?? 4.1 ??? ???? ?? ???????? K? ?? ??? ??? 25 ??? ??? ? ???.

1
Chapter4??
2
?? 4.1 ??? ???? ?? ???????? K? ?? ??? ??? 25 ???
??? ? ???.

• ? ?? ?????, ??? ??? ???? ?? ???? ???? ?? ?
  ?? ?? ???? ??????? ??? ???.
• ???, ??? ???? ?? ? ? ????
  ? ?? ??? ????. 25???
• 
  ??.

3
??? ? 4.2?? ???? ? ??? ?? ??? ?? ????.
4
?? 4.2 ?? ????? K? ??

• ?? 4.1??? ? ?? ?? ? ??? 25???? 10??? ????.
• ? Stumm? Morgan14? ?? ???? ??? ??? ???? ???? ??
  ????? ???.

5
?? 4.2 ?? ????? K? ??

• 10???? ??? ?? ??? ??? ??? ?(23)? ????.
• ?? ????, ?? ??? 25???? ??? 0.85? ? ??. ??? ???
  ?????? ? ?? ??? ???? ?? ??? ? ?? ??(??)?
  ????, ??? ????? ??? ????.

6
?? 4.2 ?? ????? K? ??

• ????? ?? ??? ??? ???? ??? 10-1000 atm?? ???? ??
  ??? ???? ???? ??? ??? ? ??. ??? ????, ???? ????
  ?? ? ??? ??? ???? ?(24)? ?? ??? ??? K? ???? ???
  ??? ? ??.
•                 
        (24)
• ???, ? ?????? ??? ?? ? ??( )?
  ????(P 1 atm), K? ?????? P? ?????. ? ??
  ? ??? ?? ?????? ????, ? (24)? ??? ????.

7
?? 4.2 ?? ????? K? ??

•                      (25)
• ???, ? ??????? ??????, ? ??? ?? ????,
  ? ??? ????. ???, ? ??????(
  ).
•  Stumm? Morgan14? ????? ???? ??? ?? ??? ?? ???
  ??? ??????, ?? ?? ????? ???? ??? ??? ????. 1000
  atm? ??(?? ?? 10,000m)?? ???? ???? ? ??
  ?????? 8.1? ??.

8
Example 4.3 Activity Corrections for the
Carbonate System

• In exact calculations with the carbonate system
  in a groundwater ( )
  we need activity corrections. pH is measured
  operationally with standard buffers, that is, as
  (infinite dilution). It is convenient to
  retain concentration units for the carbonate
  species (conservative quantities like total
  inorganic carbon or alkalinity have to be
  expressed as concentrations). Thus we apply our
  corrections to the equilibrium constants, K, and
  then make our calculations numerically or
  graphically as before.

9
Example 4.3 Activity Corrections for the
Carbonate System

• Solution
• Using the Guntelberg approximation equation (3),
  Table 4.3, we obtain

10
Example 4.3 Activity Corrections for the
Carbonate System

• and for , the divalent carbonate ion has a
  valence Z 2
• In this example, the corrections on p? values for
  activity coefficients are not very large. We did
  not use an activity correction for assuming that
  pH measurements correspond most closely to an
  activity measurement.

11
Example 4.4 Activity Coefficient of
Nonelectrolytes

• Find the activity coefficient of dissolved oxygen
  , in seawater ( ).
• Solution Morel and Herlng16 give the general
  empirical equation for neutral molecules
• where f is the activity coefficient of the
  neutral molecule and I is the ionic strength, M.
  At ionic strengths less than 0.1 M, the activity
  correction is less than 2. In seawater it
  becomes significant. For molecular oxygen in
  seawater, the activity coefficient is
  according to the equation above.

12
Example 4.4 Activity Coefficient of
Nonelectrolytes

• Actual studies of dissolved oxygen in seawater in
  the laboratory have yielded the following (more
  accurate) equation fur the activity coefficient.
• which yields an activity coefficient of
  . Neutral molecules have activity coefficients
  greater than 1.0 in electrolyte solutions and
  this is known as the "salting out" effect.

13
Example 4.5 Langmuir Adsorption Model
Dissolved Adsorbed
ConcentrationM ConcentrationM,ConcentrationS-M
mol L-1 mol L-1
4.57 10-7 5.43 10-7
6.28 10-5 4.34 10-5
0.000148 6.37 10-5
0.000244 7.24 10-5
0.000345 7.71 10-5
0.000450 7.69 10-5
0.000655 8.16 10-5
0.000759 8.35 10-5

• ??? ?? ????? ? 1??? ?? ??? 5.98??? ?? ?? ??????
  ?? ????. ???? ???? ???? ?? Langmuir ????
  ?  ??? ? ??? ????

14
Example 4.5 Langmuir Adsorption Model

• ? ??? ??? ??? ???? ?(75)? ??? ? ? ??.
• ??? ??? ?? ??/?? ???? ??? ???
• ? ?? ? ?? ??? ????. ? ??. ??
  ??? 10-3 M?? ??, ??? ??? ? ??? ?
  ??(??? ??? ?? 4.4? ????? ?? ??? ???? ???? ??). 

15
Example 4.5 Langmuir Adsorption Model

• ?? 4.5? ??? ??? ??? ????. ??? 9 10-5 mol L-1?
  ?? ??? ??? ???? ???? ?? ????(?)? ????. ??? ????
  ???(??)? ?? Langmuir? ??? ????.
• ???? ?? ??? ?? 4.6? ?????. ??? ?? ??
  ? ?? ? ?????. ???? ? ?? 1.1039 104
  L/mol ??. ????, ??? ? ??? ??. ???
  ??? ?????
  . Q.E.D??.

16
?? 4.6 ?? ??? ?? ??? ??? ?? ?? ?? ??

• ??? ?? ?? ??? ???, pH 7 ?  I 0.1 M?? ?? ?? ???
  ???.
•                               
• Dzombak and  Morel26? ??? ?? ??, ?? ?? ????? ??
  ?? ??? ????.
• ? I 0.1 M, pH 7??? ?? ?? ?? ? ??? ?? ?? 4.9?
  ????.
•                   

17
?? 4.6 ?? ??? ?? ??? ??? ?? ?? ?? ??

• ? (89a)? ? ???? ?? ??(??) ? ??? ?? ???.
•             
•                                       
• ? ?? P? ??? ??
•     
•                         
•                           

18
?? 4.6 ?? ??? ?? ??? ??? ?? ?? ?? ??

• ?? ?????,  pH 7 ? I 0.1 M?? HFO? ??? ???? H
  ??? ?? ?? ??? ?? 0.127? ??? ?? ?? ??? ?? ????. ??
  ??? HFO? I gt 0.01 M? ???? pH ?? 7?? ?? ?? ? 9??
  ? ??? ?? ????.

19
?? 4.7 ?-??, ???, ?? ???

• ????? ???? ???? ? ????
  ??? ? ?? ???? ??? ???. ??????? ??, ????. log?? ?
  pH? ??? ?????. pH ??? ?? ?? ? ???? ??? ??? ???
  ????. ? ????, ????? ??? ? ??. ??? ??? ???????
  ????? ???? ? ??? ??? ??? ??? ???.
• ?? ????? ? ? ? 4.2? ??? ?? ?? ?? ??? ????. ???
  ???? ??? ? ?? ????? ?? ????. ????? ??(?? ??)
  ????? ?? ??? ? ??. 
• ???
• ????

20
?? 4.7 ?-??, ???, ?? ???

• ? ????? Type I ????? ?? ?? ??? Type II ?????. ??
  ?????, ??? ???? ?? ?? ? ?? ????? ??? ? ? ??.
• ??? ? ???? ??????? Na? ??? ? ??.
• ???? ??? ???? ? ??? ????? Na ???
  ??? ??? ?? ?? ????.
• ???? ???? ?? ????? ??? ??? ??? ? ??. ? ????? ????
  ????? ??.
• ??? ????? ???? ??(??? ??? ???). 

21
?? 4.7 ?-??, ???, ?? ???

• ??? ??? ?????? ????. ?? ???? ?? ?? ?? ??? ????(??
  ??). ??? ????? ??? ???? ??(?? ??).

22
?? 4.7 ?-??, ???, ?? ???

• ?? ? ??? ?(i)-(vi)? ??? ?? ??? ? ??. ??? ? ?? ??
  ??? ?? ? ????? ??? ????.

Components Components Components Components Components Components
Species
1 1 0 1 6.3
2 1 0 0 0
3 1 0 -1 -10.2
4 0 1 0 0
5 0 0 -1 -14
6 0 0 1 0

23
?? 4.7 ?-??, ???, ?? ???

• ? ?????? ???? ?? ???? ??.
•      TOT Carbonate
•     TOT Na
•     TOT H
• ???? ?? ????? ? ?? H??? ???? ?? ??? ??? ?? ??.
  H?? ??? ???? ?? ?? pH ????. ? ?????? ???? ???
  ????? ????(???) pH ?? ? ??? ???? pH ?? ???? ??? 
  ???. TOT H ?? ????? ??????.
• ?? ??? ?? ?????? ????.

24
?? 4.7 ?-??, ???, ?? ???

• ?? ??, ? ??? ???? ??? pH?? ?? ??? ???. ??? ?????
  ???, ??? ??? ???? ?????? ??? ??? ?? 4.10? ??
  ????? ?? ?????. 
• M ???? ???? ?? ??? pH 8.2??
  ????. 
• ??? ????, ???? ??? 
  , pH 8.2?? ?????. ??? ??? ?? ?
  ??? ?? ???  ,
  , , pH
  8.22??.

25
?? 4.8 f(pH)? ?? ???? ? ??? 

• ? ????? ??? ??? ?? ???? ???? ?? ?????. ??? ?? ?
  ??? ???? ??.
• ??? ??? pH?? ? ????? ?????.
• ???? ????? ???? ???? ? ???? ????.
• ? ????? ?? ? ?? ???
  ????(??? ??? ????? Cüntelberg ?? ??? Davies ????
  ???? ?? ??? ??? ????? ?? ? ??).  

26
?? 4.7 ?-??, ???, ?? ???
?? 4.10 ?? 4.7? ?? ??? Log C? pH? ??
27
?? 4.7 ?-??, ???, ?? ???

• ?? ??? ??? ???? ????? ????. ?? ????? ?? ?????
  ???? Handbook of Chemistry?
  Physics? ????. ?? ?? ???? ?? ??? ??? ????? ????.
• ????? ??? ???? ???? ???? ?? ?????, ?,

28
?? 4.7 ?-??, ???, ?? ???

• ??? ?? OH-? (ova) ????? ???? ???, ??? ???? (H)?
  ??? ??? ??? ? ?? ?,
• ?? ? ?? ??? ?? ? ? ??.
• Species
•   Components

29
?? 4.7 ?-??, ???, ?? ???

• ????? ????, ??? ?? ?? ?? ???  Fe(III)
  ???? ??? ? ??. ??? ? ??? ????? ??
  ?????  ????? ?????. ?? ??? ?? ?? ???? ????? ????
  ????? ?? ???? ????.
• ????? ?? pH ??? ? ?????? ?? ????? ??. ??? ????
  ?????? pC ? pH? ??? ???? ???? ????? ?? pH? ???
  ???.

30
?? 4.7 ?-??, ???, ?? ???

• ? ?????(mass action expressions)? ??? ?? ???? ???
  ?? ????? ??? ?? ??????. ???
  
• ? ?? ?? ??? ??? ???.
• ???? ??? ???? ??? ? ???? ?? ????
• ??? ?? ???? ??? ???? Type III ?????.
• ??? ?? ?????? ?????.

31
?? 4.7 ?-??, ???, ?? ???

• ? ??? ???? ????? ????? ??? ??? ??. ? ????? pH?
  ?? ?? ?? ?? ???.

Components Components Components Components Components
Species Species Species Species Species
1 1 3 3.3
2 1 2 0.5
3 1 1 -2.6
4 1 0 -9.8
5 1 -1 -18.5
6 0 -1 -14.0
7 0 1 0
??? ?? 4.11? ???? ??. ??? ?????? ???? ??.
32
?? 4.9  -FeOOH??  Pb(II)? ?? ???

•   a-FeOOH(geothite)?? M Pb(II)? ??? ? pH?
  ???? ???? ?? ??? ????. ????? ??? ??? ??. ??? ?
  ???? ??? ??? Cd, Cu, Zn, Pb, Hg? ?? ??? ????
  ????? ?? ?? ???? ??? ??? ????.
• ??????? ???? ?? log C ? pH? ??? ?????.  ??
  ????(capacitance) 2.9 ? ?? ??? ???? ???
  ????. ??? ?? ??? 14.7 ? ????. ?? ??? ??
  SOH 0.000135 , ????? ?? 0.1
  ,
• ????? 0.01 ??.

33
?? 4.9  -FeOOH??  Pb(II)? ?? ???
?? 4.1 25 ?, ??(??)?? ? ???? ?? log C?
pH? ??(?? 4.8)
34
?? 4.9  -FeOOH??  Pb(II)? ?? ???

• ?? ?????? ????
• ??? 
•         
• ?? "gt"? ? ?? ???? ???. ? ??? ??(
  ? ????, ???)? ?? ?????. ? ??????? ??
  ??? ?? ??? ? ??. ??? ? ?? ?? ??(??) ??
  ? ?????, ??-? ??? ??? ? ?? ?? ??(??)
  ?? ? ??? ? ??. ??? ???? ?? ????
  ??? ???? ??? ??? ? ?? ? ??? ??? ???. 

35
?? 4.9  -FeOOH??  Pb(II)? ?? ???

• ????? , , ? ??? ???? ????. ? ???,
  ??, ?? ??? ??? ???? ?? ?? ?? ??? ??? ?? ?????. ??
  7?? ???? ?? ??? ? ?? ????? ??? ??? ? ??. ???? ???
  ???? ??(capacitance model)? ??? pH? ?? ?? ????
  ???, ??????? ?? ??? ????? ??.
•    Components(????) , surface
• charge, ,
  '(four components)

36
?? 4.9  -FeOOH??  Pb(II)? ?? ???

• ? ?????? ????? ??? FeOOH? ???? ????.
• Surface charge
• ????? ??? ?? ????.

37
?? 4.9  -FeOOH??  Pb(II)? ?? ???

• ????? ?????, ??? ??? ????? ? ??? ??? ???? ?? ?? ?
  ? ??.
• (i)                    
• (ii)                    
• (iii)                   
• (iv)                    
• (v)                    
• (vi)                    
• (vii)                   

38
?? 4.9  -FeOOH??  Pb(II)? ?? ???
A B C D E F
1 FeOOH surfCharge Pb2 H log K
2 adsorbent charge 1 total free
3 FeOOH 1 0 0 0 0
4 FeOO- 1 -1 0 -1 -9
5 1 1 0 1 6.7
6 FeOOPb 1 1 1 -1 -0.52
7 (FeOO)2Pb 2 0 1 -2 -6.72
8 Pb2 0 0 1 0 0
9 H 0 0 0 1 0
10 1.00 0.00 1.00E-0.6 1.00E-0.7
11 constantCap model "constantCap", "diffuseLayer" or "tripleLayer" model "constantCap", "diffuseLayer" or "tripleLayer" model "constantCap", "diffuseLayer" or "tripleLayer" model "constantCap", "diffuseLayer" or "tripleLayer" model "constantCap", "diffuseLayer" or "tripleLayer"
12 14.7 specific surface area in m2 specific surface area in m2 specific surface area in m2 specific surface area in m2 specific surface area in m2
13 1.35E-0.4 no. of active surface sites in mol/g no. of active surface sites in mol/g no. of active surface sites in mol/g no. of active surface sites in mol/g no. of active surface sites in mol/g
14 0.1 conc. of adsorbent in g/l) conc. of adsorbent in g/l) conc. of adsorbent in g/l) conc. of adsorbent in g/l) conc. of adsorbent in g/l)
15 0.01 ionic strength in mol/l ionic strength in mol/l ionic strength in mol/l ionic strength in mol/l ionic strength in mol/l
16 2.9 capacitance of inner layer in F m-2 capacitance of inner layer in F m-2 capacitance of inner layer in F m-2 capacitance of inner layer in F m-2 capacitance of inner layer in F m-2

• ? ?? ??? ?? Westall? ??? MICROQL.? Beat Müller?
  ???? ????? MacµQL? ???? ??????? ??? ??? ?? ????.

39
?? 4.9  -FeOOH??  Pb(II)? ?? ???

• FeOOH? ????? 10?, 2?? 1.0? ???? ??? ?????. ?
  ??(??)? ??? 0.10.000135 mol/L??.
•  
• 7?? ??? ??? ?? 3??? ??? ??? ?? 4.1? ? ??? ?????.
• pH 6.3????, ?? ???? ???? ????.
• ??? ???? pH 6.?? ??? ?? ?? ??.
• pH? 7?? ? ?, ??? ?? ?? ???? ??????(????? ??
  ).
• ? ???? ?? ???? ??(mol/L)? ???? ??? ?? ?? ???
  ????.

40
?? 4.9  -FeOOH??  Pb(II)? ?? ???

• 2? ?? ??? ? ??? ?? ????
  ??, ?? pH??? ? ????, ?? pH???
  ??, , ? ????.

41
?? 4.10 H2O??? ??? ????? ???? ??

• ???? ??? ???, ????? nitrate? ??? ???. ????(??)
  ???? ??? ??, ??? ? ??? ?????(??????) ?? ? ????. ?
  ??? 5104 mol/L? ????. pH? ??? ?? ????, ????,
  nitrate? ??? ???. ?? ???? ????? ????.
• 5.52. ? ?? Müller.17? ????.
• ?? ? ?? ???? ????. ??? ???? ?? ??? ??? H2? O2?
  ??? ??? H2O ? ??????? ??? ? ??. ??? ??? ?????
  H2(g)? O2(g)? ???? ?? ??? ???? ?? ??.
• Species
• Components

42
?? 4.10 H2O??? ??? ????? ???? ??

• ???? ????, ??????? ? ???? ?? ?? ??.
• ?? pH ????, ??? ?????? ? ????? ??.
• ????? ??? ???? ???? ???, ?? ??, nitrate ???
  ??????.
• ???? nitrate? ???? ?? ????, ?? ????? ? ??
  ????? ? ??? ??????? ? ??????? ???? ? ?? ????.
• ??? ??? ??? ?? ?, ? ????? ??? ????? ????? ????.
• ?(half) ??? MINTEQ? MINEQL.21.22? ????  ??? ???
  ??.

43
?? 4.10 H2O??? ??? ????? ???? ??

• ?? ? ?????? ???? ????? ???? . ??? ? ????  ?????
  ???? ?? ?? ??? ??? ?? ??.

• ?????? ??? ??? ? ?? ?? ??? ??? ??.

44
?? 4.10 H2O??? ??? ????? ???? ??

• ?? ???? ?? 4.13? ??????.
• ?? pH ???? ? ????, ?? ????? ????? ?
  nitrate? ??? ???.
• pH 5?? pH? ????, ? ?????? ?? ?? ???
  ????. ??? ??? pH? ???? ?? nitrate???? ????.
• ? 5.52? ? ? ????,  ?????? ?
  ? ?? ?? ??(??? ??? pH 4?? M, pH 10?? ??
  ?? M ????? ??? pH 4? ? ? , pH10??
  ? ? M).