Acetic acid reaction stoichiometry

The synthesis of chlorarul [118-75-2] (20) has been improved. The old processes starting from phenol or 2,4,6-trichlorophenol have been replaced by new ones involving hydroquinone chlorination. These processes allow the preparation of chlorarul of higher purity, avoiding traces of pentachlorophenol. Different types of chlorination conditions have been disclosed. The reaction can be performed according to the following stoichiometry, operating with chlorine in aqueous acetic acid (86,87), biphasic medium (88), or in the presence of surfactants (89). 

From the reaction stoichiometry, for each mole of acetic acid one mole of oxygen was used. So the equal molar oxygen consumption is ... 

Fig. 9. Effect of water on the stoichiometry of the Pb(IV)- -Co(II) reaction in acetic acid at temperatures of 23 °C (Q) and 37 °C ( ). From Benson et by courtesy of The Faraday...

Henry has examined in detail the oxidation of several olefins both by thallic perchlorate in an aqueous perchloric acid medium and by thallic acetate in aqueous acetic acid. The reaction displays mixed stoichiometry... 

The oxidation of ethylene by palladous acetate in acetic acid has been examined by Moiseev et This reaction shows mixed stoichiometry ... 

Knowledge of stoichiometry of the induced reaction could help to distinguish whether chromium(V) or chromium(IV) species are involved in the oxidation of benzaldehyde. Thus, the Cr(V) hypothesis predicts that for each molecule of benzaldehyde oxidized two molecules of manganese dioxide should be formed, whereas the Cr(IV) predicts that one molecule of manganese dioxide should be formed for each two molecules of benzaldehyde oxidized. Unfortunately, the attempt to determine the stoichiometry of the induced reaction failed because the oxidized manganese species was not precipitated during the reaction presumably due to formation of acetate complexes in the concentrated acetic acid solution. 

The liquid phase hydrolysis reaction of acetic anhydride to form acetic acid is carried out in a constant volume, adiabatic batch reactor. The reaction is exothermic with the following stoichiometry... 

Having determined 60bserved> the mole fraction of acetic acid present is obtained from Eq. (5.5.3), which takes into account the stoichiometry of the reaction [Eq. (5.5.1)] and the fact that an equimolar feed was used. Equation (5.5.3) shows that the mole fraction of acetic acid present in the reaction mixture is obtained directly from the chemical shift values of the H resonance of the OH groups of the pure compounds and the observed chemical shift of the OH resonance of the reaction mixture ... 

Baciocchi et al. [J. Am. Chem. Soc., 87 (3957), 1965] have studied the chlorination of dichloro-tetramethylbenzene in acetic acid at 30° C. The reaction of interest has the following stoichiometry. 

The reaction of 2-fluoro-2,2-dinitroethanol (119) with divinylether (118) under different conditions gives three products, namely, the expected vinyl acetal (120) and the bis-acetal (121) from addition of one and two equivalents of 2-fluoro-2,2-dinitroethanol, respectively, and the vinyl ether (122), which results from franx-etherification of (118) with loss of acetaldehyde. Shackelford and co-workers found that by altering the nature of the Lewis acid catalyst and the reaction stoichiometry they were able to alter the distribution ratio of these products. 

For both reactions a RhCl3/CH3l/TPO catalyst in acetic acid as reaction solvent affords propionic acid in more than 80 % yield according to the respective stoichiometries of Equations 12 and 13. Although acetic acid is present in excess in the reaction medium, it does not participate in the homologation as reactant. Only traces of propionic acid are produced in the absence of methyl acetate, ethyli-dene diacetate or acetic anhydride under our reaction conditions. Homologation of carboxylic acids has been reported by Knifton (10) to require more severe reaction conditions (220 °C, > 100 bar). 

The voltammetric reduction of a series of dialkyl and arylalkyl disulfides has recently been studied in detail, in DMF/0.1 M TBAP at the glassy carbon electrode The ET kinetics was analyzed after addition of 1 equivalent of acetic acid to avoid father-son reactions, such as self-protonation or nucleophilic attack on the starting disulfide by the most reactive RS anion. Father-son reactions have the consequence of lowering the electron consumption from the expected two-electron stoichiometry. Addition of a suitable acid results in the protonation of active nucleophiles or bases. The peak potentials for the irreversible voltammetric reduction of disulfides are strongly dependent on the nature of the groups bonded to the sulfur atoms. Table 11 summarizes some relevant electrochemical data. These results indicate that the initial ET controls the electrode kinetics. In addition, the decrease of the normalized peak current and the corresponding increase of the peak width when v increases, point to a potential dependence of a, as discussed thoroughly in Section 2. 

The most reliable technique for the analysis of superoxides is that developed by Seyb and Kleinberg. In this method the superoxide sample is treated with a mixture of glacial acetic acid and diethyl or dibutyl phthalate. The superoxide reacts with the acetic add to yield oxygen, hydrogen peroxide, and potassium acetate. The amount of superoxide in the sample is related to the amount of oxygen evolved which is measured with a gas buret. The stoichiometry of the analytical reaction is ... 

After a time t, if kmol/m3 of acetic acid (A) has reacted, its concentration will be (CA0 - x) where CAo is the initial concentration. From the stoichiometry of the reaction, if x kmol/m3 of acetic acid has reacted, x kmol/m3 of ethanol also will have reacted and the same number of moles of ester and of water will have been formed. The rate equation may thus be written ... 

The procedure for the preparation of the platinum compounds is an extension of the method described by Kharasch and Ashford.5 A glacial acetic acid solution of chloroplatinic acid is mixed with the appropriate olefin, and in the ensuing reaction the platinum is reduced from the 4+ oxidation state to the 2 + state. The overall stoichiometry of these reactions is not known however, the reduction of the platinum is1 accompanied by the partial oxidation of the olefin. 

Mixed-ligand precursors are also frequently employed in CSD processing. For example, titanium tetraisopropoxide, which is too reactive to be directly employed in most CSD routes, may be converted into a more suitable precursor by a reaction with either acetic acid or acetylacetone (Hacac). Such reactions are critical in dictating precursor characteristics and have been studied extensively. - Using these reactions, crystalline compounds of known stoichiometry and structure have been synthesized that may subsequently be used as known precursors for film fabrication.Mixed-hgand molecules (carboxylate-alkoxide and diketonate-alkoxide ) represent complexes that are not easily hydrolyzed. A typical structure for one of these compounds is shown in Figure 27.3e. 

Currently ranked 41st in American volume of production, vinyl acetate is made by the vapor phase reaction of ethylene with acetic acid at 170-200°C. Pressures of 5-8 atm and a palladium catalyst supported on carbon are required to give conversions of 10-15% on ethylene and 15-30% on acetic acid. Equation 19.28 is an overall representation of the stoichiometry of the complex process. 

Reaction SMILES is an extension to standard SMILES used to represent a specific reaction. It uses punctuation to distinguish reactants from products. For example, the reaction SMILES CC(=0)0.CN CC(=0)NC.0 represents the reaction of acetic acid with methylamine to form N-methylacetamide plus water. As with standard SMILES, explicit H atoms are typically not shown, although they may be. For example, the same reaction can represented as [CH3]C(=0)[0FI].[CH3][NH2] [CH3]C(=0)[NH][CH3].[H]0[H]. The punctuation is used to separate reactants from products, and the period is used to separate reactants or products from each other. There are no rules in reaction SMILES that enforce correct reaction stoichiometry or other aspects of actual chemical reactions. 

Bawn and Williamson [9] examined the catalyzed oxidation of acetaldehyde in solution in acetic acid at 25°C. Whereas uncatalyzed oxidation has mediocre reproducibility, catalyzed oxidations are reproducible within 2%. The catalyst was cobalt acetate in solution in the cobaltous form. The partial oxygen pressure varied from 550 to 950 torr. Under such conditions, as in the case of photochemical oxidations, the stoichiometry of the reaction follows the overall equation... 

We know from the conservation of mass that when we run a reaction in a batch reactor the mass of products must be equal to the mass of reactants so long as nothing has escaped from the reactor. This holds absolutely and is independent of the chemical reaction type, mechanism, or stoichiometry. All that chemical reactions do is to rearrange the atoms and mass in the molecules. In essence the labels on the mass change but that is all. If the reaction in solution leads to a gas such as the reaction of baking soda with vinegar water (that is, sodium bicarbonate with dilute acetic acid), then a mass change can take place because one of the products is a gas and can escape the vessel ... 

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