Direct observation of liquid pre-crystallization intermediates during the reduction of aqueous tetrachloroaurate by sulfide ions.
Phenomena preceding precipitation of gold(i) sulfide in the reaction of aqueous tetrachloroauric acid with sodium sulfide have been studied applying several time-resolved in situ techniques. As can be deduced from UV-vis absorption spectroscopy, soluble species ("pre-nucleation clusters") emerge within several seconds and slightly change with time; the spectra, along with the previous data for the immobilized products, are indicative of disordered matter with Au(I)-S bonding and the gap of about 1.5 eV. In situ tapping-mode atomic force microscopy (AFM) directly imaged "soft" droplet-like species from 20-50 nm to about 200 nm in the lateral size and the continuous film condensed on the highly oriented pyrolytic graphite (HOPG) support. Small-angle X-ray scattering (SAXS) revealed quasi-particles ("liquid clusters") growing to about 12 nm for 30 min, and slowly afterwards. Dynamic light scattering (DLS) was preferentially due to the larger species, although the liquid clusters within 20 nm comprise more than 80% of the total volume of the fluid products. The entities, which exist in solution for many hours before sudden gold sulfide sedimentation, are considered as "dense liquid" intermediates involved in a non-classical nucleation pathway.
Institute of Chemistry and Chemical Technology of the Siberian Branch of the Russian Academy of Sciences, Akademgorodok, 50/24, 660036, Krasnoyarsk, Russia. yumikh@icct.ru.
Yuri
Y
Mikhlin
Anton
A
Karacharov
Maxim
M
Likhatski
Tatyana
T
Podlipskaya
Ivo
I
Zizak