Specific heat translational

Guirao and Bach (1979) used the flux-corrected transport method (a finite-difference method) to calculate blast from fuel-air explosions (see also Chapter 4). Three of their calculations were of a volumetric explosion, that is, an explosion in which the unbumed fuel-air mixture is instantaneously transformed into combustion gases. By this route, they obtained spheres whose pressure ratios (identical with temperature ratios) were 8.3 to 17.2, and whose ratios of specific heats were 1.136 to 1.26. Their calculations of shock overpressure compare well with those of Baker et al. (1975). In addition, they calculated the work done by the expanding contact surface between combustion products and their surroundings. They found that only 27% to 37% of the combustion energy was translated into work. 

Differences in specific heats can be obtained in a similar fashion. Since translational and rotational contributions to Cp at elevated temperatures are minor, the differences to be accounted for are entirely due to vibrational effects. The most effective way to accomplish this is to identify the incremental contribution of each atom or group to Cp, and add or subtract this value from... 

For a temperature of 298.15 K, a pressure of 1 bar, and 1 mole of H2S, prepare a table of (1) the entropy (J/mol K), and separately the contributions from translation, rotation, each vibrational mode, and from electronically excited levels (2) specific heat at constant volume Cv (J/mol/K), and the separate contributions from each of the types of motions listed in (1) (3) the thermal internal energy E - Eo, and the separate contributions from each type of motion as before (4) the value of the molecular partition function q, and the separate contributions from each of the types of motions listed above (5) the specific heat at constant pressure (J/mol/K) (6) the thermal contribution to the enthalpy H-Ho (J/mol). 

These methods provide an accurate means of investigating translation-vibration and translation-rotation transfer. The passage of a sound wave through a gas involves rapidly alternating adiabatic compression and rarefaction. The adiabatic compressibility of a gas is a function of y, the ratio of the specific heats, and the classical expression for the velocity, V, of sound in a perfect gas is... 

Whether rotation-vibration transfer occurs, and how important it is, are questions of considerable dispute. The experimental observation by Millikan106,107, that vibrational deactivation of CO in collision with p-H2 is more than twice as efficient as in collision with o-H2, seems to provide some evidence that rotational energy participates in vibrational relaxation. The only significant difference between o- and p-H2 in the context of this experiment would appear to be the difference in rotational energy states, as illustrated by the fact that at 288 °K (the temperature of the experiment) the rotational specific heat of o-H2 is 2.22, while that of p-H2 is 1.80 cal.mole-1.deg-1. Cottrell et a/.108-110 have measured the vibrational relaxation times of a number of hydrides and the corresponding deuterides. On the basis of SSH theory for vibration-translation transfer the relaxation times of the deuterides should be systematically shorter than those of the hydrides. The... 

Einstein s theory of specific heat leads to the same result. This theory connects the molecular motion in solid bodies with Planck s theory of radiation, and has been confirmed in the main by the experimental researches of Nernst and his collaborators in the last few years. Einstein assumes that the heat motion in solid bodies consists of vibrations of the atoms about a point of equihbrium, as distinct from the translational motion of the molecules which we assume for gases. The energy of these vibrations—and this is the characteristic feature of the theory, and also of Planck s theory of radiation—is always an integral multiple of a quantity of energy e, which, in turn, is the product of a universal constant (. e. a constant independent of the nature of the substance) and the frequency i/ (number of vibrations R,... 

Debye, P. Zur Theorie der spezifischen Warmen. [On the theory of specific heats.] Annalen der Physik 39, 789-839 (1912). English translation in Collected Papers of Peter J. W. Debye, pp. 650-696. Interscience New York (1954). 

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