Gold extracted by amalgamation or cyanidation contains a variety of impurities, including zinc, copper, silver, and iron. Two methods are commonly employed for purification: the Miller process and the Wohlwill process. The Miller process is based on the fact that virtually all the impurities present in gold combine with gaseous chlorine more readily than gold does at temperatures equal to or greater than the melting point of gold. The impure gold is therefore melted and gaseous chlorine is blown into the resulting liquid. The impurities form chloride compounds that separate into a layer on the surface of the molten gold.

The Miller process is rapid and simple, but it produces gold of only about 99.5 percent purity. The Wohlwill process increases purity to about 99.99 percent by electrolysis. In this process, a casting of impure gold is lowered into an electrolyte solution of hydrochloric acid and gold chloride. Under the influence of an electric current, the casting functions as a positively charged electrode, or anode. The anode dissolves, and the impurities either pass into solution or report to the bottom of the electrorefining tank as an insoluble slime. The gold migrates under the influence of the electric field to a negatively charged electrode called the cathode, where it is restored to a highly pure metallic state.

Although the Wohlwill process produces gold of high purity, it requires the producer to keep on hand a substantial inventory of gold (mainly for the electrolyte), and this is very costly. Processes based on direct chemical purification and recovery from solution as elemental gold can greatly speed gold processing and virtually eliminate expensive in-process inventories.

Refining from scrap

The processing of gold scrap varies not only with the gold content but also with the amenability of the gold in the scrap to extraction. Thus, the bulk of the gold may be recovered by leaching techniques using cyanidation or aqueous chlorination, and the residue may then be treated by smelting to recover the balance. Generally, scrap with a gold content of less than 0.1 percent, unless readily recoverable by leaching, is recycled back to a pyrometallurgical process. Metallic scrap gold from jewelry production is frequently melted on-site and reused.

Assaying

Fire assay is considered the most reliable method for accurately determining the content of gold, silver, and platinum-group metals (except osmium and ruthenium) in ores or concentrates. This process involves melting a gold-bearing sample in a clay crucible with a mixture of fluxes (such as silica and borax), lead oxide (called litharge), and a reducing agent (frequently flour). The fluxes lower the melting point of the oxidic materials, allowing them to fuse, and the molten litharge is reduced by the flour to extremely fine drops of lead dispersed throughout the charge. The drops of lead dissolve the gold, silver, and platinum-group metals, then coalesce and gradually descend through the sample to form a metallic layer at the bottom of the crucible. After cooling, the lead “button” is separated from the slag layer and heated under oxidizing conditions to oxidize and eliminate the lead. The shiny metallic bead that is left contains the precious metals. The bead is boiled in nitric acid to dissolve the silver (a process called parting), and the gold residue is weighed. If platinum metals are present, they will alter the appearance of the bead, and their concentration can sometimes be determined by use of an arc spectrograph.

In the jewelry industry, gold content is specified by karat. Pure gold is designated 24 karats; therefore, each karat is equal to 4.167 percent gold content, so that, for example, 18 karats equals 18 × 4.167, or 75 percent gold. “Fineness” refers to parts per thousand of gold in an alloy; e.g., three-nines fine would correspond to gold of 99.9 percent purity.