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Розчинність і сольватація перхлоратів лужних металів та тетраалкіламонію у змішаних розчинниках вода – диполярний апротонний розчинник: Автореф. дис..

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OoOAeA?AEAAIEE OI?AA?NEOAO

Ia i?aaao ?oeiieno

IAE OAOssIA A?EAI??AIA

OAeE 541.8

?ic/eii?noue ? nieueaaoaoe?y ia?oei?ao?a eoaeieo iaoae?a oa
oao?aaee?eaiii?th o ci?oaieo ?ic/eiieeao aiaea – aeeiiey?iee ai?ioiiiee
?ic/eiiee

niaoe?aeuei?noue 02.00.04 – o?ce/ia o?i?y

AAOI?AOA?AO

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?i?/ieo iaoe

Oa?e?a 1999

Aeena?oaoe?y ? ?oeiien

?iaioo aeeiiaii a Oe?a?inuee?e ?iaeaia?ii-iaaeaaia?/i?e aeaaeai??

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

Aacoaeee Aaneeue
Aeaieeiae/,

Oe?a?inueea
?iaeaia?ii-iaaeaaia?/ia

aeaaeai?y,
i?ioani? eaoaae?e o?i?? ?

o?i?/ii?
oaoiieia??

Io?oe?ei? iiiiaioe aeieoi? o?i?/ieo iaoe, i?ioani?

Aeaie Aa?ai
Ai?eniae/,

Oa?e?anueeee
aea?aeaaiee oi?aa?neoao,

caa?aeoaa/
eaoaae?e ooieoe?iiaeueieo iaoa??ae?a

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

Aoeaa?i A?eoi?
?aaiiae/,

Oa?e?anueeee
aea?aeaaiee iie?oaoi?/iee

oi?aa?neoao,
caa?aeoaa/ eaoaae?e caaaeueii?

? iai?aai?/ii?
o?i??

I?ia?aeia onoaiiaa Iaoe?iiaeueiee oaoi?/iee
oi?aa?neoao Oe?a?ie

“Ee?anueeee
iie?oaoi?/iee ?inoeooo”

eaoaae?a o?ce/ii? ?
eiei?aeii? o?i??, i. Ee?a

Caoeno a?aeaoaeaoueny “27” o?aaiy 1999 ?. i 14-00 aiaeei? ia can?aeaii?
niaoe?ae?ciaaii? a/aii? ?aaee Ae 64.051.14 Oa?e?anueeiai aea?aeaaiiai
oi?aa?neoaoo (310077, i. Oa?e?a, iaeae. Naiaiaee, 4, aoae. 7-80)

C aeena?oaoe??th iiaeia iciaeiieoeny a Oeaio?aeuei?e iaoeia?e
a?ae?ioaoe? OAeO

Aaoi?aoa?ao ?ic?neaii “26” ea?oiy 1999 ?.

A/aiee nae?aoa? niaoe?ae?ciaaii? ?aaee

eaiaeeaeao o?i?/ieo iaoe, aeioeaio
Eia?iiaa E.I.

Caaaeueia oa?aeoa?enoeea ?iaioe

Aeooaeuei?noue ?iaioe: C aaeeeiai ia?ae?eo o?i?/ieo ? o?ceei-o?i?/ieo
aeanoeainoae ?ic/ei?a oa i?ioean?a, ui a ieo a?aeaoaathoueny, i?ia?aeia
?ieue iaeaaeeoue nieueaaoaoe?? ?ic/eiaieo ?a/iaei. Oea iaeei c
iaeaaaeeea?oeo oaeoi??a, yeee aieeaa? ia ?ic/eii?noue aeaeo?ie?o?a.

E?euee?nia oai??y ?ic/eiiino? a?aeiineoueny aei iaeiaio aeine?aeaeaieo
?icae?e?a caaaeueii? oai??? ?ic/ei?a, ia caaaeath/e ia aaeeeee ianya
iaeiie/aiiai i?aeoe/iiai iaoa??aeo a oe?e aaeoc?. Nenoaiaoe/ia
aeine?aeaeaiiy nieueaaoaoe?? aeaeo?ie?o?a a ??ciiiai?oieo ?ic/eiieeao ye
?iaeea?aeoaeueieo, oae ? ci?oaieo, ? iaeiei c oeyo?a ia?aaeaa/aiiy
aaee/ei ?o ?ic/eiiino?.

C i?iaeaiith nieueaaoaoe?? aeaeo?ie?o?a o?nii iia`ycai? ieoaiiy aoaeiae
? no?oeoo?e ?ic/eiiee?a oa ?ic/ei?a ia ?o iniia?. E?euee?ni?
oa?aeoa?enoeee nieueaaoaoe?? ( aia?a?y A?aana, aioaeuei?y oa aio?ii?y
nieueaaoaoe?? ( ? ooiaeaiaioaeueieie oa?iiaeeiai?/ieie e?euee?nieie
aaee/eiaie, ui a?aeia?aaeothoue aieea i?e?iaee ?ic/eiaii? ?a/iaeie, ??
eiioeaio?aoe??, i?e?iaee ?ic/eiieea ? eiai no?oeoo?e ia caaaeuei?
aeanoeaino? ?ic/ei?a. *a?ac oa oeueiio ieoaiith i?eae?ey?oueny aaeeea
oaaaa ye iaeaeooaeuei?oiio a caaaeuei?e oai??? ?ic/ei?a.

?iaioa ? i?iaeiaaeaiiyi aeine?aeaeaiue ?ic/eiiino? aeaeo?ie?o?a o
aiaeii-nie?oiaeo nenoaiao, ui aeeiioaaeeny ia eaoaae?? caaaeueii? o?i??
? o?i?/ii? oaoiieia?? Oe?a?inueei? ?iaeaia?ii-iaaeaaia?/ii? aeaaeai??.

Iaoa ?iaioe: anoaiiaeaiiy caeiiii??iinoae aieeao i?e?iaee ? neeaaeo
?ic/eiieea, i?e?iaee ? ?ici??o ?ii?a, a oaeiae oaiia?aoo?e ia
?ic/eii?noue ? nieueaaoaoe?th ia?oei?ao?a eoaeieo iaoae?a ?
oao?aaee?eaiii?th o aeeiiey?ieo ai?ioiiieo ?ic/eiieeao (AeA?) oa ?o
aiaeieo noi?oao.

A caaea/o aeine?aeaeaiiy aoiaeeei:

Aenia?eiaioaeueia aeine?aeaeaiiy:

-?ic/eiiino? ia?oei?ao?a eae?th (KClO4), ?oa?ae?th (RbClO4), oeac?th
(CsClO4), oao?aiaoee- (Me4NClO4) ? oao?aaoeeaiii?th (Et4NClO4) a
nenoaiao ci?oaieo ?ic/eiiee?a aiaea-AeA?, aea AeA? — aoeaoii (AI),
iaoeeaoeeeaoii (IAE), aeeiaoeeoi?iai?ae (AeIO), aeeiaoeenoeueoieneae
(AeINI) ? aoeaoii?o?ee (AI) i?e 298.15 E;

-?ic/eiiino? KClO4 ? Me4NClO4 a ci?oaiiio ?ic/eiieeo aiaea-AI i?e
oaiia?aoo?ao 288.15, 293.15, 298.15, 303.15, 308.15E.

Aecia/aiiy:

-aaee/ei noaiaea?oieo aia?a?e A?aana ia?aiino aeaeo?ie?o?a c aiaee a AI,
IAE, AeIO, AeINI, AI oa ?o aiaei? noi?o?;

-oa?iiaeeiai?/ieo oa?aeoa?enoee ia?aiino KClO4 ? Me4NClO4 c aiaee a AI
oa eiai aiaei? noi?o? ia anueiio ?ioa?aae? neeaae?a ci?oaiiai ?ic/eiieea
i?e 288.15-308.15E.

Iaoeiaa iiaecia:

– aia?oa i?iaaaeaii nenoaiaoe/ia aeine?aeaeaiiy ?ic/eiiino? KClO4,
RbClO4, CsClO4, Me4NClO4 ? Et4NClO4 a ci?oaieo ?ic/eiieeao aiaea-AeA?
(AeA? – AI, IAE, AeIO, AeINI, AI) ia anueiio ?ioa?aae? neeaae?a noi?o?
i?e 298.15 E, a oaeiae aeine?aeaeaii oaiia?aoo?io caeaaei?noue
?ic/eiiino? ia?oei?ao?a eae?th ? oao?aiaoeeaiii?th a ci?oaiiio
?ic/eiieeo aiaea-aoeaoii?o?ee i?e 288.15 – 308.15 E;

– a ?iaio? aia?oa aecia/aii aeiaooee ?ic/eiiino? KClO4, RbClO4, CsClO4,
Me4NClO4 ? Et4NClO4 a ci?oaieo ?ic/eiieeao aiaea-AeA? (AeA? – AI, IAE,
AeIO, AeINI, AI) ia anueiio ?ioa?aae? neeaae?a i?e 298.15 E;

– aecia/aii oa?iiaeeiai?/i? oa?aeoa?enoeee ia?aiino KClO4 ? Me4NClO4 o
aiaeii-aoeaoii?o?eeueieo ?ic/eiieeao i?e 288.15-308.15 E

– aia?oa iaaaaeaia e?euee?nia ioe?iea aia?a?e ooai?aiiy ii?iaeieie aeey
aaeeeeo ca ?ici??ii oao?aaee?eaiii?eieo ?ii?a ia iniia? oa?iiaeeiai?/ieo
oa?aeoa?enoee ia?aiino aeaeo?ie?o?a;

– aeiaaaeaii, ui aia?a?y ooai?aiiy ii?iaeieie caeaaeeoue a?ae
iiaa?oiaaeo aeanoeainoae ci?oaiiai ?ic/eiieea.

I?aeoe/ia cia/aiiy: Aenia?eiaioaeuei? cia/aiiy ?ic/eiiino? ? aeiaooe?a
?ic/eiiino? aeine?aeaeaieo aeaeo?ie?o?a a ci?oaieo ?ic/eiieeao iathoue
naiino?eio oe?ii?noue ye aeia?aeeia? aeai?.

Iaaaaeai? a ?iaio? oa?iiaeeiai?/i? aaee/eie ia?aiino aeaeo?ie?o?a i?ae
?ic/eiieeaie oa aeyaeai? caeiiii??iino? aeathoue iiaeeea?noue
ia?aaeaa/aoe ?ic/eii?noue aeaeo?ie?o?a, ?o iiaaae?ieo a oiio /e ?ioiio
AeA? ? iiaeooue aooe aeei?enoai? i?e ia/eneaii? ??aiiaaa o ?ic/eiao.

Ia caoeno aeiinyoueny oae? iniiai? iieiaeaiiy:

1. Iaa?oiooaaiiy caeaaeiinoae :

– ?ic/eiiino? ? noaiaea?oieo aia?a?e A?aana ia?aiino aeine?aeaeaieo
aeaeo?ie?o?a a?ae neeaaeo ci?oaiiai ?ic/eiieea aiaea-AeA?.

– ?ic/eiiino? oa oa?iiaeeiai?/ieo aaee/ei ia?aiino a?ae neeaaeo
ci?oaiiai ?ic/eiieea aiaea-AeA? ? a?ae oaiia?aoo?e aeey nenoai
KClO4-aiaea-AI ? Me4NClO4-aiaea-AI.

2. ?ioa?i?aoaoe?y aieeao aia?a?? ooai?aiiy ii?iaeieie (G(tr( ia
nieueaaoaoe?th oao?aaee?eaiii?eieo ?ii?a. Caeaaei?noue (G(tr( a?ae
iiaa?oiaaiai iaoyao ci?oaiiai ?ic/eiieea.

Caeaaeiino? aia?a?? A?aana ia?aiino a?ae ?ici???a ?ii?a aeaeo?ie?o?a oa
?ic/eiiino? a?ae ae?aeaeo?e/ii? i?iieeiino? ?ic/eiieea.

Iniaenoee aianie aaoi?a iieyaa? a i?iaaaeaii? aenia?eiaioo oa io?eiaii?
iaoeiaeo ?acoeueoao?a, ?o iaoaiaoe/i?e ia?iaoe?, oi?ioethaaii? aeniiae?a
oa ocaaaeueiaiue. A ?iaio?, yeo iioae?eiaaii o ni?aaaoi?noa? c ?o?iiaei
I.A. iniaenoee aianie aaoi?a iieyaa? a i?iaaaeaii? aenia?eiaioo oa
aecia/aii? aeaieo c eiinoaio anioe?aoe??.

Ai?iaaoe?y ?iaioe: Ie?ai? /anoeie aeena?oaoe?eii? ?iaioe aoei
i?aaenoaaeaii ia Anaoe?a?inuee?e iaoeiai-iaoiaee/i?e eiioa?aioe?? c
i?e?iaeie/eo iaoe “5-o? Ea?eoeinuee? /eoaiiy” (Iieoaaa, 20-22 o?aaiy
1998 ?.)

Ioae?eaoe??: Ca oaiith aeena?oaoe?? iioae?eiaaii 5 ?ia?o a oe?a?inueeeo
oa ca?oa?aeieo aeaaeai?/ieo aeaeaiiyo, a oaeiae oace iaoa??ae?a
eiioa?aioe??.

No?oeoo?a oa ianya ?iaioe: Aeena?oaoe?y neeaaea?oueny ?c anooio, o?ueio
aeaa, i?aenoie?a ?iaioe, nieneo e?oa?aoo?e oa aeiaeaoeo. Aeeeaaeaia ia
146 noi??ieao iaoeiiieniiai oaenoo, i?noeoue 10 oaaeeoeue oa 21
iaethiie. A?ae?ia?ao?y ia?aoiao? 160 iaeiaioaaiue.

Iniiaiee ci?no ?iaioe.

O anooi? iaa?oioiaaii aeooaeuei?noue ?iaioe, noi?ioeueiaaii iniiaio iaoo
oa caaea/? aeine?aeaeaiiy, iieacaia iaoeiaa iiaecia ? i?aeoe/ia
oe?ii?noue ?iaioe.

A ia?o?e aeaa? ?icaeyiooi aieiai? oa?aeoa?enoeee ?ic/eiiino?, aeiaooeo
?ic/eiiino? oa nieueaaoaoe?? aeaeo?ie?o?a. Iaaaaeaii iaeyae e?oa?aoo?e,
i?enay/aiee ??ciei iaoiaeai aecia/aiiy aeiaooe?a ?ic/eiiino? oa aia?a?e
A?aana ia?aiino aeaeo?ie?o?a i?ae ?ic/eiieeaie. Iiaeaii aeanoeaino? oa
no?oeoo?i? oa?aeoa?enoeee ??aeeeo ai?ioiiieo ?ic/eiiee?a AI, IAE, AeIO,
AeINI, AI oa ?o aiaeieo noi?oae.

A ae?oa?e aeaa? iaaaaeaii iien aenia?eiaioaeueii? /anoeie aeena?oaoe??.
Iienaii iaoiaee io?eiaiiy oa i/enoee ia`?eo?a aeine?aeaeaiiy ? iaoiaeeea
aecia/aiiy ?ic/eiiino? aeaeo?ie?o?a oa caniae ia?iaee
aenia?eiaioaeueieo aeaieo.

Aaee/eio ?ic/eiiino? ia/enethaaee ca ??aiyiiyi:

m (1000

N = ((( ,

(1)

M ( V

aea m – iana nie?, yea caeeoeeanue i?ney aeia?thaaiiy ?ic/eiieea o
i?ia?, I – iiey?ia iana nie?, V – ia`?i i?iae a ie.

Aeiaooie ?ic/eiiino? Esp ciaoiaeeee ca ??aiyiiyi:

ESP=(C(Y((( )2,
(2)

aea ( ( nooi?iue aeenioe?aoe??, Y – na?aaeiuei?iiee eiao?oe??io
aeoeaiino? aeaeo?ie?oo, ia/eneaiee ca ??aiyiiyi Aeaa?n. Nooi?iue
aeenioe?aoe?? aoei ia/eneaii ca iaoiaeii iine?aeiaiiai iaaeeaeaiiy,
a?aoiaoth/e eiinoaioo aeenioe?aoe??, yeo aoei io?eiaii c
eiiaeoeoiiao?e/ieo aeine?aeaeaiue iaoeo nenoai ? ia/eneaii ca i?ia?aiith
aeioeaioa eaoaae?e iai?aai?/ii? o?i?? OAeO Eaeoa?ia I.I.

Noaiaea?oio aia?a?th A?aana ia?aiino aeaeo?ie?o?a c aiaee a AeA? oa ?o
noi?o? (G(tr ia/enethaaee ca ??aiyiiyi:

(G(tr=2.3(RT(lg(KSPW/KSPS),
(3)

aea Espw ? Esps – aeiaooee ?ic/eiiino? aeaeo?ie?o?a o aiae? oa
ci?oaieo ?ic/eiieeao a?aeiia?aeii.

Iaaaaeaii caniae ioe?iee iioeaie aenia?eiaioaeueieo aeaieo, a oaeiae
noia?i? iioeaee. Iioeaee aecia/aiiy ?ic/eiiino? aeaeo?ie?o?a ia
ia?aaeuoaaee 2-3%.

O?aoy aeaaa i?enay/aia aiae?co ?acoeueoao?a aenia?eiaioo,
iaa?oiooaaiith aeniiae?a, ye? i?noyoueny a aeena?oaoe?ei?e ?iaio?.

?ic/eii?noue ? nieueaaoaoe?y KClO4, RbClO4, CsClO4, Me4NClO4 ? Et4NClO4
a ci?oaieo ?ic/eiieeao aiaea-AeA? i?e 298.15 E.

?ic/eii?noue ia?oei?ao?a eoaeieo iaoae?a ? oao?aaee?eaiii?th a
ci?oaieo ?ic/eiieeao aiaea-AeA? i?e 298.15 E i?eaaaeaia o oaaeeoe? 1.

Oaaeeoey 1

?ic/eii?noue (N) KClO4, RbClO4, CsClO4, Me4NClO4 ? Et4NClO4 a ci?oaieo
?ic/eiieeao aiaea-AeA? i?e 298.15 E

ia.% AeA? N, iieue/e

KClO4 RbClO4 CsClO4 Me4NClO4 Et4NClO4

1 2 3 4 5 6

aiaea-AI

0 0,1458 0,0704 0,0828 0,0737 0,2137

10 0,1465 0,0700 0,0862 0,0821 0,2913

20 0,1480 0,0746 0,0908 0,0939 0,4197

30 0,1646 0,0818 0,1016 0,1169 0,6869

40 0,1819 0,0897 0,1110 0,1423 0,9273

50 0,1884 0,0934 0,1165 0,1509 101145

60 0,1862 0,0895 0,1149 0,1521 0,9961

70 0,1660 0,0780 0,0983 0,1354 1,0144

80 0,1292 0,0567 0,0745 0,1014 0,9099

I?iaeiaaeaiiy oaaeeoe? 1

1 2 3 4 5 6

90 0,0644 0,0284 0,0361 0,0442 0,5834

100 0,0102 0,0038 0,0051 0,0076 0,1532

aiaea-IAE

10 0,1436 0,0699 0,0856 0,0847 0,3091

20 0,1451 0,0735 0,0923 0,0962 0,4406

30 0,1588 0,0791 0,1006 0,1204 0,5943

90 0,0414 0,0161 0,0232 0,0324 0,5452

95 0,0238 0,0058 0,0070 0,0183 0,2952

100 0,0060 0,0012 0,0011 0,0065 0,0888

aiaea-AeIO

10 0,1545 0,0728 0,0894 0,0833 0,2848

20 0,1630 0,0773 0,0980 0,0949 0,3852

30 0,1857 0,0892 0,1121 0,1131 0,4788

50 0,2410 0,1169 0,1495 0,1497 0,6963

70 0,3498 0,1652 0,2067 0,1824 0,8392

90 0,6794 0,3067 0,3516 0,1914 0,9401

100 0,8883 0,3930 0,4104 0,1390 0,9640

aiaea-AeINI

10 0,1483 0,0701 0,0861 0,0761 0,2728

30 0,1569 0,0751 0,0953 0,0913 0,3713

50 0,1969 0,0950 0,1248 0,1123 0,4769

70 0,3894 0,1842 0,2307 0,1592 0,6010

90 1,4141 0,6861 0,8138 0,2692 0,8491

100 2,5752 1,3199 1,4418 0,3434 1,7180

aiaea-AI

10 0,1676 0,0793 0,0984 0,0949 0,3549

30 0,2213 0,1150 0,1434 0,1680 0,9604

50 0,2357 0,1219 0,1611 0,2379 1,4965

70 0,1887 0,0993 0,1343 0,2451 1,7707

90 0,0784 0,0447 0,0634 0,1510 1,7321

100 0,0151 0,0088 0,0151 0,0661 1,1140

Iae.1 Caeaaei?noue ?ic/eiiino? KClO4 ? Et4NClO4 a?ae neeaaeo ci?oaiiai
?ic/eiieea aiaea – AeA? i?e 298.15 E: 1 – AI, 2 – AI, 3 – AeIO, 4 –
AeINI

O aiaeii-eaoiiiaeo ?ic/eiieeao ia?oei?aoe eoaeieo iaoae?a iathoue
aeecuee? cia/aiiy ?ic/eiiino? ye o aiaeii-aoeaoiiiaeo noi?oao, oae ? o
aiaeii-iaoeeaoeeeaoiiiaeo. E??i oiai, ?ic/eiiino? on?o aeine?aeaeaieo
aeaeo?ie?o?a a nenoai? aiaea-AI i?aeoe/ii ni?aiaaeathoue c aaee/eiaie
?ic/eiiino? a nenoai? aiaea-IAE, ui na?ae/eoue i?i iaaaeeeo ??cieoeth o
aeanoeainoyo oeeo ?ic/eiiee?a iaeiiai aiiieia?/iiai ?yaeo. Caeaaeiino?
?ic/eiiino? a?ae neeaaeo ci?oaiiai ?ic/eiieea iiaeia iiae?eeoe ia aeaa
oeie. Aei ia?oiai a?aeiinyoueny caeaaeiino? o aiaeii-eaoiiiaeo oa
aiaeii-aoeaoii?o?eeueieo ?ic/eiieeao, aei ae?oaiai ( o nenoaiao
aiaea-AeIO ? aiaea-AeINI. O ia?oiio aeiaaeeo caeaaeiino? ?ic/eiiino?
a?ae neeaaeo iathoue aeno?aioi ( iaeneioi ?ic/eiiino? ye aeey
ia?oei?ao?a eoaeieo iaoae?a, oae ? aeey oao?aaee?eaiii??aeo nieae. O
ae?oaiio aeiaaeeo ?ic/eiiino? iinooiiai c?inoathoue c? ca?eueoaiiyi
ai?noo iaaiaeiiai eiiiiiaioo noi?o? aeey an?o aeine?aeaeaieo ia?oei?ao?a
(iae.1).

?ic/eii?noue ia?oei?ao?a eoaeieo iaoae?a ??cei c?inoa? a nenoaiao c AeIO
? AeINI a iaeano? neeaaeo 70-100 ia. % (35-100 iie. %), ui, nei??oa ca
ana, iia`ycaii c ooai?aiiyi e?enoaeinieueaao?a. Iaeiae aeyaeoe ?o
i?enooi?noue iai ia aaeaeiny, oiio ui aiie iathoue no?eeo oi?io eeoa a
?ic/ei?.

Ci?ithaaiiy ?ic/eiiino? aeine?aeaeaieo ia?oei?ao?a c? ci?ithaaiiyi
neeaaeo ci?oaiiai ?ic/eiieea iaoiiaeaii ci?ithaaiiyi noaiaea?oieo
aia?a?e A?aana ia?aiino aeaeo?ie?o?a (G(tr, yeeo aoei ia/eneaii ca
??aiyiiyi (3) (oaae.2).

Oaaeeoey 2

Noaiaea?oi? aia?a?? A?aana ia?aiino (G(tr aeaeo?ie?o?a c aiaee o AeA? oa
?o aiaei? noi?o? i?e 298.15 E

ia.% AeA? (G(tr, eAeae/iieue

KClO4 RbClO4 CsClO4 Me4NClO4 Et4NClO4

1 2 3 4 5 6

aiaea-AI

0 0 0 0 0 0

10 0,11 0,14 -0,07 -0,43 -1,32

20 0,20 -0,05 -0,19 -0,88 -2,95

30 -0,11 -0,32 -0,54 -1,71 -5,36

40 -0,245 -0,46 -0,65 -2,29 -6,83

50 -0,08 -0,37 -0,58 -2,25 -7,81

60 0,56 0,30 0,01 -1,71 -6,50

70 1,83 1,51 1,34 -0,48 -6,04

80 3,75 3,47 3,20 1,52 -4,36

90 9,11 7,60 7,44 5,69 0,41

100 16,89 16,76 16,53 14,70 10,29

aiaea-IAE

0 0 0 0 0 0

10 0,25 0,17 0,01 -0,49 -1,56

20 0,41 0,11 -0,17 -0,89 -3,06

30 0,27 0,01 -0,31 -1,64 -4,32

90 10,15 9,84 9,36 7,75 5,11

95 12,81 14,07 13,90 10,44 7,70

100 18,06 20,82 21,82 14,67 13,29

aiaea-AeIO

0 0 0 0 0 0

10 -0,16 -0,06 -0,26 -0,47 -1,23

20 -0,27 -0,22 -0,56 -0,95 -2,54

30 -0,70 -0,74 -1,03 -1,60 -3,46

50 -1,47 -1,58 -1,93 -2,47 -5,05

70 -2,49 -2,45 -2,67 -2,68 -5,53

I?iaeiaaeaiiy oaaeeoe? 2

1 2 3 4 5 6

aiaea-AeINI

0 0 0 0 0 0

10 -0,06 0,03 -0,17 -0,14 -1,13

30 -0,29 -0,26 -0,61 -0,96 -2,58

50 -1,26 -1,26 -1,77 -1,82 -3,74

70 -4,27 -4,11 -4,41 -3,24 -4,75

aiaea-AI

0 0 0 0 0 0

10 -0,36 -0,42 -0,63 -0,99 -2,28

30 -1,45 -2,12 -2,09 -3,36 -7,36

50 -1,26 -1,73 -2,19 -4,49 -10,13

70 0,62 -0,13 -0,59 -1,52 -11,41

90 6,08 4,72 4,35 0,60 -11,01

100 12,67 11,41 10,14 4,00 -6,22

Aia?a?? A?aana ia?aiino ia?oei?ao?a eoaeieo iaoae?a iathoue aeecuee?
aaee/eie aeey an?o aeine?aeaeaieo nenoai aiaea-AeA? a iaeano? neeaae?a
0-50 ia.% iaaiaeiiai eiiiiiaioo ? i?aeoe/ii ia caeaaeaoue a?ae eiai
i?e?iaee, ui na?ae/eoue i?i noaa?eueio no?oeoo?o aiaee aei 50 ia.% AeA?
(iae.2)

Oao?aaee?eaiii?ei? ?iie iathoue aaeee? ?ici??e, oiio aeey ieo cia/io
?ieue a ooai?aii? ?ic/ei?a a?ae?a?a? aia?a?y ooai?aiiy ii?iaeieie. I?e
oeueiio /ei a?eueoee ?aae?on ?iio, oei iaio? aaee/eie (G(tr. I?eaaaeai?
ia iaethieo 2 caeaaeiino? aia?a?e A?aana ia?aiino aeaeo?ie?o?a a?ae
neeaaeo ci?oaiiai ?ic/eiieea aiaea-AI ? aiaea-AI (aeey LiClO4, NaClO4,
Pr4NClO4, Bu4NClO4 i Ph4AsClO4 aeei?enoai? aeia?aeeia? aeai?)
i?aeoaa?aeaeothoue oeth caeiiii??i?noue. Ii??aithth/e caeaaeiino? (G(tr
aeey R4NClO4 a?ae neeaaeo ci?oaiiai ?ic/eiieea, iiaeia eiinoaooaaoe, ui
iie?ioaiiy nieueaaoaoe?? oao?aaee?eaiii?eieo ?ii?a ei?aeth? c aaee/eiith
iiaa?oiaaiai iaoyao i?aai?/ieo eiiiiiaio?a. A?aeiii, ui iiaa?oiaaee
iaoya ?ic/eiieea aecia/a? aia?a?th ooai?aiiy ii?iaeieie, yea aeey
noa?e/ieo oa inaaaeinoa?e/ieo ?ii?a iiaea aooe ia/eneaia ca ??aiyiiyi:

Aii?=4(r2(,
(4)

aea r – ?aae?on ?iia (ii?iaeieie), ( – iiaa?oiaaee iaoya.

(a)

Iae. 2 Caeaaeiino? (G(tr a?ae neeaaeo ci?oaiiai ?ic/eiieea aiaea-AI(a):
KClO4(1), RbClO4(2), CsClO4(3), Me4NClO4(4), Et4NClO4(5), Pr4NClO4(6),
Bu4NClO4(7); aiaea-AI(a): LiClO4(1), NaClO4(2), KClO4(3), RbClO4(4),
CsClO4(5), Me4NClO4(6), Et4NClO4(7) i Ph4AsClO4(8); aiaea-AeIO (a) ?
aiaea-AeINI (a): KClO4(1), RbClO4(2), CsClO4(3), Me4NClO4(4) ?
Et4NClO4(5).

A?aoiaoth/e, ui iiaaae?iea eao?ii?a eoaeieo iaoae?a ? oao?aee?eaiii?th
(ai?ii aeey an?o nieae iaeiaeiaee) a?ae??ciy?oueny eeoa aia?a??th
ooai?aiiy ii?iaeieie, a ?io? neeaaeia?, ui aoiaeyoue a aia?aaoeeo
nieueaaoaoe?? oeeo ?ii?a, iaei /ei a?ae??ciythoueny, aaee/eio aia?a??
ooai?aiiy ii?iaeieie iiaeia ia/eneeoe ca ??aiyiiyi:

(G(tr(=(G(tr(R4NClO4) – (G(tr(MClO4)
(5)

((103, I/i

(a)

((103, I/i

(a)

Ae?enii, caeaaeiino? (G(tr( a?ae ( iathoue e?i?eiee oa?aeoa? (iae.3)

Iae.3 Caeaaei?noue (G(tr a?ae iiaa?oiaaiai iaoyao ci?oaiiai ?ic/eiieea
(: a)aiaea-AI; a)aiaea-AeIO

Ia i?eeeaae? aiaeii-aoeaoii?o?eeueii? nenoaie aeine?aeaeaia caeaaei?noue
nieueaaoaoe?? ai?ii?a a?ae ?o ?ici??o (iae. 4a) aeey KCl, KBr, KI, KClO4
i KBPh4. Aaee/eie (G(tr aeey oeeo aeaeo?ie?o?a aoei ia/eneaii c
aeei?enoaiiyi iaoeo oa e?oa?aoo?ieo aeaieo. I?e/iio, ye ? aeey eao?ii?a,
ca?eueoaiiy ?aae?ono ai?ii?a ? oaeoi?ii, ui i?ecaiaeeoue aei iie?ioaiiy
nieueaaoaoe?? aeaeo?ie?o?a. Caeaaeiino? aaee/ei (G(tr aeaeo?ie?o?a c
aiaee a aoeaoii?o?ee a?ae aaee/eie, iaa?iaii? aei ?aae?ono ?ii?a, ia?
e?i?eiee oa?aeoa? ye aeey ai?ii?a, oae ? aeey eao?ii?a (iae. 4a).

Nieueaaoaoe?y aeine?aeaeaieo aeaeo?ie?o?a a nenoaiao aiaea-AeIO ?
aiaea-AeINI ia? iiae?aiee oa?aeoa?. O ca`yceo c aaeeeith ?ic/eii?noth
nieae a oeeo ?ic/eiieeao aia?a?? A?aana ia?aiino i?eaaaeai? aei 70 ia.%
iaaiaeiiai eiiiiiaioo. A oeeo ?ic/eiieeao, ye ? o
aiaeii-aoeaoii?o?eeueieo, nieueaaoaoe?y ia?oei?ao?a iie?ioo?oueny c
?inoii ?aae?ono ?ii?a, a oaeiae c? ca?eueoaiiyi ai?noo iaaiaeiiai
eiiiiiaioo. Ii??aiyiiy ?ic/eiiino? aeaeo?ie?o?a a ?iaeea?aeoaeueieo
i?aai?/ieo ?ic/eiieeao aeicaieeei anoaiiaeoe, ui aeey aeine?aeaeaieo
iaie

(a)

1/r (109, i-1

(a)

Iae. 4 Caeaaeiino? (G(tr a) a?ae neeaaeo ci?oaiiai ?ic/eiieea aiaea-AI
aeey KCl(1), KBr(2), KI(3), KClO4(4) i KBPh4(5); a) a?ae aaee/eie,
iaa?iaii? aei ?aae?ono ?ii?a: 1-eao?ii?a, 2-ai?ii?a.

ia`?eo?a niinoa??aa?oueny e?i?eia caeaaei?noue eiaa?eoio ?ic/eiiino?
a?ae aaee/eie, iaa?iaii? aei ae?aeaeo?e/ii? i?iieeiino?. Ioaea, iiaeia
c?iaeoe aeniiaee, ui iae? aeiaaaee aeeiiey?ieo ai?ioiiieo ?ic/eiiee?a
iie?ioothoue nieueaaoaoe?th aeine?aeaeaieo ia?oei?ao?a. I?e/iio,
ca?eueoaiiy ?ici???a ?ii?a (ye eao?ii?a, oae ? ai?ii?a) ? oaeoi?ii, ui
ciaioo? aia?a?th A?aana ia?aiino aeaeo?ie?o?a c aiaee o aiaeii-i?aai?/i?
?ic/eiieee, a ae?aeaeo?e/ia i?iieei?noue iiaea neoaeeoe oa?aeoa?enoeeith
nieueaaooth/i? cae?aiino? ?ic/eiiee?a. Oaeiae a ?iaio? iaaaaeaii
oa?aeoa?enoeeo i?ioeano nieueaaoaoe?? c iiceoe?e aiii- ?
aaoa?inieueaaoaoe?? ?ii?a a aeine?aeaeaieo ci?oaieo ?ic/eiieeao.

Oa?iiaeeiai?ea ia?aiino KClO4 i Me4NClO4 c aiaee o
aiaeii-aoeaoii?o?eeuei? ?ic/eiieee i?e ??cieo oaiia?aoo?ao.

I?iaaaeaii aeine?aeaeaiiy oaiia?aoo?ii? caeaaeiino? ?ic/eiiino? a?ae
neeaaeo ci?oaiiai ?ic/eiieea aiaea-AI i?e 288.15, 293.15, 298.15,
303.15, 308.15 E. Ia iniia? oeeo aeaieo ia/eneaii (G(tr, a iio?i (I(tr i
(S(tr ca ??aiyiiyie:

-(S(tr=(((G(tr/(T)P, (H(tr=(G(tr+T(S(tr
(6)

?ic/eii?noue aeaeo?ie?o?a e?i?eii c?inoa?, a nieueaaoaoe?y ciaioo?oueny
c? ca?eueoaiiyi oaiia?aoo?e aeey an?o neeaae?a ci?oaiiai ?ic/eiieea.
Caeaaeiino? (H(tr ? O(S(tr a?ae neeaaeo noi?o? aeey KClO4 i Me4NClO4
iathoue neeaaeiee oa?aeoa?: i?e ai?no? 90 ia. % (~75 iie. %) AI ia oeeo
oa?iiaeeiai?/ieo ooieoe?yo i?enooi?e iaeneioi (iae.5), yeee iinooiiai
cieea? c ?inoii oaiia?aoo?e.

(a)

(a)

Iae.5 Caeaaeiino? Y((H(tr ? -T(S(tr) a?ae neeaaeo ci?oaiiai
?ic/eiieea aiaea-AI aeey KClO4(a) i Me4NClO4(a) i?e oaiia?aoo?ao
288.15(1), 293.15(2), 298.15(3), 303.15(4), 308.15(5).

Caeaaeiino? (G(tr aeey KClO4 i Me4NClO4 a?ae neeaaeo noi?o? ci?oaiiai
?ic/eiieea i?e ??cieo oaiia?aoo?ao iathoue iaeiaeiaee oa?aeoa? ?
a?ae??ciythoueny eeoa e?euee?nieie aaee/eiaie aia?a?e A?aana ia?aiino,
ye? c?inoathoue c? ca?eueoaiiyi oaiia?aoo?e. Oiaoi, ca?eueoaiiy
oaiia?aoo?e ? oei oaeoi?ii, yeee ciaioo? nieueaaoaoe?th aeaeo?ie?o?a.

I?e iaaaeeeiio ai?no? aoeaoii?o?eeo (0-12 iie.% aai 0-30 ia.%) aaee/eie
(G(tr aeey KClO4, a iniaeeai (G(tr aeey Me4NClO4 iaei ci?iththoueny i?e
ca?eueoaii? oaiia?aoo?e a?ae 293.15 aei 308.15 E. Oaeei /eiii o
aeine?aeaeaiiiio ?ioa?aae? oaiia?aoo? no?oeoo?a ci?oaiiai ?ic/eiieea c
iaaaeeeei ai?noii aoeaoii?o?eeo, aea iniiaiei eiiiiiaioii ? aiaea,
i?aeoe/ii ia ci?ith?oueny. I?e a?eueoeo aeiaaaeao iaaiaeiiai eiiiiiaioo
ca?eueoaiiy aia?a?e A?aana ia?aiino aeaeo?ie?o?a i?e ca?eueoaii?
oaiia?aoo?e noa? a?eueo cia/iei.

Acaaae? ia caeaaeiinoyo iiaeia aecia/eoe o?e iaeano? neeaae?a ci?oaiiai
?ic/eiieea: 0-50 ia.%, 50-90 ia.%, 90-100 ia.% AI, ui aeia?a
niinoa??aa?oueny i?e 303.15E oa 308.15E. Oae? iaeano? aeae?eythoue ? o
no?oeoo?? ci?oaiiai ?ic/eiieea aiaea-AI, eiaei?e c yeeo a?aeiia?aea?
a?eueo /e iaio noaa?eueia iieiaeaiiy. Oiae?, a?aieoe? iaeanoae
(aeno?aioie) ia caeaaeiinoyo (H(tr ? -T(S(tr aeey KClO4 oa Me4NClO4 a?ae
neeaaeo ci?oaiiai ?ic/eiieea aiaea-aoeaoii?o?ee na?ae/aoue i?i ia?ao?ae
iaei??? noaa?eueii? no?oeoo?e aei ae?oai? a oe?e nenoai?. I?e/iio,
nenoaia c oao?aaee?eaiii?eieie ?iiaie a?eueo /ooeeaa aei ci?i a
no?oeoo?? ?ic/eiieea, i?ae iaio? ca ?ici??ii eao?iie eoaeieo iaoae?a a
aeine?aeaeaiiio iaie ?ioa?aae? oaiia?aoo?.

Aeniiaee ?iaioe

1. Anoaiiaeaii caeiiii??iino? aieeao i?e?iaee ? neeaaeo ?ic/eiieea,
i?e?iaee ? ?ici??o ?ii?a, a oaeiae oaiia?aoo?e ia ?ic/eii?noue ?
nieueaaoaoe?th ia?oei?ao?a eoaeieo iaoae?a ? oao?aaee?eaiii?th o
aeeiiey?ieo ai?ioiiieo ?ic/eiieeao oa ?o aiaeieo noi?oao.

2. Aecia/aii ?ic/eiiino? ia?oei?ao?a eoaeieo iaoae?a ? oao?aaee?eaiii?th
a ci?oaieo ?ic/eiieeao aiaea-AeA? (AI, IAE, AeIO, AeINI, AI) ia anueiio
?ioa?aae? neeaae?a i?e 298.15 E, a oaeiae i?iaaaeaii oaiia?aoo?ia
aeine?aeaeaiiy ?ic/eiiino? ie?aieo nieae a aoeaoii?o?ee? oa ?o aiaeieo
noi?oao i?e 288.15- 308.15 E.

3. Ia/eneai? ? oaaoeueiaai? aeiaooee ?ic/eiiino?, noaiaea?oi? aia?a??
A?aana ia?aiino aeine?aeaeaieo aeaeo?ie?o?a c aiaee a ci?oai?
aiaeii-i?aai?/i? ?ic/eiieee c a?aooaaiiyi i?ioeano anioe?aoe??.

4. Anoaiiaeaii, ui aaee/eie ?ic/eiiino? ? (G(tr ia?oei?ao?a eoaeieo
iaoae?a aeecuee? o an?o aeine?aeaeaieo nenoaiao aiaea-AeA? a iaeano?
neeaae?a 0-50 ia.% iaaiaeiiai eiiiiiaioo ? i?aeoe/ii ia caeaaeaoue a?ae
eiai i?e?iaee, ui na?ae/eoue i?i noaa?eueio no?oeoo?o aiaee aei 50 ia.%
AeA?, aea i?aai?/iee ?ic/eiiee a?a? ?ieue eeoa ?icaaaethaa/a.

5. Anoaiiaeaii, ui aeey aaeeeeo oao?aaee?eaiii?eieo ?ii?a oaeoi?ii, ui
aecia/a? aaee/eio (G(tr aeaeo?ie?o?a i?e iaeeo aeiaaaeao AeA?, ? aia?a?y
ooai?aiiy ii?iaeieie (G(tr(, ye?e aeaii e?euee?nio ioe?ieo ? iieacaii
e?i?eio caeaaei?noue (G(tr( a?ae iiaa?oiaaiai iaoyao ci?oaiiai
?ic/eiieea.

6. Iieacaii e?i?eio caeaaei?noue lgCian a?ae iaa?iaii? aaee/eie
ae?aeaeo?e/ii? i?iieeiino? 1/( a aeine?aeaeaieo iaie AeA?, oiaoi
?ic/eiieee ??cii? i?e?iaee ia’?aeio? oaea oi?aa?naeueia
iae?iaeanoea?noue ye ae?aeaeo?e/ia i?iieei?noue.

7. Anoaiiaeaii e?i?eio caeaaei?noue i?ae aaee/eiaie aia?a?e A?aana
ia?aiino aeaeo?ie?o?a oa aaee/eiith, iaa?iaiith aei ?aae?ono ?ii?a.
Oaeei /eiii, ?ici?? ?ii?a ? oaeoi?ii, ui aecia/a? nieueaaoaoe?th
aeaeo?ie?o?a.

8. Ia/eneaii KSP, (G(tr, (H(tr i (S(tr aeey ia?oei?ao?a eae?th ?
oao?aaee?eaiii?th a ci?oaieo ?ic/eiieeao aiaea-AI i?e 288.15-308.15 E.
Anoaiiaeaii, ui nieueaaoaoe?y aeine?aeaeaieo aeaeo?ie?o?a ciaioo?oueny
c? ca?eueoaiiyi oaiia?aoo?e, a ooieoe?? (H(tr i (S(tr yaeythoueny a?eueo
/ooeeaeie aei ci?i no?oeoo?e ci?oaiiai ?ic/eiieea. I?e/iio, nenoaia c
?iiaie aaeeeeo ?ici???a (R4N+) a oeueiio a?aeiioaii? e?aua, i?ae
aiaeia?/ia c ?iiaie eoaeieo iaoae?a (iaaaeee? ?iie).

Iniiaiee ci?no aeena?oaoe?? aeeeaaeaii a ioae?eaoe?yo

1. Ee?aaa A.A., Iae O.A., Aacoaeue A.Ae. ?anoai?eiinoue e noaiaea?oiua
yia?aee Aeaana ia?aiina ia?oei?aoia uaei/iuo iaoaeeia, oao?aiaoee- e
oao?ayoeeaiiiiey ec aiaeu a aiaeii-aoeaoiiiaua ?anoai?eoaee // AEo?iae
iauae oeiee.-1997.-O.67.- Aui.4.- N.575-578.

2. Aacoaeue A.Ae., Ee?aaa A.A., Iae O.A. ?anoai?eiinoue e nieueaaoaoeey
ia?oei?aoia uaei/iuo iaoaeeia, oao?aiaoee- e oao?ayoeeaiiiiey a nianyo
aiaea – aeeiiey?iue ai?ioiiiue ?anoai?eoaeue // Aanoiee iaoee e
oaoieee.-1997.- Aui.1.- N.56-61.

3. Ee?aaa A.A., Iae O.A., Aacoaeue A.Ae. ?anoai?eiinoue ia?oei?aoia
uaei/iuo iaoaeeia e oao?aaeeeeaiiiieaauo nieae a nianyo aiaea –
aeeiiey?iue ai?ioiiiue ?anoai?eoaeue // Oe?aeineee oeie/aneee
aeo?iae.-1998.-O. 64.-N5. – N.13-17.

4. Ee?aaa A.A., Iae O.A., Aoeiia I.A., Aacoaeue A.Ae. ?anoai?eiinoue e
nieueaaoaoeey ia?oei?aoia uaei/iuo iaoaeeia e oao?aaeeeeaiiiiey a
aiaeii-aoeaoiieo?eeueiuo ?anoai?eoaeyo // Aanoiee Oa?ueeianeiai
oieaa?neoaoa. Oeiey.-1998.- N2.- N.188-192.

5. Iae O.A., E??a?a I.I., Aacoaeee A.Ae. Iie?oa?i?/ia aeine?aeaeaiiy
?ic/eiiino? ? nieueaaoaoe?? ia?oei?ao?a eae?th oa oao?aiaoeeaiii?th o
aiaeii-aoeaoii?o?eeueieo ?ic/eiieeao // I`yo? Ea?eoeinuee? /eoaiiy:
Anaoe?a?inueea iaoeiai-iaoiaee/ia eiioa?aioe?y c i?iaeai i?e?iaeie/eo
iaoe. Ca??iee noaoae. Iieoaaa: Iieoaanueeee iaaeaaia?/iee ?inoeooo,
1998. -N.206-209.

6. Ee?aaa A.A, Iae O.A., Aacoaeue A.Ae. ?anoai?eiinoue e nieueaaoaoeey
ia?oei?aoia uaei/iuo iaoaeeia, oao?aiaoee- e oao?ayoeeaiiiiey a
aiaeii-eaoiiiauo ?anoai?eoaeyo. //AEo?iae iai?aaie/aneie
oeiee.-1998.-O.43.- N10.-N.1618-1622.

Iae Oaoyia A?eai??aia. ?ic/eii?noue ? nieueaaoaoe?y ia?oei?ao?a eoaeieo
iaoae?a ? oao?aaee?eaiii?th o ci?oaieo ?ic/eiieeao aiaea — aeeiiey?iee
ai?ioiiiee ?ic/eiiee.

Aeena?oaoe?y ia i?aaao ?oeiieno ia caeiaoooy iaoeiaiai nooiaiy
eaiaeeaeaoa o?i?/ieo iaoe ca niaoe?aeuei?noth 02.00.04 – O?ce/ia o?i?y.
Oe?a?inueea ?iaeaia?ii-iaaeaaia?/ia aeaaeai?y. Oa?e?a. Oe?a?ia. 1999.

Caoeuathoueny ?acoeueoaoe aenia?eiaioaeueiiai aeine?aeaeaiiy ?ic/eiiino?
KClO4, RbClO4, CsClO4, Me4NClO4 ? Et4NClO4 ia anueiio ?ioa?aae? neeaae?a
ci?oaiiai ?ic/eiieea aiaea-AI, aiaea-IAE, aiaea-AeIO, aiaea-AeINI,
aiaea-AI i?e 298.15E, a oaeiae ?acoeueoaoe oaiia?aoo?ii? caeaaeiino?
?ic/eiiino? ie?aieo nieae a aoeaoii?o?ee? oa ?o aiaeieo noi?oao i?e
288.15-308.15 E. I?iaiae?ciaaii nieueaaooth/o cae?ai?noue aeine?aeaeaieo
?ic/eiiee?a ca aia?a??th A?aano ia?aiino aeaeo?ie?o?a c aiaee o
aiaeii-i?aai?/i? noi?o? (G(tr. Anoaiiaeaii, ui aaee/eie ?ic/eiiino? ?
(G(tr ia?oei?ao?a eoaeieo iaoae?a aeecuee? o an?o aeine?aeaeaieo
nenoaiao a iaeano? neeaae?a 0-50 ia.% iaaiaeiiai eiiiiiaioo ? i?aeoe/ii
ia caeaaeaoue a?ae eiai i?e?iaee, a aeey aaeeeeo ca ?ici??ii
oao?aaee?eaiii?eieo ?ii?a oaeoi?ii, ui aecia/a? (G(tr i?e iaeeo
aeiaaaeao AeA?, ? aia?a?y ooai?aiiy ii?iaeieie, ui caeaaeeoue a?ae
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