Cuprous Oxide 氧化亚铜

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氧化亚铜

氧化亚铜氧化亚铜为一价铜的氧化物,鲜红色粉末状固体,几乎不溶于水,在酸性溶液中歧化为二价铜。

中文名称:氧化亚铜
中文别名:一氧化二铜;红色氧化铜;氧化亚铜(I)
英文名称:Cuprous Oxide
CAS号:1317-39-1
EINECS号:215-269-1;215-270-7
分子式: Cu2O
分子量: 143.09

物化性质
性状:深红色或深棕色结晶性粉末。在潮湿空气中易氧化,溶于酸和浓氨水,不溶于水。
密度:6.0g/cm3 氧化亚铜微晶
熔点:1500K
闪点:1800°C
沸点:1800℃。
溶解度:practically insoluble
折射率:2.705
禁带宽度:1.8--2.2eV(直接带隙)
氧化亚铜为一价铜的氧化物,红色或暗红色八面立方晶系结晶性粉末。相对密度6.0。熔点1235℃。在1800℃失去氧。不溶于水和醇,溶于盐酸、氯化铵、氨水,微溶于硝酸。溶于盐酸生成白色氯化亚铜结晶粉末。遇稀硫酸和稀硝酸生成铜盐。在空气中会迅速变蓝。能溶于浓碱、三氯化铁等溶液中。在湿空气中逐渐氧化成黑色氧化铜。
在酸性溶液中歧化为二价铜,说明在溶液中,二价铜离子的稳定性大于一价铜离子,例如氧化亚铜和硫酸反应,生成硫酸铜和铜。
Cu2O+H2SO4=CuSO4+Cu+H2O
氧化亚铜与氨水和氢卤酸反应,因生成络合物,不歧化成二价铜和铜
溶于浓氨溶液形成无色配合物 [Cu(NH3)2]+,其在空气中被氧化为蓝色的 [Cu(NH3)4(H2O)2]2+
氧化亚铜可溶于盐酸生成 HCuCl2(氯化亚铜的配合物),也可溶于硫酸及硝酸分别形成硫酸铜及硝酸铜。

用途
氧化亚铜用于制船底防污漆(杀死低级海生动物)。用作杀菌剂(86.2%铜大师WP、WG)陶瓷和搪瓷的着色剂、红色玻璃染色剂,还用于制造各种铜盐、分析试剂及用于电器工业中的整流电镀、农作物的杀菌剂和整流器的的材料等。
果树期和幼果期

制法
由硫酸铜溶液中加入葡萄糖溶液,再加入氢氧化钠溶液即可制得
反应方程式:CH2OH(CHOH)4CHO + 2Cu(OH)2 → CH2OH(CHOH)4COOH + Cu2O + 2H2O (反应条件:碱性、加热)
CH2OH(CHOH)4CHO + 2Cu(OH)2 +NaOH→ CH2OH(CHOH)4COONa + Cu2O(沉淀) + 3H2O (新教材写法)

毒性
按中国农药毒性分级标准,氧化亚铜属低毒杀菌剂。86.2%铜大师(WG、WP)大鼠急性经口LD50 1400毫克/千克,急性经皮LD50大于4000毫克/千克。对兔皮肤和眼睛有轻微刺激,大鼠亚慢性经口LD50 500毫克/千克,对鱼类低毒,水蚤LC50(48小时)0.06毫克/升。

毒性防护
本品粉尘在空气中含量达到0.22~14mg/m3时,工作1~2h后会引起急性中毒,表现为头痛、无力、咽和结膜发红、恶心、肌肉痛、有时呕吐和腹泻、疲乏、体温升高。一天以后体温可恢复正常,但仍无力,头痛,眩晕,脉数加快,淋巴细胞增多。
慢性中毒表现为:接触铜化合物的工人的局部皮肤、头发及眼结膜有时变成浅黄色或黑绿色,齿龈上有暗红色或绛红色边。对皮肤有刺激作用,粉尘刺激眼睛,并引起角膜溃疡。 对急性中毒者用一定浓度的K4[Fe(CN)6]溶液洗胃,服牛奶等措施。 空气中最高容许浓度为0.1mg/m3。 可戴口罩、防尘眼镜,穿防护工作服,工作后要洗淋浴。

质量指标
质量标准 国家标准 GB/T 1620-79
指 标 项 目 指 标
优等品
总还原率(以Cu2o计)%≥ 98.0
金属铜(Cu) 含量%≤ 1.0
氧化亚铜 (Cu2O计)含量%≥ 97.0
总铜(Cu) 含量%≥ 87.0
氯化物(Cl) 含量%≤ 0.5
硫酸盐(以SO4计) 含量%≤ 0.5
水份 %≤ 0.5
丙酮溶解物含量 %≤ 0.5
稳定性试验后还原率减少量 %≤2.0
筛余物(45μm)%≤ 0.3
75μm筛上硝酸不溶物%≤ 0.1
非铜金属含量%≤ 0.5
注:根据用户要求可提供500目(超细级)产品。

包装储运
用内衬聚乙烯塑料袋的铁桶包装,每桶净重25kg或50kg。应有“剧毒”标志。 本品为剧毒物。贮存于干燥、通风良好的库房内,不得与氧化剂混放。容器必须密封,防止与空气接触变成氧化铜而降 低使用价值。不可与强酸、强碱及食用物品共贮混运。装卸时要轻拿轻放,防止包装破损。 失火时可用水、砂土、各种灭火器扑救。

储运注意事项
氧化亚铜应贮存于干燥通风良好的库房内, 不得与氧化剂混放。容器必须密封,防止与空气接触变成氧化铜而降低使用价值。不可与强酸、强碱及食用物品共贮混运。失火时,可用水浇救。
在空气中会迅速变蓝。能溶于浓碱、三氯化铁等溶液中。在湿空气中逐渐氧化成黑色氧化铜。

 

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cuprous oxide
Fungicide
FRAC M1; multi-site: inorganic

  Cuprous Oxide

NOMENCLATURE
Common name cuprous oxide (E-ISO, accepted in lieu of common name); oxyde cuivreux (F-ISO, accepted in lieu of common name)
IUPAC name copper(I) oxide; dicopper oxide
Chemical Abstracts name copper oxide (Cu2O)
CAS RN [1317-39-1] EEC no. 215-270-7

PHYSICAL CHEMISTRY
Composition Contains 86% Cu++. Mol. wt. 143.1 M.f. Cu2O Form Red-brown powder. M.p. 1235 ºC B.p. 1800 ºC V.p. Negligible Solubility Practically insoluble in water and organic solvents. Soluble in dilute mineral acids and in aqueous ammonia and its salts. Stability Liable to oxidation to cupric oxide and to conversion to a carbonate on exposure to moist air.

COMMERCIALISATION
History Fungicidal properties as seed protectant reported by J. G. Horsfall (N. Y. St. Agric. Exp. Stn. Bull., 1932, No. 615). First marketed by Sandoz AG in 1943. Subsequently used for foliage protection. Manufacturers Ingeniería Industrial; Nordox; Sulcosa; Syngenta

APPLICATIONS
Biochemistry Copper-II ion (Cu++) is taken up by the spores during germination and accumulates until a sufficiently high concentration is achieved to kill the spore cell; the activity is limited to the prevention of spore germination. Mode of action Foliar fungicide with preventative action. Deposits must be on the crop before fungal spores begin to germinate. Uses Control of blights, downy mildews, rusts, and leaf spot diseases in a wide range of crops, including potatoes, tomatoes, vines, hops, olives, pome fruit, stone fruit, citrus fruit, beetroot, sugar beet, celery, carrots, coffee, cocoa, tea, bananas, etc. Applied at 0.75-1 kg/ha. Phytotoxicity Non-phytotoxic when used as directed, except to brassicas and copper-sensitive plants. Russetting is possible with some varieties of fruit. Formulation types WG; WP. Compatibility Not compatible with highly alkaline pesticides, or with fenvalerate, parathion, chlorpyrifos or dicloran. Selected products: 'Copper Nordox' (Nordox); 'Copper-Sandoz' (Syngenta); 'Cúprox' (Ingeniería Industrial)

OTHER PRODUCTS
'Chem Copp' (Chemet) Discontinued products: 'Yellow Cuprocide' * (Rohm & Haas)

ANALYSIS
Product determined iodometrically or by conversion to sulfate followed by electrolytic determination (CIPAC Handbook, 1992, E,42; ibid., 1998, H, 96; AOAC Methods, 1984, 6.015-6.016; MAFF Ref. Book, 1958, No. 1, p. 16); metallic copper in cuprous oxide may be determined (L. C. Hurd & A. R. Clark, Ind. Eng. Chem. Anal. Ed., 1936, 8, 380). Residues determined by reaction with concentrated sulfuric acid, and colorimetric estimation of derivatives or by atomic absorption spectroscopy (AOAC Methods, 14th Ed., 3.020-3.028, 3.033-3.034, 3.013-3.016).

MAMMALIAN TOXICOLOGY
Oral Acute oral LD50 for rats 1500 mg/kg. Skin and eye Acute percutaneous LD50 for rats >2000 mg/kg. Moderate to minimal irritation to skin. Inhalation LC50 for rats 5.0 mg/l air. NOEL No chronic toxic effects have been observed in rats receiving 500 mg/kg copper in their diet. No record of occupational diseases attributable to copper. Other Sheep and calves are somewhat copper-sensitive, and livestock should not be allowed to graze on newly sprayed fields. Toxicity class WHO (a.i.) II EC classification Xn; R22

ECOTOXICOLOGY
Birds Not harmful; no significant history of ill-effect on birds. Fish LC50 (48 h) for young goldfish 60, adult goldfish 150, young guppies 50 mg/l. Daphnia LC50 (48 h) 18.9 mg/l. Bees LD50 >25 mg/bee. Worms Under conditions of moderate use and cultivation, the hazard to earthworms, and hence to soil structure, is insignificant.

ENVIRONMENTAL FATE
Animals Copper is an essential element and is under homeostatic control in mammals. Plants Plants resist copper accumulation and translocation to stems, leaves or seeds. Most plants growing on soils containing up to 1000 ppm copper showed only slight elevation in copper content compared to plants grown in normal soils. Soil/Environment Copper is strongly adsorbed to surfaces of minerals and organic matter, hence soil mobility is very low. In water, copper ions have a strong tendency to form complexes or to be adsorbed, followed by sedimentation. In the sediment, copper reacts with organic matter or sulfides; these reactions reduce bioavailability.