Apparent dissociation constants of hydrogen sulfide in chloride solutions

Spectrophotometric measurements are reported for the first apparent dissociation constant of hydrogen sulfide in seawater over the temperature range 7.5–25°C and 2–35.8‰ salinity. These data are described by the expression $\text{p}\text{K}{}_1\text{′ = 2.527 ? 0.169 Cl}{}^{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{+ 1359.96/T}$. The second apparent dissociation constant in potassium chloride solution was estimated potentiometrically using a sulfide specific ion electrode. A value of ～13.6 was found for pK₂′ at a KCl concentration of 0.67 M. It is suggested that explicit reference to the sulfide ion, S^2?, in describing equilibria in marine waters be dropped in favor of a formulation involving the bisulfide ion, HS^?.