Zinc phosphide 磷化锌

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磷化锌

管制信息
磷化锌(*)
本品根据《危险化学品安全管理条例》受公安部门管制。
九十年代末,二十世纪初很流行的老鼠药的主要成分,由于有剧烈的毒性,一般都是毒老鼠的。不过一些家宠不小心误食都致命。还有一些想不开的人也吃老鼠药而自杀,后来被禁用。

名称
中文名称:磷化锌 磷化锌结构式
英文名称:Zinc phosphide
中文同义词:磷化锌、亚磷酸锌、耗鼠尽
英文同义词:
ZINC PHOSPHIDE
blue-ox
caswellno922
delusal
epapesticidechemicalcode088601
gopha-rid
mous-con
mous-con
phosphuredezinc
phosphuredezinc(french)
phosvin
CAS编号:1314-84-7
危险货物编号:43038
UN编号:1714
化学式:Zn3P2
分子质量:258.09

理化特性
含量:一级≥90%;二级≥80%。
性状:为暗灰色等轴晶系结晶或粉末,干燥状态下非常稳定,有大蒜气味。
沸点:1100℃
熔点:420℃
相对密度(水=1):4.55(13℃ )
燃烧热(kJ/mol):2451
挥发性:不能挥发。
溶解度:不溶于水及乙醇,可溶于苯,二硫化碳.能溶于盐酸,硫酸而产生磷化氢.
自燃温度:
爆炸极限:
油水分配系数:

稳定性和反应活性
主要用途:用作杀鼠剂和粮食仓库的熏蒸剂。
避免接触的条件:接触潮湿空气。
禁配物:强氧化剂、强酸、潮湿空气。

储存与运输
储存注意事项
储存于阴凉、干燥、通风良好的库房。远离火种、热源。防止阳光直射。包装必须密封,切勿受潮。应与氧化剂、酸类、食用化学品等分开存放,切忌混储。配备相应品种和数量的消防器材。储区应备有合适的材料收容泄漏物。

包装方法
装入厚纸盒内,净重1 公斤,严封后再装入12毫米厚的木箱,箱内衬垫两层牛皮纸。装入纸袋内,每袋净重 5克,严封后装入纸盒内,每盒净重不超过半公斤,螺纹口玻璃瓶、铁盖压口玻璃瓶、塑料瓶或金属桶(罐)外普通木箱。

运输注意事项
运输时运输车辆应配备相应品种和数量的消防器材及泄漏应急处理设备。装运本品的车辆排气管须有阻火装置。运输过程中要确保容器不泄漏、不倒塌、不坠落、不损坏。严禁与氧化剂、酸类等混装混运。运输途中应防曝晒、雨淋,防高温。中途停留时应远离火种、热源。运输用车、船必须干燥,并有良好的防雨设施。车辆运输完毕应进行彻底清扫。铁路运输时要禁止溜放。

 

危险性概述
急性毒性
LD50:12 mg/kg(大鼠经口);40 mg/kg(小鼠经口) LC50:234 mg/m3(大鼠吸入)

健康危害
吸入、误服磷化锌可致磷化氢中毒,表现有不同程度的胃肠症状,以及发热、畏寒、头晕、兴奋及心律紊乱等。严重者有气急、少尿、抽搐、休克及昏迷等。

环境危害
对环境有危害,对水体可造成污染。

燃爆危险
本品遇湿易燃,高毒。

其它有害作用
该物质对环境有危害,应特别注意对水体的污染。

急救措施

皮肤接触
脱去污染的衣着,用流动清水冲洗。

眼睛接触
提起眼睑,用流动清水或生理盐水冲洗。就医。

吸入
迅速脱离现场至空气新鲜处。保持呼吸道通畅。如呼吸困难,给输氧。如呼吸停止,立即进行人工呼吸。就医。

食入
饮足量温水,催吐。就医。
中毒时可口服硫酸铜催吐,可使其转化为无毒的磷化铜沉淀,而阻止其吸收。但禁用牛奶,鸡蛋,油类等脂肪食物以免加速磷的溶解,促进其吸收,加重中毒症状。

消防措施
危险特性
本品遇湿易燃。与氧化剂能发生强烈反应。遇水、潮湿空气或酸分解释出剧毒和自燃的磷化氢气体。遇浓硫酸和王水发生爆炸。遇高热分解释出高毒烟气。

有害燃烧产物
氧化硒、磷化氢、氧化锌。

灭火方法
消防人员须戴好防毒面具,在安全距离以外,在上风向灭火。灭火剂:干粉、二氧化碳、砂土。禁止用水和泡沫灭火。

废弃处置方法
建议用控制焚烧法处置。若可能,重复使用容器或在规定场所掩埋。

泄漏应急处理
应急处理
隔离泄漏污染区,限制出入。切断火源。建议应急处理人员戴自给式呼吸器,穿防毒服。不要直接接触泄漏物。小量泄漏:小心扫起,收集于密闭容器中。大量泄漏:收集回收或运至废物处理场所处置。

操作注意事项
密闭操作,提供充分的局部排风。防止粉尘释放到车间空气中。操作人员必须经过专门培训,严格遵守操作规程。建议操作人员佩戴防尘面具(全面罩),穿胶布防毒衣,戴橡胶手套。远离火种、热源,工作场所严禁吸烟。使用防爆型的通风系统和设备。避免产生粉尘。避免与氧化剂、酸类接触。尤其要注意避免与水接触。配备相应品种和数量的消防器材及泄漏应急处理设备。倒空的容器可能残留有害物。

接触控制/个体防护
【工程控制】 严加密闭,提供充分的局部排风。
【呼吸系统防护】 可能接触其粉尘时,必须佩戴防尘面具(全面罩)。紧急事态抢救或撤离时,应该佩戴空气呼吸器。
【眼睛防护】 呼吸系统防护中已作防护。
【身体防护】 穿胶布防毒衣。
【手防护】 戴橡胶手套。
【其他防护】 工作现场禁止吸烟、进食和饮水。工作完毕,淋浴更衣。保持良好的卫生习惯。


 

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phosphine
Insecticide, rodenticide
IRAC 8B; fumigant

 

NOMENCLATURE
phosphine
IUPAC name phosphine
Chemical Abstracts name phosphine
Other names hydrogen phosphide; phosphorus trihydride CAS RN [7803-51-2] EEC no. 232-260-8

aluminium phosphide
Common name aluminium phosphide (E-ISO, accepted in lieu of a common name); aluminum phosphide (JMAF, accepted in lieu of a common name)
IUPAC name aluminium phosphide
Chemical Abstracts name aluminum phosphide
CAS RN [20859-73-8] EEC no. 244-088-0

magnesium phosphide
IUPAC name magnesium phosphide
Chemical Abstracts name magnesium phosphide
CAS RN [12057-74-8] EEC no. 235-023-7

zinc phosphide
Common name zinc phosphide (E-ISO, JMAF, accepted in lieu of a common name); phosphure de zinc (F-ISO, accepted in lieu of a common name)
IUPAC name trizinc diphosphide
Chemical Abstracts name zinc phosphide
CAS RN [1314-84-7] EEC no. 215-244-5

PHYSICAL CHEMISTRY
phosphine
Mol. wt. 34.0 M.f. H3P Form Colourless, odourless, flammable gas; (tech., garlic or rotting fish odour). M.p. -132.5 ºC B.p. -87.4 ºC V.p. High Henry 33 269 Pa m3 mol-1 Solubility In water 26 cm3/100 ml (17 ºC). In ethanol 0.5, ether 2, oil of turpentine 3.25 (all in vol. phosphine per vol. solvent, 18 ºC). In cyclohexanol 285.6 cm3/100 ml (26 ºC). Stability Oxidised to phosphoric acid by oxidising agents and atmospheric oxygen. F.p. It is spontaneously flammable in air (due to the presence of traces of other hydrides of phosphorus) with an explosion limit of 26.1-27.1 mg/l

aluminium phosphide
Mol. wt. 58.0 M.f. AlP Form Dark grey or yellowish crystals. M.p. >1000 ºC V.p. Very low, even at 1000 ºC S.g./density 2.85 (25 °C) Stability Though stable when dry, it reacts with moist air, violently with acids, producing phosphine.

magnesium phosphide
Mol. wt. 134.9 M.f. Mg3P2 Form Yellow-green crystals. M.p. >750 °C S.g./density 2.055 Stability Stable when dry, but reacts with atmospheric moisture, and violently with acids, producing phosphine; used to generate this fumigant, reacting more rapidly than aluminium phosphide.

zinc phosphide
Composition Tech. grade is 80-95% pure. Mol. wt. 258.1 M.f. P2Zn3 Form Amorphous grey-black powder, with a garlic-like odour. M.p. 420 ºC (when heated in the absence of oxygen) V.p. Negligible in the dry state S.g./density 4.55 Solubility Practically insoluble in water (decomposes slowly). Slightly soluble in carbon disulfide and benzene. Practically insoluble in alcohols. Stability Stable when dry, but decomposes slowly in moist air; it is decomposed violently by acids to produce phosphine, which is a potent mammalian poison, and impurities which render the gas spontaneously flammable.

COMMERCIALISATION
phosphine
Manufacturers United Phosphorus

aluminium phosphide
History Introduced as a source of fumigant insecticide by Dr. Werner Freyberg Chemische Fabrik (now Detia Freyberg). Patents GB 461997; US 2117158 Manufacturers Ag Pesticides; Aimco; Detia Freyberg; Excel; Sharda; United Phosphorus; Youngil

magnesium phosphide
History Introduced by Degesch AG to generate phosphine and so fumigate stored foodstuffs. Patents DE 923999 to Edmund Manufacturers Detia Freyberg; United Phosphorus

zinc phosphide
History It has long been used as a poison against rodents. Manufacturers Ag Pesticides; Aimco; Bell; Excel; HACCO; Liphatech Inc.; Sharda; UAP; United Phosphorus

APPLICATIONS
phosphine
Uses As a fumigant, to control a broad spectrum of insects for non-food commodities in sealed containers or structures.

aluminium phosphide
Mode of action Insecticide and rodenticide which is a respiratory, metabolic, and nerve poison. Evolves a non-flammable mixture of phosphine (the toxicant), ammonia and carbon dioxide. Uses Fumigation control of insect and rodent pests in stored grains (wheat, rye, barley, rice, sorghum, maize, etc.), seed grains, grain products (flour, noodles, semolina, etc.), pulses (peas, beans, lentils, etc.), tobacco, tapioca (roots and flour), oil seeds, expeller cake, nuts, nut kernels, dried fruit, coffee beans, cocoa beans, tea, etc.; and in empty warehouses, silos, packing materials, transport containers, etc. Phytotoxicity Living plants, fresh vegetables and fruits, with few exceptions, should not be fumigated. Formulation types GE; Fumigant. Selected products: 'Agtoxin' (Ag Pesticides); 'Al-Phos' (Aimco); 'Celphide' (Excel); 'Celphos' (Excel); 'Phostoxin' (Detia Degesch); 'Quickphos' (United Phosphorus); 'Shaphos' (Sanonda); 'Timifos' (Tide)

magnesium phosphide
Mode of action Insecticide and rodenticide which is a respiratory, metabolic, and nerve poison. Liberates phosphine, which is the toxicant. Uses As for aluminium phosphide. Also used for control of moles, voles, rats, hamsters, and rabbits by fumigation of burrows. Phytotoxicity Living plants, fresh vegetables and fruits, with few exceptions, should not be fumigated. Formulation types GE; Fumigant. Selected products: 'Magnaphos' (United Phosphorus); 'Magtoxin' (Detia Degesch)

zinc phosphide
Mode of action Rodenticide (for single ingestion). Reacts with stomach acids to liberate poisonous phosphine, which enters the bloodstream, and results in damage to the liver, kidneys and heart. Uses Bait rodenticide for control of rats, mice, voles, ground squirrels, and gophers. Also used in tracking powder form for house mouse control. Formulation types AB; CP; PA; RB; SB. Selected products: 'Agzinphos' (Ag Pesticides); 'Commando' (Excel); 'Fokeba' (Vipesco); 'Ratol' (United Phosphorus); 'Rattekal-Plus' (Frunol); 'Zawa' (Sanonda); 'Zinc-Tox' (Aimco)

OTHER PRODUCTS
phosphine
'Eco2Fume' (Cytec)

aluminium phosphide
'Celphine' (Excel); 'Detia-Gas-Ex-B' (and Ex-T, Ex-P) (Detia Degesch); 'Fumitoxin' (Pestcon); 'Gastoxin' (Bernardo); 'Gran Quick Phos' (Agricultura Nacional); 'L-Fume' (Excel); 'Talunex' (Luxan) Discontinued products: 'DeliciaGastoxin' * (Delicia); 'Phostek' * (Killgerm)

magnesium phosphide
'Degesch Plates' (Detia Degesch); 'Fumi-Cel' (Degesch America); 'Fumi-Strip' (Degesch America) Discontinued products: 'Detiaphos' * (Detia Degesch)

zinc phosphide
'Arrex' (BASF); 'Ridall-Zinc' (LiphaTech Inc.); 'ZP' (Antec) Discontinued products: 'Denkarin Grains' * (Denka)

ANALYSIS
phosphine
Phosphine present during fumigation can be determined using commercially available detector tubes, by glc (B. Chakrabarti & H. E. Wainman, Chem. Ind. (London), 1972, p. 300) or by aspiration through aqueous mercuric chloride and measuring the change in electrical conductivity (A. H. Harris, Proc. GASGA Tech. Seminar, TDRI, Slough, 1986). Methods for residues in foods reviewed, with details by J. L. Daft in Comp. Anal. Profiles, p. 274.

aluminium phosphide
Product and residue analysis depend upon determining the phosphine liberated by acid treatment. Measurement is by glc (B. Berck et al., J. Agric. Food Chem., 1970, 18, 143; T. Dumas, J. Assoc. Off. Anal. Chem., 1978, 61, 51; Anal. Methods Residues Pestic., 1988, Part II, M8; K. A. Scudamore, Anal. Methods Pestic. Plant Growth Regul., 1988, 16, 251; K. A. Scudamore & G. Goodship, Pestic. Sci., 1986, 37, 385).

magnesium phosphide
Product analysis by determining the phosphine liberated on treatment with acid, by glc (T. Dumas, J. Assoc. Off. Anal. Chem., 1978, 61, 51) or phosphate produced after reaction with bromine water (R. B. Bruce et al., J. Agric. Food Chem., 1962, 10, 18).

zinc phosphide
Product analysis by reaction with acid, the phosphine produced is estimated by titration (CIPAC Handbook, 1970, 1, 703), or oxidised to phosphoric acid which is estimated by standard methods (J. W. Elmore & F. R. Roth, J. Assoc. Off. Agric. Chem., 1943, 26, 559; 1947, 30, 213; B. L. Griswold et al., Anal. Chem., 1951, 23, 192).

MAMMALIAN TOXICOLOGY
phosphine
Reviews FAO/WHO 6, 7 (see part 2 of the Bibliography). Skin and eye No absorption through the skin. Inhalation Powerful respiratory poison. LC50 (4 h) for rats 11 ppm (0.015 mg/l) (R. S. Waritz & R. M. Brown, Am. Ind. Assoc. J., 36, 452-458 (1975)). Inhalation at 10 mg/m3 can cause death within 6 h, and at 300 ml gas/m3 for one hour, there is danger to life. No symptoms of chronic poisoning are observed. ADI (JMPR) Not necessary on basis of no residue in food [1966]. Other Phosphine is a potent, acute mammalian poison, but feeding trials with fumigated foodstuffs have shown no chronic effects on rats (U. Hackenberg, Toxicol. Appl. Pharmacol., 1972, 23,147). Toxicity class WHO (a.i.) FM; EPA (formulation) I

aluminium phosphide
Oral Acute oral LD50 for rats 8.7 mg/kg. Toxicity class WHO (a.i.) FM EC classification F; R15/29| T+; R28| R32| N; R50

magnesium phosphide
Oral Acute oral LD50 for rats 11.2 mg/kg. Toxicity class WHO (a.i.) FM EC classification F; R15/29| T+; R28| N; R50

zinc phosphide
Oral Acute oral LD50 for rats 45.7, sheep 60-70 mg/kg (M. A. Nekrasova, Sb. Rab., Leningr. Vet. Inst., 1964, No. 25, 372). Skin and eye Acute percutaneous LD50 for rabbits 2000-5000 mg/kg. Non-irritating to skin and eyes. Toxicity class WHO (a.i.) Ib; EPA (formulation) I EC classification F; R15/29| T+; R28| R32| N; R50, R53

ECOTOXICOLOGY
phosphine
Fish LC50 (96 h) for rainbow trout 9.7 ´ 10-3 ppm. Daphnia EC50 (24 h) 0.2 mg/l.

zinc phosphide
Birds Acute oral LD50 for mallard ducks 37.5, bobwhite quail 13.5, pheasants 9 mg/kg (D. W. Hayne, Mich. Agric. Exp. Stn., Q. Bull., 1951, No. 33, 412); for fowls, the lethal dose is 7-17 mg/kg (G. D. Shearer, J. Comp. Pathol. Therap., 1945, 55, 301). Fish Acute LC50 for bluegill sunfish 0.8, rainbow trout 0.5 mg/l.

ENVIRONMENTAL FATE
EHC 73 (WHO, 1988; a review of phosphine and metal phosphides). Animals In mammals, phosphine is probably metabolised to non-toxic phosphates. Plants In stored products, phosphine undergoes oxidation to phosphoric acid.