Use of Gibbs equation in irreversible thermodynamics. II. Caloric equations for components and partial pressure

1972 ◽  
Vol 37 (4) ◽  
pp. 1218-1226 ◽  
Author(s):  
I. Samohýl
2020 ◽  
Vol 45 (2) ◽  
pp. 133-153
Author(s):  
Thoralf Chrobok ◽  
Horst-Heino von Borzeszkowski

AbstractFirst, the special-relativistic Theory of Irreversible Processes for a multi-component fluid is formulated. It is based on (i) the balance equations of the particle number and the energy-momentum for the total system (i. e., the mixture of the components) as well as the sub-systems (i. e., the components) and (ii) the dissipation inequality and the Gibbs equation for the mixture. In order to allow for reactions between the single components, in contrast to the total system, the sub-systems are assumed to be open, which means that their particle number and energy-momentum are not constrained by conservation laws. Without making any assumptions on the thermodynamic behavior of the interacting components, one arrives at a thermodynamic description of the mixture showing now heat conduction and viscosity. In particular, this makes it possible to calculate the entropy production and, thus, to identify thermodynamic currents and forces. In a second part, the post-Newtonian limit of this theory is calculated to show that for the mixture there result relations known from classical Extended Thermodynamics that partly are corrected by entrainment terms. The mathematical origin and physical consequences of these terms are discussed.


Author(s):  
A. S. Farlenkov ◽  
N. A. Zhuravlev ◽  
Т. A. Denisova ◽  
М. V. Ananyev

The research uses the method of high-temperature thermogravimetric analysis to study the processes of interaction of the gas phase in the temperature range 300–950 °C in the partial pressure ranges of oxygen 8.1–50.7 kPa, water 6.1–24.3 kPa and hydrogen 4.1 kPa with La1–xSrxScO3–α oxides (x = 0; 0.04; 0.09). In the case of an increase in the partial pressure of water vapor at a constant partial pressure of oxygen (or hydrogen) in the gas phase, the apparent level of saturation of protons is shown to increase. An increase in the apparent level of saturation of protons of the sample also occurs with an increase in the partial pressure of oxygen at a constant partial pressure of water vapor in the gas phase. The paper discusses the causes of the observed processes. The research uses the hydrogen isotope exchange method with the equilibration of the isotope composition of the gas phase to study the incorporation of hydrogen into the structure of proton-conducting oxides based on strontium-doped lanthanum scandates. The concentrations of protons and deuterons were determined in the temperature range of 300–800 °C and a hydrogen pressure of 0.2 kPa for La0.91Sr0.09ScO3–α oxide. The paper discusses the role of oxygen vacancies in the process of incorporation of protons and deuterons from the atmosphere of molecular hydrogen into the structure of the proton conducting oxides La1–xSrxScO3–α (x = 0; 0.04; 0.09). The proton magnetic resonance method was used to study the local structure in the temperature range 23–110 °C at a rotation speed of 10 kHz (MAS) for La0.96Sr0.04ScO3–α oxide after thermogravimetric measurements in an atmosphere containing water vapor, and after exposures in molecular hydrogen atmosphere. The existence of proton defects incorporated into the volume of the investigated proton oxide from both the atmosphere containing water and the atmosphere containing molecular hydrogen is unambiguously shown. The paper considers the effect of the contributions of the volume and surface of La0.96Sr0.04ScO3–α oxide on the shape of the proton magnetic resonance spectra.


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