Interactions of Molecules with cis and trans Double Bonds: A Theoretical Study of cis- and trans-2-Butene.

Noncovalent interactions of cis- and trans-2-butene, as the smallest model systems of molecules with cis and trans double bonds, were studied to find potential differences in interactions of these molecules. The study was performed using quantum chemical methods including very accurate CCSD(T)/CBS method. We studied parallel and displaced parallel interactions in 2-butene dimers, in butane dimers, and between 2-butene and saturated butane. The results show the trend that interactions of 2-butene with butane are the strongest, followed by interactions in butane dimers, whereas the interaction in 2-butene dimers are the weakest. The strongest calculated interaction energy is between trans-2-butene and butane, with a CCSD(T)/CBS energy of -2.80 kcal mol(-1) . Interactions in cis-2-butene dimers are stronger than interactions in trans-2-butene dimers. Interestingly, some of the interactions involving 2-butene are as strong as interactions in a benzene dimer. These insights into interactions of cis- and trans-2-butene can improve understanding of the properties and processes that involve molecules with cis and trans double bonds, such as fatty acids and polymers.

Real-time application and modelling of the NOx-sorption reaction on a particulate calcium carbonate surface-flow filter exposed to combustion exhaust.

Of major interest, especially in city environments, and increasingly inside vehicles or industrial plants, is the drive to reduce human exposure to nitrogen oxides (NOx). This trend has drawn increasing attention to filtration, which has developed remarkably owing to the capabilities of recently developed mathematical models and novel filter concepts. This paper reports on the study of the kinetic modelling of adsorption of nitrogen dioxide (NO2), collected from the tailpipe of a diesel engine, reacting to calcium nitrate salt (Ca(NO3)2) on a surface flow filter consisting of a coating of fine ground limestone or marble (CaCO3) in combination with micro-nanofibrillated cellulose (MNFC) acting as binder and humectant applied onto a multiply recycled newsprint substrate. The coating and substrate are both porous, but on different pore size scales, with the coating having significantly lower permeability. To maximise gas-coating contact, therefore, the coating deposition is pixelated, achieved by pin coating. An axially dispersed gaseous plug flow model (dispersion model) was used to simulate the transport within the coating pore network structure, following earlier flow modelling studies, and a kinetic reaction model was used to examine NO2 to NO3- conversion in correlation with experimental results. Modelling results indicate a 60.38% conversion of exposed NO2 gas to Ca(NO3)2 under the specific conditions applied, with an absolute relative error between the predicted and experimentally estimated value being 0.81%. The model additionally enabled a prediction of effects of changing parameters over a limited perturbation range, thus assisting in predicting filter element consumption, with attention given to the active component CaCO3 surface as a function of particle size in relation to the gas contact exchange, promoting the reaction over time. It is intended that the Ca(NO3)2 formed from the reaction can go on to be used as a value-added fertiliser, thus contributing to circular economy.

Volumetric properties and spectroscopic studies of pyridine or nicotine solutions in liquid polyethylene glycols.

Densities and molar excess volumes of the solutions of pyridine or nicotine in liquid polyethylene glycol, PEG200 and PEG400, have been determined at several temperatures. The experimental molar excess volumes are negative, thus indicating strong attractive interactions between the components, as could be expected considering their highly polar nature and good hydrogen bond abilities. For the pyridine systems, this negativity is slightly increased as the temperature rises, while the opposite tendency is observed for the nicotine mixtures. When pyridine and nicotine solutions are compared, the former-particularly those with PEG400-exhibit substantially more negative molar excess volumes than the latter. The effect of the polymer chain length on the results for the nicotine solutions is almost negligible. However, this is not the case when pyridine is one of the components: a longer chain induced considerably higher compression on mixing. The Fourier-transform infrared analysis allowed interpretation of the negative experimental molar excess volumes in terms of specific inter- and intramolecular interactions.