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Atkins & de Paula: Elements of Physical Chemistry 5e

Chapter 20
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Question 1
The transmittance of a 0.015 mol dm -3 aqueous solution of the [Cu(NH3)4]2+ ion was measured to be 0.84 at 600 nm through a cuvette of optical path length 1.0 mm. Determine the molar absorption coefficient. a) 9.0 10-6 dm 3 mol-1 cm -1 b) 6.3 103 dm 3 mol-1 cm -1 c) 5.5 102 dm 3 mol-1 cm -1 d) 50 dm 3 mol-1 cm -1

Question 2
The absorbance of a solution of two laser dyes, cresyl violet and oxazine, was found to be 7.30 10-7 at a wavelength of 350 nm and 7.06 10-6 at a wavelength of 550 nm for a path length of 1.0 cm. Use the following data for the molar absorption coefficients of the dyes at these wavelengths to determine the concentration of cresyl violet in the solution.

a) 0.015 mol dm -3 b) 0.005 mol dm -3 c) 0.010 mol dm -3 d) 0.020 mol dm -3

Question 3
The longest wavelength absorption in the UV visible spectrum of acetone, CH3COCH3, occurs at 335 nm. Predict the energy required to excite an electron from a lone pair orbital on the oxygen atom to an antibonding orbital centred on the carbonyl group. a) 3.70 eV b) 0.270 eV c) 2.99 eV d) 1.67 eV

Question 4
The first ionization energy of nitric oxide, NO, is 9.27 eV. Calculate the velocity of the photoelectrons ejected when a sample of nitric oxide gas using radiation of energy 21.22 eV from a helium lamp source. a) 1.45 106 m s -1 b) 6.36 106 m s -1 www.oup.com/uk/orc/bin/9780199226726/01student/mcqs/ch20/?view=za
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b) 6.36 106 m s -1 c) 2.05 106 m s -1 d) 1.09 106 m s -1

Oxford University Press | Online Resource Centre | Chapter 20

Question 5
The first band in the photoelectron spectrum of hydrogen, H2, occurs close to 15.4 eV and consists of a progression of peaks separated by 285 meV corresponding to transitions to excited vibrational states of the H2+ ion. Calculate the wavenumber of the vibration of the lowest electronic state of the H2+ ion. a) 4400 cm -1 b) 2300 cm -1 c) 2850 cm -1 d) 1760 cm -1

Question 6
The second band in the photoelectron spectrum of oxygen, O2, at 17 eV corresponds to ionization to the excited A2u state of the O2+ ion. The band consists of a long vibrational progression of peaks separated by approximately 900 cm -1. The vibrational wavenumber of the ground X3gelectronic state of a neutral oxygen molecule is 1580 cm -1. Which of the following statements is consistent with the observed photoelectron spectrum? a) Ionization occurs from an antibonding orbital in O2. b) Ionization occurs from a bonding orbital in O2. c) Ionization occurs from a nonbonding orbital in O2. d) It is not possible to make any deductions about the nature of the ionization process.

Question 7
When a solution of iodine, I2, molecules in tetrachlorometane solution is irradiated with radiation of wavelength 436 nm from a 50 W lamp source, the rate of production of iodine atoms by photodissociation when total absorption occurs is 1.45 1020 s -1. Calculate the quantum yield for photodissociation. a) 1.32 b) 0.83 c) 0.66 d) 0.12

Question 8
The quantum yield for the quenching of an excited fluorescing state was measured to be 0.34 with a lifetime of 4.1 ns. Calculate the lifetime of the state in the absence of a quencher. a) 6.2 ns b) 4.8 ns c) 3.4 ns d) 10.1 ns

Question 9
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Oxford University Press | Online Resource Centre | Chapter 20

The decay of photoexcited propanone in the presence of dicyanoethene in solution was investigated by measuring the fluorescence lifetime of the excited state for different concentrations of quencher. By constructing a Stern-Volmer plot of the following data, determine the rate constant for quenching.

a) 3.5 109 mol-1 dm 3 s -1 b) 1.7 109 mol-1 dm 3 s -1 c) 2.9 109 mol-1 dm 3 s -1 d) 4.8 109 mol-1 dm 3 s -1

Question 10
Chlorophyll molecules act as both donors and acceptors in fluorescence resonance energy transfer. The fluorescence lifetime of chlorophyll molecules in a dilute solution of an organic solvent wa found to be 1.2 ns. When chlorophyll molecules were instead embedded in a biopolymer, the fluorescence lifetime was measured to be 820 ps. Given that R0 = 5.6 nm for chlorophyll molecules, estimate the separation between the donoracceptor pairs in the polymer. a) 5.6 nm b) 6.3 nm c) 8.9 nm d) 11.9 nm
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