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Exam 3

Chem 311
Fall 2010
Short answer (10 pts each)
1)

Draw an energy diagram (the Jablonski Diagram) that illustrates why fluorescent
molecules emit less energetic photons than the photons used for excitation? By
contrasting this energy diagram to the energy diagram for a typical molecule that
does not fluoresce, explain why most fluorescent molecules have rigid, aromatic
structures.

2)

Sketch a diagram of a typical UV/vis spectrometer with a diode array detector.

3)

List and describe the different strategies used to insert a sample into the IR beam
of an FT-IR. Why cant a typical cuvette used in UV/VIS applications be used in
conjunction with FT-IR analysis?

4)

The FT-NMR experiment is a pulsed technique? Explain the nature and function
of the pulse.

5)

What is the nature of the reverse-phase HPLC packing (stationary phase)?

6)

Design a reasonable reversed-phase gradient elution HPLC method for the


analysis of a complex mixture of peptides. Identify the compositions of the two
mobile phases A and B and Sketch a plot of % mobile phase B (y-axis) as a
function of run time (x-axis).

7)

Explain why atomic absorption and emission lines are so narrow ( 0.01 nm) and
molecular absorption and fluorescence tend to produce broad spectra that spread
over 50-300 nm.

Multiple Choice (3 pts each)


1.

Which of the following regions of the electromagnetic spectrum consists of


photons that are more energetic than visible light?

A)
B)
C)
D)
E)

IR
Radiowaves
Microwaves
X-rays
All of the above

2.

Energy differences between nuclear spin states can be probed using

A)
B)
C)
D)
E)

IR
Radiowaves
Microwaves
X-rays
Visible

3.

In UV absorption spectroscopy, which of the following statements are true?

A)
B)

E)

* transitions are lower in energy than * transitions.


A conjugated system of double bonds in a molecule shifts the absorption maxima
to higher wavelengths.
A conjugated system of double bonds in a molecule often shifts the absorption
maxima into the infrared region.
A conjugated system of double bonds in a molecule shifts the absorption maxima
to lower wavelengths.
A and C.

4.

A 0.1 M solution of copper (II) nitrate appears blue due to

A)
B)
C)
D)

absorption of blue light by valence electrons.


absorption of orange light by core electrons.
excitation of a d-electron to an f-orbital.
absorption of orange light by ground state d-electrons in an octahedral splitting
configuration.
reflectance of blue light off the cobalt crystals.

C)
D)

E)

5.

Emission from a fluorescent molecule is often measured at a 90 angle to the


excitation beam in efforts

A)
B)
C)
D)
E)

to select the wavelength of maximum excitation.


to select the wavelength of maximum emission
to minimize excitation photons from being scattered in the direction of the
detector.
to increase selectivity.
A and D.

6.

FT-IR is used mostly for

A)
B)
C)
D)
E)

quantification of organic molecules.


functional group analysis of organic molecules.
heavy metal analysis.
molecular weight determination.
structural analysis of organic molecules.

7.

The function of the Michaelson interferometer in an FT-IR instrument is to

A)
B)
C)
D)
E)

disperse the IR radiation as a function of wavelength.


measure the intensity of the IR radiation.
modulate the interference patterns of the light beam from the source.
perform the Fourier Transform on the data.
produce a broad band of IR radiation

8.

In FT-NMR the function of the magnet is to

A)
B)
C)
D)
E)

suspend the sample tube in mid air.


provide a source of radio frequency radiation.
measure the relaxation of the excited nuclei after the pulse.
produce a rapid pulse of radio frequency radiation.
split the degeneracy of the nuclear spin states into two different energy levels.

9.

There are no spin-spin splitting between 13C and 1H nuclei in a typical 13C NMR
experiment because

A)

C)
D)
E)

relaxation of the excited 13C nuclei is too short to allow for effective coupling with
protons.
13
C nuclei make up only about 1% of all carbon, which minimizes the interaction
between the nuclei.
13
C nuclei are excited in a 13C NMR experiment.
molecules generally do not contain equivalent carbon atoms.
broadband decoupling is used by continuously pulsing the proton tuning coil.

10.

The 1H NMR spectrum of CH3CH2COOCH2COOCH3 contains

A)
B)
C)
D)
E)

two triplets, a doublet and singlet.


two singlets, a quartet and a triplet.
one quartet and two doublets.
one triplet, one doublet and two singlets.
four singlets.

B)

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