Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://www.inorg.chem.msu.ru/sis/r450/ard/ard_01.pdf Äàòà èçìåíåíèÿ: Fri Jan 14 19:26:52 2005 Äàòà èíäåêñèðîâàíèÿ: Mon Oct 1 23:23:22 2012 Êîäèðîâêà:

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. .
. ..

THE PHYSIC-CHEMICAL ANALYSIS AS A BASIS OF THE DIRECTED INORGANIC SYNTHESIS
E. I. ARD A SHNIK O V A

Methods of the physic-chemical analysis and phase diagrams are used for effective conducting such chemical processes as a synthesis of new substances, material property modifications by means of doping, the pure substances extraction by means of recrystallization or sublimation and others. Using a lot of examples of inorganic substances obtaining it is shown a critical role of phase diagrams for development of new experimental synthetic methods. The principle terminology of the physic-chemical analysis is given. , , , ­ - . . . journal.issep.rssi.ru

.., 2004

­ , . ­ . - : , , (, ). , . : , , , , , , ­ ­ . , , . "" , . ( , , ) , . ( ) - . - ­ , . ­ . , ,

30

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, 8, 2, 2004



. H: · 1 ­ Al2O3­Na3AlF6 (T - x) = 1 , ­ , ­ 1 ( ­ ); · 1 ­ Na2SO4­H2O (T - x) = 1 ( ); · 25° ( .. ) ­ HNO3­H2O ( - - ) = 25° , ­ ; · SO3 ( .. ) ­ H2SO 4­H 2O ( - - ) = 25° , ­ ( ). , ­, . (, , ), , , , , , , , , . , - 2, , , , , [1, 2]. ­ , . , , , , . . : - , . -: , 1 x ­ Na3AlF6 . , (1 - x) ­ Al2O3 . 2 .. : . 1998. 10. . 50.

­, , , . , ( ) . , . , ( ), . -, - , , , , ( ). . , ( ), . " " (.. . 1996. 6. . 41; .. . 1997. 3. . 115; .. . 1998. 11. . 96; .. . 1999. 10. . 108; .. . 2000. 2. . 93; .. . 2000. 5. . 31; .. . 2000. 8. . 54 .) - . , . - [1, 3] ­ VIII . ­ .. . . .. ( .. , . 3) - : .
3

. [4].

.. - ­

31



.. [1]: 240 , . , . , , . . , . ­ (, , ), , . . - . . -, .. , .. . - .. . : . .. , , . , . 1­4, 6, 7 , ­ L, ­ . , . , . 2 S. . 3 ­ ­ , . [5] - ­ , . ­ ( ), ( ). , . , , , , . , , . , (-, -, ..) ­ . , , ­ . . , , , . -, -, ..., . "" " " , . , , . , Na2SO4­H2O Na2SO4 10H2O, Na2SO4 + 10H2O Na2SO4 10H2O. , , , . , ( ), . . ( 1).

32

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(. 6, 7)



LiBr KBr, , : L LiBr() + KBr() .

(. 1)

(. 2)

(. 3, 4)

1.

LiBr­KBr , - . LiBr­KBr (. 1) , , KBr. . 1, 550°, . 730° LiBr KBr. () 334° ­ ( ), . . A , °C 700 500 LiBr + L 300 0 LiBr 20 e LiBr + KBr 40 60 80 L a KBr + L b Te 100 KBr

(, . 1) : 1) ( ) KBr, . KBr() + L. KBr() ; 2) ( b ) ­ ( L + LiBr() + + KBr()); 3) , (LiBr + KBr). () : LiBr KBr ( b ). (KBr() + L). , . L. PbTe­SnTe PbSe­SnSe PbTe PbSe, , (.. : . 1997. 4. . 65). . 2 3 PbTe­SnTe PbSe­SnSe, . , Sne Pbe, Pb1 - Sne (. 2 ­ S) , . Pb1 - SnSe (. 3 ­ ) < 0,55, SnSe PbSe. , : (S + L) ( + L), L ­ .

. %

. 1. LiBr­KBr

.. - ­

33



1200 , K 1450 1160 S+L 1120 1080 0 PbTe 20 40 60 80 . % SnTe 100 SnTe S , °C L 1250 A 1050 850 B C L

0 BaF

25
2

50 . % LaF3

75

100 LaF3

. 2. PbTe­SnTe 1400 , K L 1200 +L

. 4. BaF 2­LaF

3

012345

c

Ba 1000 +

1­x

LaxF

2+x

BaF

2

Ba

0,69

La0,31F2,31

T, °C nD 100 SnSe n 10 H, /2 lg ( )­1 t, 50% lim, ° a,

800

0 PbSe

20

40

60

80

. % SnSe

1354 1,48 1,40 80 ­10,7 12,5 6,200

1484 1,51 1,43 250 ­ 4,3 11,0 6,097

{111}
500 K h = 5

. 3. PbSe­SnSe

, : 1079­1196 Pb1 - SnTe 1135­1350 Pb1 - SnSe. , , : , 1160 PbTe­SnTe Pb0,77Sn0,23Te, PbSe­SnSe Pb0,64Sn0,36Se. Pb0,77Sn0,23Se 1215 K. BaF2­LaF3

. 5. ­

BeF2­LiF , ( ), LiBeF3 Li2BeF4 BeF2­LiF (. 6). (0­6,8 . % LiF)
2LiF · BeF2 60 80

, °C

Ba1 - LaF2 + , , BaF2­LaF3 (. 4), BaF2 (A) . (. 5 ­ .. , , 1991) , Ba0,69La0,31F2,31 (. 4 ).

700

500

300 0 BeF2 20 40 100 LiF

. % LiF

. 6. BeF 2­LiF

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LiF · BeF

L

2



, , , 550­500°. Li2BeF4 Li2BeF4 () Li2BeF4 () Li2BeF4 (Li2BeF4 () + L), . LiBeF3 280°, BeF2 Li2BeF4 : LiBeF3
()

­ Na2SO4 7H2O: Na2SO4 + 7H2O Na2SO4 7H2O.

: Na2SO4 7H2O() Na2SO4 10H2O() Na2SO4
()

Na2SO4

()

+L

24°

BeF2

()

+ Li2BeF4

()

. +L 32,4°. Na2SO4 7H2O : Na2SO4 7H2O Na2SO4 10H2O + Na2SO4 .

LiBeF3 , , L . 280°. Na2SO4­H2O Na2SO4­H2O. . 7 ­ ( ) 1 ( ). Na2SO4 10H2O ( ): Na2SO4 + 10H2O Na2SO4 10H2O,

1 , . (. 8 [2]).

, ( ''), . 7: (Na2SO4 10H2O() + L) ­ (Na2SO4 7H2O() + L) ­ . , . ( 3­5 . % Na2SO4) , . , 32,4° L . (Na2SO4 () + L) 32,4° .

60 L + Na2SO4 L 20 L + 0 e e' ­20 0 H2O 10 + Na2SO4 · 10H2O 20 30 . % Na2SO4 . 7. Na 2SO4­H2O 40 p Na2SO4 · 10H2O + Na2SO Na2SO4 · 10H2O L + Na2SO4 · 10H2O Na2SO4 · 7H2O p'
4

, °C

40

50 Na2SO
4

.. - ­

35





. 8. , [2]

1 , , ( ) 2. , ­ ­ ­. CuO­SrO­SrF2 , Sr2CuO3 La2CuO4 , . CuO­SrO­SrF2 Sr2CuO2F2 . Sr2CuO2F2 . , Sr2CuO2F2 + > 0 ( ) : Sr2CuO3 ( NH4F 400°) . , , ­ : Sr2Cu(O, F)4 + ( = 46 ). , , ­
, L, . , Na2SO4 10H2O Na2SO4 . 2 , Na2SO4 10H2O , Na2SO4 . : , (L Na2SO4 10H2O() + + ) ­ ( ).
1

( , , .) ­ . , - , , , , [3]. . " " (.. . 1997. 12. . 34; .. . 1998. 11. . 96; .. . 2000. 5. . 31 .). , . .. (1900­1986) 1953 . : (1953­1984 .), (1984­1988 .), ( 1988 .). .. .. .
1. .. : . .: - , 1987. 151 . 2. . . .: , 1988. . 1. 555 . 3. .., .., .. . .: , 1976. 503 . 4. .. , // . 1996. 6. . 414. 5. .., .. . . .: - , 1999. 28 .

***
­ , , (2003 .). ­ - , , , . 100 , .

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, 8, 2, 2004