CHEMISTRY 315

IR, MS, UV SPECTROSCOPY

PROBLEM SET

All Sections

CHEMISTRY 315
IR, MS, UV SPECTROSCOPY PROBLEM SET
Consult the Lab Manual, the textbooks by Solomons and by Pavia, et al., and the following
discussion to help you with the analyses.
In the Lab Manual section, Spectroscopy I, there is a section titled "Using On-line Databases
to Help Solve Organic Chemistry Spectroscopy Problems". You should review it so you can
use on-line sources to help you analyze some of the problem spectra and as a source for
literature spectra. The GMU Organic Chemistry web page
(http://mason.gmu.edu/~sslayden/Lab/index.html) has links to the databases. You really will
find this material easier to master if you take the logical approach outlined in the manual and
in Pavia.
If you are unfamiliar with a compound's name, look it up on-line, or in the textbook, Merck,
CRC, or Aldrich catalog. The Lab Manual has a list of reference sources in the section
"Finding and Citing Information for the Laboratory".
Part I: Answer the questions in the space provided on the page.
1. a) For each of the compounds below, first write a structural formula and then indicate
which of them is likely to absorb in the UV region. Briefly explain your reasoning.
A. cyclohexanol

C6H12O

B. 2,4-hexadienal

C6H8O

C. 2-methyl-5-vinylpyridine

C8H9N

Cyclohexanol is likely to absorb UV. The reason is that it has an OH group on it that have 2
unshared pairs of electrons that absorb the UV.
b) An unknown oxygen-containing compound is suspected of being an alcohol, a ketone, or a
carboxylic acid. Its IR spectrum shows both a broad strong peak at 3100-3400 cm-1 and a sharp
strong peak at 1700 cm-1. What kind of compound is it? Explain what you would see in the
spectra of the two compounds that you did not choose that allows you to differentiate these
three classes of compounds.
The compound is a carboxylic acid as the broad strong peak at 3100-3400 cm-1 corresponds to
C=O bond and the sharp strong peak at 1700 cm-1 corresponds to O-H bond.
For alcohol, a strong broad peak will be observed between 3200-3600 cm-1.
For ketone, a strong medium peak will be observed around 1725 cm-1.

c) Specific compounds are named in the boxes below and the functional group part of the
name is in boldface. For each boldface functional group, draw an expanded structural formula.
Indicate the approximate wavenumbers of the IR absorption peaks that could be used to
distinguish between the members of each of the pairs of compounds in a row. Mention at least
one distinguishing absorption peak for each compound in the pair that is absent in the
spectrum of the other compound (except for the compound in the lower right box).
Example:
acetonitrile and methylamine
CN

NH2 (primary amine)

Nitriles have a CN triple bond stretch at ~2250 cm-1; sharp

Primary amines have an NH stretch around 3500-3300 cm-1 that appears as two bands (the CN
single bond stretch at 1350-1000 cm-1 is weak and difficult to distinguish).

A.

B.

C.

1-propanol

methyl ethyl ether

-OH
Alcohols have a OH single bond
stretch at 3200-3600 cm-1; strong
broad

-CO
Ethers have a CO single bond stretch at
1000-1330 cm-1; strong medium

1-pentyne

1,3-pentadiene

CC
Alkynes have a triple bond stretch at
2100-2200 cm-1; sharp

C=C
Alkenes have a double bond stretch at 1600
- 1680 cm-1; sharp

pentanal

2-pentanone

-CHO
Aldehydes have a C=O bond stretch at
1710-1750 cm-1; strong
They also have a C-H bond stretch at
2820-2850 & 2720-2750 cm-1;
medium, two peaks

-C=O
Ketones have a C=O bond stretch at 17101725 cm-1; medium to sharp

2. Shown on the next page are the IR spectra of the four isomeric butyl chlorides. The spectra
are clearly different, as are their structures. Focus on two of the absorption regions in the
spectra: ~1380 cm-1 and ~525 cm-1. Notice the variability in intensity and appearance of the
peaks in those two regions for the isomers. Mark these regions on the spectra on the next page.
a) For the two IR spectra below, specify in the white space on the spectra, whether they
contain an n-butyl, sec-butyl, isobutyl, or tert-butyl group. Circle the peaks that justify your
choices using the spectra on the next page for comparison. Remember to compare the two
important absorption regions specified above.
b) Which of these two spectra is of an aromatic compound? Mark the peaks that justify your
choice. Put all your answers on this page.

At 1385 cm-1, the above IR spectrum contains two peaks split in the same fashion as of t-butyl
chloride. At 525 cm-1, a sharp strong peak exists for both spectra (above and t-butyl chloride).
Thus, the above molecule contains t-butyl chloride.
This is an aromatic compound as it contains multiple medium weak stretch bands at 14001600 cm-1 which correspond to the C=C bond.

At 1385 cm-1, the above IR spectrum contains a sharp peak of the same fashion as of n-butyl
chloride. At 525 cm-1, the absence of a sharp strong peak for both spectra (above and n-butyl
chloride) indicates that the above molecule contains n-butyl chloride.

3. Go to the NIST web site (http://webbook.nist.gov/chemistry/) and find the mass spectrum
for 2-bromobutane.
To print the mass spectrum, scroll down and click on View image of digitized spectrum (can
be printed in landscape orientation).
Change the page orientation to Landscape in the File | Print| Properties window. If you
get an error message, reload the page and try to print again.
Calculate the molecular weight of 2-bromobutane to guide you where to look for the highest
mass peaks. Remember, the mass spectrum itself will show only the integral mass, not the
molecular weight, which is an average of all the atomic isotopes present in the sample.
Before you leave the website, make sure you write on the printed copy the mass numbers of
the peaks of highest M/z (they may be very small) and several other peaks. It is easier to see
them on the monitor screen than on a black and white printout.
a) On the printed spectrum of 2-bromobutane, indicate the two isotopic molecular ion peaks
and their M/z ratios (refer back to the discussion in the lab manual on MS).
b) On the printed spectrum of 2-bromobutane, indicate the M/z for the peak of greatest
intensity. What fragmentation of the 2-bromobutane accounts for its presence? Draw the
structure of the charged fragment.
Attach the printouts to your other answers from Part I.

Part II: Each Combined Spectra Problem on the following pages contains some combination
of this information: IR spectrum, mass spectrum or molecular ion peak, major UV peak,
element % mass. On each spectrum, neatly label the major absorption peaks with the structural
fragment that causes the absorption. On the answer sheet that follows each problem, fill in the
requested information so that you assemble all the structural information that can be obtained
from the spectra. Then, using this information, propose the structure and identity of the
compound. A logical analysis of the data to support the identification should be written in the
"Combined Analysis" section. You can confirm the identity from literature or on-line sources.
A completed example is given.

Example Spectra Problem The spectra here have been marked to indicate major
absorptions. Other answers are entered on the next page.

Answer to Example Problem

Mass Spectrum Analysis:
The integral molecular weight of the unknown is 88. Because this is an even number, the
compound has either no nitrogen atoms or an even number of N atoms. The highest m/z peaks
do not show evidence of the presence of atoms such as Cl or Br (which would have two peaks
in 75:25 and 50:50 ratios, respectively).
Elemental Analysis:
None was given.
UV-visible Analysis:
No information was given.
IR Analysis:
The absorption at 3000 cm1 (and not to the left) shows only aliphatic (saturated) CH groups.
The carbonyl, C=O, absorbs strongly at 1740 cm1. The two intense peaks between 1000-1300
cm1 indicate the carbonyl belongs to the ester group. The C=O absorption is within the range
for an ester group.
Combined Analysis:
The IR shows the only functional group present is an ester. There is no aromaticity or other
unsaturation in the molecule (except for the C=O). The ester group accounts for 44 amu of the
88 integral mass. The remaining mass (88-44= 44) belongs to one or more hydrocarbon
groups. The basic structure must be R(CO2)R' where R could be a hydrogen bonded to the C
of the ester (but R' cannot be H, since the functional group would be a carboxylic acid, not an
ester).
Since the hydrocarbon group(s) must be saturated, there must be 3 carbons (36 amu) and 8
hydrogens (8 amu) = 44 amu. The molecular formula is thus C3H8O2. If R=H, then R'=
isopropyl or n-propyl. The two remaining possibilities are for R and R' to be methyl and ethyl
(or vice versa). [Note: A more detailed analysis of the fingerprint region would show this is
not either of the propyl formates. A more detailed analysis of the fragmentation in the mass
spectrum would also eliminate these.]
Entering the molecular formula into the search page of an on-line spectroscopy database, and
comparing the known spectra with the unknown's spectra matches only one of the
possibilities.
Unknown Identity: Synonym:
Thus, the unknown is identified as ethyl acetate acetic acid, ethyl ester
Molecular Formula:

Structure:

O
C3H8O2

CH3 C O CH2CH3

1.

Answer to Problem 1
Mass Spectrum Analysis:
The integral molecular weight of the unknown is 106. Because this is an even number, the
compound has either no nitrogen atoms or an even number of N atoms. The highest m/z peaks
do not show evidence of the presence of atoms such as Cl or Br (which would have two peaks
in 75:25 and 50:50 ratios, respectively).
Elemental Analysis:
None was given.

UV-visible Analysis:
No information was given.
IR Analysis:
The absorption at 1600 and 1475 cm1 shows the presence of an aromatic compound. Peaks
greater than 3000 cm-1 further point to the aromatic compound.
Combined Analysis:
The IR shows the molecule is mono substituted aromatic. There is no other unsaturation in the
molecule. Benzene (C6H5) accounts for 77 amu of the 106 integral mass. The remaining mass
(106-77= 29) belongs to one or more hydrocarbon groups.
Since the hydrocarbon group(s) must be saturated, there must be 2 carbons (24 amu) and 5
hydrogens (5 amu) = 29 amu. The molecular formula is thus C8H10.
Entering the molecular formula into the search page of an on-line spectroscopy database, and
comparing the known spectra with the unknown's spectra matches only one of the
possibilities.
Unknown Identity: Synonym:
Thus, the unknown is identified as ethyl benzene ethyl benzol
Molecular Formula:

C8H10

Structure:

2. UV: max 205 nm, log e = 2.2

%C 49.3; %H 9.7

Answer to Problem 2
Mass Spectrum Analysis:
The integral molecular weight of the unknown is 73. Because this is an odd number, the
compound has odd number of N atoms. The highest m/z peaks do not show evidence of the
presence of atoms such as Cl or Br (which would have two peaks in 75:25 and 50:50 ratios,
respectively).
Elemental Analysis:
The elemental analysis indicates the presence of 3 C (0.493 * 73 = 36) atoms and 7 H (0.097 *
73 = 7) atoms. The C3H7 group accounts for 43 amu of the 73 integral mass. The remaining
mass (73-43= 30) belongs to an atom or a group of atoms.
UV-visible Analysis:
No concrete information obtained.
IR Analysis:
The absorption at 3300 cm1 shows the presence of N-H bond. The amide, C=O, absorbs
strongly at 1670 cm1. The C=O absorption is within the range for an amide group.
Combined Analysis:
The IR shows the only functional group present is an amide. There is no aromaticity or other
unsaturation in the molecule (except for the C=O). This implies that the remaining mass (7343= 30) belongs to one N and one O atoms. The basic structure must be R-CO-NH-R,where
both R and R' cannot be H.
The molecular formula is thus C3H7ON. Entering the molecular formula into the search page
of an on-line spectroscopy database, and comparing the known spectra with the unknown's
spectra matches only one of the possibilities.
Unknown Identity: Synonym:
Thus, the unknown is identified as n-methyl acetamide
Molecular Formula:

C3H7NO

Structure:

3. UV: max 280 nm, log e = 1.3

Answer to Problem 3
Mass Spectrum Analysis:
The integral molecular weight of the unknown is 98. Because this is an even number, the
compound has either no nitrogen atoms or an even number of N atoms. The highest m/z peaks
do not show evidence of the presence of atoms such as Cl or Br (which would have two peaks
in 75:25 and 50:50 ratios, respectively).
Elemental Analysis:
None was given.

UV-visible Analysis:
The information shows the presence of a ketone.
IR Analysis:
The absorption at 3000 cm1 (and not to the left) shows only aliphatic (saturated) CH groups.
The absorption at 1465 cm-1 shows the presence of CH2 group. The carbonyl, C=O, absorbs
strongly at 1740 cm1. The absence of alcohols, esters and aldehydes indicates that the
carbonyl belongs to the ketone group. The C=O absorption is within the range for a ketone
group.
Combined Analysis:
The IR shows the only functional group present is a ketone. There is no aromaticity or other
unsaturation in the molecule (except for the C=O). The ketone group accounts for 28 amu of
the 98 integral mass. The remaining mass (98-28= 70) belongs to one or more hydrocarbon
groups. The basic structure must be cyclic molecule bonded to the C of the ketone.
Since the hydrocarbon group(s) must be saturated, there must be 5 carbons (60 amu) and 10
hydrogens (10 amu) = 70 amu. The molecular formula is thus C6H10O.
Entering the molecular formula into the search page of an on-line spectroscopy database, and
comparing the known spectra with the unknown's spectra matches only one of the
possibilities.
Unknown Identity: Synonym:
Thus, the unknown is identified as cyclohexanone
Molecular Formula:

C6H10O

Structure:

4. UV: max 217 nm, log e = 3.8

%C 84.8; %H 7.1

Answer to Problem 4
Mass Spectrum Analysis:
The integral molecular weight of the unknown is 198. Because this is an even number, the
compound has either no nitrogen atoms or an even number of N atoms. The highest m/z peaks
do not show evidence of the presence of atoms such as Cl or Br (which would have two peaks
in 75:25 and 50:50 ratios, respectively). The rule of thirteen points to a molecular formula of
C15H18 or C14H14O.
Elemental Analysis:
The elemental analysis indicates the presence of 14 C atoms and 14 H atoms. The C14H14 group
accounts for 182 amu of the 198 integral mass. The remaining mass (198-182= 16) belongs to
one oxygen atom. The molecular formula is C14H14O.
UV-visible Analysis:
Nothing concrete was obtained.
IR Analysis:
The absorption at 1500 cm1 shows aromatic compound. The aromatic compound is monosubstituted because of a range of peaks between 1600 2000 cm-1. The ether, C-O, absorbs
strongly at 1100 cm1. The C-O absorption is within the range for an ether group.
Combined Analysis:
The IR shows the only functional group present is an ether. There is aromaticity present. The
O atom accounts for 16 amu of the 198 integral mass. The remaining mass (198-16= 182)
belongs to one or more aromatic groups. The basic structure must be ROR'.
Since the aromatic group is mono substituted, there must be 7 carbons (84 amu) and 7
hydrogens (7 amu) = 91 amu. This implies that there are two mono-substituted aromatic
compounds with ether as the functional group between them. The molecular formula is thus
C14H14O.
Entering the molecular formula into the search page of an on-line spectroscopy database, and
comparing the known spectra with the unknown's spectra matches only one of the
possibilities.
Unknown Identity: Synonym:
Thus, the unknown is identified as Benzene, 1,1-[oxybis(methylene)]bisMolecular Formula:

C14H14O

Structure:

5. UV: max 208 nm, log e = 1.5

%C 33.2; %H 4.6

Answer to Problem 5
Mass Spectrum Analysis:
The integral molecular weight of the unknown is 108. Because this is an even number, the
compound has either no nitrogen atoms or an even number of N atoms. The highest m/z peaks
show evidence of the presence of Cl.
Elemental Analysis:
The elemental analysis indicates the presence of 3 C atoms and 5 H atoms. From the mass
spectrum analysis, the presence of Cl is known. The C3H5Cl group accounts for 76 amu of the
108 integral mass. The remaining mass (108-76= 32) belongs to two oxygen atoms. The
molecular formula is C3H5O2Cl.
UV-visible Analysis:
The UV-visible analysis corresponds to the presence of a carboxylic acid.
IR Analysis:
The very broad absorption at 3100 cm1 shows O-H group. The carbonyl, C=O, absorbs
strongly at 1740 cm1. The two intense peaks between 1200-1300 cm1 indicate the carbonyl
belongs to the carboxylic acid group. The C=O absorption is within the range for a carboxylic
acid group.
Combined Analysis:
The IR shows the only functional group present is a carboxylic acid. There is no aromaticity or
other unsaturation in the molecule (except for the C=O).
Entering the molecular formula into the search page of an on-line spectroscopy database, and
comparing the known spectra with the unknown's spectra matches only one of the
possibilities.
Unknown Identity: Synonym:
Thus, the unknown is identified as (S)-(-)-2-chloropropionic acid
Molecular Formula:

C3H5O2Cl

Structure: