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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.
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
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.
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
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
0.15
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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