Bomb calorimetric studies on normal alkan-1-ols, stereoregular polymethylmethacrylates, [alpha][alpha]-olefinic polymers, trioxane and oxygenated polymers

Abstract

Precision bomb calorimetry measurements have been carried out in four areas of investigation. The general areas of investigation are: 1) justification of the incremental method for hydrogen-bonded liquids; 2) enthalpies of combustion and formation of five α-olefin polymers; 3) configurational enthalpy in isomers of polymethylmethacrylate, and 4) heats of combustion of trioxane and polymers of methyl, vinyl ether, ethyl vinyl ether, and propylene oxide. In the study of hydrogen-bonded liquids, enthalpy of combustion measurements were made on pentan-1-ol, heptan-1-ol, and nornan-1-ol. Experimental procedures used in handling hygroscopic liquids and analyzing the combustion products are presented. Enthalpies of combustion for pentan-1-o1, heptan-1-ol, and nonan-1-ol are -795.87 ± 0.16 kcal mol ⁻¹, -1108.51± 0.19 kcal mol⁻¹, and 1421.36 ± 0.25 kcal mol⁻¹, respectively. Enthalpies of formation for both liquid and gas phase were found to vary linearly with n for values of n= 2, 3, 4, 5, 7, 8, 9, 16. The methylene increment in the liquid alcohols is reported as -5.987 ± .032 kcal mol⁻¹. The gas phase increment is reported as -4.848 ± .020 kcal mol⁻¹. The deviation of these observed increments for alcohols from that accepted for paraffins are discussed. In the second are of investigation, enthalpy of combustion measurements were made on polymers of propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, 1-octene, and 1-haxadecene. Enthalpy of fusion measurements were also made in order to determine the enthalpy of formation of the totally amorphous (liquid) polymer above the glass temperature..