ثلاثي أكسيد الزرنيخ

Arsenic trioxide
Arsenic trioxide
Ball-and-stick model of the As4O6 molecule
الأسماء
أسماء أخرى
Arsenic(III) oxide,
Arsenic sesquioxide,
Arsenicum album,
Arseneous oxide,
Arseneous anhydride,
White arsenic[1]
Identifiers
رقم CAS
3D model (JSmol)
ChemSpider
DrugBank
ECHA InfoCard 100.014.075 Edit this at Wikidata
رقم EC
  • 215-481-4
رقم RTECS
  • CG3325000
InChI InChI={{{value}}}
SMILES
الخصائص
الصيغة الجزيئية As2O3
كتلة مولية 197.841 g/mol
المظهر White solid
الكثافة 3.74 g/cm3
نقطة الانصهار
نقطة الغليان
قابلية الذوبان في الماء 2 g/100 ml (25°C)
see text
قابلية الذوبان soluble in dilute acids and alkalies, practically insoluble in organic solvents [2]
الحموضة (pKa) 9.2
البنية
البنية البلورية cubic (α)<180°C
monoclinic (β) >180°C
الشكل الجزيئي See Text
Dipole moment Zero
الكيمياء الحرارية
الإنتالپية المعيارية
للتشكل ΔfHo298 		−657.4 kJ/mol
Standard molar
entropy So298 		? J.K–1.mol–1
فارماكولوجيا
رباط البروتينات 75% bound
المخاطر
Very toxic (T+)
Carc. Cat. 1
Dangerous for the
environment (N)
توصيف المخاطر R45, R28, R34,
R50/53
تحذيرات وقائية S53, S45, S60,
S61
NFPA 704 (معيـَّن النار)
Flammability code 0: لن يشتعل. مثل الماءHealth code 3: التعرض لفترة قصيرة قد يتسبب في جروح خطيرة مؤقتة أو باقية. مثل غاز الكلورReactivity code 0: مستقر في العادة، حتى تحت ظروف التعرض للنار، ولا يتفاعل مع الماء. مثل النيتروجين السائلSpecial hazards (white): no codeNFPA 704 four-colored diamond
0
3
0
الجرعة أو التركيز القاتل (LD, LC):
14.6 mg/kg (rat, oral)
مركبات ذا علاقة
Arsenic trisulfide
Phosphorus trioxide
Antimony trioxide
ما لم يُذكر غير ذلك، البيانات المعطاة للمواد في حالاتهم العيارية (عند 25 °س [77 °ف]، 100 kPa).
YesY verify (what is YesYX mark.svgN ?)
مراجع الجدول

ثلاثي أكسيد الزرنيخ Arsenic trioxide هو مركب كيميائي له الصيغة As2O3 ، ويكون على شكل بلورات بيضاء. وهذا الأكسيد الهام تجارياً للزرنيخ هو السابق الرئيسي لمنتجات الزرنيخ الأخرى، بما فيها مركبات الزرنيخ العضوية. ويـُنتج منه نحو 50,000 طن سنوياً.[3] والكثير من استخداماته هي موضع جدل بسبب السمية العالية لمركبات الزرنيخ.

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الخواص

  • ينحل ثالث أكسيد الزرنيخ بالماء والمحلات الأخرى بصعوبة، لكنه ينحل في الأحماض والقلويات مشكلاً الأملاح الموافقة حسب المعادلات:
As2O3 + 6NaOH → 2Na3AsO3 + 3H2O
As2O3 + 6HCl → 2AsCl3 + 3H2O
  • يوجد ثالث أكسيد الزرنيخ بشكلين حسب البنية البلورية له، إحداهما مكعبة وهي ثابتة عند درجات الحرارة العادية، وأخرى أحادية الميل تكون ثابتة عند درجات حرارة فوق 221°س.


التحضير

  • يوجد أكسيد الزرنيخ الثلاثي في الطبيعة.
  • يحضر مخبرياً إما من حرق فلز الزرنيخ بالهواء حسب المعادلة:
2As + 3/2O2 → As2O3
  • يحضر أكسيد الزرنيخ الثلاثي صناعياً من تحميص معدن الزرنيخ الذي يوجد غالباً على شكل كبريتيد مع فلز الحديد حسب المعادلة:
2FeAsS + 5O2 → Fe2O3 + As2O3 + 2SO2

البنية

Arsenolite-xtal-3D-balls-D.png Claudetite-I-layer-3D-balls.png Claudetite-II-layer-3D-balls.png
arsenolite
(cubic)
claudetite I
(monoclinic)
claudetite II
(monoclinic)

الاستخدامات

  • يعد أكسيد الزرنيخ الثلاثي مصدراً لإنتاج جميع مركبات الزرنيخ الأخرى.

Medical

Arsenic trioxide is indicated in combination with tretinoin for treatment of adults with newly-diagnosed low-risk acute promyelocytic leukemia whose acute promyelocytic leukemia is characterized by the presence of the t(15;17) translocation or PML/RAR-alpha gene expression; and for induction of remission and consolidation in patients with acute promyelocytic leukemia who are refractory to, or have relapsed from, retinoid and anthracycline chemotherapy, and whose acute promyelocytic leukemia is characterized by the presence of the t(15;17) translocation or PML/RAR-alpha gene expression.[4][5][6]

Arsenic trioxide is used to treat a type of cancer known as acute promyelocytic leukemia (APL).[7] It may be used both in cases that are unresponsive to other agents, such as all-trans retinoic acid (ATRA) or as part of the initial treatment of newly diagnosed cases.[7] This initial treatment may include combination therapy of arsenic trioxide with all-trans retinoic acid (ATRA).[8]

Effectiveness appears similar to Realgar/Indigo naturalis, which can be taken by mouth and is less expensive but is less available.[9] It works by encouraging the proteosome breakdown of retinoic acid receptor alpha, by moving the protein on to the nuclear matrix and increasing ubiquitination.[10]

In the 1970s, Chinese researcher Zhang Tingdong and colleagues discovered this use.[11] It was approved for leukemia treatment in the United States in 2000.[12] University of Hong Kong developed a liquid form of arsenic trioxide that can be given by mouth.[13] Organoarsenic compounds, such as feed additives (roxarsone) and medication (neosalvarsan), are derived from arsenic trioxide.[بحاجة لمصدر]

Manufacturing

Industrial uses include usage as a precursor to forestry products, in colorless glass production, and in electronics.[3] Being the main compound of arsenic, the trioxide is the precursor to elemental arsenic, arsenic alloys, and arsenide semiconductors. Bulk arsenic-based compounds sodium arsenite and sodium cacodylate are derived from the trioxide.[بحاجة لمصدر]

A variety of applications exploit arsenic's toxicity, including the use of the oxide as a wood preservative. Copper arsenates, which are derived from arsenic trioxide, are used on a large scale as a wood preservative in the U.S. and Malaysia, but such materials are banned in many parts of the world. This practice remains controversial.[3] In combination with copper(II) acetate, arsenic trioxide gives the vibrant pigment known as Paris green used in paints and as a rodenticide. This application has been discontinued.[بحاجة لمصدر]

Alternative medicine

Despite the well known toxicity of arsenic, arsenic trioxide was used in traditional Chinese medicine, where it is known as pi-shuang (صينية: 砒霜؛ پن‌ين: pīshuāng؛ حرفياً: 'arsenic frost'�). In homeopathy, it is called arsenicum album. Some discredited patent medicines, e.g., Fowler's solution, contained derivatives of arsenic oxide.[14]

الاستخدامات الطبية

الانتاج والتواجد الطبيعي

Historic arsenic mine Sankt Blasen, Austria

Arsenic trioxide can be generated via routine processing of arsenic compounds including the oxidation (combustion) of arsenic and arsenic-containing minerals in air. Illustrative is the roasting of orpiment, a typical arsenic sulfide ore.

2 As 2S 3 + 9 O 2 → 2 As 2O 3 + 6 SO 2

Most arsenic oxide is, however, obtained as a volatile by-product of the processing of other ores. For example, arsenopyrite, a common impurity in gold- and copper-containing ores, liberates arsenic trioxide upon heating in air. The processing of such minerals has led to numerous cases of poisonings,[15] and after the mine is closed, the leftover trioxide waste will present environmental hazard (as was the case with the Giant Mine, for example). Only in China are arsenic ores intentionally mined.[3]

In the laboratory, it is prepared by hydrolysis of arsenic trichloride:[16]

2 AsCl
3 + 3 H
2O → As
2O
3 + 6 HCl

As 2O 3 occurs naturally as two minerals, arsenolite (cubic) and claudetite (monoclinic). Both are relatively rare secondary minerals found in oxidation zones of As-rich ore deposits.


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السمية

انظر أيضاً: Arsenic poisoning

Arsenic trioxide is readily absorbed by the digestive system. Ingestion of as little as 0.1 grams can be fatal.[3]

Chronic arsenic poisoning is known as arsenicosis. This disorder affects workers in smelters, in populations whose drinking water contains high levels of arsenic (0.3–0.4 ppm), and in patients treated for long periods with arsenic-based pharmaceuticals. Long-term ingestion of arsenic trioxide either in drinking water or as a medical treatment can lead to skin cancer. Reproductive problems (high incidences of miscarriage, low birth weight, congenital deformations) have also been indicated in one study of women exposed to arsenic trioxide dust as employees or neighbours of a copper foundry.

In the U.S., the OSHA 1910.1018 occupational permissible exposure limit for inorganic arsenic compounds in breathing zone air is 0.010 mg/m3.

المصادر

Taschenbuch chemische Substanzen, Willmes, Verlag Harri Deutsch, ISBN 3-8171-1662-4

الهامش

  1. ^ Shakhashiri BZ, "Chemical of the Week: Arsenic", University of Wisconsin-Madison Chemistry Dept.
  2. ^ Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
  3. ^ أ ب ت ث ج Sabina C. Grund, Kunibert Hanusch, Hans Uwe Wolf "Arsenic and Arsenic Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, VCH-Wiley, 2008, Weinheim.
  4. ^ خطأ استشهاد: وسم <ref> غير صحيح؛ لا نص تم توفيره للمراجع المسماة Trisenox FDA label
  5. ^ خطأ استشهاد: وسم <ref> غير صحيح؛ لا نص تم توفيره للمراجع المسماة Trisenox EPAR
  6. ^ "Drug Approval Package: Trisenox (Arsenic Trioxide) NDA #21-248". U.S. Food and Drug Administration (FDA). 12 July 2001. Archived from the original on 3 February 2024. Retrieved 3 February 2024.
  7. ^ أ ب خطأ استشهاد: وسم <ref> غير صحيح؛ لا نص تم توفيره للمراجع المسماة AHFS2019
  8. ^ Zhu J, Chen Z, Lallemand-Breitenbach V, de Thé H (September 2002). "How acute promyelocytic leukaemia revived arsenic". Nature Reviews. Cancer. 2 (9): 705–713. doi:10.1038/nrc887. PMID 12209159. S2CID 2815389.
  9. ^ Howard SC. "Proposal for the inclusion of arsenic therapies in the WHO Model List of Essential Medicines for the treatment of acute promyelocytic leukemia" (PDF). WHO. Archived from the original (PDF) on 9 March 2022. Retrieved 15 November 2019.
  10. ^ Zhu J, Koken MH, Quignon F, Chelbi-Alix MK, Degos L, Wang ZY, Chen Z, de Thé H (April 1997). "Arsenic-induced PML targeting onto nuclear bodies: implications for the treatment of acute promyelocytic leukemia". Proceedings of the National Academy of Sciences of the United States of America. 94 (8): 3978–3983. Bibcode:1997PNAS...94.3978Z. doi:10.1073/pnas.94.8.3978. PMC 20553. PMID 9108090.
  11. ^ Rao Y, Li R, Zhang D (June 2013). "A drug from poison: how the therapeutic effect of arsenic trioxide on acute promyelocytic leukemia was discovered". Science China Life Sciences. 56 (6): 495–502. doi:10.1007/s11427-013-4487-z. PMID 23645104.
  12. ^ Bian Z, Chen S, Cheng C, Wang J, Xiao H, Qin H (2012). "Developing new drugs from annals of Chinese medicine". Acta Pharmaceutica Sinica B. 2: 1–7. doi:10.1016/j.apsb.2011.12.007.
  13. ^ Au WY, Kumana CR, Kou M, Mak R, Chan GC, Lam CW, Kwong YL (July 2003). "Oral arsenic trioxide in the treatment of relapsed acute promyelocytic leukemia". Blood. 102 (1): 407–408. doi:10.1182/blood-2003-01-0298. PMID 12814916.
  14. ^ Gibaud S, Jaouen G (2010). "Arsenic-Based Drugs: From Fowler's Solution to Modern Anticancer Chemotherapy". Medicinal Organometallic Chemistry. Topics in Organometallic Chemistry. Vol. 32. pp. 1–20. Bibcode:2010moc..book....1G. doi:10.1007/978-3-642-13185-1_1. ISBN 978-3-642-13184-4.
  15. ^ "Giant Mine – Northwest Territories Region – Indian and Northern Affairs Canada". Archived from the original on 27 June 2006. Retrieved 28 August 2007.
  16. ^ خطأ استشهاد: وسم <ref> غير صحيح؛ لا نص تم توفيره للمراجع المسماة Brauer

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