Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://www.inorg.chem.msu.ru/sis/r450/ard/ard_02.pdf Äàòà èçìåíåíèÿ: Fri Jan 21 13:18:04 2005 Äàòà èíäåêñèðîâàíèÿ: Mon Oct 1 23:23:37 2012 Êîäèðîâêà:

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. ..

INORGANIC FLUORIDES
E. I. ARD A SHNIK O V A

Superlight alloys ­ fluxes and high temperature superconductors ­ are in close relationship with inorganic fluorides. It is shown that their chemical activity , crystal structure and other properties dramatically depend on fluorine atomic structure and on characteristics of chemical bonds in fluorides. The main problems of experimental work with fluorides are discussed. The modern branches of their practical use are considered. , . . .

, , : "fluorine" "", "" (, ) "". , 1886 F2 CaF2 ( ) . , . , , . , ( , ), (, , ) ­ "". , . .

.., 2000

, : · (R = 0,64 å, R = 1,33 å), · (4 . ),

www .issep.rssi.ru

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(327,8 ± 0,2 /) , · F F+ + - (I1 = 1681,04 ± 0,15 /). . ( , , , - d-). . . . , KF 856°, LaF3 ­ 1493°, DyF3 ­ 1154°; CaF2 ­ 2630°C, () ­ 2000­2500°. , ( ). SbF3 ­ 492,4 100 25°, (< 0,25 /) ThF4 , CaF2 , LaF3 . : F2 ­ F, ­ . , , , . , : F2 - 219,7° -188,2°, ClO3F -146,0° - 46,7°, NF3 - 206,8° -129,0° . . , 154,8 ± ± 2,1 /, , , F­F . F2 F­F. , . . : ( ) H2 , NH3 , H2O, SO2 , (, , ), Ag, V, Ti, Cr Cl2 , O2 , Xe. , , , . . (, KrF2 O2F2). H....F . , . , . HF , ( F­F, H­F 0,92­0,95 å, H....F 1,0­1,5 å, F­F­F 120,1°):

H

F H F H

F

( ) , (- 83,36°) (19,69° 1 ). HF 6. , 56° (HF)6 , (HF)n , n = 2­12 ( n = 3­6). 56°C 65 . H....F (NaHF2 , KHF2 , NH4HF2 ­ ), (, HF H2O - 36° ), ( HF), :
- HF + aq H+·aq + F -·aq + HF2 ·aq

(HF)nF -·aq,

n = 2­4 ,
- KF + HF K+ + HF2 , - SbF5 + HF H2F+ + SbF6 ,

3HF

- HF2 + H2F+

( )

..

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( , , , Al, Ga, In, B, Si, P .) ( , CO2 , NO) . , : (BF3 , SiF4 , PF5). . UF3 , UF4 , UF5 , UF6 U­F. , 1500, 1036, 348 64°. , Ba, Sr, Ca, Mg, Be, 1353° BaF2 565°C BeF2 , . "" ( ) ( [BeF4]2 - ). , ( 6 7) . : , , -. ­ , Hg3 - SbF6 Ag2F. , , ­Hg­Hg­ ­Ag­Ag­. Hg3 - SbF6 - [SbF6]-. : [BF4]-, [PF6]-, [AsF6]-, [SiF6]2 -. -, , () . ( ), [AsF6]-, [ZrF7]3 -, [ReF8]-. [MHaln]m -, Hal = F­I ( ), . [FeF6]3 - Fe3+ (, -) , Fe3+ ([FeF6]3 - 1016 > [Fe(SCN)6]3 - 103). : [BeIIF4]2 -, [BIIIF4]-, [Hf IVF6]2 -, [PVF6]-. , . . F - F2 . (). F - CuF 2 -, CoF 2 -, XeOF + 6 6 3 (ReF7 , PdF6 , AuF5 , TbF4). , "" . , . . (MF6), . . CaF2 . , , . " ". . 1 , . 2 CaF2 .

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. ( ) M­F . , ( ) 8, ­ 4. CaF2 = 5,438 å. , , , , () . ­ (). . , , . ­ XeF2 , 1962 [XeF][PtF6], XeF4 , XeF6 . . 3 , -. (. 4) F­Xe­F, Xe­F , Xe­F . XeF2 . , ( 129°C). 350° Xe XeF4 .
Ca F

, . . : ReF7 + H2O TiF4 + H2O HReO4 + HF, TiO2 xH2O + H2TiF6

. 1. CaF2

,

. 2. . . " " (.: , 1986. . 2)

. 3. , (Argonne National Laboratory) ( [5])

..

57



Xe F

: 3BiF 2Bi + BiF3 . F - O2 - ( OH-) . ( R 2 - =1,36 å), , O . - . . , ( ). : Na2O CaO 6SiO2 HF () NaF + SiF4 + CaF2 + H2O ( ),

. 4.

Na2O CaO 6SiO2 HF () Na2SiF6 + CaSiF6 + H2O ( ). , , , ­ . . , ( ) . ( ) . + (, NH4F + O2) , . . : F0 KrF2 O2F2 > F2 > XeF6 > ClF5 > XeF4 > ClF3 > > XeF2 > ClF > IF2 > BrF5 > BrF3 HF, NH4F,

­ . , . ( ) HF: CuF2 + H2O CaF2 + H2O LnF3
H2O t t t

CuO + 2HF, CaO + 2HF,

LnOF

H2O t

LnOxF3

- 2x

H2 O t

Ln2O3 ,

Ln ­ , La, Y. , , ( ), . . ­ (, ), (, BiF3). . , . -

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KF, NH4HF2 , KHF2 , MF2 (M = Pb, Zn, Cu, Cd, Ca), MF3 MOF (M = Bi, ), BF3 KBF4 , , . () , .
, BaF2 , SrF2 , CaF2 LnF3 , LnOF, BiOF CuF2 , CuF2 H2O ( ) F2 (20 t 450°C) NF3 (20 t 300°C) ClF3 (250 t 350°C) HF NH4HF2 F- (120­150 , 1012­1015 /2) F2 + - (60Co) F- XeF2 (200­400°C)

P2O5 . XeF2 . ­ ( ) - , . ( ) 19F. 18F ( 110 ). 1 ( XeF2). ( 1993 ) : 2 - 2 -. 2 1 2 C 1 : 2, 2 -. ( ). . 1. : BeF2 (), Al2O3 + Na3AlF6 (), () ZrF4 (HfF4) () K2ZrF6 (K2HfF6) (), K2TaF4 (). 2. (Be, Sc, Th, Zr .) (, (NH4)2BeF4). 3. : Nb Ta ­ K2NbOF5 H2O K2TaF7 ,
1 ( ) (TC = 138 K).



-

, , BaF2 , LnOF. " " ­ (, ) . . ­ " ", . , - YBa2Cu3O6F2 (TC = 94 K), SrCu(O,F)4 + (TC = 46 K) Cs3LnF7 (Ln = Ce, Pr, Nd, Tb, Dy, Tm), MAgF3 (M = Na­Cs). 250­400°. . XeF2 ­ ,

..

59



Be Al ­ Na2BeF4 , Na3AlF6 , Zr Hf ­ K2ZrF6 , K2HfF6 . , , 950° , Na3AlF6 (87­90%), CaF2 , (). ( Na3AlF6 1000°, Al2O3 2050°C), (82% Na3AlF6 + 18% Al2O3) 935° ( ) Na3AlF6­Al2O3 (. 5). , , , . ( ), . , . KBF4 , KHF2 , . ( , , , d- f- ). UF6 ( 235U 238U), UF4 LiF­BeF2 ( ), LiF ( ).
t, °C

. , , , , . () . , , (H2SiF6 , Na2SiF6 , ). , ( ), - , . . , , ­ : , ( ), , , , , . , .. " " ( . 1998. 2. . 95).
1. .. . .: , 1985. 224 . 2. .. . .: , 1990. 162 . 3. .., .., .., .. // . . . 1993. . 38. . 389­398. 4. .. // . . 1997. . 23, 2. . 83­91. 5. Celebration Volume to ommemmorate the entenary of the Isolation of Fluorine by Henry Moissan on 26th June, 1986 // J. Fluorine Chem. 1986. Vol. 33. 399 p.

980

.. , .. ***

960

940 e Na3AlF
6

10

20 Al2O3, .%

. 5. Na3AlF6­Al2O3

­ , . ­ - , , , . 80 , .

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