Formic acid from ethylene

In the determination of formic acid in more complicated reaction-mixtures (for example, in the presence of buffers,22 69a in solutions containing non-volatile acids,49- 67 and in solutions containing ammonia234), it was necessary to distil the formic acid from the reaction solution (after destruction of the excess periodate with ethylene glycol or arsenite) before it could be titrated. 

Ozone hydro gen peroxide formic acid Carboxylic acids from ethylene derivs. 

Figure 5.6 Alcohols, aldehydes, ketones and acids 15, ethylene glycol 16, vinyl alcohol 17, acetaldehyde 18, formaldehyde 19, glyoxal 20, propionaldehyde 21, propionaldehyde 22, acetone 23, ketene 24, formic acid 25, acetic acid 26, methyl formate. (Reproduced from Guillemin et at. 2004 by permission of Elsevier)...

Photolytic. Photolysis products include carbon monoxide, ethylene, free radicals, and a polymer (Calvert and Pitts, 1966). Anticipated products from the reaction of acrolein with ozone or OH radicals in the atmosphere are glyoxal, formaldehyde, formic acid, and carbon dioxide (Cupitt,... 

Chemical/Physical. Gaseous products formed from the reaction of cyclohexene with ozone were (% yield) formic acid (12), carbon monoxide (18), carbon dioxide (42), ethylene (1), and valeraldehyde (17) (Hatakeyama et al., 1987). In a smog chamber experiment conducted in the dark at 25 °C, cyclohexane reacted with ozone. The following products and their respective molar yields were oxalic acid (6.16%), malonic acid (6.88%), succinic acid (0.63%), glutaric acid (5.89%), adipic acid (2.20%), 4-hydroxybutanal (2.60%), hydroxypentanoic acid (1.02%), hydroxyglutaric acid (2.33%), hydroxyadipic acid (1.19%), 4-oxobutanoic acid (6.90%), 4-oxopentanoic acid (4.52%), 6-oxohexanoic acid (4.16%), 1,4-butandial (0.53%), 1,5-pentanedial (0.44%), 1,6-hexanedial (1.64%), and pentanal (17.05%). 

Chemical/Physical. Gaseous products formed from the reaction of cyclopentene with ozone were (% yield) formic acid (11), carbon monoxide (35), carbon dioxide (42), ethylene (12), formaldehyde (13), and butanal (11). Particulate products identified include succinic acid, glutaraldehyde, 5-oxopentanoic acid, and glutaric acid (Hatakeyama et al., 1987). 

Beckett and Hua (2000) investigated the sonolytic decomposition of 1,4-dioxane in aqueous solution at 25 °C at discrete ultrasonic frequencies. They found that the highest first-order decomposition rate occurred at 358 kHz followed by 618, 1,071, and 205 kHz. At 358 kHz, 96% of the initial 1,4-dioxane concentration was decomposed after 2 h and the pH of the solution decreased to 3.75 from 7.50. Major decomposition intermediates were ethylene glycol diformate, methoxyacetic acid, formaldehyde, glycolic acid, and formic acid. 

Onsager inverted snowball theory (Com.) relation to Smoluchowski equation in, 35 relaxation time by, 34 rotational diffusion and, 36 Ozone in the atmosphere, 108 alkene reactions with, 108 Crigee intermediate from, 108 molozonide from, 108 ethylene reaction with, 109 acetaldehyde effect on, 113 formic anhydride from, 110 sulfur dioxide effect on, 113 sulfuric acid aerosols from, 114 infrared detection of, 108 tetramethylethylene (TME) reaction with, 117... 

A series of polyhydric alcohols, ranging from ethylene glycol to hexitols was examined, at 20° and in the presence of a large excess of lead tetraacetate, by Hockett and coworkers.44 The compounds yielded a family of oxidation-rate curves in which the position of a curve was a function of the number of free carbinol groups in an unbroken series, but there was no simple stoichiometric relation between the number of alcohol groups and the amount of oxidant consumed. At least part of this complexity appeared to be caused by simultaneous oxidation of the formic acid produced in the reaction. The formic acid was converted smoothly to carbon dioxide in about quantitative yield when water was added to the acetic acid solution and the reaction temperature was raised45 - 48 to 35-45°. However, other... 

Unlike formic acid, acetic acid is absolutely stable in SC water to 500° C at 34.5 MPa. At 400° C the presence of acetic acid (1.0M) triples the rate of formation of ethylene from ethanol however, the formation of the liquid byproduct ethyl acetate accounts for 46% of the ethanol which reacted. Normally the presence of a strong acid (such as H2S0i,) is required to catalyze the formation of the acetate from ethanol and acetic acid. Consequently, the formation of the acetate (along with diethylether as a minor, <1%, additional product) surprised us. This result seems to indicate the ability of SC water to act as an acid catalyst at high temperatures when Kw>10-1 ... 

Figure 5.1.6 Comparison of the energy efficiencies and current densities for C02 reduction to formic acid, syngas, and hydrocarbons (methane and ethylene) reported in the literature with those of water electrolyzers. Efficiencies of electrolyzers are total system efficiencies, while the CO2 conversion efficiencies only include cathode losses and neglect anode and system losses. Adapted from [17],...

Poisoning by ethylene glycol (CH2OHCH2OH) is due to aldehydes, glycolate, oxalate, and lactate, resulting from an initial attack by alcohol dehydrogenase. This is similar to the activation of methanol to formaldehyde and subsequent oxidation by aldehyde dehydrogenase to formic acid. 

The liquid phase processes resembled Wacker-Hoechst s acetaldehyde process, i.e., acetic acid solutions of PdCl2 and CuCl2 are used as catalysts. The water produced from the oxidation of Cu(I) to Cu(II) (Figure 27) forms acetaldehyde in a secondary reaction with ethylene. The ratio of acetaldehyde to vinyl acetate can be regulated by changing the operating conditions. The reaction takes place at 110-130°C and 30-40 bar. The vinyl acetate selectivity reaches 93% (based on acetic acid). The net selectivity to acetaldehyde and vinyl acetate is about 83% (based on ethylene), the by-products being CO2, formic acid, oxalic acid, butene and chlorinated compounds. The reaction solution is very corrosive, so that titanium must be used for many plant components. After a few years of operation, in 1969-1970 both ICI and Celanese shut down their plants due to corrosion and economic problems. 

Trans-l,2-bis[tris(trimethylsilyl)silyl]ethylene 5 was obtained from the reaction of tris(tri-methylsilyl)silyllithium with formic acid methyl ester [7]. The corresponding dianion 6 was obtained as the only reaction product in a fast reaction of 5 with two equivalents of potassium tert-butoxide in the presence of two equivalents of crown ether as the first example of a vinylidene-bridged oligosilyl a,co-dianion (Eq. 3), which is in good analogy with our previously synthesized alkynylidene- and alkylidene-bridged compounds [3,4, 8]. 

The state function of So. The contributions of the ground state functions of phenyl group(equivalent to benzene in the H-electron approximation), -CH=CH- (equivalent to ethylene) and carboxyl group(e-quivalent to formic acid) are 83 % and the CT functions which connect the LE functions in order to form the molecule, those from the OMO of benzene to the UMO of ethylene, from ethylene(OMO) to carboxyl group (UMO), from etlwlene(OMO) to benzene(UKO) and from carboxyl group(OMO) to ethylene(UIK)) are totally 16 When examining the contributions of... 

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