I?I?NOA?NOAI INA?OE OE?A?IE

Oe?a?inueeee aea?aeaaiee

o?i?ei-oaoiieia?/iee oi?aa?neoao

ia i?aaao ?oeiieno

eieueoeiaa Ieaia Aaiiaae??aia

oaee 542.61:546.681

Aeno?aeoe?y iie?aaeaiaieueo?aiiaeo aaoa?iiie?eiiieaen?a

aae?th oa ?? canoinoaaiiy a aiae?c?.

02.00.02 — aiae?oe/ia o?i?y

aaoi?aoa?ao

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?i?/ieo iaoe

aei?i?iiao?ianuee — 1999.

aeena?oaoe??th ? ?oeiien.

?iaioa aeeiiaia a aei?i?iiao?ianueeiio aea?aeaaiiio oi?aa?neoao?.

iaoeiaee ea??aiee aeieoi? o?i?/ieo iaoe, i?ioani? Oeeaaiie Ethaeieea
Iaae?aia , aei?i?iiao?ianueeee aea?aeaaiee oi?aa?neoao, i?ioani?

Io?oe?ei? iiiiaioe: aeieoi? o?i?/ieo iaoe, I?ioani?, aeaaeai?e ai
aeui? oeiee Oe?a?ie, Oaa/oe ?aai ieaen?eiae/, aeiiaoeueeee
aea?aeaaiee oi?aa?neoao, caa.eaoaae?ith aiae?oe/ii? o?i??

eaiaeeaeao o?i?/ieo iaoe, aeioeaio aa?eaeia a?o?e?e na?a?eiae/,

aea?aeaaia iaoaeo?a?eia aeaaeai?y oe?a?ie, aeioeaio

I?ia?aeia onoaiiaa:

o?ceei-o?i?/iee ?inoeooo ai oe?a?ie, i. iaeana.

Caoeno a?aeaoaeaoueny 4 /a?aiy 1999 ?. ia 11 aiaeei? ia can?aeaii?
niaoe?ae?ciaaii? a/aii? ?aaee ae 08.078.01 i?e oe?a?inueeiio
aea?aeaaiiio o?i?ei-oaoiieia?/iiio oi?aa?neoao? ca aae?anith: 320005, i.
aei?i?iiao?ianuee, i?. aaaa??ia, 8.

c aeena?oaoe??th iiaeia iciaeiieoenue o a?ae?ioaoe? oe?a?inueeiai
aea?aeaaiiai o?i?ei-oaoiieia?/iiai oi?aa?neoaoo ca aae?anith: i.
aei?i?iiao?ianuee,

i?. aaaa??ia, 8.

aaoi?aoa?ao ?ic?neaiee 27 ea?oiy 1999 ?.

a/aiee nae?aoa?

niaoe?ae?ciaaii? a/aii? ?aaee ___________________________
i?i?aee? ?.ae.

Caaaeueia oa?aeoa?enoeea ?iaioe

Aeooaeuei?noue oaie. Aeine?aeaeaiiy i?ioean?a ooai?aiiy, no?eeino? oa
aeanoeainoae aaoa?iiie?eiiieaen?a (AIE) Aae?th no?oeoo?e Eaa?ia ia?
aaeeea cia/aiiy aeey ?icaeoeo aiae?oe/ii? o?i?? oeueiai aeaiaioa.
Ia?niaeoeaa aeei?enoaiiy AIE Aae?th a aiae?c? iia’ycaia c aenieith
naeaeoeai?noth a?aeiia?aeieo iaoiaeee, aea ?o /ooeea?noue iiee ia
a?aeiia?aea? aeiiaai no/anii? aiae?oe/ii? o?i??, ui iiynith?oueny
iaaeinoaoiuei aenieith no?ee?noth AIE Aae?th oa ia?aeaeueiei oi?ioaaiiyi
aeecueeeo ca nai?ie aeanoeainoyie ?ciiie?eiiieaen?a (?IE). ??oaiith
oe??? i?iaeaie iiaea ni?eyoe aeno?aeoe?y AIE eeniaai?uoth/eie
i?aai?/ieie ?ic/eiieeaie, yea oe?iei aeei?enoa?oueny i?e aiae?c?
Oinoi?o, E?aii?th, Aa?iai?th oa Ieo’yeo. Aea/aiiy aeno?aeoe?eii?
caeaoiino? AIE Aae?th, a oaeiae iiooe iaea?eueo no?eeeo oi?i a ?yaeo
GaMoxW12-xO405- aoaea ni?eyoe ia eeoa ?icaeoeo o?i?? aaoa?iiie?niieoe,
a ? a?eueo oe?ieiio canoinoaaiith AIE Aae?th a aiae?c?. Naia oeueiio ?
aoea i?enay/aia aeena?oaoe?eia ?iaioa.

Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie, ieaiaie, oaiaie. Aeena?oaoe?eia
?iaioa aeeiiaia a?aeiia?aeii c aea?aeathaeaeaoiith oaiith 158-96
“Ooai?aiiy, a?aeiiaeaiiy, no?oeoo?a aaoa?iiie?niieoe ?ii?a iaoae?a.
?aaeoe?? aaoa?iiie?ai?ii?a c i?aai?/ieie eao?iiaie a eiiiiao???”
eii?aeeiaoe?eiiai ieaio ?aaee c aeieia?/ii? oa aiae?oe/ii? o?i?? AI
Aeui? oeiee Oe?a?ie, ?a?no?aoe?eiee ?0196V000271.

Iaoa ? caaea/? aeine?aeaeaiiy. Iaoa ?iaioe iieyaaea o aea/aii?
aeno?aeoe?? iie?aaeaiiaieueo?aiiaeo AIE aae?th eeniaai?uoth/eie
i?aa-i?/ieie ?ic/eiieeaie oa canoinoaaii? ?? aeey aea/aiiy
eiiieaeniooai?aiiy oa oaeineiiaeaiiy iaoiae?e aecia/aiiy Aae?th o
aeaeyae? AIE: i?aeaeuaiiy ?o /ooeeaino? oa aea??eiaino?, a oaeiae o
iiooeo iaea?eueo no?eeeo eiiieaen?a o ?yaeo GaMoxW12-xO405- aeey
iiaeaeueoiai ?o canoinoaaiiy a aiae?c?.

O a?aeiia?aeiino? c iinoaaeaiith iaoith ae??ooaaeenue oae? iniiai?
caaea/?:

— aea/aiiy aeno?aeoe?eii? caeaoiino? ieeniaieo oa a?aeiiaeaieo
iie?aaeaiaieueo?aiiaeo aaoa?iiie?eiiieaen?a Aae?th ? anoaiiaeaiiy
iiaeeeaino? ?o a?aeie?aieaiiy a?ae ?ciiie?eiiieaen?a;

— aeei?enoaiiy naeaeoeaii? aeno?aeoe?? AIE Aae?th no?oeoo?e Eaa?ia aeey
a?eueo aeaoaeueiiai aea/aiiy oiia ooai?aiiy, a oaeiae ioe?iee no?eeino?
aeine?aeaeoaaieo niieoe;

— aeei?enoaiiy aeno?aeoe?eiiai eiioeaio?oaaiiy oa iai?yieo iaoiae?a
iii-aeaiiy aeey ?ic?iaee /ooeeaeo iaoiaeee aecia/aiiy Aae?th o aeaeyae?
AIE.

Iaoeiaa iiaecia. Aeyaeai? caeiiii??iino? ci?ie aeno?aeoe?eii?
caeaoiino? iie?aaeiaieueo?aiiaeo AIE Aae?th a caeaaeiino? a?ae ?o
neeaaeo oa ciaeaeai? iioeiaeuei? oiiae ?o aeno?aeoe??, ye? aeicaieeee
?aeiiaiaeoaaoe aeei?enoaiiy aeno?aeoe?? eiiieaena GaMo10W2O405- aeey
aecia/aiiy Aae?th. Aeine?aeaeaia aeno?aeoe?y iie?aaeiaieueo?aiiaeo ?IE,
ui aeaei iiaeeea?noue c a?aooaaiiyi aeaieo ?*-niaeo?ineii?? anoaiiaeoe
iayai?noue ?IE c iaaiei nooiaiai iie?ia??caoe?? a nenoaiao c ??ciei
ni?aa?aeiioaiiyi [Mo]:[W].

Aia?oa c canoinoaaiiyi aeno?aeoe?? aecia/ai? eiinoaioe no?eeino?
aeayeeo AIE o aea/a?iiio ?yaeo. Caeiiii??iino? ?o ci?ie ei?aeththoue ?c
neeaaeii e?aaiaeii? noa?e AIA.

Iaoiae aeno?aeoe?eiiai neioaco aeei?enoaii aeey iaea?aeaiiy /enoeo
e?enoae?a nieae iao??th ci?oaiie?aaiaeieo AIE Aae?th, ui aeicaieeei
aea/aoe ?o aeanoeaino? o a?aenooiino? iaaeeeoeo e?aaiae?a.

Ciaeaeai? aenia?eiaioaeuei? i?aeoaa?aeaeaiiy ci?oaiiai iaoai?cio
aeno?aeoe?? AIE, yeee aeeth/a? a?ae?aoii-nieueaaoi? oa
aeiii?ii-aeoeaioi?i? aca?iiae??. ?ic?aoiaaia eiinoaioa aeno?aeoe??
iie?aaeiaieueo?aiiaaeaoo. C?iaeaii ni?iao aea/aiiy — eciia??caoe?? AIE
ca aeiiiiiaith aeno?aeoe??.

I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a. Cai?iiiiiaaia iaoiaeeea
neioaco /enoeo nieae AIE iao??th.

Ciaeaeai? oai?aoe/i? caeiiii??iino? aeicaieeee ?ic?iaeoe ?yae iaoi-aeee
aecia/aiiy Aae?th c iie?ioaieie iao?ieia?/ieie oa o?i?ei-aiae?oe/-ieie
aeanoeainoyie. ?ic?iaeai? aeno?aeoe?ei? oa aacaeno?aeoe?ei? iaoiaeeee
aiae?co aeicaieythoue i?aeaeueoe /ooeea?noue aecia/aiiy Aae?th o
aeaeyae? AIE aei ??aiy iaoiaeee c canoinoaaiiyi enaioaiiaeo aa?aiee?a.
I?e oeueiio i?aeae-uo?oueny naeaeoeai?noue ii a?aeiioaiith aei ?yaeo
aeaiaio?a (In, Co, Cd, Mo, W). Iaiao?aeia /ooeea?noue (0.008 iea/ie Ga3+
) aeinyaa?oueny eiia?ioaaiiyi aeno?aeoe?eiiai eiioeaio?oaaiiy c iaoiaeii
iiiaeaiiy (iai?yiei aecia/ai-iyi Aae?th ca Iie?aaeaiii, ai?no yeiai a
AIE o 10 ?ac?a a?eueoee, i?ae Aae?th).

Aeai? c aeno?aeoe?? iie?aaeaiaieueo?aiiaeo ?IE iiaeooue aooe
aeei?enoai? i?e aecia/aii? ia eeoa Aae?th, a oaeiae P, Si, Ge oa As.

?ic?iaeaia aeno?aeoe?eia iaoiaeeea ?icae?eaiiy oa ia?aeaeueiiai
aecia-/aiiy Aae?th oa aeaiaio?a, ye? ooai?ththoue aiaeia?/i? AIE (P, Si,
Ge, As).

Cai?iiiiiaai? iaoiaeeee iiaeooue aooe aeei?enoai? aeey aecia/aiiy
Aae?th o aieueo?aiai?uoth/eo iaoa??aeao, ?iae??, iai?ai?ia?aeieeiaeo
nenoaiao oeio Ga — P.

Iniaenoee aianie caeiaoaa/a iieyaa? a iaea?aeaii? oa ocaaaeueiaii?
aenia?eiaioaeueieo aeaieo, iaaaaeaieo o aeena?oaoe??, a ioae?eaoe??
iaoa??ae?a aeine?aeaeaiue. Iaaiai?aiiy ?acoeueoao?a i?iaaaeaia aaoi?ii
ni?eueii c iaoeiaei ea??aieeii.

Ai?iaaoe?y ?iaioe. Iaoa??aee ?iaioe aeiiia?aeaeenue ia Oe?a?inuee?e
eiioa?aioe?? c aiae?oe/ii? o?i?? (Oaeai?iae, 1998 ?.), I?aeia?iaeiiio
eiia?an? c aiae?oe/ii? o?i?? (Iineaa, 1997 ?.), I?aeia?iaei?e
eiioa?aioe?? “Aeaai?iaei? ? ??aee?ni? iaoaee” (Aeiiaoeuee, 1997 ?.),
Oe?a?inuee?e eiioa?aioe?? c iai?aai?/ii? o?i?? (Ee?a, 1996 ?.), IV
I?aeia?iaei?e eiioa?aioe?? “Aeueyin o?ainac” (Aei?i?iiao?ianuee, 1997
?.).

Ioae?eaoe??. ?acoeueoaoe aeena?oaoe?eii? ?iaioe aeeeaaeaii o 10
ae?oeiaaieo i?aoeyo: 5 noaooyo oa 5 oacao aeiiia?aeae.

No?oeoo?a oa ianya ?iaioe. Aeena?oaoe?y aeeeaaeaia ia 147 noi??ieao
ae?oeiaaiiai oaenoo, neeaaea?oueny ?c anooio, 4 ?icae?e?a, iaaiai?aiiy
?acoeueoao?a aeine?aeaeaiue, aeniiae?a, nieneo e?oa?aoo?ieo aeaea?ae,
yeee ai?uo? 158 iaeiaioaaiue ?ia?o a?o/eciyieo oa ?iicaiieo aaoi??a.
?iaioa i?noeoue 17 oaaeeoeue, 52 ?enoiea.

INIIAIEE CI?NO ?IAIOE

O anooi? iaa?oioiaaii aeooaeuei?noue oaie, noi?ioeueiaaii iaoo
aeine?aeaeaiue oa niiniae ?? aeinyaiaiiy, ioa?aeoa??ciaaii iaoeiao
iiaecio ? i?aeoe/io oe?ii?noue ?iaioe.

Ia?o?e ?icae?e aeena?oaoe?? i?enay/aii aiae?co canoinoaaiiy aeno?aeoe??
AIE aeey i?aeaeuaiiy /ooeeaino? aecia/aiiy aeayeeo aeaiaio?a. ?icaeyiooi
oaeoi?e, ui aieeaathoue ia aeno?aeoe?th AIE oa oiiae ?o a?aeie?aieaiiy
a?ae ?ciiie?eiiieaen?a, a oaeiae aeaye? aniaeoe iaoai?cio aeno?aeoe??
niieoe oe?iai eeano. Iaaaaeai? e?oa?aoo?i? aeai? i?i iai?yi? iaoiaeeee,
caniiaai? ia aeno?aeoe?? AIE, noaie aeno?aeoe?eiiai ?icae?eaiiy
aeaiaio?a, ooai?thth/eo AIE. Iniaeeaa oaaaa i?enay/aia oa?aeoa??noeoe?
?nioth/eo iaoiaeee aecia/aiiy Aae?th o aeaeyae? AIE. Aiae?c e?oa?aoo?ieo
aeaea?ae i?aeoaa?aeaeo? a?aenooi?noue aeaieo c aeno?aeoe?? AIE Aae?th ?
aeooaeuei?noue oaeeo aeine?aeaeaiue.

O ae?oaiio ?icae?e? iienaii iaoiaeeeo aeine?aeaeaiiy aeno?aeoe?eii?
caeaoiino? AIE Aae?th, yea iieyaa? o oioiiao?oaaii? aiaeii? oa
i?aai?/ii? oac oa ciaoiaeaeaii? nooiaith aeeo/aiiy ca oi?ioeith: R=100
Ao/(Ao+Aa),%.

Eiio?ieue i?aaeeueiino? oe??? iaoiaeeee cae?enithaaany ca aeiiiiiaith
o?i?/iiai aiae?co aiaeieo oac oa ?aaeno?aeo?a ia ai?no ca’ycaiiiai a AIE
Iie?aaeaio ca ?aaeoe??th c ?iaeai?ae-?iiaie.

?ic/eie AIE Aae?th iaea?aeoaaee oeyoii eei’yo?iiy ?aaeoe?eii? noi?o?
eiiiiiaio?a (Ga3+, MoO42-, WO42-, H3O+) ca iaoiaeeeith, ?ic?iaeaiith o
iiia?aaei?o aeine?aeaeaiiyo ia eaoaae?? aiae?oe/ii? o?i?? AeAeO.

Caa?aaeaiiy neeaaeo AIE i?e aeno?aeoe?? i?aeoaa?aeaeaii aeaieie
?*-niaeo?ineie?? oa o?i?/iiai aiae?co aeae?eaieo c aeno?aeo?a niieoe.

Ii??aiyiiy aeno?aeoe?eii? caeaoiino? aeayeeo eeniaai?uoth/eo
i?aai?/-ieo ?ic/eiiee?a ( aooaiie, ?ciai?eiaee nie?o, oeeeeiaaenaiie,
aooeeaoeaoao, iaoee?ciaooeeeaoii) ii a?aeiioaiith aei AIE Aae?th
(oaae.1) iieacaei aoaeoeai?noue aeei?enoaiiy a yeino? aeno?aaaioo
iaoee?ciaooeeeaoiio (I?AE). I?e oeueiio ia?ao?ae ?IE a i?aai?/io oaco ia
ia?aaeuo? 15%.

Oaaeeoey 1.

Nooi?iue aeeo/aiiy AIE GaMo10W2O405- aeayeeie i?aai?/ieie ?ic/eiieeaie
(R,%).

Aeno?aaaioEiioeaio?aoe?y H2SO4, M

0.250.501.001.251.50I?AE183578100100i-aooaiie1121435259?ciai?eiaee
ni??o917384550oeeeeiaaenaiie613293642aooeeaoeaoao00000

I?e aeine?aeaeaii? aeno?aeoe?eii? caeaoiino? iie?aaeiaieueo?aiiaaeao?a
o ?yaeo GaMoxW12-xO405- (x=1-3, 6, 9-11) anoaiiaeaia iiaeeea?noue
?iceeaaeo AIE c o=11 i?e i?aeeeneaii?, ui na?ae/eoue i?i eiai
iaaeinoaoith no?ee?noue. AIE GaMo10W2O405- ? a?eueo no?eeei ? ia
?iceeaaea?oueny iaa?oue o 4.0 I H2SO4 (?en.1). I?aeaeuaiiy
aeno?aeoe?eii? caeaoiino? iie?aaeiaieueo?aiiaaeao?a c ?inoii e?eueeino?
aoii?a Iie?aaeaio o e?aaiae? aeicaiey? ?aeiiaiaeoaaoe canoinoaaiiy aeey
aecia/aiiy Aae?th aeinoaoiuei

no?eeiai oa caeaoiiai eaaei ?en.1. Nooi?iue
aeeo/aiiy AIE

aeno?aaoaaoeny AIE GaMo10W2O405-. GaMoxW12-xO405- a I?AE,
x=11(1),

A oie aea /an nooi?iue aeeo/aiiy x=10(2), 9(3), 6(4),
3(5), 2(6), 1(7).

aeayeeo a?eueo iane/aieo Aieueo?aiii AIE na?ae/eoue i?i oa, ui aiie
oaeiae iiaeooue aooe aeei?enoai? ye aiae?oe/i? oi?ie a aeno?aeoe?eieo
iaoiaeeeao aecia/aiiy Aae?th.

Ciaeaeaia caeaaei?noue aeno?aeoe?eieo aeanoeainoae AIE a?ae e?eueeino?
aoii?a iaea?eueo aeaeo?iiiaeoeaioi?iiai iaoaeo o e?aaiae? (Ii) ?
aeieacii iayaiino? aeiii?ii-aeoeaioi?ii? aca?iiae?? i?ae
aaoa?iiie?ai?iiii oa eeniaai?uoth/ei aeno?aaaioii. I?e oeueiio aoii
eenith aeno?aaaioo ? aeiii?ii aeaeo?ii?a, a aoii Iie?aaeaio AIE —
aeoeaioi?ii. C?inoaiiy e?eueeino? aoii?a Iie?aaeaio o e?aaiaei?e noa??
AIE i?ecaiaeeoue aei i?aeaeuaiiy nieueaaoaoe?eii? aca?iiae?? AIE —
i?aai?/iee ?ic/eiiee, ui a naith /a?ao aaaea aei i?aeaeuaiiy
aeno?aeoe?eii? caeaoiino? AIE. I?i iayai?noue oaeeo aca?iiae?e
na?ae/eoue oaeiae caeaaei?noue aaee/ei ci?uaiiy iaeneioi?a nioa
iiaeeiaiiy a aeaeo?iiieo niaeo?ao AIE i?e ia?aoiae? inoaii?o a
?aaeno?aeo a?ae e?eueeino? aoii?a Iie?aaeaio o e?aaiae?. Iiae?ai?
caeiiii??iino? oa?aeoa?i? oaeiae aeey ?IE (oaae.2).

Oaaeeoey 2.

Cnoa a aeaeo?iiieo niaeo?ao a?aeiiaeaieo AIE oa ?IE i?e
aeno?aeoe??.

Ni?aa?aeiioaiiy [Mo]:[W] a eiiieaen??IE

AIE

max, iimax, iiH2OI?AE , iiH2OI?AE ,
ii10:273366865839865268:472065862842856146:67166595784485284:868365132—
—-3:967964732——

Aiaeia?/i? ci?ie niinoa??aathoueny ? a ?*-niaeo?ao AIE, inaaeaeaieo c
aeno?aeo?a. Aea /?oea caeaaei?noue aeno?aeoe?eieo aeanoeainoae AIE a?ae
eiai ca?yaeo (oaae.3) iiaea aooe iiyniaia eeoa c iiceoe?e
a?ae?aoii-nieueaaoii? oai???.

Oaaeeoey 3.

Ii??aiyiiy aeno?aeoe?eii? caeaoiino? iie?aaeiaieueo?aiiaeo AIE c ??cieie

oeaio?aeueieie aoiiaie (I?AE, 0.5 i H2SO4).

AIEPMo10W2O403-GeMo10W2O404-SiMo10W2O404-GaMo10W2O405-R,%100959338

Oaeei /eiii, ciaeaeai? aeieace ci?oaiiai iaoai?cio aeno?aeoe?? AIE, i?e
yeiio iathoue i?noea ye a?ae?aoii-nieueaaoi?, oae ? aeiii?ii-aeoeaioi?i?
aca?iiae?? AIE — ?ic/eiiee.

Aeno?aeoe?y a?aeiiaeaieo oi?i AIE Aae?th i?eioeeiiai ia a?ae??ciy?oueny
a?ae aeno?aeoe?? ieeneaieo AIE, aea ia?ao?ae a?aeiiaeaieo
?ciiie?eiiieaen?a a i?aai?/io oaco i?e oeueiio ca?eueoo?oueny. Oiio
canoinoaaiiy a aiae?c? aeno?aeoe?? a?aeiiaeaieo AIE Aae?th ia ?
aeioe?eueiei o ca’yceo c oei, ui iiaeeiaiiy “oieinoiai” ?ic/eio i?e
oeueiio iiaea ??cei c?inoaoe.

?IE, ui ooai?ththoueny o nenoaiao c aaeeeei ai?noii Aieueo?aio,
aeno?aaothoueny iaaaaaoi e?aua, i?ae iie?aaeaiia? ?IE (oaae.4).

Oaaeeoey 4.

Aeno?aeoe?y a?aeiiaeaieo ?IE, ye? ooai?ththoueny o nenoaiao xMo+(12-x)W,

1.8 M H2SO4.

x1234610R,%856360584242

Oea iia’ycaii c iiaeeea?noth ooai?aiiy o ?ic/eiao c aaeeeei ai?noii
Aieueo?aio ?IE ia iniia? iaoaaieueo?aiaoo eaa?iianueei? no?oeoo?e
H2W12O406-, aiaeia?/iiai ca nai?ie aeanoeainoyie AIE. O ?ic/eiao c
aaeeeei ai?noii Iie?aaeaio a?eueo a??ia?aeiei ? ooai?aiiy ?IE ia iniia?
aaena-, aaioa- oa ieoaiie?aaeaoo (Mo6O192-, Mo7O246-, Mo8O264-). Oea
i?aeoaa?aeaeo? aiae?c ?*-niaeo??a aeae?eaieo c aeno?aeo?a nieae ?IE c
??ciei ni?aa?aeiioaiiyi [Mo]:[W]. Anoaiiaeaii, ui i?e i?aeeeneaii?
?ic/ei?a c aaeeeei ai?noii Iie?aaeaio a iueiio ooai?ththoueny a
iniiaiiio ?IE ia iniia? aaioa- oa ieoaiie?aaeaoo oa iacia/ia e?euee?noue
aaena-?IE. A aeno?aeoao aoee ciaeaeai? eeoa aaioa- oa ieoa-?IE. Oaeei
/eiii, neeaaei? ??aiiaaae a eeneeo ?ic/eiao iie?aaeiaieueo?aiao?a
noi?iaiaeaeothoue aeno?aeoe?th ?IE.

Ca ?acoeueoaoaie aeaoaeueiiai aea/aiiy ia?aiao??a aeno?aeoe??
aaoa?iiie?ai?iio GaMo10W2O405- cai?iiiiiaaia oaea ??aiyiiy aeno?aeoe??:

[H 2GaMo10W2O40wmetafile8? ??P?????????????
???????????yyy????.????1?????? ???????  
???&??yyyy?????Ay¬ya?I ???&?
?MathType??P????&??yyyy???????????X5c’
AtAe^&C?&?_?=H3-x[H2GaMo10W2O40]x- 10 I?AEi?a , aea x=0-2.

Nieueaaoia /enei (10) aoei ciaeaeaia ye oaiaain eooa iaoeeo
eiaa?eoi?/ii? caeaaeiino? eiao?oe?aioo ?iciiae?eo AIE (D) a?ae
eiioeaio?aoe?? I?AE o noi?o? c ?ia?oiei ?ic/eiieeii (CCl4). Aiaeia?/ii
caeaaei?noue lgD — lgC(H+) aeicaieeea ciaeoe /enei i?ioii?a, ye?
i?eeiathoue o/anoue o i?ioiioaaii? AIE (aoaeoeaia iniiai?noue).
Anoaiiaeaii, ui aaoa?iiie?ai?ii caeaaeii a?ae eiai eiioeaio?aoe??
i?e?aeio? a i?ioean? aeno?aeoe?? a?ae iaeiiai aei o?ueio i?ioii?a
(?en.2). Iaeneiaeueia cia/aiiy aoaeoeaii? iniiaiino? (3 H+ i?e NAIE=4.4
10-3 iieue/e) a?aeiia?aea? iayaiino? o AIE Aae?th o?ueio neeueieo oa
aeaio a?eueo neaaeeo i?ioii?a. Cie-aeaiiy aoaeoeaii? iniiaiino? i?e
i?aeaeuaii? eiioeaio?aoe?? AIE (i?aaa a?eea e?eai? ?en.2) iiynith?oueny
ciaiueoaiiyi eiai aeenioe?aoe??, a i?e ciaiueoaii? eiioeaio?aoe?? AIE —
iiaeeea?noth ia?aoiaeo AIE a i?aai?/io oaco

o aeaeyae? ieceica?yaeaeaieo eii-

ieaen?a.

Ca aeiiiiiaith iaaaaeaiiai ?en.2. Caeaaei?noue aoaeoeaii?
iniiaiino?

??aiyiiy aeno?aeoe?? ?ic?aoiaaia AIE Aae?th a?ae eiai
eiioeaio?aoe??.

eiinoaioa aeno?aeoe?? AIE Aae?th

aeey iaeneiaeueiiai cia/aiiy aoaeoeaii? iniiaiino? (3H+). Aiia
aei??aith? 1.30+0.07.

Aeno?aeoeey — oa -?ciia??a GaMo10W2O405- aea/aeanue c iaoith
ciaoiaeaeaiiy oiia ?o ?icae?eaiiy. Anoaiiaeaia caeaaei?noue
aeno?aeoe?eieo aeanoeainoae AIE a?ae ?o a?aeiinii? no?eeino?. I?e
a?aeiiaeaii? -oi?ie a?aeaoaa?oueny ?? ?ciia??caoe?y o a?eueo no?eeo
-oi?io, oiio ?ioa?aaee aeno?aeoe?? a?aeiiaeaieo ?ciia??a ni?aiaaeathoue.
Ui aei aeno?aeoe?? ieeneaieo oi?i, oi aeey ia? oa?aeoa?ia ?ioa
caeiiii??i?noue: aeno?aeoe?y ieeneaii? -oi?ie noi?iaiaeaeo?oueny ??
?iceeaaeii. Oiio iiaeeea?noue ?icae?eaiiy ?ciia??a AIE iieyaa? o iiooeo
oiia, ca yeeie iaeei c ?ciia??a ?oeio?oueny, a ae?oaee aeno?aao?oueny.
Oae? oiiae aoee ciaeaeai? aeey ieeneaieo ?ciia??a: i?e aaaaoi?aciai?
aeno?aeoe?? AIE Aae?th ?c 0.5 M H2SO4 iiaeeeai cia/ii i?aeaeueoe /anoeo
-oi?ie o noi?o?. C?in?aiiy eeneioiino? aeno?aeoe?? i?ecaiaeeoue aei
iinooiiaiai ?oeioaaiiy -?ciia?o ? ia?aaaaeiiai ia?aoiaeo -oi?ie a
aeno?aeo.

O?ao?e ?icae?e aeena?oaoe?? i?enay/aii aea/aiith iiaeeeaino?
canoinoaaiiy aeno?aeoe?? aeey neioaco oa ciaoiaeaeaiiy oiia ooai?aiiy
AIE Aae?th. Cai?iiiiiaaii niin?a neioaco ia caa?oaeiaieo aeii?oeaie ?IE
aaoa?iiie?eiiieaen?a, yeee iieyaa? a aeno?aaoaaii? AIE c aiaeieo
?ic/ei?a oa aeae?eaii? ?o c ?aaeno?aeo?a. *enoioa caeiaooeo oaeei /eiii
niieoe i?aeoaa?aeaeaia aeaieie o?i?/iiai aiae?co ia ai?no Aae?th,
Iie?aaeaio oa Aieueo?aio. Iayai?noue /enoeo, ?ic/eiieo o aiae? e?enoae?a
AIE Aae?th aeicaieeea ?ic?aooaaoe ?noeii? iiey?i? eiao?oe??ioe
iiaeeiaiiy oe??? niieoee o aiaeieo ?ic/eiao.

Naeaeoeaia oa iiaia aeno?aeoe?y iaoee?ciaooeeeaoiiii aeicaiey?
aeae?eyoe AIE c ?aaeoe?eii? noi?o? ? oei naiei ciaoiaeeoe ?aaeueio
eiioeaio?aoe?th i?iaeoeoo ?aaeoe?? ooai?aiiy AIE ca aoaeue yeeo oiia ??
i?i-aaaeaiiy. Anoaiiaeaii, ui o aeiaaeeo Aae?th aeno?aeoe?y AIE ia
ci?uo? ??aii-aaae o a?e i?aeaeuaiiy aeoiaeo AIE: ia oea aeaco? iiaia
a?aenooi?noue aae?th a aeno?aeoao i?e aeno?aaoaaii? iaiaa??oi? noi?o?
Ga3+-x MoO42—(12-x)WO42—H3O+ iaa?oue ?c cia/ii i?aeeeneaieo ?ic/ei?a.
Oea iiynith?oueny oei, ui AIE Aae?th no?oeoo?e Eaa?ia oi?io?oueny eeoa
i?e iaa??aaii?, ? iiaeaeueoa eiai aeno?aeoe?y ?aea a oiiaao
“caii?iaeaii?” ??aiiaaae.

??aiiaaaeia eiioeaio?aoe?y AIE ciaoiaeeeanue ca aeiiiiiaith iai?yiiai
iaoiaea, yeee a?oioo?oueny ia aeno?aeoe?eiiio aeae?eaii? AIE c
?aaeoe?eii? noi?o?, eoaeiiio ?iceeaae? eiai a aeno?aeo? oa aecia/aii?
Iie?aaeaio, yeee aoiaeeoue aei eiai neeaaeo ca ?aaeoe??th c
?iaeai?ae-?iiaie. Oea aeicaieeei aaciina?aaeiuei ?ic?aoiaoaaoe aeo?ae
AIE ye a?aeiioaiiy ciaeaeaii? a ?aeno?aeo? e?eueeino? Iie?aaeaio aei
oai?aoe/ii? e?eueeino?, yea a?aeiia?aea? 100% ooai?aiiy AIE: =100
nMociaeae./nMooai?.,%.

Canoinoaaiiy aeno?aeoe?? AIE aeaei iiaeeea?noue ooi/ieoe oiiae
ooai?aiiy AIE Aae?th. Ia a?aei?io a?ae iiia?aaei?o aeine?aeaeaiue
anoaiiaeaii, ui i?aeaeuaiiy eiioeaio?aoe?? eeneioe a ?aaeoe?eii? noi?o?
nooo?ai ia aieeaa? ia aeo?ae AIE Aae?th. I?e i?aeaeuaii? z=C(H+)/C(Mo+W)
a?ae 1.33 (oai?aoe/ia cia/aiiy ca ??aiyiiyi ?aaeoe?? Ga3++x
MoO42-+(12-x) WO42-+

+16H+=GaMoxW12-xO405-+8H2O ) aei z=2.00 aeo?ae eiiieaena o a?aenooiino?
iaaeeeoeo ?ii?a e?aaiaeo c?inoa? a?ae 60% aei 70%.

A?eueo aieeaiaei oaeoi?ii i?aeaeuaiiy aeoiaeo AIE ? eiioeaio?aoe?y
?ii?a e?aaiaeo. Ciaeaeai? caeaaeiino? aeoiaeo AIE
Aae?th a ?yaeo

GaMoxW12-xO405- a?ae iaaeeeoeo a?aeiia?aeiiai e?aaiaeo
(xMoO42-+(12-x)WO42-) i?e iaci?iiiio pH(z) aeicaieeee ?ic?aooaaoe
eiinoaioe no?eeino? aaoa?iiie?eiiieaen?a c ??ciei ni?aa?aeiioaiiyi Mo:W
ca ??aiyiiyi:

[AIE]

=

[Ga3+] [MoO42-]x [WO42-]12-x

Iiaeeea?noue aecia/aiiy ??aii- ?en.3. Caeaaei?noue
GaMoxW12-xO405

aaaeii? eiioeaio?aoe?? AIE aeicaiey? a?ae neeaaeo
e?aaiaea.

?ic?aoiaoaaoe eiioeaio?aoe?? ?ioeo /anoeiie a ?aaeoe?ei?e noi?o?.
Iaea?aeai? eiinoaioe (?en.3) ? oiiaieie, ine?eueee i?e ?o ?ic?aooaaii?
aoei c?iaeaia i?eiouaiiy i?i ooai?aiiy AIE c iiii/anoeiie, aea a oiiaao
oaeeo neeaaeieo nenoai, ye iie?ieniai?iie, oeae iaoiae ?
caaaeueiii?eeiyoei. Ine?eueee oeae iaoiae iiaea aooe canoiniaaiee eeoa
ii a?aeiioaiith aei caeaoieo eaaei aeno?aaoaaoeny eiiieaen?a, aeai? aeey
AIE c o=1 oa 2 acyo? c iiia?aaei?o aeine?aeaeaiue. Aiae?c iaaaaeaii? ia
?en.3 caeaaeiino? na?ae/eoue i?i aeioe?euei?noue aeei?enoaiiy a
aacaeno?aeoe?eieo iaoiaeeeao aecia/aiiy Aae?th iie?aaeiaieueo?aiiaeo AIE
c o=2-4 ye iaea?eueo no?eeeo. Aei oiai ae iaiaaeaia e?euee?noue aoii?a
Iie?aaeaio o e?aaiae? aeicaiey? eaaei eiio?iethaaoe nooi?iue
a?aeiiaeaiiy AIE.

Naeaeoeaia a?aeiiaeaiiy AIE GaMo4W8O405- a?ae?aceiii o n??/aiieeneiio
na?aaeia?u? (?en.4) aaaea aei ooai?aiiy 4-aeaeo?iiii? nei? c iaeneioiii
iiaeeiaiiy i?e 900 ii. Ooai?aiiy 4-aeaeo?iiii? nei? i?aeoaa?aeaeo?oueny
iaoiaeii ?ciiiey?ii? na??? oa o?i?/iei aiae?cii iaea?aeaiiai o oaa?aeiio
noai? AIE ia ai?no Mo(V). Iioei?caoe?y oiia a?aeiiaeaiiy GaMo4W8O405-
a?ae?aceiii aeicaieeea cai?iiiioaaoe iaoiaeeeo aacaeno?aeoe?eiiai
aecia/aiiy Aae?th c aeei?enoaiiyi oeueiai eiiieaeno c /ooeea?noth 10-5
iieue/e ?en.4. Caeaaei?noue a?aeiiaeaiiy AIE

Ga3+. A?aaeothaaeueiee a?ao?e GaMo4W8O405- (1) oa
a?aeiia?aeiiai

iieno?oueny ??aiyiiyi: ?IE (2) a?ae
pH.

A=(0.025+0.001)+(5090+390) CGa,

eiao?oe??io ei?aeyoe?? 0.999. Ia a?aei?io a?ae aeno?aeoe?eiiai
aecia/aiiy Aae?th o aeaeyae? GaMo10W2O405-, a?aeiiaeaiiy GaMo4W8O405-
a?ae?aceiii iiaea aooe canoiniaaii i?e aecia/aii? Aae?th o
aieueo?aiai?uoth/eo iaoa??aeao.

*aoaa?oee ?icae?e aeena?oaoe?? i?enay/aii canoinoaaiith aeno?aeoe??
GaMo10W2O405- aeey iie?auaiiy aiae?oe/ieo oa?aeoa?enoee aecia/aiiy
Aae?th o aeaeyae? AIE. Iiaeeea?noue aeei?enoaiiy aeno?aeoe??
GaMo10W2O405- a aiae?c? aoea i?iaeaiiino?iaaia ?ic?iaeith
aeno?aeoe?eii-niaeo?ioioiiao?e/ii? iaoiaeeee aecia/aiiy Aae?th o
aeaeyae? oeueiai AIE. Oea aeicaieeei cia/ii iie?aueoe aiae?oe/i?
oa?aeoa?enoeee aecia/aiiy o ii??aiyii? c iaoiaeeeith, a ye?e
canoiniao?oueny i?yia oioiiao?oaaiiy ieeneaiiai AIE GaMo10W2O405-:
ciaioeoe iiaeeiaiiy “oieinoiai” ?ic/eio, i?aeaeueoe /ooeea?noue
aecia/aiiy aei 10-5 iieue/e Aae?th caaaeyee eiioeaio?oaaiith. I?e
oeueiio ae??oaia ieoaiiy onoiaiiy caaaaeath/iai aieeao oaeeo aeaiaio?a,
ye P, Si, As, Ge. Oea aoei aeinyaiooi caaaeyee caeaoiino? Aae?th
ooai?thaaoe AIE no?oeoo?e Eaa?ia eeoa i?e iaa??aaii?, a oie /an ye AIE
P, Si, As, Ge ooai?ththoueny i?e e?iiaoi?e oaiia?aoo??. Oaeei /eiii,
caaaaeath/? aeaiaioe a?aeie?aieththoue a?ae Aae?th aeno?aaoaaiiyi ?o
AIE, a iio?i iaeo?ae?cothoue aiaeio oaco aei pH 3 (iioeiaeueiee pH
ooai?aiiy AIE Aae?th) ? iaa??aathoue. Oeae iaoiae ? cia/ii e?auei o
ii??aiyii? c ?icae?eaiiyi oeeo aeaiaio?a i?yiith aeno?aeoe??th ?o AIE,
ine?eueee ?ioa?aaee aeno?aeoe?? /anoeiai ia?ae?eaathoueny (oaae.3). Aei
oiai ae oaeee niin?a aeicaiey? cae?enithaaoe iaeii/ania aecia/aiiy
Aae?th oa ia?ae?/aieo aeaiaio?a c iaeiiai ?ic/eio.

Aeey aeinyaiaiiy a?eueo aeniei? /ooeeaino? aecia/aiiy Aae?th o aeaeyae?
AIE cai?iiiiiaaii aeaa iai?yiee: a?aeiiaeaiiy AIE a i?aai?/i?e oac? c
canoinoaaiiyi iiia?aaeiueiai aeno?aeoe?eiiai eiioeaio?oaaiiy oa iai?yia
aecia/aiiy Aae?th ca Iie?aaeaiii, ui aoiaeeoue aei neeaaeo AIE.

A?aeiiaeaiiy AIE a i?aai?/ieo ?ic/eiao ? a?eueo neeaaeiei a ii??aiyii?
c i?ioeanii a?aeiiaeaiiy a aiaeieo ?ic/eiao, oiio a yeino? a?aeiiaieea
aoei aeei?enoaii oei?eae ieiaa (II). A?aeiiaeaiiy AIE Aae?th oei?eaeii
ieiaa (II) a I?AE a?aeaoaa?oueny ieoo?ai, i?e oeueiio ia a?aei?io a?ae
aiaeieo ?ic/ei?a AIE, ooai?th?oueny i?iaeoeo c /?oei o?eniaaiei nooiaiai
a?aeiiaeaiiy: aeaioaeaeo?iiia neiue, iaeneioi iiaeeiaiiy yei? (710 ii)
ia caeaaeeoue a?ae eeneioiino? a?aeiiaeaiiy. Ia caaaeath/e ia oa, ui ca
aeaieie ?*-niaeo?ineii?? ieiai iiaea aoiaeeoe aei neeaaeo AIE,
cai?uath/e a iueiio Iie?aaeai aai Aae?e (ia ui aeaco? a?aenooi?noue
iieine eieeaaiue oao?aaae?a GaO4 i?e 460 ni-1), iiaeeiaiiy a?aeiiaeaieo
aeno?aeo?a i?iii?oe?eia ii/aoeia?e eiioeaio?aoe?? Aae?th, ui aeicaiey?
canoiniaoaaoe oeth ?aaeoe?th a aiae?c?. A caeaaeiino? a?ae nooiaith
aeno?aeoe?eiiai eiioeaio?oaaiiy AIE (10- /e 2-e?aoia) iiaeeeaa
aecia/aiiy Aae?th o aeaio ?ioa?aaeao eiioeaio?aoe?e:

10-6 — 10-5 iieue/e oa 10-5 — 8 10-4 iieue/e.

A?aeiiaeaiiy AIE Aae?th oei?eaeii ieiaa (II) a aeno?aeo?
oa?aeoa??co?oueny cia/iith naeaeoeai?noth ii a?aeiioaiith aei ?yaeo
aeaiaio?a (oaae.5). Naeaeoeai?noue aecia/aiiy Aae?th oeei iaoiaeii ii
a?aeiioaiith aei In, Co, Cd, Mo oa W iaa?oue a?eueo aeniea, i?ae o
iaoiaeeeao ?c canoiaoaaiiyi ?iaeai?iiaeo aa?aiee?a. Oea aeicaieeei
cai?iiiioaaoe aeaio iaoiaeeeo aeey aecia/aiiy 0.05 — 0.20 % Aae?th a
nieaaao ?iae?th aac iiia?aaeiueiai a?aeie?aieaiiy iniiae.

Oaaeeoey 5.

Oa?aeoa?enoeea naeaeoeaiino? aecia/aiiy Aae?th a?aeiiaeaiiyi
GaMo10W2O405- a aeno?aeo? oei?eaeii ieiaa (II). (Aeacaiee iiey?iee
iaaeeeoie ?iio ii a?aeiioaiith aei Aae?th, i?e yeiio ii/eia? i?iyaeyoeny
eiai caaaaeath/ee aieea).

?iiIn3+Al3+Cu2+Co2+Ni2+Mg2+Cd2+Zn2+MoO42-WO42-Iaaeeeoie>5000502001000200
500100101000200

Iiaeeea?noue a?ae?ie?co ?iae?th aeeeth/aia caaaeyee no?ia?e
iine?aeiaiino? ci?ooaaiiy ?aaaaio?a i?e ooai?aii? AIE: aei i?aeeeneaiiai
aei pH 3 ?ic/eio, yeee i?noeoue Aae?e oa ?iae?e, aeiaeathoue ?aaeoea
(noi?o i?aeeeneaiiai aei z=1.33 iie?aaeaoo oa aieueo?aiaoo o
noao?iiao??/iiio ni?aa?aeiioaii?).

I?aaeeuei?noue iaoiaeeee ia?aa??aia i?e aiae?c? iano Ga — In: i?e
ai?no? 0.125% Ga ciaeaeaii (0.129+0.013)%, Sr=0.035 (P=0.95, n=5).

Oni?oia aeno?aeoe?eia a?aeie?aieaiiy AIE Aae?th a?ae ?ciiie?eiiieaen?a,
ui ooai?ththoueny a oiiaao iaaeeeoeo ?aaaaioo (?ii?a e?aaiaeo), aea?
iiaeeea?noue i?aeaeuaiiy /oaoeeaino? aecia/aiiy Aae?th ca ?aooiie
canoinoaaiiy iai?yieo iaoiae?a. Oaeoi? iiiaeaiiy o oeueiio aeiaaeeo
aei??aith? 10 (a iieaeoe? AIE ia 1 aoii Aae?th i?eoiaeeoueny 10 aoii?a
Iie?aaeaio). I?aea?? iaea?eueo /ooeeaeo ?aaeoe?e aecia/aiiy Iie?aaeaio
aeicaiey? oaeei /eiii iie?auaoe aiae?oe/i? oa?aeoa?enoeee aecia/aiiy
Aae?th o aeaeyae? AIE.

Cai?iiiiiaaii o?e aa??aioe iai?yiiai aeno?aeoe?eiiai aecia/aiiy Aae?th:
c canoinoaaiiyi aei??thaaiiy iiaeeiaiiy MoO42- a ?aaeno?aeo?, c
aeei?enoaiiyi ?aaeoe?? MoO42- c ?iaeai?ae-?iiaie oa ca aeiiiiiaith
eiiieaeniiiiao??/iiai oeo?oaaiiy iie?aaeaoo. An? o?e iaoiaeeee caniiaaii
ia iiia?aaei?e aeno?aeoe?? AIE Aae?th iaoee?ciaooeeeaoiiii ?c
na?aaeiaeua 1.5 I H2SO4 oa ?iceeaae? a i?aai?/i?e oac? ca aeiiiiiaith
eoao, yeee noi?iaiaeaeo?oueny ?aaeno?aeoe??th eiiiiiaio?a AIE (Ga3+,
MoO42-, WO42-) o aiaeiee ?ic/ei.

Cae?enieoe ia?oee aa??aio iai?yiiai aecia/aiiy Aae?th iiaeeeai caaaeyee
?ioaineaiiio iiaeeiaiith iie?aaeaoa a OO-iaeano? niaeo?a (max=210 ii).
Iiaeeiaiiy aieueo?aiao-?ii?a i?e oeueiio ? cia/ii iaiueoei ? i?e
ni?aa?aeiioaii? Mo:W=10:2 eiai aeeaae iiaeeeai ia a?aoiaoaaoe. Iiey?iee
eiao?oe?aio, ia?a?aoiaaiee ia Aae?e, neeaaea? 56000. Aea
a?aeoai?thaaii?noue ?acoeueoao?a nooo?ai caeaaeeoue a?ae iiaeeeaino?
/anoeiaiai ?ic/eiaiiy aeno?aaaioo a aiae?. Ine?eueee a?eueo?noue
i?aai??/ieo ?ic/eiiee?a iathoue aaeeea iiaeeiaiiy a OO-iaeano? niaeo?a,
iaa?oue iacia/ia ?ic/eii?noue aeno?aaaioa a aiae? iiaea noaoe
caaaaeath/ei oaeoi?ii i?e i?iaaaeaii? aiae?co. Ca oeeo oiia iaoiaeeea,
caniiaaia ia aei??thaaii? iiaeeiaiiy ?iaeai?aeiiai eiiieaeno Iie?aaeaio
? a?eueo iaae?eiith. Eiiieaen MoO(SCN)3 ooai?th?oueny a eeneiio
na?aaeia?u? a i?enooiino? a?aeiiaieea — anei?a?iiai? eeneioe oa
eiiieaenaioa, yeee caiia?aa? aieeao Aieueo?aio — eeiiiii? eeneioe.
Aei??thaaiiy cae?eniththoueny i?e 460 ii. Iiey?iee eiao?oe??io a
ia?a?aooieo ia Aae?e aei??aith? 87500. ??aiyiiy a?aaeothaaeueiiai
a?ao?eo: A=(0.026+0.009)+(87500+1130) CGa . Eiao?oe??io ei?aeyoe??
0.992. Cai?iiiiiaaia iaoiaeeea ia?aa??aia i?e aiae?c? iaoiaeii
aeiaeaoe?a noaiaea?oiiai c?acea nieaao Aethi?i?th (I 207 AE 5I2 ? 2071),
yeee i?noeoue oaeiae 3.52% Cu, 6.91% Si, 1.17% Zn, 0.088% Mn, 0.865% Mg,
0.071% Ti, 0.338% Fe, 0.103% Ni, 0.245% Pb. ?acoeueoaoe iaaaaeai? a
oaae.6.

Oaaeeoey 6.

Aecia/aiiy Aae?th a noaiaea?oiiio c?aceo nieaao Aethi?i?th ca
aeiiiiiaith iai?yii? iaoiaeeee ii iiaeeiaiith MoO(SCN)3 a ?aaeno?aeo?.

Aeiaeaii Ga,%Ciaeaeaii
Ga,%Sr0.150.13+0.020.1320.200.22+0.030.1110.300.29+0.020.0700.400.39+0.0
20.054

Onoiaiiy aieeao N?e?oe?th aeinyaiaii oeyoii iiia?aaeiuei? aeno?aeoe??
a?aeiia?aeiiai AIE, yeee oi?io?oueny ia oieiae?.

Iieacaii, ui iai?yia aecia/aiiy Aae?th o aeaeyae? AIE iiaea aooe
cae?eniaia ia eeoa ca aeiiiiiaith niaeo?ioioiiao??/ieo iaoiaeee.
E?ioeaaith noaae??th aecia/aiiy iiaea aooe oeo?oaaiiy aenaiaiaeaeaiiai c
AIE Iie?aaeaio. Oea aea? iiaeeea?noue cai?iiiioaaoe aeni?anio iaoiaeeeo
aecia/aiiy Aae?th, /ooeea?noue yei? ? cia/ii a?eueoith, i?ae o aeiaaeeo
eiiieaeniiiiao??/iiai oeo?oaaiiy Aae?th. Caaaeyee aeanyoee?aoiiio
iiiaeaiith i?e ia?a?aooieo ia Aae?e aeno?aeoe?eii-oeo??iao?e/ia
iaoiaeeea aeicaiey? aecia/aoe aei 1 10-4 iieue/e Aae?th.

A?aoiaoth/e iiaeeea?noue aeno?aeoe?eiiai ?icae?eaiiy Aae?th oa
aeaiaio?a, caeaoieo ooai?thaaoe AIE, aeno?aeoe?eii-oeo?eiao?e/ia
iaoiaeeea iiaea aooe aeei?enoaia aeey iiaiiai aiae?co
iai?ai?ia?aeieeiaeo nieaa?a oeio Ga-P, Ga-As, Ga-Ge. Ine?eueee
eiiieaeniiiiao?e/ia oeo?oaaiiy ca’ycaiiai a AIE Iie?aaeaio a ?aaeno?aeo?
aeicaiey? aecia/aoe ia eeoa Aae?e, a ? PV, AsV, GeIV oa ?io? aeaiaioe,
oey iaoiaeeea aea? iiaeeea?noue aecia/aoe iaeaeaa eiiiiiaioe ia?ae?/aieo
nieaa?a c iaei??? iaaaaeee. I?e oeueiio oi/i?noue aecia/aiiy aoaea
cia/ii aeuith, i?ae i?e canoinoaaii? i?yiiai eiiieaeniiiiao??/iiai
oeo?oaaii? Aae?th oa ciaoiaeaeaii? ai?noo ae?oaiai aeaiaioo ca
??cieoeath. Iaoiaeeea aoea ai?iaiaaia i?e aiae?c? ?ic/ei?a, ye?
iiaeaeththoue neeaae iai?ai?ia?aeieeiai? nenoaie Ga-P c ??ciei ai?noii
Aae?th. ?acoeueoaoe iaaaaeai? a oaae.7.

Oaaeeoey 7.

?acoeueoaoe aiae?co ?ic/ei?a, ye? iiaeaeththoue neeaae
iai?ai?ia?aeieeiai? nenoaie Ga-P ca iaoiaeeeith iai?yiiai
eiiieaeniiiiao?e/iiai oeo?oaaiiy (n=7, P=0.95).

AeaiaioGaPAeiaeaii,%50.050.0Ciaeaeaii,%48.5+1.648.5+1.8Sr0.0280.029Aeiae
aii,%33.366.7Ciaeaeaii,%32.8+2.365.1+1.7Sr0.0760.020

AENIIAEE

1. Aia?oa aea/aia aeno?aeoe?y 14 ieeniaieo oa a?aeiiaeaieo
iie?aaeiaieueo?aiiaeo aaoa?iiie?eiiieaen?a Aae?th a ?yaeo
GaMoxW12-xO405- (x=1, 2, 3, 6, 9, 10, 11). Anoaiiaeaii, ui iaea?eueo
aoaeoeaiei aeno?aaaioii ? iaoee?ciaooeeeaoii, yeee aei oiai ae aeicaiey?
iaea?eueo iiaii ?iciiae?eyoe AIE oa ?IE. Ciaeaeaia /?oea caeaaei?noue
aeno?aeoe?eieo aeanoeainoae AIE o aea/a?iiio ?yaeo a?ae e?eueeino?
aoii?a Ii a e?aaiae?, c a?aooaaiiyi yei? iaea?eueo ia?niaeoeaiith aeey
aeei?enoaiiy a aiae?c? ? oi?ia GaMo10W2O405- . Iioeiaeueia eeneioi?noue
aeno?aeoe?? oeueiai AIE — 1.5 I I2SO4.

2. Aea/aia aeno?aeoe?y ?IE, ye? ooai?ththoueny a nenoaiao c ??ciei
ni?aa?aeiioaiiyi Ii:W. Anoaiiaeaii i?aeaeuaiiy aeno?aeoe?eieo
aeanoeainoae ?IE i?e a?aeiiaeaii?, a oaeiae iaaaaaoi e?au? aeno?aeoe?ei?
aeanoeaino? aieueo?aiiaeo ?IE a ii??aiyii? c iie?aaeaiiaeie. Iaea?aeai?
?acoeueoaoe iiaeooue aooe aeei?enoai? i?e aeno?aeoe?eiiio aecia/aii? ia
eeoa Aae?th, a e aeaiaio?a, caeaoieo ooai?thaaoe aaoa?iiie?niieoee (P,
Si, Ge oa ?io?).

3. Aeine?aeaeai? ia?aiao?e aeno?aeoe?eii? ??aiiaaae a nenoai?
GaMo10W2O405- — H2SO4 — I?AE. Anoaiiaeaii, ui a i?ioean? aeno?aeoe??
AIE nieueaaoo?oueny 10 iieaeoeaie I?AE. Aeine?aeaeaiiyi i?ioiioaaiiy
aaoa?iiie?ai?iio i?aeoaa?aeaeaia iayai?noue o AIE aae?th o?ueio neeueieo
oa aeaio a?eueo neaaeeo i?ioii?a. Cai?iiiiiaaia ??aiyiiy aeno?aeoe??:

[H2GaMo10W2O40]3-+(3-x)H+ = H3-x[H2GaMo10W2O40]x-aiae +10 MIAE=

= H3-x[H2GaMo10W2O40]x-i?a 10 I?AE, aea o=0-2, yea a?aoiao? ci?iia
cia/aiiy aoaeoeaii? iniiaiino? AIE. ?ic?aoiaaia eiinoaioa aeno?aeoe??
aei??aith? (1,30 0,07).

4. Ca aeiiiiaith iaoiae?a ?* — oa aeaeo?iiii? niaeo?ineii??
aeine?aeaeaii iaoai?ci aeno?aeoe?? AIE Aae?th. Ciaeaeai?
i?aeoaa?aeaeaiiy ye aeiii?ii-aeoeaioi?ieo, oae ? a?ae?aoii-nieueaaoieo
aca?iiae?e a nenoai? AIE — i?aai?/iee ?ic/eiiee.

5. Cai?iiiiiaaia canoinoaaiiy aeno?aeoe?? aeey neioaco ia caa?oaeiaieo
aeii?oeaie ?IE ?ic/eiieo nieae aaoa?iiie?niieoe, a oaeiae aeey
aeine?aeaeaiiy oiia ooai?aiiy AIE. Aea/aia caeaaei?noue aeoiaeo AIE a?ae
??cieo oaeoi??a (eiioeaio?aoe?y i?ioii?a, ?ii?a e?aaiaea), ui aeaei
iiaeeea?noue ?ic?aooaaoe eiinoaioe no?eeino? AIE o aea/a?iiio ?yaeo.
Iaea?eueo no?eeeie ? AIE c 2-4 aoiiaie Iie?aaeaio a e?aaiae? (?g =32),
caaaeyee /iio ?o canoinoaaiiy ? ia?niaeoeaiei a aacaeno?aeoe?eieo
iaoiaeeeao aecia/aiiy Aae?th, ui i?aeoaa?aeaeaii ciaeaeaieie oiiaaie
naeaeoeaiiai a?aeiiaeaiiy AIE GaMo4W8O405-.

6. Aeine?aeaeaia a?aeiiaeaiiy AIE Aae?th a i?aai?/i?e oac? oei?eaeii
ieiaa ??), naeaeoeai?noue yeiai aeicaiey? cai?iiiioaaoe aeei?enoaiiy
oe??? ?aaeoee? i?e aecia/aii? 0.05 — 0.20% Aae?th a ?iae?? aac
iiia?aaeiueiai a?aeie?aieaiiy iniiae.

7. Cai?iiiiiaai? aeno?aeoe?eii-niaeo?ioioiiao?e/i? iaoiaeeee iai?yiiai
aecia/aiiy Aae?th ca Iie?aaeaiii, ca’ycaiei a AIE. Ciaeaeaia
iiaeeea?noue aeno?aeoe?eiiai ?iciiae?eo aae?th oa aeaiaio?a, caeaoieo
ooai?thaaoe AIE ia oieiae?, aeicaiey? aeei?enoaoe oe? iaoiaeeee aeey
iiaiiai aiae?co iai?ai?ia?aeieeiaeo nenoai oeio Ga — P.

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

1. Eieueoeiaa A.A., Aeoieeei A.A., Oeuaaiie E.I. Yeno?aeoeey
iieeaaeiaieueo?aiiauo aaoa?iiieeeiiieaenia aaeeey.// Oe?. oei.
aeo?i.-1998.-o.64.-? 2.-N.126-129.

2. Eieueoeiaa A.A., Aeoieeei A.A., Oeuaaiie E.I. Iaoiaeu iiauoaiey
/oanoaeoaeueiinoe ii?aaeaeaiey aaeeey a aeaea aaoa?iiieeeiiieaenia.//
Oe?. oei. aeo?i.-1998.-o.64.-? 4.-N.118-120.

3. Eieueoeiaa A.A., Aeoieeei A.A., Oeuaaiie E.I. Einaaiiia
yeno?aeoeeiiii-niaeo?ioioiiao?e/aneia ii?aaeaeaiea aaeeey a aeaea
aaoa?iiieeeiiieaenia.// Caa. eaa.-1998.-o.64.-? 10.-N.8-9.

4. Eieueoeiaa A.A., Aeoieeei A.A., Oeuaaiie E.I.
Niaeo?ioioiiao?e/aneia ii?aaeaeaiea aaeeey a aeaea ainnoaiiaeaiiiai
aeae?aceiii GaMo4W8O405-.//Oe?. oei. aeo?i.-1998.-o.64.-? 5.-N.44-47.

5. Eieueoeiaa A.A., Aeoieeei A.A., Oeuaaiie E.I. Ii?aaeaeaiea eiinoaio
onoie/eainoe iieeaaeiaieueo?aiiauo eiiieaenia aaeeey.// A?niee AeAeO.
Na??y o?i?/ia.-1998.-? 2.-N.30-34.

6. Tsiganok L.P., Tkach V.I., Vishnikin A.B., Maltseva G.V., Glukhova
O.I., Karandeeva N.I., Vakulitch A.N., Koltsova E.G. Perspectives of
using of the 12-heteropolycomplexes with Keggin structure in analysis.//
Abstr. of Int. Congress on Analytical Chemistry.-Moscow, 1997.-v.1.-P.
G-59.

7. Aeoi?e?i A.A., Oeeaaiie E.I., Oea/ A.?., Aeooiaa I.?., Ea?aiae??aa
I.?., Naaaae??aa I.I., Eieueoeiaa I.A. Aea/aiiy ?aaeoe?e ooai?aiiy,
neioac oa no?oeoo?a aaoa?iiie?eiiieaen?a aae?th.// Oac. aeii. XIV Oe?.
eiioa?. c iai?aai?/ii? o?i??.- Ee?a, 1996.-N.188.

8. Eieueoeiaa A.A., Aaeoee/ A.I., Aeoieeei A.A., Oeuaaiie E.I.
Ii?aaeaeaiea aieueo?aia e aaeeey a aeaea eci- e aaoa?iiieeeiiieaenia.//
Oac. aeiee. II Iaaeaeoia?. eiioa?. “Aeaai?iaeiua e ?aaeeea iaoaeeu”.-
Aeiiaoee, 1997.-/.II.-N.44.

9. Aaeoee/ A.I., Eieueoeiaa A.A., Aeoieeei A.A., Oeuaaiie E.I.
I?eiaiaiea aaoa?iiieeeiiieaenia a aiaeeca e i/enoea iauaeoia
ie?oaeathuae n?aaeu.// Oac. aeiee. IV Iaaeaeoia?. eiioa?. “O?aioe?y oa
Oe?a?ia, iaoeiai — i?aeoe/iee aeina?ae o eiioaeno? ae?aeiao
iaoe?iiaeueieo eoeueoo?.”- Aeiai?iiao?iane, 1997.- o.II.- /.II.-N.87.

10. Aeoi?e?i A.A., Oeeaaiie E.I., Eieueoeiaa I.A., Aaeoe?/ A.I.,
Aeoi?e?ia I.A., Nieieiaa I.A. Aaoa?iiie?ai?iie — aiae?oe/i? oi?ie
aecia/aiiy aeaiaio?a: iioei?caoe?y o?i?ei-aiae?oe/ieo ia?aiao??a.// Oac.
aeii. Anaoe?a?inuee?e eiioa?. c aiae?oe/ii? o?i??.-Oaeai?iae, 1998.-N.
24.

Eieueoeiaa I.A. Aeno?aeoe?y iie?aaeiaieueo?aiiaeo aaoa?iiie?eiiieaen?a
aae?th oa ?? canoinoaaiiy a aiae?c?.- ?oeiien.

Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa o?i?/ieo iaoe
ca niaoe?aeuei?noth 02.00.02 — aiae?oe/ia o?i?y.- Oe?a?inueeee
aea?aeaaiee o?i?ei-oaoiieia?/iee oi?aa?neoao, Aei?i?iiao?ianuee, 1998.

Aeena?oaoe?th i?enay/aii aea/aiith aeno?aeoe?? iie?aaeiaieueo?aiiaeo
aaoa?iiie?eiiieaen?a Aae?th no?oeoo?e Eaa?ia c caaaeueiith oi?ioeith
GaMoxW12-xO405-. ciaeaeaie oiiae a?aeie?aieaiiy aaoa?iiie?eiiieaen?a
Aae?th a?ae ?ciiie?niieoe oa aaoa?iiie?eiiieaen?a ?ioeo aeaiaio?a (P,
Si, Ge). C canoinoaaiiyi aeno?aeoe?eiiai iaoiaeo aea/aia no?ee?noue oa
iniaeeaino? ooai?aiiy eiiieaen?a ?yaeo GaMoxW12-xO405-. Iieacaia
aoaeoeai?noue canoinoaaiiy aeno?aeoe?? aeey i?aeaeuaiiy /ooeeaino?
aecia/aiiy Aae?th o aeaeyae? aaoa?iiie?eiiieaen?a. ?ic?iaeai? i?yi? oa
iai?yi? iaoiaeeee aecia/aiiy Aae?th a ??cieo ia’?eoao c canoinoaaiiyi
aeno?aeoe?eiiai eiioeaio?oaaiiy.

Eeth/ia? neiaa: aeno?aeoe?y, aaoa?iiie?niieoee, ?ciiie?niieoee, Aae?e,
Iie?aaeai, Aieueo?ai, eiioeaio?oaaiiy, iai?yi? iaoiaee.

Eieueoeiaa A.A. Yeno?aeoeey iieeaaeiaieueo?aiiauo aaoa?iiiee-eiiieaenia
aaeeey e aa i?eiaiaiea a aiaeeca. — ?oeiienue.

Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa oeie/aneeo iaoe
ii niaoeeaeueiinoe 02.00.02 — aiaeeoe/aneay oeiey.-Oe?aeineee
ainoaea?noaaiiue oeieei-oaoiieiae/aneee oieaa?neoao, Aeiai?iiao?iane,
1998.

Aeenna?oaoeey iinayuaia eco/aieth yeno?aeoeeiiiie niiniaiinoe
iieeaaeiaieueo?aiiauo aaoa?iiieeeiiieaenia aaeeey no?oeoo?u Eaaaeia n
iauae oi?ioeie GaMoxW12-xO405-. Iaeaeaiu oneiaey ioaeaeaiey
aaoa?iiieeeiiieaenia aaeeey io eciiieeniaaeeiaiee e aaoa?iiieeeiiieaenia
ae?oaeo yeaiaioia (P, Si, Ge). N i?eiaiaieai yeno?aeoeeiiiiai iaoiaea
eco/aia onoie/eainoue e ia?aciaaiea eiiieaenia ?yaea GaMoxW12-xO405-.
Iieacaia yooaeoeaiinoue eniieueciaaiey yeno?aeoeee aeey iiauoaiey
/oanoaeoaeueiinoe ii?aaeaeaiey aaeeey a aeaea aaoa?iiieeeiiieaenia.
?ac?aaioaiu i?yiua e e einaaiiua iaoiaeeee ii?aaeaeaiey aaeeey a
?acee/iuo iauaeoao n eniieueciaaieai yeno?aeoeeiiiiai eiioeaio?e?iaaiey.

Eeth/aaua neiaa: yeno?aeoeey, aaoa?iiieeniaaeeiaiey,
eciiieeniaaeeiaiey, aaeeee, iieeaaeai, aieueo?ai, eiioeaio?e?iaaiea,
einaaiiua iaoiaeu.

Koltsova E.G. The extraction of gallium molybdotungsten
heteropolycomplexes and it’s analytical application.- Manuscript.

Thesis for a candidate’s degree of chemistry by speciality 02.00.02 —
analytical chemistry.- Ukrainian State Chemical Technological
University, Dneepropetrovsk, 1998.

The dissertation is devoted to investigation of the extractability of
gallium molybdotungsten heteropolycomplexes with Keggin structure. The
conditions of the extraction of 14 reduced and oxydized
heteropolycomplexes of common formulae GaMoxW12-xO405- (x=1, 2, 3, 6, 9,
10, 11) and 7 molybdotungsten isopolycompounds by oxygen-containing
organic solvents have been found. It is shown that using of
methyl-isobutyl-ketone as extractant provides most effective separation
of gallium heteropolycomplex from isopolycomplexes. There were not found
great differences in extractability of reduced and oxydized
molybdotungsten heteropolycompounds. Taking into consideration the
increase in extractability of reduced isopolycomplexes compared to
oxydized ones it seems most perspective using in analysis the extraction
of oxydized gallium heteropolycompounds: in this case the interfereing
effect of molybdotungstate is minimized.

The extraction properties of molybdotungsten heteropolyanions depend
from the ratio Mo:W — it was found the correlation between the
extractability and the amount of molybdenum atoms in the ligand of
heteropolycomplex. According to this correlation the application of
GaMo10W2O405- as an analytical form for gallium determination including
the extraction procedure were recommended.

Parameters of the extraction equilibrium of gallium molybdotungsten
heteropolyanion were found and the extraction equation was suggested. It
was found that heteropolyanion is solvated by 10 molecules of
methyl-isobutyl-ketone. The number of heteropolyanion protonisation in
extraction process vary from 1 to 3 ions H+.

Stability and formation peculiarities of GaMoxW12-xO405- complexes were
investigated using the extraction method. The calculation of stability
constants of studied heteropolycomplexes allows to suggest using the
most stable complexes with x=2-4 ( lg =32 ) for gallium determination.
Selective reducing of heteropolyanion GaMo4W8O405- by hydrazine is
recommended for determination of 10-5-10-4 mole/l gallium without
separation from isopolycomplexes by extraction step.

It is shown that the extraction by oxygen-containing solvents is very
effective for preparation the pure soluble in water crystallic
heteropolycomplexes of gallium.

The conditions of separation of gallium heteropolycomplexes from
heteropolycomplexes of other elements ( P, Si, Ge ) have been found.
This method is used for simultaneous determination of gallium and
phosphorus in system modelling the composition of Ga-P semiconduct
alloy.

It is shown that the extraction is very effective for increasing the
sensitivity of gallium determination as heteropolycomplex. The direct
and indirect methods of gallium determination in various objects were
developed using the extraction concentration. The
extraction-spectrophotometric method of gallium determination by
reducing H5GaMo10W2O40 in organic phase is very selective and allow to
determine 0.05 — 0.20 % gallium in indium alloys without pre-separation.

Sensitivity of indirect method ( 0.008 mkg/ ml Ga3+) is provided by the
ratio Ga:Mo=1:10. The molar absorption coefficient of gallium
determination as MoO(SCN)3 after the extraction of GaMo10W2O405- is
87500. This indirect method were tested on determining gallium in
aluminium alloy. The other variant of indirect gallium determination
with using of heteropolycomplexes is based on measuring the absorption
of molybdate in ultraviolet ( the molar absorption coefficient is
56000).

The indirect extraction-titrimetric method were also proposed. The
combination of the extraction concentration with indirect determination
provides the sensitivity 10-4 mole/ l gallium.

Key words: extraction, heteropolycompounds, isopolycompounds, gallium,
molybdenum, tungsten, concentrating, indirect methods.

IIIINOA?NOAI INAIOE OE?AIIE

OE?AIINUeEEE AeA?AEAAIEE

OIIIEI — OAOIIEIAI*IEE OIIAA?NEOAO

ia i?aaao ?oeiieno

Eieueoeiaa Ieaia Aaiiaaei?aia

OAeE 542.61: 546.681

Aeno?aeoe?y iie?aaeiaieueo?aiiaeo aaoa?iiie?eiiieaen?a aae?th oa ??
canoinoaaiiy a aiae?c?.

02.00.02 — aiaeioe/ia oiiiy

AAOI?AOA?AO

aeena?oaoei? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa oiii/ieo iaoe

Aeiii?iiao?ianuee — 1999.

Aeena?oaoei?th ? ?oeiien.

?iaioa aeeiiaia a Aeiii?iiao?ianueeiio aea?aeaaiiio oiiaa?neoaoi.

Iaoeiaee ea?iaiee aeieoi?
oiii/ieo iaoe, i?ioani?

Oeeaaiie Ethaeieea Iaaeiaia,

Aeiii?iiao?ianueeee aea?aeaaiee

oiiaa?neoao, i?ioani?

Ioioeieii iiiiaioe:

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

aeaaeai?e AI Aeui? oeiee Oe?a?ie,

Oaa/oe ?aai Ieaen?eiae/,

Aeiiaoeueeee aea?aeaaiee oi?aa?neoao,

caa. eaoaae?ith aiae?oe/ii? o?i??

eaiaeeaeao o?i?/ieo iaoe, aeioeaio

Aa?eaeia Aioaeie Na?aieiae/,

Aea?aeaaia Iaoaeo?aieia Aeaaeaiiy

Oe?a?ie, aeioeaio

I?iaiaeia onoaiiaa:

O?ceei-o?i?/iee ?inoeooo AI Oe?a?ie, i.Iaeana.

Caoeno aiaeaoaeaoueny “___” __________ 1999 ?. i ___ aiaeeii ia
caniaeaiii

niaoeiaeiciaaii? a/aii? ?aaee Ae 08.078.01 i?e Oe?a?inueeiio
aea?aeaaiiio oiiiei-oaoiieiai/iiio oiiaa?neoaoi ca aae?anith: 320005,
i.Aei?i?iiao?ianuee, i?. Aaaa??ia,8.

C aeena?oaoei?th iiaeia iciaeiieoenue o aiaeiioaoei Oe?a?inueeiai
aea?aeaaiiai oiiiei-oaoiieiai/iiai oiiaa?neoaoo ca aae?anith:

i. Aeiii?iiao?ianuee, i?. Aaaa?iia, 8.

Aaoi?aoa?ao ?icineaiee ___________________

A/aiee nae?aoa?

niaoeiaeiciaaii? a/aii? ?aaee ___________ I?i?aee? ?.Ae.

iaa?oue

Похожие записи