Chuong7CAF002

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

1 NG DNG THUYT PHN T UVVIS TRONG PHN TCH CC YU T CHT LNG NC 1.1 S lc lch 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 kp 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 ngha 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 vi s cng tc ca nhiu nh vt l ni 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 nh (7g) t 44.000 lt nc khong gn ni Bad Nauheim, Germany. S khm ph
139
Qun l cht lng nc nui trng thy sn
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 bi kh quyn. Mt nm sau , Walther Noel Hartley m t rt t m v s hp th UV ca O3 vi 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 mi 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 ngoi, tia t ngoi, 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 gi l photon chuyn ng vi 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 vi 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 vi vn tc v c bc sng i i vi n l cho bi h thc:
=
h h = mv p
Trong :
p = mv l ng lng ca ht
l bc sng (de Broglie)
h = 6,625.10 -34 J.s l hng s Planck. 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 .
140
Phn tch cht lng nc
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 thi gian (giy) Trong 1 giy bc x i c c cm v bc sng cm, vy: =
c
Lu : Bc x truyn trong chn khng vi 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 gi 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
Mt ngi ch cm nhn c mt vng ph in t rt nh gi l vng nhn thy (kh kin) bao gm cc bc x c bc sng t 396760 nm. Hai vng tip gip vi vng nhn thy l vng hng ngoi v vng t ngoi.
141
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, gi l trng thi c bn Khi chiu mt bc x in t vo mt 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 vi 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 vi 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 hi mt nng lng c trng cho n, ngha l i hi 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 vi 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, ngha l cc tia ny b phn t hp th. 1.2.4 S hp th bc x v mu sc ca cc cht nh sng nhn thy bao gm tt c di 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 mt s tia mu (, da cam, vng, lc, lam, chm, tm). Mi tia mu ng vi mt khong bc sng hp hn (xem Bng 7-1). Cm
142
Phn tch cht lng nc
gic cc mu sc l mt chui cc qu trnh sinh l v tm l phc tp khi bc x trong vng kh kin chiu vo vng mc ca mt. Mt tia mu vi mt khong bc sng xc nh. Chng hn bc x vi bc sng 400430 nm gy cho ta cm gic mu tm, tia sng vi 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 vi mt ta cht khng mu. Th d, thy tinh thng hp th cc bc x vi bc sng nh hn 360 nm nn n trong sut vi cc bc x kh kin. Thy tinh thch anh hp th bc x vi bc sng nh hn 160 nm, n trong sut i vi 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 li gy cho ta cm gic mu lc (ta thy cht c mu lc). Ngc li, nu cht hp th tia mu lc th i vi mt ta n s c mu . Ngi ta gi mu v mu lc l hai mu ph nhau. Trn hai mu ph nhau li 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 Tia b hp th Mu ca cht hp th (nm) (mu nhn thy) Mu 400 430 Tm Vng lc 430 490 Xanh Vng da cam 490 510 Lc xanh 510 530 Lc ta 530 560 Lc vng Tm 560 590 Vng Xanh 590 610 Da cam Xanh lc 610 750 Lc
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. 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 li cho mt ta cm gic mu .
143
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 vi ranh gii ca vng kh kin. Tng ng vi 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 ngha 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 vi 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. Mt khc, mt hp cht i hi nh biu cao ngha 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
144
Phn tch cht lng nc
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 dch I: Cng nh sng sau khi qua dung dch. IR: Cng nh sng phn x bi thnh cuvette v dung dch, 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 = K 1l I Io = K 1C I
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: nh lut Lambert Beer : A = lg( 0 ) = * C * l 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).
145
I I
Trong phn tch nh lng bng phng php trc quang ngi 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 ngi ta ch o dung dch 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 li 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 hp th quang
Khong tuyn tnh LOL (Limit of Linear Response) l khong nng tun theo nh lut Beer ( A = * l * C ) ngha l khi nng tng th hp th quang A tng. Ngoi gii hn LOL l s lch khi nh lut Beer, ngha l khi nng tng th hp th 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... ngha 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.
146
Phn tch cht lng nc
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 li 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 A X, dung mi c hp th quang l Adm, ta c: A = Ax + Adm o c chnh xc Ax th Adm = 0, c ngha l phi chn max ca dung mi khc xa vi max cht tan. Nhng cht c chn lm dung mi thng c hp thu min ranh gii t ngoi chn khng. Bng7-2. Cc dung mi thng s dng trong vng UVVIS Dung mi Bc sng gii hn Dung mi s dng (nm) Nc ct 190 Benzen HCl 190 Cloroform Etanol, Metanol 210 Tetra Clorocarbon n- Butanol 210 Dietyl Eter n- Hexan 210 Aceton Cyclohexan 210 1,4 Dioxan Bc sng gii hn s dng (nm) 280 245 265 218 330 215
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 lC 2 + ....... + i lC i + ...... + n lC n

truyn quang T:
T= I I m A = lg( 0 ) do A = lg T Io I
147
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 loi n trn. Mt yu cu i vi ngun sng l phi n nh, tui 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 loi t trong mt bng thu tinh cha kh Deuteri hoc hydro c ca s bng thch anh bc x t ngoi i ra v n khng truyn qua c thy tinh. Khi si 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:
* D2 + Ee D2 D + D + h
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 li c tc 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 gii 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 gii cng cao.
148
Phn tch cht lng nc
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 dnh (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 phi 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 vi cc thuc th v c v hu c. Nng cc cht xc nh theo nh lut Lambert Beer. Khong xc nh nng theo phng php l 10-2 10-6 mole. Gii hn pht hin ca phng php 10-7mole. Cc hp cht l phc cn o phi c max khc xa vi 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.
149
1.3.1 Phng php so snh So snh cng mu ca dung dch cn xc nh vi cng mu ca dung dch chun bit nng . iu kin: c hai dung dch trn phi c nng nm trong khong tun theo nh lut Beer. Cx ---------------------- Ax Ctc ---------------------- Atc Ta cn xc nh Cx :
Cx = Ax * C tc Atc
Khi s dng 2 dung dch chun:

C x = C1 + C 2 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, loi 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 vi th tch Vx. Ax+ a: hp thu ca dung dch c thm chun. Ca: Nng cht chun thm vo.
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:
150
Phn tch cht lng nc
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 dch, dung dch gi l dung dch 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 dch ny lm dung dch so snh. p dng cng thc: C x = C a
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 dch thm chun. Ly t nht 4 ln ca dung dch cn xc nh nng cho vo 4 bnh nh mc V(mL). Sau thm chnh xc mt lng V1, V2, V3 mL dung dch tiu chun c nng tng ng Ca1, Ca2, Ca3 vo 3 bnh nh mc trn. Tin hnh phn ng to mu. Bnh cn li lm dung dch so snh, cng chun b ging nh phng php cng thc. hp thu ca cc dung dch thm so vi dung dch so snh. 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 phng php thm chun s dng th.
C th c kt qu trn th hoc s dng phng trnh hi qui c dng:
151
A = aC + b Ax = b Cx = b/a 1.3.3 Phng php ng chun
(hi quy tuyn tnh y = ax + b)
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 vi thuc th. o hp th quang A ca dung dch max so vi cc dung dch 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 dch xc nh: chun b v phn ng to mu vi 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 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 2.000 1.500 H s h thu A p 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
152
Phn tch cht lng nc
Hnh 7-7. Biu xc nh phng trnh hi quy tng quan ca phng php ng chun.
Sau khi thit lp ng chun, ta c dng phng trnh y = ax + b vi y l hp th quang, x l nng . i vi dung dch 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 ni 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 nghch. 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 phng 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). 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 dch 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: p dng cng thc A = lg( 0 ) = * C * l vi dung dch 1 ta c: = 0.252/(2.10-4*1) = 1,26.103l.mol-1cm-1. p dng cng thc A = lg( 0 ) = * C * l vi dung dch 2 ta c:
I I I I
153
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 li 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. V d 3: xc nh hng s phn ly ca Methyl da cam (k hiu HIn), ngi ta o hp th quang A ca 3 dung dch cng nng Methyl da cam cc pH khc nhau:
-
Dung dch 1 trong HCl 0,1M; Dung dch 2 trong NaOH 0,1 M; Dung dch 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)
Vi [In-] = x; [HIn] = y ta c: x + y = CHIn = C

154
Phn tch cht lng nc
In = Hin =
A2 v ton b cht ch th dng InC *l A1 v ton b cht ch th dng HIn C *l
(7.3) (7.4)
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+ + InK=
Ka
[ H + ][ In ] In pK = pH lg = pH lg HIn 1 HIn 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.

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 mi tri lun b thay i theo thi 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 thi gian c th phn nh gn ng gi tr thc. S mu thu thp cn ln v nhp 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) nhp thu mu cho nc nui thy sn nh mu sng thi gian thu mu cn tin hnh khi lu lng thp, ao h cn xem xt chu trnh sinh hc v cn tng nhp thu mu thi 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.
155
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 7.4.
2.2 Cch bo qun mu
2.2.1 Mu nc Ty theo ch tiu cht lng nc m cch ly mu v bo qun 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, ri cho vo cc snh, em sy nhit 105 oC trong 24 gi. ngui mu trong bnh ht m, lc ny sn sng phn tch.
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 4oC 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 11 NO2- v NO3P;G 200 4oC 12 PO43P;G 100 4oC 13 TN,TP P;G 500 4oC
P: Plastic bottle G: Glass bottle
156
Phn tch cht lng nc
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 li (cng nhiu cng tt), ri ly mt mu i din loi mu cn phn tch (ch tiu nc hoc bn y). mi im, cn thu ng thi 3 v tr, ri cho vo 3 x (mi 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 li. 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 vi 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 vi 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.
3 PHNG PHP PHN TCH MT S CH TIU MI TRNG NC
3.1 Nhit 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 t 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 mi 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 .
157
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 vi 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 dch theo phng trnh Nernt. in th sinh ra t t bo t l vi nng ion H + trong mu nc, in th ny c o bng mt in th k v c thit b c bit dch 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 vi mu nc bng mt tia Aming cui in cc. Khi tip xc vi 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 dch HCl 0,1M v c bao bc bi 1 mng thy tinh c nhy cm rt cao vi 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 dch in cc. Theo Peters (1975) th t bo Galvanic i vi vic xc nh pH c th c vit nh sau: Ag / AgCl, HCl (0.1M) / mng thy tinh / mu nc / Hg2Cl2, KCl / Hg. 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 phng php Nephelometric. Ngoi ra c th xc nh lng vt 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
158
Phn tch cht lng nc
mt que hay trn mt si 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 vi chm tia ti c gi 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) vi 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 dch 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 ha tan. o c tng lng cht rn ho tan (TDS). Mu cn c lc loi b vt cht khng ha tan, v nc c lc cho bc hi v phn cn li c cn tnh hm lng cht 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 ngui 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
159
Nung cc s (a snh) nhit 550oC trong 30 pht, sau lm ngui 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 ngui 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 si 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 khi lng giy lc (Wo) Lc u mu nc trc khi lc. 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

160
Phn tch cht lng nc
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 mt dng in ca dung dch. 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 li i vi 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 ngi M-APHA, 1989; Arce v Boyd, 1980), mi trng nc l v mn th dn in cao hn nhiu. dn in v nng mui c lin quan rt cht v nng cc ion trong mi trng, dn in tng cng vi s tng nng mui. Vic o c chnh xc dn in thng khng c i hi cao i vi nui trng thy sn, m thay vo vic o nng mui 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 mui ca nc mt cch tt nht th cn tnh tng nng 7 ion quan trng trong mi trng lm cho nc thin nhin c nng mui 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 mui 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.
161
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 vi lng I2 c trong mu nc lc ban u: MnO2 + 2I- + 4H+ = Mn2+ + I2 + 2H2O I2 c gii phng ra s ha tan trong nc v c xc nh bng phng php chun vi dung dch 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 vi tinh bt hnh thnh mt phc cht c mu xanh. Khi tt c I2 trong dung dch c chun ht vi 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 dch 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 dch MnSO4: Ha tan 50 g MnSO4.5H2O hay 41 g MnCl2.4H2O vi nc ct thnh 100 mL. Dung dch KI-NaOH: Ha tan 50 g NaOH v 15 g KI (hay 14 g NaI) vi nc ct thnh 100 mL. H2SO4 (d=1,84) hay H3PO4 c (d= 1,88). Dung dch Na2S2O3 tiu chun 0,1N: Pha mt ng Na2S2O3 tiu chun 0,1N trong 1000mL nc ct Dung dch Na2S2O3 0,01N: S dng cng thc N1V1 = N2V2 pha dung dch c th nh sau: Ly 50 mL dung dch Na2S2O3 0,1N pha long vi 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 dch 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 vi nc ngt, 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 dch va c acid ha trn, cho vo bnh tam gic 100 mL.
162
Phn tch cht lng nc
Chun bng dung dch Na2S2O3 0,01N cho n khi dung dch c mu vng nht, cho 3 git ch th h tinh bt, lc u dung dch c mu xanh, tip tc chun cho n khi dung dch chuyn t mu xanh sang khng mu th dng li. 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 dch Na 2S2O3 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 mg
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 cc gi tr ny da trn mi quan h gia nhit , ha tan ca oxy v p sut khng kh. u d oxy bao gm 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 dch in cc KCl bo ha ngn cch vi mi trng ngoi bi 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 vi 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 th thu qua mng, phn ng vi cc cathode v b kh thnh hydroxide vi t l 4 moles OH -/mole oxy theo phng trnh sau: O2 +2H2O + 4e- 4OH163
Sau 1 dng in chy qua cc anode (in cc bng bc) v OH - phn ng vi bc to thnh dng oxit bc theo phng trnh sau: 2Ag0 + 2OH- = Ag2O + H2O + 2e-. Do , 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 vi 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 vi vic to ra 10 mg/l 30 oC. Bn cnh , nhit cn nh hng i vi 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 bi nng mui. 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 mui 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 vi dung dch NaOH tiu chun v phenolphthalein lm cht ch th xc nh im tng ng CO2 + NaOH = NaHCO3 (7.6)
Khi phn ng (7.6) t im tng ng, mt git d dung dch 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 dch 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 dch NaOH tiu chun 0,1N: Ha tan ng chun NaOH 0,1N vi nc ct thnh 1000mL Dung dch NaOH 0,01N: Ha tan 100mL dung dch NaOH 0,1N vi nc ct thnh 1000mL.
164
Phn tch cht lng nc
Dung dch m pH= 8,3: Dung dch Na2B4O7 0,05M: Ha tan 1,91g Na2B4O7.10H2O vi nc ct thnh 100mL. Dung dch H3BO3 0,2M: Ha tan 1,24 g H3BO3 vi nc ct thnh 100mL. Ly 20mL dung dch Na2B4O7 0,05M cho vo 30mL dung dch H3BO3 0,2M. Ta s c dung dch m c pH=8,3. Dung dch 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 1. 50mL mu nc.
Bnh 2
2. 3 git ch th phenolphthlein, lc u, dung dch c mu hng nht.
2. 3 git ch th phenolphthlein, lc u, dung dch khng mu.

3. Dung dch NaOH 0,01N chun t t cho
n khi dung dch trong bnh c mu hng nht ging nh bnh 1 th dng li ( mu hng ch bn trong 1 pht). Ghi th tch V1 (mL) dung dch NaOH 0,01N s dng.
4. Lm li 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. 3.8.5 Tnh kt qu CO2 ( mg / L) = VTB x N x 44 x 1000 50
Vtb: l th tch trung bnh dung dch NaOH 0,01N ca cc 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
165
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 vi 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 mi 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 dch H2SO4. Trong mi trng acid, vi s hin din ca mt lng tha I-, lng MnO4- cn li 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 bng phng php chun vi dung dch Na 2S2O3 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 Dung dch 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 dch chuyn t khng mu sang mu hng nht th dng li, ghi th tch dung dch KMnO4 s dng (V1). Lm li nh trn mt ln na ly gi tr trung bnh. Nng dung dch KMnO 4 c iu chnh chnh xc bng cng thc: V1N1 = V2N2 . Dung dch c bo qun trong chai nu. Dung dch KMnO4 0,05N tnh kim: Ha tan 500mL dung dch KMnO4 trong 500mL nc ct c ha tan 8g NaOH, cho vo bnh mu nu s dng. Dung dch KI 10%: Ha tan 10g KI vi nc ct thnh 100mL. Dung dch H2SO4 4M: Ha tan 22,2mL H2SO4 m c vi nc ct thnh 100mL. Dung dch Na2S2O3 0,1N: Ly 1 ng Na2S2O3 0,1N chun pha long vi nc ct thnh 1.000mL.
166
Phn tch cht lng nc
Dung dch Na2S2O3 0,05N: Ly 500mL dung dch 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 dch tr nn trong sut, cho vo 0,5mL formaline nguyn cht s dng c lu. Dung dch NaOH 0.4N: Ly 40mL dung dch 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):
Bng 7.6. Cc bc tin hnh phn tch COD Bnh 1 1. 50mL mu nc. 1. 2. 5mL dung dch NaOH 0,4N. 2. 3. 5mL dung dch KMnO4 0,05N. 3. 4. em un cch thy im si ng 4. mt gi, ly ra ngui 10 pht. 5. Tip tc vo 5mL KI 10% v 5mL dung dch H2SO4 4M, lc u dung 5. dch c mu vng nu. 6. Dng dung dch Na2S2O3 0,05N chun cho n khi dung dch c mu vng 6. nht, cho vo 3 git ch th h tinh bt
Bnh 2 50mL nc ct. 5mL dung dch NaOH 0,4N. 5mL dung dch KMnO4 0,05N. em un cch thy im si ng mt gi, ly ra ngui 10 pht. Tip tc vo 5mL KI 10% v 5mL dung dch H2SO4 4M, lc u dung dch c mu vng nu. Dng dung dch Na2S2O3 0,05N chun cho n khi dung dch c
167
1%, lc u dung dch c mu xanh, tip tc chun t t cho n khi dung dch tr nn khng mu th dng li, ghi th tch (V1) dung dch Na2S2O3 0,05N s dng. 7. Ly bnh cn li chun tng t nh bnh trn ly gi tr trung bnh.
mu vng nht, cho v 3 git ch th h tinh bt 1%, lc u dung dch c mu xanh, tip tc chun t t cho n khi dung dch tr nn khng mu th dng li ghi th tch (V2) dung dch Na2S2O3 0,05N s dng. 7. Ly bnh cn li chun tng t nh bnh trn ly gi tr trung bnh.
Tnh kt qu
COD (mg / L) = (V2 V1 ) x N x 8 x 1000 VM
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.
3.9.2 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 vi H2SO4. Mu nc ny sau c un nng v cc cht hu c b oxy ha thnh CO 2 v H2O, trong khi Dichromate b kh theo phng trnh sau: Cht hu c + Cr2O72- + H+ 2Cr3+ + CO2 + H2O Lng tha dichromate c th xc nh c bng cch chun vi 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 nng sut sinh hc s cp ca thy vc nh: phng php bnh ti- bnh sng, phng php ng v phng x C 14, phng php xc nh hm lng cc sc t quang hp trong nc, phng php xc nh sinh khi thc vt ni, phng php xc nh theo hm lng oxy trong nc.
168
Phn tch cht lng 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 li khi khng c nh sng, do s hp thu CO2 t mi trng v lng O2 c thi ra cng b dng li. Qu trnh h hp hp th O2 v thi ra CO2 tin hnh vi tc ngang nhau trong ti v ngoi sng. Do da trn hm lng O2 ha tan trong bnh ti 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:
-
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
3.10.2Dng c v ha cht Dng c H thng bnh sng- bnh ti: Cc bnh ti 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 Ton b ha cht xc nh ha tan theo phng php Winkler (xem mc 3.7.1). 3.10.3Tin hnh Dng a secchi o trong ca nc, nhn trong vi 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. mi v tr dng 6 bnh BOD 125mL (4 bnh sng v 2 bnh ti), thu y mu nc v tr theo nng sut sinh hc s cp. Ly 2 bnh sng phn tch O 2 ban u (DO), 4 bnh cn li dng gi t ng v tr cn thu mu nc 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

169
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 3.11Chlorophyll-a 3.11.1Nguyn tc Phng php chit 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 chit sut bi acetone Phng php ny c b sung bi Lalli (1984). Trong phng php ny, chlorophyll c chit xut trong acetone v o mc hp thu quang ph 4 bc sng. 3.11.2Tin hnh Ho cht Dung dch 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 thi 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)
170
Phn tch cht lng nc
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 vi 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 vi dung dch 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 dch CdCl2 2%: Ha tan 2 g CdCl2 vi nc ct thnh 100mL. Dung dch HCl 4M: Cho 25mL HCl c (12M) vo v pha long thnh 100mL vi nc ct. Dung dch 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 li nng chnh xc bng dung dch Na 2S2O3 0,1N tiu chun. Cch tin hnh nh sau: dng bnh tam gic 100mL, cho vo 20mL dung dch I2 va pha trn (dng buret xc nh th tch I2, khng dng ng ht), dng dung dch Na2S2O3 0,1N tiu chun, chun cho n khi dung dch c mu vng, tip tc chun cho n khi dung dch c mu vng nht, cho 3 git h tinh bt, lc u dung dch c mu xanh, tip tc chun cho n khi dung dch chuyn t mu xanh sang khng mu th dng li, ghi th tch dung dch Na2S2O3 0,1N s dng. Lm li nh trn mt ln na ly gi tr V trung bnh. Sau hiu chnh nng dung dch I2 cho chnh xc bng biu thc: N1V1 = N2V2 Dung dch I2 0,01N: ly 50mL I2 0,1N dng nc ct pha long thnh 500mL. Dung dch Na2S2O3 tiu chun 0,1N: Pha mt ng Na2S2O3 tiu chun 0,1N trong 1000mL nc ct
171
(khng mu)
Dung dch Na2S2O3 0,01N: S dng cng thc N1V1 = N2V2 pha dd c th nh sau: Ly 50mL dung dch Na2S2O3 0,1N pha long vi nc ct thnh 500mL. Ch th h tinh bt 1%: Ho tan 0,49 g K2S2O3 trong 100mL nc m (t 80900C) khuy u cho n khi dung dch 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 mi l 1mL dung dch CdCl2 2%, y np l li 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 dch I2 0,01N. Chuyn dung dch 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 dch Na2S2O3 0,01N chun cho n khi dung dch 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 dch chuyn t mu xanh sang khng mu th dng li, ghi tng th tch V1 (mL) dch Na2S2O3 0,01N s dng. Lm tng t nh trn cho l cn li, ghi th tch V 2(mL) dch 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 dch I2 0,01N, lc u dung dch c mu vng nu . Dng dung dch Na2S2O3 0,01N chun cho n khi dung dch tr nn mu vng nht, cho 3 git ch th h tinh bt vo, lc u dung dch c mu xanh, tip tc chun cho n khi dung dch chuyn t mu xanh sang khng mu th dng li ghi th tch V0 Na2S2O3 0,01N s dng. Lm tng t nh trn cho bnh cn li ly th tch V0 trung bnh. Tnh kt qu
H 2 S (mg / L) =
172
(V0 VTB ) x N x 17 x 1000 125
Phn tch cht lng nc
VTB: Th tch trung bnh dung dch 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. 3.12.2Phng php Methylene blue Nguyn tc Nguyn tc ca phng php ny da trn phn ng ca sulfide (S 2-), 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 S 2c 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 dch PRE 1: 500mL HCl 37% pha thnh 1000mL vi nc ct. Dung dch A: Ha tan 4g C8H14Cl2N2 trong PRE 1 thnh 1000mL. Dung dch B: Ha tan 16g FeCl3.6H2O trong PRE 1 thnh 1000mL. Dung dch chun Dung dch 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 dch Na2S.9H2O 5mg/L: ha tan 5mL dd Na2S.9H2O 100mg/l vi 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.
173
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 vi 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 H 2S cha trong tng sulfide, t tnh ra hm lng H2S.
3.13 cng tng cng
Vic xc nh cng tng cng ca nc c thc hin theo phng php chun Complexon. 3.13.1Nguyn tc Trong mi trng pH=10 ion Ca2+ v Mg2+ s kt hp vi 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 vi ion Ca2+ v Mg2+ hnh thnh phc cht khng bn vng c mu hng ca ru vang. Khi dng EDTA chun , cc ion Ca 2+ v Mg2+ s kt hp vi 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 gii 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 dch m thng l NH4OH, NH4Cl.
174
Phn tch cht lng nc
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 3.13.3Thuc th Dung dch Na2H2Y (EDTA) tiu chun 0,1N: Cch 1:Ha tan 18,612 g EDTA (C10H14O8N2Na2.2H2O) (sau sy 80oC, ngui 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, ngui ti nhit phng, sau dng nc ct pha long thnh 1000mL, dung dch ny sau khi pha long xong phi chun li bng dung dch NaCO 3 tiu chun 0,1ppm bit nng chnh xc ca dung dch. Cch tin hnh nh sau: Dng buret 10mL dung dch CaCO3 tiu chun 0,1ppm, cho vo 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 dch c mu hng ru vang, dng dung dch Na2H2Y mi pha trn chun trn t cho n khi dung dch chuyn t mu hng ru vang sang mu xanh l th dng li, ghi th tch dung dch Na 2H2Y s dng. iu chnh nng dung dch Na2H2Y cho chnh xc bng biu thc: V1N1 = V2N2. Cch 2: Pha long 1 ng Na2H2Y (EDTA) 0,1N vi nc ct thnh 1000mL. Dung dch Na2H2Y 0,01N: ly 50mL dung dch Na2H2Y 0,1N dng nc ct pha long thng 500mL. Dung dch 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 dch MgSO4 0,05N v 0,5mL dung dch Na2H2Y 0,1N lc u. Dung dch CaCO3 tiu chun 0,1N: Ha tan 5 gam CaCO3 trong vi git dung dch HCl 1:1, pha long vi nc ct thnh 200mL, un si 5-10 pht, dng dung dch NH4OH iu chnh pH ca mi trng v bng 7 sau pha long vi nc ct thnh 1000mL. Dung dch 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 ci, chy thy tinh sch. Cn 0,5g
175
ch th Eriochrome black T cho vo 100g NaCl trn trn u v nghin mn, cho vo l nu y np kn. 3.13.4Tin hnh Trc khi tin hnh cn iu chnh 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 dch 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 dch Na2H2Y 0,01N chun t t cho n khi dung dch chuyn t mu hng ru vang sang mu xang l th dng li, ghi th tch dung dch Na2H2Y 0,01N s dng V. Lm li nh trn ln na ly gi tr V trung bnh. Nu s chuyn mu khng r, tc l trong dung dch c cc ion cn nh: Fe 3+, Cu2+ th cn tin hnh chun li vi mu nc khc v cch tin hnh nh sau: Sau khi cho 2mL dung dch m pH=10 vo mu nc ta cn thm vo 1mL dung dch KCN 5% che cc ion cn, sau mi thm cht ch th vo v tin hnh chun nh trn.
3.13.5 Tnh kt qu V xN x 50 x 1000 VM
cng tng cng (mg CaCO3/L)
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 di 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 vi 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 th trong nc c ion CO 32-. Phng php xc nh kim l phng php chun acid.
176
Phn tch cht lng nc
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 gi l kim carbonate. CO32- + H+ = HCO33.14.2 kim tng cng
Cho ch th methyl orange vo mu nc dung dch c mu vng cam. Chun bng dung dch H2SO4 0.01N cho n khi dung dch 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 vi 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 dch PRE 1: ha tan 27mL H2SO4 98% vi nc ct thnh 1000mL Phenolphtalein 1%: ha tan 1g Phenolphtalein trong 100mL C2H5OH Dung dch H2SO4 0,1N: ha tan 100mL PRE 1 vi nc ct thnh 1000mL hay pha long 1 ng H2SO4 0,1N chun vi nc ct thnh 1000mL. Dung dch methyl orange 0,1%: ha tan 0,1g methyl orange vi nc ct thnh 100mL Tin hnh ong 100mL mu nc cn phn tch vo bnh tam gic 250mL Thm vo 3 git dung dch Phenophthalein, dung dch c mu hng nht. Chun bng dung dch H2SO4 0,01N n khng mu, ghi th tch (V1 mL) H2SO4 001N s dng chun . Sau thm tip 3 git dung dch methyl orange, dung dch c mu vng cam. Tip tc chun bng dung dch 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. Tnh kt qu kim tng cng (mg/ CaCO3/L)
V xN x 50 x 1000 VM
177
V = (V1 + V2) : tng th tch dung dch H2SO4 0,01N cho c 2 ln chun N: nng ng lng dung dch 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 gia cc ion HCO 3-, CO32-, kh CO2 ha tan, do nc thng ng thi mang hai tnh cht i nhau: tnh acid v tnh kim. Trong thc nghim, hai khong pH chun c s dng biu th s khc bit trn tng ng vi hai lai cht ch th l methyl orange (pH = 4,24,5) v phenolphthalein (pH = 8,28,4) 3.15.1Nguyn tc Dng dung dch 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 vi 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 vi ch th phenolphthalein, dung dch t khng mu chuyn sang mu hng (tm)nht, c gi l acid tng cng 3.15.2Dng c v thit b Bnh tam gic 250mL ng ong 100mL Burett 3.15.3Chun b ha cht Dung dch NaOH tiu chun 0,1N: ha tan 1 ng chun NaOH 0,1N vi nc ct thnh 1000mL Dung dch NaOH 0,02N: Ly 200mL dung dch NaOH 0,1N ha tan cng vi 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
178
Phn tch cht lng nc
3.15.4Tin 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 dch 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 nc mu cho vo bnh tam gic, cho vo 3 git ch th phenolphthalein. Dung dch khng mu 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 3.15.5Tnh 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, Fe 2+ 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 vi SCN - hnh thnh mt 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 dch Thiocianate ammonium hay potassium: Ha tan 50g NH4SCN hay KSCN trong mt t nc ct sau pha long thnh 100mL.
179
Dung dch Potassium persulfate: Ha tan 1,7g K 2S2O8 trong mt t nc ct sau pha long thnh 100mL. HCl c d= 1,18 Dung dch 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 dch ny. Cho tng git KMnO4 0,1N vo cho n khi dung dch tr nn mu hng nht th dng li. Sau pha long thnh 1.000mL. Dung dch Fe3+ tiu chun 0,1mg/mL: Ly 50mL dung dch 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 cho vo mi bnh cc ha cht sau: Bng 7. 8. Tin trnh phn tch hm lng Fe tng s 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. 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 dch khng dch c mu mu. mu. Dng dung dch Fe3+ tiu chun 0,1mg/mL chun t t cho n khi dung dch c mu mu ging bnh 1 th dng li ghi th tch V1 dung dch Fe3+ tiu chun s dng. Lm li nh trn mt ln na ly gi tr V 1 trung bnh. Xc nh Fe2+ Ly 2 bnh tam gic 100mL, cng kch thc, ln lt cho vo mi 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 dch dch c mu mu. khng mu. Dng dung dch Fe3+ tiu chun 0,1mg/mL chun t t cho n khi dung dch c mu mu ging bnh 1 th dng li, ghi th tch
180
Phn tch cht lng nc
V2 dung dch Fe3+ tiu chun s dng. Lm li 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) =
3.16.2 Phng php o-phenanthroline
Nguyn tc St b kh thnh dng Fe2+ bng cch un si vi acid v hydroxylamine v c x l vi 1, 10 phenanthroline pH 3,2 - 3,3. 3 phn t phenanthroline to hp cht cng cua vi mi 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 dch A - HCl m c Dung dch B - Dung dch Hydroxylamine 10%: ha tan 10g NH2OH.HCl vi nc ct thnh 100mL. Dung dch C - Dung dch m pH = 5: ha tan 250g CH3COONH4 trong 150mL nc ct sau thm 700mL CH3COOH m c. Dung dch D - Thuc th o-phenanthroline: ha tan 0,1g o-phenanthroline trong 100mL nc ct lm nng 800C. Dung dch chun Dung dch Fe2+ 200mg/l: ho tan 1,4g Fe(NH4)2(SO4)2.6H2O vi 20mL H2SO4 m c vi 50mL nc ct. Sau thm vi git KMnO 4 0,1N dung dch s c mu hng nht, pha long thnh 1000mL. Dung dch Fe2+ 100mg/l: ong 50mL dung dch 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
181
(mg/l) 1 2 3 4 5 6 Tin hnh 0,0 0,4 0,8 1,2 1,6 2,0
Fe2+ 100mg/l (mL) 0,0 0,4 0,8 1,2 1,6 2,0
bin lc c S%o = S%o vi nc mu (mL) 100,0 99,6 99,2 98,8 98,4 98,0
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 ) 1mL dung dch A 1mL dung dch B Sau , em un trn bp cho cn cn khong 10-15mL, em ngui. nh mc li vi nc ct thnh 25mL, Tip tc thm vo 5mL dung dch C v 0,5mL dung dch 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 vi h s pha long s cho kt qu nng ca mu m ta cn o.
3.17 Silicate (SiO2)
3.17.1Nguyn tc SiO2 v cc dn xut ca n trong nc thng xc nh bng phng 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 ti di dng H2SiO3 (acid Silicic), acid Silicic s kt hp vi 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 3.17.2Thu 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 dch Molybdate ammonium 10%: Ha tan 10g (NH 4)2MoO4 hay (NH4)6Mo7O24.4H2O trong mt t nc ct nng pha long thnh 100mL, cho vo bnh polyethylene s dng.
182
Phn tch cht lng nc
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 thnh 100mL. 4. Dung dch Na2B4O7.H2O 1%: Ha tan 10g Na2B4O7.H2O trong mt t nc ct, sau pha long thnh 1000mL. 5. Dung dch K2CrO4 0,63%: Ha tan 0,63g K 2CrO4 trong mt t nc ct, sau pha long thnh 100mL. 3.17.4Tin hnh Ly 2 bnh tam gic 100mL, cng kch thc ln lt cho vo mi bnh cc ha cht nh sau: 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 dch K2CrO4 0,63% chun vo 1,5mL H2C2O4.2H2O 10%, t t cho n khi dung dch c mu vng lc u, dung dch c mu vng. ging nh bnh 1 th dng li, ghi th tch dung dch 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 vi 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 Ca 2+, Mg2+ (nc cng), trong mi trng baz mnh cc ion ny s to thnh cc hydroxide dng keo, lm cho dung
183
dch b vn c cn tr qu trnh so mu. khc phc hin tng trn, phi dng mui Seignett (KNaC4H4O6), hay EDTA (EDTA) cho vo mu nc phn tch, cc mui ny kt hp vi cc ion Ca2+ v Mg2+ hnh thnh cc hp cht ha tan, khng mu trong dung dch. M2+ + KNa C4H4O6 = K+ + Na+ + M C4H4O6 M2+ + Na2H2I = Na2MI + 2H+
Thuc th: Dung dch NH4Cl tiu chun N-NH4+ 1mg/mL: Ha tan 0,3822g NH4Cl trong mt t nc ct khng m (un nng 100 oC trong 2 gi), sau pha long thnh 100mL. Dung dch N-NH4+ tiu chun 0,01mg/mL: Ly 1mL dung dch 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 dch Seignett: Ha tan 50 g KNaC4H4O6.4H2O trong mt t nc ct khng m, sau pha long thnh 100mL. Dung dch 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 dch 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 nghim Dung dch N-NH4+ 0,01N mg/mL Nc ct khng m (mL) Mu nc Dung dch Seignett
184
thit lp mu chun phn tch TAN bng phng php 1 0,1 9,9 0 0,2 2 0,2 9,8 0 0,2 3 0,3 9,7 0 0,2 4 0,4 9,6 0 0,2 5 0,5 9,5 0 0,2 6 0,6 9,4 0 0,2 7 0,7 9,3 0 0,2 8 0,8 9,2 0 0,2 9 0,9 9,1 0 0,2 10 1,0 9,0 0 0,2 11 0 0 10 0,2
Phn tch cht lng nc
hay trion B (mL) Dung dch Nessler 1,0 (mL) Nng N-NH3 tng 0,1 s
1,0 0,2
1,0 0,3
1,0 0,4
1,0 0,5
1,0 0,6
1,0 0,7
1,0 0,8
1,0 0,9
1,0 1,0
1,0 ?
Ly ng nghim th 11 (mu nc) em so mu vi 10 ng cn li. Mu trong ng nghim th 11 trng vi mu ng nghim no th nng TAN (tng m amn) bng vi 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 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 3.18.2Phng php Indophenol Blue Nguyn tc Phn ng Berthelot da trn s th hin mu xanh ca dung dch khi ammonia phn ng vi phenol v alkaline hypochlorite v c gi l phng php Indophenol hoc phng php Phenate. Phng php ny c p dng cho phn tch mu nc thi vi 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 li phn ng vi ammonia to thnh Indophenol c mu xanh, c minh ha qua phng trnh sau:
2 - O- + NH3 + 3 ClOPhenol O- -N= = O + 2H2O + OH- + 3Cl-
Indophenol (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 dch. Nng
185
ca tng m amn - TAN (NH3 v NH4+) s c xc nh bi my so mu quang ph bc sng 630 nm (i vi 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 dch A: ha tan 4g phenol vi dung dch ethanol 95% thnh 500mL. Dung dch B: ha tan 0,375 g sodium nitroprusside (sodium nitroferricyanide) vi nc ct thnh 500mL. Dung dch C: ha tan 7,5 g trisodium citrate v 0,8g NaOH vi nc ct thnh 500mL. Dung dch D: dung dch oxy ho: Ly 2 mL sodium hypochlorite (NaOCl, 5%) pha vi dung dch C thnh 100mL (chun b ngay trc khi s dng). Dung dch chun Dung dch (NH4)2SO4 500mg/l: ho tan 0,2358g (NH4)2SO4 ) vi nc ct khng m thnh 100mL. Dung dch (NH4)2SO4 5mg/l: pha 1mL dd (NH4)2SO4 500mg/l) vi 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. STT Nng mu Th tch dung dch Th tch nc bin lc c chun (mg/l) (NH4)2SO4 5mg/L S = S ca mu nc (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 ti nhit phng khong 1-2 gi cho phn ng xy ra hon ton (mu th hin r).
186
Phn tch cht lng nc
Phn tch bc sng 640 m i vi 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 dch PRE 1: nc ct khng m Dung dch PRE 2: phenole stock solution: ho tan 312,5g phenol trong methanol thnh 500mL. Dung dch PRE 3: sodium hypochlorite 5% Dung dch PRE 4: dung dch NaOH 67.5%: ha tan 67,5g NaOH thnh 100mL nc ct khng m. Dung dch A- Ha tan 150g Na3PO4.12H2O v 150g C6H5O7.2H2O trong 1000mL nc ct khng m. Dung dch B- Ha tan 75mL PRE 2 vi 0.1g Na2[Fe(CN)5NO].2H2O trong 100mL nc ct khng m. Dung dch C- Ha tan 75mL PRE 3 vi PRE 4 thnh 100mL. Dung dch chun: Dung dch (NH4)2SO4 500mg/L: ha tan 0,2358g (NH4)2SO4 trong 100mL nc ct khng m. Dung dch (NH4)2SO4 5mg/L: pha 1mL dung dch (NH4)2SO4 500mg/L thnh 100mL vi 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. STT Nng mu chun Th tch dung dch Th tch nc ct khng (mg/l) (NH4)2SO4 5mg/l (mL) m (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
187
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 li bng cch pha long, sau khi ghi kt qu t my ta x l l vi 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 vi 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 ca mu (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 TAN c trong mu nc.
C= Ab a
3.19 Nitrite (NO2-)
3.19.1Nguyn tc Nitrite (NO2-) trong mi trng acid mnh s hnh thnh HNO 2, HNO2 mi hnh thnh s kt hp vi acid sulfanilique cho ra mui Diazonium sulfanilique. NaNO2 + 2HCl + HSO3-C6H4-NH2 = HSO3-C6H4-N=N-Cl+ NaCl + H2O Sau mui diazonium sulfanilique s kt hp vi 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 bi my so mu quang ph bc sng 543 m. Phng php ny c gi l phng php Griess llosvay, Diazonium. 3.19.2Cc 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.
188
Phn tch cht lng nc
Thuc th PRE 1: Cn 5g sulfanilic acid v 250g natri acetate ha tan vi nc ct thnh 500mL. PRE 2: ha tan 0,5g 1-naphthylamine v 25mL acetic acid vi nc ct thnh 500mL. Dung dch A: Ha tan 100mL PRE 1 vi 100mL PRE 2. Dung dch B: Dung dch acetic acid nguyn cht. Dung dch chun Dung dch NaNO2 500mg/l: ha tan 0,2463g NaNO2 trong 100mL nc ct. Dung dch NaNO2 5mg/l: ha tan 1mL dd NaNO2 500mg/l vi nc ct 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 7.15. 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
189
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 mui tng ng vi nng mui ca mu nu phn tch mu nc l. Ch , nu mu hng qu m ta nn lm li bng cch pha long, sau khi ghi kt qu t my ta x l l vi 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 bi CuSO4. NO2- mi hnh thnh v NO2- sn c trong nc s c xc nh bi phng php diazonium. Kt qu thu c t phng php kh Cadmium l tng hm lng ca N-NO3-/N-NO2-, mun tnh hm lng N-NO3- th ly tng hm lng ca N-NO3-/N-NO2- tr i cho hm lng N-NO2-.
3.20.2 Phng php phenoldisulfonic acid
Nguyn tc Nitrate (NO3-) c trong nc tc dng vi 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
HSO3
OH + NO3 SO3H
-
HSO3
OH
NO2
+ H2O
(1)
SO3H Nitrophenol dissulfonic (phc cht khng mu) O N- OK + 3H2O SO3H (2)
Phenol dissulfonic acid OH
HSO3
NO2 + 3KOH
HSO3
SO3H
Thuc th
190
phc cht mu vng
Phn tch cht lng nc
Dung dch 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 dch NH4OH nguyn cht (khong 25%). Nu khng c, c th thay bng 68 g KOH ha tan thnh 100mL vi nc ct. Dung dch Nitrate tiu chun N-NO2- 0,01 mg/mL: Ha tan 0,722g KNO3 (sau khi sy kh 105oC v ngui 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 mi ng nghim cc ha cht sau: 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 dch 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 dch 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 NO 3th trong chn s c kt ta. Ha tan kt ta bng 1 mL dung dch 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 vi 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. 3.20.3Phng 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 dch A - Ha tan 5g natri salicylate thnh 1000mL vi nc ct.
191
Dung dch B - Dung dch H2SO4 98% Dung dch C - Ha tan 100g C4H4KNaO6.4H2O thnh 1000mL vi nc ct. Dung dch D - Dung dch NaOH 10N: ha tan 400g NaOH thnh 1000mL vi nc ct. Dung dch chun Dung dch KNO3 500mg/l: ha tan 0,3609g KNO3 trong 100mL nc ct. Dung dch KNO3 50mg/l : ha tan 10mL dd KNO3 500mg/l thnh 100mL vi 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: 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 Nng mu chun Th tch dung dch Th tch nc bin lc c (mg/l) KNO3 50mg/L (mL) S%o = S%o ca mu (mL) 1 0,0 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 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.
192
Phn tch cht lng nc
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 vi 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 hi qui tnh ra nng ca mu
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 vi 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 dch Amonium molybdate Cn 25 g (NH4)6Mo7O24.4H2O ha tan trong 175 mL nc ct ong 280mL H2SO4 m c pha vi 400mL nc ct, ngui Trn ln hai dung dch li ri pha long vi nc ct thnh 1000mL Dung dch SnCl2 Cn 2,5g SnCl2.H2O ha tan trong 100mL Glycerin (Cung cp nhit). Bo qun dung dch t lnh Dung dch chun P-PO43Dung dch KH2PO4 500mg/l: ha tan 0,2197g KH2PO4 trong 100mL nc ct Dung dch KH2PO4 5mg/l: ha tan 1mL dd KH2PO4 500mg/l thnh 100mL vi nc ct Thit lp mu chun
193
Chn 6 bnh tam gic c dung tch 100mL, cng kch thc, khng mu ln lt cho vo cc ha cht sau: 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 vt cht l lng c trong nc vo bnh tam gic, cng vi 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 hi qui tng quan gia hp th quang v nng cht tan cn phn tch tng t nh 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 vi 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 bi my so mu quang ph bc sng 880 m. Thuc th H2SO4 5N: Pha 70 mL H2SO4 m c vi nc ct thnh 500 mL. Dung dch Potassium antimonyl tartrate: Ha tan 0,12 g K(SbO)C4H4O6.1/2H2O trong 400 mL nc ct. sau pha long thnh 500 mL.
194
Phn tch cht lng nc
Dung dch ammonium molybdate: ha tan 20 g (NH4)6Mo7O24.4H2O trong 500 mL nc ct. 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 vi 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 loi thuc th theo th t nu trn. Cho php cc thuc th trn nhit phng trc khi phi hp. Nu c xut hin trong thuc th hn hp th lc u ri yn cho n khi c khng cn xut hin. Thuc th ny n nh trong 4 gi. Dung dch m (stock phosphate solution): Ha tan 219,5 mg KH2PO4 trong 1000mL nc ct c dung dch c nng cht chun l 50 g/mL hay 50 mg/L Dung dch chun (Standard phosphate solotion): Ha tan 50 mL dung dch m vi 1000 mL nc ct c c dung dch 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 dch 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 ngoi 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.
195
3.22 Tng m (TN) v tng ln (TP)
3.22.1Phng php Kjeldahl Nguyn tc Cc dng m hu c b oxy ha bi acid H 2SO4 m c vi 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 dch 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 mi 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 loi 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 si loi chuyn dng cho qu trnh cng ph (chng nc b bn ra ngoi khi si) vo mi ng. thm mi ng mu nc v mu trng 10 mL H2SO4 m c, trn u, i n khi mu ngui li.
ii. Sau khi ngui, 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. iii. t cc ng mu v gi ln my cng ph.

iv. M my cng ph v my ht (qu trnh cng ph nc bc hi nn phi dng
my ht).
v. Ci t chng trnh iu khin nhit :
Temp1 = 110oC, gi nhit ny trong vng 20 pht (khng k thi gian nhit tng t nhit phng ln 110oC).
196
Phn tch cht lng nc
Temp2 = 200oC, gi trong vng 20 pht (khng k thi 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 375 oC. Nhit cng cao th 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 ngui hon ton, pha long phn acid
sulphuric cn li trong ng vi 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 para-nitro-phenol (4-nitrophenol), sau chun li mi trng acid bng vi git dung dch H2SO4 20%; Dung dch sau cng c thm 1 git H 2SO4 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 , vi phng php cng ph Kjeldahl, kt qu hm lng m thu 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 TN = TKN + N-NO2- + N-NO3Nu trc khi cng ph mu chng ta loi 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 mi 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 li 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.
197
ii. Sau khi ngui, thm10 mL H2O2 m c, mu qua m trc khi cng ph.
iii. t cc ng mu v gi ln my cng ph. iv. M my cng ph v my ht (qu trnh cng ph nc bc hi nn phi dng my ht).
v. Ci t chng trnh iu khin nhit :
Temp1 = 110oC, gi nhit ny trong vng 30 pht (khng k thi gian nhit tng t nhit phng ln 110oC). Temp2 = 200oC, gi trong vng 30 pht (khng k thi gian nhit tng t 110oC ln 200oC). Temp3 = 375oC, gi nhit ny n khi mu cng ph c mu trng 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 lm lnh hon ton, pha long phn acid
sulphuric cn li trong ng mt cch cn thn vi 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 git 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 vi 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 ri pha thnh 1000 mL
198
Phn tch cht lng nc
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 vi nc ct. Bo qun trong chai, l mu nu trnh nh sng. 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 121 oC 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 phng 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.
199

Chuong7CAF002

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chuong7CAF002

Uploaded by

Copyright:

Available Formats

Phn tch cht lng nc

PHN TCH CHT LNG NC

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Hnh 7-2. Cc ph ca sng in t

Qun l cht lng nc nui trng thy sn

1.2.3 S tng tc gia vt cht v bc x in t

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

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

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

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 dch chun:

Phn tch cht lng nc

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

C th c kt qu trn th hoc s dng phng trnh hi qui c dng:

Qun l cht lng nc nui trng thy sn

A = aC + b Ax = b Cx = b/a 1.3.3 Phng php ng chun

(hi quy tuyn tnh y = ax + b)

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

A1 = 0,475. A2 = 0,130. A3 = 0,175

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

Phn tch cht lng nc

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+ + InK=

[ H + ][ In ] In pK = pH lg = pH lg HIn 1 HIn 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.

La chn v ra k chai, l ng mu.

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

2.3 Phng php thu mu

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

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

ISS (mg / L) = TSS OSS

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

2. 3 git ch th phenolphthlein, lc u, dung dch c mu hng nht.

2. 3 git ch th phenolphthlein, lc u, dung dch khng mu.

tch V2 (mL) dung dch NaOH 0,01N s dng.

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

P (mg O2/L/ngy) = DOCS DOCT

Qun l cht lng nc nui trng thy sn

Phn tch cht lng nc

Qun l cht lng nc nui trng thy sn

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