Arsenic trioxide (As2O3) structure, properties and uses

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Anthony Golden

The arsenic trioxide is an inorganic compound whose chemical formula is AstwoOR3. Arsenic in its metallic state is rapidly transformed into this oxide, which is a very toxic poison that can have acute and chronic manifestations..

Since arsenic and oxygen are elements of the p block, with a relatively low electronegativity difference, it is expected that AstwoOR3 is composed of a covalent nature; that is, that the As-O bonds predominate in its solid, over the electrostatic interactions between the As ions3+ metwo-.

Solid arsenic trioxide. Source: Walkerma from Wikimedia Commons.

Acute intoxication with arsenic trioxide occurs by ingestion or inhalation, the most important manifestations of this being: severe gastrointestinal disorders, cramps, circulatory collapse, and pulmonary edema..

However, despite its toxicity, it has been used industrially; for example, in the conservation of wood, in the production of pigments, semiconductors, etc. Likewise, it was formerly used in the treatment of numerous diseases.

Arsenic trioxide is an amphoteric compound, soluble in dilute acids and alkalis, insoluble in organic solvents, and relatively soluble in water. It occurs as a solid (top image), with two crystalline forms: cubic and monoclinic.

Article index

  • 1 Structure of arsenic trioxide
    • 1.1 Claudetite
    • 1.2 Liquid and gaseous
    • 1.3 Arsenolite
  • 2 Properties
    • 2.1 Trade names
    • 2.2 Molecular weight
    • 2.3 Physical appearance
    • 2.4 Odor
    • 2.5 Flavor
    • 2.6 Boiling point
    • 2.7 Melting point
    • 2.8 Flash point
    • 2.9 Solubility in water
    • 2.10 Solubility
    • 2.11 Density
    • 2.12 Vapor pressure
    • 2.13 Decomposition
    • 2.14 Corrosivity
    • 2.15 Heat of vaporization
    • 2.16 Dissociation constant (Ka)
    • 2.17 Refractive index
  • 3 Reactivity
  • 4 Nomenclature
  • 5 Uses
    • 5.1 Industrial
    • 5.2 Physicians
  • 6 References

Structure of arsenic trioxide

Claudetita

At room temperature, AstwoOR3 crystallizes into two monoclinic polymorphs, both found in the mineral claudetite. They have trigonal pyramid units AsO3, which are joined by their oxygen atoms to compensate for the electronic deficiency of the unit on its own.

In a polymorph the AsO units3 they are linked forming rows (claudetite I), and in the other they are linked as if they were weaving a net (claudetite II):

Structure of polymorph claudetite I. Source: Ben Mills [Public domain].
Structure of the polymorph claudetite II. Source: Ben Mills [Public domain].

Liquid and gaseous

When all those structures that define monoclinic crystals are heated, the vibrations are such that several As-O bonds are broken, and a smaller molecule ends up prevailing: As4OR6. Its structure is shown in the image below.

As4O6 molecule. Source: Ben Mills [Public domain]

It could be said to consist of a dimer of AstwoOR3. Its stability is such that it supports 800 ° C in the gas phase; but, above this temperature it fragments into As moleculestwoOR3.

Arsenolite

The same Ace4OR6 can interact with each other to crystallize into a cubic solid, the structure of which is found in the mineral arsenolite.

As4O6 molecules in the arsenolite solid. Source: Ben Mills [Public domain]

Note that the image is showing the structure from a higher plane. Comparing with claudetite, its structural difference with arsenolite is evident. Here, they are discrete molecules of As4OR6 that units are maintained by Van der Waals forces.

Properties

Tradenames

-Arsenolite

-Arsodent

-Trisenox

-Claudetita

Molecular weight

197.84 g / mol.

Physical appearance

-White cubic crystals (arsenolite).

-Colorless monoclinic crystals (Claudetite).

-White or transparent solid, vitreous, amorphous lumps or crystalline powder.

Odor

Toilet.

Taste

Tasteless.

Boiling point

460 ºC.

Melting point

-313 ºC (Claudetite).

-274 ºC (Arsenolite).

ignition point

485 º C (sublimates).

Water solubility

17 g / L at 18 ºC (20 g / L at 25 ºC).

Solubility

Soluble in acids (especially hydrochloric acid) and alkalis. Practically insoluble in chloroform and ether.

Density

-3.85 g / cm3 (cubic crystals);

-4.15 g / cm3 (rhombic crystals).

Vapor pressure

2.47 10-4 mmHg at 25 ºC.

Decomposition

It is not combustible, but on heating it can create toxic smoke that may include arsine..

Corrosiveness

In the presence of moisture it can be corrosive to metals.

Heat of vaporization

77 kJ / mol.

Dissociation constant (Ka)

1,110-4 at 25 ºC.

Refractive index

-1,755 (Arsenolite)

-1.92-2.01 (Claudetite).

Reactivity

-Arsenic trioxide is an amphoteric compound, but it functions preferentially as an acid.

-May react with hydrochloric acid or hydrofluoric acid, forming arsenic trichloride or arsenic trifluoride.

-Likewise, it reacts with strong oxidants, such as nitric acid, causing arsenic acid and nitrous oxide..

-Arsenic trioxide can react with nitric acid, producing arsine or the element arsenic, depending on the reaction conditions..

AcetwoOR3   +   6 Zn + 12 HNO3 => 2 AsH3   +    6 Zn (NO3)two    +    3 HtwoOR.

This reaction served as the basis for the creation of the Marsh Test, used to detect arsenic poisoning..

Nomenclature

AttwoOR3 It can be named according to the following nomenclatures, knowing that arsenic works with valence +3:

-Arsenous oxide (traditional nomenclature).

-Arsenic (III) oxide (stock nomenclature).

-Diarsenic trioxide (systematic nomenclature).

Applications

Industrial

-It is used in the manufacture of glass, specifically as a bleaching agent. It is also used in the manufacture of ceramics, electronic products, and fireworks.

-It is added as a minor component to copper-based alloys, to increase the corrosion resistance of the alloy metals.

-The AcetwoOR3 is the starting material for the preparation of elemental arsenic, to improve electrical connections, and for the production of arsenide semiconductors

-The AcetwoOR3, as well as copper arsenate, they are used as wood preservatives. It was used in combination with copper acetate to make the Paris green pigment, used to make paints and rodenticides..

Doctors

-Arsenic trioxide is a compound that has been used for centuries in the treatment of many diseases. It was used as a tonic in the treatment of nutritional disorders, neuralgia, rheumatism, arthritis, asthma, chorea, malaria, syphilis and tuberculosis.

-Likewise, it has been used in the local treatment of skin diseases, being used to destroy some superficial epitheliomas..

-Fowler's solution was used in the treatment of skin diseases and leukemia. The use of this medicine is discontinued..

-In the 1970s, Chinese researcher Zhang Tingdong conducted research on the use of arsenic trioxide in the treatment of acute promyelocytic leukemia (APL). Which led to the production of the drug Trisenox, which was approved by the US FDA.

-Trisenox has been used in APL patients who do not respond to "first-line" treatment, consisting of all-trans retinoic acid (ATRA). Arsenic trioxide has been shown to induce cancer cells to undergo apoptosis.

-Trisenox is used as a cytostatic in the treatment of refractory promyelocytic subtype (M3) from APL.

References

  1. Shen et al. (2001). Studies on the clinical efficacy and pharmacokinetics of low-dose arsenic trioxide in the treatment of relapsed acute promyelocytic leukemia: a comparison with conventional dosage. Leukemia 15, 735-741.
  2. Science Direct. (2014). Arsenic Trioxide. The Sevier. Recovered from: sciencedirect.com
  3. Wikipedia. (2019). Arsenic trioxide. Recovered from: en.wikipedia.org
  4. PubChem. (2019). Arsenic (III) oxide. Recovered from: pubchem.ncbi.nlm.nih.gov
  5. Deborah M. Rusta and Steven L. Soignetb. (2001). Risk / Benefit Profile of Arsenic Trioxide. The Oncologist vol. 6 Supplement 2 29-32.
  6. The New England Journal of Medicine. (July 11, 2013). Retinoic Acid and Arsenic Trioxide for Acute Promyelocytic Leukemia. n engl j med 369; 2.

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