The Thermal Temperature Coefficient of the Calomel Electrode Potential between 0° and 70°C

Abstract

The initial thermal temperature coefficient of the calomel electrode potential has been measured between 0° and 70°C for aqueous 1.0, 0.1, and 0.01m potassium chloride, sodium chloride, lithium chloride, hydrochloric acid and 0.5, 0.05, and 0.01m calcium chloride. Thermal diffusion of the electrolyte was impeded by the use of Vycor intermediate (thirsty glass) glass plugs in the salt bridges between the two banks of electrodes, one of which was kept at 35° while the other was varied from 0° to 70°. The thermal emfs of the fifteen cells investigated exhibited a slight curvature concave to the temperature axis. The hot electrode had the (+) polarity (cathodic in a battery sense) in all cases. Experimental data can be fairly represented by quadratic equations, and least squares values of the quadratic constants are given. The initial thermal temperature coefficients are compared with prior thermal emf data on the calomel electrode. The relative thermal emfs of the same electrode in different salts at constant chloride ion concentration are compared with values deduced from prior thermal emf observations on calomel and silver chloride electrodes or calculated from the transport entropies of chlorides obtained in thermal diffusion studies.

Ion selective electrodes, potentiometry, and potentiometric titrations

“…Factors determining stability and reproducibility (576) Reproducible E ± 10 µV (417) Reports thermal temperature coefficients between 0 and 70 °C (191) Fabrication and use in polarographic determination of H, H2S, S02, CO, 0, Cl…”

The Thermodynamics and Electrode Kinetic Behavior of Nickel in Acid Solution in the Temperature Range 25° to 300°C

“…[2], derived from thermodynamics by Unfortunately, the Cp data required for Eq. [2] are not available for most ionic species (17)(18)(19)(20)(21) and attempts by Lewis (22) at solving it by assuming that the Cp value of ionic species are zero do not correspond with experimental data, as is shown in Table I, and the need for ionic Cp data is clear. Recently Criss and Cobble (23)(24)(25) have devised a theoretical method for solving Eq.…”

The Thermal Temperature Coefficient of the Calomel Electrode Potential Between 0° and 70°C

“…= tKC* (KC1) --t~C* (MC1)/z~ [15] where the B's are the quadratic coefficients of Eq. [1]. The reference values of C*(KC1) in dependent determinations from other observers, sometimes at other concentrations and temperatures, as listed in the last column.…”