Документ взят из кэша поисковой машины. Адрес оригинального документа : http://www.elch.chem.msu.ru/rus/seminars/kotov2.pdf Дата изменения: Sat Jun 28 16:55:37 2014 Дата индексирования: Sat Apr 9 23:54:47 2016 Кодировка:

..., . .. ()


,
, .

·A

n+

+B

m-

An+, B

m-







·An+ + Bm- An+, Bm- An+, Bm- An+, Bm· a1 > a2 > a3

a-?


-
Kip =4Na3/3000 exp(-z1z2e2/kTaD) exp(z1z2e2K/kTD(1+Ka)) Kip0 f Kip =4Na3/3000 exp(-z1z2e2/kTaD) exp(z1z2e2K/kTD(1+Ka)) «S» «H»
K = 8 Ne2/1000kTD

a Kip0 z1z2 = -1 K
0 ip

a=5е, T=298K, D=78,5 = 1,3 z1z2 = -12

K

0 ip

= 10

7



z1z2 = -1 D 15 40

z1z2 = -8 D 40 130


Kip =4Na3/3000 exp(-z1z2e2/kTaD/(1+Ka))
K = 8 Ne2/1000kTD
0 0 1 2 3 4 5 6 constant ( 100) = 7 8 9 10 11 12 13 14 15 756.219 554.262 779.574 864.564 896.628 908.727 913.293 915.016 915.666 915.912 916.004 916.039 916.052 916.057 916.059 916.06

NaI CH3OH (200C D=33.6) 0,05M 0,2M 0,5M 1,0 M D=31.9 D=27,3 D=18.8 D=11.7



· · · , red-ox , , ,

· · N- · - · - -


K (H.A.Benesi and J.H.Hildebrand) -
- - -

C0l/ = 1/K * 1/ + 1/
Co ­ (Co << ) l ­ ­ · + B = AB ( ABn 1/n )



· · . . «» . Kip0 , . ( ) ­

·


K
·

· · · ·

·

(P.Hemmes, J.N.Constanzo and F.Jordan ) Kip0 , 1:1 2/F (1+)/F : 2/F = (1+)/F *1/ + 1/Kip0 . F -. . 1 Kip0 : = (-/)/ = (1+ ). , . b y = ax + b Kip0 . 0.00000045
0.0000004 0.00000035 0.0000003 0.00000025 0.0000002 0.00000015 0.0000001 0.00000005 0 0 0.0002 0.0004 0.0006 0.0008 0.001 y = 0.0003x + 1E- 07 R2 = 0.9983

ip

0




Kip0
· , 2-4 22/F (2+)/F , = (4+ 8). · , Kip0 . .
1.739в10
-4

1.5в10

-4

y

1в10

-4

5в10

-5

0 0 0 0 0.01 x 0.02 0.021




lnKip0 = -z1z2e2/kTaD + ln(
7 6 ln Ko

4Na3/3000)
1 2 3

MPz+ + I- MPz+, IEV2+ + I- EV2+, I-

5 4 3 2 1 0 0 .0 15

|z1z2|/D 0.02 0.02 5 0.03 0.03 5 0 .0 4

- a = 4,23 е -z1z2 = 1,0 -z1z2 = 1,3 N...I 3,832 е a = const ?


-
0.0015 M MQI (H3)2CO 0.0005 M MQI CHCl
3

20400



max

2. 5

A

5000

max
4000 3000

`

20200

2

20000

1. 5
19800

1
19600

2000

0. 5
19400

1000

19200 0 0.2 0.4 0.6 0.8 1

0 0 0. 2 0. 4 0. 6 0. 8 1

0 0 0. 2 0. 4 0. 6 0. 8 1


­

1-MePzI (2,6-H)

4-MePy (3,5-H)

1H


MQ+,I-


-

-

a const CoA63+,l
-

a=4,7е f= 0.30

a=5,0е f=0.18 (ZINDO/S)



7000 6000 5000 4000 3000 2000 1000

, dm mol cm

3

-1

-1

1 2 3




N

D

0 0,0 0,2 0,4 0,6 0,8 1,0

1 ­ ­l4 (D = 2.3) 2 ­ ­ (D = 2.3) 3 ­ ­ (D = 2.3) D An+ + Bm- An+, Bm- An+, Bm- An+, Bm- An+, BmCCl - 6500 4 CHCl ­ 4000 ­ 2500 3 ­ 1500

= 18500

19200

19300

22300 m-1


i-PnPzI MQI
v MQI v -
2380 0 2360 0 2340 0 2320 0 2300 0 2280 0 2260 0 2240 0 2220 0 2200 0 2180 0 0 0.00 2 0.0 04 0.006 0.008 0.01 0.012

v i-PnPzI CHCl3

14 12 10
9.65 9.6 9.55 9.5 9.45 9.4 9.35 9.3 9.25 9.2 9.15 0 0.01 0.02 0.03 0.04 0.05 0.06 0. 07 0.08

/2(1- )

2

y = 180.56x - 0.0768 R2 = 0.9952

CHCl3 CH2Cl
2

8 6 4 2

K=180 (CHCl3) K = 16 (CH2Cl2)
y = 16.586x + 0.0704 R2 = 0. 99




0.08

0 0 -2 0.01 0.02 0.03 0.04 0. 05 0. 06 0. 07



4 3.5 3 2.5 2 1.5 1 0.5 0 -0.5 0 0.002 0.004 0.006 0.008 0.01 0.012





MPzI 0.5I2


Kip =4Na3/3000 exp(-z1z2e2/kTaD(1+Ka))

·

z1z2 >0

-

20 - , D

=6.8 е