electrohimiya_toplivnyh_el_zac
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I–L+A–R |
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ER |
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C D |
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~E0 |
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. 4.14. < +
C * , , & - , ! & ! # ) * ! & ) # )^ . I )^ ! # -B ) # ! -. , ) ! A , -
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# ! & - |
* A . 0 < (EL) CD (ER) . 4.14 |
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B " # & # |
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! B # , EL œ ER. M (4.59) |
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(4.60) : |
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- 4 (I L A R) . |
(4.61) |
I # , R, A, L – - * . -. # ! & , & & & G " # & # - , & , . 4.13. %. F B , # B ! & & ) #-
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! – ! & ?+– ?2. ; . 4.13 , ! ) # B -# ! & -?+– ?2 (–?. #, ! B , - . B ) # * ) :
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* 2H2O + H M*3 |
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2O + H M.. |
(4.62) |
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+ M(e |
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+ M(e ) |
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" # ! & . 4.13 - , & & ! –!*. & B , V,,
EV E0 VF , |
(4.63) |
& ~EV ~E0 – ! & V # .#, V # & . # , ~E0* = Œ·~E0 ~EV* = Œ·~EV. -,
EV * ( E0 VF) |
(4.64) |
B * ! & B < CD, ) * ) B ! .
! ) , & &-( ( . 4.13). & ! –! *,# ) B :
iV 0 ekef W (Ef )(W E*)nH3O , |
(4.65) |
& kef – ! ! & A , * |
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& ! –! ; W(Ef) – -# ! # ) # ; W~E* –# & , ?3 + * #
& , ) & # ! , |
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3O |
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?3 +, B " # & # . ) # B kef W(Ef):
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4 m(kT)2 |
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kef |
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(4.66) |
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h3 |
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Wef |
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4 l |
22m(Ex |
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)1/ 2 3 |
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(4.67) |
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& m – ! ; Ex – # & ) # ; l – G-# & ) # ( B , & # ).
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% (W~E0*) B ) # # F # :
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*) exp |
E0 * |
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(4.68) |
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kT |
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(4.66) – (4.68) (4.65), :
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(kT)2 |
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4 l(2m) |
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)1/ 2 |
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iV 0 4 em |
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exp |
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(Ex |
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exp |
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nH |
3O . |
(4.69) |
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I & V, (4.69)~E0 ~EV. M (4.64) ,
EV * E0 * VF , |
(4.70) |
& , V (4.69) :
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exp( |
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(4.71) |
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V V |
V 0 |
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M # G V = Vr + •, & • – - B , Vr – ) , i = i0, (4.71) -:
i i0 exp( F ) . |
(4.72) |
RT |
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B (4.72) ) ! - |
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' . B |
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- * , - -B , & * ! # , -#G .
& * * #, # . !-! , ! , B G & ) / ) B & ) # -, ) # & - B .
4.5.0/(=/ 3 ' & '/ 00 (6 ( & +-(* ) =( (0'= 3@(0 3. : '@(0 ( 5 3 = &0 *& & ' ' [ 0 / ' & '/ 00 =( (0'= 3@(0 3. = & (0 3 =( (0 * 8' 35'
% & ) # # -) , # : - B (•) . < ! , , # -& ! –! , ! -, ) & , * & ! &-
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) & . B , ) & , # B !-. % ( - B (4.55)) B # , -B B # . 0(4.55), (4.56), B #, - # B
V Vr |
(4.73) |
* :
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(1 ) F |
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0 exp |
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exp |
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(4.74) |
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& i0 B (4.57).
) ) & * B ! ˆ ! Œ, -. 0! ) :
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(1 ) F |
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i i0 exp |
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exp |
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(4.75) |
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( B # # . - B ! # (4.75) B ) # - . ' ) B B #G 20 . % ! & (4.75) :
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(4.76) |
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' # , ) ) - , # B - . ; & ! * #, B -(R ) !-! ) :
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RT |
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(4.77) |
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di i0 F |
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M ! & B , # ) i0 -,) . * * -. - * ) , – ) . % ) , i0 œ 10–3 A/ 2 ( - / B ! ,
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B / ), ) )-i0 • 10–6 </ 2 ( , / ,).
& # B - G 20 . ! # ) -. !
B B |
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(4.78) |
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i i0 exp |
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, & # ž: |
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RT |
ln i0 |
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ln i . |
(4.79) |
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B * |
(4.80) |
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a b ln i , |
! ' . a b * -' . & ! *, - & # B .) ' R B :
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(4.81) |
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di i |
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. . ! ) #G .
4.6.# ( & =: =( (0'= 3@(0 ; + 30 ( 0' 8' *-*& = &0 *& & ' & = &(0/ ' '
4.6.1. '' |
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& ! –! . ! & #, , * B-* " # & # & , . - B ! ,! , ). , & & , - ) & #* ! ( , ), # &, )^ ! B " # & # , & -. I * , !- , & * # , , - * )^ ! . ?# B * ! &
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! . & , * - B # , * - -) ! . ? # , * #, - . I # * , * . % ! – ! & , B & .
; # B !-, # #* -
& )^ ! . ; |
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*, ! : |
(4.82) |
M z ze M. |
B B , ! #* & Mz + ! :
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M z$ |
M Z . |
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(4.83)
M « $» « » * )^ ! & - , & . & , -Q, & A :
Q D |
dC |
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(4.84) |
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dx |
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& D – ! , – . % & ) # & , ". . ? . ( B * & ) ! , -& . F B B , & - & . M ! , &• 5·10–2 . M # # ? –( ,(4.84) & B # * ) :
+ dC ( |
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C $ |
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Q D) |
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(4.85) |
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dx ' x 0 |
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& $ – )^ ! & , . -B ) # ! . # Q #/ 2,) z ! , -# & & :
i DzF |
C $ |
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(4.86) |
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, # ! D – 2/ .&) #G & , && - *. ! Mz+ , & * & , * * . 0 # i G :
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DzF |
C $ |
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(4.87) |
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M # (4.86) (4.87), B # # -* i , $ :
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i i |
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(4.88) |
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C ) # # * -* , ) # - , ) , . . - ) . ! B #- # ? V & !- –! . & i = 0, & Mz+ &B , )^ ! : = $. ' &
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V 0 |
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RT |
lnC |
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(4.89) |
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i 0 |
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zF |
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& Vr0 – ) ! . I -& ! , ! :
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V 0 |
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RT |
lnC |
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(4.90) |
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i i |
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zF |
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M i = 0, i = i V * ! -#* i B ! , . ( B & B •D, * - B :
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Vi i Vi o |
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RT |
ln |
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(4.91) |
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zF $ |
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(4.89) – (4.91) (4.88), B # #* -:
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F ( |
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i i )1 |
exp |
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& . |
(4.92) |
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& B žD ( #G 20 ), ! # B ) # # -•D :
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i D F |
(4.93) |
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& , B (4.93) , ! •D # .
' # * . 4.15.
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# , </ |
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. 4.15. < + +/I !!
@ # < - B *. C # – ! ) #, * -B *, ) B . CD – ! )-# & , -. D * # & ! ) # ) - , ! DE # # .
! ) #G , *! 10–5 2/. % - & ! # . & , * ! , , -& & , # -# 10–4 #/ . M # ! -
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(4.87), B # # * # ! -! !-10–4 </ 2. # , ! ,! #- * & ! , & ! # - . ! , - , # # i = DzFC/r, & r –. ## B ) # .
4.6.2.* ''
0
& #
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i i0 |
CO, |
exp |
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CR, |
exp |
(1 ) F |
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(4.94) |
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G, $ |
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RT |
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RT CR, $ |
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& • – B , BG, / G, $ R, / R, $. , -& & BG & B- , B # B ) # & .# ) #G B # )-) B , (4.94) :
i i0 |
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exp |
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(4.95) |
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RT . |
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G, $ |
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B G, / G, $ (4.88) (4.95), :
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(4.96) |
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i i0 )1 |
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&exp |
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i ' |
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RT |
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ii |
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ln |
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(4.97) |
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(4.96) B # : |
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exp F , |
(4.98) |
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RT |
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) # & - B . ' & B #:
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(4.99) |
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) G # - * * , * # , * , , .
4.6.3. # 0
B B !-& ! ) & !-* B * & ! & .& !, * # # .! !! . ) -( , ! , !- , ! ) - * & . ! !B ) # # ) & , ) # # ! . -) * # ) B -! ! , * -B , ! -! B . F , -B . ?- * ) * B ! -! . !-! B ) #. , ! ) * ! , ! -, B # -
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