Application of the Local Vibrational Mode Framework for the Spectroscopic Estimation of Free Hydroxyl Group Fractions in Pure Liquid Methanol-d3.

Methanol and hexane mixtures covering the whole solubility range are studied by Fourier transform infrared attenuated total reflectance spectroscopy in order to evaluate OH groups that are H-bond-free. The mixtures from 0 to 0.25 and from 0.75 to 1.00 mole fractions form homogeneous solutions, whereas those from 0.25 to 0.75 mole fractions are inhomogeneous, forming two phases. Factor analysis (FA) was used to find out if free OH groups were present. These were found in minute quantities at the lowest mole fraction by evaluating the OH stretch absorption. The bulk of the absorption is due to the greater than 99.9% of hydrogen-bonded methanol molecules, with a band maximum situated at 3340 cm(-1). The stretch band of the free OH groups absorbs at 3654 cm(-1), with a full width at half maximum of 35 cm(-1). The concentration is very weak but constant at less than 5 mM in the mole fraction between 0.252 and 0.067. Below this range, OH concentrations are even smaller. This represents less than 1% of the amount of methanol at the mole fraction of 0.067 (0.543M). Above 0.25 mole fraction, free methanol OH groups are not observed. Since the free OH band is very weak, almost at the noise level, we verified its presence with mixtures of hexanol in hexane. There, we found a similar free OH band with almost the same band characteristics, but with almost three times the concentrations found with methanol, which we attribute to the difference in the hydrocarbon chain length. The present study indicates clearly that solutions of methanol in hexane contain free OH groups but in minute quantities and only in the low methanol concentrations. This situation is much different from that observed in solutions of methanol in CCl(4), where free OH groups are clearly observed at all concentrations except at the concentration limits. Whereas in CCl(4), methanol is believed to form H-bonded chains, the situation is different in n-hexane: methanol in the low concentration region would form reverse micelles with the OH groups in the core and the CH(3) groups mixed with n-hexane molecules.

FN-NIR study of dissociation of decan-1-ol in the liquid phase—I

We use classical atomistic molecular dynamics simulations of two water models (SPC/E and TIP4P/2005) to investigate the orientation and reorientation dynamics of two subpopulations of OH groups belonging to water molecules at the air/water interface at 300 K: those OH groups that donate a hydrogen bond (called "bonded") and those that do not (called "free"). Free interfacial OH groups reorient in two distinct regimes: a fast regime from 0 to 1 ps and a slow regime thereafter. Qualitatively similar behavior was reported by others for free OH groups near extended hydrophobic surfaces. In contrast, the net reorientation of bonded OH groups occurs at a rate similar to that of bulk water. This similarity in reorientation rate results from compensation of two effects: decreasing frequency of hydrogen-bond breaking/formation (i.e., hydrogen-bond exchange) and faster rotation of intact hydrogen bonds. Both changes result from the decrease in density at the air/water interface relative to the bulk. Interestingly, because of the presence of capillary waves, the slowdown of hydrogen-bond exchange is significantly smaller than that reported for water near extended hydrophobic surfaces, but it is almost identical to that reported for water near small hydrophobic solutes. In this sense water at the air/water interface has characteristics of water of hydration of both small and extended hydrophobic solutes.

Fourier transform near-infrared (FT-near-IR) and FT-IR spectra have been measured for cis-9-octadecen-1-ol in CCl4 solutions at various concentrations and temperatures partly to investigate its self-association and partly to explore its near-IR spectrum. Both spectra have demonstrated the appearances of bands due to free terminal OH groups of the linear dimer (open-chain dimer) and oligomer of the alcohol. They are observed at 3621 and 7070 cm−1 in the IR and near-IR regions, whose frequencies are lower by 16 and 34 cm−1, respectively, than those of the corresponding bands due to a free OH group of the monomer. The spectral changes in both regions suggest that (1) at concentrations below 0.10 M, the alcohol exists mostly as the monomer and dimer, and with increasing temperature the dimer dissociates into the monomer; and (2) as the concentration is increased, it associates to form aggregates (such as tetramer), and with temperature increase the aggregates dissociate into the dimer and monomer. The molar absorption coefficient of the band due to the first overtone of the stretching mode of the terminal OH groups has been determined to be 0.139 dm3 mol−1 cm−1. It is approximately 8% of that of the first overtone of the monomeric OH group (1.63 dm3 mol−1 cm−1). The anharmonicity of an OH stretching mode of the alcohol has been investigated for various OH groups, free, terminal, and hydrogen-bonded, by comparing the frequencies of the bands due to the OH stretching modes with those of the bands due to the corresponding first overtones. The anharmonicity of the stretching mode of the terminal OH groups of the associated species is very similar to that for the free OH group of the monomer.

Insight into the interaction between hydrogen bonds in brown coal and water

Inter- and intramolecular hydrogen bonding and their temperature-dependent changes in a poly(4-vinylphenol)/poly(methyl methacrylate)(PVPh 30%/PMMA 70%) blend were investigated using near-infrared (NIR) and infrared (IR) spectroscopy. Band assignments of the fundamentals and first overtones of the OH stretching mode of a free OH group and OH groups in C=O···HO and OH···OH (dimer, trimer, and oligomer) hydrogen bonding of PVPh 30%/PMMA 70% were carried out by comparison between its NIR and IR spectra and comparison with NIR and IR spectra of phenol. The comparison of the NIR spectra of the PVPh 30%/PMMA 70% blend (hereafter, we denote it as PVPh30%) with the corresponding IR spectra reveals that to observe bands arising from the free OH and OH···OH dimer, which is a weaker hydrogen bonding, NIR is better while to investigate bands originating from OH groups in the OH···O=C and OH···OH (oligomer) hydrogen bonds, which are stronger hydrogen bonding, IR is better. Thus, a combination of IR and NIR spectroscopy has provided convincing results for the hydrogen bonding of PVPh30%. The relative intensity of the two bands at 7058 and 6921 cm-1 (I7058/I6921) due to the first overtones of the OH stretching modes of the free OH group and the OH group in the dimer, respectively, increases significantly above 90 °C, which is close to Tg of PVPh. In concomitance with the intensity increase in the relative intensity of the free OH band, the intensity of a band at 1706 cm-1 due to the C=O stretching mode of the C=O···HO hydrogen bond of PVPh30% decreases above 90°C. These results suggest that above the Tg of PVPh the C=O···HO hydrogen bond is broken gradually and that the free OH increases. Of note is that below Tg the intensities of NIR bands due to the OH first overtones of free OH group and OH groups in the OH···OH dimer gain intensity in parallel with temperature increase, and above Tg the intensity of the band derived from the OH···OH group increases linearly much slower than that of the band due to the free OH. Moreover, a band due to an OH···OH oligomer decreases linearly. Hence, it is very likely that the OH···OH oligomers dissociate into free OH groups. Anharmonicity of O-H bonds, which is sensitive to a hydrogen bond, was estimated for the free OH and OH bonds in the C=O···HO and OH···OH (dimer, trimer, and oligomer) hydrogen bonding by comparison between the NIR and IR spectra in the OH stretching band regions.

Recent experimental studies have shown that the vibrational dynamics of free OH groups at the water-air interface is significantly different from that in bulk water. In this work, by performing molecular dynamics simulations and mixed quantum/classical calculations, we investigate different vibrational energy transfer pathways of free OH groups at the water-air interface. The calculated intramolecular vibrational energy transfer rate constant and the free OH bond reorientation time scale agree well with the experiment. It is also found that, due to the small intermolecular vibrational couplings, the intermolecular vibrational energy transfer pathway that is very important in bulk water plays a much less significant role in the vibrational energy relaxation of the free OH groups at the water-air interface.

Effect of varying water content on the structure of butyl alcohol/water mixtures: FT-NIR two-dimensional correlation and chemometric studies

The suitability of carboxymethyl guar derivatives as thickeners in reactive printing of viscose fabrics is investigated. We show the influence of different guar thickeners on the stiffness of viscose fabric printed with monoreactive vinylsulphone dyes. The conse quences of interactions that are proportional to the bending rigidity of prints are confirmed with the quantity of residual add-on and with IR spectroscopy. The interactions depend on the macromolecular structure of the guar thickener, its degree of polydispersity, and the number of free reactive OH groups able to react with guar molecules. We conclude that higher bending rigidity is the result of physicochemical binding of guar molecules on the viscose fibers by means of hydrogen and/or ether bonds by free OH groups. Hydroxyl groups of monoreactive dyes also increase bending rigidity as a result of chemical interaction with the OH groups of guar and viscose.

Two novel zeolites SSZ-33 and SSZ-35 were investigated with respect to their acidic properties using different probe molecules to characterize the accessibility and acid strength of Lewis and Brønsted acid sites. Ammonia, pyridine, pivalonitrile, and acetonitrile-d3 were used as probe molecules, and the results were correlated with 27Al and 1H magic angle spinning (MAS) NMR. Both SSZ-33 and SSZ-35 zeolites were found to possess bridging Si−OH−Al groups of virtually uniform and high acid strength. For both SSZ-33 and SSZ-35, there is the typical presence of highly disturbed OH groups (IR band around 3500 cm-1), which amounts to almost half of the overall Brønsted acidity. It was found that almost all bridging Si−OH−Al groups in SSZ-33 are located in the 12-MR rings. Both acetonitrile-d3 and pyridine sorptions suggest the presence of two types of Lewis sites in SSZ-35, differing in acid strength and electron-acceptor properties, whereas in the SSZ-33 zeolite only one type is present. The relative strength of these sites is higher than that of the Brønsted type for SSZ-35 and is of comparable strength for SSZ-33. 1H and 27Al MAS NMR measurements during thermal treatment allowed the assignment of NMR peaks to different surface OH species and the establishment of their relation to IR bands. NMR spectroscopy enabled the quantitative analysis of both free and hydrogen-bonded OH groups separately, showing that for both zeolites the amount of disturbed sites is higher than the number of free OH groups.

The effect of pH of hydrothermal treatment for the pores and surface of silica gel — a new type of silanol sites —

The original infrared spectra in the OH stretch region that Riemenschneider and Ludwig (thereafter, RL) have obtained for pure water and aqueous salt solutions are very similar to what we have previously reported [J.-J. Max and C. Chapados, J. Chem. Phys. 115, 6803 (2001)]. In our 2010 paper, we claimed that “free” OH is not present in pure liquid water. The difference spectra from the salt solutions and pure water spectrum give small negative components situated near 3655 cm−1. Because this position is in the range where free OH groups should absorb RL assigned the negative peaks to free OH removed from pure water. That is, RL consider that pure liquid water contains free OH groups which are removed in the salt solutions. Obviously, the removal of all free OH present in pure water will produce maximum negative intensities in the difference spectra. In this response, we present unpublished difference spectra between several salt solutions and pure water where negative peaks are higher than that claimed by RL for pure water. Since this is impossible it demonstrates that the assignment proposed by RL to free OH is incorrect. The negative peaks come from the difference between large components that differ a little between salt solutions and pure water [J.-J. Max and C. Chapados, J. Chem. Phys. 115, 6803 (2001)]. Recall that the ionized salts do not absorb but perturb the surrounding water molecules.

The effect of temperature on self-association of (R)-(−)-octan-2-ol, (S)-(+)-octan-2-ol, and the racemic mixture in the pure liquid phase has been studied by two-dimensional (2D) Fourier transform near-infrared (FT-NIR) correlation spectroscopy. Both the conventional FT-NIR and 2D correlation spectra of pure enantiomers and the racemic mixture are identical to each other and do not reveal the chiral discrimination effect. The similarity of temperature relationships of population of the free OH groups for the optically active and racemic samples confirms the above conclusion. Of particular note is that the asynchronous spectra of all studied samples develop the peaks due to the free terminal OH groups in the open chain associates. This observation reveals a remarkable population of the linear species. The comparison of present results with previous studies on other isomers of octanol indicates that the degree of self-association decreases upon branching in the order octan-1-ol > octan-2-ol > octan-3-ol.

Two kinds of Er3+-doped tellurite glasses with the compositions (in mol%) of 60TeO2–30WO3–10La2O3–1Er2O3 and 60TeO2–30ZnO–10Bi2O3–1Er2O3 were prepared. Using different dehydration gases, we found that blowing a gas mixture of dry oxygen and CCl4 ensures most efficient glass melt dehydration. The free and hydrogen-bonded OH groups can be well excluded from the tellurite and tellurium–tungstate glasses, and the absorption coefficient of free OH groups in dehydrated glasses was equal to 0.68 and 1.25 cm−1, respectively. The strong 1.5- and 2.7-µm emissions were observed from the glasses, which increased with the decrease in OH content.

There are many hydrogen bonds in coal, which affect the chemical structure and properties of coal. FTIR has been applied to the characterization study of the hydrogen bonds of Dongpang coals, which were under drop weight impact. There exists five kinds of hydrogen bonds in the coal: free OH groups, OH...π, OH...OH, cyclic OH tetramers and OH...N. Absorption strength of intermolecular hydrogen bonds markedly declined after impact. Free OH groups mechanical-power chemical reacted in drop weight impact testing. The infrared spectrum were curve-resolved into their component bands. The absorption strength of various hydrogen bonds decreased with the increase of impact energy, but the trend was slowing. By statistical relationship between then, we find then complying with power function relationship. By comparing the exponents of fitted equations, we concluded that failure sensitivity sequence of hydrogen bonds to the impact: free OH groups > cyclic OH tetramers > OH...N > OH...π > OH...OH.