課程名稱︰物理化學二
課程性質︰化工必修
課程教師︰陳立仁
開課學院：工學院
開課系所︰化工系
考試日期（年月日）︰2007/5/28
考試時限（分鐘）：120min
是否需發放獎勵金：Yes
（如未明確表示，則不予發放）
試題：（範圍Ch.9~10）
Problem 1.(15%)
The variation in the partial pressure of azomethane with time was
followed at 600K, with the results given below.
t/s P/Pa
=========================
0 10.9
1000 7.63
2000 5.32
3000 3.71
4000 2.59
Find out whether the reaction follows zero-, first- or second-order
kinetics and evaluate the rate constant at 600K for the reaction of
decomposition CH3N2CH3(g) -> CH3CH3(g) + N2(g)
Problem 2.(15%)
Identify any initiation, propagation, retardation, inhibition, and
termination steps in the following two chain mechanisms:
(a) (1) AH -> A‧+ H‧
(2) A‧-> B‧+ C
(3) AH + B‧-> A‧+ D
(4) A‧+ B‧-> P
(b) (1) A2 -> A‧+ A‧
(2) A‧-> B‧+ C
(3) A‧+ P -> B‧
(4) A‧+ B‧-> P
Problem 3.(15%)
In an experimental study of a bimolecular reaction in aqueous solution,
the second-order rate constant was measured at 25度C and at a variety
of ionic strengths. The results are tabulated below. It is known that
a singly charged ion is involved in the rate-determining step. What is
the charge on the other ion involved?
I/(mol dm^-3) k/(dm^3 mol^-1 s^-1)
==============================================
0.0025 1.05
0.0037 1.11
0.0045 1.16
0.0065 1.21
Problem 4.(20%)
Many enzyme-catalysed reactions are consistent with a modified version
of the Michaelis-Menten mechanism in which the second step is also
reversible. That is,
ka
E + S ------> ES
k-a
ES ------> E + S
kb
ES ------> E + P
k-b
E + P ------> ES
(a) For this mechanism derive the reaciton rate of the formation of
product P in terms of the substrate and product concentrations.
Anolog to the Michaelis constants defined in the class; also
define the Michaelis constants in this case.
(b) Find the limiting behaviour of theis expression for large and
small concentrations of substrate.
Problem 5.(20%)
The mechanism for the thermal decomposition of F2O by the reaction
F2O(g) -> 2F2(g) +O2(g)
k1
(1) F2O + F2O ------> F + OF + F2O
k2
(2) F + F2O ------> F2 + OF
k3
(3) OF + OF ------> O2 + F + F
k4
(4) F + F + F2O ------> F2 + F2O
Derive a rate law in terms of concentrations of F2O by using the
steady-state approximation.
Problem 6.(15%)
T. Gierczak, R.K. Talukdar, S.C. Herndon, G.L. Vaghjiani, and A.R.
Ravishankara (J. Phys. Chem. A 101, 3125(1997)) measured the rate
constants for the bimolecular gas-phase reaction of methane with
the hydroxyl radical in several isotopic variations. From their
data, the following Arrhenius parameters can be obtained:
A/(dm^3 mol^-1 s^-1) Ea/(kJ mol^-1)
CH4 + OH -> CH3 + H2O 1.13*10^9 14.1
CD4 + OH -> CD3 + DOH 6.0*10^8 17.5
CH4 + OD -> CH3 + DOH 1.01*10^9 13.6
Compute the rate constants at 298K, and interpret the kinetic
isotope effects.
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※ 編輯: Maniacc 來自: 125.228.212.163 (05/29 17:48)