Aluminium chloride, basic

The order of reaction with respect to aluminium chloride was ill-defined. Since nitrobenzene and aluminium chloride form a 1 1 complex which exhibits the simple monomeric molecular weight in nitrobenzene solution185, and since even in solutions of aluminium chloride and benzoyl chloride in nitrobenzene the aluminium chloride is preferentially associated with the solvent184, then in nitrobenzene solutions of aluminium chloride and benzenesulphonyl chloride the lesser basicity of the latter relative to benzoyl chloride means that the aluminium chloride must be mainly associated with nitrobenzene and in equilibrium with aluminium chloride associated with the sulphonyl chloride184. By analogy with... 

Freeder, B. G. et al., J. Loss Prev. Process Ind., 1988, 1, 164-168 Accidental contamination of a 90 kg cylinder of ethylene oxide with a little sodium hydroxide solution led to explosive failure of the cylinder over 8 hours later [1], Based on later studies of the kinetics and heat release of the poly condensation reaction, it was estimated that after 8 hours and 1 min, some 12.7% of the oxide had condensed with an increase in temperature from 20 to 100°C. At this point the heat release rate was calculated to be 2.1 MJ/min, and 100 s later the temperature and heat release rate would be 160° and 1.67 MJ/s respectively, with 28% condensation. Complete reaction would have been attained some 16 s later at a temperature of 700°C [2], Precautions designed to prevent explosive polymerisation of ethylene oxide are discussed, including rigid exclusion of acids covalent halides, such as aluminium chloride, iron(III) chloride, tin(IV) chloride basic materials like alkali hydroxides, ammonia, amines, metallic potassium and catalytically active solids such as aluminium oxide, iron oxide, or rust [1] A comparative study of the runaway exothermic polymerisation of ethylene oxide and of propylene oxide by 10 wt% of solutions of sodium hydroxide of various concentrations has been done using ARC. Results below show onset temperatures/corrected adiabatic exotherm/maximum pressure attained and heat of polymerisation for the least (0.125 M) and most (1 M) concentrated alkali solutions used as catalysts. 

Regioselective reductive openings of mixed phenolic-benzylic cyclic acetals, using BH3-NMe3-AlCl3, under mild conditions to yield a benzylic ether and free the phenol group have been attributed to association of boron with the more basic oxygen (benzylic) followed by reaction with aluminium chloride.309... 

We have studied the properties of hydrolysis products formed from aluminium sulphate (AS), basic aluminium sulphates (BAS) and basic aluminium chlorides (BAC) in water as a function of the concentration of the salt, its dosage, pH, alkalinity and ionic strength of the solution. Samples characteristics are given in Table 1. 

I. M. Solomentseva, N. G. Gerasimenko and S. Barany, Surface Properties and Aggregation of Basic Aluminium Chloride Hydrolysis Products, Colloids Surf. A 151, 113-126 (1999). 

The nitro compound, nitrosyl chloride, and basic aluminium chloride formed a number of addition products, which are in equilibrium ... 

Recent work on the dimerisation of 1,1-diphenylethylene by aluminium chloride produced conclusive evidence that direct initiation does not lead to the total ctmsump-tion of the catalyst. This excellent piece of research diowed that about 2.5 aluminium atoms are needed to give rise to one carbenium ion. Similar indications were reported by Kennedy and Squires for the low temperature polymerisation of isobutene by aluminium chloride. They underlined the peculiar feature of limited yields obtained in flash polymerisations with small amounts of catalyst. The low conversions could be increased by further or continuous additions of the Lewis acid. Equal catalyst increments produced equal yield increments It was also shown that introductions of small amounts of moisture or hydrogen chloride in the quiescent system did not reactivate the polymerisation. This work was carried out in pentane and different purification procedures for this solvent resulted in the same proportionality between polymer yield and catalyst concentration. Experiments were also performed in which other monomers (styrene, a-methylstyrene, cyclopentadiene) were added to the quiescent isobutene mixture. The polymerisation of these olefins was initiated but limited yields were again obtained. Althou the full implications of these observations must await more precise data, we agree with the authors interpretation that allylic cations formed in the isobutene polymerisation, while incapable of activating that monomer, are initiators for the polymerisation of the more basic monomers added to the quiescent mixture. The low temperature polymerisation of isobutene by aluminium chloride was also studied... 

Roeper et al. have studied NiCl2 in aluminium chloride/EmimCl ILs via cyclic voltammetry and EXAFS [192], Acidic melts exhibit metal stripping peaks, while in basic melts no metal stripping peaks are observed. EXAFS again reveals that the d-element, in this case Ni, is tetrahedrally coordinated by chloride ions in the basic melt. In the acidic melts, the structure is more complicated as the Ni is coordinated by six chloride ions, which, however, are also coordinating to Al ions. In an interesting further study, Mallick et al. report the formation of Cr-Cr metal-metal bonds in [Bmim]2[CrCl3]3[OMe]2 (Fig. 10) [193],... 

Basic groups giving an anion exchange resin can be inserted by first combining with chloromethylether, in the presence of a catalyst such as aluminium chloride. The product, when treated with trimethylamine, yields a quaternary ammonium compound with basic properties such as shown below ... 

Solomentseva, I.M., Gerasimenko, N.G., and Barany, S., Surface properties and aggregation of basic aluminium chloride hydrolysis products. Colloids Surf. A, 151, 113, 1999. 

Kagaya, S., Shimizu, K., and Arai, R., 1999, Separation of titanium dioxide photocatalyst in its aqueous suspensions by coagulation with basic aluminium chloride, Wat Res. 33 1753-1755. 

Volatile metal halides, usually chlorides and fluorides, also form the heart of several processes used to produce surface layers, rich in aluminium, chromium, or silicon, or combinations of these. In these processes, the workpiece to be coated is buried in a powder bed and heated to reaction temperature. The bed consists of a mixture of inert alumina filler, a master alloy powder that contains the aluminium, etc., and an activator such as ammonium chloride. Basically, at about 630°C, the activator volatilizes and the aluminium chloride vapour reacts with the master alloy to produce a volatile aluminium chloride, which then reacts with the workpiece surface to deposit aluminium. The deposited aluminium proceeds to diffuse into the surface layers of the workpiece to produce a diffusion coating. The process is driven basically by the difference in aluminium activity between the master alloy and the worlqtiece. These processes are well documented in principle, but their execution to provide reproducible and reliable results still involves considerable experience, or rule of thumb. These processes will be described in detail in Chapter 10. Finally, a chlorination treatment is used to remove tin from tin-plated steel. This uses a normally deleterious reaction to advantage and profit in the recovery of both tin and steel for recycling. Fluorination is used in the manufacture of polymers and fluorocarbon consequently, materials suitable for construction of these plants must be resistant to fluorine attack. 

Strubinger, S.K.D., Sun, I-W, Cleland, W.E., and Hussey, C.L. (1990) Electrochemical and spectroscopic studies of rhenium (IV) monomeric and dimeric chloride complexes in the basic aluminium chloride-1-methyl-3-ethylimidazolium chloride room- temperature molten salts, Inorg. Chem. 29,4246-4252. 

Ionic liquids based on chloroaluminates (the most common form of Lewis acidic or basic ionic liquids) are formed by reacting a quaternary ammonium chloride salt [QAm]" with aluminium chloride (AICI3) in various ratios [94]. Common examples are l-ethyl-3-methyl imidazoUum chloride ([EMIm]Cl) and l-(l-butyl)pyridinium chloride ([BuPy]Cl) [95]. A Lewis base, neutral species or acid is formed by varying the ratio of the two components of the ionic liquid. Using the letter N to represent the mole fraction of AICI3 in the melt [96], the following classification is given for these ionic liquids ... 

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