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npUBO,ryrTK O6pa3OBIIeIEII,IMII
BOS,UefiCTBrrsMr{
TaK !I COpotI4OHIrbIX
COCTOgItrfrqaCTI4U,
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A
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o- c zno yr
Tio2
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(r/z)ozg) ) (r/2)o2(Or, 2 - xeMocoporu{s:(Ll2)o2@) + (L/21o,(*); r - BaJrerrr{BaHr4e
rroBepxr{ocrHbrx
.ue@KToB;yo,"+ (1/2)02 (9) , o,,"i
4 - BaJreq[BarMeoobel&ftrx.uemeKToB: vo + G/2')o/gl
r ori 5 - MetryoeJrbrrrM rloBepxrrocrrtrfr KrIcJopoA:
(Ll2)oz(s't , o,,", 6 - Melry3eJbltrfi odEelrlfilft KrrcJroP o , U :( 1 / 2 ) 0 2 ( s )r o . [ 3 2 1
a.UCOpXapaKTep[cTrIKI{ rIOJIyrrpoBo.uII,IKoBOrO
BJMfl@D( Ea sJreKTpoqMsi,rlreoKr{e
6eHTa. 3To BJMtrure Moxer 6ETb odycroBreEo KaIc aAcopoql{oHHIIM }IsMeueE}IeM
BII3IIBaIOIU{IIII,ICKATGIIIIeSOIIHOfi
3apgla a.UCOp6eHTa,
BeJII{qIIHIIUOBepXEOCTIIOTO
aATaK I4 lrpsMblMBsaI{Mo.ueficTBI4eM
ero uplltroBepxHocTllot o6racr[,
.&rarpaMMbr
copotrpyeMrx rracrEll c gJIeftTpIFIecKtr aIcTIIBHIIMII.qe(FKTa n rloJryIrpoBo,utrma.
o,uraKo B o6oE cryqaflx BoBIuKaWre saKolloMepHocr]I aAcopdutrollEoro tr3MeHerII4a aneKTpo(FsnqecKtrx xapaKTepIIcrI4K a,[cop6elrra B 3EalntTeJlbEoficretrelu
saBtrCsTOT XapaKrepa xeMocopounoffioro qpouecca.
, I
.
r.r.
ltsorepmr aAcopolstr{
Iuaccrqeclqfr Mero.q trByqemfi aAcopolFrn SaKmqaercs B ycraEoBJIeEtrII3aBtrctrrrlocTtrMetl0l TepMo.ulEaMrrlecKtrpaaEoBecHbIMKoII[qecTBoM aAcopoEpoBatrofo
rasa, TeMtrepaTypoftB ero UapLEaJIbEIIM
,[aEIeIMeM B trpoorpaEcrBe, OKpyAaDqeM aAcopoeET. 06brwo qptr trccJle.uoBam aAcop6u@ tro,q.qepfrIlBaDr llocroffiri
qyD reMtrepaTypy tr uo (DopMetrowqaeMlrx trsoTeIX cy.qsr o xapaKTepe a.qcop6u}Itr.
B llpocrenleM cJryqae trAeaJlbEofi, gEeprerEqecKtr o,qEopo,ulofi troBepxHocrtr
aAcopdr&offioe paBEoB€ctreEeBSaul|o.[eftcTBywtx qacTuu omcHBaercff tr3orepMofi JleFltrpa
[33]:
4601b9d r7
, i 5x, i l n p o l i e t p o ; c i < r t i
focyH'a0epcxref
r.l-{5JIhoTfi!ia
N = N.,,/[r+]
(1.1)
ctrpaBeIJIr4BO[.UJrsEe,4{CCOr_U4aTrrBHOfi
a,4COp6UUr4
C HaCbUeHr{eM, COOTBeTCTByp4nt oopagoBarrlmMorroriroleKyJrspEoro
cJroa. 3,[ecb N - icoHqerrTparlrffa.Ucop6upoBalrBblxqacrtrtlt Nr - [JrorHocrb rIeHTpoBaAcop6wtr4t p - AaBJIeEtIeB ra3oaofi Saee;
b = boexp{-Ql&T},
(1.2)
Q - Terurora a.UcopOLpII4;
B fipocreft[eM cryr{ae
bo " a.1ot(yor)t"
;
!{A .- MoJleKynrprsfi Bec aIcopor4poBal$Iofiqacrrtr-Fr.
B cJry.rae lprccorfrartrBHofi aAcopoutr{, Rorla alcopo4pywarrcff qacrrtrIa pacla.uaercg Ea n "ocKoJE(oB", Rax,&[ft LIB KoropHx gaHllrMaercBoft qeErp a,{cop6I.u[II, UMEEM
* : ".,r['.[*J"]
(1.3)
B trpelerax MaJux ,uaBJerflfr u3orepMa Jlefftflopa [epexo.U{T B rr3orepMy IeHpI,I,
orrr{cbrBamynJserelhryDo0Jrac rb a.ucopdrlrM
:
n = l-3-
(1.4)
IIJIJd
N = N.t_i_J
(1.5)
coorBeTcTBeErro,qJrflrre.U{ccot_S{aruBHof
rr [rccou{arrrBEoft alcopolutrr.
Ha oru,ITeEadm,qaDTc.flrlr ,U)yrI,Ie rr.rnH]r3oTepM, He cBol@llecg K (1.1) (1.5). K EauooJleeqacTo BcTpeqawn cff rr3oTepMaM
B cryqaflx cyoMorioMoIeKyJrfipHrlx EoKpHTd oruocfi Tcs :
cTeIIeHEastr3oTepMaOpelhluuua tsll
N = CP7,
(1.6)
r,4e c a 7 - EelcoTopbrerlocTorutHHe, saBtrcsryre oT IIapH a,qcop6aT-a,ucop6eHT,
Jofapn(hfl{qec$as r{soTepMaopyrrr.rura t 35]
N = A + B l n P ,
(1.7)
r,IIE A I{ B - trOCTOSHHIIE.
HapyEe8lrs upocroft
JIeIIT[oopoBcKofi KaprIEsI
a,4copolutrI
cBl4.uereJibcrByloT o
Ea OItrrTe TeX UJII4 I,IHblX.4OrIyqeEIM, SaJIO)$eHIrnXB OCHOBy MOHe$ITIOJIETIIIOCTtr
, a.UeKBaTHo Om{CbIBaIoAeJIn. IIO9TOMy qpu IlocrpoefiIm reOperl{lIOCKIDI MO.qeJIeft
ulD( sKotreptrMeEtaJlbHlre .uaIIEbIe, ooEl{Iro l4cnoJlb3ynT o[4II I43 ]IByX rlyTeft: JM60
J|X6O yqI'ITbIBanr
BBO,4STgpe.4oTaBJrel{Ilre O EeO,UIOpO,EIOftIIOBepXHOCTV G6,37],
rIacrI4.IaMI,I [4,38] '
po,qa BsauMo.ueficrBl.rs Mer(4y a,4copOI4poBaHHNMI{
pa3rrrriroro
B cryqae BBe.[eEtrs nollsrl{a BeoJr{opo,uroff rloBepxHocrl,.r cq],ITaloT, r{To Bclo
riloffio pa36l{Tb Ea yqacTKI,I, XapaKTepll3ylouuecs pa3JMr$lNMI4 TerlI{JM, B 6oree o6qeM cryqae, pasfiIqI$IMI4 odparlnlNM aIJroTaMtr a.{copdlsltr oi
bi = boiexp{-Qi/kT}.
BBo,qs @yltrclun pac[pe.4ecop644orrHbrME Kog@trI4eHTaw
IloaepxEocTb
JIEIilfl TEIUIOT AACOP6I.uIIIUJIU OdPATIIHX KO9GFfi.PIEIITOB A,UCOP6I]I4II,,4J1'I CTENEHI4
3 atroJIIIeErIfl IIOBepXEOCTI{ UoryqaeM Bbrpar(eH[e
h."
f..*
= s troruo
,=
,
J*ftutr(e)de
JF
brnin
a.it
P/(P+b(O))
(1.8)
- BepofirlrocTb sarIoJIIIeHI4fi a.UCOpoIIIIOlIHofo MeCTa C Ba.UaH0(b) - nJIoTHocrI,I pacqpe,[eJleHus TenJIoT a.Ucopof (a),
r.uII! u odpaTabrx a,ucopdlEroHlrHx Ko3@fl-u{eHToB. Bbloop pasJMrlHbIX BI'I.4oB @y}fic$d pacllpe.[eJlelMs rrpl{Bo.u{T K pa3HbIM 3aKoIIaM a.4copolII4oHIMX paBHoBecl,ff'
r.4e
HbIMsEaqeElleM b(a);
1B
TenJIOTe
B'IaCTBOCTU, SKCIIOEeEII4aJIbIIoepaC[pe,4eJIeH]Ie MeCT a.UCopoq]II4 nO
a paBIIoMepHOe pacffpeAeJlea.qcoporyM rrprrBo.&rT K r4soTepMe opefuI.uJuD(a t3el,
HI4e Q - K BO3HI4KIIOBeIIItr0fisOTepMbI Qpytruocra taol '
Bse.[eIMe Ileo.Eiopo.Elofi IIo TeIUIore a.UcopOLUUIIIoBepxHocTI'I .UeJIaer JIerKo
TenJIoTbI
ootscrrr4Moft I/I Eaofio.4aeMyD IIa oEITe BaBI4cI4MocTb l[{cFpeEql4aJlbHoft
'
a.ucop6$Il{ ot cTeneIII4 satrOJIIIeHlIfl IIOBepXHOCTI{ [36]
OObIEIo TeIIJIoTa a.4cop6l-Ultr yMellbllaeTofi c pocToM cTeneI{I4 SanoJrHeHI4fiI1oMOXeT 6bITb CBSSaIIO c
qTo c no3urlfr xeo,uropoDrofi IIoBepxHocTII
BepxHocm,
IIepBOSaqaJIbH]trUsaIIOJIHeHI,IeMMecT aAcopOU]II4, xapaKTepl'I3yl0[llD(cs
MaKcl'IMaJIb-
HNMUQ,ayxeIIoMepeI'D(llCTOqeHlIErrpol4cxo,ryIT3arIOJIIIeHileMecr'xapaKTepltgyryD(cs
Bce MeIIbllII4MtI TSIIJI9TaMI,I aICopOLU4I4. Hafipl4luep, coBMecrlloe ]4ca,qcopoqwl ,ulg seo,4rotl3orepM, I43O6ap I{ ]I3ocTep
rroJrbsoBarrue ypaBneHrfr
paclTpe'qeJIeHI{eM Q'
gKcIIoHeilII4aJIb}rblM
poFroft troBepxEoorl{, XapaKTepI,ISyeMoft
MeIIfieTcs Ha JII4IIethlNfi saKoH
rrplrBo,U4T K 3aB[cI,IMOcTu Q : Qo-c]ne, KoTopas
yMerrbrrreH[rl Q C pOCTOM e B CJIyqae c[paBe,qJI]IBoCTI{ paBHoMepEoIo pacqpe.qeJleHrls no ?erIJIoTe a.4COp6Uru{.
3a,uaqefi Teopr4r4 IIeO.UIOpO,ETOfinoBepxHocTl'l SBJIflJIOCb Onpe.ueIleutpalrgoft
JreEr/reEa ocIIoBe aIcopOI-EIoHHbErAaIIHHX XapaKTepa Heo,UIopo,UlocTI'I noBepxEocEbIJIpa3Tr.r. B oOtreM BI4Ie gTa odpaTEafl saAarla 6bua pe[eHa Telficltr{5lMt4r].
a.qBIIIy
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pacfipeAeJleEl{s
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cop6ryIl{ rroJryqaTb BI4.q {VEKIrytr[
saAarl
pa3oM, TeOpUfl rreo.uropolsloft IIOBepXEOCTII B &aqecTBe o.urofi u3 cBoltx
B[lIeJIa "UaCIIOpTI.I3aLUtr0"KOHKpeTHOfi IIOBepXEOCT]I. o,UIaKO' KaIC Cm)aBe.ILfi![BO
pa3JII{1IH1IMITI
tr3oyKaBHBaeTcs B t4l, paBJIIrtIIIbIeagcopdaTp, xapa6TepI{3yscb
a,qcopoellTa' IrpI{BO'UflT K CyqecTBoTepMaM[ a.ucop64[11 ,4JIs O,UIOTOI{ TOrO fie
TeIIBaHrnOEa O,nFOfi l{ TOfi x(e trOBepXHOCT}IpasJII4tIIIrB SaKOIIOB pacqpeleJlelMs
JroT aAcopolulrlr, qTo IIpI{ yqeTe BosMotKIOro pasJILrlMrI CaMl[ IIeHTpOB aICOpoLUM
qpOBOJEITb "[aC[OpTI43alUE0"
,UIfi pa3JII/rrIHbrXraSOB IIogBOJIffeT B JIyqneM cJyqae
a,qcopoellTa IIo oTIIoueEIlIo K sa.UaEllol(y KoEtpeTIIoMy
sa.UaElloto
noBepxIIocTII
ra3y.
B HeKOTOpOMpo.4e aJIbTepEaTrBOft TeOpIM IIeO,EIOpO.SIOft IIOBepXEOCTII ffElgSaKOEOMepIlOCTefi, ocEoBaltrft[ft Ea
eTcg llo.u(o,u K oIMCaEIIIO IIeJIeET![opoBcKlIx
yqeTe BosMorreroro B3Ar{MO,{efiCTBr{fiMelftIJ aAqacTuqaMu. EoJIee ToIo' oFIII I[ Te
[loxe saKOHOMepHOCTr,r,Ha6Jrr0.4aeMile[pI4 lIsyrIeEIoI a,UCOpoI[{OHHbIXqpoqeccoB'
fyT 6ETb OrMCaHrr c fipl{BJeqeru.reM fioooro I43 yKasaIIHbIX [O,U(O.UOB. STOT oaKT
.u,o cero.4tgumero .ulff BIloclIT lrSBecTIIyp Eeo.EIOSIIaqHOCTb B TpaICTOBKy oKctrepr4MeIITaJIbHI[Kpe SyJIbTaToB .
Ea
B Ka.IeCTBe BOBMOXIIbIXB3aUMO.4eftCTBI,il Me,r.JJ a.UqaclltrIaMU' BJIIiIgWg
:]aKoHoMepEocTlr a,ucopduroHlrnx rlpoueccoB, ooHrIHO paCCMaTpLIBaDT CJIe,IIJW4e:
qacTUIl [42] ' KyJIo/U4noJrb-.UluoJrbrroe, xapaKTep$oe .UJIfi @IsaIcopdrpOBaIIHIlX
gKpaEIrpoBIoI'
Ic xeMOCopo4pOBaIIOTIIoCtrteecfl
paBJII
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ltoBcKoe c
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pellerKy
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qacTInI.
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penapTcg
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B
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3a.4arM, yl[ITbIBaW{e
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TO
B .qeficTB$Terbrlocrlr
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rlpoflBJrsTbcrrKaK rleolEopo.trrocTb troBepxEocTrI, TaK I4 BBaI4MoAeficTBr4e
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BKJIa.U-BKaEIoM lcorrKperHoMcryqae, tro Bcefi Br.r&orocTl4,gaBlrcrrToT qpqpoF
Koril(perHoil rrapH a.Ucop6ar-a.Ucop0errr,
1.s.
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Cropocrb. aIcopdryur Henoroporo BeqecrBa rra rroBepxnocrlr rBep.qoro reJra otrficblBaeTcrrypaBIIeHr4eM
Trtna
# = ep(r-al"
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r.Ue a - cTeneEbBarrofirerMrrrroBepxEocrr4,oqpe.UeJrseMoft
KEK € = N/N.; N(t)KolilleETpar.us aAcopor4poBaEuxK MOMerrTy
t qacT[u,. N. - KorqerlTpaBpeMeHr4
r.us Mecr a,[cop6ryM; EA u Er - gHeprr4traRTuBar.url4a,ucopdr.uEl u lecop6rIfi!
cooTBeTcTBerrEo;
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Mrro&llTeJtrr, BooHl{Icaro{e B Teoplu[ cKopocrefi peaKr.ryfrlI B KIIEerI4qecRo[ Teop]II4
rasoB; p - llaBJreElreB lasoBoft oa3e. ilepBbrfrqreH ffpaBoft qacrr4 ypaBlreEus
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B ra3oByn (!a3y.
B pa[ffax reopwr JleErlffopa ypaBEellrre (1.9) trpr4HuMaerBr4I
d
iiE
N= -
^oS
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P
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(N*-N)e
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-
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a
(1.10)
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y - qacToTa KoJreoaHrda.qqacTr4w,.s - rrJroqalb
3.Uecbn -Macca a.FracTrn_Ut
rroBepxEocru, BarfloraeMas
olErofi a.qqacruqefi;i = Koexp{-EA/kr} - KoB@rU,reHT IrpI{JIItrIaEtIfi,
i o u-rexp{+E-lkr} - cpe[Iee BpeMa upedneaiua a.uqacr]u6r
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rloBepxHocrlr. M.: Ii[B.q-Bo
19s2. 8d,55.S.336-343.
1931-1939.
77
8.
Boudart
t4. //
J.Amet.chem.soc.1952.Vol.
74.
P.
1531--1540.
Botbre4zunenx'0.O.// Wp:d. @rs. xl$,trtr{.Le47. I. 2r. c. r3!7-L322.
O.O. // Iau xe. 1952. T. 26. c. L462-L47o,
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qro trptrMerrtrTeJlbrro
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xwrtngag Bce cra3arlnoe BbII[e, a Talore To, r{To op < oo, ,4I8 RI{HeTI4ICu
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SAIIIICATb
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e.44,
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n
e.4s),
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= -R2ht + const,
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I06
paoore
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rpollpoBolFocrtr cueqelfrofi I{ qacrnrtrro BoccraHoBJlerrHoftIIreItrCtr zno qpu
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u
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IIepBHfi rurefl k'Nv(Nso
- Nr)
omIcNBaer cKopocrb
r" = 11n6BaHHEXKOMIUTeKCOB;
B oobeMe r4JM, qro, BosMorclo, 6oree
copdryloErloM cocrofiHlE{,
B KarlecrBe
t"l-l=li
oOpasoBalryIfi
a]Icop6?Do-
N, - KoHuellTpaurs pa.uIKaJIoB
[paBI4JIbHo, ID( KoIilIeIITpaqI4s B lrpe.ua.uMox(er Bblcryrlarb 1{ Fl3a,4copo-
Koroporo
TzL
I.EIEi Nso - KoltrleHTpar.ufi Mecr xeMocopolutrr, T.e. RoHueHTparllrfl aroMoB cBepxcTexlloMeTpl,rrlecKoro MeTaJIJIa. cs{Tag, qro Nso ! h [Me*]o, r,4e h - ToJIIIltlEa MOCrlrICa, [Me*]o - OoEer\rHag.4oa,4cop6lu,IoifiragKOIiUeHTpaUI4g CBepXCTeXr4OMerplrrlecKolo
MeTaJIJIa, Mu TeM
caMbIM no.{qepKl4BaeM, qTo
ltpaKTr4qecK[
Bce
MetrySeJIbHile aToME MeTaJIJIa, CyqeCTBylff&Ie B MOCTtme, B CI4Jry MaJiOCTr4 h
.umaJIOB, COOTBeTCTBy@yD yKaBaHrrbrMBbrrrre [poqeccaM, rrpoTeKauqr4M rro saKcHaM rlepBoro Ir BToporo IIopfi,UKoB B oTlroueHr,rI,I xeMocop6rpoBaHrrHx paE4ICaJIoB.
oTMerl.ilr, .ITo RoIIcraHTa cKopocll4 k" Mo]t€T BaB]{cerb or IcoHueHTpatII4]4 cBokl = k' N.r,
k
k .|+ k",
.=
k: = k""
#=*,
pemeHr,re
KoToporo y.qoBJre
TBopseT BbrpaxteHr.flo
(x.-x) (-x.)
r r - = -(x-)t
{t
t,
xr
)
(2.87\
(2.eL)
N=.
t*r""n{-/^---.}
3.UeCb Ns. -
"rN"o
- CTaIgIoHapIIas
&OHIIeHTpallEs xeMOcopOUpoBaIIi{Hx pa.UIKa-
r = xt/ (-*z) . 1
1n6-...u"!t)";
rrpoBolEocrtr B oroM cryqae c yqeroM
N, = (1ue*lo - [I'{e*]) h
loa
JIrn K[IIerI4KI'I
coorHouelild
yMeIIblIIeH]'Ifl sreKTpo-
(2.e21
u
* */^?'
o
r'uer = xl + ax,x,>
trowrMTb
Eerpy.Eo
-- .""n[-/^"pl-l r
(2.88)
-"
r t""
paselMe
P I I o . 2 . 1 .3
OagoBas rpaeKToptrs
rpu
o ( t ) ! o o - ( o o - 0 6 )
yE{rEBafi,
{J " j
L'.[
|
(o
t?
,6ltl
o_ -{ oo ,
(2.e5)
1/2
*'
o@ << oo.
(2.96')
rITo rllrl Juooblx t llMeer Mecro HepaBeIIcrBo z exp(-y'I- t) < 1, BbIHa MaJIEXBpeMeIraX (y'r- t < 1) MO*eT 6blrb rrpe.ucTaBJleEo B
(2.95)
B&Ue
oo-
CITCTEMH
o
re
!ecopf4un
-- - {^-*
z-'
yq{THBafl,
(2.e7)
rITo B BToM cJryqae reKy[ure SIIaqeH],Ifl o He cfirbEo
orJMqanrc.fl
y.qoBrerBoprrreJrbHo
t
allffpoKcl{Mlrpyer
Eeoorb[trD(
oo, Brqlax€Erle (2.e7,
Ww
CTb
ctrepnMeHlaJrbEo y cTarIoBJIeI[IyD KI{IIe T}ItIe CKyF SaBI,ICIIMO
BrDa[eEEe (2.88) ritoaet 6HTb llpe.qcraBleHoB Br,qe
r22
(2.e4)
r,qe o. - cTar.Eo8apEoesEaqeH}Ie ofleKrpollpoBo,ulocTl,I a,4copoeETa.
cooTIIoueEI,IeMBeJII/rqI4IIcTal-[4ocJlyqa8x, oTJII{rIa@t,D(cff
B ,r}yx IIpe.qeJIbTrHrr
pa,umaroB I4 HarlarbEofi greKTpofipouapEofi KoEuellrpar@ xeMocop0lrpoBaE+,D(
Bo,Eocrtr alcopOeETa, BbrpaseltrIe (2.94) rlgllHllMaer cJleAyrilryfr Bur:
o(t)
uctroJrb3yeMoM
IIp}I odpadoTKe oKcrrepuMeaTaJrbHbtx,qaHHbrx
t34,LL2).
f1/2
;"""t;; 4
["]-,":-":,
,n,
qPlI x > xl
ttll
(2.8s')
Hecrorctril [email protected]{3oopa]faqeft Tot{KI,Ino FasoBoft Tpaeroplll4 (p[c.
qTO xr IIpe,UCTaBJISeT
ftOIIqeIITpalIloXeCOoOfiCTaI-U4OIIapHyIo
2.13)trOKa3bIBaeT,
pa1reaJloB, COoTBeTcTBynqyn
BHellIHlIM.ycJloBI,IgM.
sa.4aIIIIbIM
MOCOpOrpoBaEHbtX
...nf*,*'*,*
* .r.n[ *, I * t * ' 1 '
I = /}--.
"
t/;- )
t{;)
(2.e3)
BlrpafiellIle
o(t) =
k,- krx - kr*' , Fpe.{cTaBJITIDr.4e xi II x2 - KOpBII KBa,rcaTIIOrO TpexqreHa
paBHoBecl4fl:
ycroltqBoro
cocroslild
I{
HeycroltwBoro
wre cooofi To'trg'I
i'z=
' - ""n{-/i-.- .}
:
N=(t)
o = A(T) y'[ue*]
-k.x-krx2,
-x r/T\ = :!-;-
aeElIe
I4
BEcoKofi rro,FrnrEocrr{ srrD( .qe{eRToB Motyr
6brrb .uocryrrHH a.ucoporpyroqrd\4cs
qacTlqaM. TaKn{ o6pa3oM, N=o
N. " h 1r're*Jo- N" = h [Me*], r.4e [Me]* TeRyqee ssaqetfie oobeMloft
KoErIeHTpar-pM ,qoHopoB, npo[opr-u4oHaJibHoe , KaK
yKa3brBaJrocb BElre, RBa,qpary oJleKTponpoBo,utocrr4 a.ucopoeHTa .
BTopoft u rperrfr qrelnJ ypaBHerflrs, (2.s6) orMcbrBaror Kr4HeruKy rftoeJM pa-
oo.unrx pa.E{KaroB B oobeMe.
BBOAq OoO3HaqeHUfl: x = N=/N=o,
trepeltrlr[eM ypaBEellfie (2.86) B Brrle
- (2.9o),
KI4EeTfiKy Odpa3oBaIfiIs
OIII4CbIBamUUX
Peuertr{eM ypaHerfld (2.88')
qpfi ID( B3alo'lo.4eftcrBlat c tleoHtoqHHMI'I aToMaMI4
pa.UmaJIoB
xeMocopdlrpoBallHblx
MeTaJrJra upl4 yileTe o6paTEoro qpouecca - ruoeJM palElIcaJIoB, fiBJIffeTCfi Bblpa-
(2.89)
o - a
o .---j-
(2.e0)
-
-
+
t w
or
3K-
(2.e8)
upl{ a,{copolEtrtaroMapHoro aSora [123]. r{To Kacaercfi cral-u4oHaofio.qaeMyn
oo, TO, KAK BI4.4rOE3 BLIpaXerflM(2.88)
HapHblx3Eaqerufr gJIeKTpOrrl)oBo,EIOCTlI
(
2
.
9
2
r
,
(
2
.
e
3
)
,
rE
oTKyAa,
BCtrOMtIHag, 9TO K'=
K Nv, K2= K Nv+ K,
IIeTpy'UrO
[OIyqI,ITb:
Ni.(t) -N*-
n
N_ ,
'
(2.1oo)
r,Ue Ao = l" - oBupaxerue (2.100) c[paBe.UJr]rBo
JM6o rDfi K"u K"', T.e.
qpoqecca peKoMOrEraUE4
npl{ cradoM qpofiBJreEr4r.I
xeMocopdrrpoBarufirx pa,U4KaJIoB rro cpaBlleErrn c Io( ruoerbn rlo BaKoHy peaKr_U4r,r
uepBoro [oprr.qIca, ml6o, Hao6opor, rrptr K"'> x", no a cry.rae JMdo BecbMaMaJrbrxKorirleHTpauil pa.EmaJIoBB ooreMe: N, < (K")2/ K' (2:r-"'- K") = Nnz, JM6o y$e rrplt
trx ogeEb doJlbEofiRollqeHrpalpflt:Nv > 2(2K",- K")/ K,= N"r. oqeBr4,Uio,rITo
o6a grltx cJryr{asranxe rapairrlrpynr rrper4MyqecrBerrnoe
rrporerarue rrl6e;ur a.qcoporpoBaltrN( pa.@raJroB rro pea&rwr [epBoro [ops.qfa B orrroEerilFr rrx IIoB ToM cJryqae, fior.ua
tr N,r< Nv < Nvz, T.e. B cryrlae cpe.EIL!(
o6Ber,tr$D(
KorilIeETpaud pa,uEcaJroB
I{ peKoMortrIarproErroro
MexarilsMa rr$ rere]rreruIoft III:OeJDI,.qJlflBeJMlrr{Hr{,xapaKTepr{By@eficrau{oEapEyo oJreKTponpoBolEocrb a.UcopdeHTa,troryqaeM BblpaileHrle
Ao a^
_
/;-" -/-+
a - ---j
(2.101)
OTMCTI4I\,I,TITO BHPAXEHI4'I, AIIAJIOTFIITbIE (2.100)
II
(2.1O1),
IIOJYTIEHHNE B
PA-
6oTe [120], Eatlfifi cBoe gKcrrepuMeHTaJrbHoe
no,{TBeplMerrueBo MIIorrD( cr{crepa,umar-oKcl,IEDffia,ucopoeHTtr,34,57,L2o),
Max cBooo@.@rfi
pa,umaJroBc noBepxHocrr4 rroJlyllpoBo.Ufl{Ko'lcrre3EoBerolea.ucoporrpoBarfisrx
Boro a.qcopoelrra qpr{Bo.UI{T
K yBerr.$reHnosJreRrporrpoBo,Utocrr.ruocJre.Eero Ba
cqer BbrcBooo)MeHlrg
aroMa MeraJIJIaI4 nocJreAyqeft ero I{oHLIgaI"Utr{:
x" e (Rl:.uef.)" ? R(s) + ue.2 nliy + ue] + e
(2 . Loz)
Cwrraff, rrro tI B oroM cryqae fio,s4Tupyueft cra&Iefi rrBJrsercfi paclla,u rroBepxnocrnoro KoMrrJrerca(R6-....u"f')",
paBnoa He ycrarioBJrerlleoJrercrporrnoro
Bec}lfi rrpl,I ]toHrr3aulMnpI{Mec}I, KuIIerlIKa qpoUecca Mofier 6bITb orMcalla reM fte
ypaBrreH[eM(2.s6), o.uraKo c,4)yrnMr4 HaqaJrbnbtM[I
ycJroBrrsMtr,
cooTBeTcTByD(lagoBoftTpaeKTopr,M
[&rMlI".uecopoluoHHoft
o6racrr4" Kpr.rBofi
Ea pnc.2.13, T.e.
dNs/ dt < 0. 06bFtrIO fipoqecc rlIoeJM pa,umaJloB, a ToqHee, ooycroBrelfiryn
grlrM RrrHerr4Ky r.I3MerreHrrsoJreKTporrpoBo.Urocrlra.qcop6eHTa r{ccJre.qyroTnpl4
peBKoMficqe3lloBerirMpa,uftaJroBI{s oobeMa, oKpyxa@ero a]IcopdeHT.B srot[
ypaBHeHI{s(2.87) aBJIseTcs
cryqae Nv = 0 lI peuleEl{eM
x(t) = x
\
{ I
e x p ( - K 2t )
K,l
1 x , " , * C5l. '
(2.1o3)
- Xaaxexp(-K2t)
(
rAe X*, - KorillerlTparufl xeMocopo[poBaHrrEx pa.uE(aJroB(B e:fiEildiax N"o) B
Har{arbrfiffi MoMeHT[poreKaHr{a ooparHoro trpoqecca. B oKc[eprd,reETe 9To (B
3aBr,rcr4MocTr.r
oT MeTo.uareHepalu{I/IpaFucaloB) MoxceToHTb MoMeHT BhlKJuorlerfl,Is
l r c r o l E r r { K a c B e r a , H r 4 T r , r H a K a J n r Br a
. rr IrI.,rIra. ( c M . , H a n p r o , l e p , t 1 l ) . 8
EaqaJlbHbreMoMeHTH
BpeMeHI{IIOCIe BbIIUmqeElIg]ICTOEI]IKaIeEepaLpIlI pa.UmaJIOB,
y.UoBJrerBoprrwreycJroBrrro
Kzt < 1, .UJrsKoHrleHTpar-pnr
xeMocoporrpoBarfffix paBbrpar(eHrre
,u{KaJroBcqpaBe,uJrr{Bo
L24
(2 - L04l
tr ,UJIfl KI,IIIETURtrYBEJIIIFIEE}IS9JIEKTPOIIPOBO,UIOC?I{
A.UCOPOEHTA
UOTYqAEM CJIEAYIOqee BbrpaaeErlo:
( 2 .r . o 5 )
,t'= @:- 4tr"' ,
KOTOpOe B CJryqaetrpeEeopeeDrocrl4 rrpoqeccoM peKoMortrIarrytrI
xelaocop6rponauHbrxpaJE{aJroB, qTo BoSMofirrotrptr ycJIoBtI[ o..( 6o, rrpl{H}rMaeTBI4I
( 2 .r - o 6 )
3 a M e r r u \ t , l I T o B B b r p a [ e E l 4 f l x( 2 . ] - 0 5 ) y I ( 2 . L O 6 ' B K a q e c T B e N " * , ( T . e , & o E qEEIPAI@I XEMOCOPc.IIPOBAIIHTD(
UCTOTIHI4CArEPA.UIRAJIOBB MOMEHTBTECTIOqEIilIS
EepaLuM) rrctroJrb3oBallo Nso, T.e. cquTaercff, r{To
sToMy MoMeETy BpeMeru ylre BHrrreJrBa cTarlfioHap.
B erou
N
o " x
t
r + -fiI:I xrt
Ao.o
e=____l-+
c
,
x
1--K
-
agcop6erTa
rrpoqecc
cJryqae ,4,rs EarlaJbEofi
yBeJnrrteHrrE
cKopocru
(t < K;1), odycroB:reffroro [poqeccaMr{ rudewr
qaeM BHpaneflue
xeMocoporyEr
K
oJlerrporrpoBo.urocrl4
pa,u{rcaJroB, rroJry-
r - d-r
-;
1
1o - l l K
r+ K,
\
-
do "-t"l
-l
d E = t - [ l - ' J ---..-;-' " /
\
(2.ro7)
1 + 1 1 - + l K - r
\
o ' . ,
o
J
orKyAa
# l." -"lrr;"i
5H
l,..'['-
(2.108)
trlB Brlpaxerurff (2.10s) Blt4ro, qro B pagJllrlrHbrxrrpeAeJrbnbtxcryr{asx, orJllfllatoIIpD(C'ISaKOIIOM
rE6eJE{ XeMooopolfpoBarffil,lxpa.44rcaJloB(MoHoMoreRyfl.flpHafilrJpi.
omroJeKyrfipEas peaKr.plaB orHomelrrtrIrtx KoErIerITpaUE{), cropoctt
r43Merrerrrrrr
sJreRTpOtrpOBO,&IOCTtr
IIpE Bb[(JIDqeErII4
[CTorfittrCa reEepalu4ir pa.4maroB rrpouop_
rr4ollaJrbEaEx KoErIeETpar.wI, cyqecrBosasmeft B oKpytrarcqeMo65eMe ro MoMeHTa
BbtKllorreEtfl.JIetcrB[TeJbEo. TaK RaK o'- o2 - N", = (/r- - K2) / 2K3, To
B Cryqae x, r xr{rt - "'.1 t ol nory*r3"
a- |
#l.o
r'I-- x
--zr:Kz-Kr-Nv
EcrtrrK2 . \(ol
(2.1oe)
- "'_l t ol , ro
yr -*,'l'.- t /T
d 6|
*'-t/q
ffilro-t----j
l ' K 3 - K-lN
,|
(2.11o)
3aMefltr'|, rITo yKasaEtroft [polopr&oHaJlbrrocrtr y.qoBJrerBopserr4 iraqaJrbHas
cKopocrb trsMeEeEr{soJreKrpollpoBoErocrtr IIplI a,4cop6qrM pa.uEcaroB. neftcrBffTeJrbEo,trctroJlbsysBb{paeeme Q.94'), rroJrygaeM
y'f,-'5
dat
- -:T/i' orryra rq)rl K2 > 4KrKl
# l. o
125
#lr"-*, t'-K,-N'
B llporBotronoffioM
(2.111)
cJyqae qpll K2 < 4KrK]
do |
/Tl
r:&l. o-/ 4YK 1 K3 -Kr-N"'
(2 . LL2'
IilTaK, crporoe peEeme KrffetrlFlecKoro ypaBHerrr4a,orE4cbrBaruero rrBMeHeHI4e
sneKTpotrIrcBo.EocrtrtroJrylrpoBolutrIKa
llptr a.[copdlu[Ir pa.UmaJroB,no3BoJrse
T BarqrmrMrb, ,rro @opMarI4a o ftoIilleHTpaUM pa.uma{oB B oKpyxtaltrlefi agcopoett
(!a3e rroser dETb uoryqeEa ug u3Mepelilfr KaK cralgroHapErx BEageruffi gJreKTpoqpoBo.EocTtr, ycTarraBJMBar@cs IIo lq)ouecTBltl1oqpe.ueJleErroroBpeMeHr4
rrocJie
BIc,InqeEIIfftrcTolIEI{RareHepaITII,I pa.EmaJIoB, TaK I,I I43 l.I3Meperu[fr HaIIaJbHbIx
cRopocTe[ trBMeEeEtrfioJreKTporrpoBo.Frocrrrrlpll BKrFqeHId4lrJrtr Bulc.moqeH]rr4rroToKa pa,umaJroB,oopadarHBaqero rroBepxEocrba.ucopoeETa,T.e.
= ,
(*'l=[.'J*=[tJ"oo:
('-L)
*l
Ir qpe8le, a = ooLo/o7; o - cTatuoHapHoe SHarIeHI4e gJIeKTpo[poBo.4IoV*
tr V^rr. - EaqaJlbHble cKopocTl4 lISMeHeIII4g SJIeKTpOIIpOBO,EIOCTI,I
uP
vwP
(doldt)t+o
IIptr BKIOqeEIdII/t BIIK,U0qeHI,II{
IloToKa pa,4{KaJIOB;(N" / N"o) ; .
- OTEOCUTeJIbEafi
pa.U{KaroB.Bce Befi{qr,Tr6r,3aKOHrIeHTpaWfl
: [Rv] / [Ro]
K,rroqeEHleB KpyrJrHe cKooKn, [pe,UcraBJrsnr coooft orrroctrreJrbHbre sHaqeHrdfl
cooTBeTcTByur[qXuapaMeTpoB.
Ilpouootronoffioe paccMorpeulloMy cryrrap Ir3MerIeH[e gJIeKTporDoBoIfIocTIt
a.qcopoeETaEpoEcxo,U{Trrptr alcopdrlM TaRlIx aKTr{BHHxrracTrltl KaK aroMbrBoK aEarorEttrroMys@KTy nprrBoltl4Trr paryr.qopol.[au MeraJUroBllrs,Lz4,rzsl;
oJMByrJreBoAopoloB[126] Ba cqeT oopasoBarMslI xeMocopdutr{ H-aroMoB. tI
B grax cwqaflx IcaK cKopocTb a,Ucoporu{oltrroro[BMeHeHr4rrsJreKTpoqpoBoErocTlI' TaK tr BeJIIIFIImaee CTaLU{oEapIIOro
BIIaqeHI{flOIIpeIeJIfiaTCs cOBoKyriHocTbF
[poqeccoB, colrpoBo8lar@D( xeMocopoluF [ 12?] .
lllBoroql.IcJlel{rilreercuepmvtenru IIo aAcopor-uEl H-aToMoB, B![IIOJrHeHHbre
Ha
paBJII[tIHrU(
OKCtrIaXRaK MOIIOKpTICTaJUII'IIIeCKOfO'
TaK ]4 nOJIItr{plICTaJIJIIrtlIeCKOTO
TuIIa' o.EIoBHarIEo IoKagaJIII cyqecrBoBaEle IIa noBepxEocrll o&cu.[oB BapErfiemrofi r.r He3apfffteltriofiFopu
xeMocopor.rlrcBaHrrrrx
H-aroMoB [8e,loe,],o2,
LLO,L25,r.28I . I{CXO.4gU3 oomfpEoro sKcrlepflMeETaJrbrloro
MarepffaJra,B pa6ore [127] 6hula B[epBHe qpe,uJlor€Ila cJreAyroag cxeMa, HeflporuBoperr{Bo oltrIcHBaqag xeMocopolliloH-aroMoB:
I
tl
-+
n
i.,
I I I
(
(Ht)"
f
t:
;
H + e
l "
;---:+
K
(2. r.14)
I
2
l
u trj"
l '
t
J*r
(H2 )"+
(H2)
"
(H. )
u
r,4e, KaK il lrpe'(.4e, I4IUeKCbI s r4 v OsIIaqanT cooTBeTcTBeHHO aICOpor4pOBarIHOe
126
1# = *,rn"r[r- j. k,rn]rrer*,r""r[r":ri
ff
- K 3 t H ,1l n " 1 lurlt
1S
= * .r " " :
[.- #l
( 2 . 1 1 3)
IAe,RaK
cTtr;
I,I cBooo,IlEoecocroflElrfi. Ha ocHoBalfl&r Tofo, rITo Borrpoc 06 l4IeETl,rft.trcau{u
xeMocopolrpoBaHlroro cocrogHl4fl aroMapHoro Bo,uopoAa
.qocraroqEo rrorpooEo
paccMarpl'IBaJlcfi
B pa3.ueJle2.4.2, ocraHoBI4MCfi
6oree [o4)o6Ho IIa Berr4rrr4rle
]r
KuIIeTlIIceI{3MeHeHI'Ifl3JleKTporrpoBo.UlocTlr
TIoJItIKpI{craJIJII,rtIecKoro,
cneqeHEoro B
BOCCTaHOBI4TeTbHoft
cpere a.ucopoeHTa,ooycJoBremroro arcopoqfiefi H-aroMoB,
B odueM Brrre peueHl{e, olMcblBarmlee fiporeKall]Ie [pouecca no cxeMe
(2.114) ' BeCbMa rpoMoSlliro. .[eftcteureftEo, om{caHue KI{HerI{Kr4
rr3MeHeHrirfi
gJrel{TporrpoBoElocr}iIIpI,I a.ucop6ul,[,rH_aroMoB
norpeoyer r4ccJre.uoBaHr,rg
noBe]Ie_
HIIg D{IIaMI.rqecKoficucTelH Ea TIJIOC&OCTI4
CJle.UynqeroB}IJIa:
'
(2.115)
R ,r n]r r er
- ',r r H :r ,
K5r
(2 . 116)
KOTOpOe'XOTSrr Moxcerobrrb rrpoBe.ueEo
craHraprHbrMcrlocoooM [].2s1, reM He
MEIIEE MOI(ET6HTb C IOCTATOIIHOftCTENEEbNTOqHOCTIISAMEECEO6OIEE
IPOCTbIM
I{ HarJlfilrrblM aHaJMSoM CXeMbr(2.r.14) B paSJMrrHnx qpereJlbHblx cryqasx,
coor_
BeTCTByIourD( paSJII/tqHI{MTeMnepaTypaM T I,r KOIrUenTpau}rsM cBodo.uftrx
H_aTOMOB
tH,l .
llrs Haqara paccMorpr4M TaKyn ooracrb r ll tHv], r.qe Morclo fipeHeope.rb
ooparlfiw qpoqeccoM B cryneHl{ rr
I4 llo60rtrIblr\,fl4 rlpoueccaMr.I rrr - v, [pI4BO.qfl[[vM K lloBepxHocrHoft peKoMoffiaq]d{ H-aroMoB, T.e, paccMorpr4M
ooJree
qpocTyDcxe[ry:
r
H.. ---;+
r
^
tI
t
H
a
---:+
a
2
Ht.
+
e
(2.]-L7)
O'IeB[Eo' qro c*opocrb Ea&orure*]rs Hs Ha rroBepx'ocrr.
cJryqae BbrpaneEtreM
o[pe.ueJlfiercfi B oroM
d r H r
= K , t H " J ( r - e ) - K a t H .(l L - e
+#
) ,
(2.118)
r'4e o = [H.] / [H.o] - CTeUeEb3aIIOJIEeIIILS
IIOBepXEOCTI4
Hs_ aTOMaM[; [Hro]
- MAKCUMAJIbEO
BO3MOMOE3AIIOIEEIItrEtrOBEPXEOCTI!
XEMOCOPo}II]OBAHIINM
BOAOPOIoM, T.e. wcJlo ero IIeErpoB alcopouM; g - crerler{b oarroJlHelr}rE
rroBepxEoc_
TE H-aroMaMtr' XerpcoporfpoBaEHbrMtrB 3apsrfterfiofi
@pMe. SaMern{, r{ro rr B
AaffioM KOmperEoM cJryqae ocEoBEOetrsMeEell}Ie snelcrporrpoBo.4rocrr{
Moc?r[KoB
ooycJro&,reEo"Jrerrq)ywo, .ueficrBtreM" H-aroMoB, B KaqecrBe
BHoBb o6pasyn_
qIXcA .qOEopOBr/roryT BblcTytraTb,&aE
oTMeqalocb BFq[e, (o_n)2-_rpyrrnl,
BoBEIIKaWe rIpE B3anMoletcrBrur H-aroMoB c KtlcJropos6rr\,tr{
I{oIIaMr{ pelrer*lr.
MaJEe roJnInFrI lrocrmoB h B gToM cJryqae qpr{Bo.qfiT
K ToMy, trro BoBMolcHHe
3{meRTESapa:ftemff troBepxEocrr[ IIpaKTEqecRlIHe qprlBo.urrr
K sarr4oy 30H lI He
BJII{.EDT
IItr EA KtrEETtrKY qPOUECCA,EIr IIA EEPEEOC EOCI.ITETEfi
TOKA. CqI.ITAfl,
qro B paccMalprBaeMoft odJlacrr.r
r I.r [Hv] e'.. 7, Irerpy.uro rroKasarb, qro
peuteEueMypaBEeEr.IS(2.118) .EBJLEeTCfi
BblpaxeH[e
Kt
[Hv]
"=I^- liii-it,[,-" -*.['.f,ffi].]1.
q Tr;l
L27
(2.11e)
B
xeMocop6upoBalunnx
tH:l qpe,UcTaBJrfler codofi $omleurpal$n
H-aToMoB, oopasylqu4x,UByxsJIeKTpoIIHylo
BapflSeffiOA (DOnIe H-aToMoB, T.e.
cBsgb c troBepxEocTbn, uMeeM
(2'r2o)
tH:l - (tel - [e]o)h,
r,[e te] tr [e]o - TeKyqafl ]I EaqaJIbIIafi KOHIIeIITpaLUM 9JIeKTpOHOBqpOBODD,|OCcJle,[yer
Ttr. OTcD,[a u Es K[HertrKE, olurc[rBanqeft cra.Um rr cxeMbl (2-LL7),
ywTrmaa,
B ToM cry,rae,
qto
RorAa ,[oMrrErrpyer ooparEafi
peaKlu{fi
r,
gTa
cBESb
oyIer
UMETb BI{I
e k j ,'
*:=
k.
(2.127)
CBtr.qETEJI6CTBYWd O TOM, IITO IIPI{ BEICOKID(KOHIIEHTPAIgISX [HV] CTEIICHb 3AIIOJIHeEtrg IIOBepXUOCTII HS-aTOMOB trepeCTaeT SaBIICeTb Ot KOHIIeITTpaIII]r H-ATOMoB B oobeMe.
'
*=f,,"",
pearu[Is
EaROEerl' .uJrs peaKrstr{ rv,
ca, uoJryqaeM BEpaaeEtre
Bbrcryrlaqeft
1"'11'}]
# =++t+['-""n{-*,t'*P
r.I€ c = (tr z)-l
qvK,| h-l ;
Kr'
q - 3apflI
EoctrTerefi ToKa; p = K,|/ KrtH.oJ, llb
M O E a Xr < [ K 2 ( 1 + p [ H , l ) l - r
+ p 1n"J)l-r
do
( 2. r 2 2 )
SJIeKTpoHoB; v - noAaurcIoctr
12.]-22') BI'IEIo' liro Ha HaqarbHHx Bpe-
doldt.dKz[Hv]t,
a
IIPII
c r -f H l
v-
(2'123')
'
B ooracru ,uocrarorlEo BblcoKtrx reMfleparyp, Kor,ua cqpaBe,uJlrlBo ycJIoBI4e
lB"l <. K2[II.o] / Kl , BEpa*eIII4e(2.123) trplIluMaer doree trpocroft BIII:
$f " c rrr"J,
(2 . r24l
oTxy.4a cJle,[yeT, qTo oTHoc[TeJIbIIaffKolllleErparyl8 H-aToMoBB OKpyxanqeMa.qCOpdeETOoEeMeMOXeT6ETb B![paxeHa rlepeB cKOpOCTbI{SMeIIeIMSero sJIe&TpOqpoBo.EocTrl
lH" l,
Tfr;i;
cJleAy@n/t oopa3oM :
(do/dt\
=Ia-o/aq,-
(2.L251
(2.L23) ' Ms
BHpa,reHIleM
B doree ooqeM cryrrae, orMcbIB€eMoM
H-arOMOB[OrytlaeM
KOIIUeHTpar.Ultr
";-
T
[8, ],
=
Tfr;I; ?FT
(2. 126)
Jnllllb B TeqeHI4e ,uocTaToqEo KopoTKoro
EarMHaeT yMeHbmaTbcfl' qTo IIpu .4Oc'
TaToqEo B[IooKEX TeM[epaTypax odycJloBJleno qposBJIeB]IeM oCpaTHoft peaKLMII
Iv 14 oopaTfioft peaRIWI
cTyrreEI,I II I[ ilIoeJrbr n-aToMoB 3a crler pea&I[[[ III,
CTyIIeIIE I. yKaBa1gIOe O6CTOATeIbCTBO IIpIIBO,TIT K TOMy, IITO BMeCTO cxeMLI
(2.LL:-) .UJrA.qOCTaTorrHo
BHCOKm TeMlepaTyp cJ1elyeT paccMaTpI{BaTb cxeMy
r{To JEofi4Tl4pyroeft cra,rytefi I{sMeHeII[fi
sreKrpogpgBo,Erocrtr sBJIfieTca CTytreIIb II . 3To cJIe,IIJeT II3 MaJIocTI{ (qpfi II6BHIIIeHcra&frr r' TaK I'I craL[4oHapHo[
KaR BneprI4I[ aRrI'IBaIIflI
BbIx relfieparypax)
yoTarlaBJrrrBarueficff,
oopa3oM, ,4ocTaToqHo 6HTaKm,
Hs-aToMoB,
Korlr(eHrpaluor
qpelEIoJIofrI{B rrptl groM,
cTpo.
Caser uex,rJ cratpIoBapEblMl/t Kolil.Iesrpau{sM4 cBooo,uilJx H-aroMoB B oobeMe
tr XeMocopOrpoBarrHllMl4 Hs-aTOMaMI{ 6y,UeT olIpeleJlsTbcs TeM, KaKafl I43 peaKl-Prft
(rrr,
rv llJu odparnas r)B raruslx ycJloBl4ax orllrra fiBJltlercs Aol,guflfpynueft.
r28
To
(2.L28)
tr'
B KarrecrBe
roMr4HupyFrrlero qroqec-
k,,
ez
I:e=Fl.HvJ,
e..J.2s)
Koropoe" lrry*aa e << ,. upr4rl'rMaer
Brr.u
" "
( ,Ki1l2
IEJ
/-/[Hv]
(2.13o)
TaKnt odpagoM, garroJlEeEtretroBepxEocrfi a.{cop6eHTa Hs-aroMaMr{ Mox(er JMoo
rre SaBucerb or tr3MeEeEtrff[Hv], JM6O LrsMeIIflTbCS
rrpofioprprolraJrbEo ["r]t2
llJt[ [Hvl . IIepByr] cr4Tyarym cJre,uJer o)fi]r,qarbB cryqae oorbu!fi RoHlerirparril
[Hv] tr qpu 6oJrbuD( crerreEfix 3arloJrrrerrr48
rroBepxHocrr4, BTopaF c]rryarr,rf ]rMeer Mecro Eptr ,qocraroqEo 6orbmo( crerleuffx BanoJrrlenllgrloBepxnocrrr I4 MaJIux
[Hv] tr otrpeAeJlserca rJIaBHbrM
oopa3oM rrol3]rrctoc?bro Hs-aroMoB, Tperbs cr4_
TYAIIIS
UMEET MECTO IIP}! MANOft BEJIIIIIIfiIE
gHEPII4I4
CBfl3I{
HS-ATOMOB
C NOBCPX-
rrocrbD alcopoeETa.
ll;rs c&opocru trBMeEeHr.rflKoruer{Tpar.uM gJreKTpoHoBqpoBo.uorocrrr }rMeeM
ypaBrrelMe
g{tl=k2tu,l -[rn]tre:
(2.131)
o${ocr{TeJIbHoI
do/dT,!/T.
TIIler=B/di
yclJIoBI{e da/at = const coxpaEgeTcfl
qpoMeryrKa BpeMeEIr, trocJle qero doldt
(2.114),
rrr,
t>[K2(1+
Bblxo.4flT
Ha craunoHap
sHarleElls cKopocTll oJleKTpotrpoBo,ulocm
#=i+-E-ifrJ
sBraercfl
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+|eJ.-rS=Kzru.lh-l,
orKy'ua, ytltrTblBasBbrpafreme(2.119) ' [OryqaeM
lilcxo,[fltrg cKagallltoro Bme, crMTaeM, qro cral-EroHapEoe
gHarIeI{?Ie[Hs] ycraEaB.,IllBaercf,oqeEb orrcTlo r[ oqpeAeJrsercs o,UIr4M r4B Bbtpaxerud (2.L27)
- (2.130). yWlEAaf, yCJIOBUe
OrercTpoHefiTpaJrbHocTr.r
(2.!2o)
h.t"l
rn]] + luellrr = [H+l + [e]o h ,
rAe tue:l , KaK E IIpeMe,
KoHrIeETpar-U4rr
cBepcTexnoMeTpr4rrec6ux
aToMoBMeTaruIa, ypaBrreEue(2.131) MOXfiOtrepelMcaTbB Br4Ie
d
ral
Kz[Hj]
-
K2(tel
-
telo)
telh,
l a . L r z )
perleHlreM
KoToporoflBJrseTcaBt[paaeE}Ie
arth
z ^ f * t
o
=*x,t.n+-r'
/f+lR-
K
FAe X = =r
+ arth
,/T*-T
\ z . L J J )
tH'I
t
K'= ft2le]oh
,
omcuBaroqee KI4r{eTI4KytrsMeEeHrr.{
K a h #I e ] '
gJIEKTPOIIPOBOETOCT}I
ATCOPoEETA. IYTEM IPEIETbIGIX
IIEPEXO.UOB JIEIKO IIORA_
sarb' qrq ICtrHertrKa llptrrtoft peaKlu4{ rr cryrreE}r orMcbrBaercfl Bbrpar(eHr4eM
f=*'',
5 3ara: No3053
(2.134)
I29
ue
xi= Kzlr.l/
o
r
fnlr+
I
[e]o, I Rllgernrca ooparflofi peaKII[u - BblpaxeHueM
r
*A -V -, I9 1= K . + c o n s t ,
PAo Kr= hK2telo;
const
= ln(1+
(2.L35)
oolAomx).
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rrprBo-
EIT R BHPAIEIItrD
F='.'
(2 . L36)
qro B cury nupaxerud e.L27 r,u. *o= rr{7 e)2 lH)/ R24h . SaMerr/rM,
-2.130) 3aBtrCI{MOCTb
IISMepgeMOFO
Ea OIIIITe llapaMeTpa Lao/oz oT RoEIIeHrpautrI [Hv] Moaer 6brrb KaK JtrEreltEof, TaK rlt KopHeBoft. Baoeras Brrepel
([o.q]ooEo oro dyler
troKasaEo B rJIaBe 3), yKa,fieM,qro rrp]I fie cJrrrrrrKoM
6oJbmD( KorrrleETpar.Msx
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c rb
As- = "or,'tlil- v
(2 . L3'7' )
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o '
u orllocr.rreJrbEoer.r3Mellefll1e
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oHHOTOCOCy,Ua
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odpa3oM:
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== {.-o9a!1
(2.138)
Ilonygemsle Bbrpax(enrlg,ormcbrBaw,Ie KIrHerrE{yI/r BeJMrrEIy orKJII4Ica gJrenTpoIIpoBo,UrocTr{oKcr4$Ioro aAcopoeETafipu alcopdqru.r aroMapHoro Bo.qopo.qa,B
o6qeM cry\rae ocraDTcs c[paBe,4JrrtBbrMn
n LJtfl aAcop6ryM rnobrx pa.U&carbrsrx
qacTnlqoEopEoro
rma. o.UtaKo B KalI(4oMnoEKpeTrroMcryr{ae ,uolfimnpyw&l
[poqeccoM' oqpeleJlfl@Il, KaK Kllllerffiy' TaK 11craIII{oHapHrIe3EaqeH}Ifi 3JlefiTporrpoBo,Eocrfi,Moaer 6nrr no6ot rr3 qpoqeccoB cxeMbr (2.Lr4), ofipe.{eJraerdrfi clleryr(pncoftKoltrcpeTEoficr{creMbr[12e] .
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[46,1]-5,130-1321gKc[epI/MeETaJIbHoycraEoBreHo, qro K[IHerIIKa LISMeHeIIlIfi oJleKrpofipoBo.ulocr]I
zno IIo,4 BJMaIMeMIIapoB MeTaJrJroB
BnJroTb,qo CTarlroHapHoroBHaqeErrs Xopouo
oIMCEBaeTCfi BbrpaXeHI4eM
= r"'"t,
a[*r-J
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3Ta SaBLICEvtOCTbCTaHOBIITTCfl
OTIeBLIJTIOfi,eCJM, KaK I4 B Cflyqae a.{cop6u,trI
aToMoB BOAOpO.qa, CrMTaTb, qTO IISMerreHUe o KoHTpoJffpyeTcfl cKopocTbro [epe_
xo.ua aAcopofipoBarrEtsx aroMoB MeraJrJia, &oHr]eETpar.[rs RoTopbrx [Me"]
cff rlocTofiffiofi,
B sapsfteltrryn (DopMy Met:
.rd
i!
tMg'l.r
= K , [ u e "r r
= K , t M e/l"rJ- f^;rF \l
11- _ .-l '
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1t'le.l.
cuuraer-
(2.140)
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trapaMeTpoB:c = K,[Me"J/Aa_, p = Ao. /ao.
B rJaBe 3 6ylet tro,q)ooHoorptcaEa sKcrrepnMerrraJrbrrafi
npoBep(a [oryrlell-
I30
n*r B gToM pa3reJle BEpaftelufr, cBaBbIBaw$ ftolil{ellTpauM
aKTIIBHbrxqacrr.flI
B oKpyaamleM a.4cop6eETodbeMe c uBMeEeIIlIeMero gJrerTpolrpoBo.urocrtr
B craII?IOEapIIOM
tr KEHeTEqecKoM
peauMax, a raKjr(e Srccfiepr4MerrraJrblrbre
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lfTalc, l,u tro.E)ooEopaccMorpeJrr{pa3JrrlrqEbre
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HOCTbrIOW[poBo,uruKoBbD(aacopoeEToB pasHblx Kpr{craJJMrrecKrD(TrrIoB.
oco_
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rnrrKa. I{c?oqMc o_aroMoB _ IItrpoJIM co. qpl,t p =
= or9 Top tr TEI*I = 116ooc
Pr4c.3. 16.
I0merluca oJreKrpoupoBoEocT4 rrJrerucl'I
oKcu,4a rlruuca B
qpoqecce a,ucopolutrrN_aroMoB rrptr lroMEarEoft
Te[,Eepa_
rype
O-aroMoB, Iorop'e troflyqaJucb B gToM orIbITeIIyreM III{poJMBa
Eo*cqgs yr,4gpo,qa. I,l3 pucyEl(a B[EO, rrro EaEecerr*e Ea troBepxEocrb
rureEKtrOKCEAarIrFKa aroMrr l@a
(cBepxcTextroMeTpeqecKtre
) fiBJraDTcaaKTtrBHbIMtr
IIeElpaMtr a.q_
copoqm o-arorroB. AEaroruwoe 6Ero troRa3aEotr AJrrI aAcopOltlrr aroMoB
a3oTa
t381. B 3TOMCJryqae4ptrBereEEoeypaBrleEtre(3.11) BTEOJEAeTCA
B 60nee uEporcoMtrETepBaJreBpeMerq tr trptr 6orbu[
oOre[,Erx KoErIetsTpaLEflx aKTEBET{X
qacTtrII.
SaMermu, qro B cryqae a.UcopouM o- I4 N_aroMoBEa ruleElcax zno trIltr
ToM_
treparypax selrn6 29909 B rlqporoM trETepBaJrercoguegtpalEfi aKTEBEbIx qacrnl
xopouo BblrloJlEaercaRmertrqecKoe ypaBlleEtre, BEBe,[eEEoeEa ocEoBe
rlpuMeEeItr{s (FpMa.r6Eo[ Krorermcs, Koropoe Mo[er OETb BarltrcaEo cnelyul@,r
oopagoM:
Aoo/o, = kt
,
( 3 . 1 2)
r.qe t - BpeMa; Aoo=oo- ot (cM. rJIaBy 2, Brrpaserue (2.44)).
O.EaKo B odracrtr yMeperr'brx (r < zoo.c) tr Hr{BKrrN TeM[eparyp trpuueEtrMocrb 9Toro ypaa'ems Eapy[aercs. B pa60Te t3el or@p'lrec*u 6buro
EanreEO ypaaEeEue (cM. rraBy 2, BDrpaftelile(2.e8))
Aoo/La
-
kt
,
( 3 . 1 3)
r'4€ Aoo= t,- t i o@- MtrEuMaJlbgoe
SIIaqeEI{e SJleKrpoqpoBo.ulocn{ B ycJloBtrtlr
'uamloro orrblTa, tr3 KOTOpOTOCJIe.Uyer,vro B trowuposo,qlflEcoaofi mleflrce trMe_
nTcs rq)uMecEileqeIITptr oJrelcrpoqpoBo,ElocrurHe yrlacrBywle IIo rofi
riJM Eiolr
rprrllrEe B xeMocopOIOMaToMoBa3ora r{JII{ Kr4cJropola.
Ha puc. 3.16 rroRa3arra xopouas trpllMeElrMocrbgroro ypaBrreElrff
.qJrsa3oTa.
I'lB cKa3affioro B orEorrreHr{lrarcopdr[EI aroMoB R[cJropoAa r{ a3ora cneAyer
3aMertrTb, lrro rrpaxTrueciaa gpr.r Jmobtxclrryar&rfx HaqaJrbrrascKopocrb
usMerre6 3axag lf 3053
I6I
ytrOMflEtrs oJlercryoqpoBo.urocTEIUIeIIKU OKCU.qaUIIIRa IIOA HILISEI{eMa,4COpoIuIu
4yTblxBgToMpaB,[eJIeaKuellTopHtrxqacTnl,KaKIIBcIyqae'uoEopE[EqacTuu'
IlpouoplsoaaJlbuaKoEIeETpaI.uuqacrruIBllpocrpaEclae'qptrJleralqeMKIIoBepxEocTtr IUIeEKtrOKCIUa, l.e. BErIoJIIlflerCsBEpaaeulle
(3.14)
aToMapabrx qacrlnl s rasoBot 0a3e. cRa3aIEOe OsEar,ue tAl - KoErleErpar.ufi
MeEIy tIucJIoM a'qcopoEpoBaEnblx
qaer, qro Bcer,4a l,IMeercs qpoflopu[olraJlbllocrb
gacTm Ea OKctrUofi trJIeIIrce zno qptr ,UoCTaToqEo MaJIHx SaIIoJIIIeEtrsX ee IIOBepxHoCTtr U qrrcJIOM cBOdolE[D( HOctrTeJIefi ToKa, Ea KoTOpoe tr3MeHruI-acb UX trepBeJMWEa. 3TO OTflOCUTCSK aACOpoLUII!KaK aKqacTnl.
c.UeJlalililfr BbIBO,4XOpOEOKoppeJltrpyeT c
ueIITOpHlD(, TaK tr ,qoEopHbrx
peSyJIlTaTaMtr, uolyqeEHHl[{ B paooTax
[28,40] IIO yCTaEOBJIeE]m yKasaF'FrJ:r
coOTnoUIeEIfr MeTO,[,oMtrSMepeIItrF xofiJIoBCRofi SJIC B llpoUecce aICopoLUItr alolloB
BorraqaJrbEas
(Ao a.qcopotFt)
Bo.uopo,ua,KtrcJlol)o.[augo.ua'aTaKx(eaToMoBMIIorExMeTaJUIoB'gTocBtrIe_
yKasaIIEyD qpotropq[OTeJrbCTByeT o EeCoJIbllIoMlI EeCyqecTBeHEoM BJItrfiEtrII Ea
sJIeKrpoIIoB qpoBo,@rocrtr
flaJrbrrocrb MaJrilx trsMeEeItrfi xorJroBcKofi llolFl4tclocrll
a,qcopouEl aKTtrBHLIX qaCrEI Ea IUIeEICe OKCII.{a I[EIIca trpu Ee6oJ6B 4poqecce
IIIID( 3aTIoJIIIeEUEXee rloBepxllocTl4.
BcecKasaltrloe06a.ucopo4elaKqeIITopEbIxaToMapruuI4MoJIeKyJIFpHblxqacTPuMeIIeHI{ff paspaooraffiilx
odud BEBoA oO ooocEoBalnlocrtr
rruI uo.urBepMaet
(IIJIaBIIIX\'i Oopa3OM zno) B
OKctrIoB
IIJIeEOTTETD( CneqeEIIbIx trOJIyIIpoBOSII{KOBbIX
qpeEla3llaqeEHbrx
.UJtfi KoJII[qecrBeIIHIlx
IIflC,
BBcoKoqyBcrBr4TerbHlrx
IcaqecrBe
MaJIIIX KOIIUeETpaLUd aToMapflEx n MoJIeKyJIEpHHX aKqeFff3Meperflfr ucrresaqe
pgle cryrlaeB oKoro 1o7-1Oe aroTOpHbtx u ,qoEopHEX qaoTl'flI' COCTaBJISWD( B
K IIIIC'
cpe.F' [pi{reraueft
rpocrpaEcrBa
MoB B KyoI[tlecKoM caETl{Merpe
3.3.2.
CBooo,sue Pa.EdKaJu
OKC}IIaX B
BaMU sJIeKrpI{tIecKrIe o@KTH IIa IIOJIytrpoBo,uflII(OBbIX
06Eapy8effiJe
qpoqeccexeMocopoltnraToMaplfilx.IacTI4I6HJMtrorcooEol.Isyqelill[41]u'u,Ilfl
cJlyqagxellocop6ulupa3JM,trIofitrpllpoFcBo6o.uuxpaMtaJroB:cH2'cH]'c2H5'
OKa3aJIocb' qro 8ce 9Tu qacrnlFl nocgt arqeuroprufr
c.HroHr,oH,NH,NH2 u,4)'
oKcI4SflX troJry11o oTrrglreglm K sJIeKgpoIIaM Upl4\recgofi trpoBo,Un/tocTll
xipaxiep
''oopaTnua'' B lasoBoft
cpe,ue B
IIpaB[JIo'
KaK
a,qcop6ul'I'
a
I,D(
IIpoBo'@EcoB,
Ee
oopaTl4'ocrfi
pasyMeeTcfi,
o0
odracTl.I IIoBEItreEHHx TeMlepaTyp. ?e'Ib I'IIeT,
IIpOIIOCJIe
OKCI4Ia
IIJIeHIOI
pa,4ma,noB, a SJIeKTpOEIIOTO cocTofiilfts
alcop6r@
250-3000c B BaKyyMe ruu ruIeprsofi uo
cBme
rpeBartrs ee trpE TeMtreparype
pa'u[caJloB trocJle
xeMocopdEpoBalilux
xe
Cylr6a
cpe.qe.
olccll,uy
K
orEoEeHltro
pa'@taJtoB
KOMIIJIeKCOB
TaKOfi O6pa6oTKtr Otrpe,ueJlfieTcfl pac[afioM trOBepxEocTIIilX
EaIIeIITpaxxeMocopdl@I(qaqeBcerogTocBepxcTextroMeTprqecKueaToMHMeTaJIJIaoKcII.ua)uBH'ueIeIil,IeMBrasoBMo6beM,KaKtrpaB}Ulo'BaJIeIITEo-EacEI{ ru)yrll)( coeFtHelil[fi'
EerrHllx xuMtrqecKm yrreBo.4opoEftD(
ol]blTIIoRaSaJI'IIToBceuccJle,uoBal{mleIiaMtraJIKI4JIbIIHe'III'4)oKcI{JIbHbIeu
aMl{Iropa,scca.ruBllpoqeccexeuocopdt.uurSHarMTeJibIlbIMoopasoMyMeIIbIIIaDT
gJIeKTpoqpoBoEIocTblIyBeJIIFI}IBaFTpaooTyBExoIaTaIcID(oKcI4ElbIxlloJryqpoqro
oollapyt(eaElre
BO.EII4ICOB,KaK zno, Tio2, cdo, wot' MoO3I4 El' SaMerm\/r'
9(nFRTbIBecbMaBeJi'IKI,I'BocooeltrIocTl.IecJMpeqb}I.4eToBfi{aHIIlIxeMocopdgJIeKTpOIrpoBoJrIocTb cIIeqeEIIblx TOIIKtrX (C TOfiUHaMtr
ul4r4 aKT[BH!rX qacTItrI Ea
MeHbmelMtM)noIyKpI,IcTaIIIirqecKI,D(-troIyqpoBo.uIlIKoBbIxIIJIeIIoK.TaK'oIeK10<
rpoupoBo4rocrb raruD( [JIeIIoK B rrp]rcyrcrBl,Il{ cBooo.ulblx cH3-pa,ulKaJIoBc KOIiqenrparyteil gaxe toocu-3 I4 MellbuteMoxer B BaBrcr,rMocrltor ycroBrd grcne}TSMEEflTbCg
IIA IEC'I?KII I4 COTHIIIIPOUEIITOB
NO OTHOIIICHITtrO
PI{MEHTA
K CE IIEPBOEaqaflbHow 3rraqeHrflo.
yMeEbmerfiregJreKTpollpoBo.EtocrlrB qpoqecce xeMocopOutr{ aJrrctrJrbHbrx
pamKaJOB IIa IIOJIyIIpOBO.UIIIKOBbIX
OKC]IgaX n-TIIIIa OobrEIO HOCTITIIpI4 noBbueHH}Jx
TeM[epaTypax odpaTlo,trfr xapaKTep, o.uraKo B o.&rrD(14 Tex fie ycJroBr{sx BeJMwtrIa g(meKTa BaBrircr{Tor xr,rMrrqecKofi r.fi,u{BrA/aJrbHocrtr alcopoesra, HaupfiMep, pacrroJralas llccJreloBaHEbre rraMrr oKcr4.U B nops,Ure yoDrBarMsrrsMege_
Erfi lrx sJreKTpoqpoBo$rocTtr[o.u BJtr{firlleM xeMocopouru{, c(a]r€M, cH2-pa.utrcaJroB, Irptr trporDrx paBHrrx ycroBnqx omJTa, noJryqaeMcreIyWM prrA aK?r[BrrocTl{
a.qcopoeEToB:
ZnO > TiO2
> CdO > WO3 > UoOl
.
JIerKo BaMerIITb, qTo B oroM psAy JreBee pactroJroaeHr{Te oKcI{]El, c MeTaJUIaMtr
pa.U{KaJIEOxoTEee OopaByFTMeTaJIJIOopraErFrecKUe
KoTopHXCBOoOJtFHe
coe.UtrIeIItrfl.
OErr troKagar ratq[e, qTo usMeHerrlfegJteKTporpoBolFocrrr KaKoro-JMdo o.uEOrO OKCtrIa (Eatrpnrep, zno) B cwqae xeMocopoluM rra EeM paBJrrFrHru aJrbKUIEHIX pa.@CaJIOB,TaKAe trptr qpoqlD( paBEIlx ycJIoBI[gx oIIbITa, g satteTEoil
cTetreEu SactrcuT oT xllrMtr(IecKofilll)I/rpo,u cBodo.utrD(pa.@{aJroB. EcJErI,ICCJeAOBaITFHe trpocTe'IMe
aJIKtrJIbHbIe paIumaJIH pacIIoJIoaI{Tb B IIopR,u{e y6EBaro8
rlx BJII{AEtr^f,Ea 9JIeKTpOqpOBO,UIOCTb
rUreEOK, tr3TOTOBJIeITHTD(
tr3 Bblopaffioro
IraMEoKcula, To EoWrIuTcr creAy@d ps,q aKTlrBEocrII a.qcop6aroB:
cH2 > cH3 > c2H5 > caHT .
HeooxoEDro orMerETb ro oocrosrerbcrBo, qro gTa trocJreloBareJrbEocrb xopouro colJracyeTcff c ydEBaMeM B BToMps.6t xnMnqecKofi aKTrBHocTtr trep€trtrcJIeEr{Fr pa.qrutaJloB[42], EO EaXO.UITCflB trpOTI4BOpetIIM
C BeJIIltrIItAaMtr,
EaUpI!Mep, gJleKTporrEoro cpo,UcTBa EeKoTopHxuB rrr,ff [43]. [IprBelemrHe pe3yJrbTA$I
C EECOMEEffiOCTbD
YKAsIIBADT
EA AOI,IIIEI(PYUIIJTN
3EAIIIIIMOCTI
(IIFU
MAIbIX
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trx xtrMErrecKoftaKTBEocl% tr, qro Ba&ro, Bo BJMfiruItree Ea oJrercrpolpoBo,uHocTb clleqeFr$rr IUI€EOKoKctr[oB' a Ee cotrpoBo&,{ar[ero ee Bapfl[eHtrg uoBepxEocl% a.qcopoeEra. JIrs ebrsBnema trprpo.u qeHrpoB a.[copoqro pa,4rKaJroB
6HJu trpoBe.qeErrgKcIIepuMeETbr
uo JrerEpoBaEroopaBJrI{lrEbrME
(Na, zn,
MeTaJUraMtr
Ti, Fe tr rc. ) rrJIerIoK, rrsroToBJrerrHExI,I3 OKCtrIa UrrrKa. JlerrpoBalue trpoBo,@JIocb ,FyMa Mero.qaMl{:Mero,qoMaroMapHilx [yqlcoB JM6o Mero.uoM paBEo_
BecEoIo [apa trpU MaJrr{x.qaBJleHrrsx(Na, zn).
Ha pEc. 3.L7 g. r.18 uoKasaHE pegyJlbTarblonHToBrlo BJMgEm Ea sJroKTpoqpoBo.UocTb a.IcopdrFnr cH2- tr cur-pa.UmaJroBHa rrJreglcaxo6ctrIa rFr{Ka,
JrerqpoBanFlrr aroMaMEIIEETCa[41] tr Trrrarra t441. Bu.uro, qro qeM 00rb[e BeJrtr\uEa oo, T.e. qeM 6oJ6Ee B oopasqe I{p]rMecHrEaTorrroB, TeM 6o.rlbue BeJItrquEa cTatluoEapEoro trBMeBemfl sneKTporrpoBorErocrtr,T.e. oorbue cretreEb Ba_
IIOJIEEEtrA
trOBEPXEOCTtr
IIJIEEKEXEMOCOPOIrPOBATTITrJUH
MATEPTAJIAMI,I.
C YBEJUIqEroeM rltrcna a.qcopdl&ornrtJrUeErpoB, KoropbrMtr, KaK cJle,4yer llg qptrBeAer.nlJr
3,4ECb
POSYJIbTATOB
OIIIITOB,
flBJIADTCfl
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ATOMH METAJIJIOB,
YObICTPSET-
cs ralc8e tr a.qcopdlEoffias
rcEEerrrrcatrgMerreErrg oJrercrpoqpoBo,ryocrtr nerEpoBaffiofi rL,IeEKtr.B coorBercrBrEr c EaEefi rnnotesofi o trpffpole rIeEryoB xeMocopolFnr aJugJGrrwy paJ@aJIoB Moelo qpe.UIoJIofiLITb,qro qeM aIcTtrBEea oEtr
B3anoIeficTByDT C aTOMaMrrlaErroro MeTaJUra:zn, Ti, Na, pb I Ap. (olurIn
lo '10, xlrll
-la'10,
xln-l
trJItr B KOEeqUTEpasEocTsx
-Ao- = 1g
(3.17)
rlpl$reEn|ocrb trocJre.Eoro ypaBEeHr4ffI( oultcaHr{n BJMfiHTTE
rra sJrercrpoupoBo.qHocTb trJIeEoIczno alcopdqru pa.UlKaJIoB tro6agarra Ea rrpllryepe cHr_pa,UEraJIa
(P}IC.3.19
20
Puc.3.17.
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40
60 t,run
0
/0
20
J0 t.nuu
I0merma BJreKrpotrpoBolurocrtr rureEKE oKcuAa r.uffiKaB
qpoqecce alcop6r.@ cHz-dtrpa.umaroBrq)tr roooc
Pa.Umafi{ troJryqaJurcb (foro.msou EapoB KereEa rrpll
p = 0,5 Top o _ uocJle a.{copouc.rzn_aToMoB; _
6
lo
(/) s nocre (2) a,ucop6uq.r zn-aroMoB
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oJreKrpo[poBoEocrn rurelrKr.r zno B rlpoqecce
A.UCOP6I.UEI
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TeM[epaType B SABT4CUMOCTT{
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(6ee aroMoB rtrTaEa)
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a&TIBEocru). ,lB cKagaEroro creAyer, qro Upoqecc xeMocopdlru aJrKnrbrulx
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trJreEKtroKctrAa Moffio qpe.qcTaBtrTbcne,rymun,to6pa3oM:
d o- f f = k d[ R
f R] vt :[ ] t e l .
--aE
(3.15)
,
rAe k - RuBerr{rrecRas troctofiHrrafl, saBtrcruas oT TeMleparypH. }{s groro
ypaBEeErrfl,KaK rroKa3arroB rJraBe 2 (Btrpaaeril{e(2.44)),
rlerpy,4ro BHBecrtr
ypaBrreHtre ryLqa
(3.16)
I64
.ITO CIIP'IMJIEHITE 9RCIIEP}IMEIITAIbEOfi
-5t- - -"[+-].=o=u i
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',
(3.18)
llrg ua.ruur gsaqeruM e 6y.uer r4uerb Mecro [pocrafl rrpo[opr.urouaJrblrocrb MeEA]l
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BnoJIHeyIoBJIeTBoptITe.rIbHoe
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n Kr{cJropo,{a
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cwqae arcopdrr,nn NH- E Nlr2-pa.@{aJloB.}IMeercff Mlroro gKCrIepIlMeEraJIbHbD(
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zo.llocneto5a II .H., MscHlJJcoO
il.A. // [lJi CCCP, rgeo. T.167. C.625-634.
2L.fhonas G., Lander J.J. // J. Chem. Phys. 1956. Vol.6. P.1136-l-141.
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BupafiaerJIrs BToporo nops.6a noBepxxocrgoft peroMdrcrar.[Ergra ae BeJrrlrrrrqra
Cg
TAK:
N , / N =
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1t2
hl
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r,4e h - paccTosErre,4oycJroBEoroMecTa oTcqeTa (B aalIIeMcJlygae - SaTBop);
pa.4rRaJIOB
N r[ No- KOErIeETpar.UItr
Ea ypOBReh Il yCJIOBIIOM
WJIeBOMypOBEeho;
5 = lrrgzlsol"';
u - cpe.ursfl cKopocrb tracrruI; II - rreplorerp cocy'qa, s [rlJloqa,ub
ceqeflufl cocy.[a; D - Koo(Epff&eEr ]trI@yslel rracrrtrI; t v d. - Koe(mLu{errrE(BeposrEocrb) peKoMdmarE4rracrrtrL T.e. orlloueEl{e qncer pe3yJrbraTrtBHbrx coylaperffd qacrltrI o rloBepxHocrb rIJrI{ MeEAy coooft K ooqeMy 'tr,Icry
coyfiapelfiffi. SaMe?n , qro Mero,[ Cr,ftrra [1] upeAycMarpr4Baer, qro pa,UaJrbuoe
TIaCTItrIEe I4MeeTMeCTa. 3TO BTEOJEISpactrpeAeJlellllre KoHIIeIITpaLUtr4
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^/2 << r ..
(4.3)
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r,[e r - ,[JrrtEacBooo,uroro [pooera; r - pa.u(yc cocy.qa.
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tracrn"L ttporenaqeft no ne$nony nops:u{y, AJrs oqpeIeJrerufi a6coJlloTgblx BEaqeEIfr z Heodxo,utr\,toBIIaTb JItIIItbpacqpe.4eJleElleoTHoctrTeJlbltllx rIacTLq BAoJIb
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tracTuq EporeKaer rro BTopoMyrroprlJury, To B gToM cryqae Eeooxo,Uoro gHarb
TaK[e IJrfi KaRoro-JMoo sHaqeHrrsh aocoJrr0TrrynKoHuerrrpatEoosrlx qacrr,ul.
IlEoFowcreruue rlrccJreAoBalMfl rroKa3aJrr{,!ITo, KaK rrpaB}rJro,reTeporeErras
peroMdlfiar.U{s cBodo.Uiltx aroMoB r,r pa.Utr{aJroB rrporercaer rro [epBoMy rrops.By,
a, cJIeIoBaTeJIbIIO,,4'Iff Oqpe.UeJIeIIlIfi
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B 9TOMCIyqae II3
7 EeOoXO.UOTO
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V = f (h). JITfi 3TOTOMO)ftIOIIO HAITAEIfrO!,ry
pacrlpe,{eJleEm oTEoctrTeJlbmlx BeJrr{rtrrH v : 1ao/dt1
,- o BAOJTbIIa[paBJrs171
tn("{,r)
t9(rn/Ho. ra)
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TaRr,[u oopa3oM conocTaB.[eE]Ie IIoKasaJIo xopoluyn cxo.UruocTb peByJIbTaroB Bcex
Tpex MeTo.qoB, xoTs ,&ta[aSollbl Kolil{eHTpaLuIu H-aToMoB' IIplI KOTOp6IX 3rl,I MenpuMeHr4Mbr,.rpe3BH.laltlo paBJILrIIlH. Mero.u ImC IIpI'IMeHfiM ]IJIfl ooJlacrrl
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groil
K aKTI'IBHNM gacrIoIaM (pnc.
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Maro qyBcrBllTeJIbHHMI{ K Hrllr.
SaMeTrD, TaKtre, qTo'MeToA fmc oJaro,Uaps 6oJIbEo[ qyBcTBlITeJIbIlocTII MO&eT
o /
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cH3 pa,U/UCaJIOB
B KBapIIeBOMlpIJIItrI4)e OT paCCTOgrut
h rureHoKcerrcopoB Io MecTa reHepar-uMpa.uftaJroB npr4
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I - zsoc;Z - t+oi B - z+t; 4 - zes; S _ 3oooc
SaBl4clatocrb orHocl[TeJrbEoftK OEqeHTpAII[II (rflNo) HaroMoB B peaKLuoEIIoM cocyAe, uslaeperurofi pa3rlltllEblMr{
Mero,UaMrr (Z _ uoJryfipoBo.UilEcoB[il ceHcop, Z _ LsEcpo_
KaJroplrMerp, 3 - Er(mysr.rortrftfr Mero,q Bpe,qe), or orEo_
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Ke By,Ua (J/,r")
qeft
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EA CTEKJIEIDI{ PAsJII/rIIHHXTEMlepaTypax
cTeKJIa. ycroBlrg
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(4.1)
B groM om{Te xopoEo BErroJrEflercs, o qeM Morrfio cy,urrb rro
oopMyra
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pe_
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c aHepflleil
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a rar$(e aroMoB
B o I o p o A a [ 4 ] , K r { c J l o p o , 4 a[ 5 ] I , I a s o r a [ 6 ] ,
peKoMd:tri.arwr aKTr[BHbrx rracrl,tr] Ha or,ueJrbJIrf r.rccre.uoBarMff rereporerfiroft
peKoMdIIBalrEr
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pa3JII'rrIHHX
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rlccopOeEToB. B sroM cryqae qpuMeHllMa cJle,uyroas (popMyra CleITa c yqeroM
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I
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v
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qaflx
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B OTIIX CJLY-
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T.70
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ceHco[#J".
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IitS
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lnv 1
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B sT]or sKcuep[MEHTAX.
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Ilpu oroM rlorpeugocrb
tr3MepeEtrs3a cqeT Brcla,[a 02 B rrsMepeHtrfiaToMapEoro Kl4cJlopo,ua
8a BEcoTe
1oo KM (torl/tol oro;ro 10 ) cocraB}IT Bcero (5 I z;.ro'tt, B AarbEeltneM
yMellbtlaf,cb c yBeJltrrleuneM
BEcorbr. 3Ta ctrTyar.Es .ueficrBurerbBa ,uJIa.{ereKTopoB, pactroJloaeHElIx"otKpblTtnt" oopagoM, B aEaJM3arope, o,ulaKo, .[ereKTopH
paCtrOJIOAeErr
tro uSJIOAeFrilJM
BH[e COO6paSeIM,n,|
B CUeLUaJTbIIOfi
U3MeptrTerbHofi
troJtocrtr, coooqarueilcff c arMocoepofi KaEaJroM.IIptr gToM cJreAyer yqlrrEBarb,
qro ga cqer rtroeJM aroMoB IIa creErcax KaHaJrarr troJrocrtr qpol{cxo.u{T o6oraqeHue rasa MoJIeKyJrfipHbrM
RucJropo,{oM(IIo cpaBEerilnoc aTMoc(pprum), ,uo lreMeIIaeTBeJItrTItrHrI
florpemocT€fi Ba cqeT BruIa.ua02. Ta$, .uJrflucrroJrb3oBall]IsB
gKCIIEPUMEETE
AEAJM3ATOPA KOEIIEETPAUruI
ATOMOB B IIOJIOCTII COCTABJISET
ll3MeperMfl RorflIelirpaluIlI aroMapHoro KficJlopo,uac noMoqbp ceHcopa c noJlyqyBCTBI.ITeIbHIff\,9{
yCTaIIOBJIOIIHOTO
IIa MeTeOpaKeTe
9JIOMOHTaMI{'
IIpOBO.UII4KOBUMI4
MP-12, rlpoBelelnr 27 ,qeKa6ps ]-e79 ro.ua B nyrrKTe "BoJForpaI". I43Mepelufl
BeJrI{cbEa BocxoAsqeft BerBu rpaeKTopttr4paKertr Ea orpe3Re rlyrl{ c 96 KM .4o
B 18 r{ 11 MTIII
Bep[II4IIH TpaeKTOpI4rIIIa rOZ rU. IIyCX paKerbl COCTOSJICS
MecrHoro BpeMeElI. leoMarlgrTHafl I,r coJIHelIHagaRTlIBHocrI{ Bo BpeMfi gKcrlepuIIoTOK pa'ryIougJlyqeHlIflCOJIMeIITa XapaKTep[3oBafi{Cb CJIeAyW{I\{rIBeJIITFIIEIaMII:
InIa F.^- = L64.tO-" Bt,/ll'.ru, Cpe.uree3HaqeH[e noToKa pa.ryIou3ryqeHfifl
lurlerc Ko = 3. CeEcop 6bUIyCTa3a rpII MecfiUaF,|0,,= ztg'to'"Bt/ut'Jll,
qaCT[
qTO
paKerH
TaK,
rrpO,{OJIbIIaff
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B rrpocrpallcrBe Ba
ocl,r parerbr. TaK Karc parera cradI.IJMBIrpoBaJIacb
JIeJrbEa
c,{er dHcrporo BpaqeHfiff(oKoro s o6/c), To Ha Bocxo,u&eft BerBtr ceHcop osr
opr4errrlrpoBaHBxo.urr,rMorBepcrueM Brrepe.{ rro BeKTopy cKopocrrr. IIpu o6pa6orEaft,ueltrraflB paoorax [48] oyru(Is{oEaJbKe rrepaFraux .qalrHtrxrrcrroJrb3oBaJracb
Hafl cBsab Meril]J/KoHrleErpau4efi aroMoB KrlcJlopo,qaB cBooo.ulofi arMoc(repe I.I
r[x KorrqeHTpaqlteftB llpu60pe, [peAcraBJrs{m{ilt co60fi c(FpllrrrecKyn rroJrocrb,
c arMoc@poft TpyoKofi, ,qrF cryqas cBooo.ulo MoJIeKyJIffpIIoro
coe,u,rnffrcfiU/ncF
TeqeEtrfl IIptr IIyJIeBOMyrJle aTaICUC yrreToMrl4oefil aToMoB.
qpe,ucraBleHll pe3yJrbrarbl I{eMepeEId gJleKTponpoBo.Ulocrrl
Ha pac, t.zt
nIIc, [oJryrreEsle c rloMoqbDTeJIeMerpI4IIc 6opra paKerE MP-12' a raxse IIeKoTOPbIE ORCIIEPUMEHTAJIbHI{E I[ MO,UEJIbHNE ,4AIIHilE APYTID(
= l-oe.
208
TAKTE
IDUBE-
Puc.4,23.
Pactrpe,qerenue$onlenTparyfr 0-arolaoe B Bepxueft arMoc@pe
t - Mero.[ IIIC, zt.rz.zs,"Bolrorpa.u"(nacrosqas pa6ora)i
2,3 - Macc-aneKTpoMerprrsi 4,5 - pesorraEcrras
crreKTpocKolrr.rfl; 6 - cepeopffsle rrJreIIKI4; 7,8 - MopacqeT6l
.qeJIbHIJe
/60
OKOJIO
:.0'a roroleurparlu B arMoc(Fpe, qro odycroBfi[Baer BeJmqrtr(y[orpeurrocrrr Ha
BHcoTeoKoJro1oo K[r paBEofi o,s - o,7N.
Moreryrsprufr KtrcJropo,qB Boodyfr,qeruroMcocrorrnrtr{ oz(las) (cmlletrufr
tcnclopo.u) oIIaiMTeJIbIIo clIJIbEee BJII4fler Ea usMepeEug. Hallpln|ep, usMeIIeIMfi gJrerTporrpoBo.EocrtrIUreHoKzno Iro.u geftcrBlreM o2(rAe) u o-aroMoB paBErr trptr orrEoEermr to2(rA;)1/tol = 3,5.1o . norpemrbcri, odycroBreEras
BIOIa,{OM
O2(rAs),COCTaB[fieT
Ha Bncore 1Oo I(M (to2(lAe)')/lo] - ro-t; ororo:.:.0-2t.
BJmflrure raKE( aKTTTBHHX
IcoMnoEeHToB,
rcar N; oH; n, na ItrIC qpn rrpoqtot
paBHbrxycJroBr4flxcotr3MeprrMo
c BJrrrsrMeM
aroMapHoro Kr4cJropoAatsol. BKJaI N
u ott, 6ygyw qpofloprg{orrarer r[x ofiroctrTeJlbuoMyco.qepfiarfloo(uo cpannerunoc
o) B aTMoc(Fpe, cyqecTBeltrftnr
odpagoMMotreTcKaBEBaTbca
Ea BbrcoTax MeHee
60 - 70 ICr,. IIpI4\,teHeEIeB aIIaJIgSaTope ceJIeKTtrBHEx,qeTexTopoB ITcK,IFtIaeT
BJItrtrtue aroMapEoro BoAopo,qa.I4ccJe,uoBarfl.re
a.ucopoluor[apoB Hzo Ha rrJrerrKax
zno [50] cBrulereJrbcrByer o Kpafue rIeBHalMTeJrbHoM
IID(BJMEptrI [pr.r reM[epaType EneIIoK rtrrse loooc. I43MeEeH,Ie
oJrexTporlpoBo,ulocrr{nJreHoKrro,q AeficrBrleM rlapoB l{2o tr o-aToMoB cou3Mep}il,ro[pr4 orHorrreH]rr{
KorqerrTparyil tHrol/tol=
ABTOPOB.
l/. xn
4
6
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4 6
L0), cn-1
209
gKctrepuMerlTaJlbHrle
peByJrbTaTbI
Ieltr{
aHaJIorI{lIEbIx
l,!3Meperfld,
rloJlyr{eHHblx
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odcrotrerbcrBa
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I/Dt cpaBl{IlrBATb. B IIEJIOM' O.UIIAKO, NOJYqEHIftIE METO.4OMIIIIC
HAXOIATCfi
PEsYIbTATbI [5]-]
B
COOTBETCTBI,Itr C UMEWIMI{Cfl
AAIIHEMI{, TAK, IiAofiO.qAETCff
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ryqeHriltx c rroMoqb[ nIIC pe3yJrbraroB c MoleJrbp t52], pacctMTaruiofi
IIJIfl
yCJOB?fr. SAMerut, rl?o rIpuMeEeElIeflIIc B 3TOft Ooracru gBJlfiercfl
SuMrII4X
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sHaqurerbHo ycllemHeex mfpe, TaK KaIc uoJIyIrpoBo,uMICoBbIe
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A TAK]KE IIPOCTOTOft
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noJryrrpoBoElrrlcoBNM
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I-umKa' Ilorpyr€Imyn B rroJrspHyrcr4Jrr[Jryqle [poroEoAoHopHyro reulrocrb (cM,
p a 3 . { e r3 . 4 ) .
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TAB IIPOIIYCKAETC'I
HEKOTOPOE
BPEMflHA,U
x(ll.UtocTbF(Molmorag 0ap6oTl4poBaTb
qepeg rc,tufoctr), a gaTeM"BalufpaeTcfl',
B aEaJMsarope.B 3TOM Cryqae o6btqio ycraHaBJrr,rBaercrr
paBHoBeclleMeruil
RlrcJlopo.4oM
B raSe-HoclITeJIe, HaIIpI,rMepB BO,4OpO,qe,
tt pacTBopeHHNM
B BbI_
opalfiroM,{rff s1ofi UeJrr[pacTBop[Tere. rIeM Oofibne ,UIIsreKTpI4qecKasnocrofiH_
Hafi c qpoToHo.qorlopEoto pacrBoprrreJrfl (Bo.ua, crtrfprbr, BolFo_IIoKcaEoBbre
cMecr'tu rc. ) ' TeM dbrcrpee ycrarraBJrltBaercfi crar-urotapuarr Kouqerrrpar_u,rfi
a.uCOPO}IPOBAIfiIOTO KIICJIOPO,4A
CTAIT4OIIAPHOE SEAqCEIIE
HA
IIJIEEftE
OKCII.4A
SJIEKTPOIIPOBOIFIOCTII
IIffiKA,
CEHCOPA,
A
CJIE.IOBATEJIbIIO,
COOTBETCTBYIOqCE
II
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KtrcJropo.ua
ueHTpar-utr{
B ra3e-HoctrreJre, yMrroxerrHoilna xoe(@u.glent Eyiisexa,
N
rTE
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N -
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=
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B
P,r
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4
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1
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PACTBOPUTEJIb I4 IASOHOCI,I_
Cxelff,I raBoarIaJIIrTIfiIecKID(gqeeK IJIfi [apoBofi (o) ]I
nc,r.ucoft(d') @as
I - cocy.U;2-cencop (nrenrazno); B_rcograrTbr;
4 - ocreKJoBamloe &eJle3o; S - MarIil4THarIMeruaJrKa
2I0
)
COOTBETCTBEIIHO; F - KOOGPfl.IIEIIT bYHSEHA (OTHOEEIME PABIIOBECHUX
SaMerm\r' o.EIaB IPIJ[tocrI{ I4 B rase Ha.q xEu{ocrblo).
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TEJIb
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Cryqae, ecJM rIoA rIoJIy[pOBO.UfiIICOBOftTIJIeHKOft'
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(- 5OO O6ll'/fi{I{) Marlil,IfHafi MeulaJIKa, I{StoToBJIeHIIafi I43 CTeiq[RI{HOfi TpyoKLt .&{aMerpoM 3-4 MM I4,qJtrtrIoft l5-2o MM c BIIagHHbIMBlryrpb r{eJIeBHbIMcrep$ei{bKoM.
"cIIfiTId4"
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peaKI-uM (cM. rJ. 3) a,4y,uaJleHrrfi
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B no,qaqe Kr4cJropola K rIJIeIilce I4
qro B cl,ulbHoft crenecop6rpoBaruroto KtlcJlopo,ua c MotolcyJIaMI,I pacrBopl{TeJlg,
- ycraHoBJIeHI4fl
Hlr oqpe.ueJlfier BeJMquHy tI BocllpollSBo,ulMocrb caMoto g@&Ta
c TauuoHapHoft 3JIeKrporrpoBo.ulo c TI{ ceBcopa .
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xo.u{r4afi cKopocTb
BCJMI{}IIIAMIIKOHCTAHT CrcOPOCTEftA.4COP6IIIDTI{ TJIABHLIMOOPA3OM PEAKUI4II B3A_
a.Ucopol,rpoBalllloro Kl{cJlopo.4a c pacrBopl{TereM (cM. fJ. 3). TaK,
l4rvlo,UeftcTBus
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OHAPHOft 9JIEKTPOIIPOBO.UHOCTII
B BO,qOpO.Ue I4CnOJIb3yKol.ua ,qJIs aIlaJMSa Ira KI,ICJIOpO.U
B ?oM cryqae,
rIoBBoJIfier rrpoBo.u4Tb aHa]t04,urocrb - aueroHl{Tpl,ut, 3To oocrofiTerbcrBo
JM3 raSOB IIa KIICJIOpO,UC rIOMOIIlbloyKaSaIrHOro pacTBopI4TeJIs nplr Kol\,fiarHoli
TeMnepaType 6eB nepeMeul4Balll{s, qro 3HarlrITeJIbHoooJlelqaeT qpoBeleHl4e aHa-
rfiercs
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(3.29) am rrJreERr4
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pacrBopr4TeJrsxB arMoc@pe Bo,qopo.qa
[IIpu Kor\firarEofi TeMleparype (I-4)
lr B BaKyyMe upllr 25ooc (5)
I - Bo.ua (&I,u{ocrb (c = ?B) lI
Hacbuerfiftil fiap)i 2 - Merr4roBbM crtrrpr
(e = 36); 3 - orllJoBbrficrerpr (rolsrocrr
(e - 26) II Eacbuemftd nap);
0
4 - oyruroBbffi clu{pr (€ = 17 )
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PASTI,FIItr{XKOEIICHTPAU,IftPACTBOPCHIIOIOB XI4'E{OCTI{KI,ICJIOPO,4A
I,I, KPOMC TOTO,
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14 SAMEHHXI,IJU{OCTII.CKA3AIfiOE OTIIOCIITCa IC .4AHIIrIM, IIOKAsAHHI,IM
RAK HA PI4_
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rrpoBo&rJrcfl B )I[I,IE{OCTr4fipil HaJMqI,III na.q irefi paBHoBecEoff flapoBoft ',Ilo.uyrxKr4",
B KOTOpOft paBHOBeCI{ag o6%ewlag ftoEqeHTpa4uq KilCJIOpO.UafipeBocxo]trrJra
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B ra_
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Tex r(e
B IA3OTIAPOBOft6A3E, B CBff3I,I C STIIM SAMEqAHI{EM AHAJIITSHA KI,ICJIO_
YCJIOBJ,ISX
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HACbIIqEIIHI'IX
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B CB'Is}I C MATOff 3AB}ICIIMOCTbNB STID( YCJIOBIIfiXBOCIIPOII3BO.UTI\'OCTII
PCSYJIbTATOB OT BOSMOTIbIXKOJIEOAHId TOJIIqI{H}IIIJIEIIKI4IIC,I.u(OCT}I
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fi
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ceHcopa B ireHacblueHrloft ra3o[apoBofi (pa3e ]d B Is,r.u4oHaJMq[eM sa,UaruIoft (Jtr06oft) Marofi KoHueHTpaIIrrr KtrcJropo.qa B ra3e-HocllTeJe (Bo,uopo.ue, a3ore, tHeprHoM raBe 14 lp. ). Ha ocHoBaHI4lI
BTID( I,IsMepelflfr Kog{@fl]ileHT EyH3eHa B Moxfio pacclMTarb no cre,qyrueft
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B b r p a x e E r 4 e( 4 . 2 0 )
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gly rurcElcy. BoBMotEIoeoTcyTcTBse 3 r44rtocrrofi IIJrerrKecrurorrrEocTr{(EAJIrqe
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rorcJlopo.qa B cEcreMe ra3-xol.qKocrIfifr crofi-trJeEca rloJrytrpoBo.ErrEca (oJMBreD/rrc
cr{cTeMe troJrytrpoBo.uruKoBaf uJreErca- llc.r.Bocfb), Ee roBopa yxe o HaJrrlrrrr4tr
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T.C.
B YCJIOB}IflX,
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royroro rItrIa a&qerlTopoBgJIeKTpoIIoBtroJlyrrpoBo.Eflma,a I4MerrHoaJrKr4Jrbribrx
pa,u{KaJIOB [54].
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trreHol{ zno c aAcopdfipoBatsHblMtl Ea H]D( aJIKIIJIbIIHMI,I pa,u[RaJlaMr4
I{JM Kr.IcJIoporoM B arMoc(Fpe HerlacHqerrHtrx rrapoB yKasaHHbrx pacrBoplrreJrefi,
a s cnyqae
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a.ucopdr&eil Ha Hr.E KrrcJropora llJru &e cBooo.ufiD( aJlrg,urbH[x pa,4maJroB
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cr{rlra.nal,| nfic
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B
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cn;6 - 2n".6 geu Oolrne sJre&gporloJloxureJlbnocrbMeraJIJIaB grI/D( KowJIeKcax, TeM oorbEe lIoIIHocTb cBg3LIyrJIepo.U-MeraJrJI,IIpI{ sroM yrJlepo,U EBJIffercfl orplIIIareJIbIIbIM KoIIIIoM l$trlorfi. TaR, B cryqae cBflBI4 c-K llollHocrb
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pasJI],FIHbtXOpIIOBepXIIOCTHbIXKOMIIJIeKCOBTlIrIS (Zn'*6- 'n-t)" " IpICyTCTBI{I,I
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a.{copoqpo_
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pa6or B odcyMaeMoM rlafipaBJreHa fipr4uepe HeKoroprlx (Frgruco-xlBnrqecKr.D(
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ra3a B paoore ts6]
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B arcMBrroMa3ore, qpe.UcraBJrsrcqeM
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u r.rccJle,qoBaHr4s
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pa3prrla B ToM, qTo, Bapbrfpyfl HeKoTopHe[apaMeTpN pa3prr,4a, Mo,tcrorrJraBHor4
B rrtr[poKoM
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(I{croEilnca N_aroMoB)
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or
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N-aroMOB Ea6JUO.4aerCsllpll o,u{oM !I TOM Xe [oporoBoM
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cTaI-uIonJIeHKI,I, Ilponopul4oHaJlblras
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r]le const
paspElla.
3aMerIa,r. r{To aHarofuwlas BaBI{cI'IMoctl nadnoAa.nacb B no.uoolillx paoorax u
B cryqae oopa3oBaifl.Is aloMoB Bo,uopo.ua t5el B pa3pfi.ue Bo.{opoAa. B yxaeansaBI,IcI4Mocrb conocraBJlella c ,4aHI{!IMI4
uoft padore HaltueHHaff c rloMollblo IIC
c
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noryqeHrlble Mero.uoM IIIC. Ha
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fAC
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t 60 I noKa3aHa rll)}lMeill{Mocrb
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roB r{ccJre.{oBalMs 6NJM BbIopaHE 6yraH I,I lI3oOyr[JIeE B rasoBoft ma3e IfpI4 pa3HNX .UaBJIeHI{fiX11 TaKi(e Cxru(eEHble yrJIeBo.uopoIFI. 3Kc[epId\,'leHTH [poBo.ryIJMCb B
sanaRHHbIX aMnyJIaX C BCTpOeHHbIMUTy,4a CeHCOpaMI{- nJIeIIKaMU ORCI'Ua III&IKa.
z-n3ryqeEufl'
B KaqecrBe I,rcrottEl&ca I43JIyrIeHug cJIytK{JI KooarbroBbfr ficrotrHrtrc
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B noJIy[pOBO.Uflme
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qpeBaJMpyFqefi xeMocopoluer Ha oKcuAe H-aroMoB, ooycroBfi{Baroqefi yBeJII{rIeHIregJleKTpolrpoBo.Urocrtl[mc-oKc[.qa rl4rirca, TaK RaK B gTt!( ycroBurlx aKuerrropEJe cBoftcrBa oopa3ywD(cfl KpyrrHrrxpa,umaJroB cJa6o trposBrsroTcfl. 0cKorrKypEpyE@{r\ifir
c a.4cop6lu4efiH-aToMoBB a,qcJroefipoqeccaMl,l, qplrBoHoBHbrMr,r
gBJIflDTCflI.D(peKOMoI,ffiaL[IflU
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a raKae
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oopaBoBarue H _aroMoB B
a'4cJroe[o.u BJMfiHr,reM
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K IIyJn'. BaMerlo,r,
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or reMleparypn; 1e"t
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fipr ycJroBrru [H"] =
= const A a = ooqpft t = O IpIIBO.trIT
K BhrpAX(eHIIIO
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o
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236.
T,
1975. T. 20. c. 19-38.
1063-1067.
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ce'copaMr{ o''paBtra'o u c ron ToqK[ 3pe'trs, qro
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MoJreKyJIcI{IIrJIerIIoro KtrcJlopo.uaB pacrBope. SEas pacrI'orl- ronrerrpaws
to, B reKca.UeKaEe,Moffio oUelurb KoIIIIeETpalUmcI4iIFJIerEoroKtrcnbpft'locrr
Jropo,uaB ra3oBofi (!a3e.
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to, - BecbMacJloffiaf, ga.qaqa. B Eacroflqee BpeMfl
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ts7l. o.EaKo n oqeErcaM KoElleErpalErft, troJryqeHr{rJxc ero IIoMoqbF, ryaHo
IcOtro,uo.uTb c oqpe.ueJleEllofiocTopoelocTbn. KaK yae oTMeqaJlocb, BeJIIIFIIIHa
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ycJloBrfr fipe.EapureJlbEofi llo.uoroBl([ oKcrIIa [18e]. KpoMe roro, ITpu aHaJltr3e
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247
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CTEEOK
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[1O3,1O4]
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.
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ro.rrJ rcBaBtrcrars{o'ap'r'(
]
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h : Ap/ (znvnr)1/z,
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cpelsreM BpeMerMxc{sHlr MoJreKyJGr,a,qcoporpoBamroftHa rroBepxHocr[. KoJEFrecpaBHo
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N"=ir,
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28
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3L7
Chapter
2. Theory
CONTENTS
2.L.
Foreword.i.
chapter
1. Phy6ico-chenical
basls
of the senionductor
sensor
1 . 1.
l*rat
L.2.
The role
of
the
sensors? . . . . .
the electronic
of
theory
of chemisorption
the
notions about inpact
properties
electrophysical
of
in
2.J.
Electrophysical
I
seniconductor
11
1.3.
various
Adsorption
isotherurs.
).7
1.5.
Adsorption
kinetics.
20
1.6.
characteristical.
L.7.
Adsorption
forns
ranges of gas-solid
temperature
lnter22
inpact
on the
properties
electrophysical
of
bending
of
seniconductor
of adsorptive
charging
of
the
surface
of
subsurface
layers
conductivity
seuriconduci.or adsorbent irork functl-on......
The role of biographical
surface
process
the
of
seniconductor
charging.
of
for
states
biographical
charging
adsorptive
characteristics
el.ectrophysical
conductor
32
surface
1.10.2.
Adsorption
1,10.3.
Adsorptlon
response of
of seniconductor
electrophysical
sensors
based
on
pective
1.12.
hpact
of itg
defects
in
change of
its
concentration
serniconductor
sites
3.4.
chapter
Production
of
studies
of
the
inpact
sensitive
sensors
of
active
adsorbent
on the oxide
sensor
semiconductor
L2o
particl136
conductivity....
and procedures
elements
for
applications
active
par136
detection.
Donor particles....
L43
143
Atonic hydrogen.
L49
3.2.2. Metal atoms..
Acceptor particles.
3.3.1.
sinpLe gas atoms and molecules. . . . . .
3.3.2.
Free radicals.
semiconductor
sensors
in
156
156
condensed media.
-
L62
.
l-68
175
4.2.
PyrolyEis
48
4.3.
56
4.4.
char_acteristicg
of
adsorbent
surface
and
studies
4.5.
atoDs and radicals
of
on hot
filamentE.
La1
in
catalytlc
L89
oxides.
on rnetal
4.7.
4.8.
in the bulk of solids.
Therrno- and photo-spillover
68
nultiphase
4.9.
72
4.10.
Adsorption
partlcles
the
on metal
hydrogen
atoms
in
the
197
atoml'c,
rnoLecular
and cluster
Detal
2oI
oxides.
lower
l,leasurements of the Earth's
oxygen
concentration
by the atonic
sensor
192
193
of
systems.
of
L77
L77
r79
183
adsorbed layers.
on sone elementary processe6 of heterogeneous
Photolysis
from Demetal atoms
Evaporation
of superstolchiometric
surface.
tal-oxide
on the surface and
of active Particles
diffuslon
Lateral
4,6.
and
77
of
of sinple molecules
Gas-phase photolysis.
actions
res-
the
experimenprocesses... ....
in
applications
sone physl"co-chenical
sensor
4. seniconductor
44
change
own nature on adsorptive
of
The nature
characteristics.
charqing
role in the surface
and their
324
110
particles.
and radical
L32
Reconbination
barrier-disordered
conductivity
Process .
References.
of atonic
3. Experinental
4.1.
of the adsorbent
electrophysical
adaorption
uolecular
Carbon nonoxide.
Adsorption
tal
60
irnpact on the
98
donor particl,es.
of molecular
References.
seni-
oxides.
Adsorption
bulk point
3.3.
on the
adsorbents.
of acceptor Particles.
of donor particles.
l.lole-
oxygen
es adsorption
in
charging
of Polycrystalline
Adsorption
particles.
acceptor
charge relaxa-
the
of
1.10.1.
1.11.
Adsorption
3,2.1.
36
surface
adsorbent
ticles
39
of
chapter
chenisorptive
adsorptive
polycrystalline
on sintered
References.
and
ti-on. . .
Inpact
polycrystalline
sintered
of molecular
hydrogen.
on
recharging
surface
surface
semiconductor
account
2.4.2.
2.4.3.
3.2.
the value
1.10.
of
97
cular
I
energy
bands..
with
83
90
93
inpact
Adsorption
of
chenisorptive
KineticE
properties
2.4.1.
{
3.1.
seniconductors.....
fnpact
Adsorption
of adsorption.
actions.
1.9.
adsor-
conductivity
i
of adsorption
L.4.
1.7.2.
83
.
semiconductor
used as sensors' working eleDents.
polycrystalline
adsorbents.....
sintered
2.4.
adsorbents.
1.7.1.
adresponse of seniconductor
parameters.
Tlre methods
seniconductors.....
are the semi,conductor
developnent
adsorptive
electrophysical
detecting.....
of quantitative
principles
of selection
of
2.2.
technique.
1.8.
ceneral
bents
on
of
sorbents
thermosPhere
with
profile
semiconductor
206
techniques.
325
4.11.
Ii{easureuents
of
atnospheric
4.12.
low
oxygen
pressure
Semiconductor
roon
in
the
sensors
plasna-chemical
concentrations
and
processes.
gases
in
studies
of
6.3.
at
temperature.
radiation-
Singlet
2L0
6.3.1-.
2L7
6.3.2.
References.
5.
Interactions
excited
between
particles
and
Electronically
excited
5.2.
Heterogeneous
quenching
5.3.
Technigues
gas-phase
the
solid
states
of
of
6.4.
electronically
surface.
zzo
atons
zzo
and nolecules....
electronically
excited
5.4.
5.5.
230
for
deternination
particles
ted
Detection
of
sensors.
oxygen
5.5.2.
Detection
Singlet
of
electronically
on
singlet
zJo
particles
oxide
properties
vith
semi-
surfaces.
of
oxygen
References.
exci-
phase..
excited
deactivatj.on
Physico-chemical
the
gas
in
electronically
5.5.1.
5.5.3.
of
concentration
conductor
Singlet
242
singlet
with
oxygen
deactivation
on
oxygen
deactivation
on
oxygen.....
242
ZnO-sensors......
glass
quartz
and
surfaces.
5.5.4.
5.6.
tic
248
singl.et
Singlet
5,7.
oxygen
interaction
with
zink
oxide
filns
of
dyes
and
atons
of
rare
gases
arona-
oxide
254
between
netastable
seniconductor
surfaces.
5.7.1,
Heterogeneous
processes
5.7.2,
The Au/Zno-structure-based
stabl-e
atons,
tastable
5.7.3.
tivity
of
and
256
involving
gas
rare
meta_
.
257
sensors
of
gas
rare
ne-
atoms..
The mechanisrn
under
Prospective
262
of
change
action
of
development
of
electronically
of
Au/Zno-sensors,
rare
the
excited
gas
conduc-
netastable
sensor
metbods
atons.
for
.
particles.
274
276
6.
Seniconductor
Enission
solid
6.1.1.
senso*s
partictes
active
6.1.
surfaces....
Atonj,c
app)-ication
ernission
preadsorbed
of
active
fron
in
the
solid
studies
of
surfaces......
particles
frorn
242
disordered
.
242
hydrogen
enission
fron
amorphous
antinony
surface.
6 . L . 2 , Silver
2a3
atorns
solid
emission
during
their
aggregation
on
surfaces.....
6 . 1 . 3 . cold
ernission
surfaces
2go
of
on quartz
silver
under
atorns
impact
of
frour
silver-fil-n
ultrasonic
vib-
rations.
6 . 1 . 4 . A1kyl
294
radicals
ernission
fron
disordered
seleniun
surface.
Oxygen
ver
265
detec-
References.
chapter
250
surface.
hydrocarbons...
Interactions
tion
6.4.1.
with
atons
2g5
enission
nolecular
under
interaction
oxygen.
of
reduced
si.I_
294
326
from
disordered
enission
sotid
304
surfaces..
frorn mechnically
disor-
surface.
oxygen
30s
emj.ssion
from
vanadiurn
pentoxide
307
. .
oxygen photoenission
Singlet
5.4.2.
par-
ticles.
quartz
Singlet
face.
Chapter
ernission
oxygen
dered
and
.....
oxygen
singlet
singlet
oxygen
pe
gas
into
photosensitized
phase
Singl-et
oxygen
surface
of
from
in
the
transition
309
surface.,.......
formation
solid-dye-oxygen
photosensitized
applied
solid
formation
netal
oxides
and
esca309
systems.
on
the
.
313
3L'7
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Mscxrxos
I4ropt Alexceenuu
Cyxapco Baneprt .slxosnesrl
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fleuarr oQceruaa
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