Cac Phuong Phap Phan Tich Hoa Hoc Nuoc Bien

HA HC BIN
Cc phng php phn tch ha hc nc bin
on B
NXB i hc Quc gia H Ni 2001

T kho: Nng , ch th, i dng, nc bin, nguyn t, phn t, ng v, hu
c, v c, t l, thnh phn
Ti liu trong Th vin in t i hc Khoa hc T nhin c th c s dng

cho mc ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao
chp, in n phc v cc mc ch khc nu khng c s chp thun ca nh
xut bn v tc gi.
ON B
HO HC BIN
Cc phng php
phn tch ho hc nc bin
(Gio trnh dng cho sinh vin chuyn ngnh Hi dng hc)
NH XUT BN I HC QUC GIA H NI
MC LC
M U ................................................................................................................................. 6
CHNG 1. XC NH MUI NC BIN ............................................................. 8
1.1. XC NH CLO V MUI NC BIN BNG PHNG PHP
CHUN BC NITRAT (PHNG PHP KNUDSEN).............................................. 8
1.1.1. Gii thiu chung ..................................................................................................... 8
1.1.2. Phng php Knudsen .......................................................................................... 10
1.1.3. Thit b v dng c ............................................................................................... 13
1.1.4. Cc ho cht.......................................................................................................... 15
1.1.5. Ly v bo qun mu nc ................................................................................... 17
1.1.6. Qu trnh xc nh................................................................................................. 18
1.1.7. Tnh ton kt qu .................................................................................................. 22
1.1.8. Th t cng vic ................................................................................................... 24
1.2. XC NH CLO CA VNG NC NHT VEN B..................................... 25
1.2.1. Gii thiu chung ................................................................................................... 25
1.2.2. Phng php xc nh........................................................................................... 26
1.2.3. Thit b v dng c ............................................................................................... 26
1.2.4. Ho cht ................................................................................................................ 26
1.2.5. Ly v bo qun mu nc ................................................................................... 27
1.2.6. Qu trnh xc nh................................................................................................. 28
1.2.7. Tnh ton kt qu .................................................................................................. 29
1.2.8. Th t cng vic ................................................................................................... 30
CHNG 2. XC NH CC KH HO TAN TRONG NC BIN.......................31
2.1. XC NH KH XY HO TAN BNG PHNG PHP CHUN IT
(PHNG PHP VINCLER) ............................................................................................ 31
2.1.1. Gii thiu chung ................................................................................................... 31
2.1.2. Phng php Vincler ............................................................................................ 32
2.1.3. Thit b v dng c ............................................................................................... 35
2.1.4. Ho cht ................................................................................................................ 36
2.1.5. Ly mu nc v c nh xy ho tan ................................................................. 39
2.1.6. Qu trnh xc nh................................................................................................. 39
2.1.7. Tnh ton kt qu .................................................................................................. 42
2.1.8. Th t cng vic ................................................................................................... 45
2.2. XC NH OXY HO TAN TRONG NC BIN KHI C KH SUNFUHYDRO45
2.2.1. Phng php xc nh........................................................................................... 45
2.2.2. Thit b v dng c ............................................................................................... 46
2.2.3. Ho cht ................................................................................................................ 46
2.2.4. Ly v bo qun mu nc ................................................................................... 47
2.2.5. Qu trnh xc nh v tnh ton kt qu ................................................................ 47
2.3. XC NH KH SUNFUHYDRO HO TAN TRONG NC BIN ...................... 48
2.3.1. Gii thiu chung ................................................................................................... 48
2.3.2. Phng php xc nh........................................................................................... 49
2.3.3. Thit b v dng c ............................................................................................... 51
2.3.4. Ho cht ................................................................................................................ 51
2.3.5. Ly mu nc v c nh H2S .............................................................................. 52
CHNG31. XC NH CC THNH PHN CA H CCBNT TRONG NC

BIN..........................................................................................................................58
3.1. XC NH PH NC BIN BNG PHNG PHP SO MU ............................ 58
3.1.1. Gii thiu chung ................................................................................................... 58
3.1.2. Phng php so mu xc nh pH nc bin ....................................................... 61
3.1.3. Dng c v ho cht.............................................................................................. 61
3.1.4. Ly mu nc v xc nh pH .............................................................................. 64
3.1.5. Tnh ton kt qu .................................................................................................. 67
3.1.6. Th t cng vic ................................................................................................... 71
3.2. XC NH KIM NC BIN .......................................................................... 72
3.2.1. Gii thiu chung ................................................................................................... 72
3.2.2. Phng php xc nh kim nc bin............................................................ 74
3.2.3. Dng c v thit b................................................................................................ 75
3.2.4. Ho cht ................................................................................................................ 75
3.2.5. Ly v bo qun mu nc ................................................................................... 77
3.2.6. Qu trnh xc nh................................................................................................. 78
3.2.7. Tnh ton kt qu .................................................................................................. 79
3.2.8. Th t cng vic ................................................................................................... 81
3.3. TNH TON CC THNH PHN H CACBONAT TRONG BIN ...................... 82
3.3.1. G ii thiu chung .................................................................................................. 82
3.3.2. Phng php tnh cc thnh phn h cacbonat ..................................................... 84
CHNG 4. XC NH CC HP PHN DINH DNG V C V CC CHT
HU C TRONG NC BIN.................................................................................89
4.1. NGHA V NGUYN TC CHUNG PHNG PHP SO MU XC NH
CC HP PHN DINH DNG V C TRONG NC BIN................................... 89
4.1.1. ngha.................................................................................................................. 89
4.1.2. Nguyn tc chung phng php so mu xc nh cc hp phn dinh dng v c
trong bin ........................................................................................................................ 90
4.2. XC NH PHT PHT TRONG NC BIN ...................................................... 92
4.2.1 Phng php xc nh............................................................................................ 92
4.2.3. Ho cht ................................................................................................................ 95
4.2.4. Ly v bo qun mu nc ................................................................................... 96
4.2.5. Qu trnh xc nh................................................................................................. 97
4.2.6. Tnh ton kt qu ................................................................................................ 100
4.2.7. Th t cng vic ................................................................................................. 102
4.3. XC NH SILICAT TRONG NC BIN ........................................................... 103
4.3.1. Phng php xc nh......................................................................................... 103
4.3.2. Dng c v ho cht............................................................................................ 103
4.3.3. Ly v bo qun mu nc ................................................................................. 104
4.3.4. Qu trnh xc nh............................................................................................... 105
4.3.5. Tnh ton kt qu ................................................................................................ 107
4.4. XC NH NITRIT TRONG NC BIN ............................................................. 107
4.4.1. Phng php xc nh......................................................................................... 107
4.4.2. Dng c v ho cht............................................................................................ 108
4.4.3. Ly v bo qun mu nc ................................................................................. 110
4.4.4. Qu trnh xc nh............................................................................................... 110
4.4.5. Tnh ton kt qu ................................................................................................ 111

4.5. XC NH NITRAT TRONG NC BIN............................................................ 112
4.5.1. Phng php xc nh......................................................................................... 112
4.5.2. Thit b v dng c ............................................................................................. 114
4.5.3. Ho cht .............................................................................................................. 114
4.5.4. Ly v bo qun mu nc ................................................................................. 117
4.5.5. Qu trnh xc nh............................................................................................... 117
4.5.6. Tnh ton kt qu ................................................................................................ 118
4.5.7. Ch .................................................................................................................. 118
4.6. S DNG THIT B SO MU XC NH CC HP PHN DINH DNG
TRONG NC BIN....................................................................................................... 119
4.6.1. Nguyn tc chung ............................................................................................... 119
4.6.2. Qu trnh xc nh............................................................................................... 120
4.6.3. Tnh ton kt qu ................................................................................................ 121
4.6.4. Th t cng vic ................................................................................................. 122
4.7. XC NH HM LNG CHT HU C TRONG NC BIN QUA NHU CU
XY HO HC (COD) ................................................................................................... 123
4.7.1. Gii thiu chung ................................................................................................. 123
4.7.2. Phng php xc nh COD nc bin .............................................................. 124
4.7.3. Dng c v thit b.............................................................................................. 126
4.7. 4. Ho cht ............................................................................................................. 127
4.7.5. Ly v bo qun mu nc ................................................................................. 127
4.7.6. Qa trnh xc nh............................................................................................... 127
4.7.7. Tnh ton kt qu ................................................................................................ 129
LI NI U
Gio trnh HO HC BIN, phn 2: Cc phng php phn tch ho
hc nc bin c bin son ging dy cho sinh vin chuyn ngnh Hi
dng hc, i hc Quc Gia H Ni. y cng l ti liu tham kho tt cho
sinh vin cc ngnh Thu vn, Thu ho v Mi trng ca cc trng i hc
khc c lin quan n lnh vc nghin cu bin, ng thi cng l ti liu tham
kho i vi cc th nghim vin ang lm cng tc phn tch ho hc nc bin
Vit Nam.
tp trung vo nhng kin thc thuc v phn tch ho hc nc bin,
gio trnh ch trng gii thiu c s nhng phng php ho hc v quy trnh
thu mu, phn tch mu nc bin xc nh cc hp phn ho tan trong n.
y khng i su v chi tit vo cc cch pha ch dung dch, cch cn, ong,
cch ty v lm sch ho cht, cch s dng cc dng c, thit b phn tch...
Nhng kin thc ny sinh vin c trang b t cc chuyn trc , t
cc t thc tp Vt l i cng, Ho hc i cng v Ho hc phn tch,
hoc tm hiu trong cc ti liu chuyn mn. Bi vy, yu cu i vi sinh vin
khi hc gio trnh ny l phi c cc kin thc c bn v Ho hc bin (phn 1),
Ho hc i cng v Ho hc phn tch. Trong qu trnh hng dn sinh vin
hc tp, gio vin c th nhc li v m rng thm nhng kin thc c lin quan.
Tc gi rt mong nhng gp b sung v hon thin gio trnh. Cc
kin xin gi v a ch B mn Hi dng hc, Trng i hc Khoa hc T
nhin, i hc Quc Gia H Ni.
Tc gi
M U
Ngy nay, cc nghin cu ho hc bin khng ch dng li vic xem xt
hin trng phn b cc yu t ho hc ti vng bin nghin cu m i su vo
c ch v bn cht ca cc qu trnh v hin tng, l ngun gc hnh thnh
cc hp phn ho hc nc bin, quy lut phn b v bin ng ca chng, mi
quan h gia cc yu t vi nhau v vi mi trng, vi sinh vt, vi qu trnh
tng tc bin-kh quyn-thch quyn-sinh quyn, vi chu trnh vt cht v chu
trnh sinh-a-ho. Cc nghin cu ho hc bin vi quy m v ni dung nh
vy gip ch rt nhiu cho cc nghin cu vt l, ng lc, sinh hc, sinh
thi, ti nguyn v ngun li sinh vt v phi sinh vt... ca vng bin, c bit
trong vic nghin cu v kim sot mi trng bin.
Thc t, Hi dng hc ngy nay v ang s dng mt s my mc,
thit b c th o trc tip t nc bin mt vi tnh cht v hp phn ho hc
nh mui, dn in, c, xy ho tan, pH... vi chnh xc cao. C
thit b nh CTD-Rosette, RCM-9, RCM-12 hoc Aquashuttle, Nvshuttle... cn
o c ng b mt s yu t theo cu trc thng ng v c th ghi s liu
vo bng t, rt tin li cho vic x l kt qu trn my tnh. Tuy nhin xc
nh nng ca phn ln cc yu t ho hc nc bin, hin ti vn phi s
dng cc phng php phn tch ho hc truyn thng nh chun mu nc,
so mu ca mu vi dung dch chun... Ch khc l nu trc y vic phn tch
ho hc nc bin c thc hin hon ton bng cc thao tc th cng th ngy
nay Hi dng hc c cc thit b ph tr (my so mu quang in, ph
quang k, sc k kh, quang ph hp th nguyn t...) gip cho vic phn tch
c nhanh chng, chnh xc v loi b c cc sai s ch quan ca ngi
phn tch. Song vi phng chung nn kinh t ca t nc hin nay, cc my
mc, thit b o v phn tch hin i nh vy thng khng ph hp vi ngun
ti chnh ca cc ti, d n v cc c s o to v nghin cu khoa hc bin.
Trong i a s cc trng hp, phng php phn tch ho hc truyn thng
vn l hu hiu i vi cc nghin cu ho hc bin nc ta v nhiu nc
trn th gii, ngay c khi c cc thit b o hin i i km.
Gio trnh ny trnh by mt s phng php ho hc chun v thng dng

xc nh cc hp phn ho hc ho tan trong nc bin, l cc phng php
phn tch truyn thng, c chnh xc cao, v ang c ng dng rng ri,
ph hp vi quy m v iu kin nghin cu bin Vit Nam. y tp trung
vo cc phng php v quy trnh, t bc thu mu nc n phn tch ho hc
mu nc xc nh mt s yu t ho hc thng c quan tm nht v
thm ch khng th thiu c trong cc chuyn iu tra kho st bin: l cc
yu t ho hc bin nh mui, xy ho tan, kim, cc hp cht dinh
dng v c Phtpht, Nitrt, Nitrat, Silicat v mt vi yu t mi trng bin
nh pH, kh c Sunfuhydro, nhu cu xy ho hc.
Chng 1
XC NH MUI NC BIN
1.1. XC NH CLO V MUI NC BIN BNG PHNG PHP
CHUN BC NITRAT (PHNG PHP KNUDSEN)
1.1.1. Gii thiu chung

mui nc bin l i lng c trng nh lng cho lng cc cht
khong rn ho tan (cc mui) trong nc bin. l mt trong cc thng s vt
l c bn ca Hi dng hc ch th khi nc, tnh ton cc yu t ng lc
v tm hiu nh tnh mt s c trng sinh thi phn b sinh vt bin... Xc
nh chnh xc mui nc bin l nhim v quan trng v khng th thiu
ca mi nghin cu hi dng.
Ngy nay, Hi dng hc s dng cc my v cc thit b o mui
nc bin thng qua vic o dn in, o t trng, o tc truyn m... Cc
phng php s dng my hoc cc thit b o mui nh trn c gi chung
l cc phng php vt l, c u im l thao tc n gin v c c ngay gi
tr mui nc bin m khng cn qua mt bc tnh ton trung gian no. Mt
s thit b hin i c ch to v thng xuyn c ci tin trong khong 10
nm gn y ca M, Nht Bn, Nauy... cn c kh nng o mui lin tc t
mt bin n su hng nghn mt (o profile thng ng mui), c th s
ho kt qu o v ghi vo bng t, hoc c cp chuyn dng truyn thng tin t
u o n my tnh v x l ngay cc kt qu trong khi u o vn ang
su lm vic. Mt u th khc ca cc thit b o l c th gn nhiu u o c
chc nng khc nhau (o nhit , pH, xy ho tan, c, cng bc x,
sc t quang hp...) v do vy c th ng b o nhiu yu t mi trng ti v
tr kho st.
Nhc im chung ca mt s my v thit b xc nh mui nc bin

l chnh xc ca php o khng cao, thng ch t 0,1%o (tr mt s my
hoc thit b hin i, tinh vi) v ph thuc rt nhiu vo chnh xc ca php
o nhit nc bin tnh ton cc s hiu chnh. iu ny thng gp thy
cc my hoc thit b o mui da trn nguyn l o t trng nc bin
hoc o tc truyn m, hoc gp thy cc thit b o dn in c sn
xut t nhng nm 70, 80 v trc na. Ngay mt s thit b hin i ngy nay
cng c loi c ch to v sn xut ra ch vi mc ch kim tra cht lng
mi trng (v d my WQC ca Nht Bn) nn chnh xc ca php o
mui khng cao. Trong nhiu trng hp, kt qu o mui nh vy khng
tho mn yu cu ca Hi dng hc, nht l yu cu ca cc bi ton v ng
lc khi nc. Mt c im khc dn n tnh trng cha ph dng Vit Nam
cc my v thit b o mui nc bin c chnh xc cao (v ni chung l
cc thit b o cc yu t mi trng bin) l chng c gi thnh qu cao so vi
phng kinh t hin ti ca t nc, trong i a s cc trng hp u khng
ph hp vi ngun ti chnh ca cc d n, ti hoc cc c s nghin cu v
o to khoa hc bin. Nhiu loi my o mi, hin i v chnh xc (v d
CTD-Rosette ca hng Seabird Electronics Inc, hoc Aquashuttle hay Nvshuttle
ca hng Chelsea Instruments...) khng nhng c gi thnh cao m cn i hi
nhng tiu chun k thut i km, nh l phi c tu nghin cu ln, v tr lp
t trn tu v cc iu kin lm vic phi chun - nhng yu cu ny hin ti
ngnh khoa hc bin nc ta cha th p ng v tho mn trn vn.
Phng php ho hc xc nh mui nc bin mc d "cng knh" hn
cc phng php vt l do phi chun b trc ho cht v cc dng c ly mu
v phn tch (cng khng phc tp v tn km lm), song li cho chnh xc
cao (0,02%o) tho mn yu cu ca Hi dng hc. l phng php chun
mu nc bin bng dung dch Bc Nitrat (AgNO3), hay phng php xc
nh mui theo Clo. Phng php ny do M. Knudsen xut nn cn
c gi l phng php Knudsen, c U ban Quc t v Nghin cu bin
cng nhn t nm 1902. Cho n nay, y l phng php ho hc duy nht ca
Hi dng hc dng xc nh Clo v mui nc bin.
Cng cn ni thm l, mc d Hi dng hc hin nay s dng cc thit

b c chnh xc cao o mui nc bin, song phng php Knudsen
vn c s dng rng ri trong Hi dng hc Vit Nam v th gii bi quy
trnh phn tch n gin, chnh xc cao v chi ph t hn nhiu so vi cc
phng php vt l. c bit, khi chng ta cn t chc cng mt lc nhiu i
kho st m li khng kh nng trang b my o cho tt c cc i th vic ly
mu nc phn tch mui theo phng php Knudsen l bt buc.
1.1.2. Phng php Knudsen
Nh bit, trong nc bin tng hm lng ca 11 thnh phn chnh
(gm cc ion v phn t l Cl- SO4-2, (HCO3-+CO3-2), Br-, F-, H3BO3, Na+, Mg+2,
Ca+2, K+, Sr+2) chim ti 99,99% tng lng cc cht khong ho tan. iu
c ngha l tr s mui nc bin c quyt nh bi tng hm lng ca
ch 11 thnh phn ny, trong ng k nht l Cl- (55,04%) v Na+ (30,61%),
tip l SO4-2 (7,68%) v Mg+2 (3,69%).
Mc d mui nc bin c th bin i trong nhng gii hn kh rng,
nhng t l khi lng gia cc thnh phn chnh ca n hu nh khng i
mi vng bin trn th gii, tr cc vng ca sng, m ph, vng vnh kn v
cc bin km trao i nc vi i dng. iu ny c Marxet pht hin
t nm 1819. Hn 50 nm sau, vo nm 1876, Ditmar cng khng nh
Marxet trn c s nghin cu thnh phn mui nc bin nhiu vng trn th
gii v tng kt thnh quy lut c bn ca Ho hc hi dng: "Trong nc
i dng xa b, t s gia nng ca cc ion chnh lun khng i, khng
ph thuc vo tr s tuyt i ca mui".
T quy lut ny c th d dng suy ra rng xc nh mui nc bin
(c coi tng ng vi tng nng 11 thnh phn chnh), ch cn xc nh
chnh xc hm lng mt thnh phn chnh no , ri bng cc tnh ton n
gin theo mi quan h bit s xc nh c gi tr mui. Ion Clo c
chn cho mc ch ny v s c mt ca n trong nc bin vi nng ln
nht chnh l mt m bo cho vic xc nh n mt cch nhanh chng v chnh
xc bng cc phng php ho hc n gin (nng trung bnh ca Cl- trong
10
nc b mt i dng l 19,3534 g/kg).

xc nh hm lng ion Clo trong nc bin, ngi ta cho dung dch
Bc Nitrat (AgNO3) c nng bit trc tc dng vi mt th tch mu nc,
khi ion Clo ca mu b kt ta dng AgCl mu trng sa. Tuy nhin, do
trong nc bin cn c mt ng thi cc halogen khc (F-, Br-, I-) nn kt ta
trng sa k trn ngoi AgCl cn c c AgF, AgBr v AgI. Bi vy, ci gi l
"hm lng ion Clo" xc nh theo cch ny thc cht l tng hm lng cc
halogen c trong mu nc bin - gi l Clo.
Trn c s cc ngh quyt ca Hi ngh quc t v Hi dng hc hp ti
Stckhm (Thu in) nm 1889 v 1901, M. Knudsen v cng s thc hin
mt khi lng ln cc cng vic nhm xc nh chnh xc mi quan h nh
lng gia mui vi Clo nc bin. Cc tc gi cng xy dng nh
ngha v cc i lng ny nh sau:
- mui nc bin l trng lng cn kh tnh bng gam (cn trong chn
khng) ca mt kilogam nc bin, vi iu kin tt c cc halogen trong
c thay th bng lng Clo tng ng, nhng mui ccbonat c thay
bng xit v cc cht hu c b phn hu ht 480oC.
- Clo nc bin l tng trng lng (tnh bng gam sau khi quy i
tng ng sang lng Clo) ca cc halogen c trong 1kg nc bin. (Nm
1940, Jacobxen v Knudsen khi da vo Clo ca nc bin tiu chun
Copenhagen a ra mt nh ngha khc: Clo, v tr s tng ng vi
s gam Bc tinh khit cn thit lm kt ta ht cc halogen c trong
0,3285234 kg nc bin).
- i vi nc i dng v cc bin trao i tt vi i dng, mi quan
h gia mui (tnh bng g/kg, k hiu S%o), t trng ti 0oC (k hiu 0) v
Clo (tnh bng g/kg, k hiu Cl%o) nh sau:
S%o = 1,805 Cl%o + 0,030
2
0= 0,068 + 1,4708Cl - 0,00157 Cl + 0,000398 Cl
11
(1.1)
3
(1.2)
Ngoi cng thc nu trn, nhng nm sau ny mt s tc gi cn xy dng

nhng cng thc v mi quan h gia tng nng cc ion (tnh bng g/kg, k
hiu I%o), mui v Clo ca nc bin, v d:
Lymen v Fleming (1940): I%o = 0,069 + 1,8112 Cl%o
Kocx (1963): S%o = 1,80655 Cl%o
Kocx (1966): I%o = 1,81578Cl%o v I%o = 1,005109 S%o
Thc t nghin cu ho hc bin chng t rng gi tr I%o gn vi
mui thc ca nc bin hn l gi tr S%o, song s sai khc ca chng khng
ng k, ch vo khong 0,004%o khi mui nc bin nm trong khong
30-40%o.
Nh vy, vic xc nh mui nc bin c quy v xc nh Clo.
Thc cht ca phng php Knudsen xc nh Clo l dng dung dch Bc
Nitrat (AgNO3) c nng bit trc chun mt th tch mu nc bin
(thng l 15 ml) cho ti khi cc halogen trong b kt ta ht dng mui
Bc mu trng sa. Phn ng thu gn ca qu trnh ny (v d vi Clo) nh sau:
Ag+ + Cl- AgCl (trng sa)
(1.I)
Bit c th tch dung dch AgNO3 s dng kt ta ht cc halogen

c trong lng mu nc k trn, d dng xc nh c hm lng tng cng
ca chng, tc l Clo ca mu nc.
xc nh chnh xc thi im cc halogen b kt ta ht (cn gi l thi
im tng ng), l thi im m trong mu nc ang chun khng cn
cc ion halogen t do na, ngi ta s dng dung dch Kali Cromat (K2CrO4)
lm ch th mu. Nu thm vi git ch th mu vo mu nc ri em chun
th kt ta mu da cam (Ag2CrO4) s c to thnh cng vi kt ta trng sa.
Nhng do Ag2CrO4 km bn vng nn n li b phn ly v cc ion Bc mi ti
to ny s tip tc kt hp vi cc halogen t do ca mu nc, ngha l mu da
cam li bin mt. Mu da cam s n nh v khng bin mt khi v ch khi qu
12
trnh kt ta cc halogen thc s kt thc. Phn ng thu gn ca qu trnh hnh

thnh mu da cam nh sau:
CrO4-2 + 2 Ag+ Ag2CrO4 (da cam)
(1.II)
C hai im cn ch khi s dng phng php Knudsen:

Th nht: nh lng ca phn ng (1.I) ph thuc vo pH ca mu nc
bin. Nu mu nc qu kim tnh (nhiu OH-) th lng dung dch AgNO3 tiu
hao khi chun mu s nhiu hn mt cht so vi lng AgNO3 thc s kt
ta ht cc halogen, theo c ch:
2Ag+ + 2OH- 2AgOH Ag2O + H2O
Qua thc nghim thy rng, phng php Knudsen p dng tt nht khi pH
ca mu nc nm trong khong 7,5-8,6. y l khong pH ca nc bin v
i dng mi vng trn th gii (tr mt vi vng c bit) nn c th yn
tm s dng phng php Knudsen trong mi trng hp.
Th hai: Phng php Knudsen c xy dng trn c s quy lut c bn
ca Ho hc hi dng, t dn n cng thc 1.1 v cc cng thc khc nh
nu. Bi vy n ch ng vi nc bin khi, cc bin, vnh hoc vng nc
lu thng tt vi bin khi v cc khu vc t chu nh hng ca nc lc a.
Cc vng nc ca sng, vng vnh kn, m ph ven bin... c thnh phn ion
rt khc vi nc bin v do khng c tnh hng nh v t l nng cc
hp phn chnh, s khng p dng c phng php ny (mc 1.2 s trnh by
phng php xc nh Clo ca cc i tng nc ).
1.1.3. Thit b v dng c
Biuret v Pipet bin l cc thit b c bn xc nh Clo ca nc bin
theo phng php Knudsen. Chng c cu trc c bit, khc vi cc Biuret v
Pipet thng thng s dng trong cc phng th nghim.
Nt c bit th nht ca cc loi Biuret v Pipet bin l b phn iu
chnh chnh xc dung dch vch s "0". Trc y M. Knudsen ch to cc
13
thit b ny vi vic thit lp vch "0" nh van 2 ng. Khi dung dch c bm
vo Biuret (hoc ht vo Pipet) cc l van c ng m bng tay mt cch hp
l sao cho dung dch chim ton b th tch Biuret (hoc Pipet) ti vch s
"0".
Ngy nay cc Biuret v Pipet bin c cu trc n gin m vn t c
chnh xc cao. Vch s "0" c thit lp t ng nh mt ng mao dn hnh
"m hc" nm phn trn cng ca thit b. S "0" ca thang chia ng vi
u mt ca m hc, l thot ca m hc c ng knh khong 1mm. Pipet
bin s dng ring cho mc ch phn tch Clo c dung tch chnh xc bng
15 ml. Mun ly y dung dch vo Biuret (hoc Pipet), ch cn bm (hoc ht)
dung dch vo thit b cho ti khi c mt t trn qua m hc (d nhin lng trn
qua ny phi c thu gom vo mt bnh cha no ). Nh vy vch s "0"
c thit lp m khng cn c thao tc g thm.
Nt c bit th 2 ca Biuret bin dng xc nh Clo l mi chia
nguyn ca n c th tch ng bng 2 ml v c vch du thnh 20 phn u
nhau. Nh vy th tch mi phn l 0,1ml v khong cch gia hai vch lin
nhau l 0,05 chia. iu ny cho php c bng mt thng v tr mt khum
ca dung dch trong Biuret chnh xc ti 0,01 chia.
Biuret v Pipet bin nht thit phi c bng kim nh km theo. Vic s
dng chng bt buc phi tun th mt cch nghim ngt cc quy trnh, ng tc
v cc iu kin lm vic (s nu phn sau).
Ngoi Biuret v Pipet t ng, cn c thm cc dng c sau:
- Cc chun th tch khong 300 ml, s dng loi cc t bnh thng.
- My khuy c hoc my khuy t. Trng hp khng c my khuy c
th dng a khuy thu tinh nhng u a phi bc cao su trnh va p vo
thnh cc chun lc lm vic.
- ng nh git (dng cho dung dch cht ch th).
- Cc bnh v chai l xm mu cha dung dch Bc Nitrat (th tch t 3
14
n 5 lit), np bng cao su.

- Bnh bo qun nc bin tiu chun c th tch 300 ml, nt thu tinh
mi v c chp thu tinh hoc cao su chng bay hi.
- Chu ra, bnh cha cht thi... v cc dng c thng thng khc.
1.1.4. Cc ho cht
Nc bin tiu chun
Bit rng dung dch Bc Nitrat rt d b bin i nng khi tip xc vi
nh sng, trong khi , chnh xc ca vic xc nh Clo nc bin bng
phng php Knudsen li ph thuc quyt nh vo s n nh ca nng
dung dch ny. Do vy, kim tra nng dung dch Bc Nitrat l cng vic bt
buc v thng xuyn.
kim tra nng dung dch Bc Nitrat, ngi ta s dng "nc bin
tiu chun". l nc tng mt i dng c ly v, lc k v x l theo
mt quy trnh nghim ngt, Clo ca n c xc nh chnh xc v v gi tr
gn vi 19,38%o. Nc bin c Clo 19,38%o s c mui 35%o - l gi
tr trung bnh mui nc tng mt i dng th gii.
Trong Ho hc bin thc hnh thng s dng nc bin tiu chun c
iu ch sn ti cc phng th nghim chuyn mn, c Clo chnh xc bng
19,38%o. Nc bin tiu chun sau khi iu ch c bo qun trong cc
Ampun thu tinh hn kn hai u, th tch khong 250ml, nhn gn trn Ampun
c ghi y cc thng tin v tr s Clo, ni v thi im sn xut, thi hn
s dng... (hnh 1.1). Nc bin tiu chun ca an Mch c a dng nhiu
nht trn th gii. Vit Nam thng s dng loi nc bin tiu chun do
Lin X c ch to (trc y cng hay dng loi do Trung Quc sn xut).
Nm 1980, Vin Nghin cu bin Hi Phng (nay l Phn vin Hi dng hc
Hi Phng) ch to c nc bin tiu chun c Clo chnh xc bng
19,128%o, c a vo tiu chun Vit Nam v c mt s c quan
nghin cu bin trong nc s dng.
15
PHNG TH NGHIM HO HC BIN

---------------------------------------------------------
NC BIN TIU CHUN

N=19.128%o V=250ml
Hnh 1.1: Ampun nc bin tiu chun
Dung dch Bc Nitrat (AgNO3)

tin li trong vic tnh ton kt qu, nng dung dch Bc Nitrat cn
c chn theo nguyn tc: nu chun V ml nc bin tiu chun th th tch
dung dch chi dng (biu din qua chia trn Biuret) c gi tr ng bng
Clo ca nc bin tiu chun. V d nu ta chun 15 ml nc bin tiu chun
c Clo 19,38%o th s c trn Biuret cng phi l 19,38 chia. Cch chn
nng dung dch Bc Nitrat nh vy s lm n gin rt nhiu vic tnh ton
kt qu, bi v s c trn Biuret ni chung rt gn tr s Clo ca mu nc.
S sai khc khng nhiu gia hai gi tr ny s c hiu chnh.
la chn nng dung dch Bc Nitrat tho mn yu cu trn, ta phi
da vo tr s Clo ca nc bin tiu chun. Chng hn nu dng nc bin
tiu chun c Clo bng 19,38%o (t trng tng ng l 1,02674) th nng
dung dch Bc Nitrat (g/l) phi l:
(4,791 . 15 . 1,02674)/2 = 36,89
Trong 4,791 l s gam tinh th Bc Nitrat tinh khit cn thit kt ta
ht 1 gam Clo; 15 l s mililit nc bin tiu chun dng chun ; 2 l th
tch (ml) mt chia nguyn ca Biuret. Vic chng minh cng thc ny khng
kh, y khng trnh by.
V mui Bc Nitrat thng khng c tinh khit tuyt i nn thay cho
gi tr 36,92, ngi ta thng ly 37,1 gam tinh th Bc Nitrat pha thnh mt
lt dung dch. Lng tinh th sau khi cn c a ngay vo bnh xm mu v
pha vi mt t nc ct cho tan ht, sau b sung nc ct cho n th tch cn
16
thit, lc u xo trn dung dch. Nc ct pha dung dch phi tht tinh
khit v khng c ln Clo. Dung dch pha ch xong phi hon ton trong sut,
nu khng trong sut phi t vo ch ti cho n khi hon ton trong sut mi
c s dng. Tu theo s lng mu cn phn tch, c th chun b sn t 3
n 5 lt v bt ng trong bng ti vi ba ngy.
Ch rng dung dch Bc Nitrat rt d bin i nng khi tip xc vi
nh sng nn ngoi vic dng cc bnh thu tinh mu cha chng, mi bin
php cch ly dung dch vi nh sng (bc vi en dy, ni ti) l rt cn thit.
Dung dch cht ch th Kali Crommat 10% (K2CrO4)
Vi mc ch l ch th mu cho thi im tng ng, nng dung dch
K2CrO4 khng cn thit phi c chnh xc cao. Tuy vy, ch phm pha ch
dung dch phi tinh khit, khng c ln tp cht c th tc dng c vi Bc
Nitrat hoc lm i mu hn hp lc chun .
Dng cn k thut ly 10 gam mui K2CrO4 sch v ho vi 90 ml nc
ct, ta c dung dch Kali Crommat 10%.
Ngoi 3 ho cht trn, cn c hn hp ra Crm + axt Sunfuric long (gi
l nc Crm) ra dng c, m bi trn cc van ca Biuret, Pipet v mt
vi ho cht ty ra thng thng khc.
1.1.5. Ly v bo qun mu nc
Khi thit b ly nc bin c ko ln boong tu, cc kho st vin bt
u thc hin cng vic ly mu. Vi mc ch ly mu xc nh Clo, c th
s dng chai l bt k (bng thu tinh hoc nha), nhng phi sch v c nt kn
trnh bay hi nc. Mu xc nh Clo c ly sau cc mu xc nh
pH v Oxy ho tan.
Cc chai l s dng ln u cn c ra cn thn bng nc Crm v
nc ngt, sau ngm bng nc bin t 1 n 1,5 thng v ch nc ang
ngm chai l i trc lc s dng. Trc khi ly mu nc vo l cn phi trng
l 2-3 ln bng chnh nc cn ly. Khng nn ly nc y l trnh bt nt
17
do nhit thay i lm dn n th tch nc trong l. Khi chuyn mu i xa

phi buc chng nt cn thn.
1.1.6. Qu trnh xc nh
Trc lc bt u lm vic, mi thit b v dng c phi c ra sch
bng nc Crm v trng bng nc ct, sp xp dng c trn bn lm vic cng
vi cc ho cht cn thit sao cho tht tin li. Ch lm vic phi c chiu
sng tt nhng khng c nh sng mt tri trc tip ri vo.
Kim tra nng dung dch Bc Nitrat
Nng dung dch Bc Nitrat rt d bin i di tc dng ca nh sng
nn vic kim tra n phi c thc hin hng ngy (trc lc phn tch mu).
Trc ht trng Biuret bng chnh dung dch Bc Nitrat cn kim tra, sau
ly y dung dch vo Biuret cho ti vch s "0". Cn phi thy r trong
Biuret khng c bt kh, nu c phi lm li.
Tip , dng Pipet sch kim nh (loi th tch c nh 15 ml) ly 15
ml nc bin tiu chun cho vo cc chun c ra sch bng nc ct
(trc khi ly nc bin tiu chun, Pipet cng phi c trng cn thn bng
chnh nc bin tiu chun). khng gy si bt khi cho nc bin tiu chun
vo cc chun , u Pipet phi t st vo thnh cc. Khi cht lng chy
ht vo cc, ch 15 giy sau mi c nhc u Pipet ra khi thnh cc v t
Pipet vo v tr quy nh. Nht thit khng c thi vo cht lng cn dnh
u Pipet.
Tip nh 5 git K2CrO4 10% vo lng nc bin tiu chun ly.
Kim tra li mt ln na dung dch Bc Nitrat trong Biuret ng vch "0"
cha, c bt kh trong Biuret khng? Nu mi yu cu c tho mn th bt
u chun nc bin tiu chun.
Trong qu trnh chun cn khuy lin tc ph v cc kt ta trng
sa. Nu kt ta khng b ph v, n s bao bc v gi lun mt lng halogen
no ca nc bin tiu chun, v do s lm sai lch php hiu chnh nng
18
dung dch Bc Nitrat. Lc u c th m to van Biuret dung dch Bc

Nitrat chy nhanh xung cc chun . Khi xut hin cc vt da cam th
hm van li v cho dung dch chy tng git mt tht cn thn (gn n thi
im tng ng c th ch cho chy tng na git mt). Vic chun c
coi l kt thc khi v ch khi mu da cam xut hin r nt, phn b ng u
trong cht lng cc chun v khng b mt i sau 20-25 giy tm ngng
chun v khuy. Ghi li s c trn Biuret vi chnh xc 0,01 chia.
Tin hnh chun li nc bin tiu chun ln th hai vi tt c quy trnh
v iu kin hon ton tng t. Nu s c trn Biuret ca 2 ln chun
khng khc nhau qu 0,02 th gi tr trung bnh ca 2 s c c s dng
tnh ton kt qu. Nu s sai khc vt qu 0,02 th phi chun li ln th ba
v ly 2 kt qu tho mn yu cu trn. Nu ln th 3 vn c s sai khc ngoi
gii hn cho php th c th do dung dch Bc Nitrat cha c xo trn u, ta
phi lc bnh tht k xo trn li dung dch.
Vi cch chn nng dung dch Bc Nitrat nh nu mc 1.1.4 th v
nguyn tc s c trn Biuret phi bng gi tr Clo ca nc bin tiu chun,
tc l s c phi bng 19,38 (trong trng hp ny s dng nc bin tiu
chun c Clo 19,38%o). Tuy nhin do mc sch ca ho cht, do sai s
ca cc php cn, ong... m iu ny khng t c. Nhng r rng i lng
= N - A (N l Clo ca nc bin tiu chun, A l s c trn Biuret khi
chun nc bin tiu chun) s c trng cho chnh xc ca dung dch
Bc Nitrat. Gi tr tuyt i ca cng nh th dung dch Bc Nitrat cng t
yu cu. Khi s dng cc bng hi dng tnh ton Clo v mui nc
bin theo kt qu chun Bc Nitrat, gi tr ch c nm trong gii hn:
-0,150 0,145
Nu nm ngoi khong ny th dung dch Bc Nitrat c nng cha t
yu cu, cn phi hiu chnh li n. C hai kh nng sau:
+ Trng hp >+0,145 (A nh so vi N): iu ny c ngha l th tch
dung dch Bc Nitrat chi ph qu t m vn kt ta ht c lng halogen trong
19
15 ml nc bin tiu chun, ni cch khc, dung dch qu m c. Vy lng

nc ct cn thit thm vo lng dung dch cn li l:
X (mililit) = (V0 - VT). /A
(1.3)
+ Trng hp <-0,150 (A ln so vi N): iu ny chng t dung dch qu

long. Vy lng tinh th AgNO3 cn thit thm vo lng dung dch cn li
l:
Y (gam) = (V0 - VT). .37,1/1000.A
(1.4)
Trong c 2 cng thc trn, V0 l th tch dung dch iu ch lc ban u, VT

- th tch dung dch dng trng dng c v chun , (V0-VT) l th tch
cn li ca dung dch cn c hiu chnh.
V d: Khi chun nc bin tiu chun c Clo N = 19,38, ln th
nht ta tm c s c trn Biuret l A1 = 19,16, hiu chnh Biuret ng vi s
c ny l +0,01; cc gi tr tng t ca ln th 2 l A2 = 19,17 v 0,00 (hiu
chnh Biuret theo s c c trong bng kim nh ca n). S c trung bnh
hiu chnh l:
A= (19,16 + 0,01 + 19,17 + 0,00):2 = 19,17.
Vy = N-A = 19,38 - 19,17 = +0,21.
Gi tr ny vt khong quy nh v c du dng nn dung dch Bc
Nitrat chun b l qu m c. Gi s lc u ta iu ch 5 lt dung dch, sau
hai ln th nghim dng ht 110 ml ( trng Biuret, Pipet v chun ). Theo
cng thc (1.3), lng nc ct cn thit thm vo lng dung dch cn li
l:
X = (5000-110).0,21/19,17 = 53,57 ml
Sau khi hiu chnh lng dung dch cn li, dung dch cn c lc u
v phi c kim tra li chun (cc bc hon ton nh nu).
Ngoi vic dng cc cng thc trn, c th s dng cc bng tnh sn hoc
20
cc ton lp sn tm c nhanh chng s gam AgNO3 hoc s mililit

nc ct cn thit hiu chnh nng cho mt lt dung dch. Cc bng hoc
cc ton ny c in trong cc sch chuyn mn.
Chun mu nc bin
Mu nc sau khi t trong phng th nghim t 1 gi tr ln nhit
ca n bng vi nhit phng, th c th em chun . Trc ht np dung
dch Bc Nitrat t yu cu vo Biuret. Tip trng Pipet bng chnh mu
nc cn phn tch v ly 15 ml mu cho vo cc chun sch, b sung thm 5
git dung dch K2CrO4 vo lng mu va ly. Kim tra li mt ln na cc yu
cu ca php phn tch, nu tho mn th bt u chun mu nc. Cng vic
tip theo c tin hnh ng nh m t i vi vic kim tra nng dung
dch Bc Nitrat. Khi mu da cam xut hin n nh v khng mt i sau 20-25
giy tm ngng chun v khuy th kt thc th nghim v ghi li s c trn
Biuret. Lm li th nghim ln th hai ly gi tr trung bnh ca 2 ln phn
tch. Nu c mt nghi ng no v s ng n ca vic chun (nh mu
sc thi im kt thc, c bt kh trong Biuret, vch s "0" cha c xc
lp...) cn phi chun li.
Mt s iu ch
- Cht kt ta trng sa AgCl cn c thu hi tinh ch li, v Bc l
kim loi qu him.
- Khi phn tch tip mu khc, khng nht thit phi trng cc chun
bng nc ct v cc ht kt ta trng sa AgCl ca ln chun trc nu c
st li trong cc cng khng nh hng ti chnh xc ca ln chun sau.
Nhng nu mu nc trc chun khng ng (v d kt thc sm hn
hoc mun hn thi im tng) th phi trng cc tht sch bng nc ct. Ni
chung nu khng qu khan him nc ct th nn trng sch cc chun .
- Trong qu trnh lm vic, nu Pipet hoc Biuret b bn, nh xut hin cc
vt nhn hay cc git l lng bm vo thnh bn trong th phi ra n bng hn
hp nc Crm. Khi tm thi kt thc cng vic hoc sau mt ngy lm vic,
21
phi np nc ct vo y Pipet v np dung dch AgNO3 vo y Biuret, sau

ph chng bng o vi en dy.
1.1.7. Tnh ton kt qu
Nh bit, khi kim tra nng dung dch AgNO3 bng nc bin tiu
chun, ta tm c s c trng cho s sai khc cht t gia s c trn Biuret
(A) v Clo ca nc bin tiu chun (N). Dng dung dch AgNO3 kim tra
ny chun mu nc, ta c c s c trn Biuret l a. C th chc chn
rng gi tr ca a rt gn vi Clo ca mu nc, ch sai khc mt lng rt
nh k m thi. D dng suy ra rng, nu s c a = A th s sai khc k = , v
nu a cng gn A th k cng cng gn . Nh vy gi tr ca k hon ton ph
thuc vo gi tr v a. Trong Ho hc bin thc hnh, gi tr k c tnh trc
theo v a v cho sn thnh bng (bng 1.1) hoc ton .
Bng 1.1. Gi tr s hiu chnh k theo a v (trch t bng hi dng)
=-0,150
=-0,145
=-0,140
=-0,135
=-0,130
a=
a=
a=
a=
a=
22.90
23.03
23.17
22.65
22.78
22.92
23.06
23.20
-0.27
...
...
...
...
...
-0.26
19.38
19.52
19.67
19.82
19.97
-0.15
19.06
19.21
19.36
19.51
19.66
-0.14
18.74
18.89
19.04
19.19
19.35
-0.13
18.42
18.57
18.72
18.87
19.03
-0.12
18.08
18.23
18.39
18.54
18.70
-0.11
...
...
...
...
...
-0.10
13.38
13.57
13.76
13.95
14.14
12.78
12.98
13.18
13.38
13.58
k=
23.14
-0.28
22
+0.01
Sau khi tm c s hiu chnh k, Clo ca mu nc c xc nh theo

cng thc sau:
Cl%o = a + k
(1.5)
Dng cng thc (1.1), (1.2) c th tnh c mui v t trng ca mu

nc theo Clo. Vi cc bng hi dng chuyn dng hin nay (v d bng
1.2) c th xc nh nhanh chng mui, t trng, mt , th tch ring, th
tch ring quy c ca nc bin theo Clo v nhit ti ch (in situ).
Bng 1.2. Tr s mui (S), mt quy c (0) v t trng (17,5)
ca nc bin (trch t bng hi dng)
Cl %o
S %o
17,5
Cl %o
S %o
17,5
18.00
32.52
26.13
24.84
18.50
33.42
26.86
25.53
.01
.54
.14
.85
.51
.44
.87
.54
.02
.56
.16
.86
.52
.46
.88
.55
...
...
...
...
...
...
...
...
18.10
32.70
26.27
24.97
18.60
33.60
27.00
25.66
.11
.72
.29
.99
.61
.62
.02
.68
.12
.74
.30
25.00
.62
.64
.03
.69
...
...
...
...
...
...
...
...
18.20
32.88
26.42
25.11
18.70
33.78
27.15
25.80
.21
.90
.43
.13
.71
.80
.16
.82
.22
.92
.45
.14
.72
.82
.18
.83
.23
.94
.46
.15
.73
.84
.19
.84
...
...
...
...
...
...
...
...
18.30
33.06
26.56
25.25
18.80
33.96
27.29
25.94
.31
.08
.58
.26
.81
.98
.31
.96
.32
.10
.59
.28
.82
34.00
.32
.97
23
V d:
- clo ca nc bin tiu chun l N = 19,380
- S c trn Biuret khi chun nc bin tiu chun ln th nht l
A1=19,52, hiu chnh s c ng vi 19,52 l 0,00; ln th hai l A2=19,53, hiu
chnh s c ny l -0,01. S c trung bnh ( c hiu chnh) sau 2 ln
chun nc bin tiu chun l A=(19,52+0,00+19,53-0,01):2=19,52.
- Gi tr = N-A = 19,38-19,52 =-0,14 chng t dung dch Bc Nitrat ny
t yu cu chun mu nc.
- S c trn Biuret khi chun mu nc l 18,82, hiu chnh s c ca
Biuret ng vi 18,82 l +0,03. S c thc l a = 18,82 + 0,03 = 18,85.
- S k tm c t bng bng 1.1 theo v a l k=-0,12.
- Clo ca nc bin l Cl=a+k = 18,85-0,12=18,73%o.
- Tra bng 1.2 ta c S=33,84%o, o = 27,19 v 17,5 = 25,84.
y mt ln na nhc li rng cng thc Knudsen v cc bng tnh sn
ch p dng c vi nc i dng v cc bin h. Nhng bin kn, vng,
vnh...v cc khu vc lu thng km vi i dng hoc nhng vng nc chu
nh hng mnh ca dng lc a th phi s dng cc cng thc hoc cc bng
ring.
1.1.8. Th t cng vic
Bc 1: Kim tra s sch s ca dng c, trong trng hp cn thit phi
ra li.
Bc 2: Np dung dch AgNO3 vo y Biuret sau khi trng n bng
chnh dung dch ny. Tip kim tra chun ca dung dch Bc Nitrat theo
nc bin tiu chun, nu cha t yu cu phi hiu chnh li (xem mc 1.1.6.
chng ny).
Bc 3: Np dung dch AgNO3 t yu cu vo y Biuret.
24
Bc 4: Sau khi trng Pipet bng chnh nc mu phn tch, ly 15 ml

nc mu cho vo cc chun sch, cho tip 5 git dung dch K2CrO4 10%
vo lng mu va ly.
Bc 5: Chun mu nc bng dung dch Bc Nitrat c hiu
chnh, cho ti khi mu da cam n nh. Khi c s nghi ng v chnh xc phi
chun li. Ghi kt qu chun vo s.
Bc 6: Thu hi kt ta mui Bc vo bnh cha.
Bc 7: Lm li t bc 3 n bc 6 cho mu khc.
Bc 8: Vic tnh ton kt qu c tin hnh sau khi chun ht s mu,
hoc sau mt ngy lm vic. Cc kt qu tnh ton cn c ngi th hai kim tra.
1.2. XC NH CLO CA VNG NC NHT VEN B

Nc cc khu vc bin ven b, nht l cc vng ca sng, cc m ph,
vng vnh kn... thng c mui rt thp. Tuy vy, cc nguyn t thuc nhm
halogen vn thng c mt trong nc vi hm lng cao hn cc hp phn
khc. Khi nghin cu nhiu qu trnh khc nhau cc i tng nc ny, ion
Clo vn c ch mt cch thch ng. Trong thc t, ngi ta thng s
dng cc "h s Clo", v d h s Kim-Clo (Alk/Cl) hay h s Sunfat-Clo
(SO4/Cl)... c trng cho tng khu vc nc hoc tnh ton cc c trng
ng lc a phng v t l xo trn gia cc loi nc trong qu trnh tng
tc bin-lc a.
Nh ch ra mc 1.1.2 chng ny, cc khu vc chu nh hng trc
tip ca lc a nh k trn c t l gia cc hp phn chnh ho tan trong nc
khng ging nh i dng v cc bin h, m chng thng xuyn b thay
i mnh di tc ng trc tip hoc gin tip ca thu triu, cc dng lc a
cng nh hng lot cc qu trnh kh tng, thu vn a phng v con ngi.
Hin nhin, vic xc nh Clo theo phng php Knudsen cng vic s dng
cc bng hi dng i vi cc vng nc ny khng thch hp.
25
1.2.2. Phng php xc nh

Theo ch tiu phn loi ca Hi dng hc, nc c mui nh hn 1%o
l nc nht, t 1 n 24,69%o l nc l v ln hn 24,69%o l nc mn. Ch
c hai trng hp sau mi s dng c phng php Knudsen v cc bng Hi
dng xc nh Clo v mui nc bin. xc nh Clo ca nc
nht (trng hp th nht), v nguyn tc ngi ta vn s dng phng php
chun mu nc bng dung dch AgNO3 c nng bit trc, cho n khi
cc halogen trong mu b kt ta ht. Ch khc vi phng php Knudsen ch,
do hm lng Clo trong nc loi ny rt nh nn dung dch AgNO3 cng phi
c nng nh tng ng v Clo ca loi nc ny c biu din bng
miligam ion Clo trong mt lt nc (mgCl-/l), ch khng phi g/kg (%o) nh
trong trng hp nc bin. y cng cn nhn mnh rng, vi phng php
chun mu nc bng dung dch Bc Nitrat ta cng ch xc nh c tng s
cc halogen c trong mu. Bi vy, th nguyn mgCl-/l bao gm c cc ion
halogen c quy i tng ng sang Clo. Cc phn ng m t nguyn tc
ny hon ton tng t trng hp nc bin (xem mc 1.1.2).
- Biuret c dung tch 50 ml, chia bnh thng (1 chia nguyn c th
tch 1ml v c chia thnh 10 phn). Biuret phi c kim nh km theo.
- Pipet cc loi 100 ml, 50 ml, 25 ml, 5 ml, 1 ml.
- Cc loi bnh nh mc hnh tr, hnh nn, bnh chun , bnh ng dung
dch Bc Nitrat v cc dng c thng thng khc.
1.2.4. Ho cht
Dung dch Bc Nitrat
V hm lng halogen trong nc nht rt thp (ch nm trong gii hn t
mt vi n di 1000 mgCl-/l - cha n 1%o) nn cn phi c hai loi dung
dch Bc Nitrat cng hai loi dung dch chun kim tra chng.
26
Dung dch Bc Nitrat loi 1: mi mililt dung dch tng ng vi 2,5 mg

Cl-, ngha l lng Bc c trong 1 ml dung dch loi ny va kt ta ht
2,5 mgCl-.
Dung dch Bc Nitrat loi 2: mi mililit dung dch tng ng 1 mg Cl(lng Bc c trong 1 ml dung dch loi ny va kt ta ht 1mg Cl).
chun b dung dch loi 1, ngi ta ly 12,0 gam Bc Nitrat tinh khit
v pha thnh 1 lt dung dch; vi dung dch loi 2, ly 4,8 gam Bc Nitrat pha
thnh 1 lt (hoc ly 400 ml dung dch loi 1 pha thnh 1 lt loi 2). Cn ch
rng nc ct pha dung dch phi khng c Clo, dung dch pha xong phi
trong sut. Cch s l dung dch cha t yu cu v bo qun dung dch ging
nh nu mc 1.1.
Cc dung dch chun
kim tra nng cc dung dch Bc Nitrat, ngi ta s dng hai loi
dung dch chun tng ng sau:
Dung dch chun NaCl loi 1: Trong 1 ml dung dch c 2,5 mgClDung dch chun NaCl loi 2: Trong 1 ml dung dch c 1 mgCl chun b cc dung dch chun, cn phi c mui NaCl tinh khit (cch
lm sch mui NaCl y khng trnh by). Vi dung dch chun loi 1, cn
tht chnh xc 4,1210 g tinh th NaCl ri pha vi nc ct thnh 1 lt; vi dung
dch loi 2, ly 1,6484 g tinh th NaCl pha thnh 1 lt.
Thuc ch th mu
Thuc ch th mu K2CrO4 10% c chun b nh mc 1.1.4.
Ly v bo qun mu nc cc vng nc nht cng tng t nh ly
mu nc bin, nhng cn ch l phi s dng 50 ml (hoc 100 ml ) phn
tch (ch khng phi 15 ml) nn cn phi ly nhiu hn. Trc khi phn tch,
mu nc cng phi t trong phng mt thi gian cn thit n c cng nhit
27
ca phng.
Th nghim nh tnh
Trc ht phi lm php th nh tnh xem cn phi s dng dung dch
Bc Nitrat loi no. Mun vy, ly 5 ml mu nc cn phn tch cho vo bnh
tam gic, cho tip 2 git ch th mu v sau chun mu bng dung dch
Bc Nitrat loi 1. n thi im tng ng (l thi im mu da cam n nh
sau 20-25 giy - xem mc 1.1), nu th tch dung dch Bc Nitrat dng (k
hiu l V) ln hn 2 ml, iu c ngha l hm lng cc halogen trong mu
(k hiu Cl) ln hn 1000 mgCl/l - ta c th p dng phng php Knudsen nh
i vi nc bin. Nu 1ml < V 2ml, ngha l 500 mgCl/l < Cl 1000 mgCl/l
ta cn dng dung dch Bc Nitrat loi 1 phn tch mu nc, nu V 1 ml ta
cn dng dung dch Bc Nitrat loi 2.
Kim tra nng dung dch Bc Nitrat
V dung dch Bc Nitrat rt hay bin i di tc dng ca nh sng v
nhit nn kim tra nng ca n l vic lm rt cn thit v thng xuyn.
Dung dch Bc Nitrat loi no th dng chun loi kim tra.
Ly 25 ml (hoc 20 ml) dung dch chun cho vo bnh tam gic ri b sung
nc ct n 100 ml (c th dng bnh chia thay cho bnh tam gic). Sau
cho thm 1 ml ch th mu v chun hn hp bng dung dch Bc Nitrat
tng ng vi chun ly. Ch l tt c cc Biuret, Pipet trc khi s dng
phi tht sch v phi trng n bng chnh dung dch cn ly. Trong khi chun
phi khuy lin tc. Vic chun s kt thc ti thi im tng ng.
Ghi li s c trn Biuret v lm li th nghim ly s c ln th hai. Gi tr
s c trung bnh ca hai ln chun s c s dng tnh ton kt qu.
Nng tht ca dung dch Bc Nitrat tnh tng ng theo lng Clo,
k hiu l TAgNO3 (mgCl-/ml), c xc nh theo cng thc sau:
TAgNO3 (mgCl-/ml) = (V +v).[Cl-]/(n + n)
28
(1.6)
Trong [Cl-] l hm lng ion Cl- c trong 1 ml dung dch chun, V - th

tch Pipet ly dung dch chun (25ml hoc 20ml) v v - hiu chnh ca
Pipet, n - s c trung bnh trn Biuret v n - hiu chnh ca Biuret ng vi s
c ny.
V d: kim tra nng dung dch Bc Nitrat loi 1, ta ly 25ml dung
dch chun loi 1 (1ml c 2,5 mgCl-), hiu chnh ca Pipet ny l -0,05. Ln
chun th nht c s c trn Biuret l 25,28, ln th 2 - 25,32. S c trung
bnh sau 2 ln chun l 25,30 v hiu chnh Biuret ng vi s c ny l
+0,05. Vy nng thc ca dung dch Bc Nitrat loi 1 theo cng thc 1.6 l:
T = (25-0,05) 2,5/(25,30+ 0,05) = 2,461 (mgCl-/ml)
Xc nh Clo ca mu nc
Cn c vo php th nh tnh, ta la chn c dung dch Bc Nitrat
thch hp v tin hnh kim tra nng thc ca n. Nu php th cho bit phi
dng Bc Nitrat loi 1 th phn tch mu ta phi ly 50 ml nc mu (trng
hp phi dng Bc Nitrat loi 2 th phi ly 100 ml nc mu) ri cho vo bnh
tam gic. Cho thm 1 ml ch th mu vo v sau chun mu bng dung
dch Bc Nitrat chn trong khi khng ngng khuy mnh. Vic chun
c kt thc ti thi im tng ng. c kt qu v khi vo s.
Clo (mgCl-/l) ca mu nc c tnh theo cng thc sau:
Cl (mgCl-/l) = (n +n).T.1000/(V +v)
(1.7)
Trong , n l s c trn Biuret v n l s hiu chnh ca n; V- th tch

Pipet ly mu nc phn tch (50 ml hoc 100 ml) v v l s hiu chnh ca
n; T - nng thc ca dung dch Bc Nitrat c s dng.
V d: Php th nh tnh cho bit phi dng dung dch Bc Nitrat loi 1 c
nng tht ( c kim tra) l 2,461. Do phi dng Pipet c dung tch
50ml ly 50 ml mu nc, s hiu chnh ca Pipet l -0,03. S c trn Biuret
29
sau khi chun l 21,20 v hiu chnh Biuret ng vi s c ny l +0,04. Vy

Clo ca mu theo cng thc 1.7 l:
Cl (mgCl-/l) = (21,20+0,04). 2,461.1000/(50-0,03)= 522,87
y khng th dng cc bng hi dng tm gi tr mui v t
trng ca nc, v cc bng ch s dng i vi nc i dng v bin h.
Mun tm mui, phi t tm mi quan h ca n vi Clo. iu ny rt kh
nn thng ngi ta ch xc nh Clo l .
1.2.8. Th t cng vic
Bc 1: Kim tra s sch s ca dng c, nu cn phi ra li.
Bc 2: Kim tra chun ca c hai loi dung dch Bc Nitrat nh m
t trn. Trc khi kim tra dung dch loi no phi trng Biuret bng chnh
dung dch loi y.
Bc 3: Lm php th nh tnh la chn dung dch Bc Nitrat thch
hp. cho tin li, php th nh tnh nn c thc hin cng mt lc cho c
lot mu hoc mt phn ca lot mu. Sau phn loi v ring chng ra,
mi loi s dng mt dung dch Bc Nitrat thch hp.
Bc 4: Tu theo kt qu php th nh tnh m ly 50 ml mu nc (vi
trng hp chn dung dch Bc Nitrat loi 1) hoc 100 ml mu nc (vi trng
hp chn dung dch loi 2) phn tch.
Bc 5: Ghi kt qu phn tch vo s chuyn mn. Sau tip tc phn
tch mu khc.
Bc 6: Vic tnh ton kt qu c tin hnh sau khi chun ht s mu,
hoc sau mt ngy lm vic. Kt qu tnh ton phi c ngi th hai kim tra li.
30
Chng 2
XC NH CC KH HO TAN TRONG NC BIN
2.1. XC NH KH XY HO TAN BNG PHNG PHP CHUN IT
(PHNG PHP VINCLER)

Cng vi tr s pH, kh xy ho tan l yu t thu ho quan trng xc nh
cng ca hng lot qu trnh sinh-ho xy ra trong mi trng nc bin.
Vi kh nng hot ng ho hc mnh, xy ho tan trong bin l mt hp phn
rt linh ng, s phn b theo khng gian v bin i theo thi gian ca n chu
tc ng ca hng lot hin tng v qu trnh, trong ng k nht l cc qu
trnh tng tc bin-kh quyn, hot ng ca thu sinh vt, nhim mi
trng...
Chnh v vy, xy ho tan trong nc bin c xem l mt trong nhng
yu t ch th cho khi nc, cho nhiu qu trnh ho-l xy ra trong ng
thi cn c s dng nh mt ch tiu c bn nh gi mc nhim mi
trng, nht l nhim cht hu c. Xc nh hm lng xy ho tan l cng
vic khng th thiu c ca cc nghin cu Ho hc bin.
biu th nh lng kh xy ho tan trong nc bin, ngi ta thng
dng hai dng nng : nng tuyt i v nng tng i. Nng tuyt
i l s th tch hoc trng lng (mililit, miligam, micro nguyn t gam...) kh
xy ho tan trong 1 lt nc bin (mlO2/l, mgO2/l, AT-O/l...). Nng tng
i l t s phn trm ca nng tuyt i v nng bo ho xt iu kin
ti v tr v thi im ly mu, cn gi l iu kin ti ch (in situ). Trong bng
2.1 c a ra mt s gi tr nng bo ho ca kh xy ho tan trong nc
bin ti cc iu kin nhit v mui khc nhau.
31
Bng 2.1. Nng bo ho (mlO2/l) kh xy ho tan

trong nc bin (trch t bng hi dng)
Nhit
mui (%o)
(oC)
10
20
30
35
10.29
9.97
9.65
9.00
8.36
8.04
9.03
8.75
8.49
7.94
7.40
7.13
10
8.02
7.79
7.56
7.09
6.63
6.41
15
7.22
7.02
6.82
6.43
6.03
5.83
20
6.57
6.40
6.22
5.88
5.52
5.35
30
5.57
5.42
5.27
4.95
4.65
4.50
Ngy nay ngnh Hi dng hc c cc my hoc thit b o trc tip

hm lng xy ho tan trong nc bin. Mt s thit b hin i c th o lin
tc hm lng xy ho tan t mt bin n su hng nghn mt v ghi kt
qu o vo bng t. Cng tng t cc thit b o mui, cc thit b o xy
ho tan trong nc bin thng t tin v mc d rt tin li trong kho st
thc a nhng nhn chung kt qu nhn c thng khng t chnh xc
mong mun ca Hi dng hc m ch c ngha kim tra cht lng mi
trng (tr mt s thit b hin i). Bi vy, phng php ho hc tuy cng
knh phc tp do phi chun b trc cc ho cht v dng c thu mu v phn
tch mu song li t tn km v c chnh xc cao, vn l phng php hu
hiu nht hin ang c s dng rng ri trong Hi dng hc Vit Nam v th
gii xc nh xy ho tan trong nc bin. l phng php chun Iot
(Iotdometre) do Vincler xut, cn gi l phng php Vincler, c chnh
xc 0,02 mlO2/l tho mn yu cu ca Hi dng hc. Phng php ny cn
c s dng rt hiu qu trong vic xc nh cc ch tiu mi trng nh BOD,
COD... (xem mc 4.7 chng 4), hoc xc nh nng sut sinh hc s cp thng
qua hiu ng bin i hm lng xy trong cp bnh en-trng.
2.1.2. Phng php Vincler
Nu a vo mu nc bin c xy ho tan mt lng no dung dch
32
mui Mangan2 (nh MnCl2 hoc MnSO4) v sau l dung dch Natri kim
(NaOH), hoc Kali kim (KOH), th lp tc chng s phn ng vi nhau ngay
trong lng mu nc to ra kt ta Mangan2 hydroxuyt mu trng Mn(OH)2.
V d:
MnCl2 + 2NaOH = Mn(OH)2 + 2NaCl
(2.I)
Mangan2 hydroxuyt l mt cht kh mnh s phn ng ngay vi xy t do

ho tan trong mu nc v c nh chng li kt ta mu nu, l axit
Manganic:
2Mn+2(OH)2 + O2 = 2Mn+4O(OH)2 (mu nu)
(2.II)
phn ng ny Mangan2 chuyn thnh Mangan4, cn xy phn t

chuyn thnh anion theo c ch thu gn sau:
2Mn+2 + O20 = 2Mn+4 + 2O-2
D dng thy rng lng Mangan4 c to ra t l vi lng xy t do
ho tan trong mu nc. Do vy ch cn xc nh chnh xc lng Mangan4 l
s xc nh c lng xy trong mu. Cc phn ng 2.I v 2.II c gi l
phn ng c nh xy. Vic c nh xy phi thc hin ngay sau khi ly mu.
Mu nc c nh xy c em v phng th nghim phn tch.
Lng Mangan4 ni trn c xc nh bng phng php Vincler. Trc
ht cn ph v kt ta mu nu (trong ton b lng xy t do ca mu
c c nh) bng axit Clohydric (hoc axit Sunfuric), c s tham gia ca Kali
Iotua (KI c th a vo mu cng lc vi kim khi thc hin phn ng 2.I, v
s c mt ca n khng nh hng ti cc phn ng 2.I v 2.II). Kt qu ca qu
trnh ph v kt ta ny l to ra It t do trong mu:
Mn+4O(OH)2 + 2KI-1 + 4HCl=Mn+2Cl2 + 2KCl + 3H2O + I2o
(2.III)
R rng lng It t do c to ra phn ng ny t l vi lng

Mangan4, cng c ngha l t l vi lng xy c trong mu nc. Vy ta ch
cn xc nh chnh xc lng It t do k trn. Dng dung dch Natri Thyosunfit
33
(Na2S2O3) c nng bit trc chun hn hp phn ng 2.III, khi

ch c It t do phn ng vi Thyosunfit:
I2 + 2Na2S2O3 = 2 NaI + Na2S4O6
(2.IV)
Nu bit th tch dung dch Na2S2O3 chi dng phn ng ht vi lng

It t do k trn, th s tnh c hm lng xy ho tan trong mu nc.
xc nh thi im ngng chun (cn gi l thi im tng ng), l thi
im m trong hn hp ang chun khng cn It t do na, ngi ta dng
dung dch tinh bt lm ch th. Khi chun gn n thi im tng ng
(iu ny ph thuc kinh nghim ca ngi phn tch), cho vo hn hp mt t
dung dch tinh bt, mu xanh It lp tc hin ln. Hn hp nhum mu ny
c tip tc chun mt cch thn trng cho n khi mt mu hon ton.
C hai iu ch sau y:
Th nht: Mu nc bin xc nh xy ho tan bng phng php
Vincler khng c c mt cc cht xy ho, v d mui ca axit Nitric, mui
ca st 3... Cc cht ny khi c trong mu s c vai tr tng t MnO(OH)2
phn ng 2.III, ngha l chng xy ho anion Iot ca KI v gii phng It. Do
vy, lng It t do trong mu s tng ln v khng ch c mt qu trnh to ra
n, v ng nhin s tiu hao thm mt lng no Thyosunfit nh thy
phn ng 2.IV. Trn thc t, nhng cht xy ha nu trn thng c nng
nh khng ng k trong nc i dng v bin thong, chng ch c ngha
vng nc gn b hoc cc vng nc chu nh hng ca ngun thi cng
nghip v sinh hot. Mu nc ly nhng khu vc ny cn phi tnh n s c
mt ca cc cht xy ho.
Th hai: Mu nc bin xc nh xy ho tan bng phng php
Vincler cng khng c c mt cc cht kh, bi v chng s chim ly mt
lng no It t do, ging nh Thyosunfit phn ng 2.IV. Do , lng
Thyosunfit chi dng thc t s t hn. Mt trong nhng cht kh c th xut hin
trong nc bin l kh Sunfuhydro (H2S). Nu mu nc c H2S, ta cn phi loi
b nh hng ca n trc khi xc nh xy ho tan (phng php loi b nh
34
hng ca kh H2S s c trnh by mc 2.2 chng ny). Tuy nhin, kh

Sunfuhydro thng ch xut hin nhng khu vc nc b nhim, y cc
vc su, cc vng vnh km lu thng v km thong kh.
- Biuret c dung tch 25 ml, tt nht l dng loi t ng xc lp vch s
"0". Biuret phi c kim nh km theo.
- Pipet dung tch 15 ml, tt nht l dng loi t ng v cng phi c bng
kim nh; Pipet dung tch 1ml (c t nht hai chic); Pipet dung tch 5ml c gn
qu bp ly axit (1 chic). Cc Pipet phi sch v ch chuyn s dng cho
mt loi ho cht.
- Bnh hnh nn chun mu nc, th tch t 250-500 ml.
- Chai thu tinh mu ly mu nc v c nh xy ho tan, dung tch
khong 150 ml, c nt thu tinh mi nhn v phn di ca nt phi mi vt
(hnh 2.1) - gi l l xy. Cn c bit ch l l xy ch c s dng cho mc
ch ly mu v c nh xy ho tan m khng c s dng vo mc ch
khc. Th tch ca l tnh n phn vt ca nt phi c xc nh mt cch
chnh xc v c hiu chnh km theo. Nhng s liu v th tch cng s hiu
chnh v nhn hiu ca l xy cn c ghi ln thnh bn ngoi. trnh nhm
ln cc nt, nhn hiu l cng phi c ghi ln nt ca n. Cc l xy cn c
bo v trong hp g, c m, c np nhm trnh bt nt khi vn chuyn.
No12
146,5
l
Hnh 2.1. L xy
35
- Ngoi cc dng c nu trn cn phi c cc loi bnh nh mc hnh cu,

hnh tr, cc chai l cha ho cht v bo qun dung dch, cc dng c v
thit b thng thng khc.
2.1.4. Ho cht
Cc ho cht s dng phn tch xy ho tan phi tht tinh khit, khng
c c ln cc tp cht, nht l cc cht xy ho hoc cht kh. S c mt ca
chng s dn n sai s nh nu trong cc ch mc 2.1.2. Mi ho cht
trc khi s dng phi c kim tra sch, trong trng hp cn thit phi
tinh ch li (phng php kim tra v ty sch ho cht y khng trnh by).
Dung dch Mangan Clorua (hoc Mangan Sunfat)
Dng cn k thut ly 250 gam tinh th MnCl2.4H2O (hoc MnSO4. 4H2O)
ho vi 200-300 ml nc ct. Nu dung dch c th phi lc n. Th tch sau
khi lc c b sung nc ct n 500 ml.
Hn hp dung dch Kim-Kali Itua
Dung dch Kali Itua (KI) dng thc hin phn ng 2.III gii phng It.
Do s c mt ca KI trong kim khng nh hng n cc phn ng c nh
xy 2.I v 2.II nn cho tin li, ngi ta chun b sn hn hp Kim-Kali
Itua. chun b hn hp ny, cn chun b ring hai dung dch kim v Kali
Itua, sau ho trn chng li.
Ly 75 gam KI (c th thay bng 68 gam NaI) ho vi 50 ml nc ct, ta
c dung dch Kali Itua (hoc dung dch Natri Itua), gi l dung dch a. Ly
250 gam NaOH (hoc 350 gam KOH) ho vi 150-200 ml nc ct ta c dung
dch kim Natri (hoc kim Kali), gi l dung dch b. Trn hai dung dch a v b,
sau tng th tch hn hp ti 500 ml bng nc ct. Nu hn hp b c th
bt ng n vi ngy, sau gn ly phn trong. Hn hp c bo qun
trong bnh xm mu.
Cc bnh ng dung dch mui Mangan2 v hn hp Kim-Kali Itua phi
36
c nt cao su kn, qua nt cm c Pipet. Vch du 1 ml ca Pipet phi lun

ngp trong dung dch, khng cn ht m vn ly 1 ml.
Dung dch axit Clohydric 2:1 (hoc axit Sunfuric 1:4)
Dung dch HCl 2:1 c chun b bng cch thm hai th tch axit nguyn
cht (trng lng ring 1,19) vo mt th tch nc ct. Dung dch H2SO4 1:4
c chun b bng cch thm 1 th tch axit nguyn cht (trng lng ring
1,84) vo 4 th tch nc ct.
Khi pha axit vo nc, phn ng pht nhit rt mnh nn phi lm tht t
t, cn thn v ch c dng a thu tinh khuy trn. Cn c bit ch l
ch c thm axt vo nc m khng c lm ngc li. Trng hp lm
ngc li s rt nguy him, c th gy n bnh hoc bng v ht nc b si t
ngt v bn tung ln cng vi axt.
Dung dch chun 0,02N Natri Thyosunfit
Ly 5 gam tinh th Na2S2O3.5H2O ho thnh mt lt dung dch. C th
chun b sn 3-5 lt tu theo s lng mu cn phn tch.
Nng dung dch Thyosunfit thng khng n nh do s c mt ca axit
Cacbonic v cc vi khun phn hu, nht l trong iu kin thi tit nng nc.
Khi chun b dung dch ny, tt c chai l cha v bo qun dung dch phi
v trng. Chai l sau khi c ra bng nc Crm v trng bng nc ct phi
c sy kh v nt kn bng nt n bng.
Nc ct pha dung dch phi v trng v loi ht Cacbonic t do trong
n bng cch un si t 1-1,5 gi, sau ngui ngay trong bnh. Bnh nc
ct c y kn bng nt cao su c cm mt ng thu tinh rng trong c
bng v vi ti xt. C th dng nc ct mi iu ch pha dung dch. Bnh
bo qun dung dch phi xm mu hoc c bc bng giy en, nt bnh c
cm thm ng thu tinh cha vi ti xt.
trnh s ph hoi ca vi khun cn thm 3ml Clorofooc (CHCl3) cho
mi mt lt dung dch.
37
Dung dch tinh bt 0,5%

Ly 0,5 gam tinh bt ho vi mt lng khng ln nc ct trong ng
nghim v lc lin tc. Sau b sung nc ct si cho n 100 ml v tip tc
un si trong 1-3 pht, cho n khi dung dch c mu sng hn.
Dung dch tinh bt rt chng hng do vi khun phn hu nn sau khi
ngui phi thm vo n vi git axit Xalic hoc vi git Clorofooc. kim tra
cht lng dung dch tinh bt, ngi ta cho n tc dng vi cc dung dch c
It. Nu mu xanh lam hin ln chng t dung dch sch, nu c mu tm hoc
nu chng t cht lng tinh bt km. Trng hp ny phi s dng loi tinh
bt tt hn.
Cc dung dch chun kim tra nng dung dch Thyosunfit
Mc d dng mi kh nng bo v chun ca dung dch
Thyosunfit, song n vn c th b bin i t nhiu do nhng nguyn nhn khc
nhau. kim tra chun v xc nh s hiu chnh chun cho dung dch
Thyosunfit, c th dng mt trong ba dung dch chun sau:
a) Dung dch 0,02N Kali Bicrmmat K2Cr2O7
b) Dung dch 0,02N Kali Biodat KH(IO3)2
c) Dung dch 0,02N Kaliitua xuyt KIO3 (cn gi l Kali Iodat).
Lng cn cn ly ho vi nc ct thnh 1 lt cc dung dch ny l:
0,9808 gam tinh th K2Cr2O7 cho dung dch a, 0,6500 gam tinh th KH(IO3)2
cho dung dch b v 0,1734 gam tinh th KIO3 cho dung dch c.
Bnh cha cc dung dch chun phi c nt thu tinh mi nhn. Cc ho
cht iu ch cc dung dch chun phi tinh khit v kh, trng hp cn
thit phi ty sch v kt tinh li. Trc khi pha ch thnh dung dch, tinh th
phi c sy li 180-200oC.
Dung dch Kali itua 10%
Ly 10 gam KI sch pha vi 90 ml nc ct. Dung dch ny dng kim
38
tra chun ca Thyosunfit (xem mc 2.1.6: Qu trnh xc nh). Bi vy ho

cht KI phi tht tinh khit, khng c ln tp cht.
2.1.5. Ly mu nc v c nh xy ho tan
Ly mu nc v c nh xy ho tan cn phi lm ngay sau khi ly mu
xc nh pH. L xy cn phi c ra tht sch v trc khi ly mu phi c
trng 2-3 ln bng chnh nc mu cn ly. Nc mu c ly t my ly nc
(Batmet) vo l qua mt vi cao su, u ca vi c gn mt ng thu tinh nh
cm thng xung tn y, tia nc chy vo l khng c qu mnh
trnh to ra cc bt kh trong . Khi nc y trn, nhc ng thu tinh tht
cn thn ra khi l trong khi tia nc ng vn tip tc chy. Ch khi ng thu
tinh ra khi ming l mi kho van ca my ly nc li. Nh vy ta c mt
l xy thc s y trn nc mu.
Cn phi thy r trong thnh l khng c bt kh (nu c phi ly li).
Ngay sau , ln lt cho vo l nhng ho cht sau: 1 ml dung dch Mangan
Clorua (hoc Mangan Sunfat), 1 ml dung dch Kim-Kali Itua.
Khi a cc ho cht k trn vo l mu, u Pipet cn phi ngp n 1/2
chiu cao ca l cc ho cht ch c th nm pha di. Sau khi cho ho
cht vo, Pipet c nhc t t ra khi mng l. Nht thit khng c dng
ln Pipet i vi hai ho cht k trn. Nu dng ln, phn ng 1 s xy ra ngay
trong Pipt, trong trng hp ny phi ra chng bng axit Clohydric ui
ht kt ta ra. Sau khi a cc ho cht vo l mu, y nt l li sao cho
trong n khng c c bt kh (nt thu tinh mi vt c tc dng trnh hin
tng ny). Tip khuy trn mnh kt ta trong l bng cch o lc 10 ln
kt ta phn b ng u trong l. L mu c nh xy nh k trn c
bt ng ni ti.
Xc nh h s hiu chnh ca dung dch Thyosunfit
y l vic lm hng ngy trc khi bt u phn tch mu nc. Trc
39
ht, trng Biuret bng chnh dung dch Thyosunfit chun b, sau np dung
dch vo y Biuret. Cn phi thy r vch s "0" ca Biuret c thit lp v
trong thnh Biuret khng c bt kh bm vo, nu khng t c hai yu cu
ny th phi lm li.
Tip theo, ly 10 ml dung dch KI 10% v 50 ml nc ct cho vo bnh nn
(c th ho tan trc tip 10 gam KI sch vi 50 ml nc ct ngay trong bnh
ny). Sau dng Pipet t ng ly tht chnh xc 15 ml dung dch K2Cr2O7
0,02N (hoc dung dch KH(IO3)2 0,02N) v 10 ml dung dch H2SO4 1:4 (hoc
dung dch HCl 2:1) cho vo bnh nn k trn. o lc cn thn hn hp trong
bnh, khi It c gii phng theo phn ng sau:
K2Cr2O7 + 6 KI + 14HCl = 8 KCl + 2 CrCl3 + 7 H2O + 3 I2
phn ng ny Cr+6 b kh thnh Cr+3 bi axit Iotuahydro (HI) c to ra
trong qu trnh trung gian, cn anion It b xy ho thnh It phn t. Hin
nhin ta bit trc c lng It t do to ra trong phn ng trn v bit
c th tch (15 ml) v chun (0,02 N) ca dung dch K2Cr2O7.
Chun hn hp trong bnh nn bng dung dch Thyosunfit t Biuret
trong khi khng ngng o lc bnh. Khi cht lng c mu vng ti th b sung
thm vo 1 ml dung dch tinh bt v 50 ml nc ct. Lc cht lng s c
mu xanh lam do It b nhum mu. Tip tc chun hn hp tht cn thn
cho n mu xanh l cy nht (l mu ca Cr+3). Ti thi im ny - thi im
tng ng, trong bnh nn khng cn It t do na. Khi ghi s c trn
Biuret chnh xc ti 0,01 ml vo s chuyn mn.
Ton b qu trnh trn c lm li 2-3 ln vi iu kin lm vic hon
ton tng t. Nu s c ca mi ln khc nhau khng qu 0,05 ml th s c
trung bnh c s dng tnh ton kt qu. Nu s sai khc vt qu 0,05 ml
th cc dung dch chun b cha tt, cc ho cht khng c tinh khit. Cn
phi khc phc bng vic pha ch li cc dung dch.
Nu dng dung dch 0,02N Kaliiotua oxuyt (KIO3) xc nh h s hiu
chnh cho dung dch Thyosunfit, th cng vic cng hon ton tng t nh
40
m t, ch khc l ly 2 ml HCl 2:1 (ch khng phi 10 ml H2SO4 1:4) v chun

n mt mu hon ton (ch khng phi n mu xanh l cy nht, v khng
c Cr+3 nh trng hp trn). Trong trng hp ny, phn ng oxy ho kh gii
phng It c vit nh sau:
KIO3 + 5 KI + 6 HCl = 6 KCl + 3 H2O + 3 I2
Cui cng, h s hiu chnh chun ca dung dch Thyosunfit c tnh
bng cng thc:
KNa = (a1 + 1)/(btb + 2)
v chun thc ca n l:
N = 0,02 KNa
(2.1)
(2.2)
Trong a1 l th tch Pipet ly dung dch chun (15 ml), 1 - s hiu

chnh ca n, btb- s c trung bnh trn Biuret sau hai hoc ba ln chun , 2
- hiu chnh s c ny.
V d: Th tch Pipet ly dung dch chun l 15 ml v c s hiu chnh cho
n l -0,04. S c trn Biuret ln th nht l 14,77, ln th hai l 14,73, trung
bnh l 14,75 v c hiu chnh l -0,55. Theo cng thc (2.1) ta c:
KNa = (15,00 - 0,04)/(14,75 - 0,05) = 1,018
chun ca dung dch Thyosunfit theo pha ch l 0,02, vy chun
thc ca n sau khi hiu chnh l:
N = 0,02 . 1,018 = 0,02035
Xc nh xy trong mu nc c nh xy
Cng vic c th bt u lc kt ta trong l xy n nh v lng xung
mt na nh th tch ca l, nhng khng c qu mt ngy m sau khi ly
mu.
Trc ht, m cn thn nt l xy, sau dng Pipt ly 5ml axit HCl 2:1
(hoc axt H2SO4 1:4) cho tht cn thn vo l, khng c chm hoc khuy
o cc kt ta trong l bng u Pipet. Sau khi thm 5ml axt v y nt l li,
41
s c khong 5ml nc mu b y ra khi l (ng nhin lng nc b y ra

ny khng c xy t do v do vy cng khng c It t do trong n). Sau
gi cht nt l v o ngc lin tc ho tan cc kt ta trong l. Nh vy
phn ng (3) gii phng It c thc hin.
Sau khi kt ta b ho tan hon ton, rt n sang bnh hnh nn v chun
hn hp bng dung dch Thyosunfit c kim tra nng . n khi hn hp
c mu vng ti th thm vo 1ml dung dch tinh bt, mu xanh lam s xut
hin. Tip tc chun hn hp cho n khng mu. Sau rt mt t cht lng
khng mu ny vo l xy trng l v li chuyn phn nc trng sang
bnh nn, lc ny hn hp li c mu xanh lam, nhng cng khng mnh.
Tip tc chun tht thn trng cho n khi hn hp mt mu hon ton, ghi
li s c trn Biuret chnh xc ti 0,01 ml. y cn ch rng, thi im
tng ng l khi cht lng mt mu hon ton ch khng phi mu xanh l
cy nht nh khi kim tra chun ca dung dch Thyosunfit.
Lc bt u v kt thc phn tch mi lot mu, cn phi ghi li nhit
ca phng lm vic.
Tnh ton cc dng nng tuyt i
a) Nng xy ho tan tnh bng mililit kh xy trong mt lt nc bin
c xc nh theo cng thc:
DO (ml/l) = (8.n.N.K.1000)/1,429(V-2)
(2.3)
Trong DO (Dissolved Oxygen) l nng kh xy ho tan trong nc

bin (ml/l), 8 l trng lng ng lng ca xy, n - s mililit dung dch
Thyosunfit tiu th khi chun mu nc bin ( l s c trn Biuret
c hiu chnh), N - chun ca dung dch Thyosunfit (theo pha ch l 0,02)
v K - h s hiu chnh chun ca n, (V-2) - th tch l xy sau khi tr i
2 ml ho cht thm vo lc c nh mu (gm 1 ml dung dch MnCl2 v 1 ml
hn hp dung dch NaOH + KI), 1,429 l trng lng tnh bng miligam ca
42
mt mililit xy iu kin chun (T=0oC, P =760 mm Hg). Trong cng thc

2.3 k trn, v N = 0,02 nn:
8.N.1000 /1,429 = Const = 111,96
Do 2.3 s c vit gn hn. Mt khc, nu lm vic vi mi mt loi l
xy nht nh th th tch V ca n c xc nh chnh xc t trc. Vy nu
gi: M = 111,96/(V-2) th:
DO (ml/l) = M.n.K
(2.4)
Trong bng hi dng ca Zubov thnh lp nm 1957 v cc bng hi

dng sau ny c a ra gi tr ca h s nhn M cho cc l xy c th tch khc
nhau. Ch cn bit trc th tch l, tra bng s c ngay gi tr M.
b) Nng xy ho tan tnh bng miligam kh xy trong mt lt nc bin
(mgO2/l) c xc nh bng tch s ca nng ml/l vi 1,429.
c) Nng xy ho tan tnh bng Micro phn t kh xy (mol) trong 1 lt
nc bin (-M/l) c xc nh nh sau:
V trng lng phn t ca xy l 32 nn 1 -M xy tng ng bng
32.10-6 g hay 0,032 mg. Trng lng ca 1 ml xy l 1,429 mg, nn 1 ml xy =
1,429:0,032 = 44,66 -M xy. Ta ch cn nhn 44,66 vi nng ml/l l c
c nng dng -M/l ca xy ho tan trong nc bin.
d) Tng t nh dng nng -M/l, nng xy ho tan tnh bng
Micro nguyn t trong 1 lt nc bin (-AT/l) c xc nh bng tch s ca
nng ml/l vi 89,32.
Tnh ton nng tng i
Nng tng i ca xy ho tan c tnh nh sau:
O2 (%) = O2 (ml/l) .100/ O2'
(2.5)
Trong O2' l nng bo ho kh xy ho tan (ml/l) iu kin cho

trc, l cc iu kin p sut P=760 mm Hg, mui v nhit bng vi
43
mui v nhit ca mu nc ti thi im ly mu (in situ). Gi tr O2' c

tnh sn theo cc iu kin nhit mui cho trc v cho trong bng hi dng
(bng 2.1 u mc ny).
V d: Sau khi phn tch mu nc bin, tm c nng tuyt i xy
ho tan trong mu l 6,25 ml/l. Ti thi im ly mu, mu c nhit 20oC v
mui 32%o.
Tra Bng hi dng (bng 2.1) ti iu kin nhit-mui ny ta tm c
O2'= 5,46 ml/l. Vy:
O2 (% ) = (6,25.100) : 5,46 = 114 %
Ta ni rng nng tng i ca xy ho tan l 114% bo ho. Trong
trng hp ny nc bin qu bo ho xy.
V d: Trong qu trnh phn tch xy ha tan ta c cc s liu v kt qu
tnh ton nh sau:
- H s hiu chnh chun dung dch Thyosunfit l 1,018.
- L xy s dng ly mu c th tch c nh 105,8 ml nn h s nhn M
=1,079.
- Nhit v mui in situ ca nc bin l 20oC v 30%o, nn O2=5,52
ml/l.
- S c trn Biuret sau khi chun mu nc l 4,24, hiu chnh Biuret
ng vi s c ny l +0,03, vy s c thc l 4,28.
- Nng xy ho tan (ml/l) l: 1,079.4,28.1,018 = 4,70.
- Nng xy ho tan (mg/l) l: 4,70.1,429 = 6,72.
- Nng xy ho tan (-M/l) l: 4,70.44,66 = 209,90.
- Nng xy ho tan (-AT/l) l: 4,70.89,3 = 419,70.
- Nng tng i ca xy ho tan l: (4,70.100):5,52 = 85,14%.
44
2.1.8. Th t cng vic

Bc 1: Chun b cc dng c, thit b v ho cht cn thit ly mu v
c nh xy. Quy trnh ly mu v c nh xy nh m t mc 2.1.5.
Bc 2: Xc nh h s hiu chnh chun dung dch Thyosunfit, ghi kt
qu hiu chnh v nhit phng th nghim vo s.
Bc 3: Khi kt ta ng yn trong l xy, tin hnh ph v kt ta
bng axit HCl hoc H2SO4 v chun mu bng dung dch Thyosunfit kim
tra nng . Cng vic tin hnh nh m t mc 2.1.6.
Bc 4: Ghi kt qu chun chnh xc dn 0,01 ml vo s.
Bc 5: Lm li bc 3, bc 4 cho mu khc.
Bc 6: Vic tnh ton kt qu thng c thc hin sau ngy lm vic
hoc sau khi phn tch xong c lot mu. Kt qu tnh ton phi c ngi th hai
kim tra li.
2.2. XC NH OXY HO TAN TRONG NC BIN KHI C KH
SUNFUHYDRO

Khi c kh Sunfuhydro trong mu nc bin, do n c tc dng vi It nn
trc khi dng phng php Vincler xc nh xy ho tan ca mu cn phi
c thm mt bc ph loi tr nh hng ca H2S. Bc ph ny nhm
chuyn ton b lng H2S v cc dng kh khc ca Lu hunh c th c trong
mu nc sang dng mui kp Thu ngn Sunft-Clorua (HgCl2.2HgS). Nu
thm vo mu nc bin c H2S mt lng no (c d) dung dch mui Thu
ngn Clorua th qu trnh to mui kp trong mu kt ta H2S xy ra nh sau:
3HgCl2 + 2H2S = HgCl2.2HgS + 4HCl
2R2S2O3 + 3HgCl2 + 2H2O = HgCl2.2HgS +2R2SO4+ 4HCl
y R l mt kim loi no .
45
(2.V)
(2.VI)
Nh vy, ton b lng H2S v cc dng kh khc ca Lu hunh c trong

mu b kt ta di dng mui kp HgCl2.2HgS. Mui kp ny khng tc
dng vi It v s c mt ca n khng nh hng n kt qu xc nh xy
ho tan bng phng php Vincler.
Cn nh rng lng HgCl2 cho vo mu phi d. Nu HgCl2 khng d th
mui Thu ngn Sunfit (HgS) c to thnh s tch ri mui Thu ngn
Clorua (HgCl2) m khng to thnh mui kp, v khi mui n HgS s chim
ly mt phn It t do tng t nh Thyosunfit trong phn ng 2.IV ca phng
php Vincler xc nh xy ho tan: HgS + I2 = HgI2 + S. Trong trng hp nh
vy, kt qu xc nh xy ho tan khng chnh xc.
y ta c th yn tm rng, lng d tha mui Thu ngn Clorua thm
vo mu s khng nh hng n kt qu phn tch xy ho tan. Bi v nu mu
nc cng c tha KI (KI c a vo mu khi c nh xy) th:
HgCl2 (d tha) + 2KI (d tha) = HgI2 + 2KCl
v:
HgI2 + 2KI (d tha) = K2(HgI4)
Cc thnh phn c to ra trong 2 phn ng ph ny khng nh hng ti

vic xc nh xy ho tan.
Sau khi lm kt ta H2S v cc dng kh khc ca Lu hunh c trong
mu di dng mui kp Thu ngn Sunfit-Clorua th mu nc c x l
bnh thng nh trng hp khng c H2S (xem mc 2.1).
Ton b dng c, thit b c nh xy v phn tch mu tng t trng
hp khng c H2S (xem mc 2.1.3), nhng do H2S d b phn hu khi c nh
sng nn l oxy phi xm mu, nu khng phi bc l bng vi en.
2.2.3. Ho cht
Ngoi cc ho cht cn thit nh mc 2.1.4, phi c thm mt ho cht
na l hn hp dung dch HgCl2 trong NaCl. Cch chun b hn hp ny l: ly
46
0,25 gam HgCl2 v 20 gam NaCl ho vi 100 ml nc ct.

Ch rng HgCl2 l mt cht c rt mnh (ch 0,2-0,4g lm cht
ngi) nn khi bo qun v s dng mui ny phi ht sc cn thn: khng dng
mm ht Pipet khi ly dung dch, khng dng ln dng c ong, ht vi cc ho
cht khc, bo v dung dch trong t kn c kho v phi ghi "c" ln nhn ca
bnh cha, sau khi s dng xong khng cc l cha HgCl2 trn bn...
V H2S khng xut hin thng xuyn trong nc bin, nn khng ph
thi gian v ch th trc ht cn kim tra nh tnh s c mt ca n trong mu
nc (phn ny s c m t k hn mc 2.3). Nu nhng giy ch vo nc
mu, mu ca giy thm ln (vng hoc nu hoc en) th nc mu c H2S. Khi
, tin hnh ly mu v lm kt ta H2S. Cc bc c tin hnh nh sau:
- Trng l xy 2 ln bng chnh nc mu cn ly, sau ly nc mu
vo y trn l (cch ly mu nh m t mc 2.1.5).
- Dng Pipt ly 1 ml dung dch hn hp HgCl2 trong NaCl cho vo l
mu, u Pipt phi ngp su khong 1/3 chiu cao ca l. Sau y nt l cn
thn v lc mnh nhiu ln. Nh vy ta thc hin cc phn ng 2.V, 2.VI c
nh H2S v cc dng kh ca Lu hunh di dng mui kp Thu ngn. Tip
li m nt l ra cn thn v cho ngay vo cc ho cht c nh xy
(gm 1ml mui Mangan2 v 1 ml hn hp Kim-Kali Itua). Cc bc tin
hnh nh m t mc 2.1.5.
2.2.5. Qu trnh xc nh v tnh ton kt qu
Cc bc ca qu trnh xc nh hon ton tng t nh m t mc
2.1.6, ch khc l dung dch tinh bt c th cho ngay vo t u v lng O2
trong mu c H2S thng rt t. Khi tnh ton kt qu cn lu l, ngoi 2 ml
ho cht c nh xy nh m t mc 2.1.5, trc trong l mu cn c
thm 1 ml ho cht c nh H2S, nn i lng (V-2) trong cng thc (2.3)
phi c thay bng (V-3).
47
2.3. XC NH KH SUNFUHYDRO HO TAN TRONG NC BIN

Kh Sunfuhydro (H2S) v cc dng kh khc ca Lu hunh l mt hp
phn khng c mt thng xuyn trong nc bin, chng thng ch xut hin
trong iu kin ym kh, ngha l nhng ni khng c hoc thiu xy ho tan.
l cc tng su v y cc vc nc, cc khu vc t ng km lu thng
nc, cc vng bin ven b b nhim do sn phm cng nghip, sinh hot thi
ra...
Sunfuhydro c sinh ra trong qu trnh phn hu cc sn phm hu c c
Lu hunh hoc s kh cc Sunfat trong nc bin do vi khun k kh thc
hin. L mt cht kh mnh nn H2S thng b xy ho tan trong nc xy ho
v do vy n khng th xut hin nhng vng nc sch, thong kh hoc lu
thng tt vi bin khi. Bi vy, s xut hin kh Sunfuhydro trong nc bin l
mt du hiu ca nhim mi trng.
Tc ca phn ng xy ho kh Sunfuhydro trong nc bin ph thuc
cht ch vo hm lng xy ho tan trong nc v nhit mi trng. Phn
ng xy ra cng chm nu nng xy cng nh v nhit cng thp. Bi
vy, gia lp nc bn trn thong kh v lp nc tng su i khi xut hin
mt lp trung gian, ng thi c mt c O2 v H2S. Vic xc nh ranh gii
ca lp ny rt cn thit gii quyt hng lot cc vn thu vn, thu ho,
thu sinh, c bit trong nghin cu qu trnh trao i thng ng ca nc
bin.
C hai kh nng ch yu xut hin H2S trong nc bin:
Mt l: S kh sinh ho cc Sunfat ho tan do vi khun k kh thc hin,
thng xy ra cc vng nc b nhim. Trong qu trnh ny, cc Sunfat b vi
khun kh thnh Sunft v Sunft b kh thnh H2S, c s tham gia ca H2CO3
hay CO2 ho tan trong nc. V d:
48
Vi khun
CaSO4 CaS ; CaS + H2CO3 H2S + CaCO3

Hai l: S phn hu trong iu kin thiu xy xc cc ng thc vt giu
Lu hunh, thng xy ra cc lp nc su v gn y.
Xc nh nh tnh
Do H2S khng phi l thnh phn thng xuyn c mt trong nc bin
nn nu c nghi ng v s c mt ca n trong mu nc th trc ht phi lm
php th nh tnh kim tra. C th s dng 2 cch sau y:
- Ngi mu (Sunfuhydro c mi c trng l mi trng thi).
- Dng giy ch th. Nhng giy ch vo nc mu, nu mu giy thm
ln (vng hoc nu hoc en) th c H2S. Cng ca mu t l vi hm lng
H2S trong mu. C th l, nu mu giy ch chuyn thnh en hoc nu thm th
mu nc c nhiu H2S, chuyn thnh mu hung - lng H2S va phi v
chuyn thnh mu vng - t H2S.
Giy ch l giy thm c tm dung dch Ch Axett [Pb(CH3COO)2] 10%.
C th t chun b giy ch nh sau: Ly 10 gam Ch Axett ho vi mt t nc
ct. Nu dung dch b vn c v c ln Pb(OH)(CH3COO) th nh thm vo
vi git axt Axetc (CH3COOH). Tip b sung nc ct vo dung dch cho
100 gam. Tm giy thm vo dung dch va chun b, sau sy kh giy
ny.
Xc nh nh lng
Sunfuhydro tn ti trong nc bin di dng axt yu (H2S) v cc dn
xut phn ly ca n (HS-, S-2). Do cha nh r c t l ca cc tiu phn
trong h (v iu ny cng khng cn thit) nn bng phng php ha hc ta
ch xc nh c tng nng chung ca c h Sunfuhydro l S = [H2S]+
[HS-] + [S-2]. Bit rng, phn ng xy ho-kh gia cc tiu phn ca h H2S (v
49
d S-2) vi It din ra trong mi trng a xt l:

S-2 + I2o 2I-1 + So
Cn trong mi trng kim n xy ra theo chiu hng l:
S-2 + 4I2o + 8OH- 4H2O + 8I-1 + SO4-2
Bi vy, xc nh tng nng chung ca c h bng phng php kh
It nh trn th phi chuyn mi trng nc bin vn mang tnh kim yu v
mi trng axt. Ch trong mi trng axt, cc tiu phn HS- v S-2 mi chuyn
v dng axt yu H2S.
Nu cho thm vo mu nc bin cn phn tch mt lng c d dung dch
It c nng bit trc v c axt ho bng HCl th phn ng gia H2S
c trong mu v It thm vo l:
I2 + H2S 2HI + S
(2.VII)
Hin nhin lng It tiu th cho qu trnh xy ho ton b lng H2S c

trong mu t l vi chnh hm lng H2S ca mu. Lng It ny c xc nh
bng hiu gia lng It ban u (cho thm vo) v lng It cn li (sau khi
phn ng 2.VII xy ra hon ton). xc nh lng It cn li, ta chun
hn hp k trn bng dung dch Natri Thyosunfit Na2S2O3 c nng bit trc.
Phng trnh phn ng gia It v Natri Thyosunft c vit nh sau:
I2 + 2Na2S2O3 Na2S4O6 + 2NaI
(2.VIII)
Nu lng dung dch It ban u cng c xc nh tng ng theo th

tch Thyosunfit th hiu gia lng dung dch Thyosunfit ny v lng dung
dch Thyosunfit dng chun It d tha s t l vi hm lng H2S
trong mu nc phn tch.
Vi phng php nu trn c th gp 2 sai s sau y:
Mt l: Do dung dch It c mc bay hi ln nn hn ch hin tng
ny th khng c m l trong khng kh. Cng c th x l bng cch cho vo
50
trong dung dch c It mt lng d mui Iotua, khi ion Iotua s kt hp vi

It to thnh ion tri Iotua (I-1 + I2o I3-1) v do lng It bay hi khng ng
k. Ngoi ra, nu lm vic trong iu kin nhit phng th nghim di 25oC
v nu hm lng It trong dung dch khng ln hn 4% th s mt mt It do
bay hi cng khng ng k.
Hai l: Ion Iotua c th b xy ho trong mi trng axt bi xy ca kh
quyn. Phn ng din ra nh sau:
4I-1 + O2 + 4H+1 2I2 + 2H2O
Hin tng ny lm tng thm mt lng It, do dn n sai s phn
tch. hn ch sai s va nu, ngi ta ch axt ho trc tip dung dch c I2+
KI trc khi xc nh H2S v bo qun dung dch axt ho trong bnh c cha
CO2.
- Biurt dung tch 25 ml, tng t nh nu trong mc 2.1.3. xc nh
xy ho tan.
- Ngoi nhng Pipt dng xc lp nng thc ca dung dch
Thyosunfit (nh nu mc 2.1.3), cn c thm cc Pipt c kim nh, dung
tch 1ml, 5ml, 10ml (mi loi 1 chic) dng ly dung dch It v cc Pipt
dung tch 1ml, 2ml (mi loi 1 chic) ly dung dch axt.
- Bnh nh mc dung tch 200-250ml ly mu.
- Bnh thp cha kh CO2 nn, c van v ng h p lc.
- Cc dng c v thit b phn tch thng thng khc.
2.3.4. Ho cht
Dung dch chun Na2S2O3 0,02N v cc dung dch kim tra chun ca
n (K2Cr2O7 0,02N hoc KIO3 0,02N, KI 10%) c chun b nh nu mc
2.1.4 xc nh xy ho tan.
51
Dung dch chun It 0,02N trong KI

Ho tan 40 gam KI tinh khit vi 50 ml nc ct, sau cho thm vo 2,54
gam It kt tinh sch. Sau khi tinh th It tan ht th b sung nc ct vo hn
hp v nng th tch chung ln 1 lt. Cn ch l tinh th KI phi tht sch, nu
khng phi kh sch n (phng php kh sch KI y khng trnh by). Hn
hp dung dch va chun b c bo qun trong bnh xm mu v y bng nt
thu tinh, khng dng nt cao su v n s b hi It ph hu.
Dung dch HCl 1:1
Dung dch ny c chun b bng cch thm mt th tch axt m c (t
trng 1,19) vo mt th tch nc. Ch c thm axt vo nc m khng c
lm ngc li.
Dung dch tinh bt: Chun b nh khi xc nh xy ho tan
Natri Bicacbont (NaHCO3)
Dng cn k thun cn tng lng 0,2 gam tinh th NaHCO3 v gi kn
bng giy bng m. Ho cht ny dng sn xut kh CO2 trong trng hp
khng c bnh thp cha sn kh nn.
2.3.5. Ly mu nc v c nh H2S
Sau cc php th nh tnh bit chc trong mu nc c H2S, ta tin hnh
ly mu vo bnh. Bnh mu l bnh thu tinh nh mc, dung tch khong 200250 ml c xc nh chnh xc t trc, c nh du vch mc th tch v
c ra tht sch v sy kh trc khi s dng.
Trc ht np kh CO2 t bnh thp vo y bnh mu. Nu khng c sn
CO2 th c th dng 0,2 g NaHCO3 ng gi v cho lng thuc ny vo bnh
mu, bnh ny trc c sn 2 ml dung dch HCl 1:1. Khi phn ng to
kh CO2 s xy ra:
NaHCO3 + HCl = NaCl + H2O+ CO2
Tip theo, dng Pipet kim nh ly mt lng hn hp dung dch
52
0,02N It trong KI cho vo bnh mu. Lng It phi c d so vi lng H2S c

trong mu, do vy lng hn hp dung dch cn ly bao nhiu l tu thuc vo
hm lng H2S ca mu. iu ny c th cn c vo php th nh tnh hoc
kinh nghim ca ngi nghin cu. Nu lng H2S trong mu va phi, c th
ch cn ly 1 ml hn hp dung dch k trn, nu nhiu c th ly n 5 ml, nhiu
hn - 10 ml. cho chc chn, thng a vo bnh mu 10 ml hn hp dung
dch ny. y chnh l lng It ban u a vo mu. Ton b cng vic trn
c tin hnh cho c lot bnh mu, s lng bnh c d kin trc theo s
tng cn ly mu ti trm kho st.
Sau khi cho ho cht vo bnh mu, y kn bnh li v vo ni mt,
ch c m nt bnh khi ly mu. Tip lp vi dn nc vo my ly nc.
Vi dn phi c 2 on, on bng cao su c gn vi my ly nc v on
bng thu tinh cm vo tn y bnh mu. Sau trng vi dn bng chnh
nc mu bng cch m van my ly nc cho nc mu chy t do qua vi.
Khi ly mu nc vo bnh, tia nc khng c chy qu mnh trnh
to bt kh trong bnh. Bnh mu cn c ly nc mu n vch mc v
sau ng ngay nt bnh li. Khi phn ng 2.VII tiu hao lng It ban u
trong bnh xy ra, ngha l ton b lng H2S trong mu b It a thm vo
xy ho ht.
Lc ny, cht lng trong bnh mu phi c mu vng It v lng It ban
u thm vo mu l c d. Nu khng t c yu cu ny chng t trong
bnh thiu It, khi phi ly li mu nc vi quy m ln hn bng cch tng
lng hn hp dung dch It trong KI. Sau khi ly mu, bnh mu c chuyn
ngay n ni phn tch xc nh lng It cn li.
Xc nh h s hiu chnh chun dung dch Na2S2O3
Cng vic c tin hnh nh m t mc 2.1.6 khi xc nh xy.
Xc nh tng quan gia lng dung dch It ban u v lng dung dch
53
Thyosunfit
Cc bc tin hnh nh sau:
Bc 1: Np kh CO2 vo y bnh nh mc (dung tch ca bnh khong
200-250 ml v c xc nh chnh xc t trc). C hai cch np kh CO2
vo bnh nh mc nh nu mc 2.3.5.
Bc 2: Cho thm vo bnh nh mc k trn 10 ml dung dch 0,02N It
trong KI. Nu trc bnh c np kh CO2 t bnh thp th tip tc cho thm
vo bnh 1 ml dung dch HCl 1:1. Nu phi to kh CO2 t NaHCO3 v HCl th
khng cn thm dung dch HCl na (v trong bnh c sn).
Bc 3: Sau khi trong bnh nh mc c 3 loi ho cht trn (gm
CO2, hn hp dung dch 0,02N It trong KI v dung dch HCl 1:1) th b sung
nc bin khng c H2S (nc tng mt c lc k) vo bnh cho n vch
mc. ng nt bnh tht cht v lc u.
Bc 4: dung dch trong bnh nh mc vo bnh tam gic ri chun
n bng dung dch Thyosunfit hiu chnh chun. Khi cng vic gn kt
thc ( l lc mu vng It ca hn hp cn r nt), ta b sung vo hn hp
ang b chun mt t dung dch tinh bt th hn hp s chuyn thnh mu
xanh. Tip tc chun cn thn cho n khi hn hp khng mu.
Bc 5: Rt mt t dung dch khng mu ngc tr li bnh nh mc
trng bnh, ri li chuyn phn nc trng bnh sang bnh tam gic. Lc ny hn
hp li c mu xanh nhng cng rt yu (nu khng c mu xanh th vic
chun bc 4 trc c th b qu). Tip tc chun tht thn trng
hn hp cho n khi mt mu hon ton, ghi li s c trn Biuret chnh xc ti
0,01 ml.
Bc 6: Lp li ton b 5 bc k trn ln th hai. Nu s c trn Biurt
ca hai ln chun khng chnh nhau qu 0,05-0,1 ml th s c trung bnh
c s dng tnh ton kt qu. Nu s sai khc vt gii hn ny th phi
lm li th nghim ln th 3 ly hai ga tr gn nhau nht.
54
Xc nh H2S trong mu nc
Mu nc sau khi c nh H2S cn phi c phn tch ngay, cng sm
cng tt. Nu lu, lng It cn li trong mu s bay hi v kt qu phn tch
trong trng hp ny s khng chnh xc.
mu nc c nh H2S qua bnh tam gic ri chun n bng chnh
dung dch Thyosunfit s dng trong php xc nh tng quan. Qu trnh
chun mu nc tng t nh bc 4 v bc 5 m t trn. Ghi li kt
qu chun .
Theo quy c, nng H2S (thc cht l tng nng ca c h
Sunfuhydro, k hiu S) c biu din tng ng qua s mililit kh H2S (xt
iu kin chun) c trong 1 lt nc bin. T cc phng trnh phn ng gia
It vi H2S (2.VII) v gia It vi Thyosunfit (2.VIII), rt ra rng 1 ng
lng gam It, v do 1 ng lng gam Na2S2O3 tng ng vi 1/2 phn t
gam H2S. Trng lng phn t ca H2S l 34,08 nn 1/2 phn t gam H2S s l
17,04. 1ml kh H2S ti iu kin chun nng 1,5393 mg. T suy ra cng thc
sau:
S ( mlH 2 S / l ) =
17 , 04 .( m n ). N .K . 1000
( V d ). 1, 5393
(2.6)
Trong m l s mililit dung dch Thyosunfit dng xc nh tng

quan gia dung dch It v dung dch Thyosunfit, n - s ml dung dch
Thyosunfit dng chun mu nc, N - chun ca dung dch
Thyosunfit (0,02) v K l h s hiu chnh chun, V - th tch bnh nh mc,
d - tng th tch cc dung dch ho cht cho thm vo bnh (gm hn hp
dung dch It trong KI v dung dch HCl 1:1).
Cng thc trn c vit gn hn khi thay ton b cc gi tr bit:
S(mlH 2S / l) =
221.(m n )..K
(V d)
55
(2.7)
Nu ta s dng cng mt loi bnh nh mc c th tch V bit trc v

cng mt lng ho cht cho vo bnh y th h s nhn cho mi bnh nh mc
M =221/(V-d) s c tnh trc v lp thnh bng. Do :
S (ml H2S/l) = M(m-n)K
(2.8)
V d:
- xc nh chun thc ca dung dch Thyosunfit, ta dng Pipet dung
tch 10ml c s hiu chnh +0,03 v ly c 10,03 ml dch chun K2Cr2O7
0,02N. S c trung bnh trn Biuret sau 2 ln chun Thyosunfit vo cng
lng dung dch chun ny l 10,18, hiu chnh s c ny l 0,00. Vy h s
hiu chnh chun dung dch Thyosunfit l K=10,03/10,18 = 0,985.
- Dng chnh Pipet k trn ta ly c 10,03 ml dung dch chun 0,02N It
trong KI v dng Pipt khc ly 2 ml dung dch HCl 1:1 cho vo bnh nh mc
c dung tch V=250 ml, b sung nc bin khng c H2S n vch mc ca
bnh. Khi chun hn hp trn bng dung dch Na2S2O3 kim tra chun,
ta tm c s c trn Biuret l: ln th nht m1=9,98, ln th hai m2=9,96,
trung bnh cho 2 ln c l 9,97, hiu chnh s c ny l +0,01 nn s c thc
l m=9,98.
- Khi xc nh lng H2S trong mu nc bin tng ng vi lng It cn
li, ta ly 250 ml mu nc chun bng dung dch Thyosunfit (mu nc
c sn 2ml dung dch HCl 1:1 to kh CO2). S c trn Biuret trong
trng hp ny l n=6,86. T (2.7) ta c:
S ( mlH 2 S / l ) =
221 .( 9 , 98 6 ,68 ). 0 , 985

= 2 ,85 ( mlH 2 S / l )
250 (10 ,33 + 2 )
2.3.8. Th t cng vic

Bc 1: Chun b dng c v thit b cn thit.
Bc 2: Kim tra chun ca dung dch Na2S2O3.
Bc 3: Xc nh tng quan gia dung dch Na2S2O3 v dung dch I2, gm
56
cc vic sau:
- Np kh CO2 vo y bnh nh mc. Ly 10 ml dung dch chun 0,02N
It trong KI v 1 ml dung dch HCl 1:1 cho vo bnh nh mc k trn. C th
thay cng vic ny bng cch cho vo bnh nh mc sch 2 ml HCl 1:1 v cho
tip vo mt lng 0,2 g NaHCO3, sau cho vo 10 ml hn hp dung dch
It trong KI.
- B sung nc bin khng c H2S n vch mc ca bnh.
- Chuyn dung dch t bnh nh mc sang bnh tam gic v chun n
bng dung dch Thyosunfit kim tra chun.
Bc 4: Ly mu nc v c nh H2S, gm cc vic sau:
- Chun b lot bnh nh mc ly mu. S lng bnh tng ng vi s
tng cn ly mu.
- Np kh CO2 vo cc bnh bng mt trong hai cch nu.
- Ly mt lng nht nh (thng l 10 ml) dung dch 0,02N It trong KI
v nu bnh c np kh CO2 t bnh thp th ly thm 1 ml dung dch HCl 1:1
cho vo cc bnh mu chun b. y nt v bo qun chng ni mt.
- Khi my ly nc c a ln boong tu kho st th tin hnh ly nc
mu vo bnh cho n vch mc v chuyn ngay n ni phn tch.
Bc 5: Chun mu nc bng dung dch Thyosunfit kim tra
chun v xc nh tng quan vi It. Ghi kt qu chun vo s chuyn
mn.
Bc 6: Lp li bc 5 cho mu khc.
Bc 7 Vic tnh ton kt qu c th thc hin sau khi phn tch xong lot
mu hoc cui ngy lm vic. Kt qu tnh ton phi c ngi th hai kim
tra li.
57
Chng 3
XC NH CC THNH PHN
CA H CCBNT TRONG NC BIN
3.1. XC NH PH NC BIN BNG PHNG PHP SO MU

Nc l cht phn ly cc k yu, sn phm phn ly l cc ion H+ v OH-:
H2O H+ + OHTheo nh lut tc dng khi lng, trng thi cn bng ta c:
K=[H+].[OH-]/[H2O]
hay
K[H2O] = [H+].[OH-]
Trong K l hng s phn ly (hng s cn bng nhit ng). V nng

phn t gam ca nc c coi l khng i (c gi tr bng 1000/1855,56
Mol/l) nn K[H2O] cng khng i v c gi l hng s tch nng ion ca
nc.
Cc qu trnh khc nhau c th lm bin i nng ion Hydro v
Hydroxyl trong nc, song tch nng ca chng lun l mt hng s. Ngha
l, nu c mt qu trnh no lm tng nng H+ (v d s phn ly ca cc
mui bicacbonat ho tan trong nc) th nng OH- phi gim tng ng (v
ngc li), sao cho tch nng ca chng khng i. trng thi cn bng ng
vi nhit 22oC v p sut 760 mm Hg, nc sch trung tnh c hng s phn
ly K 1,8.10-16 nn hng s nng K.[H2O]1.10-14, do [H+]=[OH-]10-7.
Trong mi trng nc t nhin ni chung, ion Hydro tn ti vi nng
rt nh (bc nng vo khong 10-5-10-9 ion-gam/l, vi nc bin l 10-7-10-9
58
ion-gam/l). Bi vy tin li cho vic biu din nh lng nng ca n

ngi ta s dng tr s pH:
pH = -lg [H+]
Vi cch biu din ny th mi trng nc trung tnh ([H+]=[OH-]) c
pH=7, axt tnh ([H+]>[OH-]) c pH<7 v kim tnh ([OH-]>[H+]) c pH>7.
Trong nc bin, nng ion Hydro (do tr s pH) c lin quan cht ch
vi hm lng kh Cacbonic ho tan, ni ng hn, pH nc bin ph thuc
trc tip vo mi tng quan gia axt Cacbonic (H2CO3) v cc dn xut phn
ly ca n:
CO2 + H2O H2CO3 H+ + HCO3HCO3- H+ + CO3-2
Theo nh lut tc dng khi lng, cc hng s phn ly ca axit ny l:
K1 = [H+].[HCO3-]/[H2CO3]
K2 = [H+].[CO3-2]/[HCO3-]
Gi tr K1 o c ti 22oC v p sut 760 mmHg l 4.10-7, ln hn 4 bc
so vi gi tr K2 (4,2.10-11). Bi vy s phn ly ca axit Cacbonic ch yu l
phn ly bc mt. Do :
[H+] = K1 [H2CO3]/[HCO3-]
iu ny cho thy nng ion Hydro ph thuc ch yu vo nng ion
Bicacbonat (HCO3-) theo quan h t l nghch. Nhng trong nc bin, ngun
chnh to ra ion HCO3- khng phi do phn li axit Cacbonic m do phn li nhng
mui bicacbont nh Ca(HCO3)2, Mg(HCO3)2... vn c nhiu trong nc. Bi
vy, s ho tan cc mui ny s lm tng nng HCO3-, do gim [H+] tc l
tng pH, ngc li, s ho tan kh CO2 vo nc bin s lm tng nng axt
H2CO3 v do tng [H+] tc l gim pH.
Nhit v p sut thu tnh cng c nh hng ng k n pH ca nc
59
bin. Nu nhit (hoc c p sut) tng th hng s phn li ca H2CO3 v H2O

tng ln, dn ti pH gim. Tuy nhin, nu nhit tng th ho tan ca kh
CO2 trong nc bin li gim v do pH tng ln. Cc hp phn khc nh cc
axt Borc (H3BO3), axt Silisc (H2SiO3), axit Phtphoric (H3PO4)... mc d
cng phn ly v to ra H+ nhng chng t c ngha i vi pH nc bin bi
nng ca chng rt nh v hng s phn li rt b. Kh Sunfuhydro (H2S) c
nh hng ti pH nhiu hn, nhng khng phi ch no v bao gi cng c.
Nc bin, trong c ho tan nhiu axit yu v cc mui ca n, c
xem l mt dung dch m pH. Nc bin mi vng trn th gii u mang
tnh kim yu, c pH kh n nh v thng ch bin i trong gii hn rt hp
(7,6-8,4). iu ny dn ti vic s dng pH nh mt ch s ca khi nc.
i vi nc vng bin ven b, nht l vng ca sng, do t l thnh phn mui
Cacbonat rt khc nhau, nn cng vi kim ca nc, pH cn c s dng
tnh ton s lan truyn ca nc lc a vng ny.
Mc d tn ti vi nng cc k nh b, song s c mt ca ion Hydro
trong nc bin quyt nh rt nhiu tnh cht quan trng ca mi trng.
Trc ht, pH c xem nh ci "nn" trn xy ra cc phn ng ho hc,
sinh-ho hc, v d nh s n mn b tng ca nc bin, kh nng ho tan t
b v y, iu kin tn ti v pht trin ca thu sinh vt... trong c
nhiu loi rt nhy cm vi s bin i pH nc bin. Do c lin quan cht ch
vi hm lng cc axit yu v mui ca chng c mt trong nc bin, nht l
axit Cacbonic v cc mui Cacbonat, nn pH cn l mt thnh phn quan trng
trong cc mi cn bng ca cc h cn bng ni chung, h Cacbonat ni ring
trong bin.
Hin nay, Hi dng hc ang s dng hai phng php xc nh tr s
pH nc bin: phng php o in v phng php so mu. Phng php o
in l khch quan v chnh xc hn. Tuy nhin cc thit b o pH nc bin c
chnh xc cao (0,01) v tin li trong vic lp t ng b cng cc thit b
o nhit , mui, xy ho tan... li rt t tin v i hi nhng iu kin
k thut tng thch. Mt s thit b o pH cm tay tuy n gin v r tin
60
nhng li khng t c chnh xc mong mun ca Hi dng hc, m ch

c tnh cht kim tra cht lng mi trng. Do vy, trong nhiu trng hp vn
phi s dng cc phng php phn tch ho hc xc nh pH nc bin.
Phng php so mu xc nh pH nc bin rt n gin, khng i hi
nhng my mc phc tp, cng knh m vn t chnh xc cao tho mn yu
cu ca Hi dng hc.
3.1.2. Phng php so mu xc nh pH nc bin
Nguyn tc ca phng php so mu xc nh pH nc bin l: c hai dung
dch, trong mt dung dch bit trc tr s pH, khi cho thm ch th mu
pH vo c hai dung dch m chng cho mu ging nhau th tr s pH ca dung
dch th hai bng tr s pH ca dung dch th nht.
Trong thc t nghin cu ho hc bin, ngi ta phi chun b sn lot
dung dch m chun c tr s pH khc nhau v sp xp chng theo th t pH
tng dn (hoc gim dn) trong mt hp nh, gi l "bng cc dung dch m
chun" hay "hp bng mu". Bng cc dung dch m chun c ch to ti
phng th nghim chuyn mn bao gm nhiu ng nghim ng knh nh
nhau, trong cha cc dung dch m c ch th mu pH (ch th mu
thng l Crezol hoc Thymol xanh). Cc dung dch m c pha ch vi
t l thch hp sao cho pH ca bng bin i t 7,60-8,55 (bc 0,05 n v
pH). Khong tr s pH nh trn bao hm tt c cc gi tr pH thng gp v
quan trc c mi vng bin.
Hp bng cc dung dch m chun cn c bo qun ht sc cn thn v
ch c m ra lc so mu. Nu mu ca bng b bin i so vi lc ch to th
phi thay n bng bng mu mi, ng nhin c th ch cn thay mt vi dung
dch m ca bng nu chng b hng. Tuy vy, khng nn s dng bng mu
qu 6 thng m khng c kim tra li.
3.1.3. Dng c v ho cht
Hp bng cc dung dch m chun
61
Ton b hp bao gm cc dng c v ho cht sau:

a- B dung dch m chun c ch th mu cha trong cc ng nghim
thu tinh trung tnh, khng mu v c hn kn, khong pH t 7,60 n 8,55,
bc l 0,05 n v pH.
b- Dung dch ch th (hai l). Cn ch l phi s dng ng dung dch ch
th dng nhum mu cc dung dch m chun ca hp bng mu.
c- Pipet dung tch 0,5 ml ly dung dch ch th, 2 chic.
d- Nhit biu bch phn c kim nh, 2 chic.
e- Gi bng g c nhng l cm bo v cc ng nghim, Pipet, nhit
k, l cht ch th.
Trong iu kin Vit Nam, khi khng c c hp bng mu tiu chun
nh m t, ta vn c th chun b c dng c ny vi chnh xc tng
t phc v kp thi cho cc t kho st. Cc ho cht chun b cc dung
dch m ca bng mu gm:
- Dung dch axit Boric (H3BO3) 0.1 N
- Dung dch mui Borac (Na2B4O7.10H2O) 0.1 N
- Dung dch ch th Crezol 0,02 %
Cc dung dch c s ny c chun b t ch phm tinh khit v ng
trong cc l thu tinh mu c nt mi. Cn ch l ch chun b chng trc khi
pha ch thnh b dung dch m chun. Mun to ra cc dung dch m c pH
mong mun, ta ho trn cc dung dch axit Boric v mui Borat vi nhng th
tch khc nhau theo ch dn bng 3.1.
Bng 3.1: T l pha ch cc dung dch m chun
pH
Th tch cn ly (ml)
pH
Th tch cn ly (ml)
mong mun
H3BO3
Na2B4O7
mong mun
H3BO3
Na2B4O7
7.60
8.50
1.50
8.10
6.92
3.08
62
pH
Th tch cn ly (ml)
pH
Th tch cn ly (ml)
mong mun
H3BO3
Na2B4O7
mong mun
H3BO3
Na2B4O7
7.65
8.38
1.62
8.05
6.72
3.28
7.70
8.24
1.76
8.20
6.50
3.50
7.75
8.10
1.90
8.25
6.28
3.72
7.80
7.95
2.05
8.30
6.06
3.94
7.85
7.80
2.20
8.35
5.82
4.18
7.90
7.64
2.36
8.40
5.57
4.43
7.95
7.47
2.53
8.45
5.32
4.68
8.00
7.30
2.70
8.50
5.06
4.94
8.05
7.12
2.88
8.55
4.79
5.21
ch to hp bng mu, trc ht cn chun b lot ng nghim thu tinh

trung tnh, sch, kh, c kch thc hon ton ging nhau. Dng Pipet t ng
ly 0,5 ml Crezol 0,02 % cho vo ng nghim, sau cho tip dung dch H3BO3
v Na2B4O7 theo t l nh bng trn, ta c c mt dung dch m c pH xc
nh v c ch th mu. Ngay lp tc nt ng nghim li bng nt cao su hoc
nt bc v ph kn nt bng Parafin sao cho khng kh khng lt vo ng
nghim. Lc u ng nghim ho trn dung dch v ghi tr s pH ca dung
dch m ln mp trn ca ng nghim. Tip tc chun b cc dung dch m
khc.
Trong qu trnh ch to bng mu, nht thit phi theo di v ghi li nhit
phng th nghim. S n nh nhit phng th nghim lc ch to bng
mu l tiu chun m bo chnh xc ca bng. Ton b thng tin khi ch to
bng mu cn c lp thnh h s.
Vi tr s pH t 7,60 n 8,55, bc 0,05, hp bng mu m chng ta
chun b c nh m t c chnh xc cao v s dng c tt c cc
vng bin Vit Nam. Tuy nhin, vn rt cn kim tra chnh xc ca dung dch
m bng phng php o in, ng thi cng khng nn s dng n sau hai
63
thng k t khi ch to m khng c s kim tra.

B ng nghim ly mu
Cc ng nghim thu tinh trung tnh, khng mu c ng knh ng nht
v bng ng knh ca cc ng nghim cha dung dch m chun trong hp
bng mu. Cc ng nghim ny cn c nh s v c vch mc bng vi
chiu cao ca ct dung dch m chun. Mi ng nghim phi c mt nt ring,
thng l nt cao su.
ng cao su nh dn nc.
Hp so mu (Comparat), hnh 3.1: y l dng c tr gip cho vic so mu
bng mt xc nh tr s pH ca cc mu nc ly vng bin ven b, ca
sng... c mu vng t nhin do cc ht l lng, ph sa to nn.
Hnh 3.1
Comparat dng so mu xc
nh pH nc bin
3.1.4. Ly mu nc v xc nh pH
Vi mc ch xc nh pH, mu nc cn c u tin ly trc cc mu
khc v ly ngay sau khi ko my ly nc t di bin ln. S u tin ny
nhm hn ch kh nng thm nhp CO2 t kh quyn vo mu.
Trc ht cn chun b sn b ng nghim sch, kh ly mu, s lng
ng nghim tng ng s mu cn ly (cc ng nghim ly mu phi hon ton
tng t cc ng nghim ca bng mu). Lp ng dn nc vo my ly nc
v m van trng ng dn v cc ng nghim. Sau khi trng ng nghim 23 ln bng chnh nc mu cn ly, dng Pipet ly mt lng ch th mu theo
ch dn ghi trong h s hp bng mu (thng l 0,5 ml) cho vo ng nghim
64
(i vi bng mu m chng ta chun b nh m t mc 3.1.3 th phi ly

0,5 ml Crezol 0,02%, tc l ng bng lng ch th s dng khi ch to bng
mu). Sau ly nc mu qua ng cao su vo ng nghim cho n vch mc
(khng c tia nc qu mnh v si bt trong ng nghim). y kn ng
nghim bng nt cao su v khuy trn hn hp bng cch lc u m khng
c o hoc xc ng nghim. Tip tc ly mu khc (nu c) vi quy trnh
hon ton tng t. Sau khi mu ca mu ho trn u, c th tin hnh so
mu vi bng chun ngay ti hin trng hoc a mu n ni quy nh so
mu. Ton b qu trnh ny phi c thc hin nhanh chng nhit ca
mu nc lc phn tch (so mu) khng khc nhiu so vi nht in situ ca
n. Tuy vy, ngi ta vn phi o nhit ca mu nc lc phn tch tnh
ton cc s hiu chnh pH. Mun vy ng thi vi vic ly mu nc nh
m t, ngi ta cn ly chnh mu nc vo mt ng nghim khc (ng ny
khng cn cho ch th mu) v cm vo mt nhit biu. ng nghim c cm
nhit biu v ng nghim c nc phn tch lun lun cnh nhau. Do vy, ch
cn c nhit biu ny lc phn tch mu l ta c nhit ca mu nc ti thi
im phn tch. Qu trnh so mu ca mu nc vi bng chun c tin hnh
nh sau:
Cm ly u trn ca ng nghim c mu phn tch ( trnh lm nng mu
bng nhit ca tay mnh), a n li gn b dung dch m chun v dng li
ti v tr m mu sc ca chun v mu gn trng nhau. Sau chn ra hai ng
nghim dung dch chun ca bng c mu gn nht vi mu ca mu, trong
mt ng c mu axit hn v mt ng c mu kim hn. ng nghim c nc
phn tch c t gia hai ng nghim chun la chn v tt c c t
trc nn trng nhn cho d. Cn ch l khng nh sng mt tri trc
tip ri vo. Tr s pH ca mu nc c xc nh nh php ni suy bng mt.
Khi ni suy, cn phi ch c mu sc ln cng mu. V d mu ca mu
nm gia khong mu ca hai dung dch m chun c pH bng 8,30 v 8,35, v
nu khng cn kh nng no gii quyt s gn nhau hn na v mu sc ca
chun v mu th c th kt lun pH ca mu bng 8,33. Nu mu ca mu
nghing v pha mu ca chun c pH bng 8,30 th pH ca mu l 8,32, nu
65
gn hn na - 8,31. Ghi kt qu phn tch vo s, km theo ghi lun c nhit

in situ, nhit mu lc phn tch (nh ni trn) v nhit ca bng
mu lc phn tch. c c nhit bng mu lc phn tch, ngi ta cm
mt nhit biu vo mt ng nghim cha nc ct v trong sut thi gian kho
st lun lun t ng nghim ny cnh b ng nghim dung dch chun ca hp
bng mu. Lc phn tch ch cn c nhit biu ng nghim ny l c c
nhit ca bng mu ti thi im phn tch. Sau khi phn tch xong, y ngay
np hp bng mu li ( trnh s tip xc qu lu ca n vi nh sng) v ra
sch cc ng nghim c nc mu.
Nhng vng nc gn b, nht l vng ca sng, mu nc ly ln thng
c mu vng t nhin do c nhiu ht l lng, ph sa... nn vic so mu bng
mt trong trng hp ny gp kh khn. loi tr nh hng ca mu t nhin
k trn, ngoi vic ly 1 mu nc phn tch nh nu trn cn ly thm 2
mu nc cho vo hai ng nghim nhng khng thm ch th mu v ly nc
ct cho vo mt mt ng nghim khc. Vic so mu c thc hin nh
Comparat. V tr cc ng nghim c cha mu nc phn tch, nc ct, nc
bin khng c ch th mu v hai dung dch m chun chn s b c t
trong Comparat nh s hnh 3.2. Vi cch b tr nh vy, tia sng trc khi
ti mt ngi phn tch u phi i qua cc lp dung dch c tnh cht nh nhau,
l lp nc bin c mu t nhin (cng l mu nc) v lp nc ct (cng
l dung dch chun).
Nc bin c mu t nhin
v khng c cht ch th
Nc ct
Nc bin c mu t nhin
v khng c cht ch th
Chun 2
Chun 1
Mu phn
tch
Tia sng i qua cc dung dch ti mt ngi phn tch
Hnh 3.2: S v tr cc ng nghim cha mu v chun trn Comparat
66
Vo ma ng, khi khng c cc iu kin thun li v nh sng v thi

tit dn n khng th phn tch pH ngay ti hin trng, ngi ta phi ly mu
vo bnh c th tch khong 100 ml, c nt cao su kn hoc nt thu tinh mi.
Trc khi y nt, cn cho thm vo mu 3-4 git Clorofooc (CHCl3). Mu
ny c bo qun ni ti v nhit khng cao. Tuy vy, mu nc cn
c phn tch cng sm cng tt v khng c qu 24 gi k t khi ly
mu. Trc khi phn tch nhng mu nc ny, nhit ca mi mt mu nht
thit phi c o v phi ghi vo s vi li ch gii l vic xc nh pH c
tin hnh sau thi gian bao lu k t khi ly mu.
Tr s pH tm c qua vic so mu nh m t trn (k hiu l pHQT)
cha phi l gi tr pH tht ca mu, bi v, kt qu ny cha tnh n s thay
i pH do nhit v mui, l hai nhn t c nh hng ng k n pH
nc bin. V vy, cn phi a thm vo kt qu phn tch cc s hiu chnh.
S hiu chnh pH theo mui (k hiu pHS)
Do pha ch cc dung dch m chun bng nc ct nn mui ca
chng nh hn nhiu so vi mui ca nc bin v do vy lng ion ni
chung ca dung dch m chun cng nh hn. iu c nh hng ng k
n hot tnh ca cc ion Hydro. Ngoi ra, mui ca nc bin cn nh
hng n s phn ly ca cht ch th v do vy nh hng ti mu sc ca mu
nc phn tch. Hi ng U ban Quc t Nghin cu bin nm 1958 cng
nhn s hiu chnh pHS do mui gy ra i vi nc i dng c mui
35%o l -0,26 pH. Ngi ta cng tnh sn s hiu chnh ny theo cc gi tr
mui khc nhau v ghi li thnh bng (bng 3.2). Ch cn bit mui nc
bin, tra bng ny s c c s hiu chnh pHS.
Bng 3.2: S hiu chnh pHS theo cc gi tr mui khc nhau
S%o
pHs
S%o
pHs
S%o
pHs
S%o
pHs
0,2
+0,20
-0,09
19
-0,20
30
-0,24
0,4
+0,18
-0,11
20
-0,20
31
-0,25
67
S%o
pHs
S%o
pHs
S%o
pHs
S%o
pHs
0,6
+0,16
10
-0,12
21
-0,21
32
-0,25
0,8
+0,14
11
-0,13
22
-0,21
33
-0,26
+0,12
12
-0,14
23
-0,22
34
-0,26
+0,06
13
-0,15
24
-0,22
35
-0,26
+0,02
14
-0,16
25
-0,23
36
-0,26
-0,01
15
-0,17
26
-0,23
37
-0,26
-0,04
16
-0,18
27
-0,23
38
-0,26
-0,06
17
-0,19
28
-0,24
-0,08
18
-0,19
29
-0,24
Cc s hiu chnh pH theo nhit :

C 3 loi s hiu chnh pH theo nhit :
S hiu chnh th nht (k hiu pHT) gy ra do s thay i nhit ca
bng mu lc phn tch (Tb) so vi lc ch to. S thay i ny dn n s thay
i hng s phn ly ca axit Boric v mui Borac c trong dung dch m
chun. S hiu chnh pHT c tnh sn theo gi tr Tb v cho thnh bng, v
d bng 3.3 i vi loi hp bng mu ch to 18oC. Ch cn c nhit hp
bng mu lc phn tch, tra bng ny ta s c s hiu chnh th nht.
S hiu chnh th hai gy ra do chnh lch nhit ca mu nc vi nhit
ca dung dch m chun ca hp bng mu ti thi im so mu. S chnh
lch nhit ny c nh hng n mc phn ly ca cht ch th trong mu
v trong dung dch chun v do vy nh hng n mu sc.
S hiu chnh ny c xc nh bng biu thc (Tb-Tw') trong Tb v
Tw l nhit ca bng mu v ca mu ti thi im phn tch, - h s nhit
ca s bin i pH gy ra do bin i hng s phn ly ca cht ch th - l
s thay i pH khi nhit thay i 1oC. Vi Crezol , = +0,009, vi
Thymol xanh = +0,008.
S hiu chnh th 2 cng c tnh sn theo hiu (Tb-Tw') v cho thnh
bng (bng 3.4).
68
Bng 3.3: S hiu chnh pHT theo nhit bng mu (Tb) ti thi im phn tch (so vi lc
ch to ti 18oC)
Tb
pHQT
(oC)
7,7
7,8
7,9
8,0
8,1
8,2
8,3
8,4
8,5
8,6
16
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,02
18
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
0,00
20
-0,01
-0,01
-0,01
-0,01
-0,01
-0,01
-0,01
-0,01
-0,01
-0,02
22
-0,01
-0,01
-0,02
-0,02
-0,02
-0,02
-0,02
-0,02
-0,03
-0,03
24
-0,02
-0,02
-0,03
-0,03
-0,03
-0,03
-0,03
-0,04
-0,04
-0,04
26
-0,03
-0,03
-0,03
-0,04
-0,04
-0,04
-0,05
-0,05
-0,05
-0,05
28
-0,03
-0,04
-0,04
-0,04
-0,05
-0,05
-0,06
-0,06
-0,06
-0,06
30
-0,04
-0,05
-0,05
-0,05
-0,06
-0,06
-0,07
-0,07
-0,07
-0,08
Bng 3.4: S hiu chnh pH theo hiu nhit bng mu v mu nc (Tb-Tw')

ti thi im phn tch (Crezol : = +0,009, Thymol xanh: = +0,008)
tb - tw' (oC)
Crezol-
Thymol-xanh
tb - tw' (oC)
Crezol-
Thymol-xanh
0,01
0,01
11
0,10
0,09
0,02
0,02
12
0,11
0,10
0,03
0,02
13
0,12
0,10
0,04
0,03
14
0,13
0,11
0,04
0,04
15
0,14
0,12
0,05
0,05
16
0,14
0,13
0,06
0,06
17
0,15
0,14
0,07
0,06
18
0,16
0,14
0,08
0,07
19
0,17
0,15
10
0,09
0,08
20
0,18
0,16
S hiu chnh th ba gy ra do s thay i nhit mu nc lc phn tch
69
so vi nhit in situ ca n. S thay i ny nh hng n hng s phn ly

ca nc v ca axit Cacbonic. S hiu chnh th 3 c xc nh bng biu
thc (Tw'-Tw) trong Tw l nhit in situ ca mu nc v Tw l nhit
mu ti thi im phn tch, - h s nhit ca s bin i pH gy ra do bin
i hng s phn ly ca nc v ca axit Cacbonnic. Tr s o c bng -0,01
v s hiu chnh th ba cng c tnh sn theo hiu (Tw'-Tw), cho thnh bng
(bng 3.5).
Bng 3.5: S hiu chnh pH theo hiu ca nhit in situ v nhit mu ti thi im phn
tch (Tw'-Tw)
pHQT
Tw' - Tw
(oC)
7,6
7,7
7,8
7,9
8,0
8,1
8,2
8,3
8,4
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,02
0,02
0,02
0,02
0,02
0,02
0,02
0,02
0,02
0,03
0,03
0,03
0,03
0,03
0,03
0,03
0,03
0,03
0,03
0,04
0,04
0,04
0,04
0,04
0,04
0,04
0,05
0,04
0,04
0,05
0,05
0,05
0,05
0,05
0,06
0,06
0,05
0,05
0,06
0,06
0,06
0,06
0,06
0,07
0,07
0,06
0,06
0,07
0,07
0,07
0,07
0,07
0,08
0,08
0,07
0,07
0,07
0,08
0,08
0,08
0,08
0,09
0,09
0,08
0,08
0,08
0,09
0,09
0,09
0,10
0,10
0,10
10
0,09
0,09
0,09
0,10
0,10
0,10
0,11
0,11
0,11
11
0,09
0,10
0,10
0,11
0,11
0,11
0,12
0,12
0,12
Sau khi tm c tt c cc s hiu chnh, tr s pH thc ca mu nc

c xc nh theo cng thc:
pH = pHQT + pHS + pHT + (Tb-Tw') + (Tw'-Tw)
(3.1)
Cng thc ny do K. Bukh ngh v c Hi ng Quc t Nghin

cu bin cng nhn. Trong cng thc trn, pHQT l tr s pH tm c qua so
70
mu bng mt; pHS - hiu chnh pH theo mui; 3 i lng cn li l cc s

hiu chnh pH theo nhit .
Biu din pH nc bin theo cng thc (3.1) rt tin li cho vic tnh ton
cc dng tn ti ca axit Cacbonic v cc c trng cn bng ca h Cacbont
trong bin.
Ngoi cch biu din trn ngi ta cn biu din tr s pH ti 0oC (k hiu
pHo). Biu din dng pHo loi tr nh hng ca nhit v bi th n
hon ton phn nh s thay i t l ca kh CO2 ho tan v cc dng dn xut
ca axit Cacbonic (HCO3', CO3'').
pHo = pH + Tw
(3.2)
Trong l h s nhit ca s thay i pH khi quy chuyn v 0oC. Gi

tr c tnh sn theo cc tr s pH tnh t cng thc (3.1) v cho thnh bng
(bng 3.6)
Bng 3.6: Gi tr h s khi quy chuyn v pHo
pH
7.6
7.7
7.8
7.9
8.0
8.1
8.2
8.3
8.4
8.5
8.6
(10-4)
86
90
93
96
100
103
106
110
113
116
120
V d: mui ca mu nc l 26%o. Nhit in situ ca mu l

Tw=25oC, nhit ti thi im so mu ca bng mu l Tb=28oC, ca mu nc
l Tw'=26oC. Kt qu so mu l pHQT = 8,10.
- Tra cc bng dn ng vi cc thng tin trn ta c: pHS=-0,23; pHT=0,05; (Tb-Tw') =+0,02; (Tw'-Tw)=+0,01. Thay cc gi tr ny vo cng thc
(3.1) ta c tr s pH thc ca mu nc l: pH= 7,85
- Gi tr h s (ni suy t bng 3.6) ng vi pH=7,85 l 0,00945. Theo
cng thc 3.2 ta c pHo= 8,086.
3.1.6. Th t cng vic
Bc 1: Chun b cc dng c, thit b v ho cht cn thit.
71
Bc 2: Mc ng cao su nh vo my ly nc, trng ng cao su v ng

nghim ly mu 2-3 ln bng chnh nc mu cn ly.
Bc 3: Ly mu
a) Cho vo ng nghim cn ly mu mt lng cht ch th mu ng nh
ch dn hp bng chun, sau ly mu nc phn tch vo n vch mc.
Nht thit khng c tia nc to thnh cc bt kh trong ng nghim. Ngay
lp tc y nt ng nghim li trnh s xm nhp ca Cacbonic t kh quyn
vo mu.
b) Ly tip nc phn tch vo mt ng nghim khc v cm vo mt
nhit biu. ng nghim c mu nc phn tch v ng nghim c nhit biu
lun lun c cnh nhau chng c cng nhit .
c) Nu mu c mu vng t nhin th phi ly tip nc mu vo 2 ng
nghim na (trng hp ny phi so mu trn Comparat).
Bc 4: Lc u ng nghim c mu v cht ch th ho trn. Lp li t
bc 2 cho mu tng khc (nu c). Chuyn tt c n ni phn tch.
Bc 5: Cch so mu nh m t phn qu trnh xc nh. Ghi gi tr
pH tm c v nhit in situ, nhit bng mu, nhit mu lc phn tch
vo s quan trc.
Bc 6: Vic tnh ton kt qu c th thc hin sau ngy lm vic. Kt qu
tnh phi c ngi th hai kim tra.
3.2. XC NH KIM NC BIN

Nc bin v i dng c kh nng trung ho c mt lng no axit
thm vo n. Kh nng ny do mt s hp phn mang tnh baz to ra v ngi
ta gi kh nng l " kim" ca nc bin. Kh nng nhn thm Proton (H+)
ca nc bin c c chnh l do s c mt trong nc cc anion ca cc axt
yu. C th biu din nh lng kim chung ca nc bin (k hiu Alk)
72
nh sau:
Alk = [HCO3-] + 2[CO3-2] + [H2BO3-] + [HSiO3-] +
[H2PO4-] + 2[HPO4-2] + [HS-] + ([OH-]-[H+])
y cn phn bit r khi nim kim vi tnh cht mi trng kim
(yu) ca nc bin. Mi trng mang tnh cht kim, trung tnh hay axit c
quyt nh bi nng ion Hydro (pH), cn kim l tng nng cc anion
ca cc axit yu c mt trong nc bin.
Trong s cc thnh phn to nn kim chung ca nc bin nh trn, c
ngha nht chnh l cc anion HCO3- v CO3-2 ca axit Cacbonic (H2CO3) v
anion H2BO3- ca axit Boric (H3BO3) bi chng c hm lng ln nht. Cc
anion khc c hm lng khng ng k nn thng b b qua, ch c tnh
n trong mt s trng hp cn thit. Do kim chung ca nc bin
c coi gn ng l tng ca kim Ccbonat v kim Borac:
Alk = AlkC + AlkB
Trong :
AlkC = [HCO3-]+ 2 [CO3-2] l kim Cacbonat;

AlkB = [H2BO3-] l kim Borac.
V mt nh lng, kim c xc nh bng s miligam ng lng

ca cc anion ca cc axit yu (ch yu l ca axit H2CO3 v H3BO3) c trong 1
lt nc bin (meg/l). Gi tr tuyt i ca kim c o bng lng axt
mnh (v d HCl) cn thit thm vo 1 lt mu nc bin cho ti khi pH ca
mu n nh trong khong 5,5 n 5,7.
Ngoi cch biu din tr s tuyt i ca kim nh trn, ngi ta cn
biu din bng tr s tng i. l cc h s kim Alk/S (h s kim-mui)
hoc Alk/Cl (h s kim-Clo) hay Alk/SO4 (h s kim-sunfat), trong S, Cl
v SO4 tng ng l mui, Clo v hm lng ion Sunfat ca nc bin.
kim nc bin v i dng kh n nh do tnh n nh ca cc anion
Cacbonat, n thng ch dao ng trong khong 2,0 n 2,5 meg/l. Tng t
73
nh vy, h s kim cng thng l hng s i vi nc i ng. Tuy nhin,

cc vng nc gn b, cc vnh kn, cc vng ca sng... h s kim bin i
trong gii hn rt rng (c th t vi nghn n hng trm nghn). V d nc
vnh Taganp ca bin Azp c h s kim-Clo bin i t 4385 n 134000.
kim (hoc cc h s kim) ca nc bin c s dng (cng vi pH)
tnh ton cc dng tn ti ca axit Cacbonic trong nc bin. Ngoi ra
kim cn c s dng trong cc tnh ton v cn bng CO2, cn bng h
Cacbonat, tnh mc xo trn nc vng gn b, ca sng. Do tnh n nh
cao ca kim trong nc bin nn n cn c s dng nh mt ch s ca
khi nc.
3.2.2. Phng php xc nh kim nc bin
Nh trn nu, gi tr tuyt i ca kim nc bin c o bng
lng axt mnh (v d HCl) cn thit thm vo 1 lt nc bin cho ti khi pH
n nh trong khong 5,5 n 5,7. Bi vy, nguyn tc ca phng php xc
nh kim l chun trc tip mu nc bin bng dung dch axit Clohydric
(HCl) c nng bit trc, khi phn ng gia HCl vi cc mui ca cc
axit yu trong mu nc s xy ra. V d i vi cc mui ca axit Cacbonic (k
hiu cc mui ny l RHCO3 trong R l cation kim loi no ), phn ng
xy ra nh sau:
RHCO3 + HCl RCl + CO2 + H2O
(3.I)
phn ng trn ch xy ra mt chiu, cn phi ui kh CO2 mi c to

thnh ra khi cht lng ang b chun , nu khng, s xut hin ca n trong
hn hp s to thnh axit Cacbonic v mui ca axit ny, s lm tiu hao thm
mt lng HCl no .
ui CO2 ra khi cht lng, trong qu trnh chun mu nc ngi ta
khng ngng thi vo mu nhng lung khng kh khng c CO2. Thi im
kt thc qu trnh chun c nhn bit nh thuc ch th mu hn hp (s
ni ti mc 3.2.4).
74
3.2.3. Dng c v thit b

- Mirco Biuret dung tch 10ml, c chia 0,01ml. Biuret phi c kim
nh v c h s hiu chnh km theo.
Khng kh khng c CO2
Hnh 3.3: Bnh chun xc nh kim nc bin
- Cc Pipet 100 ml, 20 ml, 10 ml, 1 ml mi loi 1 chic, tt c u c

kim nh v c hiu chnh km theo.
- Cc bnh nh mc 1 l, 0,5 l, 0,25 l c kim nh v hiu chnh.
- Bnh chun th tch khong 30 ml c ng thi khng kh khng c
CO2 vo (hnh 3.3).
- Cc dng c thng thng khc ca phng th nghim.
Tt c cc bnh ong, chai l... phi ra cn thn v c sy kh trc lc
lm vic. Nu chai l s dng ln u th sau khi ra sch phi np y nc ct
v gi nguyn hin trng t 10-12 ngy loi tr hin tng ho tan thu tinh.
3.2.4. Ho cht
Dung dch chun chnh axit Clohydric (HCl) 0,1N
75
Dung dch ny c chun b t 8,3 ml axit HCl m c (t trng 1,19)

ho vi nc ct thnh 1 lt. Ch c cho axt vo nc m khng c lm
ngc li.
Dung dch chun lm vic axit Clohydric 0,02N
Dung dch ny c chun b t 100 ml dung dch chun chnh ho vi
nc ct thnh 500 ml. Dung dch chun lm vic c bo qun trong bnh c
trng Parafin pha trong, c nt cao su kn. Khi lm vic cn thay nt cao su
kn bng nt cao su c 2 l cm, 1 l cm ng ni vi Biuret v l cn li cm
ng thu tinh bn trong c cha vi ti xt.
Dung dch mui Borac 0,02N (Na2B4O7.10 H2O)
Dung dch ny cn c gi l Bura, dng xc nh h s hiu chnh
nng ca dung dch HCl. chnh xc ca vic xc nh kim nc bin
ch yu ph thuc vo Bura.
Ly chnh xc 0,9536 gam Borac kt tinh cho vo bnh ong 250 ml, b
sung nc ct cho n n vch mc. Th tch bnh ong phi c kim nh
v c hiu chnh.
H s hiu chnh chun ca dung dch Borac (KB) c tnh theo cng
thc sau:
KB = V/(V1 + )
(3.3)
Trong V l th tch quy c ca bnh (250 ml), V1-th tch thc ca

bnh, -hiu chnh th tch thc ca bnh theo nht .
V d: Th tch bnh ong theo quy c l loi V=250ml; th tch thc ca
bnh sau khi kim tra li l V1=249,88 ml; ti 25oC hiu chnh th tch bnh l
25=-0,26 nn KB=1,0015. Ti 16oC c 16=+0,16 nn KB=0,9998.
Cn ch trc khi pha thnh dung dch, mui Borac phi c kt tinh li
nhit khng qu 55oC, ch c iu kin th mi c tinh th Borac ngm
10 phn t H2O.
76
Thuc ch th mu hn hp
Ly 32 mg Metyl , kh trn vi 1,18 ml NaOH 0,1N trong chn m no
hoc chn s. Sau khi nghin k hn hp thnh mt th thng nht th ra chn
bng 80 ml ru Etylic 96%, sau cho thm vo hn hp thu c 4,8ml cn
c cha 0,1% Metylen xanh. Cn c cha 0,1% Metylen xanh c chun b
bng cch ho 0,1g Metylen xanh kh vi 100 ml ru Etylic 96%.
Thuc ch th mu hn hp phi trung tnh, tc l phi c mu gia xanh l
cy nht v nu. Nu thuc c mu xanh l cy nht, ngha l n qu kim, ta
phi nh dung dch HCl 0,1N vo cho n mu qui nh, nu c mu nu qu axit, ta phi cho thm dung dch NaOH 0,1N vo n.
Thuc ch th mu hn hp rt hay b mt phm cht nn khng c chun
b qu nhiu. Khi thy c s sai lch (i mu, vn c) th phi chun b thuc
mi. Thuc c bo qun trong bnh xm mu.
Vi ti xt
Ho cht ny dng loi kh Cacbonic ra khi lung khng kh thi vo
cht lng trong qu trnh chun . Vi ti xt phi kh v cn c ry k, lc
bi tr thnh dng bt, ht nh v mn. Ho cht c bo qun trong bnh c
nt bc, mt ngoi nt c hn kn bng Parafin hi nc trong khng kh
khng lm hng n.
kim tra cht lng vi ti xt, ngi ta cho n vo mt ng thu tinh,
nhng mt u ng vo nc Bari v thi khng kh qua trong vng 5-10
pht. Nu nc Bari khng i mu th ch phm tt. Nc Bari c chun b
t 4 gam Ba(OH)2 ho vi 100 ml nc ct khng c CO2 (l nc ct mi c
un si trong vng na gi). Nc Bari thu c phi trong sut, nu c phi
lng ng v gn ly phn trong.
Mu nc bin xc nh kim thng c ly sau cc mu xc nh
pH v xy ho tan. Bnh ng mu bng thu tinh mu xanh hay da cam (v
77
chng t b n mn), dung tch khong 300-500ml. Bnh mu cn c ngm

lin tc nc bin cho n lc s dng v trc khi ly mu n phi c trng
2-3 ln bng chnh nc mu cn ly. Mu nc phi c ly y bnh trong
bnh khng cn khng kh.
Sau khi ly mu c th tin hnh xc nh kim ngay. Trng hp
khng phn tch ngay c th c th gi mu trong mt khong thi gian no
vi iu kin nc mu khng bay hi mt v khng c s trao i CO2 gia
mu vi kh quyn. Mun vy, nt bnh phi kn v phi c ph bng Parafin.
Mt khc, trnh lm bin i hm lng CO2 trong mu do cc qu trnh sinh
ho hc, cn phi bo qun mu ni ti v nhit thp.
Xc lp chun thc ca axit Clohydric
Trng 2 ln Micro Biuret bng chnh dung dch chun lm vic HCl 0,02N
chun b, sau np dung dch vo y Biuret.
Dng Pipet kim nh (tt nht l loi t ng) ly tht chnh xc 10 ml
dung dch 0,02N Bura (Na2B4O7) cho vo bnh chun (hnh 3.3), cho thm
vo 8 git ch th mu hn hp.
Thi khng kh khng c CO2 vo trong vng 5 pht, sau chun
hn hp bng dung dch HCl t Biuret trong khi khng ngng thi khng kh
khng c CO2 vo. Qu trnh chun ch dng li khi cht lng c mu hng
nht v mu khng mt i trong vng 2-3 pht.
Ton b cng vic trn c lm t 2-3 ln. Nu s c trn Biuret sau mi
ln chun khng khc nhau qu 0,05 ml th s c trung bnh c s dng
tnh ton kt qu. H s hiu chnh chun ca dung dch axit Clohydric
(KHCl) c tnh theo cng thc sau:
KHCl = Vn.KB/(a +)
(3.4)
Trong , KB l h s hiu chnh chun ca dung dch Bura; Vn - th

tch thc ca Pipet ly dung dch Bura ( c hiu chnh); a - s c trung bnh
78
trn Micro Biuret v -hiu chnh Biuret ng vi s c ny. V d: Th tch

ca Pipet ly dung dch Bura l 10ml, hiu chnh Pipet l -0,04 vy th tch
thc ca n l Vn=9,96 ml. H s hiu chnh chun ca dung dch Bura l
KB=1,0022, s c trung bnh trn Biuret l 9,982 v hiu chnh s c l
+0,012. Thay cc gi tr trn vo (3.4) ta c KHCl=0,9988. chun dung dch
chun lm vic HCl theo quy c l 0,02, vy chun thc ca n l NHCl=
0,02 . 0,9988 = 0,01998.
Xc nh kim ca mu nc bin
Mu nc c em vo phng th nghim mt thi gian cn thit n c
cng nhit ca phng. Trc ht np dung dch chun HCl c kim tra
vo y Biuret.
Tip theo, dng Pipet t ng kim nh ly 20 ml mu nc cho vo
bnh chun ra sch v sy kh (phi trng Pipet bng chnh nc mu),
cho thm vo 8 git ch th mu hn hp v thi khng kh khng c CO2 vo
trong vng 5 pht.
Tip chun mu nc bng dung dch HCl t Biuret trong khi khng
ngng thi khng kh khng c CO2 vo. Lc u c th m c van cho dung
dch HCl chy nhanh, sau cho chy chm dn v cui cng chy tng git hoc
na git mt.
Vic chun ch ngng li khi cht lng c mu hng nht v n nh
trong vng 3 pht. Ghi kt qu chun vo s. Ch : khi xc lp chun ca
HCl bng nh sng no th khi xc nh kim ca mu nc cng phi dng
nh sng .
Tnh tr s kim chung
Tr s kim chung ca nc bin (Alk) biu din bng miligam ng
lng trong 1 lt nc bin c tnh theo cng thc sau:
79
Alk (meg / l ) =
(a + 1 ).N .K HCl .1000

V + 2
(3.5)
Trong a l s c trn Biuret khi chun mu nc v 1 l hiu chnh

ca s c ny; N - chun quy c ca dung dch chun lm vic HCl (0,02);
KHCl -h s hiu chnh chun; V- th tch mu nc ly phn tch v 2 l
hiu chnh Pipet ly mu nc.
Tnh tr s kim Cacbonat v kim Borac
kim Cacbonat AlkC c tnh gn ng theo cng thc:
AlkC = Alk - AlkB
(3.6)
Trong AlkB l kim Borac. Nm 1955, Havy thit lp c mi

quan h gia kim Borac vi Clo (Cl%o) v hot ca ion Hydrro trong
nc bin, nh sau:
2,2.10 5.Cl %o
Alk B =
1 + a(H + ) / K B*
(3.7)
Trong , a(H+) l hot ion Hydro, c tnh thng qua tr s pH ca

nc bin (thc t, khi xc nh pH bng phng php so mu hay o in, ta
ch xc nh c nng ca cc ion Hydro hot ng); KB* - hng s nng
bc mt ca axt Boric trong nc bin (v hng s nng s c gii thch
r mc 3.3 chng ny). y ch tnh n hng s nng bc mt v cc
hng s phn ly bc 2 v bc 3 ca axit Boric nh khng ng k. Trong cc
bng hi dng chuyn dng hin nay (bng 3.7) c a ra cc gi tr hng s
nng KB* ng vi iu kin nhit-mui khc nhau.
Bng 3.7: Gi tr hng s nng bc mt (KB*.10-8) ca axit Boric trong nc bin (trch t
bng Hi dng)
Clo %o
T=5oC
10 oC
15 oC
20 oC
25 oC
30 oC
16
0.112
0.129
0.144
0.158
0.174
0.191
17
0.117
0.132
0.148
0.166
0.182
0.200
80
Clo %o
T=5oC
10 oC
15 oC
20 oC
25 oC
30 oC
18
0.123
0.138
0.155
0.174
0.191
0.204
19
0.126
0.141
0.158
0.178
0.195
0.214
20
0.132
0.148
0.166
0.182
0.204
0.224
21
0.135
0.151
0.170
0.191
0.209
0.229
25
0.158
0.178
0.200
0.219
0.240
0.257
3.2.8. Th t cng vic

Bc 1: Chun b mi dng c cn thit.
Bc 2: Xc lp chun thc ca dung dch chun lm vic HCl.
a- Trng Biuret bng dung dch chun lm vic HCl pha ch, sau np
dung dch ny vo y Biuret.
b- Trng Pipet bng dung dch chun Borac 0,02N kim nh v dng n
ly 10 ml dung dch ny cho vo bnh chun , cho thm vo 8 git ch
th mu.
c- Thi khng kh khng c CO2 vo bnh trong 5 pht. Sau chun
hn hp bng dung dch HCl trong khi khng ngng thi khng kh khng c
CO2 vo bnh. Khi cht lng c mu hng nht th tm ngng chun .
d- Theo di mu ca cht lng trong 3 pht trong khi vn thi khng kh
khng c CO2 vo . Nu mu bin mt th tip tc chun tht cn thn cho
n khi mu n nh (cn ch l t lc bt u n lc thc s kt thc phi
khng ngng thi khng kh khng c CO2 vo).
e- Ghi s c ri lm li ln th 2 ly s c trung bnh, sau tnh ton
h s hiu chnh.
Bc 3: Chun mu nc bin.
a- Np dung dch chun HCl kim tra vo y Biuret.
b- Trng Pipet bng nc mu v dng n ly 20 ml mu cho vo bnh
81
chun (bnh chun trc phi c ra sch v sy kh), cho tip vo

8 git ch th mu. Thi khng kh khng c CO2 vo trong vng 5 pht.
c- Chun hn hp bng dung dch HCl trong khi khng ngng thi
khng kh khng c CO2 vo. Qu trnh tip tc nh khi xc lp chun thc
ca dung dch HCl.
d- Ghi s c trn Biuret vo s.
Bc 4: Vic tnh ton kt qu c th thc hin sau ngy lm vic. Kt qu
tnh phi c ngi th hai kim tra.
3.3. TNH TON CC THNH PHN H CACBONAT TRONG BIN
3.3.1. G ii thiu chung

Cc hp phn v c ca Cacbon tn ti trong nc bin di dng kh
Cacbonic (CO2), axit Cacbonic (H2CO3) v cc dn xut phn ly ca n (HCO3-,
CO3-2). Cc tiu phn ny lin h tng h vi nhau trong mi cn bng ng v
cng nhau to thnh h cacbonat. Quan im hin i cho rng i dng l mt
h ng lc h phc tp v thng nht, trong bao gm nhiu h thnh phn
m h cacbonat l mt trong cc h thnh phn phc tp nht. Nng tng
cng cc hp phn ca h ccbonat (k hiu C) c biu din di dng:
C = [CO2] + [H2CO3] + [HCO3-] + [CO32-]
i lng C t l vi mui nc bin, song mi quan h ny khng
cht ch lm, nht l nhng vng c mui thp. i vi nc i dng c
mui cao v nhit 812oC, khi p sut kh CO2 ho tan trong nc cn
bng vi p sut ring ca kh CO2 trong kh quyn v c gi tr
PCO2=(270320)10-6at, th mi quan h ca C vi Clo nc bin (theo Buch
K.) c biu din gn ng l:
C = 0,108 Cl%o (1,5%) mM/l
Nh cp n cc mc 3.1 v 3.2 chng ny, kh CO2 ho tan, ion
Hydro v kim l cc thnh phn c lin quan trc tip ti h cacbonat. Nhn
82
tng qut hn na, h cacbonat ca bin cn c quan h trc tip v c vai tr

rt quan trng trong c ba qu trnh tng tc: thu quyn-kh quyn, thu
quyn-thch quyn v thu quyn-sinh quyn. Bi vy nghin cu h cacbonat
ca bin rt c ngha i vi nhiu lnh vc khoa hc nh: lch s tri t, lch
s kh quyn, lch s sinh quyn, a cht hc, a ho hc, kh tng hc... Bc
tranh tng qut v mi cn bng ng ca h cacbonat trong bin m t trn
hnh 3.4.
CO2 (kh quyn)
Mt bin
CO2 (ho tan) + H2O H2CO3
Quang
hp
hp
+ HCO3-
OH +
H+
+ CO3-2
Sinh vt
+
CaCO3 (ho tan) Ca+2 (hoc Mg+2...)
y bin
CaCO3 (rn)
Hnh 3.4: S h cacbonat trong bin
Trong mi cn bng ng, cc tiu phn ca h cacbonat lin h tng h

vi nhau v chuyn ho cho nhau. Bt c mt s bin i d nh ca mt tiu
phn no cng ko theo s bin i ca cc tiu phn khc v lm cho h
chuyn sang trng thi cn bng mi.
S trn cn ch r s cn bng gia p sut kh CO2 trong kh quyn v
trong nc duy tr nng tt c cc hp phn ca h cacbonat trong nhng
gii hn nht nh. Trong cc gii hn , i vi mi trng hp c th, nng
cc tiu phn trc ht c xc nh bi tng quan gia qu trnh sn sinh
v tiu th CO2. V d, gim nng CO2 xung khng nhiu lm (thng xy
ra trong qu trnh quang hp lp nc tng trn) th mt phn ion
hydrocacbonat s chuyn sang ion cacbonat v pH s tng. Ngc li, cc lp
nc su v gn y nng CO2 c th tng cao do qa trnh phn hu cht
83
hu c, lm chuyn gn ht ion cacbonat sang hydrocacbonat v pH gim.

Nh vy, v nguyn tc khng th xc nh nng cc tiu phn ca h
bng phng php phn tch ho hc, bi v nu tch ring bt k mt tiu phn
no ra o c s lm thay i ngay trng thi cn bng ca h. Ch c th tnh
ton chng thng qua mt s yu t khc d xc nh nh kim, pH v cc
hng s nhit ng nh hng s nng , hot , h s hot .
3.3.2. Phng php tnh cc thnh phn h cacbonat
Da trn nguyn tc cn bng ho hc v nh lut tc dng khi lng,
nm 1932 Bukh, Havy v cc cng tc vin xy dng l thuyt h cacbonat
trong bin.
Axt Cacbonic c hai bc phn li:
H2CO3 H+ + HCO3HCO3- H+ + CO3-2
Theo nh lut tc dng khi lng, nhit 22oC v p sut 760 mmHg,
ta c:
[H+].[HCO3-]/[H2CO3] = K1 = 4.10-7
(3.8)
[H+].[CO3-2]/[HCO3-] = K2 = 4,2.10-11
(3.9)
y K1 v K2 l hng s cn bng nhit ng ca axt Cacbonit (hng s

phn ly bc 1 v bc 2), ph thuc vo nhit v p sut, cc k hiu mc
vung ([..]) ch nng cc tiu phn. i vi nc bin, do c nhiu thnh
phn ion trong n nn trong cng thc (3.8), (3.9) phi thay nng cc tiu
phn bng hot ca n. Do :
a ( H + ).a ( HCO 3 ) a ( H ) f HCO3 HCO 3

=
= K1
a ( H 2 CO3 )
f H 2CO3 [H 2 CO3 ]
84
(3.10)
+
2
a ( H + ).a (CO 3 2 ) a ( H ) f CO3 CO 3
=
= K2
a ( HCO 3 )
f HCO3 HCO 3
(3.11)
Trong k hiu a(..) ch hot ca ion v f - h s hot ca n.

i vi nc bin c mui trung bnh, l thuyt hin i v dung dch
ch cho php tnh cc h s hot theo lc ion. V vy, ngy nay ngi ta
khng s dng cc hng s nhit ng K1, K2, m s dng cc hng s nng
K1* v K2*. Cc hng s ny bt bin i vi nhit v p sut, nhng li bin
i theo mui. Vi nc bin c mui trung bnh, hot ca axit H2CO3
khng phn li c coi gn ng bng nng ca n. Do t 3.10, 3.11 ta
c:
a(H+).[HCO3-]/a(H2CO3) = K1.fH2CO3/fHCO3 = K1*
(3.12)
a(H+).[CO3-2]/[HCO3-] = K2.fHCO3/fCO3 = K2*
(3.13)
a vo cc hng s nng K1* v K2* khc phc c vic s dng

cc h s hot f, thc ra chng c tnh ti trong khi xc nh chnh cc
hng s ny bng thc nghim (tng t nh khi xc nh pH ta ch xc nh
c nng ca cc ion Hydro hot ng). vic s dng c thun li,
ngi ta thng biu din hng s nng qua logarit m ca n:
pK1*= -lg(K1*) v pK2*= -lg(K2*)
Buch K. thit lp c mi lin h gia pK1*, pK2* vi Clo ca nc
bin ti nhit 20oC v cc s hiu chnh cho n di nh hng ca p sut
thu tnh thng qua su H:
pK1*= 6,47 - 0,188 (Cl%o)1/3 ;
pK1*= -0,48.10-4H
pK2*= 10,38 - 0,510 (Cl%o)1/3 ;
pK2*= -0,18.10-4H
Gi tr K1* v K2* i vi nc i dng c Clo 15-20%o v nhit

khc nhau c tnh trc v cho trong cc bng hi dng chuyn dng (bng
3.8).
85
Nh vy trong hai phng trnh 3.12 v 3.13 c cha 3 n s l [HCO3-],

[CO3-2] v a(H2CO3). tnh c chng cn s dng phng trnh th ba, l
cng thc kim Cacbonat c ni ti mc 3.2 chng ny.
AlkC= [HCO3-] + 2[CO3-2]
(3.14)
Gii h 3 phng trnh 3.12, 3.13 v 3.14 ta c:

[HCO3-] = AlkC/[1+(2K2*/aH+)] (mg-ion/l)
(3.15)
[CO3-2] = AlkC/[2+(aH+/K2*)] (mg-ion/l)
(3.16)
Ring i vi a(H2CO3) c xc nh nh sau:

V CO2 + H2O H2CO3 nn a(H2CO3)=a(H2O).a(CO2). Bit rng
a(H2O)=1-0,000969Cl%o v a(CO2) = pCO2.o, trong pCO2 l p sut ring
ca kh CO2 (gi tr cn tnh) cn o l ho tan ca CO2 trong nc ct (cho
sn trong cc bng hi dng chuyn dng). Thay cc gi tr ny vo 3.12, c
ch n [HCO3-] tnh c theo 3.15, ta c:
Alk C .10 1.a ( H + )

pCO 2 ( at ) = *
K 1 . o .a ( H 2 O )(1 + 2 K 2* / a ( H + ))
(3.17)
Bng 3.8: Gi tr hng s nng K1* v K2* ca axit Cacbonic trong nc bin (trch t
bng Hi dng)
Nhit (oC)
Cl
%o
10
12
14
16
18
20
22
24
26
28
30
K1* (10-8)
15
0.74
0.77
0.80
0.83
0.86
0.89
0.92
0.95
0.97
0.99
1.01
16
0.75
0.78
0.81
0.84
0.87
0.91
0.93
0.96
0.99
1.01
1.03
17
0.76
0.79
0.82
0.86
0.89
0.92
0.95
0.98
1.00
1.02
1.05
18
0.77
0.81
0.84
0.87
0.90
0.93
0.97
0.99
1.02
1.04
1.06
19
0.79
0.82
0.85
0.88
0.92
0.95
0.98
1.03
1.05
1.06
1.08
20
0.80
0.83
0.87
0.90
0.93
0.97
1.00
1.04
1.06
1.07
1.10
K2* (10-9)
86
Nhit (oC)
Cl
%o
10
12
14
16
18
20
22
24
26
28
30
15
0.60
0.63
0.66
0.69
0.73
0.76
0.79
0.83
0.86
0.90
0.93
16
0.63
0.67
0.71
0.74
0.78
0.81
0.85
0.88
0.92
0.96
0.99
17
0.67
0.71
0.74
0.78
0.83
0.86
0.90
0.93
0.97
1.01
1.05
18
0.71
0.75
0.79
0.83
0.87
0.91
0.95
0.99
1.03
1.07
1.11
19
0.75
0.79
0.83
0.88
0.92
0.96
1.01
1.05
1.10
1.14
1.18
20
0.80
0.84
0.89
0.93
0.98
1.02
1.07
1.12
1.16
1.21
1.26
C th chuyn pCO2 vi th nguyn atmotphe tnh c t (3.17) thnh

nng CO2 vi th nguyn Mol/l (phn t gam) hay ml/l tu thuc th nguyn
ca S, theo cng thc:
CO2 = pCO2. S
(3.18)
y S l ho tan ca kh CO2 trong nc bin ng vi p sut ring

ca n trong kh quyn bng 1 at. Gi tr S cng c tnh trc v cho sn
trong cc bng hi dng.
Vic tnh ton c th n gin hn nu vit 3.17 di dng
pCO2 = AlkC.
(3.19)
Trong l h s nhn, bao gm tt c cc i lng bin i trong 3.17,

tr AlkC. Gi tr ca ph thuc vo Clo, nhit , pH, v cha tnh ti nh
hng ca p sut thy tnh, cng c tnh trc v cho trong cc bng hi
dng. Da theo cc cng thc 3.15, 3.16 v 3.19 tnh c nng cc hp
phn ca h cacbonat nc bin ph thuc vo nhit , mui, kim v
pH. Kt qu cho bng 3.9.
Bng 3.9: Nng cc hp phn ca h cacbonat nc bin khi pCO2 = 3.10-4 at
S
kim
%o
Alk
AlkC
35
20
2.38
2.28
pH
8.20
[H2CO3 + CO2]
[HCO3-]
[CO3-2]
mg/l
mM/l
mg/l
mM/l
mg/l
mM/l
0.228
0.0102
1.740
1.740
0.540
0.270
87
S
%o
T
o
kim
Alk
AlkC
35
2.38
2.28
30
20
2.05
1.97
pH
[H2CO3 + CO2]
[HCO3-]
[CO3-2]
mg/l
mM/l
mg/l
mM/l
mg/l
mM/l
8.15
0.423
0.0190
1.970
1.970
0.306
0.153
8.17
0.233
0.0104
1.585
1.585
0.380
0.190
T bng 3.9 thy rng trong mi trng hp, hp phn HCO3- lun lun
chim u th v hp phn (H2CO3+CO2) c nng b nht. Tuy nng
(H2CO3+CO2) nh b nhng n li l nhn t c bn nh hng n trng thi
cn bng ca h cacbonat trong bin. iu ny c th hin r trn s h
cacbonat hnh 3.4.
88
Chng 4
XC NH CC HP PHN DINH DNG V C V CC
CHT HU C TRONG NC BIN
4.1. NGHA V NGUYN TC CHUNG PHNG PHP SO MU XC
NH CC HP PHN DINH DNG V C TRONG NC BIN
4.1.1. ngha
Theo cch gi, cc cht dinh dng v c trong bin bao gm rt nhiu
nguyn t cn thit i vi i sng sinh vt, nh H, C, O, P, N, Si, S, Mg, Ca,
K... Tuy nhin trong mi trng hp, 3 nguyn t P, N, Si bao gi cng l
khng th thiu c i vi s sng.
Cc hp cht v c ca Phtpho, Nit, Silic tn ti trong nc bin vi
nng rt nh v rt hay bin i theo c khng gian v thi gian. S bin i
ca chng ph thuc cht ch vo qu trnh quang hp, bi trong qu trnh ny
thc vt phi s dng cc cht dinh dng v c tng hp nn cht hu c
u tin trong bin.
Phtpho dinh dng v c tn ti trong nc bin di dng axit
Phtphoric (H3PO4) cng cc dn xut phn ly ca n (H2PO4-, HPO4-2, PO4-3),
gi chung l cc Phtphat. Trong nc bin, axit Photphoric c th kt hp vi
mt vi phn t nc to nn nhng phn t phc tp hn, ch yu l dng
H3PO4.2H2O. Nng tng cng cc Phtphat trong nc bin c th bin i
t 0-100 mgP/m3.
Nit dinh dng v c trong nc bin tn ti cc dng lin kt khong.
l Amni (NH4+), Nitrit (NO2-) v Nitrat (NO3-). Trong 3 dng lin kt
khong ny th Amni l dng u tin v Nitrat l dng cui cng ca qu trnh
89
ti sinh Nit v c trong bin. Nhu cu Nit v c ca qu trnh quang hp

trong bin cng gim dn t NO3- n NH4+. Nng tng cng Nit v c
trong bin dao ng trong khong 0-500 mgN/m3.
Silic dinh dng v c tn ti trong nc bin dng axit Silisic (H2SiO3)
v cc dn sut phn ly ca n (HSiO3-, SiO3-2), gi chung l cc Silicat. Trong
nc bin, axit Silisic c kh nng to thnh nhng phn t phc tp hn nh
kt hp vi mt s phn t nc v tn ti dng mSiO2.nH2O, trong nhiu
nht l dng Metasilisic (H2SiO3)n. So vi cc hp phn dinh dng khc, Silic
v c tn ti trong nc bin vi nng cao hn (bc nng c th ti 103104 mgSi/m3) do ho tan trong nc ca n kh cao v do n c ngun d tr
di do t lc a.
Nghin cu cc hp cht dinh dng v c trong nc bin rt c ngha
i vi cc nghin cu ho hc bin, sinh hc bin v mi trng. Cc nghin
cu v qu trnh sn xut s cp trong bin ch ra rng, nhu cu s dng
Cacbon, Silic, Nit v Phtpho v c trong quang hp ca thc vt ni
(Phytoplankton) c t l (tnh theo khi lng) l C:Si:N:P = 42:28:7:1, ln hn
nhiu so vi t l tn ti t nhin ca chng trong nc bin. Chnh v vy, 3
nguyn t P, N, Si, nht l P v N c coi l ch tiu gii hn quang hp trong
bin. Vic s dng cc cht dinh dng v c trong quang hp ca thc vt bin
to nn sn phm s cp l khu quan trng bc nht trong chu trnh chuyn
ho vt cht v nng lng trong h sinh thi bin.
4.1.2. Nguyn tc chung phng php so mu xc nh cc hp phn
dinh dng v c trong bin
Cho n nay, phng php so mu vn ang c s dng rng ri xc
nh cc hp phn dinh dng v c P, N, Si trong nc bin. Phng php ny
da trn tnh cht ca mt s dung dch c kh nng to thnh hn hp nhum
mu khi cho chng tc dng vi nhng ho cht c trng. Mu ca hn hp c
th hin ln rt r ngay c trong trng hp nng cht tan trong dung dch rt
nh. Hin nhin, cng mu ca hn hp t l vi nng cht tan v dy
lp dung dch.
90
Vi nguyn tc so snh mu ca dung dch cn xc nh nng vi mu

ca cng loi dung dch y nhng bit trc nng , ta c th tm c nng
dung dch cn xc nh. Dung dch bit trc nng c gi l dung
dch chun, hay n gin hn gi l "chun" .
Phng php so mu bng mt
Trong cch so mu bng mt, th thut cn bng mu l quan trng nht.
Bit rng, khi cng mu ca hai dung dch cng loi cn so snh trng
thi cn bng th nng v chiu dy lp dung dch ca chng c quan h sau
y:
C1/C2 = h2/h1
(4.1)
Trong C1, C2 v h1, h2 tng ng l nng v chiu dy cc dung dch

1 v 2.
T thy rng, khi so mu hai dung dch cng loi, cng mu nhng
cng mu khc nhau, ch cn thay i ct chiu cao ca ch mt dung dch
bng cch thm vo hoc bt i mt lng thch hp, ta s c trng thi cn
bng mu.
chnh xc ca phng php so mu bng mt c lin quan vi cc yu
t sau:
- Trng thi mt ca ngi phn tch. iu ny ph thuc rt nhiu vo
kinh nghim ca phn tch vin.
- nh hng ca nng cc dung dch: Cng thc 4.1 ch ng khi t s
h2/h1 kh gn n v, ngha l C1 v C2 khng khc nhau nhiu lm. Nu t s
trn khc xa n v th vic so mu khng c ngha. Bi vy, cch khc phc
tt nht l phi c nhiu dung dch chun vi nng khc nhau, c th la
chn d dng dung dch chun c mu gn nht vi mu dung dch cn phn
tch. Kinh nghim phn tch cho thy tng quan chiu cao ca cc ct dung
dch trng thi cn bng mu ch c php nm trong gii hn 1: 0,7 (hoc
0,6).
91
- Ngoi ra, chnh xc ca phng php cn ph thuc vo sch ca

ho cht, mui trong mu nc phn tch, nhit v nh sng mi trng
ni lm vic, khong thi gian t lc thu mu n lc phn tch, khong thi
gian phn tch... Nhng nhn t ny u c nh hng n mu sc v cng
mu ca cc dung dch chun v mu nc. ng nhin c th khc phc c
nhng nh hng ny bng cch lm sch ho cht, tng mui ca dung dch
chun, khng ch nhit v nh sng ni lm vic, khng nn lu mu qu lu,
cc thao tc phi nhanh chng v chnh xc...
S dng cc thit b hin i trong phng php so mu
Thay cho vic so mu bng mt, ngi ta ch to nhng my v thit b
so mu (nh my so mu quang in, ph quang k...). So mu bng cc thit b
so mu l khch quan v t chnh xc cao, nhng li cn cc my mc tinh
vi, hin i v t tin. Do vy cch ny ch tin li khi lm vic trn b, trong
phng th nghim hoc trn cc tu nghin cu ln. Chi tit v phng php so
mu bng my so mu s c ni ti mc 4.6 chng ny.
4.2. XC NH PHT PHT TRONG NC BIN
4.2.1 Phng php xc nh

Nh ni mc 4.1.1, trong mi trng nc bin axit Phtphoric v
axit Silisic c th chuyn thnh nhng dng phc tp hn nh kt hp vi mt
vi phn t nc:
H3PO4 + 2H2O = H7PO6
H2SiO3 + 3H2O = H8SiO6
Trong dung dch long, nhng hp cht phc tp ny nu c tc dng
vi Amoni Molipdat s to ra cc axit d a (gi l Heteropolyaxit) nhum mu
rt mnh. C th l, Amoni Molipdat khi tc dng vi H7PO6 s cho
Heteropolyaxitphtphoric {H7P(Mo2O7)6}, khi tc dng vi H8SiO6 s cho
Heteropolyaxitsilisic {H8Si(Mo2O7)6}. Trong cc Heteropolyaxit ny, gc
(Mo2O7)-2 thay th hon ton xy cc axit tng ng H7PO6 v H8SiO6.
92
Cc Heteropoliaxyt k trn nhum mu vng rt mnh v c th dng mu

ny lm c s so mu vi cc dung dch chun cng loi xc nh Phtpht
v Silicat. Nhng v nc bin lun c mt ng thi c hai hp phn Phtphat
v Silicat nn nu ch dng mu vng so mu th ta ch bit c tng nng
ca Phtpht v Silicat, ch khng th bit nng ring tng hp phn.
xc nh ring tng hp phn, ngi ta phi s dng cc cht kh c trng.
Nh tc dng vi cht kh c trng, Molipen c ho tr 6 trong cc
Heteropolyaxit k trn b kh v sn phm nhum mu xanh rt mnh (gi l
mu xanh Molipen).
xc nh Phtpht, cht kh c trng c s dng l Thic Clorua
(SnCl2) m c im ca n l ch kh Molipen trong Hetero-polyaxit c
Phtpho. xc nh Silicat, cht kh c trng c s dng l mui Mor
(NH4)2Fe(SO4)2.6H2O. Mui Mor ch kh Molipen trong Heteropolyaxit c
Silic. Nh vy, mc d cng s dng mu xanh Molipden lm c s so mu
vi dung dch chun, nhng trong mi trng hp s dng cht kh c trng ta
ch xc nh c mt hp phn tng ng. Tm lc nguyn tc ca phng
php ny c th hin qua s hnh 4.1.
Nc bin (c P, Si) + Molipdat Amoni Heteropolyaxit (mu vng)
Mu xanh Molipden
Heteropolyaxit
(mu vng)
+ Thic Clorua
+ Mui Mor
(xc nh Phtphat)
Mu xanh Molipden
(xc nh Silicat)
Hnh 4.1: S nguyn tc xc nh Phtphat v Silicat

Nu so mu bng mt, dng c quan trng nht l cp ng tr Hener. Cp
ng tr Hener gm hai ng tr thu tinh c hnh dng v kch thc hon ton
nh nhau, dung tch khong 100 ml. Pha gn y ca mi ng c mt van nh
cho dung dch chy qua trong trng hp cn bt i mt lng dung dch
93
thay i chiu cao ca n. y ca ng phi phng v nhn ng thi c gn

gng phn x nh sng. Thnh ngoi ca cc ng c khc vch chia (hoc
c gn chung mt thc o) xc nh chiu cao ct dung dch trong ng (hnh
4.2).
Km theo cp ng tr Hener l hp so mu Hener (cn gi l Calorimet).
Hp so mu Hener l mt hp kn, gn y c l nh nh sng i vo
gng gn di ng tr v phn x ln pha trn ti mt ngi phn tch. C th
dng g hoc ba cc tng ch to hp so mu, nhng phi m bo lng
nh sng i vo hai gng phn x l nh nhau. S dng Calorimet khi lm vic
vi mc ch loi tr nh hng ca nh sng mi trng xung quanh, ch cn
li mt dng nh sng phn x t gng qua lp dung dch trong cc ng tr ti
mt ngi phn tch.
Ngoi cp ng tr Hener v Calorimet, cn thit phi c cc chai l, bnh
ong hnh tr, hnh cu, cc bnh ng ho cht, ng nghim, cc loi Pipet,
giy lc... v cc dng c thng thng khc.
100
90
80
70
60
50
40
30
20
Gng phng
Hnh 4.2: Cp ng tr Hener
94
4.2.3. Ho cht
Hn hp dung dch Amoni Molipdat trong axit Sunfuric
Ho trn mt th tch dung dch 10% Amoni Molipdat (a) vi ba th tch
dung dch 50% axit Sunfuric (b). Cc dung dch (a) v (b) chun b nh sau:
Dung dch a: Ly 25 gam Amoni Molipdat tinh th ho vi nc ct
thnh 250 ml. Nu dung dch thu c b c th phi un nng cn thn n.
Trong trng hp cn thit phi lc qua phu thu tinh sch, c ra bng
axit Sunfuric long v nc ct.
Dung dch b: Pha long cn thn 1 th tch H2SO4 m c vo mt th tch
nc ct. Ch ch c b sung t t axit vo nc m khng lm ngc li.
Cc dung dch (a) v (b) phi c bo v cn thn trong cc bnh ring
bit v ch ho trn chng trc khi s dng. Sau khi ho trn theo t l dn,
dung dch Amoni Molipdat trong axit Sunfuric phi c bo qun trong bnh
thu tinh xm mu v t ni ti.
Dung dch Thic Clorua
Ly 25 gam bt thic sch ho hc (hoc thic l) cho vo ng nghim c
vch mc 10 ml, sau cho thm vo 2 ml axit Clohydric m c v thn
trng hm nng trn hi nc. Sau khi thic tan ht th nng th tch dung
dch ln ti vch bng nc ct. ng nghim cha Thic Clorua c y kn
bng nt qua cm sn Pipet hoc ng ht. Dung dch Thic Clorua cn
phi lun lun mi, khng c s dng dung dch chun b qu 24 gi
xc nh Phtphat.
Dung dch chun Kali dihydro photphat (KH2PO4)
a. Dung dch chun chnh KH2PO4
Dung dch chun chnh c chun b t ch phm tinh khit ho hc.
Dng cn phn tch ly chnh xc 1,097 gam KH2PO4 tinh th v chuyn lng
cn ny vo bnh cu dung tch 1 lt qua phu thu tinh. Ra chn cn v phu
95
nhiu ln bng nc ct. Th tch cui cng ca dung dch l 1 lt. bo qun
dung dch cn phi cho thm vo 2 ml Clorofooc (CHCl3). Bnh ng dung
dch phi tht sch v c nt mi tht tt. Dung dch ny c th s dng trong
thi gian 2-3 thng. Dung dch chun chnh c chun b nh trn c nng
250 mgP/l tc l 1 ml dung dch c 0,25 mg Phtpho nguyn cht.
b. Dung dch chun lm vic KH2PO4
Dng pipet ly 1 ml dung dch chun chnh cho vo bnh cu dung tch 100
ml v nng th tch ti vch mc bng nc ct. Mt mililit dung dch chun
lm vic c 0,0025 mg Phtpho nguyn cht. Dung dch chun lm vic ch
chun b trc lc lm vic.
Nc bin khng c Phtpht
loi tr nh hng ca mui, ngi ta khng dng nc ct chun
b dung dch chun lm vic nh va m t m phi s dng nc bin khng c
Phtpht. Mun c nc bin khng Phtphat, phi chun b mt ho cht ph
sau y: Ly 0,3 ml dung dch xyt nitrat st 1,0N (hoc mt xyt st khc) ho
vi 0,3 ml dung dch kim (KOH hoc NaOH) 1,0N, th tch chung c nng
ln n 100 ml bng nc ct. Ho cht ph ny khi thm vo nc bin tng
mt mt lng khng nhiu s kt ta c Phtphat ca nc bin di dng
Phtpht st. Khi kt ta ng yn, gn ly phn trong sut bn trn v lc n
qua mt phu mn c ra s b bng axit Sunfuric long (1:20) v nc
ct. Nc bin khng Phtphat thu c bng cch trn vn c th cha mt
lng Phtphat khng nhiu, lng ny s c xc nh nh "th nghim trng"
s ni phn sau.
Sau khi trng l v nt bng chnh nc bin cn ly, mu nc c
ly y vo l (ti thiu l 200 ml) v chuyn n vo phng th nghim mt thi
gian thch hp n c c nhit ca phng. Vic xc nh Phtpht cn
c tin hnh cng sm cng tt nhng khng c qu 6 gi k t khi ly
mu. Nu mu lu hn na th Phytoplankton trong mu c th thc hin
96
quang hp v tiu th Photphat, ng thi cng c th xy ra ti sinh Phtphat

t cc cht hu c trong mu. Nu khng th xc nh ngay trong vng 6 gi k
t khi ly mu th phi bo qun mu bng Clorofooc (thm 2 ml Clorofooc cho
1 lt mu) v t ni ti, nhit thp. Tuy nhin vic phn tch phi cng sm
cng tt.
Chun b lot mu phn tch
Trc ht lot mu nc phn tch c rt vo cc ng tr sch cho n
vch 100 ml, ng tr v nt ca n c trng 3 ln bng chnh mu nc cn
phn tch. Ghi s th t cc ng tr tng ng vi s hiu cc mu.
iu ch thang chun
Thang chun gm cc dung dch chun c nng Phtphat khc nhau v
c bit trc. Mi mt dung dch chun ca thang c iu ch bng cch
pha long 100 ln mt th tch nht nh dung dch chun lm vic (c nng
0,0025 mgP/l). V d, nu ly 0,2 ml dung dch chun lm vic pha long vi
nc bin khng Photphat thnh 100 ml th dung dch chun va nhn c c
nng 5 gP/l (hay l 5 mgP/m3); nu ly 0,4 ml - ta nhn c chun 10
gP/l; ly 0,6 ml - nhn c chun 15 gP/l; ly 1 ml - nhn c chun 25
gP/l v.v..
Vic pha long dung dch chun lm vic iu ch thang chun c
tin hnh nh sau: Dng Micro Pipet ly tht chnh xc nhng th tch thch hp
dung dch chun lm vic cho vo cc ng tr c vch mc 100 ml, sau b
sung nc bin khng Phtpht cho n vch.
c th so mu nhanh chng v chnh xc, nng ca thang chun cn
phi gn vi nng Photphat d kin ca mu phn tch. iu ny ph thuc
rt nhiu vo kinh nghim ca nghin cu vin. Thng thng, nng
Photphat ca mu nc bin vng nhit i t khi nm ngoi gii hn 0-60
gP/l, v vy nn chun b mt s dung dch chun thng gp nh 5, 10, 20, 30,
97
40, 50 v 60 gP/l.
To mu cho thang chun v lot mu phn tch
Thm ng thi vo mi mt ng tr cha mu nc phn tch v mi mt
ng tr ca thang chun mt lng 2 ml dung dch Amoni Molipdat trong Axit
Sunfuric v 2 git Thic Clorua. y nt cc ng tr li v khuy trn chng
bng cch o ngc. Khi dung dch c Photphat, mu xanh Molipen s hin
ln, cng ca mu t l vi nng Photpht trong cc dung dch. Trong
khong 5 pht k t khi khuy trn, mu s hin ln hon ton v n nh trong
vng 25-30 pht. Ta ch c php so mu ca chun v mu trong khong thi
gian ny. Sau thi gian n nh, mu ca c mu v chun u b bin i. V
vy, s lng mu trong lot mu chun b cn phi thch hp vic so mu
chng ch thc hin trong vng 25-30 pht.
Cn bng mu ca dung dch chun v mu
Vic so mu c tin hnh trong cp ng tr Hener. Trc ht, rt mt t
mu nc phn tch hin mu hon ton vo mt ng tr Hener, ng tr cn
li rt mt t dung dch chun c mu gn nht vi mu ca mu nc phn tch.
Cn bng mu ca chng bng cch cho chy t t qua van ca ng Hener dung
dch no c mu m hn (thng l mu nc), cho n khi mu 2 ng tr
nh nhau. Trong qu trnh cn bng mu, mt ngi phn tch lun nhn t pha
trn cc ng tr thng theo chiu dy cc dung dch.
Kt qu ch c chp nhn khi chiu cao ca cc cht lng trong hai ng
tr Hener khng khc nhau nhiu lm (khng c vt qu t l 1: 0,6-0,7).
Nu s khc nhau vt qu gii hn ny th phi thay th dung dch chun khc
c mu gn hn na vi mu ca mu.
Ghi kt qu so mu vo s chuyn mn bao gm chiu cao v nng
dung dch chun, chiu cao mu (theo s c trn thang chia ca ng Hener).
Sau ra sch cc ng Hener tip tc so mu mu khc. Trong trng hp
nng Phtphat ca cc mu trong lot mu chun b xp x nhau, tc l
mu ca cc mu gn tng t nhau th c th ch cn s dng mt dung dch
98
chun c mu gn nht vi mu ca mu.

Khi c nhiu mu cn phn tch, phi chia chng thnh tng lot ring bit.
S lng mu ca mi lot phi thch hp vic so mu c kt thc trong
vng 25-30 pht k t khi hin mu hon ton. Thm vo , mi mt lot mu
phi chun b mt thang chun mi (v mu ca thang chun cng ch n nh
trong vng 25-30 pht). Vic so mu c th thc hin di nh sng t nhin,
nh sng n Neon hoc n cao p thu ngn.
Th nghim trng
Nh ni trn, cc ho cht, nc ct hoc nc bin khng Phtphat
vn c th cha mt lng Phtphat no y. xc nh lng ny cn phi
thc hin "th nghim trng". Ly 100 ml nc ct cho vo mt ng tr, mt ng
tr khc cha dung dch chun c nng yu nht (thng l chun 0,5 P/l
hoc nh hn). Thm ng thi 2 ml Amoni Molipdat trong axit Sunfuric v hai
git Thic Clorua vo c hai ng tr k trn. Khuy trn u chng v khi cc
dung dch hin mu hon ton th tin hnh so mu trong cc ng tr Hener
nh m t. Ghi kt qu ca th nghim trng vo s.
Vi th nghim trng k trn, c th xc nh c lng Photphat c trong
nc ct v ho cht. Bng cch tng t c th xc nh c lng Photphat
c trong nc bin khng Photphat. Tng lng Photphat tm c trong th
nghim trng khng c vt qu 2-3 gP/l. Nu vt gi tr ny chng t cc
ho cht, nc ct, nc bin khng Phtphat l qu "bn", cn phi thay th
chng bng cc loi "sch" hn.
Ch :
- trnh phi a thm s hiu chnh nhit , vic so mu nn tin hnh
khi c s ng nht nhit ca mu v dung dch chun.
- nhng vng gn b v ca sng, nc bin thng b c hoc b
nhum mu vng do c cc ht ph sa. Trc khi phn tch cn phi ly ra cc
cht vn trong n bng cch lc mu qua phu lc c giy lc dy. Phu c
99
ra s b bng axit Sunfuric long (1:20) v sau trng li bng nc ct. Nu

sau khi lc, mu vn cn mu vng, chng t vn cn cc ht keo trong ,
ngi ta phi kt ta chng li bng cch thm 1ml H2SO4 8% v 1 ml BaCl2
10% cho mi mt 200 ml mu nc nghin cu. Mu ny c bt ng qua
2 gi, sau lc li n v tin hnh phn tch nh m t.
Xc nh s hiu chnh " bn"
Cn c vo s liu ca th nghim trng thc hin i vi nc ct, s hiu
chnh " bn" ca ho cht v nc ct c tnh theo cng thc:
Y = a.h1/h2
(4.2)
Trong Y l nng Photphat trong ho cht v nc ct, h1 - chiu cao

ct cht lng trong ng Hener cha dung dch chun c nng yu nht v a l
nng ca n, h2 - chiu cao ct nc ct c ho cht trong ng tr Hener.
Cn c vo s liu ca th nghim trng thc hin i vi nc bin khng
Photphat, s hiu chnh " bn" ca nc bin khng Phtphat l:
X = a'.h'1/h'2
(4.3)
Trong X l nng Photphat trong nc bin khng Photphat, h1' chiu cao ct cht lng trong ng tr Hener cha dung dch chun c nng
yu nht v a' l nng ca n, h2'- chiu cao ct nc bin khng Photphat c
ho cht trong ng tr Hener cn li.
" bn" tng cng c tnh theo cng thc:
Z=X+Y
()
Tnh ton nng Phtphat ca mu nc phn tch

Nng Photphat ca mu phn tch c k n cc s hiu chnh c tnh
theo cng thc sau:
P (gP/l) + Y = (C + Z).h/H
100
(4.5)
Trong P l nng Photphat ca mu nc (gP/l), C - nng dung

dch chun c chn ra so mu, h - chiu cao ca dung dch chun, H chiu cao ca mu nc, Z v Y bit.
Trong cng thc v 4.5, s hiu chnh " bn" ca ho cht v nc ct Y
ch c ngha nu c s chnh lch v chiu cao cc ct cht lng khi so mu
mu nc phn tch vi dung dch chun, ngha l h phi khc H t nhiu. Thc
cht l trong mu nc phn tch v trong dung dch chun u c mt lng
ho cht nh nhau, do nu c s trng hp mu sc khi chiu cao 2 ct cht
lng bng nhau (h=H) th nh hng ca " bn" Y b loi tr. Trong trng
hp ny gi tr ca Y cng thc v 4.5 "c xem" l bng 0 mc d theo th
nghim trng n vn c mt gi tr xc nh no y.
Nu cc dung dch chun lm vic v cc dung dch ca thang chun c
chun b ch bng nc ct (khng c nc bin khng Photphat) th trong cng
thc v 4.5 khng c mt gi tr X. Nhng trng hp ny phi a thm vo
cng thc 4.5 s hiu chnh theo mui ca mu nc. S hiu chnh ny (k
hiu l k) c tnh sn theo cc gi tr mui khc nhau v cho thnh bng
(bng 4.1). Khi , kt qu c tnh theo cng thc sau:
P (gP/l) = k[(C + Y).h/H - Y]
(4.6)
Bng 4.1: H s hiu chnh theo mui khi xc nh nng Phtphat trong nc bin bng
phng php so mu
S%o
0
k
1.00
S%o
8
k
1.18
S%o
16
k
1.25
S%o
24
k
1.31
S%o
32
k
1.34
1.04
1.19
17
1.26
25
1.31
33
1.34
1.05
10
1.20
18
1.26
26
1.32
34
1.35
1.09
11
1.22
19
1.27
27
1.32
35
1.35
1.11
12
1.23
20
1.28
28
1.32
36
1.35
1.12
13
1.23
21
1.29
29
1.32
37
1.36
1.14
14
1.24
22
1.29
30
1.33
38
1.36
1.16
15
1.25
23
1.30
31
1.33
39
1.37
101
4.2.7. Th t cng vic

Bc 1: Khi thun tin, chun b sn dung dch chun chnh KH2PO4, dung
dch H2SO4 50% v Amoni Molipdat 10%. Cc chai l, dng c cn c ty
ra sch v sy kh trc khi s dng.
Bc 2: Chun b dung dch Amoni Molipdat trong axit Sunfuric v dung
dch Thic Clorua nh m t.
Bc 3: Chun b dung dch chun lm vic KH2PO4 c nng 0,0025
mgP/l.
Bc 4: Lm cc th nghim trng v tnh ton kim tra ngay bn ca
ho cht, nc ct... Nu khng t yu cu (gi tr bn tng cng ln hn
3gP/l) th phi thay ho cht, nc ct khc.
Bc 5: Chun b lot mu phn tch (s lng va phi phn tch trong
vng 25-30 pht).
Bc 6:. Ly 100 ml mi mu nc nghin cu lot mu chun b cho
vo cc ng tr n vch mc 100, ghi li s hiu mu v s hiu ng tr.
Bc 7: iu ch thang chun gm 4 hoc 5 dung dch chun c nng
khc nhau nhng gn vi nng Phtphat d kin ca lot mu nc.
Bc 8: Thm ng thi vo mi mt mu v mi mt chun mt lng 2
ml Amoni Molipdat trong axit Sunfuric v 2 git Thic Clorua, y nt v
khuy trn chng bng cch o lc. Sau 5 pht mu ca c mu v chun hin
ln hon ton th tin hnh so mu.
Bc 9: So mu ln lt tng mu vi nhng chun c mu gn nht. Vic
so mu c thc hin cp ng tr Hener bng cch cn bng mu. Ghi li cc
kt qu so mu.
Bc 10: Cng vic c lp li t bc 5 n bc 9 cho lot mu khc;
c lp li t bc 2 cho ngy lm vic khc.
Bc 11: Tnh ton kt qu c th thc hin sau khi phn tch xong s mu
102
hoc sau ngy lm vic. Kt qu tnh phi c ngi th hai kim tra.
4.3. XC NH SILICAT TRONG NC BIN

mc 4.2.1 phng php xc nh Photphat ni r v nguyn tc xc
nh Silicat, y ch nhc li nhng nt c bn nht.
Trong nc bin, axit Silisic c th kt hp vi mt s phn t nc to
thnh hp cht phc tp hn (H8SiO6). Khi cho hp cht phc tp ny tc dng
vi Amoni Molipdat s to ra Heteropoliaxitsilisic H8Si(Mo2O7)6 nhum mu
vng. Dng cht kh c trng l mui Mor, Molipden ca Hetero-poliaxit ny
s b kh v sn phm c mu xanh Molipden.
Nhng thit b v dng c phn tch nc bin xc nh Silicat c
chun b nh khi xc nh Phtphat. Ch khc l cc bnh cha dung dch chun
chnh v chun lm vic cng mt s bnh cha khc phi trng Parafin bn
trong tr trnh s ho tan thu tinh.
Cc ho cht bao gm:
Dung dch Amoni Molipdat 10% v axit Sunfuric 50%
Hai dung dch ny c chun b nh khi xc nh Photphat. Ch khc l
chng khng c ho trn vi nhau thnh hn hp Amoni Molipdat trong
axit Sunfuric m lun c bo qun ring.
Nc bin khng c Silic
Ly nc bin khi tng mt v lc n qua mt phu s ln, trong phu s
c t t giy lc c ri mt lp Nhm xyt nung . Khi nc bin i qua
lp Nhm xyt ny, Silic ca n b gi li. Nc bin khng c Silic c cha
trong bnh trng Parafin hoc cha trong bi ng nhm.
C th dng nc ct thay cho nc bin khng c Silic, nhng khi tnh
103
ton phi c thm s hiu chnh theo mui.

Dung dch mui Mor (NH4)2Fe(SO4)2.6H2O
Ly 100 gam mui Mor kh v un nng va vi 400 ml nc bin khng
Silic. Sau thm vo 7 ml H2SO4 50%. Nu hn hp xut hin kt ta hoc
vn c ( l St xyt) th phi n lng ng v gn ly phn trong sut.
Phn trong sut c b sung thm 450 ml H2SO4 m c, tinh khit. Sau khi
dung dch ngui, th tch chung c nng ln thnh 2 lt bng nc bin
khng Silic.
C th chun b dung dch ny trong bnh cha thng nhng sau phi
bo qun n bnh trng Parafin
Dung dch chun chnh Natri Silicat Na2SiO3 (c th thay bng Na2SiF6)
Ly 1,0696 gam Thch anh (SiO2) tn nh vi 6 gam Xa (Na2CO3) kh
trong chn bch kim. un nng thn trng hn hp nhit cao cho n khi
thnh cht lng ng nht (khi un CO2 bay ln). Sau khi ngui, chuyn hn
hp vo bnh 1 lt v ra chn bch kim nhiu ln bng nc bin khng Silic.
Th tch cui cng ca dung dch l 1 lt. Bo qun dung dch ny trong bnh
trng Parafin. Dung dch c chun b nh trn c nng 500 mgSi/l.
Dung dch chun lm vic
Ly 10 ml chun chnh ho vi 90 ml nc bin khng Silic. Dung dch
ny c nng 50 mgSi/l. Dung dch chun lm vic ch chun b trc lc lm
vic v bo qun n trong bnh trng Parafin.
Nn s dng nhng l ng mu c mu xanh l cy (v thu tinh mu kh
ho tan hn). Trc khi ly mu, cn phi trng l vi ln bng chnh nc cn
ly. Mu phi c phn tch cng sm cng tt nhng khng c qu 12
gi k t khi ly mu. Mun mu lu hn phi a dung dch H2SO4 50%
vo mu vi t l 4 git cho 100 ml mu v bo qun n ni ti, nhit thp.
104
V Silic v c thng tn ti trong nc bin vi nng ln, c th ti
hng nghn gSi/l, nn c hai cch so mu p dng cho hai trng hp khc
nhau: trng hp th nht khi nng Silic ca nc bin ln hn 500 gSi/l
v trng hp th hai - nh hn. Vic nhn bit nh tnh gi tr ny v la chn
cch so mu thch hp ph thuc rt nhiu vo kinh nghim ca ngi nghin
cu.
Trng hp th nht: Khi nng Silic ca mu ln hn 500 gSi/l
- Chun b lot mu: Ly 100 ml mi mu nc cho vo cc ng tr c
vch mc 100 (ng tr phi c trng bng nc mu), ghi li s hiu ng tr
tng ng vi s hiu mu.
- iu ch thang chun: Thang chun trong trng hp ny phi c nng
ln hn 500 gSi/l v gn vi nng d kin ca mu. Nu ly 1 ml dung
dch chun lm vic (nng 50 mgSi/l) ho vi nc bin khng silic thnh
100 ml th nng ca chun ny l 500 gSi/l. Cn chun b thang chun c t
4-5 dung dch chun vi nng khc nhau nhng gn vi nng Silic d
kin ca mu.
- To mu cho chun v mu: Sau khi c thang chun, cho thm ng
thi vo lot ng tr cha mu chun b v cc ng tr c dung dch chun 4
git H2SO4 50% (nu khi ly mu nc thm H2SO4 bo qun mu ri th
lc ny khng phi cho thm axit vo mu na). Tip theo cho thm vo tt c
cc ng tr 2 ml Amoni Molipdat 10% v y nt cc ng tr li, khuy u
bng cch o lc.
- So mu ca mu vi chun: Sau 20 pht khuy o cc dung dch, mu
vng ca chun v mu hin r th tin hnh so mu cc ng tr Hener, ging
nh m t khi xc nh Phtphat. Kt qu so mu c ghi vo s. Tip tc
so mu mu khc cho ht s mu c trong lot mu chun b.
Sau khi phn tch ht lot mu, tip tc chun b lot mu mi v thang
105
chun mi phn tch vi quy trnh hon ton tng t.

y s dng mu vng lm c s so mu. Thc t mu vng ny l
mu ca c hai loi Heteropoliaxit c cha Silic v Phtpho (xem phn phng
php xc nh Phtphat, mc 4.2.1). Do kt qu nhn c sau khi tnh ton
phi c tr i gi tr nng Phtphat ca mu nc. Tuy nhin trong mt s
trng hp khi nng Silic ln hn nng Phtphat nhiu ln th c th b
qua php tr ny m vn khng nh hng n kt qu phn tch. mt s vng
bin, nht l cc vng bin ven b, ca sng... nng Silic v c c th t
trn mt vi nghn gSi/l trong khi nng Phtphat rt nh, c khi ch t
2-3 gP/l.
Trng hp th hai: Khi nng Silic ca mu nh hn 500 gSi/l.
trng hp ny, mu vng rt yu do nng Silic nh nn khng th s
dng mu ny lm c s so mu. ng nhin y phi iu ch thang
chun c nng nh. V d nu ly 0,5 ml dung dch chun lm vic pha
thnh 100 ml th chun ny c nng 250 gSi/l. Cn chun b thang chun c
t 4-5 dung dch chun nng khc nhau nhng gn vi nng Silic d kin
ca mu.
Sau khi chun b lot mu v thang chun, thm cc ho cht vo c mu
v chun ging nh cch th nht. Sau 3-5 pht cho thm 5 ml dung dch
mui Mor vo tt c chun v mu, y nt cc ng tr li v khuy u bng
cch o lc. Nm pht sau mu xanh Molipden hin ln v n nh trong vng
30 pht. Vic so mu cho ht lot mu cng c thc hin trong khong thi
gian ny, ging nh khi xc nh Phtphat. Trong trng hp ny (dng mui
Mor), kt qu nhn c sau khi tnh ton chnh l nng thc ca Silic trong
mu nc.
Sau khi phn tch ht lot mu chun b, tip tc chun b lot mu
mi v thang chun mi phn tch. Vi mc ch xc nh Silicat, khng cn
thc hin cc th nghim trng bi v nng Silic c trong ho cht, nc ct,
nc bin khng Silic nh b khng ng k so vi nng ca n trong nc
106
bin. Tuy nhin, nu mun t c chnh xc cao hn th phi lm th

nghim trng.
Nng Silicat xc nh bng phng php so mu bng mt c tnh
theo cng thc sau:
Si (gSi/l) = C.h/H
(4.7)
Trong C v h l nng v chiu cao ct dung dch chun trong ng tr

Hener, H - chiu cao ct nc phn tch trong ng tr Hener cn li.
Khi tnh ton kt qu cn ch nhng im sau y:
1. Nu s dng cch th nht phn tch (dng mu vng so snh) th
kt qu nhn c t cng thc trn phi tr i gi tr nng Phtphat ca mu
nc. Ch b qua php tr trong mt s trng hp khi nng Photphat khng
ng k so vi nng Silicat.
2. Khi cn t chnh xc cao tc l phi thc hin cc th nghim trng,
cng thc tnh ton cn phi c thm cc s hiu chnh cho " bn" ca ho
cht, nc ct v nc bin khng Silic. Dng cng thc tnh ton v ngha
cc s hiu chnh tng t nh khi tnh ton xc nh Phtphat.
3. Nu s dng nc ct (ch khng phi nc bin khng Silic) pha
ch cc dung dch th trong kt qu tnh ton phi c hiu chnh theo mui
ca mu nc. S hiu chnh ny c tnh sn theo cc gi tr mui khc
nhau v cho thnh bng c in trong cc ti liu chuyn mn.
4.4. XC NH NITRIT TRONG NC BIN

Phng php xc nh Nitrit (NO2-) trong nc bin da trn tnh cht ca
axit Sunfonic {(NH2)C6H4(SO2OH)} c th kh c Nitrit ca nc bin to
thnh hp cht c tn Fenildinitro-Sunfoniaxit. Phn ng c m t nh sau:
107
SO2(OH)
C6H4
SO2(OH)
HNO2
C6H4
NH2
+ H2O
N = NOH
(Axit Sunfonic)
(Fenidinitro-Sunfoniaxit)
Nu cho Fenidinitro-Sunfoniaxit tc dng vi - Naphtylamin (C10H7NH2)

th hp cht to ra sau s nhum mu . Cng mu t l vi nng
Nitrit ca dung dch. Phn ng c m t nh sau:
SO2(OH)
C6H4
SO2(OH)
C10H7NH2 C6H4
N = NOH
(Sunfoniaxit)
+ H2O
N = N - C10H6NH2
( )
(mu )
Phng php xc nh Nitrit theo nguyn tc trn c Gris a ra nm

1879 v c Iloxvai ci tin thm nm 1889, nn cn gi l phng php GrisIloxvai. Cho n nay phng php ny vn ang c ng dng trong nghin
cu ho hc bin nhiu nc trn th gii.
Nh bit, NO2- l sn phm trung gian ca qu trnh m ho t NH4+
n NO3- v do vy n rt bt n nh, c khi vng mt hon ton trong nc
bin. V vy, trc khi xc nh Nitrit cn phi lm php th nh tnh kim
tra s c mt ca n (php th nh tnh s c trnh by mc .4).
Tt c cc dng c, thit b xc nh Nitrit u c chun b ging nh
khi xc nh Phtphat. Cc ho cht bao gm:
Axit Axetic CH3COOH m c (dm c)
Axit Axetic 12%:
Ly 25ml Axt Axetic m c ho vi nc ct thnh 200ml.
Axit Sunforic (NH2)C6H4(SO2OH)
108
Ly 1 gam axit Sunfonic sch ho hc ho vi axit Axetic 12% cho 300

ml. C th chun b ho cht ny bng cch sau: ly 1 gam axit Sunfonic sch
ho vi 15 ml axt Axetic c v 15 ml nc ct, un nng hn hp trong khi
khng ngng khuy trn. Sau nng th tch ln 300 ml bng nc ct.
- Naphtylamin C10H7NH2
Ly 0,4 gam sch (c mu pht hng) ho vi vi git axit Axetic c ri
trn vi 300 ml Axit axetic 12%. Dung dch thu c phi trong sut, nu c
mu ti (c tp cht) th cn phi iu ch li n bng cch ly 0,4 gam ho
vi 20-30 ml nc ct, un nng hn hp cho n si. Sau khi ngui, tp cht s
ni ln trn mt dung dch di dng kt t mu tm xm. Lc ly phn trong
sut v ho n vi 300 ml axit Axetic 12%.
Hn hp Gris
Ho trn dung dch axit Sunfonic v - Naphtylamin chun b nh trn
theo t l 1:1. Hn hp Gris nhn c phi khng mu. Ch l c hai ho
cht axit Sunfonic v - Naphtylamin c chun b ring v bo qun trong
bng ti. Ch trc khi s dng mi ho trn chng vi nhau to thnh hn
hp Gris.
Dung dch chun chnh Natri Nitrit (hoc Kali Nitrit)
Ly 4,9270 gam NaNO2 kh sch ( c sy nhit 105-110oC cho
n trng lng khng i) ho vi nc ct thnh 1 lt. Sau cho thm 2
git Clorofooc bo v n. Dung dch ny tng i n nh v c th gi n
c 2-3 thng. i vi KNO2 th lng cn ly l 6,0770 gam. Nng Nitrit
(biu din qua nguyn t Nit) ca dung dch ny l 1 gN/l.
Dung dch chun trung gian
Pha long 100 ln dung dch chun chnh bng cch ly 1 ml chun chnh
ho vi nc ct thnh 100 ml. Nng dung dch chun trung gian l 0,01
gN/l hay 1 ml dung dch c 0,01 mg Nit. Dung dch ny c th gi c trong
7 ngy.
109

Pha long 10 ln dung dch chun trung gian bng cch ly 10 ml chun
trung gian ho vi 90 ml nc ct. Nh vy, 1 mililit dung dch chun lm vic
c 0,001 miligam Nit, hay nng ca n l 1000 gN/l. Dung dch chun lm
vic ch c chun b trong ngy lm vic
Nc bin khng c Nitrit
Nc bin khi tng mt thng khng c NO2- nn c th s dng ngay
n. C th dng php th nh tnh kim tra li (s ni phn sau).
Mu nc c th c ly trc tip t my ly nc vo cc ng tr dung
tch 100 ml cho ti vch mc nu vic phn tch c tin hnh ngay khng
lu qu 3-4 gi sau khi ly mu. Nu khng phn tch ngay c th mu nc
phi ly vo l c nt tht kn, cho vo mu 3-4 git Clorofooc v bo qun n
ni ti, nhit thp.
Bt u ngy lm vic cn chun b dung dch chun lm vic v ho cht
Gris nh m t.
Th nghim nh tnh
Ly 10 ml mu nc ho vi 1 ml Gris v hm nng hn hp 70-80oC.
Sau 10 pht em so mu vi chnh mu nc va ly (nhn bng mt). Nu c
Nitrit th mu nc c Gris s xut hin mu hng. Cng mu hng phn
nh tng i hm lng Nitrit ca mu nc.
Phn tch nh lng
- Chun b lot mu: Ly 100 ml mi mu nc cho vo cc ng tr c
vch mc 100. Ghi s hiu ng tr tng ng vi s hiu mu.
- iu ch thang chun: Dng Micro Pipet ly ln lt 0,2; 0,4; 0,6; 0,8 v
110
1 ml dung dch chun lm vic ho vi nc bin khng c Nitrit thnh 100

ml. Cc dung dch ca thang chun s c nng tng ng l 2, 4, 6, 8, 10
gN/l. Ta c th iu ch cc dung dch chun c nng khc vi cc gi tr
trn, sao cho n gn vi nng Nitrit d kin trong mu nc.
- To mu cho chun v mu: Sau khi mu nc v thang chun c cng
nhit th cho thm vo mi mt mu v mi mt chun 5 ml Gris, y nt cc
ng tr, khuy u dung dch bng cch o lc v bt ng chng trong
vng 1 gi. Sau thi gian ny mu hng s hin ln hon ton v ta c th tin
hnh so mu gia chun v mu trn ng tr Hener nh khi xc nh Phtphat
v Silicat. Ghi kt qu so mu vo s.
Khi phn tch ht s mu ca lot mu, tip tc chun b lot mu mi
v thang chun mi. S lng mu ca mi lot cn phi thch hp ch c
php so mu trong thi gian mu n nh.
Nu nc bin tng mt (hoc nc ct) dng chun b dung dch chun
v thang chun thc s khng c Nitrit th kt qu phn tch c tnh theo cng
thc:
NO2 (gN/l) = C.h/H
(4.8)
Trong NO2 l nng Nitrit ca mu nc biu din qua Nit nguyn

cht v H l chiu cao ca n trong ng tr Hener; C, h l cc ga tr tng t
ca dung dch chun trong ng tr cn li.
Nu nc bin tng mt (hoc nc ct) c Nitrit (c th kim tra qua php
th nh tnh) th phi thc hin th nghim trng nhm xc nh " bn" ca
n. Trong trng hp ny, cc cng thc xc nh " bn" v xc nh nng
Nitrit ca mu nc c dng tng t nh khi xc nh Photphat.
Nu s dng nc ct chun b dung dch chun th kt qu tnh ton
phi c hiu chnh theo mui. S hiu chnh ny c tnh sn v cho
trong cc bng hi dng.
111
4.5. XC NH NITRAT TRONG NC BIN

Phng php thng dng xc nh Nitrat (NO3-) trong nc bin l
phng php Diphenilamin. Khi cho Diphelinamin {(C6H5)2NH} tc dng vi
nc bin trong mi trng axit Sunfuric (H2SO4), n s b Nirat c trong nc
bin xi ho v sn phm to ra l mui Hynoit-Ymol (mt dn xut ca Hynoit
Dipheni-benzidin) c mu tm xanh. Cng ca mu t l vi nng Nitrat
trong nc. Qu trnh oxi ho Diphenilamin trong mi trng axit c m t
nh sau:
HC
CH
2 HC
H
C
HC = CH
HC
mt 2H+
CH
CH
HC = CH
Mi trng H2SO4
(Diphelinamin (C6H5)2NH)
HC - CH
HC
HC =CH H
C-N=C
HC=CH
HC CH
C=N-C
CH
HC=CH
HC =CH
H HC=CH
HC=CH
(Diphenibenzidin - khng mu)

mt tip 2H+
Mi trng H2SO4
HC - CH
HC
HC =CH
C-N=C
HC=CH
HC=CH
C = C
HC =CH
HC=CH
HC CH
C=N-C
O
HC=CH
O = S =O
Hynoit-Ymol - tm xanh
112
OH
CH
Nhiu cng trnh nghin cu bn cht cc phn ng xi ho-kh cho rng,

s xi ho bi cht xi ho l Nitrat ch xy ra khi mi trng c lng Clo.
Bi vy rt c th s xi ho Diphenilamin nh m t khng phi do chnh
Nitrat v axit Nitric (HNO3) m do Clo t do v axit Nitrit (HNO2) c to ra
trong cc phn ng trung gian sau y:
HNO3 + 3HCl NOCl + 2H2O + Cl2
NOCl + H2O HCl + HNO2
bn ca mu tm xanh ph thuc vo t s gia Diphenilamin v Nitrat
v ph thuc vo nng axit Sunfuric c mt trong phn ng. Bi vy, tt nht
l nn chn dung dch Diphenilamin v axit Sunfuric c nng cao trong khi
hm lng Nitrat ca nc bin rt khc nhau. Thc nghim chng t rng khi
t s ng lng Nitrat trn ng lng Diphenilamin cng gn n v th
mu cng xanh; nu Nitrat cng nhiu so vi Diphenilamin th mu cng tm
xanh hn.
Tc ph hu mu ngoi s ph thuc vo lng tha Diphenilamin cn
ph thuc vo nng axit Sunfuric c trong hn hp. Nu nng H2SO4
cng cao th mu cng bn vng. nhit cng cao, s hin mu cng sm. V
d 20oC mu tm xanh cc i hin ra sau 5-6 gi, sau mu c xanh dn i,
0oC mu t cc i khng sm hn sau hn 20 gi.
Cc cht xi ho khc nh Nitrit, Clorat, Bromat, Iodat, cc Peoxyt v
mui st u c th oxi ho c Diphenilamin v cho mu xanh. Nhng
trong nc bin, ch Nitrit l c hm lng ng k hn so vi cc cht nu trn.
Bi vy, phng php Diphenilamin cho ta kh nng xc nh tng nng
Nitrat v Nitrit ca nc bin. Tuy nhin, tc xi ho Diphenilamin bng
Nitrit ln gp nhiu ln so vi xi ho bng Nirat. C th nu xi ho bng
Nitrit th mu cc i xut hin sau khong 15 pht, trong khi nu xi ha
bng Nitrat th mu pht trin trong vng vi gi. V th khng nn tin hnh so
mu qu sm khi mu tm xanh do xi ho bng Nitrat cha n nh. Nu so
mu qu sm th c th ch xc nh c Nitrit l chnh.
113
Ngoi phng php Diphenilamin xc nh trc tip Nitrat nh nu trn,

hin nay phng php gin tip cng ang c s dng rng ri trong ho hc
bin. Nguyn tc ca phng php gin tip l kh ton b Nitrt c trong mu
nc cho n Nitrt bng ct Cadimi m ng (phng php ny y khng
trnh by), sau xc nh hm lng Nitrt ca mu (phng php xc nh
Nitrit c trnh by mc 4.4). Nh vy, hm lng Nitrt (biu din qua
lng Nit nguyn cht) trong trng hp ny chnh l tng hm lng Nitrat
v Nitrt. Ly tng ny tr i hm lng Nitrt thc ca mu ta c hm lng
Nitrat cn tm.
Cn phi la chn cn thn b ng nghim bng thu tinh khng mu,
ng knh nh nhau, c nt thu tinh mi. Nhng ng nghim ny dng
chun b thang chun v ng mu nc phn tch (khong 20-30 chic).
Ngoi ra cn phi c cc loi Pipet, cc bnh ong, bnh nh git...v cc
dng c thng thng khc. Cc loi Pipet v bnh ong phi c kim nh. Vi
trng hp xc nh trc tip Nitrat bng phng php Diphenilamin, vic so
mu c tin hnh theo cch ni suy bng mt tng t xc nh pH nn khng
cn s dng cp ng tr Hener.
4.5.3. Ho cht
Dung dch Diphenilamin trong axit Sunfuric
Ly 1 gam Diphenilamin ho vi 100 ml H2SO4 m c (t trng 1,84).
Sau ly 100 ml nc ct cho vo bnh ong c vch 1 lt, cho tip vo 5
ml dung dch Diphenilamin va chun b v rt tht cn thn axit Sunfuric m
c vo n vch mc. Xo trn chng bng que khuy thu tinh. Sau khi dung
dch ngui, b sung tip axit cho n vch v li xo trn chng.
Dung dch Diphenilamin rt bn vng v c th lu. Nu dung dch
chun b c mu xanh nht nhn bit th chng t trong n khng c cht
kh, nu n khng mu (c cht kh) th phi ci to li n.
114
Trc khi ci to phi kim tra nh tnh xem c thc s cn ci to hay

khng? Php kim tra nh tnh da vo mu ca thang chun m ta chun b
c vi s tham gia ca Diphenilamin "bn" (cch iu ch thang chun s
c ni phn sau). Nu trong vng 2-3 gi, mi dung dch ca thang chun
u hin mu th Diphenilamin vn s dng c xc nh Nitrat. Nu mt
hoc mt s no y dung dch ca thang chun phn nng nh khng hin
mu th phi thc s ci to li Diphenilamin.
ci to li dung dch, phi dng dung dch KNO3 mi iu ch (0,7 gam
KNO3 trong 1 lt nc ct). Thm ho cht ny cho mi mt 1 lt Diphenilamin
mt lng ng bng lng dung dch chun lm vic (cng l KNO3) c ci
chun u tin hin mu ca thang chun (tnh t u yu ca thang). V d, ta
iu ch c thang chun l 0,5, 1,0, 1,5, 2,0 v.v..., chun u tin hin mu
tnh t u yu ca thang l chun trong c 1,5 ml dung dch chun lm vic,
th phi thm 1,5 ml KNO3 mi iu ch cho mi mt lt dung dch
Diphenilamin cn ci to.
Dung dch chun chnh Kali Nitrat (KNO3)
Ly 0,3610 gam KNO3 sch, ho tan trong 500 ml nc ct. bo qun,
phi thm vo dung dch 15-20 git Thu ngn Clorua bo ho (c th thay bng
Clorofooc), nhng sao cho th tch ca n vn l 500 ml. Dung dch chun chnh
nhn c bng cch pha ch nh trn c nng 100 mgN/l v c th gi c
trong thi gian di.
Ly 1 ml chun chnh pha vi nc ct thnh 100 ml. Dung dch ny c
nng 1 mgN/l. Ch iu ch dung dch chun lm vic trong ngy lm vic.
Dung dch Natri Clorua 20%
Ly 20 gam NaCl sch c kt tinh ho vi 80 ml nc ct. Dung dch
ny nhm to ra ci "nn" Clo trong thang chun (s ni r mc iu ch
thang chun).
115
Dung dch bo ho Thu ngn Clorua (HgCl2)

Ly 2,5 gam HgCl2 ho vi 100 ml nc ct. Khi dung dch bo ho th
HgCl2 cn li s lng xung y bnh. Dung dch ny l cht c mnh i hi
phi tht cn thn khi s dng, vn chuyn v bo qun, bnh cha dung dch
phi c dn nhn ghi ch c. y l dung dch dng bo qun cc dung
dch chun v mu nc, tuy nhin c th thay th n bng Clorofooc nu khng
c HgCl2.
iu ch thang chun
Thang chun c iu ch t dung dch chun lm vic c nng 1
mgN/l. ong chnh xc bng Pipt cho vo cc bnh c vch mc 100ml nhng
lng dung dch chun lm vic nh sau: 0.5; 1.0; 1.5; 2.0; 3.0; 4.0; 5.0; 6.0;
7.0; 8.0 v 10 ml. Pipet phi c trng bng dung dch chun lm vic trc
khi ly n. Sau cho tip vo cc bnh ny mt lng dung dch NaCl 20%
thch hp, lng ny phi tng ng vi mui ca mu nc nghin cu. V
d khi mui ca mu nc l 10-12%o th phi thm 5 ml NaCl 20%, nu
mui l 32- 35 %o th phi thm 16 ml... Trong trng hp lot mu nc ly
ln c mui gn nhau th tt c cc chun ca thang u c thm cng mt
lng NaCl 20% tng ng vi mui ca mu.
Nu mu nc ly t bin ln c phn tch ngay, ngha l mu khng cn
phi bo qun th cc chun lc ny cng khng cn phi thm cc ho cht bo
qun, m b sung ngay nc ct cho n vch mc 100. Trng hp mu nc
khng c phn tch ngay (do cc iu kin khch quan) th mu phi c bo
qun bng Clorua thu ngn hoc Clorofooc (xem mc 4.5.4), lc ny bt buc
cc chun cng phi c bo qun bng chnh cc ho cht bo qun mu
nc. C th l, nh vo mi mt bnh ca thang chun 3-4 git dung dch
HgCl2 bo ho (hoc Clorofooc) sau b sung nc ct vo cho n vch mc
100. Trong c hai trng hp, sau khi b sung nc ct cn khuy trn u dung
dch cn thn bng cch o lc.
Thang chun c chun b nh trn s c nng tng ng l 5, 10, 15,
116
20, 30, 40, 50, 60, 70, 80, 100 gN/l. Khi phi chun b thang chun c nng
cao t 500 g N/l tr ln th c th iu ch n trc tip t dung dch chun
chnh. Thang chun ch chun b trong ngy lm vic, khng s dng n ngy
hm sau.
Ly mu xc nh Nitrt tng t nh ly mu xc nh Phtphat v
Silic. Mu c phn tch cng sm cng tt. Nu khng phn tch c ngay
trong vng 6 gi k t khi ly mu th phi bo qun mu bng cch thm 3-4
git Clorua thu ngn bo ho (hoc Clorofooc) cho 100 ml mu.
Bt u mt ngy lm vic, ta chun b dung dch chun lm vic v thang
chun nh m t. Tip chun b lot mu nc phn tch vi s lng
thch hp.
To mu cho chun v mu
ong tht chnh xc 2 ml mi mt chun ca thang chun (k t nng
nh n ln) v cho ln lt vo cc ng nghim sch kh. Pipet phi c
trng 2 ln bng chnh chun cn ly. Sau ong 2 ml mi mu nc cn phn
tch cho ln lt vo cc ng nghim sch v kh khc (Pipet cng phi c
trng bng chnh mu nc cn ly). Tt c cc ng nghim phi hon ton nh
nhau v trnh nhm ln, chng phi c nh s tng ng vi cc chun
v s hiu cc mu. Tht cn thn, thm tip 5 ml Diphenilamin vo tt c cc
ng nghim c dung dch chun v mu nc. Khuy trn hn hp trong cc
ng nghim bng que thu tinh ln lt t nng nh n ln. Trc que
khuy phi lun lun c gi trong ng nghim c y axit Sunfuric 3:2 (60
ml H2SO4 m c ho vi 40 ml H2O).
Nn chun b c chun s "0" vo mt ng nghim m ch c 2 ml
nc ct v 5 ml Diphenilamin. Chun s "0" dng xc lp hiu chnh "
bn" ca ho cht Diphenilamin.
117
Sau mt thi gian (vi ting), mu tm xanh Hynoit- Ymol trong cc ng

nghim s hin ln. Cng ti thi im ny c th bit c c cn phi ci to
li Diphenilamin hay khng? Nu phi ci to li ho cht th ton b cng vic
to mu cho chun v mu phi lm li t u vi s tham gia ca dung dch
Diphenilamin mi.
Cng mu so mu 18-20oC c pht trin trong 2-3 gi v n
nh trong khong 2 gi tip theo. Cc dung dch c nng Nitrat ln th mu
pht trin nhanh hn v c th so mu chng sau 2 gi k t khi to mu. Nhng
dung dch c nng Nitrat nh th phi sau 3 gi mi nn so mu. Khng nn
so mu sau 4 gi v lu hn, v lc ny mu b ph hu dn. Vi thi gian hin
mu nh trn nhit ca mu v chun nh nhau.
So mu ca mu vi chun
Vic so mu c tin hnh qua php ni suy bng mt hoc nh cc thit
b so mu nh my so mu quang in, ph quang k... Khi so mu bng mt,
ng nghim c nc nghin cu c t gia hai ng nghim chun c mu
gn nht (ging nh khi xc nh pH). p s c gii quyt bng php ni
suy. Ghi kt qu ni suy vo s chuyn mn.
Kt qu so mu bng php ni suy nh m t (hoc so mu trn cc thit
b so mu) c chp nhn lm kt qu phn tch Nitrt ca mu nc. Tuy
nhin cn ch l phng php Diphenilamin cho kh nng xc nh tng nng
Nitrat v Nitrit nu tin hnh so mu qu sm. V vy, kt qu cui cng
nhn c c th phi hiu chnh theo s c mt ca Nitrit trong mu.
4.5.7. Ch
Ton b cng vic xc nh Nitrat phi tun theo ng quy trnh ch dn,
vic ong o phi tht chnh xc, dng c v ho cht phi tht sch s. Cc ng
nghim cha dung dch ca thang chun v mu nc cn c ra cn thn
bng axit Sunfuric c (ngm trong axit t 5-6 ngy), sau sy kh. Nu
118
khng c my sy, cc ng nghim phi c y axit gia hai ln xc nh

lot mu.
4.6. S DNG THIT B SO MU XC NH CC HP PHN DINH
DNG TRONG NC BIN
4.6.1. Nguyn tc chung

Nh nu mc 4.1, hin nay Ho hc bin ang s dng rng ri cc
my v thit b so mu (nh my so mu quang in, ph quang k...). l cc
phng tin tr gip cho ngi phn tch lm vic t hiu qu cao hn. Phn
ny gii thiu nhng nt c bn nht v my so mu quang in (vi ph quang
k v cc thit b so mu hin i khc c th tm c trong cc ti liu chuyn
mn ti cc phng th nghim).
B phn quan trng ca my so mu quang in l t bo quang in. N
c nhim v ng mch in khi c nh sng chiu vo. Cng dng in
qua mch (th hin trn ng h o) t l thun vi cng nh sng chiu
vo t bo quang in. Km theo my cn c nhng Cuvet v knh lc. Cuvet l
mt cc thu tinh trong sut (thng c dng hnh hp hoc dng tr) dng
cha dung dch khi so mu. Knh lc sng c nhim v thay i cng nh
sng chiu vo dung dch ng trong Cuvet.
Theo nh lut c bn ca quang hc, nh sng chiu vo mt vt th trong
sut s c phn tch thnh cc thnh phn phn x, hp th v truyn qua.
Nhng thnh phn ny c mi lin h theo nh lut bo ton l:
I o = IP + Ih + It
(4.9)
Trong Io l cng dng nh sng ti (ngun sng), IP- phn x b

mt vt th, Ih -vt th hp th, It - truyn qua vt th.
Do ngun sng ca my l c nh, mt khc khi lm vic vi my so mu
quang in, ngi ta lun dng mt loi Cuvet nn dng phn x mt Cuvet
cng l c nh, dn n iu l cc dng Io v IP khng lin quan n s bin
i ca Ih v It. T suy ra cng dng truyn qua It ch ph thuc (t l
119
nghch) vo cng dng hp th Ih. Khi dng truyn qua It chiu vo t bo

quang in, mch in c ni lin. Cng dng in trn mch ph thuc
vo cng dng It v do vy n cng ph thuc vo cng dng Ih.
my so mu quang in, vt th c chiu sng chnh l Cuvet c cha
dung dch hin mu. Khi nh sng i qua lp dung dch, n s b hp th mt
phn (Ih) - phn ny t l vi cng mu ca dung dch, ngha l t l vi
nng cht tan trong dung dch, phn cn li (It) c a ti t bo quang
in. Nhng b phn khc nhau ca my c nhim v bin It (cng c ngha l
bin Ih) thnh tn hiu v th hin trn mt ng h. Gi tr m ng h biu
din gi l "mt quang hc ca dung dch". Hin nhin, mt quang hc
ca dung dch t l vi nng ca n.
Trong trng hp nng dung dch qu nh, tc l dng hp th Ih nh
th dng nh sng truyn qua It c th xp x bng dng nh sng ti Io. It ln
nh vy c th lm cho t bo quang in "qu ti". Trng hp ny phi s
dng knh lc gim bt Io, cng c ngha l gim bt It.
Nu o c mt quang hc ca dung dch cn phn tch nng , so
snh vi mt quang hc ca dung dch chun ( bit trc nng ) ta c th
d dng xc nh c nng ca dung dch cn phn tch.
S dng my so mu quang in xc nh nng cc nguyn t vi
lng trong nc bin rt tin li. N c th xc nh nhanh chng nng ca
dung dch, s lng mu phn tch trong mi lot mu cng nhiu gp bi so vi
vic so mu bng cc ng tr Hener. Thm vo , nhng sai st ch quan ca
ngi phn tch cng b loi tr.
Chun b lot mu, iu ch thang chun v to mu cho chng
Cc qu trnh ny c thc hin nh m t khi xc nh Phtphat,
Silic, Nitrit, Nitrat bng phng php so mu bng mt. Ch khc l do tc so
mu trn my nhanh hn nhiu so vi so mu trn ng tr Hener nn s lng
120
mu ca mi lot cng cn phi chun b nhiu hn phn tch trong thi

gian n nh mu, s lng dung dch chun ca thang chun cn t hn. Khi
mu ca chun v mu n nh th c th bt u so mu trn my.
o mt quang hc ca cc dung dch chun
Trc khi o mt quang hc ca cc chun, cn kim tra ngun in v
cc b phn ca my cn thn. Trng hp my chy "khng ti" m kim ng
h khng ch ng vch s "0", ta cn chnh li v tr ca kim bng mt s nt
chc nng ca my.
Sau khi kim tra my an ton v nhn thy mu ca chun v mu n
nh, ta rt mt dung dch chun vo Cuvet v t Cuvet ny vo v tr trn my,
bt cng tc my, ghi s c mt quang hc trn ng h v tt my. Lm li
ln na ly s c trung bnh. Ra sch Cuvet v tip tc o mt quang
hc ca dung dch chun khc.
o mt quang hc ca mu nc
Qu trnh c thc hin nh khi o mt quang hc cc dung dch
chun. Cn ch rng khi o mt quang hc ca chun m dng Cuvet v
knh lc no th khi o cho mu cng phi dng chnh Cuvet v knh lc . Tt
hn l khng nn nhc knh lc ra khi v tr ban u trong sut qu trnh xc
nh.
Xy dng tng quan chun D-C
y D l mt quang hc ca dung dch chun v C l nng ca n.
Trn mt phng to D-C (trc tung l D, trc honh l C), ta xc nh nhng
im c to D, C tng ng theo s liu o mt quang hc ca cc dung
dch chun. K ng thng trung bnh qua cc im ta c ng chun D-C.
V mt l thuyt, quan h D-C l tuyn tnh bc nht (ng thng), do vy
ch cn hai cp s liu D-C l ta c c ng thng chun v ng chun
ny s i qua mi im c to D-C khc nhau. Nhng do nhng sai s ngu
121
nhin nn cc im khng nm trn ng thng. V vy ta cn phi c nhiu

cp s liu D-C v thay cho vic k ng thng trung bnh qua cc im, ta s
xc nh ng chun bng phng php hi quy tuyn tnh bc nht. Phng
trnh biu din tng quan D-C c dng:
D = a.C + b
(4.10)
Trong a, b l cc h s tng quan.

ng thng xy dng t phng trnh tng quan 4.10 chnh l ng
chun D-C trung bnh. V mi mt lot mu c mt thang chun ring, ngha l
c mt ng chun D-C ring nn khng uc s dng ng chun ca lot
mu ny cho lot mu khc v ngc li.
Tnh nng cht tan ca mu nc
T gi tr o mt quang hc ca mu nc, cn c vo ng chun DC ca lot mu (hoc phng trnh hi quy 4.10) d dng tm c nng
cht tan ca mu. ng chun D-C c coi nh ton cho lot mu.
Tnh cc s hiu chnh
tm c s hiu chnh " bn" ca ho cht, nc ct v nc bin
khng c yu t xc nh, ta phi lm th nghim trng. Th nghim trng c
thc hin bng vic o mt quang hc ca nc ct c ho cht c trng,
hoc "nc bin sch" c ho cht c trng. T ng chun hoc phng
trnh tng quan, d dng xc nh c " bn" ca cc i tng trn.
4.6.4. Th t cng vic
Bc 1: Chun b lot mu v iu ch thang chun. Cn chun b c chun
s 0 xc nh cc s hiu chnh.
Bc 2: To mu cho thang chun v mu.
C hai bc ny c thc hin nh m t cc mc trc.
Bc 3: Khi mu ca chun v mu n nh th tin hnh o mt
122
quang hc cho tng dung dch chun v tng mu ca lot mu chun b. Ghi
kt qu o vo s chuyn mn.
Bc 4: Lp li t bc 1 cho lot mu khc v thang chun khc.
Bc 5: Vic tnh ton kt qu c thc hin sau khi phn tch ht lot
mu hoc sau ngy lm vic. Cn c bit ch l mi mt lot mu u c
thang chun ring ca n nn khng c s dng tng quan D-C ca lot mu
ny cho lot mu khc.
4.7. XC NH HM LNG CHT HU C TRONG NC BIN QUA
NHU CU XY HO HC (COD)

Trong nc bin c tn ti nhng hp phn v sinh c kh nng tiu th
kh xy ho tan bng cc phn ng ho hc. Ngun gc v hm lng nhng
hp phn ny trong nc bin rt khc nhau, bn cht v tnh cht ho hc ca
chng cng rt khc nhau v cn t c nghin cu. Chng hn, theo quan h
ho hc gia chng vi xy hoc mt s cht khc th i a s trong chng c
tnh kh, mt s li c tnh xy ho. Tuy nhin, d mang c trng no th
nhng hp phn ny cng vn c kh nng tiu th mt lng xy ho tan trong
nc bin. Tp hp nhng cht v hp cht c kh nng tiu th xy ho tan
nh trn to nn "nhu cu xy ho hc" ca nc bin (tc l kh nng tiu th
xy trong cc phn ng xy ho kh xy ra trong nc), k hiu l COD
(Chemical Oxygen Demand).
Nhng hp phn c kh nng tiu th xy trong nc bin bng con ng
ho hc nh nu thng c ngun gc l cc cht hu c, ch yu l nhng
hp cht phc tp v a dng ca Cacbon. Nh vy, nhu cu xy ho hc ca
nc bin c to nn ch yu do hp phn cht hu c c mt trong nc. Do
c th dng COD c trng nh lng cho hm lng ca hp phn ny.
Tuy nhin v i a s cc cht hu c c trong nc bin u mang c trng
kh nn COD ca nc bin ch yu c trng cho kh nng tiu th xy ho
tan trong qu trnh xy ho cc cht hu. Vi ngha , COD ca nc bin
123
c gi l " xy ho ca nc bin".
Ngun cung cp cc cht hu c cho nc bin ch yu l do qu trnh
phn hu tn tch hu c v cc sn phm ca qu trnh hot ng sng ca
ng thc vt bin, cc xc ng thc vt cht... Ngoi ra, cht hu c cn c
cung cp t cc dng lc a, t ngun nc thi ca cng nghip v sinh hot
(c bit l cng nghip ch bin c, giy v du la). Chnh v vy, COD ca
nc bin cn c coi l mt ch tiu ca nhim mi trng. Nghin cu
COD ca nc bin cng c ngha l nghin cu lng cht hu c trong bin,
l mt thng s quan trng trong vic tnh ton chu trnh chuyn ho vt cht
v nng lng trong h sinh thi bin.
4.7.2. Phng php xc nh COD nc bin
xy ho c ht cc cht hu c c trong 1 th tch nc bin, ngi
ta cho th tch nc bin y tc dng vi mt cht xy ho hot ng ho hc
cao. Tr s "nhu cu xy ho hc" ca nc bin c xc nh bng lng cht
xy ho tiu th trong qu trnh ny v biu din bng s miligam xy ca
cht xy ho .
Phng php xc nh COD ca nc bin theo nguyn tc trn c B.
A. Skopinshev xut nm 1948-1950 vi ni dung "xy ho nc bin bng
Kali Pemanganat" (cn gi l phng php Skopinshev). V nguyn tc, khi cho
KMnO4 tc dng vi cc cht hu c (trong nc bin) th Mangan ho tr 7 c
th chuyn thnh ho tr 4, 3 hoc 2 tu thuc vo iu kin ca mi trng xy
ra phn ng l axt, trung tnh hay kim.
Mn+7 + 3e- Mn+4 + e- Mn+3 + e- Mn+2
C th, nu mi trng l axt tnh (c nhiu H+) th Mangan7 ca KMnO4
s chuyn thnh Mangan2. V d phn ng gia KMnO4 v cht hu c l axt
Oxalic H2C2O4 xy ra trong mi trng axit nh sau:
2KMnO4+5H2C2O4+3H2SO4 K2SO4+2MnSO4+8H2O+10CO2
Hoc vit dng ion l:
124
2(MnO4)- + 5(C2O4)-2 + 16H+ 2Mn+2 + 8H2O

Nhng khng th s dng mi trng axit xc nh COD ca nc bin,
v trong iu kin nh vy cc mui Clorua vn c rt nhiu trong nc bin
cng b xy ho v gii phng Clo v do vy s tiu hao thm mt lng
KMnO4. Bi vy, nu hm lng Clo trong mu nc ln hn 0,3%o (ngng
ny cn nh hn nhiu so vi Clo ca nc bin) th xc nh COD ca
mu, ch c th s dng mi trng l trung tnh hoc kim yu. Mi trng
nc bin hon ton tho mn iu kin ny v pH ca nc bin ch dao ng
trong khong hp 7,6 n 8,4.
Trong mi trng trung tnh (hoc kim yu), phn ng gia Kali
Pemanganat v cht kh hu c c trong nc (v d nh H2C2O4) xy ra nh
sau:
2KMnO4 + 3H2C2O4 2MnO2 + K2CO3 + 5CO2 + 3H2O
(4.I)
phn ng ny : Mn+7 + 3e- = Mn+4

xc nh lng KMnO4 chi dng cho phn ng xy ho-kh cc cht
kh hu c ca mt th tch nc bin, u tin ngi ta a vo th tch y mt
lng xc nh dung dch KMnO4 c nng bit trc, gi l lng ban u
(phi c d). Sau khi phn ng xy ho-kh xy ra hon ton (tng tc ca
phn ng bng cch un si hn hp), ngi ta xc nh lng KMnO4 cn li.
Hiu ca lng KMnO4 ban u vi lng cn li s l kt qu cn tm.
Phng php tt nht xc nh lng KMnO4 cn li l phng php
chun It. Nu cho lng KMnO4 cn li tc dng vi KI trong mi trng
axit th It c gii phng. Phng trnh phn ng l:
2KMnO4 + 10 KI + 8 H2SO4 = 6K2SO4 + 2MnSO4 + 8H2O + 5I2
(4.II)
Xc nh c lng It t do ny cng c ngha l xc nh c lng

KMnO4 cn li. Lng It k trn c xc nh bng vic chun hn hp
phn ng 4.II bng dung dch Thyosunfit c nng bit trc, ging nh khi
xc nh xy ho tan (xem mc 2.1 chng 2). Th tch dung dch Thyosunfit
125
tiu hao trong qu trnh ny tng quan vi lng It t do phn ng 4.II v

do tng quan vi lng KMnO4 cn li.
vic tnh ton n gin, lng KMnO4 ban u a vo mu cng c
xc nh tng quan vi th tch dung dch Thyosunfit (s c ni r mc
4.7.6 chng ny). Do vy, hiu s gia lng dung dch Thyosunfit tng quan
vi lng KMnO4 ban u v lng dung dch Thyosunfit tng quan vi lng
KMnO4 cn li, s t l vi lng KMnO4 chi dng xy ho ht cc cht
hu c ca mu nc. S miligam xy c trong lng KMnO4 tiu hao trong
qu trnh ny nh lng cho COD ca mu nc.
4.7.3. Dng c v thit b
- Biuret dung tch 25 ml, tt nht l dng loi t ng xc lp vch s "0".
Biuret phi c kim nh km theo. C th dng Biuret phn tch xy ho tan.
- Pipet t ng 10 ml (1 chic), Pipet 100, 50 ml (mi loi 1 chic), Pipet
1ml (1 chic). Cc Pipet cng phi c kim nh.
- Bnh tam gic 250 ml, nt c nh s (6 chic).
- ng lm lnh dng lm lnh mu sau khi un si (6 chic). Dng ca
ng nh m t trn hnh 4.3.
Hnh 4.3: Bnh tam gic v thit b lm lnh
126
- L un in hoc n cn, bp du.

- Cc chai l v dng c thng thng khc.
4.7. 4. Ho cht
Dung dch 0,02N Natri Thyosunfit (Na2S2O3)
Dung dch ny cng cc dung dch chun xc nh h s hiu chnh
chun cho n (nh K2Cr2O7 0,02N hoc KH(IO3)2 0,02N...) v dung dch tinh
bt ch th mu c chun b nh phn xc nh xy ho tan (xem mc
2.1, chong 2).
Dung dch 0,02N Kali Pemanganat
Ly tht chnh xc 0,32 gam tinh th KMnO4 ho vi mt lt nc ct, nh
vy 1 ml dung dch c 0,16 mgO2. Trc khi s dng phi bt ng dung
dch trong bng ti 10 ngy, sau thn trng gt b cn mu sng. Dung dch
c bo qun trong bnh xm mu.
Dung dch Axit Sunfuric 1:3
Ly 25 ml H2SO4 m c (t trng 1,84) ho vi 75 ml nc ct, cho thm
vo vi git KMnO4 lm sch cht kh. Yu cu dung dch phi c mu
hng nht n nh.
Mui Kali Iotua (KI) kt tinh
Cn sn v gi thnh nhiu gi, mi gi 0,5 gam v bo qun n ch kn.
C th s dng ngay dung dch KI 10% thay cho cc gi KI ny.
L ly mu nc bin xc nh COD cn phi sch v c nt kn. Trc
khi ly mu phi trng l 2-3 ln bng chnh nc cn ly. Vic xc nh phi
cng sm cng tt v khng nn qu mt ngy m.
4.7.6. Qa trnh xc nh
Kim tra chun dung dch Thyosunfit
127
Cng vic ny phi thc hin mi ngy mt ln trc lc xc nh COD.

Qu trnh kim tra chun v xc nh h s hiu chnh chun ca dung
dch Thyosunfit c thc hin nh khi xc nh xy ho tan (xem mc 2.1,
chng 2).
Xc nh tng quan Thyosunfit - Kali Pemanganat
V nguyn tc, ta bit trc lng KMnO4 ban u a vo mu. Nhng
v lng KMnO4 cn li c xc nh theo th tch Thyosunfit nn cho n
gin vic tnh ton kt qu, lng KMnO4 ban u cng c xc nh theo th
tch Thyosunfit (xem phn phng php xc nh). Cng vic ny phi c
thc hin mi ngy mt ln trc lc xc nh COD ca lot mu nc.
Cho vo bnh tam gic 0,5 gam KI kt tinh (hoc 5 ml dung dch KI 10%),
100 ml nc ct v 2 ml H2SO4 1:3. Sau dng Pipet kim nh (tt nht l
loi t ng) ly tht chnh xc 10 ml dung dch 0,02N KMnO4 cho tip vo
bnh tam gic. Khi phn ng 4.II gii phng It xy ra. Dng Thyosunfit
kim tra nng chun hn hp k trn. Trong qu trnh chun khng
ngng o lc bnh ho trn hn hp. Trc khi gn kt thc, cho vo hn
hp ang b chun 1 ml dung dch tinh bt, cht lng s c mu xanh lam.
Tip tc chun hn hp tht cn thn cho n mt mu hon ton. Ghi s c
trn Biuret vo s chuyn mn.
Xc nh COD ca mu nc
Ly chnh xc 100 ml mu nc (bng Pipet 100ml) v 10 ml dung dch
0,02N KMnO4 cho vo bnh tam gic, c bnh c y bng ng lm lnh c
vng m thu tinh (hnh 4.3). un si hn hp tng tc phn ng, thi
gian si ng 10 pht. Nh vy phn ng 4.I xy ho cc cht hu c trong mu
xy ra hon ton. Sau lm ngui hn hp ng 30 pht trong chu lm
lnh cho n nhit phng.
Mu nc sau khi lm ngui s c mu tm hng hoc tm xanh. Khi , tt
c cc cht kh hu c c trong mu nc u b Kali Pemanganat xy ho ht.
By gi ta cn xc nh lng KMnO4 cn li.
128
Ngay sau khi lm ngui, ngi ta cho vo mu mt gi KI (0,5 gam) cn

sn v 5 ml dung dch H2SO4 1:3. Khi lng KMnO4 cn li s phn ng vi
KI trong mi trng axit gii phng It nh thy phn ng 4.II. Ngay
lp tc chun hn hp ny bng dung dch Thyosunfit kim tra chun
v xc nh tng quan, cho n khi hn hp c mu vng nht th cho vo
1 ml dung dch tinh bt, dung dch s c mu xanh lam. Tip tc chun
hn hp n khng mu. Ghi s c trn Biuret vo s.
Nu sau khi lm ngui, mu c mu nu hung chng t hm lng cht
hu c trong mu ln hn d on, n ni lng 10 ml dung dch KMnO4
0,02N a vo mu khng xy ho chng. Cn phi lm li vi qui m
ln hn: ly chnh xc 50 ml mu cng 50 ml nc ct cho vo bnh tam gic
(ch khng phi ly 100 ml mu na). Lng cc ho cht khc a vo mu v
qu trnh chun hon ton nh m t.
V trong nc ct cng c th cha cht hu c nn cn phi lm th
nghim kim tra, trong coi nc ct nh nc mu v ta cng xc nh "COD
ca nc ct" nh i vi mu.
php xc nh COD c chnh xc, cn tun th nhng im sau:
- Bnh tam gic phi c ra tht k v trc mi ln dng phi c
trng cn thn bng nc ct.
- Bp phi c li st y bnh nng u v phi iu chnh c sao
cho trong vng 3-5 pht k t khi bt u un th mu nc si, trong khi nc
si ngn la khng nn qu mnh trnh nc bn tung ln. Thi im si
c tnh t khi bt u xut hin cc bng hi. Thi im ny cn c ghi li
v phi theo di ng h ng 10 pht sau khi si th bt u lm lnh mu.
Thi gian lm lnh 30 pht.
xy ho ca nc bin c tnh theo cng thc sau:
129
COD(mgO2 / l ) =
8.(a b).N .K .1000

V
(4.11)
Trong , 8 l trng lng ng lng ca xy; a- th tch dung dch

Thyosunfit s dng trong php xc nh tng quan; b- th tch dung dch
Thyosunfit s dng khi chun mu nc; N- chun ca dung dch
Thyosunfit; K- h s hiu chnh chun; V - th tch mu nc ly phn
tch.
130
TI LIU THAM KHO CHNH
1. on B,1990, Gio trnh Ho hc nc t nhin. NXB i hc Tng hp

H Ni, 149 tr.
2. Lu Vn Diu, 1996, Nghin cu c im thu ho v cht lng nc
vng bin ven b Qung Ninh-Hi Phng (t vnh H Long n bn o
Sn). Lun n PTS, HTH H Ni, 158 tr.
131

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HA HC BIN

Cc phng php phn tch ha hc nc bin

NXB i hc Quc gia H Ni 2001

Ti liu trong Th vin in t i hc Khoa hc T nhin c th c s dng

NH XUT BN I HC QUC GIA H NI

CHNG31. XC NH CC THNH PHN CA H CCBNT TRONG NC

4.4.5. Tnh ton kt qu ................................................................................................ 111

Gio trnh ny trnh by mt s phng php ho hc chun v thng dng

1.1.1. Gii thiu chung

Nhc im chung ca mt s my v thit b xc nh mui nc bin

Cng cn ni thm l, mc d Hi dng hc hin nay s dng cc thit

nc b mt i dng l 19,3534 g/kg).

0= 0,068 + 1,4708Cl - 0,00157 Cl + 0,000398 Cl

Ngoi cng thc nu trn, nhng nm sau ny mt s tc gi cn xy dng

Bit c th tch dung dch AgNO3 s dng kt ta ht cc halogen

trnh kt ta cc halogen thc s kt thc. Phn ng thu gn ca qu trnh hnh

C hai im cn ch khi s dng phng php Knudsen:

n 5 lit), np bng cao su.

PHNG TH NGHIM HO HC BIN

NC BIN TIU CHUN

Hnh 1.1: Ampun nc bin tiu chun

Dung dch Bc Nitrat (AgNO3)

do nhit thay i lm dn n th tch nc trong l. Khi chuyn mu i xa

dung dch Bc Nitrat. Lc u c th m to van Biuret dung dch Bc

15 ml nc bin tiu chun, ni cch khc, dung dch qu m c. Vy lng

+ Trng hp <-0,150 (A ln so vi N): iu ny chng t dung dch qu

Trong c 2 cng thc trn, V0 l th tch dung dch iu ch lc ban u, VT

cc ton lp sn tm c nhanh chng s gam AgNO3 hoc s mililit

phi np nc ct vo y Pipet v np dung dch AgNO3 vo y Biuret, sau

Sau khi tm c s hiu chnh k, Clo ca mu nc c xc nh theo

Dng cng thc (1.1), (1.2) c th tnh c mui v t trng ca mu

Bc 4: Sau khi trng Pipet bng chnh nc mu phn tch, ly 15 ml

1.2.1. Gii thiu chung

1.2.2. Phng php xc nh

Dung dch Bc Nitrat loi 1: mi mililt dung dch tng ng vi 2,5 mg

Trong [Cl-] l hm lng ion Cl- c trong 1 ml dung dch chun, V - th

Trong , n l s c trn Biuret v n l s hiu chnh ca n; V- th tch

sau khi chun l 21,20 v hiu chnh Biuret ng vi s c ny l +0,04. Vy

2.1.1. Gii thiu chung

Bng 2.1. Nng bo ho (mlO2/l) kh xy ho tan

Ngy nay ngnh Hi dng hc c cc my hoc thit b o trc tip

Mangan2 hydroxuyt l mt cht kh mnh s phn ng ngay vi xy t do

phn ng ny Mangan2 chuyn thnh Mangan4, cn xy phn t

R rng lng It t do c to ra phn ng ny t l vi lng

(Na2S2O3) c nng bit trc chun hn hp phn ng 2.III, khi

Nu bit th tch dung dch Na2S2O3 chi dng phn ng ht vi lng

hng ca kh H2S s c trnh by mc 2.2 chng ny). Tuy nhin, kh

- Ngoi cc dng c nu trn cn phi c cc loi bnh nh mc hnh cu,

c nt cao su kn, qua nt cm c Pipet. Vch du 1 ml ca Pipet phi lun

Dung dch tinh bt 0,5%

tra chun ca Thyosunfit (xem mc 2.1.6: Qu trnh xc nh). Bi vy ho

m t, ch khc l ly 2 ml HCl 2:1 (ch khng phi 10 ml H2SO4 1:4) v chun

Trong a1 l th tch Pipet ly dung dch chun (15 ml), 1 - s hiu

s c khong 5ml nc mu b y ra khi l (ng nhin lng nc b y ra

Trong DO (Dissolved Oxygen) l nng kh xy ho tan trong nc

mt mililit xy iu kin chun (T=0oC, P =760 mm Hg). Trong cng thc

Trong bng hi dng ca Zubov thnh lp nm 1957 v cc bng hi

Trong O2' l nng bo ho kh xy ho tan (ml/l) iu kin cho

mui v nhit ca mu nc ti thi im ly mu (in situ). Gi tr O2' c

2.1.8. Th t cng vic

2.2.1. Phng php xc nh

Nh vy, ton b lng H2S v cc dng kh khc ca Lu hunh c trong

HgI2 + 2KI (d tha) = K2(HgI4)

Cc thnh phn c to ra trong 2 phn ng ph ny khng nh hng ti