Sotnikov_Vatolin_vce
.pdf2H+ +2e=H2
"
,
"
. # "
.
4.7.
" ,
, ! ! ,
! " ! ( S )
(τ ). +, (4.10)
v = − |
1 d nMe |
= |
1 |
d nMe2+ |
. |
(4.15) |
|
s dτ |
|
s |
dτ |
|
|
, ! ! /, (v ) !
" (i ), !
-",
i = zFv . |
(4.16) |
&
" !
, "
. ! "
! i
" ε . * i |
ε ! |
|
". & |
" |
! |
" |
. |
80
) -
! !
!. "
Me= Mez+ + ze
!, , , . .
*, , ! ! Mez+ . !
! ! !
!. ( !
(!), "
|
z F |
ε |
|
|
|
R T |
|
(4.17) |
|
i =i e |
|
|
− 1 . |
|
|
|
|
|
|
* i − ! Mez+ ,
! ! ! "
!
i = zF |
D c, |
(4.18) |
|
δ |
|
D − " ! , c − 4
, δ − ! .
( " (!)
"
. 4.2. , ! ,
. . ! -" . #
" !
. # (
) !
81
i . 0 !! !,
! " , |
! |
!
" !.
& !
" ! !, "
:
|
|
β z F |
ε |
− |
α z F |
ε |
|
|
|
|
R T |
R T |
|
(4.19) |
|||
i =i0 |
|
− e |
|
|||||
e |
|
|
|
|
. |
|||
|
|
|
|
|
|
|
|
|
%. 4.2. &
!
82
* i0 − , " / 2
! ;
αβ − " !,
" "
" α + β = 1. &
. 4.3. 0 ! !
“ lni − ε ” !
i0 , α β .
, !-! !, ,
! , " (4.19)
! " . &
! ! ! , ,
, .
, !.
%. 4.3. & ,
! !
83
) ! |
|
! "
. ' !
, "
! ( , , , !, ).
"
, !, , , , , .
' !
, ! ,
, , , , .
&" ! (" !)
" -
(&) , .
% & – (4.1) ! ,
! " . &
3C +Al2O3 . - =2Al +3CO , |
(4.20) |
!,
( ), .
! , . # "
! (4.20) !
CO ( ),
" . +
84
! ! " !.
. 4.4.
, " !
". % ! . 1
(4.1) , . . ! (4.20), ! " ! . "
! . ',
, Al3+
Al ( ). , "
" ( ),
CO .
32 C + 32 O2-= 23 CO + 3e
Al3+ + 3e = Al
|
e |
|
+ |
|
|
|
|
||
|
1 |
|
|
|
3 |
2 |
|||
|
|
4 e -
%. 4.4. " ! ! :
1 - " ( );
2 - ! CO;
3- (Na+, F-, Al3+, O2-);
4- ( )
85
) "
, , ,
", ') ( ),
":
E > [− G(4.1) /(3F)]. |
(4.21) |
, , , !
" "
" ! .
& " ! ! "
|
( NaF, AlF6 ), |
|
|
10 .% Al2O3 . ( |
" ! |
1220-1235 , |
|
! 1 . & " |
G(4.1) ≈ 305 ) / |
Al , |
, (4.21) ,
1,06 &. % , ! ,
" ,
! (100150 0), ! ( ,
", , ), ! !
( -", -"). # "
4,0-4,5 &.
&" !
" !,
" . & !
,
,
" . +,
" !
86
2CuSO4 +2H2O=2Cu +2H2SO4 +O2 |
(4.22) |
# " |
|
2Cu2+ +4e=2Cu , |
( ) |
|
|
2H2O=4H+ +O2 + 4e |
( ) |
&.
4.8.2.!
&
"
" . ) ! !
" , ! ε ,
! , . ' !, , ! ,
! ε , (4.10)
( ) , ε i >ε i , –
( ), ε i <ε i . ' !
! !
. ) ε
! ( ) " !,
. "
! (4.9), ε i0 ! 4.1 4.2. # " !, ,
! ,
(4.9)
87
. (,
" (4.22)
- ( ): ε 0 =+0,337 &; - ( ): ε 0 =+1,229 &.
2min ≈ ε 0 -ε 0 =1,229 - 0,337 ≈ 0,9 &.
&( . 4.1)
(" ) . #
,
" . ,
, "
(") .
! ,
!
ε ε .
2H+/H2
& , !
" ! – " "
( ). (
! , !
( , )
.
' !. 5,
! ! ,
". & !
,
88
. .
" ( ). (
! ! .
. # " !
". -
" , ! "
! . 6
,
! .
# " !
". (, , ,
, 88-89% ,
(1,2-2,2%), (4,5-6,5%), !
(2,5-2,6%), (0,4-0,5%) . # "
99,99%.
"
! ! ! . (,
Me=Mez+ + ze
2H+ + 2e = H2
', " ,
, ! . #
! " !
(!5.4).
89