Acetylene dissociation

Acetylene black is derived from feeding acetylene into high-lempcralure retorts whereupon the acetylene dissociates into carbon and hydrogen. This reaction is exothermic (other carbon black processes arc endothermic). Temperature control of the furnace is effected by throttling the acetylene feed. 

Fig. 14. Variation in the rate constants for electron impact acetylene dissociation, methane dissociation, argon ionization and argon metastables formation along the axis of the tube.

Chemical kinetics of methane and acetylene dissociation and other gas phase reactions are studied for him coating applications under atmospheric pressure plasma conditions. In order to determine the plasma parameters, OES, V-I measurement, micro-photography and numerical simulations are used. From the determined EVDF and n, electron impact plasma chemical reaction rates are determined. On the basis of rate of different possible reaction. 

There are many compounds in existence which have a considerable positive enthalpy of formation. They are not made by direct union of the constituent elements in their standard states, but by some process in which the necessary energy is provided indirectly. Many known covalent hydrides (Chapter 5) are made by indirect methods (for example from other hydrides) or by supplying energy (in the form of heat or an electric discharge) to the direct reaction to dissociate the hydrogen molecules and also possibly vaporise the other element. Other known endothermic compounds include nitrogen oxide and ethyne (acetylene) all these compounds have considerable kinetic stability. 

A considerable amount of carbon is formed in the reactor in an arc process, but this can be gready reduced by using an auxiUary gas as a heat carrier. Hydrogen is a most suitable vehicle because of its abiUty to dissociate into very mobile reactive atoms. This type of processing is referred to as a plasma process and it has been developed to industrial scale, eg, the Hoechst WLP process. A very important feature of a plasma process is its abiUty to produce acetylene from heavy feedstocks (even from cmde oil), without the excessive carbon formation of a straight arc process. The speed of mixing plasma and feedstock is critical (6). 

In the case of 1,3-diphenylisoindole (29), Diels-Alder addition with maleic anhydride is readily reversible, and the position of equilibrium is found to be markedly dependent on the solvent. In ether, for example, the expected adduet (117) is formed in 72% yield, whereas in aeetonitrile solution the adduet is almost completely dissociated to its components. Similarly, the addition product (118) of maleic anhydride and l,3-diphenyl-2-methjdi.soindole is found to be completely dissociated on warming in methanol. The Diels-Alder products (119 and 120) formed by the addition of dimethyl acetylene-dicarboxylate and benzyne respectively to 1,3-diphcnylisoindole, show no tendency to revert to starting materials. An attempt to extrude carbethoxynitrene by thermal and photochemical methods from (121), prepared from the adduct (120) by treatment with butyl-lithium followed by ethyl chloroform ate, was unsuccessful. 

Increase in flame temperature often leads to the formation of free gaseous atoms, and for example aluminium oxide is more readily dissociated in an acetylene-nitrous oxide flame than it is in an acetylene-air flame. A calcium-aluminium interference arising from the formation of calcium aluminate can also be overcome by working at the higher temperature of an acetylene-nitrous oxide flame. 

Although collision-stabilized reaction complexes take part in chain propagation, the complex spectra of ions observed for ethylene and acetylene suggest that this mechanism undoubtedly must compete with consecutive reactions of species produced by unimolecular dissociation of the complexes and by collisional dissociation of other ions. ... 

Application to Ethylene Radiolysis. The predominant ions in the mass spectrum of ethylene (1) are ethylene, vinyl, and acetylene ions, which together account for over 85% of the total ionization. A total of 38% of all ions are C2H4+, and since kF(ethylene) = 25.9 e.v./ion pair, the parent ion should be produced with a yield of at least 1.5 ions/100 e.v. absorbed in ethylene. Similar calculations for the probable yields of the other major ions lead to estimates of 0.96 vinyl ions/100 e.v. and 0.94 acetylene ions/100 e.v. Successive dissociations are relatively unimportant in ethylene. 

Acetylene Ion. No evidence for the contribution of ion-molecule reactions originating with acetylene ion to product formation has been obtained to date. By analogy with the two preceding sections, we may assume that the third-order complex should dissociate at pressures below about 50 torr. Unfortunately, the nature of the dissociation products would make this process almost unrecognizable. The additional formation of hydrogen and hydrogen atoms would be hidden in the sizable excess of the production of these species in other primary acts while the methyl radical formation would probably be minor compared with that resulting from ethylene ion reactions. The fate of the acetylene ion remains an unanswered question in ethylene radiolysis. 

The total yield of hydrogen under the conditions of these measurements was about 1.6 molecules/100 e.v. If one-half resulted from the primary dissociation also leading to acetylene ion, a yield of 0.8 acetylene ions/100 e.v. may be estimated. This value is a minimum since acetylene ion production can also be accompanied by hydrogen atom formation and is highly uncertain but consistent with the mass spectral fragmentation pattern of acetylene and W which lead to an estimate of ca. 0.94 acetylene ions/100 e.v. 

The reaction takes place probably by a kind of inverse Wittig reaction , corresponding to the thermal dissociation of an oxaphosphetene resulting from a [2+2] cycloaddition between the phosphine oxide and the activated acetylenic compounds (Scheme 2) [11,12]. 

Chiral lactones were also obtained by cyclocarbonylation of chiral acetylenic alcohols with Pd and thiourea (H2NCSNH2) (Scheme 32). No loss in chirality was observed, but large amounts of Pd and thiourea were used (10 mol %) since the catalyst deactivates by forming metal particles. The catalytic precursor (Pdl2 > PdCl2) and the ratio of thiourea to Pd were very important, thiourea being necessary for this reaction. The active species was supposed to be [Pd(thiourea)3l]I, which forms in situ from [Pd(thiourea)4]l2 and [Pd(thiourea)2]l2. It had to be a partially dissociated species since [Pd(thiourea)4](Bp4)2 was inactive [121]. 

In the free state acetylene can decompose violently, e.g. above 9psig (0.62 bar) undissolved (free) acetylene will begin to dissociate and revert to its constituent elements. This is an exothermic process which can result in explosions of great violence. For this reason acetylene is transported in acetone contained in a porous material inside the... 

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