Tarnishing

C (Mond process). The silver-white metal is ccp. The metal is not tarnished by air but is attacked by acids (except cone. HNO3). It is resistant to Fj. It is used extensively in alloys, particularly in steels and cast iron and as a coinage metal. Used in glass (green) in catalysts (particularly for hydrogenation). Western world production 1981 662 000 tonnes. 

The kinetics of reactions in which a new phase is formed may be complicated by the interference of that phase with the ease of access of the reactants to each other. This is the situation in corrosion and tarnishing reactions. Thus in the corrosion of a metal by oxygen the increasingly thick coating of oxide that builds up may offer more and more impedance to the reaction. Typical rate expressions are the logarithmic law,... 

In a study of tarnishing the parabolic law, Eq. VII-30, is obeyed, with kj = 0. The film thickness y, measured after a given constant elapsed time, is determined in a... 

Hydrogen sulphide reacts slowly with many metals (more rapidly if they are heat ) to yield the sulphide of the metal and (usually) hydrogen, for example the tarnishing of silver. 

Silver has little tendency to formally lose more than one electron its chemistry is therefore almost entirely restricted to the + 1 oxidation state. Silver itself is resistant to chemical attack, though aqueous cyanide ion slowly attacks it, as does sulphur or a sulphide (to give black Ag S). hence the tarnishing of silver by the atmosphere or other sulphur-containing materials. It dissolves in concentrated nitric acid to give a solution of silver(I) nitrate. AgNOj. 

Pure silver has a brilliant white metallic luster. It is a little harder than gold and is very ductile and malleable, being exceeded only by gold and perhaps palladium. Pure silver has the highest electrical and thermal conductivity of all metals, and possesses the lowest contact resistance. It is stable in pure air and water, but tarnishes when exposed to ozone, hydrogen sulfide, or air containing sulfur. The alloys of silver are important. 

The element is a steel gray, very brittle, crystalline, semimetallic solid it tarnishes in air, and when heated is rapidly oxidized to arsenous oxide with the odor of garlic. Arsenic and its compounds are poisonous. 

Technetium is a silvery-gray metal that tarnishes slowly in moist air. The common oxidation states of technetium are +7, +5, and +4. Under oxidizing conditions technetium (Vll) will exist as the pertechnetate ion, TcOr-. The chemistry of technetium is said to be similar to that of rhenium. Technetium dissolves in nitric acid, aqua regia, and cone, sulfuric acid, but is not soluble in hydrochloric acid of any strength. The element is a remarkable corrosion inhibitor for steel. The metal is an excellent superconductor at IIK and below. 

Ruthenium is a hard, white metal and has four crystal modifications. It does not tarnish at room temperatures, but oxidizes explosively. It is attacked by halogens, hydroxides, etc. Ruthenium can be plated by electrodeposition or by thermal decomposition methods. The metal is one of the most effective hardeners for platinum and palladium, and is alloyed with these metals to make electrical contacts for severe wear resistance. A ruthenium-molybdenum alloy is said to be... 

The element is a steel-white metal, it does not tarnish in air, and it is the least dense and lowest melting of the platinum group of metals. When annealed, it is soft and ductile cold-working greatly increases its strength and hardness. Palladium is attacked by nitric and sulfuric acid. 

The metal has a bright silvery metallic luster. Neodymium is one of the more reactive rare-earth metals and quickly tarnishes in air, forming an oxide that spalls off and exposes metal to oxidation. The metal, therefore, should be kept under light mineral oil or sealed in a plastic material. Neodymium exists in two allotropic forms, with a transformation from a double hexagonal to a body-centered cubic structure taking place at 863oC. 

The metal is relatively stable in dry air, but tarnishes in moist air and forms a losely adhering... 

The metal has a silvery appearance and takes on a yellow tarnish when slightly oxidized. It is chemically reactive. A relatively large piece of plutonium is warm to the touch because of the energy given off in alpha decay. Larger pieces will produce enough heat to boil water. The metal readily dissolves in concentrated hydrochloric acid, hydroiodic acid, or perchloric acid. The metal exhibits six allotropic modifications having various crystalline structures. The densities of these vary from 16.00 to 19.86 g/cms. 

Deteriora.tlon. Apart from physical damage that can result from carelessness, abuse, and vandaUsm, the main problem with metal objects Hes in thek vulnerabihty to corrosion (see Corrosion and corrosion control) (127,128). The degree of corrosion depends on the nature and age of the object. Corrosion can range from a light tarnish, which may be aesthetically disfiguring on a poHshed silver or brass artifact, to total mineralization, a condition not uncommon for archaeological material. 

Another ak pollutant that can have very serious effects is hydrogen sulfide, which is largely responsible for the tarnishing of silver, but also has played a destmctive role in the discoloration of the natural patinas on ancient bronzes through the formation of copper sulfide. Moreover, a special vulnerabihty is created when two metals are in contact. The electromotive force can result in an accelerated corrosion, eg, in bronzes having kon mounting pins. 

Hydrogen sulfide has traditionally been a problem in the tarnishing of silver and the discoloration of bronze patinas. This gas can be dealt with in the filters of the climate-control system as well as through the use of proper absorbing agents. For example, a paper treated with activated charcoal is fabricated especially for absorbing H2S within a microclimate. 

Lead is one of the most stable of fabricated materials because of excellent corrosion resistance to air, water, and soil. An initial reaction with these elements results in the formation of protective coatings of insoluble lead compounds. For example, in the presence of oxygen, water attacks lead, but if the water contains carbonates and siUcates, protective films or tarnishes form and the corrosion becomes exceedingly slow. 

The corrosion behavior of plutonium metal has been summarized (60,61). a-Plutonium oxidizes very slowly in dry air, typically <10 mm/yr. The rate is accelerated by water vapor. Thus, a bright metal surface tarnishes rapidly in normal environments and a powdery surface soon forms. Eventually green PUO2 [12059-95-9] covers the surface. Plutonium is similar to uranium with respect to corrosion characteristics. The stabilization of 5-Pu confers substantial corrosion resistance to Pu in the same way that stabilization of y-U yields a more corrosion-resistant metal. The reaction of Pu metal with Hquid water produces both oxides and oxide-hydrides (62). The reaction with water vapor above 100°C also produces oxides and hydride (63). 

A problem associated with the use of abrasive metal poHshes is that the fresh metal, which has been exposed by the cleaning, rapidly oxidizes or tarnishes. Thus, many modem poHshes contain inhibitors. Sulfur compounds, eg, alkyl benzyl thiols, commonly are used, as are mercapto esters such as lauryl thioglycolate [3746-39-2] and dialkyldisulfides (52—54). 

Although abrasive polishing is the most common metal polishing operation, other forms of polishing and chemical brightening are used ia iadustrial operations. Aluminum tmck trailers often are cleaned and brightened by treatments with strong acids or alkaHes, which chemically remove oxides. Chemical methods can also remove tarnish from other metals (55,56). 

Corrosion Inhibitors. Steel-reinforcing wire and rods embedded in concrete containing quinoline or quinoline chromate are less susceptible to corrosion (72) (see Corrosion and corrosion control). Treating the surface of metals with 8-hydroxyquinoline [148-24-3] makes them resistant to tarnishing and corrosion (73). Ethylene glycol-type antifreeze may contain quinoline, 2-chloro-, 4-amino-, 8-nitro-, or 8-hydroxyquinoline to prevent corrosion (74). 

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