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(wasq@elch.chem.msu.ru)

http://www.elch.chem.msu.ru/rus/prgfnm.htm




4.1












()

4.2

j = - k ci grad

j = - Di grad ci
i

I



d ln fi Di = k RT 1 + d ln ci






j =

zi z ciui X =- i ciui grad | zi | | zi | Di = ui RT | zi | F d ln fi 1 + d ln ci

: j + j = 0
i =i + zi F = const



RT | zi | F - Di0 = ui0



l R= s =

4.3

1 l = [/] sR
=



= [Ci 2 / ] z+ + c z- - c
:

i = z+ N A j+ + z- N A j- = - z+ Fu+ c+ grad - | z- | Fu- c- grad i =- z+ + cF grad (u+ + u- )
= + +
-

i = - grad = - z+ + c grad
-

+ = Fu

+

- = Fu

()
c 0 0 = 0 + +
0 -

()

1 : lg = const - lg c 2 0 : = - const c

(.)





U = E1 + E2 + iR E1, E2 0 j 0




ti = ui | zi | ci i | z |c = =ii uk (| zk | ck k )
( )

4.4-4.5
t- =
- + +
t+ + t- = 1
-

i

t+ =
( )

+ + +

-

( H ) t-Q 2O · -n n ( ) = H2O F RT c2 ln · = (2t- - 1) F c1 cFV · t+ = Q

i0 = ti0

0

--

: zie0X 2 P | zi | e0 N A 0 RT kT kT v= i = i0 = i0 Di0 = Di0 = 2 6r 6ri | zi | F 2 | zi | e0 N A 6ri 0X/F - ze F i0 = const = 0 6ri

-




Mathias Hecht, W. Ronald Fawcett, J. Phys. Chem. 1995, 99, 1311-1316




2 0 3 0

4.6

r =
3 1/ 2

1

| zi | e N A | zi | e N A 2 N A i10 = = 6 6 0 kT

c =| zi | b


/ () X - X

X X i = ( i0 - | zi | b c ) 1 - i0 - | zi | b c - i0 X X

X (2 - 2 )e (2 - 2 )e 2 N A i10 = = X 24 0 kT 24 0 kT 0 kT
2 0 3 0 3

1/ 2

c =b

p

c

(. )


--
= 0 - (2b + bp 0 ) c


0.001

(1903-1976)

0

-

= - bp
0

0

c c - 2b 1 + aB c

+ 2b c = + b c 1 - b c

-

= 0 -

(2b + bp 0 ) c 1 + aB c

0.1



X = 20-40 / ui X > 1



0

-
> 2

5.5 CaCl2 SrCl2 BaCl2
S. M. Gadzhiev, O. M. Shabanov, A. O.Magomedova, S. A. Dzhamalova, Russian Journal of Electrochemistry, 39(2003) 1083­1088.



< 35 M+·A-·M
+

M M+·A
-

+

.. (1857-1942)



-

M + aNH3 = [M(NH3)a-x]+ + e­(NH3)
x