IIAeA?OIIA OEOAIA.
Ia aeieth oeoaia i?eoiaeeony ieiei 0,2% io iauaai /enea aoiiia caiiie
ei?u, o.a. ii yaeyaony iaeiei ec aanueia ?ani?inoai?iiuo a i?e?iaea
yeaiaioia. Aeiey oee?eiiey ninoaaeyao 3(10-3 e aaoiey — 5(10-5%.
Oioy niaea?aeaiea a caiiie ei?a aeaaea aaoiey aieueoa, /ai, iai?eia?,
eiaea eee ?oooe, iaeiaei e oeoai e aai aiaeiae au? n?aaieoaeueii ieioi
inaiaiu i?aeoeeie e eiiaaea o?aeoothony eae “?aaeeea” yeaiaiou.
Iaoneiaeaii yoi eo ?aniue?iiinoueth, aneaaenoaea /aai i?eaiaeiua aeey
i?iiuoeaiiie ?ac?aaioee ianoi?iaeaeaiey ano?a/athony eeoue a iaiiiaeo
ianoao caiiiai oa?a. Ae?oaie aaaeiie i?e/eiie yaeyaony o?oaeiinoue
auaeaeaiey ?anniao?eaaaiuo yeaiaioia ec eo i?e?iaeiuo niaaeeiaiee.
Oee?eiiee ioe?uo a 1789 a., oeoai — a 1791 a. Ioe?uoea aaoiey
iineaaeiaaei eeoue a 1923 a. Yeaiaio ? 104 aue aia?aua (1964 a.)
neioace?iaai A. I. Oe??iaui n nio?oaeieeaie. A NNN? aeey iaai auei
i?aaeeiaeaii iacaaiea eo?/aoiaee (Ku), a NOA — ?aca?oi?aeee (Rf).
Ecaanoii ianeieueei ecioiiia yoiai yeaiaioa, ec eioi?uo iaeaieueoae
n?aaeiae i?iaeieaeeoaeueiinoueth aeecie aoiia (ieiei 2 iei.) iaeaaeaao
261Ku. Ia iaiiiaeo aoiiao auei iieacaii, /oi n oeie/aneie oi/ee c?aiey
eo?/aoiaee iiaeiaai aaoieth.
I?e?iaeiue oeoai neaaaaony ec ecioiiia 46 (8,0), 47 (7,3), 48 (73,9), 49
(5,5), 50 (5,3%); oee?eiiee — 90 (51,5%), 91 (11,2), 92 (17,1), 94
(17,4), 96 (2,8%); aaoiee — 174 (0,2), 176 (5,2), 177 (18,6), 178
(27,1), 179 (13,7), 180 (35,2%).
A iniiaiii ninoiyiee aoiiu eiatho no?iaiea aiaoieo yeaeo?iiiuo iaiei/ae
3d24s2 (Ti), 4d25s2 (Zr), 5d26s2 (Hf) e aeaooaaeaioiu. Aicaoaeaeaiea
/aou??oaaeaioiuo ninoiyiee Oi (3d33s1), Zr (4d35s1), Hf (5d36s1)
o?aaoao cao?aou niioaaonoaaiii 80, 59 e 167 eAeae/iieue, o.a.
inouanoaeyaony ai?acaei eaa/a, /ai o yeaiaioia iiaea?oiiu aa?iaiey.
Oeoai ano?a/aaony a ieia?aeao eeueiaieo (FeTiO3) e ?ooee (TiO2).
Cia/eoaeueiua eiee/anoaa oeoaia niaea?aeao oaeaea iaeioi?ua aeaeaciua
?oaeu, a /anoiinoe o?aeueneea oeoaiiiaaiaoeou. Oee?eiiee ano?a/aaony
aeaaiui ia?acii a aeaea ieia?aeia oee?eiieea (ZrSiO4) e aaaeaeaeaeoa
(ZrO2). Aeey aaoiey ioaeaeueiua ieia?aeu iiea ia iaeaeaiu. A aeaea
i?eiane (ii?yaeea 1 aoiii. %) ii anaaaea niaea?aeeony a ?oaeao Zr.
Ie/oiaeiua eiee/anoaa oeoaia iinoiyiii niaea?aeaony a i?aaieciao
?anoaiee e aeeaioiuo, ii aai aeieiae/aneay ?ieue ia ynia. Oeoai e aai
aiaeiae ia oiene/iu.
A naiaiaeiii ninoiyiee yeaiaiou iiaea?oiiu oeoaia iau/ii iieo/atho ioo?i
ainnoaiiaeaiey eo oei?eaeia iaaieai ii noaia:
YCl4 + 2 Mg = 2 MgCl2 + Y.
?aaeoeey i?iaiaeeony i?e iaa?aaaiee enoiaeiuo aauanoa aei 900 (N a
aoiinoa?a a?aiia (iiae aeaaeaieai).
Ainnoaiiaeaiea oei?eaeia oeoaia e aai aiaeiaia iaaieai nii?iaiaeaeaaony
cia/eoaeueiui auaeaeaieai oaiea: 531 (Oi) e 322 (Zr) eAeae/iieue.
Ae?oaei eo ainnoaiiaeoaeai yaeyaony iaoaeee/aneee iao?ee, ?aaeoeee n
eioi?ui au? aieaa yecioa?ie/iu (i?eaeeceoaeueii ia 355 eAeae/iieue).
Iaeaieaa /enoua ia?acoeu Ti, Zr e Hf auee iieo/aiu ioo?i oa?ie/aneiai
?aceiaeaiey ia ?aneae?iiie aieueo?aiiaie i?iaieiea ia?ia oao?aeiaeeaeia
iiae oiaiueoaiiui aeaaeaieai.
Ii oece/aneei naienoaai yeaiaiou iiaea?oiiu oeoaia yaeythony oeie/iuie
iaoaeeaie, eiathueie aeae noaee. *enoua iaoaeeu oi?ioi iiaeaeathony
iaoaie/aneie ia?aaioea. Ii aeaaea iacia/eoaeueiua i?eiane iaeioi?uo
yeaiaioia (I, I, N, C e ae?.) niiauatho ei o?oieinoue. Eo oa?aeoa?iua
eiinoaiou:
Ti Zr Hf
Ieioiinoue, a/ni3 4,5 6,5 13,3
Oaiia?aoo?a ieaaeaiey, (N 1670 1855 2220
Oaiia?aoo?a eeiaiey, (N 3170 4330 5690
Yeaeo?ii?iaiaeiinoue (Ig = 1) 2 2 3
A aeaea /enouo eiiiaeoiuo iaoaeeia ana o?e yeaiaioa iaeaaeatho aunieie
noieeinoueth ii ioiioaieth e ?acee/iui oeie/aneei aicaeaenoaeyi. Aieaa
?aaeoeeiiiiniiniaiu iie a iaeei?acae?iaeaiiii ninoiyiee, i?e iau/iuo
oaiia?aoo?ao ec anao eeneio eaaei acaeiiaeaenoaotho eeoue n HF. Eo/oei
?anoai?eoaeai aeey ieo yaeyaony nianue ieaaeeiaie e acioiie eeneio,
?aaae?othuay ii noaia:
3 Y + 18 IF + 4 HNO3 = 3 H2[YF6] + 4 NO + 8 H2O.
I?e aunieeo oaiia?aoo?ao Ti, Zr e Hf noaiiayony oeie/anee i/aiue
aeoeaiuie. A yoeo oneiaeyo iie yia?ae/ii niaaeeiythony ia oieueei n
aaeiaaiaie, eenei?iaeii e na?ie, ii oaeaea n oaea?iaeii e acioii.
Ii?ioee eo niiniaiu iiaeiuaoue aieueoea eiee/anoaa aiaei?iaea.
I?e iauae aunieie onoie/eainoe /enouo eiiiaeoiuo iaoaeeia e ?acee/iui
oeie/aneei aicaeaenoaeyi yeaiaiou iiaea?oiiu oeoaia i?iyaeytho e
iaeioi?ua eiaeeaeaeoaeueiua iniaaiiinoe. Oae, ii ioiioaieth e nieyiie
eee na?iie eeneioa oee?eiiee cia/eoaeueii onoie/eaaa oeoaia, a ii
ioiioaieth e aeaaeiiio oei?o eee oea?neie aiaeea — iaiai?io. Iiae
aeaenoaeai IF oeoai ia?aoiaeeo a o??oaaeaioiia ninoiyiea, a oee?eiiee e
aaoiee — a /aou??oaaeaioiia. I?e iaee/ee eiiia F( ana o?e iaoaeea
iinoaiaiii ?aaae?otho aeaaea ni neaauie eeneioaie. Eiioeaio?e?iaaiiie
acioiie eeneioie oeoai (iiaeiaii ieiao) ieeneyaony aei ia?anoai?eiie
oeoaiiaie eeneiou. A e?aieeo ?anoai?ao neeueiuo uaei/ae ii?ioie aai
?anoai?yaony n auaeaeaieai aiaei?iaea e ia?aciaaieai nieae oeoaiiaie
eeneiou. Oee?eiiee e aaoiee ii ioiioaieth e uaei/ai i/aiue onoie/eau.
Acaeiiaeaenoaea oeoaia ni ooi?ii ianooiaao oaea ieiei 150 (N, n ae?oaeie
aacaie — i?e 300(400 (N. A eenei?iaea ii?ioie oeoaia caai?aaony auoa 500
(N, a acioa — auoa 800 (N. Ii?ioie oee?eiiey ainieaiaiyaony ia aicaeooa
oaea ieiei 250 (N. Naeeaaieai aai a eenei?iaea iiaeao auoue iieo/aia
oaiia?aoo?a aei 4650 (N.
Iau/ii iiaa?oiinoue iaoaeee/aneiai oee?eiiey e oeoaia iie?uoa i/aiue
oiieie, ii ieioiie ie?ieie ieneaea, iieiinoueth eciee?othuae iaoaee io
aiaoieo aicaeaenoaee. I?e iaeioi?uo oneiaeyo (iai?eia?, i?e eiioaeoa Zr
c i/aiue aeaaeiui aicaeooii) ie?iea iiaeao noaoue oienoie, ?uoeie e
eaaei ioaeaeythuaeny a ?acoeueoaoa oiai eee eiiai neo/aeiiai
aicaeaenoaey (iai?eia?, nio?ynaiey). Aiacaiii inaiaiaeae?iiay io ia?
iaoaeee/aneay iiaa?oiinoue ia/eiaao yia?ae/ii ?aaae?iaaoue n eenei?iaeii
e aeaaie aicaeooa, /oi eiiaaea aaae?o e naiiaicai?aieth iaoaeea.
Neaaeoao ioiaoeoue, /oi ai?yuee ia aicaeooa oee?eiiee iioooeoue
i?aeoe/anee iaaiciiaeii.
Eaaeaeue iieue Ti, Zr eee Hf niiniaai ni?ae?iaaoue aei 1 iiey
aiaei?iaea, ii auno?i yoa ni?aoeey inouanoaeyaony eeoue i?e aunieeo
oaiia?aoo?ao (i?eaeeceoaeueii n 400 aeey Oi e n 700 (N aeey Zr).
Cia/eoaeueii eaa/a onoaiaaeeaaaony ?aaiiaanea, anee iaoaee aue
i?aaeaa?eoaeueii i?ieae?i a aoiinoa?a I2. I?inoaeoei iaoiaeii neioaca
yoeo aeae?eaeia yaeyaony aeinoaoi/iia iaa?aaaiea e caoai iaaeeaiiia
ioeaaeaeaiea iaoaeea a aoiinoa?a aiaei?iaea iiae oai eee eiui aai
aeaaeaieai. I?e iaeii niaea?aeaiee ni?ae?iaaiiiai aiaei?iaea aiaoiee
aeae iaoaeea nouanoaaiii ia eciaiyaony, ii i?e aieueoai ii i?aa?auaaony
a na?ue eee /??iue ii?ioie (n ieioiinoueth 3,8 aeey OiH2 e 5,5 a/ni3
aeey ZrH2). Ia?aciaaiea aeae?eaeia YI2 ec yeaiaioia eae?o n aeiaieueii
cia/eoaeueiui auaeaeaieai oaiea: ieiei 125 (Oi) eee 167 eAeae/iieue
(Zr). A iau/iuo oneiaeyo yoe aeae?eaeu onoie/eau ia aicaeooa (ii i?e
iiaeaeeaaiee caai?athony). Iie aeiaieueii eia?oiu oaeaea ii ioiioaieth e
aieueoeinoao aauanoa, ia yaeythueony neeueiuie ieeneeoaeyie. An? yoi
oeacuaaao, eae aoaeoi, ia ia?aciaaiea i?e ni?aoeee aiaei?iaea
ii?aaeae?iiuo oeie/aneeo niaaeeiaiee. Iaeiaei iiaeiaiua niaaeeiaiey
aeieaeiu auoue /?acau/aeii iaonoie/eau, oae eae iiaeiu?iiia iaoaeeii
eiee/anoai aiaei?iaea iaiyaony a caaeneiinoe io aai aeaaeaiey e
iineaaeiaaoaeueii oiaiueoaaony i?e iaa?aaaiee. Eioa?anii, /oi
ia?aciaaiea aeae?eaea oeoaia iaaethaeaeinue oaeaea i?e aeeeoaeueiii
aeaenoaee ia iaoaee e?aieie nieyiie eeneiou; iniiaiay ?aaeoeey eae?o ii
o?aaiaieth:
4 Oi + 6 HCl = 2 TiCl3 + 2 TiH2 + H2.
Aeae?eae oeoaia yaeyaony oi?ioei eaoaeecaoi?ii iaeioi?uo ?aaeoeee
aeae?e?iaaiey i?aaie/aneeo niaaeeiaiee. Ii iaoiaeeo eniieueciaaiea
oaeaea a ii?ioeiaie iaoaeeo?aee (eae ?aneeneeoaeue). Aeae?eae oee?eiiey
i?aaenoaaeyao eioa?an aeey yaea?iie yia?aaoeee (eae caiaaeeeoanue
iaeo?iiia). Oa?ie/aneei ?aceiaeaieai iaieo aeae?eaeia iiaoo auoue
iieo/aiu oiieea ie?iee niioaaonoaothuaai iaoaeea ia ?acee/iuo
iaoa?eaeao, /oi aaaeii aeey ?yaea iaeanoae oaoieee.
I?e iaa?aaaiee Oi e Zr niiniaiu ni?ae?iaaoue oaeaea eenei?iae (aei 30
ao. %), i?e/?i iiaeiuaiea nii?iaiaeaeaaony eeoue i/aiue iaaieueoei
oaaee/aieai iau?ia iaoaeeia. A iaiueoeo eiee/anoaao iie ni?ae?otho e
ae?oaea aacu (N2 e i?.).
I?aeoe/aneia cia/aiea Ti e Zr iniaaiii aaeeei aeey iaoaeeo?aee
niaoeeaeueiuo noaeae. Iaa iaoaeea eniieuecothony e a ea/anoaa
naiinoiyoaeueiuo eiino?oeoeaiuo iaoa?eaeia. Eo niaaeeiaiey iaoiaeyo
i?eiaiaiea a ?acee/iuo io?aneyo i?iiuoeaiiinoe. Aaoiee e aai niaaeeiaiey
iiea ii/oe ia eniieuecothony.
A iaoaeeo?aee oeoaiii e oee?eiieai iieuecothony a aeaea nieaaia n
aeaeacii — oa??ioeoaia e oa??ioee?eiiey, niaea?aeaueo 15(50% Oi eee Zr.
Au?aaioea yoeo nieaaia i?iecaiaeeony iau/ii ioo?i i?ieaeeaaiey
i?e?iaeiuo ieia?aeia Ti eee Zr n oae?i a i?enoonoaee aeaeaciie ?oaeu.
Aeiaaaea e noaee oaea 0,1% oeoaia i?eaea?o ae oa??aeinoue e
yeanoe/iinoue, /oi aeaeaao oaeoth noaeue i/aiue oi?ioei iaoa?eaeii aeey
ecaioiaeaiey ?aeuenia, aaaiiiuo inae e eie?n e o. ae. Aaaaeaieai a
noaeue oaea 0,1% Zr neeueii iiauoaao a? oa??aeinoue e ayceinoue, /oi
iniaaiii oeaiii aeey ecaioiaeaiey a?iiaauo ieeo e ueoia. Eae Oi, oae e
Zr ia?aaeei aaiaeyo oaeaea a ?acee/iua nieaau Nu e Al.
Eae eiino?oeoeeiiiue iaoa?eae oeoai eiaao i/aiue aeaaii?eyoiia ioiioaiea
i?i/iinoe e ianna a ni/aoaiee n aunieie oa?ie/aneie e ei??iceiiiie
noieeinoueth. Ii eniieuecoaony a naiieaoino?iaiee. Oee?eiiee
(inaiaiaeaeaiiue io i?eiane aaoiey) yaeyaony iaeiei ec aaaeiaeoeo
eiino?oeoeeiiiuo iaoa?eaeia i?e nii?oaeaiee aoiiiuo ?aaeoi?ia. Ii?ioie
iaoaeee/aneiai oee?eiiey i?eiaiyaony eiiaaea a ninoaaao aeey iao?iiiuo
caiaeia. Yoio aea ii?ioie a niane n ieo?aoii oee?eiiey eniieuecoaony
aeey ecaioiaeaiey naaoiauo neaiaeia, aeathueo i?e nai?aiee iiiai naaoa
ii/oe aac aeuia. Oeoai eiiaaea i?eiaiyaony a ea/anoaa eaoaeecaoi?a i?e
?acee/iuo ?aaeoeeyo, i?ioaeathueo n o/anoeai naiaiaeiiai acioa e
aiaei?iaea. I?e o?aiee oeoaia i noaeei ia iineaaeiai ioeaaaaony i/aiue
oiieay e ieioiay ie?iea iaoaeea, /oi iiaeao auoue eniieueciaaii a
yeaeo?ii?iiuoeaiiinoe aeey ecaioiaeaiey aunieiiiiuo nii?ioeaeaiee. A
iau/iuo oneiaeyo oeoai ia nia/eaaaony ?oooueth. Iiaa?oiinoue
iaoaeee/aneiai oee?eiiey aeae?ioiaia e ia nia/eaaaony aiaeie eee
aiaeiuie ?anoai?aie, /oi aaaeii aeey eiiaeainaoeeiiiuo onoaiiaie. Aaoiee
iaoiaeeo eniieueciaaiea aeaaiui ia?acii a yeaeo?iiiie oaoieea (eaoiaeu
oaeaaeceiiiuo o?oaie e ae?.) e yaea?iie yia?aaoeea (eae iiaeioeoaeue
iaeo?iiia). Aeey iaeee oeoaia e oee?eiiey (a aoiinoa?a a?aiia) iaeaieaa
i?eaiaeii /enoia na?aa?i.
Aaeaaiaeiay ie?iaay au?aaioea oeoaia ioeaieaaaony nioiyie ouny/ oiii.
Aeey oee?eiiey iia eiaao aeanyoie ouny/, a aeey aaoiey — eeoue nioith
oiii.
A naieo aaaeiaeoeo e iaeaieaa oa?aeoa?iuo i?iecaiaeiuo yeaiaiou
iiaea?oiiu oeoaia /aou??oaaeaioiu. Nai oeoai n?aaieoaeueii eaaei
ia?acoao iaeionoie/eaua niaaeeiaiey, a eioi?uo ii o??oaaeaioai.
I?iecaiaeiua aeaooaaeaioiiai oeoaia iaiiiai/eneaiiu e aanueia
iaonoie/eau. Oi aea ioiineony e i?iecaiaeiui o??o- e aeaooaaeaioiiai
oee?eiiey e aaoiey, niaaeeiaiey eioi?iai ii oeie/aneei naienoaai i/aiue
aeecee e niioaaonoaothuei niaaeeiaieyi oee?eiiey. Oaeei ia?acii, ii
?yaeo Ti(Zr(Hf eae?o iiieaeaiea onoie/eainoe iecoeo aaeaioiinoae, o.a.
yaeaiea, ia?aoiia oiio, eioi?ia eiaei ianoi a iiaea?oiia aa?iaiey.
I?e iaa?aaaiee yeaiaioia iiaea?oiiu oeoaia a aoiinoa?a eenei?iaea iie
nai?atho n ia?aciaaieai aaeuo aeeieneaeia (YI2). Iineaaeiea i/aiue
ooaiieaaee e i?aeoe/anee ia?anoai?eiu ie a aiaea, ie a ?acaaaeaiiuo
?anoai?ao eeneio e uaei/ae. I?e iaa?aaaiee n eiioeaio?e?iaaiiie na?iie
eeneioie iie ia?aoiaeyo a ?anoai? eeoue iaaeeaiii, ii eaaei iiaoo auoue
ia?aaaaeaiu a ?anoai?eiia ninoiyiea aeaenoaeai HF eee nieaaeaieai ni
uaei/aie. Aeeieneaeu Ti e Zr iaoiaeyo ?aciiia?aciia i?aeoe/aneia
i?eiaiaiea. A /anoiinoe, aeeieneae oeoaia neoaeeo aeey ecaioiaeaiey
i/aiue oi?ioae aaeie e?anee (“oeoaiiaua aaeeea”).
Iaa?aaaiea OiO2 (o. ie. 1870 (N) auoa 2200 (N aaae?o e /anoe/iiio
iouaieaieth eenei?iaea n ia?aciaaieai neiaai Oi3O5 (TiO2(Ti2O3) e caoai
o?iii-oeieaoiaiai Oi2O3. A noaeieueiie i?iiuoeaiiinoe aeeieneae oeoaia
i?eiaiyaony i?e ecaioiaeaiee ooaiieaaeeo no?eie, a ea?aie/aneie — /anoi
aoiaeeo a ninoaa yiaeae, aeaco?ae e oa?oi?iaie iannu. Eneonnoaaiii
iieo/aaiua a yeaeo?e/aneie ia/e i?ic?a/iua e?enoaeeu ?ooeea eiatho
iieacaoaeue i?aeiieaiey (2,6), aieueoee /ai aeiac (2,4), e a oanoue ?ac
aieaa aunieoth aeenia?neth naaoa. Iiyoiio au?aaaouaaaiua ec ieo
ae?aaioeaiiua eaiie ii e?anioa i?aainoiaeyo a?eeeeaiou. Aeeieneae oeoaia
neoaeeo oi?ioei eaoaeecaoi?ii i?e iaeioi?uo i?aaie/aneeo ?aaeoeeyo.
Aaeaaiaeiay ie?iaay aeiau/a TiO2 cinoaaeyao ieiei 1 iei. o.
I/aiue ooaiieaaeee (o. ie. 2850 (N) e a nieaaeaiiii ninoiyiee
/?acau/aeii onoie/eaue ii ioiioaieth e ?acee/iui oeie/aneei
aicaeaenoaeyi aeeieneae oee?eiiey i?eiaiyaony aeaaiui ia?acii aeey
ecaioiaeaiey iaiaoii?iuo ecaeaeee (oeaee aeey ieaaee eaa?oea e o. i.).
I?iaiaeyuea yeaeo?e/aneee oie ioo?i ia?aiina eiiia I2- oa??aeua ?anoai?u
a ZrO2 iaeioi?uo ae?oaeo ieneaeia (iai?eia?, Y2O3) eniieuecothony eae
oa??aeua yeaeo?ieeou i?e eiino?oe?iaaiee aunieioaiia?aoo?iuo oiieeaiuo
yeaiaioia. Aaaaeaiea ZrO2 a yiaeue niiauaao iineaaeiae aieueooth
e?aiinoue e yeanoe/iinoue, a oaeaea iaeioi?oth onoie/eainoue ii
ioiioaieth e oaiia?aoo?iui e oeie/aneei aicaeaenoaeyi. Niaea?aeauea ZrO2
co?eea yaeythony iniaaiii onoie/eauie ii ioiioaieth e aeaenoaeth
uaei/ae. Aeeieneae aaoiey aieaa ooaiieaaeee (o. ie. 2900 (N), /ai ZrO2.
Aeey anao yeaiaioia iiaea?oiiu oeoaia auee iieo/aiu (acaeiiaeaenoaeai
yeaiaioia i?e iaa?aaaiee) aiaeiae/iua ii ninoaao aunoei ieneaeai
noeueoeaeu, naeaieaeu e oaeeo?eaeu (e?iia HfTe2). Oeaao eo ei?e/iaaue
(e?iia ae?eoiai OiS2 e /??iiai OiTe2). Oa?ie/aneay onoie/eainoue yoeo
aauanoa iaaeaao a ?yaeo S(Se(Te, e i?e 600(700 (N iiaoo i?ioiaeeoue
niioaaonoaothuea ?aaeoeee auoaniaiey. Iiuoaie ia ni?anniaaiiuo ii?ioeao
onoaiiaeaii, /oi ii ?yaeai Ti(Zr(Hf e Te(Se(S oiaiueoaaony iaoaeee/aneee
e aic?anoaao nieaia?aciue oa?aeoa? niaaeeiaiee. I?iecaiaeiua oeoaia e
ZrTe2 iaeaaeatho iaoaeee/aneie yeaeo?ii?iaiaeiinoueth, ZrSe2, ZrS2,
HfSe2 yaeythony iieoi?iaiaeieeaie, a HfS2 — ecieyoi?ii.
Aeiaieueii oa?aeoa?iu aeey yeaiaioia iiaea?oiiu oeoaia i?iecaiaeiua
ninoaaa YO3, aaea O — S, Se, Te, eioi?ua iiaoo auoue iieo/aiu
iaiin?aaenoaaiiui acaeiiaeaenoaeai yeaiaioia i?e iaa?aaaiee. Ii
ioiioaieth e aicaeooo e aiaea iie onoie/eau, i?e iaa?aaaiee ia aicaeooa
nai?atho n ia?aciaaieai aeeieneaeia aoiaeyueo a ieo yeaiaioia. Oei? oaea
ieaea 300 (N ia?aaiaeeo eo a niioaaonoaothuea oei?eaeu YNl4 (e SCl2,
SeCl4 eee TeCl4). Onoie/eainoue yoeo aauanoa e aeaenoaeth
eiioeaio?e?iaaiiie INI oiaiueoaaony a ?yaeo S(Se(Te. E?aieei ?anoai?ii
NaOH eee eiioeaio?e?iaaiiie I2SO4 iie i?e iaa?aaaiee ?aceaaathony, a a
eiioeaio?e?iaaiiie HNO3 ieeneythony ni ac?uaii.
I?e aunieeo oaiia?aoo?ao yeaiaiou iiaea?oiiu oeoaia niaaeeiythony n
oaea?iaeii, ia?acoy ea?aeaeu oeia YN. ?aaeoeee eaeoo n auaeaeaieai
oaiea: 192 (Ti), 200 (Zr) e 217 eAeae/iieue (Hf). Ea?aeaeu Ti, Zr e Hf
i?aaenoaaeytho niaie iaoaeee/aneiai aeaea e?enoaeeu ni no?oeoo?ie oeia
NaCl, i/aiue oa??aeua e ooaiieaaeea (o. ie. niioaaonoaaiii 3250, 3735 e
3890 (N). Nieaa ninoaaa HfC(4TiC yaeyaony naiui ooaiieaaeei ec anao
ecaanoiuo aauanoa (o. ie. 3990 (N). A i?ioeaiiieiaeiinoue ea?ai?oiaeo,
yoe ea?aeaeu oi?ioi i?iaiaeyo yeaeo?e/aneee oie (eeoue iaiiiaei ooaea
niioaaonoaothueo iaoaeeia), n /ai naycaii eniieueciaaiea ea?aeaea oeoaia
i?e ecaioiaeaiee aeoaiauo eaii. Aai /anoi aaiaeyo a ninoaa ea?iaoia,
eniieuecoaiuo aeey ecaioiaeaiey ?aciiia?aciuo oa?iinoieeeo eiino?oeoeee
(eiiaoie aaciauo oo?aei e ae?.). Aaeaeo naiae aunieie oa??aeinoe OiC e
ZrC eiiaaea i?eiaiythony a ea/anoaa oeeoiaaeueiiai iaoa?eaea. I?e
aeinoaoi/iii iaa?aaaiee ea?aeaeu oeoaia e aai aiaeiaia ?aaae?otho n
aaeiaaiaie, eenei?iaeii e acioii.
Aeecei?iaenoaaiiu ea?aeaeai e iioiaee ia ieo ii naienoaai neeeoeeaeu.
Iaeaieaa oeie/iuie oi?iaie aeey ieo yaeythony YSi e YSi3.
I?e aunieeo oaiia?aoo?ao yeaiaiou niaaeeiythony n acioii. Iieo/athueany
i?e yoii iaoaeee/aneiai aeaea ae?eoua ieo?eaeu Ti, Zr e Hf eiatho
ninoaa, ioaa/athuee oi?ioea YN. Iie ia?acothony ec yeaiaioia ni
cia/eoaeueiui auaeaeaieai oaiea (niioaaonoaaiii 334, 364 e 368
eAeae/iieue) e i?aaenoaaeytho niaie i/aiue oa??aeua, ooaiieaaeea (o. ie.
2930, 2950 e 2980 (N) e i?e iau/iuo oneiaeyo oeie/anee eia?oiua
aauanoaa, i?iaiaeyuea yeaeo?e/aneie oie cia/eoaeueii eo/oa
niioaaonoaothueo naiaiaeiuo iaoaeeia. Iaa?aaaieai aei e?aniiai eaeaiey
ZrCl4 a oiea aiieaea iiaeao auoue iieo/ai ei?e/iaaue ieo?eae ninoaaa
Zr3N4 (i?iiaaeooi/iuie i?iaeoeoaie i?e yoii yaeythony ZrCl4(4NH3 e
Zr(NH2)4). Oeoai a oao aea oneiaeyo ia?acoao TiN, eioi?ue aaeaeo naiae
/?acau/aeiie oa??aeinoe i?eiaiyaony eiiaaea (aianoi aeiaciie iuee) aeey
oeeoiaee ae?aaioeaiiuo eaiiae e o. ae. Acaeiiaeaenoaea aai n ai?y/ei
?anoai?ii u?ei/e i?ioaeaao ii o?aaiaieth:
2 TiN + 4 KOH + 2 H2O = 2 K2TiO3 + 2 NH3 + H2
Ecaanoai e aeaieiie ieo?eae Li5TiN3, aiaeiae/iue i?iecaiaeiui e?aiiey e
aa?iaiey.
Aeey oinoeaeia oeoaia e aai aiaeiaia oa?aeoa?iu oeiu Y2?, Y? e Y?2. Yoi
oa??aeua na?ua aauanoaa, oa?ie/anee onoie/eaua e ia ?aaae?othuea n INl,
H2SO4 eee HNO3 (ii ?anoai?ythueany a niane HF + HNO3). Ecaanoiu oaeaea
aeaieiua niaaeeiaiey ninoaaa Li5TiP3 e Li5TiAs3.
Ioaa/athuea aeeieneaeai YI2 aeae?ieneaeu Y(II)4 iiaoo auoue iieo/aiu
aeaenoaeai uaei/ae ia niaaeeiaiey oeia YNl4. Iie i?aaenoaaeytho niaie
nooaeaienoua inaaeee, ii/oe ia?anoai?eiua a aiaea (ii eaaei ia?acothuea
eieeieaeiua ?anoai?u). Aeae?ao aeeieneaea oeoaia eiaao aioioa?iue
oa?aeoa?, i?e/?i e iniiaiua, e iniaaiii eeneioiua aai naienoaa au?aaeaiu
aanueia neaai. I?e ia?aoiaea e Zr e Hf eeneioiua naienoaa au? aieaa
ineaaaaatho, a iniiaiua oneeeaathony. O aeae?ieneaeia Y(II)4
i?aiaeaaeatho iniiaiua naienoaa, iiyoiio iie ?anoai?ythony a neeueiuo
eeneioao, oiaaea eae ?acaaaeaiiua u?ei/e ii/oe ia aeaenoaotho aeaaea ia
Ti(OH)4.
Ia?aoiae Zr(OH)4 (I? = 1(10-54) e Hf(OH)4 e aieaa aaaeiie aiaeie oi?ia
YI(II)2 inouanoaeyaony i?e 140 e 155 (N niioaaonoaaiii. ?anoai?aiea
iaieo aeae?ieneaeia a e?aieeo ?anoai?ao neeueiuo uaei/ae aaae?o e
ia?aciaaieth eiiia Y(II)5( eee Y(II)6(; ia?aue ia?acoaony i?e
eiioeaio?aoeee NaOH aei 10 i., aoi?ie i?e aieaa aunieie. Ec 15 i.
?anoai?a NaOH aue auaeaeai aaoiao Na2[Hf(OH)6].
Niee aeae?aoia aeeieneaeia n iaoaeeaie — oeoaiaou, oee?eiiaou e aaoiaou
iieo/atho nieaaeaieai aeeieneaeia n ieneaeaie yeaiaioia eee uaei/aie.
Aeey ia?acothueony nieae iaeaieaa oa?aeoa?iu oeiu I2YI3 e I4YI4 (aaea I
— iaeiiaaeaioiue iaoaee). Aieueoeinoai eo ia?anoai?eii a aiaea, a
?anoai?eiua iiaeaa?aathony iieiiio aeae?ieeco.
Ec oeoaiaoia, oee?eiiaoia e aaoiaoia iaeaieaa eioa?anai AaOiO3. Nieue
yoa yaeyaony naaiaoiyeaeo?eeii. Iia iaeaaeaao naa?oaunieie
aeeyeaeo?e/aneie i?iieoeaaiinoueth a oe?ieii eioa?aaea oaiia?aoo? (n
iaeneioiii i?e 120 (N). Naaiaoiyeaeo?e/aneea naienoaa AaTiO3 iaoneiaeaiu
aiciiaeiinoueth niauaiey eiiia Oi4( io n?aaeieo iieiaeaiee a
e?enoaeee/aneie ?ao?oea. Oaeia niauaiea aaae?o e aicieeiiaaieth
aioo?aiieo aeeiieueiuo iiiaioia, niiniaiuo i?eaioe?iaaoueny ii aiaoiaio
iieth.
Oeoaiao aa?ey eniieuecoaony aeey iieo/aiey yeaeo?e/aneeo eiiaeainaoi?ia
eneeth/eoaeueii aieueoie ?ieinoe e aaia?aoeee iiuiuo oeueo?acaoeiauo
aiei. A i?eioeeia, n aai iiiiuueth iaoaie/aneay yia?aey (iai?eia?,
ieaaie/aneeo aiei) iiaeao auoue iaiin?aaenoaaiii i?aa?auaaia a
yeaeo?e/aneoth.
Aeey yeaiaioia iiaea?oiiu oeoaia oa?aeoa?iu ia?ieneaeiua niaaeeiaiey.
Ia?ieneae oeoaia aeaaea a ie/oiaeiuo eiioeaio?aoeeyo niiauaao aiaeiiio
?anoai?o eioaineaioth ae?eooth ie?aneo. Aai ia?aciaaieai (a
neeueiieeneie n?aaea) iieuecothony iiyoiio eae /?acau/aeii
/oanoaeoaeueiie ?aaeoeeae e ia oeoai e ia ia?ieneae aiaei?iaea.
Ioaaonoaaiiui ca ie?aneo yaeyaony eii TiO2((, niaea?aeauee ia?ieneaeioth
a?oiio a o??o/eaiiii oeeeea n oeoaiii. Ioaa/athuee aio noeueoao aue
auaeaeai a aeaea e?aniiai e?enoaeeiaeae?aoa OiO2SO4(3H2O. Naycue iaaeaeo
onoie/eaui a eeneie n?aaea ia?ienieaoeiiii e onoie/eaui a uaei/iie
n?aaea ia?ieniaieiiii iiaeao auoue i?aaenoaaeaia o?aaiaieai:
TiO22+ + 3 H2O2 = TiO84( + 6 H+.
Oae eae iniiaiua naienoaa aeae?ieneaeia OiIV e aai aiaeiaia au?aaeaiu
neeueiaa eeneioiuo, ii ioiioaieth e aiaea niee aanoeaaoiuo eaoeiiia Y4(
onoie/eaaa oeoaiaoia, oee?eiiaoia e aaoiaoia. Ii aeae?ieec yoeo nieae
i/aiue cia/eoaeai e aeaaea a e?aieeo ?anoai?ao aaae?o e ia?aciaaieth
aeaooaaeaioiuo eaoeiiia oeoaieea (TiO2+), oee?eiieea (ZrO2+) e aaoieea
(HfO2+) ii noaia:
Y4+ + I2I = YI2+ + 2 I+
Iiiaea niee oeoaia e aai aiaeiaia yaeythony i?iecaiaeiuie eiaiii yoeo
?aaeeeaeia, a ia Y4+. Oaeiau (TiO)SO4(2H2O, YINl2(8H2O (aaea Y — Zr eee
Hf) e ae?. Aeaeueiaeoee eo aeae?ieec (iniaaiii i?iecaiaeiuo oeoaia)
eae?o a iaiueoae, ii an? aea neeueiie noaiaie.
Noeueoao /aou??oaaeaioiiai oeoaia Ti(SO4)2 ia?acoaony i?e
acaeiiaeaenoaee OiCl4 c SO3 e SO2Cl2. Ii i?aaenoaaeyao niaie
aanoeaaoiia, /?acau/aeii aea?ineiie/iia aauanoai. Aai oa?ie/aneia
?aceiaeaiea (a aoiinoa?a nooiai a?aiia) eae?o n iouaieaieai SO3 e
ia?aciaaieai OiOSO4 (auoa 150) eee OiO2 (auoa 430 (N). A aiaeiie n?aaea
iiaeao auoue iieo/ai oieueei noeueoao oeoaieea — OiOSO4(2H2O.
Noeueoaou /aou??oaaeaioiuo oee?eiiey e aaoiey ecaanoiu e a aacaiaeiii
ninoiyiee, e a aeaea e?enoaeeiaeae?aoia Y(SO4)2(4H2O.
A ia?acoaiuo noeueoaoaie Oi, Zr e Hf eiiieaenao n ae?oaeie noeueoaoaie
eii?aeeiaoeeiiiia /enei oeaio?aeueiiai aoiia i?e ia?aoiaea io Oi e Zr e
Hf iiauoaaony. Oae, eiiieaenu oeia I2Y(SO4)3 ecaanoiu aeey anao o??o
yeaiaioia, a oeia I4Y(SO4)4 — oieueei aeey oee?eiiey e aaoiey.
I?e iaeiia?aiaiiii iaee/ee ecauoea ENCS noeueoao oeoaieea iaaeeaiii
?anoai?yaony a aeeaeeii aiieaea. Ec ia?acothuaainy e?aniiai ?anoai?a aue
auaeaeai eiiieaeniue ?iaeaieae ninoaaa E2[TiO (NCS)4](2NH3, a aeaenoaeai
ia iaai ENH2 iieo/ai ao?ue aieae oeoaieea — OiO(NH2)2, iaaeeaiii
aeae?ieecothueeny ai aeaaeiii aicaeooa. Iiae aeaenoaeai ecauoea ENH2 ii
ia?aoiaeeo a i?aiaeaai-ei?e/iaaue OiO(NHK)2 aniuoeaathuee i?e
nii?eeiniiaaiee n aicaeooii e aiaeie. Iaa?aaaiea OiO(NH2)2
nii?iaiaeaeaaony iouaieaieai aiieaea e ia?aciaaieai neia-/??iiai
ieo?eaea oeoaieea — (TiO)3N2. Iineaaeiee ia acaeiiaeaenoaoao n aiaeie e
?acaaaeaiiuie ?anoai?aie eeneio eee uaei/ae, a i?e iaa?aaaiee ia
aicaeooa ia?aoiaeeo a TiO2.
Ieo?ao /aou??oaaeaioiiai oeoaia aue iieo/ai i?e (80 (N ii ?aaeoeee:
TiCl4 + 4 ClNO3 = 4 Cl2 + Ti(NO3)4.
Ii i?aaenoaaeyao niaie aanoeaaoiia e?enoaeee/aneia aauanoai (o. ie. 58
(N), a aaeooia i?e 40 (N aicaiiythuaany. Ia aicaeooa ieo?ao oeoaia
?aceaaaaony n ia?aciaaieai aaeiai ieniieo?aoa OiO(NO3)2, eioi?ue i?e
iaa?aaaiee ia?aoiaeeo a OiO2. Iaa niaaeeiaiey i/aiue aea?ineiie/iu e
aeae?ieeoe/anee ?aceaaathony aiaeie.
Aacaiaeiua Zr(NO3)4 e ZrO(NO3)2 ii aieueoeinoao naienoa aiaeiae/iu
niioaaonoaothuei i?iecaiaeiui oeoaia. Iaeiaei a aiaeiuo ?anoai?ao
ieo?aou oee?eiiey cia/eoaeueii onoie/eaaa. Aeey ieo ecaanoiu
e?enoaeeiaeae?aou ZrO(NO3)2(2H2O e Zr(NO3)4(5H2O. Iineaaeiyy nieue eaaei
iouaieyao /anoue aiaeu e ia?aoiaeeo a ieo?ao oee?eiieea. Aeey aaoiey
ecaanoiu e?enoaeeiaeae?aou HfO(NO3)2 n 2 e 6 iieaeoeaie aiaeu e eaoo/ee
aaeaeoeo HfO(NO3)2(N2O5.
Ia?oei?aou YI(ClO4)2 ecaanoiu a aeaea e?enoaeeiaeae?aoia (n 6 I2I aeey
Ti e n 8 I2I aeey Zr). Eioa?anii, /oi nieue oeoaieea, ieioi ?anoai?eiay
a aiaea, aaiciea, NNI4 e aeeienaia, oi?ioi ?anoai?eia a nie?oa e
aoeaoiia.
Ec i?iecaiaeiuo ae?oaeo eenei?iaeiuo eeneio aeey Zr e Hf iniaaiii
oeie/iu aeae?ioinoaou Y(I?I4)2. Iie ioee/athony oai, /oi i?aeoe/anee
ia?anoai?eiu a eeneioao (e?iia IF) e iiyoiio iiaoo auoue inaaeaeaiu a
neeueiieeneie n?aaea. Yoi aea?o aiciiaeiinoue ioaeaeyoue Zr e Hf io anao
ae?oaeo iaoaeeia (e?iia ?a). Iaei?anoai?eiu a eeneioao e eiaeaou iaieo
iaoaeeia.
Aeey oeoaia e aai aiaeiaia ecaanoiu aeeiaieyou, ia?acothueany ii noaia:
YNl4 + 4 ROH = 4 HCl + Y(OR)4.
Yoe aeeiaieyou i?aaenoaaeytho niaie aeeaeeea eee oa??aeua eaoo/ea
aauanoaa, ?anoai?eiua a aaiciea, ii aeae?ieeoe/anee ?aceaaathueany
aiaeie. I?e ?anoai?aiee a niioaaonoaothueo nie?oao iie niiniaiu
ia?aciauaaoue eiiieaeniua eeneiou oeia I2[Y(OR)6]. Eioa?anii, /oi a
oa??aeii ninoiyiee Oi(OC2H5)4 oao?aia?ai, a a aaicieueiii ?anoai?a
o?eia?ai.
Ec ae?oaeo i?iecaiaeiuo Ti, Zr e Hf iaeaieueoaa cia/aiea eiatho
aaeiaaieaeu oeia YA4. Iieo/atho eo iau/ii i?ieaeeaaieai niane aeeieneaea
yeaiaioa n oae?i a aoiinoa?a aaeiaaia. ?aaeoeey eae?o ii noaia:
YI2 + 2 N + 2 A2 = 2 NI + YA4.
Oa?aeoa? aaeiaaieaeia i?e ia?aoiaea io Ti e Zr nouanoaaiii eciaiyaony.
Oae, TiCl4 i?aaenoaaeyao niaie i?e iau/iuo oneiaeyo aeeaeeinoue, a ZrCl4
yaeyaony oeie/iie nieueth. Ca eneeth/aieai ZrF4 (e HfF4) aaeiiaaeaeu YA4
oi?ioi ?anoai?eiu a aiaea.
Iaeioi?ua naienoaa aaeiaaieaeia oeoaia niiinoaaeaiiu ieaea:
TiF4 TiCl4 TiBr4 TiI4
Oaieioa ia?aciaaiey, eAeae/iieue 1643 803 681 510
Oeaao aanoea. aanoea. ae?eo. o?iii-e?ani.
Oaiia?aoo?a ieaaeaiey, (N
(23 (39 159
Oaiia?aoo?a eeiaiey, (N 283 136 231 377
Eae ?anoai?eoaeue iai?aaie/aneeo niaaeeiaiee TiCl4 eo/oa anaai
?anoai?yao aauanoaa n oeie/iie iieaeoey?iie no?oeoo?ie. ?anoai?eiinoue a
i?i nieaia?aciuo niaaeeiaiee, eae i?aaeei, oai auoa, /ai aieueoa ?acia?u
aieiia.
I?e iinoaiaiiii aeiaaaeaiee TiCl4 e aeeaeeiio aiieaeo ia?acoaony ae?eoue
inaaeie aiieaeaoa OiCl4(6NH3. A aeaenoaeoaeueiinoe ii i?aaenoaaeyao
niaie nianue ninoaaa Ti(NH2)3Cl + 3NH4Cl, oae eae i?e ioiuaaiee aai
aeeaeeei aiieaeii NH4Cl oaeaeyaony e inoa?ony e?aniue Ti(NH2)3Cl.
Iaa?aaaiea iineaaeiaai a aaeooia nii?iaiaeaeaaony iouaieaieai NH3 n
ia?aciaaieai a inoaoea caeaiiaaoi-aieoaiai ieo?ioei?eaea NTiCl.
I?iaeoeoaie oa?ie/aneiai ?aceiaeaiey aiieaeaoia TiBr4 e TiI4 yaeythony
niioaaonoaaiii NTiBr e NTiI. Iineaaeiee auoa 400 (N ia?aoiaeeo a OiN.
Acaeiiaeaenoaea Ti(NO3)4 n KNH2 a aeeaeeii aiieaea aaae?o e ia?aciaaieth
ei?e/iaaiai Ti(NH2)4, eioi?ue eaaei ia?aoiaeeo ai ac?ua/aoue Ti(NH)2.
Aeae?ieec aaeiaaieaeia YA4 i?ioaeaao a iniiaiii ii noaiai:
ZrA4 + I2I ( ZrOA2 + 2 HA e
TiA4 + 2 H2O ( TiO2 + 4 HA.
Ia?acothueeny a ?acoeueoaoa aeae?ieeca aeae?ao aeeieneaea oeoaia
ia/eiaao inaaeaeaoueny oaea i?e ?I = 1,5. Eneeth/aieai yaeythony
ooi?eaeu, ia?acothuea n aiaeie eiiieaeniua eeneiou oeia I2[YIF4] e
iiyoiio ii/oe ia iiaeaa?aathueany aeae?ieeco aeaaea i?e iaa?aaaiee
?anoai?ia, ec eioi?uo iiaoo auaeaeyoueny e?enoaeeiaeae?aou TiF4(2H2O e
ZrF4(3H2O. A iineaaeiai ec ieo onoaiiaeaii iaee/ea aeeia?iuo iieaeoe n
ooi?eaeiuie iinoeeaie ii oeio F3ZrFFZrF3.
Ienioei?eaeu oee?eiiey e aaoiey auaeaeaiu ec ?anoai?a a aeaea
e?enoaeeiaeae?aoia YINI2(2I2I. Ieiei 150 (N oei?eae oee?eiieea
iaacaiaeeaaaony, a auoa 250 (N ?aceaaaaony ii noaia:
2 ZrOCl2 = ZrCl4 + ZrO2.
I?yiui neioacii aacaiaeiue oei?eae oee?eiieea aue iieo/ai i?e (15(N a
NNI4 ii noaia:
ZrCl4 + Cl2O = 2 Cl2 + ZrOCl2.
Ii i?aaenoaaeyao niaie aaeia e?enoaeee/aneia aauanoai, ia?anoai?eiia a
iaiiey?iuo ?anoai?eoaeyo e neeueii aeae?ieecoaiia aiaeie. Aai
e?enoaeee/aneay ?ao?oea neaaaaony ec iieeia?eciaaiiuo ioo?i ia?aciaaiey
naycae (Zr(O(Zr(O( aieiiia [ZrOCl4]2( e eaoeiiia [ZrO]2(.
Aanueia oa?aeoa?iui naienoaii aieueoeinoaa aaeiaaieaeia YA4 yaeyaony eo
neeueii au?aaeaiiay neeiiiinoue e ?aaeoeeyi i?eniaaeeiaiey. Iauei
i?eia?ii aeey anao o??o yeaiaioia iiaea?oiiu oeoaia iiaoo neoaeeoue
ae?eoua (Ti) eee aanoeaaoiua (Zr, Hf) aeaieiua niaaeeiaiey ninoaaa
YCl4(POCl3 e YCl4(2POCl3 ieaayueany niioaaonoaaiii i?e 104 e 105 (N
(Ti), 205 e 185 (N (Zr) eee 222 e 198 (N (Hf).
Aeey anao ?anniao?eaaaiuo niaaeeiaiee i/aiue oa?aeoa?ii
eiiieaeniia?aciaaiea n niioaaonoaothueie aaeiaaiiaiaei?iaeiuie eeneioaie
e iniaaiii n eo nieyie. Iaeaieaa oeie/iu eiiieaeniua i?iecaiaeiua n
iauae oi?ioeie I2YA6 (aaea I — iaeiiaaeaioiue iaoaee). Iie oi?ioi
e?enoaeeecothony e iiaeaa?aathony aeae?ieeco ai?acaei iaiaa, /ai
enoiaeiua aaeiaaieaeu YA4. Yoi oeacuaaao ia onoie/eainoue eiiieaeniuo
eiiia YA6( a ?anoai?a.
A oi a?aiy eae ii/oe ana eiiieaeniua niee Zr e Hf aanoeaaoiu, ie?anea
i?iecaiaeiuo oeoaia neeueii caaeneo io i?e?iaeu aoiaeyuaai a ieo
aaeiaaia:
Eiiieaeniay eeneioa H2[TiF6] H2[TiCl6] H2[TiBr6] H2[TiI6]
Oeaao nieae aanoeaaoiue ae?eoue e?aniue o?iii-e?aniue
Onoie/eainoue nieae eiiieaeniuo eeneio oeia I2YA6, a iauai, aic?anoaao
ii ?yaeo Ti(Zr(Hf e oiaiueoaaony a ?yaeo aaeiaaiia F(Cl(Br(I.
I?iecaiaeiua o??oaaeaioiuo yeaiaioia aieaa eee iaiaa oa?aeoa?iu eeoue
aeey oeoaia. O?iii-oeieaoiaue ieneae Oi2O3 (o. ie. 1820 (N) iiaeao auoue
iieo/ai i?ieaeeaaieai TiO2 aei 1200 (C a oiea aiaei?iaea. A ea/anoaa
i?iiaaeooi/iiai i?iaeoeoa i?e 700(1000 (N ia?acoaony neiee Ti2O3.
A aiaea Ti2O3 i?aeoe/anee ia?anoai?ei. Aai aeae?ieneae ia?acoaony a
aeaea o?iii-ei?e/iaaiai inaaeea i?e aeaenoaee uaei/ae ia ?anoai?u nieae
o??oaaeaioiiai oeoaia. Ii ia/eiaao inaaeaeaoueny ec eeneuo ?anoai?ia i?e
?I = 4, eiaao oieueei iniiaiua naienoaa e a ecauoea uaei/e ia
?anoai?yaony. Iaeiaei i?iecaiaeyueany io HTiO2 oeoaieou iaoaeeia (Li,
Na, Mg, Mn) auee iieo/aiu nooei ioo?i. Ecaanoia oaeaea neia-/??iay
“oeoaiiaay a?iica” ninoaaa Na0,2TiO2.
Aeae?ieneae oeoaia (III) eaaei ieeneyaony eenei?iaeii aicaeooa. Anee a
?anoai?a iao ae?oaeo niiniaiuo ieeneyoueny aauanoa, iaeiia?aiaiii n
ieeneaieai Ti(OH)3 eae?o ia?aciaaiea ia?ieneaea aiaei?iaea. A
i?enoonoaee Na(II)2 (naycuaathuaai I2I2) ?aaeoeey i?ioaeaao ii
o?aaiaieth:
2 Ti(II)3 + O2 + 2 H2O = 2 Ti(OH)4 + H2O2.
Acioiieeneua niee Oi(OH)3 ainnoaiaaeeaaao aei aiieaea.
Oeieaoiaue ii?ioie OiCl3 iiaeao auoue iieo/ai i?iioneaieai niane ia?ia
OiCl4 c ecauoeii aiaei?iaea neaicue iaa?aooth aei 650 (N o?oaeo.
Iaa?aaaiea aucuaaao aai aicaiieo (n /anoe/iui ia?aciaaieai aeeia?iuo
iieaeoe Ti2Cl6) e caoai aeeniooaoeeth ii noaia:
2 TiCl3 = TiCl4 + TiCl2.
Eioa?anii, /oi oaea i?e iau/iuo oneiaeyo oao?aoei?eae oeoaia iinoaiaiii
ainnoaiaaeeaaaony iaoaeee/aneie iaaeueth, ia?acoy /??iia niaaeeiaiea
ninoaaa CuTiCl4 (o. a. NuCl(TiCl3).
O??ooei?enoue oeoai ia?acoaony oaeaea i?e aeaenoaee ia TiCl4 aiaei?iaea
a iiiaio auaeaeaiey (Zn + eeneioa). I?e yoii aanoeaaoiue ?anoai?
ie?aoeaaaony a oa?aeoa?iue aeey eiiia Ti3+ oeieaoiaue oeaao, e ec iaai
iiaeao auoue auaeaeai e?enoaeeiaeae?ao ninoaaa OiCl3(6H2O. Ecaanoai e
iaeionoie/eaue cae?iue e?enoaeeiaeae?ao oiai aea ninoaaa, auaeaeythueeny
ec ianuuaiiiai HCl ?anoai?a TiCl3. No?oeoo?a iaaeo oi?i, ?aaii eae e
aiaeiae/iuo e?enoaeeiaeae?aoia NrCl3, ioaa/atho oi?ioeu [Y(II2)6]Cl3 e
[Y(II2)4Cl2]Cl(2I2I. I?e noiyiee a ioe?uoii ninoaea ?anoai? TiCl3
iinoaiaiii iaanoeaa/eaaaony aaeaeo ieeneaiey Ti3+ aei Ti4+ eenei?iaeii
aicaeooa ii ?aaeoeee:
4 TiCl3 + O2 +2 H2O = 4 TiOCl2 + 4 HCl.
Eii Oi3+ yaeyaony iaeiei ec i/aiue iaiiiaeo ainnoaiiaeoaeae, aeiaieueii
auno?i ainnoaiaaeeaathueo (a eeneie n?aaea) ia?oei?aou aei oei?eaeia. A
i?enoonoaee ieaoeiu Oi3+ ieeneyaony aiaeie (n auaeaeaieai aiaei?iaea).
Aacaiaeiue Ti2(SO4)3 eiaao cae?iue oeaao. A aiaea ii ia?anoai?ei, a
?anoai? aai a ?acaaaeaiiie na?iie eeneioa eiaao iau/ioth aeey nieae Ti3+
oeieaoiaoth ie?aneo. Io noeueoaoa o??oaaeaioiiai oeoaia i?iecaiaeyony
eiiieaeniua niee, aeaaiui ia?acii oeiia I[Ti(SO4)2](12H2O (aaea I — Ns
eee Rb) e M[Ti3(SO4)5] (n ia?aiaiiui a caaeneiinoe io i?e?iaeu eaoeiia
niaea?aeaieai e?enoaeeecaoeeiiiie aiaeu).
Niaaeeiaiey aeaooaaeaioiuo yeaiaioia iiaea?oiiu oeoaia ieioi eco/aiu.
Oaieioa ia?aciaaiey TiO (o. ie. 1750 (N) ninoaaeyao 518 eAeae/iieue. Ii
iieo/aaony a aeaea cieioenoi-ae?eoie eiiiaeoiie iannu iaa?aaaieai a
aaeooia aei 1700 (N ni?anniaaiiie niane TiO2 + Ti. Eioa?aniui niiniaii
aai ia?aciaaiey yaeyaony oa?ie/aneia ?aceiaeaiea (a aunieii aaeooia i?e
1000 (N) ieo?eea oeoaieea. Iioiaeee ii aeaeo ia iaoaee, o?iii-ei?e/iaaue
TiS iieo/ai i?ieaeeaaieai TiS2 a oiea aiaei?iaea (ia?aiia/aeueii i?e
yoii ia?acothony noeueoeaeu i?iiaaeooi/iiai ninoaaa, a /anoiinoe Ti2S3).
Ecaanoiu oaeaea TiSe, TiTe e neeeoeeae ninoaaa Ti2Si.
Ana YA2 (?aaii eae e /??iue naiiainieaiaiythueeny ia aicaeooa IfBr2)
ia?acothony i?e iaa?aaaiee niioaaonoaothueo aaeiaaieaeia YA3 aac
aeinooia aicaeooa ca n/?o eo ?aceiaeaiey ii noaia:
2 YA3 = YA4 + YA2.
I?e ianeieueei aieaa aunieeo oaiia?aoo?ao aaeiaaieaeu YA2 naie
iiaeaa?aathony aeeniooaoeee ii noaia: 2 YA2 = YA4 + Y (iai?eia?,
aeeniooaoeey ZrI3 eae?o i?e 310, a ZrI2 — i?e 430 (N).
Aeaooei?enoue oeoai iiaeao auoue iieo/ai oaeaea ainnoaiiaeaieai TiCl4
aiaei?iaeii i?e 700 (N. Ii oi?ioi ?anoai?ei a aiaea (e nie?oa), a n
aeeaeeei aiieaeii aea?o na?ue aiieaeao TiCl2(4NH3. ?anoai? TiCl2 iiaeao
auoue iieo/ai ainnoaiiaeaieai TiCl4 aiaeueaaiie iao?ey. A ?acoeueoaoa
ieeneaiey eenei?iaeii aicaeooa aanoeaaoiue ?anoai? TiCl2 auno?i ao?aao,
caoai noaiiaeony oeieaoiaui (Ti3+) e, iaeiiaoe, aiiaue iaanoeaa/eaaaony
(Ti4+). Iieo/aaiue aeaenoaeai u?ei/e ia ?anoai? TiCl2 /??iue inaaeie
Ti(OH)2 eneeth/eoaeueii eaaei ieeneyaony.
PAGE
PAGE 10
Нашли опечатку? Выделите и нажмите CTRL+Enter
