Quantitative NMR spectroscopy of binary liquid mixtures (aldehyde + alcohol). Part III: (1-decanal or 3-phenylpropanal or 2-chlorobenzaldehyde) + (methanol or ethanol or 1-propanol)

•Formation of hemiacetal/poly(oxymethylene) hemiacetals in liquid binary mixtures.•Aldehyde (1-decanal or 3-phenylpropanal or 2-chlorobenzaldehyde) and alcohol (methanol or ethanol or 1-propanol).•Quantitative 13C-NMR spectroscopy at temperatures between 255 K and 295 K.•High conversion rates: (2-phenylpropanal + 1-propanol (50 + 50)) at T = 273 K: mole fraction of hemiacetal ≈ 57%.•Formation of acetals in systems with 2-chlorobenzaldehyde.

The thermodynamic properties of binary liquid mixtures of (aldehyde + alcohol) are strongly influenced by chemical reactions in particular around and below ambient temperature. In two previous publications the chemical reaction equilibrium was investigated by 13C – Fourier transform NMR-spectroscopy at temperatures between 255 K and 295 K for a series of aldehydes (acetaldehyde, 1-propanal, 1-butanal, 1-heptanal) with three alcohols (methanol, ethanol, 1-propanol). Here these investigations are extended to three more aldehydes (1-decanal, 3-phenylpropanal and 2-chlorobenzaldehyde, respectively). The results for the binary systems with decanal or 3-phenylpropanal as the aldehyde in the binary mixture (aldehyde + alcohol) confirm the expectations from the first parts of this series, i.e., that the majority of the constituents of the mixture is present as hemiacetal and the first two poly(oxymethylene) – hemiacetals. The numerical results for the chemical reaction equilibrium constants from the previous investigations can be used to predict quantitatively the speciation in binary systems of ((either 1-decanal or 3-phenylpropanal) + (either methanol or ethanol or 1-propanol)). However the experimental results with 2-chlorobenzaldehyde reveal a different behaviour. In all investigated systems (2-chlorobenzaldehyde + alcohol) the most important reaction product was the corresponding acetal whereas the amounts of hemiacetal were very small. While the amounts of hemiacteal could still be quantified, it was not possible to quantify the amount of any poly(oxymethylene) – hemiacetal.

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