Dataset Papers in ChemistryVolume 2013 (2013), Article ID 329406, 6 pageshttp://dx.doi.org/10.7167/2013/329406

Dataset Paper

Infrared Absorption Spectra of Monohydric Alcohols

Irina Doroshenko,¹ Valeriy Pogorelov,¹ and Valdas Sablinskas²

¹Physics Department, Taras Shevchenko National University of Kyiv, 4 Glushkova Avenue, Kyiv 01601, Ukraine²Physics Department, Vilnius University, 9-3 Sauletekio Avenue, 01513 Vilnius, Lithuania

Received 20 April 2012; Accepted 17 May 2012

Academic Editors: C. Bock, P. Fuentealba, M. Koyama, and R. Spezia

Copyright © 2013 Irina Doroshenko et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

FTIR spectra of homologous series of monohydric alcohols which belong to the class of partly ordered liquids were registered. The molecules of monohydric alcohols containing hydroxyl group are able to form hydrogen-bonded clusters in the condensed phase. The existence of clusters is clearly observed from the position and the contour of the stretch OH band in the vibrational spectra of liquid alcohols. In this work, the experimentally registered FTIR spectra of liquid n-alcohols from methanol to decanol are presented as well as the same spectra of methanol, ethanol, propanol, butanol, pentanol, and hexanol in gas phase.

1. Introduction

The clustering phenomena and structural peculiarities of partly ordered liquids are of great interest in the scientific community. This interest is even growing in context of recent trends and developments in studies on modern multifunctional materials, heterogeneous systems, and nanotechnologies. Among such partly ordered liquids are monohydric alcohols that usually build broad variety of H-bond aggregates. They are quite simple and convenient models to investigate properties of molecular systems sized over the mesoscopic scale (~1–100 nm).

The cause of cluster formation in alcohols is the intermolecular hydrogen bond. The vibrational spectra of liquid alcohols differ from their spectra in gas phase or in matrix by the absence of the vibrational band of free hydroxyl group vibrations. Instead of this, the red-shifted diffuse band, which is usually associated with the presence of molecular aggregations (clustering), is observed. However the mechanism of the diffuse band formation and its structure are still the unsolved problems. The importance of the problems connected with the alcohol clustering and structure and, in particular, with the mechanisms of the diffuse absorption band formation is reflected in the great number of experimental [1–9], theoretical [10–14], and combined works [15–19] published in the recent years.

The properties of a great number of partly ordered liquids are determined mainly by the characteristics of the hydrogen bond network. Monohydric alcohols are the convenient objects for the investigation of such intermolecular interaction as hydrogen bond. In this work, we present the experimentally registered FTIR spectra of the homologous series of monohydric alcohols in liquid and gaseous states.

2. Methodology

The experimental registration of the presented spectra was made in the laboratory of Fourier transform infrared absorption spectroscopy at the Physics Department of Vilnius University, Lithuania. All spectra were registered using Bruker’s FTIR spectrometer VERTEX 70 in the spectral range from 750 to 4000 cm⁻¹. In order to increase signal-to-noise ratio, each spectrum was taken as an average of 128 scans. Liquid-phase samples of the monohydric alcohols with purity >99.9 from Fluka were used as received. Gas-phase samples were obtained by the natural evaporation in vacuum process from the liquid surface.

Spectra of liquid n-alcohols were registered by attenuated total reflection (ATR) method at the resolution 4 cm⁻¹. The spectrometer was equipped with liquid-N₂-cooled mercury cadmium telluride (MCT) detector. Blackman-Harris 3-term apodization function and zero filling 2 were used during processing of interferograms. Single-pass ZnSe ATR crystal was used for capturing of the ATR spectra. Angle of incidence of IR beam was set to 70 degree, what insured total reflection from ZnSe-alcohol interface for all the title alcohols.

Spectra of the alcohols in gaseous state were measured using conventional single-pass 10 cm gas cell equipped with KBr windows with the resolution 0.5 cm⁻¹ using deuterated triglycine sulfate (DTGS) detector. Blackman-Harris 3-term apodization function and zero filling 128 were used during processing of interferograms. Pressure of each alcohol was set close to its saturated pressure at 20°C: 13 mbar for methanol, 5.5 mbar for ethanol, 2 mbar for 1-propanol, 0.7 mbar for 1-butanol, 0.2 mbar for 1-pentanol, and 0.1 mbar for 1-hexanol.

The gas cell was filled with an alcohol using standard vacuum technique. Atmospheric oxygen and nitrogen were removed from the alcohols by five freeze-pump-thaw cycles.

In this paper, the experimentally registered Fourier transform infrared absorption (FTIR) spectra of the first ten members of the homologous series of monohydric alcohols with the linear structure of the molecule CH₃–(CH₂)n–OH, n = 0–9, in liquid phase are presented.

The registered by authors at room temperature FTIR spectra of liquid methanol (CH₃OH), ethanol (C₂H₅OH), propanol (C₃H₇OH), butanol (C₄H₉OH), pentanol (C₅H₁₁OH), hexanol (C₆H₁₂OH), heptanol (C₇H₁₅OH), octanol (C₈H₁₇OH), nonanol (C₇H₁₅OH), and decanol (C₁₀H₂₁OH) are presented in Figures 1–10, respectively. The recorded by authors FTIR spectra of gaseous alcohols at room temperature (methanol, ethanol, propanol, butanol, pentanol, and hexanol) are presented in Figures 11–16, respectively.

Figure 1: FTIR spectrum of liquid methanol CH₃OH.

Figure 2: FTIR spectrum of liquid ethanol C₂H₅OH.

Figure 3: FTIR spectrum of liquid propanol C₃H₇OH.

Figure 4: FTIR spectrum of liquid butanol C₄H₉OH.

Figure 5: FTIR spectrum of liquid pentanol C₅H₁₁OH.

Figure 6: FTIR spectrum of liquid hexanol C₆H₁₃OH.

Figure 7: FTIR spectrum of liquid heptanol C₇H₁₅OH.

Figure 8: FTIR spectrum of liquid octanol C₈H₁₇OH.

Figure 9: FTIR spectrum of liquid nonanol C₉H₅₁₉H.

Figure 10: FTIR spectrum of liquid decanol C₁₀H₂₁OH.

Figure 11: FTIR spectrum of gaseous methanol.

Figure 12: FTIR spectrum of gaseous ethanol.

Figure 13: FTIR spectrum of gaseous propanol.

Figure 14: FTIR spectrum of gaseous butanol.

Figure 15: FTIR spectrum of gaseous pentanol.

Figure 16: FTIR spectrum of gaseous hexanol.

3. Dataset Description

The dataset associated with this Dataset Paper consists of 16 items which are described as follows.

Dataset Item 1 (Spectrum). FTIR spectrum of liquid methanol CH₃OH (Figure 1). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 2 (Spectrum). FTIR spectrum of liquid ethanol C₂H₅OH (Figure 2). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 3 (Spectrum). FTIR spectrum of liquid propanol C₃H₇OH (Figure 3). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 4 (Spectrum). FTIR spectrum of liquid butanol C₄H₉OH (Figure 4). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 5 (Spectrum). FTIR spectrum of liquid pentanol C₅H₁₁OH (Figure 5). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 6 (Spectrum). FTIR spectrum of liquid hexanol C₆H₁₃OH (Figure 6). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 7 (Spectrum). FTIR spectrum of liquid heptanol C₇H₁₅OH (Figure 7). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 8 (Spectrum). FTIR spectrum of liquid octanol C₈H₁₇OH (Figure 8). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 9 (Spectrum). FTIR spectrum of liquid nonanol C₉H₅₁₉H (Figure 9). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 10 (Spectrum). FTIR spectrum of liquid decanol C₁₀H₂₁OH (Figure 10). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 11 (Spectrum). FTIR spectrum of gaseous methanol CH₃OH (Figure 11). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 12 (Spectrum). FTIR spectrum of gaseous ethanol C₂H₅OH (Figure 12). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 13 (Spectrum). FTIR spectrum of gaseous propanol C₃H₇OH (Figure 13). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 14 (Spectrum). FTIR spectrum of gaseous butanol C₄H₉OH (Figure 14). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 15 (Spectrum). FTIR spectrum of gaseous pentanol C₅H₁₁OH (Figure 15). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

Dataset Item 16 (Spectrum). FTIR spectrum of gaseous hexanol C₆H₁₃OH (Figure 16). FTIR spectrum is the dependence of the infrared absorbance (measured in arbitrary units (a.u.)) on the wavenumber (measured in the reversed centimeters (cm⁻¹)).

4. Concluding Remarks

In this work, the experimentally registered IR absorption spectra of monohydric alcohols in liquid and gaseous state are presented. The collected experimental data can be useful for the investigations of the structure and properties of partly ordered liquids, dynamics and kinetics of cluster formation processes in hydrogen-bonded systems, peculiarities of phase transitions from gas to liquid in such objects, and so forth.

Dataset Availability

The dataset associated with this Dataset Paper is dedicated to the public domain using the CC0 waiver and is available at http://dx.doi.org/10.7167/2013/329406/dataset.

Acknowledgment

This work was supported by the State Fund for Fundamental Researches of Ukraine (Grant no. F41/138-2011).

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