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MCAT-Peterson%27s MCAT Success

MCAT-Peterson%27s MCAT Success

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A. NUCLEAR MAGNETIC RESONANCE

Nuclear magnetic resonance (NMR) is a powerful tool for the determination of
molecular structure. As its name implies, it utilizes the magnetic properties of
atomic nuclei (most commonly using hydrogen nuclei) to infer structural informa-
tion by measuring the energies at which “resonances,” or absorptions of radio
frequency energy, take place.
The nucleus of a hydrogen atom is simply a proton. Like an electron, it can
have two spin states, each one generating a magnetic moment. When no
external magnetic field is present, these states have equal energies, but in the
presence of an external field, alignment of the magnetic moment against the field
corresponds to a slightly higher energy. The difference between the two states is

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proportional to the strength of the external field. The commonly used magnetic
field strength of 14,092 gauss produces an energy gap corresponding to radio
frequency photons having a frequency of 60 MHz (60 3 106

sec21

).
Different hydrogen nuclei within the same molecule will require slightly
different energies to promote them to the excited state. These differences arise
because of shielding by the electrons surrounding the nuclei. A highly shielded
hydrogen nucleus—e.g., one bonded to an electron-donating group—will require a
photon of greater energy for promotion than will a less-shielded nucleus. These
differences are slight, on the order of parts per million, but they can be accurately
measured.

As an example of an nmr spectrum, consider acetaldehyde, CH3CHO. The
three methyl hydrogens all experience an equivalent magnetic environment fairly
well-shielded, since the carbon is not highly electron-withdrawing, while the
hydrogen on the CHO is less shielded owing to the electronegative oxygen
nearby.

The “Acetaldehyde Spectrum” shows it displayed in the conventional way. To
generate the spectrum, the spectrometer varies the applied magnetic field, which
increases to the right on the x-axis, while holding the photon energy of the radio
frequency source constant. (Some spectrometers obtain an identical spectrum by
varying the photon frequency at constant magnetic field.)
Note the following features of the spectrum:

• Each signal corresponds to each kind of proton.
• The step-shaped curves above the signals show the integrated areas
beneath each of those signals; the height of each step is proportional to
the area under the corresponding signal.
• The peak marked TMS gives the radio frequency absorption of a small
amount of the reference compound tetramethylsilane, which is added to
the acetaldehyde. TMS is used because its hydrogens are all equivalent and
are extremely well shielded.

Acetaldehyde Spectrum

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• As anticipated, the absorption of the methyl hydrogens, which were pre-
dicted to be well shielded, is closer to the absorption of TMS than is the ab-
sorption of the CHO hydrogen. The difference between the absorption of a
given hydrogen and that of the reference TMS hydrogens is called the
chemical shift, which is customarily measured in units of “delta,” where
each delta unit is a part per million shift from TMS. The hydrogen on the
CHO is found at 9.9 ppm, while the methyl hydrogens are found at 2.2 ppm.

The table below lists typical values of the chemical shift for common hydrogen-
containing groups. Note that many of the values are variable, depending upon
other atoms or groups in the molecule.

Spin-Spin Coupling

We have so far omitted an important characteristic of nmr spectra, that of
“splitting” of peaks due to interaction of neighboring hydrogens. The acetaldehyde
spectrum provides an excellent example of such splitting.
First, consider the effect of the methyl hydrogens on the NMR absorption by
the CHO hydrogen. If all of the methyl hydrogen nuclei were exactly the same,
there might be a shift in this absorption, but there would be no splitting; how-
ever, since the CH3 hydrogens can be aligned either with or against the external
field, the CHO hydrogen can “feel” either an increase in the total magnetic field
or a slight decrease. The result is a splitting into N 1 1 peaks, where N is the
number of adjacent interacting hydrogens. Here N is 3 (i.e., from the three methyl
hydrogens), resulting in four peaks in the absorption of the CHO hydrogen.
Note that the peak for the CHO hydrogen is split because it has multiple
near-neighbors (and not because there are multiple CHO hydrogens). Note also
that splitting is reciprocal, so that if one group of hydrogens causes a splitting in
the absorption spectrum of a second group, then the converse will also occur.
The NMR signals from —OH groups and —NH groups may be broadened
owing to exchange of protons between different molecules and, in the case of
—NH, owing to the magnetic moment of the nitrogen nucleus. Thus, any broad
peaks may be diagnostic for these functional groups.

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B. INFRARED SPECTROSCOPY

Important structural information about a molecule is revealed by its infrared
spectrum. Absorption of light of the correct infrared frequencies excites molecular
vibrations; e.g., a vibration in which a singly bonded carbon and hydrogen move
back and forth as if their bond were a spring.
Vibrational frequencies measured by infrared spectroscopy are usually
reported in wave numbers, with units of cm21

. The frequency in wave number
units is determined by taking the reciprocal of the wavelength (expressed in cm)
of the exciting photon. Since wavelength is inversely proportional to photon
energy, the frequency in wave numbers is directly proportional to the photon
energy.

A second common means of reporting infrared data is through wavelength
measured in microns (µ), where 1 micron 5 1026

m. The two systems are

related through the expression

frequency (wave numbers) 5 104

/wavelength in microns.

The table below gives some common infrared absorption frequencies. The
exact position of the absorption depends on details of the molecule. In general,
frequencies decrease as the atoms participating in the vibration become more
massive, and increase as the bond order (i.e., single, double) increases.

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An example of an infrared spectrum, that for 1-butene, is shown in the figure
below with some of the absorptions labeled:

Not all vibrations will appear in an infrared spectrum. Those that are found,
which are termed infrared active, are those that alter the dipole moment of the
molecule.

Thus, of the two substituted alkenes,

(a) H2C5CH2

(b) (C2H5—HC5CH2

the C5C stretching frequency will be evident in the spectrum of the less
symmetrical molecule (b), but not (a).

PRACTICE PROBLEMS

1. Amino acids

A. have one amino and one carboxylic
acid group.
B. have low melting points.
C. exist as dipolar ions only.
D. have different ionic forms depending
on the pH.

2. Naturally occurring amino acids

A. have mostly the S configuration.
B. react with each other to form
peptide linkages.
C. are soluble in water.
D. All of the above

3. Which statement is true about the
structures of carbohydrates?

A. Carbohydrates are polyhydroxy
aldehydes or ketones or compounds
that can be hydrolyzed to form them.
B. Carbohydrates include glucose,
starch, and glycogen only.
C. Carbohydrates are all aldohexoses.
D. All carbohydrates are epimers.

4. Glucose anomers differ only

A. by their glycosidic linkages.
B. in their number of carbon atoms.
C. in their configuration about carbon-1.
D. in the number of chiral carbons.

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5. Oils are liquids because they

A. contain cis-unsaturated acid chains
that do not fit well together.
B. contain saturated acid chains that fit
together well due to tetrahedral
bond angles.
C. undergo hydrogenation.
D. have high melting points.

6. Phosphoglycerides are

A. carboxylate esters.
B. phosphate esters.
C. carboxylate esters and phosphate
esters.
D. triacylglycerols.

7. Infrared spectroscopy can generally be
used to distinguish between

A. alcohols and ketones.
B. enantiomers.
C. cis-trans isomers.
D. conformers.

8. The number of signals in the NMR
spectrum of 2-bromopropene is

A. 0
B. 2
C. 3
D. It cannot be determined.

9. The NMR spectrum of CH2Br-CHBr2
shows

A. a triplet downfield and a doublet.
B. two triplets.
C. two doublets.
D. a doublet downfield and a triplet.

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ANSWER KEY AND EXPLANATIONS

1. D

2. D

3. A

4. C

5. A

6. C

7. A

8. C

9. A

1. The correct answer is (D). Some amino acids contain a second acidic group (e.g., aspartic
acid) or a second basic group (e.g., lysine). Glycine is not optically active. In basic solution the
dibasic form of amino acids predominates, while in acidic solution the protonated form is in
highest concentration.

2. The correct answer is (D). Except for glycine, naturally occurring amino acids are optically
active. Stereochemical studies show that all have the S configuration about the carbon atom
bonded to the alpha amino group. Amides are formed by the reaction between amino groups
and carboxyl groups to form peptides. In fact, the —NHCO— group is called a peptide linkage.
Amino acids are nonvolatile crystalline solids with high melting points and are water soluble.
These properties are explained by a dipolar structure, 1H3N—CHR—COO2

.

3. The correct answer is (A). Although glucose, starch, and glycogen are vital biochemical
compounds, there are numerous other carbohydrates. Cellulose, which we use for paper,
clothing, and shelter, is just an example of another carbohydrate. Monosaccharides are aldoses
or ketoses and are usually also pentoses or hexoses. Dissacharides and polysaccharides can be
hydrolyzed to monosaccharides.

4. The correct answer is (C). Aldoses and their glycosides have cyclic structures that can differ
in the configuration about C-1. The C-1—OH is on the right in the a anomer and on the left in
the b glucose anomer.

5. The correct answer is (A). Fats are all glycerides, composed of glycerol and carboxylic acids.
These fatty acids are both saturated and unsaturated, the latter exhibiting mostly cis configura-
tions about the double bonds. Fats with mostly saturated fatty acids have higher melting points
because the tetrahedral carbons fit more tightly together than the cis fatty acid chains, making
for stronger intermolecular forces. Oils or liquid fats have high numbers of unsaturated fatty
acid chains that conversely cause lower melting points.

6. The correct answer is (C). Phosphoglycerides are lipids that are similar to fats but contain
only two acyl groups (R—C⎯⎯O) and a phosphate group in place of the third. The parent
molecule is called diacylglycerol phosphate or phosphatidic acid.

7. The correct answer is (A). The infrared spectrum of an organic molecule gives the most
information about its structure. Each functional group generally has a range of characteristic
absorption frequencies: Carbonyl bonds in aldehydes and ketones absorb at about 1700 cm-1

,

while —OH groups absorb at much higher energies of approximately 3300 cm-1
.

8. The correct answer is (C).

Br

C

C

H

H

CH

3

a

b

c

a,b, and c indicate the three different kinds of protons. a and (b,c) are clearly chemically
inequivalent protons, that is, protons with different environments. b and c, however, are
stereochemically inequivalent, and therefore their environments differ as well. Consequently,
one would expect three NMR signals to match with three different protons.

9. The correct answer is (A). The NMR spectrum has a doublet associated with —CH2

2

protons

because they are split by the —CH2

proton, and a triplet for the —CH2

proton, split by the

two —CH2

2

protons.

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