Fourier heat conduction as a phenomenon described within the scope of the Second law

摘要

The historical development of the Carnot cycle necessitated the construction of isothermal and adiabatic pathways within the cycle that were also mechanically "reversible" which lead eventually to the Kelvin-Clausius development of the entropy function S where for any reversible closed path l, f_l dS = 0 based on an infinite number of concatenated Carnot engines that approximated the said path and where for each engine △Q_1/T_1+△Q_2/T_2 = 0 where the Q’s and T’s are the heat absorption increments and temperature respectively with the subscripts indicating the isothermal paths (1;2) where for the Carnot engine, the heat absorption is for the diathermal (isothermal) paths of the cycle only. Since ’heat’ has been defined as that form of energy that is transferred as a result of a temperature difference and a corollary of the Clausius statement of the Second law is that it is impossible for heat to be transferred from a cold to a hot reservoir with no other effect on the environment, these statements suggested that the local mode of transfer of ’heat’ in the isothermal segments of the pathway does imply a Fourier heat conduction mechanism (to conform to the definition of ’heat’) albeit of a “reversible” kind, but on the other hand, the Fourier mechanism is apparently irreversible, leading to an increase in entropy of the combined reservoirs at either end of the material involved in the conveyance of the heat energy. These and several other considerations lead Benofy and Quay (BQ) to postulate the Fourier heat conduction phenomenon to be an ancillary principle in thermodynamics, with this principle being strictly local in nature, where the global Second law statements could not be applied to this local process. Here we present equations that model heat conduction as a thermodynamically reversible but mechanically irreversible process where due to the belief in mechanical time reversible symmetry, thermodynamical reversibility has been unfortunately linked to mechanical reversibility, that has discouraged such an association. The modeling is based on an application of a “recoverable transition”, defined and developed earlier on ideas derived from thermal desorption of particles from a surface where the Fourier heat conduction process is approximated as a series of such desorption processes.We recall that the original Carnot engine required both adiabatic and isothermal steps to complete the zero entropy cycle, and this construct lead to the consequent deduction that any Second law statement that refers to heat-work conversion processes are only globally relevant. Here, on the other hand, we examine Fourier heat conduction from MD simulation and model this process as a zero-entropy forward scattering process relative to each of the atoms in the lattice chain being treated as a system where the Carnot cycle can be applied individually. The equations developed predicts the “work” done to be equal to the energy transfer rate. The MD simulations conducted shows excellent agreement with the theory. Such views and results as these, if developed to a successful conclusion could imply that the Carnot cycle be viewed as describing a local process of energy-work conversion and that irreversible local processes might be brought within the scope of this cycle, implying a unified treatment of thermodynamically (i) irreversible, (ii) reversible, (iii) isothermal and (iv) adiabatic processes.