Decomposition, spontaneous

The problem asks for the partial pressure of N2 O4 that will make the decomposition spontaneous when T — 298 K and p of NO2 = 1 bar. The value of ZlG must be zero before it can become negative. Therefore, to find the threshold pressure of N2 O4 that makes the decomposition spontaneous, set A G = 0 and J N02 = 1 bar and then rearrange to solve for the partial pressure of N2 O4 ... 

Covering CaSi with dilute hydrochloric acid causes vigorous decomposition. Spontaneously igniting silanes are formed, with white silicic acid as the residue. 

It is a liquid, b,p. 363 K, but if heated it decomposes and hence must be distilled under reduced pressure decomposition may occur with explosive violence and this can occur even at room temperature if impurities are present. Combustible material, for example paper and wood, ignite spontaneously with explosive violence on contact with the acid, and it can produce painful blisters on the skin,... 

The solvents listed in Table 2.1 were chosen to cover a broad range in solvent properties. In fact hexane was initially also among them, but unfortunately the rate of the reaction in this solvent is extremely low. It turned out that in this solvent spontaneous decomposition of 2.4a competes with the Diels-Alder reaction. 

Nitronium salts are colourless, crystalline and very hygroscopic nitronium perchlorate and sulphate are unstable and liable to spontaneous decomposition, whereas nitronium tetrafluoroborate and other complex fluoro-salts are relatively stable. 

Because the electrolyte contains excess alkaH which could cause spontaneous decomposition of the hydrogen peroxide, the H2O2 in the product... 

Cmde diketene obtained from the dimeriza tion of ketene is dark brown and contains up to 10% higher ketene oligomers but can be used without further purification. In the cmde form, however, diketene has only limited stabHity. Therefore, especiaHy if it has to be stored for some time, the cmde diketene is distiHed to > 99.5% purity (124). The tarry distiHation residue, containing trike ten e (5) and other oligomers, tends to undergo violent Spontaneous decomposition and is neutralized immediately with water or a low alcohol. Ultrapure diketene (99.99%) can be obtained by crystallization (125,126). Diketene can be stabHized to some extent with agents such as alcohols and even smaH quantities of water [7732-18-5] (127), phenols, boron oxides, sulfur [7704-34-9] (128) and sulfate salts, eg, anhydrous copper sulfate [7758-98-7]. 

Decomposition of diphenoylperoxide [6109-04-2] (40) in the presence of a fluorescer such as perylene in methylene chloride at 24°C produces chemiluminescence matching the fluorescence spectmm of the fluorescer with perylene was reported to be 10 5% (135). The reaction follows pseudo-first-order kinetics with the observed rate constant increasing with fluorescer concentration according to = k [flr]. Thus the fluorescer acts as a catalyst for peroxide decomposition, with catalytic decomposition competing with spontaneous thermal decomposition. An electron-transfer mechanism has been proposed (135). 

Health and Safety Factors. Malononitrile is usually available as a soHdifted melt in plastic-Hned dmms. Remelting has to be done carefully because spontaneous decomposition can occur at elevated temperatures, particularly above 100°C, in the presence of impurities such as alkaHes, ammonium, and 2inc salts. Melting should be carried out by means of a water bath and only shordy before use. Occupational exposure to malononitrile mainly occurs by inhalation of vapors and absorption through the skin. Malononitrile has a recommended workplace exposure limit of 8 mg/m, an LD q (oral, rats) of 13.9 mg/kg, and is classified as slight irritant (skin irritation, rabbits). Transport classification RID/ADR 61, IMDG-Code 6.1, lATA/ICAO 6.1. 

The iodine compound is more stable and separates as so-called nitrogen trHodide monoammoniate [14014-86-9], NI NH, an insoluble brownish-black soHd, which decomposes when exposed to light in the presence of ammonia. In reactions of the halogens with the respective ammonium salts, however, the action is different. Chlorine replaces hydrogen and nitrogen chloride [10025-85-1], NCl, separates as oily, yeUow droplets capable of spontaneous explosive decomposition. 

Complexing agents, which act as buffers to help control the pH and maintain control over the free metal—salt ions available to the solution and hence the ion concentration, include citric acid, sodium citrate, and sodium acetate potassium tartrate ammonium chloride. Stabilizers, which act as catalytic inhibitors that retard the spontaneous decomposition of the bath, include fluoride compounds thiourea, sodium cyanide, and urea. Stabilizers are typically not present in amounts exceeding 10 ppm. The pH of the bath is adjusted. 

Titanium Dibromide. Titanium dibromide [13873-04-5] a black crystalline soHd, density 4310 kg/m, mp 1025°C, has a cadmium iodide-type stmcture and is readily oxidized to trivalent titanium by water. Spontaneously flammable in air (142), it can be prepared by direct synthesis from the elements, by reaction of the tetrabromide with titanium, or by thermal decomposition of titanium tribromide. This last reaction must be carried out either at or below 400°C, because at higher temperatures the dibromide itself disproportionates. 

Corrosion products and deposits. All sulfate reducers produce metal sulfides as corrosion products. Sulfide usually lines pits or is entrapped in material just above the pit surface. When freshly corroded surfaces are exposed to hydrochloric acid, the rotten-egg odor of hydrogen sulfide is easily detected. Rapid, spontaneous decomposition of metal sulfides occurs after sample removal, as water vapor in the air adsorbs onto metal surfaces and reacts with the metal sulfide. The metal sulfides are slowly converted to hydrogen sulfide gas, eventually removing all traces of sulfide (Fig. 6.11). Therefore, only freshly corroded surfaces contain appreciable sulfide. More sensitive spot tests using sodium azide are often successful at detecting metal sulfides at very low concentrations on surfaces. 

An explosive decomposition in an ethylene oxide (EO) distillation column, similar in its results to that described in Section 7.3.2, may have been set off by polymerization of EO in a dead-end spot in the column base where rust, a polymerization catalyst, had accumulated. Such deadends should be avoided. However, it is more likely that a flange leaked the leaking gas ignited and heated an area of the column above the temperature at which spontaneous decomposition occurs. The source of ignition of the leak may have been reaction with the insulation, as described... 

Decomposition reactions are a special class of propagating flames where a molecule can undergo spontaneous exothermic reaction. The most widely reported incidents in which decomposition reactions occur are for acetylene where decomposition primarily gives carbon and hydrogen, as shown in the following reaction ... 

Boranes are extremely reactive compounds and several are spontaneously flammable in air. Arac/tno-boranes tend to be more reactive (and less stable to thermal decomposition) than niiio-boranes and reactivity also diminishes with increasing mol wt. C/oio-borane anions are exceptionally stable and their general chemical behaviour has suggested the term three-dimensional aromaticity . 

The monoxides SeO and TeO have transient existence in flames but can not be isolated as stable solids. PoO has been obtained as a black, easily oxidized solid by the spontaneous radiolytic decomposition of the sulfoxide P0SO3. 

A different reaction takes place between an ethereal solution of the disulfide and hydrogen azide this reaction proceeds according to Eq. (15). Probably the principal step of this reaction is the spontaneous decomposition of the disulfide into nitrogen, sulfur, and... 

Selbst-zersetzuog, /. spontaneous decomposition autolysis, -zerstorung,/. self-destruction. -zeugung, /. spontaneous generation, abiogenesis. 

Metal chelates afford a better initiating system as compared to other redox systems since the reactions can be carried out at low temperatures, thus avoiding wastage reactions due to chain transfer. Homopolymer formation is also minimum in these systems. It was observed by Misra et al. [66,67] that the maximum percentage of grafting occurs at a temperature much below the decomposition temperature of the various metal chelates indicating that the chelate instead of undergoing spontaneous decomposition receives some assistance either from the solvent or monomer or from both for the facile decomposition at lower temperature. The solvent or monomer assisted decomposition can be described as ... 

The oxidation of hydrogen to water (Hj -t- i Oj -> HjO) is thermodynamically spontaneous and the energy released as a result of the chemical reaction appears as heat energy, but the decomposition of water into its elements is a non-spontaneous process and can be achieved only by supplying energy from an external source, e.g. a source of e.m.f. that decomposes the water electrolytically. Furthermore, although the heat produced by the spontaneous reaction could be converted into electrical energy, the electrical... 

There is still another basic objection to using the sign of AH as a general criterion fir spontaneity. Endothermic reactions that are nonspontaneous at room temperature often become spontaneous when the temperature is raised. Consider far example, the decomposition of limestone ... 

Dibenzoylmcthane has been prepared by the hydrolysis of dibenzoyl acetic acid 1 by the slow spontaneous decomposition of acetyl dibenzoyl methane 2 by the action of metallic sodium,3 sodium ethylate,3 sodium methylate,4 alchoholic potash,4 or sodamide 5 on mixtures of acetophenone and ethyl benzoate and by the action of alcoholic potash,6 sodium methylate,7 or sodium ethylate 8 on benzalacetophenone dibromide. 

In the context of 12, the diazo keto function and the thiolactam are in proximity. This circumstance would seem to favor any process leading to the union of these two groupings. It is conceivable that decomposition of the diazo function in 12 with rhodium(n) acetate would furnish a transitory electron-deficient carbene which would be rapidly intercepted by the proximal thiolactam sulfur atom (see 20, Scheme 4). After spontaneous ring contraction of the... 

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