化学动力学 化学与环境工程学院 主讲:谢修银
DESCRIPTION
化学动力学 化学与环境工程学院 主讲:谢修银. 下一页. 上一页. 第八章 化学动力学基础. 8.1 化学动力学的任务和目的. 8.2 化学反应速率. 8.3 化学反应的速率方程. 8.4 具有简单级数的反应. 8.5 几种典型的复杂反应. 8.6 温度对反应速率的影响. 下一页. 上一页. 8.1 化学动力学的任务和目的. 量子力学 (宏观). 热 力 学 (宏观). 统 计 热力 学. 动 力 学. A. B. ?. 100K. 100K. 80K. 200K. 300K. 300K. 320K. - PowerPoint PPT PresentationTRANSCRIPT
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8.1 8.2 8.3 8.4 8.5 8.6
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8.1
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8.1.1
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8.1.2
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8.1.3 Tp
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8.2
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8.2.1 Velocity Rate
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t t
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rate of reaction
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t(1)
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(2) ()(IRUV-VISESRNMR)
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8.3
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8.3.1 overall reaction
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8.3.2 elementary reaction
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8.3.3(molecularity of reaction) 123
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8.3.4 reaction mechanism
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8.3.5 (rate equation of chemical reaction)
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8. 3. 6law of mass action aAbB gGhH r r = k[A] [B] A Bn = + + kpkkT
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, 2. 3.
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8.3.7 pseudo order reaction
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8.4 n
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8.4.1 first order reaction
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---differential rate equation of first order reaction
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--integral rate equation of first order reaction
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halflife time
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1. k t(s)(min)(h)(d)(a)
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14d6.85%(1) (2) (3) 90%
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8.4.2 (second order reaction) 2
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CA1/2 CA,0
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1. k [] -1 [] -1 2.
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8.4.3 (third order reaction) 3
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()1. k []-2[]-1
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8.4.4 (Zeroth order reaction) A P r = k0
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Differential and Integral equation of Zeroth order reaction
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1.k[][]-13.xt2.
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cA t xt 1. cA,t k k k8.4.5
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2.
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nA Pt =0 cA,0 0t =t cA xcAtt-dcA/dtln(-dcA/dt)lncAn
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lnt1/2lnann
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8.5 r~T
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8.5.1 vant Hoff) 10 K2~4390 K10 min290 K10 K2
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8.5.2 12
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345
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8.5.3
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3 k 4
- r~T1vant Hoff 1. >0, 2.
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8.6
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8.6.1 Tolman
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8.6.2
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8.6.3 lnk1/T
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BmE
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8.6.4
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(2),kT2
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8.6.5 1
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8.6.6
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8.7
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8.7.1 (Opposing Reaction)
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1-1t =0 a 0t =t a-x xt =te a-xe xe
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t [A][A]0Kck1k-1
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1.2.3.K=k1/k14.ct
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8.7.2 (Parallel or Side Reaction)
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[A][B] [C]t=0 a 0 0t=ta-x1-x2 x1 x2 1
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2
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1.2. 3.
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4. 5.
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8.7.3 (Consecutive Reaction)
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(rate determining step)
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c-t
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y
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8.8 (chain reaction)
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8.8.1 (straight chain reaction)
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1chain initiation 2chain propagation 3chain termination
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(Steady State Approximation)
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1
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2H2
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12C
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[I]
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1(1)k-1(2)k22k2[H2]
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2 ,k-1>>k2(1)
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8.8.2 (Chain-Branching Reaction)
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(Chain-Branching Reaction)
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2H2(g)+O2(g)2H2O(g) () HOOHHO2
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()
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1.ab2.(4)(5)abbc (4)(5), (9)ab
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3.(6)-(8)bc4.c5.730 K
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8.8.3 1.2.3.4.(EPR)(NMR)
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5.7.6.8.(6)(7)
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1.C2H6C2H4+H22.r =k[C2H6]3.Ea=284.5 kJmol-14.CH3,C2H5
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5.
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8.6.
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8.8.4
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8.8.5 10-50 km
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NOCl
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8.9 ABA
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8.9.1 20
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8.9.2
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8.9.3
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8.9.4 AB AB
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8.9.5 A A2A
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8.9.6
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8.9.7 impact parameter b AB
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impact parameter
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8.9.8 q
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8.9.9 cross section of reaction) brbr
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8.9.10 (threshold energy of reaction) EcEc EcEa
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8.9.11 (1)(2)(1)(2)1mol
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8.9.12 TBEcEaEa Ec
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8.9.13 probability factor P=k()/k()
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(1) (2) (3)
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8.9.14 A k
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8.10
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8.10.1 (transition state theory) 1935(Eyring)Polany) ,, (absolute rate theory)
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8.10.2 (Morse)Ep r0,De,a.
- r>r0,, ABr
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8.10.3 : ABC3: ,ABC=180,ABC,EP=EP(rAB,rBC),
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8.10.4 : ABC=180o, EP=EP(rAB,rBC)rABrBC
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RBC,A,RTT CTPPAB DA,B,COEP,,
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8.10.5 : EyringPolanyiLondonLondon-Eyring-PolanyiLEP Sato London-Eyring-Polanyi-SatoLEPS
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8.10.6 (reaction coordinate) RTTP
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8.10.7 (saddle point) TRPD
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(O) DrABrBC,D RTP
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R-T-PR-T-P A+BCEb EbE0
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8.10.8 : (a)rABrBC (b)rABrBC (c)(d)
- 8.10.9 ,n,(hn
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f
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8.10.10 (n)
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8.10.11 1.2.3.4.
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8.11 RRKM
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1922Lindemanntheory of unimolecular reaction A*A*P
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time lag
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RRKM 50Marcus 30RRKRice-Ramsperger-KasselRRKM
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8.12 ---
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(molecular reaction dynamics) EylingPolanyi D.R.Herschbach1986
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:1 234
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(principle of micro reversibility) t-tu-u
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-state to state reaction -
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8.13
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8.13.1 cage effect
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8.13.2 one encounter 10-12~10-11s100~1000
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8.13.3 1 2 3 4
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8.13.4
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8.14 ()S1T1
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8.14.1 e =hn =hc/lu =Lhn Einstein
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8.14.2 1. 1818GrotthusDraperGrotthus-Draper2. 19081912EinsteinStark Einstein-Stark
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3.Beer-Lambert cdItI0(e)
- 8.14.3 (quantum efficiency) >1H2+Cl22HCl1106
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212HBr+hnH2+Br2
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r Ia
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8.14.4 (multiplicity of molecule) M M=2S+1 SMZM=1 M=3
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(singlet state) S=0M=1S S0 S1S2
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(triplet state) S0S=1M=3 TT1,T2
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TS
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S1T1 S0S1T1 S0S1S0T110-5 T1
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(Jablonski) JablonskiSTST
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1.vibration relaxation
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2.internal conversion
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3.intersystem crossing S1T1
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4.fluorescenceS1S010-9-10-6 s
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5.phosphorescenceT1S010-4-10-2S0T1T1
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S1S0+hniT1S0+hnpA*PA*+BA+B*A*+M A+M +Q
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(1)1. 2.800 K
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(2)1. S1S0 T1S0 2. S0S1 S1S2 S0T1 T13. 10-9~10-6s 10-4~10-2s
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8.14.5
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8.14.6 1.DrG>02. 3.
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8.14.7 (sensitizer)H2+hn 2H Hg
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8.14.8 chemiluminescence
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8.15
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8.15.1 1.2.1091015 13. 4. pH
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8.15.2 Michaelis-Menten,Briggs,Haldane,Henry (E)(S)ES,(P)(E)
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8.15.3
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8.15.4 [E]0[ES][E]
- 8.15.5 1.[S]>>KMr =k2[E]0[S]2.[S]
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8.15.6 KMKMrmrm KM=[S]