EUeA?ANUeEEE AeA?AEAAIEE OI?AA?NEOAO

?IAI? ?AAIA O?AIEA

A?THOIAAOeUeEA ??EIA AIEIAeEIE??AIA

OAeE 531.3:541.124.13:54-39.126.2,661.729

EAOAE?OE*IA OA?IIAeENIOe?AOe?ss

(-IENEAOEE-O?AO-AOOEEIA?IENEAeO

O AIAeIIIO NA?AAeIAEU?

02.00.04 — o?ce/ia o?i?y

Aaoi?aoa?ao aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?i?/ieo iaoe

Euea?a — 1999

Aeena?oaoe??th ? ?oeiien

?iaioa aeeiiaia o Euea?anueeiio aea?aeaaiiio oi?aa?neoao? ?iai? ?aaia
O?aiea I?i?noa?noaa ina?oe Oe?a?ie

Iaoeiaee ea??aiee aeieoi? o?i?/ieo iaoe, i?ioani?

Eiaaeue/oe ?aaai I?ieiiiae/,

caa?aeoaa/ eaoaae?e o?ce/ii? oa eiei?aeii?

o?i??
Euea?anueeiai aea?aeaaiiai oi?aa?neoaoo

?iai?
?aaia O?aiea

Io?oe?ei? iiiiaioe:

Aeieoi? o?i?/ieo iaoe, i?ioani? Oo?ianueeee Aiaoie?e Aioiiiae/,

A?aeae?eaiiy o?ceei-o?i?? ? oaoiieia?? ai?th/eo eiiaeei ?inoeoooo
o?ce/ii? o?i??

IAI Oe?a?ie, i. Euea?a, caa?aeoaa/ a?aeae?eo o?i?? ? a?ioaoiieia??
ai?th/eo eiiaeei.

Aeieoi? o?i?/ieo iaoe, i?ioani? Aaiao Iioo??e Noaiaiiae/, Euea?anueeee

aea?aeaaiee iaaee/iee oi?aa?neoao ?iai? Aeaieea Aaeeoeueeiai, i?ioani?
eaoaae?e caaaeueii?, a?iiai?aai?/ii? oa o?ceiei?aeii? o?i??.

I?ia?aeia onoaiiaa:

?inoeooo o?i?? aenieiiieaeoey?ieo niieoe IAI Oe?a?ie, i. Ee?a.

Caoeno a?aeaoaeaoueny 29 ea?oiy 1999 ?. i 14 aiae 00 oa ia can?aeaii?
niaoe?ae?ciaaii? ?aaee Ae 35.051.10 c o?i?/ieo iaoe o Euea?anueeiio
aea?aeaaiiio oi?aa?neoao? ?iai? ?aaia O?aiea ca aae?anith: i.Euea?a,
aoe. Ee?eea ? Iaoiae?y, 6, o?i?/iee oaeoeueoao, aoaeeoi??y ? 2.

C aeena?oaoe??th iiaeia iciaeiieoeny o iaoeia?e a?ae?ioaoe?
Euea?anueeiai aea?aeaaiiai oi?aa?neoaoo ?iai? ?aaia O?aiea (i.Euea?a,
aoe. Ae?aaiiaiiaa, 5)

Aaoi?aoa?ao ?ic?neaiee 26 aa?aciy1999 ?ieo

A/aiee nae?aoa?

niaoe?ae?ciaaii? A/aii? ?aaee,

aeieoi? o?i?/ieo iaoe, i?ioani?
ss?aiei C.I.

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue i?iaeaie. C?inoath/a iio?aaa o iie?ia?ieo iaoa??aeao,
ye? aeei?enoiaothoueny a ??cieo iaeanoyo oaoi?ee, aeiaaa? iiooeo iiaeo
aenieiiieaeoey?ieo niieoe ia iniia? iiiiia??a ?c niaoeeo?/ieie
aeanoeainoyie. Oeei aecia/a?oueny, a naith /a?ao, aeooaeuei?noue iiooeo
a?aeiia?aeieo ?i?oe?thth/eo nenoai, ye? aeicaieyee a ?aae?coaaoe
iie?ia?ecaoe?ei? i?ioeane i?e iecueeeo oaiia?aoo?ao o aiaeieo ?ic/eiao.
Cia/iee ?ioa?an aeeeeea? oaeiae iiaeeea?noue cae?eniaiiy i?ioeano
iie?ia?ecaoe?? aaciina?aaeiuei c o/anoth iaoaeaaeo iiaa?oiiue oa
io?eiaiiy iie?ia?ieo iie?eoue c iaoith aioeei?ic?eiiai caoenoo oa
iaaeaiiy iiaa?oi? iaaieo aeanoeainoae.

Iaoa ?iaioe. Noai?aiiy aenieiaoaeoeaieo iecueeioaiia?aoo?ieo
?i?oe?thth/eo nenoai ia iniia? (-ieneaoee-o?ao-aooeeia?ieneaeo aeey
ia’?iieo oa iiaa?oiaaeo iie?ia?ecaoe?eieo i?ioean?a o aiaeieo ?ic/eiao.

Iaoeiaa iiaecia ?iaioe. Noai?aii iiao aoaeoeaio ?i?oe?thth/o nenoaio ia
iniia? (-ieneaoee-o?ao-aooeeia?ieneaeo aeey i?ioean?a iie?ia?ecaoe?? o
aiaeieo ?ic/eiao. Aeey oeueiai :

aenia?eiaioaeueii anoaiiaeaii caeiiii??iino? ?aaeoe?? oa?i?/iiai
?iceeaaeo aiaei?ic/eiiiai ia?ieneaeiiai ?i?oe?aoi?a
(-ieneaoee-o?ao-aooeeia?ieneaeo a i?enooiino? a?aeiiaiee?a: anei?a?iiai?
eeneioe, o?oeoice, aetheice oa ?ii?a iaoae?a ci?iiiai nooiaiy ieeneaiiy;

aia?oa aeyaeaii iniaeeaino? i?io?eaiiy oe??? ?aaeoe?? i?e eiioaeo?
eiiiiiaio?a aeine?aeaeoaaii? nenoaie c iaoaeaaeie iiaa?oiyie;

aieueoaiia?iiao?e/ii anoaiiaeaii ooai?aiiy iiaa?oiaaeo eiiieaen?a
anei?a?iiaa eeneioa — (-ieneaoee-o?ao-aooeeia?ieneae;

aia?oa cae?eniaii eaaioiai-o?i?/iee ?ic?aooiie aeaeo?iiii-i?inoi?iai?
no?oeoo?e (-ieneaoee-o?ao-aooeeia?ieneaeo oa eii?aeeiaoe ?aaeoe??
aiiie?oe/iiai ?iciaaeo ia?ieneaeo ii (I(I( ca’yceo;

cai?iiiiiaaii noaio a?aeiiaeaiiy (-ieneaoee-o?ao-aooeeia?ieneaeo ?iiaie
iaoae?a o ieae/eo nooiaiyo ieeneaiiy a i?enooiino? anei?a?iiai? eeneioe.

I?aeoe/ia oe?ii?noue ?iaioe. C iaoith ?aae?caoe?? iie?ia?ecaoe?eieo
i?ioean?a o aiaeieo ?ic/eiao ?ic?iaeaii ?i?oe?thth/o ieneaeii-a?aeiiaio
nenoaio c o/anoth i?aai?/iiai aee?eia?ieneaeo ((-ieneaoee-o?ao
aooeeia?ieneaeo), ?ii?a iaoae?a ci?iiiai nooiaiy ieeneaiiy oa
anei?a?iiai? eeneioe.

Aeine?aeaeaii aeaeiiiiceoe?th ia?ieneaeo a i?enooiino? ?ii?a Fe3+,
Cu2+, Mn2+, Ti3+, Ce3+.

?ic?iaeaii iiey?ia?ao?/io iaoiaeeeo eiio?ieth ca ai?noii ia?ieneaeo a
neeaaei?e ?i?oe?thth/?e nenoai? a i?ioean? eiai ?iceeaaeo.

Iieacaia iiaeeea?noue aeei?enoaiiy cai?iiiiiaaii? ?i?oe?thth/i? nenoaie
ia iniia? (-ieneaoee-o?ao-aooeeia?ieneaeo, anei?a?iiai? eeneioe i?e
eiioaeo? c iaoaeaaeie iiaa?oiyie (cae?ci ia?ee A?IEI, noaeue 20, i?aeue)
aeey neioaco iie?ia?ieo ie?aie ia iniia? iaoeeiaiai ao??o
ia?ooi?a?i?eieneia?ooi?aooaiiai? eeneioe.

Ia caoeno aeiinyoueny ianooii? iieiaeaiiy:

E?iaoe/i? caeiiii??iino? oa?iiaeenioe?aoe?? ia?ieneaeiiai ca’yceo
(-ieneaoee-o?ao-aooeeia?ieneaeo a neeaaeieo ?i?oe?thth/eo nenoaiao: a) a
i?enooiino? anei?a?iiai? eeneioe ? nieae ia?ao?aeieo iaoae?a ia?oiai
?yaeo; a) nenoaie (-ieneaoee-o?ao-aooeeia?ieneae — anei?a?iiaa eeneioa
i?e eiioaeo? c iaoaeaaeie i?aeaeth ? noaeeth.

Eaoae?oe/iee aieea i?aeii? oa noaeaai? iiaa?oiiue ia i?ioean
aeenioe?aoe?? (I(I( ca’yceo (-ieneaoee-o?ao-aooeeia?ieneaeo.

Iniaeeaino? eaoae?oe/iiai ?iceeaaeo ia?ieneaeiiai ?i?oe?aoi?a a
i?enooiino? anei?a?iiai? eeneioe caeaaeii a?ae aaee/eie eiioaeoii?
iiaa?oi? aeoeaiiai iaoaeo.

Iiaeeea?noue canoinoaaiiy ?ic?iaeaieo ?i?oe?thth/eo nenoai aeey neioaco
iie?ia?ieo oa??a ia iiaa?oi? i?ae? ? noae?.

Ai?iaaoe?y ?iaioe. Iniiai? ?acoeueoaoe aeine?aeaeaiue aeiiia?aeaeeny oa
aoee iaaiai?ai? ia ianooiieo eiioa?aioe?yo: Iaoeia?e eiioa?aioe?? aei
150-??//y “Euea?anueei? iie?oaoi?ee” “Noai ? ia?niaeoeae ?icaeoeo
o?i?/ii? iaoee oa i?iieneiaino? a Cao?aeiiio ?aa?ii? Oe?a?ie”, Euea?a,
17-19 o?aaiy 1994 ?.; Iaoeia?e eiioa?aioe?? “I?iaeaie i?aai?/iiai
neioaco”, Euea?a, 25 eenoiiaaea 1994 ?.; I-io Oe?a?inueeiio
aeaeo?io?i?/iiio c’?cae?, Ee?a (Ioua-Aiaeeoey), 15-17 o?aaiy 1995 ?.;
Iaoeiai-i?aeoe/i?e eiioa?aioe?? “Euea?anuee? o?i?/i? /eoaiiy”,
i?enay/ai?e 50-??//th o?i?/iiai oaeoeueoaoo EAeO, Euea?a, 26 o?aaiy 1995
?.; Ca?oi?e eiioa?aioe?? iaoeiaeo i?aoe?aiee?a Euea?anueeiai
aea?aeaaiiai oi?aa?neoaoo ?i. Iaaia O?aiea o 1995 ?.; VIII-?e
Oe?a?inuee?e eiioa?aioe?? c aenieiiieaeoey?ieo niieoe, Ee?a, 24-26
aa?aniy 1996 ?.; VI-?e Iaoeia?e eiioa?aioe?? “Euea?anuee? o?i?/i?
/eoaiiy — 97”, Euea?a, 29-30 o?aaiy 1997 ?.

Ioae?eaoe??. Iniiaiee ci?no aeena?oaoe?eii? ?iaioe aeeeaaeaii a 12
ae?oeiaaieo i?aoeyo.

No?oeoo?a ? ci?no ?iaioe. Aeena?oaoe?eia ?iaioa neeaaea?oueny ?c
anooio, 4 ?icae?e?a, aeniiae?a oa ia?ae?eo aeei?enoaieo e?oa?aoo?ieo
aeaea?ae (142 aeaea?aea). ?iaioa aeeeaaeaia ia 118 noi??ieao
iaoeiiieniiai oaenoo, i?noeoue 34 ?enoiee oa 24 oaaeeoe?.

Iniaenoee aianie aaoi?a. Iinoaiiaea caaea/? aeine?aeaeaiue
aeeiioaaeanue i?e aaciina?aaei?e o/ano? aaoi?a. Aiae?c e?oa?aoo?ieo
aeaieo, i?iaaaeaiiy aenia?eiaio?a oa ?ioa?i?aoaoe?y io?eiaieo
?acoeueoao?a aeeiiai? aaoi?ii iniaenoi ca?aeii aeac?aie iaoeiaiai
ea??aieea.

CI?NO ?IAIOE

?ICAe?E 1. ?I?Oe?TH*? NENOAIE IA INIIA? I?AAI?*IEO IA?IENEAe?A A
I?IOeANAO ?AAeEEAEUeII? IIE?IA?ECAOe??

Ocaaaeueiaii e?oa?aoo?i? aeai? c i?iaeaie ?i?oe?thaaiiy ?aaeeeaeueii?
iie?ia?ecaoe?? i?aai?/ieie ia?ieneaeaie oa iieacaii aieea ??cieo
oaeoi??a ia oeae i?ioean. ?icaeyiooi oeyoe ?ioaineo?eaoe?? oa?iie?co
ia?ieneae?a o aiaeieo na?aaeiaeuao caaaeyee canoinoaaiith ?ii?a iaoae?a
?c ci?iiei nooiaiai ieeneaiiy, a oaeiae noai?aiith iai?ioi?o
ieneaeii-a?aeiiaieo nenoai. I?aee?aneaia aeooaeuei?noue aeine?aeaeaiiy
iaaeinoaoiuei aea/aii? a?oie iie?ooieoe?iiaeueieo ?i?oe?aoi??a —
ia?ieneae?a c ooieoe?iiaeueieie iaia?ieneaeieie a?oiaie. A ?yae? ?ia?o
iieacaii nooo?aee aieea i?enooiino? a iie?ia?ecaoe?ei?e nenoai? oaa?aei?
oace ia e?iaoe/i? oa aeoeaaoe?ei? ia?aiao?e i?ioean?a ?aaeeeaeiooai?aiiy
oa ?i?oe?thaaiiy iie?ia?ecaoe?? ca o/anoth i?aai?/ieo ia?ieneae?a.
I?aeoaa?aeaeaii iaiao?aei?noue canoinoaaiiy ye oi?aa?naeueiiai
iiey?ia?ao?/iiai iaoiaeo aiae?co aeey eiio?ieth ca ai?noii ia?ieneaeo a
neeaaeieo nenoaiao a i?ioean? eiai ?iceeaaeo.

Iaa?oioiaaii aeioe?euei?noue aeine?aeaeaiiy ?i?oe?thth/i? caeaoiino?
nenoaie ia iniia? iie?ooieoe?iiaeueiiai ia?ieneaeo (-IAI c
??ciiiai?oieie aeoeaoth/eie aeiaeaoeaie c iaoith aecia/aiiy iioeiaeueieo
oiia i?io?eaiiy i?ioeano iie?ia?ecaoe?? ia iiaa?oi? iaoaeo ? a ia’?i?
?aaeoe?eii? noi?o?.

?ICAe?E 2. OA?AEOA?ENOEEA AeINE?AeAEOAAIEO ?A*IAEI OA AENIA?EIAIOAEUeI?
IAOIAeEEE

Iaaaaeaii o?ce/i? eiinoaioe ia’?eo?a aeine?aeaeaiiy oa iienaii iniiai?
aenia?eiaioaeuei? iaoiaeeee, ye? aeei?enoiaoaaeenue a aeai?e ?iaio?.

E?iaoeeo i?ioean?a ?aaeeeaeiooai?aiiy a ?i?oe?thth/eo nenoaiao ia
iniia? aeine?aeaeoaaiiai ia?ieneaeo aea/aee iiey?ia?ao?/ii c
aeei?enoaiiyi aaoiiaoe/iiai iiey?ia?aoa IO-1 a ?aaeei? eeane/ii?
iiey?ia?ao??. Aeaeo?io?i?/i? ia?aoai?aiiy iniiaieo eiiiiiaio?a
?i?oe?thth/i? nenoaie (-IAI oa AE — i?e eiioaeo? c iaoaeaaith iiaa?oiath
i?iaiaeeee iaoiaeii iaa?oiaiai aeeneiaiai aeaeo?iaeo.

Oa?i?/iee ?iceeaae (-IAI o aiaeiiio na?aaeiaeu? i?iaiaeeee a neeyieo
caiayieo aiioeao, a ?i?oe?thth/eo nenoaiao — a neeyiiio ?aaeoi??. Ai?no
ia?ieneaeo a oa?iie?cao? aiae?coaaee iiey?ia?ao?/ii.

Eaaioiai-iaoai?/i? ?ic?aooiee aeaeo?iiii-i?inoi?iai? no?oeoo?e (-IAI ?
i?iaeoeo?a eiai o?aaiaioaoe?? ?aae?coaaee ca aeiiiiiaith iaeaoo i?ia?ai
II?AN 6 c aeei?enoaiiyi AII ?AI ?N/AO.

?ICAe?E 3. CAEIIII??IINO? OA?IIAeENIOe?AOe?? (-IAI

A ?I?Oe?THTH*EO NENOAIAO*

* ?icae?e aeeiiaiee i?ae ea??aieoeoaii aeioe. Ai?aa/aanueei? O.?.

I?ioeane ?i?oe?thaaiiy c o/anoth (-IAI, ye aoei anoaiiaeaii
iiia?aaei?ie aeine?aeaeaiiyie, aoaeoeaii cae?eniththoueny eeoa i?e
canoinoaaii? ieneaeii-a?aeiiaieo nenoai, ye? aeoeaothoue ?iciaae -I-I-
a?oie ? iaeii/anii ni?eythoue cieaeaiith oaiia?aoo?e aeoeaiiai ?iceeaaeo
ia?ieneaeo. A ca’yceo c oeei aeey aea/aiiy iniaeeainoae i?ioeano
oa?iiaeenioe?aoe?? (-IAI a neeaaeieo ?i?oe?thth/eo nenoaiao ? aecia/aiiy
e?iaoe/ieo ia?aiao??a ia iiaeooue aooe canoiniaai? o?aaeeoe?ei?
(oeo?eiao?e/i?) iaoiaee aiae?co a ca’yceo c i?io?eaiiyi ia?aeaeueieo
ieneaeii-a?aeiiaieo ?aaeoe?e. Oiio c iaoith ?ic?iaee iaoiaeo
e?euee?niiai eiio?ieth ai?noo (-IAI a aeine?aeaeoaaieo nenoaiao
ii?iaoaaee aieueoaiia?iiao??th ia i?aeiiio, ?oooiiio, cae?ciiio,
aiaeueaaiiaaiiio i?aeiiio, naeioeaaiio aeaeo?iaeao. Iaea?eueo i?eaeaoiei
aeey oe??? iaoe aeyaeany ?oooiee eaiaeueiee aeaeo?iae.

(-IAI — iiey?ia?ao?/ii aeoeaiee (?en.1). O aiaeiiio na?aaeiaeu? ia oii?
i?o?aoo aiii?th iiey?ia?aie aeia?a noi?iiaai?, ia?aiao?e
iiey?ia?ao?/iiai a?aeiiaeaiiy (-IAI a?aeoai?ththoueny. A ae?aiacii?
eiioeaio?aoe?e (3(10-3(3(10-4) I caeaaei?noue no?oio a?aeiiaeaiiy (-IAI
a?ae eiioeaio?aoe?? ? i?yiie?i?eiith, iieno?oueny ??aiyiiyi ?eueeiae/a,
ui na?ae/eoue i?i aeeooc?eio i?e?iaeo no?oio.

?en.1. Iiey?ia?aie ia oii? 0,2 I aiaeiiai ?ic/eio NH4NO3:

oii;

1,3(10-3 I ?ic/ei AE;

1,4(10-3 I ?ic/ei (-IAI;

2,5(10-3 I ?ic/ei (-IAI ? 3,5(10-3 I ?ic/ei AE.

Oa?iie?c aiaeieo ?ic/ei?a (-IAI aac aeiaeaoe?a i?e ?I=4,2 a
oaiia?aoo?iiio ?ioa?aae? (383(418) E a?aeaoaa?oueny c Aaeo.=(122,5(2)
eAeae/iieue. Cieaeaiiy ?I aei 2,4 coiiaeth? aeayea ciaioaiiy oaeaeeino?
?iceeaaeo ia?ieneaeo ? caeaaei?noue eiinoaio oaeaeeino? i?ioeano a?ae
oaiia?aoo?e ia iieno?oueny ??aiyiiyi A??ai?ona.

sse a?aeiii, ?iie iaoae?a ci?iiiai nooiaiy ieeneaiiy canoiniaothoueny
aeey cieaeaiiy oaiia?aoo?e aeoeaiiai ?iceeaaeo ia?ieneaeo. C iaoith
ciaioaiiy e?eueeino? ?ii?a a nenoai? ? iaeii/anii aeey i?aeaeuaiiy
aoaeoeaiino? ?oiuei? ae?? ?aoe?iiaeueiei aeaea?oueny canoinoaaiiy a
oaeeo nenoaiao i?aai?/ieo niieoe, caeaoieo aei ?iieueieo ia?aoai?aiue.
Iaie aoee ii?iaoaai? o?oeoica, aetheica, anei?a?iiaa eeneioa.
Anoaiiaeaii, ui aeiaeaoee aetheice ? o?oeoice iii?oii ia aieeaathoue ia
e?iaoeeo ?iceeaaeo (-IAI, a oie /an ye anei?a?iiaa eeneioa (AE) cia/ii
i?enei?th? i?ioean. Ii?iaoaai? i?aai?/i? niieoee ca a?aeiiaiith
aeoeai?noth iiaeia ?ici?noeoe a ianooiiee ?yae: AE > o?oeoica >
aetheica.

Iiey?ia?ao?/i? aeine?aeaeaiiy e?iaoe/ieo ia?aiao??a oa?i?/iiai
?iceeaaeo (-IAI a i?enooiino? nenoai AE-?iie Ian+ (a naia Mn2+, Cu2+,
Fe3+, Ti3+, Ce3+) iieacaee, ui iaeaeuo aoaeoeai?noue a i?ioean?
?iceeaaeo -I-I- ca’yceo (-IAI i?iyaeythoue nenoaie AE-Fe3+ ? AE-Cu2+
(oaae.1).

?acoeueoaoe aea/aiiy e?iaoe/ieo ia?aiao??a oa?iiaeenioe?aoe?? (-IAI a
i?enooiino? AE, i?aeii? iiaa?oi? oa ?ii?a i?ae?, noaeaai? iiaa?oi? oa
?ii?a cae?ca i?aeoaa?aeaeothoue cia/ii aeoeai?oo ae?th iiaa?oiiue
(i?aeii? oa noaeaai?) a ii??aiyii? c ae??th a?aeiia?aeieo ?ii?a iaoae?a,
aeiaeaieo o aeaeyae? nieae.

Oaaeeoey 1.

Ca’ycie iiae aaee/eiith ieneaeii-aiaeiiaiiai iioaioeiaeo (E0) iiiia
iaoaeia oa oaeaeeinoth ia?aoai?aiiy (-IAI a nenoaii (-IAI-AE-Ian+.
N(-IAI= NAE=7,5(10-3 iieue/e; N(Ian+)=5(10-5 iieue/e. O=298 E

? i/i Nenoaia ?aaeoe?y ?iio iaoaeo A0, A (1/2, aiae

1

2

3

4

5

6

7 (-IAI

(-IAI-AE

(-IAI-AE-Nu2+

(-IAI-AE-Fe3+

(-IAI-AE-Mn2+

(-IAI-AE-Ce3+

(-IAI-AE-Ti3+ —

Nu2+ + e ( Nu+

Fe3+ + e ( Fe2+

Mn2+ — e ( Mn3+

Ce3+ — e ( Ce4+

Ti3+ + e ( Ti2+

Ti3+ — e ( Ti4+ —

+0,153

+0,771

+1,51

+1,61

+0,37

+0,06 100

53,40

0,72

1,04

1,89

2,21

2,90

Aeoeaoth/a ae?y iaoaeaaeo iiaa?oiiue iia’ycaia ye c iayai?noth a
?aaeoe?ei?e nenoai? ?ii?a a?aeiia?aeiiai iaoaeo, ye? ooai?ththoueny
aiane?aeie /anoeiaiai ?ic/eiaiiy iiaa?oi?, oae ? iii?oiei aieeaii
aaeni?aoe?eieo i?ioean?a ia e?iaoeeo ?iceeaaeo (-IAI a aeine?aeaeoaaieo
nenoaiao, ui i?aeoaa?aeaeo?oueny ?acoeueoaoaie aea/aiiy eaoae?oe/ii?
caeaoiino? aeiaeaoeo AE-cieue Fe(OH)3 (eiioeaio?aoe?y ?ii?a Fe3+ a cie?
7,5(10-5 iieue/e). Ia aeeaey/enue ia oa, ui a aeai?e i?e?iaaoa?iaaii?e
nenoai? ia i?noyoueny o aeo?aeiiio noai? ?iie Fe2+, ?iceeaae (-IAI
a?aeaoaa?oueny a 5 ?ac?a oaeaeoa (k=1,5(10-3 n-1 i?e 363 E), i?ae a
i?enooiino? aeiaeaoeo AE-Fe2+ c o??th ae eiioeaio?aoe??th ?ii?a cae?ca (
k=0,34(10-3 n-1 i?e o?e aea oaiia?aoo??). Ioaea, iaeneiaeueio
aeoeai?noue i?e ?iceeaae? (-IAI i?iyaeythoue nenoaie (-IAI-AE-?iie
cae?ca, i?iaeoeiaai? iiaa?oiath cae?ca, aai (-IAI-AE-cieue Fe(OH)3, ye?
i?noyoue aeoaea iae? e?eueeino? ?ii?a Fe2+, ui ooai?ththoueny a
?acoeueoao? ieneaeii-a?aeiiaieo i?ioean?a a i?enooiino? AE, yea
a?aeiiaeth? ?ii? Ia(n+1)+ aei Ian+. Iayai?noue iiaa?oi? ?icae?eo oac ?
ae??aei oaeoi?ii o aecia/aii? e?iaoeee ?iceeaaeo (-IAI. I?e oeueiio
?noioiith iiaea aooe ye aaeni?aoe?y (-IAI /e AE aai anioe?ao?a (-IAI-AE
ia iiaa?oi?, oae ? iia’ycaia c oeei ci?ia ?aaeoe?eii? caeaoiino?
ia?ieneaeii? a?oie.

C iaoith aeyniaiiy iiaaae?iee iniiaieo eiiiiiaio?a ?i?oe?thth/i?
nenoaie ((-IAI oa AE) i?e eiioaeo? c iaoaeaaith iiaa?oiath, iaoiaeii
iaa?oiaiai aeeneiaiai aeaeo?iaeo (IAeA) aeine?aeaeai? aeaeo?io?i?/i?
ia?aoai?aiiy eiiiiiaio?a nenoaie ia noaeaa?e iiaa?oi? (O18I9O).
Anoaiiaeaii, ui (-IAI a aeine?aeaeoaaieo oiiaao ((=700-2500 ia/oa., oii
— 0,2 I aiaeiee ?ic/ei NH4NO3) aeaeo?io?i?/ii iaaeoeaiee (?en.2, e?eaa
1). AE iii?oii ci?ith? oa?aeoa? aiiaeiiai i?ioeano (?en.2,e?eaa 2),
noaoe?iia?iee iioaioe?ae cnoaa?oueny a eaoiaeio iaeanoue (A=0,2 A). A
ae?aiacii? iioaioe?ae?a -(0,5(0,4) A niinoa??aa?oueny c?inoaiiy no?oio c
iaeneioiii i?e A=-(0,3( 0,2) A. I?e ia?aiai?oc? aeu?e 0,6 A aiiaeiee
i?ioean ??cei aaeueio?oueny. I?e/iio, aiiaeiee no?oi AE c?inoa? c
eiioeaio?aoe??th aei iaaii? a?aieoe?; i?e eiioeaio?aoe?yo aeueo 3(10-3 I
a?i caeeoa?oueny iino?eiei, ui na?ae/eoue i?i aaeni?aoe?th AE ia
noaeaa?e iiaa?oi?. I?e aeiaeaaaii? aei ?ic/eio, yeee i?noeoue AE, (-IAI
ci?ie aeaeo?io?i?/ieo ia?aoai?aiue a nenoai? ia niinoa??aa?oueny,
Ano.=-0,58 A. Aiiaeiee no?oi i?e aea?iiey?iiio ai?no? a nenoai? (-IAI ?
AE cieaeo?oueny i?eaeecii ia 6% ca ?aooiie ?oiuei? anioe?aoeaii?
aca?iiae?? (?en.2, iicia/aii ioieoe?ii). Oaeei /eiii, iniiaia cia/aiiy
i?e aeaeo?io?i?/ieo ia?aoai?aiiyo a aeine?aeaeoaai?e nenoai? ia?
iiaa?oiaaa aeoeai?noue iaoaeo ii a?aeiioaiith aei AE.

?en.2. Aieueoaiia?ia?aie ia noaeaaiio IAeA:

(-IAI;

AE. N(-IAI=NAE=7,5(10-3 I; (=700 ia/oa.

Iaoiaeaie a?neiceiao???, ?*- oa OO-niaeo?ineii??, iiey?ia?ao??
aeiaaaeaii anioe?aoeaio aca?iiae?th i?ae AE ? (-IAI, yea aeeeeea?
aeoeaaoe?th ia?ieneaeiiai ca’yceo. Oa?aeoa? a?aeoeeaiiy a’yceino? a?ae
aaeeoeaiino?, ci?ia iioe/ii? aonoeie a aeine?aeaeoaai?e nenoai?, a
oaeiae iayai?noue a iieaeoe? AE ooieoe?iiaeueieo (II, N=I, N=N a?oi
i?aeoaa?aeaeothoue ooai?aiiy aeae?eueeio oei?a niaoeeo?/ieo anioe?ao?a
AE c iieaeoeith (-IAI i?e ??cieo ni?aa?aeiioaiiyo eiiiiiaio?a AE:(-IAI =
4:1, 1:1, 1:2.

Aeine?aeaeaii aieea aaee/eie aaiiao?e/ii? iiaa?oi? i?ae? a i?enooiino?
AE ia oa?iiaeenioe?aoe?th (-IAI. I?e a?aeiioaiiyo ia’?io ?aaeoe?eii?
noi?o? aei ieiu? eiioaeoii? iiaa?oi? E<2,4(10-1 i ?nio? e?iaoe/ia iaeanoue, eiee oaeaeeino? oa?iie?co ia?ieneaeiiai ca’yceo ca ?aooiie aeoeaoth/i? ae?? ?ii?a i?ae? a ia’?i? ?ic/eio ? ia i?aei?e iiaa?oi? ni?ai??i? (?en.3a,a). A oe?e e?iaoe/i?e iaeano? oaeaeeino? i?ioeano c?inoathoue ?c ca?eueoaiiyi ieiu? eiioaeoii? iiaa?oi? aei aeinyaiaiiy iaaiiai cia/aiiy. Aia?a?y aeoeaaoe?? i?ioeano cieaeo?oueny (?en.4). I?e aeineoue aaeeeeo ieiuao iiaa?oi? (E<3,0(10-2 i) aei 300 E ia?aaaaea? iecueeiaia?aaoe/iee aaoa?iaaiiee i?ioean ?iceeaaeo (-IAI, eiee aeoeaaoe?ei? aeo?aoe eiiiainothoueny aecioa?i?/i?noth aaeni?aoe?? iieaeoe ia?ieneaeo ia iaoaeaa?e iiaa?oi?. I?e aeueo oaiia?aoo?ao ia?aaaaea? aeani?aoe?y ? ci?ith?oueny oiiio?i?y i?ioeano ?iceeaaeo. ?aaeoe?y ia?aaaaeii a?aeaoaa?oueny aiiiaaiii ? niinoa??aa?oueny a?eueoee aieea oaiia?aoo?e ia ?? oaeaee?noue. I?e E~6,0(10-2 i a oaiia?aoo?iiio ?ioa?aae? (293(313) E caeaaei?noue eiinoaioe oaeaeeino? a?ae oaiia?aoo?e a a??ai?on?anueeeo eii?aeeiaoao ? i?yiie?i?eiith. I?e iaioeo eiioaeoieo ieiuao (E>8,5(10-2 i) cia/aiiy eiinoaio oaeaeeino? aeae? iinooiiai
cieaeothoueny ? i?e oaiia?aoo?ao ieae/eo 300 E aia?a?y aeoeaaoe??
i?ioeano iano?eueee c?inoa?, ui oaeaee?noue ?aaeoe?? nooo?ai
niia?eueith?oueny (?en.4).

Ioaea, aeoeaoth/a ae?y iaoaeaai? iiaa?oi? ia i?ioean oa?iie?co -I-I-
ca’yceo (-IAI ? iane?aeeii i?io?eaiiy aeaio ia?aeaeueieo i?ioean?a.
Ii-ia?oa, aca?iiae?y ia?ieneaeo c ?iiaie, i?iaeoeiaaieie iiaa?oiath, a
ia’?i? oa ?oiy ianooiia ?aaaia?aoe?y anei?a?iiaith eeneioith, yea
caaacia/o? ae?th oeeee?/ieo ieneaeii-a?aeiiaieo ia?aoai?aiue; ii-ae?oaa,
aeoeaaoe?y ?iceeaaeo ia?ieneaeo a ?acoeueoao? ooai?aiiy iiaa?oiaaeo
eiiieaen?a iiaa?oiy — AE — ia?ieneae (?en.5).

?en.3. Caeaaei?noue oaeaeeino? ?iceeaaeo (-IAI (a) oa i?eaaaeaii?
eiinoaioe oaeaeeino? ?iceeaaeo (-IAI (a) aiae aaee/eie aaiiao?e/ii?
iiaa?oii iiaei a i?enooiinoi AE. N(-IAI=NAE=7,5(10-3 I. 1 — 293 E; 2 —
298 E; 3 — 303 E; 4 — 307 E; 5 — 313 E.

?en.4. Ci?ia aia?a?? aeoeaaoe?? i?ioeano oa?iiaeenioe?aoe??
(-IAI N(-IAI=7,5(10-3 I) a caeaaeiino? a?ae aaee/eie aaiiao?e/ii?
iiaa?oi? i?ae?. Oaiia?aoo?iee ?ioa?aae:

(293(305) E;

(305(313) E.

?en.5. Noaia ?iceeaaeo (-IAI iiaa?oiath iaoaeo a i?enooiino?
anei?a?iiai? eeneioe.

?ICAe?E 4. AeINE?AeAEAIIss OIIA IIE?IA?ECAOe??

I?E ?I?Oe?THAAII? (-IAI

Eaaioiai-o?i?/iee ?ic?aooiie aeaeo?iiii-i?inoi?iai? no?oeoo?e (-IAI

C iaoith io?eiaiiy aeinoia??ii? ?ioi?iaoe?? i?i o?i?/i? ia?aoai?aiiy,
ye? a?aeaoaathoueny a neeaaeieo iie?ia?ecaoe?eieo nenoaiao, ui
aeeth/athoue aeine?aeaeoaaiee ia?ieneae ((-IAI) a ii?aeiaii? c
aeoeaoth/eie aeiaeaoeaie, iaie i?iaaaeaii ?ic?aooiie
aeaeo?iiii-i?inoi?iai? no?oeoo?e (-IAI oa eii?aeeiaoe ?aaeoe??
aiiie?oe/iiai ?iciaaeo ia?ieneaeo ii -I-I- ca’yceo. Aiane?aeie
iioei?caoe?? aaiiao??? aeyaeaii nooo?a? ci?ie no?oeoo?e iieaeoee (-IAI,
iniaeeai cia/i? aeey i?aeaoiiieo a?aenoaiae ? aeea?ae?aeueieo eoo?a. Oae
aeiaaeeia ca’yceo -I-I- o aeo?aei?e aeey ?ic?aooieo no?oeoo?? noaiiaeea
0,148 ii, a iioei?ciaai?e — 0,128 ii. Aeey iioei?ciaaii? aaiiao???
?ic?aoiaaii aaee/eio aeeiieueiiai iiiaioo (3,199 Ae), oaieioo ooai?aiiy
(-388,86 eAeae/iieue), ?iciiae?e aeaeo?iiii? aonoeie ia aoiiao oa
aaee/eie aoaeoeaieo ca?yae?a aoii?a a iieaeoe?. Iaea?eueoee iaaaoeaiee
ca?yae eieae?ciaaiee ia aoii? eenith a?ae?ieneeueii? a?oie. Ia
??aiioe?ii? a nain? ?iciiae?eo ca?yae?a ? aeaa aoiie eenith ia?ieneaeii?
a?oie. Cia/ii a?eueoee ca?yae (a iaeeieoeyo aeaiaioa?iiai ca?yaeo,
i?eeiyoiai ca -1) cina?aaeaeaiee ia aoii? eenith, c’?aeiaiiai c
o?aoaooeeueiei ?aaeeeaeii, ui ocaiaeaeo?oueny c eiai aeaeo?iiiaeiii?ieie
aeanoeainoyie. Aiae?c canaeaiinoae aoiiieo i?a?oaeae ca Iaee?eaiii
iieacaa, ui iaea?eueo canaeaiith ? pz AI aoiia eenith a?ae?ieneeueii?
a?oie. Oeae aoii ia? iaea?eueoee ?iaeaen ca’ycoaaiino? (noio
canaeaiinoae 2s, 2px, 2py, 2pz AI), yeee noaiiaeoue 6,3262, oiaoi ia
iueiio eieae?ciaaia iaeneiaeueia aeaeo?iiia aonoeia.

Aoiie eenith ia?ieneaeii? a?oie a?ae??ciythoueny, ye aaea aeacoaaeinue,
ca aaee/eiith ca?yaeo, a oaeiae ca aeaeo?iiiith aonoeiith, yea
noaiiaeoue 6,1476 ? 6,1610 aeey aoii?a eenith a?aeiia?aeii, yeui
ioia?oaaoe aoiie a iieaeoe? (-IAI a?ae aoiia aiaeith a?ae?ieneeueii?
a?oie. sseui i?iaanoe aiaeia?th i?ae aeaeo?iiiith aonoeiith
(canaeai?noth AI) ? eeane/iith aaeaioi?noth, oi iiaeia neacaoe, ui
aaeaioi?noue aoii?a eenith noaiiaeoue 6,3262, 6,1476 ? 6,1610. Iaeieae/a
aaeaioi?noue na?aae aoii?a aoaeaoeth niinoa??aa?oueny aeey o?aoeiiiai
aoiia, yea iaioa a?ae aaeaioiino?, i?eeiyoi? a eeane/i?e i?aai?/i?e
o?i?? ? noaiiaeoue 3,9471. A iieaeoe? (-IAI 28 i?a?oaeae caiiaiai?
aeaiia aeaeo?iiaie. A ?aaeoe?yo a?aeiiaeaiiy ia?aianaiiy aeaeo?ii?a
aoaea a?aeaoaaoenue ia ieae/o aaeaioio iieaeoey?io i?a?oaeue, aia?a?y
yei? ??aia 197,00 eAeae. C aeaeo?iiii? nooeoo?e (-IAI oaeiae aeieeaa?,
ui iaca’ycoth/? II eieae?ciaai? ia aoiiao eenith ia?ieneaeii? a?oie. Oea
icia/a?, ui o?aaiaioaoe?y ia?ieneaeo a?aeaoaaoeiaoueny ii i?noeth -I-I-
ca’yceo. A iiaeaeueoiio ?ic?aoiaoaaee aeaeo?iiii-i?inoi?iao no?oeoo?o
o?aaiaio?a: a?ae?ieniaoeeueiiai ? ieneo?aoaooeeueiiai ?aaeeeae?a. Aeaye?
?ic?aoiaai? ia?aiao?e i?eaaaeai? a oaaeeoe? 2.

?aaeeeaeuei? o?aaiaioe, ye aeaeii c oaaeeoe?, oa?aeoa?ecothoueny
a?aei?iieie a?ae aeo?aeiiai ia?ieneaeo ia?aiao?aie. Iniaeeai oe?
a?aei?iiino? noinothoueny aia?a?? ieae/i? aaeaioii? i?a?oae?. ??cieoey o
837 eAeae a?aeia?aaea? aenieo ?aaeoe?eio aeoeai?noue aoiia eenith a
?aaeeeaeueieo /anoeieao, cie?aia a ?aaeoe?? i?e?aeiaiiy aeaeo?iio.
Aeineoue nooo?aith ? oaeiae ??cieoey o aaee/ei? oaieiaiai aoaeoo
ia?ieneaeo ? o?aaiaio?a (112,71 eAeae/iieue), ui na?ae/eoue eeoa i?i
iai?eaeaoi?noue aaeeoeaii? noaie aeey ?ic?aooieo oaieiaeo aoaeo?a, yea
oe?iei aeei?enoiao?oueny a eeane/i?e o?ce/i?e o?i??.

Ianooiiei aoaiii aoa ?ic?aooiie eii?aeeiaoe ?aaeoe?? aiiie?oe/iiai
?iciaaeo ia?ieneaeo ii -I-I- ca’yceo. Eiaeia e?eaa iioaioe?aeueii?
aia?a?? ?aaeoe?? o?aaiaioaoe?? (-IAI a iaaeeaeaii? ?cieueiaaii? iieaeoee
yaey? niaith ci?io oaieioe ooai?aiiy a

Oaaeeoey 2.

Ia?aiao?e o?aaiaio?a iieaeoee (-IAI, ?ic?aoiaai? iaoiaeii ?I-3

*anoeiea Ca?yae ia aoii? eenith Aeaeo?iiia aonoeia ia aoii? eenith
Aeeiieueiee iiiaio,

Aeaaae Oaieioa ooai?aiiy,

(If, eAeae/iieue

II-(NI2)2-I( (0,2963 6,2963 2,876 (207,87

(NI3)3-N-I( (0,2167 6,2167 2,174 (68,28

(-IAI (0,1610 6,1610 3,194 (388,86

*anoeiea Aia?a?y ?ii?caoe??, eAeae/iieue Aia?a?y aeui? caeiyoi? II,
eAeae Aia?a?y ieae/i? aaeaioii? II, eAeae Oe?eia

caai?iiaii? ciie, eAeae/iieue

II-(NI2)2-I( 4751,43 (1059,40 (640,66 418,74

(NI3)3-N-I( 4953,31 (1073,01 (640,35 432,66

(-IAI 4288,60 (1025,00 197,00 1222,00

caeaaeiino? a?ae a?aenoai? di-i aeey o?eniaaieo cia/aiue eoo?a
“?ice?oaiiy” o?aaiaio?a. I?i?ioi aia?a?? ia e?ea?e a?aeiia?aea?
??aiiaaaei?e i?aeaoiii?e a?aenoai? aeey noaoe?iia?iiai noaio (-IAI. I?e
ciaioaii? a?aenoai? iiiaae ??aiiaaaeio niinoa??aa?oueny ??cea
ca?eueoaiiy If, coiiaeaia yaea?iei ? aeaeo?iiiei a?aeooiaooaaiiyi.
Ca?eueoaiiy a?aenoai? di-i i?eaiaeeoue aei c?inoaiiy ooieoe?? a?aeeeeeo
aei a?aenoaiae, aeecueeeo 0,2 ii, a iio?i niinoa??aa?oueny ??cea
ciaioaiiy If, yea a e?ioeaaiio a?aeiia?aea? aaee/ei? If iaaca?iiae?th/eo
i?ae niaith o?aaiaio?a. Iaeneioi If a?aeiia?aea? iioaioe?aeueiiio
aa?’??o ?aaeoe?? aiiie?oe/iiai ?iceeaaeo (-IAI. Ii eiai aenio? iiaeia
ioe?ieoe aia?a?th aeoeaaoe?? aiiie?oe/ii? aeenioe?aoe?? ia?ieneaeo
(oaae.3).

Oaaeeoey 3.

Caeaaei?noue aaee/eie aia?a?? aeoeaaoe?? ?iciaaeo (-IAI a?ae eooa
“?ice?oaiiy” o?aaiaio?a

Eoo, a?aaeone 0 5 10 20 30 40 50 70 100

Aaeo., eAeae/iieue 124,00 117,48 140,28 211,45 473,62 211,96 293,92
152,54 456,76

Eoo, a?aaeone 110 120 130 140 150 160 170 180

Aaeo., eAeae/iieue 469,50 454,17 424,00 407,39 318,06 305,09 246,10
223,13

I?i?iaeueiiio cia/aiith aia?a?? aeoeaaoe?? a?aeiia?aea? eoo 5i,
iaeneiaeueiiio — 30i. Oea icia/a?, ui iani?aaae? ineieee ?iciaaeo
?ice?oathoueny i?ae eooii o aocueeiio ei?eaei?? 0i -10i, a iaeneiaeueia
cia/aiiy aia?a?? i?e 30i iieaco?, ui oaeei oeyoii ?aaeoe?y i?eiee ia
a?aeaoaa?oueny. Ni?anoaaeaiiy c aenia?eiaioaeueii aecia/aiith aaee/eiith
aia?a?? aeoeaaoe?? (122,5 eAeae/iieue) aeaco? ia aeoaea aeia?a
ocaiaeaeaiiy ?ic?aooieiaeo aeaieo c aenia?eiaioaeueii ciaeaeaieie.
I/aaeaeii oeyo ?aaeoe?? i?ioiaeeoue i?e eoo? 0i, yeee iaea?eueoa
iaaeeaea?oueny aei ?aaeueii? aaee/eie.

Aenia?eiaioaeueii i?aeoaa?aeaeaii o/anoue ?ii?a iaoae?a ci?iiiai
nooiaiy ieeneaiiy a ?aaeoe?? ?iciaaeo (-IAI. Iiaeeea?noue eaoae?co
?iciaaeo ia?ieneaeo i?aeoaa?aeaeo?oueny ciaioaiiyi aia?a?? aeoeaaoe??
i?ioeano ?iciaaeo (-IAI, yea cieaeo?oueny, iai?eeeaae, aei aaee/eie
89,1(2 eAeae/iieue (o aeiaaeeo ?ii?a Cu2+). Noaia aiae?co o/ano? ?ii?a
iaoae?a ci?iiiai nooiaiy ieeneaiiy a ?aaeoe?? ?iciaaeo ia?ieneaeo,
cai?iiiiiaaia Aaaa?ii ? Aaenii, ia ia?aaeaa/a? oeyo?a o/ano? ?ii?a a
?aaeoe?? o?aaiaioaoe?? ia?ieneaeo, a eeoa eiinoaoo? ?acoeueoao ?aaeoe??.
Ie aaaaea?ii, ui ?aaeoe?y i?io?ea? /a?ac noaae?th ooai?aiiy eiiieaeno c
ia?aiinii ca?yaeo. I?e oeueiio ia?aianaiiy aeaeo?iio cae?enith?oueny ii
aioo??noa?iiio iaoai?cio. I?e eiino?othaaii? i?ii?aeiiai eiiieaeno
caaeaaaee eiai ca?yae +2, yeee aoa eieae?ciaaiee ia aoii? cae?ca. A
eiiieaen? c iioei?ciaaiith aaiiao???th cae?ci iana ca?yae +0,40a.
A?ae’?iiee ca?yae eieae?co?oueny ia aoii? eenith, aaciina?aaeiuei ia
ca’ycaiiio ?c cae?cii. Aeey eiiieaeno ?ic?aoiaaii oaieioo ooai?aiiy
(-14548,81 eAeae/iieue), aaee/eio aeeiieueiiai iiiaioo (4,683 Ae). 62
aeaeo?iie a eiiieaen? ?ici?uai? ia 30-oe aea?/? caeiyoeo ? ia aeaio
iaiieiaeio caiiaiaieo II. Ca?aene aeieeaa?, ui ioeueoeieaoi?noue
eiiieaeno ??aia 3, oiaoi a?i yaey? niaith a??aaeeeae. A ooai?aii?
eiiieaeno i?eeiathoue o/anoue s-1, p-3 ? d-5 AI aoiia cae?ca. Aia?a??
iaeiie?aoii caeiyoeo i?a?oaeae a?aeiia?aeii ??ai? -15,617 ? -13,940 aA.
A eiiieaen? a ??aiiaaaeiiio noai? aeaeo?iiia aonoeia ci?uo?oueny a
noi?iio aoiia Fe. I?e oeueiio iaea?eueo canaeaiith ? aoiiia i?a?oaeue
cae?ca d(x2-y2) (1,81a), yea eaaeeoue a ieiuei?, aea niinoa??aa?oueny
iaea?eueoa ia?ae?eaaiiy i?a?oaeae. Aiane?aeie inoeeeyoe?e aoii?a ?
cae?eniaiiy ieie eieeaaeueieo ?oo?a a eiiieaen? iiaea a?aeaoaaoenue
ci?uaiiy aeaeo?iiii? aonoeie, ui a e?ioeaaiio i?aenoieo i?eaaaea aei
aaoa?ie?oe/iiai ?ic?eao ca’yceo -I-I- c ooai?aiiyi ?aaeeeaeo (NI3)3N-I ?
eiiieaenii? nie? [HO-CH2-CH2-O…Fe]2+. Ooai?aiiy oaeiai eiiieaeno ?
iaea?eueo oa?iiaeeiai?/ii aea?aeiei.

Io?eiaiiy iie?ia?ieo ie?aie ia iaoaeaaeo iiaa?oiyo c o/anoth (-IAI

Iiia?aaeiuei iaea?aeai? caeiiii??iino? e?iaoeee oa?iiaeenioe?aoe??
(-IAI a i?enooiino? aeoeaaoi?a (AE) ? iaoaeaaeo iiaa?oiiue
ocaiaeaeothoueny c iiaeeeainoyie neioaco iie?ia?ii? ie?aee ia iiaa?oi?
noae? 20, cae?ca A?IEI ? i?ae?. I?ioean ie?aeiooai?aiiy aeine?aeaeoaaee
oeyoii iie?ia?ecaoe?? iaoeeae?eeaoo (IA) ? iaoeeiaiai ao??o
ia?ooi?a?i?eieneia?ooi?aooaiiai? eeneioe (OI) ia iaae? iaoaeaaa
iiaa?oiy-iiiiia?, ?i?oe?eiaaii? (-IAI a i?enooiino? AE oa ?ii?a, ui
aaia?othoueny iiaa?oiath iaoa??aeo i?aeeeaaeee. A ca’yceo c iaeith
?ic/eii?noth iiiiia??a o aiae? iie?ia?ecaoe?th i?iaiaeeee o
aiaeii-nie?oiaiio (30 ia.% aoaiieo) ?ic/ei?. sse ia?aiao?, ca
aeiiiiiaith yeiai ioe?ithaaee aieea eiiiiiaio?a ?i?oe?thth/i? nenoaie ia
i?ioean ie?aeiooai?aiiy, aea?aee i?eaaaeaio iano iie?ia?ii? ie?aee m,
yeo ?ic?aoiaoaaee ca oi?ioeith: m=m2-m1/S, aea m1 — iana iaoaeaai?
ieanoeiee aei iaianaiiy, ea; m2 — iana iaoaeaai? ieanoeiee c iie?ia?iith
ie?aeith, ea; S — ieiua aaiiao?e/ii? iiaa?oi? iaoaeo, iie?eoa ie?aeith,
i2.

Iaei??th c aaaeeeaeo oiia iaea?aeaiiy ye?niiai iie?ia?iiai iie?eooy c
oi?ioith aaeaac??th aei iiaa?oi? ? iiia?aaeiy ?? a?aeiia?aeia
i?aeaioiaea. E??i oiai, ia caaaeaee iioeiaeueii cae?enith?oueny
eiioeaio?oaaiiy iiiiia?o, ?i?oe?aoi?a ? aeoeaaoi?a ia iaae?
iaoae-aiaeiee ?ic/ei aiane?aeie iaiaeiaeiai? iiaa?oiaai? aeoeaiino?
ie?aieo eiiiiiaio?a nenoaie. A iaoiio aeiaaeeo aeei?enoiaoaaeanue
ia?ooi?iaea?aiiiaa eeneioa (IOIE) ye iiaa?oiaai-aeoeaia ?a/iaeia, yea
oa?aeoa?eco?oueny aenieith iiaa?oiaaith aeoeai?noth ?, e??i oeueiai,
aeecueea ca i?e?iaeith aei ooi?iiiiia?o.

Iie?ia?ecaoe?y IA, ?i?oe?eiaaia (-IAI a i?enooiino? o??? e?eueeino?
?ii?a cae?ca, ye? aaia?othoueny iaoaeaaith iiaa?oiath, o a?aenooiino? AE
ia a?aeaoaa?oueny iaa?oue i?ney 1 aeiae aeo?eioaaiiy aeo?aeii?
iie?ia?ecaoe?eii? nenoaie. A i?enooiino? AE i?ioean ?icii/eia?oueny aaea
/a?ac 5-7 oaeeei. Iaeiae o aeiaaeeo i?aeiiai c?acea iayaiee o?eaaeee
?iaeoeoe?eiee ia??iae. sseui cai?iiiiiaaiee neeaae iie?ia?ecaoe?eii?
noi?o? aoa iioeiaeueiei aeey iaea?aeaiiy iie?iaoae?eeiaiai iie?eooy
iaoaeaaeo ieanoeiie, oi i?e cai?i? IA ia OI iie?ia?ecaoe?y ia
a?aeaoaa?oueny. Oiio c iaoith caoaeaeaiiy iie?ia?ecaoe?? OI i?ioean
cae?enithaaee a i?enooiino? IA. Ii?yaeie aaaaeaiiy iiiiia??a ia aieeaa?
ia oaeaee?noue ooai?aiiy ie?aee ia iiaa?oi? iaoaeo.

?acoeueoaoe aeine?aeaeaiiy i?ioean?a iie?ia?ecaoe?? IA ? OI,
?i?oe?eiaaieo aaoa?iaaiieie nenoaiaie ia iniia? (-IAI (oaae.4),
iieacothoue, ui /enoee IA a i?enooiino? (-IAI oa AE ooai?th? ia cae?cieo
(ia?ee A?IEI) oa noaeaaeo (noaeue 20) ieanoeieao iie?ia?io ie?aeo c
i?aeoe/ii iaeiaeiaith i?eaaaeaiith ianith. Aaaaeaiiy a iie?ia?ecaoe?eio
nenoaio OI i?eaiaeeoue aei ca?eueoaiiy iane iie?ia?iiai iie?eooy,
iniaeeai iii?oiiai o aeiaaeeo aeei?enoaiiy c?ace?a ?c cae?ca ia?ee
A?IEI. Iayai?noue a nenoai? IOIE ia i?eaiaeeoue aei aeaeueoiai
ca?eueoaiiy iane iie?ia?o ia iiaa?oi?. I?e/iio o aeiaaeeo iie?ia?ecaoe??
IA aieeao IOIE ia niinoa??aa?oueny: iana ie?aee i?aeoe/ii iaeiaeiaa, a
oie /an ye IOIE ni?ey? i?aeaeuaiith ?ic/eiiino? OI a ia’?i? ?ic/eio,
ciaiooth/e eiai eiioeaio?aoe?th ia iiaa?oi? ieanoeiee, ui coiiaeth?
cieaeaiiy aeoiaeo iiaa?oiaaiai iie?ia?o. Iaeiae iaiao?aeii a?aei?oeoe,
ui, ia aeeaey/enue ia iaioo oiaueio ie?aee, ooai?aii? a i?enooiino?
IOIE, ?aeue?o i?aeeeaaeee i?aaeth?oueny, i/aaeaeii, ca ?aooiie
i?aeaeuaiiy iiaa?oiaai? aeoeaiino? eiiiiiaio?a iie?ia?ecaoe?eii?
nenoaie.

Oaaeeoey 4.

I?eaaaeaia iana iie?ia?ii? ie?aee ia ??cieo iaoaeaaeo iiaa?oiyo.

Nenoaie: 0,1 ian.% (-IAI; 0,13 ian.% AE; 0,12 ian.% IOIE.

*an iie?ia?ecaoe?? 60 oa., oaiia?aoo?a 15(10 N

? i/i Nenoaia nIA, ian. % nOI, ian. % S(104, i2 (m(0,02)(

102, ea(i-2

1

2

3

4

5

6 (-IAI-AE-IA-Fe*

(-IAI-AE-IA-OI-Fe*

(-IAI-AE-IA-Fe**

(-IAI-AE-IA-OI-Fe**

(-IAI-AE-IA-IOIE-Fe*

(-IAI-AE-IA-OI-IOIE-Fe* 2,8

2,8

3,0

2,9

2,8

2,9 —

5,9

6,0

5,7 6,8

7,0

3,4

3,4

6,8

7,4 1,18

6,11

1,40

3,77

1,20

4,74

Fe* — ieanoeiee ?c cae?ca ia?ee A?IEI;

Fe** — ieanoeiee c? noae? 20.

Anoaiiaeaii, ui iie?ia?i? ie?aee c iie?iaoeeae?eeaoo aeneoathoue i?e
85(5 oN ia i?ioyc? 15-20 oaeeei, a ie?aee, io?eiai? i?e noi?ni?e
iie?ia?ecaoe?? IA ? OI, aeiaaathoue a?eueoeo ye o?eaaeino? (aeecueei 2
aiaeei), oae ? oaiia?aoo?e nooee (100(5 oN). Iiaeia aaaaeaoe, ui i?ae
/an aenoooaaiiy eeaeeeo ie?aie a?aeaoaa?oueny i?ioean iiaeaeueoi?
iie?ia?ecaoe??, i?e/iio ie?aee, iaea?aeai? a i?enooiino? OI, aeiaaathoue
aeui? oaiia?aoo?e aeey caaa?oaiiy i?ioeano iie?ia?ecaoe??. I?ney
cae?i/aiiy oeueiai i?ioeano iie?ia?ia ie?aea noa? aeaaeeith, aeeneo/ith
? ia ? eeaeeith. Oaeei /eiii, ci?ithth/e oaiia?aoo?iee ?aaeei ?
o?eaae?noue nooee iiaeia io?eioaaoe a?aeiia?aei? ooi?ai?ni? iie?ia?i?
iie?eooy.

A E N I I A E E

Cai?iiiiiaaii aaaaoieiiiiiaioio ?i?oe?thth/o nenoaio c o/anoth
(-ieneaoee-o?ao-aooeeia?ieneaeo, yea i?eaeaoia aeey ?i?oe?thaaiiy
iecueeioaiia?aoo?ii? (285(295 E) iie?ia?ecaoe?? iaoeeiaiai ao??o
ia?ooi?a?i?eieneia?ooi?aooaiiai? eeneioe c iaea?aeaiiyi iie?ia?o ye a
ia’?i?, oae ? ia iaoaeaa?e iiaa?oi?.

Aecia/aii e?iaoe/i? ia?aiao?e oa?iiaeenioe?aoe??
(-ieneaoee-o?ao-aooeeia?ieneaeo o aiaeieo ?ic/eiao a i?enooiino?
anei?a?iiai? eeneioe oa ?ii?a iaoae?a ci?iiiai nooiaiy ieeneaiiy i?e pH
na?aaeiaeua ??aiiio 2(5.

Aeey e?euee?niiai eiio?ieth ci?ie eiioeaio?aoe??
(-ieneaoee-o?ao-aooeeia?ieneaeo a neeaaeieo ?i?oe?thth/eo nenoaiao
?ic?iaeaii aeinoaoiuei a?aeoai?thaaio (a?aeoeeaiiy 4%) iiey?ia?ao?/io
iaoiaeeeo. Anoaiiaeaii, ui no?oie a?aeiiaeaiiy
(-ieneaoee-o?ao-aooeeia?ieneaeo a oaeeo nenoaiao iathoue eaac?aeeooc?eio
i?e?iaeo i?e pH=2(5 a ae?aiacii? eiioeaio?aoe?e aeaiiey?ecaoi?a
(3(10-3(3(10-4) iieue/e.

I?ioean oa?iie?co (-ieneaoee-o?ao-aooeeia?ieneaeo o aiaeiiio ?ic/ei?
(pH=4) iieno?oueny e?iaoe/iei ??aiyiiyi ia?oiai ii?yaeeo c aia?a??th
aeoeaaoe?? (122,5(2) eAeae/iieue a ae?aiacii? oaiia?aoo? (383(418) E.
I?e cieaeaii? pH aei 2 oaeaee?noue i?ioeano ciaioo?oueny a 1,5(2 ?ace, a
oaiia?aoo?ia caeaaei?noue eiinoaio oaeaeeino? ia? iai?yiie?i?eiee
oa?aeoa?, ui na?ae/eoue i?i eiieo?aioi?noue iaoai?ci?a
oa?iiaeenioe?aoe?? (-ieneaoee-o?ao-aooeeia?ieneaeo a aeaiiio
oaiia?aoo?iiio ?ioa?aae?.

A i?enooiino? anei?a?iiai? eeneioe, yea, ye iaie iieacaii, ooai?th? c
iieaeoeaie (-ieneaoee-o?ao-aooeeia?ieneaeo ?ioa?iaae?ao c aeoeaiaaiei
(I(I( ca’yceii, oaiia?aoo?a aeoeaiiai ?iceeaaeo ia?ieneaeo cieaeo?oueny
a na?aaeiueiio ia 600.

Iaoiaeaie a?neiceiao???, ?*- oa OO-niaeo?ineii??, iiey?ia?ao??
aeiaaaeaii anioe?aoeaio aca?iiae?th i?ae anei?a?iiaith eeneioith ?
(-ieneaoee-o?ao-aooeeia?ieneaeii, yea aeeeeea? aeoeaaoe?th ia?ieneaeiiai
(I(I( ca’yceo. Iayai?noue a iieaeoe? anei?a?iiai? eeneioe
ooieoe?iiaeueieo (OH, C=O, C=C a?oi coiiaeth? ooai?aiiy aeae?eueeio
oei?a niaoeeo?/ieo anioe?ao?a c iieaeoeith
(-ieneaoee-o?ao-aooeeia?ieneaeo i?e ??cieo ni?aa?aeiioaiiyo eiiiiiaio?a
anei?a?iiaa eeneioa : (-ieneaoee-o?ao-aooeeia?ieneae = 4:1, 1:1, 1:2 i?e
pH=4. A ?acoeueoao? cieaeaiiy pH aei 2 anioe?aoeaia aca?iiae?y
i?aaeth?oueny.

Aeiaeaoee ?ii?a iaoae?a ci?iiiai nooiaiy ieeneaiiy (Cu2+, Fe3+, Mn2+,
Ce3+, Ti3+) eaoae?cothoue ?iceeaae (I(I( ca’yceo. I?aeoe/ii
aaciina?aaeiuei c iieaeoeith ia?ieneaeo ?aaaothoue ?iie iaoae?a ieae/iai
nooiaiy ieeneaiiy ? i?e iayaiino? a nenoai? i?aai?/ieo a?aeiiaiee?a
ieneaeii-a?aeiiaia nenoaia i?aoeth? oeeee?/ii. Aeine?aeaeoaai? ?a/iaeie
ca a?aeiiaiith aeoeai?noth ?icoaoiaothoueny a ?yae : anei?a?iiaa eeneioa
> o?oeoica > aetheica.

Oaeaee?noue oa?iiaeenioe?aoe?? (-ieneaoee-o?ao-aooeeia?ieneaeo i?e
eiioaeo? c i?aeiith oa noaeaaith iiaa?oiyie iii?oii i?enei?th?oueny :
a?ae k=1,51(10-4 n-1 (323 E, N(Cu2+)=5(10-5 iieue/e) aei k=9,1(10-4 n-1
(313 E, SCu=1,72(10-3 i2); ? a?ae k=0,1(10-4 n-1 (294 E, N(Fe2+)=1(10-5
iieue/e) aei k=0,9(10-4 n-1 (294 E, SFe=4(10-3 i2). Oea iia’ycaii c
ooai?aiiyi iiaa?oiaaeo eiiieaen?a iaoae — anei?a?iiaa eeneioa —
ia?ieneae, i?i ui na?ae/aoue ?acoeueoaoe aieueoaiia?iiao?e/ieo
aeine?aeaeaiue, a oaeiae c aeuith eaoae?oe/iith aeoeai?noth ?ii?a
iaoae?a, aaia?iaaieo aaciina?aaeiuei c iaoaeaai? iiaa?oi? a ?aaeoe?eiee
ia’?i a ii??aiyii? c ?iiaie iaoae?a, aaaaeaieie o aeaeyae? nieae.

A ?acoeueoao? aeaoaeueieo aeine?aeaeaiue oaiia?aoo?ii? caeaaeiino?
eiinoaio oaeaeeino? ?aaeoe?? oa?iiaeenioe?aoe?? -I-I- ca’yceo a nenoai?
(-ieneaoee-o?ao-aooeeia?ieneae — anei?a?iiaa eeneioa a i?enooiino?
i?aeieo ieanoeiie c ??ciith ieiuath aaiiao?e/ii? iiaa?oi? a ?ioa?aae?
(293(313) E aeyaeaii iaeanoue e?iaoeee oa?iie?co c iecueeeie aia?a?yie
aeoeaaoe?? i?e (293(305) E ? E<3,0(10-2 i. I?iaaaeaii eaaioiai-o?i?/iee ?ic?aooiie aeaeo?iiii-i?inoi?iai? no?oeoo?e (-ieneaoee-o?ao-aooeeia?ieneaeo c iioei?caoe??th aaiiao???. Aeyaeaii nooo?ao ci?io no?oeoo?e iieaeoee ia?ieneaeo aiane?aeie iioei?caoe??, iniaeeai cia/io aeey aeiaaeeie ca’yceo (I(I( oa aeaia?aiieo eoo?a. Aeey iioei?ciaaii? aaiiao??? ?ic?aoiaaii aaee/eio aeeiieueiiai iiiaioo (3,199 Ae), oaieioo ooai?aiiy ((388,86 eAeae/iieue), aaee/eie aoaeoeaieo ca?yae?a aoii?a a iieaeoe?. Iaea?aeaia iioeiaeueia no?oeoo?a ?, i/aaeaeii, iaea?eueo aeecueeith aei ?noeiii?. ?ic?aooiie eii?aeeiaoe ?aaeoe?? aiiie?oe/iiai ?iciaaeo (-ieneaoee-o?ao-aooeeia?ieneaeo ii (I(I( ca’yceo oa aiae?c caeaaeiino? aaee/eie aia?a?? aeoeaaoe?? ?iciaaeo ia?ieneaeo a?ae eooa “?ice?oaiiy” o?aaiaio?a iieacaee, ui ?aaeoe?eia eii?aeeiaoa a?aeiia?aea? aeoaea aocueeiio ei?eaei?o cia/aiue eoo?a ? iani?aaae? oeyo ?aaeoe?? i?ioiaeeoue i?e eoo? 00, yeee iaea?eueoa iaaeeaea?oueny aei ?aaeueii? aaee/eie. Aenia?eiaioaeueii i?aeoaa?aeaeaii o/anoue ?ii?a iaoae?a ci?iiiai nooiaiy ieeneaiiy a ?aaeoe?? ?iciaaeo (-ieneaoee-o?ao-aooeeia?ieneaeo. Aaaaea?oueny, ui ?aaeoe?y o?aaiaioaoe?? ia?ieneaeo i?io?ea? /a?ac noaae?th ooai?aiiy eiiieaeno c ia?aiinii ca?yaeo. I?e oeueiio ia?aianaiiy aeaeo?iio cae?enith?oueny ii aioo??noa?iiio iaoai?cio. Iaea?aeai? ci?oai? (iaoeeae?eeao-ooi?iiiiia?) iie?ia?i? ie?aee ia noaeaa?e (noaeue 20), cae?ci?e (ia?ee A?IEI) oa i?aei?e iiaa?oiyo a i?enooiino? ?i?oe?thth/i? nenoaie (-ieneaoee-o?ao-aooeeia?ieneae - anei?a?iiaa eeneioa i?e oaiia?aoo?? 288 E. Ciaioaiiy ?iaeoeoe?eiiai ia??iaeo i?ioeano iie?ia?ecaoe?? aeinyaa?oueny aeiaeaaaiiyi aeoeai?oiai iiiiia?o - iaoeeae?eeaoo. INIIAI? ?ACOEUeOAOE AeENA?OAOe?? AEEEAAeAII A IANOOIIEO IOAE?EAOe?ssO: O?enoeia Ai?aa/aanueea, ??eia A?thoiaaoeueea, ?aaai Eiaaeue/oe. Aeaeo?io?i?/ia aeine?aeaeaiiy ?i?oe?thth/i? eiiiiceoe?? ia iniia? (-ieneaoee-o?ao-aooeeia?ieneaeo // Noai ? ia?niaeoeae ?icaeoeo oai?/ii? iaoee oa i?iieneiaino? a cao?aeiiio ?aa?ii? Oe?a?ie: Oace aeiiia?aeae iaoeiai? eiioa?aioe?? aei 150-??//y “Euea?anueei? iie?oaoi?ee”, Euea?a, 17-19 o?aaiy 1994 ?. - Euea?a, 1994. - N.108. O.?.Ai?aa/aanueea, I.I.Eiaaoc, ?.A.A?thoiaaoeueea, ?.I.Eiaaeue/oe. Aeine?aeaeaiiy neeaaeii? ?i?oe?thth/i? nenoaie ia iniia? (-ieneaoee-o?ao-aooeeia?ieneaeo a i?ioean? iie?ia?ecaoe?? // Oace aeiiia?aeae iaoeiai? eiioa?aioe?? “I?iaeaie i?aai?/iiai neioaco”, Euea?a, 25 eenoiiaaea 1994 ?. - Euea?a, 1994. - N.70. ?.I.Eiaaeue/oe, ?.A.A?thoiaaoeueea, O.?.Ai?aa/aanueea. Aieea noaeaai? iiaa?oi? ia e?iaoeeo oa?iiaeano?oeoe?? (-ieneaoee-o?ao-aooeeia?ieneaeo // A?niee Euea?a. oi-oo. Na?. o?i. - 1995. - Aei.35. - N.7-10. O.?.Ai?aa/aanueea, ?.A.A?thoiaaoeueea, ?.I.Eiaaeue/oe, I.I.Eia?iiaa, I.E.Iiaee?nneay. Aeaeo?io?i?/ia aeine?aeaeaiiy ?i?oe?thth/i? eiiiiceoe?? ia iniia? (-ieneaoee-o?ao-aooeeia?ieneaeo // Oace aeiiia?aeae ?-ai Oe?a?inueeiai aeaeo?io?i?/iiai c’?caeo, Ee?a, 15-17 o?aaiy 1995 ?. -Ee?a, 1995. - N. 40. ?.A.A?thoiaaoeueea. Aieea ?ii?a i?ae? ia oa?iiaeano?oeoe?th (-ieneaoee-o?ao-aooeeia?ieneaeo a i?enooiino? anei?a?iiai? eeneioe // Oace aeiiia?aeae iaoeiai-i?aeoe/ii? eiioa?aioe?? “Euea?anuee? o?i?/i? /eoaiiy”, Euea?a, 26 o?aaiy 1995. - Euea?a, 1995. - N.69. ?.A.A?thoiaaoeueea, O.?.Ai?aa/aanueea, ?.I.Eiaaeue/oe. E?iaoeea ?aaeeeaeiooai?aiiy a ?i?oe?thth/eo eiiiiceoe?yo ia iniia? (-ieneaoee-o?ao-aooeeia?ieneaeo // Oace aeiiia?aeae VIII Oe?a?inueei? eiioa?aioe?? c aenieiiieaeoey?ieo niieoe, Ee?a, 24-26 aa?aniy 1996 ?. Ee?a, 1996. - N.18. ?.A.A?thoiaaoeueea, ?.?.A?oei. Anioe?aoeaia aca?iiae?y i?ae eiiiiiaioaie ?i?oe?thth/i? nenoaie ia iniia? (-ieneaoee-o?ao-aooeeia?ieneaeo // A?niee Euea?a. oi-oo. Na?. o?i. - 1997. - Aei.37. - N.74-76. ?.A.A?thoiaaoeueea. Eaoae?c iaoaeaaith iiaa?oiath oa?iiaeenioe?aoe?? ia?ieneaeiiai -I-I- ca’yceo (-ieneaoee-o?ao-aooeeia?ieneaeo // A?niee Euea?a. oi-oo. Na?. o?i. - 1997. - Aei.37. - N.77-79. A?thoiaaoeueea ?.A., Eiaaeue/oe ?.I. Eaaioiai-o?i?/iee ?ic?aooiie aeaeo?iiii-i?inoi?iai? no?oeoo?e (-ieneaoee-o?ao-aooeeia?ieneaeo // Oace aeiiia?aeae VI iaoeiai? eiioa?aioe?? “Euea?anuee? o?i?/i? /eoaiiy-97”, Euea?a, 29-30 o?aaiy 1997 ?. - Euea?a, 1997. - N.96. ??eia A?thoiaaoeueea. Io?eiaiiy iie?ia?ieo ie?aie ia iaoaeaaeo iiaa?oiyo c o/anoth (-ieneaoee-o?ao-aooeeia?ieneaeo // Oace aeiiia?aeae VI iaoeiai? eiioa?aioe?? “Euea?anuee? o?i?/i? /eoaiiy-97”, Euea?a, 29-30 o?aaiy 1997 ?. - Euea?a, 1997. - N.143. ?.I.Eiaaeue/oe, ?.A.A?thoiaaoeueea, O.?.Ai?aa/aanueea. Eaaioiai-o?i?/iee ?ic?aooiie aeaeo?iiii-i?inoi?iai? no?oeoo?e (-ieneaoee-o?ao-aooeeia?ieneaeo // Oe?.o?i.aeo?i. 1998. - O.64. - ?.5. - N.66-70. A.I.Eiaaeue/oe, E.A.A?thoiaaoeeay, E.?.Ai?aa/aaneay. Eaoaeec oa?iiaeennioeeaoeee (-ieneyoee-o?ao-aooeeia?ieneaea eiiaie, aaia?e?oaiuie iaoaeee/aneie iiaa?oiinoth iaaee // AE.iau.oeiee. - 1998. - O.68. - Aui.10. - N.1686-1689. A I I O A Oe ? ss A?thoiaaoeueea ?. A. Eaoae?oe/ia oa?iiaeenioe?aoe?y (-ieneaoee-o?ao-aooee-ia?ieneaeo o aiaeiiio na?aaeiaeu?. - ?oeiien. Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa o?i?/ieo iaoe ca niaoe?aeuei?noth 02.00.04 - o?ce/ia o?i?y. - Euea?anueeee aea?aeaaiee oi?aa?neoao ?i. ?aaia O?aiea, Euea?a, 1999. Caoeua?oueny 12 iaoeiaeo i?aoeue, ye? i?noyoue ?acoeueoaoe aeine?aeaeaiue eaoae?oe/ii? oa?iiaeenioe?aoe?? (-ieneaoee-o?ao-aooeeia?ieneaeo ((-IAI) o aiaei?ic/eiieo ?i?oe?thth/eo nenoaiao. Anoaiiaeai? e?iaoe/i? caeiiii??iino? oa?iie?co ia?ieneaeiiai ?i?oe?aoi?a (-IAI a i?enooiino? oaeeo a?aeiiaiee?a ye anei?a?iiaa eeneioa, o?oeoica, aetheica oa ?iie iaoae?a ci?iiiai nooiaiy ieeneaiiy. Aia?oa aeine?aeaeai? iniaeeaino? ia?aa?ao oe??? ?aaeoe?? i?e aca?iiae?? eiiiiiaio?a nenoaie c iiaa?oiyie iaoae?a. Cai?iiiiiaaii noaio a?aeiiaeaiiy (-IAI ?iiaie iaoae?a a ieae/iio nooiai? ieeneaiiy a i?enooiino? anei?a?iiai? eeneioe. ?ic?iaeaii iiey?ia?ao?/io iaoiaeeeo eiio?ieth ca ai?noii ia?ieneaeo a ?i?oe?thth/?e nenoai? a i?ioean? eiai ?iceeaaeo. I?iaaaeai? eaaioiai-o?i?/i? ?ic?aooiee aeaeo?iiii-i?inoi?iai? no?oeoo?e (-IAI c iioei?caoe??th aaiiao???, a oaeiae eii?aeeiaoe ?aaeoe?? aiiie?oe/iiai ?iciaaeo ia?ieneaeo ii -I-I- ca'ceo. Aenia?eiaioaeueii i?aeoaa?aeaeaii o/anoue ?ii?a iaoae?a ci?iiiai nooiaiy ieeneaiiy a ?aaeoe?? ?iciaaeo (-IAI. Aaaaea?oueny, ui ?aaeoe?y o?aaiaioaoe?? ia?ieneaeo i?io?ea? /a?ac noaae?th ooai?aiiy eiiieaeno c ia?aiinii ca?yaeo. I?e oeueiio ia?aiin aeaeo?iio cae?enith?oueny ii aioo??noa?iiio iaoai?cio. Iieacaii iiaeeea?noue canoinoaaiiy cai?iiiiiaaii? ?i?oe?thth/i? nenoaie, yea aeeth/a? (-IAI, anei?a?iiao eeneioo i?e eiioaeo? c iaoaeaaeie iiaa?oiyie (cae?ci ia?ee A?IEI, noaeue 20, i?aeue), aeey neioaco iie?ia?ieo ie?aie ia iniia? iaoeeiaiai ao??o ia?ooi?a?i?eieneia?ooi?aooaiiai? eeneioe. Eeth/ia? neiaa: i?aai?/iee ia?ieneae, ?i?oe?thth/a neoaia, aeoeaoth/? aeiaeaoee, iiey?ia?ao?y, iaoaee. S U M M A R Y Bryuchovetc’ka I.V. A catalytic thermal decomposition of (-oxyethyl-tert-butylperoxide in the aqueous medium. - Manuscript. Thesis for obtaining the scientific degree of Candidate of Chemical Sciences. Speciality 02.00.04 - Physical Chemistry. - Ivan Franko State University of L’viv, L’viv, 1999. Twelve scientific works, which containing the results of the studies of the catalytic thermal decomposition of (-OEP in the aqueous initiated systems, are defends. The kinetic patterns of the thermal decomposition of peroxide initiator in the presence of reductants (ascorbic acid, fructose, glucose and mixed-valence ions of metals) is determined. For the first time the details of this reaction during the interaction of the components of system with the metals surface is determined. The scheme of reduction of the (-OEP by metal ions in the lower degree of oxidation in the presence of ascorbic acid is proposed. The polarographic procedure of control of the peroxide content in the initiated system is developed. The quantum-chemical calculation of electron-spatial structure of the (-OEP with the optimization of its geometry is performed. The coordinate of homolytic decomposition reaction of the -O-O- bond is calculated. The participation of the mixed-valence metal ions in the process of the (-OEP decomposition is confirmed experimentally. It is proposed that reaction of peroxide decomposition proceeds through the step of the charge-transfer complex formation. In this case the electron transfer realizes according to the inner-sphere mechanism. The possibility of using of the proposed initiated system ((-OEP-ascorbic acid) during its contact with the surface of the metals (iron, steel, copper) for the synthesis of the polymer films on the base of methyl ether of the perfluorovinyloxyperfluorobutane acid also is shown. Key words: organic peroxide, initiated system, activated additions, polarography, metals. A I I I O A Oe E ss A?thoiaaoeeay E. A. Eaoaeeoe/aneay oa?iiaeennioeeaoeey (-ieneyoee-o?ao-aooee-ia?ieneaea a aiaeiie n?aaea. - ?oeiienue. Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa oeie/aneeo iaoe ii niaoeeaeueiinoe 02.00.04 - oece/aneay oeiey. - Eueaianeee ainoaea?noaaiiue oieaa?neoao ei. Eaaia O?aiei, Eueaia, 1999. Caueuaaony 12 iao/iuo ?aaio, eioi?ua niaea?aeao ?acoeueoaou enneaaeiaaiee eaoaeeoe/aneie oa?iiaeennioeeaoeee (-ieneyoee-o?ao-aooeeia?ieneaea ((-IYI) a aiaei?anoai?eiuo eieoeee?othueo nenoaiao. Oeaeue aeaiiie ?aaiou - nicaeaiea aunieiyooaeoeaiuo ieceioaiia?aoo?iuo eieoeee?othueo nenoai ia iniiaa (-IYI aeey iauaiiuo e iiaa?oiinoiuo iieeia?ecaoeeiiiuo i?ioeannia a aiaeiuo ?anoai?ao. Aeey yoiai yenia?eiaioaeueii onoaiiaeaiu eeiaoe/aneea caeiiiia?iinoe oa?iieeca ia?ieneaeiiai eieoeeaoi?a (-IYI a i?enoonoaee ainnoaiiaeoaeae oeia anei?aeiiaie eeneioe, o?oeoicu, aetheicu e eiiia iaoaeeia ia?aiaiiie noaiaie ieeneaiey (Fe3+, Cu2+, Mn2+, Ti3+ e Ce3+). Aia?aua enneaaeiaaiu iniaaiiinoe i?ioaeaiey yoie ?aaeoeee i?e acaeiiaeaenoaee eiiiiiaioia nenoaiu n iiaa?oiinoyie iaoaeeia. I?aaeeiaeaia noaia ainnoaiiaeaiey (-IYI eiiaie iaoaeeia a iecoae noaiaie ieeneaiey a i?enoonoaee anei?aeiiaie eeneiou, eioi?ay iiaeoaa?aeaeaao, /oi aeoeae?othuaa aeaenoaea iaoaeee/aneie iiaa?oiinoe ia i?ioeann oa?iieeca -I-I- nayce (-IYI yaeyaony ?acoeueoaoii i?ioaeaiey aeaoo ia?aeeaeueiuo i?ioeannia. Ai-ia?auo, acaeiiaeaenoaea ia?ieneaea n eiiaie, i?iaeooee?iaaiiuie iiaa?oiinoueth, a iauaia e eo iineaaeothuay ?aaaia?aoeey anei?aeiiaie eeneioie, eioi?ay iaania/eaaao ooieoeeiie?iaaiea oeeeee/aneeo ieeneeoaeueii-ainnoaiiaeoaeueiuo i?aa?auaiee; ai-aoi?uo, aeoeaaoeey ?aceiaeaiey ia?ieneaea a ?acoeueoaoa ia?aciaaiey eiiieaenia iiaa?oiinoue-anei?aeiiaay eeneioa-ia?ieneae. ?ac?aaioaia iiey?ia?aoe/aneay iaoiaeeea eiio?iey ca niaea?aeaieai ia?ieneaea a eieoeee?othuae nenoaia a i?ioeanna aai ?aceiaeaiey eae iaeaieaa oieaa?naeueiay i?e ii?aaeaeaiee ia?ieneaeiuo a?oii a iiiaieiiiiiaioiuo eieoeee?othueo nenoaiao, iineieueeo aeey eco/aiey iniaaiiinoae i?ioeanna oa?iiaeennioeeaoeee (-IYI a neiaeiuo eieoeee?othueo nenoaiao e ii?aaeaeaiey eeiaoe/aneeo ia?aiao?ia ia iiaoo auoue eniieueciaaiu o?aaeeoeeiiiua oeo?eiao?e/aneea iaoiaeu aiaeeca a nayce n i?ioaeaieai ia?aeeaeueiuo ieeneeoaeueii-ainnoaiiaeoaeueiuo ?aaeoeee. I?iaaaeaiu eaaioiai-oeie/aneea ?an/aou aeaeo?iiii-i?ino?ainoaaiiie no?oeoo?u (-IYI n iioeiecaoeeae aaiiao?ee. Iieo/aiiay iioeiaeueiay no?oeoo?a yaeyaony iaeaieaa aeeceie e enoeiiie. ?ann/eoaia eii?aeeiaoa ?aaeoeee aiiieeoe/aneiai ?aniaaea ia?ieneaea ii -I-I- nayce. Iieacaii, /oi ?aaeoeeiiiay eii?aeeiaoa ioaa/aao i/aiue oceiio ei?eaei?o cia/aiee oaeia "?aceaoa" o?aaiaioia. A aeaenoaeoaeueiinoe iooue ?aaeoeee i?ioiaeeo iiae oaeii 00, i?e eioi?ii ?ann/eoaiiay aaee/eia yia?aee aeoeaaoeee ?aniaaea ia?ieneaea i?eaeeaeaaony e iiuoiie. Yenia?eiaioaeueii iiaeoaa?aeaeaii o/anoea eiiia iaoaeeia ia?aiaiiie noaiaie ieeneaiey a ?aaeoeee ?aniaaea (-IYI. I?aaeiieaaaaony, /oi ?aaeoeey o?aaiaioaoeee ia?ieneaea i?ioaeaao /a?ac noaaeeth ia?aciaaiey eiiieaena n ia?aiinii ca?yaea. I?e yoii ia?aiin aeaeo?iia inouanoaeyaony ii aioo?enoa?iiio iaoaiecio. Iieacaia aiciiaeiinoue i?eiaiaiey i?aaeeiaeaiiie eieoeee?othuae nenoaiu, aeeth/athuae (-IYI, anei?aeiiaoth eeneioo i?e eiioaeoa n iaoaeee/aneeie iiaa?oiinoyie (aeaeaci ia?ee A?IEI, noaeue 20, iaaeue), aeey neioaca iieeia?iuo ieaiie ia iniiaa iaoeeiaiai yoe?a ia?ooi?aeieeieneia?ooi?aooaiiaie eeneiou. Eeth/aaua neiaa: i?aaie/aneee ia?ieneae, eieoeee?othuay nenoaia, aeoeae?othuea aeiaaaee, iiey?ia?aoey, iaoaeeu. - PAGE 2 - - PAGE 3 -

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