Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://electr003.chem.msu.ru/rus/fnm/fnm12_2.pdf Äàòà èçìåíåíèÿ: Fri Sep 7 09:26:28 2012 Äàòà èíäåêñèðîâàíèÿ: Mon Oct 1 20:49:34 2012 Êîäèðîâêà:

(wasq@elch.chem.msu.ru)

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



- -

-





H2O

1.5

,

, - .

106 80

10

9

1012 ,

4.49

1015 1.78

10

18







1 D = 10
-18

. = 3.336*10

-30

·




- (, 1912 .)
2 0 - 1 M 4 = NA + 3 3kT + 2

· (, , E kT ). · .

-c

n -1 [3 ] = r 2 n +2
3 2

n2 =



. ., . .: - . ., 1960, 2



. (1935 .) exp(- t /):

() = +

( - )
1 +
22

- j

( - )
1 + 2
2

­ « ». . -- : 1 = 8 ­ ( = 78) 2 = 1 ­ ( = 6)

1 2 () = + + 1 + i 21 1 + i 2
. ., . .: - . ., 1960, 3

2














· · · - · · - ,

1.1-1.4

., 1887 .
· · · ·

.
: HA H+ + A
­ ­

: MOH M+ + OH

. (1888 .)

. (1923 .)
- (1879-1947) H+ +

2c c 2 = K= 1 - ( - )

?



( )
(1920 .)
2 z1 z2e0 B F =- + n +1 2 4 0 r r

2.1-2.2

dU F =- ; F (r0 ) = 0 dr
2 z1 z2e0 U = 4 0 r0

n > 1 ( )

1 1 - n

A=1.7476 (NaCl)
2 z1 z2 e0 G = N A A 4 0 r0

1 1 - n

G

NaCl

= 762 /

(1882 ­ 1970)



., Z. Phys. 1 (1920) 45
· ­ · ­ · W2 = 0

2.3

·

=
W=
H
NaCl s

4 0 ri
ze 8 0 ri
22 i0

zi e0

Gs = NA (W1+W3)
2 zi2 e0 -Gs = N A 8 0 ri 2 zi2 e0 -H s = N A 8 0 ri

zi e0


0

dq =

1 - 1 -

1 1 T d -2 dT

-
NaCl s

() = ­768 / H

() = ­1121 /



·
2 zi2 e0 -Gs = N A 8 0



1 ri

1 1 1 1 - 1 - +

( ) · , , ... · .
2 zi2 e0 -Gs = N A 8 0

1 1 -

1 ri + rs / s

2 (1 + s ) 4 = 16 s

· + -. · .



Gs(
) =- G - G + zWe - zF

2.4

Gs ( ) = Gs ( ) + zi F
0.1


(nh)

2.8


-

(Debye) 1884-1966

(HÝckel) 1896-1980



a =

G i = N i
0 s

--
N
j i

,T , p

as s = + RT ln 0 as
( ) =1 : · ; · ; · =1 .

ai i = + RT ln 0 ai
0 i

M + A- : as = a+ + a-

-

( )

a± = a+ + a-

-

: · , , , ; · .

Ba

( OH )

2

2 22 2 = a+ a- = + c+ - c- = 3 c+ c- ±

E = E0 +

RT RT RT ln a+ = E 0 + ln + c+ = E 0 + ln ± c+ zF zF zF



., . (1923 .)
· · , = const · · d 2 2 + 2 dr r · d =- - =(nzi e0 ) i dr 0 d 2 2 d + 2 ze0 dr r dr ni = ni 0 exp - i kT ze 1 · i0 e - r kT = A1 r · ­
2 e0 ( ni 0 zi 2 ) kT

3.2-3.4

2 e0 = (ni 0 zi2 ) =- 0 kT , 1/ -
2


a

0

A1 =

ze0 i 4

0

ze0 e a A1 = i 4 0 1 + a

ze0 i 4 0 a = -
2 zi2e0 U = - 8 0




-
1) ­

RT ln f

N i

2 zi2e0 = N AU = - N A 8 0



ln f lg f

N i

2 zi2e0 =- 8( 0 kT )

3/ 2

2 zi2e0 ( n z ) = - 8( 0 kT ) 2 i0 i N ±

3/ 2

1 2i103 N A J ; J = (ci zi2 ) 2

N i

=- zi2 h J ; lg f

=- | z+ z- | h J ; c 0.01 /

2)

lg f

N ±

=-

| z+ z- | h J |z z |h J ; c 0.1 / =- + - 1 + a 1 + aB J

3)

lg f

N ±

=-

| z+ z- | h J + CJ ; c 1 Â 2 / 1 + aB J


...
/ -

· ., .: | z+ z- | h J + CJ + DJ 2 1 + aB J · .: lg f
N ±

· ln f ± =- k 3 c (., 1918 .)
ln ± = - km1/ 3 + k2 m 1

=-

· · / · · · .. · · Computation





3.6



--



. (1926 .)
(i) (j)
2 1 zi z j e0 c j = c* exp - j kT 4 r 0

(j) r
2 1 zi z j e0 P (r ) = 4r 2c* exp - j kT 4 r 0

rmin =-

2 zi z j e0

8 0 kT

.. (1958 .)

K



2 3 zi z j e0 4000rmin N A = exp - 4 kTr (1 + Br 3 0 min mi

n

J)





-
1.0 0.8

F

-

AlF AlF
25

4

AlF6 AlF5 + F AlF52- AlF4- + F32-

x

0.6

0.4

0.2

Al2 F AlF
0 .1 0 .2 x (A lF 3)
36

39

0.0 0 .0

0 .3

0 .4

0 .5

5
620 602

5

556



4

4
615

3



547



3
555

620



2

2

1

1

0 400 600

,

-1

800

0 400 600

,

-1

800



M=Li v M3AlF6 AlF4 AlF5 AlF6
23max

M=Na v 55 110 110 v
max

M=K v 45 60 60 v
max

v 30 43 45
AlF4
-

556 625 565 525

550 620 555 520

540 618 551 515

18000 16000 14000

Intensity, counts

12000 10000 8000 6000 4000 2000 0 400 500 600 700

K
2-

AlF5

Li Na

Raman shift, cm

-1



RCl+AlCl
AlCl4
­

3 4 ­ ­ 7

1-Ethyl-3-methylimidazolium chloride (EMIC)

Al2Cl7

­

AlCl3 + Cl­ AlCl

2AlCl3 + Cl­ Al2Cl
AlCl3

AlCl4 Cl­

­

Al2Cl7

­

AlCl3