5.9. ｧ9 [89 5" [6]. 縺 ｨ ｨ ｨ , ﾁ ｨ (7 閨6),

Transcription

1 , 86 ﾀ 縺8 縺 ﾀ5 縺7 959 ｨ ｨ ｧ ｨ ｨ ｨ (957 67, , ) 799 9ｨ ｨ ｨ. ﾀ ｨ , ｨ , 縺 ｨ PACS numbers: 5.5.+v, 66..Ed, 8..Fi (5).. ｧ995 9ｨ 59799: (5)... ﾀ ｨ ｨ ｨ ｨ ｨ ｨ 5979 (6) ｨ ｨ 595 (66) (67) ｧ995 9ｨ ( ｧ6) ｨ , 5ｨ ﾁ , ﾁ ｨ ｨ 5ｨ , ｨ ｨ, ｧ , 5 78, 縺9979 9, (7) (7) [email protected] * ﾁ ｨ ﾁ , ｨ ｨ ｨ , ﾁ ｨ ｨ ｨ, ｨ 縺 ｨ 9 58ｨ ｨ ｨ ｨ ｨ ﾁ ( ), 8759 ( ) (> ) 655 [ 5 ] (5 ) , ｨ A 6ｦ B ﾀ ｨ []. 縺5 ｨ , 95 ｧ , ｨ [, ]. ﾀ , ｨ ｨ , ｨ , [5] ｨ 5979, ﾁ "- #.9. ｧ9

2 5.9. ｧ9 [89 5" [6]. 縺 ｨ ｨ ｨ , ﾁ ｨ (7 閨6), 縺89755 [7] 閨 ﾁ [8], 閨 ｨ ｨ , : , ｨ 5975, ｨ ｨ 55 55ｨ ｨ 9889ｨ, ｨ , ﾁ999 7 閨 ｨ ｨ , 5ｨ 595 ｨ , 996 5, ﾀ ｨ ｨ ﾀ5ｨ (55955, ), ｨ ｨ. 89, ｨ , , ｨ [, 7, 8] ｨ , ｨ , ｨ , ｨ ｨ ｨ ｧ995 9ｨ 59799: ｨ ( ) , ｨ 59 ﾁ , (755855, , ) [9]. 5 ｨ C H 8 O , ｨ 5979 (ｨ ｨ ), 8 75, , ﾁ , ｨ ( , ｨ , ﾁ ) 57 ﾁ , ﾁ [] ｨ , 65ｨ ｨ ｨ , ｨ ﾀ ｨ ﾀ , 95 ｨ ﾁ : ) , , ) , , ) , , ｨ ｨ ｨ, ﾀ ｨ (798. ) ｨ T, n ｨ s [, ]: m ｷ pm e k B T = e ns ; 5 m e, e ｨ 5975; k B ｨ ( !), ｨ , , ﾁ (68779) 8659 ﾁ , ｨ 59759, R A [, ]. 5 ln m, ,,,,,5,6,7,8,9, p=p s ﾀ ｨ He ( p s , m 8 (5 8) []: T ｷ ;, T ｷ ;9, T ｷ ;65. ｭ6 9

3 7. 7, ] 9 縺 罍ﾀ5 縺5 縺6 縺676 9 縺 ﾀ76 罍縺58 縺597 5 ｧ [5] m ｷ e 9pZ 6ｦ ; ｭ6 9 6pZR nr ｭpm a k B T 6 9 = 5 m a , Z , 95 ﾁ577 (), () ｨ ｨ ｨ (8. [6, 7] []) (), (), ｨ ﾁ ﾁ577 (), () ｨ , ｨ ( , 9 5, ), 65ｨ ﾀ ｨ : ,7 [8] [9], , 95 ｨ ｨ ｨ O 7 (8. [], 8. 8) ｨ (755, ), [] 9 ｨ [] , ｨ , ﾀ795 ｨ , [], ｨ ﾀ ｨ ｨ [] (9. ).. ﾀ ｨ , m ｷ ;7 8 (5 8) 7, : m ｷ ｷ 7 8 (5 8) 7. 縺 : , ｨ : m ｷ m exp 7 E A ; ｭ6 9 k B T 5 ｨ E A ｨ ｨ E A ｷ (67957, 595 [] [, ]) 5 E A ｷ ; ｨ m (5 8) E, ｨ , ｨ 9, 67957, ｨ [5] E A ｷ , [, ] (), ｨ E A ｷ x E A 6ｦ x E A ; 5 x i i E Ai ｨ ｨ i , 95 ｨ ｨ ｨ ｨ ｭ ;D ｨ []. 6. ﾀ ｨ ｨ ｨ : ｨ [6 5 8] ｨ ｨ , l [9 5, ], CH I, O 9 C H 5 Br [], X 6ｦ e 7 7! r X 7 ; 5 X ｨ , e 7 ｨ 5975, r , ﾀ m, ｨ E A, E ｧ95898 m, 8 (5 8) 7 E A, 7 T, m, 8 (5 8) 7 E, , ｨ ﾀ ﾀ59 - 閨 He He Ne Ar Kr Xe H, D ,,7,7,,6,6,5,979,95, ,5, 8 7 6,8,,,75,9 67,,5,5,6,6,6,6 75 8,,,, ,,7 7, 7,,9,5,5 7, 7,78 7,6 7,

4 5.9. ｧ9 [ ｨ X ﾁ r ｷ em e : e ｨ ｨ [9 5 ] , n 77 ( ) t e ' ｭrn ' 7 8. ﾀ5ｨ ｨ ｨ ｨ , ｨ ﾁ ｨ ｨ t e ' ｭrn t ; 5 t ( ｨ 5975, ) ｨ T ｷ m, 8 (5 8) 7 r, ﾁ59 CCl CH I C H 5Br - 閨 閨 ,, , 閨58 - ﾀ 閨58 - ﾀ59,, ,78, 5,, ,78, 5,,6 5,68, 7,9,78,,, 7, 5,,78, 7 7,,,7,,,77,,6,,8,5,5 5,85,8,8 8,6,,7,6 6,, ｨ ｨ , , ｨ ｨ , , 95 ｨ "959589" 799 9ｨ , ｨ M 6ｦ X > M X > M 6ｦz X 7z 7!k 7 a M 6ｦz 6ｦ X 7z : ｭ X 55 ｨ , , M X [9], M 6ｦz X 7z [, ], M 6ｦz, X 7z , z , e i e i ｷ ez, 5 e 縺9599, ｨ [5], [6] [] , ｨ ｨ , ｨ [ 5 6] ( [, ]). ﾀ , ﾁ ｨ ｨ ｨ 9 s [ 5 8, 7, 5] 99 l [6]; ｨ ｨ , s=c, 5 c ｨ ｨ 9 l [] 99 L [6]. ﾀ ｨ ｨ ｨ [8], 9855 [9], , 縺 [, ], m n [] p 7 7 m i ｷ m i 7 b i n ; ｭ56 9 zi e b i ｷ 6pZ 6ｦ z z e s ez i q p pek B Tr i 6ｦ 7 7 e ; ｭ66 9 q ek B T q ｷ zz z 6ｦ z m 6ｦ m m z 6ｦ m z ; r i ｷ 6pR i Z ; 5 z i ｭi ｷ ; 6 9, Z , m i i , ﾁ () 65 ｨ , R i ｨ ﾁ ﾁ i , ﾁ ｨ ﾁ ｨ ﾁ ﾁ59 [, 8]. ﾀ i ﾁ R i, ｨ m i ｷ zie 6pR i Z : ｭ (5) ｨ ｨ , ﾁ : p 7 7 b i n 5 : ｭ86 9 m i

5 7. 7, ] 9 縺 罍ﾀ5 縺5 縺6 縺676 9 縺 ﾀ76 罍縺58 縺597 5 ｧ , ﾁ R i A, Z ｷ ; ﾀ, e ｷ ;e, T ｷ s 7 縺 s ｷ em i n 955 m i ; 75 8 (5 8) 7 p 7 7, b i n =mi ｨ (8) , 799 9ｨ ｨ - 5ｨ ｨ , ｨ [, ] [7] , ｨ ﾁ ﾁ ｨ a [, 7]: a ｷ p ｭD 6ｦ D 6 9R ; ｭ D, D 5ｨ ﾁ ﾁ ﾁ ﾁ899, R [] a ｷ p ｭD 6ｦ D 6 9`B 7 exp ｭ 7`B=R 6 9 : ｭ `B ｷ r B, 5 r B , [, ] r B ｷ ee 8pek B T : ｭ6 9 5 ﾁ575 () e, e , e 85ｨ 99 9ｨ , k B , T 85ｨ , 95 ﾁ57 () (9) 679 r B! k ｨ [9, 5] ｭ rb `B k ｷ ｭD 6ｦ D 6 9`B exp r dr 7 7 R r ｭr B 7 R 6 9 : ｭ ｭR 5 r B ｭ = exp s ds ｷ d exp 6ｦ O ｭd 6 9 ; d 5 ; d s d ｭ k ｷ ｭD 6ｦ D 6 9 r B R exp 7 ; d ｷ R : ｭ6 9 d r B 縺95595 a =k 87ｨ ｨ 9 K ｷ K acc [, 5] () 9 (), ｭd ｷ R =r B () 8 ﾁ []. ﾀ ﾁ , , K acc, ｨ ﾁ575 6 (8., 67957, [5] ﾁ577 (8.) 9 (8.5)). 659, 95 ﾁ577 () 9 () , ｨ 縺857 [6] , 5 58, E a ｷ p ｭD 6ｦ D 6 9`B ｷ em 6ｦ e m e ; ｭ m i 5ｨ ﾁ ﾁ , ｨ ﾁ ﾁ ﾁ ﾁ k B T=e i ｷ D i =m i. 957 (6) () 679 r B =R ｨ [5, 5] 縺857 5 k ｷ k F ｭ p6 9 ; F ｭ p6 9 ｷ I ｭp6 9 p ; p ｷ ee ｭm 6ｦ m 6 9E = : k B T pe ｭm e 6ｦ m e 6 9 ｭ ｨ F ｭ p6 9 87ｨ 9 ﾁ9575 縺857, I ｭs6 9, s ｷ p, 59 ﾁ99759 ﾁ , I ｭs6 9 ｷ X n ｷ ｭs=6 9 6ｦn n! ｭn 6ｦ 6 9! : 999 F ｭ p , ｨ , ｭe ' e (T ｷ ) ｭE ｷ p ｷ, ｭE ｷ p ｷ F ｭ p6 9 ｷ ｭpp 6 9 7= exp p : 縺98ｨ 95, ｨ ｨ ( [5]) K ｷ a k ｷ pr B d exp d ; d ｷ R r B : ｭ ﾁ ﾁ [6] R =`B A 6ｦ B 7 6ｦ A 6ｦ 7! a 6ｦ 7 A 6ｦ B 7 A 6ｦ ; k 6ｦ a 7 7 k 7 A 6ｦ B 7 7 6ｦ B 7! B 7 A 6ｦ B 7 : ｭ86 9

6 56.9. ｧ9 [89 ﾀ , A 6ｦ B 7 A 6ｦ 9 B 7 A 6ｦ B 7, 87ｨ [] K 759 (8), [], ｨ , "75895" A 6ｦ B 7 8 ｨ ﾁ ﾁ a B 7 (95 A 6ｦ, B 7 ) ﾁ n i ｷ n exp 7 U ; k B T 5 n B 7 ( ); U ｨ , ｨ : U ｷ e pe r 7 r ; r ｷ ｭa 6ｦ r 6ｦ ar cos c6 9 = ; 5 r ｭr A 6ｦ (8987 B 7 ) B 7, c , 85599ｨ B 7. ﾀ79 c ｷ ｨ B 7 A 6ｦ B [,, 6] ｨ 9 85ｨ : K ｷ a6ｦ k 6ｦ ｷ a 7 k 7 ｷ p ｭ rd a exp 7 U r dr ; k B T ｭ r d , ｨ ﾁ c ｷ : d dr r exp 7 U ｷ : k B T ｭ (9) , ｭc ｷ 6 9, B A 6ｦ B ｨ , ﾁ a 5 r d ｨ 9 K, 795ｨ (9). 655, (9) " " , ｨ ｨ , , 9 95ｨ 縺595, , 5 R 5 r B , 7989 ﾁ exp ｭr B =r6 9, 59 95, , r R. 5 ｨ (9) : K ｷ ;6pr B d exp d ; d R r B : ｭ (5) 9 () 8559, 95 K ｷ ; exp 7 5 : K d 6585 ｨ ｨ R 5 r B , , ｨ ｨ , [9, 5]: A 6ｦ B 7 A 6ｦ 6ｦ B 7 7! a 7 A 6ｦ B 7 ; B 7 A 6ｦ B 7 6ｦ A 6ｦ 7! a 6ｦ A 6ｦ B 7 ; A 6ｦ B 7 A 6ｦ 6ｦ B 7 A 6ｦ B 7 7! a A 6ｦ B 7 : ｭ ｨ ｨ 599, ｨ ｨ , (8), () 95ｨ ｨ ｨ , 5ｨ ﾁ ﾁ9-959 ｨ s ｷ e X z i m i n i ; ｭ6 9 i , n i , i ｷ ｨ 9 95 A 6ｦ, B 7, A 6ｦ B 7 A 6ｦ 9 B 7 A 6ｦ B ｨ ｨ ｨ (8), (8) 9 (): k N 7 a n n 6ｦ k 6ｦ n 7 a 6ｦ n N 7 a 6ｦ n n ｷ ; k N 7 a n n 6ｦ k 7 n 7 a 7 n N 7 a 7 n n ｷ ; a 6ｦ n N 7 k 6ｦ n 7 a 7 n n 7 a n n ｷ ; a 7 n N 7 k 7 n 7 a 7 n n 7 a n n ｷ ; 5 N A 6ｦ B ｨ ｨ K ｷ a6ｦ k 6ｦ ｷ a 7 k 7 ｭ6 9 ｭ56 9 ｭ66 9 ｭ76 9 ; n ｷ n ; n ｷ n : ｭ K (8) ｨ N ｷ N 7 n 7 n ; ｭ N A 6ｦ B 7, ｨ (), (5) 65859ｨ (5), (6) (8. 975). 7, ｭK N , 95 n ｷ n ｷ n, 98 (), (5) : K n 6ｦ n 7 N ｷ ; K ｷ a k ;

7 7. 7, ] 9 縺 罍ﾀ5 縺5 縺6 縺676 9 縺 ﾀ76 罍縺58 縺597 5 ｧ K N n ｷ N, K N 5, K N ｨ p n ｷ N =K. 55, 85 K N, K N 95ｨ ｨ : x ｷ n N 5 ; x ｷ n N 5 : ｭ () 5 (7) (), (6), (9) () 95ｨ x ｷ K N 6ｦ a6ｦ 6ｦ a 7 a K N 6ｦ a 7= ｭK N 6 9 ; ｭ6 9 a x ｷ K N x ; K ｷ a : ｭ6 9 k (), (), 98 () ｨ ｨ ﾁ ﾁ9959 ｨ : s ｷ e m 6ｦ m 6ｦ ｭm 6ｦ m 6 9K N x N : ｭ6 9 縺9599, [] ｨ ｨ l ｷ s C N = 6ｦ C N 7= : N (), () l 59 N. 縺 , 95 ﾁ57 () K N ( !), (8. 975) K N < ｨ ｨ 縺857 ｨ ﾁ ｨ ﾁ ﾁ595 9 ｨ ﾁ ﾁ ｨ ( 6795, ｨ 縺 ) 557- ﾁ99 [] 縺857 [6] ｨ ｨ 76 8 ( ｨ ) ｨ , ｨ 59 ｨ , ﾁ5797ｨ ﾁ ｨ [7] ｨ ｨ 縺8588, ｨ ｨ , V (798. ). ﾀ5ｨ ｨ [ 5, 5 5 7, 5, 6, 7, ] ｨ 縺857 [6] [6] (8. 75 閨59 [5, 55], , ) , I, SbCl , , SF [5, 6] (798. 5, 6) ｨ ｨ ﾀ , ﾀ ｨ ( , 75585, 5585, 57585, 69799, 595, ) 5ｨ ｨ , 65ｨ ( V ｨ : , , , ｨ , ｨ 59 9 ﾁ , s, 縺 7 8 7,5,,5,,5,,5 5 E, ｨ ﾁ ﾁ9959 ｨ % , 5 % ｨ , % [5]

8 58.9. ｧ9 [89 7, 6,5 J, 9 8 6, 7 9 s, 縺 ,5 5, 6 5,5,,5 5 E, ｨ ﾁ ﾁ9959 ｨ % , 8 % ｨ , % [55] E, : ﾁ55 ( ), SF 6, ppm 9795, O 縺 [6, 56]) ｨ 縺 ｨ [7, 58] ｨ ﾁ ﾁ [59, 6, 6] 6589, ｨ , , 6795, , , ｨ ｨ : (E ) (E ), ｨ ｨ , , 679 ｨ ｨ ｨ 5975 ( ｨ [6]) ｨ [6] , ｨ 59755, , , ｨ [65] ｨ ( 縺 []). ﾀ 縺 ﾁ ﾁ ｨ ｨ , ( ｨ ) ｨ : 99ｨ [ ], ｨ J, E, : 5 ppm I, 6 ppm SbCl 5, 7 ppm I, 8 ppm I. 659 (E ), ｨ ｨ 縺875989, 95 ｨ ｨ ｨ 9997ｨ , ｨ 5975 (ｨ [66]) 5899ｨ 9, ｨ ｨ ｨ ｨ ( ｨ 955) ｨ 5975 ﾁ9895 [67, 68] 縺 , ｨ ｨ (978 ﾁ

9 7. 7, ] 9 縺 罍ﾀ5 縺5 縺6 縺676 9 縺 ﾀ76 罍縺58 縺597 5 ｧ ), 8 75 ｨ 閨 [7, 8, 7, 9, ] , ｨ ｨ ﾀ5ｨ ｨ 縺 7 8 7, ｨ ｨ ( , ) ﾀ ｨ ｨ 縺 ﾀ , 5595 ｨ ( I, O 9 7.) ｨ () x ｷ n=n 75 [9, 5], 5 n ( ) 955, N ｨ ( ) ｨ 989 ｨ ｨ 5975, ｨ E [57, 6, 69, 7]. 7, [69, 7] ﾁ E < , 679 E ｷ , 679 E , 679 ｨ ｨ [6] , ﾁ (55855, ) , , ｨ ｨ : "8579", , 89, , ｨ ｨ 5-95 ｨ 99, , ｨ , 9577ｨ ｨ [, 7, 8] , 99ｨ , 89, ｨ , 7595 [69] , ﾁ ｨ ｨ ｨ , ｨ ｨ ﾁ ﾁ59 5 ｨ , ｨ [7, 58] ｨ 閨 ｨ [7, 58] ﾁ ｨ ｨ ( 閨75-58) [57, 6, 65, 7] ｨ ｨ ( ) 5585 [7], ｨ [6, 6, 69] ｨ ｨ ｨ [7], ｨ ﾁ ﾁ , ｨ 5975, ｨ , 578ｨ [7, 75] ｨ ｨ 閨 [76] , ｨ [9, 5, 76] ｨ ｨ 55 [5, 77], 9 ｨ ｨ , ｨ ﾀ5ｨ ﾁ [] , ﾁ (995). 55 ｨ ｨ ﾁ , 陦縺 ﾁ ﾁ ﾁ98977 (996 ﾀ 縺55) ｨ ｨ , CaCl , ｨ ｨ d ｷ ; ﾁ ﾁ ｨ ｨ ﾁ ｨ [, 5] y , ｨ 9 ｨ ﾁ ﾁ ｨ ﾁ95 95, 95 ｨ , , ( ) ｨ ｨ : ) c ｨ ｨ, ｨ ｨ ｨ 9 ｨ ｨ 989 ( ｨ ｨ []); ) ｨ ; ) (8. 975). ﾀ ｨ 989,

10 6.9. ｧ9 [89 j, 7 8 6,5,,5, t, y ﾁ : E ｷ 7; , E ｷ ; , E ｷ 8; , E ｷ ; , 5 E ｷ 5; j, E, ﾁ ｨ , ﾁ ｨ 975ｨ I ﾁ ; 8 8 7, v ｷ ;78 8, N k ｷ 7;5 6. 縺 ｨ 縺 i k i , U i ｷ x i U, J i ｷ y i J (J ｷ 77, U ｷ ; x i, y i ) s i c i s i ｷ s y i x i ; s ｷ Jd SU ｷ ;6 7 Om 7 sm 7 ; c i ｷ kin k ; v i 5 S 6558 ｨ 5975, v i ｷ V 6ｦ iv (V ｷ 6; ﾁ ) s i ｷ ｭs i =s 6 9, a i ｷ ｭl i =l6 9, l i ｷ s i =c i, l ｷ s V =N k, 5 p b i ｷ s i c =c i, 5 c ｷ ; : (7), (8), K, K ﾁ579ｨ ｨ ｨ ｨ ﾀ5755 ｨ ﾁ99 [] [5] , , , , ｨ 865k i......,5 5 5 s i a i ,,,,6,,95,9 b i ,,, , 65 ｨ s i =N i, 5 N i , 578ｨ I M > M 6ｦ I 7 : ｭ N i ｷ K c i, 5 K (), 5957ｨ ﾀ ｨ ｨ , (), (8), , : ) ｭN i K < 6 9: s i ｷ e ｭm 6ｦ m 6 9N i ; ｭ56 9 ) ｭN i K, N i K 5 6 9: r N i s i ｷ e ｭm 6ｦ m 6 9 ; ｭ66 9 K ) ｭN i K 6 9, (), () (), () 8559, N i K, 5 ｨ s i =N i ｷ const. 縺5 ｨ ｨ 8999ｨ , N i K > ( ) (5), (6) , , (5): s i ｷ ;6l ｷ e ｭm c 6ｦ m 6 9K ; ｭ76 9 i (6): s i p c ｷ ;s r K p ｷ e ｭm i c 6ｦ m 6 9 : ｭ86 9 K

11 7. 7, ] 9 縺 罍ﾀ5 縺5 縺6 縺676 9 縺 ﾀ76 罍縺58 縺597 5 ｧ ﾀ m 6ｦ m , 7 8 (5 8) 7 ｧ ｨ ｨ ｨ 閨58, 9, 9, 5,5 6 m 6ｦ m 7 m 7 m 7 m 6ｦ m 7 8,7 5,8 6,8 8,5 5,5 5 [78] [79] [8] [8] [8] [8] [8] [85] [85] [85] [86] 7,5,5 - 閨58 6,6, [8] [87], [9] - 縺9 5,,9 [8] 7 [89] [9] -5,8 [8] -65,7,5 [8] [89], [9] 585,5 [88] 5 5 [96] CCl,6,9 [96] 6958, [95] [87] [88] [89] [9] [9] [9] 5,5, [9] [9] [9] [95] ﾁ ; , , , , 9, , ｨ [9]. ﾀ5859 ﾁ , 657, 75ｨ 59, ﾁ ﾁ ｨ [7] [7] ﾁ ｨ sd 5 ; ｭ96 9 ｭm 6ｦ m 6 9eE 5 E ｷ U=d , s [95, 96], 7595 [7] ｨ y ( ). ﾀ , ﾁ (5 8) 7. 5 ｨ ｨ , ｨ ﾁ , ｨ , , , , o ｨ ﾀ5ｨ [], V 95 V R 66 9 R 縺8 ﾀ : V, V , , 縺 , ﾀ ﾁ , R 66 9, R j, t t, a ﾁ E ｷ ; ﾀ s ｷ 7 7 縺

12 6.9. ｧ9 [ ｨ 5975 ﾁ ｨ H H 5I CH (CH ) OH 595 (CH ) CO C 6H 5NO 778 ﾁ r, 8 7 e=e r i, A r B, A d ｷ R =r B ｷ r i =r B E, p, E ｷ p, E ｷ K, 8 K, 8,88,,7 6,5,,8 8 ;6 76 ;7 7,8 5,,5 5, 7,6,5,5 ; 75 7; 79,8 6,8, 6,7,9,,65 6,5,79 8,7,8, 6,7,6 6,,,9, 8,,8 7,,6,6,98, 6,,,8 8 6; ｨ ｨ ﾀ ｨ 9 75 ｨ 95 ｨ K, K K , ｨ (9. ). ﾀ ﾁ57-7 (7) ﾁ (8. 9. ), Z ｷ ; ﾀ ｨ ﾁ ﾁ R 85ｨ : m ｷ m ｷ m ｷ ; R 7 sm ｭB c6 9 7 : ｭ R ﾀ58999 () (7), K ｷ 7;6 76 R : ｭ (8) K 5758 K ｨ 5 c : K ｷ ; : ｭ6 9 K c K, K , , ｨ (5 ﾁ ) (5 ﾁ e) K, K 58- ｨ , ｨ , ｨ ｨ ( ) ﾁ ( ) ｨ ｨ ﾁ ﾁ99597 ｨ ｨ R, m, K, K, K, (7), (8) , : K N ｷ K K c ｷ ; <, K N ｷ ｷ K K c ｷ 6;8 > (), () 98 ﾁ577 (5) ｨ ﾁ ﾁ ; 75 R 5 exp 5 R ｷ : ｨ ｨ ﾁ ﾁ R ｷ A, ﾁ577 (), (), (5) 9 (6) 65859ｨ : j, 7 m ｷ ;5 76 sm ｭB c6 9 7 ; K ｷ 8;95 75 ; K ｷ 6; 7 sm ; K ｷ 6;9 75 sm : ｭ ｨ ｨ 55979ｨ 5, , 679 % K N ;, 95 N ; , N ｷ K c i, 655 c i ; , E, 縺

13 7. 7, ] 9 縺 罍ﾀ5 縺5 縺6 縺676 9 縺 ﾀ76 罍縺58 縺597 5 ｧ ｨ [7] 7595 [98] ｨ ｨ , , ｨ 95, 8799 ｨ 縺95-99, ｨ [], 5, 85759ｨ, [6] ｨ : ) 99997ｨ (599) 7597ｨ , ﾁ ﾁ , ) (95, 9658) (959 67, ) , 95 ﾁ- 9ｨ f n ｷ W n 7 ｭr ;... ; r n f ｭr6 9, 5 W n n , f ｭr , n 7 899, r ( ). 69 ﾁ99 f ｭr ｭD n 7 6ｦ D 6 9 D f 6ｦ div f ｭm 6ｦ m n hf n 7; i6ｦ 6ｦ m n 7 hf n 7 i 7 m hf i ｷ : ｭ D, m, F ｭD n 7 ; m n 7 ; F n ｨ ﾁ ﾁ ﾁ ﾁ899, , (5658), F n 7; ｨ ｨ 閨 ﾁ99 f ｨ 9 9 r ｷ R : f ｷ ; r! : f! ; ｭ ｭ f dv ｷ ; r! : f! ; ｭ66 9 V 5 V 5898, 597ｨ , ｨ k a 86987ｨ ｭ k ｷ i n ds ; ｭ76 9 S ｭ a ｷ 7 i n ds : S ｭ i ｷ 7 ｭD n 7 6ｦ D 6 9 Hf 6ｦ f ｭm 6ｦ m n 7 6 9hF n 7; i6ｦ 6ｦ m n 7 hf i 7 m hf i , n ﾁ575 S, ｨ ﾀ , 859 [98] k ｷ p ｭD 6ｦ D 6 9 l B A F ｭ p6 9 ; ｭ l B ｷ r B, F ｭ p6 9 ﾁ99 縺857 (8. ()) A ｭ y ｭ S ｭy6 9 A 7 ｷ plb exp d s 6ｦ p ｭ 7 cos y6 9 I ｭs; cos y6 9s ds sin y dy ; ｭ56 9 ｭ I ｭs; cos y6 9 ｷ I ｭm 7 7 p t 6 9 exp 7 t dt ; m ｷ p cos y s ; S ｭy6 9 ｷ p 6ｦ : 6ｦ p cos y y cos y ｷ 7 p ; d ｷ d=, 5 d ｷ R =r B (5), I 59 ﾁ99759 ﾁ (5) d 5, p : A 7 ｷ plb d exp : ｭ56 9 d ﾀ (5) (9) 縺857 (7) d 5, p, 5 p d 5 9 ﾁ99 縺 縺857 ｭ exp p ｭx6 9 exp px F ｭ p6 9! p p ｦ exp ｭ 7=d 6 9 p pp p pp d p 7 7 = S 7 p dx : x ｭ [98] 6585, 縺 d! , , 5 d 5, ﾁ577 (5), (5) 99ｨ 縺 , 98 (5) 95, , ｨ 縺 , ｨ [99] p p ｷ E=E, E ｷ e= ｭ6perB E 5 E, , 679 E 5 E

14 6.9. ｧ9 [ 縺 , T ｷ. 98 ｨ , ｭe=e 縺 縺9599, 95 ｨ ｨ (ｨ , 6755, ﾁ ) 縺 a p d : a ｷ a 6ｦ exp 7 d F ｭ p6 9 ; ｭ a (), F ｭ p6 9 ﾁ957 縺 ｨ , ｨ 7589; d! [98], ｨ ｨ ｨ q ｷ p r d =r B, 5 r d , s ed r d ｷ : ｭ56 9 pek B T 8588 d ﾀ ｨ 9, q <, 65ｨ ﾀ [98], hf ; i ｷ 7 ed L ｭx6 9 pe r r ; x ｷ de i k B T ; r ｷ r r ; ｭ L ｭx6 9 ｷ coth x 7 x 7 ﾁ99 755, E i ｷ ｷ e=per ﾀ (55) () hf i ｷ hf i ｷ ﾁ ﾁ , ｨ ｨ 9 5ｨ ﾁ ﾁ : a ｷ p ｭD 6ｦ D 6 9 r d Q ; Q ｷ ｭ =d x dx sinh x ; d ｷ R 6ｦ R r d : ｭ R ik i-5 9 k ( ｨ , 8557) ｨ ﾀ , 65ｨ 95 ｨ ｨ 875ｨ ｨ ｨ : k ｷ D 6ｦ D rb Q ; ｭ576 9 ｭ dd Q ｷ exp P ｭs6 9 H ｭs6 9 ds ; ｭ586 9 d ｭ ｭ exp P ｭs6 9 H ｭs6 9 ｷ s ds ; P ｭs6 9 ｷ f ｭs6 9 ds ; f ｭs6 9 ｷ C ｭs6 9 W ｭs; x6 9 ｷ exp C ｭs6 9 ｷ s ｭ 7 W ｭs; x6 9 s 7 d x R ｭs; x6 9 dx ; s R ｭs; x6 9 ; R ｭs; x6 9 ｷ ｭs 6ｦ d 7 s d x6 9 = ; W ｭs; x6 9 dx ; d ｷ R r B ; d D ｷ rd r B ; d ｷ R 6ｦ R r d : 9957 (58) 679 d 5 d D : Q ｷ r p ｭd 6ｦ d6 9 d exp : ｭ596 9 e ｭd 6ｦ d6 9d = d 8588 e ｷ ; ｨ , d ｷ R =r B : k ｷ D 6ｦ D r B d 77= exp K ｷ a k ｷ ;7pr B d exp 7 ; d ｷ R ; d r B ｭ66 9 : d ｭ66 9 縺 , , , ﾁ577 (), A 6ｦ B 7 A 6ｦ B , : A 6ｦ B 7 A 6ｦ 6ｦ B 7 7! a 7 B 7 A 6ｦ B 7 6ｦ A 6ｦ 7! a 6ｦ A 6ｦ B 7 A 6ｦ B 7 ; A 6ｦ B 7 A 6ｦ B 7 ; ｭ66 9 A 6ｦ B 7 6ｦ A 6ｦ B 7 7! a A 6ｦ B 7 A 6ｦ B 7 : ｭ (6) , 65ｨ 95 5ｨ ﾁ ﾁ a 6ｦ 9 a ﾁ () ﾁ575 (5). 5ｨ ﾁ ﾁ a 7599 (6)

15 7. 7, ] 9 縺 罍ﾀ5 縺5 縺6 縺676 9 縺 ﾀ76 罍縺58 縺597 5 ｧ a () ｨ ｨ : a ｷ p ｭD 6ｦ D 6 9 r dd ; ｭ k ｷ a ｷ ;5 ｭD 6ｦ D 6 9 rdd 7 K d 76 exp 7 d : ｭ696 9 r dd ｷ = d d : pek B T ｭ ﾁ ｨ r dd ﾁ575 (6) (77,7), r dd , d ｭd ｨ ( (6) d ｷ d ). 縺9599, 95 ﾁ57 (6) ｨ r dd ｷ ｷ ｭmm m =pk B T 6 9 =, 5 m 85ｨ (67957, ), m, m : A 6ｦ B 7 A 6ｦ B 7 7! k 7 A 6ｦ B 7 A 6ｦ B 7 7! k 6ｦ A 6ｦ B 7 A 6ｦ 6ｦ B 7 ; B 7 A 6ｦ B 7 6ｦ A 6ｦ ; ｭ666 9 A 6ｦ B 7 A 6ｦ B 7 7! k A 6ｦ B 7 6ｦ A 6ｦ B 7 : ｭ ｨ ｨ ｨ, [] 9 58 ｨ [] , ｨ , ﾁ ｨ 縺595, ｨ 9 5 ﾁ , p r ｷ ｭ rB, 5 r B () (66), (67) ｨ 8 9, 89, (6), (67) ﾁ575 (9): K ｷ p ｭ rdd R exp 7 U r B T r dr ; U ｷ 7 d d pe r ; 5 R , , U 9 ｨ ﾀ79 R 5 r dd K p r dd d 6 exp d ; d ｷ R : ｭ686 9 r dd a =k ｷ K, , 9. 7, (67957, ﾁ ) A 6ｦ ｭAB6 9 m, 5 AB ( ), m , ｨ 閨 ﾁ ｨ [7, 58] ｨ 759 A 6ｦ 6ｦ AB 7! a 7 A 6ｦ ｭAB6 9 ; k A 6ｦ ｭAB6 9 6ｦ AB 7! a 7 A 6ｦ ｭAB6 9 ; ｭ76 9 k A 6ｦ ｭAB6 9 m 7 6ｦ AB 7! am 7 A 6ｦ ｭAB6 9 m : km : a i, k i i , ｨ ｨ ｨ 8 ﾁ A 6ｦ i ｨ (56), (6) 955 a n ｷ ;7p ｭD n 7 6ｦ D 6 9 r d ; ｭ76 9 k n ｷ ｭD n 7 6ｦ D 6 9 rb 7 d 77= exp 7 ; d ｷ R ; ｭ76 9 d r B 5 R , p ｨ A 6ｦ , r d ｷ R r B ｨ ﾁ ﾁ , R (7) 8559, (7) K, ﾁ575 (6). 縺 N ｨ AB, n 55979ｨ A 6ｦ, n i 55979ｨ A 6ｦ ｭAB6 9 i n i ｨ ｨ : dn dt ｷ a nn 7 k n ; dn dt ｷ a n N 7 k n ; dn m dt ｷ a m n m 7 N 7 k m n m : ｭ76 9

16 66.9. ｧ9 [89 98 (7) 8559, i t i ｷ r d ｷ d 7= exp : ｭ76 9 k i D 6ｦ D i 7 d ﾀ R R 7 A, r B 6 A, D t i (t i 7 8), 65ｨ 95 ｨ (7) 955 n ｷ ｭK N6 9n ; n i ｷ ｭK N6 9 n i 7 ｷ ｭK N6 9 i n ; i 5 : ｭ76 9 縺98ｨ 95, K N < , i 965-5, 7ｨ , 679 K N > ｨ ｨ 5- ｨ 9597ｨ , , , 76ｨ ｨ 5989 ｨ , ｨ ｨ ｨ ﾁ ｨ ｨ ﾁ ｨ ｨ ｨ ( ﾁ , ) , ｨ 9 785ｨ ｨ ｨ , ﾀ , , ｨ ｨ ｨ 59 ﾁ ( K ), ( K ).. 縺 ｨ ｨ ｨ ( ) , ｨ k ｷ k exp ｭ 7E A =k B T 6 9, 5 E A ｨ ｨ , 95 ｨ ｨ ｨ ( ). 縺595, ｨ ｨ ﾁ ﾁ ｨ ﾁ ﾁ ( ) (679-57, []) ｨ , ﾁ ｨ [], []. 縺 , 95 ﾁ ｨ ﾁ ﾁ ｨ : 5899, ｨ ﾁ ﾁ ﾁ ﾁ899 9 ｨ ﾁ ﾁ K, K K ｨ N, ｨ K N 5, ｨ , 679 K N , 679 K N > , 縺 , ﾀ ｨ 9, ( 縺 ｨ ｨ ﾁ ﾁ a A 6ｦ B 7 > A 6ｦ B 7 8p ｭD 6ｦ D 6 9 r B D 6ｦ D rb k d 7 exp 7 d r B ｷ e 8pek B T d ｷ R r B A 6ｦ B 7 6ｦ A 6ｦ > A 6ｦ B 7 A 6ｦ ;7p ｭD 6ｦ D 6 9 r d D 6ｦ D rb A 6ｦ B 7 6ｦ A 6ｦ B 7 > A 6ｦ B 7 A 6ｦ B 7 p ｭD 6ｦ D 6 9 r dd ;5 ｭD 6ｦ D 6 9 rdd A 6ｦ ｭAB6 9 n 7 6ｦ AB > A 6ｦ ｭAB6 9 n ;7p ｭD n 7 6ｦ D 6 9 r d D n 7 6ｦ D rb d 77= exp 7 d d 76 exp 7 d d 77= exp 7 d p r d ｷ d rb R d ｷ d = r dd ｷ ｷ ｭR pek B T r B6 9 = d ｷ R r dd p r d ｷ d rb R d ｷ r B r B

17 7. 7, ] 9 縺 罍ﾀ5 縺5 縺6 縺676 9 縺 ﾀ76 罍縺58 縺597 5 ｧ ｨ ), ｨ ｨ ﾁ957 縺 ﾀ ｨ ｨ ｨ ｨ 5975, 99 ﾁ ｨ , ( ), ｨ ｨ , , , 55, ｨ ｨ ｨ ｨ ｨ ｨ 59795: (.: , 99) ｨ 59795: (.: , 958) ｨ (.: 75799, 97). Thomson J J, Thomson G P Conduction of Electricity through Gases Vol. rd ed. (Cambridge: Univ. Press, 98) ｧ995 9ｨ (.-.: 縺79 7, 96) 6. Felici N J Direct Current A 7 (97) 7. 縺 ｨ (.:, 979) 8. 55, 閨758 9 ﾀ, (995: 999, 977) ﾀ (.: 999, 968). Davis H T, Brown R G Adv. Chem. Phys. Non-simple Liq. 9 (975). Levine J, Sanders T M (Jr) Phys. Rev. Lett (96). Levine J L, Sanders T M (Jr) Phys. Rev. 5 8 (967). Ferrell R A Phys. Rev (957). Kuper C G Phys. Rev. 7 (96) 5. Tyndall A M The Mobility of Positive Ions in Gases (Cambridge: The Univ. Press, 98) 6. Cohen M H, Lekner J Phys. Rev (967) 7. Lekner J Phys. Rev. 58 (967) 8. Harrison H R, Springett B E Chem. Phys. Lett. 8 (97) 9. Jahnke J A, Silver M Chem. Phys. Lett. 9 (97). Springett B E, Jortner J, Cohen M H J. Chem. Phys. 8 7 (968). Miller L S, Howe S, Spear W E Phys. Rev (968). Bakale G, Schmidt W F Z. Naturforsch. 8 5 (97). Minday R M, Schmidt L D, Davis H T J. Phys. Chem. 76 (97). Davis H T, Schmidt W F, Brown R G, in Electrons in Fluids: the Nature of Metal-Ammonia Solutions (Eds J Jortner, N R Kestner) (Berlin: Springer, 97) p Bakale G, Schmidt W F Chem. Phys. Lett. 6 (97) 6. Holroyd R A, Allen M J. Chem. Phys. 5 5 (97) 7. Holroyd R A, Dictrich B F, Schwartz H A J. Phys. Chem (97) 8. Holroyd R A J. Chem. Phys (97) 9. Beck G, Thomas J K Chem. Phys. Lett. 95 (97). Beck G, Thomas J K J. Chem. Phys (97). Beck G, Thomas J K J. Chem. Phys (97). Allen A O, Holroyd R A J. Phys. Chem (97) (.: 999, 966). 69ｨ 88 9, 縺 (.: 97, 978) 5. Gallagher T J Simple Dielectric Liquids. Mobility, Conduction, and Breakdown (Oxford: Clarendon Press, 975) 6. Onsager L J. Chem. Phys. 599 (9) 7. Smoluchowski M Phys. Z (96) 8. Blumentrits A Ann. Phys. (Leipzig) 95 (99) 9. Falkenhagen H Phys. Z. 5 (9). Wien M Phys. Z (98). Bjerrum N K. Dan. Vidensk. Selsk. Mat.-Fys. Medd. 7 9 (96). Onsager L, Fuoss R M J. Chem. Phys (9). Krauss C, Fuoss R J. Am. Chem. Soc. 55 (9). D5by5 5 Trans. Am. Electrochem. Soc (9) 5. Copenhafer D T, Krauss C J. Am. Chem. Soc (95) 6. Fuoss R J. Am. Chem. Soc (958) , 縺 ｨ 5979 (.: 98-5 閨8, 989) 8. 9 ﾁ9 7, ﾀ99589 ﾀ (.:, 979) 9. Zhakin A I Electrohydrodynamics: Basic Concepts, Problems and Applications (Kursk: Technical Univ. Press, 996) 5. ｧ (78: 98-5 閨78, 999) 5. Zhakin A I, in Electrohydrodynamics (CISM Courses and Lectures, No. 8, Ed. A Castellanos) (Wien: Springer, 998) p Langevin P Ann. Chim. Phys. 8 (9) ﾁ (.:, 975) 5. Gemant A Phys. Z (98) 55. Gemant A Elektrophysik der Isolierstoffe (Berlin: J. Springer, 9) 56. Durant P, Fournie P, in Proc. Lancaster Conf., Lancaster, UK, 97, p. 57. Felici N J Direct Current B 9 (97) , (978) ﾀ, () 5 (968) 6. ｧ9 9, () (98) 6. ｧ9 9, , (5) 7 (98) 6. Zahnn M, Chatelon H J. Appl. Phys (977) 6. ｧ5 6 9, 閨75 9 ﾀ (.: 999, 979) 6. Felici N J, Lacroix J C J. Electrostat. 5 5 (978) 65. Atten P, Lacroix J C J. Electrostat. 5 9 (978) 66. Little R P, Whithney W T J. Appl. Phys. (96) , 589, ﾀ (98) (995) 69. ｧ () 7 (98) , ｧ () 7 (98) , A9575 ﾁ ﾁ ( ﾀ578: ﾀ 閨8, 99) 7. Voinov M, Dunnett J J. Am. Electrochem. Soc. 9 (97) 7. Atten P, in Electrohydrodynamics (CISM Courses and Lectures, No. 8, Ed. A Castellanos) (Wien: Springer, 998) p. 7. ｧ () (986) 75. ｧ () 8 (988) 76. ｧ9 9,. 閨 ( ﾀ ﾀ5575) ( : , 988) Castellanos A, in Electrohydrodynamics (CISM Courses and Lectures, No. 8, Ed. A Castellanos) (Wien: Springer, 998) p. 78. Adamczewski I Ann. Phys. (Leipzig) 8 9 (97) 79. Grovski O, Terlecki I Acta Phys. Pol (959) 8. Grovski O Nature 9 7 (96) 8. Hummel A, Allen A O, Watson F (Jr) J. Chem. Phys. (966) 8. Schmidt W Z. Naturforsch. 6 6 (968) 8. Secker P E, Lewis T J Br. J. Appl. Phys (965) 8. Gray E, Lewis T J Br. J. Appl. Phys. 6 9 (965) 85. Belmont M R, Secker P E J. Phys. D: Appl. Phys. 5 (97) 86. Schmidt W, Allen A J. Chem. Phys (97) 87. LeBlanc O J. Chem. Phys. (959) 5*

18 68.9. ｧ9 [ Chong P, Inishi Y Tech. Rep. Osaka Univ. 55 (96) 89. Terlecki I Nature 9 7 (96) 9. Minday R M, Schmidt L D, Davis H T J. Chem. Phys. 5 (97) 9. Brignell J E, Buttle A J. Phys. D: Appl. Phys. 56 (97) 9. Essex V, Secker P E J. Phys. D: Appl. Phys. 6 (968) 9. Essex V, Secker P E J. Phys. D: Appl. Phys. 7 (969) 9. Taylor R, House H, in Proc. of the th Intern. Conf. on Conduction and Breakdown in Dielectric Liquids, Dublin, Ireland, July 5 ﾀ 7, 97 (Dublin: The Conference, 97) p , 5 5 ﾀ (966) 96. Dikarev B et al., in Proc. of 999 IEEE th Intern. Conf. on Dielectric Liquids (ICDL'99), Nara, Japan, July ﾀ 5, 999 (Piscataway, NJ: IEEE, 999) p () 7 (986) 98. ｧ (7) 58 () 99. Pontiga F, Castellanos A IEEE Trans. Ind. Appl. 86 (996). Gennes P G, Pincus P A Phys. Kondens. Mater. 89 (97) (97). 98 6ｨ ｨ ( ﾀ ) (.: 97, 965). Atrazhev V M, Timoshkin I V, in Proc. of 996 IEEE th Intern. Conf. on Conduction and Breakdown in Dielectric Liquids, Rome, Italy, July 5 ﾀ 9, 996 (New York: IEEE, 996) p.. Khrapak A G, Volykhin K F, in Proc. th Intern. Conf. on Conduction and Breakdown in Dielectric Liquids (Rome, Italy, 996) p. 9 Ionic conductivity and complexation in liquid dielectrics A.I. Zhakin Kursk State Technical University, ul. 5 Let Oktyabrya 9, 5 Kursk, Russian Federation Tel. (7-7) Fax (7-7) [email protected] Electronic and ionic conductivity in non-polar liquids is reviewed. Theoretical results on ionic complexation (ion pairs and triplets, dipole-dipole chains, ion-dipole clusters) in liquid dielectrics in an intense external electric ｨｦeld are considered, and the relation between the complexation process and ionic conductivity is discussed. Experimental results supporting the possibility of complexation are presented and compared with theoretical calculations. Onsager's theory about the effect of an intense external electric ｨｦeld on ion pair dissociation is corrected for the ｨｦnite size of ions. PACS numbers: 5.5.+v, 66..Ed, 8..Fi Bibliography references Received November, revised May