Phan Tich Chat Luong Nuoc

Phn tch cht lng nc
CHNG 7
PHN TCH CHT LNG NC

1 NG DNG THUY T PHN T UVVIS TRONG PHN TCH CC YU T CHT LNG NC
1.1 S lc l ch s nghin cu v quang ph Quang ph hc l mt mn hc chnh yu trong thin vn hc, n c ng dng thnh cng nghin cu v kh quyn trong hnh tinh chng ta. Cch y 200 nm, Joseph von Fraunhofer (1787-1826) ln u tin sn xut loi my o quang ph m tnh nng khng c g snh k p lc by gi. ng y khm ph ra rt nhiu cc ng ti trong quang ph ca nh sng mt tri. ng y c th xc nh chnh xc di bc sng ca nhiu Fraunhofer lines (vch) v thut ng ny ngy nay vn c dng. Tuy nhin, trong thi gian ny ng y khng hiu c nhng c s vt l v ngh a v nhng vn m ng y khm ph ra.
Hnh 7-1. Thit b Spektralapparat thit k bi Gustav R. Kirchhoff v Robert W. Bunsen (1823)
Thnh tu quan trng k tip v Fraunhofer lines l qu trnh tm ra nguyn l vt l ca s hp thu v pht x vo nm 1859 v i s cng tc ca nhiu nh vt l n i ting nh Gustav R. Kirchhoff (1824-1887), Robert W. Bunsen (1811-1899) ti Heidelberg. Thit b m h s dng l Spektralapparat, h ghi nhn c qu trnh pht x rt c bit ca nhiu nguyn t khc nhau. Vi phng php ny h tip tc khm ph ra 2 nguyn t mi l Csium v Rubidium, h chit c mt lng rt
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Qun l cht lng nc nui trng thy sn
nh (7g) t 44.000 lt nc khong gn ni Bad Nauheim, Germany. S khm ph ny l nn tng cho s khm ph tip theo v s hp thu v pht x ca hp thu phn t. Nm 1879 Marie Alfred Cornu thy rng, nhng tia c bc sng ngn ca bc x mt tri trn b mt tri t b hp th b i kh quyn. Mt nm sau , Walther Noel Hartley m t rt t m v s hp th UV ca O3 v i di bc sng 200 v 300 nm v n tr nn r rng hn khi h pht hin ra rng O3 cha y trong bu kh quyn. In 1880, J. Chappuis khm ph ra s hp thu trong vng kh kin (400840nm). Nm 1925 Dobson pht trin mt my quang ph m i rt n nh s dng lng knh bng thch anh. 1.2 i cng v quang ph Trong quang ph hc, nh sng nhn thy (nh sng kh kin), tia hng ngo i, tia t ngo i, tia Rnghen, sng radio... u c gi chung mt thut ng l bc x. Theo thuyt sng, cc dng bc x ny l dao ng sng ca cng in trng v cng t trng, nn bc x cn c gi l bc x in t. Sau thuyt sng, thuyt ht cho thy bc x gm cc ht nng lng g i l photon chuyn ng v i tc nh sng (c = 3.108 m/s). Cc dng bc x khc nhau th khc nhau v nng lng h ca cc photon. y, nng lng ca bc x c lng t ha, ngha l nng lng ca bc x khng phi lin tc m cc lng t nng lng t l v i tn s ca dao ng in t theo h thc Planck.
= h
h = 6,625.10 34 J.s : hng s Planck. Louis de Broglie a ra thuyt thng nht c khi nim sng v khi nim ht ca sng nh sng. nh sng va c tnh cht sng va c tnh cht ht. Tng qut hn l bc x c bn cht sng ht. Ni dung nh sau: Ht c khi lng m chuyn ng v i vn tc v c bc sng i i v i n l cho bi h thc:
=
Trong :
h h = mv p
p = mv l ng lng ca ht
l bc sng (de Broglie)

h = 6,625.10 -34 J.s l hng s Planck.
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Phn tch cht lng nc
1.2.1 Cc i lng o bc x in t Bc sng : L qung ng m bc x i c sau mi dao ng y . n v: m, cm, m , nm,

A
o
. (1cm = 108
= 10 7 m =104 m)
Tn s : L s dao ng trong mt n v th i gian (giy) Trong 1 giy bc x i c c cm v bc sng cm, vy: =

c
Lu : Bc x truyn trong chn khng v i vn tc c = 2,9979.10 8 m/s (thng ly trn 3.10 8 m/s) n v: CPS ( VNG DY), Hz, KHz, MHz. (1CPS=1Hz; 1MHz=103 KHz=106Hz) Nng lng bc x: Cc dao ng t (phn t chng hn) ch c th pht ra hoc hp th nng lng tng n v gin on, tng lng nh nguyn vn g i l lng t nng lng:
= h =
hc
= hc
n v: Jun (J), Calo (Cal), electron von (eV). 1.2.2 Cc dng bc x Bc x in t bao gm 1 dy cc sng in t c bc sng bin i trong khong rt rng: t c mt sng raio n c A (1010 m) tia Rnghen hoc nh hn na. Ton b dy sng c chia thnh cc vng ph khc nhau.
o
Hnh 7-2. Cc ph ca sng in t
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Mt ng i ch cm nhn c mt vng ph in t rt nh g i l vng nhn thy (kh kin) bao gm cc bc x c bc sng t 396760 nm. Hai vng tip gip v i vng nhn thy l vng hng ngo i v vng t ngo i. 1.2.3 S tng tc gia vt cht v bc x in t iu kin bnh thng, in t ca phn t nm trng thi lin kt, nn phn t c mc nng lng thp, g i l trng thi c bn Khi chiu mt bc x in t vo m t mi trng vt cht, s xy ra hin tng cc phn t vt cht hp th hoc pht x nng lng, hay c gi l trng thi kch thch . Nng lng m phn t pht ra hay hp th vo l:
E = E2 - E1 = h
Trong , E1 v E2 l mc nng lng ca phn t trng thi u v trng thi cui
(hay cn gi l trng thi kch thch) l tn s ca bc x in t b hp th hay pht x ra.

Nu E > 0 th xy ra s hp th bc x in t. Nu E < 0 th xy ra s pht x nng lng. Theo thuyt lng t, cc phn t v cc bc x in t trao i nng lng v i nhau khng phi bt k v lin tc m c tnh cht gin on. Phn t ch hp th hoc pht x 0, 1, 2, 3,n ln lng t h m thi. Khi phn t hp th hoc pht x s lm thay i cng ca bc x nhng khng lm thay i nng lng ca n, bi v cng bc x in t xc nh bng mt cc ht phton c trong chm tia, cn nng lng bc x in t li ph thuc tn s ca bc x. V th khi chiu mt chm bc x in t v i mt tn s duy nht i qua mi trng vt cht th sau khi i qua nng lng ca bc x khng h thay i m ch c cng bc x thay i. Cc phn t khi hp th nng lng ca bc x s dn n thay i cc qu trnh trong phn t (quay, dao ng, kch thch electron) hoc trong nguyn t (cng hng spin electron, cng hng t ht nhn) Mi mt qu trnh nh vy i h i mt nng lng c trng cho n, ngh a l i h i bc x in t c tn s hay chiu di sng nht nh kch thch. Do s hp th chn lc ny m khi chiu chm bc x in t v i mt di tn s khc nhau i qua mi trng vt cht th sau khi i qua chm bc x ny s b mt i mt s bc x c tn s xc nh, ngh a l cc tia ny b phn t hp th.
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Phn tch cht lng nc
1.2.4 S hp th bc x v mu sc ca cc cht nh sng nhn thy bao gm tt c d i bc x c bc sng t 396-760 nm c mu trng (nh sng tng hp). Khi cho nh sng trng (nh sng mt tri) chiu qua mt lng knh, n s b phn tch thnh m t s tia mu (, da cam, vng, lc, lam, chm, tm). Mi tia mu ng v i m t khong bc sng hp hn (xem Bng 7-1). Cm gic cc mu sc l mt chui cc qu trnh sinh l v tm l phc tp khi b c x trong vng kh kin chiu vo vng mc ca mt. Mt tia mu v i mt khong bc sng xc nh. Chng hn bc x v i bc sng 400430 nm gy cho ta cm gic mu tm, tia sng v i bc sng 560 nm cho ta cm gic mu lc vng. nh sng chiu vo mt cht no n i qua hon ton th i v i mt ta cht khng mu. Th d, thy tinh thng hp th cc bc x v i bc sng nh hn 360 nm nn n trong sut v i cc bc x kh kin. Thy tinh thch anh hp th bc x v i bc sng nh hn 160 nm, n trong sut i v i bc x kh kin v c bc x t ngoi gn. Mt cht hp th hon ton tt c cc tia nh sng th ta thy cht c mu en. Nu s hp th ch xy ra mt khong no ca vng kh kin th cc bc x khong cn li khi n mt ta s gy cho ta cm gic v mt mu no . Chng hn mt cht hp th tia mu ( = 610730 m) th nh sng cn l i gy cho ta cm gic mu lc (ta thy cht c mu lc). Ngc li, nu cht hp th tia mu lc th i v i mt ta n s c mu . Ngi ta g i mu v mu lc l hai mu ph nhau. Trn hai mu ph nhau l i ta s c mu trng. Ni cch khc, hai tia ph nhau khi trn vo nhau s to ra nh sng trng. Quan h gia mu ca tia b hp th v mu ca cht hp th (cc mu ph nhau) c ghi bng sau: Bng 7-1. Quan h gia mu ca tia b hp th v mu cht hp th Mu ca cht hp th Tia b hp th (mu ca tia cn li) Mu (nm) Vng lc Tm 400 430 Vng da cam Xanh 430 490 Lc xanh 490 510 ta Lc 510 530 Tm Lc vng 530 560 Xanh Vng 560 590 Xanh lc Da cam 590 610 Lc 610 750
Lu : Gia cc tia mu cnh nhau khng c mt ranh gii tht r rt.
Vic phn chia nh sng trng thnh 7, 8 hay 9 tia mu cn ty thuc vo lng knh v s tinh t ca mt ngi quan st.
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Mt cht c mu, th d nh mu chng hn l do n hp th chn lc trong vng kh kin theo mt trong cc kiu sau: Cht hp th tia ph ca tia (tc l hp th tia mu lc) Cht hp th cc tia tr tia mu . Cht hp th hai vng khc nhau ca nh sng trng sao cho cc tia cn l i cho mt ta cm gic mu .
mt hp cht c mu, khng nht thit max ca n phi nm vng kh kin m ch cn cng hp th vng kh kin ln. Ni mt cch khc tuy gi tr cc i ca vn hp th nm ngoi vng kh kin nhng do vn hp th tri rng sang vng kh kin nn hp cht vn c mu. Tt nhin c c s hp th thy c vng kh kin th max ca cht cng phi gn v i ranh gi i ca vng kh kin. Tng ng v i mt bc chuyn in t, ta thu c ph hp thu c dng: Hai i lng c trng ca ph hp thu l v tr v cng - V tr cc i hp thu, gi tr max ty thuc vo E m hp cht ny hp thu cc vng ph khc nhau. Bn chiu rng ca vn ph in t dao ng kh rng khong 5060m. - Cng th hin qua din tch hoc chiu cao ca nh biu (peak). Cng vn ph ph thuc vo xc xut chuyn mc nng lng ca in t. Xc sut ln cho cng vn ph ln. Mt hp cht mu c ph hp thu tt khi nh biu (peak) cao v bn chiu rng vn ph hp.
A () Peak Bn chiu rng vn ph
max
Hnh 7-3. nh v bn chiu rng vn ph
Khi bn chiu rng vn ph hp, th khi thay i nh th hp thu A thay i ln. iu ny rt c ngh a trong phn tch nh lng. Gi s hp cht X c Amax 500nm. Khi chng ta o bc sng 510nm... th hp thu o c s khc rt xa i v i bc sng 500nm. T ta thy rng mi hp cht mu c mt gi tr max nht nh v n phn nh nhy ca phng php.
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Phn tch cht lng nc
Mt khc, mt hp cht i hi nh biu cao ngh a l khi ta o bc sng max th ta c hp th quang cc i, khong lm vic rng. 1.2.5 nh lut Lambert Beer Khi chiu mt chm tia sng n sc i qua mt mi trng vt cht th cng ca tia sng ban u ( Io ) s b gim i ch cn l I T s T s
I 100 0 0 = T c gi l truyn qua. I0 I0 I 100 0 0 = A c gi l hp th. I
Nguyn tc ca phng php biu din theo s :
Hnh 7-4. S m t s hp th nh sng ca mt dung dch
Trong : Io: Cng ban u ca ngun sng IA: Cng nh sng b hp thu bi dung d ch I: Cng nh sng sau khi qua dung dch. IR: Cng nh sng phn x b i thnh cuvette v dung d ch, gi tr ny c loi b bng cch lp li 2 ln o. Gia IA, I, dy truyn nh sng (l) v nng (C) lin h qua quy lut Lambert Beer l nh lut hp nht ca Bouguer: Lambert (1766) Beer (1852) :
lg lg
Io = K1 l I Io = K1 C I
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truyn quang (T) hay hp th (A) ph thuc vo bn cht ca vt cht, dy truyn nh sng l v nng C ca dung dch. C th vit:
I nh lut Lambert Beer : A = lg( 0 ) = * C * l I
Trong : l h s hp thu phn t, C nng dung dch (mol/L), l dy truyn nh sng (cm), A l hp th quang. (Lu phng trnh trn ch ng i vi tia sng n sc). Trong phn tch nh lng bng phng php trc quang ng i ta chn mt bc sng nht nh, chiu dy cuvet l nht nh v lp phng trnh ph thuc ca hp th quang A vo nng C. Kho st khong tun theo nh lut Lambert Beer: Khi biu din nh lut Lambert Beer trn th ty theo cch thc hin php o, ta thng gp ng biu din s ph thuc hp thu A vo cng C ca dung dch c dng: y = ax + b H s gc a cho bit nhy ca phng php, trong phng php trc quang ng i ta ch o dung d ch trong khong tun theo nh lut Lambert Beer tc l khong nng m gi tr khng thay i. H s gc a cng ln v khong tun theo nh lut Beer cng rng l iu kin thun l i cho php xc nh. S lch khi nh lut Beer: S lch khi nh lut Beer c biu din bng s sau: A LOL
C
Hnh 7-5. Gii hn ca nh lut Beer v s h p th quang
Khong tuyn tnh LOL (Limit of Linear Response) l khong nng tun theo nh lut Beer ( A = * l * C) ngh a l khi nng tng th hp th quang A tng. Ngoi gi i hn LOL l s lch kh i nh lut Beer, ngh a l khi nng tng th hp th
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Phn tch cht lng nc
quang A hu nh khng tng na. Nguyn nhn ca qu trnh ny l do nng dung dch qu ln. Ngoi ra, khong tuyn tnh LOL cn b nh hng ca mc n sc ca nh sng s dng, pH ca dung dch, lc ion, s pha long... ngh a ca cc i lng: - H s hp thu mol : ph thuc bn cht mi cht, bc sng , nhit , chit sut (theo nng ). Gi tr tnh l thuyt ca mt bc chuyn c php cho 1 electron l = 105 mol-1.cm-1.
A (l.mol-1cm-1) lC
cao cho ta bit c nhy ca phn ng, l thc o nhy ca phng php. Trong phn tch trc quang, = 103105 mol-1. cm-1 l nhy dng cho phng php trc quang, ph thuc vo chit sut m chit sut l i ph thuc vo nng . Khi chit sut tng ln th gim v khng thay i th phi thc hin C 10-2 mol/L. - hp th quang A: L i lng khng c n v, c tnh cht quan trng l tnh cng hp th quang. Gi s 2 cht A v B c nng CA v CB, hp thu ti bc sng l: A = AA + AB = l *(ACA + BCB) Nu mt cht tan X no c hp th quang l AX, dung mi c hp th quang l Adm, ta c: A = Ax + Adm o c chnh xc Ax th Adm = 0, c ngh a l ph i chn max ca dung mi khc xa v i max cht tan. Nhng cht c chn lm dung mi thng c hp thu min ranh gi i t ngoi chn khng. Bng7-2. Cc dung mi thng s dng trong vng UVVIS Dung mi Nc ct HCl Etanol, Metanol n- Butanol n- Hexan Cyclohexan Bc sng gi i hn s dng (nm) 190 190 210 210 210 210 Dung mi Benzen Cloroform Tetra Clorocarbon Dietyl Eter Aceton 1,4 Dioxan Bc sng gi i hn s dng (nm) 280 245 265 218 330 215
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Trong hn hp c nhiu cu t khng lm thay i tng tc, khng phn ng ha hc, khng dch chuyn cn bng, th c th xc nh hn hp cc cu t theo h thc sau:
A = 1 lC1 + 2 lC2 + ....... + i lCi + ...... + n lCn
- truyn quang T:
T= I I m A = lg( 0 ) do A = lg T Io I
V T tnh theo % nn: A = 2 lg T Nu T = 100% th A = 0 (ngha l khng hp th nh sng (I = Io) Nu T = 1% th A = 2 Nu T = 0 % th A = (hp thu hon ton nh sng) 1.2.6 Nguyn l cu to ca my quang ph Ngun sng Ngun sng cho my quang ph l chm bc x pht ra r n. My quang ph dng n hydro hay n Deuterium cho ph pht x lin tc trong vng UV t 200380m (nhng thng s dng 200-340 m) v n tungsten halogen o vng 380-1000 m. lm vic cho c hai vng th phi c 2 lo i n trn. Mt yu cu i v i ngun sng l phi n nh, tu i th cao v pht bc x lin tc trong vng ph cn o. n Deuterium: cu to sm mt si t ph xit v mt cc kim lo i t trong mt bng thu tinh cha kh Deuteri hoc hydro c ca s bng thch anh bc x t ngo i i ra v n khng truyn qua c thy tinh. Khi s i t c t nng, electron sinh ra kch thch cc phn t kh Deuteri (hoc hidro) bin thnh nguyn t v pht ra phton theo phn ng:
* D + D + h D2 + Ee D2
Ee = E D = ED + ED + h
* 2
y l nng lng electron kch thch, bc x pht ra l mt ph c bc sng t 160 nm n vng kh kin. B n sc B n sc c chc nng tch bc x a sc thnh bc x n sc, bao gm knh lc, lng knh hay cch t. Cch t l mt bng nhm hay cc kim loi Cu, Ag. Au... c vch thnh nhng rnh hnh tam gic song song. Khi chiu nh sng qua cch t, phn cn l i c tc
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Phn tch cht lng nc
dng to nn vn nhiu x c bc sng khc nhau, khi quay cch t s to ra ph nhiu x ging nh trng hp nh sng qua lng knh. u im l cho phn gi i tt, tn sc tuyn tnh, rng ca di n nh, chn bc sng n gin, gn nh, d ch to nn hin nay s dng cch t to nh sng n sc c a chung. Cch t dng cho UVVis c 1200 vch/mm (thng dao ng t 3003600 vch/mm, s vch cng nhiu th nng sut phn gi i cng cao.
Detector
Hnh 7-6. S cu to ca my quang ph
Lng knh ca my quang ph dng lng knh littrow (lng knh 300) bng thch anh, c c im nh sng i qua lng knh hai ln do phn x mt sau. Detector Detector l b phn o tn hiu nh sng trc v sau khi i qua dung d nh (ng trong cuvet). Cc tn hiu sau khi i ra Detector s c s c khuch i, lu gi v x l trn my tnh. Cuvet ng mu Cuvet phi lm bng cht liu cho bc x vng cn o i qua. Cuvet thy tinh khng thch hp cho vng UV. Cuvet thch anh cho bc x i qua t 1901000 nm. Cuvet nha ch dng trong vng Vis v ch s dng c 1 vi ln. 1.3 S dng phng php trc quang trong nh lng ha hc Yu cu v cc hp cht cn xc nh l ph i bn, t phn ly, n nh, khng thay i thnh phn trong khong thi gian nht nh thc hin php o (1020 pht). H s ln c gi tr t 1035.104 L.mol-1cm-1, c th thc hin phn ng to mu v i cc thuc th v c v hu c.
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Nng cc cht xc nh theo nh lut Lambert Beer. Khong xc nh nng theo phng php l 10-2 10-6 mole. Gi i hn pht hin ca phng php 10-7mole. Cc hp cht l phc cn o phi c max khc xa v i max ca thuc th trong cng iu kin tc l >2 ln na bn chiu rng ca vn ph (khong 80 -100 m). Th d, khi phn tch Fe2+ bng phng php O-Phenanthroline. Sau khi thm thuc th ta c phc mu vng cam (max=510 m), trong khi thuc th 1,10Orthophenanthroline c max = 250 m. 1.3.1 Phng php so snh So snh cng mu ca dung dch cn xc nh v i cng mu ca dung dch chun bit nng . iu kin: c hai dung d ch trn phi c nng nm trong khong tun theo nh lut Beer. Cx ---------------------- Ax Ctc ---------------------- Atc Ta cn xc nh Cx :
Cx = Ax * Ctc Atc
Khi s dng 2 dung d ch chun:

C x = C1 + C2 C1 * ( Ax A1 ) A2 A1
Vi A1, A2, C1, C2 l hp thu v nng ca dung dch chun tng ng sao cho A1 < Ax < A2 c ngha C1 < Cx < C2 1.3.2 Phng php thm chun Phm vi ng dng l xc nh cc cht c hm lng vi lng hoc siu vi lng, lo i b nh hng ca cht l. C 2 phng php l phng php s dng cng thc v phng php th. - Phng php s dng cng thc
C x = Ca Ax Ax + a Ax
Trong :
Ax: hp thu ca dung dch xc nh tng ng v i th tch Vx. Ax+ a: hp thu ca dung dch c thm chun. Ca: Nng cht chun thm vo.
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Phn tch cht lng nc
Cx: Nng cht cn xc nh trong th tch Vx Cng thc c thit lp t : Ax = lCx A(x+a) = l(Cx + Ca) Cx c biu din theo n v ca Ca. Cch thc hin: Ly 3 ln ca dung dch cn xc nh nng cho vo 3 bnh nh mc c th tch VmL. Bnh 1: Thm thuc th v cc cht to mi trng pH cho dung d ch, dung d ch g i l dung d ch xc nh Cx, hp thu quang tng ng l Ax. Bnh 2: Thm mt lng chnh xc dung dch tiu chun bit chnh xc nng Ca, tin hnh phn ng to mu ging nh bnh 1. Dung dch c hp thu tng ng l A(x+a). Bnh 3: ch thm cc cht to pH cho dung dch, ly dung d ch ny lm dung dch so snh. p dng cng th c: C x = Ca
Ax . T Cx c trong th tch Vx(mL) c th qui v Ax + a Ax Co = C xVo (mg / L) Vx
th tch ban u ca mu Vo (mL): - Phng php s dng th
C t nht 3 dung d ch thm chun. Ly t nht 4 ln ca dung d ch cn xc nh nng cho vo 4 bnh nh mc V(mL). Sau thm chnh xc mt lng V1, V2, V3 mL dung d ch tiu chun c nng tng ng Ca1, Ca2, Ca3 vo 3 bnh nh mc trn. Tin hnh phn ng to mu. Bnh cn l i lm dung d ch so snh, cng chun b ging nh phng php cng thc. hp thu ca cc dung dch thm so v i dung d ch so snh.
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A Ax + a3 Ax + a2 Ax + a1 Ax Ca1 Ca2 Ca3 C
Hnh 7-7. Biu xc nh phng trnh hi quy tng quan ca ph ng php thm chun s dng th.
C th c kt qu trn th hoc s dng phng trnh hi qui c dng: A = aC + b Ax = b Cx = b/a 1.3.3 Phng php ng chun u im l chnh xc, thc hin c nhiu ln. - Chun b t 6 dung dch chun (trong khong tun theo nh lut Beer). - Thc hin phn ng mu v i thuc th. - o hp th quang A ca dung d ch max so v i cc dung d ch so snh c chun b ging nh dung dch tiu chun nhng khng cha ion cn xc nh. - Biu din s ph thuc A theo C trn th hoc tnh theo phng trnh hi qui A=aC + b (a v b l h s cn tm ca phng trnh hi quy tng quan) (xem Bng 7-3) - Dung d ch xc nh: chun b v phn ng to mu v i thuc th ging nh mu chun. Bng 7-3: Dung dch chun dng xy dng ng chun Dung dch chun C (mg/L) A 1 0,00 0,010 2 0,05 0,480 3 0,10 0,930 4 0,15 1,370 5 0,20 1,830 6 0,25 2,281
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(hi quy tuyn tnh y = ax + b)
Phn tch cht lng nc
Sau khi o c gi tr hp th quang ca cc dung dch chun, chng ta c th tin hnh xy dng ng chun v tm ra phng trnh hi quy tng quan:
2.500 H s h p thu A 2.000 1.500 1.000 0.500 0.000 0.00 0.05 0.10 0.15 0.20 0.25 0.30 Nng y = 9.0543x + 0.0184 R = 0.9999
2
Hnh 7-7. Biu xc nh phng trnh hi quy tng quan ca ph ng php ng chun.
Sau khi thit lp ng chun, ta c dng phng trnh y = ax + b v i y l hp th quang, x l nng . i v i dung d ch xc nh, ta tin hnh phn ng v o c h s hp thu ca mu (A mu = y), ta c th tnh c nng ca mu cn xc nh theo phng trnh:
x= yb a
S tng quan gia hp th quang A v nng C khi l = const l n i dung ca nh lut Beer. Khong nng tha mn nh lut ny khi r > 0,999. H s tng quan r bin i trong khong -1 r 1 (R2 = 0-1) - Khi r 1 c s tng quan cht ch gia x v y theo t l thun. - Khi r -1 c s tng quan cht ch gia x v y theo t l thun. - Khi r 0 hai i lng ny khng cn tng quan. 1.4 chnh xc trong phng php trc quang: Trong phn tch trc quang cng nh bt k ph ng php no khc c th chia sai s thnh 2 nhm: - Sai s do tin hnh phn ng ha hc (ha cht, thao tc, dng c...) - Sai s ca tn hiu o hp thu ca dung dch (do h thng o).
153
chnh xc trong phng php ny ph thuc vo hng lot nguyn nhn khc nhau rt phc tp bao gm sai s ngu nhin v sai s h thng, trong sai s quan trng nht l sai s ca tn hiu trong qu trnh o hp thu quang hc. 1.5 Mt s v d p dng phng php nh lng trc quang V d 1 hp th quang A ca dung d ch anilin 2.10-4M trong nc o bc sng =280nm l 0,252. Chiu di nh sng i qua cuvet l 1cm. Tnh truyn quang ca anilin 1,03.10-3M khi o cng di bc sng nhng dng cuvet 0,5cm. Gii:
I p dng cng thc A = lg( 0 ) = * C * l v i dung dch 1 ta c: I
= 0.252/(2.10-4*1) = 1,26.103l.mol-1cm-1.
I p dng cng thc A = lg( 0 ) = * C * l v i dung d ch 2 ta c: I
A = 1,26.103 * 0,5 * 1,03.10-3 = 0.649 M: A = -lgT suy ra: lgT = -A = -0,649, do T = 0,224 = 22,4%
Vy truyn quang T = 22,4% V d 2: hp th quang A o c t cc mu chun v mu nc thu t ao nui c cha ion PO43- nh sau: Nng mu chun (mg/L) 0,00 0,05 0,10 0,15 0,20 0,25 hp th quang A 0,010 0,480 0,930 1,370 1,830 2,281 hp th quang A ca mu nc ao ca 3 ln lp l i l: 1,256; 1,245; 1,264. Tnh nng PO43- trong mu nc ao. Gii: T cc nng mu chun v hp th quang A. T kt qu thit lp phng trnh hi qui ta c: y = 9,0543 x + 0,0184 (r2 = 0,9999). T kt qu ca 3 ln phn tch lp li ta c A = y = 1,255 T ta c x =
y 0,0184 1,255 0,0184 = = 0,137 mg / L 9,0543 9,0543
Vy nng PO43- trong mu nc ao l 0,137 mg/L.

154
Phn tch cht lng nc
V d 3: xc nh hng s phn ly ca Methyl da cam (k hiu HIn), ng i ta o hp th quang A ca 3 dung dch cng nng Methyl da cam cc pH khc nhau: Dung d ch 1 trong HCl 0,1M; Dung d ch 2 trong NaOH 0,1 M; Dung d ch 3 c pH = 4,34; A1 = 0,475. A2 = 0,130. A3 = 0,175
Cho bit o bc sng = 510nm v chiu di nh sng i qua cuvet l 1cm. Tnh hng s phn ly K ca Metyl da cam? Gii: hp th quang ca dung dch 3:
A3 = In In * l + HIn [HIn]* l
[ ]
(7.1) (7.2) (7.3) (7.4)
Vi [In-] = x; [HIn] = y ta c: x + y = CHIn = C
In =
A2 v ton b cht ch th dng InC*l A1 v ton b cht ch th dng HIn C *l
Hin =
Thay (7.3) v (7.4) vo (7.1) ta c:

A3 = A2 . x y + A1 . C C
(7.5)
Qui c:
x y = ; = (1 ) 0,175 = 0,130 + 0,475 (1-) C C
= 0,869 Hng s phn ly ca HIn: HIn H+ + In- ;

K=
Ka
[ H + ][ In ] In = lg = pH lg pK pH HIn HIn 1 0,869 = 7.34 0,82 = 3,52 K = 3,02.10-4. 1 0,689
pK = 4,34 - lg
Vy hng s phn ly ca methyl da cam l K = 3,02.10-4.
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2 PHNG PHP THU V BO QUN MU
2.1 Chun b thu mu 2.1.1 Nhn nh s thay i cht lng nc Cht lng nc ti m i tr i lun b thay i theo th i gian (ph thuc vo lu lng v mc tc ng ca cc ngun nhim), do vy cn o cc gi tr cc i, cc tiu v trung bnh ca cc thng s theo th i gian c th phn nh gn ng gi tr thc. S mu thu thp cn ln v nh p thu mu cn cao lm c iu ny . Tuy nhin, vic tng cao s mu v nhp thu s gy tn km nhiu v kinh ph v nhn lc. Cho nn cn tnh sao cho va tin cy va khng qu nhiu chi ph Theo GEMS (H thng quan trc mi trng ton cu) nh p thu mu cho nc nui thy sn nh mu sng th i gian thu mu cn tin hnh khi lu lng thp, ao h cn xem xt chu trnh sinh hc v cn tng nh p thu mu th i im c nng sut sinh hc cao. 2.1.2 Cc iu cn lu khi thu mu La chn v ra k chai, l ng mu. Dng tay cm chai, l nhng vo khong gia dng nc cch b mt nc 30-40cm. Hng ming chai, l ly mu hng v pha dng nc ti. Th tch nc ph thuc vo thng s cn kho st. y kn ming chai, l, ghi r l lch mu thu. Bo qun mu ng qui nh nu bng 1. 2.2 Cc bo qun mu 2.2.1 Mu nc Ty theo ch tiu cht lng nc m cch ly mu v bo mu khc nhau, cch bo qun mu c trnh by Bng 7-4. 2.2.2 Mu t Mu t sau khi thu, phn tch cng sm cng tt. Nu mun bo qun lu cn lm nh sau: Tri mu cng mng cng tt trn bao nilon v phi kh trong iu kin nhit phng. Sau nghin mn, r i cho vo cc snh, em sy nhit 105oC trong 24 gi. ngui mu trong bnh ht m, lc ny sn sng phn tch.
156
Phn tch cht lng nc
Bng 7-4: Dng c thu mu v cch bo qun mu theo ch tiu phn tch STT Ch tiu Dng c Th tch Bo qun bo qun (mL) 1 Alkalinity P;G 200 4oC 2 Hardness P;G 100 4o C 3 DO P;G 100 1mL MnSO4, 1mL KINaOH 4 CO2 P;G 100 0,5 mL CHCl3 5 COD P;G 100 2mL H2SO4 4M 6 Chlorophyll-a P;G 500 Lc, 4oC, l nu 7 SiO2 G 100 HCl 1:1 8 TAN P;G 500 4oC 9 Nitrate P;G 100 4oC 10 Nitrite P;G 100 4oC P;G 200 4o C 11 NO2- v NO312 PO43P;G 100 4o C 13 TN,TP P;G 500 4oC
P: Plastic bottle G: Glass bottle
2.3 Phng php thu mu Phng php thu mu chnh xc s gp phn tng tnh chnh xc ca kt qu phn tch. Ty mc ch nghin cu m vic thu mu mang tnh cht c bit hay i din cho ao c p dng ph bin hn. thu mu hn hp i din cho ao, c th thc hin cc bc sau: 2.3.1 Nguyn tc chung Thu nhiu im trong ao (3-5 im hoc hn), sau trn mu l i (cng nhiu cng tt), ri ly mt mu i din lo i mu cn phn tch (ch tiu nc hoc bn y). mi im, cn thu ng th i 3 v tr, ri cho vo 3 x (m i mu/ x), tip tc lm nh th cho cc im khc trong ao. Sau khi thu mu s c 3 x hn hp mu i din cho ao, tng ng 3 ln lp l i. 2.3.2 Dng c thu mu v cch thu - Nn s dng ng PVC (ng knh 10 cm, di 1 - 1,2m) thu mu nc hoc bn y ao. - i v i mu nc, chiu cao ct nc cn thu ty theo ao nng hay su, trnh khuy ng nn y ao khi thu mu nc. Trong trng hp y ao b khuy ng trong khi ang thu mu nc, th nn b mu thu mu khc gn ni . - i v i mu bn y, nn thu nh nhng trnh vt cht dinh dng trong bn b thi ra Sau khi thu mu cn loi b rc, si, ... Cn trn mu hn hp cho tht u ri cho vo chai nha 200mL mang v phng phn tch.
157
3 PHNG PHP PHN TCH MT S CH TIU MI TRNG NC
3.1 Nhi t xc nh nhit ca nc, ngi ta thng dng nhit k thy ngn c chia t 0-50oC (ti a l 100oC). Mun xc nh nhit ca nc tng mt, ta c bu thy ngn ca nhit k vo trong nc su 15-20 cm, cho n khi nhit trong nhit k khng i (khong 5 pht), sau nghing nhit k v c nhit ca nc xong m i ly nhit k ln khi mt nc. Mun xc nh nhit ca nc tng gia hay tng y ca thy vc, ta cm nhit k vo np bnh thu mu nc, th bnh xung ng v tr cn xc nh nhit , cho nc vo y bnh, yn 5 pht sau ko ln v c ngay nhit nc tng . Chng ta cng c th o nhit bng my, hin nay mt s my o pH hay DO c ch to c th o c c ch tiu nhit . 3.2 pH 3.2.1 Bng hp giy so mu Giy c tm dung dch ch th mu thch hp, sy kh cho vo hp s dng. Khi c thm t giy s hin mu. Ty thuc pH ca nc, giy s hin mu khc nhau. Sau em so mu v i bng mu tiu chun km theo trn np hp, ta s bit c pH ca nc. 3.2.2 Phng php in th-my o pH Ion H+ hot ng (pH) c xc nh trc tip bng php o in th. Sc in ng E ca t bo Galvanic c lin quan n hot ng ca ion H+ trong dung d ch theo phng trnh Nernt. in th sinh ra t t bo t l v i nng ion H+ trong mu nc, in th ny c o bng mt in th k v c thit b c bit d ch sang tr s pH hin trn mn nh ca my. T bo Galvanic bao gm 1 in cc thy tinh, v 1 in cc Calomel tip xc v i mu nc bng mt tia Aming cui in cc. Khi tip xc v i mu nc, in cc Calomel s xy ra phn ng: Hg2Cl + 2e- 2Hg + 2Clin cc thy tinh gm 1 in cc Ag-AgCl ngm trong dung d ch HCl 0,1M v c bao bc bi 1 mng thy tinh c nhy cm rt cao v i ion H+. in th ny ca in cc s xut hin khi ion H+ c mng thy tinh hp th. S hp th 1 ion H+ trn mng thy tinh s phng thch 1 ion Li+ t mng thy tinh vo dung d ch in cc. Theo Peters (1975) th t bo Galvanic i v i vic xc nh pH c th c vi t nh sau: Ag / AgCl, HCl (0.1M) / mng thy tinh / mu nc / Hg2Cl2, KCl / Hg.
158
Phn tch cht lng nc
Tt c in th trong t bo Galvanic u khng thay i, tr in th gia mng thy tinh - mu nc v gia mu nc - dung dch KCl trong in cc Calomel. 3.3 trong (Transparency), c (Turbidity) C nhiu cch xc nh trong v c ca nc, nhng k thut ph bin nht cho vic nui thy sn l s dng a secchi o trong. c c th c o chnh xc bng cch s dng my o c theo ph ng php Nephelometric. Ngoi ra c th xc nh lng v t cht l lng trong nc thng qua lng cht rn ho tan (TDS) v tng lng cht rn l lng (TSS) 3.3.1 o trong bng a Secchi a secchi dng hnh trn lm bng vt liu khng thm nc (inox, thic, tole...) chia a lm 4 phn u nhau, sn hai mu en v trng xen k nhau. a c treo trn mt que hay trn mt s i dy c nh du khong cch mi khong chia l 5 hoc 10cm. Khi o, cm u dy th t t cho a ngp nc v ghi nhn ln 1 khong cch t mt nc n a khi khng cn phn bit c hai mu en trng trn mt a. Sau cho a secchi su hn v tr va ri v ko ln n khi va phn bit c hai mu en trng, ghi nhn khong cch ln 2 trong ca nc ao o bng a secchi l trung bnh ca hai ln ghi nhn khong cch. 3.3.2 o c bng phng php Nephelometric Thit b o c c cc b phn d nh sng c t v tr vung gc (90o) so v i chm tia ti c g i l my o nh sng khuch tn. Phng php ny c da trn vic so snh cng nh sng tn sc ca mu (trong iu kin xc nh) v i cng nh sng khuch tn ca mu chun i chng trong iu kin tng t. Cng nh sng khuch tn cng cao th c cng cao. Formazin polymer c s dng lm cht l lng trong mu chun. c ca nng cht l lng bng formazin c xc nh n 4000 NTU. Ngoi ra, mt s thit b o c c thit k xc nh c theo n v mg/L (Model QWC-22A-TOA, Nht). Cht l lng tiu chun c s dng lm dung d ch i chng l Kaolin tinh ch (theo h thng cng nghip Nht bn-JIS). C th o c d dng bng cc my o nu trn. 3.4 Tng cht rn ha tan (TDS) v tng cht rn l lng (TSS) Cht rn hin din trong nc bao gm vt cht ha tan v khng ho tan. o c tng lng cht rn ho tan (TDS). Mu cn c lc lo i b v t cht khng ho tan, v nc c lc cho bc hi v phn cn li c cn tnh hm lng cht
159
rn ha tan. Tng lng cht rn ha tan bao gm vt cht hu c v v c ho tan, biu th bng mg/L. Tng lng cht rn l lng (TSS) c tnh bng cch cn trng lng nhng cht cn li trn giy lc c s dng khi lc nc phn tch cht rn ho tan. TSS biu th lng vt cht khng ha tan l lng trong nc v c biu th l mg/L. Vt liu v dng c dng phn tch tng cht rn ha tan v tng cht rn l lng gm: Giy lc si thy tinh, t nung 550oC, bnh lm ngu i ht m, h thng lc chn khng, cn phn tch. 3.4.1 Tng cht rn ha tan TDS (Total Dissolved Solid) Thu mu vo bnh 1 lt v y kn. Bo qun lnh 4oC Ngm giy lc thy tinh trong 24 gi, sau sy kh Nung cc s (a snh) nhit 550oC trong 30 pht, sau lm ngu i trong bnh ht m v cn khi lng ca cc s (W1) Lc nc bng h thng lc chn khng. Ly 100mL c lc cho vo cc s c chun b sn. t cc s vo t sy nhit 95oC. Sau gia tng nhit ln 105oC trong 1gi. Lm ngu i a v cn trng lng 2 (W2) Tng lng cht rn ha tan c tnh theo cng thc sau:
TDS (mg / L) =
(W2 W1 ) x 1000 V
Trong : W2: Trng lng a ln 2 (mg) W1: Trng lng a ban u (mg) V: Th tch mu nc 3.4.2 Tng cht rn l lng - TSS (Total Suspended Solid) Thu mu vo bnh 1 lt v y kn. Bo qun lnh 4oC Lc mu bng giy lc c cu to bng cht liu s i thy tinh ng knh 47 mm, c lc 0,22-0,45 m. nh s mu trn giy lc. Sy giy lc 105oC trong 2-3 gi. Cn v ghi kh i lng giy lc (Wo) Lc u mu nc trc khi lc.
160
Phn tch cht lng nc
Lc mu nc, ghi th tch mu nc lc (V mL) Sy 105oC trong 2-3 gi, ht m 30 pht trong bnh ht m, cn khi lng (W1) Nung 550oC trong 2-3 gi, ht m 30 pht trong bnh ht m, cn khi lng (W2) Cc ch tiu v vt cht l lng c tnh theo cng thc sau:
TSS (mg / L) = OSS ( mg / L) =
(W1 W0 ) x 1000 V (W1 W2 ) x 1000 V
ISS ( mg / L) = TSS OSS
V: th tch mu nc lc (mL) W: khi lng (mg) TSS: tng vt cht l lng (mg/L) OSS: vt cht hu c l lng (mg/L) (OSS = Organic Suspended Solid) ISS: vt cht v c l lng (mg/L) (ISS = Inorganic Suspended Solid) 3.5 dn in (EC) dn in l kh nng mang m t dng in ca dung d ch. Kh nng ny ty thuc vo s hin din ca cc ion, tng nng , tnh linh ng, ha tr ca cc ion v nhit lc o c. Cc dung dch ca hu ht cc hp cht v c l cc cht dn tt nhng ngc l i i v i cc phn t hu c c tnh dn in km. n v o dn in l micromho/cm (mho/cm) hoc theo h thng n v o lng quc t (SI) l millisiemens/m (mS/m); 1 mS/m=10 mho/cm v 1 mho/cm=1 S/cm. Trong nc ngt, dn in thng t 50 n 1.500 mho/cm (Theo Hip hi sc khe cng ng ng i M-APHA, 1989; Arce v Boyd, 1980), mi trng nc l v mn th dn in cao hn nhiu. dn in v nng mu i c lin quan rt cht v nng cc ion trong mi trng, dn in tng cng v i s tng nng mu i. Vic o c chnh xc dn in thng khng c i h i cao i v i nui trng thy sn, m thay vo vic o nng mu i ca nc thng c s dng hn. My o n in thng c s dng c tnh nhanh mc khong ha ca nc thin nhin v mc nhim ngun nc thi cng nghip. 3.6 Nng mui Thut ng nng mui ch tng nng cc ion ha tan trong nc. n v tnh l mg/L hoc phn ngn (). c tnh nng mu i ca nc mt cch tt nht th
161
cn tnh tng nng 7 ion quan trng trong mi trng lm cho nc thin nhin c nng mu i l: Na+, K+, Ca2+, Mn2+, Cl-, SO42-, v HCO3- v cc ion ny thng chim hn 95% trong tng s cc ion ha tan trong nc. o nng mui chng ta c th s dng t trng k, nhng mc chnh xc ca dng c o ny khng cao. Trong lnh vc thy sn, thit b o nng mu i c s dng ph bin nht l khc x k v my o nng mui. 3.7 Oxy ha tan (DO) 3.7.1 Phng php Winkler Nguyn tc Trong mi trng baz mnh, oxy ha tan trong nc s oxy ha ion Mn2+ thnh Mn4+ c kt ta nu. Mn2+ + 2OH- + 1/ 2 O2 = MnO2 + 2H2O Sau MnO2 c ha tan bng H2SO4 m c. Trong mi trng acid, MnO2 l cht oxy ha mnh, c kh nng oxy ha I- thnh I2 bng ng v i lng I2 c trong mu nc lc ban u: MnO2 + 2I- + 4H+ = Mn2+ + I2 + 2H2O I2 c gi i phng ra s ha tan trong nc v c xc nh bng phng php chun v i dung d ch Na2S2O3. H tinh bt c s dng lm cht ch th xc nh im tng ng trong qu trnh chun ny: Khi I2 c mt trong dung dch, n s kt hp v i tinh bt hnh thnh mt phc cht c mu xanh. Khi tt c I2 trong dung d ch c chun ht v i Na2S2O3, dung dch s tr nn khng mu. Thu mu Thu mu nc vo l nt mi nu 125 mL, cho ha cht c nh bng 1 mL MnSO4 v 1mL dung d ch KI-NaOH, y np l li, lc u, trong l xut hin kt ta. Ch , khi thu mu v sau khi c nh khng bt kh xut hin trong chai khi thu mu nc. Thuc th - Dung d ch MnSO4: Ha tan 50 g MnSO4.5H2O hay 41 g MnCl2.4H2O v i nc ct thnh 100 mL. - Dung d ch KI-NaOH: Ha tan 50 g NaOH v 15 g KI (hay 14 g NaI) v i nc ct thnh 100 mL. - H2SO4 (d=1,84) hay H3PO4 c (d= 1,88). - Dung d ch Na2S2O3 tiu chun 0,1N: Pha mt ng Na2S2O3 tiu chun 0,1N trong 1000mL nc ct
162
Phn tch cht lng nc
- Dung d ch Na2S2O3 0,01N: S dng cng thc N1V1 = N2V2 pha dung dch c th nh sau: Ly 50 mL dung d ch Na2S2O3 0,1N pha long v i nc ct thnh 500 mL. - Ch th h tinh bt 1%: Ha tan 0,49 g K2S2O3 trong 100 mL nc m (t 80-90oC) khuy u cho n khi dung d ch mu trong sut, cho vo 0,5 mL formaline nguyn cht s dng c lu. Tin hnh - Sau khi c nh bng ha cht, yn cho kt ta lng. Tip tc lc u mt ln na kt ta hon ton, sau yn 5 pht i v i nc ng t, 10 pht i mu nc l mn. - Cho tip 2 mL H2SO4 hay H3PO4 m c (vn khng cho bt kh xut hin trong l) - Lc u cho n khi kt ta ha tan. Dung dch c mu vng nu - ong 50 mL dung d ch va c acid ha trn, cho vo bnh tam gic 100 mL. - Chun bng dung d ch Na2S2O3 0,01N cho n khi dung d ch c mu vng nht, cho 3 git ch th h tinh bt, lc u dung d ch c mu xanh, tip tc chun cho n khi dung dch chuyn t mu xanh sang khng mu th dng l i. - Ghi th tch (V1 mL) dung dch Na2S2O3 0,01N s dng chun mu. - Lm tng t 2 hoc 3 ln, ghi th tch dung d ch Na2S2O3 0,01N dng chun . Tnh V trung bnh ca Na2S2O3 0,01N dng chun
VTB = (V1 + V2 + V3 ) / 3
Tnh kt qu
DO ( mg / L) = VTB x N x 8 x 1000 VM
Trong : VTB: l th tch trung bnh dung dch Na2S2O3 0,01N (mL) trong cc ln chun . N : l nng ng lng gam ca dung dch Na2S2O3 s dng. 8 : L ng lng gam ca oxy. VM : l th tch (mL) mu nc em chun . 1000: l h s chuyn i thnh lt 3.7.2 Phng php in cc oxy ha tan) - my o oxy Theo phng php ny th p sut ring phn ca oxy ha tan c o trc tip. Sau p sut ring phn c chuyn i thnh nng (mg/L). My o oxy tnh ton
163
cc gi tr ny da trn mi quan h gia nhit , ha tan ca oxy v p sut khng kh. u d oxy bao g m 1 in cc dng (anode) c lm t Ag/AgCl, 1 in cc m (cathode) c lm t kim loi qu nh platinum, vng, tungsten hoc rhodium v dung d ch in cc KCl bo ha ngn cch v i mi trng ngoi b i mng cm ng polyethylene, teflon, polypropylene hoc vt liu tng t c dy thng 25m hoc mng hn (c kh nng thm oxy). Cc in cc trong h thng ny c 1 hiu in th gia chng thng khong 0,7 volts. Khi oxy trong mu nc tip xc v i mn cm ng, mn c kh nng thm oxy v t l m oxy i qua mng cm ng c lin quan n p lc ca oxy trong mu nc. Khi cung cp mt hiu in th cho u d th oxy phn t thm thu qua mng, phn ng v i cc cathode v b kh thnh hydroxide v i t l 4 moles OH-/mole oxy theo phng trnh sau: O2 +2H2O + 4e- 4OHSau 1 dng in chy qua cc anode (in cc bng bc) v OH- phn ng v i bc to thnh dng oxit bc theo phng trnh sau: 2Ag0 + 2OH- = Ag2O + H2O + 2e-. Do , s chnh s khc bit v p lc oxy gia trong v ngoi mng cm ng lm cho oxy thm thu qua mng. V vy, nu p lc oxy bn ngoi mng cm ng thp th dng in gia 2 in cc s t hn so v i khi p lc oxy bn ngoi cao. Ngoi ra, tnh thm ca mng cm ng b nh hng rt ln bi nhit (Mancy v Jaffe, 1966) (Trch dn bi Boyd & Tucker, 1992). Th d, dng in to ra 10 mg/L oxy ha tan 10oC ch bng 1/ 4 so v i vic to ra 10 mg/l 30oC. Bn cnh , nhit cn nh hng i v i dng in gia 2 in cc thng qua mi quan h v nhit v p lc oxy. Do , hu ht cc my o oxy ha tan trong nc thng c thit k c b phn hiu chnh nhit t ng trnh sai s do s nh hng ca nhit ln s liu o c. Hm lng oxy ha tan trong nc cng b nh hng b i nng mu i. Hm lng oxy ha tan trong nc mc bo ha gim khi gim p sut khng kh v tng nng mui. V vy, hu ht cc my o oxy thng c thit k c s hiu chnh p sut v nng mu i tng chnh xc trong o c. 3.8 Carbon dioxide (CO2) 3.8.1 Nguyn tc CO2 t do trong nc c xc nh bng phng php trung ha v i dung d ch NaOH tiu chun v phenolphthalein lm cht ch th xc nh im tng ng CO2 + NaOH =
164
NaHCO3
(7.6)
Phn tch cht lng nc
Khi phn ng (7.6) t im tng ng, mt gi t d dung d ch NaOH s lm cho mi trng c tnh kim yu (pH 8-10) phenolphthalein s chuyn t khng mu sang mu hng. Mun c kt qu chnh xc ta phi dng dung d ch m c pH tiu chun bng 8,3 theo di s chuyn mu ca phenolphthalein m xc nh chnh xc im tng ng ca phn ng 3.8.2 Phng php thu v bo qun mu Thu mu trong chai nt mi trng 125 mL, c nh mu bng 0,5mL Chloroform 3.8.3 Chun b ha cht - Dung d ch NaOH tiu chun 0,1N: Ha tan ng chun NaOH 0,1N v i nc ct thnh 1000mL - Dung d ch NaOH 0,01N: Ha tan 100mL dung d ch NaOH 0,1N v i nc ct thnh 1000mL. - Dung d ch m pH= 8,3: Dung d ch Na2B4O7 0,05M: Ha tan 1,91g Na2B4O7.10H2O v i nc ct thnh 100mL. - Dung d ch H3BO3 0,2M: Ha tan 1,24 g H3BO3 v i nc ct thnh 100mL. - Ly 20mL dung d ch Na2B4O7 0,05M cho vo 30mL dung d ch H3BO3 0,2M. Ta s c dung dch m c pH=8,3. - Dung d ch ch th phenolphthalein 1%: Ha tan 1g ch th phenolphthalein (C20H14O4) trong 100mL cn 600. 3.8.4 Tin hnh Dng bnh tam gic 100mL, ln lt cho vo bnh cc ha cht nh sau (Bng 7.5): Bng 7.5. Cc bc tin hnh phn tch hm lng CO2 Bnh 1 1. 50mL dung dch m pH= 8,3 2. 3 git ch th phenolphthlein, lc u, dung dch c mu hng nht. 1. 50mL mu nc. 2. 3 git ch th phenolphthlein, lc u, dung dch khng mu. 3. Dung d ch NaOH 0,01N chun t t cho n khi dung dch trong bnh c mu hng nht ging nh bnh 1 th dng l i ( mu hng ch bn trong 1 pht). Ghi th tch V1 (mL) dung dch NaOH 0,01N s dng. 4. Lm l i cc bc 1 n 4 mt ln na ghi th tch V2 (mL) dung dch NaOH 0,01N s dng. 5. Tnh VTB = (V1 + V2)/2. Bnh 2
165
3.8.5 Tnh kt qu
CO2 (mg / L) = VTB x N x 44 x1000 50
Vtb: l th tch trung bnh dung dch NaOH 0,01N ca c ln chun . N: l nng ng lng ca dung dch NaOH s dng. 44: ng lng g ca CO2. 50: th tch nc em chun .
3.9 Tiu hao oxy ha hc (Chemical Oxygen Demand - COD) 3.9.1 Phng php oxy bng KMnO4 trong mi trng kim Thu v bo qun mu Thu mu trong chai nt mi trng 125 mL, c nh mu bng 2 mL H2SO4 4M Nguyn tc Vic xc nh hm lng COD c da trn nguyn tc cc hp cht hu c trong nc c th b oxy ha thnh CO2 v H2O bi cc cht oxy ha mnh (KMnO4) trong mi trng kim. Trong mi trng baz, ion MnO4- s tc dng v i ion OH- nh gc (OH) t do. MnO4- + OH- = MnO42- + (OH) Gc (OH) ny khng bn n s phn hy cho ra oxy nguyn t. 2(OH) = [O] + H2O Oxy nguyn t trng thi m i sinh l cht oxy ha mnh, c kh nng oxy ha hon ton cc hp cht hu c thnh CO2 v H2O. CxHyOz + (2x + y/2 - z) [O] = xCO2 + y/2H2O Sau mi trng c acid ha bng dung d ch H2SO4. Trong mi trng acid, v i s hin din ca mt lng tha I-, lng MnO4- cn l i s b kh hon ton thnh Mn2+ v mt phn I- b oxy ha thnh I2. 10KI + 2KMnO4 + 8H2SO4 = 5I2 + 2MnSO4 + 6K2SO4 +8H2O I2 c to thnh c xc nh bnh phng php chun v i dung d ch Na2S2O3 tiu chun ging nh phng php xc nh Oxy ha tan trong nc theo phng php Winkler. T lng I2 c to thnh trong mu tht v mu trng ta tnh c lng oxy cn thit oxy ha hon ton cc hp cht hu c trong mu nc thnh CO2 v H2O. Thuc th
166
Phn tch cht lng nc
- Dung d ch KMnO4 0,1N: Ha tan 1 ng KMnO4 0,1N trong mt t nc ct, sau pha long thnh 1.000mL. iu chnh nng chnh xc bng dung dch chun C2H2O4 tiu chun 0,1N v 15mL H2SO4 1:4 lc u em un nng nh 80oC. Sau dng dung dch KMnO4 va pha trn chun t t cho n khi dung d ch chuyn t khng mu sang mu hng nht th dng l i, ghi th tch dung dch KMnO4 s dng (V1). Lm li nh trn mt ln na ly gi tr trung bnh. Nng dung d ch KMnO4 c iu chnh chnh xc bng cng thc: V1N1 = V2N2 . Dung dch c bo qun trong chai nu. - Dung d ch KMnO4 0,05N tnh kim: Ha tan 500mL dung d ch KMnO4 trong 500mL nc ct c ha tan 8g NaOH, cho vo bnh mu nu s dng. - Dung d ch KI 10%: Ha tan 10g KI v i nc ct thnh 100mL. - Dung d ch H2SO4 4M: Ha tan 22,2mL H2SO4 m c v i nc ct thnh 100mL. - Dung d ch Na2S2O3 0,1N: Ly 1 ng Na2S2O3 0,1N chun pha long v i nc ct thnh 1.000mL. - Dung d ch Na2S2O3 0,05N: Ly 500mL dung d ch Na2S2O3 0,1N dng nc ct pha long thnh 1.000mL. - 7. Ch th h tinh bt 1%: Ho tan 1 gam tinh bt trong 100mL nc m (t 80oC-90oC) khuy u cho n khi dung d ch tr nn trong sut, cho vo 0,5mL formaline nguyn cht s dng c lu. - Dung d ch NaOH 0.4N: Ly 40mL dung d ch NaOH 10N, dng nc ct pha long thnh 1.000mL Tin hnh Dng 2 cp bnh tam gic 100mL, ln lt cho vo tng cp bnh cc ha cht sau (Bng 7.6):
167
Bng 7.6. Cc bc tin hnh phn tch COD Bnh 1 Bnh 2 1. 50mL nc ct. 1. 50mL mu nc. 2. 5mL dung dch NaOH 0,4N. 2. 5mL dung dch NaOH 0,4N. 3. 5mL dung dch KMnO4 0,05N. 3. 5mL dung dch KMnO4 0,05N. 4. em un cch thy im si ng 4. em un cch thy im si ng mt gi, ly ra ngui 10 pht. mt gi, ly ra ngui 10 pht. 5. Tip tc vo 5mL KI 10% v 5mL dung 5. Tip tc vo 5mL KI 10% v 5mL dch H2SO4 4M, lc u dung dch c dung d ch H2SO4 4M, lc u dung mu vng nu. dch c mu vng nu. 6. Dng d ch dch Na2S2O3 0,05N chun 6. Dng d ch dch Na2S2O3 0,05N cho n khi dung dch c mu vng chun cho n khi dung dch c nht, cho v 3 git ch th h tinh bt mu vng nht, cho v 3 git ch th 1%, lc u dung dch c mu xanh, h tinh bt 1%, lc u dung dch c tip tc chun t t cho n khi dung mu xanh, tip tc chun t t dch tr nn khng mu th dng l i ghi cho n khi dung d ch tr nn khng th tch (V1) dung dch Na2S2O3 0,05N mu th dng l i ghi th tch (V2) s dng. dung d ch Na2S2O3 0,05N s 7. Ly bnh cn li chun tng t nh dng. bnh trn ly gi tr trung bnh. 7. Ly bnh cn l i chun tng t nh bnh trn ly ga tr trung bnh. Tnh kt qu
COD ( mg / L) =
(V2 V1 ) x N x 8 x 1000 VM
3.9.2
N: nng dung dch Na2S2O3 chun V1: th tch dung dch Na2S2O3 chun mu nc cn phn tch. V2: th tch dung dch Na2S2O3 chun mu nc ct. VM: th tch mu nc em phn tch. Phng php Dichromate
Nguyn tc Trong phng php ny cc hp cht hu c trong nc b oxy ha thnh CO2 v H2O bi cht oxy ha mnh (K2Cr2O7) trong mi trng acid. Mt lng bit trc K2Cr2O7 c thm vo mu nc s b acid ha v i H2SO4. Mu nc ny sau c un nng v cc cht hu c b oxy ha thnh CO2 v H2O, trong khi Dichromate b kh theo phng trnh sau: Cht hu c + Cr2O72- + H+ 2Cr3+ + CO2 + H2O
168
Phn tch cht lng nc
Lng tha dichromate c th xc nh c bng cch chun v i ferrous ammonium sulfate - Fe(NH4)2(SO4)2.6H2O. 6Fe2+ + Cr2O72- + 14H+ 6Fe3+ + 2Cr3+ + 7H2O Lng dichromate tiu th cho vic oxy ha cc cht hu c c th c tnh ton t mN (mili ng lng) ca K2Cr2O7 thm vo mu tr mN ca Fe(NH4)2(SO4)2.6H2O s dng trong vic chun kh lng K2Cr2O7 tha. 3.10 Nng sut sinh hc s cp C nhiu cch xc nh xc nh nng sut sinh hc s cp ca thy vc nh : phng php bnh t i- bnh sng, phng php ng v phng x C14, phng phc xc nh hm lng cc sc t quang hp trong nc, phng php xc nh sinh kh i thc vt ni, phng php xc nh theo hm lng oxy trong nc. Phng php bnh ti bnh sng c s dng ph bin hn c. Hm lng oxy t do trong nc c xc nh theo phng php Winkler 3.10.1 Nguyn tc Phng php bnh ti sng da trn nguyn tc trong c th thc vt lun lun xy ra hai qu trnh ngc nhau, qu trnh to thnh v qu trnh phn hy cc vt cht hu c. Qu trnh to thnh cc hp cht hu c bng con ng quang hp s b dng l i khi khng c nh sng, do s hp thu CO2 t mi trng v lng O2 c thi ra cng b d ng l i. Qu trnh h hp hp th O2 v th i ra CO2 tin hnh v i tc ngang nhau trong t i v ngoi sng. Do da trn hm lng O2 ha tan trong bnh t i v bnh sng ta c th tnh c cng quang hp ca thc vt ph du trong nc. Trong thc t i khi cng quang hp ca thc vt c coi l nng sut sinh hc s cp. Theo Winberg (1960), sc sn xut ca thy vc theo nng sut sinh hc s cp (P) c trnh by bng sau: Dng c - H thng bnh sng- bnh t i: Cc bnh t i c chun b nh sau: dng hc n bi en ton b thnh bnh v y bnh. - a secchi: xem phn xc nh trong ca nc. Ha cht Thy vc ngho dinh dng: P1 t 1-2 mg/L O2/ ngy, m Thy vc dinh dng trung bnh: P1 t 2-5 mg/L O2/ ngy, m Thy vc giu dinh dng: P1 t 5-15 mg/L O2/ ngy, m Thy vc rt giu dinh dng: P1 t 15-20 mg/L O2/ ngy, m
3.10.2 Dng c v ha cht
169
- Ton b ha cht xc nh ha tan theo phng php Winkler (xem mc 3.7.1). 3.10.3 Tin hnh Dng a secchi o trong ca nc, nhn trong v i 2 xc nh tng sng. Nu thy vc tng sng nh th ch cn thu mu v t bnh v tr gia ao v cch mt nc khong 20-30cm. Nu thy vc c tng sng ln (su), khi thu mu nc cn t bnh gc ao, gia ao, tng mt v tng y. m i v tr dng 6 bnh BOD 125mL (4 bnh sng v 2 bnh t i), thu y mu nc v tr theo nng sut sinh hc s cp. Ly 2 bnh sng phn tch O2 ban u u (DO), 4 bnh cn li dng gi t ng v tr cn thu mu nuc trn, yn trong 24 gi ly ln phn tch hm lng O2 ha tan trong mi bnh (DOCS v DOCT). 3.10.4 Tnh kt qu P (mg O2/L/ngy) = DOCS DOCT R (mg O2/L/ngy) = DO DOCT P (mg O2/L/ngy) = DOCS DO P : Nng sut sinh hc (tng lng oxy c to ta t qu trnh quang hp) R: H hp ca thy sinh vt (tng lng oxy tiu hao do qu trnh h hp) P: Nng sut sinh hc thc (s chnh lch gia oxy sinh ra t quang hp v oxy tiu hao do h hp. P l s dng (+) khi thc vt c gia tng sinh khi, P l s m (-) khi thc vt gim sinh khi. DOCS: Hm lng oxy cui (C) bnh sng (S), c o sau 24 gi DOCT: Hm lng oxy cui (C) bnh ti (T), c o sau 24 gi DO: Hm lng oxy u (), c o lc bt u 3.11 Chlorophyll-a 3.11.1 Nguyn tc Phng php chi t sut bi Ethanol 90% (Nusch, 1980). Cc sc t trong nc sau khi c lc qua mng lc ng knh 47mm, kch thc lc 0,22-0,45m. Chng c chit sut bi ethanol. Sau c o bc sng 665 nm v 750 nm cc pheophytin c o cng bc sng sau khi x l acid. Phng php chi t sut bi acetone Phng php ny c b sung bi Lalli (1984). Trong phng php ny, chloropyll c chit xut trong acetone v o mc hp thu quang ph 4 bc sng.
170
Phn tch cht lng nc
3.11.2 Tin hnh Ho cht Dung d ch acetone nguyn cht Tin hnh - Ct nh giy lc mu cho vo ng nghin, - Thm 10mL acetone 100% v nghin trong mt pht - Lc qua giy lc GFF 25mm0,2m, ng th i thu mu dch chit sut vo chai, l 10mL nu. - Bo qun lnh v ti cho n khi o mu - o mu cc bc sng 630, 647, 664 v 750 nm. Tnh kt qu Chl-a = [11,85(E664-E750) - 1,54(E647-E750) - 0,08(E630-E750)]/[(1/d) x (V1*1000)/V2] (g/L) V1: th tch acetone (10 mL) V2: th tch nc mu c lc d: di truyn quang (cuvet 1cm). 3.12 Hydrogen sulfide (H2S) 3.12.1 Phng php Iodine Nguyn tc H2S trong mu nc c cha H2S s b kt ta CdS khi phn ng v i CdCl2. CdCl2 + H2S = CdS + 2HCl Sau CdS c ha tan bng mt lng tha I2 chun, trong mi trng acid. CdS + I2 + 2HCl = S + CdCl2 + 2HI. Lng tha I2 c xc nh bng phng php chun v i dung d ch Na2S2O3 tiu chun v h tinh bt c dng lm cht ch th xc nh im tng ng, ging nh qu trnh xc nh oxy ha tan trong nc bng phng php Winkler. I2 + I2 tinh bt + 2Na2S2O3 = Na2S4O6 + 2NaI + tinh bt. (mu xanh) Thu v bo qun mu Tin hnh thu mu trong chai nt mi nu, c nh mu bng 1mL CdCl2 Thuc th - Dung d ch CdCl2 2%: Ha tan 2 g CdCl2 v i nc ct thnh 100mL.
171
(khng mu)
- Dung d ch HCl 4M: Cho 25mL HCl c (12M) vo v pha long thnh 100mL v i nc ct. Dung d ch I2 0,1N: Ha tan 80 g KI trong 500mL nc ct khng, tip tc cho vo12,7 g I2 khuy u cho tan ht, sau pha thnh 1.000mL. Dung ny sau khi pha xong phi xc nh l i nng chnh xc bng dung d ch Na2S2O3 0,1N tiu chun. cch tin hnh nh sau: Dng bnh tam gic 100mL, cho vo 20mL dung d ch I2 va pha trn (dng buret xc nh th tch I2, khng dng ng ht), dng dung d ch Na2S2O3 0,1N tiu chun, chun cho n khi dung d ch c mu vng, tip tc chun cho n khi dung d ch c mu vng nht, cho 3 git h tinh bt, lc u dung dch c mu xanh, tip tc chun cho n khi dung d ch chuyn t mu xanh sang khng mu th dng l i, ghi th tch dung dch Na2S2O3 0,1N s dng. Lm l i nh trn mt ln na ly gi tr V trung bnh. Sau hiu chnh nng dung d ch I2 cho chnh xc bng biu thc: N1V1 = N2V2 - Dung d ch I2 0,01N: ly 50mL I2 0,1N dng nc ct pha long thnh 500mL. - Dung d ch Na2S2O3 tiu chun 0,1N: Pha mt ng Na2S2O3 tiu chun 0,1N trong 1000mL nc ct - Dung d ch Na2S2O3 0,01N: S dng cng thc N1V1 = N2V2 pha dd c th nh sau: Ly 50mL dung dch Na2S2O3 0,1N pha long v i nc ct thnh 500mL. - Ch th h tinh b t 1%: Ho tan 0,49 g K2S2O3 trong 100mL nc m (t 80900C) khuy u cho n khi dung d ch mu trong sut, cho vo 0,5mL formaline nguyn cht s dng c lu. Tin hnh Thu mu nc vo 2 l nt mi 125mL, sau m np l ra, cho ln lt vo m i l 1mL dung d ch CdCl2 2%, y np l l i lc u mt ln na, yn 24 gi (nu c H2S s c kt ta mu vng di y bnh). M np l ra dng ng cao su ht b phn nc trong trn kt ta (ch : khi ht cn ng cao su gn mt nc ch khng c cm su vo y bnh v cho nc chy nh ra ngoi, nu nc chy mnh kt ta b vn ln v cun tri ra ngoi, lm kt qu khng chnh xc ). Ha tan kt ta bng 5mL HCl 4M v 5mL dung d ch I2 0,01N. Chuyn dung d ch t l nt mi sang bnh tam gic 100mL, trng l nt mi bng 30mL nc ct, nc ct ny cng cho vo bnh tam gic. Dng dung d ch Na2S2O3 0,01N chun cho n khi dung d ch mu vng nht, cho vo 3 git ch th h tinh bt, lc u dung dch c mu xanh sau tip tc chun t t cho n khi dung d ch chuyn t mu xanh sang khng mu th dng l i, ghi tng th tch V1 (mL) dch Na2S2O3 0,01N s dng.
172
Phn tch cht lng nc
Lm tng t nh trn cho l cn l i, ghi th tch V2(mL) d ch Na2S2O3 0,1N s dng. Tnh VTB = (V1+V2)/2. Bnh chun: Dng 2 bnh tam gic 100mL, ln lt cho vo tng bnh cc ha cht nh sau: 30mL nc ct, 5mL HCl 4M v 5mL dung d ch I2 0,01N, lc u dung dch c mu vng nu . Dng dung d ch Na2S2O3 0,01N chun cho n khi dung d ch tr nn mu vng nht, cho 3 git ch th h tinh bt vo, lc u dung d ch c mu xanh, tip tc chun cho n khi dung d ch chuyn t mu xanh sang khng mu th dng l i ghi th tch V0 Na2S2O3 0,01N s dng. Lm tng t nh trn cho bnh cn l i ly th tch V0 trung bnh. Tnh kt qu
H 2 S (mg / L) =
(V0 VTB ) x N x17 x1000 125
- VTB: Th tch trung bnh dung d ch Na2S2O3 s dng trong 2 ln phn tch mu nc - V0: th tch trung bnh ca dung dch Na2S2O3 trong 2 ln phn tch mu trng - N: Nng ng lng ca dung dch Na2S2O3 s dng. - 17: ng lng g ca H2S. 3.12.2 Phng php Methylene blue Nguyn tc Nguyn tc ca phng php ny da trn phn ng ca sulfide (S2-), ferric chloride v dimethyl-p-phenylenediamine to nn methylene blue. Ammonium phosphate c thm vo sau khi hin mu kh mu ca ferric chloride. Sau nng S2c xc nh bi my so mu quang ph bc sng 664 nm. Thu mu v bo qun Tin hnh thu mu trong chai nt mi nu, bo qun lnh 4oC Thuc th Dung d ch PRE 1: 500mL HCl 37% pha thnh 1000mL v i nc ct. Dung d ch A: Ha tan 4g C8H14Cl2N2 trong PRE 1 thnh 1000mL. Dung d ch B: Ha tan 16g FeCl3.6H2O trong PRE 1 thnh 1000mL. Dung dch chun
173
- Dung d ch Na2S.9H2O 100mg/L: ha tan 0,750g Na2S.9H2O trong 1000mL nc ct khng oxy (nc ct khng oxy: un nc ct ln si khong 10 pht em khi bp bt kn ngay ). - Dung d ch Na2S.9H2O 5mg/L: ha tan 5mL dd Na2S.9H2O 100mg/l v i nc ct thnh 100mL Thit lp mu chun Bng 7.7. Cc bc thit lp mu chun phn tch H2S theo phng php Methylene blue STT Nng mu Th tch dung dch chun Th tch nc ct chun (mg/L) Na2S.9H2O 5mg/L (mL) (mL) 1 0,00 0,0 100,0 2 0,02 0,4 99,6 3 0,04 0,8 99,2 4 0,06 1,2 98,8 5 0,08 1,6 98,4 6 0,10 2,0 98,0 Tin hnh - ong 20mL mu nc. - Ln lt cho thuc th vo 1mL thuc th A, 1mL thuc th B - Ch 5 pht khi mu xanh xut hin chng ta em o hp th quang bc sng 665nm. Tnh kt qu tng ng v i nng C ca mu chun ta c hp th quang A. Da vo s tng quan ny chng ta c th lp phng trnh tng quan dng A = aC + b Trong : A: hp th quang C : nng cht chun (mg/L) Sau khi thit lp phng trnh, chng ta o hp th quang ca mu cn phn tch v th vo phng trnh chng ta s tnh c nng ca S2- c trong mu nc.
C= Ab a
tnh hm lng H2S khi thu mu nc chng ta phi o pH v nhit . Da vo bng tra (xem Chng 3, Mc 5, Bng 3.5) xc nh t l phn trm ca H2S cha trong tng sulfide, t tnh ra hm lng H2S.
174
Phn tch cht lng nc
3.13
cng tng cng
Vic xc nh cng tng cng ca nc c thc hin theo phng php chun Complexon. 3.13.1 Nguyn tc Trong mi trng pH=10 ion Ca2+ v Mg2+ s kt hp v i thuc th EDTA (Ethylene DiamineTetra-acetic Acid) (EDTA - K hiu Na2H2Y ) hnh thnh phc cht bn vng, khng mu Calcium hay Magnesium ethylene diamine tetraacetate. Eriochrome black T (C20H13O7N3SNa) c s dng lm cht ch th xc nh im tng ng. Eriochrome black T kt hp v i ion Ca2+ v Mg2+ hnh thnh phc cht khng bn vng c mu hng ca ru vang. Khi dng EDTA chun , cc ion Ca2+ v Mg2+ s kt hp v i EDTA hnh thnh phc cht bn vng, khng mu, v khi c Eriochrome black T t do, dung dch c mu xanh l . M2+ + M-Eriochrome black T + Na2H2Y = Na2MY + 2H+ + Eriochrome black T (Mu hng ru vang) (mu xanh l) Trong qu trnh chun ion Ca2+ v Mg2+ bng Na2H2Y lun gi i phng ra 2 ion H+, phn no lm acid ha mi trng, do trong qu trnh chun phi cho dung dch m vo mi trng pH ca mi trng khng i trong sut qu trnh chun , dung d ch m thng l NH4OH, NH4Cl. Nu trong mu nc c cha mt lng ng k ion Fe3+, Cu2+, Ni2+,... th s chuyn mu ca cht ch th s khng r rng, nn cn phi che nhng ion ny trc khi chun bng cch dng cc ion CN- hoc S2- che cc cation . 3.13.2 Thu v bo qun mu Thu mu trong chai nha v bo qun lnh 4oC 3.13.3 Thuc th - Dung d ch Na2H2Y (EDTA) tiu chun 0,1N: Cch 1:Ha tan 18,612 g EDTA (C10H14O8N2Na2.2H2O) (sau sy 80oC, ngu i trong bnh ht m) trong 400mL nc ct sau pha long thnh 1000mL. Nu khng c mui C10H14O8N2Na2.2H2O ta c th pha t acid t do C10H14O8N2, cch pha nh sau: Ha tan 14,6 g C10H14O8N2 v 4,5 g NaOH trong khong 400 mL nc ct khuy u cho cc ha cht ha tan hon ton, ngu i t i nhit phng, sau dng nc ct pha long thnh 1000mL, dung d ch ny sau khi pha long xong ph i chun l i bng dung d ch NaCO3 tiu chun 0,1ppm bit nng chnh xc ca dung dch. Cch tin hnh nh sau: Dng buret 10mL dung d ch CaCO3 tiu chun 0,1ppm, cho vo
175
bnh tam gc 250mL tip tc cho vo 90 mL nc ct (2 ln ct) v 2mL dung dch m pH=10 lc u, dung d ch c mu hng ru vang, dng dung d ch Na2H2Y mi pha trn chun trn t cho n khi dung d ch chuyn t mu hng ru vang sang mu xanh l th dng l i, ghi th tch dung dch Na2H2Y s dng. iu ch nh nng dung d ch Na2H2Y cho chnh xc bng biu thc: V1N1 = V2N2. Cch 2: Pha long 1 ng Na2H2Y (EDTA) 0,1N v i nc ct thnh 1000mL. - Dung d ch Na2H2Y 0,01N: ly 50mL dung d ch Na2H2Y 0,1N dng nc ct pha long thng 500mL. - Dung d ch pH=10: Ha tan 6,7g NH4Cl trong 57mL NH4OH m c (d=0,91) sau dng nc ct pha long thnh 100mL tip tc cho tip 1mL dung d ch MgSO4 0,05N v 0,5mL dung d ch Na2H2Y 0,1N lc u. - Dung d ch CaCO3 tiu chun 0,1N: Ha tan 5 gam CaCO3 trong vi git dung dch HCl 1:1, pha long v i nc ct thnh 200mL, un si 5-10 pht, dng dung d ch NH4OH iu ch nh pH ca mi trng v bng 7 sau pha long v i nc ct thnh 1000mL. - Dung d ch MgSO4 0,05N: Ha tan 1,232g MgSO4.7H2O trong mt t nc ct, sau pha long thnh 100mL. - Ch th Eriochrome black T: Ly 100g NaCl tinh khit phn tch em rang hoc sy kh 110oC, ngui nghin mn bng c i chi thy tinh sch. Cn 0,5g ch th Eriochrome black T cho vo 100g NaCl trn trn u v nghin mn, cho vo l nu y np kn. 3.13.4 Tin hnh Trc khi tin hnh cn iu ch nh pH ca mu nc v bng 7-8, sau tin hnh phn tch theo cc bc sau: - Dng ng ong 100mL, ong 100mL mu nc iu chnh v 7-8 cho vo bnh tam gic 250mL, tip tc cho vo 2mL dung d ch m pH=10, v mt lng nh ch th Eriochrome black T (mt nhm bng ht u), lc u nu c ion Ca2+, Mg2+ trong mu nc s c mu hng ru vang. - Dng dung d ch Na2H2Y 0,01N chun t t cho n khi dung d ch chuyn t mu hng ru vang sang mu xang l th dng l i, ghi th tch dung d ch Na2H2Y 0,01N s dng V. Lm l i nh trn ln na ly gi tr V trung bnh. Nu s chuyn mu khng r, tc l trong dung d ch c cc ion cn nh: Fe3+, Cu2+ th cn tin hnh chun li v i mu nc khc v cch tin hnh nh sau: Sau khi cho 2mL dung d ch m pH=10 vo mu nc ta cn thm vo 1mL dung d ch KCN 5% che cc ion cn, sau mi thm cht ch th vo v tin hnh chun nh trn.
176
Phn tch cht lng nc
3.13.5 Tnh kt qu cng tng cng (mg CaCO3/L)

V xN x 50 x1000 VM
- V l th tch dung dch Na2H2Y (mL) dng chun . - N l ng lng ca dung dch Na2H2Y s dng. - VM: th tch mu nc em chun 3.14 kim tng cng Trong nc thin nhin kim c gy ra do s hin din ca cc mui acid yu, tn ti d i cc dng bicarbonate nh: KHCO3, NaHCO3, Ca(HCO3)2, Mg(HCO3)2... cc cht ny c to thnh trong t do tc dng ca CO2 v i nhng cht khong c trong t nh CO2 + CaCO3 + H2O Ca(HCO3)2 Mt s trng hp, kim trong nc c gy ra do ion carbonate, bicarbonate, silicates, phosphates, ammonium v hp cht hu c bin i trong nc. Tuy nhin, cc ion ng quan tm l HCO3-, CO32-, OH-. Khi pH nc ln hn 4,5 th trong nc tn ti ion bicarbonate, khi pH ln hn 8,34 thi trong nc c ion CO32-. Phng php xc nh kim l phng php chun acid. 3.14.1 kim carbonate hay kim phenolphthalein Cho phenolphthalein vo mu nc, mu hng xut hin nu mu nc c cha ion CO32-. Chun bng H2SO4 0,01N cho n khi mt mu (pH =8,34), khi ion CO32- c trung ha. V vy kim phenoltalein cn c g i l kim carbonate. CO32- + H+ = HCO33.14.2 kim tng cng Cho ch th methyl orange vo mu nc dung d ch c mu vng cam. Chun bng dung d ch H2SO4 0.01N cho n khi dung d ch tr thnh mu cam (mi trng acid, pH khong 4,5). Khi tt c cc ion OH-, CO32-, HCO3-, NH4+, PO43-... c trung ha hon ton. V vy, phn tch v i ch th methyl orange chng ta c kim tng cng HCO3- + H+ H2O + CO2 Thu v bo qun mu Thu mu trong chai nha v bo qun lnh Thuc th Dung d ch PRE 1: ha tan 27mL H2SO4 98% v i nc ct thnh 1000mL
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Phenolphtalein 1%: ha tan 1g Phenolphtalein trong 100mL C2H5OH Dung d ch H2SO4 0,1N: ha tan 100mL PRE 1 v i nc ct thnh 1000mL hay pha long 1 ng H2SO4 0,1N chun v i nc ct thnh 1000mL. Dung dch methyl orange 0,1%: ha tan 0,1g methyl orange v i nc ct thnh 100mL Dung dch chun - Dung d ch KHCO3 1N: ha tan 10,011g KHCO3 v i nc ct thnh 100mL - Dung d ch KHCO3 0,1N: ha tan 10mL dung dch KHCO3 1N v i nc ct thnh 100mL. Tin hnh ong 100mL mu nc cn phn tch vo bnh tam gic 250mL Thm vo 3 gi t dung d ch Phenophthalein, dung d ch c mu hng nht. Chun bng dung d ch H2SO4 0,01N n khng mu, ghi th tch (V1 mL) H2SO4 001N s dng chun . Sau thm tip 3 git dung d ch methyl orange, dung d ch c mu vng cam. Tip tc chun bng dung d ch H2SO4 0,01N n pH bng 4,5 dung dch t mu vng cam chuyn sang mu cam, ghi th tch (V2 mL) H2SO4 0.01N. Lm tng t nh mu nc i v i mu chun KHCO3 i chng. Tnh kt qu kim tng cng (mg/ CaCO3/L)
V xN x 50 x1000 MM
- V = (V1 + V2) : tng th tch dung dch H2SO4 0,01N cho c 2 ln chun - N: nng ng lng dung d ch H2SO4 - VM: th tch mu ong em chun 3.15 acid (Acidity) acid biu th kh nng phng thch ion H+ trong nc, do s c mt ca cc loi acid nh : acid carbonic, acid tanic, acid humic bt ngun t s phn hy cht hu c, mt khc do s thy phn cc mui t cc acid mnh nh Sulfat nhm, st to thnh. Khi b cc acid v c thm nhp vo, nc s c pH rt thp Trong nc thin nhin lun duy tr mt th cn bng ngia cc ion HCO3-, CO32-, kh CO2 ha tan, do nc thng ng th i mang hai tnh cht i nhau: tnh acid v tnh kim.
178
Phn tch cht lng nc
Trong thc nghim, hai khong pH chun c s dng biu th s khc bit trn tng ng v i hai lai cht ch th l methyl orange (pH = 4,24,5) v phenolphthalein (pH = 8,28,4) 3.15.1 Nguyn tc Dng dung d ch kim mnh nh phn acid ca c acid v c mnh cng nh acid hu c hoc acid carbonic yu. Lng acid v c mnh khi nh phn thng v i ch th methyl orange, chun t mu chuyn thnh mu da cam v c gi l acid methyl Sau tip tc nh phn xc nh acid tng cng v i ch th phenolphthalein, dung d ch t khng mu chuyn sang mu hng (tm)nht, c gi l acid tng cng 3.15.2 Dng c v thit b - Bnh tam gic 250mL - ng ong 100mL - Burett 3.15.3 Chun b ha cht - Dung d ch NaOH tiu chun 0,1N: ha tan 1 ng chun NaOH 0,1N v i nc ct thnh 1000mL - Dung d ch NaOH 0,02N: Ly 200mL dung d ch NaOH 0,1N ha tan cng v i nc ct thnh 1000mL - Ch th Phenolphthalein 0,5%: cn 0,5g phenolphthalein ha tan trong 50mL Ethanol 98%, cho nc ct vo thnh 100mL - Ch th Methyl orange 0,05%: cn 0,05g methyl orange ha tan trong nc ct thnh 100mL 3.15.4 Tin hnh phn tch Nu mu nc l nc ung, nc cp sinh hot, trc khi chun nn thm 1 git Na2S2O3 0,1N loi b lng Cl- cn d. Nu pH nc < 4,5 - ong 100mL nc mu cho vo bnh tam gic, sau cho vo 3 git methyl orange. Dung dch c mu . - Dng NaOH 0,02N chun cho n khi xut hin mu da cam. Ghi nhn th tch dung d ch NaOH (V1 mL) dng tnh acid methyl hay cn gi l acid khong. - Tip tc thc hin bc xc nh acid tng cng. Nu pH nc >4,5 - ong 100mL n c mu cho vo bnh tam gic, cho vo 3 git ch th phenolphthalein. Dung dch khng mu
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- Dng NaOH 0,02N chun cho n khi dung dch chuyn t khng mu sang mu hng (tm) nht. Mu phi bn t nht 5 pht. Ghi th tch V2 mL dung dch NaOH 0,02N dng tnh acid tng cng 3.15.5 Tnh kt qu acid khong (mg CaCO3/L)
V1 x 1000 VM
(V1 V2 ) x 1000 VM
acid tng cng (mg CaCO3/L)
(Khi pH mu nc ln hn 4,5 th V1 = 0 ) 3.16 St tng s (Fe2+ v Fe3+ ) 3.16.1 Phng php so mu Thiocianate Nguyn tc Cc mui ha tan ca st trong nc thng c xc nh bng phng php so mu Thiocianate. Phng php ny da trn nguyn tc trong mi trng acid, Fe2+ b oxy ha thnh Fe3+ bng mt tc nhn oxy ha thch hp. Fe3+ mi to thnh v Fe3+ c sn trong mu nc s kt hp v i SCN- hnh thnh m t phc cht c mu mu, cng m hay nht ph thuc vo hm lng ion Fe3+ c trong mu nc ban u. 10Fe2+ + 10H+ + K2S2O7 = 10Fe3+ + K2S2O8 + 5H2O K2S2O7 + 3SCN- = Fe(SCN)3 (Mu mu) Thuc th - Dung d ch Thiocianate ammonium hay potassium: Ha tan 50g NH4SCN hay KSCN trong mt t nc ct sau pha long thnh 100mL. - Dung d ch Potassium persulfate: Ha tan 1,7g K2S2O8 trong mt t nc ct sau pha long thnh 100mL. - HCl c d= 1,18 - Dung d ch Fe3+ tiu chun 0,2mg/mL: Cho 20mL H2SO4 m c vo 50mL nc ct, ha tan 1,4g Fe(NH4)2(SO4)2.6H2O vo dung d ch ny. Cho tng git KMnO4 0,1N vo cho n khi dung d ch tr nn mu hng nht th dng l i. Sau pha long thnh 1.000mL. - Dung d ch Fe3+ tiu chun 0,1mg/mL: Ly 50mL dung d ch Fe3+ tiu chun 0,2mg/mL pha long thnh 100mL. Tin hnh - Xc nh st tng s Ly 2 bnh tam gic 100mL, cng kch thc ln lt m i bnh cc ha cht sau:
180
Phn tch cht lng nc
Bng 7. 8. Tin trnh phn tch hm lng Fe tng s trong nc Bnh 1 Bnh 2 1. 50mL nc ct. 1. 50mL mu nc 2. 1,5 mL HCl c lc u. 2. 1,5 mL HCl c lc u 3. 2,5mL K2S2O8, lc u. 3. 2,5mL K2S2O8, lc u 4. 1,5 mL KSCN, lc u dung 4. 1,5 mL KSCN, lc u dung d ch khng dch c mu mu. mu. Dng dung dch Fe3+ tiu chun 0,1mg/mL chun t t cho n khi dung d ch c mu mu ging bnh 1 th dng l i ghi th tch V1 dung d ch Fe3+ tiu chun s dng. Lm l i nh trn mt ln na ly gi tr V1 trung bnh. - Xc nh Fe2+ Ly 2 bnh tam gic 100mL, cng kch thc, ln lt cho vo m i bnh cc ha cht nh sau: Bng 7.9. Tin trnh phn tch hm lng Fe2+ trong nc Bnh 1 Bnh 2 1. 50mL mu nc. 1. 50mL nc ct. 2. 1,5 mL HCl c lc u 2. 1,5 mL HCl c lc u 3. 1,5 mL KSCN, lc u dung 3. 1,5 mL KSCN, lc u dung d ch dch c mu mu. khng mu. Dng dung d ch Fe3+ tiu chun 0,1mg/mL chun t t cho n khi dung d ch c mu mu ging bnh 1 th dng l i, ghi th tch V2 dung d ch Fe3+ tiu chun s dng. Lm l i nh trn mt ln na ly gi tr V2 trung bnh. Tnh kt qu Fe tng s (mg/L) = Fe3+ (mg/L) =
0,1 x V x 1000 50
0,1 x V2 x 1000 50 0,1 x (V1 V2 ) x 1000 50
Fe tng s (mg/L) =
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3.16.2 Phng php o-phenantroline Nguyn tc St b kh thnh dng Fe2+ bng cch un si v i acid v hydroxylamine v c x l v i 1, 10 phenanthroline pH 3,2 - 3,3. 3 phn t phenanthroline to hp cht cng cua v i m i mt nguyn t Fe2+ thnh dng phc cht c mu -cam. Sau c xc nh bi my so mu quang ph bc sng 510nm. Thuc th - Dung d ch A - HCl m c - Dung d ch B - Dung dch Hydroxylamine 10%: ha tan 10g NH2OH.HCl v i nc ct thnh 100mL. - Dung d ch C - Dung dch m pH = 5: ha tan 250g CH3COONH4 trong 150mL nc ct sau thm 700mL CH3COOH m c. - Dung d ch D - Thuc th o-phenanthroline: ha tan 0,1g o-phenanthroline trong 100mL nc ct lm nng 800C. Dung dch chun - Dung d ch Fe2+ 200mg/l: ho tan 1,4g Fe(NH4)2(SO4)2.6H2O v i 20mL H2SO4 m c v i 50mL nc ct. Dau thm vi git KMnO4 0,1N dung dch s c mu hng nht, pha long thnh 1000mL. - Dung d ch Fe2+ 100mg/l: ong 50mL dung d ch Fe2+ 200mg/l pha long thnh 100mL Thit lp mu chun Chn 6 bnh tam gic c dung tch 100mL, cng kch thc, khng mu ln lt cho vo cc ha cht sau: Bng 7.10. Cc bc thit lp mu chun phn tch Fe tng s bng phng php o-phenantroline. STT Nng mu chun Th tch dung dch Th tch nc ct hay nc (mg/l) Fe2+ 100mg/l (mL) bin lc c S%o = S%o v i nc mu (mL) 1 0,0 0,0 100,0 2 0,4 0,4 99,6 3 0,8 0,8 99,2 4 1,2 1,2 98,8 5 1,6 1,6 98,4 6 2,0 2,0 98,0 Tin hnh - Ln lt ong 25mL ca 06 mu chun vo 06 bnh tam gic - ong 25mL mu nc cn phn tch vo bnh tam gic, - Thm vo: (cng cch lm cho mu chun v mu nc )
182
Phn tch cht lng nc
1mL dung dch A 1mL dung dch B Sau , em un trn bp cho cn cn khong 10-15mL, em ngui. nh mc l i v i nc ct thnh 25mL, Tip tc thm vo 5mL dung dch C v 0,5mL dung d ch D, Lc u, em so mu bc sng 510nm
Ch , nu mu dung dch qu m ta nn lm li bng cch pha long, sau khi ghi kt qu t my ta x l l v i h s pha long s cho kt qu nng ca mu m ta cn o. 3.17 Silicate (SiO2) 3.17.1 Nguyn tc SiO2 v cc dn xut ca n trong nc thng xc nh bng ph ng php so mu Molybdosilicate. Phng php ny da trn nguyn tc trong mi trng pH t 3-4 SiO2 v cc dn xut ca n s tn t i d i dng H2SiO3 (acid Silicic), acid Silicic s kt hp v i Molybdate ammonium hnh thnh phc cht Molybdosilicic acid c mu vng, cng m hay nht ph thuc vo hm lng H2SiO3 c trong mi trng. H2SiO3 + 12(NH4)2MoO4 + 24HCl = H8Si(Mo2O7)6 + 24NH4Cl + 9H2O 3.17.2 Thu mu v bo qun Thu mu trong chai nt mi trng 125mL, c nh mu bng 1 mL HCl 50% 3.17.3 Chun b thuc th - 1. Dung d ch Molybdate ammonium 10%: Ha tan 10g (NH4)2MoO4 hay (NH4)6Mo7O24.4H2O trong mt t nc ct nng pha long thnh 100mL, cho vo bnh polyethylene s dng. - 2. Dung dch HCl 50%: Ha tan 50mL dung dch HCl trong 50mL nc ct. - 3. Dung dch H2C2O4.2H2O 10%: Ha tan 10g H2C2O4.2H2O trong mt t nc ct, sau pha long thng 100mL. - 4. Dung dch Na2B4O7.H2O 1%: Ha tan 10g Na2B4O7.H2O trong mt t nc ct, sau pha long thnh 1000mL. - 5. Dung d ch K2CrO4 0,63%: Ha tan 0,63g K2CrO4 trong mt t nc ct, sau pha long thnh 100mL. 3.17.4 Tin hnh Ly 2 bnh tam gic 100mL, cng kch thc ln lt cho vo m i bnh cc ha cht nh sau:
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Bng 7.11. Cc bc tin hnh phn tch SiO2 Bnh 1 Bnh 2 1. 50mL mu nc 1. 25mL dung dch Na2B4O7.H2O 1%, v 2. 1mL HCl 50% v 2mL 29,5mL nc ct, lc u dung dch khng (NH4)6Mo7O24.4H2O lc u. mu. yn 10 pht, sau tip tc cho 2. Dng dung d ch K2CrO4 0,63% chun t vo 1,5mL H2C2O4.2H2O 10%, t cho n khi dung dch c mu vng ging nh bnh 1 th dng l i, ghi th tch lc u, dung dch c mu vng. dung d ch K2CrO4 0,63% s dng. 3.17.5 Tnh kt qu
SiO2 ( mg / L) = V x 1000 50
Vi V l th tch dung dch K2CrO4 0,63% s dng. 3.18 Ammonia (NH3) v Ammonium (NH4+) 3.18.1 Phng php Nessler (American Public Health Association, 1989) Nguyn tc Trong mi trng baz mnh NH4+ s bin thnh NH3. NH3 mi hnh thnh v NH3 sn c trong mu nc s tc dng v i phc cht Indo mercurate kalium (K2HgI4), hnh thnh phc cht c mu vng nu, cng mu m hay nht ty thuc vo hm lng NH3 c trong mu nc. 2 K2HgI4 + NH3 + 3KOH = Hg(HgIONH2) + 7KI + 2 H2O (mu vng) K2HgI4 + NH3 + KOH = Hg(HgI3NH2) + 5KI + H2O (mu nu) Nhng trong nc thin nhin thng cha cc ion Ca2+, Mg2+ (nc cng), trong mi trng baz mnh cc ion ny s to thnh cc hydroxide dng keo, lm cho dung d ch b vn c cn tr qu trnh so mu. khc phc hin tng trn, phi dng mu i Seignett (KNaC4H4O6), hay EDTA (EDTA) cho vo mu nc phn tch, cc mui ny kt hp v i cc ion Ca2+ v Mg2+ hnh thnh cc hp cht ha tan, khng mu trong dung d ch. M2+ + KNa C4H4O6 = K+ + Na+ + M C4H4O6 M2+ + Na2H2I = Na2MI + 2H+
184
Phn tch cht lng nc
Thuc th: - Dung d ch NH4Cl tiu chun N-NH4+ 1mg/mL: Ha tan 0,3822g NH4Cl trong mt t nc ct khng m (un nng 100oC trong 2 gi), sau pha long thnh 100mL. - Dung d ch N-NH4+ tiu chun 0,01mg/mL: Ly 1mL dung d ch N-NH4+ 1mg/mL, dng nc ct khng m pha long thnh 100mL. - Nc ct khng m: Cho 20mL H2SO4 c vo 1 lt nc ct, lc u ri em ct li mt ln na. - Dung d ch Seignett: Ha tan 50 g KNaC4H4O6.4H2O trong mt t nc ct khng m, sau pha long thnh 100mL. - Dung d ch EDTA: Ha tan 50g EDTA trong 60mL nc ct khng m, sau cho vo 10g NaOH khuy u cho ha tan v pha long thnh 100mL. - Dung d ch Nessler: Ha tan 15g HgI2 v 10g KI trong 500mL nc ct khng m, sau cho vo 40g NaOH, Khuy u cho NaOH ha tan hon ton, lng vi ngy v gn ly phn nc trong cho vo bnh nu s dng. Nu khng c sn HgI2 th pha nh sau: Ha tan 9g HgCl2 v 15,5 g KI trong 5mL nc ct khng m, sau cho vo 40g NaOH, khuy u cho NaOH ha tan hon ton lng vi ngy, gn ly nc trong cho vo bnh nu s dng. Tin hnh: Chn 11 ng nghim c dung tch 25mL, cng kch thc, khng mu ln lt cho vo cc ha cht sau: Bng 7.12. Cc bc Nessler ng nghi m Dung d ch N-NH4+ 0,01N mg/mL Nc ct khng m (mL) Mu nc Dung d ch Seignett hay trion B (mL) Dung d ch Nessler (mL) Nng N-NH3 tng s thit lp mu chun phn tch TAN bng phng php 1 0,1 9,9 0 0,2 1,0 0,1 2 0,2 9,8 0 0,2 1,0 0,2 3 0,3 9,7 0 0,2 1,0 0,3 4 0,4 9,6 0 0,2 1,0 0,4 5 0,5 9,5 0 0,2 1,0 0,5 6 0,6 9,4 0 0,2 1,0 0,6 7 0,7 9,3 0 0,2 1,0 0,7 8 0,8 9,2 0 0,2 1,0 0,8 9 0,9 9,1 0 0,2 1,0 0,9 10 1,0 9,0 0 0,2 1,0 1,0 11 0 0 10 0,2 1,0 ?
Ly ng nghim th 11 (mu nc) em so mu v i 10 ng cn li. Mu trong ng nghim th 11 trng v i mu ng nghim no th nng TAN (tng m amn) bng v i nng TAN trong ng . Khi so mu cn cc ng nghim trn nn mu trng, v nhn kt qu t trn xung di phn bit mu r rng. Phng php
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ny so mu bng mt thng nn rt n gin v d thc hin nhng chnh xc khng cao, t c chnh xc cao chng ta c th p dng so mu quang ph. Ch , kt qu thu c t phng php ny l hm lng tng m amn (TAN), TAN = N-NH3 + N-NH4+. tnh c hm lng N-NH3 v N-NH4+ khi thu mu nc chng ta phi o pH v nhit , da vo tra (xem phn l thuyt Chng 3, Mc 7.1) xc nh t l NH3 cha trong TAN, t tnh ra kt qu: Tnh kt qu Hm lng N-NH3 (mg/L) =
TAN x I 100
Hm lng N-NH4+ (mg/L) = TAN - N-NH3 - I l t l phn trm ca N-NH3 cha trong TAN 3.18.2 Phng php Indophenol Blue Nguyn tc Phn ng Berthelot da trn s th hin mu xanh ca dung d ch khi ammonia phn ng v i phenol v alkaline hypochlorite v c g i l phng php Indophenol hoc phng php Phenate. Phng php ny c p dng cho phn tch mu nc thi v i cng tng cng nh hn 400mg/L v nng nitrite nh hn 5mg/L (Scheiner, 1976) Trong phng php Indophenol, phenol v Hypochlorite phn ng trong mi trng kim hnh thnh phenylquinone-monoimine, ri tr l i phn ng v i ammonia to thnh Indophenol c mu xanh, c minh ha qua phng trnh sau:
2 - O- + NH3 + 3 ClOPhenol O-N= = O + 2H2O + OH- + 3ClIndophenol (mu xanh)
Cng mu ty thuc vo nng hin din ca ammonia, v sodium nitroprusside c thm vo lm tng cng hin mu trong dung d ch. Nng ca tng m amn - TAN (NH3 v NH4+) s c xc nh b i my so mu quang ph bc sng 630 nm (i v i nc ngt) v 640 nm (nc l- mn) Tin trnh phn tch nc mn, l Thu mu vo chai nha 125mL, bo qun lnh cho n khi phn tch mu xong Thuc th - Dung d ch A: ha tan 4g phenol v i dung dch ethanol 95% thnh 500mL. - Dung d ch B: ha tan 0,375 g sodium nitroprusside (sodium nitroferricyanide) v i nc ct thnh 500mL.
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Phn tch cht lng nc
- Dung d ch C: ha tan 7,5 g trisodium citrate v 0,8g NaOH v i nc ct thnh 500mL. - Dung d ch D: dung d ch oxy ho: Ly 2 mL sodium hypochlorite (NaOCl, 5%) pha v i dung dch C thnh 100mL (chun b ngay trc khi s dng). Dung d ch chun - Dung d ch (NH4)2SO4 500mg/l: ho tan 0,2358g (NH4)2SO4 ) v i nc ct khng m thnh 100mL. - Dung d ch (NH4)2SO4 5mg/l: pha 1mL dd (NH4)2SO4 500mg/l) v i nc ct khng m thnh 100mL. Thit lp mu chun Chn 6 bnh tam gic c dung tch 100mL, cng kch thc, khng mu ln lt cho vo cc ha cht sau: Bng 7.13. Cc bc thit lp mu chun phn tch TAN bng phng php indophenol blue cho mu nc l, mn. Th tch nc bin lc c STT Nng mu Th tch dung dch S = S ca mu nc chun (mg/l) (NH4)2SO4 5mg/L (mL) (mL) 1 0 0 100 2 0,2 4 96 3 0,4 8 92 4 0,6 12 88 5 0,8 16 84 6 1,0 20 80 Tin hnh phn tch Dng pipete ht 3 mL mu nc v mu chun cho vo cc ng nghim khc nhau. - Thm 1 mL dd A, trn u. - Thm 1 mL dd B (nitroprusside), trn u. - Thm 2 mL dd D (dd oxy ho), trn u. - trong t i nhit phng khong 1-2 gi cho phn ng xy ra hon ton (mu th hin r). Phn tch bc sng 640 m i v i cuvet 1 cm di truyn quang. Mu Zero l nc bin lc c S = S ca mu nc Tin trnh phn tch nc ngt Thu mu vo bnh 1lt, bo qun lnh cho n khi phn tch mu xong Thuc th - Dung d ch PRE 1: nc ct khng m - Dung d ch PRE 2: phenole stock solution: ho tan 312,5g phenol trong methanol thnh 500mL. - Dung d ch PRE 3: sodium hypochlorite 5%
187
- Dung d ch PRE 4: dung d ch NaOH 67.5%: ha tan 67,5g NaOH thng 100mL nc ct khng m. - Dung d ch A- Ha tan 150g Na3PO4.12H2O v 150g C6H5O7.2H2O trong 1000mL nc ct khng m. - Dung d ch B- Ha tan 75mL PRE 2 v i 0.1g Na2[Fe(CN)5NO].2H2O trong 100mL nc ct khng m. - Dung d ch C- Ha tan 75mL PRE 3 v i PRE 4 thnh 100mL. Dung d ch chun: - Dung d ch (NH4)2SO4 500mg/L: ha tan 0,2358g (NH4)2SO4 trong 100mL nc ct khng m. - Dung d ch (NH4)2SO4 5mg/L: pha 1mL dung d ch (NH4)2SO4 500mg/L thnh 100mL v i nc ct khng m. Thit lp mu chun: Chn 6 bnh tam gic c dung tch 100mL, cng kch thc, khng mu ln lt cho vo cc ha cht sau: Bng 7.14. Cc bc thit lp mu chun phn tch TAN bng phng php indophenol blue cho mu nc ngt. Th tch nc ct khng STT Nng mu chun Th tch dung dch m (mL) (mg/l) (NH4)2SO4 5mg/l (mL) 1 0 0 100 2 0,2 4 96 3 0,4 8 92 4 0,6 12 88 5 0,8 16 84 6 1,0 20 80 Tin hnh Ln lt ong 25mL mu nc v 25 mL tng nng mu chun cho vo bnh tam gic 50mL. Sau , cho vo tng bnh cc dung dch sau: - 1mL thuc th A - 1mL thuc th B - 1mL thuc th C Ch 20-25 pht, xut hin mu xanh (mu s n nh sau 25 pht n 24 gi) em o hp th quang bc sng 630 m. Ch , nu mu xanh qu m ta nn lm l i bng cch pha long, sau khi ghi kt qu t my ta x l l v i h s pha long s cho kt qu nng ca mu m ta cn o. Tnh kt qu Cc mu chun thit lp c em o hp th quang, tng ng v i nng C ca mu chun ta c hp th quang A. Da vo s tng quan ny chng ta c th lp phng trnh tng quan dng A = aC + b
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Phn tch cht lng nc
Trong : A: hp th quang C : nng ca mu (mg/L) Sau khi thit l phng trnh, chng ta o hp th quang ca mu cn phn tch v th vo phng trnh chng ta s tnh c nng ca TAN c trong mu nc.
C= Ab a
3.19
Nitrite (NO2-)
3.19.1 Nguyn tc Nitrite (NO2-) trong mi trng acid mnh s hnh thnh HNO2, HNO2 mi hnh thnh s kt hp v i acid sulfanilique cho ra mui Diazonium sulfanilique. NaNO2 + 2HCl + HSO3-C6H4-NH2 = HSO3-C6H4-N=N-Cl+ NaCl + H2O Sau mu i diazonium sulfanilique s kt hp v i thuc th . napthylammine cho ra . Napthylammine diazonium sulfanilique. HSO3-C6H4-N=N-Cl + C10H9NH2 = HSO3-C6H4-N=N-C10H8NH2 + HCl . napthylammine diazonium sulfanilique l mt hp cht c mu hng, cng m hay nht ty thuc vo hm lng NO2- c trong mu nc lc ban u. Nng c xc nh b i my so mu quang ph b c sng 543 m. Phng php ny c gi l phng php Griess llosvay, Diazonium. 3.19.2 Cc bc phn tch Thu mu v bo qun Thu mu vo chai nha 125mL, bo qun mu lnh cho n khi phn tch mu xong. Thuc th - PRE 1: Cn 5g sulfanilic acid v 250g natri acetate ha tan v i nc ct thnh 500mL. - PRE 2: ha tan 0,5g 1-naphthylamine v 25mL acetic acid v i nc ct thnh 500mL. - Dung d ch A: Ha tan 100mL PRE 1 v i 100mL PRE 2. - Dung d ch B: Dung d ch acetic acid nguyn cht. Dung dch chun - Dung d ch NaNO2 500mg/l: ha tan 0,2463g NaNO2 trong 100mL nc ct. - Dung d ch NaNO2 5mg/l: ha tan 1mL dd NaNO2 500mg/l v i nc ct thnh 100mL. Thit lp mu chun
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Chn 6 bnh tam gic c dung tch 100mL, cng kch thc, khng mu ln lt cho vo cc ha cht sau: Bng 7.15. Cc bc thit lp mu chun phn tch nitrite bng phng php Griess llosvay, Diazonium. Mu nc ngt STT Nng mu Th tch dung dch Th tch nc ct (mL) chun (mg/L) NaNO2 5mg/L (mL) 1 0 0 100 2 0,1 2 98 3 0,2 4 96 4 0,3 6 94 5 0,4 8 92 6 0,5 10 90 Mu nc l, mn STT Nng mu Th tch dung dch Th tch nc bin lc c S%o chun (mg/L) NaNO2 5mg/L (mL) = S%o ca mu (mL) 1 0 0 100 2 0,1 2 98 3 0,2 4 96 4 0,3 6 94 5 0,4 8 92 6 0,5 10 90 Tin hnh - Lm ng chun: ong ln lt 20mL tng nng chun cho vo 6 bnh tam gic c k hiu nng chun b. - ong 20mL mu nc cn o vo bnh tam gic khc. - Ln lt cho thuc th vo: 1mL thuc th A v 5mL thuc th B - Ch 40 pht dd s c mu hng nu c nitrite (mu s n nh sau 40 pht n 4 gi ), ta em so mu bc sng 530 m. - Mu Zero l nc bin lc c nng mu i tng ng v i nng mu i ca mu nu phn tch mu nc l. Ch , nu mu hng qu m ta nn lm l i bng cch pha long, sau khi ghi kt qu t my ta x l l v i h s pha long s cho kt qu nng ca mu m ta cn o. Qu trnh tnh ton kt qu tng t nh phng php Indophenol blue o TAN hay phng php Methylen blue o H2S. 3.20 Nitrate (NO3-) 3.20.1 Phng php kh Cadmium Nitrate (NO3-) trong nc s b kh ton b thnh nitrite (NO2-) bi ct Cadmium c x l b i CuSO4. NO2- mi hnh thnh v NO2- sn c trong nc s c xc nh b i phng php diazonium.
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Phn tch cht lng nc
3.20.2 Phng php phenoldisulfonic acid Nguyn tc Nitrate (NO3-) c trong nc tc dng v i phenol disulfonic acid to thnh phc cht khng mu nitrophenol disulfonic. mi trng baze mnh, phc cht ny c mu vng. Cng mu vng cng m th nng NO3- cng cao
OH HSO3 + NO3 SO3H Phenol dissulfonic acid OH NO2 + 3KOH SO3H SO3H HSO3
-
HSO3
OH NO2 + H2O SO3H (1)
Nitrophenol dissulfonic (phc cht khng mu) O N- OK + 3H2O (2)
HSO3
Thuc th
phc cht mu vng
- Dung d ch acid Phenoldisulfonic: Ha tan 3g phenol trong 20mL H2SO4 c trong mt cc thy tinh chu nhit, ngui cho vo l nu s dng. - Dung d ch NH4OH nguyn cht (khong 25%). Nu khng c, c th thay bng 68 g KOH ha tan thnh 100mL v i nc ct. - Dung d ch Nitrate tiu chun N-NO2- 0,01 mg/mL: Ha tan 0,722g KNO3 (sau khi sy kh 105oC v ngu i trong bnh ht m) trong mt t nc ct, sau pha long thnh 100mL. Ly 1mL dung dch va pha long trn pha long thnh 100mL, ta s c dung dch N-NO3- tiu chun 0,01mg/mL. Tin hnh Chn 12 ng nghim cng kch thc, c dung tch 25mL, ln lt cho vo m i ng nghim cc ha cht sau:
191
Bng 7.16. Cc bc thit lp mu chun phn tch nitrate bng phng php phenoldisulfonic acid. ng nghim 1 2 3 4 5 6 7 8 9 10 Dung d ch N-NO3 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 0,01 mg/mL (mL) Nc ct (mL) 9,8 9,6 9,4 9,2 9,0 8,8 8,6 8,4 8,2 8,0 Mu nc (mL) 0 0 0 0 0 0 0 0 0 0 Dung d ch acid Phenoldisulfonic 1 1 1 1 1 1 1 1 1 1 (mL) NH4OH c (mL) 1 1 1 1 1 1 1 1 1 1 Nng N-NO3 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 (ppm)
11 2,2 7,8 10 1 1 2,2
Ly 10mL mu nc, cho vo chn s em un cch thy cho n kh. Nu c NO3th trong chn s c kt ta. Ha tan kt ta bng 1 mL dung d ch acid phenoldisulfonic, khuy u cho kt ta ha tan, cho dung dch trong chn s vo mt ng nghim th 12, sau ra sch chn bng 10mL nc ct, nc ra ny cng cho vo ng nghim, tip tc cho vo ng nghim 1mL NH4OH c lc u, em so mu v i cc ng nghim trong gam mu ging nh phng php xc nh TAN bng phng php Nessler. c kt qu chnh xc chng ta c th p dng phng php so mu quang ph. 3.20.3 Phng php salycilate Thu mu v bo qun Thu mu vo bnh 1 lt, bo qun mu lnh cho n khi phn tch mu xong. Thuc th Dung d ch A - Ha tan 5g natri salicylate thnh 1000mL v i nc ct. Dung d ch B - Dung dch H2SO4 98% Dung dc C - Ha tan 100g C4H4KNaO6.4H2O thnh 1000mL v i nc ct. Dung d ch D - Dung dch NaOH 10N: ha tan 400g NaOH thnh 1000mL v i nc ct.
Dung dch chun - Dung d ch KNO3 500mg/l: ha tan 0,3609g KNO3 trong 100mL nc ct. - Dung d ch KNO3 50mg/l : ha tan 10mL dd KNO3 500mg/l thnh 100mL v i nc ct. Thit lp mu chun
192
Phn tch cht lng nc
Chn 6 bnh tam gic c dung tch 100mL, cng kch thc, khng mu ln lt cho vo cc ha cht sau: Bng 7.17. Cc bc thit lp mu chun phn tch nitrate bng phng php Salicilate. Mu nc ngt STT Nng mu chun Th tch dung dch Th tch nc ct (mL) (mg/L) KNO3 50mg/l (mL) 1 0,0 0 100 2 2,0 4 96 3 4,0 8 92 4 6,0 12 88 5 8,0 16 84 6 10,0 20 80 Mu nc l mn STT 1 2 3 4 5 6 Nng mu chun (mg/l) 0,0 0,1 0,2 0,3 0,4 0,5 Th tch dung dch KNO3 50mg/L (mL) 0 2 4 6 8 10 Th tch nc bin lc c S%o = S%o ca mu (mL) 100 98 96 94 92 90
Tin hnh Ly 10 mL mu nc, cho vo 1mL thuc th A em sy 1050C cho n cn ngui. Cho vo 1mL thuc th B Ch 10 pht Cho tip 20mL thuc th C V 5mL thuc th D, dd s c mu vng anh nu c nitrate. Ch 15 pht xut hin mu vng anh (mu n nh sau 15 pht n 6 gi), sau o hp th quang bc sng 410m.
Ch , nu mu vng anh qu m ta nn lm li bng cch pha long, sau khi ghi kt qu t my ta x l l v i h s pha long s cho kt qu nng ca mu m ta cn o. Ghi kt qu hp th quang A v da vo phng trnh h i qui tnh ra nng ca mu
193
3.21
Orthophosphate (PO43-)
3.21.1 Phng php xanh molybden Nguyn tc Ln ha tan trong nc c lc qua mng lc 0,45 m. Cc mui orthophosphate trong mi trng acid, ion PO43- s cho mt phc cht mu vng chanh v i thuc th Molybdate ammonium. PO43- + 12(NH4)2MoO2 + 24H+ = (NH4)2PO4.12MoO3 + 21NH4+ + 12H2O (-phospho molybdate NH4+) Dng -phospho molybdate NH4+, trong s hin din ca cc cht kh nh SnCl2, v.v..d b kh thnh dng - phospho molybdate NH4+c mu xanh. Cng mu m hay nht ph thuc vo hm lng ion PO43- c trong mu nc lc ban u. (NH4)3PO4.12MoO + Sn2+ + 16H+ = (NH4)3PO4.(4MoO2.2MoO3)2 + Sn4+ + 8H2O V c xc nh bi my so mu quang ph bc sng 690 m. Ha cht - Dung d ch Amonium molybdate Cn 25 g (NH4)6Mo7O24.4H2O ha tan trong 175 mL nc ct ong 280mL H2SO4 m c pha v i 400mL nc ct, ngui Trn ln hai dung dch li r i pha long v i nc ct thnh 1000mL - Dung d ch SnCl2 Cn 2,5g SnCl2.H2O ha tan trong 100mL Glycerin (Cung cp nhit). Bo qun dung dch t lnh - Dung d ch chun P-PO43Dung d ch KH2PO4 500mg/l: ha tan 0,2197g KH2PO4 trong 100mL nc ct Dung d ch KH2PO4 5mg/l: ha tan 1mL dd KH2PO4 500mg/l thnh 100mL v i nc ct Thit lp mu chun Chn 6 bnh tam gic c dung tch 100mL, cng kch thc, khng mu ln lt cho vo cc ha cht sau:
194
Phn tch cht lng nc
Bng 7.18. Cc bc thit lp mu chun phn tch orthophosphate bng phng php xanh molypden . Nng mu chun Th tch dung dch Th tch nc ct STT (mg/l) KH2PO4 5mg/l (mL) (mL) 1 0 0 100 2 0,2 4 96 3 0,4 8 92 4 0,6 12 88 5 0,8 16 84 6 1,0 20 80 Tin trnh phn tch - Ly ln lt 50mL nc mu c lc loi b v t cht l lng c trong nc vo bnh tam gic, cng v i 50mL tng nng chun cho vo 6 bnh tam gic c k hiu sn nng . - Cho vo 2mL dd amonium molybdate, lc u - Cho vo 5 git SnCl2, lc u - o hp th quang bc sng 690m Tnh kt qu Tnh nng P-PO43- hin din trong mu da trn vic phng trnh h i qui tng quan gia hp th quang v nng cht tan cn phn tch tng t nh cc cc phng php Methylen blue (phn tch H2S), Indophenol blue (phn tch TAN), Salicilate (Phn tch NO3-)... 3.21.2 Phng php Acid ascorbic (4500-P E: Standard methods, 1998) Nguyn tc Ammonium molybdate v potassium antimonyl tartrate trong acid trung tnh phn ng v i orthophosphate to thnh 1 dng acid d a (heteropolyacid) acidphosphomolybdate b kh thnh dng c mu xanh tp trung molybde bi acid ascorbic. Nng ca P-PO43- s c xc nh b i my so mu quang ph bc sng 880 m. Thuc th - H2SO4 5N: Pha 70 mL H2SO4 m c v i nc ct thnh 500 mL. - Dung d ch Potassium antimonyl tartrate: Ha tan 0,12 g K(SbO)C4H4O6.1/2H2O trong 400 mL nc ct. sau pha long thnh 500 mL. - Dung d ch ammonium molybdate: ha tan 20 g (NH4)6Mo7O24.4H2O trong 500 mL nc ct.
195
- Acid Ascorbic 0,1M: ha tan 1,76 g trong 100 mL nc ct. Dung dch n nh khong 1 tun 4oC. - Thuc th kt hp (combined reagent): Trn cc thuc th trn li v i nhau theo t l sau c 100 mL thuc th kt: 50 mL H2SO4 5N 5 mL potassium antimonyl tartrate 15 mL ammonium molybdate 30 mL acid ascorbic. Trn u mi khi cho vo tng lo i thuc th theo th t nu trn. Cho php cc thuc th trn nhit phng trc khi ph i hp. Nu c xut hin trong thuc th hn hp th lc u r i yn cho n khi c khng cn xut hin. Thuc th ny n nh trong 4 gi. - Dung d ch m (stock phosphate solution): Ha tan 219,5 mg KH2PO4 trong 1000mL nc ct c dung d ch c nng cht chun l 50 g/mL hay 50 mg/L - Dung d ch chun (Standard phosphate solotion): Ha tan 50 mL dung d ch m v i 1000 mL nc ct c c dung d ch chun c nng 2,5 g/mL hay 2,5 mg/L Tin trnh phn tch - Ly 50 mL mu nc v mu chun cho vo bnh tam gic 125 mL sch v kh. - Thm 0,05 mL ch th mu phenolphthalein. Nu xut hin mu th thm tng git dd H2SO4 5N cho n khi dung d ch va mt mu. - Thm 8 mL thuc th kt hp (combined reagent) ri khuy u. - Sau 10 pht nhng khng qu 30 pht, o hp th quang tng mu bc sng 880 m, s dng mu trng lm dung dch i chng. - Khc phc mu b c hay nhiu mu: Nu cc mu sau khi cho vo cc thuc th m c mu hoc c th phi chun b mu trng bng cch thm tt c cc thuc th vo ngo i tr acid ascorbic v antimonyl potassium tartrate. Ly hp th quang ca tng mu chun v mu nc tr i cho hp th quang ca mu trng loi tr sau s do nhiu mu Qu trnh thit lp mu chun, xy dng ng chun v tnh kt qu (xc nh nng cht tan cn phn tch) tng t nh phng php xanh molypden. 3.22 Tng m (TN) v tng ln (TP) 3.22.1 Phng php Kjeldahl Nguyn tc
196
Phn tch cht lng nc
Cc dng m hu c b oxy ha bi acid H2SO4 m c v i xc tc K2SO4 v CuSO4 hoc H2O2 trong iu kin nhit cao (375-385oC) s chuyn ha hon ton thnh m ammonium (NH4+). Ammonia (NH3) cng chuyn thnh ammonium. Sau khi thm vo dung d ch baz, ammonia c ha tan trong mi trng kim v b hp thu bi acid boric hay acis sulfuric, ammonia c th c xc inh bng phng php so mu quang ph Indophenol blue. Cc dng ln hu c cng b oxy ha (trong iu kin tng t nh m hu c) s chuyn ha thnh orthophosphate. Orthophosphate c th c xc nh bng phng php so mu quang ph ascorbic acid hay xanh molypden. Do , phn tch tng m (TN) v tng ln (TP) chng ta c th thc hin cng ph trn cng mt mu, sau m i tin hnh phn tch hai ch tiu trn theo cc phng php dng phn tch cc dng mui m v ln v c ha tan. Thit b thc hin qu trnh v c ha m, ln hu c chng ta cn dng my cng ph mu (digestion apparatus). Hin nay trn th trng c bn nhiu lo i my cng ph mu, th d nh BD-26 (BD-26 Block Digestor), c th ci t chng trnh iu khin nhit trong qu trnh cng ph mu. Tin trnh cng ph mu nc i. Chun b cc mu nc (V = 50 hoc 100 mL) cho vo cc ng cng ph; s dng 2-3 ng mu trng (nc ct); thm 2-3 vin s i lo i chuyn dng cho qu trnh cng ph (chng nc b bn ra ngoi khi si) vo m i ng. thm mi ng mu nc v mu trng 10 mL H2SO4 m c, trn u, i n khi mu ngu i l i. Sau khi ngu i, thm 10 mL H2O2 m c (c th dng 6,7 g K2SO4 v 0,365 g CuSO4), mu qua m trc khi cng ph. t cc ng mu v gi ln my cng ph. M my cng ph v my ht (qu trnh cng ph nc bc hi nn phi dng my ht). Ci t chng trnh iu khin nhit : Temp1 = 110oC, gi nhit ny trong vng 20 pht (khng k th i gian nhit tng t nhit phng ln 110oC). Temp2 = 200oC, gi trong vng 20 pht (khng k th i gian nhit tng t 110oC ln 200oC). Temp3 = 300oC, gi nhit ny n khi mu cng ph c mu trng Ch , c th tng nhit cng ph ln n 375oC. Nhit cng cao th
ii. iii. iv. v.
197
thi gian cng ph cng ngn. Tng thi gian cng ph 3 bc trn c tnh khong 90 pht. vi. Sau khi qu trnh cng ph hon thnh, tt my, ngui.
vii. Khi cc mu c cng ph v ngu i hon ton, pha long phn acid sulphuric cn l i trong ng v i 25 mL nc ct khng m r i ton b phn nc ny vo ng ong (V = 250 mL). Trung ha dung dch bng cch nh NaOH 40% (10 M) c s hin din ca cht ch th para-nitro-phenol (4nitro-phenol), sau chun li mi trng acid bng vi git dung d ch H2SO4 20%; Dung dch sau cng c thm 1 git H2SO4 20% gi dung dch c mi trng pH di 7,0 (5,0-7,0). Xc nh hm lng tng m (TN) v tng ln (TP) Xc nh hm lng m TAN ca mu nc di dng N-NH4 bng phng php Indophenol blue v Orthophosphate (P-PO43-) bng phng php Xanh molypden hay Acid ascorbic. Ch , v i phng php cng ph Kjeldahl, kt qu hm lng m m thu c c gi l tng m Kjeldahl (Total Kjeldahl Nitrogen - TKN). TKN bao gm hm lng m hu c v TAN c trong mu nc (TKN = N-Hu c + TAN). Trong trng hp ny nu mun tnh c tng m (TN) chng ta phi xc nh thm hm lng m nitrite v nitrate TP = TKN + N-NO2- + N-NO3Nu trc khi cng ph mu chng ta lo i b TAN bng cch nng pH ca mu nc ln 9,5, khi NH4+ s chuyn hon ton thnh NH3. un nh mu, NH3 s thot ra khng kh sau m i cng ph mu. Trong trng hp ny kt qu hm lng m thu c chnh l m hu c (TKN = N-Hu c). Hm lng ln thu c t phng php cng ph Kjeldahl l tng ln (TP). Tin trnh cng ph mu bn y i. Mu bn thu v kh trong iu kin nhit phng, k n sy kh nhit 105oC. Mu sau khi sy c nghin mn, ry qua l i v gi trong l kn n khi phn tch. Cn 0,15-0,25g mu bn cho vo ng cng ph, thm 2-3 vin nh (loi chuyn dng cho my cng ph) vo mi ng, tip tc thm 50 mL nc ct khng m 10 mL H2SO4 , lc u, ngui hon ton. Sau khi ngu i, thm10 mL H2O2 m c, mu qua m trc khi cng ph.
ii.
198
Phn tch cht lng nc
iii. iv. v.
t cc ng mu v gi ln my cng ph. M my cng ph v my ht (qu trnh cng ph nc bc hi nn phi dng my ht). Ci t chng trnh iu khin nhit : Temp1 = 110oC, gi nhit ny trong vng 30 pht (khng k th i gian nhit tng t nhit phng ln 110oC). Temp2 = 200oC, gi trong vng 30 pht (khng k th i gian nhit tng t 110oC ln 200oC). Temp3 = 375oC, gi nhit ny n khi mu cng ph c mu trng Tng th i gian cng ph 3 bc trn c tnh khong 90 pht. Sau khi qu trnh cng ph hon thnh, tt my, ngui.
vi.
vii. Khi cc mu c cng ph v lm lnh hon ton, pha long phn acid sulphuric cn li trong ng mt cch cn thn v i 25 mL nc ct khng m ri ton b phn nc ny vo ng ong (V = 250 mL). Trung ha dung dch bng cch nh NaOH 40% (10 M) c s hin din ca cht ch th paranitro-phenol (4-nitro-phenol), sau chun li mi trng acid bng vi git dd H2SO4 20%; Dung dch sau cng, thm 1 gi t dd H2SO4 20% gi dung dch c pH di 7,0 (5,0-7,0). Xc nh hm lng tng m (TN) v tng ln (TP) Xc nh hm lng m TAN ca mu nc di dng N-NH4 bng phng php Indophenol blue v Orthophosphate (P-PO43-) bng phng php Xanh molypden hay Acid ascorbic. i v i mu bn y, kt qu hm lng m thu c l tng m (TKN = TN). Kt qu hm lng ln thu c l tng ln (TP) 3.22.2 Phng php cng ph persulfate Nguyn tc Trong mi trng kim iu kin nhit 110oC, m hu c v m v c b oxy ha bi K2S2O8 s chuyn ha thnh nitrate (NO3-). Ln hu c cng b oxy ha thnh orthophosphate. Cc thuc th - NaOH 1 M: ha tan 40 g NaOH trong 800 mL nc ct, ngui r i pha thnh 1000 mL - Thuc th Oxy ho (OR): ha tan 50 g potassium peroxodisulphate (K2S2O8) v 30g acid boric trong 350 mL NaOH 1 M ri pha thnh 1000 mL v i nc ct. Bo qun trong chai, l mu nu trnh nh sng.
199
Tin trnh - Dng l nha 30 mL, cho vo 25 mL mu nc v cc mu chun ri thm vo 3,3 mL thuc th oxy ho (B). Trn u. - y np l nha ri cho vo ni autoclave khong 20 pht 121oC v p sut 15 psi. Cho php lm lnh 1 gi. - Thc hin t nht 3 mu trng bng nc ct trong sut. Xc nh hm lng tng m (TN) v tng ln (TP) Hm lng tng m c th xc nh c bng cc phng php xc nh bng cc phng php phn tch nitrate (Phenoldisulfunic acid, Salycilate hay kh Carmidium). Ln hu c cng b oxy ha thnh orthophosphate v c xc nh hm lng bng phng php Xanh molypden hay Ascorbic acid. Kt qu hm lng m thu c khi phn tch bng ph ng php cng ph persulfate l tng m - TN (bao gm NHu c, TAN, N-NO2- v N-NO3-) v hm lng ln thu c l tng ln - TP.
200

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Phn tch cht lng nc

PHN TCH CHT LNG NC

Qun l cht lng nc nui trng thy sn

l bc sng (de Broglie)

Phn tch cht lng nc

1.2.1 Cc i lng o bc x in t Bc sng : L qung ng m bc x i c sau mi dao ng y . n v: m, cm, m , nm,

Tn s : L s dao ng trong mt n v th i gian (giy) Trong 1 giy bc x i c c cm v bc sng cm, vy: =

Hnh 7-2. Cc ph ca sng in t

Qun l cht lng nc nui trng thy sn

Trong , E1 v E2 l mc nng lng ca phn t trng thi u v trng thi cui

(hay cn gi l trng thi kch thch) l tn s ca bc x in t b hp th hay pht x ra.

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Nguyn tc ca phng php biu din theo s :

Hnh 7-4. S m t s hp th nh sng ca mt dung dch

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Hnh 7-6. S cu to ca my quang ph

Qun l cht lng nc nui trng thy sn

Khi s dng 2 dung d ch chun:

Phn tch cht lng nc

th tch ban u ca mu Vo (mL): - Phng php s dng th

Qun l cht lng nc nui trng thy sn

A Ax + a3 Ax + a2 Ax + a1 Ax Ca1 Ca2 Ca3 C

(hi quy tuyn tnh y = ax + b)

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Vy nng PO43- trong mu nc ao l 0,137 mg/L.

Phn tch cht lng nc

(7.1) (7.2) (7.3) (7.4)

Vi [In-] = x; [HIn] = y ta c: x + y = CHIn = C

A2 v ton b cht ch th dng InC*l A1 v ton b cht ch th dng HIn C *l

Thay (7.3) v (7.4) vo (7.1) ta c:

x y = ; = (1 ) 0,175 = 0,130 + 0,475 (1-) C C

= 0,869 Hng s phn ly ca HIn: HIn H+ + In- ;

[ H + ][ In ] In = lg = pH lg pK pH HIn HIn 1 0,869 = 7.34 0,82 = 3,52 K = 3,02.10-4. 1 0,689

Vy hng s phn ly ca methyl da cam l K = 3,02.10-4.

Qun l cht lng nc nui trng thy sn

2 PHNG PHP THU V BO QUN MU

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

3 PHNG PHP PHN TCH MT S CH TIU MI TRNG NC

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

ISS ( mg / L) = TSS OSS

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

3.10.2 Dng c v ha cht

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

A2 v ton b cht ch th dng InCl A1 v ton b cht ch th dng HIn C l