OE?A?INUeEEE AeA?AEAAIEE

O?I?EI-OAOIIEIA?*IEE OI?AA?NEOAO

Ia i?aaao ?oeiieno

I?IOeAIEI Ay/aneaa Na?a?eiae/

OAeE 541.138.3:669.268.7

AEAEO?IA?AeIIAEAIIss NIIEOE, UI I?NOssOUe O?II,

O I?ENOOIINO? IO?AOEII? OA AI?IIIOeOIAI? EENEIO

Niaoe?aeuei?noue 02.00.05 – aeaeo?io?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 Oe?a?inueeiio aea?aeaaiiio o?i?ei-oaoiieia?/iiio
oi?aa?neoao? I?i?noa?noaa ina?oe Oe?a?ie

Iaoeiaee ea??aiee:aeieoi? o?i?/ieo iaoe, i?ioani?, caa?aeoth/ee
eaoaae?ith o?ce/ii? o?i?? OAeOOO, aee?aeoi? IAe? Aaeueaaiio?i?? OAeOOO

Aeaieeia Oae?en Eineiiae/Io?oe?ei? iiiiaioe:aeieoi? o?i?/ieo iaoe,
i?ioani?, caa?aeoth/ee eaoaae?ith iai?aai?/ii? o?i??
Aei?i?iiao?ianueeiai aea?aeaaiiai oi?aa?neoaoo

Aa?aaethe A?eoi? Oaaei?iae/,eaiaeeaeao oaoi?/ieo iaoe, noa?oee iaoeiaee
ni?a?ia?oiee Oe?a?inueeiai IAe? oaoiieia?? iaoeiiaoaeoaaiiy, i.
Aei?i?iiao?ianuee

Iaa??iee A?eoi? Ieoaeeiae/I?ia?aeia onoaiiaa:?inoeooo caaaeueii? oa
iai?aai?/ii? o?i?? IAI Oe?a?ie, i. Ee?a

Caoeno a?aeaoaeaoueny «3» /a?aiy 1999 ?. i 1400 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: 320640, 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.

Aaoi?aoa?ao ?ic?neaiee «23» ea?oiy 1999 a.

A/aiee nae?aoa? niaoe?ae?ciaaii? a/aii? ?aaee, e.o.i., aeioeaio

?. Ae. I?i?aeeaCAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue ?iaioe. Aeaeo?ie?oe/ia o?iioaaiiy – aoaeoeaiee oa
iioe?aiee niin?a ia?iaee iiaa?oi? iaoaeaaeo ae?ia?a. Iaeia/a
o?aaeeoe?eia oaoiieia?y o?iioaaiiy c o?iiiaieeneeo ?ic/ei?a ua ia
aeineiiaea, a oyaeaiiy i?i e?iaoe/i? caeiiii??iino? oa iaoai?ci
aeaeo?ia?aeiiaeaiiy niieoe o?iio iaiaeiicia/i? ? ia??aeei noia?a/eea?.
Oiio iaeiie/oaaiiy iiaeo aenia?eiaioaeueieo aeaieo ? ?ic?iaea
oai?aoe/ieo eiioeaioe?e o aaeoc? aeaeo?iinaaeaeaiiy o?iio ia ao?a/athoue
nai?? aeooaeueiino?.

Eeane/iei iaoiaeii iie?ioaiiy oaoiieia?/ieo oa?aeoa?enoee
aeaeo?iinaaeaeaiiy iaoae?a ? aaaaeaiiy aei neeaaeo aeaeo?ie?oo ??cieo
i?aai?/ieo niieoe, aea ca ??aee?nieie aeiyoeaie oeae niin?a ia
ciaoiaeeoue canoinoaaiiy o o?iiiaieeneeo ?ic/eiao. I?ioa, inoaii?i /anii
aeoeaii iaaiai?th?oueny ieoaiiy uiaei aeei?enoaiiy ?yaeo i?aai?/ieo
niieoe, cie?aia io?aoeii? eeneioe, ye aeiaaaee aei aeaeo?ie?o?a
o?iioaaiiy. Iaeiae ?ieue io?aoeii? eeneioe o i?ioean? inaaeaeaiiy o?iio,
?? aieea ia aeanoeaino? iie?eoo?a, ui ooai?ththoueny, aea/ai? ua
iaaeinoaoiuei.

Aeueoa?iaoeaith aenieioiene/iei o?iiiaieeneei ?ic/eiai ? aeaeo?ie?oe ia
iniia? niieoe o?eaaeaioiiai o?iio. ?o ?ic?iaea cae?enith?oueny ia??aeei
aii??e/iei oeyoii. Oiio anoaiiaeaiiy iaoai?cio inaaeaeaiiy iaoaeo c
aeaeo?ie?o?a, ui i?noyoue nie? o?eaaeaioiiai o?iio, noaiiaeoue aaaeeeao
iaoeiao i?iaeaio.

Aeena?oaoe?eia ?iaioa aeeiiaia a?aeiia?aeii aei aea?aeathaeaeaoieo IAe?:
«Aeine?aeaeaiiy caeiiii??iinoae aaeni?aoe?? i?aai?/ieo niieoe, e?iaoeee
i?aeoacieo i?ioean?a oa iaoiae?a iaianaiiy iaoaeaaeo oa iaiaoaeaaeo
iie?eoue», ? 31940990 (I?iina?oe Oe?a?ie, 1994 — 1996 ??.); «?ic?iaeoe
oaoiieia?/i? i?ioeane o?iioaaiiy, ye? aeicaieythoue cieceoe o 2 — 5
?ac?a eiioeaio?aoe?th aenieioiene/ieo niieoe oanoeaaeaioiiai o?iio aai
cian?i ?o aeeeth/eoe o aeaeo?ie?oao oa no?/ieo aiaeao», ? 02.02.03/002A
— 93 (AeEIO Oe?a?ie, 1995 ?.); «Aeine?aeaeaiiy aieeao naeaeoeaii?
aaeni?aoe?? IA? ia e?iaoeeo ? iaoai?ci aeaeo?iaeieo i?ioean?a i?e
aeaeo?iinaaeaeaii? iiaeo iaoaeaaeo ? ieneaeieo iaoa??ae?a c
i?iaiiciaaieie aeanoeainoyie», ? 31971090 (I?iina?oe Oe?a?ie, 1997 —
1999 ??.).

Iaoith ?iaioe aoei anoaiiaeaiiy caeiiii??iinoae aieeao io?aoeii? oa
ai?iiioeoiai? eeneio ia aeaeo?ia?aeiiaeaiiy niieoe, ui i?noyoue o?ii, o
aiaeieo ?ic/eiao.

Aeey aeinyaiaiiy iinoaaeaii? iaoe caeaaaeiny aeioe?eueiei:

— aeine?aeeoe aieea iai?aai?/ieo oa i?aai?/ieo aeiaaaie ia i?ioean
iaiiaiiai aeaeo?ia?aeiiaeaiiy ieniai?ii?a oanoeaaeaioiiai o?iio;

— aea/eoe e?iaoe/i? caeiiii??iino? oa iaoai?ci aeaeo?iinaaeaeaiiy o?iio
c oi?i?aoieo ? ae?oeeiaoieo ?ic/ei?a nieae o?eaaeaioiiai o?iio;

— anoaiiaeoe aieea io?aoeii? eeneioe ia oaeaee?noue inaaeaeaiiy o?iio c
o?iiiaieeneeo aeaeo?ie?o?a;

— aeine?aeeoe ei?ic?eii-aeaeo?io?i?/io iiaaae?ieo iie?eoo?a, ui
iaea?aeothoue c aeaeo?ie?o?a c i?aai?/ieie aeiaaaeaie.

Iaoeiaa iiaecia. Iia? aeai? i?i aieea ??cieo iai?aai?/ieo ? i?aai?/ieo
aeiaaaie (na?aae ieo ? io?aoeii? eeneioe) ia e?iaoeeo iaiiaiiai
aeaeo?ia?aeiiaeaiiy ieniai?ii?a Cr(VI) aeicaieeee anoaiiaeoe, ui
aeaeo?io?i?/i?e noaae?? ia?aaeo? aaoa?iaaiia o?i?/ia ?aaeoe?y, a ye?e
aa?ooue o/anoue aeiaaaee-eaoae?caoi?e. ?ic?yae i?iaeoeo?a oe??? ?aaeoe??
iieaaoaiee /a?ac «i?noeiaee» iaoai?ci ia?aiino ca?yaeo.

Ia i?aenoaa? nenoaiaoe/iiai aeine?aeaeaiiy e?iaoe/ieo caeiiii??iinoae
?ic?yaeo ?ii?a Cr(III) ?icaeioo? iia? oyaeaiiy i?i iaoai?ci i?ioeano
aeaeo?iinaaeaeaiiy o?iio c aiaeieo ?ic/ei?a eiai o?eaaeaioieo niieoe,
ca?aeii c yeei a?ae?ieneae-?iie a?athoue ?ieue eaoae?caoi??a i?e
?ic?yae? ?ioa?iaae?ao?a – niieoe Cr(II). Anoaiiaeaii, ui iaaeeooc?ei?
a?aie/i? no?oie inaaeaeaiiy o?iio iaoiiaeai? aeieoaaiiyi aeaeo?iaeii?
iiaa?oi? iaei?ic/eiieie a?ae?ieneaeieie niieoeaie o?iio.

Iieacaii, ui i?e/eiith aiiiaeueii? ei?ic?eii-aeaeo?io?i?/ii? iiaaae?iee
oa i?aeaeuaii? ei?ic?eii? no?eeino? aii?oieo iie?eoo?a, ye?
inaaeaeothoueny c aeaeo?ie?o?a o?iioaaiiy, ui i?noyoue io?aoeio eeneioo,
? oi?ioaaiiy ia iiaa?oi? inaae?a no?eei? ianeaoth/i? ie?aee.

I?aeoe/ia cia/aiiy. Cai?iiiiiaaiee o ?iaio? iaoai?ci aeaeo?iinaaeaeaiiy
o?iio, a oaeiae eiiieaen aenia?eiaioaeueieo aeaieo i?i aieea ??cieo
oaeoi??a ia aeaeo?ia?aeiiaeaiiy niieoe, ui i?noyoue o?ii, oa ia
ei?ic?eii-aeaeo?io?i?/io iiaaae?ieo iie?eoue ? iaoeiaith iniiaith aeey
iiaeo oaoiieia?e iaianaiiy o?iiiaeo aaeueaaiiinaae?a ?c i?iaiiciaaieie
aeanoeainoyie.

Iniaenoee aianie aaoi?a iieyaa? o i?iaaaeaii? aenia?eiaioaeueieo
aeine?aeaeaiue, ia?iaoe? e ocaaaeueiaii? io?eiaieo aeaieo, o ioae?eaoe??
?acoeueoao?a ?iaioe. Iinoaiiaea iaoe oa caaea/ aeine?aeaeaiiy, a oaeiae
iaaiai?aiiy ?acoeueoao?a i?iaaaeaii ni?eueii c iaoeiaei ea??aieeii.

Ai?iaaoe?y ?acoeueoao?a. ?acoeueoaoe ?iaioe aoee i?aaenoaaeai? ia
i?aei. eiio.-aenoaaoe? «I?iaeaie ei?ic?? oa i?ioeei?ic?eiiai caoenoo
eiino?oeoe?eieo iaoa??ae?a» (Ei?ic?y — 94) (1994 ?., i. Euea?a); I-?e
oeaio?aeueii-, no?aeii- oa i?ai?/ii?a?iiaenuee?e ?aa?iiaeuei?e
eiioa?aioe?? ii ia?iaoe? iiaa?oi?: oaoiieia??, iaaeieeoi? na?aaeiaeua oa
noaiaea?oecaoe?y (Iiaa?oiy 95) (1995 ?., i. Iaeaiaa, Eeoaa); VI I?aei.
iaoeiai-oaoi. eiio. «Iia? eiino?oeoe?ei? noae? ? nieaae oa iaoiaee ?o
ia?iaee aeey i?aeaeuaiiy iaae?eiino? oa aeiaaia?/iino? ae?ia?a» (1995
?., i. Caii??aeaey); III I?aei. eiio.-aenoaaoe? «I?iaeaie ei?ic?? oa
i?ioeei?ic?eiiai caoenoo eiino?oeoe?eieo iaoa??ae?a» (Ei?ic?y — 96)
(1996 ?., i. Euea?a); 47-?e ui??/i?e eiioa?aioe?? I?aeia?iaeiiai
Aeaeo?io?i?/iiai Oiaa?enoaa (ISE) (1996 ?., Aani?ai — Aaeaoiioth?aae,
Oai?ueia); IV I?aei. Eiio. «O?aioe?y oa Oe?a?ia, iaoeiai-i?aeoe/iee
aeina?ae o eiioaeno? ae?aeiao iaoe?iiaeueieo eoeueoo?» (1997 ?., i.
Aei?i?iiao?ianuee); IV I?aei. eiio.-aenoaaoe? «I?iaeaie ei?ic?? oa
i?ioeei?ic?eiiai caoenoo iaoa??ae?a» (Ei?ic?y — 98) (1998 ?., i.
Euea?a).

Ioae?eaoe??. Ca iaoa??aeaie aeena?oaoe?? iioae?eiaaii 4 noaoo? ? 7 oac ?
iaoa??ae?a eiioa?aioe?e, aeaiiiiaaii 2 noaoo?.

No?oeoo?a oa ianya aeena?oaoe??. Aeena?oaoe?y neeaaea?oueny c? anooio,
4-o ?icae?e?a, aeniiae?a, nieneo aeei?enoaieo e?oa?aoo?ieo aeaea?ae (222
iaeiaioaaiiy). Aeena?oaoe?y aeeeaaeaia ia 144 noi??ieao, i?noeoue 35
?enoie?a oa 9 oaaeeoeue.

INIIAIEE CI?NO ?IAIOE

O anooi? iaa?oioiaaia aeooaeuei?noue oaie, noi?ioeueiaaia iaoa ?iaioe,
iaaaaeai? a?aeiiino? i?i ca’ycie ?iaioe c aea?aeaaieie iaoeiaeie
i?ia?aiaie, i?i iaoeiao iiaecio oa i?aeoe/ia cia/aiiy ?iaioe, i?i
iniaenoee aianie aaoi?a, a oaeiae i?i ai?iaaoe?th ? ioae?eaoe??.

O ia?oiio ?icae?e? i?eaaaeaiee iaeyae e?oa?aoo?ieo aeaieo i?i
caeiiii??iino? aeaeo?ia?aeiiaeaiiy niieoe oanoeaaeaioiiai oa
o?eaaeaioiiai o?iio, a oaeiae i?i aieea ia oe? i?ioeane i?aai?/ieo
?a/iaei. Ia i?aenoaa? e?oa?aoo?iiai iaeyaeo noi?ioeueiaai? caaea/?
aeine?aeaeaiiy.

O ae?oaiio ?icae?e? iienaia iaoiaeeea aenia?eiaioaeueieo aeine?aeaeaiue.

Ia’?eoaie aeine?aeaeaiiy aoee aeaeo?ie?oe o?iioaaiiy ia iniia?
o?iiieae??aiai aaeoio oa o?iiiaiai aia?ae?eaeo, ui i?noyoue ??ci?
aeiaaaee, na?aae ieo io?aoeio e ai?iiioeoiao eeneioe. O o?iiiaieeneeo
?ic/eiao ?c aeiaaaeith io?aoeii? eeneioe ia?aa?aa?
ieenethaaeueii-a?aeiiaia aca?iiae?y ieniai?ii?a Cr(VI) oa HCOOH. O
?iaio? iaaaaeai? e?iaoe/i? ia?aiao?e oe??? ?aaeoe??. I?ioyaii 0,5 — 1
aiaeeie i?ney aaaaeaiiy HCOOH o ?ic/ei ci?iith eiioeaio?aoe?e
eiiiiiaio?a iiaeia ciaoooaaoe. Aiae?c aeaeo?ie?o?a i?iaiaeeee ii
a?aeiiei iaoiaeeeai oioiiao?e/iei (oioieiei?eiao? EOE-2-OOE-4.2) ?
iioaioe?iiao?e/iei (?iiii?? YA-74) iaoiaeaie.

Aieueoaiia?ia?aie (AAA) iaea?aeoaaee ca aeiiiiiaith iioaioe?inoao?a
IE-50-1.1 oa I-5848 iioaioe?iaeeiai?/iei iaoiaeii ca o?eaeaeo?iaeiith
noaiith. ?iai/eie aeaeo?iaeaie neoaeeee cieioee ? o?iiiaee (Cr —
aaeueaaiiiie?eooy).

Aeaeo?iinaaeaeaiiy ? ?ic/eiaiiy o?iio aeine?aeaeoaaee iaoiaeii
ia?oe?aeueieo noaoe?iia?ieo i,E — caeaaeiinoae. O ?yae? aeine?ae?a
aeei?enoiaoaaee iaa?oiaee oeee?iae?e/iee aeaeo?iae. Oaeaee?noue
inaaeaeaiiy ? ?ic/eiaiiy o?iio aecia/aee a?aa?iao?e/iei iaoiaeii. I?e
oeiio e?euee?noue ia?aeaeueieo aenia?eiaio?a aa??thaaee a?ae 2 aei 5,
a?aeoeeaiiy aenia?eiaioaeueieo cia/aiue oaeaeeino? inaaeaeaiiy ?
?ic/eiaiiy a?ae na?aaeiueiai ia ia?aaeuoaaee 5 %.

O o?aoueiio ?icae?e? ?icaeyioo? e?iaoe/i? caeiiii??iino? ? iaoai?ci
aeaeo?ia?aeiiaeaiiy niieoe Cr(VI) ? Cr(III) o i?enooiino? io?aoeii? oa
ai?iiioeoiai? eeneio.

?ic?yae iie?o?iiao-?ii?a aei iaoaeo yaey? niaith noeoii?noue
iine?aeiaieo nooiai?a a?aeiiaeaiiy Cr(VI) aei Cr(III) ? Cr(III) aei
Cr(0), eiaeiee c yeeo ? aaaaoinoaae?eiei. Ae?oaee nooi?iue cae/aeii ?
a?eueo oiia?eueiaiei (Cr(III) iaeiie/o?oueny a eaoie?o?), aea eiai
aea/aiiy o o?iiiaieeneeo aeaeo?ie?oao iia’ycaia ?c na?eicieie
iaoiaee/ieie oo?oaeiaiiyie. Oiio e?iaoeea ?ic?yaeo ?ii?a Cr(III) aei
Cr(0) aoea ?icaeyiooa o ?ic/eiao ia iniia? nieae o?eaaeaioiiai o?iio.
Aeine?aeaeaiiy aeaeo?iinaaeaeaiiy o?iio c aeaeo?ie?o?a ia iniia? Cr(III)
ia o?eueee aeicaiey? iiaeaethaaoe ae?oaee nooi?iue a?aeiiaeaiiy a
?ic/eiao o?iiiai? eeneioe, aea e ia? naiino?eia cia/aiiy.

Iaiiaiee ?ic?yae ieniai?ii?a oanoeaaeaioiiai o?iio:

CrmO3m+12- + (6m+2) H+ + 3me- m Cr3+ + (3m+1) H2O(1)

ia aaaaoueio aeaeo?iaeieo iaoa??aeao oneeaaeith?oueny ?o ianeaaoe??th ?
ei?ic??th a ?ic/eiao o?iiiai? eeneioe, a oaeiae ni?eueiei i?io?eaiiyi
?ic?yaeo ?ii?a aiaeith. Iaeiei ?c iaaaaaoueio iaoa??ae?a, ui ia
?oeiothoueny o aiaeiiio ?ic/ei? CrO3, ? cieioi. Ca aeaieie oeeee?/ii?
aieueoaiia?iiao??? ?ic?yae ieniai?ii?a Cr(VI) aei Cr(III) ia Au —
aeaeo?iae? i?ioiaeeoue i?e iioaioe?aeao a?eueo iaaaoeaieo, ai?ae
iioaioe?aee, ui a?aeiia?aeathoue a?aeiiaeaiith iiiiiieaeoey?iiai oa?o
ieneae?a cieioa, a oaeey a?aeiiaeaiiy aiaeith aeia?a a?aeie?aieth?oueny
a?ae oaee? ?ic?yaeo ?ii?a CrmO3m+12-.

I?e noaeiio ai?no? CrO3 a aeaeo?ie?o? e iaeiaeia?e oaeaeeino? neaioaaiiy
iioaioe?aeo (v) cieioiai aeaeo?iaea aaee/eia aonoeie no?oio i?ea ia AAA,
ui a?aeiia?aea? ?aaeoe?? (1) (imax), ca?eueoo?oueny i?e c?inoaii?
eiioeaio?aoe?? aeaeo?io?i?/ii iaaeoeaii? a aeaieo oiiaao n??/aii?
eeneioe (?en. 1a). Cia/aiiy imax c?inoa? oaeiae i?e ca?eueoaii?
eiioeaio?aoe?? CrO3 (i?e noaeiio ni?aa?aeiioaii? [CrO3]:[H2SO4]).
?ic?aoiaaia a i?eiouaii? oiia?eueiaii? aeeooc?? ienio?iiiaeo ?ii?a
cia/aiiy imax a?eueo i?ae ia ii?yaeie ia?aaeuo? aenia?eiaioaeueii
aecia/aio aaee/eio. Iaoee i?yieo o eii?aeeiaoao lg imax — lg v
aei??aith? (0,2 … 0,4) < 0,5. Aaaaeaiiy io?aoeii? eeneioe aei ?ic/eio CrO3 oaeiae i?eaiaeeoue aei ca?eueoaiiy oaeaeeino? aeaeo?ia?aeiiaeaiiy niieoe Cr(VI). O oeeo aeaeo?ie?oao aaee/eia imax neaaei caeaaeeoue a?ae oaeaeeino? ?icai?oee iioaioe?aeo (aeea. ?en. 1a). C io?eiaieo aeaieo aeieeaa?, ui iaeneiaeuei? no?oie ?aaeoe?? (1) ia ? noai?i aeeooc?eieie, ? noaae?? ?ic?yaeo ieniai?ii?a Cr(VI) o i?enooiino? a aeaeo?ie?o? H2SO4 aai HCOOH ia?aaeo? o?i?/ia ?aaeoe?y, a ye?e aa?ooue o/anoue cacia/ai? aeiaaaee. Oey ?aaeoe?y ? aaoa?iaaiiith, ai eaoiaeiee no?oi imax /ooeeaee aei ci?ie noaia iiaa?oi? aeaeo?iaea. Ie i?eionea?ii, ui i?e aaaaeaii? aei ?ic/eio o?iiiai? eeneioe niieoe, ui i?enei?ththoue ?ic?yae ieni?ii?a Cr(VI), ia aeaeo?iae? ooai?ththoueny ?aaeoe?eii-caeaoi? /anoee – iiaa?oiaa? eiiieaene (iie?)-o?iiao-?ii?a ? a?aeiia?aeieo aeiaaaie (A-): CrO3-–(CrO3)m-1–O- + A- + 2H+ CrO3-–(CrO3)m-1–A + 2H2O.(2) ?ieue aeiaaaie o oeeo eiiieaenao iieyaa? a ooai?aii? i?noe?a, ui iieaaoothoue ia?aiin aeaeo?ii?a, /ei ? iiynith?oueny eaoae?oe/iee aoaeo. I/aaeaeii, ui oaeee iaoai?ci ?ic?yaeo ?ii?a CrmO3m+12- iiaeiai caa??aaoeny i?e aaaaeaii? aei aeaeo?ie?oo aoaeue-yeeo aeiaaaie, ui i?enei?ththoue ?ic?yae Cr(VI). I?e oeueiio cia/aiiy imax caeaaeeoue a?ae i?e?iaee aeiaaaee-eaoae?caoi?a (oaae. 1). Oaaeeoey 1 Caeaaei?noue imax a?ae i?e?iaee aeiaaaee (1 M CrO3 + 0,3 M aeiaaaee, v = 5 iA/n) Aeiaaaeaimax * 10-2, A/i2Aeiaaaeaimax * 10-2, A/i2–0,08HNO311,46H2SO416,55HCl13,50HCOOH1,35CH3COOH0,00NaF8,15CCl3COOH0 ,01HBF43,23HClO40,15 *a?ac oa ui aeiaaaee-eaoae?caoi?e a inoaoi/iiio i?aenoieo ?aaaia?othoueny i?ney noaae?? ?ic?yaeo o?iio, oaee? a?aeiiaeaiiy CrmO3m+12- a??i?oa eeaneo?eoaaoe ye eaoae?oe/i?. Ae?enii, cia/aiiy a?aie/iiai no?oio, ?ic?aoiaai? a i?eiouaii? oiia?eueiaii? aeeooc?? eaoae?caoi?a, ia ii?yaeie iaioa aaee/ei imax, aecia/aieo aenia?eiaioaeueii. Oea icia/a?, ui noaae?y ?aaaia?aoe?? eaoae?caoi?a ia?aa?aa? aeinoaoiuei oaeaeei, ? noa? iiaeeeaei ?icaeyaeaoe oaeoe/ii eaoae?oe/io oaeeth no?oio ?aaeoe?? (1) ye oi?iaeueii e?iaoe/io, iaoiiaeaio oiia?eueiaiith iiia?aaeiueith o?i?/iith ?aaeoe??th (CE - iaoai?ci). I?e ia aeoaea aaeee?e iiey?ecaoe?? oaeaee?noue i?ioeano e?i?oo? aeaeo?io?i?/ia noaae?y, oiio ii/aoeia? ae?eyiee AAA o ?ic/eiao c aeiaaaeith H2SO4 aeia?a aei?yieythoueny a eii?aeeiaoao lg i - E, a?aee?ey ciaeaeaii na = 0,51. sseui 0,5, oi na = 1, oiaoi a aeaeo?io?i?/i?e noaae?? iia?eueiei ? ia?aiin ia?oiai aeaeo?iia. Aeey aeaeo?ie?o?a, ui i?noyoue io?aoeio eeneioo, io?eiaia cia/aiiy na = 0,28. I/aaeaey/ee, iano?eueee iii?oia a?aeoeeaiiy a?ae 0,5 ? oyaiei ? icia/a?, ui a oeueiio aeiaaeeo ii/aoeiaa ae?eyiea AAA a?aeiia?aea? ci?oaiiio ?aaeeio ?iaioe aeaeo?iaea (oaeaeeino? aeaeo?io?i?/ii? ? iaaeaeo?io?i?/ii? noaae?e noi??i?). I?e aea/aii? ?aaeoe?? (1) ia o?iiiaiio aeaeo?iae? iieacaii, ui c ?inoii eiioeaio?aoe?? H2SO4 aai HCOOH oaeaee?noue ?ic?yaeo ?ii?a CrmO3m+12- c?inoa?, oiaoi cacia/ai? aeiaaaee e o aeaiiio aeiaaeeo ? eaoae?caoi?aie a?aeiiaeaiiy o?iiiai? eeneioe. Iaiaeiaeia? oaeaeeino? a?aeiiaeaiiy iie?o?iiao-?ii?a ia Au- ? Cr- aeaeo?iaeao o cia/i?e i??? iaoiiaeai? a?aei?iiinoyie a ?oi?e aaeni?aoe?ei?e iiaaae?ioe?, a?ae?io?eueiino?, i.i.c. ? oaea ?ioa. Aeine?aeaeaiiy e?iaoeee ?ic?yaeo ?ii?a CrmO3m+12- ia Cr - aeaeo?iae? oneeaaeiaii ooai?aiiyi ie?aie ieneaeieo oa a?ae?ieneaeieo niieoe, ui aeieothoue eiai iiaa?oith. E??i oiai, ia o?iiiaiio aeaeo?iae? oaee? ?ic?yaeo ieniai?ii?a Cr(VI) ? ?ii?a aiaeith /?oei ia ?iciaaeiaai?. C i?aeaeuaiiyi eiioeaio?aoe?? H2SO4 aai HCOOH oo?oaeiy?oueny ooai?aiiy ia eaoiae? a?ae?ieniniieoe o?eaaeaioiiai o?iio, oiio ui oe? eeneioe ca'ycothoue Cr(III) o ?ic/eii? eiiieaene, a io?aoeia eeneioa, aei oiai ae, ? aooa?iith aeiaaaeith ? ia?aoeiaeaea? ?inoo pHs. O ?acoeueoao? ineaaeaiiy aeieoaaiiy aeaeo?iaea niinoa??aa?oueny ca?eueoaiiy no?oio iaiiaiiai ?ic?yaeo Cr(VI). Aeaeo?iinaaeaeaiiy o?iio c ?ic/ei?a eiai o?eaaeaioieo niieoe. Ca a?aenooiino? HCOOH aai NH2CH2COOH a aeaeo?ie?oao aai i?e iaaaeee?e ?o e?eueeino? ia ia?oe?aeueieo i,E - e?eaeo niinoa??aa?oueny iaeneioi, yeee i?e c?inoaii? eiioeaio?aoe?? oeeo i?aai?/ieo aeiaaaie ia?aoai?th?oueny ia ieiuaaeeo a?aie/iiai no?oio (ia?,Cr) (?en. 2). I?e cieaeaii? pH ? ca?eueoaii? eiioeaio?aoe?? io?aoeii? eeneioe aai ae?oeeio aeno?aeia ae?eyiea ia i,E - e?ea?e ci?uo?oueny o a?e iaaaoeaieo iioaioe?ae?a. Iaeneiaeueia aonoeia no?oio inaaeaeaiiy o?iio c?inoa? i?e ca?eueoaii? eeneioiino? oa e?eueeino? HCOOH aai NH2CH2COOH a aeaeo?ie?o?. O oe?eiio, aieea ??cieo /eiiee?a ia e?iaoeeo inaaeaeaiiy o?iio c oi?i?aoieo ? ae?oeeiaoieo ?ic/ei?a aiaeia?/iee, oiio inaaeaeaiiy iaoaeo c oeeo aeaeo?ie?o?a iiaeiii i?ioiaeeoe ii iaeiiio iaoai?cio. I?e ciaioaii? eiioeaio?aoe?? Cr(III) a aeaeo?ie?o? oa caa?aaeaii? noaei? e?eueeino? ae?oeeio aaee/eia ia?,Cr iaeaea ia ci?ith?oueny, aea aeniiiaioe?eia ae?eyiea i,E - e?eai? c?ooo?oueny a a?e iaaaoeaieo iioaioe?ae?a. sseui ae i?iii?oe?eii ciaioeoe eiioeaio?aoe?? Cr(III) ? ae?oeeio, oi ia?,Cr iii?oii cieaeo?oueny, a i?ioean ?ic?yaeo ?ii?a o?iio aei iaoaeo iieaaoo?oueny. A?aeiii, ui aeaeo?iinaaeaeaiiy o?iio c ?ic/ei?a Cr(III) i?ioiaeeoue nooi?i/anoi c ooai?aiiyi ?ioa?iaae?ao?a – niieoe Cr(II): + e- + 2e- Cr(III) Cr(II) Cr(0). (3) Ia i?aenoaa? a?aa?iao?e/ieo, aiethiiiao?e/ieo ? eoeiiiiao?e/ieo aei???a iiaoaeiaai? ia?oe?aeuei? i,E - e?ea? aeey eiaeiiai nooiaiy a eaioethc? ia?aoai?aiue (3) (?en. 3). sse aeieeaa? c io?eiaieo aeaieo, iaoaeaaee o?ii ii/eia? inaaeaeoaaoeny i?e oaeeo aeaeo?iaeieo iioaioe?aeao, eiee iaiiaia a?aeiiaeaiiy Cr(III) aei Cr(II) oaea i?ioiaeeoue ia a?aie/iiio no?oi?. ?iie aeaiaaeaioiiai o?iio iaeiie/othoueny a ia'?i? ?ic/eio ia anueiio aeine?aeaeaiiio ?ioa?aae? iioaioe?ae?a, oiaoi eeoa aeayea /anoeia aeaiaaeaioiiai o?iio a?aeiiaeth?oueny aei iaoaeo. Oaeei /eiii, iaea?eueo iia?eueiith noaae??th o eaioethc? (3) ? aeaeo?ia?aeiiaeaiiy niieoe Cr(II). Iaoee ii/aoeiaeo ae?eyiie caeaaeiinoae E,lg i aeey inaaeaeaiiy o?iio aei??aith? -0,130 A, ca?aee?ey na = 0,45, oiaoi i?e ?ic?yae? Cr(II) oiia?eueiaiei ? ia?aiin ia?oiai aeaeo?iia. I?enei?aiiy ?ic?yaeo ?ii?a o?iio aei iaoaeo i?e ca?eueoaii? pH (a cia/eoue ? pHs) na?ae/eoue i?i eaoae?oe/io ae?th ?ii?a OH- i?e a?aeiiaeaii? Cr(II). I/aaeaeii, o?ii inaaeaeo?oueny i?e ?ic?yae? a?ae?ienieiiieaen?a aeaiaaeaioiiai o?iio, ui ooai?ththoueny o i?eaeaeo?iaeiiio oa?? i?e iai?i? i?aai?/ieo e?aaiae?a (Ln) ia a?ae?ieneae-?iie o eiiieaenieo ?iiao Cr(II)L(2+n). I?e ca?eueoaii? eiioeaio?aoe?? i?aai?/iiai e?aaiaeo ??aiiaaaa ?aaeoe?? ooai?aiiy a?ae?ienieiiieaen?a Cr(II) ci?uo?oueny ae?ai, ui i?ecaiaeeoue aei aaeueioaaiiy aeaeo?iinaaeaeaiiy iaoaeo, yea niinoa??aa?oueny a aenia?eiaio?. C o?aooaaiiyi aeuaiaaaaeaiiai iiaeia i?eionoeoe ?aaeoe?eio noaio aeaeo?iinaaeaeaiiy o?iio: Cr(III)L(3+n)s + e- Cr(II)L(2+n)s (a?aie/iee no?oi),(4)Cr(II)L(2+n)s + OH- Cr(II)OH+s + Lns,(5)Cr(II)OH+s + e- Cr(I)OHs,(6)Cr(I)OHs + e- Cr(0) + OH-s.(7) Ia i?aenoaa? ?aaeoe?eii? noaie (4-7) o i?eiouaii? e?i?eii? ?cioa?ie aaeni?aoe?? Cr(II)OH+ ia aeaeo?iae?, ie iaea?aeaee e?iaoe/ia ??aiyiiy aeey ?aaeoe?? aeaeo?iinaaeaeaiiy o?iio, ui ye?nii aeia?a iieno? aieea eiioeaio?aoe?e Cr(III), i?aai?/iiai e?aaiaeo, a oaeiae pH ia oaeaee?noue aeaeo?io?i?/iiai i?ioeano. A?aecia/eii, ui ia??ai? c a?ae?ieneae-?iiaie eaoae?oe/io aeoeai?noue noiniaii inaaeaeaiiy o?iio i?iyaeythoue ? oei?eae-?iie, oiio ui aaaaeaiiy aei aeaeo?ie?oo aeiaaaee KCl iieaaoo? ?ic?yae ?ii?a o?iio aei iaoaeo. Aieea ??cieo oaeoi??a ia a?aie/iee no?oi inaaeaeaiiy aaaeei iiynieoe c iiceoe?e aeeooc?eii? e?iaoeee. Oae, aenia?eiaioe ii aeaeo?iinaaeaeaiith o?iio c oi?i?aoiiai aeaeo?ie?oo ia iaa?oiaiio oeee?iae?e/iiio aeaeo?iae? (IOeA) iieacaee, ui i?e c?inoaii? oaeaeeino? iaa?oaiiy (w) niinoa??aa?oueny aeayea ca?eueoaiiy a?aie/iiai no?oio inaaeaeaiiy o?iio. I?ioa iaoee i?yii? o eii?aeeiaoao lg ia?,Cr - lg w, ??aiee 0,33, iaioa cia/aiiy 0,7, aeanoeaiai a?aie/iei aeeooc?eiei no?oiai ia IOeA. Iaaii, a?aie/i? no?oie inaaeaeaiiy o?iio ? ?icieoeie a a?eueo-iaio oe?ieiio ?ioa?aae? iioaioe?ae?a iaeneioiaie, iia'ycaieie c aeieoaaiiyi eaoiaea a?ae?ieneaeieie niieoeaie Cr(III). C? c?inoaiiyi eaoiaeii? iiey?ecaoe?? i?aeneeththoueny a?ae?ieniooai?aiiy o i?eaeaeo?iaeiiio oa?? ? a?aeiia?aeii aeieoaaiiy aeaeo?iaeii? iiaa?oi? a?ae?ieneaeii o?iio (III). sseui aeieoaaiiy eiiiaino? i?enei?thaaeueio ae?th aeaeo?e/iiai iiey, oi ia i,E - e?ea?e aoaea oi?ioaaoeny ieiuaaeea no?oio. Oe?eaai, ui oea yaeua niinoa??aa?oueny o?eueee aeey aeaeo?ie?o?a, ui i?noyoue aeinoaoith e?euee?noue HCOOH aai NH2CH2COOH. Ca?eueoaiiy eiioeaio?aoe?? aooa?a-e?aaiaea ? cieaeaiiy pH, i/aaeaeii, iiaeiii oo?oaeithaaoe a?ae?ieniooai?aiiy ? i?eaiaeeoe aei c?inoaiiy ia?,Cr, ui ocaiaeaeo?oueny c aenia?eiaioaeueieie aeaieie. I?eaaaeaiee iaoai?ci aeaeo?iinaaeaeaiiy o?iio aeicaiey? i?iaiae?coaaoe ?ieue i?aai?/ieo aeiaaaie, ye? aaiaeyoue aei neeaaeo oeeo aeaeo?ie?o?a, ? cai?iiiioaaoe ?yae e?eoa???a ?o aeiai?o. Cie?aia, aaaeeeao ?ieue a?a? o?eae?noue eiiieaenieo niieoe i?aai?/iiai e?aaiaeo c ?iiaie Cr(II), ui ia iiaeiia aooe aeoaea aenieith, uia ia onoiooe ae?ai ??aiiaaao ?aaeoe?? ooai?aiiy a?ae?ienieiiieaen?a Cr(II). O /aoaa?oiio ?icae?e? ?icaeyiooee aieea ??cieo /eiiee?a ia oaeaee?noue inaaeaeaiiy e aeanoeaino? iie?eoue, ye? iaea?aeothoue ?c o?iiiaieeneeo aeaeo?ie?o?a ?c aeiaaaeith io?aoeii? eeneioe. Cacia/eii, ui ni?iae a yeino? aeiaaaee aeei?enoaoe a?eueo no?ee? aei ieeneaiiy i?aai?/i? eeneioe (ai?iiioeoiao, ioeoiao) ia aeicaieeee iaea?aeaoe ye?ni? iie?eooy. Aaaaeaiiy io?aoeii? eeneioe aei aeaeo?ie?oo o?iioaaiiy i?eaiaeeoue aei ci?ie oaeaeeino? aeaeo?iinaaeaeaiiy iaoaeo (oaae. 2), i?e/iio iaea?eueo? oaeaeeino? inaaeaeaiiy a?aeiia?aeathoue eiioeaio?aoe?yi 0,1 M ? 0,4 M HCOOH. Oaaeeoey 2 Aieea eiioeaio?aoe?? HCOOH ia oaeaee?noue aeaeo?iinaaeaeaiiy o?iio c aeaeo?ie?oo 1 M CrO3 + 0,05 M H2SO4; icaa = 3*103 A/i2; T = 298 K [HCOOH], M0,000,070,110,220,340,450,560,67iCr*10-2, A/i29,09,312,610,510,810,89,96,3 A ?ioa?aae? eiioeaio?aoe?e 0 M [HCOOH] 0,2 M i?e oaiia?aoo?? 288 - 303 K inaaeaeothoueny iaaeeneo/? iie?eooy. I?e [HCOOH] 0,2 M inaaee iaaoaathoue aeca?eaeueiiai aeeneo. Aeeneiooai?thth/a ae?y HCOOH iiaea aooe iia'ycaia c /anoeiaith ?oeiaoe??th eaoiaeii? ie?aee a?ae?ieneaeieo niieoe o?iio, aai c iiae??aiaiiyi (aii?o?caoe??th) no?oeoo?e iaoaeiiie?eoo?a, ui ooai?ththoueny c oi?i?aoieo aeaeo?ie?o?a. Eiioeaio?aoe?th o?iiiaiai aia?ae?eaeo a aeaeo?ie?o? ne?ae i?aeo?eioaaoe a ?ioa?aae? 0,8 - 1,2 M. I?e [CrO3] < 0,8 M ??cei cieaeo?oueny aeaeo?ii?ia?aei?noue ?ic/eio, a i?e [CrO3] > 1,2 M inaaeaeothoueny n???,
oi?noeoaao? iie?eooy, ? iii?oii i?enei?th?oueny ieeneaiiy HCOOH
o?iiiaith eeneioith.

Aa??thaaiiy eiioeaio?aoe??th H2SO4 a ?ioa?aae? 0,01 — 0,08 M iaei
a?aeaeaa?oueny ia aonoei? no?oio aeaeo?iinaaeaeaiiy o?iio. Aeyaeaii, ui
inaaeaeaiiy iie?eoo?a c aeaeo?ie?o?a, ye? i?noyoue HCOOH, iiaeeeai e o
a?aenooi?noue n??/aii? eeneioe, aea i?e oeueiio oaeaee?noue inaaeaeaiiy
iaaaeeea, ? ooai?ththoueny iaaeeneo/?, n??i-ei?e/iaa? iie?eooy.

Oaeaee?noue inaaeaeaiiy o?iio iiiioiiii i?aeaeuo?oueny i?e c?inoaii?
eaoiaeii? aonoeie no?oio. I?e ca?eueoaii? oaiia?aoo?e aeaeo?ie?oo a?ae
283 aei 303 K oaeaee?noue aeaeo?iinaaeaeaiiy iaoaeo i?aeoe/ii ia
ci?ith?oueny, a i?e i?aeaeuaii? oaiia?aoo?e aei 308 K ? a?eueoa – ??cei
cieaeo?oueny.

I?iaaaeai? aeine?aeaeaiiy aeicaieeee aecia/eoe iioeiaeueiee neeaae
aeaeo?ie?oo ? ?aaeeie aeaeo?ie?co: CrO3 – 1,0 0,2 M; H2SO4 – 0,05 ±
0,02 M; HCOOH – 0,34 0,11 M; icaa = 2,5 *103 – 1 104 A/i2; T =
280 – 300 K.

Ca?aeii c ?acoeueoaoaie ei?ic?eieo aei?iaoaaiue, ca?eueoaiiy e?eueeino?
io?aoeii? eeneioe a aeaeo?ie?o? o?iioaaiiy i?eaiaeeoue aei c?inoaiiy
ei?ic?eii? no?eeino? inaae?a (oaae. 3). I?eioeeiiai a?ae??ciy?oueny
ei?ic?eia iiaaae?iea iie?eoo?a, ui aoee io?eiai? c aeaeo?ie?o?a 1,00 M
CrO3 + 0,05 M H2SO4 (aeaeo?ie?o I) ? 1,00 M CrO3 + 0,05 M H2SO4 + 0,34 M
HCOOH (aeaeo?ie?o II), o na?aaeiaeu? 1 M HCl: ia?o? aeoeaii
?ic/eiththoueny i?e aeineoue iaaaoeaieo iioaioe?aeao oaea i?e e?iiaoi?e
oaiia?aoo??, ae?oa? – ciaoiaeyoueny i?e oeeo oiiaao o no?eeiio ianeaiiio
noai? ? naii/eiii ia aeoeaothoueny.

Oaaeeoey 3

Oaeaee?noue ei?ic?? iie?eoo?a, ui inaaeaeai? c aeaeo?ie?oo 1 M CrO3 +

+ 0,05 M H2SO4 + x M HCOOH, o 3 % NaCl i?e 323 K

x0,000,110,220,34Vei?, iea/(ni2*aiae)64,19,23,91,8

Iiey?ecaoe?eia e?eaa aiiaeiiai ?ic/eiaiiy o?iio c aeaeo?ie?oo I o 0,5 M
H2SO4 ia? eeane/iee aeaeyae: i?e aeoeaiiai ?ic/eiaiiy, ae?eyiee
ianeaiiai ? o?ainianeaiiai noaio (?en. 4, e?eaa 1). I?e aaaaeaii? aei
aeaeo?ie?oo o?iioaaiiy io?aoeii? eeneioe ia i,E — e?ea?e cieea? ae?eyiea
aeoeaiiai ?ic/eiaiiy, aacno?oiiaee iioaioe?ae c?inoa?, eaoiaeia ?
o?ainianeaia ae?eyiee ci?uothoueny o iai?yieo iiceoeaieo iioaioe?ae?a
(aeea. ?en. 4, e?eaa 2). Aiaeia?/iee aeaeyae iathoue i,E — e?ea? a 1 M
HCl. Eeoa a na?aaeiaeu? 12 M HCl ia AAA iie?eooy, ui inaaeaeaia c
aeaeo?ie?oo II, c’yaey?oueny ae?eyiea aeoeaiiai ?ic/eiaiiy.

Aieueoaiia?iiao?e/i? aeai? i?aeoaa?aeaeothoueny a?aa?iao?e/iei
aei??thaaiiyi oaeaeeino? ?ic/eiaiiy iie?eoo?a o 0,5 M H2SO4 i?e ??cieo
aeaeo?iaeieo iioaioe?aeao. Ia?oe?aeueiee no?oi aiiaeiiai ?ic/eiaiiy
o?iio, ui inaaeaeaiee c aeaeo?ie?oo I, i?e c?inoaii? E ca?eueoo?oueny,
aeinyaa? iaeneiaeueiiai cia/aiiy, a iio?i cieaeo?oueny. ?ic/eiaiiy
iie?eoo?a c aeaeo?ie?oo II iiiioiiii niia?eueith?oueny i?e i?aeaeuaii?
aeaeo?iaeiiai iioaioe?aeo.

?ai?oa anoaiiaeaii, ui o?iiia? inaaee, iaea?aeoaai? c aeaeo?ie?o?a ?c
aeiaaaeith HCOOH, a?aecia/athoueny aii?oiith no?oeoo?ith (ia a?aei?io
a?ae e?enoae?/ieo iie?eoo?a c aeaeo?ie?o?a o?iioaaiiy aac i?aai?/ieo
aeiaaaie). A?aeiii, ui aii?oi? iaoaee e nieaae /anoi iathoue aenieo
no?ee?noue aei ei?ic??. Iaeiae i?ney oa?iiia?iaee ii/aoeiai aii?oieo
iie?eoo?a, io?eiaieo c aeaeo?ie?oo II, ?oiy no?oeoo?a noa?
e?enoae?/iith, aea aeaeyae aiiaeieo i,E — e?eaeo ye?nii ia ci?ith?oueny
– i?e aeoeaiiai ?ic/eiaiiy ia ieo ia c’yaey?oueny. Oiio aiiiaeueia
aiiaeia iiaaae?iea o?iiiaeo iie?eoo?a, ui inaaeaeothoueny c aeaeo?ie?oo
II, ca’ycaia ia no?eueee c aii?oi?noth ?oiuei? no?oeoo?e, ne?eueee c
aeeth/aiiyi aoaeaoeth aei ?o neeaaeo. Aeaea?aeii aoaeaoeth a iie?eoo? ?
io?aoeia eeneioa, ? oiio ci?ithaaiiy ?? eiioeaio?aoe?? a aeaeo?ie?o?
o?iioaaiiy aieeaa? ia ei?ic?eii-aeaeo?io?i?/i? aeanoeaino? inaae?a. Oae,
i?e c?inoaii? e?eueeino? HCOOH a aeaeo?ie?o? niinoa??aa?oueny cieaeaiiy
e?eoe/ii? aonoeie no?oio ianeaaoe?? (aae aei iiaiiai cieeiaiiy ae?eyiee
aeoeaiiai ?ic/eiaiiy), a oaeiae ca?eueoo?oueny cia/aiiy aacno?oiiaiai
iioaioe?aeo ia AAA (?en. 5).

Iaaii, oiane?aeie naeaeoeaiiai ?ic/eiaiiy a?eueo aeoeaiiai eiiiiiaioa
(iaoaeo) ia iiaa?oi? aeine?aeaeoaaieo iie?eoue ooai?th?oueny ianeaoth/a
ie?aea, yea caaaa/aia aoaeaoeai aai eiai niieoeaie ? oiio ia? aenieo
no?ee?noue aei ei?ic?? oa aiiaeiiai ?ic/eiaiiy a aa?aneaieo
na?aaeiaeuao. Ia ei?enoue oeueiai i?eiouaiiy na?ae/eoue ianooiia.

1) O 12 M HCl inaae c aeaeo?ie?oo II ianeao?oueny i?e a?eueo iaaaoeaiiio
iioaioe?ae? (i?eaeecii ia 400 iA), i?ae iie?eooy c aeaeo?ie?oo I, ui
aiai?eoue i?i i?eioeeiiao a?aei?ii?noue neeaaeo ? aeanoeainoae
ianeaoth/eo ie?aie ia oeeo inaaeao.

2) Ca/euaiiy iiaa?oi? o?ii-aoaeaoeaaiai inaaeo aa?aceaii i?ae oa?ii
aeaeo?ie?oo (1 M HCl, 4 M HCl) i?ecaiaeeoue aei naii?ic/eiaiiy iaoaeo oa
cnoao ei?ic?eiiai iioaioe?aeo a iaaaoeaio noi?iio. Aei oiai ae
?acoeueoaoo aaaea i?aeaeuaiiy oaiia?aoo?e ?ic/ei?a nieyii? eeneioe.

3) Iaoiaeii ?AN iieacaia (Joshi A., Kulkarni S.K.) iayai?noue o
iiaa?oiaaiio oa?? inaae?a, io?eiaieo ?c o?iiiaieeneiai aeaeo?ie?oo c
aeiaaaeith HCOOH, iii?oii? e?eueeino? aoaeaoeth o oi?i? a?ao?oo ? -COOH,
a oaeiae aeneiaeaii i?eiouaiiy i?i oa, ui aoaeaoeue a ia’?iieo oa?ao
oeeo iie?eoue i?enooi?e o oi?i? aii?oiiai ea?a?aeo o?iio.

4) A?aeiii, ui aoaeaoeue ? iaoa??aee, ui i?noyoue aoaeaoeue (na?aae ieo
ea?a?aee o?iio), a?aecia/athoueny aenieith ei?ic?eiith no?ee?noth ?
iaaaeeeith oaeaee?noth aiiaeiiai ?ic/eiaiiy.

Aeine?aeaeai? iie?eooy a?ae??ciythoueny a?ae «cae/aeieo» o?iiiaeo ia
o?eueee aenieith ei?ic?eiith no?ee?noth, aea ? ieceith ?ioeo oe?iieo
aeanoeainoae, iai?eeeaae, c?inoaiiyi ?oiuei? i?e?ioaa?aeino? a 1,5 — 2
?ace i?ney oa?iiia?iaee i?e 573 — 773 K. Caaaeyee iano?eueee
oi?eaeueiiio eiiieaeno o?ceei-o?i?/ieo ? iaoai?/ieo aeanoeainoae
aaeueaaiiiie?eooy, ui inaaeaeothoueny c aeaeo?ie?o?a o?iioaaiiy c
aeiaaaeith io?aoeii? eeneioe, iiaeooue ciaeoe oe?iea canoinoaaiiy o
no/ani?e i?iieneiaino?.

Iniiai? aeniiaee

1. Aiae?c aenia?eiaioaeueieo aeaieo ii aieeao ??cieo i?aai?/ieo ?
iai?aai?/ieo niieoe ia iaiiaia aeaeo?ia?aeiiaeaiiy ieniai?ii?a Cr(VI)
aeicaieea aeyaeoe, ui noaae?? ia?aiino ia?oiai aeaeo?iia ia?aaeo?
aaoa?iaaiia o?i?/ia ?aaeoe?y aca?iiae?? ieniai?ii?a Cr(VI) ? aeiaaaie,
ui i?enei?ththoue oeae aeaeo?iaeiee i?ioean.

2. O ?acoeueoao? aea/aiiy aieeao io?aoeii? eeneioe ia e?iaoeeo iaiiaiiai
aeaeo?ia?aeiiaeaiiy o?iiiai? eeneioe iieacaii, ui io?aoeia eeneioa
iaeaaeeoue aei niieoe, o i?enooiino? yeeo i?enei?th?oueny ?ic?yae
ieniai?ii?a Cr(VI), a oaeiae ia?aoeiaeaea? a?ae?ieniooai?aiith o
i?eaeaeo?iaeiiio oa??.

3. Ia i?aenoaa? nenoaiaoe/iiai aea/aiiy e?iaoeee ?ic?yaeo oi?i?aoieo oa
ae?oeeiaoieo eiiieaen?a Cr(III) i?aeoaa?aeaeaii, ui oeae i?ioean
i?io?ea? noaae?eii. Iaea?eueo iia?eueiith ? noaae?y i?e?aeiaiiy
aeaeo?iia aei ?ioa?iaae?ao?a – eiiieaen?a Cr(II). I?e ?ic?yae? ?ii?a
Cr(II) eaoae?oe/io aeoeai?noue aeyaeythoue a?ae?ieneae- oa oei?eae-?iie.
Aeieoaaiiy iiaa?oi? aeaeo?iaea iaei?ic/eiieie a?ae?ieneaeieie niieoeaie
Cr(III) o ?yae? aeiaaee?a i?eaiaeeoue aei iiyae iaaeeooc?eieo a?aie/ieo
no?oi?a inaaeaeaiiy o?iio.

4. Io?aoeia e ai?iiioeoiaa eeneioe, ye? aaiaeyoue aei aeaeo?ie?o?a
o?iioaaiiy ia iniia? Cr(III), ca’ycothoue ?iie Cr(III) oa Cr(II) o
eiiieaeni? niieoee, ia?aoeiaeaeathoue a?ae?ieniooai?aiith ia eaoiae? ?
oaeei /eiii a?athoue iiaea?eio ?ieue: aaeueiothoue inaaeaeaiiy iaoaeo ia
ii/aoeia?e ae?eyioe? ia?oe?aeueii? i,E — e?eai? oa i?eaiaeyoue aei
c?inoaiiy iaeneiaeueii? aonoeie no?oio.

5. C aeaeo?ie?o?a o?iioaaiiy c aeiaaaeith io?aoeii? eeneioe
inaaeaeothoueny aii?oi? iie?eooy c aiiiaeueii aenieith no?ee?noth aei
ei?ic?? oa aiiaeiiai ?ic/eiaiiy. I?e/eiith oaeiai aoaeoo ? ooai?aiiy ia
iiaa?oi? iie?eooy ianeaoth/i? ie?aee c aenieeie caoenieie aeanoeainoyie.

6. Ia i?aenoaa? ?acoeueoao?a aeine?aeaeaiiy e?iaoeee ? iaoai?cio
aeaeo?ia?aeiiaeaiiy niieoe, ui i?noyoue o?ii, o i?enooiino? i?aai?/ieo
aeiaaaie aei aeaeo?ie?o?a o?iioaaiiy ia iniia? nieae Cr(III)
?aeiiaiaeiaaii aaiaeeoe i?aai?/i? aeiaaaee-e?aaiaee, ui ooai?ththoue
o?eae? eiiieaene c Cr(III) ? ia aeoaea noaa?euei? eiiieaene c Cr(II).
Aeey iaea?aeaiiy aeeneo/eo iie?eoo?a ?c aenieith no?ee?noth aei ei?ic??
o eeneeo na?aaeiaeuao ?aeiiaiaeiaaii aeei?enoiaoaaoe aeaeo?ie?o
neeaaeo: CrO3 – 1,0 0,2 M; H2SO4 – 0,05 ± 0,02 M; HCOOH – 0,34
0,11 M; ?aaeei aeaeo?ie?co: icaa = 2,5 *103 – 1 104 A/i2; T = 280 –
300 K.

INIIAIEE CI?NO AeENA?OAOe?? AEEEAAeAII O ?IAIOAO:

1. Ei??iceiiii-yeaeo?ioeie/aneia iiaaaeaiea iie?uoee, inaaeaeaaiuo ec
o?iiiaieeneiai yeaeo?ieeoa n aeiaaaeie io?aaueeiie eeneiou / O.E.
Aeaieeia, A.?. Iiiia, A.N. Ao?ueeia, A.N. I?ioeaiei // Yeaeo?ioeiey. —
1997. — O. 33. — ? 5. — N. 543 — 547.

2. Aeaieeia O.E., I?ioeaiei A.N. Yeaeo?iainnoaiiaeaiea niaaeeiaiee
oanoeaaeaioiiai o?iia ia cieioii yeaeo?iaea // Yeaeo?ioeiey. — 1998. —
O. 34. — ? 3. — N. 301 — 306.

3. Aeaieeia O.E., I?ioeaiei A.N. Aeeyiea io?aaueeiie eeneiou ia
yeaeo?iainnoaiiaeaiea niaaeeiaiee oanoeaaeaioiiai o?iia // Yeaeo?ioeiey.
— 1998. — O. 34. — ? 6. — N. 641 — 644.

4. I?ioeaiei A.N., Ainoioeeay ss.E., Iiiia A.?. Yeaeo?iinaaeaeaiea
o?iia ec yeaeo?ieeoa ia iniiaa Cr(III) ia a?auathuainy oeeeeiae?e/aneii
yeaeo?iaea // Aii?. oeiee e oei. oaoiieiaee. — 1998. — ? 1. — N. 23 —
24.

5. Io?aaueeiay eeneioa a ea/anoaa aeiaaaee e o?iiiaieeneui yeaeo?ieeoai.
I. Yeaeo?iinaaeaeaiea o?iia / O.E. Aeaieeia, A.?. Iiiia, A.N. I?ioeaiei,
A.N. Ao?ueeia, N.A. ?iiaiaiei // Oe?. ain. oei. — oaoiie. oi-o. —
Aeiai?iiao?iane, 1996. — 18 n. — ?on. — Aeai. a AIOA Oe?aeiu 24.10.96. ?
2092-Oe96.

6. Aeaieeia O.E., I?ioeaiei A.N., A?aiaiei A.A. Io?aaueeiay eeneioa a
ea/anoaa aeiaaaee e o?iiiaieeneui yeaeo?ieeoai. II. Eeiaoeea
ieeneeoaeueii-ainnoaiiaeoaeueiiai acaeiiaeaenoaey Cr(VI) e HCOOH // Oe?.
ain. oei. — oaoiie. oi-o. — Aeiai?iiao?iane, 1996. — 21 n. — ?on. —
Aeai. a AIOA Oe?aeiu 24.10.96. ? 2090-Oe96.

7. Ei?ic?eia iiaaae?iea ?aioaaiiaii?oieo iie?eoo?a o?iiii oa eiai
nieaaaie / O.E. Aeai?eia, ?.?. Iiiia, ?.I. Ca?y, A.N. I?ioeaiei //
Iaoa??aee i?aei. eiio.-aenoaaee «I?iaeaie ei?ic?? oa i?ioeei?ic?eiiai
caoenoo eiino?oeoe?eieo iaoa??ae?a» (Ei?ic?y — 94). — Euea?a:
O?ceei-iaoai?/iee ?inoeooo ?i. A.A. Ea?iaiea IAI Oe?a?ie. — 3 — 7
aeiaoiy 1994. — N. 138.

8. Popov E., Protsenko V., Danilov F. Corrosion resistant X-ray
amorphous coatings // Abstr. of the Ist central, eastern and northern
Europe regional conference on surface treatment: technologies,
environmental and standardization. — Palanga. — 4 — 8 of September
1995. — P. 41.

9. Aeaieeia O.E., Iiiia A.?., I?ioeaiei A.N. Caueoiua aaeueaaie/aneea
?aioaaiiaii?oiua iie?uoey // Iaoa?eaeu VI Iaaeaeoia?. iao/ii-oaoi. eiio.
«Iiaua eiino?oeoeeiiiua noaee e nieaau e iaoiaeu eo ia?aaioee aeey
iiauoaiey iaaeaaeiinoe e aeieaiaa/iinoe ecaeaeee». — *anoue 3. —
Caii?iaeuea: CAOO. — 27 — 29 naioya?y 1995. — N. 136 — 137.

10. Aeaieeia O.E., Iiiia A.?., I?ioeaiei A.N. Aeeyiea oa?iiia?aaioee ia
no?oeoo?o, iee?ioaa?aeinoue e ei??iceiiii-yeaeo?ioeie/aneea naienoaa
aaeueaaiiiie?uoee, inaaeaeaaiuo ec o?iiiaieeneiai yeaeo?ieeoa n
aeiaaaeie io?aaueeiie eeneiou // Iaoa?eaeu III Iaaeae. eiio. — aunoaaee
«I?iaeaiu ei??icee e i?ioeaiei??iceiiiie caueou eiino?oeoeeiiiuo
iaoa?eaeia» (Ei??icey — 96). — Eueaia: Oeceei-iaoaie/aneee einoeooo ei.
A. A. Ea?iaiei IAI Oe?aeiu. — 28 — 30 iay 1996. — N. 131 — 133.

11. Danilov F.I., Popov E.R., Protsenko V.S. Corrosion and
electrochemical behavior of X-ray amorphous chromium coatings // Abstr.
of the 47th Meeting of the International Society of Electrochemistry. —
Veszprem — Balatonfured, Hungary. — 1 — 6 of September 1996. — P6c-8.

12. Yeieiaecaoeey aaeueaaiioeie/aneeo oaoiieiaee ia iniiaa oiene/iuo
o?iiiauo yeaeo?ieeoia / O.E. Aeaieeia, A.A. Enaaieia, A.?. Iiiia, A.N.
I?ioeaiei, E.A. Oea/aiei // Iaoa?eaeu IV Iaaeae. Eiio. «O?aioeey e
Oe?aeia, iao/ii-i?aeoe/aneee iiuo a eiioaenoa aeeaeiaa iaoeeiiaeueiuo
eoeueoo?». — Aeiai?iiao?iane: «Iieea?aoeno». — 1997. — O. II. — *anoue
II. — N. 91 — 93.

13. No?oeoo?a e ei??iceiiiia iiaaaeaiea o?iiiauo e
oeeie-ia?aaioeaauo aaeueaaiiiie?uoee / O.E. Aeaieeia, A.?. Iiiia, A.N.
I?ioeaiei, Ae.A. Nooiieei, A.A. Aa?aneiia // Iaoa?eaeu IV Iaaeae. eiio.
— aunoaaee «I?iaeaiu ei??icee e i?ioeaiei??iceiiiie caueou» (Ei??icey —
98). — Eueaia: Oeceei-iaoaie/aneee einoeooo ei. A. A. Ea?iaiei IAI
Oe?aeiu. — 9 — 11 ethiy 1998. — N. 212 — 214.

AIIOAOe?ss

I?ioeaiei A.N. Aeaeo?ia?aeiiaeaiiy niieoe, ui i?noyoue o?ii, o
i?enooiino? io?aoeii? oa ai?iiioeoiai? eeneio. — ?oeiien.

Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa o?i?/ieo iaoe ca
niaoe?aeuei?noth 02.00.05 — aeaeo?io?i?y. — Oe?a?inueeee aea?aeaaiee
o?i?ei-oaoiieia?/iee oi?aa?neoao, Aei?i?iiao?ianuee, 1999.

Aeine?aeaeaii e?iaoeeo aeaeo?ia?aeiiaeaiiy niieoe Cr(VI) ? Cr(III), a
oaeiae aieea io?aoeii? oa ai?iiioeoiai? eeneio ia oe? i?ioeane ? ia
aeanoeaino? iie?eoo?a. ?icaeyiooi ?ieue aeiaaaie, ui i?enei?ththoue
aeaeo?ia?aeiiaeaiiy Cr(VI), o iaoai?ci? aeaeo?iaeiiai i?ioeano.
Cai?iiiiiaaii iaoai?ci inaaeaeaiiy o?iio c aeaeo?ie?o?a ia iniia?
Cr(III). Aeine?aeaeaii ei?ic?eii-aeaeo?io?i?/io iiaaae?ieo iie?eoo?a ?c
aeaeo?ie?o?a o?iioaaiiy, ui i?noyoue io?aoeio eeneioo.

Eeth/ia? neiaa: o?ii, aeaeo?ia?aeiiaeaiiy, aeaeo?iinaaeaeaiiy, iie?eooy,
io?aoeia eeneioa, ai?iiioeoiaa eeneioa.

AIIIOAOeEss

I?ioeaiei A.N. Yeaeo?iainnoaiiaeaiea o?iiniaea?aeaueo niaaeeiaiee a
i?enoonoaee io?aaueeiie e aieiioenoniie eeneio. — ?oeiienue.

Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa oeie/aneeo iaoe ii
niaoeeaeueiinoe 02.00.05 — yeaeo?ioeiey. — Oe?aeineee ainoaea?noaaiiue
oeieei-oaoiieiae/aneee oieaa?neoao, Aeiai?iiao?iane, 1999.

Enneaaeiaaia eeiaoeea yeaeo?iainnoaiiaeaiey niaaeeiaiee Cr(VI) e
Cr(III), a oaeaea aeeyiea io?aaueeiie e aieiioenoniie eeneio ia yoe
i?ioeannu e naienoaa ia?acothueony iie?uoee.

Ia iniiaaiee eco/aiey iaiieiiai yeaeo?iainnoaiiaeaiey o?iiiaie eeneiou
ia cieioii e o?iiiaii yeaeo?iaeao onoaiiaeaii, /oi noaaeee ia?aiina
ia?aiai yeaeo?iia i?aaeoanoaoao aaoa?iaaiiay oeie/aneay ?aaeoeey
acaeiiaeaenoaey ieniaieiiia Cr(VI) e aeiaaaie, onei?ythueo aeaiiue
yeaeo?iaeiue i?ioeann. Eaoaeeoe/aneee yooaeo aeiaaaie iauyniyaony
«iinoeeiaui» iaoaieciii ia?aiina ca?yaea. Io?aaueeiay eeneioa
i?eiaaeeaaeeo e /eneo niaaeeiaiee, a i?enoonoaee eioi?uo onei?yaony
?ac?yae ieniaieiiia Cr(VI), a oaeaea i?aiyonoaoao aeae?ieniia?aciaaieth
a i?eyeaeo?iaeiii neia.

Yeaeo?iinaaeaeaiea o?iia ec yeaeo?ieeoia ia iniiaa Cr(III) i?ioaeaao
noaaeeeii, i?e/ai iaeaieaa iaaeeaiiie yaeyaony noaaeey i?eniaaeeiaiey
yeaeo?iia e eioa?iaaeeaoai – eiiieaenai Cr(II). Aeae?ieneae- e
oei?eae-eiiu i?iyaeytho eaoaeeoe/aneoth aeoeaiinoue ii ioiioaieth e
?aaeoeee yeaeo?iinaaeaeaiey o?iia. Aeiee?iaaiea yeaeo?iaeiie iiaa?oiinoe
iaei?anoai?eiuie aeae?ieneaeiuie niaaeeiaieyie Cr(III) iiaeao
i?eaiaeeoue e iiyaeaieth iaaeeoooceiiiuo i?aaeaeueiuo oieia inaaeaeaiey
o?iia. I?aaeeiaeaiiue a ?aaioa iaoaieci ?ac?yaea eiiieaeniuo eiiia
Cr(III) iicaieyao ?ane?uoue ?ieue i?aaie/aneeo eeaaiaeia, eniieuecoaiuo
a yeaeo?ieeoao o?iie?iaaiey. A yeaeo?ieeou o?iie?iaaiey ia iniiaa
Cr(III) ?aeiiaiaeiaaii aaiaeeoue i?aaie/aneea aeiaaaee-eeaaiaeu,
ia?acothuea i?i/iua eiiieaenu n Cr(III) e ia i/aiue noaaeeueiua
eiiieaenu n Cr(II).

Enneaaeiaaii aeeyiea ?acee/iuo oaeoi?ia ia nei?inoue inaaeaeaiey iaoaeea
e aiaoiee aeae iie?uoee ec oi?ieaoniaea?aeauaai o?iiiaieeneiai
yeaeo?ieeoa, ii?aaeaeaiu iioeiaeueiua ninoaa yeaeo?ieeoa e ?aaeeiu
yeaeo?ieeca: CrO3 – 1,0 0,2 M; H2SO4 – 0,05 ± 0,02 M; HCOOH – 0,34
0,11 M; iiau = 2,5 *103 – 1 104 A/i2; T = 280 – 300 K.

Ec o?iiiaieeneuo yeaeo?ieeoia n aeiaaaeie io?aaueeiie eeneiou
inaaeaeathony aeanoyuea aii?oiua iie?uoey n iniaui
ei??iceiiii-yeaeo?ioeie/aneei iiaaaeaieai. Oae, a eeneuo ?anoai?ao (0,5
M H2SO4) ia aiiaeiuo i,E — e?eauo yoeo inaaeeia ionoonoaoao iaeanoue
aeoeaiiai ?anoai?aiey iaoaeea. Yoa iniaaiiinoue aiiaeiiai iiaaaeaiey
nio?aiyaony iinea oa?iiia?aaioee iie?uoee, i?eaiaeyuae e eo
e?enoaeeecaoeee. I?e/eiie iaaethaeaaiuo yooaeoia yaeyaony ia?aciaaiea ia
iiaa?oiinoe iie?uoey ianneae?othuae ieaiee, iaiaauaiiie oaea?iaeii eee
oaea?iaeniaea?aeaueie niaaeeiaieyie. Enoi/ieeii oaea?iaea a iie?uoee
yaeyaony io?aaueeiay eeneioa, e iiyoiio eciaiaiea aa eiioeaio?aoeee a
yeaeo?ieeoa o?iie?iaaiey ei??aee?oao n ei??iceiiii-yeaeo?ioeie/aneeie
oa?aeoa?enoeeaie inaaeeia.

Eeth/aaua neiaa: o?ii, yeaeo?iainnoaiiaeaiea, yeaeo?iinaaeaeaiea,
iie?uoea, io?aaueeiay eeneioa, aieiioenoniay eeneioa.

SUMMARY

Protsenko V.S. Electroreduction of compounds containing chromium in the
presence of formic and aminoacetic acids. — Manuscript.

Dissertation for the degree of the candidate of chemical sciences on
speciality 02.00.05 — electrochemistry. — Ukrainian State Chemical
Technology University, Dniepropetrovsk, 1999.

The kinetics of electroreduction of compounds Cr(VI) and Cr(III), also
the effect of formic and aminoacetic acids on these processes and on the
properties of coatings were investigated. The role of the additives
accelerating electroreduction Cr(VI) in the mechanism of electrode
process was surveyed. The mechanism of the chromium deposition from
electrolytes on a basis Cr(III) has been offered. The corrosion and
electrochemical behaviour of coatings deposited from electrolytes
containing formic acid was investigated.

Key words: chromium, electroreduction, electrodeposition, coating,
formic acid, aminoacetic acid.

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