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Arsenic

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Arsenic Basic information
Arsenic Chemical Properties
  • Melting point:817 °C(lit.)
  • Boiling point:613 °C(lit.)
  • Density 5.727 g/mL at 25 °C(lit.)
  • form powder
  • color Silver to black
  • Specific Gravity5.727
  • Resistivity33.3 μΩ-cm
  • Water Solubility insoluble
  • Sensitive Air Sensitive
  • Merck 13,802
  • Exposure limitsTLV-TWA 0.2 mg(As)/m3 (ACGIH), 0.5 mg (As)/m3 (MSHA), 0.01 mg(As)m3 (OSHA); ceiling 0.002 mg(As)/m3/15 min (NIOSH); carcinogenicity: Human Sufficient Evidence (IARC).
  • Stability:Stable. Incompatible with acids, oxidizing agents, halogens. Heat and air-sensitive.
  • CAS DataBase Reference7440-38-2(CAS DataBase Reference)
  • NIST Chemistry ReferenceArsenic(7440-38-2)
  • EPA Substance Registry SystemArsenic(7440-38-2)
Safety Information
MSDS
Arsenic Usage And Synthesis
  • DescriptionArsenic is a metalloid of the nitrogen group. Two allotrope forms of elemental arsenic have been reported: yellow arsenic and grey arsenic, the latter being usually the more stable form. Arsenic readily oxidises in air to arsenic trioxide (As2O3). Arsenic is mostly found either in its native state or as arsenic sulfide in the form of realgar (As4S4) or orpiment (As2S3). Arsenic can exist in three different valence states (zerovalent, trivalent and pentavalent). Arsenic forms covalent bonds with carbon, oxygen and hydrogen. The toxicity varies widely and depends on the physical state of the compound and its absorption/elimination rate. Trivalent arsenics (As(III)) are derivatives of the arsenous acid (H2AsO3-arsenite) and arsenic trioxide (AsO3). Examples of pentavalent arsenic (As(V)) include derivatives of the arsenic acid (H3AsO4 -arsenate). Organic arsenic-based compounds, that is, compounds containing arsenic-carbon bonds, are usually less toxic than their inorganic counterparts. This is mainly due to their quicker excretion from the human body. Arsenic is known to be one of the most toxic heavy metals. Compounds containing arsenic have a long history of use as poisons, but they also have a long historical medicinal use.
  • Chemical Propertiesgrey powder or chunks
  • Chemical PropertiesElemental arsenic, as, occurs to a limited extent in nature as a steel-gray, amorphous metalloid.
  • Physical propertiesArsenic is classed as a semimetal, meaning that it is neither a metal like aluminum or lead,nor quite a nonmetal such as oxygen, sulfur, or chlorine. Arsenic’s main allotrope is a silverygray,brittle, metal-like substance. Its other two isotopes are unstable crystalline substances.
    Gray arsenic exhibits an unusual property in that its boiling point (614°C) is lower than itsmelting point (817°C). As its temperature changes, it sublimates, which means it goes fromthe solid state, skipping the liquid state, into a vapor state. Cooling the vapor of sublimation,the black allotrope condenses out and in turn changes from the black to the gray allotrope. Ifyellow arsenic is rapidly cooled from its sublimation point, yellow arsenic will condense outand will not revert back to gray arsenic upon cooling.
    The following information is for the gray semimetal form of arsenic only. Its melting pointis 817°C, its sublimation point varies between 613°C and 814°C depending on the atmosphericpressure, and its density is 5.776 g/cm3.
  • IsotopesThere are a total of 35 isotopes of arsenic, ranging from As-60 to As-92, withhalf-lives spanning from a few nanoseconds to 80 days. Although some references claimthere are no stable isotopes of arsenic, arsenic-75 is classed as a stable isotope thatmakes up 100% of arsenic found in the Earth’s crust.
  • Origin of NameDerived either from the Latin word arsenicum or the Greek word arsenikon, both meaning a yellow pigment. It is possible that the Arabic word azzernikh was also an ancient name for arsenic.
  • OccurrenceArsenic is the 53rd most abundant element and is widely distributed in the Earth’s crust.It occurs naturally in several minerals, but high-grade deposits are rare. Most of the mineralsand ores that contain arsenic also contain other metals. Some major sources of arsenic are theminerals orpiment, scherbenkobalt, arsenopyrite, niccolite, realgar, gersdorffite, and smaltite.In addition, most sulfide ores of other metals also contain some arsenic. The three major mineralsthat produce arsenic are: realgar (arsenic monosulfide, AsS), orpiment (arsenic trisulfide,As2S2), and arsenopyrite (iron arsenosulfide, FeAsS).
    Today, most arsenic is recovered as a by-product from the smelting of nickel, copper, iron,and tin. It is also recovered from the flue dust of copper- and lead-smelting furnaces.
  • CharacteristicsArsenic in the elemental form is a brittle, grayish crystal that becomes darker when exposedto air. It is seldom found in the pure elemental form but rather in minerals (compounds). Ithas a long history of use as a poison, and many alchemists were poisoned when using it intheir attempts to produce gold from base metals.
    Arsenic has limited commercial use.
  • HistoryElemental arsenic occurs in two solid modifications: yellow, and gray or metallic, with specific gravities of 1.97, and 5.75, respectively. Gray arsenic, the ordinary stable form, has a triple point of 817°C and sublimes at 616°C and has a critical temperature of 1400°C. Several other allotropic forms of arsenic are reported in the literature. It is believed that Albertus Magnus obtained the element in 1250 A.D. In 1649 Schroeder published two methods of preparing the element. It is found native, in the sulfides realgar and orpiment, as arsenides and sulfarsenides of heavy metals, as the oxide, and as arsenates. Mispickel, arsenopyrite, (FeSAs) is the most common mineral, from which on heating the arsenic sublimes leaving ferrous sulfide. The element is a steel gray, very brittle, crystalline, semimetallic solid; it tarnishes in air, and when heated is rapidly oxidized to arsenous oxide (As2O3) with the odor of garlic. Arsenic and its compounds are poisonous. Exposure to arsenic and its compounds should not exceed 0.01 mg/m3 as elemental As during an 8-h work day. Arsenic is also used in bronzing, pyrotechny, and for hardening and improving the sphericity of shot. The most important compounds are white arsenic (As2O3), the sulfide, Paris green 3Cu(AsO2)2· Cu(C2H3O2)2, calcium arsenate, and lead arsenate; the last three have been used as agricultural insecticides and poisons. Marsh’s test makes use of the formation and ready decomposition of arsine (AsH3). Arsenic is available in high-purity form. It is finding increasing uses as a doping agent in solid-state devices such as transistors. Gallium arsenide is used as a laser material to convert electricity directly into coherent light. Natural arsenic is made of one isotope 75As. Thirty other radioactive isotopes and isomers are known. Arsenic (99%) costs about $75/50g. Purified arsenic (99.9995%) costs about $50/g.
  • UsesIn metallurgy for hardening copper, lead, nonferrous alloys; automotive body solder. In semiconductor materials. In the manufacture of low-melting glass. As wood preservative, herbicide, pesticide.
  • UsesOver the years a number of practical uses for arsenic developed, particularly related toits poisonous nature. Today, it is not of great commercial value except as an insecticide andherbicide.
    It is used in the semiconductor industry to coat solid-state devices. Some compounds areused in paints and fireworks. The major uses are in medicine, where its toxic properties areimportant for the treatment of diseases.
  • UsesArsenic is used for hardening metals suchas copper and lead and as a doping agentin solid-state products of silicon and germanium.Its salts are used in making herbicidesand rodenticides, in semiconductors, and inpyrotechnics. Arsenic trioxide is being usedin experimental research for treating solidtumors such as gastric cancer and head andneck tumors.
  • UsesInorganic arsenic compounds were widely used as pesticides from the mid 1800s to the mid 1900s and were used in medicine until the 1970s, primarily for treatment of leukemia, psoriasis, and asthma. The use of arsenic for treatment of acute promyelocytic leukemia resumed in the 1990s. By the mid 1970s, arsenic use was shifting from pesticides to wood preservatives, and by 1980, wood preservatives were the primary use. Total agricultural-chemical use (in pesticides and fertilizers) declined to about 15% to 20% of total arsenic consumption by the early 1990s and has remained at about 4% since 1995 (Edelstein 1994, Reese 1998, ATSDR 2007, Brooks 2009).
    Since the mid 1990s, arsenic trioxide used in wood preservation has accounted for 86% to 90% of total U.S. arsenic consumption. Wood treated with chromated copper arsenate (CCA), known as “pressure-treated wood,” has been used widely to protect utility poles, building lumber, and foundations from decay and insect attack. However, a voluntary phase-out of CCA for certain residential uses (e.g., in wood for decks, play structures, fencing, and boardwalks) that went into effect December 31, 2003, has reduced this use of arsenic. CCA continues to be used in wood products for industrial use. Other uses of arsenic in the 1990s included use in glass (3% to 4%) and nonferrous alloys (1% to 4%) (ATSDR 2007, Brooks 2009).
    By the 1990s, there was renewed interest in the use of arsenic for treatment of acute promyelocytic leukemia (ATSDR 2007). Arsenic trioxide is approved by the U.S. Food and Drug Administration for treating this type of leukemia when other chemotherapy treatments have failed (MedlinePlus 2009). Arsenic is also used in the production of lead alloys used in lead-acid batteries. It may be added to alloys used for bearings, type metals, lead ammunition, and automotive body solder, and it may be added to brass to improve corrosion resistance. High-purity arsenic is used in a variety of semiconductor applications, including solar cells, light-emitting diodes, lasers, and integrated circuits (ATSDR 2007).
  • DefinitionA nonmetallic element of atomic number 33, group Va of periodic table, aw 74.9216, valences of 2, 3, 5; no stable isotopes.
  • DefinitionA toxic metalloid element existing in several allotropic forms; the most stable is a brittle gray metal. It belongs to group 15 (formerly VA) of the periodic table. Arsenic is found native and in several ores including mispickel (FeSAs), realgar (As4S3), and orpiment (As2S3). The element reacts with hot acids and molten sodium hydroxide but is unaffected by water and acids and alkalis at normal temperatures. It is used in semiconductor devices, alloys, and gun shot. Various compounds are used in medicines and agricultural insecticides and poisons.
    Symbol: As; m.p. 817°C (gray) at 3 MPa pressure; sublimes at 616°C (gray); r.d. 5.78 (gray at 20°C); p.n. 33; r.a.m. 74.92159.
  • Definitionarsenic: Symbol As. A metalloid elementof group 15 (formerly VB) ofthe periodic table; a.n. 33; r.a.m.74.92; r.d. 5.7; sublimes at 613°C. Ithas three allotropes-yellow, black,and grey. The grey metallic form isthe stable and most common one.Over 150 minerals contain arsenicbut the main sources are as impuritiesin sulphide ores and in the mineralsorpiment (As2S3) and realgar(As4S4). Ores are roasted in air toform arsenic oxide and then reducedby hydrogen or carbon to metallic arsenic.Arsenic compounds are used ininsecticides and as doping agents insemiconductors. The element is includedin some lead-based alloys topromote hardening. Confusion canarise because As4O6 is often sold aswhite arsenic. Arsenic compoundsare accumulative poisons. The elementwill react with halogens, concentratedoxidizing acids, and hot alkalis.Albertus Magnus is believed tohave been the first to isolate the elementin 1250.
  • General DescriptionA grayish metallic solid that turns black upon exposure to air. Insoluble in water. Toxic by ingestion.
  • Air & Water ReactionsTurns black on exposure to air. Insoluble in water.
  • Reactivity ProfileArsenic reacts incandescently with bromine trifluoride, even at 10°C [Mellor 2:113 1946-47]. Causes bromoazide to explode upon contact. Ignites if ground up together with solid potassium permanganate [Mellor 12:322 1946-47]. Is oxidized by sodium peroxide with incandescence [Mellor 2:490-93 1946-47]. A combination of finely divided Arsenic with finely divided bromates (also chlorates and iodates) of barium, calcium, magnesium, potassium, sodium, or zinc can explode by heat, percussion, and friction [Mellor 2:310 1946-47]. Bromine pentafluoride reacts readily in the cold with Arsenic. Ignition usually occurs. Reacts vigorously with fluorine at ordinary temperatures [Mellor 9:34 1946-47].
  • HazardConfirmed carcinogen and mutagen. OSHA employee exposure limit:
  • HazardMost of the compounds of arsenic are toxic when in contact with the skin, when inhaled,or when ingested. As with arsenic’s cousin phosphorus above it in group 15 of the periodictable, care must be taken when using arsenic. The compound arsenic trioxide (As2O3), anexcellent weed-killer, is also carcinogenic. Copper acetoarsenite, known as Paris green, is usedto spray cotton for boll weevils. A poisonous dose of arsenic as small as 60 milligrams can bedetected within the body by using the Marsh test.
  • Health HazardOne of the allotropic forms, yellow arsenic,is a severe human poison. The fatal dosein humans is 1–2 mg/kg body weight. Allarsenic compounds are toxic, the toxicityvarying with the oxidation state of themetal and the solubility. Thus, the trivalentinorganic compounds of arsenic, suchas arsenic trichloride, arsenic trioxide, andarsine, are highly toxic—more poisonousthan the metal and its pentavalent salts.The organic arsenic compound Lewisite isa severe blistering agent that can penetratethe skin and cause damage at the point ofexposure. Lewisite was used as a poison gasin World War I. Less soluble arsenic sulfideexhibits a lower acute toxicity.
    Arsenic is absorbed into the body througha GI route and inhalation. The acute symptomsinclude fever, GI disturbances, irritationof the respiratory tract, ulceration of thenasal septum, and dermatitis. Chronic exposurecan produce pigmentation of the skin,peripheral neuropathy, and degeneration ofliver and kidneys.
    The toxic effects of arsenic are attributedto its binding properties with sulfur. It formscomplexes with coenzymes. This inhibitsthe production of adenosine triphosphate (ATP), which is essential for energy in bodymetabolism. 2,3-Dimercapto-1-propanol isan antidote against acute intoxication. 2,3-Dithioerythritol is reported to be a moreeffective and less toxic antidote (Boyd et al.1989). Arsenic is carcinogenic to humans.Ingestion by an oral route has caused anincreased incidence of tumors in the liver,blood, and lungs. The mutagenic and genotoxiceffects of arsenic have been reviewed(Basu et al. 2001).
    Peraza et al. (2003) studied toxicity andmetabolism of inorganic arsenic in kidneyat low level subcytotoxic concentrations.Human renal proximal tubule epithelial cells(HK-2) were used as model in their study.The authors found that HK-2 cells werecapable of biotransforming inorganic arseniccompounds in a pathway involving reductionof arsenate to arsenite.
    Bernstam et al. (2002) measured percutaneousabsorption of As(III) and As(V) invitro using artificial human skin. The permeabilityconstant (Kp) for As(V) and As(III)were determined from this study as 4.3× 10-5 cm/h and 10.1× 10-5 cm/h respectively.As(III) at exposure doses as low as10 μg/L could cause significant morphologicalchanges, disruption of cell membrane andinhibition of deoxyribonucleic acid (DNA)and protein syntheses. The authors noted thatconcentrations of tri- or pentavalent arsenicat levels above 100 μg/L in showering- orhand-washing waters could manifest harmfuleffects.
  • Health HazardPoisonous by inhalation of dust or by ingestion. Regardless of exposure route, symptoms in most cases are characteristic of severe gastritis or gastroenteritis. All chemical forms of Arsenic eventually produce similar toxic effects. Symptoms may be delayed.
  • Industrial usesArsenic (symbol As) is a soft, brittle, poisonouselement of steel-gray color and metallic luster.In atomic structure it is a semimetal, lackingplasticity, and is used only in alloys and incompounds. The bulk of the arsenic used isemployed in insecticides, rat poisons, and weedkillers, but it has many industrial uses, especiallyin pigments. It is also used in poisongases for chemical warfare.Metallic arsenic is stable in dry air. Whenexposed to humid or moistened air, the surfacefirst becomes coated with a superficial goldenbronze tarnish, which on further exposure turnsblack. On heating in air arsenic will vaporizeand burn to As2O3.
  • Safety ProfileConfirmed human carcinogen producing liver tumors. Poison by subcutaneous, intramuscular, and intraperitoneal routes. Human systemic skin and gastrointestinal effects by ingestion. An experimental teratogen. Other experimental reproductive effects. Mutation data reported. Flammable in the form of dust when exposed to heat or flame or by chemical reaction with powerful oxidizers such as bromates, chlorates, iodates, peroxides, lithium, NC4, m 0 3 , Khfn04, Rb2C2, AgN04, NOCl, IF5, CrO3, CIF3, Cl0, BrF3, BrFj, BrN3, RbGBCH, CsC3BCH. Slightly explosive in the form of dust when exposed to flame. When heated or on contact with acid or acid fumes, it emits highly toxic fumes; can react vigorously on contact with oxidizing materials. Incompatible with bromine azide, dirubidium acetylide, halogens, palladium, zinc, platinum, NCh, AgNO3, CrO3, Na2O2, hexafluoroisopropylideneamino lithum.
  • Potential ExposureArsenic compounds have a variety of uses. Arsenic and its compounds are used as an alloy additive, in electronic devices; in veterinary medicines; in agriculture as insecticides, herbicides, larvicides, and pesticides. Some arsenic compounds are used in pigment production; the manufacture of glass as a bronzing or decolorizing agent; the manufacture of opal glass and enamels, textile printing; tanning, taxidermy, antifouling paints; to control sludge formation in lubricating oils. Metallic arsenic is used as an alloying agent for heavy metals; and in solders, medicines, herbicides. EPA has estimated that more than 6 million people living within 12 mi of major sources of copper, zinc, and lead smelters-may be exposed to 10 times the average United States atmospheric levels of arsenic. The agency says that 40,000 people living near some copper smelters may be exposed to 100 times the national atmospheric average.
  • CarcinogenicityArsenic and inorganic arsenic compounds are known to be human carcinogens based on sufficient evidence of carcinogenicity in humans.
  • ShippingUN1558 Arsenic, Hazard Class: 6.1; Labels: 6.1-Poisonous materials.
  • IncompatibilitiesIncompatible with strong acids; strong oxidizers; peroxides, bromine azide, bromine pentafluoride, bromine trifluoride; cesium acetylene carbide, chromium trioxide; nitrogen trichloride, silver nitrate. Can react vigorously with strong oxidizers (chlorine, dichromate, permanganate). Forms highly toxic fumes on contact with acids or active metals (iron, aluminum, zinc). Hydrogen gas can react with inorganic arsenic to form highly toxic arsine gas.
  • Waste DisposalElemental arsenic wastes should be placed in long-term storage or returned to suppliers or manufacturers for reprocessing. Arsenic pentaselenide-wastes should be placed in long-term storage or returned to suppliers or manufacturers for reprocessing. Arsenic trichloride: hydrolyze to arsenic trioxide utilizing scrubbers for hydrogen chloride abatement. The trioxide may then be placed in long-term storage. Arsenic trioxide: long-term storage in large shiftproof and weatherproof silos. This compound may also be dissolved, precipitated as the sulfide and returned to the suppliers. Arsenic-containing sewage may be decontaminated by pyrolusite treatment. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. In accordance with 40CFR165, follow recommendations for the disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by contacting your local or federal environmental control agency, or by contacting your regional EPA office.
  • RegulationsConsumer Product Safety Commission (CPSC)
    Fireworks devices shall not contain arsenic sulfide, arsenates, or arsenites.
    Department of Transportation (DOT)
    Inorganic arsenic compounds are considered hazardous materials, and orthoarsenic acid is considered a marine pollutant; special requirements have been set for marking, labeling, and transporting these materials.
    Environmental Protection Agency (EPA)
    Clean Air Act
    Mobile Source Air Toxics: Arsenic compounds are listed as mobile source air toxics for which regulations are to be developed.
    National Emissions Standards for Hazardous Air Pollutants: Arsenic compounds are listed as hazardous air pollutants.
    Prevention of Accidental Release: Threshold quantity (TQ) = 15,000 lb for arsenous trichloride; = 1,000 lb for arsine.
    Urban Air Toxics Strategy: Arsenic compounds are identified as one of 33 hazardous air pollutants that present the greatest threat to public health in urban areas.
    Clean Water Act
    Limits have been established for arsenic in biosolids (sewage sludge) when used or disposed of via land application, surface disposal, or incineration. Liquid hazardous wastes containing arsenic and/or compounds at levels ≥ 500 mg/L (as As) are prohibited from underground injection.
    Effluent Guidelines: Arsenic and arsenic compounds are listed as toxic pollutants.
    Water Quality Criteria: Based on fish or shellfish and water consumption = 0.018 μg/L for arsenic; based on fish or shellfish consumption only = 0.14 μg/L for arsenic. Numerous inorganic arsenic compounds are designated hazardous substances.
    Comprehensive Environmental Response, Compensation, and Liability Act
    Reportable quantity (RQ) = 1 lb for arsenic, arsenic acid, arsenic disulfide, arsenic pentoxide, arsenic trioxide, arsenic trisulfide, arsenic oxide, arsenic trichloride, sodium arsenate, lead arsenate, calcium arsenate, potassium arsenate, sodium arsenite, potassium arsenite, calcium arsenite.
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