Accession Number : AD0603728
Title : STUDY OF THE PHOTOCATALYZED DECOMPOSITION OF WATER AND OF THE MECHANISMS OF INTRAMOLECULAR ELECTRON TRANSFER IN ORGANIC COMPOUNDS.
Descriptive Note : Final rept.,
Corporate Author : MASSACHUSETTS INST OF TECH CAMBRIDGE
Personal Author(s) : Heidt,Lawrence J.
Report Date : 14 MAY 1964
Pagination or Media Count : 162
Abstract : Gross and net quantum yield measurements were made for the photochemical conversion by light of 2537 A of up to 1.4% of the ferrous to ferric sulfate and of the accompanying production of gaseous H2 in aqueous H2SO4 at 25C. The data support the hypothesis that in solution 2M or less in dilute H2SO4, FeSO4 exists mostly as ion pairs which in 6.0 M H2SO4 are partly replaced by contact type FeSO4 complexes. The ultraviolet absorption spectra of aniline, nitrobenzene, benzaldehyde and benzoic acid were correlated with each other and with that of benzene. The shifts in the various absorption maxima brought about by solvents of different hydrogen bounding capability and dipole moment were found to follow a simple linear relationship. Molecular orbital calculations are presented which explain the ultraviolet absorption spectra of aniline, N-methyl-, N-ethyl-, N, N dimethyl- and N, N diethylaniline. The calculations reveal that the goround and six lowest excited electronic energy levels of these compounds are mixtures of electronic configurations contributed by the benzene group and by charge transfer from the amino to the phenyl group.
Descriptors : (*PHOTOCHEMICAL REACTIONS, WATER), (*WATER, DECOMPOSITION), (*ATOMIC ENERGY LEVELS, ORGANIC COMPOUNDS), CATALYSTS, IRON COMPOUNDS, SULFATES, SULFURIC ACID, HYDROGEN, OXYGEN, AROMATIC COMPOUNDS, AMINES, ALDEHYDES, CARBOXYLIC ACIDS, NITROBENZENES, SOLVENTS, ULTRAVIOLET SPECTROSCOPY, ABSORPTION SPECTRA, MOLECULAR STRUCTURE, CHEMICAL BONDS
Distribution Statement : APPROVED FOR PUBLIC RELEASE