The ultraviolet absorption spectra of «-butyl nitrite, ¿-butyl nitrite, n-amyl nitrite and isoamyl nitrite in the 2100 to 4000 A. region have been determined in the gas state and in the following solvents: cyclohexane, isooctane, carbon tetrachloride, chlorobenzene, diethyl ether, di-isopropyl ether, p-dioxane, ethyl acetate, acetone, a number of alcohols and water. The peak positions for «-alkyl and isoalkyl nitrites in the 3000-4000 Á. band systems are almost completely independent of solvent. The peak positions for ¿-alkyl nitrites appear to show a blue shift with increasing dielectric constant of the solvent. The usual solvent effects are complicated by a possible shift in the trans-cis ratio in «-alkyl and isoalkyl nitrites. The short wave length maxima between 2050 and 2250 A. show a blue shift with increasing dielectric constant of the solvent, which may be associated with an allowed nx type electronic transition.
The electronic absorption spectra for NO2-N2O4 mixtures has been measured in various non-polar and polar solvents. In non-polar solvents the spectrum is very similar to NO2-N2O4 mixtures in the gas state. However, in solvents with unshared electron pairs available particularly ethers, esters, ketones and tertiary amines, a complex multi-banded spectrum is observed at room temperature. This spectrum appears to be characteristic of NO2-N2O4 in those solvents and to be the result of the same electron donor-acceptor type molecular complexes reported previously in the literature at lower temperatures in the solid state. In olefins and n-alkyl amines reactions occur and the products formed are discussed.
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