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Комплексні сполуки титану (IV) та цирконію (IV) з ортофосфатною та оксиетилідендифосфоновою кислотами: Автореф. дис… канд. хім. наук / І.В. Романова

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IAOe?IIAEUeIA AEAAeAI?ss IAOE OE?A?IE

?INOEOOO CAAAEUeII? OA IAI?AAI?*II? O?I??

?i. A.?.AA?IAAeNUeEIAI

?IIAIIAA ??EIA A?EOI??AIA

OAeE 541.49+546.821+546.831

EIIIEAENI? NIIEOEE

OEOAIO (IV) OA OeE?EII?TH (IV) C I?OIOINOAOIITH OA
IENEAOEE?AeAIAeEOINOIIIAITH EENEIOAIE

02.00.01. – iai?aai?/ia o?i?y

A A O I ? A O A ? A O

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?i?/ieo iaoe

EE?A -1999

Aeena?oaoe??th ? ?oeiien.

?iaioa aeeiiaia a ?inoeooo? ni?aoe?? oa i?iaeai aiaeiaeieia??

IAI Oe?a?ie.

Iaoeiaee ea??aiee: aeieoi? o?i?/ieo iaoe, aeaaeai?e

No?aeei Aieiaeeie?
Aaneeueiae/.

aee?aeoi? ?NIA IAI
Oe?a?ie

Io?oe?ei? iiiiaioe: aeieoi? o?i?/ieo iaoe, no.i.ni?a.

Iaii?ee Iao?i
Aiae??eiae/,

caa.a?aeae?eii
?inoeoooo o?ce/ii? o?i??

?i.E.A.Iena?aeaanueeiai
IAI Oe?a?ie

aeieoi? o?i?/ieo iaoe,
a.i.i?ioani?a

Aio?aioeaaa Iaae?y
Ieoae?aia,

Iaoe?iiaeueiee aa?a?iee
oi?aa?neoao

I?ia?aeia onoaiiaa: Ee?anueeee Oi?aa?neoao ?i.Oa?ana Oaa/aiei,

o?i?/iee oaeoeueoao.

Caoeno a?aeaoaeaoueny “24” ethoiai 1999 ?. i 10 aiaeei? ia can?aeaii?
Niaoe?ae?ciaaii? a/aii? ?aaee Ae 26.218.01 a ?inoeooo? caaaeueii? oa
iai?aai?/ii? o?i?? ?i. A.?.Aa?iaaenueeiai IAI Oe?a?ie ca aae?anith:
252680, Ee?a-142, i?. Iaeaae?ia, 32/34 (eiioa?aioe-cae).

C aeena?oaoe??th iiaeia iciaeiieoenue a a?ae?ioaoe? ?inoeoooo caaaeueii?
oa iai?aai?/ii? o?i?? ?i. A.?.Aa?iaaenueeiai IAI Oe?a?ie.

Aaoi?aoa?ao ?ic?neaiee “17” n?/iy 1999 ?.

A/aiee nae?aoa? Niaoe?ae?ciaaii?

a/aii? ?aaee, aeieoi? o?i?/ieo iaoe
A.A.Iaiia.

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue ?iaioe. Iai?aai?/i? ?iiiiai?iieee, iniaeeai a?ae?aoiaai?
ieneaee oa oinoaoe aeaiaio?a III-V a?oie Ia??iaee/ii? nenoaie, aaea
a?eueoa 50 ?ie?a ?aoaeueii aeine?aeaeothoueny, ye iaea?eueo ia?niaeoeai?
iaoa??aee aeey aeei?enoaiiy o i?ioeanao ni?aoe?eii? ia?a?iaee
iai?ii?iaiiai yaea?iiai iaeeaa, a oaeiae o ??oaii? i?iaeai
eiioeaio?oaaiiy ?aae?iioee?ae?a oa iiaeaeueoiai ?o ciaoeiaeaeaiiy.
I?aeaeuaia oaaaa aei iai?aai?/ieo ?ii?o?a iia’ycaia c ?o aenieith
o?i?/iith, oa?i?/iith, ?aae?aoe?eiith oa i?e?ia?ieia?/iith no?ee?noth oa
iniaeeai c aino?inaeaeoeaiei oa?aeoa?ii ?o ni?aoe?eii? ae?? ii
a?aeiioaiith aei a?eueoino? ?aae?iaeoeaieo ?cioii?a oa ?ii?a aaaeeeo
iaoae?a. Ni?aoe?ei? aeanoeaino? oaeeo iaoa??ae?a caeaaeaoue a?ae
aaiiao?e/ii? aoaeiae iao?eoe? oa a?ae i?e?iaee ooieoe?iiaeueieo a?oi ia
iiaa?oi? ni?aaioo.

Ia no/aniiio aoai? aeieia?/ieo aeine?aeaeaiue iaoa??aee ia iniia?
oinoao?a oeoaio oa oee?eii?th (OO ? OOe) caeiathoue iaeia c i?ia?aeieo
i?noeue. Aieiaiei iai?yieii ?ia?o ? ?ic?iaea iaoiae?a neioaco iiaeo
iaoa??ae?a oa aeine?aeaeaiiy ?o iieaeoey?ii? aoaeiae. A a?eueoino?
aeiaaee?a i?ioean neioaco caiaeeoueny aei ci?oaiiy ?iai/eo ?ic/ei?a
(nieae O?(IV) i Zr(IV) c i?oioinoaoiith eeneioith, /e ?? nieyie) ?
iiaeaeueoiai aei?noeiai aieeao ia io?eiai? niieoee. Iiaeia ciaeoe
o?eueee iiiaeeiie? ?iaioe, a yeeo ?iaeeeny ni?iae aeine?aeeoe o?i?th
i?ioean?a ia?oiai aoaio neioaco oeeo aaaeeeaeo iaoa??ae?a, a naia
aca?iiae?th a aiaeieo ?ic/eiao, yea aaciina?aaeiuei ca’caia c
eiiieaeniooai?aiiyi. I?ae oei c?icoi?ei, ui naia ia oeueiio aoai?
caeeaaeathoueny iniiae iieaeoey?ii? no?oeoo?e iai?aai?/iiai
?iiiiai?iieea ? a?i ? aecia/aeueiei ii a?aeiioaiith aei oi?ioaaiiy
ni?aoe?eieo aeanoeainoae.

O ca’yceo c oeei iniiaiei caaaeaiiyi oe??? ?iaioe aoei aeaoaeueia
aeine?aeaeaiiy iniaeeainoae eiiieaeniooai?aiiy Ti(IV) i Zr(IV) c
i?oioinoaoiith (IO) oa ieneaoee?aeaiaeeoinoiiiaith eeneioaie (IAAeO),
inoaiiy aea/aeanue ye ia?niaeoeaiee oaeaooth/ee aaaio.

Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie. ?iaioa aeeiiaia o
a?aeiia?aeiino? c ieaiii iaoeiai-aeine?aeieo ?ia?o ?inoeoooa ni?aoe?? oa
i?iaeai aiaeiaeieia?? IAI Oe?a?ie : aea?aeaaii-athaeaeaoieie oaiaie 174
IO (1991-1996), 5A (1996), 6IO (1996-1997), 7IO (1997-1998).

Iaoa ?iaioe. Aeyaeaiiy aieeao eiiieaeniooai?aiiy ia oi?ioaaiiy a
?ic/ei? iie?yaea?ieo niieoe oa oai?aoe/ia iaa?oiooaaiiy iiaeeeaino?
ni?yiiaaiiai neioaco ni?aaio?a c aaaaeaiiyi o eiai no?oeoo?o
aeiaeaoeiaiai iie?oinoaoiiai e?aaiaeo, ia ?ieue yeiai ia?aii a?aeiiee
eiiieaenii – ieneaoee?aeaiaeeoinoiiiao eeneioo (IAAeO).

Iaoeiaa iiaecia aeine?aeaeaiue. Aia?oa i?iaaaeaii nenoaiaoe/i?
aeine?aeaeaiiy eiiieaeniooai?aiiy oeoaio oa oee?eii?th o aiaeieo
?ic/eiao c i?oioinoaoiith oa ieneaoee?aeaiaeeoinoiiiaith eeneioaie a
caeaaeiino? a?ae ?I ?ic/eio, eiioeaio?aoe?e oa ni?aa?aeiioaiue
eiiiiiaio?a. Iaoiaeaie ?I–iioaioe?iiao??? oa ssI?-niaeo?ineii??
anoaiiaeaii neeaae eiiieaen?a oa eiai ci?io ia i?ioyc? /ano. Aeyaeaii
oiiae, a yeeo ooai?ththoueny iie?yaea?i? niieoee, caeaoi? i?iyaeyoe
?iiiiai?ii? aeanoeaino?.

Aia?oa, ia iniia? aeaieo ssI?-niaeo?ineii??, c?iaeaii aeniiaie i?i
iayai?noue aca?iiae?? i?ae i?oioinoaoiith oa ieneaoee?aeaiaeeoinoiiiaith
eeneioaie o aiaeieo ?ic/eiao, ui a?aee?eaa? iiaeeea?noue aeey
iiaeeo?eaoe?? oinoao?a oeoaio oa oee?eii?th oaeaooth/eie a?oiaie.

I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a. ?acoeueoaoii
i?iaaaeaieo aeine?aeaeaiue eiiieaeniooai?aiiy nieae oeoaio oa oee?eii?th
a aiaeieo ?ic/eiao c i?oioinoaoiith eeneioith aoei io?eiaiiy aeaieo, ye?
iiaeia aeei?enoiaoaaoe aeey i?iaiicoaaiiy aeanoeainoae ni?aaio?a ? aeey
ni?yiiaaiiai neioaco iiaeo iaoa??ae?a ia iniia? oinoao?a oeoaio oa
oee?eii?th. Iaea?aeai? ?acoeueoaoe iiaeia oaeiae ?icaeyaeaoe, ye aacia?
aenia?eiaioe aeey aaaaeaiiy eiiieaeniooai?thth/eo a?oi IAAeO o iao?eoeth
ni?aaioo ia noaae?? eiai oi?ioaaiiy.

Iniaenoee aianie caeiaoaa/a. Io?eiaiiy an?o aenia?eiaioaeue-ieo
aeaieo, ?o ia?iaea oa aiae?c, oi?ioethaaiiy aeniiae?a c?iaeaii
aaciina?aaeiuei aaoi?ii. Iinoaiiaea aeine?aeaeaiue, iaaiai?aiiy
iaea?aeaieo ?acoeueoao?a oa i?aeaioiaea ioae?eaoe?e aeeiiaia ?acii c
iaoeiaei ea??aieeii, aeaaeai?eii, ae.o.i. A.A.No??eei. Aeine?aeaeaiiy
iaoiaeii ssI? oa o?aeoiaeo niaeo??a i?iaaaeaii ?acii c ae.o.i.
I.A.Eino?ii?iith oa e.o.i. A.A.O?a/aanueeei.

Ai?iaaoe?y ?iaioe. Iniiai? ?acoeueoaoe ?iaioe aeiiia?aeaeenue ia
6 Iaoeiai-oaoi?/iiio nai?ia?? ii oinoi?o “Iaoeia? ? iaoa??aeiciaa/?
i?iaeaie o?i?? oinoi?o oa eiai niieoe” (i.Euea?a, 1993) oa XIV
Oe?a?inuee?e eiioa?aioe?? c iai?aai?/ii? o?i?? (i.Ee?a, 1996 ?.).

Ioae?eaoe??. Ca ?acoeueoaoaie ?iaioe iioae?eiaaii 6 noaoae oa oace
2 aeiiia?aeae.

Iaoiaeieia?y. Aenia?eiaioaeueia /anoeia ?iaioe aeeiiaia c
aeei?enoaiiyi iaoiaeo ssI? ia yae?ao 1I, 13N ? 31?, ?I-iioaioe?iiao???
oa aeaiaioiiai aiae?co.

No?oeoo?a ?iaioe. Aeena?oaoe?eia ?iaioa neeaaea?oueny c anooio,
iaeyaeo e?oa?aoo?e, aenia?eiaioaeueii? /anoeie, 5 ?icae?e?a iaaiai?aiiy
?acoeueoao?a, aeniiae?a ? nieneo aeei?enoaieo e?oa?aoo?ieo aeaea?ae (180
iaeiaioaaiue). ?iaioa i?noeoue 14 oaaeeoeue e ?ethno?iaaia

26 ?enoieaie. Caaaeueiee ianya aeena?oaoe?? – 143 noi??iee.

INIIAIEE CI?NO ?IAIOE.

A iaeyae? e?oa?aoo?e (?icae?e 1), yeee neeaaea?oueny c aeaio /anoei,
i?iaaaeaii aiae?c e?oa?aoo?ieo aeaieo uiaei aca?iiae?? nieae oeoaio oa
oee?eii?th c i?oioinoaoiith eeneioith (aeeth/a? neioac niieoe ??ciiai
neeaaeo oa aea/aiiy ?o o?ce/ieo ? o?i?/ieo aeanoeainoae, a oaeiae
io?eiaiiy ?iiiiai?iieo iaoa??ae?a) oa iaeyae eiiieaeniooai?thth/eo
aeanoeainoae IAAeO. Oaeiae a aeaiiio ?icae?e? iaa?oioiaaii aea??
ia’?eo?a oa iaoiae?a aeine?aeaeaiiy.

A aenia?eiaioaeuei?e /anoei? (?icae?e 2) ei?ioei iienaii iaoiaee
aeine?aeaeaiiy oa oiiae i?iaaaeaiiy aenia?eiaioo, cacia/aii aeei?enoai?
?aaeoeae oa i?eeaaee.

?icae?e 3 i?enay/aii aeine?aeaeaiith iniiaiino? oa aoaeiae IAAeO,
ianaiia?aae, ieoaiith i?i iiaeeea?noue ooai?aiiy eiiieaen?a c eae??i oa
aeenioe?aoe?th nie?oiai? a?oie. Aeey oeueiai aeei?enoaii aeaa iaoiaee:
?I-iioaioe?iiao??y ? ssI?-niaeo?ineii?y ia yae?ao 1I, 13N ? 31?.
I?iaaaeaii oeo?oaaiiy ?ic/eiii EII na??? ?ic/ei?a IAAeO (eiioe. 1.10-3;
1.10-2; 1.10-1 iieue/e) oa iaoeeaiaeeoinoiiiai? eeneioe (IAeO), aiaeiaa
IAAeO, aea aei ?? neeaaeo ia aoiaeeoue nie?oiaa a?oia:

IAAeO IAeO

E?ea? oeo?oaaiiy na??? ?ic/ei?a IAAeO oa IAeO iaaaaeaii ia
?en.1.A?ae?aco i?ney i?eaiooaaiiy ?ic/ei?a e?ea? oeo?oaaiiy IAAeO ? IAeO
ianooo?ai a?ae??ciythoueny a eoaeiiio na?aaeiaeu? (e?ea? 1,3), no?eaee
?I a?aeaoaathoueny i?e 2 oa 3-o aea?aaeaioao. Anoaiiaeaiiy ??aiiaaae
i?ecaiaeeoue aei cieaeaiiy ?I a iaio nenoaiao ? cnoao ae?oaiai no?eaea
?I aei 4 (IAeO) ? 5 (IAAeO) aea.EII (2,4). Cieaeaiiy ?Eaeen. /aoaa?oiai
oa i’yoiai i?ioiio IAAeO oa /aoaa?oiai IAeO iiaeia iiynieoe ooai?aiiyi
eiiieaen?a c eae??i, i?e/iio o aeiaaeeo IAAeO a i?ioean? i?eeia?
o/anoue nie?oiaa a?oia (cieaeaiiy ?I o ii??aiyii? c IAeO).

Ca?eueoaiiy eiioeaio?aoe?? IAAeO ( N= 1.10-2 iieue/e) ia aeeeeea?
nooo?a? ci?ie o oiae? e?eai? (5). I?e N=1.10-1 iieue/e ia e?ea?e
oeo?oaaiiy IAAeO ? o?e no?eaea ?I i?e 2, 3-o oa 4 aea.EII (e?eaa 6),
cieaeaiiy ?I, iaoiiaeaia aca?iiae??th c eae??i, ia niinoa??aa?oueny.

?en.1. E?ea? ?I-iioaioe?iiao?e/iiai oeo?oaaiiy IAeO (1,2) oa IAAeO
(3-6), a?ae?aco i?ney i?eaiooaaiiy ?ic/ei?a (1,3) oa i?ney anoaiiaeaiiy
??aiiaaae (2,4-6).

NIAeO=1.10-3 iieue/e; NIAAeO=1.10-3(3,4), 1.10-2 (5), 1.10-1(6).

Aeey ??oaiiy ieoaiiy i?i aeenioe?aoe?th nie?oiai? a?oie a
eiioeaio?iaaieo ?ic/eiao (1.10-1 i/e ) aeei?enoaii iaoiae ssI?. A
niaeo?ao 1I niinoa??aaany o?eieao iaoeeueieo i?ioii?a, a niaeo?ao 31? ?
13N1 – eaaae?oieao (aca?iiae?y c i?ioiiaie NI3-a?oie), a niaeo?? 13N2
o?eieao (aca?iiae?y N2-?). A oaae.1 iaaaaeaii cnoa oeaio?o aaae
neaiae?a o?ueio yaea? ii a?aeiioaiith aei aeo?aeii? oi?ie oa cia/aiiy
Jc-p a caeaaeiino? a?ae oi?ie IAAeO a ?ic/ei?.

Oaaeeoey 1.

Iieiaeaiiy oa cnoa neaiae?a 1I, 13N, 31? (i.ae.) oa cia/aiiy Jc-p aeey
??cieo oi?i IAAeO.

Oi?ia I N1 N2 ? Jc-p

Ae Aeae Ae Aeae ae Aeae Ae Aeae

H5L 1,6 0 19,6 0 70,5 0 19,8 0 152

H3L2- 1,49 0,11 20,2 -0,6 71,5 -1 19,2 0,6 140

H2L3- 1,41 0,8 20,7 -0,5 71,7 -0,2 19,4 -0,2 130

L5-,KL4- 1,32 0,9 23,2 -2,44 74,5 -2,7 18,7 0,7 137

Cnoa on?o neaiae?a ssI? niinoa??aa?oueny a i?ii?aeeao ?I=1-3 oa 6-7, a
oaeiae i?e cia/aiiyo ?I=10-13 (aeea.oaae.). Iaea?eueoee cnoa neaiae?a N2
? N1 a?aeaoaa?oueny i?e ?I>10 , a?i cia/ii ia?aaeuo? ca aaee/eiith cnoa
a?aeiia?aeieo neaiae?a i?e aeenioe?aoe?? oinoiiiaeo a?oi. Oea iiaeia
iiynieoe eeoa aeenioe?aoe??th nie?oiai? a?oie, yea ?icoaoiaaia o
aaciina?aaei?e aeecueeino? aei aoii?a aoaeaoeth, ? ooai?aiiyi ai?ii?a
L5-. Aiae?c iai?yieo cnoa?a ??cieo yaea? i?e aeenioe?aoe?? aeicaieea
aeyaeoe iayai?noue aiaeiaaeo ca’yce?a a /anoeiai i?ioiiiaaieo oi?iao oa
cai?iiiioaaoe iiaeae? ai?iiieo oi?i.

A ?icae?eao 4 -5 iaaaaeaii ?acoeueoaoe aea/aiiy i?ioean?a
eiiieaeniooai?aiiy O?(IV) oa Zr(IV) c i?oioinoaoiith eeneioith oa IAAeO
iaoiaeii ?I-iioaioe?iiao???. I?iaaaeaii oeo?oaaiiy aeo?aeieo eiiiiiaio?a
oa ?o noi?oae c? ni?aa?aeiioaiiyie I:IO,IAAeO=1:0,25; 1:0,5; 1:1; 1:2 ?
1:4, aeo?eiaieo aei anoaiiaeaiiy ??aiiaaae, i?e aeaio eiioeaio?aoe?yo
nie? iaoaeo (1.10-3 ?1.10-2 iieue/e). I?e eiioeaio?aoe?yo 1.10-2 iieue/e
? 1.10-1 iieue/e i?iaiaeeee aeine?aeaeaiiy ci?ie ?I ia i?ioyc? /ano a
na??? ?ic/ei?a c? ni?aa?aeiioaiiyi 1:1 ? 1:2 ? ??ciith e?euee?noth EII
(a?ae 1 aei 7 aea?aaeaio?a). E?ea? ?I-iioaioe?iiao?e/iiai oeo?oaaiiy
aeey nenoaie I3?I4- TiCl4-I2I iaaaaeaii ia ?en.2.

?en.2. E?ea? ?I-iioaioe?iiao?e/iiai oeo?oaaiiy noi?oae TiCl4 ?

I3?I4 c? ni?aa?aeiioaiiyie 1:1,25(1), 1:0,5(2), 1:1(3), 1:2(4),

1:4(5).NO?= 1.10-3 (—-) ? 1.10-2 iieue/e (____).

A?aei?iiino? e?eaeo i?e aeaio eiioeaio?aoe?yo:

Iayai?noue inaae?a i?e NO?=1.10-2 iieue/e oa an?o ni?aa?aeiioaiiyo
eiiiiiaio?a (e??i 1:4), i?e iaiueo?e eiioeaio?aoe?? inaaee ia
aeiaaeathoue.

Cnoa no?eae?a ?I a noi?iio a?eueoeo cia/aiue, iniaeeai a eeneiio
na?aaeiaeu?, i?e i?aeaeuaii? eiioeaio?aoe??.

Aeey aecia/aiiy neeaaeo inaaeo i?e ??cieo ni?aa?aeiioaiiyo (1:0,5; 1:1
oa 1:2) aoei aecia/aii ai?no oeoaio oa oinoaoii? eeneioe o o?eueo?aoao.
Io?eiai? ?acoeueoaoe aeicaieeee c?iaeoe aeniiaie, ui i?e an?o
ni?aa?aeiioaiiyo c ?ic/eio aeiaaea? niieoea aea?iiey?iiai neeaaeo –
[Ti(OH)2HPO4]0 (?I7 8-10 [Ti(OH)2HPO4]0 [Ti(OH)2 (HPO4 )2]2- [Ti(OH)2 (PO4)2]4-
[Zr(OH)2HPO4]0 [Zr(OH)2 (HPO4)2]2-

1:4 2-6 >6 [Ti(OH)2 (HPO4 )2]2- [Zr(OH)2 (H2PO4 )2]0 [Zr(OH)2
(HPO4)(H2PO4)]- [Zr(OH)2 (PO4)2]4-

NI=1.10-2 iieue/e.

Ni?aa I:IO ?I Neeaae eiiieaen?a a ?ic/ei? oa inaae?

O? Zr

1:0,5 2 8-9 >10 [Ti(OH)2HPO4]n [Ti(OH)2KPO4]n [Ti(OH)2]2PO4+
[Zr(OH)2HPO4]n [Zr(OH)2KPO4]n

1:1 2 3-9 >10 [Ti(OH)2HPO4]n [Ti(OH)2KPO4]n [Ti(OH)3PO4]2-
[Zr(OH)2HPO4]n [Zr(OH)2KPO4]n

1:2 2 3-6 >7 [Ti(OH)2HPO4]n [Ti(OH)2KPO4]n [Ti(OH)3 (PO4)2]4-
[Zr(OH)2(KHPO4)(H2PO4)]n [Zr(OH)2(KHPO4)2]n

1:4 2-6 >7 [Ti(OH)2 (HPO4 )2]2- [Ti(OH)2 (PO4)2]4-
[Zr(OH)2(KHPO4)(H2PO4)]n [Zr(OH)2(KHPO4)2]n

Iniiai? a?aei?iiino?, oa?aeoa?i? aeey nenoai c oee?eii??i: no?eaee ?I ia
e?eaeo oeo?oaaiiy niinoa??aathoueny i?e iaio?e e?eueeino? aea?aaeaio?a
eoao, ui iiaeia iiynieoe ??ciei neeaaeii aeo?aeieo oi?i a?ae?ieneae?a
iaoae?a – [O?(OH)3+ ]n ? [Zr(OH)2 2+]n. I?e eiioeaio?aoe?? 1.10-3
iieue/e ia aeiaaeathoue inaaee, ye ? a nenoai? c oeoaiii, i?e eiioe.
1.10-2 iieue/e – inaae?a iaia? eeoa i?e ni?aa?aeiioaii? 1:0,25.

Neeaae eiiieaen?a oeoaio ? oee?eii?th (aeea.oaae.) i?e iaio?e
eiioeaio?aoe?? ni?aiaaea?. I?e i?aeaeuaii? eiioeaio?aoe?? ?ica?aeiino?
aeieeathoue o ca’yceo c a?aei?iiinoyie a i?e?iae? iaoae?a. I?e
iaeiaeiaeo oiiaao oee?eii?e eaaoa ooai?th? iie?yaea?i? eiiieaene
neeaaeo 1:1 oa 1:2, oiae? ye aeey oeoaio inoaii? niieoee ?ic/eii?.

A nenoaiao c oee?eii??i (ni?aa.1:0,5 oa 1:2) anoaiiaeaii cieaeaiiy
?I ia i?ioyc? /ano ? cnoa no?eaea ?I a noi?iio a?eueoeo aea?aaeaio?a
eoao. Oea iaoiiaeaii ooai?aiiyi iie?yaea?iiai eiiieaeno [Zr(OH)2KPO4]n
(aiaeia?/ii oeoaio). Cieaeaiiy ?Eaeen. i?ioiio a oaeeo eiiieaenao (aeey
aeaio iaoae?a) iiaeia iiynieoe ooai?aiiyi iie?ia?ii? no?oeoo?e, yea
neeaaea?oueny c oa??a –I –I –I – . Iaca’ycai? c iaoaeii oinoi?i? a?oie
?icoaoiaothoueny i?ae oa?aie ? c’?aeiai? aiaeiaaeie ca’yceaie. Oaeei
/eiii i?ioiie ia?aaoaathoue a ioi/aii? aenieica?yaeaeaieo ?ii?a, ui
i?eaiaeeoue aei iineaaeaiiy ?o ca’yceo c aoiiaie eenith. A?aenooi?noue
inaae?a o nenoaiao c oee?eii??i i?e /ioe?ueioe?aoiiio iaaeeeoeo
inoaiiueiai ie iiynith?ii ooai?aiiyi eiiieaen?a neeaaeo 2:1 –
[Zr4(OH)8(HPO4)2]4+ (ooai?aiiy oao?aia??a oa?aeoa?ii aeey oee?eii?th).

Oa?aeoa? e?eaeo ?I-iioaioe?iiao?e/iiai oeo?oaaiiy aeey nenoai ca
o/anoth IAAeO iiae?aiee aei nenoai c i?oioinoaoiith eeneioith. A?eueo?
cia/aiiy aea?aaeaio?a EII, i?e yeeo i?ioiaeyoue no?eaee ia e?eaeo
oeo?oaaiiy, iia’ycai? c a?eueoith iniiai?noth eeneioe ? e?euee?noth
ca’ycaieo oinoi?ieo a?oi. I?e NI =1.10-3 iieue/e a nenoaiao ia
aeiaaeathoue inaaee, NI =1.10-2 ? 1.10-1 – inaaee aeiaaeathoue i?e
iaaeeeoeo iaoaeo ? aea?iiey?ieo ni?aa?aeiioaiiyo eiiiiiaio?a.

?ic?aooiee neeaaeo eiiieaen?a i?iaiaeeee ii noai?, aiaeia?/i?e
nenoaiai c oinoaoiith eeneioith. Oaeiae a?aoiaoaaee oa, ui oi?ia
e?aaiaeo o neeaae? eiiieaeno ia iiaea aooe a?eueo i?ioiiiaaiith, i?ae a
aeii?ioth/?e oi?i? IAAeO a ?ic/ei? (i?e a?aenooiino? iaoaeo). Neeaae
eiiieaen?a a inaae? ? a ?ic/ei? a caeaaeiino? a?ae eiioeaio?aoe??,
ni?aa?aeiioaiiy eiiiiiaio?a oa ?I na?aaeiaeua, iaaaaeaii a oaae.3.

Oaaeeoey 3

Neeaae eiiieaen?a oeoaio oa oee?eii?th c ieneaoee?aeaiaeeoinoiiiaith
eeneioith.

NI =1.10-3 iieue/e

Ni?aa I:IAAeO ?I Neeaae eiiieaen?a a ?ic/ei? ? a inaae?

O? Zr

1:0,25 >3 [(Ti(OH)2 )2H3L]2+ [(Zr(OH)2 ) 2 )H3L ]2+

1:0,5 >7 [(Ti(OH)2)2HL]0 [(Zr(OH)2)2HL]0 [(Zr(OH)2)2L]-

1:1 >3 >7 [Ti(OH)2H2L]- [Ti(OH)2HL]2- [Zr(OH)2H2L]- [Zr(OH)2HL]2-

1:2 >3 >7 [Ti(OH)2H2L]- [Ti(OH)2 (H2L)2]4- [Zr(OH)2H2L]- [Zr(OH)2
(H2L)(HL)]5-

1:4 >3 >7 [Ti(OH)2 (H2L)2]4- [Ti(OH)2 (H2L)(HL)]5- [Zr(OH)2(H2L)(H3L)]3-
[Zr(OH)2(HL)2]6-

NI =1.10-2 iieue/e

Ni?aa I:IAAeO ?I Neeaae eiiieaen?a a ?ic/ei? ? a inaae?

O? Zr

1:0,25 >2 [Ti(OH)2K2 HL]n [Zr(OH)2 KH2L]n

1:0,5 >7 [(Ti(OH)2K2 HL]n [Zr(OH)2K2 HL]n

1:1 >3 >7 [Ti(OH)2K2 HL]n [Ti(OH)2L]3- [Zr(OH)2KH2L]n [Zr(OH)2K2 HL]n

1:2 >3 >7 [Ti(OH)2 (H2L)2]4- [Ti(OH)2 (H2L)(HL)]5- [Zr(OH)2 KH2L]n
[Zr(OH)2 (H2L)(HL)]5-

1:4 >3 >7 [Ti(OH)2 (H2L)2]4- [Ti(OH)2 (H2L)(HL)]5- [Zr(H2L)(H3L)]-
[Zr(H2L)2]2-

I?e iaeiaioeo eiioeaio?aoe?yo (NI =1.10-3 iieue/e) neeaae eiiieaen?a
oeoaio oa oee?eii?th iaeiaeiaee. Aea/aiiy nenoai c a?eueoith
eiioeaio?aoe??th (1.10-2 i/e) aeyaeei ooai?aiiy iie?yaea?ieo niieoe (ia
i?ioyc? /ano ?I cieaeo?oueny), a yeeo iaeei aai aeaa i?ioiie
cai?uothoueny ia ?iie eae?th. Cai?uaiiy aeaio i?ioii?a a nenoai? c
oeoaiii a?aeaoaa?oueny i?e ?I>3, c oee?eii??i >7 (aeea.oaae.).

sse ? a nenoaiao c i?oioinoaoiith eeneioith i?iya ?iiiiai?iieo
aeanoeainoae iiaeia iiynieoe ooai?aiiyi no?oeoo?, a yeeo i?ae ieiueiaie
aenieica?yaeaeaieo ?ii?a ?icoaoiaaii iaca’ycai? oinoiiia? oa nie?oia?
a?oie.

A?aei?iiino? o neeaae? eiiieaen?a oeoaio oa oee?eiieth c IAAeO
aeyaeythoueny i?e ni?aa?aeiioaii? 1:2: oeoai ooai?th? eiiieaene c aeaiia
e?aaiaeaie a eeneiio oa eoaeiiio na?aaeiaeu?, oee?eii?e – eeoa a
eoaeiiio. E??i oiai i?e ni?aa?aeiioaii? 1:4 aeey oee?eii?th oa?aeoa?ii
ooai?thaaoe eiiieaene, aei neeaaeo yeeo a?i aoiaeeoue o
iaa?ae?ie?ciaaiiio noai?.

?icae?e 6 i?noeoue aeai? uiaei aea/aiiy aeaieo nenoai (N=1.10-1
iieue/e) iaoiaeii ssI? ia yae?ao 31?. Iaoith oeeo aeine?aeaeaiue aoei
io?eiaiiy aeiaeaoeiaeo a?aeiiinoae i?i oi?io a?ae?ieneae?a oeoaio oa
oee?eii?th o neeaae? eiiieaen?a (e?euee?noue a?ae?ieneeueieo a?oi) oa
iiaeeea?noue ni?a?nioaaiiy oi?i I(II)?-oHn-oL. ?aoaeueii aea/aeenue
nenoaie c? ni?aa?aeiioaiiyi I:E=1:1 ? 1:2, ye aeiiii?aei? aeei?enoaii
niaeo?e nenoai 2:1 ? 1:4 a eoaeiiio na?aaeiaeu?.

A niaeo?ao nenoai I-I3?I4 (1:1, ?ic/ei iaae inaaeii, ?I=1,5-10)
neaiae 31? ia cao?eniaaii, ui aeaco? ia a?aenooi?noue iiiiyaea?ieo
niieoe. I?e ni?aa?aeiioaii? 1:2 (O?, ?I=1-5) niinoa??aaany neiaeao 31?
(?=0,38 i.ae.), yeee a?aeiia?aea? neaiaeo iaca’ycaii? oinoaoii? eeneioe
(?en.4). A inaae? caeeoa?oueny eiiieaen aea?iiey?iiai neeaaeo
[Ti(OH)2EPO4]n (5 aea.eoao). I?e aeiaeaaaii? oinoiai aea?aaeaioo EII
inaae iinooiiai ?ic/eiy?oueny, ui noi?iaiaeaeo?oueny cnoaii neaiaeo 31?
a neeueia iiea. ?ic/eiaiiy inaaeo ? i?aeaeuaiiy ?I, ii??aiyii c /enoith
i?oioinoaoiith eeneioith (aeea.?en.), aeaco? ia o/anoue o
eiiieaeniooai?aii? ae?oaiai caeeoeo eeneioe ? iaioo e?euee?noue
a?ae?ieneeueieo a?oi, ca’ycaieo c oeoaiii: [Ti(OH)(PO4)2]3-(6 aea.EII).

A nenoai? Zr-IO aei ?I=5,5 neaiae 31? a ?ic/ei? a?aenooi?e, iio?i
c’yaey?oueny neaiae ?=0,38 i.ae., ui iiynith?oueny ooai?aiiyi eiiieaeno
neeaaeo 1:1 a inaae?, a ?ic/ei? caeeoie oinoaoii? eeneioe.. A?ae ?I 5,5
aei 7,8 a?aeaoaa?oueny cnoa neaiaeo oa eiai ?icuaieaiiy ia ?ioaineaiee
neiaeao ? neaaeee AA-eaaae?oieao, ye? ia?ae?eaathoueny.

?en.4. Caeaaeiino? n-?I (1,2) oa ?-?I (3,4,5) aeey nenoai

I-I3?I4 (ni?aa.1:2): I-O? (1,3), Zr(5), I3?I4 (2,4).

Cnoa a?aeaoaa?oueny a oiio ae i?ii?aeeo ?I, ui ? aeey i?oioinoaoii?
eeneioe, ui na?ae/eoue i?i i?e?aeiaiiy aei eiiieaeno neeaaeo
[Zr(OH)2IPO4]n ae?oaiai caeeoeo I?I42- c ooai?aiiyi [Zr(OH)2(HPO4)2]2-.
Iayai?noue neaaeeo neaiae?a eaaae?oieaoo aeaco? ia ooai?aiiy iaaaeeei?
e?eueeino? eiiieaeno c aeaiia iaaea?aaeaioieie caeeoeaie eeneioe,
[Zr(OH)2(PO4)(HPO4)]3- .

A niaeo?ao nenoai I-IAAeO niinoa??aa?oueny aaeeea e?euee?noue
neaiae?a 31?. I?e ci?ooaaii? aeo?aeieo ?ic/ei?a oeoaio oa oee?eii?th c
IAAeO aeiaaeathoue inaaee, ui iiai?noth ia ?ic/eiythoueny a eoaeiiio
na?aaeiaeu?.

A niaeo?ao nenoaie Zr-IAAeO (1:1, eenea na?aaeiaeua) neaiae 31? o
?ic/ei? iaae inaaeii ia cao?eniaaii. Aeey nenoaie O?-IAAeO i?e
?I=1,5-1,75 (ui a?aeiia?aea? 0-4 aea?aaeaioai eoao) io?eiaii neeaaeiee
niaeo? c /ioe?ueio neaiae?a, iaeei c ieo ii ?icoaooaaiith a?aeiia?aea?
neaiaeo a?eueii? IAAeO (20 i.ae.), ?io? ?icoaoiaai? a iaeano? 21-15
i.ae.(?en.5). I?e aeiaeaaaii? 5 aea?aaeaio?a EII (?I=2,7) an? neaiaee
ceeaathoueny a iaeei. Iiae?ai?noue niaeo??a ssI? 31? nenoai O?-IAAeO
(?ic/ei) aei niaeo??a oaa?aeeo oinoao?a oeoaio, io?eiaieo ?ai?oa, iiaeia
iiynieoe oei, ui a eeneiio na?aaeiaeu? IAAeO ooai?th? eiiieaene ca
o/anoth iaei??? oinoiiiai? a?oie. Iaeei neaiae a niaeo?? (?I=2,7, 5
aea.EII) iiaeia iiynieoe ooai?aiiyi eiiieaeno, a yeiio oinoiiia? a?oie
aea?aaeaioi?. I?e aeiaeaaaii? oinoiai aea?aaeaioo EII a niaeo??
c’yaey?oueny AA-eaaae?oieao (22,7-20,1 i.ae.), ui ia?ae?eaa?oueny c
neiaeaoii N (19,6 i.ae.) (aeea.?en.). E??i oiai ? aeaa neaiaea neaiaea
iaeiaeiai? ieiu? 33,05 (D) ? 17,38 (A).

?en.5. Niaeo?e ssI? 31? nenoai O?-IAAeO-EII c? ni?aa.1:1:n
oaZr-IAAeO-EII (1:1:4).

Oaeiae ia ?en. iaaaaeaii niaeo? nenoaie Zr-IAAeO-EII (1:1:4,
?I=9,5), oa?aeoa? eiai iiae?aai aei niaeo?o oeoaio i?e oiio ae cia/aii?
?I: neaiaee 27 i.ae.(D) oa 15,87(A) i?eaeecii ??aii? ieiu?, eaaae?oieao
AA c oeaio?ii 18,08 i.ae. An? neaiaee cnoioo? o a?e neeueiiai iiey ,
ieiua neaiae?a D i E a?eueoa (o ii??aiyii? c oeoaiii), neaiae N
a?aenooi?e. Neaiae D iaie a?aeianaii aei eiiieaen?a c? ni?aa?aeiioaiiyi
I:IAAeO=2:1, neaiae A ciaoiaeeoueny o iaea?eueo neaaeiio iie?, eiai
iiaeia a?aeianoe aei eiiieaeno neeaaeo 1:2. ??ai?noue ieiu aeaio
neaiae?a (D i E) aeaco? ia oa, ui aiie a?aeiinyoueny aei iie?yaea?iiai
eiiieaeno (caaaeueiee neeaae 3:3). Eaaae?oieao (O? ? Zr) iiaea
a?aeiia?aeaoe ooai?aiith aeeia?ieo eiiieaen?a 2:2 (o neeaae? yeeo ?
ia??aiioe?ii? caeeoee eeneioe), neaiae N (O?) aea? iaca’caia a eiiieaen
oinoiiiaa a?oia.

I?e ni?aa?aeiioaii? 1:2 a nenoai? c oeoaiii inaaee ia aeiaaeathoue,
ui iiaeia iiynieoe ooai?aiiyi eiiieaen?a c aeaiia e?aaiaeaie. A nenoai?
c oee?eii??i i?e ci?oaii? aeo?aeieo eiiiiiaio?a iae?aco ooai?th?oueny
aaeue, ui ?ic/eiy?oueny c i?aeaeuaiiyi ?I. A niaeo?ao 31? iaio aea/aieo
nenoai i?e ?I=2 cao?eniaaii ii aeaa ?ioaineaieo neaiaee c iaeiaeiaeie
cia/aiiyie o?i?/ieo cnoa?a (20 ? 18 i.ae.). A?aenooi?noue cnoao neaiaeo
a neeueia iiea ii a?aeiioaiith aei oeoaio a aeiaaeeo oee?eii?th, yea
niinoa??aaeinue aeey eiiieaen?a c i?oioinoaoiith eeneioith oa IAAeO
(ni?aa.1:1) iiaeia iiynieoe oei, ui aei neeaaeo eiiieaeno oee?eii?e
aoiaeeoue o iaa?ae?ie?ciaaiiio noai? (aeea.oaae.3). A?aoiaoth/e /enei
aea?aaeaio?a, iaiao?aeieo aeey ooai?aiiy eiiieaen?a – 6 (aeey oeoaio) oa
4 (aeey oee?eii?th), aeo?aeii? oi?ie a?ae?ieneae?a oa iai?yieo cnoa?a
i?e i?aeaeuaii? ?I ?ic/eio ( a neaaea iiea aeey oeoaio oa neeueia aeey
oee?eii?th), iaie cai?iiiiiaaii ianooii? oi?ie eiiieaen?a:

20 i.ae. – [Ti(OH)(H3L) (H2L)]2-, [Zr(H3L)2]0;

18 i.ae. – [Ti(OH)2(H3L)2]2-, [Zr(H2L)2]2-.

A niaeo?ao eiiieaen?a oee?eii?th i?e i?aeaeuaii? ?I, e??i oeeo
neaiae?a, cao?eniaaii AA-eaaae?oieao, yeee iiaeia a?aeianoe aei
eiiieaeno [Zr(H2L)(H3L)]- c ia??aiioe?iieie oinoiiiaeie a?oiaie.

Oe? aeine?aeaeaiiy iieacaee, ui a aeaieo nenoaiao aeiaeaaaiiy
iaeiaeiaiai /enea aea?aaeaio?a i?ecaiaeeoue aei ooai?aiiy aeae?eueeio
eiiieaen?a caaaeueiiai neeaaeo I(II)?-oHn-oL, ye? ??ciyoueny e?euee?noth
iieaeoe aiaee.

I?aeoe/iiio aeei?enoaiith io?eiaieo ?acoeueoao?a i?enay/aii ?icae?e 7. C
aeei?enoaiiyi aeaio iaoiae?a anoaiiaeaii iayai?noue aca?iiae?? i?ae
aeaiia eeneioaie a ?ic/ei? oeyoii ooai?aiiy ni?eueii? nenoaie aiaeiaaeo
ca’ce?a. Iaea?eueo aoaeoeaiei aeciaii ni?aa?aeiioaiiy I3?I4-IAAeO=1:0,1.
Oeae oaeo aeei?enoaii aeey io?eiaiiy ni?aaioo ia iniia? oinoaoo oeoaio c
aaaaeaiith ia noaae?? neioaco IAAeO. I?iaaaeaiiy aenia?eiaio?a c
cieue-aaeue iaoiaeeeith i?aeoaa?aeeei iioeiaeuei?noue aeuacaaaeaiiai
ni?aa?aeiioaiiy: aaaaeaiiy naia oaei? e?eueeino? IAAeO ia aieeaa? ia
eiai ye?noue. Aecia/aiiy iaei?ino?oeo oa?aeoa?enoee io?eiaiiai ni?aaioo
i?aeoaa?aeeei eiai a?eueoo aoaeoeai?noue o ii??aiyii? c iaiiaeeo?eiaaiei
oinoaoii oeoaio. Aei aeaiiai ?icae?eo oaeiae aeiaea?oueny aeo
aei?iaoaaiue a ?inoeooo? i?iaeai iaoa??aeiciaanoaa IAI Oe?a?ie
iaea?aeaiiai ni?aaioo aeey aeaaaeaiiy ?ii?a no?iioe?th c i?aai?cio
i?aeaeine?aeieo oaa?ei, aeai? na?ae/aoue i?i aeineoue aenieo
aoaeoeai?noue io?eiaiiai ni?aaioo.

AENIIAEE.

1. Aea/aii iniiai? caeiiii??iino? i?ioean?a aca?iiae?? oeoaio oa
oee?eii?th c i?oioinoaoiith oa ieneaoee?aeaiaeeoinoiiiaith (IAAeO)
eeneioaie o aiaeieo ?ic/eiao c iaoith anoaiiaeaiiy aca?iica’yceo i?ae
iniaeeainoyie eiiieaeniooai?aiiy a oeeo nenoaiao oa ooai?aiiyi
iie?yaea?ieo niieoe, ui i?iyaeythoue ?iiiiai?ii? aeanoeaino?.

2. Noi?nia aeei?enoaiiy iaoiae?a ?I-iioaioe?iiao?e/iiai oeo?oaaiiy
oa ssI?-niaeo?ineii?? (1I, 13N oa 31?) i?aeoaa?aeeei i’yoeiniiai?noue
IAAeO. I?iaaaeaiiy aeine?aeaeaiue i?e ??cieo eiioeaio?aoe?yo eeneioe
aeyaeei, ui a ?icaaaeaieo ?ic/eiao (1.10-3-1.10-2 iieue/e)
i’yoeiniiai?noue ?aae?co?oueny ca ?aooiie eiiieaeniooai?aiiy c ?iiii
eae?th , a a?eueo eiioeaio?iaaieo ?ic/eiao (1.10-1 iieue/e)
ooai?th?oueny ai?ii L5-(?I>12).

3. Iaoiaeii ?I-iioaioe?iiao??? aia?oa aecia/aii neeaae eiiieaen?a
O? (IV) ? Zr(IV) c i?oioinoaoiith eeneioith oa IAAeO o aiaeieo ?ic/eiao
i?e o?ueio eiioeaio?aoe?yo iaoae?a (1.10-3 , 1.10-2 ? 1.10-1 iieue/e) oa
??cieo ni?aa?aeiioaiiyo eiiiiiaio?a. Aeyaeaii, ui a on?o nenoaiao i?e
eiioeaio?aoe?yo >1.10-2 iieue/e ooai?ththoueny ia?ic/eii? iie?yaea?i?
niieoee aea?iiey?iiai neeaaeo oa ?ic/eii? c aeaiia iieaeoeaie e?aaiaeo
(inoaii? ?ic/eii? aeey oeoaio). ?iie aiaeith a oaeeo iie?yaea?ieo
niieoeao caeaoi? cai?uoaaoenue ?iiaie eae?th.

4. Aiae?c niaeo??a ssI? 31? oa aeai? ?I-iioaioe?iiao??? aeyaeee
iayai?noue a eiiieaenao, e??i aeii?ioth/eo oi?i I(II)22+, iaoae?a o iaio
a?ae?ie?ciaaiiio noai?. Aeyaeaii caeaaei?noue /enea II-a?oi a?ae
i?e?iaee oa aeaioaoiino? e?aaiaeo, ni?aa?aeiioaiiy iaoae:e?aaiae. Oaeiae
iieacaia iiaeeea?noue ni?a?nioaaiiy oi?i I(II)?-oHn-oL.

5. Aeyaeai? caeiiii??iino? i?ioean?a eiiieaeniooai?aiiy o aiaeieo
?ic/eiao aeicaieeee i?ae?a?aoe iioeiaeueio e?euee?noue IAAeO aeey
aaaaeaiiy ?? a iao?eoeth ni?aaioa ia iniia? oinoaoo oeoaio. Iiaee
ni?aaio io?eiaii c aeei?enoaiiyi cieue-aaeue iaoiaeo. Aecia/aiiy eiai
ni?aoe?eieo oa?aeoa?enoee aeyaeei i?aeaeuaiiy aoaeoeaiino? oinoaoo
oeoaio i?e aaaaeaii? a eiai iao?eoeth aeiaeaoeiaeo eiiieaeniooai?thth/eo
a?oi. Iaea?aeaii iiceoeai? ?acoeueoaoe i?e aei?iaoaaii? ni?aaioo a
?inoeooo? i?iaeai iaoa??aeiciaanoaa IAI Oe?a?ie ii aeaaaeaiith
no?iioe?th c i?aai?cio i?aeaeine?aeieo oaa?ei.

Iniiaiee ci?no aeena?oaoe?? aeeeaaeaii a ?iaioao:

1. Eino?iieia I.A., O?aoueyeiaa E.I., O?a/aaneee A.A., ?iiaiiaa E.A.
ssI? (1I, 13N, 31?) –niaeo?u e no?iaiea ieneyoeeeaeaiaeeoinoiiiaie
eeneiou // Oe?.oei.aeo?i. –1993. –O.59. -?7.

-N.679-683.

2. ?iiaiiaa E.A., No?aeei A.A., Oaeiaeia N.A., Eino?iieia I.A.
Eiiieaeniua niaaeeiaiey ieneyoeeeaeaiaeeoinoiiiaie eeneiou n oeoaiii //
AE.iai?a.oeiee. –1995. –O.40. -?10. –N.1655-1660.

3. No?aeei A.A., ?iiaiiaa E.A., Ai?ooi A.E., Oaeiaeia N.A. Enneaaeiaaiea
eiiieaeniia?aciaaiey oee?eiiey n i?oioinoi?iie eeneioie a aiaeiuo
?anoai?ao // AE.iai?a.oeiee. –1996. –O.41. -?8. –N.1290-1293.

4. ?iiaiiaa E.A., No?aeei A.A., Ai?ooi A.E., Oaeiaeia N.A.
Eiiieaeniia?aciaaiea oeoaia n i?oioinoi?iie eeneioie a aiaeiuo ?anoai?ao
// Oe?.oei.aeo?i. –1997. –O.63. -?1. -N.8-12.

5. ?iiaiiaa E.A., No?aeei A.A., Oaeiaeia N.A., Eino?iieia
I.A.Eiiieaeniua niaaeeiaiey oee?eiiey n ieneyoeeeaeaiaeeoinoiiiaie
eeneioie // Oe?.oei.aeo?i. –1997. –O.63. -?2.

-N.77-82.

6. ?iiaiiaa E.A., O?a/aaneee A.A., Eino?iieia I.A., No?aeei
A.A.Eiiieaeniia?aciaaiea oeoaia e oee?eiiey n i?oioinoi?iie e
ieneyoeeeaeaiaeeoinoiiiaie eeneioaie // Oe?.oei.aeo?i. –1998. –O.64.
-?10. -N.83-89.

7. ?iiaiiaa E.A., No?aeei A.A., Oaeiaeia N.A. Eiiieaeniua niaaeeiaiey
oeoaia e oee?eiiey n ieneyoeeeaeaiaeeoinoiiiaie eeneioie // Oacenu ?EV
Oe?aeineie eiioa?aioeee ii iai?aaie/aneie oeiee. –Eeaa. –1996. –N.107.

8. ?iiaiiaa E.A., O?a/aaneee A.A., No?aeei A.A. Eco/aiea acaeiiaeaenoaey
nieae Ti(IV) e Zr(IV) n i?oioinoi?iie eeneioie // Oacenu 6
Iao/ii-oaoie/aneiai naieia?a ii oinoi?o. –Eueaia. –1993. –N.74.

?iiaiiaa ?.A. Eiiieaeni? niieoee oeoaio (?V) oa oee?eii?th (IV) c
i?oioinoaoiith oa ieneaoee?aeaiaeeoinoiiiaith eeneioaie. Aieea
eiiieaeniooai?aiiy ia oi?ioaaiiy ni?aoe?eieo aeanoeainoae. –?oeiien.

Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa o?i?/ieo
iaoe ca niaoe?aeuei?noth 02.00.01 – iai?aai?/ia o?i?y. ?inoeooo
caaaeueii? oa iai?aai?/ii? o?i?? IAI Oe?a?ie ?i. A.?.Aa?iaaenueeiai,
Ee?a, 1999.

Aeena?oaoe?y i?enay/aia nenoaiaoe/iiio aeine?aeaeaiith
eiiieaeniooai?aiiy nieae oeoaio oa oee?eii?th c i?oioinoaoiith eeneioith
oa IAAeO a aiaeieo ?ic/eiao, a oe?ieiio ae?aiacii? ?I, i?e ??cieo
ni?aa?aeiioaiiyo eiiiiiaio?a, c aeei?enoaiiyi iaoiae?a
?I-iioaioe?iiao?e/iiai oeo?oaaiiy oa ssI? ia yae?ao 1I, 13N ? 31?.
Anoaiiaeaii neeaae ? aoaeiao iiii- oa iie?yaea?ieo eiiieaen?a, ui
ooai?ththoueny a nenoaiao . Iieacaii iiaeeea?noue aeei?enoaiiy noi?o?
aeaio eeneio o neioac? ni?aaio?a ia iniia? oinoao?a oeoaio oa
oee?eii?th.

Eeth/ia? neiaa: eiiieaene, iie?yaea?i? niieoee, oeoai, oee?eii?e,
oinoaoe, ?iiiiai?ii? aeanoeaino?.

Romanova I.V. Complexes of Titanium (IV) and Zirconium (IV) with
o-Posphoric and Hydroxyethylidenediphosphonic Asids. –Manuscript.

Thesis for a candidate’s degree by speciality 02.00.01 – inorganic
chemistry. V.I.Vernadsky Institute of General and Inorganic chemistry of
Ukrainian National Academy of Science, Kyiv, 1999.

The thesis is devoted to a systematic investigation of complex
formation salts of Ti(IV) and Zr(IV) with o-posphoric and
hydroxyethylidenediphosphonic asids in aqueous solutions, in broad
pH-range, at different constituent rations by means of polynuclear NMR
(1H, 13C and 31P) and pH-potentiometry. The composition and structure of
mono- and polynuclear complexes, wich formed in solution, have been
established. It has been shown that a mixture of these acids can be used
in the syntethis of titanium and zirconium-based sorbents.

Key words: complexes, polynuclear compaunds, titanium , zirconium,
ion-exchange properties.

?iiaiiaa E.A. Eiiieaeniua niaaeeiaiey oeoaia (EV) e oee?eiiey (EV) n
i?oioinoi?iie e ieneyoeeeaeaiaeeoinoiiiaie eeneioaie. –?oeiienue.

Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa oeie/aneeo iaoe
ii niaoeeaeueiinoe 02.00.01 – iai?aaie/aneay oeiey. Einoeooo iauae e
iai?aaie/aneie oeiee ei.A.E.Aa?iaaeneiai IAI Oe?aeiu, Eeaa, 1999.

Aeenna?oaoeey iinayuaia eco/aieth iniiaiuo caeiiiia?iinoae i?ioeannia
acaeiiaeaenoaey oeoaia e oee?eiiey n i?oioinoi?iie e
ieneyoeeeaeaiaeeoinoiiiaie eeneioaie a aiaeiuo ?anoai?ao n oeaeueth
onoaiiaeaiey acaeiinayce iaaeaeo iniaaiiinoyie eiiieaeniia?aciaaiey a
yoeo nenoaiao e ia?aciaaieai iieeyaea?iuo niaaeeiaiee, eioi?ua
i?iyaeytho eiiiiaiaiiua naienoaa.

Niaianoiia eniieueciaaiea iaoiaeia ?I-iioaioeeiiao?e/aneiai oeo?iaaiey e
ssI?-niaeo?ineiiee (1I, 13N e 31?) iiaeoaa?aeeei aiciiaeiinoue
?aaeecaoeee iyoeiniiaiinoe IYAeO a ?aaeoeeyo. A ?acaaaeaiiuo ?anoai?ao
(1.10-3-1.10-2 iieue/e) iia ?aaeecoaony ca n/ao acaeiiaeaenoaey n eiiii
eaeey, a aieaa eiioeaio?e?iaaiiuo ?anoai?ao (1.10-1 iieue/e) ia?acoaony
aieii L5-(?I>12).

Iaoiaeii ?I-iioaioeeiiao?ee ii?aaeaeai ninoaa eiiieaenia oeoaia e
oee?eiiey n i?oioinoi?iie eeneioie e IYAeO a aiaeiuo ?anoai?ao a
caaeneiinoe io eiioeaio?aoeee e niioiioaiey eiiiiiaioia. Ai anao
nenoaiao ia?acothony ia?anoai?eiua iieeyaea?iua niaaeeiaiey, a eioi?uo
eii eaeey niiniaai caiauaoue eii aiaei?iaea.

Aiaeec niaeo?ia ssI? (31?) e aeaiiuo ?I-iioaioeeiiao?ee ii?aaeaeeee
iaee/ea a ninoaaa eiiieaenia, e?iia aeiieie?othuae oi?iu I(II)22+ ,
iaoaeeia a iaiaa aeae?ieeciaaiiii ninoiyiee. Iaeaeaia caaeneiinoue /enea
aeae?ieneeueiuo a?oii io i?e?iaeu e aeaioaoiinoe eeaaiaea, a oaeaea io
niioiioaiey iaoaee eeaaiae.

Iaeaeaiiua caeiiiia?iinoe i?ioeannia eiiieaeniia?aciaaiey a eco/aiiuo
nenoaiao, iicaieeee iiaeia?aoue iioeiaeueiia eiee/anoai IYAeO aeey
aaaaeaiey aa a iao?eoeo ni?aaioia ia iniiaaiee oinoaoia oeoaia.
Eniuoaiey iieo/aiiiai ni?aaioa iiaeoaa?aeeee iiauoaiea yooaeoeaiinoe
oinoaoia oeoaia i?e aaaaeaiee a aai iao?eoeo aeiaaai/iuo
eiiieaeniia?acothueo a?oii.

Eeth/aaua neiaa: eiiieaenu, iieeyaea?iua niaaeeiaiey, oeoai ,oee?eiiee,
oinoaou, eiiiiaiaiiua naienoaa.

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