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Реакції алкілгалогенідів з механічно активованим хлоридом калію: Автореф. дис… канд. хім. наук / Ю.В. Дадалі, НАН України. Ін-т фіз.-орган. хімії та

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IAOe?IIAEUeIA AEAAeAI?ss IAOE OE?A?IE

?INOEOOO O?CEEI-I?AAI?*II? O?I?? OA AOAEAO?I??

?i. E.I. Eeoaeiaiea

Aeaaeae? TH??e Aieiaeeie?iae/

OAeE
541.124-145:542.941.7:547.224

?AAEOe?? AEE?EAAEIAAI?Ae?A C IAOAI?*II AEOEAIAAIEI OEI?EAeII EAE?TH

02. 00. 04 O?ce/ia o?i?y

Aaoi?aoa?ao

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?i?/ieo iaoe

Aeiiaoeuee – 1998

Aeena?oaoe??th ? ?oeiien.

?iaioa aeeiiaia a ?inoeooo? o?ceei-i?aai?/ii? o?i?? oa aoaeao?i??

?i. E.I. Eeoaeiaiea IAI Oe?a?ie

Iaoeiaee ea??aiee : eaiaeeaeao o?i?/ieo iaoe, noa?oee iaoeiaee

ni?a?ia?oiee
I?o/aiei Na?a?e Aiaoie?eiae/,

?inoeooo
o?ceei-i?aai?/ii? o?i?? oa aoaeao?i??

?i. E.I.
Eeoaeiaiea IAI Oe?a?ie, n. i. n.

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

ss?ei-Aaa?a Ieeiea
Eoe’yiiae/.

Aeiiaoeueeee
aea?aeaaiee oaoi?/iee oi?aa?neoao,

i?ioani?;

– eaiaeeaeao
o?i?/ieo iaoe, noa?oee iaoeiaee

ni?a?ia?oiee
Eaieai Eaii?ae I?eaio?eiae/.

?inoeooo
o?ceei-i?aai?/ii? o?i?? oa aoaeao?i??

?i. E.I.
Eeoaeiaiea IAI Oe?a?ie, caaaeoaa/

aaeaeeo.

I?ia?aeia onoaiiaa – Aeiiaoeueeee aea?aeaaiee oi?aa?neoao,

I?i?noa?noai ina?oe
Oe?a?ie.

Eaoaae?a
iai?aai?/ii? o?i??.

i. Aeiiaoeuee.

Caoeno a?aeaoaeaoueny “ 10 “ a?oaeiy 1998 ?ieo i 14 aiaeei?

ia can?aeaii? niaoe?ae?ciaaii? a/aii? ?aaee Ae 11. 216. 01 ?inoeoooo
o?ceei- i?aai?/ii? o?i?? oa aoaeao?i?? ?i. E.I. Eeoaeiaiea IAI Oe?a?ie /
340114, i. Aeiiaoeuee, aoe. ?.Ethenaiao?a, 70 /.

C aeena?oaoe??th iiaeia iciaeiieoenue o a?ae?ioaoe? ?inoeoooo
o?ceei-i?aai?/ii? o?i?? oa aoaeao?i?? ?i. E.I. Eeoaeiaiea IAI Oe?a?ie /
340114, i. Aeiiaoeuee, aoe. ?.Ethenaiao?a, 70 /.

Aaoi?aoa?ao ?ac?neaiee “ 27 “ aeiaoiy 1998 ?.

A/aiee nae?aoa?

niaoe?ae?ciaaii? a/aii? ?aaee Ae 11. 216. 01
Oaiae?ee I.I.

9

AEOOAEUeI?NOUe I?IAEAIE. Iaaecae/aeia aeieia?/ia noaiiaeua o ?aa?iiao
cina?aaeaeaiiy o?i?/ii? i?iieneiaino? iio?aao? ?ic?iaee iao?aaeeoe?eieo
i?aeoiae?a aei aeaioiaeaiiy i?iaeoeoe?? oiieiai i?aai?/iiai neioaco oa
?icaeoeo iiaeo iaoeiaeo iai?yie?a, ye? eaaeaoue a iniia? inoaii?o.
Iaeiei c oaeeo iiaeo iai?yie?a ? oaa?aeioaciee iaoaiio?i?/iee neioac oa
o?i?y iaoaiiaeoeaiaaieo ?aaeoe?e ca o/anoth oaa?aeeo ?a/iaei. Ia?aaaaith
oaa?aeioacieo i?ioean?a iaae o?aaeeoe?eieie ? i?io?eaiiy ?aaeoe?e aac
?ic/eiiee?a ? i?aeaeuaieo oaiia?aoo?, a?aenooi?noue iia?/ieo
i?iaeoeo?a. Cia/ia c?inoaiiy ?aaeoe?eii? caeaoiino? oaa?aeeo ?a/iaei a
oiiaao iaoai?/ii? ia?iaee aeeeeeaia aeoioethaaiiyi iaoai?/ii? aia?a?? o
aeaeyae? ??cieo aeaoaeo?a no?oeoo?e e?enoaeo oa ? caaaeueiei yaeuai:
?acii c a?aeiiei aoaeoii aeoeaaoe?? ?aaeoe?e c iai?aai?/ieie noano?aoaie
e iie?ia?aie aiii aeyaey? naaa oaeiae ? a ?aaeoe?yo ?c i?aai?/ieie
niieoeaie. Aeine?aeaeaiiy a aaeoc? aaoa?ioacieo iaoaiiaeoeaiaaieo
i?aai?/ieo ?aaeoe?e o?eueee ii/eiathoueny, aei oiai, a e?oa?aoo??
i?aeoe/ii a?aenooi? aeai? i?i iaoai?cie e e?iaoeeo ?o i?io?eaiiy, a oiio
/ene? e ioeeaio?eueiiai cai?uaiiy a ae?oaoe/iiio ?yae?. ?acii c oei, o
?ic/eiao ?aaeoe?? ioeeaioeeueiiai cai?uaiiy iaeaea noaee eeaneeith
no/anii? i?aai?/ii? o?i??. Oiio, aiie iiaeooue neoaeeoe iiaeaeueieie
aeey aea/aiiy oeyo?a oa iaoai?ci?a iaoaiiaeoeaiaaieo ia?aoai?aiue
i?aai?/ieo niieoe.

CA’ssCIE ?IAIOE C IAOEIAEIE I?IA?AIAIE, IEAIAIE OA OAIAIE ?INOEOOOO:
?iaioa aeeiiaia a eaai?aoi??? iaoaeieiiieaeniiai eaoae?co ?iOIA IAI
Oe?a?ie a ca’yceo c iaoeiai-aeine?aeiith oaiith “?aaeoe?eia caeaoi?noue,
naeaeoeai?noue oa eaoae?c a oaa?aeioacieo i?ioeanao i?aai?/iiai neioaco”
(Oeo?: 2.1.4.83).

IAOA OA CAAeA*? AeINE?AeAEAIIss:

1. Iiooe aoaeo?a iaoai?/ii? aeoeaaoe?? ?aaeoe?e ioeeaio?eueiiai
cai?uaiiy a ae?oaoe/iiio ?yae? a nenoai? “aee?eaaeiaai?ae (ia?e) – n?eue
aaeiaai?aeo eoaeiiai iaoaeo (oaa?aea oaca)”.

2. Anoaiiaeaiiy e?iaoe/ieo caeiiii??iinoae oa iaoai?ci?a i?io?eaiiy
?aaeoe?e cai?uaiiy aaeiaaio a aee?eaaeiaai?aeao ca o/anoth oaa?aeeo
nieae aaeiaai?ae?a eoaeieo iaoae?a.

3. Aeyaeaiiy i?e?iaee o?i?/ii aeoeaieo noai?a oaa?aei? iiaa?oi?, ye?
aeeeeeathoue ?aaeoe?? cai?uaiiy.

IAOEIAA IIAECIA IAeA?AEAIEO ?ACOEUeOAO?A. Aeyaeaii yaeua iaoai?/ii?
aeoeaaoe?? ?aaeoe?e ioeeaio?eueiiai cai?uaiiy i?e a?aenooiino?
?ic/eiieea o nenoai? “aee?eaaeiaai?ae (ia?e) – n?eue aaeiaai?aeo
eoaeiiai iaoaeo (oaa?aea oaca)” i?e e?iiaoi?e oaiia?aoo??.

Aeyaeai iiaee oei aaoa?ie?oe/ieo ia?aoai?aiue – eaioethaiaa
ioeeaio?eueia cai?uaiiy aaeiaaio a RX (R = Me, Et; X = Br, I) a nenoai?
“iaoai?/ii ia?iaeaiee ii?ioie KCl – ia?e RX”. Iieacaii, ui o?i?/ii
aeoeaieie oeaio?aie, ye? aeeeeeathoue ?aaeoe?? cai?uaiiy, ? iiaa?oiaa?
iiiiaaeain?? a ai?iiieo i?aea?aoeao e?enoaeo V1Cl oa aeeaaeain?? –
anioe?aoe ai?iiii? ? eao?iiii? aaeain?e V2Cl. ?ieue aeacaieo aeoeaieo
oeaio??a o ?aaeoe?? iieyaa? a aeaeo?io?euei?e ni?aae?? ioeeaio?eueiiio
cai?uaiith; i?eionea?oueny, ui ?aaeoe?y i?iaeiaaeaiiy eaioethao i?io?ea?
ca SN2 – iaoai?ciii i?e aeaeo?io?euei?e ni?aae?? aeaeo?e/ii iiceoeaieo
aaeain?e (V+-SN2), ye? ?aaaia?othoueny a eiaeiiio aeo? o?i?/iiai
ia?aoai?aiiy RX a RCl. E?i?eiee ia?ea eaioethao (caaeaaeue aeoeaieo
oeaio??a) a?aeaoaa?oueny a ?acoeueoao? ia?aiino ia aaeain??
(aeeaaeain??) aeaeo?iia c aeii?oeiaiai X- – eiio c aeieeiaiiyi
ia?aiaai?oieo F-oeaio??a.

I?AEOE*IA CIA*AIIss IAeA?AEAIEO ?ACOEUeOAO?A. ?ic?iaeaia iaoiaeeea
aenia?eiaioo oa ia?iaee e?iaoe/ieo aeaieo iaoai?/ii aeoeaiaaieo ?aaeoe?e
ioeeaio?eueiiai cai?uaiiy o nenoai? “aee?eaaeiaai?ae (ia?e) – n?eue
aaeiaai?aeo eoaeiiai iaoaeo (oaa?aea oaca)”. Iaoiaeeea iiaea aooe
iioe?aia ia ?io? aacia? noano?aoe oa oaa?ae? nie? i?e aea/aii? e?iaoeee
iiaa?oiaaeo iaoaiiaeoeaiaaieo ?aaeoe?e. ?icaeiai? oyaeaiiy i?i iaoai?cie
aaoa?ioaciiai ioeeaio?eueiiai cai?uaiiy a ae?oaoe/iiio ?yae?. Iaea?aeai?
?acoeueoaoe aeiiiaiththoue eeane/i? oyaeaiiy i?i iaoai?cie
ioeeaio?eueiiai cai?uaiiy.

INIAENOEE AIANIE CAeIAOAA*A. I?aeaioiaea oa i?iaaaeaiiy e?iaoe/ieo
aeine?aeaeaiue, ia?iaea aeaieo ia IAII oa ?ioa?i?aoaoe?y iaea?aeaieo
?acoeueoao?a aeeiiai? aaciina?aaeiuei aaoi?ii ?iaioe (a on?o
iioae?eiaaieo ?iaioao). Ni?aaaoi?e iioae?eiaaieo ?ia?o ii oai?
aeena?oaoe??: N.A.I?o/aiei – iaoeiaee ea??aiee, a on?o ioae?eaoe?yo –
ieaioaaiiy aenia?eiaioo, iaaiai?aiiy oa ?ioa?i?aoaoe?y ?acoeueoao?a;
A.A. Caiaueeia – iaaiai?aiiy oa ?ioa?i?aoaoe?y e?iaoeee ?aaeoe?e (o
aeacai?e ioae?eaoe??); A.A. Eiaaeaiei – AI? – aeine?aeaeaiiy (o
aeacai?e ioae?eaoe??).

AI?IAAOe?ss ?ACOEUeOAO?A AeENA?OAOe??. ?acoeueoaoe ?iaioe
aeiiia?aeaeeny oa iaaiai?thaaeenue ia I?aeia?iaeiiio neiiic?oi?
“I?aeoaciee eaoae?c: iaoai?ci oa canoinoaaiiy a i?aai?/iiio neioac?”
(?in?y, Naieo-Iaoa?ao?a, 24-26 /a?aiy, 1997); ia XVI Iaiaeaea?aneiio
c’?cae? ii caaaeueii? oa i?eeeaaeii? o?i?? (?in?y, Naieo-Iaoa?ao?a,
25-29 o?aaiy, 1998); ia I?aeia?iaei?e eiioa?aioe?? c o?ce/ii? o?i??
CPC’98 (Aano?ae?y, A?enaai, eeiaiue 1998); ia iaoeiaeo eiioa?aioe?yo
ani??aio?a – ?iOIA IAI Oe?a?ie (Aeiiaoeuee, 1995-1996).

IOAE?EAOe?ss ?ACOEUeOAO?A ?IAIOE. Ca iaoa??aeaie aeena?oaoe??
iioae?eiaaii noaoae – 5.

NO?OEOO?A OA IANssA ?IAIOE. Aeena?oaoe?y aeeeaaeaia ia 168 noi??ieao
ae?oeiaaiiai oaenoo e neeaaea?oueny ?c anooio, 6 ?icae?e?a, caeeth/aiiy,
aeniiae?a, ia?ae?eo oeeoiaaii? e?oa?aoo?e c? 180 iaeiaioaaiue, i?noeoue
21 oaaeeoeth, 41 ?enoiee.

AENIA?EIAIOAEUeI? IAOIAeE. Iaoai?/io aeoeaaoe?th ii?ioe?a nie?
i?iaiaeeee ia i?e?ia?a?aoe?eiiio ieei? MMVE – 0.005 (50 Aoe) a ?aaeoi??
?c 4 noaeaaeie eoeyie ieoiiith aia?aiiai?oaeaii?noth 340 Ao/ea.
Aeo?a/aiiy aee?eaaeiaai?ae?a oa (aai) iaeiie/aiiy aee?eoei?eae?a o
aacia?e oac? ?aaeoi?a ?a?no?oaaee iaoiaeii A?O: aeei?enoiaoaaee
o?iiaoia?ao EOI-8IAe c iieoi’yii-eii?caoe?iei aeaoaeoi?ii ? eieiieaie
aeiaaeeiith 3 i oa 1 i, ye? aoee caiiaiai? ia?ooiiith oacith 5% SE-30 ia
o?iiaoii? NAW. Niaeo?e AI? ?a?no?oaaee ia ?aae?iniaeo?iiao?? 3 ni
ae?aiaciio RADIOPAN SE/X – 2544 c oeee?iae?e/iei ?aciiaoi?ii (c iiaeith
TE011). On? ?aaeoe?? cai?uaiiy aea/aee i?e e?iiaoi?e oaiia?aoo??.

?AAEOe?? IOEEAIO?EUeIIAI CAI?UAIIss A OIIAAO AACIA?A?AII? IAOAI?*II?
IA?IAEE

I?e iaoai?/i?e ia?iaoe? o a?a?iieei? i?e e?iiaoi?e oaiia?aoo?? oaa?aeeo
nieae aaeiaai?ae?a eoaeieo iaoaeia MY (MY=NaCl, KCl, CsCl, KBr) a
i?enooiino? ia?ia aee?eeiaeeae?a RI (R=Me, Et, n-Pr) a inoaii?o
a?aeaoaa?oueny o?eaio?i?/ia cai?uaiiy aaeiaaio:

RI + MY
RY + MI (1)

Oaeaee?noue o?eaio?i?/ii? ?aaeoe?? caeaaeeoue a?ae ?ioaineaiino?
iaoai?/ii? ia?iaee. Iaoai?/ii ia ia?iaeaia n?eue ia ?aaao? c iii?oiith
oaeaee?noueth c aee?eaaeiaai?aeaie iaeaea i?e 120oC. Aeiaeaaaiiy a
?aaeoi? aiaee i?eaiaeeoue aei cia/iiai ciaiueoaiiy oaeaeeino? iiaeeiaiiy
RI, ? a i?enooiino? 0.1 iee aiaee aee?eaaeiaai?aee c iii?oiith
oaeaee?noueth ia ?aaaothoue. ?aaeoe?? RI ?c KCl noi?iaiaeaeothoueny
o?eaini?aoe??th RCl oa RI a iao?eoeth KCl. C a?aooaaiiyi aeacaiiai yaeua
aeo?ae i?iaeoeoo – iaoeeoei?eaeo ia i?i?aaaiaaiee MeI ? aeecueeei aei
e?euee?noiiai oa noaiiaeoue 916%. A o?eai?aaeoe?yo EtI ?c ii?ioeii KCl
aeae?ey?oueny EtCl ? aoeeai, a a aeiaaeeo n-PrI – ia?aeaeueii c n-PrCl
aeieea? i-PrCl oa i?ii?eai. Aeyaeaii, ui ?aaeoe?? cai?uaiiy aaeiaaia a
aee?eaaeiaai?aeao aeieeathoue i?e eiioaeo? ia?e RX (R=Me, Et, n-Pr,
i-Bu; X= Br, I) c iiia?aaeiuei aeoeaiaaiith iiaa?oiath nie? MY (MY=NaCl,
KCl, CsCl, KBr) ? i?e a?aenooiino? aacia?a?aii? iaoai?/ii? ia?iaee (a
iino-aoaeo?).

?AAEOe?? IOEEAIO?EUeIIAI CAI?UAIIss IA IIIA?AAeIUeI AEOEAIAAII?
IIAA?OI? ENl AAC IAOAI?*IIAI AIEEAO

Iiia?aaei? iiae??aiaiiy KCl ai?iaeiaae 30 oa. i?ecaiaeeoue aei
iaeiie/aiiy ia iiaa?oi? cie? aeoeaieo noai?a, ye? ni?iiiaei? aanoe
?aaeoe?th (1) aac iino?eii? iaoai?/ii? ia?iaee (iino-aoaeo). A oeueiio
?ac? cai?uaiiy i?io?ea? cia/ii iia?euei?oa: ci?ia eiioeaio?aoe??
noano?aoo RX (R=Me, Et) a aacia?e oac? ?aaeoi?a ai?iaeiaae 3 aiaeei
iacia/ia. E?iaoeea oeeo ?aaeoe?e aea/aeany ca iaeiie/aiiyi i?iaeoeoo RCl
a aacia?e oac? ?aaeoi?a. Ia a?aei?io a?ae o?eaio?i?/ieo ?aaeoe?e EtI ?
EtBr, i?e a?aenooiino? iaoaiiia?iaee ?acii c EtCl aeieeiaiiy aoeeaio ia
niinoa??aa?oueny. O ?aaeoe?? ?c n-PrI ?acii c i?iaeoeoii cai?uaiiy
n-PrCl a?aenooi? i-PrCl oa i?ii?eai. O oie aea /an ?aaeoe?y i-BuBr a
oeeo oiiaao i?ecaiaeeoue aei ia?aeaeueiiai aeieeiaiiy ?ciaooeeaio oa
t-BuCl. Anoaiiaeaii, ui ?aaeoe?? ?ia?aothoueny iiiaaeaiiyi o ?aaeoi?
ne?aeiaeo e?euee?noae aiaee oa cian?i ia eaeooue aac iiia?aaeiuei?
aeoeaaoe?? nie?. Oa?iiae?iai?/io iaaea?aei?noue i?io?eaiiy ?aaeoe?? MeI
c oaa?aeioaciith iaaeoeaiaaiith n?eeth KCl i?aeoaa?aeaeo? ? ?ic?aooiie
ci?iaiiy ooieoe?? A?aana: G +5.04 eAeae/iieue. ?ic?aooiie ooieoe??
A?aana aeey aeacaii? nenoaie c aeoeaiaaiith n?eeth, c?iaeaiee ia iniia?
a?oai? aenia?eiaioaeueii? ioe?iee eiinoaioe ??aiiaaae ?aaeoe?? ii
aeeaei? ?? i?io?eaiiy ( 0.33), iieaco?, ui a oiiaao aeoioeueiaaii? a
e?enoae? KCl iaoai?/ii? aia?a?? ?aaeoe?? cai?uaiiy ? oa?iiae?iai?/ii
aea?aei?oeie: G -0.92 eAeae/iieue. Aeoiaee MeCl, EtCl, n-PrCl ia
i?i?aaaiaaiee noano?ao RI – i?aeoe/ii e?euee?noi? oa noaiiaeyoue,
a?aeiia?aeii, 916%, 1003%, 925%, a i?iaeoeoa EtCl o ?aaeoe?? c EtBr –
965%.

AAeNI?AOe?ss RX IA IIAA?OI? KCl

Oaaeeoey 1. Ia?aiao?e ??aiyiiy (2) Eaiaith?a aeey aaeni?aoe?? RX ia
aeoeaiaai?e iiaa?oi? KCl

RXKa, 103 Ia-1Cm, ieiieue/i2MeI 0.90.220.82.0EtI
4.20.925.21.5EtBr1.20.226.62.1MeCl 8.82.51.60.1EtCl 17.76.63.50.4 EtCl
*12.86.84.30.8*I?ei?oea: ia?aiao?e iiaeai? uiaei i?iaeoeoo ?aaeoe?? c
EtBr I?io?eaiiy ?aaeoe?e cai?uaiiy aaeiaaio a RX ia iiia?aaeiuei
iaoaie/ii aeoeaiaai?e iiaa?oi? KCl (0.5 a) ni?yaeaia c i?ioeanaie
aaeni?aoe?? noano?ao?a oa aeieeath/eo o ?aaeoe?? aee?eoei?eae?a.
Aaeni?aoe?eia ??aiiaaaa anoaiiaeth?oueny i?aeoe/ii iae?aco, i?e/iio
eiioeaio?aoe?y aaeni?aiaaiiai noano?aoo a noai? ??aiiaaae cia/ii
a?ae??ciy?oueny a?ae ioey. A oiae? ?aaeoe?? noano?ao aeo?a/a?oueny neaai
ye c aaciai? oace ?aaeoi?a, oae ? c aaeni?aiaaiiai noaio, e oiio eiai
iiaa?oiaaa eiioeaio?aoe?y i?aeoe/ii ia ci?ith?oueny ai?iaeiaae anueiai
/ano aea/aiiy ?aaeoe??. Oea icia/a?, ui ?aaeoe?y ia ii?ooo?
aaeni?aoe?eii? ??aiiaaae, a naia aaeni?aoe?y ? iaeoaeaeoith noaae??th
?icaeyiooiai i?ioeano. Aaeni?aoe?y noano?ao?a e i?iaeoeo?a ?aaeoe??
aea/aeanue a oiiaao ia?aa?eueoaiiy noano?aoo ia iiaa?oi? KCl.
Aaeni?aoe?y RX (aeey RX = EtI i?e ia?oe?aeueiiio oeneia? ia?e
aoeeeiaeeaeo P(EtI)1200 Ia) ? RCl ia iaoai?/ii ia?iaeai?e iiaa?oi? KCl
caaeia?eueii iieno?oueny ??aiyiiyi ?cioa?ie aaeni?aoe?? Eaiaith?a:

wmetafile8? ??,???????????
???????????yyy????.????1?????????????
`a???&??yyyy?????Ay«y ???&?
?MathType???????u????????????-?????????›???u?th??????
aea Cm(RX) – iaeneiaeueia iiaa?oiaaa eiioeaio?aoe?y RX a aaeni?aoe?eiiio
iiiioa??, Ka(RX) – eiinoaioa aaeni?aoe?eii? ??aiiaaae RX. Aecia/ai? c
e?i?eieo aiaii?oic ??aiyiiy (2) ia?aiao?e aaeni?aoe?? RX i?aenoiiaai? a
oaaeeoe? 1.

E?IAOEEA ?AAEOe?E CAI?UAIIss AAEIAAIO A RX IA IIAA?OI? IIIA?AAeIUeI
AEOEAIAAII? NIE? KCl

E?iaoeea ca?eueoaiiy noia?ii? (c a?aooaaiiyi aaeni?aiaaii? ia iiaa?oi?)
e?eueeino? i?iaeoeoo RCl, ui aeieea? o ?aaeoe?? ia i?ioyc? 3 aiaeei
(?en. 1), caaeiaieueiy? ??aiyiith:

wmetafile8? ??/???????????
???????????yyy????.????1?????????????
????&??yyyy?????Ay¬yAI???&??MathType??P????u?th??????

wmetafile8? ?? ???O????????&?

?yyyy????Word?Microsoft Word??????????P
???u?????????????I???Courier New?I????-?????????uIy???????en.
1. E?iaoeea iaeiie/aiiy iaoeeoei?eaeo a ?aaeoe?? MeI c ii?ioeii KCl,
yeee ?aeaenoaaa ai?iaeiaae 10 oa. (e?eaa 1), 3 aiaeei (e?eaa 2) oa 18
aiaeei (e?eaa 3) i?ney iaoai?/ii? ia?iaee.

??aiyiiy (3) ? eiia?iaoe??th aeaio e?iaoe/ieo ??aiyiue ia?oiai ii?yaeeo.
Oea a?aeiia?aea? neooaoe??, eiee noano?ao ia?aeaeueii ?aaao? ia aeaio
aeaeao ?aaeoe?eieo oeaio??a, ye? aaia?iaai? ia iiaa?oi? KCl a oiae?
iiia?aaeiuei? iaoaiiia-

?iaee. A?aoiaoth/e, ui ia i?ioyc? /ano aenia?eiaioo (3 aiaeei) ci?iaiiyi
eiioeaio?aoe?? noano?aoo iiaeia ciaoooaaoe, k1 e k2 – iathoue cia/aiiy
eiinoaio oaeaeeino? caaeaae? ?aaeoe?eieo oeaio??a I oa II aeaeo, a
ia?aiao?e 1 ? 2 – a?aie/ieo cia/aiue e?eueeino? i?iaeoeoo, ui aeieea? ia
aeacaieo oeaio?ao, a?aeiia?aeii. Oeaio?e I oa II aeaeo ?noioii
a?ae??ciythoueny nai?th ?aae- oe?iith caeaoi?noth: cia/aiiy k1 a?eueoa
ca k2 i?eaeecii ia ii?yaeie oa noaiiaeyoue aeey ?aaeoe?? c
iaoeeeiaeeaeii a?aeiia?aeii (2.00.3)10-3 oa (1.90.5)10-4 n-1 .

Ia i?eeeaae? ?aaeoe?? MeI ( 16.67 ieiieue) c iiia?aaeiuei ia?iaeaiei
ii?ioeii KCl (0.5 a) oa aeo?eiaiei i?ney oeueiai ia i?ioyc? ??ciiai /ano
aei ii/aoeo ?aaeoe?? anoaiiaeaii, ui ai?iaeiaae 3 aiaeei o?eaaeino?
?a?no?aoe?? e?iaoeee iiaeia ciaoooaaoe o?ce/iith ?aeaenaoe??th aeoeaieo
oeaio??a iiaa?oi? KCl (?en.1, e?ea? 1,2). O?ce/ia ?aeaenaoe?y aiineoue
iii?oiee aianie o e?iaoeeo i?ney aeo?eioaaiiy ia?iaeaii? nie?,
iai?eeeaae, 18 aiaeei aei ii/aoeo ?aaeoe?? (e?eaa 3).
Iae?aaeoe?eiicaeaoi?o? oeaio?e I aeaeo ?aeaenothoue oaeaeoa, i?ae
oeaio?e II aeaeo. Aeo?eiea ia?iaeaii? nie? ai?iaeiaae 11 ae?a i?e
e?iiaoi?e oaiia?aoo?? i?ecaiaeeoue aei i?aeoe/ii iiaii? ?aeaenaoe??
aeoeaieo noai?a: ieiua iiaa?oi? nie? i?e oeueiio cia/ii ia ci?ith?oueny,
aea cai?uaiiy aaeiaaio a RI ia oae?e iiaa?oi? c iii?oiith oaeaee?noueth
ia eaea.

AIEEA OA?A?AII? II?IOEII KCl AeICE IAOAI?*II? AIA?A?? IA E?IAOEEO
?AAEOe??

Aieea aeice oa?a?aii? ii?ioeii KCl aia?a?? ia e?iaoeeo cai?uaiiy
aaeiaaio a aee?eeiaeeaeao aea/aee ia i?eeeaae? ?aaeoe?? EtI. Ca?eueoaiiy
aeice oa?a?aii? aia?a?? i?eaiaeeoue aei c?inoaiiy ieoiii? iiaa?oi?
ii?ioeo KCl. Aeacaia caeaaei?noue ia? aeaeyae e?eai? c iane/aiiyi oa
a?aeiia?aea? ??aiyiith:

Soae = S*oae
(1-exp(-sDoae)),
(4)

aea S*oae – a?aie/ia aaee/eia ieoiii? iiaa?oi?, a s – eiinoaioa, yea
oa?aeoa?eco? aoaeoeai?noue aeieeiaiiy iiai? iiaa?oi? (aaee/eia, iaa?iaii
i?iii?oe?eia aei ieoiii? ?iaioe aeieeiaiiy iiai? iiaa?oi?). Neiaaoii c
Soae c?inoa? ?aaeoe?eia caeaoi?noue iiaa?oi? nie?: i?e iino?eiiio
cia/aii? M iane cie? KCl aaee/eia ii/aoeiai? oaeaeeino? ci?iaiiy
caaaeueii? e?eueeino? aoeeoei?eaeo wmetafile8? ??????????????
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i
=imax(1-exp(-iDoae)),
(5)

aea i – eiinoaioe, ui oa?aeoa?ecothoue aoaeoeai?noue ia?aoai?aiiy
iaoai?/ii? aia?a?? a eaiae aeieeiaiiy aeoeaieo oeaio??a i-oiai aeaeo
(i=1,2) o oiae? iiia?aaeiuei? ia?iaee KCl, imax – iaeneiaeuei? a?aie/i?
cia/aiiy ia?aiao??a i. I?e ieoiieo aeicao, a?eueoeo i?ae D*450 Aeae/a
(oea aea?aaeaioii 20 oa. iiia?aaeiuei? ia?iaee 0.5 a ii?ioeo KCl)
aaee/eie imax i?aeoe/ii ia caeaaeaoue a?ae Doae.

Cia/aiiy ia?aiao??a i*, S*oae, i ? s, ui aecia/ai? aeey ?aaeoe??
aoeeeiaeeaeo c ??aiyiue (4) oa (5), i?aenoiiaai? o oaae. 2.

Oaaeeoey 2. Cia/aiiy ia?aiao??a ??aiyiue (4), (5)

S*oae, i2/a1*, ieiieue/a2*, ieiieue/as103 , a/Aeae1103 , a/Aeae2103
, a/Aeae0.420.041.350.042.920.066.00.56.20.46.40.5 Aa??thaaiiy iane
nie? M i?e oiia?, ui ieoiia aeica iiia?aaeiuei oa?a?aii? ii?ioeii
aia?a?? DoaeD*, i?eaiaeeoue aei e?i?eii? ci?ie ia?aiao??a imax o
?aaeoe?yo c MeI oa EtI. Cia/aiiy eiinoaio k1 ? k2 o iaaeao
aenia?eiaioaeueieo iioeaie ia caeaaeaoue a?ae M. E?i?eia caeaaei?noue
ia?aiao??a imax a?ae iane I nie? aeicaiey? a?aeianoe cia/aiiy
iaeneiaeueii? a?aie/ii? e?eueeino? i?iaeoeoo imax(RCl), ui aeieea? ia
aeoeaieo oeaio?ao I oa II aeae?a, aei iaeeieoe? iane ia?iaeaii? nie?
i*(RCl)=imax(RCl)/I. A oaeiio ?ac? e?iaoeea iaeiie/aiiy caaaeueii?
ieoiii? e?eueeino? i?iaeoeoo *(RCl)= (RCl)/M ae?aceoueny ??aiyiiyi

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???uAth??????

Einoaioe s oa i aeey i=1,2 a iaaeao aenia?eiaioaeueieo iioeaie
ca?aathoueny. Oea, i/aaeaeii, icia/a?, ui iiaa iiaa?oiy oa ?aaeoe?ei?
oeaio?e iaio aeae?a aeieeathoue ia?aeaeueii – aiane?aeie iaeiiai
i?ioeano. Iiaeeeai a aoei i?eionoeoe, ui ?ieue aeoeaieo noai?a, ui
aeeeeeathoue ?aaeoe?th, iiaea a?ae?a?aaaoe /anoeia iiaa?oiaaeo Cl- –
eii?a, ye? neaai noaa?e?ciaai? e?enoae?/iei iieai (iai?eeeaae, o?, ui
ciaoiaeyoueny ia iiaa?oiaaeo ceaiao). Aeey ia?aa??ee oeueiai i?eiouaiiy
ii??aiy?ii a?ai?/io e?euee?noue iieaeoe EtCl, ui aeieea? a ?aaeoe?? c 1
a aeoeaiaaii? nie? ia oeaio?ao iaio aeae?a, NEtCl =NA (1* + 2*) 2.51018
(iieaeoe/a), c aaee/eiith iiaii? e?eueeino? Cl- – eii?a iiaa?oi? 1 a
nie?, NCl* 21018 (eii?a/a). Cia/aiiy NEtCl ciaeaeaii c iaea?aeaieo
ia?aiao??a i*, S*oae, a e?euee?noue NCl* iiaa?oiaaeo Cl- – eii?a – c
S*oae oa aaee/eie ia?aiao?o ?ao?oee e?enoaeo. Oaeo ca?ao ?ic?aoiaaieo
cia/aiue, NEtCl NCl*, icia/a?, ui o ?aaeoe?th iiaeooue aooe caeo/ai? ia
o?eueee /anoeia Cl- – eii?a, ye? neaai iia’ycai? e?enoae?/iei iieai, a
i?eiaeii?, on? ?icoaoiaai? ia iiaa?oi? Cl- – eiie.

A oie aea /an, a?aeiii, ui ia o?ce/ii ?aeaenoaaaoae iiaa?oi? ?aaeoe?y
ia eaea. I?e oeueiio iiaa?oiy nie? e, oaeei /eiii, e?euee?noue
iiaa?oiaaeo Cl- – eii?a ia ci?ith?oueny. Oei naiei, o ?ie? aeoeaieo
noai?a, ui aeeeeeathoue ?aaeoe?? ia iaoai?/ii ia?iaeai?e iiaa?oi?,
aenooiathoue ia ye?nue aeoeai? Cl- – eiie, a ?io? aeaoaeoe e?enoae?/ii?
no?oeoo?e. I/aaeaeii, ui aiie ia iiaeooue iie?eaaoe onth iiaa?oith
e?enoaeo. Oiaoi, ?ac o ?aaeoe?? iiaeooue aeo?a/aoeny an? Cl- – eiie
iiaa?oi?, oi aeoeai? noaie – aeaoaeoe, ye? aeeeeeathoue cai?uaiiy,
iiaeii? ?aaaia?oaaoeny a aeo? o?i?/iiai ia?aoai?aiiy. Oeae aeniiaie
iacaeaaeii i?aeoaa?aeaeo?oueny e?iaoe/ieie aeaieie.

E?IAOEEA IAEIIE*AIIss RCl O ?AAEOe?ssO C RI (R = Me, Et) OA EtBr

Oaaeeoey 3. Na?aaei? cia/aiiy eiinoaio k1 ? k2 ??aiyiiy (6) iaeiie/aiiy
RCl oa cia/aiiy ia?aiao??a Ai(RCl) ??aiyiiy (7) i?e aa??thaaii?
eiioeaio?aoe?? RX ia iiaa?oi? KCl

RXk1 103,

c-1k2 104,

c-1iAi(RCl),
i2/aMeI1.90.71.70.310.110.0120.300.06EtI2.30.91.50.510.050.0120.110.01Et
Br1.20.30.90.410.0630.00320.2480.005 C?inoaiiy aaee/eie Naaen(RX)
iiaa?oiaai? eiioeaio?aoe?? noano?ao?a i?eaiaeeoue aei ca?eueoaiiy
ii/aoeiai? oaeaeeino? ?aaeoe?? W0. Cia/aiiy eiinoaio oaeaeeino? k1 ? k2
caaeaae? aeoeaieo oeaio??a I oa II aeae?a o ?aaeoe?yo c RX a iaaeao
aenia?eiaioaeueieo iioeaie ia caeaaeaoue a?ae Naaen(RX) oa i?e?iaee
noano?aoo (oaae. 3). Ia a?aei?io a?ae eiinoaio oaeaeeino? ki, cia/aiiy
*i(RCl) e?i?eii c?inoathoue i?e ca?eueoaii? Naaen(RX); caeaaei?noue
*i(RCl) a?ae Naaen(RX) ia?aaea?oueny ??aiyiiyi:

*i(RCl) = Ai(RCl)Naaen(RX) (7)

Cia/aiiy Ai(RCl) caaaeai? o oaae. 3. Io?eiai? e?iaoe/i? caeaaeiino?
aaea?oueny iiynieoe, yeui i?eeiyoe, ui aeoeai? oeaio?e, ye? aeeeeeathoue
?aaeoe?th (iicia/eii ?o ViCl), ?aaaia?othoueny a aeo? o?i?/iiai
ia?aoai?aiiy RX aei RCl, i?eeiay o/anoue o eaioethaiaiio i?ioean?
cai?uaiiy aaeiaaio a aee?eaaeiaai?ae? c e?i?eiei ia?eaii eaioethao:

wmetafile8? ??

Ae?enii, ca?aeii aei noaie (8)-(9) i?e oiia?, ui ci?iith
eiioeaio?aoe?e oei?eae-eii?a oa aaeni?aiaaiiai ia iiaa?oi? KCl noano?aoo
ia i?ioyc? 3 aiaeei i?iaaaeaiiy ?aaeoe?e iiaeia ciaoooaaoe, io?eio?i
ianooiia ??aiyiiy aeey ci?ie ai?iaeiaae /ano aaee/eie *(RCl):

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aea ki(RX) ? kit – eiinoaioe oaeaeeino? i?iaeiaaeaiiy oa ia?eao
eaioethaa, a?aeiia?aeii, [ViCl]o – ii/aoeiaa iiaa?oiaaa eiioeaio?aoe?y
aaia?iaaieo a oiae? iiia?aaeiuei? iaoaiiia?iaee aeoeaieo oeaio??a i-ai
aeaeo, [Cl-]o – ii/aoeiaa eiioeaio?aoe?y oei?eae-eii?a ia iiaa?oi? nie?,
S*oae – a?aie/ia ieoiia ieiua iiaa?oi?. ??aiyiiy (10) caaeiaieueiy?
aii???/iei caeaaeiinoyi (6) – (7) i?e ki=kit,

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?????&??yyyy?????Ay?yA ????&??MathType???
???u?????????”????-?????_???e???u?th??????

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???????????yyy????.????1?????????????
?a???&??yyyy?????Ay©y )???&??MathType???
???u?????????”????-?????u???????u?th??????

A?aoiaoth/e, ui o ?aaeoe?yo RI aaee/eie eiinoaio oaeaeeino? ia?eaaiiy
eaioethao ia caeaaeaoue a?ae i?e?iaee noano?aoo (oaae.3), c a?aeiioaiue
Ai(MeCl)/Ai(EtCl) io?eio?ii cia/aiiy noano?aoii? naeaeoeaiino?
ki(MeI)/ki(EtI) ?aaeoe?? i?iaeiaaeaiey eaioethao, ui noaiiaeyoue 2.00.6
oa 3.10.8 aeey aeoeaieo oeaio??a I oa II aeae?a, a?aeiia?aeii. sse aoei
ne?ae niiae?aaoeny, iaea?eueo ?aaeoe?eii caeaoi? oeaio?e ia?oiai aeaeo ?
iaiueo naeaeoeaieie.

IAOAI?CI ?AAEOe?E CAI?UAIIss AAEIAAIO A RX IA IIAA?OI? IIIA?AAeIUeI
AEOEAIAAII? NIE? KCl

Oei?eae-eiie ia iiaa?oi? iaoai?/ii aeoeaiaaiiai ii?ioeo KCl iiaeooue
aooe eieae?ciaai? aai a aoceao ai?iiieo i?aea?aoie, aai ciaoiaeeoeny o
i?aeaoceiaeiao. A?aeiia?aeii aei c?iaeaii? aeua ioe?iee, a o?i?/iee
i?ioean iiaeooue caeo/aoeny an? oei?eae-eiie, ye? ciaoiaeyoueny ia
iiaa?oi?. A?aoiaoth/e, ui aeey e?enoae?a KCl aeaoaeoe a aeaeyae?
i?aeaoceiaeiiiai oei?o ia oa?aeoa?i?, ne?ae i?eeiyoe, ui oei?, yeee
aoiaeeoue aei neeaaeo i?iaeoeoo ?aaeoe?? cai?uaiiy – RCl, aa?aoueny c
aocea e?enoae?/ieo a?aoie. Noao?iiao?e/iei iane?aeeii oaeiai cai?uaiiy ?
aeieeiaiiy aaeain?? a ai?iiieo i?aea?aoeao11 Neio?iiiee i?ioean, i?e
yeiio aaeain?y, ui aeieea? a ?acoeueoao? ioeeaio?eueii? aoaee aoceiaei
oei?eae-eiiii oa iaeii/anii caiiaith?oueny a?aeo?aeiith a?oiith –
aaeiaai?ae-eiiii, aeaea?oueny iaeiaiueo eiia??iei /a?ac noa?e/i?
ia?aoeiaee.

. Oiio, aeoiaey/e c? noao?iiao??? ?aaeoe?? (8), aei?a/ii aeiionoeoe, ui
?ieue aeoeaieo oeaio??a ViCl, ye? aeeeeeathoue cai?uaiiy, iiaeooue
aeeiioaaoe aaeain?? a ai?iiieo i?aea?aoeao e?enoaeo KCl, eieae?ciaai?
ia?aaaaeii o i?eiiaa?oiaaiio oa?? /anoeiie. Ai?iii? aaeain??, ui iathoue
aoaeoeaiee iiceoeaiee ca?yae, aeyaeythoue aeaeo?io?eueio ni?aae?th
ioeeaio?eueiiio cai?uaiith. I?e oeueiio ?o ?ieue iieyaa? a iiey?ecaoe??
ca’yceo C-X oa ca’ycoaaii? a?aeo?aeii? a?oie – X- – eiia (X- = I-, Br-).
Aeieeath/ee aiane?aeie /anoeiaiai ?icae?eaiiy ca?yae?a iiceoeaiee ca?yae
ia -aoii? aoaeaoeth, ni?ey? ioeeaio?euei?e aoaoe? oei?eae-eiiii c
iiaeeciiai aocea e?enoae?/ieo a?aoie c aeieeiaiiyi i?iaeoeoo cai?uaiiy.
Noao?iiao?e/iei iane?aeeii ?icaeyiaiiai aeoo o?i?/iiai ia?aoai?aiiy RX
aei RCl ? ?aaaia?aoe?y ai?iiii? aaeain?? oa iiyaa aeii?oeiaiai X- – eiio
a ai?iiieo i?aea?aoeao (?en.2).

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?yyyy????Word?Microsoft Word??????????
Sa???u?????????????I???Courier New?I????-?????????uy??????

A?aenooi?noue -ae?i?ioaaiiy c aeae?eaiiyi a?aeiia?aeiiai ieao?io a
ia?aoai?aiiyo EtX (X=Br, I) oa n-PrI icia/a?, ui a oeeo aeiaaeeao
iiaiiai ?acae?eaiiy ca?yaeo c i?ii?aeiei aeieeiaiiyi ea?aeao?iio aai
eiiii? ia?e ia a?aeaoaa?oueny, oiaoi iiaeeeai i?eionoeoe, ui cai?uaiiy
aaeiaaio i?io?ea? ca V+-SN2 iaoai?ciii. Ia?aeaeueia aeieeiaiiy
?ciaooeeaio oa t-BuCl a ?aaeoe?? i-BuBr ?c KCl iiaea aeacoaaoe ia
i?io?eaiiy ?aaeoe?? ca V+-SN1 iaoai?ciii.

Aeieeiaiiy aee?eoei?eaeo a?aeiia?aeii iaoai?ciia? (?en.2) a?aeaoaa?oueny
iiaeeco aeaeo?io?eueiiai oeaio?o – ai?iiii? aaeain??. Oea iiaea aooe
i?e/eiith a?aeiinii aenieeo cia/aiue eiinoaioe aaeni?aoe?eii? ??aiiaaae
aeey RCl (oaae. 1): i/aaeaeii, ui oaieioa aaeni?aoe?? RCl ia aaeain??11
A aeecueeiio ioi/aii? aaeain?? iiceoeaiee ca?yae ia neiiiainiaaiee.

ViCl, ui iana aoaeoeaiee iiceoeaiue ca?yae, aiane?aeie
aeaeo?inoaoe/iiai aieeao iiaea aooe iinooiuei aeuith ca oaieioo
aaeni?aoe?? ia aeaeo?iiaeo?aeueieo (iaeiaiueo ca?yaeaeaieo) ae?eyieao
iiaa?oi?.

I?eionoeiee iaoai?ci ia?eao eaioethao (9): caaeaaeue aeoeaiiai oeaio?a,
oiaoi ai?iiii? aaeain??, a?aeaoaa?oueny aiane?aeie ia?aiino ia inoaiith
aeaeo?iia c aeii?oeiaiai X- – eiia (X- = I-, Br-) c aeieeiaiiyi
F-oeaio?a (?en. 3). I?inoi?iaa eieae?caoe?y aeii?oeiaiai X- – eiio oa
ai?iiii? aaeain?? o?eueee iaeia eiei iaeiiai (?en.2) iieaaoo? ia?aiin
aeaeo?iia. Oaeee iaoai?ci iiynith?, ia ia?oee iiaeyae, noia?a/eea?
aenia?eiaioaeuei? oaeoe: caaeaaeue aeoeaieo noai?a aeeeeea?oueny
?aaeoe??th cai?uaiiy11 Caaeaaeue aeoeaieo noai?a ia iiaea aooe
iane?aeeii o?ce/ii? ?aeaenaoe??, oiio ui inoaiiy i?io?ea? iia?euei?oa.

, aea eiinoaioa oaeaeeino? ia?eao eaioethao ia ? ooieoe??th Caaen(RX).

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?cHw?n??Times New Roman Cyr????&??cHw?n??Times New
Roman????&?$?cHw?i? ????*·F????????S? ?thyi~?5
???&??cHw?o??`?`??????&?$?cHw?i?
???Oe????????S??thyi~?5???&?$?cHw?i?
???ae·F????????S??eu??O????&?$?cHw?i? ??????&?$?cHw?i? ??? ·F????????S?????????????&?$?cHw?i? ???ae·F????????S?????????????&?$?cHw?i? ????·F????????S??io¶?O?4???&?^?cHw?i?V???h ·F-?????? ? ? V! ?? ?? ?? ?? ??. ??????????A??oE?yyO???‡O????-???&?P?cHw?i?H???d·F-?????? ? ? ? ?? ?? ?? ?? ??- ??????????T?k???™io:???&?j?cHw?i?b????en. 3. Iaoai?ci ia?eaa eaioethao a eaioethaia?e ?aaeoe?? cai?uaiiy aaeiaaio a aee?eaaeiaai?ae? ia iiaa?oi? aeoeaiaaii? nie? KCl. Iacaeaaeii aeieeiaiiy F-oeaio??a o iao?eoe? KCl aiane?aeie i?io?eaiiy ?aaeoe?? cai?uaiiy (8-9) cao?eniaaii iaoiaeii AI?. Anoaiiaeaii, ui ia?aoai?aiiy RX aei RCl coi?iaiaeeoueny iiyaith oa iaeiie/aiiyi o nie? ia?aiaai?oieo oeaio??a (IIOe) ?c g-oaeoi?ii, ??aiei 2.0000. Aiaeii/an naia iaoai?/ia ia?iaea KCl o a?a?iieei? ia i?eaiaeeoue aei aeieeiaiiy ia?aiaai?oieo oeaio??a a iii?oi?e eiioeaio?aoe??; inoaii? aeieeathoue eeoa aiane?aeie ?aaeoe?? na?aeiia?iaeaii? nie? c noano?aoii - RX. Aeey ?icae?eaiiy aiane?a aeoeaieo noai?a eiaeiiai aeaeo a ooai?aiiy IIOe i?iaiaeeee ?aaeoe?? ?c MeI, EtI, EtBr naeaeoeaii ia aeoeaieo noaiao 1 aeaeo (Nenoaia 1) oa 2 aeaeo (Nenoaia 2). Aeey oeueiai aeei?enoiaoaaee ianooiiee cao?ae: a?aoiaoth/e, ui ca ia?o? i?aaiaeeie ia na?aeiia?iaeai?e iiaa?oi? o ?aaeoe?? aeo?a/athoueny i?aeoe/ii an? aeoeai? noaie I aeaeo ( 2 10-3 n-1), a ae?oa? aeo?a/athoueny iacia/ii, ?aaeoe?th coieiyee i?ney ia?oeo 30 oa. (Nenoaia 1). A oe??? nenoai? 1 iniiaiee aianie a AI? neaiae iiaeii? aeaaaoe IIOe, ui ooai?eeeny ianaiia?aae c aeoeaieo noai?a I aeaeo. O?ce/ia ?aeaenaoe?y noai?a I aeaeo oaeiae i?io?ea? oaeaeoa: anoaiiaeaii, ui aiie i?aeoe/ii iiai?noth ?aeaenothoue ai?iaeiaae 1.5 - 2 ae?a, oiae? ye aeey ?aeaenaoe?? noai?a II aeaeo iaiao?aeii cia/ii a?eueoa /ano. Iiia?aaeiy aeo?eiea ia?iaeaii? nie? i?ioyaii aeacaiiai /ano (Nenoaia 2) aeaea ciiao naeaeoeaii i?iaanoe ?aaeoe?th ia aeoeaieo noaiao II aeaeo e, oei naiei, ?icae?eeoe aianee noai?a iaio aeae?a aei aeieeiaiiy ia?aiaai?oieo oeaio??a. A iaio nenoaiao e?iaoeea iaeiie/aiiy RCl a?aeiia?aea? ??aiyiith *(RCl)= i*(1-exp(-ki’ t)), (13) aea i* - a?aie/i? ieoii? cia/aiiy caaaeueii? e?eueeino? RCl, ki’ - eiinoaioe oaeaeeino? aeo?a/aiiy aeoeaieo noai?a o a?aeiia?aei?e nenoai?. Cia/aiiy ki’ a iaaeao aenia?eiaioaeueieo iioeaie ca?aathoueny c a?aeiia?aeieie cia/aiiyie kit eiinoaio oaeaeeino? caaeaae? aeoeaieo noai?a I oa II aeae?a (aeea. oaae. 3), oiaoi a ?icaeyiaieo nenoaiao iniiaiee aianie o ?aaeoe?th aiinyoue aeoeai? noaie I oa II aeae?a a?aeiia?aeii. A iaio nenoaiao ?aaeoe?y cai?uaiiy noi?iaiaeaeo?oueny aeieeiaiiyi ia?aiaai?oieo oeaio??a. O a?aeiia?aeieo ?i niaeo?ao AI? neaiaee iinooiuei a?ae??ciythoueny ca oi?iith e?i??: aeey ia?oiai aeaeo oeaio??a neaiae a?aeiia?aea? ?cio?iiiiio eieaeueiiio e?enoae?/iiio iieth (?en. 4), oiae? ye o aeiaaeeo oeaio??a ae?oaiai aeaeo - iieth aen?aeueii? neiao??? (?en. 5). Aiae?c niaeo??a i?aeoaa?aeaeo? c?iaeaia aeu? i?eiouaiiy, ui aeoeaieie noaiaie I aeaeo ? iiiiaaeain?? a ai?iiieo i?aea?aoeao e?enoaeo (?cio?iiia ioi/aiiy, ?cio?iiiee g-oaeoi?), a II aeaeo - ia?a, yea neeaaea?oueny c ai?iiii? aaeain??, iia’ycaii? c eao?iiiith (aeeaaeain?y, aen?aeueia neiao??y eieaeueiiai iiey, ai?cio?iiiee g-oaeoi?). wmetafile8? ??a???AE????? ???u????P?????"????-?????ue???????????-???? ????ue?”/??? 'e???????yyy????????ue?,_GI???-?AE???%a?Iueuauee uoue3/4uyu y…u)yTu9yHuRy0uay oqyo?en. 5. AI?-niaeo? ia?aiaai?oieo oeaio??a, ui aeieeathoue o nenoai? 2. wmetafile8? ??????I????? ???u????P?????"????-?????ue???????????-???? ????uF/????en. 4. AI?-niaeo? ia?aiaai?oieo oeaio??a, ui aeieeathoue o nenoai? 1. Aecia/ai? cia/aiiy eiioeaio?aoe?? ia?aiaai?oieo oeaio??a Ci (oaae. 4) ye ieae/a iaaea aaee/eie [ViCl]o aeo?aeii? eiioeaio?aoe?? aeoeaieo noai?a a?aeiia?aeiiai aeaeo (aei 80% F-oeaio??a iiaea, iai?eeeaae, aeiooe a aoiinoa?? iia?o?y a iane?aeie oaiini?aoe?? eenith e + O2 = O2-). Cia/aiiy Ci ca?aeii aei cai?iiiiiaaiiai iaoai?cio ?aaeoe?? (9) ia caeaaeaoue a?ae eiioeaio?aoe?? aaeni?aiaaiiai noano?aoo. Oaaeeoey 4. Ia?aiao?e niaeo??a AI? ia?aiaai?oieo oeaio??a, ui aeieeathoue o ?aaeoe?? iiia?aaeiuei ia?iaeaii? nie? KCl c RX. Nenoaia 1Nenoaia 2 RXCaaen(RX), ieiieue/i2C1 105, ieiieue/i2g*Caaen(RX), ieiieue/i2C2 105, ieiieue/i2g//*g*MeI15.4722.000011.81132.00112.0001EtI21.4621.999817.4622 .00082.000122.662--EtBr421.9998842.00092.0001* I?ei?oea: aaniethoia iioeaea aecia/aiiy cia/aiue g-oaeoi?a noaiiaeoue 0.0006 ?AAEOe?EIA CAeAOI?NOUe AEOEAIEO NOAI?A O ?AAEOe?ssO IOEEAIO?EUeIIAI CAI?UAIIss AAEIAAIO A RX Ia iniia? ??aiyiiy (11) ? aeaieo oaae. 4 c?iaeaia ioe?iea aa?oiuei? iaae? aaee/eie eiinoaioe oaeaeeino? ?aaeoe?? (8) i?iaeiaaeaiiy eaioethao ki(RX). Cia/aiiy ki(RX) oae aea ye ? eiinoaio caaeaae? oeaio??a kit (oaae. 3) a?ae??ciythoueny i?eaeecii ia ii?yaeie aeey aeoeaieo noai?a I oa II aeaeo (oaae. 5). Oaaeeoey 5. Eiinoaioe oaeaeeino? ?aaeoe?? i?iaeiaaeaiiy ki(RX) oa ia?eao eaioethao kit(RX) a eaioethaiaiio ioeeaio?eueiiio cai?uaii? a aee?eaaeiaai?aeao ia iiaa?oi? KCl RXki(RX) i4/ieiieue2 nkit(RX) 104, c-1i=1i=2i=1i=2MeI2.91.20.220.082732.40.1EtI1.70.80.110.062332.30.5EtBr1 .10.80.060.051230.90.4I/aaeaeii, neiaaoi?noue a ci?i? ?aaeoe?eii? caeaoiino? aeoeaieo noai?a I ? II aeaeo a ?aaeoe?yo (8) oa (9) coiiaeaia iaeiith i?e/eiith: a iaio ?aaeoe?yo cia/io ?ieue a?ae?a?athoue aeaeo?iiiaeoeaioi?i? aeanoeaino? aeoeaiiai oeaio?o. Ciaiueoaiiy aaee/eie aoaeoeaiiai iiceoeaiiai ca?yaeo i?e ia?aoiae? a?ae iiii- aei aeeaaeain?? i?eaiaeeoue aei cieaeaiiy ?aaeoe?eii? caeaoiinoe. Iane?aeeii oaei? eiiiainaoe?? ? aeecuee?noue cia/aiue aeiaaeeie eaioethao ni aeey noai?a iaio aeae?a ViCl wmetafile8? ??u??????????? ???????????yyy????.????1?????? ????????a???&??yyyy?????Ay¤y $???&??MathType??? ???u?????????"????-????????1/2???u?th?????? O aea/aieo oiiaao aa?oi? a?aieoe? aaee/ei ni aeey i=1,2 ciaoiaeyoueny a iaaeao 80000 - 150000. Cia/aiiy ki(EtX) i?iaeiaaeaiiy (ioeeaio?eueiiai cai?uaiiy) eaioethao aeey ?aaeoe?e EtI oa EtBr (oaae.5) a iaaeao aenia?eiaioaeueieo iioeaie ni?aiaaeathoue i?ae niaith. Aeey ii??aiyiiy, eiinoaioe oaeaeeino? ?aaeoe?? O?ieaeueooaeia aeacaieo noano?ao?a ?c oei?eae-eiiaie a aoeaoii? a?ae??ciythoueny a 4 ?ace. A?aenooi?noue iii?oii? /ooeeainoe aei i?e?iaee a?aeo?aeii? a?oie aeey ?aaeoe?e ia iiaa?oi? KCl iiaea aooe iane?aeeii eiiiainaoe?? ca?eueoaiiy aia?a?? ca’yceo (yeee ?ic?eaa?oueny) aoaeaoeue-ioeeaiooa i?e ia?aoiae? a?ae EtI aei EtBr c?inoaiiyi noaa?e?caoe?? a?aeo?aeii? a?oie (aaeiaai?ae-eiia) e?enoaeii: aeii?oeiaee Br--eii c iaiueoei eiiiei ?aae?onii iaiueoa niioai?th? e?enoae ?, oaeei /eiii, e?ioa noaa?e?co?oueny e?enoae?/iei iieai KCl. A caiae? c iaoai?ciii (8)-(9) cia/aiiy eiinoaio oaeaeeino? ia?eao eaioethao o ?aaeoe?yo aee?eaaeiaai?ae?a (oaae.3) caeaaeaoue ia a?ae no?oeoo?e i?aai?/iiai ?aaeeeaeo R noano?aoo RX, a a?ae i?e?iaee a?aeo?aeii? a?oie X-. Cia/aiiy eiinoaio kit(I) oaeaeeino? ia?eao eaioethao a ?aaeoe?yo RI i?eaeecii o aeaa ?ace a?eueo?, i?ae a?aeiia?aei? cia/aiiy eiinoaio kit(Br). Iaeiae aeacaia ??cieoey a eiinoaioao iaiueoa, i?ae iiaeeeai aoei a i/?eoaaoe, aeoiaey/e c cia/aiue aia?a?? nii??aeiaiiino? aei aeaeo?iio aoii?a eiaeo oa a?iio. Iiaeeeai, ciaiueoaiiy aa?iyoiino? ia?aiino aeaeo?iia ca ?aooiie c?inoaiiy nii??aeiaiiino? aei aeaeo?iio i?e ia?aoiae? a?ae eiaeo aei a?iio /anoeiai eiiiaino?oueny ciaiueoaiiyi a?aenoai? i?ae aeii?oeiaei aaeiaai?ae-eiiii oa aaeain??th aiane?aeie iaiueoiai eiiiiai ?aae?ona a?ii?ae-eiia; inoaii?, i/aaeaeii, iiaeiii iieaaooaaoe ia?aiin aeaeo?iia a e?enoae?. AENIIAEE: 1. Aeyaeaii yaeua iaoai?/ii? aeoeaaoe?? ?aaeoe?e ioeeaio?eueiiai cai?uaiiy a nenoai? “aee?eaaeiaai?ae - n?eue aaeiaai?aeo eoaeiiai iaoaeo (oaa?aea oaca)”: i?e ia?iaoe? o a?a?iieei? i?e e?iiaoi?e oaiia?aoo?? nieae aaeiaai?ae?a eoaeieo iaoae?a MY (M= Na, K, Cs; Y= Cl, Br, I) a i?enooiino? ia?e aee?eaaeiaai?ae?a RX (R = Me, Et, n-Pr; X = Cl, Br, I) a inoaii?o i?io?eathoue ?aaeoe?? ioeeaio?eueiiai cai?uaiiy. I?e iayaiino? a RX -aoii?a aiaeith (R = Et, n-Pr, t-Bu) ia?aeaeueii cai?uaiith i?io?eathoue ?aaeoe?? -ae?i?ioaaiiy, ye? i?eaiaeyoue aei aeieeiaiiy a?aeiia?aeiiai ieao?io. 2. Aeyaeaiee iino-aoaeo iaoai?/ii? aeoeaaoe?? ioeeaio?eueiiai cai?uaiiy o nenoai? “aee?eaaeiaai?ae - n?eue aaeiaai?aeo eoaeiiai iaoaeo (oaa?aea oaca)”: ?aaeoe?? cai?uaiiy aaeiaaia a RX (R = Me, Et, n-Pr; X = Br, I) oaeiae iathoue i?noea ia iiia?aaeiuei aeoeaiaaieo iiaa?oiyo oaa?aeeo nieae oei?eae?a eoaeieo iaoae?a MCl (M = Na, K, Cs) oa KBr ? i?e a?aenooiino? iaoai?/iiai aieeao. Aeoiaee i?iaeoeo?a ?aaeoe?e RX c KCl - a?aeiia?aeieo aee?eoei?eae?a, ia i?i?aaaiaaiee noano?ao aeecuee? aei e?euee?nieo. O ?aaeoe?? i-BuBr c iiia?aaeiuei aeoeaiaaiith n?eeth KCl ia?aeaeueii c i?iaeoeoii cai?uaiiy i-BuCl aeieea? o?ao-aooeeoei?eae oa ?ciaooeeai. 3. ?ic?iaeaia iaoiaeeea aea/aiiy e?iaoeee ?aaeoe?e ioeeaio?eueiiai cai?uaiiy aaeiaaio a aee?eaaeiaai?aeao c iiia?aaeiuei aeoeaiaaiith n?eeth KCl. Aeacaia iaoiaeeea iiaea aooe ?iniianthaeaeaia ia ?aaeoe?? ?ioeo aaciaeaeieo noano?ao?a c iaoai?/ii aeoeaiaaieie oaa?aeeie ?aaaaioaie. 4. Aeyaeaiee iiaee oei aaoa?ie?oe/ieo ia?aoai?aiue - eaioethaiaa ioeeaio?eueia cai?uaiiy aaeiaaia a aee?eaaeiaai?aeao. E?iaoeea ?aaeoe?e RI (R = Me, Et) oa EtBr c iaoai?/ii aeoeaiaaiith n?eeth KCl a?aeiia?aea? eaioethaiaiio iaoai?cio c e?i?eiei ia?eaii eaioethao. 5. Anoaiiaeaii, ui iiia?aaeiy iaoai?/ia aeoeaaoe?y KCl i?eaiaeeoue aei aeieeiaiiy ia iiaa?oi? nie? i?eiaeii? aeaio aeae?a o?i?/ii aeoeaieo noai?a ViCl (i=1,2), ye? aeeeeeathoue ?aaeoe?? ioeeaio?eueiiai cai?uaiiy ? cia/ii a?ae??ciythony nai?th ?aaeoe?eiith caeaoi?noth. Iiaa?oiaaeie aeoeaieie noaiaie ? ioeuei??i? aeaoaeoe no?oeoo?e e?enoaeo KCl: iiiiaaeain?? a ai?iiieo i?aea?aoeao (i=1) oa aeeaaeain?? - anioe?aoe, ye? neeaaeathoueny c ai?iiii? aaeain??, iia’ycaii? c eao?iiiith (i=2). 6. Caaeaaeue aeoeaieo noai?a a?aeaoaa?oueny aiane?aeie ia?aiino aeaeo?iia ia aaeain?th c? noi?aeiiai aeii?oeiaiai aaeiaai?ae-eiia X- c aeieeiaiiyi o iao?eoe? KCl ia?aiaai?oieo oeaio??a, ye? ia aeoeai? o cai?uaii?: iiiiaaeain?? V1Cl ia?aoai?ththoueny a F - oeaio?e, ui aeathoue o niaeo?? AI? iiiaeeiieo aocueeo e?i?th ?c g-oaeoi?ii 2.0000; aeeaaeain?? V2Cl - a ia?aiaai?oi? oeaio?e, niaeo? yeeo oa?aeoa?eco?oueny ianeiao?e/iei neaiaeii c ai?cio?ii??th g-oaeoi?a (g// = 2.0010 oa g = 2.0001). 7. Ioe?iai? cia/aiiy eiinoaio oaeaeeino? (i?iaeiaaeaiiy eaioethao) ioeeaio?eueiiai cai?uaiiy a RX i?e aeaeo?io?euei?e ni?aae?? iiii- oa aeeaaeain?e. Ia i?eeeaae? ?aaeoe?e c RI (R = Me, Et) io?eiai? a?aeiinii iecuee? cia/aiiy noano?aoii? naeaeoeaiino? ki(MeI)/ki(EtI), ui aei??aiththoue 2.00.6 ? 3.10.8 aeey i=1 ? 2, a?aeiia?aeii, a oaeiae - iecueeo /ooeea?noue aei i?e?iaee a?aeo?aeii? a?oie: ?aaeoe?eia caeaoi?noue nie? c EtI oa EtBr aeey noai?a iaio aeae?a iii?oii ia a?ae??ciy?oueny. 8. Cia/aiiy eiinoaio oaeaeeino? kit e?i?eiiai ia?eao eaioethaa o ?aaeoe?yo aee?eaaeiaai?ae?a caeaaeaoue ia a?ae no?oeoo?e i?aai?/iiai ?aaeeeaea R noano?aoo RX, a a?ae i?e?iaee a?aeo?aeii? a?oie X-: oae o ?yae? RI (R = Me, Et) aaee/eie kit a iaaeao aenia?eiaioaeueieo iioeaie iaeiaeia?, oiae? ye o ?aaeoe?yo c EtBr cia/aiiy eiinoaio kit i?eaeecii a 2 ?ace iaiueo? ca a?aeiia?aei? cia/aiiy eiinoaio aeey RI (R = Me, Et). INIIAIEE CI?NO AeENA?OAOe?? AEEEAAeAII A ?IAIOAO: 1. Ieo/aiei N.A., Aeaaeaee TH.A. Iaoaiiaeoeae?iaaiiua ?aaeoeee caiauaiey aaeiaaia a aeeeeaaeiaaieaeao. I. O?eaioeie/aneea ?aaeoeee MeI n KCl e ?aaeoeee MeI n i?aaeaa?eoaeueii aeoeae?iaaiiie nieueth a ionoonoaea iaoaie/aneie ia?aaioee.// AEI?O. - 1998. - O. 34, ? 2. - N. 190 - 194. 2. Ieo/aiei N.A., Aeaaeaee TH.A. Iaoaiiaeoeae?iaaiiua ?aaeoeee caiauaiey aaeiaaia a aeeeeaaeiaaieaeao. II. Aaeni?aoeey RX (R = Me, Et; X = Cl, I) ia iiaa?oiinoe KCl.// AEI?O. - 1998. - O. 34, ? 2. - N. 195 - 198. 3. Ieo/aiei N.A., Aeaaeaee TH.A. Iaoaiiaeoeae?iaaiiua ?aaeoeee caiauaiey aaeiaaia a aeeeeaaeiaaieaeao. III. Aeeyiea aeicu iiaeiuaiiie yia?aee ia eeiaoeeo ?aaeoeee yoeeeiaeeaea n i?aaeaa?eoaeueii aeoeae?iaaiiie iiaa?oiinoueth KCl. // AEI?O. - 1998. - O. 34, ? 4. - N. 502 - 506. 4. Ieo/aiei N.A.,Caiaueeia A.A.,Aeaaeaee TH.A. Iaoaiiaeoeae?iaaiiua ?aaeoeee caiauaiey aaeiaaia a aeeeeaaeiaaieaeao. IV. Oeaiiie iaoaieci ?aaeoeee RI (R=Me, Et), i?ioaeathueo ia iiaa?oiinoe iaoaie/anee aeoeae?iaaiiie niee KCl. // AEI?O. - 1998. - O. 34, ? 5. - N. 670 - 674. 5. Ieo/aiei N.A., Aeaaeaee TH.A., Eiaaeaiei A.A. Iaoaiiaeoeae?iaaiiua ?aaeoeee caiauaiey aaeiaaia a aeeeeaaeiaaieaeao. V. Aaia?e?oaiua iaoaie/aneie ia?aaioeie KCl aeoeaiua ninoiyiey, aucuaathuea ?aaeoeee a RI ( R = Me, Et). // AEI?O. - 1998. - O. 34, ? 9. - N. 1293 - 1296. AIIOAOe?ss Aeaaeae? TH.A. ?aaeoe?? aee?eaaeiaai?ae?a c iaoai?/ii aeoeaiaaiei oei?eaeii eae?th. - ?oeiien. Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa o?i?/ieo iaoe ca niaoe?aeuei?noth 02.00.04 - O?ce/ia o?i?y. - ?inoeooo o?ceei-i?aaie/ii? o?i?? oa aoaeao?i?? ?i. E.I.Eeoaeiaiea IAI Oe?a?ie, Aeiiaoeuee, 1998. Aeyaeaii yaeua iaoai?/ii? aeoeaaoe?? ?aaeoe?e ioeeaio?eueiiai cai?uaiiy o a?aenooiino? ?ic/eiieea a nenoai? “aee?eaaeiaai?ae - n?eue aaeiaai?aeo eoaeiiai iaoaeo (oaa?aea oaca)” i?e e?iiaoi?e oaiia?aoo??. Aeyaeaii iiaee oei aaoa?ie?oe/ieo ia?aoai?aiue a nenoai? “iaoai?/ii ia?iaeaiee ii?ioie KCl - ia?a RX” - eaioethaiaa ioeeaio?eueia cai?uaiiy aaeiaaio a RX (R = Me, Et; X = Br, I) c e?i?eiei ia?eaii eaioethao: aeoeai? noaie ?aaaia?othoueny a eiaeiiio aeo? o?i?/ieo ia?aoai?aiue RX a RCl. Iieacaii, ui o?i?/ii aeoeaieie noaiaie ViCl (i = 1,2), ui aeeeeeathoue ?aaeoe?? cai?uaiiy, ? iiaa?oiaa? iiiiaaeain?? a ai?iiieo i?aea?aoeao e?enoaeo e anioe?aoe ai?iiii? oa eao?iiii? aaeain?e - aeeaaeain?? (aaeain?eiee iaoai?ci). I?eionea?oueny, ui ?aaeoe?y cai?uaiiy (i?iaeiaaeaiiy eaioethao) i?io?ea? ii SN2 - iaoai?cio i?e aeaeo?io?euei?e ni?aae?? aeaeo?e/ii iiceoeaieo aaeain?e: V+-SN2. Caaeaaeue aeoeaieo noai?a a?aeaoaa?oueny a ?acoeueoao? ia?aiino ia aaeain?? aeaeo?iia c? noi?aeiiai aeii?oeiaiai aaeiaai?ae-eiio X- c aeieeiaiiyi a iao?eoe? KCl ia?aiaai?oieo oeaio??a (ii oeio F-oeaio??a). Eeth/ia? neiaa: iaoai?/ia aeoeaaoe?y, eaioethaiaa ioeeaio?eueia cai?uaiiy, aeoeaiee oeaio?, aaeain?y, ai?iiia i?aea?aoea, aeaeo?io?eueia ni?aae?y. AIIIOAOeEss Aeaaeaee TH.A. ?aaeoeee aeeeeaaeiaaieaeia n iaoaie/anee aeoeae?iaaiiui oei?eaeii eaeey. - ?oeiienue. Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa oeie/aneeo iaoe ii niaoeeaeueiinoe 02.00.04 - Oece/aneay oeiey. - Einoeooo oeceei-i?aaie/aneie oeiee e oaeaoeiee ei. E.I.Eeoaeiaiei IAI Oe?aeiu, Aeiiaoee, 1998. Iaia?oaeaii yaeaiea iaoaie/aneie aeoeaaoeee ?aaeoeee ioeeaioeeueiiai caiauaiey aac ?anoai?eoaey a nenoaia “aeeeeaaeiaaieae - nieue aaeiaaieaea uaei/iiai iaoaeea (oaa?aeay oaca)” i?e eiiiaoiie oaiia?aoo?a. Iaia?oaeai iiaue oei aaoa?ieeoe/aneeo i?aa?auaiee a nenoaia “iaoaie/anee ia?aaioaiiue ii?ioie KCl - ia?u RX” - oeaiiia ioeeaioeeueiia caiauaiea aaeiaaia a RX (R = Me, Et; X = Br, I) n eeiaeiui ia?uaii oeaie: aeoeaiua oeaio?u ?aaaia?e?othony a eaaeaeii aeoa oeie/aneeo i?aa?auaiee RX a RCl. Iieacaii, /oi oeie/anee aeoeaiuie oeaio?aie ViCl (i = 1,2), aucuaathueie ?aaeoeee caiauaiey, yaeythony iiaa?oiinoiua iiiiaaeainee a aieiiiie iiae?aoaoea e?enoaeea e ia?u aieiiiie e eaoeiiiie aaeainee - aeeaaeainee (aaeaineiiiue iaoaieci). I?aaeiieaaaaony, /oi ?aaeoeey caiauaiey (i?iaeieaeaiey oeaie) i?ioaeaao ii SN2 - iaoaiecio i?e yeaeo?ioeeueiii niaeaenoaee yeaeo?iiieiaeeoaeueiuo aaeainee: V+-SN2. Aeaaeue aeoeaiuo ninoiyiee i?ienoiaeeo a ?acoeueoaoa ia?aiina yeaeo?iia ia aaeaineth n aeeceaaeauaai i?eianiiai aaeiaaieae-eiia X- n ia?aciaaieai a iao?eoea KCl ia?aiaaieoiuo oeaio?ia ( ii oeio F-oeaio?ia). Eeth/aaua neiaa: iaoaie/aneay aeoeaaoeey, oeaiiia ioeeaioeeueiia caiauaiea, aeoeaiue oeaio?, aaeainey, aieiiiay iiae?aoaoea, yeaeo?ioeeueiia niaeaenoaea. ABSTRACT Yu.V.Dadali. The reactions alkyl halides with mecanically activated potassium chloride. - Manuscript. Thesis, Candidate of Sciences (Chemistry), Speciality 02. 00. 04 - “Physical chemistry”, The Institute of Physical-Organical Chemistry and Coal Chemistry National Academy of Sciences of Ukraine, Donetsk, 1998. The mechanical activation phenomenon of nucleophilic substitution reactions in system “alkyl halide RX - halide of alkaline metal salt (solid phase)” at the room temperature without the solvent is discovered. It is determined new kind of the geterolytical transformations in system “mecanically treated powder KCl - vapors RX” as chain mechanism of halogen substitution in RX (R = Me, Et; X = Br, I) with linear chain rupture: active centers are reproduced in each act of the chemical transformation RX into RCl. It is showed the role of active centers V2Cl (i = 1,2) caused substitutions reactions is played by monovacancies V1Cl in anionic sublattice of crystal and units of anionic and cationic vacancies (vacancies mechanism). It is supposed that the substitution reaction (the continuation reaction of chain) proceeds in according to SN2-mechanism by electrophilic assistance of electrically positive vacancies: V+-SN2. The destruction of active centers is caused by the electron transfer from the near localizied extrinsic halide-ion X- onto the vacancy and the appearance of paramagnetic centers ( in type F-center) onto matrix ECl. Key words: mechanical activation, chain nucleophilic substitution, active center, vacancy, anionic sublattice, electrophilic assistance.

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