Erratum: Hindered Intermolecular Rotation in the Solid State: Thermal and Dielectric Phenomena in Lo

It has been assumed that the potential energy barrier hindering rotation of chain molecules about their long axes in the solid state has one deep minimum and Ω other minima with a potential energy V above that of the deeper well. Molecular models suggest Ω should be between 8 and 18. Application of the Bragg‐Williams cooperative approximation to this system leads to first‐order thermal and dielectric transitions. Dielectric and thermal data on n‐C22H45Br, n‐C30H61Br, and n‐C28H58 show that the transitions are first‐order. The static dielectric constant of the polar compounds calculated from Onsager's equation on the basis Ω=12 agree closely with experiment. The model suggests the existence of two Debye‐type loss regions below the transition temperature. Loss data confirm this and further indicate Ω is close to 12. There is no evidence of resonance absorption. Ω may also be found from the entropy of transition at constant volume, R lnΩ. Thermal data on all three compounds are consistent with a value of Ω o...

[1]  C. P. Smyth,et al.  Molecular Rotation in Some Long-chain Fatty Acid Esters in the Solid State1,2 , 1951 .

[2]  K. Higasi,et al.  On High Frequency Power Loss of Dielectrics , 1951 .

[3]  W. M. Heston,et al.  Dielectric Constants, Viscosities, Densities, Refractive Indices and Dipole Moment Calculations for Some Organic Halides1 , 1950 .

[4]  E. R. Andrew Molecular Motion in Certain Solid Hydrocarbons , 1950 .

[5]  H. F. Cook,et al.  Dielectric Behaviour of Methyl Palmitate in the Microwave Region , 1950, Nature.

[6]  V. Daniel A Co-operative Transition in a Mixed Ketone Shown by a Change of Dielectric Constant , 1949, Nature.

[7]  C. P. Smyth,et al.  Molecular Rotation in the Solid Forms of Some Long-Chain Alcohols , 1949 .

[8]  R. F. Patterson,et al.  The Density and Transition Points of the n-Paraffin Hydrocarbons , 1944 .

[9]  A. Muller Further Investigations of Solid n-Paraffins. (Repulsion Potential and Compressibility) , 1941 .

[10]  K. Cole,et al.  Dispersion and Absorption in Dielectrics I. Alternating Current Characteristics , 1941 .

[11]  J. Kirkwood The Dielectric Polarization of Polar Liquids , 1939 .

[12]  C. P. Smyth,et al.  The Possibility of Molecular Rotation in the Solid Forms of Cetyl Alcohol and Three Long-Chain Ethyl Esters , 1938 .

[13]  S. H. Piper,et al.  The n-Fatty Acids and Certain of Their Derivatives , 1937 .

[14]  L. Onsager Electric Moments of Molecules in Liquids , 1936 .

[15]  C. P. Smyth,et al.  The Constancy of Two Dipole Moments in the Vapor State and Their Apparent Variation in Solution , 1935 .

[16]  A. Muller An X-Ray Investigation of Normal Paraffins Near Their Melting Points , 1932 .

[17]  R. A. Oriani THE ENTROPIES OF MELTING OF METALS , 1951 .

[18]  C. P. Smyth,et al.  The Mechanism of Rotation of Long-chain Alkyl Bromides and Other Molecules in the Solid State1 , 1950 .

[19]  A. Maradudin,et al.  Theory of dielectrics , 1949 .

[20]  W. Shockley,et al.  Order-Disorder Transformations in Alloys , 1938 .