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PHN 1: HA HC NC

Chng 1: MT S KIN THC C BN V HA NC


1. 1. Nc v tnh cht ca nc
1.1.1. Thnh phn, cu to v tnh cht ca nc
a. Thnh phn, cu to ca nc
Nc l mt hp cht ho hc rt c bit, trong mi nguyn t hiro gp mt
in t vo i in t dng chung vi nguyn t oxy to thnh lin kt cng ha
tr. Trong mi phn t nc c hai nguyn t hiro v mt nguyn t oxy.
H2

O2

3000 C

H2O

Hai nguyn t hiro lin kt vi oxy to gc lin kt 105o.

Trong nguyn t oxy, ht nhn ca n thng c in tch rt mnh. Chnh v th


n c xu hng ko in t bt khi nguyn t hiro nh hn. Kt qu l chng c u
th trong mi lin kt cng ha tr. Do , trong phn t nc c in tch dng gn
vi nguyn t hiro v c in tch m gn vi nguyn t oxy.
Hyro c 3 ng v Proti (1H), Dtri (2H) v Triti (3H). Trong thin nhin 1H
chim t 99,985 99,986% tng s nguyn t; 2H chim t 0,0139 0,0151% tng s
nguyn t; ng v 3H c tnh phng x, vi chu k bn hy l 12,4 nm.
Oxy cng c 6 ng v: 14O, 15O, 16O, 17O, 18O, 19O nhng ch c 3 ng v thin
nhin l 16O (chim 99,759% tng s nguyn t), trong khi 17O (chim 0,037%) v
18
O (chim 0,037%).
Hiro c pht hin vo th k th 16, do nh gi kim thut ngi thy s l
paraxen (1493-1541). Oxy c pht hin ln u tin vo nm 1711 do Karl Wilhem
Scheele do mt nh ha hc ngi thy in (1742-1786).
Nc c M = 18 l nc thng, chim 99,8% tng lng nc t nhin.
Nc c M 19 l nc nng, chim 0,2% tng lng nc t nhin.
Hm lng cc loi nc nng trong t nhin phn b rt khc nhau. Nguyn
nhn l do hng lot cc qu trnh vt l, ha hc, sinh hc xy ra khc nhau to ra s
phn b cc ng v (H v O) khc nhau.
Nc l mt phn t phn cc, nn cc phn t nc c tnh cht hp dn ln
nhau nh lc ht tnh in. S hp dn ny to nn mi lin kt hiro, nh nhit
thng chng trng thi lng. Gia cc nhm phn t nc tn ti xen k vi cc
phn t nc n l: mH2O (H2O)m c H < 0.
Gi tr m thay i theo nhit ( th hi m = 1; th rn m = 5;...).
trng thi rn, cu trc c bn gm mt phn t nc trung tm v bn phn
t xung quanh, tp hp thnh hnh t din (hnh 1).
1

S bn ha cu trc ca nc khng nhng do c mt cc ion l trng ca n,


m cn do a thm vo nhng phn t to c lin kt hiro vi cc phn t nc.
Mt khc, cu trc ca nc c lm bn, khi nc cn nm trng thi lng v khi
trn ln n vi cht khc.

b. Mt s tnh cht ca nc
- Nc thng v nc nng c nhng tnh cht vt l khc nhau:
Bng 1. Mt s tnh cht vt l ca nc
Nc nng

Nc thng
1
2 16 ( 2 )

Tnh cht vt l
T khi (d) 277oK

2 16 ( D2 )

1,1056

To nng chy (oK)

273

276,8

To si (oK)

373

374,42

- p sut kh quyn l 1 atm, nc ng c OoC, si 100oC, rt cao so vi


im si ca cc hp cht tng t cng nhm.
- Nhit si ca nc gim khi p sut bn ngoi gim (Bng 2)
Bng 2. Mi lin h gia nhit si v p sut ca nc thng
Nhit si t (oC)

10

20

30

40

50

100

p sut P (mmHg)

4,5

9,2

17,5

31,8

55,3

92,5

760

- Nc l mt loi dung mi rt tt, c kh nng ha tan mt s cht rn, khi nng


cht tan trong nc cng ln th nhit si cng cao v nhit ng c ca
dung dch cng thp.
- ho tan ca cc kh trong nc ph thuc vo nhit v p sut.
- Sc cng b mt ca nc ln hn sc cng b mt ca cc cht lng khc.
- Nc l cht lng khng c mu, trong sut, cho nh sng v sng di i qua (hp
th nh sng sng ngn mnh hn) gip cho qu trnh quang hp c th thc hin
su trong nc.
- Nc c khi lng ring (t trng) cc i 3,98oC ( 4oC) khng phi l im
ng bng, do vy m nc n ra khi ng bng. T trng ca nc thay i theo
nhit .
i vi nc tinh khit s thay i ny nh sau:
2

Bng 3. S thay i t trng ca nc tinh khit i vi nhit


t(oC)

T trng (kg/dm3)

t(oC)

T trng (kg/dm3)

0,99987

20

0,99828

1,00000

25

0,99707

10

0,99973

30

0,99567

15

0,99913

100

0,95838

- Nhit bay hi ca nc (540 cal/g) ln hn nhit bay hi ca cc cht khc, cho


nn nc c s dng rng ri trong cc qu trnh truyn nhit.
- Nhit ha tan ca nc cao hn cc cht lng khc (tr NH3) v to iu kin gi
nhit im kt tinh ca nc.
- Nhit dung ring ca nc (1cal/g.oC) cao hn ca cc cht lng khc (tr NH3)
nn c th n nh nhit cc vng a l khc nhau.
- Nc c th ng vai tr l mt cht kh, cht oxy ho:
2H2O - 4e 4H+ + O2

E0 = - 1,230V

2H2O + 2e 2OH- + H2

E0 = - 0,828V

- Tt c cc qu trnh trao i cht ca t bo phi thng qua nc, bao gm: Cc


qu trnh ng ho; cc qu trnh d ho v ln men.
- Nc l trung tm cuc sng ca vi khun.
1.1.2. S ha tan cc cht trong nc
Nc l mt dung mi c bit: nhit thng trn b mt tri t, nc l
cht lng c khi lng phn t nh nht li phn cc mnh, v vy c kh nng xm
nhp ha tan rt nhiu cc cht v c, hu c thnh dung dch. Vi phn t nh v
phn cc mnh, nc cng c kh nng thm t v phn r cc cht kh tan to thnh
cc h phn tn nh keo, huyn ph.
a. S ha tan cht rn trong nc
Nc c th to lin kt hiro vi cc cht ha tan. Cc cht ha tan c th
dng ion cng c th khng dng ion. C hai loi ny u c th ha tan trong nc.
S ha tan bao ch yu gm 2 qu trnh: l hc v ho hc (hirat ho).
- Qu trnh l hc thng thu nhit: a > 0.
- Qu trnh hirt ho thng to nhit: b < 0.
Nhit ca qu trnh ho tan (l lng nhit to ra hay thu vo khi ha tan mt
mol cht tan vo nc):
= a + b

(1-1)

Nu > 0 : th qu trnh ha tan l thu nhit.


Nu < 0 : th qu trnh ha tan l to nhit.
V d: Ha tan NaCl vo nc, qu trnh c th chia lm 2 bc:
- Bc 1: Ph v cu trc tinh th ca cht tan to thnh tiu phn ring bit. Tip
l ph v lc lin kt lin phn t gia cc phn t dung mi to ra cc khong
trng cho cc tiu phn ca cht tan xm nhp. Trong a s trng hp u thu nhit.
3

- Bc 2: Xy ra tng tc gia cc tiu phn ca cht tan v cc phn t dung mi


to thnh dung dch, tc xy ra qu trnh solvat ha. Qu trnh ha tan l to nhit.
Nhit ho tan ca dung dch, chnh l tng nhit ca cc gi tr trn.
Ty qu trnh no chim u th m gi tr H (hiu ng nhit ca phn ng) c
th (+) hoc (-) hay ni cch khc qu trnh ha tan thu nhit hoc ta nhit. Thc t,
nhit ha tan NaCl trong nc khong 3KJ/mol.
ha tan ca mt cht l nng bo ha ca dung dch cha cht tan
mt nhit xc nh. ho tan thng c k hiu l S (S tnh theo mol/l hay g/l).
Dung dch bo ha l dung dch cha lng cht tan bng ha tan ca n ti
mt nhit xc nh.
Dung dch qu bo ha l dung dch cha lng cht tan ln hn ha tan ca
n ti mt nhit xc nh.
b. ha tan cht kh trong nc
S c mt ca cht kh ho tan c vai tr rt ln i vi cc c tnh ho, sinh
hc ca nc, c bit l oxy v kh cacbonic.
S tn ti ca cc cht kh trong nc lm bin i pH v tnh th oxy ho
kh (Eh) ca nc, gy nh hng xu n cht lng ca nc.
S ha tan ph thuc vo bn cht ca cht kh, nhit ca nc, khong
ha ca nc v p sut ca cht kh .
Xt s gia tng tan ca kh trong dung dch: gi s ang xy ra cn bng gia
cht kh v cht lng, ngha l s phn t kh thot ra hoc tan vo dung dch vi tc
bng nhau. Nu ta tng p sut, s phn t kh trong mt n v th tch s gia tng,
kh s tan vo dung dch vi tc ln hn tc thot ra, lc ny nng kh tan
trong dung dch s tng cho n khi mt cn bng mi c thit lp v d nhin lc
ny dung dch s cha mt lng kh tan nhiu hn. S ph thuc ha tan ca cht
kh v p sut ring phn ca kh trn mt nc tun theo nh lut Henry:
ho tan ca mt cht kh trong cht lng mt nhit khng i t l thun
vi p sut ring phn ca kh tc dng ln cht lng.
Gi Si (mg/l) l ha tan ca kh i:
Si = k.Pi

(1-2)

k : hng s Henry, ph thuc vo bn cht ca cht kh v nhit .


Bng 4. S ph thuc ca hng s Henry (k) vo nhit
Nhit (oK)

k
O2 ( 10-5)

CO2 ( 10-5)

H2S ( 10-5)

273

67,45

3349,51

6825,24

275

63,48

3000,97

6397,08

277

60,52

2788,34

5998,05

279

57,47

2602,91

5626,21

291

43,83

1736,89

3966,99

298

38,76

1407,76

3332,03

nh lut Henry ch ng trong trng hp kh tan khng phn ng vi dung


mi, v d: ng vi trng hp kh O2 tan trong nc, nhng khng ng vi trng
hp HCl tan trong nc v y xy ra s phn ly ca HCl.
V d: Xc nh ho tan (S) ca O2 279oK di p sut p = 0,2163.105 N/m2.
Tra bng 4 ta c: k = 57,47.10-5
S = 57,47.10-5 . 0,2163.105 12,43 mg/l.
ha tan cc cht kh trong nc tng khi nhit nc gim.
Cht kh l hp cht c ha tan ln hn cht kh l n cht do cc phn t
hp cht thng l phn t phn cc.
Thng thng khi khong ca nc tng ln th ha tan ca cc kh gim.
ha tan ca O2 s gim 25% khi tng lng mui ha tan trong nc ti 40 gam.
c. ha tan cht lng trong nc
Cht c cng bn cht phn cc ha tan tt vo nhau, m s phn cc ca mt
cht c xc nh bi cu trc ca n (dng lai ho, s tng tc gia cc electron
lp v in t,...). Do , gia cu trc v tan c mt mi quan h xc nh.
Thng thng cc cht lng phn cc thng d ha tan trong nc; Cc cht
hu c thng kh ha tan trong nc.
1.1.3. nh lut tc dng khi lng
a. Tc phn ng
Trong qu trnh phn ng nng cc cht phn ng gim dn cn nng cc
cht sn phm tng dn. Phn ng xy ra cng nhanh th trong mt n v thi gian th
nng cc cht phn ng gim xung v nng cc cht sn phm tng ln cng
nhiu. Nh vy, c th dng bin thin nng ca mt cht bt k trong phn ng
theo thi gian lm thc o tc phn ng.
Tc phn ng l i lng c trng cho din bin nhanh hay chm ca mt
phn ng. N c o bng bin thin nng ca cc cht phn ng hay sn
phm phn ng trong mt n v thi gian.
Xt phn ng:

A = M + N

Tc trung bnh ca cht A: v =

C1 C2
C C2
C
= 1
=
t
t2 t1
t1 t2

v : vn tc trung bnh trong khong thi gian t t1 n t2;

C: s bin thin nng mol ca cht kho st t C1 n C2.

Khi t 0 th v tc thi l: v =

dC
dt

Tng qut: aA + bB cC + dD th tc phn ng: V = K [ A] a [ B] b =

dC
dt

b. Hng s cn bng
Cn bng ho hc l trng thi ca mt qu trnh thun nghch khi vn tc ca
phn ng thun bng vn tc ca phn ng nghch v do nng cc cht khng
bin i na.
5

Xt phn ng cn bng:
A(K)

+ B(K)

k1

C(K) + D(K)

k2

Gi k1 v k2 ln lt l hng s vn tc ca phn ng thun v nghch. Gi s


phn ng thun cng nh phn ng nghch u thuc loi n gin (ngha l phn ng
ch xy ra trong mt giai on, bc phn ng ring phn ca mi cht bng h s t
lng nguyn ti gin ng trc mi cht trong phn ng).
Thc nghim cho thy, vi phn ng ng th th: vn tc ca phn ng t l
thun vi tch nng cc cht tham gia.
Vn tc phn ng thun l:

v1 = k1[A][B]

Vn tc phn ng nghch l:

v2 = k2[C][D]

Gi s lc bt u phn ng, ch c A, B hin din. Vn tc phn ng thun v1


lc u rt ln, vn tc phn ng nghch v2 bng khng. Phn ng cng xy ra lu,
nng cc cht A, B cng gim , nng cc sn phm C, D cng tng.
Nh vy, v1 gim dn theo thi gian, cn v2 tng dn theo thi gian. Sau mt thi
gian vn tc phn ng thun v1 s bng vn tc phn ng nghch v2, lc ny phn ng
t trng thi cn bng:
v1 = v2 k1[A][B] = k2[C][D]

KC =

k1

k2

[C][D]
[A][B]

V k1 v k2 l cc hng s vn tc phn ng, ch ty thuc nhit (v ty thuc


bn cht ca phn ng), cho nn ng vi mt nhit xc nh (v mt phn ng xc
nh), ta c:
KC =

[C][D]
k1
=
[A][B]
k2

CB

(1-3)

CB: cn bng, ch nng cc cht C, D, A, B lc t trng thi cn bng.


KC c gi l hng s cn bng ca phn ng lin h n nng (mol/l). Kc ch
ph thuc nhit v bn cht ca phn ng, m khng ph thuc vo nng cc cht
trong phn ng.
Tng qut:

mA + nB pC + qD

KC =

k1
[C]p[D]q
=
[A]m[B]n
k2

k1, k2 : c trng cho hng s tc ca phn ng thun nghch, ch ph thuc


vo bn cht phn ng v nhit .
Vi [A], [B], [C], [D] l nng ca A, B, C, D lc cn bng.
Kc: hng s cn bng ch ph thuc vo bn cht h phn ng v nhit .
c. Hng s in ly
S in ly ca cht in ly yu l mt qu trnh thun nghch nn ta c th p
dng nh lut tc dng khi lng.
Gi s c cn bng:

HA H+ + A6

Ta c:

[H + ] [ A ]

(1-4)

[ HA]

[H+], [A-]: nng mol


Hng s cn bng K gi l hng s in ly hoc hng s ion ha, c trng cho
kh nng in ly ca mt cht; K cng ln th s in ly cng mnh, cht in ly phn
ly ra cc ion cng nhiu v ngc li. K ph thuc vo bn cht ca cht in ly, dung
mi v nhit .
d. Tch s ha tan
Gi s c cht in li t tan AnBm trong nc c cn bng:
AnBm Am+ + Bn(cht rn)

(trong dung dch)

Qu trnh thun nghch t trng thi cn bng, ta c dung dch bo ha cht in


ly t tan. p dng nh lut tc dng khi lng vo cn bng d th ta c:

T An Bm = a An m + .a Bn n

(1-5)

Nh vy, trong dung dch bo ha cht in ly t tan tch s hot cc ion vi


s m tng ng l mt hng s, hng s ny c tn l tch s tan.
V cht in ly kh tan c nng rt nh, nn a s trng hp c th coi hot
bng nng , khi biu thc tch s tan c dng n gin:

T An Bm = [ A m + ]n [ B n ]m

(1-6)

Gi tr T cng b th cht in li cng t tan v ngc li.


Gi tr T l mt hng s xc nh mt nhit xc nh.
Tch s tan l hng s cn bng, ln ca n ch ph thuc vo bn cht cht
tan, nhit .
Tch s tan c lin h cht ch vi tan S (biu th bng nng mol) ca cht
in ly t tan.

T An Bm = m m .n n .S m + n

(1-7)

Bng 5. Tch s tan ca mt s hp cht in ly t tan (T) 20oC


Cht in ly

Cht in ly

AgCl

2,8.10-10

BaSO4

1,5.10-9

AgBr

5.10-13

BaCO3

1,6.10-9

AgI

8,5.10-17

BaCrO4

1,2.10-10

Ag2S

1.10-50

Al(OH)3

5.10-33

Ag2CrO4

1,9.10-12

Cr(OH)3

7.10-31

AgCNS

1.10-12

CaSO4

2,4.10-5

ZnS

1.10-20

PbS

4.10-26

1.1.4. Hot cc ion trong dung dch


a. Khi nim v hot
Hot l nng hiu dng ca cc ion trong dung dch.
Biu thc:
Trong :

a = f.C

(1-8)

C: l nng thc
a: l hot .
f : l h s hot .

- Vi dung dch long cht in ly yu, tng tc cc ion khng ng k:


f = 1, a = C.
- Vi dung dch cht in ly mnh hoc dung dch m c ca cht in ly yu:
0 < f < 1 v a < C.
Thc t cho thy nng cc ion trong dung dch cng ln th s tng tc
tng h gia chng cng mnh, s khc nhau gia a v C cng ln, f cng nh v
ngc li.
Trong nc t nhin, nng cc ion thng rt nh (< 200 mg/l) nn s khc
nhau gia a v C thng khng ln. Nhng vi nc c khong ha rt cao
(>500mg/l) th s khc nhau gia a v C li l ln.
b. Cch tnh h s hot

* Tnh lc ion:
Lc ion c trng cho cng trng lc chung ca cc ion trong dung dch.
Nhm nh gi tc ng tnh in ca cc ion trong dung dch.
K hiu:
Lc ion c tnh theo cng thc:
1
2

= (C1Z12 + C2 Z22 + ... =

1 n
Ci Zi2

2 i =1

(1-9)

Trong Ci: nng th i v Zi: in tch ca n.


V in tch ca cc ion l khng i, hm lng cc ion trong nc thng c
tnh bng mg/l nn ngi ta c th chuyn i cng thc trn bng cng thc:
1
2

= (C1 K1 + C2 K 2 + ... + Cn K n )

(1-10)

C1, C2, Cn: nng mi loi ion (mg/l).


K1, K2, Kn: h s t l chuyn i c tnh sn.
Bng 6. Gi tr h s t l chuyn i K
Ion

Ion

K+

0,026.10-3

NO3-

0,016.10-3

Na+

0,043.10-3

HCO3-

0,016.10-3

Ca2+

0,10.10-3

Cl-

0,028.10-3

* Tnh h s hot :
Trong thc t ch c th xc nh h s hot trung bnh f . Chng hn vi
cht in ly AmBn:

f =

(m+n)

f +m . f n

(1-11)

Cng thc thc nghim tnh h s hot f ph thuc vo gi tr ca 298oK


nh sau:
- Vi dung dch c lc ion 0,01, h s hot f tnh theo cng thc:
lg f = 0,5. 2

(1-12)

- Vi dung dch c lc ion 0,01 < 0,5 th h s hot f c tnh theo cng thc:
lg f =

0,5. 2

(1-13)

1+

- Vi dung dch c lc ion > 0,5 th h s hot f c tnh theo cng thc:
lg f =

0,5. 2
1 + 0,33.10 8.r

+A

(1-14)

r : bn knh ion ngm nc tnh theo cm.


Ch : Mt s ion c bn knh ngm nc vo khong 3.10-8 cm, th d OH-, F-, Cl-,
Br-, I-, NH4+, Ag+,; r 4.10-8 cm cho: Na+, H2PO4-, Pb2+, SO42-, PO43-,...
Mt s ion ngm nc khc c bn knh to ln, c bit ion H+ ngm nc c
bn knh rt ln: 9.10-8 cm.
A: h s thc nghim ph thuc vo bn cht ca cht in ly v dung mi.
Bng 7. Gi tr h s hot f theo v in tch ion Z

H s hot f
Z=1

Z=2

Z=3

0,000

1,00

1,00

1,00

0,001

0,96

0,87

0,72

0,002

0,95

0,81

0,63

0,003

0,92

0,72

0,48

0,010

0,9

0,63

0,35

T bng gi tr trn cho thy: lc ion cng ln v ion c in tch cng ln, th h
s hot f cng nh, tc l s khc gia nng v hot cng ln. Cn khi lc
ion nh, vi cc ion c in tch thp, th f 1.
Mt s v d
V d 1: Xc nh lc ion ca dung dch hn hp HCl 0,1M v CaCl2 0,2M.
Gii:
HCl v CaCl2 trong dung dch coi = 1.
9

HCl = H+ + ClCaCl2 = Ca2+ + 2Cl[H+] = 0,1M; [Ca2+] = 0,2M; [Cl-] = 0,1 + 0,4 = 0,5M.

1
2

= (0,1.12 + 0,5.12 + 0,2.2 2 ) = 0,7


V d 2: Tnh hot ca cc ion K+ v Cl- trong dung dch KCl 0,01M.
Gii:
KCl = K+ + ClLc ion ca dung dch:

1
2

= (0,01.12 + 0,01.12 ) = 0,01

= 0,1

H s hot ca cc ion:

lg f K + = lg f Cl = 0,5.12.0,1 = 0,05M

f K + = f Cl = 0,5.12.0,1 0,9M
Hot ca cc ion: aK + = aCl = 0,9.0,01 = 9.103 M
V d 3: Tnh hot ca nhng ion trong dung dch hn hp: KCl 10-3M v MgSO4
10-3M.
Gii:
Lc ion ca dung dch:

1
2

= (12.10 3 + 12.10 3 + 2 2.10 3 + 2 2.10 3 ) = 5.10 3

= 7.10 2

H s hot ca cc ion:

lg f K + = lg f Cl = 0,5.12.0,07 = 0,035M f K + = f Cl = 0,92M


lg f Mg2+ = lg f

SO42

= 0,5.2 2.0,07 = 0,14M f Mg2+ = f 2 = 0,72M


SO
4

aK + = aCl = 0,92.103 = 9,2.104 M ;


aMg2+ = a

SO42

= 7,2.104 M

V d 4: Trong 1 lt dung dch CaCO3 bo ho c cha 0,292 gam Mg2+ v 0,851 gam
Cl- th hm lng CO32- ( tnh theo hot ) l bao nhiu ? Bit CaCO 3 = 3,6 .10 9 .
Gii:
CaCO3 ho tan theo phng trnh:
CaCO3 Ca2+ + CO32-

CaCO 3 = a Ca 2 + .a CO 2 = f Ca 2 + .[ Ca 2 + ]. f CO 2 .[ CO 32 ]
3

2+
2
Trong dung dch: [Ca ] = [CO 3 ]

10

f Ca 2 + = f CO

2
3

= f

nn ta c:

CaCO 3 = [ CO 32 ] 2 . f
[CO 32 ] =

3,6 .10 9
6 .10 5
=
f2
f

=
f2

V CaCO 3 rt nh nn nng cc ion Ca2+ v CO32- rt nh. Khi tnh trong


trng hp ny c th b qua cc ion Ca2+ v CO32- m ch quan tm ti 2 ion Mg2+ v
Cl-.
[ g 2 + ] = 0,292 gam =

[Cl ] = 0,851gam =

0,292
0,012
24

0,851
0,024
35,5

1
2

= (0,012.2 2 + 0,024.12 ) = 0,036


lg f =

[ CO

2
3

0,5.2 2 0,036
1 + 0,036

f = 0,48

6 .10 5 6 .10 5
]=
=
= 12 ,5 .10 5 = 7 ,5 mg / l
f
0 , 48

1.2. Nc thin nhin


1.2.1. Gii thiu chung

Nc thin nhin chim 1% tng lng nc trn tri t, bao gm cc loi nc


c ngun gc thin nhin nh nc sng, ao, h, sui, bin, i dng. Nc thin
nhin l mt h d th nhiu thnh phn, v nc thin nhin lun cha nhng lng
cc cht tan v khng tan c ngun gc t v c v hu c.

Tng tr lng nc t nhin trn Tri t khong t 1.385.985.000 km3 n


1.457.802.450 km3. Nc t nhin tp trung phn ln bin v i dng (trn
97,61%), sau l cc khi bng cc (1,83%), ri n nc ngm (0,54%). Nc
11

ngt tng mt chim mt t l khng ng k (0,02%),... Lng nc trong kh quyn


chim khong 0,001%, trong sinh quyn 0,002%.
Nc cn cho nhu cu sng ca mi c th. Nc chim ti 80 - 90% trng
lng sinh vt sng trong mi trng nc v 44% trng lng c th con ngi.
Nc p ng cc yu cu a dng ca con ngi: ti tiu cho nng nghip, sn xut
cng nghip, to ra in nng v t thm v p cho cnh quan.
Hng nm c khong 5 triu km3 nc bay hi t t v cc ngun nc mt
(sng, h, i dng,...) sau ngng t v ma xung, lng nc do khi nc trn
bay hi hp th xp x gn 3.1020kcal/nm.
Bng 8. Th tch cc ngun nc t nhin trn th gii
Th tch, 1000 km3

1.348.000

97,312

Bng

29.000

2,093

Nc ngm

8.000

0,577

H, sng sui

200

0,014

Nc chy trn mt t

40

0,003

1.385.240

100

Ngun nc

i dng

Tng cng

Lng nc ngt c con ngi s dng c ngun gc ban u l nc ma


c chng 105.000 km3, trong khong 1/3 chy ra sng, cn li 2/3 quay tr li kh
quyn do bc hi b mt v thot hi nc thc vt. Nu xem 1/3 lng nc ma
k trn (khong 40.000 km3) l ngun nc cung cp tim nng cho con ngi th vi
s dn hin ti, mi ngi mi ngy nhn c trung bnh 16 lt nc.
1.2.2. Cc qu trnh hnh thnh thnh phn ha hc ca nc thin nhin
a. Khi nim chung v s hnh thnh thnh phn ha hc ca nc thin nhin

S hnh thnh thnh phn ha hc ca nc thin nhin ph thuc vo iu kin


hnh thnh, qu trnh di chuyn ca n, thnh phn v cc c tnh ha hc ca cc
cht m n tip xc. Bao gm cc qu trnh ch yu sau:
- Qu trnh ho hc (ho tan, hp th, oxy ha kh,).
- Qu trnh sinh ha (quang hp, phn gii,).
- Qu trnh vt l (bc hi, ng bng, ma, tan bng,).
S tc dng tng h ca nc vi mi trng xung quanh c th lm tng hm
lng cc cht trong nc, c th lm gim hm lng cc cht trong nc v cng c
th thay i thnh phn ha hc ca nc thin nhin.
b. Cc yu t nh hng n qu trnh hnh thnh thnh phn ha hc ca nc
thin nhin

* nh hng do qu trnh phong ha ca :


Cc tnh ton ca cc nh a cht cho thy: trng lng cc nhm trong v tri
t c t l phn b: macma 65%, bin cht (mentamorphic) 25% v trm tch 10%.
macma gm hai loi: xm nhp v phn xut c xut x t qu trnh
hot ng ca ni la.
12

trm tch l kt qu tc ng ca nhng cu t (c thnh phn trong kh quyn


hoc thy quyn) ln b mt v tri t v l kt qu ca qu trnh lng. Nhng
trm tch quan trng l nham thch, ct v vi.

mentamorphic c to thnh t macma v trm tch do tc ng ca


p sut v nhit cao. Trong xy ra cc qu trnh ha hc v vt l l nhng qu
trnh dn ti nhng khong bn nhit v c t trng c bit.
Qu trnh phong ho ca bao gm:
- Phong ha vt l
- Phong ha sinh hc
- Phong ho ho hc
Nhng qu trnh phong ho ha hc tng i n gin xy ra nh: Qu trnh
ho tan cht kt tinh, qu trnh phong ho do CO2, qu trnh thu phn, qu trnh
phong ho oxy ho kh.
Kt qu ca cc qu trnh phong ha : sn phm c ho tan trong nc v b
cun tri theo dng chy v lm cho thnh phn ha hc ca nc thay i. Tuy nhin,
trong qu trnh di chuyn trong nc, tnh di ng ca cc nguyn t rt khc nhau:
- Cc cht di ng mnh: Cl, Br, I, S
- Cc cht d di ng: Na, K, Mg, Ca
- Cc cht t di ng: SiO2, P, Mn
- Cc cht di ng rt yu: Fe, Al, Ti
Do tnh di ng ny m ta thy nc bin tp trung cc cht c tnh di ng mnh
nht nh Na+, Cl- chim u th.

* nh hng ca nc khi tip xc vi t:


Thnh phn ha hc ca t ph thuc vo tng loi t v v tr loi t tn
ti.
Nc trong t lu thng nh nhng rnh nh vi ng knh trn 10 m. Khi
nc thm qua cc loi t khc nhau th s thay i thnh phn ha hc ca nc
cng khc nhau.
13

Nc khi tip xc lu di vi t, ngoi kh nng ha tan cc cht trong t cn


c kh nng trao i cht vi t v nh vy cng lm thay i thnh phn ho hc
ca nc. C th:
- t hp ph cc cation ca nc: t l mt h keo, cc ht keo u mang in
tch m. V vy keo t c kh nng hp ph cc cation ca nc rt mnh.
- t c kh nng trao i cc ion vi nc: Khi hm lng mt loi cation no
ca nc kh cao th c th trao i vi cation khc trong t.

* nh hng ca cht hu c:
Cht hu c trong nc c hiu l tn tch hu c ang phn hy, tn ti trong
nc c hai dng ha tan v l lng, khng bao gm sinh vt sng, tr sinh vt c
kch thc rt nh nh vi sinh vt v to n bo, cng khng bao gm cc tn tch
hu c th, c kch thc ln, c th ly ra khi nc.
Cc cht hu c sng v cc sn vt m n sinh ra trong qu trnh sng c nh
hng rt ln n thnh phn ha hc ca nc t nhin.

* nh hng ca kh hu:
Kh hu c th lm thay i cc qu trnh phong ha; thay i hot ng sng ca
cc vi sinh vt; thay i qu trnh oxy ha kh trong nc

* nh hng ca nc ngm:
Nc ngm tip xc vi nham thch nhiu nht, nn thnh phn ha hc ca
nc ngm ch yu ph thuc vo tng nham thch v t cha n.
Thnh phn ha hc v khong ha ca nc ngm tng su bin i theo
ma t hn nc mt. Nc ngm di su c th hu nh khng cha cht hu c
v vi khun. Tuy nhin, kh nng nhim cc nguyn t vi lng trong nc ngm
cao hn nc mt, in hnh l nhim Fe, Mn, As, F-, Br-, S2-,
1.2.3. Th kh ha tan v nng ion hyro (H+)

Ni chung cc cht kh trong kh quyn u c mt trong nc do kt qu ca hai


qu trnh c bn l khuch tn v i lu.
C nhiu loi kh ha tan trong nc v c nh hng ti thnh phn ha hc ca
nc. Chng ta nghin cu mt s kh ch yu ha tan trong nc.
a. Kh oxy

Oxy l loi kh t ha tan trong nc v khng tc dng vi nc v mt ha hc.


Oxy ha tan trong nc dng phn t t do gi l lng oxy ha tan, vit tt l
DO (Dissolved Oxygen). Oxy ha tan trong nc l iu kin ch yu cho s tn ti
ca nhiu cht hu c sng trong nc v nhiu qu trnh ha hc khc nhau xy ra
trong nc.
Mt s quy lut v s ha tan oxy t pha kh vo nc:
- C hai nhm ch yu c tc dng lm giu oxy trong nc: oxy trong khng kh
ha tan vo nc v oxy c to ra do qu trnh quang hp.
- Cc ngun ch yu lm gim oxy ha tan trong nc: oxy cn oxy ho cc cht v
c, hu c c trong nc; oxy cn cho sinh vt sng s dng h hp; oxy b gii
hp khi nc.

14

- Trong nc, oxy tham gia ch yu vo cc qu trnh: Oxy ha cc cht hu c bng vi


sinh vt, oxy ho cc cht nit bng vi sinh vt v oxy ho cc cht ha hc khc.
- nhit nht nh, nng bo ha ca oxy trong nc ch ph thuc vo p
sut ring phn ca oxy trong pha kh (tun theo biu thc nh lut Henry).
- Khi nhit cng tng, nng mui tng, qu trnh h hp tng dn n ha
tan ca oxy cng gim.
Bng 9. nh hng ca nhit n ha tan ca oxy trong nc
toC

Nng bo ha (mgO2/l)

toC

Nng bo ha (mgO2/l)

14,65

20

8,84

10

11,00

30

7,29

- Hm lng oxy ha tan gim dn theo chiu su ca nc.


- Khi mui tng, ha tan oxy gim.
Bng 10. nh hng ca nng mui n ha tan ca oxy trong nc
toC

10

20

30

S gim tan ca oxy (mg/l) ng


vi bin i mi mui (1g/l)

0,08405

0,06217

0,04777

0,04085

- Hm lng oxy trong nc t nhin thng dao ng t 0 n 14 mg/l.


- Trong nc ngt lng oxy ha tan (DO) 0oC v 1 atm l 14,65 mg/l. Ngi ta
thng ly DO 250C, 1 atm bng 8 mg/l.
- Mc tiu th oxy trong nc bi cc cht nhim c biu th qua ch s nhu
cu oxy sinh ha (Biochemical oxygen Demand - BOD) hay nhu cu oxy ha hc
(Chemical Oxygen Demand - COD).
b. Kh cacbonic

H CO32- - CO2 trong nc ng vai tr rt quan trng v n tham gia vo qu


trnh trao i gia kh quyn v nc trn lp nc b mt.
Mt s quy lut v s ha tan cacbonic t pha kh vo nc:
- Ngun cung cp CO2 ho tan trong nc: t khng kh, sn phm ca qu trnh
oxy ha cc hp cht hu c v s thi ra trong qu trnh h hp ca vi sinh vt.
- Ngun lm gim CO2 trong nc: qu trnh gii hp; qu trnh xm thc ca mui
cacbonat v qu trnh quang hp sinh vt tiu th CO2.
- CO2 l mt kh d ha tan trong nc v ha tan trong nc tng ln theo chiu
gim ca nhit . Nng CO2 lp b mt tun theo nh lut Henry.
- Trong nc, kh CO2 c th tn ti dng t do hoc dng kt hp vi nc.
CO2 kt hp vi nc ph thuc vo gi tr pH ca nc.
Khi pH < 5: CO2 + H2O H2CO3
Khi pH 5: H2CO3

H+ + HCO3-

Khi pH 8: HCO3-

H+ + CO32-

- Trong thc t c th tng hoc lm gim hm lng ca kh CO2 trong nc b mt.


15

- trm tch, CO2 tham gia phn ng:


CaCO3 + CO2 + H2O

Ca(HCO3)2 Ca2+ + 2HCO3-

Qu trnh ny dn n s thay i pH ca mi trng.


c. Cc kh khc

i vi cc loi kh khc ha tan trong nc th H2S l loi kh ng ch .


Trong lp nc mt c oxy ha tan th hm lng H2S ch tn ti trong mt
khong thi gian ngn v n b oxy ha rt mnh.
Trong nc ngm, hm lng H2S c khi t mc cao, lp nc ngm cng
su hm lng H2S cng cao.
d. Nng ion H+

Trong nc nguyn cht tn ti cn bng:


H 2O

H 3O +

n gin ta vit:

H2 O

H+

2980K:

[H+] = [OH-] = 10-7M.

Tch s ion ca nc:

KW = [H+][OH-] = 10-14.

Ta c:

pH = - lg[H+]

H2O

Mi trng axt:

pH < 7

Mi trng baz:

pH > 7

Mi trng trung tnh:

pH = pOH = 7

OH-

OH-

(1-15)

Trong nc thin nhin, nng ion H+ khng phi ch ph thuc vo s in ly


ca nc m ch yu ph thuc vo t l hm lng H2CO3 ; HCO3- v CO32- v mt
s ion khc c trong nc.
Cn bng cacbonat ha tan (h ng)

i vi dung dch h cacbonat n gin, c 6 cu t ha tan: CO2, H2CO3,


HCO3-, CO32-, H+, OH-. H gm 4 phng trnh quan h:
H2CO3 CO2(aq) + H2O
+

H2CO3 H + HCO3

[C 2 (aq)]
[ 2 C 3 ]

H 2CO3

[ + ][C 3 ]
=
[ 2 C 3 ]

Tng CO2 ha tan ([H2CO3*]): [H2CO3*] [CO2 (aq)] + [H2CO3]


(t: 1-18)
-

(1-16)
(1-17)
(1-18)

[ + ][C 3 ]
1 =
[ 2 C 3 *]
[ + ][C 32 ]

HCO3

H+ + CO32-

2 =

H2O

H+ + OH-

H 2 O = [ + ][H ]

[C 3 ]

(1-19)
(1-20)

Lc ny trong h gm c cc cu t: CO2 (aq), H2CO3, HCO3-, CO32-, H+, OH-.


Nng tng hp cc hp phn ca h (CT) c biu din di dng:
16

CT = [H2CO3*] + [HCO3-] + [CO32-]


[ HC 3 ] =

2
3

[C ] =

K 1 [ H 2 C 3 *]
[ + ]

2 [ HC 3 ]
+

[ ]

;
2
+

[ ]

K 1 [ H 2 C 3 *]
+

[ ]

K 1 K 2 [ H 2 C 3 *]
[ + ] 2

CT = [H2CO3*] + [HCO3-] + [CO32-] = [H2CO3*] (1 +


1

[ H 2 C 3 *] = C T [ 1 +

K1 K 2

1
K K
+ 1 + 22 )
+
[ ] [ ]

] -1

+ 2

[ ] [ ]

(1-21)

Cc cng thc trn cho php nh lng phn trm tng dng cacbonat c trong
nc. Chng hn: Trong ngun nc bin, gi tr K1 o c ti 220C v p sut 1atm
l 4.10-7, ln hn bn bc so vi gi tr K2 (4,2.10-11). Bi vy, s phn ly ca axt
cacbonic ch yu l phn ly bc mt. Khi :
[ + ] =

K 1 [ H 2 C 3 *]
[ HC 3 ]

iu ny cho thy nng ion [H+] ph thuc ch yu vo nng bicacbonat


[HCO3-], theo quan h t l nghch.
Nu ngun chnh to ra ion HCO3- l do phn ly ca cc mui Ca(HCO3)2,
Mg(HCO3)2,khi lm tng nng HCO3-, nh th lm gim nng H+, tc l
tng pH. Gi s trong dung dch cha mt lng ng k ion Ca2+:
HCO3- H+ + CO32-

2 =

a + a C 2
3

a C

a+ = 2

a C

CaCO3 Ca2+ + CO32

a+ = 2

m a =f.C

a =

.a Ca 2 + =

a C 2
3

T = a Ca 2 + .a C 2 a C 2 = 2

a C

T
a Ca 2 +

2
.a 2 + .a C
3
T Ca

2
. f .C f 2 + .C Ca 2 +
T HCO3 HCO3 Ca

(1-22)

Nhit v p sut thy tnh c nh hng ng k n pH ca nc. Nu nhit


(hoc c p sut) tng th hng s phn ly ca H2CO3 v H2O tng ln, dn n pH
tng. Nu nhit tng th ha tan ca kh CO2 trong nc li gim, khi pH
tng.
250C, hng s phn ly axt H2CO3, HCO3-:

[ + ][C 3 ]
= 10 6, 65
1 =
[ 2 C 3 ]

H2CO3 H + HCO3
-

2-

[ + ][C 32 ]

= 10 10,33

HCO3 H + CO3

2 =

[ ] [ 2 C 3 ]

=
1
[C 3 ]

[ ] [ C 3 ]

=
2
[C 32 ]

[ C ]
+

17

(1-23)

Bng 11. Gi tr hng s nng K1*, K2* ca axit cacbonic trong nc bin

%oCl

Nhit
10

14

20

24

28

30

-8

K1(10 )
15

0,74

0,8

0,89

0,95

0,99

1,01

20

0,8

0,87

0,97

1,04

1,07

1,10

K2(10-9)
15

0,6

0,66

0,76

0,83

0,9

0,93

20

0,8

0,89

1,02

1,12

1,21

1,26

(K1*, K2*: hng s nng bin i theo mui)


T biu thc trn cho thy: K1, K2 l hng s, t l vi nng h cacbonat ph
thuc vo nng ion H+, tc l ph thuc vo pH nc.
- Biu thc K1:
pH = 6,35, [ + ] = 10 6,65 = K 1

[HCO3-] = [H2CO3 ]

pH < 6,35, [ + ] > 10 6, 65

[HCO3-] < [H2CO3 ]

pH > 6,35, [ + ] < 10 6, 65

[HCO3-] > [H2CO3 ]

- Biu thc K2:


pH = 10,33, [ + ] = 10 10,33 = K 2

[HCO3-] = [CO32- ]

pH < 10,33, [ + ] > 10 10,33

[HCO3-] > [CO32- ]

pH > 10,33, [ + ] < 10 10,33

[HCO3-] < [CO32- ]

Bng 12. T l (% mol) ca cc thnh phn trong h CO32- bin i theo pH


pH

Tng quan hm lng gia cc


thnh phn trong h cacbonat
(tnh theo mol/L)

% mol ca cc thnh phn


H2CO3

HCO3-

CO32-

3,35

[H2CO3 ] = 1000 [HCO3-]

99,99

0,1

4,35

[H2CO3 ] = 100 [HCO3-]

99

6,35

[H2CO3 ] = [HCO3-]

50

50

7,35

[H2CO3 ] = 0,1[HCO3-]

9,1

90,9

0,1

98

0,1

90,9

8,3
9,3

[HCO3 ] = 100 [H2CO3 ]


[HCO3-] = 100 [CO32- ]
[HCO3 -] = 10 [CO32-]
-

2-

10,3

[HCO3 ] = [CO3 ]

50

50

11,3

[CO3 2-] = 10 [HCO3-]

9,1

90,9

T bng 12 c th rt ra mt s c im sau v s tn ti h cacbonat:

18

- Trong khong pH thng gp trong thm lc a (4,35 <pH 8,3), h cacbonat ch


yu tn ti hai dng H2CO3 v HCO3-.
- Dng khng phn ly H2CO3 chim chnh trong h cacbonat khi pH thp.
- Khi nc c pH ~ 8,3 bt u xut hin CO32-.
Nh vy, [H2CO3], [ HCO3-], [CO32-] c mi tng quan t l vi nhau.
1.2.4. Cc ion ch yu c trong nc thin nhin
a. Ion Cl-

Ngun gc nguyn thy ca cc ion Cl- l t kh HCl v mt phn nh t s


phong ha, ha tan cc khong vt c cha clo trong thch quyn.
Trong nc i dng, ion Cl- c ngun gc kh HCl c thot ra t hot ng
phun tro y i dng v mt phn t nc sng trn cc lc a.
Trong nc sng, nc h,c th khng c hoc rt t ion Cl-, nhng trong
nc bin th hm lng Cl- rt cao. Hm lng Cl- trong nc t nhin c th bin
i t 0 n 170g/l.
Ngy nay, ion Cl- trong nc mt (trn lc a) cn c ngun gc t hot ng
nhn sinh, nhng ng k nht l t nc thi cng nghip cha lng ln clo, c
thi vo cc vc nc t nhin c th lm tng khong ha, lm bin i kiu ha
hc ca nc, do lm suy gim cht lng, nh hng xu n h sinh thi ca vc
nc, c bit l cc vc nc tnh nh h, m,
Ngun gc chnh to nn ion Cl- trong nc t nhin do cc nguyn nhn sau:
- ha tan cc mui clorua rt cao, cao hn tt c cc mui khc.
- Hot ng ca sinh vt, c bit l hot ng ca con ngi l ngun ln cung cp
Cl- cho cc loi nc t nhin.
- Trong nham trm tch cng c nhiu ion Cl-, lng ion Cl- cng tham gia vng
tun hon ca Cl- trong t nhin.
- Do cc qu trnh phong ha cc dung nham.
- Mt phn ln clo trong nc do dung nham ca ni la phun ra cung cp.
b. Ion SO42-

Ngun gc nguyn thy ca cc ion SO42- t kh H2S. Khi trong kh quyn xut
hin oxy, H2S dn b oxy ha thnh axt sunfuric v nc t nhin cng bt u cha
ion SO42-.
Ngun gc chnh to nn ion SO42-:
- Trong nham trm tch c cha thch cao CaSO4.2H2O, khong vt sunfua.
- Oxy ha lu hunh trong t nhin.
- Oxy ha cc hp cht sunfua c trong dung nham, c bit l cc dung nham ca ni la
- Hot ng ca con ngi m ch yu l ngnh cng nghip.
- Do qu trnh phn gii xc ng thc vt.
Hm lng trung bnh SO42- trong nc i dng chim 9,28% trong tng hm
lng cc anion (tnh theo ml/kg). Hm lng ca ion SO42- tuy t nhng u cng

19

c. Trong cc h nc ngt hm lng SO42- cao hn trong nc sng. Trong nc


bin, hm lng SO42- gim dn theo su.
c. Ion kim loi kim (ch yu l K+, Na+)

Ngun gc nguyn thy ca cc ion kim loi kim K+, Na+ ha tan trong nc l
t s phong ha, ha tan cc macma trn b mt Tri t.
Trong nc t nhin, hm lng ion Na+ thng ln hn ion K+ v ion K+ tham
gia vo chu trnh thc vt mnh hn, mt khc, trong mi trng nc, ion K+ cn
phn ng vi axt silixic ha tan v cc thnh phn khc hnh thnh cc khong th
sinh nh t st,
Trong nc i dng, ion Na+ c hm lng ln nht trong cc cation, cn ion
K+ c hm lng nh nht trong cc cation. Cc ion cn li c hm lng rt t. Chng
hn, trong nc bin hm lng Rb khong 0,2 mg/l; Li ch khong 0,1 mg/l.
Hm lng trung bnh trong nc i dng: Na+: chim 77,34% tng cc cation
(tnh theo ml/kg), ion K+ ch chim 1,64%.
Ion Na+ c trng cho nc c khong ha cao. Khi hm lng Na+ t vi
g/l th n l ion ch yu c trong nc.
d. Cc ion Ca2+, Mg2+

Ngun gc nguyn thy ca cc ion Ca2+, Mg2+ trong nc thin nhin l t s


phong ha ha hc cc loi v khong vt trn b mt Tri t bi nc ma, nc
ngm, (cha axt cacbonic v cc axt khc):
CaCO3 + CO2 + H2O Ca2+ + 2HCO3Nhng khi trong nc c hm lng HCO3- cao s din ra qu trnh to kt ta.
y l nguyn nhn chnh gy ra cc nham trm tch vi.
Cc ion Ca2+, Mg2+ c ha tan vi hm lng ln, chng l cc ion chnh ca
nc thin nhin.
Trong nc c khong ha cao th hm lng Ca2+ nh hn hm lng Mg2+.
Trong nc i dng, hm lng trung bnh ca Ca2+ chim 3,37% trong tng cation;
Mg2+ chim 17,62% (tnh theo ml/kg).
e. Cc ion HCO3-, CO32-

HCO3-, CO32- trong nc thin nhin c ngun gc t kh CO2 trong kh quyn,


trong khng kh t v khong cacbonat trn b mt tri t, c bit l trong nc c
khong ha thp.
Trong nc lc a, c bit l nc c ngun gc kh quyn, nc ngm trong
cc thnh phn to trm tch cacbonat v nc c ngun gc macma, ion HCO3- c
hm lng ln nht trong cc ion chnh (v d: nc khong Vnh Ho, c hm lng
HCO3- ti 2445mg/l). Ion HCO3- cng l dng tn ti thng chim phn ln trong h
cacbonat ca nc t nhin. Ion CO32- trong nc(ch tn ti pH 8,3) t gp hn v
nu c, cng thng c hm lng nh hn so vi ion HCO3-, Cl-, SO42-. Cc ion ny
xut hin trong nc do qu trnh ha tan cc mui cacbonat c tc dng ca CO2:
MCO3 + CO2 + H2O M2+ + 2HCO3f. Hp cht sunfua

Trong nc thin nhin, cc hp cht sunfua c th tn ti th kh H2S ha tan,


dng HS-, S2- ca axt H2S v ca cc mui ca hai dng . S in ly ca H2S:
20

H2S H+ + HS-

1 =

HS- H+ + S2-

2 =

[ + ][S ]
= 0,91.10 7
[ 2 S ]
[ + ][ S 2 ]

[ S ]

= 2.10 15

1.2.5. Cc nguyn t vi lng v cht hu c trong nc thin nhin


a. Cc nguyn t vi lng trong nc thin nhin

Cc thnh phn vi lng trong nc l nhng thnh phn tn ti vi hm lng <


1mg/L, tc l thuc c hm lng phn triu, phn t (ppm mg/L, ppb g/L)
hoc nh hn na. Cc thnh phn vi lng c tnh hm lng c hai dng: dng
ha tan (bao gm c kh ha tan) v dng l lng.
C th chia thnh phn vi lng trong nc thnh hai nhm sau:
- Cc thnh phn v c vi lng: Hg, As, Se, Cd, Pb, Cu, Zn,,, Br, I, F, xianua,
sunfua, tn ti trong nc nhiu dng nh cation, anion, phc v c, phc hu c,
kh (dng ha tan); ion hp ph vo cc cht l lng v cht keo trong nc, cc vi kt
ta ca cc khong th sinh c hnh thnh trong nc (dng l lng v dng keo).
- Cc thnh phn hu c vi lng: phenol v dn xut, thuc bo v thc vt, cht
ty ra, du, m,
Cc nguyn t thuc nhm halogen (tr clo), l nguyn t vi lng c trong nc
thin nhin. Chng c tc dng rt ln trong qu trnh sng ca sinh vt. V d nh flo,
nu khng c flo hoc c qu nhiu flo (> 1,5 mg/l) u gy cc bnh v rng. Nu
thiu it gy cc bnh ni tit
Cc nguyn t thuc nhm kim loi nng (Cu, Ni, Co, Pb, Hg, Cd ) c rt t
trong nc thin nhin.
Nguyn t phng x c tnh cao nht trong nc thin nhin. Hm lng ca
chng rt nh nhng li rt d nhn thy. Cc nguyn t phng x thng c trong
nc thin nhin l Radon v Radi.
Ty theo hm lng v dng tn ti ca cc thnh phn v c, hu c vi lng trong
nc c th l yu t c li hoc gy nguy him cho s sng ca sinh vt v con ngi.
b. Cht hu c trong nc thin nhin

Trong nc thin nhin tn ti cc cht hu c c th chia lm hai loi.


- Loi 1: Bao gm cc cht hu c cu to nn c th cc loi sinh vt sng trong
nc nh cc loi ng vt, thc vt sng trong nc.
- Loi 2: Bao gm cc cht hu c do sinh vt thi ra trong qu trnh sng ca chng
hoc trong qu trnh phn gii cc cht hu c t c th cc sinh vt sau khi cht.
Cc cht hu c thng c thnh phn rt phc tp. Ngoi cc nguyn t chnh
nh cacbon, hyro, oxy cn c nhiu loi nguyn t khc nh N, P, K, Ca, Fe, Na,
Tt c nhng cht ny u c th l ngun cung cp cc cht cho nc thin nhin.
Hm lng v mc khong ha cht hu c trong nc c xc nh v
nh gi bi hng lot cc thng s sau:
- Cc thng s biu th gin tip: oxy ho tan (DO) v bo ha oxy; nhu cu oxy
ha hc (COD); nhu cu oxy sinh ha (BOD); t s COD/BOD; s tiu th thuc tm
( oxy ha); hm lng cc ion nit v c; hm lng phophat ho tan,
21

- Cc thng s biu th trc tip: tng cacbon hu c (TOC - total organic carbon),
cacbon hu c ha tan (DOC - dissolved organic carbon); nit hu c; photpho hu c,
1.3. Ha hc nc sng
1.3.1. c im chung

Thnh phn ha hc ca nc sng c quyt nh bi c tnh vn c ca con


sng y. c tnh y bao gm cc yu t sau: Ngun nc cung cp, cu to a cht,
kh tng, thu vn, kh hu, tc dng chy,
Bng 13. Thnh phn ho hc trung bnh ca nc sng h

Thnh phn

% trng lng

Thnh phn

% trng lng

CO32-

35,2

Ca2+

20,4

SO42-

12,4

Mg2+

3,4

Cl-

5,7

Na+

5,8

SiO2

11,7

2,1

NO3-

0,9

(FeAl2)O3

2,7

khong ha ca nc sng thng nh hn cc loi ngun nc khc v nc


sng tip xc vi cc tng nham thch trong thi gian rt ngn do nc sng lun
chuyn ng, kh nng ha tan cc cht rt thp.
1.3.2. ng thi ca cc ion ch yu nht

Da vo khong ha ca sng, ngi ta chia sng lm 4 cp:


- Sng cp I c khong ha rt thp:

< 200 mg/l.

- Sng cp II c khong ha trung bnh:

200 500 mg/l.

- Sng cp III c khong ha cao:

200 500 mg/l.

- Sng cp IV c khong ha rt cao:

> 1000 mg/l.

Hu ht nc cc con sng trn tri t u l sng cp I hoc cp II.


C hai ngun cung cp nc cho sng l ngun nc trn mt t (nc ma, nc
tuyt v bng) v ngun nc ngm (nc trong tng t bi, nc trong tng ngm).
Kh hu c nh hng rt ln ti ngun cung cp nc cho sng, lm cho lng
nc cung cp cho sng thay i, thnh phn ha hc ca cc ngun nc cung cp
cho sng thay i v do lm cho thnh phn ha hc ca nc sng cng thay i.
Nh vy, mi con sng u c ng thi thy ha c th.
Nhn chung i vi cc con sng c khong ha trung bnh v thp, khi khong
ha tng ln th hm lng cc ion cng tng ln tng ng, c bit l hm lng Cl- v
HCO3- tng rt nhanh. i vi cc con sng c khong ho cao, khi khong ha tng
ln th hm lng cc ion cng tng theo, nhng c bit hm lng HCO3- gim.
1.3.3. ng thi ca cc hp cht hu c

Cc cht hu c trong nc sng tn ti di dng trng thi cc cht mc nt b


xi t t v m ly chy vo sng v cc sn vt c phn gii t cc cht hu c
to ra.
a. oxy ha ca nc (COD - Chemical Oxygen Demand)
22

xc nh hm lng ca cc cht hu c tn ti trong nc ngi ta dng i


lng ch oxy ha ca nc, vit tt l COD.
oxy ha ca nc l s miligam oxy cn thit oxy ho ht cc cht hu c
c trong 1 lt nc. Nh vy qua lng oxy cn dng c th tnh ra hm lng cc hp
cht hu c c trong nc.
b. Phn loi nc sng

Da vo oxy ho ngi ta chia nc sng ra cc loi:


- Nc sng c COD rt thp:

COD 2 mg/l.

- Nc sng c COD thp:

COD = 2 5 mg/l.

- Nc sng c COD trung bnh:

COD = 5 10 mg/l.

- Nc sng c COD hi cao:

COD = 10 20 mg/l.

- Nc sng c COD cao:

COD = 20 30 mg/l.

- Nc sng c COD rt cao:

COD > 30 mg/l.

1.3.4. ng thi ca cc cht kh ha tan v ca ion H+


a. ng thi ca cc cht kh ha tan

Hm lng ca cc cht kh ha tan vo nc ph thuc vo cc yu t:


- Bn cht ca cht kh;
- Nhit ca nc;
- Cng ca cc qu trnh quang hp trong nc;
- Thnh phn ca ngun nc b sung cho sng;
- p sut ring phn ca cc kh trn b mt nc.
Thng thng hm lng oxy trong nc sng khng vt qu 15 mg/l v hm
lng CO2 khng qu 30 mg/l.

* Kh oxy:
Hm lng oxy trong nc sng ph thuc vo nhiu yu t.
Nhn chung v ma h, hm lng oxy trong nc sng vo khong 6 8 mg/l v
nhit cao; v ma ng, th khong 8 12 mg/l v nhit ca nc thp. Hm
lng ny cn ph thuc vo ngun sinh vt sng trong nc v kh hu ca khu vc
sng chy qua.

* Kh CO2:
ng thi ca kh CO2 trong nc sng tng t ng thi ca oxy.
V ma ng hm lng CO2 cao v sinh vt trong nc t hot ng nn lng
CO2 tiu th t, ng thi ngun nc chnh cung cp cho sng v ma ng l nc
ngm thng c nhiu CO2.
V ma h, nhit cao, hot ng ca cc vi sinh vt nhiu nn hm lng ca
CO2 gim nhiu, ch vo khong 1 - 3 mg/l. Thm ch c lc khng cn CO2 trong
nc, nn vi sinh vt phi ly CO2 trong khng kh.
b. ng thi ca ion H+

23

Hm lng ion H+ trong nc sng ph thuc nhiu vo ma v.


- Gi tr pH ca hu ht cc con sng trong ma ng t 6,8 - 7,8 cn trong ma h
cao hn, t 7,8 - 8,8.
- Cc con sng c b sung bng ngun nc ca cc m ly th thng c pH thp
(pH < 6). Cc con sng khu vc nhit i v ma h pH c th tng ln ti 9.
1.4. Ha hc nc ngm
1.4.1. c im chung

Nc ngm tip xc trc tip v hon ton vi t v nham thch: nc ngm c


th l cc mng mng bao ph cc phn t nh b ca t, nham thch; l cht lng
c cha y trong cc ng mao dn nh b gia cc ht t, ; nc ngm c th
to ra cc tia nc nh trong cc tng ngm nc.
Cht lng nc ngm ph thuc vo cu trc a tng m nc thm qua. Do vy
nc chy qua cc tng a tng cha ct hoc granit thng c tnh axit v cha t cht
khong. Khi chy qua a tng cha vi th nc thng c cng v kim
hydrocacbonat kh cao. Ngoi ra, cc c trng chung ca nc ngm l:
- c thp.
- Nhit v thnh phn ho hc tng i n nh.
- Khng c oxy, nhng c th cha nhiu kh H2S, CO2,
- Cha nhiu cht khong ho tan, ch yu l st, mangan, canxi, magie, flo.
- Khng c s hin din ca vi sinh vt.
Nc ngm cng c chia thnh cc tng, lp khc nhau v thnh phn ha hc
ca cc tng lp cng khc nhau.
nh hng ca kh hu i vi nc ngm khng ng u.
Thnh phn ca nc ngm khng nhng chu nh hng v thnh phn ha hc
ca tng nham thch cha n m cn ph thuc vo tnh cht vt l ca cc tng nham
thch .
Nc ngm t chu nh hng ca sinh vt nhng chu nh hng nhiu ca vi
sinh vt. tng su do khng c oxy v nh sng nn vi sinh vt ym kh hot ng
mnh, chi phi nhiu n thnh phn ha hc ca nc ngm. V vy thnh phn ha
hc ca nc ngm cha nhiu cht c ngun gc vi sinh vt.
Nc ngm khng c oxy. Khi pH < 5,5, trong nc ngm thng cha nhiu
kh CO2. y l kh c tnh n mn kim loi v ngn cn vic tng pH ca nc.
Thng nc ngm c nng kh CO2 khong 30 - 50 mg/l, nhiu ni nc ngm
mch su (200 300 m) nng CO2 c th ln n 320 mg/l. Cc bin php lm
thong c th ui kh CO2, ng thi thu nhn oxy h tr cho cc qu trnh kh st v
mangan. Ngoi ra, trong nc ngm c th cha kh H2S c hm lng n vi chc
mg/l. y l sn phm ca qu trnh phn hy ym kh cc cht hu c c trong nc.
1.4.2. S phn tng ca nc ngm
a. Nc tng trn

T mt t thm xung to ra tng nc ngm ny, sau li c tho tiu ra


sng, h. V vy nc tng ny giao lu mnh.

24

Thnh phn ha hc ca nc tng trn ph thuc vo: thnh phn ha hc ca ngun


nc mt, thnh phn ha hc ca lp tng t cha n, kh hu, thi tit
Do s bay hi ca nc mt t, nc ngm tng trn c th theo cc mao dn
ln gn hoc thm ch ln ti mt t mang theo nhiu mui khong, khi nc bay hi
li phn mui khong ny cho t. y l mt trong nhng yu t quan trng lm
cho t kh hn bin thnh t chua mn.
b. Nc tng gia

Nc tng ny nm bn di mt gc xm thc, ph thuc cht ch vo mc


bc l v a cht thu vn.
Nc t trn t thm xung ti tng nc ngm ny thng rt chm, c bit
l vi tng nham thch t thm nc. V vy, nc tng ny l nc chm giao lu.
Trong tng ny, thnh phn nguyn thu ca nc ban u b thay i nhiu do nc
v nham thch tc dng mt thit vi nhau hoc do s trn ln cc ngun nc khc.
c. Nc tng di

Nc tng ny cch bit hon ton vi mt t v hu nh khng giao lu. C


nhiu gi thit khc nhau v ngun gc ca tng nc ny:
- Do nc tng trn thm xung.
- Do nc bin thm vo m c.
- Do nc t rt lu b chn vi bi cc tng nham thch hnh thnh m c.
- Do di p lc rt ln m nc trong cc nham thch hay bn tch ra m c
1.4.3. Nc khong v nc c thnh phn c bit
a. Nc khong

Nc khong l loi nc ngm c cha nhiu cht c tnh cht kch thch v
phng din sinh hc. Cc loi nc ny c dng trong vic iu dng sc kho
v cha bnh.
Nc ngm c khong ha ln hn 1,0 g/l c th gi l nc khong. Khi
khong ho ln hn 50 mg/l th gi l nc mn.
Ngi ta thng cn c vo hm lng mt s cht c tc dng kch thch sinh
hc trong nc khong phn loi nc khong.
Hm lng CO2 t do ti thiu c gi l nc khong l 0,250 g/l. Hm
lng CO2 t do xp x bng 0,750 g/l mi c gi l nc khong cacbonic.
Thc ra gii hn gia nc nht v nc khong khng r rt. C nhng loi
nc c khong ho rt thp, nhng c cha mt s cht c tc dng cha bnh nn
vn c gi l nc khong. Ngi ta cng c th phn loi nc khong theo nhit
: nc lnh (nhit ca nc < 253oK), nc m (nhit ca nc t 253 310oK), nc nng (nhit ca nc > 315oK)
b. Nc c thnh phn c bit

Trong nc ngm c loi nc cha rt t cc ion v khng n nh. c bit


trong loi nc ny c cha hm lng ion H+ cao nn c gi l nc axt v gi tr
pH thng nh hn 4.
Ngun gc ca cc loi nc ny l do cc hp cht ca S trong nham thch b
oxy ho dn dn to thnh H2SO4 tan trong nc. Qu trnh ny thng xy ra tng
25

nc ngm su di t, cng c th xy ra trong nham thch trm tch lp trn


cng do hot ng ca ni la cung cp.
1.5. Ha hc nc bin
1.5.1. c im chung

Nc bin chim 99% ton b lng nc trn tri t, n bao ph 71% b mt


tri t. Th tch nc bin khong 1304.106 km3.
V bin v cc i dng thng nhau nn thnh phn ha hc ca nc bin
tng i ng nht theo thi gian v khng gian.
Nc bin c khong ho rt cao, thng vo khong 35 g/l. Nng mui
trong nc bin ln hn trong nc ngt 2000 ln.
V bin v cc i dng thng nhau nn thnh phn cc cht trong chng tng
i ng nht. Hm lng mui c th khc bit nhiu trong cc i dng nhng t
l v nhng thnh phn chnh th hu nh khng i.
Din t theo ngn ng ha hc th nc bin l dung dch ca 0,5 mol NaCl, 0,05
mol MgSO4 v vi lng ca tt c cc nguyn t c mt trong ton cu.
1.5.2. Cc ion ch yu c trong nc bin

khong ho ca nc bin hon ton ph thuc vo lng cc ion ch yu c


trong nc bin.
Trong nc bin Na+, Cl-, Mg2+ chim 90%; K+, Ca2+, SO42- chim 3%; cc cht
cn li chim 7% tng lng cc cht.
Bng 14. Cc thnh phn ch yu ca nc bin
STT

Cht

Hm lng trung
bnh (mg/l)

STT

Cht

Hm lng trung
bnh (mg/l)

Na

10500

16

2460

380

17

Cl

18980

Be

0,00005

18

Br

65

Mg

1270

19

0,06

Ca

400

20

Fe

0,01

Ba

0,03

21

Zn

0,01

20

22

28

Al

0,01

23

Cu

0,003

Si

24

Mn

0,002

10

Sn

0,003

25

Co

0,005

11

Pb

0,003

26

Ni

0,005

12

0,6

27

Ag

0,0003

13

0,07

28

Cd

0,0001

14

As

0,003

29

Cr

0,00005

15

Bi

0,0002

30

Hg

0,00003

26

Hm lng cc ion ch yu c trong nc bin c mt th t xc nh. C


khong 11 thnh phn ion chnh - chim khong 99,99% tng hm lng cc cht
khong ha tan.
- V anion:Cl- (55,04%) > SO42-(7,68%) > HCO3- + CO32-.
- V cation: Na+ (30,61%) > K+ > Mg2+ (3,69%) > Ca2+.
Bng 15. Hm lng cc nguyn t vi lng ha tan trong nc bin
tn ti di dng cc hp cht khc nhau:
Nguyn t

Dng tn ti chnh

Nguyn t

Dng tn ti chnh

Fe

Fe2+, FeCl+, Fe(OH)3

NO3-

Cu

CuCO3, Cu(CO3)22-, Cu(OH)+

F-

2+

HPO42-, NaHPO4,

Zn

Zn , ZnCl , ZnSO4

As

As(OH)3, As(OH)4-

Br

Br-

Pd

PdCl42-

IO3-

Cd

CdCl+, CdCl2

Si

H4SiO4, H3SiO4-

Pb

PbCl-, PbCl2, PbCO3

Te

TeO32-, HTeO3-

Hg

HgCl42-, HgCl3-, HgCl2

MgHPO4, PO43-

Nhn chung hm lng ion trong nc bin rt n nh v mt t l gia chng.


Nguyn nhn ca tnh n nh l do nc bin c tnh giao lu rt mnh nn kh nng
trn ln l rt cao. V li, th tch nc bin rt ln, mt s thay i nh, cc b s
khng nh hng n thnh phn ha hc ca nc bin.
kim: L tng nng anion ca cc axt yu c mt trong nc bin. Trong
cc loi ion ch yu ca nc bin th HCO3- v CO32- ca axt cacbonic (H2CO3) v
H2BO3- ca axt 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.
nhng vng ca sng h s kim (= kim/ mui) thng rt cao (khong
760), i dng (khong 660 - 680), khu vc cc ngun nc lc a ra bin
cng nhiu th h s kim cng tng (c th ln n 1000).
1.5.3. mn ( mui) ca nc bin

mn ca nc bin l i lng c trng nh lng cho lng cc cht


khong rn ha tan (cc mui) trong nc bin.
mui ca 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
vi i dng. iu ny c Marxet (pht hin nm 1819) v Ditmar (khng nh
nm 1876) trn c s nghin cu thnh phn mui nc bin nhiu vng trn th
gii v tng kt thnh quy lut c bn:
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.

27

T quy lut ny c th xc nh chnh xc hm lng ca mt loi ion no , ri


bng tnh ton n gin mi lin h bit th d dng suy ra hm lng ca cc ion
khc v do vy c th xc nh c mn ca nc bin. Ion Cl- c chn cho
mc ch ny v s c mt ca n trong nc bin vi nng ln nht.
Nng trung bnh ca Cl- trong nc b mt i dng l 19,3534 g/kg.
Trn c s cc ngh quyt ca hi ngh quc t v hi dng hc nm 1889 v
1901 ti Stckhm (Thu in), M. Knudsen v cng s khng nh:
mui ca 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 clo tng ng, nhng mui cacbonat c thay th bng oxt v cc
cht hu c b phn hy ht 4800C.
clo nc bin l tng lng (tnh bng gam sau khi quy i tng ng
sang clo) ca cc halogen c trong 1 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) v clo (tnh bng g/kg, k hiu Cl) nh sau:
S = 0,034 + 1,8050.Cl

(1-24)

Nhng nm sau ny, mt s tc gi cn xy dng nhng cng thc mi v mi


lin h gia tng nng cc ion (tnh bng g/kg, k hiu I) chng hn:
Lymen v Fleming (1940): I = 0,069 + 1,8112.Cl
Kocx (1963):

S = 1,80655.Cl

Kocx (1966):

I = 1,81578.Cl ;...

Thc nghim chng t I%o gn vi mui thc ca nc bin hn gi tr


S; song s sai khc ca chng khng ng k, ch vo khong 0,004 khi
mui nc bin nm trong khong 30 - 40.
Tuy nhin mn ca cc i dng cng c dao ng. S dao ng ny ph
thuc vo qu trnh cn bng ca qu trnh bc hi v ngng t ca nc bin. Qu
trnh ny ph thuc vo nhiu yu t nh v tr a l, kh hu, ma, Chng hn
vng nhit i c mn S = 35,7 ; cc bc v cc nam S = 34,5.
mn ca nc bin cn thay i theo su. Ngi ta nhn thy rng t mt ca
i dng ti su khong 5000m mn dao ng trong khong t 34,9 - 36,5.
1.6. Phng php nghin cu ho nc v yu cu s dng nc
1.6.1. B tr h thng trm o c cht lng nc

Ty theo nhu cu s dng nc m ngi ta b tr cc trm o c cht lng


nc. Vic b tr v tr v s lng cc trm o phi lm sao o c c nhng c
trng nht ca cht lng ngun nc phc v cho cc nhu cu trn v phi theo di
s bin i cht lng cc ngun nc c bin php x l cn thit, kp thi.
1.6.2. Phng php ly mu nc
a. Cc loi mu nc

Ty vo mc ch phn tch khc nhau (ho hc, sinh vt, vi sinh vt,) m cc
phng php, thit b ly mu v cch x l mu khc nhau.

28

- Mu n: l loi mu gin on, thng c ly th cng hay t ng t nc


trn b mt, hoc mt su nht nh hoc di y. Mi mu thng ch i
din cho cht lng nc thi im v a im ly mu.
- Mu gin on (theo thi gian v theo v tr).
- Mu lin tc (ly lu lng nh trc v lu lng thay i): Cha mi thnh
phn ca nc trong sut giai on ly mu, loi mu ny c th pht hin c s
thay i cht lng nc.
- Mu lot (theo chiu su hoc theo din tch): Tc l ly theo su khc nhau
cng mt v tr hoc mt v tr nht nh ca mt vng nc nhiu v tr khc nhau.
- Mu t hp: Tun th vi mt s mc gii hn c da trn gi tr trung bnh
ca cht lng nc.
Khng nn dng mu trn xc nh hm lng ca nhng ch tiu ca nc d
b thay i nh pH, cc kh ha tan.
b. Mt s ch dn khi ly mu nc

V tr ly mu ph thuc vo mc ch nghin cu. Thi gian v tn sut ly mu


ph thuc vo mc bin ng ca cc cht, c th theo cc thi gian trong ngy.
Trong ngy nng, pH ca nc c th tng, c bit l nc c kh nng m thp do
kh nng trao i CO2 ca thc vt thy sinh v nng photpho c th s b gim i.
Lng nc cn ly ti thiu m bo cho cc php phn tch, thng 1 - 2 lt.
Dng c ng mu phi c lm sch bng cc bin php cn thit nh ra bng cc
cht ty ra hoc dung dch axt. i vi phn tch vi sinh vt th dng c ng mu
cn phi c v trng. Ngoi ra vt liu lm bnh cha mu phi tr v mt ha hc
v khng c kh nng hp thu cc cht c trong mu nc.
Khi ly mu i vi ngun nc chy nh sng, sui,...th nn ly mu ch
nc chy mnh nht.
Mu ly cc h thin nhin, h cha, cc ao, m,... th nn ly mu cc v tr
v su khc nhau. Khng nn ly mu trung bnh i vi loi mu ny.
Mu ly t cc mch, cc loi ging, cc b h cha nc nhn to th nn ly
nhng su cn thit.
Mu nc ma phi ly vo lc tri ma v ghi r thi im ly mu.
Mu t cc trm v cc vi nc sinh hot thng thng c ly trc tip ti
cc ng dn nc ra.
Mu nc thi nn ly trung bnh, trc khi ly mu cn nghin cu k yu cu,
mc ch s dng nc v cc iu kin sinh hot khc.
c. Bo qun v x l mu nc trc khi phn tch

Trong khong thi gian t lc ly mu nc n khi phn tch, hm lng ca


cc hp phn c th b thay i vi mc khc nhau.
Nhit v pH ca nc l hai i lng bin i nhanh nht, v vy hai ch tiu
ny cn c xc nh ngay ti ni ly mu. Hm lng mt s kh cn phi c xc
nh ngay nh: O2, CO2, H2S, Cl2.
i vi vic xc nh kim loi nng trong nc th cn tun th theo nhng quy
trnh nghim ngt bo qun mu.

29

Vic bo qun v x l mu nc trc khi phn tch thnh phn ca n phi


tun theo tiu chun vit nam TCVN 5993 - 1995 v ISO 5667 - 3 - 1985.
Bo qun mu nc l nhm gi gn cc yu t, ng thi duy tr tnh cht v
tnh trng mu nc trong mt khong thi gian ngn trc khi em phn tch.

* Ly mu phn tch ch tiu ha l: Trng hp ly mu phn tch ch tiu ha l th


cn phi np mu y bnh sao cho khng c khng kh trn mu. iu hn ch
s tng tc gia pha lng vi pha kh v s lc khi vn chuyn. Cc loi bnh
polyetylen (PE) thch hp cho vic ly mu thng thng xc nh cc thng s
vt l, ha hc ca nc t nhin. Bnh PE ly mu c ra sch v trng qua ngun
nc c ly mu 3 ln.

* Ly mu phn tch ch tiu vi sinh: Trc khi ly mu nc, cc dng c, chai l


cn thit phi c tit trng. Dng chai thy tinh c nt mi vn cht. Th tch chai
l 250ml. Ra sch chai sau sy kh kh trng 160oC trong thi gian 2 gi.
- Ly nc ti vi: t ming vi nc cn thn bng bng tm cn vi ngn la
to. M nc, cho chy tht mnh trong vng 1 pht, sau vn nh tia nc chy
thm vi pht, ri hng ly 2/3 chai (trong chai cn c khong trng lc mu trc
khi lm xt nghim).
- Ly nc ti ging, sng, h: Buc chai ly mu vo dy qung ri qung xung
ging, sng, h su cch mt nc 0,5m. Sau khi nc vo y chai (khng cn
bt kh ni ln) th ko ln, kh trng ming chai, bt nc ri y np.
Bng 16. Dng c cha mu, v iu kin bo qun mu nc
ca mt s thng s (trong 1 lt mu nc)
TT

Phn tch

Chai ng

iu kin bo qun
o

Thi gian
bo qun ti a

TSS

PE

Lnh 4 C

4 gi

pH

PE

Khng

6 gi

kim

PE

Lnh 4oC

24 gi

TT

C nh ti ch
(Winkler)

6 gi

Oxy ha tan
(DO)

BOD

PE

Lnh 4oC

4 gi

COD

PE

Lnh 4oC

24 gi

NH 3

PE

NO3-

PE

PO4

3-

10

Lnh 4oC, H2SO4 c v


23 ml CHCl3
Lnh 4oC

24 gi
24 gi

TT

Lnh 4 C; 1-2 ml CHCl3

24 gi

Cd

PE

5 ml HNO3 c

11

As

PE

5 ml HCl

12

Hg

PE

1 ml HNO3 c

13

Pb

PE

3 ml HNO3 c v
2 ml CH3COOH c
30

Ghi ch: PE: Chai polyethylen;

TT: Chai thu tinh

1.6.3. Yu cu s dng mt s ngun nc


a. Nc dng cho cng nghip

* Cng nghip lm giy:


- c v mu ca nc phi thp giy lm ra c trng cao. Trong nc
khng c c cht l lng mt giy nhn, khng sn.
- Hm lng st trong nc phi thp giy khng b vng theo thi gian.
- cng trong nc phi thp giy d dn v khng dn in.
- pH ca nc phi trung bnh, nu qu cao th kh lm, cn nu thp qu giy
d mn, mc.

* Cng nghip dt:


- pH = 6,8 7,5;
- Hm lng st < 0,1 mg/l.
b. Nc dng cho nng nghip

Thng thng nc c khong ho trong khong 0,8 1,0 g/l l nc thch


hp cho nng nghip. Nu khong ha ln ti 4 g/l l nc chua, mn khng dng
cho nng nghip c.

* H s ti Ka: theo thc nghim ph thuc vo hm lng cc cht trong nc:


- Nu [Na+] < [Cl-]:

a =

288
5[Cl ]

- Nu [Na+] > [Cl-] v [Na+] < [SO42-] + [Cl-]: a =

288
[ Na ] + [Cl ]

- Nu [Na+] > [Cl-] + [SO42-]:

288
10[ Na ] 5[Cl ] 9[ SO42 ]

a =

Nng cc ion tnh theo mlg/l.


31

Da vo Ka ngi ta chia nc s dng cho nng nghip thnh 4 loi:


- Ka > 18: nc rt tt.
- Ka = 18 6: nc dng ti c.
- Ka = 5,9 1,2 : nc dng c th ti c nhng khng tt.
- Ka < 1,2: khng th ti c.

* Cc cht l lng trong nc: thng l cc ht bn, ct, ph sa, cc cht ny c


th lm cho t ph nhiu hoc c th lm cho t chua mn dn. Kch thc cc ht
cht l lng trong nc hp l l 0,2 0,005 mm.

* Nhit : c nh hng ln n cht lng ca nc ti. Tt nht l nc ti c


nhit thch hp cho tng loi cy trng.

* Cc yu t khc:
- Dng nc ti khng c ln cc axt t do nh HCl, H2SO4.
- Nng cc loi mui: ZnSO4, Na2SO4, Na2CO3, NaCl...phi thp v nu hm lng
ca chng cao s gy keo t t, lm cho t cng li khng thch hp cho cy trng.
- Nc thi u khng th dng lm nc ti.
c. Nc dng cho nui c

- Nhu cu v oxy: Hm lng oxy ha tan trong nc cng cao cng tt. Gii hn
cho php hm lng oxy ho tan trong nc (DO) l 3 mg/l. Nu nh hn th c bt
u kh th v nu DO < 0,5 mg/l th c s cht.
- Cc cht khc: Cc thnh phn ho hc khc phi c to cho cc sinh vt
trong nc pht trin tt, lm ngun thc n di do cho c.
- pH: thch hp cho vic nui c t 7 8. Nu pH < 6 lm gim tc dng h hp,
gim kh nng hp th thc n, c s chm ln.
d. Nc dng cho ni hi

- Tc dng lm han g ni hi: Ni hi b g ch yu l do trong nc c axt v oxy


ha tan gy ra. Nc dng cho ni hi yu cu hm lng cc loi mui cacbonat
khng qu 15 mg/l v hm lng oxy khng c qu 0,1 mg/l. c bit vi ni hi
cao p phi loi tr ht kh oxy ha tan.
- Tc dng lng ng cn: nh hng ca lp cn dn n nhit ca ni hi
km, gy lng ph nhin liu ng thi lm thnh ni hi c nhit khng ng nht.
V bn cht ca cn lng ng l do nhit cao nn cc mui canxi, magi v
mt s kim loi khc bin thnh kt ta. V d:
Ca(HCO3)2

t0

Mg(HCO3)2

t0

CaCl2 + MgSO4
CaCl2 +
CaSO4 (tan)
MgSO4
FeCl3 +
2Fe(OH)2

CaCO3 +

CO2 +

MgCO3 +

= CaSO4

CO2 +

H 2O
H 2O

+ MgCl2

Na2CO3 = CaCO3 + 2NaCl


+ Na2SiO3 = CaSiO3 + Na2SO4
+ Na2SiO3 = MgSiO3 + Na2SO4
3H2O
Fe(OH)3 + 3HCl
0
t
Fe2O3 + 3H2O

32

- Tc dng si bt: khi trong nc c cc mui kali, mui natri, x phng, du m


, chng thng lm gim sc cng b mt ca nc, d to ra cc bt kh tan c tc
dng gy ra p sut khng u trn b mt cc tuabin hi, lm gim tui th tuabin.
e. Nc dng cho b tng

Tc dng ca nc i vi b tng ch yu l qu trnh cc cht trong nc tc


dng vi cc cht c trong b tng lm cho b tng b ph hu dn. Tnh xm thc ca
nc c th chia lm 5 loi:
- Xm thc ca CO2 ho tan: Lng CO2 d s ho tan cc mui cacbonat trong b
tng lm cho b mt b tng b ph hy dn.
CaCO3 + CO2 + H2O = Ca(HCO3)2
MgCO3 + CO2 + H2O = Mg(HCO3)2

- Xm thc do kh kim: Khi hm lng [HCO3-] < 131 mg/l th s xy ra hin tng cc
mui cacbonat v Ca(OH)2 trong b tng tan ra cng lm cho cng trnh b ph hy.
- Xm thc ca cc loi axt: khi nc c pH thp. S xm thc ca axt ch yu
l qu trnh ho tan cc mui cacbonat trong b tng lm cho b tng b ph hy dn.
- Xm thc ca cc loi mui sunfat: Khi hm lng SO42- trong nc cao th SO42cng vi nc thm vo b tng to ra CaSO4.2H2O. Mui ny c h s gin n cao
lm cho b tng b rn nt.
- Xm thc ca mui magi: tng t SO42-.
f. Nc dng cho sinh hot

Nc dng cho sinh hot ca con ngi l nc p ng y cc yu cu sau:


- Nc khng c thnh phn c hi: l cc ion kim loi nng, cc cht khc nh
H2S, NH4+, NO2-, v cc cht hu c.
- khong ho ca nc phi thp: cng ca nc thch hp vi i sng l
20H0 (0H), trng hp c bit khng c vt qu 40H0. V rng nc c cng
cao hay khong ho cao s c nhiu tc hi cho i sng.
n v o: - c (oH): 1oH = 10mg CaO/l nc.
cng (mg CaCO3/L) = cng tng cng - cng canci.
cng < 50mg CaCO3/l : nc mm ; 50 - 150mg CaCO3/l : nc trung bnh
cng 150 - 300mg CaCO3/l : nc cng;
cng > 300mg CaCO3/l : nc rt cng.
Hm lng Fe trong nc mt d c t cng lm cho cht lng nc gim i
nhiu. Khi hm lng Fe > 1mg/l th nc bt u vn c, c v v mi kh chu. Khi
hm lng Fe qu ln lm nc c mu vng v c vng ni ln rt kh s dng.
- Tnh cht vt l ca nc phi tt: khng c mi, v kh chu, phi khng c mu
sc v trong sut.

33

Chng 2:

HA HC PHN TCH NH LNG

2.1. Phng php phn tch th tch


2.1.1. Khi nim chung
a. Nguyn tc

Da vo th tch v nng cc cht tc dng va vi nhau (tng ng


nhau) xc nh hm lng cc cht cn tm.
V d: Mun xc nh nng dung dch NaOH ta ly V th tch dung dch NaOH cho
tc dng vi dung dch HCl bit nng . Gi V l th tch dung dch HCl va
dng ht, khi :
V . NNaOH = V. NHCl

(2-1)

- Dung dch tiu chun: l dung dch bit chnh xc nng ca n.


- Dung dch chun : l dung dch cha bit nng . Ta dng dung dch tiu
chun xc nh n.
- im tng ng: l im khi dung dch tiu chun v dung dch chun tc
dng va vi nhau. Ngi ta xc nh im tng ng bng cht ch th mu.
Trong thc t im dng chun c th khng trng vi im tng ng v iu
gy ra yu t sai s chun .
b. Cc phng php phn tch th tch

iu kin phn tch:


- Cc phn ng phi xy ra hon ton theo mt phng trnh ha hc xc nh.
- Tc phn ng phi nhanh.
- Khng c phn ng ph xy ra.
- C th xc nh c im tng ng.
Trong thc t ngi ta chia ra lm 4 phng php chnh:
- Phng php trung ha.
- Phng php kt ta.
- Phng php phc cht.
- Phng php oxy ho kh.
c. Nng dung dch trong phng php phn tch th tch

biu th thnh phn ca mt dung dch, ngi ta dng nng dung dch.
Vy nng dung dch l lng cht tan c trong mt lng xc nh dung dch hoc
dung mi, lng cht tan ln to dung dch m c, ngc li l dung dch long.

* Nng phn trm theo khi lng (%): s gam cht tan trong 100 gam dung dch:
C% =

m Ct
100
m dd

(2-2)

V d 1: Dung dch NaOH 20% ngha l c 100g dung dch th c 20g NaOH tan trong
.

* Nng % theo th tch: Biu th s ml cht tan c trong 100ml dung dch.
34

V d 2: Ancol etylic 700 ngha l trong 100ml dung dch ru ny cn c 70ml


C2H5OH nguyn cht v 30ml nc.

* Nng mol: S mol cht tan c trong 1 lt dung dch:


nct
Vdd (l )

CM =

(2-3)

* Nng ng lng: Mt loi nng khc thng c s dng tnh ton


trong cc phng php phn tch th tch l nng ng lng c nh ngha l
s ng lng gam ca cht tan trong mt lt dung dch.

CN =

n'
V

(2-4)

V: th tch (lt)
n: s ng lng gam cht tan c trong dung dch.
V d 3: Dung dch HCl 2N: l dung dch c cha 2 ng lng gam hoc 2 36,5g
HCl nguyn cht.
p dng nh lut ng lng cho cc phn ng trong dung dch:
Gi s phn ng :

A + B C

Gi:
NA, NB : nng ng lng gam ca 2 dung dch A v B
VA VB: th tch ca 2 dung dch A v B phn ng va vi nhau
Theo nh lut ng lng ta c:
NA .VA = NB .VB

(2-5)

y l biu thc ton hc p dng nh lut ng lng cho dung dch.

* S lin quan gia cc loi nng .


- S lin quan gia cc nng phn trm (C%): Trn m1 gam dung dch c C1%
vi m2 gam dung dch c C2%, c dung dch c C%, ta c:
m1.C1 + m2.C2 = (m1 + m2)C

(2-6)

Nu pha long bng nc th coi nng C% ca nc bng 0.


- S lin quan gia cc nng mol (CM):
V1.C M 1 + V2.C M 2 = (V1 + V2)CM

(2-7)

Nu pha long bng nc th coi nng CM ca nc bng 0.


- Gia nng mol v nng phn trm:
CM =

10dC %
M

(2-8)

M:

khi lng phn t cht tan

CM:

nng mol ca dung dch

d:

khi lng ring ca dung dch

C%:

nng % ca dung dch


35

- Gia nng ng lng v nng phn trm ca dung dch:


10dC %
D

(2-9)

CN = n.CM

(2-10)

CN =

D: ng lng gam
- Gia CM v CN:
n: s e m 1 ptg cht trao i
d. Cc cch chun trong phn tch th tch

* Cch chun trc tip:


Thm t t dung dch chun vo dung dch nh phn, thuc th R tc dng trc
tip vi cht nh phn X (dung dch chun ) theo phn ng:
R + X Q + Y
Da vo th tch v nng ca dung dch chun. Tnh lng cht X.
V d 1. Xc nh NNaOH bng dung dch tiu chun HCl.
Ti im tng ng: VNaOH . NNaOH = VHCl . NHCl
V d 2. chun ha dung dch NaOH, ngi ta ho tan 1,2600 gam axt oxalic
H2C2O4.2H2O v nc v thm nc n 500,00 ml. Chun 25 ml dung dch thu
c ht 12,58 ml NaOH. Tnh [NaOH].
Gii:
- Tnh theo nh lut hp thc (lht):
aA
n0 (tng mol ban u)

CA.VA

To phn ng cc i: max =
H2C2O4 +
n0

bB

cC

dD

CB.VB
C A .V A C B .V B
=
a
b

2NaOH Na2C2O4 +

2H2O

C.12,58
1000

1,260
25

H 2 C 2 O4 500

1,260 25 C.12,58
=
.
126,00 500 2.1000

max

Suy ra: [ NaOH ] =

2.1,260.25,00.1000
= 0,07949(mol / l )
126,00.500,00.12,58

- Tnh theo ng lng (lg):


2 C 2 O 4 .2 H 2 O =

M H 2C2O4 . 2 H 2O
2

126,00
= 63,00( gam)
2

Nng ng lng ca:


[H2C2O4] =

1,2600 1000
.
= 0,04000 N
63,00 500,00

36

Nng ng lng ca NaOH = nng mol


Suy ra: V NaOH N NaOH = V H 2C2O4 N H 2C2O4

12,58. NNaOH = 25,00. 0,04000

NNaOH = 0,07949N = 0,07949M

* Cch chun ngc:


Gi X: l cht cn xc nh nng , M l cht bit nng , c th tc dng
vi X to cht bn.
Cho M d tc dng vi X: M + X MX
Dng dung dch tiu chun Y xc nh lng M d:
Md + Y MY
cng thc tnh nng cht X nh sau:
VM . NM = VX . NX + VY . NY
X =

V M N M VY N Y
VX

V d 3. xc nh SO42- trong nc ta dng dung dch Ba2+ d bit nng cho


tc dng vi SO42-.
Gii:
2+

Ba

2-

+ SO4

BaSO4

Sau chng ta dng dung dch tiu chun EDTA chun Ba2+ d:
Ba2+ + EDTA = Ba. ADTA
V Ba 2 + .N Ba 2 + = V SO 2 .N SO 2 + V EDTA .N EDTA
4

N SO 2 =
4

V Ba 2 + .N Ba 2 + V EDTA .N EDTA
V SO 2
4

* Cch chun gin tip:


Cht X l cht cn xc nh. Cho M tc dng vi cht X:
M + X MX
Xc nh M trong MX bng dung dch tiu chun Y:
MX + Y Z
t ta c:

VX.NX = VY.NY = VZ.NZ

V d 4. xc nh Ca2+ trong mu nc ta cho ion C2O42- tc dng vi Ca2+ to kt


ta bn:
Gii:
Ca2+ + C2O42- CaC2O4
Sau chun bng dung dch KMnO4 trong mi trng axt mnh:
5CaC2O4 + 2KMnO4 + 8H2SO4 = 2MnSO4 + K2SO4 + 5CaSO4 + 10CO2 + 8H2O
37

V d 5. nh lng Cu ngi ta ho tan 1,080 gam qung ng. Thm KI d. Sau


chun it gii phng ra ht 15,65 ml Na2S2O3 0,0950M. Tnh % Cu trong qung.
Gii:
Phng trnh phn ng:
2Cu2+ + 5I- (d) 2CuI + I3Cu2+ b th bng I3-.
Chun I3- bng Na2S2O3: 2S2O32- + I3- S4O62- + 3I- Tnh theo lht:
2Cu2+

5I-

no

m( g )
Cu

max

m
63,546.2

2CuI + I3-

S mol sau phn ng, n


I3-

2S2O32-

no

m
63,546.2

0,9050.15,65
1000

max

m
63,546.2

0,9050.15,65
1000.2

lht:

m
0,0950.15,65
=
63,546.2
1000.2

%Cu =

0,09448
100 = 8,75%
1,080

S4O62- + 3I-

m = 0,09448g;

- Tnh theo quy tc lg:


2Cu2+

+ e + I-

2CuI

3I- - 3e I3 Cu

2+

= M Cu

I 3 =

2+

s lg Cu

2+

m
Cu

= s lgI3-;

M I
3

I3 + 2e 3I2S2O32-

S4O62-

- 2e

M I

I 3 =

S 2 O 2 = M S 2 O 2
3

: khng thay i.
[ S 2 O 2 ] = 0,0950M = 0,0950N
3

S lg I 3 = s S 2 O 2 s lg Cu 2+ = s lg[ S 2 O 2 ] =
3

38

0,0950.15,65
1000

0,0950.15,65.63,546
m 0,0950.15,65
=
m=
= 0,09448( g )
1000
1000
Cu

%Cu =

0,09448
100 = 8,75%
1,080

2.1.2. Phng php trung ha


a. C s ca phng php

Phng php trung ha da trn c s ca phn ng trung ha.


H+ + OH- = H2O
2980K, chng ta c tch s ion ca nc:
KW = [H+][OH-] = 10-14 v pH + pOH = 14
Trong qu trnh chun th nng H+ v OH- thay i tc l pH thay i.
Trong phng php ny, xc nh nng ca baz, ngi ta dng cht chun
l axt mnh; xc nh nng ca axt, ngi ta dng cht chun l baz mnh.
b. Cht ch th mu dng trong phng php trung ha

Dng cht ch th mu nhn bit im tng ng.


Cht ch th mu dng trong phng php trung ha l cht ch th axt - baz.
l nhng hp cht hu c biu l tnh axt yu hoc baz yu c th thay i mu
theo pH ca dung dch.
Bn thn cc cht ch th ny l cc axt yu hoc cc baz hu c yu m dng
phn t hoc ion chng c mu khc nhau. iu ny do s phn ly hoc lin hp ca
cht ch th km theo s chuyn v cu trc bn trong dn n s i mu.
Phn ng in hnh ca ch th axt - baz di dng sau:
HInd + H2O H3O+ + Indhoc:
Ind- + H2O HInd + OHTrong cc dung dch axt mnh, ch th HInd l dng chim u th, tng ng vi
mu axt v Ind- s l mu kim ca n. Trong cc dung dch kim cc ion Ind- s
chim u th tng ng vi mu kim ca cht ch th .
V d: Phenolphtalein l mt axt hu c yu, khng mu trong dung dch axt v c
mu trong mi trng kim. Trong mi trng kim mnh mu ca chng b mt
chm.
Trong dung dch n tn ti cn bng:

COO-

COOH
HO

HO

Khong mau

Cau tao phan t cua phenolphtalein


39

+ H+

Bng 17. Mt s ch th axt - baz quan trng


S bin i mu
Axt
Baz

Khong bin i
pH

Loi ch th

Vng

2,5 4,5

(2)

Vng

2,9 4,0

(2)

Khng

tm

8 10

(1)

Qu tm

Xanh

68

(1)

Methyl : MR

Vng

4,2 6,2

(2)

Phenol

Vng

6,4 8,0

(1)

STT

Cht ch th

Methyldacam: MO

Methyl vng

Phenolphtalein: PP

(1) - Ch th axt;

(2) - Ch th kim

c. Cc yu t nh hng n s i mu ca cht ch th

* nh hng ca cc ion trong dung dch: Cc cht in ly trong dung dch c tc


dng n mu sc ca cht ch th trn hai kha cnh: Thay i cng mu ca mt
trong hai dng mu ca cht ch th; nh hng n cn bng ca cht ch th. Do
trong nhiu trng hp phi hiu chnh li pH ca khong i mu ca cht ch th.

* nh hng ca nhit : Khi thay i nhit ca dung dch s lm thay i s i


mu ca cht ch th, v lm thay i kh nng phn ly ca dung mi, ca axt, baz,
mui v c ca cht ch th.

* nh hng ca dung mi: Khi thay i dung mi th s phn ly ca axt - baz thay
i. Ch th axt - baz do cng thay i theo dung mi. l nguyn nhn gy nn
s nh hng ca dung mi n s i mu ca ch th.
d. ng chun axt mnh bng baz mnh hoc ngc li

Nu cht chun v cht b chun l axt mnh v baz mnh th c th hnh dung
phn ng axt - baz tng th bng phng trnh:
H3O+ + OH- = 2H2O
V d: Tin hnh kho st qu trnh chun 100 ml dung dch HCl 0,1N bng dung
dch NaOH 0,1N.
Trong qu trnh ny, t buret chng ta nh tng git dung dch NaOH 0,1N
xung bnh nn ng 100 ml dung dch HCl 0,1N.
NaOH + HCl = NaCl + H2O
OH- + H+ = H2O

* S bin i pH ca dung dch HCl trong qu trnh chun :


n gin chng ta coi th tch chung ca dung dch trong qu trnh chun
l khng i. iu ny cng khng nh hng nhiu n kt qu phn tch.
- Trc khi chun : trong dung dch ch c HCl l axt mnh in ly hon ton.
HCl = H+ + ClHCl 0,1N tng ng vi 0,1M.
[H+] = [HCl] = 0,1M pH = 1.
40

- Trc im tng ng:


Khi 90% dung dch HCl c chun , HCl cn li 10 ml.
[ H + ] = [ HCl ] =

10.0,1
= 0,01M pH = 2.
100

Khi 99% dung dch HCl c chun .


[ H + ] = [ HCl ] =

1.0,1
= 0,001M pH = 3.
100

Khi 99,9% dung dch HCl c chun .


[ H + ] = [ HCl ] =

0,1.0,1
= 0,0001M pH = 4.
100

- Ti im tng ng: Khi 100% dung dch HCl c chun bi NaOH, trong
dung dch ch c NaCl, mui ny c pH = 7.
- Sau im tng ng:
Dung dch bt u d NaOH l baz mnh, in ly hon ton.
NaOH = Na+ + OH-

[OH-]

= [NaOH]

[NaOH] = 0,1N tng ng 0,1M.


Khi 100,1% dung dch HCl c chun :
[OH ] = [ NaOH ] =

0,1.0,1
= 1.10 4 ; pOH = 4 pH = 10.
100

Khi 101% dung dch HCl c chun :


[OH ] = [ NaOH ] =

1.0,1
= 1.10 3 ;
100

pOH = 3 pH = 11.

Khi 110% dung dch HCl c chun :


[OH ] = [ NaOH ] =

10.0,1
= 1.10 2 ; pOH = 2 pH = 12.
100

Khi 200% dung dch HCl c chun :


[OH ] = [ NaOH ] =

100.0,1
= 0,1
100

; pOH = 1 pH = 13.

* Lp bng bin thin v v ng cong chun .

1
2
3
4
5
6
7
8
9

% chun

0
90
99
99,9
100
100,1
101
110
200

pH

1
2
3
4
7
10
11
12
13

15
10

pp

pH

STT

5
MO

0
0

50

100

150
%

41

200

250

* Nhn xt:
- im tng ng ca php chun c pH = 7 trng vi im trung tnh.
- ng cong chun c mt on dc ng vi khong t 99,9% ti 100,1% dung
dch HCl c chun . on ny ngi ta gi l bc nhy ca php chun .
Trong phm vi bc nhy, ch cn thay i mt t dung dch tiu chun ( 0,1%)
th gi tr pH thay i 6 n v t 4 n 10.

* Chn cht ch th:


Nguyn tc chung l phi chn cht ch th c khong i mu trong phm vi
bc nhy ca php chun . Tt nhin nu trng im tng ng hoc gn im
tng ng cng tt.
Vic chn cht ch th nh vy gip ta trnh c sai s ln trong php chun .
Trong phm vi bc nhy ch cn thm mt dung dch tiu chun lm cho dung
dch chun c pH thay i t ngt v lp tc lm cht ch th i mu, bo hiu im
tng ng v ngng chun li. Sai s ca php chun khng ng k.
Trong php chun trn chng ta c th dng cht ch th:
- Chn MO cho php chun axt mnh bng baz mnh. MO c khong i mu
pH = 2,5 4,5, khi mu sc ca dung dch chuyn t mu hng sang mu vng th
ngng chun . Ta thng hay chun qu 1, 2 git dung dch tiu chun nn cng
gn im tng hn.
- Chn PP cho php chun baz mnh bng axt mnh, PP c khong i mu
pH = 10 8. Ngng chun khi mu dung dch chuyn t tm sang khng mu.
2.1.3. Phng php kt ta
a. C s ca phng php

Phng php chun kt ta da trn phn ng to thnh cht kt ta trong qu


trnh chun .
Yu cu ca cc phn ng:
- Cc cht kt ta to ra phi c tch s ha tan cng nh cng tt, tc l ha tan
ca cht rt nh.
- Tc phn ng to kt ta phi nhanh.
- Cc kt ta khng c kh nng hp ph cc cht khc c trong dung dch.
- Khng xy ra hin tng cng kt.
- Phi c kh nng xc nh im tng ng.
Vic ng dng nhng phng php chun kt ta trong cht chun khng
phi l mui bc m l nhng hp cht khc cn tng i hn ch.
b. ng chun kt ta

Trong qu trnh chun theo phng php kt ta th nng cc ion to ra


hp cht kt ta s thay i lin tc. V vy trong phng php ny v ng cong
chun , chng ta phi kho st qu trnh bin i cc ion to kt ta trong qu trnh
chun .

42

Trong s cc phng php kt ta, ngi ta dng nhiu nht l phng php bc
xc nh ion halogenua v SCN- (hoc ngc li).
Ag+ + X- = AgX
X-: Ion halogenua v SCNV d: Kho st qu trnh chun 100 ml dung dch NaCl 0,1N bng dung dch
AgNO3 0,1N. Bit TAgCl = 10-10.
Phn ng xy ra trong qu trnh chun :
NaCl + AgNO3 = AgCl + NaNO3
y:

[NaCl] = 0,1N tng ng 0,1M.


[AgNO3] = 0,1N tng ng 0,1M.

Tch s ha tan ca AgCl:

TAgCl = [Ag+][Cl-] = 1.10-10

thun li cho qu trnh tnh ton ta gi:


pAg = -lg[Ag+] ; pCl = -lg[Cl-]
V vy:

pAg + pCl = 10

* Kho st hoc pAg hoc pCl trong qu trnh chun :


- Trc khi chun :
Trong dung dch ch c NaCl 0,1M:
NaCl = Na+ + Cl[Cl-] = 1.10-1M pCl = 1.
- Trc im tng ng:
Khi 90% dung dch NaCl c chun , NaCl cn li 10 ml.
[Cl ] = [ NaCl ] =

10.0,1
= 0,01M pCl = 2.
100

Khi 99% dung dch NaCl c chun .


[Cl ] = [ NaCl ] =

1.0,1
= 0,001M pCl = 3.
100

Khi 99,9% dung dch NaCl c chun .


[Cl ] = [ NaCl ] =

0,1.0,1
= 0,0001M pCl = 4.
100

- Ti im tng ng:
Khi 100% dung dch NaCl c chun bi AgNO3, trong dung dch ch c
mui AgCl, nn:
[Cl ] = [ Ag + ] = AgCl = 10 10 = 10 5 M ;

pCl = pAg = 5
- Sau im tng ng:
Dung dch bt u d AgNO3
Khi 100,1% dung dch NaCl c chun :
43

AgNO3 = Ag+ + NO3[Ag+]

Nn

= [AgNO3] =

0,1.0,1
= 1.10 4 M
100

pAg = 4 pCl- = 6
Khi 101% dung dch NaCl c chun :
[Ag+]

= [AgNO3] =

1.0,1
= 1.10 3 M
100

pAg = 3 pCl- = 7
Khi 110% dung dch NaCl c chun :
[Ag+]

= [AgNO3] =

10.0,1
= 1.10 2 M
100

pAg = 2 pCl- = 8
Khi 200% dung dch NaCl c chun :
[Ag+]

= [AgNO3] =

100.0,1
= 1.10 1 M
100

pAg = 1 pCl- = 9

* Lp bng bin thin v v ng cong chun .


pH

90

99

99,9

100

100,1

101

110

200

10
8
pCl

STT % chun

6
4
2
0
0

50

100

150

200

250

* Nhn xt:
- Bc nhy ca php chun c pCl = 4 6.
- im tng ng ca php chun c pCl = 5.

* Cht ch th:
- Phng php Mohr: Trong php chun ny ngi ta dng cht ch th l CrO42. CrO42- tc dng vi Ag+ cho kt ta Ag2CrO4 mu nu c ha tan 8,4.10-5
mol/L ln hn ha tan ca AgCl (1.10-5 mol/L):
2Ag+ + CrO42- = Ag2CrO4
Khi cho t t ion Ag+ vo dung dch chun cc ion Cl-, CrO42- th AgCl s kt
ta trc, Ag2CrO4 s kt ta sau.
44

nhn bit im tng ng ca php chun , chng ta phi tnh ton hm


lng K2CrO4 c trong dung dch sao cho khi t ti im tng ng, tc l khi
NaCl c chun hon ton mi xut hin kt ta Ag2CrO4 mu .
Chng ta bit:

TAgCl = [Ag+][Cl-] = 10-10


Ag 2CrO4 = [ Ag + ] 2 [CrO 42 ] = 10 12

Ti im tng ng: [Ag+] = [Cl-] = 10-5 M


khi [Ag+] = 10-5M mi c kt ta Ag2CrO4 th hm lng CrO42- c trong
dung dch c tnh ton theo tch s tan ca Ag2CrO4.
Ag 2CrO4 = [ Ag + ] 2 [CrO 42 ] = 10 12
[CrO42 ] =

[CrO 42 ] =

nn:

Ag2CrO4
+ 2

[ Ag ]

[ Ag + ] = 10 5 M

10 12
= 10 2 M
5 2
(10 )

K2CrO4 = 2K+ + CrO42[CrO42-] = [K2CrO4] = 10-2M


Nh vy chn nng K2CrO4 trong dung dch chun l 10-2M th ti im
tng ng mi bt u xut hin Ag2CrO4 kt ta mu . S chun kt thc khi
trong dung dch chun t kt ta trng bt u chuyn sang xut hin kt ta .
Cn ch n nng axt ca mi trng. Theo phng php ny cn phi
c tin hnh trong mi trng trung tnh hoc gn trung tnh.
- Phng php Volhard: Da trn phn ng gia Ag+ v SCN-, dng ion Ion Fe3+
lm cht ch th.
Ag+ + SCN- AgSCN(rn)
Sau khi t im tng ng, lng CNS- d s to vi Fe3+ phc sunfuaxianua
st c mu mu.
Fe3+ + 3SCN- Fe(SCN)3
Nh vy im tng ng ca php chun c xc nh cn c vo s to
thnh phc Fe(SCN)3 c mu . Php chun cn c thc hin trong mi trng axt
ngn nga s kt ta Fe(III) di dng hiroxit.
Bng 18. Mt s phng php kt ta o bc
Cu t
cn xc nh

Phng php xc nh
im cui

Cl-, Br-

Phng php Mohr

SCN

Ghi ch

Phng php Volhard

Khng cn tch mui bc

BH4

Phng php Volhard


bin dng

Chun trc tip theo lng Ag+


d trong phn ng:
BH4 + 8Ag+ + 8OH-
8Ag(rn) + H2BO3 + 5H2O

Br-, Cl-, I-, SeO32-

Ch th hp ph
45

2.1.4. Phng php phc cht


a. Nguyn tc

Cng nh cc phn ng khc dng nh phn, cc phn ng to phc cn phi


xy ra nhanh, hp thc v nh lng.
Cc phng php to phc da trn phn ng to phc ca cc cht. Trong phn
tch th tch ngi ta thng dng cc phng php sau y: Phng php thu ngn
(II), phng php bc, phng php complexon.
Phng php complexon: Da trn phn ng to phc ca cc ion kim loi vi
nhm thuc th hu c c tn chung l complexon.
Phng php complexon l phng php phn tch chun da trn vic dng
phn ng ca ion kim loi to phc vi complexon, to thnh cc mui ni phc, bn,
t phn ly, tan trong nc.
b. Chn cht chun

Complexon l cc dn xut ca axt aminopoli cacboxilic. Th d axt


etylendiamin tetraaxetic hay complexon II, vit tt l EDTA:
HOOC - CH2

CH2 - COOH
N - CH2 - CH2 - N
CH2 - COOH

HOOC CH2

Tuy nhin EDTA t tan trong nc nn kh s dng. Ngi ta thng dng mui
dinatri ca EDTA gi l complexon III hay trilon B, vit tt l Na2H2Y.
HOOC - CH2

CH2 - COOH
N - CH2 - CH2 - N
CH2 - COONa

NaOOC CH2

lm cht chun, v n c tinh khit cao, c cng thc ha hc bn iu kin thng


thng.
Trong phn ng vi kim loi, mui ny phn ly hon ton to ra ion phc:
Na2H2Y = 2Na+ + H2Y2Tnh cht qu gi nht ca cht chun EDTA l kh nng phn ng ca n vi
cc ion kim loi theo t l 1:1 khng ph thuc vo in tch cation.
Ion H2Y2- rt d to phc rt bn v tan trong nc vi nhiu ion kim loi. Tt c
cc cation phn ng vi EDTA, tr cc kim loi kim u to thnh cc phc bn,
l c s cho phng php chun .
V d: ng glicocoliat:
O=C-O

O-C=O
Cu

H2N - H2N

NH2 - NH2

H2Y2- ha tan vi cc ion kim loi nh Ca2+, Mg2+, Fe2+, Mn2+, Cu2+,...cc cation
kim loi ny k hiu l Me2+.
Me2+ + H2Y2- MeY2- +
46

2H+

Theo phng trnh trn th vic to phc MeY2- c quan h cht ch vi [H+], tc
l pH ca dung dch. cn bng to phc trn chuyn dch theo chiu thun, ngha l
to phc hon ton th pH ca dung dch phi cao (pH > 7). iu ny cho thy trong
phng php phc cht phi s dng s to phc trong mi trng baz.
c. Cht ch th dng trong phng php complexon

Cht ch th mu dng trong phng php complexon l cht ch th c kh nng


to vi ion kim loi phc c mu khc vi mu ring ca cht ch th. Cht c
gi l cht ch th kim loi. Nh vy php chun ion kim loi bng EDTA gm 2
giai on:
- Phn ng gia ion kim loi t do v complexon.
- Phn ng gia complexon v ion kim loi trong phc.
Cht ch th ny c mt trong dung dch chun mt gi tr pH no c kh
nng to phc tan, c mu vi cation kim loi cn xc nh. Nhng phc ny km bn
hn phc to bi vi EDTA v cation kim loi .
Cht ch th thng c s dng rng ri trong php chun complexon l
Eriocrm T en ( k hiu H2Ind- ): l mt axt a bc yu. Trong dung dch c pH < 7
tn ti di dng:
OH
-

OH
N=N

O3 S
NO2

Cht ch th ny c phm vi i mu khc nhau.


H2Ind-

pH = 6,3

H2Ind2-

Xanh

pH = 11,6

Ind3-

Vang da cam

Khi s dng cht ch th ny trong chun xc nh hm lng cc cation kim


loi thng dng pH = 6,3 11,6 nn tn ti dng H2Ind2- c mu xanh. H2Ind2- to
phc tan, km bn vi cation kim loi c mu . Nh vy nu chnh dung dch chun
c pH = 6,3 11,6 khi cho cht ch th Eriocrm T en vo dung dch s c mu
nu trong dung dch c cc cation kim loi. Dng EDTA chun dung dch ny
th vic kt thc chun khi dung dch chun c mu chuyn sang mu xanh.
Eriocrm T en to phc hoc hng vi ion kim loi Mg2+, Zn2+, Cd2+ thng
c dng chun trc tip cc ion trong mi trng pH = 10 dng hn hp
m NH3 - NH4+.
V d 1: Chun cation Ca2+ v Mg2+ trong nc t nhin bng EDTA, cht ch th l
Ericrm T en.
Trc tin ta dng dung dch m c pH = 10 iu chnh pH ca dung dch
chun c pH l 10. Cho vi git cht ch th Ericrm T en vo:
HInd2- + Me2+

Me2+ : Ca2+, Mg2+;

MeInd- + H+
MeInd- c mu .

47

Dng dung dch tiu chun H2Y2- chun dung dch ny. Ti im tng ng
H2Y chim ht Me2+ y HInd2- ra c mu xanh:
2-

H2Y2- + MeInd- MeY2- + HInd2- + H+


Vic kt thc chun khi dung dch chun i mu t tm sang xanh lam.
C th dng cht ch th Murext (k hiu H4Ind-) trong php chun complexon.
Murext l mui amoni ca axt pupuric C8H5O2N5, l mt loi bt mu thm. Dung
dch nc murext c mu tm thay i theo mi trng: pH 9 mu tm , pH = 9 10: mu tm, pH > 11 - tm xanh.
Trong mi trng axt mnh H4Ind- c cng thc cu to nh sau:
O-

NH - C
O=C

C = NH
C-N=C

NH - C

C=O
C = NH

H4Ind- tc dng vi cation kim loi thnh phc mu hng. Dng EDTA chun
dung dch th ti thi im tng ng EDTA dnh ht cation kim loi y H4R- ra
nn dung dch chun c mu tm hu.
+

Murext l cht ch th tt cho vic chun trc tip cc ion Ca2+, Cu2+, Ni2+,

Ag .
V d 2: Chun dung dch Ca2+ trong nc t nhin bng dung dch tiu chun
EDTA vi cht ch th murext.
u tin dng dung dch NaOH iu chnh pH ca dung dch chun c pH =
12. Cho tip mt t murext vo:
H4R- + Ca2+ CaH2R- + 2H+
Dung dch chun lc ny c mu hng.
Dng dung dch tiu chun H2Y2- chun dung dch ny. Ti im tng
ng:
CaH2R- + H2Y2- CaY2- + H4RDung dch lc ny c mu tm hu.
Vic chun kt thc khi dung dch chun i t mu hng sang mu tm hu.
b. Qu trnh chun

Trong phng php phc cht, kho st qu trnh chun ngi ta da vo


hng s khng bn Kkb ca phc MeY2-.
2-

2+

MeY Me

4-

+ Y

kb

[ Me 2 + ][Y 4 ]
=
[ MeY 2 ]

Cng ging nh phng php kt ta, da vo Kkb c th tnh c [Me2+] hay


[Y4-] thay i trong qu trnh chun . T v c ng cong chun .

48

2.1.5. Phng php oxy ho kh


a. Nguyn tc

L phng php phn tch nh lng s dng cc phn ng oxy ha kh, tc l


s dng cc phn ng trong c s trao i electron.
Ox1 + Kh2 Kh1 + Ox2
Phn ng ny bao gm 2 bn phn ng:
Ox1 + ne Kh1
Kh2 - ne

Ox2

Yu cu ca phn ng:
- Cc phn ng xy ra theo mt chiu xc nh.
- Phn ng phi xy ra hon ton.
- Tc phn ng phi nhanh.
- Phi xc nh c im tng ng.
b. Mt s khi nim c bn

* Th in cc ca kim loi:
Khi nhng mt thanh kim loi Me vo nc hay dung dch mui ca n s xut
hin mt tng in kp trn b mt kim loi v lp dung dch st b mt kim loi. S
chnh lch th trong tng in kp c gi l th in cc ca kim loi, k hiu l .
iu kin tiu chun v nng ca cation kim loi trong dung dch l 1 mol/l,
th in cc c so snh vi in cc hiro tiu chun v gi l th in cc tiu
chun ca kim loi, k hiu l 0.
iu kin khng phi l iu kin chun, nng cation kim loi thay i, th
in cc ca kim loi c tnh theo biu thc ca Nerst:

Me

n+

/ Me

= 0 Me n + / Me +

RT
ln[Me n + ]
nF

(2-11)

* Th oxy ho kh: Khi nhng mt thanh kim loi tr v mt ha hc vo dung dch


cha cp oxy ho v kh th trn b mt thanh kim loi v dung dch cng xut hin mt
tng in kp v th chnh lch trong tng in kp c gi l th oxy ho - kh.
Th oxy ho - kh c k hiu l EOx/Kh.
V d: nhng mt thanh Pt vo dung dch cha cp Fe2+ v Fe3+. in cc ny c k
hiu: Pt Fe3+ / Fe 2 + v th ca cp oxy ho - kh ny c k hiu: Fe3+ / Fe 2 + .
Cng ging nh th in cc ca kim loi, xc nh th oxy ho - kh ngi
ta cng phi to lp mt pin in gm mt in cc l in cc cn o th oxy ho kh v in cc cn li l in cc hiro tiu chun.
Trong iu kin khng phi l tiu chun v nng cc dng oxy ho, kh u
l 1 mol/l th E o c gi l E tiu chun, k hiu l Eo.
Trong iu kin khng phi tiu chun v nng cc dng oxy ho - kh khc 1
mol/l th E o c l th oxy ho - kh ca cp oxy ho - kh trong iu kin cho.
Chng ta c th tnh th oxy ha - kh qua biu thc Nerst:
49

= 0 +

RT [Ox]
ln
nF [ Kh]

(2-12)

vi [Ox] v [Kh] tnh theo mol/l.


2980K, F = 96500, chuyn ln sang lg, ta c cng thc:
= 0 +

RT [Ox]
lg
nF [ Kh]

(2-13)

Bng 19. Th oxy ho - kh tiu chun ca mt s cp oxy ha - kh:


Dng oxy ho

Dng kh

K hiu

E0(vn)

Fe2+

Fe

Fe2+/Fe

- 0,44

2-

2-

S/S

- 0,51

I2

I-

I2/2I-

+ 0,54

Cl2

Cl-

Cl2/2Cl-

+ 1,36

MnO4-

Mn2+

MnO4-/Mn2+

+ 1, 52

F2

F2/2I

+ 3,03

SO42-

SO32-

SO42-/SO32-

- 0,58

Cu2+

Cu

Cu2+/Cu

+ 0,17

Fe3+

Fe2+

Fe3+/Fe2+

+ 0,77

4+

2+

Sn

Sn

4+

2+

+ 0,15

Sn /Sn

V d 1: Th oxy ho - kh ca cp MnO4-/Mn2+ ph thuc vo [H+] theo phng


trnh:
MnO4- + 8H+ + 5e Mn2+ + 4H2O

0,059 [ MnO4 ][ H + ]8
= +
lg
5
[ Mn 2 + ]
0

* Hng s cn bng ca phn ng oxy - ha kh.


Trong phn ng oxy ho - kh:
- Cp no c E ln l cp ng vai tr cht oxy ha.
- Cp no c E nh hn l cp ng vai tr cht kh.
Trong qu trnh phn ng xy ra, E ca cp oxy ha gim dn, ng thi E ca
ca cp kh tng dn, ti thi im EOx = EKh th phn ng t ti trng thi cn bng
(c hng s cn bng Kcb).
V d 2: Xt phn ng:

2Fe3+ + Sn2+ 2Fe2+ + Sn4+

Cp oxy ha: Fe3+/Fe2+;


Ti thi im cn bng:

Sn4+/Sn2+

Cp kh:
Fe

C =

3+

/ Fe

2+

[ Fe 2 + ][ Sn 4 + ]
[ Fe 3+ ][ Sn 2 + ]

50

Sn

4+

/ Sn

2+

(*)

TTCB:

Ox = Kh

o
Ox
oKh =

0,059 [ Fe 2 + ][ Sn 4 + ]
lg
n
[ Fe 3+ ][ Sn 2 + ]

0
Ox
0Kh =

0,059
lgKc
n

0
lg K C = 16,9.n( Ox
0Kh )

hay

Trong n l s electron trao i trong phn ng oxy ha - kh.


Nh vy trong phn ng trn (*):
lgKC = 16,9.2(0,77 - 0,15) = 20,956 ; KC = 1020,956.

* Chiu ca phn ng oxy ha - kh: Chng ta da vo th oxy ha kh xc nh


c chiu ca phn ng oxy ha kh.
c. Chun bng phng php oxy ha kh

Trong qu trnh chun bng phng php oxy ho kh, nng cc cht oxy
ha v cht kh lun thay i, nn th oxy ha kh ca cc cp oxy ho kh lun thay
i. V vy trong phng php ny chng ta kho st s thay i E theo qu trnh
chun . th biu din E trong qu trnh chun l ng cong chun . Da
vo ng cong chun ta cng xc nh c bc nhy th, im tng ng,
chn cht ch th thch hp cho phng php chun .
V d 1: Chun 100 ml dung dch FeSO4 0,1N bng dung dch tiu chun KMnO4
0,1N trong mi trng [H+] = 1M.
Phn ng xy ra:
10FeSO4 + 2KMnO4 + 8H2SO4 5Fe2(SO4)3 + 2MnSO4 + K2SO4 + 8H2O
Dng ion thu gn:
5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O

* Kho st th oxy ha kh (E) trong qu trnh chun :


V phn ng thun nghch, nn thi im no ca qu trnh chun , trong dung
dch chun lun tn ti cp oxy ha MnO4-/Mn2+ v cp kh Fe3+/Fe2+.

Ox

0,059 [ MnO4 ][ H + ]8
= 1,52 +
lg
5
[ Mn 2 + ]

Kh = 0,77 +

0,059 [ Fe 3+ ]
lg
1
[ Fe 2 + ]

Khi tnh ton E trong qu trnh chun , c th tnh theo 2 cng thc trn, tt
nhin kt qu nh nhau. Thng thng trc im tng ng tnh theo EKh; cn sau
im tng ng tnh theo EOx.
- Trc im tng ng.
Khi 50% Fe2+ c chun :

= 0,77 +

0,059 50
lg
= 0,77V
1
50

Khi 90% Fe2+ c chun :

= 0,77 +

0,059 90
lg
= 0,826V
1
10

51

Khi 99,9 % Fe2+ c chun :

= 0,77 +

0,059 99,9
lg
= 0,947V
1
0,10

= 0,77 +

0,059 [ Fe 3+ ]
lg
1
[ Fe 2 + ]

- Ti im tng ng.
i vi cp kh v cp oxy ha:

(a)

= 1,52 +

0,059 [ MnO4 ][ H + ]8
lg
5
[ Mn 2 + ]

0,059 [ MnO4 ]
5 = 5 1,52 +
lg
1
[ Mn 2 + ]

(v [H+] = 1M).

(b)

(a) + (b) :

[ Fe 3+ ][ MnO4 ]
6 = 0,77 + 5 1,52 + 0,059 lg
[ Fe 2 + ][ Mn 2 + ]

Theo phng trnh ion thu gn trn, ta c:


[Fe3+] = 5[Mn2+];
[Fe2+] = 5[MnO4-]

nn

[ Fe 3+ ][ MnO4 ]
=1
[ Fe 2 + ][ Mn 2 + ]

v th

6E = 0,77 + 5 1,52
=

0,77 + 5 1,52
= 1,395V
6

T ta c cng thc tng qut tnh E im tng ng:


=

0
a. 0Kh b. Ox
= 1,395V
a+b

a: s e trao i ca cp kh; b: s e trao i ca cp oxy ha.


- Sau im tng ng.

E tnh theo cng thc:

= 1,52 +

0,059 [ MnO4 ][ H + ]8
lg
5
[ Mn 2+ ]

Khi 100,1 % Fe2+ c chun :

= 1,52 +

0,059 0,1
lg
= 1,485V
5
100

Khi 101 % Fe2+ c chun :

= 1,52 +

0,059
1
lg
= 1,496V
5
100

Khi 110 % Fe2+ c chun :

= 1,52 +

0,059 10
lg
= 1,508V
5
100

Khi 200 % Fe2+ c chun :

= 1,52 +

0,059 100
lg
= 1,52V
5
100

* ng cong chun .

52

% chun

E0vn

0,534

50

0,77

90

0,826

99,9

0,947

100

1,395

100,1

1,485

101

1,496

110

1,508

200

1,52

STT

1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0

50

100

150

200

250

* Nhn xt.
ng cong chun ca phng php oxy ha kh ging ng cong chun
ca phng php trung ho.
- Bc nhy:

E = 0,944 1,475 V

- im tng ng: E = 1,395 V.


Khi E ca cp oxy ha - kh khc bit nhau th bc nhy cng di php chun
cng chnh xc.
d. Cht ch th dng trong phng php oxy ho kh

Trong i a s cc trng hp cht ch th trong phng php oxy ha kh l


nhng cht oxy ha hoc kh m dng oxy ha v dng kh ca n c mu khc nhau.
V vy mu ca cht ch th ph thuc vo th oxy ha kh ca dung dch. Mi cht
ch th oxy ha kh c mt khong i mu xc nh.
Gii thiu mt s cht ch th thng c s dng:
- Diphenylamin: c s dng di dng dung dch 1% trong axt sunfuric c.
Cht ny c th tiu chun E0 = + 0,76V. Dng oxy ha c mu tm, dng kh khng
mu.
- Diphenulbenzidin: Cht ch th c cng thc cu to:
- NH -

- NH -

c s dng di dng dung dch 1% trong axt sunfuric c. Cht ny c th


tiu chun E0 = + 0,76V. Dng oxy ha c mu tm, dng kh khng mu.
- Phc Fe2+ vi 2,2 - dipiridin: Cng thc cu to:
Fe
N

Cht ch th ny c E0 = + 1,06 V. Dng oxy ha c mu xanh nht, dng kh c


mu .

53

- Bn thn dung dch tiu chun cng va l cht ch th: Trong v d trn th
KMnO4 va l dung dch tiu chun va l cht ch th (ion MnO4- c mu tm cn
ion Mn2+ khng c mu).
- Cht ch th ngoi khng l cht oxy ha - kh: Thng dng trong phng php
it (cht ch th l h tinh bt hp th to hp cht c mu xanh en).
I2 - 2e 2IV d: Chun I2 bng dung dch tiu chun natrithiosunfat (Na2S2O3).
Na2S2O3 + I2 = 2NaI + Na2S4O6
Cho cht oxy ha cn nh phn tc dng vi lng d ion I- ri chun lng
I- va to thnh bng dung dch chun thiosunfat vi cht ch th l h tinh bt.
2.2. Phng php phn tch ha l
2.2.1. Phng php o mu quang in
a. Bn cht ca nh sng

nh sng va mang tnh cht sng va mang tnh cht ht. Nu gi:
: bc sng bc x ( di sng) - l qung ng m bc x i c sau mi
dao ng y .
c - tc truyn sng nh sng, trong chn khng: 3.10-8 m/giy.
: tn s ca bc x - l s dao ng trong mt n v thi gian (giy). Trong
mt giy bc x i c c (cm) v bc sng l (cm).
Vy:

= c hoc =

(1cm = 108A0 = 107nm = 104m ;

(2-14)

1ec = 10-7J = 2,3884 cal = 0,6241.1012 eV)

Bc sng cng ln th tn s sng cng gim v ngc li, gi l lng t nng


lng v vi mi bc x d pht ra hoc hp th u bng mt s nguyn ln ca .
nh sng nhn thy c c bc sng nm trong khong 400 700nm. Trong
di sng ny nh sng trng l tp hp cc tia sng n sc ng vi cc mu t , da
cam, vng, lc, lam, chm, tm.
Trong vng ph ny, ngi ta tch c nhng bc x vi bc sng ch sai
khc nhau c 1 - 0,1 nm. cc vng ph khc nhau, nh nhng dng c thch hp nh
lng knh, cch t... t nhng bc x a sc ngi ta c th tch ring c nhng bc
x c cng bc sng gi l bc x n sc (bc x gm ch mt loi photon c nng
lng nh nhau).
b. S th hin mu sc ca dung dch

Khi bc x chiu vo cc phn t, n c th b khuch tn hoc hp th bi cc


phn t v mt phn cho i qua. S khuch tn khng lm thay i tn s bc x l s
khuch tn thng, cn s khuch tn lm thay i tn s bc x l s khuch tn t
hp.
Mu ca dung dch l mu ca nh sng n sc m dung dch khng hp th,
cho i qua.
Cng mu sc ca dung dch ph thuc vo bn cht cc cht c trong dung
dch, nng dung dch v b dy lp dung dch m nh sng chiu qua.
54

Nhng im c bn v s khuch tn:


- S khuch tn thng
nh sng i qua cht kh, cht lng hoc cht kt tinh thng b nhng phn t
cc mi trng lm khuch tn mt phn theo khp mi phng. nh sng khuch
tn c cng yu hn so vi nh sng ti, nhng phn ln c bc sng khng
i. Kt qu nghin cu cho thy cng ca nh sng khuch tn t l thun vi lu
tha bc bn ca tn s nh sng. Do trong nh sng khuch tn, phn bc sng
ngn ca quang ph c cng ln hn phn bc sng di. Trn c s ngi ta
gii thch mu xanh ca nn tri l do kt qu chuyn dch sng ca nh sng mt
tri v pha bc sng ngn khi n b khuch tn bi bu kh quyn ca Tri t. Mu
xanh ca nc bin cng c th c gii thch tng t.
Trong s khuch tn thng, lng t nh sng h 0 va chm vi phn t v b
khuch tn cng vi tn s 0 . S va chm nh vy gi l s va chm n hi.
Trong s va chm ny, phn t tc dng vi vect in ca nh sng, khi momen
lng cc D b khch thch v electron bt buc phi dao ng vi tn s ca nh sng.
Momen in dao ng nh th li pht nng lng theo mi hng, tc l khuch tn
nh sng m khng lm thay i tn s ca n.
- S khuch tn t hp
Chiu vo mt cht no mt chm tia sng n sc tn s 0 c cng
mnh th trong quang ph ca nh sng khuch tn, bn cnh vch khuch tn thng
vi tn s 0 khng i, cn c nhng vch khc yu hn nhiu ng vi tn s ln
hn hoc b hn 0 v phn b i xng bn ny hoc bn kia 0 . Nhng vch hp
thnh t khuch tn t hp.
y xy ra s va chm khng n hi: Phn t mc dao ng c bn nhn
mt phn nng lng ca photon va chm vi n chuyn ln mc dao ng cao
hn. Cn photon b mt mt phn nng lng v khuch tn vi tn s 0 .
Trong phng php ny, ngi ta chiu vo mu mt chm nh sng n sc ri
phn tch nh sng khuch tn phng vung gc vi tia sng ti.
Tia laser
Mao quan cha mau

Anh sang khuech tan


en bo phan tch

Ngy nay, ngi ta thng dng cc laser kh. V d:


Laser He-Ne cho tia 6328A0;
Laser Ar cho cc vch 4579, 4658, 4765, 4880, 5145 A0 (thng dng vch Ar+
4880 v 5145A0).
c. nh lut v hp th nh sng

Khi chiu mt chm nh sng n sc, song song, c cng I0 (tnh bng
erg.cm2/sec; 1 erg = 107 J = 6,2415 1011 eV ) vung gc vi b dy l ca mt mi
55

trng hp th, th sau khi qua lp cht hp th ny (dung dch), cng ca n cn


l I (erg.cm2/sec) . Thc nghim chng t:
ln

I0
= k .n
I

(2-15)

k: h s t l ph thuc vo cht hp th v tn s ca bc x;
n: s mol cht nghin cu t trn ng i ca bc x.
Thng ngi ta o cng hp th ca mt cht dng dung dch vi dung
mi khng hp th bc sng o c. Trong dung dch, i lng n t l vi nng
mol ca cht tan v chiu dy l ca dung dch. dng logart thp phn, ngi ta
thay h s k bi h s . Khi phng trnh c dng:
lg

I0
= .l.C
I

(2-16)

y l biu thc ton hc ca nh lut hp th bc x mang tn: Lamber Beer.


i lng lg(I0/I) c gi l mt quang (k hiu D, c gi tr t 0 - ) hoc hp th.
D = lg

I0
= .l.C
I

(2-17)

l - chiu dy ca lp cht hp th tnh bng cm;


C - nng ca cht hp th, tnh bng mol/L;
- h s hp th mol (h s tt mol).
T phng trnh trn cho thy: c gi tr bng D, khi nng cht hp th bng
n v (C = 1 mol/l) v dy ca lp cht hp th cng bng n v (l = 1cm). Nh
th c n v l/mol.cm.
Trong thc nghim, ngi ta c nh chiu dy lp dung dch, i vi mt loi dung
dch cng iu kin th = const nn khi o T hoc D u c th xc nh c C.
Theo nh lut Lambe - Bia (Lambert - Beer): khi hp th tia n sc, i vi dung
dch cho, mt quang ( hp th) ph thuc bc nht vo nng cht hp th.
Ty theo tng cht, nh lut c th c tun theo trong nhng khong nng
no , thng l nhng nng thp. nng cao th c s sai lch ng k,
iu ny c th l do s thay i mc lin hp hoc phn ly ca phn t khi thay
i nng .
Ch : nh lut hp th nh sng ny ch ng cho nh sng n sc, tc l nh
sng c xc nh.
Trong phng php quang ph nghim, o cng hp th, ngi ta thng
so snh cng ca tia bc x trc v sau khi qua cht hp th. c trng cho
cng hp th ngi ta dng cc i lng sau:
I I0
.100
I0

truyn qua: =
0

% truyn qua = .100


0

% hp th =

(2-18)
(2-19)
(2-20)

56

d. Vng quang ph hp th

c im hp th nh sng ca cc hp cht mu l s hp th chn lc. H s


hp th phn t ca hp cht mu v mt quang ca dung dch khc nhau i vi
chm nh sng i qua c cc bc sng khc nhau. V vy ph hp th cng l mt
c trng in hnh ca cc hp cht mu.
Khi s dng phng php so mu nh lng mt cht cn phi dng tia n
sc no m khi chiu qua dung dch, dung dch c kh nng hp th ln nht. xc
nh bc sng nh sng hp th cc i ngi ta o gi tr mt quang hoc h s
hp th phn t ca dung dch mu vi nhng bc sng khc nhau, cch nhau 10
20 nm. gi tr bc sng no m mt quang o c l ln nht th l bc
sng thch hp nh lng hp cht mu ny.
e. Phng php xc nh

* Cu to dng c o
S khi dng c o:
1

Trong s :
(1): b phn to ngun sng: gm c bng n thng, cc b phn iu chnh v
n nh dng in cung cp cho n.
(2): b tia sng n sc: Vi my n gin l cc knh lc mu, cc my hin i
dng cch t hoc knh quang ph to cc tia sng n sc.
Vi my dng knh lc mu th phi chn loi knh ch cho nhng tia sng m
dung dch hp th c i qua.
Vic chn knh lc mu thch hp theo nguyn tc trn c th da vo bng sau y.
Vi cc my hin i, ngi ta ghi sn bc sng nh sng ph hp vi cc ch
tiu ha cht tng ng, chng ta ch da vo m chn nh sng thch hp.
Bng 20. Nguyn tc chn la knh lc mu
Mu dung dch

(nm)

Mu ca knh

(nm)

Tm

400450

Lc nh vng

400450

Chm

450480

Vng

450480

Chm nh lc

480490

Da cam

480490

Lc nh chm

490500

490500

Lc

500560

Tm

500560

Lc nh vng

560575

Chm

560575

Vng
Da cam

Chm nh lc

575590

Lc nh chm

590625

Lc

625700

575590
590625
625700

(3): b phn cha dung dch o: dung dch o ng trong cc cuvet. Cu to


cuvet phi c ng nht v mi mt.

57

(4): t bo quang in v b phn x l: Khi It chiu vo t bo quang in th


trong n sinh ra dng in tng ng. Dng in ny c khuch i v x l trong
b vi x l bin thnh nhng tn hiu cn o.
(5): b phn hin th: Cc tn hiu sau khi x l c truyn qua b phn hin
th. B phn hin th c th l thanh chia ca T hoc D, c th l mn hin s tinh
th lng cc gi tr T hoc D, c th hin s ngay ra cc i lng o theo mg/l, tu
thuc cu to my.

* Phng php o.
- Phng php so snh vi mt dung dch tiu chun.
Ta c dung dch tiu chun c nng l Ctc, o D trn my c Dtc.
Dung dch cn o c Cc, o trn my c Dc.
Dtc
C
= tc
Dc Cc

D
Cc = Ctc. c
Dtc

Cn ch l dung dch tiu chun v dung dch cn o phi hon ton ng nht
nh nhau.
Phng php th.
Trc ht l xy dng th tiu chun:
Pha mt lot dung dch tiu chun ca cht cn
o ng vi cc nng tng dn: C1, C2, C3, C4,
C5,

Dx

Tin hnh o mt quang D ca dy


dung dch chun ny D1, D2, D3, D4, D5, vi
cng cuvet v knh lc mu s dng o cc
dung dch chun. Trn c s xy dng ng
chun bng phng php hi quy tuyn tnh A =
f(c).

Cx

tin hnh nh lng cht x trong dung dch phn tch, ta tin hnh pha ch
nh dung dch tiu chun trn, ri o mt quang Dx, da vo th chun s xc
nh c Cx.
2.2.2. Phng php o ph dng ngn la
a. Nguyn tc chung
1
4

2
3

Trong s :
(1) My bm khng kh: cung cp khng kh cho b phn t.
(2) Nhin liu: Dng kh t. Ty theo cu to ca my m nhin liu c th l
butan hoc axetylen tinh khit.
58

(3) B phn ht v trn dung dch cn o vi khng kh v kh t. B phn ny


ging nh cacbuarator ca ng c t trong. Chng c nhim v ht cc dung dch
cn o sau trn vi kh t v khng kh v phun vo bung t.
(4) Bung t: Dung dch cn o, nhin liu, khng kh c phun ln v t
chy; khi chy chng ta cn iu chnh ngn la cho thch hp.
(5) Knh lc mu: Cc my thng thng ch c hai knh lc mu: knh o Na v knh
o K. Cc my hin i nh JENWAY.PFP7 cn c thm knh lc mu o Ca, Ba, Li.
(6), (7) L t bo quang in, b vi x l v b phn hin th ging nh phng
php o mu.
b. Phng php o ph pht x nguyn t

Nguyn l c bn ca phng php nh sau: Di tc dng ca nhit ngn


la, cc nguyn t, phn t hoc ion ca cht b kch thch s chuyn sang trng thi
cc dao ng ca in t pht x. Cng pht x c o bng dng c quang hc
ri t tnh ra nng cht cn xc nh.
phn tch mt cht no trong mu phn tch bng phng php o ph pht
x dng ngn la ta tin hnh cc bc sau:
- Trc ht phi dng ngun nng lng bin mu thnh hi ri chuyn nguyn
t cn xc nh thnh nguyn t (giai on nguyn t ha mu).
Bng 21. Nhit ca mt s ngn la thng dng (theo Poluectov)
Hn hp chy

Nhit ngn la (oC)

Propan - khng kh

1700 1800

Hiro - khng kh

2000 2045

Axetylen

2125 2397

Hiro -oxy

2550 2660

Axetylen - oxy

3100 3137

Propan - N2O

2850 2900

- Tip theo dng nng lng kch thch nguyn t, chuyn nguyn t ln trng
thi kch thch. Thi gian nguyn t trng thi kch thch rt ngn (khong 10-8 giy)
ri li tr v trng thi cn bng v gii phng nng lng hp th c dng cc
bc x (pht x).
- Dng mt h thng phn gii quang hc tch chm bc x thnh nhng tia
n sc, ng vi mi tia n sc to ra mt vch ph. Loi ph ny gi l ph pht x
nguyn t.
- Da vo v tr ca vch ph ta c th xc nh nh tnh c cc nguyn t trong
mu phn tch. o cng vch ph ta c th xc nh nh lng nguyn t ny.
Cng vch quang ph (I, n v erg.cm2/giy) lin h vi nng C bng
phng trnh Schaibelomakin:
I = a.Cb

(2-21)

Trong :

59

a: h s t l.
b: hng s thc nghim; b = 1 khi nng c nh; b < 1 khi nng C
(mol/L)ln.
c. Phng php o ph hp th nguyn t dng ngn la

Nguyn l c bn ca phng php nh sau: L s hp thu nng lng (bc x


n sc) ca nguyn t trng thi hi (kh) khi chiu chm tia bc x c bc sng
xc nh i qua m hi nguyn t, th cc nguyn t t do s hp th bc x c bc
sng ng ng vi nhng tia bc x m n c th pht ra c trong qu trnh pht x.
Ph sinh ra trong qu trnh ny gi l ph hp th nguyn t.
thc hin php o ph cn phi c cc bc sau:
- Chn cc iu kin ph hp chuyn mu phn tch t trng thi ban u (rn
hay dung dch) thnh trng thi hi ca cc nguyn t t do (qu trnh nguyn t ha
mu). Nhng thit b thc hin qu trnh ny gi l h thng nguyn t ha mu.
- Chiu chm tia pht x ca nguyn t cn phn tch qua m hi nguyn t va
iu ch c trn. Cc nguyn t ca nguyn t cn xc nh trong m hi s hp
th nhng tia bc x nht nh v to ra ph hp th ca n. y mt phn cng
ca chm sng b mt loi nguyn t hp th v ph thuc vo nng ca nguyn
t trong mi trng hp th. Ngun cung cp chm tia sng pht x ca nguyn t cn
xc nh gi l ngun bc x n sc.
- Da trn nguyn tc ca php o ph hp th nguyn t, nn dng c dng trong
phng php ny gm c nhng b phn chnh nh sau: ngun sng, b hp th, thit
b quang hc, thit b thu v ghi.
- Ngun sng: Ngun sng chnh thng dng trong phng php phn tch quang
ph hp th nguyn t l cc n catt rng. n ny l bnh hay ng hnh tr bng
thy tinh c cc in cc dng t nng. Bnh c np y mt kh tr no c
p sut thp (Ar, Ne, He, Xe,). c vng bc x t ngoi, ca ra ca n c ch
to bng thch anh hoc thy tinh c bit.
- B hp th: b hp th dng chuyn cht phn tch sang trng thi m trong
cc cht cn xc nh s tn ti di dng nhng nguyn t t do, c kh nng hp th
nh sng ca ngun nh sng bn ngoi. C th dng cc n kh lm b hp th.
Nghin cu s ph thuc ca cng mt vch ph hp th ca mt nguyn t
v nng C trong mu phn tch, l thuyt v thc nghim cho thy: trong mt vng
nng C nh, mi quan h gia cng vch ph hp th v nng ca nguyn
t trong m1 hi cng tun theo nh lut: Lambe - Bia:
D = 0,43.K.C.l

(2-22)

K: H s hp th, ph thuc vo chiu di sng;


C - Nng nguyn t cn xc nh c trong ngn la; ppm, ppb.
l - Chiu dy ca lp hp th; trong my o ph hp th nguyn t th l chiu
di ca ngn la (chiu di ca n nguyn t ha); cm
D - Mt quang ca ngn la; nm
Da vo gi tr mt quang, ngi ta xc nh nng nguyn t ca nguyn
t cn xc nh trong th tch mu.
60

2.2.3. Phng php kch hot ntron

Phng php phn tch da trn c s ca phn ng ht nhn, c nhy v


chnh xc cao; p dng c cho c cc nguyn t a lng, vi lng trong nhiu i
tng khc nhau, khng chu nh hng bi nhiu yu t cht nn. Mu phn tch
khng a vo nhng cht l nh thuc th, cht ha tan, nh cc phng php
phn tch ha hc khc. Kt qu phn tch khng ph thuc vo trng thi ha hc ca
nguyn t.
Phng php ny c kh nng phn tch a nguyn t, trong nhiu loi mu, c
th phn tch 20 - 30 nguyn t ng thi. Kt hp phng php kch hot ntron vi
cc phng php tch ha phng x (kch hot ntron c x l ho) tng nhy
phn tch.
Phn tch kch hot ntron da trn s bn ph mu bng chm ntron, lm bin
i cc ht nhn bn c trong mu thnh cc ht nhn phng x. Phn ng ht nhn
biu din qu trnh trn c vit nh sau:
A
X
Z

1
n
0

A+1 *
X
Z

A+1
X
Z

Khi b kch hot bng ntron, s ht nhn phng x to thnh v tc phn r


ca chng (gi l hot ) t l vi s ht nhn bn ban u. Khi phn tch mt nguyn
t, ta c th o c hot ca ng v phng x ng vi nguyn t . Hot ny
t l vi s m ghi c ca mt lng t no do ng v phng x pht ra. V
vy, da vo s m ny c th xc nh c hm lng ca nguyn t trong mu,
thng qua phng trnh kch hot ntron:
m=

M .A
e .t1
.
f . . (1 e .t ).6, 02.1023

(2-23)

Trong :
m: khi lng (gam) nguyn t cn phn tch trong mu.
M: trng lng nguyn t ca nguyn t cn xc nh.
A: hot phng x ca ng v con c to thnh; n v phng x l
becoren, k hiu l Bq.
f: mt dng ntron s dng kch hot mu; ht/cm2/gy.
: tit din phn ng bt ntron; barn, 1 barn =10-24cm2.
: ph bin ca ng v bn ban u ca nguyn t.
t: thi gian chiu mu (thi gian kch hot ntron); giy.
t1: thi gian ngui mu (tnh t lc kt thc chiu n khi bt u o).
: hng s phn r phng x ca ng v con.

61

Chng 3:

PHNG PHP PHN TCH

MT S CH TIU CHT LNG NC


3.1. Cc ch tiu vt l
3.1.1. Ch s pH

pH l ch s c trng cho nng ion H+ c trong dung dch, thng c


dng biu th tnh axit v tnh kim ca nc.
Trong nc, pH c tnh theo cng thc:
pH = - lg[H+] v c thang n v t 0 - 14.
Khi

pH = 7 nc c tnh trung tnh.


pH < 7 nc c tnh axit.
pH > 7 nc c tnh kim.

pH l mt trong nhng thng s quan trng v c s dng thng xuyn nht


trong ha nc, dng nh gi mc nhim ngun nc, cht lng ca nc
thi, nh gi cng ca nc, s keo t, kh nng n mn,... v trong nhiu tnh
ton trong cn bng axt - baz.
Vi qu trnh to men trong t bo v qu trnh hp th cc cht dinh dng vo
t bo ca a s vi sinh vt, khong gi tr pH ti u l 6,5 - 8,5.
pH c th c xc nh bng giy ch th mu hoc bng pH cc hydro hoc
cc thy tinh.
* Phng php xc nh pH:

- c hng dn ca nh sn xut trc


khi s dng my o pH.
- Hiu chun thit b: Khi phn tch pH, cn
phi thc hin chun my o theo khong gi
tr pH ca mu nc. Tu thuc vo tnh cht
ca mu nc m s dng dung dch chun
pH thch hp.
+ Nu cc mu cn o c tnh trung tnh,
hiu chnh my vi dung dch pH chun = 7.
+ Nu cc mu cn o c tnh axt, hiu
chnh my vi dung dch pH chun = 5.
+ Nu cc mu cn o c tnh kim, hiu
chnh my vi dung dch pH chun = 9.
- o mu nc, c kt qu trn my.
- Sau khi o pH ca nc thi cha du m v cc hp cht ha hc, cn phi ngm
in cc ca my o trong dung dch HCl 12% trong khong thi gian 2 gi v sau
ra li in cc bng nc ct hai ln phc hi nhy ca in cc.
3.1.2. Nhit

Nhit ca nc l i lng ph thuc vo iu kin mi trng v kh hu.

62

Nhit l iu kin xc nh c im cc qu trnh sinh, ha hc, v.v.. din ra


trong mi trng nc. Nhit c nh hng n s ha tan oxy v qu trnh t lm
sch ngun nc. Do , nhit ca nc v nhit mi trng xung quanh l
nhng tc ng trc tip nh hng ti thnh phn v cht lng, nh hng ti cc
qu trnh x l bng phng php ha hc. o nhit ca ngun nc ni ly mu
v nhit khng kh xung quanh l yu t cn thit trong qu trnh xt nghim mu
nc ni chung.
Nhit c nh hng khng nh n cc qu trnh x l nc v nhu cu tiu
th. Nc mt thng c nhit thay i theo nhit mi trng. V d: min
Bc Vit Nam, nhit nc thng dao ng t 13 - 340C, trong khi nhit
trong cc ngun nc mt min Nam tng i n nh hn 26 - 290C.
Nhit ca nc thng thng c xc nh cng vi pH hay DO bng my o.
3.1.3. mu

Nc mt thng c mu cao, l mt phn do cc cht l lng trong nc


mang mu. Nc sng, sui chy qua nhng vng t t lm cho nc c mu
trong sut thi k l.
mu thng do cc cht bn trong nc to nn. Cc hp cht st, mangan
khng ho tan lm nc c mu nu , cc cht mn humic gy ra mu vng, cn cc
loi thy sinh to cho nc mu xanh l cy. Nc b nhim bn bi nc thi sinh
hot hay cng nghip thng c mu xanh hoc en.
Nc thi thng c mu nu en hoc nu.
Mu ca nc c phn thnh 2 dng: Mu thc do cc cht ha tan hoc dng
ht keo l lng, cc cht hu c, Mu biu kin l mu ca cc cht l lng trong
nc to nn. Trong phn tch nc, ngi ta xc nh mu thc ca nc, ngha l
sau khi lc b cc cht khng tan.
Khi phn bit gia mu biu kin vi mu thc l rt quan trng. Nhn chung
cng mu thng tng khi pH tng, v vy cn kim tra pH khi xc nh mu.
xc nh mu ngi ta s dng cc ha cht chun l K2PtCl6 v CoCl2, c
th dng k thut trc quang hoc ng so mu (thng c gi l ng Nessler). n
v mu chun hin nay l Pt-Co (PCU, Platinum-Cobalt Color Units), mt s
trng hp s dng n v TCU (True Color Units).
Nc thin nhin thng c mu thp hn 200Pt-Co. mu biu kin trong
nc thng do cc cht l lng trong nc to ra v d dng loi b bng phng
php lc. Trong khi , loi b mu thc ca nc (do cc cht ho tan to nn)
phi dng cc bin php ho l kt hp.
Theo tiu chun ca WHO (World Health Organization) v US (United States),
EPA (Environmental Protection Agency) th mu trong nc ung 15 TCU.
3.1.4. c

Nc l mt mi trng truyn nh sng tt. Khi trong nc c cc vt l nh


cc cht huyn ph, cc ht cn t ct, cc vi sinh vt, kh nng truyn nh sng b
gim i. Nc c c ln chng t c cha nhiu cn bn.
c trong nc l do cc ht rn l lng, cc cht hu c phn r hoc do cc
ng thc vt thy sinh gy nn. c lm gim kh nng truyn nh sng trong
dung dch nc, gy mt m quan khi s dng nc, nh hng n cht lng sn
63

phm. Cc vi khun c th xm nhp vo cc ht rn l lng nn gy tr ngi cho giai


on kh trng nc v c th tr thnh nguyn nhn gy bnh t ngun nc. c
l mt vn quan trng trong h thng cp nc cng cng bi v 3 l do chnh: m
quan, kh nng lc v kh trng nc.
n v chun o c l s cn tr quang hc do 1mg SiO2 ha tan trong 1 lit
nc ct gy ra. n v o c: 1 n v c = 1mg SiO2/1lt nc.
c cng cao: nc nhim bn cng ln.
c cng c th c o bng my so mu quang in vi knh lc mu
c bc sng 580 - 620 nm. Cch tin hnh nh sau: ly nc trong quay li tm 3000
vng/pht, trong vng 10 - 15 pht, ly dch trong ca nc a ln my so mu,
chnh my v s khng. Sau ly cc mu th cho vo cuvet v o trn my so mu.
S o c biu th c ca mu th. Lu : s o c trn my so mu vi
bc sng 600 - 620 nm cng ln th c cng ln.
o c ca nc bng my o c. n v o c thng c k
hiu l NTU (Nephelometric Turbidity Units), FNU (Formazin Nephelometric Unit),
JTU (jackson turbidity unit), FTU (Formazin Turbidity Unit);1 NTU tng ng vi
0,58mg formalin trong 1 lt nc.
Nu phi pha long mu nc cn xc nh c, c ca mu s bng
c o c sau pha long nhn vi h s pha long.
Ngoi vic dng SiO2 lm huyn ph chun, ngi ta cn dng cc huyn ph
chun khc nh formazin hoc styren ivinylbenzen.
n v o c thng l mg SiO2/l, NTU, FTU; trong n v NTU v FTU l
tng ng nhau. Nc mt thng c c 20 - 100 NTU, ma l c khi cao n
500 - 600 NTU. Nc cp cho n ung thng c c khng vt qu 5 NTU.
Nc ung thng thng thng c c nm trong khong t 0 - 1 NTU.
Hm lng cht rn l lng cng l mt i lng tng quan n c ca nc
3.2. Cc ch tiu ha hc
3.2.1. xy ho tan (Dissolved Oxygen - DO).
a. Khi nim chung

Tt c cc sinh vt sng b ph thuc vo oxy dng ny hay dng khc duy


tr qu trnh trao i cht nhm sn sinh ra nng lng cho s sinh trng hoc sinh
sn. Qu trnh hiu kh l vn c quan tm nht khi chng cn oxy t do.
Oxy ho tan trong nc cn thit cho nhng sinh vt hiu kh. Bnh thng oxy
t do trong nc nm trong khong 8 - 10 mg/l. Cc cht gy nhim c trong nc
thng lm gim kh nng ha tan ca oxy trong nc.
Oxy trong nc thng c to ra do s ho tan t kh quyn hoc do quang
hp ca to. Khi nng DO thp, cc loi sinh vt nc gim hot ng hoc b cht.
Do vy, DO l mt ch s quan trng nh gi s nhim nc ca cc thu vc.
b. Phng php Winkler xc nh hm lng oxy ha tan

* Nguyn tc
Phng php Winkler v nhng ci tin ca chng l nhng k thut tiu chun
xc nh oxy ha tan hin nay.

64

Phng php ny kh n gin, d thc hin v cho php t chnh xc cao


khi hon thnh cn thn tt c khu khi tin hnh nh lng.
Phng php da trn c s phn ng m Mn+2 trong mi trng kim
(dung dch c cho vo trong mu nc trong cng hn hp vi dung dch KI) b O2
trong mu nc xy ho n hp cht Mn+4, s ng lng ca hp cht Mn ho tr 2
lc c kt hp vi tt c O2 ho tan.
MnCl2 + 2NaCl

2NaCl + Mn(OH)2

Mn(OH)2 + O2

2MnO(OH)2

Trang

Vang nau

S ng lng ca Mn(IV) c to thnh dng kt ta mu vng nu bng


s ng lng xy ho tan trong nc. Khi thm axit H2SO4 vo trong mu, hp cht
Mn(IV) hay ni khc i l s ng lng ca O2 ho tan, chnh bng s ng lng
I2 c trong mu nc.
MnO(OH)2 + 2H2SO4 + KI = MnSO4 + K2SO4 + 3H2O + I2
I2 t do c tch ra, d dng nh lng dung dch chun Na2S2O3.
I2 + 2 Na2S2O3 = 2NaI + Na2S4O6
Bit th tch v nng Na2S2O3 khi chun ta
d dng tnh c hm lng xy ha tan trong mu
nc. V th khi xc nh O2 ho tan trong nc c
thc hin trong 3 giai on:
Giai on I: C nh O2 ha tan trong mu (c nh
mu)
Giai on II: Tch I2 bng mi trng axt (axt
ha, x l mu)
Giai on III: Chun I2 bng Na2S2O3 (phn
tch mu)
Hn ch ca phng php: phng php Winkler xc nh O2 ha tan trong nc
khng p dng vi nhng mu nc c cht xy ho (vng nc b nhim bn nc
thi cng nghip) c kh nng xy ho anion I-, hoc cc cht kh (ihydrosunfua
H2S) kh I2 t do.

* Ha cht cn thit.
- Dung dch MnCl2: Ha tan 250g MnCl2.4H2O trong 620ml nc ct ng vo
l trng.
- Dung dch KI/NaOH: Ho tan 150g KI trong 200ml nc ct, ho tan 500g NaOH
trong 500ml nc ct (khi ho tan va khuy va lm lnh). Trn 2 dung dch ny vi
nhau v thm nc ct n 1l. ng vo l nu, nt cao su.
- Dung dch tinh bt
Cch pha th 1: Ha tan 0,5g tinh bt d tan vi 1lt nc ct, ri thm 100ml
nc ct v khuy, un n si. C th thm 3git CCl4 hoc CHCl3 dit vi khun.
Cch pha th 2: Cho 2g tinh bt d tan vo trong 1lt nc ct. Dng NaOH 20%
va cho va khuy vo dung dch tinh bt (ht khong 30ml dung dch kim) cho ti
khi c mt dung dch trong sut, hi snh. yn trong 1 gi, dng dung dch HCl
20% va cho va khuy trung ha kim, cho n khi phn ng axt yu (th o

65

giy o pH = 6 l c). Thm hn hp 1ml axt axetic 99% bo qun. Dung


dch mt nm mi hng.
- Dung dch nguyn chun K2Cr2O7 0,1 N: Cn 4,903g tinh th ha tan v nh mc
n 1 lt bng nc ct hoc l dng K2Cr2O7 N/10.
H2SO4 c; Dung dch H2SO4 25%.
Ch : Khi pha phi axt vo nc, khng lm ngc li. ong lng axt trong
ng ong m khng dng pipet.
- Dung dch KI 1M: Ha tan 8,3g KI vo trong 500ml nc ct. Trn u ri cho
vo l nu.
- Dung dch Na2S2O3 0,1 N: Ha tan 25g tinh th Na2S2O3 . 5H2O trong 1lt nc ct,
un si ngui ( ui ht CO2). Thm 6 ht NaOH rn ri cho vo l hoc dng
Na2S2O3 N/10.
Dung dch va pha khng c nng chnh xc v vy cn phi xc nh li
nng . L do l trong tinh th Na2S2O3 thng ln Na2S, Na2CO3, Na2SO3 ... v
Na2S2O3 d b vi khun phn gii, b xy trong khng kh xy ha.

* Cch tin hnh


Np dung dch mi pha ln buret.
Cho vo bnh nn 10ml dung dch H2SO4 25%, 10ml KI 1M, 10ml K2Cr2O7. Lc
u yn 5 pht, chun bng Na2S2O3 0,1 N cho n mu vng nht, ri cho 3 git
h tinh bt. Tip tc nh tng git Na2S2O3 cho n ht mu xanh tm (ch n mt mu
xanh tm ca dung dch tinh bt ch khng th mt mu ca Cr3+ c). Ghi th tch
Na2S2O3, tiu tn V(ml). Nng dung dch Na2S2O3 c tnh theo cng thc:

N =

10. 0,1
V

Tng qut:

VK 2Cr2O7 . N K 2Cr2O7
V

T dung dch Na2S2O3 bit chnh xc nng , ta pha dung dch Na2S2O3 0,01
N l dung dch chun xc nh O2 ha tan.

* Tnh ton
Hm lng O2 ho tan trong nc c tnh theo cng thc:
mg O2/L =

V . N . 8 . 1000
V0

Trong :
V:

S ml dung dch Na2S2O3 0,01N dng ht

N:

Nng dung dch chun Na2S2O3

V0:

Th tch mu nc x l phn tch

8:

ng lng ca O2

1000:

H s i thnh lt
66

Ch : Trong giai on c nh, chng ta thm 2ml ho cht (1ml MnCl2 + 1ml
KI/NaOH) vo trong chai mu 125ml, nn lng nc thc t c nh lng (tr
phn ho cht cho vo) l:
25 x

125 2
= 24,6 (mL)
125

V nh vy hm lng O2 ha tan trong nc chnh xc l:


V . N . 8 . 1000
24,6

mg O2/L =

3.2.2. Nhu cu oxy sinh ha (Biochemical oxygen Demand - BOD)


a. Khi nim chung

BOD l lng oxy cn thit vi sinh vt oxy ha cc cht hu c c kh nng


phn hy sinh hc trong iu kin hiu kh. n v tnh l (mg/l). Khi nim c kh
nng phn hy ngha l cht hu c c kh nng dng lm thc n cho vi sinh vt.
Cha t h u c

O2

CO 2

Vi sinh va t

H 2O

Te ba o m i (ta n g sinh kho i )

Lng oxy s dng trong qu trnh ny l oxy ha tan trong nc, oxy do qu
trnh quang hp.
Ch tiu BOD c xc nh bng cch o c lng oxy m vi sinh vt tiu th
trong qu trnh phn hy cc cht hu c. Ch tiu BOD cng cao chng t lng
cht hu c c kh nng phn hy sinh hc nhim cng ln.
Nc thi sinh hot c BOD 80 - 240 mg/l
Nc thi cng nghip c BOD 200 - 30000 mg/l
BOD5 l thng s c s dng ph bin nht chnh l oxy cn thit oxy
ha sinh hc trong 5 ngy nhit 20oC trong bng ti ( trnh hin tng quang
hp trong nc). Bnh thng 70 - 80% oxy c s dng trong 5 ngy u. Theo
l thuyt, phn ng c th xem l hon ton trong 20 ngy, y l khong thi gian
kh di. Kinh nghim cho thy t l BOD5/BODtng cng tng i cao nn thi gian
5 ngy l hp l. T l ny cao hay thp ty thuc vo vi sinh vt c b sung trong
phn tch BOD v bn cht ca cht hu c.
Qu trnh oxy ha cc cht hu c trong nc c th xy ra theo hai giai on:
- Giai on 1: Ch yu oxy ha cc hp cht cacbua hydro, qu trnh ny xy ra
20 C.
o

CnHm

(n + m) O2

Vi khuan

n CO2

m/2 H2O

- Giai on 2: Oxy ha cc hp cht nit.


2NH3

2NO2-

+
+

3 O2 Vi khuan

O2

2 nNO2- +
2 NO3-

Vi khuan

2H

2 H2O

b. Phng php xc nh BOD5

Nc pha long cn phi cy thm vi sinh vt v ngun vi sinh vt i vi nc


nh sau:
67

A. Nc mt (sng, sui, ao, h): pha long nc thi sinh hot.


B. Nc thi: l nc ly t cui ca dng thi.
DO ca nc pha long cy vi sinh vt sau 5 ngy nhit 20oC khng
c gim qu 1 mg/l so vi DO ban u.
Trung bnh mu nc c pH nm trong khong 6,5 7,5.
Nu mu nc cha lng ln to v
cc ph du thc vt, th chng cn c lc
qua li lc ph du trc khi xc nh
BOD5.
Vi mu nc cha cc cht c hi i
vi vi sinh vt nh kim loi nng, cht dit
khun, cn phi nghin cu cch loi tr
cc nh hng ring ca chng.
Clo t do v clo lin kt c th loi tr
bng dung dch natrisunft 0,5 mg/l.
Trong nc thi thng c hm lng
cht hu c kh ln v lng oxy ha tan khng p ng cho 5 ngy 200C.
xc nh BOD5 thng dng phng php pha long mu nc bng cch b sung
vo nc mt s cht khong lm bo ha oxy ha tan (v tan oxy gii hn trong
khong 9 mg/l 200C).
Dch pha long c chun b chai ming to. Bo ha oxy bng cch thi kh
vo 1 lt nc ct, lc u nhiu ln n khi bo ha oxy ha tan sau thm cc
dung dch nh sau:
- 1ml dung dch m photphat pH = 7,2 (ha tan 8,5 gam KH2PO4, 21,75 gam
K2HPO4, 33,4 gam Na2HPO4.7H2O, 1,7 gam NH4Cl trong nc ct, nh mc ti 1lt).
- 1 ml magiesunfat (ha tan 2,25 g MgSO4.7H2O trong 100 ml nc ct).
- 1ml canxiclorua (ho tan 2,75 g CaCl2 trong 100 ml nc ct).
- 1ml FeCl3 (ha tan 0,25 gam FeCl3.6H2O trong nc ct nh mc ti 1 lt).

* Xc nh BOD5: Mu nc trong l y, nt kn. Trc khi phn tch cn trung ha


v pH = 7 bng axt sunfuric 1N hoc natri hiroxt 1N. Nu cn th tin hnh pha
long da vo ch s BOD:
Nu BOD5 khng vt qu 7mg/l th khng pha long, thc hin o gi tr BOD
trc tip: Mu c ly vo t nht 2 bnh BOD 200 - 300 ml. o gi tr DO ngay i
vi bnh th nht v cc bnh cn li sau 5 ngy 200C:
BOD5 = DOo - DO5
Nu c lng mu nc c gi tr BOD>7 mg/l th mu nc phi pha long.
12 mg O2/l pha long theo t l 1:1 (1 phn nc + 1 phn dung dch pha long).
30 mg O2/l pha long theo t l 1:4 (1 phn nc + 4 phn dung dch pha long).
60 mg O2/l pha long theo t l 1:9 (1 phn nc + 9 phn dung dch pha long).
300 mg O2/l pha long theo t l: 2 phn nc + 98 phn dung dch pha long.
600 mg O2/l pha long theo t l: 1 phn nc + 99 phn dung dch pha long.

68

1200 mg O2/l pha long theo t l: 0,5 phn nc + 999,5 phn dung dch pha
long.
Khi pha long cn ch khng oxy cun theo. Mu nc (sau khi pha long)
c cho vo chai phn tch BOD c dung tch 300ml, cho y, y nt kn. Mt chai
5 ngy trong bng ti 200C. Mt chai em xc nh DO thi im ban u.
Chai sau 5 ngy em phn tch.

* Kt qu c tnh nh sau:
BOD5 = (C1 C2)/P
C1: Nng oxy ha tan (DO) sau khi pha long thi im ban u phn tch,
mgO2/l
C2: Nng oxy ha tan sau 5 ngy, 200C, mgO2/l
P: H s pha long.
He so pha loang P =

The tch mau nc em phan tch


The tch mau nc em phan tch + the tch dung dch pha loang

H s pha long: da vo pha long c khuyn ngh trong TCVN 60011995 v da vo gi tr COD, la chn h s pha long thch hp.
- i vi mu c nng COD< 0 mg/l th h s pha long tng ng l 5.
- i vi mu c nng 50<COD<120 mg/l th h s pha long tng ng l
10.
- i vi mu c nng COD>120 mg/l th h s pha long tng ng l 20.
Trng hp phi b sung vi sinh vt vo mu th (c th l ngun nc cng)
m bo cho qu trnh phn hy cc cht hu c. BOD5 s tnh theo cng thc:
BOD5 (mg/L) =

(C1

C2)

(B1

B2) F

B1, B2: Ch s DO trc v sau khi (mg/L) ca mu nc pha long c cy thm


ngun vi sinh vt.
F: t s gia th tch dch b sung vi sinh vt trong mu v trong i chng.
F =

% (hay ml) dch bo sung vi sinh vat trong C1


% (hay ml) dch bo sung vi sinh vat trong B1

* Phng php phn tch BOD c mt s hn ch:


- Yu cu vi sinh vt trong mu phn tch cn phi c nng cc t bo sng
ln v cc vi sinh vt b sung phi c thch nghi vi mi trng.
- Nu nc thi c c hi phi x l s b, loi b cht c , sau mi tin
hnh phn tch, ch gim nh hng ca cc vi khun nitrat ho.
- Thi gian phn tch qu di, v vy trong nghin cu hoc trong gim st cn phi
xc nh h s t l gia BOD v COD, ri tin hnh phn tch.
Ch tiu BOD khng phn nh y v lng tng cc cht hu c trong nc
thi, v cha tnh n cc cht hu c khng b oxy ha bng phng php sinh ha
v cng cha tnh n mt phn cht hu c tiu hao to nn t bo vi khun mi.
69

Do nh gi mt cch y lng oxy cn thit oxy ha tt c cc cht hu


c trong nc thi ngi ta s dng ch tiu nhu cu oxy ha hc.
3.2.3. Nhu cu oxy ha hc (Chemical Oxygen Demand - COD)
a. Khi nim chung

COD l lng oxy cn thit oxy ha cc cht hu c thnh CO2 v H2O di


tc dng ca cc cht oxy ha mnh.
Lng oxy ny tng ng vi hm lng cht hu c c th b oxy ha c
xc nh khi s dng mt tc nhn oxy ha hc mnh trong mi trng axt.
COD l ch tiu nh gi mc nhim ca nc (nc thi, nc mt, nc
sinh hot) k c cht hu c d phn hy v kh phn hy sinh hc.
Khi phn tch COD, cc cht hu c s chuyn thnh CO2 v H2O, v d c
glucoz v lignin u b oxy ha hon ton. Do gi tr COD ln hn BOD v c th
COD ln rt nhiu ln so vi BOD khi mu nc a phn nhng cht kh phn hy
sinh hc, v d nc thi giy c COD >>BOD do hm lng lignin cao.
Mt trong nhng hn ch ch yu ca phn tch COD l khng th xc nh phn
cht hu c c kh nng phn hy sinh hc v khng c kh nng phn hy sinh hc.
Thm vo phn tch COD khng cho bit tc phn hy sinh hc ca cc cht
hu c trong nc thi iu kin t nhin.
u im chnh ca phn tch COD l cho kt qu trong khong thi gian ngn
hn so vi BOD.
Phng php ph bin nht xc nh COD l phng php bicromat.
b. Phng php xc nh

Nguyn tc:
Chat hu c

K2Cr2O7

H+

Ag2SO4

CO2

t0

H2O + 2 Cr3+ + 2K+

Bc sunfat l xc tc cho phn ng oxy ho cc hp cht mch thng,


hirocacbon thm v pyridin. Trong khi clo gy cn tr do qu trnh phn ng vi
bicromat gy sai s d:
Cr2O72-

+
+ 6 Cl + 14 H

Cl2

+ 2H2O + 2 Cr

3+

Hm lng Cl- trong mu phi nh hn 1000mg/l. C th che Cl- bng thy


ngn sunfat:
2Cl- + Hg2+ HgCl2. Hng s bn = 1,7.1013
Lng biromat d c chun bng dung dch Mohr Fe(NH4)2(SO)4 v s
dng dung dch ferroin lm cht ch th. Phng trnh phn ng c biu din nh
sau:
Cr2O72-

Fe2+

H+

Fe3+

H 2O

Ch th s chuyn t mu xanh lam sang mu nht.


Fe(C12H8N2)32+ + Cr2O72- Fe(C12H8N2)33+

70

Cr 3+

- Phng php xc nh.


Phn ln cc cht hu c u b oxy ha
bi K2Cr2O7 trong mi trng axit, nhit
1500C.
Da vo hm lng cht hu c trong mu,
chn hm lng cht oxy ha c hay long
(0,1N hay 0,025N) cho thch hp. Sau khi phn
ng oxy ha xy ra hon ton, ta nh phn
lng dicromatkali d bng Fe(NH4)2SO4 theo
phng trnh:
6Fe2+ + Cr2O72- + 14H+
6Fe3+ + 3Cr3+ + 7 H2O
Tr s COD chnh l lng oxy tnh t hm lng K2Cr2O7 tham gia phn ng
oxy ha.
Tin hnh.
Ly 20 ml mu nc cho vo bnh c sinh hn hi lu, thm HgSO4 (nu trong
mu c hm lng 10 mg Cl-/l th thm 0,1 gam HgSO4) v 10 ml dung dch K2Cr2O7
0,25N v vi ht thu tinh.
Lp ng sinh hn vi nt thy tinh nhm. Thm vo t t 30 ml H2SO4 c c cha
Ag2SO4 qua phn cui ng sinh hn v lc dung dch hn hp trong khi thm axt.
un hi lu trong 2 gi.
ngui v trng sinh hn hi lu bng nc ct.
Pha long dch hn hp bng nc ct ti 150 ml. ngui, chun dicromat d
bng dung dch mui Mohr Fe(NH4)2(SO)4 v ch th ferroin.
Tin hnh song song vi mu trng 20 ml nc ct.
Tnh kt qu
COD (mg/L) =

(a b) N 8000
So ml mau th

a : Th tch dung dch mui Mohr dng chun mu trng; ml


b : Th tch dung dch mui Mohr dng chun mu th; ml
N : Nng ng lng ca dung dch mui Mohr
3.2.4. Ch s cht rn l lng
a. Khi nim chung

Cht rn l lng ni ring v tng cht rn ni chung c nh hng n cht


lng nc trn nhiu phng din. Hm lng cht rn trong nc thp lm hn ch
sinh trng hoc ngn cn s sinh sng ca thy sinh.
Cc cht rn c trong nc l:
- Cc cht v c l dng mui ha tan hoc khng tan.

71

- Cc cht hu c nh xc cc vi sinh vt, to, ng vt nguyn sinh, ng thc vt


ph du,..., cc cht hu c tng hp nh phn bn, cc cht thi cng nghip.
Cht rn trong nc phn thnh 2 loi theo kch thc ht:
- Cht rn qua lc c ng knh ht nh hn 1m (10-6m), bao gm dng keo v
dng ha tan.
- Cht rn khng qua lc c ng knh ln hn 1m, bao gm cc ht l xc rong
to c kch thc ht 10-5 - 10-6m dng l lng; ct sn, ct c kch thc trn 10-5m
c th lng cn.
Mt s ch tiu biu th hm lng cht rn nh sau:
- Tng cht rn TS (Total Solid): l trng lng kh cn li sau khi cho bay hi 1
lit mu nc (ph sa, mn b hu c, to) trn ni cch thy ri sy kh 1030C ti
khi trng lng khng i. n v tnh mg/l hoc g/l.
- Cht rn l lng dng huyn ph SS (Suspended Solid): l phn trng lng kh ca
cht rn cn li trn giy lc si thy tinh, khi lc 1 lt mu nc qua phu lc Gooch ri
sy kh 103 - 1050C ti khi trng lng khng i. n v tnh mg/L hoc g/L.
- Cht rn ha tan DS (Dissolved Solid): Hm lng cht rn ha tan bng hiu
gia tng s cht rn vi huyn ph. n v tnh mg/l hoc g/l.
DS = TS - SS
- Cht rn bay hi VS (Volatile Solid): Hm lng cht rn bay hi l phn mt i
khi nung lng cht rn huyn ph SS 5500C trong khong thi gian nht nh.
Thi gian ny ph thuc vo loi mu nc (nc cng, nc thi hoc bn). n v
tnh mg/l hoc phn trm (%) ca SS hay TS. Hm lng cht rn bay hi trong nc
biu th cho cht hu c c trong nc.
- Cht rn c th lng: L s ml phn cht rn ca 1 lt mu nc lng xung
y phu sau mt khong thi gian (thng l 1 gi).
b. Phng php xc nh

- Cn phi loi b vt th ni ln cng nh tp hp cc vt th khng ng nht


chm trong mu nc.
- Nu mu nc c khong cao, cn thit phi ra giy lc bng nc ct nhiu
ln trc khi sy giy lc.
- Khng ko di thi gian lc mu nc v cc ht keo c trong nc s b gi li
trn giy lc.
- Hm lng cn ti a trong phn mu phn tch khng vt qu 200mg chng
khng cn tr qu trnh bay hi ca nc.
- Tin hnh phn tch mu trng (nc ct 2 ln) hiu chnh kt qu phn tch nh sau:
(m1 m2) (m2t m1t) 1000
SS (mg/L) =
V

Trong :
m1, m2: khi lng giy lc trc v sau khi lc mu tng ng (mg).
m1t, m2t: khi lng giy lc trc v sau khi lc mu trng tng ng (mg).
V: th tch mu nc phn tch (ml).
Cng c th xc nh lng SS bng my quang ph hp th nguyn t.

72

3.2.5. Ch s Fe

St l nguyn t phn b rng trong t, thng trng thi c tan thp.


Do cc phn ng ha hc, sinh hc, chng chuyn ha thnh dng ha tan, ch yu l
Fe(II) thm vo nc ngm.
Trong nc ngm, st thng tn ti di dng ion Fe2+, kt hp vi cc gc
bicacbonat, sunfat, clorua; i khi tn ti di keo ca axit humic hoc keo silic. Khi
tip xc vi oxy hoc cc tc nhn oxy ho, ion Fe2+ b oxy ha thnh ion Fe3+ v kt
hp ta thnh cc bng cn Fe(OH)3 c mu nu . Tuy nhin trong iu kin ym
kh Fe3+ b kh thnh Fe2+.
Trong nc thin nhin, ch yu l nc ngm, c th cha st vi hm lng
n 40 mg/l hoc cao hn.
Vi hm lng st cao hn 0,5mg/l, nc c mi tanh kh chu, lm vng qun
o khi git, lm hng sn phm ca cc ngnh dt, giy, phim nh, hp. Cc cn st
kt ta c th lm tc hoc gim kh nng vn chuyn ca cc ng dn nc.
Hm lng st trong nc ngm dao ng trong khong: 0,5 50 mg/l. Trong
nc thin nhin st c th tn ti di dng Fe2+, Fe3+ v cc hp cht hu c ha tan
hay khng ha tan. Khi pH v nng oxy ha tan rt thp trong nc ch c ion Fe2+.
ha tan ca mui Fe2+ thng thng i ln, thy phn tng i nh, cho nn
Fe2+ kh to thnh kt ta tch ra. c bit trong nc ao h c cha axt humic, pH
ca nc ny thng gn bng 4, Fe2+ kt hp vi axt humic to thnh phc cht rt
kh b oxy ha bi oxy ha tan. Khi nng ha tan tng i ln, tr s pH cao Fe2+
s b oxy ha thnh Fe3+.
Fe2+ - e Fe3+ + 11.5kcal
Fe3+ s thy phn thnh Fe(OH)3 kh ha tan
Fe3+ + 3H2O Fe(OH)3 + 3H+
Khi pH ca nc ln hn hay bng 8, th Fe2+ trong nc b oxy ha vi tc
rt nhanh. Trong nc b mt v hm lng oxy ha tan tng i nhiu pH ca nc
ny thng trung tnh hay kim yu, hu nh ch c Fe(OH)3 trng thi keo khng
ha tan v nng Fe2+ trng thi dung dch tht rt nh. C nhiu loi tham gia vo
vic oxy ha Fe2+ Fe3+ nh Leptothrix ochracea v Crenothrix polyspora ng ch
nht l loi Thiobacillus (Thiobacillus ferrooxydanns) l loi vi khun c kh nng
oxy ha Fe2+ Fe3+ trong mi trng axt, y s oxy ha v c Fe2+ Fe3+ kh
c th xy ra.
St tn ti di nhiu dng khc nhau, ty theo nc b mt hay nc ngm m
st s tn ti di dng Ion ha tr 2 hoc ha tr 3 v dng hydroxyt kt ta. Hm
lng st trong nc phi m bo < 0,3 mg/l.
Khi trong nc c Fe, chng gy c mu:
2
Fe oxi hoa

Fe : mau nau o

Vic x l nc b nhim Fe (Dn gian gi l nhim phn) rt kh, a s cc h


dn s dng nc ngm u dng ct lc hoc lc s b thy nc trong c ngh rng
sch. Tuy nhin nu qua my nc nng, hoc cha trong b s thy lng cn mu .
C th dng phng php oxy ha st bng oxy khng kh x l st: Bn cht
ca phng php l s oxy ha st (II) v tch chng ra khi nc di dng st (III)
hiroxt. Trong nc ngm thng tn ti Fe(HCO3)2.
73

Fe(HCO3)2 + 2H2O Fe(OH)2 + 2H2CO3


H2O + CO2 H2CO3 H+ + HCO3Nu trong nc c oxy ha tan st (II) hiroxyt thnh st (III) hiroxyt.
4Fe(OH)2 + 2H2O + O2 4Fe(OH)3
Fe(OH)3 kt ta thnh cc bng cn mu vng d tch ra khi nc. T hp 3
phng trnh trn ta c:
4Fe2+ + 8HCO3- + O2 + 2H2O 4Fe(OH)3 + 8H+ + 8HCO3Tiu chun gii hn cho php ca cc nc EU l 0,2 mg/l, ca WHO l 0,3 mg/l.
C th xc nh hm lng Fe bng phng php hp ph quang ph nguyn t.
3.2.6. Clorua (Cl -)

Clo (Cl-) c mt trong nc l do cc cht thi sinh hot, nc thi cng nghip
m ch yu l cng nghip ch bin thc phm, ngoi ra do s xm nhp ca nc
bin vo cc ca sng, vo mch nc ngm.
L mt trong s cc Ion quan trng trong nc cp, v mn ca nc l do ion Cl
to nn. Nc c Cl- vi lng 300mg/l c th gy cm gic mn, nc mn vi nng
Na+, Cl- trong nc cao s gy ri lon in gii i vi c th con ngi v tc hi
n cy trng.
Clorua lm cho nc c v mn. Ion ny thm nhp vo nc qua s ho tan cc
mui khong hoc b nh hng t qu trnh nhim mn cc tng cha nc ngm hay
on sng gn bin. Vic dng nc c hm lng clorua cao c th gy ra bnh v
thn. Ngoi ra, nc cha nhiu clorua c tnh xm thc i vi b tng
Clorua l mt trong nhng ion rt quan trng trong ch dinh dng ca con ngi, l
mt b phn chnh. N c mt trong hu ht cc ng ng cung cp nc, nu gi s trong
nc cng c mt ca Na+ th nc s c v mn ca mui nu nng ca Clo 250 ppm.
Hin nay ngi ta vn cha c nhng kt lun chnh thc v s gy hi i vi
con ngi khi hm lng clo trong nc l cao. Ion Cl- l rt quan trng i vi sc
khe con ngi. N khng nhng c vai tr quan trng trong cn bng cc cht in ly
trong mu m cn sn xut ra axt trong d dy, HCl.
Mt lng ln ion clo c th c nhng nh hng n mn ng ng bng kim
loi v gy hi n s pht trin ca ng- thc vt. Do vy kim tra hm lng clo
trong nc l rt quan trng. Cho n nay c nhiu phng php xc nh lng clo
cn li trong nc t nhin cng nh nc sinh hot.
in hnh l cc phng php trng lng, phng php chun da vo phn
ng kt ta vi bc nitrat (ch khc nhau vic s dng cc ch th khc nhau nhn
ra im cui ca qu trnh chun ) v phng php o in th s dng in cc
chn lc ion clorua. Trong cc phng php c in th phng php trng lng
c xem l c chnh xc tng i cao, nhng thi gian tin hnh ko di v
khng ph hp khi xc nh clo nhng nng thp c bit l cc lng vt clo.
Ngy nay, phng php dng in cc chn lc ion l rt tin li, nhanh v chnh xc
ngay c khi ion nh phn c trong dung dch nhng nng rt nh.
Chng ta c th tin hnh xc nh clo trong nc bng cc phng php: php
o iod (chun oxy ha - kh), phng php Mohr, phng php Fajans (chun
kt ta).
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