Nickel, Ruthenium, Rhodium, Palladium, Osmium, and Platinum

S. Czerczak, J. Gromiec
{"title":"Nickel, Ruthenium, Rhodium, Palladium, Osmium, and Platinum","authors":"S. Czerczak, J. Gromiec","doi":"10.1002/0471435139.TOX041.PUB2","DOIUrl":null,"url":null,"abstract":"Nickel (1–3) is a transition element in group VIII of the periodic system belonging with palladium and platinum to the 10 (nickel) triad. It is a silver-white metal with characteristic gloss and is ductile and malleable. It occurs in two allotropic forms. The specific density of nickel is 8.90 g/cm3, melting point 1455°C, and boiling point 2730°C. Nickel is not soluble in water, but it does dissolve in dilute oxidizing acids. It is resistant to lyes. Nickel is obtained by processing sulfide and laterite ore concentrates using pyrometallurgic and hydrometallurgic processes. The resultant nickel matte obtained by roasting and smelting is subjected to further cleaning by electro-, vapo-, and hydrometallurgic refining methods. Some portion of the matte is roasted to obtain commercial nickel oxide agglomerate. Pure, 99.9% nickel can be obtained by electrolytic refining process. Nickel has been used predominantly as a component of alloys. \n \n \n \nInformation on the acute and chronic poisonings by nickel metal in people is limited and, in the majority of cases, refers to effects of the combined exposure to dusts or fumes comprising mixtures of metallic nickel, and its oxides and salts. Contact hypersensitivity to nickel and its salts, however, is quite well documented. Ruthenium, a transition element, belongs to group VIII (iron) of the periodic classification and to the light platinum metals triad. It is a hard and brittle metal that resembles platinum. Ruthenium compounds are usually dark brown (ranging from yellow to black). Ruthenium forms alloys with platinum, palladium, cobalt, nickel, and tungsten. \n \n \n \nElemental ruthenium occurs in native alloys of iridium and osmium (irridosmine, siskerite) and in sulfide and other ores (pentlandite, laurite, etc.) in very small quantities that are commercially recovered. \n \n \n \nRuthenium is used in electronics and electrical engineering, and also in the chemical industry. Ruthenium metal is used as a catalyst in the oxidizing reactions and in the synthesis of long-chain hydrocarbons. Because of its catalytic activity, it is also used in the catalytic converters for motor car engines. Ruthenium is used to increase the hardness of platinum alloys designed to make electric contacts, to make resistance wires, circuit breakers, and other components. It is also employed as a substitute for platinum in jewelry and to make the tips of fountain pen nibs. \n \n \n \nCertain derived ruthenium(III) complexes are used in cancer therapy to prevent metaplasia or to inhibit tumor cell growth. Ruthenium 106 is also used for that purpose. Ruthenium(III) complexes may be also applied to treat diseases resulting from exposure to nitric oxide. Ammoniated ruthenium oxychloride (Ruthenium Red) has been used as staining agent in microscopy. \n \n \n \nRhodium is a transition element belonging to the cobalt group and to the light platinum triad at the same time. There is only one stable isotope: 103Rh. Rhodium, in the elemental state, is a quite soft, forgeable, silver-white metal. It occurs in nature extremely rarely (abundance: 1 × 10−70 % by wt) in the form of alloys with other platinum metals (e.g., in crude platinum) or accompanies gold. Because it is a very precious and expensive metal, rhodium is resistant to the action of cold chlorine and fluorine and insoluble in acids and aqua regia. \n \n \n \nPure rhodium is prepared by the reduction of its ammonium salt (dichloropentaaminorhodium). \n \n \n \nRhodium is used for the manufacture of thermocouples (in the form of platinum–rhodium alloy: 10% Rh and 90% Pt), laboratory vessels (crucibles), catalysts (as an additive to Pt and Pd), spinnerets for synthetic and glass fibers, surgical tools (Ph, Pt, and Ir alloys), and electroplating. Besides, rhodium is used in jewelry, RhCl3 is capable of controlling some viruses. Anticarcinogenic activity of some rhodium compounds has also been confirmed. \n \n \n \nNo toxic rhodium and rhodium compounds levels have been determined either for blood or urine. As the exposure of animals to rhodium results in respiratory function disorders, it seems useful to monitor the pulmonary function in the case of rhodium poisoning. Considering that central nervous system disorders have been observed among animals exposed to rhodium, it seems advisable to monitor this system in the case of rhodium poisoning in humans. \n \n \n \nPalladium, a transition element belonging to Group III in the periodic table (nickel group) and light platinum metals, is a medium-hard, moderately forgeable, ductile silver-white metal. In its compounds, palladium usually assumes oxidation state +2 and +4, forming bivalent and tetravalent salts. A characteristic feature of palladium is its high hydrogen absorption, which allows for use its in the form of palladium sponge or palladium black as a catalyst in reduction processes. Contrary to other platinum metals, palladium is considerably less resistant to chemicals. At elevated temperatures palladium reacts with oxygen, fluorine, chlorine, sulfur, and selenium. Palladium dust may constitute fire and explosion hazards. Palladium compounds show different water solubility. \n \n \n \nPalladium metal is practically nontoxic. The acute effects of palladium compounds depend on the type, dose and administration of the compound. In general, the effects are stronger after IV or IP administration than orally. Water-soluble palladium compounds, namely, those soluble in systemic fluids, show stronger toxic activity than do the insoluble ones. \n \n \n \nOsmium, a transition element belongs to the odd series 81 (iron) family, and at the same time to the heavy platinum metals. It has seven stable isotopes. Osmium is a very hard and brittle gray-blue metal. It forms hexagonal crystals. \n \n \n \nNo data have been found in the relevant literature concerning the toxic effects of osmium metal in experimental animals. However, it oxidizes at relatively low temperatures to the volatile osmium tetroxide, which shows strong irritating activity to eyes, respiratory tract and skin. \n \n \n \nPlatinum, an intermediate element belonging to group VIII (nickel, palladium, platinum) of the periodic table and at the same time to the heavy platinum group, is a relatively soft, very malleable, ductile, silver-white metal of very high melting point and high density. It occurs mainly in the form of stable isotopes: 190Pt (0.01%), 192Pt (0.08%), 194Pt (32.9%), 195Pt (33.8%), 196Pt (25.2%), and 198Pt (7.2%). It is rare in the earth crust (abundance 2 × 10−6% by weight). Nevertheless, platinum is the most abundant element of the heavy platinum group. \n \n \n \nPlatinum is obtained mainly from copper and nickel ores, and platinum alloys and by recovery from the catalyst and other waste. The main stages of platinum production include extraction of the precious-metal concentrate from the ore followed by separation through a complex refining process, during which the concentrate is dissolved in aqua regia, and the platinum is precipitated in the form of ammonium(IV) hexachloroplatinate. The precipitate is then calcinated at 600–700°C to give platinum sponge, which is then hardened by melting at high temperatures, such as in the electric arc. The resultant gray platinum sponge contains 99.95–99.9% pure metal. \n \n \n \nPlatinum has been widely used in various industries, such as chemical, ceramic, electronic, automotive, petroleum. It is also used in medicine, dental surgery, and for jewelry manufacture. Pure platinum and its alloys are used to produce special-purpose chemical apparatus, laboratory equipment (crucibles, evaporating dishes, platinum wire nets, electrodes), spinning dies for spinning chemical and glass fibers, and electric contacts. Platinum/iridium alloys are used to make length and weight standards. The industrial application of platinum is associated mainly with its catalytic activity. Platinum is used to make surgical instruments and implants. \n \n \n \nThe industrial application of platinum is not limited to its pure metal or alloy forms; it is used also in the form of chemical compounds to electroplate metal surfaces. \n \n \nKeywords: \n \nNickel; \nNickel compounds; \nRhodium; \nRhodium compounds; \nPalladium; \nPalladium compounds; \nOsmium; \nOsmium compounds; \nPlatinum; \nPlatinum compounds; \nCancer; \nBiological materials; \nChlorides; \nCarbonates; \nOxides; \nSulfides; \nKinetic models; \nRefining plants; \nLung cancer; \nInhalation; \nMetal; \nDermal exposure; \nRadioactivity","PeriodicalId":19820,"journal":{"name":"Patty's Toxicology","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2012-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"6","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Patty's Toxicology","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/0471435139.TOX041.PUB2","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 6

Abstract

Nickel (1–3) is a transition element in group VIII of the periodic system belonging with palladium and platinum to the 10 (nickel) triad. It is a silver-white metal with characteristic gloss and is ductile and malleable. It occurs in two allotropic forms. The specific density of nickel is 8.90 g/cm3, melting point 1455°C, and boiling point 2730°C. Nickel is not soluble in water, but it does dissolve in dilute oxidizing acids. It is resistant to lyes. Nickel is obtained by processing sulfide and laterite ore concentrates using pyrometallurgic and hydrometallurgic processes. The resultant nickel matte obtained by roasting and smelting is subjected to further cleaning by electro-, vapo-, and hydrometallurgic refining methods. Some portion of the matte is roasted to obtain commercial nickel oxide agglomerate. Pure, 99.9% nickel can be obtained by electrolytic refining process. Nickel has been used predominantly as a component of alloys. Information on the acute and chronic poisonings by nickel metal in people is limited and, in the majority of cases, refers to effects of the combined exposure to dusts or fumes comprising mixtures of metallic nickel, and its oxides and salts. Contact hypersensitivity to nickel and its salts, however, is quite well documented. Ruthenium, a transition element, belongs to group VIII (iron) of the periodic classification and to the light platinum metals triad. It is a hard and brittle metal that resembles platinum. Ruthenium compounds are usually dark brown (ranging from yellow to black). Ruthenium forms alloys with platinum, palladium, cobalt, nickel, and tungsten. Elemental ruthenium occurs in native alloys of iridium and osmium (irridosmine, siskerite) and in sulfide and other ores (pentlandite, laurite, etc.) in very small quantities that are commercially recovered. Ruthenium is used in electronics and electrical engineering, and also in the chemical industry. Ruthenium metal is used as a catalyst in the oxidizing reactions and in the synthesis of long-chain hydrocarbons. Because of its catalytic activity, it is also used in the catalytic converters for motor car engines. Ruthenium is used to increase the hardness of platinum alloys designed to make electric contacts, to make resistance wires, circuit breakers, and other components. It is also employed as a substitute for platinum in jewelry and to make the tips of fountain pen nibs. Certain derived ruthenium(III) complexes are used in cancer therapy to prevent metaplasia or to inhibit tumor cell growth. Ruthenium 106 is also used for that purpose. Ruthenium(III) complexes may be also applied to treat diseases resulting from exposure to nitric oxide. Ammoniated ruthenium oxychloride (Ruthenium Red) has been used as staining agent in microscopy. Rhodium is a transition element belonging to the cobalt group and to the light platinum triad at the same time. There is only one stable isotope: 103Rh. Rhodium, in the elemental state, is a quite soft, forgeable, silver-white metal. It occurs in nature extremely rarely (abundance: 1 × 10−70 % by wt) in the form of alloys with other platinum metals (e.g., in crude platinum) or accompanies gold. Because it is a very precious and expensive metal, rhodium is resistant to the action of cold chlorine and fluorine and insoluble in acids and aqua regia. Pure rhodium is prepared by the reduction of its ammonium salt (dichloropentaaminorhodium). Rhodium is used for the manufacture of thermocouples (in the form of platinum–rhodium alloy: 10% Rh and 90% Pt), laboratory vessels (crucibles), catalysts (as an additive to Pt and Pd), spinnerets for synthetic and glass fibers, surgical tools (Ph, Pt, and Ir alloys), and electroplating. Besides, rhodium is used in jewelry, RhCl3 is capable of controlling some viruses. Anticarcinogenic activity of some rhodium compounds has also been confirmed. No toxic rhodium and rhodium compounds levels have been determined either for blood or urine. As the exposure of animals to rhodium results in respiratory function disorders, it seems useful to monitor the pulmonary function in the case of rhodium poisoning. Considering that central nervous system disorders have been observed among animals exposed to rhodium, it seems advisable to monitor this system in the case of rhodium poisoning in humans. Palladium, a transition element belonging to Group III in the periodic table (nickel group) and light platinum metals, is a medium-hard, moderately forgeable, ductile silver-white metal. In its compounds, palladium usually assumes oxidation state +2 and +4, forming bivalent and tetravalent salts. A characteristic feature of palladium is its high hydrogen absorption, which allows for use its in the form of palladium sponge or palladium black as a catalyst in reduction processes. Contrary to other platinum metals, palladium is considerably less resistant to chemicals. At elevated temperatures palladium reacts with oxygen, fluorine, chlorine, sulfur, and selenium. Palladium dust may constitute fire and explosion hazards. Palladium compounds show different water solubility. Palladium metal is practically nontoxic. The acute effects of palladium compounds depend on the type, dose and administration of the compound. In general, the effects are stronger after IV or IP administration than orally. Water-soluble palladium compounds, namely, those soluble in systemic fluids, show stronger toxic activity than do the insoluble ones. Osmium, a transition element belongs to the odd series 81 (iron) family, and at the same time to the heavy platinum metals. It has seven stable isotopes. Osmium is a very hard and brittle gray-blue metal. It forms hexagonal crystals. No data have been found in the relevant literature concerning the toxic effects of osmium metal in experimental animals. However, it oxidizes at relatively low temperatures to the volatile osmium tetroxide, which shows strong irritating activity to eyes, respiratory tract and skin. Platinum, an intermediate element belonging to group VIII (nickel, palladium, platinum) of the periodic table and at the same time to the heavy platinum group, is a relatively soft, very malleable, ductile, silver-white metal of very high melting point and high density. It occurs mainly in the form of stable isotopes: 190Pt (0.01%), 192Pt (0.08%), 194Pt (32.9%), 195Pt (33.8%), 196Pt (25.2%), and 198Pt (7.2%). It is rare in the earth crust (abundance 2 × 10−6% by weight). Nevertheless, platinum is the most abundant element of the heavy platinum group. Platinum is obtained mainly from copper and nickel ores, and platinum alloys and by recovery from the catalyst and other waste. The main stages of platinum production include extraction of the precious-metal concentrate from the ore followed by separation through a complex refining process, during which the concentrate is dissolved in aqua regia, and the platinum is precipitated in the form of ammonium(IV) hexachloroplatinate. The precipitate is then calcinated at 600–700°C to give platinum sponge, which is then hardened by melting at high temperatures, such as in the electric arc. The resultant gray platinum sponge contains 99.95–99.9% pure metal. Platinum has been widely used in various industries, such as chemical, ceramic, electronic, automotive, petroleum. It is also used in medicine, dental surgery, and for jewelry manufacture. Pure platinum and its alloys are used to produce special-purpose chemical apparatus, laboratory equipment (crucibles, evaporating dishes, platinum wire nets, electrodes), spinning dies for spinning chemical and glass fibers, and electric contacts. Platinum/iridium alloys are used to make length and weight standards. The industrial application of platinum is associated mainly with its catalytic activity. Platinum is used to make surgical instruments and implants. The industrial application of platinum is not limited to its pure metal or alloy forms; it is used also in the form of chemical compounds to electroplate metal surfaces. Keywords: Nickel; Nickel compounds; Rhodium; Rhodium compounds; Palladium; Palladium compounds; Osmium; Osmium compounds; Platinum; Platinum compounds; Cancer; Biological materials; Chlorides; Carbonates; Oxides; Sulfides; Kinetic models; Refining plants; Lung cancer; Inhalation; Metal; Dermal exposure; Radioactivity
镍,钌,铑,钯,锇和铂
镍(1-3)是第八族的过渡元素,与钯和铂属于10(镍)三元组。它是一种银白色的金属,具有特有的光泽,具有延展性和延展性。它以两种同素异形体出现。镍的比密度为8.90 g/cm3,熔点1455℃,沸点2730℃。镍不溶于水,但能溶于稀的氧化性酸。它对碱液有抵抗力。镍是通过对硫化物和红土矿精矿进行火法冶金和湿法冶金加工获得的。通过焙烧和熔炼得到的镍锍经过电、汽和湿法冶炼方法进一步清洗。部分磨砂经过焙烧得到商用氧化镍团块。采用电解精炼工艺可获得纯度为99.9%的纯镍。镍主要用作合金的成分。关于镍金属对人的急性和慢性中毒的资料有限,在大多数情况下,是指综合接触含有金属镍及其氧化物和盐类混合物的粉尘或烟雾所产生的影响。然而,对镍及其盐的接触性超敏反应是有充分记录的。钌是一种过渡元素,属于周期分类的第八族(铁),属于轻铂金属三元组。它是一种坚硬而易碎的金属,类似铂金。钌化合物通常是深褐色(从黄色到黑色不等)。钌与铂、钯、钴、镍和钨形成合金。元素钌存在于铱和锇的天然合金中(铱矿、绢石),也存在于硫化物和其他矿石中(镍褐矿、劳氏矿等),但数量很少,可用于商业开采。钌用于电子和电气工程,也用于化学工业。金属钌在氧化反应和长链烃的合成中用作催化剂。由于其催化活性,它也被用于汽车发动机的催化转化器。钌被用来提高铂金合金的硬度,铂金合金用于制造电触点、电阻线、断路器和其他部件。它也被用作珠宝中铂的替代品,并用于制作钢笔笔尖的笔尖。某些衍生的钌(III)配合物用于癌症治疗,以防止化生或抑制肿瘤细胞生长。钌106也被用于这个目的。钌(III)配合物也可用于治疗因暴露于一氧化氮而引起的疾病。用氨化氯化氧化钌(钌红)作为显微镜染色剂。铑是一种过渡元素,同时属于钴族和轻铂族。只有一种稳定的同位素:103Rh。在单质状态下,铑是一种非常柔软、可锻造的银白色金属。它在自然界中很少以与其他铂金属(如粗铂)的合金形式出现(丰度:1 × 10−70% wt)或伴随金。因为它是一种非常珍贵和昂贵的金属,铑耐冷氯和氟的作用,不溶于酸和王水。纯铑是通过还原它的铵盐(二氯五胺)来制备的。铑用于制造热电偶(以铂铑合金的形式:10% Rh和90% Pt),实验室容器(坩埚),催化剂(作为Pt和Pd的添加剂),合成纤维和玻璃纤维的喷丝器,手术工具(Ph, Pt和Ir合金)和电镀。此外,铑被用于珠宝首饰,RhCl3能够控制一些病毒。一些铑化合物的抗癌活性也已得到证实。在血液和尿液中都没有检测到有毒铑和铑化合物的含量。由于动物接触铑会导致呼吸功能紊乱,因此在铑中毒的情况下监测肺功能似乎是有用的。考虑到在接触铑的动物中已经观察到中枢神经系统紊乱,在人类铑中毒的情况下监测该系统似乎是可取的。钯是元素周期表中属于第三族(镍族)和轻铂金属的过渡元素,是一种中等硬度、中等可锻性、延展性的银白色金属。在其化合物中,钯通常呈+2和+4氧化态,形成二价和四价盐。钯的一个特点是它的高吸氢性,这使得它可以在还原过程中以海绵钯或钯黑的形式用作催化剂。与其他铂金属相反,钯对化学物质的抵抗力要弱得多。 在高温下,钯与氧、氟、氯、硫和硒发生反应。钯尘可能构成火灾和爆炸危险。钯化合物表现出不同的水溶性。钯金属实际上是无毒的。钯化合物的急性效应取决于化合物的类型、剂量和施用。一般来说,静脉注射或口服给药后的效果比口服更强。水溶性钯化合物,即可溶于全身液体的钯化合物,表现出比不溶性钯化合物更强的毒性活性。锇是一种过渡元素,属于奇数系81(铁)族,同时也是重铂金属。它有七种稳定的同位素。锇是一种非常坚硬易碎的灰蓝色金属。它形成六角形晶体。在相关文献中没有发现金属锇对实验动物的毒性作用。但在较低的温度下氧化生成挥发性的四氧化锇,对眼睛、呼吸道和皮肤有较强的刺激活性。铂是元素周期表中第八族(镍、钯、铂)的中间元素,同时也是重铂族,是一种相对柔软、可塑性强、延展性好的银白色金属,熔点高、密度大。它主要以稳定同位素的形式存在:190Pt(0.01%)、192Pt(0.08%)、194Pt(32.9%)、195Pt(33.8%)、196Pt(25.2%)和198Pt(7.2%)。它在地壳中很少见(丰度为2 × 10 - 6%)。然而,铂是重铂族中最丰富的元素。铂主要从铜、镍矿石和铂合金中获得,也可以从催化剂和其他废料中回收。铂生产的主要阶段包括从矿石中提取贵金属精矿,然后通过复杂的精炼工艺进行分离,在此过程中,精矿溶解在王水中,铂以六氯铂酸铵的形式沉淀。然后,沉淀物在600-700°C下煅烧,得到海绵铂,然后在高温下(如电弧中)熔化硬化。所得的灰色铂海绵含有99.95-99.9%的纯金属。铂广泛应用于化工、陶瓷、电子、汽车、石油等行业。它也用于医药、牙科手术和珠宝制造。纯铂及其合金用于生产专用化学仪器、实验室设备(坩埚、蒸发盘、铂丝网、电极)、纺丝化学纤维和玻璃纤维的纺丝模具、电触点。铂/铱合金被用来制定长度和重量标准。铂的工业应用主要与其催化活性有关。铂金用于制造手术器械和植入物。铂的工业应用不仅限于其纯金属或合金形式;它也以化合物的形式用于金属表面电镀。关键词:镍;镍化合物;铑;铑化合物;钯;钯化合物;锇;锇的化合物;铂;铂化合物;癌症;生物材料;氯化物;碳酸盐;氧化物;硫化物;动力学模型;精炼植物;肺癌;吸入;金属;皮肤接触;放射性
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