1

L C (Ch bin)











MT S PHNG PHP
PHN TCH MI TRNG

















NH XUT BN I HC QUC GIA H NI
2

LI NI U

Ngy nay, cc vn mi trng tr thnh mi quan tm ca nhn loi. Nhiu ni trn th
gii v Vit Nam mi trng ang b suy thoi, ti nguyn thin nhin tr nn cn kit, h sinh thi
mt cn bng, cht lng cuc sng suy gim. Mt trong nhng nguyn nhn chnh l do hnh vi,
nhn thc v thi ca con ngi i vi mi trng sng ca mnh cn hn ch. Trong lut bo v
mi trng (1993) ch r: "Nh nc c trch nhim t chc thc hin vic gio dc, o to,
nghin cu khoa hc v cng ngh, ph bin kin thc khoa hc v php lut bo v mi trng".
Gio dc mi trng tt c cc cp hc tr nn v cng quan trng trong thi k cng nghip ho
v hin i ho t nc.
Ngh nh s 1363/Q-TTg ngy 17 thng 10 nm 2001 ph duyt n v nu ra 5 hot ng
c th, trong hot ng s 1 l xy dng chng trnh, gio trnh, bi ging v gio dc bo v mi
trng cho cc bc hc, cp hc v cc trnh o to. Thc hin ch trng trn, B Gio dc v
o to t chc bin son cun sch "Khoa hc mi trng" xut bn nm 2001, lm ti liu hc
tp v tham kho cho cc trng i hc v Cao ng.
thc hin tip vic xy dng chng trnh, gio trnh chng ti tin hnh bin son cun sch
"Mt s phng php phn tch mi trng".
Ni dung cun sch gm 2 phn chnh:
Phn 1: Gii thiu c s ca mt s phng php phn tch ph bin trn th gii dng trong
phn tch mi trng, l cc phng php trc quang, quang ph hp th nguyn t, cc phng
php phn tch in ha, phng php cc ph, cc phng php sc k, khi ph, kt hp sc k kh -
khi ph phn tch cc cht nhim thng gp trong mi trng nh kim loi nng, ha cht bo
v thc vt... ng thi cng gii thiu mt s phng php dng nh gi kt qu ca cc s liu
phn tch.
Phn 2: Gii thiu phng php ly mu, bo qun mu v phng php phn tch mt s ch
tiu quan trng trong cc thnh phn mi trng: t, nc, khng kh. Mi phng php phn tch
c trnh by theo trnh t: nguyn l phng php, trnh t phn tch, tnh ton nh gi kt qu
phn tch.
Cun sch: "Mt s phng php phn tch mi trng" l mt gio trnh trong chng trnh o
to c nhn khoa hc mi trng, trang b cho hc sinh, sinh vin nhng kin thc thc hnh v phn
tch mi trng. Sch cn l ti liu tham kho cho nhng nh qun l mi trng, nhng k thut vin
phn tch trong cc phng th nghim ha hc, sinh hc v mi trng.
Do nhng hn ch v thi gian bin son, chc chn cun sch khng trnh khi sai st, chng ti
mong nhn c kin ng gp ca ngi c cun sch c hon thin.
H Ni, ngy 22/12/2002
Tp th tc gi
3
Phn 1. Nhng vn chung
Chng 1. M u
1.1. Mi trng
Mi trng bao gm tt c cc yu t l hc, ho hc, cc cht hu c v v c ca
kh quyn, thch quyn v i dng. Mi trng sng l tp hp cc iu kin xung
quanh c nh hng n c th sng, c bit l con ngi. Mi trng quyt nh
cht lng v s tn ti ca cuc sng.
Mt s nh nghin cu s dng thut ng vi mi trng ch r mi trng
chc nng (functional environment), ngha l mi trng ring bit ca cc c th c
bit. Theo ngha en, thut ng ny lin quan n mi trng nh, ngha l mi trng
trc tip nh hng ca c th.
1.2. Phn tch mi trng
Phn tch mi trng c th c nh ngha l s nh gi mi trng t nhin v
nhng suy thoi do con ngi cng nh do cc nguyn nhn khc gy ra. V vy,
phn tch mi trng bao gm cc quan trc v cc yu t mi trng ni chung. y
l vn rt quan trng v qua chng ta c th bit c yu t no cn c quan
trc v bin php no cn c p dng qun l, gip chng ta c th trnh khi cc
thm ho sinh thi c th xy ra.
Trong nhng nm gn y, nghin cu sinh thi khng ch l s tip cn v cht
lng m cn c s lng. c th hiu bit v nh gi v mt h sinh thi i hi
phi quan trc y s bin ng theo khng gian v thi gian ca c cc yu t mi
trng, c v s lng v cht lng c lin quan n cu trc v chc nng ca h.
l cc tnh cht l, ho v sinh hc ca h sinh thi.
1.3. S la chn phng php phn tch mi trng
Vic la chn phng php v cc quy trnh trong phn tch mi trng i hi
phi c nhiu kinh nghim. Cc phng php la chn phi tr li c nhng cu hi
sau:
S dng phng php phn tch no?
Lng mu c cho nhiu phng th nghim khng?
Yu t no hn ch s pht hin, chnh xc ca cc phng php phn
tch c s dng.
Ngi s tin hnh phn tch?
4
Nhng vn g cn ch trnh lm bn mu trong qu trnh bo qun
mu.
Cc ch tiu no cn phn tch phn nh thc t kh nng c hi ca
mi trng? Hm lng hay dng tn ti ca cc nguyn t ho hc.
1.4. Gi tr ca cc s liu trong phn tch mi trng
Mt vic kh khn vi cc nh nghin cu l phi xc nh c nhng ch tiu
phn tch no l cn thit. Vic xc nh thnh phn cc nguyn t l hay cn cn
phi phn tch cc phn t hay cc nhm chc ca cc cht?
V d: Khi phn tch hm lng tng s cc nguyn t nh Hg, Pb, P,...c th s
khng nh gi ht c tim nng gy hi cho sc khe con ngi. iu ny cng
tng t nh vic nh gi mi quan h gia hm lng tng s ca cc cht trong
t vi kh nng s dng ca cy trng.
Ch c mt phn trong hm lng tng s l d tiu i vi thc vt. Do vy vn
kh khn l s dng phng php ho hc no phn nh ng cc hot ng ca
h r thc vt. Trn thc t kt qu ny thng rt hn ch . V d vi cy rau dip
(lettuce), hm lng ch trong cy c quan h vi lng ch chit rt t t bng HNO
3

1M. Trong khi vi cy yn mch (Oat), hm lng ch trong cy li tng quan vi ch
chit rt bng HNO
3
0.01M hoc NH
4
CH
3
COO 1M. Vic phun dung dch CuSO
4
ln
l hoc t lm tng hm lng ng trong cy la m, nhng hm lng ng trong
cy li khng c tng quan vi lng ng d tiu c xc nh trong dung dch
chit rt NH
4
CH
3
COO 1M, axit mnh hoc cht to phc (EDTA).
Mc d c nhng hn ch nht nh, cc quan trc cc yu t ring bit vn cn
c tin hnh nh xc nh cc vng b nhim ghi nhn cc thay i v mc
cc cht nhim v cc dn liu ca cc yu t bn ngoi nh gi, ma, a hnh,...
nghin cu xu hng bin i, c th xc nh mt chui quan trc. V d: s
liu bng 1.1 a ra mc nhim 4 loi ch th c phn tch.
Bng 1.1. nh hng ca hng t ngun i vi s tch lu
ca ion kim loi trong mu
Mu
im ly mu
C a y Ru t
Pb (ppm)
A 10 130 120 -
B 49 1528 1200 -
C 86 - - 270
D 150 - - 230
Zn (ppm)
A 102 675 1213 -
B 146 1135 4870 -
C 350 - - 450
D 270 - - 416
5
Cd (ppm)
A 8 68 93 -
B 13 83 137 -
C 9 - - 7.1
D 9 - - 7.7

S liu bng 1.1 cho thy mc nhim thay i theo hng a l (hng
A,B,C,D). Tuy nhin nu vic la chn c nh hng s cho thy mc nhim so
vi cc vng khc.
Nhng quan trc tng t cng c th c p dng vi mi trng nc. Nhng
vic phn tch n thun cc mu nc lc s hn ch ngha ca cc s liu phn
tch. Trn thc t cc cht l lng v cc cht lng ng cc h nc c th gii
phng ra cc cht c hi trong cc chui thc n hoc i sng ca cc sinh vt thy
sinh.
Cn l lng thng l nhng hn hp phc tp bao gm cc cht hu c, v c v
phc hu c - v c. Gia chng li c s tng tc khc nhau nh cc keo st trong
nc mn c th hp ph trn 2,5% axit mn. S c mt ca cc axit humic s lm
tng kh nng hp ph ca cc cht l lng. S thay i ca cc cht in ly s lm
thay i qu trnh ny (trong nc ngt lng axit humic c hp ph l nh hn
0,4%). Do vy ti ni tip gip gia vng nc ngt v nc mn (vng ca sng) s
c s bin i t ngt v s phn b ca cc kim loi nng gia pha rn v lng.
V cc sinh vt bin c xu hng tch lu cc kim loi nng khi sng trong mi
trng nhim nn chng c th c coi nh cc vt ch th. Cc s liu ny c th
so snh vi kt qu iu tra trung bnh trong ng vt gip xc (tm, cua...). i vi
thc vt, hm lng ion kim loi ca mt sinh vt c bin ng ln (hng chc ln) so
vi v tr tng i ca n i vi ngun nhim, nhng hm lng ny l tng i
n nh trong vng ly mu v c s khc nhau ln so vi cc gi tr c xc nh.
Ti mt ni xc nh s dao ng hm lng ca mt cht c th l 20%. V vy
s khc nhau nhng ni khc nhau phi ln hn s liu thng k c ngha.
1.5. nh hng ca cn bng
Cc s liu trong bng 1.1 c xem xt trn c s cc cn bng nh di y.
V ru l vt bm trn cy nn s tch lu cc ion kim loi c th trc ht l t
bi v kh xung quanh. V vy, hm lng ca mt s cht c th b gim nc ma
ra tri. Cc cy mc trn t c kh nng s dng cc cht rt khc nhau v ph
thuc vo cc tnh cht ca t. Kh nng hp thu cc cht ca cy cng b gim st
khi c s cnh tranh gia cc cht hp thu. Nu h thng khng qu phc tp, qu
trnh hp thu cc cht c th c biu din bng phng trnh ton hc nh sau:
(x/m) a = k
1
.Ca.Sv/ ( 1+k
1
Ca + k
2
Cb + k
3
Cc + ...)
Trong : (x/m)a : L s lng m loi a ht thu trn 1g cht
6
S
v
: L gi tr cc i (hoc bo ho), Ca, Cb,Cc l hm lng ca cc loi
cnh tranh a,b,c ; k
1
, k
2
, k
3
l h s ht thu tng ng. Trong trng hp k
2
Cb hoc k
3

Cc >> k
1
Ca th (x/m)a s gim rt mnh.
Cc qu trnh trong h thng cn bng c trnh by hnh 1.1 .




















Vai tr quan trng trong h thng ny l hot ng ca vi khun, nh trng hp
nhim thu ngn (Hg). S chuyn ho gia hp phn thu ngn v c thnh ion
metyl thu ngn (II) (CH
3
Hg
+
) xy ra rt ph bin tng mt ca cc cht trm tch
hoc cc phn hu c l lng.
Tc chuyn ho ph thuc vo qu trnh thy ngn xm nhp vo cht hu c.
Dng lin kt hu c - kim loi s nhanh chng c c v thc vt s dng, chng c
xu hng tch lu trong c th sinh vt. S tch lu Hg trong h thng h hoc vng
ca sng nh sau: Cht trm tch cha 90 - 99% thy ngn (khong 10% l CH
3
Hg
+
),
pha nc t 1 n 10% (hu ht dng lin kt v c vi cc cht l lng), sinh vt
<0,1% (ch yu l CH
3
Hg
+
). c bit cc loi gip xc trong sinh quyn bin (nh
trai, s, tm cua...) c kh nng tch lu thy ngn rt cao.
Mt s vi khun c kh nng chng chu vi nng Hg cao v c th chuyn ho
cc hp cht hu c - thy ngn thnh dng thy ngn t do khng ho tan. Hn na
trong iu kin k kh, cc vi khun kh sunphat cng c kh nng sinh ra
Bi Sol kh
Cht kh
ION CHT V C
N GIN
CHT HU C
HA TAN
+
Phc h
ha tan
CHT RN VI SINH VT
SINH VT
Nc trao i
O
2
Hp ph trao
i ion
Cht lng ng
Hot ng ca
vi sinh vt
Trm tch sinh hc hoc
vt th v c
Hnh 1.1. S h thng cn bng v tc ng qua li gia chng trong h nc t nhin
CO2
KH QUYN
O
2

7
hydrosunphua c nh Hg
2+
di dng sunphua, vi khun khng chuyn ho hp
cht ny thnh metyl thu ngn.
Xem xt cc cn bng phc tp trong hu ht cc h thng t nhin, iu cn lu
khng ch l vic la chn cc ch th m cn l cc kh khn trong vic ly, vn
chuyn v bo qun mu. V l thuyt, iu cn thit l lm ngng tr tt c cc qu
trnh ho hc cng nh sinh hc bng cc phng php thch hp. Cc qu trnh bin
i ny s c gim ti mc ti thiu nhit thp hoc s dng nhng phng th
nghim di ng. Tuy nhin tn ti mt vn l: h thng cn bng trong t nhin
lun lun b xo trn. V d nh ly mt mu nc pha trn trm tch (hoc tch cc
cht l lng) s lm cho mt hp phn hoc cc cht ho tan thit lp mt cn bng
mi. Tuy nhin, v mt tng s vn khng thay i v s l cc dn liu cho s
nhim.
Vn tip theo cn ch nh gi mc nhim l phi la chn cc
phng php phn tch c chnh xc thch hp v cn c tin hnh trong thi
gian nht nh.
8
Chng 2. chnh xc v tin cy ca php phn tch
2.1. Bo m v kim sot cht lng trong phn tch mi trng
Bo m v kim sot cht lng i hi tt c cc phng th nghim phi tun
th theo cc hng dn c a ra m bo kt qu phn tch c tin cy cao.
Bo m cht lng thng qua hng lot cc nguyn l v s gim st cht ch
chnh xc ca kt qu phn tch c tin cy v tnh php l cao. Vn bo m cht
lng bao gm c vic ly mu v bo qun mu ca cc phng th nghim v trch
nhim cng nh k nng ca cc c nhn phn tch v ngi chu trch nhim. Vi
ngha rng hn th c k hoch cng c bao gm trong vic kim sot cht lng.
Kim sot cht lng phng th nghim bao gm: cc ti liu v phng php tiu
chun, cc php th, chun b cc ng chun v kim tra thng xuyn cc thuc
th, my mc, xc nh chnh xc v tin cy ca php phn tch, chun b s
kim tra.
Chun b ng chun:
Cc ng chun c xy dng trn c s cc php o mu hoc sc k kh cc
nng khc nhau v c chun b hng ngy trc khi phn tch mu. Nu kt qu
o c sai s 15% th cn phi xy dng li ng chun.
2.2. Sai s v chnh xc
Sai s c th hin qua kt qu phn tch ca cc ln lp li. Nu mt mu c
phn tch lp li nhiu ln trong cng mt iu kin th kt qu cng s khc nhau do
sai s th nghim hoc do thao tc. Cc kt qu ny s phn b mt cch ngu nhin
xung quanh mt gi tr trung bnh l gi tr trung bnh cng ca cc php o. Khi cc
kt qu o phn b nh dng hnh qu chung c gi l ng cong phn b chun
hoc ng Gauss (Gaussian Curve) nh hnh 2.1 (trong nhiu mu mi trng b
nhim bn th kt qu s khng theo s phn b chun).






Hnh 2.1. ng cong phn b chun
Gi tr trung bnh ( x ) c tnh bng
n
x

( x: cc gi tr o, n: s ln o).
9
lch chun (S) s xc nh chiu rng ca th phn b v c tnh nh
sau:
S =
( )
1
2

n
x x

Trong trng hp hm phn b chun th 68,27% din tch nm trong khong x
1S; 95,45% nm trong khong x 2S, v 99,70% nm trong khong x 3S. Gi tr
3S xung quanh gi tr trung bnh l gii hn trn v di trong th kim tra. Tt c
cc gi tr nm ngoi x 3S c xem l khng bnh thng. iu ny chng t rng
c vn no trong qu trnh phn tch cn phi c xem xt ngay.
lch chun cng c th c tnh theo cng thc nh sau:
S =
( )
1
2
2

n
n
x
x

Trong : :
2

x Tng bnh phng ca cc gi tr o

:

x Tng cc gi tr o
n : S php o
Mc d sai s hoc kt qu phn tch lp li c th c biu din di dng ca
lch chun nhng ln gi tr phn tch c th lm thay i ng k lch chun
ln cc gi tr tng ng. C th minh ho iu ny qua 2 v d sau y:
V d 1: Hm lng tng s hyrocacbon du m - TPH (total petroleum
hydrocarbon, TPH) trong mu b nhim bn vi 6 ln phn tch l 5,3 - 4,9 - 5,1 - 5,5 -
4,7 v 5,0 mg/L. Xc nh lch chun nh sau:

x x
2
5 , 30
0 , 5
7 , 4
5 , 5
1 , 5
9 , 4
3 , 5

45 , 155
00 , 25
09 , 22
25 , 30
01 , 25
01 , 24
09 , 28

= 5 , 30 x 45 155
2
, x =

( ) 25 930
2
, x =

n =6
26,01
10
S = l / mg ,
,
,
29 0
1 6
6
25 930
45 155
=

V d 2: Nu kt qu phn tch TPH trong mu c gi tr ln gp 10 ln
ngha l 53 - 49 - 51 - 55 - 47 v 50 mg/l th lch chun s l :
x =
5
6
93025
15545
= 2,86 mg/l
Nu gi tr o c ln hn, v d nh 530 - 490 - 510- 550 - 470 v 500 mg/l th
S = 28,6 mg/l. Nh vy lch chun khi bin i theo ln cc gi tr o c l
khng c ngha tr khi ln ca gi tr phn tch c xc nh trc.
Ni mt cch khc, sai s phn tch s lun c gi tr khi lin quan vi gi tr ca
mu o. Mt cch biu th khc l lch chun tng i (RSD - Relative Standard
Deviation) hoc h s bin thin (Coefficient of Variance - CV). y l t s gia
lch chun v gi tr trung bnh i s:
RSD = % 100 .
x
S

Trong v d 1 v 2 trn, RSD s l :
% 708 , 5 100 .
08 , 5
29 , 0
=

% 708 , 5 100 .
8 , 50
86 , 2
=
Nh vy, RSD hai v d ny l bng nhau trong khi S c s khc nhau r rt
(0,29 v 2,8 mg/l).
Mt cch khc biu th sai s l sai s chun ca gi tr trung bnh (M), y l t
s gia S v cn bc hai ca s ln o (n).
M =
n
S

Trong phn tch mi trng, thng thng vic lp li nhiu ln l kh thc hin
c. V vy sai s ca php phn tch c tnh ton thng qua khc nhau phn
trm tng i (Relative percent difference - RPD). T s ny c xc nh thng
qua s phn tch lp li hai ln mu trong mt iu kin xc nh. l t l phn
trm gia hiu s ca kt qu gia hai ln phn tch vi gi tr trung bnh cng ca
chng.
RPD =
( ) ( )
% x
a a
a a hoc a a
100
2
2 1
1 2 2 1

+


Trong : a
1
v a
2
l gi tr ca hai ln phn tch mt mu
11
V d 3: Hm lng Cl
-
trong hai ln phn tch mt mu l 9,7 v 11,1 mg/l. Sai s
s c xc nh nh sau:
RPD =
( )
5 13 100
2
7 9 1 11
7 9 1 11
, % x
, ,
, ,
=

%
chnh xc ca gi tr phn tch l mc chnh xc ca n so vi hm lng
thc t c trong mu. chnh xc c nh gi qua vic cho thm vo mu mt
lng nht nh dung dch chun c nng bit. Da trn phn trm nng cho
thm c pht hin iu chnh chnh xc cho kt qu phn tch. Nhn chung
trong phn tch mu mi trng, khng yu cu cc php tnh iu chnh sai s ca
kt qu phn tch. Tuy nhin trong nhng php phn tch c bit no , vic iu
chnh sai s c th c t ra. Khi phn tch mt s cht hu c trong nc thi,
U.S.EPA (The United States Environment Protection Agency) a ra bn vng cho
lng phn trm c xc nh. Nu gi tr ca bt k mt php phn tch no nm
ngoi cc vng ny th cc ch s QC cho php phn tch s khng c p ng.
Mt ma trn lng b sung pht hin c c th c xc nh bng hai cch:
Phng php xc nh phn trm thu hi t lng tiu chun thm vo chng hn nh
phng php ca U.S. EPA
(1)
v phng php tnh phn trm thu hi gia mu cn o
v dung dch chun
(2)
. Lng tm thy c tnh ton bi hai phng php s cho cc
gi tr khc nhau.
Cch xc nh 1 (U.S. EPA):
% lng tm c =
( )
100 x
k
x x
u i


Trong : X
i
: Gi tr o c cho mu ho trn
X
u
: Gi tr o c cho mu khng ho trn th tch sau khi
ha trn.
K : Gi tr bit nng ca mu chun trong mu ho trn
Cch xc nh 2:



Nng l thuyt c th tnh nh sau:

( )
( )
( )
( )
s u
s s
s u
u u
V V
xV C
V V
xV C
+
+
+

Trong : C
u
: Nng o c ca mu
C
s
: Nng ca dung dch tiu chun
V
u
, V
s
: L th tch ca mu v dung dch tiu chun
Phn trm lng thu hi theo cc cch tnh trn y c th c minh ha trong
cc v d sau y:
Nng o c
% lng tm c
Nng l thuyt
=
x 100
12
V d 4: Mt mu nc thi c xc nh c nng xianua l 3,8 mg/l. Sau khi
cho thm 10ml dung dch tiu chun c nng xianua l 50 mg/l vo 100ml mu
nc thi trn. Nng ca xianua trong hn hp thu c l 8,1 mg/l.
- Tnh phn trm lng thu hi t dung dch ny (sau khi pha ln) theo cch tnh 1.
+ Da theo nng xc nh:
X
i
= 8,10 mg/l
X
u
= (3,8 mg/l . 100 ml)/ 110 ml = 3,454 mg/l
K = (50 mg/l . 10 ml)/ 110 ml = 4,545 mg/l
% lng thu hi = (8,10 mg/l - 3,454 mg/l).100%/ 4,545 mg/l = 102,2%
+ Da trn khi lng (phng php chuyn i) khi lng tng s ca ion CN
-

trong 110 ml mu v dung dch tiu chun l:
8,1 mg/l x 0,110l = 0,891mg
Khi lng ion CN
-
tnh theo phn trm trong 100ml mu cn xc nh ban u:
3,8 mg/l x 0,100 L = 0,38 mg
Khi lng ion CN
-
trong 10 ml dung dch tiu chun l:
50 mg/l x 0,010 L = 0,500 mg
- Tnh phn trm lng tm c nh trong cch xc nh 2.
+ Tnh ton da trn nng :
Nng CN
-
o c sau khi c b sung thm bng dung dch chun l
8,1mg/L. Nng thc t ca CN
-
sau khi pha trn s c gi tr bng nng CN
-
ban
u trong mu + nng CN
-
trong lng dung dch tiu chun b sung thm. Hay:
(3,8 mg/l . 100 ml + 50 mg/l . 10 ml)/ 110 ml = 8,00 mg/l
% lng tm c = (8,10 mg/l . 100)/ 8,00 mg/l = 101,2%
+ Tnh ton da trn khi lng (phng php chuyn i):
Khi lng xianua o c trong tng s 110 ml dung dch (100 ml mu + 10 ml
dung dch chun b sung thm) s l:
8,1mg/l x 0,110l = 0,891 mg
Khi lng thc t ca xianua trong 110 ml dung dch ny l:
(3,8mg/L x 0,100L) + (50mg/L x 0,01L) = 0,880 mg
% lng tm c = % , x
,
,
2 101 100
880 0
891 0
=
V d 5: Mt mu o c 11,7 mg/l. Nu b sung thm 5 ml dung dch chun c
nng 100 mg/l vo 50 ml dung dch ny s c dung dch c nng o c l
18,8 mg/l.
Tnh lng b sung tm thy c nh trong cch tnh 1 v 2 (tnh trn c s nng
).
Cch xc nh 1:
X
i
= 18,8 mg/l
13
X
u
= (11,7 mg/l . 50 ml)/ 55 ml = 10,64 mg/l
K = (100 mg/l . 5 ml)/ 55 ml = 9,09 mg/l
% lng tm c = (18,80 mg/l - 10,64 mg/l).100/ 9,09 mg/l = 89,8%
Cch xc nh 2:
Nng o c =18,8 mg/l
Nng thc = (11,7 mg/l . 50 ml + 100 mg/l . 5 ml)/ 55 ml = 19,7 mg/l
% tm c = 18,8 mg/l . 100%/ 19,7 mg/l = 95,3%
Khi lng tm thy l nh hn 100% theo US. EPA (cch tnh 1) s cho gi tr
thp hn khi tnh theo cch th 2 (v d 5). Tuy nhin nu lng tm li c m ln
hn 100% s cho gi tr ngc li (v d 4).
i vi vic phn tch cc mu t v cht thi rn th khng cn phi iu chnh
nh i vi mu nc. V t v cht thi rn phi dng mt cht lng chit rt,
nh v d 6 di y.
V d 6: Mt mu t c chit rt xc nh hydrocacbon du m (PHC) bng
phng php o ph hng ngoi. Hm lng PHC trong mu xc nh c l 285
mg/ kg. Thm 2 ml dung dch chun PHC c nng 1000 mg/l vo 40 gam mu.
Nng PHC mu ny o c l 326 mg/kg. Xc nh tin cy ca php phn tch
theo phn trm lng tm c t lng b sung ca dung dch chun.
Khi lng ca PHC trong mu thm dung dch chun l:
40 g x mg ,
g
mg
04 13
1000
326
=
Khi lng ca PHC trong mu trc khi b sung dung dch tiu chun cha PHC
l:
40 g x mg ,
g
mg
40 11
1000
285
=
Lng b sung = 2ml x mg ,
ml
mg
00 2
1000
1000
=
% tm c = % , x
mg ,
mg , mg ,
8 96 100
40 11
00 2 04 13
=

Nh vy, khi lng mu c b sung bng dung dch PHC chun l 40 g ch
khng phi 43 g (thm 2 ml dung dch chun c t trng khong 1,5 g/ml) theo tnh
ton trn. Thc t l 2 ml dung mi thm vo s trn ln vo cht chit rt. V vy,
khi lng ca mu sau khi chit rt (tc l khi lng ca phn cht rn cn li) hu
nh khng thay i so vi trc khi chit rt chng.
Phn trm pht hin c t lng b sung thm vo mu ni trn c th c xc
nh theo cng thc US. EPA nh sau:
X
i
= 326 mg/kg
X
u
= 285 mg/kg
14
K = kg / mg
kg
g
x
g
ml
mg
mlx
50
1
1000
40
1000
1000
2
=

% pht hin c =
( )
% , x
kg / mg
kg / mg kg / mg
0 82 100
50
285 326
=

Khng c s iu chnh chnh xc v khi lng hoc th tch no c a vo
trong cch tnh ton trn. V vy, X
u
c ly l 285 mg/kg.
Lng phn trm pht hin c trong v d trn c tnh theo cch 2 s l:

( ) ( )
% , x
kg / mg kg / mg
kg / mg
3 97 100
50 285
326
=
+

2.3. th kim tra
C hai loi th kim tra l th kim tra chnh xc v th kim tra sai s.
th kim tra chnh xc c xy dng t cc lng pht hin c (%) trong cc
phn tch thng thng. th kim tra sai s c th c xy dng trn c s s khc
nhau phn trm tng i (RPD) ca nng phn tch trong mu v s liu phn tch
lp li. Cc khc nhau phn trm tng i (RPDs) c tnh ton cho phn trm
lng pht hin c trong ma trn cc nng tiu chun v phn tch lp li cc ma
trn cht chun trong mi t. Khong 20 im (hoc mt s lng hp l cc im s
liu) c a ra s phn nh tn sut hoc s ln phn tch. Nu nhng mu khng
pht hin c, cn phi pha thm dung dch chun c cha cht phn tch v RPD cn
phi c xc nh cho mt ma trn cc lng pht hin c. Cc s liu ny c th
c kim tra da vo cc thng tin c sn trn th kim tra. Bt k mt vn no
xut hin trong php phn tch c th c nhn bit thng qua lch ln so vi gi
tr trung bnh.
Trong php phn tch bnh thng, mt mu phn tch s c pha vi mt nng
chun bit, v s xc nh c phn trm lng pht hin c. th kim tra
c xy dng nh hnh 2.2.











S ln phn tch
Tn sut
+3S
+2S
S
-2S
-3S
15
Hnh 2.2. th kim tra chnh xc
Gii hn cnh bo cn trn UWL (Upper Warning Limits) v cn di LWL
(Lower Warning Limits) c xc nh mc 2S. Gii hn kim tra cn trn UCL
(Upper Control Limits) v cn di LCL (Lower Control Limits) c xc nh mc
3S xung quanh gi tr trung bnh. Nu s liu no nm ngoi vng UCL v LCL,
th sai s phn tch cn phi c xc nh v c lm chnh xc li.
Lng thu hi tt nht l nm trong gii hn gia UWL v LWL. Nu c 7 s liu
lin tip nm pha trn hoc pha di gi tr trung bnh s chng t c sai s trong
phn tch. Cn thit phi c 2/3 s im phn tch nm trong phm vi ca lch
chun quanh gi tr trung bnh.
th kim tra c trnh by trn xc nh c sai s v chnh xc ca php
phn tch, nhng chnh xc khng c th hin r rt, v d nh khi th c
xy dng khng chnh xc. Tuy nhin th kim tra l rt hu ch trong nh gi cht
lng s liu phn tch mi trng. th kim tra sai s cng c c xy dng trn
c s cc gi tr RPD t kt qu phn tch lp li cc mu. Gi tr trung bnh v lch
chun s c xc nh. Cc gii hn UWL, LWL, UCL v LCL cng c xc nh
ti 2S v 3S. Phng php ny c coi nh hnh thc kim tra sai s b sung
cng vi th kim tra lng thu hi trn. Cc th kim tra l mt phn quan
trng ca chng trnh kim tra cht lng (QC Programs) trong phn tch mi
trng.
16

chng 3. Phng php trc quang
3.1. Phng php so mu quang in
Phng php so mu quang in l phng php phn tch da trn s so snh
cng mu ca dung dch nghin cu vi cng mu ca dung dch tiu chun
c nng xc nh.
Phng php ny c dng ch yu xc nh lng nh ca cc cht, tn t
thi gian so vi cc phng php ho hc khc.
a. nh lut c bn ca phng php so mu:
Nu chiu mt dng sng (cng I
0
) vo mt cuvet ng dung dch th mt
phn ca n (cng I
r
) b phn x t mt cuvet, mt phn khc (cng I
a
) b
dung dch hp th, phn cn li (cng I
t
) i qua cuvet. Ta c:
I
0
= I
a
+ I
r
+ I
t

Khi s dng mt loi cuvet c th xem cng dng nh sng phn x l khng
i, v thng khng ln nn c th b qua. Khi phng trnh trn c dng:
I
0
= I
a
+ I
t

I
0
v I
t
c th o trc tip cn I
a
tm c theo cng thc I
a
= I
0
- I
t
. Da trn
nghin cu thc nghim Bug (Bougueur) v Lmbe (Lambert) thit lp nh lut
v pht biu nh sau: Nhng lp cht c chiu dy ng nht trong nhng iu kin
khc nh nhau, lun hp th mt t l bng nhau ca chm sng chiu vo nhng lp
cht .
Biu thc ton hc ca nh lut l:
I
t
= I
0
. e
-kl

Trong : l : Chiu dy lp hp th
k : H s tt, h s ny ch ph thuc vo bn cht cht tan v bc
sng nh sng chiu vo dung dch. Do dnh lut hp th nh sng Bug -
Lmbe ch ng cho tia n sc.
Khi nghin cu s hp th nh sng ca dung dch, Bia (Beer) thit lp c
mi tng quan gia h s tt k vi nng cht hp th theo phng trnh:
k =
'
. C
Kt hp nhng nghin cu ca Bug - Lmbe - Bia th:
I
0
. e
-
,
C l

hay I
t
= I
0
. 10
- C l

17
Nu nng C c tnh theo mol/l; chiu dy lp dung dch (l) o bng cm th
c gi l h s tt phn t hay h s hp th phn t; l mt i lng khng i
ph thuc vo bc sng nh sng, bn cht ca cht tan, nhit dung dch.
b. Cc i lng thng dng trong phng php so mu:
T s gia cng chm sng sau khi i qua dung dch (I
t
) vi cng chm
sng chiu vo dung dch (I
0
) gi l truyn qua, k hiu bng T.
T =
I
I
t
0
= 10
- C l

i lng T ng vi chiu dy lp dung dch bng 1 cm gi l h s truyn qua.
Logarit ca i lng nghch o vi truyn qua gi l mt quang D hay
tt E (extinction):
D = E = lg
1
T
= lg
I
I
t
0
= . C .l
T nh ngha ny thy rng l mt quang D t l thun vi nng cht tan
trong dung dch.
c. Vng quang ph hp th
c im hp th nh sng ca cc hp cht mu l s hp th chn lc. H s
hp th phn t ca hp cht mu v mt quang ca dung dch khc nhau i vi
chm nh sng i qua c cc bc sng khc nhau. V vy ph hp th cng l mt
c trng in hnh ca cc hp cht mu.
Khi s dng phng php so mu nh lng mt cht cn phi dng tia n
sc no m khi chiu qua dung dch, dung dch c kh nng hp th ln nht. xc
nh bc sng nh sng hp th cc i ngi ta o gi tr mt quang hoc h s
hp th phn t ca dung dch mu vi nhng bc sng khc nhau, cch nhau 10 - 20
nm. gi tr bc sng no m mt quang o c l ln nht th l bc sng
nh sng thch hp nh lng hp cht mu ny.






D
max

max

(nm)
D
Hnh 3.1. Vng quang ph hp th

18
d. Knh lc mu
m bo nhy v chnh xc ca php xc nh, ngi ta khng cho dung
dch hp th mt chm nh sng m ch cho nhng tia n sc b dung dch mu hp
th cc i i qua. Mun tch c nhng tia sng ny ngi ta phi dng knh lc
sng (knh lc mu).
Knh lc sng l tn gi chung cc mi trng nh thy tinh, mng tng hp... ch
cho nhng tia sng thuc mt vng xc nh ca quang ph i qua.
Knh lc sng trong phng php so mu, phi m bo cho nh sng n sc
truyn qua t cc i nhng bc sng trng vi bc sng hp th cc i v i
qua knh lc mu phi b dung dch hp th chn lc cao nht. Mun vy trc khi o
mt quang dung dch mt hp cht mu cha bit
max
(bc sng nh sng b hp
th cc i) cn tin hnh phng php thc nghim: quay cc knh lc mu xem knh
no cho nh sng mu b hp th mnh nht, hoc c th da vo mu sc ca dung
dch xc nh tm knh lc mu thch hp theo bng sau:
Bng 3.1. Cc knh lc s dng cho cc dung dch mu
MU CA DUNG DCH MU CA KNH LC SNG
Tm
Xanh
Xanh lc
Lc xanh
Lc
Lc vng
Vng
Da cam

Lc vng
Vng
Da cam

nu
Tm
Xanh
Xanh lc
Lc xanh

e. Phng php xc nh nng cc cht
Khi tin hnh mt lot php xc nh, phng php thun li nht l phng php
ng chun. xy dng ng chun ta o mu cc dung dch chun ca cht
vi cc nng hoc hm lng bit.
Tin hnh o gi tr mt quang D (hay phn trm truyn qua) ca dy dung
dch chun ny v xy dng ng chun bng phng php hi qui tuyn tnh. Trc
honh biu din gi tr D, trc tung biu din gi tr nng hoc hm lng ca cht
chun.
Nu nng dung dch mu nm trong khong tun theo nh lut Bug - Lmbe -
Bia th tt c gi tr mt quang nhn c nm trn mt ng thng. Sau o gi
tr mt quang ca dung dch mu nghin cu vi cng cuvet v knh lc mu s
dng o cc dung dch chun. Da vo ng chun, ta xc nh c nng
dung dch mu nghin cu. Hnh 3.2 s minh ha vic xy dng mt thang chun
trong xc nh hm lng photpho (P
2
O
5
) bng php hi qui tuyn tnh, im chm l
im thc nghim v ng thng l ng hi qui:
19
y = 0.501x
R
2
= 0.9857
0
0.1
0.2
0.3
0.4
0.5
0 0.2 0.4 0.6 0.8 1
D
mg P2 O5

Hnh 3.2. ng chun trong phng php xc nh photpho
V l thuyt, cc im khi xy dng ng chun phi nm trn mt ng thng,
nhng trong thc t do c nhng sai s kh trnh khi, chng c chnh lch t nhiu.
V mu ca dung dch bin i theo thi gian (thng b nht dn), cho nn do vy
khng nn ko di thi gian o, do s lng mu phi hn ch. Nhng nu dung
dch c mu bn th khng i hi kht khe nh vy.
3.2. Phng php quang k ngn la ( flamephotomet )
Phng php quang k ngn la l mt dng phn tch quang ph pht x. Nguyn
l c bn ca phng php nh sau: Di tc dng ca nhit ngn la cc nguyn
t, phn t hoc ion ca cht b kch thch s chuyn sang trng thi cc dao ng ca
in t pht x. Cng pht x ny c o bng dng c quang hc ri t tnh
ra nng cht cn xc nh. Phm vi s dng quang k ngn la rt ln. Rt nhiu
nguyn t c th dng phng php ny xc nh trc tip hoc gin tip vi tc
nhanh v c chnh xc cao.
a. C s l thuyt: S hp th hoc pht x nng lng nh sng lm cho nguyn
t (hoc phn t, ion) chuyn t trng thi bnh thng sang trng thi kch thch v
ngc li.
trng thi bnh thng nguyn t c nng lng nh nht, khi hp th nng
lng chng chuyn sang trng thi kch thch. Thi gian nguyn t trng thi kch
thch rt ngn (thng l 10
-8
giy) ri li chuyn v trng thi cn bng km theo s
pht x.
S pht x ph thuc vo mc nng lng ca chng trng thi bnh thng v
trng thi kch thch.
E = E
2
- E
1
= h
Nh vy mi mt nguyn t hay ion bin i t trng thi bnh thng sang trng
thi kch thch c c trng bng mt tr s nng lng nht nh. V vy, s pht x
nguyn t ca bt k mt nguyn t no cng c thnh phn quang ph c trng hay
cu to vch quang ph c trng.
20
ng dng trong php phn tch nh lng ngi ta chn ly mt vch quang
ph c trng nht tc l vch ph xut hin cui cng khi gim dn nng cht. S
thay i cng ca vch ny s xc nh lng nguyn t cn phn tch.
S kch thch quang ph pht x tng ln khi tng ngun nng lng ban u cung
cp, tc l nhit . Tuy nhin, mt s nguyn t (nh kim loi kim, kim th) c th
pht x nh sng nhit khng cao lm, v vy vic xc nh nhng nguyn t ny
khng cn thit phi t nhit rt cao. Nhn chung nhn dc nhng vch
quang ph cn c nhit thch hp cho tng nguyn t.
Bng 3.2. Nhit ca mt s ngn la thng dng
(Theo Poluectov)
Hn hp chy Nhit ngn la(
0
C)
Propan - khng kh 1700 - 1800
Hidro - khng kh 2000 - 2045
Axetylen 2125 - 2397
Hidro - oxi 2550 - 2660
Axetylen - oxi 3100 - 3137
Propan - N
2
O 2850 - 2900

Khi tng nng nguyn t c th xy ra hin tng hp th pht x, tc l nhng
nguyn t khng b kch thch s hp th mt phn nng lng pht x. V th nn bt
u t mt gii hn nng no (i vi mi nguyn t xc nh) th quan h gia
cng pht x I v nng C s khng l tuyn tnh (hnh 3.3), tc l phng php
quang k ngn la ch ng v dng c trong phm vi nng nht nh i vi
tng nguyn t.





Hnh 3.3. Quan h gia cng pht x v nng nguyn t
Ngoi ra cn ch ti nhng iu kin sau:
+ Qu trnh xy ra trong ngn la: iu kin nhit cao thng c s bay hi
ln, phn t cc mui phn li tham gia phn ng vi cc thnh phn khc, kt qu l
cng mt lc trong ngn la tn ti mt lng electron t do, ion, phn t, nguyn
t...Cn bng gia nhng dng ny ph thuc vo nhit ca ngn la, thnh phn
hi ca dung dch, iu kin oxi ho - kh. V vy thnh phn dung dch cha nguyn
lgI
lgC
21
t cn xc nh c nh hng n kt qu phn tch. loi tr nh hng ny, cn
chun b dung dch chun c thnh phn ging nh thnh phn dung dch phn tch.
+ Thnh phn dung dch khng nhng nh hng n cc qu trnh xy ra trong
ngn la m cn nh hng ti qu trnh bm mu. Nhit , sc cng b mt...s thay
i lng dung dch c ht qua vi phun tham gia vo trong ngn la, nn sng
ca ngn la cng s thay i. iu s gy nn sai s cho php phn tch.
+ S c mt ca cc ion l vi lng ln trong dung dch s lm chuyn dch cn
bng trong cc phn ng phn li v ion ho trong dung dch. V d nh cng pht
x ca canxi v ca cc kim loi kim khc gim xung khi c mt nhm v khi to
thnh mt hp cht kh phn li (nCaO.Al
2
O
3
). Lng canxi cng nhiu th gi tr n
cng ln.
+ Cc cation kim loi kim c nh hng n s pht x ca nhau, thng lm
tng cng pht x. nh hng ca cc cation kim loi kim gim theo th t sau:
Cs > Rb > K > Na > Li
+ nh hng ca anion: Khi c mt mt vi anion trong dung dch s lm gim
nng v cng pht x ca nguyn t kim loi. Anion nitrat NO
3
-
c nh hng
nht n s pht x ca kim loi kim. Mc nh hng tng dn theo th t sau:
SO
4
2-
< Cl
-
< PO
4
3-

+ Rt nhiu cht c mt trong dung dch thng t pht x vi nhng bc sng
gn vi bc sng phn tch ca nguyn t xc nh. iu lm tng kt qu xc
nh. V d, khi xc nh nitrat cn ch vch quang ph ca canxi, khi xc nh kali
cn ch vch ca liti v rubii.
b. Quang k ngn la
Cu to:
Bt k mt quang k ngn la no cng gm nhng b phn chnh nh sau:
+ Ngun pht x: gm my bm khng kh ni vi ng phun m chuyn dung
dch sang trng thi sol kh a vo ngn la, b phn cp hi t a vo n.
+ Thit b n sc: thng l cc knh lc phn lp, mi nguyn t c knh lc
mu ring, thng c cc knh lc ca natri, kali, canxi...
+ My thu pht x: o cng pht x. a s cc nc thng dng t bo
quang in.
+ in k nhy (n 10
-10
A). l kiu in k gng quay.
S dng:
Chun b mt thang dung dch chun bit nng , c thnh phn tng t vi
thnh phn dung dch phn tch.
M bnh nn khng kh v kh t axetylen (trc khi i vo vi phun v n t,
kh t v khng kh cn c lm sch bng dung dch H
2
SO
4
c). iu chnh p
sut kh t v khng kh cho thch hp tc l lm sao cho ngn la chy tt (nu ngn
la c mu vng v c khi l tha kh t, iu chnh sao cho ngn la u khng c
mu) v dung dch b ht vo n nh, va phi.
Quay knh lc tng ng.
22
M cng tc, a v dung dch chun c nng ln nht. Nu ch s ca in k
ch ngoi thang th phi gim mng chn c c ch s trn in k. Tip tc o
thang chun vi nng t thp n cao. S c phi lp li hai ln. Mi ln thay i
dung dch u phi ra n bng nc ct v kim in k phi ch v 0. V th
chun.
Thay dung dch chun bng dung dch phn tch. c tr s trn in k.
Da th xc nh c nng cht cn phn tch.
ng vi kh t, ng t bo quang in. Ra vi phun bng nc ct. Thng kh
ton b h thng.
3.3. Phng php quang ph hp th nguyn t (AAS)
Nh bit, vt cht c cu to t cc nguyn t v nguyn t l phn t nh
nht cn gi c tnh cht ca nguyn t. Trong iu kin bnh thng nguyn t
khng thu hay pht ra nng lng di dng cc bc x lc ny nguyn t tn ti
trng thi c bn. l trng thi bn vng v c mc nng lng thp nht ca
nguyn t. Khi trng thi hi nguyn t t do nu chiu mt chm tia sng c nhng
bc sng xc nh vo m hi nguyn t th cc nguyn t t do s hp th cc
bc x c bc sng nht nh, ng vi nhng tia bc x m n c th pht ra c
trong qu trnh pht x. Lc nguyn t nhn nng lng di dng cc tia bc
x v n chuyn ln trng thi kch thch, c nng lng cao hn trng thi c bn.
l tnh cht c trng ca nguyn t trng thi hi. Qu trnh gi l qu trnh hp
th nng lng ca nguyn t. Ph sinh ra trong qu trnh ny c gi l ph hp th
nguyn t.
Nghin cu s ph thuc ca cng mt vch ph hp th ca mt nguyn t
v nng C trong mu phn tch, l thuyt v thc nghim cho thy rng: trong mt
vng nng C nh, mi quan h gia cng vch ph hp th v nng ca
nguyn t trong m hi cng tun theo nh lut Bug - Lmbe - Bia:
D = 0,43. K.C.l
K : H s hp th, ph thuc vo chiu di sng
C : Nng nguyn t cn xc nh c trong ngn la
l : Chiu dy ca lp hp th
D : Mt quang ca ngn la ( D= lg I
0
/ I)
Da vo gi tr mt quang, ngi ta xc nh nng nguyn t ca nguyn t
cn xc nh trong th tch mu. Biu thc trn chng t mt quang ca lp hp th
t l thun vi nng ca nguyn t cha trong ti bc sng hp th ng vi
nguyn t . Tnh t l ny c bo ton trong mt khong nng nht nh, ty
thuc vo tnh cht ca nguyn t cn xc nh v tnh cht ca n. S ph thuc trn
l c s thc tin ca phng php phn tch hp th nguyn t nh lng.
a. Nguyn l v thit b ca php o quang ph hp th nguyn t (AAS):
C s l thuyt ca php o AAS l s hp th nng lng (bc x n sc) ca
nguyn t t do trng thi hi (kh) khi chiu chm tia bc x qua m hi ca
23
nguyn t y trong mi trng hp th. V vy mun thc hin c php o ph hp
th nguyn t cn phi c cc qu trnh sau:
+ Chn cc iu kin v mt loi thit b ph hp chuyn mu phn tch t
trng thi ban u (rn hay dung dch) thnh trng thi hi ca cc nguyn t t do.
l qu trnh nguyn t ho mu. Nhng thit b thc hin qu trnh ny gi l h
thng nguyn t ho mu.
+ Chiu chm tia sng pht x ca nguyn t cn phn tch qua m hi nguyn t
va iu ch c trn. Cc nguyn t ca nguyn t cn xc nh trong m hi s
hp th nhng tia bc x nht nh v to ra ph hp th ca n. y, mt phn
cng ca chm sng b mt loi nguyn t hp th v ph thuc vo nng
ca nguyn t trong mi trng hp th. Ngun cung cp chm tia sng pht x ca
nguyn t cn xc nh gi l ngun bc x n sc.
+ Da trn nguyn tc ca php o ph hp th nguyn t nn dng c dng trong
phng php ny gm c nhng b phn chnh nh sau: ngun sng, b hp th, thit
b quang hc, thit b thu v ghi.




Hnh 3.4. S nguyn tc ca mt my o quang ph hp th nguyn t
1. n catt rng 2. B ngt chm sng
3. Ngn la 4. My n sc
5. B phn quang 6. B khuch i
7. Microampe 8. B t ghi
+ Ngun sng: Ngun sng chnh dng trong phng php phn tch quang ph
hp th nguyn t l cc n catt rng. n ny l bnh hay ng hnh tr bng thu
tinh c cc in cc dng t nng. Bnh c np y mt kh tr no c p
sut thp (agon, neon, heli, xenon...). c vng bc x t ngoi, ca ra ca n c
ch to bng thch anh hoc thu tinh c bit.
Catt rng ca n c ch to bng mt kim loi tinh khit (hoc bng vt liu
khc) di dng ng hnh tr m mt pha trong ca n c ph bng mt cht c
cha nguyn t cn xc nh.
Tnh n nh ca n khi lm vic l yu t rt quan trng, n nh hng n
chnh xc v nhy ca phng php phn tch. Tnh n nh c xc nh bng
tnh n nh ca ngun duy tr khi lm vic, bng c tnh cu trc v nhng tnh cht
c th ca n. Tnh n nh ca n khi lm vic c bit c ngha trong trng
hp s dng thang rng.
1
2
3
4
5
6
7 8
24
Ngoi nhng loi n catt rng trong thc t phn tch ngi ta cn dng cc n
khng cc cao tn. l cc bnh bng thch anh hay bng thu tinh c ng knh t
10mm n 20 mm, trong c a vo mt kim loi tng ng (hay hp cht ca n
v mt kh tr (c p sut vi mmHg) dng duy tr s phng in trong n. S
phng in trong n c sinh ra khi t n vo trong mt trng in t ca my
pht c tn s lm vic 100 - 2450 MHz. Cng c th s dng nhng ngun ph hp
th nh l n hidro, n xenon, n teri, nhng cc n cn cha c s dng
rng ri trong phn tch quang ph hp th nguyn t.
+ B hp th: B hp th dng chuyn cht phn tch sang trng thi m trong
cc cht cn xc nh s tn ti di dng nhng nguyn t t do, c kh nng hp
th nh sng ca ngun sng bn ngoi. C th dng cc loi n kh lm b hp th.
Cc kh thng dng t n l propan, butan, axetylen, hidro.
Cht oxi ho khi t chy l oxi, c s dng di dng tinh khit hoc di
dng hn hp vi khng kh v mt vi loi kh khc.
c tnh c bn ca ngn la l nhit v thnh phn kh ca n, thnh phn kh
ph thuc vo dng kh t v cht oxi ho. Nhit v thnh phn kh ca ngn la
xc nh mc phn li ca cc hp cht a vo v c to thnh trong ngn la.
Tu thuc vo t l gia cacbon v oxi, ngn la s c tnh kh hay tnh oxi ho. Ngn
la c tnh kh khi C > 0, c tnh oxi ho khi C < 0 v l trung ho khi C = 0.
c tnh ca dung mi trong mu c a vo ngn la c th nh hng n
nhit , thnh phn kh v lm cho ngn la c tnh kh hoc tnh oxi ho.
Trong ngn la, s nguyn t ho cc nguyn t hoc cc hp cht ca chng xy
ra trong nhng iu kin khc nhau, tu thuc vo hp cht ca nguyn t dng bn
vng vi nhit hoc khng bn vi nhit.
B phn phun v n l hai phn rt quan trng ca b hp th. Chng c tc dng
quyt nh n nhy v chnh xc ca php phn tch. Thit b phun c dng
chuyn dung dch phn tch thnh trng thi sol kh a vo ngn la.
n cng gi vai tr ng k trong vic xc nh tnh n nh v v vy n cng
xc nh c nhy v chnh xc ca php phn tch. n thng c mt khe lin
hoc c mt s dy cc l ring bit.
Hin nay ngi ta nghin cu thnh cng cc phng php nguyn t ho cht
phn tch trong b phn hp th, l phng php khng dng ngn la v phng
php kt hp (l - ngn la). Nh nhng phng php ny m nhy tng ln rt
nhiu khi xc nh mt lot cc nguyn t.
K thut nguyn t ho khng ngn la
K THUT NGUYN T HO KHNG NGN LA RA I SAU K
THUT NGUYN T HO TRONG NGN LA. NHNG K THUT NY
PHT TRIN RT NHANH V HIN C NG DNG RT PH BIN V K
THUT NY CUNG CP CHO PHP O AAS C NHY RT CAO C KHI
GP HNG TRM N HNG NGHN LN PHP O TRONG NGN LA.
25
Php o khng ngn la i hi mt lng mu tng i nh. Thng thng mi
ln o ch cn t 20 n 50 l do khng cn nhiu mu phn tch, vic chun b
mu cng d dng hn.
V nguyn tc k thut nguyn t ho khng ngn la l qu trnh nguyn t ho
tc khc trong thi gian rt ngn nh nng lng ca dng in cng sut ln v trong
mi trng kh tr.
Dng c nguyn t ho theo k thut ny gm cc nhm chnh nh sau:
- Cc loi cuvet grapht
- Cc loi cc grapht
- Cc loi thuyn lm bng kim loi chu nhit nh Tali
Qu trnh nguyn t ha khng ngn la thng gm 3 giai on:
+ Sy kh mu: thng nhit 100 - 150
0
C trong thi gian 20 n 40 giy vi
lng mu nh hn 100 l - nhit v thi gian sy ph thuc vo bn cht ca cc
cht trong mu v dung mi ha tan.
+ Tro ha: t chy cc cht hu c v nung luyn mu nhit thun li cho
giai on nguyn t ha - nhit tro ha ph thuc vo bn cht ca mi nguyn t
v dng hp cht m nguyn t tn ti - nhit tro ha thng thp hn nhit
tro ha gii hn ca nguyn t t 30 - 50
0
C ; thi gian tro ha thng t 20 - 60 giy
vi lng mu a vo cuvt nh hn 100 l trong 1/3 thi gian dng nng
nhit t nhit sy n nhit tro ha t; 2/3 thi gian dng luyn mu
nhit tro ha chn.
+ Nguyn t ha: l giai on quyt nh cng ca vch ph, thi gian rt
ngn, t 3 n 6 giy, i khi c th n 10 giy. Tc tng nhit rt ln (1500 -
2000
0
C/ 1 giy) t ngay tc khc n nhit nguyn t ha.
Nhit nguyn t ha ca mi nguyn t ph thuc vo bn cht ca nguyn t,
trng thi v thnh phn ca mu.
+ Thit b quang hc: Thit b ny bao gm, dng c quang hc (my n sc hay
knh lc ) dng tch cc vch phn tch ca ngun, cc thu knh, cc mng chn v
cc gng ph a cc chm sng t ngun qua b phn hp th.
+ Thit b thu v ghi: Thit b ny gm b ghi nh sng bao gm b nhn quang v
cc thit b in nui b khuych i dng quang in. B ghi c th l thit b c
biu kin, thit b t ghi hoc thit b hin s cng cc s in tng ng ca ngun
nui hay l thit b in.
b. Nhng u im v nhc im ca php o AAS:
Cng nh cc phng php phn tch khc, phng php phn tch ph hp th
nguyn t cng c nhng u im v nhc im nht nh.
u im:
+ Php o ph hp th nguyn t c nhy v chn lc cao. Gn 60 nguyn
t ho hc c th c xc nh bng phng php ny vi nhy t 1.10
-4
n 1.10
-
5
%. c bit nu s dng k thut nguyn t ho khng ngn la th c th t n
nhy n.10
-7
%.
26
Chnh v c nhy cao nn phng php phn tch ny c s dng rng ri
trong nhiu lnh vc xc nh lng vt cc kim loi. c bit l trong phn tch
cc nguyn t vi lng. Cng do nhy cao nn trong nhiu trng hp khng phi
lm giu trc nguyn t cn xc nh.
+ C th xc nh ng thi hay lin tip nhiu nguyn t trong mu. Cc kt qu
phn tch rt n nh, sai s nh. Trong nhiu trng hp sai s khng qu 15% vi
nng mc ppm.
Nhc im:
+ Phi c mt h thng my tng i t tin.
+ V c nhy cao nn s nhim bn c nh hng ln n kt qu phn tch
hm lng vt.
+ Phng php ch cho ta bit thnh phn nguyn t ca cht trong mu phn
tch m khng ch ra trng thi lin kt ca nguyn t trong mu. V th y ch l
phng php phn tch thnh phn nguyn t.
c. i tng v phm vi ng dngca phng php:
i tng chnh ca phng php l phn tch lng nh v lng vt cc nguyn
t kim loi ca cc cht v c v hu c trong cc loi mu khc nhau nh qung, t,
, nc, cc sn phm nng nghip, phn bn...
Ngoi cc kim loi mt s phi kim nh Si, P, As, Te... cng c th xc nh chnh
xc bng phng php ny.
Trong khong hai chc nm tr li y php o ph hp th nguyn t pht
trin rt nhanh. N c s dng nh l mt cng c phn tch c lc cho nhiu
ngnh khoa hc v kinh t. Hin nay nhiu my o ph hp th nguyn t c sn
xut vi nhiu tnh nng u vit. V vy php o ph hp th nguyn t l mt trong
nhng php o u vit trong h thng cc phng php phn tch hin nay.
27
Chng 4. Phng php in ha
4.1. Cc chn lc ion
Phng php phn tch in th l mt trong cc phng php phn tch ra i
sm nht. Nguyn tc ca phng php l o th cn bng ca cc nghin cu xc
nh nng cn bng ca cht phn tch hoc theo di s bin thin nng ca n
khi n tham gia vo phn ng ha hc.
Khi nhng cc lm bng Pt vo dung dch cha cht oxiha - kh lin hp s c
hin tng trao i electron gia cc v cht trong dung dch. S trao i ny s gy
nn phn ng in ha.
Nu nh tc ca qu trnh kh nhanh hn qu trnh oxi ha th cht oxi ha
nhn electron nhiu hn, Pt s nhng e cho cht oxi ha, lc b mt Pt s mang
in tch dng, n s ht cc ion mang in tch m vo to nn lp in kp. Gia
hai mt ca lp in kp s xut hin mt th v th E s c o trong phng
php phn tch ny.
Khi tc ca qu trnh oxi ha bng tc ca qu trnh kh lc lng cht
oxi ha v lng cht kh khng thay i na. Th t ti trng thi cn bng. Th
cn bng c lin quan n nng hay chnh xc hn l lin quan n hot ca cht
oxi ha v cht kh theo phng trnh Nerst :
E = E
0
+
0 059 ,
.lg
n
a
a
ox
kh

Trn thc t khng xc nh c gi tr th cn bng ca mt cc ring bit m
ch xc nh th ca n so vi mt cc dng lm cc chun. Trong phn tch in th
cc ny c gi l cc so snh (thng l cc cc loi 2 nh cc calomen bo ha
hoc cc bc clorua). Cc cn o th cn bng gi l cc o hoc cc ch th.
Trong s cc loi cc ch th dng trong phn tch in ha c mt loi cc rt c
bit c ch to t nhng loi mng c bit, th ca cc ph thuc mt cch chn
lc vo hot cht cn xc nh. Cc cc ny c gi l cc chn lc ion.
Nhng cng trnh nghin cu ca Nerst v ca Reisenfeld v tnh cht c bn ca
b mt mng v th xut hin trn ranh gii gia mng v dung dch gip hai nh
bc hc ny a ra khi nim v ranh gii pha ca hai cht lng khng trn ln vi
nhau.
in ha hc v mng c chnh thc nghin cu t nm 1890 trong cc cng
trnh ca Ostwald - ngi pht hin ra mng bn thm l loi mng cho chuyn qua
n nhng loi ion xc nh.
Ngay t thi gian u ngi ta ngh n ra hai loi mng: mng c (gm mng
lng, mng rn) v mng l xp. Trong s cc loi mng c, ngi ta ch to c
28
cc loi mng thy tinh rt mng v t pht minh ra cc mng thy tinh l loi
cc c th ph thuc chn lc vi hot ca ion hidro trong cc dung dch. Nh khoa
hc ngi Nga l Nikolxki xy dng thuyt trao i ion ca cc mng thy tinh.
Eisenman v cc cng s xy dng hc thuyt v th khuch tn trong mng thy
tinh.
Tip theo nh khoa hc ngi Hungari l Pungor v cc cng s nghin cu
thnh cng cc loi mng rn chn lc ion ch to cc cc. Cc mng u tin l
cc mng d th cha kt ta bc halogenua. Sau ngi ta nghin cu v ch to
cc mng chn lc ion n tinh th. Frant v Ross ch to c cc chn lc vi
ion florua trn c s dng n tinh th lan tan florua.
Trong nhng nm gn y cc nguyn l sinh hc c ng dng ch to cc
cc enzim trong mng ca cc c ph mt lp cht mang polime cha enzim.
Cht cn xc nh s phn ng trong lp enzim v to nn sn phm gy ra tn hiu c
th o c.
4.1.1. L thuyt v cc th mng ca cc cc chn lc ion
Cc khi nim c s:
Mt cc chn lc ion gm c thn cc bn trong cha dung dch cht in li c
thnh phn v nng xc nh (dung dch1), cui cc l mt mng chn lc ion (c
th l mng rn ng th hoc d th hoc n tinh th, mng thy tinh hoc mng
lng) v bn trong thn cc c mt cc so snh nhng vo dung dch trong.







Hnh 4.1. S nguyn tc ca cc chn lc ion (CLI)
S h in ha khi o th ca cc chn lc ion l:
Cc so snh 1 Dung dch 1 Mng Dung dch 2 Cc so snh 2
Dd trong Dd phn tch
Th in ng ca nguyn t in ha trn l:
E = E
2
+
M
- E
1

Cc cc so snh 1 v 2 thng l cc cc loi 2 c th xc nh v khng i, do
khi dng cc CLI trong phn tch ch c th mng
M
l c ngha quyt nh.
Tng s th ca cc bn trong v th mng gi l th ca cc CLI, E
CLI

Cc so snh
trong 1
Dung dch
trong 1
Mng

Cc so snh 2
Cc CLI
Dung dch phn
tch 2
Que khuy
29
E
CLI
= E
2
+
M

Trong trng hp n gin nht, khi mng ca cc CLI ngn cch hai dung dch
trong v dung dch nghin cu ch cha ion cn xc nh j v trong c hai dung dch
hon ton khng c ion khc nh hng ti th mng c quyt nh bi ion j, th
th mng c xc nh theo h thc :

M
=
RT
z F
a
a
j
j
.
ln
( )
( )
1
2

Trong : z l in tch ca ion j, a
j
(1) v a
j
(2) l hot tng ng ca j trong
cc dung dch 1,2.
Trong trng hp trong dung dch phn tch c ion K l ion ngn cn s xc nh
hot ca ion j, th th ca CLI c xc nh theo phng trnh Nikolxki. Trong
phng trnh ny c s ph thuc ca th vo h s chn lc ca cc cho ion K i
vi ion cn xc nh j. H s chn lc thng l hm s ca thnh phn dung dch
nghin cu v gip ta nh hng c nh hng ca cc ion cn tr ti s xc nh
ion cn phn tch.
Bc nhy th gia cc v mi trng trong trng hp n gin tun theo
phng trnh :
E = E
0
+ 2,303 .
RT
nF
lna
x

E
0
: Th in cc trong mi trng vi hot ca cc ion a = 1, ngha l in
cc chun.
R : L hng s kh
T : L nhit tuyt i ca mi trng (
0
K )
F : S Faraay
n : S thay i in tch ca ion cn xc nh do kt qu ca phn ng in ha.
a
x
: Hot ca ion X trong mi trng nghin cu.
20
0
C, phng trnh c dng:
E = E
0
-
0 058 ,
n
pX (vi pX = - lg X )
Th ca cc ph thc tuyn tnh vo pX cho php chng ta s dng cc trong
thc tin phn tch.
4.1.2. Mt vi loi in cc ch th thng thng
in cc mng kali: in cc mng kali xc nh hot ca ion K
+
, c cu
to t mt ng thy tinh hoc ng nha, phn cui ca ng l mng mng chn lc ion.
Bn trong ng c y dung dch KCl 0,1M, in cc so snh bc clorua c
nhng trong dung dch ny.
30
in cc mng kali nhy vi ion kali trong phm vi nng xc nh: vi in cc
EM.K-01 ca Lin X (c) gii hn ny l t 10
-1
n 1.10
-4
M. Khi c mt Na
+
vi t
l K
+
: Na
+
l 1 : 20 v NH
4
+
vi t l K
+
: NH
4
+
l 1 : 200 th cc ion Na
+
v NH
4
+
s
cn tr php xc nh K
+
bng in cc EM.K 01.
Trc khi bt u lm vic, cn ra khoang bn trong ca in cc hai ln bng
nc ct ti nhit phng v hai ln bng dung dch KCl 0,1M. Sau rt vo in
cc 1,5 - 2,5 ml KCl 0,1M ri nhng in cc so snh bn trong vo.
in cc vo dung dch KCl 0,1M t nht l mt ngy m v sau vn gi
trong dung dch ny. Dng dung dch KCl chun kim tra in cc sau khi chun
b xong.
Dd KCl mol/l
a
K
+
pK
0,2000 0,718 0,1436 0,84
0,1000 0,770 0,0770 1,11
0,0500 0,816 0,0408 1,39
0,0100 0,902 0,0090 2,04
0,0050 0,927 0,0046 2,34
0,0010 0,965 0,0010 3,02
0,0005 0,0005 3,30
0,0001 0,0001 4,00
kim tra in cc cn thit lp mt mng o, in cc K c nhng vo trong
dung dch KCl chun, in cc so snh c nhng trong dung dch KCl bo ha.
Gia hai dung dch ny c ni bng mt cu dn lm y bng aga trn vi
litiaxetat. o tr s sau khi nhng in cc vo dung dch sau 5 pht.
Nu in cc hot ng tt, tin hnh o th ca dung dch th nghim. Da vo
thang chun gia th v pK tnh ra c hot ca K
+
trong dung dch nghin cu.
- 0 ,0 8
- 0 ,0 6
- 0 ,0 4
- 0 ,0 2
0
0 ,0 2
0 ,0 4
0 ,0 6
0 ,0 8
0 2 4 6 8 10
pK
E ( m V )

Hnh 4.2. S ph thuc th ca mch o khi dng in cc mng K vo gi tr pK
in cc mng nitrat: in cc mng nitrat EM - NO
3
- 01 do Lin X ch to c
cu to tng t nh in cc kali, ch khc l mng c bo ha bng ion NO
3
-
.
Khoang bn trong ca in cc cha dung dch KNO
3
0,1M v dung dch KCl 0,005M,
sau nhng in cc so snh bn trong vo. in cc so snh bn ngoi thng dng
l in cc calomen hay in cc bc clorua.
Th ca in cc mng nitrat trong gi tr pH t 2 - 9 v hot NO
3
-
t 0,001 -
1M tun theo phng trnh :
31
E = E
0
- 0,058.
P
NO
3
-
.
Cc anion khc nh Cl
-
, HCO
3
-
, SO
4
2-
vi t l l NO
3
-
: Cl
-
= 1 : 1; NO
3
-
: HCO
3
-
=
1 : 5; NO
3
-
: SO
4
2-
= 1 : 5 s cn tr vic xc nh NO
3
-
.
Trc khi dng in cc nitrat mi, cn phi ra khoang bn trong cc hai ln
bng nc ct v hai ln bng dung dch KNO
3
v KCl vi nng nh trn, sau
rt vo 1,5 - 2,5 ml dung dch ny ri nhng in cc so snh bn trong vo. in cc
sau khi chun b xong, c gi qua mt ngy m trrong dung dch KNO
3
0,1 M v
sau ny vn gi trong dung dch .
Sau khi chun b in cc xong, tin hnh kim tra s ph thuc th ca cc vo
gi tr pNO
3
. Thit lp mng o gm in cc so snh v in cc nitrat u nhng
trong dung dch NaNO
3
chun. Sau 5 pht, ghi s trn my o.
Nng
NaNO
3

(mol/l)
a
NO
3
pNO
3
-

0,1000 0,765 0,0765 1,11
0,0500 0,812 0,0406 1,30
0,0100 0,900 0,0090 2,04
0,0050 0,926 0,0046 2,34
0,0010 0,964 0,0010 3,02
0,0005 0,975 0,0005 3,30
0,0001 1,000 0,0001 4,00
Xy dng th theo kt qu o th trong 3 - 4 dung dch chun. Khi thay i gi
tr pNO
3
-
theo n v dc ca th l 58 mV.

0
100
200
300
400
500
0 2 4 6
pNO3
E (mV)

Hnh 4.3. S ph thuc ca th ca mch o khi dng in cc
mng nitrat vo gi tr pNO
3
-
Cc in cc nhy vi kh:
in cc nhy vi kh u tin c xem nh l b thu xc nh th c s
dng l in cc dng xc nh CO
2
trong khng kh. Hin nay c cc in cc
nhy vi kh xc nh NH
3
, SO
2
, H
2
... v cc cht kh khc. Nguyn tc lm vic
ca cc in cc ny da trn s ch th ca ion c to thnh do phn t kh phn
ng vi nc.
CO
2
+ H
2
O = HCO
3

-
+ H
+

32
NH
3
+ H
2
O = NH
4
+
+ OH
-

HF + H
2
O = H
3
O
+
+ F
-
H
2
S + H
2
O = HS
-
+ H
3
O
+

Th ca in cc nhy vi kh c xc nh bng phng trnh:
E = E
0
+
RT
nF
lgC
kh
Do vy cng c kh nng xc nh hm lng kh trong mu thng qua vic xc
nh th.
Kh khn c bn i vi cc in cc nhy vi kh l vic xy dng nhng iu
kin thit lp nhanh cn bng gia cht kh v cht lng v vic chn in cc bn
trong kh khuch tn v tham gia thit lp cn bng to nn nhng ion c xc
nh bng in cc chn lc ion.
Cu to ca cc in cc nhy vi kh:






Hnh 4.4. in cc vi mng kh thm qua
1 - V in cc
2 - in cc chn lc ion
3 - Mng ch th
4 - Dung dch cht in gii
5 - Mng kh thm qua
6 - Lp m
7 - in cc so snh
Hnh 4.5. in cc vi khong trng kh
1 - in cc chn lc ion
2 - Cht in li chun
3 - Mng in cc chn lc ion
4 - Khe h khng kh
5 - in cc so snh
6 - Dung dch phn tch
7 - Khuy t
c tnh ca mt vi in cc nhy vi kh


Nguyn
t nhy
Cht
in li
bn
trong
Gii hn
di
php o
Gc
nghing
pH ca
cht
in li
bn
trong
Cht
cn
tr
ng dng
CO
2
H
+

NaHCO
3
0,01M
= 10
-5
+ 60 < 4
NH
3
H
+
= 10
-6
- 60 > 11
1
2
3
4
5
6
7
1
2
3
4
5 6
7
33
Et
2
NH
H
+

Et
2
NH
2
Cl
0,01M
= 10
-5
- 60 > 11 NH
3

SO
2
H
+

NaHSO
3

0,1M
= 10
6
= 10
-4

+ 60
HSO
4
-
m
Cl
2

NO
2

Kh thi thc phm,
vang, cht t
NO
2
H
+

NaNO
2

0,02M
5.10
-7
+ 60
m
xitrat
SO
2

CO
2

Kh thi, khng kh,
nitrua trong thc
phm.
H
2
S S
2-

m
xitrat
= 10
-8
- 30 < 5 O
2

Phn tch ung, s
ln men.
HF F
-
H
+
1M = 10
-3
- 60 ...2
C C
m
HSO
4
-

= 10
-3
- 60 < 2 S tinh luyn
Cc in cc nhy vi kh hin nay c s dng xc nh cc ion nitrat
trong t, trong nc bin vi vic kh trc NO
3
-
n amonic; in cc loi ny cn
dng xc nh SO
2
trong cc mu sinh hc, nghin cu thnh phn cc kh thot
ra trong cc qu trnh to thnh t, trong qu trnh h hp v dinh dng ca thc vt,
ngoi ra cn s dng in cc loi ny xc nh cc cht c hot tnh sinh hc.
Cc in cc so snh: in cc so snh hin nay thng c s dng cng vi
cc in cc chn lc ion l in cc bc clorua. y l in cc thun tin, n gin,
bn v khng i hi phi bo qun ngoi vic lm y bn trong cc bng dung dch
KCl. in cc bc clorua c v lm bng thy tinh, cui cc c si aming tip xc
gia in cc vi mi trng bn ngoi. Bn trong ng c dung dch kali clorua, dy
dn bc c b mt xp c ph bng kt ta bc clorua.
Th ca in cc c xc nh theo nng dung dch KCl. Khi nng KCl
khng thay i th gi tr th ca in cc cng khng thay i.
Khi phn tch mu ngoi thc a nn dng dung dch KCl bo ha.
Th ca in cc bc clorua:
Dung dch KCl E(V) 25
0
C
Dung dch KCl bo ha + 0,202 (20
0
C)
KCl 1,0N + 0,238
KCl 0,1N + 0,290
HCl 0,1N + 0,289
HCl 1,0N + 0,218
Cu dn in:
Cu dn in dng thit lp mng in vi cc cc chn lc ion l mt ng thy
tinh hnh ch U, ng knh bn trong 3 - 5 mm; di khong 5 - 6 cm; c np y
aga trong dung dch mt mui bo ha (KCl, KNO
3
,

LiCH
3
COO...). Khi dng cc
chn lc ion kali, np vo trong cu dn in dung dch litiaxetat cn khi dng cc bc
clorua ngi ta np dung dch kali nitrat.
34
chun b cu dn in ly 3 g aga nghin nh cho vo trong cc, thm vo
100 ml nc ct v gi qua m. Sau t ln bp, un cn thn v thm t t 10g
mui, khuy u bng tha thy tinh n khi tan hon ton.
un hn hp trn nhit 50

- 60
0
C ri rt cn thn hn hp vo ng ch U; gi
cho n khi hn hp ngui i. Cn ch rng trong qu trnh cho hn hp vo v gi
hn hp ngui khng to bt kh trong ng.
Gi cu dn in trong dung dch mui bo ha (mui np vo trong ng). Trc
khi dng, dng nc ct ra qua cu dn in, dng giy lc lau kh. Mt u cu
c trong dung dch nghin cu cn u kia nhng vo trong dung dch KCl bo
ha c cm in cc so snh.
S dng cc in cc chn lc ion trong iu kin ngoi thc a.
Cc in cc ch th lm bng thy tinh v cc in cc chn lc bng mng c th
dng xc nh hot ca cc ion trong cc iu kin ngoi thc a, ngha l xc
nh trc tip trong t nu m ca t khng nh hn 15%, trong nc thin nhin,
nc thi, nc cng nghip, nc ti. Khi lm vic ngoi thc a, ngun in cho
my l pin.
Trc khi ra thc a cn kim tra cc in cc ch th theo cc dung dch chun.
Tt c cc in cc ch th, tr in cc chn lc ion bc clorua, u phi nhng trong
dung dch bi v nu mng b kh thm ch ch trong thi gian ngn cng c tc hi
n cc, lm ri lon chc nng ca cc.
Cn xy dng th chun trc ti nhit tin hnh php o ngoi thc a.
Phn tch nc trong iu kin thc a tin hnh tng t nh phn tch dung
dch trong phng th nghim.
Khi o hot ca cc ion trong t, in cc ch th lm bng thy tinh v in
cc so snh c cm vo t vi khong cch chnh xc 5 - 6 cm. Khi dng in cc
mng cn o l trc vi su bng su ca php o v ng knh l tng
ng vi ng knh ca cc. Sau khi nhng cc in cc vo trong t cn n nh
lm cht xung quanh cc. Sau 15 - 30 pht, tu thuc vo m ca t, tin hnh o
hot ion cn xc nh.

Hnh 4.6. in cc bc clorua
1 - V in cc
2 - Si amiang
3 - Dung dch KCl
4 - L rt
5 - Nt cao su
6 - Dy dn bng bc
7 - Lp bc clorua
4
5
1
3
7
6
2

35

Bng 4.1. S dng mt s in cc chn lc ion trong phn tch mi trng
Cht phn tch Kiu in cc iu chnh cng
ion (ISA)
NH
4
+
Cm ng kh pH iu chnh theo ISA
Br Cc rn NaNO
3
5M
CO Cm ng kh m CO
2
a

Cl
-
Cc rn
Mng lng
Cc lin hp
NaNO
3
5M
-
-
Clorin Cc rn Thuc th iua
CN
-
Cc rn NaNO
3
5M
F
-
Cc lin hp
Cc rn
TISAB
b
-
Florua borat Mng lng (NH
4
)
2
SO
4
2M
I
-
Cc rn NaNO
3
5M
NO
3
-
Mng lng (NH
4
)
2
SO
4
2M
Oxit nit Cm ng kh m axit

Oxi ha tan Mng lng -
ClO
4
-
Mng lng (NH
4
)
2
SO
4
2M
S
2-
Cc rn SAOB
c
SCN
-
Cc rn NaNO
3
5M
Ghi ch: a : m xitrat (Natri xitrat/ axit xitric)
b : Dung dch m iu chnh cng ion tng s gm: axit 1,2 -
xyclohecxylendinitriltetraaxetic v xitrat hoc tactrat.
c : Dung dch m chng oxit ha S
2-
gm: Trilon-B 0,2M; dung
dch NaOH 2M v axit ascobic.
C th s dng cc phng php ng chun hoc phng php thm xc
nh nng ca mt cu t trong mi trng.
V d: xc nh Cl
-
trong mu nc thi bng phng php thm, trc tin
em o th ca mu nc thi gi s gi tr th ghi c l 17,5 mV (E
1
), sau tin
hnh nh sau: ly 5 ml dung dch chun Cl
-
nng 75 ppm cho vo bnh nh mc
100 ml, inh mc n vch mc bng mu nc thi cn phn tch. Chuyn dung dch
ra cc v tin hnh o bng cc chn lc ion. Th o c s l 35,3 mv (E
2
). S dng
cng thc:


Trong : C
y
: Nng cht chun
: T l ca th dung dch chun trong ton b th tch em o
C =
C
y
[(1+)x10
E/S
- 1]
36
S : dc ca in cc
E : E
2
- E
1

p dng cng thc cho v d trn: C
y
= 75 ppm; = 5 ml/ 100ml = 0,05;
E = 35,3 - 17,5 = 17,8 mV; S = 58,1 mV
Do nng ca Cl
-
trong mu phn tch l 3,34 ppm
4.2. Phng php cc ph
Phng php cc ph l phng php phn tch do nh bc hc Tip Khc (c)
Iaroslap Hayropski pht minh nm 1922. Phng php ny c s dng rng ri
nh lng cc cht v c v hu c trong cc i tng khc nhau. Nh s hon
thin ca k thut cc ph nn ngy nay c hng lot cc phng php cc ph
khc nhau: cc ph mt chiu dng khuch tn, cc ph xoay chiu, cc ph hn hng,
cc ph xung vi phn...
4.2.1. Cc ph mt chiu dng khuch tn (cc ph c in)
Nguyn l ca phng php:
C s ca phng php l nghin cu ng biu din s ph thuc ca cng
dng in vo th ca bnh in phn c cu to c bit cha ion cn kho st:
I = f (E )
ng biu din s ph thuc c gi l ng Von-Amper hay cn gi l
ng cc ph hoc sng cc ph.
c ng Von-Ampe ta dng my cc ph. S n gin ca my nh sau:









Hnh 4.7. S nguyn l my cc ph Hnh 4.8. Sng cc ph
K - Catt; A - Ant; G - in k;
R - in tr; B - Ngun
Na sng
Dng d
Dng gii hn
i
-E
E
1/2

K
A
+
-
G
B
R
37
Catot hay dng l in cc git thy ngn lm in cc ch th cn anot l y
thy ngn hay in cc calomen bo ha lm in cc so snh.
Th E t vo s to nn phn cc catot (
K
) v anot (
A
). Cn bng tng qut ca
th bn ngoi t vo c th biu th nh sau :
E =
K
+
A
+ i
R

y i
R
l s gim th khi dng i qua dung dch. Cc thnh phn
A
v i
R
trong
cc ph c khuynh hng tin ti cc tiu do b mt ln ca in cc so snh v
trong dung dch so snh c cht in li tr (nn), lm gim in tr R ca dung dch.
Do th bn ngoi t vo ch gy nn s phn cc ca in cc git thy ngn. Nu
dng in cc git thy ngn lm in cc ch th v in cc so snh l cc calomen
bo ha (th ca cc ny trong cc ph c quy c bng khng) th :
E = -
K

S ph thuc gia th ca in cc git thy ngn v cng dng in biu th
bng th di dng ng cong cc ph (cc ph ). Dng tng qut ca cc ph
c biu din hnh 4.8.
Khi t c th kh (hoc oxiha) ca ion no c trong dung dch, qu trnh
in phn c bt u, cng dng in tng ln r rt. S tng ln ca cng
dng ch khi trong dung dch cn lp khuch tn st in cc c cha ion gy nn
dng in phn. Khi nng ion bng khng th qu trnh tng cng dng s
ngng li. Khi bt u hin tng phn cc nng . Khi khng c cc ion c
kh (hay c oxi ha) lp st in cc, cng dng lc ny c gi l dng
gii hn khuch tn, n c gi tr khng i do c s khuch tn cht t dung dch n
lp st in cc.
Cng dng khuch tn gii hn t l vi tc khuch tn cht n in cc,
tc l t l vi nng ca cht c trong dung dch.
i
d
= K.C
K : h s t l
Phng trnh trn chnh l phng trnh dng khuch tn gii hn.
D.Incovic a ra phng trnh chi tit:
i
d
= 605.n.D
1/2
. m
2/3
.
1/6
. C
n : S electron tham gia phn ng.
D : H s khuch tn
m : Khi lng thy ngn thot ra t mao qun trong mt n v thi gian.
: Chu k git thy ngn.
C : Nng ca cht.
38
Gi tr h s t l K ph thuc vo c tnh ca in cc s dng, c tnh ca ion
c kh hoc c oxi ha, c tnh ca cht in li tr v nhit ca dung dch
cc ph.
Trong trng hp kh cation, gi tr dng khuch tn gii hn c lin quan n
nng ca nguyn t phn tch ch l mt phn ca dng tng s i
t.
i
d
= i
t
- (i
k
+i
g
+i
h
)
i
k
: Dng t in
i
g
: Dng in phn yu do cc tp cht trong dung dch gy nn.
i
h
: Dng di chuyn.
Dng di chuyn xut hin l do s di chuyn ca cc ion di tc dng ca lc
in trng, loi tr cn thm vo trong dung dch phn tch cht in li tr.
Dng in phn yu c loi tr bng cch tinh ch cn thn cht in li tr.
Dng t in sinh ra do lp in kp ca dng khuch tn st in cc tch in,
dng ny ni chung cng kh loi tr. Dng t in v dng in phn yu gp li
thnh dng d.
Dng d trong nhiu trng hp ln n mc khng th o c sng cc ph,
c bit khi xc nh cc kim loi nng trong t, trong nc v trong thc vt i hi
tin hnh nhy cao.
lm gim dng d mt cch ng k hin nay trong tt c cc my cc ph u
c thit b b chnh. S dng thit b b chnh cho php nhn c dng sng cc ph
tt hn rt nhiu v nh th s nng cao hn nhy v lp li ca kt qu.
Khi s dng ct thy ngn s thu c nhng kt qu tt v khi s tng ca
dng b chnh nh hn nhiu so vi s tng ca dng khuch tn.
Nguyn nhn lm tng dng khuch tn l do hin tng chuyn ng tip tuyn
ca git thy ngn, chuyn ng ny gy nn vic khuy trn lp dung dch cnh
git, trn ng cong cc ph c xut hin cc i. loi tr cc i ngi ta thm
vo dung dch nhng cht hot ng b mt nh aga-aga, gelatin... khi chuyn ng
tip tuyn cu thy ngn s gim i.
Sng cc ph ca ion xc nh thng b sai lch do c xut hin sng ca oxi, oxi
cha trong dung dch ca ion xc nh c trn in cc git thy ngn:
0
2
+ 2 H
+
+ 2 e H
2
0
2
(trong mi trng axit)
0
2
+ 2 H
2
0 + 4 e 2 H
2
0
2
(trong mi trng kim)
H
2
0
2
+ 2 H
+
+2 e 2 H
2
0 (trong mi trng axit)
H
2
0
2
+ 2 e 2 OH
-
(trong mi trng kim)
loi oxi, trc khi phn tch cc ph ngi ta cho kh H
2
hay N
2
sc qua dung
dch. Trong trng hp nhng dung dch c tnh axit, loi oxi c th dng CO
2
, cn
39
trong mi trng kim thng dng natri sunfit, thm 0,1g Na
2
SO
3
trong 100 ml dung
dch c th kh hon ton c oxi trong thi gian khong 5 pht.
Phn tch cc ph nh tnh v nh lng:
Khi xc nh nh tnh ion c kh (hoc oxi ha) ngi ta da vo gi tr th
bn sng E
1/2
. Gi tr th bn sng bng gi tr th ca in cc ch th khi cng
dng bng 1/2 gi tr ca dng gii hn.
Gi tr th bn sng khng ph thuc vo nng ca cht phn ng, khng ph
thuc vo vn tc chy ca git thy ngn qua mao qun v cc yu t khc. y l
mt hng s c trng cho ion trong mt nn nht nh. V th vic la chn cht in
li tr (cht nn) c ngha to ln trong phn tch cc ph. Hin nay, ngi ta dng cc
cht in li c thnh phn khc nhau (cc axit, cc mui trung tnh, cc dung dch
kim, cc cht to phc khc nhau) lm cht nn. i vi a s cht nn, ngi ta
thnh lp c cc nguyn t c kh nng c kh hoc c oxi ha v cc gi tr
th bn sng. Cc bng gi ny c ghi trong cc sch chuyn kho hoc cc s tay.
Khi phn tch mt nguyn t hay mt vi nguyn t phi chn cht in li tr (cht
nn) loi tr nh hng ca cc ion km theo.
Gi tr ca dng gii hn hay chiu cao ca sng cc ph trong nhng iu kin
nht nh t l vi nng ion cn kho st. xc nh chnh xc chiu cao ca sng,
ngi ta thng dng phng php ca Hon.
Theo phng php ny ngi ta k 3 ng thng trn sng, t cc giao im li
k cc ng song song vi trc honh.
Khong cch gia cc ng thng ny l chiu cao sng cc ph. T im gia
ca chiu cao sng cc ph k ng thng song song vi trc honh. T giao im
ca ng ny vi sng cc ph, k ng thng song song vi trc tung. ng
thng ny ct trc honh ti im l gi tr th bn sng. Gi tr th bn sng l gi tr
tnh i vi in cc calomen bo ha.





Hnh 4.9. Phng php xc nh chiu cao ca sng
phn tch cc ph, ngi ta thng ly nhng lng th tch nh (3 - 5 ml),
s rt ngn c thi gian ui oxi ra khi dung dch.
Trong phn tch nh lng, xc nh nng ngi ta s dng cc phng
php: phng php cc dung dch chun, phng php thm v phng php ng
chun. Thun li nht khi phn tch hng lot mu l phng php ng chun.
h
i
-E
E
1/2

40
th ng chun: trc tung ghi gi tr chiu cao ca sng (h, mm), trc honh
ghi gi tr nng C. ng chun thng i qua im gc to . i khi th
khng i qua gc to m ct trc tung hoc trc honh mt im no y. Trong
trng hp ct trc tung c ngha l cha han ton trit tiu dng d hay trong dung
dch nn b nhim nguyn t cn xc nh; khi ct trc honh c ngha l dng khuch
tn gii hn c tnh cha hon ton.
4.2.2. Cc ph hn hng (hay Von-Ampe ha tan)
C s l thuyt ca phng php:
tin hnh cc ph hn hng, ngi ta thng thc hin qua 2 giai on:
+ in phn lm giu cht cn phn tch ln b mt cc o di dng mt kt
ta (kim loi, hp cht kh tan). Cc o thng l cc thy ngn treo c kch thc
nh nh git thy ngn trong cc ph c in, cc a quay bng vt liu tr (nh than
thy tinh, than nho tinh khit, than ngm tm platin...), cc mng thy ngn trn b
mt cc rn tr. Qu trnh in phn thng tin hnh trn cc my cc ph thng
thng ti th khng i khi khuy dung dch vi vn tc u. Nu dng cc rn a
th dng cc cc quay quanh trc ca n, nu dng cc thy ngn tnh th khuy dung
dch bng my khuy t.
+ Ha tan kt ta, lm giu v ghi o gi tr cng dng ti th thay i khng
gin on (s ha tan ant).
ng cong biu din s ph thuc ca cng trong qu trnh ha tan ant c
dng pic. Theo chiu su pic ngi ta tm c nng ca ion kim loi trong dung
dch v theo th ca pic s bit c bn cht ca kim loi.
Hnh di y biu din sng cc ph ca ion Pb
2+
nng 2.10
-4
M trong dung
dch KCNS 0,1M. Hnh 11(b) l ng cc ph hn hng (von - ampe ha tan) ca
dung dch cha ion Pb
2+
nng 10
-6
, KCNS 0,1M khi in phn lm giu trong 5
pht ti th (-0,7V). Dng cc thy ngn treo c kch thc tng t git thy ngn
khi o cc ph, tc phn cc ha tan ant l 25 mV/s c hai ng cong c ghi
cng mt nhy ca in k.
Qua ta thy phng php cc ph hn hng c nhy cao hn phng php
cc ph c in rt nhiu.
Nhng yu t ch yu xc dnh cng dng ant l: nng kim loi trong
dung dch, bn knh git thy ngn, th tch dung dch, thi gian in phn, th in
phn, nhng iu kin thy ng lc hc trong thi gian in phn, tc thay i
trong thi gian ghi v mt vi yu t khc.





41









Hnh 4.10. Cc ng cc ph c in (a) v cc ph hn hng (b) ca Pb
2+
trong nn KSCN
S ph thuc vo nhiu yu t ca i
A
chng t qu trnh xy ra trong cc hn hng
l phc tp. C th chia chng chia thnh 2 nhm:
Nhng qu trnh xy ra khi in phn.
Nhng qu trnh lin quan vi s ha tan ca kim loi t hn hng.
Cng ca dng in phn i
d
do phn ng Me
n+
+ ne + Hg Me (Hg) gy
nn, ph thuc vo nng ca ion kim loi trong dung dch (C
0
), v ph thuc vo
din tch S ca in cc ch th.
i
d
= K
d
. S. C
0

y K
d
l hng s ca dng in phn, ph thuc vo nhng iu kin thy
ng lc hc khi in phn v ph thuc vo ha tr ca ion kim loi v nhiu yu t
khc.
Tu thuc vo s phi hp ca 3 yu t: bn knh git thy ngn (r), thi gian in
phn (t), th tch dung dch (v) m nng kim loi trong dung dch sau khi in phn
(C
1
) c th bng hoc nh hn nhiu so vi nng ban u (C
0
). Mc tiu hao ca
dung dch () sau khi in phn c xc nh bng phng trnh (A.G. Xtromberg,
1962):
= 1 - e
-b

b =
4
2
. .
.
. .
K
n F
r
t
v
d

Theo cc dn liu cu A.G. Xtromberg, mc tiu hao ca dung dch c nh
hng n c tnh ca s ph thuc ca cng dng anot ha tan kim loi t hn
hng v nng ca ion kim loi trong dung dch :
i
A
= 3.K
A
. C
0
. v.
1
1
r
e
b
. ( )

(a)
K
A
l hng s dng anot, K
A
ph thuc vo h s khuch tn ca kim loi trong
hn hng, tc thay i th khi ghi cc ph, bn knh git thy ngn...
E1/2
E
p

I
c
kC
Pb
0

Pb
2+

I
a

Hg
0

Hg
2+

Pb
2+

Pb
0
(Hg)
I
c

-E
(a)
(b)
42
Nu b < 0,1 th b v phng trnh trn c dng :
i
A
=
12
0
.
. . . . .

nF
K K C r t
d A

Phng trnh ny ng khi tin hnh phn tch vi th tch dung dch ln, thi gian
in phn ngn v bn knh git thy ngn nh. Nng cc ion kim loi cn li trong
dung dch trong trng hp ny thc t khng i.
Gi tr pic ant t l vi nng ca ion kim loi trong dung dch, thi gian in
phn v bn knh ca thy ngn.
Nu b > 3 th 1, phng trnh trn s c dng :
i
A
= 3.K
A
. C
0
.v.(1/ r)
Khi th tch dung dch nh, thi gian in phn ln, bn knh git thy ngn ln
th cng dng anot t l thun vi nng kim loi trong dung dch, th tch dung
dch, t l nghch vi bn knh git thy ngn v khng ph thuc vo thi gian in
phn. Nng ion trong dung dch khi kt thc qu trnh in phn thng nh hn
5% so vi nng ban u.
Phng trnh (a) c tun theo trong khong gi tr b:
0,1 < b < 3
K thut tin hnh xc nh:
xc nh mt hay mt vi nguyn t, ngi ta t vo bnh in phn mt th
c gi tr cao hn th bn sng ca nguyn t b kh m nht l 0,2 - 0,3 V. Ti th
ny trong thi gian cho, tin hnh in phn dung dch th nghim v thng xuyn
khuy u dung dch. Sau khi dung dch khng b xo trn, ngi ta bt u ha tan
ant kim loi t hn hng khi th gim u.







Hnh 4.11. ng Von - Ampe ha tan ca mt s kim loi trong nn K
2
C0
3
0,1M
(Nng ca Zn
2+
, Cd
2+
, Bi
3+
, Cu
2+
l 10
-8
M; Pb
2+
v Te
+
l 10
-7
M in phn 5
pht ti E = -1,4 V so vi cc calomen bo ha, cc lm vic l git thy ngn treo).
Trong phng php Von - Ampe ha tan thng nhng vo bnh in phn cha
dung dch phn tch 3 cc:
I
a

Cu Bi
Te
Pb
Cd
Zn
E
0,0 -1,2
43
Cc lm vic l cc trn xy ra phn ng kt ta cht cn phn tch di dng
kim loi hoc hp cht kh tan.
Cc so snh, thng l mt loi cc loi II nh cc calomen hoc cc bc clorua.
Cc so snh c th khng i v phi gi th ny khng i trong sut qu trnh lm
vic, c bit khi tin hnh lin tip cc thc nghim trong thi gian in phn di.
m bo c iu , cn ch to cc so snh c din tch b mt ln mt
dng qua cc nh.
Cc ph tr thng l mt cc platin.
C 3 loi cc lm vic chnh:
Cc git thy ngn tnh di dng git treo hoc git ngi.
Cc rn hnh a.
Cc mng thy ngn c iu ch ti ch trn b mt cc rn a.
Trong cc ph hn hng ngi ta hay dng nht l cc git thy ngn tnh. l
mt git thy ngn c kch thc nh (ng knh 0,8 - 1,5 mm) v bt ng c
treo trn mt mao qun bng thy tinh hoc t trn mt mt thy tinh hi lm gia
c mt on nh v gn platin dn in. m bo tnh chnh xc v lp li
ca cc php xc nh, yu cu ch yu ca cc git thy ngn tnh l phi c kch
thc khng i v c lp li cao, v sau mi mt ln o phi to mt git khc c
kch thc nh git dng trong ln o trc. Thng thng ngi lm phn tch
khng th ch to c cc git treo tnh c cht lng cao v v vy ch c cc hng
mi sn xut c cc treo tt. Cc git thy ngn tnh ca hng PAR (M) v cc
git thy ngn treo kiu Kemula ca hng Brinkmann (M) l cc tt nht.
Nu c c mt git Hg tnh c cht lng tt th vic phn tch s rt thun li
v:
+ Khong th cho php dng cc thy ngn rt rng, xc nh c mt s rt ln
kim loi. Trong mi trng axit khong th dng c tt nht l -0,15 n -1,2 V;
trong mi trng trung tnh v kim khong th c m rng nhiu: t - 0,15 n gn
- 2 V.
+ Thun li cho vic chn iu kin phn tch nh chn thnh phn dung dch nn,
chn th in phn c bit khi phn tch cc kim loi trong mu c thnh phn phc
tp v c th tham kho, nghin cu nhng ti liu khc v phn tch cc ph bit
tnh cht cc ph ca cc cht kh cc khc nhau trong cc nn cc ph khc nhau.
+ Xc nh nng cht phn tch: Nng ca kim loi trong dung dch phn
tch thng c xc nh bng phng php thm. Khi phn tch nhiu mu c cng
mt thnh phn c th s dng phng php ng chun. Cng c nhng trng hp
gim nh hng do s bin i kch thc ca ht, do s thay i nhit , thi
gian in phn v cc yu t khc n kt qu phn tch, c tc gi s dng cht
chun trong. Khi s dng cht chun trong tnh nng ngi ta khng dng chiu
cao pic ca qu trnh ha tan ant kim loi t hn hng m dng t l chiu su gia
44
pic ca nguyn t cn xc nh v pic ca nguyn t a vo trong dung dch lm cht
chun trong.
4.2.3. Cc ph xung
Nhng phng php phn cc in cc hot ng bng nhng xung in p gin
on c bin v b rng (thi gian tn ti) xc nh gi l nhng phng php cc
ph xung. C hai phng php cc ph xung c bn hin ang c s dng ph bin:
Phng php cc ph xung bin i u (Normal pulse polarography - NPP)
Phng php cc ph xung vi phn (Differential pulse polarography - DPP)
4.2.3.1. Phng php cc ph xung bin i u (NPP)
Trong phng php ny in cc git thy ngn c phn cc bng mt in p
mt chiu chn trc v c gi khng i trong sut qu trnh , in p ny c
gi l in p khi im, tng ng vi chn sng trong phng php cc ph c in,
trong mi mt chu k git, in cc c phn cc b xung bng mt xung vung
gc c khong tn ti rt ngn (40 n 100 ms) c a vo st nt trc khi git ri
(hoc chu k kt thc). Sau thi gian xung b ngt v th in cc tr v in p
khi im. Bin xung tng dn theo thi gian vi mt tc u ging nh tc
qut th tuyn tnh trong cc ph c in. Cng dng cc ph c ghi theo mt
trong hai cch sau :
Ghi cng dng cc ph ti mt thi im xc nh sau khi t xung (thng
l 17 ms trc khi ngt xung), phn ln cc my hin ang s dng thc hin theo
cch ny.
Ghi cng dng cc ph hai ln, ln th nht trc khi t xung v ln th hai
sau khi t xung (trong 2 khong thi gian ging nhau: 17 ms trc khi t xung v 17
ms trc khi ngt xung). Cch ny cho hiu qu tt hn nhng kh phc tp.
Phng php NPP c th t nhy 2.10
-7
M cho c hai qu trnh thun nghch
v bt thun nghch.
4.2.3.2. Phng php cc ph xung vi phn (DPP)
Trong phng php ny, in cc c phn cc bng mt in p mt chiu bin
thin tuyn tnh vi mt tc chm, nhng cui mi mt chu k git (git ri cng
bc nh mt b g) trn khung in p bin i mt chiu, ngi ta dt thm mt
xung vung gc vi bin thay i trong khong 10 - 100 mV v di xung t 40 -
100 ms. Cng dng cc ph c ghi hai ln, ln mt ti thi im
1
, thng l
trong 17 ms trc khi np xung v ln th hai ti thi im
2
, thng l 17 ms trc
khi ngt xung. Hai gi tr ny c a vo b so snh v kt qu chuyn ra b ghi l
hiu s ca hai gi tr . ng cc ph c dng pc. u im ni bt ca phng
php ny l c nhy cao vi cc hp cht v c v hu c cc qu trnh thun
nghch v khng thun nghch v quan trng hn l ng I - E c dng nh cc i,
sau mi mt nh dng in li tr v trng thi nn, do phng php c phn
gii rt cao, c th t n 50.000 (v d c th ghi 10
-7
M Cd
2+
khi c mt 5.10
-3
M

45
Cu
2+
m khng cn tch). iu ny cho php phn tch trc tip nhiu cht trong cng
mt dung dch. Mt hng phn tch c nhiu trin vng l s dng kt hp DPP vi
von-ampe ha tan, v d c th xc nh 10
-9
M Pb
2+
vi thi gian khng qu 3 pht.
C th ni, hin nay DPP l phng php cc ph hon chnh nht v phng php
ny c nhy cao, chn lc cao v c tnh vn nng i vi hu ht cc i tng
phn tch.

46
Chng 5 : Cc phng php phn tch sc k
5.1. M u
Nm 1906, nh bc hc Nga Michael Tvest cho dung dch cc sc t thc vt
trong ete du ha ln ct nhi bt mn canxi cacbonat, ng thy cc sc t b hp ph
ln trn u ct. Khi cho ete du ha ln ct, cc sc t di chuyn trong ct t trn
xung di, mi sc t c mt tc ring, tch thnh nhng vng hay vng mu xp
chng ln nhau, hnh thnh mt h m Tvest gi l sc . ng t tn cho phng
php tch ny l sc k (Chromatography). Trong ting Hi Lp chroma l mu,
graphein l vit. Tn gi ny ngy nay vn c s dng mc d phng php ny
cn c dng tch cc cht khng mu.
5.2. Mt s khi nim
5.2.1. Qu trnh sc k
Sc k l mt nhm cc phng php ha l dng tch cc thnh phn ca mt
hn hp. S tch sc k c da trn s phn chia khc nhau ca cc cht khc nhau
vo hai pha lun tip xc v khng ha ln vo nhau: mt pha tnh v mt pha ng
(trong th nghim ca Tvest): pha tnh l canxi cacbonat, pha ng l ete du ha.
Qu trnh tch sc k gm 3 giai on chnh:
a. a hn hp ln pha tnh (v d a dung dch cc sc t ln u ct
canxicacbonat). Cc cht c gi trn pha tnh.
b. Cho pha ng chy qua pha tnh (v d: dung mi ete du ha qua ct), pha
ng s ko theo cc cht di chuyn trn pha tnh vi tc khc nhau, tch khi nhau
v c v tr khc nhau trn pha tnh to thnh sc . Giai on ny gi l khai trin
sc k
Nu tip tc cho pha ng chy qua th cc cht c th ln lt b ko ra ngoi pha
tnh (v d: ra khi ct). l qu trnh ra gii v dung mi dng c l dung mi
ra gii (eluent) dch hng c cui ct gi l dch ra gii (eluate).
Nu cc cht c tch trn pha tnh (sc k khai trin) ta c th ly tng phn pha
tnh c mang cht (phn on bt trn ct) em chit ly cht.
Nu cc cht c tch ra ngoi pha tnh (sc k ra gii) ta c th hng thu ly
cc phn on dch ra gii c cha cc cht cn phn tch.
c. Pht hin cc cht : Cc cht mu c th pht hin d dng, cc cht khng mu
c th pht hin bng n t ngoi hay bng cc thuc th. Trong sc k ra gii c th
47
pht hin cc cht khi chng i ra khi ct bng cch cho dung dch ra gii i qua
mt b phn pht hin gi l detect (etect) t sau ct.
5.2.2. Phn loi cc phng php sc k
- Theo bn cht vt l cc pha:
Pha ng c th l mt cht lng hay cht kh, pha tnh c th l mt cht rn (ht
xp hay bt mn) hay mt cht lng (c gi trn mt cht mang rn). Do , da
vo bn cht cc pha ta phn bit cc phng php (trong tn ca phng php, pha
ng c nu trc pha tnh);
Sc k lng - lng (Liquid - liquid chromatography LLC )
Sc k lng - rn ( Liquid - solid chromatography LSC )
Sc k kh - lng (Gas - liquid chromatography GLC)
Sc k kh - rn (Gas - solid chromatography GSC)
Hai phng php u gi chung l sc k lng (LC)
Hai phng php cui gi l sc k kh (GC)
- Theo hin tng sc k:
Sc k hp ph (adsorption chromatography) pha tnh l cht rn c kh nng hp
ph, l cc phng php sc k lng - rn v kh - rn.
Sc k phn b (partition chromatography) pha tnh l cht lng khng ha ln
c vi pha ng, cht lng ny c bao trn b mt mt cht rn gi l gi hay
cht mang v phi l cht tr, khng tham gia vo sc k. Sc k phn b bao gm sc
k lng - lng v sc k kh - lng.
Sc k trao i ion (ion - exchange chromatography) pha tnh l cht nha trao i
ion (hp cht cao phn t c mang nhng ion c kh nng trao i vi cc ion cng
du ca dung dch hn hp sc k).
Sc k theo loi c (size - exclusion chromatography) cn gi l sc k trn gel.
Cc phn t c ln s c loi, cc phn t nh hn s c tch theo kch thc do
cc phn t nh di chuyn chm hn.
- Theo k thut v phng tin sc k:
a. Theo phng php gi pha tnh:
Sc k trn ct (column chromatography: CC) pha tnh c cha trong mt ct
bng kim loi hay thy tinh.
Sc k lp mng (thin layer chromatography; TLC) pha tnh c trng u v
gi trn mt phng ca bn thy tinh, nha hay nhm. Lp mng pha tnh thng l:
silicagel, nhm oxyt, celuloze, cht nha trao i ion, v c chiu dy khong 0,2 - 0,5
mm.
Sc k giy (paper chromatography - PC) pha tnh (lng) c thm trn mt
loi giy lc c bit gi l giy sc k.
48
b. Theo cch cho pha ng chy ta c:
Sc k khai trin (development chromatography) cho pha ng ko cc cht chy
v tch trn pha tnh (sc nm trn pha tnh). Sc k ra gii (elution
chromatography) cho pha ng chy v ko cc cht ln lt ra ngoi pha tnh (ra khi
ct, ra khi giy).
Ghi ch: Sc k lp mng v sc k lp giy gi chung l sc k mt phng (planar
chromatography ).
SC K LNG C TH TIN HNH TRN CT, TRN MT PHNG (LP
MNG, GIY).
Sc k kh c tin hnh trn ct.
Sc k khai trin thng c thc hin trn mt phng (giy v lp mng). Sc k
ra gii thng tin hnh trn ct.
- Phn loi sc k theo bn cht cc pha:








Ghi ch: GSC : Sc k kh - rn GLC : Sc k kh - lng
LSC : Sc k lng - rn IEC : Sc k trao i ion
BPC : Sc k pha lin kt IC : Sc k ion
LLC : Sc k lng - lng SEC : Sc k loi c
AC : Sc k i lc PC : Sc k giy
TLC : Sc k lp mng
5.2.3. S tch sc k v sc
- S tch sc k v sc :
Khi cho mt dung dch cha cht A v B chy qua mt ct cha cht hp thu.
Nng ca cht A v B trong dung dch s gim i do mt phn cc cht ny phn
b chuyn vo cht hp thu. Nng ca cc cht tan A, B trn cht hp thu s tng
dn v A, B b tch ra khi dung dch. ng thi cng xy ra mt qu trnh ngc li,
cc cht A, B trn ct hp th li phn b tan tr li vo dung dch. Qu trnh ny ph
SC K
Kh (pha ng) GC Lng (pha ng) LC
GSC
GLC
Ct
Phng
LSC BPC LLC SEC AC TLC
PC
IEC IC
49
thuc vo h s phn b ca A, B trong dung dch v cht hp thu cho n khi t cn
bng:
Tc hp thu = tc gii hp
Tuy nhin v pha ng (dung dch) lun di chuyn nn cn bng trn li b ph v,
v mt cn bng mi li c thit lp. C nh vy qua rt nhiu cn bng (c khi
hng nghn cn bng pha) cc cht A, B c tch ra khi nhau do kh nng phn b
ca A v B vo cht hp thu hay kh nng b gi trn ct ca A v B l khc nhau.
V d: Cho mt dung dch cha ion ng v ion coban ln trn mt ct c cht hp
thu (1), nh th ng v coban b hp thu trn ct (2). Sau tip tc cho dung mi
qua ct, ng v coban s b ko dn xung v dn dn chng tch ra thnh cc lp
(3), dung mi tip tc c cho qua ct v hai lp Cu
2+
v Co
2+
s c tch ra khi
nhau (4,5), ti thi im t
2
s thy c hai di tch ring khi nhau trn ct: ta c sc
ngay trn ct. Nu dng y ta c sc k khai trin.










Nu tip tc thm dung mi, ti thi im t
3
, di Co
2+
s tch ra khi ct, nh thit
b detect ta s thu c tn hiu di dng mt nh hay mt pic, thi im t
4
di
Cu
2+
ra khi ct li v cho ta thm mt pic tng ng. Ta thu c mt sc gm hai
pic ring bit ng vi hai cht trn. y l phng php sc k ra gii v sc thu
c gi l sc ra gii. V tr ca pic trn trc thi gian l c s nh tnh cht
tng ng v din tch di pic l c trng nh lng ca cht.
Trong qu trnh ny ta thy c mt s khc bit v kh nng phn b trong cht
hp thu trn ct: Cu
2+
c hp thu mnh hn nn s y Co
2+
ra, s d c hin tng
l v:
tan ca ng trong dung mi nh hn so vi coban.

i lc ca cht hp thu i vi Cu
2+
mnh hn so vi Co
2+
.

V hai l do trn nn ng s b gii hp t hn. Nng ion Co
2+
trong dung mi
t nh n cc i ri gim n 0.
t
4

Cu
2+
+Co
2
+
Cu
2+
Co
2
Cu
2+

Co
2

Cu
2
+

Co
2

Cu
2
+

Detector
t
0
t
1
t
2

t
3

Dung dch
mu
Tn hiu
Detector
Pha ng
Hnh 5.1. S tch sc k v sc
50
Tc di chuyn ca di ph thuc vo tc di chuyn ca pha lng (pha ng)
v mc hp thu ca cht hp thu i vi cht tan. Cht no b hp thu mnh nht s
di chuyn chm nht v n b dung mi gii hp t nht.
C nh vy trong iu kin thch hp ta s tch c hon ton cc cht ra khi
nhau.
Do tc dung lm chm (Retardation), do s phn b hp thu khc nhau ca pha
tnh i vi tng hp phn trong hn hp, ngi ta c th tch ra tng hp phn trong
hn hp. V nguyn tc ca phng php sc k l: Da vo s phn b khc nhau ca
cc hp phn trong hn hp gia hai pha ng (moving phase) v tnh (stationary
phase).
- Tc di chuyn ca mt cht :
Tc di chuyn ca mt cht c th c c trng bi h s phn b ca n
gia hai pha hoc bi cc i lng v s lu gi ca cht trn pha tnh (thi gian
lu, th tch lu).
a- Thi gian lu v th tch lu: Thi gian lu l thi gian cn mt cht di
chuyn qua ct sc k, khi ra khi ct nh thit b detect ghi nhn tn hiu v xut
hin pic trn sc (tnh t lc bm mu n khi xut hin pic).










t
M
: L thi gian lu ca mt cht khng b lu gi, ngha l tc di chuyn ca
n bng tc di chuyn trung bnh ca dung mi, thi gian ny cn c gi l thi
gian cht. t
R
cng ln, cht cng b lu gi mnh v tc di chuyn ca n cng nh.
Thi gian lu hiu chnh t
R
c tnh theo cng thc :
t
R
= t
R
- t
M

Nu trn trc honh ca sc , dng n v o l th tch dung mi th ta c cc
i lng tng t: th tch lu V
R
v th tch lu hiu chnh V
R
, th tch V
M
c gi
l th tch cht ca ct hay cn gi l th tch rng V
0
.
V
R
= V
R
- V
M

W
thi gian
tn hiu detector
ng nn
t
R

t
M

Hnh 5.2. Sc ca mt cht.

51
b- H s phn b :
K = C
S
: C
M

Trong C
S
v C
M
l nng cht tan trong pha tnh v pha ng khi cn bng
c thit lp. Khi nng nh K ph thuc vo bn cht cc pha, cht tan v nhit
. K cng ln th cht phn b cng nhiu trong pha tnh v s di chuyn cng
chm.
c- H s dung lng K(H s phn b khi lng) :
K= Q
S
: Q
M

Trong : Q
S
v Q
M
l lng cht tan phn b trong pha tnh v pha ng, Kph
thuc vo bn cht cc pha, bn cht cht tan, nhit v c im ca ct. tch
mt hn hp cht, ngi ta thng chn ct, pha ng, v cc iu kin phn tch khc
sao cho K nm trong khong t 1 n 8.
- S dong pic v hnh dng pic:
a - Hnh dng pic: Hnh dng l tng ca pic l pic i xng, nhng thc t pic
sc k ch gn i xng. Chiu rng ca pc c o 1/10 chiu cao ca pic.
b- S dong pic: S dong pic l kt qu ca s di chuyn nhanh, chm khc nhau
ca cc phn t ca cng mt cht khi i qua ct sc k. Cc pic ra chm bao gi cng
t hn.
c- Hiu lc ca ct: Hiu lc ca ct thng c o bng hai thng s: S a l
thuyt N v chiu cao a l thuyt H. Ta c th coi nh ct sc k c chia thnh N
lp hay N tng mng, mi mt lp s phn b cht tan vo hai pha t trng thi cn
bng. Nhng tng mng gi nh ny c gi l a l thuyt. Nu ct sc k c chiu
di l L th: H = L/N. Ct c N ln l ct c hiu lc cao.
d- phn gii: phn gii R
S
l t s khong cch gia hai pic v rng
trung bnh ca pic.
R
S
= 0,75 hai pic tch khng tt, cn xen ph nhau nhiu
R
S
= 1,0 hai pic tch kh tt, cn xen ph nhau 4%
R
S
= 1,5 hai pic tch hon ton (ch xen ph 0,3 %)
5.3. Sc k lng hiu nng cao
Sc k lng hiu nng cao (High performance liquid chromatography-HPLC) cn
c gi l sc k lng cao p hay sc k lng hin i. Trong phng php ny pha
tnh c dng l nhng ht c kch thc rt nh khong 10 micromet c hiu xut
tch rt cao. C ht nh i hi phi dng bm nn dung mi qua ct.
5.3.1. My sc k lng hiu nng cao
- S d nguyn tc ca mt my sc k lng hiu nng cao nh sau:

52









1 - Bnh cha dung mi
2 - Bm cao p
3 - B bm mu
4 - Ct sc k
5 - etect
6 - My ghi tn hiu

- Cc thnh phn chnh ca my sc k lng hiu nng cao
a. Bnh cha dung mi:
Thng lm bng thy tinh, i khi lm bng thp khng r, trong phng php
ra gii thng thng ch cn mt bnh cha dung mi, trong phng php ra gii
gradient thng dng 2, 3, 4 bnh cha cc dung mi khc nhau v h dung mi ra
gii l hn hp ca cc loi dung mi trn trn ln vi nhau theo t l dc xc
nh. Cn loi cc ht v cc kh ha tan trong dung mi.
b. H thng bm:
Bm dng trong phng php phi to c p sut cao (3000 - 6000 psi hay
khong 250 - 500 at), lu lng bm khong 0,1 n 10 ml/ph, phi tr vi cc dung
mi. H thng bm ny phi c kh nng bm pha ng qua ct p sut cao m
khng b ngt qung hoc to nhp sng c th lm sai lch cc pic thu c. C nhiu
kiu bm dng trong cc my HPLC, nhng kiu pitng xoay chiu hin nay c
dng ph bin nht.
c. H bm mu (H tim mu):
Mu c bm vo ct nh h thng van mu. Ngi ta bm mu vo vng mu
vi th tch thng l t 10 n 20 l.
d. Ct sc k:
2
3
5
1
4
6
Hnh 5.3. S my sc k lng hiu nng cao

53
Kiu ct thng ph thuc vo phng php dng tch, nhng thng l nhng
ct bng thp khng r, c c l chnh xc ng knh t 3 n 4 mm v di t 10 n
30 cm (nhng ct dng cho SEC thng rng hn v di n 100 cm). Loi ct ny c
hiu lc rt cao, c s a l thuyt ln n 100.000 a cho 1 m chiu di ct.
e. Detect :
L b phn pht hin cc cht khi chng ra khi ct v ghi nhn cc tn hiu ghi
trn sc . Hin ang s dng cc loi detect sau:
Detect t ngoi (UV): Dng n thy ngn cho vch 254 nm. Nhiu cht hp
th bc sng ny.
Detect t ngoi v kh kin ( UV- VIS ): Dng ph quang k la chn bc
sng t 195 n 750 nm. Loi ny hin nay c dng nhiu nht.
Detect in ha v detect hunh quang c nhy v chn lc cao hay
dng trong phn tch vt. Dng detect in ha c th pht hin c nhng lng
picrogam (10
-12
g).
5.3.2. Cc phng php sc k hiu nng cao
a. Sc k phn b hiu nng cao:
Gm hai loi: Sc k lng-lng v sc k pha lin kt.
- Sc k lng - lng (LLC): Pha tnh l cht lng c bao trn b mt ca cc ht
cht mang, tc l c hp ph trn cht mang.
- Sc k pha lin kt (BPC): Pha tnh c gn ha hc vi cht mang to ra lin
kt siloxan ni nhm c - silic vi silicagen.
b. Sc k hp ph hiu nng cao (sc k lng-rn LSC):
Pha tnh l cht rn m trn b mt c cha cc nhm hidroxyl phn cc. Pha ng
l mt dung mi khng phn cc.
c. Sc k trao i ion hiu nng cao (IEC):
Pha tnh rn cha cc nha trao i ion di dng bt mn, pha ng thng l
dung dch nc.
d. Sc k lng hiu nng cao trn gel (sc k loi c SEC):
Phng php ny c ng dng ch yu cho cc cht c phn t lng ln. Cht
nhi cho SEC l nhng ht xp ca silicagel hay cc polime c kch thc nh
(khong 10 m). Pha tnh l dung mi nm trong cc l xp ca ht, pha ng l dung
mi chy gia cc ht. Ch nhng phn t nh mi khuch tn vo lp xp, khi ra
gii cc phn t s ln lt ra theo c t ln n nh.
5.4. Sc k kh (GC - Gas chromatography)
Sc k kh l phng php c dng tch cc cht th kh bay hi, vi pha
ng l cht kh, gi l kh mang (carrier gas).
54
Nh nu trn, c th chia php sc k kh thnh sc k kh rn (GSC - gas
solid chromatography) trong pha tnh rn l mt cht hp ph, y l sc k kh hp
ph v sc k kh lng (GLC - gas liquid chromatography) trong pha tnh lng c
bao hay gn trn mt cht mang rn (solid support) y l sc k kh phn b.
S dng phng php sc k kh c kh nng tch c hon ton nhng cht hu
c tng t, v d nh o-; m-; p - xylen khng th tch c bng phng php chng
ct phn on nhng tch c kh n gin bng sc k kh, cng nh s dng
tch nhng hn hp rt phc tp nh kh thi t cha trn 300 hp phn. Vi vic ra
i ca nhiu loi detect, nhiu phng php mi xut hin nh: sc k kh - khi ph
(GS - MS), sc k kh - hng ngoi (GC- IR)... lm tng kh nng phn tch ca sc
k kh .
MY SC K KH
S nguyn tc ca mt my sc k kh nh sau:






Kh mang:
Kh mang l mt kh tr nh nit, heli, argon, hidro... trong heli l kh mang
ph bin nht. Kh c cha trong bom kh c gn van gim p v iu chnh. Kh
mang cn c tinh khit cao v phi khng tng tc vi mu, ch mang mu i qua
ct. Tn hiu detect c ph thuc vo s khc nhau v tnh cht gia kh mang v
cht cn phn tch.
B bm mu:
Thng dng bm tim bm trc tip mu qua mt vch polime silicon chu
nhit cao vo ct hoc vo phng un nng mu mu lng c th bay hi nhanh
chng. Yu cu cn thit l mu phi c p sut hi c th c lm bay hi
trong phng mu. Nhit phng mu c th cao hn nhit trong ct mt cht
qu trnh bay hi c thc hin d dng.
Ct sc k:
Ct c t trong l c th iu chnh nhit trong qu trnh thc hin.
1
2
3
4
5
6
Hnh 5.4. S my sc k kh
1- Bnh kh mang; 2 - Bung bm mu; 3 - L;
4 - Ct sc k; 5 - Detector; 6 - My ghi
55
Ct thng dng nht trong phn tch l nhng ng bng thp khng r (ng, thp)
hoc bng thy tinh di t 1 n 10 m v c ng knh t 2 n 4 mm. Chng c
un hoc cun trn cho khp vi phng l. Ct c nhi bng nhng phn t rn
hot ng nh mt pha tnh (GSC): l nhng ht nh xp gn trn mt trong ct
hoc pha tnh c tm trn cc ht nh . Trong sc k kh lng (GLC), pha tnh
c gi trn cht mang, l nhng ht cht rn nh, bn nhit, tr v mt ha hc,
c l c 1- 5 m, b mt ring ln t 1- 10 m
2
/g.
Pha tnh phi chu nhit, ha lng nhit phn tch, tr v ha hc. Thng
hay s dng cc polime xp hoc gel aluminosilicat kh nc.
Detect:
Yu cu v detect rt nghim ngt: Mi hp phn c trong 0,1 l mu phi c
pht hin mc 1%, cho nn phi nhanh chng pht hin c 0,002 l (c khi
lng c 10
-6
g) mu. Cc etect hin nay o c nhng lng nh hn n my
bc. Hin nay trong phng php GC ngi ta s dng nhng loi etect sau:
etect dn nhit (TCD) : Vic vn hnh ca etect da trn s cn bng nhit
ca mt dy dn un nng. Khi c cht cn phn tch i qua th dn in ca hn
hp kh s thp i, dy s nng ln, xut hin mt tn hiu in. etect dn nhit
thch hp c vi nhiu cht cn phn tch.
etect ion ha ngn la (FID): Khi t chy cc hp cht hu c trong ngn
la, chng s to ra cc ion. Cc in cc gn ngn la s pht hin ra s c mt ca
cc ion bng s xut hin mt dng in nh chy qua mch in .C th o c
nhng dng ngay c khi chng ch xp x bng 10
-12
A. y l etect c dng
nhiu nht, pht hin c n 10
-9
g .
etect hp th in t (etect bt in t - ECD): Nh c ngun phng x
nh
3
H hoc
63
Ni, kh mang b ion ha to nn mt dng nht nh trong mch
detect. Khi mt cht phn tch hp th in t c gii hp n s lm gim dng ny
c bit khi hp cht c cha nguyn t c m in cao. Dng s gim i, to ra tn
hiu ghi c. etect c bit nhy cm vi nhng hp cht cha halogen. etect
hp th in t rt thun li cho vic phn tch mi trng. nhy cao, t ti 10
-12

g.
Thng tin GC
Sc thng thng biu th trn hai trc x v y, trong tn hiu detect ghi trn
trc y v thi gian ghi trn trc x.
Khi mt hp phn ca mu c gii hp v pht hin nh etect th tn hiu
s c ghi li. Thi gian ghi c pic tn hiu l hm ca K
D
v v th n cung cp
thng tin nh tnh v mu ging nh th bn sng trong cc ph, v s nhn bit c
mt hp phn trong mu.
Thng tin nh lng t sc c rt ta t ch tn hiu detect l hm ca thi
gian. Din tch di pic t l vi lng cht phn tch. Lng ny c th biu th bng
n v mol hoc n v khi lng, tuy nhin hng s t l s khc nhau:
56
S
A
= din tch di pic = R A
Trong : R l din tch trn mt mol khi A c biu th bng mol, R l din tch
trn mt gam khi A biu th bng gam.












Hnh 5.5. Sc ca hn hp cha cc cht cn phn tch A v B
a - nng l hm lng ra gii; b- tn hiu hm ca thi gian
N - nng cht cn phn tch (mmol/ml)
5.5. Tch chit cc cht nhim hu c v lm sch mu
a. Tch chit mu:
Cc cht nhim hu c trong nc, t, trm tch, nc cng rnh, cht thi rn
v cc vt liu khc phi c chit tch bng dung mi hu c thch hp trc khi
a vo ct sc k (GC). Cc cht chit rt ny ng thi cng lm tng nng cc
cht cn phn tch theo cc gi tr ppb hoc ppt. Ph thuc vo bn cht cc cht, cc
k thut chit rt khc nhau s c s dng nh s sau y:











N
0 6 50
55
A B
V2
V
1

V
3

V
m

V
RA

V
'
RA

VRB
V
'
RB

W
A
WB
Th tch
(ml)

Phun mu V = 0
0
30
240
260 280
t
1

t
2

t
3

W
A

W
B

t(s)

Phun mu, t = 0
t
m

t
RA

t
'
RA

t
RB

t
'
RB

Tn
hiu
Chit rt cc cht nhim hu c
Chit pha
rn
Chit rt
bng phu
phn tch
Tip tc
chit h
lng-lng
Phng php
Soxhlet
Phng php
Sng m
Tch chit cht lng
vt qu mc ti hn
Mu t, cht thi
Chit h
lng-lng
57


- Chit h lng - lng (liquid-liquid extraction)
Cc mu nc thng c s dng cc cht lng tch chit (LLE). Th tch
mu nc c tch chit nhiu ln bng cht lng (dung mi hu c) khng trn ln.
S la chn cc dung mi hu c phi p ng cc yu cu sau:
1. Khng trn ln vi nc.
2. Cc cht nhim hu c phi ha tan trong dung mi ny (kh nng ha tan ca
chng phi ln hn trong nc).
3. T trng ca dung mi ny phi ln hn nc khi cht chit rt c tch ra
trong phu chit hoc mt dng c tch chit lin tc cht lng - cht lng, ngc li
dung mi phi c t trng nh hn nc khi s tch chit vi phn trong bnh thy tinh
nh.
Ph thuc vo s trn ln ca mu cht lng vi dung mi, cc cht nhim s
ha tan vo trong dung mi chit rt.
H s phn b s tng ng t l ca cc cht ha tan trong dung mi theo cc
cng thc:
P = C
dung mi
/ C
nc

V P khng ph thuc vo t l th tch v l hng s nhit nht nh. Nu
tng th tch dung mi chit rt th cc cht ha tan vo chng s tng ln. Trong
trng hp th tch dung mi chit rt khng thay i, th chia nh v chit nhiu ln
cng s tng hiu qu ca qu trnh tch chit. V d nh tch chit cc cht bn bay
hi hu c s c hiu qu cao hn khi s dng chit rt ba ln vi 60 ml metylen
clorua so vi chit 1 ln bng 180 ml.
- Chit rt pha rn (solid phase extraction)
Cc cht hu c c th c tch chit t cht lng bng cch tch chit cht lng
- cht rn. Qua trnh ny rt n gin, nhanh chng v r hn LLE. Phng php ny
cn ly mt th tch bit cht lng cho chy qua mt ng c cha cc cht hp ph
thch hp, cc cht nhim hu c trong mu s c hp ph trn b mt cht rn
hp ph, sau c gii hp bng mt cht dung mi thch hp. Mu s c cho
vo t pha trn ng hp ph v iu chnh cho tc chy 1-2 git/giy. Nu ng hp
ph ln c th cho tng tc d chy. ng s c ra bng dung mi khng phn cc
cho cc cht phn tch phn cc v ngc li. Cui cng cc cht phn tch s c
gii hp bng dung mi thch hp. Dung mi phn cc s dng cho cht phn tch
phn cc v ngc li. Mu c th c c c bng cch lm bay hi dung mi.
S la chn cc cht hp ph da vo tnh phn cc ca cc cht phn tch (bng
5.1)
Bng 5.1. Cc cht chit rt pha rn
- Hp phn khng c cc

- Hp phn c cc trung
Octadecyl (C-18) lin kt vi Silic, Octyl (C-8)
lin kt vi Silic
Phenyl-, ethyl- v cyclohexyl lin kt vi Silic
58
bnh
- Hp phn phn cc
Silic, florisil, Silicagen, Cyano-, Diclo-, v nhm
amin lin kt vi silic, silicat v nhm.
Phng php ny c u im l: nhanh, hiu qu cao, khng cn bc
lm giu mu v khng i hi lng ln cc dung mi hu c.
Tch chit Soxhlet (Soxhlet extraction):
Phng php ny thch hp cho chit cc cht hu c khng bay hi hoc bn bay
hi. Mu c cho vo dng c tch chit ri ngm vo dung mi. Qu trnh tch chit
c thc hin nh hng lot cc thao tc bao gm c bay hi v c c. Chit rt
soxhlet vi dung mi florocacbon thng c s dng tch cc hyro cacbon ca
du m t t, tuy nhin phng php ny t c s dng v phng php ny cn
nhiu thi gian v tn nhiu dung mi.
Tch chit cht lng vt qu mc ti hn (surpercritical Fluid Extractiron).
Cht lng vt qu mc ti hn l cc cht nm trn nhit v p sut ti hn.
V d nh CO
2
, NO
2
thng s dng cc cht lng vt qu mc ti hn tch. Cc
mu rn c a vo bnh chit ri dng h thng bm to p sut cao. Cht hu
c phn tch s hnh thnh cht lng v tch ra. p sut s c iu chnh v mc
bnh thng nh cc van v cht lng vt qu mc ti hn ny s chuyn thnh dng
kh v c hp th bng cc dung mi thch hp nh metylenclorua.
Qu trnh tch chit ny cng c th c y nhanh khi cho thm mt lng nh
cc cht ng dung mi (nh axeton hoc metanol).
Phng php ny c u im l nhanh, hiu qu cao, khng cn phi lm giu
mu v khng i hi lng ln dung mi hu c.
b. Lm sch:
Cc cht chit mu c th c lm sch bng nhiu k thut khc nhau:
- S chia tch axit - baz:
Phng php ny p dng phn chia cc cht hu c axit hoc baz vi cht
hu c trung tnh. Dung mi sau khi tch chit mu s c lc vi nc c tnh kim.
Cc cht hu c axit s phn tch trong mt lp nc trong khi cc cht hu c axit v
trung tnh vn ha tan trong dung mi hu c v c tch ra. Sau lp nc s
c tch ra v axit ha n pH < 2 ri chit bng metylenclorua. Lp hu c lc ny
s cha cc thnh phn c tnh axit. Cc cht phenol, clorophenoxy axit, thuc dit c
v cc cht hu c bn bay hi s c bay hi lm sch bng phng php ny.
- Lm sch bng ct nhm:
Oxit nhm dng ht xp c kh nng tn ti trong mi trng axit, trung tnh v
kim c s dng trong ct sc k. Cc cht phn tch c chia tch nh tnh cht
phn cc ha hc khc nhau ca chng. Ct c nhi y bng nhm, sau ph ln
trn bng Na
2
SO
4
khan, cht c tch chit s cho ln trn cng.
Nhm c chun b vi nhiu mc hot tnh khc nhau bng cch cho thm
nc cho mc 1 (c chun b bng cch nung nng t
0
> 400
0
C n khi khng
cn nc thot ra). Trong cc cht nhim thng thng cc este phtalat v
59
nitrozamin s c tch ra. Nhm pH = 9 - 10 l hot ng nht khi tch cc hp
phn kim v trung tnh nh kim, ancaloit, steroit, ru, v cc cht mu.
Khng s dng mt s dung mi nh axeton hoc etylaxetat. Cc dng ny ca
nhm c th b polime ha, tch nc v ngng t.
Cc dng trung tnh t hot ng hn dng baz v c dng tch anehyt,
xeton, este v lacton... Dng axit (pH = 4 - 5) c dng tch cht axit mnh v cc
cht mu axit. Ct nhm cng c dng tch cc cht thi ca du m.
- Lm sch bng silicagen:
Gel silic l mt dng v nh hnh c tnh axit yu, c to ra bng cch x l axit
H
2
SO
4
vi natri silicat. C hai loi gel silic, dng hot ha (activated form) c
chun b bng cch un nng cc gel silic 150
0
C trong vi gi, dng ny c s
dng tch cc hyrocacbon. Dng khng hot ha (deactivated form) cha 10 -
20% nc v c dng tch cc cht do (plasticcizers), steroit, tecpenoit,
ankanoit, glycosit, thuc nhum, m, ng, este v cation kim loi kim. Trong phn
tch mi trng, gel silic c dng lm sch mu c cha cc hp phn thuc bo
v thc vt n gin, PCBs, cc hydrocacbon thm a nhn, v cc hp cht phenol.
Cc cht metanol v etanol lm gim hot tnh hp ph.
- Ct lm sch Florisil:
Florisil l mt dng magie silicat c tnh axit, c dng lm sch mu chit c
cha cc cht bo v thc vt c gn clo, photpho, cc este phthalat, nitrozamin, cc
haloete, cc vng thm cha nit v cc hydrocacbon cha clo. Florisil cng c
dng tch cc cht vng thm t hn hp cc cht bo v nhn thm cng nh tch
este, xeton, glycosit, steroit, ankanoit v mt s hydratcacbon. N cng tch c cc
hp phn nit t cc hydrocacbon.
Ct s c nhi y florisil, ph ln trn bng Na
2
SO
4
khan. Cc dung mi thch
hp s c cho i qua ct. Cc cht cn tr s c gi li trong ct.
- Lm sch bng gel thm lc (gel permeation clean up):
S lm sch ny da trn c s kch thc ca cc mng xp v ca cc keo k
nc. Cc l hng phi ln hn kch thc phn t cn c tch.
S lm sch bng gel thm lc (GPS) c s dng lm sch cc mu chit rt
t cc phn t tng hp phn t ln, cc cht do polyme, protein, m, steroit, virut,
nha t nhin v cc hp cht cao phn t khc. Metylenclorua c s dng lm
dung mi cho s tch chit. Cho 5 ml cht lng chit rt ln ct GPC. Cc cht phn
tch s c tch ra trong cc dung mi thch hp v c lm giu phn tch.
- Lm sch lu hunh (Sulfua clean up):
Lu hunh c trong nhiu loi cht thi cng nghip, to bin, cc mu phn tch.
Lu hunh thng gy cn tr qu trnh phn tch, lm trng lp cc ph ca nhiu
cht. Chng hn khi phn tch thuc tr su, lu hunh c th che lp nhiu cht nh
lindan, andrin v heptaclo. Lu hunh cng c kh nng ha tan tng t nh cc
thuc tr su c clo v c photpho v khng c kh nng tch bng phng php
Florosil.
60
Loi b lu hunh bng cch x l mu chit vi mt trong cc cht sau: ng,
thy ngn hoc natri-amoni-tetrabutyl sunfat.
- Lm sch bng axit sunfuric-pemanganat (pemanagnate sulfuric acid clean up):
Cc cht cn tr trong mu chit c th c loi tr bng cht oxi ha mnh nh
KMnO
4
hoc H
2
SO
4
c hoc hn hp c hai hp cht ny. Trong mi trng hp
trn, cht phn tch phi bn vng ha hc vi cc cht oxi ho. V d cht cn tr
phn tch polyclorinat biphenyl c th b loi tr vi mt lng nh KMnO
4
- H
2
SO
4
.
PCBs - bn ha hc vi iu kin ny v khng phn ng vi hn hp axit -
pemanganat trong thi gian tip xc ngn nh vy.
5.6. Phn tch cht nhim hu c bng sc k kh
Sc k kh (GC - Gas chromatography) l k thut ph bin trong phn tch nh
lng cc cht nhim hu c trong cc mu nc cng nh cc cht khng dng
lng. Trong phn tch mi trng, i hi phi phn tch nhiu cht c hm lng rt
nh, dng vt. S pht hin nng thp c th thc hin thng qua vic lm sch
cc cht v lm giu mu.
Cc mu nc cha cc cht hu c bay hi c th phn tch trc tip bng GC
(khng cn cc bc tch chit mu). i vi mu t v cht thi rn th cn thit
phi c chit rt bng mt dung mi no . iu quan trng l cn phi bit c
cht cn xc nh v mt s tnh cht l ha hc ca n, nh cu trc cc nhm chc,
thnh phn nguyn t, tnh phn cc, trng lng phn t, im si, bn nhit. iu
ny s gip ch nhiu cho qu trnh phn tch. Sau khi bit c cc tnh cht ny s
rt d dng tin hnh phn tch sc k kh ca mt hn hp nhiu thnh phn bng cch
la chn cc ct v cc my o thch hp.
- La chn ct phn tch
Hiu qu ca mt ct sc k trong vic phn tch cc hp phn hu c ph thuc
vo c im cu to ca n v tnh phn cc ca cc phn t cht xc nh. V vy
tnh phn cc ca ct sc k l tnh cht quan trng khi la chn cc ct khc nhau.
Cc ct khng phn cc s c hiu qu nht khi phn tch cc phn t khng phn
cc, cc ct phn cc c s dng phn tch cc hp phn c tnh phn cc. Cc
hydrocacbon bo c cha lin kt n C-H thuc nhm khng phn cc trong khi
chng cha cc lin kt i C = C nh olephin v cht thm l nhng cht c cc.
Ngc li cc cht hu c c cha oxi, nit, lu hunh, phtpho hoc nguyn t
halogen s c tnh phn cc ln hn. V d nh axit cacboxylic, xeton, aldehyt, ester,
ru, ete, amin, cht thm cha nit, nitroamin, nitril, halocacbon, PCBs v photphat
hu c. V vy ct t phn cc s c la chn ko di s bn vng ca ct.
Bng 5.2. Tnh phn cc ca pha tnh GC thng dng
Tnh phn cc
PHA TNH
V d
Khng phn cc



Phn cc yu
Polyimetylsiloxan

Polyphenylmetylsiloxan

Polyphenylmetylsiloxan
AT-1; BP-1; DC-200;
SPB-1; ULTRA-1
AT-5; BP-5; DB-5;
RSL-200; ULTRA-2
AT-20; BP-10; DB-17;
61





Phn cc






Phn cc mnh
(axit)

Polyxianopropylphenyl
i-metylpolysiloxan
Polyxianopropylphenyl-
metylsiloxan
Polytrifloropropylsiloxa
n

Polyphenylxianopropyl-
metylsiloxan
Polyetylenglycol


Estepolyetylenglycol
RSL-300; SPB-20
AT-1301; DB-1301;
Rtx-1301
AT-1701; GB-1701;
RTX-1701; SPB-1701
AT-210; DB-210; RSL-
400; SP-2401
AT-225; HP-225; OV-
225; RSL-500
AT-WAX,BP-20;
CP/WAX-51; HP-20M;
Superox-II
AT-1000; OV-351, SP-
1000; Superox FA

Cc ct mao qun c lm bng SiO
2
(Silica) c tnh tr v hiu qu tt trong
phn tch sc k. i khi cng c th s dng ct mao qun bng thy tinh hoc thp
khng r.
ng knh trong ca ct l mt yu t quan trng pht hin v tch cc hp
phn khc nhau. Nhng ct hnh ng hp c ng knh trong (ID) l 0,20 - 0,25 v
0,32 mm s c kh nng phn tch tt nht cc hp phn tng t v cc cht ng
phn. Cc ID cng nh th kh nng phn tch cng ln. Tuy nhin, nu ID cng nh
th dung tch mu ly cng cng nh. Cc ID ln hn nh kch thc 0,53 v 0,75 mm
c kh nng phn tch thp. Tuy nhin cc ID ln li c xem l thch hp hn cho
php phn tch cc mu mi trng v mu thng cha cc cht nhim nng
kh cao. Hn na cc ct c ID ln (0,53 - 0,75 mm) cng c nhy phn tch
cc cht c hm lng nh.
Dung tch mu ca ct c th tng ln bng cch tng ch nhit. iu ny ph
thuc vo tnh phn cc ca cc cht phn tch v ca ct sc k - cc ct phn cc s
c kh nng cao vi cc cht phn cc, trong khi cc ct khng phn cc li c kh
nng cao vi cc cht khng phn cc.
Cc ct sc k c th c ph mt lp cht khng hot ng l hc hoc ha hc.
Khi c ph cht khng hot ng v l hc, ct c gi l ct khng lin kt. Cn
khi c lm cho mt hot tnh ha hc c gi l ct c lin kt. Loi ct lin kt
ha hc ny thng c dng nhiu hn v c th s dng nhit cao m t b ph
hy, v c th ngm trong cc dung mi loi b cc cht khng bay hi bm vo
thnh ct.
dy ca mng ca ct sc k cng l c im cn ch khi la chn ct.
Mng dy s tng kh nng phn tch ca cc ct khng phn cc v kh nng duy tr
cc cht phn tch.V vy, n va c u im ng thi cng c nhc im khi phn
tch mu. Thng s dng cc mng dy (> 1m) phn tch kh hoc phn tch cc
mu c nng cao. Mt khc, cc mng mng (< 0,25m) thng c dng
phn tch cc cht c im si cao (> 300
0
C) v dng cho cc ct ngn hn 10 - 15 m.
62
Quan h gia dy ca mng v ID ca ct sc k c th c biu din thng qua
phng trnh sau:

=

Cc ct sc k c gi tr tng t nhau s c kh nng phn tch ging nhau
trong cng mt iu kin phn tch. V d nh 1 ct sc k c ID l 0,32 m v dy
l 0,8 m s c th thay tng ng cho ct c ID l 0,53 m v c dy mng l
1,3 m. dy mng tiu chun (0,25 - 0,8 m) s c kh nng phn tch vi hu ht
cc cht ha hc.
Hiu qu phn tch cc cht gn ging nhau s c tng ln cc ct c chiu
di ln hn. Tuy nhin, ct c chiu di ln hn s i hi thi gian phn tch lu
hn v tng kh nng gi mu. Nh phn tch trn, kh nng phn tch s l tt
hn khi cc ct c ID nh hn. V vy chiu di ct v kch thc ID thch hp nht
s cho kh nng phn tch tt nht cc cht trong mu phn tch trong khong thi
gian mong mun.
- etect: s la chn cc etect l yu t quan trng nht trong phn tch.
etect ion ha ngn la FID (Flame Ionization etect) c s dng cho tt c cc
mc ch phn tch. Gii hn ca php phn tch tng i cao, c bit l TCD v
thng c dng cho phn tch kh.
Khi s dng FID, cc mu nc c th c xc nh trc tip m khng cn phi
tch chit. Khi p dng cc bc tch chit thch hp, cc hp cht hu c trong nc,
cht rn v trong khng kh u c th c xc nh ngay khi chng c hm lng
thp. Cacbon disunfit c dng ph bin trong phn tch nhiu cht hu c trong
khng kh bng GC-FID.
etect ring cho cc cht halogen (Halogen specific etect), chng hn nh
etect bt in t (Electron capture etect, ECD), etect dn in phn...(Hail
electrolytic conductivity etect, HECD) cho kt qu tt i vi cc hp phn cha
nguyn t halogen. Hu ht cc cht hu c cha nit u c th c xc nh bng
etect photpho - nit (Nitrogen Photphorus etect, NPD) trong chc nng o nit
(nitrogen mode), cc hp cht photpho hu c s s dng chc nng o photpho
(Photphorus mode). etect quang k ngn la (Flame photometric etect, FPD)
cng c hiu qu tng t xc nh cc hp phn cha photpho. Tuy nhin FPD
c s dng ph bin o cc cht hu c cha lu hunh. etect quang ion ha
(Photoionization etect, PID) l nhy vi cc cht cha lin kt ni i C = C nh
cc vng thm v olephin, cng nh cc sn phm thay th ca chng.
- ng chun (calibration curve):
Trc khi phn tch mu, cn thit phi xy dng mt ng chun vi t nht l 4
cht chun. C hai cch xy dng ng chun: phng php ng chun ngoi
(External standard method) v phng php ng chun trong (Internal standard
method).
Bn knh ct (m)
2 x dy ca mng (m)
63
Phng php ng chun ngoi l xy dng mt ng chun da trn din tch
hoc chiu cao th tng ng vi cc nng phn tch bit. Cc yu t ng
chun c tnh ton da trn t s gia nng vi din tch hoc chiu cao v c
gi c nh (constant) trn mt phm vi ca nng . xc nh nng ca cht
phn tch, gi tr o c ca mu s c so snh vi cc gi tr ca th chun
trong phm vi xy dng. Hoc gi tr trung bnh ca t l c tnh ton s c so
snh vi gi tr o mu. Mt ng chun n im c th c s dng nu din tch
hoc chiu cao o c ca cht phn tch nm trong phm vi 20% so vi cht
chun.
Phng php ng chun trong c s dng thch hp hn phng php ng
chun ngoi. Nhng lng bng nhau ca mt hoc nhiu cht chun trong (Internal
standard) c cho vo nhng th tch nh nhau ca cht chit rt. Cc kt qu o
c (response factor - RF) s c tnh ton nh sau:
RF = As . Cs/Ais . Cis
Trong : As v Ais: l din tch (hoc chiu cao) o c mu v cht chun
trong (Internal standard).
Cs v Cis l cc nng tng ng ca chng.
Do vy, RF ca cc cht phn tch c th c xc nh thng qua cc cht chun
cha cht chun trong. Nu gi tr RF vt qua phm vi c xc nh ca cht
chun trong vng 20%, khi s dng mt gi tr trung bnh RF trong phng
trnh trn xc nh hm lng ca cht phn tch trong mu. Mt cch khc, mt
ng chun c xc nh gia cc gi tr t s As/Ais vi RF.
Nng cht phn tch trong mu s bng:
As.Cis.D/Ais.RF
Trong : D l h s pha long
i vi cht lng, nng ca cht phn tch thng biu din di dng g/l.
- Tnh ton:
ng chun ngoi (External standard calibration):
Din tch hoc chiu cao o c so snh vi ng chun hoc t cc yu t
ng chun:
Nng (g/l) = Aunk . Qstd . Vtot. D/ astd . Vijn. Vsample
Trong :
Aunk : Din tch hoc chiu cao o c ca cht phn tch
Qstd : Lng tiu chun c xc nh (ng)
Vtot : Th tch tng dung dch chit rt (l)
D : H s pha long
Astd : Din tch hoc chiu cao o c ca cht chun
Vijn : Th tch cht cht rt c em o (l)
Vsample : Th tch mu c chit rt (ml)
64
i vi cc mu cht rn, hm lng ca cht phn tch cng c tnh tng t,
tr gi tr khi lng mu W s thay th cho th tch mu V.
Do vy:
Hm lng (mg/kg) = Aunk . Qstd . Vtot. D/ astd . Vijn. W
Hm lng c tnh nh trn dng cho mu trng thi phn tch (khng phi
dng mu kh kit). Hm lng c chuyn sang cht kh bng cch nhn kt qu
ny vi % cht kh.
V d: Ly 50 ml mu nc chit bng 2 ml hexan. Mt th tch cht chit rt v
cht chun c em xc nh l 4 ml, vi nng l 50 g/l. Din tch o c ca
cht phn tch trong cht chit rt mu v dung dch cht chun tng ng l 28,500
v 24,800. Xc nh nng ca cht phn tch trong mu.
A = 28,500
A = 24,800
Q = 4ml x 50 g/1l x 1 l/ 1000000 l x 1000 mg/1 g = 0,2 ng
V = 2 ml x 1000 lml = 2000 l
V = 4 l
V = 500 ml
D = 1, cht chit rt khng c pha long.
Nng ca cht phn tch trong mu l:



Mt cch tnh khc: Khi mt cht chit rt t mu v cht chun c a vo xc
nh trong ct sc k l bng nhau (4l), nng ca cht phn tch trong mu c th
c tnh theo mt cch n gin nh sau:
Nng ca cht phn tch (g/l) = Nng o c (trong cht chit rt) c
xc nh t ng chun:
mg/l x ml chit rt/ ml mu x D
Trong v d trn, nng ca cht phn tch trong cht chit rt l:
28,500/24,800 x 50g/l = 57,5 g/l
Nh vy, nng cht phn tch trong mu l:
57,5 g/l x 2 ml/500 ml x 1 = 0,23 g/l
Phng php tiu chun trong (Internal standard method).
Nng cht phn tch c xc nh t RF bng cch s dng cng thc sau:



28,500 x 0,2ng x 2000 ml x
1
24,800 x 4 ml x 500 ml
= 0,23 ng/ ml = 0,23
mg/l
C =
A x C
A x RF
65
5.7. Phn tch d lng ha cht bo v thc vt
5.7.1. Nhm Cacbamat, Ure v Triazin
MT S LNG LN CC LOI THUC BO V THC VT
(PESTICIDES) THUC NHM CACBAMAT C CHA CHC URE HAY VNG
TRIAZIN. CC CHT NY BAO GM 3 LOI PH BIN DA THEO CU
TRC L:
R
1
R
2
N - C - O - (nhm thay th)
O

O
N - C - N (nhm thay th)
R
2
R
1

N
N N

Trong , R
1
v R
2
l cc nhm alkyl hoc cc nhm aryl, hoc nguyn t hidro.
Cc cht cha nhm metyl c gn N cn c gi l cacbamat metyl nit. Khi mt
hoc c hai nguyn t oxy c thay th bng S th c gi l thiocacbamat. Triazin
l vng cha 3 nguyn t N, cc loi hp cht thuc nhm ny c th c phn tch
bng cc k thut GC, GC/MS hoc HPLC.
- Thuc bo v thc vt cacbamat:
+ i vi cc hp cht ny tt nht l s dng k thut phn tch HPLC. Cc hp
phn ca chng c phn tch trn ct phn tch C18, sau c thy phn bng
NaOH 0,05N. Lc ny cacbamat c chuyn thnh cc metylamin, cc cht ny s
phn ng vi -phthaladehyt v 2-mecaptoetanol hnh thnh dng dn sut hunh
quang (fluorecent derivatives). Cc cht dn xut ny c xc nh bng my o
hunh quang. Dung dch phn ng -phthaladehyt trong metanol n 10 ml gm
axetonnitrit c cha 100 l 2-mecaptoetanol, sau pha long n 1000 ml bng dung
dch natriborat 0,05N.
+ Chit rt mu: Cc mu nc sch c th s dng o trc tip. Thng thng
cn 200 - 400 l. Cc mu nc thi c th c chit bng metylen clorua. Cc cht
rn nh t, trm tch, cht thi rn, bn, du... c chit bng axetonnitrit. Cc cht
rn v bn c sy kh 105
0
C, sau s dng axetonnitrit chit. Hn hp c
lc t nht mt gi bng my lc phng. Du v cht thi cha du thng c chit
bng hn hp hexan v axetonnitrit trong vi gi.
Vi cc mu nhim nng v bn c th lm sch bng cch x l dch chit vi
20 ml etylen glycol v cho bay hi dung dch trong nc nhit 50 - 60
0
C. Phn
etylen glycol cn li c kt hp vi khong vi ml metanol. Hn hp ny c a
qua ct C18 v phn tch bng HPLC.

Cacbamat

Ure

Triazin
66
- Thuc bo v thc vt Ure (Urea pesticides):
Tng t nh cacbamat cc cht thuc nhm ny c th xc nh nh HPLC. Cc
mu cht lng c chit rt bng metylen clorua, dch chit rt c lm giu bng
cch lm bay hi bt metylen clorua v thay dung mi bng metanol. Cc cht rn
c chit bng amoniacetat (0,8g/l), v s dng cht hp ph c sn trong ct
C18. Sau s dng metanol ha tan cc ha cht bo v thc vt, ri lm giu
bng cch cho bay hi. Mu c tch chit trong vng 7 ngy, v c gi di
0
0
C, phn tch trong vng 3 tun. Dch chit sau c a vo xc nh trn my
HPLC.
- Triazin:
y l thuc tr c c th xc nh bng nhiu phng php khc nhau nh
HPLC, GC v GC/MS.
5.7.2. Thuc bo v thc vt nhm c clo (organochlorine pesticides)
Thuc tr su c clo bao gm cc loi cht hu c c gn clo c s dng lm
thuc tr su. Chng c th c xc nh bng cc phng php nh GC-BCD hay
GC/MS.
Chit rt mu:
Mu cht lng c chit bng hexan hoc metylen clorua. Cht lng cng c th
c chit bng cch s dng ct C18.
Nu cht chit rt c xc nh bng GC/MS, dung mi c th l metylen clorit
hoc hexan. Nu xc nh bng GC-ECD th s dng dung mi khng cha clo nh
hexan hay isooctan. t, trm tch v cht thi rn c chit rt bng phng php
soxhlet vi cc dung mi nh trn. Mu nn c trn vi Na
2
SO
4
khan trc khi
chit. Dung dch chit cn c lm sch loi b cc tp cht gy cn tr trong khi
xc nh.
i vi mu khng kh, cc cht ny c th c xc nh bng phng php
NiOSH v US-EPA. Khng kh c cho qua mt ct hp ph c cha bt polyuretan
hoc cromosorb 102. Thuc bo v thc vt (BVTV) c chit ra bng dung mi hu
c nh toluen, hexan hoc dietyl ete, sau xc nh bng GC - ECD. Dch chit c
th cn thit phi lm sch bng florisil loi tr cht lm nhiu.
5.7.3. Thuc bo v thc vt nhm c photpho (organophosphorus
pesticides)
CC CHT C PHOTPHO C CU TO CHUNG NH SAU:
RO
RO
P-O (hoc S) - (nhm thay th)
O (hoc S)

TRONG R L NHM ANKYL HOC ARYL. NHM THAY TH C
TH L BT K MT LOI HU C NO M C TH B TCH RA KHI
LIN KT VI OXY HOC SUNPHUA. HAI LOI IN HNH L:
67
C H
3
O
C H
3
O
P - O - C = C H C - O C H
3
O C H
3 O

C
2
H
5
O
C
2
H
5
O
P - O - NO
2
S
(parathion)

- Phn tch mu cht lng v cht rn:
Phng php thng c s dng phn tch cc thuc tr su c photpho l
GC v GC/MS hoc HPLC. Tuy nhin, cha c cc nghin cu h thng v chnh
xc v mc tin cy ca phng php HPLC. etect c s dng trong phng
php GC l nit - photpho etect (NPD-nitrogen phosphorus etect), hoc etect
quang k ngn la (FPD - Flame Photometric etect). Do vy, bt k loi ha cht
bo v thc vt no c xc nh bng GC-NPD hoc GC-FPD u phi s dng cc
ct mao qun thch hp. Cc etect halogen, nh o dn in hoc etect vi in
lng c th s dng trong phn tch GC ch cho cc cht bo v thc vt cha nguyn
t halogen.
Cc mu cht lng c chit bng metylen clorua. Mu cht rn c chit bng
metylen clorit - axeton (1:1) bng soxhlet hoc sng m (sonication). Cht chit
metylen clorit cui cng phi c chuyn snh hexan hoc iso octan hoc metyl -
tert - butyl ete. Dung mi sau nn c hn hp vi axeton trong khi chuyn i dung
mi. Cht chit rt c th c lm sch bng florisil. Sau em xc nh trn my
GC hoc GC/MS.
- Phn tch mu khng kh:
Cc loi thuc bo v thc vt trong khng kh c gi li bi cc b phn lc
khc nhau, nh cromosorb 102, este xenlulo, XAD-2, mng PTPE (1m), hoc mng
lc si thy tinh. Sau dng dung mi tch, thng l toluen hoc cc dung mi
hu c thch hp. Cht chit rt c xc nh bng GC (s dng NPD hoc FPD)
hoc GC/MS.
5.8. Sc k ion (IC)
Sc k ion ra i nm 1975 v c pht trin rt nhanh. y l mt phng php
phn tch cng c n gin c s dng rng ri xc nh lin tip nhiu anion
ph bin trong mi trng. Cc anion nh NO
3
-
, NO
2
-
, PO
4
3-
, SO
4
2-
, SO
3
2-
, F
-
, Cl
-
, Br
-
,
I
-
, halogenoxi, nhiu ion ca axit hu c...c xc nh nhanh chng qua mt bc
phn tch n gin, lin tip. Cc u im chnh ca phng php l:
- C th xc nh c mt vi anion trong cng mt php phn tch.
- Phn bit c cc halogen (Br
-
, Cl
-
...) v cc anion trng thi oxi ha khc
nhau (NO
3
-
, NO
2
-
, SO
4
2-
, SO
3
2-
...); cc anion ny thng nh hng ln nhau trong
phng php phn tch nc.
- n gin v nhanh chng.
(mevinphos)
68
Phng php ny bao gm vic tch sc k cc cht phn tch tan trong nc v
pht hin cc ion tch bng mt etect o dn in. Phng php ny cng c
th s dng phn tch cc halogenoxi nh peclorat (ClO
4
-
) hoc hypoclorit (ClO
-
)
cc axit hu c yu, ion kim loi v cc aminankyl. Cc cht phn tch c th xc nh
bng phng php sc k ion c trnh by bng sau:
Bng 5.3. p dng cc phng php sc k ion trong phn tch mi trng
Cht phn tch Cng thc / V d
Cc anion v c ph bin F
-
, Cl
-
, Br
-
, I
-
, NO
3
-
, NO
2
-
, PO
4
3-
, SO
4
2-
, SO
3
2-
,
CO
3
2-
, PO
3
3-
, HPO
4
2-
, CNO
-

Halogenoxi ClO
4
-
, ClO
3
-
, ClO
2
-
, ClO
-
, BrO
4
-
, BrO
3
-
, IO
4
-
, IO
3
-

Pyrophotphat, polyphotphat v
metaphotphat
P
2
O
7
4-
, P
3
O
10
5-
, P
4
O
13
6-
, P
2
O
6
2-

Thiosunfat v thioxianat S
2
O
3
2-
, SCN
-
,
Cc anion v c khc nhau CrO
4
2-
, BO
3
3-
, AsO
4
3-
, SeO
4
2-
, SeO
3
2-
, MnO
4
2-
,
WO
4
2

Ion kim loi (kim loi kim v
kim th)
Li
+
, Na
+
, K
+
, Mg
2+
, Ca
2+

Ion kim loi chuyn tip ph bin
(a)
Fe
2+
, Zn
2+
, Cu
2+
, Mn
2+
, Ni
2+

Ion amoni NH
4
+
Crm ha tr 6 Cr
6+ (b)

Xyanua CN
- (c)

Cc anion hu c ca dng axit
cacboxylic
Axetat, fomat, oxalat, maleat, phtalat, tatrat
Cc axit hu c sunfonat Benzen sunfonat, p-toluen sunfonat
Axit clophenoxi v thuc dit c 2:4-D, silvex, 2,4,5-T
Cc amin Etylamin, trimetylamin, isobutylamin, mopholin,
xyclohexylamin
Ch thch:
a: Sau khi ra khi ct, tin hnh phn ng, xc nh bng tia UV bc sng
530 nm. Dung mi ra gii l: pyridin-2,6-axit icacboxylic.
b: Sau khi qua ct thc hin phn ng so mu v xc nh trc quang, cng c
th xc nh bng sc k ion vi ct c ch ha hc, s dng etect o dn in.
c: Phn hy axit sau khi tin hnh sc k ion vi ct c ch ha hc
Mu dng dung dch c bm vo dng dung mi ra gii cacbonat/
bicacbonat. Dung mi ra gii c bm qua ct trao i ion (ct cha cc ht nha
trao i ion). Cc ion trong mu c i lc vi cc ht nha khc nhau, do vy chng
chuyn ng qua ct vi cc tc khc nhau, nh th chng c tch ra. phn
tch cc anion trong mu ngi ta s dng mt baz c kh nng trao i anion yu.
Dung mi ra gii v cc anion tch c a qua mt ct c ch, l mt tc nhn
69
trao i cation c tnh axit mnh nhm lm gim dn in ca dung mi ra gii
tng cng kh nng pht hin cc ion trong mu. Khi cc ion tch s chuyn
sang dng axit c tnh dn in cao hn (v d: NO
3
-
chuyn thnh HNO
3
) v c xc
nh bng detect o dn in. Cc ion c xc nh bng thi gian lu v c
nh lng bng cch so snh chiu cao ca pic/ din tch pic vi cc cht chun. Php
o dn in c nhy cao v l cch xc nh c trng cho c cc ion hu c v
v c.
nhy v kh nng xc nh ca cc ion phn tch s tng ng k nh k thut
c ch ha hc v t c ch (Dionex, 1995). Trong c ch ha hc ngi ta dng phn
ng ha hc lm gim nng ca cc phn t dn in trong pha ng. Khi
nim ny c th c hiu r hn qua mt v d sau: Gi s c mt hn hp anion cn
phn tch, hn hp c tch trn mt ct phn tch cha nha trao i ion dng
HCO
3
-
. Phn ng trao i l:
R-HCO
3
+ X
-
+ Na
+
R - X + HCO
3
-
+ Na
+

V nha l cht trao i anion nn Na
+
khng tham gia vo qu trnh nhng c
vit vo phng trnh trung ha in tch. Dung dch NaHCO
3
thu c s ra khi
ct v i vo ct c ch - l b trao i cation dng H
+
. Phn ng trao i sau s xy
ra:
R - H + Na
+
+ HCO
3
-
R - Na + H
2
CO
3

Khi dung dch c ra gii tch ra t ct c ch s c cha axit cacbonic khng
ion ha (CO
2
tan trong H
2
O) nn c tnh dn in nh. Tn hiu gn nh bng khng.
Nhng khi X
-
c ra gii t ct tch ra th nc gii hp c cha NaX v sau khi i
qua ct c ch s cha HX (v d HCl nu l anion Cl
-
). dn s rt ln v HX l
mt axit kh mnh (mnh hn axit cacbonic).
Dung mi ra gii ngoi cacbonat v bicacbonat cn c nhiu dung dch khc
c s dng trong phn tch mi trng. Mt s dung mi ra gii ph bin c nu
bng sau (bng 5.4).
Bng 5.4. Mt s dung mi ra gii thng thng trong sc k ion
a
Dung mi ra gii S dng thng thng
Natricacbonat/ natribicacbonat Cc anion v c thng thng: F
-
, Cl
-
, NO
3
-
v
SO
4
2-

Natrihyroxyt Cc anion v c thng thng: F
-
, Cl
-
, NO
3
-
v
SO
4
2
; cc anion hu c: axetat, xitrat v fumarat
Natritetraborat/axit boric Cc anion v c thng thng: F
-
, NO
3
-
, SO
4
2-
;
haloxi v cacboxylat chng hn nh axetat v fomat
Axit metansunfonic Cc ion kim loi kim v kim th v c tnh kim:
Na
+
, K
+
, Ca
2+
, NH
4
+

Axit metansunfonic/
axetonnitrin
Cc ion kim loi kim v kim th v c tnh kim:
Li
+
, Na
+
, K
+
, Mg
2+
, NH
4
+
; cc ankylamin:
metylamin, trietylamin v mopholin
Ch thch:
70

a
etect: dn c ch
Dung dch NaOH c s dng rt rng ri trong nhiu php phn tch.
Ion Na
+
c tch khi dung mi ra gii ct cht c ch, v ion H
+
(trong
dung dch in phn) kt hp vi ion OH
-
trong dung mi ra gii to ra H
2
O c
dn in km hn dung mi ra gii NaOH. Nh vy, cc nh hng thc t l, (1)
dn in ca dung mi ra gii nn NaOH gim, v (2) dn in ca cc anion phn
tch tng bi v chng dng axit.
C hai nh hng ny u lm tng ng k t l tn hiu nhiu, nh vy lm gim
ngng xc nh v nhy.
Sc k ion l mt phng php phn tch thun tin nht xc nh hu ht cc
anion v c, bao gm c cc halogenoxi trong nc sinh hot, nc thi v nc r r
t cht thi rn. Phng php ny c hi bo v mi trng M thng qua v tr
thnh mt phng php chun (US EPA, 1990 v AWWA, 1993). Mt s ct trao i
ion c sn xut bn nh Ion Pac (Dionex, 1995) hay tng ng, c th tch
isocratic cc anion v c thng thng trong vng cha n 10 pht khi s dng dung
mi ra gii cacbonat/bicacbonat v nhy mc nh hn ppm, s dng etect
dn in c ch. Ngoi ra, khi s dng iu kin graien dung dch v thay i cng
ion ln gp hn hai ln th nhiu ion bc 1, 2 v 3 c th c tch ra trong mt ln
chy sc k. Sc k ion graien kt hp vi c ch ha hc c th trnh c s kt
hp dung mi ra gii v cho php tch mt s ln cc ion v c v hu c. Nhiu axit
hu c sunfonat thng c trong nc tch t khu chn lp cht thi nguy hi c
xc nh bng sc k ion nh thay i c dung mi v cng ion trong h dung mi
ra gii graien.
i vi mt ct trao i anion, cc ht bao ph l cc nhm cha aminankanol bc
4 hoc aminankyl bc 4. Kch thc ht ca hp cht bao ph; cu trc loi mng
mng v lin kt ngang trong xp s xc nh phn gii ca anion trong ct
(Dionex, 1995). Cc ct ny c nhiu hng cung cp bn trn th trng. Mt ct
bo v c s dng bo v ct tch khi cc cht hu c v cc ht.













71





























Bnh cha dung
mi ra gii
Bm
Phun mu
Ct tch
Ct c ch (kh)
Pin dn
B ghi
My tnh
Giai on np mu
Giai on tch
Giai on pht hin
Giai on ghi s
liu
Hnh 5.6. S sc k ion c ct c ch v pht hin bng dn
72
Chng 6. Phng php khi ph
Khi cho mt cht trng thi kh va trm vi mt dng electron hay photon th
phn t cht c th bt ra 1 hay 2 electron tr thnh cc ion dng mang in
tch 1 hay 2 hoc phn t ca cht c th nhn electron tr thnh ion m.
M + e M
+
+ 2e
M + e M
2+
+ 3e
M + e M
-
Hin tng ny gi l hin tng ion ha phn t. Ngoi ra khi va chm mnh hn
th phn t cn c th b ph v thnh nhiu phn khc nhau mang in tch dng
hoc m, qu trnh ny gi l s phn ha (fragmentation).
Phng php khi ph da trn nguyn tc chung l tch v o khi lng ca tt
c cc ion ny v ghi chng trn mt bn ph. Sau da vo cc quy lut chung
phn tch thnh phn cc cht theo bn khi ph ghi c.
V k thut, qu trnh phn tch khi ph phi thc hin qua cc bc sau:
Ha hi tt c cc mu cht phn tch
Ion ha phn t
Tch bit cc ion theo khi lng
Ghi nhn cc ion
6.1. S hnh thnh ca khi ph
6.1.1. S ion ha
a. Phng php ion ha bng va chm electron:
y l phng php ion ha ph bin nht. Trong bung ion ha, cc electron pht
ra t catot lm bng vonfram hoc reni khi t nng, s chuyn v anot vi vn tc
ln. Cc phn t cht nghin cu trng thi hi s va chm vi cc electron v nhn
nng lng t electron v chng s b ion ha.
b. Ion ha bng in trng mnh:
Ti bung ion ha, ngi ta t cc b pht trng l cc mi nhn di dng
cc dy dn mnh hay cc li nhn t mt in p vo trong. Di tc dng ca
in trng mnh, cc electron s bt ra khi phn t cht nghin cu. Trong phng
php ny cc ion phn t c to thnh vn gi nguyn trng thi c bn. Ngoi hai
phng php ny, cn c mt phng php khc nh ion ha ha hc (ion ha nh s
tng tc gia cc ion), ion ha nh s phng in, ion ha nh s t nng (ngun
nhit, tia lazer)... Tuy nhin, cc phng php ny t c s dng hn.
6.1.2. My khi ph
Cc ion c to thnh s c phn ct thnh cc thnh phn c khi lng khc
nhau trong cc my khi ph. Mt my khi ph thng c 4 khi chc nng chnh.
l:
73
H thng np mu, ngun ion ha, b phn tch, b ghi tn hiu. Trong quan
trng nht l b phn tch phn ct cc ion c khi lng khc nhau thnh tng
mnh ion. B phn tch ny c mt s loi sau: b phn tch t, b phn tch t cc, b
phn tch theo thi gian v b phn tch cng hng ion-xyclotion. Trong , my c
b phn tch t l loi my truyn thng.
Theo tnh nng b ghi, my khi ph thng thng c hai loi: my khi ph k
vi tn hiu khi ph c ghi bng knh nh dng vch m khc nhau; v my
khi ph k vi tn hiu c ghi di dng xung in hoc a vo b nh ca my
tnh, tn hiu s c a ra di dng bng s hoc dng th thch hp.
6.1.3. Qu trnh hnh thnh khi ph
- Qu trnh trong bung ion ha: Khi cc electron t catot bn ra cch phn t
nghin cu khong cch nh hn 0,5 A
0
, cc electron s truyn nng lng cho phn
t. Cc phn t sau khi nhn nng lng s b kch thch, cc electron trong phn t s
chuyn sang mc nng lng cao hn v c th mt i mt hoc mt s electron to
nn ion phn t. Khi nng lng ca cc electron gy ion ha ln (50 - 80 eV),
trong qu trnh ion ha, phn t s nhn nng lng (cao hn th ion ha) b sung dn
n cc ion phn t b kch thch. Mt phn nng lng kch thch s chuyn thnh
nng lng dao ng, mt phn tiu tn cho qu trnh kch thch electron. Cc electron
b kch thch c th chuyn ln mc nng lng phn lin kt v phn t b phn ct
lin kt . Qu trnh ny xy ra trong khong thi gian rt ngn 10
-12
- 10
-13
s. Tuy
nhin, nu vic chuyn electron ln mc nng lng kch thch nhng cha iu
kin b gy lin kt v s phn r nhanh khng th thc hin c th thi gian
sng ca ion phn t s tng ng k v tin ti bng chu k dao ng ca phn t. Khi
, nng lng kch thch s bin thnh nng lng dao ng, s kch thch s lan
truyn trong ton mch phn t v nu ti mt lin kt no ca mch b yu i th
nng lng kch thch phn ct lin kt v phn t b b gy ti lin kt ny. Xc
sut b gy mt lin kt ph thuc vo bn ca lin kt, gi tr nng lng kch
thch, v ph thuc vo n nh ca cc ion to thnh.
- Trong ion phn t: Electron c th b bt ra t mt lin kt bt k. Trong ion, s
nhanh chng xy ra s phn b li mt in tch trong ton mch v in tch s
ti v tr c electron t do hoc electron p hay d, thng l cc nhm chc cha ni
i hoc cc ni i lin hp (V d C = O; C N; C = S; nhn thm...). ln ca
pic ion phn t ph thuc vo bn ca n ngha l kh nng khng b phn ct trong
thi gian chuyn t bung ion ha n b thu nhn .
Khi gim nng lng electron gy ra ion ha s lm gim nng lng ion phn t
nh vy s gim xc sut phn ct tip tc dn n lm gim cng cc mnh, lm
tng cng tn hiu ca ion phn t.
Khi gim nng lng ca electron gy ra ion ha n 10 -15 eV th cng
tng i ca pic ca ion phn t tng nhanh - phng php cho php nhn bit tn
hiu ca cc ion phn t trong nhiu tn hiu ca khi ph . Phng php ny s
dng c hiu qu khi phn tch nh lng hn hp hidrocarbon phc tp v xc nh
cu to phn t ca cc cht.
74
- i vi cc nguyn t c nhiu ng v, ngoi tn hiu ca ion M
+
, cn c th c
tn hiu ca cc ion phn t c khi lng (M-1)
+
hoc (M+1)
+
; (M+2)
+
... gy nn
nhiu tn hiu ln cn cnh tn hiu ca M
+
, t l cc tn hiu so vi tn hiu ca M
+

t l vi thnh phn cc ng v ca nguyn t trong t nhin. V d, t l ca
15
N
v
14
N trong t nhin l 0,37%, th vi cc hp cht cha Nit, tn hiu ca ion (M+1)
+

c cng bng 37% cng ca M
+
.
Khi lng v thng gp trung bnh ca cc ng v ca mt s nguyn t
trong hp cht hu c.
ng v Khi lng thng gp tng i
1
H
2
H
1,0078
2,0141
100
0,015
12
C
13
C
12,0000
13,0034
100
1,12
14
N
15
N
14,0031
15,0001
100
0,366
16
O
17
O
18
O
15,9949
16,9991
17,9992
100
0,037
0,024
32
S
33
S
34
S
35
S
31,9721
32,9715
33,9679
100
0,789
4,433
0,018

Chng hn nh nguyn t cacbon trong thin nhin tn ti
12
C 100%,
13
C 1,1%.
Nh vy, nu mt hp cht ch cha 1 nguyn t cacbon nh CH
4
th ion M
+
c chiu
cao l 100% (
12
CH
4
) th ion M
+
+ 1 s c t l 1,1% (
13
CH
4
). phn t etan c chc 2
nguyn t cacbon, nn ion M
+
c chiu cao l 100% (
12
C
2
H
6
) th ion M
+
+ 1 s c
chiu cao 2 x 1,1% = 2,2% (
13
CH
3
12
CH
3
). Nh vy nu phn t c n nguyn t C th
chiu cao ca ion M
+
+ 1 s c t l n x 1,1% so vi chiu cao ca ion M
+
.
- Mnh ion hnh thnh do s b gy ca mt lin kt no ca ion phn t khi
ion phn t nhn nng lng b sung. Khi nng lng ca cc electron gy ion ha
trong khong 8 - 12 eV th vi cc cht hu c, v nguyn tc khng c mnh ion.
khong t 15 - 20 eV ch b gy c mt s lin kt yu nn khong ny cng ch
c mt s t vch. Khi nng lng t 30 - 50 eV n nh hn 100 eV th c th b gy
bt k mt lin kt no. Xc sut b gy mt lin kt no ph thuc vo bn ca
lin kt cng nh n nh ca cc ion dng c hnh thnh. C th biu din
qu trnh ion ha bng s :

+
+
+
+ +
+ +
M e M
e M ne M
e M e M
n
2
2

] 3 [
] 2 [
] 1 [

iu kin nng lng thp (8 - 15 eV) qu trnh ion ha thng xy ra theo phn
ng [1]. y l qu trnh quan trng nht trong phn tch khi ph.
75
Khi cht phn tch tip xc vi electron c nng lng khong 70 eV hoc ln hn
6000 kJ.mol
-1
, phn t s b ion ha v sau c th chuyn thnh cc mnh ion:
e 2 M e M + +
+

M
+
= F
t
+
+ N
t

M
+
l ion phn t; F
t
+
l mnh ion; cng c th l gc ion; N
t
l phn t hoc gc
trung ha. V d, i vi propanon.
CH
3
.CO.CH
3
+ e = [CH
3
.CO.CH
3
]
+
(m/z =58)
[CH
3
.CO.CH
3
]
+
= [CH
3
.CO]
+
+ CH
3
(m/z =43)
C nhiu kh nng b gy cc phn t phc tp to thnh cc mnh ion. V d hp
cht gm nhiu hp phn khc nhau ABC khi va chm vi cc electron c th xy ra
cc kh nng sau:
ABC + e ABC
+
+ 2e
ABC
+
A
+
+ BC

hoc
ABC
+
AB
+
+ C

A
+
+ B
6.2. kh nng phn gii ca my khi ph
- Kh nng lm vic ca mt my khi ph c c trng bng nng sut phn
gii ca my. Nng sut phn gii R ca mt my khi ph l kh nng c th phn
bit c hai pic ng vi khi lng gn nhau nht M v M M trn khi ph .
R =
M
M

Kh nng phn gii 1000 (R = 1000) c ngha l mt ion c khi lng m=1000
th c th tch bit c ion c khi lng nng hn hay nh hn n 1 n v
(M =1). i vi ion c khi lng l 100 th c th tch khi ion khc c khi lng
nng hn hay nh hn n 0,1 n v (M =0,1). i vi ion c khi lng M = 28 th
c th tch khi ion c khi lng nng hn hay nh hn n 0,028 n v. V d nh
ion C
2
H
4
c th tch khi ion CO v hiu s khi lng M = 0,036 n v (M
CO
=
27,994915; M
C2H4
= 28,0313000).
Nh vy nu R cng ln th my cng c kh nng phn bit c cc ht c khi
lng cng gn nhau.
6.3. ng dng sc k kh - khi ph phn tch cc cht nhim hu c
Phn tch khi ph c th dng xc nh cng thc cu to cng nh c th
cng nh c th dung phn tch nh lng khi dng phn tch nh lng, ngi ta
da vo s ph thuc ca cng vch I v nng .
I = K.C
Trong I l cng vch ph v C l nng .
76
Phng php sc k kh khi ph (GC/MS - gas chromatography/ Mass
Spectroscopy) l nhng k thut hin i xc nh trong mt phm vi rng cc cht
hu c cha bit v c p dng rt rng ri trong phn tch mi trng.
Nguyn l ca phng php da trn s phn tch cc ph ca mt hn hp trn
GC, tip theo l s xc nh chng bng khi ph. Cc cht c phn chia nh cc
ct GC thch hp, sau cc hp phn c ra gii t ct s chu tc ng ca
electron hoc cht ion ha ha hc. Cc ion phn t s c xc nh nh cc c
trng ca khi ph. V vy cc cht c mt trong mu s c xc nh nh cc ion s
cp hoc th cp (primary and secondary ions) v nh thi gian lu ca chng.
phn tch cc cht nhim hu c trong mu mi trng, US.EPA phn
chia chng thnh hai loi l cht hu c d bay hi v cht hu c bn bay hi (hnh
6.1). Cc cht hu c d bay hi bao gm cc cht hu c t nhiu bay hi ti p sut
v nhit xung quanh. Tuy nhin, s phn chia ny da trn k thut phn tch hn
l da vo cu trc ha hc ca cht nhim. V d nh dng clo v p-xylen l rt
khc nhau v cu trc v tnh cht ha hc. Tnh cht duy nht ghp chng trong
mt nhm l tnh bay hi. Mc d cc cht nhim bay hi thng c im si
thp, nhng cng c mt s cht c im si cao nh hi nc, etylbenzen, xylen,
diclobenzen...
















a. Cc cht hu c d bay hi (do phng php lm sch v lm giu - purge and
trap method):
C 2 cch chuyn cc cht phn tch d bay hi vo ct sc k kh l k thut
lm sch, lm giu, v gii hp nhit. Trong phng php lm sch v lm giu, ngi
ta thi heli hoc nit vo mt lng mu nc trong vng 11 pht (thng ly 5 ml
cho nc thi v 25 ml cho nc ung). Cc cht phn tch c sc cho bay hi v
D BAY HI
BN BAY HI
NHNG MU I HI PHI
CHIT THEO H LNG - LNG;
HOC LNG - RN.
Cht chit rt axit
CHT LNG CHIT RT
C A VO CT
SC K KH.
Cht chit rt
kim/trung tnh
CHT LNG CHIT
RT C A VO
CT SC K KH.
CC CHT NHIM HU C
Hnh 6.1. S phn loi cc cht nhim hu c da vo k thut chit rt mu
77
c a n b phn thu hi bao gm than hot tnh, tenax v silicagen. Sau , cc
phn lm giu ny s c t nng 180
0
C trong 4 pht. Cc cht phn tch c
gii hp v vn chuyn n ct sc k kh bng kh mang (carrier gas).
i vi mu t v cc cht thi rn, th cn mt lng nht nh mu, sau x l
bng metanol (thng dng l 10 - 100 ml ph thuc vo nng c tnh ca cht
phn tch trong mu v s c mt ca cc cht khc). Ly mt lng nh cht chit rt
metanol cho vo 5 ml nc phn ng trong phng th nghim v a vo 1 ng sc kh
sau c sc bng 1 kh tr. Cht phn tch c thu hi bng cht hp ph, sau
c gii hp bng nhit v vn chuyn n ct sc k kh.
Tnh ton nng cht phn tch trong cht rn c th c minh ha bng th d
sau:
2 g t c chit rt bng 10 ml metanol. Ly 100 l metanol sau khi x l vi
mu t cho vo 5 ml dung dch thuc th chn lc (Reagent grade water) sc kh
v thu hi cc hp phn hu c bay hi. Hm lng ca cht phn tch xc nh c
l 22 mg/l. Tnh hm lng ca n trong t c th theo 1 trong 2 cch sau y:
1. Tnh khi lng:




Ngha l c 0,11 mg cht phn tch trong 5 ml nc trong ng sc kh trn ln vi
cht chit rt metanol, hay c trong 100 l cht chit rt metanol.
Vy lng cht phn tch c trong 2 g t s l:

hay 5500 mg/kg.
2. Phn tch th nguyn:




= 5500 g/ kg t
b. Cc cht hu c bn bay hi:
Cc cht hu c kh bay hi c gp trong mt nhm gi l nhm bn bay hi
(semivolatile). Chng bao gm c nhng cht hu c c kh nng bay hi rt thp nh
iphenylclorinat v cc cht thm a nhn (polinuclear arometics). Vic phn tch cc
10 ml (hoc 10.000 ml) chit rt
0,11mg x
100 ml chit rt
= 11 mg cht trong 10 ml cht chit rt metanol (hay trong 2 g t)
22 mg/l = 22mg x
5 ml nc
1000 ml nc
= 0,11 mg trong 5 ml nc
22 mg cht
1 lt nc
x
1 lt nc
1000 ml nc
x
1000 ml
metanol
1 ml metanol
x
5 ml nc
1000 ml metanol
x
10 ml metanol
2 g t
x
1000 g t
1 kg t
22 x 5 x 1000 x 10 x 1000
1000 x 1000 x 2
= g cht/ kg t
78
cht hu c bn bay hi bng phng php sc k kh khng khc nhiu so vi cc
cht hu c d bay hi. S khc nhau c bn l cc cch chit rt mu phn tch.
iu chnh my:
Trc khi tin hnh phn tch, cn phi kim tra v iu chnh cho my m bo
kh nng thc hin tt cc chc nng. Cc my GC/MS u c km theo cc cht iu
chnh nh peflotributylamin (PFTBA). c trng khi lng ion ca hp cht ny
(hoc mt cht iu chnh no khc) v din tch ph tng ng s cho php kim tra
cc chc nng ca my. m bo chnh xc v sai s cho php ca kt qu
xc nh, US.EPA a ra cc cht iu chnh dng cho phn tch cc cht hu c
trong mi trng bng GC/MS. Bao gm 4-bromoflorobenzen (BFB),
decaflorotriphenyl photphin (DFTPP) tng ng cho cc cht d bay hi v bn bay
hi.
Decaflorotriphenylphotphin oxit (DFTPPPO) l cht kim tra iu khin iu
chnh cho phn tch bng LC/MS i vi mt s thuc tr su cha nit. H thng
GC/MS phi c kim tra bo m tt c cc chc nng ca my phi t chnh
xc theo yu cu. Cc tnh cht c bn m/z i vi cht iu chnh BFB v DFTPP
c trnh by bng 6.1 v 6.2.
Bng 6.1. Yu cu ca cht iu chnh BFB cho phn tch cht hu c d bay hi
Khi lng ion thng gp
50 15 - 40% ca khi lng 95
75 30 - 60% ca khi lng 95
95
Pic c bn, thng gp tng i
100%
96 5 - 9% ca khi lng 95
173 < 2% ca khi lng 174
174 > 50% ca khi lng 95
175 5 - 9% ca khi lng 174
176 95 - 101 ca khi lng 174
177 5 - 9% ca khi lng 176
Bng 6.2. Yu cu ca cht iu chnh DFTPP cho phn tch cht hu c bn bay hi
Khi lng ion thng gp
51
a
30 - 60% ca khi lng 198
68 < 2% ca khi lng 69
70
b
< 2% ca khi lng 69
127
c
40 - 60% ca khi lng 198
197
d
< 1% ca khi lng 198
198 Pic c bn, thng gp
tng i l 100%
199 5 - 9% ca khi lng 198
275
e
10 - 30% ca khi lng 198
79
365
f
> 1% ca khi lng 198
441 C mt nhng nh hn khi
lng 443
442
g
> 40% ca khi lng 198
443
h
17 - 23% ca khi lng 442

a: T 10 - 80% ca khi lng 198 khi s dng phng php 525 (nc ung).
b: Cn phi c p ng yu cu ca CLP
c: T 10 - 80% ca khi lng 198 cho phng php 525 (nc ung) v 25 -
75% ca khi lng 198 p ng yu cu ca CLP.
d: < 2% ca khi lng 198 cho phng php 525 (nc ung).
e: T 10 - 60% ca khi lng ca 198 cho phng php 525 (nc ung).
f: > 0,75% ca khi lng 198 p ng yu cu ca CLP.
g: > 50% ca khi lng ca 198 cho phng php 525 (nc ung) v 40 -
100% ca khi lng 198 p ng yu cu ca CLP.
h: 15 - 24% ca khi lng ca 198 cho phng php 525 (nc ung) v p
ng nhu cu CLP.

80
Chng 7. Cc loi nc v cc phng php phn tch nc
7.1. i cng v cc loi nc
7.1.1. Nc thin nhin
Nc thin nhin bao gm cc loi nc c ngun thin nhin nh sng ngi, h ao, sui, mch
ngm, bin, i dng. C th ni nc thin nhin l mt h d th nhiu thnh phn, v nc thin
nhin lun cha nhng lng no cc cht tan v khng tan c ngun gc v c cng nh hu c.
Cc cht c a vo t kh quyn, t t v cc ngun cha hoc cc mch nc chy qua. Cc
cht cn c to thnh do hot ng sng v s phn hu ca cc c th ng vt, thc vt sng
trong nc hoc y cc ngun nc. Cc hot ng ca con ngi trong cc lnh vc khc nhau ca
sn xut v i sng hng ngy cng nh hng ti thnh phn nc trong thin nhin. Vic bn phn
v s ci to t bng phng php ha hc, cc ph thi ca cc nh my, cc khu cng nghip c
bit l nc thi cng nghip v hot ng khc ca con ngi cng a vo nc thin nhin nhng
cht v c v hu c.
C nhiu cch phn loi nc thin nhin, nguyn tc ca s phn loi ph thuc vo mc
ch phn loi v nghin cu nc:
Da vo ngun gc ca nc, c th chia thnh cc loi: nc kh quyn (nc ma, tuyt), nc
ngm, nc b mt (nc sng, ngi, h ao, bin..).
Da vo nguyn tc v mc ch s dng nc, c cc loi nh nc n, nc sinh hot, nc k
thut, nc cha bnh v.v..
Da vo hm lng v c tnh ca cc cht c trong nc, chia thnh: nc ngt (cha hm
lng cht tan < 0,1%), nc khong (hm lng cht tan t 0,1 - 2,5%), nc bin (hm lng cht
tan t 2,5 - 5,0%), nc mui (hm lng cht tan > 5% ). Ngoi ra ngi ta cn phn chia thnh cc
loi nh nc cng, nc mm, nc trong, nc c, nc c mu, nc c mi v.v..
Nc thin nhin c c trng bng mt lot cc tnh cht nh c, mi v, kim,
cng, cn khng tan v.v.. S tn ti ca cc loi vi sinh vt khc nhau, cc qun th ph du, cc loi
rong ru cng c th lm cho nc b nhim bn.
Da trn cc tnh cht ha l c th chia cc hp phn ha hc thnh 3 nhm ln nh sau:
a. Cc cht ha tan trong nc di dng cc ion v phn t. Cc ion v c trong nc vi hm
lng ln nht l Na
+
, K
+
, Ca
2+
, Mg
2+
, Cl
-
, HCO
3
-
, CO
3
2-
, SO
4
2-
. Cc ion c hm lng nh hn l Fe
2+
,
Fe
3+
, Mn
2+
, Br
-
, I
-
, F
-
, BO
2
-
, HPO
4
2-
, HSO
3
-
, HS
-
, HSiO
3
-
. Cc ion v c cn li c hm lng rt nh
trong nc c gi l cc ion ca cc nguyn t vi lng v siu vi lng. Cc kh c hm lng ln
l cc O
2
, CO
2
, N
2
, H
2
S. Cc kh nh CH
4
, Ar, Rn,... c hm lng nh. Cc cht tan hu c thng
gp trong nc t nhin l focmaldehit, phenol.
b. Cc hp phn to nn nhng h keo trong nc bao gm cc h keo v c nh SiO
2
, Al(OH)
3
,
Fe(OH)
3
, cc h keo hu c nh cc cht mn. Cc h keo thng lm cho nc c mu.
c. Cc cht to vi nc cc phn t nh ct, st v cc hp cht hu c khc nhau.
81
Cc hp phn sinh hc ca nc thin nhin bao gm: cc loi vi khun, virut, ng vt c kch
thc ln, rong ru, to... Trong nc thin nhin c cha mt lng thc n cho cc thy sinh vt. V
vy thnh phn nh lng v nh tnh ca chng ph thuc nhiu vo thnh phn ha hc ca nc.
i vi cc vi sinh vt trong nc, bn cnh nhng vi sinh vt c li cn c nhng vi sinh vt c hi.
V vy trong vic phn tch nc th xc nh ch tiu vi sinh vt cng c ngha ht sc quan trng.
7.1.2. Nc thi
Cng vi s pht trin ca vn minh nhn loi, nhu cu v nc ngy cng tng, lng nc cng
nghip cng nh nc sinh hot thi ra ngy cng nhiu gy nhim ng k n nc mt v mi
trng. Do nhiu vng nc mt b nhim cc loi hp cht ha hc v cc loi vi sinh vt c
hi.
Trong nhng nm gn y nguy c lm nhim mi trng do cc cht hu c, c bit l cc
sn phm cng nghip v khai thc ch bin du m gy ra ngy cng tng ln. Vic nhim cc loi
thuc tr su, dit c, cc cht ty ra tng hp cng l mi e da ng k n s tn ti ca cc loi
thy sinh v con ngi. Ngoi ra cn phi k ti cc cht thi phng x thi ra t cc phng th
nghim.
C th ni nc thi l mt h d th phc tp bao gm rt nhiu cht tn ti di cc trng thi
khc nhau. Nu nh nc thi cng nghip cha rt nhiu cc ha cht v c v hu c th nc thi
sinh hot li cha rt nhiu cc cht di dng protein, cacbonhydrat, m, cc cht thi ra t ngi v
ng vt, ngoi ra cn phi k n cc loi rc ri nh giy, g, cc cht hot ng b mt... Cc hp
cht v c thng gp y l cc ion nh K
+
, Na
+
, Ca
2+
, Mg
2+
, Cl
-
, CO
3
2-
, SO
4
2-
. Ngoi ra nc thi
sinh hot cn cha cc vi khun, virut, rong, ru.
Vi nhng ngnh sn xut khc nhau th trong nc thi s c nhng loi ha cht khc nhau
nh:
- Khai khong: cc kim loi, cc axit v c
- Gia cng g: flo, km
- gm : Ba, Cd, Li, Mn, Se
- da : Ca, H
2
S, Na
2
S, Cr, Zn, Ni...
- Luyn cc : NH
3
, H
2
S, cc kim...
- Cng nghip sn : Ba, ClO
3
-
, Cd, Co, Pb, Zn, Mn...
- Ha dc : B, Br, NH
4
+
,

K, cc axit, kim, cc cht hu c...
- Thy tinh : H
3
BO
3
, As...
Trong s cc ha cht gy nhim bn ngun nc th Hg, Be, Cd, Pb, As, Se c c tnh rt cao.
Nc thi sinh hot c thnh phn ha hc n gin hn, ch yu bao gm: K, Na, Fe, Pb, Zn,
Ni, Mn, Hg, Ag, Co.
Vic phn tch nc thi rt kh khn v phc tp. Khi phn tch cn phi tin hnh cc qu trnh
tch, lm giu, la chn cc phng php c nhy, chn lc cao. Mt trong nhng c tnh gy
kh khn cho vic phn tch nc thi l tnh cht khng bn vng ca n.
i vi nc n vic phn tch ha hc n gin hn v loi nc ny c x l v mt c
ha v sinh hc.
82
7.2. phn tch nc
7.2.1. Phn tch nc thin nhin
Vic phn tch nh gi cht lng nc thin nhin ph thuc vo mc ch s dng loi
nc , nhng ni chung phn tch y mt mu nc thin nhin cn xc nh kho st mt s
loi ch tiu sau y:
- Cc thng s v vt l v cm quang nh nhit , v, c, t trng.
- Cc thng s v thnh phn ha hc nh hm lng cc cation, anion v cc cht hu c.
- i vi nc sinh hot, ngoi cc ch tiu trn, cn phi xc nh v nh gi c v ch tiu vi
sinh vt.
7.2.2. Phn tch nc thi
Thnh phn nc thi khc nhiu so vi nc thin nhin, v th phn tch nc thi li theo mt
s khc. Mu nc thi thng phn tch ngay trong ngy ly mu. Sau y l cc ch tiu cn phn
tch i vi nc thi:
Nhit
Mu sc
Mi v
c
pH
Lng kt ta
bn tng i ca nc
Cc cht l lng
Tng s mui tan
Cc cht mu, cht hu c c hi
Kim loi nng
7.2.3. Nhng iu cn ch khi phn tch nc
Phi ly v bo qun mu ng quy cch, v tun theo mt cch nghim ngt cc quy tc ly
mu. Thng thng mu phi ng trong bnh polietylen.
Phi chn phng php phn tch thch hp.
Phi s dng ng quy cch cc dng c v ha cht.
7.3. Ly v bo qun mu nc
7.3.1. Xc nh v tr ly mu
Mu ly xc nh tnh cht thng thng ca nc c th ly ngu nhin t b mt vo thi
gian bui sng. Tuy nhin, khi nghin cu mt cch chi tit hn, cn phi t k hoch v xc nh v
tr ly mu trc.
i vi vng nc rng, nh ao, h, mu ly phi i din cho nc ton b vng. Cn phi ly
nc ngun thi vo v ra khi h cng nh tc ng ca con ngi n ngun nc.
83
Tu theo vng nc nng hay su m c th ly mu mt tng, hai tng (tng mt v tng
y), ba tng hoc nhiu hn na. cc sng, sui c th ly dc theo dng nc v theo chiu ngang
nu rng. nhng ni c ngun nc thi, cn ly cc im trc v sau im ha nhp ca ngun
nc thi.
7.3.2. Ly mu nc
V tr ly mu ph thuc vo mc ch ca nghin cu. Thi gian v tn sut ly mu ph thuc
vo mc bin ng ca cc cht, c th theo cc thi gian trong ngy. Trong cc ngy nng, pH ca
nc c th tng c bit l nc c kh nng m thp do kh nng trao i CO
2
ca thc vt thy
sinh, v nng P c th s b gim i.
Trong nhiu trng hp ly mu vo bui sng l thch hp v lc s bin ng cc cht din
ra chm. Trong trng hp chung, c th ly mu 3 thng mt ln, nhng khi nghin cu chi tit c
th ly mu theo chu k 7 hoc 14 ngy t ma xun n ma thu.
Trong trng hp nc ng nht, c th ch cn ly mt mu n l cng i din cho mi
trng nc thi im ly mu. V d nh dng sui chy v khng khc bit nhiu th c th ly
su trung bnh gia sui. Tng t nh vy khi ly mu trong h cha nc hoc trong b cha
nc. Tuy nhin tnh ng nht gia cc tng nc cng cn phi khng nh bng vic ly mt lot
cc mu cc su khc nhau kim tra s b trc. Nu ly nc qua my bm, ng dn hoc
vi nc th cn phi nc chy khong 5 - 6 lt trc khi ly mu.
Trong trng hp cht lng nc b bin i theo thi gian th mu cng cn phi c ly theo
cc thi gian thch hp. Nh trong trng hp c s thay i ca dng chy, ca cc ngun nc
thi...mu c th c ly nhiu ngun khc nhau ph thuc vo ngun nc. Cn phi trnh ly
mu nhng khu vc c bit nh vng nc ng, c di mc nhiu, hoc c nc ngm xm nhp
vo.
Lng nc cn ly ti thiu m bo cho cc php phn tch, thng t 1 n 2 lt. Dng c
ng mu cn phi c lm sch bng cc bin php cn thit nh ra bng cc cht ty ra hoc
dung dch axit. i vi phn tch vi sinh vt th dng c ng mu cn phi c v trng.
C th lm gim cc tc ng ca cc qu trnh xy ra trong mu bng vic thm cc ha cht cn
thit, iu chnh pH hoc gi mu nhit thp (4
0
C).
7.3.3. Ly v bo qun mu
Mc tiu chnh ca cng vic ny l nhm chuyn mu n cc ni phn tch v m bo s bin
i ca mu l ti thiu, cht phn tch s khng c s thay i ng k v hm lng. Tuy nhin,
trong nhiu trng hp, tnh cht ca nc c th b thay i, v d nh Na
+
hay Ca
+ +
c s bin ng
rt t trong khi Mo v cc vitamin th b bin i rt nhiu.
V vy, dng c ly mu v dng c ng mu phi m bo sch v phi p dng cc bin php
cn thit gim s bin i ca mu n mc ti thiu.
a. Ly mu nc:
Khi ly mu nc cn phi m bo khng lm xo trn cc tng nc. Ngi ta thng dng 4
loi dng c ly mu sau:
- Dng c ly mu hnh tr m:
84
Loi Ruttner v Kemmerer: c dng hnh tr m, dung tch t 1 n 3 lt c np y mi u.
Cc np ny c th c m ra hoc ng vo nh mt h thng dy. ng Ruttner lm bng nha, cn
ng Kemmerer lm bng ng. Khi np ng c m ra, nc s i qua, n su cn ly mu,
ngi ta thng ko, h ng ln xung vi ln (dao ng trong khong 25 cm) trc khi ng np li
ly mu.
Dng c ly mu Friedinger: Dng c ny c dng gn ging vi loi Ruttner v Kemmerer,
nhng np c m ra 90
0
. Tt c cc phn bn trong u khng lm bng kim loi. Dung tch dao
ng t 3,5 - 5 lt, dng c ny c khung gn nhit k.
- Dng c ly mu c thot kh, c hp:
Dng bnh Dussart: Dng c ny rt n gin, c th t lm ly c. Dng mt bnh c c hp
(dng c chai) c nt cao su vi hai ng nh. Mt ng c ko di xung tn y bnh, cn mt ng
ch cn xuyn qua np cao su. u trn ca hai ng nh ny c ni vi nhau bng mt ng nh hnh
ch U hoc ni bng ng cao su mm. Mt vt nng buc pha di bnh ko bnh chm xung
nc. ng ch U c buc cht vo c bnh v ni vi dy ko iu khin khi ly mu. Th bnh
n su cn thit, ko ng ch U, nc s trn vo bnh, y khng kh thot ra.
Dng c ly mu Valas: Tng t nh dng c Dussart nhng phn ng m c t tnh v cu
to phc tp hn. Sau khi m ly mu, np s c y kn li. Dng c ny thng s dng
ly mu phn tch vi sinh vt.
- Dng c ly mu bng bm:
Dng mt ng bng cao su hoc nha ( nng) th xung su cn thit. Dng bm ht
to dng nc lin tc v mu nc c ly. Nu cn phn tch cc cht kh th u ng cn t st
y bnh ng mu v t nht lng nc chy qua t nht khong gp 3 ln th tch bnh ng mu.
ly mu nc mt tng nht nh, ng cao su cn t khong gia ca hai a nha, t song
song vi nhau c ng knh khong 10 cm.
Dng c ly mu ny s dng cc loi bm tay trnh s tip xc ca kim loi vi nc. N c
u im l t lm xo trn mu nc. Th tch ca ng di 10 m, thit din 1 cm
2
ch l 1 lt. Dng c
ny thch hp ly cc mu hn hp vi cc su khc nhau.
- Dng c ly mu nc c nhiu chc nng khc nhau:
Dng c ly mu Von dorn : y l dng c c dng rt ph bin ly mu nc. Gm mt
ng hnh tr bng cht do, 2 van cao su ni vi nhau bng ng cao su pha trn v pha di ng.
Hai van cao su ny c th ng m nh mt chic kha pha ngoi ng tr. Khi th dng c xung
nc, 2 van cao su u m, n su cn thit s c ng li nh h thng iu khin (messenger).
Mu c chuyn sang bnh cha nh l nh thnh hnh tr.
7.3.4. Mt s ch dn khi ly mu nc
Khi ly mu i vi ngun nc chy nh sng, sui...th nn ly mu ch nc chy mnh
nht.
Mu ly cc h thin nhin, h cha, cc ao m...th nn ly mu cc v tr khc nhau v
nhng su khc nhau. Khng nn ly mu trung bnh i vi loi mu ny.
Mu ly t cc mch, cc loi ging, cc b h cha nc nhn to th nn ly nhng su
cn thit.
Mu nc ma ch cn hng vo lc tri ma v cn ghi r thi im ly mu.
85
Mu t cc trm v cc vi nc sinh hot, thng thng c ly trc tip ti cc ng dn nc
ra.
Mu nc thi, nn ly mu trung bnh, trc khi ly mu cn nghin cu k yu cu, mc ch
s dng nc v cc iu kin sinh hot khc
7.3.5. Bo qun mu nc trc khi phn tch
Trong khong thi gian t lc ly mu nc n khi phn tch, hm lng ca cc hp phn c
th b thay i vi mc khc nhau.
Nhit v pH ca nc l hai i lng bin i nhanh nht, v vy hai ch tiu ny cn xc
nh ngay ti ni ly mu. Hm lng mt s kh cng cn phi c xc nh ngay nh 0
2
, C0
2
, H
2
S,
Cl
2
.
i vi vic xc nh cc kim loi nng trong nc th cn tun th theo nhng qui trnh sau y
bo qun mu: thm cc ha cht tinh khit vo trong 1 lt mu nc.
Ag : Thm 5 ml HNO
3
c
Al : Thm 5 ml HCl c
As : Thm 5 ml HCl
Ca : Thng khng cn phi x l
Cd : Thm 5 ml HNO
3
c
Co : Ging nh Cd
Cr : Thm 5 ml HNO
3
c
Cu : Thm 5 ml HNO
3
c
Fe : Thm 25 ml HNO
3
khi xc nh tng hm lng st. Thm 25ml CH
3
C00Na 1M
dng xc nh cc dng khc nhau ca st.
Hg : Thm 1 ml HNO
3
c
Mg : khng cn phi x l
Mn : Thm 5 ml HNO
3
c
NH
3
: Thm 1 ml H
2
SO
4
c v 2 - 3 ml CHCl
3
v bo qun nhit 3 - 4
o
C.
Ni : Thm 5 ml HNO
3

PO
4
3-
: Thm 1 - 2 ml CHCl
3
Pb : Thm 3 ml HNO
3
c v 2 ml CH
3
COOH c
Zn : Thm 1 ml H
2
SO
4
c
SO
4
2-
: Thm 2 - 4 ml CHCl
3

CN
-
: Gi mu nhit 3 - 4
o
C, tng pH, cn xc nh ngay
SiO
3
2-
: ng trong bnh polietylen, khi hm lng SiO
2
cao cn thm 1ml H
2
SO
4
(1:3).
F
-
: Phi ng trong bnh polyetylen
Cl
-
: Thm 2 - 4 ml CHCl
3
Borat : ng trong bnh polyetylen, hoc bnh thy tinh khng c bo (nn xc nh ngay
sau khi ly mu).
SCN
-
: Nn xc nh ngay, khng nn qu 1 ngy m.
86
Phenol : Nu hm lng vt qu 100 mg/l th khng cn x l mu v khng c lu gi
qu 5 ngy m, nu hm lng <100 mg/l c th thm vo 4 g NaOH/1l, nu hm lng < 0,5 mg/l
cn phn tch ngay sau khi ly mu.
HCHO : Khng cn x l, cn phn tch ngay
ng v tinh bt : Khng nn xc nh chm hn 1 ngy m sau khi ly mu.
7.4. Xc nh thnh phn ha hc ca nc
7.4.1. Xc nh pH
Ngy nay, vic xc nh pH tr nn n gin do s pht trin ca khoa hc cng ngh. Gi tr pH
c xc nh bng php o trn my o pH (pH meter). im cn lu khi o pH l vic bo qun
in cc, do cc c im v kh hu ca vng nhit i. Trc khi tin hnh o cn phi kim tra li
my bng cch iu chnh my vi cc dung dch m c gi tr pH = 4,01; 7,00; 10,00. in cc phi
lun c bo qun trong dung dch bo qun.
7.4.2. cng
cng ca nc do cc kim loi kim th ha tr hai, ch yu l Ca v Mg gy nn. Ngi ta
thng phn bit cng cacbonat v cng phi cacbonat. Lng ion Ca v Mg tng ng vi cc
anion ca cc axit v c mnh nh HCl, H
2
SO
4
, HNO
3
gi l cng phi cacbonat. cng ton
phn l tng ca hai loi cng trn.
cng thng c biu th bng s mili ng lng gam ca cc ion Ca, Mg trong 1 lt nc
hoc i khi bng thang cng ca c, k hiu l
0
H (1 n v cng ca c tng ng vi 10
mg CaO/l).
a. Xc nh cng ca nc bng phng php chun Complexon:
Phng php ny da trn phn ng to phc ca cc ion Ca
2+
, Mg
2+
vi anion
etylendiamintetraaxetat (k hiu l Y
4-
). Cc phc c bn khng cao, phc CaY
2-
c hng s bn
l 10
10,7
, bn hn phc MnY
2-
c hng s bn l 10
8,7
. V nng ca cc ion Ca
2+
v Mg
2+
trong nc
thng khng cao, nn phn ng chun xy ra hon ton, ngi ta thng tin hnh chun
trong mi trng m NH
4
OH + NH
4
Cl c pH =10,00. Dung dch chun l Complexon III. xc
nh im tng ng ngi ta dng ch th ET_OO (Eriocrom T en). Trong mi trng chun ,
cht ch th s phn ng vi ion Ca
2+
v Mg
2+
to thnh phc c mu .
Trnh t phn tch:
Ly 100 ml nc cn xc nh cng, thm vo 10 ml dung dch m (nu kim ca mu
nc ln th phi dng dung dch HCl 0,1N iu chnh cho pH dung dch bng 7 - 8 theo giy ch
th tng hp trc khi thm dung dch m), thm mt lng nh cht ch th (khong bng mt ht
xanh), dung dch c mu . Chun dung dch bng dung dch chun Complexon III, cho ti khi dung
dch chuyn t mu sang mu xanh. Nu trong dung dch c mt cc ion cn tr nh Fe
3+
, Cu
2+
th
cn chun li vi mu nc khc v cch tin hnh nh sau: sau khi cho 10 ml dung dch m, ta
thm vi git KCN 5% che ion cn tr ri mi thm cht ch th v tin hnh chun nh trn.
Tnh kt qu:
cng ton phn ca nc c tnh nh sau:
x =
V
l md a lg/ 1000 * 2 * 025 , 0 *

87
Trong : a : l th tch dung dch Complexon III tiu tn
V : l th tch mu nc ly phn tch (ml)
0,025 : nng dung dch Complexon III
2 : s ng lng gam cng tng ng vi 1 mol Complexon III.
Ha cht:
Dung dch Complexon III 0,025M: ha tan 9,306 g Complexon III trong 1 lt nc ct hai ln.
KCN 5%: cn 5 g KCN ha tan trong 100ml nc ct hai ln.
Eriocrom T en: cn 0,05 g cht ch th trn vi 10 g NaCl.
m NH
4
OH + NH
4
Cl (pH=10): ha tan 25 g NH
4
Cl trong 100 ml nc, thm 200 ml NH
4
OH
20%, sau thm nc ct n 1 lt.
b. Xc nh Ca v Mg:
xc nh hm lng Ca v Mg trong nc sinh hot, nc ung, cc loi nc b mt, nc
thi, ngi ta thng dng phng php chun Complexon III (Trilon B).
Phc EDTA-Ca bn hn EDTA-Mg. Khi pH ca dung dch nm trong khong 12-13, EDTA-Ca
bn vng trong khi EDTA-Mg b phn hy v to ra hydroxit-Mg. Do c th chun Ca trong
mi trng ca NaOH c pH = 12 - 13, vi ch th Murexit.
Xc nh Ca:
Trnh t phn tch:
Cho mu nc vo bnh tam gic c V = 250 ml, th tch mu nc c ly khng cha qu
15 mg Ca. Dng nc ct pha long thnh 100 ml, nu thy cn thit. Nu mu nc c tnh axit th
cn trung ha bng dung dch NaOH. Nu mu nc c kim cao hn 6 ml/l th cn thm vo
lng tng ng dung dch HCl 0,1N, un si dung dch v ngui. Sau thm vo 2 ml NaOH
2M v mt t cht ch th murexit. Chun t t bng dung dch EDTA 0,025M cho n khi dung
dch chuyn t mu hng sang mu tm.
Tnh kt qu:
x =
V
a 1000 *
(mgCa/l)
a : L th tch dung dch EDTA 0,025M
V : L th tch mu nc chun (ml)
1000 : 2 x 0,025 x 20 x 1000
Ha cht:
EDTA 0,025M: Xem phn trn.
NaOH 2M : ha tan 8 g NaOH trong 100 ml nc ct hai ln.
HCl 0,1N : pha 8,2 ml HCl c trong 1lt nc ct hai ln.
Xc nh Mg:
Sau khi xc nh Ca nh trn, tin hnh xc nh tng s Ca + Mg ti cc gi tr pH = 10 vi
ch th Eriocrom T en.
Trnh t phn tch:
88
Ly vo bnh tam gic c V = 250 ml, lng th tch nh trong xc nh Ca. X l mu nh
lm i vi Ca. Thm vo 5 ml hydroxilamin 10%, vi git KCN 10%, v mt lng nh ch th
Eriocrom T en. Ri tin hnh chun bng 0,025M.
Tnh kt qu:
y =
( )
V
x x x V V 1000 24 025 , 0
2 1

mg/l
V
1
: Th tch EDTA chun Ca + Mg (ml)
V
2
: Th tch EDTA chun Ca (ml)
V : Th tch mu nc (ml)
Ha cht:
+ Hydroxilamin 10%: ha tan 10g NH
2
OH.HCl trong 100 ml nc ct hai ln.
7.4.3. Xc nh Cu
Hm lng ng trong cc loi nc thin nhin v trong cc ngun nc sinh hot thng
khng ln lm, dao ng trong khong t 0,001 - 1 mg/l. Trong nc, Cu thng tn ti di cc dng
ion Cu
2+
, hoc di cc dng phc xianua, tactrat...
xc nh Cu ngi ta thng dng phng php trc quang vi dietyldithiocacbamat (DDC).
Phn ng gia Cu
2+
vi Pb-DDC xy ra ti gi tr pH = 1 - 1,5. Trong trng hp ny cng vi
Cu cn c Bi, Hg, Ag tham gia phn ng. Cc nguyn t cn li khng tham gia phn ng, nn
phng php ny c chn lc cao. Hg v Ag khng gy cn tr v phc ca chng khng c mu.
Bimut (Bi) khng ch gy cn tr khi nng ca n vt qu 30g/l. Nu nng Bi vt qu gii
hn th cn phi lc phc DDC- kim loi vi 25 ml HCl 5M trong 5 pht, khi phc Bi-DDC b phn
hu cn Cu-DDC khng b phn hy.
Khi trong mu c cha phc Cu-xianua, th cn phi ph hu phc bng cch thm 0,5 ml
H
2
SO
4
(1:1); 5 ml HNO
3
c vo 200 - 250 ml mu, cho mu vo cc chu nhit ri t ln bp, lm
bay hi dung dch cho n gn cn kh (qu trnh ph hy ny nn tin hnh trong t ht). ngui,
thm vo 1 ml HCl c v lm bay hi n kh. ngui, thm vo nc ct hai ln, un nng dung
dch n si ha tan ht lng mui rn, lc v chuyn ton b dung dch thu c vo bnh nh
mc thch hp, nh mc bng nc ct hai ln v gi ly phn tch.
Trnh t phn tch:
Ly mt th tch nc cn phn tch trong mu cha khong 0,2 - 6,0 g Cu/l, cho vo phu
chit dung tch 200 - 500 ml. Pha long mu nc nu cn n th tch 100 ml ri thm vo 5 git HCl
(1:1), t buret thm vo mt cch chnh xc 10 ml Pb-DDC trong toluen. Cn thn y nt phu chit
li v lc trong hai pht. Gi yn phu chit cho hai tng phn lp, tch b phn tng nc pha
di, phn tng hu c cha Cu-DDC c mu vng c chuyn vo cuvet v tin hnh so mu ti
bc sng = 430 nm.
Lp ng chun:
Ly vo cc phu chit 0,00 ; 0,2 ; 0,5 ; 1,0 ; 2,0 ; 3,0 ; 4,0 ; 5,0 ; 6,0 ml dung dch chun Cu
2+
c
nng 1 g Cu/l, pha long bng nc ct n 100 ml v tin hnh nh vi mu.
Tnh kt qu:
Da vo ng chun xy dng mi tng quan y = a . x + b
89
Trong : y : Hm lng Cu
2+

x : Mt quang o c
Ha cht:
Pb-DDC trong toluen: Chun b mt phu chit sch c V = 1000 ml, thm vo 50 - 100 ml
nc ct hai ln, 0,1 g Na-DDC trong lng nc ti thiu ri thm vo phu chit lng nh
Pb(NO
3
)
2
kt ta ht Pb-DDC. Thm vo phu chit 250 ml toluen, y nt phu chit v lc mnh,
ton b kt ta Pb-DDC s tan ht vo trong toluen, tch b tng nc, phn tng hu c c lc
qua giy lc vo bnh mu nu, dung dch ny bn trong khong ba thng.
HCl long: Pha dung dch HCl 0,01N
Dung dch Cu
2+
nng 1 g Cu/ml: Ha tan 3,906 mg CuSO
4
.5H
2
O trong 1 lt nc ct hai
ln.
7.4.4. Xc nh Pb bng phng php trc quang ithizon
Hm lng Pb trong nc thin nhin rt nh, nm trong khong 0,001 - 0,02 mg/l. Trong nc
sinh hot cng c lng vt Pb do ng nc c lm bng Pb. Trong nc thi, c bit nc thi
ca cc nh my sn xut Pb, Zn hm lng Pb c th ln ti 6 - 7 mg/l. Ch trong nc thi c th
dng tan hoc di dng mui kh tan nh sunfat, cacbonat, sunfua.
ithizon - diphenylthiocacbazon l thuc th hu c c kh nng to phc cng cua vi Pb
2+
.
Phc Pb-ithizonat c mu tan trong toluen, phc mu ny c so mu ti bc sng = 520 nm.
Pb-ithizonat c chit chn lc v nh lng t dung dch c pH = 8 - 9, c cha lng d
CN
-
l cht dng che nhiu kim loi khc cng b chit vi Pb. Trong mi trng trn cng b chit
vi Pb ch c Ta, Bi, Sn. y Tali khng cn tr, nhng Bi v Sn gy cn tr, do vy chng cn c
tch trc t mi trng axit. Thm hydrazin vo dung dch mu nc, un nng kh Sn (IV)
xung Sn (II) v kh cc cht khc. Sau khi ngui thm dung dch kalinatritactrat vo, a dung
dch n pH = 2,5 - 3 bng axit Tactric, ri tin hnh chit nhiu ln, mi ln bng 5 ml ithizon trong
toluen cho ti khi mu xanh ca ithizon khng i. Tch ly tng nc. Tin hnh chit nh vy
khng nhng tch c thic m cn tch c c Hg, Ag, Cu.
Nu trong mu c cha lng ng k cht hu c th cn phi v c ha chng bng hn hp
cc axit mnh nh H
2
SO
4
v HClO
4
, cc cht oxi ha cn kh trc bng hydrazin.
Trnh t phn tch:
Thm vo cc 100 ml mu nc c pha long hoc c nc trong cha t 0,01 - 0,1
mg Pb. S dng bp cch thy, lm bay hi dung dch n khi cn 30 ml, chnh pH ti 7 theo giy ch
th tng hp. Thm vo 10 ml hydroxilamin 10% v un nng hn hp t
0
= 90 - 95
0
C trong khong
12 pht. ngui dung dch, dng axit HCl long hoc axetic long chnh pH dung dch ti 3. Chuyn
ton b dung dch trn vo phu chit, t buret thm cn thn 10 ml dung dch dithizon v tin hnh
chit cho n khi mu xanh dithizon khng thay i. Tch ly tng nc, ri chnh pH ca dung dch
ti 8 - 9 bng dung dch amoniac, thm vo 5 - 10 ml dung dch KCN 10%. Sau chuyn ton b
dung dch vo phu chit, thm vo chnh xc 10 ml dung dch dithizon v tin hnh chit cho ti khi
mu xanh ca dithizon khng thay i. Gp tt c cc phn dithizon chit c li, chuyn vo mt
phu chit sch ri tin hnh ra bng dung dch amoniac long, khi phc ca Pb-dithizonat c
mu .
Lp ng chun:
90
Thm vo mt lot cc: 0; 2,5; 5,0; 10,0; 20,0; 30,0; 40,0; 50,0 ml dung dch chun cha 0,002
mgPb/ml v thm nc ct vo mi cc n th tch 100 ml. Nh vy ta c cc dung dch c hm
lng tng ng 0; 0,05; 0,1... mg Pb/l. Ri tin hnh tng t nh i vi mu.
Tnh kt qu:
Da vo ng chun xy dng mi tng quan y = a.x +b
y : Hm lng Pb trong mu
x : Mt quang o c. T thay gi tr mt quang o c ca mu vo phng
trnh trn ta s tnh c hm lng Pb c trong mu.
Ha cht:
Dithizon: Ha tan 50 mg dithizon trong 100ml toluen, trong phu chit th tch 1000ml. Thm
vo 200ml nc ct v 5 - 10ml dung dch NH
3
c. y nt phu chit cn thn v lc trong hai
pht. Lc ny dithizon chuyn sang tng nc, sau khi hai tng phn lp, tch b phn dung
mi pha trn, li thm vo tng nc 20ml toluen, lc hn hp, tch b phn toluen. Cn thn thm
vo phu chit 200ml toluen v dung dch HCl long cho n khi tng nc c phn ng axit r, th
bng giy ch th pH. y nt phu li v lc hn hp chuyn hon ton dithizon sang tng hu c.
Chuyn tng hu c sang mt phu chit khc, ra n vi ln mi ln bng 50ml nc ct hai ln
cho n khi tng nc ht phn ng axit. Tch b phn tng nc, tng hu c cha dithizon
c chuyn vo bnh mu nu sch v kh, bo qun dung dch nhit thp v trnh nh sng.
Dung dch bn trong vi thng.
Dung dch lm vic: Ly mt th tch dung dch dithizon gc pha cng vi mt th tch toluen,
ng trong bnh thy tinh mu nu sm. Dung dch bn trong mt tun.
Dung dch ra amoniac long: Pha 175ml NH
3
c bng nc ct hai ln ti th tch 1 lt.
Kalinatritactrat 10%: Ha tan 10g KNaC
4
H
4
O
6
.2H
2
O trong 100ml nc ct hai ln.
KCN 10%: Ha tan 10g KCN trong 100ml nc ct hai ln c kim ha.
Dung dch 0,002 mgPb/ml: Ha tan 3,197mg Pb(NO
3
)
2
trong nc ct hai ln thnh 1 lt.
7.4.5. Xc nh Zn bng phng php trc quang dithizon
Km trong nc t nhin ch yu t cc ngun nc thi, c bit nc thi ca cc nh my
luyn kim, cng nghip ha cht, cc nh my si tng hp. Cc dng tn ti ca Zn trong nc l cc
ion n, ion phc vi xianua, cacbonat, sulphua...
Ni chung khi ly mu nc phn tch cn thm 1ml axit H
2
SO
4
c vo 1 lt nc, tr trng
hp mu c cha xianua.
xc nh Zn trong nc ngi ta thng phng php trc quang dithizon l phng php cho
php xc nh n vi phn trm miligam km trong 1 lt nc.
Ion Zn to phc vi dithizon to thnh km-dithizonat c mu hng. Phn ng gia Zn v
ithizon xy ra ti pH = 5 v dung dch c cha lng d S
2
O
3
2-
, CN
-
dng che Cd, Ni, Pb. Do
nu trong mu nc khng c cc ion ny hoc c nhng vi hm lng nh hn km th khng cn
dng xianua. Thic (II) cn c oxi ha trc thnh thic (IV) bng H
2
O
2
v un si k phn hu
ht H
2
O
2
cn d. Cc cht oxi ha c dithizon cn c loi tr trc khi xc nh. Fe (III) cn
c loi tr trc bng cch kt ta n di dng hydroxit v lc b.
Trnh t phn tch:
91
Ly 100 - 200 ml nc cn phn tch cho vo phu chit, mu nc cn c pha long trc
hoc lm bay hi cha khong 0,005 - 0,03 mg Zn. Dng axit axetic hoc NaOH long chnh pH
ca dung dch ti 7, ri thm vo chnh xc 20 ml dung dch m c pH = 5 v 20 ml dung dch che.
T buret thm vo chnh xc 10 ml dithizon, y nt phu, lc cn thn trong khong 2 pht. Qu trnh
chit kt thc khi mu ca dithizon gi nguyn mu xanh. Gp tt c cc phn dithizon c chit li,
chuyn vo mt phu chit sch kh khc ri tin hnh ra dithizon d bng dung dch amoniac long
nh i vi ch. Khi phc Zn-dithizonat c mu hng xut hin. Phc mu ny c em so mu
ti bc sng = 530 nm.
Lp ng chun:
Chun b 7 phu chit sch, thm vo ln lt tng phu 0; 10; 20; 30; 40; 50; 60ml dung dch c
nng 0,0005 mg Zn/ml. Thm nc ct hai ln vo c th tch l 100ml ri tin hnh nh i
vi mu phn tch.
Tnh kt qu:
Da trn vic lp thang chun s xc nh c mi tng quan hm s y = a.x +b.
Trong : y: hm lng Zn trong mu
x: mt quang
Ha cht:
Dung dch che : Ha tan 120 g Na
2
S
2
O
3
.5H
2
O, 0,15 g (NH
4
)
2
C
2
O
4
.2H
2
O, 1,5 g KCN (nu cn),
24 g CH
3
COONa.3H
2
O, 10 ml NH
3
2N, 70 ml HCl 1N trong nc ct hai ln ri chuyn vo bnh nh
mc 1 lt v nh mc n vch mc.
Dung dch m pH = 5: Ly 73,4 ml CH
3
COOH 1N v 50 ml NaOH 1N thm nc ct n
500 ml v lc u.
Dithizon: S dng nh trong xc nh Pb.
7.4.6. Xc nh Hg bng phng php trc quang dithizon
Thy ngn i khi c trong nc chy ra t cc m v trong nc thi sn xut cc cht mu,
dc phm v cht n. Vic xc nh Hg l rt quan trng v cn thit, v cc hp cht ca n thng
rt c.
xc nh thy ngn thng dng phng php chit trc quang dithizon. Phng php ny rt
c trng v chn lc i vi Hg, v n c chit hon ton t mi trng c axit rt cao, trong
mi trng ny tuyt i a s cc kim loi khc khng b chit. Phng php cho php xc nh t
vi phn trm miligam ti hng chc miligam trong 1lt nc.
Nu mu nc lu mi tin hnh phn tch th cn thm vo 1 ml HNO
3
c cho 1 lt mu.
Trong mi trng axit ch c Ag, Cu, cng b chit vi Hg. che hai nguyn t ny phi dng
Complexon III v thioxianat (SCN
-
).
Trong mi trng m axetat c cha Complexon III v thioxianat (SCN
-
) ch c Au (III) v c
th c Pt (II) c nh hng n vic xc nh, nhng hai nguyn t thng t khi c mt trong nc.
Cht hu c c mu thng tch nc bng toluen. Nu mu c cha nhiu cht hu c th cn
v c ha trc khi xc nh.
Trnh t phn tch:
92
Cho vo phu chit mt th tch nc thch hp trong c cha 0,005 - 0,1 mg Hg, pha long
n 100 ml bng nc ct hai ln. Thm vo 20 ml dung dch m, 10 ml complexon III, 10 ml
KSCN.T buret thm chnh xc 10 ml dithizon, y nt phu chit, lc cn thn trong khong 2 pht.
Qu trnh chit kt thc khi mu xanh ca dithizon khng thay i. Gp tt c cc phn dithizon
chit c li, chuyn vo mt phu chit sch kh. Dng dung dch amoniac long 5% ra
dithizon d. Tch b phn tng nc, khi phc Hg-dithizonat c mu da cam xut hin. Phc
mu ny c so mu ti bc sng = 490 nm.
Lp ng chun:
Php lp ng chun tng t nh khi xc nh cc nguyn t khc. ng chun y c
lp vi cc dung dch ng vi 0; 0,05; 0,1 mg Hg/l. Tin hnh tng t nh i vi mu phn tch.
Tnh kt qu:
Tng t nh i vi cc nguyn t khc ta xy dng hm tng quan
y = a.x +b.
Trong : y: hm lng Hg trong mu
x: mt quang
Ha cht:
Dung dch m axetat (pH = 4): Ha tan 57 ml CH
3
COOH c v 82 g CH
3
COONa.3H
2
O
trong nc ct thnh 1 lt.
Complexon III 0,05N : Ha tan 9,306 g EDTA trong nc ct thnh 1 lt.
KSCN: Pha dung dch 0,1M.
7.4.7. Xc nh Fe
Hm lng ca Fe c trong nc thin nhin ph thuc rt nhiu vo ngun nc v nhng vng
m ngun nc chy qua. Ngoi ra cn ty thuc vo pH v s c mt ca mt s cht nh CO
3
2-
, O
2
,
S
2-
v cc cht hu c tan trong nc, chng s oxi ha hay kh st v c th lm cho Fe nm dng
tan hay kt ta.
xc nh Fe trong nc, thng dng phng php so mu vi cc thuc th nh axit
sunfoxalixilic hoc o-phenaltrolin.
Mun xc nh st nm cc dng khc nhau, mt iu quan trng cn phi ch l cch ly
mu. xc nh tng lng st c trong mu cn phi x l mi mu nc vi 25 ml HNO
3
c.
Nu mun xc nh Fe trong mu cc dng khc nhau, th mi lt nc cn phi x l bng 25
ml dung dch m CH
3
OONa 1M.
a. Xc nh Fe bng thuc th o-phenalthrolin:
Thuc th o-phenalthrolin phn ng vi ion Fe
2+
to thnh phc cht c mu tm . Khong pH
cho qu trnh to phc kh rng t 3 - 9. Mn c nh hng rt ln n qu trnh xc nh, nn khi mu
phn tch c mt Mn th khng nh lng c Fe bng phng php ny. Lng Cu > 10 mg/l cng
gy nh hng khi xc nh nhng c th loi tr nh hng bng cch tin hnh phn ng trong
khong pH t 3 - 4.
Nu trong mu c cha lng ln cc cht hu c th trc cn phi v c ha.
Trnh t phn tch:
93
Ly lng mu nc cn phn tch sao cho lng Fe trong khng qu 0,2 mg cho vo bnh
nh mc 50 ml. Thm 1 ml HCl long, c n th tch cn khong 40 ml. Lm ngui, thm 1ml
hydroxilamin kh Fe
3+
thnh Fe
2+
, ri thm 1ml o-phenalthrolin. Nh tng git NH
3
n khi giy
ch th cng g chuyn sang mu xanh. nh mc bng nc ct, lc u. Sau tin hnh so mu ti
bc sng = 540 nm.
Lp ng chun: Ly ln lt vo mi bnh 0; 0,5; 1,0; 2,0; 5,0; 10,0; 20,0; 30,0; 40,0; 50,0 ml
dung dch 0,005 mgFe/ml, ri tin hnh tng t nh i vi mu.
Tnh kt qu:
Da vo ng chun xc lp hm tng quan y = a.x + b.
y : Hm lng Fe trong mu
x : Mt quang
Ha cht:
o-phenalthrolin : Ha tan 0,28 g o-phenalthrolin trong nc ct thnh 100ml.
Hydroxilamin 10%: Ha tan 10g hydroxilamin trong nc ct thnh 100ml.
HCl : Dung dch long (1:9).
Dung dch NH
3
c.
CH
3
COONa 1M: Ha tan 68g CH
3
COONa.3H
2
O trong 500 ml nc, thm 25 ml CH
3
COOH
6M sau thm nc ct n 1 lt.
b. Xc nh Fe bng thuc th axit sunfoxalixilic:
Ion Fe
3+
phn ng vi thuc th axit sunfoxalixilic trong mi trng kim to thnh phc c mu
vng. Lng ln Al, Cu c trong mu s cn tr php xc nh.
Trnh t phn tch:
Cn ly lng mu nc thch hp trong c cha t 0,01 - 1,00 mg Fe, cho vo cc c dung
tch 100 ml. Thm 0,5 ml HNO
3
c, lm bay hi n cn khong 10 ml. Sau pha long bng nc
ct, lc, thu ton b nc lc v nc ra vo bnh nh mc 100 ml, thm nc ct n khong 90 ml.
Thm 2 ml dung dch NH
4
Cl, 2 ml dung dch axit sunfoxalixilic v 2 ml dung dch NH
3
. Thm nc
ti vch mc, lc u, sau 5 pht o mt quang ca dung dch.
Lp dng chun:
Ln lt ly vo mi cc 0; 1; 2; 3; 4; 5; 6; 7;8; 9; 10 ml dung dch c nng 0,1mg Fe/ml. Ri
tin hnh tng t nh i vi mu phn tch.
Tnh kt qu:
Da vo ng chun lp hm tng quan y = a.x +b
y- hm lng Fe c trong mu
x- mt quang o c
Ha cht:
Axit sulphosalixilic 20%
NH
3
c
NH
4
Cl 2N: Ha tan 107g NH
4
Cl trong 1 lt nc ct hai ln
HNO
3
c
94
7.4.8. Xc nh Mn
Trong nc Mn thng nm hai dng tan v khng tan. dng tan Mn tn ti di dng ion
Mn
2+
, cn dng khng tan l kt ta hydroxit. Hm lng Mn c trong nc tu thuc vo ngun
nc, hm lng Mn cao trong nc thi ca nh my luyn kim v nh my ha cht.
xc nh tng lng Mn c trong nc ngi ta thng dng phng php trc quang (so
mu). Khi Mn s b oxi ha thnh Mn
7+
bi cht oxi ha mnh nh amonipesunphat (NH
4
)
2
S
2
O
8
.
Ch khi ly mu phi thm vo mi lt nc 5 ml HNO
3
c.
Trnh t phn tch:
Cho 50 - 100 ml mu nc vo cc 150 ml sao cho lng Mn trong l 0,005 - 1 mg, thm 2 ml
HNO
3
, nh tng git dung dch AgNO
3
cho n khi kt ta ht ion Cl
-
thm tip 1 - 2 ml dung dch
AgNO
3
, lng ri lc. Nu hm lng clorua v cc cht hu c ln th phi tin hnh v c ha
mu, khng th loi tr Cl
-
bi AgNO
3
khi hm lng ca chng qu ln v s gy hin tng hp ph
Mn. Thm 0,5g pesunfat vo nc lc. un dung dch ti gn si khong 10 pht. ngui ri
chuyn vo bnh nh mc c dung tch 100 ml, thm nc ti vch mc. Tin hnh so mu ti bc
sng = 525 nm.
Lp ng chun:
Cho vo 10 cc 150 ml chu nhit ln lt theo th t 0; 0,5; 1; 2,5; 5; 10; 20; 30; 40; 50 ml dung
dch chun Mn c nng 0,01 mg/ml. Ti tin hnh nh i vi mu phn tch.
Tnh kt qu:
Da vo thang chun thit lp mi tng quan hm s y = a.x +b
Trong : y- hm lng Mn
x- mt quang o c
Ha cht:
HNO
3
c
AgNO
3
: Ha tan 17g AgNO
3
trong 500 ml nc ct hai ln
(NH
4
)
2
S
2
O
8
mui rn.
Dung dch chun: Ha tan 0,2748 g MnSO
4
trong 1 lt nc ct hai ln c axit ha bng
H
2
SO
4
, dung dch ny c nng 0,1 mg/ml. Pha long dung dch ny 10 ln ta c dung dch c
nng 0,01 mg/ml.
7.4.9. Xc nh Cr
Trong mi trng axit, cromat v dicromat phn ng vi diphenylcacbazit to thnh hp cht tan
mu tm rt thun li cho vic o mu. Phn ng ny dng d nh lng Cr c hm lng t 0,005
- 1,00 mg/l.
Cc ion Hg
2+
v Hg
2
2+
(khi hm lng > 200 mg/l), V, Mo
6+
cng c kh nng to phc mu vi
thuc th , tuy nhin nhng ion ny thng c rt t trong nc. St vi hm lng ln hn 1 mg/l
cng phn ng vi thuc th to thnh hp cht c mu vng nu, nhng c th loi tr Fe bng cch
thm vo lng nh H
3
PO
4
. Nu trong mu c cha lng ln Mn th phi oxi ha bng pesunfat
trong mi trng kim hoc trung tnh, n s to thnh kt ta MnO
2
, v c lc b bng bng thy
tinh.
95
Nu mu nc c tnh kim hay trung tnh th rt kh xc nh ring Cr
3+
v Cr
6+
. Bi v khi axit
ha, nu trong dung dch c cht kh nh Fe
2+
, sunfit v cc cht hu c...th Cr
6+
s b kh xung
Cr
3+
. Trong trng hp ny ch nn xc nh tng hm lng Cr. Mun xc nh ring ta phi tch
ring Cr
3+
bng cch kt ta n bng MgO (pH = 10,5 - 11). Khi Cr(OH)
3
kt ta trn b mt MgO,
cn Cr
6+
vn tan trong dung dch. Lng ln cht hu c, cc cht kh v ion Cl
-
khng cn tr php
xc nh.
a. Xc nh Cr
6+
:
Trnh t phn tch:
Ly lng mu phn tch vo bnh nh mc sao cho trong c khong 0,005 -0,1 mg crom.
Mu nc c cho vo bnh nn c 25 ml, thm vi git phenolphtalein, nu dung dch c mu hng
th thm tng git H
2
SO
4
1N ti khi mt mu, ghi th tch dung dch H
2
SO
4
1N dng: nu dung
dch khng c mu th thm tng git NaOH 1N. Thm bng y git H
2
SO
4
1N hoc NaOH 1N vo
mu trung ha. Sau thm 1 ml H
2
SO
4
, 0,2 ml axit photphoric v 2 ml dung dch
diphenylcacbazit, thm nc ti vch mc, lc u. Sau 5 - 10 pht th em so mu ti bc sng =
540 nm.
Lp ng chun:
Chun b 10 bnh nh mc c dung tch 100ml. Ln lt ly vo mi bnh 0; 1; 2; 5; 10; 15; 20;
30; 40; 50 ml dung dch c nng 0,002 mgCr/ml. Ri tin hnh tng t nh i vi mu phn tch.
Tnh kt qu:
Da vo ng chun thit lp mi tng quan hm s y = a.x + b
Trong : y: hm lng Cr
x: mt quang o c
b. Xc nh tng hm lng Cr:
Ly lng mu nc cn phn tch cho vo cc c th tch 250 ml sao cho lng Cr trong
khong 0,005 - 1 mg. Trung ha bng H
2
SO
4
hoc NaOH 1N. Sau thm 0,3 ml H
2
SO
4
1N, 5 - 10
ml dung dch amonipesunfat, un si dung dch 20 - 25 pht ( phn hu ht pesunfat d). Lm bay
hi bt dung dch cn khong 50 ml. Chuyn tt c vo bnh nh mc v tin hnh nh xc nh
Cr
6+
.
Ha cht dng cho xc nh cc dng Cr:
NaOH 1N: Ha tan 40 g NaOH trong 1 lt nc ct hai ln.
H
2
SO
4
1N: Ht 28 ml H
2
SO
4
c vo 500 ml nc ct hai ln ri nh mc ti 1 lt.
H
3
PO
4
c 85%
Diphenylcacbazit 0,5% trong axeton: Ha tan 0,25g diphenylcacbazit trong 50 ml axeton.
Amonipesulphat 0,1% : Ha tan 0,1 g amonipesulphat trong 100 ml nc ct hai ln.
Dung dch chun: Ha tan 2,8285 g K
2
Cr
2
O
7
trong 1 lt nc ct hai ln c dung dch c
nng 1 mg/ml. S dng dung dch ny pha thnh dung dch c nng 0,002 mg/ml.
7.4.10. Xc nh Ni bng thuc th dimetylglioxim
Trong nc sinh hot v nc t nhin thng khng c Ni hoc ch l lng vt. Ni ch c trong
nc mt s h hoc sng m ngun nc chy qua nhng vng ni v vng m c Ni. Ni c trong
nc thi ca mt s nh my luyn kim v ha cht c s dng Ni. Trong nc Ni tn ti di dng
Ni
2+
, dng phc xianua v dng t tan nh sunfua, cacbonat, hydroxit...
96
xc nh Ni ngi ta thng dng phng php so mu khi hm lng Ni nm trong khong 1
- 20 mg/l, nu hm lng Ni ln hn 5 mg/l th c th dng phng php khi lng, cn khi hm
lng 0,02 mg/l dng phng php cc ph.
Mu nc ly xong cha phn tch ngay th phi thm 2 - 5 ml HNO
3
c vo 1 lt mu nc.
Nu cn nh lng ring Ni dng tan v khng tan th khi ly mu ta phi lc ngay ri mi ng
chai bo qun v xc nh Ni dng tan v tng lng Ni, t suy ra hm lng Ni dng khng
tan.
Trong mi trng amoniac yu, khi c mt cht oxi ha mnh ion Ni
2+
phn ng vi
dimetylglioxim to thnh phc cht c mu .
St, crm v ng cn tr php xc nh nn cn loi b trc. loi b Fe thm 2 ml H
2
O
2
3%
vo 100 ml mu phn tch, un si v kt ta hydroxit bng dung dch ammoniac, lc b kt ta.
Loi b Cu bng cch axit ha mu bng HCl n pH = 2, sau sc kh H
2
S, lc b kt ta,
nc lc trc khi phn tch phi un si k ui ht H
2
S d.
Trnh t phn tch:
Cho vo bnh nh mc 100 ml mt th tch mu sao cho lng Ni trong mu l 0,01 - 0,25 mg.
Thm vo 10 ml dung dch nc brom bo ha, lc hn hp. Sau thm 12 ml dung dch
ammoniac, 4 ml dung dch dimetylglioxim ri thm nc ct ti vch mc. Sau tin hnh o mt
quang ti bc sng = 540 nm.
Lp ng chun:
Chun b 8 bnh nh mc c dung tch 100 ml, ln lt ly vo mi bnh 0; 2,5; 5; 10; 20; 30; 40;
50 ml dung dch c nng 0,005 mg/ml. Ri pha long thnh 50 ml bng nc ct. Ri tin hnh
nh i vi mu phn tch.
Tnh kt qu:
Da vo ng chun thit lp mi tng quan hm s y = a.x +b
Trong : y : hm lng Ni trong mu
x : mt quang o c
Ha cht:
Dung dch nc brom bo ha
Amoniac c
Dimetylglioxim 1,2% : Ha tan 1,2 g mui natri dimetylglioxim trong nc ct v pha long
thnh 100ml.
Dung dch chun : Ha tan 1 g dy Ni vo 15 ml HNO
3
c, thm 5 ml H
2
SO
4
(1:3), un n
bc khi trng. Ha tan phn cn v thm nc ct n 1 lt. Dung dch ny c nng 1 mgNi/ml.
T dung dch ny pha thnh dung dch c nng 0.005 mg/ml.
7.4.11. Xc nh Asen (As) bng phng php trc quang
Trong nc As thng nm dng asenat. As hu nh khng c trong nc ngm, n ch c
trong cc ngun nc thi ca cc nh my luyn kim, cng ngh ha hc, cc nh my da v sn xut
cht mu.
xc nh asen ngi ta thng dng phng php so mu vi thuc th Ag-
dietyldithiocacbamat. Bng phng php ny c th xc nh c n 0,05 mg asen trong 1 lt nc.
97
Di tc dng ca dng hidro mi sinh, asenat b kh thnh asin (AsH
3
) v sau phn ng vi
Ag-dietyldithiocacbamat to hp cht c mu khi c mt ca piridin.
Trong iu kin ny, H
2
S cng phn ng vi thuc th to thnh hp cht c mu tng t. Ta
phi loi b nh hng ca H
2
S bng cch cho hp th trn ng c ng giy lc c tm ch axetat
hoc bng cch v c ha n nh mt cht hu c. SbH
3
cng c kh nng phn ng tng t nh
AsH
3
nhng n ch to thnh hp cht mu hng nht khi c hm lng n cao hn 0,1 mg/l, cho nn
thc t c th b qua.
Lng ln cht hu c trong nc cng gy cn tr php xc nh cn loi b chng bng cch
v c ha mu. Ly lng mu sao cho c 0,002 - 0,4 mg As, thm vo 2-3 ml H
2
SO
4
c, 5 ml HNO
3
c v 0,5 ml 3%, lm bay hi dung dch n khi bc khi trng. ngui, thm 5 ml nc ct,
chuyn ton b vo bnh ct, trng nhiu ln bng nc ct v thm nc ct ti th tch khong 50 ml.
Nu lng cht hu c c trong nc t th ta c th lm giu asen bng cch cng kt n vi st
hydroxit. Ly 100 - 1000 ml mu sao cho lng asen trong khng nh hn 0,002 mg, cho vo phu
chit, thm vo 0,5 - 1 ml dung dch FeCl
3
(ha tan 115 g FeCl
3
trong 1 lt nc ct hai ln). Trung
ha bng NH
4
OH (1:1) n khi xut hin kt ta. Lc nh phu chit khong 15 pht, yn cho kt
ta lng xung, tch ly phn kt ta cho vo bnh ct ca my ct. Lp li kt ta mt ln na trong
phu chit tch ht kt ta. Nu cn kt ta th tch v gp n cng vi kt ta trc. Ha tan kt
ta bng mt lng va HCl (1:4). Nu kt ta khng tan ht th lc b. Thm nc ct ti khong
50 ml.
Trnh t phn tch:
Trc khi tin hnh phn tch cn kim tra xem hm lng asen c trong cc thuc th.
Ly khong 50 ml mu nc cn phn tch cho vo bnh tam gic sao cho lng asen trong
khong 0,002 - 0,01 mg. Thm vo 15 ml dung dch HCl long. Sau thm tip 6 ml dung dch
KI v 0,5 ml dung dch SnCl
2
. Lc u hn hp v yn 15 pht. Nhi giy lc tm ch axetat vo
ng thy tinh. Ly 15 ml dung dch hp th Ag- dietyldithiocacbamat vo bnh hp th ri ni tt c
cc b phn ca bnh hp th vi nhau. Cho vo bnh tam gic 5 g km ht hay 2 - 3 g km bt, y
ngay bnh li. Zn s kh H
+
gii phng ra hyro. Hyro mi sinh s kh asen to thnh asin bay ra v
b dung dch trong bnh hp th. Phn ng xy ra trong 60 pht. Nu thy phn ng xy ra chm th
cho thm 0,5 ml SnCl
2
, 5 - 15 ml HCl c qua phu.
Sau khi phn ng xong, chuyn dung dch bnh hp th vo cuvet v em o mt quang ti
bc sng 560 nm.
Lp ng chun:
Pha mt dy dung dch chun c cha 0; 2; 5; 10; 20; 30; 40; 50 ml dung dch chun c nng
0.001 mg/ml. Tin hnh nh i vi mu phn tch.
Tnh kt qu:
Da vo ng thit lp mi tng quan hm s y = ax + b
Trong : y : Hm lng As trong t
x : Mt quang o c



98


Hnh 7.1. Dng c xc nh asen
7.4.12. Xc nh Cl
-
bng phng php chun Morh
Clorua c kh nhiu trong nc thin nhin, trong cc ngun nc thi Cl
-
ph thuc vo qu
trnh sn xut cng nghip. Mt trong nhng tiu chun nh gi nhim bn ca nc l hm
lng Cl
-
.
Khi hm lng Cl
-
trong nc trn 2 mg th c th nh lng n bng phng php chun
AgNO
3
.
Phng php ny s dng K
2
CrO
4
lm ch th, khi Cl
-
kt ta ht di dng AgCl th mt git
AgNO
3
d s lm xut hin kt ta mu nu Ag
2
CrO
4
. Trong phng php ny cng vi Cl
-
cn c
Br
-
, I
-
cng b chun . Xianua cng nh hng, tuy vy anion ny c th b ph hu trc bng H
2
O
2

trong mi trng kim. Cc anion sulphit, sulphua v thiosulphat cng ngn cn vic xc nh. C ba
anion ny c loi b bng H
2
O
2
. Sunfit c ph hu trong mi trng trung tnh, hai anion cn li
trong mi trng kim. Ion photphat cng cn tr vic xc nh nu hm lng ca n ln hn 25
mg/l. Fe
3+
ngn cn vic xc nh khi hm lng ca n ln hn 10 mg/l.
Trnh t phn tch:
Ly 100 ml mu nc lc. Nu mu nc c phn ng axit hoc kim th trung ha theo ch
th phenolphtalein. Sau khi trung ha xong, thm vi git dung dch axit long dung dch mt mu
hng (nu c). Nu mu nc c pH = 7 - 10 th khng cn x l trc. Thm vo 1ml dung dch
K
2
CrO
4
ri tin hnh chun bng dung dch AgNO
3
cho n khi dung dch chuyn sang mu da
cam nu.
Tnh kt qu:
Hm lng Cl
-
trong nc c tnh theo cng thc sau:
(mgCl
-
/l) =
V
N a 1000 . 45 , 35 . .

a : Th tch dung dch chun AgNO
3
(ml)
N : Nng ng lng ca AgNO
3

V : Th tch dung dch mu (ml)
7.4.13. Xc nh NO
3
-

Ion NO
3
thng c mt trong tt c cc loi nc. Tuy vy, hm lng NO
3
-
trong nc mt v
nc ngm thng khng ng k. Mt s loi nc thi c hm lng NO
3
-
cao.
Khi hm lng NO
3
-
trong nc t 0,5 - 50 mg/l th nn xc nh bng phng php trc quang
vi thuc th axit disunfofenic.
Nt len bng tm dung
dch ch axetat
Bnh phn
ng
ng hp th
99
Hm lng Cl
-
ln hn 10 mg/l s ngn cn vic xc nh. nh hng c loi tr bng cch
pha long dung dch hoc thm Ag
2
SO
4
vo lm kt ta Cl
-
.
Trnh t phn tch:
Dng 100 ml mu nc cha khng qu 5 mg NO
3
-
, trung ha n pH = 7, chuyn vo chn s v
c cn trn bp cch thy. Thm 2 ml dung dch axit disunfofenic vo phn cn trong chn v dng
a thy tinh nh, sch ha tan hon ton, nu cn va khuy va un cch thy. Thm vo 20 ml
nc ct, 6 - 7 ml NH
3
c hoc 5 - 6 ml KOH 12N. Nu trong dung dch c kt ta cc hydroxit kim
loi th phi lc qua phu lc thy tinh xp hoc phi thm vo dung dch EDTA trong NH
3
ha tan
kt ta. Chuyn dung dch trong sut vo bnh nh mc c 50 ml, nh mc bng nc ct v tin
hnh o mt quang ti bc sng = 410 nm.
Xy dng ng chun: Lm bay hi n kh trn bp cch thy 50 ml dung dch chun NO
3
-
.
Thm 2 ml dung dch axit disunfofenic vo phn cn kh, khuy nh bng a thy tinh nh n khi
tan hon ton, nh mc bng nc ct ti 100 ml.
Chun b mt lot bnh nh mc c dung tch 50 ml, ln lt thm vo mi bnh 0; 0,1; 0,3; 0,5;
0,7; 1; 2; 5; 10; 15; 20; 30 ml dung dch chun c mu nh chun b trn. Thm vo 2 ml dung
dch axit disunfofenic v cng mt lng KOH nh lm vi mu. nh mc bng nc ct ti th
tch 50 ml, ri tin hnh so mu.
Tnh kt qu:
Da vo ng chun thit lp mi tng quan hm s y = a.x + b
Trong : y : Hm lng NO
3
-
c trong mu
x : Mt quang o c
T xc nh c hm lng NO
3
-
c trong mu nc em i phn tch.
7.4.14. Xc nh bc (Ag)
Bc thng c trong nc chy ra t mt s m v thng c trong nc thi ca cng nghip
nh. Trong nc bc tn ti di dng phc tan hoc hp cht khng tan, ch yu l bc halogenua.
xc nh bc trong nc c th dng phng php trc quang dithizon hoc rodanin. bo qun
mu nc khi phn tch bc cn thm 5 ml HNO
3
c vo 1lt nc.
Ion Ag
+
phn ng vi rodanin to thnh kt ta , khi lng bc nh th to thnh dung dch keo.
lm n nh dung dch keo , thng dng dung dch gelatin. Phn ng ny kh c trng v
chn lc i vi bc. Trc khi xc nh cn ph hu cc vn c bng cch v c ha mu nc.
Trnh t phn tch:
Ly 50 ml dung dch mu trong sut ( c v c ha), cho vo cc dung tch 100 ml, thm
vo 2 ml dung dch kalinatritactrat, 2 ml NH
3
, 1 ml gelatin. Sau khi trn u hn hp, thm vo 0,5 ml
rodanin v sau 5 pht th tin hnh o mt quang.
Xy dng ng chun: ng chun c lp vi dy dung dch c cha 0; 0,5; 1; 8; 10 ml
dung dch c cha 0,01 mgAg/ml. Ri pha long bng nc ct hai ln ti th tch 50 ml. Tin hnh
nh i vi mu phn tch.
Tnh kt qu:
Da vo ng chun thit lp mi tng quan hm s y = a.x + b
Trong y : Hm lng Ag c trong mu
100
x : Mt quang o c
T s xc nh c hm lng Ag c trong mu
Ha cht:
Kali natri tactrat 20%
Amoniac 10%
Gelatin 1%
Rodanin 0,03% trong axeton, ng trong chai mu nu, ch mt, dung dch bn trong 2
tun.
7.4.15. Xc nh Beri (Be)
Beri l kim loi mu xm sng, khng gp trong thin nhin dng tinh khit, t khi 1,85; nhit
nng chy 1284
0
C; nhit si 2471
0
C; beri clorua v beri sunfat n nh trong nc, nng ca
chng gim n 30 - 35% so vi nng ban u ch trong khong 5 giy.
Hm lng trong nc thin nhin ca Be dao ng trong khong 0,00001 - 0,0012 mg/l. Hm
lng Be cao trong nc thin nhin thng gp cc ni c va beri v trong nc c lng ln cc
ion F
-
v SO
4
2-
. Beri thng c trong nc thi ca cc nh my luyn kim, ch to my, x l du m
v cc x nghip in t.
i vi ngi v ng vt mu nng, khi hm lng Be trong nc cao s gy nhim c cp
tnh v tc ng tch lu. Cc mui NO
3
-
, Cl
-
v SO
4
2-
ca Be rt c. Khi hm lng Be
2+
(mg/kg
trng lng c th) dng mui sunfat l 80 th 50% chut b cht; dng clorua l 92. C hai dng
hp cht ny u c kh nng tch lu.
Vi lng 0,00001 mg/kg th trng hay 0,0002 mg/l nc th khng gy nguy him.
i vi ng vt sng trong nc, khi hm lng mui bericlorua l 15 mg/l nc cng th lm
cht c tu, 0,05 mg/l lm cht rn nc. Khi hm lng mui berisunfatl 1,3 mg/l nc mm th lm
cht c r.
Khi nng Be l 10 mg/l th lm gim trong ca nc; 0,5 - 1,0 mg/l s km hm cc qu
trnh t lm sch sinh hc trong h cha v qu trnh sinh sn ca h vi thc vt; nng 0,005 mg/l
th khng c nh hng n qu trnh t lm sch ca h cha.
Nng Be t 15 - 20 mg/l s km hm s ny mm ca ht rau dip v ci canh.
Nng gii hn cho php (mg/l):
+ Nc ung: Tu theo tiu chun tng nc, Lin X (c) l 0,0002
+ Nc s dng nng nghip v nc sinh hot : Lin X (c) l 0,0002
+ Nc ti cho tt c cc loi t (ti lu di): 0,5
Phng php xc nh:
C th xc nh Be theo phng php quang ph hp th nguyn t, phng php ph pht x
plasma ICP (Inductively Coupled Plasma) v phng php trc quang. Tuy nhin, phng php trc
quang cho chnh xc km hn so vi hai phng php trn.
101
Phng php Aluminon
Nguyn l: Dung dch thuc th aluminon phn ng vi Be to thnh hp cht mu sm, hp
th cc i ti bc sng 515 nm. Thm mt lng nh cht to phc EDTA s ngn cn nh hng
ca Al, Co, Cu, Fe, Mn, Ni, Ti, Zn v Zirconi hm lng va phi n qu trnh xc nh Be.
Trong iu kin nh vy khi hm lng Cu khng vt qu 10 mg trong lng mu phn tch s
khng nh hng n php xc nh. Nu lng cao hn th cn tng lng EDTA thm vo. Phc
ca Cu hp th khng ng k bc sng 515 nm. C th loi tr nh hng ny bng cch thm
mt lng Cu tng ng vo thang chun.
Bo qun mu:
Axit ha ton b mu phn tch trong khi bo qun gi cc kim loi trong dung dch v ngn
nga chng bm ln thnh bnh. Nu nc sch khng c cc cht l lng th mi lt mu thm vo
1,5 ml HNO
3
c a pH ca mu n 2. Nc mt ao h v nc thi c th cha cc trm tch
th cn phi thm nhiu axit hn.
Dng c:
My so mu quang in, knh lc mu xanh lc, bc sng 515 nm, cuvet dy 5 cm.
Thuc th:
Dung dch Beri gc: Ha tan 0,9837 g berisunfat ngm 4 phn t nc, tinh khit 99,9% trong
100 ml nc ct, nu cn th lc sau thm nc ct ti 500 ml, 1 ml dung dch ny cha 100 g Be.
Dung dch chun s dng: Ht 5 ml dung dch gc cho vo bnh nh mc 100 ml ri nh
mc bng nc ct ti vch mc, 1 ml dung dch ny cha 5 gBe.
Dung dch EDTA: Ha tan 2,5 g EDTA trong 30 ml nc ct, thm vo 1 git metyl 0,05%
pha trong ru. Trung ha dung dch bng NH
4
OH c, lnh v thm nc ct n 100 ml.
Dung dch m aluminon: Cn 500 g CH
3
COONH
4
cho vo trong cc dung tch 2 lt trong
c sn 1 lt nc ct. Thm vo 80 ml axit axetic c v khuy cho n khi c dung dch ng
nht, nu cn th lc. Ha tan 1 g aluminon (aurintricacboxilic axit triamnonium) trong 50 ml nc ct
ri vo cc cha dung dch m trn. Ha tan 3 g axit benzoic (C
7
H
6
O
2
) trong 20 ml ru metylic
ri thm vo cc ng dung dch m trn, nh mc bng nc ct ti vch mc 2 lt.
Gelatin: Cn 10 g gelatin cho vo trong cc c th tch 400 ml c sn 250ml nc ct. t
cc trn bp cch thy v khuy cho n khi gelatin tan hon ton. Rt gelatin nng vo trong bnh
nh mc 1 lt c sn 500 ml nc ct. ngui n nhit phng thm nc ct ti vch mc v
lc u. dung dch gielatin v dung dch m trn vo l thy tinh ti mu c th tch 4 lt. Lc u,
gi ni lnh v ti, dung dch bn trong khong t nht 1 thng.
Trnh t phn tch:
X l mu: Nu trong mu c cht hu c m cn xc nh hm lng Be tng s th phi x l
mu bng dung dch HNO
3
v H
2
SO
4
. Cn ch xc nh Be ha tan th lc qua mng lc 0,45 m.
To phc vi thuc th aluminon: Dng pipet ht 0; 0,1; 0,5; 1; 2; 3; 4 ml dung dch Be chun s
dng cho vo cc bnh nh mc 100 ml. Ly 50 ml dung dch mu hoc lng mu cha t hn 200
g Be cho vo bnh nh mc 100 ml. Thm vo mi bnh 2 ml EDTA ri thm nc ct ti th tch
khong 75 ml, lc u. Thm 15 ml dung dch m aluminon, ri thm nc ct ti 100 ml v lc u
hn hp. Gi yn 20 pht sau khi thm aluminon, ch khng ni sng, lc nu thy cn thit. o
102
mt quang trong cuvet c chiu dy 5 cm ti bc sng = 515 nm (knh lc mu xanh lc). Dung
dch so snh l mu trng.
Tnh kt qu:
Da vo ng chun xy dng mi tng quan hm s y = ax+b.
Trong : y : Hm lng Be
x : Mt quang
T thay gi tr mt quang o c ca mu vo s xc nh c hm lng Be.
chnh xc v lch:
Kt qu ca 32 phng th nghim khi phn tch mu tng hp cha 250 g Be/l; 40 g As/l; 240
g Se/l; 6 g V/l; cho thy Be c phn tch vi lch chun tng i l 7,13% v sai s tng
i l 13%.
7.5. Xc nh mt s tnh cht khc ca nc
7.5.1. Xc nh hm lng oxi ha tan trong nc (DO)
Lng oxi ha tan trong nc rt nh thng khong 8 - 10 mg/l. bo ha ca oxi ha tan
trong nc ngt sch 0
0
C l 14 - 15 mg/l. Thng thng lng oxi ha tan trong nc ch chim 70
- 85% lng bo ha. Lng oxi ha tan trong nc thin nhin v nc thi ph thuc vo cc hot
tnh sinh ha, ha hc v l hc trong nc. Phn tch DO l mt trong nhng mc tiu quan trng
nh gi mc nhim nc, kim tra nhng hot tnh v qu trnh x l cht thi.
xc nh DO c th s dng cc phng php nh: Phng php ci tin azid, phng php
in cc mng nhy vi oxi v my o.
Phng php ci tin azid c s dng cho mu nc cng c, cc mu nc sng...
Nguyn l ca phng php ny nh sau: Trong mi trng kim Mn
2+
b oxi ha tan trong nc
oxi ha n Mn
4+
di dng MnO
2

Mn
2+
+ 2OH
-
+ 1/2 O
2
= MnO
2
+ H
2
O
Khi c mt H
+
, Mn
4+
b I
-
kh n Mn
2+

MnO
2
+ 2I
-
+ 4H
+
= Mn
2+
+ 2H
2
O + I
2

Dng Na
2
S
2
O
3
chun lng I
2
gii phng ra vi ch th h tinh bt, t xc nh c hm
lng oxi ha tan.
Trnh t phn tch:
Ly 300 ml mu nc cho vo chai c th tch ln hn 300 ml. Thm vo 2 ml dung dch MnSO
4

v 2 ml dung dch I
-
. y nt v dc ngc chai 15 ln trn u dung dch. Thm cn thn 2 ml H-
2
SO
4
c vo thnh chai ri y nt v dc ngc chai vi ln. Ly 204 ml dung dch tng ng vi
200 ml mu nc cho vo bnh tam gic, thm vo 3 - 4 git tinh bt ri chun bng dung dch
Na
2
S
2
O
3
0,025N n khi dung dch mt mu xanh v tr nn trng ng.
Tnh kt qu:
Lng oxi ha tan c tnh theo mg/l. C 1 ml dung dch Na
2
S
2
O
3
0,025N tng ng vi 0,2
mg DO.
Ha cht:
Dung dch MnSO
4
: Ha tan 480 g MnSO
4
.4H
2
O trong nc ct, lc ri nh mc ti 1 lt.
103
Dung dch I
-
trong kim: Ha tan 500 g NaOH (hay 700g KOH) v 135 g NaI (hay 150 g KI)
trong nc ct v nh mc ti 1 lt. Thm vo dung dch ny NaN
3
ha tan trong 40 ml nc ct.
H
2
SO
4
c
H tinh bt 1%
Dung dch Na
2
S
2
O
3
0,025N: Ha tan 6,205 g Na
2
S
2
O
3
.5H
2
O trong nc ct mi si ri lm
lnh bng nc ct, thm nc ct ti 1 lt.
Ngoi phng php trn ngi ta cn dng phng php xc nh hm lng oxi ha tan trong
nc bng cch o trn in cc.
Di y l bng th hin hm lng oxi ha tan (mg/l) trong nc p sut 760 mmHg v
m tng i l 100% (theo EAWAG, 1973):
0
C 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9
0 14,60 14,56 14,52 14,48 14,44 14,40 14,36 14,33 14,29 14,25
1 14,21 14,17 14,13 14,09 14,05 14,02 13,98 13,94 13,90 13,87
2 13,83 13,79 13,75 13,72 13,68 13,64 13,61 13,57 13,54 13,50
3 13,46 13,46 13,39 13,36 13,32 13,29 13,25 13,22 13,18 13,15
4 13,11 13,08 13,04 13,01 12,98 12,94 12,91 12,88 12,84 12,81
5 12,78 12,74 12,71 12,68 12,64 12,61 12,58 12,55 12,52 12,48
6 12,45 12,42 12,39 12,36 12,33 12,29 12,26 12,23 12,20 12,17
7 12,14 12,11 12,08 12,05 12,02 11,99 11,96 11,93 11,90 11,87
8 11,84 11,81 11,78 11,76 11,73 11,70 11,67 11,64 11,61 11,58
9 11,56 11,35 11,50 11,47 11,44 11,42 11,39 11,36 11,34 11,31
10 11,28 11,25 11,23 11,20 11,17 11,15 11,12 11,10 11,07 11,04
11 11,02 10,99 10,97 10,94 10,91 10,89 10,86 10,84 10,81 10,79
12 10,76 10,74 10,72 10,69 10,67 10,64 10,62 10,59 10,57 10,55
13 10,52 10,50 10,47 10,45 10,43 10,40 10,38 10,36 10,34 10,31
14 10,29 10,27 10,24 10,22 10,20 10,18 10,15 10,13 10,11 10,09
15 10,07 10,04 10,02 10,00 9,98 9,96 9,94 9,92 9,98 9,87
16 9,85 9,83 9,81 9,79 9,77 9,75 9,73 9,71 9,69 9,67
17 9,65 9,63 9,61 9,59 9,57 9,55 9,53 9,51 9,49 9,47
18 9,45 9,43 9,41 9,39 9,37 9,36 9,34 9,32 9,30 9,28
19 9,26 9,24 9,23 9,21 9,19 9,17 9,15 9,13 9,12 9,10
20 9,08 9,06 9,05 9,03 9,01 8,99 8,98 8,96 8,94 8,92
21 8,91 8,89 8,87 8,86 8,84 8,82 8,81 8,79 8,77 8,76
22 8,74 8,72 8,71 8,69 8,67 8,66 8,64 8,63 8,61 8,59
23 8,58 8,56 8,55 8,53 8,51 8,50 8,48 8,47 8,45 8,44
24 8,42 8,41 8,39 8,38 8,36 8,35 8,33 8,32 8,30 8,29
25 8,27 8,26 8,24 8,23 8,21 8,20 8,18 8,17 8,16 8,14
104
26 8,13 8,11 8,10 8,08 8,07 8,06 8,04 8,03 8,01 8,00
27 7,99 7,97 7,96 7,94 7,93 7,92 7,90 7,89 7,88 7,86
28 7,85 7,84 7,82 7,81 7,80 7,78 7,77 7,76 7,74 7,73
29 7,72 7,70 7,69 7,68 7,66 7,65 7,64 7,63 7,61 7,60
30 7,59 7,57 7,56 7,55 7,54 7,52 7,51 7,50 7,49 7,47

Nu gi y l hm lng O
2
ha tan trong nc mt p sut xc nh th ta c.
y = S.P
m
/ 760
Trong : P
m
: p sut ti thi im xc nh
S : L hm lng O
2
ha tan trong nc ti p sut 760 mmHg
theo bng trn.
7.5.2. Xc nh nhu cu oxi ha hc (COD)
Ch s ny dng nh gi hm lng cht hu c ca nc thi v s nhim nc t nhin.
COD l lng oxi cn thit cho qu trnh oxi ha ha hc cc cht hu c trong nc thnh CO
2
v
nc.
xc nh COD ngi ta thng s dng mt cht oxi ha mnh trong mi trng axit, cht
thng c s dng l K
2
Cr
2
O
7
. Khi xy ra phn ng:

Cht hu c + K
2
Cr
2
O
7
+ H
+
CO
2
+ H
2
O + 2Cr
3+
+ 2K
+


Lng d Cr
2
O
7
2-
c chun bng dung dch mui Fe
2+
vi ch th axit phenylanthranilic,
mu ch th chuyn t tm sang xanh l cy.
Trnh t phn tch:
Ly 20 ml mu nc cho vo bnh hi lu, ri thm vo HgSO
4
(10 mg Cl
-
th cn 0,1 g HgSO
4
).
Thm vo 10 ml dung dch K
2
Cr
2
O
7
0,025N v mt vi ht thy tinh. Lp ng sinh hn thy tinh nhm.
Thm vo t t 30 ml H
2
SO
4
c c cha Ag
2
SO
4
qua phn cui ng sinh hn v lc u hn hp
trong khi thm axit. un hi lu trong hai gi. ngui v ra sinh hn hi lu bng nc ct. Pha
long hn hp bng nc ct ti th tch khong 150 ml, ngui. Chun lng dicromat d bng
mui Fe
2+
, vi ch th axit phenylanthranilic. Cng tin hnh mt th nghim mu trng nh i vi
mu phn tch.
Tnh kt qu:
COD (mg/l) = (a - b).N. 8000/ 20 ml mu
a : Th tch Fe
2+
chun mu trng (ml)
b : Th tch Fe
2+
chun mu (ml)
N : Nng ng lng ca dung dch Fe
2+

Ha cht:
K
2
Cr
2
O
7
0,025N: Ha tan 12,259 g K
2
Cr
2
O
7
sy kh hai gi 105
0
C, trong nc ct v
thm nc ti vch mc.
Ag
2
SO
4

t
0
105
H
2
SO
4
c c thm 22 g Ag
2
SO
4
cho mt chai 9 lt.
Dung dch Fe
2+
0,1N: Ha tan 39 g Fe(NH
4
)
2
SO
4
.6H
2
O tinh khit trong nc ct, thm 20 ml
H
2
SO
4
c, ngui ri nh mc ti 1 lt.
Ag
2
SO
4
tinh khit ha hc.
HgSO
4
tinh khit ha hc.
Ch th 1%: Ha tan 0,2 g axit phenylanthranilic trong 100 ml Na
2
CO
3
0,2%.
7.5.3. Xc nh nhu cu oxi sinh ha (BOD)
Nhu cu oxi sinh ha l lng oxi s dng trong qu trnh oxi ha cc cht hu c bi cc vi
sinh vt. Trong nc khi xy ra qu trnh oxi ha sinh hc th cc vi sinh vt s dng oxi ha tan. V
vy vic xc nh tng lng oxi ha tan cn thit cho qu trnh phn hu sinh hc l rt quan trng
nh gi nh hng ca dng chy i vi ngun nc.
Trong thc t, ngi ta khng th xc nh c lng oxi cn thit phn hu hon ton cht
hu c, m ch cn xc nh lng oxi cn thit cho 5 ngy u vi nhit 20
0
C trong phng ti
trnh qu trnh quang hp, ch tiu ny k hiu l BOD
5
.
Phng php xc nh:
- Chun b dung dch pha long: Nc pha long c chun b chai to, rng ming bng cch
thi khng kh sch 20
0
C vo nc ct v lc nhiu ln cho n khi bo ha oxi, sau thm 1 ml
dung dch m photphat, 1ml dung dch MgSO
4
, 1 ml CaCl
2
v 1 ml FeCl
3
, ri nh mc ti 1 lt bng
nc ct. Trung ha mu nc phn tch n pH = 7 bng H
2
SO
4
1N hay bng NaOH 1N. Pha long
mu nc trc khi xc nh bng nc hiu kh chun b trc theo cc mc sau:
0,1 - 1% i vi nhng mu nc c dng chy mnh
1 - 5% i vi nhng mu nc cng cha hoc lng
5 - 25% i vi nc b oxi ha
25 - 100% i vi nc sng b nhim
Khi pha long cn ht sc trnh khng oxi cun theo. Sau khi pha long xong cho mu vo
trong hai chai xc nh BOD (thng l chai c th tch 300 ml), ng kn nt chai, mt chai dng
5 ngy ni ti ti nhit 20
0
C, mt chai dng xc nh DO ban u trong mu pha long.
Tnh kt qu:
Lng BOD c tnh theo mg O
2
/l
BOD
5
=
P
D D
2 1


Trong :
D
1
: L lng oxi ha tan (mg/l) ca dung dch mu pha long sau 15 pht.
D
2
: L lng oxi ha tan (mg/l) trong mu sau 5 ngy
P : L h s pha long c tnh nh sau


Th tch mu nc em i phn tch
Th tch mu nc + th tch nc pha long
P =
106
Ha cht:
Dung dch m photphat: Ha tan 8,5 g KH
2
PO
4
, 21,75 K
2
HPO
4
, 33,4 g Na
2
HPO
4
.7H
2
O v
1,7g NH
4
Cl trong khong 500 ml nc ct ri nh mc ti 1 lt.
Dung dch MgSO
4
; Ha tan 22,5 g MgSO
4
.7H
2
O trong nc ri nh mc ti 1 lt.
CaCl
2
: Ha tan 27,5 g trong 1 lt nc ct
FeCl
3
: Ha tan 0,25 g FeCl
3
.6H
2
O trong 1 lt nc ct
H
2
SO
4
1N v NaOH 1N
7.5.4. Xc nh mu sc
Ni chung nc thin nhin sch khng c mu. Trong thc t nc thng c mu do s c mt
ca mt s cht mu hu c v cc hp cht ca Fe
3+
. Nc thi c th c sc thi khc nhau. Trong
nhiu trng hp mu ca nc cn do cc vi sinh vt, cc ht bn, cc thc vt sng trong nc, cc
sunfua, cc cht l lng gy nn. Trc khi xc nh mu, cn lc mu nc. i vi nc c cha
nhiu cht l lng, cn lng ri xc nh mu ca phn nc trong. Vic xc nh chnh xc v
hon ton khch quan mu ca nc l vic tng i kh, nhiu khi phi m t v sc thi v cng
mu bng li ch khng phi bng con s nh lng.
C th xc nh mu sc ca nc bng mt da trn s so snh vi mt lot mu chun hoc
bng cch ghi ph hp th ca mu nc trong min kh kin. Cch th nht r rng khng c
chnh xc, ch cho ta bit sc thi v cng gn ng ca mu ( m nht). Cch th hai chnh
xc, khch quan, nhng i hi phi c thit b t tin v khng thc hin c trong nhng iu
kin phn tch ti ch.
Di y l phng php xc nh mu sc ca nc theo cch so snh vi dy dung dch chun
c mu sc tng t v vic so snh c thc hin bng cch o trn my so mu quang in. Trong
thc t nc thng c mu sc gn vi mu ca dung dch hn hp K
2
Cr
2
O
7
v CoSO
4
, nn ngi ta
thng dng dy dung dch ca hn hp lm dy chun so snh xc nh mu ca nc.
Trnh t tin hnh:
ng chun: Chun b 10 ng o Nessler, dng pipet ly ln lt vo mi ng 1, 2, 3, 4, 5, 6, 8,
10, 12, 14 ml dung dch I v thm dung dch II n th tch 100 ml. mu ca dy dung dch chun
c biu din trn thang mu theo bng sau:
Th tch dung dch I (ml) 0 1 2 3 4 5 6 8 10 12
Th tch dung dch II (ml) 100 99 98 97 96 95 94 92 90 84
mu 0 5 10 15 20 25 30 40 50 80
o mt quang ca dung dch chun trn my so mu, s dng cuvet c chiu dy 1 - 10 mm.
xc nh mu ca mu nc, cho nc vo cuvet v tin hnh o mu nh lm i vi mu.
Ha cht v dng c:
My so mu quang in
ng o Nessler, th tch 100 ml
Dung dch I: Ha tan 0,0876 g K
2
Cr
2
O
7
, 2 g CoSO
4
.7H
2
O v 1 ml dung dch H
2
SO
4
c trong
nc ct thnh 1 lt
Dung dch II: Dung dch H
2
SO
4
long (1:1000)
107
7.5.5. Xc nh dn in ring
Nc tinh khit hu nh khng dn in, v nc phn ly rt t. Nhng cc cht tan trong nc
phn ly thnh cc cation v anion nn cc loi nc thin nhin cng nh nc thi li c tnh dn
in. dn in ring theo nh ngha l gi tr nghch o ca in tr ring (l in tr ca dung
dch nm gia hai cc c b mt 1 cm
2
v cch nhau 1 cm) ca dung dch. Ti mt nhit xc nh
dn in ring ph thuc vo nng cc cation v anion, tc l vo thnh phn ca dung dch.
xc nh dn in ring ca dung dch ngi ta dng my o dn (c th o in tr
trong khong 50 - 100000 ), dng cc cc platin v bnh ng dung dch nghin cu km theo my.
Mu nc xc nh dn in th khng c x l v nn xc nh ngay sau khi ly mu.
o dn in ca dung dch, ngi ta cho dung dch vo bnh o, nhng vo hai cc
platin, ni hai cc vi my o. dn in ring c tnh theo cng thc:
= K/R
Trong : : dn in ring
R : in tr o c
K : Hng s t l thng, c gi l hng s bnh o hoc hng s h cc. K
ph thuc vo cu to, kch thc ca h cc v hnh dng ca bnh o. Trc khi xc nh dn
in ring ca dung dch nghin cu phi xc nh K, hoc thng ni l chun ha h cc. chun
ha h cc ngi ta o in tr ca dung dch KCl c nng xc nh. K c tnh theo cng thc:
K = 1278.R.10
-6

Trong : R : Gi tr trung bnh ca in tr dung dch o c
1278 : dn in ring cu dung dch KCl 0,01M 20
0
C,
-1
.cm
-1
.
Trnh t tin hnh:
Chun ha h cc: Trng bnh o 3 ln, mi ln bng vi ml dung dch KCl 0,01M, trng h cc
cng bng dung dch . Ngm dung dch v h cc trong my iu nhit c nhit 20
0
C (kim
tra bng nhit k c chnh xc 0,1
0
C). o in tr ca dung dch trn my o dn v xc nh K
da vo cng thc trn. Cho dung dch chun vo 5 - 10 bnh v tin hnh o nh vy, ly kt qu
trung bnh tnh K.
nc vo hai bnh c trng trc 3 ln mi ln bng vi ml nc cn xc nh dn,
ngm cc bnh vo b nc ca my iu nhit iu chnh sn 20
0
C, cho n khi nc trong bnh
c c nhit . Nhng h cc vo bnh th nht nhiu ln ra h cc. Nhng h cc vo bnh
th hai v o in tr. Ghi kt qu R o c. Nu phi o nhiu mu c dn khc nhau, th mi
mu dng 3 bnh, hai bnh ra h cc, bnh th 3 o dn.
C th o nhit khc nhau, nhng phi xc nh chnh xc nhit ca nc. Ri dng
bng hiu chnh a v dn 20
0
C. dn 20
0
C c tnh theo cng thc:
= K.f.10
6
/R.
Trong : K : Hng s h cc
f : H s hiu chnh nhit
R : in tr o c.
108
Ha cht v dng c:
Dung dch KCl 0,01M: Ha tan 0,7456 g KCl tinh khit ha hc c sy kh 100
0
C v
ngui trong bnh ht m trong nc ct hai ln thnh 1 lt dung dch 20
0
C.
My o dn (dng dng xoay chiu), c th o c in tr t 50 -100000 .
My iu nhit.
109
Chng 8. Phn tch kh

8.1. Ly mu khng kh
Tng thp nht ca kh quyn n cao 11 km c gi l tng i lu. Cc kh trn ln trong
tng i lu c thnh phn tng i n nh v c ngha ln i vi i sng sinh vt. y, s
vn chuyn khng kh xy ra mnh v hnh thnh cc m my c xem nh l nhng yu t thi tit
c nh hng ti cc h sinh thi ca sinh quyn.
Bng vic s dng cc dng c c bit, ngi ta c th xc nh c cc tnh cht khc nhau
ca khng kh. Nhng phng php sau y c s dng ly mu khng kh. C 2 nhm
phng php chnh:
- Phng php tip cn ly mu t:
S dng chai hoc ng ly mu (hnh 8.1) c lm y bng cht lng c kh nng ha tan t cc
cht kh. Trong nhiu trng hp hay s dng nc c axit ha. Khi nc c tho i, khng
kh s xm nhp vo thay th. Trong phng th nghim, mu khng kh c th c chuyn sang dng
c phn tch bng cch cho cht lng tng t vo bnh ly mu.







Hnh 8.1. ng ly mu kh
Nhc im ca phng php ny l mt s cht kh c th ha tan vo cht lng. Ngc li,
cht lng cng c th bay hi vo trong mu kh. Hn na, khi ly mu kh cng nh khi chuyn cht
kh vo dng c phn tch cn phi s dng mt lng kh ln cc cht lng.
- Phng php ly mu kh:
Trong phng php ny, kh c ly vo trong bnh ly mu nh h thng bm hoc my ht
cho n khi th tch ca bnh c trao i vi khng kh t nht l 6 ln. Trong phng th nghim,
khng kh trong bnh ly mu c chuyn trc tip ti dng c phn tch bng cht lng (thch hp
nht l dng thy ngn).
Thng thng, kim tra nhng hp phn c bit nh hi cn, hi cht c trong khng kh
ca vng cng nghip, mu kh c th c a trc tip vo trong cc dng c o ti v tr cn xc
nh. Bn cht ca php o c l khc nhau t n gin nh ng hp ph vi nhng cht c bit
cho vng mu sc tng ng vi hm lng ca chng, n cc dng c t tin o CO v SO
2
.
110
Khng kh cn phn tch c bm qua "bnh phn ng" ni c sn cc cht ha hc cn thit. Sn
phm c hnh thnh c th c xc nh bng phng php so mu hoc mt s k thut khc.
ly mt lng nh mu kh, c th s dng bm ht bng nha c np y rt thun tin
ly mu v chuyn mu kh sang dng c o.
Mt s dng c khc ly mu kh l mt bnh c th bm kh vo p sut ln hn kh
quyn (nh qu bng chng hn). Do c nn p sut ln nn chng d dng chuyn sang dng c
o. Tuy nhin, do b nn p sut cao nn cc kh c th khuych tn qua v bnh vi cc tc khc
nhau. V vy, khng nn mu lu qu s nh hng n thnh phn ca chng.
i vi mt cht kh no c kh nng ha tan tt trong nc, c th dng nc hp th lm
tng hm lng ca chng cho qu trnh phn tch. Thng s dng nc c thm nhng cht thch
hp tng kh nng hp th ca chng.
Kh c phn tch c lc qua mng lc xc nh cc phn t rn bng knh hin vi hay
phng php ha hc.
quan trc khi x t nh my hoc xe c vo trong khng kh vic phn tch cn phi tin
hnh c dng t kit v ti ng x ca xe.
S dng c ly mu kh ngoi kh quyn:






8.2. Xc nh mt s tnh cht vt l ca khng kh
Cng gi: Gi c xem l yu t sinh thi quan trng v n c kh nng lm thay i khng
kh v cc yu t mi trng nh nhit , nh sng, cn bng nc,...Gi cng l yu t nh hng
n i sng ca thc vt cng nh ng vt.
Bawfort a ra 12 cp nh gi da vo tc gi nh sau (bng 8.1)
Bng 8.1. Phn loi gi
Cp gi Loi gi Tc gi (km/h)
0
1
2
3
4
5
6
7
8
Lng gi (Calm)
Kh chuyn ng nh (light air)
Gi rt nh (Light breeze)
Gi nh (Gentle breeze)
Gi mt (Fresh breeze)
Gi trung bnh (Moderate breeze)
Gi mnh (Strong breeze)
Gn lc (Near gale)
Lc (Gale)
< 1
1 - 5 (3)
6 - 11(9)
12 - 19 (16)
20 - 28 (24)
29 - 38 (34)
39 - 49 (44)
50 - 61 (55)
62 - 74 (68)
u ht
B lc bi v gi Bnh hp th B lc bo v Bm ht ng h o
lu lng v
nhit k
111
9
10
11
12
Lc mnh (Strong gale)
Bo (Storm)
Bo mnh (Violent storm)
Bo rt mnh (Hurri cane)
75 - 88 (82)
89 - 102 (96)
103 - 117 (110)
> 117
* S trong ngoc ch gi tr trung bnh
C nhiu dng c khc nhau dng o tc gi (c gi chung l my o gi Anemometer).
- Loi quay vng: C hnh dng nh hnh 8.2 gm 3 na hnh cu hng gi v lm quay ng
h o gn trc xung quanh. Loi ny c s dng rt ph bin cc trm kh tng. Tc gi
c tnh bng m/s hoc km/h.








Hnh 8.2. Thit b o gi kiu hnh chn Hnh 8.3. Thit b o gi kiu ci xay
Mt dng khc nh hnh 8.3 c 1 vng trn dt v 1 chong chng quay, c th mang vc v di
chuyn d dng.
- Loi o gi dng a p lc: a p lc c ng knh khng 30 cm. Khi gi tc ng vo a
ny s c chuyn thnh s chuyn ng ca t l chia trn bng chia .
Hng gi: Hng gi c xc nh da vo a bn t tnh. Cc hng c chia lm 16 t
l theo hng a l (hnh 8.4).


Hnh 8.4. a bn t tnh

p sut kh quyn: Khi ln cao p sut s gim, trung bnh s gim i 1/30 khi ln cao 275 m.
Tuy nhin, t l v thnh phn ca kh quyn th hu nh khng thay i tng gn mt t. p sut
khng kh khng ch thay i theo cao m cn thay i theo nhit . Ti cao 0 m (so vi mt
bin trung bnh) th p sut khng kh l 1013,25 milibars (760 mmHg). Do s bin ng ca p sut
kh quyn gia cc vng khc nhau nn hnh thnh s chuyn ng ca khng kh trn b mt t. p
112
sut kh quyn c lin quan ti nhiu yu t vt l nh thi tit v kh hu. p kh quyn cng l mt
ch tiu mi trng.
o p sut, ngi ta s dng my o (Barometer) da trn nguyn tc nng cao hay h thp
ca ct thy ngn bn trong ng thy tinh. Kt qu c biu din bng mmHg hoc milibars.
Nhit : Nhit l yu t sinh thi c cp ti rt nhiu v tc ng quan trng ca n ti
qu trnh tng hp vt cht, sinh trng v pht trin ca sinh vt.
Cc sinh vt c kh nng thch ng vi bin dao ng rng ca nhit c gi l
Eurythermal, v dao ng hp c gi l Stenothermal.
Nhit bin ng mnh trong mi trng khng kh v nc v c nh hng ti mi trng,
nht l m v gi. Tuy nhin, s dao ng nhit theo ngy m, ma c ngha quan trng hn
trong sinh thi hc so vi cc s liu n l.
Nhit k o nhit ti a v ti thiu c dng nh hnh 8.5.
Cu to gm 1 ng hnh thy tinh c dng ch U, bnh cha nhnh bn tri c dng ng hnh
thng, cn bn phi c dng hnh qu l. Phn di ca ng hnh ch U c cha y thy ngn v
phn cn li l Creosote. Bnh cha pha tri c lm y mt cch lin tc bng Cresote, cn
bnh cha dng qu l bn phi l ngt qung. Thc nhit c ch to c nh tng nhnh
tri v phi ca ng ch U, pha tri l nhit ti thiu, cn nhnh phi l nhit ti a. S xut
hin mt lp mng trn b mt lp thy ngn, nu nh c st trong mao qun, lp ny s di chuyn
theo mc thy ngn.
Bui sng, ngi ta dng mt nam chm t tnh hnh mng nga t mc thy ngn hai
nhnh. nhit k trong bng rm 24 gi, nhit s c ghi li 2 nhnh ca nhit k. Nhit ti
thiu c ghi nhn nhnh bn tri v nhit ti a c ghi nhn nhnh bn phi.



Hnh 8.5. S nhit k Hnh 8.6. S m k

Mnh vi mng
D
W
113
m tng i (RH): m biu th hm lng hi nc c trong khng kh, thng thng
dao ng trong khong 0,02 - 4% khi lng. m ph thuc rt nhiu vo cao v nhit .
m s gim dn khi ln cao v gn nh bng khng cao 8 - 10 km. m tuyt i l lng hi
nc c mt trong khng kh (biu th bng t l v khi lng) v c biu th l lng hi nc
bo ha c trong khng kh nhit v p sut no . Bin m c nh hng n qu trnh bay
hi nc. N c nh hng n nhit , nh sng v c vai tr quan trng nhm iu chnh s phn
b v hot ng ca sinh vt.
o m tng i ngi ta dng my o m loi quay s (Dial type hydrometer), loi ghi
th (Hydrographs), hay b cm ng in t (Electrical sensing device). Tuy nhin, loi o m
(Psychrometer) c s dng nhiu nht.
My o m (Psychrometer) gm 2 bu nhit k (hnh 8.6), mt bn kh (O) v mt bn t (W).
Bu nhit k t c duy tr m tuyt i bng cch bc quanh n mt lp vi mng c nhng
vo trong nc.
8.3. Mt s tnh cht ha hc ca khng kh
Hn hp ca nhiu loi kh vi cc ht nh rn v lng to thnh 1 lp v kh quyn bao quanh
Tri t n cao trn di 10.000 km. Trong , khong 95% vt cht ca kh quyn tp trung
cao di 19 km.
Bng 8.2. Thnh phn ca khng kh kh, sch cao ca mt nc bin
Cht kh Hm lng *
N
2
O
2

CO
2

CO
N
2
O (i nit oxit)
NO
2
(Nit ioxit)
SO
2

He(Heli)
Ne (Neon)
Ar (Argon)
Kr (Krypton)
Xe (Xenon)
NH
3
(Amoniac)
H
2
(Hydro)
CH
4
(Metan)
O
3
(Ozon)
78,085 %
20,916 %
320 ppm
0,1 ppm
0,5 ppm
0,02 ppm
1 ppm
5,24 ppm
18,18 ppm
9340 ppm (0,934%)
1,14 ppm
0,087 ppm
0 n vt
0,5 ppm
2 ppm
0,02 - 0,07 ppm
(thay i theo ma)
* : % theo th tch
Bng 8.2 cho thy, thnh phn ca khng kh sch v kh cao ngay trn mt bin, thnh
phn chnh l N
2
v O
2
v tng i n nh theo thi gian. Mc d mt lng ln cc loi nhin liu
114
ha thch c t chy trong th k ny, hm lng O
2
trong kh quyn vn khng thay i k t
khi o c cc s liu chnh xc u tin. O
2
s dng cho cc qu trnh t chy, h hp v phn hy
cht hu c li c b li nh qu trnh quang hp.
Cc loi oxit ca nit, lu hunh, cc bon v ozn c xem l nhng cht gy nhim quan
trng. C s bin i chm v s tch t CO
2
v iu ny c th c nh hng n kh hu Tri t.
Hi nc c mt trong kh quyn c nng thay i thng xuyn. Bi v cc sol kh (aerosol)
c mt trong khng kh v nhiu lc, nhiu ni cht nhim quan trng.
Nhng cht ring bit: Nhng cht ring bit trong khng kh c th gp dng rn hoc lng.
Cc dng rn nh khi, bi. Cn dng lng nh sng m, sng mui. Chng l nhng phn t c
kch thc ln hn phn t nhng li nh tn ti trong khng kh v c gi l sol kh.
Hm lng ca cc cht c bit ny trong khng kh thay i mnh. N c ngun gc t cc qu
trnh t nhin nh gi, ni la, phn hoa, bo t, cc phn phn hy ca cc cht hu c,... v c th
do hot ng ca con ngi nh cng nghip khai khong, t nhin liu,...
Cc cht l lng trong khng kh c th gy nhiu bnh nh d ng, hen xuyn, vim phi, vim
cung phi. Trong t nhin mt s loi cy c kh nng ht thu bi lm sch khng kh.
Nhng phng php sau y c s dng nh gi cc cht c bit trong khng kh:
1. Phng php trng lc: Dng nh gi cc cp ht bi 1 m cc vng cng nghip hoc
thnh ph. Phng php ny dng mt bnh thy tinh rng ming, sch ni cn xc nh. Sau mt
thi gian nht nh (vi gi hoc vi ngy), bi lng c thu gom v em cn. Kt qu c biu
din bng gam (khi lng bi trn mt n v din tch trong mt n v thi gian).
2. Phng php va p: Phng php ny s dng dng c va p nh hnh 8.7. Nguyn l
chung ca phng php ny l cc phn t bi rn s khng c kh nng b thi i khi c s thay i
nhanh chng hng thi, chng b cn li v ri xung ti cc b mt Con (Collecting surface). Tuy
nhin, phng php ny khng c kh nng thu c cc ht bi c kch thc rt nh.












Da vo cng sut ca my ht (hay my bm) m bit c lng khng kh thi qua dng c
va p ny. T c th tnh c khi lng bi trn mt n v th tch khng kh (nh mg/m
3
).
u ra
u vo
Hnh 8.7. Thit b va p

115
3. Phng php kt ta tnh in: Phng php ny s dng dng c tnh in c cha mt ct
ion tch in m rt cao (15.000 - 30.000 V.D.C) v mt dng c ht thu c tch in dng t my
bin th (hoc my chnh lu).
Trong phng php ny, mt th tch kh nht nh c a qua dng c kt ta tnh in. Cc
phn t rn s c tch in m ct ion m s c kt ta v thu nhn ng tch in dng. Cc
phn t rn c tp trung em cn khi lng v c th em m s lng di knh hin vi.
4. Phng php lc: Trong phng php ny mt th tch ln khng kh c cho qua mt mng
lc (hoc giy lc bit trc khi lng). Sau , em cn li khi lng v tnh ton lng bi
(khi lng bi/ th tch kh). Phng php ny c th tch c cc ht bi c kch thc c 0,05
m.
Bi v cch tch bi trong khng kh: Cc th l lng trong khng kh lm nh hng n nh
sng. N c th bm bi gy bn qun o, dng, lm mt mu cc cng trnh xy dng v i khi
xut hin cc phn ng ha hc.
Kch thc ca chng c th thay i, thng thng trn 90% c ng knh trn 30 m, v ln
nht l 1000 m. Nhng ht ln hn d dng b lng ng do trng lc. Nhng ht nh (< 100 m) c
th tn ti l lng trong khng kh trong nhng thi gian khc nhau.
Nhng ht c kch thc 5 - 7 m t khi xm nhp vo phi, m ch yu l ht kch thc 0,25 - 5
m.
Mt cc ht m c o bng dng c o c (Nephelalometer) da trn nh hng ca
cc ht bi m n s truyn nh sng. Khng kh vi tc c nh (0,01 m
3
/ pht) c cho qua
mt knh quang hc ti 1 bung chiu sng bng 1 chm tia sng. Mt s tia sng b phn tn do cc
ht nh (< 20 m) v cng ca bc x ny s c o bng dng c o.
Dng c o ny ch cho chnh xc cao khi kch thc ca ht bi l tng t nhau.
Mt dng c khc l cho mt lng khng kh nht nh i qua mt mi trng lc trng, mi
trng s b lm "ti" i khi c cc cht bi kh c gi li. T kt qu ny c th xc nh c
lng cht bi trong khng kh.
Cc cht c bit: Qu trnh sn xut cng nghip c th thi ra nhiu phn t mn nh hn axit,
bi silic, vi, hp phn kim loi,... thm ch rt nh nh ch hnh thnh do t xng du (< 1m). Hm
lng ch thng rt nh < 1 ng/m
3
vng khng nhim, n 3 g/m
3
ng ph, hoc 50 - 70
g/m
3
ng giao thng c mt xe c ln. Cc phn t ny rt d xm nhp vo phi.
phn tch cc cht c bit trong khng kh, c th lc mt th tch ln khng kh trong mt
thi gian di. Mt phn cht thu c (khong 10%) c ha tan trong axit, lc ri em xc nh cc
nguyn t cn thit bng cc phng php phn tch vi lng (nh hp th nguyn t). Hm lng ch,
km, st trong cc cht bi kh thnh ph dao ng trong khong 0,1 - 6 g/m
3
.
a. CO (cacbon oxit):
CO l kh c ph bin trong kh quyn. Khi xe t chy, kh thi chy kit thng cha <1%
CO, nhng khi tng ga c th cha 5% hoc cao hn.
Hm lng CO trong khng kh ph thuc nhiu vo mt xe chy v mc dng v khi
ng.
V d, hm lng CO ng giao thng c trnh by bng 8.3.
116
Bng 8.3. S bin ng hm lng CO trong khng kh ng giao thng theo thi gian
Hm lng CO (ppm) Thi gian
Ngy 1
Ngy 2 Ngy 3
10 gi sng
11 gi sng
12 gi tra
1 gi chiu
3 gi chiu
5 gi chiu
9,3
9,0
10,4
8,7
7,9
12,4
8,0
11,8
10,4
8,2
10,5
-
-
3,6
6,3
11,1
5,2
7,4

CO kh c hi i vi con ngi. N phn ng vi hemoglobin nhanh gp 300 ln so vi O
2

hnh thnh cacboxy hemoglobin, hn ch qu trnh vn chuyn O
2
trong mu. mc thp, CO gy
triu chng au u, chng mt, mt mi, nh hng n thn kinh. Cao hn, c th dn n bun nn,
tim p nhanh, kh th thm ch t vong.
Vic quan trc nng CO trong khng kh cn c tin hnh u n v lin tc nh gi
mc nhim.
Mt phng php c p dng rng ri phn tch CO l da vo kh nng hp th chn lc
di bc x hng ngoi.
Mu kh c a qua mt b phn lc th (nh h thng bm) trong iu kin nhit thp
lm ng bng hi nc. Sau a vo t bo o (hnh 8.8). Mt t bo tng t (i chng) c
np y nit, v c hai c chiu bng nh sng . Nng lng i qua ti h thng o t hai t bo
s khng bng nhau nu mu cha CO (v s hp th phn t). S khc nhau ny s c xc nh v
chuyn n b ghi.
Vi cc my o ti hin trng, sai s khi o nng 10 ppm c th l 1,5 ppm.
Nhng my phn tch kh hng ngoi hin i c ch to xc nh nhng kh ring bit rt
thch hp o CO trong khng kh. Tuy nhin cng c th b nh hng bi mt s loi kh khc
cng c bc sng tng t.
u ly
mu
B phn
lm lnh
Qut
B nh c
Mu
Ngun
IR

Lc
So snh
B ghi
Hnh 8.8. S pht hin CO

117
Phng php khc xc nh CO l chuyn CO thnh CH
4
nh cc phn ng ha hc thch hp.
Sau , xc nh lng CH
4
to thnh.
b. CO
2
(kh cacbonic):
CO
2
l kh rt quan trng trong qu trnh quang hp ca cy xanh. Qu trnh quang hp nhiu
loi cy xanh s tng khi hm lng CO
2
tng ln. Tuy nhin, khi hm lng CO
2
trong khng kh qu
cao s km hm qu trnh h hp ca cc c th sng.
Theo cc nh nghin cu v kh hu th khi c s thay i hm lng CO
2
trong kh quyn, d ch
rt nh, cng c th c nh hng ln n kh hu. Do vy, theo di s bin i hm lng CO
2
trong
kh quyn s c ngha thc tin hn so vi s bin ng ca O
2
v mt sinh thi hc.
Lng CO
2
tch lu trong i dng l rt ln v n thng c s trao i vi kh quyn. Trn lc
a, qu trnh h hp ca sinh vt cng vi qu trnh t chy sinh khi, nhin liu v cc hot ng
trong sn xut nng nghip cng ng gp ng k vo ngun CO
2
trong kh quyn.
Xc nh CO
2
bng dng c Zecondroff (hnh 8.9).










Ha tan 0,53 g Na
2
CO
3
trong 100 ml nc ct c un si v ngui. Thm 0,1 g
phenolphtalein, lc u. Ly 1ml dung dch ny pha long bng nc ct n 100 ml c dung dch
phn ng.
Cho 10 ml dung dch phn ng ca Na
2
CO
3
vo trong dng c Zecondroff (hnh 8.9). dng c
trong mi trng trong sch, bm kh bng qu bp cao su, lc nh sau mi ln bm kh. Lp li cho
n khi va xut hin mu hng trong dung dch Na
2
CO
3
. Ghi s ln bm kh (X). Ra sch dng c,
ri cho 10 ml dung dch phn ng vi Na
2
CO
3
mi vo v t dng c Zecondroff vo ni cn xc
nh CO
2
.
Lp li ng tc bm kh nh trn n khi dung dch Na
2
CO
3
xut hin mu hng. Ghi s ln
bm kh (S).
Kt qu c tnh nh sau:
CO
2
(%) = X/ S.25
Trong : X: S ln bm kh mi trng sch
S : S ln bm kh mi trng cn o.
c. NO
x
(cc oxit nit):
Cc kh NO
x
thi ra cc ng c xe m nhin liu c t chy, iu kin khng ti l <
30 ppm v tng ln n > 1000 ppm trong lc chy hoc tng tc. Cc kh NO
x
c th gy hin tng
ng ra
Bm
Hnh 8.9. Dng c ly mu CO
2


118
sng m mc d hm lng ca chng thp trong kh quyn (gii hn c a ra l 0,05ppm/nm
theo US).
NO
2
(nit ioxit) trong kh quyn c th b kh thnh NO (nit xit) di tc dng ca cc tia cc
tm.
NO
2
phnngquangho
kh

NO + O
O
2
+ O O
3

Oxi nguyn t c mt cng c th phn ng vi cc hydrocacbon (CH
4
, C
2
H
4
, toluen,...) hnh
thnh cc cht nhim th sinh nh focmandehit, peoxiaxetyl nitrat (PAN).
NO v NO
2
c th c xc nh da trn nguyn l ca vic s dng cc tia hng ngoi.
xc nh NO
2
thng dng mt my lc hi (Scrubbing). Mt dung dch c kh nng chuyn
chng thnh hp cht mu. Phn ng to thnh mu thng bao gm axit sunfuaric v mt amin thm
(N-1-(naphtyl) - etylen diamin dihydro clorua). Mt chm sng c chiu qua t bo cha mu,
cng mu s c xc nh nh my so mu quang in.
xc nh NO
x
trc ht cn oxi ha chng n NO
2
bng cch cho qua dung dch kali
pemanganat ( axit ha). Mu kh s c ln vi ozn c hnh thnh:
NO + O
2
NO
2
*
+ O
3

Qu trnh bin i NO
2
*
(hot tnh) sang NO
2
s gii phng nng lng di dng bc x:
NO
2
*
NO
2
+ h (nh sng)
Cng pht sng c o bng t bo nhy
c. SO
2
(sunfua dioxit):
Lng SO
2
c pht thi vo kh quyn t qu trnh sn xut cng nghip (nh my sn xut
axit, nh my in), giao thng...
0
1
2
3
4
5
6
7
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22
ppm SO2
Ngy
Tun

Hnh 8.10. Gi tr trung bnh ca SO
2
tai mt im quan trc trong 3 tun
Cng nh CO, vic quan trc cn phi c tin hnh theo thi gian trung bnh (v d nh 0,02
ppm/ nm, 0,10 ppm/ 2 gi). Nhng thng tin a ra cng cn ch r thi gian quan trc v n v o
c.
SO
2
cng l kh gy nhim ph bin. Ngun pht thi chnh l do t chy nhin liu ha thch.
N c th gy nh hng n mt, h thng h hp, au u hoc th gp. Trong kh quyn, SO
2
c
th kt hp vi nc hnh thnh axit to nn ma axit gy nh hng n sc khe con ngi, i
sng ca ng, thc vt v ph hy cc cng trnh vn ha.
Phng php Castle mi (New Castle Method)
119
Hnh 8.11 gii thiu s mt loi dng c xc nh SO
2
.
Khng kh c a qua mt dng c (khong 0,01 m
3
/ h), qua h thng lc tch bi sau
qua si dy bc nng loi tr cc cht nh hydro sunfua, ozon, clorin,... Kh sau khi lc c
chuyn qua dung dch brom. Mt phn brom s b SO
2
kh ri c a n in cc. Cng dng
in sinh ra s tng quan vi hm lng SO
2
trong khng kh. o i chng bng cch cho khng
kh qua ct lc bng than hot tnh loi SO
2
. Nu tin hnh phn tch cn thn, lng bi v lng
SO
2
b hp ph c gim n ti thiu th sai s mc di 15%.










Phng php o dn in (Conductimetric method):
Cho mt th tch kh bit qua mt dung dch H
2
SO
4
v H
2
O
2
. SO
2
c mt trong khng kh b
xi ha n H
2
SO
4
v vy lm tng dn in ca dung dch. T kt qu o dn c th tnh c
lng SO
2
trong khng kh.
Phng php in ha (Electrometric method):
Mu khng kh c cho qua mt dung dch in ly KBr 0,1M trong H
2
SO
4
2N. Lng SO
2
trong
khng kh s ha tan v lm gim nng bromua. Do , nng thay i c o bng in cc, t
tnh ra SO
2
trong khng kh. Phng php ny thch hp o lin tc mu kh.
Phng php West - Gacke (Pararosanilin method):
Mt th tch kh bit c cho qua dung dch natri tetraclomecurat 0,1N. Dung dch ny sau
c cho phn ng vi formaldehyd v pararosanilin s to thnh mu tm.
S dng phng php so mu quang in t tnh ra c lng SO
2
trong khng kh. Phng
php ny cho php xc nh SO
2
trong phm vi dao ng t 0,002 n 5ppm.
Phng php pht x ngn la (Flame emission method):
Phng php ny o tng lng lu hunh (SO
2
, SO
3
, H
2
S v mecaptan) trong khng kh. Mu
khng kh c cho qua hn hp d hydro v t chy trong mt quang k ngn la (Flame
photometer). nh sng pht ra c o bc sng 394 nm v tng hm lng lu hunh c th c
xc nh.
- Hydrocacbon sau khi t nhin liu: Cc hydrocacbon cn li sau khi t nhin liu cc ng
c ch yu l cc ankan, cc hp cht thm cng vi cc sn phm xi ha tng phn ca chng
(formaldehyd, acetaldehyd,...). Cc hydrocacbon s c hm lng cao nht vo cc gi c mt giao
thng cao vo cc bui sng. M, hm lng trung bnh trong 3 gi (t 6 - 9 gi) l 0,24 ppm.
Nhng gi sau , di nh sng mt tri, s xy ra phn ng quang ha v hnh thnh cc cht
ng
vo b
lc
Than lc
B lm sch
Bm
H thng
cm ng
H thng
cp brm
B phn phn
ng
B o
B
ghi
KBr
Br2
H2S
Hnh 8.11. S pht hin SO
2

120
nhim khc nh: NO
2
, O
3
, aldehyd, xeton, peroxycaxyl nitrat (PAN, nh CH
3
COO
2
NO
2
) v ankyl
nitrat. Cc sn phm th sinh ny s lm tng lng sng m quang ha.
Vi c ch phc tp nh vy, hm lng ca tng hp phn n l s c s dao ng rt rng
trong ngy (bng 8.4).
Bng 8.4. Hm lng cc cht nhim gy sng m quang ha
Cht nhim Khong dao ng
- Cacbon oxit
- Tng hydrocacbon
Cht thm
Aldehyd
Anken
- Nitric oxid
- Nit dioxit
- Peroxyaxyl nitrat
- zon
200 - 2.000
20 - 50
10 - 30
5 - 25
2 - 6
1 - 15
5 - 20
1 - 4
2 - 20

Ngun thi hydrocacbon (metan, etan, toluen,...) ch yu l t qu trnh t nhin liu ha thch
v cng nghip ha cht. Cc hydrocacbon trong khng kh c th kt hp vi cc ha cht khc nh
nit hnh thnh cht nhim th sinh v gy nn sng m quang ha gy c hi cho con ngi
v cc sinh vt khc.
Vic phn chia v xc nh cc loi hydrocacbon thng da trn phng php sc k hoc
phng php o ph.
+ Phng php sc k: Hn hp kh c bm t bnh cha kh (nit hoc heli) qua mt ng dn
di pha trong c ph bng du khng bay hi. Mi hp phn ca hn hp s c thi trong ng
vi cc tc khc nhau do phn ng ca chng vi lp v ng dn. Detect gn u ra ca ng s
cho bit kt qu ca mi hp phn thi qua. Do iu chnh chnh xc tc thi kh v nhit , mi
hp phn kh s c xc nh da trn c s thi gian thi qua ng.
+ Phng php o ph: Dng kh c i qua dng c o ph. Cc loi phn t s c phn bit
nh cc vch ph khc nhau. Trong qu trnh ion ha, cc cht hu c s bin thnh cc ion hoc cc
hp phn ring r. Tt c cc hp phn c tch in s c chuyn qua dng c o in tch v
min t tnh. Chng c phn tn da trn c s t l khi lng/in tch.
8.4. Mt s phng php phn tch nh tnh kh
phn tch nh tnh cc kh c trong mu phn tch, cn tin hnh cc php th c bn sau:
a. Dung dch nc c phn ng kim:

Hp th kh bng H
2
SO
4
v kho st dung dch Hp th kh bng KOH
Mu th vi thuc th Nessler Phn ng vi natri nitro pruxit Mu th vi Ba (OH)
2

Kt ta Kt ta trng V axeton V axetandehit Kt ta trng: CO
2

121
mu vng:
NH
3

hay vng:
metylamin,
imetylamin
Mu tm:
metylamin
Mu xanh l:
imetylamin.
Khng phn ng
NH
3
v
trimetylamin

b. Dung dch nc c phn ng axit
Hp th kh bng KOH v kho st dung dch
Mu nc vi AgNO
3

Kt ta trng:
HCl, Cl
2

Kt ta trng
hi vng: HBr
Mu th vi thuc
th Lunghe -Ilosvai
*

Phn ng vi
natrinitropruxit v
km sunfat
Phn ng vi
cadmi axetat
Lc vi nc clo v chit bng
cloroform
Mu nu hi vng:
HBr c mt HCl
Mu hng:
cc kh nit
Mu hng: SO
2
Kt ta vng:
H
2
S
* Thuc th Lunghe - Ilosvai:
Trn khi ngui mt dung dch ca 2g axit sunfanilic trong hn hp ca 400 ml nc v 100 ml
axit axetic kt tinh (cn tin hnh ha tan vi iu kin khng c mt khng kh) v dung dch ca 0,5
g -naphtylamin trong 100 ml axit axetic kt tinh pha long bi 400ml nc.
c. Kho st kh ban u:
Phn ng vi anilin To ra mu xanh
Beclanh hay st
sulfoxianua
Mu th vi palai
imetyl glioximat v
niken clorua
Phn ng vi bari
hiroxit
Kt ta khng mu ca
iphenyl ure: c mt
photphen; HCl khng cn
tr phn ng
HCN v (CN)
2
;
(CN)
2
c mt HCN
Kt ta :
HCN v (CN)
2

Kt ta trng: CO
2
Mun pht hin nhanh v nhy mt s cu t trong hn hp kh c th dng giy
lc thm cc dung dch khc nhau. V d:
- Lu hunh ioxit
- Hiro asenua
- Hiro xianua
- Photgen
- Cc oxit nit
- Clo
- Cacbon sunfua
- Cacbon oxit
- Hiro sunfua
- Tinh bt, kali ioua, kali ioat
- Thy ngn (II) clorua
- Cng g , bc nitrat
- iphenylamin, v p- imetylamino-benzandehit
- Thuc th Lunghe- Ilosvai
- ortoliddin
- Dietylamino, ng axetat
- Palai (II) clorua
- Ch axetat
Nhiu hng (v d hng Drager Werk) ch to ra nhng dng c dng xc nh vt kh,
trong t nhng ng cha cc thuc th cho php xc nh nh tnh v bn nh lng mt s kh
v hi (tnh ra mg/l).
122
Amoniac
Benzen
Metyl bromua
Hi nc
Lu hunh ioxit
0,05 - 5
50
3 - 50
1 - 100
0,05 - 10,0
Cc hirocacbon ca phn on xng v benzen
Clo
Hiro xianua
Ru etylic
5 - 100
0,002 - 0,5
0,001 - 0,15
2,50
Cc kh nitro
Cacbon oxit (theo %)
Thy ngn
Hiro sunfua
Cacbon sunfua
0,02 - 1,0
0,01 - 0,5
5.10
-4

0,05 - 2,0
0,04 - 50,0

Pht hin cacbon oxit: dung dch palai (II) clorua dng b kh bi cacbon oxit, ng thi to
ra palai kim loi.
Cho kh kho st vi tc 1 l/gi i qua bn bnh ra kh nh, trong bnh th nht v bnh
th ba np dung dch KOH 33%, bnh th hai - oleum, bnh th t - axit sunfuric c. Cc bnh ny
dng tinh ch kh khi etylen, axetylen, cc hi benzen, amoniac v hidrosunfua, nhng cht ny
cng phn ng vi palai (II) clorua. Sau kh tinh ch i vo bnh ra nh cha dung dch
Pd(Cl)
2
0,005N, bnh ny c cu to m bo cho cacbon oxit hp th mnh. Nu sau vi pht c
nhng tinh th nh mu en ca Pd lng xung th tha nhn nng cacbon oxit bng 0,1%. S xut
hin nhanh vn c (sau 3 pht) v s hnh thnh kt ta nh ca Pd sau 15 pht chng t nng
cacbon oxit bng 0,03%, cn vn c xut hin sau 15 pht v kt ta to thnh sau 1 gi xc nhn
hm lng cacbon oxit bng 0,015%.
Mu th vi giy lc tm dung dch palai (II) clorua km nhy hn.
Mt phng php rt nhy pht hin cacbon oxit c Vin Tiu chun Quc gia M xy
dng. Trong silicagen c tm bng dung dch amoni molipat v palai sunfat gi vai tr cht
xc tc. Phc silico-molipat to ra s kh cacbon oxit ti xanh molipen.
Pht hin axetylen: Thuc th Ilosvai tng tc vi axetylen to ra mt kt ta mu sm, cn
vi butaien (iaxetylen) cho kt ta mu gch. Cc kt ta mu vng s thu c khi tng tc vi
propin; vinyl axetylen v butin-1, butin-2, cng nh cc iolefin khng to ra kt ta.
8.5. Phng php nh lng mt s ch tiu trong khng kh
8.5.1. Xc nh hm lng bi
a. Phng php khi lng xc nh bi lng:
Nguyn l: Phng php da trn s cn dng c hng mu c phn ng cht bt dnh trc v
sau khi ly mu xc nh nhanh lng bi lng trong thi gian khng ma. Kt qu c biu th
bng g/m
2
.ngy hoc mg/m
2
. ngy.
123
Dng c:
Khay hng mu: bng nhm hoc bng thy tinh - khay hng c chiu dy 1mm. chiu cao 11
mm. ng knh trong 85 mm, din tch hng 57cm
2
. c bi mt lp vadlin vi khi lng trong
khong t 50 mg - 60 mg; sy trong t sy t 5 - 10 pht nhit 40
0
C to mt bng u trn
khay.
Khay c y np, cho vo ti PE, xp trong hp bo qun.
Ly mu:
Khay ly mu bi lng kh c t trn cc gi cao ng nht cch mt t 1,5m hoc
3,5m.
im ly mu phi b tr ni thong gi t mi pha, khong cch gia cc im ly mu vi
cc vt cn (nh cao tng, cy cao...) phi m bo sao cho gc to thnh gia nh ca vt cn vi
im o v mt nm ngang khng ln hn 30
0
.
S lng mu, s phn b cc im ly mu trong khu vc quan tm c xc nh theo cc yu
cu c th nhng khng t hn 4 mu cho mi im o.
Thi gian hng mi mu bi lng kh khu cng nghip, dn c tp trung khng t hn 24 gi
nhng khng qu 7 ngy.
X l mu:
Dng khn sch lau cn thn bn ngoi khay, sau t vo t sy, sy nhit 40
0
C trong 2
gi.
Sau khi sy, cn khay hng trn cn phn tch vi chnh xc 0,1mg.
Tnh ton kt qu:
Bi lng =
t S
m m
.
1 2


Trong : m
1
, m
2
: Kt qu cn khay trc v sau khi hng mu (g, mg)
S : Din tch hng mu m
2

t : Thi gian hng mu, ngy (24 gi)
b. Phng php xc nh lng bi lng tng cng:
Nguyn l: Phng php da trn vic cn lng bi thu c trong bnh hng mu bao gm
dng ha tan trong nc. S dng xc nh lng bi lng tng cng thng, kt qu c biu th
bng g/m
2
hoc tn/km
2
.
Dng c:
Dng c ly mu: Bnh hng mu c hnh tr, y phng, ng knh khng nh hn 12 cm,
chiu dy khong nh hn 2 ln ng knh ming. Chiu dy ca thnh bnh khng qu 3 mm.
C th lm bng thy tinh, nha hoc kim loi khng r.
Ha cht:
Ha cht chng to, nm...cloroform hoc hiro peroxit, benzen clorua... loi tinh khit phn
tch.
Nc ct hai ln.
Ly mu:
124
V tr t im hng mu nh phng php trn.
Thi gian ly mu l 10 ngy hoc 30 ngy.
Trc khi ly mu c ra sch, trng nc ct, y np.
Trc khi t ly mu cho vo bnh hng 250ml nc ct, 2-4ml ha cht chng to, nm.
Trong thi gian ly mu, cn b sung nc ct gi mu, trnh bnh hng b kh. Trong qu
trnh hng mu nu lng nc ma hng c trung bnh t 2/3 cao ca bnh hng, thay bnh
hng khc hng mu tip, cc mu ny ti mi im trong cng khong thi gian ly mu (10 hoc
30 ngy) c th x l ring bit ri cng gp kt qu.
Cch tin hnh:
Xc nh cc cht khng ha tan trong nc m
1
:
- B cc vt ngoi lai khng mang tnh cht bi: c th dng panh gp cc vt ngoi lai c kch
thc ln hn 1 mm, trc khi b cc vt ny i cn trng qua nc ct, nc ct thu c nhp vo
mu chung. Hoc c th lc qua ry 1 mm, dng nc ct trng ra bnh hng cho qua ry v nhp
nc ny vo mu chung.
- Lc ton b mu qua phu lc thy tinh xp, sch, kh bit trc khi lng.
- Dng nc ct ra cn trn phu, nc ny nhp vo mu chung.
- Sy kh phu lc thy tinh xp vi cn 105
0
C trong 2 gi lm ngui trong bnh ht m, cn
vi chnh xc 0,1 mg.
Hiu ca hai ln cn phu thy tinh xp trc v sau khi lc l lng cht khng tan trong nc,
m
1
.
Xc nh lng cht ha tan trong nc m
2
:
- Xc nh ton b th tch ca mu sau khi lc bng ng ong: V ml.
- Ly i din 250 ml dung dch mu lc cho vo cc t, cho bc hi ht trn bp cch thy, sau
sy kh 105
0
C trong 2 gi, cho ngui trong bnh ht m ri cn trn cn phn tch vi chnh
xc 0,1 mg.
- Sy n khi lng khng i.
- Tng lng cht ha tan trong nc: m
2
=
250
.m V
(g hoc mg)
Lng bi lng tng cng thng tnh bng g/m
2
hay mg/m
2
:
B
LT
=
S
2 1
m m +

S: l din tch ming bnh hng, m
2
.
Trong trng hp ly mu 10 ngy, lng bi lng thng l tng ca 3 kt qu bi lng (10 ngy)
trong thng .
8.5.2. Xc nh nit oxit v nit ioxit
Nit oxit v nit ioxit c xc nh bng phng php gin tip nh sau. Dng dung dch
pemanganat x l hn hp kh cha cc oxit nit. Khi nit oxit v nit i oxit c oxi ha n
nitrat:
5NO + 3MnO
4
-
+ 4H
+
5NO
3
-
+ 3Mn
2+
+ 2H
2
O
125
10NO
2
+ 5H
2
O 5HNO
2
+ 5HNO
3

5NO
2
-
+ 2MnO
4
-
+ 6H
+
5NO
3
-
+ 2Mn
2+
+ 3H
2
O
Lng nitrat to ra tng ng vi hm lng ton phn ca nit oxit va nit i oxit.
Lng pemanganat dng oxi ha cc nit oxit n nitrat, c xc nh bng cch thm
mt lng d dung dch st (II) sunfat sau chun lng d bng dung dch kali pemanganat, cn
hm lng nitrat th chun tip theo bng dung dch st (II) sunfat trong mi trng axit sunfuric c.
Xc nh im tng ng theo phn ng to thnh sn phm kt hp Fe
2
(SO
4
)
3
.2NO lm cho dung
dch c mu hng.
Tin hnh xc nh: Vic xc nh c tin hnh trong pipet c chun ha v c cu trc
c bit. Rt chn khng trong pipet trc, ri a qua phu vo 25 ml dung dch kali pemanganat
0,5N v trng phu bng mt lng nc o trc. Sau cho hn hp kh kho st vo pipet qua mt
kha 3 nhnh, cn bng nhit v p sut, lc mnh pipet trong vng 10 pht. Sau khi lm lnh pipet
trong nc ln ( to ra p sut thp) cho vo 25 ml dung dch st (II) sunfat 0,5N v mt t
nc ( trng phu) v lc pipet trong mt lc. Ht cht lng b mt mu ra khi pipet qua kha 3
nhnh vo bnh hnh nn v trng k pipet bng nc ct. Chun lng d st (II) sunfat bng dung
dch kali pemanganat 0,5N. Nh vy xc nh c lng dung dch kali pemanganat tiu tn oxi
ha NO v NO
2
.
Mun xc nh hm lng ton phn ca nit ( chuyn thnh nitrat) ngi ta chuyn ton b
dung dch cn chun vo bnh nh mc dung tch 500 ml, trng bng mt lng nh nc ct. Ri
va cn thn thm nhng lng nh axit sunfuric c, va lin tc lm lnh bnh bng hn hp nc
v nc , dng axit sunfuric a th tch dung dch n vch mc. Dng pipet ht 2 mu, mi mu
100 ml dung dch thu c vo mt bnh nn c dung tch 500 ml. Thm vi tinh th kali bicromat (
ui oxi ha tan) v va lin tc xoay bnh va chun bng dung dch st (II) sunfat 0,5N. u tin
dung dch khng mu, ri c mu lc hi vng nht, v ti im tng ng c mu hng. Lng d
ca st (II) sunfat to cho dung dch mu ta m.
Tnh kt qu: Theo nhng phng trnh phn ng trnh by trn, lng chung ca cc kh NO
v NO
2
tng ng vi lng nitrat to thnh. Da theo nhng phn ng trn xc nh th tch
cu nit oxit v nit i oxit ta c phng trnh sau:

ml NO = - ml NO
2
= -


Trong : N : Lng chung ca cc kh NO v NO
2
(ml)
P : Lng dung dch kali pemanganat 0,5N dng oxi ha (ml)
Trong chun lng nitrat bng php chun tip theo vi st (II) sunfat, 1 ml st (II) sunfat
0,5N tng ng vi 5,6 ml kh trn.
8.5.3. Xc nh hm lng lu hunh ioxit
Xc nh lu hunh theo phng php trc quang thorin:
P
0,1786
N
2
3N
2
P
0,1786
126
Phng php ny c dng xc nh nng ca lu hunh ioxit trong khng kh xung
quanh khong nng t 3,5 - 150 g/ m
3
vi th tch mu ly l 2 m
3
v th tch dung dch mu l
50 ml. Vi nhng nng cao hn, phi pha long trc khi xc nh.
Nguyn l: Cho mu khng kh i qua dung dch hyro peroxit ( c axit ha) trong mt thi
gian quy nh. Lng SO
2
c trong mu s c hp th v oxi ha thnh SO
4
2-
. Kt ta lng SO
4
2-

di dng BaSO
4
bng mt lng Ba(ClO
4
)
2
d. Bari d c xc nh bng cch cho to phc mu
vi thorin v o bc sng 520 nm.
Ha cht:
Hyro peroxit (H
2
O
2
) 27 - 30%
Dung dch hp th: Pha long 10 ml dung dch hyro peroxit 27% vi nc thnh 1000 ml.
iu chnh pH dung dch v khong 4 - 4,5 bng dung dch axit pecloric, dng in cc pH kim
tra.
Axit pecloric nng 0,1 mol/ l: Cho 4,3 ml dung dch axit pecloric 72% vo bnh nh mc,
thm nc ct n vch mc v trn u.
Dung dch bari peclorat: Ha tan 0,252 g Ba(ClO
4
)
2
trong mt lng nh axit pecloric 0,1
mol/ l trong bnh nh mc 250 ml ri nh mc n vch mc bng axit pecloric 0,01 mol/ l.
Bari peclorat/dioxan: Cho 10 ml dung dch bari peclorat v 40 ml nc vo bnh nh mc
1000 ml, thm ioxan n vch mc v trn u.
Dung dch H
2
SO
4
0,5M: T ng nghim tiu chun pha ra thnh 1l dung dch.
Thorin 0,25%: Ha tan 0,25 g thorin trong 40 ml dung dch sunfat tiu chun v thm nc ct
n th tch dung dch 100 ml.
Quy trnh xc nh: T bnh hp th, ly ra 5 ml dung dch, trn u vi 10 ml dung dch bari
peclorat/ioxan v 0,25 ml thorin. Khi cng mu ca dung dch t l vi lng bari d v t l
nghch vi lng ion SO
4
2-
c trong mu. Da theo ng chun tnh hm lng SO
2
c trong mu.
Trong khi tin hnh, thorin c th to phc vi nhiu ion kim loi lm cn tr php xc nh, do
vic lc bi giai on thu mu c th loi b c nh hng ny. S c mt ca PO
4
3-
s to
thnh kt ta Ba
3
(PO
4
)
2
lm cn tr php xc nh.
Khi hm lng SO
2
ln, c bit nhng ngun thi tnh, c th dng phng php hyro
peroxit/bari peclorat/thorin thay cho phng php trc quang thorin. Trong phng php ny ngi ta
chun mu bng dung dch bari peclorat vi ch th thorin. Ti im cui ca qu trnh chun ,
dung dch xut hin mu hng.
8.5.4. Xc nh CO bng phng php sc k
Nguyn l: Cho mt th tch mu khng kh i qua ct sc k tch CO ra khi cc thnh phn
kh khc. Kh CO va tch ra thnh metan bng dng kh hyro vi xc tc niken nng (c th dng
cc cht xc tc v cht h tr khc).
CO + 3H
2
= CH
4
+ H
2
O
Tn hiu sc k nhn c t l vi lng CO c trong mu.
Ha cht thit b:
- Cc kh:
127
Hyro c s dng lm kh mang trong tch sc k kh, lm cht kh CO thnh metan v
cng cn cho hot ng ca detector ngn la ion ha.
Nit, hli: i vi mt s u t, kh nit hoc heli hoc hn hp c hai kh ny c thm
vo kh t tng nhy v n nh.
Cc kh metan v CO chun.
- Ct sc k: Dng ct sc k tch CO ra khi cc thnh phn khc c trong mu. iu quan
trng l cc nguyn liu nhi ct khng thng xuyn gi nc v ct s c ra ngc gia cc ln
phun mu.
Quy trnh tin hnh:
Trong khi tin hnh cn ch nhng im sau:
- Khong nhng nng d kin
- Tn hiu o sc k v nng ti thiu c th pht hin so vi tn hiu nhim
- S mu gin on c o trong mt n v thi gian
- tri ca "im khng" v thi gian tri
- lp li ca cc php o
- Hiu sut chuyn ha
- Khong nhit cc mu s c ly.
1. Chun b xc tc: Bo ha niken nitrat hecxahyrat (Ni(NO
3
)
2
.6H
2
O) trong 25 ml nc ct, lc
b phn khng tan. Ngm 10 g iatomit c kch c t 0,125 - 0,15 mm trong dung dch ny, lc chn
khng v lm kh qua m nhit 110
0
C. Nung trong khng kh 5 gi nhit 500
0
C.
2. Chun b ng chuyn ha: Nhi iatomit x l vi niken nitrat vo mt ng thp khng r.
3. L chuyn ha: Lp rp h thng ly mu, ng chuyn ha vo my sc k kh. iu chnh h
thng sao cho n c th hot ng theo cch thc ng vng. Trong giai on ny nt iu khin t
ng v b ghi u khng cho hot ng. Bt my sc k v iu chnh theo cc ch dn ca nh sn
xut.
iu chnh nhit l chuyn ha n 350
0
C v vn hnh h thng trong 10 gi kh cc niken
oxit thnh niken kim loi.
4. Xc nh: Dng bm ly mu ht lin tc kh qua vng mu v ng vng ca n. Lu lng
ca dng kh mu (khong 100 cm
3
/giy) lm sch v lm y vng mu. Vo nhng thi im
thch hp trong chng trnh ly mu, kh cha trong vng mu s c phun t ng vo h thng
sc k o hm lng CO.
Kt qu:
Nng CO c xc nh bng cch so snh cc din tch pic thu c t cc hn hp kh
chun v mu.
Nng CO c tnh chuyn t mg/m
3
thnh ppm nh sau:
- nhit 25
0
C v p sut 101,3 kPa;
1 ppm 1,14 mg/m
3
- cc nhit khc v p sut 101,3 kPa;
1 ppm 1,14 x (373,1 + t)/ 298,1 mg/m
3
128
Trong : t - Nhit tnh bng
0
C.
8.5.5. Xc nh ozn
Nguyn l:
Tc ng ca ozn ln dung dch kali ioua s gii phng iot t do:
2KI + O
3
+ H
2
O 2KOH + I
2
+ O
2

Sau khi axit ha, ngi ta chun it thot ra bng dung dch natri thiosunfat c mt h tinh bt.
Phng php ny c th xc nh mt lng nh ozn.
Ha cht:
Na
2
S
2
O
3
0,1N: Ha tan 6,205 g Na
2
S
2
O
3
.5H
2
O trong nc ct nng, thm nc ct n 1 l.
Ch th h tinh bt: cn 1 g h tinh bt ha tan trong 100 ml nc, thm vo vi git
focmanehyt.
Tin hnh phn tch:
Ly mt th tch kh o c ca kh cha ozn vo mt pipet chun ha c dung tch 1,5 l
cha 20 ml dung dch kali ioua 0,1%, thm vo 2 ml dung dch tinh bt 1% v 200 ml nc. Sau 5
pht lc mnh, it t trong dung dch trung tnh s gii phng ra mt lng tng ng vi hm
lng ozn trong kh. Sau khi lc pipet, dung dch phn ng c axit ha bng axit sunfuric long.
Chun lng I
2
t do bng natri thiosunfat vi ch th h tinh bt cho n khi dung dch mt mu v
tr nn trng ng. C 1 ml dung dch natri thiosunfat 0,1N dng chun tng ng vi 0,24 mg
ozn c trong mu.
S c mt ca clo v nit oxit gy cn tr cho php xc nh.
8.5.6. Phng php inophenol xc nh hm lng amoniac
Nguyn l:
Phng php da trn c s tc dng ca amoniac vi hypoclorit v phenol c s tham gia ca
cht n nh phn ng l natri nitro pruxit, to ra hp cht mu xanh, hp ph cc i ti bc sng
625nm.
Phng php c s dng xc nh hm lng amoniac trong khng kh tng ln v trung
bnh ngy m trong khong t 0,1 n 1,0 mg/m
3
.
Cc amin thm v focmandehyt gy cn tr php xc nh.
Dng c:
- My ht kh c lu lng k c vch chia n 0,005 lt/pht; nhit k, p k, m k.
- Bnh hp th Ricte c vch o 6ml hoc dng c hp th khc.
- My so mu c knh lc mu 625nm, hoc quang ph k, cuvet c b dy 10mm.
- ng nghim c nt mi dung tch10ml.
- Phu Bucne.
Ha cht v thuc th:
S dng loi tinh khit ha hc hay tinh khit phn tch.
Natri hyroxit : NaOH
Kali ioua: KI - dung dch 10%
129
Amoni clorua NH
4
Cl
Natri nitro pruxit Na
2
[Fe(CN)
5
] NO
Natri cacbonat Na
2
CO
3
axit sulfuric H
2
SO
4
(d = 1,18) dung dch 10% theo th tch
Natri clorua: NaCl
axit salixilic: [HO(C
6
H
4
)COOH].
Natri thiosunfat : Na
2
S
2
O
3
.5H
2
O dung dch 0,05mol/l.
axit oxalic H
2
C
2
O
4

Phenol C
6
H
5
OH.
Clorua vi CaOCl
2
Nc ct hai ln kh amoniac.
Chun b ha cht:
- Dng c hp th: pha long 0,5 ml axit sunfuric (d = 1,84) trong 1 lt nc. Bo qun dung dch
trong bnh hnh ng c y kn bng nt c ng thy tinh cha y tinh th axit oxalic.
- Thuc th phenol: Ha tan 5 g phenol mi chng ct, 25 mg natri nitro pruxit trong 100ml nc.
Bo qun thuc th khng qu 6 thng 4
0
C.
- H tinh bt, dung dch 0,5%: trn u 0,25 g tinh bt vi 10 ml nc, cho thm 40ml nc nng
60-70
0
C un n si, dung dch sau 1 pht th lm lnh.
- Thuc th hipoclorit: Ha tan 10 g NaOH v 11,7g NaCl trong 100 ml nc bo ha clo (vi
nng t 0,6 - 0,8g clo). Thuc th c bo qun khng qu 6 thng. Thuc th phi cha
lng clo t 0,6 n 0,8g clo trong 100 ml.
Tin hnh xc nh hm lng clo hot tnh: Ly 20 ml dung dch thuc th cho vo bnh cu c
nt mi, thm 10 ml H
2
SO
4
10%, 10ml KI 10%. y kn bnh cu v trong bng ti khong 10 pht,
sau chun I
2
gii phng ra bng Na
2
S
2
O
3
0,05mol/l n mu vng nht. Thm mt vi git h
tinh bt, chun tip bng Na
2
S
2
O
3
n khi dung dch mt mu -1 ml dung dch natri thiosunfat 0,05
mol/l tng ng vi 0,00354 g clo.
C th dng clorua vi chun b thuc th.
- Dung dch chun amoniac gc: 100 g amoniac trong 1 ml: ha tan 0,3141 g NH
4
Cl trong 1 lt
nc. Bo qun dung dch khng qu hai thng.
- Dung dch chun amoniac s dng c hm lng 1 g amoniac trong 1 ml. Dung dch ny c
chun b bng cch pha long dung dch chun gc 100 ln bng dung dch hp ph.
Ch pha dung dch ny trc khi dng.
Ly mu:
- xc nh hm lng tng ln amoniac, cho khng kh cn nghin cu i qua hai ng hp th
mc ni tip vi nhau, mi ng c cha c 5 ml dung dch hp th vi lu lng 0,5 l/pht, lin tc
trong thi gian t 10 n 30 pht.
- xc nh hm lng amoniac trung bnh ngy m c th ly mu theo hai cch:
+ Ly mu nh xc nh hm lng tng ln NH
3
vi s ln khng t hn 6, cch nhau u trong
mt ngy m.
130
+ Cho khng kh (trong mu) cn nghin cu i qua dung dch hp th c cha 50ml dung dch
hp th vi lu lng 0,2 lt/pht lin tc trong 24 gi.
Phi theo di qu trnh ly mu, nu dung dch b cn th cn b sung nc ct.
Tin hnh phn tch:
- Dng nc ct hai ln thm vo dung dch trong bnh hp th n 10 ml.
- Ht 2 ml dung dch mu th cho vo ng nghim nt mi, thm 3 ml dung dch hp th, 1 ml
thuc th phenol. Sau va lc cn thn ng nghim va cho thm 0,5 ml thuc th hipoclorit.
- Sau 2 gi tin hnh o mt quang ca dung dch, s dng cuvet 1cm, bc sng 625nm,
dung dch so snh l nc ct.
Thi gian cho thuc th cui cng n lc o mt quang ca dung dch i vi tt c cc mu
phi nh nhau.
- Chun b mu trng t dung dch hp th; o mt quang ca 5ml dung dch thuc th iu
ch thnh mu trng; gi tr o mt quang ca mu trng khng c vt qu 0,02. Nu qu
phi kim tra sch ca nc, dng c, cuvet v cht lng dung dch.
- Lng NH
3
trong mu th c xc nh theo phng php ng chun theo hiu s gia mt
quang ca mu em i phn tch v mt quang ca mu trng.
ng chun c lp nh sau:
Dng 6 bnh nh mc 50ml ri thm vo cc lng dung dch nh sau:
Tn dung dch 1 2 3 4 5 6
Dung dch chun s dng 1 2 4 6 8 10
Dung dch hp th
Hm lng NH
3
tng ng trong 5ml
dung dch mu th (mg)
0,1 0,2 0,4 0,6 0,8 1,0

Ly 5 ml dung dch t mi bnh trn cho ng nghim nt mi ri tin hnh lm nh dung dch th
nghim.
Tnh kt qu:
Hm lng amoniac (C) trong khng kh c tnh bng mg/m
3
theo cng thc.
C = a.B/ B
a
.V
o

a : Lng NH
3
trong dung dch mu ly phn tch, mg
B : Tng lng dung dch mu th, ml
B
a
: Th tch dung dch mu th ly phn tch, ml
V
o
: Th tch mu khng kh a v iu kin tiu chun, m
3
.
Khi xc nh nng trung bnh ngy m, th tch khng kh khng cn a v iu kin chun.
131
Chng 9. Phn tch t
9.1. phn tch mt s tnh cht l ha hc c bn ca t
9.1.1. Thnh phn c gii t
t l mt h thng d th gm nhng phn t khong, khong - hu c v hu c c kch thc
khc nhau, t phn t n nhng nguyn t c hc c kch thc ln nh st, limn, ct v gim cui.
Trong nghin cu t, nhiu khi cn phi xc nh kch thc ca nhng hp phn ny v mt s
lng v cht lng.
Thnh phn c gii c ngha quan trng, n c trng cho ngun gc pht sinh ca t, cc tnh
cht t v ph ca t. Vic phn loi t v c bn cng da vo thnh phn c gii ca t. V
d, t ct, ct pha, t tht, t st... i vi dinh dng ca cy trng th thnh phn c gii t li
cng c vai tr to ln, t c thnh phn c gii nng, gi c nhiu cht dinh dng hn. Nhiu tnh
cht vt l ca t nh xp, tr m, tnh thm, kh nng gi kh, gi nhit...u ph thuc vo
thnh phn c gii.
a. Phn loi nhng nguyn t c hc trong t
Nguyn t c hc ca t tn ti 3 dng: khong, hu c v hu c khong (cn gi l humat).
Trong th nhng hc c nhiu bng phn loi nguyn t c hc theo ln ca chng v bng phn
loi ca Katrinski c tha nhn rng ri nht. Trong bng phn loi ny tc gi chia thnh:
vn, si, cui, ct, limn v st.
Bng 9.1. Phn loi nhng nguyn t c hc ca t (theo Katrinski)
ng knh (mm) Tn gi
> 3 Phn vn ca t
3 - 1 Si, cui
1 - 0,5 Ct th
0,5 - 0,25 Ct trung bnh
0,25 - 0,05 Ct mn
0,05 - 0,01 Limn th
0,01 - 0,005 Limn trung bnh
0,005 - 0,001 Limn mn
< 0,001 St
> 0,01 Ct vt l
< 0,01 St vt l
Tt c nhng phn t c kch thc ln hn 1 mm gi l "phn xng" ca t, nhng phn t
nh hn 1 mm gi l "phn mn" ca t. N.M. Xibicxep (1899) phn chia nhng phn t ca t
thnh "ct vt l" - tc l nhng cp ht ln hn 0,01 mm v "st vt l" - nhng cp ht nh hn 0,01
mm. Nhng khi nim ny hin nay c s dng rng ri trong phn loi t theo thnh phn c gii.
132
b. Chun b t phn tch thnh phn c gii i vi nhng t cha cacbonat.
i vi nhm t ny vic chun b phn tch thnh phn c gii rt phc tp, ngi ta thng s
dng cc dung dch mui khc nhau nh: natrioxalat (Na
2
C
2
O
4
); pirophotphat (Na
4
P
2
O
7
) v
hecxametaphotphat (Na
6
P
6
O
18
). Ty thuc vo hm lng cacbonat v dung tch hp ph ca t m
s dng Na
2
C
2
O
4
0,5N vi lng khc nhau. Vic s dng cc dung dch mui natri x l mu t
l y nhng cacbonat ca t di dng cc mui khng tan, do trong t s c hnh thnh
nhng nguyn t c hc mi. Nhng hp cht mi ny l (Ca,Mg)C
2
O
4
; (Ca
2
,Mg
2
)P
2
O
7
;
(Ca
3
,Mg
3
)P
6
O
18
; Na
2
Ca
2
(PO
3
)
6
. Trong thc t vic x l t bng nhng mui kim trn y thng
c kt hp vi nhng phng php c hc, ngha l nghin, tn t.
P.F.Menhicp (1952) ngh phng php pirophotphat nh sau: Cho t t dung dch
pirophotphat 5% vo mu t phn tch n trng thi sn st. i vi t mn v t cacbonat c
thnh phn c gii nng th s dng t 20 - 25 ml cho 10 g t, cn i vi t ct pha v t ct th s
dng 15 ml cho 15 g t. i vi t khng mn v khng cha cacbonat c thnh phn c gii nng
th s dng 5 ml; t tht, ct pha v ct th s dng 3 ml cho 10 g t. Mu c nho trn trong 20
pht, sau dng chy s c bt u cao su nghin, tn trong 5 pht v vo cc. Va nghin tn
va gn cho n khi xut hin nc trong khi t lng. Cho t qua ry kch thc 0,1 hoc 0,25 mm
vo ng ong c dung tch 1 lt. Thm nc vo ng ong cho n 1 lt v phn tch thnh phn c
gii theo phng php pipet ca Katrinski.
Phng php hecxa - metaphotphat x l mu t: ly khong 300 g t, nu l t mn th
trc ht phi loi clo bng cch ra t qua giy lc trn phu, dng nc ct ra nhiu ln cho n
khi ht ion Cl
-
(dng AgNO
3
5% trong mi trng c axit ha bng HNO
3
10% th phn ng
clo). t sau khi ra sch em phi trong phng n trng thi kh khng kh, ry qua ry 1 mm v
ly 20 g phn tch.
Dung dch dng x l mu t c chun b nh sau: ly 3,7g Na
6
P
6
O
18
+ 7,94 g Na
2
CO
3
ha
tan trong 1 lt nc. Natricacbonat thc y s thy phn ca hecxa-metaphotphat thnh octophotphat.
ly 20 ml dung dch ny thm vo mu t c ra (nu l t mn) v 10 ml i vi t khng
mn, dng a thy tinh u c gn cao su khuy cn thn v sau khong 15 - 20 pht dng nc ct
chuyn dn t sang bnh tam gic dung tch 250 ml.
un dung dch huyn ph ny trong 1 gi, sau chuyn t vo ng ong c dung tch 1 lt qua
ry c 0,1 mm, cn c nh v ra khng cho cc phn t st bm vo. Dung dch t trong ng
ong trng thi huyn ph, v xy ra hin tng t keo. Nu qu trnh t keo xy ra chm th c th
thm mt t dung dch x l vo dung dch huyn ph. Trng hp qu trnh t keo xy ra nhanh th
cn thn gn phn nc trong v thm nc ct cng vi mt phn dung dch x l.
c. Nguyn tc v k thut phn tch thnh phn c gii t
Cc phng php phn tch thnh phn c gii t bao gm: phng php ngoi ng rung,
phng php ry, phng php trong mi trng nc (phng php lng gn, phng php t trng
k, phng php pipet).
- Phng php ngoi ng rung (xc nh nhanh, khng c dng c):
Phng php t: Tm t mu t ri dng hai lng bn tay v thnh si di 5 - 6 cm. K
thut tm t t cn ch va , khng kh qu, khng nho qu, ngha l m lc ny tng ng
vi "gii hn chy di". Sau khi v thnh si, tip tc un thnh vng trn. S th hin hnh dng ca
vng trn tng ng vi thnh phn c gii t c minh ha bng 9.2.
133
Bng 9.2. Xc nh thnh phn c gii theo phng php ngoi ng rung






















Phng php ny nu c thc hin cn thn, cng cho nhng kt qu tt, gn ng vi kt qu
phn tch trong phng.
- Phng php phn tch thnh phn c gii trong mi trng nc ng yn tnh (phng php
pipet ca Katrinski - Gluskop).
Phng php ny do Gluskop xut nm 1912. n nm 1922, Robison ngh dng ng ht
vi th tch 25 ml ly dung dch huyn ph, cho nn cn c gi l ng ht Robinson hay pipet.
Nm 1930, ti Hi ngh Quc t Th nhng, phng php ny c cng nhn l phng
php tiu chun xc nh thanh phn c gii t v c s dng rng ri nhiu nc trn th
gii.
Trnh t phn tch: mu t phn tch sau khi phi trong phng n trng thi "kh khng kh",
dng ci chy s gi t v ry qua ry c 1mm. Trn u, ly 3 mu phn tch theo cc yu cu:

t tht v tht
nng (g)
t ct v
ct pha (g)
- xc nh ht m khng kh (1) 4 - 5 10
134
- xc nh lng tiu hao khi x l bng HCl (2) 10 - 15 20 - 30
- chun b ung dch huyn ph (3) 10 -15 20 - 30

Lng t ly phn tch nhiu hay t tu thuc vo c tnh ca t, t c thnh phn c gii
cng nh th lng t ly phn tch cng nhiu v ngc li.
Mu t s 2 v 3 cho vo bt s v kim tra mc cha cacbonat ca t bng cch cho nh
git HCl 10% vo mu. Nu t c cacbonat th xut hin bt kh CO
2
bay ra v lc ny cn tip tc
x l bng dung dch HCl 0,2N cho n khi khng thy xut hin bt CO
2
. Vic ph hy cacbonat khi
phn tch thnh phn c gii l cn thit v Ca v Mg trong t c vai tr cht kt dnh, chng lin kt
cc nguyn t c hc li vi nhau to thnh nhng on lp c kch thc ln hn.
Tip tc HCl 0,2N vo mu t, dng a thy tinh khuy, lng mt thi gian ri gn phn
nc trong bt s theo a thy tinh qua phu lc. Hai mu t c x l song song cho n khi
nh HCl 0,2N khng thy xut hin bt kh th dng li.
Sau khi ph hy cacbonat, dng dung dch HCl 0,05N chuyn dn mu t bt s ln giy lc
t trong phu. Mu t dng xc nh lng tiu hao khi x l HCl cn chuyn ln giy lc t
trong phu nhng cn trc khi lng ca giy lc. t trn phu tip tc c ra bng HCl
0,05N cho n khi ht phn ng vi Ca
2+
. th phn ng, dng ng nghim hng mt t dch lc,
thm hai git ch th phenolphtalein v dng NH
4
OH 10% trung ha theo tng git cho n khi xut
hin mu hng, phn ng lc ny hi kim. Thm vi git CH
3
COOH 10% axit ha dung dch,
thm vi git (NH
4
)
2
C
2
O
4
4% v un n si. Nu c Ca
2+
th s xut hin tinh th CaC
2
O
4
rt r. Nu
ht Ca
2+
(khng c kt ta) chuyn ht t ln phu bng dung dch HCl 0,05N. Tip tc ra mu t
trn phu lc bng nc ct cho n khi ht phn ng vi clo. th phn ng, dng ng nghim
hng mt t dung dch lc, dng vi git HNO
3
10% axit ha dung dch sau thm vi git
AgNO
3
5%, Nu cn clo s xut hin kt ta mu trng AgCl.
i vi nhng mu t khng c cacbonat th dng ngay axit HCl 0,05 N x l, sau cng
chuyn qua phu lc, ra cho n khi ht canxi v clo nh trnh t trn.
Mu t dng tnh lng tiu hao khi x l HCl, sau khi ra, t v giy lc c cho vo
trong cc s hoc nhm cn trc khi lng, sy kh 105
0
C n khi lng khng i ri cn.
Cn c vo hiu s khi lng, xc nh lng tiu hao khi x l HCl.
Mu t dng phn tch thnh phn c gii, sau khi ra sch Ca
2+
v clo, dng a thy tinh
chc thng giy lc, dng nc ct c ra trc tip vo bnh c dung tch khong 750 cm
3
. Thm nc
ct vo bnh n th tch khong 250 cm
3
v thm NaOH 1N theo dung tch hp ph ca t. C 1 ml
NaOH 1N tng ng vi 10mgl ca dung tch hp ph. Vic thm NaOH 1N mc ch ph v
hon ton cc vi on lp v chuyn sang cc nguyn t c hc.
V cc mu t dng phn tch thnh phn c gii nhiu khi cha xc nh dung tch hp ph
trc, cho nn thun tin ngi ta quy nh lng NaOH 1N (ml) thm vo cc loi t bng sau.
Bng 9.3. Lng NaOH 1N dng cho cc loi t khc nhau

Loi t
Lng NaOH 1N
(ml)
135
1) t feralit : Tng 0 - 50 cm
Cc tng di
2) t feralit trn sn phm vi: Tng 0 - 50 cm
Cc tng di
3) t macgalit: Tng 0 - 50 cm
Cc tng di
4) t ph sa
t ph sa c tng ra tri, bc mu
Cc loi ph sa khc
1 - 2
1 - 1,5
1,5 - 3
2 - 3,0
2 - 5
2 - 3
0,5 - 1,5
0,5 - 1,5
1 - 3

Sau em un si th huyn ph 1 gi, thi gian tnh t lc bt u si. Lm ngui dung dch
v chuyn ton b dung dch vo ng ong c dung tch 1 lt qua ry c 0,25 mm. Dng nc ct ra
phn cha trn ry v sau thm nc ct n 1 lt. Nh vy, phn cn li trn ry gm nhng cp
ht c kch thc t 0,25 - 1,0 mm, phn cha trong ng ong l nhng cp ht c kch thc < 0,25
mm. Phn cha trn ry cho vo chn s bit khi lng, sy 105
0
C n khi lng khng i.
Nu cn tch cp ht ct kh 1 - 0,5 mm th dng thm ry 0,5mm v s thu c 2 cp ht ct th: 1 -
0,5 mm v ct trung bnh 0,5 - 0,25 mm.
Tin hnh phn tch cc cp ht phn trong ng ong da vo vn tc lng ca phng trnh
Stockes. Tng quan gia kch thc cp ht v su ng ht (pipet) trong dung dch nh sau:
- i vi cp ht < 0,050 mm th su ng ht l 25 cm
- i vi cp ht < 0,010 mm th su ng ht l 10 cm
- i vi cp ht < 0,005 mm th su ng ht l 10 cm
- i vi cp ht < 0,001 mm th su ng ht l 7 cm
Thi hn ly mu t nhng su khc nhau c tnh t khi ngng khuy c dung dch, thi
hn ny thay i ph thuc vo nhit v t trng th rn ca t. Trong khi phn tch cn gi iu
kin nhit c nh. V d, nhng ng ong cha mu c t trong mt b nc lm bng mica trong
sut, nc trong b c iu ha nhit nh hai vi nc nng v lnh, hoc ng ong c y
np gi nhit, hn ch khng cho nhit dao ng gy nh hng n vn tc chm lng.
theo di nhit , t nhit k vo ng ong cha nc v gi nhit nh iu kin ca
nhng ng dung dch t. Bi v khong thi gian gia nhng ln lc - ht i vi nhng cp ht <
0,05; < 0,01 v < 0,005 mm khng lu lm nn nhit c th ch o mt ln. Khi cn ly cp ht <
0,001 mm, nn o nhit ba ln: sau khi lc dung dch, trc khi ht v 1 ln vo gia hai thi im
trn. Ly nhit trung bnh sau 3 ln o, i chiu vi tc lng tng ng chn phn tch.
V t trng th rn, nn ly gi tr chnh xc ca tng loi t nghin cu. Tuy nhin, trong phn
tch c th dng nhng tr s tng i gn ng cho mt s trng hp.
Bng 9.4. T trng th rn ca mt s nhm t chnh Vit Nam
su (cm) Nhm t feralit (t vng) Nhm t ph sa trng la
0-20
20-50
50-100
2,55-2,65
2,60-2,65
2,65
2,65 (chung cho c cc tng di)
136
100-150
150-200
2,70
2,70

bng ch dn thi hn ly mu dung dch huyn ph trong ng ong cc su khc nhau
tng ng vi vn tc lng ca cc cp ht theo phng trnh Stockes trong iu kin nhit v t
trng th rn ca t khc nhau.
Vn tc chm lng ca cc cp ht (V) tnh theo phng trnh Stockes:
V (cm/s) =

d d
r g

1 2
. . .
9
2

r : Bn knh ca cp ht (mm)
d
1
: T trng th rn ca t
d : T trng cht lng khi dng phn tch
g : Gia tc trng trng khi vt ri t do bng 981cm/s
: nht ca cht lng (poaz)
Dng c phn tch thnh phn c gii t bng pipet theo Katrinski c trnh by hnh 22.



K thut ly mu dung dch huyn ph bng dng c ny nh sau: khuy dung dch huyn ph
trong ng ong bng que khuy. Que khuy gm mt ng cao su hnh trn gn vi a thy tinh hoc
que kim loi khng g. Tm cao su hnh trn c c thnh nhiu l ng knh mi l khong 3 mm.
Que khuy cho chuyn ng t trn xung di v ngc li 10 ln trong 20 giy. Theo thi hn
tnh sn (xem ph lc 8) nhng ng ht xung n su quy nh ht ly thnh phn cp ht cn tm,
dung dch c ht vo pipet mt cch t t. Ly 25 ml dung dch huyn ph khi xc nh thnh phn
cp ht < 0,005 mm trong thi hn 30 giy, i vi cp ht < 0,01 mm trong thi hn 25 giy v cp
ht < 0,05 mm trong thi hn 20 giy. Mu ly xong cho bc hi trn bp cch ct hoc trn ni cch
thy, sau sy nhit 105
0
C n nhit khng i. Khi lng cc c cn sn. Sau khi
cn xong tnh kt qu.
Hm lng cc cp ht c tnh ra phn trm theo cng thc:
Hnh 9.1. Dng c pipet ly mu khi xc nh thnh phn c gii
137
X =
m b
a
.
100 . 1000 .

x : Thnh phn cn tm tnh ra %, thnh phn ny nh hn kch thc cp ht no , v
d < 0,05 mm; < 0,01 mm...
a : Khi lng ca thnh phn nh hn kch thc cp ht cn tm (g)
b : Th tch dung dch huyn ph (ml)
m : Khi lng t kh tuyt i ly khi phn tch (g)
Trong thc t phn tch khng nn tnh theo t kh tuyt i, m nn tnh theo t kh khng
kh, lm nh vy s c nhiu thun li trong vic tnh kt qu. Mun vy, nhn cng thc trn vi h
s kh kit (k). H s k c xc nh theo cng thc
k =
100
100
hy
W +

Theo cng thc ny W
hy
l ht m khng kh ( m hydroscopic).
Khi lng thnh phn c kch thc xc nh (0,05 - 0,01; 0,01 - 0,005 mm; 0,005 - 0,001 mm
v < 0,001 mm) c tnh bng cch tr khi lng hoc hm lng phn trm ca thnh phn tip
theo.
V d c th v cch tnh:
1) Khi lng t kh khng kh ly khi phn tch l 10 g
2) Khi lng thnh phn c kch thc 1 - 0,25 mm l 0,81 g
3) Lng tiu hao khi x l bng HCl l 0,232 g
4) Khi lng thnh phn trong 25 cm
3
dung dch
Kch thc cp ht (mm)
< 0,05
< 0,01
< 0,005
< 0,001
Khi lng thnh phn cp ht (g)
0,116
0,075
0,015
0,009
5) Thnh phn cp ht tnh ra % so vi khi lng t kh:
Khi lng cp ht (mm)
1- 0,25

< 0,05

< 0,01

< 0,005

< 0,001
Thnh phn (%)
=
10
. 100 . 81 , 0 k
= 8,18
=
25 . 10
. 1000 . 100 . 116 , 0 k
= 46,8
=
25 . 10
. 1000 . 100 . 075 , 0 k
= 30,3
= 06 , 6
25 . 10
. 1000 . 100 . 015 , 0
=
k

= 64 , 3
25 . 10
. 1000 . 100 . 009 , 0
=
k

138
Khi thm vo dung dch huyn ph 2 ml NaOH 1N, tng ng 0,08 g, nu tnh vi lng t
dng phn tch 10g th chim t l 0,8%. Nh vy thc t hm lng cp ht nh hn 0,001 mm ch
bng 3,64 - 0,8 = 2,84%.
6) Khi lng thnh phn (%) so vi khi lng t
Kch thc cp ht (mm)
1 - 0,25
0,05 - 0,01
0,01 - 0,005
0,005 - 0,001
< 0,001
Thnh phn (%)
= 8,18
= 46,8 - 30,3 = 16,5
= 30,3 - 6,06 = 24,24
= 6,06 - 3,64 = 2,42
= 3,64 - 0,8 = 2,84
7) Lng tiu hao khi x l bng HCl:
34 , 2
10
01 , 1 . 100 . 232 , 0
=
8) Thnh phn cp ht c kch thc 0,25 - 0,05 mm so vi khi lng t kh l:
100 - (8,18 + 16,5 + 24,24 + 2,42 + 2,84 + 2,34) = 43,48%
i vi nhng t c thnh phn c gii nh, dng ry khi phn tch c th phn chia thm nhng
thnh phn chi tit hn. V d, c th dng ry c 0,1 mm. Nh vy, cng vi c ry c kch thc 0,5
v 0,25 mm c th chia c 1 - 0,5; 0,5 - 0,25 v 0,25 - 0,1 mm. Hm lng ca chng trong t
c tnh bng %. Tng lng ca chng cng vi nhng thnh phn thu c khi ht bng ng ht
cng gp li, ly 100% tr cho ton b cc thnh phn trn s thu c thnh phn cp ht 0,1 - 0,05
mm, nh vy c th thu c mt c trng chi tit hn i vi cc thnh phn ct ca t nh. i
vi nhng t cha cacbonat lng tiu hao khi x l bng HCl nn phn chia thnh ct ring gi l
thnh phn tng hp cng gp vo trong 100% ca thnh phn c gii t.

d. Cc phng php th hin kt qu phn tch thnh phn c gii t:
Kt qu phn tch thnh phn c gii thng ghi thnh bng, trong bng s liu ny bn cnh
nhng thnh phn cp ht cn ghi thm ct m khng kh v lng tiu hao khi x l bng HCl.
Tr s v lng tiu hao c trng cho s c mt t nhng cacbonat v nhng mui d ha tan
trong t.
d hnh dung nhng kt qu phn tch thu c, ngi ta thng th hin di dng th.
V d, phng php phu din, phng php hnh trn (hnh 9.2; 9.3).

139

Hnh 9.2 - Phng php th biu din thnh phn c gii t
theo su phu din t.
1 - Lng tiu hao khi x l HCl 0,05N
2 - Ct th
3 - Ct mn
4 - Limon th
5 - Limon trung bnh
6 - Limon mn
7 - St.
Vic th hin trn th theo phng php phu din hin nay c s dng rng ri trong th
nhng bi v n c th biu th c nhng dn liu phn tch theo su cc tng pht sinh khc
nhau.
Trc tung ghi su, trc honh ghi hm lng % thnh cp ht. Khi v nh tnh tr s sau cng
tip theo tr s trc trc honh.
20%
54%
16%
9%
1%

Hnh 9.3. - Phng php hnh trn biu din thnh phn c gii t
(Din tch hnh trn = 100%)
e. ng dng thc tin ca phn tch thnh phn c gii
C nhiu bng phn loi thnh phn c gii t, nhng bng phn loi ca Katrinski hin nay
c dng rng ri trong th nhng hc. Theo bng phn loi ny th vic xc nh tn gi v phn
chia cc nhm t u da vo kt qu phn tch thnh phn c gii. t gi theo thnh phn c gii
cn c vo hm lng ct vt l v st vt l v theo u th tri ca cc thnh phn; si, san 1 - 3 mm,
ct 1 - 0,05 mm, limon th 0,01 - 0,05 mm, limon 0,01 - 0,001 mm v st < 0,001 mm.
140
Bng 9.5. Phn loi t theo thnh phn c gii ca Katrinski
Hm lng st vt l
(cp ht < 0,01 mm)
Hm lng ct vt l
(cp ht > 0,01 mm)
t
Kiu
ptzn
Kiu t ng
c; t ; t
vng
t mn
Kiu
ptzn
Kiu t ng
c; t ; t
vng
t mn
t c gi
theo thnh phn
c gii
0-5
5-10
10-20
20-30
30-40
40-50
50-65
65-80
> 80
0-5
5-10
10-20
20-30
30-45
45-60
60-75
75-85
> 85
0-5
5-10
10-15
15-20
20-30
30-40
40-50
50-65
> 65
100-95
95-90
90-80
80-70
70-60
60-50
50-35
35-20
< 20
100-95
95-90
90-80
80-70
70-55
55-40
40-25
25-15
< 15
100-95
95-90
90-85
85-80
80-70
70-60
60-50
50-35
< 35
Ct xp
Ct dnh
Ct pha
Tht nh
Tht trung bnh
Tht nng
St nh
St trung bnh
St nng
g. Xc nh thnh phn c gii (Theo FAO - UNESCO)
Nguyn l: Tch phn khong ca t thnh nhng cp ht c kch thc khc nhau v xc nh t
l ca chng. Qu trnh phn tch p dng cho ton b vt liu t, ngha l gm vt liu th v .
Nhng phng php ny ch p dng i vi nhng t mn (< 2 mm).
Phn quan trng trong phn tch l x l s b mu lm phn tn ton b cc cp ht nguyn
sinh. Do , cc vt liu c tnh dnh kt (thng c ngun gc th sinh), v d: cht hu c, CaCO
3

cn phi loi, trong mt s trng hp, setquioxit cng cn phi loi tr. Tuy nhin cn nhn mnh,
i vi mc ch sn xut nng nghip th vic loi tr ny v c bn khng cn thit. V vy, ty theo
mc ch nghin cu, vic x l s b l khng bt buc. Vi mc ch nh gi cc c trng ha hc
t, cn tin hnh tch cht hu c bi H
2
O
2
v CaCO
3
bi mt dung dch m c tnh axit yu pH = 5.
Dng c:
Bp cch thy
Bp in
My lc
My ry
ng h bm
Cc xc nh m
H thng ry c y (ng knh khong 20 cm)
Phu nang bng ng (ng knh khong 23 cm)
Ry nh c 50 m (ng knh khong 8 cm)
ng ong thy tinh dung tch 1 lt
T sy
Ha cht:
H
2
O
2
30%
Dung dch m axetat nng 1M: ha tan 680 g CH
3
COONa.3H
2
O trong khong 4 lt nc,
chnh ti pH = 5,0 bng 250 ml CH
3
COOH, thm nc ct n 5 lt.
Thuc th lm phn tn: Dung dch pirophotphat 5%: ha tan 50 g Na
4
P
2
O
7
.10H
2
O trong chai
c dung tch 1 lt, sau thm nc ct n vch 1 lt.
141
C th thay th bng dung dch natri hecxametaphotphat 3%: ha tan 30 g (NaPO
3
)
6
trong
nc cha trong chai c dung tch 1 lt, sau thm nc ct n vch mc.
Dung dch NaCl bo ha: ha tan 350 g NaCl trong 1 lt nc nng, lm ngui.
Trnh t phn tch:
i vi t c cha cacbonat (
O H
pH
2
> 6,8) th tin hnh loi cacbonat bng x l bi dung dch
m axit yu. Nu t khng cha cacbonat (
O H
pH
2
6,8) th tin hnh oxi ha cht hu c.
1) Loi cacbonat: Cn khong 20 g t mn, cho vo cc dung tch 1 lt (nu hm lng cacbonat
nhiu hn 10% th c th cn nhiu hn 20 g t). Thm khong 100 ml dung dch m v un nng
trn bp cch thy (100
0
C). y cc bng ming knh. Sau khi ngng si bt, thm khong 25 ml
dung dch m n khi s si bt khng ti din sau khi thm tip dung dch m mi. Trong trng
hp hm lng cacbonat rt nhiu, c th thm 5 ml axit axetic bng thay cho dung dch m. Trong
trng hp ny th dng giy qu th pH.
Li tm v gn hoc qua m ri dng xiphng ht dung dch bn trn.
Trng hp b t keo (peptit ha), thm mt vi mililit dung dch NaCl bo ha.
Ch : Phng php ra ny nhm loi canxi axetat t dung dch l lng v n c th chuyn
sang dng canxi oxalat khng tan.
2) xi ha cht hu c: Cn khong 20 g t mn, cho vo cc dung tch 1 lt. Thm 15 ml nc
v 15 ml H
2
O
2
30% (trong trng hp x l s b th khng cn thm H
2
O hoc thm t), y cc
bng ming knh. Trng hp si bt mnh, t cc vo trong b nc lnh. Cng c th ngn s si
bt bng cch thm vi git cn. qua m, hm sau t ln bp cch thy (khong 80
0
C) v thm
u n 5 - 10 ml H
2
O
2
30% cho n khi phn hy cht hu c xy ra hon ton (thng thng dung
dch bn trn tr nn trong).
Thm H
2
O n th tch khong 300 ml. t ln bp nng v un si cn thn trong 1 gi loi
ton b H
2
O
2
cn d. Ly cc ra v ngui. Li tm hoc gn cc vt liu lng trong bnh v dng
xiphng ht. Thm khong 300 ml H
2
O v lm phn tn li kt ta. Nhc li 8 - 9 ln cho n khi xut
hin peptit ha. Mun vy phi ra nhiu ln (hn 4 ln), sau thm mt vi ml dung dch NaCl bo
ha xc tin peptit ha.
Ch : i vi nhng t c cha thch cao cn ra nhiu ha tan chng.
3) Tch hp cht st: Thao tc ny thng thc hin sau nhng x l s b, trc khi lm phn
tn t.
Thuc th:
Dung dch m natri xitrat 0,3M v natri icacbonat 0,1M: ha tan 88 g Na -xitrat.2H
2
O v
8,4g NaHCO
3
trong nc v thm nc ti vch 1 lt.
Natri ithionit
Trnh t phn tch:
Thm khong 200 ml dung dch m vo 20 g t mn cha trong cc dung tch 1 lt. un nng
trn bp cch thy ti khong 75
0
C (khng c vt qu 80
0
C v S nguyn t s kt ta). Dng tha
thm khong 1 g natri ithionit v khuy lin tc khong 1 pht sau khuy ngt qung trong 5 pht.
Nhc li 3 - 4 ln. Li tm v gn lc hoc cho lng ri dng xiphng ht.
142
i vi nhng mu cha nhiu hn 5% Fe
2
O
3
c dng chit d rt, cn nhc li trnh t thm 1 -
2 ln: mu nu hoc mu ca mu chng t cha loi Fe hon ton. Ra thm 1 ln na vi khong
250 ml hoc 500 ml NaCl 1M. Tip tc lm nh khu cui cng ca phn oxi ha cht hu c.
4) Lm phn tn t: Chuyn ht dch l lng vo chai nha dung tch 1 lt (nu khng x l s
b, cn khong 20 g vo chai). Thm 25 ml thuc th phn tn, dng nc a th tch n khong
400 ml, ri nt chai, lc qua m (16 gi).
5) Tch ring cc cp ht: Ry dung dch l lng qua ry c 50 m qua phu t trn ng ong.
Dng nc a th tch trong ng ti 1 lt. Ra cp ht ct trn ry v chuyn vo cc, cho bay hi
trn bp cch thy, sy 105
0
C khong 1 gi.
6) Xc nh cp ht ct: Chuyn ct va sy kh trn vo ry trn cng ca mt chng ry
theo th t 1000 m, 500 m, 25 m, 100 m, 50 m v y.
Ry khong 10 pht trn my ry, c thit t bin : rng 7,0 v khong cch 4 ( v tr
lp t ny cc ry s rung vi tn s 3000 dao ng/pht v bin khong 2mm). Ra sch cc cp
ht tng ry vo cc cc cn trc, sy, cn. Khi lng A qua E l cp ht ct.
Nu c vt liu t li ry y (< 50 m) th chuyn n sang dng l lng trong ng ong
lng ng nh cch lm phn tch ring cc cp ht.
7) Xc nh limon (slit) v st (clay):
Cp ht < 50m: Vt liu < 50 m c th ng li trong qu trnh ry (xem: xc nh cp ht ct),
do vy cn y ng ong bng nt cao su v lc u. t ng ong trn bn, m nt v dng pipet ht
20 ml gia tm ng ong. Chuyn dung dch vo cc cn trc, cho bay hi trn bp cch thy v
sy qua m 105
0
C. Ly cc ra v lm ngui trong bnh ht m ri cn (khi lng kh F cho cp
ht < 50 m).
Cp ht < 20m: y np ng ong v lc u. t ng ong ln bn di ng ht pipet. Sau
ng 5 pht, dng pipet ht 20 ml su nh bng 1. Chuyn dch l lng va ly vo cc cn
trc, cho bay hi trn bp cch thy, sy kh 105
0
C, cn.
Khi lng mu G l cp ht < 20 m.
Cp ht < 2m: Sau 5
h
30 dng pipet ht 20 ml su ca bng 1. Chuyn dung dch mi ly
vo cc cn trc, cho bay hi trn bp cch thy, sy kh 105
0
C v cn.
Khi lng H l cp ht < 2 m.
Ch : Sau mi ln ly mu bng pipet, o nhit ca dung dch l lng.
Bng 9.6. su (cm) ly mu cp ht ph thuc vo nhit (
0
C).
Nhit
(
0
C)
5 pht
(< 0,02 mm)
5
h
30'
(< 0,002
mm)
Nhit
(
0
C)
5pht
(< 0,02 mm)
5
h
30'
(< 0,002
mm)
19
20
21
22
23
24
10,5
10,8
11,0
11,3
11,6
11,9
6,9
7,1
7,2
7,4
7,6
7,8
28
29
30
31
32
33
13
13,3
13,6
13,9
14,2
14,4
8,6
8,8
9,0
9,1
9,3
9,5
143
25
26
27
12,1
12,4
12,7
8,0
8,2
8,4
34
35
36
14,8
15,1
15,4
9,7
9,9
10,1

Kt qu tnh theo khi lng sau khi sy kh. l tng ca tt c cc cp ht ring bit.
Cch tnh:
St (clay) (< 2 m) = (H x 50) - 0,75 g
*
(khi lng K).
Limon (silt) (2-20 m) = (G x 50) - 0,75 - K (khi lng L)
Limon (20-50 m) = (F x 50) - 0,75 - K - L (khi lng M)
Ct ( > 50 m) = A + B + C + D + E (khi lng N)
Khi lng mu = K + L + M +N (tnh theo gam)
Khi lng cc cp ht theo % tnh nh sau:

% st (< 2 m) =



% limon (2-20 m) =



% limon (20-50 m) =


% ct (2000 -1000 m) =


% ct (1000-500 m) =


% Ct (250-500 mm) =


% Ct (100-250 m) =


% Ct (50-100 mm) =
khi lng mu
L
x 100
M
khi lng mu
x 100
khi lng mu
A
x 100
khi lng mu
B
x 100
C
khi lng mu
x 100

D
khi lng mu
x 100
E
khi lng mu
x 100
K
khi lng mu
x 100
144

Ch : Vi cch tnh nh trn th cc cp ht st, limon v ct tnh ra % l ca t mn (tr
cacbonat v cht hu c b loi trc). Cp ht th > 2 mm nu c, tnh ra % ca tng s t. Nu
tt c cc cp ht cn tnh ra tng s t th:

% st, limon, ct =

Trng hp tch Fe th % st t do s tnh c vo phn ngoc n ca cng thc.
8) Xc nh st mn (< 0,2 m):
Nguyn l: V tc lng chm ca ht st nn khng thun tin cho lng trong ng ong. Do
phi dng my li tm tng tc lng.
Trnh t phn tch: Sau khi dng pipet ly mu cp ht < 2 m, y nt ng ong v lc u.
yn tnh khong 1 gi v ly khong 200 ml dung dch l lng cho vo chai li tm c dung tch 250 ml.
Khong cch gia b mt dung dch l lng v tm my li tm trong khi quay l khong 16 cm.
Cho my quay vi vn tc 1800 vng/ pht theo thi gian ch dn bng 2 (tr thi gian bt u
v kt thc).
Ch : Nu quay 2500 vng/ pht th thi gian s t hn. Trong trng hp ny s dng chai
nha. Tt my li tm, ly cc chai ra khi my v t di pipet. Dng pipet ht 20 ml su
khong 4,5 cm. o nhit ca dch l lng. Chuyn th tch ly vo cc cn trc, cho bay hi
trn bp cch thy, sy nhit 105
0
C qua m. Lm ngui cc trong bnh ht m v cn khi lng
cp ht P (g).
Tnh kt qu:
% st mn (< 0,2 m) =

Bng 9.7. Tc li tm, thi gian quay v nhit xc nh cp ht st mn < 0,2 m.
Nhit
0
C 1800 vng/pht 2500 vng/pht
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
32,0
31,0
30,0
29,5
29,0
28,0
27,5
27,0
26,5
26,0
25,0
24,5
24,0
23,5
23,0
16,5
16,1
15,7
15,3
15,0
14,6
14,2
14,0
13,5
13,3
13,0
12,8
12,5
12,3
12,0
100 - % (cp ht > 2mm + cacbonat + cht hu c)
100
. % st, limon, ct ca t mn
(P . 50) - 0,75
khi lng mu
x 100
145
35
36
37
38
39
40
22,5
22,0
22,0
21,5
21,0
20,5
11,8
11,5
11,3
11,1
10,9
10,6
9) St phn tn trong nc:
Nguyn l: l hm lng st xc nh c khi khng x l s b mu khi khng thm tc
nhn phn tn trc khi lc vi nc.
Trnh t phn tch:
Cn khong 10 g t mn cho vo chai dung tch 1 lt. Thm khong 400 ml nc v lc qua m.
Chuyn sang ng ong lng, dung tch 1 lt v thm nc n vch mc. Sau 5
h
30 dng pipet ht 20
ml su theo bng 1. Chuyn dung dch l lng va ly vo cc cn trc, cho bay hi trn bp
cch thy, sy 105
0
C qua m. Lm ngui cc trong bnh ht m ri cn (khi lng cp ht Q (g)).
Cch tnh:



s : Khi lng mu kh khng kh tnh ra gam.
mcf : H s m.
10) Mt s phng php khc trong phn tch thnh phn c gii t.
Nhn chung nhiu nh khoa hc trn th gii tha nhn phng php pipet l phng php
chnh xc nht, thun tin nht. Tuy nhin, mt s nc li s dng nhng phng php ring.
V d, M kch thc cp ht st c quy nh l < 0,002 mm; dng H
2
O ph hy cht hu
c v HCl ph hy cacbonat. Cp ht limon c quy nh c kch thc t 0,05 - 0,002 mm, trong
khi , cng cp ht limon ny c Hi Th nhng Quc t quy nh l 0,02 - 0,002 mm.
Cc nc ny s dng my lc nh l bin php c hc phn tn cc cp ht v khi phn
loi ngi ta s dng tam gic u vi thang phn loi nh sau:
1. Ct (Sand)
2. Ct pha tht (Loamy - sand)
3. Tht pha ct (Sandy - loam)
4. Tht (Loam)
5. Tht pha limon (Silty - loam)
6. Limon (Silt)
7. Tht pha st v pha ct (Sandy clay - loam)
8. Tht pha st v pha limon (Silty clay - loam)
9. Tht pha st (Clay - loam)
10. St pha limon (Silty - clay)
11. St pha ct (Sandy - clay)
St (%) =
50 x Q
s
x 100 x mcf

Hnh 9.4. Thnh phn c gii phn loi theo
hnh tam gic u
146
12. St (Clay)
Cn ch rng khi phn loi cc cp ht c tc gi dng tam gic u (hnh 9.3), c tc gi li
dng tam gic vung vi trc tung biu th % ca hm lng cp ht st; trc honh (cnh y) biu
th % ca hm lng cp ht ct cn cnh huyn trng.
Thnh phn c gii theo nhng phng php ca M c trnh by bng hnh tam gic u (hnh
9.3) bao gm 12 loi; 3 nhm cp ht: st; limon v ct c biu th ba cnh. nh tam gic vung
tng ng 100%. T y tam gic n nh chia thnh 10 hng, mi hng tng ng 10%. Hm lng
ca ba nhm cp ht: ct, limon, st c biu th ba ng thng song song vi y tam gic. Theo
im giao nhau ca ba ng thng trong tam gic s bit c loi t cn tm.
9.1.2. Xc nh dung trng ca t
Dung trng (khi lng ca mt n v th tch) ca t l t s gia khi lng t kh tuyt i
trng thi t nhin (k c nhng l hng) ca mt th tch xc nh vi khi lng ca nc c cng
th tch 4
o
C.
Dung trng c trng cho cht ca t, trong th nhng hc, dung trng s dng :
- Tnh tr lng nhiu nguyn t v chuyn chng t % sang th tch.
- nh gi mt cch khch quan qu trnh ra tri theo chiu su v vic chuyn di cc nguyn
t t tng ny sang tng t khc.
- Tnh hng hay xp ca t.
C nhiu phng php xc nh dung trng nhng thun tin v ph bin nht hin nay l phng
php dng ng ng.
Trnh t phn tch:
t nhng ng ng hnh tr c th tch 100 m
3
ln khu vc ca thnh phu din t c lm
bng phng, t nht phi xc nh 3 ln lp li v nh vy phi s dng 3 ng song song cng mt lc.
t cc khun nh hng ln trn nhng ng ny, sau dng chong (nm) t ln trn cng, dng
ba g ng cc ng vo t (hnh 9.5).













1, 2 : ng ng c kch thc khc nhau

Hnh 9.5. Dng c ly mu t xc nh dung trng

147
6 : Ba g
9 : Gi ng ng ng
10 : Chong
Nh h thng chong v ng khun nh hng nn cc ng ng c ng thng v ln su
vo t. Khi ng ng ln su vo t ht c nhc chong ra, dng dao hoc xng o, gt, nhc
ng ng ra. Dng tm g mng ri lt ngc ng ng, dng dao sc gt bng phng t mt y
di ca ng. y np, sau gt pha u trn cng bng phng nh vy. Lau chi sch t dnh
bm xung quanh ng. Dng dao xn cy t trong ng vo hp nhm ln trng hp khng c hp
nhm th dng ti polyetilen hoc giy bng m gp sn thnh phong b. em cn hp nhm cng
vi t ti chnh xc 0,01 g.
Sau c th s dng mu t ny xc nh t trng th rn, ht m cc i...
Bit c khi lng hp nhm (hoc khi lng ti polyetilen, ti giy) khi lng t v hp
c th tnh c khi lng t kh tuyt i. Bit khi lng t kh tuyt i v th tch ca ng
ng ta s tnh c dung trng theo biu mu sau:
Bng 9.8. Biu mu ghi v tnh kt qu dung trng ca t
t, cy
trng, a
im
Tng
su
(cm)
S hp
nhm
hoc ti
Khi lng
b (hp
nhm hoc
ti (a)
Khi lng
b + t t
(b)
Khi
lng t
ti
(P
1
= b-a)
ht m
khng kh
(W
hy
%)
Khi lng t kh
tuyt i
P = P1x100/(100+
W
hy
)
Th tch
ng
ng (V)
cm
3
Dung trng
Dv = P/V



Theo thang nh gi ca Katrinski:
Dung trng nh hn 1 g/cm
3
: t giu cht hu c
T 1,0 n 1,1 : in hnh cho t trng trt
1,2 : t hi cht
1,3 n 1,4 : t qu cht
1,4 - 1,6 : in hnh cho tng cy; 1,6 n 1,8 - tng tch t
qu cht.
9.1.3. Xc nh cht hu c trong t
S tch lu cht hu c dng mn trong t l do hot ng vi sinh vt, thc vt cng nh bn
phn hu c. Hm lng, thnh phn mn quyt nh hnh thi v cc tnh cht l, ha hc, ph ca
t. Trong tng mn cha gn 90% nit dng d tr v phn ln cc nguyn t dinh dng nh P, S,
nguyn t vi lng, l kho d tr cht dinh dng cho cy trng.
Hin c nhiu phng php xc nh cht hu c ca t: phng php t kh, phng php t
t (Chiurin, Walkley - Black), phng php t mn trong t sy 150
o
C, thi gian 20 pht (Nikitin)
v phng php oxi ha mn 24 gi nhit 20
o
C (P.Antanova). Di y l mt s phng php
ph bin Vit Nam.
148
a. Xc nh cht hu c theo phng php Chiurin:
Nguyn l: Cht hu c ca t, di tc dng ca nhit , b dung dch K
2
Cr
2
O
7
+ H
2
SO
4
(1:1)
oxi ha:
3C + 2K
2
Cr
2
O
7
+ 8H
2
SO
4
3CO
2
+ 2K
2
SO
4
+ 2Cr
2
(SO
4
)
3
+ 8H
2
O
Lng K
2
Cr
2
O
7
cn d c dng dung dch mui c tnh kh l FeSO
4
hay mui Morh
(FeSO
4
.(NH
4
)
2
SO
4
.6.H
2
O) chun:
K
2
Cr
2
O
7
+ 6FeSO
4
+ 7H
2
SO
4
Cr
2
(SO
4
)
3
+ 3Fe
2
(SO
4
)
3
+ K
2
SO
4
+ 7H2O
Cht ch th cho qu trnh chun ny thng dng l axit phenylanthranilic (C
13
H
11
O
2
N), mu
chuyn t mn sang xanh l cy, hoc iphenylamin (C
12
H
11
N), mu s chuyn t lam tm sang
xanh l cy.
Trong qu trnh chun , Fe
3+
to thnh c th nh hng ti qu trnh chuyn mu ch th, v
vy trc khi chun c th cho thm mt lng nh H
3
PO
4
hoc mui cha ion F
-
to phc
khng mu vi Fe
3+
.
Trnh t phn tch:
t phn tch mn v m phi c chun b cn thn: ly 5 - 10 g t ry qua ry 1 mm,
nht ht xc thc vt ri gi nh, ry qua ry 0,25 mm, trn u.
Dng cn phn tch cn 0,2 g (t ngho mn - di 1% th cn 0,4 g, cn t giu mn th cn
0,1 g) cho vo bnh tam gic 100 ml.
Dng burt cho t t chnh xc 10 ml K
2
Cr
2
O
7
0,4N vo bnh. Lc nh bnh, trnh t bm ln
thnh bnh. y bnh bng mt chic phu nh. un trn bp cch ct cho dung dch si nhit
180
0
C trong 5 pht.
Ly ra ngui, dng nc thm 10 - 20 ml vo xung quanh thnh bnh ra icromat bm
vo. Cho vo 4 git ch th axit phenylanthranilic 0,2 % v chun bng dung dch mui Morh 0,2N
n khi dung dch chuyn t mu tm mn sang mu xanh l cy.
ng thi lm mt th nghim trng: cn 0,2 g t nung ht cht hu c cho vo bnh tam gic,
cho vo ng 10 ml K
2
Cr
2
O
7
0,4N v tin hnh cc bc nh phn tch mu:
Tnh kt qu:

Cht hu c = x K

V
0
: S ml mui Morh dng chun th nghim trng
V : S ml mui Morh dng chun mu th nghim
N : Nng ng lng ca dung dch mui Morh
a : Lng mu t ly phn tch (g)
K : H s chuyn i t mu kh khng kh sang mu kh tuyt i.
Ha cht:
K
2
Cr
2
O
7
0,4N trong H
2
SO
4
(1:1): cn 40 g K
2
Cr
2
O
7
tinh khit, nghin bng chy trong ci s,
ha tan trong 500 ml nc. Nu cn, un nng nh tan hon ton. ngui, lc ri nh mc n 1
lt. dung dch vo bnh nh mc 2 lt ri rt t t H
2
SO
4
c (d = 1,84) vo, va rt va lc nh,
nu qu nng th phi ngui ri mi rt tip, cho n th tch 2 lt. Nng ca dung dch ny c
(V
0
- V).N.0,003.1,724.100
a
149
kim tra bng dung dch FeSO
4
(hoc mui Morh) 0,2N. C trng hp sau khi pha xong, mt vi
hm thy c tinh th mu hnh kim xut hin, trong trng hp ny ch cn thm t nc, lc u
tinh th s mt.
Dung dch mui Morh 0,2N: cn 80 g (NH
4
)
2
SO
4
.FeSO
4
.6H
2
O ha tan trong nc, thm 20
ml H
2
SO
4
c, nh mc n 1 lt. Nng ca dung dch ny c xc nh bng cch chun vi
dung dch KMnO
4
0,1 N: ly 10 ml mui Morh cho vo bnh tam gic 250 ml, thm 1 ml H
2
SO
4
c,
50 ml nc ct chun bng dung dch KMnO
4
0,1N n khi xut hin mu hng bn trong 1 pht.
Ch th axit phenylanthranilic: 0,2 g ha tan trong 100 ml Na
2
CO
3
0,2%. S chuyn mu en
dn v sau ny khng nh hng g n vic s dng ch th.
Ch thch:
Trong phng php ny phi ch khng ch nhit khi un oxi ha mu. Nhit cao qu
180
0
C s dn ti vic phn hy cromic. Nikitin B.A (1972) a ra phng php oxi ha cht hu c
bng cch un trong t sy ti nhit 150
0
C trong 20 pht.
t cha nhiu clorua cng nh hng n kt qu phn tch v c mt phn Cr
2
O
7
2-
tiu tn cho
oxi ha Cl
-
:
Cr
2
O
7
2-
+ 6Cl
-
+ 14H
+
2Cr
3+
+ 3Cl
2
+ 7H
2
O
V vy khi phn tch t mn cn ra sch ht Cl
-
trc khi phn tch cht hu c.
b. Xc nh cht hu c theo phng php Walkley - Black:
Nguyn l: Phng php da trn nguyn tc oxi ha cht hu c ca t bng dung dch K
2
Cr
2
O
7
.
Sau chun li lng K
2
Cr
2
O
7
d, t tnh c hm lng cht hu c. im khc phng
php ny so vi phng php Chiurin ch: nhit dng cho qu trnh oxi ha c to ra do qu trnh
ha tan H
2
SO
4
c trong dung dch kali icromat.
Trnh t phn tch:
Cn 1 g t kh khng kh cho vo bnh tam gic 500 ml. Thm 10 ml dung dch K
2
Cr
2
O
7
1N.
Thm 20 ml H
2
SO
4
c vo (thm nhanh theo kh nng c th thm). Lc nh v gi 30 pht. Thm
200 ml nc ct v 10 ml H
3
PO
4
85%. Thm 1 ml ch th iphenylamin. Chun bng dung dch
FeSO
4
0,5N n khi dung dch c mu xanh l cy.
Ha cht:
Ha tan 49,039 g K
2
Cr
2
O
7
trong nc ct v thm th tch n 1 lt.
FeSO
4
0,5N: ha tan 139 g FeSO
4
.7H
2
O trong 800 ml nc, thm 20 ml H
2
SO
4
c ri nh
mc n th tch 1 lt.
iphenylamin: ha tan 0,5 g ch th trong 20 ml nc ri thm tip 100 ml H
2
SO
4
c.
Tnh kt qu:
V
0
- V
1

C(%) = N x x 0,39 x K
a
N : Nng ng lng ca mui FeSO
4
.
V
0
, V
1
: L th tch mui FeSO
4
dng chun th nghim trng v chun mu.
a : Lng mu ly phn tch (g)
K : H s chuyn i t mu kh khng kh sang mu kh tuyt i.
150
0,39 : 3 x10
-3
x 100% x 1,3
3 : ng lng gam ca C
1,3 : H s b cho qu trnh oxi ha cha hon ton cht hu c trong phng php ny.
% cht hu c = 2 x C(%)
Trc y dng h s 1,72 nhng hin nay thy h s 2 l thch hp hn (ISRIC, 1986).
Ch thch:
Trc khi chun lng K
2
Cr
2
O
7
cn d ( c 2 phng php) cn phi ngui dung dch oxi
ha, nu khng mt phn Fe
2+
dng chun lng K
2
Cr
2
O
7
cn d c th b oxi khng kh oxi ha.
Vi 10 ml K
2
Cr
2
O
7
1N ch c th oxi ha ti a 25 mg C v vy khi p dng phng php
Walkley - Black cn ht sc ch lng mu ly i phn tch.
i vi nhng t hm lng mn < 2,6% c th ly 1 g mu em i phn tch, nu hm lng
mn cao hn nn ly 0,2 g t cn khi hm lng mn > 13,5% th lng mu ly l 0,1 g (L c -
Tp ch khoa hc t 10 - 1998).
Nu dng ch th ferroin (0,695 g FeSO
4
.7H
2
O) v 1,485 g 0 - phenaltrolin amonohidrat
(C
12
H
8
N
2
.H
2
O) trong 100 ml nc th dng 4 git ch th - khi kt thc chun , mu ca dung dch
chuyn t xanh sang .
C th dng phng php so mu xc nh cht hu c bng cch o mu Cr
3+
ti bc sng
625 nm. Dng saccaroz (C
12
H
12
O
11
) lm dung dch chun kh Cr
6+
trong K
2
Cr
2
O
11
lm dung dch
chun kh Cr
6+
trong K
2
Cr
2
O
7
thnh Cr
3+
.
9.1.4. chua v cch xc nh chua ca t
chua l yu t ph quan trng ca t, n nh hng n cc qu trnh l ha v sinh hc
trong t v c tc ng n cy trng. a s cy trng thch ng t trung tnh (pH t 6 n 7); mt
s c th chu t chua nh ch (pH t 4,5 n 5,5), khoai ty (pH t 4,8 n 5,4).
t chua l do c mt cc ion H
+
v Al
3+
trong dung dch t cng nh trong cc phc h hp th
ca t c kh nng trao i gy nn.
Kh nng to thnh H
+
v Al
3+
cng ln th t cng chua v ngc li chua ca t ph thuc
vo cc phng php xc nh, trong cht chit rt c ngha ln trong trao i cc ion H
+
v Al
3+
.
Trn cng mt loi t, s dng cht chit rt NaOH 0,01N (pH = 12) s c chua ln (19
mgl/ 100g t) trong khi vi NaCH
3
COO 1N (pH = 8,2) th chua thp hn (6,0 mgl/ 100g t);
v thp nht l khi tc ng vi t bng NaCl 1N (pH = 6,0), chua xc nh c l 0,2 mgl/
100g t. Nguyn nhn l do anion OH
-
c kh nng lin kt mnh vi H
+
(hng s phn li ca H
2
O l
10 - 14) trong khi lin kt ca CH
3
COO
-
vi H
+
l nh hn (hng s phn li ca CH
3
COOH l 1,8.10
-
5
), cn Cl
-
hu nh khng lin kt vi H
+
.
chua ca t thng thng c chia lm 2 loi:
- chua hin ti ( chua hot tnh): l chua gy nn do cc ion H
+
t do trong dung dch
t v c xc nh khi tc ng t vi nc ct v biu th bng pH
H2O
.
- chua tim tng: c xc nh khi chit rt t bng dung dch mui. Da vo cht chit rt,
chua tim tng li c chia thnh chua trao i v chua thy phn:
151
chua trao i: s dng cht chit rt t l cc dung dch mui trung tnh nh KCl, NaCl,
BaCl
2
. Cc cation ca cc mui ny y H
+
v mt phn Al
3+
ra khi phc h hp ph, Al
3+
b thy
phn to thnh chua ca t. chua trao i l 1 ch s xc nh nhu cu bn vi cho t.
chua thy phn: chua ca t c xc nh khi s dng cht chit rt l mt mui thy
phn (gm gc axit yu v baz mnh, nh CH
3
COONa). Thng thng chua thy phn c tr s
ln hn chua trao i. V lc ny gn nh ton b H
+
v Al
3+
trao i c trao i ra ngoi
dung dch t.
chua thy phn cng thng c s dng tnh lng vi bn ci to t chua. Theo
nghin cu ca Vin Khoa hc K thut Nng nghip th t la Vit Nam ch nn trung ha 1/2
chua thy phn l tt nht.
a. Xc nh pH bng phng php cc chn lc hyro:
Hin nay phng php o pH trc tip trn my (pH meter) c dng ph bin. Chng va
nhanh, chnh xc v phm vi pH xc nh c rng (pH : 1 - 9).
Nguyn l: Ion H
+
c chit rt ra bng cht chit rt thch hp (nc ct hoc mui trung tnh),
dng 1 in cc ch th (in cc chn lc hyro) v 1 in cc so snh xc nh hiu th ca dung
dch. T tnh c pH ca dung dch.
Trong cc loi pH meter, in cc ch th thng dng l in cc thy tinh, in cc so snh l
in cc calomen.
Trnh t phn tch:
Lc 10 gam t ( qua ry 1 mm) 15 pht trn my lc (hoc lc tay 30 pht) vi 25 ml KCl 1N
(vi pH
KCl
) hoc nc ct (pH
H2O
). Sau yn 2 gi (khng qu 3 gi), lc 2 - 3 ln ri o pH ngay
trong dung dch huyn ph.
Hiu chnh my o pH: My trc khi o phi hiu chnh bng cch o dung dch m pH tiu
chun. Chnh cho kim ch ng tr s pH ca dung dch m.
o mu: Gi cho in cc cch mt mu t l 1 cm v ngp nc khong 2 cm. Khi my n
nh, c gi tr pH trn my.
Ghi ch: in cc thy tinh c ngm trong nc ct khi khng dng. T l t v dch chit c
khc nhau ph thuc phng php. V vy trong kt qu phn tch cn ghi r t l t: dch chit rt v
cht chit rt. V d: pH trong KCl 1N - 1:5 W/V. Ngha l pH khi chit rt bng KCl 1N vi t l
t dung dch chit rt l 1:5 (khi lng/ th tch). Nu khng ghi ch g th thng c hiu l
pH
H2O
theo t l t nc l 2:5.
Pha dung dch m tiu chun:
Dung dch KHC
8
H
4
O
4
0,05 M: 10,21 g KHC
8
H
4
O
4
pha thnh 1000 ml.
Hn hp KH
2
PO
4
+ NaHPO
4
0,025M: 3,10 g KH
2
PO
4
pha thnh 1000 ml; 3,55 g Na
2
HPO
4

pha thnh 1000 ml.
Trn ln 2 dung dch ny thnh 2 lt hn hp. Thi hn s dng khng qu 2 thng.
Dung dch Na
2
B
4
O
7
0,01M: 3,81 g Na
2
B
4
O
8
.10H
2
O pha thnh 100 ml
Dung dch KHC
4
H
4
O
6
bo ha: 6 g KHC
4
H
4
O
6
trong 1 lt nc ct.
Cc dung dch trn pha xong ng trong bnh polyetilen, thi hn dng khng qu 3 thng.
Tr s pH ca cc dung dch m trn nh sau:
Nhit
o
C KHC
8
H
4
O
6

KHC
8
H
4
O
4
KH
2
PO
4
. Na
2
B
4
O
7

152
bo ha 0,05M NaHPO
4

0,025M
0,01M
15
20
25
30
35


3,56
3,55
4,00
4,00
4,00
4,01
4,02
6,90
6,88
6,86
6,85
6,84
9,27
9,22
9,18
9,14
9,10
Da vo chua trao i (pHKCl), chua ca t c chia ra nh sau:

pH 4,5 5,0 5,5 6,0
Xp loi rt chua chua va chua nh gn trung tnh trung tnh
b. Xc nh chua trao i theo phng php Daicuhara:
Nguyn l: S dng cht chit rt KCl, ion K
+
s y H
+
v Al
3+
trao i ra khi h phc hp th
(keo t):


K + 4K
+
[KD] 4K
+
+ H
+
+ Al
3+


Al
3+
+ 3HOH Al(OH)
3
+ 3H
+

Dng NaOH tiu chun chun H
+
to thnh vi ch th mu phenolphtalein.
Nc chit ny c th kt hp o pH
KCl
xc nh nhm di ng (Al - trao i) v Ca, Mg trao i.
Trnh t phn tch:
Cn 40 g t ( qua ry 1 mm) lc 1 gi vi 100 ml dung dch KCl 1N (hoc lc vi pht ri
yn mt ngy), sau tin hnh lc.
Ly 50 ml dch lc + 3 git phenolphatalein ri chun bng NaOH 0,02N tiu chun n xut
hin mu hng khng bin mt trong vng 1 pht.
Tnh kt qu:

H
t
(mgl/ 100g t) = . 100

H
t
: chua trao i
V : S ml NaOH chun mu
N : Nng ng lng ca NaOH (0,02N)
W : Lng t em phn tch (40 g)
K : H s pha long (100/50 = 2)
Rt gn c:
H
t
(mgl/100 g t) = V . 0,1
Ha cht:
V.N.K
W
H
+

Al
3+

153
NaOH 0,02N: Ly 200 ml NaOH 0,1N pha thnh 1000 ml trong bnh nh mc. Dng axit
chun (H
2
SO
4
0.02N) kim tra li nng .
Phenolphtalein 0,1 g phenolphtalein ha tan trong 60 ml ru etylic ri pha thnh 100 ml bng
nc ct.
KCl 1N: 75 g KCl pha thnh 1 lt.
Ghi ch: chua trao i xc nh bng chun ch p dng t chua. Khi t c pH
KCl
> 7,5
s khng xc nh c v phenolphtalein to thnh mu hng ngay trong dung dch mu.
c. Xc nh H
+
v Al
3+
trao i theo phng php Xclp (1939):
Nguyn l: Khi tc ng vi t bng dung dch mui trung tnh (KCl chng hn) th ng thi c
H
+
v Al
3+
trao i u c y ra khi tng hp th trao i ca keo t:

K + 4KCl [KD] 4K
+
+ H
+
+ Cl
-
+ AlCl
3


Khi AlCl
3
li b thy phn to thnh H
+
:
AlCl
3
+ 3HOH Al(OH)
3
+ 3HCl
T 1 ion Al
3+
thy phn s to thnh 3 ion H
+
. Nh vy thc cht khi chun xc nh chua
trao i bao gm c H
+
trao i, H
+
t do trong dung dch t, H
+
c to thnh do Al
3+
trao i
c xc nh theo cng thc:
Al
3+
trao i = chua trao i - H
+
trao i.
Xlcp s dng NaF lin kt vi Al
3+
, do s xc nh c ring H
+
trao i:
Al
3+
+ 6F
-
AlF
6
3-

Lc ny trong dung dch ch cn H
+
t do, dng phng php chun xc nh chng. Thng
thng Al
3+
di ng tn ti iu kin pH
KCl
< 5,5.
Do vy Al
3+
ch c ngha ln cc t chua, v c xc nh cng vi khi xc nh chua
trao i.
Trnh t phn tch:
Cn 100 g t lc vi 250 ml KCl 1N trong 1 gi ri lc.
Xc nh chua trao i: Ly 50 ml dch lc vo bnh tam gic 250 ml, un si 5 pht, cho vo
2 git phenolphtalein, ngui ri chun vi NaOH 0,02N tiu chun n mu hng bn vng (trong
1 pht).
Xc nh H
+
trao i (gm H
+
trao i v H
+
c sn trong dung dch t).
Ly 50 ml dch lc trn vo bnh tam gic 250 ml, un si 5 pht, cho vo 5 ml NaF 3,5%,
ngui, cho vo 2 git ch th phenolphtalein, dng NaOH 0,02N (dung dch tiu chun) chun n mu
hng.
Tnh kt qu:

chua trao i (mgl/100 g t) = . 100 = V
1
. 0,1


H
+
trao i (mgl/100 g t) = . 100 = V
2
. 0,1
H
+

Al
3+

V
1
.N.K
W
V
2
.N.K
W
154


Al
3+
trao i (mgl/100 g t) = .100 = (V
1
- V
2
).0,1
W
Hay Al
3+
trao i = chua trao i - H
+
trao i
V
1

: S ml NaOH chun mu khng c NaF
V
2

: S ml NaOH chun mu c NaF
N : Nng ng lng ca NaOH (0,02N)
W : Lng t cn (100 g)
K : H s pha long (250/50 = 5)
Al
3+
thng c biu th bng mg/100g t. Ly kt qu mgl/100g t x 9 hoc:

(V
1
- V
2
).N.K.9
Al
3+
(mg/100 g t) = . 100
W
Ha cht:
NaOH 0,02N tiu chun
KCl 1N: 75 g KCl pha thnh 1 lt
Phenolphtalein 0,1%: 0,1 g phenolphtalein pha trong ru elylic 100 ml.
NaF 3,5%: 3,5 g NaF pha trong nc ct 100 ml. NaF pha xong phi chnh pH n trung tnh.
Ghi ch:
Khi cho u lng NaF nh nhau vo mu, c th lm i chng kh H
+
t do trong dung dch
NaF.
Thc t lng NaF cho vo c th khng c nh, ph thuc vo lng Al
3+
. Lng 5 ml NaF ch
tc dng vi 1,80 mgl Al
3+
l tt nht. Khi Al
3+
ln hn 6,3 mgl/100g t th s khng . C th
tnh lng NaF 3,5% cn thit:
V
NaOH
. N
NaOH
.2
NaF 3,5 %(ml) =
0,85
d. Xc nh chua thy phn theo phng php Kappen:
Nguyn l: Dng 1 mui kim mnh axit yu (thng l CH
3
COONa) trao i H
+
v Al
3+
t
keo t:

K + 4 CH
3
COONa [K] 4Na
+
+ CH
3
COOH + (CH
3
COO)
3
Al

Ngoi tc dng trao i ca Na
+
, ion CH
3
COO
-
c kh nng lin kt vi H
+
v Al
3+
lm tng
cng qu trnh trao i. Do vy kt qu trao i s trit hn dng mui trung tnh ( chua trao
i). Qu trnh thy phn ca (CH
3
COO)
3
Al lm tng H
+
trong dung dch:
H
+

Al
3+

(V
1
- V
2
).N.K
155
(CH
3
COO)
3
Al + HOH CH
3
COOH + Al(OH)
3

Chun trc tip lng H
+
to thnh bngdung dch CH
3
COONa 1N (pH=8,2) trong 1 gi ri
lc.
Ly 50 ml dch lc + 2 git phenolphtalein ri chun bng NaOH 0,02N ti mu hng (bn trong
1 pht).
Tnh kt qu:
V.N.1,75.K
H
tf
(mgl/100 g t) = .100
W
V : Th tch (ml) NaOH chun
N : Nng ng lng NaOH (0,02N)
K : H s pha long (100/50 = 2)
W : Khi lng t (40g)
1,75 : Dng CH
3
COONa trao i 1 ln khng trit . Mun trao i hon ton H
+
, Al
3+

cn lp li nhiu ln, nh vy mt thi gian v phc tp. Qua thc nghim cho thy nhn vi h s
1,75 l thch hp (h s thc nghim).
H
tf
: chua thy phn (mgl/100 g t)
Rt gn: H
tf
(mgl/100 g t) = V.0,175
Ha cht:
CH
3
COONa 1N (pH = 8,2): 136,1 g CH
3
COONa.3H
2
O ha bng nc ct n 1 lt. iu
chnh cho pH = 8,2 (va lm i mu ch th phenolphtalein).
Ha cht khc: xem xc nh chua trao i trn.
- Ghi ch: chua thy phn thng c s dng tnh no baz ca t v tnh lng vi
bn (theo nghin cu ca Vin Khoa hc K thut Nng nghip vi t la nc ta ch cn trung ha
1/2 chua thy phn). Nu ly su cn trung ha 1/2 chua thy phn s l:
CaO (tn/ha) = 0,42 . Htf
Trong : H
tf
tnh theo mgl/100 g t
9.1.5. Xc nh dung tch trao i cation ca t
Dung tch trao i cation ca t hay kh nng trao i cation (CEC - cation exchange capacity)
l lng ion ln nht c t hp ph c kh nng trao i v c biu th bng mgl/100g t. y
chnh l qu trnh hp ph l ha hc c thc hin nh keo t. Cn phn bit qu trnh trao i
cation (do keo m m nhn) vi trao i anion (do keo dng m nhn). Di y ch cp n
vic xc nh dung tch trao i cation.
Xc nh dung tch trao i cation theo phng php amoniaxetat (phng php Schachtschabe).
Nguyn l: Dng CH
3
COONH
4
1N lm bo ha dung tch hp ph trao i cation ca t. Phn
ng trao i nh sau:


K + nCH
3
COONH
4
K 6NH
4
+
+ (n-6)CH
3
COO
-
+ Ca
2+
+ Mg
2+
+

K
+
+ H
+

Ca
2+

Mg
2+

K
+

H
+

156

Sau cation NH
4
+
hp ph c trao i ra bng cation K
+
(KCl 0,1N):
K] 6NH
4
+
+ nKCl K] 6K
+
+ 6NH
4
+
+ (n-6)KCl
Lng NH
4
+
trao i ny c xc nh bng chun bng NaOH 0,1N vi s c mt ca
focmalin (HCHO):
4NH
4
+
+ 6HCHO = (CH
2
)
6
N
4
+ 6H
2
O + 4H
+

(hecxametilentetraamin)
Vi 4NH
4
+
s gii phng 4H
+
. Do vy da vo lng NaOH tiu tn m tnh c lng NH
4
+

hay lng cation trao i.
Trnh t phn tch:
Cn 10 gam t (qua ry 1 mm) cho vo phu Mehlich chun b sn.
Dng 100 ml CH
3
COONH
4
1N (pH = 7) chia 10 ln (10 ml x 10 ln) bo ha t bng NH
4
+
.
Ra t 3 ln bng ru etylic (15 ml x 3 ln). Dch trao i xc nh thnh phn cation trao i
(Ca
2+
, Mg
2+
, Al
3+
, K
+
,...) nu cn thit.
Chuyn ton b phu v t sang bnh nh mc 250 ml, ri dng 250 ml KCl 0,1N trao i (25
ml x 10 ln) ln th tch n 250 ml. Ly 25 ml dch trao i ny + 10 ml focmaln 20% + 5 git
phenolphtalein, ri chun bng NaOH 0,05N tiu chun n mu hng nht (bn trong 1 pht).
Tnh kt qu:
V.N.K
CEC = . 100
W
CEC : dung tch trao i cation (mgl/100 g t)
V : Th tch NaOH chun (ml)
N : Nng NaOH chun (0,05N)
W : Lng t cn (10 g)
K : H s pha long (250/25 = 10)
Rt gn: CEC (mgl/100 g t) = V . 5
Ha cht:
CH
3
COONH
4
1N: 77 g CH
3
COONH
4
pha thnh 1 lt bng nc ct (dng NH
4
OH hoc
CH
3
COOH iu chnh cho pH = 7).
KCl 0,1N: 7,5 g KCl pha thnh 1 lt.
Focmalin 20%: pha t focmanlin thng dng (khong 38%). Sau trung ha bng NaOH
0,05 N vi ch th phenolphtalein.
Phenolphtalein 0,1% (pha trong cn, ru).
NaOH 0,05N tiu chun.
Ghi ch:
Phng php dng CH
3
COONH
4
c dng ph bin nhng ph hp nht vi t trung tnh v
khng cacbonat. N cng c s dng cc t chua nh.
157
NH
4
+
c th b gi cht bi cc khong st 1:1 (kaolinit) v mn nn kh thu li c. Do vy
t nhiu st, kt qu c th thp hn thc t.
Lng t cn c th thay i ph thuc t. Thng thng t thnh phn c gii nng c th
cn 5 g t + 5 g ct sch ( c x l bng H
2
SO
4
c) tng cng tc trao i.
C th lm chun trng vi focmalin (i chng) loi tr H
+
cha c trung ha. Kt qu
xc nh mu phi tr i lng chun ny (nu c).

9.2. Xc nh mt s kim loi nng trong t
Trong dinh dng ca thc vt v vi sinh vt, ngoi cc nguyn t nit, photpho v kali, cc kim
loi nng nh bo, mangan, ng, km, coban, molipen... c ngha ln. Mt lng nh ca cc
nguyn t ny cn thit cho nhiu qu trnh sinh hc xy ra trong cc c th thc vt v ng vt.
Ngun cung cp ch yu cc kim loi nng trong t l cc to thnh t. Trong qu trnh to thnh
t v hot ng sng ca thc vt v ng vt xy ra qu trnh phn b li cc kim loi nng theo
phu din t.
Hm lng cc kim loi nng trong cc loi t khng vt qu 10
-4
%, tr mangan hm lng
ca n trong mt s trng hp, v d nh trong cc thnh to mi ca mangan - st i khi c tnh
n phn trm.
Tuy nhin mangan vn c xp vo cc kim loi nng khi tnh n hm lng thp ca n trong
cc c th sng v vai tr sinh ha to ln ca n trong i sng ng, thc vt.
Khi nghin cu hm cc kim loi nng trong t ngi ta thng xc nh hm lng tng s v
hm lng c th s dng c i vi dinh dng ca thc vt nh thng c gi l dng di ng
ca cc kim loi nng.
- Chn phng php xc nh, chun b t v cc thuc th:
Khi tin hnh nghin cu hm lng cc dng khc nhau ca cc kim loi nng cn la chn cc
phng php xc nh chng, phng php phi m bo c chnh xc, nhy v chn lc.
Ch c th xc nh mt lng nh cc cht bng cc phng php c nhy cao. Tuy nhin cc
phng php c nhy cao thng c chnh xc thp, v d nh phng php khi lng c sai
s tng i tnh theo phn trm 0,01%, phng php trc quang l 2 - 3%, phng php cc ph
dng khuch tn l 5 - 10%.
Mu t c nghin trong ci m no v ry qua ry lm bng si capron v khung ry lm t
cc vt liu hu c .
Nc dng cho phn tch l nc ct c ct li hay cho i qua nha trao i ion, thng s
dng nc ct hai ln.
Cc axit v amoniac cng c tinh ch bng cch ct hay s dng thuc th loi c bit tinh
khit. Cc thuc th khc c tinh ch theo m t trong phng php xc nh ca tng nguyn t.
Cc thuc th thng b bn nguyn t km v th khi xc nh nguyn t ny cn phi tin hnh th
nghim kim tra s c mt ca n trong cc thuc th s dng.
Thnh phn ca thy tinh ch to cc dng c th nghim cng cn phi c lu tm, c bit
khi xc nh bo.
158
Nhng ha cht dng pha dung dch chun nn kt tinh li. Thng hay pha hai loi dung dch
chun: dung dch chun gc v dung dch chun s dng. Dung dch chun gc thng c pha vi
hm lng 0,1 mg nguyn t trong 1 ml; cn nhng lng cn vi hm lng nguyn t nh vy cho
php chng ta c th trnh c sai s. Dung dch chun s dng c chun b bng cch pha long
dung dch chun gc. Khi pha long 10 ln ta c dung dch cha 0,01 mg hay 10 g/ml. Khi pha
long 100 ln nhn c dung dch c hm lng 0,001 mg hay 1 g/ml. V nhng dung dch qu
long khng bn nn ngi ta ch chun b cc dung dch ny trong ngy tin hnh phn tch v ch
gi trong ngy .
- Tnh kt qu xc nh cc kim loi nng:
Kt qu xc nh cc kim loi nng trong t c biu th bng mg trong 1 kg t (mg/kg) hoc
biu th bng ppm (parts per milion) ngha l mt phn mt triu tng ng vi 10
-4
%.
9.2.1. Phng php phn hy mu truyn thng
a. Chun b mu:
- Lm kh cc mu t: Nhng mu t ti cn phi a v trng thi kh khng kh. Lm kh
mu nn tin hnh ch sch, thong, trng hp c bit c th dng t sy, khng ch nhit t
30 - 40
0
C. Dn mu t (trng lng 800 - 1000g) thnh lp mng trn giy thuc hoc giy bng m,
nht ht r cy, , si...c ln trong mu. p nh mu t mu c kch thc 5 - 10 mm. C th
dng my hay ci s khng c cc kim loi nng p nh mu trc khi ly mu trung bnh.
Vic chn, nghin v ry mu t c tin hnh trong phng ring c thit b thng gi v ht
bi tt.
- Ly mu trung bnh: T mu ban u ly ra khong 200 g, dng thit b trn u mu. Nu
khng c thit b ny c th dng php chia t ly mu (Hnh 9.6). Mu t c trn ri ri u
trn giy sch thnh mt lp mng c dng hnh vung. Chia hnh vung theo hai ng cho thnh 4
phn bng nhau. Ly hai phn i din (phn 1 v 3 hoc 2 v 4) gp li vi nhau, hai phn cn li c
th b i hoc dng vo vic khc.

Hnh 9.6. Phng php chia t ly mu
Sau khi chn xong, mu c nghin nh trng ci m no, ry qua ry c ng knh 1 mm.
Nn dng loi ry lm bng si capron v khung lm bng cc vt liu hu c. Mu t sau khi ry
c dng xc nh cc kim loi nng.
b. Phn hy t khi xc nh hm lng tng s cc kim loi nng:
Trong t, cc kim loi nng ch yu tham gia trong thnh phn cc khong nguyn sinh, th sinh
v trong cc hp cht v c, hu c khc nhau. xc nh hm lng tng s cc kim loi nng
trong t cn phi thiu hy cc cht hu c v phn hy phn khong ca t nhn c nhng
mui d ha tan.
Mun phn hy t ngi ta thng s dng 2 phng php: phng php nung chy t vi hn
hp cacbonat ca cc kim loi kim v phng php phn hy bng cc axit v c c.
159
Qu trnh nung chy vi hn hp cacbonat ca cc kim loi kim c tin hnh trong cc chn
platin c np nhit 1000
0
C. Sau khi nung chy, ngi ta nhn c mui kim ca axit silicic v
cc hp cht d ha tan khc. Chuyn hn hp chy sang dng dung dch, dng axit clohyric tch
axit silicic, ri tin hnh xc nh cc kim loi nng trong dung dch. Khi x l hn hp bng axit
clohyric (HCl d = 1,19) s to nn mt lng tng i ln kt ta ht nh SiO
2
, kt ta ny c th
gi mt lng ng k cc kim loi nng v nh vy kt qu phn tch s gim xung. Axit clohyric
dng x l hn hp c th cha cc kim loi nng di dng tp cht v cng c th ha tan mt
lng platin chn ng mu, nguyn t ny s cn tr vic xc nh cc kim loi nng (v d
molipen, vanai...).
Phng php phn hy mu bng hn hp axit HF v H
2
SO
4
l phng php c s dng nhiu
nht khi xc hm lng tng s cc kim loi nng. Phng php ny m bo phn hy hon ton mu
t v tch axit silicic di dng SiF
4
. Tuy nhin trong trng hp ny c mt vi phn khong (hay
mt phn trong ) nh topaz, analuzit zirkon, sillimanit s khng b ph hy v vy t cha nhiu
cc loi khong ny khng nn ph hy mu bng HF.
Vic la chn cc phng php phn hy mu t tu thuc vo nhng kim loi nng cn xc
nh trong mu. V HF (loi tinh khit phn tch) c cha hn hp cc kim loi nng, cho nn khi
xc nh cc kim loi nng nh km, coban cn phi ct HF trong cc dng c ct c bit ch to t
palai hay platin. Axit clohyric loi c bit tinh khit khng cn phi tinh ch.
Khi s dng HF phi ht sc cn thn, cn eo gng tay cao su v ch lm ni c thit b thng
gi tt.
Khi xc nh km, ng, coban trong t phi dng axit flohyric ct li 3 ln phn hy
mu t v sau ha tan kt ta, axit clohyric phi dng loi ct 2 ln.
i vi cc nhm kim loi nng khc (molipen, vanaddi, mangan...) khng nht thit phi nh
vy. Khi xc nh cc nguyn t ny ch cn axit flohyric loi tinh khit ha hc (khng cn ct li)
v axit clo hyric ct li mt ln. Nhng theo qu trnh phn tch nhm cc nguyn t ny i hi
phi chng phn cn li 2 n 3 ln vi nc sau khi phn hy mu ( tch flo trit hn), nung
phn cn li 1 - 2 pht trn n kh hay trong l nung v tip theo cn x l nc lc c cn bng
axit pecloric (HClO
4
) tch crm. Khi phn hy mu bng hn hp HF v H
2
SO
4
cn ch n
lng mu ly phn hy; khng nn ly lng mu ln hn 3 g v khi lng mu l 5 - 6 g th kh
c th phn hy hon ton phn khong ca t v kh tch SiO
2
.
Di y l mt vi cch phn hy mu bng hn hp HF v H
2
SO
4
i vi 2 nhm kim loi
nng nu phn trn.
+ Khi xc nh ng, km, coban trong t, tin hnh phn hy theo phng php sau:
Cn mu t xc nh hm lng tng s cc kim loi nng trn cn phn tch. i vi t st v
t st pha ly 1,5 g mu, cn vi t ct v ct pha ly 2 - 3 g mu. Sau khi cn mu xong, cho mu
vo chn platin v nung nng trong l nung nhit 500 - 550
0
C trong 3 gi phn hy cht hu
c. Trnh nung nhit cao hn v c kh nng lm mt cc kim loi nng. Sau khi nung mu xong
ngui, cho vo chn 1 - 2 ml nc ct 2 ln, 1 ml H
2
SO
4
(d = 1,84) v 20 ml axit flohyric, t chn
ln bp in kn v un n khi xut hin kh SO
2
mu trng. Khng nn un qu mnh (khng vt
qu 200 - 250
0
C) trnh lm bn cc cht trong chn ra ngoi.
Sau khi xut hin kh SO
2
, ly chn ra khi bp in, ngui v thm vo khong 10 - 15 ml HF
ri li tip tc un trn bp cho n khi kh hon ton. Chuyn chn sang bp in c kh nng un
160
nng hn, tip tc un n khi ht kh SO
3
bay ra. Nhc chn ra khi bp in, ngui ri cho vo
chn 10 ml HCl 22% (loi c bit tinh khit) v 10 ml nc ct 2 ln ha tan phn kh cn li.
Tip tc t ln bp v un nng nh khong 30 - 40 pht.
Khi phn cn li tan ht, em lc dung dch qua giy lc bng trng (ng knh 9 cm)
c ra trc bng HCl 10% loi ht vt cc kim loi nng. Sau khi lc xong, ra giy lc bng
nc ct 2 ln nng c axit ha bng HCl n khi ht vt st. Gp hai phn nc lc v nc ra
li vi nhau (khong 100 ml) ri chng ct dung dch n th tch khong 50 ml. Dung dch ny dng
xc nh cc kim loi nng (km, coban, ng) theo cc phng php khc nhau.
+ Khi xc nh molipen, vanaddi, mangan t mt mu t, dng phng php ph mu
sau:
Cn 2,5 - 3 g t c nghin nh n dng bt cho vo chn platin, t chn vo l nung ri
t nng n nhit 500 - 550
0
C v gi nhit ny t nht 3 gi phn hy cht hu c.
ngui, cho vo chn 2 ml nc ct 2 ln, 2 ml H
2
SO
4
c, 20 ml HF 30 - 40%. t chn ln bp in
v y np kn, un n khi xut hin kh SO
3
th thm vo 0,5 ml H
2
SO
4
v 10 ml HF, li chng mu
n kh. tch flo v phn axit cn li trong chn, ta chng phn kh trong chn 2 ln, mi ln vi 5
ml nc. t nh phn kh cn li trn n kh hay trong l nung tch hon ton axit. Lm lnh
chn, x l phn cn li trong chn bng 20 ml HCl 22%, y chn li ri un trn bp in n khi tan
hon ton phn cn li. Thm vo 10 ml nc ct 2 ln, lc dung dch qua giy lc v hng vo bnh
250 ml, ra dung dch bng nc nng c axit ha bng HCl (98:2) n khi ht phn ng ca st
trong nc lc vi KSCN. Chng dung dch lc n kh, cho vo bnh 5 ml HCl 22%, 2 ml HClO
4
v
li chng dung dch n kh tch crm. Thm vo phn kh 5 ml nc ct 2 ln, li chng n kh
tch ht vt HClO
4
. Thm vo phn kh trong bnh 2 ml HCl chuyn mui sang dng clorua,
chng kh dung dch. Thm 20 ml HCl 22% v 15 ml v un nng nh ha tan phn kh. Chuyn
dung dch vo bnh nh mc 50 ml. Thm nc ct n vch mc. Phn dung dch ny c dng
xc nh molipen, vanai, mangan.
9.2.2. Phng php phn hy mu bng k thut vi sng (microwave)
a. Gii thiu v k thut vi sng:
Vi sng (microwave) l sng cc ngn hay cn gi l sng vi ba c bc sng t 1 mm n 1 m.
Nng lng ca vi sng l nng lng in t. Trong phn tch ngi ta thng s dng vi sng vi
tn s 2,45 MHz.
Cc phng php t truyn thng thng da trn cc hin tng dn nhit, i lu v bc
x. Nhit c truyn t bn ngoi vo thng qua s tip xc trc tip hoc gin tip. Lng nhit ny
s lan ra ton b vt c t nng nh s chnh lch nhit ti hai im khc nhau, s chnh lch
ny t l nghch vi dn nhit ca vt c t nng. Phng php ny c nhc im l chm v
khng n nh.






i lu nhit
Hn hp axit-mu
Nhit t nng t bn ngoi
Hn hp axit-mu
(Hp th nng lng
vi sng)
161



Hnh 9.7. Ph mu theo
phng php truyn thng
Hnh 9.8. Ph mu theo
phng php vi sng

S t nng vi sng ngc li vi phng php t nng truyn thng. Nhit c sinh ra ngay
ti trung tm ca vt c t nng v lan theo t hng trong ra ngoi.
Phng php ny c u im l:
- Khng c qun tnh nhit (c khi bt u v kt thc).
- y l nng lng sch, d to v d kim sot.
- t nng nhanh
- C tc dng c bit vi cc phn t c lin kt phn cc.
Nng lng vi sng c pht ra t mt ngun pht sng in t (magnetron). Bn cht ca vi
sng l sng in t gm hai yu t: yu t t trng v yu t in trng. Qu trnh chuyn ha
nng lng in t thnh nng lng nhit bao gm 2 c ch: c ch chuyn dn ion v c ch quay
cc phn t. Nhit sinh ra cho s chuyn dn ion nh l kt qu ca s tng tr khng ca mi trng
chng li s dch chuyn ca cc ion trong trng in t. Cn c ch quay cc phn t l qu trnh
quay phn t phn cc theo s i hng ca in trng. S t nng bng k thut vi sng da trn
s hp th trc tip nng lng vi sng ca mu, do vy cc hin tng nh dn nhit, i lu v bc
x nhit ch ng vai tr th yu trong qu trnh cn bng nhit.
u im ca phng php phn hy mu bng vi sng trong phn tch kim loi nng:
- Tin hnh cc phn ng phn hy mu rt nhanh, tit kim thi gian. c bit c hiu qu i
vi cc mu kh phn hy bng cc phng php thng thng.
- Lng mu s dng t, thng t 0,5 - 5 g.
- Hiu sut ca phn ng phn hy rt cao do vy kt qu phn tch thu c chnh xc hn so
vi cc phng php khc.
- Tiu hao ha cht t, do vy chi ph cho qu trnh x l thp.
- Thit b d s dng, an ton v bo v mi trng.
b. Phn hy mu bng vi sng:
S c bn ca mt quy trnh chun









Nghin trn mu
PHN HY MU - V C HA MU
Phn tch bng cc phng
php phn tch cng c:
- ICP & ICP-MS
- AAS
- UV/VIS
- Chun in th
- Sc k ion
- Cc ph
- ...
Mu
162





Cc hn hp axit dng cho phn hy mu:
Cc axit thng s dng trong qu trnh phn hy mu l H
2
SO
4
, HNO
3
, HCl, HF, HClO
4
, H
2
O
2
.
Vic s dng hn hp cc axit ny trong qu trnh phn hy mu ph thuc vo nguyn t cn
xc nh. V d nh khi xc nh cc nguyn t nh Ba, Sr, Pb, Ca, Ag, Hg khng nn s dng axit
sunfuric cng ph mu v mui sunfat ca cc kim loi ny t tan.
Cc axit ny c nhit si khc nhau (H
2
SO
4
98% : 340
0
C; HCl 20,4% : 110
0
C; HNO
3
65% :
120
0
C; HF 40% : 108
0
C; HClO
4
72% : 203
0
C) do ty theo hn hp axit ph hy mu ta phi s
dng cc bnh ph mu ph hp. i vi cc axit c nhit si thp ngi ta thng s dng loi
bnh nha teflon ph mu. Cn cc axit c nhit im si cao (axit sunfuric) ngi ta thng
phi s dng cc loi bnh lm t thy tinh borosilicat hoc thch anh (ch khng s dng bnh loi
ny khi c mt axit flohyric).
Bng 9.9. Mt s v d so snh gia phng php ph mu vi sng v phng php truyn thng
i tng phn tch Lng mu V c ha bng phng
php vi sng
V c ha bng phng
php c in
Mu thc phm 0,1 - 2 g 15 - 30 pht 2 - 4 gi
Mu bn thi 0,1 - 2 g 10 - 40 pht 2 - 4 gi
Mu a cht 0,1 - 1 g 10 - 50 pht 4 - 16 gi
Mu du 0,5 - 5 g 50 - 75 pht 2 - 8 gi
Mu cao phn t 5 g 50 - 75 pht 2 - 4 gi
c. Mt s hng dn v an ton khi s dng thit b phn hy mu bng vi sng:
Khi c mt cc cht oxi ha mnh (H
2
O
2
, HClO
4
, HNO
3
..) khng c s dng cc cht bi trn
c gc du v m.
Khng trn trc tip cc cht oxi ha mnh nh H
2
O
2
, HClO
4
...vi cc mu dng nn hu c v
v c m phi x l trc bng axit (sunfuric, sunfonitric, nitric...).
Khi s dng cc cht oxi ha mnh phi lu khng mu qu kh trong thi gian tin hnh x
l.
Khng c s dng cc axit bc khi (m c).
i vi cc cht ht m mnh (nh tinh bt) khng c trn trc tip vi cc cht oxi ha, hoc
thm ch vi axit trc khi lm t chng bng nc.
c bit ch khi s dng axit nitric vi cc cht hu c cha xenlulo, v chng c kh nng to
ra cc hp cht nitro-xenlulo d gy n.
9.2.3. Chun b mu thc vt xc nh hm lng cc kim loi nng
Mu thc vt xc nh hm lng cc kim loi nng cn phi c phi, sy kh hoc gi trong
t m nhit 30 - 40
0
C. i vi nhng cy c c, thc vt thn m (cy ng,...) c ct s b
thnh nhng phn nh hn cho mu chng kh v tin cho vic nghin nh mu.
163
Sau khi sy kh, mu c nghin nh bng cc loi my xay, my nghin hoc s dng thuyn
tn tn nh. Cc dng c ny phi m bo khng lm nhim bn cc kim loi nng vo mu. Mu
thc vt sau khi nghin nh c th dng mt trong hai phng php tro ha kh v tro ha t phn
hy mu.
Phng php tro ha kh:
i vi phng php tro ha kh, mc nghin v "lm cht" trong chn gi vai tr quan trng.
Mu nghin qu nh, nm hon ton di y chn s ngn cn s xm nhp ca oxi lm chm qu
trnh tro ha mu. V th mu trong chn phi xp tng kh nng xm nhp ca oxi lm cho qu
trnh phn hy mu din ra nhanh hn.
Lng mu ly tro ha tu thuc vo hm lng ca kim loi nng cn xc nh trong mu.
xc nh ring tng nguyn t ngi ta thng ly lng mu nh sau:
ng: 0,2 - 0,5 g Km: 0,05 - 0,2 g
Mangan: 1 - 2 g Coban: 5 - 10 g
Molipen: 1 - 4 g Bo: 0,25 - 1 g
Thc t ngi ta thng xc nh ng, km, mangan, molipen trong cng mt mu, khi
lng mu ly thng l 5 g. xc nh bo v coban ngi ta ly cc loi mu ring: coban: 5 -
10 g; bo: 0,25 - 1 g
Tro ha: Ngi ta thng tin hnh tro ha kh trong l nung nhit 450 - 500
0
C, thi gian
tro ha l 5 - 8 gi. Trong qu trnh tro ha cht hu c, nhng hp cht ca cc kim loi nng c
nhit nng chy khc nhau c to thnh. ttrnh mt cc kim loi nng, nhit trong l
nung cn phi khng ch di 500
0
C (Troitxky, 1957).
tro ha, tt nht nn dng chn lm bng thch anh, nu khng c loi ny c th dng chn
s hoc chn thy tinh chu nhit. Khi dng chn s nu nung nhit qu 500
0
C c th dn n
vic nung chy sn phm tro ha vi men ca thnh chn.
Thnh phn mu tro ha c nh hng ln n qu trnh tro ha. i vi mu thc vt khng
nhng thnh phn mu c nh hng n qu trnh tro ha m ngay c ni thc vt sinh trng v
pht trin cng c nh hng n qu trnh tro ha mu. Ngi ta tin hnh th nghim v thy rng
nhng cy thuc h ha tho trng pha nam tro ha nhanh hn nhng cy trng pha bc
(Gribovxcaia - 1968). iu cho thy mt s khng ng u v kim v SiO
2
trong t bo thc vt
nhng vng khc nhau. Mt lng ln SiO
2
s ngn cn qu trnh tro ha hon ton mu thc vt.
Phn cn li khng ha tan ca axit silicic, to thnh do kt qu ca qu trnh tro ha mu thc vt c
th cha mt lng ng k hn hp cc kim loi nng.
tro ha ta cn mu (mu trng thi kh khng kh) cho vo chn ri t vo l nung. Mu
thc vt trong chn cng xp cng tt, iu s lm tng tc ca qu trnh tro ha. Trong qu
trnh nung mu, nn khng ch nhit tng t t. Nhit tng qu nhanh c th lm mu bn ra
ngoi trong qu trnh t nng mu.
Sau , trong qu trnh tro ha nn cn thn m ca l nung tng thm s tham gia ca oxi vo
mu tro ha nhm nng cao tc tro ha v phn tro nhn c s khng c hn hp cacbon. Thi
gian tro ha ph thuc vo thnh phn mu tro ha, mc nghin mu v lng mu em tro ha.
tng tc oxi ha phn mu hu c cn li, ta thm vo trong chn 1 - 2 ml HNO
3
c, trng
kh trn bp in v nung nng trong l nung nhit 450 - 500
0
C trong 1 gi. Lp li qu trnh x
164
l mu bng axit ri chng v nung trong l n khi oxi ha hon ton cht hu c , sau ha tan
phn kh bng axit HCl 10%, lc dung dch qua giy lc bng trng vo bnh nh mc 100 ml.
Nu trong chn v trn giy lc c mt lng ln phn khng ha tan (bao gm SiO
2
v hn hp
cc cht kh tan khc) th tt nht nn ph hy phn khng tan ny trnh mt cc kim loi nng cn
xc nh. chuyn hp cht kh tan ny sang trng thi ha tan, ta chuyn ton b phn ny ln trn
giy lc ri sy kh giy lc. Cho giy lc ny vo chn platin ri thiu hy trong l nung nhit
450 - 500
0
C. Qu trnh thiu hy tin hnh n khi nhn c phn tro khng c hp cht cacbon.
Thm vi git nc lm t phn mu tro ha rri thm vo 0,2 ml H
2
SO
4
, 5 ml HF ph hy
v tch SiO
2
. Chng mu n kh trn bp in. Nu lng tro cn li ln th cn phi x l bng HF
mt ln na. Trong trng hp ny, khi x l mu bng HF ln u ta khng cn chng mu n kh
m ch chng n khi xut hin kh SO
2
.
Ha tan mu bng HCl 10% ri lc qua giy lc ( c ra sch trc bng HCl long) sau
gp cc phn dung dch li vi nhau.
Phn dch lc cui cng c dng xc nh cc kim loi nng trong thc vt theo cc phng
php khc nhau.
Tro ha t:
Khi tro ha t, cc cht hu c c oxi ha di tc dng ca nhng cht oxi ha mnh nh:
H
2
SO
4
, HNO
3
, HClO
4
. Phng php ny n gin v mt thc hin v u vit hn phng php kh
v mt tc , c bit trong trng hp mu thc vt c cha mt lng ln phn tro khng tan. Nu
tun theo nghim ngt nhng iu kin tro ha ta c th loi tr kh nng mt kim loi nng.
- Tro ha bng hn hp H
2
SO
4
v HNO
3
(Troitxky, 1957): ly 5 g mu cho vo bnh Kenan
dung tch 300 ml, cho vo 5 ml H
2
SO
4
c (d = 1,84) v 5 ml hoc nhiu hn HNO
3
(d = 1,4). un
nh bnh trnh si bt mnh (ngoi ra khi un nng nh ta c th duy tr lu tc dng ca HNO
3
v
n d b phn hy v bay hi).
Sau khi ui ht hi HNO
3
, lm lnh bnh, nu nh cha oxi ha hon ton cht hu c trong
mu, ta li thm HNO
3
vo v un nng mu nhit cao hn trong khong 10 pht ri lm lnh.
Khi oxi ha hon ton cht hu c trong mu, dung dch tr nn trong sut.
- Tro ha mu bng hn hp cc axit H
2
SO
4
v HNO
3
v HClO
4
: ly 5 g mu thc vt trng thi
kh khng kh cho vo bnh Kenan dung tch 300 ml. Thm vo 5 ml H
2
SO
4
c (d = 1,84) v 7 ml
HNO
3
(d = 1,4) v c mi gam mu th thm vo 4 ml HClO
4
(d = 1,54). qu trnh tro ha mu
c tnh hnh mt cch an ton, th tch H
2
SO
4
trong bnh khng c nh hn 2 ml, c bit trong
giai on HNO
3
bc hi, v khi th tch H
2
SO
4
nh hn 2 ml, c th n bnh do s phn hy amoni
peclorat, c to thnh trong qu trnh oxi ha cht hu c. Sau khi cho ht cc axit vo bnh, un
nng dn dn trn bp in hoc n kh n 100
0
C, n khi xut hin NO
2
mu nu. ly bnh ra v
ngui. iu ny cn thit v n lm chm qu trnh phn hy HNO
3
. Sau bnh c t nng n
khi xut hin kh SO
2
mu trng. Phn ng cn c tin hnh t t.
Sau khi xut hin SO
2
, un nng bnh t 5 - 10 pht, ri tng nhit ln v tip tc un nng 1 -
2 pht. giai on ny cht hu c ca mu b phn hy hon ton, dung dch tr nn khng mu.
Nu mu b tro ha cn c cacbon th thm vo 1 - 2 ml HNO
3
ri t nng bnh n khi xut
hin kh SO
3
. Vic x l ny tin hnh cho n khi no dung dch tr nn khng mu.
Sau khi ngui, un pha long dung dch trong bnh n 50 ml, lc vo bnh nh mc dung
tch 100 ml. Dung dch ny c dng xc nh cc kim loi nng. Phng php nh lng
tng t nh khi xc nh chng dng di ng.
165
9.2.4. Mt s v d v gii hn pht hin ca cc phng php phn tch
cng c trong phn tch cc kim loi nng
Trong phn tch lng vt cc nguyn t kim loi nng vic la chn phng php cng ng vai
tr ht sc quan trng. Mi phng php c kh nng pht hin v c nhy khc nhau i vi cc
nguyn t kim loi nng.
Gii hn pht hin y c tnh bng n v g/ ml


Phng php phn tch As
Cd
Cu Pb Zn Hg Se
Phng php quang ph
- UV/VIS 0.05 0.04 0.03 0.08 0.02 0.08 0.2
- AAS (ngn la) 0.02 0.05 0.2 0.6 0.02 15 0.3
- AAS (l graphite) 0.004 0.001 0.003 0.002 0.00006 0.2 0.006
- Pht x h quang 20 2 0.05 2 3 20 100
- Ph pht x plasma 0.05 0.005 0.005 0.02 0.005 0.02 0.02
- Hunh quang tia X 1 0.7 1 2 1 1 1
- Ph khi lng 0.006 0.3 0.1 0.03 0.01 0.06 0.1
Phng php in ha
- Cc ph 0.1 0.2 0.2 0.4 0.5 1 0.5
- Cc ph xung vi phn 0.004 0.002 0.002 0.003 0.003 - 0.00002
- in cc chn lc ion - 0.03 0.01 0.03 - - -
9.2.5. Xc nh ch (Pb
2+
) trong t
Hm lng ch trung bnh trong cc t ca Lin X (c) l 1,2.10
-3
% (12 mg/kg), trong thc vt
5.10
-5
%, trong t xtrylia : 10 - 130 ppm; Trung Quc l 25 ppm, trong cc t M l 17 - 26
ppm. Hm lng ch cao hn trong t thng lin quan n t b nhim do hot ng sn xut
ca con ngi.
Ch c cc mui Pb(NO
3
)
2
v Pb(CH
3
COO)
2
tan trong nc. Trong dung dch axit clohydric, ch
(II) nm dng phc vi clorua [PbCl
3
]
-
. Trong cc dung dch axit yu, ch b thy phn v pH cao
hn 7, ch di dng kt ta hidroxit mu vng nu; trong mi trng kim d b ha tan to thnh
ion Pb(OH)
4
2-
. V vy trong qu trnh phn tch cn lu kh nng thy phn ca Pb (II).
Ch cng b giy lc v cc dng c thy tinh hp ph mnh, trong cc dung dch axit khi c mt
H
2
O
2
s hp ph Pb gim i ng k.
Phng php xc nh:
- Phn hy t: Phn hy t bng axit: Khi xc nh Pb trong t ngi ta x l mu bng axit
HF cng axit HNO
3
hay HClO
4
. Qu trnh phn hy tin hnh trong l nung ( phn hy cht hu c),
ti nhit khng vt qu 500
0
C trnh mt kim loi nng do bay hi.
phn hy mu t v mu qung ngi ta cng s dng hn hp HNO
3
v cc cht oxi ha
nh H
2
O
2
, HClO
4
, KClO
3
. Khi x l bng hn hp ny cc cht hu c b khong ha, cc hp cht
166
kh tan ca ch chuyn hon ton sang dng dung dch. Qu trnh phn hy tin hnh trong bnh
Kenan v sinh hn khng kh di dng ng thy tinh.
Phn hy bng phng php nung chy: phn hy mu t khi xc nh ch, c th s dng
hn hp Na
2
CO
3
+ MgO (1:2) hoc hn hp Na
2
CO
3
+ ZnO (1:4). Qu trnh phn hy tin hnh ti
nhit khng cao qu 700-800
0
C trong thi gian 1,5-2 gi. Lm lnh ri ha tan trong nc nng.
Ch chuyn vo trong nc di dng Pb(OH)
4
2-
.
- Xc nh ch: xc nh mt lng nh ch, thng s dng phng php chit trc quang vi
thuc th ithizon. Trong mi trng trung tnh hoc kim yu ithizon to vi ion Pb(II) thnh hp
cht ch ithizonat. Trong cc dung mi hu c ch ithizonat c mu . tan ca ch (II)
ithizonat trong CHCl
3
cao gp 17 ln so vi trong CCl
4
.
H s hp th phn t bng 6,86.10
4
, hp th cc i bc sng 520 nm; gii hn pht hin ca
phng php l 0,05 g Pb/ml. nh lut Bia c tun theo n khong nng 70 g Pb trong 50
ml CCl
4
.
iu kin thch hp chit phc l ti pH = 8 - 10. Ti mi trng kim pH > 10,5 v trong mi
trng axit pH < 3,5 nu tin hnh chit trong CHCl
3
(hay ti pH < 4,5 nu chit bng CCl
4
) ch
ithizonat s b ph hy v ch s chuyn sang tng nc.
Trnh t phn tch:
Cn 2,5 g t nghin n trng thi bt mn cho vo bnh Kenan, thm vo y 15 ml HNO
3
c
v vi git H
2
O
2
, y bnh bng phu thy tinh cung di dng lm sinh hn. un nng nh n khi
xut hin cc oxit ca nit. ngui bnh ri thm tip nhng phn HNO
3
v H
2
O
2
mi tin hnh un
cho n khi mu t tr nn trng. X l mu bng HCl v lc vo cc thy tinh chu nhit. Chng
dung dch lc n kh, thm vo cc HCl 1:1, un si n 80 - 90
0
C, lc v ra phn khng ha tan
ca t. Cho dung dch lc vo bnh nh mc v nh mc bng nc ct n vch mc.
Ly mt th tch dung dch trn cho vo phu chit, thm 5 - 10 ml amoni xitrat 10% v 1 - 2 git
ch th thimol xanh. Dng amoniac trung ha dung dch n pH 9-10 (ch th c mu xanh). Sau
thm 5ml dung dch ithizon 0,001% trong CCl
4
ri lc u phu. Sau khi phn lp, rt phn hu c
vo phu chit khc. Tin hnh chit li ch trong mu n khi mu ca ithizon khng thay i. Gp
ton b phn chit. Thm vo phu chit c hn hp cc dithizonat ca cc kim loi 10 ml HCl 0,02N
v lc mnh chuyn ch sang tng nc; chuyn phn tng nc vo phu chit khc. Ra phn
hu c bng nc v nc ra ny cng gp vo phu chit cha dung dch ch.
Thm vo dung dch cha ch 5 ml amoniaxitrat 10% v trung ha bng ammoniac n pH = 9.
Thm 1 ml KCN 5%, 5 ml dung dch ithizon 0,001% trong CCl
4
v lc mnh. Sau khi phn lp, rt
phn hu c vo bnh nh mc dung tch 25 - 50ml (hoc ng nghim chia ) v lp li qu trnh
chit ch n khi mu ca ithizo khng thay i. nh mc th tch n vch mc bng CCl
4
. Lc u
v o mu bc sng 520 nm. Dung dch so snh l CCl
4
.
Ha cht:
Dung dch chun gc: 0,1 mg Pb/ml. Ha tan 0,1598 g Pb(NO
3
)
2
kt tinh li v sy kh
110
0
C trong nc, thm 1 ml HNO
3
v thm nc ct n vch mc.
Dung dch chun s dng: 1 g Pb/ml.
Dung dch ithizon 0,001% trong CCl
4

Dung dch gc: Ha tan 0,4 g ithizon trong 200 ml CCl
4
. Chuyn dung dch vo phu chit
1,5 - 2 lt, thm vo y 500 ml NH
4
OH long (1:200), lc 3-5 pht. Loi b phn tng hu c. Ra
167
phn nc mt vi ln bng CCl
4
, mi ln 5 - 10 ml; cho n khi CCl
4
c mu xanh; sau thm vo
phu chit 12,5 ml H
2
SO
4
1:5, lc u. Thm 400 ml CCl
4
v lc phu, rt dung dch ny vi ln bng
nc ct 2 ln tch ht lng axit d (thng t 2-3 ln). Lc dung dch ithizon qua giy lc kh
(giy lc c ra bng HCl v nc ct hai ln) vo trong l thy tinh mu nu. Dung dch phi
c bo qun lnh.
T dung dch ny pha long bng CCl
4
ta c dung dch ithizon s dng c nng 0,01%.
9.2.6. Xc nh thy ngn (Hg
2+
) trong t
Thy ngn t kh quyn khi xm nhp vo t s b cc cht hu c v cc hyroxit ca cc kim
loi ht thu; mangan hiroxit c kh nng ht thu thy ngn mnh nht.
Theo Vinagradova A.P hm lng thy ngn trong t l: 1-14.10
-6
%, theo Glauseva V.P v cc
cng s hm lng thy ngn trong t dao ng trong gii hn 1.10
-7
-1.10
-6
%. Hm lng trung bnh
ca thy ngn trong thy quyn l 0,03 g/l, trong thc vt: n.10
-5
- n.10
-7
%. Trong t khong pH =
6, thy ngn b c nh cht nht.
Thng hay phn tch hp cht thy ngn (II). Cc hp cht ny tan tt trong nc nhng cng b
thy phn mnh. Khi pH >5 s xut hin di dng HgO kt ta mu vng, khi pH >11,5 bt u b
ha tan. Hp cht ca thy ngn vi halogen [Hghal]
+
...[Hg(hal)
4
]
2-
l nhng hp cht d bay hi.
Hg
2+
cn tham gia to phc vi cc anion CN
-
, SCN
-
, S
2
O
3
2-
, NO
2
-
hoc vi NH
3
.
Hg c th b hp ph bi dng c thy tinh, polyetylen, teflon cng hp ph mt lng nh thy
ngn. Thy tinh pirec, thch anh hp ph thy ngn t nht. lm gim kh nng hp ph cn phi
x l trc thy tinh bng HNO
3
c v ra nc hoc bng dung dch cromic.
Phng php xc nh:
Phn hy t: C th dng phng php thiu kt hoc x l mu bng axit. Trong phng php
thiu kt khng dng cc mui cacbonat ca kim loi kim v khi c th mt hon ton thy ngn.
xc nh thy ngn ngi ta dng phng php thiu kt trong cc iu kin kh khi thy ngn
s c kh n kim loi ri ct trong dng c c bit, thng s dng canxi oxit v bt st, ch oxit,
ch oxit v canxi nitrat lm cht thiu kt. Hg thu c s c ha tan trong HNO
3
.
Trong phng php x l mu bng axit ngi ta thng dng H
2
SO
4
khi c mt cht oxi ha
nh HNO
3
, cc mui nitrat hoc KMnO
4
. Qu trnh ph mu khi un nng cho n khi mu tr nn
trng, sau loi cht oxi ha cn d bng cch thm vo cc cht kh nh ur, focmalin. phn
hy mu thc vt hoc cc i tng sinh hc khc ngi ta dng hn hp H
2
SO
4
v HClO
4
khi c
mt natri molipat. y nhanh qu trnh phn hy ngi ta tm t mu trc bng dung dch
HNO
3
c.
Trong mi trng axit khi c d thuc th, ithizon phn ng vi Hg(II) to thnh phc
Hg(HDZ)
2
tan trong cc dung mi hu c. Dung dch thy ngn (II) ithizonat trong CHCl
3
v CCl
4

c mu vng-da cam; hp th cc i bc sng 485 nm. H s hp th phn t bng 7,1.10
4
; nh
lut Bia tun theo trong khong nng n 50 g Hg trong 50 ml dung dch chit.
iu kin thch hp to phc v chit phc l trong dung dch H
2
SO
4
0,5-1N hay HNO
3
0,5 -
1N.
Trnh t phn tch:
Thiu hy 1 g t nghin n trng thi bi bng hn hp PbO
2
+Ca(NO
3
)
2
; 1 g t c mi
mn trong ci vi 2 g PbO
2
v 0,15 g Ca(NO
3
)
2
lm kh trc trong bnh ht m. Cho hn hp vo
168
phn 1 ca dng c v un nng, lc u un nh phn trn ngn la n kh v sau nung . Khi
thiu kt dng c c t hi nghing. Sau 5 - 6 pht nung nng, di chuyn ngn la n kh n 3,
t nng phn ny sau li chuyn xung di, lm lnh. Ha tan thy ngn thng hoa trong 1ml
HNO
3
1:1 ri chuyn dung dch vo phu chit. Ra ng nghim mt vi ln bng nc ct ri gp c
vo phu chit trn. Pha long dung dch bng nc ct n nng HNO
3
1N. Sau rt vo phu
dung dch KMnO
4
0,1N n khi dung dch c mu hng ri lc u. Sau 1 - 2 pht kh lng MnO
4
-

cn d bng Na
2
SO
3
20%, lc u. Thm vo phu chit 4 ml dung dch ithizon 0,001% trong CHCl
3

v lc phu chit 1 pht. Tin hnh chit ithizonat n khi ithizon khng i mu. Sau khi tch lp,
rt phn chit vo cuvet v o mt quang bc sng 485 nm.
Dung dch chun gc:
Ha tan 0,3336 g Hg(NO
3
)
2
.0,5H
2
O tinh khit ha hc trong 1 ml HNO
3
c ri thm nc ct
n 1 lt, c dung dch chun c nng c nng 0,1 mg Hg/ml. ng chun c xy dng t
dung dch chun c hm lng 2g Hg/ml trong HNO
3
1N.
9.2.7. Xc nh dng di ng ca mt s nguyn t
Nhng hp cht ca cc kim loi nng d dng chuyn vo trong cc dung dch chit rt khc
nhau c gi c gi l dng di ng ca cc kim loi nng.
Nhng hp cht ha tan trong nc, nhng dng trao i v nhng hp cht ha tan trong cc
axit c nng thp cng nh trong cc dung dch m u c xp vo cc hp cht di ng. Cc
dung dch dng chit rt cc hp cht di ng hin c rt nhiu, thng l cc dung dch axit v cc
dung dch m. Cc dung dch ny khc nhau v lc tc dng ca chng i vi t v mt s trng
hp dung dch chit rt c s dng nh l mt thuc th nhm ri xc nh mt s kim loi nng
quan trng trong , ngi ta s dng nhng thuc th khc nhau.
S la chn mt dung dch chit rt thch hp chit rt kim loi nng di ng trong t c
nh gi bng cch so snh nhng s liu phn tch nhn c vi cc kt qu ca cc th nghim
ngoi ng c s dng cc phn vi lng cc cy trng v trong nhng iu kin th nhng khng
ging nhau; t gii thch v mc m bo ca t v cc kim loi nng i vi dinh dng ca
thc vt.
c nhiu nghin cu cng phu chn la, so snh cc dung dch chit rt nhm v cc dung
dch chit rt ring bit cc kim loi nng. Cc dung dch chit rt nhm thng c cp n l:
Dung dch axetat-lactat theo phng php Egner-Rim-Doming (phng php AL).
Dung dch HCl 1N (phng php Rinhkis).
Dung dch EDTA 0,01M + dung dch m amoni axetat pH = 4,7 (amoni axetat 0,5N v axit
axetic 0,5N).
Dung dch m oxalat (phng php Grigg).
Dung dch m amoni axetat pH = 4,8 theo phng php ca Krupski-Alecxandrova (dng
cho t cacbonat v trung tnh).
Dung dch Baron pH = 4 (gm amoniaxetat, amonisunfat v axit axetic).
Vi tng nguyn t, s dng cc dung dch chit rt ring sau y:
B : nc ct nng (theo Berger v Truog).
Cu : HNO
3
0,43 N (theo Vesterhoff); HCl 1N (theo Rinhkis).
169
Zn : KCl 1N (theo Rinhkis); EDTA + (NH
4
)
2
CO
3
(theo Trierveiler v Lindsay); HCl 0,1N
(theo Zommer).
Mo : dung dch m oxalat pH = 3,3 (theo Grigg).
T cc kt qu phn tch t, phn tch cy trong cc th nghim trong chu v ngoi ng, nhiu
nh nghin cu rt ra nhn xt:
Dung dch chit rt c axit cng mnh th lng cc kim loi nng c chit rt ra cng ln.
Lng cc kim loi nng c chit rt ra bng HCl 1N l ln nht.
Ba Lan, Cng ha Sc s dng HCl 1N lm dung dch chit rt nhm xc nh km, ng,
mangan; Lin X (c) dng dung dch m amoni axetat (pH = 4,8) lm dung dch chit rt nhm
xc nh mangan, km, ng v coban trong t trung tnh v t cacbonat (hm lng cacbonat
khng qu 10%).
Lin X (c) s dng ph bin h thng dung dch chit rt do I.V.Peive v G.I.Rinhkis a ra
xc nh dng di ng ca cc kim loi nng i vi t khng phi cacbonat.
Trong h thng ny chit rt mi kim loi nng ngi ta s dng nhng thuc th ring.
Phng php ny c phng th nghim ha hc t Hc vin th nhng mang tn V.V.
Docutraev ci tin. T l gia t v dung dch chit rt l 1:10, lc trong 1 gi.
9.2.7.1. Xc nh bo di ng
chit rt bo di ng t t ngi ta thng x l t bng nc si. Phng php ny c
Berger v Truog a ra nm 1939. Hin nay phng php ny c ci tin v t l gia t, nc
v thi gian un si.
Chit bo di ng t t: Cn 20 - 50 g t kh khng kh ry qua ry 1 mm cho vo bnh lm
t thch anh hay t thy tinh khng bo. Thm nc ct vi lng gp hai lng t cn theo t l 1 : 2
( i vi t than bn 1:10). un nng bnh n si v gi si trong 10 pht. Bnh un phi c sinh
hn, nu khng c th thay bng mt ng thy tinh di 25 - 30 cm lm t thy tinh khng bo, cm vo
nt lie. Lc dung dch nng qua giy lc khng tn. Ly 20 - 40 ml (tu thuc vo hm lng bo)
dung dch lc trong cho vo bt thch anh hay bt platin, thm vo 1 ml dung dch NaOH hay KOH
1N ri chng dung dch trn bp cch thy n kh. Nung phn kh ny trong l nung ti nhit 450
- 500
0
C n khi ph hy hon ton cht hu c v nitrat (1-2 gi). Sau c th dng phng php
carmin hay phng php quinalizarin xc nh bo.
a. Xc nh bo di ng bng phng php carmin:
Ha tan phn kh sau khi nung trong 5 - 10 ml dung dch H
2
SO
4
0,5N, nghin cn thn bng mt
que thy tinh kh lm t thy tinh khng bo. Lc dung dch qua giy lc khng tn, hng dung dch
lc.
Dng pipet ht ly 1 ml cho vo ng nghim nt nhm, thm chnh xc 9 ml dung dch carmin
0,005% trong H
2
SO
4
(d = 1,84), nt ng nghim, lc u v gi nguyn 12 - 18 gi, sau o mt
quang trong cuvet dy 3 cm, y cuvet bng np thy tinh. Kt qu phn tch c tnh theo ng
chun.
Cn ch l dung dch phn tch v dung dch chun c ly cng bng mt pipet.
Ha cht:
H
2
SO
4
c loi tinh khit c bit hay tinh khit ha hc. Nng c xc nh bng t
trng k.
170
Kim tra xem c NO
3
-
trong axit ny bng cch rt 9 ml nc ct vo trong ng nghim sch,
kh, sau rt vo 1 ml H
2
SO
4
c, lc u. Sau khi ngui, thm t t, dc theo thnh ng 5 ml dung
dch iphenylamin trong H
2
SO
4
c vo trong ng nghim. Nu c nitrat, trn ranh gii gia hai cht
lng xut hin mt vng hoc mt vng mu xanh nc bin.
Axit b bn NO
3
-
v nhng axit c mu nht cng khng nn dng xc nh bo. xc nh
bo tt nht l s dng loi c bit tinh khit, c th s dng loi tinh khit ha hc th trc
khng c NO
3
-
v bo.
Dung dch carmin 0,005% trong H
2
SO
4
c. Cn phi th trc cht lng carmin: cho dung
dch axit boric vo ng nghim ri thm vo mt lng va phi dung dch carmin trong axit sunfuric
c. Thm dung dch carmin cn phi lng ti thiu. Nu dung dch axit boric c mu xanh nc
bin th carmin c th s dng c. Sau khi kim tra, cn trn phn tch 50mg carmin cho vo bnh
nh mc 1 lt, thm 500 - 600 ml H
2
SO
4
c (d = 1,84) khuy u dung dch cho n khi ha tan hon
ton (tt nht l qua m), sau thm H
2
SO
4
c n vch mc. y bnh v lt ngc bnh mt
vi ln dung dch tr nn ng nht.
Dung dch carmin ng trong l nt nhm ch ti. Dung dch c mu , nu dung dch c
mu khc, khng thun li nh lng bo.
Axit boric: H
3
BO
3
xy dng ng chun cn phi dng H
3
BO
3
kt tinh li hai ln. tan ca axit boric ti 0
0
C
l 2 g trong 100 ml nc ct, ti 20
0
C l 5 g v ti 100
0
C l 40 g. Cn 10 - 12 g axit boric, ha tan khi
un nng v khuy lin tc trong 100 ml nc ct. un dung dch n si, lc dung dch nng qua
giy lc bng trng, hng dung dch lc vo trong bnh rng lm t thy tinh khng bo. Lm lnh bnh
bng vi nc hoc nc . Dng phu Busner lc H
3
BO
3
qua giy lc bng trng, ra axit ny bng
3-4 ln bng nhng lng nh nc ct lnh. Ly H
3
BO
3
, lm kh ngoi khng kh, trn t giy lc,
y bng mt t giy lc khc, cng loi. Chuyn kt ta vo trong cc cn rng y, khng y np
cc cn ri t cc vo trong bnh ht m c cha H
2
SO
4
c n khi lng khng i. Axit boric kt
tinh li c gi trong cc cn y np v trong bnh ht m.
Dung dch chun gc: Cn 0,2858g axit boric kt tinh li trn cn phn tch sau chuyn
lng cn vo bnh nh mc 500 ml nt nhm. Ha tan bng H
2
SO
4
0,5N sau nh mc n vch
mc cng bng chnh dung dch axit ny. y nt v lt ngc bnh vi ln trn u dung dch. Ta
c dung dch chun gc c hm lng bo l 0,1mg/ml.
H
2
SO
4
0,5N: ly 14 ml H
2
SO
4
c ha tan, thm nc n 1 lt.
Dung dch chun s dng: Dng H
2
SO
4
0,5N pha long dung dch chun gc ln 10 ln ta
c dung dch chun s dng c hm lng bo l 0,01 mg/ml.
Thang chun: Dng 2 micro buret c th tch 1 hoc 2 ml, mt ng dung dch chun s dng,
mt ng H
2
SO
4
0,5N. Ly cc th tch dung dch chun s dng: 0,00; 0,05; 0,10; 0,20; 0,40; 0,60;
0,80; 1,00 ml cho vo ng nghim sch, kh lm t thy tinh khng bo hoc lm t thch anh; sau
thm cc th tch H
2
SO
4
0,5N vo th tch dung dch trong mi ng ng bng 1 ml. Lc u ri
thm vo mi ng nghim chnh xc 9 ml dung dch carmin 0,0055. Lc u v gi yn trong 24 gi
mu n nh hon ton, ta c thang mu chun.
b. Xc nh bo theo phng php quinalizarin:
Nguyn l: Phng php da trn s thay i mu tm ca quinalizarin (1, 2, 5, 8- tetra
oxianthraquinon) trong mi trng H
2
SO
4
c sang mu xanh nc bin khi c mt bo. Khi c mt bo,
171
quinalizarin s to thnh mt hp cht ni phc. nhy ca quinalizarin cao hn so vi carmin v h
s hp th phn t cao hn ( = 7000 ti bc sng 615 nm).
V mu ca hp cht phc boquinalizarin ch tun theo nh lut Bia khi hm lng bo khng
vt qu 1g nn trong ng chun cng ch xy dng vi hm lng bo t 0 - 1 g.
Trnh t phn tch: Ly 1 ml dung dch phn tch cho vo ng nghim hay ng tr lm t thy
tinh khng bo hoc lm t thch anh c th tch l 20 - 25 ml.
Tu thuc vo nng axit s dng, dng buret thm 19,0 - 22,0 ml dung dch quinalizarin trong
axit sunfuric. y nt ng nghim, lc u dung dch v gi yn 12-18 gi cho mu n nh hon
ton sau o mu trn my trong cuvet 3 cm, dng ming thy tinh y cuvet.
Ha cht:
H
2
SO
4
93,56 - 95,60% loi c bit tinh khit hoc tinh khit ha hc.
Dung dch quinalizarin trong axit sunfuric: ha tan 10 - 20 mg quinalizarin trong 1 lt H
2
SO
4

c. Do s ml dung dch ny thm vo mu ph thuc vo hm lng phn trm H
2
SO
4
nn cn phi
xc nh hm lng ca n.
a cn phn tch bn tri t cc cn hoc bnh tam gic c nt nhm dung tch 100 ml; a cn
bn phi t qu cn 2 g. Dng pipet c qu bp bng cao su thm cn thn H
2
SO
4
c vo cc cn
hoc bnh tam gic cho n khi cn thng bng.
y cc cn hoc bnh tam gic v xc nh chnh xc lng H
2
SO
4
ly. Khi cho axit vo cn
ch khng cho axit ri ra a cn hay ra pha ngoi cc cn hay bnh tam gic. Chuyn ton b lng
axit cn vo bnh nh mc 500 ml trong c sn 100 - 200 ml nc ct. Ra cn thn cc cn,
hay bnh tam gic mt vi ln bng nc chuyn ht axit sang bnh nh mc. Thm nc n vch
mc v khuy u. Dng pipet ly 3 ml mu, mi mu 25 ml cho vo bnh tam gic 250 ml, thm vo
2 git ch th metyl da cam 0,1% v dng dung dch NaOH 0,1N chun.
Hm lng H
2
SO
4
theo phn trm c tnh theo cng thc:
H
2
SO
4
(%) =
2
00 0,004904.1 V.
=
2
4904 0, . V

Trong : V : th tch NaOH 0,1N d dng chun (ml)
0,004904 : lng H
2
SO
4
tnh ra gam, tng ng vi ng 1 ml dung
dch NaOH 0,1N.
2 : lng H
2
SO
4
tnh theo gam.
Tu thuc vo hm lng phn trm H
2
SO
4
tm c, i vi 1 ml dung dch th nghim hoc
dung dch chun ly cc lng quinalizarin khc nhau:
Hm lng H
2
SO
4

(tnh theo %)
Dung dch quinalizarin
(ml)
93-94
94,5
95 v cao hn
22,0
20,0
19,0
Khi s dng axit c nng cao hn 94,5%, thun li hn c l nn pha long c dung dch
c nng 93 - 94%.
172
Thng pha 1 - 2 l hoc nhiu hn dung dch quinalizarin trong axit sunfuric. Dung dch c gi
trong l thy tinh nt nhm, t ch ti.
Thang chun: Dng nc ct pha long dung dch chun gc c cha 0,1mg bo/1ml ra 100ml ln
ta c dung dch chun s dng. Dng micro buret cho vo cc ng nghim nt nhm sch, kh lm
bng thch anh hoc thy tinh khng bo. Cc th tch dung dch chun s dng nh sau (ml): 0,00;
020; 0,40; 0,60; 0,80; 1,00, dng nc ct hai ln a th tch ln ng 1ml.
Thm vo mi ng 9ml dung dch quinalizarin trong H
2
SO
4
, y ng nghim, lc u ri gi yn
trong khong thi gian t 12-18 gi, sau o mt quang v xy dng ng chun.
9.2.7.2. Xc nh ng di ng
a. Xc nh ng di ng theo Rinhkis:
Nguyn l: Phng php da trn qu trnh chit rt ng di ng t t bng dung dch HCl 1N.
T l gia t v dung dch l 1:10. Lc trn my lc 1 gi sau nh lng Cu di dng phc mu
ca ng vi dietyldithiocarbaminat trong CCl
4
.
Trnh t phn tch: Cn trn cn phn tch 5 g t kh khng kh ry qua ry 1 mm, cho mu
vo bnh tam gic nt nhm dung tch 100 ml. Thm chnh xc 50 ml HCl 1N, lc trn my lc 1 gi
sau lc qua giy lc bng trng.
Dng pipet ht 10 - 25 ml dung dch lc (tu thuc hm lng ng) cho vo phu chit 50 - 100
ml, thm 5 ml dung dch amonixitrat 5%, 1 git phenolphthalein ri thm tng git ammoniac n khi
dung dch c mu hng nht. Cho vo chnh xc 15 ml dung dch ch dietyldithiocarbaminat trong
CCl
4
, lc trn my lc 10 pht. dung dch trong phu phn lp ri rt lp CCl
4
cha phc ca ng
vi thuc th c mu vng qua giy lc kh vo cuvet 2cm. o mu vi knh lc mu 453 nm, dung
dch so snh l CCl
4
.
Kt qu phn tch tnh theo cng thc:
X =
b
a

X : Hm lng ng trong t mg/kg
a : Lng ng trong th tch ly phn tch, tm thy theo ng chun (g)
b : Khi lng t, tng ng vi th tch ly phn tch (g)
Ha cht:
Dung dch ch dietyldithiocarbaminat trong CCl
4
: Lc 664 mg natridietyldithiocarbaminat vi
1lt CCl
4
trong phu chit; thm vo phu dung dch ch nitrat (489mg Pb(NO
3
)
2
ha tan trong 100ml
nc ct hai ln). Lc phu 5 pht. cho phn lp ri lc lp CCl
4
c ch dietyldithiocarbaminat tan
trong qua giy lc kh vo trong bnh tu tinh mu nu. Dung dch c gi trong t lnh.
Dung dch chun CuSO
4
: Ha tan 3,993 g CuSO
4
.5H
2
O kt tinh li trong nc ct hai ln,
nh mc n 1 lt, c dung dch cha 1mgCu/ml. Pha long dung dch ny 100 ln (10ml pha long
n 1 lt) thu c dung dch cha 0,01 mgCu/ ml; li pha long dung dch 10 ln ta c dung
dch cha 1 g Cu/ ml, s dng dung dch ny pha thang chun.
Thang nh gi (mg Cu/kg):
Rt ngho ng :
Ngho ng:
Trung bnh:
0,3
0,3 - 1,5
1,5 - 3,3
173
Cao: > 3,3
b. Xc nh ng di ng theo Vesterhoff:
Hin nay nhiu nc tha nhn phng php xc nh ng di ng trong dung dch HNO
3

(dng chit rt ng) ca Vesterhoff l phng php chun.
Trnh t phn tch:
Ly 10 g t cho vo bnh tam gic 250 ml, thm vo 100 ml HNO
3
(30 ml HNO
3
d = 1,39 nh
mc n th tch 1 lt bng nc ct hai ln), lc 2 gi ri lc. Ly 25 ml dung dch lc cho vo bnh
tam gic. Thm vo 2 ml dung dch KMnO
4
0,5% v un dung dch n si. Cho vo dung dch nng
0,5 ml axit oxalic 5% lm mt mu dung dch. dung dch ngui ri chuyn dung dch vo phu
chit 100 ml (ra bnh tam gic bng nc ct) v a th tch n 50 ml. Cho vo phu chit 1 ml
dung dch Na
3
PO
4
bo ha, 4 ml dung dch natrixitrat 50% v 4 ml dung dch NH
4
OH c (d = 0,92).
Sau mi ln thm thuc th vo u phi lc phu chit cn thn.
Cho vo chnh xc 15 ml dung dch ch dietyldithiocarbaminat trong CCl
4
, lc phu chit 2 pht.
cho phn lp, lc ch dietyldithiocacbaminat trong CCl
4
qua phu lc kh vo cuvet chiu dy 2
cm. o mt quang vi knh lc mu xanh l cy (536 nm); CCl
4
l dung mi so snh.
ng chun c xy dng t dung dch c hm lng ng l 10 g Cu/ml. xy dng
ng chun ngi ta cho vo cc phu chit 0; 0,2; 0,5; 1,0; 2,0; 3,0; 4,0 ml dung dch ng, thm
nc ct 2 ln n th tch 50 ml ri tip tc x l nh i vi dung dch phn tch.
Thang nh gi (mg Cu/kg):
nh gi t ct t st v st pha
Tt
Trung bnh
Km
> 3,5
2,1 - 3,5
< 2,0
> 2,5
1,6 - 2,5
< 1,5
9.2.7.3. Xc nh mangan di ng
a. Phng php Dobritxcaia:
Nguyn l: Phng php da trn qu trnh chit rt mangan di ng bng dung dch H
2
SO
4
0,1N.
T l gia t v dung dch l 1: 10. Thi gian tng tc l 1 gi, oxi ha mangan n trng thi ha tr
7 bng pesunfat khi c mt bc nitrat v axit photphoric.
Trnh t phn tch: Cn trn phn tch 5 g t kh khng kh ry qua ry 1 mm. Cho lng cn
vo trong bnh tam gic nt nhm dung tch 100 ml; thm vo 50 ml H
2
SO
4
0,1N; lc trn my lc 1
gi, lc dung dch qua giy lc mn bng trng.
Ly 10 - 15 ml dung dch lc cho vo cc chu nhit dung tch 50 ml. Thm vo y 5 ml HNO
3

c v 2 ml H
2
O
2
30%; chng trn bp in n kh. Lp li qu trnh oxi ha bng HNO
3
v H
2
O
2
2 -
3 ln. Sau thm 3 ml HNO
3
v chng n kh. Thm vo phn kh 25 ml H
2
SO
4
10%. un trn
bp in n khi phn kh tan hon ton, thm vo cc 15 ml nc, 2ml H
3
PO
4
(d =1,7) v 2 ml
AgNO
3
1%, un 5 - 10 pht; nu thy c th cn tip tc un n si ri lc dung dch qua giy lc
bng xanh. Thm vo dung dch nng trong cc khong 2 g amonipesunfat (thm lm vi ln) khuy
dung dch cn thn bng que thy tinh, t cc ln trn bp in, un 10-15 pht oxi ha nhanh v
hon ton mangan n axit manganic, khi xy ra qu trnh phn hy mnh lit amonipesunfat v c
kh ozon thot ra. Sau khi ht kh thot ra, ly cc ra khi bp, ngui, chuyn dung dch vo bnh
nh mc 50 ml. Thm nc ct hai ln n vch mc. o mt quang trong cuvet dy 1cm hay 2
cm ti bc sng 536 nm, dung dch H
2
SO
4
5% dng lm dung dch so snh.
174
ng chun c xy dng t dung dch KMnO
4
0,1N (t ng chun). Ly 10 ml dung dch ny
cho vo bnh nh mc 100 ml, thm nc ct hai n vch mc, khuy u. T dung dch mi pha
ny ly 10 ml cho vo bnh nh mc 100 ml ri thm nc ct hai ln n vch mc. Dung dch ny
c nng 0,001N. Trong 1 ml dung dch cha 11 g mangan. Dng pipet ly 2; 5; 10; 20; 25 ml
dung dch KMnO
4
0,001N cho vo bnh nh mc 50 ml. Thm nc ct n vch mc v o mt
quang ngay vi knh lc mu xanh l cy (536 nm), dng cuvet c chiu di nh khi o vi dung dch
phn tch.
Kt qu phn tch tnh theo cng thc:
X =
b
a 11 .

X : Hm lng Mn trong t mg/kg
a : Lng dung dch KmnO
4
0,001N nhn c theo ng chun i vi th tch dung dch th
nghim ly phn tch (ml)
b : Khi lng t, tng ng vi th tch dung dch th nghim ly phn tch (g)
11 : Hm lng Mn tnh theo g trong 1 ml dung dch KMnO
4
0,001N
b. Xc nh Mn di ng theo Schachtschabel:
nh gi hm lng Mn di ng trong t, Schachtschabel (1957) ngh tin hnh xc nh
mangan tan trong sunfit v mangan d c kh.
- Xc nh mangan tan trong dung dch sunfit: Cn 5 g t ry qua ry 1mm cho vo bnh tam
gic 250 ml, thm vo 0,2 g than hot tnh v 50 ml dung dch chit rt, lc trn my lc 1 gi. Sau
lc dung dch qua giy lc bng trng, kh. phn tch c th s dng nhng phn dung dch lc u
tin. Ly 15 - 20 ml dung dch lc cho vo bnh nh mc 50 ml, che nh hng kh ca clo v
to phc vi ion st, thm vo bnh 2,5 ml hn hp gm thy ngn sunfat, axit nitric, bc nitrat v axit
photphoric. Sau oxi ha mangan ln trng thi ha tr 7 ngi ta thm vo 2 g amoni pesunfat.
t bnh vi dung dch vo trong my n nhit 20 - 30 pht nhit 90 - 95
0
C n khi ngng thot
bt kh. Nu dung dch c mu nu th cn phi ly nhng phn dch lc mi (5 - 10 ml) ri lp li qu
trnh x l nh trn. Dung dch lc sau khi ngui c thm nc n vch mc ri o mu nh
m t trn.
Ha cht:
Dung dch chit rt: Cn 123,3 g MgSO
4
.7H
2
O v 2 g Na
2
SO
3
ha tan trong nc ri nh
mc n th tch 1 lt bng nc.
Dung dch thy ngn sunfat: ha tan 75 g Hg
2
SO
4
trong 400 ml HNO
3
(d = 1,4) v 300 ml
H
3
PO
4
(d = 1,7) thm vo 0,2 g AgNO
3
v dng nc ct a th tch n 1 lt.
- Xc nh mangan d kh (pH = 8,0): Qu trnh chit rt mangan tin hnh bng dung dch
magie sunfat c thm 2 g hiroquinon trong 1 lt dung dch. Tt c qu trnh chit rt v xc nh
mangan sau ny tin hnh nh khi xc nh mangan tan trong dung dch sunfit.
- Thang nh gi Mn d kh pH = 8,0
175
Ngho
Trung bnh
Giu
< 20 mg/kg (ppm)
20 - 30 mg/kg
> 30 mg/kg
9.2.7.4. Xc nh km di ng
Km di ng c chit rt t t bng dung dch kali clorua 1N. Phng php ch s dng cho
t axit. T l gia t: dung dch l 1:10, lc 1 gi trn my. Cui cng xc nh km bng phng
php o mu di dng phc vi dithizon theo mu n.
Trnh t phn tch: Cn trn cn phn tch 2,5 g t kh khng kh ry qua ry 1 mm, cho mu
vo chn thch anh dung tch 50 ml. Thm vo 25 ml dung dch KCl 1N, lc trn my lc 1 gi ri lc
qua phu lc thch anh, dng giy lc bng trng tinh ch khi cc vt kim loi nng.
Ly 5 ml dung dch lc cho vo phu chit 50 ml, thm vo 2 git ch th metyl da cam, tin hnh
trung ha bng dung dch natri axetat 5% n khi ch th chuyn sang mu vng, li thm vo 0,2 ml
dung dch natri axetat 5% v 2 ml dung dch thiosunfat 50%. Chit km hai ln bng dung dch
dithizon 0,02% trong CCl
4
, ln u dng 2 ml, ln sau 1 ml. Sau mi ln thm dithizon, phu chit
c lc trn my 3 pht, gi yn cho tch tng ri chuyn tng hu c vo phu chit sch khc.
Chit li tng nc bng dung dch dithizon mi; dung dch dithizon cng c rt vo phu chit
sch trn.
Thm vo phu chit cha km dithizonat 25 ml dung dch ammoniac 0,01N, lc 1-2 pht. Lp
km dithizonat c mu c chuyn vo bnh nh mc kh 25 ml, ri thm CCl
4
n vch mc. o
mt quang trong cuvet chiu dy 1 cm, ti bc sng 536 nm, dung dch so snh l CCl
4
.
xy dng thang chun cho vo cc phu chit 0; 0,5; 1; 2; 3; 4; 5 ml dung dch km c nng
1g Zn/ml; thm nc ct n 5 ml ri cho vo 2 git metyl da cam v tin hnh phn tch nh i
vi dung dch th nghim.
Kt qu phn tch tnh theo cng thc: X =
b
a

X : Hm lng km di ng trong t mg/kg
a : Lng km trong th tch ly phn tch, tm thy theo ng chun g
b : Khi lng t tng ng vi th tch mu ly phn tch (g).
Ha cht:
Tt c cc ha cht dng xc nh km u phi tinh ch cn thn bng dithizon.
Dung dch chun km: Cn 0,2 g km kim loi tinh khit trn cn phn tch cho vo bnh nh
mc 1 lt v ha tan trong lng nh nc ct hai ln c 1 ml H
2
SO
4
c (d = 1,84). Sau khi tt c km
ha tan, dng nc ct hai ln a th tch n vch mc. Trong 1 ml dung dch ny cha 200 g
km. Pha long dung dch ny 200 ln c dung dch cha 1 g Zn/ml.
Thang nh gi (mg Zn/ kg):
Rt ngho
Ngho
Trung bnh
Giu
Rt giu
< 0,2
0,2 - 1,0
2 -3
4-5
>5
176
Ghi ch: i vi t ngp nc c th dng HCl 0,05N lm dung dch chit rt: 10 g t v 20
ml HCl 0,05N. Lc 5 pht ri lc.
9.2.7.5. Xc nh coban di ng
Phng php da trn qu trnh chit coban di ng trong t bng HNO
3
1N. T l gia t:
dung dch l 1:10, lc trn my lc 1 gi. Xc nh coban bng phng php o mu di dng phc
mu vi mui nitrozo-R.
Trnh t phn tch: Cn 10 g t kh khng kh ry qua ry 1 mm trn cn phn tch, cho mu
vo bnh tam gic nt nhm dung tch 250 ml. Thm vo chnh xc 100ml HNO
3
1N lc trn my lc 1
gi, lc qua giy lc bng trng.
Ly 25 ml dung dch lc cho vo cc thy tinh chu nhit, thm vo 1 ml HNO
3
c, 1 ml H
2
O
2

chng trn bp in n kh. Qu trnh x l ny c lp li mt ln na v chng dung dch n khi
bt u kt tinh mui. Rt vo cc 6 ml nc ct hai ln axit ha bng HCl (1:10), un dung dch
n si. Thm vo 1 ml dung dch natri xitrat 40% v un si khong 1 pht, pH ca dung dch cn
phi ln hn 5,5 (kim tra theo giy ch th vn nng). Nu cha t n gi tr mong mun, c th
dng natri xitrat iu chnh. Thm vo dung dch phn tch 1 ml dung dch mui nitrozo-R 0,05%
ri un si. Nu dung dch phn tch c mu vng th thm tip 1ml dung dch nitrozo-R na, 5 ml
nc ct hai ln ri un dung dch n si. dung dch ngui, thm vo 3 ml hn hp H
3
PO
4
v
HNO
3
(5 phn H
3
PO
4
85% v 1 phn HNO
3
c), khuy dung dch nhanh v cn thn. Chuyn dung
dch vo bnh chia ri pha long n 10 ml. o phc mu ca phc coban vi mui nitrozo-R trong
cuvet 2 cm, knh lc mu xanh l cy (536 nm), dung dch so snh l nc ct hai ln.
Thang chun c chun b nh sau: Cn 0,477 g CoSO
4
.7H
2
O cho vo cc v ha tan bng nc
ct hai ln. Chuyn dung dch vo bnh nh mc 1 lt, axit ha bng 1ml H
2
SO
4
(d = 1,84) ri thm
nc ct hai ln n vch mc.
Dung dch nhn c cha 100 gCo/ml. Ly 50 ml dung dch ny pha long bng nc ct hai
ln n th tch 500 ml c dung dch cha 10 gCo/ml, c dung dch chun s dng. Ly cc th
tch 0,5; 1; 2; 3; 4; 5; 6; 7; 8; 9 ml dung dch chun s dng cho vo bnh nh mc 100 ml. Thm
nc ct hai ln n th tch 50 ml, thm 5 ml dung dch natri xitrat 20% v 5 ml dung dch natri
axetat 40%, thm 10ml dung dch mui nitrozo-R 0,05% ri un n si. ngui, thm vo 5 ml hn
hp HNO
3
v H
3
PO
4
, nh mc n vch mc bng nc ct hai ln. Tin hnh o mt quang nh
i vi dung dch phn tch.
Kt qu phn tch c tnh theo cng thc:
X =
N
b . a

X : Hm lng coban trong t (mg/kg)
N : Lng t tng ng vi th tch dung dch ly phn tch (g)
a : Lng coban tm thy theo th chun g/ml.
b : Th tch dung dch so mu (ml)
Ha cht:
axit nitric tinh khit ha hc: Ht 68,9 ml HNO
3
c (d = 1,40) thm nc ct 2 ln n th
tch 1 lt c dung dch HNO
3
1N.
Natri xitrat 3 ln th (dung dch 20%).
Natri axetat 40%.
177
Mui nitrozo-R (dung dch nc 0,05%).
Hn hp axit nitric v octhophotphoric: Hn hp 2 axit trn theo t l 100ml H
3
PO
4
v 20ml
HNO
3
.
H
2
O
2
.
9.2.7.6. Xc nh molipen di ng
Phng php so mu ca Grigg (theo Dobritxcaia - 1969):
Cn mu t ry qua ry 1 mm vi lng : 15 g i vi t st, 25 g i vi t ct v ct pha;
cho mu vo bnh nt nhm, rt vo 150 ml hay 250 ml (tng ng vi lng mu l 15 g hay 25 g)
dung dch m oxalat ca Grigg c pH = 3,3, lc dung dch 1 gi. Lc dung dch qua giy lc bng
trng, ly 125 ml hay 200 ml dung dch cho vo cc chu nhit ri cho dung dch bay hi ti khi th
tch dung dch cn 1/4. ph hy cc oxalat v cht hu c trong dch lc ngi ta thm vo cc 3ml
H
2
O
2
30% v 3 ml HNO
3
c, tip tc chng n kh. Thm vo 5 ml nc ct hai ln ri chng kh
tch ht vt axit pecloric. Thm vo tip 5 ml HCl 22% chuyn mui sang dng clorua ri li
chng dung dch n kh. Ha tan phn kh bng cch un nng trong 11 ml HCl 22%, chuyn dung
dch vo bnh nh nc 50 ml, thm vo 15 ml dung dch NaF 4% ( to phc vi nhm, st v titan),
5ml dung dch natri nitrat 20% ( ngn nga vic kh molipen n ha tr thp hn +5), thm nc
ct n vch mc, khuy u dung dch. Chuyn ton b dung dch vo phu chit 100 ml, ra thnh
bnh bng 2 - 3 ml nc, ri rt c vo phu chit trn. Thm vo phu chit 4 ml kali thioxianat 20%
( to thnh phc molipen thioxianat), lc u, cho vo phu 3 - 4 ml dung dch SnCl
2
10%, lc
phu v sau khi mu nu ca phc st-thioxianat hon ton mt (Fe
3+
chuyn thnh Fe
2+
) th cho
vo phu chit 20 ml dung dch ru n-butylic ( c ra trc bng nc v dung dch thic clorua
bo ha) v chit phc molipen thioxianat cn lc mnh phu chit 1 pht. cho phn lp ri
tch lp nc pha di phu chit ra nhng gi li khong 1 ml lp nc. Phn chit trong phu c
th li c mu hng do mt phn Fe
2+
c oxi ca khng kh oxi ha chuyn thnh Fe
3+
, v th cn
phi ra tip phn chit bng dung dch mui thic bng cch cho vo phu chit c phn chit 20 ml
dung dch mui thic mi pha (2 ml SnCl
2
10% + 18 ml nc), lc u phu chit. Sau khi phn chit
hon ton mt mu hng th tch b lp nc, cn phn chit trong tng hu c cho vo cuvet 3 cm.
Thm vo cuvet 1 ml ru etylic loi nhng git nc cn ln v 1 - 2 git dung dch mui thic,
khuy dung dch trong cuvet cn thn bng que thy tinh nh. Phn chit lc ny s tr nn trong sut,
khng c mu hng, em o mt quang ca phn chit vi knh lc mu xanh nc bin (435 nm)
(ch tin hnh o mt quang t nht l sau 20 - 30 pht k t khi thm ru n-butylic). Dung dch so
snh l ru n-butylic, khng x l bng thic v nc.
ng chun c xy dng nh sau: Cho vo cc bnh nh mc 50 ml cc th tch : 0,5; 1,0;
2,0; 3,0; 4,0 v 5,0 ml dung dch molipen chun c hm lng 1 g Mo/ml; thm vo mi bnh 11 ml
HCl 6N, 3 ml FeCl
3
c hm lng 5 mg Fe
3+
/ml, khuy cn thn cc bnh ny ri thm nc ct n
vch mc. Sau tin hnh nh i vi dung dch phn tch.
Ha cht:
Dung dch m oxalat: ha tan 25 g amonioxalat v 12,6 g axit oxalic trong nc ct 2 ln khi
un nng ri thm nc ct n 1 lt.
Axit clohidric 22% (6N, d=1,1): Ct hn hp gm 550 ml HCl c v 450 ml nc ct 2 ln
trong dng c ct lm bng thy tinh, thu c 500 ml HCl 22%.
Thic (II) clorua 10%: Nung chy thic kim loi trong chn s v nghin nhanh bng chy s
n khi nhn c bt thic mn. Cn 5,3 g bt ny v ha tan khi un nng trong 20 ml HCl 6N.
178
Dung dch nn chun b trc khi dng. C th chun b dung dch ny t mui SnCl
2
tinh khit ha
hc bng cch ha tan 10 g mui ny khi un nng trong 20 ml HCl 6N, sau thm mt t thic kim
loi.
Ru n- butylic: Ra n-butylic bng nc ct hai ln loi ht cht oxi ha c trong , cho
250 ml ru vo trong phu chit ln, thm vo 250 ml nc ct hai ln, lc 1 pht, sau khi tch tng,
rt lp nc pha di, cn lp ru tin hnh bo ha bng thic (II) clorua (c 100 ml ru butylic
thm vo 10 ml SnCl
2
10%, lc 3 - 5 pht; thm vo 5 ml ru etylic, khuy u).
Dung dch chun molipen: Ha tan mui amonimolipat tinh khit trong NH
4
OH c khi un
nng lin tc ( mi thi im dung dch u phi c phn ng kim), sau lm lnh ri kt ta
amonimolipat bng ru etylic, cho kt ta vo gia nhng t giy lc lm kh mui.
Ly 5 - 6 g mui kt tinh cho vo chn s ri nung trong l nung nhit 450 - 480
0
C trong
thi gian 40 - 60 pht. Cn 1,5 g MoO
3
thu c ri ha tan trong 10 ml NaOH 1N, thm vo dung
dch 10 ml HCl 22%, dng nc ct hai ln nh mc n 1 lt. Ta c dung dch cha 1 mg Mo/ml.
Pha long dung dch ny 1000 ln, c dung dch chun s dng.
Ch thch :
+ C th tch cht hu c ra khi dung dch phn tch bng cch chng th tch mu n kh trn
bp cch thy, sau t chn s vi phn kh vo trong l nung, nung 450
0
C trong 4 gi.
+ C th dng ete (tinh khit ha hc) thay cho ru n-butylic chit phc ca molipen vi
thioxianat.
9.2.7.7. Xc nh dng di ng ca ng, km, coban, mangan khi chit rt cc nguyn t ny trong t bng dung
dch m amoni axetat
Phng php da trn s chit rt Cu, Co, Zn v Mn bng dung dch amoniaxetat (pH = 4,8). T
l gia t: dung dch chit rt l 1:5. Thi gian lc trn my lc l 30 pht (Crupxky, 1994). Phng
php ny dng cho t cacbonat v khng cacbonat.
a. Chun b dung dch m: Dung dch c chun b t axit axetic v amoniac. Pha long 108ml
axit axetic c (98%) bng nc ct 2 ln n th tch 600 - 700 ml, thm vo 75 ml NH
4
OH 25%,
khuy u; sau khi ngui a th tch dung dch n 1 lt. Kim tra pH ca dung dch bng pH meter.
Axit axetic v amoniac dng chun b dung dch m cn phi tinh ch khi vt cc kim loi nng.
Axit axetic c ct trong bnh thy tinh c sinh hn nhm. Khi ct, cn thm mt lng va phi
natri axetat khan vo bnh ct. Nng axit c kim tra theo t trng.
tinh ch amoniac khi vt cc kim loi, ngi ta rt NH
4
OH 25% vo y bnh ht m ln,
phn trn bnh ht m t cc cc thy tinh ln c rt vo nc ct hai ln n 1/2 th tch cc.
y np bnh ht m v gi yn t nht l 48 gi. nhn c amoniac c nng cao hn cn x l
nc bo ha amoniac mt ln na bng cch thay dung dch amoniac trong bnh ht m bng dung
dch amoniac 25% mi. Nu x l nc bo ha amoniac 2 ln c th nhn c amoniac c nng
20%. Kim tra t trong dung dch amoniac nhn c, tnh lng amoniac, axit axetic cn thit pha
dung dch m theo t l nu trn.
b. Chit rt cc kim loi nng: Cn trn cn phn tch 50 g t ry qua ry 1mm, cho lng
cn trn vo bnh tam gic nt nhm th tch 500 ml, cho vo chnh xc 250 ml dung dch m
amoniaxetat, lc trn my lc 1 gi. Lc qua giy lc bng trng. Ly 150 ml dung dch lc cho vo
bt s, cho vo bt 10 ml HNO
3
(d = 1,4), 10 ml H
2
O
2
30%, ri chng dung dch trong bt trn bp
cch thy n trng thi st. Thm vo 2 ml HNO
3
, 2 ml H
2
O
2
ri chng n kh. Ha tan phn kh
trong 50 ml nc ct hai ln (c 3 - 4 ml HCl ct li 2 ln) khi un nng. Lc dung dch thu c vo
179
bnh nh mc 100 ml, ra giy lc bng nc ct hai ln c axit ha bng HCl. Dng nc ct 2
ln a th tch dung dch n vch mc v ly dung dch ny xc nh cc kim loi nng. Nu xc
nh Zn, cn chun b phn dch chit rt ring trong dng c thch anh. Sau nh lng theo cc
phng php nu.
9.2.7.8. Xc nh hm lng Cu, Pb, Zn di ng trong dung dch chit rt amoni axetat theo phng php Von-Ampe
ha tan
Ly 10 g t kh khng kh cho vo bnh tam gic 250 ml, thm vo 100 ml dung dch m
amoni axetat c pH = 4,8. Lc trn my lc 1 gi. Lc dung dch qua giy lc bng trng. Ly 80 ml
dung dch lc cho vo cc hay bt thch anh, thm vo 1 ml HNO
3
c v chng trn bp in n
trng thi st. Thm vo 2 ml HNO
3
c na, ri li chng dung dch trong cc. Qu trnh x l mu
bng HNO
3
tin hnh n khi phn cn li cha t nc c mu trng hay mu vng sng. Sau
chng lng cha trong cc n kh, xi nh phn kh bng HCl c ri chng dung dch trong cc
n trng thi mui m. Ha tan mui khi un nng trong 20 ml nc ct hai ln c axit ha
bng HCl (1:100). Lc dung dch qua giy lc c ra trc bng HCl long, hng dung dch lc
vo trong bnh nh mc 50 ml. Ra phn cn li trn giy lc bng nc ct nng axit ha ri a
th tch dung dch n vch mc.
xc nh ng, km, ch, ngi ta ly 8 ml dung dch cho vo cc dung tch 50 - 100 ml, thm
vo 0,5 ml dung dch Cd (4 g/ml) dng lm dung dch chun trong, mt lng nh axit ascorbic.
Khuy u dung dch ha tan hon ton axit ascorbic. Thm vo trong cc 1,5 ml dung dch m
amoni axetat (NH
4
OH 1M; NH
4
Cl 2,7M, CH
3
COOH 2M) chuyn dung dch vo bnh in phn to
git thy ngn; cho hiro (hay nit) qua dung dch ri tin hnh in phn ti th -1,2 V trong 3 pht.
Sau ngng cho hiro qua; gi yn dung dch 30 giy, bt u ghi ng biu din qu trnh ha tan
anot cc kim loi ng, ch, km. Sau khi ghi c mi mt pic u cn dng khng cho th bin thin
trong mt khong thi gian ngn. Nng ca nguyn t c xc nh theo phng php ng
chun.
9.3. S dng phng php quang ph hp th nguyn t xc nh cc
kim loi nng
T khi quang ph hp th nguyn t ra i, nhiu nh nghin cu vn dng xc nh lng
vt cc nguyn t trong cc i tng khc nhau.
L.A.Lerner v D.N.Ivanov 1970 xc nh hm lng ng, km, mangan, coban trong cc
dung dch chit rt t: HCl 1N; HNO
3
1N; HCl 0,1N; HNO
3
0,1N; H
2
SO
4
0,1N; CH
3
COOH 0,5N;
CH
3
COONH
4
1N; dung dch m amoni axetat (pH = 4,8).
Nhng s liu nhn c ch ra rng: c th xc nh trc tip Mn trong tt c cc dung dch chit
rt trn; km trong tt c cc dung dch chit rt trn tr amoniaxetat; ng v coban ch trong 2 dung
dch chit rt HCl 1N v HNO
3
1N.
Khi dng cc dung dch axit mnh khc nhau v tnh cht nhng c cng nng ng lng,
chit rt cc kim loi nng th kt qu xc nh hm lng ca chng rt gn nhau.
Khi s dng dung dch KCl 1N, ch chy ca ngn la b vi phm nhiu.
T l gia t v dung dch chit rt l 1:10, thi gian lc l 1 gi.
Dy cc mu u ca cc nguyn t cn xc nh c chun b bng cch ha tan cc mui tinh
khit ca cc nguyn t cn xc nh trong cc dung dch chit rt tng ng. i khi c th tin hnh
phn tch theo cc mu u trong nc.
180
nhy khi xc nh cc nguyn t nh sau:
Nguyn t
Vch phn
tch (A
0
)
Dng ca
n (A)
Chiu rng
ca khe
(m)
Chiu cao ca chm
sng i qua trn
phn trn ca n
kh (mm)
nhy
g/ml/1%
Cu
Co
Zn
Mn
3247,54
2407,25
2138,56
2794,82
8
20
10
14
50
25
300
100
2
2
2
2
0,05
0,1
0,02
0,07
Khi cc iu kin lm vic ca cc thit b n nh, th qua vi phun, a cc dung dch mu
u v dung dch phn tch vo trong ngn la ri xc nh cc gi tr mt quang D tng ng.
Theo cc gi tr mt quang thu c v nng cc mu t tng ng, v th chun trn
hai trc; da vo gi tr mt quang o c ca mu phn tch v ng chun ngi ta xc nh
c nng ca nguyn t cn phn tch.
Khi xc nh cc nguyn t c nng cao th mt quang tng ng D
L
ca cc nguyn t
s c gi tr cao hn ng k so vi gi tr mt quang ca s hp th khng chn lc D (D
L
D),
khi cn phi hiu chnh kt qu gi tr s hp th khng chn lc.
S hiu chnh kt qu theo s hp th khng chn lc c thc hin nh sau: Sau khi o cc gi
tr mt quang (D
L+
) theo cc vch hp th ca cc nguyn t tng ng, tin hnh xc inh gi tr
mt quang D, khi s dng di ph lin tc ca n hiro, hay l nhng vch khng hp th ca st
(nhng vch gn vi cc vch phn tch) c pht ra t n phng in kp nhiu nguyn t. Mt
quang D
L
ca nguyn t cn xc nh s bng D
L
= D
L+
- D

. S dng gi tr D
L
v th chun v
xc nh c nng cha bit. S hiu chnh theo s hp th khng chn lc gn lin vi vic thc
hin hai qu trnh o lin tc khi nghim ngt tun theo tt c cc iu kin phn tch.