This review is variously a presentation, reflection, synthesis and report with reference to more recent developments of an article - in a journal which has ceased publication - entitled "Some Electrode Theorems with Experimental Corroboration, Inclusive of the Ag/AgCl System" Internet Journal of Chemistry, (http://www.ijc.com), Special Issues: Vol. 2 Article 24 (1999). The results from new lemmas relating charge densities and capacitance in a metallic electrode in equilibrium with an ionic solution are used to explain the data and observed effects due to Esin, Markov, Grahame, Lang and Kohn. Size effects that vary the measured e.m.f. of electrodes due to changes in the electronic chemical potential are demonstrated in experiment and theory implying the need for standardization of electrodes with respect to geometry and size. The widely used Stern modification of the Gouy-Chapman theory is shown to be mostly inapplicable for many of the problems where it is employed. Practical consequences of the current development include the possibility of determining the elusive single-ion activity coefficients of solution ions directly from the expression given by a simplified capacitance theorem, the potential of zero charge and the determination of single ion concentrations of active species in the electrode reactions from cell e.m.f. measurements.
The Carnot cycle and its deduction of maximum conversion efficiency of heat inputted and outputted isothermally at different temperatures necessitated the construction of isothermal and adiabatic pathways within the cycle that were mechanically "reversible", leading eventually to the Kelvin-Clausius development of the entropy function S with differential dS = dq/T such that [symbol: see text]C dS = 0 where the heat absorption occurs at the isothermal paths of the elementary Carnot cycle. Another required condition is that the heat transfer processes take place infinitely slowly and "reversibly", implying that rates of transfer are not explicitly featured in the theory. The definition of 'heat' as that form of energy that is transferred as a result of a temperature difference suggests that the local mode of transfer of "heat" in the isothermal segments of the pathway implies a Fourier-like heat conduction mechanism which is apparently irreversible, leading to an increase in entropy of the combined reservoirs at either end of the conducting material, and which is deemed reversible mechanically. These paradoxes are circumvented here by first clarifying the terms used before modeling heat transfer as a thermodynamically reversible but mechanically irreversible process and applied to a one dimensional atomic lattice chain of interacting particles subjected to a temperature difference exemplifying Fourier heat conduction. The basis of a "recoverable trajectory" i.e. that which follows a zero entropy trajectory is identified. The Second Law is strictly maintained in this development. A corollary to this zero entropy trajectory is the generalization of the Zeroth law for steady state non-equilibrium systems with varying temperature, and thus to a statement about "equilibrium" in steady state non-thermostatic conditions. An energy transfer rate term is explicitly identified for each particle and agrees quantitatively (and independently) with the rate of heat absorbed at the reservoirs held at different temperatures and located at the two ends of the lattice chain in MD simulations, where all energy terms in the simulation refer to a single particle interacting with its neighbors. These results validate the theoretical model and provides the necessary boundary conditions (for instance with regard to temperature differentials and force fields) that thermodynamical variables must comply with to satisfy the conditions for a recoverable trajectory, and thus determines the solution of the differential and integral equations that are used to model these processes. These developments and results, if fully pursued would imply that not only can the Carnot cycle be viewed as describing a local process of energy-work conversion by a single interacting particle which feature rates of energy transfer and conversion not possible in the classical Carnot development, but that even 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 by conflating the classically distinct concept of work and heat energy into a single particle interactional process. A resolution to the fundamental and long-standing conjecture of Benofy and Quay concerning the Fourier principle is one consequence of the analysis.
The behaviour of a flexible anionic chain of 150 univalent and negatively charged beads connected by a harmonic-like potential with each other in the presence of an equal number of positive and free counterions, is studied in molecular dynamics simulations with Langevin thermostat in a wide range of temperatures. Simulations were carried out for several values of the bending parameter, corresponding to fully flexible polyion, moderately and strongly stiff polyion as well as for the case when bend conformation is preferable to the straight one. We have found that in all cases three regimes can be distinguished, which can be characterized as "random coil", observed at high temperatures; "extended conformation" observed at moderate temperatures (of the order of 1 in reduced units), and compact "globular conformation" attained at low temperatures. While the transition between high-temperature random and extended conformations is gradual, the transition from the extended coil to the globular state, taking place at a temperature of about 0.2 in reduced units, is of abrupt character resembling a phase transition.
This study was aimed at establishing the interactions prevailing in an anionic surfactant, sodium dodecyl sulfate, and dopamine hydrochloride in an alcoholic (ethanol) media by using volumetric, conductometric, and tensiometric techniques. Various methods were utilized to estimate the critical micelle concentration (cmc) values at different temperatures. The entire methods yielded the same cmc values. The corresponding thermodynamic parameters viz. the standard free energy of micellization (Gmico), enthalpy of micellization (Hmico), and entropy of micellization (Smico) were predicted by applying the pseudo-phase separation model. The experimental density data at different temperatures (298.15 K, 303.15 K, 308.15 K, and 313.15 K) were utilized to estimate the apparent molar volumes (Vϕo) at an infinite dilution, apparent molar volumes (Vφcmc) at the critical micelle concentration, and apparent molar volumes (ΔVφm) upon micellization. Various micellar and interfacial parameters, for example, the surface excess concentration (Γmax), standard Gibbs free energy of adsorption at the interface (ΔGoad), and the minimum surface area per molecule (Amin), were appraised using the surface tension data. The results were used to interpret the intermolecular interactions prevailing in the mixed systems under the specified experimental conditions.