The rationality of two reported data, which are cited in the paper titled as above, is discussed. One of them is dependable, and another is not. The justification has been given in detail.

Some basic matters concerning with the heat effect at electrode–electrolyte interface are briefly introduced in this paper. They include the concepts and definition about the electrochemical Peltier heat (EPH) and the Peltier coefficient for the electrode process, the absolute scale, the fundamental equations on this scale for thermoelectrochemistry, and the issues of the entropy changes on this scale and EPHs for the standard hydrogen electrode reaction as well as other standard electrode reactions. The EPH of electrode–electrolyte interface is specially emphasized to be a quantity related to reversible process; thereupon it can be measured and also be calculated by the change in the function of state, or entropy, on the absolute scale. The changes in entropy on the absolute scale, EPHs and the electrochemical Peltier coefficients for some of the most common standard electrode reactions in aqueous solution at 298.15 K are given.

The electromotive forces of a symmetrical concentration cell with transference, Ag; AgCl|LaCl3 (m*):LaCl3 (m)|AgCl; Ag, were measured over the concentration range from 8.762 × 10−4 mol kg−1 to 6.788 × 10−2 mol kg−1 at 298.15 K to obtain the mean activity coefficients of LaCl3. The mean activity coefficient for reference solution at 298.15 K and the ion size parameter for LaCl3 in the extended Debye–Hückel equation are evaluated by using an approach extrapolating concentration to unlimited dilution. A modified Debye–Hückel equation with new parameters has been established for the studied concentration range. A comparison is done of the thermodynamic data of LaCl3 that are determined by this experiment with those reported by previous literatures, and evaluated by some models.

In response to Rockwood's query about the standard state of electron and the handling of the entropy of electron on the absolute scale, an answer is made. Usually, the standard state for a chemical substance is specified based on a classical physical law. The standard state of electron on the absolute scale is determined according to the free electron model on the Fermi–Dirac statistics. However, the thermodynamic handling of the same particle on the different scales must be completely identical, and the difference is only designated values of the thermodynamic parameters. For the standard hydrogen electrode reaction, the electron entropy and the partial molar entropy of hydrogen ion, respectively, are 65.29 J mol−1 K−1 and zero on the conventional scale, and zero and about −22.3 J mol−1 K−1 on the absolute scale at 298.15 K. The other query, related to units used for fugacity, the conversion entropy of electron from gas-phase to metal-phase, the partial molar entropy of electron in the platinum, and the Peltier heat at the platinum/copper joint, is also expatiated.

A method for measuring the electrochemical Peltier heat (EPH) of a single electrode reaction has been developed and an absolute scale is suggested to obtain EPH of the standard hydrogen electrode. The scale is based on ϕ0* = 0 and ΔS0* = 0 for any electrode reaction at zero Kelvin, in accord with the third law of thermodynamics. The relationships between entropy, enthalpy and free energy changes on this scale and on the conventional scale are derived. Calorimetric experiments were made on the Fe(CN)63−/Fe(CN)64− system at five different concentrations at 298.15 K, and EPH for the standard hydrogen electrode reaction is obtained. EPHs and the entropy change on the absolute scale for the studied redox are linearly related to concentration of electrolyte. The reversible electric work is almost concentration independent in the range of concentration studied.

A metallic solution model with adjustable parameter k has been developed to predict thermodynamic properties of ternary systems from those of its constituent three binaries. In the present model, the excess Gibbs free energy for a ternary mixture is expressed as a weighted probability sum of those of binaries and the k value is determined based on an assumption that the ternary interaction generally strengthens the mixing effects for metallic solutions with weak interaction, making the Gibbs free energy of mixing of the ternary system more negative than that before considering the interaction. This point is never considered in the models currently reported, where the only difference in a geometrical definition of molar values of components is considered that do not involve thermodynamic principles but are completely empirical. The current model describes the results of experiments very well, and by adjusting the k value also agrees with those from models used widely in the literature. Three ternary systems, Mg–Cu–Ni, Zn–In–Cd, and Cd–Bi–Pb are recalculated to demonstrate the method of determining k and the precision of the model. The results of the calculations, especially those in Mg–Cu–Ni system, are better than those predicted by the current models in the literature.