OA?E?ANUeEEE AeA?AEAAIEE OI?AA?NEOAO
Ia i?aaao ?oeiieno
Iane?e Ieueaa A?eai??aia
OAeE 543.252.1
AIEEA ?IIIEO EIIIIIAIO?A IAO?EOe?
IA AIAE?OE*IEE NEAIAE IIOAIOe?IIAO???
C AI?IINAEAEOEAIEIE AEAEO?IAeAIE
02.00.02 —aiae?oe/ia o?i?y
AAOI?AOA?AO
aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy
eaiaeeaeaoa o?i?/ieo iaoe
Oa?e?a —1999
Aeena?oaoe??th ? ?oeiien
?iaioo aeeiiaii a Oa?e?anueeiio aea?aeaaiiio oi?aa?neoao?
Iaoeiaee ea??aiee eaiaeeaeao o?i?/ieo iaoe, aeioeaio
Eia?iiaa E?ae?y Iaae?aia
Oa?e?anueeee aea?aeaaiee oi?aa?neoao,
aeioeaio eaoaae?e o?i?/ii? iao?ieia??
Io?oe?ei? iiiiaioe: aeieoi? o?i?/ieo iaoe, i?ioani?
*i?eaiei Oaae?? Ieaenaiae?iae/,
caa?aeoaa/ eaoaae?e aiae?oe/ii? o?i??
Aei?i?iiao?ianueeiai aea?aeoi?aa?neoaoo;
eaiaeeaeao o?i?/ieo iaoe, aeioeaio
Ca?a/ainueeee Ieoaeei Aiaoie?eiae/,
aeioeaio eaoaae?e aiae?oe/ii? o?i??
Oe?a?inueei? oa?iaoeaaoe/ii? aeaaeai??
(i. Oa?e?a)
I?ia?aeia onoaiiaa O?ceei-o?i?/iee ?inoeooo ?i. I.A.Aiaaonueeiai IAI
Oe?a?ie, a?aeae?e aiae?oe/ii? o?i?? ? o?ceei-o?i?? eii?aeeiaoe?eieo
niieoe (i. Iaeana)
Caoeno a?aeaoaeaoueny “ 10 ”aa?aniy 1999 ?. i 1600 aiaeei? ia can?aeaii?
niaoe?ae?ciaaii? a/aii? ?aaee Ae 64.051.14 a Oa?e?anueeiio aea?aeaaiiio
oi?aa?neoao? (Oe?a?ia, 310077, i.Oa?e?a, ie. Naiaiaee, 4, aoae. 7-80)
C aeena?oaoe??th iiaeia iciaeiieoeny a Oeaio?aeuei?e iaoeia?e
a?ae?ioaoe? Oa?e?anueeiai aea?aeaaiiai oi?aa?neoaoo
Aaoi?aoa?ao ?ic?neaiee ”05” eeiiy 1999 ?.
A/aiee nae?aoa? niaoe?ae?ciaaii?
a/aii? ?aaee Eia?iiaa E.I.
CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE
Aeooaeuei?noue oaie. ?icaeoie iioaioe?iiao??? a inoaii? o?e aeanyoee?ooy
coiiaeaiee noai?aiiyi oa canoinoaaiiyi aeaeo?io?i?/ieo naini??a –
?iiinaeaeoeaieo aeaeo?iae?a (?NA) c ??aeeiieie oa oaa?aeioacieie
iaia?aiaie, a?aeaoe yeeo caeaaeeoue a?ae aeoeaii? /e ??aiiaaaeii?
eiioeaio?aoe?? eiie?aoii? ?iiii? oi?ie. Iniaeeai aaaeeeaith noaea iiyaa
ai?iinaeaeoeaieo aeaeo?iae?a, ai naia i?e aiae?c? ai?ii?a iaiao?aeii
?ic??ciyoe ?iii? oi?ie, ooai?ai? iaeiei ? oei aea aeaiaioii.
I?e aei??thaaiiyo c ?NA aeieeathoue iaai? iaiaaeaiiy, iia’ycai? c
aieeaii ia aiae?oe/iee neaiae ?NA ?ioeo eiiiiiaio?a ia’?eoo aiae?co –
oae caaieo iao?e/ieo.
Ii/eiath/e c 1966 ?ieo, eiee iiyaa eaeueoe?e- oa ooi?eaenaeaeoeaiiai
aeaeo?iae?a caii/aoeoaaea ?icaeoie ?iiiiao???, ia?aaaaeia a?eueo?noue
aeine?aeaeaiue a oe?e aaeoc? aoea iia’ycaia c ?ic?iaeith iiaeo oa
aaeineiiaeaiiyi a?aeiieo oei?a naini??a. Aeooaeueiei aeey ?icoe?aiiy
i?eeeaaeieo iiaeeeainoae naini??a ? ?icaeoie iaoiaeieia?? aei??thaaiue ?
?ic?iaea iaoiaeee, ui aacothoueny ia o?i?/iiio /e ?ic?aooieiaiio
niiniaao onoiaiiy iao?e/ieo aoaeo?a. Aeey oeueiai iaiao?aei? e?euee?ni?
oa?aeoa?enoeee caaaae, ui aeieeathoue i?e ?iaio? c ?NA.
Ca’ycie ?iaioe c iaoeiaeie i?ia?aiaie, ieaiaie, oaiaie. Aeena?oaoe?eio
?iaioo aeeiiaii a?aeiia?aeii iaoeiai-aeine?aei?e oaiaoeoe? eaoaae?e
o?i?/ii? iao?ieia?? OAeO, ye neeaaeiao /anoeo aeine?aeaeaiue ca
?icae?eii IOI AeEII N?N? “Nicaeaiea n?aaenoa iao?ieiae/aneiai
iaania/aiey iiiaioeaeaaiai eniieueciaaiey, aeeth/athueo noaiaea?oiua
ia?acoeu aauanoa, iao?ieiae/aneeo yeaeaaeaioia e o. i., ea?aeeiaeueii
oeo/oathueo iao?ieiae/aneia iaania/aiea i?e auionea e eniieueciaaiee
aiaeeoe/aneie oaoieee e iaoiaeee aiaeeca” (iaeac AeEII ? 454 a?ae
02.07.90), oa IAe? “O?ceei-o?i?/i? canaaee ooieoe?iioaaiiy cania?a
aei??thaaiiy ia iniia? ?iiiiai?iieo iaoa??ae?a” i?aeaoc?anueei? iaoeiai?
i?ia?aie Oe?a?ie “Aeinoaiaea?oecaoe?ei? aeine?aeaeaiiy iiaeo iaoiae?a oa
cania?a iao?ieia?/iiai caaacia/aiiy aei?iaoaaiue ? eiio?ieth
o?ceei-iaoai?/ieo ? o?i?/ieo aeanoeainoae no/anieo iaoa??ae?a oa
ae?aaiinoeee ae?ia?a ? neeaaeieo nenoai c ?o canoinoaaiiyi” (1996-1999
?iee).
Iaoa aeine?aeaeaiiy —e?euee?niee iien oaeoi??a, ui aieeaathoue ia
aiae?oe/iee neaiae iioaioe?iiao??? c ai?iinaeaeoeaieie aeaeo?iaeaie, ?
noai?aiiy iao?ieia?/ieo canaae iioaioe?iiao?e/iiai aecia/aiiy ai?ii?a
(i?o?aoo, ia?oei?aoo, oao?aooi?iai?aoo, aeiaeaoeeenoeueoaoo oa ?i.).
Aeey aeinyaiaiiy iaoe ne?ae aoei ?ica’ycaoe ianooii? caaea/?:
aeine?aeeoe ??ci? oeie aoaeo?a iao?eoe? i?e aei??thaaiiyo c
ai?iinaeaeoeaieie aeaeo?iaeaie na??eiiai aeioneo ia iniia?
ieanoeo?eiaaieo iaia?ai (ci?ithaaiiy eiao?oe??io?a aeoeaiino?
iioaioe?aeooai?thth/iai ?iio oa aeeooc?eiiai iioaioe?aeo; ?iiiiai?iia
eiieo?aioe?y; ci?ia o?i?/ii? oi?ie iioaioe?aeooai?thth/iai ?iia);
?ic?iaeoe ?aeiiaiaeaoe?? aeey onoiaiiy iioeaie, coiiaeaieo ci?iith
o?i?/ii? oi?ie iioaioe?aeooai?thth/iai ai?iia (a?ae?ie?c
oao?aooi?iai?aoo, aa?aaaoe?y aeiaeaoeeenoeueoaoo (DS-), eiieo?oth/?
?aaeoe?? eiiieaeniooai?aiiy aeey HgI3-) i?e a?aaeothaaii? oa aiae?c?;
noai?eoe iiaeae? a?aeaoeo ai?iinaeaeoeaieo aeaeo?iae?a, i?eaeaoi? aeey
anueiai ae?aiaciio eiioeaio?aoe?e iioaioe?aeooai?thth/iai ?iia;
iaea?aeaoe iiaeae? eiao?oe??io?a aeoeaiino? ai?ii?a ??cii? i?e?iaee
(i?o?ao, ia?oei?ao, oao?aooi?iai?ao, aeiaeaoeeenoeueoao) o ?ic/eiao
iaeiiai oa aeaio aeaeo?ie?o?a;
iioei?coaaoe oiiae aecia/aiiy eiao?oe??io?a naeaeoeaiino? oa anoaiiaeoe
iiaeeea?noue ?o aeei?enoaiiy ye noaei? oa?aeoa?enoeee iaia?aiieo
aeaeo?iae?a aeey a?aoiaaiiy aieeao ?iiiiai?iii? eiieo?aioe??;
ioa?aeoa?ecoaaoe iiaeeeaino? iaeii/aniiai aecia/aiiy aeaio eiiiiiaio?a
ca aeiiiiiaith nenoaie ?NA, aiae?oe/i? neaiaee yeeo ia?ae?eaathoueny;
?ic?iaeoe iaoiaeeee iioaioe?iiao?e/iiai aecia/aiiy ai?ii?a c oeiiaeie
ai?iinaeaeoeaieie aeaeo?iaeaie, ui aacothoueny ia ?ic?aooieiaiio niinia?
onoiaiiy iao?e/ieo aoaeo?a.
Iaoeiaa iiaecia iaea?aeaieo ?acoeueoao?a:
Aia?oa iaea?aeaii ??aiyiiy, ui iienothoue aieea ?iiiiai na?aaeiaeua ia
a?aeaoe ai?iinaeaeoeaiiai aeaeo?iaea a oe?ieiio ae?aiacii?
eiioeaio?aoe?e iioaioe?aeooai?thth/iai ai?iia (i?o?ao-, ia?oei?ao-,
oao?aooi?iai?ao-ai?iie).
Aecia/aii eiao?oe??ioe aeoeaiino? ai?ii?a NO3-, ClO4-, BF4-, ? DS-, ye?
iaiiaeeeai ioe?ithaaoe ia iniia? a?ae?aoaoe?eii? oai???; aeey ai?ii?a
BF4- ? DS- – aia?oa. Iaea?aeai? aii??e/i? iiaeae? aeicaieythoue
ia/enethaaoe eiao?oe??ioe aeoeaiino? ai?ii?a i?e aoaeue-yeiio cia/aii?
?iiii? neee c ae?aiaciio aeine?aeaeaieo, ia a?aei?io a?ae e?oa?aoo?ieo
aeaieo, ui a?aeiinyoueny eeoa aei ie?aieo, aeineoue a?aeaeaeaieo iaeia
a?ae iaeiiai, cia/aiue ?iiii? neee.
Aia?oa iaea?aeaii eiao?oe??ioe aeoeaiino? aeiaeaoeeenoeueoaoo a
nieueiaeo ?ic/eiao (NaCl, NaNO3), ui aeicaiey? i?iaiicoaaoe aoaeoe
aeniethaaiiy i?e canoinoaaii? aeiaeaoeeenoeueoaoo aeey iiaa?oiaaiai
a?aeie?aieaiiy /e ?iiii? oeioaoe??.
Ae?noaea iiaeaeueoee ?icaeoie iaoiaeieia?y canoinoaaiiy eiao?oe??io?a
naeaeoeaiino? aeey a?aooaaiiy aieeao ?iiiiai?iii? eiieo?aioe?? ia
aiae?oe/iee neaiae iioaioe?iiao??? c iaia?aiieie aeaeo?iaeaie. I?e
aeine?aeaeaii? iioeaie iaeii/aniiai aecia/aiiy aeaio eiiiiiaio?a
aaaaeaii iia? ci?ii?, ui iieaaoothoue iioei?caoe?th oiia aecia/aiiy.
Aia?oa iaea?aeaii ocaaaeueiai? oa?aeoa?enoeee iiaeeeainoae iaeii/aniiai
aecia/aiiy aeaio eiiiiiaio?a c ?NA, aiae?oe/i? neaiaee yeeo
ia?ae?eaathoueny.
Aia?oa iieacaii, ui aeey iaeii/aniiai aecia/aiiy i?o?aoo oa ia?oei?aoo
iiaeia canoiniaoaaoe aeaa ia?oei?aonaeaeoeai? aeaeo?iaee, eiao?oe??ioe
naeaeoeaiino? yeeo ??ciyoueny ia iaio i?ae o /ioe?e ?ace.
Cia/aiiy iaea?aeaieo ?acoeueoao?a. Iaea?aeai? ?acoeueoaoe iathoue
oai?aoe/ia cia/aiiy aeey oaiiiao?eee iioaioe?iiao?e/iiai aiae?co
(caeiiii??iino? aeaieiiiiiaioieo aecia/aiue a oiiaao ia?ae?eaaiiy
aiae?oe/ieo neaiae?a ?NA), oai??? ?ic/ei?a aeaeo?ie?o?a (iiaeae?
eiao?oe??io?a aeoeaiino? no?oeoo?i?oeioth/eo ai?ii?a), oai??? iaoiae?a
iiaa?oiaaiai a?aeie?aieaiiy (caeiiii??iino? aeniethaaiiy ai?iiii? IA?).
I?aeoe/ia cia/aiiy iaea?aeaieo ?acoeueoao?a iia’ycaia c ae??oaiiyi
caaea/ iao?ieia?/iiai caaacia/aiiy aei??thaaiue c ai?iinaeaeoeaieie
aeaeo?iaeaie oa aeioneo ?NA. Iiaeae? aeaeo?iaeiiai a?aeaoeo oa aeai? i?i
eiao?oe??ioe aeoeaiino? ai?ii?a caaacia/othoue a?aaeothaaiiy
iioaioe?iiao?e/ieo i?eeaae?a c a?aeiia?aeieie ?NA a oeaeao aeoeaiino?
iioaioe?aeooai?thth/iai ai?iia, ui aeicaiey? aecia/aoe naia aeoeai?noue
ai?ii?a a ??aeeiieo na?aaeiaeuao. Iaea?aeai? caeaaeiino? a?aeiinii?
iioeaee a?ae oiia iaeii/aniiai aecia/aiiy aeaio eiiiiiaio?a c ?NA
aeicaieythoue a?aeiiaeoenue a?ae aii??e/iiai iiooeo i?e neeaaeaii?
eiie?aoieo iaoiaeee aiae?co c i/?eoaaieie iao?ieia?/ieie
oa?aeoa?enoeeaie. Oeueiio ni?eythoue ? ioe?iee ae?aiacii?a
eiioeaio?aoe?e, aea iiaeeeaa iaeii/ania aecia/aiiy aeaio ai?ii?a,
iaaaaeai? aeey iaea?eueo iioe?aieo a aiae?oe/i?e i?aeoeoe?
ai?iinaeaeoeaieo aeaeo?iae?a. Aeey iioaioe?iiao?e/iiai aecia/aiiy
ai?ii?a AF4-, aeiaeaoeeenoeueoaoo, ?ooo? o aeaeyae? HgI3- ?ic?iaeaii
?aeiiaiaeaoe?? c i?eaiooaaiiy a?aaeothaaeueieo ?ic/ei?a oa i?aeaioiaee
i?iae, ui aeicaieythoue onoiooe iioeaee, coiiaeai? ci?iith o?i?/ii?
oi?ie iioaioe?aeooai?thth/iai ai?iia i?e a?aaeothaaii? oa aiae?c?.
Eiao?oe??ioe aeoeaiino? aeiaeaoeeenoeueoaoo a nieueiaeo ?ic/eiao (NaCl,
NaNO3) aeicaieythoue i?iaiicoaaoe aoaeoe aeniethaaiiy, a a?aeoae ?
naeaeoeai?noue oa aoaeoeai?noue aeeo/aiiy i?e canoinoaaii?
aeiaeaoeeenoeueoaoo aeey iiaa?oiaaiai ?icae?eaiiy ?ic/eiaieo ?a/iaei oa
?iiii? oeioaoe??.
Iniaenoee aianie caeiaoaa/a iieyaa? a: aenia?eiaioaeueieo
aeine?aeaeaiiyo ? ia?iaoe? ?acoeueoao?a aenia?eiaioo; ?ic?iaoe?,
aei?iaoaaii? oa ai?iaaaeaeaii? iaoiaeee aecia/aiiy; ?ic?iaoe?
?aeiiaiaeaoe?e c iao?ieia?/iiai caaacia/aiiy aei??thaaiue c
ai?iinaeaeoeaieie aeaeo?iaeaie. Ni?eueii c iaoeiaei ea??aieeii
iinoaaeaii caaea/?, nieaiiaaii aenia?eiaio, iaaiai?aii ? ocaaaeueiaii
?acoeueoaoe. A ?iaioao, ui iioae?eiaaii a ni?aaaoi?noa? c e.o.i., aeioe.
I.I.?aoaoiye, iniaenoee aianie caeiaoaa/a neeaaeathoue ?acoeueoaoe, ui
noinothoueny ai?iinaeaeoeaieo aeaeo?iae?a. A ?iaio?, iioae?eiaai?e o
ni?aaaoi?noa? c ae.o.i., i?io. I.A.Aoaa?anueeei, caeiaoaa/ai
aeine?aeaeaii iiaaae?ieo eiaeeaenaeaeoeaieo aeaeo?iae?a o ai?iiiaooa?ieo
nenoaiao.
Ai?iaaoe?y ?acoeueoao?a aeena?oaoe??. ?acoeueoaoe aeine?aeaeaiue
ii?eethaeiaii ia Ananithci?e eiioa?aioe?? “Iaoiaeu aiaeeca iauaeoia
ie?oaeathuae n?aaeu” (Iineaa, 1983); VI Iaiaeaea?anuee?e aeeneonn??
“?acoeueoaou yenia?eiaioia e eo ianoaeaeaiea ia iieaeoey?iii o?iaia”
(Oa?e?a, 1983); IV ?anioae?eainuee?e eiioa?aioe?? c aeaeo?io?i??
(Oa?e?a, 1984); II ?anioae?eainuee?e eiioa?aioe?? c aiae?oe/ii? o?i??
(Oaeai?iae, 1985); I?ae?anioae?eainuee?e iaoeiai-oaoi?/i?e eiioa?aioe??
“?aoaiea yeieiae/aneeo i?iaeai ia i?aaei?eyoeyo oeie/aneie e
iaooaoeie/aneie i?iiuoeaiiinoe” (Aieaia?aae, 1989); I?aeia?iaei?e
eiioa?aioe?? c eii?aeeiaoe?eii? o?i?? XXVIII ICCC (Aa?a, IAe?, 1990);
I?aeia?iaeiiio eiia?an? c aiae?oe/ii? o?i?? (Iineaa, 1997); ??
Oe?a?inueeiio aeaeo?io?i?/iiio c’?cae? (Aei?i?iiao?ianuee, 1999).
No?oeoo?a aeena?oaoe??. Aeena?oaoe?y neeaaea?oueny c? anooio ? i’yoe
?icae?e?a. Iiaiee ianya ?iaioe noaiiaeoue 128 noi??iie, aeena?oaoe?y
i?noeoue 18 ?enoie?a, 45 oaaeeoeue ? nienie aeei?enoaieo e?oa?aoo?ieo
aeaea?ae c? 131 iaeiaioaaiiy.
INIIAIEE CI?NO ?IAIOE
A ia?oiio ?icae?e? iaaaaeaii iaeyae e?oa?aoo?ieo aeaieo i?i iniiai? oeie
aieeao eiiiiiaio?a iao?eoe? oa niiniae ?o onoiaiiy a iioaioe?iiao??? c
iaia?aiieie ?NA; iaa?oioiaaii iinoaiiaeo caaea/ aeine?aeaeaiiy.
Iieacaii, ui aeai? i?i eiao?oe??ioe aeoeaiino? ai?ii?a NO3- ? ClO4-
ia/eneaii? ? iaaeinoaoiuei ocaiaeaeai?, a aeey ai?ii?a BF4- ?
aeiaeaoeeenoeueoaoo i?aeoe/ii a?aenooi?, ui oiaiiaeeeaeth? a?aaeothaaiiy
a?aeiia?aeieo aeaeo?iae?a ca oeaeith aeoeaiino?. A?aenooi? caaaeuei?
oyaeaiiy i?i iiaeeeaino? iaeii/aniiai aecia/aiiy aeaio eiiiiiaio?a a
oiiaao ia?ae?eaaiiy aiae?oe/ieo neaiae?a ?NA (ae?aiaciie eiioeaio?aoe?e,
??aaiue iioeaie) oa i?i e?eoa??? aeai?o ICE aeey ioeueoeaeaeo?iaeii?
nenoaie.
A ae?oaiio ?icae?e? iaaaaeaii oiiae aenia?eiaioo, ?acoeueoaoe aecia/aiiy
?ino?oiaioaeueieo iioeaie ? ?aeiiaiaeaoe?? c onoiaiiy iioeaie,
coiiaeaieo ci?iith o?i?/ii? oi?ie iioaioe?aeooai?thth/iai ?iia.
A ?iaio? aeei?enoaii aeaeo?iaee c ieanoeo?eiaaieie ??aeeiieie
iaia?aiaie, i?ecia/ai? aei aecia/aiiy iaeiica?yaeieo ai?ii?a (NO3-,
ClO4-, BF4- ); ?ooo?(??) o aeaeyae? eiaeeaeieo eiiieaen?a HgI3- oa
eiaeeaenaeaeoeai? aeaeo?iaee c oaa?aeeie iaia?aiaie Orion 94-53, Crytur
53-17. Aeaeo?iaee, naeaeoeai? aei ai?ii?a aeiaeaoeeenoeueoaoo,
iaea?aeaii iiaeeo?eaoe??th NO3- – naeaeoeaieo aeaeo?iae?a.
A oiiaao aeine?aeaeaiue aeiaaeeia? iioeaee aei??thaaiiy a.?.n.
a?aeiia?aeaee caeiio ii?iaeueiiai ?iciiae?eo; noaiaea?oia a?aeoeeaiiy
a.?.n. neeaaeaei aeecueei (0,2 iA. A?aeiinia noaiaea?oia a?aeoeeaiiy i?e
aecia/aii? eooiaiai eiao?oe??ioo a?aaeothaaeueii? oa?aeoa?enoeee ia
ia?aaeuoaaei (0,01; ?ino?oiaioaeueia iioeaea aecia/aiiy eiioeaio?aoe??
iaeiica?yaeieo ?ii?a neeaaea? aeecueei 2,5%.
Aenia?eiaioaeueii ? ia/eneaiiyie aeine?aeaeaii iioeaee, ui coiiaeai?
ci?iith o?i?/ii? oi?ie iioaioe?aeooai?thth/iai ai?iia (a?ae?ie?c ?ii?a
oao?aooi?iai?aoo, i?oeaeiooai?aiiy a ?ic/eiao aeiaeaoeeenoeueoaoo,
eiieo?oth/? ?aaeoe?? eiiieaeniooai?aiiy aeey ai?iia HgI3-).
Iioeaie, ui coiiaeai? a?ae?ie?cii BF4-, iiaeia oieeiooe, yeui ?ic/eie
NaBF4 c iiey?iith eiioeaio?aoe??th a?ae 1.10-2 iieue/e ? aeua caa??aaoe
i?ioyaii 1-2 ae?a a oaoeiiiaiio iinoae?, a ?ic/eie c iaioith
eiioeaio?aoe??th aiooaaoe ?icaaaeaiiyi eiioeaio?iaaieo aaciina?aaeiuei
ia?aae aei??thaaiiyie.
Aeaeo?iae aeey aecia/aiiy ?ooo? (II) ia? a?aeaoe aei eiiieaeniiai ai?iia
HgI3-, yeee caeia? i?ii?aeia iieiaeaiiy a iine?aeiaiino? nooi?i/aoeo
eiiieaen?a ? ia?aaaaea? a aeineoue aocueeiio ae?aiacii? ??aiiaaaeieo
eiioeaio?aoe?e eiaeeaeo. Iiaia ia?aoai?aiiy ?ooo? (II) a eiiieaen HgI3-
iaiiaeeeaa: iaeneiaeueiee aeo?ae HgI3- neeaaea? 75% a?ae caaaeueii?
eiioeaio?aoe?? ?ooo? (II). Aeey iia??thaaiiy oa a?aaeothaaiiy HgI3-
-naeaeoeaieo aeaeo?iae?a cai?iiiiiaaii ?ic/eie c iino?eiith
??aiiaaaeiith eiioeaio?aoe??th eiaeeae-?ii?a. Uia aeii?oee ?ooo? o
?aaeoea? KI ia aieeaaee ia caaaeueio eiioeaio?aoe?th ?ooo? (II),
a?aaeothaaeuei? ?ic/eie iathoue i?noeoe 0,1 iieue/e iaca’ycaiiai
eiaeeaeo i?e eiioeaio?aoe?? ?ooo? (II) a?ae1.10-5 aei 1.10-2 iieue/e, ?
1.10-3 iieue/e iaca’ycaiiai eiaeeaeo i?e eiioeaio?aoe?? ?ooo? (II) a?ae
1.10-7 aei1.10-5 iieue/e. Oaeo ae ??aiiaaaeio eiioeaio?aoe?th eiaeeaeo
ne?ae noai?thaaoe a ?ic/ei?, ui aiae?cothoue. Ni?aa?aeiioaiiy
eiioeaio?aoe?e ?aaaaio?a a a?aaeothaaeueieo ?ic/eiao iaaaaeaii a oaae.
1.
Oaaeeoey 1
Ca’ycie i?ae caaaeueiith ? ??aiiaaaeiith eiioeaio?aoe?yie eiaeeaeo a
nenoai? ?oooue(II) – eiaeeae
[I-], iieue/e n(I-)
1,0.10-3 3,110 n(Hg2+)+1,0.10-3
0,10 3,941n(Hg2+)+0,10
Ai?iie aeiaeaoeeenoeueoaoo c eiioeaio?aoe??th aeua ca e?eoe/io
eiioeaio?aoe?th i?oeaeiooai?aiiy (cmc) ooai?thoue i?oeaee:
DS- + ( Na+ ( {Na(DS}m, (1)
aea ( – nooi?iue ca’ycoaaiiy i?ioe?ii?a; ?iaeaen m a?aeiineoueny aei
i?oeaey?iiai noaio.
Ia ?en.1 iaaaaeaii a?aaeothaaeueio oa?aeoa?enoeeo iiaeeo?eiaaiiai
aeaeo?iaea c a?aeaoeii ia ai?iie DS-. Ae?eyiea I e?i?eiiai a?aeaoeo c
eooiaei eiao?oe??ioii, aeecueeei aei cia/aiiy 2,303 RT/F, a?aeiia?aea?
aeii?oeaey?i?e iaeano?, aea lg [DS-] = lg c, ? a?aaeothaaeueia
oa?aeoa?enoeea a?aeiia?aea? ??aiyiith:
E = E( – k lg n. (2)
?en.1 Caeaaei?noue a.?.n. a?ae eiioeaio?aoe?? aeiaeaoeeenoeueoaoo
iao??th a ?ic/eiao c iino?eiith ?iiiith neeith (1 iieue/e NaCl)
I?oeaee IA? a i?enooiino? nieae, ui i?noyoue i?ioe?iie, a?ae?a?athoue
?ieue nai???aeiiai aooa?a a?aeiinii ?ii?a IA?. Oiio a i?oeaey?iiio
na?aaeiaeu? (ae?eyiea II) ??aiiaaaeia eiioeaio?aoe?y ?ii?a IA?
ci?ith?oueny iaio iii?oii, i?ae caaaeueia eiioeaio?aoe?y IA?. Oi/ea
ia?aoeio e?i?eieo a?ae??ce?a a?aeiia?aea? cmc. A i?oeaey?iiio
na?aaeiaeu? a?aaeothaaeueia oa?aeoa?enoeea ae?aaea?oueny ??aiyiiyi
E = E( – k lg const + ( k lg{ cmc + ( 1–( ) (n – cmc ) + n salt }.
(3)
I?e n >> cmc caeaaei?noue a.?.n. ii/eia? a?aeiia?aeaoe eao?iiiiio
a?aeaoeo, o a?aenooiino? oiiiaiai aeaeo?ie?oo
E = const + ( k lg n. (4)
c eooiaei eiao?oe??ioii, iaioei ca ia?ino?anueea cia/aiiy (( = 0,74 (
0,04).
Ca eii?aeeiaoaie oi/ee ia?aoeio e?i?eieo ae?eyiie aecia/aii cia/aiiy cmc
NaDS a ?ic/eiao NaCl c eiioeaio?aoe??th a?ae 0,01 aei 2 iieue/e, a
?ic/eiao CuSO4 c eiioeaio?aoe??th a?ae 5.10-3 aei 0,05 iieue/e oa
aeayeeo ?ioeo.
Uia oieeiooe iioeaie, coiiaeaieo i?oeaeiooai?aiiyi, ?aeiiaiaeiaaii
?ic??ciyoe i?oeaey?i? ? aeii?oeaey?i? ?ic/eie, aeei?enoiaoth/e aeaa
??ci? aeiaeaiee i?ioe?iia. I?e aecia/aii? aeiaeaoeeenoeueoaoo oea
iiaeooue aooe aeiaeaiee oei?eaeo iao??th —oae?, ui a?aeiia?aeathoue
eiioeaio?aoe?yi Na+ 0,1 ? 1 iieue/e. A aeii?oeaey?ieo ?ic/eiao aaaaeaiiy
ae?oaiai aeiaeaieo ci?ith? a.?.n. i?eaeecii ia 12 iA (aiane?aeie
ci?ithaaiiy eiao?oe??ioo aeoeaiino? aeiaeaoeeenoeueoao-?iia; ca aeaieie
?icae. 3), a i?oeaey?ieo – i?eaeecii ia 50 iA (aiane?aeie ci?ithaaiiy
cmc).
A o?aoueiio ?icae?e? iaaaaeaii ?acoeueoaoe aeine?aeaeaiiy aieeao ?iiiiai
na?aaeiaeua ia a?aeaoe ai?iinaeaeoeaieo aeaeo?iae?a. I?i aieea
na?ae/eoue ci?ia aaee/eie E( i?e ci?i? eiioeaio?aoe?? ?ic/eio (?en.2):
E(= E + k lg c(A) = E( – Eaeeo – k lg ((A). (5)
?en.2 Caeaaei?noue aaee/ei A( (1),
ui iaea?aeai? c
BF4- – naeaeoeaiei aeaeo?iaeii o ?ic/eiao NaBF4,
? caeaaei?noue Eaeeo (2), ?ic?aoiaaia ca ??aiyiiyi Aaiaea?niia.
A ?icaaaeaieo ?ic/eiao ia?aaaaea? ci?ia aeeooc?eiiai iioaioe?aeo
(?en.2), a a?eueo eiioeaio?iaaieo (aeua 10-2 iieue/e) – ci?ia
eiao?oe??ioo aeoeaiino? iioaioe?aeooai?thth/iai ?iia.
E?euee?niee iien a?aeaoeo ai?iinaeaeoeaieo aeaeo?iae?a a ae?aiacii?
eiioeaio?aoe?e a?ae 1.10-4 aei 0,1 iieue/e iaea?aeaii ca ??aiyiiyi:
E = E( – (k +b2) lg {c(A)+ b1} – k (b3 I1/3 + b4 I), (6)
aea b1 —aii??e/iee ia?aiao?, ui oa?aeoa?eco? aianie aei caaaeueii?
eiioeaio?aoe?? iioaioe?aeooai?thth/iai ai?iio A, yeee coiiaeaiee
?ic/eiaiiyi iaia?aie /e aeani?aoe??th ?ii?a c ?? iiaa?oi?;
b2 –ia?aiao?, ui oa?aeoa?eco? ci?io aeeooc?eiiai iioaioe?aeo;
b3 ? b2 –ia?aiao?e aii??e/ii? caeaaeiino? eiao?oe??io?a aeoeaiino? a?ae
?iiii? neee:
lg ((A) = b3 I1/3 + b4 I. (7)
Ia?aiao?e ciaoiaeeee ?aa?an?eiei aiae?cii. Aeyaeeinue, ui ia?aiao?e b1
? b2 ? i?aea?iieie aeey eiaeii? na??? aei??thaaiue c NO3–naeaeoeaiei
aeaeo?iaeii ? cia/eii ci?iththoueny a?ae na??? aei na???. Aeey
aei??thaaiue c ClO4– ? BF4– naeaeoeaieie aeaeo?iaeaie oe? ia?aiao?e
aeyaeeenue noaoenoe/ii iacia/eieie.
Ia?aiao?e ??aiyiiy (7) ioe?iaii ca ci?iith E( i?e ? > 10-2 iieue/e
(oaae.2).
Oaaeeoey 2
Ia?aiao?e ??aiyiiy (7) aeey ia/eneaiiy eiao?oe??io?a aeoeaiino? ai?ii?a
Ai?ii Neeaae ?ic/eio
(ae?aiacii ?, iieue/e) Oaiia-?aoo?a *enei
na??e b3
(s2b) b4
(s2b)
BF4-
NaBF4+NaCl
(10-2 – 3,0)
(10-2 – 3,0)
(10-2 – 3,0)
(10-2 – 3,0)
(10-2 – 3,0)
25 (C
5 (C
15 (C
35 (C
45 (C
18
8
6
9
9
-0,498
(1,7(10-5)
-0,403
(6,4(10-5)
-0,443
(5,7(10-4)
-0,434
(1,2(10-4)
-0,358
(2,5(10-4)
–
–
–
–
–
ClO4-
NaClO4
(10-2 – 0,1)
NaClO4+NaCl
(10-2 – 3,0)
25 (C
25 (C
7
11
-0,402
(1,3(10-5)
-0,412
(1,9(10-5)
–
0,075
(3(10-6)
NO3-
NaNO3
(10-2 – 1,0)
KNO3
(10-2 – 1,0)
KNO3 + KCl (1:1)
(10-2 – 2,0)
25 (C
25 (C
25 (C
12
12
15
-0,312
(2,9(10-5)
-0,15
(1,8(10-4)
-0.244
(1,8(10-4)
–
-0,15
(9,6(10-5)
-0.088
(1,6(10-4)
Aeyaeeinue, ui eiao?oe??ioe aeoeaiino? ai?iia DS- iaaoaathoue aeueo
cia/aiue, i?ae aeey iai?aai?/ieo ai?ii?a (?en.3), ui ocaiaeaeo?oueny c
aio?o?eueiei oa?aeoa?ii DS-. I?e eiioeaio?aoe?yo NaCl, aeueo ca 0,6
iieue/e, eiao?oe??ioe aeoeaiino? DS- a?eueo? ca iaeeieoeth. Oe?eaai
a?aecia/eoe, ui naia i?e oe?e eiioeaio?aoe?? NaCl a i?oeaey?iiio
na?aaeiaeu?, ca?aeii e?oa?aoo?iei aeaiei, ii/eia?oueny ia?aaoaeiaa
noa?e/ieo i?oeae a oeee?iae?e/i?. NaNO3 /eieoue iaioo aeniethth/o ae?th
ia DS-, i?ae NaCl: a i?enooiino? NaNO3 eiao?oe??ioe aeoeaiino? DS-
iathoue iaio? cia/aiiy, i?ae a i?enooiino? NaCl.
?en. 3 Caeaaei?noue eiaa?eoi?a eiao?oe??io?a aeoeaiino? ai?ii?a
a?ae ?iiii? neee:
1 – DS- ia oii? NaCl;
2 – NO3- a ?ic/eiao KNO3+KCl (1:1);
3 – ClO4- ia oii? NaCl;
4 – BF4- ia oii? NaCl.
Aeine?aeaeaii oaiia?aoo?io caeaaei?noue eiao?oe??io?a aeoeaiino? ai?iia
AF4-. Aeaeyae caeaaeiino? lg ((BF4-) a?ae oaiia?aoo?e iaeiaeiaee aeey
anueiai aeine?aeaeaiiai ae?aiaciio cia/aiue ?iiii? neee c i?i?ioiii i?e
25 (N.
Iaea?aeai? aeai? i?i eiao?oe??ioe aeoeaiino? ai?ii?a caaacia/othoue
a?aaeothaaiiy a?aeiia?aeieo aeaeo?iae?a o oeae? aeoeaiino? a ?ic/eiao c
?iiiith neeith aeua 10-2 iieue/e. Aiie oaeiae iathoue naiino?eia
cia/aiiy, ai oa?aeoa?ecothoue niaoeeo?eo iiaaae?iee ai?ii?a a
??ciiiai?oieo ?iiieo i?ioeanao. Oae, aeai? i?i eiao?oe??ioe aeoeaiino?
DS- a i?enooiino? iai?aai?/ieo nieae aeicaieythoue i?iaiicoaaoe aieea
iai?aai?/ieo nieae ia iiaa?oiaai-aeoeai? aeanoeaino? aeii?oeaey?ieo
?ic/ei?a IA?.
aeey 5 ?NA) oa ?icaeyiooi iiaeeeaino? iaeii/aniiai aecia/aiiy aeaio
eiiiiiaio?a ?c canoinoaaiiyi ioeueoeaeaeo?iaeieo nenoai.
Ca oi?ioeith iioe?aiiy iioeaie aeine?aeaeaii aieea aeiaaeeiaeo iioeaie
aei??thaaiiy a.?.n. oa iioeaie a?aaeothaaeueieo ia?aiao??a ia iioeaeo
aecia/aiiy eiao?oe??io?a naeaeoeaiino? (?en. 3). ?aeiiaiaeiaaii
aecia/aoe eiao?oe??ioe naeaeoeaiino? i?e (A > 10 iA, aea
(A – a?aeoeeaiiy a.?.n. a?ae ooieoe?? aeey iniiaiiai ?iia, coiiaeaia
eiieo?oth/ei ?iiii.
?en. 4 Caeaaei?noue a?aeiiniiai noaiaea?oiiai a?aeoeeaiiy
eiao?oe??ioo naeaeoeaiino? a?ae cia/aiiy (A;
aeey ??cieo c?ace?a iaeiioeiieo aeaeo?iae?a na??eiiai aeioneo ?ieiee
nooo?ai a?ae??ciyeenue (oaae.3).
Oaaeeoey 3
Eiao?oe??ioe naeaeoeaiino? ??cieo aecaiiey??a iaeiioeiieo aeaeo?iae?a
) 1 2 3 4 5 6
EM-ClO4-01
, 10-3
,10-3
(I=1,0) 0,98
0,03 0,58
0,01 0,20
0,01 0,28
0,02 0,98
0,04 1,02
(I=0,3) –
– 208
11 195
10 150
14 150
14 –
8,0
0,1 6,8
0,2 7,65
0,1 7,4
0,1 7,5
0,1 –
–
??aeeiiiiaia?aii? ai?iinaeaeoeai? aeaeo?iaee, i?ecia/ai? aeey aecia/aiiy
ClO4-, NO3-, BF4- ? o.i., oaeoe/ii ? iaeiioeiieie, ai, iacaeaaeii a?ae
iiiaieeaoo?ii? iacae aeaeo?iaea, ?o naeaeoeai?noue a?aeiia?aea? iaeiiio
? oiio ae ?yaeo naeaeoeaiino? ca?aeii e?iio?euei?e na???:
R– ( ClO4– ( I– ( NO3– ( Br– ( Cl–,
aea R– — aenieie?iio?eueiee i?aai?/iee ai?ii.
Oiae? nenoaia ??aiyiue, ia ye?e aaco?oueny aecia/aiiy aeaio eiiiiiaio?a
c ioeueoeaeaeo?iaeiith nenoaiith, iaaoaa? aeaeyaeo:
, (8)
, (9)
aea A ? A—?iie, aei yeeo aeaeo?iaee aeyaeythoue a?aeiia?aeii a?eueoo ?
iaioo naeaeoeai?noue; ?iaeaene 1 ? 2 a?aeiia?aeathoue aeaii aecaiiey?ai
iaeiioeiieo aeaeo?iae?a.
Aeey ioe?iee oiia iaeii/aniiai aecia/aiiy aeaio eiiiiiaio?a c aeaiia ?NA
a?aeiinio iioeaeo aecia/aiiy aoei i?aaenoaaeaii ye ooieoe?th aeaio
ci?iieo: a?aeiioaiiy eiao?oe??io?a naeaeoeaiino? aeaeo?iae?a
x = K2Pot / K1Pot, (10)
aea K1Pot – iaioee c aeaio eiao?oe??io?a naeaeoeaiino?;
?
y = K1Pot cB / cA, (11)
ui aei??aith? oyaiiio a?aeiiniiio c?inoo eiioeaio?aoe?? ?iia A ca
?aooiie aieeao eiieo?oth/iai ?iia A.
C aaaaeaiiyi oeeo ci?iieo oi?ioee iioe?aiiy iioeaie iaaoee aeaeyaeo:
; (12)
, (13)
aea 6,5.10–4 = (sc/c)2 — eaaae?ao a?aeiinii? iioeae aecia/aiiy i?e
a?aenooiino? aieeao eiieo?oth/eo ?ii?a.
Caeaaei?noue a?aeiinieo aeiaaeeiaeo iioeaie aeaieiiiiiaioieo aecia/aiue
a?ae ci?iieo x ? y iaaaaeaii ia ?en. 5.? 6.
= 0,05;
1,2 — sE = 0,2 iA; sk/k = 0,01;
3,4 — sE = 1 iA; sk/k = 0,03.
?en. 6 Caeaaei?noue a?aeiiniiai noaiaea?oiiai a?aeoeeaiiy
aecia/aiiy eiioeaio?aoe?e ?ii?a A (1) oa A (2) a?ae a?aeiioaiiy
eiao?oe??io?a naeaeoeaiino?;
= 0,05.
Ia iniia? oaeeo caeaaeiinoae iaea?aeaii ocaaaeueiaio ioe?ieo
iiaeeeainoae iaeii/aniiai aecia/aiiy aeaio eiiiiiaio?a c aeei?enoaiiyi
ioeueoeaeaeo?iaeii? nenoaie (ae?aiaciie eiioeaio?aoe?e iniiaiiai oa
eiieo?oth/iai ?ii?a, i/?eoaai? iioeaee aecia/aiiy). Oae, ae?aiacii
iaeii/aniiai aecia/aiiy aeaio ?ii?a c a?aeiiniith iioeaeith ia aeua 20%
a?aeiia?aea? cia/aiiyi y a?ae 0,075 aei 1,8.
Aeey na??eieo ?NA a oaae. 4 iaaaaeaii ni?aa?aeiioaiiy eiioeaio?aoe?e,
i?e yeeo iiaeeeai aecia/aoe iaeei ai?ii (iniiaiee /e eiieo?oth/ee) oa
aeaa ai?iie iaeii/anii. E?euee?ni? oa?aeoa?enoeee a?aieoeue aecia/aiiy
iaaaaeaii aeey aeaeo?iae?a, ye? i?e iaeiieiiiiiaioiiio aecia/aii? ?
“iaee?aueie” aeey iniiaiiai ?iia, ? iaeii/anii “iaea??oeie” —aeey
eiieo?oth/iai.
Iieacaii, ui canoinoaaiiy ioeueoeaeaeo?iaeii? nenoaie ?icoe?th?
ae?aiacii aecia/aiiy iniiaiiai ?iia i?eaeecii ia i?aoi?a ii?yaeee.
Oaaeeoey 4
Oiiae aecia/aiiy iniiaieo ? eiieo?oth/eo ai?ii?a c canoinoaaiiyi
aeaio ?NA c ??cieie eiao?oe??ioaie naeaeoeaiino?
c(A):n(A)
Iniiaiee ?ii (A) Eiieo?oth/ee ?ii
(A)
aa?oiy iaaea aecia/aiiy A (aieea A a?aenooi?e) aecia/aiiy
A ? A, o = 0,6 ieaeiy iaaea aecia/aiiy A (aieea A a?aenooi?e)
ClO4– NO3– 2,0.10–4 120 3000 200000
NO3– NO2– 2,4.10–2 1 25 1700
NO3– Cl– 4,4.10–3 6 135 9000
BF4– NO3– 3,3.10–3 7,5 180 12000
ClO4– BF4– 0,13 0,2 4,5 300
??ciyoueny ia iaio i?ae o 4 ?ace. ?acoeueoaoe aecia/aiue ca
?ic?iaeaiith iaoiaeeeith na?ae/aoue i?i a?aenooi?noue nenoaiaoe/ieo
iioeaie a ia?aaeaa/aiiio ae?aiacii? y a?ae 0,03 aei 2. Aeiaaeeia?
iioeaee aecia/aiiy oaeiae a?aeiia?aeathoue i/?eoaaiei caeaaeiinoyi: i?e
y Oaaeeoey 5
?acoeueoaoe aecia/aiiy i?o?aoo ? ia?oei?aoo a ?ic/eiao NaNO3 ? NaClO4
?
?ic/. Caaeaii, iieue/e y Ciaeaeaii, iieue/e
1 n(NO3–) = 1,00
n(ClO4–) = 9,94.10–5 2 n(NO3–) = 1,07 ( 0,03
n(ClO4–) = (7,0 ( 0,9).10–5
2 n(NO3–) = 1,00
n(ClO4–) = 3,03.10–4 0,7 n(NO3–) = 1,02 ( 0,02
n(ClO4–) = (3,0 ( 0,3).10–4
3 n(NO3–) = 1,00
n(ClO4–) = 5,04.10–4 0,4 n(NO3–) = 1,00 ( 0,03
n(ClO4–) = (5,2 ( 0,6).10–4
4 n(NO3–) = 1,00
n(ClO4–) = 7,02.10–4 0,3 n(NO3–) = 0,98 ( 0,07
n(ClO4–) = (7,4 ( 0,9).10–4
5 n(NO3–) = 1,00
n(ClO4–) = 9,96.10–4 0,2 n(NO3–) = 0,98 ( 0,10
n(ClO4–) = (1,03 ( 0,10).10–3
6 n(NO3–) = 1,00
n(ClO4–) = 3,05.10–3 0,07 n(NO3–) = 1,09 ( 0,13
n(ClO4–) = (2,9 ( 0,3).10–3
7 n(NO3–) = 1,00
n(ClO4–) = 5,09.10–3 0,04 n(NO3–) = 1,13 ( 0,18
n(ClO4–) = (4,8 ( 0,4).10–3
8 n(NO3–) = 0,99
n(ClO4–) = 7,10.10–3 0,03 n(NO3–) = 1,3 ( 0,6
n(ClO4–) = (7,0 ( 1,0).10–3
9
n(NO3–) = 0,93
n(ClO4–) = 7,06.10–2 0,003 *n(NO3–): -0,7; 0; -1,0;
n(ClO4–) = (6,9 ( 0,6).10–2
10 n(NO3–) = 0,91
n(ClO4–) = 9,04.10–2 0,002 *n(NO3–):0; 1,36; 0;
n(ClO4–) = (8,9 ( 0,6).10–2
AENIIAEE
Aecia/aii ia?aiao?e iiaeaeae aeaeo?iaeiiai a?aeaoeo, ui aeicaieythoue
ioe?ithaaoe aieea ie?aieo /eiiee?a ?iiiiai na?aaeiaeua (?iiia neea,
eiieo?oth/? ?iie, ci?ia o?i?/ii? oi?ie iioaioe?aeooai?thth/eo ?ii?a) ia
aiae?oe/iee neaiae iioaioe?iiao??? c ai?iinaeaeoeaieie iaia?aiieie
aeaeo?iaeaie.
Iaea?aeai? ??aiyiiy aeey ia/eneaiiy eiao?oe??io?a aeoeaiino? ai?ii?a a
?ic/eiao ?iaeea?aeoaeueieo aeaeo?ie?o?a oa a i?enooiino? oiiiaeo
aeaeo?ie?o?a aeicaieythoue noai?eoe oeaee aeoeaiinoae ai?ii?a i?o?aoo,
ia?oei?aoo, oao?aooi?iai?aoo, aeiaeaoeeenoeueoaoo, aeey yeeo ?
iai?eaeaoiith eiioeaioe?y oiiaieo oeae ?iiieo aeoeaiinoae ca
a?ae?aoaoe?eiith oai???th Aaeona-?ia?iniia.
I?e aecia/aii? ?ooo? c HgI3— -naeaeoeaieie aeaeo?iaeaie aeey onoiaiiy
iioeaie, coiiaeaieo ia?aoai?aiiyi HgI3— o aeu? oa ieae/? eiaeeaei?
eiiieaene, ne?ae i?aeo?eioaaoe iino?eio ??aiiaaaeio eiioeaio?aoe?th
eiaeeae-?ii?a o ?ic/eiao aeey a?aaeothaaiiy oa a ?ic/eiao, ui
aiae?cothoueny. Ia/eneaii ni?aa?aeiioaiiy ?aaaaio?a aeey i?eaiooaaiiy
?ic/ei?a c iino?eiith ??aiiaaaeiith eiioeaio?aoe??th eiaeeae-?ii?a.
I?e iioaioe?iiao?e/iiio aecia/aii? ?ii?a IA? aeey onoiaiiy iioeaie,
coiiaeaieo i?oeaeiooai?aiiyi, ne?ae ?ici?ciaaaoe i?oeaey?i? ?
aeii?oeaey?i? ?ic/eie, canoiniaoth/e a?aeii? aeiaeaiee i?ioe?ii?a.
Iaaaaeaii /enaeuei? cia/aiiy e?eoa???a aeey ?ici?ciaaaiiy i?oeaey?ieo oa
aeii?oeaey?ieo ?ic/ei?a aeiaeaoeeenoeueoaoo iao??th.
Iaae?ei?noue aecia/aiiy eiao?oe??io?a naeaeoeaiino? i?aeaeuo?oueny ca
oiia, eiee a?aeoeeaiiy a.?.n. aiane?aeie ?iiii? eiieo?aioe??
ia?aaeuothoue 10 – 20 iA, a noia eiioeaio?aoe?e iniiaiiai oa
eiieo?oth/iai ?ii?a caeeoa?oueny iino?eiith i?e ci?ithaaii?
eiioeaio?aoe?? iniiaiiai ?iia. Nenoaiaoe/ia aeine?aeaeaiiy
ai?iinaeaeoeaieo aeaeo?iae?a na??eiiai aeioneo na?ae/eoue i?i oa, ui
aecia/aiiee a oeeo oiiaao eiao?oe??io naeaeoeaiino? ? iino?eiei
a?aaeothaaeueiei ia?aiao?ii eiie?aoiiai aecaiiey?o iaia?aiiiai
aeaeo?iaea.
Iaeii/ania aecia/aiiy aeaio eiiiiiaio?a a oiiaao ia?ae?eaaiiy
aiae?oe/ieo neaiae?a aeaio ?NA aeicaiey? ?icoe?eoe ae?aiacii aecia/aiiy
ia i?aoi?a ii?yaeee ii??aiyii c aecia/aiiyi iaeiiai eiiiiiaioa a
i?enooiino? eiieo?oth/eo ?ii?a. Aeey aeai?o oiia iaeii/aniiai aecia/aiiy
aeioe?eueii ?icaeyaeaoe iioeaeo aecia/aiiy ye ooieoe?th ci?iieo
x = K2Pot / K1Pot, y = K1Pot cB / cA, aea K1Pot - iaioee c aeaio
eiao?oe??io?a naeaeoeaiino?. Iaea?aeai? a?ao?/i? caeaaeiino?
aeicaieythoue i?iaiicoaaoe iiaeeeaino? iaeii/aniiai aecia/aiiy c
eiie?aoieie ?NA (ae?aiaciie eiioeaio?aoe?e ? iioeaee aecia/aiiy
iniiaiiai ? eiieo?oth/iai ?ii?a).
Aeey aeaieiiiiiaioieo aecia/aiue iiaeooue canoiniaoaaoenue iaeiioeii?
iaia?aii? aeaeo?iaee, eiao?oe??ioe naeaeoeaiino? yeeo ??ciyoueny ia iaio
i?ae o 4 ?ace. Ia oe?e iniia? ?ic?iaeaii iaoiaeeeo iaeii/aniiai
aecia/aiiy i?o?aoo oa ia?oei?aoo a oaoiieia?/ieo ?ic/eiao oa ?icoiiao
i?o?aoo ia?aaioeth (II).
Nienie iioae?eiaaieo i?aoeue ca oaiith aeena?oaoe??
Eiaeiiaa E.I., Ianeee I.A. Enneaaeiaaiea aeeyiey i?iaeoeoia aeae?ieeca
BF4- -eiia ia ooieoeeth yeaeo?iaea YI - BF4 – 01. Eeiaoe/aneea e
?aaiiaaniua oaeoi?u. Auai? oneiaee aeey i?yiie iioaioeeiiao?ee // Aanoi.
Oa?uee. oi-oa. Na?. Oa?iiaeeiaieea e yeaeo?ioeiey ?anoai?ia a iaaiaeiuo
n?aaeao. – 1983. – ?.242 – N.50-55.
Eiaeiiaa E.I., Ianeee I.A. Iao?ieiae/aneia iainiiaaiea aeeyiey
oaiia?aoo?u ia iioaioeeiiao?e/aneia ii?aaeaeaiea oao?aooi?ai?ao-eiiia a
aiaeiuo ?anoai?ao // AE. aiaeeo. oeiee. – 1985. – O. 40, ? 3. –
N.452-454.
Eiaeiiaa E.I., Ianeee I.A., O?iyi A.I. Eiyooeoeeaiou aeoeaiinoe
ia?oei?ao-eiiia a aiaeiuo ?anoai?ao // Aanoi. Oa?uee. oi-oa. Na?.
Oeceei-oeiey yeaeo?ieeoia e eii?aeeiaoeeiiiuo niaaeeiaiee. – 1987. – ?
300. – N.59-62.
Eiaeiiaa E.I., Ianeee I.A., Eyo E.I. Iioaioeeiiao?e/aneia oeo?iaaiea
oao?aooi?iai?ao-eiiia / Aanoi. Oa?uee. oi-oa. – 1986. – ? 289.
Oeceei-oeiey ?anoai?ia. Yeaeo?ioeiey. – N.66-69.
Eiaeiiaa E.I., Ianeee I.A., Iiii/aaa A.A. ?ac?aaioea iaoiaeeee
ii?aaeaeaiey ieo?ao-eiiia a ?anoai?a iaoiaeii eiiiiao?ee //Aanoi.
Oa?uee. oi-oa. – 1988. – ? 319. Yeaeo?ioeiey. Eiiiua ?aaiiaaney a
?anoai?ao. – N.36-38.
Iioaioeeiiao?e/aneia e niaeo?ioioiiao?e/aneia enneaaeiaaiea naycuaaiey
i?ioeaieiiia ieoeaeeaie aeiaeaoeeenoeueoaoa iao?ey e iaaee / Eiaeiiaa
E.I., Ianeee I.A., ?aoaoiye A.A. e ae?. // Aanoi. Oa?uee. oi-oa. Oeiey.
– 1998. ? 2. N.223-229.
Eiaeiiaa E.I., Ianeee I.A. Iiaeaee yeaeo?iaeiiai ioeeeea iaia?aiiuo
yeaeo?iaeia ii ioiioaieth e eiiai ieo?aoa e aeiaeaoeeenoeueoaoa
//Aii?inu oeiee e oei. oaoiieiaee.- 1999. - ? 1. – N.216 – 218.
A.n. 1343337 NNN?, IEE G 01 N 27/52. Niinia iioaioeeiiao?e/aneiai
ii?aaeaeaiey ieo?ao- e ia?oei?ao-eiiia a ?anoai?a/ E.I.Eiaeiiaa,
I.A.Ianeee (NNN?). – 3820338/24-25; Cayaeaii 05.12.84; Iioae. 07.10.87,
Athe. ? 37. – 4 n.
Eiaeiiaa E.I., Ianeee I.A. Naeaeoeaiinoue yeaeo?iaeia YI-AF4-01 a
aiaeiuo ?anoai?ao // Oa?ueeiane. oi-o. – Oa?ueeia, 1984. – 16 n. Aeai. a
Oe?IEEIOE 03.10.84 ? 1590Oe – 84Aeai.
Eiaeiiaa E.I., Ianeee I.A., Eicee O.A., Iiii/aaa A.A. Naeaeoeaiinoue
yeaeo?iaeia YI-NO3-01 e YI-ClO4-01 a aiaeiuo ?anoai?ao // Oa?ueeiane.
oi-o. – Oa?ueeia, 1986. – 25 n. Aeai. a Oe?IEEIOE 13.01.87 ? 354–Oe 87.
Bugaevsky A.A., Loginova L.P., Maslij O.G. Use of complexonates for
pH-independent ion buffers creation // Proc. International Conf. on
Coord. Chem. – Gera(DDR). – 1990. – P. 2-67.
Eiaeiiaa E.I., Ianeee I.A., ?aoaoiye A.A., Eeauaaieeiaa A.I.
Eniieueciaaiea eiyooeoeeaioia naeaeoeaiinoe aeey eioa?i?aoaoeee
?acoeueoaoia eiiiiao?e/aneiai aiaeeca iiiaieiiiiiaioiuo nenoai // Oacenu
aeiee. ?? ?ani. eiio. ii aiaeeoe/aneie oeiee. – Oaeai?iae. – 1985. –
N.115.
Loginova L., Maslij O., Reshetnyak E. The possibilities of computational
methods of interferences elimination in measurements with ion-selective
electrodes// Proc. International Congr. on Anal. Chem. – Moscow(Russia).
– 1997. – P.G-67.
Iane?e I.A. Aieea ?iiieo eiiiiiaio?a iao?eoe? ia aiae?oe/iee neaiae
iioaioe?iiao??? c ai?iinaeaeoeaieie aeaeo?iaeaie. –?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. –Oa?e?anueeee aea?aeaaiee
oi?aa?neoao, Oa?e?a, 1999.
Aeena?oaoe?th i?enay/aii ?icaeoeo iao?ieia?/iiai caaacia/aiiy
aei??thaaiue c ai?iinaeaeoeaieie iaia?aiieie aeaeo?iaeaie. Iaea?aeaii
ia?aiao?e iiaeaeae, ui iienothoue aieea ia aiae?oe/iee neaiae /eiiee?a
?iiiiai na?aaeiaeua (?iiia neea, eiieo?oth/? ?iie, ci?ia o?i?/ii? oi?ie
iioaioe?aeooai?thth/eo ai?ii?a). Iaea?aeaii ??aiyiiy aeey ia/eneaiiy
eiao?oe??io?a aeoeaiino? NO3-, ClO4-, BF4- ? aeiaeaoeeenoeueoaoo, ui
caaacia/othoue aecia/aiiy ai?ii?a ca oeaeith aeoeaiino?. Aia?oa
cai?iiiiiaaii e?eoa??? aeai?o aeaeo?iae?a aeey ioeueoeaeaeo?iaeii?
nenoaie oa iaea?aeaii ocaaaeueiai? oa?aeoa?enoeee iiaeeeainoae
iaeii/aniiai aecia/aiiy aeaio eiiiiiaio?a c ?NA (ni?aa?aeiioaiiy
eiioeaio?aoe?e, iioeaee aecia/aiiy).
Eeth/ia? neiaa: ai?iiinaeaeoeai? aeaeo?iaee, i?o?ao, ia?oei?ao,
oao?aooi?iai?ao, aeiaeaoeeenoeueoao, eiao?oe??ioe aeoeaiino?,
eiao?oe??ioe naeaeoeaiino?, iaeii/ania aecia/aiiy.
Ianeee I.A. Aeeyiea eiiiuo eiiiiiaioia iao?eoeu ia aiaeeoe/aneee neaiae
eioaioeeiiao?ee n aieiinaeaeoeaiuie yeaeo?iaeaie.-?oeiienue.
Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa oeie/aneeo iaoe ii
niaoeeaeueiinoe 02.00.02 – aiaeeoe/aneay oeiey. –Oa?ueeianeee
ainoaea?noaaiiue oieaa?neoao, Oa?ueeia, 1999.
Aeenna?oaoeey iinayuaia ?acaeoeth iao?ieiae/aneiai iaania/aiey ecia?aiee
n aieiinaeaeoeaiuie iaia?aiiuie aeaeo?iaeaie. Iieo/aiu ia?aiao?u
iiaeaeae, iienuaathueo aeeyiey eiiiuo eiiiiiaioia iao?eoeu ia
aiaeeoe/aneee neaiae (eciaiaiea eiyooeoeeaioia aeoeaiinoe e
aeeoooceiiiiai iioaioeeaea; aeeyiey, naycaiiua n naeaeoeaiinoueth;
eciaiaiea oeie/aneie oi?iu iioaioeeaeii?aaeaeythuaai eiia). Aia?aua
i?aaeeiaeaiu e?eoa?ee auai?a eiinaeaeoeaiuo yeaeo?iaeia (ENY) aeey
ioeueoeyeaeo?iaeiie nenoaiu. Iieo/aiu iaiauaiiua oa?aeoa?enoeee
aiciiaeiinoae iaeiia?aiaiiiai ii?aaeaeaiey aeaoo eiiiiiaioia a oneiaeyo
ia?ae?uaaiey aiaeeoe/aneeo neaiaeia ENY.
A ia?aie aeaaa i?eaaaeai iaci? eeoa?aoo?iuo aeaiiuo ia iniiaiuo oeiao
iaoathueo aeeyiee e niiniaao eo ono?aiaiey a iioaioeeiiao?ee n
iaia?aiiuie ENY.
Ai aoi?ie aeaaa i?eaaaeaiu oneiaey yenia?eiaioa, ?acoeueoaou
ii?aaeaeaiey eino?oiaioaeueiuo iia?aoiinoae e ?aeiiaiaeaoeee ii
ono?aiaieth iia?aoiinoae, aucaaiiuo eciaiaieai oeie/aneie oi?iu
iioaioeeaeii?aaeaeythueo aieiiia. Iia?aoiinoae ca n/ao aeae?ieeca
aieiiia BF4- iiaeii ecaaaeaoue, nio?aiyy ?anoai?u NaBF4 n iiey?iie
eiioeaio?aoeeae io 1.10-2 iieue/e e auoa ia aieaa 1-2 nooie a oaoeiiiaie
iinoaea e aioiay ?anoai?u n iaiueoae eiioeaio?aoeeae iaiin?aaenoaaiii
ia?aae ecia?aieyie. Yeaeo?iae aeey ii?aaeaeaiey ?oooe (II) eiaao ioeeee
ia eiiieaeniue aieii HgI3-, eioi?ue yaeyaony i?iiaaeooi/iui a
iineaaeiaaoaeueiinoe nooiai/aouo eiiieaenia e i?aiaeaaeaao a oceii
aeeaiaciia ?aaiiaaniuo eiioeaio?aoeee eiaeeaea. Aeey iiaa?ee e
a?aaeoe?iaee HgI3- naeaeoeaiuo yeaeo?iaeia i?aaeeiaeaiu ?anoai?u n
iinoiyiiie ?aaiiaaniie eiioeaio?aoeeae eiaeeae-eiiia. I?eaaaeaiu
o?aaiaiey aeey auai?a ninoaaa ?anoai?ia. I?yiia eiiiiao?e/aneia
ii?aaeaeaiea aieiiia aeiaeaoeeenoeueoaoa (DS-) e ae?oaeo
iiaa?oiinoii-aeoeaiuo aauanoa i?eaiaeeo e iaiaeiicia/iui ?acoeueoaoai a
nayce n ieoeaeeiia?aciaaieai. Ia iniiaa enneaaeiaaiey caaeneiinoae
e?eoe/aneie eiioeaio?aoeee ieoeaeeiia?aciaaiey e eiyooeoeeaioia
aeoeaiinoe DS- io eiioeaio?aoeee NaCl noi?ioee?iaaiu e?eoa?ee,
iicaieythuea ?acee/aoue ieoeaeey?iua e aeiieoeaeey?iua ?anoai?u.
A o?aoueae aeaaa i?eaaaeaiu ?acoeueoaou enneaaeiaaiey aeeyiey eiiiie
neeu ia a?aaeoe?iai/iua oa?aeoa?enoeee aieiinaeaeoeaiuo yeaeo?iaeia. A
?acaaaeaiiuo ?anoai?ao i?aiaeaaeaao aeeyiea eiiiie n?aaeu ia
aeeoooceiiiue iioaioeeae, a aieaa eiioeaio?e?iaaiiuo (auoa
10-2 iieue/e) – eciaiaiea eiyooeoeeaioa aeoeaiinoe
iioaioeeaeii?aaeaeythuaai eiia. Eiee/anoaaiiia iienaiea ioeeeea
aieiinaeaeoeaiuo yeaeo?iaeia auei iieo/aii ia iniiaa o?aaiaiey
E = E( – (k +b2)lg {c(A)+ b1} – k (b3 I1/3 + b4 I),
aaea b1 —yiie?e/aneee ia?aiao?, oa?aeoa?ecothuee aeeaae a iauoth
eiioeaio?aoeeth iioaioeeaeii?aaeaeythuaai eiia A, nicaeaaaaiue
?anoai?aieai iaia?aiu eee aeani?aoeeae eiiia n aa iiaa?oiinoe;
b2 –ia?aiao?, oa?aeoa?ecothuee eciaiaiea aeeoooceiiiiai iioaioeeaea; b3
? b2 –ia?aiao?u yiie?e/aneie caaeneiinoe eiyooeoeeaioia aeoeaiinoe
aieiia io eiiiie neeu: lg ((A) = b3 I1/3 + b4 I.
I?eaaaeaiu cia/aiey ia?aiao?ia aeey 12 nenoai (aieiiu NO3-, ClO4-, BF4-,
DS-). Aeey aieiia BF4- enneaaeiaaia oaiia?aoo?iay caaeneiinoue
eiyooeoeeaioia aeoeaiinoe: iia i?ioiaeeo /a?ac ieieioi i?e 25 (N, aeae
caaeneiinoe lg ((BF4-) iaeeiaeia aeey anaai enneaaeiaaiiiai aeeaiaciia
eiiiie neeu. Aieii DS- eiaao aieaa aunieea cia/aiey eiyooeoeeaioa
aeoeaiinoe, /ai iai?aaie/aneea aieiiu: i?e eiioeaio?aoeee NaCl auoa 0,6
iieue/e cia/aiey ((DS-) aieueoa 1. Iieo/aiiua ?acoeueoaou iaania/eaatho
a?aaeoe?iaeo aieiinaeaeoeaiuo yeaeo?iaeia ii oeaea aeoeaiinoae.
A /aoaa?oie aeaaa i?eaaaeaiu ?acoeueoaou nenoaiaoe/aneiai enneaaeiaaiey
naeaeoeaiinoe aieiinaeaeoeaiuo yeaeo?iaeia na?eeiiai auionea e
?anniio?aiu aiciiaeiinoe iaeiia?aiaiiiai ii?aaeaeaiey aeaoo eiiiiiaioia
n iiiiuueth ioeueoeyeaeo?iaeiie nenoaiu. Iieacaii, /oi iaaeaaeioth
oa?aeoa?enoeeo naeaeoeaiinoe ENY iiaeii iieo/eoue a oneiaeyo, eiaaea
ioeeiiaiey a?aaeoe?iai/iie oa?aeoa?enoeee, iaoneiaeaiiua iaoathuei
aeeyieai eiiia-eiieo?aioia, i?aauoaao 10 iA. Enneaaeiaaiu iia?aoiinoe
iaeiia?aiaiiiai ii?aaeaeaiey aeaoo eiiiiiaioia n iiiiuueth nenoaiu
iaeiioeiiuo ENY. I?eaaaeaiu caaeneiinoe iia?aoiinoae io ia?aiaiiuo
x = K2Pot / K1Pot, y = K1Pot cB / cA (K1Pot – iaiueoee ec aeaoo
eiyooeoeeaioia naeaeoeaiinoe), /oi iaeaa/aao auai? oneiaee
iaeiia?aiaiiiai ii?aaeaeaiey. Iieo/aiu iaiauaiiua oa?aeoa?enoeee
aiciiaeiinoae iaeiia?aiaiiiai ii?aaeaeaiey aeaoo aieiiia (niioiioaiea
eiioeaio?aoeee, iia?aoiinoe ?acoeueoaoia). Iieacaii, /oi aeey
iaeiia?aiaiiiai ii?aaeaeaiey iiaeii eniieueciaaoue aeaa iaeiioeiiuo ENY,
eiyooeoeeaiou naeaeoeaiinoe eioi?uo ?acee/athony ia iaiaa /ai a 4 ?aca.
A iyoie aeaaa i?eaaaeaii iao?ieiae/aneia iainiiaaiea ?ac?aaioaiiuo
iaoiaeee iioaioeeiiao?e/aneiai ii?aaeaeaiey aieiiia a eiie?aoiuo
iauaeoao aiaeeca.
Eeth/aaua neiaa: aieiinaeaeoeaiua yeaeo?iaeu, ieo?ao, ia?oei?ao,
oao?aooi?iai?ao, aeiaeaoeeenoeueoao, eiyooeoeeaiou aeoeaiinoe,
eiyooeoeeaiou naeaeoeaiinoe, iaeiia?aiaiiia ii?aaeaeaiea.
Maslij O.G. The background ionic effect on the response of the anion
selective membrane electrodes. – Manuscript.
Thesis for a nandidate of chemical science degree by speciality
02.00.02 – analytical chemistry. – Kharkiv State University, Kharkiv,
1999.
The dissertation has been devoted the development of metrological
foundation of measurements with anionic selective membrane electrodes.
Quantitative description of ionic interference on the ISE response (the
ionic strength effect, the interfering anion effect, change of chemical
form of main anions) was found. The models of activity coefficients of
NO3-, ClO4-, BF4- and dodecyl sulfate have been developed. For the first
time it was suggested the criterions of electrode choice for
multi-electrode systems. The characteristics of possibilities of
simultaneous determination of two components (concentration ranges,
standard deviation) were generalized.
Key words: anion selective electrodes, nitrate, perchlorate,
tetrafluoroborate, dodecyl sulfate, activity coefficients, selectivity
coefficients, simultaneous determination.
y = 0,6
/ c
c
s
x
1
2
35
30
25
20
15
10
5
8
6
4
2
0
2
/c, %
c
s
y
x=4
1
3
4
100
80
60
40
20
0
2.0
1.5
1.0
0.5
0.0
D?
A,B
/K
A,B
K
s
1.0
0.8
0.6
0.4
0.2
0.0
100
80
60
40
20
0
oeiaeaaeUaae
0.0
0.2
0.4
0.6
0.8
1.0
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
0.1
4
3
2
1
lg
g?
E(, B
)
-
4
c(BF
1
2
0.10
0.09
0.08
-0.01
-0.02
0.10
0.08
0.06
0.04
0.02
0.00
(DS)
-
I
II
0.22
0.21
0.20
0.19
0.18
0.17
-3.4
-3.6
-3.8
-4.0
-4.2
-4.4
-4.6
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