Effect of Intermolecular Interactions between CH Frequencies on the Infrared Spectra of N-Paraffins and Polythene

Abstract

A systematic study has been made of the infrared absorption band near 725 cm—1 which arises from the rocking vibration of methylene groups in n‐paraffins and in polyethylene. In unoriented crystals of n‐paraffins, this band exhibits two components of equal intensity below the transition point; above the transition temperature and in the liquid state only the higher frequency component is found. In solid cold‐drawn polyethylene the two components are of unequal intensity, the low frequency component being the stronger; in liquid polyethylene only the lower frequency component is found. Studies were made of polyethylene in various states of crystallinity and orientation, using both polarized and unpolarized radiation. The results obtained can be consistently interpreted, if the higher frequency component is attributed to crystallites in the polyethylene and the lower frequency component is assumed to be due partly to the crystalline and partly to the amorphous form of the polyethylene. It is concluded that the doubling of this frequency arises from some interaction between methylene groups which is peculiar to the crystalline state of long chain n‐paraffins below their transition points.