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Chemical Physics Letters 431 (2006) 294299

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Rotational isomerism of butanols: Infrared, near-infrared and


DFT study
Mirosaw A. Czarnecki *, Dagmara Wojtkow, Krzysztof Haufa
Faculty of Chemistry, University of Wrocaw, F. Joliot-Curie 14, 50-383 Wrocaw, Poland

Received 7 July 2006; in nal form 26 September 2006


Available online 30 September 2006

Abstract

Infrared and near-infrared spectra of all butanols were recorded in dilute CCl4 solutions as a function of temperature. The stability of
the trans and gauche conformers was evaluated from the temperature dependence of the relative band intensities. The spectra reect var-
ious conformations of the free OH group, whereas the inuence of CC rotations on mOH and 2mOH bands was not observed. The position
of these bands determines the type of conformer resulting from immediate environment of OH group, whereas the relative population of
particular conformers strongly depends on steric eects of the groups in a- and b-position.
2006 Elsevier B.V. All rights reserved.

1. Introduction Many eorts have been undertaken to obtain the theo-


retical spectra of butanols [1723]. From ab initio calcula-
The rotation of an OH group around CO bond gives tions it was found 14 stable conformers of n-butanol [17].
rise to distinct conformers. This eect, known as rotational This number includes the rotations around both the CO
isomerism, has been observed in well-resolved vibrational and CC bonds. In contrast, the matrix isolation spectra
spectra of numerous alcohols in the gas phase, in matrices of n-butanol at 15 and 35 K reveal three and two bands,
or in diluted solutions in apolar solvents [115]. A progress respectively [17]. More recent calculation using the highest
in instrumental and computational methods made possible possible level shows the presence of four stable conformers
to observe the bands due to dierent rotational isomers of n-butanol [18]. Three of the four conformers have the
even in neat alcohols [1116]. In the pure liquid state or same energies within the uncertainty of calculations
in concentrated solutions the monomer absorption is (1 kJ mol 1). Thus, no energetically favoured conformer
obscured by an absorbance of the nonbonded terminal could be found. Based on DFT calculations Xu et al.
OH groups in the open-chain associates [15,16]. Therefore, reported nine stable conformers of sec-butanol [19], while
the spectral measurements in inert solvents are the most in the overtones spectra (Dm = 3, 4 and 5) only two distinct
convenient experimental method for examination of the bands appear. Thus, it was assumed that the seven con-
rotational isomerism [36]. In solution below 0.02 M the formers contribute to the high frequency band (A) and
alcohols are free from the intermolecular hydrogen bond- the two conformers contribute to the low frequency band
ing and under this condition the structure of the OH (B). In the overtones spectra of iso-butanol are observed
stretching band results solely from the presence of distinct three distinct bands including absorption of ve stable con-
rotational isomers. formers found by DFT calculations [20]. The relative ratio
of the band intensities depends on Dm level.
It is commonly assumed that the number of various
hydrogen-bonded species is identical with the number of
*
Corresponding author. Fax: +48 71 3282348. distinct OH stretching bands. However, the OH stretching
E-mail address: mcza@wchuwr.chem.uni.wroc.pl (M.A. Czarnecki). band of numerous alcohols reveals a structure due to the

0009-2614/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2006.09.096
M.A. Czarnecki et al. / Chemical Physics Letters 431 (2006) 294299 295

conformational heterogeneity. Because of continuing inter- a 0.12


est in vibrational studies on hydrogen-bonding, it is impor-
tant to understand which peaks are due to association and
0.09
which to other factors. In the literature one can nd numer-
ous papers dedicated to the rotational isomerism of buta-

Absorbance
nols, yet the available data for dierent butanols were 0.06
obtained in various laboratories and by diverse techniques.
This work, for the rst time, presents the study of the rota-
tional isomerism of all isomers of butyl alcohol in the fun- 0.03
damental and in the rst overtone regions by using the
same experimental and computational methods. This way
all results have similar systematic errors and comparison 0
of the data for dierent butanols is more reliable. An anal- 3550 3600 3650 3700
ysis of the experimental results was supported by the com-
Wavenumbers/cm-1
putational (DFT) studies.

2. Experimental and computational details b


0.12
High purity (>99%) n-butanol (1-butanol), sec-butanol
(2-butanol), iso-butanol (2-methyl-1-propanol), tert-buta- 0.09
nol (2-methyl-2-propanol) and CCl4 were purchased from
Aldrich Chemical Co. (Germany). The chemicals were Absorbance
0.06
dried under freshly prepared molecular sieves (4A). FT-
IR and FT-NIR spectra were measured at a resolution of
2 and 4 cm 1, respectively, on Nicolet Magna 860 spec- 0.03
trometer equipped with DTGS detector, and 512 scans
were accumulated. The sample chamber was purged with 0
dry nitrogen. The spectra were recorded from 20 to 70 C
3550 3600 3650 3700
in thermostated quartz cells (Hellma) of 1 mm (FT-IR) -1
and 10 mm (FT-NIR) thickness. Wavenumbers/cm
The second derivative and Fourier self-deconvolution
procedures were performed with GRAMS/386 (Galactic c 0.3

Inc.). The band envelopes were resolved into a sum of 0.25


Gaussian and Lorentzian functions using Matlab 6.5
(The Math Works Inc.) based software. The integrated 0.2
intensities of both conformers were used with the assump-
Absorbance

tion that the molar absorption coecients of the trans and 0.15
gauche conformers are similar. The relative intensities of
the trans and gauche conformers are temperature-depen- 0.1
dent, yet the total integrated intensity of the OH stretching
vibration in IR and NIR spectra (after the density correc- 0.05
tion) does not depend on the temperature. Besides, a plot
of the integrated intensity of the trans conformer against 0
that of the gauche conformer generates a straight line. 3550 3600 3650 3700
Therefore, one can conclude that the molar absorption Wavenumbers/cm-1
coecients of the trans and gauche conformers are similar
Fig. 1. FT-IR spectra of mOH of n-butanol (a), iso-butanol (b) and sec-
and temperature independent [24]. Density functional butanol (c) together with resolved trans and gauche components. The
(DFT) calculations were carried out at the B3LYP/6- spectra were recorded in 0.01 M CCl4 solution at 20 C.
311G(d,p) level of theory using GAUSSIAN 98 [25].

3. Results and discussion ers of butyl alcohol isomers, the positions of the fundamen-
tal (mOH) and rst overtone (2mOH) bands, the relative
Figs. 1 and 2 show FT-IR and FT-NIR spectra, respec- intensities of both conformers (Ag:At), the enthalpy dier-
tively, of n-butanol, iso-butanol and sec-butanol in 0.01 M ence between the trans and gauche conformers (DHT G),
CCl4 solutions together with the bands due to the trans and and the anharmonicity constants for gauche (Bg) and trans
gauche conformers resolved by curve-tting procedure. In (Bt) rotamers. The positions of the mOH and 2mOH bands
Fig. 3 are displayed Newmans projections of all conform- obtained from curve-tting were similar to those found in
296 M.A. Czarnecki et al. / Chemical Physics Letters 431 (2006) 294299

a 0.16 tert-butanol appears a single band (Fig. 4). Hence, one


can conclude that the rotations around CC bond have
an insignicant eect on the mOH frequency. The same con-
0.12 clusion was drawn by van der Maas et al. from infrared
studies of about 70 monohydric saturated alcohols [3].
Absorbance

The parameters of the primary butanols are similar both


0.08
in IR and NIR regions (Fig. 3). The small but systematic
increase in frequency of the mOH and 2mOH bands on going
0.04
from n-butanol to iso-butanol suggests the presence of the
inductive eect caused by two methyl groups in b-position
for iso-butanol. The population of the trans conformer of
0 the primary butanols is higher than that of the gauche
conformer, yet this eect is more pronounced for iso-buta-
6950 7000 7050 7100 7150 7200 7250
-1
nol (Fig. 3). Clearly, the steric eect caused by two methyl
Wavenumbers/cm groups in b-position makes the gauche position less
favourable. The value of At:Ag for sec-butanol (Fig. 3)
b 0.16
indicates that the gauche conformer is strongly preferred,
whereas the steric interaction by two substituents in a-
0.12 position for the trans conformer appears to be highly
inconvenient. For the same reason the OH stretching fre-
Absorbance

quency in tert-butanol is signicantly red-shifted as com-


0.08 pared with that of the primary butanols and gauche
conformer of sec-butanol (Fig. 3). One would expect sim-
ilar position of the mOH and 2mOH bands for tert-butanol
0.04 and the trans conformer of sec-butanol. Yet, the inductive
eect caused by three methyl groups in a-position signi-
cantly strengthens the OH bond in tert-butanol, whereas
0 this eect is less important for the trans conformer of
6950 7000 7050 7100 7150 7200 7250 sec-butanol. As a result, the OH stretching frequency for
Wavenumbers/cm -1 tert-butanol is blue-shifted relative to that of the trans
conformer of sec-butanol.
c 0.16 As seen in Fig. 3, the same type of rotamers absorbs at
similar positions both in IR and NIR regions. This suggests
that the immediate environment of the OH group deter-
0.12 mines its stretching frequency [5,7]. Another explanation
Absorbance

of this phenomenon was proposed by Krueger et al. [26].


The authors assumed delocalization of the oxygen lone pair
0.08 into the anti-bonding orbital of an a-CH. This eect occurs
when the oxygen lone pair is in the trans position to a-CH
and causes weakening of the CH bond and strengthening
0.04
of the OH bond. The gauche and trans conformers of the
primary alcohols have one and two a-CH in the trans posi-
tion to the oxygen lone pair, respectively. In the trans con-
0
6950 7000 7050 7100 7150 7200 7250
former of sec-butanol and in tert-butanol this eect does
not appear. The separation between IR bands of the trans
Wavenumbers/cm-1 and gauche conformers is 13 cm 1 for the primary butanols
Fig. 2. FT-NIR spectra of 2mOH of n-butanol (a), iso-butanol (b) and sec- and almost 20 cm 1 for sec-butanol (Fig. 3). In the over-
butanol (c) together with resolved trans and gauche components. The tone region these dierences are doubled. The values are
spectra were recorded in 0.01 M CCl4 solution at 20 C. close to those found in Raman spectra of pure 1-octanol
(15 cm 1) and 2-octanol (16 cm 1) [27]. Due to superposi-
tion of dierent CH stretching bands, it was not possible
the second derivative or Fourier self-deconvoluted spectra to observe the eect of weakening of the a-CH bond in
(Fig. 4). The values of Ag:At are the same in both spectral the trans position to the oxygen lone pair. On the other
regions, hence, in Fig. 3 the averaged values are shown. hand, our DFT calculations evidence that this CH bond
In the second derivative and Fourier self-deconvoluted is longer by 0.005 A than that in the gauche position.
spectra of n-butanol, iso-butanol and sec-butanol only two Comparable lengthening of this band was also reported
component bands were found, whereas in the spectrum of by other authors [19,21]. The uncorrected frequencies
M.A. Czarnecki et al. / Chemical Physics Letters 431 (2006) 294299 297

n-butanol gauche, 3627/7083 trans, 3640/7109

Ag:At=1:1.6 n-C3H7 n-C3H7


H
H = 2.0 [kJmol-1] O O
H H H H
Bg/Bt = -85.0/-85.0
H

iso-butanol gauche, 3628/7086 trans, 3642/7112

Ag:At =1:2.6 i-C3H7 i-C3H7


H
H = 2.9 [kJmol-1] O O
H H H H
Bg/Bt = -85.0/-85.5
H

trans, 3609/7043 gauche, 3628/7084 sec-butanol

C2H5 C2H5 At:Ag =1:5.1


H H
O O H = 1.9 [kJmol -1]
H CH3 H3C H
Bg/Bt = -87.5/-86.5

CH3
H
O
C2H5 H

3617/7060 tert-butanol

CH3 B = -86.5
H
O
H3C CH3

Fig. 3. Newman projections of the OH rotational conformers of n-butanol, iso-butanol, sec-butanol and tert-butanol, positions of the mOH and 2mOH
bands, the relative intensities of both conformers (Ag:At), DHTG and the anharmonicity constants for gauche (Bg) and trans (Bt) conformers.

obtained by DFT method are signicantly higher than the butanol absorb at the same position and are spectroscopi-
experimental ones, yet they reproduce a correct order of cally indistinguishable.
the frequencies. The calculated separation between the The anharmonicities of the OH bonds (B = 2mOH/
trans and gauche conformers of n-butanol (14 cm 1) is 2-mOH), are similar for both rotational isomers (Fig. 3). The
close to the experimental value (Fig. 3), while the analo- same conclusion was accomplished by Fang and Compton
gous values for iso-butanol (23 cm 1) and sec-butanol from the overtone studies of various alcohols [28]. The
(30 cm 1) are noticeable higher. primary butanols have the same B, while a small but
In Fig. 3 two distinct gauche conformers of sec-butanol systematic increase of these values occur for sec-butanol
are shown. In spite of many eorts we did not observe the and tert-butanol. Comparable increase in B on going from
individual peaks due to these conformers in the second 1-propanol and 1-nonanol to 2-propanol and 2-nonanol
derivative or Fourier self-deconvoluted spectra. On the was reported by Iwamoto et al. [10].
other hand, the curve tting of the spectra of sec-butanol Plotting ln(At/Ag) versus 1/T one can determine DHTG.
with three peaks (not shown) yields better numerical t Due to overlap of vapour water spectrum with the mOH
than that with two bands (Fig. 2c). Unfortunately, the t- band, the values of DHTG obtained from IR region are less
ting with three bands provides incorrect values of DHTG. reliable than those obtained from the overtone spectra.
Hence, we conclude that both gauche conformers of sec- Thus, in Fig. 3 are shown DHTG evaluated from NIR
298 M.A. Czarnecki et al. / Chemical Physics Letters 431 (2006) 294299

a 0.3 spectra. As can be seen, the values are ranging from 1.9 to
7109
2.9 kJ mol 1. iso-Butanol has higher DHTG than n-butanol
0.25
and sec-butanol, yet due to relatively high experimental
0.2 error (0.5 kJ mol 1) it is dicult to assign a physical
Absorbance

7083
meaning for this dierence. For comparison, Fang and
0.15
Swoord have reported the enthalpy dierence to be
0.1 2.9 0.4 kJ mol 1 for ethanol in the gas phase [1]. The
analogous values for 1-propanol and 2-propanol were 1.7
0.05 and less than 0.4 kJ mol 1, respectively [28]. Our DFT cal-
0
culations at the B3LYP/6-311G(d,p) basis set indicate that
6950 7000 7050 7100 7150 7200 7250 the trans conformer of the primary butanols is more stable
Wavenumbers/cm
-1 than the gauche one, whereas for sec-butanol an opposite is
observed. The DHTG values were 1.2, 1.7 and 0.5 kJ mol 1
b 0.15 for n-butanol, iso-butanol and sec-butanol, respectively.
7112 Though these values are smaller compared to the experi-
0.12
mental ones (Fig. 3), the calculations reproduce correct
order of DHTG for all studied alcohols.
Absorbance

0.09

0.06 4. Conclusions
7086

0.03 Our results evidence that dierent orientations about the


CC axes have minor impact on the mOH frequency. Posi-
0 tion of the mOH and 2mOH bands seems to be determined pri-
6950 7000 7050 7100 7150 7200 7250 marily by the type of conformer resulting from the
Wavenumbers/cm
-1 immediate environment of the OH group. However, DFT
calculations reveal that the eect of delocalization of the
c 0.25
oxygen lone pair into the anti-bonding orbital of the trans
7084
0.2
a-CH should be present as well. The inductive eect of the
methyl groups in a-position shifts the mOH and 2mOH bands
to higher frequencies, whereas the inuence of the methyl
Absorbance

0.15
groups in b-position is hardly seen. In contrast, the relative
0.1 populations of particular conformers strongly depends on
7043
steric eects of the substituents both in a- and b-positions.
0.05 The DFT calculations correctly reproduce the order of the
frequencies and relative energies of both conformers,
0 whereas the absolute values of these parameters signi-
6950 7000 7050 7100 7150 7200
-1
cantly dier from the experimental ones.
Wavenumbers/cm

d 0.3 References
7060
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Absorbance

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