Hoa Hoc Moi Truong

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LI NI U
Theo nguyn vng ng o ca tt c cc sinh vin, cn b ngnh mi trng. Sau mt
thi gian bin son v hiu chnh, GREE xin gii thiu n cc bn b gio trnh Ho
Mi Trng. B gio trnh ny gm cc phn sau:
CHNG 1 PH
1.1 Gii thiu chung
1.2 L thuyt pH
1.3 o pH
1.4 Phn tch s liu Ph
CHNG 2
ACID
2.1 Khi nim chung

2.2 Ngun gc v tnh cht ca acid
2.3 Y ngha ca acid Carbonic & Acid
2.4 Phng php xc nh
2.5 ng dng s liu v acid
CHNG 3
KIM
3.1 Khi nim chung

3.2 ngha mi trng
3.3 Phng php xc nh kim
3.4 Cc phng php biu din kim
3.5 Mi quan h gia carbonic, kim & pH trong nc t nhin
3.6 Ap dng s liu v kim
3.7 Mt s p dng khc ca kim i vi k s mi trng
CHNG 4
OXY HA TAN
4.1 Khi nim chung

4.2 ngha mi trng ca oxy ha tan
4.3 Ly mu xc nh oxy ha tan
4.4 La chn ha cht tiu chun o oxy ha tan
4.5 Phng php xc nh oxy ha tan
4.6 Phng php in cc mng o oxy ha tan
4.7 p dng s liu oxy ha tan
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CHNG 5
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NHU CU OXY SINH HO
5.1 Gii thiu chung

5.2 Bn cht ca phn ng BOD
5.3 Phng php xc nh BOD
5.4 Vn tc ca qu trnh oxy ha sinh ha
5.5 S khc nhau gia cc gi tr L & nhng gi tr nhu cu oxy theo l
5.6 thuyt
5.7 S khc nhau gia tc quan st c & tc bc 1
ng dng s liu BOD
CHNG 6
NHU CU OXY HA HC
6.1 Gii thiu chung

6.2 Cc phng php phn tch COD dng
6.3 Phn tch COD bng K2Cr2O7
CHNG 7
ST & MANGAN
7.1 Gii thiu chung

7.2 Phng php xc nh
7.3 ng dng ca s liu Fe & Mn
CHNG 8
SULFATE
8.1 Gii thiu chung

8.2 Cc phng php phn tch
8.3 ng dng s liu sulfate
CHNG 9
PHOSPHORUS & PHOSPHATE
9.1 Gii thiu chung

9.2 Tm quan trng ca hp cht Phosphorus
9.3 Cc phng php xc nh Phosphorus Phosphate
9.4 ng dng nhng s liu v phosphorus
Hy vng b gio trnh ny s gip ch nhiu cho cc bn trong qu trnh hc tp cng

nh l ngun ti liu tham kho cho cc bn trong qu trnh cng tc sau ny.
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y cng l ln u tin, cun sch in t ny c xut bn do , s khng trnh

khi nhng thiu st. cho cun sch ngy cng hon thin, phc v nhu cu thit
thc ca ng o sinh vin v cn b chuyn gia trong ngnh, xin cc bn phn hi
nhng sai st cho chng ti qua a ch tamnhinxanhvietnam@yahoo.com
TP.HCM ngy 22 thng 12 nm 2006

Ban bin tp
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CHNG 1
PH
1.1 GII THIU CHUNG
Thut ng pH c s dng rng ri biu din tnh acid hoc tnh kim ca dung
dch. pH l ch s biu din nng ca ion hydro, hay ni chnh xc hn l nng
hot tnh ca ion hydro. pH c vai tr quan trng trong hu ht cc qu trnh ca lnh
vc k thut mi trng. Trong lnh vc cp nc, pH l yu t quan trng nh hng
n qu trnh keo t ha hc, kh trng, lm mm v kim sot tnh n mn ca nc.
Trong x l nc thi bng cc qu trnh sinh hc, pH phi c duy tr trong gii hn
ti u cho s pht trin ca vi sinh vt. Cc qu trnh ha hc s dng keo t nc
thi, lm kh bn hoc oxy cc hp cht nh ion cyanua, thng i hi pH phi c
duy tr trong mt gii hn hp. V nhng l do trn v v cc mi quan h c bn gia
pH, acid v kim, cn phi hiu bit v l thuyt cng nh thc t pH.
1.2 L THUYT pH
Khi nim v pH c pht trin t hng lot cc nghin cu dn n hiu bit y
hn v acid v base. Vi s khm ph ca Cavendish nm 1366 v hydro, ngay sau
mi ngi u bit tt c acid cha nguyn t hydro. Cc nh ha hc tm thy rng
cc phn ng trung ha gia acid v base lun lun to thnh nc. T khm ph trn
v cc thng tin lin quan, ngi ta kt lun rng base cha cc nhm hydroxyl.
Nm 1887 Arrhenius thng bo l thuyt ca ng v s phn ly thnh ion (ionization).
T n nay acid c coi l cc cht khi phn ly to thnh ion hydro v base khi
phn ly to thnh ion hydroxyl. Theo khi nim ca Arrhenius, trong dung dch, acid
mnh v base mnh c kh nng phn ly cao, acid yu v base yu c kh nng phn
ly km trong dung dch nc. S ra i v pht trin cc thit b thch hp o nng
hoc hot tnh ca ion hydro chng minh l thuyt trn.
o hot ca ion hydro
in cc hydro l thit b thch hp o hot tnh ca ion hydro. Cng vi vic
s dng in cc hydro, ngi ta tm thy rng nc tinh khit phn ly cho nng ion
hydro cn bng khong 10-7 mol/l.
H2O H+ + OH-
(1 1)
ThS: Huynh Ngoc Phng Mai

Copyright 2006 gree-vn.com, All rights reserved. Xin ghi r ngun khi bn pht hnh li thng tin t trang ny.
1-1
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V nc phn ly to thnh mt ion hydroxyl v mt ion hydro nn r rng rng c

khong 10-7 mol/l ion hydroxyl cng c to thnh. Thay th vo phng trnh cn
bng ta c:
{H }{OH } = K
+
(1 2)
{H 2 O}
Nhng v nng ca nc l rt ln ([6,02 x 1023 x 1.000/18] mol/l) v gim i rt t

do b phn ly nn c th c xem l hng s (hot tnh ca n tng ng vi 1,0)
v phng trnh (1 2) c th c vit thnh:
{H+} {OH-} = Kn
(1 3)
v i vi nc tinh khit 200C,

{H+} {OH-} = 10-7 x 10-7 = 10-14
Hng s ny l tch ion hoc hng s phn ly ca nc.
Khi cho vo nc mt acid, n phn ly trong nc v hot tnh ion hydro tng ln;
tip theo, hot tnh ion hydroxyl phi gim xung tun theo hng s phn ly. V d,
nu acid c cho vo nc tng nng hot tnh {H+} n 10-1 th nng hot
tnh {OH-} phi gim n 10-13, c:
10-1 x 10-13 = 10-14
Ngc li, nu base c cho vo nc tng nng {OH-} n 10-3 th nng
{H+} gim n 10-11. V mt ghi nh quan trng l {OH-} v {H+} khng bao gi gim
n zero.
Khi nim c bn pH
Vic biu din hot tnh ion hydro di dng nng mol l khng thun tin.
khc phc kh khn ny, nm 1909 Sorenson kin ngh biu din nng hot tnh ca
ion hydro di dng logarithm m v k hiu l pH+. K hiu ca ng c thay th
bng k hiu n gin hn l pH v c biu din bng
pH = - log{H+} hoac pH = log
1
+
{H }
(1 5)
v pH thng nm trong dy t 0 n 14, vi pH 7 250C biu din tnh trung ha

tuyt i.

1-2
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Day acid
0
Day kiem
7
14
Thang pH
V hng s Kn thay i theo s thay i nhit , nn pH ca tnh trung ha cng thay
i cng vi nhit , l 7,5 00C v 6,5 600C. Tnh acid tng khi gi tr pH gim v
tnh kim tng khi gi tr pH tng.
1.3 O pH
in cc hydro l tiu chun tuyt i o pH. Nhng n khng thun li v khng
thch ng c vic s dng rng ri, c bit trong cc nghin cu ngoi hin trng
hoc i vi cc dung dch c cha cc cht hp ph ln platin en. S thay i ca
cc cht ch th c chun vi in cc xc nh tnh cht mu ca chng
cc mc thay i ca pH. T nhng nghin cu ny, c th xc nh mt cch chnh
xc vic chn cht ch th c kh nng thay i mu mt cch ng k trong dy pH
c lin quan. Vic s dng cht ch th c thay th bng vic pht trin in cc thy
tinh.
Khong nm 1925, ngi ta tm thy in cc c th c ch to bng thy tinh v
c kh nng o c hot tnh ca ion hydro m khng b nh hng ca hu ht
cc ion khc. Vic s dng n tr thnh phng php tiu chun o pH.
o bng in cc thy tinh

Cc loi my o pH s dng in cc thy tinh do nhiu cng ty ch to. Chng thay
i t cc loi my pH cng trng s dng pin vi gi vi trm USD n cc loi thit
b c chnh xc cao vi gi hn ngn USD. Cc loi my o pH s dng in 110V
c ch to t nhng nm 1940 v p ng c hu ht cc yu cu ca phng th
nghim, chng c kh nng o c pH vi chnh xc 0,1 n v. Cc my o pH di
ng s dng pin thch hp vi vic i cng trng.
Vic o pH c th c thc hin trong rt nhiu loi vt liu v cc iu kin rt
khc nhau, iu ny cho thy phi lu n loi in cc. Vic o cc gi tr pH cao
hn 10 v nhit cao tt nht c thc hin vi cc in cc thy tinh c bit.
Cc thit b o pH thng c chun bng cc dung dch pH chun.

1-3
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1.4 PHN TCH S LIU pH

S liu pH lun lun c phn tch di dng hot tnh ca ion hydro, l s o ca
tnh acid hoc kim ca dung dch. Mt cch gn ng, c th gi thit nng ca ion
hydro {H+} = {H+} nng hot tnh ca ion hydro. V vy,
pH = 2
pH = 10
pH = 4,5
{H+} = 10-2
{H+} = 10-10
{H+} = 10-4,5
pH khng o acid tng cng hoc kim tng cng. iu ny c th c trnh

by bng vic so snh pH ca dung dch acid sulfuric v acid acetic N/10. pH ca dung
dch acid sulfuric khong 1 v n c phn ly mnh hn v pH ca dung dch acid acetic
khong 3 v n phn ly yu hn.
Trong mt vi th d pOH, hoc hot tnh ca ion-hydroxyl, ca dung dch l mi quan
tm chnh. Ngi ta thng tnh pOH bng cch s dng mi quan h cho trong
Phng trnh (1-3). Php tnh gn ng c thc hin t mi quan h:
hoc
pH + pOH = 14
(1 - 6)
pOH = 14 pH
(1 - 7)
[OH-] v [H+] ca dung dch khng bao gi gim n zero.

Khi nim c bn ca pOH, hoc hot tnh ca ion hydroxyl l c bit quan trng
trong cc phn ng kt ta lin quan n vic to thnh hydroxide. V d, vic kt ta
Mg2+ trong qu trnh lm mm nc bng vi v trong qu trnh keo t ha hc s
dng phn st v phn nhm.

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CHNG 2
ACID
2.1 KHI NIM CHUNG

Hu ht cc ngun nc thin nhin, nc thi sinh hot v rt nhiu loi nc thi
cng nghip c kh nng m do h thng carbonic-bicarbonate. Trn c s ca thng
tin ny, ngi ta thng xem xt rng tt c cc ngun nc c pH nh hn 8,5 u c
acid. Thng thng im kt thc phenolphthalein ti pH 8,2 n 8,4 c s
dng nh im tham kho. Kho st ng cong ca acid carbonic cho thy rng pH
7,0 carbonic cn li phi c trung ha. N cng cho thy rng bn thn carbonic s
khng lm gim pH xung di 4.
T ng cong nh phn ca cc acid mnh v tnh cht ca ng cong, ngi ta
c th kt lun rng vic trung ha ca acid kt thc ti pH 4. V vy, t tnh cht ca
ng cong nh phn acid carbonic v acid mnh, r rng l acid ca nc t
nhin l do acid carbonic hoc acid v c mnh gy ra, acid carbonic nh hng i
vi nc c pH ln hn 4 v acid mnh c nh hng vi nc c pH nh hn 4, nh
trnh by trong Hnh 2.1.
2.2 NGUN GC V TNH CHT CA ACID
Acid carbonic l thnh phn ch yu ca tt c nc t nhin. N ha tan vo nc
mt bng qu trnh hp th t kh quyn ph thuc vo nh lut Henry, nhng ch khi
nng ca acid carbonic nh hn s cn bng ca carbonic trong khng kh.
Carbonic cng c th to thnh trong nc thng qua vic oxy ha sinh hc cc cht
hu c, c bit trong nc b nhim. Trong nhng trng hp nh vy, nu cc
hot ng quang hp b hn ch, nng ca carbonic c th vt qua cn bng v
kh carbonic s t nc thot vo khng kh. V vy ngi ta i n kt lun rng nc
mt hp th hoc gii phng mt cch cn bng kh carbonic gi cn bng vi
khng kh. Khi lng kh carbonic trng thi cn bng l rt nh v p sut ring
phn ca kh carbonic trong khng kh l rt thp.

2-1
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10
9
iem ket thuc phenolphthalein
8
7
6
Day cua o acid carbonic
5
4
iem ket thuc methyl cam
3
2
Day thc te cua o acid vo c
1
Hnh 2.1 Cc loi acid quan trng trong nc bnh thng v nc thi.
Nc ngm v nc t vng cc i lu ca h cha phn tng thng cha mt
lng ng k kh carbonic. Nng ny l kt qu ca vic phn hy sinh hc cc
cht hu c c trong nc di s hot ng ca vi sinh vt, trong iu kin ny kh
carbonic khng th t do gii phng vo kh quyn. Kh carbonic l sn phm cui cng
ca c qu trnh phn hy sinh hc hiu kh v k kh; v vy, nng ca n khng b
gii hn bi khi lng oxy ha tan ban u. Thng nc ngm c nng kh
carbonic khong 30 50 mg/L. Nc ngm ca thnh ph H Ch Minh v cc tnh
ng bng sng Cu Long thng c nng kh carbonic t 80 120 mg/L, nhiu ni
tng nc ngm mch su (200 300 m) nng CO2 c th ln n 320 mg/L.
iu ny c bit ng i vi nc thm qua cc lp t khng cha carbonate
canxi v magne trung ha carbonic qua vic to thnh carbonate.
CO2 + CaCO3 + H2O Ca2+ + 2HCO3-
(2 1)
Acid v c c mt trong nhiu loi cht thi cng nghip, c bit trong cc loi cht
thi cng nghip luyn kim v mt phn t sn phm cc loi vt liu hu c tng hp.
Cc ngun nc thin nhin cng c th cha acid v c. Nc thi t cc khu vc
hm m v ni qung s cha mt lng ng k acid sulfuric hoc mui ca acid
sulfuric nu c mt lu hunh, sulfide hoc pyrit st. Vic chuyn ha cc vt liu ny
thnh acid sulfuric v sulfate do vi khun oxy ha lu hunh thc hin trong iu kin
hiu kh.
2S + 3O2 + 2H2O
FeS2 + 1,5O2 + H2O
Vi khuan
4H+ + 2SO42-
(2 2)
Vi khuan
Fe2- + 2H+ + 2SO42-
(2 3)

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Mui ca kim loi nng, c bit l cc ion kim loi ha tr ba, nh Fe (III) v Al (III) thy
phn trong nc gii phng acid v c.
FeCl3 + 3H2O Fe(OH)3 + 3H+ + 3Cl-
(2 4)
S c mt ca cc kim loi nng c ch th bng vic to thnh kt ta khi pH ca

dung dch cha cc kim loi trn c tng ln khi trung ha.
Nhiu cht thi cha acid hu c. S c mt v tnh cht ca chng c th c xc
nh bng cch s dng ng cong nh phn nh tnh hoc sc k kh.
2.3 NGHA CA ACID CARBONIC V ACID
acid t c quan tm nht trong lnh vc v sinh hc hoc sc khe cng ng.
Kh carbonic trong nc ngt v bia nng cao hn rt nhiu cho vi cc ngun
nc thin nhin v khng nh hng c hi n sc khe. Nc cha acid v c
thng khng ngon.
Nc acid c quan tm v tnh n mn ca chng v chi ph trong vic x l cc cht
n mn. Carbonic l yu t gy n mn hu ht cc loi nc t nhin, nhng trong
rt nhiu loi nc thi cng nghip acid v c l nguyn nhn gy ra tnh n mn ny.
Kh carbonic phi c tnh ton n trong qu trnh lm mm nc khi s dng vi
soda.
Trong qu trnh x l sinh hc, pH phi c duy tr trong khong t 6 n 9,5. Tiu
chun ny thng i hi vic iu chnh pH ti mc thch hp v trong nhiu trng
hp vic tnh ton khi lng ha cht cn thit da trn gi tr acid.
Qu trnh t nhin liu ha thch trong cc nh my nhit in v xe t dn n vic
to thnh oxit nit v oxit lu hunh. Khi ha tan trong nc ma chng thy phn to
thnh acid sulfuric v acid nitric. Kt qu l ma acid lm gim pH trong cc h nc
c kh nng m thp, nh hng xu n i sng di nc v c th lm tng khi
lng ha cht nh nhm, st, silic ha tan t t vo nc b mt. V nhng l do
ny, vic kim sot oxit lu hunh v nit cn c thc hin khi thi cc loi kh t
vo mi trng khng kh.
2.4 PHNG PHP XC NH
acid carbonic v acid v c c th c xc nh bng vic s dng cc dung dch
kim tiu chun. Acid v c c o bng nh phn n pH khong 3,7 vi im kt
thc methyl cam. Kt qu nh phn mu nc n im kt thc phenolphthalein vi
pH 8,3 xc nh c acid v c v acid do cc acid yu gy nn. acid tng
cng ny c tn l acid phenolphthalein.
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acid carbonic
Nu mun c kt qu tin cy vi chnh xc cao, cn phi c bit lu khi ly mu,
bo qun mu v phn tch mu xc nh nng carbonic, khng tnh n phng
php phn tch. Trong cc ngun nc m carbonic ng vai tr quan trng, p sut
ring phn ca n thng ln hn nhiu ln p sut ca kh carbonic trong kh quyn;
v vy khi tip xc vi khng kh phi trnh hoc gi mc tht thot mc nh nht.
V l do ny, vic phn tch c th c thc hin tt nht ngay ti ni ly mu, trnh
c vic tip xc vi khng kh v s thay i ca nhit .
Mu nc phi c ly tng t nh khi ly mu xc nh oxy ha tan, chng hn
dng ng hoc pipet ngp trong nc trnh cc bt kh v cho php bnh cha mu
chy trn v cho nc thay th ch ca khng kh. Nu mu phi vn chuyn v
phng th nghim phn tch, chai ly mu phi c y kn khng kh khng lt
c vo chai. Nhit phi c gi gn vi nhit ti ni ly mu.
Phng php nh phn. gim n mc thp nht vic tip xc vi khng kh,
tt nht nn ly mu v nh phn trong cc ng nh mc hoc ng so mu. ng so
mu hoc ng nh mc phi c chy trn v vic ly mu vi th tch thch hp
c thc hin bng cch s dng siphon hoc pipet. Sau khi b sung khi lng
thch hp cht ch th phenolphthalein, tin hnh nh phn ngay gim n mc thp
nht s tht thot kh carbonic vo khng kh. Thng thng, ban u mt khi lng
ng k ca kh carbonic s b tht thot do phi khuy trong mu. Kt qu tin cy hn
c th thu c bng vic ly mu ln hai v thm mt khi lng cht nh phn
bit trc khi tin hnh khuy trn. Vic nh phn c th hon thin vi vic tht thot
kh carbonic l khng ng k. im kt thc cui cng s xut hin rt chm, do
vic nh phn s ch kt thc hon ton khi mu hng tn ti 30 giy.
Khi hydroxide natri c s dng lm cht chun, cn phi chc chn rng n khng
cha carbonate natri. Phn ng c lin quan n qu trnh trung ha xy ra theo hai
bc.
2NaOH + CO2 Na2CO3 + H2O
Na2CO3 + CO2 + H2O 2NaHCO3
(2 5)
(2 6)
v t Phng trnh (2 6) r rng l nu carbonate natri c mt trong hydroxide natri

s gy nn sai s trong kt qu phn tch. khc phc kh khn ny, dung dch
carbonate natri l mt trong nhng cht nh phn chun c gii thiu o acid
carbonic. Carbonate natri c th c s dng theo kh nng ny v phn ng mt
cch nh lng vi acid carbonic, nh trnh by trong Phng trnh (2 6). N c u
im nht nh l c th mua di dng tinh khit phn tch (PA).
Tnh ton t pH v kim. C kh nng tnh ton khi lng carbonic trong
mu nc t phng trnh phn ly ca acid carbonic. Khi pH thp hn 8,5, hng s
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phn ly bc mt ca acid carbonic c th c s dng cho bit nng ion hydro,

nng ion bicarbonate v hng s phn ly K1:
[H+] [HCO3-]
*
[H2CO3 ]
= KA1
(2 7)
Thc t, [H2CO3*] trong phng trnh ny c thit lp tng ng vi tng nng

mol ca acid carbonic v carbonic t do v rt kh phn bit gia hai dng trn ca acid
carbonic. V carbonic t do chim khong 99 phn trm tng nng , phng trnh
trn ch l phng trnh gn ng.
Vic s dng Phng trnh (2 7) c m t trong v d sau.
Nu KAl = 4,3 x 10-7, [H+] =10-7 v [HCO3-] = 4,3 x 10-7, th nng CO2 phi bng
(10-7) x (4,3 x 10-3) / (4,3 x 10 - 7) = 10-3 mol/L hoc 44 mg/L. Mc d vy, tnh ton
trn c chnh xc, cn phi k n nh hng ca cc ion khc v nh hng ca
nhit n hng s K1. T nhng nhn xt trn c th thy rng vic tnh ton kh
carbonic t do trong nc l mt qu trnh phc tp, v vy trong hng dn Standard
methods c trnh by th xc nh carbonic t do t pH, kim, cht rn ha
tan v nhit .
Vic xc nh carbonic t s o pH v kim c th cho kt qu vi chnh xc
cao, nhng khng thc s cn thit. Phng php gp phi kh khn l phi bit nng
cht rn ha tan. iu ny i hi phi phn tch ring bit bng phng php trng
lng hoc dn. Tng t, pH phi c o vi chnh xc cao, v thay i nh
s dn n sai s ln.
V d, pH sai s 0,1 s dn n sai s 25 phn trm khi xc nh carbonic. N tr thnh
cu hi xem kt qu tnh ton ny di iu kin phng th nghim bnh thng ha
trn hin trng c tin cy hn kt qu thu c bng qui trnh nh phn hay
khng, khi vic quan tm thch hp c thc hin n cc m t chi tit cho phng
php nh phn. Xem xt cc kh khn ca mi phng php, ngi ta thy rng qui
trnh nh phn thng l phng php c la chn khi nng carbonic ln hn 2
mg/L, trong khi i hi cc nng nh hn sai s s ln hn, v vy qui trnh tnh
ton c kin ngh thc hin.
Phng php hin trng. Phng trnh nh phn c rt nhiu u im v tnh
chnh xc cho tt c cc mc ch thc t.
Acid Methyl Cam
Tt c nc thin nhin v hu ht cc loi nc thi cng nghip c pH thp hn 4
u c acid v c hoc acid methyl cam. Acid v c cn c trung ha ti thi
im pH tng ln 3,7 v cht ch th pH mu thng c s dng khi my o pH
khng c sn. Trong khi , trc y methyl cam c s dng cho mc ch ny,
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nhng hin nay bromphenol c kin ngh s dng v s thay i mu r nt hn

pH 3,7. Kt qu c trnh by trong khi nim acid methyl cam nh CaCO3. V
CaCO3 c ng lng l 50, dung dch N/50 NaOH c s dng lm cht nh
phn, do 1 mL tng ng vi 1 mg acid.
acid phenolphthalein
i khi, cn phi o acid tng cng ca acid v c v acid yu trong mu nc. V
hu ht cc acid yu c trung ha pH 8,3 nn c cht ch th phenolphthalein v
metacresol mu ta c th c th s dng trong vic nh phn. Khi c mt ca cc
mui kim loi nng, ngi ta thng un nng mu v nh phn. un nng mu lm
tng tc thy phn ca mui kim loi, cho php vic nh phn kt thc nhanh chng
hn. Mt ln na, dung dch N/50 NaOH c s dng lm cht nh phn v kt qu
c trnh by di dng acid phenolphthalein nh CaCO3.
2.5 NG DNG S LIU V ACID
Vic xc nh nng carbonic c bit quan trng trong lnh vc cp nc. Trong vic
pht trin cc ngun nc cp mi, n l yu t quan trng cn phi c cn nhc
trong cc phng php v cng trnh x l. Nhiu ngun nc ngm yu cu phi x
l trnh hin tng n mn do carbonic gy ra. Khi lng ca kh carbonic trong
nc l yu t quan trng xc nh xem vic kh kh c thc hin bng lm
thong hay bng trung ha vi vi hoc hydroxide natri. Kch thc ca cc thit b,
liu lng ha cht, kho d tr v gi thnh x l ph thuc vo khi lng ca
carbonic c mt trong nc. Nng carbonic l thng s quan trng c tnh nhu
cu ha cht nh vi hoc soa.
Hu ht cc cht thi cng nghip cha acid v c u phi c trung ha trc khi
chng c x vo sng hoc ng ng thot nc hoc n trm x l. Khi lng
ha cht, kch thc ca cc thit b chm ha cht, kho lu tr v gi thnh c xc
nh a vo s liu v acid ca phng th nghim.

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CHNG 3
KIM
3.1 KHI NIM CHUNG

kim l s o kh nng trung ha acid ca nc. i khi khi nim kh nng trung
ha acid thay th cho khi nim kim cng c s dng trong mt s ti liu.
kim ca nc t nhin do mui ca cc acid yu gy nn, mc d cc cht kim yu
v kim mnh cng c th gy ra kim. Bicarbonate l dng kim ch yu v
chng c to thnh t mt khi lng ng k kh carbonic c mt trong t v
khng kh xem phng trnh sau:
CO2 + CaCO3 + H2O Ca2+ + 2HCO3Cc mui ca acid yu nh borate, silicate v phosphate c th c mt vi khi lng
nh. Mt vi loi acid hu c kh b oxy ha sinh hc, v d nh acid humic, to thnh
cc mui cng gy nn kim trong nc. Trong nc b nhim hoc tnh trng
k kh, mui ca cc acid yu nh acid acetic, propionic v hydrogen sulfide cng c
th to thnh kim. Trong mt s trng hp khc, ammonia hoc cc hydroxide
cng gy nn kim cho nc.
Trong nhng iu kin nht nh, cc ngun nc t nhin c th cha mt lng
ng k kim carbonate v hydroxide. iu kin ny thng xy ra trong ngun
nc mt c to pht trin. To s dng kh carbonic, dng t do v kt hp, trong
nc v pH thng t tr s 9 n 10. Nc l hi lun lun cha kim carbonate
v hydroxide. Nc sau khi c x l lm mm bng phng php ha hc c s
dng vi hoc sa thng cha carbonate v hydroxide.
Mc d rt nhiu cht gy ra kim trong nc, nhng mt phn ln kim ca
nc t nhin do ba cht sau gy ra theo th t ph thuc vo gi tr pH t cao n
thp: (1) hydroxide (OH-), (2) carbonate (CO32-) v (3) bicarbonate (HCO3-). Vi hu ht
cc mc ch thc t, kim do cc cht khc gy ra trong nc t nhin l khng
ng k hoc rt nh.
kim ca nc, v nguyn tc, do mui ca cc acid yu v cc loi baz mnh
gy ra v cc cht ny l dung dch m gi pH khng gim nhiu khi a acid vo
nc. V vy, kim cn l s o kh nng m ca nc v c s dng rng ri
trong lnh vc x l nc cp cng nh nc thi.

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3.2 NGHA MI TRNG

Nh bit, kim ca nc t c ngha v mt sc khe cng ng. Nc c
kim cao thng khng ngon v ngi tiu th thng tm cc ngun nc cp khc.
Nc c x l bng phng php ha hc thng c pH cao cng khng c
ngi s dng a chung. V nhng l do trn, tiu chun v kim cho nc x l
bng phng php ha hc c ban hnh.
3.3 PHNG PHP XC NH KIM
kim c xc nh bng phng php nh phn vi dung dch acid sulfuric H2SO4
N/5 (0,02N) v biu din bng n v tng ng CaCO3. V d cc mu nc c pH
trn 8,3 c nh phn theo hai bc. Trong bc th nht, mu nc c nh
phn bng dung dch acid cho n pH thp hn 8,3 ti im cht ch th phenolphthalein
i mu t hng sang khng mu. Vic nh phn trong pha hai c thc hin n pH
thp hn khong 4,5 tng ng vi im kt thc ca bromcresol green. Khi pH ca
mu nc thp hn 8,3, ch cn nh phn mt ln n pH 4,5.
Vic chn pH 8,3 l im kt thc cho bc nh phn th nht tng ng vi im ion
carbonate chuyn thnh ion bicarbonate:
CO32- + H+ HCO3-
(3 1)
Vic s dng pH khong 4,5 lm im kt thc cho bc nh phn th hai tng ng

vi im ion bicarbonate chuyn thnh acid carbonic:
HCO3- + H+ H2CO3
(3 2)
Trn c s Phng trnh pH = (pKn pKB logC0), im kt thc chnh xc cho

vic nh phn ph thuc vo nng ion bicarbonate ban u ca mu nc. Chng
ta thy rng Phng trnh trn tr thnh:
pH (im tng ng bicarbonate) = 3,19 log[HCO3-]
(3 3)

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14
13
12
11
10
9
8
pH 7
6
5
4
3
2
1
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iem uon
hydroxide
carbonate
iem uon
OH-+H+H2O CO32-+H+HCO3- HCO3-+H+H2CO3
mL acid
Hnh 3.1 ng cong nh phn ca hn hp hydroxide-carbonate.

Bicarbonate [HCO3-] nng 0,01M tng ng vi kim 500 mgCaCO3/L c im
kt thc phi l 4,19. Cc xem xt ny yu cu acid carbonic hoc carbonic c to
thnh t bicarbonate khng b mt t dung dch. iu ny rt kh khn lm chc
chn v v l do ny cc xem xt trn c ngha ln v mt l thuyt.
pH thc ca im kt thc khi xc nh kim tt nht l c xc nh bng cch
nh phn theo in th. Yu t ny c ngha c bit quan trng i vi nc t
nhin m kim tng cng l tng cc nh hng ca cc mui acid yu trong
bicarbonate ch l mt phn. pH ca im gy kt thc trn ng nh phn (xem
Hnh 3.1) l im kt thc tht. Gi tr pH ti cc im kt thc tng ng i vi cc
kim khc nhau t Phng trnh (3 3) hoc trong Standard Methods ch c gi tr
cho cc dung dch bicarbonate v khng c p dng cho nc thi sinh hot hoc
sn xut, thm ch ngay c nc t nhin.
3.4 CC PHNG PHP BIU DIN KIM
Do kim do rt nhiu cht gy nn. Cc cht ny thay i t nc sch nc b
nhim nh nc thi sinh hot v nc thi cng nghip, n cc loi bn b phn
hy. Cc phng php biu din gi tr kim cng thay i mt cch ng k; v vy
cn phi gii thch phng php biu din mt cch chi tit v xc nh cc lnh vc m
cc phng php biu din c s dng.
kim phenolphthalein v kim tng cng
Phn tch ng cong nh phn i vi kim mnh (do kim hydroxide), i vi
carbonate natri, cho thy rng tt c hydroxide u c trung ha ti thi im khi pH
gim n 10 v carbonate chuyn thnh bicarbonate ti thi im khi pH gim xung
khong 8,3. Trong hn hp cha c hydroxide v carbonate, carbonate lm thay i
ng cong nh phn im gy khc co pH 8,3 nh trnh by trong Hnh 3.1. V iu
ny, trong thc t kim o ti im kt thc phenolphthalein c coi l kim
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phenolphthalein. Hin nay, khi nim ny c s dng rng ri trong lnh vc x l

nc thi v vn c s dng trong mt s lnh vc phn tch nc.
Nu vic nh phn mt mu nc c cha c kim carbonate v hydroxide c
tip xc qua im kt thc phenolphthalein, bicarbonate phn ng vi acid v chuyn
thnh acid carbonic. Phn ng ny xy ra hon ton khi pH h thp hn khong 4,5
(xem Hnh 3.1). Khi lng acid yu cu phn ng vi hydroxide, carbonate v
bicarbonate biu din kim tng cng. V kim thng c biu din bng n
v CaCO3; cho nn dung dch H2SO4 N/50 c s dng trong vic nh phn kim.
Cc tnh ton c th thc hin nh sau:
o kiem phenol = (mL dung dch H2SO4 nh phan en pH 8,3)
o kiem tong cong = tong mL H2SO4 nh phan en pH
1.000
mL mau
(3 - 4)
5,0
4,8 1.000
(3 - 5)
4,6 mL mau
4,0
Trong vic xc nh kim tng cng, pH ti im kt thc c mt quan h trc tip

n khi lng kim carbonate ban u ca mu.
kim hydroxide, carbonate v bicarbonate
Trong phn tch nc, cc loi kim c mt trong nc v khi lng ca tng loi
thng c yu cu xc nh. Thng tin ny c bit cn cho qu trnh lm mm
nc v cho nc trong l hi. kim hydroxide, carbonate v bicarbonate thng
c tnh ton da trn cc s liu c bn khi nh phn baz mnh v carbonate
natri. Ba qui trnh sau thng c s dng tnh ton cc loi kim: (1) tnh ton
ch t s o kim, (2) tnh ton t s o kim v pH v (3) tnh ton t cc
phng trnh cn bng. Qui trnh u tin l qui trnh c in da trn cc mi quan h
thc nghim tnh ton cc loi kim khc nhau t kim phenolphthalein v
kim tng cng. Cch tnh ton ny c s dng cho cn b k thut khng c kin
thc c bn v ha hc mi trng. Cc kt qu ca phng php tnh ton ny ch l
gn ng i vi cc mu nc c pH trn 9. D vy, cc nh ha hc nc v cc k
s c lin quan n qu trnh lm mm nc, kim sot n mn, phng chng lng cn
pH cao u cn bit cn bit cc loi ion v nng ca chng. V l do ny, cn
phi c kh nng tnh ton nng ion hydroxide, carbonate v bicarbonate tt c
cc gi tr pH vi chnh xc cn thit. Vic tnh ton vi chnh xc cao ny c th
c thc hin bng qui trnh (2) hoc (3).
Qui trnh hai c chnh xc cho cc mc ch thc t v cng s dng kim
phenolphthalein v kim tng cng. Hn na, s o pH ban u phi yu cu phi
c chnh xc cao tnh ton trc tip kim hydroxide. Trong qui trnh ba, cc
phng trnh cn bng khc nhau ca acid carbonic c s dng tnh ton nng
ca cc loi kim khc nhau. Qui trnh ny cho kt qu vi chnh xc cao i
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vi cc thnh phn, thm ch khi chng c mt trong nc mg/L, khi s o pH c

thc hin chnh xc. i khi nng thp ca cc kim cng ng vai tr quan
trng. kim tng cng cng nh pH c yu cu. Hn na, cn phi xc nh s
o ca cht rn ha tan hiu chnh hot tnh ion vi so o nhit la chn hng
s cn bng thch hp. Cc k s mi trng cng nh cc nh ha hc mi trng
cn phi hiu c s ca cc qui trnh ny. Cc qui trnh c trnh by di y.
Tnh ton t s o kim
Trong qui trnh ny, kim phenolphthalein v kim tng cng c xc nh v t
cc s o ny tnh ton kim hydroxide, carbonate v bicarbonate. Cc tnh ton ny
c th c thc hin bng cch cho rng (khng chnh xc) kim hydroxide v
kim carbonate khng cng tn ti trong mt mu nc. iu ny cho php nm kh
nng sau: (1) ch c hydroxide, (2) ch c carbonate, (3) hydroxide v carbonate, (4)
carbonate v bicarbonate v (5) ch c bicarbonate. Hnh 4.6 v 4.8 biu din rng vic
trung ha hydroxide c thc hin hon ton khi lng acid a vo gim pH
n 8,3 v khi dng mt na lng carbonate b trung ha. Khi tip tc nh phn
n pH 4,5, mt khi lng khng ng k acid c s dng trung ha hydroxide
v mt khi lng acid dng bng khi lng trung ha carbonate n pH 8,3, c
s dng trung ha carbonate. iu ny l thng tin c bn xc nh cc dng
kim hin trong nc v khi lng ca tng loi. Biu biu din s nh phn vi
cc kim kt hp vi nhau c trnh by trong Hnh 3.2
Hydroxide+carbonate
carbonate
hydroxide
hydroxide
Carbonate+bicarbonate
carbonate
hydroxide
carbonate
carbonate
Phenolphthalein
iem cuoi
pH 8,3
bicarbonate
bicarbonate
Bromcresol xanh iem cuoi
bicarbonate
pH 4,5
Hnh 3.2 th nh phn mu nc cha cc dng kim khc nhau.

Ch c hydroxide. Cc mu ch cha kim hydroxide c pH cao, thng cao hn
10. Vic nh phn hon thnh ti im kt thc phenolphthalein. Trong trng hp ny
kim hydroxide bng kim phenolphthalein.
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Ch c carbonate. Cc mu ch cha kim carbonate c pH 8,5 hoc cao hn. Vic

nh phn n im kt thc phenolphthalein chnh xc bng mt na vic nh phn
tng cng. Trong trng hp ny, kim carbonate bng kim tng cng.
Hydroxide carbonate. Cc mu cha kim hydroxide v carbonate c pH cao,
thng cao hn 10. Vic nh phn t im kt thc phenolphthalein n im kt thc
bromcresol green th hin mt phn hai kim carbonate. V vy kim carbonate
c th c tnh ton nh sau:
o kiem carbonate = 2 (nh phan t pH 8,3 en 4,5)
1.000
mL mau
v kim hydroxide = kim tng cng kim carbonate carbonate

bicarbonate. Cc mu cha kim carbonate v bicarbonate c pH cao hn 8,3 v
thng thp hn 11. Vic nh phn n im kt thc phenolphthalein th hin mt
phn hai kim carbonate. kim carbonate c th c tnh ton nh sau:
o kiem carbonate = 2 (nh phan en pH 8,3)
1.000
mL mau
v kim hydroxide = kim tng cng kim carbonate

Ch c bicarbonate. Cc mu ch cha kim carbonate c pH 8,3 hoc thp hn,
thng l thp hn. Trong trng hp ny kim bicarbonate bng kim tng
cng.
Cc phng php c cp phn trc tnh ton gn ng kim c
thay th bng phng php chnh xc hn c trnh by di y.
Tnh ton t s o kim v pH
Trong qui trnh ny, s o pH, kim phenolphthalein v kim tng cng phi c
thc hin.
Hydroxide. Trc tin, kim hydroxide c tnh ton t s o pH, s dng
hng s phn ly ca nc,
[OH ] =
Kn
[H + ]
(3 6)
Tnh ton ny yu cu s pH phi chnh xc xc nh [H+]. V vi nng

hydroxide 1 mg/L tng ng vi kim 50.000 mgCaCO3/L, mi quan h trn c
th c biu din thun li hn.
kim hydroxide = 50.000 x 10(pH - pKn)
(3 - 7)

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nhit 240C, pKn = 14,00. D sao n thay i t 14,94 00C n 13,53 400C. V
vy, vic o nhit ng vai tr quan trng hiu chnh pKn. Mi quan h gia pH,
nhit v kim hydroxide c trnh by bng th trong Hnh 1.3.3. c
chnh xc cao hn, phi xc nh nng cht rn ha tan hiu chnh hot ion,
mc d trong trng hp ny vic hiu chnh l khng ng k v khng cn thit trong
hu ht cc mc ch thc t. Trong cun Standard Methods c sn biu cho
php tnh ton nhanh kim hydroxide trn c s s dng s o pH, nhit v cht
rn ha tan.
Carbonate. Khi kim hydroxide c xc nh, s dng cc qui trnh trc tnh
ton kim carbonate v bicarbonate. kim phenolphthalein biu din ton b
kim hydroxide cng vi mt phn hai kim carbonate. V vy, kim carbonate c
th c tnh ton nh sau:
kim carbonate = 2 ( kim phenol - kim hydroxide)
(3 - 8)
o kiem hydroxide, mgCaCO3/L
100
40
20
10
4
5 0C
150C
1
250C
0,4
350C
0,2
0,1
10
11
12
Hnh 3.3 Mi quan h gia kim hydroxide v pH cc nhit khc nhau.

Bicarbonate. Vic nh phn t pH 8,3 n 4,5 do mt phn hai kim carbonate
cng vi ton b kim bicarbonate cn li. R rng rng, kim bicarbonate biu
din kim cn li sau khi tr i kim bicarbonate tr thnh:
kim bicarbonate = kim tng cng ( kim carbonate kim hydroxide)( 3 - 9)
Tnh ton t cc phng trnh cn bng
Vic phn b cc loi kim khc nhau c th c tnh ton t cc phng trnh
cn bng kt hp vi phng trnh trung ha in tch (cn bng ion) trong dung dch.
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bo ton in tch, tng nng ng lng ca cc cation phi bng tng nng
ng lng ca cc anion. kim tng cng l s o nng ng lng ca
tt c cc cation v anion kt hp vi kim c trnh by nh sau:
[H+] +
o kiem
50.000
= [HCO3-] + 2[CO32-] + [OH-]
(3 10)
Cc phng trnh cn bng phi c xem xt l Phng trnh (3 6) v Phng trnh

phn ly bc hai ca acid carbonic,
{H }{CO } = K
2
{H CO3
(3 - 11)
A2
T s o pH, [H+] v [OH-] c th c xc nh bng cch s dng phng trnh (3

6). Ch cn kim khng c bit l [HCO3-] v [CO32-] v chng c th c xc
nh t li gii ng thi ca phng trnh (3 10) v (3 - 11). Sau y l cc phng
trnh kt qu:
o kiem carbonate
mgCaCO3/l
o kiem carbonate
mgCaCO3/l
50.000 [(o kiem/50.000) + [H+] (Kn/[H+])]

+
1 + ([H ]/2KA2)
50.000 [(o kiem/50.000) + [H+] (Kn/[H+])]
1 + (2KA2/[H+])
(3 12)
(3 13)
nhit 250C, Kn l 10-14 v KA2 l 4,7.10-11. Tuy nhin, cc gi tr ny thay i d

dng cng vi s thay i nhit . Hot tnh ion cng thay i ng k cng vi nng
ion, nh trnh by trong Phn 4.3. Vic hiu chnh ny kh di, Standard
Methods trnh by th nh gi carbonate v bicarbonate da trn c s xem xt
trn. th ny, cng nh Phng trnh (3 12) v (3 - 13) thu c kt qu kim
biu din di dng CaCO3. Trong nhiu trng hp c th phi xc nh nng thc
ca carbonate v bicarbonate. Vic chuyn nng t miligram trn lt ca CO32- hoc
HCO3- nh sau:
mg/L CO32- = mg/L kim carbonate x 0,6
(3 14)
mg/L HCO3- = mg/L kim bicarbonate x 1,22
(3 15)
Nng mol c th c tnh ton bng cch chia miligram trn lt cho trng lng
miligram phn t ca ion:
[CO32-] =
mg/L CO3260.000
va
[HCO3-]
mg/L CO3261.000
(3 16)

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3.5 MI QUAN H GIA CARBONIC, KIM V pH TRONG NC T NHIN

T cc phng trnh
CO2 + H2O H2CO3 + HCO3- + H+
M(HCO3)2 M2+ + 2HCO3HCO3- CO32- + H+
CO32- + H2O HCO3- + OH-
(3 - 17)
(3 - 18)
(3 - 19)
(3 - 20)
R rng rng carbonate v ba dng kim l cc phn ca mt h thng tn ti

dng cn bng v tt c cc phng trnh u lin quan n HCO3-. S thay i nng
ca bt c thnh phn no trong h thng s dn n thay i cn bng, thay i
nng ca cc ion khc v kt qu l s thay i pH. Ngc li, s thay i pH s
lm thay i cc mi quan h. Hnh 3.3 trnh by mi quan h gia carbonic v ba loi
kim trong nc vi kim tng cng l 100 mg/L v theo phm vi pH quan trng
trong thc t k thut mi trng. xy dng th ny s dng Phng trnh (2 - 7),
(3 - 7), (3 - 12), (3 - 13). Cc thng tin cho trong Hnh ch s dng cho mc ch m t
nh s khc nhau v mi quan h ca kim tng cng, nhit .
100
90
o kiem mgCaCO3/L
80
HCO3-
70
60
50
40
CO32-
30
20
CO2
10
OH-
0
6,5
Hnh 3.4
7,5
8,5
9,5
10
10,5
11
Mi quan h gia carbonic v ba dng kim ti ti cc pH khc nhau

(gi tr c tnh ton cho nc vi kim tng cng l 100 mgCaCO3/L
nhit 250C).

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3.6 P DNG S LIU V KIM

Cc thng tin lin quan n kim c s dng theo rt nhiu cch trong thc t k
thut mi trng.
Keo t ha hc
Cc ha cht c s dng keo t nc v nc thi phn ng vi nc to
thnh kt ta hydroxide khng ha tan. Ion hydro gii phng ra s phn ng vi
kim ca nc. V vy, kim tc dng m cho nc dy pH ti u cho qu trnh
keo t. kim phi c mt trong nc mt lng trung ha lng acid c
gii phng ra t cc cht keo t v hon thnh qu trnh keo t.
Lm mm nc
kim l thng s chnh phi c xem xt n trong vic tnh ton nhu cu v vi v
sa trong qu trnh lm mm nc bng phng php kt ta. kim ca nc
c lm mm phi nm trong gii hn ca tiu chun nc ung.
Kim sot n mn
kim l thng s quan trng lin quan n vic kim sot qu trnh n mn. y l
thng s cn phi bit tnh ton ch s bo ha Langelier.
Kh nng m
S o kim c s dng nh mt thng s nh gi kh nng m ca nc
thi v bn.
Cht thi cng nghip
Nhiu cng ty chnh qui cm vic x cht thi cha kim hydroxide vo ngun nc.
cc nh chc trch th thng cm x cht thi cha kim hydroxide vo cng
thot nc. kim cng nh pH l yu t quan trng khi xc nh kh nng x l sinh
hc ca nc thi.
3.7 MT S P DNG KHC CA KIM I VI K S MI TRNG
K s mi trng thng gp nhiu trng hp thc t lin quan n mi quan h
carbonic kim pH v thng phi gii thch cc mi quan h ny.
S thay i pH khi thi kh
Trong thc t, nc c thi kh kh carbonic. V carbonic l kh acid nn khi kh
carbonic dn n lm gim [H+] v v vy lm tng pH ca nc theo phng trnh (1.3
- 1.3). Khng kh bnh thng c khong 0,03% khi carbonic theo th tch. Hng s
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Henry [xem Phng trnh (2 - 15)] i vi carbonaic khong 1.500 mg/L-atm nhit
250C; v vy, nng cn bng ca carbonic vi khng kh l 0,0003 x 1.500 hoc
khong 0,45mg/L. T phng trnh (16 - 7) c th c tnh ton rng nc c
kim 100 mg/L c thi kh n trng thi cn bng vi carbonic trong khng kh phi
c pH khong 8,6. Nc vi kim ln hn phi dn n c pH cao hn trong khi thi
kh v mu nc c kim thp dn n pH thp.
S thay i pH khi c mt to
Nhiu ngun nc mt c iu kin tt cho to pht trin. nhng vng to pht
trin mnh, c bit l ni nc cn, pH c th t n 10. To s dng carbonic
cho cc hot ng quang tng hp ca chng v vic kh carbonic dn n pH cao.
Chng ta thy rng vic thi kh kh carbonic dn n pH c th tng n 8 v 9 vi
kim trung bnh. To c th gim nng carbonic t xung di nng cn bng
trong khng kh v tip theo c th gy nn vic tng pH rt cao. Khi pH tng, cc dng
kim thay i vi kt qu carbonic c th c s dng cho s pht trin ca to
vi c dng carbonate v bicarbonate theo phng trnh cn bng sau:
2HCO3- CO32- + H2O + CO2
CO32- + H2O 2OH- + CO2
(3 - 21)
(3 - 22)
V vy, vic kh kh carbonic bng to dn n chuyn cc dng kim t

bicarbonate thnh carbonate v t carbonate n hydroxide. Cn lu rng trong qu
trnh thay i ny kim tng cng bng hng s (khng i). To c th tip tc s
dng kh carbonic ca nc cho n khi pH tng n gi tr nh hng, thng trong
dy pH 10 n 11.
Vo ban m, to sn xut kh carbonic thay v tiu th n. iu ny xy ra v qu trnh
h hp ca chng trong bng ti cao hn qu trnh quang hp tng hp. Vic sn xut
carbonic ny c nh hng ngc v dn n lm gim pH. S thay i ban ngy ca
pH do qu trnh quang tng hp v h hp thng xy ra trong nc mt.
Trong nc t nhin cha mt lng ng k Ca2+, carbonate canxi kt ta khi nng
ion carbonate, theo Phng trnh (3 - 21), ln tch ha tan ca CaCO3 :
Ca2+ + CO32- CaCO3
(3 - 23)
Vic kt ta ny thng xy ra trc khi pH vt qu 10. Carbonate canxi lng cn
nh kt qu ca vic kh carbonic qua hot ng ca to to nn cc cn lng l hn
hp ca st v vi trong h. Cn lng st vi l tin thn ca vi.
kim ca nc l hi
Nc l hi cha c kim carbonate v hydroxide. C hai loi kim ny nhn
c t kim bicarbonate ca nc a vo l hi. Kh carbonic khng ha tan
trong nc l hi v c kh cng vi hi nc nng. iu ny lm tng pH v
chuyn kim t bicarbonate thnh carbonate v t carbonate thnh hydroxide nh
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trnh by trong Phng trnh (3 - 21) v (3 - 22). Di cc iu kin nh vy, pH

lun cao hn 11.

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CHNG 4
OXY HO TAN
4.1 KHI NIM CHUNG

Tt c cc sinh vt sng b ph thuc vo oxy dng ny hoc dng khc duy trnh
qu trnh trao i cht nhm sn sinh ra nng lng cho s tng trng hoc sinh sn.
Qu trnh hiu kh l vn c quan tm nht khi chng cn oxy t do.
Cc k s mi trng quan tm n iu kin kh quyn c lin quan n mi trng
cht lng, nc l cht lng ln nht v quan trng nht.
Tt c cc cht kh ca kh quyn ha tan trong nc cc mc khc nhau. C nit
v oxy c phn loi l cc cht ha tan km v v chng khng phn ng vi nc
v mt ha hc, nn ha tan t l thun vi p sut ring phn ca chng. Hn na,
nh lut Henry c th c s dng tnh ton khi lng c mt ca cc cht kh
trng thi bo ha ti bt c nhit cho no. ha tan ca c nit v oxy thay
i mt cch ng k theo nhit trong dy m cc k s mi trng quan tm. Hnh
4.1 trnh by ng cong ha tan ca hai cht kh trong nc ct hoc l nc c
hm lng cht rn thp nm cn bng vi khng kh ti p sut 760 mmHg. ha
tan s nh hn trong nc mui.
ha tan ca oxy kh quyn trong cc ngun nc ngt nm trong khong t 14,6
mg/L 00C n khong 7 mg/L 350C di p sut 1 atm. V n l kh ha tan t,
ha tan ca n thay i t l thun vi p sut ca kh quyn ti nhit cho. V tc
oxy ha sinh hc tng cng vi nhit v nhu cu oxy cng tng mt cch tng
ng, iu kin nhit cao, khi oxy ha tan c kh nng ha tan thp nht l vic
lin quan ln nht i vi k s mi trng. Hu ht cc iu kin ti hn lin quan
n thiu ht oxy ha tan, trong thc t, k thut mi trng xut hin vo nhng
thng h khi nhit cao v ha tan oxy mc thp nht. V l do ny thng
thng mc ha tan oxy khong 8 mg/L l cao nht di cc iu kin ti hn.
ha tan thp ca oxy l yu t chnh gii hn kh nng lm sch ca cc ngun
nc t nhin v cn phi x l cht thi loi b cc cht nhim trc khi x vo
ngun tip nhn. Trong qu trnh x l sinh hc hiu kh, ha tan gii hn ca oxy l
quan trng nht v n kim sot tc hp th oxy ca mi trng.

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25
o hoa tan, mg/L
20
Nit
15
oxy
10
5
0
0
5 10 15
20 25 30 35
Nhiet o, 0C
Hnh 4.1 ha tan ca oxy v nit trong nc ct c bo ha khng kh p sut
760 mmHg.
ha tan ca oxy trong nc mui thp hn so vi nc ngt. V l do ny, ha
tan i vi nhit cho gim lin tc t nc ngt n nc ca sng v nc
bin. Vic nh hng ny c ch th trong Bng 4.1, lit k ha tan ca oxy ph
thuc vo nhit v hm lng clorua. Nng clorua c s dng nh s hn
hp nc bin v nc ngt trong mu nc. Nng ca clorua trong nc bin
khong 19.000 mg/L.
Trong nc nhim gi tr bo ha cng thp hn trong nc sch. T s gi tr trong
nc nhim v nc sch tham kho nh h s . Tc oxy ha tan trong nc
nhim thng nh hn trong nc sch v t s ny c tham kho nh gi tr . C
hai gi tr v l thng s thit k quan trng trong vic la chn thit b thi kh.

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Bng 4.1 ha tan ca oxy trong nc trong cn bng vi khng kh kh p sut

760 mmHg v cha 20,9% oxy
Nhit
0
C
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Nng clorua, mg/L

0
5.000
10.000
15.000
20.000
14,6
14,2
13,8
13,5
13,1
12,8
12,5
12,2
11,9
11,6
11,3
11,1
10,8
10,6
10,4
10,2
10,0
9,7
9,5
9,4
9,2
9,0
8,8
8,7
8,5
8,4
8,2
8,1
7,9
7,8
7,6
13,8
13,4
13,1
12,7
12,4
12,1
11,8
11,5
11,2
11,0
10,7
10,5
10,3
10,1
9,9
9,7
9,5
9,3
9,1
8,9
8,7
8,6
8,4
8,3
8,1
8,0
7,8
7,7
7,5
7,4
7,3
13,0
12,6
12,3
12,0
11,7
11,4
11,1
10,9
10,6
10,4
10,1
9,9
9,7
9,5
9,3
9,1
9,0
8,8
8,6
8,5
8,3
8,1
8,0
7,9
7,7
7,6
7,4
7,3
7,1
7,0
6,9
12,1
11,8
11,5
11,2
11,0
10,7
10,5
10,2
10,0
9,8
9,6
9,4
9,2
9,0
8,8
8,6
8,5
8,3
8,2
8,0
7,9
7,7
7,6
7,4
7,3
7,2
7,0
6,9
6,8
6,6
6,5
11,3
11,0
10,8
10,5
10,3
10,0
9,8
9,6
9,4
9,2
9,0
8,8
8,6
8,5
8,3
8,1
8,0
7,8
7,7
7,6
7,4
7,3
7,1
7,0
6,9
6,7
6,6
6,5
6,4
6,3
6,1
4.2 NGHA MI TRNG CA OXY HA TAN

Trong cht thi lng, oxy ha tan l yu t xem s thay i sinh hc c thc hin
bng sinh vt hiu kh hay k kh. Loi th nht s dng oxy t do oxy cc cht hu
c hoc v c v sn xut ra cc sn phm cui cng khng c hi, ngc li loi sau
thc hin cc oxy ha nh vy qua vic kh qua mui khng hu c nh sulfate v
sn phm cui cng thng rt c hi. V c hai loi vi sinh vt thng c mt khp
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ni trong t nhin, n l iu quan trng trong iu kin thun tin cho sinh vt hiu kh
(iu kin hiu kh) phi c duy tr; ngc li vi sinh vt k kh s chim a s v kt
qu to thnh mi hi thi. V vy, vic o oxy ha tan l rt quan trng duy tr iu
kin hiu kh trong cc ngun nc t nhin tip nhn cc cht nhim v trong qu
trnh x l hiu kh c thc hin lm sch nc thi sinh hot v cng nghip.
Vic xc nh oxy ha tan thng c s dng cho cc mc ch khc nhau. N l
mt trong nhng th nghim n l quan trng nht m ngi k s mi trng s
dng. Trong hu ht cc trng hp lin quan n vic kim sot nhim cc dng
chy, n l s mong mun duy tr iu kin thun li cho vic tng trng v sinh
sn ca qun th c v cc loi sinh vt nc khc.
Vic xc nh oxy ha tan phc v nh c s ca th nghim BOD; v vy, chng l c
s ca hu ht cc th nghim phn tch quan trng c s dng nh gi nng
nhim ca nc thi sinh hot v cng nghip. Tc oxy ha sinh ha c th c
o bng vic nh lng oxy d trong h thng thi gian nht nh.
Cc qu trnh x l hiu kh ph thuc vo oxy ha tan v th nghim cho n l cn thit
nh cng c kim sot tc thi kh lm chc chn rng khi lng khng kh
c cung cp duy tr iu kin hiu kh v cng trnh vic s dng qu mc
khng kh v nng lng.
Oxy l yu t quan trng trong qu trnh n mn st v thp, c bit trong h thng
phn phi nc v trong l hi. Tch oxy t nc cp cho l hi bng phng php
vt l v ha hc l thc t thng gp trong cng nghip v nng lng. Th nghim
oxy ha tan phc v nh phng tin kim sot.
4.3 LY MU XC NH OXY HA TAN
Cn phi cn trng trong khi ly mu xc nh oxy ha tan. Trong hu ht cc
trng hp, mc oxy ha tan s thp hn bo ha v vic tip xc vi khng kh s
dn n lm sai kt qu. V l do ny, thit b ly mu c bit tng t nh thit b
c m t trong Standard Methods l cn thit. Tt c cc mu nh vy c thit
k da trn nguyn tc l vic tip xc vi khng kh l khng th trnh c trong thi
gian chai ly mu c lm y.
Hu ht cc mu nc dng xc nh oxy ha tan c thu gom ti hin trng,
khng thun tin thun tin thc hin ton b cc xc nh. V gi tr oxy c
th thay i mt cch d dng theo thi gian do hot ng sinh hc, nu mu nc
khng c n nh ngay sau khi ly mu. Qui trnh bnh thng l x l mu vi cc
loi ha cht thng dng c s dng trong th nghim xc nh oxy ha tan v sau
tin hnh nh phn khi mu nc c mang v phng th nghim. Qui trnh ny
s cho kt qu thp i vi cc mu nc c nhu cu iot cao v trong trng hp ny,
tt hn l bo qun mu bng cch thm vo 0,7 mL acid sulfuaric m c v 0,02 g
natri azide. Khi thc hin iu ny xong, cn phi cho thm 3 mL iot kim (alkali iodide) thay v bnh thng l 2 mL v mu cha mt lng acid d. Kt qu tt hn
cng thu c nu mu n nh c gi trong phng ti v trong nc cho n
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khi vic phn tch c th c hon thnh. Vic x l ha hc s dng trong n nh

l dng tt c cc hot ng sinh hc v vic nh phn cui cng c th c
thc hin sau 6 gi.
4.4 LA CHN HA CHT TIU CHUN O OXY HA TAN
Hu ht cc phng php xc nh oxy ha tan ph thuc vo phn ng gii phng ra
khi lng iod tng ng vi khi lng oxy hin din ban u, cng vi vic o
tip theo khi lng iod gii phng ra bng dung dch chun. Thiosulfate natri l cht
kh thng c s dng v dung dch tinh bt c s dng xc nh im kt
thc. Tt c cc phn ng trong th nghim oxy ha tan lin quan n qu trnh oxy ha
v kh. Tuy nhin, tinh bt c s dng nh cht ch th im kt thc v to thnh
phc iod - tinh bt vi iod t do t dung dch long to thnh mu xanh v chuyn
thnh khng mu khi tt c iod t do b kh thnh ion iod.
La chn dung dch Thiosulfate N/40
Trng lng tng ng ca oxy l 8. V nng (normality) ca hu ht cc cht
nh phn s dng trong phn tch nc v nc thi c iu chnh sao cho mi
millilit dung dch chun tng ng vi 1,0 mg ca cht c o, nh vy s dng
dung dch thiosulfate N/8. V vy, khi dung dch thiosulfate N/40 (N/8 x 1/5) c s
dng nh phn 200 mL mu, gi tr oxy ha tan tnh bng milligram trn lt l tng
ng vi th tch nh phn tnh bng miliilit. iu ny loi b s tnh ton khng cn
thit.
Chun b v chun dung dch thiosulfate N/40 (0,025 N)
Sodium thiosulfat (Na2S2O3.5H2O) c th tn ti di dng tinh khit. Tuy nhin, do
c cha gc nc, n c th b kh i to thnh hp cht c thnh phn xc nh v
thm ch c th mt nc ngay nhit phng trong iu kin m thp. Do vy,
cn phi iu ch thiosulfat di dng dung dch c nng cao hn nng cn thit
v chun li chng mi khi s dng.
Khi lng ng lng sodium thiosulfate khng th c tnh da vo cng thc
ca n v s thay i ha tr ca nhng cht kh. Chng c th c tnh ton da
vo cc cht oxy ha nh trong trng hp iodine.
2Na2S2O3.5H2O + I2 Na2S4O6 + 2NaI + 10H2O
(4 - 1)
T Phng trnh (4 - 1) c th tnh l mi phn t thiosulfate natri (Na2S2O3.5H2O) th

tng ng vi mt nguyn t iodine. Khi mi nguyn t iodine nhn mt electron
trong qu trnh phn ng to thnh ion iodine, c ngha l mi phn t thiosulfate
cung cp mt in t khi oxy ha thnh tetrathionate hay,
2S2O32- + I2 S4O62- + 2I-
(4 - 2)

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T nhng l do trn, c th kt lun l khi lng ng lng ca thiosulfate natri

bng vi khi lng phn t ; v nn s dng mt lng d bng khong 1/40 ca
khi lng phn t, (khong 6,205 g) iu ch mt lt dung dch c nng ln hn
N/40 mt cht. Thng thng th 6,5 g l .
Dung dch thiosulfate c th c chun bng potassium dichromate hoc potassium bi
- iodate. C hai c th tn ti dng tinh khit 100%. Thng thng iu ch dung dch
N/40 bng cch cn chnh xc tinh th bng cn phn tch v pha long chng vi mt
th tch xc nh bng bnh nh mc. C hai cht chun ny phn ng vi ion iodide
trong dung dch acid gii phng iodine:
Cr2O72- + 6I- + 14H+ 2Cr3+ + 3I2 + 7H2O
2IO3- + 10I- + 12H+ 6I2 + 6H2O
(4 - 3)
(4 - 4)
Lng iodine gii phng bng vi lng cht oxy ha s dng. Do , nu s dng 20
ml K2Cr2O7 N/40 hay KIO3.HIO3 th s c chnh xc 20ml N/40 dung dch thiosulfat
c s dng trong chun .
Phn ng gia Cr2O72- v I- khng xy ra ngay lp tc m cn c khong 5 pht
hon tt phn ng. Sn phm Cr3+ cho mu xanh greenish-blue vi tinh bt. iu ny
c th khc phc bng cch pha long mu trc khi chun . Chun bng
potassium bi - iodate c s dng ph bin v n l cht chun duy nht c gii
thiu trong Standard Methods.
Dung dch thiosulfate b nh hng bi hot ng ca vi khun v bi CO2. Vi khun
sulfur oxi ha thiosulfate thnh sulfate di iu kin k kh. CO2 lm gim pH l
nguyn nhn ca s phn hy ion thiosulfate thnh SO32- v S. Cc ion SO32- bin i
thnh SO42- di tc dng ca oxy ha tan. bo qun dung dch thiosulfat khi nh
hng ca vi khun v CO2 ta c th cho vo dung dch 0,4g NaOH/ Lit. Kt qu l pH
cao phng trnh s tng trng ca vi khun v gi cho pH khng b tt xung khi c
mt lng nh tha CO2 trong dung dch. Trnh hin tng tha NaOH v iu ny
cng c th lm dung dch mt tnh n nh.
4.5 PHNG PHP XC NH OXY HA TAN
Phng php o oxy ha tan c in c thc hin bng cch t nng mu ui
kh ha tan v xc nh oxy t mu kh thu c ny nh p dng phng php phn
tch kh. Phng php ny i hi mt lng mu ln v thi gian thc hin di.
Phng php Winkler hay Iodometric v nhng ci bin ca chng l nhng k thut
tiu chun xc nh oxy ha tan hin nay. Vic xt nghim ty thuc vo lng O2
oxy ha Mn2+ to thnh mt trng thi ha tr cao hn di iu kin kim v
manganese trng thi ny c kh nng oxy ha I- thnh I2 trong mi trng acid. Do
, lng I2 c gii phng bng vi lng oxy ha tan hin din trong mu. Iodine
c o vi dung dch tiu chun thiosulfate natri v c gi tn l oxy ha tan.
Phng php Winkler
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Phng php Winkler nguyn gc b nh hng ca rt nhiu cht lm cho kt qu

khng chnh xc. V d: mt s cht oxy ha nh nitrite v Fe3+ c th oxy ha I- thnh
I2 lm cho kt qu cao hn, cc cht kh nh Fe2+, SO32-, S2-, v polythionate kh I2
thnh I- v lm cho kt qua nh i. Phng php Winkler nguyn gc ch c th c
p dng vi nc tinh khit.
Cc phn ng trong phng php Winkler gm:
Mn2+ + 2OH- Mn(OH)2 (4 5)
(ket tua trang)
Nu khng c oxy hin din, kt ta trng Mn(OH)2 s c hnh thnh khi thm vo
mu MnSO4 v alkali-iodine reagent (NaOH + KI). Nu oxygen hin din trong mu,
mt s Mn (II) c oxy ha thnh Mn(IV) v to kt ta nu. Phng trnh phn ng
nh sau:
hay
Mn2+ + 2OH- + O2 MnO2 + H2O
(4 - 6)
Mn(OH)2 + O2 MnO2 + H2O
(4 - 7)
Qu trnh oxy ha Mn(II) thnh MnO2, ngi ta thng gi l s c nh oxy, qu trnh

xy ra chm, c bit l nhit thp. Cn phi lc mnh mu t nht trong 20 giy.
Trong trng hp nc hi mn hay nc bin th cn phi lc lu hn.
Sau khi lc mu mt thi gian tt c oxy phn ng, cc kt ta c php lng
phn thnh 2 lp t nht l cch b mt nc sch 5 cm k t nh, sau thm
acid sulfuric vo. Trong iu kin pH thp cho kt qu l oxy ha I- thnh I2.
MnO2 + 2I- + 4H+ Mn2+ + I2 + 2H2O
(4 - 8)
I2 khng ha tan trong nc, nhng dng phc vi iodine tha to thnh dng ha tan
tri - iodate, do trnh tht thot I2 khi dung dch:
I2 + I- I3-
(4 - 9)
Nn y kn mu v lc t nht trong 10 giy phn ng xy ra hon ton.

By gi mu sn sng chun vi thiosulfate N/40. S dng thiosulfate N/40
chun 200 mL mu. Thm vo cc cht s dng trong phng php Winkler, phi
pha long mu do cn phi ly mt lng mu ln hn 200 mL chun. Khi s
dng chai 300 mL cn dng 2 mL MnSO4 v 2 mL alkali-KI. Khi cho 4ml dung dch ny
vo phi thao tc sao cho chng y xp x 4ml mu t trong chai ra ngoi v cn phi
hiu chnh li. Khi cho vo 2 mL acid, khng xy ra s oxy ha, do vy khng cn phi
hiu chnh cho thao tc ny. thc hin vic hiu chnh khi cho vo 2 cht phn ng
u tin ta s dng 203ml mu chun .

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Chun 200 mL mu vi thiosulfate N/40, t tnh lng oxygen mg/L.

Bin i Azide ca phng php Winkler
Ion nitrite l mt trong nhng ion thng gp gy nh hng trong qu trnh xc nh
oxy ha tan. Anh hng ny xy ra trong nc sau khi x l sinh hc, trong nc
sng v trong mu BOD. N khng oxy ha Mn2+ nhng n oxy ha I- thnh I2 trong
mi trng acid. N thng gy nh hng bi tnh kh ca n, N2O2, c oxy ha
bi oxygen i vo trong mu trong khi chun , n chuyn ha thnh NO2- v gy bin
i chu k phn ng n ni c th dn n sai kt qu phn tch (thng lm tng kt
qu phn tch). Cc phn ng bao gm:
2NO2- + 2I- + 4H+ I2 + N2O2 + 2H2O
(4 - 10)
N2O2 + O2 + H2O ( 2NO2- + 2H+
(4 - 11)
Khi c s hin din ca nitrite th khng th c sn phm cui c nh. Ngay lp tc,
mu xanh ca ch th tinh bt bin mt, nhng dng nitrite t phng trnh phn ng s
phn ng vi nhiu I- to thnh I2 v mu xanh ca h tinh bt s quay tr li.
Hin tng Nitrite d dng khc phc bng cch s dng sodium azide (NaN3). Rt d
trn azide vo alkali-KI. Khi thm acid sulfuric vo cc phn ng tip theo xy ra v
NO2- b ph hy:
NaN3 + H+ HN3 + Na+
(4 - 12)
HN3 + NO2- + H+ N2 + N2O + H2O
(4 - 13)
Bng cch ny, nh hng ca nitrite c ngn chn v phng php Winkler tr
nn n gin v ph bin.
4.6 PHNG PHP IN CC MNG O OXY HA TAN
S dng mng in cc o DO ngy cng c ph bin do s pht trin ca
chng. Loi ny c bit hu hiu i vi vic xc nh profile DO trong dng chy.
in cc c th thp hn i vi s bin i su v nng DO, c th c t mn
hnh ni vi in cc trn b mt dng chy. Chng cng c th l lng trong b x l
sinh hc gim st mc DO mi thi im. Tc s dng oxygen sinh hc cng
c th c xc nh bi v tr ly mu cht lng trong 1 chai BOD v sau a in
cc vo quan st tc ph hy oxygen. Chng cng c th c s dng o
nhanh DO khi kim nh BOD. u im ca n s thy r khi phi phn tch mt lng
mu ln. Kh nng d mang theo khi i o c lm cho mng in cc tr thnh mt
thit b tuyt vi.
Mng in cc thng c kim tra bng cch o mu c phn tch ch tiu DO
bi phng php Winkler. Do , mi li t k thut phn tch Winkler s c hon
thin bng in cc. Trong sut qu trnh o DO, mt vn rt quan trng l mu phi
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di chuyn qua in cc trnh c chm kt qu nu oxygen b ph hy ngay ti

mng khi n b gim cathode. Mng in cc rt nhy vi nhit do nhit o
xung quanh phi tng ng vi o DO. V vy, cn phi chnh xc hoc thit b phi
c ch to cng vi thit b o nhit .
4.7 P DNG S LIU OXY HA TAN
S liu oxy ha tan c s dng rng ri trong nhiu lnh vc. Nhiu ng dng c
tho lun di cc iu kin tng qut trong Mc 4.1.

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CHNG 5
NHU CU OXY SINH HA

5.1 GII THIU CHUNG
Nhu cu oxy sinh ha (BOD) l lng oxy cn thit vi sinh vt oxy ha cc cht hu
c c kh nng phn hy sinh hc trong iu kin hiu kh. Khi nim c kh nng
phn hy c ngha l cht hu c c th dng lm thc n cho vi sinh vt.
BOD l mt trong nhng ch tiu c dng nh gi mc gy nhim ca cc
cht thi sinh hot, nc thi cng nghip v kh nng t lm sch ca ngun nc.
Ch tiu BOD c xc nh bng cch o c lng oxy m vi sinh vt tiu th trong
qu trnh phn hy cc cht hu c. Cc mu phi c bo qun trnh tip xc vi
khng kh ngn cn oxy thng kh ha tan vo nc khi hm lng oxy ha tan
trong mu gim. Do hm lng oxy ha tan bo ha trong nc t khong 9 mg/L
200C, nhng loi nc thi c hm lng cht hu c cao phi c pha long thch
hp bo m lng oxy ha tan phi tn ti trong sut qu trnh th nghim. Phn
tch BOD p dng qu trnh sinh hc nn phi khng ch iu kin mi trng thch
hp cho s sinh trng ca cc vi sinh vt. Cc cht c hi i vi vi sinh vt phi
c loi khi dung dch. Tt c cc thnh phn dinh dng cn thit cho s pht trin
ca vi sinh vt nh N, P v nhng nguyn t vi lng phi c b sung. Qu trnh oxy
ha hon ton cc cht hu c di tc dng ca vi sinh vt s to thnh CO2 v H2O.
Do , vi sinh vt c b sung trong phn tch BOD c gi l seed.
Phng trnh phn ng tng qut c th biu din nh sau:
CnHaObNc + (n + a/4 - b/2 - 3/4c)O2 nCO2 + (a/2 3/2c)H2O + NH3
(5 - 1)
Vn tc phn ng phn hy cht hu c trong th nghim BOD ph thuc vo nhit

v nng cht hu c c trong mu phn tch. loi tr nh hng ca nhit , th
nghim c tin hnh 200C. Theo l thuyt, phn ng c th xem l hon ton trong
vng 20 ngy, y l khong thi gian kh di. Kinh nghim cho thy, t l
BOD5/BODtng cng tng i cao nn thi gian 5 ngy l hp l. T l ny cao hay
thp ty thuc vo c tnh ca seed v bn cht ca cht hu c. Nc thi sinh
hot v nhiu loi nc thi cng nghip c BOD5 = 70 80% BOD tng. Thi gian 5
ngy cn c tc dng loi tr nh hng ca qu trnh oxy ha ammonia do
Nitrosomonas v Nitrobacter gy ra.
5.2 BN CHT CA PHN NG BOD
Nhng nghin cu ng hc cho thy rng phn ng BOD l phn ng bc 1 c ngha
l vn tc phn ng t l thun vi lng cht hu c c kh nng phn hy sinh hc.
Tc phn ng c biu din nh sau:
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dC
dt
= k 'C
dC
dt
= C
(5 - 2)
Trong , C c trng cho nng ca cht hu c c kh nng oxy ha, t l thi gian
v k l hng s tc phn ng. Nh vy, vn tc phn ng gim khi nng cht
hu c C gim.
Trong phn tch BOD, L thng c dng thay cho C:
dC
= k 'L
dt
(5 - 3)
-dL/dt biu din tc phn hy cht hu c. Ly tch phn hai v Phng trnh (5
3) ta c:
Lt
= e k 't = 10 kt
L
(5 - 4)
Trong , k = k/2,303, cng thc ny biu din lng cht hu c cn li sau khong
thi gian t bt k.
Nu gi y l BOD ti thi im t v L l lng BOD tng hoc BOD cc i:
y = L (1 10-kt)
Gi tr k phi c xc nh bng thc nghim.
V phn ng phn hy cht hu c BOD l phn ng bc 1, th biu din lng cht
hu c cn li theo thi gian c dng parabol tng t ng cong phn r ca mt
nguyn t phng x. Do , th m t lng cht hu c b oxy ha theo thi gian s
l ng parabol i xng (Hnh 5.1).
V lng oxy c dng t l thun vi lng cht hu c b oxy ha, th biu din
lng oxy s dng theo thi gian cng c dng parabol nh ng m t lng cht
hu c b oxy ha Hnh 5.1. Hnh 5.2 biu din ng cong BOD hay oxy tiu th
theo thi gian.

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Chat hu c
Chat hu c oxy hoa

Chat hu c con lai
-dC/dt = kC
Thi gian (ngay)

Hnh 5.1 Cht hu c b oxy ho
Nhu
cau
oxy
sinh
hoa
(BOD)
(b)
ng cong oi vi
nhu cau lien ket
(carbonate ceous + s nitrat hoa)
(a)
ng cong oi vi
nhu cau co carbon 20oC
y = L (1-10-kt)
Gia tr L
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Thi gian (ngay)

Hnh 5.2 ng cong BOD
(a) ng cong chun i vi qu trnh oxy ha cht hu c.
(b) nh hng ca s nitrat ha.
Trong mt s trng hp cn dng seed trong phn tch BOD. Seed c th cha vi
khun nitrat ha c kh nng oxy ha cht khng cha carbon ch o nng lng. Vi
khun nitrat ha thng tn ti vi lng tng i nh trong nc thi sinh hot cha
x l v iu may mn l tc ti sinh ca chng 200C ca chng khng qu ln
dng mt lng ng k oxy trong vng 8 10 ngy u trong th nghim BOD. Khi
cc sinh vt ny pht trin, chng oxy ha nit dng ammonia thnh cc acid HNO2
v acid HNO3 gy sai s ng k cho th nghim BOD.
2NH3 + 3O2
2NO2- + 3O2
nitrosomonat
nitrobacter
2NO2- + 2H+ + 2H2O

2NO3- + 2H+
(5 - 5)
(5 - 6)

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Khng th dng ch tiu BOD xc nh lng nit c trong mu v nit c thm

vo nc pha long cung cp cht dinh dng cn thit cho vi sinh vt nn s dn
n sai s cho kt qu th nghim.
loi tr nh hng do qu trnh nitrat ha gy ra, thi gian trong th nghim BOD
c qui nh l 5 ngy.
i vi nc thi c cha nhiu nitrat nh nc thi sau x l sinh hc, nh hng
ca vi khun nitrat ha c ngn chn bng nhng tc nhn c ch nh methylene
blue hoc allylthourea (ATU). Mc nitrat ha cng c th c lm gim ng k
nh qu trnh kh trng bng clo.
Mu nc sng v ca sng thng cha lng ng k vi sinh vt nitrat ha. Hn
na, s pht trin ca to cng gy ra sai s cho gi tr BOD.
5.3 PHNG PHP XC NH BOD
Ch tiu BOD c xc nh bng cch phn tch hm lng oxy ha tan. Thng mu
phn tch c hm lng cht hu c cao nn cn phi pha long. Tuy nhin, khi hm
lng cht hu c trong mu thp, c th tin hnh phn tch trc tip, khng phi pha
long mu.
Phng php trc tip
Vi mu c BOD5 khng vt qu 7 mg/L, khng pha long, ch cn sc kh t oxy
bo ha thch hp lc bt u th nghim. Trng hp ny thng thy i vi nc
sng.
Hai hoc nhiu chai BOD ng y mu. Mt chai c dng phn tch ngay hm
lng oxy ha tan (DO0) v nhng chai cn c 5 ngy 200C. Sau 5 ngy, xc
nh hm lng oxy ha tan cn li (DO5). BOD5 = DO0 DO5.
Phng php trc tip xc nh BOD khng bin i mu, do cho kt qu iu
kin gn nh tng t vi mi trng t nhin.
Phng php pha long
Phng php pha long xc nh BOD da trn c s tc phn hy sinh ha
cht hu c t l thun vi lng cht hu c cha b oxy ha tn ti mt thi im
no .
Trong th nghim phn tch ch tiu BOD cn (1) trnh cc cht c hi i vi vi sinh
vt, (2) pH v iu kin thm thu phi thch hp, (3) cht dinh dng, (4) nhit tiu
chun v (5) seed.
Nhiu nc thi cng nghip c BOD5 rt cao nn phi pha long nhiu ln do kh
nng ha tan gii hn oxy trong nc. Nc thi sinh hot cha nhiu cht dinh dng
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nh N v P, trong khi nhiu cht thi cng nghip thiu mt hoc i khi c hai
nguyn t ny. Do , vic s dng nc pha long l cn thit.
Nc pha long
Nhiu loi nc c th dng lm nc pha long trong th nghim BOD. Nc thin
nhin c th cha to v vi khun nitrat ha, hm lng khong thay i,... nn khng
thch hp. Nc my cng chu hu ht nhng hn ch ca cc dng nc b mt
thm vo l tnh kh ca phn clo cn li. Kinh nghim cho thy dng nc pha
long tng hp iu ch t nc ct hoc nc kh khong l tt nht.
pH ca nc pha long c th thay i t 6,5 n 8,5 khng gy nh hng n hot
ng ca vi khun saprophytic. Thng m dung dch bng hn hp phosphate pH
7,0. Dung dch m dng duy tr pH thch hp.
iu kin thm thu thch hp c duy tr bng K3PO4 v Na3PO4. Cc mui K, Na,
Ca v Mg thm vo to kh nng m v thm thu thch hp cng gp phn cung
cp cn thit cho s sinh trng v trao i cht ca vi sinh vt. FeCl3, MgSO4 v
NH4Cl cung cp Fe, S v N. Dung dch m phosphate nhm cung cp P. Trong trng
hp nhu cu oxy c cha nit phi c o, cn phi loi nit.
Nc pha long cha tt c nhng cht ch yu xc nh BOD tr vi sinh vt cn
thit. Nhiu cht c dng lm seed. Kinh nghim cho thy rng nc thi sinh
hot, c bit l nc t h thng cng chung l thch hp, thng dng 2 mL nc
thi cho mt lt nc pha long. Mt s loi nc sng cng tha yu cu, nhng phi
cn thn trnh dng nc c cha nit phi c o, cn phi loi nit.
Trong trng hp phi cung cp seed, nc pha long cn phi c ha trn vi
seed v cc cht dinh dng trc khi th nghim bo m tnh ng nht ca nc
pha long s dng.
Cui cng, nc pha long phi c sc kh n khi t bo ha oxy trc khi s
dng.
S pha long nc thi
Ngi phn tch t quyt nh mc pha long mu, thng thng nn pha long 3
t l khc nhau. Khi nng ca mu trong khong c bit, ch cn pha long 2 t
l khc nhau l . i vi mu khng bit trc nng , trong nhiu trng hp cn
phi pha long 4 t l khc nhau. Mu phn tch phi m bo c t nht 0,5 mg/L oxy
ha tan thi im cui ca giai on . Bng 5.1 biu din t l pha long cn thit
tnh theo % hoc ly trc tip vo chai BOD (dung tch 300 mL) bng pipet.

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Bng 5.1 T l pha long mu da trn nng BOD d on

% hn hp
% hn hp
0,01
0,02
0,05
0,1
0,2
0,5
1,0
2,0
5,0
10,0
20,0
50,0
100
Khong BOD
20.000 70.000
10.000 35.000
4.000 14.000
2.000 7.000
1.000 3.500
400 1.400
200 700
100 350
40 140
20 70
10 35
4 14
0-4
Dng pipet ly mu vo chai BOD 300

mL
mL
0,02
0,05
0,10
0,20
0,50
1,0
2,0
5,0
10,0
20,0
50,0
100
300
Khong BOD
30.000 105.000
12.000 42.000
6.000 21.000
3.000 10.500
1.200 4.200
600 2.100
300 420
60 210
30 105
12 42
6 21
07
Trong qu trnh phi nim ming chai BOD bng mt mng kh ngn khng kh
ha tan vo chai. Chai BOD phi c ra sch dung dch acid chromic hoc nc ty
ra. Nu dng nc ty ra, chai phi c ra li bng nc nng dit vi khun
nitrat ha. Sau ra li tht k bng nc my v trng ln cui bng nc ct hoc
nc kh khong.
Oxy ha tan ban u
Vi nhng mu c BOD < 200 mg/L, lng mu > 1,0%, kt qu phn tch s sai s
ng k nu oxy ha tan ca mu khc vi oxy ha tan ca nc pha long v khng
th hiu chnh c. Nu t l pha long < 20%, mu c n nh nhit 200C,
sc kh n bo ha, khi xem nh mu c cng nng oxy ha tan vi nc pha
long. Do , khng cn phi xc nh nng oxy ha tan ca mu. Nu t l pha
long > 20%, cn phi xc nh nng oxy ha tan ca mu.
Trong phn tch BOD, gim nng oxy ha tan sau 5 ngy phi hn 2 mg/L v
nng oxy ha tan cn li phi ln hn 0,5 mg/L, sai s th nghim khong 5%.
5.4 VN TC CA QU TRNH OXY HA SINH HA
Hng s tc ca phn ng phn hy cht hu c BOD c xem l k =0,10/ngy
200C. Gi tr ny c c t nhiu nghin cu v nc sng b nhim v nc thi
sinh hot M v Anh. Kt qu th nghim i vi nc thi cng nghip s dng
nc pha long tng hp cho thy k > 0,10/ngy v gi tr k ca cc loi nc thi
khc nhau. Gi tr k ca nc thi sinh hot thay i ng k mi ngy v gi tr trung
bnh l 0,17/ngy, khc vi gi tr 0,10/ngy nh xc nh trc y. Cc gi tr k
ca nc thi qua x l sinh hc s thp hn nc thi cha x l. Yu t khc nh
hng n kt qu o c BOD l nhit . Bin thin BOD theo thi gian c biu
din Bng 5.2.
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Bng 5.2 ngha quan trng ca hng s tc phn ng k i vi BOD

Thi gian
(ngy)
% BOD tng s dng

k = 0,05
10,9
20,6
29
37
44
50
55
68
90
1
2
3
4
5
6
7
10
20
k = 0,10
20,6
37
50
60
68
75
80
90
99
k = 0,15
29,2
50
64
75
82
87
91
97
99
k = 0,20
36,9
60
75
84
90
94
96
99
99
k = 0,25
43,8
68
82
90
94
97
98
99
99
Bng 5.2 cho thy phn ng BOD thay i rt ln ty thuc vo tc phn ng. Cc
gi tr BOD5 bng khong 68% BOD tng k = 0,1/ngy v bng 94% khi k =
0,25%/ngy.
ngha quan trng ca k trong vic xc nh hng pht trin phn ng BOD c
minh ha Hnh 5.3. i vi mt cht thi c gi tr L cho trc, gi tr BOD5 s thay
i ng k trong vng 15 ngy. Trc y, thng biu din BOD5 ngy theo L bng
cch cho k = 0,10/ngy. Hnh 5.4 cho thy gi tr L ca mt mu vi BOD5 = 200 thay
i theo gi tr k.
k = 0,30
300
BOD (mg/L)
250
k = 0,15
200
k = 0,08
k = 0,10
150
100
50
0
10
Thi gian (ngay)
15
20
Hnh5.3 nh hng ca hng s tc i vi BOD ( mt gi tr L cho trc).

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Tc phn ng thay i theo (1) bn cht ca cht hu c v (2) kh nng cc sinh

vt hin c s dng cht hu c.
5.5 S KHC NHAU GIA CC GI TR L V NHNG GI TR NHU CU OXY
THEO L THUYT
Trc y, gi tr BOD tng cng hay L ca cc cht hu c c xem bng nhu cu
oxy theo l thuyt khi c tnh t Phng trnh ha hc tng ng (xem Phng trnh
5.10). V d, s oxy ha glucose thnh CO2 v nc cn 192 gO2/mol hoc 1,065
mLO2/mol glucose.
C6H12O6 + 6O2 6CO2 + 6H2O
(5 - 10)
BOD ca dung dch glucose c nng 300 mg/L theo l thuyt l 320 mg/L. Thc t,
BOD20 dao ng t 250 n 285. Nh vy, khng phi tt c glucose c chuyn
thnh CO2 v H2O.
vi sinh vt oxy ha cht hu c, cht hu c phi l thc n cn thit cho s sinh
trng v pht trin ca vi sinh vt. Nh vy, mt phn cht hu c c chuyn vo
m t bo v di tr khng b oxy ha cho n khi vi sinh vt s dng cc cht hu c
ny trong qu trnh h hp ni bo. Khi vi sinh vt cht chng tr thnh thc n cho vi
sinh vt khc v bin thnh carbonic v nc. Vi sinh vt sng cng nh cht, dng
lm thc n cho nhng sinh vt cao cp hn chng hn nguyn sinh ng vt. Lng
cht hu c cn li khng b phn hy sinh hc l bn.
5.6 S KHC NHAU GIA TC QUAN ST C V TC BC I
Kho st gi tr BOD ca cc cht hu c ha tan vi gi thit phn ng bc 1. Trong
nhiu trng hp, bin thin BOD xy ra theo hai pha tng t nh Hnh 5.2. Tuy
nhin, pha th hai khng phi do s nitrat ha m do tc dng bc 2 ca protozoa:
trong mt hoc hai ngy u ca giai on , cht hu c ha tan b tiu th nhanh,
khong 30% n 50% b oxy ha v phn cn li c chuyn vo t bo vi sinh vt.
Khi s chuyn ha ny c hon thnh, tc oxy ha gim do qu trnh h hp ni
bo ca vi sinh vt. Mt hoc hai ngy sau tc oxy ha tng ln bc hai do s tng
mt protozoa dng vi sinh vt lm thc n. Nh vy, protozoa cng ng vai tr
rt quan trng trong th nghim BOD.
5.7 NG DNG CA S LIU BOD
S liu BOD c dng rng ri trong thc t k thut mi trng. BOD l ch tiu
quan trng nh gi tnh cht nc thi sinh hot v nc thi cng nghip. BOD l
ch tiu duy nht xc nh lng cht hu c c kh nng phn hy sinh hc. BOD
cn l ch tiu nh gi lm t sch cc ngun nhn v l tiu chun kim tra cht
lng ca cc dng thi vo ngun nc ny. BOD l c s chn phng php x
l v xc nh kch thc ca nhng thit b v nh gi hiu qu ca tng n v
trong h thng x l.
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CHNG 6
NHU CU OXY HA HC
6.1 GII THIU CHUNG
Ch tiu COD c dng xc nh hm lng cht hu c c trong nc thi sinh
hot v nc thi cng nghip. COD l lng oxy cn thit oxy ha cht hu c
thnh CO2 v H2O di tc dng ca cc cht oxy ha mnh. Phng trnh phn ng
oxy ha c th biu din n gin nh sau:
CnHaObNc + (n + a/4 - b/2 - 3/4c) O2 nCO2 + (a/2 - 3/2c)H2O + cNH3
(6 - 1)
Trong thc t hu nh tt c cc cht hu c u b oxy ha di tc dng ca cc

cht oxy ha mnh trong mi trng acid. Amino (s oxy ha -3) s chuyn thnh
NH3-N (phng trnh 1). Tuy nhin, nit hu c c s oxy ha cao hn s chuyn
thnh nitrate.
Khi phn tch COD, cc cht hu c s chuyn thnh CO2 v H2O, v d c glucose v
lignin u b oxy ha hon ton. Do , gi tr COD ln hn BOD v c th COD rt ln
hn nhiu so vi BOD khi mu cha a phn nhng cht kh phn hy sinh hc, v d
nc thi giy c COD >> BOD do hm lng lignin cao.
Mt trong nhng hn ch ch yu ca phn tch COD l khng th xc nh phn cht
hu c c kh nng phn hy sinh hc v khng c kh nng phn hy sinh hc. Thm
vo phn tch COD khng cho bit tc phn hy sinh hc ca cc cht hu c c
trong nc thi di iu kin t nhin.
u im chnh ca phn tch ch tiu COD l cho bit kt qu trong mt khong thi
gian ngn hn nhiu (3 gi) so vi BOD (5 ngy). Do trong nhiu trng hp, COD
c dng nh gi mc nhim cht hu c thay cho BOD. Thng BOD = f x
COD, trong f l h s thc nghim.
6.2 CC PHNG PHP PHN TCH COD DNG
Nhiu cht oxy ha ha hc c dng xc nh nhu cu oxy ha ha hc ca
nc b nhim. Nhiu nm trc y, dung dch KMnO4 c dng trong phn tch
COD. Mc oxy ha do permanganate thay i theo nhng loi hp cht khc nhau
v mc oxy ha thay i ng k theo nng cc tc cht s dng.
Gi tr COD xc nh bng phng php ny lun lun nh hn nhiu so vi BOD5.
iu chng t rng permanganate khng th oxy ha hon ton tt c cc cht hu
c c trong nc phn tch.
Ceric sulfate, iodate kali, v dichromate kali l nhng cht oxy ha c dng trong
phn tch COD. Trong , dichromate kali l cht oxy ha thch hp nht v dichromate
kali c kh nng oxy ha hon ton hu ht cc cht hu c thnh CO2 v nc. V tt
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c cc cht oxy ha du dng vi lng d nn cn phi xc nh lng cn tha.

Sau khi phn ng kt thc tnh ton lng cht oxy ha tht s dng oxy ha
cht hu c. K2Cr2O7 l cht rt d xc nh bt c lng d cn li no (d nh) sau
phn ng. Do , K2Cr2O7 chim u th hn nhiu cht oxy ha khc.
K2Cr2O7 c th oxy ha hon ton cht hu c trong mi trng acid mnh v mt
nhit xc nh. Cc cht hu c d bay hi c sn trong mu hoc to thnh trong
qu trnh phn hy d dng b tht thot nn qu trnh ngng t hon lu rt cn thit.
Mt s cht hu c, c bit l cc acid bo phn t lng thp, khng b oxy ha nu
khng c cht xc tc. Ag+ l tc nhn xc tc rt hiu qu c dng. Cc
hydrocacbon thm v pyridine khng b oxy ha trong iu kin th nghim.
6.3 PHN TCH COD BNG K2Cr2O7
K2Cr2O7 l hp cht tng i r tin v c tinh khit cao, sau khi sy nhit
1030C, c th dng pha dung dch nng 1N chnh xc bng cch cn v pha
long trong mt th tch thch hp. K2Cr2O7 l cht oxy ha mnh trong mi trng acid
mnh. Phng trnh phn ng tng qut c th biu din nh sau:
CnHaObNc + dCr2O7
2-
+ (8d + c)H nCO2 + (a + 8d - 3c)/2 H2O + cNH4+ + 2dCr3+

+
(6 - 2)
Trong
d = 2n/3 + a/6 - b/3 - c/2
Phng php phn tch mu c COD cao
Trong bt k phng php xc nh COD no, cht oxy ha phi cn d sau phn ng
m bo cc cht hu c b oxy ha hon ton.
Do phi c mt lng thch hp cht oxy ha cn tha sau phn ng i vi tt c
cc mu, t mi xc nh c lng thc s tham gia phn ng.
Hu nh tt c cc dung dch ca cc cht kh u b oxy ha dn dn bi oxy khng
kb ha tan vo dung dch tr khi mu c bo qun khng tip xc vi khng kh. Ion
Fe2+ l tc nhn kh hiu qu ca dichromate. Dung dch cha Fe2+ c pha t
Ferrous Ammonium Sulfate (FAS) kh tinh khit v bn vng. Tuy nhin trong dung
dch, Fe2+ b oxy ha dn dn bi O2 do cn phi chun b li mi khi s dng. Phn
ng gia FAS v K2Cr2O7 c biu din nh sau:
6Fe2+ + Cr2O72- + 14H+ 6Fe3+ + 2Cr3+ + 7H2O
Mu trng

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C phn tch COD v BOD c dng xc nh lng oxy cn oxy ha cc cht

hu c c trong mu. Php phn tch phi bo m kt qu gi tr COD ca mu khng
b nh hng ca bt k ngun cht hu c no khc gy ra. V vy mu trng cn
c xc nh trong cc th nghim COD v BOD.
Ch th
in th oxy ha kh thay i rt nhiu ti im dng ca tt c cc phn ng oxy ha
kh. Nhng bin i ny c th nhn bit d dng bng in th k. Ngoi ra cng c
th s dng ch th oxy ha kh xc nh im dng ca phn ng. Ferroin l mt
ch th hu hiu dng nhn bit phn ng kt thc khi tt c Fe2+ b oxy ha
hon ton. Khi mu xanh ca Cr3+ sinh ra do qu trnh kh Cr2O72- chuyn thnh
mu nu .
Tnh ton
(Vmau trang 150 - Vmau o) x
COD =
3
Vmau trang nhiet o phong
x 0,1 x 8000
mL mau phan tch

COD =
(A - B) x M x 8000
mL mau phan tch
Phng php xc nh mu COD thp

Phng php trn ng vi mu c COD > 50mg/L. i vi nhng mu c COD < 50
mg/L cn phi dng dung dch K2Cr2O7 long hn c th xc nh chnh xc hn
lng K2Cr2O7 cho vo v cn tha sau phn ng. iu quan trng phi ch l t l
th tch H2SO4 m c: tng th tch (mu + dd K2Cr2O7) = 1:1. Nu t l ny nh hn,
nng lng oxy ha ca dung dch s gim ng k, tri li lng dichomate tiu tn
cho mu trng s tha.
Phng php lm gim lng cht thi c hi
Gim th tch mu + tc nhn ha hc s dng
Tr ngi ca cc cht v c
Mt s ion v c c th b xy ha di iu kin th nghim COD v gy sai s tha
rt ln. Cl- l mt trong nhng ion gy sai s ln nht cho th nghim COD:
6Cl- + Cr2O72- + 14 H+ 3Cl2 + 2Cr3+ + 7H2O
Khc phc bng cch dng HgSO4
Hg2+ + 2Cl- HgCl2 (2 = 1,7 x1013)
Nitrit b oxy ha thnh nitrate cng gy ra sai s COD. Khc phc bng cch thm
sulphamic acid vo dung dch dichnmate.
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CHNG 7
ST & MANGAN
7.1 GII THIU CHUNG
C st v mangan u gy nh hng ng k n vic cp nc, c bit i vi
ngun nc ngm. Mt s ngun nc ngm khng cha st v mangan nhng mt
s khc li lun cha lng ng k. iu ny ch c th gii thch c trn c s
ha v c.
Fe tn ti trong t v khong cht ch yu di dng oxyt st (III) khng tan v pyrit
st (FeS2). mt s ni, st tn ti di dng FeCO3 t tan. V nc ngm thng
cha mt lng ng k CO2, FeCO3 c th b ha tan theo phng trnh phn ng
sau:
FeCO 3 + CO 2 + H 2 O Fe 2+ + HCO 3 - (1)
BB
BB
BB
BB
BB
BB
PP
PP
BB
PB
PP
Phn ng ny khng xy ra ngay c khi hm lng CO2 v FeCO3 cao nu c mt oxy

ha tan. Tuy nhin, trong iu kin k kh, Fe3+ b kh thnh Fe2+ mt cch d dng.
Mangan tn ti trong t ch yu di dng MnO2, rt t tan trong nc c cha CO2.
Di iu kin k kh, MnO2 b kh thnh Mn2+
St v Mangan tn ti trong ngun nc do s thay i iu kin mi trng di tc
dng ca cc phn ng sinh hc xy ra trong cc trng hp sau:
1. Nc ngm cha mt lng ng k st hoc mangan hoc c st & mangan s
khng cha oxy ha tan v c hm lng COB2B cao. St v mangan tn ti di
dng Fe2+ v Mn2+. Hm lng CO2 cao chng t qu trnh oxy ha cc cht hu
c di tc dng ca vi sinh vt xy ra v nng oxy ha tan bng khng
chng t iu kin k kh hnh thnh.
2. Ging nc tt c hm lng st v mangan thp. Nu sau cht lng nc
khng tt, chng t cht thi hu c thi ra mt t khu vc gn ging nc
to ra mi trng k kh trong lp t.
3. Trn c s nhit ng hc, Mn (IV) v Fe (III) l trng thi oxy ha bn nht ca Fe
v Mn trong cc ngun nc cha oxy. Do , chng c th b kh thnh Mn (II) v
Fe (II) ha tan ch trong mi trng k kh.
4. Nhng nghin cu gn y cho thy rng mt s vi sinh vt c kh nng s dng
Fe (III) v Mn (IV) lm cht nhn in t cho qu trnh trao i cht di iu kin
k kh dn n s hnh thnh cc dng kh Fe (II) v Mn (II). Nh vy, vi sinh vt
khng ch to ra mi trng k kh cn thit cho qu trnh kh m cn c kh nng
kh trc tip Fe v Mn.
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Qu trnh oxy ha pyrit st (FeS2) khng tan cng l nguyn nhn to ra mi trng k
kh v s hnh thnh sulfat st ha tan:
2 FeS 2 + 7O 2 + 2H 2 O 2 Fe 2+ + 4SO 4 2- + 4H +
BB
BB
BB
BB
BB
BB
PP
PP
BB
PB
PP
PP
(2)
PP
7.2 NGHA MI TRNG CA Fe V Mn

Nc cha st v mangan khng nh hng n sc khe ca con ngi. Nhng
ngun nc ny khi tip xc vi oxy khng kh tr nn c v to cm quan khng tt
i vi ngi s dng do s oxy ha st v mangan thnh Fe (III) v Mn (IV) tn ti
di dng kt ta keo. Tc oxy ha chm v cc dng kh c th tn ti trong nc
sc kh trong mt khong thi gian nht nh. iu ny c bit ng khi pH < 6 i
vi qu trnh oxy ha st v pH < 9 i vi qu trnh oxy ha mangan. Thm vo ,
st v mangan c th to thnh phc bn vi cc hp cht humic trong nc. Tc
oxy ha gia tng di tc dng ca mt s cht xc tc v c hoc do hot ng ca
cc vi sinh vt. St v magnan c mt trong nc s lm vng qun o, nh hng
n h thng cp nc do s pht trin ca vi khun oxy ha st. St cng gy mi
tanh cho ngun nc d nng rt nh. Do tiu chun i vi nc cp l < 0,3
mg Fe/L v < 0.05 mg Mn/L (U.S. Environmental Protection Agency).
7.3 PHNG PHP XC NH
C nhiu phng php xc nh st c p dng. Phng php kt ta c s
dng khi lng st c trong mu kh cao, v d trong trng hp nc thi cng
nghip. Tuy nhin, trong nc cp hm lng st nh nn phng php so mu thch
hp hn. u im chnh ca phng php so mu l rt c trng cho ion cn xc
nh v t phi x l s b mu. Ngoi ra, cng c th xc nh st bng phng php
hp ph quang ph nguyn t.
Phng php Phenanthroline
Phng php Phenanthroline l phng php tiu chun thch hp xc nh lng
st c trong nc tr khi mu c cha phosphat v kim loi nng. Phng php ny
da trn c tnh ca 1, 10-phenanthroline c kh nng kt hp vi Fe2+ to thnh
phc c mu cam. Mu to thnh c o bng quang ph k.
Thng mu phn tch tip xc vi khng kh nn mt phn Fe (II) b oxy ha thng Fe
(III) v kt ta di dng Fe(OH)3. Trong th nghim ny nht thit ton b st c trong
mu phi dng ha tan. Do , lng HCl m c cho vo mu nhm ha tan
Fe(OH)3
Fe(OH)3 + 3H+ Fe3+ + 3H2O
(3)
V 1, 10-phenanthroline ch to phc vi Fe (II), tt c st dng Fe (III) phi c kh

thnh Fe (II). Hydroxylamine c dng lm tc nhn kh, phng trnh phn ng xy
ra nh sau:
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4 Fe (III) + 2 NH 2 OH 4 Fe (II) + N 2 O + H 2 O + 4H + (4)

BB
BB
BB
BB
BB
BB
PP
PP
3 phn t 1, 10 - phenanthroline s k hp vi 1 phn t Fe2+ to phc theo

phng trnh phn ng sau:
loi tr nh hng ca phosphat v kim loi nng, acid ha mu bng HCl v trch
Fe vo diisopropyl-ether trc khi cho ch th phenanthroline.
Phng php xc nh Mangan
Trong thc t k thut mi trng, mangan ch yu lin quan n ngun cp nc.
Nng mangan t khi vt qu vi mg/L, do phng php so mu l phng php
thch hp nht. Phng php so mu theo standard Methods ph thuc vo s oxy
ha Mangan trng thi oxy ha thp thnh Mn7+, khi s hnh thnh mu rt r ca
ion permanganate. Mu to ra t l thun vi nng ca mangan trong mt khong
dao ng cho php thch hp vi nh lut Beer v o bng quang ph k. Clorua s
nh hng n kt qu th nghim do tnh kh ca Cl- trong mi trng acid. Ngoi ra,
cng c th xc nh Mn bng phng php quang ph hp ph nguyn t.
Phng php Persulfate
Phng php Persulfate l phng php thch hp dng trong phn tch ch tiu Mn v
khng cn phi x l mu trc khc phc nh hng ca Cl-. Ammonium sulfate
thng dng lm tc nhn oxy ha. V ammonium persulfate b gim cht lng trong
qu trnh tr nn cn phi lm li chun i vi mi lot mu o.
nh hng ca Cl- c th khc phc bng cch thm Hg2+ to phc HgCl2. V hng
s bn ca HgCl2 = 1.7 x 1013, nng ca Cl- gim n mc thp nn khng th
kh ion permanganate.
S oxy ha mangan trng thi oxy ha thp hn thnh permanganate di tc dng
ca persulfate i hi c mt cht xc tc Ag+. Phn ng xy ra theo phng trnh sau:
2Mn 2+ + 5S 2 O 8 2- + 8H 2 O 2MnO 4 - + 10SO 4 2- + 16H +
PP
PP
BB
BB
BB
PB
PP
BB
BB
BB
PB
PP
BB
PB
PP
PP
PP
(6)
Mu do ion permanganate to ra bn trong vi gi vi iu kin nc ct c ch lng

tt v mu c bo qun khng b nhim bi t khng kh.
7.4 NG DNG CA S LIU Fe V Mn
Khi kho st ngun nc mi, c bit l nc ngm, vic xc nh st v mangan c
ngha quan trng. T l st v mangan l thng s xc nh phng php x l cng
nh lng cht hu c c trong nc. Hiu qu ca tng n v x l c nh gi
da trn kt qu phn tch Fe v Mn. Ch tiu ny cng gip gii quyt cc vn v
h thng phn phi khi vi khun oxy ha st tn ti trong ng ng.

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Qu trnh n mn ng ng bng st v thp l nguyn nhn to ra nc trong

h thng phn phi. Do , phn tch ch tiu st gip nh gi mc n mn v tm
phng php khc phc.

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CHNG 8
SULFATE
8.1 GII THIU CHUNG

Ion sulfate l mt trong nhng anion thng gp trong nc t nhin. N l ch tiu
quan trng trong nc cp v khi hm lng SO42- trong nc cao s gy nh hng
n con ngi do tnh cht ty ra ca sulfate. T l do ny, i vi nc cp, nng
gii hn ca sulfate l 250 mg/L. Ngoi ra trong nc cp cho cng nghip v sinh
hot, ch tiu SO42- cng rt quan trng do kh nng kt hp vi cc ion kim loi trong
nc hnh thnh cn trong cc thit b un nc, l hi v cc thit b trao i nhit.
Trong x l nc thi, ch tiu SO42- cng c quan tm do vn v mi v n mn
ng ng do qu trnh kh sulfate thnh hydrogen sulfide trong iu kin k kh.
Phng trnh c biu din nh sau
hiu r nhng bin i ca sulfate, chu trnh lu hunh c trnh by trong Hnh
8.1

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H 2S
S=
SO2
SO3=
Chat thai
hu c
h
Urin
Lu
huynh
SO3
SO4=
Protein
ong vat
Protein
thc vat
Hnh 8.1 Chu trnh sulfur (lu hunh) trong t nhin.
Vn v mi
Khi khng c s hin din ca oxy, sulfate c coi nh l cht cung cp oxy (chnh
xc hn l cht nhn in t) cho qu trnh oxy ha sinh ha ca vi khun k kh. Trong
iu kin k kh, sulfate b kh thnh S2-. Ion S2- s kt hp vi ion H+ vi hng s
phn ly KA1 = 9,1.10-8. Quan hgia cc dng H2S, HS- v S2- ti cc pH khc nhau
ca dung dch cha 10-3 M H2S (hay 32 mg/L H2S) c trnh by trong Hnh 8.2.

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100
80
S=
HS-
60
%
40
H 2S
20
0
5
8
pH
10
11
Hnh 8.2 Quan h gia cc dng H2S, HS- v S2- ti cc pH khc nhau ca dung dch
cha 10-3 M H2S (hay 32 mg/L H2S).
Ti pH ( 8 trong dung dch tn ti ch yu hai dng HS- v S2-, H2S ch tn ti mt lng
rt nh, v vy p sut ring phn ca n rt thp. Do , vn mi khng xy ra. Ti
pH < 8 cn bng hng ti s hnh thnh H2S, ti pH = 7, 80% S2- dng H2S. Khi
mt lng ln sulfate b kh thnh ion sulfide, p sut ring phn ca H2S gy ra
vn v mi. Do c tnh ca kh H2S, trong khng kh hm lng ca H2S nn nh
hn 20 ppm.
n mn ng ng
S n mn nh cng (crown) ca ng bton l c bit nghim trng khi m nc
thi sinh hot c nhit cao, thi gian lu trong cng di v nng sulfate cao, iu
ny xy ra nhiu vng ca M, c bit nhng vng pha nam nc ny.
Nguyn nhn ca s n mn c cho l do H2S v H2SO4 bi qu trnh kh sulfate
thnh H2S v t H2S thnh H2SO4. Thc ra H2S, hay H2S acid, l mt acid yu, yu
hn c H2CO3 v t nh hng n bton c cht lng cao. Tuy nhin, trong h thng
cng thot nc t chy , H2S l nguyn nhn gin tip gy ra s n mn nh cng.
i vi cng thot nc t chy thng t dng trong nhng mi trng c s hin
din ca sulfate v c nhng bin i sinh hc. H thng cng l mt phn ca h
thng x l v trong qu trnh vn chuyn nc thi lun xy ra cc bin i sinh hc.
Nhng bin i ny i hi c mt ca oxy, nu lng oxy khng do qu trnh thng
gi t nhin ca khng kh trong cng, qu trnh kh sulfate thnh sulfide s xy ra.
pH thng thng ca nc thi, hu ht S2- dng H2S v mt phn ca n bay vo
lp khng kh trn lp nc thi trong cng. Nu h thng cng c thng gi tt
v thnh cng v nh cng kh ro, vic hnh thnh ca H2S khng gy ra s n mn
cng. Tuy nhin, trong trng hp thng gi km, thnh v nh cng m t, H2S s
ha tan vo lp nc trn thnh v nh cng tng ng vi p sut ring phn ca n
trong khng kh hin din trong cng. iu ny hu nh khng gy nguy hi no.
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Vi khun c kh nng oxy ha H2S thnh H2SO4 c mt khp ni trong t nhin v

trong nc thi. V d nhin l loi vi khun ny cng c mt trn thnh v nh cng
ti nhng lc lu lng ln hay theo mt s cch khc. Do iu kin hiu kh l lun
tn ti trong h thng cng, nhng vi khun hiu kh oxy ha H2S thnh H2SO4 theo
Phng trnh 1.10-4 v sau tr nn m c v n mn bton. Vi khun
Thiobacillus, c kh nng oxy ha H2S thnh H2SO4 pH 2, c cho l loi vi khun
chnh gy ra vn ny. Qu trnh hnh thnh H2SO4 c bit nghim trng nh
cng do ti qu trnh rt nc l nh nht.cc vn v mi v n mn trong h
thng cng c minh ha trong Hnh 8.3
H2S+O2
Vi khuan
H2SO4
Moi trng e vi
khuan oxy hoa H2S
Giot nc
O2
H 2S
O
H 2S 2
H2 S
O2
Khong kh O2
H 2S
H2 S
O2
H 2S
Nc thai
ieu kien S=
k kh
S= + 2H+ H2S
So
=
4
Hnh 8.3 S hnh thnh H2S v s n mn do qu trnh oxy ha H2S thnh H2SO4 trong cng.
Nhng vn ng quan tm khc
Trong khai thc khong sn (bng phng php sa lng) v than, nc thi hoc nc
r r thng c pH thp v nng sulfate cao. Lng sulfide trong khong s c
oxy ha do hot ng ca vi sinh vt v cc tc nhn ha hc to thnh acid
sulfuric.
Khng nhng iu ny lm gia tng hm lng sulfate trong nc thi ra t cc m m
cn lm gim pH v tng hm lng st v iu ny lm gim cht lng nc. Trong
trng hp ny, bin php c dng l ph kn m trnh oxy v nc i vo m
trnh phn ng trn xy ra.
Qu trnh t nhin liu ha thch cng to ra mt lng SOx, nhng kh ny khi thy
phn trong nc ma hnh thnh acid sulfuric v s gy ra vn ma acid.
8.2 CC PHNG PHP PHN TCH
C 4 phng php chun c dng phn tch hm lng sulfate trong nc, trong
phng php sc k ion l phng php tt nht v c th xc nh sulfate trong
nc nng thp n 0,1 mg/L. Ba phng php cn li l da trn lng BaSO4
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khng tan to thnh khi thm mt lng d BaCl2 vo trong mu. S khc bit gia ba
phng php cn li l s khc nhau trong phng php xc nh lng BaSO4 hnh
thnh. Trong phng php khi lng, lng kt ta BaSO4 to thnh c mang cn.
Trong phng php o c, lng BaSO4 c xc nh da trn nh hng ca
kt ta n qu trnh truyn nh sng. Trong phng php Methylthylmol Bule, lng
Ba d c xc nh bng phng php o mu t tnh ra lng Ba kt hp vi
Sulfate. Vic la chn phng php o ph thuc vo mc ch xc nh v nng
sulfate trong mu. Trong bi ny, ba phng php o da vo lng BaSO4 s c
trnh by.
Phng php khi lng
Phng php khi lng cho kt qu kh chnh xc v c s dng xc nh hm
lng sulfate trong mu c nng trn 10 mg/L. Ch , khi cnh nh lng ca
phng php ny ph thuc vo kh nng kt hp ca Ba2+ vi SO42- hnh thnh
BaSO4 t tan nh sau.
kt ta hon ton, mt lng BaCl2 d c thm vo nc c acid ha vi
HCl v c gi gn im si. Vic mu c acid ha l loi tr kt ta BaCO3
c th xy ra nhit cao i vi nc c kim cao.
Do BaSO4 c ho tan nh (Ksp = 1x10-10), c th xem nh hu ht cc kt ta to
thnh dng keo, keo ny rt kh tch ra bng cc phng php lc thng thng.
khc phc iu ny, mu c gia nhit chuyn tt cc cc ta t dng keo thnh
dng tinh th c th tch ra bng cch lc. BaSO4 tinh th thng rt nh, v vy
phi la chn loi giy lc ph hp. Khi thc hin qu trnh lc, nn thc hin ht sc
cn thn m bo ton b lng kt ta c gi li trn giy lc v cc mui khc
c loi b bng cch ra. Mc d phng php ny c chnh xc cao nhng tn
rt nhiu thi gian. Kt ta BaSO4 sau lc c xc nh bng cch hoc l cn khi
lng tro sau khi t phn hy giy lc, hoc l cn cng vi giy lc sau tr i
khi lng giy lc c cn ban u.
Phng php o c
Phng php xc nh sulfate bng cch o c da trn s hnh thnh BaSO4
dng keo sau khi thm BaCl2 vo mu. tng hiu qu hnh thnh keo BaSO4 dung
dch m acid cha cc MgCl2, KNO3, CH3COONa v CH3COOH c cho vo. Bng
vic chun ha phng php to keo BaSO4 l lng, sulfate c xc nh bng cch
ny p ng c nhiu mc ch khc nhau. Phng php ny cho kt qu rt nhanh
v c ng dng rng ri. Khi nng ca sulfate ln hn 10 mg/L, trc khi thc
hin phng php ny, mt lng nh mu c ly sau pha long thnh 50 mL
sau thc hin theo phng php cp xc nh. s liu chnh xc, trong
khi thc hin php o lun phi s dng mu chun loi b cc sai s c th xy ra
do thao tc v cc cht thm vo.

8-5
CONG TY MOI TRNG

TAM NHN XANH
GREE
Tel: (08)5150181
Fax: (08)8114594
www.gree-vn.com
Phng php o t ng dng Methylthymol Blue

Phng php ny rt c li khi o hng lot mu. mu v ha cht c lin tc
bm t ng vo thit b o v c ha trn vi nhau. Sau thi gian cn thit phn
ng ha hc, xy ra, mu c a vo b phn o xc nh mu hoc c
(trong trng hp sulfate, c c o) t xc nh c lng sulfate. Trong
phng php ny, u tin BaCl2 c t ng bm vo mu trong mi trng pH
thp to kt ta BaSO4 sau pH ca dung dch c iu chnh n 10. Sau
methylthymol c thm vo to phc xanh vi lng Ba d. Lng Methylthymol
khng to phc s c mu xm v c o t ng. D nhin, thit b cng c hiu
chnh (calibrate) vi dung dch sulfate chun v cc ho cht thm vo phi chnh xc
v khng c cht gy cn tr.
8.3 NG DNG S LIU SULFATE
Ch tiu sulfate quyt nh nc c thch hp cung cp cho sinh hot hay cng nghip
hay khng. Ch tiu sulfate cng xc nh nhng vn lin quan n mi v n mn
do vic kh sulfate thnh sulfide. Trong qu trnh x l k kh bn v nc thi cng
nghip, vic kh sulfate c lin quan vi methane v CO2. Nu kh sinh hc (biogas)
c s dng trong ng c th nng ca H2S khng nn vt qu 750 ppm (tnh
theo th tch). Ch tiu ca sulfate trong bn v trong cht thi c th c dng
nh gi hm lng H2S trong biogas. T nhng thng tin ny, k s thit k c th
quyt nh c hay khng thit b lc kh tch H2S v kch thc ca cng trnh.
Rt nhiu cht hu c c cha lu hunh nh sulfate, sulfonate hay sulfide. Trong qu
trnh x l sinh hc hiu kh, s phn hy cc cht hu c ph v cc lin kt sulfur
ny v hnh thnh SO42-.

8-6
CONG TY MOI TRNG

TAM NHN XANH
GREE
Tel: (08)5150181
Fax: (08)8114594
www.gree-vn.com
CHNG 9
PHOSPHORUS & PHOSPHATE
9.1 GII THIU CHUNG

Xc nh phosphate nhanh chng tr thnh mt vic lm cn thit ca k s mi
trng do h nhn ra rng nhiu hp cht phosphorus nh hng ln nhng qu trnh
x l cht thi. Thng thng ch c nhng dng hp cht phosphorus v c gy nh
hng nh cc dng phosphate hay cc dng phn t kh nc nh polyphosphate
hay condensed phosphate. Nhng hp cht phosphorus hu c thng khng c
quan tm.
Nc cp
Polyphosphate c s dng trong nc cp nh l mt nhn t kim sot s n mn.
Chng cng c s dng cho cc dng nc mm n nh hm lng calcium
carbonate nhm loi b s ti to mui carbonate.
B mt ca nc cp l ni pht trin ca mt s vi sinh vt nc. Nhng sinh vt t
do hay nhng sinh vt ni c gi l phiu sinh (plankton) v y l loi sinh vt rt
c cc k s mi trng quan tm. Nhng phiu sinh mang tnh ng vt gi l
phiu sinh ng vt (zooplankton) v nhng phiu sinh mang tnh thc vt c gi l
phytoplankton (phiu sinh thc vt). Sau cng l to mang tnh thc vt (trong t bo
ca nhng sinh vt ny c cha chlorophyll), chng pht trin mnh v ph thuc vo
nhng nguyn t dinh dng trong nc. Nhiu nghin cu cho thy rng nitrogen
v phosphorus l 2 nguyn t nh hng ln s tng trng ca to v vi khun v khi
lng nguyn t ny b gii hn th n cng l nhn t gii hn tc tng trng v
pht trin ca to v vi khun. nhng ni c hm lng nitrogen v phosphorus cao
lm thc y hin tng n hoa ca to gy tc ng xu n mi trng. Kinh
nghim cho thy rng hin tng n hoa khng th xy ra khi hm lng nitrogen hoc
phosphorus hoc c hai b gii hn. Mc ti hn cho phosphorus v c vo khong
0,005 mg/L hoc 5g/L trong iu kin tng trng ma h.
X l nc thi
Nc thi sinh hot rt giu cc hp cht phosphorus. Ch yu l trong nc ty ra
tng hp, cha khong t 2 3 mg/L v nhng hp cht v c khc chim khong t
0,5 1 mg/l. Hu ht nhng phosphorus v c c c l t cht thi ca con ngi
do qu trnh phn hy protein v s gii phng phosphate t nc tiu. Trung bnh mt
ngi dn M gii phng mt lng phosphorus l 1,5 g/ngy.

9-1
CONG TY MOI TRNG

TAM NHN XANH
GREE
Tel: (08)5150181
Fax: (08)8114594
www.gree-vn.com
Hu ht bt git tng hp siu cp c sn xut cho th trng gia dng cha mt

lng ln polyphosphate. a s trong chng cha t 12 13% phosphorus hoc hn
50% polyphosphate. S dng nhng nguyn liu ny nh l mt cht thay th cho x
phng lm gia tng lng phosphorus trong nc thi sinh hot. T cc s liu v
polyphosphat c bn cho ngnh cng nghip cht ty ra. Ngi ta c tnh c
rng, nc thi sinh hot s cha mt lng phosphorus v c nhiu hn gp 2 3
ln so vi khi cht ty ra tng hp cha c ph bin rng ri.
Vi sinh vt trong cc qu trnh x l nc thi sinh hc cn mt lng phosphorus
ti to v tng hp m t bo mi. Nc thi th cha mt lng phosphorus vt
qu xa so vi mc cn thit x l mt lng gii hn cht hu c. S vic ny
c l gii da trn lng phosphorus c trong nc u ra sau khi x l ca cc
cng trnh x l nc thi sinh hc. Tuy nhin, nhiu loi nc thi cng nghip khng
cha lng phosphorus cn cho s pht trin ti u ca vi sinh vt trong qu trnh
x l nc thi. Trong nhng trng hp ny, lng thiu ht c cung cp bng
cch thm phosphate v c vo.
Tnh cht ca bn
Mt vn chnh trong x l nc thi l tnh cht ca bn sau cc qu trnh x l hiu
kh v k kh. Nhng bn ny cha mt lng ln nitrogen v phosphorus p ng cho
mc ch dinh dng. Tng hm lng phosphorus cha trong bn trung bnh khong
1% v 1,5% trong bn hot tnh kh. M ni c hm lng phosphate phong ph v
r, hu ht bn c bn da trn hm lng nitrogen m n cha v ch c mt t loi
da trn hm lng phosphorus.
Ni hi
Phc hp phosphate c s dng rng ri trong ngnh cng nghip nng lng hi
nc chng ng cn trong cc ni hi. Nu s dng phosphate dng phc, chng
nhanh chng c thy phn thnh nhng orthophosphate nhit cao. Gim st
lng phosphate thng qua vic xc nh hm lng orthophosphate.
9.2 TM QUAN TRNG CA HP CHT PHOSPHORUS
C nhiu loi hp cht phosphorus c mt trong k thut mi trng. Bng 9.1 trnh
by mt s hp cht quan trng.

9-2
CONG TY MOI TRNG

TAM NHN XANH
Tel: (08)5150181
Fax: (08)8114594
www.gree-vn.com
GREE
Bng 9.1 Mt s hp cht phosphorus quan trng

Tn
Orthophosphates
Trisodium phosphate
Disodium phosphate
Monosodium phosphate
Diammonium phosphate
Polyphosphates
Sodium
hexametaphosphate
Sodium tripolyphosphate
Tetrasodium
pyrophosphate
Cng thc
Na3PO4
Na2HPO4
NaH2PO4
(NH4)2HPO4
Na3(PO4)6
Na5P3O10
Na4P2O7
Tt c nhng polyphosphate (nhng phn t thy phn thnh phosphate) thy phn
hon ton trong dung dch nc v tr li thnh nhng dng ortho m chng bt
ngun.
Na4P2O7 + H2O 2 Na2HPO4
(9 - 1)
Tc tr li nguyn mu l mt chc nng ca nhit v do n s gia tng nhanh

khi nhit tin n gn im si. Tc ny cng gia tng khi gim pH v u im l
n gi ng nguyn trng nhng mu chun b xc nh hm lng phosphate
phc. S thy phn nhng phosphate phc cng chu nh hng bi enzyme ca vi
sinh vt. Tc tr li nguyn mu rt chm trong nc lc v nhanh hn trong nc
thi. Kinh nghim cho thy rng trong mt s loi nc pyrophosphate thy phn
nhanh hn tripolyphosphate, trong mt s loi nc khc th tc thy phn l nh
nhau. C nhng cht i hi nhiu gi thm ch nhiu ngy chuyn ha hon ton
polyphosphate thnh orthophosphate, c bit nhit thp hoc pH cao.
T nhng l do trn, xc nh phosphorus hay phosphate phi bao gm c vic xc
nh polyphosphate nu mun vic o tng cc dng v c c chnh xc.
9.3 CC PHNG PHP XC NH PHOSPHORUS - PHOSPHATE
Cc k s thng quan tm n s hin din ca hm lng ortho, poly v
phosphorus hu c. May mn l c th o orthophosphate vi rt t tr ngi t
polyphosphate do kh nng n nh ca chng trong iu kin pH, thi gian, nhit
c s dng trong qu trnh o. C hai dng poly v phosphorus hu c phi c
chuyn thnh orthophosphate o.
Orthophosphate
9-3
CONG TY MOI TRNG

TAM NHN XANH
Tel: (08)5150181
Fax: (08)8114594
www.gree-vn.com
GREE
Lng phosphorus tn ti di dng orthophosphate c th c o bng nhng

phng php: trng lc, th tch, so mu. Phng php trng lc c s dng khi
hm lng phosphorus hin din ln, nhng iu ny khng xy ra trong thc t.
Phng php th tch c s dng khi nng phosphate ln hn 50 mg/L, nhng
nng ny him gp tr trng hp nc si hay chuyn ha k kh nhng cht ni.
Phng php ny gm: kt ta, lc, lm sch kt ta v chun . Phng php ny
tn thi gian. Tuy nhin, phng php so mu o nc v nc thi c th c
tha mn vi mt chnh xc cao.
C ba phng php so mu c s dng o orthophosphate. Chng c cng bn
cht vi nhng nguyn tc trn nhng khc ch l n thm vo mt s nguyn t t
nhin to mu. Yu t ha hc cn thit nh: ion phosphate kt hp vi ammonium
molybdate trong iu kin acid to thnh phc cht molybdophosphate,
PO43- + 12(NH4)2MoO4 + 24H+ (NH4)3PO4.12MoO3 + 21NH4+ + 12H2O (9 - 2)
Khi hin din mt lng phosphate ln, trng thi ca molydophoste l nhng kt ta
mu vng c th c lc v o bng phng php th tch. nng phosphate
thp hn, to thnh nhng ht keo mu vng s c xc nh hm lng bng
phng php so mu. Vi nng phosphate di 30 mg/L (thng nm trong
khong phn tch nc), mu vng ca ht keo khng th nhn bit r v iu ny c
ngha l cn phi pht trin mt mu khc. Mt cch ci thin l thm vanadium
hnh thnh dng phc hp vanadomolybdophosphoric acid c mu vng r, cho php
phn tch phophorus vi hm lng di 1 mg/L hoc nhng khong thp hn.
Lng molybdenum cha trong ammonium phosphomolybdate cng c gim to
nhng sn phm sol c mu xanh vi t l tng ng vi lng phosphate hin din.
Mt lng tha ammonium molydate khng b gim i v do khng can thip vo
qu trnh. Ascorbic acid hay stannous chloride c th c s dng nh mt nhn t
kh. Hp cht mu c to thnh l xanh molybdeum hay xanh heteropoly. Chlorur
thic c s dng nh mt nhn t kh c th c m t qua phng trnh:
(NH4)3PO3.12MoO3 + Sn2+ (molybdenum) + Sn4+
(9 - 3)
Polyphosphates
Polyphosphate c th chuyn ha thnh orthophosphate bng cch un si mu
c acid ha ti thiu 90 pht. S thy phn ny c th c thc y bi nhit trong
autoclave 20 psi. Lng acid tha thm vo xc tc tng tc thy phn phi
c trung ha trc khi tip tc thm dung dch ammonium molybdate vo. Lng
orthophosphate xut pht t polyphoste c o bng mt trong nhng phng php
k trn. Lng polyphosphate c tnh nh sau:
Tng hm lng phosphate v c orthophosphate = polyphosphate
(9 4)

9-4
CONG TY MOI TRNG

TAM NHN XANH
GREE
Tel: (08)5150181
Fax: (08)8114594
www.gree-vn.com
Phosphorus hu c
Cc k s rt quan tm n vic o lng hm lng phosphorus hu c c trong cht
thi cng nghip v c trong bn. phn tch c i hi cht hu c phi c
ph hy sao cho phosphorus c gii phng di dng ion phosphate. Cht hu c
c th b ph hy bi mt trong 3 phng php oxy ha m hoc phng php chuyn
ha da theo Standard Method. Cht oxi ha c s dng khc vi nhng cht
trong phng php chuyn ha v c th l perchloric acid, nitric acid sulfuric acid
hay persulphate. Acid perchloric l cht oxi ha mnh nht, nhng n cng l cht c
hi nht. trnh nguy him t nhng v n, loi m c bit phi c s dng trong
qu trnh chuyn ha v phi thm vo mt s ha cht. V nhng l do ny, s chuyn
ha nh acid perchloric nn c thc hin bi nhng nh ha hc c kinh nghim v
cn thn. S dng cht oxi ha l persulphate khi thc nghim chng minh rng kt
qu thu c l ph hp.
Mt khi s chuyn ha hon tt, vic o lng phosphorus gii phng c th c
lm bng bt k mt phng php o orthophosphate no. Tt c nhng dng
phosphorus (tng) c o t s xc nh phosphorus hu c. Do vy, lng
phosphorus hu c c tnh nh sau:
Tng phosphorus phosphorus v c = phosphorus hu c
(9 - 5)
9.4 NG DNG NHNG S LIU V PHOSPHORUS

S liu v phophorus tr nn rt quan trng i vi k s mi trng khi h nh gi
s c mt ca chng nh nhn t quan trng tt yu ca chu k sng. Trc y,
thng s ny c s dng gim st hm lng phosphate trong h thng nc
trnh s n mn v trnh cn r trong ni hi. Vic xc nh phosphorus tr nn rt
quan trng trong vic nh gi hiu sut sinh hc tim nng ca nc mt v trong mt
s vng nht nh c mt lng phophorus n nh m c th c x vo ngun
nc nhn, c bit l nhng h v nhng b cha. Xc nh hm lng phosphorus
l cng vic thng xuyn trong qu trnh vn hnh h thng x l nc thi v trong
qu trnh nghin cu nhim dng chy nhiu ni. Do tm quan trng ca
phosphorus l cht dinh dng trong cc phng php sinh hc x l nc thi, vic
xc nh n c lin quan n nhiu cht thi cng nghip v trong qu trnh hot ng
ca cc cng trnh x l cht thi.

9-5

Hoa Hoc Moi Truong

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CNG TY MI TRNG

GREEN EYE ENVIRONMENT

2.1 Khi nim chung

3.1 Khi nim chung

4.1 Khi nim chung

GREEN EYE ENVIRONMENT

NHU CU OXY SINH HO

5.1 Gii thiu chung

6.1 Gii thiu chung

7.1 Gii thiu chung

8.1 Gii thiu chung

PHOSPHORUS & PHOSPHATE

9.1 Gii thiu chung

Hy vng b gio trnh ny s gip ch nhiu cho cc bn trong qu trnh hc tp cng

y cng l ln u tin, cun sch in t ny c xut bn do , s khng trnh

TP.HCM ngy 22 thng 12 nm 2006

ThS: Huynh Ngoc Phng Mai

GREEN EYE ENVIRONMENT

V nc phn ly to thnh mt ion hydroxyl v mt ion hydro nn r rng rng c

Nhng v nng ca nc l rt ln ([6,02 x 1023 x 1.000/18] mol/l) v gim i rt t

v i vi nc tinh khit 200C,

v pH thng nm trong dy t 0 n 14, vi pH 7 250C biu din tnh trung ha

ThS: Huynh Ngoc Phng Mai

GREEN EYE ENVIRONMENT

o bng in cc thy tinh

ThS: Huynh Ngoc Phng Mai

GREEN EYE ENVIRONMENT

1.4 PHN TCH S LIU pH

pH khng o acid tng cng hoc kim tng cng. iu ny c th c trnh

[OH-] v [H+] ca dung dch khng bao gi gim n zero.

ThS: Huynh Ngoc Phng Mai

2.1 KHI NIM CHUNG

ThS: Huynh Ngoc Phng Mai

GREEN EYE ENVIRONMENT

iem ket thuc phenolphthalein

Day cua o acid carbonic

iem ket thuc methyl cam

Day thc te cua o acid vo c

Fe2- + 2H+ + 2SO42-

ThS: Huynh Ngoc Phng Mai

S c mt ca cc kim loi nng c ch th bng vic to thnh kt ta khi pH ca

GREEN EYE ENVIRONMENT

v t Phng trnh (2 6) r rng l nu carbonate natri c mt trong hydroxide natri

GREEN EYE ENVIRONMENT

phn ly bc mt ca acid carbonic c th c s dng cho bit nng ion hydro,

Thc t, [H2CO3*] trong phng trnh ny c thit lp tng ng vi tng nng

nhng hin nay bromphenol c kin ngh s dng v s thay i mu r nt hn

ThS: Huynh Ngoc Phng Mai

GREEN EYE ENVIRONMENT

3.1 KHI NIM CHUNG

ThS: Huynh Ngoc Phng Mai

GREEN EYE ENVIRONMENT

3.2 NGHA MI TRNG

Vic s dng pH khong 4,5 lm im kt thc cho bc nh phn th hai tng ng

Trn c s Phng trnh pH = (pKn pKB logC0), im kt thc chnh xc cho

ThS: Huynh Ngoc Phng Mai

GREEN EYE ENVIRONMENT

OH-+H+H2O CO32-+H+HCO3- HCO3-+H+H2CO3

Hnh 3.1 ng cong nh phn ca hn hp hydroxide-carbonate.

GREEN EYE ENVIRONMENT

phenolphthalein. Hin nay, khi nim ny c s dng rng ri trong lnh vc x l

o kiem tong cong = tong mL H2SO4 nh phan en pH

Trong vic xc nh kim tng cng, pH ti im kt thc c mt quan h trc tip

GREEN EYE ENVIRONMENT