Battery reference book(c) by Crompton T.R.

By Crompton T.R.

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AL, aM. . f. , is a constant for the given cell reaction, varying only with the temperature, at 1 atmosphere pressure. f. f. is thus seen to be dependent upon the activities of the hydrogen and chloride ions in the solution of hydrochloric acid, and of the hydrogen gas in the cell. 30 could be replaced by the corresponding concentrations of the hydrogen and chloride ions. and by the pressure of the hydrogen gas. 30. 31) PHzR could be used if the solution of hydrochloric acid were dilute and the pressure of the hydrogen gas low.

In this discussion the solute and solvent may be considered separately; the treatment of the activity coefficient of the solute in dilute solution will be given first. 51) where f is the activity coefficient of the solute. 52) applicable to ideal and non-ideal solutions. An ideal (dilute) solution is defined as one for which f is unity, but for a non-ideal solution it differs from unity. 53) a, = CO that is, the activity of the solute is equal to its molar concentration. The standard state of unit activity may thus be defined as a hypothetical solution of unit molar concentration possessing the properties of a very dilute solution.

57 by the mole fraction of the solvent. 3 gives the activity coefficients at various concentrations of two typical liquids used as battery electrolytes, namely sulphuric acid and potassium hydroxide. It will be seen that the activity coefficients initially decrease with increasing concentrations. Subsequently at higher concentrations activity coefficients rise becoming greater than one at high concentrations. 6. 7 shows the relationship between activity, a , and molality for sulphuric acid. For many purposes, it is of more interest to know the activity, or activity coefficient, of the solute rather than that of the solvent as discussed above.

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