Characterization of Infrared and Near-Infrared Absorptions of Free Alcoholic OH Groups in Hydrocarbon

Abstract

We have demonstrated that the near-infrared and infrared absorptions in the 8000–3200 cm⁻¹ region of an OH group of 2-nonanol, 1-nonanol, etc., in n-heptane are excellently separated by subtraction without any serious interference down to very low concentrations at which OH groups are completely free. The separated sharp absorptions are assigned to the fundamental, combination, and overtone bands that are concerned with the OH stretching of free OH. Two components of a sharp overtone band around 7100 cm⁻¹, which are observed for primary and secondary alcohols, are assigned to coexisting internal rotational isomers of an OH group around the O–C bond. The frequencies of the OH stretching fundamental and overtone bands that are assigned to internal rotational positions are consistent for all the investigated alcohols, including methanol and tertiary butanol. Comparison of the separated spectrum of 2-nonanol in n-heptane with that in 1-chlorooctane or in carbon tetrachloride makes it clear that hydrocarbon is an inert solvent that does not disturb the intrinsic nature of an alcohol OH group. There actually exists a constant anharmonicity shift of 169–175 cm⁻¹ between the double frequency (2v(OH)_o) of the observed fundamental and the observed overtone frequency ([2v(OH)]_o) for free OH of various alcohols in n-heptane.

Keywords

Infrared spectroscopy Near-infrared spectroscopy OH groups Alcohols in hydrocarbon Hydrocarbon solvent Absorption of alcoholic OH Internal rotational isomers Subtraction separation Association of OH groups

Get full access to this article

View all access options for this article.

References

Mecke

, Discuss. Faraday Soc. 9, 161 (1950).

Liddel

and Becker

E. D

, Spectrochim. Acta 10, 70 (1957).

Piccolini

and Winstein

, Tetrahedron Lett. 13, 4 (1959).

Cook

J. S.

and Reece

I. H

, Aust. J. Chem. 14, 211 (1961).

Dalton

Meakins

G. D.

Robinson

J. H.

and Zaharia

, J. Chem. Soc. 1566 (1962).

Aaron

H. S.

Ferguson

C. P.

and Rader

C. P

, J. Am. Chem. Soc. 89, 1431 (1967).

Van Ness

H. C.

Van Winkle

Richtol

H. H.

and Hollinger

H. B

, J. Phys. Chem. 71, 1483 (1967).

Joris

Von Rague Schleyer

and Osawa

, Tetrahedron 24, 4759 (1968).

Bellamy

L. J.

, Infrared Spectra of Complex Molecules (Chapman and Hall, London, 1980), Vol. 2, 2nd ed., pp. 98–101.

10.

Van der Maas

J. H.

and Lutz

E. T. G

, Spectrochim. Acta, Part A 30, 2005 (1974).

11.

Lutz

E. T. G.

and Van der Maas

J. H

, Spectrochim Acta, Part A 34, 915 (1978).

12.

Lutz

B. T. G.

and Van der Maas

J.H

, J. Mol. Struct. 436/437, 213 (1997).

13.

Fletcher

A. N.

and Heller

C. A

, J. Phys. Chem. 71, 3742 (1967).

14.

Fletcher

A. N.

, J. Phys. Chem. 73, 2217 (1969).

15.

Forland

G. M.

Libnau

F. O.

Kvalheim

O. M.

and Hoiland

, Appl. Spectrosc. 50, 1264 (1996).

16.

Forland

G. M.

Liang

Kvalheim

O. M.

Hoiland

and Chazy

, J. Phys. Chem. B 101, 6960 (1997).

17.

Asprion

Hasse

and Maurer

, Fluid Phase Equilib. 186, 1 (2001).

18.

Nodland

, Appl. Spectrosc. 54, 1339 (2000).

19.

Iwahashi

Ikumi

Matsuzawa

Moroi

Czarnecki

M. A.

and Ozaki

, Vib. Spectrosc. 20, 113 (1999).

20.

Czarnecki

M. A.

Maeda

Ozaki

Suzuki

and Iwahashi

, J. Phys. Chem. A 102, 9117 (1998).

21.

Iwahashi

Suzuki

Kitayama

Matsuzawa

Czarnecki

M. A.

Ozaki

and Wakisaka

, Appl. Spectrosc. 54, 268 (2000).

22.

Stordrange

Christy

A. A.

Kvalheim

O. M.

Shen

and Liang

, J. Phys. Chem. A 106, 8543 (2002).

23.

Bowie

B. T.

and Griffiths

P. R

, Appl. Spectrosc. 54, 1192 (2000).

24.

Iwamoto

Oguro

Sato

and Iseki

, J. Phys. Chem. B 106, 6973 (2002).

25.

Iwamoto

and Murase

, J. Polym. Sci., Part B: Polym. Phys. 41, 1722 (2003).

26.

Iwamoto

Matsuda

Sasaki

and Kusanagi

, J. Phys. Chem. B 107, 7976 (2003).

27.

Iwamoto

Amiya

Saito

and Samura

, Appl. Spectrosc. 55, 864 (2001).

28.

Socrates

, Infrared and Raman Characteristic Group Frequencies (John Wiley and Sons, Chichester, 2001), 3rd ed., pp. 94–100.

29.

Kaye

, Spectrochim. Acta 6, 257 (1954).

30.

Iwamoto

, unpublished data.

31.

Ohta

and Iwamoto

, Anal. Chem. 57, 2491 (1985).

32.

Griffiths

P. R.

and De Haseth

J. A

, Fourier Transform Infrared Spectrometry (John Wiley and Sons, New York, 1986), Chap. 7.

33.

Herzberg

, Molecular Spectra and Molecular Structure. II. Infrared and Raman Spectra of Polyatomic Molecules (D. Van Nostrand Company, Princeton, New York, 1945), pp. 201–227.