tcvn

tIu chun vit nam

tcvn 6491 : 1999 ISO 6060 : 1989

Cht lng nc xc nh nhu cu oxi ha hc

Water quality Determination of the chemical oxigen demand

H ni - 1999

TCVN 6491 : 1999

Li ni u
TCVN 6491 : 1999 hon ton tng ng vi tiu chun ISO 6060 : 1989; TCVN 6491 : 1999 do Ban k thut TCVN/TC147 Cht lng nc bin son, Tng cc Tiu chun o lng Cht lng ngh, B Khoa hc Cng ngh v Mi trng ban hnh.

TCVN 6491 : 1999

tiu chun vit nam

TCVN 6491: 1999

Cht lng nc Xc nh nhu cu oxi ho hc

Water quality Determination of the chemical oxigen demand

1 Phm vi
Tiu chun ny quy nh phng php xc nh nhu cu oxi ho hc COD ca nc. Tiu chun ny p dng c cho cc loi nc c gi tr COD t 30 mg/l n 700 mg/l Hm lng clorua khng c vt qu 1000 mg/l. Mu nc ph hp vi cc iu kin ny c s dng trc tip cho phn tch. Nu gi tr COD vt qu 700 mg/l, mu nc cn c pha long. Gi tr COD nm khong 300mg/l n 600mg/l t c chnh xc cao nht. Trong iu kin phn ng cho, cc hp cht hu c b oxi ho trit . Ngoi tr cc cht c cc nguyn t c cu trc nht nh (v d nhn pyridine, cc hp cht nit bc 4). Mt t cht k nc c th bay hi v thot khi s oxi ho. Cc cht v c b oxi ho trong iu kin phn ng l, v d : - cc ion brm, ion it; - mt s hp cht lu hunh nht nh; - cc ion nitrit; - mt s hp cht kim loi. Mt khc mt s cht nht nh c th tham gia phn ng nh l tc nhn oxi ho. Tu thuc vo mc ch s dng kt qu php th, cn lu cc tnh hung ny. Cc cht cn tr, ng ch l clorua, xin xem thm iu 10.

2 Tiu chun trch dn

TCVN 1609 : 1988 Dng c o dung tch bng thu tinh dng trong phng th nghim Buret, hoc ISO 385 -1 : 1984 Dng c thu tinh phng th nghim Buret Phn 1 : Yu cu chung. ISO 5790 : 1979 Sn phm ho cht v c dng trong cng nghip Phng php chung xc nh hm lng clorua Phng php thu ngn.

TCVN 6491 : 1999 3 nh ngha

Tiu chun ny p dng nh ngha sau Nhu cu oxi ho hc (COD): Nng khi lng ca oxi tng ng vi lng dicromat tiu tn bi cc cht l lng v ho tan trong mu nc khi mu nc c x l bng cht oxi ho iu kin xc nh.

4 Nguyn l
un hi lu mu th vi lng kali dicromat bit trc khi c mt thu ngn (II) sunfat v xc tc bc trong axit sunfuric c trong khong thi gian nht nh, trong qu trnh mt phn dicromat b kh do s c mt cc cht c kh nng b oxi ho. Chun lng dicromat cn li vi st (II) amoni sunfat. Tnh ton gi tr COD t lng dicromat b kh, 1 mol dicromat (Cr2O7-2) tng ng vi 1,5 mol oxi (O2). Nu phn mu th c cha clorua ln hn 1000 mg/l cn phi p dng quy trnh khc.

5 Thuc th v nguyn liu

Cnh bo: Phng php ny lin quan n vic x l v un si cc dung dch axit sunfuric c v dicromat. Cn phi s dng qun o bo h, gng tay v mt n. Khi xy ra ri rt, nhanh chng ra nhiu ln bng nc sch l cch lm hiu qu v n gin nht. Khi thm axit sunfuric c vo nc cn phi lun lun tin hnh rt cn thn v lc nh bnh cha. Cn phi cn thn khi chun b v x l dung dch cha bc sunfat v thu ngn sunfat v y l nhng cht c. Cc thuc th qua s dng cha mui thu ngn, bc v cromat khi thi ra ngoi cn phi c x l theo cc quy nh ca quc gia hoc a phng (xem thm ISO 5790 : 1979, ph lc B). Khi phn tch, ch s dng cc thuc th c tinh khit phn tch c tha nhn v nc ct hoc nc c tinh khit tng ng. Ch thch 1 Cht lng nc l yu t rt quan trng i vi chnh xc ca kt qu. Kim tra cht lng nc
bng cch thc hin mu trng (m t trong 8.2) v tin hnh song song mu th khng un nng nhng gi nguyn cc iu kin khc. Lu s tiu tn ca dung dch st (II) amoni sunfat (5.4) trong c hai trng hp. S khc nhau ln hn 0,5 ml chng t cht lng nc km. xc nh gi tr COD di 100 mg/l th s khc bit khng c vt qu 0,2 ml. Cht lng ca nc ct thng c th c ci thin bng cch ct li t dung dch kali dicromat axt ho hoc dung dch kali pecmanganat, dng thit b chng ct bng thu tinh ton b.

5.1 Axit sunfuric, c(H2SO4) = 4 mol/l Thm t t v cn thn 220 ml axit sunfuric ( = 1,84 g/ml) vo khong 500 ml nc ct. ngui v pha thnh 1000 ml.

TCVN 6491 : 1999

5.2 Bc sunfat - axit sunfuric Cho 10 g bc sunfat (Ag2SO4) vo 35 ml nc. Cho t t 965 ml axit sunfuric c ( = 1,84 g/ml). 1 hoc 2 ngy cho tan ht. Khuy dung dch tng nhanh s ho tan. 5.3 Kali dicromat Dung dch chun c nng 0,040 mol/l, cha mui thu ngn. Ho tan 80 g thu ngn (II) sunfat (HgSO4) trong 800ml nc. Thm vo mt cch cn thn 100ml axit sunfuric ( = 1,84 g/ml). ngui v ho tan 11,768 g kali dicromat sy kh 105 oC trong 2 gi vo dung dch. Chuyn ton b dung dch vo bnh nh mc v nh mc n 1000 ml. Dung dch bn t nht 1 thng. Ch thch 2 Nu mun, c th s dng dung dch dicromat khng c mui thu ngn. Khi , thm 0,4 g thu
ngn (II) sunfat vo phn mu th trc khi thm dung dch dicromat (5.3) vo bnh phn ng m t trong 8.1 v lc u.

5.4 St (II) amoni sunfat, dung dch chun c nng , c[(NH4)2Fe(SO4)2 6H2O] 0,12 mol/l Ho tan 47,0 g st (II) amoni sunfat ngm 6 phn t nc vo trong nc. Thm 20 ml axit sunfuric c ( = 1,84 g/ ml). Lm lnh v pha long bng nc thnh 1000 ml. Dung dch ny phi chun li hng ngy theo cch nh sau: Pha long 10,0 ml dung dch kali dicromat (5.3) n 100 ml vi axit sunfuric (5.1). Chun dung dch ny bng dung dch st (II) amoni sunfat ni trn s dng 2 hoc 3 git ch th feroin (5.6). Nng , c, ca st (II) amoni sunfat tnh bng mol trn lt, c tnh theo cng thc:
10 ,0 0 ,040 6 2 ,4 = V V

Trong : V l th tch dung dch st (II) amoni sunfat tiu tn tnh bng mililit. 5.5 Kali hidro phtalat, dung dch chun, c(K1C8H5O4) = 2,0824 mmol/l Ho tan 0,4251 g kali hidro phtalat c sy kh 105 oC, vo trong nc v nh mc n 1000ml. Dung dch ny c gi tr COD l thuyt l 500 mg/l. Dung dch bn t nht mt tun nu bo qun trong xp x 4oC. 5.6 Feroin, dung dch ch th. Ho tan 0,7 g st (II) sunfat ngm 7 phn t nc (FeSO4 7H2O) hoc 1g st (II) amoni sunfat ngm 6 phn t nc [(NH4)2Fe(SO4)2 6H2O] trong nc. Thm 1,50 g 1,10- phenantrolin ngm mt phn t nc C12H8N2 H2O v lc cho n khi tan ht. Pha long thnh 100 ml.

TCVN 6491 : 1999

Dung dch ny bn trong vi thng nu c bo qun trong ti. C bn sn cc dung dch ny trn th trng.

6 Thit b, dng c
Cc dng c thng thng ca phng th nghim, v 6.1 B chng ct hi lu, gm c mt bnh hoc ng phn ng 250 ml c c nhm ni vi mt ng sinh hn trnh mt mt ng k cc cht bay hi. C th phi lm mt sinh hn bng nc lnh hoc khng kh lnh. Lm sch dng c mi bng cch tin hnh mu trng nh c m t trong 8.2. Lm sch dng c dng xc nh COD bng cch sc vi nc ct sau mi ln chun . Khng c s dng bt k cht ty ra no. 6.2 Bp un hoc cc phng tin t nng khc, c kh nng un si mu trong vng 10 pht.

Phi bo m rng cc dng c lm vic khng gy ra qu nng cc b cho dung dch ang c un.

6.3

Buret chnh xc, dung tch 10ml, c vch chia 0,02 ml ph hp vi TCVN 1609 : 1988 (hoc ISO

385 -1). 6.4 Ht si, ht thu tinh th ng knh 2 mm n 3 mm hoc cc loi ht si khc, c lm sch

theo qui trnh c m t trong 6.1. Lu khi chun b dng c thu tinh Cc dng c thu tinh cn c ra sch cn thn v gi khng b bm bi v ch dng ring cho php th COD.

7 Ly mu v bo qun mu
Mu phng th nghim phi c u tin ly vo l thu tinh, mc d l polyethylen cng thch hp. Phn tch mu cng sm cng tt v khng qu 5 ngy sau khi ly mu. Nu mu cn phi c bo qun trc khi phn tch, thm 10ml axit sunfuric (5.1) cho 1 lt mu. Gi mu 0oC n 5oC. Lc cc l mu bo qun v phi m bo chc chn rng mu trong cc l c ng nht khi ly mt phn mu em phn tch.

8 Cch tin hnh

8.1 Xc nh

TCVN 6491 : 1999

Chuyn 10,0 ml mu (pha long nu cn thit) vo bnh phn ng (xem 6.1), thm 5,00ml 0,01ml dung dch kali dicromat (5.3). Thm vo vi ht si (6.4) vo phn mu th (thng l 10 ml) v lc trn u. Thm t t 15 ml dung dch bc sunfat trong axit sunfuric (5.2) v nhanh chng lp bnh vo ng sinh hn. a hn hp phn ng ti si trong vng 10 pht v tip tc un 110 pht na. Nhit ca hn hp phn ng cn phi t l 148oC 3oC. Lm ngui ngay bnh phn ng bng nc lnh cho n khong 60 oC v ra ng sinh hn vi lng nh nc. Tho ng sinh hn v pha long hn hp phn ng cho n khong 75 ml v lm ngui n nhit phng. Chun lng d dicromat bng st (II) amoni sunfat (5.4) s dng 1 hoc 2 git ch th feroin (5.6). Ch thch
3 Cn phi un si nh hn hp phn ng v khng xy ra tro. Hn hp b si tro chng t dung dch b t qu nng cc b, c th dn n kt qu sai. Hn hp phn ng b tro cn do t nng qu mnh hoc do ht chng si km hiu qu. 4 Mc du lng feroin thm vo khng c ch nh, nhng cn phi cho lng nh nhau cho mi ln chun . im cui l thi im chuyn mu r rt u tin t xanh lc sang nu , mc d mu xanh lc c th xut hin tr li sau vi pht.

8.2 Php th trng Tin hnh hai php th trng song song cho mi ln xc nh theo quy trnh m t trong 8.1, nhng thay th mu th bng 10,0 ml nc. Cn xem thm ch thch trong iu 5. 8.3 Th kim chng Mi ln xc nh cn kim tra k thut v tinh khit ca ho cht bng cch phn tch 10,0ml dung dch chun (5.5) theo cng quy trnh tin hnh nh vi phn mu th. Nhu cu oxi l thuyt ca dung dch ny l 500 mg/l, quy trnh th nghim t yu cu nu kt qu ca th kim chng t nht t 96% gi tr ny. Th trng phi c tin hnh nh nu ra trong 8.2.

9 Biu th kt qu
9.1 Tnh ton Nhu cu oxi ho hc COD, tnh bng miligam trn lt, c tnh theo cng thc:
1 2 _____________________

8000c(V - V ) Vo

TCVN 6491 : 1999

Trong : c Vo V1 V2 l nng ca st (II) amoni sunfat nh c tnh trong 5.4, tnh bng mol trn lt; l th tch ca phn mu th trc khi pha long (nu c) , tnh bng mililt; l th tch ca st (II) amoni sunfat s dng khi chun mu trng, tnh bng mililt; l th tch ca st (II) amoni sunfat s dng khi chun mu th, tnh bng mililt;

8000 l khi lng mol ca 1/2 O2, tnh bng miligam trn lt. Kt qu c tnh chnh xc n miligam trn lt. Nu cc gi tr COD di 30 mg/l phi ghi trong bo co l "< 30 mg/l. 9.2 ti lp S liu nhn c vi mt quy trnh rt ging nhau1) thc hin bng cc phng th nghim khc nhau vi cng mu nc thi c bn sn cho thy lch chun nh hn 10 mg/l. Khong 40 phng th nghim khc nhau phn tch mt s mu c gi tr COD = 500 mg/l. lch chun l 20 mg/l cho dung dch kali hidro phtalat v 25 mg/l cho nc thi cng nghip ly t nh my giy v bt giy. mc 50 mg/l, lch chun l 10 mg/l cho loi nc thi tng t. Trong nghin cu khc, 2 mu nc thi cng nghip c 32 phng th nghim phn tch. Mc COD l 140 mg/l v 160 mg/l, lch chun gia cc phng th nghim l gn 14 mg/l cho c 2 mu.

10 Yu t cn tr
Php th nhy vi vi yu t cn tr, v nguyn l l vi clorua. Cc tc nhn kh v c nh nitrit, sulfua, v st (II) s lm tng kt qu. Thc t c th chp nhn rng nhu cu oxi ho bao gm c cc tc nhn ny v coi nh mt phn ca gi tr COD tng s ca mu. gim s cn tr ca clorua nhng khng loi tr c hon ton bng cch thm thu ngn (II) sunfat. Cht ny cng vi ion clo hnh thnh phc tan thu ngn clorua (II). Khi hm lng ion clorua vt qu 1000mg/l, phi p dng mt quy trnh c ci bin cho ph hp. Cc hidro cacbon thm v pyridin b oxi ho khng ng k. Mt vi cht hu c d bay hi c th trnh khi s oxi ho do bay hi. Cc cht bo mch thng b oxi ho mnh bi bc sunfat-axit sunfuric (5.2).

11 Bo co kt qu
Bo co kt qu cn phi c cc thng tin sau: a) trch dn tiu chun ny;
1

) Nhu cu xy ho hc cho nc thi v nc b nhim. London, Her Majestys Stationery Office, 1978.

TCVN 6491 : 1999

b) s nhn bit chnh xc mu th; c) kt qu, c biu th bng miligam trn lt O2; d) bt k s thao tc no khc vi quy trnh quy nh hoc bt k tnh hung no c th lm nh hng n kt qu.

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