. 2002. 573. . .9(32)

162

541.135 - -

. -

© 2002 . . , . . , . . , . . ,

. . -

ann eaoee - - (TBA+ Pic ), -

. TBA+ Pic

- 1.14 10 5 4.01 10 3 298.15 -

.

( ) [1-4]. -

,

[5-7], [8], - [9],

[10], [11]. - , ,

, [12]. , (

) - ( ) - ( ).

- ML+A

[12-14]. , - , . -

[3,6,15-17]. , -

, ,

. . [5], - . -

- ,

.

,

,

,

[1-5,8,13-15,17,18]. . [19] - ,

( ).

(HPic) . -

: 360 , 460 . - [1,20] , -

. -

. Pic solv. H+solv. , , HPic. -

Pic

Na+ ( ,

, - ) , . ,

[21]. , Pic

+HNR3, ,

[15,17]. [22], -

- - .

-

163

, , . -

, , ,

. , .

aennioeaoee

, - (

- ).

- - , ( - 4H9)4NPic, TBAPic.

, . , .

. , . . . . . , -

TBA+ + Pic

TBA+Pic , AK , (I)

-, « »

(15-12), ( -) [1,2,4,5]. 2 -

, 30, [2].

, [1]. - ( , =36) -

( , LiClO4) [23]. TBAPic. -

, AK , ( 5) : - . -

. ,

5 - -

. .

. - - , - [22]. - ,

, 423.8-424.2 [24]. - .

c - 5058 ( 0.2% ) =298

1000 .

c = 2 10 4 6 10 3 .1 -

0.05 . - .

. - (0.5 1)%.

, -. 27 c 1 10 5 4 10 3 . -

.1 .1.

. -

(KA) ( 0) -

( LOPT, : . . , . . ). [25,26].

, .

1 1 = 1 / .

. . , . . , . . , . . , . . -

164

[27,28], - [29].

1.

- - - , 298.15

c 104, M ,

2 1

c 104, M ,

2 1

c 104, M ,

2 1

0.1137 1.934 3.713 0.5289 13.88 0.3462

0.305 1.394 5.003 0.4821 15.10 0.3271 0.592 1.120 5.185 0.4638 18.56 0.3240

1.005 0.9099 6.742 0.4330 21.88 0.3030

1.025 0.8787 6.881 0.4184 24.33 0.3085 1.594 0.7543 8.991 0.3943 29.15 0.2904

2.192 0.6609 9.145 0.3788 31.64 0.2999

2.656 0.6070 11.51 0.3662 35.96 0.2874 3.489 0.5526 12.09 0.3486 40.08 0.2975

, - .

(I) - . -

: =5.105 [30], =0.688 10 3

[18].

- ( 0),

( ) (R). - .2

( 1.1). - -

( ), -

( .1). - -

, R - -

( 0.5 3 ) : 0 .

.2 ( 1.2.1 1.2.3). , -

R, -

, -.

- - -. TBAPic -

-. .3, .2 -

lgKA .

- - , , -

. , . - [45] ,

lgKA

1/ . - - : lgKA = 0.457 + 46/

( .2 ). . -

0.00 0.01 0.02 0.03 0.04 0.05 0.06

0

1

2

3

41

2

3

c

.1 . - Bu 4NPic - . 1

; 2

- 1 .1 ; 3

1 .3

- - .

-

165

[46] TBAPic

- ( 303 )

lgKA = 0.46 + 44.46/ . , -

lgKA 1/

=178 (N- ) =6.2 ( ) [4,47]. , -

- lgKA 1/ , , , .

2.

( - - - , 298.15 )

1 0 lg KA R

1.1 4.12±0.013 5.17±0.05 2.49±0.13 1.79 10 2

1.2.1 8.83±0.39 6.08±0.04 0.50 5.44 10 2

1.2.2 6.62±0.23 5.78±0.03 1.20 4.19 10 2

1.2.3 3.79±0.17 4.99±0.07 3.0 3.89 10 2

1.3 77.0 8.46±0.07 2.49 1.36 10 1

1.4 3.66±0.21 4.92±0.12 2.9±0.6 1.57 10 2

2 0 lg KA 0

lg K

2.1 7.7±3.5 5.9±0.5 52±18 1.54±0.34 6.42 10 2

2.2 17±61 6.8±3.1 3.5±1.4 4.9±2.5 4.15 10 2

2.3 60±270 7.9±3.9 30±800 3±13 9.29 10 2

2.4 4.4±0.9 5.2±0.4 23.8±3.3 2.0 5.15 10 2

2.5 3.45±0.29 4.68±0.25 16±7 2.2±03 3.37 10 2

, - . - [45], -

lgKA = 8.55. 0

, - TBAPic

.

, ,

. , - , -

. - , 0 .

, , 10 5-10 3 .

20% ,

.

, [48],

.

0 [49]. 7

, 0 (

), ( ),

.

. . , . . , . . , . . , . . -

166

, .

: lgKA 10, 12, 17

[48,50], 0

103, 104 [49]. : LiClO4 ( =7.4)

: 0 = 9.5, lg KA= 4.83 [51]

0 = 117.55, lg KA=7.4 [52], .

5

1

0

1

5

2

0

0

2

4

6

8

100/

lg KA

1

2

3

4

5

)

5

1

0

1

5

2

0

2

5

3

0

0

2

4

6

8

1

0

100/

lg KA )

1

2

3

.2 . lg

KA Bu 4NPic . ) : 1

298 ; 2

303 [46]; 3

-

[45]; 4

, - , 298 ; 5

1 .3 . ) , 298 : 1

-; 2

- - [49]; 3

, .

3.

- - ( ); 298

1030,

0, 2/

lg KA

36.7 0.612

1.7 31

36.02 0.3448 139.4

32

36.02 0.3448 141.28 1.11 33

34.69 1.839 27.83 0.87 34

34.69 1.839 27.86 0.41 32

31.7 0.5445 86.1 0.99 35

31.7 0.5445 86.14 0.85 36

20.56 0.303 152.34 1.23 32

20.47 0.304 152.4 1.65 37

12.92 0.542

3.3 38

12.01 0.8824 57.7 2.89 39 1,2-

10.23 0.735 57.4 3.65 40 1,2-

10.23 0.735 59.45 3.43 41 1,1-

10 0.466 96.9 4.34 42 1,2-

8.78 0.795 51.3 4.57 42 1,3-

9.93 1.271 37.3 4.77 43 1,3- (297.95 K) 10.06 1.3262 34.85 4.67 44

5.63 0.758 60.95 7.69 44 1,2- (297.95 K) 5.04 1.031 44.82 8.60 44

- - .

-

167

- . ,

, - ( 0=77). -

lgKA 8.46,

- . - - -

( .2, 1.3, .2 ). ,

-- [49] -

- . -

.4 .

2 , 3. ,

,

.

- , 7

. , -

, - .

4.

[49] - -

-

,

% . C6H4Cl2

R=0.6

[49]

0 2.64 0.46 2.56 0.02 47

lg KA 6.86 0.20 6.83 0.01 9.45 24.83 4.152

R 0.5 0.4

0 24.8 1.3 21.1 1.7 30

lg KA 6.38 0.04 6.25 0.07 6.56 50.03 6.041

R 0.05 0.5

0 23.9 1.0 25.0 0.5 25

lg KA 5.08 0.04 5.13 0.02 5.14 74.82 7.946

R 0.87 0.25

0 36.91 0.11 37.00 0.07 36.8

lg KA 4.743 0.004 4.745 0.002 4.72 100 9.93

R 0.79 0.21

, ( -), :

TBA+Pic + TBA+ (TBA2Pic)+, 1 (II) TBA+Pic + Pic (TBAPic2) , 2 (III)

[48], « » , - , 1.19 10 14 ( )3. - 298

0

5

1

0

1

5

2

0

2

5

3

0

3

5

0

.

4

0

.

8

1

.

2

1

.

6

100/

lg 0

.3. lg

0

- Bu 4NPic

. , .2 .

. . , . . , . . , . . , . . -

168

4.2 10 5 . , , . -

, ( .2, 1.4).

, , [53]. ( ) -

. ( ) -

. , - .

, - . -

. .2 ( 2.1 2.5) . R -

. , - . , -

( 0 ), ,

( , 1.1 2.4, 1.3 2.3).

.

, - ( .2), .

, (II) (III) , ,

, . , [54] - ,

. ,

. ,

.

, , -

. -, ,

. ,

0 , .

.

, , -

. ,

: 0 , 0 . -

.

. 0

, , .

0

( . 2).

1

0 0 exp( )A B

[4, .165-170],

. , 0

c, - ,

,

- - .

-

169

0 . -

0. - , , 0

( . 3). , - , ,

.

[14], -

lgKA (3.15), ( .3). , -

.

1. . . . :

- , 1959. 958 . 2. . ., . .

. .: , 1968. 352 . 3. . . .: , 1979. 712 . 4. . . . .:

, 1990. 240 . 5. . . , -

. .: , 1972. 535 .

6. . ., . . -. : , 1979. 152 .

7. . . . 1984. .29. 5. .50-60. 8. ., . . .: , 1987. 485 . 9. . . . : . .:

, 1982. 260 . .75-88; . ., . ., . ., . . .

. 1994. .13. 6. .74-82. 10. . . -

. : , 1994. 232 .

11. . . . . 1986. .55. 9. .1409-1433; . ., - . . -

. .: , 1983. 224 . 12. . . ,

. .: , 1971. 670 . C.2048-2053; - . . . . .: , 1975. 424 .

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376. 30. . . . . .: -

. 1972. 411 .

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. ... . . . ., 1977. 23 .

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16 2002 .

Kharkov University Bulletin. 2002. 573. Chemical Series. Issue 9(32). I.N.Palval, E.M.Nikiforova, A.V.Lebed, O.N.Kalugin, N.O.Mchedlov-Petrossyan. On the problem of dis-sociation of tetra-n-butylammonium picrate in organic solvents. Conductometry in n-butylacetate.

The data on equilibrium constants of tetra-n-butylammonium association with picrate, available in lit-erature, as well as the limiting molar conductivities and Walden Pisarzhevsky products of TBA+ Pic

in organic solvents of different nature are discussed. The experimental data on TBA+ Pic

conductivity in n-butylacetate at 298.15 K, obtained in the present study within the concentration range of the elec-trolyte from 1.14 10 5 to 4.01 10 3 , were treated by using various models of equilibrium in solu-tions.