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Duke University Organic Chemistry Laboratory

Lab

SPECTROSCOPY I IR AND CARBON NMR

Overview

The final two dry labs of Chem 201 (labs 8 and 10), will cover four
Reading Assignments
important spectroscopic methods commonly used to identify and
IR: Loudon1, Sections 12.1B, 12.3 (intro
characterize organic compounds. Thinking back to lab 2 when we first
paragraphs), 12.4.
Carbon NMR: Loudon, pp. 622-628
introduced the scientific method, spectroscopy fits into part five of our
Constitutional Equivalence: section in Lab 2
flowchart: analysis. In this lab we will look at infrared (IR) spectroscopy and
Shielding and Chemical Shift: section in Lab 4
carbon nuclear magnetic resonance spectroscopy (13C NMR). In Lab 10, we will
consider the coupled techniques of gas chromatography-mass spectrometry
(GC/MS) and proton nuclear magnetic resonance spectroscopy (1H NMR). If youve covered these topics in
lecture already, these labs will serve as a reinforcement of these topics. If you have yet to cover these topics,
the labs will serve both as a primer and as a condensed lesson on spectroscopy skills that are needed for
conducting the remaining wet laboratory experiments in Chem 201 and for those who will continue to
Chem 202.

Infrared Spectroscopy
Theory
The entire spectrum of electromagnetic radiation is shown in Figure 1. You are certainly familiar with visible
light, which is a form of electromagnetic radiation detectable to the human eye. Past the lower energy end of
the visible light spectrum is infrared radiation.
The study of how matter interacts with this
radiation is called infrared spectroscopy (IR).
Organic
chemists
primarily
use
IR
spectroscopy as a general method for
identifying functional groups present in a
molecule. Very simply, this technique works
by exposing a sample to a source of IR
radiation. Depending on the identity and
properties of the bonds in the molecules
present, some of this radiation will be
Figure 1. The electromagnetic spectrum. Areas of the spectrum of particular
absorbed by the bonds and some will pass
interest to organic chemists (and their uses): infrared (IR spectroscopy),
through. (As an analogy, if we imagine
ultraviolet (UV-Vis spectroscopy). microwaves (used for heating reactions)
bonded atoms as spheres at the ends of a
gamma rays (the Hulk) and cosmic rays (Fantastic Four). Figure from Ref. 2.
spring, we can visualize the springs
vibrating, bending, twisting, or scissoring depending on the energy input.) What is usually measured is the
percent transmittance, in other words, the IR radiation that is not absorbed by the bonds in the sample, or the
related term, absorbance (absorbance = log(% transmittance/100)).
What this means for chemists in terms of analysis is that we
can use IR to characterize compounds. Each unique compound
has its own unique IR spectrum, reported as % transmittance
or absorbance (vertical axis) versus wavenumbers, or the
inverse of the wavelength (horizontal axis, cm-1). As noted
previously, the most common use of IR is to identify functional
groups present in a compound: a given functional group
always absorbs in the same general region of the spectrum
(Fig. 2). For example, the OH stretch tends to give a broad

Figure 2. Regions of the IR spectrum where peaks

from common bond types and functional groups
tend to appear. Figure adapted from Ref. 3.

Amanda Kasper, Ph.D. Organic Laboratory Manager 1225 French Family Science Center

peak in the 3300-3600 cm-1 range of an IR spectrum. This means that water, ethanol, octanol and cholesterol
will all show a peak in this region; however their fingerprint regions will differ. Additionally, if other
functional groups are present, they too will have corresponding peaks in the spectrum. Look at Appendix II
in Loudon1 (pp. A-3 A-4) and refer to it frequentlyit contains a table of absorbances for most common
functional groups.
Using the Instrument
You will have the opportunity to operate the infrared spectrometers yourself in the Organic Instrument Lab
(FFSC 1236) here at Duke. When you isolate compounds in future experiments in Chem 201 and 202, the
instruments will be available so that you can obtain spectra for your products. After a demonstration on the
proper use of the instruments from your Lab TA, you will be allowed to obtain spectra on your own.

Carbon NMR
Theory
Carbon nuclear magnetic resonance spectroscopy, also called 13C NMR (pronounced carbon 13 NMR) or
CNMR, is a very powerful technique used to determine the structure of organic compounds. Since organic
compounds are primarily comprised of carbon and hydrogen, it makes sense that this technique, along with
1
H NMR (proton NMR), is so useful. In this dry lab and the next you will learn about the different pieces
of information that we can abstract from the NMR spectrum. In lab we will focus on the application of the
technique while in lecture you have covered or will cover the details of the theory behind this method.
Introduction to the basics of an NMR spectrum.4 In 13C NMR we observe a discrete peak (also called a signal or
resonance) representing each chemically inequivalent carbon. The chemical shift value (, in ppm)
designates the position of the peak. Chemical shift values range from 0 to 220 ppm in 13C NMR. The height
of the peak is not indicative of the number of chemical shift equivalent carbons and is considered only
infrequently.
Counting the lines. 13C NMR can be used to quickly determine the number of chemically inequivalent carbons
in a molecule by simply counting the peaks as you learned in Lab 2. For example, see the 13C NMR spectrum
below of 1-bromopropane. There are three peaks corresponding to each of the three carbons in the molecule.
Each carbon occupies a unique chemical environment and therefore has a different chemical shift on the
spectrum.
1-bromopropane

H H

H H

C 2 C
Br 1 C 3 H
H H

Now consider the spectrum of 2-bromopropane (page 3). There are only two peaks in the spectrum despite
the fact that 2-bromopropane contains three carbons. This means that two of the carbons (labeled 2) must
occupy chemically equivalent positions in the molecule and therefore appear at identical chemical shift values.

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Lab 8: Spectroscopy I IR and Carbon NMR

2-bromopropane

H H
H

H H

C 1 C
2 C 2 H
Br H

Another example is cyclopentane, below. Each carbon is equivalent and therefore only one line appears on
the 13C spectrum.
cyclopentane

Chemical Shift. Like infrared spectroscopy, 13C NMR can also be used to gather functional group information.
The chemical shift () is the position of the peak in ppm in reference to a standard compound.
Tetramethylsilane (Si(CH3)4, TMS) is commonly used as a reference and its chemical shift is set at 0 ppm.
The chemical shift of a nucleus is determined by the nature of the nearby groups. In general, increasing the
electron density around a carbon, often called shielding the carbon, will shift the signal towards lower
ppm (closer to TMS). Neighboring electronegative groups decrease the electron density about a carbon (or
deshield the carbon) and shift the signal to higher ppm values (away from TMS). Additionally, carbons with
different hybridizations appear in different locations in the spectra.
You will learn more about the theoretical specifics of this phenomenon in lecture. Also refer to Lab 4 for a
more detailed, practical discussion of chemical shift. In lab we will focus on how we can use this
information to characterize organic molecules. Carbons belonging to each functional group appear in
characteristic and predictable locations in the 13C NMR and this information has been tabulated. See
Appendix IV on page A-7 of Loudon for a detailed table.
By looking at a 13C NMR spectrum you can make a conclusion about the kinds of functional groups present.
For example:
Consider again 2-bromopropane. There are only two peaks corresponding to the two kinds of carbons in the
molecule. One peak appears at 28 ppm corresponding to the alkyl carbon 2 (range 0-50 ppm) and the other

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Lab 8: Spectroscopy I IR and Carbon NMR

at 45 ppm corresponding to the alkyl halide carbon (range 10-90 ppm). The peak with the higher chemical
shift value (45 ppm) corresponds to the carbon adjacent to the electronegative Br atom (carbon 1). Carbon 2
is also deshielded by the electronegative bromine atom, but to a lesser extent and therefore it appears at a
lower chemical shift value (28 ppm).
2-bromopropane

!
2
H H

H H

C 1 C
H 2 C 2 H
Br H

Now consider propionaldehyde (below). There are three peaks corresponding to the three different kinds of
carbons. One would expect that carbon 1 would be found in the range of 120-215 and it does appear at 203
ppm. Carbons 2 and 3 are sp hybridized alkyl carbons expected between 0-50 ppm and found at 37 and 6
ppm, respectively. Carbon 2 is closer to the electronegative aldehyde functional group than is carbon 3 and
is therefore deshielded to a greater extent.
3

Propionaldehyde

!
H H

O
C 2
H 3 C 1 H
H H
!

DEPT. Another common technique used in carbon NMR is Distortionless Enhancement with Polarization
Transfer, or DEPT. Without going too deep into theory here, we can say this technique allows one to obtain
spectra that differentiate between carbons with different numbers of hydrogens attached. In a DEPT-45
spectrum, all carbons with attached hydrogens attached will show resonances, i.e. quaternary carbon signals
are absent. In a DEPT-90 spectrum, only methine carbons (carbons bonded to only one hydrogen, CH)
appear. A DEPT-135 spectrum points all methine and methyl carbon (CH3) signals up, and points methylene
(CH2) carbon signals down. (You can think of this one as odds up and evens down, with quaternary
carbons absent.) An example of propyl benzoate is shown in Fig. 3.

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Lab 8: Spectroscopy I IR and Carbon NMR

3
2
1
2

O
4

5 O

2,3

8
7

3
1

2,3

2,3
1

Figure 35. DEPT spectra of propyl benzoate. The bottom spectrum is DEPT-45, the middle is DEPT-90, and the top is DEPT-135.

Using the Instrument

The Chemistry Department operates a number of NMR spectrometers for teaching and research use.
Unfortunately, due to logistical and time constraints, it is not possible for us to allow the large number of
students in this course to operate the NMR on their own (more advanced courses within the curriculum do
allow for hands-on operation of these instruments). Instead, we will provide you with sample spectra for
compounds you isolate or synthesize, and you will interpret them based on the knowledge gained in lab
and in lecture.

Post-Laboratory Assignment
Log on to saplinglearning.com and complete the assignment associated with this lab. You have from now
until Friday at 5:00 PM to complete this assignment.

References
1

Loudon, GM. Organic Chemistry. 5th ed. Roberts & Company Publishers; 2008

http://local.content.compendiumblog.com/uploads/user/2af9dc1d-8541-42e4-a91f-6aaf97caf33a/4844a17e-a4fb-4018-9d3a31dc846044ee/Visible%20spectrum.jpg
3

Adapted from http://www.biomedcentral.com/content/figures/1471-2342-5-2-2-l.jpg

Parts of this section are excerpts from Sebahar, H.L. Steam Distillation Organic Chemistry Laboratory Handout, Duke University, 2008.

http://upload.wikimedia.org/wikipedia/commons/b/ba/DEPT_spectra.jpg

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Lab 8: Spectroscopy I IR and Carbon NMR