8.1 8.2 8.3 8.4 8.5 8.6
8.1
8.1.1
8.1.2
8.1.3 Tp
8.2
8.2.1 Velocity Rate
t t
rate of reaction
t(1)
(2) ()(IRUV-VISESRNMR)
8.3
8.3.1 overall reaction
8.3.2 elementary reaction
8.3.3(molecularity of reaction) 123
8.3.4 reaction mechanism
8.3.5 (rate equation of chemical reaction)
8. 3. 6law of mass action aAbB gGhH r r = k[A] [B] A Bn = + + kpkkT
, 2. 3.
8.3.7 pseudo order reaction
8.4 n
8.4.1 first order reaction
---differential rate equation of first order reaction
--integral rate equation of first order reaction
halflife time
1. k t(s)(min)(h)(d)(a)
14d6.85%(1) (2) (3) 90%
8.4.2 (second order reaction) 2
CA1/2 CA,0
1. k [] -1 [] -1 2.
8.4.3 (third order reaction) 3
()1. k []-2[]-1
8.4.4 (Zeroth order reaction) A P r = k0
Differential and Integral equation of Zeroth order reaction
1.k[][]-13.xt2.
cA t xt 1. cA,t k k k8.4.5
2.
nA Pt =0 cA,0 0t =t cA xcAtt-dcA/dtln(-dcA/dt)lncAn
lnt1/2lnann
8.5 r~T
8.5.1 vant Hoff) 10 K2~4390 K10 min290 K10 K2
8.5.2 12
345
8.5.3
3 k 4
8.6
8.6.1 Tolman
8.6.2
8.6.3 lnk1/T
BmE
8.6.4
(2),kT2
8.6.5 1
8.6.6
8.7
8.7.1 (Opposing Reaction)
1-1t =0 a 0t =t a-x xt =te a-xe xe
t [A][A]0Kck1k-1
1.2.3.K=k1/k14.ct
8.7.2 (Parallel or Side Reaction)
[A][B] [C]t=0 a 0 0t=ta-x1-x2 x1 x2 1
2
1.2. 3.
4. 5.
8.7.3 (Consecutive Reaction)
(rate determining step)
c-t
y
8.8 (chain reaction)
8.8.1 (straight chain reaction)
1chain initiation 2chain propagation 3chain termination
(Steady State Approximation)
1
2H2
12C
[I]
1(1)k-1(2)k22k2[H2]
2 ,k-1>>k2(1)
8.8.2 (Chain-Branching Reaction)
(Chain-Branching Reaction)
2H2(g)+O2(g)2H2O(g) () HOOHHO2
()
1.ab2.(4)(5)abbc (4)(5), (9)ab
3.(6)-(8)bc4.c5.730 K
8.8.3 1.2.3.4.(EPR)(NMR)
5.7.6.8.(6)(7)
1.C2H6C2H4+H22.r =k[C2H6]3.Ea=284.5 kJmol-14.CH3,C2H5
5.
8.6.
8.8.4
8.8.5 10-50 km
NOCl
8.9 ABA
8.9.1 20
8.9.2
8.9.3
8.9.4 AB AB
8.9.5 A A2A
8.9.6
8.9.7 impact parameter b AB
impact parameter
8.9.8 q
8.9.9 cross section of reaction) brbr
8.9.10 (threshold energy of reaction) EcEc EcEa
8.9.11 (1)(2)(1)(2)1mol
8.9.12 TBEcEaEa Ec
8.9.13 probability factor P=k()/k()
(1) (2) (3)
8.9.14 A k
8.10
8.10.1 (transition state theory) 1935(Eyring)Polany) ,, (absolute rate theory)
8.10.2 (Morse)Ep r0,De,a.
8.10.3 : ABC3: ,ABC=180,ABC,EP=EP(rAB,rBC),
8.10.4 : ABC=180o, EP=EP(rAB,rBC)rABrBC
RBC,A,RTT CTPPAB DA,B,COEP,,
8.10.5 : EyringPolanyiLondonLondon-Eyring-PolanyiLEP Sato London-Eyring-Polanyi-SatoLEPS
8.10.6 (reaction coordinate) RTTP
8.10.7 (saddle point) TRPD
(O) DrABrBC,D RTP
R-T-PR-T-P A+BCEb EbE0
8.10.8 : (a)rABrBC (b)rABrBC (c)(d)
f
8.10.10 (n)
8.10.11 1.2.3.4.
8.11 RRKM
1922Lindemanntheory of unimolecular reaction A*A*P
time lag
RRKM 50Marcus 30RRKRice-Ramsperger-KasselRRKM
8.12 ---
(molecular reaction dynamics) EylingPolanyi D.R.Herschbach1986
:1 234
(principle of micro reversibility) t-tu-u
-state to state reaction -
8.13
8.13.1 cage effect
8.13.2 one encounter 10-12~10-11s100~1000
8.13.3 1 2 3 4
8.13.4
8.14 ()S1T1
8.14.1 e =hn =hc/lu =Lhn Einstein
8.14.2 1. 1818GrotthusDraperGrotthus-Draper2. 19081912EinsteinStark Einstein-Stark
3.Beer-Lambert cdItI0(e)
212HBr+hnH2+Br2
r Ia
8.14.4 (multiplicity of molecule) M M=2S+1 SMZM=1 M=3
(singlet state) S=0M=1S S0 S1S2
(triplet state) S0S=1M=3 TT1,T2
TS
S1T1 S0S1T1 S0S1S0T110-5 T1
(Jablonski) JablonskiSTST
1.vibration relaxation
2.internal conversion
3.intersystem crossing S1T1
4.fluorescenceS1S010-9-10-6 s
5.phosphorescenceT1S010-4-10-2S0T1T1
S1S0+hniT1S0+hnpA*PA*+BA+B*A*+M A+M +Q
(1)1. 2.800 K
(2)1. S1S0 T1S0 2. S0S1 S1S2 S0T1 T13. 10-9~10-6s 10-4~10-2s
8.14.5
8.14.6 1.DrG>02. 3.
8.14.7 (sensitizer)H2+hn 2H Hg
8.14.8 chemiluminescence
8.15
8.15.1 1.2.1091015 13. 4. pH
8.15.2 Michaelis-Menten,Briggs,Haldane,Henry (E)(S)ES,(P)(E)
8.15.3
8.15.4 [E]0[ES][E]
8.15.6 KMKMrmrm KM=[S]
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