THE JOURNAL OF The Heat and Free Energy of CHEMICAL PHYsics RS. Jussur National Bureau of Slandords, Washington, D. C. (Received March Values calculated from available thermochemical and chemical thermodynamic data are sven forthe Beats and free energies of polymerization of gaseous ethylene o facous, straight. chain polyethylene (monoolefin) molecles of various lengths. Equations are given expresing ‘the number of ethylene unit per polymer molecule, long-chain molecules are all 12.186 kcal. per ethylene unit. A preliminary valve for the heat of these properties at 25°C a functions of, for wi=3. The limiting values at 25°C for ‘ethylene unit, AF, : Pobehom a 256 a with eter date to ou ese erin a ited vale forgone pein reno account is taken of are be 3 healer ethylene un Valur, vim eoncntrone of eine sa "= ~254 kcal. per ethylene unit for the heat of poly ‘ateous ethylene to solid polyethylene. This experimental value and the caleu- ‘the heat of sublimation of the partly crystallin polyetiylene, estimated to given graphically and in tabular form for the eq ta polymers at various temperatures in a mixture VOLUME 16, NUMBER 7 Polymerization of Ethylene 1948) 2.348 heal per = ~311.8 keal. per ethylene unit, ie combined tobe consistent within reasonable limite when the ideal gas state ata pressure of 1 atmosphere, Values of heats of polymerization of a number of yaxoun tne on ‘compounds to gaseous polymers, calculated with the aid of various thermochemical data, have been reported by Flory,! Evans and Polanyi? and Evans and Tyrrall.* The data used were not jin all cases sufficient to permit exact calculation of heats of polymerization of long-chain polymer molecules. For example, in some cases the heat of dimerization per mole of dimer was taken as an estimate of the heat of polymerization. This procedure neglects the anomalous increment per CH; group in the heats of formation of hydro- carbons of low molecular weight, and also neg- lects the effect of steric interference between substituent groups attached to the carbon chain ‘of the polymer molecule. The latter effect was also neglected in calculating heats of formation of polymer molecules from heats of formation of Iong-chain normal paraffin hydrocarbons, to- gether with data on heats of isomerization of ‘octanes, or lower members of the paraffin series. Most of the calculated values of heat of poly- merization given in the references cited oy apply to hypothetical polymer pace, wt ie are free from such steric effects. This fact has been pointed out by Evans and Tyrrall TE Resear riage ide ls orp, Eta iad Pla RSet Sa 387 +A, 2A casi7). KD tis possible to calculate from data now avail- able, values for the heat and free energy of poly- merization of gaseous ethylene to gaseous straight-chain monoolefin. molecules of any de- sired chain length, without introducing any such approximations as those indicated above. The results will therefore apply to the actual poly- ethylene molecules (in the ideal gas state). Polymerization is ordinarily considered to be the combination of monomer molecules to form larger molecules, each of which contains an integral number of monomer units. It is doubtful, hhowever, that the actual reactions by. which polymers are formed are as simple as this. At high températures, at east, the reaction of poly- merization, as defined above, would be expected to be accompanied by degradation reactions going on at the same time. Such degradation would, be expected to involve, among other things, the breaking of polymer chains at points far removed from the ends, where there is no distinction between the carbon-carbon bonds of the chain which were originally carbon-carbon bonds in monomer molecules and those which are bonds between adjacent monomer units. Some of the resulting polymer molecules would then contain fragments of the original monomer molecules as well as entire monomer units. In it is to be expected that some poly- cular, ae Id contain odd numbers ethylene molecules wou 661