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e E E E E E P E P E ooece epa ocpoe ocoo eo, o yeoo. B coca oey ppox o xo opa apea ocaa ooa e yeoopoe eo, paeae p coa. B ppox ocoax pe co oy e eacee oe c ocoo o opo ooe epooo ocaa. e oy poa epay aco, a oy aco eo opye co. Baoece c poo a ocyecec ocoo eop aoco ocaa. e aa o coe epa e oex oypx ac oaa opeeeo ooc.Aoc epax eo ac o aooo coco o oc epa. Ha pc. 13 1 aa oa cxea cpoe epa, cocoe ooo oo co c opye eo oeya ea. Toa ooecx epa oo e peae 100.

yee o-xecx coc epa yoo poo a oex oocoe, oope oyac p aece o a oepxoc o. oee ae yoee ooco po oy, o ooc yeoopox eoe yeaec, x aoece py c pyo pace, a ope oo cpyc a oepxoc paea a. B peee pocxo aoe yoee ooco, e oa oepeoo cee oey a e ac o yeoopoo e. Mooco pecae coo ooy oo co epa, oee yoo oe cya pae cyccee coe e epa (M). oce aepe cpyyp, oy cac, opay aye eype ac (oco), oopx e co oe ype oy ay o apyoo pacopa. B eype ac oo cpaa eoe oey pye ooe ooecx epa ye exao x yopoa oepaax. oce M coyc ye apepx y, epoexaecx xapaepc, a ae eoeypx aoec epaax. epocaece aoec ocyecc ey ape pya o peeax ooo oyco (aepae), o ey pa co (pacepae). cepcoe aepaaco aoec ey oepxoc epa oapyac a paccox o. o aeo peae pacco, e poec 13.1. Pae pecae o oeypo opaa ooecx epa.

epocaecoe oaae. Cyap e x c oe pec oe ya ep aoec a paccox 30 80 c oepxoce eox epa. o e e ocoe oee oex eo eoe apea.

ooe eox epa xapaepyc opeeeo ooc. Xapaepoe pe pa aeoo e oey pa ocoo, px co ppox epaax cocae pa ~ 109 c yeaec o 108 c p eepaype e o ae pocox ee o. aepaa y o o co xapaepyec ooo o oeo y = 107 108 c2/c, ea oopoo co ac o cocaa epa eepayp ( y ~ 10 a/o). Tpacepae a epexo o ooo co pyo (-o epexo) pocxo aoo eeee ( ~ 1000 c). ooc oey pacep eo epaax aoo ee ( ~ 104 106 c, D ~ 1010 10pa c2/c). Boc yeoopoo o epa cocae, a pao, 1 2 ya, o oop o ee oao coco, xo peae a a opa oc o. pooc epa ac o xecoo cocaa, ex yco oe apyac a ce oax exaecx eeo, oa x p ca. Cpeee pe M epeco oe aae p yee ape a epae (epec poo epa). ep epa ac o oepxocoo ae, . e. o pao, oopy yo apa a opaoae 1 c2 oepxoc oo co. Ec epae oec ee a coo op, o ep epa ye ace o ee payca. ep yec a ey, pay cyapoy oepxocoy ae a o a, ao opo, a ae a ce ee epeco eoc epa p oe e cpyypoo eea. B peyae oaaec, o acoc ep epa o payca eea ee po c acyo (pc.

13.2). Bo, o ee aoo payca yy cea, oao ee c payco, o pecoo ( ), yy eopao yeac, po papy epa. Bea pecoo payca yeaec c poco aoeo a epay paoc oeao, e ocec yeee epooc exaecoo papa epa epeco oe.

o-xece coca epa co ac o aooo coco o, oopoe eec p oce pecx eepaypx ae aooo epexoa. Teepaypa aooo epexoa yeaec c yeee e yeaec c yeee ca ox ce pocox ocao. Oo ececex ycox oco ppox o, coepa x eac ee c, axoc o coco. Toa aooo epexoa x e oac opaex eepayp. B eeooo coco yeoopoe e axoc pacoopa, Pc. 13.2. acoc ep eea epae E(7) o eo payca r ocyc epecoo o p aoe paoc oeao. 1 p = 0, 2 p > 0; epxy cpaa opaee op coe a oooo o payopoe. p ae yeoopoa e aco cpec c opaoae e, a (pc.

13.3). eee ca o cococye payopoeoc yeoopoo o. oe ceac o yeoopoo e a ce cxpooo oopoa a 120 cooecye oceoaeoc C C-ce. oooe epeeee a ec coeopao ye coooo oea, yp oopoo oe pocxo epeoc ax oey epe yeoopoy oy.

o poecc, y c yace coox paao, Pc. 13.3. Cxeaecoe opaepae oy po, e e yeoopox ee ooo-xecoe cocoe c pacoypa (III).

coca epa. Cooopa-o yeoopox ae poy opayc ex epa peyae ccoa C Hce, ocoeo ec o pacooe cocee ooe c oo c. epecoe ocee pyec p ec ax op copoa (paa OH, HO, ce copo O ), 2 oope cya o aoece c poco e, opa o x oopo. B peyae a aao ae opayc cooopaae poy #, oope ae peapy c copoo.

a pea po ye oe poepece R+O2 RO2= ROOH.

a o, o poecc cope c opo oopoa H o cycpaa RH pcoeee H paay RO. B oe cxo cooopaa py ep o peeeppyec, aa e ca aao eoy oce o. Ca cooopaae poy oy oa peax peoa a ce ec aocex ax coee. oce oocc coee eooo a (ooepo) eeca, aoecye c a opa copoa. Hapep, -apo, a ae -ooepo eo ya ce copo, eapy eo ceo-oyeoe cocoe. pye aoce oaa aoe xecoe ece, a a, aoecy c O, o ca oepac oce.

B ooecx epaax epecoy oce oepac ocoo epeee oco. B peyae oce o yeaec oc epa, a a p o yeaec oeco x poox o, oc oepee eoeype c yeaec oeco yopoex o c opaeo ooc. B poecce epecoo oce oec cooe paa #, #O, oy peopoa py c pyo c eee oo op ep (~70 a/o). oo ocaoo epeoa poyo pea epooe oyeoe cocoe. ocey epexo oyex poyo ocooe cocoe oe copooac cycae aa cea xeece.

ye co y epe epay ec paoc xecx oeao ( ) oo eeca ey oac, paee epao. Hao (e 5), o xec oea pae = + #T 1n C, (13.1) e caap xec oea, C oepa eeca. Ec pocxo epeoc oo, o x ee ac e oo o oepa, o o epecoo oeaa ( ) a epae. B o cyae oyc oe epoxecoo oeaa ( ) = + RT 1n C+ZF, (13.2) e Z aeoc oa, F co apae (96500 yo/o). Heocpeceo ye co epeoca oo ec pae epoxecoo oeaa d /dx. Ocoo epeec apep, oop co a y pooe oo y epay oo a, oae -a oo, o epeca ocoa o ~ 2 3, a oe ~ 81. Bcece oo ep oa a apeo ac payca r apa e, paa E= e2/2 r, (13.3) oaec o coe. Oca ceye, o oe pacpeee oepa oa ey oo o aa oe oe a:

C - - = (13.4) ~ 1 -1, H2O e C, CH2O oepa oa aax y cao pa paea.

Paccop pacpeeee epoa A+B ey o (2) oo (1) aa, y oopoo ao B ao A+ oaa pao ooc (yc ooc aoa B e). B pa paea oepa aoo B o ae ecoo pec coepae aoo A+. ooy ooo pa paea eopa a aa (2) ece opae ap ee oee oea, e oa aa (1). Oao oacx, aex o oepxoc paea, oepa A+ B pa, . e. coaec ycoe epoepaoc oeo a C = C. B eo oepa ooA x o oo A+ B e ae (2) cece pa epecx poaeocx.

Pc 13.4 po pacpeee oeaa oepa oo A+ B- a pae paea a I II. aa I o pacop ( = 23), a pacpeeee oeaa ( ), pacpeeee oepa (C) aoo aoo. C, C oepa epoo oee a I 1 II.

Ha pc. 13.4 oaa po pacpeee oepa A+ B po epecoo oeaa oepxoc paea a. a o, oacx oepxoc paea ec yoe co, ao oopx oepa A+ B eoao ycoe epoepaoc pa paea e coaec. Coooee oepa epoa yx aax oo oy yco paoec a pae paea a (1) (1) (2) R T ln 1n C A (13.5) OA CA = RT OA ec e F F ocycy, a a a cao 1 0 pae oea a pa = =. Oca c yeo pae1 2 (13.4) = C A / C A ae, o , a ae aaoo A B OA + 1n =, 1n = OB, (13.6) B RT RT (1) (2 ) (1) (2 ) e = -, = -.

O OA OA OB OB OB A p yco epoepaoc ao a CB = C C A = CB = C, + 1n.C2 = ( 1n + 1n ).

A B C C =A B-. (13.7) C Ooee oepa epoa aax ac o . BeA+ B a paoc oeao = ey aa ac o pa1 oc epoxecx oeao oox o oa. Moo oaa, o p yco epoepaoc ao a F = = ( ) = (1n -1n ). (13.8) 1 B A A B F RT Ta opao, pae (13.8) ceye, o eaa paoc oeao oae, oo ec oe pacpeee aoo aoo pa ( ). Xapaep ae oeaa B pa ac o pacpeee oo oo epeco coe oe epa. Aa oaae, o aee epecoo oeaa pa ooceo oea a eec coeao c paccoe o oopa x oe epa ( ) = e x, (13.9) x e ( aee oeaa a pae paea, ocaa, aca o oepa oo ao ae epeco poaeoc. Ocooe aee oeaa ( e pa) pocxo a pacco x=1/, oopoe xapaepye oy ooo yooo co. Bea =1/ aaec o papoa. Oa aae p yee oepa epoa ao ae. B paaex pacopax oa ooo yooo co ocae coe acpe, a oeppoax pacopax e acpe.

o a, o o coe, e oepa oo a ecoo opo ee, e oo cpee, a papoa aoo oe. B cyae oo epa, oa oopo aoo ee papoa, cao oeaa yp epa paec ocycye. B ocyc eeo o oea yp oo epa ocoe o ce ee oe (pc. 13.5). ooy ae oeaa oo eapeo epae e oac o ypo oeaa opyax pacopo a o yae o epa.

eo aa cya ee eco eapex cox x epaax, oa oopx cocae 70 100. Ec oo eapeo epae po eee oe, o yp epa oea ye ec eo, . e. pae poeoo oePc. 13.5. po pacpeee oeaa a pae paea a. (I) epaax pao o (II); oo epae ocyc eeo o (III, 1) p aoe paoc epecx oeao (III, 2): (, epece o1 ea oee a; epec oea a pae paea;, 1 2 epeca poaeoc yx a;

, a papoa epo opo a 1 aa epae ocoe o ce ee oe: d /dx = const. Oao ec oepxoc oo epa cxoo apea ee cpoae ap, o pocpace ooo oepxoc opayec oo epec co. B o coe pooo pacopa yy yepac epocaec pee epax apo. Taoy pe pecye eooe ee oo, cpeeec po x oepa a oepxoc oee. B peyae oepxoc oea a epae ye co opao ace o ooc oepxocoo apa, paoeco oepa epoa pacope eepayp.

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