Hydrogen Bonding in Alcohols

Citation

Rosser, Willis Andrew, Jr. (1952) Hydrogen Bonding in Alcohols. Master's thesis, California Institute of Technology. doi:10.7907/2S8Z-D418. https://resolver.caltech.edu/CaltechTHESIS:10182017-132702543

Abstract

It is usually assumed in optical absorption work that the natural stretching frequency of the hydroxyl group in an alcohol is appreciably changed by hydrogen bonding. A survey of work relating to hydrogen bonding in alcohols favors this assumption. Moreover, it appears that the deviation of alcohols in solvents such as carbon tetrachloride from Henry's law is primarily due to hydrogen bonding polymerization, the extent of such deviation being the same for the lower aliphatic alcohols and phenol.

Optical transmission measurements on dilute solutions of methyl alcohol and of ethyl alcohol in carbon tetrachloride were used to determine for these alcohols the dimerization constants associated with the reaction.

2 ROH → (ROH)₂

These constants in turn were used in support of the contention that the polymerization constants associated with the reactions

(ROH)_g-1 + ROH → (ROH)_g

are not independent of g as has been assumed on occasion.

The viscosity of solutions of alcohols in carbon tetrachloride is briefly discussed in a semi-quantitative manner.

Thesis Files