Aluminium reactivity

No fewer than 14 pure metals have densities se4.5 Mg (see Table 10.1). Of these, titanium, aluminium and magnesium are in common use as structural materials. Beryllium is difficult to work and is toxic, but it is used in moderate quantities for heat shields and structural members in rockets. Lithium is used as an alloying element in aluminium to lower its density and save weight on airframes. Yttrium has an excellent set of properties and, although scarce, may eventually find applications in the nuclear-powered aircraft project. But the majority are unsuitable for structural use because they are chemically reactive or have low melting points." ... 

Aluminium trialkyls and triaryls are highly reactive, colourless, volatile liquids or low-melting solids which ignite spontaneously in air and react violently with water they should therefore be handled circumspectly and with... 

Aluminium is a very reactive metal with a high affinity for oxygen. The metal is nevertheless highly resistant to most atmospheres and to a great variety of chemical agents. This resistance is due to the inert and protective character of the aluminium oxide film which forms on the metal surface (Section 1.5). In most environments, therefore, the rate of corrosion of aluminium decreases rapidly with time. In only a few cases, e.g. in caustic soda, does the corrosion rate approximate to the linear. A corrosion rate increasing with time is rarely encountered with aluminium, except in aqueous solutions at high temperatures and pressures. 

As copper is not an inherently reactive element, it is not surprising that the rate of corrosion, even if unhindered by films of insoluble corrosion products, is usually low. Nevertheless, although the breakdown of a protective oxide film on copper is not likely to lead to such rapid attack as with a more reactive metal such as, say, aluminium, in practice the good behaviour of copper (and more particularly of some of its alloys) often depends to a considerable extent on the maintenance of a protective film of oxide or other insoluble corrosion product. 

In the case of alloys having one constituent considerably more reactive to oxygen than the others, conditions of temperature, pressure and atmosphere may be selected in which the reactive element is preferentially oxidised. Price and Thomas used this technique to develop films of the oxides of beryllium, aluminium, etc. on silver-base alloys, and thereby to confer improved tarnish resistance on these alloys. If conditions are so selected that the inward diffusion of oxygen is faster than outward diffusion of the reactive element, the oxide will be formed as small dispersed particles beneath the surface of the alloy. The phenomenon is known as internal oxidation and is of quite common occurrence, usually in association with a continuous surface layer of oxides of the major constituents of the alloy. 

If the positive potential changes are very small and confined to a few points on a small unprotected structure, it may be practicable to reduce the potential at these points by installing reactive anodes. The anodes will probably be most effective if they can be buried between the two structures. In some circumstances a similar screen of zinc, aluminium or steel may be installed between the structures. The screen must be electrically connected to the unprotected structure since it is installed with the object of providing an electrolytic path to earth for the interaction current. 

Laister and Benham have shown that under more arduous conditions (immersion for 6 months in sea-water) a minimum thickness of 0-025 mm of silver is required to protect steel, even when the silver is itself further protected by a thin rhodium coating. In similar circumstances brass was completely protected by 0 012 5 mm of silver. The use of an undercoating deposit of intermediate electrode potential is generally desirable when precious metal coatings are applied to more reactive base metals, e.g. steel, zinc alloys and aluminium, since otherwise corrosion at discontinuities in the coating will be accelerated by the high e.m.f. of the couple formed between the coating and the basis metal. The thickness of undercoat may have to be increased substantially above the values indicated if the basis metal is affected by special defects such as porosity. 

The 2-position is largely unreactive toward electrophiles, but nucleophilic substitution occurs there with some facility, especially in acidic medium. The protonated species is about 20 times more reactive than the neutral molecule (70BSF2705). Exhaustive chlorination in the presence of antimony trichloride gave pentachlorobenzothiazole (64GEP1168911). Direct chlorination of the parent heterocycle with aluminium or ferric... 

Kennedy, J. P. and Trivedi, P. D. Cationic Olefin Polymerization Using Alkyl Halide — Alkyl-Aluminium Initiator Systems. I. Reactivity Studies. II. Molecular Weight Studies. Vol. 28, pp. 83-151. 

This mechanism is consistent with all the observations except the variation in rate with initial aluminium chloride concentration. With very reactive aromatics the ionisation step (80) is rate-determining, leading to second-order kinetics, but with less reactive aromatics the ionisation is fast compared with the subsequent reaction of the ionised complex with the aromatic (81), so that this latter then becomes rate-determining. 

Olivier and Berger335, who measured the first-order rate coefficients for the aluminium chloride-catalysed reaction of 4-nitroben2yl chloride with excess aromatic (solvent) at 30 °C and obtained the rate coefficients (lO5/ ) PhCI, 1.40 PhH, 7.50 PhMe, 17.5. These results demonstrated the electrophilic nature of the reaction and also the unselective nature of the electrophile which has been confirmed many times since. That the electrophile in these reactions is not the simple and intuitively expected free carbonium ion was indicated by the observation by Calloway that the reactivity of alkyl halides was in the order RF > RC1 > RBr > RI, which is the reverse of that for acylation by acyl halides336. The low selectivity (and high steric hindrance) of the reaction was further demonstrated by Condon337 who measured the relative rates at 40 °C, by the competition method, of isopropylation of toluene and isopropylbenzene with propene catalyzed by boron trifluoride etherate (or aluminium chloride) these were as follows PhMe, 2.09 (1.10) PhEt, 1.73 (1.81) Ph-iPr, (1.69) Ph-tBu, 1.23 (1.40). The isomer distribution in the reactions337,338 yielded partial rate factors of 2.37 /mMe, 1.80 /pMe, 4.72 /, 0.35 / , 2.2 / Pr, 2.55337 339. 

Low substrate selectivity accompanying high positional selectivity was also found in isopropylation of a range of alkyl and halogenobenzenes by /-propyl bromide or propene in nitromethane, tetramethylene sulphone, sulphur dioxide, or carbon disulphide, as indicated by the relative rates in Table 86. The toluene benzene reactivity ratio was measured under a wide range of conditions, and varied with /-propyl bromide (at 25 °C) from 1.41 (aluminium chloride-sulphur... 

Yamase and Goto406 determined first- and second-order rate coefficients for the aluminium chloride-catalysed reaction of halide derivatives of benzoic acid (lO5 = F, 1.73 Cl, 4.49 Br, 4.35 I, 0.81) and phenylacetic acid (105fc2 = F, 12 Cl, 21 Br, 9 I, 6) with benzene. The maxima in the rates for the acid chloride are best accommodated by the assumption that a highly (but not completely) polarised complex takes part in the transition state. Polarisation of such a complex would be aided by electron supply, and consistently, the acetyl halides are about a hundred times as reactive as the benzoyl compounds (see p. 180, also Tables 105 and 108). 

In exceptional circumstances the acylium ion (or the polarised complex) can decompose to give an alkyl cation so that alkylation accompanies acylation. This occurs in the aluminium chloride-catalysed reaction of pivaloyl chloride which gives acylation with reactive aromatics such as anisole, but with less reactive aromatics such as benzene, the acylium ion has time to decompose, viz. 

The use of ethylene dichloride as solvent was extended by Brown et al. 11 to the determination of the kinetics of benzoylation of other aromatics, using benzoyl chloride catalysed by aluminium chloride, and the data are included in Table 109 the relative reactivities are thus benzene, 1.0 toluene, 117 o-xylene, 1,393 m-xylene, 3,960 and p-xylene, 243 and these values are closely similar to those obtained with nitrobenzene as solvent. No exact comparison of the coefficients with those of Corriu et al. 16 is possible because of the different temperatures employed, but the rates appear to be comparable for the two sets of data after allowing for reasonable temperature dependencies. 

Gore et al.426 have used chloroform as a solvent for acetylation catalysed by aluminium chloride and at 45-55 °C find that a 2-methoxy substituent in naphthalene increases the reactivity of the 1 position 1.72 times, of the 6 position 3.8 times, and of the 8 position, 0.9 times the former and latter of these results indicate a considerable steric effect. Likewise, a 2-bromo substituent caused the reactivity of the 6 and 8 positions to be 0.63 and 0.58 times that of the corresponding positions in the unsubstituted compound. At 20-25 °C the relative reactivities of some polycyclics were as follows427 1-naphthyl, 1.0 3-phenanthryl 0.64 9-phenanthryl, 0.02 1-phenanthryl, 0.29 2-naphthyl, 0.28 2-phenanthryl, 0.12 4-phenanthryl, 0.0085. Some of these results seem to be due to steric hindrance, and the large difference in reactivity of naphthalene and biphenyl seems erroneous. 

In 1887 Colby and McLaughlin175 found that treatment of benzene with thionyl chloride in the presence of aluminium trichloride produces diphenyl sulphoxide probably via benzenesulphinyl chloride. Later on, some other diaryl sulphoxides were prepared by this procedure176-180 (equation 66 Table 10). Highly reactive aromatic compounds such as naphthyl ethers react with thionyl chloride in the absence of a catalyst181. 

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