Chemistry 422 Spring 2013 Practice Exam 1 Name: Instructions: Check the exam to make sure that it contains

exactly 6 different pages, including this one and a periodic table at the end. Some useful constants and equations: RH = 109,737 cm-1 me = 9.11 x 10-31 kg c = 3.00 x 108 m s-1 NA = 6.02 x 1023 mol-1 h = 6.63 x 10-34 J s kB = 1.38 x 10-23 J K-1 E = h c RH(1/ni2 1/nf2) n = 1, 2, 3, .

= h /2

1 amu = 1.661 x 10-27 kg

= h/p
En = n2h2/8mea2,

n (x) = 2 /a sin(nx /a)

E = (N+1)h2/8mea2
= c

= 8mea2c/(N+1)h

= 1/

E=h

xp /2

3N-6 (nonlinear molecule) or 3N-5 (linear molecule) vibrational modes Evib (n + )h, = n = 0, 1, 2,

= 1/2/2 (vibrational frequency) (k/)

= mAmB/(mA+mB) (reduced mass) Erot= J(J +1)h2/82I, J = 0, 1, 2, (2J+1)-degenerate

= r02

n2/n1 = (g2/g1)exp[-(E2-E1)/kBT]

n (x) = Aexp x 2m(V0 E) / 2

(A = constant; particle in barrier)

Part 1. Write the letter of the answer which best satisfies each statement or question in the blank at the left. Please check your answers. Credit will only be given for the

letter written in the blank (3 points each).

1. The energy needed for the hydrogen atom to make a transition from the ground state to first excited state is equal to which of the following? (A) h c RH (B) 3(h c RH)/4 (C) (h c RH)/4 (D) (h c RH)/9 2. If the mass of a particle decreases, the wavelength associated with the particle (A) increases (B) decreases (C) remains the same 3. Which of the following functions is an acceptable wave function over the interval - < x < 0? (A) x2 e-2ix (B) exp(x2/2) (C) exp(-x/2) (D) exp(-|x|/2) 4. Consider a particle in a 3D cubic box. The degeneracy of the first excited state is (A) 1 (B) 2 (C) 3 (4) 4 5. For the particle in a 2D box of length a and width b the energy of the ground state is (A) h2/(8mea2) (B) h2/(8meb2) (C) h2/(8mea2b2) (D) (h2/8me)(1/a2 + 1/b2) 6. To determine the length of a chemical bond in a diatomic molecule, we carry out spectroscopy in which region of the electromagnetic spectrum? (A) UV (B) visible (C) IR (D) microwave 7. Consider a harmonic oscillator wave function with 2 nodes. This wave function corresponds to (A) the ground state (B) the first excited state (C) the second excited state (D) the third excited state 8. The number of vibrational modes of CH4 is (A) 5 (B) 9 (C) 12 (D) 15

9. Beyond the boundaries of the box, where the potential is infinite, the wave function of the particle in the box is (A) an exponential function of the distance from the boundary (B) 0 (C) 1 (D) a sine function of the distance from the boundary 10. Which of the following operators does not commute with (A)

x?
(D)

px = i

(B) x

(C)

py = i

Part II. Short answer: Answer the following in the space provided. (12 points each) 1. The retina of a human eye can detect light when radiant energy incident on it is at least 4.0 x 10-17 J. For light of 600 nm wavelength, how many photons does this correspond to?

2. Suppose that the uncertainty in determining the position of an electron circling an atom in an orbit is 0.4 . What is the uncertainty in velocity?

3. -Carotene has 22 electrons and it absorbs light with = 481 nm. (1 nm = 10-9 m). Estimate the length (in ) of -carotene by assuming that the energy levels of each of its electrons can be calculated as a particle in a box.

Part III. Write your answer to the problems below in the space provided. Please show all work. Partial credit will be given based on work shown. (17 points each) 1. An IR spectrum for carbon monoxide (CO) shows a line at 2143.3 cm-1. (a) Calculate the force constant, k, for the carbon-oxygen bond. (12 points)

(b) Calculate the ratio of the population of CO molecules in the first excited vibrational level to the population of CO in the ground vibrational level at 25 C. (5 points)

2. A microwave spectrum of LiH shows a series of lines separated by 4.511 x 1011 s-1. The first line at 4.511 x 1011 s-1 corresponds to the J = 0 to J = 1 transition. Calculate the length (in ) of the bond between Li and H. (12 points)

(b) Calculate nJ/n0 for J = 1 at 300 K. (5 points)

I________________

II_______________ III______________

Total____________

Periodic Table of the Elements

1 1 2

H
1.00794 3 4 5 6 7 8

H
1.00794 9

He
4.002602 10

Li
6.941 11

Be
9.012182 12

B
10.811 13

C
12.0107 14

N
15

O
16

F
17

Ne
18

14.00674 15.9994

18.9984032 20.1797

Na Mg
22.989770 24.3050 19 20 21 22 23 24 25 26 27 28 29 30

Al
26.981538 31

Si
32

P
33

S
32.066 34

Cl
35.4527 35

Ar
39.948 36

28.0855 30.973761

K
39.0983 37

Ca
40.078 38

Sc
44.955910 39

Ti
47.867 40

V
50.9415 41

Cr
42

Mn
43

Fe
55.845 44

Co
58.933200 45

Ni
58.6934 46

Cu
63.546 47

Zn
65.39 48

Ga
69.723 49

Ge
72.61 50

As
74.92160 51

Se
78.96 52

Br
79.904 53

Kr
83.80 54

51.9961 54.938049

Rb
85.4678 55

Sr
87.62 56

Y
88.90585 57

Zr
91.224 72

Nb
92.90638 73

Mo
95.94 74

Tc
(98) 75

Ru
101.07 76

Rh
102.90550 77

Pd
106.42 78

Ag
107.8682 79

Cd
112.411 80

In
114.818 81

Sn
118.710 82

Sb
121.760 83

Te
127.60 84

I At
(210)

Xe Rn
(222) 118 (293)

126.90447 131.29 85 86

Cs
87

Ba
88

La
138.9055 89

Hf
178.49 104

Ta
180.9479 105

W
183.84 106

Re
186.207 107

Os
190.23 108

Ir
192.217 109

Pt
195.078 110 (269)

Au
196.96655 111 (272)

Hg
200.59 112 (277)

Tl
204.3833

Pb
207.2 114 (289) (287)

Bi
208.98038

Po
(209) 116 (289)

132.90545 137.327

Fr
(223)

Ra
(226)

Ac
(227)

Rf
(261)

Db
(262)

Sg
(263)

Bh
(262)

Hs
(265)

Mt
(266)

58

59

60

61 (145) 93

62 150.36 94 (244)

63 151.964 95 (243)

64

65

66

67

68

69

70

71

Ce
90

Pr
91

Nd
144.24 92

140.116 140.90765

Pm Sm Eu Np
(237)

Gd
157.25 96 (247)

Tb
158.92534 97

Dy
162.50 98 (251)

Ho
99

Er
100

164.93032 167.26

Tm
101 (258)

Yb
102 (259)

Lu
174.967 103

168.93421 173.04

Th

Pa

232.0381 231.03588 238.0289

Pu Am Cm

Bk
(247)

Cf

Es
(252)

Fm
(257)

Md No

Lr
(262)