Acids decomposition

Many problems have been reported (163), and the process has been abandoned because of the difficulty in handling sohds. Processes which are thought to have the best likelihood of success ate based on sulfuric acid decomposition. Three prominent cycles are based on this reaction the General Atomics iodine—sulfur cycle... 

Decomposition of Metal Chlorides by Acids. Two commercial processes employing the acidic decomposition of metal chlorides are the salt—sulfuric acid process and the Hargreaves process. Although these processes are declining in importance, they are used mainly because of the industrial demand for salt cake [7757-82-6] by the paper (qv) and glass (qv) industries. In the United States, however, Httle HCl is produced this way. 

Organomineral hydroperoxides have been prepared from hydrogen peroxide and organomineral haUdes, hydroxides, oxides, peroxides, and amines (10,33). If HX is an acid, ammonia is used to prevent acidic decomposition. 

An excess of crotonaldehyde or aUphatic, ahcyhc, and aromatic hydrocarbons and their derivatives is used as a solvent to produce compounds of molecular weights of 1000—5000 (25—28). After removal of unreacted components and solvent, the adduct referred to as polyester is decomposed in acidic media or by pyrolysis (29—36). Proper operation of acidic decomposition can give high yields of pure /n j ,/n7 j -2,4-hexadienoic acid, whereas the pyrolysis gives a mixture of isomers that must be converted to the pure trans,trans form. The thermal decomposition is carried out in the presence of alkaU or amine catalysts. A simultaneous codistillation of the sorbic acid as it forms and the component used as the solvent can simplify the process scheme. The catalyst remains in the reaction batch. Suitable solvents and entraining agents include most inert Hquids that bod at 200—300°C, eg, aUphatic hydrocarbons. When the polyester is spHt thermally at 170—180°C and the sorbic acid is distilled direcdy with the solvent, production and purification can be combined in a single step. The solvent can be reused after removal of the sorbic acid (34). The isomeric mixture can be converted to the thermodynamically more stable trans,trans form in the presence of iodine, alkaU, or sulfuric or hydrochloric acid (37,38). 

Spent acid burning is actually a misnomer, for such acids are decomposed to SO2 and H2O at high temperatures in an endothermic reaction. Excess water in the acid is also vaporized. Acid decomposition and water vaporization require considerable heat. Any organic compounds present in the spent acid oxidize to produce some of the required heat. To supply the additional heat required, auxiUary fuels, eg, oil or gas, must be burned. When available, sulfur and H2S are excellent auxiUary fuels. 

Oxygen-enriched air is sometimes used in spent acid decomposition furnaces to increase furnace capacity. Use of oxygen-enriched air reduces the amount of inerts in the gas stream in the furnace and gas purification equipment. This permits higher SO2 throughput and helps both the heat and water... 

Metallurgical (smelter) plants and spent acid decomposition plants usually produce acid of good (low) color because the SO2 feed gases ate extensively purified prior to use. In some cases, however, and particularly at lead smelters, sufficient amounts of organic flotation agents are volatilized from sulfide ores to form brown or black acid. Such acid can be used in many applications, particularly for fertilizer production, without significant problems arising. 

With strong hydrochloric acid, decomposition into cliazo-niuin salt and amine takes place,... 

As early as 1923 Hinshelwood and Topley (27) noted the exceptionally erratic behavior of palladium foil catalyst in the formic acid decomposition reaction within 140-200°C. The initially very high catalytic activity decreased 102 times during the exposure of palladium to hydrogen, which is a product of the reaction. Though the interpretation does not concern the /3-hydride formation, the authors observation deserves mentioning. 

Fig. 8. Arrhenius plots for the formic acid decomposition on palladium foil (1) and small pieces of this foil (2) at a higher temperature range, when hydrogen evolving as a product of the reaction was absorbed by Pd and transformed into the /3-Pd-H hydride phase. At the lower temperature range the reaction proceeds on the a-Pd-H phase, with a higher activation energy when the foil was hydrogen pretreated (2a), and a lower activation energy for a degassed Pd foil (3a). After Brill and Watson (57).

Volter and Alsdorf (52) obtained a relation of a very similar character for the dependence of the catalytic activity in formic acid decomposition on the composition of the nickel-copper alloys. However, extending the times of the alloy annealing for their better homogenization caused the maxima on the catalytic activity curves to disappear. 

TI4SCI4 and T SeCh melt at 440 and 442°C, respectively. They can be distilled between 650 and 700°C without decomposition. They are insoluble in H2O and organic solvents, but soluble in aqueous alkaline solutions. With cone, acids, decomposition takes place. The electric conductivity has been determined to be 1.4-10 and 2.1-10 fl cm for TI4SCI4 and TUSeCU, respectively. The probable structural formula is Tl3(TlCl4Y). The compounds thus, presumably, consist of Tli,4Cl4,4Y2/8 octahedra that are interconnected by the chalcogen atoms to linear chains (321). 

More recently Hand et al. (ref. 9) have studied the decomposition reaction of N-chloro-a-amino acid anions in neutral aqueous solution, where the main reaction products are carbon dioxide, chloride ion and imines (which hydrolyze rapidly to amine and carbonyl products). They found that the reaction rate constant of decarboxylation was independent of pH, so they ruled out a proton assisted decarboxylation mechanism, and the one proposed consists of a concerted decarboxylation. For N-bromoamino acids decomposition in the pH interval 9-11 a similar concerted mechanism was proposed by Antelo et al. (ref. 10), where the formation of a nitrenium ion (ref. 11) can be ruled out because it is not consistent with the experimental results. Antelo et al. have also established that when the decomposition reaction takes place at pH < 9, the disproportionation reaction of the N-Br-amino acid becomes important, and the decomposition goes through the N,N-dibromoamino acid. This reaction is also important for N-chloroamino compounds but at more acidic pH values, because the disproportionation reaction... 

Fig. 3 gives the conversions for acetic acid and ammonia decomposition over Ti02 and Al-Ti02 in a three-phase fluidized photoreactor. In the case of acetic acid decomposition (Inlet condition of 300 ppm), the conversion increased with alununum addition. In particular, the conversion to CO2 reached about 90% and then it was kept until 600 mins on Al-TiOa catalyst. On the other hand, in b), the anunonia removal (Inlet condition of 80ppm) also enhanced on Al-Ti02 compared to that conventional Ti02 catalyst the conversion to N2 reached above 95% in Al-Ti02. We have also observed that the ammonia conversion in a conventional batch type steady photoreactor could be obtained up to 70%. From this result, we could confirmed that... 

Fig.3. Decomposition of acetic acid and ammonia over Ti02 and AI-Ti02 in three-phase fluidized photocatalytic system, a) For acetic acid decomposition and b) For ammonia decomposition...

Figure S.S The mode of acid decomposition of an aluminosilicate glass.

A mass spectrometric study was carried out to establish tbe structure of compoimd 69. Its mass spectrum contains tbe molecular ion peak m/z 252 (16.98%) and a base peak (100%) at m/z 210, corresponding to 2-(2-hydroxypbenyl)benzimidazole (70). A tendency towards decreasing the heterocycle size is characteristic of the mass spectrometric behavior of 1,5-benzodiazepin-2-ones [61] and consequently the mass spectra of these compounds contains intense peaks of the corresponding benzimidazoles. It is also known that the mass spectrometric fragmentation of 1,5-benzodiazepines is similar to their thermal or acid decomposition. In fact, refluxing compound 69 in concentrated sulfuric acid yields benzimidazole 70 as the main product. 

Formic acid at 98% had to be used as a solvent during a catalytic hydrogenation by using the palladium/carbon system. When the solvent came into contact with the catalyst there was a release of hydrogen. Does this accident result from the acid decomposition catalysed by palladium In this case the decomposition... 

Lu GQ, Crown A, Wieckowski A. 1999. Eormic acid decomposition on polycrystaUine platinum and palladized platinum electrodes. J Phys Chem B 103 9700-9711. 

Figure 12.14 SFG spectra of the carbonyls formed during formic acid decomposition on a Pt(lll) electrode in 0.1 M H2SO4 electrolyte containing 0.1 M formic acid. The spectral position is typical of atop CO on the Pt(l 11) surface. Times at which the spectra have been recorded are from 2 to 496 s, yielding HCOOH decomposition kinetics at three electrode potentials, -0.200, -0.025, and 0.225 V vs. Ag/AgCl.

Overall, we demonstrated electrode potential- and time-dependent properties of the atop CO adsorbate generated from the formic acid decomposition process at three potentials, and addressed the issues of formic acid reactivity and poisoning [Samjeske and Osawa, 2005 Chen et al., 2003,2006]. There is also a consistency with the previous kinetic data obtained by electrochemical methods the maximum in formic acid decomposition rates was obtained at —0.025 V vs. Ag/AgCl or 0.25 V vs. RHE (cf. Fig. 12.7 in [Lu et al., 1999]). However, the exact path towards the CO formation is not clear, as the main reaction is the oxidation of the HCOOH molecule ... 

For the GC method, the generated carbon disulfide is analysed using a flame photomeric detector in the sulfur mode. The acid decomposition is carried out in a sealed glass container at 80 °C, and an aliquot of the headspace is injected into a gas chromatograph. " ... 

The analytical methods specified above, based on the evolution of carbon disulfide from the parent alkylenebis(dithiocarbamates) by hot acid decomposition using spectrophotometry or GC, are accepted as routine methods to determine alkylenebis-(dithiocarbamate) residues. The two methods are described in detail below. 

Figure 1 Apparatus for hot acid decomposition of aUsylenebis(dithiocarbamates) and distillation of carbon disulfide. 1 = Three-necked round-bottom flask 2 = air inlet tube 3 = dropping funnel 4 = Liebig reflux condenser 5 = gas washing tubes 6 = carbon disulfide absorption tube.

A monograph on mineral acid decomposition in inorganic analysis is available [16], as well as an acid decomposition site (http //www.sampleprep.duq.edu/ sampleprep). 

---