SUBJECTS 533 chromium

The metal parts of the injection molder, ie, the liner, torpedo, and nozzle, that contact the hot molten resin must be of the noncatalytic type to prevent accelerated decomposition of the polymer. In addition, they must be resistant to corrosion by HCl. Iron, copper, and zinc are catalytic to the decomposition and caimot be used, even as components of alloys. Magnesium is noncatalytic but is subject to corrosive attack, as is chromium when used as plating. Nickel alloys such as Duranickel, HasteUoy B, and HasteUoy C are recommended as constmction materials for injection-molding metal parts. These and pure nickel are noncatalytic and corrosion-resistant however, pure nickel is rather soft and is not recommended. 

Most mordant dyes are monoazo stmctures. The most important feature of this class of dyes is excellent fastness to light and washing. Mordant dyes are available ia aU shades of the spectmm with the exceptioa of bright violets, blues, and greens. To be useful, the metal complexes must be stable, ie, must not demetallize when subjected to dyebath conditions and aU aftertreatment processes, especially repeated washings. Chromium forms stable chelate rings with mordant dyes which are not affected by treatment with either weak acid or alkaU (see Coordination compounds). 

Martensitic Stainless Steels. The martensitic stainless steels have somewhat higher carbon contents than the ferritic grades for the equivalent chromium level and are therefore subject to the austenite—martensite transformation on heating and quenching. These steels can be hardened significantly. The higher carbon martensitic types, eg, 420 and 440, are typical cutiery compositions, whereas the lower carbon grades are used for special tools, dies, and machine parts and equipment subject to combined abrasion and mild corrosion. 

Chromium Exposure Levels and U.S. Government Regulations. The level of exposure to chromium compounds for employees in industry and for the general population via waste disposal and industrial emissions is the subject of much regulation, research, and controversy. Some U.S. Government regulations, such as the Comprehensive Environmental Response, Compensation, and LiabiUty Act (CERCLA), also known as the Superfund Act, make no distinction as to the oxidation state of chromium (144). However, there is valence distinction in other regulations. 

Metals in the platinum family are recognized for their ability to promote combustion at lowtemperatures. Other catalysts include various oxides of copper, chromium, vanadium, nickel, and cobalt. These catalysts are subject to poisoning, particularly from halogens, halogen and sulfur compounds, zinc, arsenic, lead, mercury, and particulates. It is therefore important that catalyst surfaces be clean and active to ensure optimum performance. 

Carbon steels heated for prolonged periods at temperatures above 455°C (8.50°F) may be subject to the segregation of carbon, which is transformed into graphite. When this occurs, the structural strength of the steel will be affected. Killed steels or low-alloy steels of chromium and molybdenum or chromium and nickel should be considered for elevated-temperature seivices. 

A cylindrical tube in a chemical plant is subjected to an excess internal pressure of 6 MN m , which leads to a circumferential stress in the tube wall. The tube wall is required to withstand this stress at a temperature of 510°C for 9 years. A designer has specified tubes of 40 mm bore and 2 mm wall thickness made from a stainless alloy of iron with 15% by weight of chromium. The manufacturer s specification for this alloy gives the following information ... 

Poor Weldability a. Underbead cracking, high hardness in heat-affected zone. b. Sensitization of nonstabilized austenitic stainless steels. a. Any welded structure. b. Same a. Steel with high carbon equivalents (3), sufficiently high alloy contents. b. Nonstabilized austenitic steels are subject to sensitization. a. High carbon equivalents (3), alloy contents, segregations of carbon and alloys. b. Precipitation of chromium carbides in grain boundaries and depletion of Cr in adjacent areas. a. Use steels with acceptable carbon equivalents (3) preheat and postheat when necessary stress relieve the unit b. Use stabilized austenitic or ELC stainless steels. 

Eigelstein, H. C., and E. N. Skinner. The Effect of Composition on the Scaling of Iron-Chromium-Nickel Alloys Subjected to Cyclic Temperature Conditions, ASTM, STP No. 165 (1954). 

The topic of chromium oxdiations has been the subject of an excellent review by Wiberg. Discussions of the chemistry of chromium reagents have also been given by Stewart, Fieser, House, ° Neustaedter and Lee. ... 

Finally, in 1797, the Frenchman L. N. Vauquelin discovered the oxide of a new element in a Siberian mineral, now known as crocoite (PbCr04), and in the following year isolated the metal itself by charcoal reduction. This was subsequently named chromium (Greek xpco ia, chroma, colour) because of the variety of colours found in its compounds. Since their discoveries the metals and their compounds have become vitally important in many industries and, as one of the biologically active transition elements, molybdenum has been the subject of a great deal of attention in recent years, especially in the field of nitrogen fixation (p. 1035). 

Chiral salen chromium and cobalt complexes have been shown by Jacobsen et al. to catalyze an enantioselective cycloaddition reaction of carbonyl compounds with dienes [22]. The cycloaddition reaction of different aldehydes 1 containing aromatic, aliphatic, and conjugated substituents with Danishefsky s diene 2a catalyzed by the chiral salen-chromium(III) complexes 14a,b proceeds in up to 98% yield and with moderate to high ee (Scheme 4.14). It was found that the presence of oven-dried powdered 4 A molecular sieves led to increased yield and enantioselectivity. The lowest ee (62% ee, catalyst 14b) was obtained for hexanal and the highest (93% ee, catalyst 14a) was obtained for cyclohexyl aldehyde. The mechanism of the cycloaddition reaction was investigated in terms of a traditional cycloaddition, or formation of the cycloaddition product via a Mukaiyama aldol-reaction path. In the presence of the chiral salen-chromium(III) catalyst system NMR spectroscopy of the crude reaction mixture of the reaction of benzaldehyde with Danishefsky s diene revealed the exclusive presence of the cycloaddition-pathway product. The Mukaiyama aldol condensation product was prepared independently and subjected to the conditions of the chiral salen-chromium(III)-catalyzed reactions. No detectable cycloaddition product could be observed. These results point towards a [2-i-4]-cydoaddition mechanism. 

Nickel is usually alloyed with elements including copper, chromium, molybdenum and then for strengthening and to improve corrosion resistance for specific applications. Nickel-copper alloys (and copper-nickel alloys see Section 53.5.4) are widely used for handling water. Pumps and valve bodies for fresh water, seawater and mildly acidic alkaline conditions are made from cast Ni-30% Cu type alloys. The wrought material is used for shafts and stems. In seawater contaminated with sulfide, these alloys are subject to pitting and corrosion fatigue. Ammonia contamination creates corrosion problems as for commercially pure nickel. 

Ductile and easily buffed chromium deposits having satisfactory corrosion resistance have been produced thus 0.005 mm-thick chromium deposits applied to steel by chemical deposition or by eiectrodeposition gave simiiar results when subjected to a salt-spray test . 

Electrodeposited chromium coatings. Electrolytic corrosion testing Coatings cathodic to the substrate-rating of electroplated test specimens subjected to corrosion tests... 

This reaction is subject to a number of errors (1) the hydriodic acid (from excess of iodide and acid) is readily oxidised by air, especially in the presence of chromium(III) salts, and (2) it is not instantaneous. It is accordingly best to pass a current of carbon dioxide through the reaction flask before and during the titration (a more convenient but less efficient method is to add some solid sodium hydrogencarbonate to the acid solution, and to keep the flask covered as much as possible), and to allow 5 minutes for its completion. 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

Chromium in steel Discussion. The chromium in the steel is oxidised by perchloric acid to the dichromate ion, the colour of which is intensified by iron (III) perchlorate which is itself colourless. The coloured solution is compared with a blank in which the dichromate is reduced with ammonium iron(II) sulphate. The method is not subject to interference by iron or by moderate amounts of alloying elements usually present in steel. 

In any case, as many authors have previously pointed out the n + rule is strictly speaking subject to about 20 exceptions, thus further hinting that it has no fundamental value.11 The best known of these anomalies occur in the neutral atoms of chromium and copper which have the following expected and observed electronic configurations, which generations of general chemistry student have been obliged to learn ... 

Since the publication by the discoverers (3) of chromium oxide catalysts a considerable number of papers devoted to this subject have appeared. Most of them (20-72) deal either with the study of the chromium species on the catalyst surface or with the problem of which of this species is responsible for polymerization. Fewer results have been published on the study of processes determining the polymer molecular weight (78-77) and kinetics of polymerization (78-99). A few papers describe nascent morphology of the polymer formed (100-103). 

Since model compounds reveal well-defined cyclic voltammograms for the Cr(CNR)g and Ni(CNR)g complexes (21) the origin of the electroinactivity of the polymers is not obvious. A possible explanation (12) is that the ohmic resistance across the interface between the electrode and polymer, due to the absence of ions within the polymer, renders the potentially electroactive groups electrochemically inert, assuming the absence of an electronic conduction path. It is also important to consider that the nature of the electrode surface may influence the type of polymer film obtained. A recent observation which bears on these points is that when one starts with the chromium polymer in the [Cr(CN-[P])6] + state, an electroactive polymer film may be obtained on a glassy carbon electrode. This will constitute the subject of a future paper. 

Chromium is the most effective alloying element to give resistance to oxidation, forming a tenacious oxide film. Chromium alloys should be specified for equipment subject to temperatures above 500°C in oxidising atmospheres. 

The reaction of zinc oxide, hydrochloric acid, sodium dichromate, and potassium chloride produced zinc yellow as a precipitate, which is a complex compound of zinc, potassium, and chromium. The complex compound is further subjected to filtration, washing, drying, milling, and packaging for use. 

The rapid autocatalytic dissolution of aluminium, magnesium or zinc in 9 1 methanol-carbon tetrachloride mixtures is sufficiently vigorous to be rated as potentially hazardous. Dissolution of zinc powder is subject to an induction period of 2 h, which is eliminated by traces of copper(II) chloride, mercury(II) chloride or chromium(III) bromide. 

Another subject of dispute was the mechanism of the photochemical, chromium carbonyl catalyzed hydrogenation of dienes /42/. The question here was whether the catalytic reaction is started by the dissociation of CO (Equation 42) or by the dissociation of the coordinated diene (Equation 43) /42, 43/. 

Berman et al. [735] have shown that if a seawater sample is subjected to 20-fold preconcentration by one of the above techniques, then reliable analysis can be performed by ICP-AES (i.e., concentration of the element in seawater is more than five times the detection limit of the method) for iron, manganese, zinc, copper, and nickel. Lead, cobalt, cadmium, chromium, and arsenic are below the detection limit and cannot be determined reliably by ICP-AES. These latter elements would need at least a hundredfold preconcentration before they could be reliably determined. 

The apparatus used for the Glow-wire test, shown in Figure 1, consists of a carriage moving on a platform. The carriage holds the 3" x 3 polymer sample which is moved horizontally towards the glowing Nickel/Chromium wire which can be heated to a temperature of 660 C and 96CPC. The polymer sample is subjected to the wire for thirty seconds with a force of 1.8 to 2.0 Newtons. 

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