First‐Order Phase Transitions of Six Normal Paraffins at Elevated Pressures

First order phase transitions were investigated for n‐nonane, n‐dodecane, n‐tridecane, n‐pentadecane, n‐octadecane, and n‐tetracosane, at pressures up to 10 kilobars and temperatures up to 135°C. By a modification of standard piezometric techniques, phase transition pressures, as well as the associated isothermal isobaric volume changes were determined at approximately 25°C intervals. Correlations established between the melting temperatures and the specific volume changes associated with phase transitions and the n‐paraffin chain lengths show a strong dependence upon whether the n‐paraffin is of odd or even species. This dependence becomes more pronounced at higher pressures. The specific volume, enthalpy, and entropy changes showed no dependence upon chain length at the same melting temperature.

[1]  A. Muller An X-Ray Investigation of Normal Paraffins Near Their Melting Points , 1932 .

[2]  W. Webb,et al.  Effect of Pressure on Viscosity of Higher Hydrocarbons and Their Mixtures , 1958 .

[3]  W. Webb,et al.  Study of the Compressions of Several High Molecular Weight Hydrocarbons , 1958 .

[4]  P. W. Bridgman Freezing Parameters and Compressions of Twenty-One Substances to 50,000 Kg/Cm , 1942 .

[5]  P. W. Bridgman Further Rough Compressions to 40,000 Kg/Cm, Especially Certain Liquids , 1949 .

[6]  Bakerian Lecture - Physics above 20,000 kg./cm.2 , 1950, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[7]  P. W. Bridgman Volume-Temperature-Pressure Relations for Several Non-Volatile Liquids , 1932 .

[8]  J. W. Spencer,et al.  Temperature‐Pressure‐Structure Effects on the Viscosity of Several Higher Hydrocarbons , 1959 .

[9]  P. W. Bridgman The Thermal Conductivity of Liquids under Pressure , 1923 .

[10]  Franz Simon,et al.  Bemerkungen zur Schmelzdruckkurve , 1929 .

[11]  P. W. Bridgman The Volume of Eighteen Liquids as a Function of Pressure and Temperature , 1931 .

[12]  Percy Williams Bridgman,et al.  The physics of high pressure , 1931 .

[13]  P. W. Bridgman The Measurement of Hydrostatic Pressures up to 20,000 Kilograms per Square Centimeter , 1911 .

[14]  P. W. Bridgman Thermodynamic Properties of Twelve Liquids between 20° and 80° and up to 12000 Kgm. per Sq. Cm. , 1913 .