Dielectric absorption in long-chain secondary alcohols and their solid solutions

1962 ◽  
Vol 58 ◽  
pp. 1953 ◽  
Author(s):  
R. J. Meakins
Keyword(s):  
Solid Solutions ◽  
Secondary Alcohols ◽  
Dielectric Absorption ◽  
Long Chain

Temperature Dependence of the Dielectric Properties of Long-Chain Aliphatic Alcohols in the Solid State

1952 ◽  
Vol 5 (4) ◽  
pp. 661 ◽  
Author(s):  
JS Dryden
Keyword(s):  
Dielectric Properties ◽  
Solid State ◽  
Temperature Dependence ◽  
Aliphatic Alcohols ◽  
Experimental Results ◽  
Secondary Alcohols ◽  
Primary Alcohols ◽  
Dielectric Absorption ◽  
Apparent Activation Energies ◽  
Long Chain

The dielectric properties of three primary and three secondary long-chain aliphatic alcohols have been investigated within the temperature range of -20 to 70 �C. The experimental results are discussed in relation to the theory of Sack on dielectric absorption in linear polar chains and to the conclusions reached in earlier papers on the dielectric properties of these compounds. The apparent activation energies in the primary alcohols are approximately three times those in the secondary alcohols. This indicates either different mechanisms of absorption in the two types of alcohols or, if the mechanisms are the same, significant differences in the energy barriers involved.

The Dielectric Properties of a Series of dl-n-Eicosanols

1951 ◽  
Vol 4 (3) ◽  
pp. 359
Author(s):  
RJ Meakins ◽  
HK Welsh
Keyword(s):  
Dielectric Properties ◽  
Low Frequency ◽  
Polar Compounds ◽  
Carbon Chain ◽  
Hydroxyl Groups ◽  
Secondary Alcohols ◽  
Polar Group ◽  
Dielectric Absorption ◽  
Ready Availability ◽  
Long Chain

Initial investigations of the dielectric properties of normal long-chain secondary alcohols were made with the symmetrical compounds because of their ready availability. The properties of long-chain polar compounds are known to vary considerably, however, with the position of the polar group in the carbon chain and it therefore seemed desirable to make dielectric measurements with some unsymmetrical alcohols. The present paper describes such an investigation of a series of dl-n-eicosanols having the hydroxyl groups in the 2-, 4-, 6-, 8-, and 10-positions, respectively. The results for the melted forms show that slight asymmetry, as in the 10-compound, has little effect on the dielectric properties, but with the more unsymmetrical 4-, 6-, and 8-compounds a considerable enhancement of the dielectric absorption is observed. This is accompanied by increased dispersion of the dielectric constant which, for the 8-compound, reaches a low frequency value of 15. Both ε" and ε' decrease during storage at room temperature. Anomalous results are obtained with dl-n-eicosan-2-ol, probably due to the molecules in the crystal lattice being alternately reversed, end-to-end. As with the symmetrical secondary alcohols, the recrystallized forms give comparatively little dielectric absorption.

The Dielectric Properties of Crystalline Long-Chain n-Primary Alcohols at Low Frequencies

1951 ◽  
Vol 4 (3) ◽  
pp. 365
Author(s):  
RJ Meakins ◽  
JW Mulley
Keyword(s):  
Dielectric Properties ◽  
Primary Alcohol ◽  
Dielectric Constants ◽  
Double Layers ◽  
Significant Feature ◽  
Hydroxyl Groups ◽  
Secondary Alcohols ◽  
Primary Alcohols ◽  
Dielectric Absorption ◽  
Long Chain

In a previous paper it was reported that certain crystalline forms of long-chain secondary alcohols show abnormally large dielectric absorption and dispersion of the dielectric constant at audio and radio frequencies. The present paper describes an extension of the investigation to n-primary alcohols and discusses the results in terms of the previously suggested theory of dielectric absorption due to the presence of hydrogen-bonded chains of hydroxyl groups. The most significant feature of the results is that the absorption is larger and occurs at much lower frequencies than for the secondary alcohols. This is considered to be due to the end-to-end arrangement of the molecules in n-primary alcohol crystals, which gives double layers of hydroxyl groups and enables the formation of more extensive hydrogen-bond chains. The dielectric constants at the lowest frequencies are almost as large as those previously reported by Hoffmann and Smyth (1949) for the " waxy " forms of n-primary alcohols. Further aspects described are the changes in dielectric properties during storage, the differences between the melted and recrystallized forms, and the effect of dispersing the molecules in an inert solid solvent. In each of these aspects the observed behaviour is similar to that previously reported for the secondary alcohols.

The Dielectric Properties of Symmetrical Long-Chain Secondary Alcohols in the Solid State

1951 ◽  
Vol 4 (2) ◽  
pp. 213 ◽  
Author(s):  
RL Meakins ◽  
RA Sack
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Dielectric Loss ◽  
Low Temperatures ◽  
Room Temperature ◽  
Molecular Chain ◽  
Hydroxyl Groups ◽  
Crystal Formation ◽  
Secondary Alcohols ◽  
Long Chain

Symmetrical long-chain secondary alcohols in the solid state show very high dielectric loss at audio and radio frequencies. This can be explained by the presence of chains of hydroxyl groups linked by hydrogen bonding and capable of reversing their direction. Further evidence of hydrogen bonding is provided by a study of the melting points of the secondary alcohols and related compounds. The amount of dielectric loss depends markedly on the manner of formation of the solid, being smallest for samples formed by recrystallization from solvents at low temperatures and largest for specimens obtained by slow cooling from the melt. The alcohols of molecular chain-lengths of 13, 15,17, and 19 carbon atoms show a considerable decrease of absorption on storing at room temperature. For alcohols of between 23 and 43 carbon atoms the loss is rather smaller with a peak at higher frequencies, but remains more constant in time. These results are interpreted in terms of competing influences of van der Waals forces and hydrogen bonds during crystal formation ; the former, which lead to a structure unsuitable for the formation of hydrogen-bond chains, are predominant at low temperatures, but become more rapidly neutralized by thermal motion, especially for the shorter molecules. The high temperature modification of the lower homologues is unstable at room temperature, and a molecular diffusion process causes the bond chains to break. Dilute systems of secondary alcohols with hydrocarbons or paraffin wax of similar molecular chain-length show very small dielectric loss suggesting a solid solution in which bond chains cannot be formed ; if the paraffin molecules are appreciably longer, the absorption is large and decreases on storing, presumably owing to the presence of a pure alcohol phase. I.

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