Hydrogen and fluoride ion molalities have been estimated potentiometri
cally in HF/H2O mixtures up to 10 mol% HF (c. 6 mol kg-1 HF) at 298 K
using the galvanic cells: Ag/AgCl/KCl(m1), HF(m2)\PbClF/Pb (two-phase
amalgam) (1) Pt/H-2\KCl(m1), HF(m2)\AgCl/Ag (2) The data show progress
ive solvation of F- by HF to form first HF2- and then H2F3-; this asso
ciation is directly responsible for the rapid rise in acidity as the a
nalytical HF concentration rises above 1 molal. No evidence was found
for any significant further association of HF with F- at molalities be
low 6.