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Gold parting

Gold parting is a metallurgical employed to separate from silver and other base metals in alloys, enabling the production of high-purity essential for coinage, jewelry, and industrial uses. This selective technique exploits 's resistance to certain chemicals while dissolving the accompanying metals, typically achieving purities of 994 to 999 fine. Historically, gold parting originated with the salt cementation method in ancient around the 6th century BCE, during the reign of King , where (a natural gold-silver ) was heated with at approximately 800°C to volatilize silver as chloride compounds, leaving purified gold behind. Evidence suggests even earlier applications, potentially as far back as 1900 BCE in the , based on artifacts like the Tod Treasure. This innovation facilitated the minting of standardized pure gold currency and spread to regions such as , , and Achaemenid Persia. In modern practice, parting has largely supplanted earlier techniques, involving the or rolling of alloys followed by immersion in dilute solutions of varying strengths (specific gravities 1.2 to 1.3) to dissolve silver into , with residual collected after boiling, decanting, and washing. The process, scalable for industrial of or precise assays, minimizes loss to 0.01–0.03% while retaining trace silver (0.05–0.1%) in the final product, often requiring corrections for accuracy in mint operations. Although effective, it generates emissions necessitating environmental controls, and alternatives like the chlorination process are sometimes preferred for large-scale operations.

Fundamentals

Definition and Purpose

Gold parting is a metallurgical process that selectively separates from silver and base metals in alloys, enabling the production of higher-purity gold materials. This separation is essential because gold and silver are frequently co-extracted from ores and form stable alloys, necessitating targeted chemical or electrochemical methods to isolate the . Historically, gold parting addressed the limitations of natural , a -silver typically containing 20–80% along with varying amounts of silver and trace elements like . served as the primary starting material in ancient , where its variable composition made consistent purity challenging without parting techniques. The primary purposes of gold parting include enhancing the economic value of gold by increasing its purity for applications in coinage, jewelry, and industrial uses, as well as standardizing metal content for reliable trade and monetary systems—such as producing nearly pure coins from alloyed bullion. It also prepares separated gold for further steps, ensuring compliance with purity standards that boost marketability and . A key challenge in gold parting arises from the chemical similarity between gold and silver, particularly their shared nobility, which complicates separation and requires methods exploiting subtle differences like the inertness of gold versus the reactivity of silver to specific reagents.

Chemical Principles

Gold parting relies on the pronounced chemical nobility of gold, which exhibits exceptional resistance to oxidation and dissolution in most acids due to its high standard electrode potential of E^\circ (Au^{3+}/Au) = +1.50 V. This nobility stems from gold's position as a late transition metal, making the reduction of Au³⁺ to metallic gold highly favorable compared to common oxidizing agents like nitric acid or sulfuric acid. Only aqua regia, a mixture of concentrated nitric and hydrochloric acids, can dissolve gold by forming stable chloroauric acid complexes (HAuCl₄). In contrast, silver, often alloyed with gold, is far more reactive, with a lower standard electrode potential of E^\circ (Ag^{+}/Ag) = +0.80 V, allowing it to be selectively oxidized and dissolved under acidic conditions. The reactivity of silver enables its conversion to highly soluble silver nitrate (AgNO₃) in nitric acid, with a solubility of approximately 2150 g/L at 20°C, facilitating efficient separation from gold. In chloride-based environments, silver forms silver chloride (AgCl), which is sparingly soluble (Ksp ≈ 1.8 × 10⁻¹⁰), precipitating as a solid to aid parting. These solubility differences underpin the selective extraction of silver from gold-silver alloys, where the alloy's microstructure allows acid penetration to target silver atoms while leaving gold intact. A key reaction in nitric acid-based parting is the oxidation of silver: $3Ag + 4HNO_3 \rightarrow 3AgNO_3 + NO + 2H_2O This redox process involves nitrate ions acting as oxidants, producing soluble AgNO₃ and nitrogen monoxide gas, while gold remains undissolved due to its inertness toward nitric acid. To ensure complete silver removal without excessive acid consumption or gold loss, inquartation dilutes the gold content to approximately 25% by adding silver, achieving a 3:1 Ag:Au ratio that maximizes surface area exposure and promotes uniform dealloying. Common impurities such as base metals like copper are preferentially dissolved in nitric acid during parting, as copper readily forms soluble copper(II) nitrate (Cu(NO₃)₂) via oxidation, further purifying the residual gold. This selective dissolution exploits the lower nobility of base metals (e.g., E^\circ (Cu^{2+}/Cu) = +0.34 V), ensuring they do not contaminate the parted gold.

Historical Development

Ancient and Early Techniques

The earliest known techniques for gold parting emerged in the prehistoric during the period, around the , where depletion was employed to remove silver from the surface of alloys through oxidation. This method involved heating gold-silver alloys to form a layer on the surface, which was then mechanically removed by or chemical means, leaving a thin layer of nearly pure . Archaeological evidence from Nahal Qanah Cave in includes gold rings and circlets dated to approximately 4000–3500 BC, analyzed as objects that exhibit signs of surface enrichment consistent with depletion , marking the initial experimentation with separating precious metals in the . Recent analysis of artifacts from the Tod Treasure, discovered at the Temple of in El-Tod, , provides evidence of salt cementation gold parting as early as the (circa 1900 BCE, during the reign of ). Isotopic studies of silver objects indicate that the silver was likely separated from gold via heating with salt, volatilizing and leaving purified gold, predating similar techniques elsewhere. By the Early Bronze Age, in the , Mesopotamian artisans at developed mercury , also known as fire , as a related but distinct surface treatment for applying to base metals or enhancing alloys, though it did not achieve true bulk parting of from silver. This entailed amalgamating with mercury to form a paste applied to objects, followed by heating to evaporate the mercury and deposit a layer, as evidenced by artifacts from the Royal Tombs of , including gilded items showing mercury residues. While innovative for decorative purposes, mercury primarily coated surfaces rather than separating metals throughout the material, limiting its role in refining electrum ores. A significant advancement occurred in the in , at , where cementation was introduced as an early documented method for bulk separation of from silver in . was hammered into thin sheets or granules and layered with —likely rock —in coarse crucibles, then heated in ovens to around 800°C, allowing chlorine gas from the to react preferentially with silver, forming soluble that was absorbed by the porous vessel walls, leaving behind purified . Archaeological excavations at Sector PN near the River uncovered crucibles with residual , traces, and furnace structures dated to the mid-, confirming this as a verified industrial-scale parting technique in the ancient world. In ancient India, the Arthashastra, attributed to Kautilya and dated to the 4th century BC, describes a salt-based separation process for purifying gold dust, emphasizing the use of thin sheets of impure gold treated with salt to facilitate the removal of base metals through heating. This method involved mixing gold dust with salt and other fluxes before melting, leveraging the chemical difference where silver and impurities form chlorides more readily than gold, allowing for their extraction and yielding higher-purity gold suitable for coinage and ornaments. The text underscores quality control, such as using touchstones to verify purity post-treatment, reflecting systematic state oversight of metallurgical practices. These ancient and early techniques were inherently limited by their low efficiency, often affecting merely the surface layers rather than the entire volume of material, which restricted their application to small-scale or decorative without enabling large-volume production of high-purity .

Medieval and Post-Medieval Advances

In the , documented one of the earliest detailed descriptions of the salt cementation process for gold parting in his De diversis artibus. He instructed the use of brick dust moistened with urine and mixed with rock or in a 2:1 to form a , into which thin gold foils were embedded alternately without touching one another, then sealed in a ceramic vessel and heated in a for at least one night. This method, building on ancient precursors like those from , selectively removed silver and base metals as chlorides while leaving purified behind, achieving silver contents below 2% in the residue. During the Islamic Golden Age, alchemists such as Jābir ibn Ḥayyān advanced knowledge of acids critical to refining, including the development of aqua regia—a mixture of nitric and hydrochloric acids capable of dissolving gold—with the first clear descriptions of nitric acid appearing in the 13th century through distillation of saltpeter with vitriol. These innovations facilitated more effective separation techniques and likely influenced European practices via translations of Arabic texts. By the 13th century, these ideas transmitted to Europe, where nitric acid parting emerged around 1300–1400, allowing for bulk separation of gold from silver alloys by dissolving the silver without attacking the gold. Albertus Magnus provided the first clear European mention of nitric acid for this purpose in the 13th century, marking a shift from labor-intensive cementation to more efficient chemical dissolution. By the , assay manuals like the Probierbüchlein, an early German text on testing, outlined and methods that formed to isolate from alloys. These involved heating impure with elemental or under controlled conditions in sealed crucibles, volatilizing impurities while enriching the gold residue, and represented a refinement of earlier sulfide-based separations for and small-scale refining. Post-medieval advancements culminated in the widespread adoption of acid-based parting at major mints, such as the Venetian Mint around 1475 and various German facilities by the early 1500s, where enabled industrial-scale coin refining and ensured high-purity for production.

19th-Century Innovations

The and of the mid-19th century generated vast quantities of gold ore often heavily alloyed with silver and other impurities, creating an urgent demand for scalable refining techniques to process large volumes efficiently. These events, peaking around in and in , , shifted gold parting from artisanal methods to industrial practices, as traditional processes proved inadequate for the influx of low-grade . In the 1860s, the Miller process emerged in as a breakthrough for large-scale silver removal, involving the introduction of chlorine gas into molten impure gold to form , which could be skimmed off. Patented in 1867 by Francis Bowyer Miller, this method allowed refiners to handle thousands of ounces daily, producing gold of approximately 99.5% purity suitable for production. Concurrently, gained traction as a cost-effective alternative to for parting in flasks or crucibles, particularly for silver-rich alloys, by heating the mixture to drive off while leaving gold intact. By 1874, Emil Wohlwill in , , invented the electrolytic Wohlwill process, which further elevated purity levels to 99.99% through anode dissolution of impure in a , depositing pure on the . This innovation addressed limitations in chemical methods by enabling precise control over impurities like metals. These 19th-century advancements collectively facilitated gold purities exceeding 99%, underpinning the global adoption of the gold standard from the onward by ensuring consistent, verifiable quality for and coinage. The transition to factory-scale operations during this era transformed gold parting into a cornerstone of modern metallurgy, supporting economic stability amid expanding mining outputs.

Traditional Processes

Salt Cementation

Salt cementation, a pyrometallurgical for separating from silver in alloys, served as the predominant non-acidic method from the until the AD, with early adoption in ancient for refining . This process was especially suited to low-silver alloys containing less than 20% silver, where it efficiently removed the while preserving integrity. The procedure begins by preparing the gold-silver alloy in thin foils or powder form, which is then intimately mixed with common (NaCl), powdered burnt or dust as a , and occasionally or other to achieve a consistency for even distribution. This mixture is layered into a clay-sealed crucible or vessel to prevent gas escape, then heated in a to 600–900°C, allowing and reaction to proceed. At these temperatures, the interacts with oxygen and silicates from the clay, generating gas or that selectively attacks silver. The core chemical reaction involves the formation of volatile silver chloride: Cl₂ + 2Ag → 2AgCl, where silver chloride sublimes and escapes as vapor, while gold remains unmelted and unaffected due to its higher melting point and chemical inertness. Impurities such as base metals form slag with the clay and are skimmed off or left behind, purifying the residual gold button. The process duration varies from several hours for initial parting to multiple days for iterative cycles, often requiring 19–20 hours per heating stage and repetition to reduce silver below 0.3%. This method's advantages lie in its rudimentary requirements—no strong acids or complex equipment needed—enabling widespread use in pre-industrial settings for achieving gold purities up to 99.7%. It effectively removed silver that cupellation alone could not, enhancing alloy quality for coinage and artifacts. However, drawbacks include labor-intensive preparation and firing, inefficiency with high-silver alloys (>20% Ag) due to slower diffusion and incomplete reaction, and potential gold losses of up to 5% from adhesion to crucible walls or volatilization.

Sulfur and Antimony Methods

The sulfur and methods for gold parting involve thermal processes that exploit the formation of insoluble to separate silver from gold-silver alloys, primarily used in historical assaying and . These techniques, documented in medieval and early texts, apply or (Sb₂S₃, also known as ) to powdered alloys, offering a faster alternative to salt-based cementation by promoting reactions in a controlled heating environment. In the procedure, the gold-silver alloy is first powdered and intimately mixed with elemental or in a suitable or mold, such as a conical fusorius made of clay or metal. The mixture is then heated to temperatures between 500°C and 700°C in a small , allowing sulfur to react selectively with silver while remains largely unaffected and collects at the bottom or center. serves as both a sulfur source and a carrier, facilitating the transport of sulfur to the silver particles and forming a slag-like layer of (Ag₂S) that can be mechanically separated; any that alloys with the gold is later removed by oxidation or volatilization. The key reaction is $2Ag + S \rightarrow Ag_2S, which occurs preferentially due to silver's higher affinity for sulfur compared to . These methods trace their origins to medieval practices, with sulfur-based parting first described by Theophilus Presbyter in the , and antimony variants detailed in 16th-century German texts such as the Probierbüchlein, where they were employed for assaying ores and refining bullion in mining regions like . Building on earlier medieval documentation of uses in , the processes were valued for their speed over cementation, completing separation in a single heating cycle rather than requiring prolonged exposure, though they carried higher risks due to volatile compounds. Efficiency in these methods typically achieves approximately 95% gold purity in one pass, with experimental recreations showing near-complete silver removal (up to 99% in optimized conditions) and reduced losses from gold encapsulation compared to purely sulfur-based approaches, as helps fluidize the mixture. The variant minimizes gold entrapment in the sulfide slag by alloying temporarily with gold, allowing cleaner separation upon subsequent . Despite their effectiveness, the and methods have notable drawbacks, including the release of toxic fumes from volatilization, which posed health risks to operators, and potential contamination of the gold with antimony residues that could require additional steps like air oxidation to achieve higher purity. These thermal, dry processes contrasted with liquid-based alternatives by avoiding acids but were eventually supplanted by safer electrolytic methods in the .

Nitric Acid Parting

parting is a selective dissolution process used to separate from silver in alloys, relying on the chemical inertness of to while silver readily forms soluble . This method, particularly effective for alloys with high silver content, involves first diluting the through inquartation to ensure complete silver removal without significant loss. The process produces a porous residue that can be further refined, making it suitable for laboratory-scale or small-batch operations. The inquartation step begins by alloying the gold-containing material with silver to achieve approximately a 25% content by weight, typically in a 3:1 silver-to-gold ratio, which prevents excessive gold dissolution during acid treatment. This dilution is accomplished by melting the with silver (or sometimes as a substitute ) and the into a homogeneous form. follows, where the is poured into to create small, high-surface-area particles that enhance the efficiency of the subsequent . In the procedural steps, the granulated is boiled in dilute , typically 20-50% concentration (such as 5.6 M initially), for about 30 minutes to several hours to dissolve the silver as , leaving behind a brown, spongy residue. The mixture is then filtered to separate the gold, which is washed with water and additional dilute acid to remove residual silver. This is repeated with stronger (up to 9.4 M or 68% concentration) to ensure thorough silver removal, followed by final washing and drying of the gold residue. Silver is recovered from the nitrate solution through precipitation methods, such as adding to displace silver or using caustic soda for further processing. The key reaction involves the oxidation of silver by (for dilute conditions), represented as: $3 \mathrm{Ag} + 4 \mathrm{HNO_3} \rightarrow 3 \mathrm{AgNO_3} + \mathrm{NO} + 2 \mathrm{H_2O} Gold remains completely inert to under these conditions. The inquartation ensures that the silver is fully accessible to the acid; if the initial gold content exceeds approximately 25-30%, some silver may remain undissolved, trapped within the resulting gold structure. This technique originated in 13th-century following the discovery of by alchemists, who adapted it from earlier selective corrosion methods, and it became a standard for small-scale in 19th-century laboratories due to its and for . Yields typically exceed 99%, with the resulting achieving purities of 99-99.9% (994-999 fine), depending on the number of treatments and composition.

Modern Methods

Miller Process

The Miller process, a pyrometallurgical method for refining , was invented in the 1860s by Francis Bowyer Miller, an assayer who worked at the Sydney Branch of the Royal Mint in , and patented in in 1867. First implemented at the Sydney Mint and later at the Auckland Mint by 1869, it became a cornerstone of industrial gold refining due to its efficiency in handling large volumes of impure gold-silver alloys, known as doré bars. In the procedure, impure doré is melted in a at temperatures of 1000–1100°C, typically covered with a flux layer of and silica to protect the melt and facilitate slag formation. gas is then introduced and bubbled through or passed over the molten alloy, selectively reacting with silver and other impurities such as , lead, iron, and to form volatile or solid . These rise to the surface as a skim or are carried off in exhaust gases, allowing them to be removed periodically; the process concludes when the exiting fumes exhibit a characteristic color change upon on a cold surface, indicating near-complete reaction. The primary reaction for silver removal is $2Ag + Cl_2 \rightarrow 2AgCl, where remains in the molten state unaffected due to the instability of gold chloride at these temperatures. The resulting gold achieves a purity of approximately 99.5% (995 ), with residual impurities primarily consisting of minor silver and . Silver and other metals are recovered from the chloride through subsequent treatments, such as dissolution in solutions, minimizing losses to about 1–2% of the gold content entrained in the . This method's advantages include rapid ing times—typically completing in a few hours—and scalability for tons of material at low cost, making it suitable for large-scale operations worldwide. However, it presents disadvantages such as the hazards associated with handling toxic gas and the production of corrosive byproducts, alongside its limitation to moderate purity levels compared to electrolytic alternatives. By the mid-1990s, estimates indicated that two-thirds of globally refined utilized this .

Wohlwill Process

The Wohlwill process is an electrolytic technique designed to achieve investment-grade purity in , typically starting from impure anodes produced by prior methods such as the Miller process. Patented in 1874 by German engineer Emil Wohlwill, the process involves the electrochemical separation of from impurities like silver and base metals, resulting in cathode deposits of exceptionally pure . It has been adopted by major industrial refineries, including Rand Refinery in , for producing high-purity suitable for and fabrication. The setup consists of an with an cast from impure (typically 90-98% pure), a in the form of a thin starter sheet of pure , and an solution of gold chloride (AuCl₃) dissolved in (HCl), approximately 120 g/L with 5–10% free HCl. The impure , often sourced from Miller process output containing residual silver and base metals, serves as the source material for dissolution. In the procedure, electrolysis is applied at a of 3-4 V and a maintained between 60-80°C to optimize and deposition rates. Gold ions dissolve from the and migrate to the , where they deposit as pure metal, while silver precipitates primarily as sludge and base metals either dissolve into the or form insoluble residues. The process operates continuously, with anodes typically lasting 16-18 hours before replacement, and the is circulated to prevent buildup of impurities. The key cathodic reaction is the reduction of gold tetrachloroaurate ions: \ce{AuCl4^- + 3e^- -> Au + 4Cl^-} At the anode, gold oxidizes to Au³⁺ ions, which complex with chloride to form the soluble AuCl₄⁻ species. The output is gold of 99.99% or greater purity, often reaching 99.999% in optimized operations, with overall recovery efficiency around 95% due to minimal losses in the slime and electrolyte. The anode slime, a byproduct rich in metals (PGMs) such as and , is collected and further processed for valuable recoveries. Energy consumption for the electrolysis is approximately 3-5 kWh per kg of refined, reflecting the low-voltage, high-amperage conditions.

Acid-Less Separation

Acidless separation, also known as , is a modern technique designed as an alternative to traditional acid-based methods for separating from high-silver alloys, particularly those containing over 50% silver such as jewelry scrap. Developed through a collaboration between the firm IKOI and Russia's Ekaterinburg Non-Ferrous Metals Processing Plant (EZ-OCM), the process was refined and patented around 2014, with commercial adoption beginning by 2016 among LBMA-accredited refineries. Unlike historical parting, which relies on chemical and generates , ALS employs thermal without any acids or chemicals, achieving zero emissions and simplifying . The procedure involves placing the in a and heating it to temperatures between 1300°C and 1450°C under a high of 10^{-2} to 10^{-3} mbar (approximately 7.5 \times 10^{-3} to 10^{-3} ), where silver and other volatile elements like volatilize as vapors while remains as a solid residue. These vapors are then condensed on a cooled surface, allowing for selective separation based on differences in vapor pressures; for instance, silver, which boils at 2162°C under atmospheric conditions, evaporates at significantly lower temperatures under due to reduced pressure. The process is fully automated, typically handling batches of 15–200 kg depending on system configuration, and results in of 99.9% purity suitable for further refining, with no metal losses reported. Key advantages include the elimination of chemical reagents, which avoids the production of NOx emissions and acidic effluents associated with traditional wet methods, making it ideal for sustainable operations in compliance with standards. Refineries such as Refinery in and MMTC-PAMP in have integrated into their workflows by 2019, leveraging its cost-effectiveness and versatility for alloys with varying compositions. As of 2025, the technology continues to see growing adoption in global precious metals refining, particularly for processing dore and scrap with high silver content, driven by increasing regulatory pressures on environmental impacts; adoption has expanded to include The in .

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    Acidless Separation (ALS) removes silver and light elements from alloys using vacuum distillation, with no chemicals, fumes, or smoke, and separates gold and ...