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Mercury sulfide
Mercury sulfide
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Mercury sulfide
Names
IUPAC name
Mercury sulfide
Other names
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.014.270 Edit this at Wikidata
EC Number
  • 215-696-3
UNII
UN number 2025
  • InChI=1S/Hg.S
    Key: QXKXDIKCIPXUPL-UHFFFAOYSA-N
  • [S]=[Hg]
Properties
HgS
Molar mass 232.66 g/mol
Density 8.10 g/cm3
Melting point 580 °C (1,076 °F; 853 K) decomposes
insoluble
Band gap 2.1 eV (direct, α-HgS) [1]
−55.4·10−6 cm3/mol
w=2.905, e=3.256, bire=0.3510 (α-HgS) [2]
Thermochemistry
78 J·mol−1·K−1[3]
−58 kJ·mol−1[3]
Hazards
GHS labelling:
GHS06: ToxicGHS07: Exclamation markGHS08: Health hazardGHS09: Environmental hazard
Danger
H300, H310, H317, H330, H373, H410
P261, P272, P280, P302+P352, P321, P333+P313, P363, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
4
0
0
Flash point Non-flammable
Safety data sheet (SDS) Fisher Scientific
Related compounds
Other anions
 Mercury oxide
mercury selenide
mercury telluride
Other cations
 Zinc sulfide
cadmium sulfide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Mercury sulfide or mercury(II) sulfide is a chemical compound composed of the chemical elements mercury and sulfur. It is represented by the chemical formula HgS. It is virtually insoluble in water.[4]

Crystal structure

[edit]
Structure of a-HgS looking at the a-axis
Structure of a-HgS looking at the c-axis

HgS is dimorphic with two crystal forms:

Preparation and chemistry

[edit]

β-HgS precipitates as a black solid when Hg(II) salts are treated with H2S. The reaction is conveniently conducted with an acetic acid solution of mercury(II) acetate. With gentle heating of the slurry, the black polymorph converts to the red form.[6] β-HgS is unreactive to all but concentrated acids.[4]

Mercury is produced from the cinnabar ore by roasting in air and condensing the vapour.[4]

HgS → Hg + S

Uses

[edit]
Cinnabar (red portion of specimen)

When α-HgS is used as a red pigment, it is known as cinnabar. The tendency of cinnabar to darken has been ascribed to conversion from red α-HgS to black β-HgS. However β-HgS was not detected at excavations in Pompeii, where originally red walls darkened, and was attributed to the formation of Hg-Cl compounds (e.g., corderoite, calomel, and terlinguaite) and calcium sulfate, gypsum.[7]

As the mercury cell as used in the chlor-alkali industry (Castner–Kellner process) is being phased out over concerns over mercury emissions, the metallic mercury from these setups is converted into mercury sulfide for underground storage.

With a band gap of 2.1 eV and its stability, it is possible to be used as photoelectrochemical cell.[8]

Neutralization with sulfur has been suggested to clean mercury spills, but the reaction does not proceed rapidly and completely enough for emergencies.[9]

See also

[edit]

References

[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia

Mercury sulfide

View on Grokipedia
from Grokipedia
Mercury sulfide, with the HgS, is an that occurs naturally as the , a bright red crystalline serving as the principal source of elemental mercury worldwide. It exists in two primary polymorphs: the red α-HgS (), which is stable and dense, and the black β-HgS (metacinnabar), which is less common and more reactive. The compound is characterized by its low in (approximately 4.5 × 10⁻²⁴ mol/L) and high stability under physiological conditions, rendering it less bioavailable than other mercury forms, though it can release toxic mercury ions under acidic or heated environments. Cinnabar deposits are primarily found in volcanic and hydrothermal regions, with significant historical mining sites in areas such as , , , and , where it is extracted via open-pit or underground methods to produce mercury for industrial applications. Historically, mercury sulfide has been valued for its vibrant red color, used as the pigment in art, cosmetics, and traditional medicines across cultures, including ancient Chinese remedies and Mayan pigments, though such uses have declined due to health concerns. Despite its relative insolubility, mercury sulfide poses toxicity risks, particularly through inhalation of dust during mining or processing, which can lead to acute poisoning at concentrations of 1.2–8.5 mg/m³, or chronic exposure causing neurological effects like tremors, renal damage, and immune alterations. Its environmental persistence contributes to mercury contamination in soils and water near mine sites, accumulating in food chains and posing risks to ecosystems and human health, with the Immediately Dangerous to Life or Health (IDLH) value set at 10 mg Hg/m³. Under international agreements like the Minamata Convention on Mercury (effective 2017), primary production and use are being phased down as of 2025, emphasizing safer alternatives for pigments and remediation of legacy mining sites.

Overview

Chemical identity

Mercury sulfide, with the molecular formula HgS, is a binary chemical compound consisting of mercury and in a 1:1 ratio. It is also known by its IUPAC name mercury(II) . The compound has a of 232.66 g/mol and is registered under the CAS number 1344-48-5. Mercury sulfide exhibits dimorphism, existing in two distinct polymorphic forms: the red α-HgS, commonly referred to as , and the black β-HgS, known as metacinnabar. These forms differ in their crystal structures but share the same chemical composition. The name "cinnabar" originates from the Latin cinnabaris, borrowed from the kinnábari, which likely derives from a Persian term meaning "," reflecting the mineral's vivid .

Natural occurrence

primarily occurs in nature as , the alpha polymorph (α-HgS), which serves as the chief of mercury and is typically found filling hydrothermal veins alongside minerals such as and . This bright red mineral imparts a distinctive scarlet hue to the host rocks, making deposits visually striking and historically easy to identify. forms through the precipitation of mercury from hot, mercury-enriched fluids associated with volcanic activity or alkaline hot springs, often in near-surface environments where temperatures allow for and crystallization in fractures. Major global deposits of cinnabar are concentrated in regions with significant tectonic and volcanic histories. The Almadén district in represents the historically largest mercury province, accounting for about one-third of worldwide production over centuries through stratabound and vein-type ores. Similarly, the Idrija mine in has been a key site since antiquity, yielding high-grade cinnabar in epithermal veins linked to . In , the Wuchuan mercury mine in Province is part of the vast Xiangqian belt, which holds approximately 70% of the nation's reserves and features extensive cinnabar-quartz-pyrite assemblages. The New Almaden deposit in , USA, another prominent vein system, supplied mercury during the 19th-century era, with cinnabar occurring in serpentinized ultramafic rocks. Less common is the beta polymorph (β-HgS), known as metacinnabar, which appears in low-temperature, near-surface mercury deposits, including sedimentary environments where it forms as a black, cubic under conditions favoring metastable . Rare occurrences of metacinnabar-like forms also arise in volcanic sublimates, where mercury vapors condense directly from high-temperature fumarolic gases in settings like active volcanoes.

Properties

Crystal structure

Mercury sulfide (HgS) exhibits polymorphism, with two primary crystal structures: the stable α-HgS () and the metastable β-HgS (metacinnabar). The α-HgS form crystallizes in the trigonal system with P3₁2₁ (No. 152), consisting of one-dimensional helical chains along the c-axis in which each Hg atom is linearly coordinated to two S atoms via short covalent bonds of approximately 2.36 , supplemented by four longer interactions to neighboring chains forming a distorted octahedral . The lattice parameters for this structure are a = 4.145 and c = 9.496 , with three formula units per . The equilibrium phase transition from α-HgS to β-HgS occurs at approximately 344 °C under , though β-HgS is kinetically metastable below this temperature and converts slowly to the stable α form. In contrast, β-HgS adopts the cubic zincblende structure with F¯43m (No. 216), featuring tetrahedral coordination for both Hg and S atoms, akin to the sphalerite structure of ZnS, where each Hg is surrounded by four S atoms at bond lengths of about 2.52 . The lattice parameter is a = 5.853 , resulting in a more isotropic arrangement compared to the anisotropic chains in α-HgS. The α-HgS phase undergoes a reconstructive to the β-HgS form upon heating above approximately 344 °C at . The β form is the high-temperature polymorph but is metastable at , slowly converting to α-HgS over time. Applied pressure can influence the transition temperatures. The structural features of these polymorphs influence their stability: the helical chain motif in α-HgS, often described in terms of layered packing of chains, underpins its high insolubility in (K_sp ≈ 10^{-52}) due to strong intrachain covalency and its characteristic arising from a direct of ~2.0 eV modulated by the chain . Conversely, the sphalerite-like bonding in β-HgS confers greater kinetic stability as a high-temperature phase but renders it metastable at ambient conditions, slowly reverting to α-HgS over time.

Physical properties

Mercury(II) sulfide exists in two polymorphs: the red α-HgS () and the black β-HgS (metacinnabar). The α form appears as a powder or crystalline solid, while the β form is a black or gray-black powder. The density of α-HgS is 8.10 g/cm³, and for β-HgS it is 7.73 g/cm³. Mercury(II) sulfide does not melt but thermally decomposes above 265 °C into mercury vapor and via the reaction 2 HgS → 2 Hg(g) + S₂(g), with significant rates observed up to 345 °C. Optically, α-HgS exhibits a direct of 2.1 eV, indicating behavior suitable for certain electronic applications, while the is 2.905 for α-HgS and 2.689 for β-HgS. Mercury(II) sulfide is insoluble in , with a solubility product constant (Ksp) on the order of 10^{-52} to 10^{-54}, and it has a Mohs of 2.0–2.5 for α-HgS and 3 for β-HgS. Both polymorphs are diamagnetic, attributable to the closed-shell electronic configurations of Hg²⁺ and S²⁻ ions.

Chemical properties

Mercury(II) sulfide (HgS) exhibits predominantly covalent bonding between mercury and sulfur atoms, with a small degree of ionic character arising from the electronegativity difference of 0.58 between Hg (2.00) and S (2.58). In the α-HgS () form, the short intra-chain Hg-S measures approximately 2.37 Å, reflecting the linear around mercury. This polarity contributes to the compound's overall stability and reactivity profile. HgS demonstrates high in air at ambient conditions and resists dissolution in dilute acids due to its low . However, it dissolves in concentrated , as shown by the reaction HgS + 10 HNO₃ → H₂SO₄ + 8 NO₂ + Hg(NO₃)₂ + 4 H₂O, or in , where the mixture facilitates oxidation and complexation. Similarly, it is resistant to most non-oxidizing acids but can be attacked by strong oxidants. In terms of behavior, HgS features mercury in the +2 and in the -2 state, rendering it a stable under reducing conditions. It serves as a source of ions in certain reactions and undergoes to elemental mercury and above 265°C, with the rate increasing significantly up to 345°C. The decomposition follows: 2 HgS → 2 Hg + S₂, highlighting its role in high-temperature processes. HgS can form colloidal suspensions in alkaline sulfide solutions, where complexes stabilize the nanoparticles without hydration shells, as evidenced by studies on β-HgS in sulfidic environments. reveals a characteristic Hg-S stretching vibration at approximately 350 cm⁻¹, confirming the covalent nature of the bond in the solid state.

Synthesis and production

Laboratory preparation

Mercury(II) sulfide (HgS) is commonly prepared in the laboratory via precipitation from an aqueous solution of mercury(II) chloride (HgCl₂) by bubbling hydrogen sulfide (H₂S) gas at room temperature, resulting in the formation of the black β-HgS polymorph, known as metacinnabar. The reaction proceeds as follows: \ceHgCl2+H2S−>[H2O,RT]HgS(β)+2HCl\ce{HgCl2 + H2S ->[H2O, RT] HgS (\beta) + 2HCl} This method yields a fine black precipitate that can be filtered and washed with water to remove soluble byproducts. The black β-HgS can be converted to the thermodynamically stable red α-HgS (cinnabar) form through a solid-state phase transition that occurs slowly at room temperature or can be accelerated by heating to 200–300°C under an inert atmosphere. The resulting red powder is the desired α-HgS. The crystal forms produced in these preparations correspond to the cubic β-HgS and hexagonal α-HgS structures. Alternative laboratory routes include the reaction of mercury(II) oxide (HgO) with elemental sulfur, where mixing the solids and heating leads to HgS formation through direct combination. Another approach involves exposing elemental mercury to sulfur vapor at approximately 200°C, producing HgS via gas-solid reaction; this dry method initially forms black β-HgS, which can then be converted to the red α-form. These methods are particularly useful for obtaining purer synthetic samples without chloride impurities. Purification of the product, especially from dry syntheses, typically involves washing the precipitate with (CS₂) to dissolve and remove any residual free , followed by drying under vacuum. Yields from these and heating procedures generally range from 90% to 95%, depending on reaction scale and purity of starting materials. Historically, in the early , laboratory preparations often employed the wet method using mercuric nitrate (Hg(NO₃)₂) and (Na₂S) in to precipitate HgS, as described in contemporary chemical texts; this approach mirrored the modern technique but utilized nitrate salts for solubility advantages.

Industrial production

The primary industrial method for producing mercury from mercury sulfide ( ore) has historically involved the ore in furnaces at approximately 600°C, where the reaction 2HgS + 3O₂ → 2Hg + 2 occurs, releasing mercury vapor that is subsequently condensed and collected as . This , conducted in rotary kilns or retorts, was the dominant technique for large-scale extraction, with the ore first crushed and concentrated before heating to ensure efficient vaporization and separation from byproducts. In integrated facilities, the SO₂ emissions from were often captured for recovery using the , where partial reduction to H₂S enables catalytic conversion to elemental , improving resource efficiency and reducing emissions. A notable historical example is the mining district in , which utilized retort-based roasting and produced around 236 tonnes of mercury annually in the early 2000s, contributing significantly to global supply before scaling down. This method remained the cornerstone of mercury production until global phase-outs, driven by environmental concerns, with primary mining operations required to phase out by 2032 under the , adopted in 2013 and allowing continuation for up to 15 years after entry into force (2017) for existing mines. As of November 2025, primary mining continues in several countries, with COP-6 discussions considering acceleration of the phase-out timeline. In contemporary contexts, mercury sulfide is produced industrially not from extraction but through processes, particularly the treatment of mercury effluents from chlor-alkali plants via to form stable HgS for long-term disposal in secure facilities like salt mines. This conversion stabilizes highly toxic metallic mercury into an insoluble form, preventing environmental release, and aligns with regulations prohibiting new . Global mercury supply as of 2023 includes approximately 600–1000 tonnes annually from secondary sources like of end-of-life products and industrial wastes, expected to increase following the full phase-out of primary .

Applications

Historical uses

Mercury sulfide, particularly in its red form known as or , has been prized as a vibrant red pigment since antiquity. In ancient , ground was used as early as the period for burial rituals and decorative purposes, with evidence from sites dating back to around 5000 BCE, though widespread application in artifacts appears by 3000 BCE. The Romans extensively employed natural in wall paintings, including the elaborate frescoes of Pompeii, where it provided a luxurious scarlet hue for architectural details and figures, often imported from mines in . During the , artists like incorporated into oil paintings for its intense, warm red tones, as seen in works such as Assumption of the Virgin (1516–1518), where it enhanced flesh tones and drapery when mixed with . In traditional medicine, mercury sulfide played a significant role in both Chinese and Indian systems. Known as zhusha in traditional Chinese medicine, cinnabar was incorporated into formulations for its purported sedative and longevity-promoting effects, often as an ingredient in elixirs aimed at enhancing vitality and treating ailments like insomnia. In Ayurvedic practices, the red sulfide of mercury, termed rasasindur, was prepared through sublimation and used as a rejuvenating agent (rasayana) to address conditions such as nervous disorders and high fever, believed to balance bodily humors. By the 16th century in Europe, mercury compounds derived from calomel (a related mercurous chloride often linked to sulfide processes) were administered for syphilis treatment, applied topically or ingested despite emerging reports of adverse effects. Alchemical traditions further elevated mercury sulfide's status, with symbolizing transformation and referred to in some Hermetic texts as "" due to its evoking mythical vitality. It was employed practically in techniques to create fire-gilt surfaces on metals and in for and coloring, though these uses carried inherent risks from mercury exposure. A notable challenge with in historical murals was its tendency to darken over time, particularly in environments with chloride exposure, such as Roman sites affected by volcanic gases. Studies from the have confirmed that this discoloration results from the formation of (HCl) reacting with the pigment to produce grayish mercury chlorides, rather than a phase shift to the black beta-HgS form. By the , awareness of mercury sulfide's —linked to chronic among artists, miners, and users—led to its gradual decline in favor of safer synthetic alternatives like red, though persisted in some applications into the early .

Contemporary uses

Due to stringent regulatory restrictions on mercury compounds, contemporary uses of mercury sulfide (HgS) are highly limited and primarily confined to specialized industrial, research, and analytical applications. In , HgS plays a key role in stabilizing liquid mercury wastes by converting them into insoluble sludge for safe landfill storage; this process involves reacting metallic mercury with to form (α-HgS), which is considered the least bioavailable mercury compound. Such stabilization techniques have been implemented in facilities across the and the since the early 2000s, aligning with guidelines for environmentally sound management of mercury wastes. In semiconductor research, α-HgS thin films are explored for photoelectrochemical (PEC) cells due to their suitable for visible light absorption. Studies from the mid-2000s demonstrated prototypes of HgS thin films deposited via chemical bath methods, showing thickness-dependent PEC performance for potential applications. For niche applications in art restoration, synthetic (HgS) is occasionally used as a to match historical colors in conservation efforts, though rarely due to toxicity concerns and regulatory bans on broader pigment use. HgS also serves as a reference standard in , particularly for calibrating (XRF) spectrometers to quantify mercury in environmental and material samples. As of 2025, uses of HgS are severely restricted under the European Union's REACH regulation (Annex XVII) and the U.S. Toxic Substances Control Act (TSCA), which mandate reporting and limit intentional addition in products.

Health, safety, and environmental impact

Toxicity

Mercury sulfide (HgS) poses health risks primarily through and , with GHS classification including skin sensitization (H317: May cause an allergic skin reaction) and aquatic hazards, signal word Warning. or can lead to severe symptoms including gastrointestinal distress, , convulsions, and systemic , as observed in case reports of accidental or intentional exposure through contaminated substances. Skin contact can cause irritation and allergic reactions, with limited absorption potential leading to systemic effects, especially from fine powders like pigments. Chronic exposure to mercury sulfide primarily involves of the Hg^{2+} ion, leading to manifested as tremors, cognitive impairments, and motor dysfunction, alongside renal damage from tubular cell injury and . Unlike highly volatile organic mercury species such as , HgS exhibits lower volatility owing to its insolubility, yet it remains persistent in biological tissues once absorbed, contributing to long-term organ accumulation in the kidneys, liver, and . In occupational settings like mining, inhalation of fine dust particles can induce and chronic respiratory irritation, while handling pigments historically used in art increases risks of dermal irritation and cumulative exposure. The toxicological mechanism of mercury sulfide involves in vivo dissociation under physiological conditions, releasing Hg^{2+} ions that preferentially bind to sulfhydryl (-SH) groups in proteins and enzymes, thereby inhibiting critical cellular functions such as Na^{+}/K^{+}-ATPase activity and defenses. This thiol-binding disrupts metabolic pathways, promotes , and leads to cellular damage, particularly in neural and renal tissues. Treatment for mercury sulfide poisoning focuses on using meso-2,3-dimercaptosuccinic acid (DMSA), which effectively binds Hg^{2+} to enhance urinary excretion and mitigate systemic effects, often administered orally in symptomatic cases. Supportive care includes , monitoring of vital functions, and if renal failure occurs. To prevent exposure, the (OSHA) enforces a (PEL) of 0.1 mg/m³ as an 8-hour time-weighted average (TWA) (skin) for airborne mercury from compounds like HgS, reflecting standards as of 2025.

Environmental considerations

Mercury sulfide, primarily occurring as the mineral , poses significant environmental risks through activities that release mercury into aquatic systems via runoff and waste. Historical cinnabar operations, such as those at in during the 1900s, have led to elevated mercury concentrations in surrounding rivers, with water levels reaching up to 20 μg/L in affected areas like the Guadalmez and Valdezogues river systems. Similarly, the New Almaden mines in contributed to ongoing contamination in the Guadalupe River, transporting an estimated 4-30 kg of mercury annually to the estuary through sediment flux. These releases occur despite cinnabar's low , as and geochemical processes mobilize mercury from mine into waterways. Although is relatively insoluble, weathering and microbial activity convert it into more bioavailable forms, such as , which enters aquatic food chains and biomagnifies through trophic levels. In contaminated regions near historical sites, tissue often exhibits mercury concentrations exceeding 1 ppm, posing risks to predators and human consumers reliant on local fisheries. For instance, in areas influenced by legacies, such as certain U.S. reservoirs and river systems, average levels in piscivorous surpass 1.0 ppm, amplifying ecological disruptions like reduced in affected ecosystems. Historically, mercury emissions from mining activities, including extraction for processing and direct production, have substantially contributed to global atmospheric mercury burdens, with anthropogenic sources overall accounting for over 60% of cumulative releases since and peaking in the late 19th and early 20th centuries. Pre-2000 emissions from such operations, combined with re-emission from legacy deposits, represented a major fraction of atmospheric mercury, exacerbating long-range transport and deposition worldwide. Remediation efforts for mercury-contaminated soils and sediments incur substantial costs, with global estimates for addressing artisanal and small-scale legacies alone requiring approximately $4 billion annually in cleanup investments. International and regional regulations address these impacts through phased restrictions on mercury sulfide sources. The , adopted in 2013 and entering into force in 2017, prohibits the establishment of new primary mercury mines and mandates the phase-out of existing ones within 15 years of ratification, aiming for full implementation across parties by the mid-2020s to early 2030s. In the , REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) restricts mercury and its compounds, including mercury sulfide, under Annex XVII to prevent environmental releases, with limits on use in products and mandatory authorization for certain applications. In the United States, the Environmental Protection Agency (EPA) oversees cleanup of mercury sulfide-contaminated sites under the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA), as exemplified by ongoing remediation at the Sulphur Bank Mercury Mine, which addresses mine wastes and affected soils to mitigate aquatic and terrestrial pollution. Mitigation strategies increasingly incorporate , where plants like Indian mustard () are trialed to stabilize and extract mercury from contaminated soils. Research in the 2020s has demonstrated 's tolerance to high mercury levels (up to 100 mg/kg soil) and its capacity for phytostabilization, reducing and preventing further leaching into water bodies through root uptake and immobilization. These plant-based approaches offer cost-effective alternatives to traditional excavation methods, particularly for large-scale legacy sites from mining.

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