Stibine (
IUPAC
The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
name: stibane) is a
chemical compound
A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
with the formula SbH
3. A
pnictogen hydride Pnictogen hydrides or hydrogen pnictides are binary compounds of hydrogen with pnictogen ( or ; from grc, πνῑ́γω "to choke" and -gen, "generator") atoms (elements of group 15: nitrogen, phosphorus, arsenic, antimony, and bismuth) covalently ...
, this colourless, highly toxic gas is the principal
covalent hydride
In chemistry, a hydride is formally the anion of hydrogen( H−). The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of ...
of
antimony
Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient time ...
, and a heavy analogue of
ammonia
Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was ...
. The molecule is pyramidal with H–Sb–H angles of 91.7° and Sb–H distances of 170.7
pm (1.707
Å). This gas has an offensive smell like
hydrogen sulfide
Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...
(rotten eggs).
Preparation
SbH
3 is generally prepared by the reaction of Sb
3+ sources with H− equivalents:
:2 Sb
2O
3 + 3 LiAlH
4 → 4 SbH
3 + 1.5 Li
2O + 1.5 Al
2O
3
:4 SbCl
3 + 3 NaBH
4 → 4 SbH
3 + 3 NaCl + 3 BCl
3
Alternatively, sources of Sb
3− react with protonic reagents (even water) to also produce this unstable gas:
:Na
3Sb + 3 H
2O → SbH
3 + 3 NaOH
Properties
The chemical properties of SbH
3 resemble those for
AsH3.
Typical for a heavy hydride (e.g. AsH
3, H
2Te, SnH
4), SbH
3 is unstable with respect to its elements. The gas decomposes slowly at room temperature but rapidly at 200 °C:
::2 SbH
3 → 3 H
2 + 2 Sb
The decomposition is
autocatalytic
A single chemical reaction is said to be autocatalytic if one of the reaction products is also a catalyst for the same or a coupled reaction.Steinfeld J.I., Francisco J.S. and Hase W.L. ''Chemical Kinetics and Dynamics'' (2nd ed., Prentice-Hall 199 ...
and can be explosive.
SbH
3 is readily
oxidized
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
by O
2 or even air:
::2 SbH
3 + 3 O
2 → Sb
2O
3 + 3 H
2O
SbH
3 exhibits no basicity, but it can be deprotonated:
::SbH
3 +
NaNH2 → NaSbH
2 + NH
3
Uses
Stibine is used in the
semiconductor
A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
industry to
dope silicon with small quantities of
antimony
Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient time ...
via the process of
chemical vapour deposition
Chemical vapor deposition (CVD) is a vacuum deposition method used to produce high quality, and high-performance, solid materials. The process is often used in the semiconductor industry to produce thin films.
In typical CVD, the wafer (substra ...
(CVD). It has also been used as a silicon dopant in epitaxial layers. Reports claim the use of SbH
3 as a
fumigant
Fumigation is a method of pest control or the removal of harmful micro-organisms by completely filling an area with gaseous pesticides—or fumigants—to suffocate or poison the pests within. It is used to control pests in buildings ( ...
but its instability and awkward preparation contrast with the more conventional fumigant
phosphine
Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula , classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting ...
.
History
As stibine (SbH
3) is similar to
arsine
Arsine (IUPAC name: arsane) is an inorganic compound with the formula As H3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. Despite its lethality, it finds some applications in th ...
(AsH
3); it is also detected by the
Marsh test
The Marsh test is a highly sensitive method in the detection of arsenic, especially useful in the field of forensic toxicology when arsenic was used as a poison. It was developed by the chemist James Marsh and first published in 1836. The metho ...
. This sensitive test detects arsine generated in the presence of
arsenic
Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, but ...
.
This procedure, developed circa 1836 by
James Marsh, treats a sample with arsenic-free
zinc
Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
and dilute
sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
: if the sample contains arsenic, gaseous arsine will form. The gas is swept into a glass tube and decomposed by means of heating around 250 – 300 °C. The presence of arsenic is indicated by formation of a deposit in the heated part of the equipment. The formation of a black mirror deposit in the cool part of the equipment indicates the presence of
antimony
Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient time ...
.
In 1837
Lewis Thomson
Lewis may refer to:
Names
* Lewis (given name), including a list of people with the given name
* Lewis (surname), including a list of people with the surname
Music
* Lewis (musician), Canadian singer
* "Lewis (Mistreated)", a song by Radiohead ...
and
Pfaff
PFAFF (german: PFAFF Industriesysteme und Maschinen AG, PFAFF Industrial) is a German manufacturer of sewing machines and is now owned by the SGSB Co. Ltd.
History
PFAFF was founded in Kaiserslautern, Germany, in 1862 by instrument maker Geo ...
independently discovered stibine. It took some time before the properties of the toxic gas could be determined, partly because a suitable synthesis was not available. In 1876 Francis Jones tested several synthesis methods, but it was not before 1901 when
Alfred Stock
Alfred Stock (July 16, 1876 – August 12, 1946) was a German inorganic chemist. He did pioneering research on the hydrides of boron and silicon, coordination chemistry, mercury, and mercury poisoning. The German Chemical Society's Alfred-Stock Me ...
determined most of the properties of stibine.
Safety
SbH
3 is an unstable flammable gas. It is highly toxic, with an
LC50
In toxicology, the median lethal dose, LD50 (abbreviation for " lethal dose, 50%"), LC50 (lethal concentration, 50%) or LCt50 is a toxic unit that measures the lethal dose of a toxin, radiation, or pathogen. The value of LD50 for a substance is ...
of 100 ppm in mice.
Toxicology
The toxicity of stibine is distinct from that of other
antimony
Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient time ...
compounds, but similar to that of
arsine
Arsine (IUPAC name: arsane) is an inorganic compound with the formula As H3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. Despite its lethality, it finds some applications in th ...
.
Stibine binds to the
haemoglobin
Hemoglobin (haemoglobin BrE) (from the Greek word αἷμα, ''haîma'' 'blood' + Latin ''globus'' 'ball, sphere' + ''-in'') (), abbreviated Hb or Hgb, is the iron-containing oxygen-transport metalloprotein present in red blood cells (erythrocyte ...
of red blood cells, causing them to be destroyed by the body. Most cases of stibine poisoning have been accompanied by arsine poisoning, although animal studies indicate that their toxicities are equivalent. The first signs of exposure, which can take several hours to become apparent, are
headache
Headache is the symptom of pain in the face, head, or neck. It can occur as a migraine, tension-type headache, or cluster headache. There is an increased risk of depression in those with severe headaches.
Headaches can occur as a result ...
s,
vertigo
Vertigo is a condition where a person has the sensation of movement or of surrounding objects moving when they are not. Often it feels like a spinning or swaying movement. This may be associated with nausea, vomiting, sweating, or difficulties w ...
, and
nausea
Nausea is a diffuse sensation of unease and discomfort, sometimes perceived as an urge to vomit. While not painful, it can be a debilitating symptom if prolonged and has been described as placing discomfort on the chest, abdomen, or back of the ...
, followed by the symptoms of
hemolytic anemia
Hemolytic anemia or haemolytic anaemia is a form of anemia due to hemolysis, the abnormal breakdown of red blood cells (RBCs), either in the blood vessels (intravascular hemolysis) or elsewhere in the human body (extravascular). This most commonly ...
(high levels of unconjugated
bilirubin
Bilirubin (BR) (Latin for "red bile") is a red-orange compound that occurs in the normal catabolic pathway that breaks down heme in vertebrates. This catabolism is a necessary process in the body's clearance of waste products that arise from the ...
),
hemoglobinuria
Hemoglobinuria is a condition in which the oxygen transport protein hemoglobin is found in abnormally high concentrations in the urine. The condition is caused by excessive intravascular hemolysis, in which large numbers of red blood cells (RBCs) ...
, and
nephropathy
Kidney disease, or renal disease, technically referred to as nephropathy, is damage to or disease of a kidney. Nephritis is an inflammatory kidney disease and has several types according to the location of the inflammation. Inflammation can ...
.
See also
*
Antimony
Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient time ...
(Sb)
*
Arsine
Arsine (IUPAC name: arsane) is an inorganic compound with the formula As H3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. Despite its lethality, it finds some applications in th ...
(AsH
3)
*
Devarda's alloy
Devarda's alloy (CAS # 8049-11-4), is an alloy of aluminium (44% – 46%), copper (49% – 51%) and zinc (4% – 6%).
Devarda's alloy is used as reducing agent in analytical chemistry for the determination of nitrat ...
, also used to produce arsine and stibine in the lab
*
List of highly toxic gases
Many gases have toxic properties, which are often assessed using the LC50 (median lethal dose) measure. In the United States, many of these gases have been assigned an NFPA 704 health rating of 4 (may be fatal) or 3 (may cause serious or perman ...
*
Marsh test
The Marsh test is a highly sensitive method in the detection of arsenic, especially useful in the field of forensic toxicology when arsenic was used as a poison. It was developed by the chemist James Marsh and first published in 1836. The metho ...
, first used to analyse AsH
3 and SbH
3
*
James Marsh, invented the Marsh test in 1836
*
Nascent hydrogen
Nascent hydrogen is an outdated concept in organic chemistry that was once invoked to explain dissolving-metal reactions, such as the Clemmensen reduction and the Bouveault–Blanc reduction. Since organic compounds do not react with H2, a special ...
References
External links
International Chemical Safety Card 0776*
{{Hydrides by group
Antimony(III) compounds
Metal hydrides