Studies were made of solutions of 1-octanol and 1-butanol in n-decane using the infrared absorption of the first overtone of the O-H stretch vibrations of the monomer and selfassociation polymers. Evaluation was made on 1-octanol solutions from 5 to 100°, without making use of a priori self-association models. Evaluations were performed by three methods involving comparisons of: (I) the monomer absorbance and the total alcohol concention, (II) the monomer absorbance and the polymer absorbance, and (III) a combination of I and II. The following new assignments were made: (1) the end O-H of linear selfassociation polymers do not contribute significant absorbance at the monomer peak in the first overtone region; (2) the monomer molar absorptivity is constant with temperature;(3) the usual "dimer" peak at 1.528 µ cannot be due to a O-H • O-H dimer as its absorbance varies directly proportionally to that of the monomer (it is tentatively assigned to an alcohol-solvent interaction); (4) the remainder of the polymer absorption is assigned solely to tetramers; and (5) the tetramers give partially overlapping peaks which are due to O-H bonds in two different tetramers. Thermodynamic values indicate a linear and a cyclic tetramer. The linear with three bonds has a AH of -16.5 kcal/mole and the cyclic with four bonds has a AH of -20.3 kcal/mole. Thus within the limits of error, all O-H first overtone absorption is explained by assigning a monomer in equilibrium with two tetramers. This holds from 10-4 M to neat 1-octanol over a 95°t emperature range. Data from other workers for other alcohols in CCk are evaluated and found to be consistent with the present assignments. Much more self-association of alcohols was observed in n-decane than was observed in CCh. In particular, kinetic data involving alcohols are explained by the physical model described.N. Y" 1959.
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