Professional Documents
Culture Documents
1.3. X l s b khi ly mu
1.3.1. Ti sao phi x l s b
Nhiu loi mu khi tch ra khi mi trng thc t, cc cht trong mu c th b thay i, b mt
hay b phn hy v th cn phi x l mu s b nhm mc ch l:
- Gi v bo ton c cht phn tch khng b mt do cch hin tng
+ S tng tc ha hc, t phn hy ca cht
+ s thy phn ca cc cht
+ S sa lng ca cht
+ S hp ph vo dng c cha mu
- Phc v cho di chuyn d dng v khng h hng mu
- Bo qun khng lm thay i thnh phn mu v cht phn tch
- Phc v cho bo qun c d dng v an ton sau khi ly
1.3.2. Cc loi mu cn x l s b: nhng loi mu ca cc cht sau y cn x l s b:
- Mu phn tch cc kim loi nng d thy phn
- Mu phn tch cc anion km bn
- Mu phn tch cc cht d b phn hy
- Cht phn tch l cc cht d b hp ph vo thnh bnh cha
- Mu phn tch mt s ch tiu sinh hc, nm mc
- Mu xc nh cc ng vt ph du
- Mu xc nh cc loi trm tch
1.3.3. Cc phng php x l s b
1.3.3.1. Phn tch kim loi v anion
- X l dng c: trng cc dng c trc tin bng mt dung dch ph hp nht, nc ct
hay acid long, dng cht no ty thuc vo cht phn tch, sau phi lm kh ht
dung mi trng
- X l mu khi ly: v d
+ X l bng acid HCl hay HNO3 (kim loi nng, cho 1 L mu)
+ X l mu bng kim NaOH long (kim loi kim, anion CN-, H2S,)
+ Mu xc nh pH (cc loi)
+ X l bng formol, alcohol (cc loi mu xc nh ch tiu sinh hc)
+ X l bng kh tr, sch
1.3.3.2. Phn tch cc cht hu c
Nhm cc cht thuc loi sau:
- Cc cht d b anh sang tc dng v phn hy
- Cc cht phi gi lnh (v d ly mu phn tch vitamin A trong mu)
- Cc cht d b oxyhoa hay kh
- Cc cht d b mt do chuyn ha sang cht khc, do t oxyhoa kh
- Cc cht d bay hi, thng hoa
- Cc cht d ng t, sa lng, bm vo thnh bnh cha ng,
y l nhng mu phi x l mu s b khi ly bo v chng bng mt cch ph hp cho
mi cht. V d: bo ha kh CO2 hay N2 cho cc cht d b oxy trong khng kh ph hy.
1.3.3.3. Cc i tng sinh hc
Vic ly mu ca cc i tng sinh hc yu cu gi rt nghim ngt cc iu kin. Nu
khng cc vi sinh vt, nm mc s b cht, hay bin dng khng cn ng vi thc t. Mt s loi
phi c nh chng bng mt dung mi hu c thch hp. V d cc loi mu sau y:
- Vi sinh vt, vi khun, nm mc
- Cc ch tiu sinh ha, COD, BOD, DO,...
- Cc mu y hc (phn tch kim loi v cc cht hu c c hi)
- Sinh vt l lng
- Cc cht l lng
G, PTFE
G, PTFE
G, PTFE
G, PTFE
G, PTFE
G
G
Cl-, SO42CN-
P, G
P, G
Nitrite
SO32H+ (pH)
Kim loi (II, III)
Hg
Cr(VI)
Kim loi kim
H acronitril
P, G
P, G
P, G
P, G
P, G
P, G
P, G
G, PTFE
H benzidines
H clor hu c
H dioxim
Halo ether
Nitro-aromatic
Du, m
Thuc tr su hu c
v phosphor hu c
H PCBs v phthalates
ethers
Chlor hu c
Radiological test
G, PTFE
4 oC
40 ngy
G, PTFE
G, PTFE
H2SO4, pH < 2, 4 oC
HNO3, pH < 2, normal
28 ngy
6 thng
48 gi
28 ngy
24 gi
3 thng
20 ngy
24 gi
36 thng
14 ngy
7 ngy
7 ngy
45 ngy
40 ngy
40 ngy
28 ngy
28 ngy
trang b, phng php, cc quyt nh v cch ly mu, thi gian, a im, tn sut thch hp, cng
tc kim tra cc hot ng ly mu. chnh l ni dung ca QA/QC trong ly mu. V vn
ny cn c mt s quyt nh c th thc hin theo cc ni dung sau y:
- Chun b nhn s ph hp
- Lp k hoch theo mc ch kho st v ly mu
- La chn a im, vng, v tr ly mu cho i tng cn ly
- Xc nh c kiu v cch ly mu cho i tng cn ly
- Xc nh tn xut v thi gian ly mu
- La chn phng php ly mu
- Chn v chun b cc dng c thch hp cho ly mu
- Chn cch x l s b khi ly mu (nu cn)
- La chn dng c cha, ng hay gi v bo qun mu
- Xc dnh v chn cc cch vn chuyn mu thch hp
- Cng vic lp bo co, bn giao mu v h s lu tr
l nhng vn chung, cnc c phng php v quy trnh ly mu c th c trong cc
tiu chun ca quc gia v quc t. Mi ngi khi thc hin ly mu u phi nm vng cc quy
trnh o, cc vn ny c th tham kho mc ph lc cui chng ny.
ng thi theo cc khi nim nu trn, cng tc ly mu phn tch phi bao gm cc vn
sau y, bt u t lc chun b i ly mu cho n khi thu c mu em v v bo qun chng.
- QA/QC i vi tt c ngi thc hin ly mu
- QA7QC trong k hoch ly mu
- QA/QC i vi cc phng php, trang b v dng c ly mu
- QA/QC i vi ha cht phc v ly mu
- QA/QC i vi cc loi dng c ng, cha v bao gi mu
- QA/QC i vi cc hot ng ly mu, ghi chp h s ly mu
- QA/QC i vi cng tc chuyn ch mu v phng th nghim
- QA/QC i vi cng tc bo qun v lu gi mu sau khi ly c
Lm tt tt c cc vn ny tc l chng ta ly c mu phn tch tha mn c tt c cc
yu cu ca ly mu. Ngha l trong mi hot ng ca cng tc ly mu phn tch t lc bt u
chun b n lc ly c mu mang v v bo qun chng, hay phn tch ngay ti hin trng khi
cn thit. Ton b mi quan h ca cc cng vic ny c th m phng theo s hnh sau:
Bng XX: cc phng php tiu chun ly mu phn tch
STT
01
02
03
04
05
06
K
hiu
tiu
chun
TCVN 5994-1995
TCVN 5996-1995
TCVN 5998-1995
TCVN 5999-1995
TCVN 6000-1995
ISO 5667-13-1993
Ly mu cho ch tiu no
Hng dn ly mu nc h ao
Hng dn ly mu nc sng sui
Hng dn ly mu nc thi
Hng dn ly mu nc bin
Hng dn ly mu nc ngm
Ly mu nc thi v bn
Ghi ch
Vic phn chia theo cch ny, chng ta thy ch mt loi cng cha nhiu th mu khc
nhau v tnh cht, v c, hu c ln ln V th phn loi ny c th rt khng khoa hc v kh
xem xt khi cn chn cc phng php x l mu phn tch cc cht cn thit.
2.2.3. Phn loi theo nhm ngnh
- Mu nng nghip:
+ Cc cy ci, tho mc
+ Cc loi hoa qu, rau c, sn phm nng nghip ti sng
+ Cc loi phn bn, t trng trt
- Mu cng nghip
+ Mu cng nghip than v in
+ Mu cng nghip ha cht
+ Mu cng nghip du kh v tng hp hu c
+ Mu cng nghip thc phm
- Mu dn dng v sinh hot
+ Cc loi mu sinh hot hng ngy ca ngi v ng vt to ra
+ Cc loi mu bnh vin
- Cc loi mu t nhin n khong, qung, t
Cc phn loi ny khi mi nhn tng l chi tit nhng khi xem xt v cch x l mu th mi thy
nhiu iu khng hay. Do theo quan im ca ha phn tch th cch u tin l tng i n
gin v thch hp nht.
2.3. Trang b x l mu phn tch
2.3.1. Yu cu ca trang b v iu kin x l mu
x l mu ty iu kin v phn loi mu, v cht phn tch m c s la chn cc trang b v
phng php x l mu cho ph hp. Ngy nay trn th trng c nhiu loi trang thit b khc
nhau dng cho x l mu t n gin n phc tp v hon ton t ng. Song bt k loi thit b
no cng phi m bo cc vn sau:
a. Thc hin QA/QC trong x l mu
b. Cn ch thm cc yu cu c th ti thiu l:
+ Theo yu cu ca mc phn tch v cp hm lng
+ Ph hp vi mi loi mu, nu n gin, ph thng th cng hay
+ Khng lm mt v khng lm nhim bn cho mu phn tch
2.3.2. Cc loi dng c n gin
- Cc loi cc un v ng nghim
- Cc loi chn, bt nung (s, thch anh, kim loi qu)
- Cc loi ng nghim un c (chu nhit)
- L nung, t sy
- Cc loi h chit lng-lng, lng-rn v lng-kh
- Bnh Kendan cc loi
2.3.3. Cc loi trang b hon chnh
- Cc loi h chng ct khc nhau
- H thng bnh Kendan ng kn, hi lu v t ng
- Cc loi l vi song (n gin v hon chnh)
- Cc h ca k thut chit lng lng lien tc
- Cc h ca k thut chit lng-rn (chit pha rn)
- Cc h ca k thut chit kh-rn (chit pha kh)
- Cc h ca k thut chit siu m
- Cc trang b ca k thut chit Soxhlet
- Cc loi thit b thng hoa mu
- Cc loi khc
Song mt iu phi nh rng d chn cch no, dng c no th cng phi m bo x l
c mu mt cch tt nht m khng lm mt cht phn tch, khng lm nhim bn v a c
cht cn xc nh v dng ph hp nht cho phng php phn tch chn. Cc loi trang thit b
ny s c ni n trong cc k thut x l mu c th.
2.4. Khi qut v bn cht cc k thut x l mu
X l mu phn tch l mt qu trnh phc tp, c ha hc, ha l hay vt l v ha hc
phc tp kt hp chuyn cc cht hay cc nguyn t hay cc ion cn xc nh c trong mu phn
tch ban u, a chng v dng tan trong mt dung mi thch hp nh nc hay dung mi hu c
sau c th xc nh c n theo mt phng php phn tch thch hp. Tuy th, nhng vic
x l mu phn tch l c thc hin theo rt nhiu k thut c nguyn l, bn cht, c ch vt l
v ha hc c khi rt khc nhau ty theo mi loi mu v yu cu phn tch nhng cht no. V d
nh x l bng acid, x l bng kim, hay tro ha kh, tro ha t, s chit lng lng, chit pha
rn, chng ct. Song mt cch i th th chng ta c th phn loi theo mt s nguyn tc, c
ch da theo cc c ch sau y ca ha hc, ha l v vt l trong qu trnh x l mu.
V th trong chng ny ch trnh by v cc nguyn tc, bn cht ca cc k thut x l
mu phn tch, m khng i su vo cu to v cch vn hnh cc loi dng c hay trang thit b.
l cc k thut sau y:
- K thut v c ha t
- K thut v c ha kh
- K thut v c ha kh t kt hp
- Cc k thut chit thng thng
- K thut chit Soxhlet (kiu thng v t ng)
- K thut chit pha rn, pha kh
- K thut chit siu m
- Cc k thut chng ct (thng, chn khng, li cun)
- K thut ln men nu
- K thut thng hoa cht phn tch
- K thut chlor ha mu bng kh chlorine mi sinh
- K thut in phn
Trong cc k thut , mi k thut ch thch hp cho mt s cht hay mt nhm cht nht
nh v mi k thut cng c mt s u v nhc im ring v phm vi ng dng ca n. Ngha l
khng th c mt cch x l mu no l ph hp c cho mi loi mu, mi cht phn tch. V th
ty theo yu cu c th ca cng vic phn tch m ngi lm phn tch phi nghin cu, xem xt
v la chn mt k thut no cho thch hp trong c s ca mnh v m bo c kt qu phn
tch ng n v tin tng. Tc l phi thc hin QA/QC trong cng vic x l v trong cng vic
phn tch t ra.
Trong khi x l hay phn hy mu, c th c rt nhiu qu trnh vt l v cc phn ng ha
hc c th xy ra ng thi, ty thuc vo mi loi nn mu, thnh phn ca mu v cc cht c
cho vo dng thc hin x l mu. Ni chung mt cch tng th c th c cc qu trnh sau y
xy ra:
- S ph v mng li cu trc ca cht mu ban u, gii phng cc cht phn tch, a
chng v dng dung dch di dng cc mui tan ca cc ion.
- Qu trnh oxy ha kh lm thay i ha tr, chuyn i dng, lm tan v cu trc vt
cht mu ban u gii phng chat phn tch v dng hp cht tan trong dung dch.
- S t chy, ph hy cc hp cht hu c v mn, to ra kh CO 2, NO2, SO2, nc v
gii phng cc kim loi trong cht mu hu c ban u, a chng v dng cc hp cht
hay mui d tan trong acid.
- S to ra cc hp cht phc bn, t phn ly lm tan cht mu, to ra cc phc dng tan
ca cc cht phn tch trong dung dch (dung mi) qua m ha tan cht mu.
- To ra hp cht d bay hi, lm mt i anion ca cht mu ban u lm mu b phn
hy to ra cc cht khc tan trong dung dch acid hay kim hay acid.
S kt tinh hay kt ta cht phn tch di dng hp cht khc, lm cht phn tch c
tch ra khi mu ban u v chuyn sang hp cht mi m chng ta ly c chng ra
khi mu ban u.
Nh vy trong qu trnh x l v phn hy mu c th c cc qu trnh vt l, cc phn ng
ha hc xy ra nh phn ng oxy ha kh, phn ng thy phn, phn ng to phc, phn ng ha
tan, phn ng kt ta ca cc phn t cht mu vi dung dch acid phn h mu v cc phn t
cht c trong mu vi nhau.
l ni chung tt c cc kh nng c th c, song trong thc t, ty thuc vo thnh phn
v bn cht ca mi loi mu, loi cht phn tch, phng php phn tch, ha cht x l mu m c
nhng qu trnh xy ra vi loi mu khi x l. Sau y chng ta s xem xt mt s k thut x l
mu c v ang c dng.
2.4.1. K thut v c ha t (x l t)
2.4.1.1. Bng acid mnh, c v c tnh oxy ha
a. Nguyn tc v bn cht
Dng acid mnh HCl, H2SO4 hay cc acid mnh, c c tnh oxy ha mnh (HNO3, HClO4)
hay hn hp 2 acid (HNO3-H2SO4) hay 3 acid (HNO3-H2SO4-HClO4) phn hy mu trong iu
kin un nng trong bnh Kendan hay trong ng nghim. Lng acid thng gp 20-15 ln lng
mu, ty loi mu. Thi gian ha tan mu (x l) trong cc h h, bnh Kendan thng t vi gi
ti vi chc gi, cng ty loi mu, bn cht ca cc cht. Cn nu trong l vi song h kn (c p
sut) th ch cn 50-60 pht. Di tc dng ca acid c v nhit , y cng c cc qu trnh vt
l v ha hc sau y xy ra, v d:
- S ph v mng cu trc ca cht mu, gii phng cc cht phn tch a chng v dung
dch di dng cc mui tan.
- Qu trnh oxy ha kh lm thay i ha tr, chuyn i dng, lm tan v cc cht mu,
gii phng cht phn tch v dng mui tan trong dung dch.
- Nu x l mu hu c phn tch kim loi th c s t chy, ph hy cc hp cht hu
c v mn to ra kh CO 2, nc v gii phng cc kim loi trong cht mu hu c v
dng mui v c tan trong dung dch.
- To ra hp cht d bay hi, lm mt i anion trong phn t cht mu lm mu b phn
hy to ra cc hp cht khc tan trong dung dch.
- Nh vy trong qu trnh x l mu y cng c th c cc phn ng ha hc xy ra
nh phn ng oxy ha kh, phn ng thy phn, phn ng to phc, phn ng ha tan,
phn ng kt ta ca cc phn t cht mu vi cc acid dng phn hy mu v cc
cht c trong mu vi nhau.
Sau y l mt vi v d th hin cc qu trnh trn, khi x l mu phn tch khc nhau:
- v d 1: ha tan qung mangan oxide bng HNO3 v H2O2.
+ MnO2 + HNO3 + H2O2 Mn(NO3)2 + H2O + NO2.
- V d 2: ha tan qung st bng vng thy
+ Fe2O2.Fe3O4 + HNO3 + HCl FeCl3 + NO2 + H2O
- v d 3: x l mu thc phm, rau qu
+ Nn mu + HNO3 + H2SO4 CO2 + H2O + mui kim loi ha tan
Cc dung dch acid dng ha tan v x l mu: trong x l t, ngi ta thng dng cc
loi dung dch acid c, song tt nhin chn loi no l ty thuc vo bn cht ca nn mu v cht
phn tch tn ti trong mu
- Cc n acid c HCl, H2SO4, HNO3, HClO4.
- Hn hp 2 acid: cng thy, HNO3-H2SO4, HF-H2SO4
- Hn hp 3 acid: HCl-HNO3-H2SO4, HNO3-H2SO4-HClO4.
- Hn hp 1 acid v 1 cht oxy ha: H2SO4-KMnO4, HNO3-H2O2,
- Hn hp 2 acid v 1 mui: HNO3-H2SO4-KMnO4,
Nhit khi x l mu l ph thuc vo nhit si ca acid dng phn hy mu. Khi
dng hn hp acid th nhit x l mu cn ty thuc thm vo thnh phn ca hn hp acid v
thng thng nhit ny nm trong gii hn gia nhit si ca acid d si nht v acid kh si
cht. i vi nhng mu kh phn hy, ta phi dng cc acid hoc hn hp cc acid c nhit si
cao v tnh oxy ha mnh.
Acid
HCl HNO3 H2SO4 H3PO4 HClO4 HF
C (%)
36
65
98
78
72
40
o
Tsi ( C) 110 121
340
213
203
120
b. Cc loi hay kiu x l t
Vic x l mu theo phng php t c th c thc hin trn cc loi trang thit b khc
nhau, ty thuc vo kh nng phng th nghim v tnh cht ca mu
- Trong iu kin thng, thit b n gin
+ Trong cc thy tinh, un nng trn bp in hay un cch thy.
+ Trong bnh Kendan thng
+ Trong bnh Kendan c hi lu
- Trong ni p sut cao: mu v acid c t trong cc hp kn sau t trong
+ T sy, bp cch ct, l nung
+ Luc trong ni nc si hay du si
- Trong l vi song (gm h kn v h)
+ H n gin: h bnh h hay h kn nhng khng iu khin nhit , p sut
+ H nhiu bnh, t ng hon ton: h h (c gim st nhit ) v h kn (c gim st
nhit v p sut).
Trong cc kiu x l trn, k thut x l t vi acid c c tnh oxy ha mnh trong bnh
Kendan hay trong l vi sng h kn ang c s dng rng ri, ph bin. cc nc pht trin, l
vi sng h kn c s dng mt cch ph bin trong x l mu do n trit , nhanh, hn ch mt
cht phn tch v nhim bn v tiu tn t ha cht.
c. Mt s th d v x l mu theo cch tro ha t
- V d 1: Ha tan mu kim loi v hp kim Cu hay Al bng acid HNO 3; ly 1 g mu
nghin nh (hay dng phoi bo) vo bnh Kendan, tm t bng vi git nc ct, thm 10 mL
HNO3 65%, 4 mL H2SO4 98%, lc u, cm phu nh vo bnh Kendan, un nh cho mu si v
phn hy cho n khi dung dch mu trong. S ha tan y lm thay i ha tr v trng thi
ca Ca, Al kim loi trong hp kim, chuyn chng thnh mui tan trong dung dch. Phn ng ha
hc chnh xy ra l:
Al + HNO3 Al(NO3)3 + NO2 + H2O
Cu + HNO3 Cu(NO3)2 + NO2 + H2O
- V d 2: ha tan mu thp chrome bng hn hp acid HNO 3 v HCl hay HNO3 v H2SO4.
Ly 0.5 g mu nghin nh (hay dng phoi bo) vo bnh Kendan, tm t bng vi git nc ct,
thm 15 mL HNO3 65%, 4 mL H2SO4 98%, lc u v un nh cho mu si v phn hy, cho n
khi dung dch mu trong. Qu trnh ny c s oxy ha kh ca Cl v N sinh ra Cl mi sinh phc
v cho phn hy mu. Di tc ng ca hn hp acid c ny v c nhit , mng li kim loi
b ph v, cc kim loi chuyn vo dung dch di dng cc mui tan. Phn ng ha hc chnh xy
ra y l:
Ni-Cr-Fe + HNO3 + HCl Ni(NO3)2 + Fe(NO3)3 + Cr(NO3)3 + NO2 + H2O
- V d 3: ha tan qung Mn oxide bng hn hp HNO 3-H2O2. xc nh Mn v cc tp
kim loi trong qung ny, qu trnh ha tan c s oxy ha kh, chuyn Mn(IV) v Mn(II) tan trong
dung dch. Ly 1 g mu qung nghin nh vo bnh Kendan, tm t bng vi git nc ct,
thm 15 mL HNO3 65%, 2 mL H2O2 30%, lc u v un nh cho mu si v phn hy cho n khi
dung dch mu trong. Phn ng ha hc xy ra l:
MnO2 + HNO3 + H2O2 Mn(NO3)2 + H2O + O2
- V d 4: X l mu rau qu bng hn hp hai acid HNO 3-H2SO4, trong bnh Kendan,
xc nh cc kim loi nng, c hi, nh Cd, Cu, Fe, Mn, Ni, Pb, Zn. Ly 5 g mu nghin mn v
trn u vo bnh kendan, thm 60 mL HNO3 65%, 5 mL H2SO4 98%, lc u v un nh cho mu
si v phn hy, cho n khi dung dch mu trong khng mu (6-8h ty loi mu). Chuyn dung
dch mu vo cc un 250 mL, lm bay hi ht dung dch acid cho n khi cn mui m, ngui,
nh mc bng dung dch HCl 2% thnh 25 mL. Trong qu trnh x l ny, cc nguyn t kim loi
c. Vi v d ng dng
- V d 1: ha tan oxid nhm bng dung dch naOH 10% nng. Ly 0.5 g mu dng bt vo
bnh Kendan, tm t bng vi git nc ct, thm 10 mL NaOH 10%, un si ha tan mu. C
ch y l chuyn trng thi tinh th rn oxid sang dng ion tan trong dung dch theo phn ng:
Al2O3 + NaOH NaAlO2 + H2O
- V d 2: Ha tan qung silicate bng dung dch NaOH 20% nng. Ly 0.5 g mu dng bt
vo bnh Kendan, tm t bng vi git nc ct, thm 15 mL NaOH 20%, un si ha tan mu.
C ch y l chuyn trng thi tinh th rn sang ion tan trong dung dch v bn dng mui
Na2SiO3 theo phn ng
SiO2.nX + NaOH Na2SiO3 + H2O + nX
d. u nhc im v phm vi ng dng
K thut tro ha t ny cng c u im l khng lm mt cc cht phn tch nht l cc
nguyn t v hp cht d bay hi. Nhng m c mt nhc im ln nht l tn nhiu kim tinh
khit cao, thng phi dng gp t 10-15 ln nhu cu cn thit mi c th x l c mu v v vy
kh nng nhim bn rt cao. Sau khi x l mu, phi loi b lng kim d bng cch trung ha vi
acid, song li lm long mu. y l mt phn vic kh khn v mt nhiu thi gi v cng hay l
nhim bn mu. V th cch ny ch c dng cho mt s trng hp khi khng c cch la chn
no khc. V d khi phn hy mu xc nh cc anion v c nh halides, nitrate, phosphate,
sulfate... trong cc di tng khng x l c bng phng php acid.
2.4.1.3. X l t trong l vi sng
a. Nguyn tc
K thut x l mu t trong l vi sng thc cht cng l phn hy mu khi un nng bng
dung dch acid mnh, c c tnh oxy ha hay bng dung dch kim c nng nh nu bn trn.
Tc nhn phn hy l cc acid v nng lng nhit cung cp cho mu do hin tng truyn nhit do
i lu t mt ngun nhit bn ngoi. i vi l vi sng, nng lng un nng mu c cung cp
bng bc x vi sng tn s cao, cc phn t mu u c nhn nng lng ng u v trc tip t
ngun vi sng, ph v cu trc nn mu t pha trong ra, v th qu trnh x l mu nhanh v trit
hn. Hn na, i vi h kn cn c p sut cao v nhit cao do hiu qu cao v rt nhanh
li tn t acid so vi phn hy iu kin thng trong bnh Kendan. Cc qu trnh vt l v ha
hc xy ra khi x l mu bng vi sng cng tng t nh cch x l mu t thng thng khc
nhng c tc nhanh hn v trit hn.
b. Trang thit b
Vic x l mu trong l vi sng c th thc hin trong h bnh h hay trong h bnh kn. Cc
thit b ny ngy nay hin din trn th trng vi nhiu loi, kch c khc nhau, phc v cho
tng mc ch nht nh. Cc thit b ny li c nhiu kiu rotor khc nhau c th thay i c
nh rotor phn hy mu, rotor lm bay hi dung mi v acid, rotor dng chit, rotor dng
sy mu, rotor dng nung mu (nh l nung cao tn)... v th rt thun tin cho cng vic x l
mu phn tch. K thut ny c s dng ph bin cc nc pht trin.
c. Cc v d ng dng
T cc v d trnh by trong mc 2.4.1.1.c v 2.4.1.2.c u c th thc hin trong cc h
h. Tuy vy nu c thc hin trong h kn th lng ha cht tiu hao ch khong v thi gian
rt ngn xung cn t 40-60 pht m hiu qu x l li trit hn, t mt cht phn tch hn.
2.4.2. K thut v c ha kh (x l kh)
2.4.2.1. Nguyn tc v qu trnh xy ra trong x l
K thut tro ha kho l k thut nung x l mu, song thc cht ch l bc u tin ca
qu trnh x l mu v sau khi nung, mu b cn li cn phi c ha tan (x l tip) bng dung
dch mui hay dung dch acid ph hp chuyn cht phn tch vo dung dch cho mt phng
php phn tch chn. Qu trnh nung x l mu c th khng thm cht ph gia, cht bo v hoc
c thm cc cht ny vo mu tr gip qu trnh x l c xy ra nhanh hn, tt hn v hn ch
mt mt cht phn tch.
Trong qu trnh nung x l mu, c th c cc qu trnh vt l v ha hc sau y xy ra ty
theo bn cht, thnh phn ca mi loi mu v ph gia thm vo, v d nh
Ph gia
KOH-Na2O2
KOH-Na2O2
KNO3-HNO3
KNO3-HNO3
Nhit
550-650
500-600
550-600
550-600
550-650
550-650
550-650
500-550
500-550
500-550
500-600
chuyn n sang dng khc, n gin hn, d ha tan vo dung dch acid hay kim trong cc giai
on x l mu k tip. Sau y l mt vi v d:
- V d 1: tro ha kh mu rau qu xc nh kim loi (Na, K, Ca, Mg, Cd, Co, Cr, Cu, Fe,
Mn, Ni, Pb, Zn). Cn 5 g mu vo chn thch anh, em sy kh t t cho n khi mu kh en, ri
em nung 3 gi u nhit 450oC, sau nng ln 530-550oC cho n khi mu ht than en, thu
c mu tro trng. Ha tan tro thu c trong 10 mL dung dch HCl 15%, un nh cho tan ht,
nh mc thnh 25 mL bng nc ct. Cc nguyn t Cd, Cu, Pb Zn s b mt mt t (8-15%) khi
nung.
- V d 2: Tro ha kh mu du m (du th) xc nh cc kim loi (Na, K, Ca, Mg, Cd,
Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn). Cn ly 5 g mu vo bt hay cc thch anh, un nh trn bp in
hay sy kh mu t t sau em nung nhit 450 oC trong 3 gi, sau nng ln 530-550 oC
n khi ht than en, thu c mu tro trng. Ha tan tro thu c trong 15 mL dung dch HCl
18%, un nh cho tan ht, nh mc thnh 25 mL bng nc ct. Cc nguyn t Cd, Cu, Pb Zn s b
mt mt t (8-15%) khi nung.
Theo cch ny thng thng mt s nguyn t trong mu b mt khi nung nh Cd (10-18%),
Cu (7-12%), Pb (8-15%)... v lng mt i li khng n nh, khng kim sot v khng ch c
trong qu trnh nung. S mt mt ny cng nhiu khi nhit nung mu cng cao hay thi gian
nung cng lu v gy v vy l mt ngun sai s ln cho kt qu phn tch. Nh v d 1, nu nung
mu nhit 530oC, Cd v Pb s mt t 8-10% nhng khi nung 600 oC th Cd v Pb s mt n
gn 20%.
2.4.2.4. Tro ha c ph gia v cht chy bo v
Nung x l mu c cht ph gia v cht bo v cng l qu trnh x l mu s b nh tc
ng ca nhit c thm tng tc h tr ca cht ph gia, thng l cht chy, acid c..., trong
thi gian nht nh ph v cu trc tinh th dng ban u ca mu phn tch, chuyn chng sang
dng d ha tan hn trong acid hay kim. Khi c cht chy, nhit nung thng thp hn so vi
khi khng c cht chy, thi gian ngn hn song li trit hn nht l cc mu phn tch c matrix
bn, chu nhit hay mu hu c th tc dng ca cht ph gia v bo v li cng quan trng. Trong
hai v d trn, nu x l mu c cht bo v th khng xy ra s mt mt cc nguyn t nh trn.
V d 1: tro ha mu rau qu xc nh kim loi (Na, K, Ca, Mg, Cd, Co, Cr, Cu, Fe, Mn,
Ni, Pb, Zn) dng cht ph gia. Cn 5 g mu vo chn thch anh, thm 1 g KNO 3, 5 mL HNO3 65%,
trn u v un nh cho mu si u v cho n kh en. Nung mu nhit 450 oC trong 3 gi,
sau nng ln 500-530oC, n khi ht than en, thu c mu tro trng. Ha tan tro thu c
trong 15 mL dung dch HCl 18%, un nh cho tan ht, nh mc thnh 25 mL bng nc ct.
V d 2: Tro ha kh mu du m (du th) xc nh cc kim loi (Na, K, Ca, Mg, Cd,
Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) dng cht ph gia l 2 g KNO 3 v 10 g sodium benzene sulfonate.
Cn ly 5 g mu vo bt hay cc thch anh, thm cht ph gia, un nh cho mu si v cho n kh
en, sau nung nhit 450 oC trong 3 gi, sau nng ln 500-530oC n khi ht than en, thu
c mu tro trng. Ha tan tro thu c trong 15 mL dung dch HCl 18%, un nh cho tan ht,
nh mc thnh 25 mL bng nc ct.
V d 3: Tro ha mu sa xc nh kim loi (Na, K, Ca, Mg, Cd, Co, Cr, Cu, Fe, Mn, Ni,
Pb, Zn), dng cht ph gia l 8 mL H 2SO4 45% v 2 g KNO3 hay LiBO2. Ly 5 g mu vo chn
thch anh, thm cht ph gia, trn u, sy cn thn cho mu kh (mu d b si bt v bn ra
ngoi) v thnh than en sau nung nhit 450 oC trong 3 gi, sau nng ln 500-530 oC n
khi ht than en, thu c mu tro trng. Ha tan tro thu c trong 15 mL dung dch HCl 18%,
un nh cho tan ht, tip tc un ui acid cho n khi cn mui m. nh mc thnh 25 mL bng
HCl 2%.
- V d 3: X l mu tm, cua, c... xc nh cc kim loi (Na, K, Ca, Mg, Cd, Co, Cr,
Cu, Fe, Mn, Ni, Pb, Zn). Ly 5 g mu vo chn thch anh, thm 5 mL H 2SO4 98% v 5 mL
Mg(NO3)2 5% trn u. x l mu t s b: sy mu cn thn trn bp in cho mu kh v
thnh than en sau nung nhit 400-450oC trong 3 gi, sau nng ln 500-530oC n khi
ht than en, thu c mu tro trng. Ha tan tro thu c trong 15 mL dung dch HCl 1:1, un nh
cho tan ht, tip tc un ui acid cho n khi cn mui m. nh mc thnh 25 mL bng HCl 2%.
y l dung dch mu dng xc nh cc kim loi nu trn bng phng php ph hp thu phn
t hay ph nguyn t
2.4.3.3. u nhc im v phm vi p dng
u im ca k thut ny l tn dng v kt hp cc u im ca phng php x l mu
ut v kh
- Hn ch s mt mt ca mt s cht phn tch
- S tro ha l trit , sau khi ha tan tro s c dung dch mu trong
- Khng phi dng nhiu acid tinh khit
- Thi gian x l mu nhanh hn tro ha t
- Khng phi ui nhiu acid d, hn ch nhim mi trng, nhim bn mu
- Ph hp cho nhiu loi mu khc nhau xc nh kim loi
- Khng cn trang thit b phc tp, hin i, t tin
Cch ny c ng dng ch yu x l mu cho phn tch cc nguyn t kim loi v mt
s anion v c nh Cl-, Br-, sulfate, phosphate... trong cc loi mu sinh hc, mi trng, mu hu
c, v c. Cch x l ny khng dng c cho xc nh cc cht hu c. Trong cc phng th
nghim bnh thng, khng c trang b l vi sng th cch x l ny vn l mt phng php
thch hp, n gin m vn m bo c c kt qu tt.
2.4.4. Cc k thut chit
2.4.4.1. C s, nguyn tc v iu kin ca s chit
a. Nguyn tc v c s ca s chit
Chit da trn c s s ha tan (hay phn b) khc nhau ca cht phn tch vo trong hai
dung mi khng trn ln vo nhau. Tc l cht phn tch tan tt trong dung mi ny nhng li
khng tan tt trong dung mi kia, ngha l s phn b ca cht trong hai dung mi l rt khc nhau
nh m chng ta ly c cht phn tch ra khi mu ban u, chuyn n vo dung mi chng ta
mong mun sau xc nh n trong dung mi chng ta va chit vo. Nh th yu t quyt nh
s tch v x l mu y l h s phn b ca cht phn tch trong cc phase v iu kin thc
hin chit tch.
b. H s phn b ca cht
H s phn b l mt hng s vt l (hng s nhit ng) c trng cho s chit. N cho ta
bit s phn b (hay ha tan) ca cc cht phn tch trong hai dung mi (hay 2 pha) khng trn ln
vo nhau theo t l hay mc no. Nu gi tr hng s ny cng ln th s phn b cng khc
nhau nhiu v vy cng thun li cho s chit tch cc cht. V d cht X c phn b vo hai
dung mi khng trn ln vo nhau (A v B) th h s phn b ny c xc nh theo biu thc sau
C ( A)
KD X
C X (B )
Trong CX(A) v CX(B) l nng cht X trong hai dung mi A v B. Nu h s phn b
KD > 99/1 xem nh cht X chuyn hon ton vo dung mi A. l iu kin ca qu trnh chit
ly cht phn tch ra khi nn mu.
c. Cc iu kin ca s chit
c c kt qu chit tt, qu trnh chit phi c cc iu kin v t c cc yu cu
sau y
- Dung mi chit phi c tinh khit cao, m bo khng lm nhim bn cht phn tch
- Dung mi chit phi ha tan tt cht phn tch, nhung khng ha tan tt cc cht c
trong mu
- H s phn b chit phi ln s chit c trit
- Cn bng chit nhanh t, thun nghch gii chit c tt
lm kh bng Na2SO4 khan v xc nh cc cht chlorphenol trong pha n-hexane bng HPLC hay
GC-MS.
- V d 2: chit cc hydrocarbon thm, a vng t mu b thi ma ng. Ly 20 g mu
nghin nh, trn u cho vo bnh chit, thm 30 mL n-hexane cha 20% dichloromethane (DCM),
25-30 g Na2SO4 khan, y np bnh, vn cht, b vo rotor chit. Tin hnh chit trong 20 pht,
yn 5 pht sau ly bnh mu ra khi rotor v tch ly phn dung mi n-hexane, v xc nh cc
cht cn phn tch trong pha n-hexane-DCM bng HPLC hay GC-MS.
- V d 3: Chit ly mt s ha cht BVTV t mu t hay mu rau qu (nh
Methylparathion, sumithion, diazinon...). Ly 20 g mu t c nghin nh, trn u vo bnh
chit, thm 20 mL EtOAc, trn u, t bnh vo h my chit, tin hnh chit trong 40 pht,
ngui yn trong 10 pht, tch ly pha hu c c cha cc cht BVTV. Di pha hu c qua ct sc
k hp ph cha Al2O3-than hot tnh-Na2SO4 khan. Ra gii ct ny bng 40 mL EtOAc. Dung
dch ra gio dng xc nh cc cht BVTV bng GC, HPLC hay GCMS.
K thut chit ny c u im l nhanh, trit v hiu sut cao nhng i hi phi c trang
b h thng chit siu m hon chnh, c rotor chit cho mi cch chit khc nhau.
2.4.4.2.4. K thut chit pha rn.
a.Nguyn tc v iu kin
- Nguyn tc chung: nguyn tc ca qu trnh chit pha rn l mu trng thi lng hay hi
cn cht chit dng rn, th ht nh, xp (5-10 m ng knh). Cht chit gi l pha tnh v
c nhi vo ct sc k nh (kch thc 10 x 1 cm hay dung lng 5-10 mL). Cht chit l cc ht
silica trung tnh, cc ht nhm oxide hay silicagel alkyl ha nhm OH - bng nhng nhm alkyl
mch thng C2, C4, C8 hay C18... hay nhm phenyl. N c ch to trong iu kin tng t nh
iu kin ch to pha tnh ca HPLC nhng cc ht ny c xp ln hn v din tch b mt xp
thng t 50-200 m2/g. Khi x l mu, dung dch cha cht phn tch c di ln ct c cha pha
rn ny. Pha tnh s tng tc vi cc cht mu v gi li mt nhm cht phn tch, cn cc nhm
khc s i ra khi ct cng vi dung mi hoa tan mu. Nh th nhm cht phn tch tn ti trn pha
tnh v s c ra gii ra khi ct bng mt dung mi thch hp. Cc cht chit pha rn c th
c ch to theo cc loi sau y
+ Cht hp ph pha thng (silica trung tnh v aluminium oxide)
+ Cht hp ph pha ngc (silica c alkyl ha nhm OH)
+ Cht c kh nng trao i ion (cationit, anionit, cp ion)
+ Cht ry hay sng lc phn t theo kch thc
+ Cht hp ph pha kh-rn (purge and trap extraction)
Chnh v c nhiu loi pha tnh nh th nn k thut chit pha rn cng c nhiu c ch v
qu trnh ng hc khc nhau, theo bn cht mi c ch . Sau y l mt s c ch v iu kin
chn h chit (pha tnh v pha ng). Ni chung pha tnh trong chit pha rn cng tng t nh pha
tnh trong HPLC.
- Cc iu kin ca chit pha rn
Qu trnh chit y thc cht vn l qu trnh phn b ca mt cht trn hai pha tnh (pha
rn) v ng (pha lng hay kh) trong nhng iu kin nht nh v nhit , pH, tc chy dung
mi qua ct chit. Nh vy h s phn b K D ca mt cht trn hai pha cng l yu t quyt nh
hiu qu ca s chit. Tm li phi c cc iu kin sau y
+ Pha tnh hp ph hay trao i chnn lc vi mt nhm cht phn tch
+ H s KD phi ln
+ Qu trnh chit xy ra nhanh, t cn bng nhanh
+ Qu trnh chit phi c tnh thun nghch cao ra gii thun li
+ S chit c thc hin trong mt iu kin nht nh, cng n gin cng tt.
a. Cc kiu chit v c ch chit pha rn
- Chit theo c ch hp ph pha thng
Trong kiu chit ny, pha rn l cc silica trung tnh, c b mt phn cc. N o dng tt vi
cc cht mu khng phn cc v t phn cc. l s tng tc hp ph ca pha tnh: cht chit rn
trong ct. Ty theo bn cht v cu trc phn t mi nhm cht phn tch v bn cht hp ph ca
silica trung tnh v cc iu kin thc hin s tch m nhm cht phn tch no b pha tnh hp ph
v b gi li trn ct. C ch ca s tng tc ny hon ton tng t nh c ch tng tc trong
HPLC pha thng. Sau y l minh ha ca tng tc
Dung mi ra gii cht phn tch trong loi ny thng l cc dung mi hu c khng hay t
phn cc v k nc hoc hn hp ca chng theo t l thch hp. V d: n-hexane, n-heptane,
CCl4, CHCl3, CH2Cl2, benzene... Cc dung mi ny c gi l pha ng v phi ha tan tt cht
phn tch.
+ V d 1: Chit x l mu xc nh nhm hp cht chlorophenol trong nc. Acid ha
250 mL mu n pH 2 bng H2SO4 10%, sau di mu ny qua ct chit loi LASi-5 tc 4
mL/pht. Di qua ct 10 mL nc ct, gii hp bng 40 mL acetonitril hay dichloromethane v xc
nh bng HPLC hay GC.
+ V d 2: Chit x l mu xc nh mt s hydrocarbon thm a vng (PAHs) hay mt
s pesticides trong nc thi. Acid ha 250 mL mu bng H 2SO4 2% n pH= 6, lc b cn nu c,
di dung dch ny qua ct loi SiOH vi tc 4 mL/pht. Gii hp cht phn tch bng ACN hay
DCM. Xc nh cc cht phn tch bng GC hay HPLC
- Chit theo c ch hp ph pha ngc
Trong kiu chit ny, pha tnh l Silica c alkyl ha nn c b mt khng phn cc. N
tng hp tt vi cc cht khng phn cc hay phn cc km. Tng tc gia cht phn tch vi
pha tnh v pha ng ty thuc vo bn cht ca cht phn tch ( phn cc, kch thc, cu trc),
pha tnh ( phn cc, din tch b mt ring...) v pha ng ( phn cc, thnh phn, tc
chy...). Tng tc ny tng t vi tng tc ca pha tnh-pha ng-cht tan gp trong HPLC pha
o. Dung mi ra gii s dng trong kiu chit pha rn pha o ny l cc dung mi c tnh phn
cc nh nc, acetonitril, methanol, ethylacetate... Minh ha cc tng tc pha tnh-pha ng-cht
tan nh sau
+ V d 1: Chit x l mu xc nh nhm hp cht chlorophenol trong nc. Acid ha
250 mL mu n pH 2 bng HNO3 1N, ly tm b cn, sau di mu ny qua ct chit loi Baker10 TPE-phenyl column, 6 mL No. 7095, tc 3 mL/pht. Ra ct bng 10 mL HNO 3 0.01N, gii
hp bng 40 mL acetonitril v xc nh bng HPLC, GC hay GCMS.
+ V d 2: chit x l mu xc nh nhm cc kim loi (Cd, Co, Cr, Cu, Fe, Ni, Pb, Zn)
trong nc: thm 1 mL thuc th Ultrex- 8-oxyquinolin vo 250 mL mu, chnh pH 8-9 bng NH 3
1N, lc u ri di mu qua ct Baker-10 C18 SPE 5 mL vi tc 2-4 mL/pht. Ra ct bng 10
mL nc ct. Gii hp cc phc kim loi trn ct bng 10 mL MeOH, xc nh cc nguyn t trong
pha MeOH bng AAS. xc nh kim loi, nn tro ha t dch chit MeOH bng HNO 3. C th
thay thuc th ny bng Na-diethyldithiocarbamate 0.1% trong EtOH.
+ Chit x l mu xc nh mt s thuc BVTV trong nc. Ly 250 mL mu nc,
chnh pH 5, lc b cn. Di dung dch qua ct chit loi LR C 18 vi tc 4 mL/pht. Ra ct bng
10 mL nc ct, ht chn khng 5 pht. Ra gii cc cht BVTV trong ct bng 20 mL EtOAc. Ly
dch ra gii ny di qua ct th 2 cha Na 2SO4-...-than hot tnh, ra gii bng 10 mL EtOAc. Lm
bay hi dung dch thu c bng dng kh Nitrogen n khi dung dch snh, nh mc thnh 2 mL
bng EtOAc. Xc nh cc ha cht BVTV bng GC hay GCMS.
- Chit theo c ch trao i ion v cp ion.
Nguyn tc: da trn c s ca qu trnh tng tc ca cht phn tch vi ion i (ca cht
trao i ion-pha tnh). Cht phn tch s b lu gi trn pha tnh v s c ra gii bng mt pha
ng thch hp.
Backer 10 SPE-P, 6 mL vi tc 3-4 mL/pht. Gii hp cht phn tch bng 20 mL DCM. Xc
nh bng HPLC hay MKEC.
u nhc im v phm vi s dng chit pha rn
Chit pha rn l k thut chit mi ra i, ang pht trin v c ng dng trong khong
vi chc nm tr li y nht l cc nc tin tin. Nhiu loi pha rn v cc dng c chit khc
nhau c thng mi ha. Cc pha rn thung da trn nn silica hot ha, bin tnh tng
chn lc v dung lng trao i. K thut ny c mt s u nhc im sau
+ c tnh chn lc vi cc hp cht hu c v th thch hp cho phn tch vt
+ Thao tc n gin, nhanh hn cc k thut khc
+ Trong qu trnh chit c c s lm giu cht phn tch.
2.4.4.5. K thut chit by hp ph dng kh (chit rn-kh)
2.4.4.5.1. Nguyn tc chung
K thut ny da trn c s l mt nhit thch hp, khi thi mt dng kh tr nng (Ar
hay He) vo dung dch mu, mt nhm cht phn tch s b bay hi v li cun theo dng kh tr
n ct hp ph, ti y cht phn tch s b gi li trn pha tnh trong khi cc cht khc i qua. V
th v bn cht n cng l s chit gia hai pha kh v rn theo c ch hp ph. gii hp, ct
c gia nhit v cht phn tch bay ra khi b mt pha tnh v theo dng kh tr i vo my phn
tch (GC) hay hp thu vo mt dung mi hu c ph hp cho cc php phn tch khc nh HPLC
hay UV-VIS. Phng php ny c dng cho cc mu rn v lng, bn hay b thi nhng ch
thch hp cho cc cht c nhit bay hi thp (< 150 oC). Nh th ty vo vic la chn pha tnh
v nhit m ngi ta c th tch c cc nhm cht ra khi nhau sau phn tch chng theo
cc phng php ph hp. Cch ny rt thch hp cho vic tch chit cc cht hu c trong cc mu
rn (bt, bn, nho). Tt nhin vic trc tin phi nh ha cc mu ny bng mt dung mi thch
hp nh nc hay mt dung mi hu c nng c nhit i si cao. Pha tnh thng l cc cht hp
ph da trn silica nh silica trung tnh hay bin tnh tng t nh cc h NP-HPLC, RP-HPLC.
2.4.4.5.2. Cc kiu chit, trang thit b v v d
Theo k thut ny trang thit b cng c hai loi l h n gin v h hon chnh, t ng
c theo chng trnh nh sn. Kh mang s dng l Ar, He hay N2 tinh khit > 99.9%.
V d 1: chit mt s hydrocarbon d bay hi trong cc loi nc hay mu rn: ct hp ph
l pha rn DSC 25x1 cm (DSC: diphenylene oxide polymer-silicagel-coconut charcoal 1:1:1), mu
c gi trong bnh cu v dng Ar thi qua bnh mu vi tc 0.8-1.0 mL/pht a cht phn
tch vo ct hp ph. Cc cht hu c benzene, bromobenzene, bromomethane, bromoethane,
chloromethane, chloroethane, ethylbenzene s c hp ph vo ct ny. Vic gii hp c tin
hnh bng dng kh tr Ar gia nhit 180oC v dn trc tip vo my GC, GCMS hay vo mt
dung mi ph hp nh n-hexane dng xc nh bng mt phng php khc.
+ V d 2: chit ly mt s hp cht pesticides d bay hi trong cc loi nc hay mu rn,
bn (method 502,2b). Ct hp ph l pha rn LC2 25x1 cm. Mu c gi l 150 oC v dng kh Ar
thi qua mu vi tc 0.8-1 mL/pht chuyn cht phn tch vo ct hp ph. Gii hp cc cht
hp ph bng dng Ar nhit 200oC trc tip vo my GC hay GCMS.
K thut ny rt thch hp cho vic x l cc loi mu xc nh cc cht hu c c nhit
si < 200oC v d bay hi trong cc loi mu rn, bn, b thi. N c u im l chn lc cho
mi nhm cht ty vo cht php ph, thch hp cho cc phng php phn tch HPLC, GC, GCMS
nn c s dng ch yu cho phn tch vi lng cc cht hu c trong cc loi mu khc nhau.
2.4.5. K thut chng ct
2.4.5.1. Nguyn tc chung: chng ct l k thut tch da trn s khc bit v im si ca cc
cht theo c th ly c mt cht hay mt nhm cht da vo mc sai bit v nhit si,
trang thit b v iu kin (nhit ) chng ct. C nhiu kiu chng ct khc nhau nh:
b. Trang b v cch thc hin: x l theo k thut ny, phi trang b h thng my
c quay v my bm chn khng iu chnh nhit v p sut thp thch hp. Sau y l mt
vi v d.
- V d 1: chng ct lm bay n-hexane ly cht phn tch nhm Vitamin A v Caroten
bng ct quay chn khng. Ly 10 g mu nghin nh vo phu chit, thm 20 g Na 2SO4 khan,
100 mL dung mi THF hay n-hexane. Lc k trong 10 pht, lc qua phu Busner, ly dung dch cho
vo v cho vo bnh ct ca my c quay ct cho dung mi bay hi n khi cn b m, ngui.
Ha tan b ny trong 5 mL MeOH, dung dch ny dng xc nh Caroten bng HPLC.
- V d 2: Chng ct tch MeOH tinh khit t MeOH k thut (nguyn liu th) v thu ly
b cn li xc nh mt s tp cht c trong MeOH k thut. Ly 200 mL MeOH vo bnh chng
ct, lp h thng c quay chn khng v chng ct MeOH cho n khi dch lng trong bnh chng
ct cn khong 2 mL, ngui. Ly b ny ha tan trong 5 mL DCM, ly tm hay lc tch b cn.
Xc nh cc tp cht hu c trong dch lc bng GC, GCMS hay HPLC.
2.4.6. K thut ln men mu
2.4.6.1. Nguyn tc v c im
Chuyn hay ha tan mu vo trong nc thnh dung dch hay th huyn ph, thm 10-15
mg men xc tc, v chnh mi trng bng acid hay kim, hay mui acetate cho ph hp (pH= 7-8),
ri a mu vo bung ln men nhit t 37- 40 oC cho n khi mu trong hon ton, tc l
cc kim loi chuyn vo dung dch. Thi gian ln men t 7-10 ngy. Kiu ny rt thch hp cho
phn tch xc nh cc kim loi trong cc mu ng ma, nc ngt gii kht, bia, ru, cc mu
nc qu chn, cam, chanh...
K thut ny c cc u nhc im v c im nh sau:
+ K thut n gin, d thc hin
+ Khng tn km ha cht nhng cn t m iu chnh c nhit
+ Mt thi gian
+ Ch p dng c cho mt s loi mu
+ K thut ny c dng ch yu l xc nh cc kim loi trong mu dng lng nh nc ngt
gii kht, cc loi nc qu, ng hay dung dch ng.
2.4.6.2. Cc phng php v v d:
- V d 1: Xc nh lng vt kim loi nng trong ng vng hoa m, nc ngt. Ha tan 5
g ng vo 80 mL nc ct, chnh pH =7-8, un nng n 40 oC, thm men xc tc, y knh ng
h, trong t m duy tr 37- 40 oC cho ln men trong 7 ngy. Thm 10 mL HCl 35%, un si, ly
tm ly dch trong, lm bay hi cn mui m. nh mc thnh 25 mL bng HCl 2%, xc nh kim
loi nng trong dung dch ny.
2.4.7. Phng php pha long bng dung mi thch hp.
2.4.7.1. Nguyn tc v c im
Nguyn tc: chn mt dung mi thch hp ha tan tt cht mu pha long n theo mt t
l nht nh sau phn tch bng mt phng php chn. V d phn tch cc kim loi kim th
trong du nht. Pha long mu 20 ln bng dung mi MIBK, xc nh bng AAS hay ICP-AES.
Cc lm ny kh n gin, d thc hin v khng cn trang thit b phc tp nhng li ch thch hp
cho mt s trng hp hn ch nh hm lng cht phn tch trong mu ln c th vn xc
nh c khi pha long. Qu trnh pha long s gim thiu cc yu t nh hng n cht phn tch
nhu thnh phn nn, nht, cn khng tan...
2.4.7.2. Cch thc hin v v d
- V d 1: Xc nh cc kim loi kim th (Ca, Ba, Sr) trong du bi trn hay du nhn. Pha
long mu 20 ln bng MIBK, ly tm b cn. Dch lc em xc nh bng FAAS hay ICP-AES.
C th pha long mu bng CCl4 v xc nh bng GFAAS.
-V d 2: Xc nh cc hydrocarbon thm trong du m. Pha long mu du 25 ln bng nhexane v DCM. Lc u, ly tm ly dch trong. Xc nh bng GC hay GCMS.
- V d 3: pha long mu huyt thanh bng nc ct xc nh kim loi K, Na, Ca, Mg.
+Xc nh K, Na: ly 0.2 mL huyt thanh pha long bng nc ct thnh 20 mL.
+ Xc nh Ca, Mg: ly 0.2 mL huyt thanh pha long bng nc ct thnh 10 mL.
+ Xc nh Cu, Zn: ly 0.25 mL huyt thanh pha long bng nc ct thnh 1 mL.
2.4.8. K thut thng hoa ly mu phn tch.
2.4.8.1. Nguyn tc chung: da trn c s tnh cht hay c im ca cht phn tch c kh nng
thng hoa trong mt iu kin nht nh khi x l mu tch n ra khi matrix. V d kim loi Hg,
Ga.. ra khi mu t , qung hay b thi rn.
2.4.8.2. Trang b, cch x l v v d.
Cc trang b phc v cho kiu thng hoa cng c nhiu loi khc nhau, t n gin ti hon chnh
v t ng theo chng trnh.
- V d: thng hoa ly Hg trong mu qung. Cho 1 g mu qung nghin mn vo trong bnh
hai bu hay cc thng hoa. Thm 0.6 g Fe kim loi, 1 g CaO khan, lc nh cho ng nht. Lm lnh
phn ng thch anh n 10oC bng b iu nhit, nc hay tuyt carbonic v t nng bu cha
mu trn n kh, quay u bnh mu Hg thng hoa cho n khi hn hp mu trong bnh c mu
sm. t thm 2 pht na. Khi thng hoa, Hg s bm vo ng thch anh c lm lnh hay
y bnh ngng to thnh mt lp sng bng. p b bu cha mu bn di, ly phn ng thch
anh c Hg bm vo, ha tan Hg trong HNO31:1 nng 80oC, lc u, yn 30 pht, thu dung dch
ny v thm 0.1 mL K2Cr2O7 1%, nh mc thnh 25 mL hay 50 mL. Dung dch ny dng xc
nh Hg bng phng php ph hp thu nguyn t ha hi lnh.
- Cch ny c th c dng th x l cc loi mu t , qung, rc thi rn, bn,ct...
xc nh Hg hay Ga hay cc hp cht c kim d bay hi.
2.4.9. K thut chlor ha mu.
2.4.9.1. Nguyn tc: Nguyn tc ca k thut ny l sc mt dng kh chlorine qua mu un nng.
Mu thng c nghin nh dng nh ha trong nc hay acid long. nhit v p sut thch
hp, cc kim loi trong mu s tng tc vi kh chlorine v chuyn v cc mui chloride tan trong
dung dch. Ha tan mu vo acid long tch cc cht phn tch dng mun tan.
2.4.9.2. Trang b, cch tin hnh v v d
H thng chlor ha mu gm cc b phn
- Bung cha mu chlor ha
- H iu ch kh chlorine, h thng iu khin tc v dn kh chlorine mi sinh vo
bung cha mu
- H thng ha tan mui thu c sau khi chlor ha
- H thng iu khin nhit cho bnh mu v b ngng t hi mu thng hoa
V d: Chlor ha qung t him ly cc nguyn t t him trng thi mui chloride
tan trong dung dch nc. Ly 5 g mu nghin nh vo bnh chlor ha, thm 50 mL nc ct, lc
u, acid ha n pH 1 bng HCl 5%, lc k, un si hn hp, t trn ni cch thy hay bp iu
nhit, dn kh chlor mi sinh vi tc 0.8 mL/pht vo bnh mu. Duy tr phn ng trong 30 pht,
ngui, thm 10 mL HCl 10%, un si v lc ly dung dch mu. y l dung dch cha mui
chloride cc nguyn t t him c trong qung.
2.4.10. Kt ta hay ha lng nhit thp
2.4.10.1. Nguyn tc chung: chn iu kin thch hp v trong mt dung mi kt ta phn on
cht phn tch di dng mt hp cht khng tan, sau tch chng ta khi hn hp mu v x l
kt ta theo cch ph hp vi phng php phn tch la chn. Phng php ny gip tch ng
thi cng lm giu cht phn tch.
Nguyn tc: Phng php x l mu ny da trn c s tnh cht hp ph hay phn b hay trao i
ca cc cht lu gi cht phn tch ln pha tnh trong ct sc k, tch chng ra khi mu
ban u. Sau dng mt dung mi thch hp (pha ng) ra gii v ha tan chng vo pha
ng tch n ra khi ct sc k ri xc nh chng trong pha ng ny bng mt phng php
ph hp. V d nh AES, AAS, UV-VIS, HPLC, GC, EC...V th trc ht phi a mu phn tch
v dng dung dch c th np vo ct sc k. S tch sc k y l da trn hai pha khng trn
vo nhau, pha tnh l cht rn, pha ng l cht lng (dung mi ra gii). V th n cng tng t
nh k thut chit pha rn. Ch yu y l sc k hp ph dng pha tnh l silicagel hay
aluminium oxide xp c tnh cht sc k tch cc nhm cht.
iu kin:
- Chn pha tnh c tnh cht chn lc cho mt nhm cht phn tch
- Chn pha ng ph hp cho cht cn x l thu c n tt nht
- Cn bng trong qu trnh sc k phi c tnh chn lc tt
- Chn iu kin sc k thch hp gp c cht phn tch vo mt nhm hay tch
tng cht th cng tt.
b. Trang b, cch x l v v d
Mun thc hin chit kiu ny chng ta phi c cc h sc k ph hp. C th ch l cc ct
tch n gin, v cng c th l cc h thng t ng hon chnh. N bao gm trc ht l ct sc
k cha pha tnh nh silicagel hay aluminium oxide xp c kh nng hp ph hay trao i ion vi
mt hay mt nhm cht phn tch. Th hai l cc dung mi ha tan mu phn tch v dung mi
ra gii cht phn tch ra khi ct sc k. Ty loi cht phn tch m chng ta c th chn h pha
sc k hp ph hay h pha trao i ion tch cht phn tch.
- V d 1: X l mu xc nh cc alkaloid. Ha tan mu v chuyn mu v dng lng
trong mt dung mi hu c thch hp, v d nh n-hexane hay acetonitril... Sau ly c dung dch
ny hay ch 1 th tch nh nht nh np vo ct sc k hp ph c pha tnh l aluminium oxide vi
tc chy 1 mL/pht cht phn tch c pha tnh hp ph v gi li. Sau dng n-hexane
hay hn hp n-hexane+DCM, t l 1:1, ra gii cht phn tch ra khi ct sc k vi tc 1.5
mL/pht. Nh vy cht phn tch s c ra gii v tan vo pha ng ra gii, v tin hnh xc
nh n trong pha ng ra gii ny bng mt trong cc phng php nh HPLC, GC, CEC...
- V d 2: X l mu xc nh cc chlorophenol trong mu t. Ha tan v chuyn mu
v dng lng trong mt dung mi thch hp v d THF, lc ly dung dch THF, lm kh bng mui
Na2SO4 khan. Ly dung dch hu c ny np vo ct sc k hp ph c pha tnh l pha ngc C 18
vi tc chy l 1 mL/pht cht phn tch c pha tnh lu gi. Sau dng 10 mL pha ng
(ACN-THF) ra gii cht phn tch ra khi ct sc k vi tc chy l 1.5 mL/pht. Nh vy
cht phn tch s tan vo pha ng ny v xc nh n trong pha ng thu c bg mt trong cc
phng php nh HPLC, GC, CEC...
- V d 3: X l mu xc nh lng vt kim loi nng trong nc bin. Ly 250 mL
mu, chnh pH =5, lc b cn, sau np ln ct sc k trao i loi DOWEX-50X12-Na (150 x
8mm) vi tc chy 1 mL/pht cc ion kim loi c gi li trn ct sc k. Khi mu chy ht,
di qua ct 5 mL nc ct hai ln. Sau dng 20 mL dung dch HNO 3 3M ra gii cht phn
tch ra khi ct sc k vi tc 1.5 mL/pht. Nh vy cht phn tch s tan vo dung mi ra gii
v c th c xc nh bng phng php phn tch ph hp nh AAS, AES, UV-VIS. Cch ny
c th dng cch x l mu cho vic xc nh cc kim loi trong cc loi nc mt, nc thi...
- V d 4: X l mu xc nh mt s anion trong mu nc (halides, nitrate, sulfate...).
Ly 250 mL mu, chnh pH =7.5-8, lc b cn, sau np ln ct sc k trao i loi DOWEX50A12-OH (150 x 8mm) vi tc chy 1 mL/pht cc ion kim loi c gi li trn ct sc k.
Khi mu chy ht, di qua ct 5 mL nc ct hai ln. Sau dng 20 mL dung dch NaOH 1M
ra gii cht phn tch ra khi ct sc k vi tc 1.5 mL/pht. Nh vy cht phn tch s tan vo
dung mi ra gii v c th c xc nh bng phng php phn tch ph hp UV-VIS hay sc k
ion.... Cch ny c th dng cch x l mu cho vic xc nh cc kim loi trong cc loi nc mt,
nc thi...
2.4.12.2. Sc k giy v sc k bn mng
a. Nguyn tc chung: qu trnh sc k y l da trn c s l trong h dung mi nht nh
th s phn b hp ph ca cc cht trn nn silicagel xp c trng trn bn thy tinh hay
polymer cng hay s hp ph ca cc cht trn bn giy xp sc k khc nhau. Trong qu
trnh sc k, cc cht s di chuyn khc nhau to ra mi cht c mt vng ring trn bn
mng v tch ra khi nhau. V th mi c tn l sc k bn mng v sc k giy.
b. Cc trang b, cch tin hnh v v d
Mun thc hin tch chit theo kiu ny chng ta phi c cc trang b sc k. N bao gm:
- Cc loi bn mng sc k l cc cht silicagel hay aluminium oxide xp c kh nng hp
ph cc cht phn tch.
- Cc h dung mi ha tan mu phn tch
- Cc bnh chy sc k v dung mi chy sc k
- Pha ng chy sc k
Ty loi cht phn tch, m chng ta c th chn h pha sc k giy hay sc k bn mng.
Bn mng hay giy sau khi chm ln c lm kh v ngm vo dung mi trong bnh sc k. Lc
ny cc cht phn tch s chy theo dung mi t di ln trn v to thnh tng vng cht. Sau khi
chy sc k, tch cc vng mu xc nh cc cht hay xc nh bng cc phng php ph phn
t (hp thu hay phn x).
- V d 1: tch mt s alkaloid t c bnh vi bng sc k bn mng. Ly 10 g mu
nghin mn v bnh nn, thm 20-25 g Na 2SO4 khan, thm 40 mL n-hexane, lc mnh 10 pht,
lng, lc hng ly dung dch. Lm bay hi dung mi bng dng kh nitrogen sch cho n khi cn
b m. Ha tan b ny trong 2 mL DCM v ly dung dch mu ny chy sc k bn mng (loi MA450) trong h dung mi A (30% n-hexane+10%THF+10%DCM+pH=6) tch ly cc alkaloid,
sau ly bn mng, tch ly vng cht, ha tan n trong mt dung mi thch hp nh DCM v xc
nh chng. Hay h dung mi khc thch hp.
- V d 2: Tch ly hp cht carotene t mu rau qu bng sc k bn mng. Ly 10 g
mu nghin nh v bnh chit, thm 25 g Na2SO4 khan, 40 mL THF, lc chit 10 pht, lc ly
dung dch THF, ct quay chn khng cho n cn b, ha tan b ny trong 5 mL n-hexane. Ly
dung dch mu ny chy sc k lp mng trn bn silica (loi Si-MA 560).
Nghin trn
Cn a g
Bng phng
php Kendan,
l vi sng
X l
Phn hy
V c ha t
thm acid
Lm bay hi acid d
C th chit lm giu,
tch nhm trc khi phn tch
AES
AAS
UV VIS
HPLC
Ion CA
ECA
c th thm cc
cht cn thit
Ly mu
Nghin trn
Cn a g
X l
Phn hy
V c ha kh
Ha tan tro b trong acid
c th thm
cht bo v
Lm bay hi acid d
C th chit lm giu,
tch nhm trc khi phn tch
AES
AAS
UV VIS
HPLC
Ion CA
ECA
c th thm cc
cht cn thit
Ly mu
ng nht, trn u
Ly V mL
C th lc b cn
X l mu bng
- Cc cch chit tch
- Chng ct
- Sc k
- C c
....
C th chit lm giu,
tch nhm trc khi phn tch
AES
AAS
UV VIS
HPLC
Ion CA
ECA
c th thm cc
cht cn thit
Ly mu
Nghin, trn u
Cn a g
Nh ha, ha tan bng
dung mi ph hp
X l mu bng
- Cc cch chit tch
- Chng ct
- Sc k
- C c
....
C th chit lm giu,
tch nhm trc khi phn tch
UV VIS
HPLC
GC
GCMS
HVCEC
Fluorescen ce
c th thm cc
cht cn thit
So snh kt qu tro ha t v kh
Ng
CX Cch tro ha
t
Pb
10
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
Ph gia bo v
Khng
H2SO4
HNO3
Mg(NO3)2
Mg(OAc)2
Hg
Zn
As
Cu
10
10
10
10
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4+K2Cr2O7
Kh
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
Khng
Khng
HNO3
H2SO4
Mg(NO3)2
Khng
HNO3
H2SO4
Mg(NO3)2
Khng
HNO3
H2SO4
Mg(NO3)2
Nhit
(oC)
Recovery
(%)
450
550
650
450
550
650
450
550
650
450
550
650
450
550
650
97-100
93-98
90-94
97-100
93-95
71-83
97-99
95-97
90-96
97-99
97-99
70-84
98-99
92-95
91-96
97-98
95-98
92-94
450
550
78-80
90-94
92-94
0
0
550
550
550
550
97-100
94-102
96-100
87-96
93-97
97-100
98-99
550
550
550
550
96-98
97-99
91-98
80-88
80-84
90-96
92-99
550
550
550
550
99-100
99-101
99-100
86-92
94-96
95-97
97-99
Co
Cd
Sb
Cr
Fe
Au
10
10
10
10
10
10
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
t:
HNO3+HClO4
HNO3+HClO4+H2SO4
HNO3+H2SO4
Kh
Khng
HNO3
H2SO4
Mg(NO3)2
Khng
HNO3
H2SO4
Mg(NO3)2
Khng
HNO3
H2SO4
Mg(NO3)2
Khng
HNO3
H2SO4
Mg(NO3)2
Khng
HNO3
H2SO4
Mg(NO3)2
Khng
HNO3
H2SO4
Mg(NO3)2
550
550
550
550
98-100
98-100
97-99
97-99
90-96
96-99
97-100
550
550
550
550
98-100
98-100
97-100
86-94
82-91
93-97
94-97
550
550
550
550
94-98
95-98
97-99
90-94
92-96
94-98
96-97
550
550
550
550
97-100
98-100
98-100
94-98
95-98
97-99
95-98
550
550
550
550
96-100
98-100
97-100
94-98
96-99
97-100
98-100
550
550
550
550
95-98
97-99
97-99
93-99
87-98
97-99
97-100
Ion
Tan
trong
nc
Silica-C8
Silica-C18
Silica-phenyl
Silica-CN
Cation
IEC
Anion
IEC
Silica-SO3H
Silica-COOH
Silica-RCOOH
Silica-NH2
Silica-C6H5SO3H
Silica-NH2, -NH
Amin t cp
Silica-diol
Silica-CN
Silica-NH2
....
Silicagel
trung
tnh
Khng Phn cc
ion
NPC
Phn
cc LSC
trung bnh
Khng phn RPC
cc
Vt ion kim Tan trong nc
loi
IEC
Silica-C8
Silica-C18
Silica-phenyl
Silica-CN
Silica-SO3H
Silica-COOH
Silica-C6H5SO3H
Dung mi ra
gii cht phn
tch
n-hexane
CHCl3
Aceton
Methanol
n-hexane
CHCl3
Ethylacetate
Methanol
Nc
Methanol
Aceton
Acetonitril
n-hexane
m
Phosphate
Acetate
Amoni
Acid long
Baz long
CHCl3
n-hexane
Aceton
Methanol
Nc
Methanol
Acetonitril
THF...
m
Acid long
Baz long
chn. Do vi ccloi mu rn, c, trc tin mu phi c gia cng hay chun b s b theo
cc cch sau ty thuc vo mi loi mu:
- Chuyn mu v dng bt (mu mui, oxt, qung, t , x than..)
- Chuyn mu thnh phi bo (mu thp, hp kim..)
- X l chuyn mu thnh dng huyn ph, bt nho (sinh hc, rau qu..).
- Dng lng ng u (mu nc cc loi hay du).
Sau y l mt vi v d ng dng cck thut nu chng 2 x l mu ly cc kim
loi xc nh chng:
3.1.3.1 K thut x l t (v c ho t)
y l k thut dng cc acid mnh, c hay hn hp ca cc acid mnh c tnh cht cxi ha
mnh,hoc dung dch kim c ha tan, phn hy mu, nhit phng hay khi un si trong
bnh kendan, hay chng ct hi lu. Nh vy mu phn hy y nh c acid mnh v nhit
thch hp. Nhit si y l nhit ca acid dng x l mu. V th nu cn c nhit si
cao th dng acid c nhit si cao nh acid H 2SO4. Nhit si ph thuc vo bn cht ca acid.
V d acid HCl c nhit 115 oC V th ty yu cu ca mu m chn acid no hay thnh phn hn
hp no t c nhit si ca hn hp phn hy musao ph hp.
Trc khi x l cc mu qung, t cn nghin thnh bt. Cc mu kim loihp kim
cn phay thnh phoi bo mng, cc mu sinh hc, rau qu phi thi nh hay xay nhuyn v dng bt
nho ng nht. Sau c th s dng 1 acid c hay cc loi hn hp sau y phn hy mu.
V d:
- Dng 1 acid mnh nh: HNO3, H2SO4, HCl..
- Dng nc cng thy (HCl+ HNO3) v hn hp 2 acid c tnh oxi ha mnh nh HNO 3 +
H2SO4), (HClO4+ H2SO4 )..
- Dng hn hp 3 acid mnh
- Dng mt acid mnh v 1 peroxid (HNO3+H2O2)
- Dng dung dch kim mnh nh: NaOH 20%, KOH 20%.
- Dng hn hp acid v cht to phc (HCl + tartaric cho Sb)
Sau y l mt vi v d x l mu xc nh mt s kim loi nh Cd, Co, Fe, Mn,Ni,Pb,
Zn.
V d 1: Phn hy hp kim nhm: ly 1,000g mu (dng phi bo) vo bnh kendan, thm
0,5mL nc ct, lc u thm 20mL HNO3 1/1, lc u cm vo bnh mt phu nh, un nh cho
mu phn hy n khi no trong l c. Chuyn ton b mu vo cc un, lm bay hi nh
ui ht acid ra cn li mui m. nh mc thnh 25mL bng acid HCl 2%.
V d 2: Phn hy qung t him nhm nh: ly 2g qung dng bt vo bnh kendan, thm
1,0mL nc ct, lc u thm 40mL nc cng thy, lc u cm vo bnh mt phu nh, un nh
cho mu phn hy n khi no trong l c. Chuyn ton b mu vo cc un, lm bay hi nh
ui ht acid ra cn li mui m. nh mc thnh 25mL bng acid HCl 2%.
V d 3: Phn hy qung st: ly 1g qung dng bt vo bnh kendan, thm 1mL nc ct,
lc u thm 20mL nc cng thy, lc u cm vo bnh mt phu nh, un nh cho mu phn
hy n khi no trong l c. Chuyn ton b mu vo cc un, lm bay hi nh ui ht
acid ra cn li mui m. nh mc thnh 25mL bng acid HCl 2%. y l dung dch mu xc
nh cc nguyn t trong qung st v xc nh c st.
V d 4: Phn hy qung Mangan: ly 1g qung dng bt vo bnh kendan, thm 1mL nc
ct, lc u thm 20mL HNO3 65%, 4mL H2O2 15%, lc u cm vo bnh mt phu nh, un nh
cho mu phn hy n khi no trong l c. Chuyn ton b mu vo cc un, lm bay hi nh
1.X l khng dng cht ph gia v cht chy. Ch nung mu nhit thchhp ph v cu
trc mng li tinh th ban u, lm cho mu d ho tan. Nhng cch ny thng t hiu qu, ch
c dng cho 1 s trng hpnn t c dng. V d
Qung H: LnCO3 F.xH2O Ln2O3 + H2O + CO2 + HF + Men Om
Qung st: Ferit.xH2O FeO + Fe2O3 + SO2 + H2O + Men Om
Qung Cu: CuS. xH2O CuO + SO2 + H2O + Men Om
2. X l c dng cht ph gia v cht chy: trn mu vi 1 cht chy hay hn hp cht chy, sau
nung mu nhit thch hp. cch ny c dng nhiu cho cho cc loi mu kh phn hy. cc
cht ny c th l:
- loi cht chy acid nh: NaHSO3, NaHCO3, NaH2PO4, pyrosunphate
- Loi cht chy kim nh: Na2CO3, KOH,NaOH, LiBO2, Na2O2, NaNO2
- Lai cht chy hu c nh C6H5SO3Na, SDS..
V d:
Qung H + NaHCO3 Ln2O3 + H2O + CO2 + HF + Men Om
t + LiBO2 + NaHCO3 Men Om + Na2SiO3 + H2O + Na2B2O7
3. Yu t quan trng khi x l theo k thut ny:
Phi chn c cc yu t thch hp sau y:
- Loi cht ph gia hay chy cn dng thch hp
- T l thnh phn gia cht chy v mu
- Nhit x l (nhit nung) thch hp v thi gian sy hay nung x l.
- Thi gian sy hay nung x l.
Sau y l vi v d c th ng dng k thut ny
+ V d 1: Phn hy qung t him nh Pasnesit: Cn ly 2,0 gam mu vo chn nung,
thm 2g Na2S2O7 + 1g NaHSO4, tm t bng 1 mL nc ct, sau em nung bt u t nhit
phng, 80 pht u t 250oC, sau nng ln 650oC v nung trong 50 pht. ngui v ly ra
x l theo phng php v c ha t bng hn hp acid (HNO3 + H2SO4) c hay cng thy theo
nguyn tc nh ni phn trn.
+ V d 2: Phn hy mu t trng trt. xc nh hm lng ton phn ca cc ion kim loi
(Li, Na, K, Ba,Ca, Mg, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, V, Zn) trong t. Cn ly 200g, t
c sy kh trong khng kh v nghin mn vo chn Pt hay chn thch anh, thm 2g LiBO 2, 1g
NaHCO3 trn u. em nung 650oC trong 45 pht, ngui, tm t bng nc ct sau x l
theo tro ha t c th bng cc hn hp sau, ty thuc cht cn xc nh:
-
HNH 3.3
+ V d 1: Phn hy qung t him nh, ly 2g mu dng bt vo cc Teflon, thm 10mL
cng thyhay hn hp (HNO3 + H2SO4 ) v 1 gam (NH4)2SO4. sau cho cc mu vo hp thp
kn chu p, y nt, vn chy v b hp mu vo t sy 180 oC. ngui chuyn vo cc un,
lm bay hi ht acid n khi cn mui m v nh mc bng dung dch HCl 2% thnh 50mL. l
dung dch xc nh cc nguyn t t him v cc kim loi khc c trong qung ny. Trc ht
tch tng t him dng kt tia mui oxalat, cn c dng xc nh cc nguyn t khc (Na,
K, Ca, Mg, Cu, Fe, Pb, Zn)
+ V d 2: Phn hy mu ha tan qung vng. Ly 2g mu dng bt vo cc Terlon, thm
30mL cng thy, 4mL H2SO4. Sau cho cc mu vo hp thp kn chu p, y nt, vn cht v
b hp mu vo t sy v sy 180oC trong 180 pht. ngui chuyn vo cc un, lm bay hi
ht acid n khi cn mui m v nh mc bng dung dch HCl 2% thnh 50 mL. l dung dch
xc nh Au v cc nguyn t loi khc khc c trong qung ny
+ V d 3: Phn hy mu qung crm. Ly 2g mu dng bt vo cc Teflon, thm 30mL
HNO3 65%, 5mL H2SO4 98%. Sau cho cc mu vo hp thp kn chu p, y nt, vn cht v b
hp mu vo t sy v sy 180 oC trong 180 pht. ngui chuyn vo cc un, lm bay hi ht
acid n khi cn mui m v nh mc bng dung dch HCl 2% thnh 50 mL. l dung dch
xc nh cc nh crm v cc nguyn t kim loi khc c trong qung ny
3.1.3.4 K thut x l mu trong l vi sng.
y cng l k thut x l t dng nng lng cao tn ca l vi sng phn hy t mu
trong mi trng ca 1 acid oxy ha mnh, hay hn hp ca hai hay 3 acid mnh, c v c tnh oxi
ha. N l k thut x l t trong l vi sng di tc dng ca nng lng cao tn nn hiu qu
cao v nhanh hn cch tro ha t bnh thng. C 2 cch ca k thut ny l x l p sut
thng (h m) v p sut cao (h ng kn). Ngy nay nhiu hng cung cp cc h l vi sng rt
tin li chop x l mu phn tch. C cc kiu x l t, x l kh, lm bay hi, chng ct
(xem chng 2).
Tt c cc v d x l t trong mc 3.1.3.1 v v d trong mc 3.1.3.3 v cch x l t
trong hp kn nu trn u c th thc hin trong l vi sng. Nhng acid th cn t hn. C th thc
hin 1 trong 2 cch sau ty theo c iu kin trang b bnh x l mu v h l vi sng.
+ Trong h m: mu trong bnh kendan hay bnh x l mu v t trong l vi sng c
iu khin c cng sut vi sng phn hy trong iu kin chn. Mu c phn hy nh
cc acid mnh v nng lng cao tn ca l vi sng nn s phn hy l nhanh v trit v tn t
acid hn khi x l t bnh thng (xem c ch hnh 3.3b).
V d 1: Phn hy qung t him nh. x l mu qung t him, ly 2g mu dng bt
vo bnh x l, thm 20mL cng thy v 0,5 gam (NH 4)2SO4, lc u. Sau cho bnh mu vo l
vi sng trong 90 pht. ngui chuyn vo cc un, lm bay hi ht acid n khi cn mui m v
nh mc bng dung dch HCl 2% thnh 50mL. l dung dch xc nh cc nguyn t t him
v cc kim loi khc c trong qung ny.
V d 2: Phn hy mu ha tan qung vng. Ly 2g mu dng bt vo cc vo bnh x l
hay ng nghim, thm 20mL cng thy, 0,5 gam (NH 4)2SO4.Sau cho cc mu vo l vi sng
trong 20 pht. ngui chuyn vo cc un, lm bay hi ht acid n khi cn mui m v nh
mc bng dung dch HCl 2% thnh 50 mL. l dung dch xc nh cc nguyn tvng bc v
cc nguyn t khc c trong qung ny
Trong h ng kn: mu phi trong bnh knh v chu p cao. Sau cng phn hy bng
hn hp nh trn. Nhng v h kn p sut cao. Nn s phn hy nhanh v trit hn, v lng
acid cn t hn. cc h thng x l mu theo cch ny hin nay cc hng c cung cp y , t n
gin n hon chnh, c chng trnh iu khin v t ng tt c.
V d 1: phn hy ha tan qung t him nh. x l mu qung t him, ly 2g mu
(dng bt) vo cc Teflon, thm 15mL cng thy, 0.5g. sau cho cc mu vo hp kn, y nt,
vn cht v b hp mu vo l vi sng trong 90 pht. ngui chuyn vo bnh nh mc v nh
mc bng nc ct thnh 50mL. l dung dch xc nh cc nguyn t t him v cc kim
loi khc c trong qung ny.
V d 2: phn hy ha tan qung vng. x l mu qung vng, ly 2g mu cho vo
cc Teflon, thm 25mL nc cn hy, 0.5g. sau cho cc mu vo hp kn, y nt, vn cht, b
mu vo l vi sng trong 60 pht. ngui cho vo bnh nh mc, v nh mc bng nc ct
thnh 50mL (c th chuyn mu ra cc un, lm bay hi,cn mui m, sau ha tan b v nh
mc bng acid HCl 2% th tt hn). l dung dch xc nh vng,bc v cc kim loi khac
trong qung ny
3.1.3.5.K thut chit lng-lng thng thng thng:
Nguyn tc, cc iu kin v trang b ca k thut chit c nu trong chng 2 mu
phn tch c trong dung mi nc, sau dng mt dung mi hu c thch hp chit cht tch
vo pha hu c dng hp cht tan tt trong dung mi hu c. V d chit cc kim loi nng t
m nc thi vo CHCl3 dng phc kim loi Me-APDC. xc nh cc kim loi nng (Cd, Co,
Cr, Cu, Fe, Mn, Ni, Pb, Zn) trong .
Cc trang b ca k thut chit ny l cc bnh chit hay phiu chit khc nhau(hnh 3,4).
N l cc dng c thy tinh ph thng ca phng th nghim nn khng mc tin. Sau y l mt s
v d v chit x l mu phc v phn tch cc cht.
V d 1: chit xc nh cc kim loi nng nng c hi(Cd, Co, Cr,Cu, Fe, Mn, Ni, Pb, Zn...)
trong mu nc thi ly 250mL mu vo cc, acid ha mu n pH=1 lc b cn, chuyn mu vo
phiu chit, thm 2mL thuc th APDC 0.1% trong ru, v 15mL CHCl 3 chit 10 pht yn 5
pht tch ly pha hu c CHCl3 vo phiu chit khc v gii chit cc kim loi bng 20 mL dung
dch HNO3 2.5M. ly dung dich nc gii chit lm bay hi mui m, sau dnh mc thnh 10
mL bng dung dch HCl 1% . y l dung dch xc nh cc nguyn t nu.
V d 2: chit xc dnh cc kim loi nng c hi(Cd, Co, Cr,Cu, Fe, Mn, Ni, Pb, Zn...)
trong mu nc bin. Ly 250mL mu vo cc. Acid ha mu n pH=2, lc b cn, chuyn mu
vo phiu chit. Thm 2 mL thuc th APDC 0.1% v 10 mL MIBK lc chit 10 pht yn 5 pht
tch ly pha hu c MIBK, lp li s chit nh th mt ln na, th 2 ln MIBK vo phiu chit
khc, v gii chit cc kim loi bng 20 mL dung dch HNO3 2.5 M. Ly dung dch nc gii chit
lm bay hi cn mui m, sau dinh mc thnh 10 mL bng dung dch HCl 1% v xc nh cc
nguyn t bng phng php ph F-AAS
V d 3: chit tch xc nh cc kim loi nng(Cd, Co, Cr,Cu, Fe, Mn, Ni, Pb, Zn..) trong
ng vng hay ng th. Ha tan 10 gam dng vo 80 mL nc ct, lc cho tan ht, chnh c
pH=1 bng acid HCl 10% lc b cn (nu c). Chuyn mu vo phiu chit. Thm 2mL dung dch
APDC 0.1%, 10 mL CCl4 lc chit 5 pht, tch ly lp hu c vo cc cha lp li s chit nh th
mt ln na tch ly phn hu c v gp phn dung mi hu c ca c 2 ln chit vo 1 phiu lc
khc. Thm 30 mL HNO3 3M lc gii chit. Tch pha ly phn dung dich nc acid c cha cc
kim loi vo cc 250 mL. un si lm bay hi nc m v nh mc thnh 10 mL bng dung dich
HCl 2% y l mu xc nh cc kim loi trong ng bng phng php F-AAS hay phng
php UV-VIS hay ICP-AES
Hnh
Cch chit ny ch c p dng cho cc cht phn tch tan trong cc mu lng (dung mi
lng ), nh mu nc thi ca nh nc sn xut ru bia, in cng nghip khai thc than, cc loi
nc khong qung cc loi. Cng c th l cc loi cht mu ha tan c trong nc, trong dung
mi hu c, hay dung dch nc ca acid hay baz long. Sau y l mt vi v d ng dng.
V d 1: chit x l mu nc bin ly cc kim loi nng (Cd, Co, Cr,Cu, Fe, Mn, Ni, Pb, Zn....)
Xem v d 2 trong mc 2.4.4, 2.4.2.2 chng 2 (trang ) v v d 1, v d 3 trong mc 2.4.4,
2.4.2.3 chng 2 (trang ).
V d 2: chit x l mu nc xc nh mt vi anion (Halogen, Nitrat, v Sunphat ). Xem v d 2
v 4 trong mc 2.4.4, 2.4.4.2 chng 2 (trang ).
V d 3: Chit x l mu nc xc nh cc cyanua (CN ) xem v d trong mc XX chng 2
(trang )
V d 4: chit tch xc dnh hm lng ion CNS trong nc thi cng nhip thc phm. Ly 250
mL mu vo cc, chnh pH v 3 bng dung dch HCl 5% lc b cn. Ly dung dch trong di qua
ct chit (loi LA-ROH 7m) vi tc 3-4 mL/pht (nh ht p sut thp). Sau khi mu chy ht,
ht kh ct trong 2 pht. Ri ra gii ct chit ly ion CNS bng 10 mL dung dch NaOH 0.5 M.
Thu dung dch ny xc nh CNS.
3.1.3.7 K thut ngm chit mu trong acid long.
Nguyn tc ca k thut ny l xay mu thnh bt, sau ly mt lng nht nh, v ngm
chit trong dung dch acid long (3-5% ). Phng php ny l chit ly cc ion kim loi c trong
mu phn tch, khi mu c ngm trong acid th cc ion kim loi s chuyn vo dung dch, dng
mui tan. V d ngm chit mu bt go trong dung dch acid HCl 5% ly cc kim loi kim v
kim th ra khi bt go v xc nh chng bng phng php ph hp thu nguyn t. Cch chit
ny n gin d lm, khng cn my mc phc tp. Ch cn nghin mu thnh bt, hay th nho,
sau thm acid vo mu v ngm chit qua m.
ngm chit ngi ta thng dng cc dung dch acid long (5-7 % ) trong nc ca acid
HCl, HNO3, hay H2SO4... sau y l vi v d ng dng.
V d 1: Ngm chit tch ly mt s kim loi (Na, K, Cd, Cu, Pb, Zn,....) t bi, chanh hay
cam. Ly 10 gam mu c nghin nh hay xay thnh bt vo bnh nn 250 mL, thm 200 mL
dung dch acid HCl 5% ngm chit. Khuy u un si, ngm chit qua m. Sau lc k 2
pht. V lc ly dung dich chit vo cc 250 mL, un si k. Lm bay hi ti cn mui m. V
nh mc thnh 25 mL bng dung dch HCl 2% (nu c vn c, lc b vn c). y l dung dch
xc nh cc kim loi v c ion nitrat, sulfat.
V d 2: ngm chit tch ly mt s kim loi (Na, K, Cd, Cu, Pb, Zn,....) trong cc rau xu
ho bp ci. Ly 10 gam mu c nghin nh hay xay thnh bt nho vo bnh nn 250 mL,
thm 100mL dung dch acid 5% ngm chit. Khuy u, un si,, lc mnh 1 pht, ngm chit
qua m. Sau lc k 1 pht, v lc ly dung dch chit vo cc 250 mL. un si k,lm bay hi
n cn mui m v nh mc thnh 25mL bng dung dch HCl 2% (nu c vn c th lc b vn
c). y l dung dch xc nh cc kim loi v mt s anion nh NO3-, SO42-.....
3.1.3.8 K thut in phn
................... Ch yu l cc ion dng v m c trong mt in th mt chiu nht nh m
chng c th nhn electron, nu l ion dng hay l cho electron, nu l ion m, tr thnh phn
t trung ha (cc nguyn t v n kt ta bm vo in cc, nh m chng ta tch c cht
phn tch ra khi mu ban u v xc nh chng theo cch chn thch hp.
V d 1: in phn x l mu xc nh ng (Cu) t mu nc thi cng nghip luyn
kim. Ly 200mL mu vo cc, acid ha n pH=2 bng acid H 2SO4 5% lc b cn. Ly dung dch
cho vo bnh in phn (cc m l bn Pt, chnh pH v 0), 10g, thm cht in ly tr (NaCl hay
KCl). in phn cho Cu bm ln in cc Pt th 0.25V trong vng 1 gi. V xc nh hm lng
Cu theo phng php in khi lng.
V d 2: in phn x l mu xc nh ch (Pb) t mu nc thi nh my acquy. Ly
200mL mu cho vo cc, acid ha n pH=1 bng acid H2SO4 5%, lc b cn. Ly dung dch cho
vo bnh in phn (cc m l bn Pt, chnh pH v 0) thm cht in ly tr (LiCl hay CsCl). in
phn cho Pb bm ln in cc Pt th 0.4V trong vng 1 gi. V xc nh hm lng Pb theo
phng php in khi lng.
3.1.3.9 Phn tch kim loi trong b thi cng nghip v c
3.1.3.9.1 Khi nim v b thi v c
B thi cng nghip v c cng c nhiu loi, rt phc tp, a dng. N ty thuc vo mi
loi cng nghip.c th gm c nh sau:
B thi cc nh my ha cht, x luyn kim, gang thp
B thi cc nh my in, than..
B thi cng nghip khai thc, tuyn v ch bin qung khong sn.....
B thi ca cng nghip nguyn liu xy dng (xi mng, gch.)
B thi ca cng nghip thy tinh, snh s.......
..........
Nh vy mi loi khc nhau s phi dng cch phn hy khc nhau, nhng u dng k
thut x l t bng cc acid khc nhau trong bnh kenddan iu kin thng hay trong l vi
sng.
3.1.3.9.2 Cch x l v v d v phn tch kim loi
Nguyn tc
Nu xc nh cc kim loi trc ht mu cn c nghin nh, trn u mu, ly mt lng
nht nh (3-5 gam ) ph hp cho nguyn t cn phn tch v x l theo cch v c ha t (ha
tan) bng cc acid mnh c tnh xy ha nh nu trn trong trang b thng thng hay trong l
vi sng ty mi phng th nghim c trang b no.
Cch x l v v d.
V d 1: b thi luyn kim, nh my in, nh tro, x l cao.....(loi hm lng SiO 2< 5%).
Ly a gam mu c nghin nh v trn u (VD a= 2.000 gam ) vo bnh kendan, tm t bng
1 mL nc ct, thm 35 mL HNO3 65%, 4mL H2SO4 98%, lc u, cm vo bnh mt phu di
ui, un si nh trn bp cch ct n khi mu trong sut l c. Sau chuyn sang cc v un
nh ui cho ht acid n cn mui m . Sau thm 5mL HCl 10% vo mui m , lc v un
nh cho tan, nh mc thnh 25 mL bng nc ct. Nu nng cc nguyn t nh, th c th ly
lng mu ln hn v cng phi tng lng acid ln cho thch hp (tng 80% thi)
Mu loi ny c th x l trong l vi sng th nhanh v trit , m li khng lo mt nguyn
t phn tch
V d 2: b thi ca cc nh my ha cht v c, luyn kim, gang thp (c hm lng SiO 2
nh). Ly a gam mu c nghin nh v trn u (VD a: 2.00 gam) vo bnh kenddan, lm t
bng 1mL nc ct, thm vo 35mL cng thy, 5mL H2SO4 98% lc u, cm vo bnh phu nh
di ui, un si nh trn bp cch ct, n khi mu trong sut l c. Sau chuyn sang cc v
un nh ui cho ht acid n cn mui m. Sau nh mc thnh 25mL bng HCl 2%. Nu nng
cc nguyn t nh, th c th ly lng mu l 5 gam v lng acid thm vo cng phi tng
thm. Mu loi ny c th x l trong l vi sng th nhanh v trit m li khng lo mt nguyn t
phn tch.
V d 3: b thi cc nh my thy tinh snh s, vt liu xy dng (hm lng SiO 2 <10% )
ly a gam mu nghin nh v trn u (VD a=2.00 gam) vo bnh kendan, tm t bng 1mL
nc ct thm 35mL cng thy ,5mL H 2SO4 98% lc u cm vo bnh phu nh di ui, un si
nh trn bp cch ct n khi mu trong sut l c. ngui, chuyn b sang cc hay chn Pt.
Tm t, thm 5 mL H2SO4 28%, 10mL HF 40% v un nh cho bc khi trng SiF6 n khi thy
xut hin kh SO2 th dng un v li thm H2SO4 v HF ri bc khi ln na. ngui. Gp dung
dch lc...........b ny. Lm bay hi ui ht acid n cn mui m. Sau nh mc thnh 50
mL bng dung dch HCl 25%. cch ny c th p dng c cho cc mu qung t cha nhiu
silicat ca cc nguyn liu xy dng nh snh s thy tinh.v.v.v.....
3.2 X l mu hu c xc nh kim loi
3.2.1 Khi nim v mu hu c
Mu hu c c nhiu loi, ang dng, phc tp, n l cc loi mu thnh phn chnh. Cht
nn l cht hu c, matrix hu c v mu hu c thng gm c cc loi
Cc loi mu thc phm rau qu, tht c ti sng, v hp ca
Cc loi ng cc,go, khoai, u
Cc loi mu nc ngt gii kht, bia ru, nc qu p...
Cc loi mu tho mc, cy l thuc nam, thuoocs bc...
Cc loi mu du, m, nhin liu cht cao phn t...
Cc loi mu y sinh hc, cc loi nc, dc liu
Cc hp cht t nhin, hydrocacbon, than cc sn phm ha thch.
Cc loi rc thi, b thi thnh ph. Bnh vin, nh my thc phm. Cc loi cng nghip
hu c.
Mc ch ca x l mu y l phc v cho cc nhim v sau y:
Xc nh mt s kim loi, c bit l kim loi nng c hi.
Xc nh cc kim hay anion ca n.
Xc nh cc hp cht hu c.
V vy ty thuc vo mi mc ch phn tch th s c cch x l mu khc nhauthichs hp
theo n.
Vi cc loi mu ny, cho vic phn hy c d dng v trit , trc ht mu cn
c xay thnh bt (cc loi ht, qu cy, c), hay ct, thi nh(cy, rau, l...) trn u v cn ly
mu phn tch hay bo qun trong iu kin di 4oC, nu cha phn tch kp ngay. Vic x l
mu c th c thc hin theo mt s k thut c nu trong chng 2 trn.
3.2.2 Cc cch x l mu v v d
3.2.2.1 K thut tro ha kh (v c ha kh)
i vi cc loi mu hu c nguyn tc chung l:
1.Trc ht c xay nghin thnh bt nho, va hay th huyn ph.
2.Dng nhit tro ha mu, t chy cht hu c v a cc kim loi v dng acid hay cc
mui ca chng. C th l cn ly mt lng mu nht nh (a=5-10 gam ) vo chn nung. Nung
cht mu mt nhit thch hp t chy ht cc hp cht hu c, v ly b v c cn li ca
mu l cc acid, cc mui...sau ha tan cc b thu c ny trong acid v c nh HCl (1:1)
HNO3 (1:2) chuyn cc kim loi vo dng cc ion trong dung dch. Quyt nh vic tro ha ay
l nhit nung v thi gian nung (nhit tro ha v thi gian tro ha). Nhit tro ha cc hp
cht hu c thng c chn thch hp trong vng t 400-500 oC, n ty theo mi loi mu v cht
phn tch.
Qu trnh tro ha kh c th c thc hin c thm cht bo v, gi cho cht phn tch
khng b mt khi tro ha. Vic c dng hay khng dng cht bo v l ty thuc vo mi loi mu
v cht phn tch c th c b mt hay khng m dng cht bo v cho ph hp.
3.2.2.1.1 Tro ha khng c cht bo v v ph gia
Cch x l: cn ly mt lng mu nht nh (thng t 2-3 gam) cho vo chn nung,bt,
hay cc, ri em nung nhit thch hp, t chy, phn hy cc hp cht hu c ca mu,
chuyn cc nguyn t kim loi v dng b (tro ca cc mui v c hay cc oxit ca chng. Ha tan
tro ny trong HCl khi chng tan c dung dch mu phn tch, v d xc nh Ca, Mg, Na, K...
trong cc mu rau qu, thc phm, chng ta c th tro ha mu m khng cn dng cht bo v. V
cc nguyn t ny khng b mt khi nung.
Cc v d:
V d 1: Phn tch mt s kim loi nh: Al, Mg, Na, K,... trong mu rau qu. Ly 5 gam mu
cho vo chn nung, sy trn bp in cho n kh dn, ri nung 3 gi u 450 oC sau nung
530oC n khi c tro khng cn en (ht than en 10-8 gi). Sau ha tan tro cn li bng 15
mL HCl 1/1, un nh cho tan ht, v ui ht acid d n cn mui m v nh mc thnh 25 mL
bng dung dch HCl 2% lc u (nu c cn th lc b). l dung dch mu phn tch cc
nguyn t ni trn.
V d 2: phn tch mt s kim loi Al, Ca, Cd, Cu, Co, Fe, Mg, Mn, Na, K, Zn,.. trong mu
thc phm, tm, c,..ly 5 gam mu vo chn nung, sy cho kh dn. Ri nung 8 gi u 450 oC
sau 520oC n khi c tro khng cn en(ht than en). Sau ha tan tro cn li bng 15mL
HCl 1/1 un nh cho tan ht v ui ht acid d n cn mui m v nh mc thnh 25 mL bng
dung dch HCl 2%. Nu dung dch c cn th nn ly tm hay lc b cn. Cch ny d b mt cc
nguyn t Cd, Pb, Zn (8-15%) khi tro ha. Nht l khi tro ha nhit trn 530 oC. V th cch
ny khng thch hp cho Cd, Cu, Pb, Zn.
V d 3: Phn tch mt s kim loi Al, Ca, Mg, Na, K...trong mu dc phm thuc v y
hc. V d xc nh cc nguyn t Al, Na, K, Fe, Mn, Ni,...trong cao h ct. Ly 1 gam mu cho
vo chn nung, sy cho kh dn. Sau em nung 3 gi u 450 oC, sau 530oC n khi c
tro khng cn en(ht than en ). Sau ha tan tro con li bng 15 mL dung dch HCl 1/1 un nh
cho tan ht, v ui ht acid d cn mui m v nh mc thnh 25 mL bng dung dch HCl 2%.
Nu dung dch c cn th lc b cn ly phn trong xc nh cc cht. Trong v d ny cc
nguyn t Cd, Cu, Pb v Zn cng b mt nh v d 2.
3.2.2.2 Tro ha kh c cht bo v v cht chy
Nguyn tc v cch lm:
i vi mt s nguyn t c th b mt khi nung, nh Cd, Pb, Zn,.. nn nu ch nung nh
trn s b mt mt t (7- 20 %), m chng ta khng th bit c, nh v d 2 trn. V vy chng
ta phi thm vo cht bo v, khi tro ha. V d xc nh Cd, Cu, Pb, Zn trong mu rau qu v
thc phm, trong cc phng php tro ha kh cc nguyn t ny thng b mt t 10- 15 %. S
mt ny li khng khng ch c trong qu trnh tro ha. V th ngi ta phi thm cht bo v l:
H2SO4, HNO3, KNO3 hay Mg(NO3)2 hay hn hp (Mg(NO3)2 + LiBO2 ), th cc nguyn t ny s
khng b mt (xem bng ph lc cui chng).
Bng 3.3 kt qu x l c cht ph gia v khng c cht ph gia bo v
Cc v d:
VD1: phn tch Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn,Cr.. trong mu rau qu (rau mung rau ci).
Ly 5 gam mu cho vo chen nung thm cht bo v l KNO3 10% 10mL H2SO4 98% trn u say
hay un cho si. Ri kh dn, nung 3 gi u 450 oC, sau 530 oC n khi c tro khng cn
en(ht than en ). Sau ha tan tro con li bng 15 mL dung dch HCl 1/1 un nh cho tan ht,
v ui ht acid d cn mui m v nh mc thnh 25 mL bng dung dch HCl 2%. Gii thch c
ch.
VD2: phn tch Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn, Cr.. trong mu thc phm (tm c tht).Ly 5 gam
mu cho vo chen nung thm cht bo v l 5mL Mg(NO3)2 10% + 10mL H2SO4 98% trn u sy
hay un cho si. Ri kh dn, nung 3 gi u 450 oC, sau 530 oC n khi c tro khng cn
en (ht than en ). Sau ha tan tro cn li bng 15 mL dung dch HCl 1/1 un nh cho tan ht,
v ui ht acid d cn mui m v nh mc thnh 25 mL bng dung dch HCl 2%, lc u. (nu
c cn th lc b)
VD3: phn tch Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn,.. trong mu thc phm sa bt, sa c c ng.
Ly 5 gam mu cho vo chn nung thm cht bo v l 12mL H2SO4 778% 5mL Mg(NO3)2 10%
trn u sy hay un cho si. Ri kh dn, nung 3 gi u 450 oC, sau 530 oC n khi c
tro khng cn en (ht than en ). Sau ha tan tro con li bng 15 mL dung dch HCl 1/1 un
nh cho tan ht, v ui ht acid d cn mui m v nh mc thnh 25 mL bng dung dch HCl
2%, lc u.
VD4: phn tch Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn,...trong mu rc thi ca thnh ph Ly 5 gam mu
cho vo chn nung thm cht bo v l 5mL LiBO 2 10% + 5mL Mg(NO3)2 10% v 5mL H2SO4 98%
trn u sy hay un cho si. Ri kh dn, nung 3 gi u 450 oC, sau 530 oC n khi c
tro khng cn en (ht than en ). Sau ha tan tro cn li bng 15 mL dung dch HCl 1/1 un
nh cho tan ht, v ui ht acid d cn mui m v nh mc thnh 25 mL bng dung dch HCl
2%, lc u. (nu c cn th lc b).
Trong vic x l mu hu c ly cc kim loi th k thut ny c nhng u v nhc im l:
Tro ha trit c mu ht cc hp cht hu c.
n gin v d thc hin
Khng tn nhiu acid tinh khit cao v khng c acid d
Hn ch c s nhim bn do dng d thuc th
Qua mu x l khng lu, kh phng php t.
Mu dung dch, mu thu c s sch.
Nhng..: nu khng dng cht bo v.
3.2.2.2 K thut tro ha t (bng acid c oxy ha mnh)
Ni chung nh nu trong chng 2 c th dng mt acid c c tnh oxy ha mnh, hay hn
hp cc acid c c tnh oxy ha mnh, hay hn hp ca mt acid c tnh oxy ha mnh v mt
khng c tnh oxy ha nh (HNO 3 + HCl) hay (HF + HClO 4) t 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 acid thng phi dng gp t 15 40 ln lng mu thi gian 10 12 gi.
Nn khi phn hy xong thng phi ui ht acid d.
Sau y l mt s hn hp acid c dng phn hy cc mu ly cc nguyn t kim loi
vo dung dch di dng cc mui tan.
+ Dng mt acid mnh hay c tnh oxy ha mnh: HCl, HNO3, H2SO4
+ Dng nc cng thy (HCl + HNO3)
+ Dng hn hp acid mnh c tnh oxy ha mnh (HNO3 + HClO4)
+ Dng mt acid mnh c tnh oxy ha mnh HNO3 vi H2O2
+ Dng hn hp a acid: (HNO3 + HClO4 + H2SO4)
+ Dng hn hp (HF + H2SO4 + HClO4) cho mu nhiu silicat.
+ Dng dung dch acid c v cht oxy ha mnh (HNO3 + H2O2)
+ Dng dung dch acid mnh cng vi cht to phc (HCl + Tartric)
Tt nhin mt hn hp ch thch hp cho mt s loi mu. V th phi kho st tm chn
cho thch hp nhm thu c hiu qu cao, khng mt cht v li ph hp vi phng php phn
tch chn. Sau y l mt s v d ng dng.
V d 1: X l mu xc nh Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zntrong mu rau qu thc phm.
Ly 5 g mu vo hp x l, thm 25 mL HNO 3 65%, trn u ri cho hp mu vo l vi sng trong
1.5h. Ly mu ra ngui, chuyn mu sang cc lm bay hi ht acid n cn mun m. Sau
ho tan nh mc thnh 25mL bng dung dch HCl 2%.
V d 2: X l mu xc nh Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zntrong mu rc thi thnh ph.
Ly 5 gam mu vo hp x l, thm 35 mL nc cng thy, trn u ri cho hp mu vo l vi
sng trong 1.5h. Ly mu ra ngui, chuyn mu sang cc lm bay hi ht acid n cn mun m.
Sau ho tan nh mc thnh 25mL bng dung dch HCl 2%.
V d 3: X l mu xc nh Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zntrong mu rc thi thnh ph.
Ly 5gam mu vo hp x l, thm 30 mL nc cng thy, 5 mL H 2SO4 98%, trn u ri cho
hp mu vo l vi sng trong 1.5h. Ly mu ra ngui, chuyn mu sang cc lm bay hi ht acid
n cn mun m. Sau ho tan nh mc thnh 25mL bng dung dch HCl 2%.
Trong h kn c p sut cao: y cng l k thut v c ha t. Ch c khc l dng thm nng
lng ca l vi sng x l mu thay cho cch gia nhit truyn thng. Mu c trong bnh
Teflon c np y, t trong v bo v chu p sut cao. t mu trong l vi sng, cc cht hu c
trong mu s b phn hy, t chy, oxyha. Nh vy mu s c phn hy trong acid p sut
cao.
+ V d 1: x l mu xc nh Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn trong mu rau qu
ti sng. Ly 5gam mu vo hp x l, thm 30mL cng thy, trn u, y np cht. Ri cho
hp mu vo l vi sng trong 50 pht. ngui, ly ra v chuyn mu sang cc, lm bay hi
ui acid v n cn mui m. Sau ha tan mui m v nh mc thnh 25mL bng dung dch
HCl 2%. Sau c th xc nh cc kim loi trong dung dch mu ny bng php o ph hp thu
nguyn t, pht x nguyn t hay phng php in ha
+ V d 2: x l mu xc nh Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn v cc nguyn t
t him trong mu qung t him. Ly 2gam mu vo hp x l, thm 20mL cng thy, trn
u, y np cht. Ri cho hp mu vo l vi sng trong 45 pht. ngui, ly ra v chuyn mu
sang cc, lm bay hi ui acid v n cn mui m. Sau ha tan mui m v nh mc thnh
25mL bng dung dch HCl 2%. Nu dung dch c cn th lc hay ly tm ly phn trong.
+ V d 3: X l mu xc nh Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zntrong mu rc
thi thnh ph. Ly 5gam mu vo hp x l, thm 25mL nc cng thy, 5mL H2SO4 98%, trn
u, y np cht. Ri cho hp mu vo l vi sng trong 50 pht. ngui, ly ra v chuyn mu
sang cc, lm bay hi ui acid v n cn mui m. Sau ha tan mui m v nh mc thnh
25mL bng dung dch HCl 2%. Sau c th xc nh cc kim loi trong dung dch mu ny bng
php o ph hp thu nguyn t hay phng php in ha
u v nhc im chnh ca k thut ny l:
+ Qu trnh x l tng i nhanh (40 100 pht)
+ X l kh trit v khng mt cht phn tch
+ t c kh nng b nhim bn, nht l trong h kn c p sut cao
+ Khng phi ui acid d nhiu, nn hn ch c s nhim bn
+ Nhng phi c h trang b l vi sng thch hp
+ Thch hp cho nhiu loi mu phn tch
3.2.2.6 K thut ln men mu
Trc tin phi chuyn hay ha tan mu vo trong nc thnh dung dch hay th huyn ph
(vi nng mu khong 5 10%) thm 10 15mg men xc tc v chnh mi trng bng acid
hay kim, hay mui acetat cho ph hp theo yu cu ln men. V d pH = 7 8 khi ln men mu
ng en, ri a mu vo bung ln men nhit t 37 40 0C cho n khi mu trong hon
ton, tc l cc kim loi chuyn vo dung dch, cn cc cht hu c, khi ln men chuyn thnh
acid, nh acid acetic, kh CO2 v nc. Thi gian ln men t 7 10 ngy. Kiu ny rt thch hp
cho phn tch xc nh cc kim loi trong cc mu ng ma, nc ngt gii kht, mt s mu
nc qu chn p nh: chui, da, chanh, cam
+ V d 1: x l mu xc nh hm lng vt kim loi nng trong ng en, ng
vng hoa m, l cc loi mu c th c x l theo cch ny. Cn 10gam ng, ha tan trong
100mL nc ct, un nng n 400C, thm men xc tc, y knh ng h v trong t m ln
men nhit 37 40 0C cho mu ln men trong 7 ngy. Sau thm 10mL acid HCl 35% un si,
ly tm ly dung dch trong xc nh cc ion kim loi. Hay lm bay hi cn mui m, sau nh
mc bng mi trng acid thch hp theo phng php phn tch chn.
+ V d 2: x l mu xc nh hm lng vt kim loi nng trong mt ong. Cn 5
gam mt ong, ha tan trong 100mL nc ct m, un nng n 40 0C, thm men xc tc, y knh
ng h v trong t m ln men nhit 37 40 0C cho mu ln men trong 8 ngy. Sau
thm 10mL acid HCl 35% un si, lm bay hi cn mui m, thm 5mL HCl 10%, nh mc thnh
50mL bng nc ct, ly tm ly dung dch trong xc nh cc ion kim loi nng.
+ V d 3: x l mu xc nh hm lng vt kim loi nng trong nc qu p. Lm
nh sau: cn 5gam mu, ha tan trong 80mL nc ct m, un nng n 40 0C, thm 15mg men xc
tc, y knh ng h v trong t m ln men nhit 37 40 0C cho mu ln men trong 8
ngy. Sau thm 10mL acid HCl 35% un si, lm bay hi cn mui m, thm 5mL HCl 10%,
nh mc thnh 25mL bng nc ct, ly tm ly dung dch trong xc nh cc ion kim loi nng.
K thut ny c nhng u v nhc im chnh l:
+ n gin, d thc hin, khng mt cht phn tch
+ Khng tn km ha cht nhiu
+ Nhng phi mt nhiu thi gian, ch qu trnh ln men lu
+ Ch mt s loi mu dng lng. hay mu tan trong nc mi p dng c k thut
ny.
3.2.2.7 K thut ngm chit trong acid long
x l mu theo kiu ny, trc ht mu phi c ha tan trong mt dung mi thch hp
nh nc ct hay nh ha mu thnh dng huyn ph, thm cht m, cht to phc, hay cht to
mi trng, ngm qua m. Sau chit cht phn tch hay hp cht phc ca n t dung dch mu
vo mt dung mi hu c thch hp. Cch x l ny n gin, khng mt cht phn tch, khng cn
my mc dng c v trang b nhiu, nhng phi ngm mu qua m v ch thch hp cho mt s
loi mu.
+ V d 1: x l mu xc nh cc kim loi kim v kim th trong cc mu ng.
Ly 5gam mu ng vo bnh nn, thm 50mL nc ct, lc cho tan ht, thm 15mL HCl 36%, lc
u, un si, lm bay hi cn mui m, ri nh mc thnh 25mL bng dung dch HCl 2%. y l
dung dch mu xc inh cc kim loi kim, kim th. Vi cc loi nc qu p cng x l c
theo cch ny xc nh cc kim loi kim v kim th.
+ V d 2: x l mu xc nh cc kim loi km v kim th trong cc loi mu bt
go, bt m, bt khoaiLy 5gam mu bt vo bnh nn, thm 50mL nc ct, lc nh ha cho
huyn ph, thm 15mL HCl 36%, lc u k, un si, y nt bnh. ngm qua m. Sau lc
hay ly tm ly dung dch, un si, lm bay hi cn mui m ri nh mc thnh 25mL bng dung
dch HCl 2%. y l dung dch mu xc nh cc kim loi kim kim th.
3.2.2.8 K thut pha long mu bng dung mi thch hp
Cch x l ny l thch hp cho xc nh cc cht c nng khng cao v loi mu c th
ha tan tt trong nc ct, hay mt dung mi hu c no to thnh dung dch mu ng th.
Cch x l ny n gin, khng mt cht phn tch, khng cn my mc dng c v trang b nhiu
nhng ch thch hp cho mt s mu tan c trong mt dung mi nht nh v cht phn tch c
nng ln, khi pha long mu vn cn xc nh c n, theo phng php chn.
+ V d 1: x l mu xc nh Cu, Zn, Fe trong huyt thanh. Ly 0.5 mL dung dch
huyt thanh, thm 1.5 mL nc ct hai ln, lc u. y l dung dch mu xc nh Cu, Fe, Zn
trong huyt thanh bng phng php AAS. Nh vy mu c pha long 4 ln.
v nc ra vo cc 250mL, thm 4mL LaCl 3 5%, lc u, un nng thm dung dch NH 3 25% n
pH = 9 v thm d 4 git. Lc u, yn kt ta khong 10 15 pht, lc ly kt ta qua giy
bng . Ha tan kt ta bng acid HCl 25% nng (15mL), cho tan ht, nh mc thnh 50mL. y
l dung dch mu xc nh As bng phng php ph hp thu nguyn t.
3.3.2.2.V c ha kh dng hn hp kim mnh v cht oxy ha
Dng mt cht oxy ha mnh (Na2O2) trong mi trng kim mnh (KOH,NaOH) khi un
nng phn hy cu tr ca cc cht hu c, v a cc kim c trong hp cht hu c v dng
cc anion ca mui ca cc kim loi kim tan c trong nc, hay trong dung dch acid long.
Sau ha tan mu tro ha tch ly cc anion ca cc nguyn t . Cch ny trit v
nhanh hn cch x l t. Nhng iu kin y l cht oxy ha v lng kim phi ng hn
lng mu cn x l.
Theo k thut ny ngi ta thng dng cc hn hp kim sau y, v cch ny c dng
c hiu qu hn cc cch ni trn.
Dng hn hp (mui + kim + cht oxy ha mnh), v d nh cc hn hp:
(NaHCO3 + KOH + Na2O2); (Na2CO3 + KOH + Na2O2); (Na2CO3 + NaOH + Na2O2); (K2CO3 +
KOH + Na2O=); (LiBO2 + KOH + Na2O2)
Cch x l v v d
+ V d 1: x l mu xc nh cc nguyn t kim: Cl, S, P, Astrong mu rau qu.
Trc ht mu phn tch cn c xay thnh bt nho, v trn u. Cn ly 5gam, vo chen nung
thch anh, thm 2g NaHCO3, 4g KOH, 6g Na2O2, 5mL nc ct trn u thnh mt hn hp nho
nh va, un nh cho mu si u (ch d si bt v bn khi un). Tip tc un nh mu n khi
ht si bt, ri un tip cho n khi thnh than en. Sau em nung, 3h u 450 0C, sau nng
ln 5300C n khi no ht than en l c. ngui, em mu ha tan trong 100mL dung dch
NH3NO3 2% pH = 4. Lc manh u, lng. Sau lc hay ly tm ly dung dch xc nh cc
cht anion: AsO4, Cl, PO4, SO4. Trong dung dch ny Cl (ni chng l nguyn t nhm Halogen
dng anion (Cl-, Br-, I-) cn S dng anion SO42-, P dng ion PO43-, As dng ion AsO43-. Ni
chung cch tro ha bng kim tt hn cch tro ha bng acid ni trn.
+ V d 2: x l mu xc nh cc nguyn t kim: Cl, Br, S, P, Astrong mu thc
phm c, tm, cuaTrc ht mu phn tch cn c xay thnh bt nho v trn u. Cn ly 5g
vo chn nung, thm 2g NaHCO3, 4g KOH, 6g Na2O2, 5mL nc ct trn u thnh mt hn hp
nho nh va, un nh cho mu si u (ch d si bt v bn khi un). Tip tc un nh mu
n khi ht si bt, ri un tip cho n khi thnh than en. Sau em nung, 3h u 450 0C, sau
nng ln 5300C n khi no ht than en l c. ngui, em mu ha tan trong 100mL dung
dch NH3NO3 2% pH = 4. Lc manh u, lng. Sau lc hay ly tm ly dung dch xc nh
cc cht anion: AsO4, Cl, PO4, SO4. Trong dung dch ny Cl (ni chng l nguyn t nhm Halogen
dng anion (Cl-, Br-, I-) cn S dng anion SO42-, P dng ion PO43-, As dng ion AsO43-.
+ V d 3: x l mu xc nh As trong qung hay b thi rn. Ly 0.5g mu qung vo chn
Zr, thm 4g KOH, un nh cho hn hp chy lng, thm cn thn 5g Na 2O2 lc u v em nung
7000C cho chy lng trong 10 pht ngui. Ly chn c mu ra lau sch y, v b c chn vo
cc dng trn 400mL c sn 400mL nc ct nng 700C, lc k cho mu tan. Ly chn Zr ra v
trng chn 2 ln bng 20 mL nc ct (tng mu di 130mL). Thm vi mnh s xp nh vo cc
mu. y knh ng h v un si nh ui ht H 2O2 khong 15 pht, ngui. Sau lc ly
dung dch qua giy bng , ra kt ta v giy lc 3 ln bng 20mL dung dch KOH 0.05% nng.
Ly nc lc v ra, c cn cn khong 65mL, thm 25mL HCl 35%, lc u v nh mc thnh
100mL. y l dung dch mu xc nh As bng phng php AAS theo k thut Hydrua ha.
Cch x l ny thch hp cc loi mu rn, nh qung t, , rc thi rn, bn, trm
tch xc nh As. Nhng hm lng Si trong cc mu ny phi nh hn 10%
3.3.2.3. K thut chng ct
Mt s nguyn t kim, hay anion c kh nng to c cc acid hay cc hp cht d bay
hi nhit thp nht nh u c th dng cch ny tch chng ra khi mu ban u. V dun
nh kim As (bay hi di dng AsH3), anion CN, S ( dng acid HCN v H2S)Mun thc hin
x l theo cch ny trc tin mu phn tch cn phi ha tan trong nc to thnh dung dch trong
hay th huyn ph ng u. Sau khi chng ct ngi ta thm acid mnh hay thuc th ph hp
vo hn hp mu to ra cht bay hi v chng ct n cho tan hay hp th vo mt dung dch
thuc th c tnh cht nh lng.
V d 1: x l mu xc nh hm lng anion S trong b thi. Ly 20gam mu c
xay hay nghin mn vo bnh chng ct hai c (hnh 3.8), thm 80mL nc ct v hai ht s xp
(SiO2), lc u v lp vo h thng chng ct. un si mu chng ct v nh tng git acid
H2SO4 45% xung bnh lin tc (2 git trong 1 giy) trong thi gian chng ct v dng k nit sch
chy qua (3 bng kh trong 1 giy), n khi ht 25mL acid H 2SO4. Khi s c phn ng to ra kh
H2S bay ln
S2- (trong mu) + H+ H2S
Kh H2S bay ra ny c dng kh nit dn vo bnh hp th c cha sn 25mL dung dch
kim NaOH 0.01M. Khi ht kh H2S bay sang bnh hp th (30 40 pht), thu ly dung dch mu
ny v xc nh hm lng NaOH d, ta s suy ra c hm lng NaOH tc dng vi H 2S, v
suy ra c hm lng anion S2Ch : Chng ta cng c th cho kh H2S sinh ra vo bnh c cha 20mL dung dch mui
Pb(NO3)2 0.1M c pH = 1. Sau ly tm b kt ta xc nh hm lng Pb d bng phng php
AAS. Th cng suy ra c hm luwowjgn ion S2- theo phn ng:
Pb2+ + S2- = PbS
V d 2: X l mu xc nh hm lng anion CN - trong b thi. Ly 20 g mu uc xay hay
nghin mn vo cc 250 mL , thm 50 mL nc ct, kim ha n pH 8, khuy k, un si, thm 2
mL dung dch mui sulfate Cd(II) v Zn(II) 1%, lc k, un si nh, nu c kt ta th tch b anion
S2- di dng cc sulfide kh tan, kim hoa tip n pH 10, khuy u, lng 1h, ly tm hay lc
b kt ta . Ly nc lc v nc ra (khong 30 mL) cho vo bnh chng ct nh v d 1 nu
trn, lc u v lp vo h thng chng ct. un si bnh mu chng ct, nh tng git acid
H2SO4 45% xung bnh lin tc v cho kh nit chy qua nh v d 1 trn trong thi gian chng
ct, n khi dng ht 25 mL H2SO4 45% th dng. Khi s c phn ng to acid HCN (dng kh)
bay ln.
CN- + H+ HCN
Kh HCN sinh ra uc dng kh Nit dn vo bnh hp th c cha sn 25 mL dung dch NaOH
0.01M. Khi ht kh bay sang bnh hp thu (30-40 pht) , thu ly dung dch mu ny v xc nh hm
lng NaOH d, ta s suy ra lng NaOH tc dng vi HCN hay lng anion CN trong mu.
V d 3: Chng ct tch ly As t cc mu b thi rn hay thc vt, rau qu: Ly 10 g mu c
xay thnh bt vo bnh phn ng , nh ha bng 50 mL nc v thm HCl 35% c nng
khong 4M, lc u, un si nh cho mu phn hy n ht. ngui, yn 5 pht, thm 2 mL dung
dch KI 5%, un cch thy v lc u kh As(V) v As(III) trong 20 pht. Chuyn ton b mu
vo bnh chng ct, thm 10 mL HCl 35%, lc u, lp h thng chng ct. Cho kh mang Ar hay
N2 chy qua theo tng bong bng (3 bong bng / s), cho my khuy chy khuyy u mu, nh
tng git NaBH4 0.1M v bnh phn ng vi tc 1 mL/pht n ht 25 mL.Lc ny AsH 3 sinh ra
uc kh mang Ar dn sang bnh hp thu c cha dung dch thuc th R (Ag-DDC trong pyridin
20 oC). Chng ct cho n khi nh ht dung dch NaBH 4 th thi, ly dung dch hp thu xc nh
As theo phng php quang ph hp thu phn t UV-VIS.
3.3.2.4. K thut chit thng thng
Cc anion ca mt s nguyn t kim tn ti trong dung dch mu l cc mui c kh nng phn ly
thnh cc anion v tc dng uc vi mt s thuc th, trng nhng iu kin ph hp th c th tch
chng ra khi mu ban u. V d: NCS, CN, S. Mun thc hin x l theo cch ny trc tin mu
phn tch cn phi uc ha trong nc thnh cc dung dch hay huyn ph ng nht. Sau iu
chnh mi trng (thm acid hay kim) v thuc th ph hp vo hn hp mu to ra hp cht
c th chit uc vo mt dung mi hu c. Sau xc nh anion trong dung mi chit thu uc.
V d 1: Chit x l mu xc nh hm lng anion CNS trong b thi. Ly 20 g mu c xay
hay nghin nh vo bnh chit, thm 50 mL nc ct, chnh pH 2 bng H 2SO4 10%, lc u, thm 1
g Na2S2O3, thm 2 mL dung dch Co(NO3)2, lc u 10 pht, thm 20 mL ru isoamylic tinh khit,
y nt phu chit, buc cht v tin hnh chit trong 10 pht, yn 5 pht cho phn lp. Tch ly
CHNG VI:
X L MU XC NH CC CHT HU C
4.1. khi nim v phn loi mu hu c
4.1.1. mu hu c, cc loi v c im ca n
Mu hu c l cc loi mu m cht nn (matrix) ca mu l cc cht hu c. V d cc mu thc
phm, go, bt, thc vt, rau qu, cy l, sa, du m v.v. cc loi mu ny c th tn ti trng
thi rn, lng, kh, hay huyn ph. Cc mu hu c cng c c cc cht v c, cc cht kim loi,
chng tn ti trong mu dng hp cht c kim hay c hu c. V th c c xc nh cc cht hu
c v xc nh cc cht v c, cc nguyn t kim loi trong mu hu c. V d nh xc nh cc
thuc tr su dit c trong mu t nng nghip, l xc nh cht hu c trong mu v c. Nhng
trong mc ny ch yu trnh by cc k thut x l mu ly cc cht hu c trong cc i tng
mu hu c v v c khc nhau xc nh chng. Cht hu c c rt nhiu, song ngi ta phn
chia thnh cc loi sau y:
1. Cc loi hp cht hydrocacbua mch thng v mch vng.
2. Cc loi hp cht carbonyl (acid v aldehyd).
3. Cc loi hp cht amino acid, cc amin v vitamin.
4. Cc loi hp cht hu c c Halogen (Cl, Br) c nit.
5. Cc loi hp chy c kim loi
6. Cc loi hp cht d vng, c phosphor v nit v.v.
Tt nhin cch phn chia ny l theo quan im ca ho hc hu c. Trong cc loi ny, nu xt v
bay hi ca chng th ngi ta li xp thnh ba nhm nh sau
- Nhm 1: l cc cht d bay hi, im si thp (im si <150oC )
- Nhm 2: cc cht c bay hi trung bnh (im si 150-200oC)
- Nhm 3: cc cht kh bay hi (im si 250oC)
Trong x l mu phn tch xc nh cc cht hu c, chng ta s cp v s dng c hai
cch phn chia ny.
4.1.2. Cc yu cu ca x l mu cho phn tch cc cht hu c.
Cc cht hu c l rt phong ph, nhiu loi cht a dng, nhiu gp hng t ln cc cht v c
mc d ch c vi nguyn t ho hc chnh l C,H,O,S, cho ra cc cht hu c b ln men, b
oxy ho, b t chy, b ph v phn t sinh ra cc sn phm khc nht l cc hp cht trong
phn t c lin kt (ni i, ni ba, mch cacbon khng no). V th, ngoi cc yu cu chung
ca x l mu phn tch ni trn, th cc k thut x l mu phn tch cc cht hu
c cng c nhng im khc vi cc cht v c. Vn c th l:
+ v tnh a dng, phc tp nn kh tch cc cht phn tch ra khi mu.
+v tnh khng bn nn d b mt khi x l hay phn hu.
+phi c nhiu loi trang b khc nhau cho mi loi cht.
+trong x l cn nhiu dung mi hu c, c dung mi im si thp.
+phi khng ch nghim ngt cc iu kin khi x l mu
+ thng phi bo qun nhit thp (t +4 n -20oC).
4.2. Cc k thut x l mu xc nh cht hu c
4.2.1 Nguyn tc chung
- ly c tt cc cht phn tch, trc ht phi chuyn mu thnh dng bt hay huyn ph
hay dung dch ng nht trong mt dung mi thch hp, nc hay dung mi hu c, tu cch x
l, loi mu, v cht phn tch.
- Sau ly mt lng nht nh v x l bng mt k thut thch hp, v d nh chng ct hay
chit, hay kt tinh d ly cht phn tch ra khi mu ban u v chuyn n vo mt dung mi
thch hp. Sau xc nh chng trong dung mi .
4.2.2. Cc phng php, k thut x l v v d
4.2.2.1. Cc k thut chng ct
4.2.2.1.1. K thut chng ct thng thng
4.2.2.1.1.A. Nguyn tc
Chn cc iu kin thch hp chng ct tch ly chng ra khi mu phn tch ban u v c
th cho n tan vo mt dung mi khc tt hn, ph hp vi phng php xc nh (phn tch )
chn. Sau xc nh n trong dung mi ny (xem thm c s ca s chit trong chng II
trn)
4.2.2.1.1.B. Cc trang b, cch lm v v d
V d 3:Xc nh h clo-phenols trong mu rn, bt(nh thc phm hay mu t).Trc ht cng
phi xy mu thnh bt nho, trn u. Cn 5g mu vo phu chit, thm 20mL nc ct trn u,
chnh pH n 2 bng acid HCl 4M, lc u, thm 20mL dung mi dietyl-ete, lc chit mnh trong 5
pht, lng yn trong 5 pht.Sau tch ly lp hu c. Lp li s chit nh th mt ln na. Gp
pha hu c trong 2 ln chit li, lm kh bng Na 2SO4 khan, ri chuyn vo bnh nh mc 50mL,
v nh mc bng dung mi chit. y l dung dch mu xc nh cc clo-phenols bng GC. Vi
cc loi mu nc nh nc thi, nc sng hLy 250mL mu, chnh pH v lm tip tng t.
Nu nng nh th ly 500mL mu.
V d 4:Xc nh h hp cht clo-phenoxy trong mu rn, bt(nh thc phm, t, bn, rau qu.
[Method 3221A]. Trc ht cng phi xy mu thnh bt hay bt nho, trn u, cn 5g vo phu
chit, thm 10mL nc ct, trn u, chnh pH n 2 bng acid HCL 4M, lc u, thm 20mL dung
mi dietyl-ete, lc chit mnh trong 5 pht, lng yn trong 5 pht.Sau tch ly lp hu c.
Lp li s chit nh th mt ln na. Gp pha hu c trong 2 ln chit li, lm kh bng 20-25g
Na2SO4 khan.Lm bay hi dung mi chit nh dng kh nit hay ct quay chn khng cn 1mL,
ngui v ho tan b rn ny trong 5mL MeOH ri xc nh bng HPLC,GCVi cc loi mu
nc nh nc thi, nc sng h,..Ly 250mL mu, chnh pH v lm tip tng t, nu nng
nh th ly 500mL mu.
V d 5:Xc nh h hp cht Carbamate trong mu rn, bt (nh thc phm, t, bn, rau qu)
[Method 8321A].Trc ht cng phi xay mu thnh bt hay bt nho, trn u.Cn 5g mu vo
phu chit, thm 10mL nc ct, trn u, chnh pH n 4-5 bng acid HCl 4M, lc u, thm
20mL dung mi Diclo-metylen (CH2Cl2), lc chit mnh trong 5 pht, lng yn 5 pht. Sau
tch ly lp hu c. Lp li s chit nh th mt ln na. Gp pha hu c trong 2 ln chit li, lm
kh bng 20-25g Na2SO4 khan.Lm bay hi dung mi chit nh dng kh nit hay ct quay chn
khng cn 1mL, ngui v ho tan b rn ny trong 5mL MeOH ri xc nh bng
HPLC,GCVi cc loi mu nc nh nc thi, nc sng h,..Ly 250mL mu, chnh pH v
lm tip tng t, nu nng nh th ly 500mL mu
4.2.2.2.2.K thut chit dng lin tc
4.2.2.2.2.A.Nguyn tc chung
Qu trnh chit y ch chit cch chit thng thng l khi chit mt trong hai pha l
chuyn ng lin tc, hay c th c hai pha cng chuyn ng nguc chiu nhau. Trong nu pha
chit (dung mi chit) c t khi ln hn dung mi (pha) cha mu nhiu, th s chit cng thun
li hn. V th qu trnh chit xy ra nhanh v hiu qu cao hn chit thng thung. Trong thc t,
ngi ta thung gi yn pha cha mu trong bnh chit, cn pha ng chit (dung mi chit) th
uc duc bm lin tc tun hon sc vo bnh chit, m khng phi lc chit k thut chit ny
hay uc dng trong chit sn xut, quy trinh chit cng ngh.
4.2.2.2.2B. Trang b cch tin hnh v v d
Mun thc hinchit theo k thut ny phi c h thng chit gm bnh chit, bnh tch pha, v
h my bm bm pha ng chit theo yu cu mong mun sc vo bnh cha mu (hnh 4.24)
Hnh 4.24. S h thng chit dng lin tc n gin
V d: Chit tch 1 s cht hu c trong nc thi [ methode 3520 ]. Ly 500 ml mu vo bnh
chit. Cho my chy, bm dung mi chit ( CCl4 + CH2Cl2 ) sc vo bnh chit tun hon lin tc
trong 30 pht. Sau lng cho phn lp v tch ly phn dung mi hu c, lm kh bng
Na2SO4 khan lm bay ht dung mi chit v ha tan b cn li trong dung mi MeOH v xc nh
cc cht trong mu ny bng phng php HPLC v GC.
4.2.2.2.3 K thut chit Soxhlet.
Na2SO4, thm 50mL dung mi chit (diclo-methylen + n-Hexan trong t l:v/v=1/2), trn u, y
np v t vo bung siu m, ng cht my siu m, chn v t cc thng s siu m thch hp
chit.Tin hnh chit trong 50 pht. ngui ly hn hp mu ra tch pha, ly dung dch pha
hu c, lm bay hi dung mi bng dng kh nit sch (hay ct quay chn khng), n khi cn b
t.Ho tan b trong 3mL (hay 5mL) dung mi MeOH. y l dung dch mu xc nh cc cht
bng phng php GC hay HPLC.
V d 2:Chit tch mt s cht hu c thuc h Pesticide trong mu t, bn, trm tch, rau
qu[Method3550b]. Ly 10g mu nghin mn vo bnh chit, thm 30g mui khan Na2SO4, thm
50mL dung mi chit (diclo-methylen + n-Hexan trong t l:v/v=2/1), trn u, y np v t vo
bung siu m, ng cht my siu m, chn v t cc thng s siu m thch hp chit.Tin
hnh chit trong 50 pht. ngui ly hn hp mu ra tch pha, ly dung dch pha hu c, lm bay
hi dung mi bng phng php ct quay chn khng khi cn 1mL, ngui,
Ta c b t.Ho tan b ny trong 5mL dung mi MeOH (hay n-Hexan). y l dung dch mu
xc nh cc cht thuc h Pesticide bng phng php GC hay HPLC hay GC-MS
Mt s v d khc c th xem trong mc 2.4.4.2.3 chng 2
Hnh 4.27.S h thng chit siu m
4.2.2.2.5 K thut chit cc cht phn tch dng kh rn.
4.2.2.2.5.A Nguyn tc chung.
Nguyn tc ca cch chit ny l cc cht phn tch cn chit phi trng thi kh hoc l mu
dng kh hay nh 1 cch thch hp, ti 1 nhit thch hp chuyn cht mu thnh kh, cn pha
tnh chit l cht rn xp. Pha tnh cht chit trong ct chit hay l dng a. Pha tnh chit
y l Silica Gel xp loi trung tnh hay pha ngc, c kh nng hp ph tt cht phn tch. V th
gi l k thut chit rn kh. Trong qu trnh chit, mu c ha kh v c dng kh mang tr
N2 hay Ar sch ( > 99,99% ) dn cht mu vo ct chit theo tnh cht hp ph ca n, cn cc cht
khc th i qua. Sau dng mt dung mi thch hp nh acetonitril hay CH 2Cl2 ra gii cht
phn tch ra khi ct chit, phn tch chng trong dung dch ny. Nu cc cht phn tch d bay
hi, ngi ta cng c th gii hp cht phn tch ra khi ct chit bng ca1hc tng nhit ct chit
lm cc cht d bay hi v nh dng kh tr sch mang cc cht phn tch trc tip vo my GC
phn tch n.
4.2.2.2.5.B Trang b, cch tin hnh v v d.
thc hin cch chit ny th phi c h chit kn ( hnh 4.28 ). Ngun cp kh tr tinh khit
( Nit hay Ar 99,99% ) v khng ch c tc dng mong mun. Cc trang b ca h chit theo
kiu ny hin nay c sn xut bi nhiu hng ch to dng c th nghim phn tch v c bn
trn th trng. Cc ct chit hay a chit c cha silica gel xp loi pha thng v pha ngc
cng c ch to v bn sn trn th trng. Cc ct chit ny thng c dung tch cht chit t 6
10 ml.
V d 1: X l mu chit tch cc cht hu c d bay hi trong nc thi [ methode 5035 v 5022 ].
Ly 250 ml mu vo bnh chit, un nng n 60o+C, sc kh tr ( Ar ) tinh khit vo bnh cha mu
theo tng 2 bong bng trong 1 giy v dn kh ny vo ct chit c cha cht hp ph c tm
bng 1 dung mi hu c thch hp trong vng 120 pht. Sau ra gii trong ct chit bng 10 ml
dung mi CH2Cl2 c 20% n hexane . ly dung dch ra ny lm kh bng Na 2SO4 khan v xc
nh cc cht ni trn. Vi cc mu rn hay bt hay rau qu b thi trc ht ta phi nghin
bt mn, sau cng ly 10 g mu, thm 30g Na 2SO4 khan, lc k vo bnh chit v cng tin
hnh nh trn.
Hnh 4.28. H thng chit kh rn
V d 2:Chit tch cc hp cht cacbonyl(aldehid hay aceton) d bay hi trong khng kh [Method
0011 v 0100].Mu khng kh c dn vo ct chit silicagel(ct chit bng silicagel xp c
ch ho trc vi dung dch nc ca 2.4-dinitro-phenylhyrazin, pH=2)vi tc 3-4 l/pht.Trong
qu trnh ny aldehid c gi li trong ct chit theo tnh cht hp ph ca silicagel, v to ra cc
sn phm th ho ca cc aldehid.V d nh fodmandehyd dinitrophenyldazzone.Sau cht phn
tch trong ct chit c ra gii ra khi ct bng 10mL dung mi acetonitril hay diclomethane, v
xc nh cc cht trong dung dch ra ny bng phng php HPLC,GC, hay ph UV-VIS.
4.2.2.26.K thut chit pha rn (rn -lng ).
4.2.2.26A.Nguyn tc chung
Da vo tnh cht hp ph ca mt s silica xp c sn xut trong iu kin thch hp,
gi l pha tnh rn(chi tit v bn cht ca phng php ny xem mc 2.4 chng ).Khi ngi ta
di dung dch mu ca pha tnh , th mt nhm cht c pha tnh hp ph v gi li trn pha
tnh, cn cc cht khc .qua.Sau dng mt lng nh dung mi thch hp ra gii cht phn
tch ra khi pha tnh v xc nh chng trong dung mi .Pha tnh ca k thut chit ny hin
csn xut v cung cp trong 2 kiu ct chit:
Np trong cc ct sc k dung tch 6-10 mL
Ch to cc dng a xp
ng thi cc hng cng cc bn c cht chit dng nguyn liu cha np vo ct v bn
ct trng, ngi dng c th t np vo ct chit theo th tch yu c mong mun ring
cho th nghim cn thit ca mnh.
4.2.2.2.6B.Trang b, cch tin hnh v v d.
Trang thit b ca k thut chit ny cng tng i n gin. N gm b phu lc p sut
thp (Hay ht chn khng), ct hay di chit v ng hng mu chit(hnh 4.29). H chit kiu ct c
th lp mt dn t dm ct n hng chc ct chit ;nu lm hng lot mu).cc ct chit
(extraction carriridge:c dung tch 5-10 mL.Cn cc da chit:emporre extraction disk)c dy 2-3
mm. ng knh l 4-9 cm, phc v chit mu lm phn tch.
K thut ny c th chit cc cht phn tch trong mu lng, mu rn, mu nungc ra.
thc hin chit theo kiu ny vi cc mu khng phi .lng, trc ht chng ta phi chn mt
dung mi ph hp, ha tan c hon ton mu thnh dung dch
Hnh 4.29: s cc h thng chit pha rn
V d 1: Chit tch xc nh mt s cht hu c trong cc loi mu nc [ methode 5252 v
3535 ]. Ly 500 ml mu chnh pH = 4 5, lc b cn ri di qua ct chit vi tc 2 4 ml/
pht ( hnh 4.29 ). Khi ht mu di qua ct chit 2 ml nc ct , ht kh 3 pht. Sau ra gii
cht phn tch ra khi ct bng 10 ml CH 2Cl2. y l dung dch mu chit cc cht hu c
nh Acetanaphthene, Aldrin, Atraton, Alpha chlordane, Caloneb, Chlorobenzilate,
Chlopropham, 4,4 DDD , 4,4 DDT, 2 Chlorobiphenil Vi cc mu rn hay bn p dng
c cch ny nhng trc ht phi chn 1 dung mi ph hp v d n hexane hay acetonitril
ha tan thnh dung dch, lc b cn b, ly dung dch v lm kh n bng Na 2SO4 khan sau
mi chit nh trn.
V d 2: Tch chit nhm Aflatoxins ( B1, B2, G1, G2) t ht u v lcly 5g mu v xay
thnh mnh nh, cho vo ct v thm 50 ml ca hn hp MeOH/ H 2O ( 85/15 ), lc 10 pht, lc
ly dung dch thm 30g Na2SO4 khan, lc u chit tch b cc cht bo bng 50 ml n hexane.
Ly dung dch MeOH di qua ct chit vi tc 1ml/pht.Sau ra gii cht phn tch ra
khi ct chit bng 10 ml hn hp CHCl 3/CH3CN ( 60/40 ). Ly dung dch ra gii ny xc
nh bng phng php HPLC hay GC.
V d 3: Chit tch xc nh mt s cht Polyciclio Aromatic trong cc loi mu nc
[ methode 5501 ]. Ly 500 ml mu chnh pH = 3 5, lc b cn ri di qua ct chit vi tc
2 5 ml/ pht, sau ra gii cht phn tch ra khi ct bng Acetonitril.y l dung dch mu
chit cc cht thuc h Hydrocacbon thm a vng nh Acenaphthene,
Thiu trang 24
K thut chuyn ha ha hc
4.2.2.4A. Nguyn tc chung:
Dng mt loi phn ng ha hc ca cht phn tch vi mt thuc th c tnh cht nh lng
trong mt iu kin thch hp, to ra mt sn phm l mt cht bn, tch cht phn tch ra
khi mu dng sn phm ca phn ng . Sau xc nh n trong sn phm . Cch ny
1.
2.
3.
4.
5.
6.
7.
8.
Mn ( mg/l )
=<0,1
0,1 0,25
0,25 0,5
F ( mg/l )
=<0,7
0,7 1,7
0,7 2,0
2,0 4,0
Cu ( mg/l )
=< 0,02
0,02 0,05
0,05 1,0
1,0 3,0
Zn ( mg/l )
=< 0,05
0,05 1,0
1,0 5,0
> 5,0
As ( mg/l )
=< 0,01
=0,01
0,01 0,05
> 0,05
Cd ( mg/l )
<0,001
=< 0,001
=< 0,001
0,002
Cr( mg/l )
< 0,05
0,05
0,05
>0,05
Ni ( mg/l )
<0,05
0,05
0,05
>0,05
CN=<0,05
0,05
0,05
>0,05
Pb ( mg/l )
<0,05
=0,05
0,05
>0,05
Se ( mg/l )
<0,01
0,01
0,01
>0,01
Hg ( mg/l )
<0,005
=<0,005
0,005
0,005
Phenol ( mg/l )
<0,001
0,001 0,05
0,05 0,5
Cht ty ra ( mg/l ) <0,02
0,02
0,02 0,05
> 0,05
Khun
Coli <50
50 - 5000
5000 - 50000
(con/100)
Eshcoli
=<20
20 - 2000
20 - 20.000
Khun cu chui
=< 20
20 - 1000
1000 - 10000
Ch gii:
Nhm 1A: cht lng cao tha mn cc nhu cu sinh hot n ung.
Nhm 1B: cht lng trung bnh dng tm c cho mc ch nh trn
Nhm 2: t yu cu cho nng nghip , ti, chn nui trng trt
Nhm 3: cht lng tm thng cho trng trt v chn nui.
V d sn xut 1000 lt bia, ngi ta thi ra trn 5-6 mt khi nc thi. Nc thi c ha tan
v cha nhiu cht, c c cht v c, cht hu c, cc cht kh, cc ht keo, ht rn khng tan l
lng, cc vi sinh vt. V th nc thi l mt hn hp phc tp. Thnh phn v tnh cht ca n l
ty thuc vo loi c thi ra t ngun sn xut hay sinh hot no. Cc cht trn vo trong nc
thi, s lm cho nc thi c tnh c hi khc nhau. Tnh c hi ny ph thuc nng ca cc
cht tn ti trong nc thi, v ty thuc vo iu kin ngnh sn xut thi ra. V d As 0.01 ppm,
Hg 0.005 ppm, Pb 0.1 ppm, NO2 0.002 ppm l gy nguy him cho con ngi v ng vt chn
nui. V th bt buc phi kim tra mi loi nc thi, pht hin cc cht ha tan, cc cht l
lng, cc vi sinh vt, vi khun nh gi nhim bn ca nc thi, c hi ca mi loi v
tm cch x l nc thi trc khi cho thi vo sng h, hay ng rung. Nu khng nc thi s l
mt ngun v cng to ln lm nhim mi trng ca con ngi, hy hoi con ngi v ca sn
xut. Nht l khi mi ngnh sn xut cng nghip cng pht trin th nc thi a ra mi trng
cng nhiu. Mt khu quan trng u tin ca cng vic ny l phi kim tra v phn tch nc thi
pht hin cc cht c trong n khuyn co v ra cc bin php x l thch hp. l mt
ni dung ca chuyn ngnh ha hc mi trng. Sau y l vi v d v cc ngun gy nhim
nc v nc thi.
Cc ngun c th gy nhim cho nc:
Song song vi cuc sng ca con ngi v s pht trin ca x hi, nc thi cng lun lun
tn ti, ch c trong mc khc nhau ca mi vng, mi th, mi quc gia m thi. N ty
thuc vo trnh khoa hc, trnh sn xut cng nng nghip, v vn minh ca cc nc, s
bo v ngun nc m nc thi b nhim khc nhau. Nhng cc ngun to ra nc thi co
th bao gm t cc lnh vc sau:
1. Sinh hot ca con ngi hng ngy, thnh th, bnh vin, nng thn thi ra a cc cht
bn vo nc.
2. S sinh sng v pht trin ca ng vt, phn thi ca chng
3. Sn xut cng nghip, cc nh my cng nghip thi ra cc cht chng tan hay phn b
l lng vo nc.
4. Khai thc khong sn cc loi a vo nc nhiu cht khc nhau
5. Sn xut nng nghip, cc nh my nng nghip, thc phm
14. Hm lng du m
15. Hm lng mt s cht hu c c hi cho sinh vt v ngi:
+ Nhm khun Coliform (chnh l E-Coli)
+ Nhm khun Streptocxx (chnh l Streptocicus fecalis )
+ Nhm khun Clorstridca (chnh l Clostridium Perfringents )
Gii quyt vn ny l c mt h thng nhiu vn ca quc gia t cc quy ch php lut,
chnh sch, n cc bin php kim tra quan trc, cng nh cc phng php cng ngh x l
v iu kin kinh t.
Ngy nay cc nc c cc chun v cc loi nc, v u quy nh r hm lng , cc ch
tiu ny c th cho cc cht tan trong nc . Xem ch tiu v cc loi nc ca vit nam v USA
( iso ).
Gii quyt cc vn trn l c mt dy chuyn ng b. bt u l phn tch kim tra pht hin
cc cht , sau l giai on x l theo nhng k thut thch hp cho mi loi nc thi v ri
li kim tra phn tch li nc thi c x l, xem n t cc yu cu cha. Song
y chng ta ch im qua mt s vn trong phm vi cho php, lm v d minh ha m
thi, cn thc t th rt a dng v phong ph. Ch yu l giai on ly mu, x l mu phn
tch kim tra v pht hin cc cht.
Cch x l mu nc phn tch kim loi.
Vic x l mu nc phn tch tho nhng i tng sau y:
1. Xc nh cc kim loi ch yu kim loi c hi.
2. Xc nh mt s kim v anion.
3. Xc nh cc cht hu c c hi.
4. Xc nh pH, kim, mui.
5. Xc nh cc cht l lng khng tan
6. Xc nh cc sinh vt ph du
7. Xc nh hm lng oxy ( DO, COD, BOD )
8. Xc nh mt s vi khun nm mc gy hi.
x l mu xc nh kim loi , mt s kim v anion, chng ta c th s dng 1 s k thut
sau y:
1. k thut chit thng thng ( chit lng lng )
2. k thut chit pha rn ( rn lng )
3. Phng php kt ta, v kt ta cht gp ( sunphua hay hidroxit ).
4. Cc phng php sc k.
5. Cc phng php chng ct.
Nguyn tc v ni dung cc k thut ny xem trong mc 2.4. sau y ch nu mt s v d c th.
V d 1 : X l mu phn tch kim loi nng c hi ( Cd, Co, Cr, Cu, Fe,Mn, Ni, Pb, Zn..)
Cc kim loi nng c hi thng c hm lng nh v gii hn cho php ca n cng nh.
Cho nn khi x l mu ngi ta thng kt hp lm giu lun. V th chit l k thut c nhiu u
vit trong i tng ny.
a/ Phng php 1: Chit thng thng (chit lng-lng) ly hm lng tng cc kim loi
nng ra khi mu ban u.
Chit bng: (APDC + MIBK) hay (APDC + CCl4)
Chit bng: (Ditizon + CCl4) hay (Ditizon + CHCl3)
+ Nguyn tc: (Xem mc chit pha lng-lng trn)
Dng thuc th to phc: APDC v dung mi chit l: CCl4 hay CHCl3 hay MIBK.
+ Cch tin hnh:
Ly 250 mL nc thi vo phu chit, acid ha n pH = 4 bng HCl.10%, thm 2 mL APDC
0.1%, thm 25 mL CCl4, lc chit mnh trong 5 pht. lng yn 5 pht, gn tch ly phn
dung mi hu c CCl4 xc nh cc kim loi. H s lm giu F = 10. Cng c th gii chit
kim loi trong pha hu c ny vo pha nc bng acid HNO 3 3M, hay v c ha pha hu c, ri
ha tan tro bng acid ly kim loi v phn tch chng trong pha nc.
b/ Phng php 2: Chit pha rn (Rn-lng)
+ Nguyn tc chung: (Xem mc chit pha rn trn)
y l mt dng ca k thut sc k rn-lng (S-L), m cht chit l dng ht Silicagel v
xp. N tng t nh cc cht pha tnh ca sc k HPLC.
+ Cch tin hnh:
Chit tch lng vt cc kim loi kim: tch chit lng vt cc kim loi kim (Li, Na,
K), y ngi ta dng cht nhi kiu hp ph trao i ln ca hng Baker (Baker-10-SPEColumn, Cat-No.7020-3). Sau khi ct chit c lm sch bng nc ct (10 mL), cho chy qua 10
mL HNO3 1N, sau ra sch li ct bng 10 mL nc ct. Ly 200 mL mu, acid ha n pH = 5,
lc b bn v np dung dch ln ct chit va chun b vi tc 2-3 mL/pht. Sau ra ct bng
2 mL nc ct. Ht chn khng ct bng phu lc Busmer trong 3-4 pht. Ri ra gii cc ion kim
loi ra khi ct (pha rn) bng 15 mL dung dch NH 4NO3 2.5M, pH = 5.5. Khi pha ng chy ht
di ln ct 2 mL nc ct. Thu ly dung dch ra ny, lm bay hi cn mui m, them cht nn,
cht m v nh mc bng acid HCl 2% thnh 10 mL. y l dung dch mu xc nh cc kim
loi kim bng php o AAS hay ICP-AAS.
Chit tch lng vt cc kim loi nng: tch chit lng vt cc kim loi nng (Cd, Co,
Cr, Ca, Fe, Zn, Ni, Pb) t mu nc, y ngi ta dng cht nhi u hp ph ra ngc C18 ca
hng Baker (Baker-10-SPE-Column, Cat-No.7020-3). Sau khi ct chit c lm sch bng nc
ct (10 mL), cho chy qua 10 mL HNO 3 1N, sau ra sch li ct bng 10 mL nc ct. Ly 200
mL mu, acid ha n pH = 4.5, lc b cn, ly dung dch them 3 mL thuc th APDC 0.1%, lc
u v cho chy vo ct chit va chun b vi tc 2-3 mL/pht. Sau ra ct bng 2 mL nc
ct. Ri ra gii cc ion kim loi ra khi ct (pha rn) bng 15 mL dung dch NH 4NO3 2.5M, pH =
5.5. Khi pha ng chy ht di ln ct 2 mL nc ct. Thu ly dung dch ra ny, lm bay hi cn
mui m, them cht nn, cht m v nh mc bng acid HCl 2% thnh 10 mL. y l dung dch
mu xc nh cc kim loi kim bng php o AAS hay ICP-AAS.
V d 2: X l mu xc nh hm lng tng ca thy ngn (Hg). Ly 100 mL nc vo
bnh dung nn tch 250 mL, thm cn thn tng git n 10 mL H 2SO4 98%, 2.5 mL HNO3
65% v lc u. Sau thm 2 mL KMnO4 2% v 8 mL K2S2O3 5%. Lc k sau 15 pht, nu
thy mt mu hng tm nht th nh thm vi git KMnO 4 2% n xut hin mu bn. un cch
thy trong 2 gi, ngui n nhit phng. Sau kh cht oxy ha cn d bng dung dch
hydroxylamin 10%, n ht mu tm v ht c MnO 2, thm 2 git K2Cr2O7 2%. y chnh l
dung dch xc nh Hg theo phng php AAS bng k thut to Hydrua. Cch ny cng
dung c x l mu xc nh Hg trong cc mu nc ngt, bia, v mi loi nc thi.
V d 3: X l mu xc nh hm lng tng ca arsen (As).Ly 200 mL mu vo bnh
Kendan, thm 5 mL H2SO4 98%, 5 mL HNO3 33%, b vo vi mnh s xp nh, chm vo bnh
mt phu nh di chui. un trn bp in n khi thy xut hin khi trng, ri ngui.
Chuyn hon ton mu sang cc 400 mL, trng bnh Kendan 2 ln bng 20 mL nc ct. Thm
40 mL dung dch LaCl3 5%, thm tng git dung dch NH 4OH 12% n pH = 9. Ha tan kt ta
trn giy lc bng 20-25 mL HCl 25% nng, trng ra giy lc 3 ln bng 15 mL HCl 5%, thu
ton b dung dch vo bnh 100 mL v thm 4 mL KI 20%, lc u, nh mc thnh 100 mL, lc
u, un cch thy 20 pht, ngui. y chnh l dung dch xc nh Hg theo phng php
AAS bng k thut to Hydrua. Cch ny cng dung c x l mu xc nh Hg trong cc
mu nc ngt, bia, v mi loi nc thi.
V d 4: X l mu xc nh hm lng tng ca Selen (Se).
Ly 200 mL mu vo bnh Kendan dung tch 400 mL, thm 10 mL HClO 4 70%, 5 mL H2O2
30%, cm vo bnh mt phu nh, un nh cho mu si, n khi no thy khi trng dy c
xut hin th ly ra v ngui. Chuyn ton b mu sang cc un 400 mL, thm 4 mL LaCl 3
10 %, khuy u v thm dung dch NH4OH 25%, n pH = 10, khuy k v un cch thy 10
pht, lc qua giy bng ly kt ta La(OH)3 c hp ph Selen, ra kt ta 2 ln bng dung
dch NH3 c pH = 9. Ha tan kt ta bng 25 mL HCl 1M nng, thu nc lc v nc ra giy
lc vo bnh nh mc 20 mL v nh mc bng nc ct. y l dung dch mu xc nh
Selen. Cch ny cng dng c x l cc loi mu nc, nc thi xc nh Telu (Te), cng
nh cc mu nc ngt, bia, ru v mi loi nc thi.
V d 5: X l mu xc nh cc kim loi trong trng thi l lng trong nc.
Cc nguyn t kim loi hay cc ion trng thi l lng trong nc tc l chng khng tan trong
nc, m kt ta hay bm theo cc ht nh tng, cc ht rn nh, tn ti trong nc, lm cho
nc khng trong. V th nc cng khng trong th lha3 nng c cc ion kim loi cng nhiu.
V th xc nh hm lng ca cc kim loi tn ti cng vi cc ht khng tan trong nc,
trc ht phi tch c cc ht l lng bng cch lc hay ly tm cng vi cht ng t. Ly
200 mL nc vo bnh x l, thm 0.5 g cht ng t, lc u mnh, yn 20 pht, v ly tm
hay lc ly phn cn. Ha tan cn ny bng dung dch acid HCl 1/1 (6M) nng, thu dung dch
nay xc nh cc kim loi bng phng php AAS hay ph phn t UV-VIS
2.1.5. X l mu nc phn tch hu c c hi:
tch cc cht hu c trong loi mu ny chng ta c th dng
_ K thut chi (chit lng lng hay chit lng rn hay trong siu m)
_ K thau65t chng ct
_ K thut sc k: ch yu sc k hp ph trn Silicagel hay nhm oxit
V d 1: X l mu tch ly cc cht hu c nhm hp cht clo-phenois trong nc cc loi
Phng php 1: Chit pha lng lng thng thng, xc nh cc clo-phenol (v d: 2- clophenol, 2,4- diclo-phenol, 2,6-diclo-phenol, 2,4,6- triclo-phenol, 2,4,5- triclo-phenol, 3,4diclophenol, 2,3,4,6- tetraclophenol, Pentaclophenol). Ly 250 mL mu nc, kim h n
pH = 14, lc b cc cn b, dng 50 mL n-Hexan chit b cc cht bo v du m. Ly phn
dung dch nc, v acid ha n pH = 2, chit ly cc clo-phenol bng 20 mL dung mi
Dietylete. Lm bay hi dung mi bng ct quay chn khng hay bng dng kh nito nng, cn
li b m mu, ha tan trong 5 mL propanol v xc nh cc Clophenol bng phng php
HPLC v GC.
Phng php 2: Chit tch 1 s cht hu c thuc h Pesticide trong mu nc[ methode
3550b]. Ly 250 ml mu vo bnh chit chnh pH =2, thm 40 ml dung mi chit ( CH 2Cl2 n
hexane theo t l V/V = 2/1 ), trn u, y np v t vo bung siu m, ng cht my siu
m, chn v t cc thng s siu m thch hp tin hnh chit trong 40 pht. ngui lc
hn hp mu ra tch pha, ly dung dch pha hu c, lm bay hi dung mi bng phng php
chng ct quay chn khng n khi cn 1 ml, ngui ta c b t. Ha tan b ny trong
5 ml dung mi MeOH hay n hexane. y l dung dch mu xc nh cc nhm Pesticide
bng phng php GC, HPLC hay GC MS.
Phng php 3: Chit pha rn. Chit tch 1 s cht hu c thuc h Pesticide trong mu
nc[ methode 3550b]. Ly 250 ml mu vo bnh chit chnh pH =2,lc b cn ri di ln ct
chit loi XAD 2, 5 m vi tc 2 4 ml/pht, cho n khi chy ht mu qua ct chit.Sau
gii chit cht phn tch ra khi ct chit bng 20 ml dung mi n hexane c 15% CH 2Cl2.
Thu dung dch ra ui cho ht dung mi bng dng kh tr sch n cn b m, ha tan b ny
trong 5 ml dung mi MeOH.y l dung dch mu xc nh cc nhm Pesticide bng
phng php GC, HPLC hay GC MS.
b qua giy lc bng . Ly dung dch lc v nc ra, thm 30 mL HCl 36%, nh mc thnh
100 mL. y l dung dch xc nh Selen. Cch x l ny c th dng c x l cc mu t
bn, trm tch, qung, b thi rn xc nh Se.
V d 8: X l mu xc nh hm lng CN -. Trc tin mu c xay nh thnh bt, trn
u, ly 10g vo bnh chit, thm 2 mL NaOH 1M, thm 50 mL nc nng (55-60oC), chnh pH n
9-10 bng NaOH, thm 10 mL huyn ph CuCO 3 (10% trong nc), t vo my siu m trong 5
pht, lc u, ly tm ly dung dch trong xc nh Cu bng AAS, ri suy ra hm lng CN - v
trong qu trnh trn c phng ng to ra phc Cu(CN)3 nh sau:
CuCO3 + 3CN- = Cu(CN)3 + CO32Ngha l 1 mol Cu tng ng vi 3 mol ion CNV d 9: X l mu xc nh hm lng CNS. Trc tin mu c xay nh thnh bt, trn
u, ly 10g vo bnh chit, thm 2 mL NaOH 1M, thm 50 mL nc nng (55-60oC), chnh pH n
0-1 bng HCl, lc u,thm 2 mL FeCl3 5%, t vo my siu m trong 5 pht, lc u, ly tm ly
dung dch phc Fe(CNS) xc nh CNS. Ta chit ly phc Fe(CNS) vo Dietylete hay MIBK
hay CHCl3. Sau xc nh phc ny bng php o ph hp thu phn t trong vng = 480-500
nm.
5.2.2.4. X l b thi phn tch cc cht hu c:
Theo sch cch c trinh by trong chng 2 muc 2.4 chng ta p dng cho x l mu
b thi phn tch cc cht hu c
V d 1: X l xc nh mt s cht hu c c hi. Dng k thut chit rn lng. Ly
10g mu c nghin nh v trn u vo bnh chit, nh ha mu bng 20 mL nc nng, lc
k 5 pht. Thm 20 mL n-Hexan, lc chit 10 pht, tch ly phn hu c, ri lp li vic chit mt
ln na. Gp 2 phn chit n-Hexan li. l dung dch mu xc nh mt s hp cht hu c
c hi, nh nhm cc clo-phenol, cc cht dn xut clo,brom ca cc hydrocacbon thm a vng.
V d 2: Chng ct tch cc hp cht h clo-phenois v pesticide t mu t,b thi [Metho
3550] Ly 10g mu nghin mn vo bnh chng ct, nh ha trong 50mL dung mi hu c, v d
diclo-methylen + n-hexan (1/1), thm 25g Na2SO4 khan, lc k v chng ct ly cht phn tch vo
bnh ngng, lm bay hi ht dung mi bng dng kh nito sch, hay ct quay chn khng n cn
b sn st. Ha tan b cn li trong 5 mL MeOH v xc nh cc cht trong dung dch mu ny
bng phng HPLC hay GC.
V d 3: Chit tch mt s cht hu c thuc h pesticide trong mu t, bn, trm tch,b
thi [Method 3550b] Ly 20g mu nghin mn vo bnh chit thm 30g mui khan Na 2SO4, thm
50mL dung mi chit (diclo-methylen + n-hexan trong t l: V/V = 2/1), trn u, y np v t
vo bungn siu m, ng cht my siu m, chn v cc thng s siu m thch hp chit.
Tin hnh chit trong 50 pht. ngui, ly hn hp mu ra tch pha, ly dung dch pha hu c,
lm bay hi dung mi bng phng ct quay chn khng n khi cn 1mL, ngui, ta c b
t. Ha tan b ny trong 5 mL dung mi MeOH (hay n-hexan). y l dung dch mu xc nh
cc cht trong nhm Pesticaide bng phng php sc k GC, GC-MS hay HPLC.
2.3. X l mu khng kh, khi v bi:
2.3.1. Khng kh, kh quyn v mi trng
Khng kh l mi trng xung quanh chng ta. Khng kh thun khit c thnh phn chnh
l Nit (78.2%), oxy (gn 19.7%), kh CO2 (khong 2%), vmt lng rt nh 5 kh khc khng
ng k (tng di 0.2%), nh ozon (0.000001%), kh NH 3, v.v. ng thi thm vo l cc loi
kh thi ca sn xut cng nng nghip, ca sinh hot ca con ngi. (Xem cc bng 1, 2, A3, A4,..
trong ph lc 1 v 2 cui.)
Nhng trong qu trnh sinh sng v pht trin cng nng nghip v c nghin cu khoa hc,
con ngi thi vo mi trng khng bit bao nhiu cht khc nhau, c cht v c, c cht hu
c, c cht dng kh, nh kh NO 2, SO2, CH4, NH3, cc hi kim loi (Hg, As), bi kim loi, hp
cht c kim (Etyl-Pb). Cc cht dng cc ht bi l lng cng khng t, nh kh nh my in,
nh my xi mng, nh my ha cht, bi khai thc than, khong sn. Trong t hp phong ph v
phc tp , c rt nhiu cht c hi, hay rt c hi vi chnh cuc sng ca con ngi, m c khi
chng ta cha thy c. C cht ph tng kh quyn bo v cho con ngi bi cc tia sng mnh
(cc cht hu c ca F, nh CH2F2, CHF3,..) Ri cc v th v kh, nht l v kh ht nhn. ng
thi cng thi ra mt khi lng khng l cc cht lng d bay hi, cc cht tan vo nc chy ra
cc sng sui. Tt c nhng vic lm a vo khng kh, mi trng sng ca chng ta bit
bao nhiu th m hu qu ang e da con ngi hng ngy.
Bng 9. Thnh phn ca khng kh, kh quyn
Thnh phn cht
Nng (%) (bnh thng) Tng lng (Tn)
N2 (Nit)
78.08
3.90. 109
O2 (Oxy)
20.94
1.20. 109
H2O (Hi nc)
20 100%
50.000 km3 (tng)
Ar (Argon)
0.93
6.70. 107
CO2 (Cacbonic)
0.035
2.80. 106
Ne (Neon)
0.0018
6.60. 104
He (Heli)
0.0005
3.70. 103
CH4 (Metan)
0.00016
4.60. 103
H2 (Kh Hydro)
0.00005
1.70. 102
O3 (Ozon)
0.000004
3.40. 102
NO2 (Dioxit nit)
0.000003
1.60. 102
Vn vn
2.3.2 Ngun gy nhim khng kh v kh quyn.
Hng ngy mi trng xung quanh chng ta lun b nhim do nhiu ngun khc nhau thi vo
khng kh. Cc th thi , c th khng c hi nhng cng c th rt c hi cho con ngi,
ng vt v cy ci ang sinh sng. cc ngun gy nhim c th l
1. Do chnh thin nhin to ra.
Ni la, ng t, sc l ca ni
Nn chy rng
Ging t, gi bo, l lt..
2. Do con ngi to ra
Trong sinh hot hng ngy thi ra, un ci, than t cc th
Do khi v bi ca cc nh my cng nng nghip thi ra
Kh thi ca cc nh my nh ha cht du kh cng nghip
Do xe t v cc phng tin my chy xng du khi thi ra
Nghin cu khoa hc , l phn ng ht nhn.
Chin tranh, th v kh.
Chi cc loi pho, dng thuc n nh c.
Tt c cc th thi vo khng kh xung quanh ta ( kh quyn tri t ), cc th cht thi bao
gm.
1. cc cht v c:
Cc kh CO, CO2, SO2, NO, NO2, Cl2,Br2, H2S, HCN
Cc hi kim loi ( Hg, Pb, Cd, Mn, Cr ), hi mui kim loi
Cc bi silic, amiang, xi mng, bt thy tinh
2. cc loi hp cht hu c.
Mt s hydro cacbua dng kh, aldehyd, alcol, axetylen, aceton..