Journal of Physical Chemistry, Vol.100, No.36, 14984-14990, 1996
Solubility of Nitrous-Acid (Hono) in Sulfuric-Acid-Solutions
The Henry’s law solubility of nitrous acid (HONO) has been studied in sulfuric acid solutions as a function of acid concentration in the range 0.3-73.6 wt % and temperature between 248 and 298 K by measuring the distribution of HONO between the gas and liquid phases using a bubbler-type gas-liquid reactor. Gas phase concentrations have been measured by highly sensitive tunable diode laser spectrometry, whereas the liquid phase has been analyzed by ion chromatography. At 298 K the Henry’s law constant of HONO in sulfuric acid is well described for H2SO4 concentrations < 53 wt % by K-H = (47.2 +/- 2.8) exp[(-0.044 +/- 0.002) C-H?2SO?4] mol kg(-1) bar(-1), with c(H2SO4) in wt %. The exponential dependence of K-H on C-H2SO4 that has been observed with increasing H2SO4 concentration is explained by the Setschenow equation. The values of Delta H-sol and Delta S-sol for the dissolution of HONO have been determined as a function of sulfuric acid concentration. The results were fitted to a four-parameter equation that allows the calculation of the effective solubility of HONO in the temperature and concentration ranges studied. In addition, the equilibrium between HONO and NO+ is discussed.