552 CHAPTER 12 • INTRODUCTION TO SPECTROSCOPY.

INFRARED SPECTROSCOPY AND MASS SPECTROMETRY

PROBLEM
12.9 Which of the following vibrations should be infrared-active and which should be infrared-in-
active (or nearly so)?
(a) CH3CH2CH2CH2C' CH C ' C stretch
(b) (CH3)2C A O C AO stretch
(c)
(simultaneous stretch of all C L C bonds)
cyclohexane ring “breathing’’

(d) CH3CH2C' CCH2CH3 C 'C stretch

(e)
..
O

..
symmetrical N—O stretch
H3C N (see resonance structures,
Eq. 1.6, p. 20)
O
..
..

(f) (CH3)3C L Cl
..
CLCl stretch
(g) trans-3-hexene C AC stretch

12.4 FUNCTIONAL-GROUP INFRARED ABSORPTIONS

A typical IR spectrum contains many absorptions. Chemists do not try to interpret every ab-
sorption in a spectrum. Experience has shown that some absorptions are particularly useful
and important in diagnosing or confirming certain functional groups. In this section, we’ll
focus on those. We’ll show you sample spectra so that you will begin to see how these absorp-
tions appear in actual spectra.
We’ll consider here only the functional groups covered in Chapters 1–11. Subsequent chap-
ters contain short sections that discuss the IR spectra of other functional groups. These sections,
however, can be read and understood at any time with your present knowledge of infrared spec-
troscopy. In addition, a summary of key IR absorptions is given in Appendix II.

A. IR Spectra of Alkanes
The characteristic structural features of alkanes are the carbon–carbon and carbon–hydrogen
single bonds. The stretching of the carbon–carbon single bond is infrared-inactive (or nearly so)
because this vibration is associated with little or no change of the dipole moment. The stretching
absorptions of alkyl CLH bonds are typically observed in the 2850–2960 cm_1 region. The
peaks near 2920 cm_1 in the IR spectrum of nonane (Fig. 12.4) are examples of such absorp-
tions. Various bending vibrations are also observed in the fingerprint region (1380 and 1470
cm_1 in nonane) and in the CLH bending region (720 cm_1 in nonane). Absorptions in these

H3CL and LCH2 L groups. Consequently, these absorptions are not often useful, but it is im-
general regions can be expected not only for alkanes but also for any compounds that contain

portant to be aware of them so that they are not mistakenly attributed to other functional groups.

B. IR Spectra of Alkyl Halides

The carbon–halogen stretching absorption of alkyl chlorides, bromides, and iodides appear in
the low-wavenumber end of the spectrum, but many interfering absorptions also occur in this
region. NMR spectroscopy and mass spectrometry are more useful than IR spectroscopy for
determining the structures of these alkyl halides.
Alkyl fluorides, in contrast to the other alkyl halides, have useful IR absorptions. A single
CLF bond typically has a very strong stretching absorption in the 1000–1100 cm_1 region.
 12.4 FUNCTIONAL-GROUP INFRARED ABSORPTIONS 553

Multiple fluorines on the same carbon increase the frequency; for example, a CF3 group typi-
cally has a stretching frequency in the 1300–1360 cm_1 region.

C. IR Spectra of Alkenes
Unlike the spectra of alkanes and alkyl halides, the infrared spectra of alkenes are very useful
and can help determine not only whether a carbon–carbon double bond is present, but also the

Table 12.2. These fall into three categories: CAC stretching absorptions, AC L H stretching
carbon substitution pattern at the double bond. Typical alkene absorptions are given in

absorptions, and A CLH bending absorptions. The stretching vibration of the carbon–carbon

TABLE 12.2 Important Infrared Absorptions of Alkenes

Functional group Absorption*

$ $
$C A C stretching absorptions
$

LCHACH2 (terminal vinyl) 1640 cm_1 (m, sh)

$
$C A CH2 (terminal methylene) 1655 cm_1 (m, sh)

$ $ $ $
H

$C A C $ $C A C
$
H H H 1660–1675 cm_1 (w)
$ $ $ $
(absent in some com-
$C A C $C A C
pounds)
$ $
H

A CL H stretching absorptions
"
ACLH 3000–3100 cm_1 (m)
A CH2

A C L H bending absorptions
L CHACH2 (terminal vinyl) 910, 990 cm_1 (s)
two absorptions
$
$C A CH2 (terminal methylene) 890 cm_1 (s)

$ $
H

$C A C (trans-alkene)
$ 960–980 cm_1 (s)
H

$ $
H H

$C A C$ (cis-alkene) 675–730 cm_1 (br)

(ambiguous and variable for
different compounds)

$ $
$C A C (trisubstituted)
$ 800–840 cm_1 (s)
H

*Intensity designations: s = strong; m = moderate; w = weak

Shape designations: sh = sharp (narrow); br = broad (wide)
554 CHAPTER 12 • INTRODUCTION TO SPECTROSCOPY. INFRARED SPECTROSCOPY AND MASS SPECTROMETRY

wavelength, micrometers
2.6 2.8 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 1516
100

percent transmittance
80

60

40 H
C
C C C
20 H
stretch stretch
H2 C CH(CH2)5CH3
bend 1-octene
0
3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 1000 800 600
(a) wavenumber, cm_1

wavelength, micrometers
2.6 2.8 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 1516
100
percent transmittance

80
almost no C C stretch
60
CH3CH2 H H
40 C C C C
20 H H CH2CH3 bend
stretch
trans-3-hexene
0
3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 1000 800 600
(b) wavenumber, cm_1

Figure 12.10 IR spectra of (a) 1-octene and (b) trans-3-hexene. Be sure to correlate the key bands indicated in
these spectra with the corresponding entries in Table 12.2.

double bond occurs in the 1640–1675 cm_1 range; the frequency of this absorption tends to be
greater, and its intensity smaller, with increased alkyl substitution at the double bond. The rea-
son for the intensity variation is the dipole moment effect discussed in the previous section.
Thus, the C AC stretching absorption is clearly evident in the IR spectrum of 1-octene at 1642
cm_1 (see Fig. 12.10a), but is virtually absent in the spectrum of the symmetrical alkene trans-
3-hexene (Fig. 12.10b). The CAC stretching vibration is weak or absent even in unsymmet-
rical alkenes that have the same number of alkyl groups on each carbon of the double bond.
NMR spectroscopy is particularly useful for observing alkene hydrogens (Sec. 13.7A).

functional group. In general, the stretching absorptions of C L H bonds involving sp2-hy-

Nevertheless, a ACLH stretching absorption can often be used for confirmation of an alkene

bridized carbons occur at wavenumbers greater than 3000 cm_1, and the stretching absorp-
tions of C L H bonds involving sp3-hybridized carbons occur at wavenumbers less than 3000
cm_1. Thus, 1-octene has a A C LH stretching absorption at 3080 cm_1 (Fig. 12.10a), and
trans-3-hexene has a similar absorption which is barely discernible at 3030 cm_1 (Fig.
12.10b). The higher frequency of AC LH stretching absorptions is a manifestation of the
bond-strength effect: bonds to sp2-hybridized carbons are stronger (Table 5.3, p. 213), and
stronger bonds vibrate at higher frequencies.
 12.4 FUNCTIONAL-GROUP INFRARED ABSORPTIONS 555

The alkene A C LH bending absorptions that appear in the low-wavenumber region of the
IR spectrum are in many cases very strong and can be used to determine the substitution pat-
tern at the double bond. The first three of these absorptions in Table 12.2—the ones for termi-
nal vinyl, terminal methylene, and trans-alkene—are the most reliable. The 910 and 990 cm_1
terminal vinyl absorptions are illustrated in the IR spectrum of 1-octene (Fig. 12.10a), and the
trans-alkene absorption is illustrated by the 965 cm_1 peak in the IR spectrum of trans-3-hex-
ene (Fig. 12.10b).

Study Problem 12.3

Each of three alkenes, A, B, and C, has the molecular formula C5H10 , and each undergoes catalytic
hydrogenation to yield pentane. Alkene A has IR absorptions at 1642, 990, and 911 cm_1; alkene
B has an IR absorption at 964 cm_1, and no absorption in the 1600–1700 cm_1 region; and alkene
C has absorptions at 1658 and 695 cm_1. Identify the three alkenes.

Solution In this problem, you can write out all the possibilities and then use the IR spectra to
decide between them. The molecular formulas and the hydrogenation data show that the carbon
chains of all of the alkenes are unbranched and that all are isomeric pentenes. Hence, the only
possibilities for compounds A, B, and C are the following:

$ ) $ )
H3C CH2CH3 H3C H

) $ ) $
H2C A CHCH2CH2CH3 CAC CAC
1-pentene H H H CH2CH3
cis-2-pentene trans-2-pentene

The C L H bending absorptions of A at 990 cm_1 and 911 cm_1 indicate that it is a 1-alkene; thus,
it must be 1-pentene. The 964 cm_1 C LH bending absorption of B shows that it is trans-2-pen-
tene. (Why is the CAC stretching vibration absent?) The remaining alkene C must be cis-2-pen-
tene; the 1658 cm_1 C AC stretching absorption and the 695 cm_1 CL H bending absorption are
consistent with this assignment.
Notice that you do not need the complete IR spectrum of each compound, but only the key
absorptions, to solve this problem.

PROBLEMS
12.10 Five isomeric alkenes A–E each undergo catalytic hydrogenation to give 2-methylpentane.
The IR spectra of these five alkenes have the following key absorptions (in cm_1):

Compound B: 833 (s), 1667 (w), 3050 (weak shoulder on C LH absorption)

Compound A: 912 (s), 994 (s), 1643 (s), 3077 (m)

Compound C: 714 (s), 1665 (w), 3010 (m)

Compound D: 885 (s), 1650 (m), 3086 (m)
Compound E: 967 (s), no absorption 1600–1700, 3040 (m)
Propose a structure for each alkene.
12.11 One of the spectra in Fig. 12.11 (p. 556) is that of trans-2-heptene and the other is that of 2-
methyl-1-hexene. Which is which? Explain.
556 CHAPTER 12 • INTRODUCTION TO SPECTROSCOPY. INFRARED SPECTROSCOPY AND MASS SPECTROMETRY

wavelength, micrometers
2.6 2.8 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 1516
100

percent transmittance
80

60

40

20

0
3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 1000 800 600
(a) wavenumber, cm_1

wavelength, micrometers
2.6 2.8 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 1516
100
percent transmittance

80

60

40

20

0
3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 1000 800 600
(b) wavenumber, cm_1

Figure 12.11 IR spectra for Problem 12.11.

D. IR Spectra of Alcohols and Ethers

When OLH groups are not hydrogen-bonded to other groups, the O LH stretching absorption
occurs near 3600 cm_1. However, in most typical samples, the OLH groups are strongly hydro-
gen-bonded and give a broad peak of moderate to strong intensity in the 3200–3400 cm_1 region
of the IR spectrum. Such an absorption, which is an important spectroscopic identifier for alco-
hols, is clearly evident in the IR spectrum of 1-hexanol (see Fig. 12.12).
The other characteristic absorption of alcohols is a strong CL O stretching peak that oc-
curs in the 1050–1200 cm_1 region of the spectrum; primary alcohols absorb near the low end
of this range and tertiary alcohols near the high end. For example, this absorption occurs at
about 1060 cm_1 in the spectrum of 1-hexanol. Because some other functional groups, such as
ethers, esters, and carboxylic acids, also show C L O stretching absorptions in the same gen-
eral region of the spectrum, the C LO stretching absorption is mainly used to support or con-
firm the presence of an alcohol diagnosed from the OLH absorption or from other spectro-

The most characteristic infrared absorption of ethers is the C L O stretching absorption,

scopic evidence.

which, for the reasons just stated, is not very useful except for confirmation when an ether is

have strong C LO stretching absorptions near 1100 cm_1.

already suspected from other data. For example, both dipropyl ether and an isomer 1-hexanol
 12.5 OBTAINING AN INFRARED SPECTRUM 557

wavelength, micrometers
2.6 2.8 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 1516
100

percent transmittance
80

60

40 C O
stretch
CH3(CH2)4CH2OH
20
O H 1-hexanol
stretch
0
3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 1000 800 600
wavenumber, cm_1

Figure 12.12 IR spectrum of 1-hexanol. Note particularly the broad OL H stretching absorption.

wavelength, micrometers
2.6 2.8 3 3.5 4 4.5 5 5.5 6 7 8 9 10 11 12 13 14 1516
100
percent transmittance

80

60

40

20

0
3800 3400 3000 2600 2200 2000 1800 1600 1400 1200 1000 800 600
wavenumber, cm_1

Figure 12.13 IR spectrum for Problem 12.12.

PROBLEMS
12.12 Match the IR spectrum in Fig. 12.13 to one of the following three compounds: 2-methyl-1-
octene, butyl methyl ether, or 1-pentanol.
12.13 Explain why the IR spectra of some ethers have two CL O stretching absorptions. (Hint:
See Fig. 12.8, p. 549.)
12.14 Explain why the frequency of the O LH stretching absorption of an alcohol in solution
changes as the alcohol solution is diluted.

12.5 OBTAINING AN INFRARED SPECTRUM

Infrared spectra are obtained with an instrument called an infrared spectrometer. In its sim-
plest concept, the IR spectrometer provides a way to carry out the absorption spectroscopy ex-
periment shown in Fig. 12.3 (p. 539). The instrument houses a source of infrared radiation, a