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The configurations of the two secondary and the two tertiary alcohols whose synthesis is described in the preceding paper have been established unambiguously by analysis of n.m.r. spectra. Four techniques were used : (i) treatment of chemical shifts by the additivity relationship; (ii) study of degree to fit to the relationship between europium-induced shift and intramolecular distance; (iii) comparison between sensitivities of shifts to europium concentration; and (iv) investigation of the behaviour of the previously assigned protons of adamantan-2-ol, and spin decoupling in the europium-expanded spectrum. All results led to the same conclusions, and justify interchange of the configurations previously assigned to the secondary alcohols. The reliability of these methods is assessed.

A procedure used to calculate chemical shifts in some fluorocarbon compounds (see preceding paper) is extended to include fluorine bonded to tin(IV). In this case secondary interactions, responsible for deviations from additivity of substituent effects in fluorocarbons, are negligible.

Amino-14N chemical shifts have been measured in some substituted anilines by use of the heteronuclear double resonance method. The shifts are shown to correlate linearly with the Hammett σ values of the ring substituents and to be related directly to electron densities at the nitrogen nucleus found by other workers. This supports arguments that we have used qualitatively in previous papers. For four compounds where 15N data are also available, the relative 14N and 15N chemical shifts are found to be identical within experimental error.

The study of molecules in the gas phase by ESCA offers several advantages. Particularly, the opportunity to make direct comparisons between theoretical and experimental results is of importance. From such comparisons a more complete understanding of several fundamental phenomena in ESCA has been gained. The present paper reviews some recent work in Uppsala along this line. The effect of electron reorganization on core binding energies in atoms and molecules is analyzed. Chemical shifts in ESCA and n.m.r. are discussed. The existence of a general relation involving these chemical shifts and nuclear spin-rotation constants is pointed out. A model for analyzing ESCA intensities of the valence electrons in molecules is presented. It is shown that the analysis may be useful in identifying the molecular orbitals.For most applications of ESCA it is highly desirable to improve the resolution and the intensity. An instrument, particularly designed to achieve this for gases, is discussed. It can also handle solid samples. It makes use of a high-emission, fine-focus electron gun, a rotating anode and a double focusing quartz crystal. The first electron spectrum recorded with this new instrument is presented.