TIU CHUN VIT NAM TCVN 6225-3 : 1996 ISO 7393/3 : 1986

CHT LNG NC XC NH CLO D V CLO TNG S PHN 3: PHNG PHP CHUN IOT XC NH CLO TNG S Water quality Determination of free chlorine and total chlorine Part three: lodometric titration method for the determination of total chlorine Li ni u TCVN 6225-3 : 1996 hon ton tng ng vi ISO 7393/3 : 1986. TCVN 6225 : 1996 do Ban k thut tiu chun TCVN/TC 147 Cht lng nc 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 CLO D V CLO TNG S PHN 3: PHNG PHP CHUN IOT XC NH CLO TNG S Water quality Determination of free chlorine and total chlorine Part three: lodometric titration method for the determination of total chlorine 1. Phm vi p dng Phn ny ca tiu chun qui nh phng php chun iot xc nh clo tng s trong nc. Phng php p dng xc nh nng clo (Cl2) t 0,01 n 0,21 mmol/l (0,71 n 15 mg/l). C nhiu cht cn tr vic xc nh (xem iu 10). Ph lc B quy nh phng php chun trc tip. Phng php ny thng c dng xc nh nng clo trn 7 mol/l (0,5 mg/l) trong nc ung x l. 2. Tiu chun trch dn ISO 5667-1- Phn 1: Hng dn lp chng trnh ly mu. TCVN 5992 : 1995, ISO 5667-2- Phn 2: Hng dn k thut ly mu. 3. nh ngha (xem bng 1) Phn ny ca tiu chun dng cc nh ngha sau: 3.1. Clo t do: Clo tn ti di dng clo nguyn t ha tan, axit hypoclor, hoc ion hypoclorit. 3.2. Clo lin kt: Phn ca clo tng s tn ti di dng cc cloramin v cloramin hu c. 3.3. Clo tng s: clo tn ti di dng clo t do hoc clo lin kt hoc c hai. 3.4. Cc cloramin: Nhng dn xut ca amoniac khi th mt, hai hoc ba nguyn t hidro bng nguyn t clo (monocloramin NH2Cl, dicloramin NHCl2 v tricloramin hoc nit triclorua NCl3) v tt c cc dn xut clo ha ca cc hp cht hu c cha nit. Bng 1 Thut ng v t ng ngha ca cc cht trong dung dch Thut ng T ng ngha Hp cht

Clo t do Clo tng s

Clo t do Clo d tng s

Clo t do hot ng Clo t do tim tng

Clo nguyn t, axit hypoclor hypoclorit Clo nguyn t, axit hypoclor, hypoclorit, cc cloramin

4. Nguyn tc Cho clo tng s phn ng vi kali iodua trong dung dch axit gii phng iot t do. Iot va sinh ra b kh ngay bng lng d chnh xc dung dch chun thiosunfat thm trc vo dung dch. Chun lng d thiosunfat bng dung dch chun kali iodat. 5. Thuc th Trong phn tch, ch dng cc thuc th tinh khit phn tch v nc quy nh 5.1. 5.1. Nc khng clo v cc cht kh Nc ct hoc nc qua trao i ion cn c kim tra cht lng nh sau: Dng hai bnh nn dung tch c 250 ml, sch cc cht kh clo (xem iu 6), cho vo theo th t sau: a) bnh u: 100 ml nc cn kim tra, khong 1 g kali iodua KI (5.2), 2 ml axit photphoric H 3PO4 (5.3) v 1 ml dung dch h tinh bt (5.6); b) bnh th hai: 100 ml nc cn kim tra, khong 1 g kali iodua KI (5.2), 2 ml axit photphoric H3PO4 (5.3) v 1 ml dung dch h tinh bt (5.6). Thm 10 git dung dch natri hypoclorit 0,1 g/l (pha long dung dch natri hypoclorit mua th trng v xc nh nng theo phng php iot). Nu nc l khng clo th bnh th nht s khng c mu, bnh th hai c mu xanh nht. Nu nc ct hoc nc qua trao i ion c cht lng khng p ng yu cu mong mun th phi clo ha n, ri sau mt thi gian tin hnh loi clo v em nc kim tra cht lng. Phng php clo ha v loi clo nu ph lc A. 5.2. Kali iodua (KI) tinh th. 5.3. Axit photphoric (H3PO4), dung dch khong 0,87 mol/l. Ha tan 64ml H3PO4 (p = 1,69 g/ml) trong nc, lm lnh v pha thnh 1000 ml. 5.4. Kali iodua, dung dch chun, c (1/6 KIO3) 10 mmol/l. Cn (chnh xc n miligam) khong 0,36g KIO3 kh, ha tan bng nc trong bnh nh mc dung tch 1000 ml, thm nc n vch v lc u. 5.5. Natri thiosunfat, dung dch chun, c (Na 2S2O3.5H2O) = 10 mmol/l. 5.5.1. Chun b dung dch Ha tan 2,48 g natri thiosunfat vo khong 250 ml nc trong bnh nh mc 1000 ml. Thm nc n vch mc v lc u. 5.5.2. Chun ha Chun ha dung dch hng ngy, hoc ngay trc khi dng nh sau: Ly 200 ml nc (5.1) vo mt bnh nn c 500 ml. Thm khong 1 g kali iodua (5.2), v sau dng pipet ly chnh xc 10,0 ml dung dch natri thiosunfat (5.5.1) cn chun ha, cho vo bnh nn, thm 2 ml axit photphoric H3PO4 (5.3) v 1 ml h tinh bt (5.6). Chun ngay bng dung

dch chun kali iodat (5.4) n khi xut hin mu xanh bn t nht 30s. Ghi s mililt dung dch iodat tiu tn. Tnh nng C1, tnh theo milimol trn lt, ca dung dch natri thiosunfat theo cng thc: C1 = trong C2 l nng ca dung dch chun kali iodat KIO3 [c (1/6 KIO3) 10 mmol/l], tnh bng milimol trn lt; V1 l th tch, ca dung dch natri thiosunfat em chun ha (V 1 = 10 ml); tnh bng mililt; V2 l th tch, ca dung dch chun kali iodat KIO 3 tiu tn trong chun , tnh bng mililt; 5.6. Tinh bt, dung dch 5 g/l, hoc cht ch th tng t mua trn th trng. 6. Thit b, dng c: dng c th nghim thng thng v buret, c u mt nh, c 30 git/ml, o c n 25ml, chia n 0,05ml. Ch khi chun b dng c thy tinh: Dng c thy tinh khng clo (ngha l sch cc cht kh clo) c chun b bng cch np y dung dch natri hypoclorit 0,1 g/l. Sau 1 gi, trng sch bng nc ct sau bng nc khng clo. 7. Ly mu Xem ISO 5667/1 v TCVN 5992 : 1995 (ISO 5667/2). 8. Cch tin hnh 8.1. Phn mu th Tin hnh xc nh ngay sau khi ly mu. Ht sc trnh lc mu, trnh mu tip xc vi nh sng hoc sc nng. Ly phn mu th khng qu 200 ml v cha khng nhiu hn 0,21 mmol/l (15 mg/l) clo tng s. Nu nng clo tng s vt qu gi tr va nu th pha long mu bng nc (5.1) v ly phn mu th nh hn 200 ml. 8.2. Xc nh Cho phn mu th (8.1) vo bnh nn c 500 ml. Dng pipt thm 10,0 ml (V 4) dung dch chun natri thiosunfat (5.5), v sau thm theo th t: khong 1 g kali iodua KI (5.2), 2ml axit photphoric H3PO4 (5.3) v 1ml h tinh bt (5.6). Chun ngay bng dung dch tiu chun kali iodat KIO 3 (5.4) n khi xut hin mu xanh bn t nht 30s. Ghi th tch iodat tiu tn (V3). 9. Biu th kt qu 9.1. Tnh ton Nng clo tng s, c (Cl2), tnh bng milimol trn lt, theo cng thc: c (Cl2) = trong C1 l nng , ca dung dch chun natri thiosunfat Na 2S2O3 (5.5), tnh bng milimol trn lt; V0 l th tch, ca phn mu th trc khi pha long (nu c), tnh bng mililt; V3 l th tch, ca dung dch chun kali iodat KIO 3 (5.4) tiu tn trong chun (8.2), tnh bng mililt;
V4C1 V3C 2 2V0 V2C2 V1

V4 l th tch, ca dung dch tiu chun natri thiosunfat Na 2S2O3 (5.5) dng trong chun (8.2) (V4 = 10 ml), tnh bng mililt. C th tnh chuyn nng mmol/l thnh nng mg/l, theo cng thc: p (Cl2) = M.c (Cl2) trong M l khi lng phn t ca clo (M = 70,1 g/mol), tnh bng gam trn mol. 9.2. lp li v ti lp Nhng s liu sau y l rt ra t phng php chun trc tip. Ch thch Phng th nghim v gim st ca c quan bo v mi trng M [1] nh gi phng php chun iot trc tip, dng phenylasinoxit thay cho thiosunfat. Vi cc mu nc c nng clo tng s c (Cl) = 3,5 v 56,7 mol/l [p (Cl2) = 0,25 v 4,02 mg/l], lch chun tng i l 0,23% v 0,76% tng ng. Mu nc ung c nng clo tng s c (Cl2) = 9,6 mol/l [p (Cl2) = 0,68mg/l], lch chun tng i l 5,2 %. Vi cc mu nc b nhim, chnh xc km hn. Ch trng hp nc sng c nng clo tng s c (Cl2) = 4,2 mol/l [p (Cl2) = 0,30mg/l], lch chun tng i l 9,7 %. Cc kt qu chun trc tip (do Cc Mi trng [2] cng b) l da trn s liu dng dung dch chun kali iodat KIO3 tng ng vi nng clo. S liu ny cho thy nng clo tng s tng ng c (Cl2) = 28,2 mol/l [p (Cl2) = 20 mg/l], lch chun tng i l 2,2% n 3,7% v vi c (Cl2) = 282 mol/l [p (Cl2) = 20 mg/l], lch chun tng i l 0,39% n 0,65%. Nhng kt qu nu trn rt t nhng php th c lp li ti cng mt phng th nghim v dng lm thc o lp li ca phng php. Cc trng hp trn u dng phng php chun trc tip (xem ph lc B). c nhng c gng nhm xc nh ti lp ca phng php bng cch phn phi mu cho nhiu phng th nghim khc nhau, nhng kt qu thu c khng ng tin cy bi v tnh khng bn ca dung dch cha clo t do v clo lin kt. Gn y, mt chi nhnh bo him cht lng ca EMSL-Cincinati [4] thy rng natri hypoclorit pha trong nc rt tinh khit v ng trong l kn, gi trong ti khi vn chuyn, c bn ng k. Kt qu l nhiu phng th nghim ca t chc hi v quc gia M c c nhng thng s phn tch clo phng php hin hnh v c nu bng 2. 10. Cc cht cn tr Khng phi ch c clo ha iodua thnh iot. Ty theo nng v ha th, s oxi ha c th c gy ra bi nhiu tc nhn oxi ha. Bi vy, phng php ch p dng c khi trong mu khng c cc cht oxi ha khc, c bit l brom, iot, cc bromamin, iodtamin, ozon, hydro peoxit, permanganat, iodat, bromat, cromat, clo dioxit, clorit, manganat, nitrit, cc ion st (III), cc ion ng (II), cc ion mangan (III). 11. Bo co kt qu Bo co kt qu cn c nhng thng tin sau: a) trch dn tiu chun ny; b) mi thng tin cn thit nhn dng mu; c) kt qu v phng php th hin kt qu; d) chi tit v bt k thao tc no khng quy nh trong tiu chun ny, hoc xem nh t chn, cng mi tnh hung c th nh hng n kt qu. Bng 2 Thng s phn tch lin phng th nghim xc nh clo t do Gi tr thc c (Cl2) p (Cl2) Phng php1) S phng th Trung bnh mg/l lch chun mg/l

mol/l

mg/l 0,50 A B C D

nghim 3 6 7 2 4 10 14 6 4 10 14 6 4 6 7 2

mol/l

mol/l

9,2 6,2 6,8 6,2 11,8 10,9 11,1 11,6 15,9 15,5 16,2 16,5 18,8 18,6 19,9 20,0

0,65 0,44 0,48 0,44 0,84 0,77 0,79 0,82 1,13 1,10 1,15 1,17 1,33 1,32 1,41 1,42

5,1 1,3 1,8 2,7 1,4 1,1 4,1 1,3 1,6 2,0 5,5 1,1 10,2 1,3 5,4 0,6

0,36 0,09 0,13 0,19 0,10 0,08 0,29 0,09 0,11 0,14 0,39 0,08 0,72 0,09 0,38 0,04

11,3

0,80

A B C D

15,5

1,10

A B C D

18,2

1,29

A B C D

1) A: ch th im cui bng h tinh bt B: chun ampe iot C: trc quang dng DPD D: chun dng DPD. Ti liu tham kho [1] Bender D.F. So snh cc phng php xc nh clo d tng s trong cc mu c thnh phn khc nhau, Bo co s EPA-600/4-78-019, Cincinnati, Ohio 45268, USA, US-EPA, 1978. [2] Cc mi trng, Ha cht kh trng trong nc v nc thi, v yu cu clo, cc phng php kim tra nc v vt liu lin quan. London, UK, HMSO, 1980. [3] Hallinan F.J. Chun thiosunfat xc nh clo d. J.Am.Chem.Soc.61, 1939:265. [4] Cng trnh nghin cu WS007 v WS008, Cincinnati, Ohio 45268, USA, Ngnh bo him Cht lng, Gim st mi trng v phng th nghim h tr, C quan nghin cu v pht trin, US-EPA, 1980. [5] Wilson V.A. Xc nh clo trong dung dch hypoclorit bng cch chun trc tip bng thiosunfat. Ind.Eng.Chem.Anal.Ed.7 1935:44.

PH LC A
(Qui nh) Chun b nc khng clo

 iu ch nc pha long c cht lng mong mun, trc ht clo ha nc ct hoc nc trao i ion n khong 10 mg/l v gi trong bnh kn t nht 16 gi. Sau loi clo bng cch chiu tia cc tm t nht na gi hoc di nh nng nhiu gi. Cui cng kim tra cht lng theo phng php quy nh 5.1.

PH LC B
Phng php chun iot trc tip xc nh clo tng s trong nc c hm lng cc cht hu c thp (Ph lc ny khng phi l mt phn ca tiu chun) B.1. Phm vi p dng Ph lc ny qui nh phng php chun iot trc tip thng dng xc nh clo tng s trong nc ung x l. Vi phn mu th 500 ml, nng thp nht c th xc nh c l 7 mol/l (0,5 mg/l). Xem iu 10 v cc cht cn tr. B.2. Nguyn tc Oxi ha kali iodua KI bng clo t do v lin kt trong dung dch axit, chun lng iot sinh ra bng dung dch chun natri thiosunfat. B.3. Thuc th Xem iu 5. B.4. Thit b, dng c Xem iu 6. B.5. Cch tin hnh B.5.1. Phn mu th Xem iu 8.1 Khi nng nh hn 0,014 mmol/l (1 mg/l) ly 1000 ml, khi nng trong khong t 0,014 mmol/l n 0,14 mmol/l (1 n 10 mg/l) ly 500 ml, v khi nng cng cao, th tch phn mu th cng nh. Ghi th tch phn mu th ly. B.5.2. Xc nh Cho phn mu th (B.5.1) vo bnh nn hoc a s trng. Thm 2 ml axit photphoric H 3PO4 (5.3) to pH 2-3, khong 1 g kali iodua KI (5.2). Lc u v chun bng dung dch chun natri thiosunfat Na2S2O3 (5.5) n khi dung dch c mu vng. Thm 1ml h tinh bt (5.6) v tip tc chun n khi mt mu xanh. Ghi th tch dung dch thiosunfat tiu tn (V 5). B.6. Biu th kt qu Nng clo tng s c (Cl2), tnh bng milimol trn lt, theo cng thc: c (Cl2) = trong C1 l nng chnh xc ca dung dch chun thiosunfat (5.5), tnh bng milimol trn lt; V0 l th tch ca phn mu th, tnh bng mililt; V5 l th tch ca dung dch chun thiosunfat (5.5) tiu tn trong chun (B.5.2), tnh bng mililt; C th tnh chuyn thnh nng miligam trn lt, theo cng thc:
C1 V5 2V0

p (Cl2) = M. c (Cl2) trong M l khi lng phn t ca clo (M = 70,91 g/mol).