TIU CHUN VIT NAM

TCVN 6182 : 1996

ISO 6595 : 1982 (E)
CHT LNG NC - XC NH ASEN TNG - PHNG PHP QUANG PH DNG BC
DIETYDITHIOCACBAMAT
Water quality - Determination of total arsenic - Silver diethyldithiocarbamate spectrophotometric
method
Li ni u
TCVN 6182:1996 hon ton tng ng vi ISO 6595:1982 (E).
TCVN 6182:1996 do Ban k thut tiu chun TCVN TC 135 F9 SC1 Nc tinh lc bin son.
Tng cc Tiu chun - o lng - Cht lng ngh, B Khoa hc, Cng ngh v Mi trng
ban hnh.
CHT LNG NC - XC NH ASEN TNG - PHNG PHP QUANG PH DNG BC
DIETYDITHIOCACBAMAT
Water quality - Determination of total arsenic - Silver diethyldithiocarbamate
spectrophotometric method
Phng php nu ra trong tiu chun ny dng cho cc nh ha hc hoc cc k thut vin
c hun luyn hoc c hng dn. Cn ch c bit v c tnh ca asen, cc dung dch
ca chng v thuc th dng phn tch. Cn ch khi s dng v dung dch sau khi phn
tch. Pyridin v clorofom phi dng trong t ht c c hiu lc. Efedrin l mt loi thuc trong
danh mc c cht phi s dng ph hp vi cc qui nh.
1. Phm vi p dng
Tiu chun ny qui nh phng php xc nh asen trong nc v nc thi bng quang ph
dng bc dietyldithiocacbamat.
C th p dng xc nh nng asen trong khong t 0,001 n 0,1 mg/l. Trong trng hp
cc cht asen kh phn hy, phn hy chng bng phng php m t trong ph lc A, iu A1.
C th xc nh nng ca n cao hn bng cch pha long thch hp cc mu th vi nc
khng cha asen.
Antimon nh hng ti vic xc nh asen (xem ph lc A, iu A2), crom, coban, molipden,
niken, thy ngn, bc, bch kim vi nng ti 5 mg/l khng nh hng ti vic xc nh.
2. nh ngha
S dng cc nh ngha sau y cho mc ch ca tiu chun ny:
Asen tng: tng trng lng nguyn t asen dng nguyn t hoc trong cc hp cht v c,
hu c.
Ch thch - Ph thuc vo th oxi ha kh v pH ca nc, asen c th dng ha tr 3 (v
d: ion asanit AsO33-) hoc asen c ha tr 5 (v d: ion asenat AsO43-), hoc As trong trng hp
cht hu c.
3. Nguyn tc
3.1. Oxi ha cc cht hu c hoc sunpht bng cch un nng vi kali pemanganat v kali
perodisunfat.
3.2. Kh asen ha tr V sang ha tr III.
3.3. Kh asen ha tr III sang AsH3 (asin) bng NaBH3 trong mi trng axit.

3.4. Hp th asin trong dung dch bc dietyldithiocacbamat trong clorofom hoc pyridin v o
quang ph [ca phc cht mu - tm c to thnh] bc sng 510 nm hoc 525 nm
tng ng vi mi dung mi.
4. Thuc th
Nu khng c qui nh no khc, dng cc loi thuc th thuc loi tinh khit phn tch v s
dng nc ct hoc nc kh ion.
Asen trong thuc th v trong nc phi khng ng k.
4.1. Axit sunfuric, p = 1,84 mg/l.
4.2. Dung dch axit sunfuric c(1/2 H2SO4) = 2 mol/l.
4.3. Dung dch natri hidroxit c(NaOH) = 2 mol/l ng trong chai nha polyetylen.
4.4. Kali pemanganat (KMnO4), dung dch 50 g/l.
Ha tan 50 g KMnO4 trong nc v pha long ti 1 000ml.
Ch ha tan hon ton thuc th.
Bo qun trong chai thy tinh ti mu.
4.5. Dung dch kali peroxodisunfat, 40 g/l.
Ha tan 40 g kali peroxodisunfat trong nc v pha long ti 1 000 ml.
4.6. Dung dch hidroxylamin hidroclorua, 100 g/l.
Ha tan 10 g hidroxylamin hidroclorua trong nc v pha long ti 100 ml.
Dung dch ny bn vng t nht l 1 thng.
4.7. Dung dch kali iodua, 150 g/l.
Ha tan 15 g kali iodua trong nc v pha long ti 100 ml.
Bo qun trong chai thy tinh ti mu.
Dung dch ny bn vng t nht l 1 thng.
4.8. Dung dch thic clorua.
Ha tan 55 g thic (II) clorua ngm 2 phn t nc trong 25 ml axit clohydric m c (p = 1,19
g/ml) v pha long vi nc ti 100 ml.
Dung dch ny n nh nu bo qun trong t lnh.
4.9. Dung dch hp thu A.
Ha tan 0,500 g bc dietyldithiocacbamat v 0,330 g 1 - ephedrin trong clorofom v pha long
vi clorofom ti 200 ml.
Dung dch ny c th bn vng t nht 1 thng nu bo qun trong chai thy tinh ti mu v nt
kn.
4.10. Dung dch hp thu B
Ha tan 1,000 g bc dietyldithiocacbamat trong pyridin v pha long vi pyridin ti 200 ml.
Bo qun dung dch trong chai ti mu.
4.11. Bt km, c ht 0,5 - 1 mm.
4.12. Dung dch ng (II) sunfat.
Ha tan 15 g ng (II) sunfat ngm 5 phn t nc trong nc v pha long ti 100 ml.
4.13. Asen, dung dch chun cha 350 mg As trn lt.

Ha tan ng 0,4620 g asen (III) oxit (As2O3) c lm kh bng silicagen trong 12 ml dung
dch natri hidroxit (4.3). Trung ha vi dung dch axit sunfuric (4.2) v pha long vi nc ti
1000 ml.
1 ml dung dch chun ny cha 0,35 mg asen.
4.14. Asen, dung dch chun cha 3,5 mg asen trn lt.
Pha long 10 ml dung dch chun asen (4.13) trong nc v thm nc ti 1 000 ml.
1 ml dung dch chun ny cha 3,5 g asen.
Dung dch ny ch n nh trong vi ngy.
Chun b dung dch ngay trc khi s dng.
4.15. Asen, dung dch chun cha 0,35 mg asen trn lt.
Pha long 1 ml dung dch asen chun (4.13) trong nc v pha long ti 1 000 ml.
1 ml dung dch chun ny cha 0,35 g asen.
Chun b dung dch ngay trc khi s dng.
5. Thit b
S dng cc thit b ca phng th ngihm thng thng, v
5.1. Quang ph k, lp cc cuvt c chiu di quang hc t 10 n 50 mm [i vi cc chiu di
quang hc ln hn 10 mm, dng cc microcuvt c dung tch nh (ti a 5 ml)].
5.2. Thit b phn ng (theo hnh 1 hoc cc thit b tng ng), gm:
- bnh nn dung tch 500 ml c ng ni thy tinh theo qui nh ca ISO 383;
- ng hp thu c ng ni thy tinh theo qui nh ca ISO 383;
5.3. Bnh nh mc dung tch 1 000 ml.
5.4. Pipet c dung tch 1 -2 -5 -10 v 20 ml.
5.5. ng ong hnh tr c dung tch 25, 100 v 500 ml.

Hnh 1 - Mu ca thit b phn ng

6. Cch tin hnh
6.1. Phn mu th
Chuyn 350 ml mu vo ng ong. Nu hm lng asen d tnh ln hn 0,1 mg/l, ly mt lng
mu nh hn v pha long ti 350 ml.
6.2. Th mu trng
Tin hnh th mu trng, dng cc thuc th nh trong phn tch mu theo cng mt trnh t k
c x l s b nhng thay mu th bng 350 ml nc khng cha asen.
6.3. Chn dung dch hp thu
Vic chn dung dch hp thu A (4.9) hoc B (4.10) l do ngi phn tch. Pyridin tuy c mi kh
chu nhng t bay hi hn clorofom v th tch dung dch B i hi t phi iu chnh hn trong
khi phn tch. H s hp th phn t khi dng dung dch hp thu B ln hn khi dng dung dch
hp thu A l 30%. Do vy cn s dng cng mt loi dung dch hp thu cho c th mu trng,
xc nh ln khi chun b lp ng chun.
6.4. Chun b ng chun
6.4.1. Chun b dung dch so snh chun

6.4.1.1. Dng pipet ly cc lng dung dch asen chun (4.14 v 4.15) nh trong bng 1 cho vo
hai lot bnh nn (5.2) v thm nc vo mi bnh ti 350 ml.
Bng 1
Th tch dung dch asen chun (4.14)

Hm lng asen tng ng

ml

g/l

0*

1,0

10

2,0

20

5,0

50

10,0

100

Th tch dung dch asen chun

ml
0*

1,0

2,0

5,0

10,0

10

20,0

20

* Thuc th ca mu th trng dng hiu chun.

6.4.1.2. Thm 20 ml dung dch axit sunfuric (4.1) vo mi bnh.
6.4.1.3. Thm 10 ml dung dch kali iodua (4.7) v 1 ml dung dch km (II) clorua (4.8).
6.4.1.4. Chuyn 5 ml dung dch hp thu A (4.9) hoc dung dch hp thu B (4.10) thch hp (xem
6.3) vo ng hp thu.
Thm 1 ml dung dch ng (II) sunfat (4.12) v 15 g km (4.11) vo mi bnh. Ni ngay ng hp
thu vi bnh. Phi m bo cho dng c phn ng c kn, c th bi mt t m khng cha
asen vo ch ni thy tinh.
yn trong 2 gi asin chuyn ha hon ton. Thm clorofom (trong trng hp dng dung
dch hp thu A) hoc pyridin (trong trng hp dng dung dch hp thu B) c th tch dung
dch hp thu 5 ml b vo lng b bay hi.
Thnh thong lc nh bnh trnh to kt ta trong vng vo ca dung dch hp thu.
Phc cht mu c th n nh trong khong 2 gi nu c bo v khi nh sng; do vy sau
khi asin chuyn ha hon ton phi tin hnh do quang ph ngay trong khong thi gian ny.
6.4.2. o quang ph
i vi tng dung dch so snh chun (6.4.1.1), dung dch t ng hp thu y vo mt cuvt
v i y vo cuvt i chiu bng dung mi ca dung dch hp thu thch hp (clorofom hoc
pyridin tng ng).
o mt quang ca dung dch th bng quang ph k (5.1), khi dng dung dch hp thu A (4.9)
th o 510 nm, hoc dng dung dch hp thu B (4.10) th 540 nm.
6.4.3. Dng ng chun
Chnh mt quang o c ca cc dung dch t ng hp thu (6.4.2) tng ng vi mi dung
dch so snh chun (6.4.1.1) bng cch tr i mt quang ca thuc th trng.

i vi mi dy dung dch chun tng ng (4.14 v 4.15), dng th c hp thu trn trc
tung, ng vi nng asen tnh bng microgam trn lt trn trc honh.
C hai ng phi tuyn tnh.
Xy dng cc ng chun thng xuyn, t nht l trong mi ln s dng thuc th mi.
6.5. Xc nh
6.5.1. X l s b
Chuyn mu th vo bnh nn (xem 5.2) v thm 20 ml dung dch axit sunfuric (4.1), 5 ml dung
dch kali pemanganat (4.4) v 50 ml kali peroxodisunfat (4.5). un nhit 90 oC trong 2 gi (c
th dng bp in hay ni cch thy). ngui ti nhit trong phng v thm 20 ml dung dch
hidroxylamin hidroclorua (4.6).
Ch thch - Lng cht oxi ha cn cho nhu cu oxi ha hc ln ti 100 mg/l.
6.5.2. Pht trin mu
Tin hnh theo m t 6.4.1.3 v 6.4.1.4.
6.5.3. o quang ph
Tin hnh theo m t 6.4.2.
7. Biu th kt qu
T th hiu chun, xc nh nng asen tng ng vi mt quang ca dung dch mu
th v dung dch th mu trng. Phi tnh ti h s pha long ca mu th (xem 6.1).
Hm lng asen, tnh bng miligam trn lt theo cng thc:

( A2 A1 ) xf
l
trong
A1 l mt quang ca dung dch mu th trng;
A2 l mt quang ca dung dch mu th;
f l h s hiu chun, milimet miligam trn lt;
l l di quang hc ca cuvt, milimet.
Bo co kt qu hm lng asen, miligam trn lt, tnh chnh xc n 0,001 mg/l trong trng
hp hm lng nh hn 0,1 mg/l; tnh chnh xc n 0,01 mg/l nu hm lng asen ln hn
0,1mg/l. (V d: hm lng asen l 0,42 mg/l). C th biu th hm lng asen bng milimol trn
lt (i vi asen, 1 mmol = 74,9 mg).
8. Bo co kt qu
Bo co kt qu bao gm cc thng tin sau:
a) ghi tham kho tiu chun ny;
b) nhn bit mu;
c) ghi kt qu v phng php biu th s dng;
d) ghi nhng c im bt thng trong qu trnh xc nh;
e) ghi bt k cc chi tit thao tc khng ch ra trong tiu chun ny hoc s t la chn khc.

PH LC A

TRNG HP C BIT V CC CHT GY NHIU

A.1. Cc hp cht asen kh phn hy
xc nh As tng trong nc cha silic florua (th d: nc thi ca nh my sn xut thy
tinh), hoc trong nc c hp cht As hu c kh phn hy, phi dng phng php x l vi
axit sunfuric v H2O2. Trong trng hp ny un nng vi axit sunfuric v thm nhiu ln H 2O2.
Tip tc qui trnh n khi xut hin khi SO3. Sau pha long mu vi nc v tin hnh nh
trong 6.4.2.
A.2. Antimon
Mui antimon b kh trong iu kin th to thnh SbH 3, cht ny phn ng vi dung dch hp
thu to thnh hn hp mu . Nu dng cuvt c chiu di ng quang 10 mm, hm lng
antimon 0,5 mg/l s tng mt quang ln 0,015%. Khi phn tch nc thi antimon nh hng
rt ln. Nu antimon c mt trong nc vi hm lng ln th khng th s dng phng php
ny phn tch.