Iineianeee ainoaea?noaaiiue oieaa?neoao
eiaie I.A. Eiiiiiniaa
Oeie/aneee oaeoeueoao
Eco/aiea acaeiiaeaenoaey a nenoaia
NaF-Bi2O3-BiF3 i?e 600 e 650(N.
Eo?niaay ?aaioa
ii iai?aaie/aneie oeiee
nooaeaioa 102 a?oiiu
Aeiia?ianeiai A.I.
Iao/iua ?oeiaiaeeoaee:
ani. 1 a/i Na?ia O.A.
e.o.i. A?aeaoieeiaa A.E.
I?aiiaeaaaoaeue:
e.o.i. A?aeaoieeiaa A.E.
Iineaa 1999 aiaeNiaea?aeaiea.
I Aaaaeaiea
…………………………………………………………….no
?. 3
II Iaci? eeoa?aoo?u
………………………………………………………… 5
No?oeoo?a oethi?eoa
………………………………………………….. 5
Ooi?eae iao?ey
………………………………………………………….. 6
No?iaiea
………………………………………………………….. 6
Naienoaa
………………………………………………………….. 6
Iieo/aiea
…………………………………………………………. 7
3. Ieneae aeniooa
………………………………………………………….. 8
No?iaiea
………………………………………………………….. 8
Naienoaa
…………………………………………………………… 10
Iieo/aiea
………………………………………………………….. 10
4. Ooi?eae aeniooa
…………………………………………………………. 11
No?iaiea
…………………………………………………………… 11
Naienoaa
…………………………………………………………… 12
Iieo/aiea
………………………………………………………….. 12
Nenoaia BiF3-Bi2O3
……………………………………………………. 13
Nenoaia NaF-BiF3
……………………………………………………… 16
Nenoaia NaF-Bi2O3
……………………………………………………. 18
Nenoaia NaF-Bi2O3-BiF3
…………………………………………….. 19
III Yenia?eiaioaeueiay /anoue
………………………………………………. 21
Enoiaeiua aauanoaa
…………………………………………………… 21
Iieo/aiea BiF3
………………………………………………………… 21
I?eaioiaeaiea ia?acoeia
…………………………………………….. 22
Iaoiaeu enneaaeiaaiey
………………………………………………… 23
Iniiaiua ?acoeueoaou e eo ianoaeaeaiea ……………………………
25
IV Auaiaeu
………………………………………………………………
…….. 43
V Nienie eeoa?aoo?u
……………………………………………………….. 44
Aaaaeaiea.
Oaa?aeua yeaeo?ieeou i?aaenoaaeytho niaie aauanoaa, i?iaiaeyuea
yeaeo?e/aneee oie a oaa?aeii ninoiyiee, i?iiaaeooi/iua a no?iaiee
iaaeaeo oaa?aeuie e?enoaeee/aneeie oaeaie n oeene?iaaiiui iieiaeaieai
eaaeaeiai aoiia eee eiia e aeeaeeeie yeaeo?ieeoaie, a eioi?uo iao
oii?yaei/aiiie no?oeoo?u e ana /anoeoeu iiaeaeaeiu.
Aeaaiaea?y ?acoii?yaei/aieth iaeiie ec iiae?aoaoie (eaoeiiiie eee
aieiiiie) oaeea aauanoaa a ii?aaeaeaiiii oaiia?aoo?iii eioa?aaea
i?iyaeytho aunieoth eiiioth i?iaiaeeiinoue a oaa?aeii ninoiyiee, /oi
iicaieyao ei iaoiaeeoue oe?ieia i?eiaiaiea a oicyenoaa: iie
eniieuecothony eae enoi/ieee oiea, oiieeaiua yeaiaiou [1], aaciaua
naini?u (iai?eia?, ooi?i?iaiaeyuea ia?acoeu nenoaiu SrF2-LaF3,
eaae?iaaiiua SrO, ?aeiiaiaeiaaiu eae ia?niaeoeaiua naini?u ii eenei?iaeo
[2]), aaia?aoi?u eenei?iaea (iai?eia?, neiaeiua ieneaeiua
eenei?iaei?iaiaeyuea ia?acoeu i?aaeeiaeaii eniieueciaaoue aeey
ioaeaeaiey eenei?iaea io ae?oaeo aacia [3]), a ea/anoaa yeaiaioia iaiyoe
au/eneeoaeueiuo ono?ienoa e a ae?oaeo iaeanoyo.
A iineaaeiea aeanyoeeaoey aunieay i?iaiaeeiinoue ii eiiai ooi?a
iaia?oaeaia o ?yaea iai?aaie/aneeo ooi?eaeia. Ii naiei naienoaai iie ia
onooiatho iiiaei ecaanoiui oaa?aeui yeaeo?ieeoai. Eo iaaeinoaoi/iay
eco/aiiinoue iaoneiaeaia a aieueoie noaiaie cia/eoaeueiie oeie/aneie
aeoeaiinoueth i?e aunieeo oaiia?aoo?ao, a oaeaea neeiiiinoueth e
ie?iaeae?ieeco.
Enneaaeiaaiey a yoie iaeanoe i?eaaee e iaia?oaeaieth a neiaeiuo
ooi?eaeiuo nenoaiao, niaea?aeaueo eaoeiiu Bi e uaei/iuo iaoaeeia,
ooi?i?iaiaeyueo niaaeeiaiee e oaa?aeuo ?anoai?ia ni no?oeoo?ie oethi?eoa
[4,5]. Eo aunieay i?iaiaeeiinoue iauyniyaony eaaeie iiey?ecoaiinoueth
eaoeiiia Bi3+, /oi oaaee/eaaao iiaeaeaeiinoue ooi?eae-eiiia. Iieacaii
oaeaea, /oi caiaia /anoe aieiiia ooi?a ia eenei?iae aua neeueiaa
iiauoaao i?iaiaeeiinoue ca n/ao iiyaeaiey aeiiieieoaeueiuo aaeainee a
aieiiiie iiae?aoaoea. E oiio aea ieniooi?eaeiua iaoa?eaeu caiaoii eo/oa
nio?aiythony ia aicaeooa, oiaaea eae /enoi ooi?eaeiua yeaeo?ieeou
/?acau/aeii neeiiiu e aeae?ieeco.
Ieniooi?eaeu aeniooa e eaeey, enneaaeiaaiiua ianeieueei eao iacaae [6],
iaiaa oaeiaiu a i?eiaiaiee, /ai n iao?eai aneaaenoaea eo
aea?ineiie/iinoe.
Iiyoiio, aieueoie i?aeoe/aneee eioa?an i?aaenoaaeyao nenoaia
NaF-Bi2O3-BiF3, eioi?ie e iinayuaia aeaiiay ?aaioa.
Oeaeueth ianoiyuae ?aaiou noaei eco/aiea acaeiiaeaenoaey a nenoaia
NaF-Bi2O3-BiF3 i?e oaiia?aoo?ao 600 e 650(N a iaeanoyo, i?eiueathueo e
BiOF e (-BiOyF3-2y.
Iaci? eeoa?aoo?u.
No?oeoo?a oethi?eoa.
No?oeoo?a oethi?eoa (i?e?iaeiue ieia?ae CaF2) iino?iaia ec eoae/aneeo
a?aiaoeaio?e?iaaiiuo yeaiaioa?iuo y/aae (?en. 1). Ia?aiao? a = 5,462 (
[7]. Eaoeiiu caieiatho iieiaeaiey a aa?oeiao eoaa e a oeaio?ao aai
a?aiae. Eoa ec aieiiia aienai a aieueoie eoa ec eaoeiiia. Oaeei ia?acii
eaoeiiu eiatho E* = 8 (eoa), a aieiiu E* = 4 (oao?ayae?).
?en. 1. No?oeoo?a oethi?eoa.2. Ooi?eae iao?ey.
2.1 No?iaiea.
Ooi?eae iao?ey e?enoaeeecoaony a no?oeoo?a oeia NaCl. I?ino?ainoaaiiay
a?oiia Fm3m, ia?aiao? yeaiaioa?iie y/aeee a = 4,634(4) ( [8].
Yeaiaioa?iay y/aeea eoae/aneay a?aiaoeaio?e?iaaiiay (?en. 2). I?e
?aciauaiee eiiia iaeiiai ni?oa a aa?oeiu e oeaio?u a?aiae yeaiaioa?iie
y/aeee eiiu ae?oaiai ni?oa caieiatho na?aaeeiu ?aaa? e oeaio? eoaa.
Aieiiu e eaoeiiu a oaeie no?oeoo?a eiatho oanoa?ioth eii?aeeiaoeeth.
Eii?aeeiaoeeiiiue iieeyae? – ieoayae?.
2.2 Naienoaa.
Ooi?eae iao?ey i?aaenoaaeyao niaie aaeia e?enoaeee/aneia aauanoai.
Oie = 997°N, Oeei = 1785°N.
(fH(298 = -569 eAeae/iieue [9].
Oi?ioi ?anoai?ei a aiaea (41,3 a/e aiaeu [10]). Acaeiiaeaenoaoao ii/oe
ni anaie ooi?eaeaie iaoaeeia III – VII a?oii e Be n ia?aciaaieai
ooi?iaoaeeaoia iao?ey, iai?eia?:
Na3AlF6.
I?e ?anoai?aiee a HF, a oaeaea i?e acaeiiaeaenoaee n aaciia?aciui
ooi?iaiaei?iaeii ia?acoao aeooi?eae iao?ey NaHF2:
NaF + HF = NaHF2.
A i?e?iaea NaF ano?a/aaony a aeaea ieia?aea aeeeeiieoa.
2.3 Iieo/aiea.
a) Iaeo?aeecaoeey ieaaeeiaie eeneioie ?anoai?ia NaOH eee Na2CO3 aei
neaaieeneie ?aaeoeee:
Na2CO3 + 2HF = 2NaF + CO2( + H2O.
I?e oia?eaaiee auaeaeyaony aacaiaeiue NaF.
NaF + HF(.
NaHF2 ?aceaaaaony aac ieaaeaiey, a ioee/ea io KHF2.
Aeey iieo/aiey /enoiai NaF i?iaeaaeiue i?aia?ao aeinoaoi/ii auaea?aeaoue
a oa/aiea ianeieueeeo /ania a nooeeueiii oeaoo i?e oaiia?aoo?a 150 –
200°N [11].
?en. 2. No?oeoo?a NaCl.3. Ieneae aeniooa (III).
3.1 Naienoaa.
Aeey ieneaea aeniooa (III) ecaanoiu aeaa noaaeeueiua (( e () e aeaa
iaoanoaaeeueiua (( e () iiaeeoeeaoeee (?en. 3) [12].
Noaoeiiao?e/aneay (-oi?ia aeaaeii-aeaeoiai oeaaoa onoie/eaa i?e
noaiaea?oiuo oneiaeyo e aieioue aei oaiia?aoo?u 730°N. Eiaao
iiiieeeiioth ?aoaoeo; i?. a?. ?21/n, ia?aiao?u yeaiaioa?iie y/aeee a =
5,848 (, b = 8,166 (, c = 7,510 (, ( = 113° [12].
I?e iinoaiaiiii iaa?aaaiee aei 730°N (-Bi2O3 i?aoa?iaaaao iieeii?oiue
ia?aoiae, oa?yy /anoue eenei?iaea, e i?aa?auaaony a (-oi?io (oi?ioea
Bi2O3-x, aaea o = 0,045-0,37). Yoa iiaeeoeeaoeey i?aiaeaaiai oeaaoa
oa?aeoa?ecoaony eoae/aneie ?aoaoeie n ia?aiao?ii a = 5,66 (, i?. a?.
Pn3m.
ss?ei-aeaeoay (-oi?ia ioee/aaony ecauoeii eenei?iaea (oi?ioea Bi2O3+x) e
i?aaenoaaeyao niaie oaa?aeue ?anoai? eenei?iaea a ieneaea aeniooa.
?aoaoea aai oaeaea eoae/aneay, ii ii n?aaiaieth n (-Bi2O3 yeaiaioa?iay
y/aeea oaaee/aia aaeaia ii anai o?ai iai?aaeaieyi. a = 10,76 ( [12]
(10,2501(5) ( a [13]), i?. a?. I23. Iaeaieaa onoie/eaa (-oi?ia i?e
aunieeo aeaaeaieyo eenei?iaea. Aa iiaeii oaeaea noaaeeece?iaaoue
eaae?iaaieai ieneaeaie e?aiiey eee naeioea a oi?ia niaaeeiaiee
M2Bi24O39, aaea I = Si, Pb [12]. Iieo/eoue aa iiaeii i?e ioeaaeaeaiee
(-iiaeeoeeaoeee iiae aeaaeaieai I2.
(-Bi2O3, oaeaea aeaeoiai oeaaoa, iiaeii iieo/eoue iaa?aaaieai aeniooeoa
(BiO)2CO3 eee ioeaaeaeaieai (-oi?iu aei oaiia?aoo?u ieiei 640°N. I?e
aeaeueiaeoai ioeaaeaeaiee iia eaaei ia?aoiaeeo a (-iiaeeoeeaoeeth.
(-Bi2O3 e?enoaeeecoaony a oao?aaiiaeueiie neiaiiee, ia?aiao?u
yeaiaioa?iie y/aeee: a = 3,85 (, n = 12,25 (. I?. a?. I4/mm. (-oi?ia
yaeyaony aieiiaeaoeoeeoiie ii ioiioaieth e oi?ioea Bi2O3.
A ?aaioa [14] iann-niaeo?aeueiui iaoiaeii enneaaeiaaia iaeanoue
aiiiaaiiinoe ieneaea aeniooa (III) i?e 1070 E. Eco/aieai ?aaiiaaney “aac
– oaa?aeay oaca” a ieaoeiiaie y/aeea onoaiiaeaii, /oi i?e yoie
oaiia?aoo?a ieneae aeniooa iiaeao eiaoue ninoaa io Bi2O2,8 aei Bi2O3,11.
Eiia?oyioiie noaeeiaoeee i?e yoie oaiia?aoo?a ioaa/aao ninoaa
Bi2O2,92(0,04.
3.2 Naienoaa.
(-Bi2O3 ieaaeony i?e 825°N [12]. Aeey oaiia?aoo?u eeiaiey a [9]
i?eaiaeeony cia/aiea 1890°N.
(fH(298 ((-Bi2O3) = – 577 eAeae/iieue [9].
Ieneae aeniooa (III) ia?anoai?ei a aiaea e ?anoai?ao uaei/ae. Eeneioaie
ia?aaiaeeony a niee aeniooa (III):
Bi2O3 (oa) + 6HCl (?) = 2BiCl3 (p) + 3H2O.
(-, (- e (-iiaeeoeeaoeee ieneaea aeniooa yaeythony aieiiiuie
i?iaiaeieeaie n iacia/eoaeueiui aeeaaeii yeaeo?iiiie i?iaiaeeiinoe,
oiaaea eae (-Bi2O3 – iieoi?iaiaeiee [11].
3.3 Iieo/aiea.
Iaeeo/oei niiniaii iieo/aiey ieneaea aeniooa n/eoaaony acaeiiaeaenoaea
?anoai?ia nieae aeniooa (III), iai?eia? ieo?aoa Bi(NO3)3 eee noeueoaoa
Bi2(SO4)3, n ecauoeii ?anoai?a uaei/e:
Bi(NO3)3 + 3NaOH = Bi(OH)3( +3NaNO3.
A inaaeie auiaaeaao aeae?ieneae aeniooa, eioi?ue caoai iaacaiaeeaatho
i?ieaeeaaieai:
Bi2O3 + 3H2O(.
4. Ooi?eae aeniooa (III).
4.1 No?iaiea.
O?eooi?eae aeniooa nouanoaoao a aeaea aeaoo iieeii?oiuo iiaeeoeeaoeee.
Onoie/eaie i?e noaiaea?oiuo oneiaeyo yaeyaony ?iiae/aneay iiaeeoeeaoeey
R-BiF3, i?e aeaaeaiee 15(3 eaa? ia?aoiaeyuay a oeniieoiiiaeiaioth
(O-BiF3). I?e aoiinoa?iii aeaaeaiee O-BiF3 iaonoie/ea e i?e ioaeeaa
eaaei ia?aoiaeeo a R-BiF3 [16].
Ia?aiao?u yeaiaioa?iie y/aeee aeey ia?aie ec iiaeeoeeaoeee (ii [15]):
a = 6,565(7) (, b = 7,016(7) (, c = 4,841(5) (. R-BiF3 ecino?oeoo?ai
ooi?eaeo eoo?ey (i?. a?. Pnma, Z = 4).
Aoii Bi a R-BiF3 ie?oaeai ainaiueth aeeaeaeoeie aoiiaie ooi?a ia
?annoiyieyo 2,217 – 2,502 (, aeaayoue aoii ooi?a iaoiaeeony ia
?annoiyiee 3,100 ( (?en. 3). Oaeia eneaaeaiea eii?aeeiaoeeiiiie noa?u
aoiia aeniooa iauyniyaony iaee/eai noa?aioeie/anee aeoeaiie ia?u
yeaeo?iiia ia aoiia aeniooa.
?en. 4. Ie?oaeaiea aoiia Bi a R-BiF3.
4.2 Naienoaa.
Ooi?eae aeniooa ia aicaeooa iaeionoie/ea. Oaea i?e eiiiaoiie oaiia?aoo?a
ai aeaaeiii aicaeooa ii ia/eiaao aeae?ieeciaaoueny, a i?e iiauoaiiuo
oaiia?aoo?ao ie?iaeae?ieec eaeao aei eiioea ii noaia:
Bi2O3
Iiyoiio i?aia?aou ooi?eaea aeniooa neaaeoao o?aieoue aac aeinooia aeaae
– a yeneeaoi?a iaae ?2I5.
Oaiia?aoo?a ieaaeaiey (a oiea HF) ninoaaeyao 757°N [16]. Oaiia?aoo?a
eeiaiey – 900°N [9].
(fH(298 (BiF3) = – 899 eAeae/iieue [9].
4.3 Iieo/aiea.
Iniiaiua niiniau iieo/aiey /enoiai o?eooi?eaea aeniooa naiaeyony e
acaeiiaeaenoaeth Bi2O3 eee Bi(OH)3 n neeueiuie ooi?e?othueie aaaioaie, a
ea/anoaa eioi?uo auee i?aaeeiaeaiu SF4, BrF3 [15] e ae?.
A ?aaioa [17] auei i?aaeeiaeaii ia?aaaouaaoue ieneae eee aeae?ieneae
aeniooa eiioeaio?e?iaaiiie ieaaeeiaie eeneioie a ieaoeiiaie /aoea i?e
iaa?aaaiee. Iieo/athueeny aeae?ao o?eooi?eaea aeniooa caoai
aeaaeae?aoe?otho a ieaoeiiauo oeaeyo a oiea nooiai ooi?iaiaei?iaea i?e
300°N.
A oie aea ?aaioa [17] i?eaaaeaia aua iaeia iaoiaeeea. O?ea?iieae
aeniooa, iieo/aaiue i?yiui acaeiiaeaenoaeai yeaiaioia, ia?aaaouaatho
ooi?eaeii aiiiiey a iaoaiieueiii ?anoai?a ii ?aaeoeee:
BiBr3 + 4NH4F = NH4BiF4 + 3NH4Br.
Auiaaoee inaaeie oao?aooi?aeniooaoa (III) aiiiiey ioaeaeytho, i?iiuaatho
yoe?ii e nooao i?e 60°N. I?ieaeeaay aai i?e 300°N iiaeii iieo/eoue
aacaiaeiue BiF3:
BiF3 + NH3( + HF(.
5. Nenoaia BiF3-Bi2O3.
Iaeaieaa iiae?iaii aeaiiay nenoaia eco/aeanue a [15,18]. Iino?iaia
oaciaay aeeaa?aiia (?en. 5). A iaeanoe, aiaaoie ooi?eaeii aeniooa
ia?acoaony oaa?aeue ?anoai? ( ni no?oeoo?ie oeniieoa LaF3 n
niaea?aeaieai ieneaea 0,7 – 3,45 iieue. % (0,02(y(0,1 a oi?ioea
BiOyF3-2y). Ii ia?a oaaee/aiey aeiee Bi2O3 ia?aiao?u aaenaaiiaeueiie
y/aeee eciaiythony neaaeothuei ia?acii: a oiaiueoaaony io 7,076(7) ( aei
7,053(7) (, a “n” oaaee/eaaaony io 7,313(7) ( aei 7,338(7) (. I?e
niaea?aeaiee ieneaea 3,45 – 6 iieue. % ia?acoaony ?yae oii?yaei/aiiuo
oac ni no?oeoo?ie, i?iecaiaeiie io oeniieoa. Eiaeeoee?iaaiea eo
?aioaaiia?aii cao?oaeiaii aneaaenoaea aeecinoe eo no?iaiey. Ia
aeeaa?aiia (?en. 5) aeey eaaeinoe aini?eyoey any iaeanoue ninoaaia 0,7 –
6 % Bi2O3 ecia?aaeaia eae oaa?aeue ?anoai? ( [15].
A iaeanoe niaea?aeaiey ieneaea 20 – 33 iieueiuo % ia?acoaony ?yae
oii?yaei/aiiuo oac ni no?oeoo?ie, i?iecaiaeiie io oethi?eoa. A ?aaioa
[15] ia?a/eneaiu eo ninoaau: 20; 21; 22,5; 25 e 33 iieue. % Bi2O3 e
?ann/eoaiu ia?aiao?u yeaiaioa?iuo y/aae, i?eaaaeaiiua a oaa. 1. A ?aaioa
[19] ooi/iai ninoaa iineaaeiae ec ieo – Bi7F11O5 (31,25 iieue. % Bi2O3).
Yoa oaca iino?iaia ec oii?yaei/aiiuo eieii/aouo eeanoa?ia [19]. I?e
oaiia?aoo?ao 290 – 410°N ana oacu i?aoa?iaaatho iieeii?oiue ia?aoiae
(i?ienoiaeeo ?acoii?yaei/aiea), ia?acoy aieiiecauoi/iue oethi?eoiaue
oaa?aeue ?anoai?, o.i. (-oaco. Caeaeeoue aa, oi anoue iieo/eoue i?e
eiiiaoiie oaiia?aoo?a aaoi?ai [15] ia oaeaeinue. (-oaca – naiia
ooaiieaaeia niaaeeiaiea a nenoaia: iaeneiaeueiay oaiia?aoo?a ieaaeaiey
ninoaaeyao 995°N [15].
I?e yeaeiiey?iii niioiioaiee Bi2O3 e BiF3 ia?acoaony noaoeiiao?e/aneee
ieniooi?eae BiOF, ecino?oeoo?iue PbFCl. Niaaeeiaiea e?enoaeeecoaony a
oao?aaiiaeueiie neiaiiee n ia?aiao?aie yeaiaioa?iie y/aeee a = 3,750(5)
(, n = 6,228(9) (. Aaoi?u [15] i?aaeiieaaatho iaee/ea iieeii?oiiai
ia?aoiaea BiOF a eoae/aneoth oethi?eoiiiaeiaioth iiaeeoeeaoeeth i?e
620°N.
Oaa. 1. ?aioaaiia?aoe/aneea oa?aeoa?enoeee ieniooi?eaeiuo oac aeniooa
ni no?oeoo?ie, i?iecaiaeiie io oethi?eoa.
Aeiey Bi2O3,
Neiaiiey Ia?aiao?u
iieue. %
a, ( b, ( c, ( (, °
20* iiiieeeiiay 4,09(1) 5,89(1) 4,13(1) 90,3(1)
21* ?iiae/aneay 4,14(1) 4,16(1) 5,88(1) —
22,5* oao?aaiiaeueiay 4,14(1) — 5,82(1) —
25* ?iiae/aneay 4,12(1) 4,10(1) 5,83(1) —
33* ?iiae/aneay 5,760(9) 5,569(8) 6,120(9) —
31,25** iiiieeeiiay 13,5238(3) 5,5285(1) 9,1886(2) 96,171(1)
* ii [15]. ** ii [19].
A iaeanoe niaea?aeaiey ieneaea aeniooa 60-68% i?e oaiia?aoo?ao auoa
450°N ia?acoaony aaenaaiiaeueiue oaa?aeue ?anoai? (. Ii eiaao aeaa
iiaeeoeeaoeee – ( e (‘, ia?aoeii ia?aoiaeyuea iaeia a ae?oaoth i?e
590-595°N. Aeey ninoaaa, niaea?aeauaai 67 iieue. % Bi2O3, caeaeaiiiai io
650°N, a [15] i?eaiaeyony ia?aiao?u aaenaaiiaeueiie ?aoaoee a = 8,33(1)
(, n = 19,03(1) (.
I?e iieueiie aeiea Bi2O3, ?aaiie 75%, ia?acoaony noaoeiiao?e/aneia
niaaeeiaiea Bi7O9F3 (aaeeinoaaiiue ec ieniooi?eaeia aeniooa aeaeoiai
oeaaoa). Aeey iaai ecaanoiu eae ieieioi aeaa iieeii?oiuo ia?aoiaea i?e
oaiia?aoo?ao 505 e 565°N. A ?aaioa [20] yoi niaaeeiaiea eco/aii iniaaiii
iiae?iaii. Onoaiiaeaia aai yeaeo?ii?iaiaeiinoue, ninoaaeythuay i?e 500E
( = 5(10-5 Ii-1ni-1. Oeacaii, /oi n iiauoaieai oaiia?aoo?u
yeaeo?ii?iaiaeiinoue auno?i ?anoao. Iieacaii oaeaea, /oi i?iaiaeeiinoue
iaania/aia i?aeoe/anee a ?aaiie noaiaie eiiaie ooi?a e eenei?iaea.
No?oeoo?a niaaeeiaiey ia iienaia.
Ec ninoaaa, niaea?aeauaai 80 iieue. % Bi2O3 auoa 515°N ia?acoaony
niaaeeiaiea Bi3O4F. I?ieiaeeoee?iaaoue aai ?aioaaiia?aiiu aaoi?ai [15]
ia oaeaeinue, aai no?oeoo?a oaeaea ia ii?aaeaeaia.
I?e oaiia?aoo?ao auoa 620°N cia/eoaeueiua eiee/anoaa (aei i?eia?ii
14 iieue. % i?e 790°N) ooi?eaea aeniooa ?anoai?ythony a (-Bi2O3,
noaaeeece?oy aai e ia?acoy oaa?aeue ?anoai? (-BiOyF3-2y.
?en. 5. Oaciaay aeeaa?aiia nenoaiu BiF3-Bi2O3.
6. Nenoaia NaF-BiF3.
Iiae?iaiia eco/aiea neiaeiuo ooi?eaeia aeniooa e uaei/iuo iaoaeeia
i?iaiaeeeinue iaiaeiie?aoii [4,5,15] (?en. 6).
Niaaeeiaiea NaBiF4 aia?aua auei iieo/aii aaoi?aie [21] ioaeeaii
niioaaonoaothuae niane NaF e BiF3 a ieaoeiiaii oeaea a aoiinoa?a aaeey
i?e 450°N. Oao?aooi?aeniooao iao?ey ecino?oeoo?ai aaaa?eieoo (-NaYF4,
ia?aiao?u yeaiaioa?iie y/aeee aai aaenaaiiaeueiie ?aoaoee: a = 6, 144 (,
n = 3,721 (. Ii aeaiiui [15] niaaeeiaiea eiaao oceoth iaeanoue
aiiiaaiiinoe (io 49 aei 51 iieue. % BiF3), a i?aaeaeao eioi?ie “a”
oaaee/eaaaony io 6,131(5) ( aei 6,147(4) (, a “n” oiaiueoaaony io
3,720(3) ( aei 3,706(3) (.
I?e 450°N NaBiF4 i?aoa?iaaaao iieeii?oiue ia?aoiae, ia?acoy eoae/aneee
oethi?eoiiiaeiaiue oaa?aeue ?anoai? Na1-xBixF1+2x. Aia?aua yoio ?anoai?
aue enneaaeiaai a [4].
Ii aeaiiui [15] a?aieoeu iaeanoe aiiiaaiiinoe eaaeao a i?aaeaeao 49 – 70
iieue. % BiF3. Aeey ia?acoeia, caeaeaiiuo io 500°N, ia?aiao?
yeaiaioa?iie y/aeee ?anoao io 5,686(4) ( aeey ninoaaa, niaea?aeauaai 60%
BiF3, aei 5,763(4) ( (70 iieue. % BiF3). Ia?acoeu n aeieae BiF3 50 – 60
iieue. % i?e caeaeeaaiee aeatho aeaa oacu: oethi?eoiiiaeiaiue oaa?aeue
?anoai? e NaBiF4.
Eioa?anii, /oi niaaeeiaiey IBiF4 aeey I = E, Rb, Tl eiatho no?oeoo?o
oethi?eoa i?e ethauo oaiia?aoo?ao io eiiiaoiie aei ieaaeaiey [5].
Aauanoaa auee eco/aiu a ?aaioa [5] a ea/anoaa aieiiiuo i?iaiaeieeia.
Iieo/aee ia?acoeu ecioa?ie/aneei ioaeeaii i?e 550°N a oa/aiea 12 /ania.
?en. 6. Oaciaay aeeaa?aiia nenoaiu NaF-BiF3.
7. Nenoaia NaF-Bi2O3.
Aeaiiuo ii nenoaia a eeoa?aoo?a ia iaia?oaeaii.
8. Nenoaia NaF-Bi2O3-BiF3.
Iiae?iaiia enneaaeiaaiea aeaiiie nenoaiu i?iaaaeaii a ?aaioa [11].
Eco/aii ecioa?ie/aneia na/aiea nenoaiu i?e oaiia?aoo?a 450°N (?en. 7).
I?aaeeiaeaia noaia o?eaiaoeyoeee.
Iniiaiui iauaeoii eco/aiey noaea iaoe?iay iaeanoue aiiiaaiiinoe
oethi?eoiiiaeiaiiai oaa?aeiai ?anoai?a, eiathuay ecauoie aieiiia ii
ioiioaieth e oi?ioea IO2, (iacaaiiay O) ia iniiaa /enoi ooi?eaeiiai
?anoai?a Na1-xBixF1+2x. Iaeanoue i?inoe?aaony a iai?aaeaiee (-BiOyF3-2y
aei niaea?aeaiey ieneaea aeniooa i?eia?ii 35 iieue. %. Ieieiaeueiia
niaea?aeaiea NaF a O i?e aeaiiie oaiia?aoo?a – ieiei 13 iieue. %. I?e
aieaa ieceii niaea?aeaiee NaF ia?acoeu aeaoooaciu.
Iaoiaeii eiiaaeainiie niaeo?ineiiee ecia?aia i?iaiaeeiinoue ia?acoeia.
Ii naiei i?iaiaeyuei oa?aeoa?enoeeai yoe aauanoaa ia onooiatho iiiaei
eniieuecoaiuo oaa?aeuo yeaeo?ieeoia, a ?aaioaoue n ieie iiaeii i?e
aeinoaoi/ii ieceeo oaiia?aoo?ao. Iiyoiio aaoi?u [11] i?aaeeiaeeee
eniieueciaaoue yoe aauanoaa a ea/anoaa oaa?aeuo aieiii?iaiaeyueo
iaoa?eaeia.
Ia/aeii enneaaeiaaiey nenoaiu iineoaeeea ?aaioa [22]. A iae enneaaeiaaiu
ia?acoeu ?ac?aca Bi2O3-NaBiF4, caeaeaiiua io 400°N (?en. 8). Iieacaii,
/oi a o?aoaieueieea NaF-BiOF-NaBiF4 iiauo oac ia ia?acoaony, a ?ac?acu
NaF-BiOF e BiOF-NaBiF4 yaeythony eaaceaeia?iuie. Caiaoiie iaeanoe
aiiiaaiiinoe ((3 iieue. % Bi2O3) ia iniiaa NaBiF4 ia iaia?oaeaii.
A ?aaioa [23] enneaaeiaaia eaoaeeoe/aneay aeoeaiinoue niaaeeiaiee
NaBi3O4A2 (aaea A – F, Cl, Br) e ecae?aoaeueiiio ieeneaieth iaoaia aei
aunoeo oaeaaiaei?iaeia. Oeacaii, /oi ia?acoeu aeaiiiai ninoaaa,
i?eaioiaeaiiua oaa?aeioaciui neioacii a ieaoeiiauo aiioeao i?e
oaiia?aoo?ao 750 – 900°N ec nianae Na2O, NaA e BiOA, auee iaeiioaciuie.
Eaoaeeoe/aneea naienoaa ia?acoeia eco/aee i?e 600 – 750°N, i?e/ai
ooi?eaeiua ia?acoeu iieacaee n?aaieoaeueii ooaeoea naienoaa. Oacu eiatho
neienooth no?oeoo?o oeia Neeeaia, ia?aiao?u aieaa iiae?iaii aeaiu a
iaoa?eaeao eiia?anna [24], eioi?ua iaeoe ia oaeaeinue.
?en.7. Noaia ecioa?ie/aneiai na/aiey
nenoaiu NaF-Bi2O3-BiF3 i?e 450°N.
Yenia?eiaioaeueiay /anoue.
1. Enoiaeiua aauanoaa.
A ea/anoaa enoiaeiuo aauanoa eniieueciaaeenue NaF e Bi2O3 ia?ee «/aea»,
Bi(OH)3 ia?ee «o/» e BiF3, neioace?iaaiiue iaie.
NaF i?aaeaa?eoaeueii iaacaiaeeaaee i?e 200(N a oa/aiea nooie [11].
I?iaeaaeiue i?aia?ao (-Bi2O3 auaea?aeeaaee 12 /ania a nooeeueiii oeaoo
i?e oaiia?aoo?a 800(N aei iieiiai oaeaeaiey neaaeia aeaae.
Enoiaeiua aauanoaa o?aieee a cae?uouo athenao a yeneeaoi?a iaae P2O5.
Eaeaioeoeeaoeey i?iaiaeeeanue iaoiaeii ?OA.
2. Iieo/aiea BiF3.
A ea/anoaa enoiaeiiai i?aia?aoa aeniooa aue acyo aeae?ieneae. Aauanoai
iaa?aaaee n eiioeaio?e?iaaiiie ieaaeeiaie eeneioie a oa/aiea ianeieueeeo
/ania. A ?acoeueoaoa ?aaeoeee:
Bi(OH)3 + 3HF = BiF3(aq( + 3H2O
iinea oia?eaaiey inoaaaeny inaaeie aeae?aoe?iaaiiiai ooi?eaea aeniooa,
eioi?ue iaacaiaeeaaee a oiea nooiai HF a oa/aiea 4 /ania i?e oaiia?aoo?a
350°N a i?eai?a (?en. 8), ninoiyuai ec enoi/ieea ooi?enoiai aiaei?iaea
(iaaeiay ?aoi?oa n NaHF2), iaaeiie o?oaee, ?aniieiaeaiiie a iae
ieeaeaaie eiaei/ee n aauanoaii e iiaeioeoaeueiie nenoaiu, caiieiaiiie
oaa?aeie uaei/ueth.
Eaeaioeoeeaoeey aacaiaeiiai BiF3 auea i?iaaaeaia iaoiaeii ?OA.
Aauanoai oaeaea o?aieee a cae?uoii athena a yeneeaoi?a iaae P2O5.
?en. 8. I?eai? aeey iaacaiaeeaaiey aeae?aoe?iaaiiiai ooi?eaea aeniooa a
oiea aaciia?aciiai HF.
3. I?eaioiaeaiea ia?acoeia.
Ia?acoeu aeey eco/aiey nenoaiu NaF-Bi2O3-BiF3 auee i?eaioiaeaiu iaoiaeii
oaa?aeioaciiai neioaca. Iaaanee enoiaeiuo aauanoa, acyoua a iaiaoiaeeiuo
niioiioaieyo (oaa. 2), acaaoeaaee ia aiaeeoe/aneeo aanao “Sartorius” n
oi/iinoueth 0,2 ia.
Ioi?anniaaiiua a oaaeaoee ia?acoeu ioaeeaaee a caiayiiuo iaaeiuo
aiioeao, caiieiaiiuo a?aiiii, n caeaeeaaieai iooai iioneaiey aiioe a
oieiaeioth aiaeo. Oneiaey ioaeeaia i?eaaaeaiu a oaa. 3.
Ioia?aoeey ia?acoeia, i?inoaaeaiiay ia ?aioaaiia?aiiao, yaeyaony
neaiciie aeey ianeieueeeo ?aaio eaai?aoi?ee, niioaaonoaey iiia?ia
iieacaiu a oaa. 4.
Oaaeeoea 2. Iaaanee aeey i?eaioiaeaiey ia?acoeia.
Iieueiua % Iannu, a Aieii.
? NaF BiO1.5 BiF3 NaF BiO1.5 BiF3 eca.
1 15 22,67 62,33 0,0056 0,0470 0,1474 0,36
2 10 36 54 0,0036 0,0724 0,1240 0,26
3 10 32 58 0,0036 0,0646 0,1336 0,32
4 10 29,33 60,67 0,0036 0,0588 0,1390 0,36
5 5 36 59 0,0017 0,0685 0,1279 0,36
6 5 38,67 56,33 0,0018 0,0777 0,1292 0,32
7 5 42,67 52,33 0,0017 0,0821 0,1150 0,26
8 5 30 65 0,0017 0,0566 0,1400 0,45
9 10 23,33 66,67 0,0036 0,0464 0,1515 0,45
10 — 49,33 50,67 — 0,0917 0,1074 0,26
11 — 42,67 57,33 — 0,0785 0,1205 0,36
12 — 66,67 33,33 — 0,1266 0,0723 0
13 5 63,33 31,67 0,0018 0,1244 0,0710 —
14 5 57,14 37,86 0,0018 0,1112 0,0842 —
4. Iaoiaeu enneaaeiaaiey.
Enneaaeiaaiea oaciaiai ninoaaa ia?acoeia auei i?iaaaeaii iaoiaeii
?aioaaiioaciaiai aiaeeca (?OA). ?OA i?iaiaeeee a eaia?a-iiiio?iiaoi?a
oeia Aeiuea n yooaeoeaiui na/aieai 228 ii, eceo/aiea Cu K(1.
?aioaaiia?aiiu iaeioi?uo ia?acoeia i?iia?yee ia eiiia?aoi?a n
oi/iinoueth 0,001 ii. Eioaineaiinoue eeiee ii?aaeaeyee aecoaeueii ii
iyoeaaeeueiie oeaea.
Eiaeeoee?iaaiea iaoiaeii iiaeai?a ecino?oeoo?iiai niaaeeiaiey e
ooi/iaiea ia?aiao?ia yeaiaioa?iie y/aeee iaoiaeii iaeiaiueoeo eaaae?aoia
i?iaiaeeee n eniieueciaaieai i?ia?aii Powder.
A ea/anoaa aioo?aiiaai noaiaea?oa i?e eiaeeoee?iaaiee eniieueciaaeny
aa?iaiee (ia?aiao? eoae/aneie ?aoaoee oeia aeiaca – a = 5,658 ( [7]).
Oaaeeoea 3. Oneiaey ioaeeaia e ?acoeueoaou ?OA.
? ia?acoea ? ioaeeaa A?aiy ioaeeaa, / Oaiia?aoo?a,
°N Oaciaue
ninoaa
1 I 6 600 O
2 I 6 600 O
3 I 6 600 O
4 I 6 600 O
5 I 6 600 O
6 I 6 600 O
7 I 12 600 O + I
II 12 + 14* 600 + 650* O + I
8 I 12 600 O + I
II 12 + 14* 600 + 650* O
9 I 12 600 O + I
II 12 + 14* 600 + 650* O + I
10 I 6 600 I + …
II 6 + 14* 600 + 650* I + …
11 I 6 600 I + …
II 6 + 14* 600 + 650* I + …
12 I 12 600 I + …
II 12 + 14* 600 + 650* I + …
III 12 + 17* 600 + 500* I + …
13 I 12 + 14* 600 + 650* O’
II 12 + 17* 600 + 500* O’ + I
14 I 12 + 14* 600 + 650* O’ + I
II 12 + 17* 600 + 500* I
* Aeiiieieoaeueiue ioaeea. Ia?aia a?aiy niioaaonoaoao ia?aie
oaiia?aoo?a, aoi?ia – aoi?ie.
Oaaeeoea 4. Niioaaonoaey ioia?aoeee ia?acoeia.
Iiia? a
aeaiiie ?aaioa 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Iiia? ia ?aioaaiia?aiiao 34 28 44 45 46 47 39 40 41 48 49 4 42 43
5. Iniiaiua ?acoeueoaou e eo ianoaeaeaiea.
?acoeueoaou ?OA anao neioace?iaaiiuo ia?acoeia i?eaaaeaiu a oaa. 3.
Ii ?acoeueoaoai ?OA ia?acoeu ?? 1-6 iinea oanoe/aniaiai ioaeeaa i?e
600°N noaee iaeiioaciuie, oiaaea eae i?e aieaa ieceie oaiia?aoo?a
(450°N) ia?acoeu ? 1 e ? 2 aeaaaee aeaa oacu (O e oaa?aeue ?anoai? ia
iniiaa (-BiOyF3-2y) [11]. Oaeei ia?acii iaia?oaeaii ?anoe?aiea iaeanoe
aiiiaaiiinoe oethi?eoiiiaeiaiiai oaa?aeiai ?anoai?a O ii n?aaiaieth n
450°N [11] a iai?aaeaiee (-BiOyF3-2y (?en. 9).
Ia?acoeu ?? 7, 8 e 9 iinea I ioaeeaa auee iiiaioaciuie. Iinea II ioaeeaa
ia?acaoe ? 8 niaea?aeae oieueei oaco O, a ?? 7 e 9 – aeaa oacu (aeey
ia?acoea ? 9 i?iaaaeai aecoaeueiue ?OA, ?acoeueoaou ?OA aeey ? 7 a oaa.
5). O.a. i?e aeaeueiaeoai iiauoaiee oaiia?aoo?u iaeanoue aiiiaaiiinoe O
?anoe?yaony aua neeueiaa (?en. 9).
Oaaeeoea 5. ?aioaaiia?aoe/aneea aeaiiua
aeey ia?acoea ? 7(II).
N L(N) 2*TH D Q I/I0 Oaca
1 57.206 26.584 3.35025 890.93 5 O
2 62.878 29.410 3.03436 1086.09 0 I
3 65.668 30.800 2.90049 1188.65 2 O, I
4 68.802 32.362 2.76403 1308.93 0 I
5 90.617 43.225 2.09123 2286.62 0 I
6 92.437 44.131 2.05039 2378.64 3 O, I
7 105.271 50.516 1.80516 3068.82 0 I
8 108.755 52.249 1.74929 3267.96 2 O, I
9 113.814 54.765 1.67473 3565.43 0 O
10 132.772 64.188 1.44973 4758.05 0 O, I
11 145.874 70.696 1.33137 5641.59 0 O, I
?en. 9. Noaia ?aniieiaeaiey ia?acoeia
ia na/aiee nenoaiu NaF-Bi2O3-BiF3.
?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aii ia?acoeia ?? 1, 4, 5, 7(II) e
8(II), eaaeaueo ia ?ac?acao NaxBi1-x(O,F)2.36 e Na0.05Bi0.95(O,F)2+y
i?eaaaeaiu a oaaeeoeao 6–10. Auee ?ann/eoaiu ia?aiao?u yeaiaioa?iie
eoae/aneie y/aeee oacu O, iiiauaiiua a oaa. 11,12.
Ia?aiao? yeaiaioa?iie y/aeee eoae/aneie oacu O a ia?acoeao ?? 1 e 4
oi?ioi oeeaaeuaaaony a eeiaeioth caaeneiinoue ia?aiao?a io ninoaaa,
iieo/aiioth a [11] (?en. 10), oiaaea eae ia?aiao? yeaiaioa?iie y/aeee
ia?acoea ? 5 ia eaaeeo ia yoie i?yiie. Ii ia?aiao? aai y/aeee a
i?aaeaeao ioeaee niaiaaeaao n ia?aiao?ii /aoaa?oiai ia?acoea. A?aieoeo
oaa?aeiai ?anoai?a O, oaeei ia?acii, neaaeoao i?iaanoe /a?ac oi/eo
ia?ana/aiey aeaoo eeiee, o.a. i?e iieueiie aeiea NaF, ?aaiie i?eia?ii
11%. I?e iaiueoeo aea eiioeaio?aoeeyo NaF ia?acoeu, ii-aeaeeiiio,
aeaoooaciu. Ninoaa oaa?aeiai ?anoai?a O a ieo ia eciaiyaony e
niioaaonoaoao a?aie/iie eiioeaio?aoeee. Aa?iyoii, iacia/eoaeueiia
eiee/anoai i?eianiie oacu, i?enoonoaothuay a ia?acoeao ? 4 e 5, ia aeaao
?aoeaenia ia ?aioaaiia?aiia, o.e. /oanoaeoaeueiinoue iaoiaea ?OA ia
i?aauoaao 8 iann. %.
Ia?aiao?u yeaiaioa?iie eoae/aneie y/aeee oacu O a ia?acoeao ? 5, 7(II) e
8(II) (ii ?ac?aco Na0.05Bi0.95(O,F)2+y) eciaiythony iacia/eoaeueii
(oienoay eeiey ia a?aoeea, ?en. 11), /oi a oeaeii oeeaaeuaaaony a iauoth
caeiiiia?iinoue – n oiaiueoaieai niaea?aeaiey iao?ey aeeyiea aieiiiiai
ecauoea ia eciaiaiea ia?aiao?a ineaaaaaao [11] (?en. 11). Aa?iyoii, yoi
acaeiiia aeeyiea eaoeiiia Na e aiaae?aiiuo aieiiia naycaii n
aicieeiiaaieai annioeeaoia Na e ecauoi/iuo aieiiia.
Ia?acoeu ?? 10 e 11 e iinea ia?aiai, e iinea iiaoi?iiai ioaeeaa (oaa. 3)
ii aeaiiui aecoaeueiiai ?OA auee iiiaioaciuie. A ia?acoeao i?enoonoaoao
oaca ia iniiaa iiiieeeiiiai Bi7F11O5 [19], iaicia/aiiay I. Oaeei ia?acii
caeaeeoue i?aaeiieiaeeoaeueii eoae/aneee aunieioaiia?aoo?iue oaa?aeue
?anoai? ia iniiaa (-BiOyF3-2y [15] ia oaeaeinue.
Aaeeinoaaiiay oaca a ia?acoea ? 14(II), a oaeaea iaeia ec aeaoo oac a
ia?acoeao ? 7(I), ? 14(I) e ? 13(II), i?ieiaeeoee?iaaia a iiiieeeiiie
neiaiiee n ia?aiao?aie, aeeceeie e aeaiiui a [19] aeey oacu Bi7F11O5.
?acoeueoaou eiaeeoee?iaaiey i?eaaaeaiu a oaa. 16, 17, 18 e 19
niioaaonoaaiii, ia?aiao?u – a oaa. 20. Ia?aiao?u aa y/aeee a ia?acoeao
?acee/athony, ec /aai neaaeoao, /oi ia iniiaa oacu Bi7F11O5 ia?acoaony
oaa?aeue ?anoai? I.
Oaaeeoea 6. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu O a
ia?acoea ? 1.
Neiaiiey – eoae/aneay.
Ia?aiao? y/aeee: a= 5.785(1) (
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 26.651 3.34190 5 895.39 1 1 1 896.5 -1.1
2 30.884 2.89282 3 1194.97 0 0 2 1195.3 -0.3
3 44.242 2.04548 4 2390.07 0 2 2 2390.6 -0.5
4 52.407 1.74440 4 3286.31 1 1 3 3287.1 -0.7
5 54.943 1.66973 2 3586.82 2 2 2 3585.9 0.9
6 64.382 1.44583 1 4783.73 0 0 4 4781.2 2.6
7 70.942 1.32736 3 5675.77 1 3 3 5677.6 -1.9
Oaaeeoea 7. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu O a
ia?acoea ? 4.
Neiaiiey – eoae/aneay.
Ia?aiao? y/aeee: a= 5.799(1) (
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 26.577 3.35103 5 890.52 1 1 1 892.1 -1.6
2 30.814 2.89928 4 1189.65 0 0 2 1189.5 0.2
3 37.976 2.36729 0 1784.41 1 1 2 1784.2 0.2
4 44.135 2.05017 4 2379.14 0 2 2 2379.0 0.2
5 52.270 1.74864 5 3270.40 1 1 3 3271.1 -0.7
6 54.788 1.67409 3 3568.16 2 2 2 3568.5 -0.3
7 64.172 1.45005 2 4755.93 0 0 4 4758.0 -2.0
8 70.775 1.33009 3 5652.49 1 3 3 5650.1 2.4
Oaaeeoea 7. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu O a
ia?acoea ? 5.
Neiaiiey – eoae/aneay.
Ia?aiao? y/aeee: a= 5.799(1) (
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 26.587 3.34980 5 891.17 1 1 1 892.0 -0.8
2 30.816 2.89904 4 1189.85 0 0 2 1189.3 0.5
3 37.963 2.36811 0 1783.18 1 1 2 1784.0 -0.8
4 44.136 2.05013 4 2379.23 0 2 2 2378.6 0.6
5 52.288 1.74807 5 3272.53 1 1 3 3270.6 1.9
6 54.776 1.67440 3 3566.80 2 2 2 3567.9 -1.1
7 64.179 1.44990 2 4756.88 0 0 4 4757.2 -0.4
8 70.751 1.33048 3 5649.14 1 3 3 5649.2 -0.1
Oaaeeoea 9. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu O a
ia?acoea ? 7(II).
Neiaiiey – eoae/aneay.
Ia?aiao? y/aeee: a= 5.801(1) (
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 26.584 3.35025 5 890.93 1 1 1 891.4 -0.4
2 30.800 2.90049 2 1188.65 0 0 2 1188.5 0.2
3 44.131 2.05039 3 2378.64 0 2 2 2377.0 1.6
4 52.249 1.74929 2 3267.96 1 1 3 3268.4 -0.4
5 54.765 1.67473 0 3565.43 2 2 2 3565.5 -0.1
6 64.188 1.44973 0 4758.05 0 0 4 4754.0 4.1
7 70.696 1.33137 0 5641.59 1 3 3 5645.4 -3.8
Oaaeeoea 10. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu O a
ia?acoea ? 8(II).
Neiaiiey – eoae/aneay.
Ia?aiao? y/aeee: a= 5.794(2) (
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 26.651 3.34191 5 895.39 1 1 1 893.6 1.8
2 30.858 2.89524 2 1192.97 0 0 2 1191.4 1.5
3 44.193 2.04763 3 2385.05 0 2 2 2382.9 2.2
4 52.335 1.74663 3 3277.90 1 1 3 3276.4 1.5
5 54.881 1.67146 0 3579.37 2 2 2 3574.3 5.1
6 64.255 1.44837 0 4766.94 0 0 4 4765.7 1.2
7 70.776 1.33007 1 5652.68 1 3 3 5659.3 -6.6
Oaaeeoea 11. Ia?aiao?u yeaiaioa?iuo y/aae oacu O
ia?acoeia ?ac?aca NaxBi1-x(O,F)2.36.
? ia?acoea 1 4 5
o 0.15 0.10 0.05
Ia?aiao? a, ( 5.785(1) 5.799(1) 5.799(1)
Oaaeeoea 12. Ia?aiao?u yeaiaioa?iuo y/aae oacu O
ia?acoeia ?ac?aca Na0.05Bi0.95(O,F)2+y.
? ia?acoea 7 5 8
y 0.26 0.36 0.45
Ia?aiao? a, ( 5.801(1) 5.799(1) 5.794(2)
?en. 10. Ia?aiao?u eoae/aneie yeaiaioa?iie y/aeee
oacu O ?ac?aca NaxBi1-x(O,F)2,36.
?en. 11. Caaeneiinoe ia?aiao?a eoae/aneie yeaiaioa?iie y/aeee oacu O io
aieiiiiai ecauoea
ia ecieiioeaio?aoao iao?ey.
Ia?acaoe ? 13(II) e ? 14(I) niaea?aeaee aeaa oacu (oaa. 13, 14), iaeia
ec eioi?uo – I, a ae?oaay – eoae/aneay oethi?eoiiiaeiaiay oaca. Ia?acaoe
? 13(I) niaea?aeae oieueei iaeio eoae/aneoth oaco (oaa. 15), a ? 14(II)
– oieueei I (oaa. 16). Iiaeii naeaeaoue auaiae i iaee/ee iaeanoe
aiiiaaiiinoe eoae/aneie oacu ni no?oeoo?ie oethi?eoa,
i?aaeiieiaeeoaeueii ia iniiaa aunieioaiia?aoo?iiai
(-BiOF. Oaeie oacu i?e oaiia?aoo?ao 400°N [22] e 450°N [11]
enneaaeiaaoaee ia iaaethaeaee e niiauaee i eaaceaeia?iinoe ?ac?aca
NaF-BiOF. Ana ia?acoeu yoiai ?ac?aca aeaaaee noaoeiiao?e/aneee (-BiOF.
Iaeeoei oaeaea ?anoe?aiea iaeanoe aiiiaaiiinoe yoie eoae/aneie oacu io
oaiia?aoo?u 500°N (ia?acaoe ? 13(II) aeaoooacai) e oaiia?aoo?a 650°N
(ia?acaoe ? 13(I) iaeiioacai). Aiaeiae/iia yaeaiea iaaethaeaee a nenoaia
NaF-Nd2O3-NdF3: i?enoonoaea NaF noaaeeece?iaaei aunieioaiia?aoo?ioth
eoae/aneoth iiaeeoeeaoeeth NdOF. Oaa?aeue ?anoai? ia iniiaa BiOF
iaicia/ai O’. Eioa?anii, /oi ia?aiao? yeaiaioa?iie y/aeee O’ (aeey
ia?acoea ? 13(I): a = 5,794(1) () niaiaaeaao n ia?aiao?ii y/aeee oacu O
(aeey ia?acoea ? 8(II): a = 5,794(1) ().
Ia?acaoe ? 12, ninoaa eioi?iai niioaaonoaoao oi?ioea BiOF, oaea iinea
ia?aiai ioaeeaa (oaa. 4) ?aniaeny ia ianeieueei oac. I?e aeaeueiaeoeo
ioaeeaao aai oaciaue ninoaa i?aeoe/anee ia eciaiyeny. Ia ?aioaaiia?aiiao
aeaeiu ?aoeaenu oacu I. Aa?iyoii i?aaeiieaaaaoeeny a [15] iieeii?oiue
ia?aoiae a eoae/aneoth iiaeeoeeaoeeth i?e 620°N i?ienoiaeeo n
iaeiia?aiaiiui eciaiaieai ninoaaa e eoae/aneee (-BiOF ia caeaeeaaaony.
O.e. iinea aeiiieieoaeueiiai ioaeeaa a oa/aiea 17 /ania i?e 500°N
oaciaue ninoaa ia?acoea ia eciaieeny, iiaeii i?aaeiieiaeeoue, /oi
eciaiaiea ninoaaa iaia?aoeii eee ia?aoiue i?ioeann cao?oaeiai
eeiaoe/anee.
Oaaeeoea 13. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu I a
ia?acoea ? 14(II).
Neiaiiey – iiiieeeiiay.
Ia?aiao?u y/aeee:
a= 13.57(2) (
b= 5.526(6) (
c= 9.179(7) (
(= 96.45(7)°
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 17.220 5.14503 1 377.77 2 0 1 376.6 1.2
2 26.672 3.33936 5 896.75 1 1 2 899.7 -3.0
3 29.311 3.04438 1 1078.96 0 0 3 1081.8 -2.8
4 29.311 3.04438 1 1078.96 -1 0 3 1081.9 -3.0
5 31.190 2.86518 1 1218.14 -4 0 2 1214.2 4.0
6 32.261 2.77245 1 1300.99 0 2 0 1309.8 -8.8
7 43.316 2.08704 1 2295.83 2 0 4 2289.2 6.7
8 44.128 2.05049 0 2378.41 1 1 4 2378.6 -0.2
9 45.521 1.99095 0 2522.79 -4 2 2 2524.0 -1.2
10 50.354 1.81059 1 3050.43 3 2 3 3050.7 -0.3
11 52.776 1.73307 0 3329.40 2 3 1 3323.7 5.7
12 54.157 1.69208 0 3492.69 -8 0 1 3492.2 0.5
13 64.030 1.45293 0 4737.10 -9 1 1 4735.9 1.2
14 64.030 1.45293 0 4737.10 7 2 2 4740.0 -2.9
15 64.030 1.45293 0 4737.10 9 0 1 4737.3 -0.2
16 69.561 1.35030 0 5484.56 -5 1 6 5480.7 3.9
17 70.714 1.33107 0 5644.11 4 0 6 5645.0 -0.9
18 70.714 1.33107 0 5644.11 -6 0 6 5648.3 -4.2
Oaaeeoea 14. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu I a
ia?acoea ? 7(II).
Neiaiiey – iiiieeeiiay.
Ia?aiao?u y/aeee:
a= 13.58(2) (
b= 5.525(5) (
c= 9.186(6) (
(= 96.48(7)°
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 29.410 3.03436 0 1086.09 0 0 3 1080.4 5.7
2 29.410 3.03436 0 1086.09 -1 0 3 1080.4 5.7
3 30.800 2.90049 2 1188.65 1 0 3 1190.3 -1.6
4 30.800 2.90049 2 1188.65 -2 0 3 1190.2 -1.6
5 30.800 2.90049 2 1188.65 -3 1 2 1192.3 -3.7
6 32.362 2.76403 0 1308.93 0 2 0 1310.3 -1.3
7 43.225 2.09123 0 2286.62 2 0 4 2287.0 -0.4
8 44.131 2.05039 3 2378.64 1 1 4 2376.4 2.2
9 50.516 1.80516 0 3068.82 0 3 1 3068.1 0.7
10 52.249 1.74929 2 3267.96 7 1 1 3268.2 -0.3
11 64.188 1.44973 0 4758.05 -6 1 5 4757.1 0.9
12 64.188 1.44973 0 4758.05 2 0 6 4761.1 -3.0
13 64.188 1.44973 0 4758.05 -4 0 6 4761.0 -2.9
14 70.696 1.33137 0 5641.59 4 0 6 5640.2 1.4
15 70.696 1.33137 0 5641.59 -6 0 6 5640.1 1.5
Oaaeeoea 15. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu I a
ia?acoea ? 13(II).
Neiaiiey – iiiieeeiiay.
Ia?aiao?u y/aeee:
a= 13.52(1) (, b= 5.543(2) (, c= 9.165(5) (, (= 96.47(5)°
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 17.248 5.13672 1 378.99 2 0 1 379.0 -0.0
2 26.629 3.34463 5 893.93 1 1 2 899.9 -6.0
3 29.377 3.03768 0 1083.72 0 0 3 1085.2 -1.5
4 29.377 3.03768 0 1083.72 -1 0 3 1085.3 -1.6
5 29.544 3.02095 1 1095.75 3 0 2 1091.4 4.3
6 30.883 2.89294 3 1194.87 1 0 3 1195.8 -0.9
7 30.883 2.89294 3 1194.87 -2 0 3 1196.3 -1.4
8 30.883 2.89294 3 1194.87 -3 1 2 1195.9 -1.0
9 42.266 2.13644 0 2190.88 4 0 3 2192.6 -1.7
10 42.266 2.13644 0 2190.88 4 2 0 2188.1 2.8
11 43.338 2.08605 1 2298.01 2 0 4 2298.1 -0.1
12 44.177 2.04834 2 2383.39 1 1 4 2383.7 -0.3
13 50.392 1.80933 0 3054.67 3 2 3 3051.2 3.5
14 50.392 1.80933 0 3054.67 -2 0 5 3051.9 2.8
15 50.392 1.80933 0 3054.67 -4 2 3 3052.3 2.3
16 50.656 1.80050 0 3084.71 -1 3 1 3086.3 -1.6
17 52.418 1.74406 2 3287.59 7 1 1 3289.6 -2.0
18 52.582 1.73900 0 3306.76 2 3 1 3307.7 -1.0
19 64.392 1.44562 0 4785.08 2 0 6 4783.2 1.8
20 64.392 1.44562 0 4785.08 -4 0 6 4785.3 -0.2
21 64.392 1.44562 0 4785.08 -6 1 5 4782.0 3.1
22 64.392 1.44562 0 4785.08 -6 2 4 4783.5 1.6
23 69.754 1.34703 0 5511.23 -2 4 1 5512.0 -0.7
24 70.886 1.32827 0 5667.94 4 0 6 5669.0 -1.1
25 70.886 1.32827 0 5667.94 -6 0 6 5672.4 -4.5
Oaaeeoea 16. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu I a
ia?acoea ?14(I).
Neiaiiey – iiiieeeiiay.
Ia?aiao?u y/aeee:
a= 13.55(2) (
b= 5.529(4) (
c= 9.179(6) (
(= 96.49(6)°
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 17.207 5.14900 1 377.18 2 0 1 377.6 -0.4
2 26.687 3.33743 5 897.79 1 1 2 899.9 -2.1
3 29.338 3.04170 1 1080.85 0 0 3 1082.0 -1.2
4 29.338 3.04170 1 1080.85 -1 0 3 1081.9 -1.1
5 31.104 2.87285 1 1211.64 4 1 0 1209.2 2.4
6 32.304 2.76882 0 1304.40 0 2 0 1308.4 -4.0
7 42.296 2.13501 0 2193.83 4 2 0 2190.5 3.3
8 43.276 2.08888 1 2291.79 2 0 4 2291.3 0.4
9 44.153 2.04941 2 2380.92 1 1 4 2379.4 1.5
10 50.400 1.80904 0 3055.65 3 2 3 3052.3 3.4
11 52.690 1.73569 0 3319.38 2 3 1 3321.5 -2.1
12 54.203 1.69075 0 3498.17 -8 0 1 3501.4 -3.3
13 64.590 1.44166 0 4811.40 -8 2 1 4809.8 1.6
14 70.761 1.33031 0 5650.62 -6 0 6 5650.1 0.5
15 70.761 1.33031 0 5650.62 4 0 6 5651.9 -1.3
Oaaeeoea 17. Ia?aiao?u yeaiaioa?iie y/aeee
oacu I a ?acee/iuo ia?acoeao.
? ia?acoea Ia?aiao?u
a, ( b, ( c, ( (, °
7 (II) 13,58(2) 5,525(5) 9,186(6) 96,48(7)
13 (II) 13,52(1) 5,543(2) 9,165(5) 96,47(5)
14 (I) 13,55(2) 5,529(4) 9,179(6) 96,49(6)
14 (II) 13,57(2) 5,526(6) 9,179(7) 96,45(7)
Bi7F11O5 [19] 13,5238(3) 5,5285(1) 9,1886(2) 96,171(1)
Oaaeeoea 18. ?aioaaiia?aoe/aneea aeaiiua
aeey ia?acoea ? 13(II).
N L(N) 2*TH D Q I/I0 Oaca
1 35.149 17.248 5.13672 378.99 1 I
2 53.925 26.629 3.34463 893.93 5 O’, I
3 59.427 29.377 3.03768 1083.72 0 I
4 59.760 29.544 3.02095 1095.75 1 I
5 62.441 30.883 2.89294 1194.87 3 O’, I
6 64.839 32.081 2.78761 1286.87 0 I?
7 85.234 42.266 2.13644 2190.88 0 I
8 87.381 43.338 2.08605 2298.01 1 I
9 89.062 44.177 2.04834 2383.39 2 O’, I
10 101.510 50.392 1.80933 3054.67 0 I
11 102.040 50.656 1.80050 3084.71 0 I
12 105.569 52.418 1.74406 3287.59 2 O’, I
13 105.898 52.582 1.73900 3306.76 0 I
14 110.642 54.950 1.66953 3587.68 0 O’
15 129.562 64.392 1.44562 4785.08 0 O’, I
16 140.309 69.754 1.34703 5511.23 0 I
17 142.577 70.886 1.32827 5667.94 0 O’, I
Oaaeeoea 19. ?aioaaiia?aoe/aneea aeaiiua
aeey ia?acoea ? 14(I).
N L(N) 2*TH D Q I/I0 Oaca
1 35.064 17.207 5.14900 377.18 1 I
2 54.088 26.687 3.33743 897.79 5 O’, I
3 59.407 29.338 3.04170 1080.85 1 I
4 62.409 30.833 2.89749 1191.13 1 O’
5 62.953 31.104 2.87285 1211.64 1 I
6 65.362 32.304 2.76882 1304.40 0 I
7 85.422 42.296 2.13501 2193.83 0 I
8 87.391 43.276 2.08888 2291.79 1 I
9 89.152 44.153 2.04941 2380.92 2 O’, I
10 101.700 50.400 1.80904 3055.65 0 I
11 105.350 52.217 1.75029 3264.23 0 O’
12 106.300 52.690 1.73569 3319.38 0 I
13 109.340 54.203 1.69075 3498.17 0 I
14 110.737 54.899 1.67097 3581.48 0 O’
15 130.213 64.590 1.44166 4811.40 0 I
16 142.617 70.761 1.33031 5650.62 0 O’, I
Oaaeeoea 20. ?acoeueoaou eiaeeoee?iaaiey ?aioaaiia?aiiu oacu O’ a
ia?acoea ? 13(II).
Neiaiiey – eoae/aneay.
Ia?aiao? y/aeee: a= 5.794(1) (
N 2*TH D I/I0 Qobs h k l Qcalc dQ
1 26.669 3.33970 5 896.57 1 1 1 893.6 2.9
2 30.880 2.89318 3 1194.67 0 0 2 1191.5 3.2
3 44.194 2.04760 4 2385.12 0 2 2 2383.0 2.1
4 52.314 1.74728 4 3275.49 1 1 3 3276.7 -1.2
5 54.840 1.67262 1 3574.43 2 2 2 3574.5 -0.1
6 64.234 1.44881 0 4764.05 0 0 4 4766.0 -2.0
7 70.829 1.32919 1 5660.10 1 3 3 5659.7 0.4
Auaiaeu.
I?iaaaeai aiaeec eeoa?aoo?iuo aeaiiuo ii nenoaia
NaF-Bi2O3-BiF3.
I?iaaaeai neioac e eaeaioeoeeaoeey aacaiaeiiai BiF3.
Iaoiaeii oaa?aeioaciiai neioaca iieo/aiu 14 ia?acoeia nenoaiu. Ia?acoeu
eco/aiu iaoiaeii ?OA.
Iiaeoaa?aeaeaia iaaiciiaeiinoue i?e aeaiiuo oneiaeyo caeaeeoue
aunieioaiia?aoo?iua oacu (-BiOyF3-2y e (-BiOF, iaa ni no?oeoo?ie
oethi?eoa. Iaia?oaeaiu iaeanoe aiiiaaiiinoe oaa?aeuo ?anoai?ia ia iniiaa
iiiieeeiiiai Bi7F11O5 e ia iniiaa eoae/aneiai (-BiOF.
Ii?aaeaeaiu ia?aiao?u yeaiaioa?iie y/aeee oethi?eoiiiaeiaiiai oaa?aeiai
?anoai?a O ia ?ac?acao NaxBi1-x(O,F)2,36 e Na0,05Bi0,95(O,F)2+y.
Onoaiiaeaii ?anoe?aiea iaeanoe aiiiaaiiinoe oethi?eoiiiaeiaiiai
oaa?aeiai ?anoai?a O i?e 600 e 650(N. Ooi/iaiu aai a?aieoeu.
Nienie eeoa?aoo?u.
Azad A.M., Larose S., Akbar S.A.// J. Mater. Sci., – 1994, V. 29, ?. 16,
P. 4135. (Oeeo. ii ?AE Oei., 6A3216, 1996.)
Alcock C.B., Li Baozhen, Fergus J.W., Wang Li // Solid State Ionics,
1992, V. 53-56, ? 1, P. 39.
Iaoaio. “Oxygen generator having honeycomb structure made of oxygen
conducting materials” William N. Lawless. U.S. US 5,205,990 (Cl 422-121;
C25B9/00), 27 Apr. 1993. (Oeeo. ii Chem. Abs., P 126998, II 1993.)
Iiaeeiaa A.I., Oaaei?ia I.I., Ceieia A.A., Caiaineay A.TH.,
Oe?ieia TH.A., Noaieia N.A., Oaaei?ia I.E., I?ieiiaoe A.A.,
Niaieaa A.I.// AE. Iai?aai. Oeiee. – 1981, O. 26, ? 3, N. 774.
Lucat C., Sorbe P., Portier J., Hagenmuller P.// Mat. Res. Bull. – 1977,
V. 12, ? 2, P. 145.
Laborde P., Reau J.-M.// Rev. Chim. Miner. – 1986, V. 23, P. 523.
Ni?aai/iee oeieea. – I., 1962, O.1, N. 419, 446.
Shannon R.D.// Acta Cryst. – 1976, V. A32, P. 761. (Oeeo. ii [11].)
Oo?iaa I.ss. Iai?aaie/aneay oeiey a oaaeeoeao. – I., 1997.
Aieueoie yioeeeeiiaaee/aneee neiaa?ue. Oeiey. – I., 1998, N. 365.
Na?ia O.A. Aeeie. ?aaioa. – I., IAO, 1999.
Medernach J.W., Snyder R.L.// J. Amer. Ceram. Soc. – 1978, V. 61,
? 11-12, p. 39.
Radaev S.F., Simonov V.I., Kargin Yu.F.// Acta Cryst., Struct. Sci. –
1992, V. B48, ? 5, P. 604. (Oeeo. ii Chem. Abs., 223545s, II 1992.)
Ia?ooeei E.I., Aeeoaiyi A.N.// Aeiee. Aeaae. Iaoe, – 1993, O. 329, ? 4,
N. 452.
Eaeei/aiei O.A. Aeenna?oaoeey ia niene. o/aiie noaiaie eaiae. oei. iaoe.
– I., IAO, 1982.
A?aeaoieeiaa A.E., Ai?caieiaa I.I., Eaeei/aiei O.A.,
Iiainaeiaa A.A.//AE. Iai?aai. Oeiee. – 1981, O. 26, ? 7, N. 1727.
Eaeei/aiei O.A., Ai?caieiaa I.I., Iiainaeiaa A.A.// AE. Iai?aai. Oeiee.
– 1981, O. 26, ? 1, N. 222.
Eaeei/aiei O.A., Ai?caieiaa I.I., Iiainaeiaa A.A.// AE. Iai?aai. Oeiee.
– 1983, O. 28, ? 9, N. 2351.
Laval J.P., Champarnaud-Mesjard J.C., Frit B., Britel A., Mikou A.//
Eur. J. Solid State Inorg. Chem. – 1994, V.31, ? 10, P. 943. (Oeeo. ii
Chem. Abs., 95105n, I 1995.)
Aa/a? ?.A., Aieiaeeiae/ E.I., Iao?iae/ E.A.// Oaa?aeua yeaeo?ieeou e eo
aiaeeoe/aneia i?eiaiaiea, 3 Ananithciue neiiiceoi. Oacenu aeieeaaeia. –
Ieine, 1990, C. 13. (Oeeo. ii ?AE Oei., 14A3232, 1990.)
Oaaei?ia I.I., ssieei Ae.Ae., Ceieia A.A., Noaieia N.A.// AE. Iai?aai.
Oeiee. – 1979, O. 24, ? 10, C. 2831.
Ea?anaaa I.N. Eo?niaay ?aaioa ii iai?aaie/aneie oeiee. – I., IAO, 1997.
Ueda W., Thomas J.M.// J. Chem. Soc., Chem. Commun. – 1988, ? 17,
P. 1148.
Ueda W., Thomas J.M.// Proc. Int. Congr. Catal., 9th, 1988, part 2, P.
960.
PAGE 45
PAGE 9
Bi2O3
aeeaeeinoue
(-Bi2O3
(-Bi2O3
(-Bi2O3
(-Bi2O3
( ia?aioeaaeae.
( – ioeaaeaeaiea
( – iaa?aaaiea
( 825°N
( ?aceia ioeaaeae.
( 646° (ec 775°)
( 660° – 670°
a I2, ( 635° (ec 820°)
iaaeeaiii
(635° – 640°
iaaeeaiii ( 625°
( 620° – 605°
( 730°
( 700° (ec 745°)
?en. 3. Iiaeeoeeaoeee Bi2O3 e eo acaeiiua ia?aoiaeu.
Нашли опечатку? Выделите и нажмите CTRL+Enter
