Among the physical methods of which use has been made to explain the structure of organic compounds, thermal measurements, particularly measurements of heats of combustion, have played a particularly important part. With the aid of data on heats of combustion, it is possible to draw conclusions on the energy relations within molecules and on the heat tones of chemical transformations. Such measurements have been carried out on highly polymeric substances. In some cases, the object was to study the reactions of formation. e.g., polymerization; in other cases it was to explain the transformations which high polymers themselves undergo. Studies of polymerization reactions by thermal methods have shown that, in distinction to monomers, a decrease in the heat of combustion with increase in the degree of polymerization is to be expected. The polymerization process is accordingly exothermic, and the difference between the heats of combustion represents the heat of polymerization which is liberated. A direct comparison of heats of polymerization found experimentally by different investigators is, however, not possible because, in most cases, no information on the degree of polymerization, branching of the chain molecules, or other significant properties of the polymers are given.

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