110年 - [非官方正解]110台灣聯合大學系統_碩士班招生考試_化學類:物理化學#104949

科目：研究所、轉學考(插大)◆物理化學 | 年份：110年 | 選擇題數：23 | 申論題數：5

試卷資訊

所屬科目：研究所、轉學考(插大)◆物理化學

選擇題 (23)

1. According to Marcus theory, which of the following factor does NOT influence the electron transfer rate constant? (A) Reorganization energy. (B) Gibbs energy difference between the product and reactant. (C) Angular momentum of electron (D) Distance between electron donor and acceptor. (E) Type of spacer between electron donor and acceptor.
2. The energy levels of the linear harmonic oscillator are (A) all nondegenerate (B) n-fold degenerate (C) (n+12 )-fold degenerate (D) (2n + 1)-fold degenerate (E) n2 -fold degenerate

3. The illustrated wave function represents the state of the linear harmonic oscillator with n =61badda197c62.jpg (A) 2 (B) 3 (C) 4 (D) 5 (E) 6

4. There is one state at e = O and there are two states at ε = 61baddbe32b29.jpg . According to the Boltzmann distribution, the population of second state is 0.15. What is the temperature (K)? (A) 180 K (B) 300K (C) 480 K (D) 90 K (E) ＞ 1000 K
5. The rate constant of a chemical reaction is NOT determined by (A) steric requirement (B) encounter rate (C) minimum energy requirement (D) temperature (E) standard reaction free energy
複選題
6. Spherical polar coordinates are used in the solution of the hydrogen atom Schrodinger equation because (A) the Laplacian operator has its simplest form in spherical polar coordinates. (B) Cartesian coordinates would give particle-in-a-box wave functions. (C) the Schrodinger equation is then separable into 3 ordinary differential equations. (D) Otherwise the atomic orbitals would violate the Pauli Exclusion Principle. (E) Schrodinger first used this coordinate system； any other coordinate system would be equally convenient.

7. Consider the thermal decomposition of 1 atm of (CH3)3COOC(CH3)3 to acetone (CH3)2CO and ethane (C2H6), which occurs with a rate constant of 0.02 61bade164ae97.jpg. After initiation of the reaction, at what time would you expect the pressure to be 2.0 atm? (A) 693 sec (B) 34.65 sec (C) 263 sec (D) 699 sec (E) Can not be determined.
8. Molecules are known to absorb radiation in which region of the electromagnetic spectrum: (A) UItraviolet (B) visible (C) infrared (D) microwave (E) all of the above

9. The van der Waals equation is expressed as 61bade2cb4c05.jpg = nRT. Which of
the following statement is true?
(A) Compression factor Z ＜ 1 when a/(RT) ＞ b.
(B) Compression factor Z ＜ 1 when a/(RT) ＜ b.
(C) Compression factor Z ＜ 1 when a/(RT2) ＜ b.
(D) Compression factor Z ＜ 1 when a ＜ b(RT).
(E) All of the above is incorrect.
10. Which of the following is "NOT" a correct aspect of the Born-Oppenheimer approximation (A) The electrons in a molecule move much faster than the nuclei. (B) Excited electronic states have the same equilibrium inter-nuclear distance as the ground electronic state. (C) The electronic and vibrational motions of a molecule are approximately (D) Electronic energy curves serve as potential energy functions for nuclear vibrational 3 motions. (E) The typical amplitude of nuclear vibration is much smaller than that characterizing the motion of electrons.
11. The benzene molecule C6H6 has how many vibrational modes (A) 6 (B)12 (C)24 (D)30 (E) 36 separable.

12. For the reaction A + B → product, the reaction rate is first order to A and first order to B. Integrate the rate law. [AJo and [B]o are the initial concentrations for A and B, respectively and [A]o is not equal to [B]o. t = time. (A) 61badea6440bc.jpg(B) 61bae15fd2806.jpg (C) 61bae167e1c1b.jpg (D) 61bae1718a985.jpg (E) All of the above is incorrect. 
13. The normal boiling temperature of ethanol is 78.5℃ and its molar enthalpy change of vaporization at this temperature is 40.3 kJ/mol. Find AU when 3.000 mol of ethanol are vaporized at 78.5℃ at a constant pressure of 1.000 atm. Neglect the volume of the liquid compared with that of the vapor and assume the ethanol vapor as an ideal gas. (A) △U = 120.9 kJ (B) △U = 0.0 kJ (C) △U = -8.77 kJ (D) △U = 130.1 kJ (E) △U= 112.1 kJ

14. The ionization energy for hydrogen atom is 13.6 eV. The ionization Energy for the ground state of 61bae2b472e7b.jpg is approximately (A)13.6(B)27.2(C)40.8 (D)54.4 (E) 122.4 eV
15. Which of the following is NOT a correct consequence of the Heisenberg Uncertainty principle: (A) The shorter the lifetime of an excited state of an atom, the less accurately can its energy be measured. (B) An electron in an atom cannot be described by a well-defined orbit. (C) The momentum of an electron cannot be measured exactly. (D) Measurement of one variable in an atomic system can affect subsequent measurements of other variables. (E) A harmonic oscillator possesses a zero-point energy.

16. The Joule coefficient, u, is defined as 61bae2d051088.jpg. a is the thermal expansion coefficient. 61bae2ea74f34.jpg is the isothermal compressibility. Which of the following equation is correct? (A)61bae4b4c3f9e.jpg(B) 61bae4c592917.jpg(C) 61bae4d6c1851.jpg (D) 61bae4df4bdd8.jpg (E)61bae4ef60ed3.jpg
17. The orbital degeneracy (excluding spin) of hydrogen atom energy levels equals (A)n-1(B)n(C)n+1(D) 2n+1(E)n2

18. The change in enthalpy is given by dH = 61bae5158b453.jpg+ Vdp. In combination with the Clapeyron equation, find out d(△H/T) and the two phases remain in equilibrium. (A) 61bae56033807.jpg (B) d(△H/I) = Rd(In T) (C) d(△HIT) =△S d(In T) (D) 61bae574610c3.jpg (E) All of the above is incorrect
19. Which of the following statements about the hydrogen atom ground state is INCORRECT: (A) It is described by the quantum numbers n =1； 1 = 0； m = 0. (B) The electron's angular momentum equals plank constant, h. (C) The wave function is spherically symmetrical. (D) The wave function decreases exponentially as a function of r. (E) The radial distribution function has its maximum at the Bohr radius.
20. At the solid-liquid-vapor triple point of a pure substance, what is the slope, dp/dT of phase transition? (A) solid-vapor line ＞ liquid-vapor line (B) solid-vapor line = liquid-vapor line (C) solid-vapor line ＜ liquid-vapor line (D) solid-vapor line = liquid-vapor line = 0 (E) all of the above is incorrect

21. Based on statistical thermodynamics, which of the following statement about heat
capacity is true?
(A) The 61bae59361538.jpg for Ar is the same as that for Ne, even though the atomic weight of Ar
is twice that of Ne.
(B) The heat capacity for monoatomic atom F is considerably larger than that for
Ne even though they have about same atomic weight.
(C) The heat capacity of liquid water is much larger than that of water vapor.
(D) Br2(g) has larger 61bae5b38e984.jpg value than that of Cl2(g).
(E) The 61bae5c75c436.jpg values for the Ar, O2(g), and Cl2(g) are in the order of Cl2(g) ＞ O2(g) ＞
Ar.
複選題

22. The velocity probability of Maxwell-Boltzmann distribution in one-direction is expressed as: 61bae5fa05724.jpg. Which of the following statement about Maxwell- Boltzmann distribution at a finite T is true? (A) The most-probable velocity for a one-dimensional gas velocity distribution is zero. (B) The Maxwell-Boltzmann speed (three dimensions) distribution approaches zero at high speeds. (C) The Maxwell-Boltzmann speed (three dimensions) distribution approaches zero at low speed. (D) The total energy of one mole perfect gas according to the Maxwell-Boltzmann distribution is 1.5RT. (E) Most-probable speed ＞ Mean speed ＞ Root mean square speed.
複選題
23. Consider the collision-induced dissociation of N2Os(g) via the following mechanism: 
61bae61a15607.jpg
The * symbol in the first reaction indicates the reactant is activated through collision. Experimental ly, it is observed that the reaction can be either first or second order under different conditions. The rate law is expressed as 61bae62f14ed9.jpg. Which of the following statement is true? (A)m = 2. (B) k'=k1 (C)61bae64b1aa4b.jpg (D)When 61bae66c2d4a0.jpg, the reaction will be first order in N2O5(g). (E) When 61bae67e18def.jpg, the reaction will be half order in N2O5(g).

申論題 (5)

1. Assume the molar Gibbs free energy of a gas is given by the equation: 61bae6ab34419.jpg, where po is the standard pressure and a and b are gas-dependent constants. Derive an equation of state for this gas. Show the final result in the form of PV = ?.
(a) Set up the Secular Determinant and solve for the energy of the Bonding and Anti-Bonding Orbitals

(b)  Use your answer in part (a) to calculate the coefficients, 61bae70e51454.jpgand C1, in the Normlized anti-bonding orbital. If you are not sure of the energy, then use 61bae726a7490.jpg = -8.0 eV to work out this part.

(c)  Assume for this part that the bonding orbital is:
61bae74168292.jpg
What fraction of the charge of an electron in the bonding orbital is on the lodine
atom?

3. Consider a transition between the ground state (Ψ0) and the i'th excited state61bae79ab52b7.jpg. Time dependent perturbation theory can be used to show that the intensity of the absorption is proportional to the square of the "transition moment",61bae7a8a1efb.jpg. The x, y and z components of the transition moment are: .
61bae76b0b162.jpg
In the case of Carbene, it has C2v symmetry has 8 electrons and the Triplet Ground state takes the electronic configuration (a1)2(a1)2(b2)2(a1)1(a1)1 as shown in the following diagram where the shape of the molecular orbital are also included
61bae84955fd2.jpg
Please determine if the electronic transition (only the highest two unpaired
electrons are shown and the paired inner orbitals are neglected) is UV allowed
or forbidden.
61bae858c61a8.jpg
For your information, the character table for C2V symmetry is:
61bae867681dd.jpg