In the Laboratory
Rotational Analysis of FTIR Spectra from Cigarette Smoke
An Application of Chem Spec II Software in the Undergraduate Laboratory
Alan R. Ford, William A. Burns, and Scott W. Reeve*
Department of Chemistry, Arkansas State University, State University, AR 72467; *sreeve@mail.astate.edu
The infrared spectroscopic study of a gas phase molecule
at rotational resolution is a common laboratory experience
for the undergraduate physical chemistry student. Indeed, this
particular experiment is such a staple of the undergraduate
chemistry curriculum that numerous descriptions of the ex-
periment have appeared in this Journal and elsewhere over
the years (1). For practical reasons, 9 of the 16 laboratory
descriptions in reference (1) involve HCl and just four spe-
cies (HCl, C2H2, HBr, CO) are utilized in 15 of the 16 ex-
periments listed. Based on our own experience and
conversations with colleagues at other institutions, we note
there are still a few shortcomings with the rotationally-re-
solved infrared experiment, specifically:
1. Each student typically analyzes the same species. While this
may simplify the lab preparation, it presents the opportu-
nity for inappropriate student collaboration.
2. The experiment and the sample lack a real-world connec-
tion. The typical physical chemistry laboratory experiment
is approached from a purely pedagogical standpoint (i.e.,
an application of quantum mechanics).
3. Data analysis ultimately results in the determination of mo-
lecular structure. Rotation and rotation–vibration spectros-
copy are among the most accurate methods of structure
determination available for gas phase systems. Unfortunately
highlighting the structure determination overlooks the sig-
nificant role rotationally resolved spectroscopic methods play
in the identification of compounds. For example, nearly half
of the species observed in interstellar space were initially stud-
ied and identified in the laboratory (2)!
4. Assigning rotational quantum numbers to the individual
rovibrational transitions is a tedious, often confusing, step
in the data analysis procedure.
A version of the classic gas phase infrared experiment
was developed for students at Arkansas State University that
addresses several of these shortcomings. The experiment es-
sentially combines a novel sample source with Chem Spec II
Figure 1. Infrared spectrum of cigarette smoke acquired at 0.5 cm᎑1
spectral resolution.
www.JCE.DivCHED.org • Vol. 81 No. 6 June 2004
W
analysis software. Chem Spec II is a noncommercial Win-
dows-based software package developed to aid in the poten-
tially complicated problem of assigning quantum numbers
to observed spectral lines (3). Designed originally to tackle
high-resolution infrared diode laser spectroscopic research
problems, the potential to use this in-house software pack-
age in the teaching laboratories was quickly recognized. The
gas phase infrared experiment is described and the capability
of the Chem Spec II software is demonstrated.
Cigarette Smoke as a Sample
Cigarette smoke is a sample source that, until recently
(one of the authors introduced the use of cigarette smoke as
a novel sample source at the 218th Meeting of the American
Chemical Society in August of 1999), has been largely ig-
nored (4). A representative spectrum for cigarette smoke at
one atmosphere total pressure is shown in Figure 1. As a gas
sample, cigarette smoke has several advantages:
• Cigarette smoke is a real-world sample that is of current
interest both from health and pollution aspects.
• Cigarettes are inexpensive and readily available. There is es-
sentially no sample preparation, thus students can concen-
trate on the spectroscopy and data analysis as opposed to
the sample preparation.
• Compared to pure HCl, HBr, CO, and C2H2, cigarette
smoke is relatively safe (HCl and HBr are corrosive, CO is
a flammable poison, and C2H2 is explosive).
• Cigarette smoke contains three components, CO, CH4, and
HCN, that are rotationally resolved at an instrumental reso-
lution of 2 cm᎑1. Students can verify the presence of these
components by analyzing the fundamental vibration of CO
at 2143.7 cm᎑1, the ν3 mode of CH4 at 3020.3 cm᎑1 (a tri-
ply degenerate vibration), and the ν3 mode of HCN at
3311.47 cm᎑1 (the C⫺H stretch) (5). In addition, there are
two infrared active bands of CO2 that can be observed with
an instrumental resolution of 0.5 cm᎑1 (the asymmetric
C⫽O stretch at 2349.3 cm᎑1 and the degenerate bending
mode at 667.3 cm᎑1) (5).
• The multicomponent nature of cigarette smoke provides
flexibility in the manner in which the instructor sets up the
experiment. For example, a traditional approach could be
taken in which students are asked to analyze the spectra of
the known components. In this scenario each student could
be required to analyze each component, or students could
be given different components. Alternatively, the sample
could be treated as an unknown and each student could be
required to identify or analyze a single component or all
the components.
• The experiment presents the opportunity for students to
apply aspects of chemistry discussed throughout their un-
dergraduate career (see Supplemental MaterialW for expla-
nation and discussion).
• Journal of Chemical Education 865
 In the Laboratory

Spectral Analysis Using Chem Spec II Software A

Assigning the appropriate J quantum number to ob-

served rotation–vibration transitions is typically a trial-and-
error process mastered only through practice. Generally the
process requires the observed data be fit several times with
varying J quantum number assignments to determine the
correct assignments. Because intuition is required with such
an approach, it is certainly understandable why this process
might prove difficult or confusing for students. To stream-
line the laboratory experience and minimize the confusion
an alternative, perhaps more pedagogical, method of assign-
ing quantum numbers to transitions would be helpful. A rela-
tively transparent alternative is provided by the infrared
simulation program, Chem Spec II. B
The infrared simulation code, written in C++ and equipped
with a Visual Basic GUI, has been specifically designed to
emulate a spreadsheet program. Chem Spec II is Windows
based, completely menu driven, and allows students to:
1. Generate a simulated rovibrational spectrum given an in-
put set of spectroscopic constants.
2. Overlay the simulated spectrum on an observed spectrum.
3. Make changes to the simulated spectrum by changing the
values of the input constants.
4. Obtain the quantum numbers associated with any rotation–
vibration transition. Figure 2. (A) The infrared prediction routines are accessed via the
Tools menu of Chem Spec II. (B) All of the parameters required for
What makes Chem Spec II novel is that it emulates spread- the spectral simulation are inputted using the IR Prediction Wiz-
sheet programs such as Excel or Quattro Pro. For students ard. Here the rotor type is being selected.
who can cut, paste, plot data, and perform calculations in a
spreadsheet, Chem Spec II represents a straightforward ap-
plication of their computer skills and allows them to focus
on the spectroscopy of the problem.
A
As carbon monoxide is a prominent feature in the ciga-
rette smoke spectra (Figure 1), the capability of Chem Spec
II is demonstrated by examining the absorption region for
the CO fundamental vibration in some detail. To initiate the
simulation, the Predict IR Spectrum option is chosen from a
pull-down menu in Chem Spec II (Figure 2A). Selecting this
option opens a Predict IR Spectrum Wizard dialog box (Fig-
ure 2B). Here the user selects the appropriate parameters to
generate the calculated spectrum. For CO, the linear rotor
type is selected. (Chem Spec II has the capability to generate
spectra for all rotor types.) Other parameters are entered by
highlighting various categories and supplying the requested
information.
Once the necessary information has been entered, the
Output Spectrum option in the Predict IR Spectrum Wizard
dialog box will write the calculated spectrum, complete with B
calculated intensities and quantum number assignments, to
the Chem Spec II spreadsheet. The Predict IR Spectrum Wiz-
ard also allows experimental spectra to be imported with the
Input Spectrum option in the parameter box (see Figure 2B).
Plotting the simulated and experimental spectra is accom-
plished using the built in Chart option located in the Tools
pull-down menu (see Figure 2A). These plots are constructed
following essentially the same sort of procedure for graphing
data in Excel or Quattro Pro. If the predicted stick spectra Figure 3. Rovibrational lines in the infrared spectrum are assigned
does not line up with the experimental data, the spectroscopic by right clicking on any line in the stick spectrum: (A) selecting Get
constants can be varied, perhaps through several iterations, Point Info in the Point menu and (B) recording the quantum number
until the predicted stick spectrum “matches” the observed assignments from the Info for Series X dialog box.

866 Journal of Chemical Education • Vol. 81 No. 6 June 2004 • www.JCE.DivCHED.org


spectrum. This step is actually instructive for students, as they
can observe the effect changing various molecular parameters
has on the position of spectral lines. Students can also change
the value of other parameters, such as the temperature, that
will of course change the intensity and appearance of the ro-
tational contours. Although it is not demonstrated here, both
the x and y axes can be scaled to zoom in or zoom out on
any spectral feature of interest, again using a set of keystrokes
similar to that found in the popular spreadsheet programs.
When the predicted stick spectrum matches the observed
spectrum, quantum number assignments are obtained by
right clicking on the appropriate stick in the predicted spec-
trum. The right click causes a menu box to appear (Figure
3A). By selecting the Get Point Info under the Point menu, a
dialog box pops up that contains the quantum number in-
formation (Figure 3B). Thus, the rotation–vibration transi-
tion highlighted in Figure 3A involves a change in rotational
quantum number of J″ = 12 → J′ = 11. Accordingly, this
transition is assigned as P(12) of the fundamental vibration
of CO.
Chem Spec II is well equipped to handle more compli-
cated molecular systems and the infrared spectrum of ciga-
rette smoke provides a ready source of additional species to
analyze. As indicated previously, rotationally resolved spec-
tra for CH4, CO, CO2, HCN, and H2O can be obtained
from a cigarette smoke sample. The rotational energy analy-
sis for the spherical rotor CH4 for example, is quite similar
to that of the linear rotor. However, coriolis effects must be
included in the simulation for the ν3 band of CH4. Coriolis
effects are included by choosing the Coriolis Effects param-
eter in the Predict IR Spectrum Wizard (Figure 2B). A plot of
the simulated stick spectrum together with the CH4 absorp-
tion spectrum near 3020 cm᎑1 is shown in Figure 4. Quan-
tum number assignments for these rotation–vibration lines
can be obtained following the procedure outlined previously
(see Table II in Supplemental MaterialW for a complete list-
ing of spectral assignments).
Hazards
The hazards associated with this experiment are similar
to those associated with exposure to secondhand tobacco
smoke.
Distribution of Software
Chem Spec II is available and can be obtained, free of
charge, by contacting the authors or at the following Web
site, http://pulaylab.uark.edu/downloads/chemspec2.zip (accessed
Mar 2004). The software has been optimized and tested and
performs well on the Windows XP platform. We have also
recently developed an Excel plug-in version of the program
that will allow students to generate and plot infrared spectra
within the Excel spreadsheet. The Chem Spec II Excel plug-
in is also available free of charge from the authors.
Acknowledgments
The Chem Spec II code was developed as part of an on-
going externally funded research program at Arkansas State
University. Therefore, we would like to acknowledge Research
www.JCE.DivCHED.org • Vol. 81 No. 6 June 2004
In the Laboratory
Figure 4. Chem Spec II generated plot containing the simulated spec-
trum for methane superimposed on the observed infrared spectrum.
Corporation, the Arkansas Biosciences Institute, as well as
the Donors of The Petroleum Research Fund, administered
by the American Chemical Society, for partial support of this
project.
W
Supplemental Material
A detailed description of the laboratory, including tables
of rotational constants and rotation–vibration transition fre-
quencies, available in this issue of JCE Online.
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