Initial vibrational and rotational energy distributions for the reactions of fluorine atoms with hydrogen chloride, bromide and iodide have been measured by the " arrested relaxation " chemiluminescence method. These reactions have been simulated by the classical trajectory method using semi-empirical 1.e.p.s. potential energy surfaces. Information theoretic analysis of the initial vibrational and rotational distributions has also been made.
An apparatus for detecting infrared emission from chemical reactions at low pressures under arrested relaxation conditions is described. It has been used to record the emission from hydrogen fluoride formed in the reaction of atomic fluorine with hydrogen, methane, ethane and formaldehyde. Information-theoretic analysis of the initial vibrational and rotational energy distributions for the latter three reactions have been made. The results of a classical trajectory study, using a 1.e.p.s. potential energy surface, for the reaction between atomic fluorine and methane are presented.
A statistical-mechanical approach, the coordinated cluster theory (CCT), originally developed by Blander et al. for molten salts, has been applied to the solvation of ions in binary mixed solvents. The relations between CCT and the stepwise-equilibria model approach of Covington and Newman have been highlighted. The non-ideal mixing of solvent molecules in the solvation shell incorporated into CCT shows that partial compensation of non-ideality effects between bulk solvent and solvation shell occurs, as intuitively expected. The theory is applied to the methanol-water solvent system to compare electrochemically derived free energies of transfer with the sum of single-ion values calculated from spectroscopic studies and Born theory electrostatic contributions.
upon Tyne NEl 7RU 23Na n.m.r. chemical shifts and iodide ion CTTS band maxima have been used as probes for ion-ion and ion-solvent interactions for NaI in ethylene glycol (EGtacetonitrile (AN) and propylene glycol (PGtacetonitrile mixtures. Since EG-AN mixtures are approximately isodielectric, changes in ion-solvent interactions on transfer from the pure solvents to EG-AN mixtures can be attributed to changes in the short-range, 'chemical' interactions. In combinatic-n with a stepwise thermodynamic model for solvation in a binary solvent taking into account non-ideal solvent behaviour, quantitative evidence for preferential solvation by the glycol component was obtained.
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