Sotnikov_Vatolin_vce
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(4.5) |
d x |
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! : Na+, Ca2+, Mg2+, SiO44- . ! j-
70
" :
ij = − j dψ , i = i j , (4.6)
d x |
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j − ",
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j- ( t j ): |
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t j = |
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(4.7) |
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71
( ! ,
CaO, SiO2, MgO, Al2O3, FeO, 0,1 - 1 /
! , ! "
(106 - 107 / ). & E
40 - 200 ) / ! .
! ! ,
!
.
# ( 10 .%) !
(FeO, Fe2O3) (MnO, V2O3, Cr2O3) " !,
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. . |
" Me2+ |
- O2- - Me3+, |
, !
" . (, !
! FeO - Fe2O3 102 / ,
! .
4.4.
( ! !,
" " (ψ )
. % ! " ! "
(ϕ ):
ϕ =ψ −ψ - .
72
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! ϕ |
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! ! " -
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! (ε i ) |
ϕ i |
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εi = ϕi − ϕ . . |
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ε i ! |
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i - |
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! ! ",
H2 =2H+ + 2e
aH+ = 1, pH2 = 1 ( " ).
& " ε i !
" , ,
( , ) :
ε i =ε i0 + RT ln |
∏ aiνi (Ox) |
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(4.9) |
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zF |
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* z − ", " ; ν i −
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. & (4.9)
( Ox ) , ! −
( Red ) . , ,
73
", .%%
!,
ci , / 3. # "
. (, , "
2SO24- =S2O82- + 2e
"
ε ε 0 + RT ln |
cS2O82- |
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2F |
cSO2 |
42- |
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Me= Mez+ + ze , |
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(4.10) |
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! ε i0 ( . 4.1). ) ,
, ! ε i0 . 4.2.
,, " , !
!. & ,
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( min) " !. + min |
! |
(ε ) (ε ): |
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min = ε -ε , |
(4.11) |
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", ! ! . &
(4.9), ! ε i0 !
. 4.1 4.2. # " !,
, ! ,
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( 4.1 |
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% |
0 |
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ε i , & |
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Li, Li+ |
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Li=Li+ + e |
+3,045 |
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K, K+ |
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K = K+ + e |
+2,925 |
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Ca ,Ca2+ |
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Ca = Ca2+ + 2e |
+2,87 |
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Na, Na+ |
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Na = Na+ +e |
+2,713 |
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Mg, Mg2+ |
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Mg = Mg2+ + 2e |
+2,38 |
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Al, Al3+ |
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Al = Al3+ + 3e |
+1,66 |
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Zn, Zn2+ |
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Zn = Zn2+ + 2e |
+0,763 |
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Fe, Fe2+ |
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Fe = Fe2+ + 2e |
+0,44 |
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Cd, Cd2+ |
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Cd = Cd2+ +2e |
+0,402 |
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Co, Co2+ |
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Co = Co2+ + 2e |
+0,27 |
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Ni, Ni2+ |
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Ni = Ni2+ + 2e |
+0,23 |
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Sn, Sn2+ |
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Sn = Sn2+ + 2e |
+0,14 |
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Pb, Pb2+ |
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Pb = Pb2+ + 2e |
+0,126 |
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H2(Pt), H+ |
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H2 = 2H+ +2e |
± 0,000 |
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Cu, Cu2+ |
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Cu = Cu2+ + 2e |
-0,337 |
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Cu, Cu+ |
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Cu = Cu+ + e |
-0,52 |
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Ag , Ag+ |
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Ag = Ag+ + e |
-0,799 |
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Au, Au3+ |
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Au = Au3+ + 3e |
-1,42 |
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75
( 4.2
"
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% |
0 |
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ε i , & |
H+, O2, H2O (Pt) |
2H2O = 4H+ + O2 +4e |
+1,229 |
Cr2+, Cr3+ (Pt) |
Cr2+ = Cr3+ + e |
+0,41 |
V2+, V3+ (Pt) |
V2+ = V3+ + e |
+0,255 |
H2(Pt), H+ |
H2 = 2H+ +2e |
± 0,000 |
OH-, O2 ( ) (Pt) |
2OH- = 1/2O2 + H2O + 2e |
-0,401 |
I-, I2 ( ) (Pt) |
I- = 1/2I2 + e |
-0,536 |
Br-, Br2 ( ) (Pt) |
Br- = 1/2Br2 + e |
-1,066 |
Cl-, Cl2 ( ) (Pt) |
Cl- = 1/2Cl2 + e |
-1,358 |
F-, F2 ( ) (Pt) |
F- = 1/2F2 + e |
-2,87 |
(4.9)
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4.5.
) , " ,
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76
CO , Al2O3 |
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(4.1) G < 0. 2 |
, G(4.1) = 0, |
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G |
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G |
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E = − |
G |
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(4.12) |
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zF |
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F − / ( F = eN A ). |
# ! |
zF |
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(4.12) ! " 3 !
( G , ) / Al). # " 1,5
CO , ! 3 eN A , . . 3F
", Al
! ". ,
z .
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4 !
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∂ E |
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∂ T |
P |
z F |
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∂ E |
= − |
V |
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(4.13) |
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∂ P T |
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z F |
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, ') "
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77
“ E − T ”. & E
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4 V < 0.
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G (4.12) |
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S (4.13) " |
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H = |
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(4.14) |
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4.6.
% ",
i - " (4.10). & ,
(4.10) ,
" ! ε i . #
" ! !
ε i ε i .
# ε i >ε i
(4.10) ( ) ,
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Mez+ , |
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+, |
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ε i <ε i |
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(4.10) |
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( ) |
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Mez+ |
! " |
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, .
78
) " "
(i ), ! , ! ! ε i -ε i ,
! " ( ε i ):
ε i = ε i -ε i .
& ! i ε
, , . & ! ,
4,
! . 2 !
" ! !,
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,! |
! |
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( ε A > 0), |
– |
( |
ε < 0). |
# " |
" ! ') ( )
:
E = ε − ε = (ε + |
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ε ) − (ε + ε ) = |
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= Emin + εA + |
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εK |
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= Emin + E . |
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' ( E ) ! " !
" ". (
" ! ! Emin ≈ 1,06 &,
E 0,8 &,
" " ~70%.
& ! !.
#, , Zn2+
, . . 4.1,
" " ! !,
, ~(-0,76 &). # "
( H+ ): 79