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B KHHCTllqeCKOe ypaBHelIHe B CTeneHH, p3BHOff COOTBeTCTBYIOIlJ.eMV CTe
XHOMeTplflICChO IY K03cp<pHl..I.lIeH ry ,:Horo KO 1n011(,HTa. ¥
B C3;\IO\.l .n.e.'1e, peal\Ll.1I1O
A+B+B=C+... (II')
CKOpOC rb p aI<ll.Hn, nponOPllJlOHa.r1bHaH KOHUCIITpaU1I5I\1 Dce).. \ lfa-
C.TBYIOIlI,HX B lien KOMnOIIeH rOB, .JJ.Ba>KJ{LI .n.OlDI\.Ha 6bITb npOnOpI 1I0Ila,1LHa
I\OllueHTpaUHU [B], T. c. onpe;I.eJIfleTCSl ypaBHenuer..l
(l) = k [A] [8] (BJ = k [A) [B) 11.3)
B 06w.er-.1 c.f1yqae }1)1f1 peal\UHH
llA + bB -;- . . . = a' A' + b' B' +. . . (I I I)
).ameTJi4eCKOe ypaBHeHuc n 'eer BII,J.
flJ = _ d [AJ = _ d [BJ _ _ 1 d [A') 1 d fB']
I a dl b dt -... - 7 dt = iT {jf =
.Il [AJD [BIb
nOI<a3aTe:m CTeneHII a, b, . . . B I<HHeTlIlIeCKOM
Ha3bIBaTb nopH,lJ,Ka:vtu peaKHnII no ROMnOHeHTa\1
nOKa3a re.ll'ii - 06Il1,I1M nopn TU(01\l peaKlLHlf. .
TaK, peal<unn TJlna
II .'"1 n
(1.4)
[A] = [A]oe- I .. t
( 1. 6a )
A=bB+cC+.. .
(IV)
KOIlucHTpau. nst o;I.HOrO H3 npOl.YKTOH peaKUHu [8 L paBHaH nY.rIIO
B Ha'-la.'TbIlhlH MO!'vICHT, U3MeHHCTCH BO BpCMCHTI no ypaBHeHHlo
[B] = b ([A] 0 - [A n = b [Ao] (1 - e -kt) ( I. 7)
H3 ypaBlIcHllSl (1.6) CJIe,,'J.ycT, liTO KonnCHTpan l151 HCXO:1.HOro Bell.le-
CTBa 311aQIlTC,TJbHO YMCHbIUaCTc.5-I BO BpeMCHn, Ha4HIIafi CO 3l1allcHHi:j t,
COII31>.ICp HMbIX C Be.1IllJJ1HOii 1 i k. Be.rUILJ nlla I A) C rpe HfTCH 1( lIy.T1lO,
O,!J.HaKO no..'IJIoe n3pacxotI.oBaHlle A OCYll\€CTBJlHCTCH J1IIlllb aCIlMn rOTIl-
LJeCKII npn t = 00. Ana.T1or1l4Ha II KIHIBaH 1I3MenenUH CJ(OpOCrH peaK-
linll BO Bpe lcHn ([} (t) = !?. IA], OT.1ULIalow.aHC5I OT KpHBOii r A) (I)
TO.:IJ,KO MacwTa6o 1 no ocn opl.IIHaT.
ll3 ypaBneHHH (1.6) c..le}1.yeT, liTO KOIIl(CHTpallliH HCXO.r!.Horo I\OM-
nOHeHTa YMCHblIlaeTCH B e pa3 3a BpCMfI t e = Ilk. TaKaH uHTepnpe
TalUIH Xapal{TCpn3ycT (pIl3Ut.IeCKlIi"'1 CMbIC"T) KOHCTaHTbI CKOpOCTll peaK-
li.HI-i ncpBoro nOpH.IT. Ka . 1Ii\.feIOll(eft pa3\lepnOCTh ce1{-l: OHa 06paTHa BeJIII-
lJ1JHe BpeMeIIII Y lellbUIeIIIIH KOHu.ellTpallHII pearHpYlOlI ero KO lnOllcH ra
B c pa3.
ypanneHun npUH5ITO
A, B, .. ., CYMMY
n p OT< KalDT J a K l)eaKI
J.HH nepBoro nopH..'J,Ka, a
A + B = a' A' + b' B' + . . .
2A=a'A'+b'B'+.. .
(V)
(\'1)
Ii
KaK )Jeal\Ll.un BToporo nopSl.J.1<a, nplltIeM peaKLlHH (V) HB.lIHeTCH peaK-
uneJl nepBoro nOp5l;I.Ka no KOMnOHeHTa 1 A liB, a peaKUH5I (\" 1) -
BToporo nOpSlJI.Ka II no }<oMnoHCHTY A 11 cYMMapno.
1l0CKO.TJbKY KOIJueHTp u.lIfI Kam,lJ:oro 113 pearHpYJOll nX KOMnoneHTOB
nponopUIIOHa,,'TbHa nepBOIf... CTeneHlI .n.aB.TleHIH::r. CKOpOCTb r330Boii peaK-
JJ.1t1l B03paCTaCT C pOCTOM OOll..lero ,Llan.TJeHHH p nponopUHOHa"T}bHO pD+b+...
T. c. npOIIOpII.nOna.1LHO crenCHH p, paBlIoIi OOIll,e ty nopSJ KY peaKu,IIn
12
13
dn n
- - = Im-
dt
( 1.9)
.ll.r:ISI peaKUlI1l H roporo nopH.!1.I{3 BpeMH nOJlynpeBpa U le.llllS-l saUHCIIT
o'f uaQa"ILl1oi'l KOHuel-lTpaUHll, a KOHCTaHTa CI{OPOCTIt - 01' Bbl60pa CH-
e reMbl eLIJIlIIHl l,JIH KOlIuel-ITpaUIIII; B 1136paHHoii HaMil CHCTeMC e111-
lUlU KOHCTdllTa CKOpOCTlI peal\Ullii BToporo 1l0p5I,lI.Ka H3:\lepfteTCH
(.J{3/ (.\-tOJlb . eel\).
BBe..1.eM TaK )Ke, KaK 11 )J.Jl5I peaKl1.HH HepBoro nopH,IT.K3 6e3pa3 lep-
Bble k.OHueIITpaUHIO CG = nlll 0 11 BpeMH 1" = flt o .& = kn of. 3-r0 n03BO-
.f1HeT npHBccTH KHHCTHlJeCKOe ypaBHcHIIc .'I1060ii peaKUHn BToporo no-
pSl..L1Ka npn IA)u = IB10 K YHIIBepcallbHoMY BH1J.Y:
1
a = __ (1.12)
1 + 't
3aBHcliMoCTb (1.12) H306pa>KcHa Ha pHC. 2. TaK }Ke, haK Ii ;J.Jl5I
pea1\U llM nepBoro 1I0p, H;J.Ka KOHl1.eHTpauull pearHpYlOllJ.liX I\OMnOHeH-
TOB, a C 1-1I1MI1 II CKOpOCTb peaKUllli nalJJIHalOT 3aMeTHO YMeHbllJaTbCH
;l)UI 3uallcHliH 't, c.oli3MepllMblx C eJU1HlIuelf, H aCII lnTOTUllCCKn CTpe-
MflTCfl K HY.'11O ,1I)lH 6ecKoHclIHO 60.TIblllorO npc!-.-ICHli peaKTuIH. ·
CJIo>KHbie peaKlI.H11 [6). YpauHeHH5I peaKunfI nepBoro II BToporo
nop5l.ll K a npe}J.craBJlHIOT c060ff HaH60.TIee npocTbIC 11 B TO LKe npe:'>'IH
n8>KHeiiwue TUnbY KHHeTUlleCKIIX 3anHcHMocTeti. 11M II , O,!J.HaKo, .n.aJIehO
He nC4epnbIBalOTCH nCrpeqalOll uecH B npaKTHKC 3aKOHOMCpHOCfJI.
KaK 6y.n. eT BH)J.HO 113 T{aJlbHeihllero, MHOI'ne peaRlI.llli IIMelOT TpeTHii
nopH;I.OK, qaCTO BcrpellaeTC5I ;lp06HbIlt nOp5l,lJ.OK peaKUHH H ,!J.a)Ke HYJIeBOil
(lIO 01.1I0MY 1f3 KOMnoneHTOB), liTO 03uallaeT He3aBIICHMOCTb CH:OpOCTII
peaKUHlf 01' KOHII.CHTpalI.IHi o)].lIoro 113 BsaI1Mo.n.eikTBYIOlIJ,HX BClllecTB.
Ha6.TIIO.D.aIOTCH HBJIeHHH KaTaJIH38 M MHfn6npOBalllHI (OTpUua'feJlbHOrO
l,aT8. r HI3a) - YCI{OPCHHH IIJlH COOTBeTCTBeHHO saMe)J..neHIHI peal<U HH
I{OMnOHeIlTOI\'I, I(OHueHTpallIHI Koroporo He M3MeHHeTCH no Xo}].y peaT{-
UIIU. PacnpOCTpaneHbl Tal0KC npou.eCCbl aBTOKaTa.rIH3a pea KlllUI ce mc
npo.n.YK ra:\ll1, B pe3Y JIbTaTe lIero CKOpOCTb peaKu JIH ,lI,0 onpe,'J,eJIeHHOrO
npe;lc.na B03paCTaeT no Mepe paCXO OBaHHH UCXO.aHbIX KOMnoneHTOB,
a He Yl\'tCHbUlaeTC5I, KaK Y .n.pyrHx rnnOB peaKlUiH. B CllCTeMax, 6J11I3KHX
K repMO'(HHaMnllCCTUi paBHOBeCHbl"vl, HalIHHaeT nrpaTb 3aMeTHYlO pOllb
peal{UHH, 06paTHaH ocnoBHoii.
B peaKUHOHHOH cpC.Ll,e, KaK npaBIVIO, OJI.HOnpeMeHHO npOTCKaeT
lie CI{O.71bhO nponecCOB. TaK, O,!J,HH H3 KOMnOHeHrOB MO/Ker paC","O!J.OBaTbC5I
no .lJ.BYM II.'ITI 60.TJee pa3.TIUllHb1M napa.'l,,'Ie..TIbHbHot peaKUIlHM. B JI.pyn1'{
c.rIYlJaHX peaKUHH MC>KJJ.Y HCXO.u.HbT!vIH KOMnOHeHTaMH He ,lI.aeT Heno-
Cpe.:lCTBeHHO KOHeqnOrO Bern.eCTBa. 06pa3yeTcH npOMe)l{YTOllHblit npo-
.n.YKT, HlIor.u.a HeCKOJ1bKO T8KHX npO..'1.YKTOB, II TO.TIbKO no 3TO!vIY CJIO)l{-
HOMY nYTlI nOCJIc.n.OBaTeJIbHbIX npeBpa CHnfI CnCTCl\'18 npHXOTJ,HT B KO-
IIC4Hoe YCTOIIllUBoe COCTOHHHC. TaKOB, Hanpn 'Iep, MexaHU3M OKliCJIe-
HUH OpraHUlJeCKHX BCIll.eCTB KHC.TIOpOJI.OM.
B CHCTel\'le, f e npOTeKalOT nOCJIeAOBaTeJIbHbIe peaKUlur, KOHUCHTpa-
l.I.HH npO:\ofe}KYTOllIlbiX npO)1,YKTOB, 113MeIHI5tCb BO BpeMeHH, 06}l3aTe.TIbHO
npOXO)J.S1T LJepe3 MaKCHMYM. TIpH aBTOKaTaJIllTuqeCKO:\1 npCBpallleTlHIl
CI\OpOC rb pcal<UHH TalOKe JI.OCTHraCT Mal<ClIl\IYMa, noc.. e llero B.1JHIHHC
113!leHIUI 1<011l1eHTpau nlf nCXO.il.HbIX npo.u.YKTOB CTaHOBHTCfI npeo6.'la-
15
Ll.1UI nar.ruJ)]JIOCTlI BBe e 6
[ ] I A ] M e3pa3 epHble hOHUCIITp a U. lllo C(-=
. 0 II BpeMH T = II I = kl TI p
hOHll.lHTpalll111 Ii Bpl'MeHJf B HOell ., OnOpUlIOHa.TlbHbiC 06bIllHbr 1
HOBHTCH YIIIIBepCa.'IbIlbIM JlH rIlO IX nepeMeHllbIX ypaBlleHue (1.6) CTa-
lIMeeT BH)J. · oro npouecca nepnoro nopfl..'J.Kcl, OHO
_ -'t
a - e (I 8)
3aBIICJlMOCTb ..nOJlH npopcarup .
110ro npeMenIl T npe..lcTan.1eHa lIaO a:UI ro ; w.eCTBa ry" 01' 6e3pa3:-o.rep-
.D,auiIeHH}I II CTeIleHII a.30aB!IeHU . c. . eJInqUHa ex He 3aBHCIIT 01'
C:\lbIc.131"OrO p p' 51 IIl1epTHhlMH npU:\ofecsaUI. cI>H3H4ecKHii
. OqeBHTJ;CH. eaKunn Hepnoro nOpHT\Ka npe..n.CTaBJUIiOT c060ii
ct
ex
7,0 I,D
0,8 0,8
0,6 0,6
fJ, o,lJ
(7,2 (1.2
o " 8 TZ 16 20 ?:
PlfC. 2. npOT€KaUHC peaKlU1II
BToporo JlOpHJ).Ka EO npeMeI-Hl.
TIIn CnOHTaHHOrO npouecca: on p e"e nCHH a cr )1,0 11 (a
""' . F1 . 51 lie KOJIUqCCTBO )
I1alIHLJHOrO pearnpYlOllI,Cro new.eCfBd, He 3aBHCHUJ.aH OT ero I\OHueHT a-
U.HH, caMonpOllsBo.'IbHO pacn8;J.aeTCSI 3a e.AlIHlllty npeMeHH n03T iY
II, BeJl IjIlHa KOHCT3HThI CKOpOCTII peaKUlI1I ncpBOro nopSlAKa e 3aBII IIT
or Bbl opa pa3MepHocrn ;J..'l51 KOHllCHTpaUHn.
peaKLl.H I BToporo nOpSl)l.Ka. PaCC:-'fOTpHi\I npocTeifwui't c.TJytIaiI peaK-
UlIll THlId II.TJII Tuna V I1PH Ha4aJIbHO;\1 YC.f10DIHI [A] = iB J =
a 3Ha4HT Ii [A] = [13 1 - Jl 6 ' - .. 0 0 11 o.
- 1l. .'IH 0 eux peaKllHIt KnneTnqeCI<Oe V p aB-
HCHne JlMeCT BI1}.J. -
o 1 2 J 4 5 7:
Pnc. l. npOT€KaHHC :-pedK1llllf
nt'pnoro nopn,n.Ka 80 Dpe teHIl.
I IHT(: rplIpoBaHlle (1.9) npH HaQa,,'1hHOM ) C. IOBIIII f = 0, 11 = 11 0 .lLaCT
k - I ( llo )
- fllo n - I
(1. (0)
1l = "0
I + knot (I.IO())
060311alJaH 4CpC3 t - Bf)eM
05 t 1 51, lleOOXO'UIMOe )]..TIH H3pac:\o.nOB3HlIH
nO.'10HHHbI na4a.:.bHoro KO.lII4eCTBa pcarnp) Jomcro Beru.CCTBa 113 yp aH-
lIeHllfi (1.10) HafU],Cl\'I: ' .
I
lor.=-
,Ot kl10
(1.)))
14
1'{aIOIlUII\I. KcDh,'].iHI 113 3.!ICMeli rap IIbI 'I( pL'a, I<UJltI COCTaB'lHIOLLlHX eVMl\fap-
Jlhlli 11 pOllCCC, H!\ICCT npocToii Mexall H3 1 (CM. pa3,1. 2) II npoTel<acT no
KlflJenllll\CKO IY ypaBHcHIIIO . .TIH peaJ<llUII nepBoro n.rIlr In-oparo TlOpfl!1.l<a.
QltHa KO lIa/IO)l{eJlUe pea 1\ lI. II II npIlDo)J.IfT 1\ TO:\'IY, lITO J{OHueHTpaU,IIH HC-
>'O..'.U LIX 1{0 lnOHE'HTOB I1JMeHHIOTC5I no Bpe IeH If no C.T10}l{HO fY 3al{OHY.
I\HHe BIlJeCJ{I1e 3ClKOJlOMepHOCTII C.10}{{1I0ii CI1CTeMbl onpe}].E'tl5IIDTCH
no npl1lll.llIny hOJ.eJlllrrciiua. On 3aI .THOqaCTC5I B Tot",l, 4TO J{a}K;J.aH 3.'le-
MCHTapHaH pcaKUIHI r<.UIurOI{01vJnOHeHTHoii CIlCTeMbl 13 ..lIo6oH MO ICHT I3pe-
I(,HJI npOTeJ{aCT ne3c1BIrCHMO or ,u,pyrnx H nO 4I1HHCTC}I 3al\OHV cii-
CTBYJOIlllIX Mace. 6a.r1aHC paCXO,"{OB3J1HH H' 06pa30S3HIfH aTIIoooro KO:\HIO-
HCIlTa CIICTe 'fbl COCT3B.'lHerCH C yqeTOM Bcex 3..1e fC'nTapHbIX npOl eCCOB,
B J\OTOpbIX Y43cTByer 3T01' KO IIIOHeHT H.!JH np0.J.YKT KOTOpLIX 011 npc -
CTaB.'IflCT. .
BTopofi Ba}KJlLlll npHHllHn. 4aCTO HCIIo.TJb3yeMbIlf npu paCCMOTpCHlI1f
CJTO}KHbIX npOli.CCCOB, 3a K.7IlOqae rCf! B TOM, qTO CKOpOCTb MIIorOCTa 'ulii-
HOl'i peal{li.UH onpC..1.e.:UICTC5I CI{OPOCTbIO ce J-IaU60. T Ice MC,1.:leHHOH CTa;J,HH.
Ooc.nC:UiHH OJ\a3blBaeTCH «Y3KHM fCCTOJ\f» rrpOllecca, II 3HallUTe.1bHOP
1f3MeneHue CI{OpOCTe" pyrllx cTaTJ,ni-i MailO B.'IIHICT Ha CYMMapHYIO CKO-
pocrb peal<lUIII. n03TO IY onpc,aeneHlIe CKOpOCTH MHorOCTa':UliiIlofl pt'aK-
UIIH CBO;J,Jl1'C5I K 1I3MepeHIIJO CKOpOCTH Me:r,.TIeHHOfr C1'a){HIt.
HeCOOTBeTCTBHe HCTHHHoro nopHaKa pea HH CTeX"OMeTp" eCKOMY
ypaBHeHHIO. CYIllCCTROBaHII peaKUUrl HY TJeBOrO, ;1.pOOHOro H OTplfua-
TC.lJbHOro IJOpH,lJ.Ka H pynIe OC06E'HHOCTII I\JlHCTHI<l1 pea..TJbHhIX npOli.ec-
COB lie npOTl'IBOpCLlar 3aJ{OH) ;J,eHCTI3YIOUUIX Macc. 3TH 3aKOHOMepHoCTII
HB.:HlJOTCH C.TIe.:tCTBlIe;\1 C.'IO}KHOro fcxaIlH3Ma pcaKUHII, B I<OTOpO 1 MorYT
IIpHJlH 1aTb Y4aCTne HeH3BCC1'HbJC npOMeiKYT04Hbie np0!lYI<Tbl. KHHeTH-
I.IE'CI{Oe ypaDueHue OJDKHO cOOTBeTcTBOBa rb HC rllIlIlOMV Me"XanIf3:\nr
ncpBUlfHOrJ peaJ I..UIH. flpnBLI4Hafi 3anIlCb C1'eXHOMeTpHLIeCKIIX COOTIIO-
mcuui! MC>K1Y pearHpYJOlll.lIMH KOMnOHCIITaMU, KaK npaBH.IJO, HC OTpa-
)1{aE'T IIC1'IIHIILIi'1 \ICXaHH3J\I nponecca If HC MO)K€'T 6LITb nOllO}Kena R OC-
Hony 33K..lJ104ellllIl 0 I{HHCTHLJeCJUIX 3aKOHoMepHOC1'5IX. HaJ(OHCU. !{.1H
01HOH If Toij )I{e CIICTeMhl MeXaHJf3 1 peaKIlHH u ce CYI\I:\lapHbIii nOpHJl,oh
B p33.1I11IJHbIX YClIOBH51X MorYT H3MCJlHTbCff. 50JlbIlllIHCTBO pea..TIbHhIX
XIIMHqecKIIX peaKunii, B TOM IJUCaile OKHC.TIHTC.TIbllbiX npOUCCCOB, npOTe-
I(BeT C 06pa30BaHIIeM npOMe}KYT04HbIX npO!{YKTOB, HeYCToi'1411BbIX npn
HH3J<JlX Te\inCpaTypax.
TaR, CTeXJlO 1eTpHqeCKa5I 3anIlCb npOl ccca rOpeHIlf! 1\IeraHd
CH 4 -+ 20 2 = eO l -1- 2H l O
crCi1I1ii. nO.:}TOMY If:iY4eHue !(IIUeTH4CChIlX 3aKOJlOi\lCpHOCTell OKa3hI-
BaeTc51 O;J.lllfM 113 HaHoo.TJE'e Ha:1.€,}KHbIX MeT011.0B I1Cc.YIe.)1.0naHH51 MexaHn3 la
x II!\UI4CCI{OrO B33IH\'tO!l,eiicTBJHI.
2. MOJIEKYJI.SlI>HbIA MEXAtI"3 XHJ\Hp..IECKHX PEAKLU1A [71
COYJlapeHHS1 MO.,1eKYJ1. Pacc loTpll 1 \teXanU3;\1 l\I1IhpOnpoueccoB, 110
I OTOPOMY B3aJD10,.1.eiic1'BYI-OT MO.fJCKY.rIbl pearnpYJDIJ..J.HX ra3?B. lI3RecTI.lo,
liTO CII..1Ll n(HiT5DKCHHfl II OTTa. KlIBaHH5=1 \ICiK:{Y Mo.TJeI<) .'1 aM II 6bICl po
\'MCHblllalOrCH c YBe. nqeHlIeM paCCT05IHII5I. n031'OMY Mo. eI<y.1JbI \forYT
.1HHTb .apyr na lpyra .1I1111b npn 3Ha4H1'e TJhHOM COJIIDKeHHII, K01'O-
poe \10:iKHO paCCMaTpnnaTb KaK cOY.l1.ap€'HHe. nOMIHvIO MO:\leHTa COYlI. a -
p eH IUl, HC KJllOlICHO BCSI Koe B3a H IO l.eHCTBIIC MeJK11.Y Mo.'1eKY .l1aM II r a3a,
re .f 60..'ICC CTO.,lb IHITeHcnBnoe, KaK XHMH4eCKaH peaKl IHI, T. e. CBH3aIl-
Hoe C nepepacnpelJ,CJICHHe I aToMOB pe .rnpYIOII1.HX Mo.neKYJI. j\\O.,leKY-
.'15tpHbIH McxaHH3M XII fII4E'CKHX peaKUHH onpe;(C.rIHeTC5I 1'eM, liTO l''''I TIe-
l<y.TJhI B3aUMOlJ,efICTBYIOT npn CTO.1KIIOBCHIHI"X, npOHCXOlJ,fI1lJ.HX B pe3Y llb-
faTC xaOTHLIeCKoro TCn.,10Boro J.BlI>KCHHSl.
nOCKO.TIbKY Ten.TIOBOe ,.1BIDKeHne t'lo.TJeKy.TI He ynop5I,J,OQeHO, OHO IlOTJ,-
4nITHe1'CH craTHCTIIqeCKIIi\" 3aKOJIaM, n03Bo.'I51JOllI.nM Bbl1.IIIC.,1Hrl> cpe;UIlo
a6COJlJOTHYJO CI<OpOCTb fO.TIeKy.l V II llaCTOT)' coyn.apeHllii. Be, !ILlHlla v
01.H03HaQnO onpe;J,c.1HCTCH TCMne.paTypOII ra3a T (a6co.1IOTTlOU) If era
Mo.1ehy.IJHpHOH Maccoii 1
- , [SRt
1 = V :I."l
(1. 13)
r)l,C R - YUIIBepca..1bHaH ra30BaH nOCTOHHHHH. 3HaqelliHI CP€'11. He I'l
CKOpOC1'H MO.TICKY.;'J HeK01'opblX ra30B II HX iT.pyrne MO.1CKy..1JHpHO-KHHe-
TIIlJCCKlle xapaK1'epnCTMKH npUBeTJ,eHLI B 1'a6.TI. 1 [8, 9]. ..
B 3.T"feMCHTapHofr KHHeTIIIJeCKOii TCOpHII ra30B B3aMMO;I,eHCTBUe )], I1-
}l\Vill.UXC51 Mo.TIeKy.1 paCC\1aTpHBaCI"C5I KaK ynpyroc cOY.r:lapenne >KCCTKHX
wapoB, IIMeIOll HX )l.nar\'lcTp 0". Dpu cOY,ZI,apCHIUIX .lI.BYX MOJTCKY,,'1 C .1.lI a-
:\leTpaMII (J 1 Ii (J ll.eHTpLl 10.TIel{y..1 c6.rIlDKaIOTCSI )1.0 paCCTOHHJI5I (Jl -
T a 6 J1 II II a I. MOJleKYJISIpHO-KUHeTlllleCKlle xapaKTepncnlKu
HeKoTopblX ra30B npl1 T= 288 0 " H P -::- 1 am
He l1.aeT HHKaKIIX OCHOBaI-lHI1 C 1 III1'3Tb, KaK 3TO nO.J.lIac npaKTHI\OBa.10Cb,
LITO <D = I?, [CI-I 4 ] (02]2 11 lITO 3'1'0 peal\llHH TpeTbero nOpH,lI,l\a. JlccTJe-
OBaTIHe IT.TIa1\feIHf \.feTana nOKa3a.TJO, qTO B peaKHJIII YlJaCTnYIOT XH'tH.-
lICCKH aKTHBIIble pa.rr.UKaJlbl - HeHaCbllli,€'IIHbIC rpynnbl aTo .toB - CH: h
CH, OH, a TalOKC a1'OMapHble BOJI,OpO'{ H KHC.TIOPO..1J:. B 3aBHCH!\.fOCTH
OT YC.'lOBllfI npn OKHC:ICHHII MCTana MorYT o6pa30BhmaTbcH If l1:pyrIle
n pOl\le>KYTo4HhIe n P0,lJ,YI{TLI, Hanpn\lep nepcKliCH Ii (pOpMa.TI!>!J.enl':1,.
Ronpoc 0 np IIMt>JlJlj\.tOC1'H 3aJ<OHa AeiicTBYJOIn.nx facc cnO H fCH l{ IIpa-
BIInbHO\IY onpe!I.e.1eHJlIO reX3H1I3Ma peaKllIIJI II ee noc..TIe.:toBaTe.TJbHhIX
16
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... u
c::. .
DellleCTUU "-' . HE'IQ.eCTBO .::; 0 . I
I -.. .
"- 0 .,. :J! ..-: S
< 0 '3 -
I;; b -< . J'; .c '"
II" 1740 2,74 11,8 14.8 H 2 O 582 4,60 4,18 13,9
N: 466 3,77 6,22 7.50 CII) 293 5,33 3,11 9,43
o. 437 3, (j 1 6,78 6,44 cll s 617 4,16 5,11 12, 1
CO 467 3.75 6,29 7,42 N 1-13 598 4.43 4,50 13,3
CO 2 372 4.(j2 4,14 8.99
2 A. H. P03.'IOBCIiUii
17
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= 2 (0'1 + 0'2)' nOC.ne qero lvlo.ileKy.rlbI, ynpyro OTTa.m<HBaHCb, y).!,a-
.TJ.HIOTCH ,n;pyr 01' )I.pyra B 'COOTBeTCTBHH C 3aKoHaMH lvlexaHHIUI. DO.rIbWeE'
C6JUDKeIU:le u.eHTpoB MO.lleKY JI neB03lvlOLKHO, a npH paCCTOHH'HH Me}KiI.Y
u.eIlTpaMH, 6q.TIblileM 0'12' B3aHMO)I.ei'1C1'BHC l\'fe}KAY 1\'lo.TIeKY:Ia Hl orcy1'-
cTBye1'.
Boo6patKaeMblH c.1Je)1. .nBH>KeHlIH M(WeKYJIbl 1 B npocrpaHCTB€ MOIKHO saMeHHTb
3KfHmaJIeHTIIbiM lI.I1JIllH.npOM Jl..lIa feTpOM a l' MO,i'IeKY la I coy.n.apHeTCH co Bcer-m ;J.pynnlH
jo,mv'IeKy.la m C .nHaMeTpa .m 0'2' BXO.ll.Hll HMH B IIpeJ eJlbI )Toro CJle.ZJ,a; !:IX lJ,eHTphl naxo.
,lL5ITCH Ha paCCTOSIHH51X, He npeBbllllalOlIJ,HX a 12 OT OCH YKasaHHoro UH':IHH;J;pa. CpCAHee
4HCJIO MOJI€KY.1J I3 UHJIHIUI,pe J1.HaMeTpOI\'1 2a 12 on pe;(e.ilHeTCH HX KOHueHTpalJ,UeH B ra30-
BO:\-I npOCTpaHCl'BC Ii 06'beMO:\'1 lJ,H.'ll-lHJwa BLICOTOH vt, BelIM4HHbI n, a 12 H V onpe;I.e.rl51IOT
tmc.lJo coy.napeHUH B e)I.HHlHte 06Le m 3a eJI.HIIHUY BpeMcIIH.
TaKaS! HHTepnpCTalJ,HH npouecca coy.rr.apeuHH npc,QCTaB.'1HeT C060H YMbIlllJIeHHO
nJ eamI3HpoBaHHYfO Kapnmy. MO.leKYJlbI He 5IB.'ISIIOTC5I }KCCTKIBW lllapmIH 11 IIC HM(:'lOT
qCTKHX npOCTpaHCTBCHHbIX rpaHHLt, cn.rlbI B3aHMO,T\eikTBH51 He HSMeHHIOTCSI c H3McIIeH1-ie 1
paCCT05IHl151 CKallKOOopa3HO. O-".H3KO BBHJ{Y 5lpKO BLlpa>KeHIIoii saBllCUMOCTH 3THX CHv'1
0'1' paccnmHHSI TaKHe npC)J.cTaB.'1eHlISI MO)f{HO npHIIHTb B KaqCCTBe 3qX!)CKTIiBHOH CXel\'lbI,
.n3lOIILen xopOlllee npH6JIIDKeHHe K .n;CiiCTBHT€v1JbHOCTiL
B 3TOH H.neaJ1H3HpOBamWH MO)J.emi B(:')lH4HHa 0' npe)J.c-raBJIHeT C060H 3qxpeKTMBIILIil
nOIlcpeq':U-IK 10JIeKy.'1bl. 3HaqeHH.51 a HCKOTOpbIX ra3013 )1.aHbl B '1'a6"1. I. B .lI.a"lbH€HllleM IbI
6Y;J.eM onYCKaTb HII;:J.€KCbI I, 2 H 12, TaK KaK B Ka>KAOM KOHKpeTHm-l ulYQaC 5IClIO, 0 KaKOM
3 (1)CKTHBHoM nonepetlHHKe l'J)I,eT peqb. 3cpcp€'KTHBHbl:fI nonepct.II1HK 1B:oroaTOMHbIX MO-
.aeKY"'I 13 HeCKO"'IbKO pa3 npcBocxO)J.HT paccToSIHHe Me}K)l.Y SI)J.pa m a1'O:\1OB.
,lJ,JISI onpe)J.eJICIIH.51 B€..JmqHHLI 3cpcpCKTHBIIoro nOIICpeqHlIJ<.a Hcno.1JL3YfOT 33HHCH\IOCTH
KHHcTutlecKo'fi TCOpHH ra30B, KOTopble CBH3blI3mOT Be.IUIqUHY (J C ;J.pynnIH napa1l1eTpa lH,
tf.OC1'ynHLIMH Hcnocpe)J.cTBeHHo:\'lY 3KcncpHMeHTa.r!bHoMY onpe;J.eJICHHIo. 06blqHO 9qxpCK-
THBHblH nOnepCqHHK paCCqnTbmaloT no B513KOCTH ra3a. npH .:rro -1 qHCJIO coy.n.apeHHi'i <paK-
TUqCCKH BbI4nc.r:IHCTCH HenocpeLlcTBeHHo lIS pe3Y.llbTaToB 3KcnepHMeHTa. rnpOIl1..€HIIYIO
,"W)J.CJIL cOY)J.apeuuit Hcno.!lb3YIOT B paBHoii CTeneHH npn BbP-lHC"'ICIIHH 4acrOTbI cOY,J,apc-
HHi'i If BHSKOCTH rasa, T. €. no OTHOllleHHIO I{ JI.BYM npOlJ,eCCaM, H [CIOU1..lnl ana..lorHqnylO
npHpo.n;y, H B03MOlKH851 norpelllHocTb TaKOH: H.D.ea..'lH3alJ,HH 0I<a3bIBaeTCH IIlHnnz..wJlbHOiL
Jl"Ha cBo6o.lI.HOrO npo6era. OnHCaIIHa5I MO)I.e.,1Jb n03BOJ1HeT BLIllHC-
JIHTb cpe)I.HlOlO qaCTOTY coy.rr.apeHfrf'I Mo.neKY JI. CpeJJ;Hee paCCTOHHHC, npo-
XO)J.HMoe MOJIeKY,,'lOll ra3a MelKAY ,lJ.BYMH coy .n.apeIlH5IMH, H:r'\'lcHyeMoc
,lJ.JIHHOfI cBo60JJ;HOrO npo6era, onpe}I,eJIHeTC5I Bblpa)KeHHeM
:\ = 1 ( 1. 14)
. V-2 - na 2 nl ' .,T 0
r,n,e N 0 = 6,023. 10 23 .MOAb -1 - qnCJIO ABOraiI.po.
BeJU:lqHHa n = pi RT [3;J.CCb R = 82,1 e.M 3 . anu,t!(MOAb '2pa8)], T. e.
KOHu.eH rpaQH5I MOlleKY.11 npH nOCTOHHHOH TeMnepaType npHl\'IO nponop-
QHOIIaJIbHa ,lJ.aBJIeHHlO. TIO.3TOMY AJIHHa cBo6o)J.IIoro np06era B03paCTaeT
C Y;\'leHbIlleHHeM ,lJ.aBJIeHHH; npH aTf\'IOC(pepHO '1 .n..aBJIeHlIH H KOMJIaTHOii
TeMnepaTYpc OHa HMeeT nOp5I)J.oK 10 -6 ClI-i, a B YC.,10BIUIX pa601'hI BaKYY:\'I-
HbIX np1160pOB, T. e. npH p === 10- 4 -10- 5 lI-ut prn. cnl., ,rr,OCTHraeT no-
pH)1.I<a HeCKO.TlbKllX MeTpOB. ,il,.'1HHa cBo60,lJ.HOrO npo6era HaMHoro 60.llLllle
cpC,lJ.Hero paCCTOHIIH5I Me}K.n;y Mo.lleKY JIaMH, KOTbpoe npn a1'!vlOcq)epnOM
.n.aB.,rreHHn Ii KOMHaTHOI { TeMI1epaType paBHO npnMepHo 30 A, He 3aBI1CBT
3 - .
01' lIpnpo,rr,bI ra3a H 06paTHO npOnOpIJ.HOHaJlbHO Jln (a lIe 11., KaI<: L\).
COLilaCHO ypam'IeHHIO (1.14), npM nocToHHH01I KOHueHrpaIU.IH (pIT ,
canst) )J.JIJ1Ha cBo6oJLHOrO npo6era He 3aBHCHT 0'1' TeMnepaTypbI.
O,QlIaKO 31'0 yc.iJOBHe CTporo cnpaBCp,JIliBO TO.rlbKO )I.JI51 HarneH H)J.eaJIH3H-
pOBanJIOI1 M01C.rI1i coy.n..apeHHii ynpyrHx mapOH. lI..TIH pea.TIbHbIX BeUJ,eCTB
C IlOBblwenllCM TeMn paTYPbl, a 3HaqH1' H cpe)J.Heii CKOpOCTH Mo.TIeKY JI
ra33, pO.rIb B3aHMO.IJ.eI1CTBHH Me}K.rr.y Mo.7IeI{YJIaMH OCJIa6eBaeT. TIpH 3TO 1
Tpe6yeTcH 60JlbillCe C6.,TIJpKeH 1e QeIITpoB JJ;BYX MOJIeKy.lI, qrOObI OHO 61>1..'10
3KBHBa.neHTHo cOY,!J.apeHHlo. Bc.TIe)I.CTBHe 31'oro 3q)(peK1'HBHblfI nonepcllHHK
:r...rOJIcKy.il (CTporo rOBopH, 30Hb! coy,n;apeuHil) HCCKOJIbKO YMeHbiliaeTcH
c pOCTOM Te:\HlepaTYP I, a )J.JIHHa cB06o,IT,HOrO np06era npH n = const
COO1'EcrCTBeHITO B03pac1'aeT. .IT.JI5I OqeHL rpy60ti Oll.eHKH MO}KHO npHHHTb
(npn It const)
A........ T I /.. (1.15)
PaccToHHHe, npoxo;J.uMoe MOJICKY JIOH l\.fe}KJ1.Y .n.BYMH coy .n;apeHHSiMH J
paBHo A, npH 31'01\1 qnc.IlO ee coy.u.apeHHH Ha paCCTOHIHIH V, T. e. 06w.eM
nyn.I 3a 1 eeK, paBHo
I
II'
I I
I :
.1
Zl = = Y2 na 2 vnN o
A
Be.,lHQHlIa t 1 = ...II z 1 npe;::I.C1'aBJI5IeT coaOH BpeMH MelKJ1.Y .lJ,BYMH
C.0Y,A3PCHIUIMII O)I.HOH MOJIeKY JIbI. qacToTa coy.n.apeHHH MOJIeKy.n QqeHb
Be.rHiKa. DpH HOpMaJIbHblX YCJIOBHHX qllC.IlO cOY,lJ.apeHnil O.n;HOll Mone-
Ky.lIbI 33 1 eeK HMeeT IlOpH}J.OK 10 10 (CM. TaO TI. 1).
TIo.rIHoe qHCJIO cOYJJ;apeHlfi1 B 1 eeK Me)l{)1.y BCe?\,IH nN 0 MOJIeF':y JIai\HI,
cO}l,epJI<alll.HMHCH B 1 CM s , paBlIo
Z = nNOz l = Y2 3Ta2vn2N (1.17)
EC.rIH ra30Bas:r cpa3a COCTOH1' H3 Mo.TIeKY JI }I.BYX THIlOB, KOHIJ.CHTpalL HH
KOTOpbIX paBHbI COOTBeTCTBeHHO n 1 H n2' qJ1CJIO cOYAapeHIIll Mo.neKy.l1bI
l cpBoro THrra C -10JleKy.n:a:-"IH B1'oporo 3a 1 cel\, Z1 = V2na 2 V1l2 N o'
(v =- spe)I,HH}{ ,lJ..1JH 06eHx MOJIeKy.n CKOpOCTb), a nOllHoe qHC,,1JO coy,rr.apc-
lIun OOOliX TunOB MOJIeKYJI
Z12 = zln1"[O = y:2 :-c.ifvnl1!zN5 (1.18)
KaK CJIeAyeT H3 ypaBHeIIIHI (1.18), B ra30BbIX C!\.leCHX lIHC.ilO cOYl-I.. a -
peHHrl MCLK.n;y MoneKY .,TlaMl1, cIloco6HbI 1H K B3aHMo)I.eHCTBHIO, OqeHb
BeJIHKO. TaK, B c1'exHOMeTpnqeCKoi-i C leCH 2H 2 + O 2 IlPH 288 0 K H
1 aflUrt QHCJ10 coy ;x.apeHHH Me:tKAY Mo.TIeKY JIaMH H 2 11 O 2 3a 1 eeK ZH 2 -0 2 =
= 8,3. 10 28 C.M - 3. OqeBH,lJ,HO, qTO JIlo6aH peaKIJ.nH B O)J.HOpO,AHoti ra30BOH
C!\.ICCH llpaKTHqeCKH 3aBepillaJIaCb 6bI 3a l Cqe3aIOllJ.e MaJIbIii npOMe}KY1'OK
BpervleIIH, eC.I1H 6bI l(alK.I(oe cOYJJ.apeHne -Mo.fIeKy.n: pearnpYIOIILlIX ra30B
Be.TIO 1< XIUvIHQeCKOl\'IY npeBpaIlJ,eHHlO, nOCKo.lIbKY Z12» nN 0*'
O)I.HaKO onbI1' nOKa3bIBaeT, qTO CKOpOCTH ra30BbIX peaKlLnH BO MHO-
fIIX c.J1YQa X OqeHb MaJIbI. OTCIO,a,a OqeBlIJ1.HO, QTO .na.TIeKO He Bce coy)\a-
peHH5I MOJIeKY JI, cnoc06HbIX K B3aHMo.n;eHCTBHIO, npHBO,lJ.5IT K 3TOMY
B3anfvl01.eHCTBHIO. Har.....t Ha,7 .TIeLKHT BbIHCHHTb npHQHHbI TaKOll He3cpcpeh.-
1'HBIIOCTH coy,rr,apenHfL C..iIC;J,YIOlll..Ue 113 3Toro BbIBO)l,bJ lIMelOT peruaIOllI. ee
3naQeUHe )J..1J5! XHMHQeCKOfl lUIHeTHKH.
(1. 16)
:;. B .D.3HHOM CJI) 1t rae lI-b] No = 2 [02J lV'o = 1,7.IO H' CM- 3 .
2*
19
18
\
:
3 epriHI aKTHBau.IH1. TOT cpaKT, 41'0 TIlIll1b He60JlbWa5:! 1.IaCTb coy.n.a-
penHfI Me}K.n.y pearIlpYIOlI HMH MOJleKY JlaMH ne.;J;e1' }{ Xlll'vlH4eCKOIvlY npe-
Bpaw.eHHIO,. n03BOJUVI BblCKa3aTL npe.L(llOJIO}KeHHe 0 cym,ecTBOBaHHH
ocoGoro aI<1'HBHOro COCTOHHl1H Bern.eCTBa, 13 KOTOpOl\l OHO CIIoco6HO
K x:mvIHl.leCKoMy B33HlvlO)J,eiIcfBIUO. JIHlIlb ne3Ha4HTe,JlbIIaH ,lJ,O..'UI Mo.neKv,n
HaXO.lI..HTCH B aKTIJBHO\.1 COC1'OHHHH. B QC;".1 )Ke 3aKJllOQaCTCH 3TO COCTO'51-
HHe II nOqef..'IY OHO B03IIl1KaCT C1'O.!IL pe11;J{o? BCilH:oe npeBpa1l.J,eHHe O.ll.lIOli
J CHCTel\'ILI !\:OMnOIIeIITOB B )J,pyrylO CBn-
t / 3ano C pa3phIBOM Me}KaTOMHbIX CBH3eii
__t_ B Mo.neKYJlaX nCpBOI1 CHCref..Ibl n 06pa-
J 30BaHHeM HOBLIX ).'10JleKY JIffplIhTX CBH-
3d.i }];pyroi:i CHCTeMbl. HeOOX01LHMOCTb
aKTHBaQHH np:n XHMHtleCKOM npenpa-
ll1.CHHH 06YC.TIOBl£eHa 3aTpaToil 3HepflHI
na pa3pbIB CTapbIX, cyn eC'rBYlO1ll.HX
iC)l{aTOl\'IHhIX CB513CU. IIpou.ecc aKTH-
Bau.HH npelUIlecTByeT rreperpyrrnH-
PHC. 3. K rr05IClIemUO .JCXaIIH3M(:I pOBJ<e aTOMOB B pearnpYIOm.Hx I\.IO-
aKTlIn3l HH. ...TJeKY lTax, T. e. xnI\uiqecKol-I peaK-
l{l1H.
PeaKl HH B03IvIO}KHa JIHlllb B TOM CJlyqae, eCJIH B3aHl'vlo,rr.cfrerBYlOllI.He
Mo"rreKY JIb! nO...rryqalOI' onpe,n;eJIeHIIbli:i 3anac 3HcprHH, )J,OCTaTOqHbIII ).l.JIH
pa3pblBa lUIH CYllLeCTBeI-JIIOrO oc.naOJICHIHI MeLKaTO).UILIX CBff3eH. AKTH-
Bau.IHI 33K.TIlotIaCTCH B rrepexo;:r.e Mo.!IeKY JI n TaKoe COCT051HHC, B KOTOPO!\'1
CT3HOBHTC5I B03IvIO}KHbIM XHMHqeCI<Oe npcBpaw.CHHC. Pa3HOCTb cpeAHcro
3anaca 3JIeprllH 1\,tO.TIeKY...'I B aKTHBHOM B HeaKTHBHOM COC1'OffIIHX HaSbI-
BaCTCH 3HCptHei:j aKTHB3U,l1H A *.
AKTHBaIUI5I l\1o.TIeKY.II Heo6xoJ1.Hi\.Ia He TbJlbKO npH 3HAoTe o p:\1liQeCKHX
peaKQHfIX, HO H npH .3K30TepMl1QCCKllx. B nOClle;J,I-.leM CJlYQae (a OIl crre-
IlJrcpntICH .ll....TJSI BCCX IIpOneCCOB ropeHHH) 06pa3YJOw.neCH npn peaKUJI5IX
HOBbIe 1.10,neKy.:InpHble CB5ISH npoqnee C'rapbIX, paHee c.yn eCTBOBaBllIHX,
M HOBaH CHCTervra KOl\.lnoneUTOB 3Hepre1'HqeCKlI yeroli4HBee CTapOll.
K.a3a"rroCb 6hI, rrepexo,li. B 3HeprCTHQeCKH 60... Y ICC YCTOI'-{qHBYIO CHCTeMY
1Lo..'I}J(eH 6bIJI npOTeKaTb Ca?\'ionpOH3Bo.llbHO. ,L:LJIH 06'bHCHCHI15I npHqHIIhI,
no KOTOpoti 31'0 He llPOHCXO,[J,HT, y,n;o6Ho BOCIIOJIb30BaTbC5I Har. ffAHhUvl
I1pH .lepOM .
Ha nJIOllI,a.1I.Ke 1 (pIlC. 3) CTOHT ca.TIa3KH. Il.flollJ,aAKa 1 pacno.TJO}KeHa
BbIIlle YPOBHIl OKPYiKaIOUI,efl MeC1'HOCTH 2. D03TOMY ca,ila3KH rvror.iIl-l 6bI
CKaTHTbCH na rr.1l0CKOC1'b 2 6e3 3aTpa1'hT ,IL0I10.1HHTeJIbHhIX ycn.fluff,
O1'JOla,4bIBa5:l no op,lJ.IlHaTe nOTeHlJ,lla.nbIlYIO 3Hepnl1o E CHCTeMhI lIS 1'pex
a1'OMOB (U"TIM rpynn aTor...loB) Bt C H D Ha pa3JlIiQHbIX C1'a)J,H51X HX rrepe-
pacnpe;I.e.neHHH lIPE pcaKQHH, a no a6Cll,HCCe - paCCT05IHHe r, xapaK-
TeJHi3Y lO 1ll. ee 31'0 nepepacnpe1Le.iIeHHe, T. e. npn6JIH2KeIHle K aTOMY C
aTOMa D H y.n.aJIeIIHe 01' Hero aTO 'la B, MLI I10JIYQaeM KPHBYlO, aHaJIO-
fllQnylO nYTH calla30K Ha pHC. 3.
rlo.Tlo}KeHHe 1 COOTBeTcTByeT 3HeprHll CHCTeMbI B HCXO;I.HONr COC1'051-
HHH, np Ii KOTOpOM aTOM (Mo.neKy.!Ia) D 6eCKOHeQnO Y)J,a.ilen 01' !\.10.Tlt'-
KY JIbI Be; no.TIOfKeHHe 2 - 3HeprHH KOHeqHbIX npo.D.YK1'OB peaKI.I.I1H BD
H C npH HX cooTBeTcTBYlOUJ,e:M Y,ll,aJIeHlur. nepcxo,TJ; CHCTeMbI 1I3 cocrOH-
HHH 1 B COCT05IHHe 2 CBH3an C OCBo6o}I{,u;eHHel\'1 .3HeprHH 1'enoi10Boro .3qJ-
Ci)eKTa peal<IlHH (B MeXaIIl-IlIeCI(oti aHa.TIOrHH - nOTeHlJ,Ha..1bHa5I 3IIeprHH
ca...TJa30K) .
flOJIOLKeIUle 8 cooTBe1'cTByeT COCTOHHllJO aKTHBau.llH, npM KOTOpOM
CHCTeMe C006w.eHa 3lIeprH5I aKTHBa HH E 31, a1'01\.1 D ,lJ,OCTaTOQHO npH-
6.ilH3HJICH K lleH1'py Mo.:rreKy.r:[bI BC, KOTOpa51 npn 9TOM npe)J;CJIbHO pac-
THHYTa. «CnycK C ropKu», oCBo6oiKAalOw.HH 3HeprHlO E 32' 3KBlIBaJICHTen
3lIeprHH aKTliBaQHH 06paTHOH peaKlJ.HH. 3HepreTIo.yqeCKaH CXel\'la peaK-
U,HH Jno6oro JI.pyroro Tllna aHa TIOrHqJIa. 113 H3JIO}KeHHOro Ot.leBliAHO Ba}K-
floe 3HepreTHt.ICCKoe COO1'HOllIeHHe, crrpaBeA TIl-IBOe .ll.JIH .r1106011 peaKIUIH:
: .
eC/lll 6bI Ha HX ny-Tn He ObUIO ropKH 3. ,[(,,151 car..lonpOH3Eo..rrbHoro cnycK3
ca.laSOK HX Heo6xo)J,lIMO nepBOHaqa.nbHO nO).J,H5ITb na 13epWHHY ropKH,
OTI<y;:r.a OIIH CKaTHTCH Ha rr.iIOCKOCTb 2. flpH 3TOM oCBo6o)K)J.ae1'cH HC TOJIbKO
;:meprH5I I1epexo)I.a OT COCTOHlIHH 1 K COCTOHHHlO 2, JIO H .IT,OlIo.!IIUrre..TJb-
Ha5I 3HepfH5I nOj{"bervra 01' cocrOHHHH 1 K COCTOHHMlO 3.
IviexaHH3 '1 XHMl1 t leeKOll peaKUHli BO MIIorOM aHaJIOrlitleH. }-Ia nYTl1
Tepl\'lo.I1.HHaMHtJecKH B03MO}KHOrO npeBparn.eHllH HMCCTCH npeIIBTcTBlie.
OHO saK.rlIQtIaCrcn B He06xo.ILHl\'IOCTH nepBOnaQa.ilbHoro pa3pbIBa HJIH
oc.Tla6.TlenHH panee cYl.I.I,eCTBOBaBlllHx Me}KaTOMHbIX CB5I3eii, XOT5f JIOBhIC
CB7ISH B 06pa3YIOIu,l1XC5I np0)I.yKTax peaKII.HH OKa}KYTC5I I1poqnee cTapblx
H npl1 ilx B03HHKHOBeHHH OCB06oJU1TCH 60v1bUJee Ko.TIl1QeCTBO 3HeprHH,
QeM 3aTpa t leHI-IOe Ha nepBo '1 3T3ne. Oc.n:aG.lleHHe CB5I3en B HCXO,rr.HbIX npo-
JI.yKTax TpeGyeT 3a1'pa1'bi .3HeprHI1, aHa.iJOf'HllHO no;:rLeIl,fY Ha ropKY 8.
3TO H eCTL nponecc aKTHBall.HH.
11pHBe.n..eHHaH npocTaH lexaHHtICCKa5I alla v 1JorH51 He TO.llbKO YJI.06naH
H.lI"rrlOcTpal li5I. PaCCM01'pHM 3HeprCTHQeCI<Oe COCT05!HHe CHCTeMLJ) B KO-
TopotI rrpoTeE:aeT o6MeHHa5I peaKu,l1H:
BC+ D = BD + C
.
:'. .
,
"
i..; :
.:{: ..
'I
.
.?
Jl\t .
{ .
* B HCKOTOPb!X nonYjHlpHbIX YQe6HlIK3X paeTC5I .rr.pyroe onpe,.'J,eJIeJII-Ie 9Hepnm
3KTHD£1II.UH, J\aK MHIIHMa..'IhHOrO 3arraca SlIeprmI, Heo6xo;'I,HMOrO :\W.TICKy.rIe )J,.II5I BeTyrr-
.,leHHH B pe8KlI.l1IO. T aKoe$ :-'U-IKpoCKOrrUqeCJwe onpe,!.(eoTIeIiHe., BooollLC rOBopH, uenb35I
C t IIlT8Tb HeUepHbIi\r, XOTH ono OTJIHqaCTCn OT .n.8HHoro panee, MaKIWCKOnHtICCKoro. 063
orrpe,rr,eJIeUHH )-lOrYT 6LITL rrpH3JIaHbl cnpaBcJ(JII1BbI.MH. Pa3JIIItllle LKe matICHHjJ 3HcIH'HH
aKTHBal lIH B KmKJ(OM 113 9THX OnpeAeJleHHii: IIeBe,i'IHKO 11 He HMCCT npaKTHqCCIWfO. 3Ha4e-
HUH. OJI.HaKO rrpH CYll.{eCTBYIOII e)1 e.) HHCTBeHHOM MeTOlle 3I{CrrCpHM€HTa.TILIJOrO OnpCiI,e-
JIeJUf5I A no TeI\mepaTypuo:\ory K03q)(}mIJ.HeHTY CKOpOCTH pCaKII.HH (CM. HH:iKe) TO lbKO M2KpO-
CKorrHlleCKoe onpejJ,e.TJeIlHe OI\a3bIB8CTCH, cTporo rOBopsI, crrpaBc;V1Hl3T.>IM [ 10 ].
20
A_ - A+ = Q
(1. ) 9)
r,1,e A+ H A_ - 3HeprHH aKTHBal l1lI COOTBCTCTBeHHO npYI 10i1 H 06paT-
Hoti peaKu.llH, Q - TeIIJ10BOH 9cpq)eKT npou.ecca.
9TH COOTHOlileHIHI MOiKHO n051CHHTb CJle)]YlOU I1MH I{HHeTI.JQeCKI1:t\Hf
I3blpa}KeHH5IMH. ,[(J'lH 06paTH]o,.:Ioi% peaKHHH
aA + bB +. . . :;- cC + dD + .
(V I I)
21
I :
I
I!
II
, II
CK?,POCTb HIHIMOii peaKll.I1ll (1)+ = k+ fA]a [B]b . . . CKOpOCTb 06paT-
HOB (D_ = k_ [C]c [D Jd . . . B COCTOHHHH paBHOBeCIHI U>+ = (1)-
lC]C [DJd . . . Il+ -K
[Aja lBlb . . . k_ - (1.20)
r)J,e l( - I\:OHCTaHTa paBHOBeCH5:l.
Tep
-IO,DJIH
MHKa ,naeT B03MO}KHOCTb BblqHCJIlfTb KOHCTaHTY paBHO-
BeCIHI ra30BOli peaKl(HH. T04:HOCTb TaKoro pacqeTa onpe,neJHleTCH Hl'vleIO-
ill.lf?\H1CH CBe,lI.eHH5IMH 0 TenJIOBOM 3cJ.)(peKTe peaKI1.UH II TeIIJroeMKocT51X
tICXO
HbIX II KOneqHbIX npO
YKTOB peaKJJ.HH. LI.JIH 60JIblIlIIHCTBa CHCTeM,
npe,n,CTaBbTJHlOIlI.HX HIITepec .u.JIH KHHeTliKH ra30BbIX peaKIJ.ufI, 3TH ,4aHIIbIe
Mory r 6bITb Han.z:r.eHbI ,
,D,OCTaTOllHoil TOqHOCTblO (CM. HlnKe). TI03TOMY,
eC..111 CK,?POCTb npHMOH peaKIJ.lIli HSBeCTHa, CKOpOCTb 06paTHofi peaKlI.HH
IvIOJKeT Obll'b BbIqH
.,"'IeHa, 1I Hao6opOT.
MexaHH3M aKTHBaQHH. PaCCMOTpHM, KaK npOlICXOAHT aKTHBaIJ,H51
pearl1pY 10 lll.nx MOJleKY
TI, OTKy.u.a 6epeTCH 3HeprHH aKTHBHbIX MObTJeKY JI.
Be..TJII4HHa 3HeprllH aKTHBaI1.HH MHorHX peaKlI.HH He IIHLKe HeCKOJIbKHX
,n:eCHTKOB KHJIOKaJIOpHfI Ha Ivl0JIb. B TO )Ke BpeM5:1 Cpe.lI.IIHH TeIIJIOBa5I
3Hepn'IH O)I.Horo MO.nH rasa ()J.BYX-TpexaTOMHoro) HMeeT nOp51)J.OK BeJIll-
}UILI (1,5-3) RT [3.n;ecb R = 1,986 Ka/l/(MoAb '2paiJ)]' llpll 500 0 C,
Kor)J.a MHorne ra30Bble peaKlI.Hl1 Y)Ke npoTeKaloT C 3aMeTHbUUI CKOpO-
CT5:ll\.iH, cpe.l(HHH Tcn.JIOBaH 3HeprHH COCTaB.rmcr 2-5 KK£l/l/ J..WAb, T. e.
3HaLIHTe.rlbHO MeHbllIe 3HeprHH aKTHBaJJ.llH. -
OODHcHeHHe npnQlIH aKTHBaI1.HH ,n:aeT Mo
eKynHpHo-KnHerllqeCKa51
Te?pHH ra30B. B 60J1blllOM KOlIJIeKTHBC XaOTHqeCKH .u.B1uKyrn.necH MOJIC-
I<Y JIbI IIaXO
HTC5l B pasHoo6pa3HbIx 3HepreTHqeCKHX COCT051HHHX. Pac-
npeJl;e.neHHe 3HcprHH IIo.n;qllHHeTCH CTaTHCTHqeCKliM 3aKOHaM. TIpn 31'01'1,'1
011(eJIb
ble Mo.aeKY JIb! MorYT Hl'vIeTb sanac 3HeprHH, 3HallllTe..TIbHO OTJIH-
qalOIlI.HHCH 0 r cpeAHeli BeJIULIHHbI.
r TIOCKO..1JbKY lJ.HCJIO CTOJIKHOBeHHH OqeHb BeJIHKO, KHHeTHqeCKaH
reopHH ra30B n03BOJI5ICT
OqHO BbIQnCJIHTb J(OJlIO MOJIeKYJI, CKOpOCTb
H 3HeprH5:1 KOTOpbIX Haxo.rr.5ITCH B rpaHuu.ax onpe)I,eJIeHHOrO HHTepBaJIa.
TaK, MO:>KIIO BblqHCJUITb )1.0JIlO aKTHBHbIX MOJIeKYJI, HMelOIll.nx 3ueprHIO
60JIbille A, KOTopan, COr.,TJaCHO saKoHY BOJIblJ,Mana, paBHa e- A1RT .
OTCIQ,n;a qHCJIO 3cpq)eKTHBHbIX coy.rr.apeHHH Zeff l\'Ie2K)I,Y pearHpYlOll.I,UMH
MO.fIeKY.1IaMH 1 H 2 B 1 CA.t 3 ra30Boil CMeCH, COBnaJI.alOll.I,ee co CKOpOCTbIO
peaKI1.HH, paBHO
-rOqnylO 3Heprmo, .n:.pyrHe HeaI{TlIBJIbIe LIaeTliUbI nO.TIyqaT ee H T. JI..
B Hepearl1pYlOllI.eM rase aKTHBHbIe MOJIeKY JIbl HaXO)I,5ITCH B paBHoBccHH
C HcaKTHBHbIMH, l\'lo.neKy.rIbI .n;e3aKTHBHpYIOTC5I II aKTlIBHPYIOTCH B paB-
HC-l\1 t.IHC..11e. DpoTeKaHHe XHMHqeCKOH peaKII..HH CtJ.BllraeT paBHoBccHe B CTO-
POHY nponecea aKTHBaU,HH no 1\.repe H3paCXOlJ:OBaHHH aKTHBHbIX MOJle-
KY.II, KOTopbIe CHOBa 06paSYlOTC51 B pe3Y JIbTaTe TerrJIOBoro ,lLBH)KeHHH.
YJl.3b11eHlIe aKTHBHbIX MObTJeKy.11 113 ccpepbI peaKlI..HH He npHOCTaIIaBJIH-
BaeT ee.
Tcn.rroBoli 3qxpeI<T nepeXOl{a H3 HeaKTHBHOlI cpOpMLI B aKTHBHYJO pa-
BeB. 3HeprHH aKTlIBaI1.Hll. 31'0 n03BOd'IfleT BbILIHCJIHTb no 3aKonaM TepMo-
J],HHaJ\.1HKli }lOJIIO aKTHBHbIX MOd'IeKY bTJ. CKOpOCTb peaKI.I.HH nponopILHo-
naJIhHa KOHIJ,eI-ITpanHH aKTHBHblX MOJIeKy.n, nOCKOJIbKY TO.TlbKO OHH cno-
C06B.bI K XHMHqCCKOJVIY npeBpalll,eHHlO; TaK no..rI)Ft:IaeTCH ypaBHeHue (1.21).
3TH Ka)KYI.I.LHeC5:1 HeCKO.,TIbKO HaHBHbIMH npe,neTaBJIeHH5I AppcHHyea
B HaCTOHmee npeM51 B YCOBepmeHCTBOBaHHOH q)OPMC B03PO)K,lLCHbI B Teo-
pHn aKTHBHpOBaHHoro KOMllJIeKca.
TeMnepaTYPHbIH Koa
£lJ"u,HeHT CKOpOCTH peaKl.I..HH. I13JIO)KeHHbIe
paHee C006pa}KeIIHH n03BO.TI5HOT onpe,n;eJlUTb, KaK Be.TIHKa ,n;OJI51 aKTIIBHhTX
MOJIeKY JI H nOqCMY CKOpOCTb XIIMHqCCKOH peaKIJ,HH TaK CHJIbHO 3aBllCHT
01' TeMnepaTypbI. B KaqeCTBe npliMepa.HIUKe npHBe)J.eHbI 3HaQeI-UI5I BeJIH-
"lIHHLI e-A!RT npll HeCKOJIbKlIX TeMnepaTypax (B OK) .II.JIH pCaKIl.HH pa3-
.TJO)KeHH51 HO,ll,HCTorO BOJI.opo.n;a, y I<OTOpOII A = 43,7 KKaAI.MoAb:
T 288
e-A!RT 6,7.10- 34
500
7,7.10- 20
1000
2 8.10- 10
, -
1500
4,2.10- 7
2000
1 ,7 . 10- 5
TIpH KOMHaTHOH TCMnepaType )J.O.TIH aKTHBHbIX l\.IOJIeK)' JI COCTaB.1IH:eT
HHqTO>KHYIO BeJlHqlIHY, nop
.l(Ka ] 0 - 33, peaKlI.IHI npaKTHLIeCKH He HMeeT
MeCTa. C nOBblmeHHeM TCMnepaTypbI qnCJIO aKTHBHbIX Mo.neKY JI Ot.IeHb
6bICTpO YBe.,rIIiQnBaeTC5I, qeM H o6yeJIOB.TIeHa 3aBHCW\10CTb CKOpOCTH
XHJ\.fHqCCKOH peaKlI.llH 01' TCMnepaTypbI. B paCCl'\'faTpHBaeMOM npHMepe
nOBbIllieHne Te!\HlepaTypbl 01' 500 )1.0 1000 0 K npHBO,gHT K YBclIHqeHHlO
qUCJ1a aKTHBHLIX Mo.HeK)' JI 60JIee qeM B MHdTJJInap,TI. pa3.
B II..eJI5IX HarlI5ILLHOCTH 1'a >Ke 3aBHCH1vrOCTb npOHJIJIlOCTpnpoBaHa rpa-
q)HKOM (pHC. 4). TIo OCM a6CIJ.HCC oTKlla)J.,bIBaeTcH a6co.,rIIOTHa5I TeMnepa-
Typa, no oen 0pLLHHaT - )I,OJI5I aKTHBHblX MOJIeKY JI, YBeJIlIqeIIHa5I lI.JI5J
YLLo6cTBa 3aDlICR B MHJIJIHOH pa3, T. e. 10 6 .e- A1RT . PaCCMaTpHBaeMd5I
3aBHCMMOCTb TaKOBa, qTO )J,JIH pa3bTJO)KeHlI5I 1
IICXO.ll,HOrO Bell.I,eCTBa I1PH
288° K H aTMoccpepHOJl,.f .n;aBlleHHH Tpe6yeTcH 10 14 .ireT, npH 600 0 K -
Y>Ke TO.TIbKO 10 ti, a npH 1000° K - Bcero 0,02 ceK, T. e. peaKlI.. HH npaK-
TUqeeKH nO,,"'IHOCTblO 3aBeprnaeTC5I 3a HeCKOJIbKO ceKYH)J,.
3HaLIHTebTIbHOe YBeJIHQeHlIe CKOpOCTH XllMHqeCKoI':'i peaKIl.nH o6yc-
JIOBJIeHO 6b1CTpbIM pOC1'OM ,lI.O..TJ:H aKTHBHbIX MOlleKY JI C nOBbllJIen HeM TeM-
nepaTypbI B CBH3H C 9KcnOIIeHl
HaJIbHbIM xapaKTepOM 3T0i1 :1anHCIl-
HOCTH. TIOCKO.TIbKY 3I(CnOneHTa e-A/I
T HMeeT TOqKY neperlI6a nph
T = A/2R, T. e. ,lLJIH 06bIQHbIX 3HaQeHUll A npn HClJ:OCTH)KllMbIX B XHMH-
qeCI<HX npoll..eccax TeMnepaTypax 5000-10 000 0 K, ,lI.ObTTIO aK1'HBHblX
Mo.nexy JI MO>KHO CLIHTaTb MOHOTOHHOH tPYHKIJ.Hefi TeMnepaTypbI.
Zeff = (I)N o = Z12 e - A1 R..T
(1.21 )
IlpH4HHa aKTllBau.I1H MOlleKy.l1 npH XI1r.'iHQeCKI1X peaKUH5IX Haxo-
,lI.HTC5I B Caf1,'IOH npHpO,l(C raS006pa3IIOrO COCT051HH5I. AK'fHBHOe COCT051HHC
HC HB.TJHeTCH qCM-TO XapaKTepHbIM AJIH onpe)J,eol1eIIIIOH MO..'IeKY JILl. Ha-
npOTHB 1'01'0, .m06aH MO..1JeKY bTJa MO)KeT aK I'HBHpOBaTbCH II .u.e3aKTHBH-
pOBaTbC5f.
TIOcToHHIIa5I CYMMa 3IIeprHH 60JIbllloro KOJIJIeKTHBa 4aCfHlI. pacnpc-
,lI.eJH:leTC5I TaKHl\I 06paSOM, qTO MaJIaH qaCTb 3TOrO KOJlJIeKTHBa Ha KO-
pOTKHii nporvre)KYTOK BpeMeIIH IIOJIyqaeT H36hITOQHYIO na,n, CpeAHeli
3Hep rIHO. B C.r:re.n:YIOIlJ,HH MOMeH r aKTHBHbIe MOJIeKY JIb! HOTep }fIOT H36bI-
22
I
111 1
r
I I
I
Ii
I
III
I
, I
I
I
I
I
i
I I
I!
23
lJCM 60JlbUle 3neprHH aKTl1BaI1.Hl1) TeM BLlIlle TCMnepaTypa, lIeo6xo-
l.lU...135i ;J,JIH IJ.OCTIUKE'JIHH 3a,IJ.aI-lHoi:i CKOpOCTM peaKll.MH. Ha pHC. 4 n pe}}.-
CTaB,!Iena ell
e U T{pyrafI 3aBHCHMOCTb JI.OJIl1 aKTlIBHbIX MOJIeKy,,1] OT TCM-
nepaTypbl: ,'1,..151 A = 35 Kl\.aJll,A.W/2b (KIHl13aH 2). CorrocTaB,rreHI1e nOKa-
3blBaeT, qTO Kpl1Ba51 ,J}IH A
35 KKa;zIA-to;76 paCnO.TIO}Ken3 ropa3Ao BbIllIe.
TlpW-Il1Ha .3TOrO oqeBH.n.Ha: Be
IHqHHa A 60JIblllC, Kor.n.a cYlllecTBY10Ill.ne
Me}KaTO
UIhH
CB5T3H B
.10JIcKY,!IaX pearnpYIOUJ.l1X KOMnOHeHTOB Cli.T!bHee,
npeO)..!,OJICHHe 3TlIX CUJI Tpe6YE'T 60JlbWeii 3aTpaTLI 3Hepn-UI, npn 3TOM
I .ll.Oll5T aKTHBHbIX Mo.!IeKY Jl COOTBeTCTneHHO
6 -AI f?T
10 .e MeHblue.
113 CKa3aHHoro BI1)J,HO, qTO Be.TJHqHHa
3HcprHH aKTHBau,l:lH HBJHleTC51 Ba)KHCihueH
xapaKrepHCTHKOH XHMHqeCKOrO npOll.ecca.
OHa onpe,rr,eLTIHeT BHCOTY 3JIepreTI{qeCKorO
6apbepa, npeo}{o.TIeJ-Hle KOToporo npe.r:r. CTa -
13.1151CT . c060ti YCLiJOBHe OCYI}leCTBJICHHH
peaI<I.J,HH. C .r:r.pyron CTOpOHbI, OHa xa-
paKTepH3yeT 3aBHCHMOCTb CKOpOCTl1 peaK-
UHH 01' Te;...1nepaTYPbI: I.lCI\.i BbIllie BeJUf t lI1Ha
3HeprHH aKTHBaIUHI, Te
'I CHLTIbHee 3Ta
3aBHCHf..'IOCTb, TC\-f 60JibIlIe TC
-InepaTYPI-IbIii
K03lpq)HHHeHT CKOpOCTH peaJ(QHH.
1/13 ypaBHcHI1H (1.21) cJleAycT
Z12 A
In d) = In No - RT
I1pH V :-- const, piT = const I.IHClIO co-
y...1.apenni:i lB Ma.TJ:O H3MeHfIeTCH C Te.f..InC-
paTYPoII. 1-10 H npH IJ = const c.TcnCHH3H 3aBHCHMOCTb Z 12 3Ha1.IHTC\:TbHO
c.,rIa6ee 3 l\cnOHeHll.Ha.rIbIIOfi 3aBHCHMOCTH e-A/R..T, H B nepBOM npH-
6.;.nnKeHlIH Be.Tm1.IHIIY Zl
l...fO)l{HO CQI1TaTb nOCTOHHHOiL B .3 ro:\., op H6L r IH-
)J{CHHH Be.rIW-lHHa In CD ,!IHHeHHO 3aBHCHT OT 06paTHoii TeMnepaTypbJ.
TaKl1M oopa30ivI, 13e.!lllllHna 3HeprHH aKTHBau.I1H xapaKTepH3yeT TCM-
ncpaTypHblti J{o3fl)(lnlUl1cHT CKOpOCTH peaKu,HH:
'1 _ [ dIn (Z12/ lvT O) _
In (11 ] :=::'-5 _ R d In
_
f - R d (lIT) d (lIT) d (liT)
- 24,0
20,0
16,0
12,D
8,0
4,0
1000
1400
1800 T,':If(
PHC. 4. 3aBHCHi\lOCTb CKOpOC:1'H
pC3KlI.HH 01' TCMIlepaTyphI:
1 - A = 43, 7 KKa
?f,tw,l{); 2 - A =
= 35, 0 KKaJ.l/.
!O_?b.
oj)
(1.22)
JIHpHbIl
i i\IeXanH3
.f. llpn 3TO\1 HeC) lI
eCTBCHHO, K3.K pacnpeJI.e..'HICTC51
.3HeprH51 a KTHBaU.Hl1 MeiK)l,y MOJICKy,,1]3J\iII 060HX KOMflOHl".HTOB 1 H 2;
B nponcccc aKTl1BalI.HH cYMMapHaH 3HeprHH 6Hl\IOJICKY.TIHpHOrO KOIvIIl,neKca
aKTHBIIbIX rvlOJlcKy.TJ 060HX KOMnOHeIITOB E 1 - + E 2 » A.
BUMolleKY JI51!HlbIii fvIexaHH3M pCaKlJ,HH I-Iau6oJIee pacnpocTpaI-IcH
.T151 OT
e.11bIIbIX cTa,LlHH C.110)KHbIX npou.eCCOB. B03r...loiKIIbI, O)J;HaKO, H .LlPY-
rHe 1\.lexaHH3f1,IbI peaKlI,I1H. P3CIIa)
H..111 T3YTojl..fepnoe npeBpaJ.JJ,eHHe HeKO-
TOpblX Belll.eCTB npoTcKalOT MOH01\.lolIeKy"T(}fpno, T. e. npoHcxo
HT caMO-
npOH3I30LTlbIlO npn )J,OCTIUKeHHI1 r.,'IOJIeJ<Y.TlaMH pearnpYIOIll.CrO KOi\'lnoHc_HTa
onpe.,n:CJICHHOro HeycToi"i\IHBOrO COCTOHHH5T.
KOHeQHafI CKOpOCTb MOHoMo"leKY,H5IpHOIJ peaKu.liH H ec pOCT C T.eM-
nepaTypoli C13l1)J.eTc.rlbc.TBYIOT 0 TOM, llfO H npn TaKOM McxaHH31vIC p,...eaK-
IHIH Tpe6YCT aKTHBall.UH. O;:r,HaKO HCTOqHMKO
.f aKTI1Ball.IUi MorYT OhITb
TO.TlbKO coy.rr.apeII1HJ Mo.
IeKY JI. TaKH
l 06pa301\.i, npH MOHOMO.
IeKY .TJHPHO}1
(cnOHTaHHOM) McxaHH3Me XH::Vll:IqeCKOrO npeBpallI.eHHH npolJ,Cc.c aKTHBau.HH
npOHCXO,-\HT 6Ul\-IO,neKy.TJfIpHO. EC'reCTBeI-IHO npe
1.nOJIO)KHTb, 1.ITO .rr.O.TlfI
MO.11eKy..TJ, pearHpYIOlll.I1X
10H0I\10,neKY .TIS::rPHO, npo.
oplI,UOHaJlbHa H
KOH-
UeHTpaUHH, npu 3TOM peaI(u.HfI Hl\'1(
CT nepBbIli IIOl
fI,il,OK; HaooopOT,
eC.TJH peaKlI.HH llMeeT nepBLJi:i nop5T
OK, TO MO)KHO npe,l1.Ilo.TJO)KHTb, 41'0
ona rvl0HOMo"leKY,!I51pHa51.
TpeTIIti THn peaKl
HrJ - TpI-IMO.iIeKY .TJ5IpHbIe - HMeeT !\.teCTO npH OJI,HO-
BpeMeIIIIOM B3al1Mo.Zl.eHCTBHI1 TpCX pearHpYIOllI,I1X MOJICKY .TI,
: e. npH
tpOBHO:\.f coy
apeHHH. KpOMe paCCMaTpI1Bae?v[bIX IIIUKe peaKU,HH C13060;l,-
HhlX aTOMOB H pa,u,l1Ka
TJOB, OIl BCTpellaerCH B neMHornx OC06bIX c.nyy.35iX.
Do..ncc C.JlO}KHble peaJ<lI.HH, qCM TpHfvIO.T(eKY.1IHpHble, Boo6w.e He peaJlll-
3VlOTCH.
TpoiiHblC coy
apeHHH l\'IO)KHO paCCMaTpHBaTb KaK :.oY,l1.apeHH
KOM-
II .iJeKCa 113 !I.BYX CTO.HKlIYBllIHXCH MOJleKY.ll C TpeTben QaCTI1u,eH. 110-
CKOJlbKY I\OIlI1.eHTpau.l151 TaKoro KOMn"TJCKCa npOnOpll.HOHa,HbJ-Ia l:,OHu. en -
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ene B OCHOBHOM npOTeKaeT Ha nOBepXHOCTH, A06aBKH, YMeHbillaJOllJ,lie
h03cj)(p n ll.HeHT .ll-IlCI)(pY3Hli U 3aTpY,!I.HHIOllJ,liC nepeHOC aKTIIBHblX U.eHTpOB
36
I
K cTeHKaM, yne,fU1QHBalOT CKOpOCTb peaK HH. npH OCTaTOqnO BbJCOKHX
aB.TJeHHBX, a 3HaqHT npn OOpbIBC u.eneii B 06'beMe nHepTHbTe JI.o6aBIUI
VBe.TIHqHBalOT qnc.TIO TpOHHblX cOY,JJ,apeHld:i, a C HHMH 11 CKOpOCTb peKOl\'I-
6UHaUliH H TOp 10SHT cYMMapHYI0 peaKU)lIo. HeKoTophIC OCOOCHIIOCTII
nponeccoB BocII.rra1\.1e.HeHHH TaIGKe 06YCJIOB.IICHbI CooTlIollleHHHMH 06PbIB3
lLeneH Ha nOBcpxHOCTH H B 06'hervle.
TOPJ\.tO}KCHHe peaKILHH XHMH4CCKH aKTHBHbIMH Jf.O aBKaMH ll:IH HHrH-
6lJTOpaMH npe)J.cTaBJl5IeT J1.PyrylO xapaKTepHYI0 OCOOCHHOCTb '_' KHHeTHKl1
nenHbIX peaKlJ.HfI. KOHIJ,eHTparUIH aKTHBHblX ueHTpOB uenHoH pcaKIUHI
HeBeJUIKa Aa}Ke BO MHOfnx 6bICTpopearHpYIOl.l.L HX cnCTe .lax - 60.!Ibllla
CKOpOCTb xHlvIHQCCKOrO B3aHMo,7J,encTBIiH 06YCJIOBJIeT-I3 pereHepaUHeli
aKTHBHbIX ueHTpOB, He paCXO,IlYIOIllHXCH npM peaKUHH. BBe.rr.CHHe B CH-
CTeMY KOMIIOHeHTOB, cnoc06HbIX 1136HpaTeJIbHO pearHpOBaTb C aI<THBHLIMH
neHTpaMH 6e3 pereHcpan.HH rroc.TIe.lI.HHX, MO)K.CT npHBOAHTb . K pe3KOMY
1'OP 'IO}KeIIHI0 peaKlLH1L I1HrH61IpOBaHlIe, T. e. OTpHuaTe.TIbHb1I1 KaTa.TIH3 B
rOMOreHITbIX rrpoucccax, 06YC TIOBJ1eHO YHI-IqTOLKeHlleM aKTHBHbIX ueHTpOB.
KI-IHeTHKa peaK lui B HHfn611pOBaHHoi:i CMeCH onpe.n. e ,,1JHeTCH yc.no-
BHHMI1 KOHKypeH HH HHfM6I-ITOpa II OCIJOBHbIX KOMnOHeHTOB peaKUliH
npH B3aID10.rr.eHCTBHH C aKTHBIIbIMH U.eHTpaMIL DpH BblCOKOM cneumpI-I.:
qeCKO 1 CpOACTBe aKTHBHblX eHTpOB II MO.TIeKy.J1IIHrH6HTopa II y IepeHHOH
CKOpOCTI1 reHepHpOBaIUI5I HOBblX aKTHBHbIX neHTpOB y)K.e He60JIhiliHe J(O-
6aBKH orpUllaTe.ITbHoto T<aTaoiTI1I3aTOpa MorYT ClIJIbHO TOpM03HTb pe8KUH :
5!B.rreHHC IIHrH6HpOBaHHfl HMeeT 60"TJb1lIOe 3HaQeHHe B XHl\HIQeCKOH
KHHeTHKe. COOTBeTCTBYIOllU1H no.n.6op Cneu.Hcl:m:qeCKHX HHrII6H fOpOB n03-
Bo,,1HeT TOpM03HTb He)KeJIaTe.TIbHbIe npOlLeCCbI. Hao60pOT, npH npOBe;Le-
I-IHH MHorHX TeXI-IO.TIorHqCCKHX npon.eCCOB B03HHKaCT ne06xo.n.HMOCTb
:2 1'ill,aTeJlbHot'I OlIHCTKe KOMnOHCHTOB 01' pa3.TIHQHbIX llHrH6HPYIOll HX ;:l,0-
6aBOK, TOpM03HIl1.IIX ueJICBYI0 peaKU1UO. 3HaQCHHe npoueCCOB HIIrH6Hpo-
B8HlIH }J:."TIH HeKOTopblX 3a}J,aQ o6ecne IeHHH B3pbIBo6c30naCHOCTH OCBe-
IlJ,.aeTCfI HI1LKe.
Pa3BeTBJleHHe l ene". KHHeTMKa u.enHoi'f peaKUHH npHHllHnHaJlbIIO
OTLTIHqaeTCH B 3aBlICH1...10CTH 01' Toro, CKO.i'TbKO--aKTllBlIbIX ueHTpOB MO}KeT
o6pa30BbIBaTbCH npH 3lIeMeII1'apH01'I'I" aKTe- 0 HO 13BeHe uenn. IvlexaHH3M
HeKOTopblX peaKlJ. H11 , npHMepbI .KOTOpbIX )J,aI0TCH HIDKe, TaKOB, qTO Ha
Ka)K.1J.OM 3BeHC uenH BCTynJIeHHe B peaKUHIO O)J.Horo aKTHBHoro ueHTpa
MO)KeT npHBO)1.II1'b K perCHepal.lHM TO,,1JbKO OAHoro HOBoro aKT. BHoro
lJ.eHTpa :::. Y MHorliX UenHbIX npoueCCOB npO)J,YKTO 1 3"TJeMCHTapHOH peaK':"
lIJIfl OKa3bIBaeTCH ne OAlIB, a ABa H,,1JH 60.TIee aKTHBHbIX aeHTpa. TaKI1C
peaKl1.110HHble JJ.enl1 Ha3hIBaIOTCH pa3Be1'DJleHIIbC\1H.
XapaKTepnaH oc06eHHocTb KHHeTHKII peaKUHu rrpH nepa3BeTB.,TleH-
HaM nenHOl\.t McxaHH3MC 3aKJII01.IaeTCH B KBaSliCTanliOHapHOCTH KOHueH-
TpaUHH aKTHBHbIX lI.eHTpOB. I1pH OTCY'fCTBHH 06pbTBa ueneli aKTHBHbIe
U.eHTpbI 06pa3YI01'C5I B TOM iRe KOJ1l1QeC1'Be, qTO II paCXO,lI.yI0TC5I; HOBbIC
aKTHBHbIe u,eHTpbI B03HHKaIOT .,rIHIllb B npoueccc HaQa.TIbHorO HHHUHHpO-
BaHHH. Ec.nII CKOpOCTb noc.TIe)1.HerO npOIl,ecca COBnaJ(aeT co CKOpOCTbID
06pbIDa II.e nH, KaK 31'0 qaCTO 6bTBaeT, YCT3HaBJIHBaeTC5I onpe,rr.eJIeHHa5I
.;: Pa3YMeeTCH, ec.nrr He npOfi30H}I.eT 06pbIBa l1.cnn H aKTlIBHblH U,CHTp BCTynHT B peaK-
UHlO 6e3 perenepal.X.Hll.
I
I
II
II.
I
I
37
I'
I
nOCTOHHHaH KOHQeHTpaQHH aKTHBHbIX lteHTpOB H CTaI.I.HOnapHbIi:i pe)KHM
peaKI.I.HII, CKOpOCTh KOTOpOH HatIHHae1' Me;VleHHO Y 'feHbIllaTbCH JIHlllb no
Mepe 1I3pacxO OBaHIHI B3aI-iMOAeHCTBYIDIIU1X KOMllOHeHTOB.
npn npOTeKaHHH pa3BeTBJleJIHOH I..:(cnnOH: peaKlJ..HH KOHQCHTpaI.I.H5I
aK1'HBIIhIX lLeH1'pOB B CHC1'CMC B03paCTaeT HesaBHCHMO OT yc,noBHi:i Ha-
qaJIbHoro HIIHl1.HHpOBaHHH, eCv1H CKOpOCTb 06pa30BaIIJUI aKTHBHblX u.eH-
TpOB B npOI ecce pa3BeTBJleHHH npeBOCxO.lt.HT CKOpOCTb peaKD.HH 06pbIBa
lteneii. B03HHKaeT aBTOYCKOP HIOI..I.I,HHC5I pe>Kln,'1 peaKII.HH, rIp lIo6peTalO-
l.QHH .TJaBHHOo6pa3HbIH xapaKTep.
Lt.!I5I npaKTHLIeCKH nO.Hnoro npeBpaIU,eH1l5I HCXO,QHbIX KOMrrOHeHTOB
B KOHeqIIbIe B npHHHHrrc .n;OCTaTOqHO O.l{Horo Haqa;,TJbHOro ueHTpa. ECJIH
pa3BCTBuTJeHHH II.erreH npeBaJIHpYIOT Ha.lJ. HX OOpbIBOM, MexaHH3M Haqa.i:lb-
Horo HHHQHHpOBaHH5I B orrpe.II.e.ilCHHbIX YClIOBH5IX OKa3blBaeTC5I Hecy-
meCTBeHIIhTM. KaK 6bI HH 6bIJI OH3HCpreTHtIeCKH HeBbIrO;rCH, 31'0 npaK-
THqeCKH He CKa3bIBaerCH Ha KHHeTHKC caMOYCKOP HI0I..I.J.eikH peaKUHH
C 6bICTpO pa3MHO}KaIOlll.H 'IHCfI aKTHBHbl1\-IH ueHTpa fH.
COCTaBllM KllHeTHqeCKOe ypaBHeHHe pa3BeTB..1eHHOH u.enHOH peaKUIUI.
I13MeHeHHer..I KOHl1. CHT paUHH YCTOi'IqHBhIX HCXOIJ:HbIX KOMIIOHeHTOB BO
BpeMeHH MOLKHO B DCpBOM npn6.rIHLKeHHH rrpcHe6peQb H yqHTbIBaTb JIIUllb
ropa3 0 60JIee 6blCTpbIe 113MeHeHH5I KOHIJ;eHTpaUHH aKTHBHhIX l1. eHT pOB fl.
DpM 31'01\1 113MeHeHH5I n orrpe,rr,e..1HlOTCH CKOpOCTblO naqallbHOro IIHMUHIl-
pOBaHH5I W 0, CKOpOCTHfvlH peaKI.J,HH pa3BeTBJIeHJUI H 06pblBa uerretL
CKOpOCTb HatIa.TJbHOrO HHH11.HHpOBaHHH He 3aBHCHT OT KOHIJ;eHTp a l1. H lI
Hl\'felOI..I.I,HXCH B CHCTe1\-fe aKTHBHbIX Il,eH1'pOB, HHI{JJ}UlpOBaHHe npe;J,CTaB-
.HHeT coGon KaI< 6bI crrOHTaHHbIH: nponecc. CKOpOCTII npOll.CCCOB pa3BCTn-
.;rIeHHH H 06pLIBa (Ha nOBepXHO_CTH HJIH npH yqaC1'HH HHfH6uTOpOB) npo-
nopl1.HOna.rrbHbI KOHueHTpaUHH neUTpOB, T. e. 9TH rrpou.eCCbI HMelOT nep"
BbIii: rrOpH)J;OK no KOMnOHeHTY C nepeI\.feHHOH KOHueHTpaltnej:L 06Ul,HH
6allanc 06pa30BaHHH aKTMBIILIX lteHTpOB onpeAe.!I5ICTC5I CYM1\.fOti - CKOpO-
CTerr Bcex Tpex rrpOQeCCOB:
= \F o -1- In - gn = lW o + (r n (1.32)
r,rr,e f H g - KOHCTaHTbI CKOpOC1'H peaKUHH pa3BeTBJIeHHH H o6pbIBa
q> = f - g.
Ilpn rp > 0 npoH3Bo HafI no Bpe [eHH KOHILeHTpaI.I.HlI KOMrrOHeHTa,
BC1'yrrmOIlI,ero B peaKUluo (aKTHBHbIX ueHTpOB), - rrO..10)l{II1'ellbHa. B 01'-
lIlitIHe 01' paccMaTpHBaBliUIXC5I paHee npOu.ec.coB CKOpOCTb peaKUHH B03-
pac1'aeT BO BpeMeHH. 31'a oc06eHHocTb 06YCJIOB..rreHa pa3 :IHO}KeHHeM
aKTHBHbTX II.eHTpoB rrpH TaKHX pC}KHMax, KOflJ:a CKOpOCTb peaKIJ;HH pa3-
BCTB..r:reHIHI 60JlbillC CKOpOCTH 06pbIBa.
EC.iIH } O Haqa.TJa peaKHHH CHCTeMa He con:ep:tKa.l1a aKTHBIIbIX ueH-
TpOB, T. e. rrpH t = 0, n = 0, HHTcrpHpOBaHHe .llaCT
n = o (ecpt - 1) (1.33)
CKOPOCTb cYMMapHoH peaKIl.HI1 <D onpe,i':(e.rrfIeTcfi CKOpOCThlO npou.ecca
pa3BeTBlleHH5I, KOHeqHbIH npOlI.YKT o6pa3yeTcH TO,!1bKO npH 3TOH peaK"
38
UHll. Ila KaiKAbIli 3JIeMeHTapHLIli aKT pa3BeTBlIE'HHH :!-enn 06 p a3 y e,TcH v
MOJleKY JI KOHelIHOrO npo)J,)'KTa, cTexHoMeTIHI4eC Hl1 K03qxtmUHCHl v
I-C\'leeT rrOp5:1)I.OK e)J.HHMIl.bI. 113 3Toro YC.TIOBH5I CJIe.n.)' eT
CD = "In = 'V of (eQJt - 1) (1.34)
3aKoHoMepHocTIt KlfHeTltKII u,enHblx peaKIJ,Hll. Pa3BHTHe l1. rrHOH
eaKII.lfH BO BpeI\'leHH H onpeJJ,eJIHeTC5I COOTHoweHHeM Be..'1HQHH f H g.
hr nI <p > 0 1l0Ka3aTev'1b 3KcnOneHTb[ B ypaBHeHHH (1.34) nOJI?}KHTeJICH,
H pCaKU.HH IIeorpaHHllcHHO caMoycKOp5IeTc.H. B HaqaJIhHbHI nepHo.n.,
Kor)J.a qd « 1 ( 1.35 )
{!J 'V \f/oft
,
BBMAY Toro, lITO CKOpOCTb Haqa bHOro JnIHu.HHpOBaHHH MaJla * ,
CKOpOCTb cYMMapHoH peaKll.Hll Ha 3TOll CTa.Lf.HI1 q CTO OKa3bII3"eTCH H
npC,TI:eJIOB tIYBcTBHTe.rrbHocTH H3Mepwrc.rrbHbIx npnoopoB, H 3al\.1CTHoe XH
Ml1lIeCKOe npeBpauJ.,cHHc OTCYTcTByeT. t
CnycTH onpe.ll.e..TJeHHblII npoMelKYToK Bpe ...lcHII BeJll1qH a e£P CT:-
HOBHTC5I 3aMeTHO 60Jlblile e.ll.HHHl.(bI, noc..1e t!ero CKOpOCTb peah.I HH B coo 1-
Bt'TCTBHH C ypaBIIeHHe .1 (1.34), J-Ia4l:1IIaCT 6hlC.TpO B03pacTaib ( e pa3
. . I/n; ) . OHa .Lf.OCfl:lraeT HeorpaHw:rCHHO 60JlbIllHX 3HaQeIIIH1, XOTfI
3a BpeMH 'to " B 6' )J. r>,loe ;1, TIfI
,IJ,O 3Toro 6bIlla npaKTHlIeCKH HeOmYTHMOH. PCl\'ffI, Heo XO' H v .:
Toro, QTOObl CI<OpOCTb peaKu,HH Bo poc.na OT HY LTIH )1,0 nI HMaJIbH H npaK.
THqeCIUI H3 'lepHMOH: BeJIHlIHHbI «D ' Ha3bIBaeTC5I nepHOjI,Ol\.1 HH, )' KU.HH T.
CvuJ.ecTBoBaHHe nepHo.lt.a 3a,D,CplKJ<H npH pa3BHTHH u.enHOH pe"\ .Kl1,lll
06vc.nOB.,TIllBaeTcH He06xo,D,HMOCTbIO HaI\:onJIeHll5I B pearnpYlOilJ,err C11
cTe 'le coofBeTcTBYIOIlI,erO KOlIHqeCTBa aKTHBHhTX ILeHTpOB; TOllbKO noc.ne
::Horo npenpall1,eUHe CTaHOBHTCH 3alvIeTHbl?\L KaLKyw. eeC5I OTCYTcTBHe. pe-
aKl1.HH 3a Bpe1\'IH npoTeKaHH5I ncpHo,!J,a HH,:1.yKll,HH onpe,n,eJIHCTC5I qYB: BH
Te.TIbHOCTblO cpe;rCTB H3MepeHHH H cnell.mpntIeCKHM xapaKTepOl\.f KHheTH
qeCKOrO ypaBHeHH5I (1.34). <1>' ,
CKOpOCTb peaKll,HH 06blqHO I OCTHraeT nopora qYBcTBHTe.TJbHOCTH
Kor,D.a cept » I, Tor,rr,a
III
III
IIII
i I
I
II
v W' f e fPt
d) 0
\0
H
1 <D' (p
'I "7 4) in -\V 0 -;;;r
' . a
H31.:IeHCHHfl Be.TIHlIHHhI w. VI cpaBIHne.7IbHO :-'.iaJIO B.::IH5II0T Ha 31-1 -
lIenHe T B CH.TIY .TlOrapHq)MH eCKoro xapaKTepa 3TOi1 3aBHCHMOCTH. TIo-
3TOMy B rrepBO 'l npH6JUDKCHHH MO)KHO CtlHfaTb
(1.36 )
11
I
canst
't'=
fp
( 1.37)
* 3TO - HCl.J.eIUlOfi npol.J.ecc c 60.TIbliiOll :mepnlell 3KTHB8IUHl, Heo6xOAIB-IOH It:I5I
o6pa30naHIHl CBo6o)I.HbIX pa.n.HK8JIOB.
39
Be. I:.HHY ne!JIIO;1.a HH,U,YKI.JJ1H 06blQnO onpe.n;e..15HOT COOTIIOWeHllH CKO-
pOClen npOll.eCCOB pa3BeTBJ1CHHH H 06pbIBa ll.eneH, a HC CKOpOCTb HR43Jlb-
Horo BIIHll.11HpOBaHHH lUlH QYBCTBHre.lIbHOCTb II3MepHTe.TIbHbIX npH60pOB.
I--Ia IHIC. 7, a nOKa3aHLl xapaKTepHbIc THnLI KHHCTI,rqeCKHX KpHBbIX
ll.enHoro npolI.ecca TI p > 0 d 2 Q:J 0
. H {P -dt 2 - > 3aBHCH1\.fOCTb CKOpOCTH pcaKQHll
0'1' BpeMeHll onnCbIBaeTCH (B HRLJaJIbHOrI CTa}l;I-IB) KpHBOi"i o6pan:r.eHHofi
BblfIUKJIOCTbIO K OCB a6cTl Hc ' ./'" 0 d2(D '
J '-' c, npH {p --........ dt 2 < 0 KHHcnIlleCKaH KplI-
BaH BorH\fT3. n p J- I 0'
J T3KOlvI MeX3liH3 'le peaKll.Hli !(l1HeTnqeCKUe KIHIBbIC
rp
Tl7 mox
m
t
TTlGX
t
t max
6
PHC. 7. KHlIC'TUqeCKHe KpUBbIC ](,,151 I errno.fi peaKIJ.HH:
a -=- CIWpOCTb pCctKIJ,IiU; 6 - l<.OJIHtleCTBO npOpeaI'HpOBaBIIIero nelqecTBa; 1 - <p >.0 t = t
(I) - W maX ' d 2 mldt 2 = 0; 2 - cp < O. <D (t = 0) = O' 2' - to < 0 t . max,
. . "t', B MOMeHT = 0 C03j1;3Ha
C1'<Il HOHapHafl KOU1\eUTpall,HfI 8KTHBlIbiX IJ,CHTpOB, <P (t = 0) = <Po.
t
a
BbIXOj!,HT H3 Hat{aJ a KOOp,n;HHaT, T. e. B MOMCHT t = 0 (J) = O. IIanoMHHM
qTO npn 1v OHO-, OH- . H TpH:\'fO.lleKy.l151pHLlX peaKll.H51X CKOpOCTh A.faKCH:
l\IaJIbUa B HaqaJIbHblH MOl\.leHT H .rr.a.nee Me .l1eHHO VMCHblTlaeTCH.
TIpll r.p 0 peaKIJ.H51 HOCHT HeCTaUJ10HapHblli wxapaKTep: ee CKOpOCTb
npOrpeCCHBHO B03paCTaCT. JIllllIb nOC.'-'Ie 113paCXO;J;OBaHII5I 60Jlbllieii qaCTII
HCX?J1.HbIX.> KOMnOneHTOB HaIIHHaeT CKaSbIBafbCH yMeJIbUleHlle- fiX KOH-
eH rp, Il.HH II pOCT CKOpOCTll peaKUHH 3aMe):VI51eTCH. Ha KpHI30H saBH-
Cl'IMOCIH (t) HMceTCH TOqKa rreperH6a, npH 66,,'IbIIIHX t CKOpOCTb peaK-
II.HH npOXO)JJIT qepC3 MaKCHl'\'fYM.
0' 4el'vf 60.rJbllIC (j), TeM KopOt.Ie nepnO}l; llH)J;Y, I<I.I;HH TCM 6bICTpce pa3BH-
BaeTC5I pCaI<I1.H51 BO BpCl\IeHH, TeI\.1 Kpyqe nO,' HH .1aeTCH KpHBa5:l <D (t).
KpHBhIe 3aBliCHivlOCTH Ko..1UQeCTBa npopeanipOBaBlllcro BeIIl,eCTB3 Tn 0'1'
BpervreHH (pnc. 7, 6) TalOKe HMelOT TOtIKY nepern6a. I1x CnCIl,HqmtfeCK3H
S-.o6p 3HaH cl)opMa, .nerKO 06HapYlliHBaervla51 npn 3KcnepHMeHTa.JJbHbIX
Hcc.ne,n;oBaHHH,x, npe c:'aB.lIHeT._. c060il 06bIQHO caMoe lIar JUI}l,HOe YK33a-
JIMe Ha pa3I3erB.TICnnbIH l.1.enHOH MeX3HH3M peaKUHH.
TIpH <p < 0 p eaK l.1. H SI HMe.eT COBceM MI-I011 xapaKTep. KOf.1I.a I (rt I » 1
liS ypaBIIeHllH (1.34) c"TJe.n;yeT '
Q:J = 'V \'(Iof
I cP I
(1.38)
40
Cr<opOC fb peaKUHH cTpeMHTC5I K nOCTOHHHOMY npc)J.eJIY, npou,ecc npllHH-
Ma eT cTaUHoHapublft xapaKTep. J11111Ib B HaLIa"TJhHbIii IIepHo , nOKa H)J..eT
uaKon,,'leHHe aKTHBHbIX l1.eI-ITpOH, CKOpOCTb pCaKl.1.H H B03paCTaeT. I10CJlC
)J.OC'fHiKeHlI5I CT3LLHOHapnoro pCiKHMa HaLIaJIbHOC llHHUHHpOBaHHe ):(aeT
J{aJ( pa3 CTO"T}bKO HOBblX aKTHBHbIX LLeHTpOB, CKOJIbKO ny>KHO, lJTo6b1
noKPhITb ,lI,ecpHUHT, B03HHKalOllJ,Mi:i B pes)' .llbTaTe npeBa.TJHpOBanlHI 06pbIBa
Ha; pa3BCTBJIeUHHMH... \
qacTHbI}I CJIY"lIaii TaKoro pe:>KHMa Ha6JllO;I,aeTC5I B iJeaKIJ,HHX C JIepa3-
BeTB.!1eHHbIMH uen5IMIL TIpH 3TOM \\7 0 MOJKeT 6blTb AOCTaTOqHO BeJIHKa,
a g rVla TJa, II CT3LLHOnapHa51 CKOpOCTb peaKLLHH ocTHraeT H3MepHMhlx
31IatJeHHH. Y peaKl1.HH C pa3BCTBJIenHbHvlH ucnHMH 06blqnO Ha6JllO aeTC
o6paTHoe COoTHouleHHc, n CKOpOCTb peaKUHH npn CTall.HOHapnoM pe2KIIMe
npeHe6pe}KHMO :\ola.11a.
CKOpOCTII peaKll.Hii pa3Be:rB.TIeIIH5I H o6pbIBa u.eneli, B COOTBeTCTBHH
C XlIMH"lIeCKHMH oco6eHHOCT5IMll K3}I{):(oti pcarnPYlOw. eti cHcTeMbI, xapaK-
TepH3YlOTCH onpe.J.eJIeHHbTMI1 saBHCHMOCT51MH OT TeMnepaTypbl H KOHueH-
TpaUHH OCT3JIbHblX KO:\lTIOHeTITOB. CrrcLLHcpHQeCKa5:l oco6eHHocTb l1.enHbIX
npoueccoB 3aIOUOqaeTC5I B TOM, 4TO peaKUHH pa3BeTBJIeHHH Tpe6YIOT 3a-
Me:rnoH 3HeprHll aKTHBal.1.HH, Tor):(a KaI< TeMnepaTypnbIH K03qxlmLLHeHT
KOHCTaHTbI CKOpOCTH 06pbIBa 6.n1130K K ny.mo. Y peaKl MII 06pbIBa ucnen
F1 I>
Bcex Tpex THOOB - npn reTeporeHHOH H OO'be:\UIOH peKOI\.10HIIau.H5IX
11 npn B3aHMo,n,erICTBHH pa,lJ.HKalIOB C aKTl1BHbIMH npHMeC51MH - 3IIep-
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., enIIble peaKI HH C 06bIllHbIM pa,n:IfKa.rlbHbIM MexaIIH3MOIvI pa3BeTB.TIe-
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npHBOJJ,HT K B03HHKHOBeJIHI{) TaK Ha3bIBaeMbiX xo rrO,i1;HbIX n.;rJai\.tcH J pac-
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npH npOTeKaHHH Hepa3BeTB.TIeHHbIX ueIIHbIX peaI<llHiL EhoT npouccc KOM-
neHcnpyeT y6bI.TIb aKTHBHbIX ILeHTpoB npn peaKaH5IX 06pbIBa llenH. OH
onpe; e TIHeT,... ,n:a.rIec J YCJIOBHH YCTanOBo/1eHMR CTaI{HOHapHoro pe)luu...la
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42
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lJ.l10HapHoro pe)l(HMa npM Hepa3BeTB..1JeHHbIX uenHbIx npoaeccax.
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COYll.apeHliiI H.,'lH na nOBcpXHOCTl1.
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.3KcnOHeHl1.HaJIbHO 3aBHCHT 0'1' TeMIIepaTypbI.
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CTeMe; CTall.HOHapHaH peaKu,H5I lIe BJII1HeT Ha 31'01' npOllecc. PaEHonCCHe
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aKU.HII yCTaHoBHTCH fO.fIbKO cnYCT5I 3HaQUTeJlbHbifI nporvIeiKYToK Bp -
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Ha npOT5DKeHHM .:)1'oro nqHIOJl"a CKOpOCTb lI.HCCOll,HalllIH npeBOCXOPJi r
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CKOpOC1'H OOOHX npou.eCCOB cpaBIIHlOTCH TOJlbKO noc rre YBe:lHtleHU5I KOH-
ILeHTpalLMH aKTl1BHbIX UCH'rpOB ]1,0 paBIIOBeCHon.
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BbIT10JIHHTbCH TOllbKO B TOM c.TIyqae, eCJll1 KaTaJIH3aTOp B paBHOI1 CTe-
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HeiL OqCBI1.D;HO, qTO rrpl1 paBIIOBeCHOlI ;1.HCCOlI.HalLHH 06PbIB n.eneli B OC-
HOBHOM IIpOHCXO;I..H1' TaM )Ke, r;I,e H HX 3apOlli!(eHHe: ec.JIH HHHl.1)1l!pOBa-
HHe reTepOreJIHOe, TO H 06PbIB u,enen npOHCXO;I.,HT Ha CTeHKax.
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T1PH 1130Tep U:lllCCKOM OlernCHHH pa3.u.eJlbHblX 11.0 Toro IWMIIOHeJlTOB 3a.n. e p}KKa onpe;!.c-
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npH COOTBeTCfBCHHO 60JIblllCH IJa\laJIbHOH Te:r-.mepaType ,nIICCOllHlipYlOlIJ,erO KmmOlleHTa
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OOpbIE lJ,eneH np01'eKalOT reTeporeHHO. 3rn q)aI\:TopbI CTporo. O)I.HHaKOBO
B.TIH5IlO1' Ha 06a npoIJ,ecca. O,n;HaKo npHcY1'cTBliC KaTaJI1l3aTOpa yCKOpHCT
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paBHonecnYI{).
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BUR Ha4aJlbHOI'O HHlIIJ,HllpOBaHH5I OKaSbIBalOT cyw.eCTBeIIlIoe BJIH5IHHe na
pa3BH1'He peaKIJ,HIL TaK, Y pH,n:a Me.l1)IeHHO pa3BHBaIOllI.HXCH npou.eCCOB
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(CI\L r.;1. 4).
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npC CTaBjlHCT c06011 KlIaCCH4eCKHlI npHMep IJ,el1HOrO npeBpaU.I.eHHH. Ee
1exaHH3M npoIlI,c, IJeM Y )J.pyrHx peaKIJ,H11; Tel\.1 He MCHee KHneTHt.ICCKHe
- 33I<OIIOMepnOCTli neJIb3H CIJH1'a1'b H3BeCTHblMH BO Bcex AeTaJ15IX.
AB1'HBHbIMH I.I.eJITpaMH HBJI5UOTC5I aTOMbI XJIOpa H BO)l,opO,ILa, noncpe-
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pea I<IJ.HH c.rre,n:YIOw.Hi.j:
CI -f- H 2 = HCI + H (XI)
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xapaKTepHbIe oco6eHHocTH TaKoro rrpOI.I.ecca.
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o6pa3Ylo1'c51 B pe3Y .T1bTaTe Tep iH4ecKofI ,n,HCCOUHau,HH XJIopa, 10.T1eKY .rIbl
KOTOpaI'O MCHce rrpo4Hbl, el\'1 MOJIeKy.fIbl Bo.rr.opotI..a: DC1 2 =- 57/{KaA/.MO/lb
Tor.n:a EaT< D H2 -.= 103 J{J({lJ1//t!Oilb. B CMeCH, He co;::r,ep2KaIlI,cii HHrH6HTo-
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44
1-101'0 BO)J.opO;:I:a MeHbllle KOHueHTpaUlili aTOMapHoro x.nopa, HO 3IIaqJi[-
'feJIbHO npeBOCXO.L(llT paBHOBeCIIoe 3HaIJeHlIe.
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Horo x TIopa Hero peKOM6MHaUH5I npOTeKalOT reTeporeHHO. KOHI.I.eHTpa-
UHH aKTHBHblX .JJ,eHTpOB, a c.TIe.rr.OBaTe TJbHO, II CKOpOCTb peaKI.I.HH He 3a-
BHCHT 01' r-,'laTepUaJIa CTeHOK peaKTopa H O1'HOllleHI1H SI V, KaK 31'0 6bI.no
nOHCHeHO B pa3J1;. 5. Eo Bcex T04xax peaK1'opa KOJH eH'rpaI.I.HH I CHTpOB
O} HHaKOBa. Pe)KHM peaI<UHH C1'aUHOHapeH, no Mepe pacxo)J.oBaHIHI HC-
Xo;J.HbIX KOMnOHeHTOB ee CKOpOCTb MejI,.T1eHHO yMcHbIllae1'C5I.
VI3.,'IO)KeHJIbIe npe)..lcTaBJIeHHH n03BO.MIlOT ..'IerKO nO.TlyqHTh KHHe1'H-
LJeCKOe ypaBHcHlle peaKu,I1H. 0603HaIJHM 'Qepe3 k ll KOHCTaI-TTY C.KOpOCTH
3.!le).o1eHTapnoil peaKUHH (X I)
<D = 2(])11 = 2k n [CI] [H 2 ] (1.39)
f1pH YCTaHOB.rreIlliH paBHOBeCHH Cl 2 2CI
[CI] = KC12y rClz] (1..10)
f,ae KCL - KOHCTaI-ITa JJ;HCCOU.HaU. HH .
H3 y:paBHeHHH (1.39) H (1.40) CJlc.n;ye1'
d [HCI] _ _ 2 d [CI 2 1. [H d - 2k K [H J IF [CI ] (1.41)
"'=' - dt' - dt - 11 C 2 2- Y 2
TaKHM oopa30M, pCaKII.HH Me}K)I.Y XJIOpOM H BO.lLOpOAO 1 HMeCT ,II,po6-
Hhli-i, nO T1YTOPHhIli nop51.n;OK: nepBbIll no BO,a,OpO.lLY H IIO T10J3HHHbIii no
X.flOpy. KOHu.eHTpau.HH XJIopa 11 BO.D,Opo,n;a CBHsaHLI C'rexHO ofCTpHt.leCKIU\.1
COOTHOIlleHHeM, 6.iIarO;I;apH QCi\'fY ypaBHeHne (1.41) JIerKO MO}KCT 6hI1'b
npoHH1'erpnpoBaIIo. EC.T1H [1-1 2 ]0 = [C1 2 1 o = no, TO
-} kll/(Cl fl = Il\V = (V 1/(J -1) V no t (1.42)
r.ng a = [C1 2 ]/no = [H 2 1/no (cp. pa3,II,. 1).
3fpcpeK1'HJ3Ha5I KOHCTaH1'a CKOpOCTH k\y/ onpc)J.e.lI51eTCH Be.nnqHHaM '
KOHcraHThI )J.HccouuaUIUI x.nopa H J<OHCTaH1'bI CKOpOCTH 3jICi\reHTapHofI
peaKUHH (X I). 113 ypanHcHHH H30XOpbI BaHT-fo4Jcpa CJIC,rryeT
dlnK cI2 D . (1.43)
d (liT) - 2R
II
; I -
I I
I .
I
TI03TOMY
k\'(I = canst .e-(A 11 + D/2)f RT (1.44)
fil.e All - 3HeprHH aKT Ball.HH peaKI.I.HH (X I). OqeBHjJ.,Ho, qTO 3clxpeKTHB-
HaH 9HeprH5I aKTHBaIJ)U1 cYI\-iMapnoro npOIJ,eCca (All -1- Di2) =
= 35,5 KKQJ1/ MOAb onpe,n,e.TJ51e1'CH :6 nepBYlO OtICpeJI.b TepMO,ILHHa nIqeCKoi'I
xapaKTepHcTHKoi1 - Ten.,rIOTOH }1.HCCOUHaUliH XJ10pa H B l\lCHLIUeii CTe-
lIenn - HC1'HHHOII 9HeprHeH aKTHBaIJ.HH onpeJJ.C.fUUOlIL efI pcaKI.I.l1lI (X I).
B pe3Y JlbTa1'e IJ.enHOrO MexaHH3Ma B3aHMO;I,eHCTBHH 1-1 2 C Cl 2 era
CKOpOCTb Be.T1UKa Y)KC npn cpaBIIHTeJIbHO YMepeHHblX TCMnepaTypax.
TaK, BpeMH H3pacxo.n:oBaHHH 1 % cTexuOMe1'pnqeCKOH CMeCH H 2 + CI 2
npl1 283 0 CHI QnV,t paBIIo Bcero 0,13 ceIL B aHaJIOrnIJIIbIX YCJIOBll51X
45
"
CMeCb I-I 2 + J 2, pearHpYIOIl1,aH 6HMO.neKY JIHpHO, J{OCTHraCT TOn }Ke CTe-
neHH npCBp3III.E'HIU:I 3a 180 f-t.
TIpTI 3aH 1 AejIcT l1H XJIol:a C BOj.J,OpO.I(OM B HarpeTbiX cocy..a.ax paBHo-
B cHe In;HccO HdU.HH x :opa ycraHaBJIl1BaeTC5I Ha CTenKax B TeqCHHe npe-
MelIU, l'vIa..'1Ol 0 no cpaBlIeHlllO co Bpe;,,'leHe\1 3aMeTHoro npCBpaIJ eHH5I.
TIpH pacnpocrpaneJIHH nJla 'feHII BpeIVI}i peaKll,HU 1\'ia TIO, TOr;1.a KaK caM
npo,U,ecc np..o eKaeT B npOCTp _ CTBe oe3 CTeIIoK, KaTa.!1H3HpYIOJlLllX )J,HC-
C? 11aIlHIO XJ!opa. ATOMapHhIH XJTOp MO)KeT B 3TOM C/IY4ac 06pa30Bbr-
B3'fbCH TOJlbKO IIPH rOMoreHIIbIX peaKlI.HHX.
B nJ1aMeHH, T. e. npn OqeHb BhICOKHX TeMnepaTyp3X HCCOllHaJ H5:I
MOJIeKy.ll x.nopa npOHCXO.I.lHT npH HX coy.n;apeHIHIX C .rIlo60i11.IaCTHuet'I 1\'1
(Cf"L pa3J1.. 4):
Cl 2 .1- M =-= 2Cl -1- 1\1 - (XIII)
BhICOKaH TeMnepaTypa np.olLecca n03BO..'HleT CI1CTeMe C1 2 + ]\,'1 qall1.e
npeoAo.rreBaTJ 3IIepreTl!tieCIultI 6apbep BhICOTOH D. TIpH BOCJ1Jla:\-fCHeHHH
Te:\'fnep..aTypa IVIIIoro HIDKe, H BepO.HTHOCTb TaKoro npoQecca C,J1IIIII K01,i
1\I3..'1a. e b HaqHHaeT HrpaT?, 3Ha1.IHTeJlbHYIO pO.l1b npoll.ecc pa3I3eTB.n:c-
HEB I.J,eneH, Hc-cYllJ,ecTneHHbIH nlHI .n:pyrHX pe}KHMax. TIO-BI1)J)1i\'fOJ\'fY
3'1'0 - TpHMO.i'IeKY.TIHpHaH p eaK ll.J1H '
H -f- 2Ch = HCI -1- 3Cl (X IV)
BbICOKa <30' epM t{HOCTb peaKI.J,HH (X II) (46 /{KaA/.J1'1O/lb) o6yc..rrOB.TIH-
BaeT paella)]; BIOpOH l\Io.neKy.1JbI XJIOpa IIPII Tpo:fIHbIX cov,n"apeHH5IX co
cpaBHHTenbH aRoH 06aBOqHOH 3Hc-prneH. J
B3al MoAencTBHe x.nopa C BO;J;OpO;J:OM 'iO}KeT HHrH6npoBaThcH KHC.:JO-
po,tl.OJ\f. 3TO o6YC.J10BJICHO pCaKIJ,Heil o6pbIBa nenn:
H + O 2 + 1\1 = H0 2 -1- M (XV)
TplIl'vIOJIC-KY.TU-IpH35i peaKll.IHI (XV), KaK 11 MHorHe }:(pyrHe npOne.ccbl npH-
Coe,IJ,HIIeHHH cBo60,QHbiX aTOMoB IT pa,D,HI<a.ilOB, He Tpe6yeT aKTHBallI1H.
LIBO aTOMapHoro BO;"""(opoAa JI3 c<pepbl TepMW-IeCKoti peaKI IUf JIpHBO HT
h 1'0:,1): , I:O h..OnLlCHTpaUH5I aTOMapHoro xnopa OKa3bIBaeTC5I !\'leIIhIIIC paB-
HOBeClIOH, COOTBeTCTBeHI-IO l'v!eIIbIIIe H CKOpOCTb CY?\-IMapnoro B3alIJ',!0)];ei-i-
CTBllH.
_ PeaKIJ.MR "BO)J,opOJl.a C KllCJIOpO)J.,OM r 20, 15]. CneI.J,HqJI-IQeCKHe oco-
6eIIIIocTH 3TOH peaKI.J.I1H npOTHBOnOJIO}KHbI oco6eHHOCTHi\-1 peaj(QHlI x,,1]opa
C BO OpO.n:O:- I. IL..IJHIIIIbIM Hepa3BeTBlleHHbL\'1 lI.CTI5I1\'i B3aJnl0 ClicTBH5I H '>. -+
.+ C] 2 3;.r.eCb npOTHBOCTOHT BeCblvra HHTenCHBHbIe pa3BeTBJIeHH.H lleI c i.
B Ka}I{)"""(O:\'f pe KIU10IIIIOM ILlIKJIe npOHCXO,iJ.lIT l[H60 pa3BeTB.TIeHHC, .TInGo
06P IB I.J,CnH., r, K!,1e lI,eIIH I1a3bIBaIOTC5I cn.TIOJllb pa3BeTB.neIJIIbnIH.
l1exaHH3M 310H peaKlllfll 130 MHorOM cxo)I,en C MexaHH3MO i pyrHx
, p. QeCCOB OKI1C IJCI- l15-I. 9TO n03BO.TI5IeT Cqtn aTb peaKll.HIO :\'lelK,l(Y H 2 H O 2 ,
I at\. )KC KaK H Me)K.J.Y H 2 H C1 2 , Mo.n;C.iIbHOH. PcaKI HoHHaH I..lenb Be.ll.CTC5I
TpCM}i aKTHBHhIIvIH I.J,crITpa)"fH: aTOMapHbD.HI BOJJ;opoAOM Ii KHcnopO,n mvl H
pa)"""(HKa.TIO:M - rl1}.(poKcn..'IOM 01-f.
I-IaH60.T1ec BepC>5ITeH CJle,qYIOIII,HfJ nponecc reHepnpoB3HHH Ha113.nbHblX
aKTHBHbIX ueHTpoB
06pa30B3BlllHeCH pa,!J,HKa TIbI OH 3aMeH5IIOTC5I aTOMapHb11'vI BO,iJ.Op01 0M
B peaKuHH npoJI.o.rnKeHHH QenH:
OH + H 2 = H 2 0.\- H (XVII)
ATO;"'lapIIhli1 BOJI.OpOA MOLKeT BCTynaTb B peaI\UHIO pa3BeTB.n:eHIUJ, o6
pa3Y51 ABa HOBLIX aI<THBHbIX u..eHTpa:
H + O 2 = OH -\- 0 (XVIII)
If?, -+ O 2 = 20H - ] 6 KKaAj,'fD/lb
(XVI)
ATOI\lapIIhIii I<HClIOP0)J, TaKlli.C .n.aeT pa3neTB.TIenHH uenH
0+ H 2 = 01-{ + H (XIX)
vb Tpex noc.TIeAHHX npOI..J.eCCOB, o6pa3YIOllI. nX peaKIJ}IOHHbliI Il.HKn, pc-aK-
UHH (X\TIII), y KOTOpOJ i A = 18 KKa/tlJ w/1b, - HaHoo.TJee z.,.le/JJleIIHaH,
ee CKOpOCTh H onpcJ.e.JIHeT cYIvlMapHYlO CKOpOCTb npcBpall.\CHH51.
B OTCYTcTBHe o6pbIBa Qencii peaKI.J.J10IlHblH QHKl:'I MOlliHO npe/l,cTa-
BHTb B BH)J;e O)J,Horo cyl\HvrapnOro rrpOllecca
H + O 2 + 3H2, = 2H 2 0 +- 3IJ (XVII IA)
CKOpOCTh KOToporo onpeJI.e.flHcTcH CKOpOCTLlO peaI<llHl1 (X\lII I). 3LLecb
o)J,HH aKTHBIIhIii QeHTp, BCTyna5I B peaKlu no , nOpO)K aeT TpH.. IIOBbIX,
13 pe3Y JlbTaTC qero npOI1CxoJJ:HT ObICTpOC caMoycKopeHIIe. T aI<OH pe)luc\'1
xapaKTepl13yeT Haqa TIbHYIO CTa HIO pcaKQHI1, KOrJJ,a KOI-I1..LeHTpaUl H aK-
THBHbIX UCHTpoB'Ma.na. C ee pOCTO .i B03pacT3cT BepoHTHoCTb oopbIBa
l enH, H pOCT CKOpOCTH peaKI..J.HH 3aMe)J..TmeTCH.
OapblE peaKI..J.HOIIHbIX QenclI npoHc-xoJ],HT npou,eccax pe,- 0i\'l6HIIa-
HI111 VKa3aHIIbIX aKTHBHhIX ueHTpoB, a TalOKe B Y}Ke H3BeCTHOH Ha\.f pe-
aI<un"u (XV). 06pa3YIOlll.UriCH 13 Hei'r pa,AHKa.,rI H O 2 CpaBIIll'reJ1bHO :r-.la TIO
ClKTHBeH. TIpn HH3KHX TC),'lnepaTypax OH npeBpallJ,aeTCH, 06LI1.IHO reTepo-
reHno, B YCTOliqHBbIe np0.il.YKTbI: H 2 0, O 2 n H 2 0 2 . ..
Ilpn 6o TJee Bb1COKHX TeMnepaT)'pax CTanOBHTCH B03MO)KBblJvl IlOBhIH
npou,ecc npo).(o.TILKeHHH llenH
H0 2 + H 2 = H 2 0 2 + H - 15 KKaA/, f.OJZb (XX)
T. c. peaJ<U 1u1 (XV) 3.n.eCh HC npHBOJJ;HT K 06pbIBY Qcnll. PC,...aI<QIUI (XX,?
nrpaeT cYll.\eCTBeHHYIO pO.TIb npn pelKHMax HHTeHCHBHOT'O oopbIBa nenell
nYTC\1 rercporeHHoii H.n:n TpHMo..rre.KYJI51pHOH peKo ...16HHal\HH J1.pyrl1x
aKTHBHbIX QeHrpoB. . "
TIpH T3K01'1 J\lcxaHH3l\'Ie 06b1QHO B03MO)KeH .TIH60 OqeHb OhICTpblH pOCT
KOHQeHTpalU1li aKTHBHbIX ll.eHTpOB, pa3:\HIO)KalOlI HXC51 B Ka}K.ll.OM Tpex-
q l1eHHoM QllKJIC, .TUI60 TaKoe LKe 6hICTpoe I1X YHlItITO:lli.eHHe B peaKTt!HIX
oGpbIBa uenH. TI03TOMY B3aHMO.ll.cfICTBHe I-I 2 - \- O 2 06HapY)Kl1BaCT xa-
paKTe.pHbIe oc06eHHOCTH HHTeHCHBHO caMOYCKOp51lOULerOCH lJpou.ecca.
PC-3KO BhIpaLKeHbI pa3JIHQHhIe ero PC}KHMhI: npeHMYU\eCTBeHHoro ,npOTe-
KalIHH pa3neTB rreHH5I lleneff, Me,tl..iICHHOll CT3QHOHapHoI"i peaKHHH (g > f)
n c Iyq3e o6pbIBa uerrei-i Ha TBCpJJ;Oli nOBepXHOCTH npB IIH3KHX ILaB.iICHH5IX
I1.TIH 60.iJbUIHX SiV, o6pLIBa u.eneii B o6beMe npH BhICOKltx / aBJIeHHHX H
He3aBHCH1\,iOCTH CKOpOCTH peaKllHH 0 r OTHOIUeIlI151 S/ V. vIHTeH.cHBJIbie
pa3nerBJIeHH5I ueneii IIIHmOJlHT I{ HaKOIlJleHHlO B ccpepe peaKlLHH...aKTHB-
47
46
II I
III!
I
1':
III
!
I
I IJ
I
.',
HhIX U.eHTpOB. r C'ranOBJIeHO, 4TO npH 3TOM KOHlLewrpaU;tIH I-I n OtI MorYT
BO MHOfO ThIC5J1I pa3 npcBOCXOJU1Tb paBHonecIIbIc.
Oc06eHIIocTH KHHCTHKH HaXO.lUIT CBoe OTpa}KCHHC B 3aI{OHOI'v1epHOCTHX
)1,.'T51 npe)(e,rrOB Bocrr.rIaMeHeHHH, paccMarJhIBae:\.fbIX HIUKe. fenepnpOBa-
HH aKTHBHhIX UeHTpOB Ha TBep,n;oii nOBepXHOCTH TaK}Ke rrpUBo,n:HT K cne-
ll.Hq.HiQeCK.?T\'lY B.lIIHIHI1fO COCT05IHH5:I nOBcpXHOCTH peaKTopa Ha CKOpOCTb
B3aH1\IO eHCTBIUI, He CBH3aHHOMY C YC,,'IOBHH 1H pCKO;..16HHal.l,I1H aKTHB-
HbIX lLCHTpOB.
OKHc.neHHe OKIfC" yrJIepo)l.a [21, 221. B3aHMO,lJ,e:f1cTBHc OI{HCH yrJ1C-
po,u,a C KIIC.HOPOJJ;OM npe.2l.CT3BJI5IeT co6oi1 Ba}KHeflwyIO JVIH rrpou.cccOB
rOpE'IIIHJ peaKIJ,.IlIo. B aJIbHeihllc:\'f MhI y6e).(HMC5I, LITO npOTeKaHHe 3TOH:
peaKIUUI BO i\IHOrHX C,'lyqaHX onpc,J,e.JI5IeT IIa6J1IOJI.aeI\Ible 3aKOHOMepnOCTH
r peHH5I II YCJTOBH5I 6ccr .eqeHH}f "J33pbIB06e30rraCHOCTH. DjTH peaI{u.HII
XapaKTepCH pa3BCTBlleHHhIH ll.enHOH IvrCXaHH3!vI n OHa OTJHIQaeTC5I P51AO),.1
oco6eHHOCTeH.
T CTanOBJleHO, LITO rOMoreHHoe OKHc.:JeHHC OKHcn yr JIepO,D,a B03MO}KHO
TO.TTbKO B npUCYTCTBHH BO.LJ:bI, BO)J,opO,4a fI.HH KaKorO-Hu6Y)]:b ).(pyroro
BOJ1.0pO)I.co,rr.ep)I{allJ,cro KOMnOHeHTa, KOTOpbIH HrpaeT pOJIb Ka ra.I1H3aTopa
peam..J,HH. Tw.aTeJTbHO BbICYUleHIIbIe CMeCH CO + O 2 lIe l\'forYT 6bITb nO,n:o-
}I<JKeIIbI 11 He peafnpYIOT npH YMepeHHOM: H?rpeBaHHH. .nHillb npH 700 e C
B TaKHX CMeCHX HaQHnaeTcH MC).1}I< HHoe re.TeporeHHoe B3aHMO,X{eikTBue.
BbICKa3hIBaHH51 0 KHHCTHtIeCKHX 3aKOHOMepHOCT5IX rOMoreUHoii pc-
aI{IJ,HII..CO C O 2 npOTHBOpeQI1BbI. f-IaH6oJIee Bep05ITJIO, Iff 0 OHa HMeeT
rrCpBbTl1 nop51,.U,OK ITO OKHCH yr,nepo,.U,a H nepBhri 1 nop 5T .ll.OK no KaTaJ1H3a-
TOpy - 11 2 0 M.TTH Hz. TIop fI .l1.0K peaKUHH no KHC"rrOp O .l1.Y npH ero cO,ll,ep-
)KaHHH B CI\.iCCH CBbIwe 5 % paBen HY JIIO. .
Onpe,n:e.lleHHe TeMnepaTYPHoro K03cpcpHlLneHTa CKOpOCTH B3aHMoLleH-
CTBH5I CO,.,C 02 ac1' nepCI\.feHHOC JI,,,'l5I pa3tf'IHQHbIX COCTaBOB H TeMnepa-
TypHbIX OO"TJaCTCH 3<.pcl)cKTHBHoe 3HaQCHHe 3HepniH aKTIIBaUHH. KaK H
nplI B3aHMo/I.elicTBHH J-I 2 C CI 2 , TervrrrepaTYPHbIIl K03CpcpHI.1,HeHT onpC.ll.e-
JIHCTC}f He TO.TTbKO BeJ1HQHHoii A MCAJ1CUHOfI CTa}{HH peaI<IJ,HH. I13McHeHHH
3cpQ)eKTHBIIoii 3HcprHH aKTHBal.!.HH A CB5I3aHbl C pa3.TIHtIH5H\'fH MCXaHH3l'VIa
pea Kl.!.iUI npH pa3JIH"QHhIX ee pelKHMax.
PeaKIlHOIIH85l lLenb HHHuHHPyeTc51 fI-I)J.POKCH"TJOl\.1:
OH+CO=C0 2 +H (XXI)
AKTHBHhrt'I ILeHTP..- rH 1pOKCHJI - pcreHepHpyeTcH H3 8To .ra BO)J,op0)I.a
no },r}Ke H3BCCTH<:,fr HaM peaKIl.H-H pa3BC1'B.J1eUH5T lLenH (X\TI I I). 06pa3YlO-
UjJIHC51 BPH 3TOH pcaKlLHH aToMapnbIH KHCJTOpO,u: MOlKeT OKHClI5ITb CO
)(0 CO 2 (HCHCH9, npH JI.Boi1HbIX IVITI Tpoih-IbIX cOY,lI,apeHHHX). TIpH BbICO-
KHX Teivr epaTypax aTO.MapHblll KI:ICJIOpO;1; YQaCTByeT B peaKI HH (XV 1 I I'),
o6paTHOH (XVI II), a Tai<lKC B 06paTHMoM npou,ecce
o -+- H2 OE -f- H (XXII)
Ocym.eCTB.TlHCTCH H ApyrorI paBHOBecHbIrI npolI.Ccc
If + H 2 0 :;-+ OH -t- H 2 (XXIII)
Y K33aHTTLlc paBHoBecHbTe npOnecchT o6YC.rIOBlIHBafOT 6blCTpoe pac-
I.IJ.en.rICIIHe BO,lI,bI na pa.lXHKa.lH:>I. B pe3y.TJb1'aTe 3Toro npH 1\.r8JIb!X (no
48 .
, JaBHeHHIO C [CO 1) KOHlJ,CHTpaIJJI5IX BO}J;0P0TJ;co/J;e!DK3W,HX KaTa.rrH H-
I 'f()ll HX .406aBOK J{et'lcTBHe Jl106blX TaKHX ,il.06aBoK paBHOlJ,eHHO, He3a-
:ICUMO OT TOro, B KaKOM Bu,1.e BO,l\OpO,l\ BO,l\HTCjJ B c epy. peaKn HH .
DpH 3TO:\-1 YCTaHaB.!]HBaeTC5T CTal{HOHapHbIlI pelKHM co cBepxpaBHoBec-
HbIMH KOHl..leIITpall,lUU\UI aKTHBHbIX .eIITpOB. .
CneIJ,HcbHQeCKa5I oc06eHHocTb 31'OH peaKl I1H 3aK.TJlOQaeTC5I B e pe3h.OM
TOpMO)KeH nI Y}Ke CpaBIII1Te.l1bHo l\.1a"TJbIMH Ao6aBK3rv H KO:\fT10HeHT0I3, 06 Ia
In\alOlJ HX BHCOKHM CpO.l{CTBOj\.i K aTO [aM BO}J.opo)(a. T KllIvIH lIHfI:6HfO
pm..HI }fBJ1HTO}'C5T raJloHjJ:bI H raJIOH}J.onpoH3BO.l{HbIC. !x HHrH6npJ' IOIl e
r!,eHCTI3HC o6yc.lIOB.rreHO 06PHBOr..'I peaKltHOHHblX u.eneH npH B3aH:\.lo,l.(eH-
fBlnI C arO:\1aMH BOAOPO,iJ.3 no pcaKu,lUIM Tuna (X I), narrpmv:rcp
H + CCI 4 = HCI + CCI:) (X X IV)
I1un.16IIpYIOIll.ee }J.eHcTBHc raJIOH.l{OnpOH3Bo,D;IIbIX 3Il311HTeJlblIO TO. bKO
rrplI Ma.ilOl'vl Co.rr.ep)KaHl1ll 130;:r.opO,lf.a, 31'0 onpe,n.eJI51eT HeKOTopble 13031\10lK-
IIOCTH raWCHIUI n,lIaMeUH.
OKHCJIeHHe yrJ1eBOAopo.rr.OB [1.3, 15], ]VleXaI-HI3M 3THX IIpoueccon
OQeHb Ctf'IOlKHbIti H 0 HeM Hi\-fCIOTC5I BeCbMa HCnOJTHbIe CBe.n.eHIUI. JCapaK-'
Tepna5I oco6eHHOCTb peaKUHH 3aK.J1lOlIaeTc.5I 13 ee J\.IHorOCTa HHIIOC1'H,
CryneHQaTOCTH rrepeXO,[La OT yrJIe130;:r.opO)(a K KOUeQHbIM npo,u.YKTaM nOJI-
lIo ro .cropanH5T (CO 2 H H 2 0 npn H36bITKe KIICJIOpO,I.(a B CI\1eCI;). ,-
PeaK1.J,H xapaKTepH3yeTC51 pa3BCTBlleHHbHd ItenIlbTl\'1 J\Ie:aHH3l\10:.\1 Ii
HMeeT aBTOKaT3JIHTHQeCKHH xapaKTep. Pa3BeTBJleHIHI IJ,cnel1 QaCTO 51[3-
CTBCIIHO BblpO}{{JI.eHbI, T. e. )l,06aBOllHbIe aKTHBHb e ll,eHTphI 06p83YlOTC51
. H3 npO -ie}l<YTOqHbTX npO)1,YKTOB nOCJIe ,lVITITeJlbHOH 3a)J,ep)I{KH. CO,ZI.ep:tKa-
HJ1( aKTHBHbIX u.eHTpOB 3,TI,eCb TaK}Ke 3HaQHTC.flbHO npeBOCXOj1.HT paBIIO-
DeCHoe. 6 -
npH YMcpeHHblx reJ\IrrepaTypax B KaIfeC1'Be no OQHLIX npO)1,YKTO
o6pa3YI01 C5I a.TTbJ:{erHLlhT 11 nepeKHcH. OHH OT.fJHQaIOTC51 60.nec BbICOKOH
pcaKI\lIOHI-IOH cnoc06HoCTbIO, lIe1\.1 HCXO)J.HbIC yr.-r1eBOlJ,OPO)J.LI" C EX ! lI.;:
CTHeM npOHCXO.l{5IT 13LIpO)K}.1.eHHbIe pa3BeTB,neHH5I. DpH BhTCOKIIX Iel\-l
nepaTypax B03 10}KHO 06pa30BaHHe pa)J.HKa.rIOB C 2 H CH.. .
B HalfaJlbHoil CT3J]:HH peaKlLHH OKHCJleHH5I yr.TJeBO}I.OpO,l!.OB ce MeX3-
HH3.\.f B H3BeCTIIoti CTCnCHlI CXOJI.eH C MeX3HH3MOM OKIICJleHH5I BO OpO}1.a.
Yr.rreno.l{.Opo,J. RH (R - yrJIeBO)J.opoAHbIll pa)J.HKa.iI) B33H!\.10)J.CHcrByeT
C aKT11BHbIl\HI ll,eH1'pa1vIH no ypaBHeHHH 1
OH + RH :- H 2 0 -1- R .
0-1- R.H = OB + R'
I
I
II
I
II
,II
I'
I
(XVII a)
(XIXa)
Pa;J.HKa.iI R. 1....10)KCT pearHpOBaTb C KIIC.JIOPOAO 'I ITO peaKIl,HH, aHa.TIO-
rHQHoi! (XVI I),
.)
R' t- O 2 = RO -I- ° (XVIII a)
TIOMI1)..IO 60.r:IbllleH C.!lOIKTIOC1'H npou.ecca H MHoroo6pa31uI npo.u;)'KTOB
pedK1UIH, OKHCJleUHe yrJIeBO}.1.0pO,lL0I3 OT.lIIIQaeTC51 01' OKHCaeHH5I BO}.I.O-
pO,lJ,a II neK01'OpbIMH Oc06euIIocTHMH aHaJIOrnQHbIX 3.lIe .teHTapHbIX npt-
QecCOB. 3HepnuI aKTllBau.1I1I peaKll,HH (XVllla) 60JILllle, t.IeM y (XVII ),
H )\OCTJ-IraeT 30 KKa/l/.MO/lb. T103TOMY TaKOH MexaHII3M pa3BCTJ3,,'leIII15I l.!.CnH
49
4 A.. l-I. POS_'lOBCKHfi
MeHee BepOHTen, qeM Y BOlI,OpOlI,a, oco6eHIJo npH Y .JCpeHHbIX TC1\.mepaTY-
pax, H IIPH 3TOM npeBaJIHpYlOT BblpO:>KJI.eIIIIhIe pa3BeTB.neHH5I, T. e.
TaKHC, B KOTOpblX YIJaCTBYlOT 60JIee cTa6H.I1bIlble rrpo.n.YKTbI. PeaKUHH
BE'JIYlll,aH K 06pa30BaHHIO nepeKHCH
R. + O 2 = R0 2 (XV£!)
B OTlllItIHe OT peaKUI1H (XV) npOTeKaeT 6HJ\'10 TJ:eKy.rIHpHO. f1poMe}l{YTOq-
Hble npO.ILYKTbI - aJIb,II.erH,1.bI, nepeKHCH R0 2 H rHJ!.ponepeKHCH R0 2 H -
MorYT BCTynaTb B peaKUHI1 paClll,enJIeHIHI, KOTOpbIC HrpaIo:r SACCb
CTOJlb )Ke cymecTBeHHYIO po.nb, K3K H OKHCJIHTeJIbHble peaIUt HH .
TIpoueccbI OKHC iJeHIUI ApyrIlx opraIUlqeCKHX COC,lJ,HHeHHH lL\lelOT
l\HIOrO 06Il ero C OIUIC.neHueM yr.neBO,l,OpO,LI,OB.
XapaKTepHOH OC06CHHOCTbIO npou.eCCOB ropeHIUI 5IB rUIeTCH OOJIbIIlaH
CKOpOCTb, IJTO OT.7IHQaeT ilX OT oonblllHHCTBa .npyrl1X npoueCCOB, cyme-
CTBeHHbJX ,1.1,.1151 XHI\.1HQeCKOH TeXHOJIOrHI1. BaJKUYIO pO TJb 13 5IB TIeHHH rope-
HHH nrpaeT (pU3HtIeCKOC COCT05IHHe pearlipYlOllI.lIX KOMnOHeHTOB. B He-
O)].HOpO)I,HOH cpe e, JIanpHl\'Iep na rpalJlH e pa3)J.e.IIa <pa3, ropeHHe npo-
TeKaeT, }<aK npaBHJIO, I\.IHoro Me,ll.,JIeHHCC, tICM 13 O,lJ,HOpO)J,HOH ropIO IeH
cMeCI1. EC.i1H yc.nOBH5I peaKUHH, rrpOTeKaIOU eH B rrna .teHH, pacnpOCTpa-
HllTb Ha BCIO Iv'Iaccy pearnpYIOIll,HX KOMnOHeHTOB, XHl\UItIeCKOe IlpeI3paTI E'-
HliC 33BeplilIITC51 sa HCIle3aIOlll,e MaoJlbIH npOMeLKYTOK npeMeHI1.
CPC)J.H npOneCCOB ropeHHH Hau60.n:ee Ba)KHbIM 5IBJI5IeTCH roper-HIe
ra30B. I30JlbIlIHHCTBO TBCP.J.bIX H )KH,LI,Kl1X KOMnOHCHTOB rOpIO'tIeH cpe,n,bI
1.0 cropaHIHI npC}J,Bap:H'reoJlbHO .HH60 IIcnap51eTCH, JIu60 pa3lIaraeTC5i
c WCTHQIILIM npeBpalI enHeIvI B oJleTyqHe npOJJ.YKTLI, cropaIOUJ,He SaTeT\.t
rOl\.loreIIHO. 2ho npOHCXO;J,HT B pe3YJIbTaTe nporpeBa nYTeM TenJIOnepe-
llaqH 113 SOHbl nt!laMeHH. LnlUlib HC"TICTyqHe rOpIOqIIe, HanplIl\.iep KOKC,
TBcp){,bIe npO.il.YKTLI nnpo.ilHsa yrlI5I, MeTa.I1JlbI, cropalOT reTeporeHIIO.
Tl03TOMY 3aKOII01.teIYHOCTl1 rOpeHI15I raSOB rrpegCTaBJI5110T HaH60.TIbllIHfI'
HJITepeC B HaYKe 0 rOpeHlIII.
PacnpOCTpaHeHHe nnaMeHH B npOCTpaHCTBe. PacCM01'pll HBneHliH,
npOHCXO)].HII.J..He B XO '10,DJrOH roplOlIeH CHCTCMe nJ)H e nOi'1)KHraUHH. TIo g -
)l{HraHI1e salVlIOlIaeTC5I B 6LICTpOM t!10Ka,,1JbHOM pasorpeBe ropIOlleli Cll-
CTeMbI ;\0 ,rlOCTaTOIJnO BbICOKOH Tel\InepaTypbI 3.1"IeKTplItleCKOlI HCKpOH,
He60.TJbUIHM OTKpbITbll\l lIoJlaMeHeM, HarpeTLI)"1 TCJ10M H T. ,lJ,. TIepBble Ka-
qeCTBeHHLIe npe)J.CTaI3 1JeHHH 0 IvlexalIH3Me pacnpOCTpaneIIHH IIJlaMeHH no
01IIOpOJl,nOH ropIO IeH Cl'\'tCCH 6bIJIH paSBHTbI B. A. J\1HXe,JlbCOIIOM [30].
HarpeBaHHe ropIOqeii Cpe,D.LI rrpHBOJI.HT K 6LICTPOMY npoTeKaHHlO
xHJvIH IecKoH peaKI HH B pa30rpeToM 9lleMeHTe. ECJII1 9Ta peaKI.I.H5I 9KSO-
Tepl\IHqCCKa51, CoCe)l.HHH CJIOII rasa Ta}OKe pa30rpeIWeTC5I nYTeIvI Ten,,1JO-
rrpOBO,'1.HOCTH OT npOJlYKTOB peaKl.J,HH H B HeM TaIOKe npOHCXO IIT XlnnI-
LJ.eCKOe lIpeBpaIll,eHHe, TaK KaK CKOpOCTb ero CH.TIbHO B03paCTae1' C no-
BhIllleJIHeM TeNlnepaTypLI. CropaHHe ::)'[oro cno51 B.lIeqeT 3a C060H IlO;.r,-
)KIIfaHHC C.7Ie.rr..YIOI.II.erO CJI05I H T. )1.. )];0 cropaHHH rOpIOqerO BCI.II.CCTBa BO
Bce:\.1 paccMaTpHBaC]\.10l\I 06'bervle. ....
TIpl1 nO,!J.}KHfaHHH rOpIOIJa5I cpe)l,a cropaeT nOCJIOHHO: 30na rOpeIIH5I
neper..'Iel.lJ,aeTcH B npOCTpaHCTBe, npOHCXO.il.HT pacnpocTpaHeHHe nJI3MeHII.
CKOPOCTb neper\'IeIIJ,eIIHH rrJIaIvIeHH no rOpIOqCll cpe)J,e onpe,lJ,e..1J5IeT HHTen-
CIIBHOCTb npol ecca ropeHIHI 11 5IBJl51eTCH ero BaJKHeHIIleH xapaKTeIHICTH-
Kofr. TIpouecc pacnpOCTpaHeHHH TI.,la:-..teUH no roprotIeI1 ra30BoH cpe):L e ,
IIpH KOTOpOl\I caMOYCKOp5IIOll\a5IC5I peaKlJ,lI5I B03HHKaeT B pearIIpYIOlII.e l
C.lIoe BCne):lCTBHC pasorpeBa nYTe .i Ten.nonpOBO..J1,HOCTH 0'1' coce.n.Hero CJI051
npO)J,YKTOB peaKUHH, npIlH5ITO n33bIBaTb ,n,cq)JIarpaUHcfl. .
r3Ka5I sOHa, B KOTOpoii npOHcxo)J,HT HHTeHcHBIILIH rro)J.orpeB cropalO-
llI.ero rasa H npoTeKacT XHMHqeCKaH peaKI H5I, HaSbIBaeTC5I pOHTOl\1 nJla-
I\.JCHH. Pa3YIVleeTCH, CppOIIT He Hl\IeeT pe3KO OtIepQeHHLIX rpaHIIU, HX nOJ10-
)KeIIJ1e cl)HKcnp yeTcH YCJ10BHO. O.lI.HaKO 3TO He BHOCHT HeonpCJ(eJIeIIJIOCTH,
Tal( KaK KOHII,eHTpan.HH H Te1u1epaTypa B sOHe rr,,'1aMeHlI H3MeH5IIOTC5I
Ol.JeHb pe3KO. To..1Jl.u.IIHa <ppOHTa I1naMeHH npH 1 Gtn.M. 06bIQHO He npeBbI-
UlaeT nCCKO..'1bKIIX )J.eC5ITbIX l\IlIJIJIHMeTpa. D03TOMY ero MO)KHO CQHTaTb
4* 51
fJIaBa 2
JI.E4>J1AfPAl.(MOHHOE rOPEHHE [12, 15, 23-291
1. nJIAM5I M 061l.\HE 3AI\OHOMEPHOCTH
Ero PAcnpOCTPAHEHH5I
fopCHHe:M npHII5ITO Ha3bIBarb caMoycl{opHIOlI eeC5I 6hIcTpoe XIDUI4e-
CKoe npeI3pameIU're, cOnpOBO)l(;I..aIOmeeCH lIHTCHCHBHbIM BbTl{e.TJeHHeM TCll,,'Ia
If Hcnycl{aHUel\I CBCTa. aTO onpe;:r.eJIeHUe He YHHBepcaJlbHO: B TaK lIa3bI-
Bael\IbIX XO.rro,lLHLIX n,naJl,.'leHaX XlnUIIJeCKa5I peaKIUUI, XOTH H eOnpOBOJK-
.lI.aeTC5I CBeqeHHe .'l, HO npOTeKaeT C YMcpeHHOll CKOpOCTblO 11 6C3 SI-IatIH-
TeJIbHOrO pa30rpeBa. O)1,HaKO xo.nO)J.HbIe n,,'Ia;v'lena BOSHHKaIOT .TIHlllb
13 OC06bIX YCJIOBH5IX II lIHTepeCYIOT Hac .1IHWb IlOCTO..1JbKY, nOCKo...'1bKY
B03:\'10)KeH UX rrepexo,a B 06bIQHbIe rOp5IQlIe n..'IaMena. COOTBeTCTBCHHO
nlIaMeHe1.1 (rop HqHM) HaSbIBaeTC5I ra3006pa3HcUI cpe,n:a, B KOTOpOH
lIJITeIICHBHa5I X11MHtIeCKa51 peaKJJ,HH npUBO)J,HT K CBeQenHIO, BLu:r.eJIenlHO
Tcn a II caMopa30rpeBY.
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lJ"cp}l<arn..11MC5I B B03,ayxe HJ1H 4HCTbIM) rOpIOqHX - yr. i I5I, )KH)J.KHX I-IeqrrH-
HbIX npo.n::YKTOB, ra3006paSHbIX yr.TIeBOJ:(.op0,.1J..OB H T. )J;. O...1.H3KO XHMUIJe-
CKne npeBparn..eHHH, COOTBeTCTBYIOI.II.He' rrOHHfHIO rOpenH5I, He orpaHH-
tIHBa19TC51 npoueCCal\IH coe)J.HIIenHH C KHC TIOpO.rr.Ol\I. B rOpIOQHX ClvleC5IX
pa3.iIIJ1IaIOT rOpIDtIee H OKHCJIlITeoJ'Ib. O}{HCJIHTe,,'1Cr...1 npH ropeHHH i\loryr
6:OITb TClK)Ke OKHCJIbI aS01'a, ranOHl1.bI, 030H.
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TOJlbKO OJl,I1H HCXOAHblH npO,lJ,YKT, crroc06HbIH I{ 6hJCTpOI\.IY paCnaj1.y, Ha-
npHr...Iep aQeTIIJICH, rU.il.pa3HH, BSpbIBqaTble BeUI,eCTBa II nopoxa. TaKHe
COellHUenH5I Bcer)].a 6bIBalOT 9H,II.OTepMUqeCKHMII. TIpoueccbI HX rOpeJIH5I
ocyrn..eCTBJI5IIOTCH sa CqeT TenJIOBOrO .9q)(peKTa peaKIjJUI paS,,1JO)KenI1H Ht!lH,
KaK y BSpbIBlIaTbIX BCIll,eCTB, BHYTpelIHero caMOOKHClreHHH c..'102KHoii '10-
JIeKYJIbI. Bce )Ke HaI160JIblIIIIH npaKTHtIeCKHH HHTepec npe;!,CT3B.rI5IIOT
npOneCCbI rOpeHH5I, cBHsaHHbIe co BsaH tO.n.eHCTBHeM pa3JIUQHbIX ropJO-
LIl1X C KHC.TIOpO,II.OM.
50
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vBe.TUIqeHHH pa;:J.l1yca KpHBH3HbI 3Toro ccrMen1'a q pOHT n.TJaMCHH c a-
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B031vlYUT,eHI-di cl)opMa nt!1aMCHH B TpexMcp- B'-
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npOTeKalOllI,lIX B HeM peaKI.LHH. I1cKJIlO1.IaH H3 paCCMOTpCHHH KOnetIHYIO
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lllHpel1He ra3a npH cropaHIiH BC.r1e,n:CTBHe narpeBaIUI5I npHBO}I,IIT K TOMY,
1.1'1'0 HecropeBlllan cpe)J,a OY)J,eT OTTeCHHTbCH na nepHtpepUID, nepeM llT,eHHe
IIt!1aMeHH 6Y.lJ.eT npOHCXO)J.HTb paBIIOl\'lepno BO Bce CTOpOHbI, c(l)epu1.IeCKaH
q10pl'vIa IUla ..leHH np H 3TOlvI He H3Men5Ie1'C5I.
llpyrofI xapaKTepIIbI:H pe)KHM pacnpOCTpaHeHHH IICB03MYJI eHHOro
n.Tla 'leHH n03HHKaer npII nO;I)KHraHHH roplO1.Jefr cpe.n;bl f01.lCQHbIM l1rvlny JIL-
+8
PUC. 8. IIcBo3Myrn.eHHoe pacnpoc-rpane-
HHe fi.lJaMeHII n ,iJ..1HHHOii Tpy6e.
* fL.rI5i JIHTCHCml>HKau.HH cropamHI npnoeraIOT K HCKYCCTBeHHOMY .n.pOOJleHHIO
(ppOIlTa n.naMCHH Ha fI1HOIH:eCTlW MeJJKHX OtrarOB ropCHIHI C ClIJIbHO pa3BHTo:tf nOBepx-
HOCTJ,IO.
52
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<ppoIITa.
53
HHf.( n.TIaMeHli no HenO)J.BIUKHOH roplOqei1 epe.n,e B,n;O.TIb HopMa.rUI K ero
nOBepXHOCTH - HopMa.rlbHoii CKOpOCTblO n.TJaI'vreHlI un.
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i roplOqci-i Cpe,L\bI.
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pOIi IT.TJaM5I pacrrpocTpaHHeTC5I npn n.rIOCKOH cpopMe Cl)poI-rra. TIOIvU[\'IO
.iIHue}IHOH CKOpOCTH CI)poHTa, Be:urqHHa Un xapaKTepH3yeT TaIOKe 061)eM-
HylO CKOpOCTb cropaIIHH ropIOIJeii CMeCH Ha e,QHHHQe nOBepXHOCTH nJIa-
IvreHH. 3TO OQCBH)I.HO H H3 pa3l\-JepHOCTH Un, KOTOPYTO l\.IO}KHO npc.rr.CTaBHTh
KaK c..}t! eel\. HJIH, qTO TO }KC, CM 3 j (C
U2 . eel().
Y pa3JIUQHbIX roplOQHX CMeceH Be.rIH4UHbI Un 3IIaQUTCjlbHO OTJIHLJaIOTC5I
TJ.P)T OT ,n;pyra. TIorvlHMO XHM1P-ICCKOH npnp0.l(bI pearUPYIow.HX Bew.eCTB
BC.iIHLJ:HIIa Un CHlILHO 3aBHCHT 01' COOTHOIUeHIUl rOplOqerO H OKHC.TIHTC.iIH
H cO,I1,Cp)KaHHH HIIepTHbIX KO!o,'lllOHeHTOB. Haqa.nLHaH TeMnepaTypa rOpIO-
LJeI
i CMeCli II o6UJ,ee )':{aB,nCHHe MeHbllIe B.rIH5II0T Ha HOpMaJlbHYIO CKOpOCTb
n.naMeHIL
HrDKe npllBe..neHbl MaKCH
'faJIbHble 3UaqeIUTH Un (B JldceK) HeKOTOpbIX
rop IOqHX cMeccli npli aTMocqJepHO
1 ,n;aB.aeIIHH.
UnPo = llb Pb
(2.1 )
Be.iUlqHHa llb npeBOCXO.J,HT IIop)..ta.TJLHYIO CKOpOCTb rr..1a
.feHH 130
CTo.nbEO pa3, BO CKO.i1bK? U"lOTHOCTb HCXO..l(HOH cpe,!J,bI 60.nb..
C n.T10Tl-IOC:H
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'fMax), cropalOlll.ero Ha 1 CJW. nOBcpxHOCTH o.na)'.feIlH
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aR
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peaKIlHH JI.BIDKYTCH B 1'0).-1
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Hofi lIC.XOJI.HOI
i CMeClI (na- UCXOBHUR cpe8a Un
IIpH1vrep, U3XOjJ,Hlll.effC5:I B 3a-
KpbITOj:i C JICBoro Konu.a
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a npo,u,YKTbI peaKHHH HCTe-
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rrH H en O;QB InKH bl npo,n,YKTbI
pcaKUHH (B c.'1yqae nO..l()KUraHIhl y 3aKpbITOrO rrpaBoro KOHua Tpy6bI),
fI.TIaMH ,JBluKeTC5I B.rreBO (B CTOPOHY OTKpblTOrO KOHQa) co ....C
?POCTblO ub,
paCIIIHp5I1OllI.HeC5:I npO,TJ;YKTbI cropaHII5I TO.TIKalOT nepe.;J; coaOH HCXO;I,UYW
C
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i
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MeI-HI, H;\.telOw.ero npOH3BOJlbHYlO CPOPMY II pacnOJIO)KeJIHOrO B nOTOKe
rOpIOQei1 C:\.ieCH. 0603HaIJUM cpe.LI.HIOIO ..TJI-IIlei:iI-IYro CKOpOCTb ra30Boro no-
TOKa QCpe3 W (C.lH/ceK), nOBepXHOCTb n.rraMeHli tlepe3 F (CJ.,..t
), nOnepeQHOC
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Ba.iJCITTHOC.TH BCeX YQaCTKOB Cl)pOHTa, crop aCT unF C..1-t CMecn. C .rr.pyrOH
CTOPOHbI, o61")eM cropcBlllero rasa paBeH 06'bCMHOtI CKOpOCTH nOTOKa wS,
T. e.
I:
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T{} ,? 8
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C Z H2 + O 2 ......
2H 2 + O 2 ......
H 2 + C1 2 .......
2CO + O 2 -1- 3,3% H 2 0 »;
42% Hz + 58% B03lI.yxa ......
51,5% CO + 46% B03)I.yxa + 2,5% H 2 0 .
TIpe.n;eJlbHbIe yrJleBoJl,opo)J.bI + B03J.YX (CTcXHOI\.reTpulleclme
cMecH) . . . . . . . . . . . . . . . . . . . .
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2,7
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0,32-0,40
PaCUIlfpeHlfe np" cropaHHM. YpaBHeHHe coxpaHCHIUI nClli,eCTBa.
PaCCMOTpJUI H){,eaJ1H3Hp013aHHblll nponecc neB03:\'IYllI,CHHOrO (Typ6y Jln-
3 all.U ell rasa H TenJ10IIcpe)J,a 1 -Iefi B CTeHKn) CTaIJ.HOHapHoro rOpeHI151
B Tpy6e, OTKpLITOI1 C o6oux KOHII,OB, Qepe3 OJJ;HH 113 KOTOphIX B):(ynacTcH
HCXO,D,na5I rOpK)Qa5I CMeCb, Qepe3 ,I1,pyrofi - OTBO
51TCH npo..l(YKTbI peaK-
Il.HH. n.TIOCKOC n.TIa:\HI, COBoa.n.alOULee C IIonepeIIHbHf CeqeHlIei\'1 Tpy6bl,
pacIIo.naraeTcH BHYTPH TPYObI HenO.lI.BH)KIIO 6.iJaro;J,apH TOI\lY, liTO ncxo}.J,-
HbIfi ras BTeKaeT co CKOpOCTbIO, paBHoif CKOpOCTH pacnpOCTpaHCHH5I n.TIa-
r...feHlI .
0603Haqnrvr QepC3 Po - n.TIOTHOCTb HCXOTJ;HOi1 CpC,n;bI, Pb - Il.TJOTHOCTb
npO,l.{,YKTOB rOpeHH5I **, HX CKOpOCTb no OTIIOlueHHIO K HeUO;TJ;Bll}KHOMY
clJpOHTY rr.TIaMCHH paBHa !lb' Ha Ka:lli}1;LIll KBaApaTI-Iblti CaUTH}leTp nOBepx-
HOCTH ll)poHTa nOTOK npHHOCHT e}KeCeKYH,I1,HO Un c..M 3 roplOIIcii e]\'leCH,
ee MaCCa pa13Ua UnPo. COOTBeTCTBCHHO OT ::)1'OrO YI13CTKa cppOIITa n.rIa-
MeHH OTBO;I;HTCH B 1 ceK Ub c-w 3 rrpOJ;YKTOB peaKUHH C :\olaccof.i UbPb- f10-
CKO..TJLKY MaCCbI cropaIolIJ,efi C)..feCH H npo,n;YKTOB pcaKu.HH paBHbI, TO
IC
Un
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F
W = Un S
(2.2)
:;c CKOpOCTb TI.TIaMeHH cMccefi CO -+ 02 3aBHCHT OT cO,aep}IWHH5I KaTa..nH3aTopa 9TOii
peaKl.um - H 2 0 (CM. f.lI. 1, pa3..n:.. 6).
** 3.n:ecb H B )I.aJ1bueihllc:\1 HHJI.eKCml 0 OTMelJ:aJOTC5I neJIlftHlHbI, xapaKTcpo3YIOlU.He
HCXO;I,HYIO, ).1.0 crOpam!H cpe;J.Y, HH;leKCO""1 b - rrpoJ1YKTa cropaHHH.
5.1
TaKHM 06pa30:M, CKOpOCTb paCnpOCTpaneHH5I TIJIaMCHH B TPy6e 6y.n. eT
BO CTonbKO pa3 60..TIbllle HOpl\'la.TJbHoi:i, BO CKOJIbI{O nOBepXHOCfh n..TIa-
55