R.S. JESSUP 664 Pe scacar ag eae cei el smonodlefin fre of L atmosphere, Ba ‘eno nl per med, & Magubocee tf a tn unit, derived from data reported by Prosen and Rossini," for the difference between the heats of combustion of liquid and gaseous normal paraffin hydrocarbons, with the value 1.21 keal. per ethylene unit for the heat of fusion of poly. ethylene at 25°C. The latter value was derived from data reported by Raine, Richards and Ryder* on the heat content of solid and liquid Polyethylene over the temperature range from 20° to 115°C, ‘The value for the heat of sublimation of solid Polyethylene at 25°C obtained in the manner indicated is 3.6 kcal. per ethylene unit. When this is subtracted from the limiting value given in Table I for the heat of polymerization of gaseous ethylene to gaseous polyethylene at 25°C, there is obtained the value, 4H, for the heat of polymerization at 25°C of gaseous ethylene to solid polyethylene. The difference between this and the experimental value above may be due in part to error in the esti- mated value of heat of sublimation of poly- ethylene, and in part to the presence of molecules of low molecular weight in the sample of poly- ethylene used in the measurement of heat of ‘combustion. As stated previously, the data given in Tables and II are for polymers consisting of straight- chain monoolefin hydrocarbons only, because data necessary for the exact treatment of other types of polymer molecule are lacking. Esti- mates based on available information indicate =25.9 kcal. per ethylene unit, peer 5 reir pe, Faraday Soc. 4; §6'(1945). ST Tne RIRATE ALN KO that the effect of branching of the polyethylene ‘on the heat and free energy of polymerization may be of the order of 0.1 kcal. per ethylene unit or less. The effect of end groups other than the assumed methyl group at one end of the chain and vinyl group at the other is probably negli- gible for sufficiently long molecules. ‘The data on free energy of polymerization may be used to calculate the equilibrium con- centrations of ethylene and its polymers in a rmixture in the ideal gas state at a pressure of 1 atmosphere. The values calculated for all the normal monoolefin hydrocarbons at several tem~ peratures are given in Table IIT, and are shown graphically in Fig. 1. Similar data are shown in Fig. 2 for a mixture of all polymers containing integral numbers of ethylene units in the molecule. ‘As a consequence of the linear relation con- necting free energy of formation at any one temperature with m, the number of ethylene units per molecule, for n2:3, the ratio, cais/ca) of mole fractions of molecules having n+4 and 1 ethylene tmits each is a constant for n>3. At high temperatures cy is relatively large for 233, and the constant ratio Cy4i/¢s is small, so that only molecules of low molecular weight are present in appreciable amounts in the equi- librium mixture. At lower temperatures. the mole fractions are all low, and the ratio Ca4s/¢s for n=3 is only slightly less than unity, so that & is comparable with ¢, for a large number of values of n>3. ‘The data reported here are of particular ine terest, since the polymerization of ethylene to normal monoolefin. hydrocarbons is perhaps the simplest polymerization reaction involving hy- drocarbons. The data are not affected by steric interference between substituent groups. at- tached to the carbon chain, or by other effects of such groups. It may be noted that the heat of polymerization of ethylene is higher than any of the values which have been reported for vinyl derivatives.® 1 *D. E. Roberts, W. W, Walton, and R. 8. Jessup, J. Research Nat. Bur, Stand, 38, 627 (1947). LK. J. Toog and W. O. Kenyon, J. Am. Chem, Soc. 67, 1378 (1545); €8, 1355 (1946); 60, 1462 (1547).