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ax a. 5 o, o poc ep aa copooaec yeee pecoeaoo oe:

Ea=-(13.97.3)+(9.41.2)lgA, (r = 0.97).

Tae oapyeo, o c poco po aa pocxo yeee a aa (pc. 7):

H=(107.88.8)+(0.490.06)S (r = 0.97).

ln[1] - k 10, c Taa Aaoe apaep pea oce eoo oco xopa (T=25C, aeop, oa epe e peae 10 %) eo k101, M-1 lg A Ea E1/H G S, c-o-1 o-1K-11 0.17 5.7 42.3 40.0 83.1 -145.0 0.000 0.12 0.24 6.5 46.4 44.0 82.2 -128.5 -0.069 0.13 3.53 4.8 30.4 27.9 75.5 -159.8 -0.170 0.14 0.33 6.5 45.6 43.1 81.4 -128.6 -0.197 0.15 0.28 6.1 44.3 41.9 81.7 -133.8 -0.150 0.16 400 - - - - - -0.466 0.17 0.05 7.0 53.0 50.5 86.3 -120.2 0.454 0.Pc. 7. acoc H o S pea12 oce eoo oco xopa (T=25C) -160 -150 -140 -130 - S, o-1 K -Hae oecaooo ea yaae, o ce oc, a o exa pea eoo 11 - 17.

Aa ax, peex a. 5, oaae, o peaoa cocooc eoo o ooe ocy xopa yeaec ceye py:

(17) < (11) < (12) < (15) < (14) < (13) < (16).

lg k = lg ko + peee ypae aea ( - cya oca aecee opmo-, ema- napa-ooex eoa) peo eo acoc (pc. 8):

lg k = -( 1.74 0.01 ) - ( 1.26 0.05 ), (r=0.998).

-H, o 14 Pc. 8. acoc oapa o-1.ca copoc oce eoa oco xopa o -2.(T=25 C, oppe ce eo 13 16) -2.-0.2 0.0 0.2 0. Opaeoe aee ocoo peaoo cep ceecye o o, o eee cxoy oeyy eoa epoooopx aecee yeae peaoy cocooc eoa.

acoc ey oapo oca copoc pea oce oeao oyo oce eoa (E1/2), oop opaae oea opa epoo epoa o oey eoa c opaoae eocoo paaa, ee e xapaep (pc. 9):

lg k = (7.1 0.5 )- ( 14.4 0.9 ) E1 / 2, (r=0.98).

Pc. 9. acoc oapa oca copoc oc13 e eoa oco xopa o oea-a oyo oce eoa (T = 25 C) -0.4 0.5 0.E1/lg k lg k a ceye peeo acoc, c poco e oeaa oyo oce eoa copoc pea yeaec. o oepae peooee o o, o aoece oca xopa c eoa, copee ceo, poeae o exay epeoca epoa.

Ha pepe eoa 11 o yeo e ppo pacope a eece aooepoc poecca oce oco xopa. B aece pacopee pa I, II, IV, VI, VIII, IX, aeo (X), 2epoa-1-o (XI), ao (XII) xopea (XIII). Bo cex pacopex eecoe ypaee pea ee :

d [ 1] - = k [ 1][ PhOH ].

dt acoc oca copoc pea o eepayp opeee aaoe apaep poecca oce (a. 6).

Taa Aaoe apaep pea oce eoa 11 oco xopa pe pacopee (T=25C, oa epe e peae 10 %) Paco- k 102, lgA Ea B H G S, pe M-1c-o-1K-o-I 37.0 - - - - - II 49.0 - - - - - IV 1.1 5.8 44.5 42.1 79.3 -124.8 VI 1.7 5.8 43.7 41.2 78.5 -125.1 VIII 1.5 5.7 42.3 39.9 78.1 -128.4 IX 24.0 - - - - - X 1.1 6.3 46.8 44.3 79.2 -117.0 XI 0.6 6.6 50.2 47.7 80.6 -110.2 XII 0.6 6.7 50.5 48.0 80.6 -109.4 XIII 28.0 - - - - - ax a. 6 o, o poc ep aa copooaec yeee pecoeaoo oe:

Ea=(3.00.4)+(8.00.4)lgA, (r = 0.99).

Tae oapyeo, o c poco po aa pocxo yeee a aa (pc. 10):

H=(93.72.6)+(0.420.02)S, (r = 0.99).

Pc. 10. acXI oc H o S XII pea oce eoa 11 oco X xopa pe pacopIV ee, T=25C VI VIII -1.3 -1.2 -1. S 10 -2, o -1 -Hae oecaooo ea yaae, o ce oc, a o, o exa pea yaao py pacopee coxpaec.

Aa ax, peex a. 6, oaae, o peaoa cocooc oca xopa o ooe eoy yeaec ceye py pacopee:

XI < XII < IV < X < VIII < VI < XIII < I < II.

To ec c yeee opoc cpe pocxo yeee oca copoc oce eoa.

coy aece xapaepc pacope pec apaep coo ocooc pacope B, opeeeoe o cy ooc ooe poco py -cepe eoa paax ypae lg k = lg k0 + B p ce acoc o, a oyea ea acoc c oeo oppe r=0.98 (pc. 11):

lg k = -(0.40.08) - (7.40.5)10-3B.

-H, o Pc. 11. acoc II XIII oapa oca coI poc oce eoa -oco xopa o ocooc pacope B, X IV T = 25 C VI VIII -XII XI 0 100 B eece ae o oce eoa oe e oc o aooepoc. o-oy o cao c e, o exa oce eoa oco xopa oe oaec o exaa oce opaecx pacopex. Ta eco, o oo cpee pocxo ccoa eoa a poo eo-ao, c oop peapye oc xopa. B opaecx pacopex ccoa eoa pocxo ee cee, ooy oo peoo cey exa pea, a epo ca oopoo pocxo opaoae eocoo paaa:

OH O OH + ClO+ ClO+ HClO.

aee eoc paa oe o aoecoa c py eoc paao c opaoae eoxoa:

O O O, -2H+ o oepac aeey oce o ece oca xopa, opay eo pacaac axop:

lg k O O O + ClO+ HOCl.

H OClO O Opaoaac peyae pacaa axopa xopoaca coa xoppye opaece coee, o oce opaoae xoppoox p oce eoa oco xopa:

O O Cl + HOCl + H2O.

O O 3. Cpaee peaoo cocooc oca xopa, eocpaa ocoaoeo co xopa 2,2,6,6epaeep-1-oca o ooe cpa Ha pepe ya-1-oa, 2-epoa-1-oa, 2-xopaoa poa-2-oa cpa peaoy cocooc cpo o ooe eocpay (MO), ocoaoeo co xopy 2,2,6,6epae-ep-1-oca (xop TEMPO) - ocy xopa. B a.

7 pee xo coca poyo, opayxc p ec MO, xopa TEMPO oca xopa a cp, pe coooee cp :

oce - 1 : 1 o/o cyae MO xopa TEMPO 1 : o/o cyae oca xopa.

cceoae e pea aoec cpa c ye oce poo p yco [oucume]0 << [ROH]0, e [oucume]0 [ROH]0 aae oepa oce cpa cooeceo. a pacxooae oce aa a eo acye ooe max = 335, 450, 360 eocpaa, xopa TEMPO, oca xopa cooeceo.

Taa Bxo poyo p oce cpo eocpao, xopo 2,2,6,6-epaeep-1-oco oco xopa Cp poy Bxo, %MO 2-Mepoa-1-o 2-Mepoaa 2-Xopao 2-Xopaa Xopycyca coa poa-2-o Aeo Xopum 2,2,6,6-mempaemununepuu-1-ocua ya-1-o yaa yaoa coa poa-2-o Aeo uocu xopa 2-Mepoa-1-o 2-Mepoaa 2-Me-2-xoppoa-1-o 2-Me-2-xoppoaa ya-1-o yaa poa-2-o Aeo Bxo a a pacxooa oce.

Bo cex cyax eece pe c co oeo oppe ocac ypaee epoo opa. oyoapecx aaopo eecx px pacca ee oca copoc epoo opa k = k[ROH] n; (k ocaa copoc opoo opa). acoc k o [ROH]0 ee e xapaep. eed [oucume] - =k[oucume][ROH] coe ypaee pea ee :.

dt eepaypo acoc oca copoc pea opeee aaoe apaep poecca (a. 8).

a ceye peex peyao, aoee peaoococo coeee ec xop TEMPO, yee oce peapy co op cpa ecoo cpee, ee c ep.

O ceeoc oce oo cy o ooe kmop/ knep, e kmop knep - oca copoc oce epo opo pocx py cooeceo. C o o pe, aoee cee ocee ec MO, a a eo kmop/ knep = 6, o pe a xopa TEMPO kmop/ knep = 1.6, a oca xopa kmop/ knep = 1.2 1.5.

Taa Aaoe apaep oce cpo pa oce (T = 25C, oa epe e peae 10 %) Cp k103, lgA Ea H G S, M-1c-o-1 o-1K-MO 2-Mepoa-1-o 3.2 6.5 49.0 46.5 85.1 -130.2-Xopao 0.12 9.0 73.7 71.2 96.0 -82.poa-2-o 19.2 10.9 71.2 69.6 83.0 -45.Xopum 2,2,6,6-mempaemununepuu-1-ocua poa-2-o 77.9 5.9 40.0 37.6 77.2 -139.ya-1-o 49.1 3.3 25.3 22.9 77.6 -193.uocu xopa 2-Mepoa-1-o 0.04 6.2 60.7 58.2 99.0 -134.ya-1-o 0.05 3.0 43.5 41.0 98.5 -189.poa-2-o 0.06 5.0 53.4 50.9 98.6 -157.Ta opao, poeeoe cpaee peaoo cocooc ax ocee, a MO, xop TEMPO ClO2 o ooe cpa oaae, o o peaoococooc cpa oce oo pacoo p ClO2 < MO < xopum TEMPO; o ceeoc oce cpo - ClO2

BBO 1. caoeo, o poya pea oce epx cpo c ae, opx - eo. p a oeye cpa peo C-H c opayc xoppoae poy. Ocee eoo oco xopa po opaoa cec poyo. Opeeea cexoep pea.

2. ye opao-eece aooepoc oce cpo:

poa-2-oa, 2-epoa-1oa, ya-1-oa, ya-2-oa, 3-ee a-1-oa, ea-4-oa, ea-2-oa, oecaoa, opeoa eoo: eoa, 3-eeoa, 4-eeoa, 4-peyeoa, 2-oeceoa, 2,6-pey-4-eeoa, 2,4-xopeoa c oco xopa. Pea xapaepyc ep opo o aoy peaey. Pacca epoaece xapaepc poecca.

3. Be pacope a ey pea oce cpo oco xopa e oapyeo. peoe exa pea cpo c oco xopa, pye cae oopoo ec epeoc epoa.

4. Beo e cpoe eoa a eo peaoococooc paax ypae aea - eee epoooopx aecee oeyy eoa po yee copoc pea: lg k = -(1.74 0.01) - (1.26 0.05). Haeo, o c yeee oeaa oyo oce eoa oeypa ocaa copoc pea lg k = (7.1 0.5 )- ( 14.4 0.9 ) E1 / yeaec:.

5. Peaoa cocooc oca xopa o ooe eoy yeaec ceye py pacopee: 2-emunpona-1-o < mao < 1,4-uoca < aemo < aemoumpu < muaemam < uxopema < enma < mempaxopema. eee ocooc pacope B po yee oca copoc pea oce eoo oco xopa: lg k = -(0.40.08) - (7.40.5)10-3B.

6. peoe exa pea oce eoo oco xopa, pye cae oopoo ec epeoc epoa o oey eoa a oeyy oca xopa.

7. p cpae peaoo cocooc eocpaa, xopa 2,2,6,6-epaeep-1-oca, oca xopa o ooe cpa ycaoeo, o aoee peaoococoe xop 2,2,6,6epaeep-1-oc, aoee ceee - eocpa.

Ocooe coepae ccepa oeo ceyx yax:

1. paoc C.A., Cyopa E.C., aaoa H.H., Xypca C.., epeoe B.B. Ocee cpo eocpao. // . AH, Cep.

x. -2000.-8.-C. 1338-1343.

2. ae .M., Cyopa E.C., oa A.B., aaoa H.H., ae .., Toco. A. Baoece 2,2,6,6-epaeep-1oca co cpa. // . AH, Cep. x.-2002.-6.-C. 901-904.

3. ae .M., Cyopa E.C. aaoa H.H., ae .. Ocee eoa oco xopa. // XIV Coy "Copeea xeca a": Te. o. - Tyace, 2002.-C.125.

4. Cyopa E.C., ae .M., aaoa H.H., ae .. Ocee cpo oco xopa. // a ooea aya oa - oepe o opaeco x: Te. o. - Eaepyp, 2002.-C.426.

5. Cyopa E.C., ae .M., aaoa H.H., ae .. eece aooepoc oce cpo oco xopa. // oepe oox yex, acpao cyeo: Te. o. -a, 2002.-C.81.

6. Suvorkina E.S., Ganiev I.M., Mikhailov V.A., Kabalnova N.N., Imashev U.B.

Influence of Solvent on the Oxidation of 2-Propanol by Chlorine Dioxide. // VI Voevodsky Conference. Physics and Chemistry of Elementary Chemical Processes: Book of Abstracts. - Novosibirsk, 2002.-C.143.

7. Ganiev I.M., Suvorkina E.S., Igoshina A.V., Kabalnova N.N., Imashev U.B, Tolstikov G.A.. Oxidation of Alcohols by Chlorite of 2,2,6,6Tetramethylpiperidine-1-oxyl. // VI Voevodsky Conference. "Physics and Chemistry of Elementary Chemical Processes": Book of Abstracts. - Novosibirsk, 2002.-C.122.

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