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

r~T1vant Hoff 1. >0, 2.

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.

r>r0,, ABr

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)

8.10.9 ,n,(hn

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)

8.14.3 (quantum efficiency) >1H2+Cl22HCl1106

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]

8.15.5 1.[S]>>KMr =k2[E]0[S]2.[S]

8.15.6 KMKMrmrm KM=[S]