Arsin Chemische Eigenschaften,Einsatz,Produktion Methoden
ERSCHEINUNGSBILD
FARBLOSES KOMPRIMIERTES FLüSSIGGAS MIT CHARAKTERISTISCHEM GERUCH.
PHYSIKALISCHE GEFAHREN
Das Gas ist schwerer als Luft und kann sich am Boden ausbreiten. Fernzündung möglich. Fließen, Schütten o.ä. kann zu elektrostatischer Aufladung führen.
CHEMISCHE GEFAHREN
Zersetzung beim Erhitzen und unter Einfluss von Licht und Feuchtigkeit unter Bildung giftiger Arsenrauche. Reagiert mit starken Oxidationsmitteln unter Explosionsgefahr. Bei Stoß, Reibung oder Erschütterung explosionsartige Zersetzung möglich.
ARBEITSPLATZGRENZWERTE
TLV: 0.05 ppm (als TWA); Beabsichtigte änderung; TLV: (0.005 ppm; A4 (not classifiable as a human carcinogen);) (ACGIH 2005).
MAK: IIb (nicht festgelegt, aber Informationen vorhanden) (DFG 2005).
AUFNAHMEWEGE
Aufnahme in den Körper durch Inhalation.
INHALATIONSGEFAHREN
Eine gesundheitsschädliche Konzentration des Gases in der Luft wird beim Entweichen aus dem Behälter sehr schnell erreicht.
WIRKUNGEN BEI KURZZEITEXPOSITION
WIRKUNGEN BEI KURZZEITEXPOSITION: Schnelle Verdampfung kann zu Erfrierungen führen. Möglich sind Auswirkungen auf das Blut mit nachfolgender Blutzellzerstörung und Nierenversagen. Die Auswirkungen treten u.U. verzögert ein. Exposition kann zum Tod führen. ärztliche Beobachtung notwendig.
WIRKUNGEN NACH WIEDERHOLTER ODER LANGZEITEXPOSITION
Krebserzeugend für den Menschen.
LECKAGE
Gefahrenbereich verlassen! Fachmann zu Rate ziehen! Zündquellen entfernen. Behälter abdichten oder an einen offenen und sicheren Ort bringen. In flüssigem Zustand NICHT in die Kanalisation spülen. Wasserstrahl NIEMALS auf die Flüssigkeit richten. NICHT in die Umwelt gelangen lassen. Gasdichter Chemikalienschutzanzug mit umgebungsluftunabhängigem Atemschutzgerät.
R-Sätze Betriebsanweisung:
R12:Hochentzündlich.
R26:Sehr giftig beim Einatmen.
R48/20:Gesundheitsschädlich: Gefahr ernster Gesundheitsschäden bei längerer Exposition durch Einatmen.
R50/53:Sehr giftig für Wasserorganismen, kann in Gewässern längerfristig schädliche Wirkungen haben.
S-Sätze Betriebsanweisung:
S9:Behälter an einem gut gelüfteten Ort aufbewahren.
S16:Von Zündquellen fernhalten - Nicht rauchen.
S28:Bei Berührung mit der Haut sofort abwaschen mit viel . . . (vom Hersteller anzugeben).
S33:Maßnahmen gegen elektrostatische Aufladungen treffen.
S36/37:Bei der Arbeit geeignete Schutzhandschuhe und Schutzkleidung tragen.
S45:Bei Unfall oder Unwohlsein sofort Arzt zuziehen (wenn möglich, dieses Etikett vorzeigen).
S60:Dieses Produkt und sein Behälter sind als gefährlicher Abfall zu entsorgen.
S61:Freisetzung in die Umwelt vermeiden. Besondere Anweisungen einholen/Sicherheitsdatenblatt zu Rate ziehen.
Aussehen Eigenschaften
Summenformel: AsH3; Farbloses, knoblauchartig riechendes Gas, explosiv.
Gefahren für Mensch und Umwelt
Wirkt in wässeriger Lösung stark reduzierend. Von Hitze fernhalten. Zu vermeidende Stoffe: Oxidationsmittel, Säuren, Halogene. Gefährliche Zersetzungsprodukte: Arsenoxide, Wasserstoff.
Giftig beim Verschlucken, Einatmen oder Aufnahme durch die Haut. MAK: 0,05 ml/m3, 0,2 mg/m3; Spitzenbegr. Kat.: II, 2.
Stark wassergefährdend (WGK 3).
Schutzmaßnahmen und Verhaltensregeln
Behälter dicht geschlossen halten. An einem trockenen, kühlen Platz lagern. Arbeiten nur im Abzug durchführen. Entstehende Gase durch Einleiten in oxidierende Lösung (z.B. Wasserstoffperoxidlsg.) entschärfen. Jeglichen Kontakt vermeiden.
Schutzbrille mit Seitenschutz erforderlich.
Chemikalienresistente Schutzhandschuhe.
Schutzkleidung tragen.
Verhalten im Gefahrfall
Bereich evakuieren. Atemschutzgerät, Gummischuhe und schwere Gummihandschuhe tragen.
Wassersprühstrahl, Kohlendioxid, Trockenlöschmittel oder geeigneter Schaum.
Erste Hilfe
Nach Hautkontakt: Nach Berührung sofort mit Seife und viel Wasser abwaschen.
Nach Augenkontakt: 15 Minuten bei gespreizten Lidern unter fließendem Wasser von außen nach innen ausspülen. Augenarzt konsultieren!
Nach Einatmen: Person sofort an die frische Luft bringen. Ggf. Beatmung durchführen, bei Atembeschwerden Sauerstoff geben.
Nach Verschlucken: 10 g Medizinalkohle zu trinken geben. Arzt rufen.
Nach Kleidungskontakt: Kontaminierte Kleidung sofort ausziehen.
Ersthelfer: siehe gesonderten Anschlag
Sachgerechte Entsorgung
Produkt: Nach Umwandlung in das entsprechende Oxid müssen diese besonders gefährlichen Stoffe der Sondermüllentsorgung zugeführt werden. (Hr. Riepl, Tel.: 8884711).
Beschreibung
Arsine is a colorless, extremely toxic, flammable
gas at room temperature and atmospheric
pressure and is heavier than air. It has a mild
garliclike odor and acts as a blood and nerve
poison. It can be fatal if inhaled in sufficient
quantity and can form flammable mixtures with
air.
Arsine is shipped as a liquefied compressed
gas in steel cylinders under its own vapor pressure
of 219.7 psia (1515 kPa, abs). Arsine is
slightly soluble in both water and organic solvents.
It reacts readily with agents such as potassium
permanganate, bromine, and sodium
hypochlorite to form arsenic compounds. Arsine
is stable at room temperature, but begins to decompose
into its elements around 446°F to
464°F (230°C to 240°C).
Chemische Eigenschaften
Arsine is a highly toxic, colorless gas with a garlic odor. It is soluble in water, benzene,
and chloroform. It is extremely flammable and explosive when exposed to heat, sparks, or
flames. Arsine decomposes on heating and under the infl uence of light and moisture, producing
toxic arsenic fumes. Arsine reacts with strong oxidants, causing explosion hazard
and may explosively decompose on shock, friction, or concussion. Workers in the metallurgical
industry involved in the production process and the maintenance of furnaces, and
in the microelectronics industry get exposed to the substance. Arsine is extensively used in
semiconductor industries, and in the manufacture of microchips.
Physikalische Eigenschaften
Colorless gas; garlic-like unpleasant odor; liquefies at -55°C; solidifies at -116.3°C; heavier than air; gas density 2.695 (air =1); sparingly soluble in cold water (~ 20 mg/100 g water or about 640 mg/L at the NTP); soluble in chloroform and benzene.
Verwenden
Arsine (AsH3), as a colorless gas, is also known as arsenic hydride. It is used to synthesize
organic compounds and as the major ingredient of several military poisons, including the
wartime gas lewisite.
Definition
A poisonous colorless gas
with an unpleasant smell. It decomposes to
arsenic and hydrogen at 230°C. It is produced
in the analysis for arsenic (Marsh’s
test).
synthetische
Arsine is produced by the reaction of arsenic trichloride, arsenic trioxide or
any inorganic arsenic compound with zinc and sulfuric acid. It is also made by
treating a solution of sodium arsenide or potassium arsenide in liquid ammonia
with ammonium bromide:
Na3As + 3NH4Br → AsH3 + 3NaBr + 3NH3
It may be also prepared by decomposition of alkali metal arsenides by water;
or arsenides of other metals with acids:
Ca3As2 + 6 HCl → 2 AsH3 + 3 CaCl2
A poor yield may be obtained if water is substituted for acids. Thus calcium arsenide reacts with water to produce about 15% arsine.
Air & Water Reaktionen
Highly flammable. On exposure to light, decomposes rapidly depositing shiny black arsenic.
Reaktivität anzeigen
ARSINE decomposes into its elements (arsenic, gaseous hydrogen) when heated to 300°C. Can form accidentally by the reaction of arsenic impurities with mineral acids (hydrochloric acid, sulfuric acid) in the presence of common metals (iron, zinc). A reducing agent---not oxidized by air at room temperature [Kirk-Othmer, 3rd ed., Vol. 3, 1978, p. 251], but may react vigorously with other oxidizing agents [Sax, 9th ed., 1996, p. 279]. Moderately explosive in combination with chlorine or nitric acid. When heated to decomposition or ignited, ARSINE emits highly toxic fumes of metallic arsenic.
Hazard
Highly poisonous by inhalation. Periph-
eral nervous system and vacular system impairment,
kidney and liver impairment.
Health Hazard
ARSINE is highly toxic by inhalation; a very short exposure to small quantities may cause death or permanent injury. ARSINE is the most powerful hemolytic poison encountered in industry.
Brandgefahr
Vapors may travel to a source of ignition and flash back. Container may explode in heat of fire. When heated to decomposition, emits highly toxic fumes. Can react vigorously with oxidizing materials. May explode when exposed to chlorine, nitric acid, or potassium plus ammonia. On exposure to light, moist ARSINE decomposes quickly, depositing shiny black arsenic.
Flammability and Explosibility
Arsine is flammable in air, having a lower explosion limit (LEL) of 5.8%. The upper
limit has not been determined. Combustion products (arsenic trioxide and water) are
less toxic than arsine itself. In the event of an arsine fire, stop the flow of gas if
possible without risk of harmful exposure and let the fire burn itself out.
Materials Uses
Arsine is noncorrosive and may, therefore, be
used with most of the commercially available
metals. However, since arsine is mainly used for
the electronics industry, stainless steel is recommended
for the gas delivery systems. Stainless
steel regulators should be used for all highpurity
applications with arsine and arsine mixtures.
Sicherheitsprofil
Confirmed human
carcinogen. Poison by inhalation. Human
red blood cell, gastrointestinal system,
central nervous system, and other systemic
effects by inhalation. Flammable when
exposed to flame. Moderately explosive
when exposed to Cl2, HNO3, (K + NH3,
open flame, or powerful shock. Dangerous,
more toxic than its oxidation product. When
heated to decomposition it emits highly
toxic fumes of arsenic. See also ARSENIC,
ARSENIC COMPOUNDS, and
HYDRIDES.
mögliche Exposition
Arsine is used in making electronic,
semiconductor components; in organic syntheses; and in
making lead-acid storage batteries. Arsine may be generated
by side reactions or unexpectedly; e.g., it may be generated
in metal pickling operations; metal drossing
operations; or when inorganic arsenic compounds contact
sources of nascent hydrogen. It has been known to occur as
an impurity in acetylene. Most occupational exposure
occurs in chemical, smelting, and refining industries. It has
been used as a poison gas. Cases of exposure have come
from workers dealing with zinc, tin, cadmium, galvanized
coated aluminum; and silicon and steel metals. A regulated,
marked area should be established where this chemical is handled, used, or stored in compliance with OSHA
Standard 1910.1045. SA is used as a military poison gas
(blood agent). It forms cyanide in the body.
Carcinogenicity
Arsenic has been considered a human carcinogen for a number of years(1),but the mechanisms underlying these processes have remained elusive due in part to the absence of an appropriate animal model. There
are a number of hypotheses for the mechanisms of arsenical action that include arsenical inhibition of DNA repair, cocarcinogenesis, and more recently the concept of arsenical production of ROS(65,66) that may act in concert with these mechanisms. It is clear from in vitro mutagenicity test systems that arsenicals are not direct-acting mutagens but rather act via some secondary mechanism(s). Given the long history and knowledge that arsenicals in air and water produce human cancers, this is a remarkable situation with regard to occupational and environmental exposures. Most studies of animals exposed to arsenate or arsenite by the oral route have not detected any clear evidence for an increased incidence of skin cancer or other cancers. Recently, a series of studies presented evidence that inorganic arsenic may be a transplacental carcinogen in animals. Waalkes et al. exposed timed pregnant mice to sodium arsenite in drinking water during gestation days 8–18. Dose-related increases in hepatocellular carcinomas and adrenal tumors in the male offspring and uterine hyperplasia in female offspring from treated dams were reported. The offspring also had increase in the number of malignant tumors. Aberrant estrogen signaling, potentially through inappropriate estrogen receptora, may play a role in the arsenic-induced tumors in these offspring.
Environmental Fate
Arsine acts predominantly as a hemolytic agent. Hemolysis
appears to be dependent on membrane disruption as a result
of arsine reactions with sulfhydryl groups and from formation
of hydrogen peroxide and adducts with oxyhemoglobin.
Failure of the kidneys and other organs is probably not only
due to the effects of red blood cell debris slugging within the
microcirculation but also to a direct toxic effect on the
organs.
Lager
cylinders of arsine should be
stored and used in a continuously ventilated gas cabinet or fume hood. Local fire
codes should be reviewed for limitations on quantity and storage requirements.
Carbon steel, stainless steel, Monel?, and Hastelloy ?C are preferred materials for
handling arsine; brass and aluminum should be avoided. Kel-F? and Teflon? are
preferred gasket materials; Viton? and Nylon? are acceptable.
Versand/Shipping
UN2188 Arsine, Hazard class: 2.3; Labels: 2.3-
Poisonous gas, 2.1-Flammable gas, Inhalation Hazard Zone
A. Cylinders must be transported in a secure upright position,
in a well-ventilated truck. Protect cylinder and labels
from physical damage. The owner of the compressed gas
cylinder is the only entity allowed by federal law (49CFR)
to transport and refill them. It is a violation of transportation
regulations to refill compressed gas cylinders without the
express written permission of the owner. Military driver shall
be given full and complete information regarding shipment
and conditions in case of emergency. AR 50-6 deals specifically
with the shipment of chemical agents. Shipments of
agent will be escorted in accordance with AR 740-32.
Inkompatibilitäten
Arsine forms explosive mixture with air.
SA reacts with strong oxidizers, nitric acid, causing an
explosion hazard. Thermally unstable; shock, friction, and
concussion sensitive; can explosively decompose. Can
explode on contact with warm, dry air. Violent reaction
with acids, halogens, mixtures of potassium and ammonia.
Decomposes to metallic arsenic (fumes) on exposure to
light, moisture or upon decomposition from heat or
ignition.
Waste disposal
Return refillable compressed
gas cylinders to supplier. Arsine may be disposed of by controlled
burning. When possible, cylinders should be sealed
and returned to suppliers. Seek guidance from regulatory
agencies as to proper disposal. 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.
Vorsichtsmaßnahmen
Occupational workers should be careful during handling/use of arsine. Workers should
use protective gloves: neoprene, butyl rubber, PVC, polyethylene, or Tefl on. Workers
should also use appropriate protective equipment. If a leak occurs in a user’s equipment,
be certain to purge the piping with an inert gas prior to attempting repairs and evacuate
all personnel from the affected area. The compressed gas cylinders should not be refi lled
without the express written permission of the owner.
Arsin Upstream-Materialien And Downstream Produkte
Upstream-Materialien
Downstream Produkte
