|Abstract or Summary
- Solubility studies on the heavy metal sulfides in liquid hydrogen
sulfide at room temperature were carried out using the isopiestic
method. The results were compared with earlier work and with a
theoretical result based on Raoult's Law. A relative order for the
solubilities of sulfur and the sulfides of tin, lead, mercury, iron,
zinc, antimony, arsenic, silver, and cadmium was determined and
found to agree with the theoretical result.
Hydrogen sulfide is a strong enough oxidizing agent to oxidize
stannous sulfide to stannic sulfide in neutral or basic solution (with
triethylamine added). In basic solution antimony trisulfide is oxidized
to antimony pentasulfide. In basic solution cadmium sulfide
apparently forms a bisulfide complex in which three moles of bisulfide
ion are bonded to one mole of cadmium sulfide.
Measurements were made extending the range over which the
volumetric properties of hydrogen sulfide have been investigated to
220°C and 2000 atm. A virial expression in density was used to
represent the data. Good agreement, over the entire range investigated,
between the virial expressions, earlier work, and the
theorem of corresponding states was found.
Electrical measurements were made on supercritical hydrogen
sulfide over the density range of 10-24 moles per liter and at
temperatures from the critical temperature to 220°C. Dielectric
constant measurements were represented by a dielectric virial expression.
Conductivity measurements were made on pure hydrogen
sulfide and on solutions containing, respectively, stannic sulfide,
lead sulfide, and triethylammonium chloride. The conductivity of
the solutions of stannic sulfide and lead sulfide showed slight increases
over the conductivity of the pure solvent. Triethylammonium
chloride solutions exhibited a conductivity that was over a thousand
times that of the pure hydrogen sulfide at the same density.
Virial coefficients derived from both compressibility data and
dielectric constant measurements showed evidence of very little
(H₂S)x polymer formation. Conductivity measurements indicate a
very small solubility for the metal sulfides in hydrogen sulfide,
which itself is very slightly ionized. Solutions of triethylammonium
chloride are ionized extensively.
Crystal growth experiments were undertaken to demonstrate
the feasibility of the solution growth of crystals of cadmium sulfide, lead sulfide, silver sulfide, and stannic sulfide from pure supercritical
hydrogen sulfide. It was shown that stannic sulfide, lead
sulfide, and silver sulfide could be grown from these solutions.
Growth rates were extremely slow.