CHNG 7

PHNG PHP PHN TCH CHUN

7.1 Tng quan
Phng php chun c gii thiu bi nh bc hc Gay-Lussac (1778 1850). Phng
php chun l phng php phn tch nh lng trong l s o chnh xc th tch ca
dung dch c nng xc nh phn ng ho ton vi cht cn phn tch. S chun
c thc hin bng cch thm t t mt dung dch chun vo dung dch c cha cht cn
cn phn tch bng buret cho n khi nhn thy phn ng xy ra hon ton thng qua cht ch
th. Phng php chun c s dng rng ri trong phn tch v nhanh chng v n gin.
7.2 Mt s khi nim
im tng ng
im tng ng l ti 1 ng lng ca cht chun tc dng hon ton vi 1 ng
lng ca cht cn phn tch. im tng ng l im l thuyt, khng th xc nh bng
thc nghim.
im kt thc (im dng chun )
L thi im gy ra s bin i tnh cht vt l hay s bin i mu ca cht ch th. Thng
c s sai bit v im tng ng v im dng chun , ngi ta gi l sai s chun .
Mc sai s ph thuc vo chnh xc ca buret chun , xc nh im dng chun
ca ngi chun .
Cht ch th
Cht ch th l cht c thm vo dung dch khi tin hnh chun nh lng. S thay i
v pH, th oxy ho kh s lm thay i mu ca ch th. Cc ch th thng dng trong
phn tch mi trng nc:
Ch th ni: l ch th cho vo dung dch trong qu trnh nh lng v d: ch th mu Methyl
dacam, phenolphthalein, h tinh bt.
Ch th ngoi: l ch th ngoi dung dch nh a thu tinh ly dung dch ri cho tc dng
vi thuc th, giy tm h tinh bt Cc loi ny t c dng trong phn tch cc ch tiu
cht lng nc trong ao nui thu sn.
Chun trc tip
Cht cn phn tch phn ng trc tip vi cht chun (dung dch chun ). V d: phn
tch cht A, ngi ta thm cht B c nng xc nh. Qu trnh chun to thnh cht AB.
im dng chun c xc nh thng qua s chuyn i mu ca cht ch th.
Chun gin tip
Phng php ny cng thng c p dng trong vic phn tch cc ch tiu cht lng
nc. Cht chun khng phn ng trc tip vi cht cn phn tch m cht chun s
phn ng vi cht trung gian c phng thch ra hoc cn d li sau phn ng.
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V d: trong phn tch oxy ho tan ta khng chun trc tip O2 trong mu m ta chun
hm lng I2 c phng thch vi cht chun l Na2S2O3 v ch th l h tinh bt.
7.3 Phn loi
7.3.1 Phng php trung ho
Phng php ny thng c dng nh lng cc acid, base trong mi trng nc nh
cc ch tiu CO2, acid, kim ca nc
V d: dng NaOH xc nh hm lng CO2 trong nc. Mt ng lng NaOH s tc
dng vi 1 ng lng CO2 trong nc.
NaOH + CO2

NaHCO3

7.3.2 Phng php chun oxy ho kh

Da trn phn ng oxy ho kh tng ng vi s trao i electron gia hai cht, mt cht
cho v mt cht nhn. Cc ch tiu cht lng nc t s dng phng php ny.
7.3.3 Phng php kt ta
Da trn phn ng ca cht cn phn tch vi thuc th to thnh cc hp cht t tan. Cc ch
tiu cht lng nc cng t s dng phng php ny.
7.3.4 Phng php chun to phc
Da vo phn ng to thnh phc cht. V d nh phng php chun complexon trong
xc nh cng ca nc.
7.4 K thut phn tch
7.4.1 Phng php xc nh CO2 t do trong nc
Nguyn l
CO2 t do phn ng vi NaOH hoc Na2CO3 to thnh NaHCO3. Phn ng xy ra hon ton
c xc nh bng ch th in th hoc s to phc mu hng vi ch th phenolphthalein
pH tng ng 8,34.
2NaOH + CO2

Na2CO3 + CO2

+ H2O 2NaHCO3

Na2CO3 + H2O

Nh vy, c 2 cch xc nh CO2 t do l chun bng NaOH hoc Na2CO3 vi ch th l

phenolphthalein im dng l pH = 8,3, khi dung dch chuyn t khng mu sang mu
hng.
Cc cht gy nhiu
Cc cation v anion gy nh hng n cn bng CO2-CO32-. Cc ion kim loi b kt ta trong
dung dch kim nh nhm, chronium, ng, st l tng kt qu phn tch, Fe2+ khng c
vt qu 1 mg/L. Cc ion kim yu nh ammonia hay amine, cc mui ca acid yu hay baz
mnh nh borate, nitrite phosphate, silicate v sulfide gy nhiu dng (tng kt qu phn
tch). Cc cht ny khng nn vt qu 5% ca hm lng CO2. Phng php chun
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khng p dng cho nc thi c cha acid khong. Tng cht rn ha tan (TDS) cao s gy
nhiu m (gim kt qu phn tch), c bit l nc bin.
Tnh kt qu
CO2 t do

Vtb N
44 1000
Vm

mg / L

Trong :
-

Vtb: l th tch trung bnh dung dch NaOH 0,01N s dng chun .

N: l nng ng lng ca dung dch NaOH s dng.

44: ng lng gram ca CO2.

Vm: th tch nc em chun .

1.000 h s i ra mg.

7.4.2 acid (acidity)

Nguyn l
Ion H+ hin din trong nc t qu trnh phn ly hoc thy phn cc cht c xc nh bng
phn ng vi cht kim chun bng k thut chun trc tip. pH ca nc thp hn 4,5 do
cha cc acid khong mnh, c th xc nh bng cch chun vi cht kim chun l
NaOH hoc Na2CO3 im dng ca ch th methyl da cam (pH = 4,5). Carbon dioxide (CO2)
gy nn tnh acid pH trong khong 4,5-8,3, c th xc nh bng cch chun vi cht
kim chun im dng ca ch th phenolphthalein (pH=8,3). Nh vy, acid khong
c xc nh bng cch chun ti im dng ca ch th methyl da cam v tng acid
c xc nh bng cch chun baz ti im dng ca ch th phenolphthalein ( acid
khong + acid carbon dioxide). acid c tnh bng n v mg CaCO3/L.
Cc cht gy nhiu
Cc kh ha tan gp phn to nn tnh acid nh CO2, H2S, NH3 c th b mt hoc tng thm
trong qu trnh thu mu, bo qun v chun . hn ch iu ny cn thc hin chun
ngay lp tc sau khi m np mu nc, trnh lc hay thay i p sut v tng nhit ca
mu nc. Mu nc c cha cc cht d b oxy ha hay d b thy phn nh Fe, Mn, Al lm
chm tc phn ng dn n sai lch im dng. Khng dng phng php chun cho
mu nc c mu hay b c v kh xc nh ng im dng chun . D lng Cl2 trong
mu nc c th lm mt mu ca cht ch th, thm 1 git Na2S2O3 0,1N kh Cl2.
Tnh kt qu

M mgCaCO3 / L
T mgCaCO3 / L

VM N 50 1000
Vm

VT N 50 1000
Vm

Trong :
T v M l acid tng cng v acid khong
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 VM v VT l th tch trung bnh dung dch NaOH chun (mL).

N: l nng ng lng ca dung dch NaOH chun .
50 l ng lng ca CaCO3
Vm l th tch mu nc (mL)
1000 l h s i ra mg.
7.4.3 kim (alkalinity)
Nguyn l
Lng acid chun trung ha baz trong nc dng xc nh kim bng k thut
chun trc tip. Cc cht gy kim bao gm HCO3-, CO32-, OH-, SiO32-, PO43-, NH3 v mt
s cht hu c khc, nhng HCO3-, CO32-, OH- chim phn ln trong tng kim. Nc
c pH > 4,5 c th cha HCO3-, nc s c mu vng vi ch th methyl cam (methyl orange).
Nc c mu hng vi ch th phenolphthalein khi trong nc c cha CO32- hoc OH- (pH >
8,3). Do , kim tng cng v kim ca cc thnh phn c xc nh qua 2 bc:
Bc 1, chun acid vi im dng (im tng ng) ca ch th phenolphthalein (pH =
8,3); Bc 2, chun acid vi im dng ca ch th methyl da cam (pH = 4,5). Phn ng
xy ra qua cc bc chun nh sau:
CO32- + H+ HCO3HCO3- + H+ H2O + CO2
Tnh kt qu

VT N 50 1000
Vm
V N 50 1000
P mgCaCO3 / L P
Vm

T mgCaCO3 / L

Trong :

T v P l kim tng cng v kim phenolphthalein

VP v VT l th tch trung bnh dung dch H2SO4 hoc HCl chun (mL).
N: l nng ng lng ca dung dch H2SO4 hoc HCl.
Vm l th tch mu nc (mL)

7.4.4 cng (hardness)

Nguyn l
Tng hm lng Ca2+ v Mg2+ tnh bng n v CaCO3 l tng cng ca nc. Eriochrome
Black-T (C20H13O7N3SNa) c s dng lm cht ch th xc nh im dng chun ,
Eriochrome black-T kt hp vi ion Ca2+ v Mg2+ hnh thnh phc cht khng bn vng c
mu hng ca ru vang. Khi dng EDTA chun trong mi trng pH=10, cc ion Ca2+ v
Mg2+ s kt hp vi EDTA hnh thnh phc cht khng mu v bn vng, phn ng s gii
phng Eriochrome Back-T t do, dung dch c mu xanh l.
M2+ +

M-E.B.T

Na2H2Y Na2MY

2H+ +

E.B.Tt do
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(Mu hng)

(Mu xanh)

im dng chun cng r khi pH cng cao, nhng khng th tng pH qu cao bi v
CaCO3 s b kt ta. Trong qu trnh chun H+ c to thnh lm gim pH, do dung
dch m NH4Cl-NH4OH c s dng gi pH n nh.
Khi c s hin din ca ion Mg2+ th im dng chun s r rng, m bo iu ny
mt lng nh mui MgEDTA c thm vo dung dch m.
Cc cht gy nhiu
Cc ion kim loi thng gy nhiu lm m hoc khng phn bit s thay i mu ca ch th
ti im dng chun hoc tiu th EDTA. Cc cht thng gy nhiu nh: Al, Ba,Cd, Co,
Cu, Fe, Pb, Mn, Ni, Sr, Zn, polyphosphate. gim hin tng gy nhiu, thm 250mg
NaCN hoc 50 mg Na2S.9H2O vo mu nc trc khi chun . Nu hm lng kim loi
qu cao th khng dng phng php chun EDTA o cng.
Tnh kt qu

H mgCaCO3 / L

Vtb N 50 1000
Vm

Trong :
H l cng tng cng
Vtb l th tch trung bnh dung dch EDTA chun (mL).
N: l nng ng lng ca dung dch EDTA.
Vm l th tch mu nc (mL)
7.4.5 Oxy ho tan (DO) trong nc
Nguyn l
Trong mi trng baz mnh, oxy ha tan (DO) trong nc s oxy ha ion Mn2+ thnh Mn4+
to kt ta nu.
Mn2+ + 2OH- + O2 MnO2 + 2H2O
Trong mi trng acid v c s hin din ca ion I-, Mn4+ b kh thnh Mn2+ v gii phng I2
tng ng vi lng O2 c trong mu nc lc ban u.
MnO2 + 2I- + 4H+ = Mn2+ + I2 + 2H2O
I2 c gii phng ra s ha tan trong nc v c xc nh bng phng php chun vi
dung dch Na2S2O3. H tinh bt c s dng lm cht ch th xc nh im dng chun
(I2 to phc mu xanh vi h tinh bt).
I2 + Tinh bt-I2 (xanh) + Na2S2O3 Na2S4O6 + NaI + H2O + Tinh bt (khng mu)
Cc cht gy nhiu
Cc cht oxy ha s oxy ha I- thnh I2 lm tng kt qu phn tch (nhiu dng). Cc cht
kh th kh I2 thnh I- lm gim kt qu phn tch (nhiu m). Hu ht cht hu c b oxy ha
trc khi M4+ b kt ta. Theo APHA et al. (1995), phng php wincler c mt s sa i
loi b cc cht gy nhiu: (i) Phng php dng NaN3 (4500-O C. Azide modification)
loi b cc cht oxy ha nh NO2-; (ii) Phng php x l mu nc vi KMnO4 v K2C2O4
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(4500-O D. Permanganate modification); (iii) Phng php x l mu nc vi

KAl(SO4)2.12H2O v NH4OH (4500-O E. Alum flocculation modification) loi b vt cht
l lng trong mu nc Trong cc phng php Wincler sa i th phng php dng
NaN3 l thch hp phn tch nc ao.
Tnh kt qu
Tnh hm lng CO2 t do theo cng thc sau:

DO mg / L

Vtb N 8 1000
Vm

Trong :
Vtb l th tch trung bnh dung dch Na2S2O3.
N l nng ng lng ca dung dch Na2S2O3.
Vm l th tch mu
7.4.6 Xc nh COD (Chemical Oxygen Demand)
Nguyn l
Hu ht cht hu c b oxy ha bi Cr2O72- v acid sulfuric trong iu kin un nng. Mu
nc c hon lu trong dung dch acid mnh v mt lng tha Cr2O72-.
Cht hu c + Cr2O72- + H+ Cr3+ + CO2 + H2O
Sau khi cng ph, lng Cr2O72- tha c chun vi Fe(NH4)2(SO4)2.6H2O (ferrous
ammonium sulfate - FAS) xc nh lng Cr2O72- tham gia phn ng, cht hu c b oxy
ha c tnh bng n v oxy (mg O2/L).
6Fe2+ + Cr2O72- + 14H+ 2Cr3+ + Fe3+ + 7H2O
Cc cht gy nhiu
Mt s cht bo mch thng bay hi s khng b oxy ha v khng tip xc vi cht oxy ha
(K2Cr2O7). Do , nu dng phng php cng ph h s dn n sai s. Phng php cng
ph h c th chp nhn khi hm lng COD trong mu nc ln hn 50 mg O2/L. i vi
mu nc c hm lng COD nh hn 50 mg O2/L phi dng phng php cng ph kn v
s dng Ag2SO4 lm cht xc tc lm tng hiu qu oxy ha.
Mu nc l, mn c cha ion Cl-, dichromate s oxy ha ion Cl- dn n sai s khi phn tch.
Hn na ion Cl- s phn ng vi Ag2SO4 to nn cht kt ta lm gim hiu qu xc tc ca
Ag2SO4.
cn ion Cl-, mt lng HgSO4 c thm vo vi t l HgSO4:Cl- l 10:1. Ion Cl- kt hp
vi Hg to thnh HgCl2, hp cht ny khng b oxy ha bi K2Cr2O7. Khi dng HgSO4
cn ion trong nc c hm lng Cl- ln hn 2000 mg/L th khng hiu qu v khi s dng
HgSO4 vi lng ln s gy nhim mi trng. V vy, phng php ny ch s dng tt
phn tch nc c hm lng Cl- nh hn 2000 mg/L (3,5).
Ion NO2- trong nc qu cao cng dn n sai s khi phn tch, 1 mg NO2- s tiu th 1,1 mg
O2 khi b oxy ha. Trong nc hm lng NO2- t khi vt qu 1 mg/L cho nn hin tng

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gy nhiu ny thng c b qua, nhng nu hm lng NO2- vt qu 1 mg/L nn dng 10

mg acid sunfamic cho mi mg NO2- cn ion ny.
Tnh kt qu

COD mgO2 / L

A B M 8 1000
Vm

Trong :
A: Th tch FAS chun cho mu trng
B: Th tch FAS chun cho mu nc
M: Nng phn t gram ca dung dch FAS

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