Spectroscopic and thermodynamic study of the H-bonding of olefins onto the isolated hydroxyl of amorphous silica

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DOI 10.1039/A903682B
Impact Factor 3.676
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Abstract

FTIR data are reported concerning the adsorption of ethene, propene, but-1-ene, trans-but-2-ene, cyclohexene and methylcyclohexene on Aerosil outgassed at 800°C. H-bonding is the only process occurring with the four lighter molecules, and a strictly Langmuir-type behaviour is found. With the two heavier species, plain physisorption also takes place, causing the solvation of H-bonded adducts, which are best defined at low coverage. From the intensity of the ν(OH) mode of the free hydroxyls as a function of pressure, the equilibrium constant for the H-bond formation is calculated in different ways, according to the role of physisorption. Several correlations are drawn for Δν(OH) and ΔG°. The contribution of the substituents to the basicity of the double bond as measured by the shift in frequency is discussed, as well as the role of H-bonding and van der Waals forces in dictating the energetics of the interaction.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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