課程名稱︰物理化學 課程性質︰化工系必修 課程教師︰戴子安教授 開課學院：工學院 開課系所︰化工系 考試日期（年月日）︰2012/6/18 考試時限（分鐘）：150min 是否需發放獎勵金：是 （如未明確表示，則不予發放） 試題 : Supporting information：kB=1.38x10^-23J/K , h=6.626x10^-34Js. 1.(40pts)Explain the following terms .Use graph if necessary. (a)Plot a representative potential energy surface diagram for a reaction A+BC-->AB+C at a fixed angle of approach. (b)Two primary assumptions used in the transition state theory. (c)The Eyring equation. (d)The relationship between the Arrhenius parameters for a bimolecular gas phase. (e)The Beer-Lambert's law. (f)Schematically illustrate the absorption/relaxtion/emission process for a diatomic molecule under light exposure. (g)Schematically illustrate and name all process occuring in T1 to S0 transition. (h)Fluorescence resonance energy transfer (i)Describe one mechanism that chlorofluorocarbon destroys ozone. (j)The Einstein relation. (k)Fick's second law (l)The material balance equation for first order reaction. (m)Kohlrausch's law of independent migration of ions. (n)The moving boundary method (o)The cage effect for liquid reactions (p)If a reaction can be catalyzed by H+ and OH- , plot the different variations of logk vs. pH. (q)In the primary kinetic salt effect , schematically illustrate how the rate constant varies with ionic strenth I. (r)For an enzyme reaction ,plot 1/v vs. 1/(S) for competitive,uncompetitive, and noncompetitive inhibition reactions. (s)The Lotka Model. (t)What is (n) for polymer chains synthesized in the step-growth polymerization for manomer conversion ,P=098 ? 2.(8pts)A solution of a dye is irradiated with 400nm light to produce a steady concentration of triplet state molecules. If the triplet state quantum yield is 0.9 , and the triplet state lifetime is 2.0x10^-5 s,what light intensity ,expressed in watts per liter ,is required to maintain a steady triplet concentration of 5.0x10^-6 mol/L in a liter of solution.Assume that all of the light is absorded. 3.(10pts)Based on the simple collision theory we discussed in class in which the reation cross section S is highly energy sensitive with realations: S=0 E<Ec ; S=3.14d^2(1-Ec/E) E>Ec.Derive the rate constant equation for a bimolecular reaction. **CH19 ppt page.8~13 4.(10pts)The uimolecular decomposition of urea in aqueous solution is measured at two different temperature and the following data are observed: data(1)T=333K , k=1.2x10^-7 data(2)T=344.5 , k=4.4x10^-7 (a)Determine the Arrhenius parameters for this reaction (b)Using these parameters , determine H* and S* as described by the Eying equation at T=333K 5.(8pts)For phenanthrene, the measured lifetime of triplet state is 3.3s,the fluorescene quantum yield is 0.12,and the phosphorescene quantum yield is 0.13 in an alcohol-ether class at 77K .Assume that no quenching and no internal conversion from the singlet state occures.Determine Kp ,Kisc, and Kisc/Kf. **CH19 ppt page.73 6.(10pts)The mechanism for formation and destuction of ozone can be explained as follows,Derive the steady state concentration of ozone and explain why the concentration occurs at some altitude on earth. **CH19 ppt page.82~84 7.(15pts)The diffusion coefficient of the protein lysizyme is 1.04x10^-6cm^2/s How long will it take this protein to diffuse an rms distance of 1um in a two dimensional thin water film? 8.(8pts)For acetic acid in dilute aqueous solution at 298K ,K=1.73x10^-5,and the relaxation time is 8.5x10^-9s for a 0.1M solution.Calculate Ka and Kd in CH3COOH---Ka--->CH3COO- + H+ ; CH3COO- + H+ ---Kd---> CH3COOH. 9.(10pts)The following results were obtained when the rate of an enzymolysis was monitored(a)without inhibitor(b)with inhibitor at a concentration of 15x10^-6mol/L: S/10^-4 mol/L 1.0 3.0 7.0 12.0 18.0 (a)v/10^-6mol/sL 0.49 0.95 1.3 1.5 1.6 (b)v/10^-6mol/sL 0.27 0.52 0.71 0.81 0.86 Is the inhibition competitive,uncompetitive,or non-competitive? 10(10pts)Consider a chain polymerization process (a) Initiation I-->R˙+R˙ (b) Propagation M+M1˙-->˙M2...+-->˙Mn (c) Termination (disproportionation) ˙Mn+˙Mm-->Mn+Mm Calculate the average polymer length in a polymer produved by the mechansim. **CH20 ppt page.124~129 Totally 130pts , good luck! --

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