc vt do xt thuc cho rau qu thi gian
cch li ngn, cha thi hi ht thu hoch. Gy ng c cp v mn tnh cho
ngi s dng.
t c nng sut cao hoc tiu dit cc su, ry, c bit l i vi
mt s loi rau qu d b su ph hoi, mt s ngi nng dn s dng qu nhiu
phn bn ho hc v phun thuc tr su vi liu lng vt qu mc an ton, phun
thuc tr su ti st ngy thu hoch. Mt khc, mt s loi rau qu c trng
vng t nhim, ti phn ti, hay nc thi bn cng l mi e do cho sc
kho ca ngi tiu dng. Nn thn trng vi nhng loi rau n l hoc rau tri
khng phi gt v nh: rau mung nc, x lch, tn , ci b xanh, ci ngt, ci
dng lm da, rau m, u a, kh qua, da leo, c chua, nho, to...
1.1.3. Cng dng ca mt s loi rau
Rau mung c v ngt, tnh hi lnh. Cng dng thanh nhit, lng huyt,
ch huyt, thng i tiu tin, gii cc cht c xm nhp vo c th. Rau mung c

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nhiu tnh nng v tc dng trong vic phng v cha bnh nh: thanh nhit gii
c ma h, lng huyt, cm mu, cha tm phin, chy mu mi, li ru
vng, kht nc mt, tai chng mt; au u trong trng hp huyt p cao; au
d dy, nng rut, chua, ming kh ng; say sn, ng c sn; gii cc cht c
trong thc n; cc chng bnh chy mu nh chy mu cam, ho nn ra mu; tiu
tiu ra mu, tr, l; sn ph kh sinh; kh h bch i; ph thng ton thn do thn,
b tiu tin; i tho ng; quai b; chng n trong ming hoc l khe ming
tr em; l nga, lot ngoi da, zona, ong cn; rm sy, mn nga; si, thy u tr
em Rau mung cung cp nhiu cht x, c vitamin C, vitamin A v mt s thnh
phn tt cho sc khe, l thc n tt cho mi ngi.
Ci bp c v ngt, tnh hn, khng c, c tc dng ho huyt thanh nhit,
thanh ph, tr m thp, mt d dy, gim c li tiu. Ci bp cng chng suy
nhc thn kinh, gim au nhc, phng chng cc bnh ung th, tim mch v nhiu
loi bnh khc.Theo ty y, ci bp c dng cha bnh thng thng nh:
mn nht, su b t, giun, au d dy. Mt s tc dng cha bnh chnh ca ci
bp c bit n phng bnh ung th v ph n, cha lot d dy, hnh t
trng, phng trnh ung th ng tiu ho
Rau ci xoong trong rau ci xoong cha hm lng vitamin C cao, li c
vitamin A, B1, B2 nn gip bo v sc kho, chng oxi ho, chng c, lm tng
sc khng, chng hin tng lo ho bnh l, gi gn nt ti tr. Rau ci xoong
gip ta n ngon ming li ty c, li tiu, c nhiu cht x nn tc dng tt i vi
d dy, c tc dng thng gan mt v gp phn lm gim bnh mu.
Rau gip c l mt loi rau gia v rt quan trng trong ba n hng ngy ca
gia nh. Ngoi vic d trng, v thm ngon rau gip c cn c nhiu cng dng
cha bnh. Theo ng y gip c c v chua, mi tanh, tnh mt c tc dng thanh
nhit gii c, li tiu, st trng, cha vim phi, th huyt, l lot c t cung, vim
khp, to bn, kit l do vi khun cp tnh... Y hc hin i cng chng minh rau
gip c c tc dng chng nhim khun, chng vi khun, nng cao sc khng v
li tiu. Theo nghin cu ca y hc hin i, trong rau gip c c cht decanoyl-

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acetalehyd c tc dng khng khun. Bn cnh gip c cng c tc dng i vi


vi rt si, cm.
Rau ci cc cha nhiu proten, acid amin, cht bo, cht x, vitamin v
lisin. L rau ci cc cn ti hay lm kh ni thong mt thay v ngoi nng gip
cha bnh ho tr em, iu tr bnh au mt, c th ly l ci cc sau khi ra
sch v h nng p ln mt.
Rau ngi cu rt thng dng trong cuc sng hng ngy bi n va d n
li d tm, c rt nhiu cng dng cha bnh cng nh cc mn n t ngi cu.
ng y coi ngi cu l v thuc c tnh n, v cay, dng iu ha kh huyt, trc hn
thp, iu kinh, an thai, kinh nguyt khng u... Ngoi ra ngi cu cn c th dng
kch thch huyt trong chm cu.
Rau x lch theo ng y Trung Quc th rau x lch v ng ngt, hi hn.
Cng nng ch ng tng, thng kinh mch, cng gn ct, li tiu tin v lm trng
rng p da. Dng cha tng huyt p vim thn mn, sa khng thng sau sinh
n... khai v thanh tm cha cc chng ung c, sng ty.
Ci tha l cy tho sng 1nm hoc 2 nm, cao 25- 70 cm. R khng phnh
thnh c. L gc, to, mu xanh nht, gn gia trng, nc; phin hnh bu dc
nhn, nguyn hay c rng khng r, men theo cung, ti gc nhng khng to thnh
cnh; cc l trn hnh gio. Hoa mu vng ti hp thnh chm ngn; hoa di 11,4 cm, c 6 nh. Qu ci di 4 - 11cm, c m; ht trn, ng knh 1- 1,5 mm, mu
nu tm. Ci tha c nhiu vitamin A,B,C. Lng vitamin C ca n rt phong ph,
ng vo bc nht trong cc loi rau.Sau khi phi kh, hm lng vitamin C vn
cn cao. Ci tha c tc dng chng scrbut, tng khp v lm tan sng. Ht ci tha
kch thch, lm d tiu, nhun trng.
1.1.4. Mt s tiu ch rau an ton
1.1.4.1. nh ngha
Trong qu trnh gieo trng , c sn phm rau an ton nht thit phi p
dng cc bin php k thut v s dng mt s nguyn liu nh nc, phn bn,
thuc phng tr su bnh . Trong cc nguyn liu ny, k c t trng u c cha

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cc nguyn t gy nhim rau v t nhiu u li mt s d lng trn rau sau


khi thu hoch.Trong thc t hin nay hu nh khng th c sn phm ca rau sch
vi ngha hon ton khng c yu t c hi. Tuy vy nhng yu t ny thc s
ch gy c khi chng li mt d lng nht nh no trn rau, di mc d
lng ny th khng c hi , mc d lng ti a khng gy hi cho ngi c th
chp nhn c gi l mc d lng cho php (hoc ngng d lng gii hn).
Nh vy nhng sn phm rau ti (bao gm cc loi rau n l, c, thn, hoa, qa)
c cht lng ng nh c tnh ca chng, mc nhim cc cht c hi v cc
vi sinh vt gy hi khng vt qu ch tiu cho php, m bo an ton cho ngi
tiu dng v nui trng c coi l rau m bo an ton v sinh thc phm, gi tt
l rau an ton (theo B Nng nghip v Pht trin Nng thn).
1.1.4.2. Cc yu t gy nhim cho rau
C nhiu yu t lm rau b nhim , song quan trng nht l cc yu t sau:
D lng thuc bo v thc vt
D lng Nitrat (NO3-)
Sinh vt gy bnh.
D lng kim loi nng
- Khi nim :
Cc kim loi nng nh Asen (As), ch (Pb) , thy ngn (Hg) , km (Zn),
thic (Sn), .... nu vt qua mc cho php cng l nhng cht c hi cho c th ,
hn ch s pht trin ca t bo v hot ng ca mu, gy thiu mu , bin ng
thn nhit , ri lon tiu ha ...
- Nguyn nhn :
* Trong thuc bo v thc vt (BVTV) v phn bn NPK c cha mt s
kim loi nng trong qu trnh ti tiu , cc kim loi nng ny b ra tri xung ao
h,sng rch, thm nhp vo mch nc ngm gy nhim ngun nc ti rau.
* Ngun nc thi ca thnh ph v cc khu cng nghip cha nhiu kim
loi nng chuyn trc tip vo rau ti.
- Bin php khc phc:

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* Khng trng rau trong khu vc c cht thi ca nh my , cc khu vc t


b nhim do qu trnh sn xut trc gy ra.
* Khng ti rau bng ngun nc c nc thi ca cc nh my cng nghip.
Nhng yu t trn l nguyn nhn ch yu lm cho rau b nhim , nh
hng n sc khe con ngi , trong ph bin nht l thuc BVTV v vi sinh
vt gy bnh . V vy yu cu cn thit l phi gieo trng th no c c nhng
sn phm rau khng b nhim , tc rau an ton i vi tt c mi ngi .
Yu cu sn xut rau an ton:
Chn t: t trng rau phi l t cao, thot nc thch hp vi sinh
trng v pht trin ca rau. Tt nht l t ct pha hoc tht nh hay t tht trung
bnh c tng canh tc dy (20- 30 cm), vng trng rau phi cch ly vi khu vc c
cht thi cng nghip v bnh vin t nht l 2 km, vi cht thi sinh hot ca thnh
ph t nht l 200m, t c th cha mt lng nh kim loi nng nhng khng
c tn d ho cht c hi.
Nc ti : V trong rau xanh, nc cha trn 90% nn nc ti nh hng
trc tip n cht lng sn phm, cn s dng nc sch ti. Nu c iu kin
nn s dng ging khoan, nht l i vi vng trng rau x lch v cc loi rau gia v.
Nu khng c ging th dng nc sng, ao, h nhng khng b nhim. Nc sch
dng pha cc loi phn bn l, ho cht bo v thc vt. i vi cc loi rau cho
qu, giai on u c th s dng nc bm t sng, h ti.
Ging: Ch gieo nhng ht ging tt v trng cy con kho mnh, khng c
mm bnh. Phi bit r l lch ni sn xut ht ging. Ging nhp ni phi qua kim
dch thc vt. Ht ging trc khi gieo cn c x l ho cht hoc nhit, trc khi
a cy con ra rung, cn x l Sherpa 0,1% phng tr bnh hi sau ny.
Phn bn: Phn chung c hoai mc v phn ln hu c vi sinh c
dng bn lt. Tu mi loi cy c ch bn, lng phn bn khc nhau. Trung
bnh bn lt dng 15 tn phn chung + 300 kg ln hu c vi sinh cho 1 ha. Phn
ho hc tu thuc yu cu x l ca cy, bn lt 30% N + 50% K, s m v kali
cn li dng bn thc.

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Ho cht bo v thc vt: Khng s dng ho cht bo v thc vt nhm I


v II. Khi tht cn thit c th s dng ho cht nhm III v IV, chn cc loi thuc
c ho cht thp, t c hi vi k sinh thin ch. Kt thc phun ha cht trc khi
thu hoch t nht 5 - 10 ngy, u tin s dng cc ch phm sinh hc, cc ch phm
tho mc, cc k sinh thin ch phng bnh. p dng nghim ngt cc bin
php phng tr tng hp (IPM) : lun canh cy trng hp l, s dng ging tt,
chng chu bnh, chm sc cy theo yu cu sinh l, bt su bng tay, dng by
sinh hc tr bm, s dng cc ch phm sinh hc, thng xuyn v sinh ng
rung, thng xuyn kim tra ng rung theo di pht hin su bnh, tp trung
tr smS dng thuc theo nguyn tc 4 ng: ng thuc, ng lc, ng liu
lng, ng cch v m bo thi gian cch ly.
Thu hoch, bao gi: Rau c thu hoch ng chn, hoc b l gi, ho,
qu b su, d dng Rau c ra k bng nc sch, ro nc, ri cho vo
bao, ti sch trc khi mang i tiu th ti cc ca hng, trn bao b phi c phiu
bo hnh, c a ch ni sn xut nhm m bo quyn li cho ngi tiu dng.
1.1.4.3. V cht lng ca rau an ton
Rau an ton phi t c cc yu t sau:
Ch tiu hnh thi: Sn phm c thu hoch ng lc, ng vi yu cu
tng loi rau, khng dp nt, h thi, khng ln tp cht, su bnh v c bao gi
thch hp (tu loi).
Ch tiu ni cht: Ch tiu ni cht c qui nh cho rau ti bao gm: D
lng ho cht bo v thc vt; Hm lng Nitrat (NO3-); Hm lng mt s kim
loi nng ch yu: Cd, Pb, Cu,Zn; Mc nhim cc vi sinh vt gy bnh
(E.coli, Salmonella), v k sinh trng ng rut (Th d: trng giun a). Tt c
cc ch tiu trong tng loi rau phi t di mc cho php theo tiu chun ca
FAO/WHO (trong khi ch Vit Nam cng b tiu chun v cc lnh vc ny).
1.2. Tnh cht ca Cd v Pb [14,22,23]
1.2.1. Tnh cht vt l
* Tnh cht vt l ca Cd:
Cadimi l cc kim loi mu trng bc nhng trong khng kh m, chng dn
dn b bao ph bi mng oxit nn mt nh kim.
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Cadimi c 8 ng v, trong

112

Cd chim 24.2%. c bit

113

Cd c thit

din bt notron rt ln nn c dng lm thanh iu chnh dng notron trong l


phn ng ht nhn.
Di y l mt s hng s vt l ca cadimi:
Bng 1.1: Hng s vt l ca Cd
Hng s vt l

Cd
[Kr]4d105s2

Cu hnh electron
Nng lng ion ho th nht (eV)

8,99

Bn knh nguyn t (A0)

1,56

Th in cc chun (V)

- 0,402

Khi lng nguyn t (vc)

112,411

Nhit nng chy (0C)

321,07

Nhit si (0C)

767

Cu trc tinh th

Lc gic b cht

* Tnh cht vt l ca Pb :
Ch l kim loi mu xm thm, rt mm, d lt mng, c cu trc kiu lp
phng tm din, s th t l 82 trong bng h thng tun hon.
Bng 1.2: Hng s vt l ca Pb
Hng s vt l
Cu hnh electron

Pb
[Xe]4f145d106s26p2

Nng lng ion ho th nht (eV)

7,42

Bn knh nguyn t (Ao)

1,75

Th in cc chun (V)

-0,126

Khi lng nguyn t (vc)

207,21

Nhit nng chy (oC)

327,4

Nhit si (oC)

1740

Cu trc tinh th

Lp phng tm din

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1.2.2. Tnh cht ha hc.


* nhit thng cadimi v ch b oxi ha khng kh to thnh lp oxt
bn, mng bao ph bn ngoi kim loi.
2Pb + O2

2PbO

* Cadimi v ch tc dng c vi cc phi kim nh halogen to thnh


ihalogenua, tc dng vi lu hunh v cc nguyn t khng kim loi khc nh
phtpho , selen ...
Cd + X2

CdX2 (X = halogen)

Pb + X2

PbX2

* nhit thng cadimi v ch bn vi nc do c mng oxit bo v


.Nhng nhit cao cadimi kh hi nc bin thnh oxit , cn khi c mt oxi, ch
c th tng tc vi nc to thnh hyroxit:
Cd + H2O

CdO + H2

2Pb + O2 + 2H2O

2Pb(OH)2

* Cadimi tc dng d dng vi axit khng phi l cht oxi ha, gii phng
kh hiro. V d:
Cd + 2HCl

CdCl2 + H2

Trong dung dch th :


2Cd + 2H3O+ +2 H2O

2[Cd(H2O)2]2+ + H2

Cn Ch c th in cc m nn v nguyn tc n tan c trong cc axit.


Nhng thc t ch ch tng tc trn b mt vi dung dch axt clohiric long v
axit sunfuric di 80% v b bao bc bi lp mui kh tan (PbCl2 v PbSO4) nhng
vi dung dch m c hn ca cc axit , ch c th tan v mui kh tan ca lp
bo v chuyn thnh hp cht tan :
PbCl2 + 2HCl

H2PbCl4

PbSO4 + H2SO4
3Pb + 8HNO3 (long)

Pb(HSO4)2
3Pb(NO3)2 + 2NO + 4H2O

Ch c th tan trong axit axetic khi c mt oxi v cc axit hu c khc:


2Pb + 4CH3COOH + O2

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Vi dung dch kim ch c th tng tc khi un nng gii phng hir


Pb + 2KOH + 2H2O

K2[Pb(OH)4] + H2

1.2.3. Cc hp cht ca Cd v Pb
1.2.3.1. Cc oxit
a. Cadimi oxit:
- CdO c mu t vng n nu gn nh en ty thuc vo qu trnh ch ho
nhit , nng chy 1813oC, c th thng hoa, khng phn hy khi un nng, hi
CdO rt c.
- CdO khng tan trong nc ch tan trong axit v kim nng chy:
CdO + 2KOH(nng chy)

K2CdO2 + H2O

- CdO c th iu ch cch t chy kim loi trong khng kh hoc nhit


phn hiroxit hay cc mui cacbonat, nitrat:
2Cd + O2

2CdO

Cd(OH)2

CdO + H2O

CdCO3

CdO + CO2

b. Ch oxit :
- Ch c hai xit l PbO, PbO2 v hai oxit hn hp l ch meta planbat Pb2O3
(hay PbO.PbO2), ch orthoplanbat Pb3O4 (2PbO.PbO2)
- Monooxit PbO l cht rn c hai dng : PbO - mu v PbO mu
vng , PbO tan cht t trong nc nn Pb c th tng tc vi nc khi c mt oxi .
PbO tan trong axit v tan trong kim mnh , khi un nng trong khng kh b xi
ha thnh Pb3O4
- ioxit PbO2 l cht rn mu nu en , c tnh lng tnh nhng tan trong
kim d hn trong axit . Khi un nng PbO2 mt dn oxi bin thnh cc oxit trong
ch c s oxy ha thp hn :
PbO2

290 320oC

(Nu en)

530 550o C

Pb2O3 390 420 C Pb3O4


(Vng )

()

PbO
(Vng)

Li dng kh nng oxi ha mnh ca PbO2 ngi ta ch ra acquy ch.

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Ch orthoplanbat (Pb3O4) hay cn gi l minium , l hp cht ca Pb c cc


s oxi ha +2 , + 4 . N l cht bt mu da cam c dng ch yu l sn
xut thy tinh pha l , men s v st , lm cht mu cho sn (sn trang tr v
sn bo v cho kim loi khng b r).
Tt c cc ihalogen c th kt hp vi halogenua kim loi kim MX to
thnh hp cht phc kiu M2[PbX4]. S to phc ny gii thch kh nng d ha tan
ca ch ihalogenua trong dung dch m c ca axit halogenhiric
V mui ca chng :
PbI2

2KI

K2[PbI4]

2HCl

H2[PbCl4]

PbCl2 +

1.2.3.2. Cc hyroxit
Cd(OH)2 l kt tu nhy t tan trong nc v c mu trng, cn Pb(OH) 2 l
cht kt ta mu trng khng tan trong nc. Khi un nng chng d mt nc bin
thnh oxit.
Cd(OH)2 khng th hin r tnh lng tnh, tan trong dung dch axit, khng
tan trong dung dch kim m ch tan trong kim nng chy, cn Pb(OH) 2 l cht
lng tnh.
Khi tan trong axit, n to thnh mui ca cation Cd2+, Pb2+ :
Cd(OH)2 + 2HCl

CdCl2 + 2H2O

Pb(OH)2 + 2HCl

PbCl2 + 2H2O

Cd ch tan trong kim nng chy, cn Pb tan trong dung dch kim mnh, n
to thnh mui hiroxoplombit:
Pb(OH)2+ 2KOH

K2[Pb(OH)4]

Mui hiroxoplombit d tan trong nc b thy phn mnh nn ch bn trong


dung dch kim d.
Cd tan trong dung dch NH3 to thnh hp cht phc:
Cd(OH)2 +4NH3

[Cd(NH3)4](OH)2

1.2.3.3. Cc mui
a. Cc mui ca Cadimi
a s cc mui Cadimi(II) u khng mu. Cc mui sunfat v nitrat ca
cadimi u tan ch c mui sunfua, ccbonat ca chng l t tan trong nc
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Cc mui clorua b hirat ho to nn cc axit tng ng v chng l cc axit


tng i mnh
Ngoi ra cadimi(II) cn to ra rt nhiu phc cht:
Cadimi(II): c kh nng to phc mnh vi nhiu thuc th hu c cng nh
v c. Cc phc ca Cd2+ vi halogenua, SCN-, CN-, NH3u l cc phc tan.
Cc phc ca cadimi(II) to vi cc thuc th hu c c mu c trng v d nh
phc vi dithizon to ra cadimi-dithizonnat c mu tm, vi EDTA, Cd2+ to
phc bn vi lg = 16,6.
Cc ihalogenua ca cadimi l cht dng tinh th mu trng, c nhit
nng chy v nhit si kh cao.
b.Cc mui ca Ch
Cc mui Pb (II) thng l tinh th c cu trc phc tp, khng tan trong
nc tr Pb(NO3)2 v Pb(CH3COO)2.
Ion Pb (II) c th to nhiu phc vi hp cht hu c nh AmoniPyrilodyn
Dithiocacbamat (APDC), in hnh l vi ithizon pH 8,5- 9,5 to phc mu
gch.
Cc ihalogenua ch u l cht rn khng mu, tr PbI2 mu vng, tan t
trong nc lnh nhng tan nhiu trong nc nng.
Tt c cc ihalogenua c th kt hp vi halogenua kim loi kim MX to
thnh hp cht phc kiu M2[PbX4]. S to phc ny gii thch kh nng d ho
tan ca ch ihalogenua trong dung dch m c ca axit halogenhidric v mui
ca chng.
PbI2 + 2KI
PbCl2 + 2HCl

K2[PbI4]
H2[PbCl4]

1.3. Vai tr, chc nng v s nhim c Cd, Pb [5,17]


1.3.1. Vai tr, chc nng v s nhim c Cd
t, ct, , than , cc loi phn phosphate u c cha cadimium . Cadimium
c trch ly t cc k ngh khai thc cc m ng, ch v km. Nh tnh cht t b
r st nn c s dng trong vic sn xut pin, acquy, m kn, hp kim alliage,

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que a hn v trong k ngh sn xut cht nha polyvinyl clorua (P.V.C),trong


cadimium c s dng nh cht lm n nh. Bi l do ny, chi tr em v cc
lon hp lm bng cht do PVC u c cha cadimium. Cadimium cng c dng
trong nhng loi nc men, sn c bit trong k ngh lm s, chn, a... C
th mt s ng dng ca Cadimi nh sau:
* M in (chim 7 %) : Cadimi c m ln b mt cht in phn hoc
my mc to ra b mt sng bng v chng n mn.
* Cc cht mu (chim 15 %): Cadimi sunfua (CdS) cho mu t vng ti
cam v cadimisunfoselenit cho mu t hng ti v nu sm. Tt c cc cht mu
ny u c dng trong cng nghip nha, gm s, sn v cc cht ph ngoi.
* Cc ph gia n nh nha (chim 10%): Cadimi stearat c s dng
nh mt cht n nh trong qu trnh sn xut nha polyvinyl clorua (PVC). Chng
n nh cc lin kt i trong polime bng cch th ch cc nhm allyl c nh
du trn nguyn t clorua khng bn. Thm cc mui bari (hoc cc mui km), cc
hp cht epoxy, cc este photphat hu c bo v polime khi clo tha hoc cc
lp clorua. Tuy nhin, cc cht n nh da trn nn Cd khng c s dng trong
sn xut PVC do cha thc phm.
* Sn xut pin (chim 67 %): Cd c s dng rng ri trong sn xut pin,
c tc dng o ngc hon ton cc phn ng in ha trong mt khong rng
nhit , tc thi hi thp, v d thu hi t cc pin cht. Ngi tiu dng s dng
cc pin ny trong cc hot ng nh: my nh rng, co ru, khoan v ca tay, cc
thit b y hc, thit b iu khin thng tin, cc dng c chiu sng khn cp, my
bay, v tinh nhn to v tn la, v cc trang b c bn cho cc vng a cc.
Bn cnh nhng tc dng trn, cadimi l mt nguyn t rt c. Cadimi
thng c tm thy trong cc khong vt c cha km, cn trong kh quyn v
nc cadimi xm nhp qua ngun t nhin (nh bi ni la, bi i dng, la rng
v cc b phong ha, c bit l ni la) v ngun nhn to (nh cng nghip
luyn kim, lc du). Cadimi xm nhp vo c th con ngi ch yu qua thc n
thc vt, c trng trn t giu cadimi hoc ti bng nc c cha nhiu

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cadimi, nhng ht th bi cadimi thng xuyn c th lm hi phi, trong phi


cadimi s thm vo mu v c phn phi i khp ni. Phn ln cadimi xm nhp
vo c th con ngi c gi li thn v c o thi, cn mt phn t (khong
1%) c gi li trong thn, do cadimi lin kt vi protein to thnh metallotionein
c thn [7]. Phn cn li c gi li trong c th v dn dn c tch ly cng
vi tui tc. Khi lng cadimi c tch tr ln, n c th th Zn2+ trong cc enzim
quan trng v gy ri lon tiu ha v cc chng bnh ri lon chc nng thn,
thiu mu, tng huyt p, ph hy ty sng, gy ung th.
1.3.2. Vai tr, chc nng v s nhim c Pb [10]
Ch v cc hp cht ca ch c ng dng rng ri trong cuc sng ca con
ngi. Ch l thnh phn chnh to nn pin, c quy, s dng cho xe, ch c s
dng nh cht nhum trng trong sn v c s dng nh thnh phn mu trong
trng men. Ch c dng trong dy cp in, u n v cc ng dn trong cng
nghip ho hc. Nhng lng ch ln c dng iu ch nhiu hp kim quan
trng nh thic hn, hp kim ch in, hp kim trcCh cn c dng lm cc
tm ngn chng phng x ht nhn do ch hp th tt cc tia phng x v tia
Rnghen (tng ca phng th nghim phng x c lt bng gch ch mi vin
thng nng hn 10Kg).
Ch l kim loi c nhiu ng dng quan trng trong cng nghip, do cng
vi s pht trin ca ngnh cng nghip khai thc ch bin, mc nhim ch ngy
cng trm trng.
Ch xm nhp qua ng tiu ho do n ung nhng rau, qu, thc phm,
ngun nc b nhim ch, qua ng h hp...Ch l mt thnh phn khng cn
thit ca khu phn n. Trung bnh liu lng ch do thc n, thc ung cung cp
cho khu phn hng ngy t 0,0033 n 0,005 mg/ kg th trng. Ngha l trung
bnh mt ngy, mt ngi ln n vo c th t 0,25 n 0,35mg ch. Vi liu
lng hm lng ch tch ly s tng dn theo tui, nhng cho n nay cha c
g chng t rng s tch ly liu lng c th gy ng c i vi ngi bnh
thng khe mnh.
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Liu lng ti a ch (Pb) c th chp nhn hng ngy cho ngi, do thc n
cung cp, c tm thi quy nh l 0,005mg/kg th trng. Ng c cp tnh do ch
thng t gp. Ng c trng din l do n phi thc n c cha mt lng ch, tuy
t nhng lin tc hng ngy. Ch cn hng ngy c th hp th t 1 mg ch tr ln, sau
mt vi nm, s c nhng triu chng c hiu: hi th thi, sng li vi vin en
li, da vng, au bng d di, to bn, au khp xng, bi lit chi trn (tay b bin
dng), mch yu, nc tiu t, trong nc tiu c poephyrin, ph n d b sy thai.
Ch c nhiu nh hng c hi n cc c quan, t chc trong c th con
ngi. c bit khi xm nhp vo c th, ch c th ph v mt cch mnh lit cc
chc nng chnh ca c th v t y dn n cc bin chng rng, t nn ma n
ri lon thn kinh hay t vong.
1.4. Cc phng php xc nh Cd, Pb
Hin nay, c nhiu phng php khc nhau xc nh cadimi v ch nh
phng php phn tch khi lng, phn tch th tch, in ho, ph phn t UVVIS, sc k lng hiu nng cao (HLPC), ph pht x nguyn t (AES), ph hp th
nguyn t ngn la (F-AAS) v khng ngn la (GF-AAS) Sau y l mt s
phng php xc nh Cadimi v Ch.
1.4.1. Phng php phn tch ho hc [13]
Nhm cc phng php ny dng xc nh hm lng ln (a dng) ca
cc cht, thng thng ln hn 0,05%, tc l mc miligam. Cc thit b v dng
c cho cc phng php ny n gin v khng t tin.
1.4.1.1. Phng php phn tch khi lng
* Nguyn tc: y l phng php da trn s kt ta cht cn phn tch
vi thuc th ph hp, sau lc, ra, sy hoc nung ri cn chnh xc sn phm
v t xc nh c hm lng cht phn tch.
* Cch tin hnh: Vi Cd, ngi ta thng cho kt ta di dng CdS trong
mi trng axit yu.Cn ch kt ta di dng PbSO4, PbCrO4 hay PbMoO4.
Phng php ny n gin khng i hi my mc hin i, t tin, c
chnh xc cao, tuy nhin i hi nhiu thi gian, thao tc phc tp v ch phn tch
hm lng ln, nn khng dng phn tch lng vt.
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1.4.1.2. Phng php phn tch th tch


* Nguyn tc: Da trn s o th tch dung dch thuc th bit nng
chnh xc (dung dch chun) c thm vo dung dch cht nh phn tc dng
ton b lng cht nh phn . Thi im thm lng thuc th tc dng va
vi cht nh phn gi l im tng ng. nhn bit im tng ng,
ngi ta dng cc cht gy ra hin tng i mu hay kt ta c th quan st bng
mt gi l cc cht ch th . Tu thuc vo loi phn ng chnh c dng m ngi
ta chia phng php phn tch th tch thnh cc nhm phng php trung ho,
phng php oxi ho kh, phng php kt ta, phng php complexon
* Cch tin hnh:
Xc nh Cd: Ngi ta c th chun cadimi trong dung dch kim
thng dng ch th Eriocrom en T hoc ch th xylen da cam. Vi hai ch th ny
s thay i mu sc u rt r rng. Trong php chun complexon dng dung
dch chun EDTA 0.01M, ch th Eriocrom en T pH=10 (dng dung dch
NH4Cl + NH3), cadimi c th c xc nh vi lng 25mg/100ml dung dch.
Trong php chun complexon th dung dch EDTA c nng c 0,10,01M, ch th xylen pH=6, cadimi c th c xc nh vi lng 100mg/100ml
dung dch.
Xc nh Pb: i vi Pb, ta c th chun trc tip bng EDTA hay chun
ngc bng Zn2+ hoc chun thay th vi ZnY2-, ch th ET - 00.
.* Cch tin hnh :
- Phng php th tch cromat
Kt ta cromat ch trong dung dch axetat amoni c axit ho bng
CH3COOH ri ho tan n bng hn hp clorua (NaCl + HCl) sau thm mt
lng KI (khng cho qu d KI v s to nn kt ta PbI2 c mu vng nh, lm
cho vic phn bit s i mu ca dung dch tr nn rt kh khn) vo dung dch v
chun lng I2 thot ra bng Na2S2O3.
2Pb(CHCOO)2 + K2Cr2O7 + H2O
2PbCrO4 + 4HCl
H2Cr2O7 + 6KI + 12HCl
2 Na2S2O3. + I2

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2PbCrO4 + 2CH3COOK + 2CH3COOH


2PbCl2+ H2Cr2O7 + H2O
2CrCl3 + 6KCl + 7H2O + 3I2
Na2S4O6 + 2NaI

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- Phng php chun complexon


- Cch 1: Chun trc tip Pb2+ bng EDTA pH trung tnh hoc kim
(pH khong 8 - 12), vi ch th ET 00.
Pb2+ + H2Y2 -

PbY2- + 2H+

Tuy nhin, ch rt d thu phn nn trc khi tng pH phi cho Pb 2+ to phc
km bn vi tactrat hoc tritanolamin.
- Cch 2: Chun ngc Pb2+ bng Zn2+. Cho Pb2+ tc dng vi mt lng
d chnh xc EDTA bit nng pH = 10. Sau chun EDTA d bng
Zn2+ vi ch th l ET 00.
Pb2+ + H2Y2-

PbY2- + 2H+

H2Y2- (d) + Zn2+

ZnY2- + 2H+

ZnInd + H2Y2-

ZnY2- + HInd

( nho)

(xanh)

- Cch 3: Chun thay th dng ZnY2-, ch th ET 00.


Do phc PbY2- bn hn ZnY2- pH = 10 nn Pb2+ s y Zn2+ ra khi phc
ZnY2-. Sau chun Zn2+ s xc nh c Pb2+:
Pb2+ + ZnY2ZnInd + H2Y2( nho)

PbY2- + Zn2+
ZnY2- + HInd
(xanh)

Phng php phn tch th tch c u im l nhanh chng v d thc hin,


tuy nhin cng ging nh phng php phn tch khi lng, phng php ny
cng khng c s dng trong phn tch lng vt, v phi thc hin qu trnh lm
giu phc tp.
1.4.2. Phng php phn tch cng c
1.4.2.1. Phng php in ho [7,13]
a. Phng php cc ph
Nguyn tc: Ngi ta thay i lin tc v tuyn tnh in p t vo 2 cc
kh cc ion kim loi, do mi kim loi c th kh khc nhau. Thng qua chiu cao
ca ng cong Von-Ampe c th nh lng c ion kim loi trong dung dch

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ghi cc ph. V dng gii hn Igh cc iu kin xc nh t l thun vi nng


ion trong dung dch ghi cc ph theo phng trnh:
I = kC
Trong phng php phn tch ny ngi ta dng in cc git thu ngn ri
l cc lm vic, trong th c qut tuyn tnh rt chm theo thi gian (thng
1-5mV/s) ng thi ghi dng l hm ca th trn cc git thu ngn ri. Sng cc
ph thu c c dng bc thang, da vo chiu cao c th nh lng c cht
phn tch.
Phng php ny c kh nhiu u im: N cho php xc nh c cht v c
v hu c vi nng 10-5 10-6M tu thuc vo cng v lp li ca dng
d. Sai s ca phng php thng l 2 3% vi nng 10-3 10-4M, l 5% vi
nng 10-5M ( iu kin nhit khng i).
V d: Cadimi c xc nh bng phng php ph pht x nguyn t h
quang vi khong nng 0,0005 0,002 %.
Vch cadimi 228,8 nm c s dng cho khong nng 0.00050.002%.
Nng cadimi 500 g/ml c xc nh bng phng php pht x ngn la v
nguyn t ny c c tnh pht x km.
Tuy nhin, phng php ny cng c nhng hn ch nh nh hng ca
dng t in, dng cc i, ca oxi ho tan, b mt in cc
Nhm loi tr nh hng trn ng thi tng nhy, hin nay c cc
phng php cc ph hin i: cc ph xung vi phn(DPP), cc ph sng vung
(SQWP) chng cho php xc nh lng vt ca nhiu nguyn t.
b. Phng php Von-ampe ho tan
V bn cht, phng php Von-Ampe ho tan cng ging nh phng php
cc ph l da trn vic o cng dng xc nh nng cc cht trong dung
dch. Nguyn tc gm hai bc:
Bc 1: in phn lm giu cht cn phn tch trn b mt in cc lm
vic, trong khong thi gian xc nh, ti th in cc xc nh.

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Bc 2: Ho tan kt ta c lm giu bng cch phn cc ngc in


cc lm vic, o v ghi dng ho tan. Trn ng Von-Ampe ho tan cho pic ca
nguyn t cn phn tch. Chiu cao pic t l thun vi nng .
u im ca phng php: xc nh c c nhng cht khng b kh trn
in cc vi nhy kh cao 10-6 10-8M.
Nhc im ca phng php: nhy b hn ch bi dng d, nhiu yu t
nh hng nh: in cc ch th, cht nn
1.4.2.2. Phng php quang ph
a. Phng php trc quang [7]
* Nguyn tc ca phng php ny: Da trn vic o hp th nh sng
ca mt dung dch phc to thnh gia ion cn xc nh vi mt thuc th v c
hoc hu c trong mi trng thch hp khi c chiu bi chm sng. Phng
php nh lng theo phng trnh c bn:
A = K.C
Trong : A: hp th quang ca cht
K: hng s thc nghim
C: nng ca cht phn tch
Phng php ny cho php xc nh nng ca cht khong 10 -5 - 10-7M
v l mt trong cc phng php c dng kh ph bin.
* Xc nh Cd: Vi cadimi xc nh hm lng cadimi bng phng php
chit trc quang dng ithizon, ngi ta chit bng CCl4 t mi trng kim mnh
cha tactrat, dung dch ithizonat ca cadimi trong dung mi hu c c mu , hp
th cc i bc sng =515 nm (knh lc sng c mu xanh l cy).
* Xc nh Pb: xc nh ch ta chuyn n v dng ch - ithizonat trong
mi trung pH = 5 6. Sau chit phc ny vo dung mi hu c CCl4 hoc
CHCl3 ri em o mt quang ca n ti = 510nm. Gii hn ca phng php
ny i vi ch l 0,05ppm.
u im ca phng php: nhy, n nh v chnh xc kh cao,
c s dng nhiu trong phn tch vi lng.

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Nhc im ca phng php: khng chn lc, mt thuc th c th to


nhiu phc vi nhiu ion.
b. Phng php ph pht x nguyn t (AES) [8]
iu kin bnh thng, nguyn t khng thu hay khng pht x nng
lng, nhng nu b kch thch th cc electron s nhn nng lng chuyn ln trng
thi c nng lng cao hn. Trng thi ny khng bn, chng c xu hng gii
phng nng lng tr v trng thi ban u bn vng di dng cc bc x. Cc
bc x ny gi l ph pht x nguyn t.
Nguyn tc ca phng php AES l da trn s xut hin ph pht x ca
nguyn t t do ca nguyn t phn tch trng thi khi c s tng tc vi ngun
nng lng ph hp. Mt s ngun nng lng thng dng kch thch ph AES
nh: ngn la n kh, h quang in, tia la in
u im: phng php AES c nhy cao (thng t n.10 -3 n n.10-4%),
t tn mu, c th phn tch ng thi nhiu nguyn t trong cng mt mu, phn
tch c lng vt kim loi trong nc, lng thc, thc phm.
Nhc im: ch cho bit thnh phn nguyn t trong mu m khng ch ra
c trng thi lin kt ca n trong mu.
Ngoi ra cn c mt s phng php xc nh Cd v Pb. Phng php ph
bin nht m hin nay thng dng l: phng php ph hp th nguyn t AAS.
c. Phng php ph hp th nguyn t (F- AAS)[9]
Nguyn tc : Khi nguyn t tn ti t do th kh v trng thi nng lng
c bn, th nguyn t khng thu hay khng pht ra nng lng. Tc l nguyn t
trng thi c bn. Song, nu chiu vo m hi nguyn t t do mt chm tia sng
n sc c bc sng ph hp, trng vi bc sng vch ph pht x c trng ca
nguyn t phn tch, chng s hp th tia sng sinh ra mt loi ph ca nguyn
t. Ph ny c gi l ph hp th ca nguyn t. Vi hai k thut nguyn t ha,
nn chng ta cng c hai php o tng ng. l php o ph hp th nguyn t
trong ngn la (F- AAS c nhy c 0,1 ppm) v php o ph hp th nguyn t
khng ngn la (GF AAS c nhy cao hn k thut ngn la 50- 1000 ln, c
0,1- 1 ppb).
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C s ca phn tch nh lng theo AAS l da vo mi quan h gia


cng vch ph v nng nguyn t cn phn tch theo biu thc:
A = a.Cx

C 2 phng php nh lng theo php o AAS l : phng php ng


chun v phng php thm tiu chun.
Thc t cho thy phng php ph hp th nguyn t c nhiu u vit nh:
nhy, chnh xc cao, lng mu tiu th t, tc phn tch nhanh. Vi u
im ny, AAS c th gii dng lm phng php tiu chun xc nh lng
nh v lng vt cc kim loi trong nhiu i tng khc nhau.
Php o ph AAS c th phn tch c lng vt ca hu ht cc kim loi
v c nhng hp cht hu c hay anion khng c ph hp th nguyn t. N c
s dng rng ri trong cc ngnh : a cht,cng nghip ha hc, ha du, y hc,
sinh hc, dc phm...
* Php o ph F-AAS:
K thut F-AAS dng nng lng nhit ca ngn la n kh ho hi v
nguyn t ho mu phn tch. Do mi qu trnh xy ra trong khi nguyn t ho
mu ph thuc vo c trng v tnh cht ca ngn la n kh nhng ch yu l
nhit ngn la. y l yu t quyt nh hiu sut nguyn t ho mu phn tch,
mi yu t nh hng n nhit ngn la n kh u nh hng n kt qu ca
phng php phn tch.
* Php o ph GF-AAS:
K thut GF-AAS ra i sau k thut F-AAS nhng c pht trin rt
nhanh, n nng cao nhy ca php xc nh ln gp hng trm ln so vi k
thut F-AAS. Mu phn tch bng k thut ny khng cn lm giu s b v lng
mu tiu tn t.
K thut GF-AAS l qu trnh nguyn t ho tc khc trong thi gian rt
ngn nh nng lng nhit ca dng in c cng sut ln v trong mi trng kh
tr (Argon). Qu trnh nguyn t ho xy ra theo cc giai on k tip nhau: sy
kh, tro ho luyn mu, nguyn t ho o ph hp th nguyn t v cui cng l

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lm sch cuvet. Nhit trong cuvet graphit l yu t quyt nh mi din bin ca


qu trnh nguyn t ho mu.
Nhng u - nhc im ca php o:
Cng nh cc phng php phn tch khc, phng php phn tch ph hp
th nguyn t cng c nhng u, nhc im nht nh l:
u im:
y l php o c nhy cao v chn lc tng i cao. Gn 60 nguyn
t ho hc c th xc nh bng phng php ny vi nhy t 1.10-4 1.10-5 %.
c bit, nu s dng k thut nguyn t ho khng ngn la th c th t ti
nhy n.10-7 %. Chnh v c nhy cao nn phng php phn tch ny c s
dng rt rng ri trong nhiu lnh vc xc nh lng vt cc kim loi. Mt u
im ln ca php o l: trong nhiu trng hp khng phi lm giu nguyn t cn
xc nh trc khi phn tch. Do , tn t mu, t thi gian cng nh ho cht tinh
khit lm giu mu. Trnh c s nhim bn khi x l mu qua cc giai on
phc tp. c bit, phng php ny cho php phn tch hng lot mu vi thi
gian ngn, kt qu phn tch li rt n nh, sai s nh.
Nhc im: Tuy nhin, bn cnh nhng u im php o AAS cng c
nhc im l ch cho bit thnh phn nguyn t ca cht trong mu phn tch m
khng ch ra trng thi lin kt ca nguyn t trong mu.
1.5. Phng php x l mu phn tch xc nh Cd v Pb [12,26]
xc nh hm lng Cd, Pb trong rau xanh, trc ht ta phi tin hnh x
l mu nhm chuyn cc nguyn t cn xc nh c trong mu t trng thi ban u
(dng rn) v dng dung dch. y l cng vic rt quan trng v c th dn n
nhng sai lch c trong kt qu phn tch do s nhim bn hay lm mt cht phn
tch nu thc hin khng tt. Hin nay c nhiu k thut x l mu phn tch, vi
i tng rau xanh th hai k thut dng ph mu gm k thut tro ha t bng
axit c hoc axit mnh (phng php x l t) v k thut tro ha kh (phng
php tro ha kh).

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1.5.1. Phng php x l t (bng axit c oxi ha mnh)


Nguyn tc ca phng php l dng axit c c tnh oxi ha mnh nh
(HNO3, HClO4), hay hn hp c axit c c tnh oxi ha mnh(HNO3 + H2O2)
phn hy ht cc cht hu c ca mu trong bnh Kendan, chuyn cc kim loi
dng hu c v dng cc ion trong dung dch mui v c. Vic phn hy c th
thc hin trong h ng kn (p sut cao), hay trong h m (p sut thng). Lng
axit thng phi dng gp t 10- 15 ln lng mu, ty thuc mi loi mu v cu
trc vt l ha hc ca n. Thi gian phn hy mu trong cc h m, bnh Kendan,
ng nghim, cc thng t vi gi n vi chc gi, cng ty loi mu, bn cht
ca cc cht, cn nu trong l vi sng h kn th ch cn vi chc pht. Thng khi
phn hy xong phi ui ht axit d trc khi nh mc v tin hnh o ph.
u nhc im ca k thut ny l
+ Khng mt mt s kim loi nh Pb, Fe, Zn, Cu
+ Thi gian phn hu lu, thng l t 10 -12 gi.
+ Tn nhiu axit tinh khit, axit d nhiu, phi ui axit sau khi x l.
+ D gy nhim bn, nu cc ho cht khng c sch cao.
+ Phi ui axit d lu, c khi kh khn khng ht c. ng thi khi un
ui axit lu li gy ra s nhim bn hay bn mt mu.
1.5.2. Phng php x l kh
Nguyn tc: i vi cc mu hu c trc ht phi c xay nghin thnh
bt, va hay th huyn ph. Sau dng nhit ha tro mu, t chy cht hu c
v a cc kim loi v dng oxit hay mui ca chng. C th l: Cn ly mt lng
mu nht nh (5- 10 g) vo chn nung. Nung cht mu nhit thch hp, t
chy ht cc cht hu c, v ly b v c cn li ca cc mu l cc oxit, cc
muisau ha tan b thu c trong axit v c nh HCl (1/1), HNO 3 (1/2)
chuyn cc kim loi v dng ion trong dung dch.Quyt nh dng tro ha y l
nhit nung v thi gian nung (nhit tro ha v thi gian tro ha) v cc cht
ph gia thm vo mu khi nung. Nhit tro ha cc cht hu c thng c chn
thch hp trong khong 400- 550 0C, ty theo mi loi mu v cht cn phn tch.

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S dng phng php ny c nhng u nhc im nh:


+ Tro ha trit c mu, ht cc cht hu c.
+ n gin, d thc hin, qu trnh x l khng lu nh phng php v c
ha t.
+ Khng tn nhiu axit tinh khit cao, v khng c axit d.
+ Hn ch c s nhim bn do dng t ha cht.
+ Mu dung dch thu c sch s v trong.
+ Nhng hay b mt mt s nguyn t phn tch (Pb, Zn, Cu, Cd), nu
khng dng cht bo v v cht chy.

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CHNG 2: I TNG V PHNG PHP NGHIN CU


2.1. i tng v mc tiu nghin cu
2.1.1. i tng v mc tiu
i vi Vit Nam, mt nc nng nghip vn gi vai tr quan trng trong
nn kinh t quc dn th vn lng thc, thc phm c ngha v cng to ln.
Rau l ngun thc phm cn thit v quan trng cung cp y cc cht cn thit
cho c th: vitamin, mui khong, m... N khng nhng em li gi tr v kinh t
m cn mang gi tr dinh dng cao m n cn n nh i sng hng ngy ca con
ngi v ng vt. Ngoi ra, rau cn c dng nh mt loi thuc cha bnh
thng thng. Hin nay v chy theo li nhun nn cht lng ca mt s loi rau
c nh hng n sc kho v gy hi cho con ngi v ng vt do nhim cc cht
c nh kim loi nng nh Cd, Pb, As, Hg, ...
Chnh v vy, i tng v mc tiu nghin cu trong lun vn ny l xc
nh hm lng Cd v Pb trong rau xanh bng phng php ph hp th nguyn t
ngn la (F - AAS).
2.1.2. Cc ni dung nghin cu
- Kho st chn cc iu kin ph hp o ph F- AAS ca Cd v Pb.
- Nghin cu cc yu t nh hng n php xc nh Cd v Pb ca php o.
- Kho st khong tuyn tnh v xy dng ng chun trong php o ph.
- Xc nh gii hn pht hin v gii hn nh lng ca php o.
- nh gi sai s v lp li ca phng php.
- ng dng phng php xc nh Cd v Pb trong mt s mu rau ca huyn
i T - Tnh Thi Nguyn.
2.2. Gii thiu phng php ph hp th nguyn t [9]
2.2.1. Nguyn tc ca phng php
C s l thuyt ca php o ph hp th nguyn t (AAS) l da trn s hp
th nng lng bc x n sc ca nguyn t t do ca nguyn t trng thi hi,
khi chiu chm tia bc x qua m hi nguyn t ca nguyn t y. Mi trng hp
th chnh l m hi cc nguyn t t do ca mu phn tch.
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Do , mun thc hin php o AAS cn phi c cc qu trnh sau:


1. Chuyn mu phn tch t trng thi ban u (rn hoc dung dch) thnh
trng thi hi ca cc nguyn t t do. y l qu trnh nguyn t ho mu.
2. Chiu chm tia pht x c trng ca nguyn t cn phn tch t ngun
bc x qua m hi nguyn t t do y. Cc nguyn t ca nguyn t cn xc nh
trong m hi s hp th nhng tia bc x nht nh v to ra ph hp th ca n.
3. Tip , nh h thng quang hc, ngi ta thu, phn ly v chn mt vch
ph hp th ca nguyn t cn phn tch o cng ca n. Cng chnh
l tn hiu hp th ca vch ph hp th. Trong mt gii hn nng xc nh, tn
hiu ny ph thuc tuyn tnh vo nng ca nguyn t cn xc nh trong mu
theo phng trnh:
A = K.Cb
A : Cng hp th
K: Hng s thc nghim
C: Nng nguyn t trong mu
b: Hng s bn cht, ph thuc vo nng (0<b1)
Phng trnh trn l c s nh lng cho php o AAS
Tu thuc vo k thut nguyn t ho mu m ngi ta phn bit ph hp
th nguyn t ngn la (F-AAS) cho nhy c ppm. Ph hp th nguyn t khng
ngn la (GF-AAS) cho nhy n ppb.
2.2.2. H trang b ca php o
Da vo nguyn tc ca php o, ta c th m t h thng trang thit b o
AAS gm cc phn sau:
1. Ngun pht chm tia bc x cng hng ca nguyn t cn phn tch.
c th l n catot rng (HCL), n phng in khng in cc (EDL) hoc ngun
bc x in lin tc c bin iu.
2. H thng nguyn t ho mu. H thng ny c ch to theo hai k thut:
- K thut nguyn t ho mu bng ngn la n kh (F-AAS).
- K thut nguyn t ho mu khng ngn la (GF -AAS).

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3. B phn n sc (h quang hc) c nhim v thu, phn ly v chn tia


sng(vch ph) cn o hng vo nhn quang in o tn hiu AAS .
4. B phn khuch i v ch th tn hiu AAS. Phn ch th tn hiu c th l :
- in k ch tn hiu AAS
- B t ghi cc pic hp th
- B ch th hin s
- My tnh (computer) vi mn hnh video, hin th, lu tr, x l s liu
v iu khin ton b h thng my o
Di y l s biu din cu to my o AAS:
(/)/)/)/)/)/)
n catt rng

Detector

B phn ch th

H thng
- nebulizzer v burner

Dung dch mu

Hnh 2.1 : S cu to my ph hp th nguyn t


2.3. Gii thiu v phng php x l t mu bng axit
i vi vic xc nh cadimi v ch trong rau xanh chng ti chn phng
php v c ha t x l mu. Mu c x l trong h m iu kin thng
bng cch s dng axit HNO3 65% v H2O2 30% un mu ti khi khi mu nu

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khng cn bc ln v axit cn. Cn c ha tan trong HNO3 2% nh mc em o.


Hoc v c ha mu trong l vi sng, s dng axit HNO 3 65% v H2O2
2.3.1. Nguyn tc ca phng php
Dng mt axit c c tnh oxi ho mnh, hay hn hp cc axit c c tnh
oxi ho mnh, hay mt axit c tnh oxi ho mnh v mt axit khng c tnh oxi ho
nh (HNO3 + HCl), hay (HF + HClO4), phn hu ht cc cht hu c ca mu
trong bnh kenan, chuyn ht cc kim loi dng hu c v dng cc ion trong
dung dch mui v c. Vic phn hu c th thc hin trong h ng kn p sut cao
hay h m (p sut thng). Lng axit thng dng phi gp t 15 10 ln lng
mu, thi gian t 10 12 gi nn khi phn hu xong thng phi ui ht axit d.
S phn hy mu l do hai tc nhn ng thi xy ra l : Nng lng nhit,
axit c.
2.3.2. C ch phn hy
Di tc dng ca axit cc ht (phn t) mu b ph hy v ha tan, tc nhn
nng lng nhit lm tan r cc ht mu. S khuch tn i lu, chuyn ng nhit
v va chm ca cc ht mu vi nhau cng lm chng b bo mn dn t ngoi vo
trong ri tan ht.
Cc qu trnh xy ra trong khi phn hy mu:
+ S ph v mng li cu trc ca ht mu gii phng cc cht phn tch
v chuyn vo dung dch di dng cc mui tan.
+ Qu trnh oxi ha kh lm thay i ha tr, chuyn i dng, lm tan v
cc ht vt cht mu gii phng cht phn tch v dng mui tan.
+ i vi mu hu c phn tch cc kim loi th c s t chy, ph hy cc
hp cht hu c v mn to ra kh CO2 v nc, gii phng cc kim loi trong
cht mu hu c v dng mui v c tan.
+ To ra hp cht d bay hi, lm mt i cc anion trong phn t cht
mulm mu b phn hy to ra cc hp cht tan trong dung dch.
+ S to thnh cc hp cht hay mui phc tan trong dung dch.
Nh vy trong qu trnh x l mu c th c cc phn ng ha hc xy ra,
nh phn ng oxi ha kh, phn ng thy phn, phn ng to phc, phn ng ha

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tan, phn ng kt ta ca phn t cht mu vi nhau v vi cc axt dng phn hy


mu. Trong qu trnh no l qu trnh chnh hay ph c quyt nh bi thnh
phn cht nn bn cht ca cht mu v cc loi axt dng phn hy v ha tan mu
2.4. Dng c - ha cht
2.4.1. Dng c my mc
Cc trang thit b, dng c cn thit cho qu trnh phn tch Cd v Pb bng
phng php ph hp th nguyn t l:
- My o quang ph hp th nguyn t Thermo electron corporation (Anh)Phng th nghim Ho Hc-i hc Khoa Hc-i hc Thi Nguyn.
- Pipet 1;2;5;10 ml.
- Pipet man.
- Bnh kendal.
- Bnh nh mc 10; 25; 50; 250; 1000 ml.
- Cc thu tinh.
- ng ong, phu.
- T sy Jeio tech (Hn Quc).
- Cn phn tch v mt s thit b khc.
2.4.2. Ho cht
- Nc ct hai ln.
- Axit c: HCl 36%; HNO3 65%; HClO4 70%: Merck.
- Cc dung dch chun Cd2+ 1000 ppm (1000 mg/l); Pb2+ 1000 ppm (1000 mg/l)
- Cc dung dch nn: CH3COONH4 PA 10% (Merck).
CH3COONa PA 10% (Merck).
LaCl3 PA 10% (Merck).
- Dung dch cc cation kim loi nghin cu nh hng.

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CHNG 3: THC NGHIM V BN LUN KT QU


3.1. Kho st cc iu kin thc nghim o ph ca cadimi v ch
3.1.1. Kho st chn vch o ph
Mi loi nguyn t ca nguyn t ho hc ch c th hp th nhng bc x
c bc sng m chnh n pht ra trong qu trnh pht x. Nhng thc t khng
phi mi loi nguyn t u hp th c tt c cc bc x m n pht ra. Qu trnh
hp th ch nhy vi cc vch c trng (gi l vch nhy). Vch no c hp th
cng nhy th khong nng tuyn tnh cng hp.
* i vi cadimi : Nguyn t Cd c 2 vch ph c trng, nhy nht 1 =
228,8 nm v 2 = 326,1 nm. Tin hnh kho st dung dch Cd2+ 1 ppm trong HNO3
2% 2 bc sng, kt qu thu c bng sau:
Bng 3.1: Kt qu kho st vch ph ca cadimi
Vch o (nm)
Abs
228,8 nm

326,1nm

Ln 1

0,3540

0,3350

Ln 2

0,3540

0,3340

Ln 3

0,3540

0,3350

Trung bnh

0,3540

0,3350

%RSD

0,1123

0,2312

* i vi ch :Tin hnh kho st hai vch ph c trng nhy nht ca ch


l 217,0 nm v 283,3 nm. Kt qu kho st hai vch ph c trng ca ch i vi
cc dung dch Pb2+ c nng 2 ppm trong HNO3 2%, NH4Ac 1% c trnh by
trong bng 3.2

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Bng 3.2: Kt qu kho st vch ph ca ch


Abs

Vch o (nm)
217,0 nm

283,3 nm

Ln 1

0,0885

0,0357

Ln 2

0,0887

0,0362

Ln 3

0,0889

0,0358

Trung bnh

0,0887

0,0359

%RSD

0,3429

0,7348

Nh vy nhn vo kt qu kho st, cng nh da vo cc ti liu tham kho,


cng nh yu cu xc nh vi lng cc nguyn t chng ti thy rng cho thy ti
vch ph 217,0 nm i vi nguyn t ch v vch ph 228,8 nm i vi nguyn t
cadimi th chnh xc v lp li cao nht. Do chng ti chn vch o ph
ca Pb l 217 nm v vch o ph ca Cd l 228,8 nm .
3.1.2. Kho st cng dng n catot rng (HCL)
n catot rng HCL l ngun pht tia bc x cng hng, n ch pht ra
nhng tia pht x nhy ca nguyn t kim loi c dng lm catot rng. Mi n
HCL u c dng in gii hn cc i m n c th chu ng c, tuy nhin
gi tr thch hp nht khi s dng n l trong vng t 60-85% gi tr cc i.
Vi n n Cd c Imax = 12mA, Pb c Imax = 15 mA, tin hnh kho st
cng n HCL trong vng t 60 80% Imax i vi dung dch Pb2+ 2ppm trong
HNO3 2%, NH4Ac 1%. Kt qu kho st cng n catt rng c trnh by
trong bng 3.3 v 3.4
Bng 3.3: Kho st cng dng n vi nguyn t Cd
% Imax

Abs-Cd

60

65

75

83

Ln 1

0,3040

0,2965

0,2882

0,2909

Ln 2

0,3042

0,2967

0,2885

0,2910

Ln 3

0,3044

0,2969

0,2888

0,2909

Trung bnh

0,3042

0,2967

0,2885

0,2909

%RSD

0,5089

0,2613

0,1400

0,2145

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Bng 3.4: Kt qu kho st cng dng n vi nguyn t Pb


% Imax

60

70

73

80

Ln 1

0,0890

0,0895

0,0795

0,0853

Ln 2

0,0889

0,0897

0,0794

0,0853

Ln 3

0,0890

0,0893

0,0795

0,0852

Trung bnh

0,0890

0,0895

0,0795

0,0853

%RSD

0,2243

0,5107

0,9325

0,8829

Abs-Pb

Qua kt qu kho st ta thy rng khi cng dng n gim th cng


hp th cu vch ph tng nhng h s bin ng tng hay sai s tng, v vy ta
phi chn c cng dng n sao cho cng ca vch ph va cao va n
nh tc sai s nh, do chng ti chn cng dng n Cd 8mA (65%) v
cng dng n Pb 10mA (70%).
3.1.3. Kho st rng khe o
rng ca khe o nh hng n tn hiu ph hp th. Theo nguyn tc
hot ng ca h thng n sc trong my ph hp th nguyn t, chm tia pht x
cng hng ca nguyn t cn nghin cu c pht ra t n catot rng, sau khi i
qua mi trng hp th s c hng vo khe o ca my, c chun trc, c
phn ly v sau ch mt vch ph cn o c chn v hng vo khe o tc
dng vo nhn quang in pht hin v
xc nh cng ca vch ph. Do vy, khe o ca my phi c chn chnh
xc, ph hp vi tng vch ph.
i vi cc nguyn t Cd v Pb chn c khe o ph hp chng ti tin
hnh kho st vi cc dung dch Cd 1ppm v Pb 2 ppm trong HNO3 2% v tin hnh
o cc khe o khc nhau. Kt qu o c trnh by trong bng 3.5 v 3.6 sau:
Bng 3.5 : Kt qu kho st khe o vi nguyn t Cd
Khe o(nm)

0,1

0,2

0,5

1,0

Ln 1

0,3132

0,3130

0,3157

0,3125

Ln 1

0,3134

0,3132

0,3157

0,3124

Ln 1

0,3135

0,3134

0,3157

0,3123

Trung bnh

0,3134

0,3132

0,3157

0,3123

Abs

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Bng 3.6 : Kt qu kho st khe o vi nguyn t Pb


Khe o(nm)

0,1

0,2

0,5

Ln 1

0,0871

0,0868

0,0875

0,0872

Ln 2

0,0870

0,0869

0,0875

0,0871

Ln 3

0,0869

0,0870

0,0875

0,0873

Trung bnh

0,0870

0,0869

0,0875

0,0872

Abs

T kt qu thu c bng trn chng ti chn khe o vi nguyn t Cd v


nguyn t Pb u l 0,5 nm v y l khe o cho kt qu phn tch c lp li cao,
sai s nh nht v 100% din tch pic ca vch ph s nm trong khe o.
3.1.4. Kho st chiu cao ca n nguyn t ho mu
Nguyn t ho mu l cng vic quan trng nht trong php o AAS. Bi v
n l giai on to ra cc nguyn t t do, l yu t quyt nh sinh ra ph AAS.
Vic chn chiu cao ngn la gip loi tr tt cc yu t nh hng, thu tn hiu n
nh, php o c nhy v chnh xc cao.
Nhit l thng s c trng ca ngn la n kh, l yu t quyt nh n
hiu sut nguyn t ho mu. M nhit ngn la thay i theo tng vng. Vng
trung tm ngn la c nhit cao, ngn la thng c mu xanh nht. Trong
phn ny, hn hp kh c t chy tt nht v khng c phn ng th cp. Cn
trong vng v v ui ngn la thng xy ra nhiu phn ng th cp khng c li
cho php o. V vy, trong php o ph hp th nguyn t, ngi ta phi chn chiu
cao thch hp ca ngn n nguyn t ho sao cho ngun n sc phi chiu vo
phn trung tm ngn la nguyn t ho mu.
* i vi nguyn t Cd: Kt qu kho st dung dch Cd2+ 1 ppm trong HNO3
2%, NH4Ac 1% cc chiu cao khc nhau ca n nguyn t ho mu c trnh
by bng 3.7

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Bng 3.7: Kt qu kho st chiu cao n nguyn t ho mu ca Cd


Chiu cao n (mm)

Abs- Cd

Ln 1

0,3127

0,3128

0,3131

0,3131

0,3026

Ln 2

0,3129

0,3128

0,3129

0,3131

0,3028

Ln 3

0,3123

0,3127

0,3130

0,3131

0,3027

Trung bnh

0,3126

0,3128

0,3130

0,3131

0,3027

* i vi nguyn t Pb: Kt qu kho st dung dch Pb2+ 2ppm trong HNO3


2%, NH4Ac 1% cc chiu cao khc nhau ca n nguyn t ho mu c trnh
by bng 3.8
Bng 3.8: Kt qu kho st chiu cao n nguyn t ho mu ca Pb
Chiu cao n (mm)

Abs- Pb

Ln 1

0,0856

0,0848

0,0852

0,0858

0,0845

Ln 2

0,0857

0,0849

0,0850

0,0858

0,0846

Ln 3

0,0857

0,0848

0,0851

0,0858

0,0845

Trung bnh

0,0857

0,0848

0,0851

0,0858

0,0845

Qua kt qu thu c y chng ti chn chiu cao ca n nguyn t ho


mu i vi cc nguyn t Cd v Pb u l 7mm v iu kin ny pic thu c c
nhy v n nh cao, sai s l nh nht.
3.1.5. Kho st lu lng kh axetilen
Trong php o F-AAS, nhit ca ngn la l yu t quyt nh qu trnh
ho hi v nguyn t ha mu. Nhit ngn la n kh li ph thuc nhiu vo
bn cht v thnh phn ca cc cht kh t chy to ra ngn la. iu c ngha
l vi mi mt hn hp kh t s cho ngn la c nhit khc nhau. Hai loi hn
hp kh v ang c s dng ph bin trong php o F-AAS l hn hp (khng
kh nn + acetylen) v hn hp (kh N2O + acetylen).
Cadimi v ch thng c nguyn t ho nhit khong 23000C
24500C nn dng hn hp khng kh nn v acetylen l thch hp nht.
chn iu kin ngn la c nhit ph hp cho php o, tin hnh kho
st dung dch Cd2+ 1ppm v Pb2+ 2 ppm trong HNO3 2%, NH4Ac 1% .

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Bng 3.9: Kt qu kho st lu lng kh axetilen i vi Cd


C2H2 (l/ph)

Abs-Cd

0,9

1,0

1,1

1,2

1,3

Ln 1

0,3125

0,3023

0,3127

0,3129

0,3124

Ln 2

0,3125

0,3022

0,3126

0,3129

0,3123

Ln 3

0,3124

0,3022

0,3126

0,3129

0,3122

Trung bnh

0,3125

0,3022

0,3126

0,3129

0,3123

Bng 3.10: Kt qu kho st lu lng kh axetilen i vi Pb


C2H2(l/ph)

0,9

1,0

1,1

1,2

1,3

Ln 1

0,0867

0,0870

0,0869

0,0871

0,0868

Ln 2

0,0866

0,0869

0,0870

0,0871

0,0866

Ln 3

0,0867

0,0869

0,0870

0,0871

0,0862

Trung bnh

0,0867

0,0869

0,0870

0,0871

0,0865

Abs - Pb

Theo kt qu thu c cc bng trn ta thy rng lu lng kh axetilen


1,2lt/ph l ph hp nht i vi php o cc nguyn t Cd v Pb. V y m bo
cho php o c nhy v n nh cao nht.
3.1.6. Tc dn mu
Tc dn mu vo bung aresol ho cng nh hng ti cng vch
ph cn o. i vi mt h thng my nht nh th tc dn mu ph thuc ch
yu vo nht ca dung dch. Trn my Thermo ca Anh, chng ti s dng h
thng bm mu t ng (ASC), dung dch mu c ht vi th tch l 20l cho
mt ln o. y l tc dn mu c chn ph hp vi hu ht cc dung dch
thng thng c nng mui khng cao.
3.2. Kho st cc yu t nh hng n php o
Trong php o ph hp th nguyn t F- AAS c rt nhiu yu t nh hng
qu trnh o, nhng c bit cc yu t ha hc rt a dng v phc tp c th dn
n nhng hng nh sau.
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* Lm gim cng vch ph ca nguyn t phn tch do to hp cht b


mt, kh ha hi v kh nguyn t ha.
* Lm tng cng vch ph do to cc hp cht d ha hi v d nguyn
t ha hay do hn ch nh hng ca s ion ha v kch thch ph pht x ca
nguyn t phn tch.
* Tng cng vch ph khi nguyn t phn tch tn ti trong nn ca mu
l nhng hp cht ha hi. Khi cc cht ny nh mt cht mang cho s ha hi
nguyn t phn tch, n lm ha hi vi hiu sut cao.
* Gim cng vch ph khi nguyn t phn tch trong nn ca mu l
nhng hp cht bn nhit, kh ha hi. Lc ny cc nguyn t nn km hm s ha
hi cc nguyn t phn tch.
* Chnh vi tc dng trn m chng ta cn phi kho st v nghin cu s
nh hng ha hc n php o l rt cn thit.
3.2.1. Kho st nh hng ca cc loi axit v nng axit
Trong php o F-AAS, mu o dng dung dch v trong mi trng axit.
Nng axit trong dung dch lun c nh hng n cng vch ph ca cc
nguyn t cn phn tch thng qua tc dn mu, kh nng ho hi v nguyn t
ho cc cht mu.
Ni chung cc loi axit d bay hi gy nh hng nh, cc loi axit kh bay
hi gy nh hng ln. Cc axit lm gim cng vch ph ca nguyn t cn
phn tch theo th t: HClO4<HCl<HNO3<H2SO4<H3PO4<HF. Ngha l axit HClO4
, HCl v HNO3 gy nh hng nh nht trong vng nng nh. Chnh v th trong
thc t phn tch ca php o ph hp th nguyn t (AAS) ngi ta thng dng
mi trng l axit HCl hay HNO3.
Chng ti tin hnh kho st nh hng ca hai loi axit c th dng ho
tan mu v to mi trng axit l HCl v HNO3 ln cng ca vch ph hp th
ca cadimi v ch trn nguyn tc c nh nng ca ion kim loi v pha trong cc
dung dch axit c nng bin thin v kho st hp th ca cc nguyn t
cadimi v ch.

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* Tin hnh kho st i vi dung dch Cd 1ppm v Pb 2 ppm trong cc axit


HCl v HNO3 vi nng bin thin t 0 n 3%. Cc kt qu c ch ra bng
3.11 v 3.12
Bng 3.11: nh hng ca cc loi axit v nng axit ti php o Cd
Nng axit (C%)

HNO3

Ln 1

0,3045

0,3051

0,3052

0,3042

Ln 2

0,3047

0,3058

0,3053

0,3046

Ln 3

0,3043

0,3050

0,3053

0,3047

Trung bnh

0,3045

0,3053

0,3053

0,3045

0,1240

0,5498

0,1860

0,3415

Ln 1

0,3045

0,3009

0,2992

0,2968

Ln 2

0,3047

0,3008

0,2990

0,2968

Ln 3

0,3043

0,3009

0,2985

0,2969

Trung bnh

0,3045

0,3009

0,2989

0,2968

0,1240

0,2328

0,2960

0,2007

%RSD

HCl

%RSD

Bng 3.12: nh hng ca cc loi axit v nng axit ti php o Pb


Nng axit (C%)

Ln 1

0,0679

0,0749

0,0760

0,0775

Ln 2

0,0683

0,0749

0,0763

0,0776

Ln 3

0,0678

0,0748

0,0763

0,0776

Trung bnh

0,0680

0,0749

0,0762

0,0776

Sai s (%RSD)

0,9040

0,2605

0,2571

0,7329

Ln 1

0,0679

0,0709

0,0723

0,0738

Ln 2

0,0683

0,0710

0,0722

0,0739

Ln 3

0,0678

0,0710

0,0723

0,0739

Trung bnh

0,0680

0,0710

0,0723

0,0739

0,9040

0,9859

0,2370

0,2045

HNO3

HCl

Sai s (%RSD)

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Nh vy nng HNO3 v HCl trong cc dung dch mu < 5% khng nh


hng ti php o ph ca Cd v Pb.
Da vo kt qu thu c bng trn chng ti thy nng axit khng nh
hng ng k n cng vch ph ca Cd v Pb. Do vy ti chn axit HNO3
nng 2% cho ph n nh nht, ng thi gi c nguyn t cn phn tch
trong dung dch. V vy trong qu trnh phn tch Cd v Pb c pha trong HNO 3
2% v lm dung dch nn.
3.2.2. Kho st thnh phn nn ca mu
Trong mt s trng hp, cc mu c cha cc nguyn t di dng cc cht
bn nhit. Cc cht ny gy kh khn, cn tr cho qu trnh ho hi nguyn t ho
mu, t lm gim nhy ca phng php phn tch v cng vch ph.
loi tr nh hng ca yu t ny ngi ta c th dng nhiu bin php khc nhau.
l:
+ Tng nhit nguyn t ho mu.
+ Thm cc cht ph gia c nng ph hp ngn cn s xut hin cc
hp cht bn nhit.
+ Tch b hai nguyn t nn khi hai bin php trn khng t hiu qu. Tt
nhin vic s dng bin php ny l hu hn.
Trong ba bin php ny th bin php th nht ch c s dng trong mt
chng mc nht nh do s hn ch ca trang thit b, bn cht ca kh t. Do
phng php thm cht nn l bin php c s dng ph bin trong php o
AAS. Vi tng php o m ta s dng cc nn khc nhau.
Trn c s l thuyt ca php o m chng ti tin hnh kho st vi cht
nn CH3COONa (NaAc) v CH3COONH4 (NH4Ac) c nng bin thin t 1-3%
i vi dung dch Cd 1ppm v Pb 2ppm trong HNO3 2%. Kt qu c ch ra
bng 3.13 sau:

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Bng 3.13: Kho st nh hng ca thnh phn nn


Nng (C%)

Cd2+ 1ppm

Pb2+ 2ppm

Abs

% RSD

Abs

% RSD

0,3147

0,2985

0,3147

0,2985

NH4Ac 1%

0,3201

0,2175

0,0725

0,1535

NH4Ac 2%

0,3143

0,4015

0,0716

0,8745

NH4Ac3%

0,3249

0,0936

0,0721

0,4659

NaAc 1%

0,3072

0,3798

0,0719

0,3424

NaAc 2%

0,3056

0,3005

0,0720

0,8570

NaAc 3%

0,3027

0,3423

0,0718

1,0187

Qua kt qu thu c chng ti thy rng nn CH3COONH4 1% cho cng


hp thu cao v n nh nht hay h s bin ng nh nht. Do chng ti s
dng nn CH3COONH4 1% tin hnh php o cadimi v ch.
Nn NH4Ac c tc dng loi b s hnh thnh cc cht bn nhit, nhng li
khng c tc dng loi b nh hng ca mt s cation v anion, v vy cho kt
qu phn tch tt nht cn c thm ph gia khc na. Thc t trong php o FAAS, cc cht ph gia thm vo thng l LaCl3, SrCl2, LiCl, KCl v AlCl3. y
LaCl3 c s dng rng ri nht, cc cht cn li ch cho mt s trng hp ring
bit. V vy chng ti chn LaCl3 l cht ph gia thm vo, tuy nhin LaCl3 c nhit
ha hi cao do nu nng LaCl3 trong mu m ln th nhit ca ngn la
khng ha hi mu. V th cn phi kho st nng nn LaCl 3 sao cho ph
hp nht. Do chng ti tin hnh kho st i vi dung dch Cd 1ppm v Pb
2ppm trong HNO3 2% + NH4Ac 1%. Kt qu thu c nh trong bng 3.14
Bng 3.14: Kt qu kho st nng LaCl3
Nng LaCl3

Cd

Pb

(%)

Abs

%RSD

Abs

%RSD

0,3105

0,2715

0,0785

0,6985

0,5

0,3200

0,2341

0,0802

0,1723

1,0

0,3225

0,2507

0,0829

0,2753

1,5

0,3212

0,4618

0,0811

0,3703

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Qua kt qu thu c ta thy ti nng LaCl 3 1% cng hp th ca Cd


v Pb cao v n nh, do chng ti chn LaCl3 1% l ph gia thm vo.
3.2.3. Kho st nh hng ca cc ion
Dung dch mu phn tch, ngoi nguyn t cn xc nh, thng cn cha
cc nguyn t khc. Cc nguyn t ny tn ti di dng cc cation hay anion tan
trong dung dch mu. Cc ion ny c th lm tng, cng c th lm gim, hoc cng
c th khng gy nh hng g n cng vch ph ca nguyn t phn tch.
Khi c nh hng th mc nh hng ca mi ion cng rt khc nhau trong tng
trng hp c th.
Trong i tng phn tch ca chng ti (rau xanh) thng c rt nhiu
cation v anion khc nhau, trong ng ch l cc cation v anion sau: K +; Na+;
Ca2+; Ba2+; Mg2+;... Cl ;SO24 ; NO3 ;... Do vy chng ti tin hnh kho st nh hng
ca cc cation v anion ny ti php o ph AAS.
3.2.3.1. Kho st nh hng ca cc cation
xem xt nh hng ca cc cation chng ti tin hnh kho st nh hng
ca tng nhm cation i vi dung dch Cd 1ppm v Pb 1ppm (trong nn HNO3
2%; CH3COONH4 1%). l cc nhm :
Nhm cation kim loi kim: K+, Na+.
Nhm cation kim loi kim th: Ca2+,Mg2+, Ba2+, Sr2+
Nhm cation kim loi nng ho tr II: Cu2+, Ni2+, Mn2+; Zn2+
Nhm kim loi ho tr III: Al3+,Fe3+.
Kt qu kho st c ch ra cc bng sau:
Bng 3.15: nh hng ca nhm cation kim loi kim
Mu

C0

C1

C2

C3

C4

200

300

400

800

Na+ (ppm)

100

200

400

500

Abs-Cd

0,3056

0,3049

0,3048

0,3054

0,3058

Abs-Pb

0,0709

0,0714

0,0726

0,0706

0,0722

Ion
K+(ppm)

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Bng 3.16: nh hng ca nhm cation kim loi kim th


Mu

C0

C5

C6

C7

C8

Mg2+ (ppm)

50

100

150

200

Ca2+ (ppm)

50

100

150

200

Ba2+ (ppm)

10

20

30

40

Sr2+ (ppm)

10

20

30

40

Abs-Cd

0,3056

0,3036

0,3062

0,3059

0,3064

Abs-Pb

0,0709

0,0714

0,0707

0,0716

0,0700

Ion

Bng 3.17: nh hng ca nhm cation kim loi nng ho tr II


Mu

C0

C9

C10

C11

C12

Cu2+ (ppm)

20

30

40

50

Ni2+ (ppm)

20

30

40

50

Zn2+ (ppm)

20

30

40

50

Mn2+(ppm)

20

30

40

50

Abs-Cd

0,3056

0,3040

0,3041

0,3043

0,3045

Abs-Pb

0,0709

0,0702

0,0718

0,0725

0,0723

Ion

Bng 3.18: nh hng ca nhm cation kim loi ho tr III


Mu

C0

C13

C14

C15

C16

Al3+ (ppm)

20

60

80

100

Fe3+(ppm)

20

60

80

100

Cr3+(ppm)

10

Abs-Cd

0,3056

0,3051

0,3069

0,3063

0,3060

Abs-Pb

0,0709

0,0716

0,0718

0,0709

0,0705

Ion

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Bng 3.19 : nh hng tng ca cation


Mu

C0

C17

C18

C19

C20

K+(ppm)

200

300

400

800

Na+ (ppm)

100

200

400

500

Mg2+(ppm)

50

100

150

200

Ca2+ (ppm)

50

100

150

200

Ba2+ (ppm)

10

20

30

40

Sr2+ (ppm)

10

20

30

40

Cu2+(ppm)

20

30

40

50

Ni2+ (ppm)

20

30

40

50

Zn2+ (ppm)

20

30

40

50

Mn2+(ppm)

20

30

40

50

Al3+ (ppm)

20

60

80

100

Fe3+(ppm)

20

60

80

100

Cr3+(ppm)

10

Abs-Cd

0,3056

0,3056

0,3049

0,3063

0,3060

Abs-Pb

0,0709

0,0700

0,0727

0,0728

0,0708

Nh vy, trong nn chn s liu nghin cu t bng 3.15 n bng 3.19


cho thy cc cation vi cc nng chn kho st u khng gy nh hng
ti cng vch ph ca Cd v Pb.
3.2.3.2. Kho st nh hng ca cc anion
Cng vi cation th anion cng c th gy nh hng n cng vch ph
ca nguyn t phn tch. nh hng ny v tnh cht cng tng t nh nh hng
ca cc loi axit. Ni chung th cc anion gc ca cc axit d bay hi thng t gy
nh hng n cng vch ph ca nguyn t cn phn tch. Trong mu phn
tch c th cha mt s anion nh: Cl-, NO3-, SO42-, F-, I-, H2PO4-
tin hnh cng vic kho st ny chng ti chun b cc dung dch mu
ca dung dch Cd 1ppm, Pb 2ppm trong dung dch HNO3 2%, NH4Ac 1% v LaCl3
1%. Kt qu kho st c ch ra trong cc bng 3.20 v 3.21:
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Bng 3.20: Kho st nh hng ca anion SO42- ,H2PO4-, F-, IMu

C0

C1

C2

C3

C4

SO24 (ppm)

50

100

150

200

H2PO4- (ppm)

50

100

150

200

F-(ppm)

50

100

150

200

I-(ppm)

50

100

150

200

Abs-Cd

0,3056

0,3049

0,3050

0,3057

0,3062

Abs-Pb

0,0709

0,0730

0,0742

0,0726

0,0720

Ion

Bng 3.21: Kho st nh hng ca tng cc anion


Mu

C0

C1

C2

C3

C4

NO3-(%)

Cl- (%)

SO24 (ppm)

50

100

150

200

H2PO4- (ppm)

50

100

150

200

F- (ppm)

50

100

150

200

I- (ppm)

50

100

150

200

Abs-Cd

0,3056

0,3052

0,3055

0,3060

0,3059

Abs-Pb

0,0709

0,0730

0,0720

0,0719

0,0715

Theo bng 3.20 v 3.21 cho thy cc anion vi cc nng nh trn u


khng gy nh hng n cng vch ph ca cc nguyn t Cd v Pb.
3.2.3.3. nh hng ca tng cc cation v anion
nh gi tng qut chng ti tin hnh kho st nh hng ca tng cc
cation v anion n qu trnh o ph ca Cd v Pb. Kt qu c th hin bng 3.22

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Bng 3.22 : nh hng ca tng cc cation v anion


Mu

C0

C1

C2

C3

C4

K+(ppm)

200

300

400

800

Na+ (ppm)

100

200

400

500

Mg2+(ppm)

50

100

150

200

Ca2+ (ppm)

50

100

150

200

Ba2+ (ppm)

10

20

30

40

Sr2+ (ppm)

10

20

30

40

Cu2+(ppm)

20

30

40

50

Ni2+ (ppm)

20

30

40

50

Zn2+ (ppm)

20

30

40

50

Mn2+(ppm)

20

30

40

50

Al3+ (ppm)

20

60

80

100

Fe3+(ppm)

20

60

80

100

Cr3+(ppm)

10

NO3-(%)

Cl- (%)

SO24 (ppm)

50

100

150

200

H2PO4- (ppm)

50

100

150

200

F- (ppm)

50

100

150

200

I- (ppm)

50

100

150

200

Abs-Cd

0,3056

0,3056

0,3052

0,3058

0,3060

Abs-Pb

0,0709

0,0710

0,0721

0,0725

0,0712

Nhn xt: T bng s liu trn chng t rng cc ion trong vng kho st
khng nh hng n php xc nh Cd v Pb. Hn na trong cc mu thc t th
hm lng cc ion trn nh hn hm lng kho st rt nhiu nn c th khng nh
rng cc ion ny khng gy nh hng n php o. y cng chnh l mt u
im ni bt ca php o F-AAS so vi phng php khc.

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3.3. Phng php ng chun i vi php o F- AAS


3.3.1. Kho st xc nh khong tuyn tnh ca Cd v Pb
Phng trnh c s phn tch nh lng ca mt nguyn t trong php o
F AAS l:
A = K. Cb
A : Cng vch ph hp th
K: Hng s thc nghim
C: Nng ca nguyn t trong mu o ph
b: Hng s bn cht (0<b1)
Trong mt khong nng nht nh th b=1, mi quan h gia A v C l
tuyn tnh A= f(C). Do xc nh hm lng Cd v Pb chng ta phi tm c
khong nng tuyn tnh ca php o dng ng chun.
xc nh khong tuyn tnh ca Cd, Pb chng ti tin hnh pha mu ca
Cd, Pb chun trong nn HNO3 2% v CH3COONH4 1% sao cho nng tng dn.
Sau o mt quang trong cc iu kin chn v ghi li kt qu thu c kt
qu sau.
Bng 3.23: Kt qu kho st khong nng tuyn tnh ca Cd
Abs-Cd

Ln 1

Ln 2

Ln 3

Trung bnh

0,0260

0,0270

0,0260

0,0260

0.5

0,0330

0,0340

0,0330

0,0330

0,0660

0,0670

0,0670

0,0670

0,1290

0,1290

0,1290

0,1290

0,1910

0,1920

0,1910

0,1910

0,2470

0,2470

0,2470

0,2470

0,2980

0,2990

0,2990

0,2990

0,3420

0,3420

0,3420

0,3420

0,4000

0,4000

0,4000

0,4000

Nng (ppm)
0.25

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Abs-Cd

T s liu ca bng 3.23 trn ta v c th :


0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0

6
7
8
Conc-Cd(ppm)

Hnh 3.1: th kho st khong nng tuyn tnh ca Cd


Qua th kho st ta thy khong tuyn tnh ca Cd t 0,25 ppm n 5 ppm
Bng 3.24: Kt qu kho st khong nng tuyn tnh ca Pb
Abs-Pb

Trung

Ln 1

Ln 2

Ln 3

0,1

0,0324

0,0325

0,0325

0,0325

0,25

0,0486

0,0485

0,0484

0,0485

0,0610

0,0610

0,0609

0,0610

0,0794

0,0795

0,0793

0,0794

0,0960

0,0960

0,096

0,0960

0,1126

0,1127

0,1127

0,1127

0,1445

0,1444

0,1446

0,1445

0,1603

0,1605

0,1606

0,1605

0,1741

0,1742

0,1742

0,1742

0,1814

0,1816

0,1815

0,1815

10

0,2119

0,2120

0,2120

0,2120

Nng (ppm)

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T s liu bng 3.24 ta v c th :


B

Abs - Pb
0.20
0.18
0.16
0.14
0.12
0.10
0.08
0.06
0.04
0.02

10

CPb

X Axis Title

Hnh 3.2: th kho st khong nng tuyn tnh ca Pb


Qua th kho st ta thy khong tuyn tnh ca Pb t 0,25 ppm n 8 ppm.
3.3.2. Xy dng ng chun, xc nh gii hn pht hin (LOD) v gii hn
nh lng (LOQ) ca Cd v Pb
T cc kt qu thu c trn chng ti dng phn mm Origin 6.0 xy
dng ng chun ca cc nguyn t cadimi v ch ng thi xc nh gii hn
pht hin v gii hn nh lng ca chng. Kt qu thu c nh sau:
3.3.2.1. ng chun ca Cadimi
T s dng phn mm Origin 6.0 xy dng ng chun ca Cd thu c
kt qu nh hnh 3.3.

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Abs-Cd

50

0.30

Y=A+B.X

0.25
0.20
0.15
0.10
0.05
0.00
0

Conc-Cd(ppm)
Hnh 3.3: th ng chun ca cadimi
Phng trnh ng chun Data1_B:
Y=A+B*X
Thng s

gi tr

sai s

-----------------------------------------------------------A

0.00904

0.00274

0.05897

9,74.10-4

------------------------------------------------------------

SD

-----------------------------------------------------------0.99932

0.0043

< 0.0001

------------------------------------------------------------

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Tra bng phn phi Student ta c gi tr t(P=0,95;f= N-1=6) = 2,447


Theo kt qu tnh ton ca phn mm Origin 6.0 ta c:
A = t(0,95; 6).SA = 2,447. 0,00274= 0,0067
B = t(0,95; 6).SB = 2,447. 9,74.10 = 0,0024
-4

Vy phng trnh hi quy y ca ng chun c dng:


Ai = (0,0090 0,0067) + (0,0589 0,0024).CCd
Trong : Ai l cng hp th o c khi o ph (Abs).
CCd l nng ca Cd (ppm).
* Gii hn pht hin (LOD)
LOD c xem l nng thp nht ca cht phn tch m h thng phn tch
cn cho tn hiu phn tch khc c ngha vi tn hiu ca mu trng hay tn hiu nn.
Gii hn pht hin Cd bng php o F-AAS theo ng chun:

LOD

3.S y
B

3.0,004
0,2( ppm)
0,059

* Gii hn nh lng (LOQ)


LOQ c xem l nng thp nht ca cht phn tch m h thng nh
lng c vi tn hiu phn tch khc c ngha nh lng vi tn hiu ca mu
trng hay tn hiu nn v t tin cy 95%.
Gii hn nh lng Cd bng php o F-AAS theo ng chun:

LOQ

10.S y
B

10.0,004
0,678( ppm)
0,059

3.3.2.2. ng chun ca ch
T kt qu thu c bng 3.24 chng ti dng phn mm Origin 6.0 xc
nh ng chun ca ch v thu c kt qu nh sau:

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0.18

Abs - Pb

Y Axis Title

0.16
0.14
0.12
0.10
0.08
0.06
0.04
0

X Axis Title

8
CPb

Hnh 3.4: th ng chun ca ch


Linear Regression for Data1_B:
Y=A+B*X

Parameter

Value Error

---------------------------------------------------A

0.04672

0.00113

0.01617

2.23629E-4

-----------------------------------------------------

SD

-----------------------------------------------------0.99952

0.00144

<0.0001

-------------------------------------

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Tra bng phn phi Student ta c gi tr t(P=0,95;f= N-1=6) = 2,447


Theo kt qu tnh ton ca phn mm Origin 6.0 ta c:
A = t(0,95; 6).SA = 2,47.0,00113 = 0,003
B = t(0,95; 6).SB = 2,47. 2,23629.10 = 0,00055
-4

Vy phng trnh hi quy y ca ng chun c dng:


Ai = (0,04672 0,003) + (0.01617 0,00055).CPb
Trong : Ai l cng hp th o c khi o ph (Abs).
CPbl nng ca Pb (ppm).
Gii hn pht hin Pb bng php o F-AAS theo ng chun:
LOD =

3* S y
B

3.0,00144
= 0,267 (ppm)
0,0162

Gii hn nh lng Pb bng php o F-AAS theo ng chun:


LOQ =

10 * S y
B

10 * 0,00144
= 0,889 (ppm)
0,0162

3.4. nh gi sai s v lp li ca php o


nh gi sai s v lp li ca php o ta dng ng chun, pha 3 mu
c nng im u, im gia v im cui ca ng chun trong cc iu
kin v thnh phn ging nh mu chun. Thc hin o mi mu 10 ln, kt qu thu
c biu din trong bng 3.25, 3.26
Sai s c tnh theo cng thc :
%X=

( At Ai )
*100%
At

Trong :
+ %X : Sai s phn trm tng i .
+ Ai : Gi tr cng hp th o c (Abs)
+ At : Gi tr cng hp th tm c theo ng chun (Abs)
lp li ca php o c xc nh theo cc i lng S2 v %RSD.
Cc i lng c tnh theo cng thc :

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S =

( A A )
t

Suy ra : S =

n 1

S2

% RSD = S *100%
Atb

Trong : + Atb : Cng hp th trung bnh


+ n : s ln o
+ S : lch chun
+ % RSD : h s bin ng ca php o.
Tin hnh thc nghim vi cc mu chun v x l cc kt qu thu c bng
thng k chng ti thu c kt qu nh sau:
Bng 3.25: Kt qu sai s v lp ca php o cadimi
Mu
CCd
(ppm)
At (Abs)

0, 25

0,0255

0,1287

0,2989

Ln o

Ai

%X

Ai

%X

Ai

%X

0,0245

3,92

0,1278

0,70

0,2958

1,04

0,0250

1,96

0,1262

1,94

0,2960

0,97

0,0253

0,78

0,1275

0,93

0,2945

1,47

0,0242

5,09

0,1270

1,32

0,2915

2,48

0,0247

3,14

0,1265

1,71

0,2912

2,58

0,0239

6,27

0,1263

1,86

0,2909

2,68

0,0249

2,35

0,1259

2,18

0,2923

2,21

0,0240

5,88

0,1272

1,17

0,2902

2,91

0,0252

1,18

0,1269

1,40

0,2905

2,81

10

0,0248

2,75

0,1268

1,48

0,2938

1,71

Atb

0,0247

3,33

0,1268

1,47

0,2927

2,09

0,001

0,002

0,007

%RSD

4,05

1,58

2,39

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Bng 3.26: Kt qu sai s v lp ca php o ch


Mu

CPb (ppm)

At (Abs)

0,0610

0,1127

0,1742

Ln o

Ai

X%

Ai

X%

Ai

X%

0,0590

3,28

0,1120

0,62

0,1720

1,26

0,0585

4,09

0,1115

1,06

0,1715

1,55

0,0583

4,43

0,1106

1,86

0,1705

2,12

0,0595

2,46

0,1117

0,89

0,1710

1,84

0,0580

4,92

0,1102

2,22

0,1700

2,41

0,0576

5,57

0,1098

2,57

0,1707

2,01

0,0588

3,61

0,1100

2,39

0,1705

2,12

0,0579

5,08

0,1095

2,84

0,1709

1,89

0,0597

2,13

0,1109

1,60

0,1701

2,35

10

0,0599

1,80

0,1113

1,24

0,1695

2,70

Atb

0,0587

3,74

0,1108

1,73

0,1707

2,03

0,0025

0,0022

0,0038

% RSD

4,26

1,99

2,23

Kt qu kho st sai s tun theo nh lut phn b Gaus. im u v


im cui ca vng tuyn tnh sai s ln (4,05% v 2,39% vi Cd ; 4,26% v
2,23% vi Pb), im gia vng tuyn tnh sai s nh nht (1,58% vi Cd ; 1,99%
vi Pb). Nh vy kt qu kho st cho thy lch chun v h s bin ng (sai s
tng i) ca php o Cd, Pb u nh nm trong gii hn cho php (10%). Qua
kt qu trn chng ti nhn thy phng php ph F-AAS l phng php phn tch
n nh, c lp li tt ng thi c chnh xc cao, hon ton ph hp vi xc
nh lng vt kim loi trong mu.

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3.5. Tng kt cc iu kin o ph F-AAS ca cadimi v ch


T cc kt qu nghin cu c trn, cc iu kin ph hp o ph FAAS ca cadimi v ch c ch ra bng 3.27
Bng 3.27: Tng kt cc iu kin o ph F- AAS ca Cd, Pb
Cd

Pb

228,8

217

0,5

0,5

65 %

70 %

1,2

1,2

Chiu cao ca burner (mm)

Nng HNO3 (C%)

nn

Nguyn t

0,2

0,267

Gii hn nh lng LOQ (ppm)

0,678

0,889

Vng tuyn tnh (ppm)

0,25-5

0,25- 8

Cc yu t
Khe o (nm)
Cng dng n (%Imax)
Lu lng kh C2H2 (ml/pht)

phn

Thnh

Thng s my o

Vch ph hp th (nm)

Nng CH3COONH4 (C%)

Gii hn pht hin LOD (ppm)

3.6. Phn tch mu thc


3.6.1. Ly mu
Qua thm d thc tin v xut pht t yu cu xc nh hm lng cadimi v
ch trong rau xanh ti khu vc huyn i T - tnh Thi Nguyn, chng ti tin
hnh ly mu nhng khu vc trng rau c ngun nc sch nh, x M Yn (ni
cung cp ngun nc sch) v cc x c cc m khong sn nh x H Thng (ni
c m a kim ViCa-Ni Pho), x Yn Lng (ni c m Than Ni Hng).
Mu rau sau khi c ly cc a im trn c ng trong ti nilon sch
v a v phng th nghim. Ra sch t bm trn rau, trng li bng nc ct mt
vi ln. ro nc, cn trng lng ti ri sy 100-1200C dit men, sau
sy li khong 500C cho n kh. Chuyn mu rau kh vo bnh ht m
ngui, em cn li xc nh trng lng kh. Sau khi cn mu c ng trong

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l kn trnh m mc. Tt c cc l ng rau u c dn nhn ghi r: tn mu,


loi rau, thi gian, a im ly mu.
Bng 3.28: a im v thi gian ly mu
STT

Loi rau

Bp ci (BC)

Ci xoong (CX)

Ci canh (CC)

Ngi cu (NC)

X lch (XL)

Mung nc (MN)

Ci tha (CT)

Mng ti (MT)

Dn (DD)

10 Gip c (GC)

a im ly mu

Thi gian ly mu

X H Thng-huyn i T- 15h30 ngy10/03/2010.


tnh Thi Nguyn
X Yn Lng - huyn i T tnh Thi Nguyn.
X H Thng-huyn i Ttnh Thi Nguyn
X Yn Lng - huyn i T tnh Thi Nguyn.
X Ph Cng - huyn i T
- tnh Thi Nguyn.
X H Thng - huyn i
T - tnh Thi Nguyn.
X H Thng - huyn i
T - tnh Thi Nguyn.
X H Thng - huyn i
T - tnh Thi Nguyn.
X Yn Lng - huyn i T tnh Thi Nguyn.
X M Yn - huyn i T tnh Thi Nguyn.

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15h30 ngy 10/03/2010

09h30 ngy 05/05/2010

09h30 ngy 15/03/2010

09h30 ngy 05/05/2010

09h30 ngy 07/05/2010

08h30 ngy 15/05/2010

08h30 ngy 15/05/2010

08h30 ngy 20/05/2010

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Bng 3.29: T l khi lng ca mt s loi rau trc v sau khi sy kh


Khi lng sau v trc

Phn trm kh

khi sy (g)

(%)

Bp ci (BC)

35,67/1000

3,567 %

M2

Ci xoong (CX)

41,54/1000

4,154 %

M3

Ci canh (CC)

53,37/1000

5,337 %

M4

Ngi cu (NC)

89,48/1000

8,948 %

M5

X lch (XL)

37,78/1000

3,778 %

M6

Mung nc (MN)

44,54/1000

4,454 %

M7

Ci tha (CT)

86,78/1000

8,678 %

M8

Mng ti (MT)

67,94/1000

6,794 %

M9

Dn (DD)

83,56/1000

8,356 %

10

M10

Gip c (GC)

110,47/1000

11,047 %

STT

Mu

Loi rau

M1

3.6.2. Kho st qu trnh x l mu


Chng ti tin hnh kho st vi 10 mu rau xanh ti huyn i T-tnh Thi
Nguyn. Mi mu c nghin cu thnh bt mn, y chng ti chn phng
php x l t bng axit.
Mu rau c x l nh sau:
Cn 1 gam mu kh nghin thnh bt mn cho vo bnh Kendal, sau tm t
bng 1 ml nc ct, cho tip HNO3 c (65%) vo trong bnh, sau thm tip 2ml
HClO4 c vo bnh, y bnh bng phu lc c ui di. un mu phn tch trong
nhiu gi. chn c t l th tch HNO3 ph hp cn cho vo ng vi 1gam
mu kh ph hp chng ti tin hnh kho st nh sau:
i vi mi mu rau kh chng ti tin hnh kho st th tch HNO 3 t 10
ml n 15ml.

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Bng 3.30: Kt qu kho st lng HNO3 ng vi 1 gam mu rau kh


VHNO3 (mL)

STT

Mu rau

10

11

12

13

14

15

Bp ci (BC)

Ci xoong (CX)

Ci canh (CC)

Ngi cu (NC)

X lch (XL)

Mung nc (MN)

Ci tha (CT)

Mng ti (MT)

Dn (DD)

10

Gip c (GC)

Du l nhng mu sau khi x l dung dch vn cn cn, dung dch thu


c vn c chng t mu cha phn hu ht.
Du + l nhng mu sau khi x l dung dch thu c trong sut hoc c
mu hi vng, l nhng mu b phn hu hon ton.
Qua kt qu kho st c trn chng ti chn lng axit HNO3 65% thch
hp cho qu trnh x l 1gam mu kh l t 11 ml n 14 ml ty vo tng mu.
Cc mu sau khi c x l s b nh trn c v c ho nh sau: Cn trn
cn phn tch mt lng mu chnh xc (5 gam) cho vo bnh Kendal, thm 55-70
ml HNO3 65% (tu vo tng loi rau), y ming bnh bng mt phu nh, qua
m. Sau , un nh trn bp in c iu chnh nhit , un si nh n khi mu
phn hu hon ton, thm 2-3 ml HClO4 v un n dung dch trong sut. Chuyn
mu sang cc ming rng, thm 1 ml HClO4, lm bay hi ht axit n cn mui m.
nh mc vo bnh 10 ml bng HNO3 2%. em mu ny xc nh hm lng
cadimi, ch bng ph hp th nguyn t F-AAS.
Mu trng: Cho 5ml nc ct, ri thm vo 55-70 ml axit HNO3 c v 23 ml HClO4.
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3.7. Thc nghim o ph v tnh ton kt qu


Dung dch mu sau khi c chun b phn trc chng ti tin
hnh o ph hp th nguyn t trn my quang ph hp th nguyn t Thermo
electron corporation (Anh) c sn phn mm xy dng v x l ng chun xc
nh nng ion ca cc nguyn t cn xc nh.
3.7.1. Phng php x l kt qu phn tch theo phng php ng chun
Da vo gi tr hp th A v ng chun xy dng, chng ti xc
nh c nng ca cadimi v ch trong cc dung dch mu qua x l. Hm
lng ca cht phn tch c tnh theo cng thc:
X

CX V
m

Trong :
X: hm lng cadimi, ch trong th tch mu em o (mg).
C X : Nng cht phn tch trong mu o ph tm c theo ng

chun (mg/l).
V: Th tch dung dch mu (10 ml).
m: Lng mu phn tch x l v nh mc thnh th tch (5 gam).
T kt qu trn ta xc nh c hm lng cadimi, ch trong 1000 gam mu
ti theo cng thc sau:
X = X.% kh
X : hm lng Cd, Pb trong 1000 gam mu ti).
3.7.2. Kt qu xc nh hm lng cadimi, ch trong cc mu rau
Chng ti tin hnh x l 10 mu rau nh cp phn 3.6.2. Chun b
dung dch o v tin hnh o mu cc iu kin ti u nh cp phn 3.5.
Cc kt qu thu c l trung bnh ca cc ln o v tr i mu trng.
Mu rau ma xun bao gm: Bp ci (BC); Ci xoong (CX); Ci canh (CC);
X lch (XL). Rau ma h bao gm : Ngi cu (NC); Mung nc (MN); Ci tha
(CT); Mng ti (MT); Dn (DD); Gip c (GC).

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Bng 3.31: Kt qu o ph F- AAS i vi nguyn t Cd

STT

Mu

Nng tnh
theo ng
Abs- Cd
chun
(ppm)
0,0302
0,3260

Hm lng
trong mu
rau ti
(mg/kg)
0,0233

Bp ci (BC)

Ci xoong (CX)

0,0294

0,3125

0,0260

Ci canh (CC)

0,0285

0,2969

0,0317

Ngi cu (NC)

0,0288

0,3025

0,0541

X lch (XL)

0,0255

0,2455

0,0185

Mung nc (MN) 0,0271

0,2735

0,0244

Ci tha (CT)

0,0519

0,6990

0,1213

Mng ti (MT)

0,0518

0,6982

0,0949

Dn (DD)

0,0355

0,4173

0,0697

10 Gip c (GC)

0,0299

0,3218

0,0711

Gii hn cho
php 46/2007
Q BYT
(mg/kg )[19]

0,2

Bng 3.32 : Kt qu o ph F- AAS i vi nguyn t Pb

STT

Mu

Hm lng Gii hn cho


Nng tnh theo
trong mu php 46/2007
ng chun
Pb
rau ti
Q BYT
(ppm)
(mg/kg)
(mg/kg )[19]
0,0498
0,3210
0,0229
Abs-

Bp ci (BC)

Ci xoong (CX)

0,0516

0,4320

0,0359

Ci canh (CC)

0,0507

0,3580

0,0382

Ngi cu (NC)

0,0532

0,5323

0,0953

X lch (XL)

0,0550

0,6457

0,0488

Mung nc (MN) 0,0573

0,7854

0,0699

Ci tha (CT)

0,0600

0,9530

0,1654

Mng ti (MT)

0,0534

0,5423

0,0737

Dn (DD)

0,0514

0,4210

0,0704

10 Gip c (GC)

0,0585

0,8578

0,1895

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3.8. Kim tra qu trnh x l mu


V kt qu phn tch thu c ph thuc vo nhiu yu t nh: phng php
x l mu, iu kin thit b, k thut thc hin... nn nh gi mc chnh xc
cng nh lp li ca phng php chng ti chn cc mu tin hnh lm
mu lp li v mu thm chun.
3.8.1. Mu lp
Chng ti dng cc mu rau trn tin hnh x l lp li 3 ln. Kt qu
c ch ra cc bng di y.
Vi mi ln o mu th lp li c xc nh theo cng thc:

(Ci Ctb )2
S
S S2
n 1
2

% RSD

S
.100%
Ctb

t.S
n

Trong : S2: phng sai


S: lch chun
Ci: Nng mu i
Ctb: Nng trung bnh
p dng cng thc ta c kt qu xc nh hm lng cadimi v ch trong rau
(vi tin cy ca php o l p=0,95 tra bng ta c t(n=3)=4,3)
Hm lng chnh xc Cd, Pb trong rau xanh c tnh theo cng thc
M = X (X: Hm lng o c)
Trong M: hm lng chnh xc mu trong cc loi rau xanh.
X: hm lng o c
: khi lng chnh lch

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Bng 3.33 : Kt qu x l s liu hm lng Cd


Mu

C1

C2

C3

Ctb

%RSD

Bp ci (BC)

0,3250 0,3262 0,3268 0,3260 0,0009 0,2761 0,0022

Ci xoong (CX)

0,3127 0,3123 0,3125 0,3125 0,0003 0,0960 0,0007

Ci canh (CC)

0,2965 0,2970 0,2972 0,2969 0,0004 0,1347 0,0010

Ngi cu (NC)

0,3020 0,3027 0,3023 0,3025 0,0004 0,1322 0,0010

X lch (XL)

0,2453 0,2456 0,2456 0,2455 0,0002 0,0815 0,0005

Mung nc (MN) 0,2734 0,2735 0,2736 0,2735 0,0001 0,0366 0,0002


Ci tha (CT)

0,6985 0,6993 0,6992 0,6990 0,0004 0,0572 0,0010

Mng ti (MT)

0,6979 0,6980 0,6987 0,6982 0,0004 0,0573 0,0010

Dn (DD)

0,4172 0,4175 0,4172 0,4173 0,0002 0,0479 0,0005

Gip c (GC)

0,3220 0,3219 0,3215 0,3218 0,0003 0,0932 0,0007

Bng 3.34 : Hm lng chnh xc Cd trong rau


Nng tnh
STT

Mu

theo ng chun
(ppm)

Hm lng trong
mu rau ti (mg/kg)

Bp ci (BC)

0,3260 0,0022

0,0233 0,0022

Ci xoong (CX)

0,3125 0,0007

0,0260 0,0007

Ci canh (CC)

0,2969 0,0010

0,0317 0,0010

Ngi cu (NC)

0,3025 0,0010

0,0541 0,0010

X lch (XL)

0,2455 0,0005

0,0185 0,0005

Mung nc (MN)

0,2735 0,0002

0,0244 0,0002

Ci tha(CT)

0,6990 0,0010

0,1213 0,0010

Mng ti (MT)

0,6982 0,0010

0,0949 0,0010

Dn (DD)

0,4173 0,0005

0,0697 0,0005

10

Gip c (GC)

0,3218 0,0007

0,0711 0,0007

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gkg

800
600

Hm lng Cd phn tch


Hm lng Cd cho php

400
200
54.4
23.3 26.0 31.7
18.5 24.4
M1

M2

M3

M4

M5

M6

121.3 94.9
69.7 71.1
M7

M8

M9

M10

Mu

Hnh 3.5: th hm lng Cd qua kt qu phn tch rau mt s x


ca huyn i T tnh Thi Nguyn
Bng 3.35: Kt qu x l s liu hm lng Pb
Mu

C1

C2

C3

Ctb

%RSD

Bp ci (BC)

0,3211 0,3210 0,3209 0,3210 0,0001

0,0312

0,0002

Ci xoong (CX)

0,4318 0,4319 0,4323 0,4320 0,0003

0,0694

0,0007

Ci canh (CC)

0,3585 0,3578 0,3577 0,3580 0,0004

0,1117

0,0010

Ngi cu (NC)

0,5320 0,5318 0,5331 0,5323 0,0007

0,1315

0,0017

X lch (XL)

0,6457 0,6459 0,6455 0,6457 0,0002

0,0310

0,0005

Mung nc (MN) 0,7850 0,7856 0,7856 0,7854 0,0003

0,0382

0,0007

Ci tha (CT)

0,9529 0,9528 0,9533

0,9530 0,0003

0,0315

0,0007

Mng ti (MT)

0,5422 0,5425 0,5422 0,5423 0,0002

0,0369

0,0005

Dn (DD)

0,4205 0,4217 0,4208 0,4210 0,0006

0,1425

0,0015

Gip c (GC)

0,8580 0,8577 0,8577 0,8578 0,0002

0,0233

0,0005

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Ta c kt qu chnh xc ca cc mu nh sau:
Bng 3.36: Hm lng chnh xc Pb trong rau
Mu

STT

Nng tnh theo


ng chun (ppm)

Hm lng trong
mu rau ti (mg/kg)

Bp ci (BC)

0,3210 0,0002

0,0229 0,0002

Ci xoong (CX)

0,4320 0,0007

0,0359 0,0007

Ci canh (CC)

0,3580 0,0010

0,0382 0,0010

Ngi cu (NC)

0,5323 0,0017

0,0953 0,0017

X lch (XL)

0,6457 0,0005

0,0488 0,0005

Mung nc (MN)

0,7854 0,0007

0,0699 0,0007

Ci tha (CT)

0,9530 0,0007

0,1654 0,0007

Mng ti (MT)

0,5423 0,0005

0,0737 0,0005

Dn (DD)

0,4210 0,0015

0,0704 0,0015

10

Gip c (GC)

0,8578 0,0005

0,1895 0,0005

g / kg
1200
1000
800
600

Hm lng Cd phn tch


Hm lng Cd cho php

400
200

189.5

16.54
22.9
M1

35.9

38.2

M2

M3

95.3
M4

73.7 7.04

48.8 69.9
M5

M6

M7

M8

M9

M10

Mu

Hnh 3.6: th hm lng Pb qua kt qu phn tch rau mt s x


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Nhn xt: Nhn vo kt qu phn tch hm lng kim loi Cd v Pb trong


mt s a im ca huyn i T tnh Thi Nguyn c th hin trn bng 3.34 ;
3.36 v hnh 3.5;3.6 chng ti nhn thy hm lng cc kim loi Cd v Pb u
di mc cho php theo TCVN 46/2007 Q BYT (mg/kg ti).
3.8.2. Mu thm chun
Chng ti chn ra 2 mu rau i i din cho ma xun v ma h trn
tin hnh lm mu thm chun. i vi mi mu chng ti thm vo nhng lng
nht nh Cd, Pb im u, gia v cui ng chun. C th nh bng sau:
Bng 3.37 : Mu thm chun
STT

Mu rau
NC

Thnh phn
Mu rau ngi cu khng thm cht phn tch Cd,Pb

NC + t1

Mu NC + 0,25 ppm Cd + 0,25 ppm Pb

NC + t2

Mu NC + 2ppm Cd + 4 ppm Pb

NC + t3

Mu NC + 5 ppm Cd + 8 ppm Pb

BC

Mu bp ci khng thm cht phn tch Cd, Pb

BC + t1

Mu BC + 0,25 ppm Cd + 0,25 ppm Pb

BC + t2

Mu BC + 2 ppm Cd + 4 ppm Pb

BC + t3

Mu BC + 5 ppm Cd + 8 ppm Pb

Kt qu c biu din di bng 3.38 v 3. 39 , kt qu ny l gi tr trung


bnh ca 3 ln o v c tr i mu trng.

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Bng 3.38: Kt qu phn tch cadimi


STT Mu rau

Kim loi Cd
Nng mu Nng chun Nng thm Hiu sut
thu c
(ppm)

NC
1

thm vo
(ppm)

vo thu c
(ppm)

thu c Sai s
(%)

0,3025

NC + t1

0,5732

0,25

0,2305

92,20

7,80

NC + t2

0,8309

2,00

1,8856

94,28

5,72

NC + t3

1,2512

5,00

4,6570

93,14

6,86

BC

0,3260

BC + t1

0,4267

0,25

0,2315

92,60

7,40

BC + t2

0,9235

2,00

1,8875

94,38

5,63

BC + t3

1,3685

5,00

4,6752

93,50

6,49

Bng 3.39: Kt qu phn tch ch


Kim loi Pb
STT Mu rau

Nng

Nng

Nng thm Hiu sut

mu thu c

chun thm

vo thu c

(ppm)

vo (ppm)

(ppm)

(%)

thu c Sai s

NC

0,5323

NC + t1

0,7145

0,25

0,2367

94,68

5,32

NC + t2

0,9231

4,00

3,8560

96,40

3,60

NC + t3

2,3570

8,00

7,7015

96,27

3,73

BC

0,3210

BC + t1

0,8120

0,25

0,2341

93,64

6,36

BC + t2

1,005

4,00

3,8425

96,06

3,94

BC + t3

2,5324

8,00

7,6792

95,99

4,01

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Nhn xt: Qua kt qu thu c cho thy hiu sut thu hi Cd, Pb u ln
hn 90% v sai s u nh hn 10%. C th sai s i vi nhng mu thm u
ng chun v cui ng chun l ln hn sai s i vi mu thm gia ng
chun, nh vy kt qu ny hon ton ph hp vi l thuyt phn b sai s Gauss.
Vy c th s dng mt trong hai phng php ng chun hoc thm
chun xc nh hm lng Cd, Pb trong rau xanh.
Trn y l kt qu p dng phng php ph hp th nguyn t ngn la F
AAS xc nh hm lng cc kim loi nng vo thc t. V thi gian nghin
cu c hn nn mun c kt qu phn tch chnh xc hn th cn phi ly mu hng
ngy vo cc thi im khc nhau trong ngy, trong nhiu thng vo cc ma khc
nhau em phn tch, ly kt qu nh gi, so snh vi kt qu phn tch bng cc
phng php khc na th kt qu thu c mi m bo chnh xc v c tnh
thuyt phc hn.

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KT LUN
Trn c s nghin cu phng php xc nh cadimi v ch trong rau bng
phng php ph hp th nguyn t F-AAS chng ti thu c cc kt qu nh sau:
1. a ra cc iu kin ph hp o ph F-AAS ca cadimi v ch.
2. Xc nh c khong tuyn tnh v lp ng chun ca cadimi v ch.
3. Xc nh c gii hn pht hin v gii hn nh lng ca php o.
4. nh gi c sai s v lp li ca php o.
5. Chn c cc iu kin ph hp ly mu x l mu rau.
6. Kim tra c kt qu x l mu bng mu lp, mu thm chun v cho kt
qu tt (sai s u nh hn 10 %).
7. Phn tch c hm lng Cd v Pb trong cc mu rau xanh x H Thng,
M Yn, Yn Lng, Ph Cng vo ma xun v ma h thuc huyn i T tnh Thi
Nguyn.
Tuy cc mu nghin cu v phn tch hm lng kim loi nng u di
mc cho php theo TCVN, nhng chng ta cng nn ch n cc mu c hm
lng kim loi vt hn cc mu bnh thng.
- Hm lng Cd theo TCVN: Mc cho php trong rau l 0,2 ppm th ng biu
din trong cc hnh huyn i T tnh Thi Nguyn u di mc cho php, mu c
hm lng Cd cao hn cc mu khc nh M7 (121,30 g/kg) .
- Hm lng Pb theo TCVN: Mc cho php trong rau l 1 ppm th ng biu
din trong cc hnh huyn i T tnh Thi Nguyn u di mc cho php, mu
c hm lng Pb cao hn cc mu khc nh M10 (189,50 g/kg) .
Chnh lng kim loi nng hin din trong cc rau xanh canh tc theo h
thng dy chuyn: t -> cy rau hp th -> con ngi dinh dng, hp th v tch
lu trong c th qua chui thc n -> nh hng n sc kho cng ng
Nh vy, phng php ph hp th nguyn t c th xc nh c hm
lng cc kim loi nng trong rau. Qua thc nghim, cho thy mt s loi rau ti
mt s khu vc ca huyn i T tnh Thi Nguyn theo cc kt qu phn tch cho
thy hm lng cadimi v ch nm trong gii hn cho php ca B Y t.
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Do thi gian lm lun vn khng di nn chng ti cha tin hnh phn tch
c nhiu loi rau v mi tng quan ca chng vi iu kin sng. Chng ti
mong rng s sm c mt ti nghin cu ton din v vn ny v kt lun
chnh xc v tnh hnh rau hin nay.

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71

TI LIU THAM KHO


Ti liu ting vit
1. Nguyn Th Ngc n nh gi hin trng nhim ch (Pb) trong rau xanh
thnh ph H Ch Minh-Tp ch pht trin KH v CN, tp 10, s 07-2007.
2. Nguyn Tinh Dung, H Vit Qu(1991), Cc phng php phn tch ha l, i
hc S phm H Ni.
3. Nguyn Tinh Dung (2000), Ha hc phn tch, phn III- Cc phng php phn
tch nh lng ha hc, NXB Gio dc.
4. Nguyn ng c(2006), Xc nh hm lng cc ion kim loi Crom, Mangan,
ng, Ch, Cadimi, Asen, Thy ngn trong nc v lp biu nhim TP
Thi Nguyn, ti nghin cu cp b - Khoa Khoa hc t nhin - i hc
Thi Nguyn.
5. Phm Th Thu H(2006), lun vn thc s - Nghin cu xc nh Cd v Pb trong
tho dc v sn phm ca n bng php o ph hp th nguyn t.
6. Trn T Hiu(2000) - Ha hc phn tch - NXB HQGHN.
7. Trn T Hiu, T Vng Nghi, Nguyn Vn Ri, Nguyn Xun Trung (2003)- Cc
phng php phn tch cng c - phn hai - i hc Khoa hc T nhin - i
hc Quc Gia H Ni.
8. Phm Lun(1998), C s l thuyt phng php phn tch ph pht x v hp th
nguyn t phn II - i hc Khoa hc T nhin- i hc Quc Gia H Ni.
9. Phm Lun (2003), Phng php phn tch ph hp th nguyn t - NXB i hc
Quc gia H Ni.
10. Phm Lun (1999/2003), Vai tr ca mui khong v cc nguyn t vi lng i vi
s sng ca con ngi, i hc Khoa hc T nhin- i hc Quc Gia H Ni.
11. Phm Lun (1987), S tay pha ch dung dch - Phn 1,2, NXB Khoa hc v k thut.
12. Phm Lun (2001/2004), Gio trnh c s ca cc k thut x l mu phn tch Phn 1,2, i hc Khoa hc T nhin- i hc Quc Gia H Ni.
13. T Vng Nghi (2001), Ha hc phn tch- C s l thuyt cc phng php ha
hc phn tch, NXB i hc Quc Gia H Ni.
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72

14. Hong Nhm (2003), Ho hc v c tp hai - NXB Gio Dc.


15. L Th Tuyt Nhung (2008), Xc nh Pb, Cd trong rau mung bng phng
php quang ph hp th nguyn t ngn la (F-AAS), Kha lun tt nghip h
i hc ti chc , i hc Khoa hc T nhin- i hc Quc Gia H Ni.
16. H Vit Qu (2007), Cc phng php phn tch cng c trong ha hc hin
i, NXB i hc S phm H Ni.
17. Phan Thanh Phng (2009), Xc nh hm lng Cd v Pb trong rau xanh
thnh ph Thi Nguyn bng phng php chit- trc quang, Lun vn thc s
khoa hc, i hc S phm - H Thi Nguyn.
18. T Th Tho (2005), Bi ging chuyn thng k trong ha phn tch, H
KHTN - H Quc gia H Ni.
19. Tiu chun Vit Nam (TCVN 46/ 2007) , v cht lng cc loi thc phm..
20. http://vietbao.vn/Doi-song-Gia-dinh/Rung-minh-chat-luong-rauxanh/45253964/111/
21. http://www.tin247.com/nhan_nhan_rau_nhiem_chi!-1-141097.html
Ti liu nc ngoi
22. Argiculture Board and National Research Council (1968),Effect of pesticide on
fruit and vegetable physiology..
23. Ballantyne.E.E (1984), Heavy metals in natural waters, Springer- Verlag.
24. Greenwood N.N, Earnshaw (1997), Chemistry of the elements, p.1201- 1226,
2ed, Elservier.
25. Lee Sing Kong (1994), From garden to kitchen: Grow your own fruit and vegetables.
26. John R.Dean (2003), Methods for environmental trace analytical, Northmbria
University, Newcastle,UK .

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