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ΚΕΦΑΛΑΙΟ 2 ΟΙ ΒΑΣΕΙΣ ΤΗΣ ΥΔΑΤΙΚΗΣ ΧΗΜΕΙΑΣ PowerPoint PPT Presentation


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ΚΕΦΑΛΑΙΟ 2 ΟΙ ΒΑΣΕΙΣ ΤΗΣ ΥΔΑΤΙΚΗΣ ΧΗΜΕΙΑΣ.

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ΚΕΦΑΛΑΙΟ 2 ΟΙ ΒΑΣΕΙΣ ΤΗΣ ΥΔΑΤΙΚΗΣ ΧΗΜΕΙΑΣ

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2

2

Werner Stumm (ETH Zurich) James Morgan (CALTECH) . AQUATIC CHEMISTRY 1971.

, :

.H (. ) .


2

CO2

:

[CO2]g =350 ppm 0,0350 %

25C :

[CO2]aq =1,146 10-5M( Henry)

CO2(aq)+2H2CO3, Ka=2 10-3


Co 2 hco 3 co 3 2 2

CO2/HCO3-/CO32- 2

1. CO2

p

2.HCO3-

p

CO2, HCO3- CO32- pH.

pH-x


2

x : CO2, HCO3- CO32-

K1 K2:


2

+

p K1=6,35 & p K2=10,33


2

1) pH<<p1 ( pH)

+


2

2. pH = pa1 (pH6,35)


2

3. p= (p1+p2) (pH8,34)

. ~0,98


2

4. pH=p2 ( )


2

5. pH>>pa2

[+] (III) :


2

C3-

CO2 .


2

(.. ) : Henry

C2 :

CO2 + H2O HCO3- + H+

O + HCO3- Ka1:


2

CO2 :

([Alk]):

HCO3- , CO32- -

: [Alk]=1,00 10-3eq/L

. pH=7

[OH-]

[HCO3-] >> [CO32-]

[HCO3-]=1,00 10-3M

Ka1 =

>[CO2(aq)]

(1,146 10-5 )

CO2


2

. pH=10

[Alk]=1,00 10-3eq/L

[Alk]=[HCO3-]+2[CO32-]+[OH-]=1,00 10-3

[CO32-]=

[HCO3-] = 4,64 10-4 eq/L

[CO32-] = 2(2,18 10-4) = 4,36 10-4 eq/L

[OH-] = 1,00 10-4 eq/L

[HCO3-]=4,64 10-4M

[CO32-]=2,18 10-4M

[Alk] = 1,00 10-3 eq/L

[Alk] pH=7


2

.

[C]=[CO2]+[HCO3-]+[CO32-]

pH = 7: [C]pH=7 = 2,25 10-4 + 1,00 10-3 + 0 = 1,22 10-3

pH=10: [C]pH=10 =0 + 2,18 10-4 + 4,64 10-4 = 6,82 10-4

pH 7

pH 10.

pH 10

- ( ) CO32-.

CO32- CO3-.

pH 10

.


2

: C pH .

pH

C

pH .

C ,

pH , [Alk].


2

pH 7 pH 10, C

1L 2 ( [Alk]=1,00 10-3eq/L):

[C]pH=7 . 1L - [C]pH=10 . 1L =1,22 10-3 mol - 6,82 10-4 mol = 5,4 10-4 mol.

5,4 10-4mol/L

{CH2O}, 30 16 mg/L .

: CO2

[Alk] pH.

[Alk] pH.


2

[Alk] CO2 .

. 2 ( [Alk]=0)

H (S) CO2 350 ppm CO2:

S = [CO2(aq)]+[HCO3-]=1,146 10-5 + 2,25 10-6 = 1,371 10-5

. 2 [Alk]=1,00 10-3eq/L (NaOH)

CO2(aq)+OH-HCO3-

S = [CO2(aq)] + [HCO3-]=1,146 10-5 + 1,00 10-3 = 1,01 10-3

pH < 7 [+]

:

[Alk] = [HCO3-] + 2[CO32-] + [OH-] - [H+]


2

(Ca)


2

CO2


2

,

( e-):


2

: P2O74- .


2

  • :

  • 2) ()


2

  • , , ( ) .

  • .

  • , (.. ferrichrome) Fe (III).

  • ( ) .


2

2


2

-

D:

pH > 10 4-

-O2CCH2 CH2CO2-

NCH2CH2N

-O2CCH2CH2CO2-

3

(pH = 11) Cu~5mg/L EDTA 200 mg/L[Na2H2C10H12O8N2.20, =372]

  • Cu2+ ;

  • - Cu2+;


2

EDTA (Y4-):

H EDTA 5,4 10-4

Cu2++Y4-CuY2-

K1=6,3 1018

Cu2+ CuY2-

Cu2+ 7,9 10-5

CuY2-

:


2

* Brnsted

H pH.

+ n+:

pH ().


2

: (NTA)

CH2COO-

-OOCCH2 N 3-

CH2COO-

To T3- 3[CO2-] 1


2

3 :

1)

3 + + 2-

K1=

2)

3)


2

pH, :

3, 2-, 2- 3-


2

pH x


2

Pb Pb(OH)2

:

-

- 2

- pH

-

Pb Pb(OH)2 pH=8,00

pH = 8,00 2-:

Pb(OH)2(s) + HT2- PbT-+OH-+ 2

:

Pb(OH)2(s) Pb2+ + 2OH-

Ksp=[ Pb2+][ OH-]2=1,61 10-20


2

:


2

:

25 mg/L N(CH2CO2Na)3 (..=257)

:

[] = 9,7 10-5mmol/mL.

To /Pb(OH)2 pH ~8


2

To NTA HT2- PbT-:

  • ,

  • :

  • pH = 8,00 [OH-]=1 x 10-6M


2

[PbT-]/[HT2-]~20-21 Pb.

Pb (20mg/L) 9,66 10-5 . (9,7 10-5 ).

PbT- pH .

pH.


2

  • 5

  • .

  • Pb(OH)2 PbCO3.

  • To PbCO3 [Alk] pH .

  • NTA (3Na) 25 ppm pH = 7 PbCO3.

  • Pb;


2

:


2

  • pH 7-10 HCO3-.

  • CO32- PbCO3 HCO3-

PbCO3(s) + HT2- Pb2+ + CO32-

PbCO3(s) Pb2+ + CO32-

sp = [Pb2+] [ CO32-] = 1.48 10-13


2

PbCO3 ( ) PbT- [HCO3-]

[PbT-]/[HT2-]=K/[HCO3-])

[HCO3-]=1,00 10-3

PbCO3(S) PbT-.

  • [NTA]= 25 ppm [Pb2+]20 ppm

  • [HCO3-]

  • [HCO3-]


2

Ca2+

pH=7 Ca2+ NTA :

Ca2++HT2- CaT-+H+

K=

1. [Ca2+] = 1,00 10-3

2.pH = 7


2

Ca2+


2

PbT- CaT-.

:

HCO3- =1 10-3

Ca2+ =1 10-3

NTA PbCO3-:

  • 1/3 .

  • Ca2+ PbT-.

  • Ca2+ Pb .


2

:

Cl- .

  • n+ , (.. Cl-).

  • Cl-, Cd

  • + CdT- .

  • Ca2+ & Mg2+ Cd .


2

.

[Me(2)m]n+ + L [Me(2)m-1L]n+ + 2

[Me(2)m]n+ + L [Me(2)m]n+ . L

[Me(2)m]n+ . L [Me(2)m-1L]n+ + 2

2 : d[MeL]/dt = k [Me][L]

v = k ([Me(2)m]n+) ([L])


2

  • (kw) H2O :

  • pH,

  • Ca2+

  • ( 10-3 Cu .. 10-8).

  • .

!!!


2

To (H3PO4) :

H3PO4 H2PO4-+H+pa1=2,17

H2PO4- HPO42-+H+pa2=7,31

HPO42-PO43- + H+pa3=12,36

P2O74- .

2PO43- + 2 P2O74- + 2OH-


2

(H4P2O7) (H5P3O10)

H4P2O7 : pKa1 2, pKa2 2,64, pKa3 6,76, pKa4 9,42

H5P3O10 : pKa1, pKa2 2, pKa3 2,30, pKa4 6,50, pKa5 9,24

:

(*) (** )

(***) P.

pH=4,5 3:

pH=9,5 2:


P 2 o 7 4

: P2O74- .


2

  • (, ) .

  • ( , ) .


2

.. 300000 AMU

C:45-55%, O:30-45%, H:3-6%, N:1-5%, S:0-1%

Fe Al:

g:

Ni, Pb, Ca, Zn:


2

  • A 20 : .

  • E . : 1991 16 . 1992: 590,000 5,000 .

  • : .

  • : .

  • =

  • : , , , .


2

(, )


2

  • ():

  • ,

  • :

(DBPs):

  • pH

  • (, )


2

HOCl + (Br-) +

TTHMs DBPs

Br- + HOCl

Cl- + HOBr

HOBr

H+ + OBr-

  • :

  • (THMs)

  • (HAAs)

  • (HANs)

  • :

  • (HKs)


2

1WHO: World Health Organization, 1993, 2USEPA: Environmental Protection Agency, 1994,

3E.C.: Commission of European Union, 1998


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