Hydrocarbon chain initiation reactions

Our readsorption model shows that carbon number distributions can be accurately described using Flory kinetics as long as olefin readsorption does not occur (/3r = 0), because primary chain termination rate constants are independent of chain size (Fig. 24). The resulting constant value of the chain termination probability equals the sum of the intrinsic rates of chain termination to olefins and paraffins (j8o + Ph)- As a result, FT synthesis products become much lighter than those formed on Co catalysts at our reaction conditions (Fig. 24, jSr = 1.2), where chain termination probabilities are much lower than jS -I- Ph for most hydrocarbon chains. The product distribution for /3r = 12 corresponds to the intermediate olefin readsorption rates experimentally observed on Co/Ti02 catalysts, where intrapellet transport restrictions limit the rate of removal of larger olefins, enhance their secondary chain initiation reactions, and increase the average chain size of FT synthesis products. 

Diffiisional restrictions increase the effectiveness of olefin interception sites placed within catalyst pellets. Very high olefin hydrogenation turnover rates or site densities within pellets prevent olefin readsorption and lead to Flory distributions of lighter and more paraffinic hydrocarbons. Identical results can be obtained by introducing a double-bond isomerization function into FT catalyst pellets because internal olefins, like paraffins, are much less reactive than a-olefins in chain initiation reactions. However, light paraffins and internal olefins are not particularly useful end-products in many applications of FT synthesis. Yet, similar concepts can be used to intercept reactive olefins and convert them into more useful products (e.g., alcohols) and to shift the carbon number distribution into a more useful range. In the next section, olefin readsorption model simulations are used to explore these options in the control of FT synthesis selectivity. 

Since the rate of cumene oxidation at 100° is rather high, on this system, on-visible, it is necessary to work with small concentrations of nickel catalyst, which can facilitate a high yield of the hydroperoxide [8, 39]. It is evident from analysis of scheme of catalyzed hydrocarbons oxidation, including participation of catalyst in chain initiation reaction under catalyst interaction with ROOH and also in chain propagation (Ct + RO ), that with decrease in [Ct the rate of reaction should be decreased, and [ROOH] should be increased [8, 15]. It has appeared that together with... 

If in the chain initiated reaction when v,- = const the induction period is independent of the efficiency of retardation action of the inhibitor but is determined by its concentration, then during autoxidation the inhibitor is more slowly consumed when it more efficiently terminate chains because ROOM is more slowly accumulated and the retardation period increases. Then the initiated oxidation of hydrocarbons is retarded only by compounds terminating chains. Autoxidation is retarded by compounds decomposing hydroperoxides. This decomposition, if it is not accompanied by the formation of free radicals, decreases the concentration of the accumulated hydroperoxide and, hence, the autoxidation rate. Hydroperoxide decomposition is induced by compounds of sulfur, phosphorus and various metal complexes, for example, thiophosphate, thiocarbamates of zinc, nickel, and other metals. 

The methodology for preparation of hydrocarbon-soluble, dilithium initiators is generally based on the reaction of an aromatic divinyl precursor with two moles of butyUithium. Unfortunately, because of the tendency of organ olithium chain ends in hydrocarbon solution to associate and form electron-deficient dimeric, tetrameric, or hexameric aggregates (see Table 2) (33,38,44,67), attempts to prepare dilithium initiators in hydrocarbon media have generally resulted in the formation of insoluble, three-dimensionally associated species (34,66,68—72). These precipitates are not effective initiators because of their heterogeneous initiation reactions with monomers which tend to result in broader molecular weight distributions > 1.1)... 

The first step in cracking is the thermal decomposition of hydrocarbon molecules to two free radical fragments. This initiation step can occur by a homolytic carbon-carbon bond scission at any position along the hydrocarbon chain. The following represents the initiation reaction ... 

Variable valence transition metal ions, such as Co VCo and Mn /Mn are able to catalyze hydrocarbon autoxidations by increasing the rate of chain initiation. Thus, redox reactions of the metal ions with alkyl hydroperoxides produce chain initiating alkoxy and alkylperoxy radicals (Fig. 6). Interestingly, aromatic percarboxylic acids, which are key intermediates in the oxidation of methylaromatics, were shown by Jones (ref. 10) to oxidize Mn and Co, to the corresponding p-oxodimer of Mn or Co , via a heterolytic mechanism (Fig. 6). 

Possible pathways of the degradation reaction may be visualized for a linear hydrocarbon chain in which the reaction centre ( ) is formed by the effect of initiation (heat, light, oxygen, shear stress, etc.), see Scheme la. A complementary reaction site is denoted as (-). For example, when ( ) is a free radical site, (-) is also a free radical site, if ( ) is a cation, then (-) is an anion, etc. The three stages of the reaction depicted in Scheme la, are initiation, propagation and termination, respectively. The dissociation energies of bonds situated in a /(-position to the reaction site ( ) are considerably lower than those... 

Scheme A. This scheme is typical of the hydrocarbons, which are oxidized with the production of secondary hydroperoxides (nonbranched paraffins, cycloparaffins, alkylaro-matic hydrocarbons of the PhCH2R type) [3,146]. Hydroperoxide initiates free radicals by the reaction with RH and is decomposed by reactions with peroxyl and alkoxyl radicals. The rate of initiation by the reaction of hydrocarbon with dioxygen is negligible. Chains are terminated by the reaction of two peroxyl radicals. The rates of chain initiation by the reactions of hydroperoxide with other products are very low (for simplicity). The rate of hydroperoxide accumulation during hydrocarbon oxidation should be equal to ...

This problem was first approached in the work of Denisov [59] dealing with the autoxidation of hydrocarbon in the presence of an inhibitor, which was able to break chains in reactions with peroxyl radicals, while the radicals produced failed to contribute to chain propagation (see Chapter 5). The kinetics of inhibitor consumption and hydroperoxide accumulation were elucidated by a computer-aided numerical solution of a set of differential equations. In full agreement with the experiment, the induction period increased with the efficiency of the inhibitor characterized by the ratio of rate constants [59], An initiated inhibited reaction (vi = vi0 = const.) transforms into the autoinitiated chain reaction (vi = vio + k3[ROOH] > vi0) if the following condition is satisfied. 

Tetralin hydroperoxide (1,2,3,4-tetrahydro-l-naphthyl hydroperoxide) and 9,10-dihydroanthracyl-9-hydroperoxide were prepared by oxidizing the two hydrocarbons and purified by recrystallization. Commercial cumene hydroperoxide was purified by successive conversions to its sodium salt until it no longer increased the rate of oxidation of cumene at 56°C. All three hydroperoxides were 100% pure by iodometric titration. They all initiated oxidations both thermally (possibly by the bi-molecular reaction, R OOH + RH — R O + H20 + R (33)) and photochemically. The experimental conditions were chosen so that the rate of the thermally initiated reaction was less than 10% of the rate of the photoreaction. The rates of chain initiation were measured with the inhibitors 2,6-di-ter -butyl-4-methylphenol and 2,6-di-fer -butyl-4-meth-oxyphenol. None of the hydroperoxides introduced any kinetically first-order chain termination process into the over-all reaction. 

All these reactions are highly endothermic. The products of these reactions are high calorific fuels. In nature fixation of COs is a dark process although initiated by light induced chain of reactions. Except in some special plants like rubber, C02 is still not completely reduced. Carbohydrates are the common stored products. Rubber plants produce hydrocarbons. 

Reactions (Rl) and (R12) are the two most important elementary reactions in combustion. H + O2 is the essential chain-branching reaction, while CO + OH is a chain-propagating step that regenerates the H atom from OH. Furthermore the CO + OH reaction is highly exothermic and responsible for a large fraction of the heat release that occurs in combustion of hydrocarbon fuels. Under moist conditions, reactions of CO with O and O2 are not competitive, but (RIO) may serve as an initiation step. 

The initial step in the oxidation of a hydrocarbon is substitution. For saturated hydrocarbons such as open- and closed-chain paraffins and the alkyl groups of other hydrocarbons, the substitution reaction moves by a free radical mechanism, and sets up a chain reaction. Such a reaction Ls best illustrated by halogenation. 

Hydrocarbons. The reaction of isoprene with toluene, ethylbenzene, or isopropylbenzene is catalyzed by sodium or potassium (72). The reactions are carried out at 125°C in a pressure autoclave by adding the isoprene slowly to the alkylarene in which the alkali metal is dispersed along with a trace quantity of 0-chlorotoluene which is used as a chain initiator. The products are chiefly monopentenylated in the side chain, and no information can be obtained on whether the addition is 1,4- or 1,2- since under these conditions the double bond migrates. The alkene products subsequently are reduced to alkanes by hydrogenation using 5% palladium on charcoal as catalyst. 

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