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

Abstract

The initial thermal temperature coefficient of the calomel electrode reported in Part I is combined with the results of thermal diffusion studies elsewhere to yield information about: the entropy of transport S* of the aqueous electrolytes KCI, NaCI, LiCI, HCI, and CaCI2; the experimentally determinable moving (transported)entropy S of the ion constituents CI-, K +, Na +, Li +, H +, and Ca + +. A four-constant equation analogous to the Fuoss-Onsager conductance equation is developed for the concentration dependence of the entropy of transport S* and is applied to the salts KCI and NaCI. The division of the moving entropy S into its nonmeasurable ionic component terms: the ionic transport entropy S* and the stationary entropy S, is attempted via two postulates: the Agar postulate and the KCl-bridge postulate which give results mutually consistent within about 0.8 eu (35 ~VF/deg), e.g., S~ (H +) = --5.22 eu from our data under the Agar postulate, and --4.42 eu under the KCl-bridge postulate. These values are in good agreement with previously reported values of --4.48, --5.5, and --5.7 based on a number of alternative postulates. Values are also obtained for the transport heat capacity C* of the electrolytes and for the measurable moving heat capacity C of the --4 ion constituents at 30 ~ A division of C into its nonmeasurable ionic components: C* and C is also carried out on the basis of Fales and Mudge's hydrogen thermal emf data via the KCl-bridge posUllate, and yields, e.g., C*o ----30 eu (Cl-), 5 (H+); ~-o =--24 (CI-),--5 (H+); ~o = 6 (el-), 0 (H+). * Electrochemical Society Active Member. Key words: calomel electrode, electrolytes, entropy of transport, heat capacity of transport, ionic entropy, ionic heat capacity, ions, thermodynamic properties of salines, thermoelectric power, transported entropy, transported heat capacity.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.6.218.72 Downloaded on 2015-07-18 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.6.218.72 ABSTRACTThe moving (transported) ionic properties S and C are partial molal properties of the ion itself and include the effect of its electrical charge on that portion of the solvation layer which travels with the ion (Eastman first and second regions). The negatives of the ionic transport properties --S* and ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.6.218.72 Downloaded on 2015-07-18 to IP

Electric Field of the Ocean Induced by Diffusion

“…On this reason extrathermodynamic assumptions are necessary for evaluation of the thermodynamic properties of individual ions. Activity coefficients of the individual ions and them derivatives were calculated by means of Equations (19)- (25) neglecting by last bracket in Equations (19), (20). There are many evidences that adequately experimental uncertainty, the Equations (19) and (20) describe non-ideal behavior of salts for any components of electrolyte solutions (activity coefficients, osmotic coefficients and them derivatives from concentrations, temperature, and pressure).…”

“…It is should be noted that Pitzer parameters are electroneutral combination of the corresponding virial coefficients. The last bracket of the Equations (19), (20) contains just the second virial (26), (27), and (29) is quality of available experimental data. At present time, there is a very good dataset of the Pitzer parameters [27].…”

“…The "absolute" entropies of transfer of sodium and chloride ions for 298 K have been published elsewhere [20]. The transference numbers in Hittorff's reference frame for 0.7 molality sodium chloride solution have been taken from [21].…”

Thermoelectric Powers and Transported Entropies in Aqueous Hydrochloric Acid

“…-~ x/c log 7• --~-Bc + Dc 2 1 q-A'A/q---log(1 W 0.03604m) [10] The molarity c is given by c/m = a --bm [11] The constants for Eq. [10] and [11] are shown in Table III we obtained Scl-. The results of these calculations are given in columns 7, 8, and 9 of Table II.…”

“…However, we obtained nearly constant values by including the mean molal ionic activity coefficient and its temperature derivative, according to Eq. [7] ~H+ (rood2) :~H+ (mod 1) -{-R ln.~/• + RT ,0 ln-~___ OT [7] as has been derived by deBethune and Daley (11) [cf.…”