Fluoride of Silicon

The simplest oxide fluoride of silicon, SiOp2, is known it is prepared by the high-temperature reaction of silica with Cap2 in an argon atmosphere. The other known oxide fluorides of silicon are a series of fluorosiloxanes, SiF30(SiF20) Sip3, of which Si2 0F6 is the best known. 

The Dielectric Coefficients of Gases. II. The Lower Hydrides of Carbon and Silicon, Oxygen, Nitrogen, Oxides of Nitrogen and Carbon, and Fluorides, of Silicon and Sulphur... 

Substances which have a deleterious effect on the taste and/or smell of the products for human consumption derived from the aquatic environment Toxic or persistent organic compounds of silicon Inorganic compounds of phosphorus and elemental phosphorus Non-persistent mineral oils and hydrocarbons of petroleum origin Cyanides, fluorides... 

Modification of alkyd resins with high proportions of silicones considerably reduces rates of attack, but the most spectacular extension of life is shown by fluorinated polymers such as polyvinylidene fluoride where erosion rates can be reduced to 0 -1 /tm/year. If this level of durability can be achieved an initial coating, if firmly adherent and free from any breaks, may often be expected to maintain protection over a metal substrate for the likely life of the structure. The considerably increased first cost, as compared with more conventional coatings, has to be balanced against the probable saving in maintenance costs or consequences of failure. 

Both acids form compounds of silicon as a result of attack on the network, silicon fluoride from hydrofluoric acid and silicyl phosphate from phosphoric acid. 

Interesting results have also been obtained with light-induced oscillations of silicon in contact with ammonium fluoride solutions. The quantum efficiency was found to oscillate complementarity with the PMC signal. The calculated surface recombination rate also oscillated comple-mentarily with the charge transfer rate.27,28 The explanation was a periodically oscillating silicon oxide surface layer. Because of a periodically changing space charge layer, the situation turned out to be nevertheless relatively complicated. 

This ability of silicon to assume coordination numbers of five and six is also very important in the already mentioned catalytic affects of fluoride ions, because... 

In addition to activation of sihcon bonds by fluoride ions as discussed in Section 2.4, silicon-silicon, silicon-carbon, silicon-hydrogen, and silicon-nitrogen bonds are activated by transition metal salts and transition metal complexes. Thus, hydrolysis of silicon-carbon bonds such as in phenyltrimethylsilane 81 can be induced by... 

Because allyltrimethylsilane 82 or benzyltrimethylsilane 83 can be regarded as combinations of the hard trimethylsilyl cation and the soff allyl or benzyl anions, pyridine N-oxide 860 reacts with excess 82 or 83 in the presence of catalytic amounts of tetrabutylammonium fluoride di- or trihydrate in THF to give 2-allyl-or 2-benzylpyridines 948 and 950 [60]. The general reaction of silicon reagents such as 82 and 83 or of trimethylsilyl cyanide 18 with fluoride to generate allyl or... 

Noyori and coworkers found that tetrafluorosilane or trimethylsilyl tri-flate catalyzes the condensation of appropriately protected glycopyranosyl fluorides with trimethylsilyl ethers or alcohols. The strong affinity of silicon for fluorine was considered to be the driving force for this reaction. In the case of Sip4, attack of a nucleophile on the glycosyl cation-SiFj ion-pair intermediate was anticipated. Thus, condensation of 2,3,4,6-tetra-O-benzyl-a- and - -D-glucopyranosyl fluorides (47a and 47fi) with methyl... 

Silver fluoride and boron detonate violently when their mixture is ground up. The same thing happened with the mixture of this fluoride with silicon. When it is mixed with potassium, it gives rise to an extremely violent detonation. At 320 C it causes the incandescence of titanium. 

Sodium beryllium fluoride (Na2BeF4) is water-soluble and sodium aluminum fluoride (Na,AlF6) is water-insoluble. A part of the silicon volatilizes off as silicon tetrafluoride (SiF4), while the other part remains in the residue as silicon dioxide (Si02). Fluorination of silicon is unnecessary and it would be economical to recover all of it as silica. This is accomplished by using soda ash, i.e., sodium carbonate (Na2C03) in the reaction mixture ... 

The covalently bonded solids such as silica cannot be easily broken by aqueous solutions. For example, the strong Si-O bonds silica is not dissolvable by boiling with concentrated acids except hydrofluoric acid because of the formation of silicon fluoride which is a gas and expels otherwise else it may form fluosilicic acid by reaction with water. 

Preparation, characterization, and properties of silicon-containing triorganotin fluorides, both symmetrical and unsymmetrical, were investigated. It was observed that introduction of a trimethylsilyl group in the alkyl chain results in a considerable enhancement of solubility in various nonpolar solvents including dense carbon dioxide. 

Figure 1. Schemes for the synthesis of silicon containing triorganotin fluorides.

Solubilities of Silicon Containing Triorganotin Fluorides at 25°C Solvent... 

Contact with liquid hydrogen fluoride causes violent evolution of silicon tetraflu-oride. (The same is probably true of metal silicides and other silicon compounds generally.)... 

Carreira and Kruger reported facile transmetallation of silicon enolates to other soft metal enolates including Gu derivatives.499 They reasoned that the use of soft metal fluoride complexes enabled silyl metal transmetallation with catalytic use of a soft metal source. The concept is illustrated in Scheme 103. Normal Lewis acid-catalyzed reactions of silicon enolates with aldehydes proceed via activation of aldehydes by carbonyl oxygen coordination to Lewis acids, as shown in the upper equation of Scheme 103. A key step for catalytic turnover is the desilyation of 233 by the... 

Many theories on the formation mechanisms of PS emerged since then. Beale et al.12 proposed that the material in the PS is depleted of carriers and the presence of a depletion layer is responsible for current localization at pore tips where the field is intensified. Smith et al.13-15 described the morphology of PS based on the hypothesis that the rate of pore growth is limited by diffusion of holes to the growing pore tip. Unagami16 postulated that the formation of PS is promoted by the deposition of a passive silicic acid on the pore walls resulting in the preferential dissolution at the pore tips. Alternatively, Parkhutik et al.17 suggested that a passive film composed of silicon fluoride and silicon oxide is between PS and silicon substrate and that the formation of PS is similar to that of porous alumina. 

Presence of HF results in the dissolution of silicon oxide and activates the surface. Fluoride species such as HF and F also react directly with the bare silicon surface. 

Which materials are best for cell design depends essentially on the type of electrolyte used. Because HF acid is quite common in the electrochemistry of silicon, materials resistant to HF are preferable. Polyvinyl chloride (PVC), polypropylene (PP), polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) can be used for the cell body. PVC is a good choice for most designs because it is inex-... 

The first models for the electrochemical dissolution process of silicon in HF assumed a fluoride-terminated silicon surface to be present in electrolytes containing HF [Ge6, Du3[. However, by IR spectroscopy it was found that virtually the whole surface is covered by hydride (Si-H) [Ni3[. No evidence of Si-F groups is found in IR spectra independent of HF concentration used [Ch9[. This is surprising insofar as the Si-F (6 eV) bond is much stronger than the Si-H (3.5 eV) bond, and so it cannot be assumed that Si-F is replaced by Si-H during the electrochemical dissolution. This led to the conclusion that if a silicon atom at the surface establishes a bond to a fluorine atom it is immediately removed from the surface. 

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