Hydrogen sulfide
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Names | |||
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Systematic IUPAC name
Hydrogen sulfide[1] | |||
Other names
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Identifiers | |||
3D model (
JSmol ) |
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3DMet | |||
3535004 | |||
ChEBI | |||
ChEMBL | |||
ChemSpider | |||
ECHA InfoCard
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100.029.070 | ||
EC Number |
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303 | |||
KEGG | |||
MeSH | Hydrogen+sulfide | ||
PubChem CID
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RTECS number
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UNII | |||
UN number | 1053 | ||
CompTox Dashboard (EPA)
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Properties | |||
H2S | |||
Molar mass | 34.08 g·mol−1 | ||
Appearance | Colorless gas | ||
Odor | Foul, pungent, like that of rotten eggs | ||
Density | 1.539 g.L−1 (0°C)[2] | ||
Melting point | −85.5[3] °C (−121.9 °F; 187.7 K) | ||
Boiling point | −59.55[3] °C (−75.19 °F; 213.60 K) | ||
3.980 g dm−3 (at 20 °C) [4] | |||
Vapor pressure | 1740 kPa (at 21 °C) | ||
Acidity (pKa) | 7.0[5][6] | ||
Conjugate acid
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Sulfonium | ||
Conjugate base
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Bisulfide | ||
−25.5·10−6 cm3/mol | |||
Refractive index (nD)
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1.000644 (0 °C)[2] | ||
Structure | |||
C2v | |||
Bent | |||
0.97 D | |||
Thermochemistry | |||
Heat capacity (C)
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1.003 J K−1 g−1 | ||
Std molar
entropy (S⦵298) |
206 J mol−1 K−1[7] | ||
Std enthalpy of (ΔfH⦵298)formation |
−21 kJ mol−1[7] | ||
Hazards | |||
Occupational safety and health (OHS/OSH): | |||
Main hazards
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Flammable and highly toxic | ||
GHS labelling: | |||
Danger | |||
H220, H330, H400 | |||
P210, P260, P271, P273, P284, P304+P340, P310, P320, P377, P381, P391, P403, P403+P233, P405, P501 | |||
NFPA 704 (fire diamond) | |||
Flash point | −82.4 °C (−116.3 °F; 190.8 K)[10] | ||
232 °C (450 °F; 505 K) | |||
Explosive limits
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4.3–46% | ||
Lethal dose or concentration (LD, LC): | |||
LC50 (median concentration)
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LCLo (lowest published)
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NIOSH (US health exposure limits): | |||
PEL (Permissible)
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C 20 ppm; 50 ppm [10-minute maximum peak][8] | ||
REL (Recommended)
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C 10 ppm (15 mg/m3) [10-minute][8] | ||
IDLH (Immediate danger) |
100 ppm[8] | ||
Related compounds | |||
Related hydrogen chalcogenides
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Related compounds
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Phosphine | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Hydrogen sulfide is a
Hydrogen sulfide is toxic to humans and most other animals by inhibiting
Hydrogen sulfide is often produced from the
Properties
Hydrogen sulfide is slightly denser than air. A mixture of H2S and air can be explosive.
Oxidation
In general, hydrogen sulfide acts as a
- 2 H2S + 3 O2 → 2 SO2 + 2 H2O
If an excess of oxygen is present, sulfur trioxide (SO3) is formed, which quickly hydrates to sulfuric acid:
- H2S + 2 O2 → H2SO4
Acid-base properties
It is slightly soluble in water and acts as a
Extreme temperatures and pressures
At pressures above 90 GPa (
Hydrogen sulfide decomposes without a presence of a catalyst under atmospheric pressure around 1200 °C into hydrogen and sulfur.[19]
Tarnishing
Hydrogen sulfide reacts with metal ions to form metal sulfides, which are insoluble, often dark colored solids. Lead(II) acetate paper is used to detect hydrogen sulfide because it readily converts to lead(II) sulfide, which is black. Treating metal sulfides with strong acid or electrolysis often liberates hydrogen sulfide. Hydrogen sulfide is also responsible for tarnishing on various metals including copper and silver; the chemical responsible for black toning found on silver coins is silver sulfide (Ag2S), which is produced when the silver on the surface of the coin reacts with atmospheric hydrogen sulfide.[20] Coins that have been subject to toning by hydrogen sulfide and other sulfur-containing compounds may have the toning add to the numismatic value of a coin based on aesthetics, as the toning may produce thin-film interference, resulting in the coin taking on an attractive coloration.[21] Coins can also be intentionally treated with hydrogen sulfide to induce toning, though artificial toning can be distinguished from natural toning, and is generally criticised among collectors.[22]
Production
Hydrogen sulfide is most commonly obtained by its separation from sour gas, which is natural gas with a high content of H2S. It can also be produced by treating hydrogen with molten elemental sulfur at about 450 °C. Hydrocarbons can serve as a source of hydrogen in this process.[23]
- S + H2 → H2S
The very favorable thermodynamics for the hydrogenation of sulfur implies that the dehydrogenation (or cracking) of hydrogen sulfide would require very high temperatures.[24]
A standard lab preparation is to treat
- FeS + 2 HCl → FeCl2 + H2S
For use in qualitative inorganic analysis, thioacetamide is used to generate H2S:
- CH3C(S)NH2 + H2O → CH3C(O)NH2 + H2S
Many metal and nonmetal sulfides, e.g. aluminium sulfide, phosphorus pentasulfide, silicon disulfide liberate hydrogen sulfide upon exposure to water:[25]
- 6 H2O + Al2S3 → 3 H2S + 2 Al(OH)3
This gas is also produced by heating sulfur with solid organic compounds and by reducing sulfurated organic compounds with hydrogen. It can also be produced by mixing ammonium thiocyanate to concentrated sulphuric acid and adding water to it.
Biosynthesis
Hydrogen sulfide can be generated in cells via enzymatic or non-enzymatic pathways. Three enzymes catalyze formation of H
2S: cystathionine γ-lyase (CSE), cystathionine β-synthetase (CBS), and 3-mercaptopyruvate sulfurtransferase (3-MST).[26] CBS and CSE are the main proponents of H2S biogenesis, which follows the trans-sulfuration pathway.[27] These enzymes have been identified in a breadth of biological cells and tissues, and their activity is induced by a number of disease states.[28] These enzymes are characterized by the transfer of a sulfur atom from methionine to serine to form a cysteine molecule.[27] 3-MST also contributes to hydrogen sulfide production by way of the cysteine catabolic pathway.[28][27] Dietary amino acids, such as methionine and cysteine serve as the primary substrates for the transulfuration pathways and in the production of hydrogen sulfide. Hydrogen sulfide can also be derived from proteins such as ferredoxins and Rieske proteins.[28]
Water heaters can aid the conversion of
Signalling role
H2S in the body acts as a
Hydrogen sulfide is involved in vasodilation in animals, as well as in increasing seed germination and stress responses in plants.[32] Hydrogen sulfide signaling is moderated by reactive oxygen species (ROS) and reactive nitrogen species (RNS).[32] H2S has been shown to interact with NO resulting in several different cellular effects, as well as the formation of another signal called nitrosothiol.[32] Hydrogen sulfide is also known to increase the levels of glutathione, which acts to reduce or disrupt ROS levels in cells.[32]
The field of H2S biology has advanced from environmental toxicology to investigate the roles of endogenously produced H2S in physiological conditions and in various pathophysiological states.[33] H2S has been implicated in cancer and Down syndrome and vascular disease.[34][35][36][37]
It inhibits Complex IV of the mitochondrial electron transport chain, which effectively reduces ATP generation and biochemical activity within cells.[32]
Uses
Production of sulfur
Hydrogen sulfide is mainly consumed as a precursor to elemental sulfur. This conversion, called the Claus process, involves partial oxidation to sulfur dioxide. The latter reacts with hydrogen sulfide to give elemental sulfur. The conversion is catalyzed by alumina.[38]
- 2H2S + SO2→ 3S + 2H2O
Production of thioorganic compounds
Many fundamental
Production of metal sulfides
Upon combining with alkali metal bases, hydrogen sulfide converts to alkali hydrosulfides such as sodium hydrosulfide and sodium sulfide:
- H2S + NaOH → NaSH + H2O
- NaSH + NaOH → Na2S + H2O
Sodium sulfides are used in the
As indicated above, many metal ions react with hydrogen sulfide to give the corresponding metal sulfides. Oxidic ores are sometimes treated with hydrogen sulfide to give the corresponding metal sulfides which are more readily purified byy
Hydrogen sulfide was a reagent in the
Miscellaneous applications
Hydrogen sulfide is used to separate deuterium oxide, or heavy water, from normal water via the Girdler sulfide process.
A suspended animation-like state has been induced in rodents with the use of hydrogen sulfide, resulting in
Occurrence
A portion of global H2S emissions are due to human activity. By far the largest industrial source of H2S is petroleum refineries: The hydrodesulfurization process liberates sulfur from petroleum by the action of hydrogen. The resulting H2S is converted to elemental sulfur by partial combustion via the Claus process, which is a major source of elemental sulfur. Other anthropogenic sources of hydrogen sulfide include coke ovens, paper mills (using the Kraft process), tanneries and sewerage. H2S arises from virtually anywhere where elemental sulfur comes in contact with organic material, especially at high temperatures. Depending on environmental conditions, it is responsible for deterioration of material through the action of some sulfur oxidizing microorganisms. It is called biogenic sulfide corrosion.
In 2011 it was reported that increased concentrations of H2S were observed in the Bakken formation crude, possibly due to oil field practices, and presented challenges such as "health and environmental risks, corrosion of wellbore, added expense with regard to materials handling and pipeline equipment, and additional refinement requirements".[43]
Besides living near gas and oil drilling operations, ordinary citizens can be exposed to hydrogen sulfide by being near waste water treatment facilities, landfills and farms with manure storage. Exposure occurs through breathing contaminated air or drinking contaminated water.[44]
In
In industrial anaerobic digestion processes, such as
Removal from water
A number of processes have been designed to remove hydrogen sulfide from drinking water.[48]
- Continuous chlorination
- For levels up to 75 mg/L chlorine is used in the purification process as an oxidizing chemical to react with hydrogen sulfide. This reaction yields insoluble solid sulfur. Usually the chlorine used is in the form of sodium hypochlorite.[49]
- Aeration
- For concentrations of hydrogen sulfide less than 2 mg/L aeration is an ideal treatment process. Oxygen is added to water and a reaction between oxygen and hydrogen sulfide react to produce odorless sulfate.[50]
- Nitrate addition
- Calcium nitrate can be used to prevent hydrogen sulfide formation in wastewater streams.
Removal from fuel gases
Hydrogen sulfide is commonly found in raw natural gas and biogas. It is typically removed by amine gas treating technologies. In such processes, the hydrogen sulfide is first converted to an ammonium salt, whereas the natural gas is unaffected.
- RNH2 + H2S ⇌ [RNH3]+ + SH−
The bisulfide anion is subsequently regenerated by heating of the amine sulfide solution. Hydrogen sulfide generated in this process is typically converted to elemental sulfur using the
Safety
The underground mine gas term for foul-smelling hydrogen sulfide-rich gas mixtures is stinkdamp. Hydrogen sulfide is a highly
Even before hydrogen sulfide was discovered, Italian physician Bernardino Ramazzini hypothesized in his 1713 book De Morbis Artificum Diatriba that occupational diseases of sewer-workers and blackening of coins in their clothes may be caused by an unknown invisible volatile acid (moreover, in late 18th century toxic gas emanation from Paris sewers became a problem for the citizens and authorities).[53]
Although very pungent at first (it smells like rotten eggs
Low-level exposure
Since hydrogen sulfide occurs naturally in the body, the environment, and the gut, enzymes exist to metabolize it. At some threshold level, believed to average around 300–350 ppm, the oxidative enzymes become overwhelmed. Many personal safety gas detectors, such as those used by utility, sewage and petrochemical workers, are set to alarm at as low as 5 to 10 ppm and to go into high alarm at 15 ppm. Metabolism causes oxidation to sulfate, which is harmless.[57] Hence, low levels of hydrogen sulfide may be tolerated indefinitely.
Exposure to lower concentrations can result in
Long-term, low-level exposure may result in
High-level exposure
Short-term, high-level exposure can induce immediate collapse, with loss of breathing and a high probability of death. If death does not occur, high exposure to hydrogen sulfide can lead to cortical pseudolaminar necrosis, degeneration of the basal ganglia and cerebral edema.[51] Although respiratory paralysis may be immediate, it can also be delayed up to 72 hours.[60] Diagnostic of extreme poisoning by H2S is the discolouration of copper coins in the pockets of the victim.
Inhalation of H2S resulted in about 7 workplace deaths per year in the U.S. (2011–2017 data), second only to carbon monoxide (17 deaths per year) for workplace chemical inhalation deaths.[61]
Exposure thresholds
- Exposure limits stipulated by the United States government:[62]
- 10 ): recommended permissible exposure ceiling (the recommended level that must not be exceeded, except once for 10 min. in an 8-hour shift, if no other measurable exposure occurs)
- 20 ppm PEL-Ceiling (OSHA): permissible exposure ceiling (the level that must not be exceeded, except once for 10 min. in an 8-hour shift, if no other measurable exposure occurs)
- 50 ppm PEL-Peak (OSHA): peak permissible exposure (the level that must never be exceeded)
- 100 ppm IDLH (NIOSH): immediately dangerous to life and health (the level that interferes with the ability to escape)
- 0.00047 ppm or 0.47 ppb is the odor threshold, the point at which 50% of a human panel can detect the presence of an odor without being able to identify it.[63]
- 10–20 ppm is the borderline concentration for eye irritation.
- 50–100 ppm leads to eye damage.
- At 100–150 ppm the olfactory nerve is paralyzed after a few inhalations, and the sense of smell disappears, often together with awareness of danger.[64][65]
- 320–530 ppm leads to pulmonary edema with the possibility of death.[51]
- 530–1000 ppm causes strong stimulation of the central nervous system and rapid breathing, leading to loss of breathing.
- 800 ppm is the lethal concentration for 50% of humans for 5 minutes' exposure (LC50).
- Concentrations over 1000 ppm cause immediate collapse with loss of breathing, even after inhalation of a single breath.
Treatment
Treatment involves immediate inhalation of
Incidents
Hydrogen sulfide was used by the British Army as a chemical weapon during World War I. It was not considered to be an ideal war gas, partially due to its flammability and because the distinctive smell could be detected from even a small leak, alerting the enemy to the presence of the gas. It was nevertheless used on two occasions in 1916 when other gases were in short supply.[69]
On September 2, 2005, a leak in the propeller room of a Royal Caribbean Cruise Liner docked in Los Angeles resulted in the deaths of 3 crewmen due to a sewage line leak. As a result, all such compartments are now required to have a ventilation system.[70][71]
A dump of toxic waste containing hydrogen sulfide is believed to have caused 17 deaths and thousands of illnesses in
In September 2008, three workers were killed and two suffered serious injury, including long term brain damage, at a mushroom growing company in Langley, British Columbia. A valve to a pipe that carried chicken manure, straw and gypsum to the compost fuel for the mushroom growing operation became clogged, and as workers unclogged the valve in a confined space without proper ventilation the hydrogen sulfide that had built up due to anaerobic decomposition of the material was released, poisoning the workers in the surrounding area.[72] An investigator said there could have been more fatalities if the pipe had been fully cleared and/or if the wind had changed directions.[73]
In 2014, levels of hydrogen sulfide as high as 83 ppm were detected at a recently built mall in Thailand called Siam Square One at the Siam Square area. Shop tenants at the mall reported health complications such as sinus inflammation, breathing difficulties and eye irritation. After investigation it was determined that the large amount of gas originated from imperfect treatment and disposal of waste water in the building.[74]
In 2014, hydrogen sulfide gas killed workers at the Promenade shopping center in North Scottsdale, Arizona, USA [75] after climbing into 15ft deep chamber without wearing personal protective gear. "Arriving crews recorded high levels of hydrogen cyanide and hydrogen sulfide coming out of the sewer."
In November 2014, a substantial amount of hydrogen sulfide gas shrouded the central, eastern and southeastern parts of Moscow. Residents living in the area were urged to stay indoors by the emergencies ministry. Although the exact source of the gas was not known, blame had been placed on a Moscow oil refinery.[76]
In June 2016, a mother and her daughter were found dead in their still-running 2006 Porsche Cayenne SUV against a guardrail on Florida's Turnpike, initially thought to be victims of carbon monoxide poisoning.[77][78] Their deaths remained unexplained as the medical examiner waited for results of toxicology tests on the victims,[79] until urine tests revealed that hydrogen sulfide was the cause of death. A report from the Orange-Osceola Medical Examiner's Office indicated that toxic fumes came from the Porsche's starter battery, located under the front passenger seat.[80][81]
In January 2017, three utility workers in Key Largo, Florida, died one by one within seconds of descending into a narrow space beneath a manhole cover to check a section of paved street.[82] In an attempt to save the men, a firefighter who entered the hole without his air tank (because he could not fit through the hole with it) collapsed within seconds and had to be rescued by a colleague.[83] The firefighter was airlifted to Jackson Memorial Hospital and later recovered.[84][85] A Monroe County Sheriff officer initially determined that the space contained hydrogen sulfide and methane gas produced by decomposing vegetation.[86]
On May 24, 2018, two workers were killed, another seriously injured, and 14 others hospitalized by hydrogen sulfide inhalation at a
In October 2019, an
Suicides
The gas, produced by mixing certain household ingredients, was used in a suicide wave in 2008 in Japan.[94] The wave prompted staff at Tokyo's suicide prevention center to set up a special hotline during "Golden Week", as they received an increase in calls from people wanting to kill themselves during the annual May holiday.[95]
As of 2010, this phenomenon has occurred in a number of US cities, prompting warnings to those arriving at the site of the suicide.[96][97][98][99][100] These first responders, such as emergency services workers or family members are at risk of death or injury from inhaling the gas, or by fire.[101][102] Local governments have also initiated campaigns to prevent such suicides.
In 2020, H2S ingestion was used as a suicide method by Japanese pro wrestler Hana Kimura.[103]
Hydrogen sulfide in the natural environment
Microbial: The sulfur cycle
Hydrogen sulfide is a central participant in the sulfur cycle, the biogeochemical cycle of sulfur on Earth.[104]
In the absence of
As organic matter decays under low-oxygen (or
Several groups of bacteria can use hydrogen sulfide as fuel, oxidizing it to elemental sulfur or to sulfate by using dissolved oxygen, metal oxides (e.g., iron oxyhydroxides and manganese oxides), or nitrate as electron acceptors.[105]
The purple sulfur bacteria and the green sulfur bacteria use hydrogen sulfide as an electron donor in photosynthesis, thereby producing elemental sulfur. This mode of photosynthesis is older than the mode of cyanobacteria, algae, and plants, which uses water as electron donor and liberates oxygen.
The biochemistry of hydrogen sulfide is a key part of the chemistry of the
Animals
Hydrogen sulfide is lethal to most animals, but a few highly specialized species (extremophiles) do thrive in habitats that are rich in this compound.[107]
In the deep sea,
Freshwater springs rich in hydrogen sulfide are mainly home to invertebrates, but also include a small number of fish:
Interstellar and planetary occurrence
Hydrogen sulfide has often been detected in the interstellar medium.[112] It also occurs in the clouds of planets in our solar system.[113][114]
Mass extinctions
Hydrogen sulfide has been implicated in several
Organic residues from these extinction boundaries indicate that the oceans were anoxic (oxygen-depleted) and had species of shallow plankton that metabolized H2S. The formation of H2S may have been initiated by massive volcanic eruptions, which emitted
See also
- Hydrogen chalcogenide – any binary compound of hydrogen with chalcogens, including hydrogen polychalcogenides
- Hydrogen sulfide chemosynthesis
- Sewer gas – complex mixture of toxic and nontoxic gases produced and collected in sewage systems by the decomposition of sewage
- Targeted temperature management, also known as induced hypothermia – Medical procedure
- Marsh gas
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- ^ http://info.publicintelligence.net/KCTEWhydrogensulfide.pdf[full citation needed]
- ^ "Chemical Suicide on Campus" (PDF). www.maryland.gov. Archived from the original on January 3, 2012.
- ^ Scoville, Dean (April 2011). "Chemical Suicides". POLICE Magazine. Retrieved 2013-12-19.
- ^ Casey, Connor (26 May 2020). "Hana Kimura Cause Of Death Revealed". ComicBook.com.
More details about her death have since come to light, as Dave Meltzer provided details about what happened on the night of her death during a recent Wrestling Observer Radio. According to Meltzer, Kimura died after inhalation of hydrogen sulfide. He explained that concerns about her health first popped up when she posted a tweet early Saturday morning indicating that she was going to cause self-harm.
- PMID 25416397.
- ^ Jørgensen, B. B.; Nelson, D. C. (2004). "Sulfide oxidation in marine sediments: Geochemistry meets microbiology". In Amend, J. P.; Edwards, K. J.; Lyons, T. W. (eds.). Sulfur Biogeochemistry – Past and Present. Geological Society of America. pp. 36–81.
- PMID 3070320.
- ^ S2CID 27303725.
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- ^ "Hydrothermal Vents". Marine Society of Australia. Retrieved 28 December 2014.
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- ISBN 9781108411981.[page needed]
- ^ a b "Impact from the Deep". Scientific American. October 2006.
- S2CID 55812439.
- doi:10.1130/G21295.1. Retrieved 2 April 2023.
Additional resources
- Committee on Medical and Biological Effects of Environmental Pollutants (1979). Hydrogen Sulfide. Baltimore: University Park Press. ISBN 978-0-8391-0127-7.
- Siefers, Andrea (2010). A novel and cost-effective hydrogen sulfide removal technology using tire derived rubber particles (MS thesis). Iowa State University. Retrieved 8 February 2013.