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