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I HC HU

TRNG I HC KHOA HC
KHOA HA
....

Kha lun Tt nghip C nhn Khoa hc

KHO ST CC IU KIN THCH HP


XC NH NITRAT, NITRIT TRONG THC PHM
CH BIN

Nguyn Th Hoa
Kha 2008 2012

Hu, 5/2012
1

I HC HU
TRNG I HC KHOA HC
KHOA HA
....

Kha lun Tt nghip C nhn Khoa hc

KHO ST CC IU KIN THCH HP


XC NH NITRAT, NITRIT TRONG THC PHM
CH BIN

Chuyn ngnh: Ha Phn tch

Sinh vin thc hin: Nguyn Th Hoa


Gio vin hng dn: TS. Nguyn Vn Ly

Hu, 5/2012
1

hon thnh kha lun ny, ti xin chn thnh cm n TS.


Nguyn Vn Ly trc tip hng dn, ch bo, gip ti trong sut
qu trnh thc hin kha lun ny.
Qua y, ti xin cm n cc thy c trong t Ha V C Phn
Tch, cc thy c trong khoa Ha trng i Hc Khoa Hc Hu,
cc bn Ha K32 ng vin, gip ti hon thnh kha lun ny.
Do thi gian lm kha lun c hn v ln u tin tip xc vi
cng tc nghin cu nn khng trnh khi nhng sai st. Vy knh
mong qu thy c v cc bn b tham kho, ng gp kin ti
thnh cng hn na trong cc lnh vc nghin cu sau ny.
Xin chn thnh cm n.

TM TT

X hi ngy mt vn minh, i sng con ngi ngy cng pht trin. Do vy,
nh gi cht lng thc phm l mt trong nhng vn m con ngi lun quan
tm.
Vi trnh khoa hc k thut ngy cng cao, ra i nhiu phng php
xc nh hm lng nitrat, nitrit trong mu thc phm. Tuy nhin phng php trc
quang l phng php c ng dng rng ri trong vic kim sot cht lng thc
phm ni chung, thc phm ch bin ni ring v phng php ny c th nh lng
nhanh chng vi chnh xc cao.
V vy, trong bn kha lun ny chng ti nghin cu qui trnh xc nh
nitrat, nitrit trong cc mu thc phm ch bin bng phng php trc quang da trn
c s phn ng to hp cht diazo ca axit sunfanilic v -naphthylamin.
Ni dung ca phng php nghin cu gm:
-

Nghin cu xc nh cc iu kin thch hp cho phn ng to mu ca hp


cht diazo gia nitrit, axit sunfanilic v -naphthylamin.

Nghin cu iu kin thch hp kh nitrat thnh nitrit.

nh gi tin cy ca phng php.

p dng qui trnh xc nh nitrat, nitrit trong mt s mu thc phm ch


bin trn th trng.

ii

DANH MC CC T VIT TT

CAC

: y ban Tiu chun ha Thc phm Quc t (Codex Alimentarius

Commission)
FAO

: T chc Nng Lng ca Lin Hp Quc (Food and Agriculture

Organization)
WHO : T chc Y t th gii (World Health Organization)
TCVN : Tiu chun Vit Nam ( Viet Nam Standards)
HPLC : Sc k lng hiu nng cao (High Performance

Liquid

Chromatography hoc High Pressure Liquid Chromatography)


LOD

: Gii hn pht hin (Limit of Detection)

LOQ

: Gii hn nh lng (Limit of Quantitation)

SA

: Acid sunfanilic ( Sulfanilic Acid)

NA

: -naphthylamin ( Alpha Naphthylamine)

Rev

: thu hi (Recovery)

RSD

: lch chun tng i (Relative Standard Deviatin)

UV-Vis : Phng php quang ph hp th phn t (Ultraviolet Visible


Spectrometry)

iii

MC LC
Trang
Li cm n ................................................................................................................... i
Tm tt ........................................................................................................................ ii
Danh mc cc t vit tt ............................................................................................. iii
Mc lc ...................................................................................................................... iv
Danh mc cc bng..................................................................................................... vi
Danh mc cc hnh .................................................................................................... vii
M U .................................................................................................................... 1
Chng 1. TNG QUAN ........................................................................................... 2
1.1. Ph gia thc phm ............................................................................................ 2
1.1.1. Vai tr ca ph gia thc phm ................................................................ 3
1.1.2. nh hng ca ph gia thc phm n sc kho con ngi ................... 3
1.2. nh hng nitrat, nitrit ln sc khe con ngi ................................................ 4
1.3. Tnh cht ca nitrat, nitrit .................................................................................. 5
1.3.1. Tnh cht ca nitrat ................................................................................. 5
1.3.2. Tnh cht ca nitrit .................................................................................. 6
1.4. Cc phng php phn tch nitrat, nitrit ............................................................ 7
1.4.1. Cc phng php phn tch nitrat ............................................................ 7
1.4.2. Phng php phn tch nitrit .................................................................... 9
1.4.3. Cc phng php xc nh ng thi nitrat, nitrit .................................. 10
1.5. Cc phng php x l mu thc phm ......................................................... 11
1.5.1. K thut v c ha t .......................................................................... 11
1.5.2. K thut v c ha kh .......................................................................... 12
1.5.3. K thut v c ha kh t kt hp ....................................................... 12
1.6. C s ca phng php trc quang ................................................................. 13
1.6.1. nh lut Bouguer Lambert Beer ..................................................... 13
1.6.2. Phn tch nh lng.............................................................................. 14

iv

Chng 2. NI DUNG V PHNG PHP NGHIN CU ................................. 16


2.1. Ni dung nghin cu ....................................................................................... 16
2.1.1. Kho st cc yu t nh hng tm iu kin thch hp cho phng
php....................................................................................................................... 16
2.1.2. nh gi tin cy ca phng php .................................................... 17
2.1.3. Kho st phng php x l mu thc phm ......................................... 19
2.1.4. Xc nh m trong mu thc phm ch bin ..................................... 19
2.1.5. Xy dng quy trnh x l mu phn tch nitrat, nitrit trong mu thc
phm ch bin ....................................................................................................... 20
2.1.6. Th p dng qui trnh phn tch trn cc i tng thc t .................... 20
2.2. Phng php nghin cu ................................................................................. 20
2.2.1. Cc phng php nghin cu ................................................................ 20
2.2.2. Thit b v ha cht ............................................................................... 21
2.2.3. Chun b dung dch thuc th v dung dch chun ................................. 22
Chng 3. KT QU V THO LUN ................................................................ 24
3.1. Kho st cc yu t nh hng tm iu kin thch hp cho phng php .. 24
3.1.1. iu kin xc nh nitrit ........................................................................ 24
3.1.2. iu kin kh t nitrat qua nitrit............................................................ 28
_Toc3256528753.2. Xy dng ng chun xc nh nitrat v nitrit ..................... 30
3.2.1. ng chun xc nh nitrit .................................................................. 30
3.2.2. ng chun xc nh nitrat .................................................................. 31
3.3. Xc nh gii hn pht hin, gii hn nh lng ............................................ 32
3.4. Kho st nh hng nitrat qua nitrit ................................................................ 33
3.5. Kho st phng php x l mu thc phm ................................................... 34
3.6. p dng quy trnh x l mu phn tch nitrat, nitrit trong mu thc phm ch
bin ................................................................................................................ 37
3.7. Xc nh nitrit, nitrat trong mu tht

39

Chng 4. KT LUN V KIN NGH ................................................................. 40


4.1. Kt lun .......................................................................................................... 40
4.2. Kin ngh ........................................................................................................ 40
TI LIU THAM KHO.......................................................................................... 41
v

DANH MC CC BNG
Trang
Bng 2.1. Cc ha cht s dng................................................................................. 22
Bng 3.1. S ph thuc hp th quang ca dung dch cc hp cht mu diazo vo
nng axit sunfanilic ............................................................................. 24
Bng 3.2. S ph thuc hp th quang ca dung dch cc hp cht mu diazo vo
nng -naphthylamin ........................................................................... 26
Bng 3.3. S ph thuc hp th quang ca dung dch hp cht mu diazo theo pH ...... 27
Bng 3.4. S thay i hp th quang pH khc nhau vi ct kh Cd-Cu ............. 29
Bng 3.5. S thay i hp th quang pH khc nhau vi hn hp huyn ph km
+ dung dch CdSO4 ................................................................................... 30
Bng 3.6. S ph thuc hp th quang ca dung dch mu diazo vo nng nitrit
v phng trnh ng chun xc nh nitrit ............................................ 30
Bng 3.7. S ph thuc hp th quang ca dung dch mu diazo vo nng nitrat
v phng trnh ng chun xc nh nitrat ............................................ 32
Bng 3.8. Gii hn pht hin v gii hn nh lng ca nitrit, nitrat ........................ 33
Bng 3.9. S thay i hp th quang khi c nh nng nitrit ............................ 33
Bng 3.10. nh hng ca phng php x l mu n hp th quang ................ 35
Bng 3.11. Gi tr hp th quang tnh s mt mt nitrit qua qu trnh x l mu ... 36
Bng 3.12. Kt qu hm lng nitrat, nitrit trong Xc xch b ViSan ........................ 39

vi

DANH MC CC HNH
Trang
Hnh 1.1. Dng ng chun trong phn tch trc quang ........................................... 14
Hnh 1.2. Dng ng thm chun ............................................................................ 15
Hnh 2.1. Ph hp th ca hp cht mu diazo .......................................................... 21
Hnh 3.1. S ph thuc hp th quang ca dung dch hp cht mu diazo vo nng
SA ........................................................................................................ 25
Hnh 3.2. S ph thuc hp th quang ca dung dch hp cht mu diazo vo nng
NA ....................................................................................................... 26
Hnh 3.3. S ph thuc hp th quang ca dung dch mu diazo theo pH ............. 27
Hnh 3.4. S ph thuc hp th quang ca dung dch mu diazo theo thi gian .... 28
Hnh 3.5. S ph thuc hp th quang ca dung dch mu diazo vo nng nitrit
.................................................................................................................. 31
Hnh 3.6. S ph thuc hp th quang ca dung dch mu diazo vo nng nitrat
.................................................................................................................. 32
Hnh 3.7. S qui trnh phn tch nitrat, nitrit trong mu thc phm ch bin ......... 37

vii

M U

Trong cuc sng hin i, thc phm ch bin l nhng sn phm i lin vi
i sng hng ngy ca mi gia nh v n tit kim thi gian v tin bc cho thc n
ba n gia nh. Nhng iu ng lo ngi nht l cht lng ca thc phm ch bin
(hm lng cht bo qun, ph gia thc phm) m ngi sn xut a vo vi mc
ch gi gn v ko di thi gian s dng ca cc loi thc phm. Mt trong s l
nitrit, nitrat (mui dim) l mt dng mui c xp vo nhm cht bo qun c chc
nng n nh mu, ngn chn s pht trin ca vi sinh vt gy c.Tuy nhin nu dng
cc mui ny ch bin, bo qun khng ng qui nh th s l mi e da cho sc
khe con ngi. V th, vic xc nh hm lng nitrat, nitrit trong thc phm ch bin
l rt cn thit nhm m bo s an ton cho ngi tiu dng.
Trong bn kha lun ny chng ti nghin cu qui trnh xc nh nitrat, nitrit
trong cc mu thc phm ch bin da trn c s phn ng to hp cht diazo ca
nitrit vi axit sunfanilic v -napthylamin. Phng php ny c mt s u im nh
nhy ca phng php cao, t b nh hng ca cc cht cn tr, c th thc hin
cc phng th nghim trang b n gin.
Hin nay c nhiu nghin cu xc nh nitrat, nitrit tuy nhin cha c nhiu
nghin cu xc nh nitrat, nitrit trn thc phm ch bin mt cch y . V vy,
mc tiu ca chng ti l nghin cu xc nh nitrat, nitrit trong cc mu thc phm
ch bin bng phng php trc quang.V vi bt k phng php no th vic nghin
cu kho st cc iu kin thch hp phng php cho kt qu chnh xc nht vn
l nhim v quan trng nht.

Chng 1

TNG QUAN
1.1. Ph gia thc phm [4]
Theo FAO: Ph gia l cht khng dinh dng c thm vo cc sn phm vi
cc nh khc nhau. Thng thng cc cht ny c hm lng thp dng ci thin
tnh cht cm quan, cu trc, mi v cng nh bo qun sn phm.
Theo WHO: Ph gia l mt cht khc hn l thc phm hin din trong thc
phm l kt qu ca mt s mt: sn xut, ch bin, bao gi, tn tr...Cc cht ny
khng bao gm s nhim bn.
Theo y ban Tiu chun ha thc phm quc t (Codex Alimentarius
Commisson - CAC): Ph gia l mt cht c hay khng c gi tr dinh dng, khng
c tiu th thng thng nh mt thc phm v cng khng c s dng nh mt
thnh phn ca thc phm. Vic b sung chng vo thc phm gii quyt mc ch
cng ngh trong sn xut, ch bin, bao gi, bo qun, vn chuyn thc phm, nhm
ci thin cu kt hoc c tnh k thut ca thc phm . Ph gia thc phm khng
bao gm cc cht nhim hoc cc cht c b sung vo thc phm nhm duy tr hay
ci thin thnh phn dinh dng ca thc phm.
Theo TCVN: Ph gia thc phm l nhng cht khng c coi l thc phm
hay mt thnh phn ch yu ca thc phm, c hoc khng c gi tr dinh dng, m
bo an ton cho sc khe, c ch ng cho vo thc phm vi mt lng nh nhm
duy tr cht lng, hnh dng, mi v, kim hoc axt ca thc phm, p ng v
yu cu cng ngh trong ch bin, ng gi, vn chuyn v bo qun thc phm.
Nh vy, ph gia thc phm khng phi l thc phm m n c b sung mt
cch ch , trc tip hoc gin tip vo thc phm, ci thin tnh cht hoc c tnh k
thut ca thc phm . Ph gia thc phm tn ti trong thc phm nh mt thnh
phn ca thc phm vi mt gii hn ti a cho php c quy nh.

1.1.1. Vai tr ca ph gia thc phm [16]


- Lm tng gi tr dinh dng: B sung vitamin, khong cht khng c hoc
b mt i trong khi ch bin. Nh thm it vo mui; thm vitamin A, vitamin D vo
sa; thm vitamin B vo bnh m, bt, go v khi xay phn ln v cm c nhiu loi
vitamin ny mt i.
- Gi cho thc phm an ton, ti lu hn
Thc phm thng b mt s vi khun, nm c, mc, men lm h hng. Cht ph gia
c th gip bo qun, lm chm qu trnh ln men, ngn chn s phn hy ca thc
phm. Nh sulfit c cho vo cc loi tri cy kh, nitrit v nitrat c cho thm vo
cc loi tht ch bin nh xc xch, tht mui, tht hp.
- Lm thay i b ngoi ca thc phm: Nhm gip cho thc phm hp dn hn
V d: Cht nh ha lecithin sa, lng trng, u nnh lm mn n c m,
khng kh cng. Cht lm bt n nh mui bicarbonat, natri phosphat c dng khi
lm bnh nng, bnh m lm cho bnh mm, xp hn...
- Lm tng mi v v sc hp dn ca thc phm: Mt s cht mu c cng
dng lm cho thc phm c v ngoi hp dn hn hoc phc hi mu sc nguyn thy
ca thc phm; duy tr hng v vitamin d b phn hy v nh sng; to cho thc
phm c dng v c trng, d phn bit.
1.1.2. nh hng ca ph gia thc phm n sc kho con ngi [2]
Hin nay, vic tm hiu s nh hng ca ph gia thc phm n sc khe
con ngi vn l mt vn phc tp. V li ch, nhng nh kinh doanh c v mnh
m vic s dng ha cht v h thng ti tr cho cc c s nghin cu thc hin
nhng cng trnh nghin cu c li cho sn xut. Ni chung cc triu chng thng
thy thuc vo loi phn ng d ng vi mt s cht ph gia nh: nga ngy, da ni
, nhc u, au bng, chng mt, kh th vv. Mt vi th d nh:
Nhm sulfite: C th gy kh th, nhng ngi b hen suyn khng nn n
thc phm c cha sulfite. Sulfite c trn trong rau qu, qu kh (nh nho kh)
hoc ng lnh, cc loi nc gii kht, trong tm tp ng hp cho ti hn v
cng tm thy trong cc loi xt c chua...
3

Nhm nitrit v nitrat (mui dim): C kh nng gy ung th khi chuyn


thnh nitrosamin lc chin nng. Cc cht ny rt hu hiu trong vic ngn cn s
pht trin v dit vi khun, c bit l khun clostridium botulinum trong hp.
Ngoi tc dng gip bo qun tt, nitrit v nitrat cn to cho tht c mu hng ti rt
hp dn. Tht ngui, jm - bng, tht hun khi, xc xch... u c cha nitrit v nitrat.
Bt ngt (MSG monosodium glutamate): C ngi khng hp vi bt ngt
nn cm thy kh chu trong ngi, chng mt, nhc u, kh ming, nng ran
mt,... Tuy nhin, cc triu chng trn ch tn ti trong mt khong thi gian ngn.
ng ha hc E951 Aspartame: Ngi khng hp vi cht aspartame
nn c th b au bng, chng mt, nhc u...
1.2. nh hng nitrat, nitrit ln sc khe con ngi
Bn thn nitrat khng c, nhng s chuyn ha ca nitrat thnh nitrit trong c
th ngi v ng vt l rt nguy him nu n tch ly nng cao [11].
Hm lng nitrat cao trong c th c th gy ra cc bnh v hng cu, d thy
nht l bnh xanh da tr nh (bnh Blue baby), ngi ta gi y l hi chng
methemoglobin v d b e do n cuc sng c bit i vi tr di 6 thng tui, do
dch axit trong d dy tr nh khng mnh nh ca ngi trng thnh. V vy, cc
loi khun ng rut d dng chuyn ha nitrat thnh nitrit [11].
Khi NO3- vo c th ngi, n tham gia phn ng kh d dy v ng rut do
tc dng ca cc men tiu ho sinh ra NO2-, nitrit sinh ra phn ng vi Hemoglobin to
thnh methaemoglobinemia lm mt kh nng vn chuyn oxy ca Hemoglobin.
Thng thng Hemoglobin cha Fe2+, ion ny c kh nng lin kt vi oxy, khi c mt
NO2- n s chuyn ho Fe2+ thnh Fe3+ lm cho hng cu khng lm c nhim v
chuyn ti O2, nu duy tr lu s dn ti t vong, phn ng: [11]
2HbFe2+(O2) + NO2- + H2O 2HbFe3+ + 2OH- + NO3- + O2
Nng nitrit cao hn 100 mg NO3-/L khi vo d dy, ti y pH thp nitrit c
chuyn thnh axit nitr c kh nng phn ng c vi amin hoc amit sinh ra

nitrosamine y l hp cht gy ung th, mi quan h ny ch mi c th nghim


trn ng vt v cha c kim chng trn ngi [11].
Do hn ch mi nguy hi do nitrit gy ra, tiu chun Vit Nam qui nh
hm lng nitrit, nitrat cho php hin din trong thc phm ch bin: Tht mui,
jambon, xc xch, lp xng...<150 ppm [8].
1.3. Tnh cht ca nitrat, nitrit
1.3.1. Tnh cht ca nitrat [6]
1.3.1.1. Tnh cht vt l
Nitrat l mui ca axit nitric. Ngi ta bit c nitrat ca tt c cc mui
kim loi. Ion NO3- khng mu nn cc mui nitrat ca nhng cation khng mu u
khng mu. Hu ht cc mui nitrat u d tan trong nc. Mt vi mui ht m trong
khng kh nh NaNO3 v NH4NO3. Mui nitrat ca nhng kim loi ho tr hai v ho
tr ba thng dng hydrat.
1.3.1.2. Tnh cht ha hc
Mui nitrat khan ca kim loi kim kh bn vi nhit (chng c th thng hoa
trong chn khng 380 -5000C), cn cc nitrat ca kim loi khc km bn vi nhit d
phn hy khi un nng.
bn nhit ca mui nitrat ph thuc vo bn cht cation kim loi.
Nitrat ca nhng kim loi hot ng ng trc magie trong dy in ha,
khi un nng b phn hy thnh nitrit v oxy.
V d:

2 NaNO3 =

2 NaNO2

O2

Nitrat ca nhng kim loi t Magie n ng, khi un nng b phn hy thnh
oxyt, nit dioxyt v oxy.
V d:

2 Pb(NO3)2 =

2 PbO

4 NO2

+ O2

Nitrat ca nhng kim loi km hot ng hn ng, khi un nng b phn hy


n kim loi.
V d:

Hg(NO3)2

Hg +
5

2 NO2 +

O2

Cch phn hy khc nhau ca mui nitrat kim loi l do bn khc nhau ca
mui nitrit v oxyt ca ca cc kim loi quyt nh. Chng hn nh NaNO2 v PbO
bn, trong khi Pb(NO2)2, Hg(NO2)2 v HgO khng bn.
Do d mt oxi, cc mui nitrat khan khi un nng l cht oxi ha mnh.
Ion NO3- trong mi trng axit c kh nng oxi ha nh axit nitric, trong mi
trng trung tnh hu nh khng c kh nng oxy ha, nhng trong mi trng kim
c th b Al, Zn kh n NH3.
V d: NaNO3 + 4 Zn + 7 NaOH + 6 H2O = 4 Na2[Zn(OH)4] + NH3
1.3.2. Tnh cht ca nitrit [6]
1.3.2.1. Tnh cht vt l
Nitrit l mui ca axit nitr. Hu ht mui nitrit d tan trong nc, mui t tan
l AgNO2. Cng nh mui nitrat, a s mui nitrit khng c mu.
1.3.2.2. Tnh cht ha hc
Nitrit ca kim loi kim bn vi nhit, chng khng phn hu khi nng chy
m ch phn hu trn 500oC. Nitrit ca cc kim loi khc km bn hn, b phn hu
khi un nng, chng hn nh AgNO2 phn hu 140oC, Hg(NO2)2 75oC.
Trong mi trng axit, mui nitrit c tnh oxy ha v tnh kh nh axit nitr.
Mui nitrit oxy ha c axit HI n I2, dung dch SO2 n H2SO4, ion Fe2+ n
Fe3+ ... cn bn thn n chuyn thnh NO.
V d:

2 HI +

2 NO2- + 2 H+

2 NO + I2

2 H2 O

Vi cc cht oxy ha mnh nh KMnO4, MnO2, th NO2- b oxy ha n NO3-.


V d: 2 KMnO4 + 3 H2SO4 + 5 HNO2 = 2 MnSO4 + 5 HNO3 + K2SO4 + 3 H2O
Mui NaNO2 c s dng rng ri trong cng nghip ha hc, nht l trong
cng nghip sn xut phm nhum azo.

1.4. Cc phng php phn tch nitrat, nitrit


1.4.1. Cc phng php phn tch nitrat
1.4.1.1. Phng php kh bng Zn [13]
C s ca phng php: Ion NO3- c kh v NO2- khi cho tc dng vi Zn
kim loi, sau NO2- c xc nh khi cho tc dng vi axit sunfanilic v naphthylamin.
Phn ng kh ph thuc vo nhit , v vy tt c cc mu phi c kh
cng mt nhit .
Cc ion nh hng: Au, Bi, Fe, Pb, Ag,c th lm gim kt qu o v mu
ca mt s ion xen ln mu ca cht hp th.
Khong xc nh ca phng php: 20 g NO3-- N/L 1,4 mg NO3-- N/L.
1.4.1.2. Phng php kh bng Cd [14]
C s ca phng php: : Ion NO3- b kh v NO2- khi cho mu chy qua ct
cha Cd kim loi, sau NO2- c xc nh khi cho tc dng vi hn hp thuc th
axit sunfanilic v -naphthylamin to hp cht azo mu . o hp th quang
bc sng = 540 nm.
Khong nng gii hn: 0,01 1,0 mg NO3-- N/L.
1.4.1.3. Phng php o th dng in cc chn lc ion [3]
C s ca phng php: Tch ion NO3- ra khi mu thc vt bng dung dch
phn nhm kali 1% (vi t l mu/dung dch = 1/5). Sau xc nh NO3- trong dung
dch nh in cc chn lc ion.
Nguyn l ca phng php l o th in cc chn lc ion, m gi tr th ph
thuc vo nng ion xc nh trong dung dch. in cc bc clorua bo ha c s
dng nh in cc so snh.
Phng php ny khng p dng c nu lng Cl- trong mu phn tch ln
hn nng NO3- trn 50 ln.
nhy phng php: 6 mg NO3- - N/L.
7

1.4.1.4. Phng php axit Cromotrophic [13]


C s ca phng php: Phn ng kt hp gia hai phn t NO3- vi mt phn
t ca axit cromotrophic (C10H8O8S2) hnh thnh nn hp cht mu vng. Sau em
o hp th quang bc sng = 410 nm.
Nu lng clo d (l cht oxy ha) v c mt nitrit cng to nn hp cht mu
vng vi axit cromotrophic. Tuy nhin khi thm mui sunfit c th loi tr c nh
hng t lng d clo (tc nhn oxi ha) v dng ur nhm chuyn ha NO2- thnh N2
loi nh hng ca nitrit.
Gii hn pht hin: 50 g NO3- - N/L.
1.4.1.5. Phng php Natri salixilat [9]
C s ca phng php: o mt quang dung dch c mu vng dng p
nitrosalixylat bc sng 420 nm. y l hp cht c to thnh gia nitrat v natri
salixilat trong mi trng axit.
OH

OH

COONa
+

NO3-

COONa

H+
O3N

(p-nitrosalixylat)

Phng php khng b nh hng bi nitrit ( 2 mg/L), clorua ( 200 mg/L),


st ( 5 mg/L).
1.4.1.6. Phng php axit Phenoldisulfonic [13]
C s ca phng php: Da trn phn ng gia nitrat v axit Phenoldisulfonic
hnh thnh nn hp cht nitrophenol. Khi kim ha th dung dch tr nn mu vng v
c cng mu ph thuc vo nng NO3- trong mu.
C6H3(HSO3)2OH + 3 HNO3 = C6H2(OH)(NO2)3 + 2 H2SO4 + H2O
C6H2(OH)(NO2)3

+ NH3 = C6H2(NO2)2ONH4

hp th o bc sng = 410 nm.


nhy ca phng php: 10-3 mg NO3- - N/L.

1.4.1.7. Phng php quang ph UV [13]


C s ca phng php: Da trn vic o hp th bng phng php quang
ph UV bc sng = 220 nm ca ion NO3-.
Cc cht hu c ha tan c th cng hp th = 220 nm v NO3- khng hp
th bc sng 275 nm nn ta c th o ln th hai bc sng = 275 nm vi mc
ch cho chnh xc gi tr nitrit.
Cht rn l lng c loi b bng cch lc mu.
nh hng ca CaCO3, Ca(OH)2 c th loi b bng cch axit ha bng HCl.
Gii hn pht hin: 40 g NO3- - N/L.
1.4.2. Phng php phn tch nitrit
Phng php dng hn hp thuc th axit sunfanilic v -naphthylamin
C s ca phng php: Cho nitrit cn xc nh tc dng vi hn hp thuc th
axit sunfanilic v -naphthylamin hnh thnh hp cht diazo mu . Sau o
hp th quang ca dung dch bc sng = 540 nm, da vo cc phng php nh
lng (ng chun, thm chun,...) xc nh nng nitrit trong mu.
Phn ng to thnh hp cht mu diazo nh sau:

NH2 + NO2- + 2H+

HO3S

HO3S

N N

2H2O

diazonium

axit sunfanilic

NH2
HO3S

NH2
N N+

HO3S

N=N
(diazonium)
Cht mu
diazo

-naphthylamin
9

+ H+

Cc yu t nh hng n phng php trc quang o nitrit: [13]


+ pH ca mi trng phn ng: Thng c tin hnh pH khong 1,7 3;
+ Nu trong mu c hp cht cha nitrogentriclorua l hp cht c mu ,
do s nh hng khi o quang;
+ Ion Cu2+ lm gim kt qu o, do n l xc tc cho s phn hy mui
diazonium;
+ Mt s ion Sb, Fe, Pb, Ag,... c trong mu s kt ta, gy cn tr php o
quang.
1.4.3. Cc phng php xc nh ng thi nitrat, nitrit
1.4.3.1. Phng php dng axit sunfanilic v -naphthylamin [7]
Nitrit trong mu c xc nh bng cch cho tc dng vi hn hp axit
sunfanilic v -naphthylamin, phn ng to ra hp cht diazo mu . Sau o
hp th quang bc sng = 540 nm.
Tng nitrat, nitrit trong mu c xc nh bng cch cho thm dung dch
EDTA v m amoni. Sau cho chy qua ct kh Cd-Cu. y nitrat b kh v
nitrit, sau nitrit c xc nh bng phng php quang ph nh trn.
thu hi ca phng php: 95 105 %.
Gii hn p dng phng php: 0,01 1,0 mg NO3- - N/L.
1.4.3.2. Phng php sc k lng hiu nng cao (HPLC) [12]
Phng php ny da trn vic tch nitrat, nitrit trn ct tch v c xc nh
bng detect UV. Hn hp pha ng l octyl amonium orthophotphat 0,01M +
metanol theo t l 30% (th tch/th tch) pH = 7, tc bm pha ng l 0,8
mL/pht, thi gian phn tch cho mt mu l 10 pht.
ng chun xc nh nitrat, nitrit xy dng trong khong 0,1 100 g/mL c
h s tng quan r = 0,999.
thu hi ca phng php: 96,6 105,7%.

10

1.4.3.3. Xc nh nitrat, nitrit trong mu sinh hc bng phng php quang ph bm


mu dng chy [14]
Phng php ny c thc hin trn h thng bm mu dng chy hai knh:
+ Knh th nht cha dung dch cht mang gm EDTA trong dung dch m
amoni. Mt ct kh c mc vo knh ny kh nitrat thnh nitrit khi xc nh
tng nitrat v nitrit.
+ Knh th hai cha dung dch thuc th axit sunfanilic v -naphthylamin.
Cht mu diazo to thnh c nhn ra v o bng detect UV- VIS ti bc sng =
540 nm.
Gii hn nh lng c xc nh l 5.10-8 M.
Trng hp cc mu sinh hc c cha nhiu protein c loi tr trc bng
hn hp NaOH-ZnSO4.
1.5. Cc phng php x l mu thc phm [5]
1.5.1. K thut v c ha t
a. Bng axit c mnh, c tnh oxy ha mnh:
Dng axit v c mnh v c (HCl, H2SO4), axit mnh c c tnh oxy ha mnh
(HNO3, H2SO4), hn hp hai axit (HNO3 + H2SO4), hay ba axit (HNO3 + H2SO4 +
HClO4) phn hy mu trong bnh Kendan hay ng nghim c un nng. Lng
axit thng gp 15 - 20 ln lng mu v cn ty thuc vo loi mu. Thi gian ha
tan mu trong cc h h, bnh Kendan thng vi gi n vi chc gi, cng ty thuc
vo loi mu, c mu, bn cht ca cc cht cn xc nh,...
Trong qu trnh x l ny cc nguyn t kim loi dng cc hp cht c kim ca
mu rau qu s b oxy ha, t chy cc cht hu c, a cc kim loi v cc mui v
c tan trong dung dch nc, qu trnh ha hc chnh l:
Mu + HNO3 + H2SO4 = CO2 + H2O + Men(SO4)m + Mex(NO3)y

11

b. X l mu trong l vi sng:
Trong cc h l n gin:
H bnh mu h;
H bnh mu ng kn (c p sut cao);
Trong cc h nhiu bnh v t ng hon ton:
H bnh mu h c khng ch nhit ;
H bnh mu ng kn (c p sut cao) c khng ch nhit v p sut;
X l trong l vi sng h kn (c p sut) th ch cn 50 - 60 pht.
1.5.2. K thut v c ha kh
Nung x l s b mu c ph gia v cht bo v l qu trnh x l mu s b
nh tc dng ca nhit thch hp, c thm tng tc h tr ca cht ph gia, thng
l cc cht chy, axit c ph v cu trc dng tinh th ban u ca mu phn tch,
chuyn n sang mt dng cc hp cht khc d ha tan tip bng axit. Khi c cht
chy, nhit nung thng thp hn khi khng c cht chy, thi gian ngn hn, song
li trit hn, m li khng mt cht phn tch. Nht l cc mu c cu trc bn, chu
nhit hay mu hu c th tc dng cu cht bo v l rt quan trng.
V d: Tro ho mu sa xc nh cc kim loi (Na, K, Ca, Mg, Cd, Co, Cr,
Cu, Fe, Mn, Ni, Pb, Zn), dng cht ph gia l 8 mL H2SO4 45% v 2 g KNO3. Ly 5 g
mu vo chn nung thch anh, thm cht ph gia, trn u, sy kh cn thn cho mu
kh v thnh than en, sau em nung 3 gi u nhit 440-4500C, ri sau
550-5300C, n khi ht than en, c tro mu trng. Sau ha tan tro thu c
trong 15 mL dung dch HCl 18%, un nh cho mu tan ht ri nh mc thanh 25 mL
bng dung dch HCl 2%.
1.5.3. K thut v c ha kh t kt hp
V l x l kh t kt hp l k tip nhau, trc tin x l t s b, sau
mi nung, nn tnh cht v din bin ca n cng tng t nh trong hai kiu
cp trn, ch c khc l sau khi x l mu khng phi ui lng axit d qu nhiu
12

nh trong x l t. Sau khi x l t ta em nung s nhanh hn v qu trnh x l s


trit hn x l t. Phng php ny hn ch c mt cht phn tch ca mt s
kim loi khi nung.
V d: X l mu sa xc nh cc kim loi (Na, K, Ca, Mg, Cd, Co,Cr, Cu,
Fe,Mn, Ni, Pb, Zn). Ly 5 g mu vo chn nung, thm 15 mL HNO3 65%, 2 mL H2SO4
98% v 5 mL Mg(NO3)2 5%, trn u, x l t s b sy mu trn bp in hay trong
t sy cho n khi kh v thnh than en. Sau em nung nhit 400-450 0C trong
3 gi, sau nung 530 0C cho mu tro ha n khi thy b khng cn en. Sau ha
tan tro thu c trong 15 mL HCl 1/1, un nng cho mu ha tan hon ton, ui ht axit
d n cn mui m, v nh mc thnh 25 mL bng axit HCl 2 %.
1.6. C s ca phng php trc quang [1]
1.6.1. nh lut Bouguer Lambert Beer
Khi chiu mt dng sng qua dung dch cht hp th nh sng th cht s
hp th chn lc mt s tia sng ty theo mu sc ca cht.
nh lut Lambert Beer m t mi quan h tuyn tnh gia nng dung dch
v hp th nh sng, c biu din bng phng trnh ton hc sau:
A = .l.C
Trong :
A : hp th quang ca cht ti bc sng
: h s hp th ca cht ti bc sng
l

: chiu dy cuvet ng mu (cm)

: nng ca cu t (mol/L)

iu kin s dng nh lut:


+ Chm tia sng n sc
+ Dung dch phi long, trong sut
+ Cht phn tch phi bn v bn di tc dng ca tia UV VIS
13

(1.1)

1.6.2. Phn tch nh lng


1.6.2.1. Phng php ng chun
+ Chun b mt dy dung dch chun c nng chnh xc, tng dn nht nh
Cx1, Cx2, Cx3, Cx4, ca cht chun cn phn tch.
+ o hp th quang Ax1, Ax2, Ax3, Ax4 ca cc dung dch chun ti bc sng
max kho st.
+ Xy dng ng chun A = f(C).
+ Chun b mu trong iu kin tng t, o hp th quang Ax .
+ Da vo ng chun suy ra nng Cx .

Hnh 1.1. Dng ng chun trong phn tch trc quang

1.6.2.2. Phng php thm chun


Dng mu phn tch lm nn, thm vo cc mu phn tch mt lng xc nh
dung dch chun ca cht phn tch c nng tng dn v thc hin phn ng to
mu c dy mu thm chun. o hp th ca cc mu thm chun ny, ta c:

14

Cx

Cx + C1

Cx + C2

...

Cx + Cn

Ax

Ax+1

Ax+2

...

Ax+n

V ng thm chun A C c dng ng nh sau

Hnh 1.2. Dng ng thm chun


Bng phng php ngoi suy (ng 1) hoc phng php hnh hc (ng 2)
ta tnh c Cx ca cht cn phn tch trong mu.

15

Chng 2
NI DUNG V PHNG PHP NGHIN CU

2.1. Ni dung nghin cu


Nghin cu xc nh nitrat, nitrit bng phng php trc quang trn c s phn
ng gia nitrit vi hn hp thuc th axit sunfanilic v -naphthylamin to ra hp
cht diazo mu . Xy dng quy trnh phn tch, t p dng phn tch mt s
mu thc phm ch bin. Chng ti nghin cu cc ni dung sau:
2.1.1. Kho st cc yu t nh hng tm iu kin thch hp cho phng php
2.1.1.1. Kho st iu kin xc nh nitrit
a. Nng v t l nng C -naphthylamin / C axit sunfanilic
C nh nng axit sunfanilic 2,5.10-4 M, thay i nng -naphthylamin
t 0,5.10-4 10,5.10-4 M v ngc li. Lp th hp th quang ph thuc vo s
thay i ri chn ra t l nng thch hp nht.
b. Mi trng pH ti u
Tin hnh ln mu dung dch chun nitrit vi hn hp thuc th axit sunfanilic
v -naphthylamin, sau o hp th quang ti mi trng pH khc nhau chn
ra c pH thch hp cho phn ng to mu diazo.
c. Thi gian n nh mu
Tin hnh ln mu dung dch chun nitrit vi hn hp thuc th axit sunfanilic
v -naphthylamin, sau o hp th quang ti bc sng hp th cc i ( = 540
nm) lin tc trong 35 pht (mi ln o cch 30 giy), chn thi gian n nh mu
thch hp cho phng php.
2.1.1.2. Kho st iu kin kh t nitrat qua nitrit
a. Chn phng php kh
Thc hin phn ng kh nitrat bng hai phng php: Ct kh Cd-Cu v hn hp
huyn ph km + dung dch CdSO4 ri so snh hiu sut kh hai phng php ny.
16

b. Chn pH kh thch hp
Thc hin phn ng kh vi hn hp huyn ph km + dung dch CdSO4
chn cc pH khc nhau chn pH thch hp.
2.1.2. nh gi tin cy ca phng php
2.1.2.1. Xc nh gii hn pht hin, gii hn nh lng
- Gii hn pht hin (LOD): L nng nh nht ca cht phn tch to ra c mt
tn hiu o c th phn bit mt cch tin cy vi tn hiu o ca mu trng (hay tn
hiu nn). Gii hn pht hin c xc nh theo qui tc 3.
y = yB + 3B hay y = yB + 3SB
Trong :

(2.1)

y: tn hiu ng vi LOD
yB: tn hiu ng vi mu trng (blank)
B (hay SB): lch chun ca tn hiu mu trng

yB v SB c xc nh, da vo phng trnh hi quy tuyn tnh c dng y = a


+ b.C (C l nng ) c thit lp theo phng php "bnh phng ti thiu". yB
c chp nhn l gi tr ca y khi C = 0 yB = a v SB c chp nhn bng Sy/C (
lch chun ca tn hiu y trn ng chun).
SB Sy/C

(y

Yi ) 2

n2

(2.2)

yi: cc gi tr thc nghim ca y; n l s im th nghim (yi, Ci)


Yi: cc gi tr ca y tnh t phng trnh ng chun (hay cc gi tr y l
thuyt)
T (2.1) ta c:

y = yB + 3SB = a + 3Sy/C

LOD c tnh t phng trnh hi quy y = a + bC nh sau:


y = a + bLOD = a + 3Sy/C bLOD = 3Sy/C LOD = 3Sy/C/b

(2.3)

- Gii hn nh lng (LOQ) l nng nh nht trn mt ng chun tin


cy.Thng ngi ta chp nhn LOQ = 10Sy/C/b hay LOQ = (3 4).LOD (2.4)

17

2.1.2.2. nh gi lp li
Tin hnh th nghim 4 - 5 ln trn mi mu thc phm ch bin bng phng
php thm chun xc nh lp li thng qua gi tr lch chun tng i
(RSD). Theo cc cng thc sau:
n

S2 =

Phng sai:

xi2

xi)2
(
i=1
n

i= 1

(2.5)

n-1

(xi l nng cht phn tch c suy ra t ng thm chun; n l s th nghim)

lch chun tng i RSD (%):


RSD =

S
100 (%)
x

(2.6)

Phng trnh Horwits:


RSDH = 21 - 0,5lgC (%)

(2.7)

(C l nng x trung bnh cc ln th nghim)


Nu tha mn iu kin RSD 0,5.RSDH th phng php c lp li tt.
2.1.2.3. nh gi thu hi
thu hi c tnh theo cng thc sau:

Re v(%)

C x a Cx
.100
Ca

(2.8)

( Trong : Cx a l nng nitrit trong mu + KNO2 cho vo trc khi x l;


Cx l nng nitrit trong mu, Ca l nng KNO2 ).
Nu thu hi nm trong khong 90 - 110% th phng php c thu hi
tt.
2.1.2.3. Cng thc tnh hm Fisher (F), Student (t) so snh cc kt qu o c

18

Vi 2 dy s liu c cc gi tr: A : na, xa, Sa2


B: nb, xb, Sb2
Cng thc tnh hm Fisher (F):
F

S a2
1
S b2

(2.9)

Cng thc tnh hm Student (t):


t TN

S2

xa xb
S

na .nb
na nb

(2.10)

S a2 .(na 1) Sb2 .(nb 1)


na nb 2

(2.11)

Trong :
n: S th nghim
xi: Gi tr trung bnh ca xi
Si 2: Phng sai ca dy kt qu i
2.1.3. Kho st phng php x l mu thc phm
Tin hnh chit nitrat, nitrit trong mu thc phm ch bin bng hai phng
php khc nhau l: ngm nhit khong t 50 - 60oC, rung siu m tm ra
phng php no chit nitrat, nitrit l hiu qu cao nht.
2.1.4. Xc nh m trong mu thc phm ch bin
ng vi mi loi thc phm ch bin, xc nh m ca chng bng cch sy
kh cc thy tinh n khi lng khng i c m1 (g), sau thm mt lng mu
vo em cn c cc v mu c m2 (g), sy kh mu nhit t 100 - 105oC n
khi lng khng i c m3 (g). m c xc nh theo cng thc sau:

m2 - m3
X = m - m .1 0 0 %
2
1

19

(2.12)

2.1.5. p dng quy trnh x l mu phn tch nitrat, nitrit trong mu thc phm
ch bin
T cc iu kin kho st c trn, tin hnh h thng li thnh mt quy
trnh phn tch hon chnh xc nh hm lng nitrat v nitrit trong mu thc phm
ch bin.
2.1.6. Th p dng qui trnh phn tch trn cc i tng thc t
2.2. Phng php nghin cu
2.2.1. Cc phng php nghin cu
2.2.1.1. C s l thuyt ca phng php [9], [15]
Phng php xc nh nitrit da trn c s phn ng ca nitrit vi hn hp
thuc th axit sunfanilic v -naphthylamin to thnh hp cht diazo mu . o
hp th quang ca dung dch bc sng = 540 nm, phn ng nh sau:
NH 2 +

HO3S

NO2-

2H +

HO3S

(axit sunfanilic)

N N

2H 2O

(diazonium)
NH2
NH2

HO3S

N N+

HO3S

N=N

+ H

(diazonium)
Cht
mu diazo

-naphthylamin

Tng nitrat, nitrit trong mu c xc nh bng cch dng bt km v dung


dch CdSO4 kh nitrat v nitrit. Sau nitrit c xc nh da vo phn ng trn.
2.2.1.2. Ph ca hp cht mu diazo
Hp cht mu diazo hp th nh sng cc i ti bc sng = 540 nm theo
hnh 2.1 sau:

20

Hnh 2.1. Ph hp th ca hp cht mu diazo


hp th quang ca dung dch bc sng = 540 nm tha mn nh lut
hp th Beer:
A = .b.c

(2.13)

Trong : A : hp th quang ca dung dch ti bc sng = 540 nm


: h s hp th ca cu t ti bc sng = 540 nm
b

: chiu dy cuvet ng mu (cm)

: nng cu t (mol/L)

2.2.2. Thit b v ha cht


2.2.2.1. Thit b v dng c
- My trc quang UV-VIS: T80+ UV/VIS Spectrometer, M sn xut.
- My o pH: 330 i/SET, c sn xut.
- Cn phn tch, my rung siu m.
- My khuy t, my ly tm.
- Cc dng c thy tinh: bnh nh mc, cc m, pipet, buret, a thy tinh,...
- Bnh tia, bp cao su,...
21

2.2.2.2. Ha cht
Cc ha cht s dng c lit k bng 2.1
Bng 2.1. Cc ha cht s dng
Tn ha cht

Xut x

Tn ha cht

Xut x

KNO2

Trung Quc

Km acetat

Trung Quc

KNO3

Trung Quc

HCl m c

Trung Quc

Axit sunfanilic

CH3COOH m c

Trung Quc

-naphthylamin

Trung Quc

Chlorofom

Trung Quc

EDTA

Trung Quc

CdSO4

Trung Quc

NaOH

Trung Quc

Zn

Trung Quc

Natri borat

Trung Quc

Than hot tnh

Trung Quc

K4[Fe(CN)6]

Trung Quc

2.2.3. Chun b dung dch thuc th v dung dch chun


2.2.3.1. Dung dch chun
- Dung dch gc KNO3 1,0 g/L: Ha tan 0,50 g KNO3 trong nc, bo qun vi
1 mL chloroform, nh mc thnh 500 mL.
- Dung dch trung gian KNO3 0,1 g/L : Pha long 10,0 mL dung dch gc thnh
100 mL bng nc ct.
- Dung dch lm vic KNO3 10 mg/L : Pha long 10,0 mL dung dch trung gian
thnh 100 mL bng nc ct.
- Dung dch gc KNO2 1,0 g/L : Ha tan 0,50 g KNO2 trong nc, bo qun vi
1mL chloroform, nh mc thnh 500 mL.
- Dung dch trung gian KNO2 0,1 g/L : Pha long 10,0 mL dung dch gc thnh
100 mL bng nc ct.
- Dung dch lm vic KNO2 10 mg/L : Pha long 10,0 mL dung dch trung gian
thnh 100 mL bng nc ct.

22

2.2.3.2. Dung dch thuc th


- Axit sunfanilic(SA) 0,05 M: Ha tan 2,1625 g axit sunfanilic trong 150 mL
nc nng, thm vo 50 mL HCl m c, nh mc thnh 250 mL.
- -naphthylamin(NA) 0,05 M : Ha tan 1,7875 g -naphthylamin trong 200 mL
nc, thm vo 2,5 mL HCl m c, nh mc thnh 250 mL.
- Dung dch Natri Borat bo ha: Cho Natri Borat vo 200 mL nc ct un
si. Thm Borat vo cho n khi khng ha tan thm c na, sau ngui v
gn ly phn dung dch trn dng.
- Dung dch EDTA 0,013 M : Ha tan 0,5g EDTA trong 100 mL nc.
- Dung dch HCl 0,16 M : Pha long 3,3 mL HCl c thnh 250 mL bng nc.
- Dung dch CdSO4 0,114 M : Ha tan 10,0 g CdSO4.8H2O trong 250 mL nc.
- Km, dung dch huyn ph: Ngay trc khi dng, cho 10 mL nc v 2 g bt
km vo mt cc nh c m. Dng my khuy t duy tr km dng huyn ph.
- Dung dch NaOH 0,05 M: Ha tan 0,1 g NaOH trong 50 mL nc.
- Dung dch lm kt ta protein v cht bo:
+ Dung dch K4[Fe(CN)6] 0,4 M: Ha tan 10,6 g K4[Fe(CN)6].3H2O
trong 100 mL nc.
+ Dung dch Zn(CH3COOH)2: Ha tan 22 g Zn(CH3COOH)2 trong nc,
thm vo 3 mL CH3COOH m c, nh mc thnh 100 mL.
- Than hot tnh.
- CuSO4.5H2O 5%: Ha tan 20 g CuSO4.5H2O trong 500 mL nc, nh mc
thnh 1000 mL.
- Dung dch NH4Cl-EDTA gc: Ha tan 13 g NH4Cl v 1,7 g EDTA trong 900
mL. iu chnh v pH=8,5 vi NH4OH m c.
- Dung dch NH4Cl-EDTA lm vic: Pha long 300 mL dung dch NH4ClEDTA gc thnh 500 mL.
- Dung dch HCl 6 N: Ha tan 25 mL HCl m c trong 50 mL nc.
23

Chng 3
KT QU V THO LUN
3.1. Kho st cc yu t nh hng tm iu kin thch hp cho phng php
3.1.1. iu kin xc nh nitrit
3.1.1.1. Nng v t l nng -naphthylamin v axit sunfanilic
a. nh hng nng axit sunfanilic n hp th quang ca dung dch hp cht
mu diazo
Ht 5 mL dung dch KNO2 10 mg/L, 3 mL dung dch HCl 0,16 M, sau thm
vo mi bnh mt th tch khc nhau ca dung dch SA c nng bng 2,5.10-3 M, ri
1,0 mL dung dch NA 2,5.10-2 M cho tt c cc bnh nh bng 3.1. nh mc n 50
mL c nng SA thay i trong khong t 0,5.10-4 10,5.10-4 M. Lc cn thn,
o hp th quang ca dung dch sau 15 pht bc sng = 540 nm. Kt qu ch
ra bng 3.1 v hnh 3.1.
Bng 3.1. S ph thuc hp th quang ca dung dch cc hp cht mu diazo
vo nng axit sunfanilic
CSA.10-4 (M)

CSA.10-4 (M)

0,5

0,323

7,5

0,374

1,5

0,373

8,5

0,367

2,5

0,383

9,5

0,363

3,5

0,382

10,5

0,356

4,5

0,382

6,5

0,378

24

0.39
0.38
0.37

0.36
0.35
0.34
0.33
0.32
0

10

12

-4

C SA.10 (M)

Hnh 3.1. S ph thuc hp th quang ca dung dch hp cht mu diazo


vo nng SA
Kt qu bng 3.1v hnh 3.1 cho thy: Khi tng nng SA t 0,5.10-4
10,5.104 M th hp th ca dung dch t cc i nng 2,5.10-4 M, khi nng
SA ln hn 2,5.10-4 M th hp th quang ca dung dch gim dn. Nh vy, nng
axit sunfanilic 2,5.10-4 M c chn l nng thch hp nht cho phng php.
b. nh hng nng -naphthylamin n hp th quang ca dung dch hp cht
mu diazo
Ht 5 mL dung dch KNO2 10 mg/L, 3 mL dung dch HCl 0,16 M, sau thm
vo mi bnh cc th tch khc nhau ca dung dch NA c nng bng 2,5.10-2 M, ri
5 mL dung dch SA 2,5.10-3 M cho tt c cc bnh nh bng 3.2. nh mc n 50
mL c nng NA thay i trong khong t 0,5.10-4 10,5.10-4 M. Lc cn
thn, hp th quang ca dung dch sau 15 pht bc sng = 540 nm. Kt qu
ch ra bng 3.2 v hnh 3.2.

25

Bng 3.2. S ph thuc hp th quang ca dung dch cc hp cht mu diazo


vo nng -naphthylamin
CNA.10-4 (M)

CNA.10-4 (M)

0,5

0,205

7,5

0,370

1,5

0,334

8,5

0,369

2,5

0,374

9,5

0,376

3,5

0,373

10,5

0,375

4,5

0,369

6,5

0,367

0.38
0.36
0.34
0.32

0.30
0.28
0.26
0.24
0.22
0.20
0

10

12

-4

CNA.10 (M)

Hnh 3.2. S ph thuc hp th quang ca dung dch hp cht mu diazo


vo nng NA
Kt qu bng 3.2 v hnh 3.2 cho thy: Khi tng nng NA t 0,5.10-4
10,5.10-4 M th hp th ca dung dch t cc i nng 2,5.10-4 M, khi nng
ln hn 2,5.10-4 M th hp th quang ca dung dch thay i hu nh khng
26

ng k. Nh vy, nng -naphthylamin 2,5.10-4 M c chn l nng thch hp


nht cho phng php. Vy ta chn c t l C -naphthylamin / C axit sunfanilic

= 1.

3.1.1.2. Mi trng pH to mui diazo thch hp


Ht 5 mL dung dch KNO2 10 mg/L, sau thm vo mi bnh cc th tch
khc nhau ca dung dch HCl 0,16 M, ri 5 mL SA 2,5.10-3 M v 0,5 mL NA 2,5.10-2
M. nh mc n 50 mL, lc u v o bng my o pH. Sau 15 pht o hp th
quang ca dung dch bc sng = 540 nm. Kt qu ch ra bng 3.3 v hnh 3.3.
Bng 3.3. S ph thuc hp th quang ca dung dch hp cht mu diazo theo pH
pH

1,14

1,50

1,67

1,78

1,82

1,95

2,00

2,03

2,07

0,136

0,256

0,280

0,312

0,337

0,351

0,361

0,372

0,370

0.40
0.35

0.30
0.25
0.20
0.15
0.10
1.0

1.2

1.4

1.6

1.8

2.0

2.2

pH

Hnh 3.3. S ph thuc hp th quang ca dung dch mu diazo theo pH


T kt qu bng 3.3 v hnh 3.3 cho thy: Khi thay i pH trong khong t
1,14 2,07 th hp th quang tng dn, n pH = 1,95 2,03 th hp th A gim
dn. Vy ta chn gi tr pH nm trong khong t 1,95 2,03 to mu diazo.

27

3.1.1.3. Thi gian n nh mu


Ht 5 mL dung dch KNO2 10 mg/L, thm 0,2 mL HCl 0,16 M, ri 5 mL SA
2,5.10-3 M v 0,5 mL NA 2,5.10-2 M . nh mc n 50 mL ri lc u. o hp th
quang ca dung dch bc sng = 540 nm lin tc trong 35 pht, mi ln o cch
30 giy, thu c kt qu hnh 3.4 .
0 .3 8
0 .3 6
0 .3 4
0 .3 2

0 .3 0
0 .2 8
0 .2 6
0 .2 4
0 .2 2
0

5 00

10 0 0

1 5 00

2 00 0

T hoi g ia n (s)

Hnh 3.4. S ph thuc hp th quang ca dung dch mu diazo theo thi gian
T hnh 3.4 cho thy: Thi gian bn mu ca hp cht diazo t 15 pht tr ln.
3.1.2. iu kin kh t nitrat qua nitrit
3.1.2.1. Chn phng php kh
3.1.2.1.1. Kh bng ct kh Cd-Cu [9]
a. Chun b ct kh Cd-Cu
Chun b hn hp Cd Cu: cn khong 25 g cadmi (Cd) kim loi dng ht,
ra Cd bng HCl 6 M cho n khi b mt Cd c mu trng bc. Gn ly Cd v ra
sch bng nc ct. Thm 100 mL dung dch CuSO4 2% v khuy cho n khi mt
mu xanh ca CuSO4. Gn ly Cd v lp li vic x l vi CuSO4 2% cho n khi bt
u xut hin kt ta keo nu (Cu kim loi). Ra cn thn bng nc ct loi ht kt
ta keo nu ny. Hn hp Cd Cu thu c c mu en.
Nhi ct: dng mt buret loi tt c dung tch 25 mL, nhi mt lp bng thy
tinh mng vo y ct, ng kha buret ri thm nc ct vo y. Nhi hn hp Cd
Cu ln ct. Ph ln trn b mt ct mt lp bng thy tinh mng.
28

Ra v hot ha ct: ra ct vi 200 mL dung dch m amoniclorua EDTA


lm vic. Hot ha ct bng cch chun b dung dch hn hp c thnh phn gm: 25
mL dung dch nitrat 1,0 mg NO3- /L v 75 mL dung dch NH4Cl EDTA lm vic.
Sau cho chy qua ct vi tc 7 - 10 mL/pht.
(Lu : trong qu trnh nhi v bo qun ct phi lun gi dung dch ngp ct, ct
phi khng c bt kh phn b gia cc ht Cd Cu)
b. Kh bng ct kh Cd-Cu
Cho 10 mL dung dch KNO3 nng 10 mg/L c pH ln lt l 9,34 v 10,0
chy qua ct kh Cd-Cu. Sau ly 5 mL NO2- kh, tin hnh ln mu theo cc
iu kin kho st. nh mc n 50 mL. Sau 15 pht o hp th quang ca
dung dch (lp li 3 ln).Kt qu ch ra bng 3.4.
Bng 3.4. S thay i hp th quang pH khc nhau vi ct kh Cd-Cu
pH

A(Ct Cd-Cu)

9,34

0,193

0,197

0,189

10,0

0,201

0,210

0,207

3.1.2.1.2. Kh bng hn hp huyn ph km + dung dch CdSO4


a. Hn hp huyn ph km + dung dch CdSO4
Dung dch CdSO4 0,114 M
Ha tan 10,0 g CdSO4.8H2O trong 250 mL nc.
Km, dung dch huyn ph: Ngay trc khi dng, cho 10 mL nc v 2 g bt km
vo mt cc nh c m. Dng my khuy t duy tr km dng huyn ph.
b. Kh bng hn hp huyn ph km + dung dch CdSO4
Cho 10 mL dung dch KNO3 nng 10 mg/L c pH ln lt l 9,34 v 10,0
vo ng ly tm, thm tip 1mL huyn ph km, 1mL dung dch CdSO4 0,114 M ri ly
tm vi tc 1000 vng/pht trong 10 pht kh nitrat thnh nitrit [10].
Sau ly 5 mL NO2- kh, tin hnh ln mu theo cc iu kin kho st.
nh mc n 50 mL. Sau 15 pht o hp th quang ca dung dch (lp li 3 ln).
Kt qu ch ra bng 3.5.
29

Bng 3.5. S thay i hp th quang pH khc nhau vi hn hp


huyn ph km + dung dch CdSO4
pH

A(Huyn ph km + d.d CdSO4)

9,34

0,212

0,214

0,217

10,0

0,223

0,227

0,224

T kt qu bng 3.4 v 3.5 cho thy: Vi pH = 9,34;10,0 hp th quang


i vi dng hn hp huyn ph km + dung dch CdSO4 cho gi tr ln hn ct kh
Cd-Cu. Nn chng ti chn phng php kh v pH dung dch kh: Kh bng hn
hp huyn ph km + dung dch CdSO4 vi pH kh l 9,34 10,0.
3.2. Xy dng ng chun xc nh nitrat v nitrit
3.2.1. ng chun xc nh nitrit
Chun b mt dy mu chun KNO2 bng cch ht cc th tch khc nhau dung
dch chun KNO2 10 mg/L vo cc bnh nh mc 50 mL, thm vo 0,2 mL dung dch
HCl 0,16 M, 5 mL dung dch SA 2,5.10-3 M, 0,5 mL dung dch NA 2,5.10-2 M. Sau
nh mc thnh 50 mL ta c dung dch KNO2 c nng nm trong khong t 0,1
2,1 mg/L. Sau 15 pht o hp th quang ca dung dch. T kt qu thu c, lp
phng trnh ng chun theo phng php bnh phng ti thiu. Kt qu thu c
theo bng 3.6.
Bng 3.6. S ph thuc hp th quang ca dung dch mu diazo vo nng nitrit
v phng trnh ng chun xc nh nitrit

CNO2 (mg NO2-/L)

0,1

0,5

0,9

1,3

1,7

2,1

0,036

0,188

0,327

0,463

0,586

0,691

ng chun

Y = 0,013 + 0,334 .X

0.9984

0,013

b (mg/L)

0,334

Sa

0,010

Sb (mg/L)

0,008

Sy/x

0,016
30

0.7
0.6
0.5

0.4
0.3
0.2
0.1
0.0
0.0

0.5

1.0

1.5

2.0

2.5

CNO (mg NO2 /L)


-

Hnh 3.5. S ph thuc hp th quang ca dung dch mu diazo vo nng nitrit


3.2.2. ng chun xc nh nitrat
Chun b mt dy mu chun KNO3 c nng 20 mg/L, pH c iu chnh
nm trong khong t 8,5 10 bng NaOH 0,05 M. Thm vo mi ng ly tm 1 mL
dung dch CdSO4 0,114 M v 1 mL dung dch huyn ph km, ri ly tm kh NO3thnh NO2-. Sau khi ly tm, ht mi ng cc th tch khc nhau dung dch NO2- c
nng 20 mg/L cho vo bnh nh mc 50 mL. Thm vo mi bnh 0,2 mL dung
dch HCl 0,16 M, 5 mL dung dch SA 2,5.10-3 M, 0,5 mL dung dch NA 2,5.10-2 M,
nh mc thnh 50 mL. Ta c dy mu chun c nng nm trong khong t 0,5
3 mg/L. T kt qu thu c, lp phng trnh ng chun theo phng php bnh
phng ti thiu. Kt qu thu c theo bng 3.7.

31

Bng 3.7. S ph thuc hp th quang ca dung dch mu diazo vo nng nitrat


v phng trnh ng chun xc nh nitrat

CNO (mg NO3-/L)

0,5

1,5

2,5

0,045

0,087

0,134

0,171

0,189

0,247

ng chun

Y = 0,005 + 0,080 .X

0,9955

0,005

b (mg/L)

0,080

Sa

0,006

Sb (mg/L)

0,003

Sy/x

0,009

0.25

0.20

0.15

0.10

0.05
0.5

1.0

1.5

2 .0

2 .5

3 .0

NO3

(m g NO /L)
3

Hnh 3.6. S ph thuc hp th quang ca dung dch mu diazo vo nng nitrat


3.3. Xc nh gii hn pht hin, gii hn nh lng
T phng trnh ng chun ca nitrit v nitrat tnh c LOD v LOQ theo
cng thc phn 2.1.2.1. Kt qu bng 3.8 sau:

32

Bng 3.8. Gii hn pht hin v gii hn nh lng ca nitrit, nitrat


Stt

Xc nh gii hn

Nitrit (mg/L)

Nitrat (mg/L)

Gii hn pht hin (LOD)

0,144

0,338

Gii hn nh lng (LOQ)

0,432

1,014

3.4. Kho st nh hng nitrat qua nitrit


Ht 7,5 mL dung dch KNO2 c nng 10 mg/L, thm vo mi bnh cc th
tch dung dch KNO3 khc nhau tng ng vi nng nitrat bng 1/10 nitrit v gp
10 ln nitrit. Sau thm 0,2 mL dung dch HCl 0,16 M, 5 mL dung dch SA 2,5.10-3
M, 0,5 mL dung dch NA 2,5.10-2 M. nh mc n 50 mL c nng KNO3
thay i trong khong t 0,15 15 mg/L, nng KNO2 c nh l 1,5 mg/L.
Mu so snh: Gm 7,5 mL dung dch KNO2 nng 10 mg/L, 0,2 mL dung
dch HCl 0,16 M, 5 mL dung dch SA 2,5.10-3 M, 0,5 mL dung dch NA 2,5.10-2 M.
Bng 3.9. S thay i hp th quang khi c nh nng nitrit
Cnitrit

Cnitrat

(mg KNO2/L)

(mg KNO3/L)

1,5

0,00

0,386

1,5

0,15

0,386

1,5

0,30

0,386

1,5

0,45

0,386

1,5

0,60

0,388

1,5

0,75

0,386

1,5

0,90

0,390

1,5

1,05

0,388

1,5

1,20

0,387

1,5

1,35

0,388

Stt

33

Cnitrit

Cnitrat

(mg KNO2/L)

(mg KNO3/L)

1,5

0,00

0,552

1,5

3,00

0,555

1,5

4,50

0,554

1,5

6,00

0,555

1,5

7,50

0,555

1,5

9,00

0,561

1,5

10,5

0,556

1,5

12,0

0,558

1,5

13,5

0,577

1,5

15,0

0,557

Stt

T kt qu bng 3.9 ta thy: hp th ca cc mu so vi mu so snh t


thay i, chng t nitrat khng nh hng n qu trnh to mu trong qu trnh kh.
3.5. Kho st phng php x l mu thc phm
Chn ngu nhin mt s mu thc phm ch bin ( y chn mu l xc xch
b ViSan).
Tin hnh x l mu nh sau: Thi nh mu, trn u ly mu i din. Cn
30 g mu, cho vo 2 cc thu tinh ring, thm vo khong 100 - 150 mL nc ct,
8 mL dung dch natri borat bo ho, 0,5 g than hot tnh.
chit nitrat, nitrit th kho st theo 2 cch nh sau:
Ngm nhit t 50 - 60oC:
Cc thy tinh th nht, em un cch thy 30 - 40 pht nhit trong khong
50-60oC. ngui, thm 5mL dung dch K4[Fe(CN)6] 0,4 M, 5mL dung dch
Zn(CH3COOH)2, 8mL dung dch natri borat bo ha. Chuyn hn hp trong cc sang
bnh nh mc 250 mL. Lc u hn hp, yn cho lng 30 pht, ri lc ly dch lc.
Siu m:
Cc thy tinh th hai, em siu m khong 30 - 40 pht. ngui, thm 5 mL
dung dch K4[Fe(CN)6] 0,4 M, 5 mL dung dch Zn(CH3COOH)2, 8 mL dung dch natri
34

borat bo ha. Chuyn hn hp trong cc sang bnh nh mc 250 mL. Lc u hn


hp, yn cho lng 30 pht, ri lc ly dch lc.
Sau , tin hnh phn ng to mu xc nh nitrit v tng nitrat, nitrit theo
cc iu kin kho st v o hp th quang. Kt qu thu c bng 3.10.
Bng 3.10. nh hng ca phng php x l mu n hp th quang
Phng php x l

Ngm chit

Rung siu m

Khng qua kh

Qua kh

Khng qua kh

Qua kh

Atb1

0,012

0,069

0,012

0,120

Atb2

0,016

0,151

0,016

0,146

Atb3

0,021

0,178

0,026

0,171

Atb

0,016

0,133

0,018

0,146

S2

0,000025

0,0032

0,0001

0,0007

Dng hm student so snh gi tr trung bnh ca hai phng php c khc


nhau khng v kt qu no tt hn.
Khi cha kh:
FTN (0,95; 3; 3) = 2,557
FLT (0,95; 3; 3) = 15,439
FTN < FLT : lch chun ca hai dy kt qu khng khc nhau ng k.
tLT (0,95; 3) = 2,776
tTN (0,95; 3) = 0,33942
tLT > tTN : X l bng hai phng php nh nhau.
Khi kh:
FTN (0,95; 3; 3) = 4,955
FLT (0,95; 3; 3) = 15,439
FTN < FLT : lch chun ca hai dy kt qu khng khc nhau ng k.
tLT (0,95; 3) = 2,776
tTN (0,95; 3) = 0,36183
tLT > tTN : X l bng hai phng php nh nhau.
35

Kt lun: Dng hm Student kim tra cc dy s liu ta thy, hai phng


php x l l khc nhau v hm lng nitrit, nitrat c chit bng phng php ngm
chit 50 - 60oC cho kt qu tt hn.
Kim tra s mt mt nitrit qua qu trnh x l
kim tra s mt mt nitrit do qu trnh x l mu, chng ti tin hnh hai th
nghim sau:
Th nghim 1: Cn 30 g mu, tin hnh x l nh qui trnh thu c dch lc. Ly
10 mL dch lc cho vo bnh nh mc 50 mL, thm chun KNO2 10 mg/L v tin
hnh to mu theo cc iu kin chn. o quang thu c A x .
Th nghim 2: Cn 30 g mu, thm vo 12,5 mL KNO2 100 mg/L. Ri tin hnh x l
nh qui trnh thu c dch lc. Ly 10 mL dch lc cho vo bnh nh mc 50 mL,
thm chun KNO2 10 mg/L v tin hnh to mu theo cc iu kin chn. o
quang thu c A x a .
Mi th nghim lp li 3 ln ly gi tr trung bnh.
T phng trnh ng thm chun cc ln th nghim, tnh c nng trung
bnh nitrit trong mu tng ng vi Cx v nng nitrit trong mu + KNO2 tng ng
vi C x a . Kt qu ch ra bng 3.11.
Bng 3.11. Gi tr hp th quang tnh s mt mt nitrit qua qu trnh x l mu
S th nghim (TN)

TN1

A x = 0,149

C (mg/L)

C x = 0,017 0,002

Rev (%)

TN2
Ax a = 0,288
Cx a = 0,189 0,001

17,2
(Ca ~ 1 mg/L)

T kt qu bng 3.11 ta thy: T gi tr thu hi thp, cho thy qa trnh


ngm chit 50 600C lm mt i hm lng nitrit ng k. Nguyn nhn l do qu
trnh x l, qu trnh kh lm cho nhy ca php o thp.

36

3.6. p quy trnh x l mu phn tch nitrat, nitrit trong mu thc phm ch
bin

Mu thc phm ch bin


Xc nh m

Thi mng
Cn mmu = 30 g, thm 100 mL nc ct, thm 8 mL Natri
borat bo ha, thm 0,5 g than hot tnh
Ngm chit 50-60 0C, 15 pht
ngui n nhit phng
Thm 5 mL K4[Fe(CN)6] 0,4 M
Thm 5 mL Zn(CH3COOH)2
Thm 8 mL Natri borat bo ha

nh mc V0 = 250 mL
lng 30 pht

Lc ly dch lc
Xc nh nitrit
+ V1 = 10 mL mu
+ Thm chun bng KNO2 10 mg/L (*)
+ 0,2 mL HCl 0,16 M
+ 1 mL EDTA 0,013 M
+ 5 mL axit sunfanilic 0,0025 M
+ 0,5 mL -napthylamin 0,025 M

Xc nh tng nitrit v nitrat

+ V3 = 10 mL mu
+Thm chun bng KNO3 50 mg/L (**)
+ iu chnh pH = 8,5 10
Kh bng: 1 mL CdSO4 0,114 M
1 mL huyn ph km trong ng ly
tm 15 mL (V4)

nh mc 50 mL (V2)

Sau 15 pht o quang

+ V5 = 10 mL dch sau khi kh


+ 0,2 mL HCl 0,16 M
+ 1 mL EDTA 0,013 M
+ 5 mL axit sunfanilic 0,0025 M
+ 0,5 mL -napthylamin 0,025 M

Tnh hm lng nitrit


nh mc 50 mL (V6)
Hm lng nitrat = tng

Sau 15 pht o quang

( nitrit + nitrat) - nitrit


Tnh tng hm lng nitrit, nitrat

Hnh 3.7. S qui trnh phn tch nitrat, nitrit trong mu thc phm ch bin
37

Trong :
(*) : Thm chun vi th tch l 0; 0,5; 5 mL dung dch KNO2 (10 mg/L)
(**): Thm chun vi th tch l 0; 0,5; 1,5 mL dung dch KNO3 (50 mg/L)
3.7. Xc nh nitrit, nitrat trong mu tht
T kt qu kho st cc iu kin thch hp cho phng php xc nh nitrit,
nitrat c p dng phn tch trn mt s mu thc phm ch bin tht. C th l
mu Xc xch b ViSan.
Quy trnh x l mu tin hnh theo quy trnh c trnh by trong mc 3.7.
Phng php nh lng l phng php thm chun.
Kt qu hm lng nitrit, nitrat trong mu c xc nh theo cc cng thc sau:
Hm lng nitrit (mg NO2-/kg) c xc nh theo cng thc:

mnitrit (1kg )

a V2 V0 1000
. .
.
( mg / kg )
b V1 1000 mmu

Tng hm lng nitrat, nitrit (mg /kg) c xc nh theo cng thc:

mnitrat , nitrit (1kg )

a V6 V4 V0 1000
. . .
.
( mg / kg )
b V5 V3 1000 mmu

Hm lng nitrat (mg NO3-/kg) c xc nh theo cng thc:

mnitrat mnitrat , nitrit mnitrit (mg / kg )

38

Bng 3.12. Kt qu hm lng nitrat, nitrit trong Xc xch b ViSan


Hm lng nitrit,
nitrat (mg/kg)
Loi mu

Xc xch
b ViSan
(NSX:
10/3/2012)

a
im

Siu
th
Thun
Thnh
Mart

lp li (%)

m
(%)

Nitrit

Nitrat

0,7
0,011

0,71

10,04

(n=3)

(n=3)

(n=3)

Nitrit

Nitrat

RSD = 11,76

RSD = 50

RSDH = 3,69

RSDH = 2,65

(n=3)

(n=3)

So snh kt qu hm lng nitrat bng 3.12 vi tiu chun Vit Nam [8] cho
thy hm lng nitrat trong mu Xc xch b thp hn ngng cho php. Vy mu
Xc xch b trn c hm lng nitrat cho php s dng.

39

Chng 4
KT LUN V KIN NGH
4.1. Kt lun
1. kho st c v la chn c iu kin thch hp cho phn ng to
mu ca hp cht diazo gia nitrit, -naphthylamin, axit sunfanilic. Cc iu kin nh
sau:
C -naphthylamin

: 2,5.10-4 M

C axit sunfanilic

: 2,5.10-4 M

pH

: 1,95 2,03

Thi gian bn mu : 15 30 pht


2. kho st iu kin thch hp kh nitrat thnh nitrit vi cc thng s
sau:
Dng hn hp huyn ph km + dung dch CdSO4
pH ca dung dch kh tt nht l 9,34 10,0
3. nh gi tin cy ca phng php thng qua vic xc nh gii hn pht
hin, gii hn nh lng, lp li.
4. p dng qui trnh phn tch nitrat, nitrit trong mu xc xch b vi
lp li cha tt.
T ngng hm lng cho php ca nitrat, nitrit trong mt s loi thc phm
ch bin theo tiu chun Vit Nam [8], cho thy hm lng nitrat, nitrit trong mu
thc phm phn tch thp hn ngng cho php.
4.2. Kin ngh
Do thi gian nghin cu cn hn hp nn ch p dng c trn mt mu thc
phm ch bin (xc xch b). Nn tin hnh vi nhiu mu tht hn c nhiu kt
qu nh gi y hn.

40

TI LIU THAM KHO


Ti liu ting Vit
[1].

Trn T Hiu, T Vng Nghi, Nguyn Vn Ri, Nguyn Xun Trung (2003),
Ha hc phn tch phn 2, Nxb i hc Quc gia H Ni, tr. 5 - 27.

[2].

Nguyn Th Hon (2009), Nghin cu phng php ng hc trc quang xc


nh hm lng nitrit trong mu nc ngm v thc phm, Lun vn thc s
khoa hc, i hc S phm Thi Nguyn.

[3].

L Vn Khoa, Nguyn Xun C, Bi Th Ngc Dung, L c, Trn Khc Hip,


Ci Vn Tranh (2000), Phng php phn tch t nc, phn bn, cy trng,
Nxb Gio dc, tr. 278 - 283.

[4].

Nguyn Ch Linh (2007), Bi ging Ph gia trong ch bin thc phm, Trng
Cao ng cng ng Kin Giang, Rch Gi.

[5].

Phm Lun (1999), Gio trnh hng dn v nhng k thut x l mu phn


tch, i hc Khoa hc T nhin H Ni, tr. 25 - 34.

[6].

Hong Nhm (2001), Ha hc v c, tp hai, Nxb Gio dc, tr. 188 189.

[7].

Kim Oanh (2001), Nitrat v sc khe con ngi , Vin la ng bng sng
Cu Long, tr1.

[8].

Quyt nh 3742/2001/Q_BYT ca B Y T v vic ban hnh Qui nh


danh mc cc cht ph gia c php s dng trong thc phm.

[9].

Quy trnh phn tch cc thng s cht lng nc v trm tch, nh gi cht
lng nc v trm tch m ph Tam Giang Cu Hai, D n IMOLA
(2006).

[10]. Tiu Chun Vit Nam (2001), Sa bt xc nh hm lng nitrat phng


php kh cadimi v o ph ( phng php sng lc), H Ni.

41

Ti liu ting Anh


[11]. Afaf Ghaleb Hafiz Abu Dayeh (2006), Determination of Nitrate and Nitrite
Contentin Several Vegetables in Tulkarm District, Faculty of Graduate Studies,
An Najah National University, pp. 7 - 10.
[12]. B. Luckas (2007), Determination of Nitrite and Nitrate in Fruit Juices by UV
Detection, Anal. Chem, pp. 1 - 4.
[13]. Greenberg A. E., Trussell R. R., Clesceri L. S. (1985), Standard methods for the
examination of water and wastewater, 16th, Ed., APHA, USA, pp. 233 243.
[14]. Keiro Higuchi and SojiMotmizu (1999), Flow-injection pectrophotometric
determination of nitrite and nitrate in biological sample, Analytical sciences,
15.
[15]. Katrina M. Miranda, Michael G. Espey, and David A. Wink (2001), A Rapid,
Simple Spectrophotometric Method for Simultaneous Detection of Nitrate and
Nitrit, pp. 63.
Ti liu internet
[16].

http://songthan.info/chi-phan-mem-download/430332/vai-tro-cua-phu-gia-thucpham-download.htmL

42

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