Formate ions

The concentration of aqueous solutions of the acid can be deterrnined by titration with sodium hydroxide, and the concentration of formate ion by oxidation with permanganate and back titration. Volatile impurities can be estimated by gas—Hquid chromatography. Standard analytical methods are detailed in References 37 and 38. 

The chromium can be stabilized in a limited way to prevent surface fixation by addition of formate ions. The formate displaces the sulfate from the complex and masks the hydroxyl ions from forming the larger higher basicity complexes. This stabilization can then be reversed in the neutralization to a pH of about 4.0 and taimage becomes complete. This simple formate addition has decreased the time of chrome tanning by about 50% and has greatly increased the consistent quaHty of the leather produced. 

The reaction has been applied to more complex enamines 13) and to dienamines 19). The reduction may be rationalized by initial protonation at the enamine carbon and subsequent decarboxylation of formate ion and addition of the hydride ion to the iminium cation. This mechanism has been given support by the reaction of the enamine (205) with deuterated formic acid 143) to give the corresponding amines. The formation of 206 on reaction with DCOOH clearly indicates that protonation at the enamine carbon is the initial step. 

The idea that dichlorocarbene is an intermediate in the basic hydrolysis of chloroform is now one hundred years old. It was first suggested by Geuther in 1862 to explain the formation of carbon monoxide, in addition to formate ions, in the reaction of chloroform (and similarly, bromoform) with alkali. At the end of the last century Nef interpreted several well-known reactions involving chloroform and a base in terms of the intermediate formation of dichlorocarbene. These reactions included the ring expansion of pyrroles to pyridines and of indoles to quinolines, as well as the Hofmann carbylamine test for primary amines and the Reimer-Tiemann formylation of phenols. 

Autoprotolysis of Formic Acid. The self-dissociation of pure formic acid yields, in addition to the formate ion, the positive ion (HCOOII2)+, according to... 

Formate ion, bond lengths in, 757 electrostatic potential map of, 757 Formic acid, bond lengths in. 757 pKa of, 756 Formyl group, 697 p-Formyl benzoic acid, p/C, of, 760 Fourier-transform NMR spectroscopy (FT-NMR), 447-448 Fractional crystallization, resolution and, 307... 

Packer and Richardson (1975) and Packer et al. (1980) made use of the fact that electrons can be generated in water by y-radiation from a 60Co source (Scheme 8-29) to induce a free radical chain reaction between diazonium ions and alcohols, aldehydes, or formate ion. It has to be emphasized that the radiolytically formed solvated electron in Scheme 8-29 is only a part of the initiation steps (Scheme 8-30) by which an aryl radical is formed. The aryl radical initiates the propagation steps shown in Scheme 8-31. Here the alcohol, aldehyde, or formate ion (RH2) is the reducing agent (i.e., the electron donor) for the main reaction. The process is a hydro-de-diazoniation. 

All anions that are the conjugate bases of weak acids produce basic solutions. For example, formic acid, HCOOH, the acid in ant venom, is a weak acid, and so the formate ion acts as a base in water ... 

SOLUTION The salt present at the stoichiometric point, sodium formate, provides basic formate ions, and so we expect pH > 7. From Table 10.1, Ka = 1.8 X 10 4 for formic acid therefore, Kb = KJKa = 5.6 X 1CT11. 

Although the reverse of this reaction cannot be carried out directly, carbon monoxide does react with hydroxide ions in hot alkali to produce formate ions ... 

Again, the Cannizzaro reduction occurs under the condensation conditions. The ortho ester HC(0Et)2 was used as a dehydrating agent in the final acetal format ion. 

The permanganate oxidation of formic acid has attracted much attention. The reaction is pH-independent above pH 5 and involves formate ion. At lower pH s the rate is much lower until permanganic acids begins to be formed at very low pH ... 

The ten-fold reduction in rate on deuteration without changing the stoichiometry provides strong evidence that both sets of products originate in a common step. The Arrhenius parameters for this reaction, E = 13.3 kcal.mole A5 = —17 eu) invite comparison with those for the oxidation of free formate ion E = 12.4 kcal.mole S AS = —15 eu). 

Oxidation of formic acid by mercuric chloride is the subject of several early kinetic studies. Dhar showed the reaction to be first-order in oxidant and substrate and to be subject to strong retardation by added chloride ions in agreement with earlier work. The reaction is also subject to retardation by added acid and presumably involves formate ion as the principal reactant. 

MOSFETT s, and silicon oxide is deposited. The source/drain positions where electrical contact is to be made to the MOSFETs are defined, using the oxide-removal mask and an etch process. For shallow trench isolation, anisotropic silicon etch, thermal oxidation, oxide fill and chemical mechanical leveling are the processes employed. For shallow source/drains formation, ion implantation techniques are still be used. For raised source/drains (as shown in the above diagram) cobalt silicide is being used instead of Ti/TLN silicides. Cobalt metal is deposited and reacted by a rapid thermal treatment to form the silicide. Capacitors were made in 1997 from various oxides and nitrides. The use of tantalmn pentoxide in 1999 has proven superior. Platinum is used as the plate material. 

D. Seebach and his coworkers have employed nltrosamlnes creatively In a number of synthetic trans format Ions. Among... 

The mechanism of carbon dioxide reduction in aqueous and nonaqueous solutions was investigated by several authors. It is now generally accepted that the reduction of carbon dioxide to formate ions is a multistep reaction with the intermediate formation of free radicals CO2 and HCO2 either in the solution or adsorbed on the electrode ... 

Transfer hydrogenolysis of benzyl acetate was studied on Pd/C at room temperature using different formate salts.244 Hydrogen-donating abilities were found to depend on the counterion K+ > NH4 + > Na+ > Li+ > H+. Formate ion is the active species in this reaction. Adsorption of the formate ion on the Pd metal surface leads to dissociative chemisorption resulting in the formation of PdH- and C02. The kinetic isotope effect proves that the dissociative chemisorption of formate is the rate-limiting step. The adsorption and the surface reaction of benzyl acetate occurs very rapidly. 

A little later, Russell et al.19 tried to obtain methanol from carbon dioxide by electrolysis. Reduction of carbon dioxide to formate ion took place in a neutral electrolyte at a mercury electrode. On the other hand, formic acid was reduced to methanol either in a perchloric acid solution at a lead electrode or in a buffered formic acid solution at a tin electrode. The largest faradaic efficiency for methanol formation from formic acid was ca. 12%, with poor reproducibility, after passing 1900 C in the perchloric acid solution at Pb in a very narrow potential region (-0.9 to -1.0 V versus SCE). In the buffered formic acid solution (0.25 M HCOOH + 0.1 M... 

Four years of study led to the discovery of glycine in the millimetre wavelength range in the hot molecular clouds of Sagittarius (around 81,500 light years away), Orion KL and W51. We can only conjecture as to the mechanism of its formation. Ion-molecule reactions in the gas phase, as well as UV photolytic processes in molecular ice, have been discussed. 

Two alternatives had been proposed earlier. The first assumed the dissociation of a CO ligand as the first step (Equation 38), and the coordination of a formate ion as the second step (Equations 39-40)... 

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